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WO2020040347A1 - Film de polyimide présentant une résistance améliorée aux agents alcalins et procédé pour le fabriquer - Google Patents

Film de polyimide présentant une résistance améliorée aux agents alcalins et procédé pour le fabriquer Download PDF

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Publication number
WO2020040347A1
WO2020040347A1 PCT/KR2018/011539 KR2018011539W WO2020040347A1 WO 2020040347 A1 WO2020040347 A1 WO 2020040347A1 KR 2018011539 W KR2018011539 W KR 2018011539W WO 2020040347 A1 WO2020040347 A1 WO 2020040347A1
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WO
WIPO (PCT)
Prior art keywords
polyimide film
polyimide
polyamic acid
film
dianhydride
Prior art date
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Ceased
Application number
PCT/KR2018/011539
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English (en)
Korean (ko)
Inventor
김기훈
이길남
최정열
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PI Advanced Materials Co Ltd
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SKCKolon PI Co Ltd
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Publication date
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Priority to CN201880096720.9A priority Critical patent/CN112585195B/zh
Publication of WO2020040347A1 publication Critical patent/WO2020040347A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions 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 C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
    • G02F1/133331—Cover glasses
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/361—Organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/361—Organic materials
    • G02F1/3615—Organic materials containing polymers

Definitions

  • the present invention relates to a polyimide film having improved base resistance and a method of manufacturing the same.
  • Polyimide (PI) is a polymer material having thermal stability based on a rigid aromatic backbone, and has excellent mechanical strength, chemical resistance, weather resistance, and heat resistance based on the chemical stability of an imide ring.
  • polyimide has attracted much attention as a highly functional material that can be used in microelectronics and optical fields based on excellent electrical properties such as insulation and low dielectric constant.
  • the polyimide may be used as a film that is attached to or added to a circuit to provide electrical insulation to the circuit and at the same time protects the circuit against moisture, light sources, impacts, and the like.
  • the film As a film protecting the circuit as described above, various examples may exist, but in the case of a composite film having an adhesive layer formed on one or both sides of the film, the film may be referred to as a coverlay in a narrow sense, and the polyimide film may be It can be preferably used for the coverlay.
  • a process of mixing and evenly dispersing carbon black in a polyamic acid as a precursor is essential. If the carbon black is not evenly dispersed in this process, problems such as poor shielding or surface defects may occur. In essence, carbon blacks differ in physical / chemical properties from polyamic acids or polyimides and are therefore not easily blended and / or dispersed in polyimides or polyamic acids.
  • the manufacturing process of the circuit may include a drill process, a plating process, a desmear process, a washing process, and the like, and the polyimide film may be exposed to the basic solution during the above process. At this time, when the polyimide film is slightly decomposed or modified by the basic solution, the carbon black contained therein may be largely dropped.
  • the shielding may be lost with the removal of the black tint from the coverlay, and the weight and thickness reduction may be accompanied as well as the surface defects due to the dropping of the carbon black, so that the function as the coverlay may be significantly reduced.
  • a polyimide film prepared using the first polyamic acid, the second polyamic acid, and carbon black having different characteristics from each other, even though it is in the form of an ultra thin film of 8 ⁇ m or less, While meeting the mechanical properties, it may have very good shielding properties and resistance to improved base components (hereinafter referred to as 'base resistance').
  • the dispersion of the carbon black is improved to improve the quality of the polyimide A film can be obtained.
  • the present invention has a substantial object to provide a specific embodiment thereof.
  • the present invention provides a polymer comprising: a first polyamic acid polymerized with a first diamine containing a first dianhydride and up to two benzene rings;
  • the present invention provides a method of making the polyimide film.
  • the present invention provides a coverlay comprising the polyimide film and an electronic device comprising the coverlay.
  • dianhydride is intended to include precursors or derivatives thereof, which technically may not be dianhydride, but nevertheless will react with the diamine to form a polyamic acid. This polyamic acid can be converted back to polyimide.
  • diamine is intended to include precursors or derivatives thereof, which may not technically be diamines, but will nevertheless react with dianhydrides to form polyamic acid, which polyamic The acid can be converted back to polyimide.
  • the crystallinity is 65% or more, the light transmittance is 0.09 or less, the base resistance index evaluated based on the polyimide film thickness before and after the base component exposure is 70% or more, the thickness may be 8.0 ⁇ m or less.
  • the first polyamic acid may form a first polyimide chain through imidization
  • the second polyamic acid may form a second polyimide chain through imidization
  • At least a portion of the first polyimide chain and the second polyimide chain may be crosslinked with each other through imidization.
  • the first polyamic acid may be a material having a relatively rigid structure in molecular structure.
  • the first polyimide chain derived from the first polyamic acid can be of relatively rigid structure.
  • This first polyimide chain can contribute to inherent the tensile strength and / or modulus inevitably required for the polyimide film, in particular for the polyimide film to have a certain mechanical strength.
  • the second polyamic acid may be a material having a relatively flexible structure on the molecular structure, a material having a relatively high crystallinity and excellent chemical resistance. Accordingly, the second polyimide chain derived from the second polyamic acid may be relatively high in crystallinity and excellent in chemical resistance.
  • the polyimide film of the present invention not only inherently possesses a level of mechanical properties corresponding to the first polyimide chain, even in a thin form of 8 ⁇ m or less.
  • the predetermined degree of crystallinity (65% or more) and chemical resistance, which are difficult to be embedded by only one polyimide chain, may be embedded by the second polyimide chain.
  • the polyimide film of the present invention is a polyimide film having a low crystallinity of less than 65%. It can have a relatively low light transmittance in comparison. This can serve as a very important advantage in polyimide films containing carbon black where shielding, shading and the like are required.
  • the polyimide film of the present invention may have the following physical properties.
  • the crystallinity of the polymer in the film state is 70% or more
  • Tensile strength is more than 200 kgf / cm 3 .
  • Modulus is 3 GPa or more
  • Light transmittance is 0.07 or less
  • the base resistance index evaluated based on the polyimide film thickness before and after base component exposure may be at least 75%.
  • the first polyamic acid has a viscosity of 50,000 cP to 300,000 cP measured at 23 ° C. when the solid content is 15% by weight, and the second polyamic acid has 23 ° C. when the solid content is 15% by weight.
  • the viscosity measured at may be 5,000 cP to 30,000 cP.
  • the polyimide film may significantly reduce heat resistance and mechanical properties.
  • the viscosity of the first polyamic acid is more than 300,000 cP, there may be a problem in terms of the manufacturing process of the film. Specifically, as the precursor composition has high viscosity, there may be a problem in the film forming process of the film, and it may be difficult to produce the film to 8 ⁇ m or less.
  • the viscosity of the second polyamic acid is less than 5,000 cP, the formation of the second polyimide chain may not be sufficient. This is not preferable in terms of improving the base resistance of the polyimide film.
  • the viscosity of the second polyamic acid exceeds 30,000 cP, the dispersibility of carbon black in the precursor composition may be lowered, which is not preferable in view of manufacturing processability of the polyimide film.
  • polyimide is vulnerable to base components such as degradation or denaturation when exposed to a base environment.
  • base components such as degradation or denaturation
  • the carbon black is largely eliminated and the thickness reduction is more serious.
  • ultra-thin polyimide films of very thin thickness for example, 8 ⁇ m or less have been required.
  • the dropout phenomenon of carbon black in the ultra-thin polyimide film is more severe than that of the polyimide film having a typical thickness of 10 ⁇ m or more. This is because even if the same absolute amount of carbon black is dropped in the normal polyimide film and the ultra-thin polyimide film, the ratio of the carbon black dropped to the carbon black of the entire polyimide film is much higher in the ultra-thin type.
  • the base component penetrates from the surface, in the case of an ultra-thin polyimide film having a close distance to the surface, relatively more carbon black may be eliminated under the same conditions.
  • the basic resistance means that the polyimide film is not easily decomposed and / or denatured even when exposed to the base environment, and the thickness of the polyimide film is reduced during the decomposition and / or denaturation. You can judge.
  • test method (a) comprising the following steps:
  • the flexible circuit board cut to 4 * 10 cm was exposed to 10% NaOH solution for 3 minutes at 55 ° C, and the desmear solution (10% NaMnO 4 + 4% NaOH) was exposed to 5 minutes at 55 ° C for washing. Repeating twice and measuring the thickness of the film (second thickness); And
  • the basic resistance index may be about 50% to 60%.
  • the polyimide film of the present invention may have a base resistance index according to the test method (a) of at least 70% or more, in particular 75% or more, in particular 80% or more. This is a markedly improved base resistance compared to conventional polyimide films.
  • the second polyimide chain is unconditionally contained in the polyimide film unconditionally.
  • the above advantages can be expressed when the content of the second polyimide chain in the polyimide film is a certain level, but if it exceeds, the advantages for the base resistance are not enhanced or improved, whereas the tensile strength of the polyimide film And / or the modulus may drop dramatically.
  • This phenomenon may be more prominent in ultra thin films of 8.0 ⁇ m or less. That is, it is important that the polyimide film contains an appropriate amount of the first polyimide chain and the second polyimide chain so that the mechanical properties and the base resistance are compatible.
  • the polyimide film of the present invention has an average particle diameter of 80 to 92% by weight of the first polyimide chain, 3 to 10% by weight of the second polyimide chain, and 5 to 10% by weight, based on the total weight thereof. 5 ⁇ m of carbon black, and the thickness of the film may be 7.5 ⁇ m or less.
  • the polyimide film of the present invention may include from 5 to 7 wt% of the second polyimide chain of 83 to 92 wt% of the first polyimide chain, based on its total weight.
  • the first dianhydride is pyromellitic dianhydride (or PMDA)
  • the second dianhydride is 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (or s-BPDA) and / or 2,3,3', 4'-biphenyltetracarboxylic Ric dianhydride (or a-BPDA).
  • Diamines with one benzene ring 1,4-diaminobenzene (or paraphenylenediamine, PDA, PPD), 1,3-diaminobenzene, 2,4-diaminotoluene, 2,6-dia Minotoluene, 3,5-diaminobenzoic acid (DABA);
  • the second diamine may be 1,3-bis (4-aminophenoxy) benzene (TPE-R) and / or 1,4-bis (3-aminophenoxy) benzene (TPE-Q).
  • the first diamine and the first dianhydride have a rigid molecular structure, and the second polyimide chain formed by combining them may realize a predetermined level of heat resistance, tensile strength and modulus required for the polyimide film.
  • the TPE-based diamine is a monomer containing three benzene rings, a monomer having excellent chemical resistance, and may mainly act to increase the crystallinity of the polymer.
  • the BPDA-based dianhydride is a relatively soft monomer on the molecular structure including two benzene rings, and excellent in chemical resistance.
  • the second polyimide chains formed by combining them can implement excellent chemical resistance.
  • carbon blacks tend to agglomerate rather than readily disperse upon simple mixing with polyamic acid.
  • first polyamic acid and the second polyamic acid which share similar chemical properties, can be relatively easily mixed.
  • the carbon black in the form of the black crude liquid is mixed with the second polyamic acid having a relatively low viscosity, thereby easily inducing the dispersion of the carbon black primarily.
  • the mixed solution is mixed with the first polyamic acid
  • the second polyamic acid is easily mixed with the first polyamic acid
  • the carbon black that has already been dispersed rapidly mixes with the second polyamic acid and the first polyamic acid in the first half. Or may be dispersed.
  • the above may be a major advantage of the manufacturing method according to the present invention.
  • an organic solvent may be used in preparing the first polyamic acid, the second polyamic acid, and the black crude liquid.
  • Non-limiting examples of organic solvents that can be used in these steps may be aprotic polar solvents.
  • Non-limiting examples of the aprotic polar solvent include amide solvents such as N, N'-dimethylformamide (DMF) and N, N'-dimethylacetamide (DMAc), p-chlorophenol, o-chloro Phenol solvents such as phenol, N-methyl-pyrrolidone (NMP), gamma butyrolactone (GBL), diglyme, and the like, and the like, and these may be used alone or in combination of two or more thereof.
  • amide solvents such as N, N'-dimethylformamide (DMF) and N, N'-dimethylacetamide (DMAc)
  • p-chlorophenol o-chloro Phenol solvents
  • o-chloro Phenol solvents such as phenol, N-methyl-pyrrolidone (NMP), gamma butyrolactone (GBL), diglyme, and the like, and the like, and these may be used alone or in
  • the method of polymerizing the first polyamic acid and the second polyamic acid For example, the method of polymerizing the first polyamic acid and the second polyamic acid,
  • the first polyamic acid, the second polyamic acid and / or black for the purpose of improving various properties of the film, such as the sliding, thermal conductivity, conductivity, corona resistance, loop hardness of the polyimide film derived from the precursor composition
  • a filler may be added.
  • the filler to be added is not particularly limited, preferred examples include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica, dibasic calcium phosphate, barium sulfate, calcium carbonate and the like.
  • the average particle diameter of a filler is not specifically limited, It can determine according to the polyimide film characteristic to modify and the kind of filler to add.
  • the average particle diameter of the filler may be from 0.05 ⁇ m to 100 ⁇ m, in particular from 0.1 ⁇ m to 75 ⁇ m, more preferably from 0.1 ⁇ m to 50 ⁇ m, in particular from 0.1 ⁇ m to 25 ⁇ m.
  • the modifying effect is insignificant, and if it exceeds this range, the filler may significantly impair the surface property of the polyimide film or cause a decrease in the mechanical properties of the film.
  • the addition amount of a filler it is not specifically limited also about the addition amount of a filler, It can determine by the polyimide film characteristic to be modified, filler particle diameter, etc ..
  • the amount of the filler added is 0.01 to 100 parts by weight, preferably 0.01 to 90 parts by weight, more preferably 0.02 to 80 parts by weight, based on 100 parts by weight of the polyamic acid solids of the precursor composition. to be.
  • the amount of filler added is less than this range, the effect of modification by the filler is less likely to appear, and if it exceeds this range, the mechanical properties of the polyimide film may be greatly reduced.
  • the addition method of a filler is not specifically limited, Of course, any well-known method can be used.
  • the obtaining of the polyimide film may include forming a polyimide film by imidating the gel film after preparing the gel film by forming the precursor composition on a support and drying the film.
  • thermal imidation method As a specific method of such imidation, the thermal imidation method, the chemical imidation method, or the composite imidation method which uses the said thermal imidation method and the chemical imidation method together is mentioned as an example, About these the following non-limiting examples It will be described in more detail through.
  • the thermal imidization method is a method of excluding an chemical catalyst and inducing an imidization reaction with a heat source such as a hot air or an infrared dryer.
  • the gel film may be heat-treated to obtain a polyimide film.
  • a gel film can be understood as a film intermediate which has self-support at an intermediate stage with respect to the conversion from polyamic acid to polyimide.
  • the precursor composition is cast in the form of a film on a support such as a glass plate, aluminum foil, endless stainless belt, or a stainless drum, and then the precursor composition on the support 50 °C to 200 °C, Specifically, the drying may be performed at a variable temperature ranging from 80 ° C to 150 ° C.
  • a process of stretching the gel film may be performed to adjust the thickness and size of the polyimide film obtained in the subsequent heat treatment process and to improve orientation, and the stretching may be performed in the machine transport direction (MD) and the machine transport direction. It may be performed in at least one direction of the transverse direction (TD) with respect to.
  • MD machine transport direction
  • TD transverse direction
  • the gel film thus obtained is fixed to a tenter and then heat treated at a variable temperature ranging from 50 ° C. to 500 ° C., specifically 150 ° C. to 500 ° C. to remove water, residual solvent, and the like remaining in the gel film. Nearly all amic acid groups can be imidated to obtain the polyimide film of the present invention.
  • the polyimide film obtained as described above may be heated to a temperature of 400 ° C. to 650 ° C. for 5 seconds to 400 seconds to further cure the polyimide film, and may remain in the obtained polyimide film. This may be done under a predetermined tension to relieve stress.
  • the chemical imidization method is a method of promoting imidization of an amic acid group by adding a dehydrating agent and / or an imidizing agent to the precursor composition.
  • the term "dehydrating agent” refers to a substance that promotes a ring-closure reaction through dehydration to polyamic acid, and includes, but is not limited to, aliphatic acid anhydrides, aromatic acid anhydrides, and N, N '. -Dialkylcarbodiimide, halogenated lower aliphatic, halogenated lower patty acid anhydride, aryl phosphonic dihalide, thionyl halide and the like. Of these, aliphatic acid anhydrides may be preferred in view of ease of availability and cost, and non-limiting examples thereof include acetic anhydride (AA), propion acid anhydride, and lactic acid anhydride. These etc. are mentioned, These can be used individually or in mixture of 2 or more types.
  • imidizing agent means a substance having an effect of promoting a ring closure reaction to polyamic acid, and may be an imine-based component such as aliphatic tertiary amine, aromatic tertiary amine, and heterocyclic tertiary amine. Can be. Of these, heterocyclic tertiary amines may be preferable in view of reactivity as a catalyst. Non-limiting examples of heterocyclic tertiary amines include quinoline, isoquinoline, ⁇ -picolin (BP), pyridine, and the like, and these may be used alone or in combination of two or more thereof.
  • imine-based component such as aliphatic tertiary amine, aromatic tertiary amine, and heterocyclic tertiary amine.
  • heterocyclic tertiary amines may be preferable in view of reactivity as a catalyst.
  • Non-limiting examples of heterocyclic tertiary amines include quinoline, iso
  • the addition amount of a dehydrating agent exists in the range of 0.5-5 mol with respect to 1 mol of amic acid groups in polyamic acid, and it is especially preferable to exist in the range of 1.0 mol-4 mol.
  • the addition amount of the imidizing agent is preferably in the range of 0.05 mol to 2 mol, and particularly preferably in the range of 0.2 mol to 1 mol with respect to 1 mol of the amic acid group in the polyamic acid.
  • the dehydrating agent and the imidating agent are less than the above range, chemical imidization is insufficient, cracks may be formed in the polyimide film to be produced, and the mechanical strength of the film may be lowered.
  • the imidization may proceed excessively rapidly, and in this case, it is difficult to cast in the form of a film or the produced polyimide film may exhibit brittle characteristics, which is not preferable. not.
  • the composite imidation method which further performs the thermal imidation method can be used for manufacture of a polyimide film.
  • the complex imidation method includes a chemical imidization process of adding a dehydrating agent and / or an imidizing agent to the precursor composition at a low temperature; And a thermal imidization process of drying the precursor composition to form a gel film and heat treating the gel film.
  • the type and amount of the dehydrating agent and the imidating agent may be appropriately selected according to the above-described chemical imidization method.
  • the precursor composition containing a dehydrating agent and / or an imidizing agent is cast in a film form on a support such as a glass plate, an aluminum foil, an endless stainless belt, or a stainless drum, and then onto the support.
  • the precursor composition is dried at a variable temperature in the range of 50 ° C. to 200 ° C., specifically 80 ° C. to 200 ° C.
  • chemical converting agents and / or imidating agents can act as catalysts so that amic acid groups can be rapidly converted to imide groups.
  • a process of stretching the gel film may be performed to adjust the thickness and size of the polyimide film obtained in the subsequent heat treatment process and to improve orientation, and the stretching may be performed in the machine transport direction (MD) and the machine transport direction. It may be performed in at least one direction of the transverse direction (TD) with respect to.
  • MD machine transport direction
  • TD transverse direction
  • the gel film thus obtained is fixed in a tenter and then heat treated at a variable temperature in the range of 50 ° C. to 600 ° C., specifically 150 ° C. to 600 ° C. to remove water, catalyst, residual solvent, etc. remaining in the gel film, Nearly all remaining amic acid groups can be imidated to obtain the polyimide film of the present invention.
  • the dehydrating agent and / or the imidating agent may act as a catalyst, thereby rapidly converting the amic acid group into the imide group, thereby enabling high imidization rate.
  • the polyimide film obtained as described above may be heated to a temperature of 400 ° C. to 650 ° C. for 5 seconds to 400 seconds to further cure the polyimide film, and may remain in the obtained polyimide film. This may be done under a predetermined tension to relieve stress.
  • the film was peeled off the SUS plate, fixed to the pin frame, and transferred to a high temperature tenter.
  • the film was heated from 200 ° C. to 600 ° C. in a high temperature tenter and then cooled at 25 ° C. and separated from the pin frame to remove about 86% by weight of the first polyimide chain and 5% by weight of the second polyimide relative to the total weight of the polyimide film.
  • a 7.5 ⁇ m thick polyimide film was prepared comprising the mid chain and 9 wt% carbon black.
  • the amounts of the first polyamic acid solution and the second polyamic acid solution were adjusted so that the polyimide film contained about 88% by weight of the first polyimide chain and 3% by weight of the second polyimide chain relative to the total weight thereof. Except that, a polyimide film having a thickness of 7.5 ⁇ m was prepared in the same manner as in Example 1.
  • the amounts of the first polyamic acid solution and the second polyamic acid solution were adjusted so that the polyimide film contained about 84% by weight of the first polyimide chain and 7% by weight of the second polyimide chain relative to the total weight thereof. Except that, a polyimide film having a thickness of 7.5 ⁇ m was prepared in the same manner as in Example 1.
  • a 7.5 ⁇ m-thick polyimide film was prepared in the same manner as in Example 1, except that the amount of the solution and the carbon black was adjusted.
  • Preparation Example 1-2 was omitted, and Preparation of the mixed solution was omitted in Preparation Example 1-3, and the dosage amount in Preparation Example 1-4 to include about 91 wt% of the first polyimide chain and 9 wt% of carbon black.
  • a polyimide film having a thickness of 7.5 ⁇ m was prepared in the same manner as in Example 1 except that the black crude liquid was directly mixed with the first polyamic acid.
  • the amounts of the first polyamic acid solution and the second polyamic acid solution were adjusted so that the polyimide film contained about 90% by weight of the first polyimide chain and 1% by weight of the second polyimide chain relative to the total weight thereof. Except that, a polyimide film having a thickness of 7.5 ⁇ m was prepared in the same manner as in Example 1.
  • the amounts of the first polyamic acid solution and the second polyamic acid solution were adjusted so that the polyimide film contained about 80% by weight of the first polyimide chain and 11% by weight of the second polyimide chain relative to the total weight thereof. Except that, a polyimide film having a thickness of 7.5 ⁇ m was prepared in the same manner as in Example 1.
  • the first polyamic acid solution and the second such that the polyimide film comprises about 95% by weight of the first polyimide chain, 5% by weight of the second polyimide chain, relative to its total weight
  • a polyimide film having a thickness of 7.5 ⁇ m was prepared in the same manner as in Example 1, except that the amount of the polyamic acid solution was adjusted and mixed.
  • a 7.5 ⁇ m-thick polyimide film was prepared in the same manner as in Example 1, except that the amount of the solution and the carbon black was adjusted.
  • a 7.5 ⁇ m-thick polyimide film was prepared in the same manner as in Example 1, except that the amount of the solution and the carbon black was adjusted.
  • Example 2 About 86% by weight of the first polyimide chain, 5% by weight, based on the total weight of the polyimide film, was prepared in the same manner as in Example 1, except that Preparation Example 1-2 was changed as follows to prepare a second polyamic acid. A 7.5 ⁇ m thick polyimide film was prepared comprising a second polyimide chain of 9 wt% carbon black.
  • the second polyamic acid solution described in Comparative Example 7 was used, such that the polyimide film comprises about 88% by weight of the first polyimide chain and 3% by weight of the second polyimide chain relative to its total weight.
  • a 7.5 ⁇ m-thick polyimide film was prepared in the same manner as in Example 1, except that the amounts of the mixed acid solution and the second polyamic acid solution were adjusted.
  • the second polyamic acid solution described in Comparative Example 7 was used, so that the polyimide film comprises about 84% by weight of the first polyimide chain, 7% by weight of the second polyimide chain, relative to its total weight;
  • a 7.5 ⁇ m-thick polyimide film was prepared in the same manner as in Example 1, except that the amounts of the mixed acid solution and the second polyamic acid solution were adjusted.
  • the base resistance index was measured using test method (a).
  • the light transmittance was measured in the visible region using an optical transmittance measuring device (Model: ColorQuesetXE, manufacturer: HunterLab).
  • Tensile strength was measured by the method given in KS6518.
  • Modulus was measured by the method set forth in ASTM D882, using the Instron 5564 model.
  • Crystallinity was measured by X-ray diffraction (XRD) analysis.
  • XRD X-ray diffraction
  • Examples 1 to 4 exhibited a relatively high crystallinity, light transmittance of 0.09 or less, very good shielding and light shielding functions, and also excellent in basic resistance. In addition, Examples 1 to 4 exhibited a level of compliance with tensile strength and modulus, which are mechanical properties.
  • Comparative Example 1 which contains no second polyimide chain at all, shows very poor base resistance, and the crystallinity is about 0, which is extremely low. The characteristics did not show superiority. From this, it can be seen that the inclusion of the second polyimide chain according to the present invention mainly plays a role in improving the base resistance, shielding, and light shielding properties.
  • Comparative Example 2 exhibited low base resistance as it contained a small amount of second polyimide chain outside the scope of the present invention.
  • Comparative Example 3 contains an excess of the second polyimide chain outside the scope of the present invention, but it can be seen that the tensile strength and modulus are significantly reduced. From these results it can be understood that it is important that the first polyimide chain and the second polyimide chain are contained within the scope of the present invention.
  • Comparative Examples 4 to 6 show that the inclusion of carbon black in the scope of the present invention is preferable in terms of achieving a low light transmittance, and in particular, Comparative Example 6 is due to the excessive content of carbon black even though the second polyimide chain is contained. Due to the low base resistance.
  • Comparative Examples 7 to 9 implement the second polyimide chain using monomers different from the monomers disclosed in the present invention. Comparing these comparative examples with Examples 1 to 3, it can be seen that the results of the examples are better when the second polyimide chain is contained in the same content. In addition, Comparative Examples 7 to 9 have a low crystallinity, and it can be seen that there is no effect of improving shielding and light shielding properties as compared with the Examples.
  • the polyimide film according to the invention comprises a first polyimide chain, a second polyimide chain and carbon black.
  • a polyimide film may be inherent to desired levels of mechanical properties and basic resistance which are difficult to be compatible with each other as the properties of each polyimide chain complementarily act, and have high crystallinity and low light transmittance. Has an advantage.
  • the polyimide film of the present invention is excellent in base resistance despite having a thin thickness of 8 ⁇ m or less, and carbon black dropout can be significantly suppressed even when the base component is exposed.
  • An advantage of the production process according to the invention is that it includes a method which can facilitate the dispersion of carbon black.
  • the production method of the present invention by mixing carbon black in the form of black crude liquid with a relatively low viscosity second polyamic acid, dispersion of carbon black can be easily induced primarily, and then the mixed solution is first polyamic acid.
  • the carbon black that has already been dispersed can quickly blend and / or disperse with the second polyamic acid throughout the first polyamic acid as the second polyamic acid is easily mixed with the first polyamic acid.

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Abstract

La présente invention concerne un film de polyimide fabriqué par imidisation d'une composition précurseur comprenant : un premier poly(acide amique) dans lequel un premier dianhydride et une première diamine portant deux cycles benzéniques ou moins sont polymérisés ; un second poly(acide amique) dans lequel un second dianhydride et une seconde diamine portant trois ou plusieurs cycles benzéniques sont polymérisés ; et du noir de carbone, où, le film de polyimide présente : un degré de cristallinité égal ou supérieur à 65 % ; une transmissivité de la lumière inférieure ou égale à 0,09 ; un indice de résistance aux agents alcalins égal ou supérieur à 70 % tel qu'évalué en termes d'épaisseur du film de polyimide avant et après l'exposition à un composant alcalin ; et une épaisseur inférieure ou égale à 8,0 µm.
PCT/KR2018/011539 2018-08-22 2018-09-28 Film de polyimide présentant une résistance améliorée aux agents alcalins et procédé pour le fabriquer Ceased WO2020040347A1 (fr)

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KR102450700B1 (ko) * 2020-11-13 2022-10-06 피아이첨단소재 주식회사 그라파이트 시트용 폴리이미드 필름 및 이로부터 제조된 그라파이트 시트
CN116444985A (zh) * 2022-01-05 2023-07-18 达迈科技股份有限公司 一种耐碱的黑色消光聚酰亚胺膜

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