TW201807224A - Method for forming a film on a metal surface - Google Patents

Abstract

The present invention provides a method for forming a film on a metal surface, which is able to form a homogeneous polymer thin film on the metal surface having an excellent durability and high mold release ability, so that it can to maintain the film surface functionality, while withstanding long duration use. The method for forming a film on a metal surface is characterized in that the resin surface is irradiated using a quantum beam; and followed by immersing the said quantum beam-irradiated resin in a solution which is prepared by dissolving a triazine thiol derivative represented by the following chemical formula 1 or chemical formula 2 having a concentration from over 5 g/l and less than 13 g/l, and thereby a modified resin is prepared on which the surface of resin is decorated by the above triazine thiol derivative; the said modified resin is film-formed on the metal surface using a vacuum vapor deposition method to form a modified resin film; and then followed by film-forming another resin layer using the above vacuum vapor deposition method to arrange a laminated resin layer, the resin used here is the same kind of resin as previously used in the decoration using triazine thiol derivative.

Description

Method for forming coating on metal surface

The present invention relates to a method for forming a coating on a metal surface, and more particularly, to a vacuum vapor deposition method using a dry method in combination. A method for forming a surface film of a metal having excellent mold release properties and durability.

Previously, methods for improving the mold releasability of a mold for molding a resin product include performing film molding, applying a mold release agent to a mold, or adding a mold release agent to a molding material.

However, in the case of film molding, there are problems that the thickness or shape of the product is limited, there are many parts of the film that cannot be used as the product, the manufacturing cost increases, and the workability of removing the product from the film decreases. In the case of a mold for an optical product, it is required to be on the surface of the molded product. Although a fine shape is formed, the problem that the transferability deteriorates occurs.

In addition, when a mold release agent is applied to a mold, problems such as adhesion of the mold release agent to a product or environmental pollution may occur, and when a mold release agent is added to a molding material, a product may occur. Problems with reduced characteristics or mold contamination.

On the other hand, instead of applying a mold release agent to a mold, film formation of a mold is also performed to improve mold release properties. Such films include: TiC, TiCN, DLC, fluorine polymer film, nickel fluoride film, nickel containing PTFE, self-lubricating chromium plating, and the like. However, the thickness of these coatings is several μm or more, which makes them unsuitable for manufacturing high-precision optical products.

Therefore, if high-precision products such as LEDs (light-emitting diodes) or optical products such as microlens array films (MLAF) are to be molded, the formation method of the metal surface film is required to have a thickness of tens of nm or less. The film has good mold release properties, can form a thin film with a uniform thickness on the mold surface, has high durability, and has a small work load on film formation.

Regarding such a metal surface treatment method, for example, a technique disclosed in Patent Document 1 (Japanese Patent Laid-Open No. 11-140626) or Patent Document 2 (Japanese Patent Laid-Open No. 2002-542392) is known. . These technologies are, for example, those in which a triazine-containing organic monomer is formed on a metal surface under a vacuum technology, and is subjected to a polymerization reaction under heat or radiation to be converted into a polymer film. In addition, regarding previous technologies , There are those disclosed in Patent Document 3 (Japanese Patent Laid-Open No. 2004-9340) or Patent Document 4 (Japanese Patent Laid-Open No. 2004-14584). These techniques are, for example, attaching a triazinethiol derivative to a metal surface by a vacuum vapor deposition method, and then irradiating with heat or ultraviolet rays, etc., while forming a fluororesin on the vapor deposition film of the triazinethiol derivative. And so on.

By the way, if it is a conventional metal surface treatment method, for example, a mold for packaging a semiconductor or a light-emitting diode (LED) with an epoxy resin or a silicon-based resin by heat curing is used, A polymer film is obtained by intermolecular reaction of a triazine thiol derivative, but the crosslinking between its polymers may not achieve satisfactory results, and there is a problem of lack of strength or durability of the film itself. The method of forming a functional film is still insufficient.

In addition, the release properties of the individual films disclosed in Patent Documents 1 or 2 are not sufficiently developed. On the other hand, the release properties of the two-layer films disclosed in Patent Documents 3 or 4 are slightly changed. Although it is good, it is difficult to deposit the film on the rising part or the edge part of the mold, and there is a problem that the uniform film-forming property of the mold for the fine-shaped part is not good.

[Previous Technical Literature] (Patent Literature)

[Patent Document 1] Japanese Patent Laid-Open No. 11-140626

[Patent Document 2] Japanese Patent Publication No. 2002-542392

[Patent Document 3] Japanese Patent Laid-Open No. 2004-9340

[Patent Document 4] Japanese Patent Laid-Open No. 2004-14584

The present invention has been made in view of the problems described above, and an object thereof is to provide a method for forming a film on a metal surface, which can form a uniform film on a metal surface with excellent durability and high release. It is moldable, and on the one hand, it can maintain the functionality of the film surface. At the same time, the film can withstand long-term use and can be used for a wide range of applications.

The present invention has the following technical features:

(1) The method for forming a coating on a metal surface of the present invention is characterized in that a quantum beam is irradiated on a resin surface, and a triazinethiol derivative represented by the following formula 1 or 2 is 5 g / l or more In addition, a solution obtained by dissolving at a concentration of 13 g / l or less is impregnated with a resin irradiated with a quantum beam, so that the surface of the resin is modified by decorating with a triazine thiol derivative. Resin, the modified resin is film-forming on a metal surface by a vacuum vapor deposition method to form a modified resin film, which Next, a resin film is formed on the modified resin film by a vacuum vapor deposition method to form a resin film, thereby providing a laminated resin layer.

(However, R ₁ is an alkyne (-CH = CH-) or an olefin (-C≡C-); R ₂ 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); M ₁ or M ₂ represents H or an alkali metal).

(However, M ₁ , M ₂ , and M ₃ represent H or an alkali metal).

(2) The method for forming a film on a metal surface according to the item (1), wherein the resin is a fluorine-containing organic compound, and the fluorine-containing organic compound has an amine group (-NH ₂ ) and amidine in the molecule. (-CONH ₂ ) or unsaturated bond.

(3) The method for forming a film on a metal surface according to the item (1) or (2), wherein the resin for forming the resin film on the modified resin film is the same as that used in the triazinethiol The same resin used for the decoration of the derivatives.

(4) The method for forming a film on a metal surface according to any one of the items (1) to (3), wherein the decorated resin and the triazinethiol derivative are compared with the triazine The thiol derivative is 140 ml of a solution prepared by dissolving at a concentration of 5 g / l or more and 13 g / l or less, so that the quantum-irradiated resin becomes a ratio of 50 g.

(5) The method for forming a film on a metal surface according to any one of the items (1) to (4), wherein the solution is selected from the group consisting of cyclohexane and benzene by mixing with water or water. A solution of at least one of the group consisting of carbon tetrachloride and diethyl ether as a solvent is a solution obtained by dissolving a triazinethiol derivative, so that the solution is at a temperature of 10 to 45 ° C. The resin was immersed in the solution for more than 8 hours.

(5) The method for forming a film on a metal surface according to any one of the items (1) to (5), wherein vacuum vapor deposition is performed after heating the metal substrate in advance.

According to the method for forming a coating film on a metal surface of the present invention, a coating film of a modified resin decorated with a triazinethiol derivative on the surface of the resin is formed on the metal surface by a dry method. By forming a resin laminated film by forming a resin film thereon, the formation of a crosslinked film of the resin film formed on the metal surface can be easily formed, a uniform film can be formed, and the metal film can be formed on the metal surface. A film with high release properties and excellent durability is possible.

Further, in the method for forming a film on a metal surface, a vacuum vapor deposition method is used as a dry method, and in this vacuum vapor deposition, a heat treatment for heating a metal for forming a film is used, whereby durability can be obtained. Higher lamination.

Therefore, even if it is applied to a mold for manufacturing a nano-grade molded product, it is easy to mass-produce a molded product having a fine structure because it has excellent mold release properties and excellent durability.

Since it can be effectively used in the field of dry film formation, it is possible to use it for mass production of molded products with fine shapes such as solar cell films, battery electrode films, optical films, and cell culture films.

1‧‧‧ crucible

2‧‧‧heater

3‧‧‧ vapor deposition material

4‧‧‧ Subshutter

5‧‧‧main shutter

6‧‧‧ crystal oscillator type thickness meter

7‧‧‧ holder

8‧‧‧gas inlet valve

9‧‧‧ lamp heater

Room 10‧‧‧ (chamber)

11‧‧‧vacuum drawing valve

M‧‧‧ substrate

FIG. 1 is a schematic diagram showing an example of a vacuum vapor deposition apparatus.

Fig. 2 is a graph showing the results of durability tests depending on the number of adhesions of the resin films obtained in the examples and comparative examples.

FIG. 3 is a graph showing the relationship between the number of resin film formation times obtained in Examples and Comparative Examples and the concentration (decoration concentration) of the triazinethiol compound solution.

Fig. 4 is a graph showing the results of durability tests depending on the number of adhesions of resin films obtained in other examples and comparative examples.

Fig. 5 is a graph showing the results of durability tests depending on the number of adhesions of the resin films obtained in other examples and comparative examples.

Fig. 6 is a graph showing the results of durability tests depending on the number of adhesions of the resin films obtained in other examples and comparative examples.

Fig. 7 is a graph showing the relationship between the number of resin film formation times obtained in other examples and comparative examples and the concentration (decoration concentration) of the triazinethiol compound solution.

FIG. 8 is a schematic view of resin film formation obtained in Examples and Comparative Examples.

[Best embodiment of the present invention]

The method for forming a film on the metal surface of the present invention will be described with reference to the following embodiments, but it is not limited to these.

The method for forming a coating on a metal surface of the present invention is a method for forming a coating on a metal surface, which is characterized by irradiating a quantum beam on the surface of a resin, and secondly, applying a triazine sulfur represented by the above formula 1 or 2 The alcohol derivative is a solution prepared by dissolving at a concentration of 5 g / l or more and 13 g / l or less, and the resin irradiated with the quantum beam is immersed, so that the surface of the resin is prepared by being decorated with the aforementioned triazinethiol derivative. The modified resin is formed by forming a modified resin film on a metal surface by a vacuum vapor deposition method, and then, on the modified resin film, the resin is further formed by a vacuum vapor deposition method. The resin film is formed to form a laminated resin layer.

(Preparation of modified resin)

In the method for forming a coating on a metal surface of the present invention, first, a thin film of a modified resin is formed on the metal surface as a first layer, and the modified resin is prepared as described below.

The surface-modified resin is not particularly limited, and any thermoplastic resin or thermosetting resin available on the market can be used. Examples of the thermoplastic resin include hydrocarbon resins such as polyethylene and polypropylene; polyvinyl chloride, polyvinylidene chloride, tetrafluoropolytetrafluoroethylene (PTFE), and tetrafluoroethylene-hexafluoride polyfluorene copolymerization (FEP), any tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE), any halogen-containing resin such as fluorine-containing resin; nylon, etc. Amine resins; Polyether resins such as polyacetal; Polyfluorene, polycarbonate, polyparaxylylene Polyester resins such as ethylene glycol esters; acrylic resins such as polymethyl methacrylate and the like.

Examples of the thermosetting resin include polyimide resins, polyamido-imide resins, polyetherimide resins, epoxy resins, melamine resins, polysiloxane resins, and furan resins.

It is particularly preferable to use a fluorine-containing organic compound, and as the fluorine-containing organic compound, it is preferable to have an amine group (-NH ₂ ), a fluorene amine group (-CONH ₂ ) in the molecule, or an unsaturated group, and the molecular weight is 1,000 or more, Examples include ethylene tetrafluoride-hexafluorinated polyfluorene copolymer (FEP), ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer (PFA), and ethylene-tetrafluoroethylene copolymer (ETFE). These are used as monomers or as a mixture.

Moreover, if it has the said amine group etc. in a terminal, it is thought that it has an interaction with a triazinethiol derivative, and is suitable for use. Thereby, the bondability with a triazinethiol derivative can be improved.

Regarding the form of the resin, any form such as a resin film and a resin powder can be used.

Especially when the resin is in a powder form, for example, the average diameter D of the resin powder is in a range of D = 5 μm to 1 mm, and more preferably, the average diameter D is in a range of D = 50 μm to 500 μm.

If the average diameter is smaller than the average diameter, it is a fine powder, and the powder itself easily aggregates, which may make it difficult to uniformly dissolve the resin powder in the solvent. In addition, if the average diameter is larger than the average diameter in the above range, In this case, the ratio of the modified area of the resin powder becomes small, and it may be difficult to obtain a strong fixing strength with the metal when the film is formed. Therefore, it is preferable to use a powder resin having an average diameter in the above range.

The resin surface is preferably irradiated with a quantum beam in advance to activate the resin surface, thereby making it possible to more easily perform resin surface decoration via a triazinethiol derivative.

The quantum beam refers to all electromagnetic waves and particle rays in a broad sense. However, in the present invention, it is particularly suitable to use a quantum beam having an ionizing effect on the irradiated resin.

Examples of the quantum beam include radiation such as X-rays, γ-rays, short-wavelength ultraviolet rays, high-speed charged particle rays, and high-speed neutron rays, electron beams, ion beams, and the like.

When the resin surface is irradiated with a quantum beam, the surface of the resin irradiated with the quantum beam emits electrons to form ions, or decomposes to form radicals, thereby activating the resin surface.

The resin is preferably the resin activated by irradiating the resin surface with a quantum beam, and immersed in a solution prepared by dissolving a triazinethiol derivative, so that the triazinethiol derivative is bonded to the resin surface In this way, the resin surface is decorated to obtain a modified resin.

As the triazine thiol derivative, a triazine thiol derivative represented by the following formula 3 or 4 can be used. Effective use of -SH of triazinethiol derivatives Characteristics, it is possible to form a coating with good adhesion on the metal.

R ₁ is a substituent containing an unsaturated group such as an alkyne (-CH = CH-) and an olefin (-C≡C-). R ₂ is -CH _3, -CH ₂ -CH _3, etc. _{-C m H 2m + 1, CH} 2 CH = CH 2 , etc. _{-C m H 2m-1, CH} 2 = CH (CH 2) 4 COOCH 2 CH ₂ -CH ₂ = CH (CH ₂ ) _m COOCH ₂ CH _2- (m is an integer from 1 to 10). M ₁ and M ₂ are alkali metals such as H or Li, Na, K, and Ca.

M ₁ , M ₂ , and M ₃ are alkali metals such as H or Li, Na, K, and Ca.

Examples of the solution of the triazine thiol derivative include dissolving the triazine thiol derivative with water or by mixing at least one of cyclohexane, benzene, carbon tetrachloride, and diethyl ether as a solvent. And made a solution.

It is particularly preferred that the temperature of the solution is 10 to 45 ° C, so that the surface of the resin can be uniformly decorated with a triazinethiol derivative.

For such a solution, a solution prepared by dissolving a triazinethiol derivative at a concentration of 5 g / l or more and 13 g / l or less, preferably 6 to 13 g / l, is used to decorate the resin surface.

Thereby, the durability of the film formation of the obtained two-layer structure resin can be improved, and it can exhibit excellent mold release performance.

Next, the resin (preferably a resin irradiated with a quantum beam) is immersed in the solution, and the triazine thiol derivative contained in the solution of the triazine thiol derivative is immersed in the solution as long as it is immersed in the solution. The concentration and number of the surface of the resin sufficiently decorated can be set to any number. An example is a resin (preferably a resin having the aforementioned average diameter) irradiated with a quantum beam in 140 ml of a solution prepared by dissolving a triazinethiol derivative at a concentration of 5 g / l or more and 13 g / l or less. Dipping was performed at a ratio of 50 g. Moreover, it is preferable to perform the immersion process for 8 hours or more. With this process, the resin surface can be evenly decorated.

In addition, the surface of the resin irradiated with the quantum beam is activated, and the triazinethiol derivative can be reliably bonded to the resin surface in the solution. Sutra The surface of the resin that emits the quantum beam emits electrons to form ions or decomposes to form free radicals. The ions or radicals formed act like reaction initiators. The triazine thiol derivative in the solvent forms a thiol radical by a reaction initiator on the resin surface. The thiol radical is formed on the resin surface by a disulfide bond or an addition of an allyl group. The double bond cleavage reaction of allyl occurred. It is considered that in this way, a coupling with a thiol radical or an addition reaction to an allyl group of other molecules, etc. is caused, thereby forming a polymer film by a chemical reaction on the resin surface.

Then, the surface was dried with the aforementioned resin decorated with a triazinethiol derivative. The drying method is not particularly limited, and examples thereof include a method of evacuating to about 10 Pa in a vacuum dryer and drying at about 40 ° C. for 4 hours. When the resin is a powder, the solution can also be filtered with filter paper to separate the decorated resin powder from the liquid on the surface, and the aforementioned resin powder on the filter paper can be evacuated in a vacuum dryer to about 10 Pa, and dried at about 40 ° C for 4 hours. Thereby, a modified resin with a decorated surface can be obtained.

(Film formation of modified resin on metal surface: first layer)

The modified resin obtained in this way is film-fixed on the metal surface, and there is no particular limitation on the fixing method as long as it is a dry method, such as cold spray coating, vapor deposition by vacuum vapor deposition, and Film formation of modified resin on metal.

For example, when the modified resin is in the form of a thin film, bonding The metal surface is then fixed by heat treatment. In the case of powder, for example, a cold spray method, a vacuum vapor deposition method may be used for vapor deposition, and then the metal surface is fixed by heat treatment.

The metal is not particularly limited as long as it is a conductive metal, and examples thereof include iron and iron alloys (stainless steel, high (magnetically conductive) nickel alloys, etc.), copper and copper alloys, nickel, gold, silver, cobalt, and aluminum. , Zinc, tin and tin alloys, titanium or chromium.

The pretreatment of metal is the case where foreign matter such as organic matter is adhered. It is necessary to perform the pretreatment to remove it. However, unless the oxide and the like significantly reduce the surface conductivity, there is no problem. The activation treatment is also the same. the same.

As for the pretreatment, as long as it is a treatment capable of purifying the metal surface, a conventional treatment can be applied, and examples thereof include treatments such as immersion in acid.

As a method for forming the modified resin film on a metal subjected to a pretreatment as necessary, a dry method such as a cold spray method, a vacuum vapor deposition method, or the like can be exemplified.

As an example, a vacuum vapor deposition apparatus is used to attach a modified resin to a metal surface. The degree of vacuum is usually 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 set explicitly, it may be, for example, 200 to 400 ° C, preferably 270 to 360 ° C, and the molecular weight and The degree of vacuum and heater temperature determine the optimal vapor deposition conditions. After using an ionization vacuum gauge to adjust the inside of the vacuum vapor deposition device to a certain degree of vacuum, the crucible of the evaporation source is heated by a heater to vaporize or sublimate the modified resin. At this time, the shutter covering the substance for forming a film is closed, and the shutter covering the evaporation source is opened. Use a crystal oscillator film thickness meter to confirm that the modified resin is being vaporized or sublimated. The evaporation rate is adjusted to the desired value, and when it is adjusted appropriately, the shutter covering the substance for forming a film is opened to start vapor deposition. In this way, a predetermined film formation rate can be ensured, and uniform film formation becomes possible.

In the vapor deposition by such a vacuum vapor deposition device, the molecules of the modified resin are heated and evaporated or sublimated in a vacuum to deposit them on a solid surface such as a metal. This is a step in which many molecules can be deposited on a metal surface to make a thin film. In a vacuum, the molecules accumulated by flying from the evaporation source are formed by crystal nuclei on the solid surface, and the thin film grows due to collisions and reactions on the solid surface due to diffusion and the like. The formation of crystal nuclei that are uniformly dispersed on the solid surface will affect the subsequent film growth state, and the molecular growth is regularly performed while the film is grown.

In addition, such vapor deposition is also a step that can be used in one or more vapor depositions. In order to improve the adhesion to different shapes, it is preferred to perform vapor deposition by changing the position of the workpiece and changing the direction several times. When the thickness of the modified resin film is thick, the durability is increased.

In addition, vacuum vapor deposition is preferably performed after heating the metal substrate in advance.

By heating the metal body, the bond between the triazinethiol derivative and a resin such as a fluorine-containing organic compound can be made stronger. The heating temperature depends on the thickness of the resin and coating such as the triazinethiol derivative and the fluorinated organic compound. For example, the heating temperature can be 150 to 400 ° C, preferably 230 to 270 ° C. Particularly preferred is At about 250 ° C.

(Film formation of resin film: second layer)

On the modified resin layer film formed as described above, the resin film is formed by a dry method (for example, a vacuum vapor deposition method) by other means.

In this way, the resin film of the second layer is further formed as a coating film having a two-layer laminated structure, whereby durability can be improved and excellent mold release properties can be obtained.

Here, as the resin, any resin may be used as long as it is the resin used in preparing the modified resin, even if it is the same kind of resin as the resin used in the modified resin, or another kind of resin. There is no particular limitation on the resin. In particular, the same kind of resin as the resin used for the modified resin is used to form the second layer of the resin film. Since the durability can be further improved and the release property is more excellent, Is better. Particularly preferred is the use of fluorine-containing organic compounds.

As a vacuum vapor deposition method for forming the aforementioned resin on a modified resin layer film by a dry method, for example, a modified resin can be vapor deposited on a metal The above-mentioned vacuum vapor deposition step on the surface, whereby the vapor deposition film of the aforementioned resin (preferably a fluorine-containing organic compound) can be easily formed on the modified resin layer film.

When the resin has the aforementioned amine group or the like at the terminal, it is considered to be suitable for use because it interacts with the triazinethiol derivative on the surface of the modified resin. For example, compounds containing tertiary fluorocarbons such as FEP are also suitable for use because they have a high release effect.

More preferably, the metal solid is heated when the fluorine-containing organic compound is adhered by vacuum vapor deposition and / or after the vacuum vapor deposition film is formed, thereby allowing the triazinethiol derivative and the fluorine-containing compound on the surface of the modified resin to be modified. Organic compounds are more strongly bonded. The heating temperature depends on the material and film thickness of the triazinethiol derivative, the fluorine-containing organic compound, and the thickness of the film. For example, the heating temperature can be 150 to 400 ° C, preferably 230 to 270 ° C. Particularly preferred is At about 250 ° C.

In this way, by forming a thin film of a resin film having a two-layer structure on a metal surface according to the present invention, the formation of a crosslinked film of a polymer thin film formed on a metal surface can be easily performed, so that the The functionality of the surface of the film is obtained, and at the same time, it is possible to improve the durability in particular with regard to excellent peel resistance and long-term efficacy.

"Example"

The following examples, comparative examples, and test examples are used to illustrate the present invention, but the present invention is not limited thereto.

(1) Pre-treatment

First, the surface of a commercially available nickel substrate (purity of 99% or more manufactured by Nilac Co.) was subjected to the following pretreatment to be cleaned.

Specifically, the nickel substrate was 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. , Clean the surface of the nickel substrate.

(2) Preparation of modified resin

A powder of tetrafluoroethylene-hexafluorinated polyfluorene copolymer (FEP) having an average particle diameter D of D = 150 μm (particle diameter range: 100 to 200 μm) was put into a transparent bag, and the pressure was reduced to about 10 Pa.

As the powder of ethylene tetrafluoride-hexafluorinated polyfluorene copolymer (FEP), Teflon (registered trademark) FEP-140J (manufactured by Mitsui-DuPont Fluorine Chemical Co., Ltd.) was used.

Next, using an electron beam irradiation device (min-EB manufactured by USHIO Electric Corporation): in the decompressed vacuum, electrons obtained at a set absorption line dose of 20 kGy and an irradiation distance of 50 mm were used. The beam was irradiated for 5 minutes. The irradiation dose at this time was about 100 kGy.

Specifically, the electron beam irradiating device is an electron beam generating unit that is arranged to be heated by a filament, and has a structure that can be packaged under high vacuum. The electrons generated by the hot cathode are accelerated by a potential difference with the irradiation window (for example, an acceleration voltage of 60 kV), and the electron beam is irradiated to the resin placed on the table of the irradiation chamber through the window. In the case of resin powder, the resin powders are evenly placed side by side, and a stainless steel mesh is provided on the powders so that the powders are not scattered due to static electricity caused by irradiation. After the irradiation distance is adjusted to a predetermined height, the irradiation chamber is closed and vacuum is evacuated. When the irradiation chamber is 5 × 10 ^-2 Pa or less, the irradiation is prepared and irradiation is performed under predetermined conditions. Stop the irradiation and open the atmosphere while introducing nitrogen into the irradiation chamber.

A powdered resin of tetrafluoroethylene-hexafluorinated polyfluorene copolymer (FEP) irradiated with electron beam was dissolved in an aqueous solution (temperature: 23 ° C.) in a triazinethiol compound (DAN) represented by Formula 5 below. The resulting solution was immersed for one day and night (12 hours), and then dried to obtain a modified resin powder.

(3) Formation of a two-layer resin laminated film on a metal surface

The vacuum vapor deposition apparatus shown in FIG. 1 is used, and the surface of the nickel substrate M which has been cleaned by the above (1) is placed on the holder 7 in the chamber 10 of the apparatus. The vacuum pump 11 was started to operate via the vacuum valve 11 of the vacuum vapor deposition apparatus shown in FIG. 1. When the vacuum degree of the ionization vacuum gauge reached 5 × 10 ^-4 Pa, the temperature of the evaporation source heater 2 was adjusted to 275. ℃, when the substrate temperature is 250 ° C, the shutter 4 is opened, and it is confirmed that the film forming rate of the modified resin powder 3 obtained through the above (2) in the crucible 1 is about 0.02 nm / sec. The nickel substrate was vapor-deposited to form a film. After reaching the predetermined film-forming rate, the main shutter 5 is further opened, and the vacuum-steam deposition of the modified resin powder is measured with a crystal oscillator-type film thickness meter 6 to obtain a modified resin layer film having a constant thickness.

Next, on the nickel substrate on which the thin film of the modified resin was formed, a powder resin film of ethylene tetrafluoride-hexafluorinated polyfluorene copolymer (FEP) was further applied using the vacuum vapor deposition apparatus of FIG. 1, In the same manner, the modified resin layer film was vapor-deposited and laminated to obtain a two-layer structure resin laminated film on a nickel substrate.

(Examples 1 to 2 and Comparative Examples 1 to 3: Influence of concentration change of triazine thiol compound aqueous solution due to modified resin film)

When preparing the modified resin powder of the above (2), 50 g of a powdered resin of tetrafluoroethylene-hexafluorinated polyfluorene copolymer (FEP) irradiated with electron beam was immersed in the triazine represented by the above formula 5 The concentration (decoration concentration) of the thiol compound (DAN) aqueous solution (140ml) was adjusted to 1.0g / l (specific ratio (Comparative Example 1), 2.5 g / l (Comparative Example 2), 5.0 g / l (Comparative Example 3), 7.5 g / l (Example 1), 10.0 g / l (Example 2), etc. Modified resin powder.

Using various modified resin powders in this manner, the modified resin film was used as the first layer (thickness: about 16.8 nm) on the nickel substrate (1) as described in (3) above, The FEP resin film was made into a second layer (thickness: about 35.3 nm), whereby a two-layered resin film was formed.

(Test example 1: Durability test)

Each of the two-layer resin-formed substrates obtained in each of Examples 1 to 2 and Comparative Examples 1 to 3 described above was subjected to a subsequent test using an epoxy resin using an automatic simple molding tester (AIMT0101 manufactured by Engineering Systems Corporation). The test results of the non-continued test times are shown in Figures 2 and 3.

As the epoxy resin, a commercially available thermosetting type containing no mold release agent (trade name: NT600 manufactured by Nitto Denko Corporation) was used.

Specifically, first, two layers of a resin film-forming substrate were placed on a hot plate heated to 160 ° C. in an automatic simple molding tester for 5 minutes. A thermosetting epoxy resin (NT-600, manufactured by Nitto Denko Corporation, Ltd.) (having a size of φ 13 × 2 mm) was applied thereon and heated for 2 minutes to harden the epoxy resin. After 2 minutes, the substrate was removed from the hot plate and cooled in air.

After cooling to room temperature, the peel test load was measured by using the automatic simple molding tester described above, and the molding test was repeated. A case where the peeling load was more than 0.2 N was regarded as the next step, and a durability test on the release property was performed depending on the number of times of the second step.

The results are shown in Figures 2 and 3.

From Figures 2 and 3, it can be seen that when the modified resin is prepared by the above (2), the solution concentration of the triazine thiol compound is adjusted to 7.5 g / l or more for every 50 g of the resin on the surface. This can improve the durability of the two-layer structure resin film formed on the metal surface, and obtain excellent mold release properties.

(Examples 3 to 7, Comparative Examples 4 to 8)

When preparing the modified resin powder of the above (2), 50 g of a powdered resin of tetrafluoroethylene-hexafluorinated polyfluorene copolymer (FEP) irradiated with electron beam was immersed in the triazine represented by the above formula 5 The concentration of a thiol compound (DAN) aqueous solution (140 ml) was adjusted to 1 g / l (Comparative Example 4), 2.5 g / l (Comparative Example 5), 5 g / l (Comparative Example 6), 6 g / l (Example 3) , 7.5g / l (Example 4), 10g / l (Example 5), 12.5g / l (Example 6), 15g / l (Example 7), 20g / l (Comparative Example 7), 30g / (Comparative Example 8) and other changes to prepare each modified resin powder.

Using various modified resin powders obtained in this way, in the above (1 On a nickel substrate, a two-layered resin film is formed as described in (3) above (Fig. 8 (1): ○ indicates FEP resin).

However, the film thickness of the first layer by the modified resin is about 16 nm, the film thickness of the second layer by the FEP is about 17 nm, and the overall laminated film thickness is about 33 nm.

(Comparative Example 9: DAN layer film + FEP resin layer film)

An electrolytic solution obtained by dissolving the DAN compound (5.5 g / l) shown in the above formula 5 and the NaNO ₃ compound (7 g / l) of the electrolyte on the nickel substrate treated with the above (1) plus the electrolyte solution is put. The electrolytic solution was placed in an electrolytic cell and subjected to electrolytic treatment under the conditions of a temperature of 40 ° C., 15 minutes, and 0.8 V, thereby forming a DAN compound represented by the above formula 5 on the nickel substrate. However, in the electrolytic treatment, in the electrolytic solution tank, the metal substrate to be processed is used as the anode, and the counter electrode is used as the cathode.

After the electrolytic treatment, it was washed with water, and unreacted materials were removed and dried.

Next, on the first film on which the DAN compound was formed on the nickel substrate by the above-mentioned wet electrolytic method, a powder resin film of ethylene tetrafluoride-hexafluoride polyfluorene copolymer (FEP) was further used. In the vacuum vapor deposition apparatus shown in the figure, FEP is vapor-deposited and laminated. Thereby, a two-layer resin laminated film having a laminated structure was formed on a nickel substrate (FIG. 8 (2): ○ indicates FEP resin).

However, when the film thickness of the first layer of the DAN compound is about 5 nm and the film thickness of the second layer of the FEP is used in combination, the overall laminated film thickness is about 33 nm.

(Comparative Example 10: FEP resin layer film monomer)

On the nickel substrate treated with (1) plus, the first layer of modified resin powder is not provided, but a powder resin film of tetrafluoroethylene-hexafluorinated polyfluorene copolymer (FEP) is used. The vacuum vapor deposition apparatus of FIG. 1 vapor-deposits FEP, thereby forming a resin film having a single-layer structure of FEP on a nickel substrate (FIG. 8 (3): ○ indicates FEP resin).

However, the laminated film thickness was about 33 nm.

(Test example 2: Durability test)

The resin-formed substrates obtained in each of Examples 3 to 7 and Comparative Examples 4 to 10 described above were subjected to a subsequent test using epoxy resin using an automatic simple molding tester (AIMT0101, manufactured by Engineering Systems Corporation). The test results followed by the number of trials are shown in Figure 4 to Figure 7.

The epoxy resin used was a commercially available thermosetting type that did not contain a release agent (trade name: NT600 manufactured by Nitto Denko Corporation).

Specifically, first, two layers of a resin film-forming substrate were placed on a hot plate heated to 160 ° C. in an automatic simple molding tester for 5 minutes. A thermosetting epoxy resin (NT-600, manufactured by Nitto Denko Corporation, Ltd.) (having a size of φ 13 × 2 mm) was applied thereon and heated for 2 minutes to harden the epoxy resin. After 2 minutes, the substrate was removed from the hot plate and cooled in air.

After cooling to room temperature, the peel test load was measured by using the automatic simple molding tester described above, and the molding test was repeated. A case where the peeling load was more than 0.2 N was regarded as the next step, and a durability test on the release property was performed depending on the number of times of the second step.

The results are shown in Figures 4 to 7.

As can be understood from Figs. 4 to 7, when the modified resin is prepared by the above (2), if the concentration of the triazine thiol compound solution (decoration concentration) is adjusted to 7.5 g / l or more, the metal can be improved. The two-layer structure of the film formed on the surface of the resin has durability (more than 500 times) and excellent mold release properties.

[Industrial possibilities]

The resin film on the metal surface formed by the method for forming a film on a metal surface according to the present invention has good durability and excellent mold release properties, and can be applied to solar cell films, battery electrode films, optical films, and cell culture films. Mass production of molded products with fine shapes.

Claims (6)

A method for forming a coating on a metal surface, characterized in that a quantum beam is irradiated on a resin surface, and a triazinethiol derivative represented by the following formula 1 or 2 is 5 g / l or more and 13 g / l or less The solution obtained by dissolving the solution is immersed in a resin irradiated with a quantum beam to thereby modulate the surface of the resin to be a modified resin decorated with the aforementioned triazinethiol derivative. The modified resin is subjected to vacuum vapor. A deposition method is used to form a modified resin film on a metal surface. Secondly, on the modified resin film, the resin is further formed into a resin film by a vacuum vapor deposition method to form a resin film, thereby setting a laminated resin layer. : However, R ₁ is an alkyne (-CH = CH-) or an olefin (-C≡C-); R ₂ 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); M ₁ or M ₂ is H or an alkali metal; However, M ₁ , M ₂ , and M ₃ represent H or an alkali metal. The method for forming a film 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 amine group (-NH ₂ ) and a sulfonium amino group (- CONH ₂ ) or unsaturated bond. The method for forming a film on a metal surface according to claim 1 or 2, wherein the resin used to form the resin film on the modified resin film is the same as that used in a decorative office with a triazinethiol derivative. The same resin is used. The method for forming a coating on a metal surface according to any one of claims 1 to 3, wherein the decorated resin and the triazinethiol derivative are compared to the triazinethiol derivative. 140 ml of a solution obtained by dissolving a concentration of 5 g / l or more and 13 g / l or less makes the quantum-irradiated resin a ratio of 50 g. The method for forming and treating a metal surface according to any one of claims 1 to 4, wherein the solution is treated with water or water. A solution prepared by dissolving at least one selected from the group consisting of cyclohexane, benzene, carbon tetrachloride, and diethyl ether as a solvent to dissolve a triazinethiol derivative, so that The solution was immersed in the solution at a temperature of 10 to 45 ° C. for more than 8 hours. The method for forming a film on a metal surface according to any one of claims 1 to 5, wherein the vacuum vapor deposition is performed after heating the metal substrate in advance.