JP5651849B2 - Resin film forming method and resin film forming system - Google Patents

Description

  The present invention relates to a resin film forming method and a resin film forming system in which resin powder is fixed to the surface of a solid substrate to form a resin film.

  Conventionally, as a method for forming a resin film of this type, for example, the technique previously proposed by the inventors of the present application and the technique disclosed in Japanese Patent Laid-Open No. 2009-226329 (Patent Document 1) is known. This is a method of forming a resin film in which a resin powder is fixed to the surface of a solid substrate to form a resin film, and a treatment for binding a triazine thiol derivative to the surface of the resin powder is performed, using a cold spray method, The resin powder is put into a gas heated to a temperature lower than its melting point, and the gas is subsonic or supersonic flow and sprayed onto the solid substrate to adhere the resin to the surface of the solid substrate, and then the solid The resin attached to the substrate is heated. In the cold spray method, for example, helium gas is used as the gas. Since helium gas is a light working gas, the flow velocity can be increased, and the high kinetic energy of the spray particles can be obtained to increase the deposition efficiency.

JP 2009-226329 A

By the way, in such a method for forming a resin film, in the cold spray method, for example, helium is used as a gas. However, since helium is relatively expensive, if it can be performed using, for example, inexpensive air as a gas. More desirable. However, when air is used as a gas, the powder resin is not sufficiently fixed, so that this conventional method has a problem that air cannot be substantially used (see the experimental example in FIG. 8).
The present invention has been made in view of the above-described problems. In the cold spray method, the resin powder can be securely and firmly fixed to the solid substrate even if air is used, regardless of the gas used. It is an object of the present invention to provide a resin film forming method and a resin film forming system that improve the bond strength.

As shown in FIG. 1, the resin film forming method of the present invention for achieving such an object includes a resin film forming method in which a resin powder W is fixed to the surface of a solid substrate K to form a resin film. The resin powder W is put into a gas heated to a temperature lower than the melting point of the resin powder W by using a cold spray method (CS), and the gas is changed to a subsonic or supersonic flow to form a solid substrate K. In the method of forming a resin film in which a resin is adhered to the surface of the solid substrate K and then the resin adhered to the solid substrate K is heated, resin powder is obtained by the cold spray method. Before injecting W, the atmospheric pressure thermal non-equilibrium plasma P generated by converting the raw material gas into plasma is applied to the target portion of the solid substrate K.
The atmospheric pressure thermal non-equilibrium plasma is generated by glow discharge at a low pressure, for example, and has a high energy due to a long free path related to electrons and molecular collisions, but a plasma having a low temperature.

Thereby, when forming a resin film on a solid substrate, first, an atmospheric pressure thermal non-equilibrium plasma is irradiated to a target portion on the surface of the solid substrate. Then, resin powder is sprayed onto a target portion on the surface of the solid substrate by a cold spray method. Thereafter, the resin attached to the solid substrate is heated to attach the resin to the surface of the solid substrate. In this case, as shown in FIG. 2 (a), since the target site is irradiated with thermal non-equilibrium atmospheric pressure thermal non-equilibrium plasma, the surface of the solid substrate is physically delicate due to electron irradiation. Concavities and convexities are not formed, and functional groups such as —OH, —NH ₂ , and —COOH are chemically formed in nitrogen oxides by ion irradiation, and the affinity with the resin as a chemical effect is enhanced. The adhesive strength at the interface is improved. Therefore, even if the gas used for the cold spray method is air, for example, nitrogen, helium, etc., as well as the usual gas, adhesion is performed reliably, and the resin is securely and firmly fixed to the solid substrate. become able to. In addition, when air is used as the gas, it is less expensive than helium gas or the like and has an economic effect.
Moreover, as shown in FIGS. 2A and 2B, for example, amines and amide compounds formed on nitrogen oxides on the solid surface are electron-donating functional groups, and have, for example, electron-withdrawing performance. In the case of resin powder such as fluororesin, it is considered that the affinity acts on the solid surface and the resin surface to promote adhesion.
From the above, since the resin powder is attached to the solid substrate by low temperature spraying and then heat-treated, it is not necessary to apply an excessive heat load to the resin, so that deterioration of the resin can be suppressed as much as possible, The chemical reaction is promoted by the functional groups formed on the surface and the resin surface, and it can be surely fixed to the solid substrate.
In this case, the resin powder can be a resin powder having electron withdrawing performance.
In particular, as the resin powder, tetrafluoropolytetrafluoroethylene (PTFE), tetrafluoroethylene / hexafluoropolypyrene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), It is effective to select from at least one fluorine-containing resin of ethylene-tetrafluoroethylene copolymer (ETFE).

And it is set as the structure which repeats the irradiation of the said atmospheric pressure thermal non-equilibrium plasma, and the injection of the resin powder by the said cold spray method as needed. That is, first, the atmospheric pressure thermal non-equilibrium plasma is irradiated to the target portion on the surface of the solid substrate. Then, resin powder is sprayed onto a target portion on the surface of the solid substrate by a cold spray method. Furthermore, the atmospheric pressure thermal non-equilibrium plasma is irradiated on the surface of the resin adhered to the solid substrate. Then, a resin powder is sprayed onto the surface by a cold spray method. As described above, the atmospheric pressure thermal non-equilibrium plasma irradiation and the resin powder injection are alternately performed twice or more. Finally, the resin attached to the solid substrate is heated. As a result, as shown in FIG. 2C, since the atmospheric pressure thermal non-equilibrium plasma, which is thermal non-equilibrium, is also irradiated to the resin layer, for example, nitrogen oxide can be used without physically damaging the resin surface. In addition, for example, a functional group such as —OH, —NH ₂ , and —COOH is chemically formed to increase the affinity with the resin to be repeatedly deposited, and the adhesive strength at the interface is improved. Therefore, the resin film can be reliably grown and easily formed thick, and the resin can be securely and firmly fixed to the solid substrate.

  If necessary, air is used as the gas used in the cold spray method. It can be made cheaper than helium gas or the like. In addition, when air is used as the gas, when the atmospheric pressure thermal non-equilibrium plasma irradiation is not performed, the powder resin is not sufficiently fixed, and thus air cannot be used substantially. By irradiating, the affinity between the surface to which the resin adheres and the resin is increased and the adhesive strength at the interface is improved, so that the resin can be firmly and firmly fixed to the solid substrate.

Furthermore, the raw material gas of the atmospheric pressure thermal non-equilibrium plasma contains hydrogen as necessary. By including hydrogen, the atmospheric pressure thermal non-equilibrium plasma is more activated, and the formation of amine-based (—NH ₂ ) functional groups is particularly promoted on the solid surface, and the affinity between the solid surface and the resin is further enhanced. As a result, the adhesive strength at the interface is improved, the amount of adhesion of the resin is increased, and the solid substrate can be securely and firmly fixed.

  Furthermore, it is set as the structure provided with the powder surface treatment process which performs the process which couple | bonds a triazine thiol derivative with the surface of the resin powder injected by the said cold spray method as needed. Thereby, in the powder surface treatment step, a treatment for binding the triazine thiol derivative to the surface of the resin powder is performed. For this reason, the triazine thiol polymerized film bonded to the resin is chemically bonded to the surface of the solid substrate, and the fixing property of the resin is improved. The reason is that the thiol group at the end of the triazine thiol polymerized film gives and receives electrons from the solid when bonded to the solid. The triazine thiol with excess electrons donates the hydrogen present in the triazine ring to the solid, and the thiol group immediately becomes a thiyl radical. The formation of thiyl radicals is thought to promote chemical reactions with the solid surface. Thereby, resin is more firmly and firmly fixed to the solid substrate.

  Further, if necessary, in the powder treatment step, the resin powder is irradiated with a quantum beam, and the resin is immersed in a dispersion in which the triazine thiol derivative is dispersed, and the triazine thiol derivative is bonded to the resin surface. Yes. The quantum beam indicates all electromagnetic waves and particle beams in a broad sense, but here has an ionizing action on the irradiated resin. X-rays, γ rays Short-wavelength ultraviolet rays, fast charged particle beams, fast neutron rays and other radiation, electron beams, ion beams, and the like. This ensures that the triazine thiol derivative is bound to the resin powder. That is, when the resin powder is irradiated with a quantum beam, the resin surface is activated. The reason is that the resin surface irradiated with the quantum beam emits electrons to become ions, or decomposes to generate radicals. This is because the generated ions and radicals act as a reaction initiator, so that ionic polymerization or radical polymerization can be easily started. In addition, since the resin surface irradiated with the quantum beam is activated, triazine thiol is reliably bonded to the resin surface in the dispersion. 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 thiyl radicals by the reaction initiator on the resin surface. A thiyl radical causes a double bond cleavage reaction of an 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.

Moreover, the resin film formation system of the present invention for achieving the above object is a resin film formation system in which a resin film is formed by fixing resin powder to the surface of a solid substrate placed on a table of a machine base. ,
An atmospheric pressure plasma apparatus having an irradiation nozzle for irradiating an atmospheric pressure thermal non-equilibrium plasma generated by converting the raw material gas into plasma on the surface of the solid substrate, and applying the resin powder to a temperature lower than the melting point of the resin powder. A cold spray device that injects the gas into a warm gas and makes the gas a subsonic or supersonic flow and sprays it from the spray nozzle onto the surface of the solid substrate to attach the resin to the surface of the solid substrate;
A nozzle holding portion for holding the irradiation nozzle and the injection nozzle so that the injection ports face the surface of the solid substrate on the table and are spaced apart from each other by a predetermined distance; and the nozzle holding portion is a surface of the solid substrate. A moving mechanism that moves relative to the plane direction of XY along the surface of the solid base material, and irradiates the target portion of the solid substrate with the atmospheric pressure thermal non-equilibrium plasma from the irradiation nozzle before the resin from the injection nozzle to the target portion. The moving mechanism, the atmospheric pressure plasma device, and a control unit for controlling the cold spray device so as to inject powder are provided.

  Thus, when the resin coating is formed on the solid substrate, the control unit controls the moving mechanism, the atmospheric pressure plasma device, and the cold spray device, and the nozzle holding unit is an XY plane along the surface of the solid substrate on the table. While moving relative to the direction, the target portion on the surface of the solid substrate is irradiated with the atmospheric pressure thermal non-equilibrium plasma from the irradiation nozzle and the resin powder is sprayed from the spray nozzle to the target portion on the surface of the solid substrate. For example, first, the nozzle holding part is moved in one direction in the X direction, and at this time, atmospheric pressure thermal non-equilibrium plasma is irradiated from the irradiation nozzle. Next, the nozzle holding part is moved in one direction of the Y direction (direction from the injection nozzle to the irradiation nozzle) by an amount corresponding to the irradiation width of the atmospheric plasma or less, and then the nozzle holding part is moved to X Move in the other direction. Next, the nozzle holder is moved in one direction in the Y direction (the direction from the injection nozzle to the irradiation nozzle) by an amount corresponding to the irradiation width of the atmospheric plasma or less, and then the nozzle holding portion is Move in one direction in the X direction. In this manner, the atmospheric pressure thermal non-equilibrium plasma is irradiated in a strip shape in the X direction, and the nozzle holding portion is moved in the Y direction so that the strip-shaped irradiation site is striped. During this movement, resin powder is injected from the injection nozzle when the injection nozzle faces the irradiated portion of the atmospheric pressure thermal non-equilibrium plasma. When the nozzle holding part is sequentially moved, irradiated, and sprayed in this way, the resin film becomes a band shape in the X direction, and the band is attached in a stripe shape in the Y direction. Therefore, it becomes possible to automatically form a resin film, and to simultaneously irradiate and jet the atmospheric pressure thermal non-equilibrium plasma and the resin powder, thereby improving the adhesion efficiency of the resin.

In this case, as described above, on the surface irradiated with the atmospheric pressure thermal non-equilibrium plasma, for example, functional groups such as —OH, —NH ₂ , and —COOH are chemically formed on the nitrogen oxide, and the resin and Is enhanced, and the adhesive strength at the interface is improved. Therefore, even if the gas used for the cold spray method is air, for example, nitrogen, helium, etc., as well as the usual gas, adhesion is performed reliably, and the resin is securely and firmly fixed to the solid substrate. become able to. In addition, when air is used as the gas, it is less expensive than helium gas or the like and has an economic effect.

According to the present invention, since the target site to which the resin adheres is irradiated with atmospheric pressure thermal non-equilibrium plasma, for example, functional groups such as —OH, —NH ₂ , and —COOH are chemically added to nitrogen oxide. Thus, the affinity with the resin is increased, and the adhesive strength at the interface is improved. Therefore, even if the gas used for the cold spraying method is air, for example, as usual gas such as nitrogen and helium, the resin is surely adhered, and the resin is reliably and firmly solid substrate. It becomes possible to adhere to. In addition, when air is used as the gas, it is less expensive than helium gas or the like and has an economic effect.

It is process drawing which shows the formation method of the resin film which concerns on embodiment of this invention. It is a figure which shows the adhesion principle of resin by atmospheric pressure thermal non-equilibrium plasma irradiation in the formation method of the resin film of this invention. It is a figure which shows the electron beam irradiation apparatus used with the formation method of the resin film which concerns on embodiment of this invention. It is a figure which shows the outline of the formation system of the resin film which concerns on embodiment of this invention used with the formation method of the resin film which concerns on embodiment of this invention. It is a perspective view which shows the principal part of the formation system of the resin film which concerns on embodiment of this invention. In the system for forming a resin film according to an embodiment of the present invention, it is a plan view of a solid substrate showing movement control of an irradiation nozzle and an injection nozzle with respect to the solid substrate. It is sectional drawing of the solid base material which shows the state which made resin adhere to the solid base material by the formation system of the resin film which concerns on embodiment of this invention. It is a graph which shows the measurement result of the resin film thickness in the case of performing a cold spray with helium gas and air as a working gas about the solid base material which does not perform atmospheric pressure thermal non-equilibrium plasma processing in an experimental example. It is a graph which compares and shows the resin film thickness by the presence or absence of an atmospheric pressure thermal non-equilibrium plasma process in connection with an experiment example. It is an optical microscope photograph of the surface of the solid base material which concerns on an experiment example and shows the formation state of the resin film by the presence or absence of atmospheric pressure thermal non-equilibrium plasma treatment. It is a figure which concerns on the experiment example and shows the method of the durability test of the resin film adhering to the solid base material. It is a graph which compares and compares the durability (measurement result of a mold release load) of the resin film by the presence or absence of an atmospheric pressure thermal non-equilibrium plasma process in connection with an experimental example. It is a graph which shows the relationship between the resin spray repeatedly by cold spray, and the resin film thickness by the presence or absence of an atmospheric pressure thermal non-equilibrium plasma process in connection with an experiment example. It is an optical micrograph which compares and compares the cross section of the solid base material by the difference in the repetition frequency of an atmospheric pressure thermal non-equilibrium plasma process and cold spray concerning an experiment example. It is an optical micrograph which compares and shows the surface of a solid base material by the difference in the frequency | count of cold spray in the solid base material which does not perform an atmospheric pressure thermal non-equilibrium plasma process in connection with an experiment example. It is an optical micrograph which compares and compares the surface of the solid base material by the difference in the repetition frequency of atmospheric pressure thermal non-equilibrium plasma processing and cold spray in connection with an experimental example. It is a graph which compares and shows the measurement result of the resin film thickness by the difference in the raw material gas of atmospheric pressure thermal non-equilibrium plasma concerning an experiment example. It is a figure which shows another example of atmospheric pressure thermal non-equilibrium plasma processing and cold spray in the formation method of the resin film which concerns on embodiment of this invention.

Hereinafter, a resin film forming method and a resin film forming system according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings.
As shown in FIG. 1, the basic method of forming the resin powder according to the embodiment is to first irradiate the target portion of the solid substrate K with the atmospheric pressure thermal non-equilibrium plasma generated by converting the raw material gas into plasma, Next, using a cold spray method, the resin powder W is introduced into a gas heated to a temperature lower than its melting point, and the gas is injected into the solid substrate K in a subsonic or supersonic flow to form a solid. Resin is adhered to the surface of the substrate K. If necessary, the irradiation of the atmospheric pressure thermal non-equilibrium plasma and the spraying of the resin powder W by the cold spray method are repeatedly performed. Thereafter, the resin attached to the solid substrate K is heated (heat treated).

  The resin targeted by the method for forming a resin film according to the embodiment of the present invention may be either a thermoplastic resin or a thermosetting resin, and examples of the thermoplastic resin include hydrocarbons such as polyethylene and polypropylene. Resin, polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene tetrafluoride (PTFE), ethylene tetrafluoride / hexafluoropolypyrene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer ( PFA), halogen-containing resins such as fluorine-containing resins such as ethylene-tetrafluoroethylene copolymer (ETFE), polyamide resins such as nylon, polyether resins such as polyacetal, polyesters such as polysulfone and polycarbonate polyethylene terephthalate Resins, polymethylmethacrylate, etc. Such as Le acid resins. Examples of the thermosetting resin include polyimide resin, polyamideimide resin, polyetherimide resin, epoxy resin, melamine resin, silicon resin, and furan resin.

  The average diameter D of the resin powder W is in the range of D = 5 μm to 1 mm. Desirably, the average diameter D is in the range of D = 10 μm to 500 μm. More desirably, the average diameter D is in the range of D = 10 μm to 200 μm. A fine powder of several μm is likely to agglomerate itself and is difficult to uniformly disperse in a solvent described later. On the other hand, if it is too large, the ratio of the modified area of the powder becomes small, and it is difficult to obtain the fixing strength at the time of film formation. Further, in a cold spray apparatus to be described later, a fine powder tends to agglomerate the powder itself, and if it is large, clogging tends to occur and the supply becomes unstable. A uniform film can be obtained by supplying a uniform powder.

  Further, as the solid substrate K, iron, copper, nickel, tin, lead, cobalt, titanium, aluminum, chromium, gold, silver, platinum, palladium, zinc, any metal, cast iron, stainless steel, permalloy, brass, Examples thereof include alloys such as phosphor bronze and cupronickel, oxides of these metals, phosphate treated metals, chromate treated metals, and the like.

  Furthermore, the method for forming a resin film according to the embodiment of the present invention includes a powder surface treatment step for performing a treatment for bonding a triazine thiol derivative to the surface of the resin powder W. In this powder surface treatment step, the resin powder W is irradiated with a quantum beam, and then the resin powder W is immersed in a dispersion in which triazine thiol is dispersed to bind the triazine thiol to the resin surface. The bonded resin powder W is dried.

First, in the irradiation of the quantum beam onto the resin surface, an electron beam was used as the quantum beam. As shown in FIG. 3, the electron beam irradiation apparatus 1 has a structure in which an electron beam generator 2 heated by a filament is arranged and sealed in a high vacuum. Electrons generated at the hot cathode are accelerated by a potential difference with the irradiation window (for example, acceleration voltage 60 kV), pass through the window, and irradiate the resin W in the irradiation chamber 3 with an electron beam. The electron beam irradiation dose was in the range of 30 to 200 kGy.
Specifically, the powder used for the modification was put into a transparent bag, evacuated to about 10 Pa, and sealed with a sealer. A transparent bag (not shown) containing the powder W is passed through the irradiation device 3 by the transfer device 4 a predetermined number of times under the electron beam generation unit 2 in which the absorbed dose is set to about 20 kGy. The irradiation absorbed dose was adjusted.

Next, the resin irradiated with the quantum beam was immersed in a dispersion liquid in which the triazine thiol derivative was dispersed to bond the triazine thiol to the resin surface. The resin was immersed in the dispersion at 10 to 45 ° C. for 8 hours or longer.
The triazine thiol derivative was selected from triazine dithiol derivatives represented by the following general formula.

In the formula, R ₁ represents CH ₂ ═CHCH ₂ —, CH ₂ ═CH— (CH ₂ ) ₈ —, CH ₂ ═CH— (CH ₂ ) ₉ —, CH ₂ ═CH (CH ₂ ) ₄ COOCH ₂ CH ₂ −, CH ₂ ═CH (CH ₂ ) ₈ COOCH ₂ CH ₂ —, CH ₂ ═CH (CH ₂ ) ₉ COOCH ₂ CH ₂ —, R ₂ is CH ₂ ═CHCH ₂ —, CH _{2 = CH- (CH 2) 8} -, CH 2 = CH- (CH 2) 9 -, CH 2 = CH (CH 2) 4 COOCH 2 CH 2 -, CH 2 = CH (CH 2) 8 COOCH 2 CH ₂ −, CH ₂ ═CH (CH ₂ ) ₉ COOCH ₂ CH ₂ —. M is an alkali composed of any one of H, Li, Na, K, and Ce.

  As the dispersion liquid in which the triazine thiol derivative was dispersed, 0.5 g of 6-allylamino-1,3,5-triazine-2,4-dithiol-sodium salt was weighed into a 500 ml aqueous solution. Sufficient stirring was performed to prepare a dissolved dispersion treatment liquid. This treatment liquid was allowed to stand at room temperature for 1 hour and confirmed to be 23 ° C. The irradiated resin was put into this treatment liquid and left for one day and night (12 hours) with stirring. The liquid once treated here was discarded.

  Finally, the resin powder W bonded with triazine thiol is dried. In this resin drying, first, the dispersion was filtered with a filter paper to separate the resin powder W and the liquid. Then, the resin powder W on the filter paper was evacuated to about 10 Pa with a vacuum dryer, and was performed at about 40 ° C. for 4 hours.

In the resin film forming method according to the embodiment of the present invention, as shown in FIGS. 4 and 5, a resin film forming system S according to the embodiment of the present invention is used. In this method, the resin powder W is fixed to the surface of the solid substrate K to form a resin film.
In the resin film forming system S, the machine base 10 is provided with a table 11 on which a solid substrate K is installed. In addition, the resin film forming system S includes an atmospheric pressure plasma apparatus 20 that irradiates a surface of a solid substrate K with an atmospheric pressure thermal non-equilibrium plasma generated by converting a raw material gas into plasma, and a resin powder W. A cold spray device in which a gas heated to a temperature lower than the melting point of W is injected, and the gas is injected onto the surface of the solid substrate K in a subsonic or supersonic flow to adhere the resin to the surface of the solid substrate K. 30.

As shown in FIG. 4, the atmospheric pressure plasma apparatus 20 includes a source gas supply unit 21 that supplies a source gas, an irradiation nozzle 22 that irradiates atmospheric pressure thermal non-equilibrium plasma generated by converting the source gas into plasma, and irradiation. A high-frequency high-voltage power supply for the nozzle 22 is provided, and a controller 23 that controls the raw material gas from the raw material gas supply unit 21 and feeds it to the irradiation nozzle 22 is provided.
The source gas supply unit 21 includes a gas cylinder group 24 that can independently supply nitrogen, a mixed gas of nitrogen and hydrogen (5%), a mixed gas of nitrogen and hydrogen (20%), and the like as a source gas, and a source gas And a compressor 25 for supplying air. Any one of these gas cylinders and the compressor 25 is selected and sent to the controller 23 through a supply pipe. In the embodiment, a mixed gas of nitrogen and hydrogen (20%) is selected.
The irradiation nozzle 22 irradiates atmospheric pressure thermal non-equilibrium plasma by glow discharge under low pressure, for example.

  As shown in FIG. 4, the cold spray device 30 includes a gas supply unit 31 that supplies a high-pressure working gas, a main pipe 32 that supplies gas supplied from the gas supply unit 31, and a midway of the main pipe 32. A gas heater 33 that heats the working gas to a temperature lower than the melting point or softening temperature of the resin powder W, a branch pipe 34 branched from the main pipe 32, and a resin provided by the working gas interposed in the branch pipe 34. Connected to the powder supply apparatus 35 for conveying the powder W, the powder input pipe 36 for joining the main pipe 32 and the branch pipe 34 and introducing the resin powder W from the branch pipe 34 into the heated gas, and the powder input pipe 36 The injection nozzle 37 sprays the resin powder W onto the solid substrate K together with the gas. The gas supply unit 31 includes a gas cylinder group 38 capable of independently supplying nitrogen, helium gas, and the like as source gases, and a compressor 39 that supplies high-pressure air as working gas. Any one of these gas cylinders and the compressor 39 is selected and sent to the controller 40 through the supply pipe. In the embodiment, air is selected. Further, at the injection nozzle 37, the working gas and the resin powder W are ejected as a subsonic or supersonic flow.

Further, as shown in FIGS. 4 and 5, the resin film forming system S has the irradiation nozzle 22 and the injection nozzle 37 facing the surface of the solid base material K on the table 11 and a predetermined distance from each other. The nozzle holding unit 12 that holds them apart, the moving mechanism 13 that moves the nozzle holding unit 12 relative to the XY plane direction along the surface of the solid substrate K, and the target portion of the solid substrate K first. Control that controls the moving mechanism 13, the atmospheric pressure plasma device 20, and the cold spray device 30 so that the resin powder W is injected from the injection nozzle 37 onto the target site after the irradiation nozzle 22 irradiates the atmospheric pressure thermal non-equilibrium plasma. Part (not shown).
In the embodiment, as shown in FIG. 5, the moving mechanism 13 is configured by, for example, an XYZ rectangular coordinate robot, and has a nozzle holding unit including an irradiation nozzle 22 and an injection nozzle 37 in the action part of the robot. A portion 12 is provided.

  In the embodiment, the control unit controls the moving mechanism 13, the atmospheric pressure plasma device 20, and the cold spray device 30, and moves the nozzle holding unit 12 in the XY plane direction along the surface of the solid substrate K on the table 11. While being relatively moved, the target portion on the surface of the solid substrate K is irradiated from the irradiation nozzle 22 with the atmospheric pressure thermal non-equilibrium plasma, and the resin powder W is applied to the target portion on the surface of the solid substrate K from the spray nozzle 37. Spray.

  Specifically, as shown in FIGS. 6 and 7, for example, first, the nozzle holding unit 12 is moved in one direction in the X direction, and at this time, atmospheric pressure thermal non-equilibrium plasma is irradiated from the irradiation nozzle 22. Next, an amount corresponding to the irradiation width of the atmospheric plasma or a width equal to or less than that (in the embodiment, a pitch L that is half the irradiation width), one direction in the Y direction (the direction R from the injection nozzle 37 toward the irradiation nozzle 22). (FIG. 4)), the nozzle holding part 12 is moved, and then the nozzle holding part 12 is moved in the other direction of the X direction. Next, an air plasma irradiation width or a width less than that (in the embodiment, a pitch L that is half the irradiation width), one direction in the Y direction (the direction from the injection nozzle 37 toward the irradiation nozzle 22). R (FIG. 4)), the nozzle holder 12 is moved, and then the nozzle holder 12 is moved in one direction in the X direction. In this manner, the atmospheric pressure thermal non-equilibrium plasma is irradiated in a strip shape in the X direction, and the nozzle holding unit 12 is moved in the Y direction so that the strip-shaped irradiation site is striped. During this movement, when the injection nozzle 37 faces the irradiation part of the atmospheric pressure thermal non-equilibrium plasma, the resin powder W is injected from the injection nozzle 37 simultaneously with the irradiation of the atmospheric pressure thermal non-equilibrium plasma of the irradiation nozzle 22. To do. When the nozzle holder 12 is sequentially moved, irradiated, and sprayed in this manner, the resin film becomes a strip shape in the X direction, and the strip is attached in a striped manner in the Y direction. Therefore, the resin film can be formed automatically.

That is, in the method for forming the resin powder W according to the embodiment, first, the target site on the surface of the solid substrate K is irradiated with the atmospheric pressure thermal non-equilibrium plasma. Then, the resin powder W is sprayed onto a target portion on the surface of the solid substrate K by a cold spray method. In this case, as shown in FIG. 2A, since the target site is irradiated with atmospheric pressure thermal non-equilibrium plasma, for example, functional groups such as —OH, —NH ₂ , and —COOH are present on the nitrogen oxide. Chemically formed, the affinity with the resin is increased, and the adhesive strength at the interface is improved. For this reason, the gas used in the cold spray method is not only the gas usually used such as nitrogen and helium, but also the air used in the embodiment, so that the adhesion is surely performed, and the resin is surely and firmly strengthened. It becomes possible to adhere to the solid substrate K. Further, since air is used as the gas, it is less expensive than helium gas or the like, and has an economic effect.
As shown in FIG. 2B, for example, amines and amide compounds formed on nitrogen oxides on the solid surface are electron-donating functional groups, such as fluororesins having electron-withdrawing performance. In the case of this resin powder, it is considered that the affinity acts on the solid surface and the resin surface to promote adhesion. Furthermore, the thiol group at the end of the triazine dithiol polymerized film transmits and receives electrons from the solid when bonded to the solid by subsequent heating. The triazine dithiol with excess electrons donates the hydrogen present in the triazine ring to the solid, and immediately the thiol group becomes a thiyl radical. The formation of thiyl radicals is thought to promote chemical reactions with the solid surface. Thereby, resin is more firmly and firmly fixed to the solid substrate.

Moreover, in embodiment, irradiation of atmospheric pressure thermal non-equilibrium plasma and injection of the resin powder W by a cold spray method are performed repeatedly. That is, first, the atmospheric pressure thermal non-equilibrium plasma is irradiated onto the target portion on the surface of the solid substrate K. Then, the resin powder W is sprayed onto a target portion on the surface of the solid substrate K by a cold spray method. Further, the surface of the resin attached to the solid substrate K is irradiated with atmospheric pressure thermal non-equilibrium plasma. Then, the resin powder W is sprayed onto the surface by a cold spray method. Thus, this atmospheric pressure thermal non-equilibrium plasma irradiation and resin powder W injection are alternately performed twice or more. As a result, as shown in FIG. 2C, since the atmospheric pressure thermal non-equilibrium plasma is also applied to the resin layer, for example, functional groups such as —OH, —NH ₂ , and —COOH are chemically formed on the nitrogen oxide. Thus, the affinity with the resin that is formed and deposited in an overlapping manner is increased, and the adhesive strength at the interface is improved. Therefore, the resin film can be reliably grown and easily formed thick, and the resin can be securely and firmly fixed to the solid substrate K.

  In this case, since air is used as the gas used in the cold spray method, the cost can be reduced as compared with helium gas or the like. In addition, when air is used as the gas, when the atmospheric pressure thermal non-equilibrium plasma irradiation is not performed, the powder resin is not sufficiently fixed, and thus air cannot be used substantially. By irradiating, the affinity between the surface to which the resin adheres and the resin is increased and the adhesive strength at the interface is improved, so that the resin can be firmly and firmly fixed to the solid substrate K.

  Furthermore, since the source gas of the atmospheric pressure thermal non-equilibrium plasma is configured to include hydrogen, by including hydrogen, the atmospheric thermal thermal non-equilibrium plasma is more activated, and the affinity between the surface to which the resin adheres and the resin is further increased. As a result, the adhesive strength at the interface is improved, the amount of resin attached is increased, and the solid substrate K can be securely and firmly fixed.

Finally, the resin attached to the solid substrate K is heated. The heat treatment atmosphere may be appropriately set such as in the air or in a vacuum. As the heat source, an appropriate one such as a resistance heating type heater or a heating lamp is used. In the embodiment, the solid substrate K is placed on the heater plate and heated.
The heat treatment temperature is set to a temperature suitable for the chemical reaction of the triazine thiol derivative at the interface between the resin and the solid substrate K.
The heat treatment temperature is 280 ° C. or lower, and the temperature at which the resin powder W is deformed is appropriately selected. It is considered that the triazine thiol derivative on the surface easily associates with the temperature at which the temperature of the powder resin is deformed, and the chemical reaction is likely to occur at the interface. When the heat treatment temperature is 280 ° C. or higher, the triazine thiol derivative is decomposed, which is not preferable as the treatment temperature.
The time required for the chemical reaction at the interface is set as the heating time. For example, the heat treatment temperature in the fluororesin is preferably 230 ° C. to 270 ° C., and the treatment time is preferably about 30 minutes.
As a result, as shown in FIG. 4, since the triazine thiol derivative is bonded to these resin powders W, the triazine thiol derivative is chemically bonded to the solid substrate or between the resin powders to improve the bonding strength. As a result, the fixing property was improved.

  Furthermore, since the resin powder W is attached to the solid substrate K by low-temperature spraying (cold spray) and then heat-treated, it is not necessary to apply an excessive heat load to the resin, so that the deterioration of the resin is suppressed as much as possible. In addition, the solid substrate K can be securely fixed. As a result, the solid base material K on which the film is formed is excellent in antifouling, rust prevention, releasability and the like on the metal substrate.

Next, experimental examples will be described. In each experimental example, the atmospheric pressure thermal non-equilibrium plasma irradiation nozzle 22 and the resin powder W injection nozzle 37 were individually moved by separate moving mechanisms 13 (see FIG. 18).
[Experiment 1]
In Experimental Example 1, as the resin, a powder of tetrafluoroethylene / hexafluoropolypyrene copolymer (FEP) having an average diameter D of D = 150 μm (particle size range: 100 to 200 μm) was used.
The powder used for modification was put into a transparent bag, evacuated to about 10 Pa, and sealed with a sealer. The transparent bag containing the powder is put in the electron beam irradiation apparatus 1 in which the absorbed dose is set to about 20 kGy, and is passed twice through the irradiation chamber 3 with the transfer device under the electron beam irradiation tube 1 to make the electron Irradiated with rays. The actual irradiation absorbed dose at this time was 37 kGy. Moreover, the electron beam irradiation was outsourced.
Then, the resin powder W irradiated with the electron beam was placed in an aqueous solution of 6-allylamino-1,3,5-triazine-2,4-dithiol-monosodium salt (0.5 g / l, temperature 23 ° C.) for a whole day and night (12 Time) soaked, then washed with ethanol and dried to obtain a modified resin powder W.

  As the solid substrate K, a substrate obtained by subjecting stainless steel to hard chrome plating was used. The size of the fixed substrate was 50 × 50 mm and the thickness was 0.5 mm.

And this fixed base material was wash | cleaned with ethanol, and the cold spray was performed about each of helium and air as the working gas, without performing atmospheric pressure thermal non-equilibrium plasma processing with respect to this.
In the cold spray, the powder feed rate was adjusted to a feed rate of 2 g / min by measuring the powder fall weight per minute from the feeder. The distance between the spray nozzle 37 and the solid substrate K was 30 mm. For helium, the pressure of the carrier gas (working gas) was adjusted with a pressure regulator by opening the main stopper of the gas cylinder. In the air, the pressure increased by the compressor was adjusted with a pressure regulator.
And as shown in FIG. 8, the pressure of carrier gas was changed sequentially and it sprayed on the solid base material K prepared previously, and obtained the cold spray membrane | film | coat. The spray particle velocity obtained by changing the pressure was measured by a velocity measuring device based on laser detection.
And the result of having measured the obtained cold spray film thickness is shown in FIG. From this result, due to the fact that the particle velocity cannot be obtained with air, the solid state of the powder resin is remarkably poor with respect to the untreated solid substrate, which is about 1/4 compared with the herlium gas, and the air is substantially reduced. It was found that it could not be used.

[Experiment 2]
Experimental Example 2 uses a substrate hard-chrome plated on stainless steel as the solid substrate K,
Three types were prepared: (1) ethanol cleaning (referred to as untreated substrate) only, (2) atmospheric pressure thermal non-equilibrium plasma treatment, and (3) blast treatment.

  For the plasma treatment, a commercially available apparatus (manufactured by Nippon Plasma Treat Co., Ltd.) was used, and air as a source gas was used. The substrate surface was processed by scanning thermal non-equilibrium plasma obtained at a pressure of 0.3 Pa, a voltage of 230 V, and a current of 2.3 A at 100 mm / s, a pitch of 2 mm, and a distance of 10 mm.

  For the blasting, a commercially available device (manufactured by Fuji Seisakusho Co., Ltd.) was used, and the abrasive powder used was a rubber-like elastic body having an average particle diameter of about 2 μm mixed with SiC. The treatment was performed by uniformly irradiating the substrate surface for 2 minutes at a distance of about 20 mm with the pressure of the compressed air set at 60 KPa.

  Cold spraying was performed as follows. The amount of powder supplied was adjusted to 2.0 g / min by measuring the weight of powder falling per minute from the feeder. Air was used as the working gas, and the pressure was set to 800 KPa using a pressure regulator with the main stopper of the gas cylinder opened. A film was formed by spraying powder onto the substrate with a carrier gas temperature of 145 ° C., a spray nozzle angle of 60 degrees, a traverse speed of 200 mm / sec, a nozzle substrate distance of 30 mm, and a pitch of 1.0 mm, and a single pass.

And about each sample, the resin film thickness was measured and the result is shown in FIG. From this result, it is about 1.8 μm for the unprocessed substrate only with ethanol cleaning, about 3.7 μm for the atmospheric pressure thermal non-equilibrium plasma processing substrate, and about 1.6 μm for the blast processing substrate. It can be seen that the processing is effective.
In addition, FIG. 10 shows an optical micrograph of the surface of the solid substrate K showing a comparison of the formation state of the resin film. From this result, it can be seen that the part that appears black in the photograph shows a resin film, and the atmospheric pressure thermal non-equilibrium plasma-treated substrate in the middle photograph is evenly adhered in the plane as compared with other substrates.

  Further, as shown in FIG. 11, a resin film peeling test was performed on each sample. In this test, an epoxy resin (NT-600 manufactured by Nitto Denko Corporation) was placed on a release film forming substrate heated to 160 ° C. with a hot plate and heated for 2 minutes. After 2 minutes, the release film forming substrate was taken out of the hot plate and air-cooled. When the temperature reached room temperature, the load at which the epoxy resin separated was measured. This was repeated, and when the separating load became 5N or more, it was judged that the adhesive was adhered, and the test was stopped.

  The results are shown in FIG. From this result, it can be seen that those subjected to the atmospheric pressure thermal non-equilibrium plasma treatment were bonded 52 times for the untreated substrate and 3 times for the blasted substrate, compared to 300 times or more apart. From this, it can be seen that the resin film formed on the atmospheric pressure thermal non-equilibrium plasma processing substrate adhered firmly to the solid substrate K.

[Experiment 3]
In Experimental Example 3, the relationship between repeated resin spraying by cold spray and resin film thickness was compared with and without atmospheric pressure thermal non-equilibrium plasma treatment.
As the solid substrate K, a substrate (50 × 50 mm, thickness 0.5 mm) obtained by plating hard stainless steel was used.

  For the plasma treatment, commercially available equipment (manufactured by Nippon Plasma Treat Co., Ltd.) was used, and air compressed by a compressor as a raw material gas was used. Thermal non-equilibrium plasma obtained at a pressure of 0.3 Pa, a voltage of 230 V, and a current of 2.3 A was scanned at 100 mm / s, a pitch of 2 mm, and a nozzle-substrate distance of 10 mm.

Cold spraying was performed as follows.
The amount of powder supplied was adjusted to 2.0 g / min by measuring the weight of powder falling per minute from the feeder. Air was used as the working gas, and the pressure was set to 800 KPa using a pressure regulator with the main stopper of the gas cylinder opened. A film was formed by spraying powder onto the substrate with a carrier gas temperature of 145 ° C., a spray nozzle angle of 60 degrees, a traverse speed of 200 mm / sec, a nozzle substrate distance of 30 mm, and a pitch of 1.0 mm, and a single pass.

Then, for each sample, atmospheric pressure thermal non-equilibrium plasma treatment and cold spray were repeated, and the resin film thickness was measured for each film formation, and the results are shown in FIG. From this result, if the atmospheric pressure thermal non-equilibrium plasma treatment was not performed, it was about 2 μm after 8 repetitions. However, if atmospheric pressure thermal non-equilibrium plasma treatment and cold spray were repeated, film formation was easy, especially after the 2nd. It can be seen that the film thickness increases rapidly.
A resin film is formed on the entire surface of the substrate in the second time, and it is considered that the film formation is more easily promoted on the resin film due to powder collision relaxation.

  Further, FIG. 14 shows an electron micrograph showing a comparison of cross sections of the solid substrate K according to the difference in the number of repetitions of atmospheric pressure thermal non-equilibrium plasma treatment and cold spray. From this result, it can be seen that the film thickness was about 0.5 μm in the second time, about 5.5 μm in the fourth time, and about 18 μm in the eighth time.

FIG. 15 shows an optical micrograph showing a comparison of the surfaces of the solid substrate K due to the difference in the number of cold spray repetitions in the solid substrate K that is not subjected to the atmospheric pressure thermal non-equilibrium plasma treatment.
FIG. 16 shows an optical micrograph showing a comparison of the surface of the solid substrate K according to the difference in the number of repetitions of atmospheric pressure thermal non-equilibrium plasma treatment and cold spray.
The part that appears black in the photograph shows the resin film. From this result, it can be seen that in the solid base material that is not subjected to the atmospheric pressure thermal non-equilibrium plasma treatment, the solid substrate is confirmed even after 8 repetitions, and the resin film is not formed on the entire surface.
When the atmospheric pressure thermal non-equilibrium plasma treatment and the cold spray are repeated, the resin film covers the solid surface at the second time. This shows that the resin film is uniformly formed on the entire surface of the substrate.

[Experiment 4]
In Experimental Example 4, the difference in the resin film thickness due to the difference in the source gas of the atmospheric pressure thermal non-equilibrium plasma was observed.
For the atmospheric pressure thermal non-equilibrium plasma treatment, a commercially available apparatus (manufactured by Nippon Plasma Treat Co., Ltd.) was used, and as the raw material gas, compressed air and a gas contained in a commercially available cylinder were used. Nitrogen (N ₂ ), nitrogen mixed with 5% hydrogen, and nitrogen mixed with 20% hydrogen were used as commercial source gases. Scanning was performed under the conditions of scanning with a gas pressure of 0.3 Pa, a voltage of 230 V, a thermal non-equilibrium plasma obtained at a current of 2.3 A, 100 mm / s, a pitch of 2 mm, and a nozzle-substrate distance of 10 mm. For comparison, a sample not subjected to atmospheric pressure thermal non-equilibrium plasma treatment was prepared.

The measurement result of the resin film thickness is shown in FIG. From this result, it was found that the raw material gas containing hydrogen improves the adhesion efficiency of the resin film than the nitrogen gas alone. By including hydrogen in the source gas, the atmospheric pressure thermal non-equilibrium plasma is more activated, the formation of amine-based (-NH ₂ ) functional groups is particularly promoted on the solid surface, and the affinity between the solid surface and the resin is increased. Since it is further enhanced, it is considered that the adhesive strength at the interface has been improved, the amount of resin adhered has been increased, and the solid substrate can be firmly and firmly fixed. In the case of air, since water is contained in addition to hydrogen, an amine-based (—NH ₂ ) functional group on the solid surface is formed, and it is considered that the same effect was observed.

  In the above-described embodiment, the irradiation nozzle 22 for irradiating the atmospheric pressure thermal non-equilibrium plasma and the injection nozzle 37 for injecting the resin powder W are held in the nozzle holding unit 12, and the movement is controlled by the moving mechanism 13. Although irradiation and jetting are possible, the present invention is not necessarily limited to this. As shown in FIG. 18, first, the entire surface of the solid substrate K is irradiated with the atmospheric pressure thermal non-equilibrium plasma by the irradiation nozzle 22, Next, the resin powder W may be sprayed to the entire surface of the solid substrate K by the spray nozzle 37, and may be changed as appropriate.

  According to the present invention, it is possible to effectively use in various fields such as forming a release film on various mold surfaces, forming a release film on a coating jig, and forming a non-adhesive film on various industrial products.

K solid base material P atmospheric pressure thermal non-equilibrium plasma W resin powder 1 electron beam irradiation device S resin film forming system 10 machine base 11 table 12 nozzle holding unit 13 moving mechanism 20 atmospheric pressure plasma device 21 source gas supply unit 22 irradiation nozzle 23 Controller 24 Gas cylinder group 25 Compressor 30 Cold spray device 31 Gas supply section 32 Main pipe 33 Gas heater 34 Branch pipe 35 Powder supply apparatus 36 Powder injection pipe 37 Injection nozzle 38 Gas cylinder group 39 Compressor 40 Controller

Claims (9)

A resin film forming method in which a resin powder is fixed to the surface of a solid substrate to form a resin film, wherein the resin powder is heated to a temperature lower than the melting point of the resin powder using a cold spray method. The gas is injected into a subsonic or supersonic flow and sprayed onto the solid substrate to adhere the resin to the surface of the solid substrate, and then the resin adhered to the solid substrate is heated. In the method of forming the resin film,
A method for forming a resin film, comprising: irradiating a target portion of the solid substrate with an atmospheric pressure thermal non-equilibrium plasma generated by converting a raw material gas into plasma before injecting the resin powder by the cold spray method.   2. The method for forming a resin film according to claim 1, wherein the resin powder is a resin powder having an electron withdrawing performance.   As the above resin powder, tetrafluoropolytetrafluoroethylene (PTFE), tetrafluoroethylene / hexafluoropolypyrene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), ethylene- 3. The method for forming a resin film according to claim 2, wherein the resin film is selected from at least one of fluorine-containing resins of tetrafluoroethylene copolymer (ETFE). 4. The method for forming a resin film according to claim 1 , wherein the irradiation of the atmospheric pressure thermal non-equilibrium plasma and the spraying of the resin powder by the cold spray method are repeatedly performed. 5. The method for forming a resin film according to claim 1 , wherein air is used as a gas used in the cold spray method. 6. The method for forming a resin film according to claim 1 , wherein the source gas of the atmospheric pressure thermal non-equilibrium plasma contains hydrogen. The method for forming a resin film according to any one of claims 1 to 6 , further comprising a powder surface treatment step for performing a treatment for bonding a triazine thiol derivative to the surface of the resin powder sprayed by the cold spray method. In the powder process, the resin powder was irradiated with quantum beams, according to claim 7 in which the resin was immersed in a dispersion obtained by dispersing the triazine thiol derivative, and wherein the coupling the triazine thiol derivative in the resin surface The formation method of the resin film of description . In a resin film forming system that forms a resin film by fixing resin powder to the surface of a solid substrate placed on a table of a machine base,
An atmospheric pressure plasma apparatus having an irradiation nozzle for irradiating an atmospheric pressure thermal non-equilibrium plasma generated by converting the raw material gas into plasma on the surface of the solid substrate, and applying the resin powder to a temperature lower than the melting point of the resin powder. A cold spray device that injects the gas into a warm gas and makes the gas a subsonic or supersonic flow and sprays it from the spray nozzle onto the surface of the solid substrate to attach the resin to the surface of the solid substrate;
A nozzle holding portion for holding the irradiation nozzle and the injection nozzle so that the injection ports face the surface of the solid substrate on the table and are spaced apart from each other by a predetermined distance; and the nozzle holding portion is a surface of the solid substrate. A moving mechanism that moves relative to the plane direction of XY along the surface of the solid base material, and irradiates the target portion of the solid substrate with the atmospheric pressure thermal non-equilibrium plasma from the irradiation nozzle before the resin from the injection nozzle to the target portion A system for forming a resin film, comprising: a control unit that controls the moving mechanism, the atmospheric pressure plasma apparatus, and the cold spray apparatus so as to inject powder.