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WO2019065624A1 - Film, film de polyimide, stratifié, élément d'affichage, élément à écran tactile, affichage à cristaux liquides et appareil d'affichage à électroluminescence organique - Google Patents

Film, film de polyimide, stratifié, élément d'affichage, élément à écran tactile, affichage à cristaux liquides et appareil d'affichage à électroluminescence organique Download PDF

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Publication number
WO2019065624A1
WO2019065624A1 PCT/JP2018/035439 JP2018035439W WO2019065624A1 WO 2019065624 A1 WO2019065624 A1 WO 2019065624A1 JP 2018035439 W JP2018035439 W JP 2018035439W WO 2019065624 A1 WO2019065624 A1 WO 2019065624A1
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Prior art keywords
polyimide
film
residue
polyimide film
diamine
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PCT/JP2018/035439
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English (en)
Japanese (ja)
Inventor
勝哉 坂寄
太田　貴之
滉大 岡田
奈保美 金澤
小林　義弘
綾 勝又
綾子 古瀬
前田　高徳
敬輔 脇田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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Priority claimed from JP2018176585A external-priority patent/JP7363019B2/ja
Application filed by Dai Nippon Printing Co Ltd filed Critical Dai Nippon Printing Co Ltd
Publication of WO2019065624A1 publication Critical patent/WO2019065624A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods

Definitions

  • the present invention relates to a film, a polyimide film, a laminate, a member for display, a touch panel member, a liquid crystal display device, and an organic electroluminescence display device.
  • Thin sheet glass is excellent in hardness, heat resistance and the like, but is difficult to bend, is easily broken when dropped, has a problem in workability, and is heavy as compared with a plastic product. For this reason, in recent years, resin products such as resin base materials and resin films are being replaced with glass products in view of processability and weight reduction, and research on resin products to be glass substitute products has been conducted.
  • a polyimide is a highly heat-resistant resin obtained by subjecting a polyamide acid obtained by the condensation reaction of an aromatic tetracarboxylic acid anhydride and an aromatic diamine to a dehydration ring closure reaction.
  • polyimide generally has a yellow or brown color, it has been difficult to use in fields requiring transparency, such as display applications and optical applications. Therefore, application of a polyimide having improved transparency to a display member has been studied.
  • Patent Document 1 as a polyimide resin having high heat resistance, high transparency, and low water absorption, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid At least one acyl-containing compound selected from the group consisting of anhydrides and reactive derivatives thereof and at least one compound selected from compounds having at least one phenylene group and isopropylidene group represented by a specific formula Polyimides are disclosed which are made to react with imino forming compounds and are described as being suitable for substrate materials such as flat panel displays and cellular telephone equipment.
  • Patent Document 2 includes a unit structure derived from an aromatic dianhydride and an aromatic diamine, and a functional group selected from the group consisting of an additive for improving tear strength, or a hexafluoro group, a sulfone group and an oxy group.
  • a transparent polyimide film is disclosed, which further comprises a unit structure derived from the monomer having the monomer.
  • Patent Document 3 discloses, as a polyimide film excellent in transparency and heat resistance, a polyimide film in which the top of the peak in the tan ⁇ curve, which is a value obtained by dividing the loss elastic modulus by the storage elastic modulus, is within a specific range. ing.
  • Patent Document 4 as a polyimide film used for a substrate of a flexible device, a colorless and transparent polyimide film having low residual stress generated with an inorganic film and excellent in mechanical physical properties and thermal physical properties is obtained.
  • Patent Document 4 when a polyimide film with an inorganic film (SiN film) is formed using the above-mentioned polyimide precursor, neither cracks nor peeling is observed after a bending test in which bending is repeated 10 times (o), cracks It is described as observed ( ⁇ ).
  • Patent Document 5 describes that as a polyimide having a low refractive index and high bending resistance, silicone diamine having 2 to 21 silicon atoms is contained in an amount of 10% by weight or more based on the weight of the diamine raw material.
  • the mobile device that can fold the screen is in the folded state when carrying it, and in the folded state when it is used. Therefore, it is required that a flexible display mounted on a mobile device does not have a display defect even if it is repeatedly bent, and a base material and a surface material for a flexible display have bending resistance when repeated bending (hereinafter referred to as , Sometimes called dynamic bending resistance).
  • the flexible display mounted on the mobile device can be restored to its original state when it is returned to a flat state even if the bent state continues for a long time
  • the base material and the surface material for a flexible display are also required to have restorability after being bent for a long time (hereinafter sometimes referred to as static bending resistance).
  • base materials and surface materials for flexible displays are not only resistant to repeated bending but also function to prevent scratching of the surface, and to prevent damage to the touch sensor and display panel located below it. Is also required.
  • the bending resistance and the surface hardness of the resin film are considered to be opposite properties as described in detail later, but a resin film having both the bending resistance and a surface hardness sufficient as a protective film is required.
  • the present invention has been made in view of the above problems, and its main object is to provide a film or a resin film which is excellent in transparency and in which a decrease in surface hardness is suppressed while improving bending resistance. Further, the present invention provides a laminate having the film or resin film, a member for display which is the film or resin film or the laminate, a touch panel member including the film or resin film or the laminate, liquid crystal An object of the present invention is to provide a display device and an organic electroluminescent display device.
  • the film of the present invention is a stress-strain curve obtained by a tensile test in which a test piece of 15 mm ⁇ 40 mm is measured at 25 ° C. at a tensile speed of 10 mm / min and a chuck distance of 20 mm according to JIS K7127.
  • the strain is 8% or more
  • the tensile modulus of elasticity in the tensile test is 1.8 GPa or more
  • the total light transmittance measured in accordance with JIS K7361-1 is 85% or more
  • the yellowness calculated in accordance with JIS K7373-2006 is 5 or less.
  • the polyimide film of the present invention is a stress-strain curve obtained by a tensile test in which a test piece of 15 mm ⁇ 40 mm is measured at 25 ° C. at a tensile speed of 10 mm / min and a distance between chucks of 20 mm according to JIS K7127. Strain at 8% or more, The tensile modulus of elasticity in the tensile test is 1.8 GPa or more, The total light transmittance measured in accordance with JIS K7361-1 is 85% or more, and the yellowness calculated in accordance with JIS K7373-2006 is 5 or less.
  • the polyimide film of the present invention preferably has a Young's modulus on the film surface of 2.3 GPa or more measured at 25 ° C. according to ISO 14577 and using a nanoindentation method, from the viewpoint of excellent surface hardness. .
  • the polyimide film of the present invention preferably contains a polyimide having a structure represented by the following general formula (1) from the viewpoint of light transmittance, bending resistance and surface hardness.
  • R 1 represents a tetravalent group which is a tetracarboxylic acid residue having an aromatic ring or an aliphatic ring, and a plurality of R 1 may be identical to or different from each other
  • R 2 represents a divalent group which is a diamine residue, and a plurality of R 2 may be the same or different, and at least a portion of the plurality of R 2 is an aromatic ring or an aliphatic ring Containing diamine residues, n represents the number of repeating units
  • R 2 represents a divalent group which is at least one selected from diamine residues having no silicon atom. Or a diamine residue having a hexafluoroisopropylidene skeleton in the main chain, or R 2 represents a divalent group which is a diamine residue, and is 2.5 mol% or more and 50 mol% of the total amount of R 2
  • the following are diamine residues having a silicon atom in the main chain, and 50 to 97.5 mol% of the total amount of R 2 is a diamine having no silicon atom and having an aromatic ring or an aliphatic ring Residues are preferred from the viewpoint of bending resistance and surface hardness.
  • R 1 in the above general formula (1) is a cyclohexanetetracarboxylic acid dianhydride residue, cyclopentane tetracarbonide Acid dianhydride residue, dicyclohexane-3,4,3 ′, 4′-tetracarboxylic acid dianhydride residue, cyclobutanetetracarboxylic acid dianhydride residue, pyromellitic acid dianhydride residue 3, 3 ', 4,4'-biphenyltetracarboxylic acid dianhydride residue, 2,2', 3,3'-biphenyltetracarboxylic acid dianhydride residue, 4,4 '-(hexafluoroisopropylidene) diphthalic acid Acid anhydride residue, 3,4 '-(hexafluoroisopropylidene) diphthalic anhydride residue, 3,3'-
  • R 2 represents a divalent group which is at least one selected from diamine residues having no silicon atom. Or a diamine residue having a hexafluoroisopropylidene skeleton in the main chain, or R 2 is a diamine residue having no silicon atom, and a diamine residue having one or two silicon atoms in the main chain And at least one divalent group selected from the group consisting of 2.5 to 50 mol% of the total amount of R 2 is a diamine residue having one or two silicon atoms in the main chain, Flexibility and surface hardness are improved when 50 mol% or more and 97.5 mol% or less of the total amount of R 2 is a diamine residue having no silicon atom and having an aromatic ring or an aliphatic ring. Or Preferred.
  • the diamine residue having the aromatic ring or the aliphatic ring in R 2 in the general formula (1) is Trans-cyclohexanediamine residue, trans-1,4-bismethylenecyclohexanediamine residue, 4,4'-diaminodiphenylsulfone residue, 3,4'-diaminodiphenylsulfone residue, 2,2-bis (4 -Aminophenyl) propane residue, 3,3'-bis (trifluoromethyl) -4,4 '-[(1,1,1,3,3,3-hexafluoropropane-2,2-diyl) bis (4,1-phenyleneoxy)] dianiline residue, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluorop Pan residue, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,
  • R 3 and R 4 each independently represent a hydrogen atom, an alkyl group or a perfluoroalkyl group.
  • the laminate of the present invention is a laminate having the film or polyimide film of the present invention, and a hard coat layer containing a polymer of at least one of a radically polymerizable compound and a cationically polymerizable compound.
  • the member for a display of the present invention includes the film or the polyimide film of the present invention, or the laminate of the present invention.
  • the display member of the present invention can be used for a flexible display.
  • the present invention also relates to the film or polyimide film of the present invention or the laminate of the present invention, A transparent electrode comprising a plurality of conductive parts disposed on one side of the film or the polyimide film or the laminate; A touch panel member is provided having a plurality of lead lines electrically connected on at least one side of an end of the conductive portion.
  • the present invention also relates to the film or polyimide film of the present invention or the laminate of the present invention,
  • a liquid crystal display device comprising: a liquid crystal display unit having a liquid crystal layer between opposing substrates disposed on one side of the film, the polyimide film, or the laminate.
  • the present invention also relates to the film or polyimide film of the present invention or the laminate of the present invention,
  • An organic electroluminescent display device comprising: the film, the polyimide film, or the organic electroluminescent display portion having an organic electroluminescent layer between opposing substrates disposed on one side of the laminate.
  • or the resin film which were excellent in transparency, and in which the fall of surface hardness was suppressed can be provided, improving a bending resistance.
  • the present invention provides a laminate having the film or the resin film, a display member which is the film or the resin film or the laminate, a touch panel member including the film or the resin film or the laminate, and a liquid crystal display And an organic electroluminescent display can be provided.
  • FIG. 7 is an A-A ′ cross-sectional view of the touch panel member shown in FIGS. 5 and 6. It is a schematic plan view which shows an example of the electroconductive member provided with the laminated body of this invention.
  • the film of the present invention is a stress-strain curve obtained by a tensile test in which a test piece of 15 mm ⁇ 40 mm is measured at 25 ° C. at a tensile speed of 10 mm / min and a distance between chucks of 20 mm according to JIS K7127. Strain at 8% or more, The tensile modulus of elasticity in the tensile test is 1.8 GPa or more, The total light transmittance measured in accordance with JIS K7361-1 is 85% or more, and the yellowness calculated in accordance with JIS K7373-2006 is 5 or less.
  • the strain at the yield point is 8% or more
  • the specific tensile modulus in the tensile test the specific total light transmission
  • the film means a thin film or flat material having a thickness of about 1 ⁇ m to 200 ⁇ m, includes a material called a sheet, and may be long.
  • the film of the present invention includes a resin film.
  • the material of the resin film include polyimide, polyamide, triacetyl cellulose, polyethylene, polypropylene, polyacetal, polyester (polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate), polyvinyl chloride, AS resin, ABS resin, polystyrene, poly Methyl methacrylate, polyacetal, polycarbonate, polyphenylene sulfide, polyarylate, polysulfone, polyether sulfone, polyether ether ketone, liquid crystal polymer, polytetrafluoroethylene, cellulose acylate, cycloolefin polymer, MBS resin, and at least one of these And the like.
  • the material type is not particularly limited as long as it satisfies the physical property values within the scope of the present invention, but organic materials, silicone materials, copolymers thereof, and mixtures thereof are preferable, among which the glass transition temperature of the film is 150 ° C. Those above are suitably used.
  • a polyimide film or a polyamide film using polyimide or polyamide as a film material is particularly preferably used.
  • the action, characteristics and the like of the film of the present invention will be described in detail below by taking a polyimide film as an example.
  • the action, characteristics and the like of the film of the present invention may be the same as those of the polyimide film of the present invention described later.
  • the polyimide film of the present invention is a stress-strain curve obtained by a tensile test in which a test piece of 15 mm ⁇ 40 mm is measured at 25 ° C. as a tensile speed of 10 mm / min and a distance between chucks of 20 mm according to JIS K7127.
  • the strain at the yield point is 8% or more
  • the tensile modulus of elasticity in the tensile test is 1.8 GPa or more
  • the total light transmittance measured in accordance with JIS K7361-1 is 85% or more
  • the yellowness calculated in accordance with JIS K7373-2006 is 5 or less.
  • the strain at the yield point is 8% or more
  • the specific tensile modulus in the tensile test the specific total light transmission
  • polyimide among resins.
  • Polyimide is known to be derived from its chemical structure and to be excellent in durability such as heat resistance.
  • polyimide films are known to form an ordered structure in which the arrangement of molecular chains in the interior form a constant structure, which makes it possible to recover the stability when repeating a flat state and a bent state at a constant cycle at room temperature. It is considered to show good results in
  • conventional resin films using transparent polyimide tend to break easily in a test in which the flat state and bending state are repeated at a constant cycle, or have a crease, and are difficult to return to flat, and have poor bending resistance. .
  • the film is bent by applying tension to the outer periphery of the film and compressive force to the inner periphery of the film, and the maximum stress ( ⁇ at the maximum stressed portion) at which the stress is maximum in the bending of the film as shown in FIG. Is represented by the following formula (1).
  • E Elastic modulus y: Maximum value of the distance from the neutral axis (axis centered at bending) (in the case of FIG. 1, half of the film thickness d) ⁇ : Curvature (test width) d: Film thickness
  • the maximum stress ( ⁇ ) is proportional to the modulus of elasticity and film thickness of the film and inversely proportional to the value obtained by subtracting the film thickness from the curvature, as shown in the equation (1). Therefore, when the elastic modulus of the film is increased, the stress applied to the film at the time of bending also increases, which causes deformation. Also in the resin film, when the elastic modulus is increased, the restorability after the bending state is deteriorated, and the bending resistance tends to be insufficient. On the other hand, the surface hardness tends to be improved by increasing the elastic modulus of the resin film.
  • the polyimide film having a large elastic modulus is deteriorated in bending resistance although the surface hardness is good.
  • the bending resistance of the resin film and the surface hardness are considered to be contradictory characteristics.
  • Substrates and surface materials for flexible displays are required not only to withstand repeated bending but also to prevent scratching of the surface and to prevent damage to the touch sensor and display panel located below it.
  • the surface material is, for example, a material having a high elastic modulus such as glass, the impact can be diffused in the surface direction to the impact from the surface of the display, and the local impact can be alleviated. As the display panel can be prevented from breakage.
  • the surface material has a high elastic modulus.
  • the elastic modulus when the elastic modulus is low, the surface material itself may be deformed to reduce the impact, but a depression or the like caused by the deformation may be fixed, and the smoothness of the display surface is greatly reduced, and the appearance is improved. It is easy to lose.
  • the stress-strain curve is a relationship curve between tensile stress and strain obtained in a tensile test, and the horizontal axis represents strain (%) and the vertical axis represents tensile stress (MPa).
  • the area up to the yield point in the stress-strain curve can be regarded as an elastic deformation area, and the area after the yield point in the stress-strain curve can be regarded as a plastic deformation area.
  • the strain (%) at the yield point is larger than a predetermined value, it is estimated that the elastic deformation area becomes wider than a predetermined value and has a property of being easily restored even if it is bent. That is, the strain amount at the yield point obtained by the stress-strain curve can be expressed as an elastically deformable deformation amount, which can be considered as a deformation amount capable of being restored to the shape before the stress is applied.
  • the film has improved recoverability after repeated bending of the film. It is estimated that it is not.
  • the stress-strain curve is It has been shown that the values of strain (%) at the yield point are different, and the bending resistance is greatly different accordingly.
  • the polyimide film according to the present invention contains polyimide and has the above-mentioned specific characteristics. As long as the effects of the present invention are not impaired, it may further contain other components, or may have other configurations.
  • the polyimide film of the present invention has a strain at a yield point of 8% or more in a stress-strain curve obtained by a tensile test measured at 25 ° C.
  • the strain at the yield point is preferably 8.5% or more, more preferably 9.3% or more, and still more preferably 9.5% or more, from the viewpoint of improving bending resistance. .
  • the upper limit of the strain at the yield point is not limited, but the strain at the yield point may usually be 90% or less.
  • the larger the tensile modulus of elasticity the larger the force required to deform, so the material that is easily deformed to a large extent is the material with a small tensile modulus of elasticity.
  • the lower limit of the tensile elastic modulus in the present invention is 1.8 Gpa, while the tensile strength of the resin film having a large tensile strength is approximately 200 N / mm 2 .
  • the amount of strain reaching tensile strength 200 N / mm 2 is calculated for films with different tensile modulus, and the relationship between the tensile modulus and strain at 200 N / mm 2 is determined, and the strain amount of the film with a tensile modulus of 1.8 GPa
  • the strain amount can be estimated to be approximately 90%. From this, about 90% is considered to be the upper limit.
  • the tensile test is carried out using a tensile tester (for example, Shimadzu Corp. autograph AG-X 1N, load cell: SBL-1KN), 15 mm wide ⁇ 40 mm long (tensile direction 40 mm ⁇ direction orthogonal to tensile direction 15 mm)
  • a test piece is cut out of a polyimide film, and the test piece is measured at 25 ° C. as a tensile speed of 10 mm / minute and a distance between chucks of 20 mm according to JIS K7127.
  • the test piece is cut out of the film, it is preferable to cut out a portion having a uniform film thickness, for example, it is preferable to cut out from the vicinity of the central portion of the film.
  • the film thickness of the film is uniform, for example, the film thickness of a total of 5 points at the four corners and the center of the cut out film is measured using a digital linear gauge (Model PDN12 digital gauge manufactured by Ozaki Mfg. Co., Ltd.) The difference between the average film thickness of the five points and the film thickness of each point is within 6% of the average film thickness.
  • the stress-strain curve is the strain obtained by dividing the amount of elongation by the test length when the tensile test is performed at a distance of 10 mm / min with respect to the distance between chucks, that is, the test length of 20 mm. %) On the horizontal axis and tensile stress (MPa) on the vertical axis.
  • the strain (%) at the yield point of the stress-strain curve of the polyimide film of the present invention can be specifically determined as follows.
  • sampling is started from a point at which strain is 0.16% and thereafter sampled every 0.21% increase (this is defined as dx). That is, dx is the difference (change amount) from the value sampled immediately before that, and only the initial value is 0.16%, and then 0.21%.
  • dy is the difference (amount of change) from the value sampled one before in the value of the tensile stress according to the strain.
  • the graph of strain% and dy / dx (average change rate) is basically a downward slope graph as shown in FIG. 3, but the maximum value of dy / dx (average change rate) is obtained Beyond the point, the inflection point of dy / dx appearing first is defined as the yield point. In the case where the inflection point is not observed, the point at which dy / dx becomes 0 for the first time is taken as the yield point.
  • the strain (%) at the yield point is a value rounded to the first decimal place according to rule B of JIS Z8401: 1999.
  • the polyimide film of the present invention has a tensile modulus of at least 1.8 GPa at 25 ° C. measured at a tensile speed of 10 mm / minute and a distance between chucks of 20 mm according to JIS K7127 for a 15 mm ⁇ 40 mm test piece.
  • the tensile modulus is preferably 2.0 GPa or more, more preferably 2.1 GPa or more, and still more preferably 2.3 GPa or more.
  • the tensile modulus is preferably 5.2 GPa or less from the viewpoint of improving bending resistance. From the viewpoint of improving the bending resistance, the tensile modulus may be 4.0 GPa or less, 3.5 GPa or less, or 2.9 GPa or less. The tensile modulus can be measured in the same manner as a tensile test at the yield point of the stress-strain curve.
  • the polyimide film of the present invention has a total light transmittance of 85% or more as measured in accordance with the aforementioned JIS K7361-1. Such high transmittance allows for good transparency and can be a glass substitute material.
  • the total light transmittance of the polyimide film of the present invention measured according to JIS K7361-1 is preferably 88% or more, more preferably 89% or more, and particularly 90% or more. Is preferred.
  • the total light transmittance measured according to JIS K7361-1 can be measured, for example, by a haze meter (for example, HM150 manufactured by Murakami Color Research Laboratory). From the measured value of the total light transmittance of a certain thickness, the converted total light transmittance of different thicknesses can be determined according to the Lambert-Beer's law, which can be used.
  • a haze meter for example, HM150 manufactured by Murakami Color Research Laboratory
  • the polyimide film of the present invention has a yellowness (YI value) of 5 or less calculated in accordance with the above-mentioned JIS K7373-2006.
  • a low degree of yellowness suppresses yellowish coloring, improves light transmission, and can be a glass substitute material.
  • the yellowness (YI value) calculated in accordance with JIS K 737-2006 is preferably 4.5 or less, more preferably 4 or less, and still more preferably 3.5 or less.
  • the degree of yellowness (YI value) can be determined by the spectrophotometric method using an ultraviolet-visible near-infrared spectrophotometer (for example, JASCO Corporation V-7100) in accordance with JIS K7373-2006.
  • tristimulus values X, Y, Z in the XYZ color system are determined, and the X, Y , Z can be calculated by the following equation.
  • YI 100 (1.2769X-1.0592Z) / Y
  • the degree of yellowness of a different thickness is the total of each transmittance at each wavelength measured at intervals of 1 nm in the range of 250 nm or more and 800 nm or less of a sample with a certain thickness.
  • a converted value of each transmittance at each wavelength of different thickness can be obtained according to the Lambert-Beer's law, and it can be calculated and used based on it.
  • the polyimide film of the present invention has a yellowish color suppressed, improves light transmittance, and can be suitably used as a glass substitute material, so that the yellow color is calculated according to the aforementioned JIS K7373-2006.
  • the value (YI value / film thickness ( ⁇ m)) obtained by dividing the degree (YI value) by the film thickness ( ⁇ m) is preferably 0.10 or less, more preferably 0.05 or less, and 0.03 It is even more preferable that In the present invention, the value (YI value / film thickness ( ⁇ m)) obtained by dividing the yellowness (YI value) by the film thickness ( ⁇ m) follows the rule B of JIS Z8401: 1999, and the second place after the decimal point It is a rounded value.
  • polyimide is obtained by reacting a tetracarboxylic acid component and a diamine component. It is preferable to imidize the precursor after obtaining a polyamic acid which is a precursor by polymerization of a tetracarboxylic acid component and a diamine component. Accordingly, the polyimide used in the present invention is one containing a tetracarboxylic acid residue and a diamine residue in the main chain.
  • tetracarboxylic acid residue refers to a residue obtained by removing four carboxy groups from tetracarboxylic acid, and represents the same structure as a residue obtained by removing an acid dianhydride structure from tetracarboxylic acid dianhydride.
  • a diamine residue means the residue remove
  • the film formation is in the state of a polyimide precursor And then heat treated to form a polyimide by heat treatment, or by forming a polyimide precursor into a polyimide by chemical imidization and then molding in a polyimide solution to remove the solvent. Also, it can be produced by a method combining the thermal imidization and the chemical imidization.
  • tetracarboxylic acid component to be a tetracarboxylic acid residue for example, a tetracarboxylic acid component having an aromatic ring is preferable from the viewpoint of improving the surface hardness of the polyimide film.
  • tetracarboxylic acid dianhydride having an aromatic ring for example, pyromellitic acid dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid dianhydride 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic acid Acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-di Carboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxypheny
  • the tetracarboxylic acid component which has an aliphatic ring is also preferable from the point of the light transmittance of a polyimide film.
  • tetracarboxylic acid dianhydrides having an aliphatic ring include cyclohexanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, dicyclohexane-3,4,3 ′, 4′-tetracarboxylic acid Anhydride, cyclobutane tetracarboxylic acid dianhydride, etc. are mentioned.
  • the tetracarboxylic acid component mentioned above can also be used individually or in mixture of 2 or more types.
  • the diamine which has an aromatic ring for example is preferable from the point of durability of a polyimide film, and surface hardness.
  • the diamine which has an aliphatic ring is also preferable from the point of the light transmittance of a polyimide film.
  • the polyimide film which concerns on this invention contains the polyimide which contains the diamine residue which has an aromatic ring or an aliphatic ring, and the diamine residue which has a silicon atom in a principal chain especially.
  • polyimide By introducing a flexible molecular skeleton having a silicon atom in the main chain between molecular skeletons containing an aromatic ring or an aliphatic ring as a main component, polyimide can easily achieve both bending resistance and surface hardness. In addition, orientation is likely to be suppressed, and birefringence is likely to be reduced.
  • diamine having an aromatic ring for example, 4,4′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-bis (4-aminophenyl) propane) Aminophenyl) hexafluoropropane, p-phenylenediamine, o-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide 4,4'-Diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenylmethane, 3,4'-diamino
  • diamine having an aliphatic ring examples include trans-cyclohexanediamine, trans-1,4-bismethylenecyclohexanediamine, 2,6-bis (aminomethyl) bicyclo [2,2,1] heptane, 2,5- Bis (aminomethyl) bicyclo [2,2,1] heptane and the like can be mentioned.
  • diamine which has a silicon atom in a principal chain
  • diamine represented by the following general formula (A) is mentioned, for example.
  • each L independently represents a direct bond or an -O- bond
  • each R 10 independently represents a substituent, and may contain an oxygen atom or a nitrogen atom
  • R 11 independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted, and R 11 may independently have a substituent, and may contain an oxygen atom or a nitrogen atom
  • k is a number of 0 to 200.
  • a plurality of L, R 10 and R 11 may be the same or different from each other)
  • the alkyl group may be linear, branched or cyclic, and may be linear or a combination of branched and cyclic.
  • the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, Examples thereof include t-butyl group, pentyl group and hexyl group.
  • the cyclic alkyl group is preferably a cycloalkyl group having 3 to 10 carbon atoms, and specific examples thereof include a cyclopentyl group and a cyclohexyl group.
  • the aryl group is preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group and a naphthyl group.
  • the monovalent hydrocarbon group represented by R 10 may be an aralkyl group, and examples thereof include a benzyl group, a phenylethyl group and a phenylpropyl group.
  • hydrocarbon group which may contain an oxygen atom or a nitrogen atom
  • examples of the hydrocarbon group which may contain an oxygen atom or a nitrogen atom include, for example, an ether bond, a carbonyl bond, an ester bond, an amide bond, and an imino bond between a divalent hydrocarbon group described later and the monovalent hydrocarbon group. Included is a group bonded via at least one of the bonds (—NH—).
  • the substituent which the monovalent hydrocarbon group represented by R 10 may have is not particularly limited as long as the effects of the present invention are not impaired, and, for example, a halogen atom such as a fluorine atom or a chlorine atom And hydroxyl groups.
  • the monovalent hydrocarbon group represented by R 10 is an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 10 carbon atoms from the viewpoint of improving bending resistance and compatibility with surface hardness. Is preferred.
  • the alkyl group having 1 to 3 carbon atoms is more preferably a methyl group, and the aryl group having 6 to 10 carbon atoms is more preferably a phenyl group.
  • the alkylene group may be linear, branched or cyclic, and may be linear or a combination of branched and cyclic.
  • the alkylene group having 1 or more and 20 or less carbon atoms is preferably an alkylene group having 1 or more and 10 or less carbon atoms, and for example, a straight chain such as methylene group, ethylene group, various propylene groups, various butylene groups and cyclohexylene groups Examples include groups in combination of linear or branched alkylene groups and cyclic alkylene groups.
  • the arylene group is preferably an arylene group having a carbon number of 6 to 12, and examples of the arylene group include a phenylene group, a biphenylene group, and a naphthylene group, and further have a substituent for the aromatic ring described later.
  • the divalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom include an ether bond, a carbonyl bond, an ester bond, an amide bond, and an imino bond (-NH-) between the above-mentioned divalent hydrocarbon groups. At least one bonded group is mentioned.
  • the substituent which the divalent hydrocarbon group represented by R 11 may have is the same as the substituent which the monovalent hydrocarbon group represented by R 10 may have. It is good.
  • the divalent hydrocarbon group represented by R 11 is an alkylene group having 1 to 6 carbon atoms, or an arylene group having 6 to 10 carbon atoms, from the viewpoint of improving bending resistance and compatibility with surface hardness. It is more preferable that it is an alkylene group having 2 to 4 carbon atoms.
  • a diamine residue having a silicon atom in the main chain has one or two silicon atoms in the main chain, from the viewpoint of achieving an improved resistance to bending while maintaining a sufficient surface hardness as a protective film. It is preferably a diamine residue, and more preferably a diamine residue having two silicon atoms in the main chain.
  • a polyimide in which a specific amount of a short flexible molecular skeleton having one or two silicon atoms in the main chain is introduced between a rigid molecular skeleton containing an aromatic ring or an aliphatic ring is an aromatic ring or an aliphatic ring. It is considered that a polyimide film having a relatively large elastic deformation area can be easily obtained while maintaining the elastic modulus derived from the molecular skeleton containing the above, and the surface hardness and the bending resistance can be easily reconciled.
  • diamines having one silicon atom in the main chain examples include diamines represented by the following general formula (A-1). Further, examples of the diamine having two silicon atoms in the main chain include diamines represented by the following general formula (A-2).
  • L is each independently a direct bond or -O- bond, and each R 10 independently has a substituent Or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom or a nitrogen atom, and each R 11 may independently have a substituent, and an oxygen atom Or a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a nitrogen atom, and a plurality of L, R 10 and R 11 may be identical to or different from each other)
  • the molecular weight of the diamine residue having one or two silicon atoms in the main chain is preferably 1000 or less, and more preferably 800 or less, from the viewpoint of improving the bending resistance and compatibility with the surface hardness. More preferably, it is 500 or less, and particularly preferably 300 or less.
  • the diamine residue having one or two silicon atoms in the main chain may be used alone or in combination of two or more.
  • the diamine having one or two silicon atoms in the main chain is a diamine having two silicon atoms from the viewpoint of light transmittance of the resulting polyimide, and in terms of bending resistance and surface hardness, Furthermore, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, 1,3-bis (5-aminopentyl) tetramethyldisiloxane, etc. However, it is preferable from the viewpoints of the availability of these compounds and the light transmittance and surface hardness of the resulting polyimide.
  • the ratio of the diamine having a silicon atom in the main chain to the total amount of diamine is not particularly limited, but from the viewpoint of improving the bending resistance of the obtained polyimide film, 1 It is preferable that it is mol% or more, It is more preferable that it is 2.5 mol% or more, It is still more preferable that it is 5 mol% or more. Moreover, it is preferable that it is 50 mol% or less, it is preferable that it is 45 mol% or less, and it is more preferable that it is 30 mol% or less from the point of the bending resistance of the polyimide film obtained, and surface hardness.
  • the total amount of the tetracarboxylic acid component and the diamine component is 100 mol%
  • the total of the tetracarboxylic acid having an aromatic ring and the diamine having an aromatic ring is It is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 75 mol% or more.
  • the polyimide may contain an aromatic ring, and (i) a fluorine atom, (ii) an aliphatic ring, and (iii) an aromatic ring may be substituted with a sulfonyl group or fluorine. It is preferable to include at least one selected from the group consisting of an alkylene group-linked structure, and further to include, in addition to these structures, a diamine residue having a silicon atom in the main chain.
  • the polyimide when the polyimide contains at least one selected from a tetracarboxylic acid residue having an aromatic ring and a diamine residue having an aromatic ring, the molecular skeleton becomes rigid and the durability is enhanced, and the surface hardness is increased.
  • the rigid aromatic ring skeleton tends to extend the absorption wavelength to a long wavelength, and the transmittance in the visible light range tends to decrease.
  • the polyimide contains (i) a fluorine atom, the light transmission is improved because the charge transfer of the electronic state in the polyimide skeleton can be made difficult.
  • the polyimide contains (i) a fluorine atom, the hygroscopicity is suppressed, so that the tendency of the plastic deformation region to expand when the hygroscopicity is high can be suppressed, and the bending resistance in a high humidity environment can be made favorable. .
  • the light transmission is improved from the point of being able to inhibit the movement of charges in the skeleton by breaking the conjugation of ⁇ electrons in the polyimide skeleton.
  • the polyimide has a structure in which (iii) aromatic rings are linked by an alkylene group which may be substituted with a sulfonyl group or a fluorine group, the charge transfer in the skeleton is broken by breaking the conjugation of ⁇ electrons in the polyimide skeleton. The light transmission is improved because it can be inhibited.
  • a polyimide containing a fluorine atom is preferably used from the viewpoint of improving the light transmittance and improving the surface hardness and the bending resistance.
  • the content ratio of fluorine atoms is preferably such that the ratio (F / C) of the number of fluorine atoms (F) to the number of carbon atoms (C) when the polyimide surface is measured by X-ray photoelectron spectroscopy is 0.01 or more Furthermore, it is preferable that it is 0.05 or more.
  • the ratio (F / C) of the number of fluorine atoms (F) to the number of carbon atoms (C) is 1 or less Is preferably, and further preferably 0.8 or less.
  • the above ratio by the measurement of X-ray photoelectron spectroscopy (XPS) can be determined from the value of atomic% of each atom measured using an X-ray photoelectron spectrometer (for example, Theta Probe, manufactured by Thermo Scientific) .
  • a tetracarboxylic acid and a diamine not having a silicon atom contains an aromatic ring and a fluorine atom. Furthermore, it is preferred that both the tetracarboxylic acid and the diamine not having a silicon atom contain an aromatic ring and a fluorine atom.
  • a tetracarboxylic acid having an aromatic ring and a fluorine atom when the total amount of the tetracarboxylic acid component and the diamine component is 100 mol%, from the viewpoint of surface hardness and light transmittance of the obtained polyimide and the point of bending resistance.
  • the total amount of the diamine having an aromatic ring and a fluorine atom is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 75 mol% or more.
  • the light transmittance of the resulting polyimide is improved in that at least 50% of the hydrogen atoms bonded to carbon atoms contained in the tetracarboxylic acid component and the diamine component are hydrogen atoms directly bonded to the aromatic ring. And from the viewpoint of improving surface hardness and bending resistance.
  • the percentage of hydrogen atoms (number) directly bonded to the aromatic ring in all hydrogen atoms (number) bonded to carbon atoms is preferably 60% or more, more preferably 70% or more .
  • the ratio of hydrogen atoms (number) directly bonded to the aromatic ring in all hydrogen atoms (number) in carbon atoms contained in the polyimide is high-performance liquid chromatography, gas chromatography mass of polyimide decomposition product It can be determined using an analyzer and NMR.
  • the sample is decomposed by an aqueous alkaline solution or supercritical methanol, and the resulting decomposition product is separated by high performance liquid chromatography, and the qualitative analysis of each separated peak is performed by gas chromatography mass spectrometry, NMR, etc.
  • the ratio of hydrogen atoms (number) directly bonded to the aromatic ring in all hydrogen atoms (number) in the polyimide can be determined by performing measurement using high performance liquid chromatography.
  • the polyimide film which concerns on this invention contains the polyimide which has a structure represented by following General formula (1).
  • R 1 represents a tetravalent group which is a tetracarboxylic acid residue having an aromatic ring or an aliphatic ring, and a plurality of R 1 may be identical to or different from each other
  • R 2 represents a divalent group which is a diamine residue, and a plurality of R 2 may be the same or different, and at least a portion of the plurality of R 2 is an aromatic ring or an aliphatic ring Containing diamine residues, n represents the number of repeating units
  • R 1 represents a tetravalent group which is a tetracarboxylic acid residue having an aromatic ring or an aliphatic ring, and a plurality of R 1 may be the same or different.
  • the tetracarboxylic dianhydride having an aromatic ring in R 1 and the tetracarboxylic dianhydride having an aliphatic ring those similar to the above can be used. These may be used alone or in combination of two or more.
  • R 1 in the general formula (1) is a residue of cyclohexanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid, from the viewpoint of light transmittance in the polyimide to be obtained, and bending resistance and surface hardness.
  • Anhydride residue Dicyclohexane-3,4,3 ′, 4′-tetracarboxylic acid dianhydride residue, cyclobutanetetracarboxylic acid dianhydride residue, pyromellitic acid dianhydride residue, 3,3 ′ 1,4,4'-biphenyltetracarboxylic acid dianhydride residue, 2,2 ', 3,3'-biphenyltetracarboxylic acid dianhydride residue, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride Residue, 3,4 '-(hexafluoroisopropylidene) diphthalic anhydride residue, 3,3'-(hexafluoroisopropylidene) diphthalic anhydride residue, 4,4'-oxydiphthalic acid Anhydride residue, and is preferably at least one tetravalent group selected from the group consisting of 3,4'-oxydiphthalic anhydride residue.
  • the tetracarboxylic acid component is particularly preferably 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, 3,4'-(hexafluoroisopropylidene) diphthalic anhydride, and 3,3 from the viewpoint of good light transmittance. More preferably, it is at least one selected from the group consisting of '-(hexafluoroisopropylidene) diphthalic anhydride, 4,4'-oxydiphthalic anhydride, and 3,4'-oxydiphthalic anhydride.
  • Tetracarboxylic acid group (group A) suitable for improving the rigidity of the resulting polyimide such as at least one member selected from the group consisting of: cyclohexane tetracarboxylic acid dianhydride, cyclopentane tetracarbon Acid dianhydride, dicyclohexane-3,4,3 ′, 4′-tetracarboxylic acid dianhydride, cyclobutanetetracarboxylic acid dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic acid anhydride, 3 4,4 '-(hexafluoroisopropylidene) diphthalic
  • the content ratio of the tetracarboxylic acid group (group A) suitable for improving the rigidity and the tetracarboxylic acid group (group B) suitable for improving the light transmittance is the light transmittance.
  • At least one of 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride and 3,4'-(hexafluoroisopropylidene) diphthalic anhydride containing a fluorine atom is used as the group B. It is preferable from the point of the improvement of the light transmittance in the polyimide obtained.
  • R 2 represents a divalent group which is a diamine residue, and a plurality of R 2 may be the same or different, and at least a part of the plurality of R 2 is aromatic There is no particular limitation as long as it contains a diamine residue having a group ring or an aliphatic ring.
  • a bivalent diamine residue the thing similar to the above can be used. These may be used alone or in combination of two or more.
  • diamine residue having an aromatic ring or an aliphatic ring contained in R 2 may each, using the same as those described above. These may be used alone or in combination of two or more.
  • the diamine residue having an aromatic ring or an aliphatic ring in R 2 in the general formula (1) is trans-, from the viewpoint of light transmittance, bending resistance, surface hardness and low hygroscopicity.
  • R 3 and R 4 each independently represent a hydrogen atom, an alkyl group or a perfluoroalkyl group.
  • the diamine residue which has a silicon atom in a principal chain as some R ⁇ 2 > is contained. Since the diamine residue which has a silicon atom in the principal chain which can be preferably used as R 2 is as described above, the description is omitted here.
  • R 2 in the general formula (1) When containing a diamine residue having a silicon atom in the main chain as R 2 in the general formula (1), in R 2 in the general formula (1), 2.5 mol% to 50 mol of the total amount of R 2 % Or less is a diamine residue having a silicon atom in the main chain, and 50 to 97.5 mol% of the total amount of R 2 has no silicon atom and has an aromatic ring or an aliphatic ring It is preferable that it is a diamine residue from the point of making bending resistance and surface hardness make compatible.
  • R 2 in the general formula (1) is preferably a diamine residue having a silicon atom in the main chain is 3.5 mol% or more of the total amount of R 2 , and more preferably 5 It is preferable that it is mol% or more. Further, from the viewpoint of reducing optical distortion, the diamine residue having a silicon atom in the main chain may exceed 10 mol% of the total amount of R 2 , or may be 15 mol% or more. On the other hand, R 2 in the general formula (1) is that the diamine residue having a silicon atom in the main chain is 45 mol% or less of the total amount of R 2 from the viewpoint of improving surface hardness and light transmittance. Preferably, it is more preferably 40 mol% or less.
  • a diamine residue having a silicon atom in the main chain or less 97.5 mol% 50 mol% or more of the total amount of R 2, silicon If it is satisfied that the diamine residue has no atom and has an aromatic ring or an aliphatic ring, a diamine residue having a silicon atom in the main chain and a silicon atom in R 2 of the general formula (1) are satisfied. It does not prevent including other diamine residue different from the diamine residue which does not have an aromatic ring or an aliphatic ring.
  • the other diamine residue is preferably 10 mol% or less, more preferably 5 mol% or less, still more preferably 3 mol% or less, and particularly preferably 1 mol% or less of the total amount of R 2 It is preferable that it is the following.
  • the diamine residue etc. which do not have a silicon atom and do not have an aromatic ring or an aliphatic ring are mentioned, for example.
  • a diamine residue having a silicon atom in the main chain of the total amount of R 2 (100 mol%), silicon atoms in the main chain
  • the remaining (100% -x%) of the remaining (100% -x%) of the mole% (x mole%) of the diamine residue having 50 has no silicon atom and has an aromatic ring or an aliphatic ring It is preferable that it is a diamine residue.
  • the R 2 in the general formula (1) 50 mol% 2.5 mol% or more of the total amount of R 2 or less, a diamine residue having one or two silicon atoms in the main chain, R 2 It is preferable from the point of being compatible with bending resistance and surface hardness that 50 mol% or more and 97.5 mol% or less of the total amount of is a diamine residue having no silicon atom and having an aromatic ring or an aliphatic ring .
  • R 2 represents a divalent group which is at least one selected from a diamine residue having no silicon atom, and a diamine residue having one or two silicon atoms in the main chain, R 50 mol% 2.5 mol% or more of 2 total less is a diamine residue having one or two silicon atoms in the main chain, the following is 97.5 mol% 50 mol% or more of the total amount of R 2 It is preferable that it is a diamine residue which does not have a silicon atom and has an aromatic ring or an aliphatic ring from the point of making a bending tolerance and surface hardness compatible.
  • R 2 in the general formula (1) is that the diamine residue having one or two silicon atoms in the main chain is 3.5 mol% or more of the total amount of R 2 Is more preferable, and more preferably 5 mol% or more. Further, from the viewpoint of reducing optical distortion, the diamine residue having one or two silicon atoms in the main chain may be more than 10% by mole of the total amount of R 2 and is 15% by mole or more. Also good. On the other hand, R 2 in the general formula (1) is 45 mol% of the total amount of R 2 in the diamine residue having one or two silicon atoms in the main chain from the viewpoint of improving surface hardness and light transmittance.
  • 50 mole% 2.5 mol% or more of the total amount of R 2 or less is a main one silicon atom in a chain or two with diamine residue, of the total amount of R 2 (100 mol%), the 50 mol% or more and 97.5 mol% or less, which is the remainder (100% -x%) of the mol% (x mol%) of the diamine residue having one or two silicon atoms in the main chain have a silicon atom
  • it is a diamine residue having an aromatic ring or an aliphatic ring.
  • the content ratio (mass%) of silicon atoms in the polyimide is 0.7 mass% or more and 6.5 mass% or less, from the viewpoint of bending resistance and surface hardness, in the polyimide used in the present invention. It is more preferable that it is 0.7 mass% or more and 5.5 mass% or less, and still more preferable that it is 0.7 mass% or more and 4.2 mass% or less.
  • the content ratio (mass%) of silicon atoms in the polyimide means the content ratio (mass%) of silicon atoms in two or more types of all the polyimides in the case of two or more types of polyimides. It can be determined from molecular weight.
  • the content rate (mass%) of the silicon atom in a polyimide is a high performance liquid chromatography, a gas chromatograph mass spectrometer, NMR, an elemental analysis, XPS / ESCA and TOF about the decomposition product of the polyimide obtained similarly to the above.
  • -It can be determined using SIMS.
  • R 2 is a diamine residue having no silicon atom. It represents a divalent group which is at least one selected, and includes a diamine residue having a hexafluoroisopropylidene skeleton in the main chain. As the diamine residue having a hexafluoroisopropylidene skeleton in the main chain, it is preferable to include a structure in which aromatic rings are linked by a hexafluoroisopropylidene group.
  • R 2 in the general formula (1) if not containing the diamine residue having a silicon atom in the main chain, R 2 in the general formula (1) is at least selected from a diamine residue having no silicon atom 1 Among these, the diamine residue which does not have a silicon atom is represented by hexafluoroisopropyl chloride as the main chain from the viewpoints of light transmittance, bending resistance, surface hardness and low hygroscopicity.
  • R 2 in the general formula (1) represents a divalent group which is at least one selected from diamine residues having no silicon atom, as a diamine residue having a hexafluoroisopropylidene skeleton in the main chain Is 3,3'-bis (trifluoromethyl) -4,4 '-[(1,1,1,3,3,3-hexafluoro) in terms of light transmittance and flex resistance and surface hardness.
  • the diamine residue having a hexafluoroisopropylidene skeleton in the main chain is 3,3'-bis (trifluoromethyl) -4,4 '-[(1,1,1,3,3,3-hexafluoropropane -2,2-Diyl) bis (4,1-phenyleneoxy)] dianiline residue, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3- One kind selected from the group consisting of hexafluoropropane residue and 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane residue
  • the above diamine residues are more preferable, and 3,3′-bis (trifluoromethyl) -4,4 ′-[(1,1,1,3,3,3-hexafluoropropane-2,2 -Diyl) bis (4,1-phenyleneoxy)] diani It
  • R 2 in the general formula (1) represents a divalent group which is at least one selected from diamine residues having no silicon atom, from the viewpoints of light transmittance and bending resistance and surface hardness
  • the diamine residue having a hexafluoroisopropylidene skeleton in the main chain is preferably 70 mol% or more, preferably 80 mol% or more, in 100 mol% in total of diamine residues having no silicon atom Is more preferable, and 90 mol% or more is more preferable.
  • the content ratio of each repeating unit in the polyimide, and the content ratio (mol%) of each tetracarboxylic acid residue and each diamine residue can be determined from the molecular weight of the feed at the time of polyimide production.
  • the content ratio (mol%) of each tetracarboxylic acid residue and each diamine residue in the polyimide is the decomposition product of the polyimide obtained by decomposition with an alkaline aqueous solution or supercritical methanol as described above.
  • n represents the number of repeating units, which is 1 or more, and usually 2 or more.
  • the number n of repeating units in the polyimide may be appropriately selected, and is not particularly limited.
  • the average number of repeating units is usually 10 to 2,000, preferably 15 to 1,000.
  • the polyimide used in the present invention can be contained singly or in combination of two or more. Moreover, the polyimide used in the present invention may have a structure different from the polyimide in a part thereof, such as a polyamide structure, as long as the effects of the present invention are not impaired.
  • the structure represented by the general formula (1) is preferably 95% or more, more preferably 98% or more, and more preferably 100% of the total number of repeating units of the polyimide. Even more preferred is As a structure different from the structure represented by the said General formula (1), the case where the tetracarboxylic-acid residue etc. which do not have an aromatic ring or an aliphatic ring etc.
  • polyamide structure examples include a polyamideimide structure containing a tricarboxylic acid residue such as trimellitic anhydride, and a polyamide structure containing a dicarboxylic acid residue such as terephthalic acid.
  • the polyimide used in the present invention preferably has a number average molecular weight or weight average molecular weight of at least 10000, more preferably at least 20000, from the viewpoint of strength when formed into a film.
  • the polyimide preferably has a weight average molecular weight of 70000 or more, more preferably 80000 or more, still more preferably 85000 or more, and particularly preferably 95000 or more. Is preferred.
  • the average molecular weight is too large, the viscosity will be high, and there is a possibility that the workability such as filtration may be reduced, so it is preferably 10,000,000 or less, more preferably 500,000 or less.
  • the number average molecular weight of the polyimide used for this invention can be measured like the number average molecular weight of the polyimide precursor mentioned later.
  • the weight average molecular weight of the polyimide used for this invention can use the measuring method of the weight average molecular weight of the polyimide described in the Example mentioned later.
  • the polyimide used in the present invention preferably has a glass transition temperature in a temperature range of 150 ° C. or more and 400 ° C. or less.
  • the glass transition temperature is 150 ° C. or more
  • the heat resistance is excellent, and preferably 200 ° C. or more.
  • the bake temperature can be reduced, and it is more preferable that the temperature is 380 ° C. or less.
  • the polyimide used in the present invention preferably has no tan ⁇ curve peak in a temperature range of -150 ° C. or more and 0 ° C. or less, whereby the surface hardness of the polyimide film at room temperature can be improved.
  • the polyimide used in the present invention may further have a tan ⁇ curve peak in a temperature range of more than 0 ° C. and less than 150 ° C.
  • the glass transition temperature of the polyimide used in the present invention can be measured in the same manner as the glass transition temperature of the polyimide film described later.
  • the polyimide film of the present invention may further contain an additive, if necessary, in addition to the above-mentioned polyimide.
  • the additive include inorganic particles for reducing optical distortion of a polyimide film, silica fillers for facilitating winding, and surfactants for improving film forming properties and defoaming properties.
  • the polyimide film of the present invention has a strain (%) at the yield point of the specific stress-strain curve, tensile modulus, total light transmittance, and yellowness.
  • the polyimide film of the present invention preferably has the characteristics described below.
  • the polyimide film of the present invention preferably has a glass transition temperature in a temperature range of 150 ° C. or more and 400 ° C. or less.
  • the temperature range having the glass transition temperature is preferably 200 ° C. or more from the viewpoint of excellent heat resistance, and is preferably 380 ° C. or less from the viewpoint of being able to reduce the baking temperature.
  • the glass transition temperature of a polyimide film refers to the temperature of a peak at which the maximum value of the peak is maximum when there are a plurality of peaks of the tan ⁇ curve.
  • a measurement range is set to -150 ° C to 400 ° C by a dynamic viscoelasticity measurement device RSA III (TA Instruments Japan Ltd.), a frequency of 1 Hz, temperature rise It can be performed at a rate of 5 ° C./min. Further, the measurement can be performed with a sample width of 5 mm and a distance between chucks of 20 mm.
  • the peak of the tan ⁇ curve refers to a peak having an inflection point which is a maximum value and having a peak width of 3 ° C. or more between valleys of the peak and noise or the like Fine vertical fluctuation is not interpreted as the above peak.
  • the polyimide film of the present invention preferably has no tan ⁇ curve peak in a temperature range of -150 ° C or more and 0 ° C or less.
  • a polyimide film with a diamine residue having a long siloxane bond in the main chain that has a tan ⁇ curve peak in a temperature range of -150 ° C to 0 ° C a temperature range of -150 ° C to 0 ° C
  • the polyimide film having no tan ⁇ curve peak can suppress the decrease in tensile modulus at room temperature, and can maintain a sufficient surface hardness as a protective film.
  • the Young's modulus measured by the following measuring method is 2.3 Gpa or more, and it is more preferable that it is 2.4 Gpa or more from the point which is excellent in surface hardness.
  • Young's modulus is measured at a temperature of 25 ° C. in accordance with ISO 14577 using a nanoindentation method.
  • a measuring apparatus uses PICODENTOR HM500 manufactured by Fisher Instruments Co., Ltd., and a Vickers indenter is used as a measuring indenter.
  • a value obtained by measuring eight arbitrary points on the surface of the polyimide film and calculating the number average is taken as a Young's modulus.
  • the measurement conditions are: maximum indentation depth: 1000 nm, weighted time: 20 seconds, creep time: 5 seconds.
  • the pencil hardness is preferably 2 B or more, more preferably B or more, and even more preferably HB or more.
  • the pencil hardness of the polyimide film is adjusted according to JIS K 5600-5-4 using a test pencil specified in JIS-S-6006 after conditioning the measurement sample under the conditions of temperature 25 ° C. and relative humidity 60% for 2 hours. It can carry out by performing the pencil hardness test (0. 98N load) prescribed in (1999) on the film surface and evaluating the highest pencil hardness which does not get damaged.
  • a pencil scratching film hardness tester manufactured by Toyo Seiki Co., Ltd. can be used.
  • the strain (%) at the yield point of the specific stress-strain curve, the elongation rate measured in the test in the tensile test for determining the tensile modulus (tensile The elongation) is preferably 5% or more, more preferably 7% or more, and still more preferably 8% or more.
  • the internal angle of the test piece is preferably 140 ° or more, preferably 145 ° or more, when the dynamic bending test is performed according to the following dynamic bending test method, from the viewpoint of excellent bending resistance. Is more preferable, and 150 ° or more is even more preferable.
  • a test piece of polyimide film cut into a size of 20 mm ⁇ 100 mm is taped to the endurance test system in a constant temperature and humidity chamber (made by Yuasa System Co., Ltd., sheet-shaped body no-load U-shaped expansion and contraction test jig DMX-FS) .
  • test piece is folded at half of the long side, and the distance between both ends of the long side of the test piece in the folded state is 6 mm, and the curvature radius of the bent portion of the test piece is 3 mm.
  • RH relative humidity
  • the internal angle measured in the test is preferably 155 ° or more when the static bending test is performed according to the following static bending test method, from the viewpoint of excellent bending resistance.
  • the angle is more preferably 160 ° or more, and still more preferably 170 ° or more.
  • FIG. 4 is a figure for demonstrating the method of a static bending
  • Test piece 1 of polyimide film cut out to 15 mm x 40 mm is bent at half of the long side, and both ends of the long side of the test piece are metal pieces 2 (100 mm x 30 mm x 6 mm) with a thickness of 6 mm from the upper and lower surfaces
  • the glass plates 3a and 3b (100 mm ⁇ 100 mm) are placed from above and below in a state in which they are arranged so as to be sandwiched and fixed with tape so that overlapping margins on both ends of the test piece 1 and the metal piece 2 are 10 mm each.
  • the test piece is held in a state of bending at an inner diameter of 6 mm.
  • test piece 4a and 4b are held between the metal piece and the glass plate in the portion where the test piece is not present, and fixed with a tape so that the glass plates become parallel.
  • the test piece thus fixed in a bent state is allowed to stand for 24 hours under an environment of room temperature 23 ⁇ 2 ° C. and 50 ⁇ 5% relative humidity (RH), and then the glass plate and the fixing tape are removed. , Release the force applied to the test piece. Thereafter, one end of the test piece is fixed, and the internal angle of the test piece is measured 30 minutes after releasing the force applied to the test piece.
  • the haze value of the polyimide film of the present invention is preferably 10 or less, more preferably 8 or less, and still more preferably 5 or less from the viewpoint of light transmittance.
  • the haze value can preferably be achieved when the thickness of the polyimide film is 5 ⁇ m or more and 100 ⁇ m or less.
  • the haze value can be measured by a method in accordance with JIS K-7136, and can be measured, for example, by a haze meter HM150 manufactured by Murakami Color Research Laboratory.
  • the birefringence in the thickness direction at the wavelength of 590 nm is preferably 0.040 or less, more preferably 0.020 or less.
  • the polyimide film of the present invention has a reduced optical distortion. Therefore, when the polyimide film of this invention is used as a member for displays, the fall of the display quality of a display can be suppressed.
  • the birefringence in the thickness direction at the wavelength of 590 nm is preferably smaller, preferably 0.015 or less, more preferably 0.010 or less, and still more preferably less than 0.008. .
  • the birefringence in the thickness direction at the wavelength of 590 nm of the polyimide film of the present invention can be determined as follows. First, using a retardation measurement device (for example, product made by Oji Scientific Instruments, product name "KOBRA-WR"), measure the thickness direction retardation value (Rth) of polyimide film with light of wavelength 590 nm at 25 ° C. Do. The thickness direction retardation value (Rth) measures the retardation value at 0 degree incidence and the retardation value at 40 degree oblique incidence, and calculates the thickness direction retardation value Rth from these retardation values.
  • a retardation measurement device for example, product made by Oji Scientific Instruments, product name "KOBRA-WR”
  • the retardation value of the oblique 40-degree incidence is measured by causing light of wavelength 590 nm to be incident on the retardation film from a direction inclined 40 degrees from the normal of the retardation film.
  • the birefringence in the thickness direction of the polyimide film can be determined by substituting it into the equation: Rth / d. Said d represents the film thickness (nm) of a polyimide film.
  • the retardation value in the thickness direction is the refractive index nx in the slow axis direction in the in-plane direction of the film (the direction in which the refractive index in the film in-plane direction is maximum), and the fast axis direction (film surface in the film plane)
  • nx refractive index in the direction in which the refractive index in the inward direction is the smallest
  • nz refractive index in the thickness direction of the film
  • the atomic percentage of silicon atoms (Si) on the surface of the film measured by X-ray photoelectron spectroscopy of the polyimide film is preferably 0.1 or more and 10 or less, and more preferably 0.2 or more and 5 or less.
  • the above ratio by the measurement of X-ray photoelectron spectroscopy (XPS) can be determined from the value of atomic% of each atom measured using an X-ray photoelectron spectrometer (for example, Theta Probe, manufactured by Thermo Scientific) .
  • the ratio (F / C) of the number of fluorine atoms (F) to the number of carbon atoms (C) on the film surface is 0.01 or more and 1 or less, which is measured by X-ray photoelectron spectroscopy of the polyimide film. Is preferable, and more preferably 0.05 or more and 0.8 or less.
  • the ratio (F / N) of the number of fluorine atoms (F) to the number of nitrogen atoms (N) on the film surface measured by X-ray photoelectron spectroscopy of the polyimide film is preferably 0.1 or more and 20 or less Furthermore, it is preferable that they are 0.5 or more and 15 or less.
  • the ratio (F / Si) of the number of fluorine atoms (F) to the number of silicon atoms (Si) on the film surface measured by X-ray photoelectron spectroscopy of the polyimide film is preferably 1 or more and 50 or less. It is preferably 3 or more and 30 or less.
  • the adhesion test when the adhesion test is conducted according to the following adhesion test method, peeling of the coating does not occur, the adhesion between the polyimide film and the hard coat layer, and the polyimide It is preferable from the point of surface hardness of a layered product which laminated a hard court layer adjacent to a film.
  • a resin composition for adhesive evaluation prepared by adding 10 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone to a solution of pentaerythritol triacrylate in 40% by mass methyl isobutyl ketone and 100 parts by mass of pentaerythritol triacrylate Is applied onto a test piece of a polyimide film cut out to 10 cm ⁇ 10 cm, and ultraviolet light is irradiated with an exposure amount of 200 mJ / cm 2 in a nitrogen stream to cure, thereby forming a 10 ⁇ m-thick cured film.
  • the cured film is subjected to a cross cut test in accordance with JIS K 5600-5-6, and the peeling operation with a tape is repeated five times, and then the presence or absence of peeling of the coating film is observed.
  • the thickness of the polyimide film of the present invention may be appropriately selected depending on the application, but is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, and still more preferably 10 ⁇ m or more . On the other hand, it is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, still more preferably 100 ⁇ m or less, and still more preferably 90 ⁇ m or less. If the thickness is small, the strength decreases, and if the thickness is large, the difference between the inner diameter and the outer diameter at the time of bending increases, and the load on the film increases, so that the bending resistance may decrease.
  • the polyimide film of the present invention may be subjected to surface treatment such as saponification treatment, glow discharge treatment, corona discharge treatment, ultraviolet light treatment, flame treatment and the like.
  • the method for producing the polyimide film of the present invention is not particularly limited as long as the method can produce the polyimide film of the present invention.
  • a method for producing the polyimide film of the present invention for example, as the first production method, Preparing a polyimide precursor resin composition containing a polyamic acid which is a polyimide precursor and an organic solvent (hereinafter referred to as a polyimide precursor resin composition preparation step); Applying the polyimide precursor resin composition to a support to form a polyimide precursor resin coating film (hereinafter referred to as a polyimide precursor resin coating film forming step); And the step of imidizing the polyimide precursor by heating (hereinafter referred to as an imidization step).
  • a step of stretching at least one of the polyimide precursor resin coating film and the post-imidized coating film obtained by imidizing the polyimide precursor resin coating film (hereinafter referred to as a stretching step) ) May be included. Each step will be described in detail below.
  • the polyimide precursor resin composition prepared in the first production method contains a polyimide precursor and an organic solvent, and optionally contains additives and the like. It may be As said polyimide precursor, the polyamic acid obtained by superposition
  • the polyimide precursor represented by the general formula (1 ′) is a tetracarboxylic acid component to be a tetracarboxylic acid residue in R 1 of the general formula (1 ′), and R 2 of the general formula (1 ′) Is a polyamic acid obtained by polymerization with a diamine component to be a diamine residue.
  • R 1 , R 2 and n in the general formula (1 ′) those similar to R 1 , R 2 and n in the general formula (1) described in the polyimide can be used.
  • the polyimide precursor represented by the general formula (1 ′) preferably has a number average molecular weight or weight average molecular weight of at least 10000 in terms of strength when formed into a film, and more preferably 20000. It is preferable that it is more than.
  • the polyimide precursor represented by the general formula (1 ′) preferably has a weight average molecular weight of 70,000 or more, more preferably 80,000 or more, from the viewpoint of improving the bending resistance. It is preferably 85,000 or more, and particularly preferably 95,000 or more.
  • the average molecular weight of the polyimide precursor can be determined by NMR (for example, AVANCE III manufactured by BRUKER). For example, after applying a polyimide precursor solution to a glass plate and drying at 100 ° C. for 5 minutes, 10 mg of solid content is dissolved in 7.5 ml of dimethylsulfoxide-d6 solvent, NMR measurement is performed, and it is bonded to an aromatic ring The number average molecular weight can be calculated from the peak intensity ratio of hydrogen atoms.
  • the weight average molecular weight of the polyimide precursor can be measured by gel permeation chromatography (GPC).
  • a polyimide precursor is N-methyl pyrrolidone (NMP) solution with a concentration of 0.5% by weight, and a developing solvent is a Tosoh GPC apparatus (HLC-8120, using a 10 mmol% LiBr-NMP solution with a water content of 500 ppm or less)
  • NMP N-methyl pyrrolidone
  • HHC-8120 Tosoh GPC apparatus
  • Measurement is carried out using a sample injection amount of 50 ⁇ L, solvent flow rate of 0.5 mL / min, and 40 ° C. using GPC LF-804 manufactured by SHODEX.
  • the weight average molecular weight is determined based on a polystyrene standard sample at the same concentration as the sample.
  • the polyimide precursor solution can be obtained by reacting the above-described tetracarboxylic acid dianhydride and the above-described diamine in a solvent.
  • the solvent used for synthesis of the polyimide precursor is not particularly limited as long as it can dissolve the above-described tetracarboxylic acid dianhydride and diamine, and, for example, an aprotic polar solvent or a water-soluble alcohol solvent etc. It can be used.
  • N-methyl-2-pyrrolidone N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone and the like.
  • organic solvent containing a nitrogen atom of: ⁇ -butyrolactone or the like it is preferable to use an organic solvent containing a nitrogen atom of: ⁇ -butyrolactone or the like.
  • the polyimide precursor solution polyamic acid solution
  • the dissolution of inorganic particles is suppressed when the polyimide precursor resin composition contains inorganic particles described later.
  • an organic solvent containing a nitrogen atom it is preferable to use an organic solvent containing a nitrogen atom, and it is preferable to use N, N-dimethylacetamide, N-methyl-2-pyrrolidone or a combination thereof.
  • an organic solvent is a solvent containing a carbon atom.
  • acid dianhydride may be added to a mixed solution of at least two diamines to synthesize a polyamic acid, or at least The two diamine components may be added to the reaction solution in stages at appropriate molar ratios to control the sequence in which each source is incorporated into the polymer chain.
  • an acid dianhydride having a molar ratio of 0.5 equivalent of a diamine having a silicon atom in the main chain is charged with a reaction solution in which a diamine having a silicon atom in the main chain is dissolved, and then reacted.
  • An amic acid in which a diamine having a silicon atom at the main chain at both ends of the anhydride is reacted is synthesized, into which the remaining diamine is fully or partially introduced, and an acid dianhydride is added to polymerize the polyamic acid. Also good.
  • diamines having a silicon atom in the main chain are introduced into the polyamic acid in a linked form via one acid dianhydride. It is preferable to polymerize the polyamic acid by such a method because it is specified to a certain extent by the positional relationship of the amic acid having a silicon atom in the main chain, and a film excellent in bending resistance can be easily obtained while maintaining the surface hardness.
  • b / a may be 0.9 or more and 1.1 or less. Preferably, it is more preferably 0.95 or more and 1.05 or less, still more preferably 0.97 or more and 1.03 or less, and particularly preferably 0.99 or more and 1.01 or less.
  • the molecular weight (polymerization degree) of the polyamic acid obtained by setting it as such a range can be adjusted moderately.
  • the procedure of the polymerization reaction can be selected appropriately from known methods, and is not particularly limited. Alternatively, the polyimide precursor solution obtained by the synthesis reaction may be used as it is, and if necessary, other components may be mixed, or the solvent of the polyimide precursor solution may be dried and dissolved in another solvent. You may use.
  • the viscosity at 25 ° C. of the polyimide precursor solution is preferably 500 cps or more and 200,000 cps or less from the viewpoint of forming a uniform coating film and polyimide film.
  • the viscosity of the polyimide precursor solution can be measured at 25 ° C. using a viscometer (eg, TVE-22HT, Toki Sangyo Co., Ltd.).
  • the said polyimide precursor resin composition may contain the additive as needed.
  • the additive include inorganic particles for reducing optical distortion of a polyimide film, silica fillers for facilitating winding, and surfactants for improving film forming properties and defoaming properties. And may be the same as those described above for the polyimide film.
  • the organic solvent used for the polyimide precursor resin composition is not particularly limited as long as the polyimide precursor can be dissolved.
  • it contains a nitrogen atom such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone and the like
  • Organic solvents; ⁇ -butyrolactone etc. can be used, but among them, it is preferable to use an organic solvent containing a nitrogen atom for the reason described above.
  • the content of the polyimide precursor in the polyimide precursor resin composition is 50% by mass or more in the solid content of the resin composition from the viewpoint of forming a uniform coating film and a polyimide film having a handleable strength.
  • the content is preferably 60% by mass or more, and the upper limit may be appropriately adjusted depending on the ingredients.
  • the organic solvent in the polyimide precursor resin composition is preferably 40% by mass or more, and more preferably 50% by mass or more in the resin composition, from the viewpoint of forming a uniform coating film and polyimide film. It is preferably 99% by mass or less.
  • the storage stability of a polyimide precursor resin composition becomes favorable that the said polyimide precursor resin composition is 1000 ppm or less from the point which can improve productivity.
  • the polyimide precursor resin composition contains a large amount of water, the polyimide precursor may be easily decomposed.
  • the water content of the polyimide precursor resin composition can be determined using a Karl-Fisher moisture meter (for example, a trace water content measuring device CA-200 type manufactured by Mitsubishi Chemical Co., Ltd.).
  • a Karl-Fisher moisture meter for example, a trace water content measuring device CA-200 type manufactured by Mitsubishi Chemical Co., Ltd.
  • the viscosity at 25 ° C. of a solid content of 15 wt% concentration of the polyimide precursor resin composition is preferably 500 cps or more and 100,000 cps or less from the viewpoint of forming a uniform coating film and polyimide film.
  • the viscosity of the polyimide precursor resin composition can be measured as a sample amount of 0.8 ml at 25 ° C. using a viscometer (for example, TVE-22HT, Toki Sangyo Co., Ltd.).
  • the surface is smooth and heat resistant as a support to be used.
  • the material is not particularly limited as long as it is a material having resistance and solvent resistance.
  • an inorganic material such as a glass plate, a metal plate whose surface is mirror-finished, and the like can be mentioned.
  • the shape of the support is selected depending on the coating method, and may be, for example, a plate, a drum, a belt, a sheet which can be wound on a roll, or the like.
  • the application means is not particularly limited as long as it can be applied with a target film thickness, and for example, known means such as die coater, comma coater, roll coater, gravure coater, curtain coater, spray coater, lip coater can be used .
  • the application may be performed by a sheet-fed application apparatus or a roll-to-roll application apparatus.
  • the solvent in the coating is dried at a temperature of 150 ° C. or less, preferably 30 ° C. or more and 120 ° C. or less until the coating becomes tack-free.
  • the drying temperature of the solvent is set to 150 ° C. or less, imidization of the polyamic acid can be suppressed.
  • the drying time may be properly adjusted according to the film thickness of the polyimide precursor resin coating film, the type of solvent, the drying temperature, etc., but it is usually 1 minute to 60 minutes, preferably 2 minutes to 30 minutes. Is preferred. When it exceeds the upper limit value, it is not preferable from the viewpoint of the production efficiency of the polyimide film. On the other hand, if the lower limit value is exceeded, rapid drying of the solvent may affect the appearance and the like of the obtained polyimide film.
  • the method for drying the solvent is not particularly limited as long as the solvent can be dried at the above temperature, and it is possible to use, for example, an oven, a drying oven, a hot plate, infrared heating, and the like.
  • the atmosphere for drying the solvent is preferably under an inert gas atmosphere.
  • the inert gas atmosphere is preferably a nitrogen atmosphere, the oxygen concentration is preferably 100 ppm or less, and more preferably 50 ppm or less. Heat treatment in the atmosphere can cause the film to oxidize, color, and degrade performance.
  • the polyimide precursor is imidized by heating.
  • an imidation process may be performed with respect to the polyimide precursor in the said polyimide precursor resin coating film before an extending process, or the said polyimide precursor resin after an extending process It may be applied to a polyimide precursor in a coating, or to both the polyimide precursor in the polyimide precursor resin coating before the stretching step and the polyimide precursor present in the film after the stretching step You may go.
  • the temperature for imidization may be appropriately selected in accordance with the structure of the polyimide precursor.
  • the temperature rise start temperature is preferably 30 ° C. or more, and more preferably 100 ° C. or more.
  • the temperature rising rate is preferably selected appropriately depending on the film thickness of the polyimide film to be obtained, and when the film thickness of the polyimide film is thick, the temperature rising rate is preferably decreased.
  • the temperature is preferably 5 ° C./min or more, and more preferably 10 ° C./min or more.
  • the upper limit of the heating rate is usually 50 ° C./min, preferably 40 ° C./min or less, and more preferably 30 ° C./min or less. It is preferable to use the above-mentioned temperature rising rate from the viewpoint of suppressing the appearance defect of the film and the strength decrease, controlling whitening accompanying the imidization reaction, and improving the light transmittance.
  • the temperature elevation may be continuous or stepwise, but it is preferable to make it continuous from the viewpoint of suppressing the appearance defect and the strength reduction of the film and controlling the whitening accompanying the imidization reaction. Moreover, in the above-mentioned whole temperature range, a temperature rising rate may be constant or may be changed halfway.
  • the atmosphere at the time of temperature rise of imidation is under inert gas atmosphere.
  • the inert gas atmosphere is preferably a nitrogen atmosphere, the oxygen concentration is preferably 500 ppm or less, more preferably 200 ppm or less, and still more preferably 100 ppm or less.
  • Heat treatment in the atmosphere can cause the film to oxidize, color, and degrade performance.
  • 50% or more of the hydrogen atoms bonded to carbon atoms contained in the polyimide are hydrogen atoms directly bonded to the aromatic ring, the influence of oxygen on the optical properties is small, and an inert gas atmosphere is not used. Also, a highly light transmitting polyimide can be obtained.
  • the heating method for imidation is not particularly limited as long as the temperature can be raised at the above temperature, and it is possible to use, for example, an oven, a heating furnace, infrared heating, electromagnetic induction heating and the like.
  • the imidation ratio of the polyimide precursor it is more preferable to set the imidation ratio of the polyimide precursor to 50% or more before the stretching step.
  • the imidization ratio By setting the imidization ratio to 50% or more before the stretching step, the film is stretched after that step, and then heated for a certain period of time at a higher temperature to perform imidization, the appearance defect of the film or Whitening is suppressed.
  • the imidation ratio can be measured by analyzing the spectrum by infrared measurement (IR) or the like.
  • the reaction In order to obtain a final polyimide film, it is preferable to advance the reaction to 90% or more, further 95% or more, and further 100% of imidization.
  • the imidization In order to advance the reaction to 90% or more, and further to 100%, the imidization is preferably maintained at a temperature rising end temperature for a certain time, and the retention time is usually 1 minute to 180 minutes, further 5 minutes to 150 minutes. It is preferable to use a minute.
  • the first production method has a stretching step of stretching at least one of the polyimide precursor resin coating film and the imidized coating film obtained by imidizing the polyimide precursor resin coating film. It may be When it has the said extending
  • the heating temperature at the time of stretching is preferably in the range of the glass transition temperature ⁇ 50 ° C. of the polyimide or polyimide precursor, and preferably in the range of the glass transition temperature ⁇ 40 ° C. If the stretching temperature is too low, the film may not be deformed and the orientation may not be sufficiently induced. On the other hand, if the stretching temperature is too high, the orientation obtained by the stretching may be relaxed at the temperature, and a sufficient orientation may not be obtained.
  • the stretching step may be performed simultaneously with the imidization step.
  • the surface hardness of the polyimide film is improved by stretching the film after imidization after the imidization rate is 80% or more, further 90% or more, further 95% or more, particularly substantially 100%. It is preferable from the point of view.
  • the draw ratio of the polyimide film is preferably 101% or more and 10000% or less, and more preferably 101% or more and 500% or less. By stretching in the above range, the surface hardness of the obtained polyimide film can be further improved.
  • the fixing method of the polyimide film at the time of stretching is not particularly limited, and is selected in accordance with the type of the stretching apparatus and the like. Moreover, there is no restriction
  • the polyimide film may be stretched in only one direction (longitudinal stretching or transverse stretching), or may be stretched in two directions by simultaneous biaxial stretching, sequential biaxial stretching, oblique stretching, or the like.
  • a manufacturing method of the polyimide film of this invention as a 2nd manufacturing method, A step of preparing a polyimide resin composition containing a polyimide and an organic solvent (hereinafter referred to as a polyimide resin composition preparation step); And the step of applying the polyimide resin composition to a support and drying the solvent to form a polyimide resin coating film (hereinafter referred to as a polyimide resin coating film forming step).
  • the polyimide dissolves well in an organic solvent, not the polyimide precursor resin composition but a polyimide resin composition in which the polyimide is dissolved in an organic solvent and an additive is contained as needed be able to.
  • the said polyimide has solvent solubility which melt
  • the above-mentioned polyimide having solvent solubility can be selected and used from the same polyimide as that described for the polyimide film.
  • a method of imidization it is preferable to use chemical imidization performed using a chemical imidization agent instead of thermal dehydration for the dehydration ring closure reaction of the polyimide precursor.
  • chemical imidization known compounds such as amines such as pyridine and ⁇ -picolinic acid, carbodiimides such as dicyclohexylcarbodiimide, and acid anhydrides such as acetic anhydride may be used as a dehydration catalyst.
  • the acid anhydride is not limited to acetic anhydride, and includes, but is not particularly limited to, propionic acid anhydride, n-butyric acid anhydride, benzoic acid anhydride, trifluoroacetic acid anhydride and the like.
  • tertiary amines such as pyridine and ⁇ -picolinic acid may be used in combination.
  • the reaction liquid obtained by reacting the precursor to the polyimide is not cast as it is, It is preferable to form a film after purification by reprecipitation or the like to remove components other than the polyimide to 100 ppm or less of the total weight of the polyimide.
  • organic solvent used for the reaction liquid which performs chemical imidization of a polyimide precursor in the polyimide resin composition preparation step for example, those described in the polyimide precursor resin composition preparation step in the first production method Similar ones can be used.
  • organic solvent used to re-dissolve the polyimide purified from the reaction liquid in the polyimide resin composition preparation step include ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono-normal-butyl ether, Ethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ortho-dichlorobenzene, xylene, cresol, chlorobenzene, isobutyl acetate, isopentyl acetate, normal-butyl acetate, normal-butyl acetate, normal-propyl acetate, normal-pentyl acetate, cyclohexanol, cyclohexanone,
  • the said polyimide resin composition may contain the additive as needed.
  • the thing similar to what was demonstrated in the said polyimide precursor resin composition preparation process in the said 1st manufacturing method can be used.
  • the method for setting the moisture content of the polyimide resin composition to 1,000 ppm or less is the same as the method described in the polyimide precursor resin composition preparation step in the first production method. Methods can be used.
  • the support and the coating method are the same as those described in the polyimide precursor resin coating film forming step in the first production method. be able to.
  • the drying temperature is preferably 80 ° C. or more and 150 ° C. or less under normal pressure. It is preferable to set it as the range of 10 degreeC or more and 100 degrees C or less under pressure reduction.
  • the second production method may further include the step of further heating the polyimide resin coating film from the viewpoint of volatilizing the remaining solvent after the polyimide resin coating film forming step. Having such a heating step is preferable from the viewpoint of improving the film strength and the chemical resistance.
  • the said heating process can be made to be the same as that of the imidation process by the heating in said 1st manufacturing method.
  • the said 2nd manufacturing method may have the extending process which extends a polyimide resin coating film after the said polyimide resin coating film formation process.
  • stretching process can be made to be the same as that of the extending
  • the second production method is preferable from the viewpoint of easily reducing the degree of yellowness (YI value) of the polyimide film.
  • the second manufacturing method it is possible to preferably form a polyimide film having a value of 0.05 or less obtained by dividing the yellowness calculated according to JIS K7373-2006 by the film thickness ( ⁇ m) is there.
  • the application of the polyimide film of the present invention is not particularly limited, and it can be used as a member such as a substrate, a surface material, etc. in which a glass product such as a thin sheet glass has been used conventionally.
  • the polyimide film of the present invention is improved in bending resistance, has a sufficient surface hardness as a protective film, and has reduced optical distortion, so that it can be suitably used as a display member capable of coping with a curved surface. it can.
  • the polyimide film of the present invention is, for example, a flexible and flexible organic EL display which can be thin and bent, a portable terminal such as a smartphone or a watch type terminal, a display device inside an automobile, a flexible panel used for a watch etc. It can be suitably used as a substrate or surface material for a flexible display.
  • the polyimide film of the present invention is a member for an image display device such as a liquid crystal display device or an organic EL display device, a member for a touch panel, a flexible printed substrate, a member for a solar cell panel such as a surface protective film or a substrate material, an optical waveguide
  • the present invention can also be applied to other components such as semiconductor components.
  • the laminate of the present invention is a laminate having the above-described film or polyimide film of the present invention and a hard coat layer containing at least one polymer of a radically polymerizable compound and a cationically polymerizable compound.
  • the laminate of the present invention uses the above-described film or polyimide film of the present invention, is excellent in transparency and has improved bending resistance, and further has a hard coat layer, so that the surface hardness is more improved Improved films or resin films.
  • the laminate of the present invention when the polyimide contained in the polyimide film contains a diamine residue having a silicon atom in the main chain, it is preferable from the viewpoint of excellent adhesion between the polyimide film and the hard coat layer. This is presumed to be due to the excellent mixing of the specific polyimide film with the hard coat layer. Moreover, in the laminated body of this invention, when the polyimide which a polyimide film contains contains the diamine residue which has a silicon atom in a principal chain, it is preferable from a point to which an optical distortion reduces. In this case, when the laminate of the present invention is used as a display member such as a surface material or a base material for a display, it is possible to suppress a decrease in display quality of the display.
  • film or Polyimide film of the present invention described above can be used as the film or polyimide film used for the laminate of the present invention, the description thereof is omitted here.
  • the hard coat layer used in the laminate of the present invention contains at least one polymer of a radically polymerizable compound and a cationically polymerizable compound.
  • the radically polymerizable compound is a compound having a radically polymerizable group.
  • the radically polymerizable group of the radically polymerizable compound is not particularly limited as long as it is a functional group capable of causing a radical polymerization reaction, and examples thereof include a group containing a carbon-carbon unsaturated double bond, Specifically, a vinyl group, a (meth) acryloyl group, etc. are mentioned.
  • these radically polymerizable groups may be respectively the same, and may differ.
  • the number of radically polymerizable groups that the radically polymerizable compound has in one molecule is preferably two or more, and more preferably three or more, from the viewpoint of improving the hardness of the hard coat layer.
  • these radically polymerizable compounds compounds having a (meth) acryloyl group are preferable among them from the viewpoint of high reactivity, and a polyfunctional acrylate monomer having 2 to 6 (meth) acryloyl groups in one molecule is preferable.
  • (meth) acryloyl refers to each of acryloyl and methacryloyl
  • (meth) acrylate refers to each of acrylate and methacrylate.
  • the radically polymerizable compound examples include vinyl compounds such as divinylbenzene; ethylene glycol di (meth) acrylate, bisphenol A epoxy di (meth) acrylate, 9,9-bis [4- (2- ( (Meth) acryloyloxyethoxy) phenyl] fluorene, alkylene oxide modified bisphenol A di (meth) acrylate (eg, ethoxylated (ethylene oxide modified) bisphenol A di (meth) acrylate etc.), trimethylolpropane tri (meth) acrylate, tri Methylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaeriol Polyol polyacrylates such as lytol tetra (meth) acrylate, dipentaerythri
  • the cationically polymerizable compound is a compound having a cationically polymerizable group.
  • the cationically polymerizable group of the cationically polymerizable compound is not particularly limited as long as it is a functional group capable of causing a cationic polymerization reaction, and examples thereof include an epoxy group, an oxetanyl group, and a vinyl ether group.
  • these cationically polymerizable groups may be identical to or different from each other.
  • the number of cationically polymerizable groups that the cationically polymerizable compound has in one molecule is preferably two or more, and more preferably three or more, from the viewpoint of improving the hardness of the hard coat layer.
  • the compound which has at least 1 sort (s) of an epoxy group and oxetanyl group as a cationically polymerizable group is preferable, and it is an epoxy group and the point of adhesiveness, and light transparency and surface hardness.
  • Compounds having two or more of at least one oxetanyl group in one molecule are more preferable.
  • a cyclic ether group such as an epoxy group or an oxetanyl group is preferable from the viewpoint of small shrinkage associated with the polymerization reaction.
  • compounds having an epoxy group are easy to obtain compounds of various structures, do not adversely affect the durability of the obtained hard coat layer, and it is easy to control the compatibility with radically polymerizable compounds
  • oxetanyl groups have a high degree of polymerization as compared to epoxy groups and are low in toxicity, and when the obtained hard coat layer is combined with a compound having an epoxy group, a cation in the coating film
  • the network formation speed obtained from the polymerizable compound is increased, and even in the region mixed with the radical polymerizable compound, an independent network is formed without leaving unreacted monomers in the film.
  • a cationically polymerizable compound having an epoxy group for example, polyglycidyl ether of polyhydric alcohol having an alicyclic ring or a cyclohexene ring or cyclopentene ring-containing compound with a suitable oxidizing agent such as hydrogen peroxide or a peracid Alicyclic epoxy resin obtained by epoxidation; polyglycidyl ether of aliphatic polyhydric alcohol or its alkylene oxide adduct, polyglycidyl ester of aliphatic long chain polybasic acid, homopolymer of glycidyl (meth) acrylate, Aliphatic epoxy resins such as copolymers; bisphenols such as bisphenol A, bisphenol F and hydrogenated bisphenol A, or their derivatives such as alkylene oxide adducts, caprolactone adducts and the like; glycidyl produced by reaction with epichlorohydrin Ether, and novolac epoxy resins such as a suitable
  • UVR-6105 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate
  • UVR-6110 bis-3,4-epoxycyclohexylmethyl adipate
  • UVR-6128 bis-3,4-epoxycyclohexylmethyl adipate
  • sorbitol polyglycidyl ether (Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-614B, Denacol EX-622), polyglycerol polyglycidyl ether (Denacol EX) -512 (denacol EX-521), pentaerythyl little polyglycidyl ether (denacol EX-411), diglycerol polyglycidyl ether (denacol EX-421), glycerol polyglycidyl ether (denacol EX-313, denacol EX-314), Trimethylolpropane polyglycidyl ether (Denacol EX-321), resortinol diglycidyl ether (Denacol EX-201), neopenty Glycol diglycidyl ether (Denacol EX-211), 1,
  • epoxy resins include Epi coat 825, Epi coat 827, Epi coat 828, Epi coat 828 EL, Epi coat 828 XA, Epi coat 834, Epi coat 801, Epi coat 801 P, Epi coat 802, Epi coat 815, Epi coat 815 XA, Epi coat 816 A, Epi coat 819, Epi coat 834X90, Epi coat 1001 B80, Epi coat 1001 X 70, Epi coat 1001 X 75, Epi coat 1001 T75, Epi coat 806 P, Epi coat 806 P, Epi coat 807, Epi coat 152, Epi coat 154, Epi coat 871, Epi coat 191 P, Epi coat YX310, Epi coat DX255, Epi coat YX8000, Epi coat YX8034 Etc (more than product name, Turbocharger bread epoxy resin) and the like.
  • a cationically polymerizable compound having an oxetanyl group for example, 3-ethyl-3-hydroxymethyl oxetane (OXT-101), 1,4-bis-3-ethyl oxetan-3-ylmethoxymethylbenzene (OXT-121) , Bis-1-ethyl-3-oxetanyl methyl ether (OXT-221), 3-ethyl-3-2-ethylhexyloxymethyl oxetane (OXT-212), 3-ethyl-3-phenoxymethyl oxetane (OXT- 211) (The above parenthesis is a trade name, manufactured by Toa Gosei.), Trade names Etanacor EHO, Etanacall OXBP, Etanacall OXTP, Etanacall OXMA (trade names, manufactured by Ube Industries, Ltd.).
  • the polymer of at least one of the radically polymerizable compound and the cationically polymerizable compound contained in the hard coat layer used in the present invention is, for example, the radically polymerizable compound and the cationically polymerizable compound. It can be obtained by adding a polymerization initiator to at least one type, if necessary, and causing a polymerization reaction by a known method.
  • a radical polymerization initiator a cationic polymerization initiator, a radical, a cationic polymerization initiator and the like can be appropriately selected and used.
  • These polymerization initiators are decomposed by at least one of light irradiation and heating to generate radicals or cations to advance radical polymerization and cation polymerization.
  • the radical polymerization initiator may be capable of releasing a substance that initiates radical polymerization by light irradiation and / or heating.
  • a radical photopolymerization initiator imidazole derivatives, bisimidazole derivatives, N-arylglycine derivatives, organic azide compounds, titanocenes, aluminate complexes, organic peroxides, N-alkoxy pyridinium salts, thioxanthone derivatives, etc. may be mentioned.
  • the cationic polymerization initiator may be capable of releasing a substance that initiates cationic polymerization by at least one of light irradiation and heating.
  • a cationic polymerization initiator sulfonic acid ester, imidosulfonate, dialkyl-4-hydroxysulfonium salt, arylsulfonic acid-p-nitrobenzyl ester, silanol-aluminum complex, ( ⁇ 6 -benzene) ( ⁇ 5 -cyclopentadi Enyl) iron (II) and the like are exemplified, and more specifically, benzoin tosylate, 2, 5-dinitrobenzyl tosylate, N-tosulculimide and the like can be mentioned, however, it is not limited thereto.
  • radical polymerization initiators and cation polymerization initiators include aromatic iodonium salts, aromatic sulfonium salts, aromatic diazonium salts, aromatic phosphonium salts, triazine compounds, iron arene complexes, etc. More specifically, chlorides, bromides, borofluorides, hexafluorophosphates, hexafluorophosphates of iodoniums such as diphenyliodonium, ditollyliodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, etc.
  • Iodonium salts such as antimonate salts, triphenylsulfonium, 4-tert-butyltriphenylsulfonium, chlorides of sulfoniums such as tris (4-methylphenyl) sulfonium, bromides, borofluoride salts, hexa Sulfonium salts such as fluorophosphate salts and hexafluoroantimonate salts, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1, Examples include 2,4,6-substituted-1,3,5 triazine compounds such as 3,5-triazine and 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine. It is not limited to these.
  • the hard coat layer used in the present invention may contain, in addition to the polymer, an antistatic agent, an antiglare agent, an antifouling agent, inorganic or organic fine particles for improving hardness, as needed. You may contain additives, such as a leveling agent and various sensitizers.
  • a polymer of at least one of a radically polymerizable compound and a cationically polymerizable compound contained in the hard coat layer used in the present disclosure is a Fourier transform infrared spectrophotometer (FTIR), a pyrolysis gas chromatograph apparatus (GC).
  • FTIR Fourier transform infrared spectrophotometer
  • GC pyrolysis gas chromatograph apparatus
  • the decomposition product of the polymer can be analyzed using a combination of high performance liquid chromatography, gas chromatography mass spectrometer, NMR, elemental analysis, XPS / ESCA, TOF-SIMS and the like.
  • the laminated body of the present invention is not particularly limited as long as it has the film or polyimide film and the hard coat layer, and the hard coat layer is formed on one side of the film or polyimide film. May be laminated, or the hard coat layer may be laminated on both sides of the film or the polyimide film.
  • the laminate of the present invention is, for example, an adhesive property between the film or the polyimide film and the hard coat layer as long as the effects of the present invention are not impaired. It may have another layer such as a primer layer for improving, or even if the film or the polyimide film and the hard coat layer are laminated via another layer such as a primer layer. good.
  • the film or the polyimide film may be positioned adjacent to the hard coat layer.
  • the laminate of the present invention may further have an impact resistant layer, an anti-fingerprint layer, an adhesive or adhesive layer, and the like.
  • the total thickness of the laminate of the present invention may be appropriately selected depending on the application, but from the viewpoint of strength, it is preferably 10 ⁇ m or more, and more preferably 40 ⁇ m or more. On the other hand, from the viewpoint of bending resistance, the thickness is preferably 300 ⁇ m or less, and more preferably 250 ⁇ m or less.
  • the thickness of each hard coat layer may be appropriately selected depending on the application, but is preferably 2 ⁇ m or more and 80 ⁇ m or less, and more preferably 3 ⁇ m or more and 50 ⁇ m or less.
  • a hard coat layer may be formed on both sides of the polyimide film.
  • the laminated body of the present invention preferably has a pencil hardness of H or more, more preferably 2H or more, and even more preferably 3H or more on the hard coat layer side surface.
  • the pencil hardness of the laminate of the present invention can be measured in the same manner as in the method of measuring the pencil hardness of the polyimide film except that the load is 9.8N.
  • the laminate of the present invention preferably has a total light transmittance of 85% or more, preferably 88% or more, and more preferably 90% or more according to JIS K7361-1. Is preferred. Such high transmittance allows for good transparency and can be a glass substitute material.
  • the total light transmittance of the laminate of the present invention can be measured in the same manner as the total light transmittance measured in accordance with JIS K7361-1 of the polyimide film.
  • the layered product of the present invention preferably has a yellowness (YI value) calculated according to JIS K7373-2006 of 20 or less, more preferably 15 or less, and more preferably 10 or less More preferably, it is particularly preferably 5 or less.
  • the laminate of the present invention has a yellowish color suppressed, improves light transmittance, and can be suitably used as a glass substitute material, so that the yellow color calculated according to the above-mentioned JIS K7373-2006.
  • the value (YI value / film thickness ( ⁇ m)) obtained by dividing the degree (YI value) by the film thickness ( ⁇ m) is preferably 0.10 or less, more preferably 0.05 or less, and 0.03 It is even more preferable that The yellowness (YI value) of the laminate of the present invention can be measured in the same manner as the yellowness (YI value) calculated according to JIS K7373-2006 of the polyimide film.
  • the haze value of the laminate of the present invention is preferably 10 or less, more preferably 8 or less, and still more preferably 5 or less from the viewpoint of light transmittance.
  • the haze value of the laminate of the present invention can be measured in the same manner as the haze value of the polyimide film.
  • the birefringence in the thickness direction at a wavelength of 590 nm of the laminate of the present invention is preferably 0.040 or less, preferably 0.020 or less, more preferably 0.015 or less, and further preferably 0. It is preferably 010 or less, and more preferably less than 0.008.
  • the birefringence of the laminate of the present invention can be measured in the same manner as the birefringence in the thickness direction at a wavelength of 590 nm of the polyimide film.
  • the application of the laminate of the present invention is not particularly limited, and can be used, for example, in the same application as the application of the polyimide film of the present invention described above.
  • Method of Producing Laminate As a method of producing a laminate of the present invention, for example, Forming a coating of a composition for forming a hard coat layer containing at least one of a radically polymerizable compound and a cationically polymerizable compound on at least one surface of the film or the polyimide film of the present invention; And curing the coating film.
  • the composition for forming a hard coat layer contains at least one of a radically polymerizable compound and a cationically polymerizable compound, and may further contain a polymerization initiator, a solvent, an additive, and the like as necessary.
  • a polymerization initiator e.g., a polymerization initiator, a solvent, an additive, and the like.
  • the radically polymerizable compound, the cationically polymerizable compound, the polymerization initiator and the additive contained in the composition for forming a hard coat layer the same ones as those described for the hard coat layer can be used.
  • the solvent can be appropriately selected from known solvents and used.
  • the composition for forming a hard coat layer on at least one surface of a film or a polyimide film May be applied by a known application method.
  • the application means is not particularly limited as long as it can be applied with a target film thickness, and examples thereof include the same means as the means for applying the polyimide precursor resin composition to a support.
  • the coating film of the curable resin composition for a hard coat layer is dried as necessary to remove the solvent.
  • the drying method for example, a method of drying under reduced pressure or drying by heating, and further a method of combining these drying and the like can be mentioned.
  • UV light emitted from light rays such as ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc, xenon arc and metal halide lamp is used.
  • the irradiation dose of the energy ray source is about 50 to 5000 mJ / cm 2 as an integrated exposure dose at an ultraviolet wavelength of 365 nm.
  • heating it is usually treated at a temperature of 40 ° C. or more and 120 ° C. or less.
  • the reaction may be carried out by leaving at room temperature (25 ° C.) for 24 hours or more.
  • the display member of the present invention includes the film or polyimide film of the present invention described above, or the laminate of the present invention.
  • a member for displays of the present invention a surface material for displays, a substrate for displays, etc. are mentioned, for example.
  • the display member of the present invention may be the above-described film or polyimide film of the present invention, or the laminate of the present invention.
  • the display member of the present invention is used, for example, as a surface material for display, disposed so as to be located on the surface of various displays.
  • the member for a display of the present invention is flexible because it has excellent transparency, improved bending resistance, and sufficient surface hardness as a protective film, similarly to the film or polyimide film of the present invention and the laminate of the present invention described above. It can be particularly suitably used for displays.
  • the member for display of the present invention can be used for various known displays, and is not particularly limited. For example, it can be used for the display described in the application of the polyimide film of the present invention.
  • the surface used as the outermost surface may be the surface by the side of a polyimide film, or hard It may be the surface on the coat layer side.
  • the display member of the present invention may have a fingerprint adhesion preventing layer on the outermost surface.
  • the method for arranging the display member of the present invention on the surface of the display is not particularly limited.
  • a method of using an adhesive layer may be mentioned.
  • the adhesive layer a conventionally known adhesive layer that can be used for adhering a display member can be used.
  • the touch panel member of the present invention comprises the film of the present invention described above, the polyimide film of the present invention described above, or the laminate of the present invention described above; A transparent electrode comprising a plurality of conductive parts disposed on one side of the film, the polyimide film, or the laminate; And a plurality of lead lines electrically connected on at least one side of the end of the conductive portion.
  • the touch panel member of the present invention is provided with the above-described film of the present invention, the above-described polyimide film of the present invention, or the above-described laminate of the present invention. Since the reduction in hardness is suppressed, it can be particularly suitably used for a flexible display, and has excellent optical properties.
  • the laminate of the present invention used in the touch panel member of the present invention has a hard coat layer containing at least one polymer of a radically polymerizable compound and a cationically polymerizable compound adjacent to both sides of a polyimide film. Is preferred.
  • the touch panel member of the present invention is not particularly limited, but it is preferable that the transparent electrode be laminated in contact with one surface side of the laminate.
  • the touch panel member of the present invention can be used, for example, by being disposed on the surface of various displays.
  • the touch panel member of the present invention and the polyimide film or laminate of the present invention as a surface material can be disposed on the surface of various displays in this order.
  • FIG. 5 is a schematic plan view of one side of an example of the touch panel member of the present invention
  • FIG. 6 is a schematic plan view of the other side of the touch panel member shown in FIG.
  • FIG. 7 is a cross-sectional view of the touch panel member shown in FIG.
  • first transparent electrode 4 disposed in contact with one surface of the laminate 10, and the other of the laminate 10 And a second transparent electrode 5 disposed in contact with the surface of the substrate.
  • first transparent electrode 4 a plurality of first conductive portions 41 which are strip-like electrode pieces extending so as to extend in the x-axis direction are arranged at predetermined intervals.
  • the first lead-out wire 7 electrically connected to the first conductive portion 41 is connected to the first conductive portion 41 at any one of the end portions in the longitudinal direction.
  • a first terminal 71 for electrically connecting to an external circuit may be provided.
  • the first conductive portion 41 and the first lead-out line 7 are generally connected in a non-active area 23 located outside the active area 22 visible to the user of the touch panel.
  • the connection between the first conductive portion 41 and the first lead-out wire 7 can adopt a connection structure in which a connection portion 24 is interposed as shown in FIG. 5, for example.
  • the connection portion 24 can be formed by extending a layer of conductive material from a longitudinal end of the first conductive portion 41 to a predetermined position in the non-active area 23.
  • a connection structure between the first conductive portion 41 and the first lead-out wire 7 can be formed.
  • connection between the first conductive portion 41 and the first lead-out wire 7 is not limited to the structure forming the connection portion 24 as shown in FIG.
  • the first conductive portion 41 which extends the longitudinal end of the first conductive portion 41 to the non-active area 23 and extends to the non-active area 23 in the non-active area 23 The two may be electrically connected by running the first lead-out wire 7 on the end of
  • the 1st 1st electroconductivity is one
  • the first lead wire 7 may be electrically connected to both ends in the longitudinal direction of the portion 41, respectively.
  • the touch panel member 20 includes a second transparent electrode 5 disposed in contact with the other surface of the laminate 10.
  • second conductive portions 51 which are a plurality of strip-like electrode pieces extending so as to extend in the y-axis direction, are arranged at predetermined intervals in the x-axis direction.
  • a second lead-out wire 8 electrically connected to the second conductive portion 51 is connected to the second conductive portion 51 at one longitudinal end thereof.
  • the second lead-out line 8 is extended to a position not overlapping with the first terminal 71 at the end 21 of the end of the laminate 10 where the aforementioned first lead-out line 7 extends. .
  • a second terminal 81 may be provided for electrical connection with an external circuit.
  • the electrical connection between the second conductive portion 51 and the second lead-out wire 8 can apply the same form as the electrical connection between the first lead-out wire 7 and the first conductive portion 41 .
  • the pattern in which the first lead-out wire 7 is a long wire and the second lead-out wire 8 is a short wire as shown in FIGS. 5 and 6 is only an embodiment of the touch panel member of the present invention. It is also possible to use a pattern in which the first lead-out wire 7 is a short wire and the second lead-out wire 8 is a long wire. Further, the extension direction of the first lead-out line 7 and the extension direction of the second lead-out line 8 are not limited to the directions shown in FIGS. 5 and 6, and can be designed arbitrarily.
  • the electroconductive part with which the touch panel member of this invention is equipped can select suitably what comprises a transparent electrode in a touch panel member, and can apply it, and the pattern of an electroconductive part is not limited to what is shown in FIG.5 and FIG.6.
  • the material of the conductive portion is preferably a light transmitting material, and, for example, an indium oxide based transparent electrode material mainly composed of indium tin oxide (ITO), indium oxide, indium zinc oxide (IZO), etc.
  • the first conductive portion 41 and the second conductive portion 51 may be formed using conductive materials of the same type as each other, or may be formed using different materials. In particular, forming the first conductive portion 41 and the second conductive portion 51 using the same type of conductive material is preferable from the viewpoint of more effectively suppressing the occurrence of warpage or distortion of the touch panel member.
  • the thickness of the conductive portion is not particularly limited, but in the case of forming the conductive portion by, for example, a photolithography method, the thickness can generally be formed to about 10 nm to 500 nm.
  • the electrically conductive material which comprises the extraction line with which the touch panel member of this invention is equipped does not ask
  • the lead-out lines can be formed using a metal material such as silver or copper having high conductivity.
  • a metal material such as silver or copper having high conductivity.
  • simple metals, composites of metals, composites of metals and metal compounds, and metal alloys can be mentioned.
  • the metal alone include silver, copper, gold, chromium, platinum, and aluminum alone.
  • MAM trilayer structure of molybdenum, aluminum, and molybdenum
  • As a composite of a metal and a metal compound a laminate of chromium oxide and chromium can be exemplified.
  • Silver alloys and copper alloys are generally used as metal alloys. Moreover, APC (alloy of silver, palladium, and copper) etc. can be illustrated as a metal alloy.
  • a resin component may be mixed with the above-described metal material as appropriate.
  • the terminal provided at the end of the lead-out wire can be formed, for example, using the same material as the lead-out wire.
  • the thickness and width of the extraction line are not particularly limited. For example, when forming the extraction line by photolithography, the thickness is generally 10 nm to 1000 nm and the width is 5 ⁇ m to 500 nm. It is formed to about 200 ⁇ m. On the other hand, when forming a lead-out line by printing such as screen printing, generally, the thickness is about 5 ⁇ m to 20 ⁇ m and the width dimension is about 20 ⁇ m to 300 ⁇ m.
  • the touch panel member of the present invention is not limited to the form shown in FIG. 5 to FIG. 7, and for example, the first transparent electrode and the second transparent electrode may be laminated on separate laminates. It may be 8 and 9 are each a schematic plan view showing an example of a conductive member provided with the laminate of the present invention.
  • the first conductive member 201 shown in FIG. 8 has the laminate 10 of the present invention and the first transparent electrode 4 disposed in contact with one surface of the laminate 10, and
  • the transparent electrode 4 has a plurality of first conductive portions 41.
  • the second conductive member 202 shown in FIG. 9 has a laminate 10 ′ of the present invention and a second transparent electrode 5 disposed in contact with one surface of the laminate 10 ′.
  • the second transparent electrode 5 has a plurality of second conductive parts 51.
  • FIG. 10 is a schematic cross-sectional view showing another example of the touch panel member of the present invention
  • the touch panel member 20 ′ shown in FIG. 10 is a first conductive member 201 shown in FIG. And the conductive member 202.
  • the surface of the first conductive member 201 which does not have the first transparent electrode 4 and the surface of the second conductive member 202 which has the transparent electrode 5 intervene through the adhesive layer 6. It is stuck.
  • an adhesive layer for bonding the laminate of the present invention and the touch panel member of the present invention for example, an adhesive layer for bonding the touch panel members of the present invention, the touch panel member and the display device of the present invention
  • a conventionally known bonding layer used for an optical member can be appropriately selected and used.
  • the configuration and materials of the transparent electrode, the lead wire and the terminal may be the same as the transparent electrode, the lead wire and the terminal used for the touch panel member of the present invention described above. it can.
  • the liquid crystal display device of the present invention comprises the film of the present invention described above, the polyimide film of the present invention described above, the laminate of the present invention described above, the film or the polyimide film or one surface side of the laminate. And a liquid crystal display unit having a liquid crystal layer between opposing substrates.
  • the liquid crystal display device of the present invention comprises the above-described film of the present invention, the above-described polyimide film of the present invention, or the above-described laminate of the present invention, so it is excellent in transparency and improves bending resistance. Since a reduction in surface hardness is suppressed, it can be particularly suitably used for a flexible display, and is excellent in optical characteristics.
  • the laminate of the present invention used in the liquid crystal display device of the present invention has a hard coat layer containing at least one polymer of a radically polymerizable compound and a cationically polymerizable compound adjacent to both sides of a polyimide film Is preferred.
  • the liquid crystal display device of the present invention may be provided with the touch panel member of the present invention described above.
  • the counter substrate included in the liquid crystal display device of the present invention may be provided with the film or the polyimide film or the laminate of the present invention.
  • FIG. 11 is a schematic cross-sectional view showing an example of the liquid crystal display device of the present invention.
  • the liquid crystal display device 100 shown in FIG. 11 includes the laminate 10 of the present invention and the first transparent electrode 4 on one surface of the laminate 10 ′ of the present invention, and the second transparent electrode 5 on the other surface. And a liquid crystal display unit 30.
  • the laminate 10 is used as a surface material, and the laminate 10 and the touch panel member 20 are bonded to each other through the adhesive layer 6.
  • the liquid crystal display portion used in the liquid crystal display device of the present invention has a liquid crystal layer formed between the substrates disposed opposite to each other, and adopting the configuration used in the conventionally known liquid crystal display device. it can.
  • the drive method of the liquid crystal display device of the present invention is not particularly limited, and a drive method generally used for a liquid crystal display device can be adopted. For example, a TN method, an IPS method, an OCB method, and an MVA method Etc. can be mentioned.
  • the opposite substrate used in the liquid crystal display device of the present invention can be appropriately selected and used according to the driving method of the liquid crystal display device and the like, and a substrate provided with the polyimide film or laminate of the present invention may be used.
  • liquid crystal constituting the liquid crystal layer various liquid crystals having different dielectric anisotropy, and a mixture thereof can be used according to the driving method of the liquid crystal display device of the present invention and the like.
  • a method of forming a liquid crystal layer a method generally used as a method of manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method. After forming the liquid crystal layer by the above method, the liquid crystal cell can be gradually cooled to room temperature to orient the enclosed liquid crystal.
  • a plurality of colored layers and a light shielding portion for defining a pixel may be further provided between the opposed substrates.
  • the liquid crystal display unit may have a backlight unit having a light emitting element or a phosphor at a position opposite to the side where the touch panel member is located, on the outside of the oppositely disposed substrate.
  • you may have a polarizing plate in the outer surface of the board
  • FIG. 12 is a schematic cross-sectional view showing another example of the liquid crystal display device of the present invention.
  • the liquid crystal display device 200 shown in FIG. 12 includes the laminate 10 of the present invention, the first conductive member 201 provided with the first transparent electrode 4 on one surface of the laminate 10 ′ of the present invention, A touch panel member 20 ′ having a second conductive member 202 provided with a second transparent electrode 5 on one surface of the laminate 10 ′ ′, and a liquid crystal display unit 30.
  • the laminate 10 , The first conductive member 201, and the first conductive member 201 and the second conductive member 202 are bonded to each other via the adhesive layer 6.
  • the configuration of the touch panel member 20 ' is, for example, 10 can be the same as the configuration of the touch panel member 20 ',
  • the conductive member used in the liquid crystal display device of the present invention is the same as the conductive member used in the touch panel member of the present invention. Use Can.
  • the organic electroluminescent display device of the present invention comprises the film of the present invention described above, the polyimide film of the present invention described above, the laminate of the present invention described above, the film or the polyimide film or the laminate And an organic electroluminescent display unit having an organic electroluminescent layer between opposing substrates disposed on one side.
  • the organic electroluminescent display device of the present invention is excellent in transparency and improves bending resistance since it comprises the above-described film of the present invention, the above-described polyimide film of the present invention, or the above-described laminate of the present invention. While the decrease in surface hardness is suppressed. It can be particularly suitably used for a flexible display, and has excellent optical characteristics.
  • the laminate of the present invention used in the organic electroluminescent display device of the present invention comprises a hard coat layer containing at least one polymer of a radically polymerizable compound and a cationically polymerizable compound adjacent to both sides of a polyimide film. It is preferable to have.
  • the organic electroluminescent display apparatus of this invention may be equipped with the touch-panel member of this invention mentioned above.
  • the opposing substrate included in the organic electroluminescent display device of the present invention may be provided with the film or the polyimide film or the laminate of the present invention.
  • FIG. 13 is a schematic cross-sectional view showing an example of the organic electroluminescent display device of the present invention.
  • the organic electroluminescent display device 300 shown in FIG. 13 comprises the laminate 10 of the present invention and the first transparent electrode 4 on one side of the laminate 10 'of the present invention, and the second transparent on the other side.
  • a touch panel member 20 including an electrode 5 and an organic electroluminescence display unit 40 are provided.
  • the laminate 10 is used as a surface material, and the laminate 10 and the touch panel member 20 are bonded to each other through the adhesive layer 6.
  • the organic electroluminescent display part (organic EL display part) used for the organic electroluminescent display apparatus (organic EL display apparatus) of this invention is an organic electroluminescent layer (organic EL layer) formed between the board
  • the organic EL display portion further includes an organic EL element including a support substrate, an organic EL layer, and an anode layer and a cathode layer sandwiching the organic EL layer, and a sealing base for sealing the organic EL element. It may be As the organic EL layer, any one having at least an organic EL light emitting layer may be used.
  • a hole injection layer, a hole transport layer, an organic EL light emitting layer, an electron transporting layer and an electron injection from the anode layer side It is possible to use one having a structure in which the layers are stacked in this order.
  • the organic EL display device of the present invention can be applied to, for example, a passive drive organic EL display and an active drive organic EL display.
  • substrate used for the organic electroluminescence display of this invention it can select suitably according to the drive system of an organic electroluminescence display etc., and can be used, and you may use what is provided with the laminated body of this invention.
  • FIG. 14 is a schematic cross-sectional view showing another example of the organic electroluminescent display device of the present invention.
  • the organic electroluminescent display device 400 shown in FIG. 14 includes the laminate 10 of the present invention, the first conductive member 201 having the first transparent electrode 4 on one surface of the laminate 10 ′ of the present invention, and It has a touch panel member 20 ′ having a second conductive member 202 having the second transparent electrode 5 on one surface of the laminate 10 ′ ′ of the invention, and an organic electroluminescence display unit 40.
  • Organic electroluminescence display device In 400 the laminate 10 and the first conductive member 201 and the first conductive member 201 and the second conductive member 202 are bonded to each other through the adhesive layer 6.
  • the constitution of the invention can be the same as the constitution of the touch panel member 20 'shown in Fig. 10.
  • the organic electroluminescent display device of the present invention can be used.
  • the that the conductive member may be the same as the conductive member for use in a touch panel member of the present invention.
  • the weight average molecular weight of the polyimide precursor is determined by using the polyimide precursor as a 0.5 wt% N-methylpyrrolidone (NMP) solution, filtering the solution through a syringe filter (pore diameter: 0.45 ⁇ m), As a solvent, using a 10 mmol% LiBr-NMP solution with a water content of 500 ppm or less, using a GPC apparatus (HLC-8120 manufactured by Tosoh Corporation, column: GPC LF-804 manufactured by SHODEX), the sample loading amount 50 ⁇ L, solvent flow 0.4 mL The measurement was performed under the conditions of 40 ° C./min.
  • NMP N-methylpyrrolidone
  • the weight average molecular weight of the polyimide precursor is a polystyrene standard sample having the same concentration as the sample (weight average molecular weight: 364, 700, 204,000, 103, 500, 44, 360, 27, 500, 13, 030, 6, 300, It is a converted value to standard polystyrene measured based on 3, 070).
  • the elution time was compared with a calibration curve to determine the weight average molecular weight.
  • ⁇ Viscosity of Polyimide Precursor Solution The viscosity of the polyimide precursor solution was measured as a sample amount of 0.8 ml at 25 ° C. using a viscometer (eg, TVE-22HT, Toki Sangyo Co., Ltd.).
  • NMP N-methylpyrrolidone
  • the solution is filtered through a syringe filter (pore diameter: 0.45 ⁇ m), and a 30 mmol% LiBr-NMP solution having a water content of 500 ppm or less is used as a developing solvent, and a GPC device (HLC-8120, detector: differential) Refractive index (RID) detector, using column: Two GPC LF-804 (manufactured by SHODEX) connected in series, sample loading amount 50 ⁇ L, solvent flow rate 0.4 mL / min, column temperature 37 ° C., detector temperature 37 ° C. The measurement was performed under the following conditions.
  • the weight average molecular weight of the polyimide is a polystyrene standard sample having the same concentration as the sample (weight average molecular weight: 364, 700, 204,000, 103, 500, 44, 360, 27, 500, 13, 030, 6, 300, 3, It is a converted value to standard polystyrene measured based on 070).
  • the elution time was compared with a calibration curve to determine the weight average molecular weight.
  • ⁇ Viscosity of Polyimide Solution The viscosity of the polyimide solution was measured as a sample amount of 0.8 ml at 25 ° C. using a viscometer (for example, TVE-22HT, Toki Sangyo Co., Ltd.).
  • the silicon atom content rate (mass%) of polyimide was computed from the molecular weight of preparation.
  • 2,2'-bis as a diamine component relative to 1 mol of 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) as an acid dianhydride component 6FDA
  • 6FDA 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride
  • TFMB trifluoromethyl
  • AprTMOS 1,3-bis (3-aminopropyl) tetramethyldisiloxane
  • both terminal amine-modified diphenyl silicone oil in Synthesis Example 10 (Shin-Etsu Chemical Co., Ltd.: X22-1660B-3, the side chain phenyl type, number average molecular weight 4400) for, - (CH 2) 3 - amino group via an Is calculated to have an average number of repeating units of diphenyl siloxane of 19.7 based on a number average molecular weight of 4400 assuming that it is bonded to silicone, and an average of 21.7 silicon atoms are contained in one molecule.
  • YI value (yellowness)> YI value is based on JIS K7373-2006 using an ultraviolet visible near infrared spectrophotometer (JASCO Ltd. V-7100) and using an auxiliary illuminant C and a 2 degree visual field by a spectral colorimetry method Based on the transmittance measured at intervals of 1 nm from the range of 250 nm to 800 nm, tristimulus values X, Y, Z in the XYZ color system are determined, and from the values of X, Y, Z, the following equation Calculated.
  • YI 100 (1.2769X-1.0592Z) / Y
  • the YI value at a thickness of 100 ⁇ m is the same as the total light transmittance for each transmittance at each wavelength measured at intervals of 1 nm in the range of 250 nm to 800 nm of a sample of a specific thickness
  • the converted value of each transmittance at each wavelength of different thickness can be determined according to Baire's law, and it can be calculated and used based on it.
  • ⁇ Thickness measurement method> The film thickness of a total of 5 points of the four corners and the center of the polyimide film test piece cut out in a size of 10 cm ⁇ 10 cm was measured using a digital linear gauge (Model PDN12 digital gauge manufactured by Ozaki Mfg. Co., Ltd.) Of the film thickness of the polyimide film.
  • ⁇ Tension test> The test piece of polyimide film cut out to 15 mm ⁇ 40 mm is conditioned at a temperature of 25 ° C. and a relative humidity of 60% for 2 hours, and in accordance with JIS K7127, the tensile speed is 10 mm / min and the distance between chucks is 20 mm.
  • the tensile test was conducted at 25 ° C., and the strain (%) at the yield point, the tensile modulus, and the elongation were measured in the stress-strain curve obtained by the tensile test.
  • a tensile tester manufactured by Shimadzu Corporation: Autograph AG-X 1N, load cell: SBL-1KN was used.
  • the test piece was cut out from near the center of the film.
  • the film thickness of a total of five points at the four corners and the center of the cut out film is measured by the method of measuring the film thickness, and the difference between the average film thickness of five points and the film thickness of each point is within 6% of the average film thickness
  • One test piece was used.
  • ⁇ Dynamic bending test> A test piece of polyimide film cut out to a size of 20 mm ⁇ 100 mm was taped to the endurance test system in a constant temperature and humidity chamber (made by Yuasa System Co., Ltd., sheet-shaped body unloaded U-shaped expansion and contraction test jig DMX-FS) . In addition, the test piece is folded at half of the long side, and the distance between both ends of the long side of the test piece in the folded state is 6 mm, and the curvature radius of the bent portion of the test piece is 3 mm. Set the status.
  • a test piece 1 of a polyimide film cut out to 15 mm ⁇ 40 mm is bent at half of the long side, and both ends of the long side of the test piece are metal pieces 2 (100 mm ⁇ 30 mm with a thickness of 6 mm) Glass plates from above and below with x 6 mm) sandwiched between the upper and lower surfaces and fixed with tape so that the overlapping margin on the upper and lower surfaces of both ends of the test piece 1 and the metal piece 2 is 10 mm each It pinched with (100 mm x 100 mm x 0.7 mm) 3a and 3b, and fixed the test piece concerned in the state where it was bent by internal diameter 6 mm.
  • test piece 4a and 4b were sandwiched between the metal piece 2 and the glass plate in a portion where there is no test piece, and fixed with a tape so that the glass plates become parallel.
  • the test piece thus fixed in a bent state is allowed to stand for 24 hours under an environment of room temperature 23 ⁇ 2 ° C. and 50 ⁇ 5% relative humidity (RH), and then the glass plate and the fixing tape are removed. , Released the force applied to the test piece. Thereafter, one end of the test piece was fixed, and the internal angle of the test piece was measured 30 minutes after releasing the force applied to the test piece. In the case where the film is completely returned without being affected by the static bending test, the inner angle is 180 °.
  • ⁇ Pencil hardness> For pencil hardness, after conditioning the measurement sample under the conditions of temperature 25 ° C. and relative humidity 60% for 2 hours, using pencil for test specified in JIS-S-6006, pencil scratching film hardness manufactured by Toyo Seiki Co., Ltd. A pencil hardness test (0.98N load) specified in JIS K5600-5-4 (1999) was performed on the film surface using a hardness tester to evaluate the highest pencil hardness without scratch.
  • the Young's modulus of the surface of a test piece of a polyimide film cut out to 15 mm ⁇ 15 mm was measured at a temperature of 25 ° C. in accordance with ISO 14577 using a nanoindentation method. Specifically, a measuring apparatus used was PICODENTOR HM500 manufactured by Fisher Instruments Inc., and a Vickers indenter was used as a measuring indenter. With respect to the surface of the test piece, a value obtained by measuring eight arbitrary points and performing number averaging is defined as a Young's modulus. The measurement conditions were: maximum indentation depth: 1000 nm, weighted time: 20 seconds, creep time: 5 seconds.
  • AA The yellowness is 5 or less, and it is not broken in the dynamic bending test, the inner angle of the test piece is 140 ° or more, and the inner angle of the test piece in the static bending test is 180 °.
  • B The yellowness is 5 or less, does not break in the dynamic bending test, the inner angle of the test piece is 140 ° or more, and the inner angle of the test piece is 155 ° or more and less than 170 ° in the static bending test.
  • C falls under at least one of the following (c1) and the following (c2): (c1) Yellowness exceeds 5 (c2) Breaking in dynamic bending test or internal angle of test specimen is less than 140 °, static In the bending test, the internal angle of the test piece is less than 155 °.
  • Synthesis Example 1 A solution of 2903 g of dehydrated dimethylacetamide and 16.0 g (0.07 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (AprTMOS) dissolved in a 500 ml separable flask 14.6 g (0.03 mol) of 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) to a temperature controlled at 30 ° C., gradually increasing the temperature to 2 ° C. or less The mixture was charged and stirred for 30 minutes with a mechanical stirrer.
  • AprTMOS 1,3-bis (3-aminopropyl) tetramethyldisiloxane
  • 6FDA 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride
  • composition example 2 A solution of 302.0 g of dehydrated dimethylacetamide and 2.49 g (10 mmol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (AprTMOS) in a 500 ml separable flask At a controlled temperature of 30 ° C, 2.22 g (5 mmol) of 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) is gradually added so that the temperature rise is 2 ° C or less. The mixture was stirred with a mechanical stirrer for 4 hours.
  • AprTMOS 1,3-bis (3-aminopropyl) tetramethyldisiloxane
  • 6FDA 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride
  • composition example 3 In the procedure of the synthesis example 2, the reaction was carried out so that the concentrations of the raw materials and solid contents shown in Table 1 were obtained, and polyimide precursor solution 3 was obtained.
  • composition example 4 In a 500 ml separable flask, 267.9 g of dehydrated dimethylacetamide and 3,3'-bis (trifluoromethyl) -4,4 '-[(1,1,1,3,3,3-hexa) 40.1 g (61.3 mmol) of fluoropropane-2,2-diyl) bis (4,1-phenylene oxy)] dianiline (HFFAPP) was added, and the liquid temperature of the solution in which HFFAPP was dissolved was controlled at 30 ° C.
  • composition example 5 A solution of dehydrated dimethylacetamide (200 g) and 1,3-bis (3-aminopropyl) tetramethyldisiloxane (AprTMOS) (1.27 g, 5.11 mmol) dissolved in a 500 mL separable flask So that the solution temperature is controlled to 30 ° C., 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) (1.14 g, 2.56 mmol), so that the temperature rise is 2 ° C. or less The mixture was gradually charged and stirred with a mechanical stirrer for 1 hour.
  • AprTMOS 1,3-bis (3-aminopropyl) tetramethyldisiloxane
  • a catalyst pyridine (32.1 g, 405 mmol) and acetic anhydride (41.4 g, 405 mmol) were added, and the mixture was stirred at room temperature for 24 hours to synthesize a polyimide solution.
  • the obtained polyimide solution was transferred to a 5 L separable flask, butyl acetate (313 g) was added, and the solution was stirred until it became uniform.
  • methanol (696 g) was gradually added to obtain a slightly hazy solution.
  • Methanol (1620 g) was added at once to the cloudy solution to obtain a white slurry. The slurry was filtered and washed five times with methanol to obtain polyimide 5 (69.6 g).
  • the weight average molecular weight of the polyimide measured by GPC was 192,000.
  • a catalyst pyridine (32.2 g, 407 mmol) and acetic anhydride (41.5 g, 407 mmol) were added and stirred at room temperature for 24 hours to synthesize a polyimide solution.
  • the obtained polyimide solution was transferred to a 5 L separable flask, butyl acetate (314 g) was added, and the solution was stirred until it became uniform.
  • methanol (698 g) was gradually added to obtain a slightly hazy solution.
  • Methanol (1630 g) was added at once to the cloudy solution to obtain a white slurry. The slurry was filtered and washed five times with methanol to obtain polyimide 6 (69.8 g).
  • the weight average molecular weight of the polyimide measured by GPC was 237,000.
  • Synthesis Example 9 A solution of 169.5 g of dehydrated dimethylacetamide and 32.0 g (100 mmol) of 2,2'-bis (trifluoromethyl) benzidine (TFMB) in a 500 ml separable flask is heated to a liquid temperature of 30 ° C. At a controlled point, 21.7 g (99.5 mmol) of pyromellitic dianhydride (PMDA) is gradually added in several portions so that the temperature rise is 2 ° C. or less, and a polyimide precursor solution 9 (20 wt% solids) was synthesized. The viscosity at 25 ° C. of the polyimide precursor solution 9 was 23,400 cps, and the weight average molecular weight of the polyimide precursor 9 measured by GPC was 83,000.
  • PMDA pyromellitic dianhydride
  • Synthesis Example 10 12.25 g of an amine-modified diphenyl silicone oil at both ends (Shin-Etsu Chemical Co., Ltd .: X22-1660B-3 (number average molecular weight 4400)) while introducing nitrogen gas into a 3 L separable flask equipped with an oil bath and a stirring rod, 3432 g of N-methyl-2-pyrrolidone (NMP) was added, followed by 222.12 g (0.5 mol) of 6FDA and stirred at room temperature for 30 minutes.
  • NMP N-methyl-2-pyrrolidone
  • modified silicone oil KF-8010 (trade name, manufactured by Shin-Etsu Silicone, molecular weight 860) was added and stirred for 4 hours to obtain a polyamic acid solution.
  • ⁇ picoline (8.4 g, 90 mmol) as a catalyst and acetic anhydride (55.2 g, 540 mmol) as a catalyst are added to the above polyamic acid solution, and the solution is stirred for 1 hour in an oil bath at 100 ° C. I got The obtained polyimide solution was dropped into a large amount of isopropyl alcohol (IPA) to precipitate out the polyimide.
  • IPA isopropyl alcohol
  • the polyimide obtained by filtration extraction was washed by stirring in IPA. After filtration again, the polyimide was sufficiently dried at 80 ° C. under reduced pressure to obtain polyimide 11.
  • the weight average molecular weight of the polyimide 11 measured by GPC was 199000.
  • the solid content concentration in Table 1 represents the solid content concentration of the polyimide precursor solution also for polyimides 5 to 7.
  • the molecular weight represents the molecular weight of the polyimide precursor for the polyimide precursors 1 to 4 and 8 to 10, and the molecular weight of the polyimide for the polyimides 5 to 7 and 11.
  • the viscosity is the viscosity of the polyimide precursor solution for the polyimide precursors 1 to 4 and 8 to 10, the viscosity when preparing the polyimide solution in the same manner as in Example 11 for the polyimides 5 to 7, the polyimide 11 is the same as in Comparative Example 6. It represents the viscosity when preparing the polyimide solution.
  • Examples 1 to 10, Comparative Examples 1 and 3 to 5 By performing the following procedures (1) to (3) using the polyimide precursor solutions 1 to 4 and 9 to 11, polyimide films having the thicknesses shown in Table 2 were respectively produced.
  • Each polyimide precursor solution was apply
  • the temperature is raised to the curing temperature described in Table 2 at a heating rate of 10 ° C./min, and held at the curing temperature described in Table 2 for 1 hour, then cooled to room temperature did.
  • Example 11 The polyimide 5 was dissolved in a mixed solvent of butyl acetate and PGMEA (8: 2, volume ratio) to prepare a polyimide solution 5 having a solid content of 25% by mass.
  • the viscosity at 25 ° C. of the polyimide solution 5 (solid content: 25% by weight) was 16612 cps.
  • a polyimide film having a thickness described in Table 2 was produced.
  • the polyimide solution 5 was applied on glass and dried in a circulating oven at 120 ° C. for 10 minutes.
  • Example 12 Comparative Example 2
  • a polyimide film was obtained in the same manner as in Example 11, except that the polyimide 5 of Synthesis Example 5 was changed to the polyimides 6 to 7 of Synthesis Examples 6 to 7 in Example 11.
  • the polyimide films of Examples 1 to 12 corresponding to the polyimide film of the present invention are resin films excellent in transparency, and in which the decrease in surface hardness is suppressed while improving the bending resistance.
  • the polyimide films of Comparative Examples 1 to 5 had a strain at the yield point of the stress-strain curve of less than 8%, and had inferior dynamic bending resistance.
  • the polyimide films of Comparative Examples 4 to 5 were also inferior in yellowness, and the polyimide film of Comparative Example 5 was further inferior in pencil hardness, and the surface was easily scratched.
  • the polyimide film of Comparative Example 6 had a strain at a yield point of 8% or more and a tensile modulus of less than 1.8 GPa, and although the bending resistance was good, the pencil hardness was inferior and the surface was easily damaged.
  • the polyimide film of Comparative Example 6 was further inferior in yellowness.
  • the commercially available polyimide film of Comparative Example 7 was significantly inferior in light transmittance and yellowness, and was inferior in bending resistance as compared with the examples. Since the polyimide film of Comparative Example 7 does not contain a fluorine atom and has a molecular structure with high hygroscopicity, it is presumed that the bending resistance is inferior even if the yield point is large.
  • a catalyst pyridine (41.4 g) and acetic anhydride (53.4 g) were added and stirred at room temperature for 24 hours to synthesize a polyimide solution.
  • butyl acetate (406 g) was added and stirred until uniform, then methanol (902 g) was gradually added to obtain a slightly hazy solution.
  • Methanol (2105 g) was added in one portion to the solution in which turbidity was observed, to obtain a white slurry.
  • the slurry was filtered and washed 5 times with methanol to obtain polyimide 12 (91 g).
  • the weight average molecular weight of the polyimide measured by GPC was 201269.
  • the solid concentration in Table 3 represents the solid concentration when the polyimide solution was prepared in the same manner as in Examples 13 to 18.
  • Molecular weight represents the molecular weight of polyimide.
  • the viscosity represents the viscosity when preparing a polyimide solution in the same manner as in Examples 13-18.
  • Example 13 The polyimide 12 was dissolved in a solvent (dichloromethane) to prepare a polyimide solution 12 with a solid content of 14% by mass.
  • the viscosity at 25 ° C. of the polyimide solution 12 (solid content: 14% by mass) was 4290 cps.
  • a polyimide film having a thickness of 50 ⁇ m ⁇ 5 ⁇ m was produced.
  • the polyimide solution 12 was applied onto a glass plate and dried in a circulating oven at 120 ° C. for 10 minutes.
  • Example 14 In Example 13, as shown in Table 4, the polyimide 12 of Synthesis Example 12 is changed to the polyimide 13 or 14 of Synthesis Example 13 or 14, and the temperature rise temperature in the step (ii) and the temperature maintained for one hour A polyimide film was obtained in the same manner as in Example 13, except that (Curing temperature) was changed as shown in Table 4.
  • Examples 19 to 36 Production of Laminates 10 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF, Irgacure 184) per 40 parts by mass of pentaerythritol triacrylate is added to a solution of pentaerythritol triacrylate in 40% by mass methyl isobutyl ketone, The resin composition for coat layers was prepared. The resin composition for a hard coat layer is coated on each polyimide film of Examples 1 to 18, and ultraviolet rays are irradiated and cured at a dose of 200 mJ / cm 2 under a nitrogen stream to form a 10 ⁇ m thick cured film. , Produced a laminate. In particular, when the polyimide film contains a silicon atom, the adhesion to the hard coat layer is good.

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Abstract

L'invention concerne un film qui présente une déformation à la limite d'élasticité apparente d'au moins 8 % et un module d'élasticité en traction d'au moins 1,8 GPa dans une courbe contrainte-déformation obtenue par un test de traction selon la norme JIS/K7127, qui présente une transmittance totale de lumière d'au moins 85 % telle que mesurée selon la norme JIS/K7361-1 et qui présente un jaunissement de 5 ou moins tel que calculé selon la norme JIS/K7373-2006.
PCT/JP2018/035439 2017-09-27 2018-09-25 Film, film de polyimide, stratifié, élément d'affichage, élément à écran tactile, affichage à cristaux liquides et appareil d'affichage à électroluminescence organique Ceased WO2019065624A1 (fr)

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CN109896753A (zh) * 2019-04-08 2019-06-18 拓米(成都)应用技术研究院有限公司 一种可折叠超薄玻璃盖板及其改性cpi涂布制备方法
CN112086024A (zh) * 2019-06-14 2020-12-15 三星显示有限公司 用于显示装置的窗构件、显示装置及用于显示装置的制造方法
JP2020204022A (ja) * 2019-06-17 2020-12-24 大日本印刷株式会社 ポリイミドフィルム、ポリイミドワニス、ポリイミドフィルムの製造方法、積層体、ディスプレイ用部材、タッチパネル部材、液晶表示装置、及び有機エレクトロルミネッセンス表示装置
JP2020203479A (ja) * 2019-06-17 2020-12-24 大日本印刷株式会社 積層体、ディスプレイ用表面材、タッチパネル部材、液晶表示装置、及び有機エレクトロルミネッセンス表示装置
WO2020255864A1 (fr) * 2019-06-17 2020-12-24 大日本印刷株式会社 Film de polyimide, vernis à base de polyimide, procédé de production de film de polyimide, corps multi-couche, élément d'afficheurs, élément de panneau tactile, dispositif d'affichage à cristaux liquides et dispositif d'affichage électroluminescent organique
CN112530993A (zh) * 2019-09-18 2021-03-19 三星显示有限公司 显示装置
JP2023503481A (ja) * 2019-11-29 2023-01-30 ピーアイ・アドバンスド・マテリアルズ・カンパニー・リミテッド ポリイミドフィルムおよびその製造方法
EP4317273A3 (fr) * 2017-12-04 2024-05-08 Kolon Industries, Inc. Procédé de fabrication d'un film à base de polyimide et film à base de polyimide fabriqué par ce procédé
US12427709B2 (en) * 2018-12-04 2025-09-30 Kolon Industries, Inc. Method for manufacturing polyimide-based film and polyimide-based film manufacture

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Cited By (12)

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Publication number Priority date Publication date Assignee Title
EP4317273A3 (fr) * 2017-12-04 2024-05-08 Kolon Industries, Inc. Procédé de fabrication d'un film à base de polyimide et film à base de polyimide fabriqué par ce procédé
US12427709B2 (en) * 2018-12-04 2025-09-30 Kolon Industries, Inc. Method for manufacturing polyimide-based film and polyimide-based film manufacture
CN109896753A (zh) * 2019-04-08 2019-06-18 拓米(成都)应用技术研究院有限公司 一种可折叠超薄玻璃盖板及其改性cpi涂布制备方法
CN112086024A (zh) * 2019-06-14 2020-12-15 三星显示有限公司 用于显示装置的窗构件、显示装置及用于显示装置的制造方法
JP2020204022A (ja) * 2019-06-17 2020-12-24 大日本印刷株式会社 ポリイミドフィルム、ポリイミドワニス、ポリイミドフィルムの製造方法、積層体、ディスプレイ用部材、タッチパネル部材、液晶表示装置、及び有機エレクトロルミネッセンス表示装置
JP2020203479A (ja) * 2019-06-17 2020-12-24 大日本印刷株式会社 積層体、ディスプレイ用表面材、タッチパネル部材、液晶表示装置、及び有機エレクトロルミネッセンス表示装置
WO2020255864A1 (fr) * 2019-06-17 2020-12-24 大日本印刷株式会社 Film de polyimide, vernis à base de polyimide, procédé de production de film de polyimide, corps multi-couche, élément d'afficheurs, élément de panneau tactile, dispositif d'affichage à cristaux liquides et dispositif d'affichage électroluminescent organique
JP7547792B2 (ja) 2019-06-17 2024-09-10 大日本印刷株式会社 積層体、ディスプレイ用表面材、タッチパネル部材、液晶表示装置、及び有機エレクトロルミネッセンス表示装置
JP7608731B2 (ja) 2019-06-17 2025-01-07 大日本印刷株式会社 ポリイミドフィルム、ポリイミドワニス、ポリイミドフィルムの製造方法、積層体、ディスプレイ用部材、タッチパネル部材、液晶表示装置、及び有機エレクトロルミネッセンス表示装置
CN112530993A (zh) * 2019-09-18 2021-03-19 三星显示有限公司 显示装置
JP2023503481A (ja) * 2019-11-29 2023-01-30 ピーアイ・アドバンスド・マテリアルズ・カンパニー・リミテッド ポリイミドフィルムおよびその製造方法
JP7382505B2 (ja) 2019-11-29 2023-11-16 ピーアイ・アドバンスド・マテリアルズ・カンパニー・リミテッド ポリイミドフィルムおよびその製造方法

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