WO2019027207A1 - Method for manufacturing polyimide film using fumed silica particles and polyimide film having low dielectric constant - Google Patents

Method for manufacturing polyimide film using fumed silica particles and polyimide film having low dielectric constant Download PDF

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WO2019027207A1
WO2019027207A1 PCT/KR2018/008624 KR2018008624W WO2019027207A1 WO 2019027207 A1 WO2019027207 A1 WO 2019027207A1 KR 2018008624 W KR2018008624 W KR 2018008624W WO 2019027207 A1 WO2019027207 A1 WO 2019027207A1
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fumed silica
silica particles
polyimide film
polyimide
film according
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PCT/KR2018/008624
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French (fr)
Korean (ko)
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백승열
이길남
임현재
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에스케이씨코오롱피아이 주식회사
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Publication of WO2019027207A1 publication Critical patent/WO2019027207A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area

Definitions

  • the present invention relates to a process for producing a polyimide film using fumed silica particles and a low-dielectric-constant polyimide film produced by the process.
  • polyimide (PI) resin refers to a high heat resistant resin prepared by solution polymerization of an aromatic dianhydride and an aromatic dianhydride or an aromatic diisocyanate to prepare a polyamic acid derivative, followed by ring-closing dehydration at a high temperature and imidization.
  • Polyimide resin is an insoluble and infusible ultra-high temperature resistant resin, and has excellent properties such as heat resistance, heat resistance, radiation resistance, low temperature property, and chemical resistance. It is a high temperature resistant material such as automobile material, Coating materials, insulating films, semiconductors, electrode protective films of TFT-LCD, and the like.
  • a hydrophilic polymer is dispersed in a polyimide resin precursor soluble in an organic solvent, and this hydrophilic polymer is subjected to firing or solvent extraction To thereby obtain a porous polyimide resin.
  • the hole becomes flat or clogged and the porosity rate becomes smaller than the ideal value, so that the permittivity can not be sufficiently lowered.
  • Korean Patent No. 1299652 discloses a construction using fluorine particles in the production of a flexible metal laminate, but the method is based on the application of monomolecular fluorine particles, and the fluorine particles are not well dispersed.
  • the present inventors have found that the electrical properties of air can be realized by using fumed silica particles having pores to realize a dielectric constant lower than that of a conventional polyimide film, and to improve dispersibility of the fumed silica particles during the manufacturing process
  • the inventors of the present invention have completed the present invention by developing a method for producing a polyimide film with improved sinking phenomenon.
  • an object of the present invention is to provide a method for producing a polyimide film having a low dielectric constant, and a polyimide film having a low dielectric constant produced according to the method.
  • the present invention provides a method for producing a polyimide precursor, comprising: 1) preparing a polyimide precursor; 2) mixing a polyimide precursor with an imidization conversion liquid containing fumed silica particles to prepare a gel film; And 3) heat treating the gel film to imidize the fumed silica particles, wherein the fumed silica particles have pores having an average particle size of 10 m or less and an average size of 300 nm or less And a manufacturing method thereof.
  • the present invention also provides a polyimide film comprising fumed silica particles, wherein the fumed silica particles have pores with an average particle diameter of 10 m or less and an average size of 300 nm or less. Thereby providing a polyimide film.
  • the polyimide film produced using the fumed silica particles according to the method of the present invention is minimized in dielectric constant, dielectric loss tangent, and moisture absorption rate and can be effectively used for an inner insulator, a buffer material, a circuit board, and the like of an electric apparatus.
  • the present invention provides: 1) a step of producing a polyimide precursor; 2) mixing a polyimide precursor with an imidization conversion liquid containing fumed silica particles to prepare a gel film; And 3) heat treating the gel film to imidize the fumed silica particles, wherein the fumed silica particles have pores having an average particle size of 10 m or less and an average size of 300 nm or less And a manufacturing method thereof.
  • Step 1) of the production process according to the present invention is a step of producing a polyimide precursor.
  • the polyimide precursor any material that can become a polyimide resin by imidization can be used.
  • the polyimide precursor may be a polyamic acid obtained by copolymerizing an acid dianhydride component and a diamine component in the presence of an organic solvent according to a conventional method.
  • the acid dianhydride component and the diamine component may be appropriately selected from those conventionally used in the production of polyamic acid.
  • the acid dianhydrides include biphenyltetracarboxylic acid dianhydride or derivatives thereof, pyromellitic dianhydride (PMDA), 3,3'4,4'-benzophenonetetracarboxylic acid anhydride, p-phenylene- And bistrimelitic acid dianhydride.
  • diamine component examples include para-phenylenediamine (pPDA), diaminophenyl ether, o-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether (ODA) Diaminodiphenyl ether, 2,4-diaminodiphenyl ether, and the like.
  • pPDA para-phenylenediamine
  • ODA 4,4-diaminodiphenyl ether
  • Diaminodiphenyl ether 2,4-diaminodiphenyl ether, and the like.
  • the acid dianhydride component and the diamine component may be mixed in a molar ratio of 1: 0.9 to 1: 1.1.
  • organic solvent examples include N, N'-dimethylformamide (DMF), N, N'-dimethylacetamide (DMAc), N-methyl-pyrrolidone (NMP) and the like.
  • step 2) of the production method according to the present invention a gel film is prepared by mixing the imidization conversion liquid containing the fumed silica particles with the polyimide precursor prepared in step 1).
  • fumed silica particles are added to the imidization conversion liquid, and the resulting imidization conversion liquid is added to the polyimide precursor, for example, polyamic acid to prepare an imidized resin mixture.
  • the imidization conversion liquid may be any material conventionally used to cause chemical hardening.
  • the imidization conversion liquid may be selected from the group consisting of a dehydrating agent, a catalyst, a polar organic solvent and a mixed solution thereof, and specifically, it may be a mixed solution of a dehydrating agent, a catalyst and a polar organic solvent. More specifically, the imidization conversion liquid may be a dehydrating agent such as acetic anhydride or the like; Tertiary amines including pyridine, beta picoline and isoquinoline; And polar organic solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and the like.
  • the imidization conversion liquid may be used in an amount of 160 to 800 parts by weight, specifically, 270 to 650 parts by weight, and more specifically 400 to 550 parts by weight, based on 100 parts by weight of the polyimide precursor.
  • the amount of the imidization conversion liquid used may vary depending on the kind of the polyimide precursor used and the thickness of the polyimide film to be produced.
  • fumed silica (fumed silica)" as used herein is to be produced by the dry process, shows a silica (SiO 2) obtained a silicon tetrachloride (SiCl 4) and heated in air to decompose. Fumed silica generally has high surface area and fine grain characteristics.
  • the fumed silica used in the present invention may be particles having pores. By using the fumed silica having pores, the polyimide film exhibiting the characteristic of low dielectric constant can be manufactured by realizing the electrical characteristics of the air.
  • the fumed silica may also be a hollow or mesoporous particle.
  • the fumed silica may be either produced from silicon tetrachloride or commercially available.
  • the fumed silica particles according to the present invention may have an average particle diameter of 10 mu m or less, specifically 0.3 to 10 mu m, more specifically 3 to 10 mu m. According to one embodiment of the present invention, the average particle diameter of the fumed silica particles may be 5 ⁇ .
  • the fumed silica particles may have pores having an average size of 300 nm or less, 100 nm or less, 50 nm or less, or 20 nm or less.
  • the fumed silica particles have an average size of 0.1 to 300 nm, 1 to 300 nm, 10 to 300 nm, 0.1 to 100 nm, 1 to 100 nm, 10 to 100 nm, 0.1 to 50 nm, 10 to 50 nm, 0.1 to 20 nm, 1 to 20 nm, or 10 to 20 nm.
  • the fumed silica particles according to the present invention may have pores having an average particle size of 3 to 10 mu m and an average size of 1 to 100 nm.
  • the specific surface area of the fumed silica particles may be 300 m 2 / g or more, specifically 300 to 2,000 m 2 / g, more specifically 600 to 1,000 m 2 / g.
  • the content of the fumed silica particles is 2 to 30% by weight, specifically 5 to 20% by weight, more specifically 13 To 17% by weight.
  • content of the fumed silica particles is within the above range, not only the mechanical properties of the polyimide film are minimized, but also the low dielectric effect of the film can be realized.
  • the fumed silica particles added to the imidization conversion liquid according to the present invention can be added as the particles themselves.
  • the fumed silica particles may be added in a dispersion state or a colloid state dispersed in a polar organic solvent so as to be more uniformly dispersed and mixed in the imidization conversion liquid.
  • a gel film can be prepared from the imidized resin mixture obtained above.
  • the imidized resin mixture is coated on a support (for example, a stainless steel plate, a glass plate, an aluminum foil, a circulating stainless belt or a stainless steel drum), and then a chemically partially imaged gel film is subjected to primary heat treatment and drying Can be manufactured.
  • the primary heat treatment may be performed at a temperature of 100 ° C to 200 ° C for 1 to 15 minutes.
  • step 3) of the production method according to the present invention the gel film prepared in step 2) is heat-treated to be imidized.
  • the chemically partially imidized gel film prepared in step 2) can be separated from the support for complete imidization and subjected to a secondary heat treatment.
  • the secondary heat treatment may be carried out at a temperature of 250 ⁇ to 850 ⁇ for 5 to 25 minutes.
  • the secondary heat treatment may be performed under a constant tension to remove residual stress in the film generated during the film formation process.
  • a process for preparing a polyamic acid as a polyimide precursor An imidization conversion liquid in which the fumed silica particles having an average particle diameter of 10 mu m or less, an average pore size of 300 nm or less and a specific surface area of 300 m < 2 > / g or more are uniformly dispersed is mixed in the polyamic acid,
  • the imidized resin mixture was coated on a support and subjected to a first heat treatment at 120 ° C for 3 minutes and dried to prepare a gel film;
  • the gel film was subjected to a secondary heat treatment at 400 DEG C for 7 minutes to produce a polyimide film.
  • the present invention provides a polyimide film comprising fumed silica particles having an average particle diameter of 10 m or less and pores having an average size of 300 nm or less.
  • the polyimide film comprising the fumed silica particles is obtained from a polyimidated resin synthesized using an imidization conversion solution comprising polyamic acid and fumed silica particles, wherein the fumed silica particles have an average particle size of 10 Mu m or less and having pores with an average size of 300 nm or less.
  • the fumed silica particles are as described above.
  • the thickness of the polyimide film according to the present invention may be 12.5 to 50 ⁇ .
  • the dielectric constant of the polyimide film according to the present invention may be 3.4 or less at 1 GHz, specifically 2.7 to 3.4 or 2.7 to 3.0.
  • the dielectric loss tangent of the polyimide film may be less than 0.02 at 1 GHz, specifically 0.005 to 0.02, or 0.005 to 0.01.
  • the moisture absorption rate of the polyimide film according to the present invention may be 2% or less, specifically 0.1 to 2%, 0.1 to 1.8%, 0.5 to 1.8% or 0.8 to 1.8%.
  • the polyimide film of the present invention exhibits low dielectric constant, dielectric loss tangent, and moisture absorption rate as described above, and can be effectively used for an inner insulator, a buffer, a circuit board, and the like of electronic equipment.
  • Example 1 Preparation of polyimide film to which fumed silica particles were applied (1)
  • the thus-prepared gel film was peeled off from the stainless plate and fixed with a frame pin. After the frame having the gel film fixed thereon was heat-treated at 400 DEG C for 7 minutes, the film was peeled off to obtain a polyimide film having an average thickness of 25 mu m.
  • a polyimide film having an average thickness of 25 ⁇ was obtained in the same manner as in Example 1, except that 101.67 g of the imidization conversion liquid obtained in Production Example 3 was used in place of the imidization conversion liquid obtained in Production Example 2.
  • a polyimide film having an average thickness of 25 ⁇ was obtained in the same manner as in Example 1, except that 102.53 g of the imidization conversion liquid obtained in Production Example 4 was used in place of the imidization conversion liquid obtained in Production Example 2.
  • a polyimide film having an average thickness of 25 ⁇ was obtained in the same manner as in Example 1, except that 103.48 g of the imidization conversion liquid obtained in Production Example 5 was used in place of the imidization conversion liquid obtained in Production Example 2.
  • a polyimide film having an average thickness of 25 ⁇ was obtained in the same manner as in Example 1, except that 104.53 g of the imidization conversion liquid obtained in Production Example 6 was used in place of the imidization conversion liquid obtained in Production Example 2.
  • a polyimide film having an average thickness of 25 ⁇ was obtained in the same manner as in Example 1 except that 105.70 g of the imidization conversion liquid obtained in Preparation Example 7 was used in place of the imidization conversion liquid obtained in Preparation Example 2.
  • a polyimide film having an average thickness of 25 ⁇ was obtained in the same manner as in Example 1, except that 104.53 g of the imidization conversion liquid obtained in Production Example 9 was used in place of the imidization conversion liquid obtained in Production Example 2.
  • a polyimide film having an average thickness of 25 ⁇ was obtained in the same manner as in Example 1, except that 105.70 g of the imidization conversion liquid obtained in Production Example 10 was used in place of the imidization conversion liquid obtained in Production Example 2.
  • the dielectric constant and dielectric loss tangent of the polyimide films prepared in Examples 1 to 6 and Comparative Examples 1 to 3 at 1 GHz were measured using an SPDR meter of Keysight. As a result, the measured dielectric constant and dielectric loss tangent are shown in Table 1 below.
  • the polyimide films prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were cut to prepare five samples each having a size of 10 mm ⁇ 10 mm.
  • the samples were dried at 130 ° C. for 3 minutes and weighed. After drying the sample, the dried sample was thoroughly impregnated with pure water. After 24 hours, the moisture on both surfaces of the sample was wiped off and the weight was remeasured to measure the moisture absorption rate according to the sample weight change after drying and after impregnation. As a result, the measured moisture absorption rates are shown in Table 1 below.
  • Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Polyamic acid solution Production Example 1 Imidization conversion amount Production Example 2 Production Example 3 Production Example 4 Production Example 5 Production Example 6 Production Example 7 Production Example 8 Production Example 9 Production Example 10 Fumed silica particles (% by weight) 5 9 13 17 21 25 0 21 25 Permittivity (1 GHz) 3.4 3.2 3.0 2.8 2.6 2.4 3.7 2.8 2.7 Dielectric tangent (1 GHz) 0.007 0.006 0.006 0.006 0.005 0.004 0.013 0.010 0.008 Moisture absorption rate 1.8% 1.6% 1.3% 1.1% 0.9% 0.8% 2.8% 2.5% 2.3%
  • the polyimide films of Examples 1 to 6 prepared by applying the fumed silica particles having a pore size of 20 nm with a particle size of 5 mu m were the polyimide films of Comparative Example 1 containing no fumed silica particles Dielectric loss tangent, and moisture absorption rate, respectively.
  • the polyimide films of Examples 1 to 6 had lower dielectric loss tangent and moisture absorption rate values than the polyimide films of Comparative Examples 2 and 3 including hollow silica particles having a pore size of 200 nm, . ≪ / RTI > Therefore, the polyimide film to which the fumed silica particles having the specific particle diameter and the specific-size pore are applied has a better dielectric constant, dielectric tangent, and dielectric constant than the polyimide film containing no fumed silica particles or the polyimide film containing the ordinary hollow silica particles. It was confirmed that the moisture absorption rate effect can be realized.

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Abstract

The present invention relates to a method for manufacturing a polyimide film using fumed silica particles, and a polyimide film having a low dielecgric constant manufactured by the method. The polyimide film manufactured by the method according to the present invention has a minimal dielectric constant and thus can ben useful in an insulator, a buffer material, and a circuit board among others, inside of electric devices and the like.

Description

흄드 실리카 입자를 이용한 폴리이미드 필름의 제조방법 및 저유전율의 폴리이미드 필름Process for producing polyimide film using fumed silica particles and polyimide film having low dielectric constant
본 발명은 흄드 실리카 입자를 이용한 폴리이미드 필름의 제조방법, 및 상기 방법에 따라 제조된 저유전율의 폴리이미드 필름에 관한 것이다.The present invention relates to a process for producing a polyimide film using fumed silica particles and a low-dielectric-constant polyimide film produced by the process.
일반적으로 폴리이미드(PI) 수지라 함은 방향족 디안하이드라이드와 방향족 디아민 또는 방향족 디이소시아네이트를 용액 중합하여 폴리아믹산 유도체를 제조한 후, 고온에서 폐환 탈수시켜 이미드화하여 제조되는 고내열 수지를 일컫는다.In general, polyimide (PI) resin refers to a high heat resistant resin prepared by solution polymerization of an aromatic dianhydride and an aromatic dianhydride or an aromatic diisocyanate to prepare a polyamic acid derivative, followed by ring-closing dehydration at a high temperature and imidization.
폴리이미드 수지는 불용, 불융의 초고내열성 수지로서 내열산화성, 내열특성, 내방사선성, 저온특성, 내약품성 등의 우수한 특성을 가지고 있어, 자동차 재료, 항공소재, 우주선 소재 등의 내열 첨단소재 및 절연코팅제, 절연막, 반도체, TFT-LCD의 전극 보호막 등과 같은 전자재료에 광범위하게 사용되고 있다.Polyimide resin is an insoluble and infusible ultra-high temperature resistant resin, and has excellent properties such as heat resistance, heat resistance, radiation resistance, low temperature property, and chemical resistance. It is a high temperature resistant material such as automobile material, Coating materials, insulating films, semiconductors, electrode protective films of TFT-LCD, and the like.
최근에는, 고도 정보화 사회에 대응하는 대량의 정보를 축적하여, 이러한 정보를 고속으로 처리하고, 고속으로 전달하기 위한 전자기기에 있어서, 이들에 사용되는 폴리이미드 수지에도 고성능화, 특히 고주파화에 대응하는 전기적 특성으로서 저유전율화 및 저유전 정접(tangent)화가 요구되고 있다.In recent years, in an electronic apparatus for accumulating a large amount of information corresponding to a highly information-oriented society and processing such information at a high speed and delivering it at a high speed, it has been desired to provide a polyimide resin, A low dielectric constant and a low dielectric tangent are required as electrical characteristics.
폴리이미드 수지의 저유전율화의 시도로서, 예를 들면, 일본 공개특허공보 제2000-44719호에서 유기 용매에 가용성인 폴리이미드 수지 전구체 중에 친수성 중합체를 분산시켜, 이러한 친수성 중합체를 소성 또는 용매 추출에 의해서 제거함으로써 다공질화하여, 다공질 폴리이미드 수지를 수득하는 것이 제안되었다. 그러나, 이와 같이 친수성 중합체를 제거하여 다공질화하는 경우에는 친수성 중합체가 폴리이미드 수지 전구체 중에 분산된 미세상 분리 형태가 그대로 유지되며 구멍이 형성되는 것이 이상적이지만, 친수성 중합체를 그대로 소성 또는 용매 추출에 의해서 제거한 후 이미드화하면, 구멍이 편평해지거나 폐색되어 공공률(porosity rate)이 이상값보다도 작아져서 유전율을 충분히 저하시킬 수 없다.As an attempt to lower the dielectric constant of the polyimide resin, for example, in Japanese Patent Application Laid-Open No. 2000-44719, a hydrophilic polymer is dispersed in a polyimide resin precursor soluble in an organic solvent, and this hydrophilic polymer is subjected to firing or solvent extraction To thereby obtain a porous polyimide resin. However, in the case of removing the hydrophilic polymer and making it porous in this way, it is ideal that the microphase separated form in which the hydrophilic polymer is dispersed in the polyimide resin precursor is maintained as it is and holes are formed. However, If imidized after removal, the hole becomes flat or clogged and the porosity rate becomes smaller than the ideal value, so that the permittivity can not be sufficiently lowered.
대한민국 특허 제1299652호는 연성 금속 적층판을 제조함에 있어 불소 입자를 사용하는 구성에 대해서 개시하고 있으나, 그 방법이 불소 입자 단분자의 적용에 대한 것이고, 상기 불소 입자는 잘 분산되지 않는다는 단점이 있다.Korean Patent No. 1299652 discloses a construction using fluorine particles in the production of a flexible metal laminate, but the method is based on the application of monomolecular fluorine particles, and the fluorine particles are not well dispersed.
이에, 본 발명자들은 공기가 갖는 전기적인 특성을 기공을 갖는 흄드 실리카 입자를 통해 기존의 폴리이미드 필름이 갖는 유전율보다 낮은 유전율을 구현하는 것은 물론, 제조공정 중 상기 흄드 실리카 입자의 분산성을 향상시켜 가라앉음 현상을 개선한 폴리이미드 필름의 제조방법을 개발함으로써 본 발명을 완성하였다.Accordingly, the present inventors have found that the electrical properties of air can be realized by using fumed silica particles having pores to realize a dielectric constant lower than that of a conventional polyimide film, and to improve dispersibility of the fumed silica particles during the manufacturing process The inventors of the present invention have completed the present invention by developing a method for producing a polyimide film with improved sinking phenomenon.
따라서, 본 발명의 목적은 저유전율의 폴리이미드 필름을 제조하는 방법, 및 상기 방법에 따라 제조된 저유전율의 폴리이미드 필름을 제공하는 것이다.Accordingly, an object of the present invention is to provide a method for producing a polyimide film having a low dielectric constant, and a polyimide film having a low dielectric constant produced according to the method.
상기 목적을 달성하기 위하여 본 발명은, 1) 폴리이미드 전구체를 제조하는 단계; 2) 상기 폴리이미드 전구체에 흄드 실리카 입자를 포함하는 이미드화 변환액을 혼합하여 겔 필름을 제조하는 단계; 및 3) 상기 겔 필름을 열처리하여 이미드화하는 단계를 포함하며, 이때, 상기 흄드 실리카 입자가 평균 입경이 10 ㎛ 이하이고, 평균 크기 300 nm 이하의 기공을 갖는 것을 특징으로 하는, 폴리이미드 필름의 제조방법을 제공한다.In order to accomplish the above object, the present invention provides a method for producing a polyimide precursor, comprising: 1) preparing a polyimide precursor; 2) mixing a polyimide precursor with an imidization conversion liquid containing fumed silica particles to prepare a gel film; And 3) heat treating the gel film to imidize the fumed silica particles, wherein the fumed silica particles have pores having an average particle size of 10 m or less and an average size of 300 nm or less And a manufacturing method thereof.
상기 목적을 달성하기 위하여 본 발명은 또한, 흄드 실리카 입자를 포함하는 폴리이미드 필름으로서, 상기 흄드 실리카 입자가 평균 입경이 10 ㎛ 이하이고, 평균 크기가 300 nm 이하의 기공을 갖는 것을 특징으로 하는, 폴리이미드 필름을 제공한다.In order to achieve the above object, the present invention also provides a polyimide film comprising fumed silica particles, wherein the fumed silica particles have pores with an average particle diameter of 10 m or less and an average size of 300 nm or less. Thereby providing a polyimide film.
본 발명의 방법에 따라 흄드 실리카 입자를 이용하여 제조된 폴리이미드 필름은 유전율, 유전 정접 및 흡습율이 최소화되어, 전기기기 등의 내부 절연체, 완충재, 회로기판 등에 유용하게 사용될 수 있다.The polyimide film produced using the fumed silica particles according to the method of the present invention is minimized in dielectric constant, dielectric loss tangent, and moisture absorption rate and can be effectively used for an inner insulator, a buffer material, a circuit board, and the like of an electric apparatus.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은, 1) 폴리이미드 전구체를 제조하는 단계; 2) 상기 폴리이미드 전구체에 흄드 실리카 입자를 포함하는 이미드화 변환액을 혼합하여 겔 필름을 제조하는 단계; 및 3) 상기 겔 필름을 열처리하여 이미드화하는 단계를 포함하며, 이때, 상기 흄드 실리카 입자가 평균 입경이 10 ㎛ 이하이고, 평균 크기 300 nm 이하의 기공을 갖는 것을 특징으로 하는, 폴리이미드 필름의 제조방법을 제공한다.The present invention provides: 1) a step of producing a polyimide precursor; 2) mixing a polyimide precursor with an imidization conversion liquid containing fumed silica particles to prepare a gel film; And 3) heat treating the gel film to imidize the fumed silica particles, wherein the fumed silica particles have pores having an average particle size of 10 m or less and an average size of 300 nm or less And a manufacturing method thereof.
본 발명에 따른 제조방법의 단계 1)은 폴리이미드 전구체를 제조하는 단계이다.Step 1) of the production process according to the present invention is a step of producing a polyimide precursor.
상기 폴리이미드 전구체로는 이미드화에 의해 폴리이미드 수지가 될 수 있는 것이라면 무엇이든 사용할 수 있다. 예를 들어 폴리이미드 전구체는, 통상적인 방법에 따라 산 이무수물 성분과 디아민 성분을 유기 용매의 존재하에서 공중합하여 얻어진 폴리아믹산일 수 있다.As the polyimide precursor, any material that can become a polyimide resin by imidization can be used. For example, the polyimide precursor may be a polyamic acid obtained by copolymerizing an acid dianhydride component and a diamine component in the presence of an organic solvent according to a conventional method.
상기 산 이무수물 성분 및 디아민 성분은 각각 폴리아믹산의 제조에 통상적으로 사용되는 것 중에서 적절히 선택될 수 있다. 산 이무수물 성분의 예는 비페닐테트라카르복실산 이무수물 또는 그 유도체, 피로멜리트산 이무수물(PMDA), 3,3'4,4'-벤조페논테트라카르복실산 무수물, p-페닐렌-비스 트리멜리트산 이무수물 등이 있다. 또한, 디아민 성분의 예는 파라-페닐렌디아민(pPDA), 디아미노페닐에테르, o-페닐렌디아민, m-페닐렌디아민, 4,4-디아미노디페닐에테르(ODA), 3,4-디아미노디페닐에테르, 2,4-디아미노디페닐에테르 등이 있다. 상기 산 이무수물 성분 및 디아민 성분은 1:0.9 내지 1:1.1의 몰비로 혼합될 수 있다.The acid dianhydride component and the diamine component may be appropriately selected from those conventionally used in the production of polyamic acid. Examples of the acid dianhydrides include biphenyltetracarboxylic acid dianhydride or derivatives thereof, pyromellitic dianhydride (PMDA), 3,3'4,4'-benzophenonetetracarboxylic acid anhydride, p-phenylene- And bistrimelitic acid dianhydride. Examples of the diamine component include para-phenylenediamine (pPDA), diaminophenyl ether, o-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether (ODA) Diaminodiphenyl ether, 2,4-diaminodiphenyl ether, and the like. The acid dianhydride component and the diamine component may be mixed in a molar ratio of 1: 0.9 to 1: 1.1.
상기 유기 용매의 예는 N,N'-디메틸포름아미드(DMF), N,N'-디메틸아세트아미드(DMAc), N-메틸-피롤리돈(NMP) 등이 있다.Examples of the organic solvent include N, N'-dimethylformamide (DMF), N, N'-dimethylacetamide (DMAc), N-methyl-pyrrolidone (NMP) and the like.
본 발명에 따른 제조방법의 단계 2)에서는, 단계 1)에서 제조된 폴리이미드 전구체에 흄드 실리카 입자를 포함하는 이미드화 변환액을 혼합하여 겔 필름을 제조한다.In step 2) of the production method according to the present invention, a gel film is prepared by mixing the imidization conversion liquid containing the fumed silica particles with the polyimide precursor prepared in step 1).
우선, 흄드 실리카 입자를 이미드화 변환액에 첨가하고, 얻어진 이미드화 변환액을 상기 폴리이미드 전구체, 예를 들어 폴리아믹산에 첨가하여 이미드화 수지 혼합물을 제조한다.First, fumed silica particles are added to the imidization conversion liquid, and the resulting imidization conversion liquid is added to the polyimide precursor, for example, polyamic acid to prepare an imidized resin mixture.
상기 이미드화 변환액은 화학적 경화를 일으키기 위해 통상적으로 사용되는 물질이면 무엇이든 사용될 수 있다. 상기 이미드화 변환액은 탈수제, 촉매, 극성 유기용제 및 이의 혼합 용액으로 구성된 군으로부터 선택될 수 있고, 구체적으로, 탈수제, 촉매 및 극성 유기용제의 혼합 용액일 수 있다. 더욱 구체적으로, 상기 이미드화 변환액은 아세트산 무수물 등과 같은 탈수제; 피리딘, 베타피콜린, 이소퀴놀린을 포함하는 3급 아민류 등의 촉매; 및 N-메틸피롤리돈, 디메틸포름아미드, 디메틸아세트아미드 등과 같은 극성 유기용제를 포함할 수 있다.The imidization conversion liquid may be any material conventionally used to cause chemical hardening. The imidization conversion liquid may be selected from the group consisting of a dehydrating agent, a catalyst, a polar organic solvent and a mixed solution thereof, and specifically, it may be a mixed solution of a dehydrating agent, a catalyst and a polar organic solvent. More specifically, the imidization conversion liquid may be a dehydrating agent such as acetic anhydride or the like; Tertiary amines including pyridine, beta picoline and isoquinoline; And polar organic solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and the like.
상기 이미드화 변환액은 폴리이미드 전구체 100 중량부를 기준으로 160 내지 800 중량부, 구체적으로는 270 내지 650 중량부로 사용될 수 있고 더욱 구체적으로 400 내지 550 중량부로 사용될 수 있다. 상기 이미드화 변환액 사용량은 사용되는 폴리이미드 전구체의 종류 및 제조되는 폴리이미드 필름의 두께 등에 의하여 달라질 수 있다.The imidization conversion liquid may be used in an amount of 160 to 800 parts by weight, specifically, 270 to 650 parts by weight, and more specifically 400 to 550 parts by weight, based on 100 parts by weight of the polyimide precursor. The amount of the imidization conversion liquid used may vary depending on the kind of the polyimide precursor used and the thickness of the polyimide film to be produced.
본 명세서에서 사용된 용어 "흄드 실리카(fumed silica)"는 건식법으로 제조되는 것으로, 사염화실리콘(SiCl4)을 공기중에서 가열분해하여 수득되는 실리카(SiO2)를 나타낸다. 흄드 실리카는 일반적으로 표면적이 크고 입자가 고운 특징이 있다.The term "fumed silica (fumed silica)" as used herein is to be produced by the dry process, shows a silica (SiO 2) obtained a silicon tetrachloride (SiCl 4) and heated in air to decompose. Fumed silica generally has high surface area and fine grain characteristics.
본 발명에 사용된 흄드 실리카는 기공을 갖는 입자일 수 있다. 기공을 갖는 흄드 실리카를 이용함으로써 공기가 갖는 전기적인 특성을 구현하여 낮은 유전율의 특징을 나타내는 폴리이미드 필름을 제조할 수 있다. 또한, 상기 흄드 실리카는 중공형 또는 메조세공형(mesoporous) 입자일 수 있다. 아울러, 상기 흄드 실리카는 사염화실리콘으로부터 제조된 것 또는 상업적으로 판매되는 것이 모두 사용될 수 있다.The fumed silica used in the present invention may be particles having pores. By using the fumed silica having pores, the polyimide film exhibiting the characteristic of low dielectric constant can be manufactured by realizing the electrical characteristics of the air. The fumed silica may also be a hollow or mesoporous particle. In addition, the fumed silica may be either produced from silicon tetrachloride or commercially available.
본 발명에 따른 흄드 실리카 입자는 평균 입경이 10 ㎛ 이하, 구체적으로 0.3 내지 10 ㎛, 더욱 구체적으로 3 내지 10 ㎛일 수 있다. 본 발명의 일 구체예에 의하면 흄드 실리카 입자의 평균 입경은 5 ㎛일 수 있다.The fumed silica particles according to the present invention may have an average particle diameter of 10 mu m or less, specifically 0.3 to 10 mu m, more specifically 3 to 10 mu m. According to one embodiment of the present invention, the average particle diameter of the fumed silica particles may be 5 탆.
또한, 상기 흄드 실리카 입자는 평균 크기 300 nm 이하, 100 nm 이하, 50 nm 이하, 또는 20 nm 이하의 기공을 가질 수 있다. 구체적으로, 상기 흄드 실리카 입자는 평균 크기 0.1 내지 300 nm, 1 내지 300 nm, 10 내지 300 nm, 0.1 내지 100 nm, 1 내지 100 nm, 10 내지 100 nm, 0.1 내지 50 nm, 1 내지 50 nm, 10 내지 50 nm, 0.1 내지 20 nm, 1 내지 20 nm, 또는 10 내지 20 nm의 기공을 가질 수 있다.The fumed silica particles may have pores having an average size of 300 nm or less, 100 nm or less, 50 nm or less, or 20 nm or less. In detail, the fumed silica particles have an average size of 0.1 to 300 nm, 1 to 300 nm, 10 to 300 nm, 0.1 to 100 nm, 1 to 100 nm, 10 to 100 nm, 0.1 to 50 nm, 10 to 50 nm, 0.1 to 20 nm, 1 to 20 nm, or 10 to 20 nm.
바람직하게는, 본 발명에 따른 흄드 실리카 입자는 평균 입경이 3 내지 10 ㎛이고 평균 크기 1 내지 100 nm의 기공을 가질 수 있다.Preferably, the fumed silica particles according to the present invention may have pores having an average particle size of 3 to 10 mu m and an average size of 1 to 100 nm.
또한, 상기 흄드 실리카 입자의 비표면적은 300 ㎡/g 이상, 구체적으로 300 내지 2,000 ㎡/g, 더욱 구체적으로 600 내지 1,000 ㎡/g일 수 있다.Also, the specific surface area of the fumed silica particles may be 300 m 2 / g or more, specifically 300 to 2,000 m 2 / g, more specifically 600 to 1,000 m 2 / g.
상기 흄드 실리카 입자의 함량은 필름 총 중량을 기준으로 2 내지 30 중량%, 구체적으로는 5 내지 20 중량%, 더욱 구체적으로 13 내지 17 중량%일 수 있다. 흄드 실리카 입자의 함량이 상기 범위 내이면 폴리이미드 필름의 기계적 물성이 최소화 될 뿐만 아니라, 상기 필름의 저유전 효과를 구현할 수 있다.The content of the fumed silica particles is 2 to 30% by weight, specifically 5 to 20% by weight, more specifically 13 To 17% by weight. When the content of the fumed silica particles is within the above range, not only the mechanical properties of the polyimide film are minimized, but also the low dielectric effect of the film can be realized.
본 발명에 따른 이미드화 변환액에 첨가되는 흄드 실리카 입자는, 입자 그 자체로 첨가될 수 있다. 다르게는, 상기 흄드 실리카 입자는 이미드화 변환액에서 보다 균일하게 분산 및 혼합되도록 극성 유기용제에 분산한 분산액 상태 또는 콜로이드 상태로 첨가될 수 있다.The fumed silica particles added to the imidization conversion liquid according to the present invention can be added as the particles themselves. Alternatively, the fumed silica particles may be added in a dispersion state or a colloid state dispersed in a polar organic solvent so as to be more uniformly dispersed and mixed in the imidization conversion liquid.
이어서, 상기에서 얻어진 이미드화 수지 혼합물로부터 겔 필름을 제조할 수 있다. 구체적으로, 상기 이미드화 수지 혼합물을 지지체(예컨대, 스테인레스판, 유리판, 알루미늄박, 순환 스테인레스 벨트 또는 스테인레스 드럼 등)에 도포한 후, 1차 열처리 및 건조를 통해 화학적으로 부분 이미드화된 겔 필름을 제조할 수 있다. 이때, 1차 열처리는 100℃ 내지 200℃의 온도에서 1 내지 15분 동안 수행될 수 있다.Then, a gel film can be prepared from the imidized resin mixture obtained above. Specifically, the imidized resin mixture is coated on a support (for example, a stainless steel plate, a glass plate, an aluminum foil, a circulating stainless belt or a stainless steel drum), and then a chemically partially imaged gel film is subjected to primary heat treatment and drying Can be manufactured. At this time, the primary heat treatment may be performed at a temperature of 100 ° C to 200 ° C for 1 to 15 minutes.
본 발명에 따른 제조방법의 단계 3)에서는 단계 2)에서 제조된 겔 필름을 열처리하여 이미드화한다.In step 3) of the production method according to the present invention, the gel film prepared in step 2) is heat-treated to be imidized.
단계 2)에서 제조된 화학적으로 부분 이미드화된 겔 필름은 완전 이미드화를 위해 지지체로부터 분리되어 2차 열처리될 수 있다. 2차 열처리는 250℃ 내지 850℃의 온도에서 5 내지 25분 동안 수행될 수 있다. 상기 2차 열처리는, 제막 과정에서 발생한 필름 내부의 잔류 응력을 제거하기 위해 일정한 장력 하에서 수행될 수 있다.The chemically partially imidized gel film prepared in step 2) can be separated from the support for complete imidization and subjected to a secondary heat treatment. The secondary heat treatment may be carried out at a temperature of 250 캜 to 850 캜 for 5 to 25 minutes. The secondary heat treatment may be performed under a constant tension to remove residual stress in the film generated during the film formation process.
본 발명의 일 구체예에 따르면, 폴리이미드 전구체로서 폴리아믹산을 제조하고; 상기 폴리아믹산에 평균 입경이 10 ㎛ 이하, 기공의 평균 크기가 300 nm 이하, 입자의 비표면적이 300 ㎡/g 이상인 흄드 실리카 입자가 균일하게 분산된 이미드화 변환액을 혼합하여 이미드화 수지 혼합물을 제조하고, 상기 이미드화 수지 혼합물을 지지체 상에 도포하고 120℃에서 3분간 1차 열처리 및 건조하여 겔 필름을 제조한 다음; 상기 겔 필름을 400℃에서 7분간 2차 열처리하여 폴리이미드 필름을 제조한다.According to one embodiment of the present invention, there is provided a process for preparing a polyamic acid as a polyimide precursor; An imidization conversion liquid in which the fumed silica particles having an average particle diameter of 10 mu m or less, an average pore size of 300 nm or less and a specific surface area of 300 m < 2 > / g or more are uniformly dispersed is mixed in the polyamic acid, The imidized resin mixture was coated on a support and subjected to a first heat treatment at 120 ° C for 3 minutes and dried to prepare a gel film; The gel film was subjected to a secondary heat treatment at 400 DEG C for 7 minutes to produce a polyimide film.
한편, 본 발명은 평균 입경이 10 ㎛ 이하이고, 평균 크기 300 nm 이하의 기공을 갖는 흄드 실리카 입자를 포함하는 폴리이미드 필름을 제공한다.On the other hand, the present invention provides a polyimide film comprising fumed silica particles having an average particle diameter of 10 m or less and pores having an average size of 300 nm or less.
구체적으로, 상기 흄드 실리카 입자를 포함하는 폴리이미드 필름은, 폴리아믹산 및 흄드 실리카 입자를 포함하는 이미드화 변환액을 이용하여 합성한 폴리이미드화 수지로부터 수득되며, 상기 흄드 실리카 입자가 평균 입경이 10 ㎛ 이하이고, 평균 크기 300 nm 이하의 기공을 갖는, 폴리이미드 필름일 수 있다.Specifically, the polyimide film comprising the fumed silica particles is obtained from a polyimidated resin synthesized using an imidization conversion solution comprising polyamic acid and fumed silica particles, wherein the fumed silica particles have an average particle size of 10 Mu m or less and having pores with an average size of 300 nm or less.
상기 흄드 실리카 입자는 상기 설명된 바와 같다.The fumed silica particles are as described above.
본 발명에 따른 폴리이미드 필름의 두께는 12.5 내지 50 ㎛일 수 있다.The thickness of the polyimide film according to the present invention may be 12.5 to 50 탆.
본 발명에 따른 폴리이미드 필름의 유전율은 1 GHz에서 3.4 이하, 구체적으로 2.7 내지 3.4 또는 2.7 내지 3.0일 수 있다. 또한, 상기 폴리이미드 필름의 유전 정접은 1 GHz에서 0.02 미만, 구체적으로는 0.005 내지 0.02, 또는 0.005 내지 0.01일 수 있다. The dielectric constant of the polyimide film according to the present invention may be 3.4 or less at 1 GHz, specifically 2.7 to 3.4 or 2.7 to 3.0. The dielectric loss tangent of the polyimide film may be less than 0.02 at 1 GHz, specifically 0.005 to 0.02, or 0.005 to 0.01.
본 발명에 따른 폴리이미드 필름의 흡습율은 2% 이하, 구체적으로는 0.1 내지 2%, 0.1 내지 1.8%, 0.5 내지 1.8% 또는 0.8 내지 1.8%일 수 있다. The moisture absorption rate of the polyimide film according to the present invention may be 2% or less, specifically 0.1 to 2%, 0.1 to 1.8%, 0.5 to 1.8% or 0.8 to 1.8%.
본 발명의 폴리이미드 필름은 상기와 같이 낮은 유전율, 유전 정접 및 흡습율을 나타내어 전자기기 등의 내부 절연체, 완충제, 회로기판 등에 유용하게 사용될 수 있다.The polyimide film of the present invention exhibits low dielectric constant, dielectric loss tangent, and moisture absorption rate as described above, and can be effectively used for an inner insulator, a buffer, a circuit board, and the like of electronic equipment.
이하, 본 발명을 하기 실시예에 의해 상세히 설명한다. 단, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명이 이들에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail by the following examples. However, the following examples are illustrative of the present invention, but the present invention is not limited thereto.
제조예 1. 폴리아믹산 용액의 제조Production Example 1. Preparation of polyamic acid solution
0.5 ℓ 반응기에 디메틸포름아미드(DMF) 320 g을 넣고 온도를 20℃로 설정한 다음, 디아미노페닐에테르(ODA) 27.59 g을 투입하여 용해시킨 뒤에 피로멜리트산 이무수물(PMDA)을 20.03 g씩 2회 투입 후 용해하였다. 용해가 끝나면, 여기에 파라-페닐렌디아민(pPDA) 3.97 g을 투입하여 30분간 반응시킨 후에 용액을 샘플링하여 분자량을 측정하였다. 이 후, 반응이 끝나면 반응기의 온도를 30℃로 승온한 뒤에 pPDA 1.00 g을 투입하여 [디아민]/[산 이무수물]의 몰비를 1:1로 조절하였다. 원료 투입을 완료하면 40℃에서 2시간 동안 반응시켜 폴리아믹산 용액을 얻었다.In a 0.5 L reactor, 320 g of dimethylformamide (DMF) was added, and the temperature was set to 20 ° C. 27.59 g of diaminophenyl ether (ODA) was added to dissolve and then 20.03 g of pyromellitic dianhydride And the mixture was added twice and dissolved. After the dissolution, 3.97 g of para-phenylenediamine (pPDA) was added thereto and reacted for 30 minutes. The solution was sampled to measure the molecular weight. After the reaction was completed, the temperature of the reactor was raised to 30 ° C., and 1.00 g of pPDA was added to adjust the molar ratio of [diamine] / [dianhydride] to 1: 1. After the addition of the raw material was completed, the reaction was carried out at 40 DEG C for 2 hours to obtain a polyamic acid solution.
제조예 2. 흄드 실리카 입자가 첨가된 이미드화 변환액의 제조(1)Preparation Example 2. Preparation of imidization conversion liquid added with fumed silica particles (1)
이미드화 변환액에 사용되는 경화용 촉매로서 베타피콜린(끓는점 144℃) 13.1 g, 탈수제로서 아세트산 무수물 95.7 g 및 극성 유기용제로서 디메틸포름아미드(DMF) 291.2 g의 혼합 용액에, 흄드 실리카 입자(입자의 평균 입경: 5 ㎛, 입자의 평균 기공 크기: 20 ㎚ 이하, 입수처: JIOS Aerogel Corporation) 3.6 g을 첨가한 후 교반하여, 흄드 실리카 입자가 첨가된 이미드화 변환액 403.6 g을 얻었다.To a mixed solution of 13.1 g of beta-picoline (boiling point 144 DEG C) as a curing catalyst used in the imidation conversion solution, 95.7 g of acetic anhydride as a dehydrating agent and 291.2 g of dimethylformamide (DMF) as a polar organic solvent, fumed silica particles 3.6 g of an average particle diameter of the particles: 5 mu m, average pore size of the particles: 20 nm or less, available from JIOS Aerogel Corporation) was added and stirred to obtain 403.6 g of an imidization conversion liquid to which the fumed silica particles were added.
제조예 3. 흄드 실리카 입자가 첨가된 이미드화 변환액의 제조(2)Production Example 3: Preparation of imidization conversion liquid added with fumed silica particles (2)
이미드화 변환액에 사용되는 경화용 촉매로서 베타피콜린(끓는점 144℃) 13.1 g, 탈수제로서 아세트산 무수물 95.7 g 및 극성 유기용제로서 디메틸포름아미드(DMF) 291.2 g의 혼합 용액에, 흄드 실리카 입자(입자의 평균 입경: 5 ㎛, 입자의 평균 기공 크기: 20 ㎚ 이하, 입수처: JIOS Aerogel Corporation) 6.7 g을 첨가한 후 교반하여, 흄드 실리카 입자가 첨가된 이미드화 변환액 406.7 g을 얻었다.To a mixed solution of 13.1 g of beta-picoline (boiling point 144 DEG C) as a curing catalyst used in the imidation conversion solution, 95.7 g of acetic anhydride as a dehydrating agent and 291.2 g of dimethylformamide (DMF) as a polar organic solvent, fumed silica particles 6.7 g of an average particle diameter of the particles: 5 mu m, average pore size of the particles: 20 nm or less, available from JIOS Aerogel Corporation) was added and stirred to obtain 406.7 g of an imidation conversion liquid to which the fumed silica particles were added.
제조예 4. 흄드 실리카 입자가 첨가된 이미드화 변환액의 제조(3)Production Example 4. Preparation of imidization conversion liquid added with fumed silica particles (3)
이미드화 변환액에 사용되는 경화용 촉매로서 베타피콜린(끓는점 144℃) 13.1 g, 탈수제로서 아세트산 무수물 95.7 g 및 극성 유기용제로서 디메틸포름아미드(DMF) 291.2 g의 혼합 용액에, 흄드 실리카(입자의 평균 입경: 5 ㎛, 입자의 평균 기공 크기: 20 ㎚ 이하, 입수처: JIOS Aerogel Corporation) 10.1 g을 첨가한 후 교반하여, 흄드 실리카 입자가 첨가된 이미드화 변환액 410.1 g을 얻었다.To a mixed solution of 13.1 g of beta-picoline (boiling point 144 DEG C) as a curing catalyst used in the imidation conversion solution, 95.7 g of acetic anhydride as a dehydrating agent and 291.2 g of dimethylformamide (DMF) as a polar organic solvent, 10.1 g, available from JIOS Aerogel Corporation) was added and stirred to obtain 410.1 g of the imidization conversion liquid to which the fumed silica particles had been added.
제조예 5. 흄드 실리카 입자가 첨가된 이미드화 변환액의 제조(4)Preparation Example 5. Preparation of imidization conversion liquid added with fumed silica particles (4)
이미드화 변환액에 사용되는 경화용 촉매로서 베타피콜린(끓는점 144℃) 13.1 g, 탈수제로서 아세트산 무수물 95.7 g 및 극성 유기용제로서 디메틸포름아미드(DMF) 291.2 g의 혼합 용액에, 흄드 실리카(입자의 평균 입경: 5 ㎛, 입자의 평균 기공 크기: 20 ㎚ 이하, 입수처: JIOS Aerogel Corporation) 13.9 g을 첨가한 후 교반하여, 흄드 실리카 입자가 첨가된 이미드화 변환액 413.9 g을 얻었다.To a mixed solution of 13.1 g of beta-picoline (boiling point 144 DEG C) as a curing catalyst used in the imidation conversion solution, 95.7 g of acetic anhydride as a dehydrating agent and 291.2 g of dimethylformamide (DMF) as a polar organic solvent, 13.9 g of JIOS Aerogel Corporation) was added and stirred to obtain 413.9 g of an imidization conversion liquid to which the fumed silica particles had been added.
제조예 6. 흄드 실리카 입자가 첨가된 이미드화 변환액의 제조(5)Production Example 6. Preparation of imidization conversion liquid added with fumed silica particles (5)
이미드화 변환액에 사용되는 경화용 촉매로서 베타피콜린(끓는점 144℃) 13.1 g, 탈수제로서 아세트산 무수물 95.7 g 및 극성 유기용제로서 디메틸포름아미드(DMF) 291.2 g의 혼합 용액에, 흄드 실리카(입자의 평균 입경: 5 ㎛, 입자의 평균 기공 크기: 20 ㎚ 이하, 입수처: JIOS Aerogel Corporation) 18.1 g을 첨가한 후 교반하여, 흄드 실리카 입자가 첨가된 이미드화 변환액 418.1 g을 얻었다.To a mixed solution of 13.1 g of beta-picoline (boiling point 144 DEG C) as a curing catalyst used in the imidation conversion solution, 95.7 g of acetic anhydride as a dehydrating agent and 291.2 g of dimethylformamide (DMF) as a polar organic solvent, (Average particle diameter: 5 mu m, average pore size of particles: 20 nm or less, available from JIOS Aerogel Corporation) was added and stirred to obtain 418.1 g of an imidation conversion solution to which fumed silica particles were added.
제조예 7. 흄드 실리카 입자가 첨가된 이미드화 변환액의 제조(6)Preparation Example 7. Preparation of an imidization conversion liquid added with fumed silica particles (6)
이미드화 변환액에 사용되는 경화용 촉매로서 베타피콜린(끓는점 144℃) 13.1 g, 탈수제로서 아세트산 무수물 95.7 g 및 극성 유기용제로서 디메틸포름아미드(DMF) 291.2 g의 혼합 용액에, 흄드 실리카(입자의 평균 입경: 5 ㎛, 입자의 평균 기공 크기: 20 ㎚ 이하, 입수처: JIOS Aerogel Corporation) 22.8 g을 첨가한 후 교반하여, 흄드 실리카 입자가 첨가된 이미드화 변환액 422.8 g을 얻었다.To a mixed solution of 13.1 g of beta-picoline (boiling point 144 DEG C) as a curing catalyst used in the imidation conversion solution, 95.7 g of acetic anhydride as a dehydrating agent and 291.2 g of dimethylformamide (DMF) as a polar organic solvent, 22.8 g of JIOS Aerogel Corporation) was added and stirred to obtain 422.8 g of the imidization conversion liquid to which the fumed silica particles had been added.
제조예 8. 흄드 실리카 입자가 포함되지 않은 이미드화 변환액의 제조Preparation Example 8. Preparation of imidization conversion liquid without fumed silica particles
이미드화 변환액에 사용되는 경화용 촉매로서 베타피콜린(끓는점 144℃) 13.1 g, 탈수제로서 아세트산 무수물 95.7 g 및 극성 유기용제로서 디메틸포름아미드(DMF) 291.2 g를 혼합 교반하여, 흄드 실리카 입자가 첨가되지 않은 이미드화 변환액 400 g을 얻었다.13.1 g of beta-picoline (boiling point 144 DEG C) as a curing catalyst to be used for the imidation conversion solution, 95.7 g of acetic anhydride as a dehydrating agent and 291.2 g of dimethylformamide (DMF) as a polar organic solvent were mixed and stirred to obtain fumed silica particles 400 g of an imidation conversion solution not added was obtained.
제조예 9. 중공 실리카 입자가 첨가된 이미드화 변환액의 제조(1)Preparation Example 9. Preparation of imidization conversion liquid added with hollow silica particles (1)
이미드화 변환액에 사용되는 경화용 촉매로서 베타피콜린(끓는점 144℃) 13.1 g, 탈수제로서 아세트산 무수물 95.7 g 및 극성 유기용제로서 디메틸포름아미드(DMF) 291.2 g의 혼합 용액에, 중공 실리카(입자의 평균 입경: 3 ㎛, 입자의 평균 기공 크기: 200 ㎚, 입수처: 백산철강) 18.1 g을 첨가한 후 교반하여, 중공 실리카 입자가 첨가된 이미드화 변환액 418.1 g을 얻었다.To a mixed solution of 13.1 g of beta-picoline (boiling point 144 DEG C) as a curing catalyst used in the imidation conversion solution, 95.7 g of acetic anhydride as a dehydrating agent and 291.2 g of dimethylformamide (DMF) as a polar organic solvent, 18.1 g) was added and stirred to obtain 418.1 g of the imidization conversion liquid to which the hollow silica particles had been added.
제조예 10. 중공 실리카 입자가 첨가된 이미드화 변환액의 제조(2)Preparation Example 10. Preparation of imidization conversion liquid added with hollow silica particles (2)
이미드화 변환액에 사용되는 경화용 촉매로서 베타피콜린(끓는점 144℃) 13.1 g, 탈수제로서 아세트산 무수물 95.7 g 및 극성 유기용제로서 디메틸포름아미드(DMF) 291.2 g의 혼합 용액에, 중공 실리카(입자의 평균 입경: 3 ㎛, 입자의 평균 기공 크기: 200 ㎚, 입수처: 백산철강) 22.8 g을 첨가한 후 교반하여, 중공 실리카 입자가 첨가된 이미드화 변환액 422.8 g을 얻었다.To a mixed solution of 13.1 g of beta-picoline (boiling point 144 DEG C) as a curing catalyst used in the imidation conversion solution, 95.7 g of acetic anhydride as a dehydrating agent and 291.2 g of dimethylformamide (DMF) as a polar organic solvent, , Average particle diameter: 3 占 퐉, average pore size of particles: 200 nm, available from Baishan Steel Co., Ltd.) were added and stirred to obtain 422.8 g of an imidation conversion liquid to which hollow silica particles were added.
실시예 1. 흄드 실리카 입자가 적용된 폴리이미드 필름의 제조(1)Example 1: Preparation of polyimide film to which fumed silica particles were applied (1)
상기 제조예 1에서 얻은 폴리아믹산 용액 100 g에 상기 제조예 2에서 얻은 이미드화 변환액 100.9 g을 섞은 후, 얻어진 혼합물을 스테인레스 판에 도포하고, 120℃ 오븐에서 열풍으로 3분간 건조하여 겔 필름을 제조하였다.After 100.9 g of the imidization conversion liquid obtained in Preparation Example 2 was mixed with 100 g of the polyamic acid solution obtained in Preparation Example 1, the resulting mixture was applied to a stainless steel plate and dried in a 120 ° C oven for 3 minutes with hot air to prepare a gel film .
이렇게 제조된 겔 필름을 스테인레스 판으로부터 떼어내어 프레임 핀으로 고정하고, 겔 필름이 고정된 프레임을 400℃에서 7분간 열처리한 후에 필름을 떼어내어 평균 두께가 25 ㎛인 폴리이미드 필름을 얻었다.The thus-prepared gel film was peeled off from the stainless plate and fixed with a frame pin. After the frame having the gel film fixed thereon was heat-treated at 400 DEG C for 7 minutes, the film was peeled off to obtain a polyimide film having an average thickness of 25 mu m.
실시예 2. 흄드 실리카 입자가 적용된 폴리이미드 필름의 제조(2)Example 2: Preparation of polyimide film to which fumed silica particles were applied (2)
제조예 2에서 얻은 이미드화 변환액 대신 제조예 3에서 얻은 이미드화 변환액 101.67 g을 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 평균 두께가 25 ㎛인 폴리이미드 필름을 얻었다.A polyimide film having an average thickness of 25 탆 was obtained in the same manner as in Example 1, except that 101.67 g of the imidization conversion liquid obtained in Production Example 3 was used in place of the imidization conversion liquid obtained in Production Example 2.
실시예 3. 흄드 실리카 입자가 적용된 폴리이미드 필름의 제조(3)Example 3: Preparation of polyimide film to which fumed silica particles were applied (3)
제조예 2에서 얻은 이미드화 변환액 대신 제조예 4에서 얻은 이미드화 변환액 102.53 g을 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 평균 두께가 25 ㎛인 폴리이미드 필름을 얻었다.A polyimide film having an average thickness of 25 탆 was obtained in the same manner as in Example 1, except that 102.53 g of the imidization conversion liquid obtained in Production Example 4 was used in place of the imidization conversion liquid obtained in Production Example 2.
실시예 4. 흄드 실리카 입자가 적용된 폴리이미드 필름의 제조(4)Example 4: Preparation of polyimide film to which fumed silica particles were applied (4)
제조예 2에서 얻은 이미드화 변환액 대신 제조예 5에서 얻은 이미드화 변환액 103.48 g을 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 평균 두께가 25 ㎛인 폴리이미드 필름을 얻었다.A polyimide film having an average thickness of 25 탆 was obtained in the same manner as in Example 1, except that 103.48 g of the imidization conversion liquid obtained in Production Example 5 was used in place of the imidization conversion liquid obtained in Production Example 2.
실시예 5. 흄드 실리카 입자가 적용된 폴리이미드 필름의 제조(5)Example 5: Preparation of polyimide film to which fumed silica particles were applied (5)
제조예 2에서 얻은 이미드화 변환액 대신 제조예 6에서 얻은 이미드화 변환액 104.53 g을 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 평균 두께가 25 ㎛인 폴리이미드 필름을 얻었다.A polyimide film having an average thickness of 25 탆 was obtained in the same manner as in Example 1, except that 104.53 g of the imidization conversion liquid obtained in Production Example 6 was used in place of the imidization conversion liquid obtained in Production Example 2.
실시예 6. 흄드 실리카 입자가 적용된 폴리이미드 필름의 제조(6)Example 6: Preparation of polyimide film with fumed silica particles (6)
제조예 2에서 얻은 이미드화 변환액 대신 제조예 7에서 얻은 이미드화 변환액 105.70 g을 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 평균 두께가 25 ㎛인 폴리이미드 필름을 얻었다.A polyimide film having an average thickness of 25 탆 was obtained in the same manner as in Example 1 except that 105.70 g of the imidization conversion liquid obtained in Preparation Example 7 was used in place of the imidization conversion liquid obtained in Preparation Example 2. [
비교예 1. 흄드 실리카 입자가 적용되지 않은 폴리이미드 필름의 제조Comparative Example 1. Preparation of polyimide film without fumed silica particles
제조예 2에서 얻은 이미드화 변환액 대신 제조예 8에서 얻은 (흄드 실리카 입자가 포함되지 않은) 이미드화 변환액 100 g을 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 평균 두께가 25 ㎛인 폴리이미드 필름을 얻었다.Except that 100 g of the imidization conversion liquid (obtained without the fumed silica particle) obtained in Production Example 8 was used in place of the imidization conversion liquid obtained in Production Example 2, and an average thickness of 25 mu m A polyimide film was obtained.
비교예 2. 중공 실리카 입자가 적용된 폴리이미드 필름의 제조(1)Comparative Example 2: Production of polyimide film to which hollow silica particles were applied (1)
제조예 2에서 얻은 이미드화 변환액 대신 제조예 9에서 얻은 이미드화 변환액 104.53 g을 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 평균 두께가 25 ㎛인 폴리이미드 필름을 얻었다.A polyimide film having an average thickness of 25 탆 was obtained in the same manner as in Example 1, except that 104.53 g of the imidization conversion liquid obtained in Production Example 9 was used in place of the imidization conversion liquid obtained in Production Example 2.
비교예 3. 중공 실리카 입자가 적용된 폴리이미드 필름의 제조(2)Comparative Example 3: Production of polyimide film to which hollow silica particles were applied (2)
제조예 2에서 얻은 이미드화 변환액 대신 제조예 10에서 얻은 이미드화 변환액 105.70 g을 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 평균 두께가 25 ㎛인 폴리이미드 필름을 얻었다.A polyimide film having an average thickness of 25 탆 was obtained in the same manner as in Example 1, except that 105.70 g of the imidization conversion liquid obtained in Production Example 10 was used in place of the imidization conversion liquid obtained in Production Example 2. [
시험예 1. 유전율 및 유전 정접 측정Test Example 1. Measurement of dielectric constant and dielectric tangent
상기 실시예 1 내지 6 및 비교예 1 내지 3에서 제조한 폴리이미드 필름의 1 GHz에서의 유전율 및 유전 정접을 Keysight사의 SPDR 측정기를 이용하여 측정하였다. 그 결과, 측정된 유전율 및 유전 정접값을 하기 표 1에 나타내었다.The dielectric constant and dielectric loss tangent of the polyimide films prepared in Examples 1 to 6 and Comparative Examples 1 to 3 at 1 GHz were measured using an SPDR meter of Keysight. As a result, the measured dielectric constant and dielectric loss tangent are shown in Table 1 below.
시험예 2. 흡습율 측정Test Example 2. Measurement of moisture absorption rate
상기 실시예 1 내지 6 및 비교예 1 내지 3에서 제조한 폴리이미드 필름을 절단하여 10 mm X 10 mm의 샘플을 5개씩 준비한 후 샘플을 130℃에서 3분간 건조하고 무게를 측정하였다. 이후 건조된 샘플을 Pure Water에 완전히 함침시킨 상태에서 24시간 경과 후 샘플 양쪽 표면의 물기를 닦고 무게를 재측정하여 건조 후와 함침 후의 샘플 무게변화에 따른 흡습율을 측정하였다. 그 결과, 측정된 흡습율을 하기 표 1에 나타내었다.The polyimide films prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were cut to prepare five samples each having a size of 10 mm × 10 mm. The samples were dried at 130 ° C. for 3 minutes and weighed. After drying the sample, the dried sample was thoroughly impregnated with pure water. After 24 hours, the moisture on both surfaces of the sample was wiped off and the weight was remeasured to measure the moisture absorption rate according to the sample weight change after drying and after impregnation. As a result, the measured moisture absorption rates are shown in Table 1 below.
실시예 1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4 실시예5Example 5 실시예6Example 6 비교예1Comparative Example 1 비교예2Comparative Example 2 비교예3Comparative Example 3
폴리아믹산 용액Polyamic acid solution 제조예 1Production Example 1
이미드화 변환액Imidization conversion amount 제조예 2Production Example 2 제조예 3Production Example 3 제조예 4Production Example 4 제조예 5Production Example 5 제조예6Production Example 6 제조예7Production Example 7 제조예8Production Example 8 제조예9Production Example 9 제조예10Production Example 10
흄드 실리카 입자(중량%)Fumed silica particles (% by weight) 55 99 1313 1717 2121 2525 00 2121 2525
유전율(1 GHz)Permittivity (1 GHz) 3.43.4 3.23.2 3.03.0 2.82.8 2.62.6 2.42.4 3.73.7 2.82.8 2.72.7
유전 정접(1 GHz)Dielectric tangent (1 GHz) 0.0070.007 0.0060.006 0.0060.006 0.0060.006 0.0050.005 0.0040.004 0.0130.013 0.0100.010 0.0080.008
흡습율Moisture absorption rate 1.8%1.8% 1.6%1.6% 1.3%1.3% 1.1%1.1% 0.9%0.9% 0.8%0.8% 2.8%2.8% 2.5%2.5% 2.3%2.3%
상기 표 1로부터, 5 ㎛ 입경을 가지면서 20 ㎚ 크기의 기공을 갖는 흄드 실리카 입자를 적용하여 제조된 실시예 1 내지 6의 폴리이미드 필름이 흄드 실리카 입자를 포함하지 않는 비교예 1의 폴리이미드 필름에 비해 더 낮은 유전율, 유전 정접 및 흡습율 값을 나타냄을 알 수 있다. From Table 1, the polyimide films of Examples 1 to 6 prepared by applying the fumed silica particles having a pore size of 20 nm with a particle size of 5 mu m were the polyimide films of Comparative Example 1 containing no fumed silica particles Dielectric loss tangent, and moisture absorption rate, respectively.
또한, 상기 실시예 1 내지 6의 폴리이미드 필름이 3 ㎛ 입경을 가지면서 200 ㎚ 크기의 기공을 갖는 중공 실리카 입자를 포함하는 비교예 2 및 3의 폴리이미드 필름에 비해 낮은 유전 정접 및 흡습율 값을 나타냄을 알 수 있다. 따라서, 특정 입경 및 특정 크기의 기공을 갖는 흄드 실리카 입자를 적용한 폴리이미드 필름이 흄드 실리카 입자를 포함하지 않는 폴리이미드 필름 또는 일반 중공 실리카 입자를 포함하는 폴리이미드 필름에 비해 보다 우수한 유전율, 유전 정접 및 흡습율 효과를 구현할 수 있다는 것을 확인할 수 있었다.In addition, the polyimide films of Examples 1 to 6 had lower dielectric loss tangent and moisture absorption rate values than the polyimide films of Comparative Examples 2 and 3 including hollow silica particles having a pore size of 200 nm, . ≪ / RTI > Therefore, the polyimide film to which the fumed silica particles having the specific particle diameter and the specific-size pore are applied has a better dielectric constant, dielectric tangent, and dielectric constant than the polyimide film containing no fumed silica particles or the polyimide film containing the ordinary hollow silica particles. It was confirmed that the moisture absorption rate effect can be realized.

Claims (15)

1) 폴리이미드 전구체를 제조하는 단계;1) preparing a polyimide precursor;
2) 상기 폴리이미드 전구체에 흄드 실리카 입자를 포함하는 이미드화 변환액을 혼합하여 겔 필름을 제조하는 단계; 및2) mixing a polyimide precursor with an imidization conversion liquid containing fumed silica particles to prepare a gel film; And
3) 상기 겔 필름을 열처리하여 이미드화하는 단계를 포함하며,3) heat treating the gel film to imidize the gel film,
이때, 상기 흄드 실리카 입자가 평균 입경이 10 ㎛ 이하이고, 평균 크기 300 nm 이하의 기공을 갖는 것을 특징으로 하는, 폴리이미드 필름의 제조방법.Wherein the fumed silica particles have pores having an average particle diameter of 10 mu m or less and an average particle size of 300 nm or less.
제1항에 있어서, 상기 흄드 실리카 입자가 평균 입경이 0.3 내지 10 ㎛인 것을 특징으로 하는, 폴리이미드 필름의 제조방법.The method for producing a polyimide film according to claim 1, wherein the fumed silica particles have an average particle diameter of 0.3 to 10 탆.
제1항에 있어서, 상기 흄드 실리카 입자가 평균 크기 1 내지 300 nm의 기공을 갖는 것을 특징으로 하는, 폴리이미드 필름의 제조방법.The process for producing a polyimide film according to claim 1, wherein the fumed silica particles have pores having an average size of 1 to 300 nm.
제2항 또는 제3항에 있어서, 상기 흄드 실리카 입자가 평균 입경이 3 내지 10 ㎛이고 평균 크기 1 내지 100 nm의 기공을 갖는 것을 특징으로 하는, 폴리이미드 필름의 제조방법.The process for producing a polyimide film according to claim 2 or 3, wherein the fumed silica particles have an average particle size of 3 to 10 mu m and an average size of 1 to 100 nm.
제1항에 있어서, 상기 흄드 실리카 입자가 비표면적이 600 내지 1,000 ㎡/g인 것을 특징으로 하는, 폴리이미드 필름의 제조방법.The method for producing a polyimide film according to claim 1, wherein the fumed silica particles have a specific surface area of 600 to 1,000 m < 2 > / g.
제1항에 있어서, 상기 흄드 실리카 입자가 필름의 총 중량을 기준으로 2 내지 30 중량%로 포함되는 것을 특징으로 하는, 폴리이미드 필름의 제조방법.The method according to claim 1, wherein the fumed silica particles are contained in an amount of 2 to 30% by weight based on the total weight of the film.
제1항에 있어서, 상기 흄드 실리카 입자가 중공형 또는 메조세공(mesoporous)형 입자인 것을 특징으로 하는, 폴리이미드 필름의 제조방법.The method according to claim 1, wherein the fumed silica particles are hollow or mesoporous particles.
흄드 실리카 입자를 포함하는 폴리이미드 필름으로서,1. A polyimide film comprising fumed silica particles,
상기 흄드 실리카 입자가 평균 입경이 10 ㎛ 이하이고, 평균 크기 300 nm 이하의 기공을 갖는 것을 특징으로 하는, 폴리이미드 필름.Wherein the fumed silica particles have an average particle diameter of 10 mu m or less and pores having an average size of 300 nm or less.
제8항에 있어서, 상기 흄드 실리카 입자가 평균 입경이 0.3 내지 10 ㎛인 것을 특징으로 하는, 폴리이미드 필름.The polyimide film according to claim 8, wherein the fumed silica particles have an average particle diameter of 0.3 to 10 mu m.
제8항에 있어서, 상기 흄드 실리카 입자가 평균 크기 1 내지 300 nm의 기공을 갖는 것을 특징으로 하는, 폴리이미드 필름.The polyimide film according to claim 8, wherein the fumed silica particles have pores with an average size of 1 to 300 nm.
제9항 또는 제10항에 있어서, 상기 흄드 실리카 입자가 평균 입경이 3 내지 10 ㎛이고 평균 크기 1 내지 100 nm의 기공을 갖는 것을 특징으로 하는, 폴리이미드 필름.11. The polyimide film according to claim 9 or 10, wherein the fumed silica particles have an average particle size of 3 to 10 mu m and an average size of 1 to 100 nm.
제8항에 있어서, 상기 흄드 실리카 입자가 비표면적이 600 내지 1,000 ㎡/g인 것을 특징으로 하는, 폴리이미드 필름.The polyimide film according to claim 8, wherein the fumed silica particles have a specific surface area of 600 to 1,000 m < 2 > / g.
제8항에 있어서, 상기 폴리이미드 필름이 1 GHz에서 2.7 내지 3.4의 유전율을 갖는 것을 특징으로 하는, 폴리이미드 필름.The polyimide film according to claim 8, wherein the polyimide film has a dielectric constant of 2.7 to 3.4 at 1 GHz.
제8항에 있어서, 상기 폴리이미드 필름이 1 GHz에서 0.005 내지 0.02의 유전 정접을 갖는 것을 특징으로 하는, 폴리이미드 필름.The polyimide film according to claim 8, wherein the polyimide film has a dielectric loss tangent of 0.005 to 0.02 at 1 GHz.
제8항에 있어서, 상기 폴리이미드 필름이 2% 이하의 흡습율을 갖는 것을 특징으로 하는, 폴리이미드 필름.The polyimide film according to claim 8, wherein the polyimide film has a moisture absorption rate of 2% or less.
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