WO2013051213A1 - Highly transparent polyimide - Google Patents
Highly transparent polyimide Download PDFInfo
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- WO2013051213A1 WO2013051213A1 PCT/JP2012/006075 JP2012006075W WO2013051213A1 WO 2013051213 A1 WO2013051213 A1 WO 2013051213A1 JP 2012006075 W JP2012006075 W JP 2012006075W WO 2013051213 A1 WO2013051213 A1 WO 2013051213A1
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- WIPO (PCT)
- Prior art keywords
- polyimide
- resin composition
- molded body
- film
- present
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- 0 CC(*)(*)C(c(cc(cc1)-c2ccc(C(O)=O)c(C(NC(CC3)CCC3NC(C)(*)*)=O)c2)c1C(O)=O)=O Chemical compound CC(*)(*)C(c(cc(cc1)-c2ccc(C(O)=O)c(C(NC(CC3)CCC3NC(C)(*)*)=O)c2)c1C(O)=O)=O 0.000 description 2
Classifications
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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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
-
- 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
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0108—Transparent
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
Definitions
- Non-Patent Document 1 a method for inhibiting the formation of a charge transfer complex and introducing transparency by introducing fluorine into the polyimide resin, imparting flexibility to the main chain, introducing bulky side chains, etc.
- Patent Documents 1 and 2 a method of expressing transparency by using a semialicyclic or fully alicyclic polyimide resin that does not form a charge transfer complex has been proposed.
- the present invention provides a polyimide obtained by heating the polyimide precursor.
- the present invention includes a process for forming a resin film by applying and drying the resin composition on a substrate, and a process for heat-treating the resin film after the drying. Provide a method. Moreover, the polyimide molded body obtained by the said manufacturing method is provided.
- the polyimide precursor of the present invention is a copolymer having structural units represented by the following formulas (I) and (II).
- 1,4-diaminocyclohexane is preferably trans 1,4-diaminocyclohexane.
- trans 1,4-diaminocyclohexane it is preferable that the three-dimensional structures of the two amino groups bonded to the cyclohexane ring are both in an equatorial configuration.
- the solvent for the above reaction is not particularly limited as long as it is a solvent capable of dissolving diamine, tetracarboxylic acids and the resulting polyamic acid.
- Specific examples of such solvents include aprotic solvents, phenol solvents, ethers and glycol solvents.
- the aprotic solvent includes N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethylimidazolidinone, tetramethyl.
- Amide solvents such as urea; Lactone solvents such as ⁇ -butyrolactone and ⁇ -valerolactone; Phosphorus amide solvents such as hexamethylphosphoric amide and hexamethylphosphine triamide; dimethylsulfone, dimethylsulfoxide, sulfolane, etc. Sulfur-containing solvents; ketone solvents such as cyclohexanone and methylcyclohexanone; tertiary amine solvents such as picoline and pyridine; and ester solvents such as acetic acid (2-methoxy-1-methylethyl).
- the polyimide of the present invention can be obtained by heating the polyimide precursor and dehydrating and closing the ring.
- the resin composition of the present invention may contain (1) an adhesion-imparting agent, (2) a surfactant or a leveling agent, in addition to the components (a) and (b).
- the composition of the present invention may consist essentially of the above components (a) and (b), and optionally additives such as an adhesion-imparting agent, a surfactant, and a leveling agent. It may consist of only the components. “Substantially” means that the composition mainly comprises the components (a) and (b) (for example, 90% by weight or more of the entire composition). Of additives.
- aluminum chelate compound examples include tris (acetylacetonate) aluminum, acetylacetate aluminum diisopropylate and the like.
- coating process does not have a restriction
- the heating step is a step of (2) removing the organic solvent remaining in the resin film in the drying step and advancing the imidization reaction of the polyamic acid in the resin composition to obtain a cured film.
- a heating process is performed using apparatuses, such as an inert gas oven, a hotplate, a box type dryer, and a conveyor type dryer. This step may be performed simultaneously with the (2) drying step or sequentially.
- a peeling step for peeling the cured film from the substrate is required after the heating step.
- This peeling step is performed after the molded body on the substrate is cooled to room temperature to about 50 ° C.
- a release agent may be applied to the substrate as necessary before applying the resin composition of the present invention. Examples of the release agent include vegetable oil-based, silicon-based, fluorine-based, and alkyd-based release agents.
- the obtained polyimide molded body can also form a pattern by a resist process according to a use.
- a resist is applied, and a pattern is formed by exposure and development.
- the resist material and the material used for etching are not particularly limited as long as they are used in a normal resist process.
- generally well-known etching solutions include hydrazine hydrate, potassium hydroxide aqueous solution, sodium hydroxide aqueous solution and the like.
- the resist is peeled off from the polyimide molded body using an organic solvent.
- organic solvent include ethanolamine, NMP, DMSO and the like, and a mixture thereof can also be used.
- the method for producing a polyimide molded body of the present invention is useful when a polyimide molded body having a thickness of 1 to 500 ⁇ m is produced. In particular, it is preferable to produce a polyimide molded body having a thickness of 1 to 100 ⁇ m in order to further improve the effects of the present invention.
- the amount of residual organic solvent in the polyimide molded body after the (3) heating step of the present invention is preferably 2% by mass or less, more preferably 1% by mass or less, and further preferably 0.5% by mass or less.
- the amount of residual organic solvent in the polyimide molded body can be measured by simultaneous differential thermogravimetric measurement (TG-DTA) and gas chromatograph mass spectrometry (GC-MS).
- the transparency of the polyimide molded body of the present invention obtained by the above production method is such that the light transmittance at a wavelength of 400 nm or more is preferably 70% or more, more preferably 75% or more at a film thickness of 10 ⁇ m.
- the birefringence of the polyimide molded body of the present invention is preferably 0.12 or less, and more preferably 0.08 or less. This value is regarded as having sufficient transparency and low birefringence as a polyimide molded body used in the fields of optical communication and display devices.
- the glass transition temperature (Tg) of the polyimide molded body of the present invention is preferably 250 to 400 ° C., more preferably 300 to 400 ° C. This value is regarded as having sufficient heat resistance as a polyimide molded body used in the fields of optical communication and display devices.
- the glass transition temperature can be measured by the method described in the examples.
- CTE and glass transition temperature (Tg) are calculated
- the tensile strength (breaking strength) is preferably 150 to 300 MPa, and more preferably 150 to 200 MPa. If the tensile strength is less than 150 MPa, the film is fragile and may be difficult to handle when used as a substrate.
- the elongation at break is preferably 5% or more, and more preferably 10% or more. If the elongation at break is less than 5%, the bending stress when the polyimide molded body is used as a substrate is weak, and the reliability of the substrate is lowered.
- the transparent substrate and protective film of the present invention are characterized by comprising the polyimide molded body.
- a conventionally known manufacturing method can be used.
- the resin composition of the present invention can be applied to a temporarily fixed substrate, dried and heated, then subjected to the resist process according to the application, and used as a transparent substrate.
- the resin composition of the present invention can be applied to a temporarily fixed substrate, dried and heated, peeled from the temporarily fixed substrate, and used as a protective film.
- the transparent substrate and protective film of the present invention have sufficient transparency, CTE is small, elastic modulus is small, and birefringence is small, such as liquid crystal display, organic electroluminescence display, field emission display, electronic paper, etc. Can be used for display devices.
- the CTE of the transparent substrate of the present invention is small, it is possible to prevent deterioration in alignment accuracy in the heating process at the time of TFT formation, and the transparency is high and the birefringence is small, so that the visibility is excellent.
- the transparent substrate of the present invention has a low elastic modulus, it can also be used as a substrate for a flexible display.
- Example 1 A 0.2-liter flask equipped with a stirrer and a thermometer was charged with 56 g (564 mmol) of N-methylpyrrolidone (NMP) and 3.43 g (30 mmol) of 1,4-diaminocyclohexane, stirred, and then dried with a dryer. 8.39 g (28.5 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride heated and dehydrated (160 ° C., 24 hours) and 4,4′-oxydiphthalic dianhydride 0.47 g (1.5 mmol) was added, and the mixture was heated and stirred in a water bath at 70 ° C. for 10 minutes to completely dissolve. Thereafter, the mixture was stirred for about 70 hours until the molecular weight became constant to obtain a polyamic acid solution.
- NMP N-methylpyrrolidone
- the weight average molecular weight and dispersity of the obtained polyamic acid were determined by gel permeation chromatography (GPC) method standard polystyrene conversion.
- the weight average molecular weight was 31,000, and the degree of dispersion was 2.4.
- the measurement conditions of the weight average molecular weight and the degree of dispersion are as follows. Measuring device: Detector L4000UV manufactured by Hitachi, Ltd. Pump: Hitachi Ltd. L6000 C-R4Achromatopac manufactured by Shimadzu Corporation Measurement conditions: Column GelpackGL-S300MDT-5 ⁇ 2 by Hitachi Chemical Co., Ltd.
- the obtained polyamic acid solution (resin composition) was diluted with NMP to a viscosity that was easy to apply.
- the residual solid content (NV) of this resin composition was measured and found to be 14%.
- the residual solid content is the ratio of the resin non-volatile content in the resin composition, and was determined by the method of measuring the resin non-volatile content described above.
- This diluted solution was filtered using a 5 ⁇ m filter (Millipore, SLLS025NS), the obtained resin composition was spin-coated on a silicon wafer, dried at 120 ° C. for 3 minutes, and a film thickness of 14 to 18 ⁇ m. A resin film was formed. This was further heated in a nitrogen atmosphere using an inert gas oven to obtain a cured film having a thickness of 10 ⁇ m. Also, salt formation during the synthesis reaction was evaluated. When the salt was not formed or the formation of the salt could be confirmed, the case where it was easily dissolved in the solvent in the resin composition was evaluated as A, and the case where the salt was formed and not easily dissolved in the solvent was evaluated as B.
- the resin composition of Example 1 was B.
- the heating conditions by the inert gas oven are as follows. Equipment: Inert gas oven manufactured by Koyo Thermo System Co., Ltd. Conditions: Temperature rise Room temperature to 200 ° C (5 ° C / min) Hold 200 ° C (20 minutes) Temperature increase 200 ° C to 300 ° C (5 ° C / min) Hold 300 ° C (60 minutes) Cooling 300 ° C to room temperature (60 minutes)
- the obtained cured film was peeled from the silicon wafer using a 4.9% by mass hydrofluoric acid aqueous solution, washed with water and dried, and then evaluated for transmittance, CTE, glass transition temperature (Tg), and mechanical strength.
- the light transmittance was determined by measuring the light transmittance at a wavelength of 400 nm or more using U-3310 (Spectrophotometer manufactured by Hitachi, Ltd.), and obtaining a value converted to 10 ⁇ m using Lambert-Beer's law.
- CTE was measured using a TMA / SS6000 thermomechanical measuring device manufactured by Seiko. Specifically, the cured film is cut into 2 mm ⁇ 3 cm, and the temperature is increased to 30 to 420 ° C. while applying a weight of 10 g / min using a TMA / SS6000 thermomechanical measuring device manufactured by Seiko (temperature increase rate 5 ° C./min. ) Heated. At that time, the gradient of the elongation of the cured film between 100 and 200 ° C. was measured to obtain CTE.
- the glass transition temperature was determined from the inflection point of the coefficient of thermal expansion at a heating rate of 5 ° C./min using TMA / SS6000 manufactured by Seiko Instruments Inc.
- the mechanical strength (elastic modulus, elongation at break, and strength at break) was obtained from a tensile test using Autograph AGS-100NH manufactured by Shimadzu Corporation.
- An elastic modulus of 5.5 GPa or less was designated as A (particularly good)
- a value greater than 5.5 GPa and less than or equal to 6.0 GPa was designated B
- a material having a modulus of elasticity greater than 6.0 GPa was designated C (not good).
- Examples 2-8, Comparative Examples 1-5 A polyamic acid was synthesized in the same manner as in Example 1 except that the amount of amine, acid and the amount thereof was changed as shown in Table 1, and a resin composition and a cured film were prepared, and these were evaluated.
- the amines 1 to 3 and the acids 1 to 4 are as follows.
- Amine 1 1,4-diaminocyclohexaneamine 2: 3,3′-bis (trifluoromethyl) benzidineamine 3: p-phenylenediamine acid 1: 3,3 ′, 4,4′-biphenyltetracarboxylic acid 2 : 3,3 ′, 4,4′-tetracarboxydiphenyl ether acid 3: cyclohexanetetracarboxylic dianhydride
- the cured films obtained in Examples 1 to 8 exhibited good transmittance even after heat treatment at a high temperature of 300 ° C. or higher, had low CTE, low birefringence, and low elastic modulus. It has been found that the polyimide precursor of the present invention provides a cured film that satisfies all of transparency, CTE, and mechanical strength. Furthermore, it was found that all of the cured films obtained in Examples 1 to 8 were excellent in chemical resistance.
- the polyimide molded body of the present invention can be used as a display substrate or a protective film.
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Abstract
Description
一方、近年、表示装置の分野では、耐破損性の向上、軽量化、薄型化等の要望から、ガラス基板やカバーガラス等の透明基板を、樹脂を用いた透明基板に置き換えることが検討されている。表示装置とは、液晶ディスプレイ、有機エレクトロルミネッセンスディスプレイ、電子ペーパー等を指す。特に、携帯電話、電子手帳、ラップトップ型パソコン等の携帯情報端末等の移動型情報通信機器用表示装置では、従来のガラス基板に代わる、樹脂を用いた透明基板に対する強い要望がある。 Polyimide resins have electrical and mechanical properties with excellent insulating properties in addition to high heat resistance. Because of having such characteristics, polyimide resin is used as a surface protective film and an interlayer insulating film of a semiconductor device.
On the other hand, in recent years, in the field of display devices, replacement of a transparent substrate such as a glass substrate or a cover glass with a transparent substrate using a resin has been studied in order to improve breakage resistance, reduce the weight, and reduce the thickness. Yes. A display device refers to a liquid crystal display, an organic electroluminescence display, electronic paper, or the like. In particular, display devices for mobile information communication devices such as portable information terminals such as mobile phones, electronic notebooks, laptop computers, and the like have a strong demand for transparent substrates using resin instead of conventional glass substrates.
本発明の目的は、十分な透明性を有し、CTEが小さく、弾性率が小さく、かつ複屈折の小さいポリイミド成形体を与えるポリイミド前駆体を提供することである。 However, when the polyimide resin of Patent Document 3 is used, although the CTE is small (for example, 20 × 10 −6 K −1 ), the elastic modulus (tensile elastic modulus) is large and the birefringence is large. It was difficult to use as a transparent substrate or protective film.
An object of the present invention is to provide a polyimide precursor that provides a polyimide molded body having sufficient transparency, a low CTE, a low elastic modulus, and a low birefringence.
本発明のポリイミド前駆体は、下記式(I)及び(II)で示される構造単位を有する共重合体である。
また、合成中の塩形成をより抑制し、より反応を制御しやすくする観点からは、(I):(II)=30:70~95:5が好ましく、(I):(II)=50:50~95:5がより好ましい。 [(A) Polyimide precursor]
The polyimide precursor of the present invention is a copolymer having structural units represented by the following formulas (I) and (II).
In addition, from the viewpoint of further suppressing salt formation during synthesis and facilitating control of the reaction, (I) :( II) = 30: 70 to 95: 5 is preferable, and (I) :( II) = 50 : 50 to 95: 5 is more preferable.
尚、上記原料テトラカルボン酸(3,3’,4,4’-ビフェニルテトラカルボン酸、4,4’-オキシジフタル酸)としては、通常これらの酸無水物を用いるが、これら酸又はこれらの他の誘導体を用いることもできる。 By using 4,4'-oxydiphthalic dianhydride (acid dianhydride obtained by heating 3,3 ', 4,4'-tetracarboxydiphenyl ether and dehydrating and ring-closing), the cured product obtained is good It is considered that the heat resistance and transparency can be exhibited and the birefringence can be reduced.
As the raw material tetracarboxylic acid (3,3 ′, 4,4′-biphenyltetracarboxylic acid, 4,4′-oxydiphthalic acid), these acid anhydrides are usually used. It is also possible to use derivatives of
良好な透明性及び耐熱性を発現し、CTEを小さくするという観点から、1,4-ジアミノシクロヘキサンは、トランス1,4-ジアミノシクロヘキサンが好ましい。トランス1,4-ジアミノシクロヘキサンを用いた場合、シクロヘキサン環に結合している2つのアミノ基の立体構造は、共にエクアトリアル配置であることが好ましい。 Further, it is considered that by using 1,4-diaminocyclohexane, the obtained cured product can exhibit good transparency and chemical resistance.
From the viewpoint of expressing good transparency and heat resistance and reducing CTE, 1,4-diaminocyclohexane is preferably trans 1,4-diaminocyclohexane. When trans 1,4-diaminocyclohexane is used, it is preferable that the three-dimensional structures of the two amino groups bonded to the cyclohexane ring are both in an equatorial configuration.
重量平均分子量が10000より小さいと、塗布した樹脂組成物を加熱する工程において、樹脂膜を形成することが難しくなり、また、形成することができても機械特性に乏しくなるおそれがある。重量平均分子量が500000よりも大きいと、ポリアミド酸の合成時に重量平均分子量をコントロールするのが難しく、また適度な粘度の樹脂組成物を得ることが難しくなるおそれがある。 The molecular weight of the polyamic acid (polyimide precursor) of the present invention is preferably 10,000 to 500,000, more preferably 10,000 to 300,000, and particularly preferably 20,000 to 200,000 in terms of weight average molecular weight.
If the weight average molecular weight is less than 10,000, it is difficult to form a resin film in the step of heating the applied resin composition, and even if it can be formed, the mechanical properties may be poor. When the weight average molecular weight is larger than 500,000, it is difficult to control the weight average molecular weight during synthesis of the polyamic acid, and it may be difficult to obtain a resin composition having an appropriate viscosity.
反応温度は-30~200℃が好ましく、20~180℃がより好ましく、30~100℃が特に好ましい。そのまま室温(20~25℃)、又は適当な反応温度で撹拌を続け、ポリアミド酸の粘度が一定になった時点を反応の終点とする。粘度はE型粘度計(東機産業株式会社製)を用い、25℃にて測定できる。
上記反応は、通常3~100時間で完了できる。 When dissolving each monomer component, you may heat as needed.
The reaction temperature is preferably −30 to 200 ° C., more preferably 20 to 180 ° C., and particularly preferably 30 to 100 ° C. Stirring is continued at room temperature (20 to 25 ° C.) or at an appropriate reaction temperature, and the end point of the reaction is determined when the viscosity of the polyamic acid becomes constant. The viscosity can be measured at 25 ° C. using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.).
The above reaction can usually be completed in 3 to 100 hours.
このような溶剤の具体例としては、非プロトン性溶媒、フェノール系溶媒、エーテル及びグリコール系溶媒等が挙げられる。具体的には、非プロトン性溶媒としては、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン、N-メチルカプロラクタム、1,3-ジメチルイミダゾリジノン、テトラメチル尿素等のアミド系溶媒;γ-ブチロラクトン、γ-バレロラクトン等のラクトン系溶媒;ヘキサメチルホスホリックアミド、ヘキサメチルホスフィントリアミド等の含りん系アミド系溶媒;ジメチルスルホン、ジメチルスルホキシド、スルホラン等の含硫黄系溶媒;シクロヘキサノン、メチルシクロヘキサノン等のケトン系溶媒;ピコリン、ピリジン等の3級アミン系溶媒;酢酸(2-メトキシ-1-メチルエチル)等のエステル系溶媒等が挙げられる。フェノール系溶媒としては、フェノール、o-クレゾール、m-クレゾール、p-クレゾール、2,3-キシレノール、2,4-キシレノール、2,5-キシレノール、2,6-キシレノール、3,4-キシレノール、3,5-キシレノール等が挙げられる。エーテル及びグリコール系溶媒としては、1,2-ジメトキシエタン、ビス(2-メトキシエチル)エーテル、1,2-ビス(2-メトキシエトキシ)エタン、ビス[2-(2-メトキシエトキシ)エチル]エーテル、テトラヒドロフラン、1,4-ジオキサン等が挙げられる。中でも、溶解性や塗膜形成性の観点からN-メチル-2-ピロリドンが好ましい。これらの反応溶媒は単独で又は2種類以上混合して用いてもよい。 The solvent for the above reaction is not particularly limited as long as it is a solvent capable of dissolving diamine, tetracarboxylic acids and the resulting polyamic acid.
Specific examples of such solvents include aprotic solvents, phenol solvents, ethers and glycol solvents. Specifically, the aprotic solvent includes N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethylimidazolidinone, tetramethyl. Amide solvents such as urea; Lactone solvents such as γ-butyrolactone and γ-valerolactone; Phosphorus amide solvents such as hexamethylphosphoric amide and hexamethylphosphine triamide; dimethylsulfone, dimethylsulfoxide, sulfolane, etc. Sulfur-containing solvents; ketone solvents such as cyclohexanone and methylcyclohexanone; tertiary amine solvents such as picoline and pyridine; and ester solvents such as acetic acid (2-methoxy-1-methylethyl). Examples of phenol solvents include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol and the like can be mentioned. Examples of ether and glycol solvents include 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether , Tetrahydrofuran, 1,4-dioxane and the like. Of these, N-methyl-2-pyrrolidone is preferred from the viewpoints of solubility and film-forming properties. These reaction solvents may be used alone or in combination of two or more.
得られたポリアミド酸溶液の全量に対するポリアミド酸成分(樹脂不揮発分:以下、溶質という)の割合は、塗膜形成性の観点から5~60質量%が好ましく、10~50質量%がさらに好ましく、10~40質量%が特に好ましい。 The polyimide precursor (polyamic acid) of the present invention is usually obtained as a solution using the reaction solvent as a solvent (hereinafter referred to as a polyamic acid solution).
The ratio of the polyamic acid component (resin non-volatile content: hereinafter referred to as solute) to the total amount of the obtained polyamic acid solution is preferably 5 to 60% by mass, more preferably 10 to 50% by mass from the viewpoint of coating film formation. 10 to 40% by mass is particularly preferable.
本発明の樹脂組成物は上記の(a)ポリイミド前駆体を含み、好ましくは有機溶剤を含む。
[(b)有機溶剤]
(b)有機溶剤は、本発明のポリイミド前駆体(ポリアミド酸)を溶解できるものであれば特に制限はなく、このような(b)有機溶剤としては上記(a)ポリイミド前駆体(ポリアミド酸)の合成時に用いることのできる溶媒を用いることができる。(b)有機溶剤は(a)ポリアミド酸の合成時に用いられる溶媒と同一でも異なってもよい。
(b)成分は、樹脂組成物の25℃における粘度が0.5Pa・s~100Pa・sとなるように調整して加えることが好ましい。 [Resin composition]
The resin composition of the present invention contains the above (a) polyimide precursor, and preferably contains an organic solvent.
[(B) Organic solvent]
(B) The organic solvent is not particularly limited as long as it can dissolve the polyimide precursor (polyamide acid) of the present invention, and (b) the above-mentioned (a) polyimide precursor (polyamide acid) is an organic solvent. A solvent that can be used in the synthesis of can be used. (B) The organic solvent may be the same as or different from the solvent used in the synthesis of (a) polyamic acid.
The component (b) is preferably added after adjusting so that the viscosity of the resin composition at 25 ° C. is 0.5 Pa · s to 100 Pa · s.
沸点が210℃より高いと乾燥工程が長時間必要となり、60℃より低いと、乾燥工程において樹脂膜の表面に荒れが発生したり、樹脂膜中に気泡が混入したりし、均一な膜が得られない可能性がある。 In addition, the boiling point of (b) the organic solvent at normal pressure is preferably 60 to 210 ° C, more preferably 100 to 205 ° C, and particularly preferably 140 to 180 ° C.
When the boiling point is higher than 210 ° C., a drying process is required for a long time. When the boiling point is lower than 60 ° C., the surface of the resin film is roughened in the drying process, or bubbles are mixed in the resin film. It may not be obtained.
本発明の樹脂組成物は、上記(a)、(b)成分の他に(1)接着性付与剤、(2)界面活性剤又はレベリング剤等を含有してもよい。
尚、本発明の組成物は、上記(a)及び(b)成分、及び任意に接着性付与剤、界面活性剤、レベリング剤等の添加剤から実質的になっていてもよく、また、これらの成分のみからなっていてもよい。「実質的になる」とは、上記組成物が、主に上記(a)及び(b)成分からなること(例えば、組成物全体の90重量%以上)であり、これらの成分の他に上記の添加剤を含み得ることである。 [Other ingredients]
The resin composition of the present invention may contain (1) an adhesion-imparting agent, (2) a surfactant or a leveling agent, in addition to the components (a) and (b).
The composition of the present invention may consist essentially of the above components (a) and (b), and optionally additives such as an adhesion-imparting agent, a surfactant, and a leveling agent. It may consist of only the components. “Substantially” means that the composition mainly comprises the components (a) and (b) (for example, 90% by weight or more of the entire composition). Of additives.
本発明の樹脂組成物は、硬化膜の基板との接着性を高めるために、有機シラン化合物、アルミキレート化合物等の(1)接着性付与剤を含有してもよい。 [Other components: (1) Adhesiveness imparting agent]
The resin composition of the present invention may contain (1) an adhesion-imparting agent such as an organic silane compound and an aluminum chelate compound in order to enhance the adhesion of the cured film to the substrate.
また、本発明の樹脂組成物は、塗布性の観点、例えば、ストリエーション(膜厚のムラ)を防ぐ観点から、(2)界面活性剤又はレベリング剤を含有してもよい。 [Other components: (2) Surfactant or leveling agent]
Moreover, the resin composition of this invention may contain (2) surfactant or a leveling agent from a viewpoint of applicability | paintability, for example, a viewpoint which prevents striation (film thickness nonuniformity).
この攪拌混合は撹拌翼を備えたスリーワンモータ(新東化学株式会社製)、自転公転ミキサー等の装置を用いることができる。また必要に応じて40~100℃の熱を加えてもよい。 The method for producing the resin composition of the present invention is not particularly limited. For example, when the solvent used when synthesizing (a) polyamic acid and (b) the organic solvent are the same, the resin composition was synthesized. A polyamic acid solution can be used as a resin composition. Further, if necessary, the component (b) and other additives may be added in a temperature range of room temperature (25 ° C.) to 80 ° C. and mixed with stirring.
For this stirring and mixing, an apparatus such as a three-one motor (manufactured by Shinto Chemical Co., Ltd.) equipped with a stirring blade, a rotation and revolution mixer, or the like can be used. If necessary, heat of 40 to 100 ° C. may be applied.
具体的には、薄膜トランジスタ(TFT)の基板、カラーフィルタの基板、透明導電膜(ITO、IndiumThinOxide)の基板等を形成するために用いることができる。 The resin composition of the present invention can be used to form a transparent substrate of a display device such as a liquid crystal display, an organic electroluminescence display, a field emission display, or electronic paper.
Specifically, it can be used for forming a thin film transistor (TFT) substrate, a color filter substrate, a transparent conductive film (ITO, Indium Thin Oxide) substrate, and the like.
本発明のポリイミド成形体は、本発明の樹脂組成物を基材に塗布、乾燥して得られた樹脂膜を形成し、これを加熱処理(イミド化)することにより得ることができる。また、該ポリイミド成形体は、使用用途・目的により、膜状、フィルム状、シート状等の形態として用いることができる。 [Polyimide molded product]
The polyimide molded body of the present invention can be obtained by forming a resin film obtained by applying the resin composition of the present invention to a substrate and drying it, followed by heat treatment (imidization). Moreover, this polyimide molded object can be used as forms, such as a film form, a film form, and a sheet form, according to a use use and the objective.
塗布工程で使用される塗布方法は、特に制限はなく、所望の塗布厚や樹脂組成物の粘度等に応じて、公知の塗布方法を適宜選択して使用できる。具体的には、ドクターブレードナイフコーター、エアナイフコーター、ロールコーター、ロータリーコーター、フローコーター、ダイコーター、バーコーター等の塗布方法、スピンコート、スプレイコート、ディップコート等の塗布方法、スクリーン印刷やグラビア印刷等に代表される印刷技術を応用することもできる。 (1) Application | coating process The application | coating method used at an application | coating process does not have a restriction | limiting in particular, According to the desired application | coating thickness, the viscosity of a resin composition, etc., it can select and use a well-known application | coating method suitably. Specifically, doctor blade knife coater, air knife coater, roll coater, rotary coater, flow coater, die coater, bar coater and other coating methods, spin coating, spray coating, dip coating and other coating methods, screen printing and gravure printing It is also possible to apply printing techniques represented by the above.
加熱工程は、イナートガスオーブンやホットプレート、箱型乾燥機、コンベヤー型乾燥機等の装置を用いて行う。この工程は前記(2)乾燥工程と同時に行っても、逐次的に行ってもよい。 Subsequently, (3) a heating step is performed. The heating step is a step of (2) removing the organic solvent remaining in the resin film in the drying step and advancing the imidization reaction of the polyamic acid in the resin composition to obtain a cured film.
A heating process is performed using apparatuses, such as an inert gas oven, a hotplate, a box type dryer, and a conveyor type dryer. This step may be performed simultaneously with the (2) drying step or sequentially.
離型剤としては、植物油系、シリコン系、フッ素系、アルキッド系等の離型剤が挙げられる。 In addition, depending on the intended use and purpose of the polyimide molded body, (4) a peeling step for peeling the cured film from the substrate is required after the heating step. This peeling step is performed after the molded body on the substrate is cooled to room temperature to about 50 ° C. In order to easily perform the peeling operation, a release agent may be applied to the substrate as necessary before applying the resin composition of the present invention.
Examples of the release agent include vegetable oil-based, silicon-based, fluorine-based, and alkyd-based release agents.
レジスト材料及びエッチングに用いられる材料は、通常のレジストプロセスで用いられるものであれば、特に制限はない。例えば、一般によく知られたエッチング溶液としては、ヒドラジン水和物、水酸化カリウム水溶液、水酸化ナトリウム水溶液等がある。 The obtained polyimide molded body can also form a pattern by a resist process according to a use. In the resist process, for example, after (3) the heating step or (4) the peeling step, a resist is applied, and a pattern is formed by exposure and development.
The resist material and the material used for etching are not particularly limited as long as they are used in a normal resist process. For example, generally well-known etching solutions include hydrazine hydrate, potassium hydroxide aqueous solution, sodium hydroxide aqueous solution and the like.
また、本発明のポリイミド成形体の複屈折は0.12以下が好ましく、0.08以下がより好ましい。光通信分野、表示装置分野に利用されるポリイミド成形体として十分な透明性、低複屈折率を有すると評される値である。 The transparency of the polyimide molded body of the present invention obtained by the above production method is such that the light transmittance at a wavelength of 400 nm or more is preferably 70% or more, more preferably 75% or more at a film thickness of 10 μm.
The birefringence of the polyimide molded body of the present invention is preferably 0.12 or less, and more preferably 0.08 or less. This value is regarded as having sufficient transparency and low birefringence as a polyimide molded body used in the fields of optical communication and display devices.
ガラス転移温度は、実施例に記載した方法で測定できる。
また、CTE及びガラス転移温度(Tg)はセイコーインスツル株式会社製TMA/SS6000によってTMA測定を行い求められる。 The glass transition temperature (Tg) of the polyimide molded body of the present invention is preferably 250 to 400 ° C., more preferably 300 to 400 ° C. This value is regarded as having sufficient heat resistance as a polyimide molded body used in the fields of optical communication and display devices.
The glass transition temperature can be measured by the method described in the examples.
Moreover, CTE and glass transition temperature (Tg) are calculated | required by measuring TMA by TMA / SS6000 by Seiko Instruments Inc.
破断伸びは5%以上が好ましく、10%以上がより好ましい。破断伸びが5%より小さいと、ポリイミド成形体を基材として用いた場合の曲げ応力が弱く、基材の信頼性が低下する。 The tensile strength (breaking strength) is preferably 150 to 300 MPa, and more preferably 150 to 200 MPa. If the tensile strength is less than 150 MPa, the film is fragile and may be difficult to handle when used as a substrate.
The elongation at break is preferably 5% or more, and more preferably 10% or more. If the elongation at break is less than 5%, the bending stress when the polyimide molded body is used as a substrate is weak, and the reliability of the substrate is lowered.
本発明の透明基板及び保護膜は、上記ポリイミド成形体からなることを特徴とする。その製造方法は、従来公知の製造方法を用いることができる。例えば、本発明の樹脂組成物を仮固定基材に塗布し、乾燥及び加熱を行い、次いで用途に応じて上記レジストプロセスを行い、透明基板として使用することができる。
また、本発明の樹脂組成物を仮固定基材に塗布し、乾燥及び加熱を行い、仮固定基材から剥離して保護膜として用いることができる。 [Transparent substrate / Protective film / Electronic components]
The transparent substrate and protective film of the present invention are characterized by comprising the polyimide molded body. As the manufacturing method, a conventionally known manufacturing method can be used. For example, the resin composition of the present invention can be applied to a temporarily fixed substrate, dried and heated, then subjected to the resist process according to the application, and used as a transparent substrate.
In addition, the resin composition of the present invention can be applied to a temporarily fixed substrate, dried and heated, peeled from the temporarily fixed substrate, and used as a protective film.
また、本発明の透明基板は、弾性率が小さいため、フレキシブルディスプレイの基板としても用いることができる。 Furthermore, since the CTE of the transparent substrate of the present invention is small, it is possible to prevent deterioration in alignment accuracy in the heating process at the time of TFT formation, and the transparency is high and the birefringence is small, so that the visibility is excellent.
Moreover, since the transparent substrate of the present invention has a low elastic modulus, it can also be used as a substrate for a flexible display.
攪拌機、温度計を備えた0.2リットルのフラスコ中に、N-メチルピロリドン(NMP)56g(564mmol)と1,4-ジアミノシクロヘキサン3.43g(30mmol)を仕込み、撹拌した後、乾燥機で(160℃、24時間)加熱し脱水閉環させた3,3’,4,4’-ビフェニルテトラカルボン酸二無水物8.39g(28.5mmol)、及び4,4’-オキシジフタル酸二無水物0.47g(1.5mmol)を、添加し、70℃のウォーターバスで10分間、加熱攪拌し完全に溶解させた。その後、分子量が一定となるまで約70時間撹拌してポリアミド酸溶液を得た。 Example 1
A 0.2-liter flask equipped with a stirrer and a thermometer was charged with 56 g (564 mmol) of N-methylpyrrolidone (NMP) and 3.43 g (30 mmol) of 1,4-diaminocyclohexane, stirred, and then dried with a dryer. 8.39 g (28.5 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride heated and dehydrated (160 ° C., 24 hours) and 4,4′-oxydiphthalic dianhydride 0.47 g (1.5 mmol) was added, and the mixture was heated and stirred in a water bath at 70 ° C. for 10 minutes to completely dissolve. Thereafter, the mixture was stirred for about 70 hours until the molecular weight became constant to obtain a polyamic acid solution.
測定装置:検出器 株式会社日立製作所社製L4000UV
ポンプ:株式会社日立製作所社製L6000
株式会社島津製作所社製C-R4AChromatopac
測定条件:カラム 日立化成工業株式会社製GelpackGL-S300MDT-5×2本
溶離液:THF/DMF=1/1(容積比)
LiBr(0.03mol/l)、H3PO4(0.06mol/l)
流速:1.0ml/分、検出器:UV270nm
ポリマー0.5mgに対して溶媒[THF/DMF=1/1(容積比)]1mlの溶液を用いて測定した。 The measurement conditions of the weight average molecular weight and the degree of dispersion are as follows.
Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
C-R4Achromatopac manufactured by Shimadzu Corporation
Measurement conditions: Column GelpackGL-S300MDT-5 × 2 by Hitachi Chemical Co., Ltd. Eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / l), H 3 PO 4 (0.06 mol / l)
Flow rate: 1.0 ml / min, detector: UV 270 nm
The measurement was performed using a solution of 1 ml of a solvent [THF / DMF = 1/1 (volume ratio)] with respect to 0.5 mg of the polymer.
また合成反応中の塩形成を評価した。塩が生じなかった場合又は塩の形成を確認できるが樹脂組成物中の溶媒に容易に溶解する場合をA、塩が形成し、容易に溶媒に溶解しない場合をBとして評価を行なったところ、実施例1の樹脂組成物はBであった。 This diluted solution was filtered using a 5 μm filter (Millipore, SLLS025NS), the obtained resin composition was spin-coated on a silicon wafer, dried at 120 ° C. for 3 minutes, and a film thickness of 14 to 18 μm. A resin film was formed. This was further heated in a nitrogen atmosphere using an inert gas oven to obtain a cured film having a thickness of 10 μm.
Also, salt formation during the synthesis reaction was evaluated. When the salt was not formed or the formation of the salt could be confirmed, the case where it was easily dissolved in the solvent in the resin composition was evaluated as A, and the case where the salt was formed and not easily dissolved in the solvent was evaluated as B. The resin composition of Example 1 was B.
装置:光洋サーモシステム株式会社製イナートガスオーブン
条件:昇温 室温~200℃(5℃/分)
ホールド 200℃(20分)
昇温 200℃~300℃(5℃/分)
ホールド 300℃(60分)
冷却 300℃~室温(60分) The heating conditions by the inert gas oven are as follows.
Equipment: Inert gas oven manufactured by Koyo Thermo System Co., Ltd. Conditions: Temperature rise Room temperature to 200 ° C (5 ° C / min)
Hold 200 ° C (20 minutes)
Temperature increase 200 ° C to 300 ° C (5 ° C / min)
Hold 300 ° C (60 minutes)
Cooling 300 ° C to room temperature (60 minutes)
(複屈折の評価)
セキテクノトロン株式会社製メトリコン2010型を用い、1300nmの波長におけるY偏波での屈折率(TE)と、X偏波での屈折率(TM)の値を測定し、(式1)によって複屈折を求めた。
複屈折=TE-TM (式1)
複屈折が0.08以下のものをA(特に良好)、0.08よりも大きく0.12以下のものをB(良好)、0.12よりも大きいものをC(良くない)とした。 The following evaluation was performed about the obtained cured film.
(Evaluation of birefringence)
Using a Metricon 2010 model manufactured by Seki Technotron Co., Ltd., the values of the refractive index (TE) in the Y polarization and the refractive index (TM) in the X polarization at a wavelength of 1300 nm are measured. Refraction was determined.
Birefringence = TE-TM (Formula 1)
A birefringence of 0.08 or less was designated as A (particularly good), a value greater than 0.08 and 0.12 or less was designated as B (good), and a value greater than 0.12 was designated as C (not good).
4.9質量%フッ酸水溶液を用いて、得られた硬化膜をシリコンウエハより剥離し、水洗、乾燥した後、透過率、CTE、ガラス転移温度(Tg)、機械強度の評価を行なった。 (Evaluation of transmittance, coefficient of thermal expansion (CTE), glass transition temperature, and mechanical strength)
The obtained cured film was peeled from the silicon wafer using a 4.9% by mass hydrofluoric acid aqueous solution, washed with water and dried, and then evaluated for transmittance, CTE, glass transition temperature (Tg), and mechanical strength.
CTEが30ppm/K以下の場合をA(特に良好)、30ppm/Kより大きく45ppm/K以下の場合をB(良好)、45ppm/Kより大きい場合をC(良くない)とした。 CTE was measured using a TMA / SS6000 thermomechanical measuring device manufactured by Seiko. Specifically, the cured film is cut into 2 mm × 3 cm, and the temperature is increased to 30 to 420 ° C. while applying a weight of 10 g / min using a TMA / SS6000 thermomechanical measuring device manufactured by Seiko (temperature increase rate 5 ° C./min. ) Heated. At that time, the gradient of the elongation of the cured film between 100 and 200 ° C. was measured to obtain CTE.
The case where CTE was 30 ppm / K or less was designated as A (particularly good), the case where it was greater than 30 ppm / K and 45 ppm / K or less was designated as B (good), and the case where it was greater than 45 ppm / K was designated as C (not good).
弾性率は5.5GPa以下のものをA(特に良好)、5.5GPaより大きく6.0GPa以下のものをB、6.0GPaより大きいものをC(良くない)とした。 The mechanical strength (elastic modulus, elongation at break, and strength at break) was obtained from a tensile test using Autograph AGS-100NH manufactured by Shimadzu Corporation.
An elastic modulus of 5.5 GPa or less was designated as A (particularly good), a value greater than 5.5 GPa and less than or equal to 6.0 GPa was designated B, and a material having a modulus of elasticity greater than 6.0 GPa was designated C (not good).
得られた硬化膜を、ジメチルスルホキシド:モノエタノールアミン=30:70の溶液に80℃で10分間浸漬し、硬化膜の薬液耐性を評価した。硬化膜にクラックが無いものをA、クラックが入ったものをBと評価した。
また、薬液耐性の評価試験前後の膜厚の変化が±0.3μm未満のものをA、±0.3以上±0.5μm以下のものをB、±0.5μmより大きいものをCとした。 (Evaluation of chemical resistance)
The obtained cured film was immersed in a solution of dimethyl sulfoxide: monoethanolamine = 30: 70 at 80 ° C. for 10 minutes, and the chemical resistance of the cured film was evaluated. A cured film having no crack was evaluated as A, and a crack having a crack was evaluated as B.
A change in film thickness before and after the chemical resistance evaluation test is less than ± 0.3 μm, A is ± 0.3 to ± 0.5 μm, and B is greater than ± 0.5 μm. .
アミン、酸及びこれらの量を表1のように変更した他は、実施例1と同様にしてポリアミド酸を合成し、樹脂組成物及び硬化膜を作製し、これらの評価を行った。
アミン1~3、酸1~4は下記の通りである。
アミン1:1,4-ジアミノシクロヘキサン
アミン2:3,3’-ビス(トリフルオロメチル)ベンジジン
アミン3:p-フェニレンジアミン
酸1:3,3’,4,4’-ビフェニルテトラカルボン酸
酸2:3,3’,4,4’-テトラカルボキシジフェニルエーテル
酸3:シクロヘキサンテトラカルボン酸二無水物
Examples 2-8, Comparative Examples 1-5
A polyamic acid was synthesized in the same manner as in Example 1 except that the amount of amine, acid and the amount thereof was changed as shown in Table 1, and a resin composition and a cured film were prepared, and these were evaluated.
The amines 1 to 3 and the acids 1 to 4 are as follows.
Amine 1: 1,4-diaminocyclohexaneamine 2: 3,3′-bis (trifluoromethyl) benzidineamine 3: p-phenylenediamine acid 1: 3,3 ′, 4,4′-biphenyltetracarboxylic acid 2 : 3,3 ′, 4,4′-tetracarboxydiphenyl ether acid 3: cyclohexanetetracarboxylic dianhydride
さらに、実施例1~8で得られた硬化膜は、いずれも薬液耐性に優れることが分かった。 The cured films obtained in Examples 1 to 8 exhibited good transmittance even after heat treatment at a high temperature of 300 ° C. or higher, had low CTE, low birefringence, and low elastic modulus. It has been found that the polyimide precursor of the present invention provides a cured film that satisfies all of transparency, CTE, and mechanical strength.
Furthermore, it was found that all of the cured films obtained in Examples 1 to 8 were excellent in chemical resistance.
また、比較例2のように、3,3’,4,4’-ビフェニルテトラカルボン酸を使用しない場合、CTEが大きくなってしまった。 On the other hand, when 3,3 ′, 4,4′-tetracarboxydiphenyl ether was not included as in Comparative Example 1, the elastic modulus and birefringence were increased.
Further, as in Comparative Example 2, when 3,3 ′, 4,4′-biphenyltetracarboxylic acid was not used, CTE was increased.
この明細書に記載の文献及び本願のパリ優先の基礎となる日本出願明細書の内容を全てここに援用する。
Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.
The contents of the documents described in this specification and the specification of the Japanese application that is the basis of Paris priority of the present application are all incorporated herein.
Claims (12)
- 請求項1に記載のポリイミド前駆体を有する樹脂組成物。 A resin composition having the polyimide precursor according to claim 1.
- 有機溶剤を含有する請求項2に記載の樹脂組成物。 The resin composition according to claim 2 containing an organic solvent.
- 表示装置の透明基板形成用の請求項2又は3に記載の樹脂組成物。 The resin composition according to claim 2 or 3 for forming a transparent substrate of a display device.
- 請求項1に記載のポリイミド前駆体を加熱して得られるポリイミド。 A polyimide obtained by heating the polyimide precursor according to claim 1.
- 請求項2~4のいずれかに記載の樹脂組成物を基材上に塗布、乾燥して樹脂膜を形成する工程と、前記乾燥後の樹脂膜を加熱処理する工程とを含むポリイミド成形体の製造方法。 A polyimide molded body comprising a step of applying a resin composition according to any one of claims 2 to 4 onto a substrate and drying to form a resin film, and a step of heat-treating the resin film after drying. Production method.
- 請求項6に記載の製造方法により得られるポリイミド成形体。 A polyimide molded body obtained by the production method according to claim 6.
- 請求項7に記載のポリイミド成形体からなる透明基板。 A transparent substrate comprising the polyimide molded body according to claim 7.
- 請求項7に記載のポリイミド成形体からなる保護膜。 A protective film comprising the polyimide molded body according to claim 7.
- 請求項8に記載の透明基板又は請求項9に記載の保護膜を有する電子部品。 An electronic component having the transparent substrate according to claim 8 or the protective film according to claim 9.
- 請求項8に記載の透明基板又は請求項9に記載の保護膜を有する表示装置。 A display device having the transparent substrate according to claim 8 or the protective film according to claim 9.
- 請求項8に記載の透明基板又は請求項9に記載の保護膜を有する太陽電池モジュール。 A solar cell module having the transparent substrate according to claim 8 or the protective film according to claim 9.
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JP2013537394A JP6261981B2 (en) | 2011-10-05 | 2012-09-25 | Highly transparent polyimide |
KR1020147007021A KR102044260B1 (en) | 2011-10-05 | 2012-09-25 | Highly transparent polyimide |
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JP2020105504A (en) * | 2018-12-20 | 2020-07-09 | コーロン インダストリーズ インク | Polyamic acid, polyimide resin, and polyimide film |
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JP2021057276A (en) * | 2019-10-01 | 2021-04-08 | 株式会社ジャパンディスプレイ | Display device |
KR102347593B1 (en) * | 2019-11-21 | 2022-01-10 | 피아이첨단소재 주식회사 | Polyimide film and method for preparing the same |
KR102346581B1 (en) * | 2019-11-22 | 2022-01-05 | 피아이첨단소재 주식회사 | Method for preparing polyimide film and polyimide film prepared thereby |
KR102396419B1 (en) * | 2019-11-29 | 2022-05-12 | 피아이첨단소재 주식회사 | Polyimide film and method for preparing the same |
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TW201319124A (en) | 2013-05-16 |
JP2018024886A (en) | 2018-02-15 |
JP6891084B2 (en) | 2021-06-18 |
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JPWO2013051213A1 (en) | 2015-03-30 |
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JP6261981B2 (en) | 2018-01-17 |
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