Plasma coating apparatus

Abstract

Provided is a plasma film forming apparatus capable of forming a self-organizing integrated molecular structure (hereinafter referred to as SAIMOS) and easily performing surface modification to water repellency, oil repellency, and hydrophilicity to be maintained for a long period of time by simultaneously activating a substrate surface and causing a chemical reaction of a precursor material of a molecular structure using plasma under atmospheric pressure, and further forming a new chemical bond between a functional group on the activated substrate surface and a reaction product SOLUTION: The atmospheric pressure plasma device has a configuration in which a pipe merging portion is provided in a plasma pipe having an adjusted length, a liquid raw material bubbler containing a liquid raw material of SAIMOS is connected to the pipe merging portion via a vaporized raw material pipe, piping is provided so that plasma and the vaporized raw material are mixed in the pipe merging portion, and a gas obtained by mixing the plasma and the vaporized raw material in the pipe merging portion is irradiated from an irradiation nozzle via a mixed gas pipe having an adjusted length from the pipe merging portion, thereby forming SAIMOS.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an apparatus that uses plasma to activate a substrate surface and promote a chemical reaction with a precursor material of a molecular structure, and then forms new chemical bonds between functional groups on the activated substrate surface and the reaction product to coat the molecular structure on the substrate surface, and coats the molecular structure on the substrate surface together with the chemical reaction at atmospheric pressure. [Background technology]

[0002] In automotive parts, electronics parts, and various other fields, there is a demand for surface modification treatments such as improving adhesion to adhesive layers and coating layers, and imparting hydrophilicity, water repellency, and water- and oil-repellency to resin surfaces. Therefore, plasma treatments have traditionally been used to improve adhesion to adhesive layers and coating layers, and to impart hydrophilicity, water repellency, and water- and oil-repellency to resin surfaces. Surface modification treatments such as hydrophilization, water repellency, and water- and oil-repellency are performed using vacuum plasma treatment equipment under conditions in a range of pressures significantly lower than atmospheric pressure. Hydrophilization treatments also involve plasma excitation of a plasma-generating gas at or near atmospheric pressure, and surface treatment of the treated object using the generated active species to modify the surface.

[0003] On the other hand, conventional plasma coating and plasma polymer deposition methods involve depositing materials onto a sample under vacuum, or at least under very low pressure compared to atmospheric pressure. Vacuum and reduced-pressure processes are typically performed in batch mode, while continuous processes such as roll-to-roll transfer require the installation of a transfer device inside the vacuum chamber, resulting in expensive and large-scale equipment.

[0004] Furthermore, with regard to hydrophilicity in particular, plasma treatment alone can cause changes over time, with some materials experiencing a reduction in effectiveness to about half of what it was immediately after treatment within a few hours. Recently, there has also been an increasing demand for the treatment effect to be maintained and last longer.

[0005] Patent Document 1 describes an apparatus for forming a self-assembled monolayer (hereinafter sometimes referred to as a SAM film), which is a thin film for functional coating, by a dry process, and a method for forming the SAM film, which uses vacuum plasma technology to easily carry out the entire film formation process from pre-treatment of the substrate to the completion of high-density formation of the SAM film.

[0006] In contrast, Patent Document 2 describes that in plasma polymerization under atmospheric pressure, a plasma jet is generated by passing a working gas through an excitation section, and a precursor material is supplied to the plasma jet independently of the working gas. The plasma jet passes over the surface of the substrate to be coated, and the coating process is easily carried out.

[0007] Furthermore, Patent Documents 3 and 4 describe that a water-repellent surface can be obtained by using a fluorine-containing compound gas such as CF4, C2F6, CClF3, or SF6 in a plasma treatment under atmospheric pressure.

[0008] Patent Document 5 describes that a silicon oxide film is formed by atmospheric pressure plasma chemical vapor deposition (hereinafter sometimes referred to as CVD) using oxygen as a decomposition gas and supplying a silicon compound such as hexamethyldisilazane (HMDS) as a film-forming raw material. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Publication No. 2022-151518 [Patent Document 2] Special Publication No. 2003-514114 [Patent Document 3] Japanese Patent Application Publication No. 07-118857 [Patent Document 4] Japanese Patent Application Laid-Open No. 2006-172943 [Patent Document 5] Japanese Patent Application Laid-Open No. 2010-259972 Summary of the Invention [Problem to be solved by the invention]

[0010] In recent years, in the field of surface treatment, there has been an increasing demand for surface modification such as water repellency, oil repellency, lipophilicity, hydrophilicity, and stain resistance. In particular, there has been an increasing demand for surface modification using a dry process under atmospheric pressure to achieve water repellency, oil repellency, and long-lasting hydrophilicity.

[0011] However, in Patent Document 2, the precursor material reagent is introduced close to the plasma generation section of the torch, which causes problems such as deposits easily forming on the electrode near the reagent inlet, affecting plasma generation. Furthermore, the introduction of the reagent into the high-temperature plasma jet also causes problems such as destruction of the molecular structure of the precursor material reagent. Furthermore, because the plasma jet and the reagent are irradiated onto the substrate immediately after mixing, limitations are placed on the shape of the plasma irradiation port of the torch, which limits the shape of the sample surface that can be treated.

[0012] Furthermore, in Patent Documents 3 and 4, since a fluorine-containing compound gas such as a fluorocarbon gas is used, it becomes necessary to enclose the device in a housing to prevent the fluorine-containing compound gas from leaking into the atmosphere, which requires an exhaust and recovery facility, resulting in problems such as an increase in the size of the device and costs.

[0013] Furthermore, Patent Document 5 has the problem that when a reagent such as hydrocarbon-containing silane or disilazane is supplied into atmospheric pressure plasma, the molecular structure of the reagent decomposes, forming a silicon oxide film and tending to increase surface roughness.

[0014] It is difficult to perform water-repellent treatment in the atmosphere using an atmospheric pressure plasma device without requiring large-scale exhaust and recovery equipment, and no technology has been found to solve these problems.Furthermore, no technology has been found to chemically bond molecules that retain the structure of the surface modification reagent raw materials.

[0015] The object of the present invention is to provide a plasma coating formation device that utilizes plasma under atmospheric pressure to simultaneously activate the substrate surface and cause a chemical reaction with the precursor material of the molecular structure, and then form new chemical bonds between the functional groups on the activated substrate surface and the reaction products, thereby forming self-assembling integrated molecular structures (hereinafter sometimes referred to as SAIMOS), and can easily modify the surface to make it water-repellent, oil-repellent, and hydrophilic for a long period of time. [Means for solving the problem]

[0016] The coating formation device according to the present invention has a plasma discharge unit having a pair of electrodes inside a housing, the tips of the electrodes being spaced apart, terminals for connecting a power source to the other ends of the electrodes, a gas inlet for introducing gas into the inside of the housing, and a flow passage consisting of a plasma piping for discharging the introduced gas. The atmospheric pressure plasma device irradiates plasma from the plasma piping by applying a voltage to the plasma discharge unit while flowing gas at high speed through the plasma discharge unit. The plasma piping has a pipe junction, and a raw material vaporization unit containing a liquid raw material for a self-organizing integrated molecular structure (SAIMOS) is connected to the pipe junction via a vaporized raw material piping. The pipes are arranged so that the plasma and the vaporized raw material are mixed at the pipe junction. The gas mixture of plasma and vaporized raw material at the pipe junction passes through a mixed gas piping and is irradiated from an irradiation nozzle to form SAIMOS. The coating forming device according to the present invention is characterized in that the length of the plasma piping is adjusted so that the portion from the tip of the plasma generating section where the gas is vaporized and mixed with the plasma is 30 mm or more. The coating forming apparatus according to the present invention is also characterized in that the length of the mixed gas piping is adjusted so that the length from the part where the plasma and vaporized raw material are mixed to the irradiation port is 300 mm or more and 2000 mm or less. [Effects of the Invention]

[0017] The plasma coating apparatus of the present invention utilizes atmospheric pressure plasma to simultaneously activate the substrate surface and cause a chemical reaction with the precursor material of the molecular structure, and further forms new chemical bonds between the functional groups on the activated substrate surface and the reaction products, thereby enabling the development of various surface properties such as water repellency, hydrophilicity, oil repellency, and lipophilicity. In particular, surface modification for water repellency can be performed using a light local exhaust system similar to that used for hydrophilization, without the need for a large-scale exhaust system.

[0018] Furthermore, since the plasma coating formation device of the present invention does not allow contact between the plasma generation unit and the SAIMOS raw material, it enables stable plasma generation without contaminating the electrodes near the plasma generation unit, and by mixing the SAIMOS raw material with a low-temperature radical flow, it stably promotes the chemical reaction between the plasma components and the SAIMOS raw material, protects the functional groups of the SAIMOS raw material that need to be protected, and enables the development of surface characteristics with the required functionality. [Brief explanation of the drawings]

[0019] [Figure 1] 1 is a schematic diagram showing the overall configuration of a film forming apparatus for forming a SAIMOS according to an embodiment of the present invention. [Figure 2] 1 is a cross-sectional view of a plasma generation unit of a film forming apparatus for forming a SAIMOS according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0020] Hereinafter, an embodiment of the present invention will be described. However, although the embodiment of the present invention will be described below, the present invention is not limited to this.

[0021] The film forming apparatus 1 according to this embodiment is an apparatus for forming SAIMOS on a film formation surface of a substrate.

[0022] In this embodiment, a substrate S having at least two surfaces is used as the material to be processed. The material constituting the substrate S is not particularly limited, and examples thereof include inorganic materials such as SiO2 (glass), Si, alumina, ceramic, and sapphire, and organic materials such as plastics and films. The substrate S may be a substrate that has been subjected to a wet cleaning process, or may be a member having a three-dimensional structure.

[0023] As shown in FIG. 1, the film forming device 1 includes a plasma generating unit 2 and a cylinder of plasma gas (see FIG. The plasma generating section 2 is connected to a plasma power source 4 for generating plasma in the plasma generating section 2, and a plasma pipe 5 through which the plasma generated in the plasma generating section 2 passes. The plasma generating section 2 further includes a SAIMOS raw material vaporizing section 6 for vaporizing the SAIMOS raw material, a raw material carrier gas inlet 7 for introducing a carrier gas for the SAIMOS raw material from a carrier gas cylinder (not shown) into the SAIMOS raw material vaporizing section 6, and a vaporized raw material pipe 8 through which the gas vaporized in the SAIMOS raw material vaporizing section 6 passes. Furthermore, the plasma pipe 5 and the vaporized raw material pipe 8 are connected to a plasma-vaporized SAIMOS raw material mixing section 9 in which the plasma passing through the plasma pipe 5 and the gas containing the SAIMOS raw material passing through the vaporized raw material pipe 8 are mixed, and a mixed gas pipe 10 is connected to the plasma-vaporized SAIMOS raw material mixing section 9. An irradiation nozzle 11 is installed at the tip of the mixed gas pipe 10, and SAIMOS is formed on the surface of the substrate S, which is the material to be processed, by the gas flowing out from the irradiation nozzle 11. The materials constituting the plasma pipe 5, vaporized raw material pipe 8, raw material mixer 9, mixed gas pipe 10, and irradiation nozzle 11 are not particularly limited, and examples include fluororesins such as PTFE and PFA, nylon, and the like.

[0024] In this embodiment, the plasma generating unit 2 shown in FIG. 2 includes a pair of high-voltage cables 21 connected to the plasma power source 4, a plasma gas inlet tube 22 as the plasma gas inlet 3, and a plasma electrode 23 on the extension of the pair of high-voltage power cables 21. The plasma electrodes 23 are bent and cross each other without touching each other, forming a plasma discharge unit 24, which is a space between them. A plasma gas flow path 25 is provided so that the plasma gas passing through the plasma gas inlet tube 22 flows, and the plasma discharge unit 24 is located beyond the plasma gas flow path. A heat-resistant wall 26 surrounds the plasma discharge unit 24. A plasma discharge tube 27 is connected beyond the plasma gas flow path 25 to form the plasma piping 5. The plasma generating unit 2 includes a housing 28, to which the high-voltage cable 21 connected to an external power source, the plasma gas inlet tube 22, and the plasma discharge tube 27 are connected. The materials for the plasma gas inlet tube 22 and the plasma discharge tube 27 are not particularly limited, and examples thereof include fluororesins such as PTFE and PFA, and nylon.

[0025] In this embodiment, the plasma electrode 23 is made of a high melting point metal such as a tungsten wire having a diameter of 0.75 mm, or a transition metal, in order to prevent the electrode material from becoming a thermal spray material.

[0026] In this embodiment, plasma gas passing through the plasma introduction tube 22 passes through the plasma gas flow path 25 and is supplied to the plasma discharge unit 24, where plasma is generated. The plasma generated in the plasma discharge unit 24 passes through the plasma discharge tube 27 and is discharged from the irradiation nozzle 11. By applying a high voltage to the pair of plasma electrodes 23 while N2 gas, for example, is flowing through the plasma introduction tube 22 as the plasma gas, N2 plasma is generated at atmospheric pressure in the separated plasma discharge unit 24. The applied voltage depends on the electrode spacing of the plasma discharge unit 24 and other factors. While there are precise calculation formulas, it is generally sufficient to calculate it as 1 kV / mm or more. For example, if a power supply of approximately 100 V to 30 kV is available, the electrode spacing of the plasma discharge unit 24 should be 0.1 to 30 mm. The plasma discharge unit 24 is surrounded by the heat-resistant wall 26, which is sandwiched between, for example, glass tubes. In this embodiment, the arc discharge is generated within the narrow space of the glass tubes. Therefore, the housing 28 does not need to be made of a highly heat-resistant material and can be made of an insulating resin material. The glass tubes are extremely thin, for example, 0.7 mm thick, to achieve a faster gas flow. As a result, the gas can pass through the plasma discharge unit 24 at an extremely high speed.

[0027] The gas is not particularly limited as long as it generates plasma by arc discharge, but from the viewpoint of cost, it is preferable to use inexpensive N2 gas or a gas containing N2.

[0028] Arc discharge occurs in the plasma discharge unit 24 due to dielectric breakdown, and the unit is in equilibrium with a high gas molecule temperature. However, when high-speed N2 gas is irradiated onto the plasma discharge unit 24 in this state, a region with a low gas molecule temperature is formed around the arc discharge, causing a glow discharge. The "low-temperature plasma" with a low gas molecule temperature ionized by the glow discharge is carried downstream by the high-speed gas flow and is vigorously irradiated from the irradiation nozzle 11. In other words, the irradiation nozzle 11 serves as a low-temperature plasma irradiation unit in which the occurrence of abnormal discharge (high-temperature plasma) is suppressed.

[0029] In this specification, the concepts of "high temperature" and "low temperature" of gas molecule temperatures merely represent the relative relationship of gas molecule temperatures, and are used only to mean that the temperature is lower than that of gas molecules ionized by arc discharge.

[0030] In this embodiment, the SAIMOS raw material vaporizer 6 is a liquid raw material vaporizer into which the SAIMOS raw material is injected. The SAIMOS raw material vaporizer 6 may be equipped with a mantle heater (not shown), which generates vapor of the SAIMOS raw material by heating, and supplies the vaporized SAIMOS raw material to the plasma-vaporized SAIMOS raw material mixer 9. The SAIMOS raw material vaporizer 6 may also be connected to a pipe through which bubbling gas is supplied via a flow meter (not shown) from a bubbling gas inlet 7 for carrying the vapor from the vapor source 17. N2, for example, is preferably used as the bubbling gas. Alternatively, the gas vaporized in the SAIMOS raw material vaporizer 6 may be sprayed without using bubbling gas. The SAIMOS raw material may be an evaporation source that undergoes dehydration condensation between OH groups formed on the surface of the sample S and OH groups formed by hydrolysis of the precursor material for the SAIMOS film, or an evaporation source that undergoes dehydration condensation between the OH groups formed on the surface of the sample S and the molecules of the SAIMOS precursor material themselves. For example, alkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, isobutylmethyldimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, dodecyltriethoxysilane, 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, 1H,1H,2H,2H-tridecafluorooctyltrimethoxysilane, n-octadecyltrimethoxysilane, and tetraethoxysilane (TEOS); 1H,1H,2H,2H-perfluorodecyldimethylchlorosilane; and tetrahydrooctylmethyldichlorosilane. Examples of such materials include chlorosilanes such as silane (FOMDS), dichlorodimethylsilane (DDMS), 1H,1H,2H,2H-perfluorodecyltrichlorosilane (FDTS), octadecyltrichlorosilane (OTS), and tetrahydrooctyltrichlorosilane (FOTS); phosphonic acid materials such as octadecylphosphonic acid and 1H,1H,2H,2H-perfluorooctylphosphonic acid; and disilazanes such as hexamethyldisilazane (HMDS). However, the materials are not limited to alkoxysilanes, chlorosilanes, phosphonic acid materials, and disilazanes that can form SAIMOS.However, it goes without saying that it is necessary to install an exhaust system (not shown) depending on the SAIMOS raw material used.

[0031] In this embodiment, plasma generated in the plasma discharge unit 24 of the plasma generation unit 2 passes through the plasma exhaust tube 27 and flows to the pipe junction 9 via the plasma pipe 5. The SAIMOS raw material vaporized in the SAIMOS raw material vaporization unit 6 also flows to the pipe junction 9 together with bubbling gas. At the pipe junction 9, the plasma generated in the plasma generation unit 2 and the SAIMOS raw material vaporized in the SAIMOS raw material vaporization unit 6 merge, initiating a chemical reaction between the plasma and the SAIMOS raw material molecules. The plasma mixed with the SAIMOS raw material molecules at the pipe junction 9 is transferred to a mixed gas pipe 10. In the case of alkoxysilane, for example, the alkoxy groups are converted to silanol groups. The gas mixture of the plasma and the SAIMOS precursor molecules, in which all or some of the alkoxy groups have been converted to silanol groups, is then sprayed onto the substrate S via the irradiation nozzle 11. The plasma components activate the surface of the substrate S, modifying the OH groups, and depositing the molecules that make up SAIMOS. The radical components of the plasma are much lighter than the SAIMOS precursor molecules, and because the speed of the radical components of the plasma is faster than the speed of the SAIMOS precursor, by the time the SAIMOS precursor molecules reach the surface of the substrate S, they have already activated the surface and modified the OH groups. On top of that, the SAIMOS precursor molecules self-organize through hydrogen bonds and form structures through dehydration condensation reactions, building SAIMOS.

[0032] Furthermore, in this embodiment, the plasma coating formation apparatus 1 has a length L1 of 30 mm or more, preferably 35 mm or more, from the tip of the plasma generating unit 2 through the plasma piping 5, where the plasma and vaporized SAIMOS raw material mix. This allows for stable formation of SAIMOS without the SAIMOS raw material adhering to the plasma electrode 23. In particular, by arranging the plasma piping 5, when the radical components of the plasma and the SAIMOS raw material molecules mix, the SAIMOS raw material molecules are not decomposed, and their primary molecular structure is maintained, allowing the chemical reaction to proceed at the portion where they bond with the surface of the workpiece. As a result, SAIMOS is formed.

[0033] Furthermore, in this embodiment, the plasma coating forming apparatus 1 has a cross-sectional area of ​​a flow path for a mixed gas of the plasma and the vaporized SAIMOS raw material between a portion where the plasma and the vaporized SAIMOS raw material are mixed and an irradiation port for the plasma and the SAIMOS precursor, which is set to Am (mm 2 ), mixed gas flow rate Qm (mm 3 / s), the time from mixing to discharge is Tm (s), and the length from the part where the plasma and vaporized SAIMOS raw material are mixed to the plasma and SAIMOS precursor irradiation port is L2 (mm), which is determined by the following formula (2).

number

[0034] Furthermore, in this embodiment, the plasma coating forming apparatus 1 uses a 1 / 4 tube for the mixed gas piping 10 between the part where the plasma and vaporized SAIMOS raw material are mixed and the outlet for the plasma and SAIOS precursor, and when the diameter of the flow path between the part where the plasma and vaporized SAIMOS raw material are mixed and the outlet for the plasma and SAIOS precursor is φ4.57 mm, the length L2 between the part where the plasma and vaporized SAIMOS raw material are mixed and the outlet for the plasma and SAIOS precursor is 300 mm or more and 2000 mm or less, and more preferably 400 mm or more and 1200 mm or less, it is possible to form stable SAIMOS with little variation in surface characteristics. In particular, by providing the mixed gas piping with an appropriate length, if the SAIMOS raw material is an alkoxysilane, a chemical reaction that converts alkoxy groups to silanol groups can take place in the gas mixture of the plasma radical components and the SAIMOS raw material before it reaches the surface of the workpiece, the substrate S. Furthermore, some of the converted OH groups have enough time to form intermolecular hydrogen bonds. If the distance or time until the mixed gas is exhausted is too long, the converted silanol groups may be further oxidized to form silicon-oxygen double bonds, or excessive intermolecular hydrogen bonding may result in excessive weight, making it difficult to form stable SAIMOS. [Example]

[0035] In the film forming apparatus 1 shown in FIGS. 1 and 2, glass, stainless steel (hereinafter sometimes referred to as SUS), and polyethylene terephthalate sheet (hereinafter sometimes referred to as PET) were placed as samples S, respectively. N2 was supplied as a plasma gas from the plasma gas inlet 3 to the plasma generation section 2 at a plasma gas flow rate of 65 L / min, and the plasma generated in the plasma generation section 2 was passed through the plasma gas exhaust tube 27, the plasma piping 5, and supplied to the piping confluence 9. In addition, triethoxyoctylsilane was used as the SIMOS raw material in the SAIMOS raw material vaporization section 6, and N2 was flowed as the bubbling gas at a gas flow rate of 5 L / min, and triethoxyoctylsilane was supplied to the pipe junction 9. The mixed gas of plasma and triethoxyoctylsilane that was joined at the pipe junction 9 passed through the mixed gas pipe 10 and was irradiated onto the sample S via the irradiation nozzle 11.

[0036] The length of the plasma pipe 5 of the coating forming apparatus 1 shown in FIG. 1 was adjusted to 10 mm (Comparative Example 1), 30 mm (Example 1), 35 mm (Example 2), 55 mm (Example 3), 80 mm (Example 4), and 100 mm (Example 5), and the adhesion of SAIMOS raw material to the plasma electrode 23 was examined. The surface characteristics of each sample S were then measured by water contact angle measurement (θ / 2 method) to confirm the water repellency. The length of L2 was fixed at 400 mm. As a result, the results shown in Table 1 were obtained.

[0037] [Table 1] 〇···SAIMOS is formed without any dirt adhering to the plasma electrode. △: Some dirt adheres to the plasma electrode, but SAIMOS is formed. × Dirt adheres to the plasma electrode, preventing SAMIOS from forming.

[0038] As shown in Table 1, it was confirmed that SAIMOS was formed by setting the length of L1 to 30 mm or more in Examples 1 to 5, and in particular, by setting it to 35 mm or more in Examples 2 to 5, SAIMOS was formed stably without dirt adhering to the plasma electrode 23.

[0039] Furthermore, as shown in Table 1, the length of the plasma pipe 5 of the coating forming apparatus 1 shown in FIG. 1 was adjusted, with the length of L1 in FIG. 1 being a constant 35 mm, and the length of L2 being 0 mm (Comparative Example 2), 150 mm (Comparative Example 3), 300 mm (Example 6), 400 mm (Example 7), 600 mm (Example 8), 1200 mm (Example 9), 2000 mm (Example 10), and 2200 mm (Comparative Example 4), and static contact angle measurements (θ / 2 method) with water were performed. For each sample S, the variation in contact angle measurements (n=3) was investigated. The results shown in Table 2 were obtained.

[0040] [Table 2] 〇 The variation in the measured water contact angle is within 10°. △: The variation in the measured water contact angle is greater than 10° and less than 15°. ×: The variation in the measured water contact angle is greater than 15°.

[0041] As shown in Table 2, when the length of L2 was 300 mm to 2000 mm in Examples 6 to 10, the variation in the contact angle with water was within 15°, and particularly when the length was 400 mm to 1200 mm in Examples 7 to 9, the variation was confirmed to be within 10°, confirming that SAIMOS was formed stably. [Industrial Applicability]

[0042] The coating formation device of the present invention sprays atmospheric pressure plasma onto the sample surface after a certain distance, allowing time for the atmospheric pressure plasma and SAIMOS raw material to mix and for the plasma and SAIMOS raw material to react and generate the SAIMOS precursor. This utilizes atmospheric pressure plasma to simultaneously activate the substrate surface and chemically react with the SAIMOS precursor material. This allows new chemical bonds to form between the functional groups on the activated substrate surface and the reaction product, thereby achieving various surface properties such as water repellency, hydrophilicity, oil repellency, and lipophilicity. This device is applicable to a variety of fields, including film surfaces, printed wiring boards, and other areas where surface modification using atmospheric pressure plasma processes is desired. Therefore, the implementation of this invention has a significant impact on various industries and is highly applicable. [Explanation of symbols]

[0043] 1 Film forming device 2. Plasma generation unit 3 Plasma gas inlet 4. Plasma power supply 5 Plasma piping 6 SAIMOS liquid raw material vaporizer 7 Bubbling gas inlet 8 Vaporization raw material piping 9 Pipe junction 10 Mixed gas piping 11 Irradiation nozzle 21 High voltage cable 22 Plasma gas inlet tube 23 Plasma electrode 24 Plasma discharge unit 25 Plasma gas flow hole 26 Heat-resistant walls 27 Plasma gas exhaust tube 28 Case S Sample

Claims

1. A pair of electrodes is provided inside the housing, The plasma discharge unit has the tip ends of the electrodes spaced apart from each other, a terminal for connecting a power source to the other end of the electrode, and a gas inlet for introducing a gas into the housing and a flow passage including a plasma pipe for discharging the introduced gas are provided; In an atmospheric pressure plasma device, a voltage is applied to the plasma discharge section while a high-speed gas is flowing through the plasma discharge section, thereby irradiating plasma from the plasma piping, a pipe junction is provided in the plasma pipe, and a liquid source vaporizer containing a liquid source for a self-organizing integrated molecular structure (SAIMOS) is connected to the pipe junction via a vaporized source pipe, and the plasma and the vaporized source are mixed at the pipe junction; A coating forming apparatus characterized in that a gas mixture of the plasma and the vaporized raw material at the pipe confluence is irradiated from an irradiation nozzle through a mixed gas pipe from the pipe confluence to form SAIMOS.

2. 2. The coating forming apparatus according to claim 1, A coating forming apparatus characterized in that the length of the plasma pipe is adjusted so that the portion where the plasma and the vapor are mixed from the tip of the plasma generating portion is 30 mm or more.

3. 2. The coating forming apparatus according to claim 1, The length of the mixed gas piping is adjusted so that the length L2 from the portion where the plasma and the vaporized raw material are mixed to the irradiation port, the cross-sectional area Am of the flow path for the mixed gas of the plasma and the vaporized SAIMOS raw material, the mixed gas flow rate Qm, and the time Tm from when the plasma and the vaporized SAIMOS raw material are mixed to when they are discharged satisfy the relationship of formula (1), The time Tm from when the plasma and the vaporized SAIMOS raw material are mixed to when they are discharged is 0.005[s]≦Tm≦0.030 [s] The coating forming apparatus is characterized in that it is composed of a portion for mixing the plasma filled with the gasified raw material and a length L2 from the portion to the irradiation port. [Equation 1]

4. 2. The coating forming apparatus according to claim 1, The coating forming apparatus is characterized in that the length of the mixed gas pipe is adjusted so that the length from the part where the plasma and the vaporized raw material are mixed to the irradiation port is 300 mm or more and 2000 mm or less.

Images