Patent Publication Number: US-2023140401-A1

Title: Method of manufacturing antifouling coating polymer using initiated chemical vapor deposition

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application claims the priority of Korean Patent Application No. 10-2021-0146369 filed on Oct. 29, 2021, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference. 
     BACKGROUND OF THE INVENTION 
     Field of the Invention 
     The present disclosure relates to an antifouling coating layer and, in more detail, a method of manufacturing an antifouling coating layer using iCVD. 
     Description of the Related Art 
     An antifouling characteristic is very important for sensors, lenses, or windows in an autonomous vehicle system. Technologies of implementing an antifouling surface are very various, and particularly, a superhydrophobic surface is representative of antifouling surfaces. 
     It attracts attention that having a superhydrophobic surface characteristic means having an antifouling effect against contaminants. A superhydrophobic surface can be formed using the principle that water flows down. 
     In order to form a superhydrophobic surface, there are a method of forming a nano structure and a method of forming a polymer thin film using a chemical characteristic. iCVD, which is a chemical vapor deposition process that deposit a thin film on a desired base material by generating a chemical reaction using an initiator and a monomer, is a process of forming a polymer organic thin film using a reaction between an initiator, which is vaporized by applying heat to a monomer and the initiator in a canister and is then radicalized by a filament, and the monomer positioned on a base material by the temperature difference between a substrate and the filament. 
     SUMMARY OF THE INVENTION 
     An objective of the present disclosure is to provide an antifouling coating layer, in detail, a method of manufacturing an antifouling coating layer having excellent antifouling characteristic and durability through quick deposition using iCVD. 
     In order to achieve the objectives, a method of manufacturing an antifouling coating layer according to an embodiment of the present disclosure include depositing a fluorine-based monomer, a crosslinking agent, and an initiator on a substrate by putting them into an iCVD chamber, wherein the fluorine-based monomer is one, or two or more selected from a group of C2FMA, C3FMA, C4FMA, C5FMA, C6FMA, C7FMA, and C8FMA. 
     A flow rate ratio of the fluorine-based monomer, the crosslinking agent, and the initiator that are put into an iCVD chamber may be fluorine-based monomer:crosslinking agent initiator=2:0.7˜1.5:1. 
     The crosslinking agent may be DVB (divinylbenzene) or GMA (glycidyl methacrylate). 
     The initiator may be TBPO (tert-butyl peroxide). 
     The fluorine-based monomer may have been heated at 60 to 90° C. 
     The crosslinking agent may have been heated at 30 to 45° C. 
     A flow rate of the fluorine-based monomer may be 8.4 to 10.4 sccm, a flow rate of the crosslinking agent may be 3.5 to 8 sccm, and a flow rate of the initiator may be 4.6 to 5.4 sccm. 
     The method of manufacturing an antifouling coating layer of the present disclosure has an effect that it can form a coating layer through quick deposition and has an excellent antifouling characteristic and excellent durability. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee. 
       The above and other objectives, features and other advantages of the present invention will be more clearly understood from the following detailed description when taken in conjunction with the accompanying drawings, in which: 
         FIG.  1    is a view showing vapor pressure curves of materials according to an embodiment of the present disclosure; 
         FIG.  2    is a view showing an FT-IR analysis result of an antifouling coating layer according to an embodiment of the present disclosure; 
         FIG.  3    is a view showing a contact angle analysis image of an antifouling coating layer according to an embodiment of the present disclosure; 
         FIG.  4    is a view showing a contact angle analysis result according to wear resistance analysis of an antifouling coating layer according to an embodiment of the present disclosure; 
         FIG.  5    is a view showing an analysis image according to a nano-cutting test of an antifouling coating layer according to an embodiment of the present disclosure; 
         FIGS.  6 A to  6 D  are views showing mechanical strength analysis results according to nano-cutting tests of an antifouling coating layer according to an embodiment of the present disclosure; 
         FIGS.  7 A to  7 D  are views showing SEM images according to nano-cutting tests of an antifouling coating layer according to an embodiment of the present disclosure; 
         FIGS.  8 A to  8 C  are views showing SEM images showing analysis positions when element analysis was performed on an antifouling coating layer according to an embodiment of the present disclosure; 
         FIG.  9 A  is a view showing an image of a copper (Cu) substrate that is a target of an antifouling coating layer according to an embodiment of the present disclosure; and 
         FIG.  9 B  is a view showing an FT-IR analysis result performed after forming an antifouling coating layer on the copper (Cu) substrate of  FIG.  9 A . 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Hereafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily achieve the present disclosure. However, the present disclosure may be modified in various different ways and is not limited to the embodiments described herein. 
     A method of manufacturing an antifouling coating layer according to an embodiment of the present disclosure may include depositing a fluorine-based monomer, a crosslinking agent, and an initiator on a substrate by putting them into an iCVD chamber. 
     The fluorine-based monomer, the crosslinking agent, and the initiator may be supply substances that are put into an iCVD chamber. 
     The flow rate ratio of the fluorine-based monomer, the crosslinking agent, and the initiator that are put into an iCVD chamber may be fluorine-based monomer:crosslinking agent initiator=2:0.7˜1.5:1. 
     The fluorine-based monomer may be one or, two or more selected from a group of C2FMA (2-methyl tridecafluorooctyl ester), C3FMA (3-tridecafluorooctyl methacrylate), C4FMA (4-tridecafluorooctyl methacrylate; C 4 F 9 C 2 H 4 OCOC(CH 3 )═CH 2 ), C5FMA (5-tridecafluorooctyl methacrylate), C6FMA (6-tridecafluorooctyl methacrylate or 2-(perfluorohexyl)ethyl methacrylate; C 6 F 13 C 2 H 4 OCOC(CH 3 )═CH 2 ), C7FMA (7-tridecafluorooctyl methacrylate) and C8FMA (8-tridecafluorooctyl methacrylate; C 8 F 17 C 2 H 4 OCOC(CH 3 )═CH 2 ). 
     The fluorine-based monomer may have been heated at 60 to 90° C. 
     The flow rate of the fluorine-based monomer may be 8.4 to 10.4 sccm. 
     The supply pressure of the fluorine-based monomer may be 1200 to 1500 mTorr. 
     The crosslinking agent may be DVB (divinylbenzene) or GMA (glycidyl methacrylate). 
     The crosslinking agent may have been heated at 30 to 45° C. 
     The flow rate of the crosslinking agent may be 3.8 to 8 sccm, and preferably, may be 6.2 to 8 sccm. 
     The supply pressure of the crosslinking agent may be may be 900 to 1200 mTorr. 
     The initiator may be TBPO (tert-butyl peroxide). 
     The initiator may have been heated at 40° C. 
     The flow rate of the initiator may be 4.6 to 5.4 sccm. 
     The supply pressure of the initiator may be may be 660 to 780 mTorr. 
     The temperature of pipes for putting the fluorine-based monomer, the crosslinking agent, and the initiator into the iCVD chamber may be 75 to 100° C. 
     The temperature of the wall of the iCVD chamber may be 75 to 100° C. 
     The ratio P M /P sat  of the partial pressure P M  of each of the supply substance (a fluorine-based monomer, a crosslinking agent, and an initiator) that are supplied into the iCVD chamber and the saturation vapor pressure P sat  of the supply substances on the substrate may be 0 to 1, and in this case, the ratio P M /P sat  of the partial pressure P M  and the saturation vapor pressure P sat  is not 0 or 1. 
     The substrate may be a glass substrate, a silicon substrate, an ITO (Indium Tin Oxide) transparent electrode, or a silver nano wire (AgNW) transparent, and the temperature of the substrate may be 10 to 50° C. 
     Hereafter, the present disclosure is described in more detail through embodiments. The present disclosure is only an embodiment for understanding the present disclosure and does not the range of the present disclosure. 
     Embodiment 1. Manufacturing of Antifouling Coating Layer 
     C6FMA (C 6 F 13 C 2 H 4 OCOC(CH 3 )═CH 2 ), DVB (divinylbenzene), and TBPO (tert-butyl peroxide) are prepared as a monomer, a crosslinking agent, and an initiator, respectively, and a glass substrate (silicon substrate) is prepared as a substrate for deposition. 
     An antifouling coating layer is manufactured through an iCVD (initiated Chemical Vapor Deposition) process by the following method. 
     First, the C6FMA is heated at a temperature of 70° C. (C6FMA canister temperature), the DVB is heated at a temperature of 35° C. (DVB canister temperature), and the TPBO is heated at a temperature of 40° C. (TPBO canister temperature) through a canister. Further, the temperature of the pipe for supplying monomers (C6FMA, DVB, TPBO) into an iCVD chamber was set as 100° C., the pressure of the chamber was set as 500 mTorr, the temperature of the chamber wall was set as 100° C., the temperature of the silicon (Si wafer) substrate was set as 40° C., and the temperature of a filament was set as 180° C. 
     Thereafter, the flow rate of the C6FMA is set as 10 sccm, the flow rate of the DVD is set as 3.5 sccm, and the flow rate of the TPBO is set as 5 sccm (C6FMA:DVB:TPBO=2:0.7:1); the pressure of the C6FMA is set as 1400 mTorr, the pressure of the DVB is set as 1050 mTorr, and the pressure of the TBPO is set as 700 mTorr, whereby an antifouling coating layer having a thickness of 780 nm is manufactured on the silicon (Si wafer) substrate through deposition for 1 hour (hr). 
     Embodiment 2. Manufacturing of Antifouling Coating Layer 
     This is performed in the same way as the embodiment 1, in which the flow rate of the C6FMA is set as 10 sccm, the flow rate of the DVB is set as 7.5 sccm, and the flow rate of the TPBO is set as 5 sccm (C6FMA:DVB:TPBO=2:1.5:1). 
     Comparative Example 1. Manufacturing of PFDMA-TPBO Antifouling Coating Layer 
     PFDMA (1H, 1H, 2H, 2H-perfluorodecyl acrylate and TBPO (tert-butyl peroxide) are prepared as a monomer and an initiator, respectively, and a glass substrate (silicon substrate) is prepared as a substrate for deposition. 
     An antifouling coating layer is manufactured through an iCVD (initiated Chemical Vapor Deposition) process by the following method. 
     First, the PFDMA is heated at a temperature of 75° C. (PFDMA canister temperature) and the TPBO is heated at a temperature of 40° C. (TPBO canister temperature). Further, the temperature of the pipe for supplying monomers (PFDMA, TPBO) into an iCVD chamber was set as 100° C., the pressure of the chamber was set as 60 mTorr, the temperature of the chamber wall was set as 100° C., the temperature of the silicon (Si wafer) substrate was set as 40° C., and the temperature of a filament was set as 180° C. 
     Thereafter, the flow rate of the PFDMA is set as 3.8 sccm and the temperature of the TPBO is set as 3.8 sccm (PFDMA:TPBO=1:1); and the pressure of the PFDMA is set as 333 mTorr and the pressure of the TBPO is set as 183 mTorr, whereby an antifouling coating layer having a thickness of 780 nm is manufactured on the silicon (Si wafer) substrate through deposition for 1 hour (hr). 
     Experiment example 1. Vapor pressure curves of deposition materials A vapor pressure curve was analyzed for each of C6FMA’, ‘C4FMA’, ‘C2FMA’, and ‘PFDMA’ that are the monomers used in the embodiments 1 and 2, and the analysis results were shown in  FIG.  1   . 
     Referring to  FIG.  1   , PFDMA that was used in an iCVD process in the related art shows high pressure at high temperature, but ‘C6FMA’, ‘C4FMA’, and ‘C2FMA’ cannot obtain high pressure even at low temperature, and the higher the pressure, the larger the input amount, so a higher deposition (coating) speed can be expected. 
     Experiment Example 1. FT-IR Analysis 
     The result of performing FT-IR analysis on the antifouling coating layer manufactured in accordance with the embodiment 2 was shown in  FIG.  2   . Referring to  FIG.  2   , FR-IR analysis results of ‘pPFDMA’ composed of only PFDMA and ‘pStacked’ composed of PFDMA and V4D4 (1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane) as comparative groups were also shown, and the antifouling coating layer manufactured in accordance with the embodiment 2 was expressed as ‘pCopolymer’. 
     Referring to  FIG.  2   , it is possible to know existence of C—F (1150˜1200 cm −1 ) and existence of DVB (800˜900 cm −1 ) that is a crosslinking agent. 
     Experiment Example 3. Contact Angle Analysis 
     Contact angles of the antifouling coating layers manufactured in accordance with the embodiments 1 and 2 were analyzed by a contact angle measurer (PHOENIXP-30) and the analysis images were shown in  FIG.  3    ((a) of  FIG.  3   : embodiment 1 and (b) of  FIG.  3   : embodiment s). 
     The contact angle of the antifouling coating layer according to the embodiment 1 is 118° according to the embodiment 1 and the contact angle of the antifouling coating layer according to the embodiment 2 is 117°. Meanwhile, the contact angle of the PFDMA-TPBO antifouling coating layer according to the comparative example 1 is 142.1°. 
     Experiment Example 4. Wear Resistance Analysis 
     Contact angle analysis according to sliding cycles (1 kgf, 3000 cycle) were performed on the antifouling coating layer manufactured in accordance with the embodiments 1 and 2, and ‘pPFDMA’ composed of only PFDMA and ‘V4D4-PFDMA’ composed of PFDMA and V4D4 (1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane) as comparative groups through an electronic rubbing tester, and the analysis results were shown in  FIG.  4   . 
     Referring to  FIG.  4   , it can be seen that the contact angle of the ‘PFDMA’ rapidly decreases as a cycle continues, and it is also can be seen that the contact angle of the ‘V4D4-PFDMA’ also slightly decreases. However, it can be seen that the contact angles of the antifouling coating layers according to the embodiments 1 and 2 does not decrease. 
     Experiment Example 5. Nano-Cutting Test 
     A wear test was performed using a wiper tip and shear strength of the coating layers were measured through a nano-cutting test to evaluate durability of the antifouling coating layers according to the embodiments 1 and 2. 
     Surface images of wear test results of 100 cycles for ‘C6FMA’ composed of only a C6FMA monomer and the antifouling coating layer according to the embodiment 2 that are comparative groups were shown in  FIG.  5   , in which, as comparative groups, (a) of  FIG.  5    is a surface image of the wear test result of 100 cycles for ‘C6FMA’ and (b) of  FIG.  5    is a surface image of the wear test result of 100 cycles for the antifouling coating layer according to the embodiment 2. 
     Further, nano-cutting test data of ‘C6FMA-V4D4’, the PFDMA-TPBO antifouling coating layer according to the comparative example 1, and the antifouling coating layers according to the embodiments 1 and 2 were shown in  FIGS.  6 A to  6 D .  FIG.  6 A  is a nano-cutting test result of the ‘C6FMA-V4D4’,  FIG.  6 B  is a nano-cutting test result of the PFDMA-TPBO antifouling coating layer according to the comparative example 1,  FIG.  6 C  is a nano-cutting test result of the antifouling coating layer according to the embodiment 1, and  FIG.  6 D  is a nano-cutting test result of the antifouling coating layer according to the embodiment 2. Further, cross-sectional SM images of the ‘C6FMA-V4D4’, the PFDMA-TPBO antifouling coating layer according to the comparative example 1, and the antifouling coating layers according to the embodiments 1 and 2 that have undergone a nano-cutting test were shown in  FIGS.  7 A to  7 C , in which  FIG.  7 A  is a cross-sectional SEM image of the ‘C6FMA-V4D4’,  FIG.  7 B  is a cross-sectional SEM image of the PFDMA-TPBO antifouling coating layer according to the comparative example 1 ((a) of  FIG.  7 B : a low-magnification SEM image and (b) of  FIG.  7 B : a high-magnification SEM image),  FIG.  7 C  is a cross-sectional SEM image of the antifouling coating layer according to the embodiment 1 ((a) of  FIG.  7 C : a low-magnification SEM image and (b) of  FIG.  7 C : a high-magnification SEM image), and  FIG.  7 D  is a cross-sectional SEM image of the antifouling coating layer according to the embodiment 2 ((a) of  FIG.  7 D : a low-magnification SEM image and (b)  FIG.  7 D : a high-magnification SEM image). 
     Surface energy (mM/m), shear strength τ s  (MPa), and a shear angle Ø (°) were measured under the condition of low vacuum of 0.015 Torr on the basis of the analysis results according to  FIGS.  6 A to  6 D  and  FIGS.  7 A  to d, and were show in the following table 1. 
     
       
         
           
               
               
               
               
             
               
                 TABLE 1 
               
               
                   
               
               
                   
                 Surface 
                 Shear 
                 Shear 
               
               
                   
                 energy 
                 strength τ s   
                 angle  ø   
               
               
                   
                 (mN/m) 
                 (MPa) 
                 (°) 
               
               
                   
               
             
            
               
                 ‘C6FMA-V4D4’ 
                 — 
                  73.6 ± 8.6 
                 18.2 ± 7.3 
               
               
                 Comparative 1 
                 — 
                  49.73 
                  9.12 
               
               
                 Embodiment 1 
                 7.33 
                  68.0 ± 12.4 
                 16.9 ± 0.2 
               
               
                 Embodiment 2 
                 8.55 
                 104.5 ± 11.7 
                 17.7 ± 4.5 
               
               
                   
               
            
           
         
       
     
     Referring to  FIGS.  5   a  to  5   c   ,  FIGS.  6 A to  6 C , and the table 1, it can be seen that the antifouling coating layer according to the embodiment 2 has a contact angle of 117° and shear strength of 104.5 MPa, it has excellent antifouling characteristic and durability. 
     Embodiment 6. Element Analysis 
     Element analysis was performed through EDX (Energy Dispersive X-ray Spectroscopy) at certain points in cross-sections of the PFDMA-TPBO antifouling coating layer according to the comparative example 1 and the antifouling coating layers according to the embodiments 1 and 2. 
       FIG.  8 A  is an SEM image in which a certain point, at which element analysis was performed on the PFDMA-TPBO antifouling coating layer according to the comparative example 1, is marked (‘Spectrum 1’ in (a) of  FIG.  8 A  and ‘Spectrum 3’ in (b) of  FIG.  8 A ),  FIG.  8 B  is an SEM image in which a certain point, at which element analysis was performed on the antifouling coating layer according to the embodiment 1, is marked (Spectrum 1′ in (a) of  FIG.  8 B  and ‘Spectrum 2’ in (b) of  FIG.  8 B , and ‘Spectrum 3’ in (c) of  FIG.  8 B ), and  FIG.  8 C  is an SEM image in which a certain point, at which element analysis was performed on the antifouling coating layer according to the embodiment 2, is marked (Spectrum 6′ in (a) of  FIG.  8 C  and ‘Spectrum 7’ in (b) of  FIG.  8 C , and ‘Spectrum 8’ in (c) of  FIG.  8 C ). 
     The element analysis result of the PFDMA-TPBO antifouling coating layer according to the comparative example 1 in  FIG.  8 A  was shown in the following Table 2 (measurement in (a) of  FIG.  8 A ) and Table 3 (measurement in (b) of  FIG.  8 A ). 
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 2 
               
               
                   
                   
               
               
                   
                 Element 
                 Weight(%) 
                 Atomic(%) 
               
               
                   
                   
               
             
            
               
                   
                 Si 
                 100 
                 100 
               
               
                   
                 Total 
                 100 
                 100 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 3 
               
               
                   
                   
               
               
                   
                 Element 
                 Weight(%) 
                 Atomic(%) 
               
               
                   
                   
               
             
            
               
                   
                 Si 
                 100 
                 100 
               
               
                   
                 Total 
                 100 
                 100 
               
               
                   
                   
               
            
           
         
       
     
     Referring to  FIG.  8 A , Table 2, and Table 3, it can be seen that fluorine (F) is not found in the PFDMA-TPBO antifouling coating layer according to the comparative example 1. 
     The element analysis result of the antifouling coating layer according to the embodiment 1 in  FIG.  8 B  was shown in the following Table 4 (measurement in (a) of  FIG.  8 B ), Table 5 (measurement in (b) of  FIG.  8 B ), and Table 6 (measurement in (c) of  FIG.  8 B ). 
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 4 
               
               
                   
                   
               
               
                   
                 Element 
                 Weight(%) 
                 Atomic(%) 
               
               
                   
                   
               
             
            
               
                   
                 C 
                 42.40 
                  61.61 
               
               
                   
                 F 
                 12.38 
                  11.38 
               
               
                   
                 Si 
                 42.64 
                  26.50 
               
               
                   
                 Sr 
                  2.57 
                  0.51 
               
               
                   
                 Total 
                 99.99 
                 100 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 5 
               
               
                   
                   
               
               
                   
                 Element 
                 Weight(%) 
                 Atomic(%) 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 C 
                 28.88 
                 49.12 
               
               
                   
                 F 
                 3.51 
                 3.78 
               
               
                   
                 Si 
                 63.43 
                 46.14 
               
               
                   
                 Sr 
                 4.17 
                 0.97 
               
               
                   
                 Total 
                 99.99 
                 100 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 6 
               
               
                   
                   
               
               
                   
                  Element 
                 Weight(%) 
                 Atomic(%) 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Si 
                 95.49 
                 98.51 
               
               
                   
                 Sr 
                 4.51 
                 1.49 
               
               
                   
                 Total 
                 100 
                 100 
               
               
                   
                   
               
            
           
         
       
     
     Referring to  FIG.  8 B , Table 4, and Table 5, it can be seen that there is a difference in element ratio according to analysis positions, but fluorine (F) exists. Meanwhile, referring to Table 6, it can be seen that only existence of a considerable amount of Si that is an element of a substrate is found and the measurement position of (c) of  FIG.  8 B  corresponds to a substrate (silicon). 
     The element analysis result of the antifouling coating layer according to the embodiment 1 in  FIG.  8 C  was shown in the following Table 7 (measurement in (a) of  FIG.  8 C ), Table 8 (measurement in (b) of  FIG.  8 C ), and Table 9 (measurement in (c) of  FIG.  8 C ). 
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 7 
               
               
                   
                   
               
               
                   
                 Element 
                 Weight(%) 
                 Atomic(%) 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 C 
                 43.18 
                 62.73 
               
               
                   
                 F 
                 10.29 
                 9.46 
               
               
                   
                 Si 
                 43.92 
                 27.29 
               
               
                   
                 Sr 
                 2.60 
                 0.52 
               
               
                   
                 Total 
                 99.99 
                 100 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 8 
               
               
                   
                   
               
               
                   
                 Element 
                 Weight(%) 
                 Atomic(%) 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 C 
                 25.37 
                 45.44 
               
               
                   
                 Si 
                 69.66 
                 53.34 
               
               
                   
                 Sr 
                 4.97 
                 1.22 
               
               
                   
                 Total 
                 100 
                 100 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 9 
               
               
                   
                   
               
               
                   
                 Element 
                 Weight(%) 
                 Atomic(%) 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 C 
                 35.44 
                 54.10 
               
               
                   
                 0 
                 4.52 
                 5.18 
               
               
                   
                 F 
                 9.34 
                 9.02 
               
               
                   
                 Si 
                 47.55 
                 31.04 
               
               
                   
                 Sr 
                 3.15 
                 0.66 
               
               
                   
                 Total 
                 96.85 
                 99.34 
               
               
                   
                   
               
            
           
         
       
     
     Referring to  FIG.  8 C , Table 7, and Table 9, it can be seen that there is a difference in element ratio according to analysis positions, but fluorine (F) exists. Meanwhile, referring to Table 8, it can be seen that only existence of a considerable amount of Si that is an element of a substrate is found and the measurement position of (b) of  FIG.  8 C  corresponds to a substrate (silicon). 
     The total values (‘Weight (%)’) in Table 4, Table 5, and Table 7 and the total value (‘Weight (%)’, ‘Atomic (%)’) in Table 9 are results excluding the measurement value of platinum (Pt) used for preprocessing in the EDX analysis process. 
     Experiment Example 7. Application to Copper Substrate 
     This was performed in the same way as the embodiment 2 and an antifouling coating layer was manufactured through an iCVD process by applying a 4-time folded copper (Cu) substrate, as in the insert of  FIG.  9 A , as a substrate in a chamber. 
     After the antifouling coating layer is formed, the 4-time folded copper (Cu) was unfolded, as in  FIG.  9 A , and then FT-IR analysis was performed at each point (deposition point), and the FR-IR analysis result was shown in  FIG.  9 B . 
     Referring to  FIG.  9 B , it can be seen that fluorocarbon (‘—CF 2 ’, ‘—CF 3 ’) are observed at the same points (‘Folded copper plate position 1’, ‘Folded copper plate position 2’, ‘Folded copper plate position 3’, ‘Folded copper plate position 4’) even in the folded state, and it can be seen that an antifouling coating layer was correspondingly formed. 
     Although embodiments of the present disclosure were described above in detail, the spirit of the present disclosure is not limited thereto and the present disclosure may be changed and modified in various ways on the basis of the basic concept without departing from the scope of the present disclosure described in the following claims.