WO2020091432A1 - Composition de précurseur de polyimide pour améliorer l'adhésivité d'un film de polyimide et film de polyimide fabriqué à partir de celle-ci - Google Patents

Composition de précurseur de polyimide pour améliorer l'adhésivité d'un film de polyimide et film de polyimide fabriqué à partir de celle-ci Download PDF

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WO2020091432A1
WO2020091432A1 PCT/KR2019/014505 KR2019014505W WO2020091432A1 WO 2020091432 A1 WO2020091432 A1 WO 2020091432A1 KR 2019014505 W KR2019014505 W KR 2019014505W WO 2020091432 A1 WO2020091432 A1 WO 2020091432A1
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precursor composition
polyimide precursor
group
polyimide
polyimide film
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PCT/KR2019/014505
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Korean (ko)
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황인환
이익상
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에스케이씨코오롱피아이 주식회사
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Publication of WO2020091432A1 publication Critical patent/WO2020091432A1/fr

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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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Definitions

  • the present invention relates to a polyimide precursor composition for improving the adhesion of a polyimide film, and a polyimide film prepared therefrom.
  • Polyimide (PI) is a polymer material with thermal stability based on a rigid aromatic backbone and has mechanical properties such as excellent strength, chemical resistance, weather resistance, and heat resistance based on the chemical stability of the imide ring.
  • polyimide is in the spotlight as a high-performance polymer material that can be applied to a wide range of industries such as electronics, communications, and optics due to its excellent electrical properties such as insulation properties and low dielectric constant.
  • the higher the molecular weight of the polyamic acid the higher the viscosity of the polyamic acid solution in a state in which the polyamic acid is dissolved in a solvent, resulting in a problem that the fluidity decreases and the process handling becomes very low.
  • polyimide resins undergo chemical changes, ie oxidation reactions, in the presence of oxygen by light, heat, pressure, shear force, and the like.
  • This oxidation reaction causes a problem of deteriorating the heat resistance and mechanical properties of the polyimide film produced by generating a change in physical properties by cutting, crosslinking, etc. of the molecular chain in the polyimide resin.
  • a method of adding a small amount of an additive such as an antioxidant is used, and the antioxidant removes oxygen atoms of an already oxidized polyimide resin, thereby stabilizing the polyimide resin.
  • an additive such as an antioxidant
  • a phosphate compound and a sulfur compound are typically used.
  • antioxidants have properties that decompose at high temperatures, and in particular, in the production of polyimide resins, it is common that high temperature heat treatment for imidization is involved, so that the antioxidants are decomposed to reduce the antioxidant effect. In some cases, there is a problem that these effects are not exerted at all.
  • a polyimide film is produced through a method of forming a gel film by forming a polyamic acid on a support and drying the gel film, and imidizing the gel film.
  • a lifting phenomenon in which a part of the phase is peeled off occurs.
  • the polyamic acid composed of the dianhydride monomer and the diamine monomer is a material having very low or little adhesion to a support made of an inorganic substrate, a problem of separation from the support may occur during the manufacturing process.
  • the object of the present invention even if the solid content of the polyamic acid solution is high, the viscosity is kept low, satisfies the heat resistance and mechanical properties of the polyimide film produced therefrom at the same time, the adhesion to the support in the manufacturing process of the polyimide film It is to provide a polyimide precursor composition that is kept excellent and a polyimide film prepared therefrom.
  • a polyamic acid solution prepared by polymerizing one or more dianhydride monomers and one or more diamine monomers in an organic solvent, a polyyi comprising an aromatic carboxylic acid having four or more carboxyl groups and an antioxidant
  • the mid precursor composition is disclosed as an essential factor for the implementation of a polyimide film satisfying the above characteristics.
  • the dianhydride monomer may satisfy the above-described properties by including an adhesive dianhydride monomer.
  • the present invention has a practical purpose to provide a specific embodiment thereof.
  • the present invention is a polyamic acid solution prepared by polymerizing one or more dianhydride monomers and one or more diamine monomers in an organic solvent;
  • Aromatic carboxylic acids having 4 or more carboxyl groups
  • the dianhydride monomer includes an adhesive dianhydride monomer represented by the following Chemical Formula 1,
  • a polyimide precursor composition having an elongation of 13% or more of a polyimide film prepared therefrom is provided.
  • X 1 and X 2 may be each independently selected from the group consisting of C1-C3 alkyl group, aryl group, carboxyl group, hydroxy group, fluoroalkyl group, and sulfonic acid group, and when X1 and X2 are plural , May be the same or different from each other, and n1 and n2 are each independently an integer of 0 to 3.
  • process handling may be improved due to a relatively low viscosity while having a high solid content, and the polyimide film produced therefrom has excellent heat resistance and mechanical properties, and a polyimide film It was found that the cutability and yield of the product were improved.
  • dianhydride dianhydride
  • dianhydride is intended to include its precursors or derivatives, which may not technically be dianhydrides, but nevertheless react with diamines to form polyamic acids. And this polyamic acid can be converted back to polyimide.
  • Diamine as used herein is intended to include precursors or derivatives thereof, which may not technically be diamines, but will nevertheless react with dianhydrides to form polyamic acids, which polyamic acids are again polydi Can be converted to mead.
  • the polyimide precursor composition according to the present invention includes: a polyamic acid solution prepared by polymerizing one or more dianhydride monomers and one or more diamine monomers in an organic solvent;
  • Aromatic carboxylic acids having 4 or more carboxyl groups
  • the dianhydride monomer includes an adhesive dianhydride monomer represented by the following Chemical Formula 1,
  • X 1 and X 2 may be each independently selected from the group consisting of C 1 -C 3 alkyl group, aryl group, carboxyl group, hydroxy group, fluoroalkyl group and sulfonic acid group, and X 1 and X 2 are plural. In the case of, they may be the same or different from each other, and n1 and n2 are each independently an integer of 0 to 3.
  • the adhesion reaction includes, for example, physical bonding between the polyimide film and the surface of the support, hydrogen bonding between the polyimide film and the metalloid oxide or metal oxide film on the surface of the support, and chemical adsorption between the polyimide film and the surface of the support. Can be.
  • the carbonyl group included in the adhesive dianhydride monomer improves the chemical adsorption reaction by the polar functional group during the adhesion reaction as described above, and the gel film is dried or supported in the process of manufacturing the polyimide film. It is possible to minimize the lifting phenomenon in which a part of the phase is peeled off.
  • the adhesive dianhydride monomer that can be particularly preferably used in the present invention is 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenone It may include one or more selected from the group consisting of tetracarboxylic dianhydride (BTDA), but is not limited thereto.
  • BTDA tetracarboxylic dianhydride
  • the aromatic carboxylic acid is 3,3 ', 4,4'-biphenyltetracarboxylic acid (3,3', 4,4'-biphenyltetracarboxylic acid, BPTA), pyromellitic acid (PMA) , 1,2,3,4-benzenetetracarboxylic acid, benzophenone-3,3 ', 4,4'-tetracarboxylic acid (benzophenone-3,3', 4,4'-tetracarboxylic acid, pyrazine tetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid (2,3,6,7-naphthalenetetracarboxylic acid) and naphthalene-1,4,5 , 8-tetracarboxylic acid (naphthalene-1,4,5,8-tetracarboxylic acid) may include one or more selected from the group consisting of.
  • aromatic carboxylic acids having 4 or more carboxyl groups are not polymerized with polyamic acid at a temperature in the process of polymerizing a polyamic acid solution or preparing a polyimide precursor composition, for example, at a temperature of 40 to 90 ° C. Subsequently, upon heat treatment for imidization, a closed ring dehydration reaction is caused, so that a carboxyl group may form a dianhydride group.
  • the terminal amine group of the polyamic acid chain or the polyimide chain can react with the dianhydride group to increase the length of the polymer chain while forming an amic acid group.
  • the amic acid group thus generated may be imidized at a high temperature to increase the length of the polyimide chain.
  • the polyimide precursor composition containing the aromatic carboxylic acid can maintain a low viscosity, thereby significantly improving process handling.
  • mechanical properties and heat resistance can be remarkably improved compared to polyimide films produced using polyamic acids of similar molecular weight.
  • the content of the dianhydride monomer is 93 to 98.8 mol%
  • the content of the adhesive dianhydride monomer is 1 to 5 mol%
  • the aromatic having 4 or more carboxyl groups The content of carboxylic acid may be 0.2 to 2 mol%.
  • an increase in the carbonyl group included in the adhesive dianhydride monomer may increase the hygroscopicity of the polyimide film, and accordingly, problems such as an increase in the dielectric constant of the polyimide film may occur.
  • the heat resistance of the polyimide film may be lowered, flexibility may be lowered, and defects may occur in the appearance of the film. It is not preferable because a desired low viscosity cannot be achieved.
  • the antioxidant may have a 5% by weight decomposition temperature of 380 ° C or higher, and specifically, 5% by weight decomposition temperature of 400 ° C or higher.
  • the antioxidant may include a compound represented by Formula 2 below.
  • R 1 to R 6 may each independently be selected from the group consisting of C1-C3 alkyl groups, aryl groups, carboxyl groups, hydroxy groups, fluoroalkyl groups, and sulfonic acid groups,
  • n is an integer from 1 to 4,
  • R 1 to R 6 are plural, they may be the same or different from each other,
  • n1 to m6 are each independently an integer of 0 to 3.
  • n in Formula 2 may be 1, m1 to m6 may be 0, and more specifically, the antioxidant may include a compound of Formula 2-1.
  • antioxidants Since these antioxidants have low volatility and excellent thermal stability, they do not decompose or volatilize during the production process of the polyimide film, and thus exhibit an effect of preventing oxidation of the amide group or the imide group of the polyimide film in the polyimide precursor composition. Can be.
  • the polyimide film is decomposed by high temperature during the manufacturing process, and thus cannot exhibit the effect of introducing the above antioxidant.
  • the antioxidant may be included in the range of 0.1 to 2 parts by weight based on 100 parts by weight of the solid content of the polyimide precursor composition.
  • the content of the antioxidant exceeds the above range, the heat resistance of the polyimide film may deteriorate, and deposition or blooming may occur in the polyimide film, thereby deteriorating mechanical properties, and film appearance. It is not desirable because it may cause defects.
  • the polyimide precursor composition may include 10 to 20% by weight of solids based on the total weight of the polyimide precursor composition.
  • the polyimide precursor composition may have a viscosity at 23 ° C of 1,000 to 20,000 cp, specifically 2,000 to 10,000 cP, and more specifically 3,000 to 6,000 cP.
  • the polyimide precursor composition having such a viscosity has an advantage of easy handling in the process in terms of fluidity, and may be advantageous in film forming. Specifically, when the viscosity of the polyimide precursor composition exceeds the above range, a higher pressure must be applied by friction with the pipe when the polyimide precursor composition is moved through the pipe during the manufacturing process of the polyimide film. Therefore, the process cost can be increased and handling can be reduced. In addition, the higher the viscosity, the more time and cost may be required for the mixing process.
  • the polyimide precursor composition may further include a silicone-based additive.
  • the polyimide precursor composition may contain 0.01 to 0.05 parts by weight of a silicone-based additive with respect to 100 parts by weight of solid content.
  • the content of the silicone-based additive exceeds the above range, the mechanical properties of the polyimide film to be produced may be deteriorated, and the silicone-based additive is decomposed at a high temperature during heat treatment for imidization, thereby increasing the adhesion between the gel film and the support. It is not preferable because it may decrease.
  • the content of the silicone-based additive is less than the above range, it is not preferable because it cannot exert a sufficient effect to improve the smoothness of the surface of the polyimide film to be produced.
  • the polyimide precursor composition may further include an alkoxy silane coupling agent.
  • it may include 0.01 to 0.05 parts by weight of an alkoxy silane coupling agent with respect to 100 parts by weight of the solid content of the polyimide precursor composition.
  • the alkoxy silane coupling agent When the content of the alkoxy silane coupling agent exceeds the above range, mechanical properties may be deteriorated, and upon heat treatment for imidization, the alkoxy silane coupling agent decomposes at a high temperature to decrease the adhesion between the gel film and the support rather. This is not desirable.
  • the alkoxy silane coupling agent is, for example, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl methyl dimethoxysilane, 3-aminopropyl methyl diethoxysilane, 3- (2 -Aminoethyl) aminopropyl trimethoxysilane, 3-phenylaminopropyl trimethoxysilane, 2-aminophenyl trimethoxysilane, and 3-aminophenyl trimethoxysilane. It can, but is not limited to this.
  • the polyamic acid solution may be produced by polymerization of one or more dianhydride monomers and one or more diamine monomers.
  • the dianhydride monomer that can be used in the production of the polyamic acid of the present invention may be an aromatic tetracarboxylic dianhydride.
  • the aromatic tetracarboxylic dianhydride is pyromellitic dianhydride (or PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (or BPDA), 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (or a-BPDA), oxydiphthalic dianhydride (or ODPA), diphenylsulfone-3,4,3', 4'-tetracarboxylic Dianhydride (or DSDA), bis (3,4-dicarboxyphenyl) sulfide dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3- Hexafluoropropane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, p-phenylenebis
  • PMDA pyromellitic dianhydrides
  • s-BPDA '-biphenyltetracarboxylic dianhydride
  • a-BPDA 2,3,3', 4'-biphenyltetracarboxylic dianhydride
  • the diamine monomers that can be used in the production of the polyamic acid solution of the present invention are aromatic diamines, and are classified as follows.
  • 1,4-diaminobenzene or paraphenylenediamine, PDA
  • 1,3-diaminobenzene 2,4-diaminotoluene
  • 2,6-diaminotoluene 3,5-diaminobenzo Diamines having one benzene nucleus in the structure, such as diacid (or DABA), etc., which have a relatively rigid structure in diamine;
  • Diaminodiphenyl ethers such as 4,4'-diaminodiphenyl ether (or oxidianiline, ODA) and 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane (Methylenediamine), 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl ) -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane , 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis (4-aminophenyl) sulfide, 4,4'-dia
  • diamine monomers that can be particularly preferably used in the present invention include 1,4-diaminobenzene (PPD) and 1,3-diaminobenzene (MPD). ), 2,4-diaminotoluene, 2,6-diaminotoluene, and 3,5-diaminobenzoic acid (DABA).
  • PPD 1,4-diaminobenzene
  • MPD 1,3-diaminobenzene
  • DABA 3,5-diaminobenzoic acid
  • the dianhydride monomer includes an adhesive dianhydride monomer represented by Formula 1 below,
  • the polyimide film is characterized in that the elongation is 13% or more.
  • X 1 and X 2 may be each independently selected from the group consisting of C1-C3 alkyl group, aryl group, carboxyl group, hydroxy group, fluoroalkyl group, and sulfonic acid group,
  • X 1 and X 2 are plural, they may be the same or different from each other,
  • n1 and n2 are each independently an integer of 0 to 3.
  • the second composition In the dianhydride monomer component in excess, in the first composition when the dianhydride monomer component is excessive, in the second composition, the diamine monomer component in excess, the first and second compositions are mixed and used in these reactions So that the total diamine monomer component and the dianhydride monomer component become substantially equimolar It can be joined to the methods.
  • the organic solvent is not particularly limited as long as it is a solvent in which the polyamic acid can be dissolved, but as an example, the organic solvent may be an aprotic polar solvent.
  • Non-limiting examples of the aprotic polar solvent include amide solvents such as N, N'-dimethylformamide (DMF) and N, N'-dimethylacetamide (DMAc), p-chlorophenol, and o-chloro And phenol-based solvents such as phenol, N-methyl-pyrrolidone (NMP), gamma brotirolactone (GBL) and digrime, and these may be used alone or in combination of two or more.
  • amide solvents such as N, N'-dimethylformamide (DMF) and N, N'-dimethylacetamide (DMAc), p-chlorophenol, and o-chloro And phenol-based solvents such as phenol, N-methyl-pyrrolidone (NMP), gamma brotirolactone (GBL) and digrime, and these may be used alone or in combination of two or more.
  • the solubility of the polyamic acid may be controlled by using auxiliary solvents such as toluene, tetrahydrofuran, acetone, methyl ethyl ketone, methanol, ethanol, and water.
  • auxiliary solvents such as toluene, tetrahydrofuran, acetone, methyl ethyl ketone, methanol, ethanol, and water.
  • organic solvents that can be particularly preferably used for preparing the polyimide precursor composition of the present invention may be amide solvents N, N'-dimethylformamide and N, N'-dimethylacetamide.
  • the polymerization method is not limited to the above examples, and it is needless to say that any known method can be used.
  • the dianhydride monomer may be appropriately selected from the examples described above, and in detail, pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) and 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (a-BPDA) may further include one or more selected from the group consisting of.
  • PMDA pyromellitic dianhydride
  • s-BPDA 4,4'-biphenyltetracarboxylic dianhydride
  • a-BPDA 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride
  • the diamine monomer may be appropriately selected from the examples described above, and specifically, 1,4-diaminobenzene (PPD), 1,3-diaminobenzene (MPD), 2,4-diaminotoluene, 2, One or more selected from the group consisting of 6-diaminotoluene and 3,5-diaminobenzoic acid (DABA) can be preferably used.
  • PPD 1,4-diaminobenzene
  • MPD 1,3-diaminobenzene
  • DABA 3,5-diaminobenzoic acid
  • the process (a) is carried out at 30 to 80 °C,
  • the polyamic acid solution may have a viscosity at 23 ° C of 1,000 to 20,000 cP.
  • process (b) is a silicone-based additive
  • an alkoxy silane coupling agent is further mixed in a polyamic acid solution, and is performed at 40 to 90 ° C
  • the process (c) is carried out at 40 to 90 °C,
  • the polyimide precursor composition formed on the support is dried at a temperature of 20 to 120 ° C. for 5 to 60 minutes to prepare a gel film, and the gel film is 1 to 8 ° C. to 450 to 500 ° C. / It can be carried out through a process of heating at a rate of minutes, heat treatment at 450 to 500 ° C for 30 to 60 minutes, and cooling at 20 to 120 ° C at a rate of 1 to 8 ° C / minute.
  • the support may be, for example, an inorganic substrate, and examples of the inorganic substrate include a glass substrate and a metal substrate, but it is preferable to use a glass substrate, and the glass substrate is soda-lime glass, borosilicate glass, and alkali-free glass. And the like may be used, but is not limited to this.
  • the adhesive force between the polyimide film and the support prepared from the gel film is measured to indirectly evaluate the adhesive force between the gel film and the support. Can be. This is because the polyimide film prepared from the gel film can be expected to exhibit similar properties in adhesion to the support.
  • the adhesive force between the polyimide film and the support may be 0.3 N / cm or more, and in particular, 0.5 to 1 N / cm.
  • the adhesive force between the gel film and the support is improved, the gel film is rolled up or partly peeled off the support It can minimize the lifting phenomenon.
  • the aromatic carboxylic acid contained in the polyimide precursor composition is not polymerized with polyamic acid in step (c), but the polyimide precursor is formed by increasing the length of the polyimide chain during heat treatment for imidization.
  • the process viscosity is good due to the low viscosity, and then the length of the polymer chain is increased in the curing process, it is possible to secure a level of heat resistance and mechanical properties similar to that of a polyimide film made from polyamic acid having a higher molecular weight. .
  • the polyimide film may be produced through a thermal imidization method, and chemical imidization method may be performed in parallel.
  • the thermal imidization method is a method of excluding chemical catalysts and inducing an imidization reaction with a heat source such as hot air or an infrared dryer.
  • the thermal imidization method may be included in the process (d), and the amic acid group present in the gel film is imidized by heat-treating the gel film at a variable temperature in the range of 100 to 600 ° C in the process (d). It can be made, and in detail, heat treatment at 200 to 500 ° C, and more specifically, 450 to 500 ° C, can imidize the amic acid group present in the gel film.
  • the polyimide precursor composition may be dried at a phosphorus temperature, which may also be included in the scope of the thermal imidization method.
  • the polyimide film of the present invention prepared according to the above manufacturing method has a thermal expansion coefficient (CTE) of 1 to 25 ppm / ° C, an elongation of 13% or more, and a thermal decomposition temperature of 1% by weight of 555 to 620 ° C.
  • CTE thermal expansion coefficient
  • Glass transition temperature is 380 °C or more
  • the modulus is 8 GPa or more
  • the tensile strength is 280 MPa or more
  • the thickness may be 10 to 20 ⁇ m.
  • a polyimide film may be prepared using a dehydrating agent and an imidizing agent according to methods known in the art.
  • the present invention can also provide an electronic device including the polyimide film.
  • the polyimide precursor composition according to the present invention comprises an adhesive dianhydride monomer, thereby forming a gel film by forming a polyimide precursor composition on a support and drying the gel film and the support in the process of imidizing the gel film. It is possible to improve the production yield by improving the adhesion.
  • aromatic carboxylic acids having 4 or more carboxyl groups included in the polyimide precursor composition have good process handling properties due to low viscosity, and since the length of the polymer chain is increased in the curing process after being formed, from polyamic acids having higher molecular weight It is possible to secure a level of heat resistance and mechanical properties similar to those of the produced polyimide film.
  • an antioxidant having a 5 wt% decomposition temperature of 380 ° C or higher included in the polyimide precursor composition has low volatility and excellent thermal stability, and thus does not decompose or volatilize during the production process of the polyimide film, and the amide in the polyimide precursor composition The oxidation of the imide group of the group or the polyimide film can be prevented, thereby minimizing the change in physical properties of the polyimide film.
  • the polyimide film has an advantage of satisfying the heat resistance and mechanical properties required for the display substrate.
  • a polyimide precursor composition was prepared having a molar ratio of 100: 98.5: 0.5: 1, 0.01 parts by weight of a silicone-based additive, 0.5 parts by weight of an antioxidant, and 0.01 parts by weight of an alkoxy silane coupling agent based on 100 parts by weight of solids.
  • Air bubbles were removed from the polyimide precursor composition through high-speed rotation of 1,500 rpm or more. Thereafter, the defoamed polyimide precursor composition was applied to a glass substrate using a spin coater. Then, under a nitrogen atmosphere and dried at a temperature of 120 ° C. for 30 minutes, a gel film was prepared. Cooling at a rate of 2 ° C / min yielded a polyimide film.
  • the polyimide film was peeled from the glass substrate by dipping in distilled water.
  • the thickness of the prepared polyimide film was 15 ⁇ m.
  • the thickness of the prepared polyimide film was measured using an Anritsu company's film thickness meter (Electric Film thickness tester).
  • Example 1 a polyimide film was prepared in the same manner as in Example 1, except that the viscosity of the monomer, additive, and polyimide precursor composition was changed as shown in Table 1 below.
  • Example 1 a polyimide film was prepared in the same manner as in Example 1, except that instead of the compound of Formula 2-1 as an antioxidant, a compound of Formula A having a 5 wt% decomposition temperature of about 377 ° C was added. .
  • Example 1 a polyimide film was prepared in the same manner as in Example 1, except that the compound of Formula B having a 5 wt% decomposition temperature of about 338 ° C. instead of the compound of Formula 2-1 as an antioxidant was added. .
  • Example 1 100 98.5 - 0.5 One Formula 2-1 0.1 0.1 0.1 5,100
  • Example 2 100 94.5 - 0.5 5 Formula 2-1 0.1 0.1 0.1 5,100
  • Example 3 100 97.5 - 0.5 2 Formula 2-1 0.1 0.1 0.1 5,100
  • Example 4 100 97 - 2 One Formula 2-1 0.1 0.1 0.1 5,100
  • Example 5 100 98.5 - 0.5 One Formula 2-1 0.5 0.1 0.1 5,100
  • Example 6 100 98.5 - 0.5
  • Example 7 100 98.5 - 0.5
  • Example 8 100 50 48.5 0.5 One Formula 2-1 0.1 0.1 0.1 4,900
  • Example 9 100 50 48.5 0.5 One Formula 2-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
  • the polyimide film obtained in Examples before peeling the polyimide film from the glass substrate, it was cut to a width of 10 mm using a cutter knife, under a condition of 23 ° C., 55% RH, and a tensile speed of 50 m / min. In the case of 50 mm ⁇ , the average value of the 180 degree peel strength was measured.
  • a TA thermomechanical analyzer Q400 model was used, and the polyimide film was cut to a width of 2 mm and a length of 10 mm, and then subjected to a tension of 0.05 N under a nitrogen atmosphere, at a rate of 10 ° C./min, 500 at room temperature. After the temperature was raised to °C, while cooling again at a rate of 10 °C / min, the slope of the section at 100 °C to 350 °C was measured.
  • thermogravimetric analysis Q50 model was used, and the polyimide film was heated to 150 ° C. at a rate of 10 min / ° C. under a nitrogen atmosphere to maintain isotherm for 30 minutes to remove moisture. Thereafter, the temperature was raised to 600 ° C at a rate of 10 min / ° C, and the temperature at which 1% weight loss occurred was measured.
  • the polyimide film was cut to a width of 4 mm and a length of 20 mm, and then heated at a rate of 5 ° C./min under a nitrogen atmosphere and a temperature range of 550 ° C. at room temperature.
  • the glass transition temperature was measured under conditions. The glass transition temperature was determined as the maximum peak of tan ⁇ calculated according to the ratio of storage modulus and loss modulus.
  • modulus and tensile strength were measured by ASTM D-882 method using Instron5564 UTM equipment of Instron.
  • the cross head speed at this time was measured under the condition of 5 mm / min.

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Abstract

La présente invention concerne une composition de précurseur de polyimide comprenant : une solution d'acide polyamique préparée par polymérisation d'au moins un type de monomère dianhydride et d'au moins un type de monomère diamine dans un solvant organique; un acide carboxylique aromatique ayant quatre groupes carboxyle ou plus; et un antioxydant, le monomère dianhydride comprenant un monomère dianhydride adhésif exprimé par la formule chimique 1. Un film de polyimide fabriqué à partir de la composition présente un allongement de 13% ou plus.
PCT/KR2019/014505 2018-10-31 2019-10-30 Composition de précurseur de polyimide pour améliorer l'adhésivité d'un film de polyimide et film de polyimide fabriqué à partir de celle-ci WO2020091432A1 (fr)

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CN114854011A (zh) * 2022-05-27 2022-08-05 中化学科学技术研究有限公司 聚酰胺酸溶液、聚酰亚胺膜及其制备方法
CN114920931A (zh) * 2022-05-27 2022-08-19 中化学科学技术研究有限公司 聚酰亚胺前体组合物、聚酰亚胺膜及其制备方法
CN115505125A (zh) * 2022-10-31 2022-12-23 杭州福斯特电子材料有限公司 聚酰亚胺组合物、聚合物、薄膜及包含其的产品

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CN117460762A (zh) * 2021-06-07 2024-01-26 杜邦电子公司 用于电子装置的聚合物
JPWO2023195206A1 (fr) * 2022-04-08 2023-10-12
KR20240107470A (ko) * 2022-12-30 2024-07-09 피아이첨단소재 주식회사 폴리이미드 전구체

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CN114805806B (zh) * 2022-05-10 2024-04-02 上海华谊三爱富新材料有限公司 降低聚酰胺酸溶液粘度的方法和聚酰亚胺膜的制备方法
CN114854011A (zh) * 2022-05-27 2022-08-05 中化学科学技术研究有限公司 聚酰胺酸溶液、聚酰亚胺膜及其制备方法
CN114920931A (zh) * 2022-05-27 2022-08-19 中化学科学技术研究有限公司 聚酰亚胺前体组合物、聚酰亚胺膜及其制备方法
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CN115505125B (zh) * 2022-10-31 2023-08-29 杭州福斯特电子材料有限公司 聚酰亚胺组合物、聚合物、薄膜及包含其的产品

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