Polyimide composition, preparation method therefor, and polyimide film using same

Abstract

The present invention relates to a polyimide composition, a preparation method therefor, and a polyimide film using same. The polyimide composition of the present invention contains: crosslinked fluorine-based resin particles; and polyamic acid, wherein the crosslinked fluorine-based resin particles include second particles obtained by removing the mesoporous inorganic particles from first particles prepared by emulsion-polymerizing mesoporous inorganic particles, a fluorine-based resin monomer, and a crosslinking agent, thereby obtaining a more porous particle structure than when particles are prepared only through emulsion polymerization.

Description

Polyimide composition, method for producing the same, and polyimide film using the same

[0001] The present invention relates to a polyimide composition and a method for producing the same.

[0002]

[0003] The speed of data transmission and reception in communication devices such as mobile communication devices is gradually increasing.

[0004] However, in communication devices, although the transmission and reception speed of data increases rapidly, there is a disadvantage in that the linearity of the communication signal increases, resulting in increased loss.

[0005] Accordingly, it is desirable to use materials with minimal signal loss in communication devices. Recently, materials with low signal loss, such as liquid crystal polymer (LCP) and polyimide (PI), have been applied.

[0006] However, liquid crystal polymers (LCPs) have the disadvantage of poor processability and poor adhesion to copper foil during substrate manufacturing.

[0007] Meanwhile, in the case of polyimide (PI), there is a limitation that makes it difficult to apply it to communication devices using the millimeter wave (mmWave) frequency band due to increased dielectric loss caused by high hygroscopicity.

[0008] According to Korean Patent Publication No. 10-2016-0090153 (hereinafter referred to as “prior document 1”), a method for manufacturing a polyimide film using particles having pores and a polyimide film with a low dielectric constant are disclosed.

[0009] In particular, according to prior art document 1, it is disclosed to implement low dielectric constant by utilizing the electrical properties of air inside hollow silica.

[0010] However, according to prior art 1, hollow silica has a high hygroscopicity, which causes the low-dielectric effect to be canceled out under high-humidity conditions. Furthermore, when the silica particle size is 1 um or larger, there are disadvantages such as a decrease in physical properties during the production of polyimide films of approximately 20 um, and defects during substrate production.

[0011] Meanwhile, according to Korean Patent Publication No. 10-2014-0114953 (hereinafter referred to as “prior document 2”), polyimide is disclosed.

[0012] In particular, according to prior art document 2, a method of producing a polyimide film by mixing fluorine-based polymer particles in a ratio of 10 to 30 wt% with polyamic acid is disclosed, and a method of implementing a low dielectric constant by forming a pore structure inside the polyimide film together with the low dielectric constant of the fluorine-based polymer material itself is disclosed.

[0013] However, according to prior art document 2, there is a disadvantage in that when fluorine particles are mixed with an organic solvent, they are not well dispersed and sedimentation occurs, making it difficult to form a uniform polyimide film.

[0014]

[0015] As mentioned above, polyimide is known as a low-k insulator for flexible substrates. However, signal loss tends to increase sharply in the mmWave range above 28 GHz, necessitating an interlayer insulating material with lower dielectric properties than currently used materials.

[0016] In the case of polyimides, dielectric properties, especially dielectric loss, have been continuously improved by changing the monomer composition, but this method has currently reached its technological limit.

[0017] Typically, fluorinated polymers undergo fibrillation and severe particle aggregation during the synthesis process, resulting in particles tens to hundreds of nanometers in size. Consequently, fluorinated polymer particles are difficult to disperse. Consequently, films containing fluorinated polymer particles are extremely difficult to manufacture, and even when manufactured, these films often exhibit degraded dielectric properties.

[0018] In addition, since the fluorinated polymer particles and the polyimide resin do not chemically bond with each other, the polyimide film including the fluorinated polymer particles has the disadvantage of a high thermal expansion coefficient.

[0019] The present invention proposes a fluorine-based polymer particle having a new chemical structure to solve such problems, and aims to provide a polyimide composition capable of forming a film having a low dielectric constant, dielectric loss, excellent mechanical properties, and low thermal expansion properties by complexing the particle with a polyimide material.

[0020] In addition, the present invention aims to provide a method for producing the above-described polyimide composition and a polyimide film formed therefrom.

[0021]

[0022] The objectives of the present invention are not limited to those mentioned above. Other objectives and advantages of the present invention not mentioned above can be understood through the following description and will be more clearly understood through the embodiments of the present invention. Furthermore, it will be readily apparent that the objectives and advantages of the present invention can be realized by the means and combinations thereof set forth in the claims.

[0023]

[0024] The polyimide composition according to the present invention for solving the above-described technical problem is characterized in that it comprises fluorine-based polymer particles having a new chemical structure.

[0025] More specifically, the polyimide composition of the present invention comprises crosslinked fluorine-based polymer resin particles; and polyamic acid; wherein the crosslinked fluorine-based polymer resin particles include first particles prepared by emulsion polymerization of mesoporous inorganic particles, a fluorine-based resin monomer, and a crosslinking agent, and second particles from which the mesoporous inorganic particles are removed.

[0026] Here, the cross-linked fluorine resin may include polytetrafluoroethylene (PTFE), and the cross-linking agent may include at least one of TAIC (Trially isocyanurate), TAC (Trially cyanurate), TMPTMA (Trimethylopropane trimethacrylate), and TMPTA (Trimethylolpropane triacrylate).

[0027]

[0028] In addition, a method for producing a polyimide composition according to the present invention for solving the above-described technical problem comprises the steps of: (a) introducing mesoporous inorganic particles, a fluorinated resin monomer, and a crosslinking agent into a reactor and performing emulsion polymerization to produce first particles; (b) treating the first particles with hydrofluoric acid to remove the mesoporous inorganic particles and produce second particles; and (c) mixing the second particles with a solution containing polyamic acid to produce a polyamic acid solution in which the second particles are dispersed.

[0029] Here, the cross-linked fluorine resin may include polytetrafluoroethylene (PTFE), and the cross-linking agent may include at least one of TAIC (Trially Isocyanurate), TAC (Trially cyanurate), TMPTMA (Trimethylopropane Trimethacrylate), and TMPTA (Trimethylolpropane Triacrylate).

[0030]

[0031] Next, a polyimide film according to the present invention for solving the above-described technical problem includes a compound in which crosslinked fluorine-based polymer resin particles and polyamic acid are chemically bonded, and the crosslinked fluorine-based polymer resin particles include second particles from which the mesoporous inorganic particles are removed from first particles manufactured by emulsion polymerization of mesoporous inorganic particles, a fluorine-based resin monomer, and a crosslinking agent.

[0032] Additionally, the compound may include a compound represented by chemical formula 1.

[0033]

[0034] [Chemical Formula 1]

[0035]

[0036] According to the present invention, the crosslinked fluorinated polymer particles of the present invention, unlike fluorinated polymer particles manufactured through conventional emulsion polymerization, can have abundant pores advantageous for improving dielectric properties while also exhibiting significantly improved solvent dispersibility. Accordingly, the present invention can provide a polyimide composition with excellent particle dispersibility.

[0037] Furthermore, according to the present invention, the crosslinking agent present in the crosslinked fluorinated polymer particles forms a chemical bond with the polymer chain of the polyimide as its chemical structure changes at high temperatures. As a result, the present invention can provide a polyimide film with improved mechanical and thermal properties.

[0038] In addition, the present invention can provide a polyimide composition and film that can be applied as a high-performance low-k substrate material and an interlayer insulating layer material.

[0039]

[0040] In addition to the effects described above, specific effects of the present invention are described below while explaining specific details for carrying out the invention.

[0041]

[0042] Figure 1 is a chemical structural formula showing the cross-linked fluorine-based polymer particles of the present invention.

[0043] Figure 2 is a chemical structural formula showing the process in which the crosslinked fluorine-based polymer particles of the present invention are chemically changed by high temperature.

[0044] Figure 3 is a chemical structural formula showing the process of chemically bonding the crosslinked fluorine-based polymer particles of the present invention and polyamic acid.

[0045] Figure 4 is a graph showing the polymerization process of the crosslinked fluorine-based polymer particles of the present invention.

[0046] Figure 5 is an image showing the EDS mapping results for the cross-linked fluorine-based polymer particles of the present invention.

[0047] Figure 6 is an SEM image of PTFE manufactured without a cross-linking agent.

[0048] Figure 7 is an SEM image of PTFE (mesoporous silica removed) manufactured with crosslinking agent TAC.

[0049] Figure 8 is a TEM image of PTFE manufactured without a cross-linking agent.

[0050] Figure 9 is a TEM image of PTFE (mesoporous silica removed) manufactured with crosslinking agent TAC.

[0051] Figure 10 is a photograph showing a state in which PTFE manufactured without a cross-linking agent is aggregated in a solvent.

[0052]

[0053] The above-described objects, features, and advantages will be described in detail below with reference to the accompanying drawings, so that those skilled in the art can easily practice the technical idea of ​​the present invention. In describing the present invention, if it is determined that a detailed description of known technologies related to the present invention may unnecessarily obscure the gist of the present invention, a detailed description thereof will be omitted. Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the drawings, the same reference numerals are used to indicate the same or similar components.

[0054] As used herein, singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, terms such as "consisting of" or "comprising" should not necessarily be construed to include all of the components or steps described in the specification, and should be construed to mean that some of the components or steps may not be included, or that additional components or steps may be included.

[0055] Hereinafter, the polyimide composition, the method for producing the same, and the polyimide film according to the present invention will be described in detail.

[0056]

[0057] polyimide composition

[0058]

[0059] A polyimide composition according to the present invention comprises crosslinked fluorine-based polymer resin particles; and polyamic acid; wherein the crosslinked fluorine-based polymer resin particles include first particles prepared by emulsion polymerization of mesoporous inorganic particles, a fluorine-based resin monomer, and a crosslinking agent, and second particles from which the mesoporous inorganic particles are removed.

[0060]

[0061] The present invention involves introducing a crosslinking agent and a mesoporous inorganic particle template during the process of manufacturing particles including fluorine-based polymer resin particles through emulsion polymerization.

[0062] Mesoporous inorganic particles with fine pores are applied as a template and a crosslinking agent is used together to polymerize a fluorine-based resin monomer.

[0063] Afterwards, when the mesoporous inorganic particle template is removed, a more porous particle structure can be obtained compared to when the particles are manufactured only through emulsion polymerization.

[0064]

[0065] In this way, the present invention can provide a polyimide film rich in pores that is advantageous for improving dielectric properties by using cross-linked fluorine-based polymer resin particles.

[0066]

[0067] The above cross-linked fluorine-based polymer resin particles may be, for example, one selected from the group consisting of polytetrafluoroethylene (PTFE), perfluoroalkoxy (PFA) resin, fluorinated ethylene propylene (FEP) copolymer, chlorotrifluoroethylene (CTFE) resin, tetrafluoroethylene / chlorotrifluoroethylene (TFE / CTFE) copolymer, ethylene chlorotrifluoroethylene (ECTFE) copolymer, and polyvinylidene fluoride (PVDF).

[0068] Most preferably, the cross-linked fluorine-based polymer resin particles may include polytetrafluoroethylene (PTFE).

[0069]

[0070] Here, the mesoporous inorganic particles may preferably include mesoporous silica.

[0071]

[0072] Here, the cross-linking agent may include at least one of TAIC (Trially isocyanurate), TAC (Trially cyanurate), TMPTMA (Trimethylopropane trimethacrylate), and TMPTA (Trimethylolpropane triacrylate). More preferably, the cross-linking agent may include TAIC (Trially isocyanurate), TAC (Trially cyanurate), or TMPTMA (Trimethylopropane trimethacrylate).

[0073]

[0074] Here, the mesoporous inorganic particles can be removed through hydrofluoric acid (HF) treatment. The hydrofluoric acid treatment can be performed by placing the first particles in a hydrofluoric acid solution and stirring.

[0075]

[0076] The above cross-linked fluorine-based polymer resin particles may contain 1 to 30 wt% of the cross-linking agent relative to 100 wt% of the total.

[0077]

[0078] Figure 1 is a chemical structural formula showing the cross-linked fluorine-based polymer resin particles of the present invention. Referring to Figure 1, it can be seen that polytetrafluoroethylene (PTFE) combined with mesoporous silica is cross-linked with TAC or TAIC to form fluorine-based polymer resin particles from which the mesoporous silica is removed.

[0079]

[0080] Here, the polyamic acid can be formed by reacting an aromatic tetracarboxylic anhydride and an aromatic diamine in an organic solvent.

[0081]

[0082] The above aromatic tetracarboxylic acid anhydride may be at least one of pyromellitic dianhydride (PMDA), biphenyltetracarboxylic acid dianhydride (BPDA), 4,4'-Benzophenonetetracarboxylic dianhydride (BTDA), 4,4'-Oxydiphthalic anhydride (ODPA), 4,4'-(Hexafluoroisopropylidene)diphthalic anhydride (6FDA), and 4,4'-(4,4'-isopropylidene-diphenoxy)bis(phthalic anhydride) (BPADA).

[0083]

[0084] The above aromatic diamine may be at least one of phenylenediamine (PDA), oxydianiline (ODA), o-phenylenediamine (OPD), Meta-phenylenediamine (MPD), 1,3-bis(4-aminophenoxy)benzene (TPER), 4,4'-bis(4-aminophenoxy)benzene (TPEQ), 2,2'-Dimethyl-4,4'-diaminobiphenyl (m-TB-HG), 2,2'-Bis(Trifluoromethyl)benzidine (TFDB), 1,3'-Bis(3-aminophenoxy)benzene (APBN), 3,5-Diaminobenzotrifluoride (DABTF), and 2,2-bis(4-[4-aminophenoxy]-phenyl)propane (BAPP).

[0085]

[0086] The above organic solvent may be at least one selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidone, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, m-cresol, p-chlorophenol, and anisole.

[0087]

[0088] Here, the aromatic tetracarboxylic anhydride may be included in an amount of 0.90 to 1.10 equivalents relative to the aromatic diamine.

[0089] Additionally, the organic solvent may be included in an amount of 70 to 90 wt% based on the total weight of the polyamic acid.

[0090]

[0091] Method for producing a polyimide composition

[0092]

[0093] Next, a method for manufacturing a polyimide composition according to the present invention will be described.

[0094]

[0095] A method for producing a polyimide composition according to the present invention comprises the steps of: (a) introducing mesoporous inorganic particles, a fluorine-based resin monomer, and a crosslinking agent into a reactor and subjecting the first particles to emulsion polymerization; (b) treating the first particles with hydrofluoric acid to remove the mesoporous inorganic particles and produce second particles; and (c) mixing the second particles with a solution containing polyamic acid to produce a polyamic acid solution in which the second particles are dispersed.

[0096]

[0097] First, in step (a), mesoporous inorganic particles, a fluorine-based resin monomer, and a crosslinking agent are introduced into a reactor and emulsion polymerized to produce first particles. Preferably, the first particles may include polytetrafluoroethylene (PTFE).

[0098] The present invention involves introducing a crosslinking agent and a mesoporous inorganic particle template during the process of manufacturing particles including fluorine-based polymer resin particles through emulsion polymerization.

[0099] Mesoporous inorganic particles with fine pores are applied as a template and a crosslinking agent is used together to polymerize a fluorine-based resin monomer.

[0100] Afterwards, when the mesoporous inorganic particle template is removed, a more porous particle structure can be obtained compared to when the particles are manufactured only through emulsion polymerization.

[0101] In this way, the present invention can provide a polyimide film rich in pores that is advantageous for improving dielectric properties by using cross-linked fluorine-based polymer resin particles.

[0102] Here, the mesoporous inorganic particles may preferably include mesoporous silica.

[0103] Here, the cross-linking agent may include at least one of TAIC (Trially isocyanurate), TAC (Trially cyanurate), TMPTMA (Trimethylopropane trimethacrylate), and TMPTA (Trimethylolpropane triacrylate). More preferably, the cross-linking agent may include TAIC (Trially isocyanurate), TAC (Trially cyanurate), or TMPTMA (Trimethylopropane trimethacrylate).

[0104]

[0105] Referring to FIG. 1, it can be seen that polytetrafluoroethylene (PTFE) combined with mesoporous silica is crosslinked with TAC or TAIC to form fluorine-based polymer resin particles from which mesoporous silica is removed.

[0106]

[0107] Next, through step (b), the first particle is treated with hydrofluoric acid to remove the mesoporous inorganic particles and produce the second particle.

[0108]

[0109] Here, the mesoporous inorganic particles are removed through hydrofluoric acid (HF) treatment. The hydrofluoric acid treatment can be performed by placing the first particles in a hydrofluoric acid solution and stirring.

[0110]

[0111] Next, through step (c), a solution containing the second particles and polyamic acid is mixed to prepare a polyamic acid solution in which the second particles are dispersed.

[0112]

[0113] Here, the polyamic acid can be formed by reacting an aromatic tetracarboxylic anhydride and an aromatic diamine in an organic solvent.

[0114]

[0115] The above aromatic tetracarboxylic acid anhydride may be at least one of pyromellitic dianhydride (PMDA), biphenyltetracarboxylic acid dianhydride (BPDA), 4,4'-Benzophenonetetracarboxylic Dianhydride (BTDA), 4,4'-Oxydiphthalic anhydride (ODPA), 4,4'-(Hexafluoroisopropylidene)diphthalic Anhydride (6FDA), and 4,4'-(4,4'-isopropylidene-diphenoxy)bis(phthalic anhydride) (BPADA).

[0116]

[0117] The above aromatic diamine may be at least one of phenylenediamine (PDA), oxydianiline (ODA), o-phenylenediamine (OPD), Meta phenylene Diamine (MPD), 1,3-bis(4-aminophenoxy)benzene (TPER), 4,4'-bis(4-aminophenoxy)benzene (TPEQ), 2,2'-Dimethyl-4,4'-diamino biphenyl (m-TB-HG), 2,2'-Bis(Trifluoromethyl)benzidine (TFDB), 1,3'-Bis(3-aminophenoxy)benzene (APBN), 3,5-Diaminobenzotrifluoride (DABTF), and 2,2-bis(4-[4-aminophenoxy]-phenyl)propane (BAPP).

[0118]

[0119] The above organic solvent may be at least one selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidone, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, m-cresol, p-chlorophenol, and anisole.

[0120]

[0121] As described above, the aromatic tetracarboxylic anhydride may be included in an amount of 0.90 to 1.10 equivalents relative to the aromatic diamine.

[0122] Additionally, the organic solvent may be included in an amount of 70 to 90 wt% based on the total weight of the polyamic acid.

[0123]

[0124] polyimide film

[0125]

[0126] Next, a polyimide film according to the present invention will be described. The polyimide film of the present invention can be formed from the polyimide composition described above.

[0127]

[0128] The polyimide film of the present invention comprises a compound in which crosslinked fluorine-based polymer resin particles and polyamic acid are chemically bonded, and the crosslinked fluorine-based polymer resin particles comprise second particles from which the mesoporous inorganic particles are removed from first particles manufactured by emulsion polymerization of mesoporous inorganic particles, a fluorine-based resin monomer, and a crosslinking agent.

[0129]

[0130] Figure 2 is a chemical structural formula showing the process by which the crosslinked fluorinated polymer particles of the present invention are chemically changed by high temperature. In addition, Figure 3 is a chemical structural formula showing the process by which the crosslinked fluorinated polymer particles of the present invention are chemically bonded to polyamic acid.

[0131]

[0132] Referring to Figures 2 and 3, the chemical structure of the cross-linked PTFE particles changes under high temperature conditions for curing the polyimide film. When TAIC is used as a cross-linking agent, it can form an isocyanate structure at high temperatures. PTFE chains having isocyanate functional groups at their terminals react with the carboxylic acid functional groups of polyamic acid to form carbamic-carboxylic anhydride, which is then converted into an amide bond through decarboxylation. Through this, a chemical bond is formed between the polyimide polymer chain and the PTFE chain.

[0133]

[0134] Preferably, the compound included in the polyimide film of the present invention may include a compound represented by chemical formula 1.

[0135]

[0136] [Chemical Formula 1]

[0137]

[0138] The polyimide film of the present invention described above can be used as a low-k substrate material and an interlayer insulating material.

[0139]

[0140] Example

[0141] Hereinafter, the structure and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, these are presented as preferred examples of the present invention and should not be construed as limiting the present invention in any way.

[0142] Anything not described here will be omitted as it is technically feasible for those skilled in this field to infer.

[0143]

[0144] 1. Examination process

[0145] (1) Tetrafluoroethylene (TFE) monomer is manufactured into particles through emulsion polymerization.

[0146] Polymerization using TFE monomer uses a high-pressure reactor (Parr autoclave system). High-pressure reaction vessel (1000 cm 3 ), ammonium persulfate (0.48g), perfluoro-3,6,9-trioxadecanoic acid (1g), water (500 cm 3 ) was injected, the reactor was sealed, and oxygen was removed through an atmosphere replacement process using nitrogen gas for 40 minutes. After that, the inside of the reactor was made into a reduced pressure state, the reactor was heated to 80 ℃, and the TFE monomer was injected until the pressure inside the reactor reached 10 bar, and polymerization was initiated while stirring at 500 rpm. The polymerization was carried out while maintaining the pressure of TFE at 10 bar throughout the reaction. After approximately 32 g of TFE was consumed, the polymerization was stopped, and filler particles composed of PTFE polymer were synthesized.

[0147]

[0148] (2) Filler particles are manufactured through emulsion polymerization by adding mesoporous silica and TFE together with a crosslinking agent (TAC, TAIC).

[0149] Add ammonium persulfate (0.48 g), perfluoro-3,6,9-trioxadecanoic acid (1 g), and water (500 cm3) to a beaker. Add additional crosslinking agent [TAC or TAIC] and mesoporous silica (20 g) to the container, and stir at 5000 rpm for 10 minutes using a high-shear mixer (L5M-A Laboratory High Shear Mixer) to make it dispersed. The dispersed solution is transferred to a high-pressure reaction vessel (1000 cm 3 ), the reactor was sealed and the atmosphere was replaced with nitrogen gas for 40 minutes. After that, the inside of the reactor was made into a reduced pressure state, the temperature was increased to 80 ℃, and the TFE monomer was injected until the pressure inside the reactor became 10 bar. Polymerization was initiated while stirring at 500 rpm. The polymerization was carried out while maintaining the pressure of TFE at 10 bar during the reaction process, and the reaction was terminated after proceeding until approximately 32 g of TFE monomer was consumed, thereby synthesizing cross-linked PTFE filler particles containing mesoporous silica.

[0150]

[0151] (3) Removal of silica from PTFE filler particles containing mesoporous silica and crosslinking agent through hydrofluoric acid treatment and recovery of polymer particles.

[0152] To remove the silica from the PTFE filler particles containing mesoporous silica and a crosslinking agent, the dried polymer is weighed. The weighed polymer is placed in 300 cm of ultrapure water. 3 After diluting, add more than 50% of hydrofluoric acid to remove silica and stir for 1 hour. At this time, the HF equivalent to react with mesoporous silica was calculated by the following formula. After stirring, 1000 cm of ultrapure water was added. 3After further dilution, PTFE filler particles are recovered through filtration. The washing process with purified water is repeated 2-3 times to completely remove hydrofluoric acid. After the hydrofluoric acid has been removed, the PTFE filler is dried and compared with the expected yield to confirm that the silica has been sufficiently removed.

[0153]

[0154] (4) Process of dispersing filler particles composed only of PTFE using a high-pressure disperser.

[0155] In the case of PTFE that did not contain a cross-linking agent pretreated with a homogenizer, it was not well dispersed in the dispersion medium, N,N-dimethylacetamide (DMAc), and existed in an aggregated state, making it impossible to process using a high-pressure disperser.

[0156]

[0157] (5) Process of dispersing PTFE filler particles containing a crosslinking agent with or without mesoporous silica using a high-pressure disperser.

[0158] PTFE filler particles containing a cross-linking agent, including mesoporous silica, were mixed with DMAc and stirred at 5,000 rpm for 10 minutes using a high-shear mixer. The pretreated filler particles were then placed in a high-pressure disperser to subject them to high shear and impact forces. After passing through a cooling coil, uniformly dispersed filler particles were cooled to room temperature. PTFE filler particles from which silica had been removed through hydrofluoric acid treatment were also dispersed using the same process.

[0159]

[0160] (6) Process of manufacturing a polyimide film by mixing the manufactured PTFE filler with polyamic acid (PAA) varnish.

[0161] DMAc was additionally added to the pre-dispersed cross-linked PTFE filler particles or the cross-linked PTFE filler particles containing silica to prepare a dispersion having a concentration of approximately 13 wt%. A portion of the dispersion solution was mixed with a polyamic acid solution having a solid content of 13 wt%, and a PTFE / polyamic acid mixed dispersion was prepared using a rotating mixer. At this time, the ratio of PTFE to polyamic acid was 30 wt%, and the solid content in the total dispersion medium was 8 to 15 wt%. The PTFE / polyamic acid mixed solution was coated on a 12 ㎛ thick electrolytic copper foil and dried at 140 ° C. for 10 minutes. Thereafter, it was heat-treated using an infrared heater up to a maximum temperature of 395 ° C. to convert it to a polyimide (PI) resin. Thereafter, the copper foil was removed from the laminated structure of the polyimide and the copper foil using a ferric chloride aqueous solution, resulting in a polyimide film having a thickness of 20 ㎛.

[0162]

[0163] 2. Test results

[0164] (1) Confirm polymerization results

[0165] Figure 4 is a graph showing the polymerization process of the crosslinked fluorine-based polymer particles of the present invention.

[0166] Referring to Fig. 4, the FT-IR results of PTFE filler particles containing TAC as a crosslinking agent, with mesoporous silica removed, after hydrofluoric acid treatment, show Si-O bending at 1100 cm -1 , 810 cm -1 ,470 cm -1 The disappearance of the silica characteristic peak at 1400–1500 cm, indicating the C=N bond, indicated that silica was removed. -1 and 1650~1750 cm -1 It was confirmed that the characteristic peaks of TAC appearing in were maintained.

[0167]

[0168] (2) Energy dispersive X-ray spectroscopy (EDS mapping) of cross-linked fluorinated polymer particles

[0169] Figure 5 is an image showing the EDS mapping results for the cross-linked fluorine-based polymer particles of the present invention.

[0170] Referring to Fig. 5, in the case of PTFE filler particles containing TAC as a crosslinking agent from which mesoporous silica has been removed, nitrogen atoms and oxygen atoms are observed, but silicon atoms are not detected, indicating that all silica has been removed through hydrofluoric acid treatment.

[0171]

[0172] (3) Scanning electron microscope (SEM) and transmission electron microscope (TEM) images of cross-linked fluorine-based polymer particles

[0173] Figure 6 is a SEM image of PTFE manufactured without a cross-linking agent. Figure 7 is a SEM image of PTFE manufactured with the cross-linking agent TAC (mesoporous silica removed). Figure 8 is a TEM image of PTFE manufactured without a cross-linking agent. Figure 9 is a TEM image of PTFE manufactured with the cross-linking agent TAC (mesoporous silica removed).

[0174] Referring to Figures 6 to 9, it was confirmed that there was a lot of fibrillation in the SEM image of the PTFE filler manufactured under standard conditions without adding a cross-linking agent, and it was observed that it had an amorphous shape in the TEM image. In the case of the PTFE filler particles containing the cross-linking agent TAC from which the mesoporous silica was removed, the fibrillated portion similar to Homo PTFE could be observed through SEM, and the particle shape of the silica was not visible, so it could be judged that the hydrofluoric acid treatment was well performed. In the TEM image, it was observed that since the mesoporous silica was removed, the silica mainly existed in a spherical particle shape in the original location.

[0175]

[0176] (4) Confirmation of dispersion of cross-linked fluorine-based polymer particles

[0177] Figure 10 is a photograph showing a state in which PTFE manufactured without a cross-linking agent is aggregated in a solvent.

[0178] Referring to Fig. 10, when PTFE filler particles manufactured under standard conditions without the cross-linking agent TAC were dispersed using a homogenizer after DMAc was added, the PTFE was observed to remain in an aggregated state and not dispersed at all.

[0179] In contrast, in the case of PTFE filler particles containing a cross-linking agent from which mesoporous silica was removed, dispersion was possible when dispersion was performed using a homogenizer and then a high-pressure disperser. It was confirmed that the PTFE filler particles containing TAC (5 wt%) from which mesoporous silica was removed through hydrofluoric acid treatment were dispersed with an average particle diameter of 265 nm. This shows that even when the template silica particles are removed, the shape is maintained to some extent without being disintegrated. In addition, it was confirmed that the PTFE filler particles containing TAIC (5 wt%) from which mesoporous silica was removed through hydrofluoric acid treatment were dispersed with an average particle diameter of 226 nm.

[0180]

[0181] (5) Analysis of dielectric properties of the polyimide film of the present invention

[0182] The dielectric properties of polyimide films containing 30 wt% PTFE filler were analyzed as shown in Table 1 below (23°C, 50% relative humidity conditions).

[0183]

[0184] Referring to Table 1, it can be confirmed that the polyimide film containing cross-linked PTFE particles according to the present invention has improved dielectric constant and dielectric loss values ​​compared to a pure polyimide film.

[0185]

[0186] Manufacturing Example Dk / Df (28GHz) 23℃, 50%RH 1dayRefPure PI (without filler) 3.27 / 0.00331#1 Mesoporous silica + TAC (3wt%) + PTFE_HF (PI manufactured by adding particles from which PTFE was polymerized by adding mesoporous silica and TAC, and then silica was removed by hydrofluoric acid treatment) 2.71 / 0.00274#2 Mesoporous silica + TAC (5wt%) + PTFE_HF (PI manufactured by adding particles from which PTFE was polymerized by adding mesoporous silica and TAC, and then silica was removed by hydrofluoric acid treatment) 2.77 / 0.00322#3 Mesoporous silica + TAIC (3wt%) + PTFE_HF (PI manufactured by adding particles from which PTFE was polymerized by adding mesoporous silica and TAIC, and then silica was removed by hydrofluoric acid treatment) PI)2.95 / 0.00368#4 Mesoporous silica + TAIC (5 wt%) + PTFE_HF (PI)2.98 / 0.00341 manufactured by adding particles in which mesoporous silica and TAIC were added, PTFE was polymerized, and then silica was removed by hydrofluoric acid treatment.

[0187]

[0188] Although the present invention has been described with reference to the drawings exemplified above, it is to be understood that the present invention is not limited to the embodiments and drawings disclosed herein, and that various modifications may be made by those skilled in the art within the scope of the technical idea of ​​the present invention. Furthermore, even if the operational effects according to the configuration of the present invention have not been explicitly described while describing the embodiments of the present invention, it is natural that the effects predictable by the corresponding configuration should also be acknowledged.

Claims

1. Cross-linked fluorine-based polymer resin particles; and Contains polyamic acid; The above cross-linked fluorine-based polymer resin particles A second particle comprising a first particle manufactured by emulsion polymerization of mesoporous inorganic particles, a fluorine-based resin monomer, and a crosslinking agent, wherein the mesoporous inorganic particles are removed. Polyimide composition.

2. In paragraph 1, The above mesoporous inorganic particles Containing mesoporous silica Polyimide composition.

3. In paragraph 1, The above mesoporous inorganic particles Removed by hydrofluoric acid treatment Polyimide composition.

4. In paragraph 1, The above cross-linked fluorine resin Containing polytetrafluoroethylene (PTFE) Polyimide composition.

5. In paragraph 1, The above cross-linking agent Containing at least one of TAIC (Trially isocyanurate), TAC (Trially cyanurate), TMPTMA (Trimethylopropane trimethacrylate), and TMPTA (Trimethylolpropane triacrylate) Polyimide composition.

6. In paragraph 1, The above polyamic acid is A compound formed by reacting an aromatic tetracarboxylic anhydride and an aromatic diamine in an organic solvent. Polyimide composition.

7. In paragraph 6, The above aromatic tetracarboxylic anhydride is pyromellitic dianhydride (PMDA), biphenyltetracarboxylic acid dianhydride (BPDA), 4,4'-Benzophenenetetracarboxylic dianhydride (BTDA), 4,4'-Oxydiphthalic anhydride (ODPA), 4,4'-(Hexafluoroisopropylidene)diphthalic anhydride (6FDA), and One or more types of 4,4'-(4,4'-isopropylidene-diphenoxy)bis(phthalic anhydride) (BPADA) Polyimide composition.

8. In paragraph 6, The above aromatic diamine is phenylenediamine (PDA), oxydianiline (ODA), o-phenylenediamine (OPD), Meta phenylene Diamine (MPD), 1,3-bis(4-aminophenoxy)benzene (TPER), 4,4'-bis(4-aminophenoxy)benzene (TPEQ), 2,2'-Dimethyl-4,4'-diamino biphenyl (m-TB-HG), 2,2'-Bis(Trifluoromethyl)benzidine (TFDB), 1,3'-Bis(3-aminophenoxy)benzene (APBN), 3,5-Diaminobenzotrifluoride (DABTF), and 2,2-bis(4-[4-aminophenoxy]-phenyl)propane (BAPP). Polyimide composition.

9. In paragraph 6, The organic solvent is at least one selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidone, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, m-cresol, p-chlorophenol, and anisole. Polyimide composition. 10.(a) A step of introducing mesoporous inorganic particles, a fluorine-based resin monomer, and a crosslinking agent into a reactor and performing emulsion polymerization to produce first particles; (b) a step of treating the first particle with hydrofluoric acid to remove the mesoporous inorganic particles and manufacture the second particle; (c) a step of mixing the second particles and a solution containing polyamic acid to prepare a polyamic acid solution in which the second particles are dispersed; Method for producing a polyimide composition.

11. In paragraph 10, The above mesoporous inorganic particles Containing mesoporous silica Method for producing a polyimide composition.

12. In paragraph 10, The above fluorine resin monomer Containing tetrafluoroethylene (TFE) Method for producing a polyimide composition.

13. In paragraph 10, The above cross-linking agent Containing at least one of TAIC (Trially isocyanurate), TAC (Trially cyanurate), TMPTMA (Trimethylopropane trimethacrylate), and TMPTA (Trimethylolpropane triacrylate) Method for producing a polyimide composition.

14. In paragraph 10, In step (c) above, The above polyamic acid is A compound formed by reacting an aromatic tetracarboxylic anhydride and an aromatic diamine in an organic solvent. Method for producing a polyimide composition.

15. In paragraph 14, The above aromatic tetracarboxylic anhydride is pyromellitic dianhydride (PMDA), biphenyltetracarboxylic acid dianhydride (BPDA), 4,4'-Benzophenonetetracarboxylic Dianhydride (BTDA), 4,4'-Oxydiphthalic anhydride (ODPA), 4,4'-(Hexafluoroisopropylidene)diphthalic Anhydride (6FDA), and One or more types of 4,4'-(4,4'-isopropylidene-diphenoxy)bis(phthalic anhydride) (BPADA) Method for producing a polyimide composition.

16. In paragraph 14, The above aromatic diamine is phenylenediamine (PDA), oxydianiline (ODA), o-phenylenediamine (OPD), Meta phenylene Diamine (MPD), 1,3-bis(4-aminophenoxy)benzene (TPER), 4,4'-bis(4-aminophenoxy)benzene (TPEQ), 2,2'-Dimethyl-4,4'-diamino biphenyl (m-TB-HG), 2,2'-Bis(Trifluoromethyl)benzidine (TFDB), 1,3'-Bis(3-aminophenoxy)benzene (APBN), 3,5-Diaminobenzotrifluoride (DABTF), and 2,2-bis(4-[4-aminophenoxy]-phenyl)propane (BAPP). Method for producing a polyimide composition.

17. In paragraph 14, The organic solvent is at least one selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidone, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, m-cresol, p-chlorophenol, and anisole. Method for producing a polyimide composition.

18. A compound comprising cross-linked fluorine-based polymer resin particles and polyamic acid chemically bonded thereto, The above cross-linked fluorine-based polymer resin particles A second particle comprising a first particle manufactured by emulsion polymerization of mesoporous inorganic particles, a fluorine-based resin monomer, and a crosslinking agent, wherein the mesoporous inorganic particles are removed. Polyimide film.

19. In paragraph 18, The above compound comprises a compound represented by chemical formula 1. Polyimide film. [Chemical Formula 1] 20. In paragraph 18, The above mesoporous inorganic particles Containing mesoporous silica Polyimide film.

21. In paragraph 18, The above mesoporous inorganic particles Removed by hydrofluoric acid treatment Polyimide film.

22. In paragraph 18, The above cross-linked fluorine resin Containing polytetrafluoroethylene (PTFE) Polyimide film.

23. In paragraph 18, The above cross-linking agent Containing at least one of TAIC (Trially Isocyanurate), TAC (Trially cyanurate), TMPTMA (Trimethylopropane Trimethacrylate), and TMPTA (Trimethylolpropane Triacrylate) Polyimide film.

24. In paragraph 18, The above polyamic acid is A compound formed by reacting an aromatic tetracarboxylic anhydride and an aromatic diamine in an organic solvent. Polyimide film.

25. In paragraph 24, The above aromatic tetracarboxylic anhydride is pyromellitic dianhydride (PMDA), biphenyltetracarboxylic acid dianhydride (BPDA), 4,4'-Benzophenonetetracarboxylic Dianhydride (BTDA), 4,4'-Oxydiphthalic anhydride (ODPA), 4,4'-(Hexafluoroisopropylidene)diphthalic Anhydride (6FDA), and One or more types of 4,4'-(4,4'-isopropylidene-diphenoxy)bis(phthalic anhydride) (BPADA) Polyimide film.

26. In paragraph 24, The above aromatic diamine is phenylenediamine (PDA), oxydianiline (ODA), o-phenylenediamine (OPD), Meta phenylene Diamine (MPD), 1,3-bis(4-aminophenoxy)benzene (TPER), 4,4'-bis(4-aminophenoxy)benzene (TPEQ), 2,2'-Dimethyl-4,4'-diamino biphenyl (m-TB-HG), 2,2'-Bis(Trifluoromethyl)benzidine (TFDB), 1,3'-Bis(3-aminophenoxy)benzene (APBN), 3,5-Diaminobenzotrifluoride (DABTF), and 2,2-bis(4-[4-aminophenoxy]-phenyl)propane (BAPP). Polyimide film.

27. In paragraph 24, The organic solvent is at least one selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidone, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, m-cresol, p-chlorophenol, and anisole. Polyimide film.

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