WO2018021747A1 - Solution de précurseur de polyimide et procédé de production associé - Google Patents

Solution de précurseur de polyimide et procédé de production associé Download PDF

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WO2018021747A1
WO2018021747A1 PCT/KR2017/007658 KR2017007658W WO2018021747A1 WO 2018021747 A1 WO2018021747 A1 WO 2018021747A1 KR 2017007658 W KR2017007658 W KR 2017007658W WO 2018021747 A1 WO2018021747 A1 WO 2018021747A1
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polyimide
polyimide precursor
precursor solution
formula
group
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PCT/KR2017/007658
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English (en)
Korean (ko)
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윤철민
김경준
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주식회사 엘지화학
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Priority claimed from KR1020170080993A external-priority patent/KR101993647B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/076,260 priority Critical patent/US11655337B2/en
Priority to CN201780025715.4A priority patent/CN109071810B/zh
Priority to EP17834689.6A priority patent/EP3392293B1/fr
Priority to JP2018538711A priority patent/JP6725100B2/ja
Publication of WO2018021747A1 publication Critical patent/WO2018021747A1/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
    • 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
    • C08K5/54—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

Definitions

  • the present invention provides a polyimide precursor solution having improved liquid mar property of the solution upon coating on a substrate.
  • Polyimide (PI) is a polymer with relatively low crystallinity or mostly amorphous structure. It is easy to synthesize, can make thin film, and does not need a crosslinker for curing. It is a polymer material that has excellent heat resistance, chemical resistance, excellent mechanical properties, electrical properties and dimensional stability. It is widely used in electric and electronic materials such as automotive, aerospace, flexible circuit boards, liquid crystal alignment films for LCDs, adhesives and coating agents. have.
  • polyimide is a high-performance polymer material with high thermal stability, mechanical properties, chemical resistance, and electrical properties, it does not satisfy the colorless and transparent property, which is a basic requirement for the display field, and also requires a lower coefficient of thermal expansion.
  • Kapton's coefficient of thermal expansion sold by DuPont, has a low coefficient of thermal expansion of about 30 ppm / ° C, but this also does not meet the requirements of plastic substrates. Therefore, many studies have been conducted to minimize optical characteristics and thermal hysteresis while maintaining basic characteristics of polyimide.
  • aromatic polyimides have a unique color of dark brown because the ⁇ electrons of benzene present in the imide main chain are generated by the bonds between the chains.
  • the theory can be explained by the reason that ⁇ electrons, ⁇ electrons, and nonbonding non-covalent electron pairs exist in the imide structure, thereby enabling electron excitation.
  • polyamideimide has been widely used as an industrial material for electric, electronic, mechanical and aviation fields since it is excellent in heat resistance, mechanical strength, electrical characteristics, and the like.
  • polyamideimide since the structure itself is different from general polyimide, polyamideimide is known to be soluble in an organic solvent, and is also used for applications in which solution molding is necessary, such as enamel varnish, coating for electrical insulation, and paint.
  • the problem to be solved by the present invention is to provide a polyimide precursor solution with improved liquid phenomena in the substrate coating process.
  • Another object of the present invention is to provide a polyimide film prepared from the polyimide precursor solution.
  • Another object of the present invention is to provide a method for producing a polyimide film using the polyimide precursor solution.
  • the present invention to solve the above technical problem
  • a resin composition comprising an organic solvent, which provides a polyimide precursor solution having a curling rate of 0% to 0.1% or less defined by the following formula (1).
  • Curl rate (%) [(A-B) / A] X100
  • A is the area in which the polyimide precursor solution is completely coated on the substrate (100 mm X 100 mm),
  • B is the area of the polyimide precursor solution or polyimide film after curling occurs from the end of the substrate coated with the polyimide precursor solution or polyimide (PI) film,
  • R 1 , R 2 , R 3 and R 4 are each independently a halogen atom selected from -F, -Cl, -Br and -I, a hydroxyl group (-OH), a thiol group (-SH), a nitro group (-NO 2 ), a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenoalkoxy having 1 to 4 carbon atoms, a halogenoalkyl having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and
  • Q 1 is —O—, —CR 18 R 19 —, —C ( ⁇ O) —, —C ( ⁇ O) O—, —C ( ⁇ O) NH—, —S—, —SO 2 —, phenyl It is selected from the group consisting of a rene group and combinations thereof, wherein R 18 and R 19 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluoroalkyl group having 1 to 10 carbon atoms.
  • the coated polyimide after coating the polyimide precursor solution on a substrate, the coated polyimide after leaving the substrate coated with the resin composition solution at a temperature of 20 °C to 30 °C, humidity 40% to 80%
  • the curling rate of the precursor solution may be 0.1% or less.
  • the polyimide film formed by curing the substrate coated with the polyimide precursor solution at a temperature of 20 ° C. to 30 ° C. and a humidity of 40% to 80% and then curing at a temperature of 320 ° C. or more may be 0.1% or less. Can be.
  • the molar ratio of the total content of the compounds of Formulas 1 and 2 and the compound of Formula 3 may be 1: 0.98 to 1: 0.99.
  • the total amount of the compound of Formula 1 and Formula 2 may include the compound of Formula 2 in an amount of 13 to 27 mol%.
  • the polyimide may include a repeating structure represented by the following Chemical Formulas 4a and 4b.
  • the distribution coefficient LogP of the organic solvent is positive, specifically, N, N-diethylacetamide (DEAc), N, N-diethylformamide (N, N -diethylformamide (DEF), N-ethylpyrrolidone (N-ethylpyrrolidone, NEP), dimethyl propaneamide (DMPA), diethyl propaneamide (DEPA) or a mixture thereof may be selected.
  • DEAc N, N-diethylacetamide
  • DEF N-diethylformamide
  • N-ethylpyrrolidone N-ethylpyrrolidone
  • DEPA diethyl propaneamide
  • the density of the organic solvent may be up to 1 g / cm 3.
  • the polyimide precursor solution may further comprise an alkoxy silane
  • the residual stress of the support comprising a polyimide prepared by imidizing the polyimide precursor further comprising the alkoxy silane is -5MPa
  • the absorbance at 308 nm of the DEAc solution containing 10 MPa or less and including the alkoxy silane compound at 0.001 mass% may be 0.1 or more and 0.5 or less at a measurement thickness of the solution of 1 cm.
  • the alkoxy silane may include one or more structures selected from compounds of Formulas 6a to 6d.
  • the coefficient of thermal expansion (CTE) in the cooling process after heating the polyimide film may be a positive value, specifically, the polyimide film n + 1 times in the range of 100 to 450 °C
  • the coefficient of thermal expansion (CTE) after a cooling process after heating (n is an integer of 0 or more) may be 0 to 15 ppm.
  • the haze of the polyimide film prepared from the polyimide precursor solution may be 1 or less.
  • the birefringence in the in-plane and thickness direction of the polyimide film may be 0.05 or more and 0.25 or less.
  • the present invention also comprises the steps of applying and coating the polyimide precursor solution on a substrate;
  • It provides a polyimide film manufacturing method comprising the step of heat-treating the precursor solution coated on the substrate at a temperature of 320 °C or more.
  • it may be to adjust the viscosity of the polyimide precursor solution to 2,000 to 8,000cp or less.
  • the polyimide precursor solution may include 8 to 18% by weight of solids.
  • the heat treatment process may be to heat for 20 to 60 minutes in the temperature range of 320 °C to 500 °C.
  • a transparent polyimide substrate for the oxide TFT or LTPS using the polyimide precursor solution is provided.
  • the present invention improves the uniformity and yield of the polyimide film by improving the liquid curling problem in the coating process of the polyimide precursor solution, and provides a polyimide precursor solution that can improve the efficiency of the process.
  • the polyimide according to the present invention includes a specific structure, it is excellent in transparency, heat resistance, mechanical strength and flexibility, such as a substrate for an element, a cover substrate for display, an optical film, an integrated circuit (IC) package, an electrodeposited film (adhesive). It can be used in various fields such as film, multilayer FPC (flexible printed circuit), tape, touch panel, protective film for optical disk, and the like.
  • Figure 2 shows the result of leaving the glass substrate coated with a polyimide precursor solution according to the embodiment and the comparative example for a predetermined time under a constant humidity conditions.
  • FIG. 3 shows the result of the glass substrate coated with the polyimide precursor solution according to the comparative example and the example when it was left for a predetermined time under a constant humidity condition and the change when the left uncured polyimide precursor solution was cured.
  • substituted means that at least one hydrogen contained in the compound or the organic group is a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a hydroxy group And substituted with a substituent selected from the group consisting of alkoxy groups, carboxylic acid groups, aldehyde groups, epoxy groups, cyano groups, nitro groups, amino groups, sulfonic acid groups and derivatives thereof having 1 to 10 carbon atoms.
  • an alkylene group having 1 to 10 carbon atoms for example, methylene group (-CH 2- ), Ethylene groups (-CH 2 CH 2- ), and the
  • the solute concentration when the polyimide precursor solution is coated on a substrate, the solute concentration must be low in order to be able to apply the viscosity of the solution. On the other hand, when the solute concentration is increased in order to increase productivity, the viscosity of the solution becomes high and cannot be applied. There has been a problem of becoming.
  • the polyimide precursor solution has a low long-term storage characteristics in the humidity conditions, and it is very difficult to maintain the long-term storage while maintaining the degree of polymerization, and in the case of the precursor solution applied on the substrate, the coated solution from the edge A curling phenomenon may be generated, which may later affect the cutting property and yield of the polyimide film.
  • the present invention aims to develop a transparent PI substrate material for oxide TFTs and LTPS by introducing a structure exhibiting expansion behavior using a polyimide structure with high heat shrinkage behavior in the in-plane direction to mitigate shrinkage behavior.
  • Another object of the present invention is to provide a polyimide film using the polyimide precursor solution and a method of manufacturing the same.
  • Curl rate (%) [(A-B) / A] X100
  • A area in a state where the polyimide precursor solution is completely coated on the substrate (100 mm ⁇ 100 mm);
  • R 1 , R 2 , R 3 and R 4 are each independently a halogen atom selected from -F, -Cl, -Br and -I, a hydroxyl group (-OH), a thiol group (-SH), a nitro group (-NO 2 ), a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenoalkoxy having 1 to 4 carbon atoms, a halogenoalkyl having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and is preferably a substituent.
  • the halogen atom may be fluoro (-F)
  • the halogenoalkyl group is a fluoroalkyl group having 1 to 10 carbon atoms containing a fluoro-based atom, fluoromethyl group, perfluoroethyl group, trifluoro
  • the alkyl group may be selected from methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group
  • the aryl group is selected from phenyl group, naphthalenyl group It may be, and more preferably may be a substituent containing a fluoro-based atom, such as a fluoro atom and a fluoroalkyl group
  • Q 1 is —O—, —CR 18 R 19 —, —C ( ⁇ O) —, —C ( ⁇ O) O—, —C ( ⁇ O) NH—, —S—, —SO 2 —, phenyl It is selected from the group consisting of a rene group and combinations thereof, wherein R 18 and R 19 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluoroalkyl group having 1 to 10 carbon atoms.
  • fluoro-based substituent means not only a “fluoro atom substituent” but also a “substituent containing a fluoro atom”.
  • curling of the solution may occur due to shrinkage of the coating layer during curing or in the condition of leaving the coating solution in a humidity condition.
  • This coating solution may not only cause the film thickness variation, but also in the case of a very small foreign material, the film may start to dry from the foreign material and sporadically increase the thickness of the film. Due to the lack of bending resistance, the film breaks or the edges are broken when being cut, resulting in poor workability and lower yield.
  • the phenomenon of liquid curling of the polyimide precursor solution and the film may occur within 30 minutes after coating the polyimide precursor solution solution, and in particular, the thickness of the edge may be thickened by starting to curl from the edge.
  • the curling rate of the solution of the coated resin composition after being left in humidity conditions is 0.1 It may be up to%, for example, at a temperature of 20 °C to 30 °C, humidity conditions of 40% or more, more specifically 40%, 50%, 60%, 70 humidity conditions in the range of 40% to 80% %, 80% in each humidity condition, for example, even after being left for 10 to 50 minutes at a humidity condition of 50%, it may exhibit a very small curl rate of 0.1% or less, preferably 0.05%, more preferably It can exhibit a near-zero curl rate.
  • the curling rate is maintained even after curing, for example, at least 10 minutes after coating the polyimide precursor solution on the substrate, for example, at a temperature of 20 °C to 30 °C, more than 40% humidity conditions, more specifically For example, after 40 to 80% of humidity conditions, that is, 40%, 50%, 60%, 70%, 80% of each humidity condition, for example, after 50 to 10 minutes at a humidity condition of 50%
  • the curling rate of the polyimide film formed by curing at 320 ° C. or higher may be 0.1% or less, that is, almost no curling may occur or even occur in a curing process by heat treatment, specifically, 0.05%, more preferably almost 0 A curling rate close to% can be achieved.
  • the solution of the polyimide precursor according to the present invention can solve the liquid phenomena, it is possible to obtain a polyimide film having more uniform characteristics can further improve the yield of the manufacturing process.
  • the tetracarboxylic dianhydride in the synthesis reaction of the tetracarboxylic dianhydride represented by Formula 1, 2 and the diamine represented by Formula 3, the tetracarboxylic dianhydride is in excess compared to the diamine It is preferable to react, for example, it may be preferable to react in the range of molar ratio of 1: 0.98 to 1: 0.99.
  • the content of the tetracarboxylic dianhydride including the structure represented by the formula (2) is 13 to 27 mol%, preferably 15 to 25 It may be included in the content of mol%.
  • the polyamide film according to the present invention may have a thermal expansion coefficient of 0 to 15 ppm or less after n + 1 heating and cooling processes in a temperature range of 100 ° C to 450 ° C, more preferably. It may have a value of 0 to 10ppm or less.
  • haze (haze) of the polyimide film according to the present invention may be 1 or less, preferably provides a polyimide film having improved transparency having a haze value of 0.9 or less or 0.7, more preferably 0.5 or less. can do.
  • the thickness of the polyimide film may be 8 to 15 ⁇ m, preferably 10 to 12 ⁇ m.
  • Formula 2 may be one or more selected from compounds of Formulas 2a to 2g.
  • Chemical Formula 3 may be selected from compounds represented by Chemical Formulas 3a to 3d.
  • the polyimide according to the present invention may include a repeating structure represented by the following Chemical Formulas 4a and 4b.
  • the content of Formula 4b may be included in 13 to 27 mol%, more preferably 15 to 25 mol%.
  • the structure of Chemical Formula 4a is a polyimide structure having a severe heat shrinkage behavior due to cooling during heating and cooling processes
  • the structure of Chemical Formula 4b is a structure having thermal expansion behavior, and has a proper ratio of polyimide structures having different characteristics from each other. By polymerization, the heat resistance of the film can be optimized in the heating and cooling process.
  • the method for reacting the tetracarboxylic dianhydride with the diamine can be carried out according to a conventional polyimide precursor polymerization production method such as solution polymerization. Specifically, it can be prepared by dissolving diamine in an organic solvent, followed by polymerization by adding tetracarboxylic dianhydride and dicarboxylic acid or dicarboxylic chloride to the resultant mixed solution.
  • the reaction can be carried out under an inert gas or nitrogen stream and can be carried out under anhydrous conditions.
  • the polymerization temperature may be carried out at -20 to 60 °C, preferably 0 to 45 °C. If the reaction temperature is too high, the reactivity may be increased to increase the molecular weight, it may be disadvantageous in terms of the process by increasing the viscosity of the precursor composition.
  • the partition coefficient at 25 may be positive and the boiling point may be 180 ° C. or lower, and more specifically, the partition coefficient LogP value may be 0.01 to 3, or 0.01 to 2, Or 0.01 to 1.
  • the distribution coefficient can be calculated using ACD / LogP module of ACD / Percepta platform of ACD / Labs, and ACD / LogP module uses QSPR (Quantitative Structure-Property Relationship) methodology based algorithm using molecular 2D structure. I use it.
  • QSPR Quadrature Structure-Property Relationship
  • the partition coefficient value is positive, it means that the polarity of the solvent is hydrophobic.
  • a polyimide precursor solution is prepared using a specific solvent having a positive partition coefficient value, and a polyimide precursor solution is prepared using the same. In this case, it can be seen that the curling properties of the solution are improved.
  • the present invention can control the liquid curling of the solution without using an additive that adjusts the surface tension of the material such as leveling agent and the smoothness of the coating film by using a solvent having a positive logP as described above,
  • additional additives such as additives, it is possible not only to eliminate the quality and process problems such as the low molecular weight material contained in the final product, but also to form a polyimide film having more uniform properties more efficiently. have.
  • the position of the foreign substance is determined by the polarity of the foreign substance in the polyimide precursor solution containing a polar solvent having a negative log P.
  • sporadic coating cracks or changes in thickness may occur.However, in the case of using a hydrophobic solvent having a positive log P, the occurrence of changes in thickness due to cracking of coatings may be reduced even when a fine foreign substance having polarity is introduced. Can be suppressed.
  • the density of the solvent according to the present invention can be measured by the standard measuring method of ASTM D1475 1g / cm 3 or less, when the density has a value of 1 or more can increase the relative viscosity can reduce the efficiency of the process. .
  • N, N-diethylacetamide (DEAc), N, N-diethylformamide (DEF), N-ethylpy It may be one selected from the group consisting of rolidone (N-ethylpyrrolidone, NEP), dimethyl propaneamide (DMPA), diethyl propaneamide (DEPA), or a mixture thereof.
  • the polyimide of the present invention may have a molecular weight of 10,000 to 200,000 g / mol, or 20,000 to 100,000 g / mol, or 30,000 to 100,000 g / mol.
  • Mw / Mn molecular weight distribution of the polyimide which concerns on this invention is 1.1-2.5.
  • the polyimide precursor obtained as a result of the polymerization reaction is imidated, whereby a transparent polyimide film can be produced.
  • the imidization process may specifically include a chemical imidization method or a thermal imidization method.
  • a dehydrating agent and an imidization catalyst are added to the polymerized polyimide precursor solution, and then heated to a temperature of 50 to 100 ° C. to imidize by chemical reaction, or the alcohol is removed while refluxing the solution.
  • Polyimide can be obtained by the method of drawing.
  • pyridine, triethylamine, picoline, or quinoline may be used as the imidization catalyst, and in addition, N- of substituted or unsubstituted nitrogen-containing heterocyclic compounds and nitrogen-containing heterocyclic compounds Oxide compounds, substituted or unsubstituted amino acid compounds, aromatic hydrocarbon compounds having a hydroxyl group or aromatic heterocyclic compounds, and especially 1,2-dimethylimidazole, N-methylimidazole, N-benzyl-2- Lower alkylimidazoles such as methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 5-methylbenzimidazole, and N-benzyl-2-methylimidazole.
  • Substituted pyridine such as isolazole derivatives, isoquinoline, 3,5-dimethylpyridine, 3,4-dimethylpyridine, 2,5-dimethylpyridine, 2,4-dimethylpyridine, 4-n-propylpyridine, p-toluenesulfonic acid, etc. May be used.
  • acid anhydrides such as acetic anhydride can be used.
  • the polyimide precursor solution may be in the form of a solution dissolved in an organic solvent, and in the case of having such a form, for example, when a polyimide precursor is synthesized in an organic solvent, the solution may be the reaction solution itself obtained. The reaction solution may be diluted with another solvent. Moreover, when a polyimide precursor is obtained as a solid powder, it may be made to melt
  • the polyimide precursor solution manufactured by the above-mentioned manufacturing method contains solid content in the quantity which makes the said composition have appropriate viscosity in consideration of processability, such as applicability
  • the content of the composition can be adjusted so that the total polyimide content is 5 to 20% by weight, preferably 8 to 18% by weight, more preferably 8 to 12% by weight or less. .
  • the polyimide precursor solution may be adjusted to have a viscosity of 2,000 cP or more, or 3,000 cP or more, and the viscosity of the polyimide precursor solution is 10,000 cP or less, preferably 9,000 cP or less, more preferably 8,000 cP or less. It is preferable to adjust to have a viscosity of.
  • the viscosity of the polyimide precursor solution exceeds 10,000 cP, the efficiency of degassing during the processing of the polyimide film is lowered. As a result, not only the efficiency of the process but also the resulting film has poor surface roughness due to foaming, resulting in electrical, optical and mechanical properties. Can be degraded.
  • the polyimide precursor solution may be applied to a substrate and heat treated on an IR oven, a hot air oven or a hot plate, and the heat treatment temperature may be 300 to 500 ° C, preferably 320 to 450 ° C, for example, 320 ° C to 400 ° C. It may be heated and cured within a temperature range of °C, it may be carried out by a multi-stage heat treatment within the temperature range. The heat treatment process may be carried out for 20 to 70 minutes, preferably for 20 to 60 minutes.
  • the organic solvent contained in the polyimide precursor solution of the present invention may be the same as the organic solvent used in the synthesis reaction.
  • this invention is a range which does not impair an effect, you may add a silane coupling agent, a crosslinking
  • the polyimide precursor solution may further include an alkoxy silane compound, the alkoxy silane compound may be selected from those represented by the following formulas 6a to 6d.
  • the absorbance at 308 nm of a DEAc solution having a residual stress of a support including a polyimide prepared by imidating the polyimide precursor is -5 MPa or more and 10 MPa or less and 0.001 mass% of the alkoxy silane compound.
  • the thickness of the solution may be 0.1 or more and 0.5 or less at 1 cm.
  • the absorbance of the alkoxy silane compound 0.001% by mass DEAc solution may be filled into a quartz cell having a measurement thickness of 1 cm, and measured by UV-1600 (manufactured by Shimadzu Corporation).
  • the alkoxy silane compound can be synthesized by reacting with an acid dianhydride and a trialkoxy silane compound, a reaction with an acid anhydride and a trialkoxy silane compound, a reaction with an amino compound and an isocyanate trialkoxy silane compound, and the like.
  • the acid anhydrides, anhydrides and amino compounds each have an aromatic ring (especially a benzene ring).
  • the content of the alkoxy silane compound may be appropriately adjusted in a range in which sufficient adhesiveness and peeling performance are expressed, and preferably, the alkoxy silane compound may be included in an amount of 0.01 to 20% by weight based on 100% by weight of the polyimide.
  • the resin film obtained in the range whose content of the alkoxy silane compound with respect to 100 weight% of polyimides is 0.01 mass% or more can acquire the outstanding adhesive force with a support body.
  • the content of the alkoxy silane compound is more preferably 0.02 to 15% by weight, more preferably 0.05 to 10% by weight, more preferably 0 0.1 to 8% by weight relative to the polyimide.
  • the polyimide film has a thickness of 5 ⁇ m to 20 ⁇ m, and the haze (Haziness) in the thickness range is 1 or less, preferably 0.9 or less, or 0.7 or less, more preferably 0.5 or less, and 5 to 30.
  • the transmittance for light with a wavelength of 380 to 760 nm in the film thickness range of ⁇ is 80% or more, and the yellowness (YI) is about 25 or less, preferably about 20 or less, more preferably about 16 or less, or 15 or less. It may be a colorless transparent polyimide film having a value. By having excellent light transmittance and yellowness as described above it can exhibit a markedly improved transparency and optical properties.
  • the polyimide film has an in-plane retardation value (R in ) of about 0 to 100 nm, a retardation value (R th ) in the thickness direction of about 200 nm or more, or an in-plane retardation value (R in ) of about 0 to 70 nm.
  • the phase difference value R th of the thickness direction may be about 300 nm or more.
  • the birefringence of the in-plane and thickness direction of the polyimide according to the present invention is the difference between the in-plane refractive index and the thickness direction refractive index, and preferably 0.05 or more and 0.25 or less.
  • the birefringence of the polyimide in the plane and the thickness direction is less than 0.05, when used for retardation film applications, it is necessary to increase the thickness of the polyimide, and coloring of the soluble polyimide may be a problem depending on the intended use.
  • the birefringence in the plane and the thickness direction exceeds 0.25, it may be difficult to control the thickness of the polyimide layer in applications where uniform birefringence characteristic expression is required.
  • the birefringence in the in-plane and thickness directions is not particularly a value when the thickness is defined, but is preferably achieved in a thickness of not less than 1 ⁇ m and less than 40 ⁇ m, more preferably not less than 1 ⁇ m and less than 30 ⁇ m. It is preferable that 5 micrometers or more and less than 25 micrometers are achieved especially about 20 micrometers.
  • an article including the polyimide copolymer is provided.
  • the molded article may be a film, a fiber, a coating material, an adhesive material, but is not limited thereto.
  • the molded article may be formed by a dry wet method, a dry method, a wet method, etc. using the composite composition of the copolymer and the inorganic particles, but is not limited thereto.
  • the molded article may be an optical film, in which case, the composition comprising the polyimide copolymer is applied to the substrate by a method such as spin coating, and then easily dried and cured. Can be prepared.
  • the polyimide according to the present invention can maintain properties such as heat resistance and mechanical strength due to a rigid structure, and in particular, can exhibit excellent heat resistance against heat shrinkage behavior that may occur during high heat processes, as well as excellent colorlessness. It can exhibit transparent characteristics such as device substrate, display cover substrate, optical film, integrated circuit (IC) package, adhesive film, multilayer FPC (flexible printed circuit), tape, touch panel, It can be used in various fields such as an optical disc protective film,
  • the display device may include a liquid crystal display device (LCD), an organic light emitting diode (OLED), and the like, and in particular, a low temperature polysilane (LTPS) process requiring a high temperature process It may be suitable for an OLED device using, but is not limited thereto.
  • LCD liquid crystal display device
  • OLED organic light emitting diode
  • LTPS low temperature polysilane
  • TFMB N-diethylacetamide
  • TFMB 2,2 ⁇ -bis (trifluoromethyl) -4,4 ⁇ -biphenyl diamine
  • TFMB 2,2 ⁇ -bis (trifluoromethyl) -4,4 ⁇ -biphenyl diamine
  • TFMB solution 7 g of pyromellitic dianhydride (PMDA) and 3.56 g of 6FDA (4,4 '-(Hexafluoroisopropylidene) diphthalic anhydride) were added at the same temperature, followed by stirring for a certain time.
  • DEAc was added to prepare a polyimide precursor solution so that the solid content concentration of the polyimide precursor solution prepared from the above reaction was 10 to 10.5% by weight.
  • the viscosity of the polyimide precursor solution was 6,800 cps.
  • TFMB 2,2 ⁇ -bis (trifluoromethyl) -4,4 ⁇ -biphenyl diamine
  • TFMB 2,2 ⁇ -bis (trifluoromethyl) -4,4 ⁇ -biphenyl diamine
  • TFMB solution 7 g of pyromellitic dianhydride (PMDA) and 4.75 g of 6FDA (4,4 '-(Hexafluoroisopropylidene) diphthalic anhydride) were added at the same temperature to dissolve and stirred for a predetermined time.
  • DEAc was added to prepare a polyimide precursor solution so that the solid content concentration of the polyimide precursor solution prepared from the above reaction was 10 to 10.5% by weight.
  • the viscosity of the polyimide precursor solution was 6,200 cps.
  • TFMB 2,2 ⁇ -bis (trifluoromethyl) -4,4 ⁇ -biphenyl diamine
  • TFMB 2,2 ⁇ -bis (trifluoromethyl) -4,4 ⁇ -biphenyl diamine
  • TFMB solution 7 g of pyromellitic dianhydride (PMDA) and 4.75 g of 6FDA (4,4 '-(Hexafluoroisopropylidene) diphthalic anhydride) were added at the same temperature to dissolve and stirred for a predetermined time.
  • DEAc was added to prepare a polyimide precursor solution so that the solid content concentration of the polyimide precursor solution prepared from the above reaction was 10 to 10.5% by weight.
  • the viscosity of the polyimide precursor solution was 5,300 cps.
  • TFMB 2,2 ⁇ -bis (trifluoromethyl) -4,4 ⁇ -biphenyl diamine
  • TFMB 2,2 ⁇ -bis (trifluoromethyl) -4,4 ⁇ -biphenyl diamine
  • TFMB solution 7 g of pyromellitic dianhydride (PMDA) and 4.75 g of 6FDA (4,4 '-(Hexafluoroisopropylidene) diphthalic anhydride) were added at the same temperature to dissolve and stirred for a predetermined time.
  • DEAc was added to prepare a polyimide precursor solution so that the solid content concentration of the polyimide precursor solution prepared from the above reaction was 10 to 10.5% by weight.
  • the viscosity of the polyimide precursor solution was 4,600 cps.
  • NMP N-methyl-2-pyrrolidone
  • TFMB 2,2 ⁇ -bis ( 10.17 g of trifluoromethyl) -4,4 ⁇ -biphenyl diamine)
  • PMDA Polyromellitic Dianhydride
  • the polyimide precursor solution was prepared by adding NMP to the polyimide precursor solution prepared from the reaction so that the solid content concentration was 10.0 to 10.5% by weight.
  • the viscosity of the polyimide precursor solution was 9,500 cps.
  • TFMB (2,2 ⁇ -bis (trifluoromethyl) -4,4 ⁇ -biphenyl is maintained at 25 ° C. diamine) 12g was dissolved. 7 g of PMDA (Pyromellitic Dianhydride) and 2.5 g of 6FDA (4,4 '-(Hexafluoroisopropylidene) diphthalic anhydride) were added to the TFMB solution, and the mixture was dissolved and stirred for a predetermined time.
  • the polyimide precursor solution was prepared by adding NMP to the polyimide precursor solution prepared from the reaction so that the solid content concentration was 10.0 to 10.5% by weight. The viscosity of the polyimide precursor solution was 8,600 cps.
  • Each polyimide precursor solution prepared in Examples 1 to 5 and Comparative Examples 1 and 2 was stirred at 1000 rpm for 30 minutes using a stirrer, and then aliquoted into about 10 mg in a 20 ml vial bottle, and then allowed to stand at room temperature and atmospheric pressure to degas. Time was measured and described in Table 1, and the defoaming characteristics of the Comparative Examples 1 and 2 and Examples 1 and 2 over time are shown in FIG.
  • Figure 1 shows the results of measuring the defoaming characteristics of the Comparative Examples 1, 2 (C, D) and Examples 1, 2 (C, D) over time, the composition of Examples 1, 2 (C, D) It can be seen that the defoaming of the solution occurs completely within 1 hour.
  • Comparative Examples 1 and 2 show that bubbles still remain in the solution even at a time of 1.5 hours or more.
  • the bubbles remaining in the solution may not only lower the surface roughness of the prepared film of the film, but also lower the electrical, optical, and mechanical properties.
  • the polyimide precursor solution coated on the glass substrate was left at 26 ° C. and 50% humidity for 10 to 40 minutes, and then each liquid curling property was observed.
  • 1 and 2 show the results of observing the liquid curling properties of the polyimide precursor solutions prepared in Comparative Example 2 and Example 1 over time, the following table 1 describes the curling rate for each composition It was.
  • the glass substrate coated with the polyimide precursor solution left at 26 ° C. and 50% humidity for a certain time was placed in an oven, heated at a rate of 4 ° C./min, and heat-treated at 350 ° C. for 30 minutes to perform a curing process. After completion of the curing process, the curl rate for each film was measured and described in Table 1 below, and in FIG. 2, the results of the curl rate after curing of the film were shown in Example 1 and Comparative Example 2.
  • the curl rate is defined by the following formula (1).
  • Curl rate (%) [(A-B) / A] ⁇ 100
  • A area of the polyimide precursor solution with the resin composition completely coated on the substrate (100 mm ⁇ 100 mm);
  • the area (B) after the occurrence of the curling phenomenon of the applied polyimide precursor solution and the PI film the width and the length of the substrate at the portion where the maximum curl inward from the edge end of the substrate Based on the calculated area.
  • the polyimide precursor solution according to the present invention hardly exhibits a curling phenomenon even after standing in a humidity condition, and, after curing, the polyimide of Comparative Example 2 While the curling phenomenon occurs more severely in the mid precursor solution, the polyimide precursor solution according to the present invention still hardly curls.
  • Haze was measured by the method according to ASTM D1003 using Haze Meter HM-150.
  • the film is prepared in a size of 5 x 20 mm and then the sample is loaded using the accessory. The length of the film actually measured was made the same at 16 mm. After setting the film pulling force to 0.02N and proceeding the first temperature increase process at a temperature increase rate of 4 / min in the temperature range of 100 to 450 °C, it is cooled at a cooling rate of 4 / min in the temperature range of 450 to 100 °C ( The change in thermal expansion during cooling was measured by TMA (Q400 by TA).
  • Example 1 10.4 0.43 0.1
  • Example 2 10.3 0.40 7.7
  • Example 3 10.3 0.39 11
  • Example 4 10.3 0.36 7.7
  • Example 5 10.3 0.37 7.7
  • Examples 1 to 5 according to the present invention can be seen that not only excellent haze characteristics, but also excellent CTE characteristics.
  • Comparative Example 1 is excellent in haze characteristics, but the CTE shows a large negative value, which means that the shrinkage characteristics according to the cooling process after heating is very large.
  • Comparative Example 2 uses the same precursor as the polyimide precursor of the present invention, and uses NMP, which is a solvent having a negative distribution coefficient, which has good CTE characteristics but high haze, and from the results of Experimental Example 1 High viscosity characteristics.
  • NMP is a solvent having a negative distribution coefficient, which has good CTE characteristics but high haze, and from the results of Experimental Example 1 High viscosity characteristics.
  • liquid curl phenomenon occurs from the results of Experimental Example 2, the efficiency in the film process is lowered, which is not preferable.
  • TFMB N-diethylacetamide
  • the DEAc solution containing 0.001 mass% of said alkoxy silane compounds was filled in the quartz cell of measuring thickness 1cm, and the absorbance when measured by UV-1600 (made by Shimadzu Corporation) was 0.13.
  • Example 2 Under the same conditions as in Example 2, an acid dianhydride component and curing conditions were prepared as described in Table 5 below to prepare a polyimide film. Especially in the case of the comparative example 3, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride (BPDA) was used together as an acid dianhydride component.
  • BPDA 4,4'-biphenyl tetracarboxylic dianhydride

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Abstract

La présente invention concerne une solution de précurseur de polyimide qui peut améliorer l'uniformité d'un film de polyimide et également améliorer l'efficacité des procédés en améliorant l'ondulation du liquide dans un procédé de revêtement de la solution de précurseur de polyimide. En outre, étant donné que le polyimide selon la présente invention présente une excellente transparence, une excellente résistance à la chaleur, une excellente résistance mécanique et une excellente flexibilité par l'inclusion d'une structure spécifique, le polyimide peut être utilisé dans divers domaines, tels que des substrats pour dispositifs, des substrats de couverture pour écrans, des films optiques, des boîtiers de circuits intégrés (CI), des films adhésifs, des circuits imprimés souples (FPC), des bandes, des écrans tactiles, des films protecteurs pour disques optiques, etc.
PCT/KR2017/007658 2016-07-26 2017-07-17 Solution de précurseur de polyimide et procédé de production associé WO2018021747A1 (fr)

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US16/076,260 US11655337B2 (en) 2016-07-26 2017-07-17 Polyimide precursor solution and method for producing same
CN201780025715.4A CN109071810B (zh) 2016-07-26 2017-07-17 聚酰亚胺前体溶液及其制造方法
EP17834689.6A EP3392293B1 (fr) 2016-07-26 2017-07-17 Solution de précurseur de polyimide et procédé de production associé
JP2018538711A JP6725100B2 (ja) 2016-07-26 2017-07-17 ポリイミド前駆体溶液及びその製造方法

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CN112074560A (zh) * 2019-02-01 2020-12-11 株式会社Lg化学 聚酰亚胺膜、使用其的柔性基底和包括柔性基底的柔性显示器
JP2021507952A (ja) * 2018-09-27 2021-02-25 エルジー・ケム・リミテッド ポリイミド前駆体溶液及びそれを用いるポリイミドフィルム

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CN112074560A (zh) * 2019-02-01 2020-12-11 株式会社Lg化学 聚酰亚胺膜、使用其的柔性基底和包括柔性基底的柔性显示器
JP2021521305A (ja) * 2019-02-01 2021-08-26 エルジー・ケム・リミテッド ポリイミドフィルム、それを用いたフレキシブル基板及びフレキシブル基板を含むフレキシブルディスプレイ
JP7125017B2 (ja) 2019-02-01 2022-08-24 エルジー・ケム・リミテッド ポリイミドフィルム、それを用いたフレキシブル基板及びフレキシブル基板を含むフレキシブルディスプレイ
US11472922B2 (en) 2019-02-01 2022-10-18 Lg Chem, Ltd. Polyimide film, flexible substrate using same, and flexible display comprising flexible substrate
CN112074560B (zh) * 2019-02-01 2023-03-07 株式会社Lg化学 聚酰亚胺膜、使用其的柔性基底和包括柔性基底的柔性显示器

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