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WO2018190179A1 - Film de polyimide, produit stratifié et matériau de surface pour unité d'affichage - Google Patents

Film de polyimide, produit stratifié et matériau de surface pour unité d'affichage Download PDF

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Publication number
WO2018190179A1
WO2018190179A1 PCT/JP2018/014168 JP2018014168W WO2018190179A1 WO 2018190179 A1 WO2018190179 A1 WO 2018190179A1 JP 2018014168 W JP2018014168 W JP 2018014168W WO 2018190179 A1 WO2018190179 A1 WO 2018190179A1
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Prior art keywords
polyimide
group
polyimide film
less
general formula
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PCT/JP2018/014168
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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
誠 溝尻
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大日本印刷株式会社
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Priority to JP2019512445A priority Critical patent/JP7088173B2/ja
Publication of WO2018190179A1 publication Critical patent/WO2018190179A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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

Definitions

  • Embodiment of this indication is related with a polyimide film, a layered product, and a surface material for displays.
  • a polyimide resin is a highly heat-resistant resin obtained by subjecting a polyamic acid obtained by a condensation reaction of an aromatic tetracarboxylic acid anhydride and an aromatic diamine to a dehydration ring-closing reaction.
  • polyimide resins generally show yellow or brown coloration, it has been difficult to use them in fields that require transparency, such as display applications and optical applications. Therefore, it has been studied to apply a polyimide having improved transparency to a display member.
  • Patent Document 1 discloses 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid dicarboxylic acid as polyimide resins having high heat resistance, high transparency, and low water absorption.
  • a polyimide resin obtained by reacting with an imino forming compound is disclosed, and is described as being suitable for a substrate material such as a flat panel display or a mobile phone device.
  • Patent Document 2 includes a unit structure derived from aromatic dianhydride and aromatic diamine, and includes an additive for improving tear strength, or a functional group selected from the group consisting of a hexafluoro group, a sulfone group, and an oxy group.
  • a transparent polyimide film is further disclosed that further includes a unit structure derived from the monomer it has.
  • Patent Document 3 discloses a polyimide film having a peak peak in a tan ⁇ curve, which is a value obtained by dividing a loss elastic modulus by a storage elastic modulus, as a polyimide film having excellent transparency and heat resistance. ing.
  • Patent Document 4 obtains a polyimide film that is colorless and transparent as a polyimide film used for a substrate of a flexible device, has a low residual stress generated between the inorganic film, and has excellent mechanical and thermal properties.
  • a polyimide film obtained by imidizing a polyimide precursor using a specific fluorine-based aromatic diamine and a silicone compound having a siloxane skeleton having 3 to 200 silicon atoms as a monomer component is disclosed.
  • a polyimide film with an inorganic film (SiN film) is formed using the polyimide precursor, cracks and peeling are not observed after a bending test in which bending is repeated 10 times ( ⁇ ). Observed ( ⁇ ).
  • Patent Document 5 an aromatic diamine and an aromatic tetracarboxylic dianhydride are mainly used for the purpose of avoiding warpage and curling in a polyimide film used for a base film such as a flexible printed wiring board.
  • a polyimide film using 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride as an essential component is disclosed as a group tetracarboxylic dianhydride.
  • Examples of conventional flexible displays include those in which the display screen is gently curved. Therefore, a base material and a surface material used for a conventional flexible display are thin, light, and can be bent. That is, unlike a glass substrate, there has been a demand for flexibility that does not break even when bent.
  • recent flexible displays have been required to be able to fold the display screen, bend it to a larger curvature, and restore without folding.
  • Mobile devices that can fold screens are often carried in a folded state, so the flexible display mounted on a mobile device will be restored to its original state when it is flattened even if it is folded for a long time.
  • the base material and the surface material for flexible displays are also required to have resilience after being bent for a long time (hereinafter, sometimes referred to as static bending resistance).
  • static bending resistance In the resin film using the conventional transparent polyimide, even if it shows a good result in a test in which the flat state and the bent state are repeated at a constant cycle, if the bent state continues for a long time, the crease is formed, There is a problem that it is difficult to return to a flat surface and inferior in static bending resistance particularly in a high humidity environment.
  • the polyimide film described in patent document 5 is inferior in transparency, it is difficult to use it for fields, such as a display use and an optical use. In view of the above, there is a demand for a resin film that has excellent transparency and improved bending resistance in a high humidity environment.
  • the present disclosure has been made in view of the above problems, and has as its main object to provide a resin film that is excellent in transparency and improved in bending resistance under a high humidity environment. Moreover, this indication aims at providing the surface material for displays which is the laminated body which has the said resin film, and the said resin film or the said laminated body.
  • the polyimide which has a structure denoted by the following general formula (1),
  • the polyimide contains an aromatic ring, and is selected from the group consisting of (i) a fluorine atom, and (ii) a structure in which the aromatic rings are connected to each other with a sulfonyl group or an alkylene group optionally substituted with fluorine.
  • 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 12 or less, A polyimide film having a humidity expansion coefficient of 10.0 ppm /% RH or less is provided.
  • R 1 represents a tetravalent group that is a tetracarboxylic acid residue
  • R 2 represents a divalent group that is a diamine residue
  • the content ratio of the diamine residue having a silicon atom is 50 mol% or less
  • n represents the number of repeating units.
  • R 2 is selected from a diamine residue having no silicon atom and a diamine residue having one or two silicon atoms in the main chain.
  • a polyimide film that represents a divalent group that is at least one kind, and a content ratio of a diamine residue having one or two silicon atoms in the main chain in the total amount of R 2 is 50 mol% or less.
  • a polyimide film having an inner angle measured by the test of 120 ° or more is provided.
  • Static bending test method A polyimide film test piece cut out to 15 mm ⁇ 40 mm is bent at a position of half of the long side, and both ends of the long side of the test piece sandwich a metal piece (100 mm ⁇ 30 mm ⁇ 6 mm) having a thickness of 6 mm from the upper and lower surfaces. Placed between glass plates (100 mm x 100 mm x 0.7 mm) from above and below with the tape fixed so that the overlap between the top and bottom surfaces of the test piece and the metal piece is 10 mm each.
  • the test piece is fixed in a bent state with an inner diameter of 6 mm. At that time, a dummy test piece is sandwiched between the metal piece and the glass plate where there is no test piece, and is fixed with tape so that the glass plate is parallel.
  • the test piece thus fixed in a bent state is left to stand for 24 hours in an environment of 60 ° C. and 90% relative humidity (RH), and then the glass plate and fixing tape are removed, and the test piece is attached to the test piece. Release this force. Thereafter, one end of the test piece is fixed, and the internal angle of the test piece 30 minutes after the force applied to the test piece is released is measured.
  • R 1 in the general formula (1) is 4,4 ′-(hexafluoroisopropylidene) diphthalic acid.
  • Anhydrous residue, 3,4 '-(hexafluoroisopropylidene) diphthalic anhydride residue, 3,3'-(hexafluoroisopropylidene) diphthalic anhydride residue, 4,4'-oxydiphthalic anhydride Provided is a polyimide film comprising a residue and at least one tetravalent group selected from the group consisting of a residue and a 3,4′-oxydiphthalic anhydride residue.
  • the diamine residue having no silicon atom in R 2 in the general formula (1) is (i) fluorine.
  • a polyimide film which is at least one divalent group selected from the group consisting of a divalent group represented by formula (2).
  • R 3 and R 4 each independently represents a hydrogen atom, an alkyl group, or a perfluoroalkyl group.
  • a polyimide film having a value obtained by dividing yellowness calculated in accordance with JIS K7373-2006 by a film thickness ( ⁇ m) of 0.10 or less.
  • R 2 represents a divalent group that is at least one selected from diamine residues having no silicon atom, and includes a diamine residue having a hexafluoroisopropylidene skeleton in the main chain, or 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, and the total amount of R 2 Among these, the content ratio of the diamine residue having one or two silicon atoms in the main chain is 2.5 mol or more and 50 mol% or less.
  • a laminate having the polyimide film of the one embodiment of the present disclosure and a hard coat layer containing at least one polymer of a radical polymerizable compound and a cationic polymerizable compound is provided. To do.
  • the radical polymerizable compound is a compound having two or more (meth) acryloyl groups in one molecule
  • the cationic polymerizable compound includes at least one of an epoxy group and an oxetanyl group.
  • a laminate which is a compound having two or more molecules.
  • a polyimide film according to one embodiment of the present disclosure or a surface material for display which is a laminate according to one embodiment of the present disclosure is provided.
  • a polyimide film according to one embodiment of the present disclosure or a surface material for a flexible display which is a laminate according to one embodiment of the present disclosure is provided.
  • the present disclosure it is possible to provide a resin film that has excellent transparency and improved bending resistance in a high humidity environment. Moreover, according to this indication, the surface material for displays which is the laminated body which has the said resin film, and the said resin film or the said laminated body can be provided.
  • FIG. 6 is a diagram showing a tan ⁇ curve of Example 2.
  • the polyimide film of one embodiment of the present disclosure contains a polyimide having a structure represented by the following general formula (1),
  • the polyimide contains an aromatic ring, and is selected from the group consisting of (i) a fluorine atom, and (ii) a structure in which the aromatic rings are connected to each other with a sulfonyl group or an alkylene group optionally substituted with fluorine.
  • 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 12 or less
  • the polyimide film has a humidity expansion coefficient of 10.0 ppm /% RH or less.
  • R 1 represents a tetravalent group that is a tetracarboxylic acid residue
  • R 2 represents a divalent group that is a diamine residue
  • the content ratio of the diamine residue having a silicon atom is 50 mol% or less
  • n represents the number of repeating units.
  • the polyimide film of the present disclosure has a peak apex only in a temperature region of 150 ° C. or higher in a tan ⁇ curve that is a value obtained by dividing the loss elastic modulus by the storage elastic modulus.
  • a peak apex is less than 150 ° C.
  • the molecular chain of the polyimide is likely to move, plastic deformation is likely to occur, and the bending resistance may be deteriorated. Since it does not exist below 150 ° C., the mobility of the molecular chain is suppressed, plastic deformation becomes difficult, and bending resistance can be improved.
  • the polyimide film of the present disclosure is more preferably one having a peak apex only in a temperature region of 200 ° C. or higher in the tan ⁇ curve from the viewpoint of improving bending resistance and surface hardness, and a temperature region of 220 ° C. or higher. It is still more preferable that it has only.
  • the peak apex is in a temperature region of 380 ° C. or lower in the tan ⁇ curve.
  • the polyimide film of the present disclosure preferably does not have a peak apex in the tan ⁇ curve in a temperature range of ⁇ 150 ° C. or higher and lower than 150 ° C., and further in a temperature range of ⁇ 70 ° C. or higher and lower than 150 ° C. Further, it is preferable that the peak of the tan ⁇ curve does not exist in the temperature region of 100 ° C.
  • the peak of the tan ⁇ curve does not exist in the temperature region of 0 ° C. or lower.
  • the main chain has a diamine residue having a long siloxane bond, or when the main chain contains a large amount of a diamine residue having a silicon atom, the peak of the tan ⁇ curve is present in such a low temperature region.
  • the silicon atom-containing diamine residue used in the present disclosure is selected so as to have a relatively small amount of a relatively short siloxane bond that does not have a peak peak in the tan ⁇ curve in such a low temperature region. is doing.
  • a decrease in tensile modulus at room temperature is also suppressed. And sufficient surface hardness as a protective film can be maintained.
  • the peak apex temperature can be used as an index of the glass transition temperature.
  • the dynamic viscoelasticity measurement is performed, for example, with a dynamic viscoelasticity measuring device RSA-G2 (TE Instruments Japan Co., Ltd.), with a measurement range of ⁇ 150 ° C. or higher and 490 ° C. or lower, and a frequency of 1 Hz. It can be performed at a temperature 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. When analyzing peaks and inflection points, the data is digitized and analyzed from the numerical values without visual evaluation.
  • RSA-G2 TE Instruments Japan Co., Ltd.
  • the peak is a value of tan ⁇ of 0.2 or more, Preferably, it has an inflection point of 0.3 or more and a maximum value, and the peak width between the valleys of the peaks is 3 ° C. or more. Small vertical fluctuations are not observed as peaks at the top of the peak.
  • the polyimide film of the present disclosure has a total light transmittance of 85% or more as measured in accordance with JIS K7361-1.
  • the total light transmittance of the polyimide film of the present disclosure measured according to JIS K7361-1 is preferably 88% or more, more preferably 89% or more, particularly 90% or more. It is preferable.
  • the polyimide film of the present disclosure has a thickness of 5 ⁇ m or more and 100 ⁇ m or less, and the total light transmittance measured in accordance with JIS K7361-1 is preferably 85% or more, and more preferably 88% or more.
  • the polyimide film of the present disclosure has a thickness of 50 ⁇ m ⁇ 5 ⁇ m, and the total light transmittance measured in accordance with JIS K7361-1 is preferably 85% or more, and more preferably 88% or more. Further, it is preferably 89% or more, and particularly preferably 90% or more.
  • the total light transmittance measured according to JIS K7361-1 can be measured by, for example, a haze meter (for example, HM150 manufactured by Murakami Color Research Laboratory).
  • the converted value of the total light transmittance of different thickness can be obtained by Lambert Beer's law and can be used.
  • the polyimide film of the present disclosure has a yellowness (YI value) calculated based on JIS K7373-2006 of 12 or less.
  • YI value yellowness calculated based on JIS K7373-2006 of 12 or less.
  • the yellowness (YI value) calculated in accordance with JIS K7373-2006 is preferably 10 or less, more preferably 7 or less, and even more preferably 5 or less.
  • the polyimide film of the present disclosure has a thickness of 5 ⁇ m or more and 100 ⁇ m or less, and the yellowness (YI value) calculated in accordance with JIS K7373-2006 is preferably 12 or less, more preferably 10 or less, It is still more preferably 7 or less, and particularly preferably 5 or less.
  • the polyimide film of the present disclosure has a thickness of 50 ⁇ m ⁇ 5 ⁇ m, and the yellowness (YI value) calculated in accordance with JIS K7373-2006 is preferably 12 or less, more preferably 10 or less. Preferably, it is 7 or less, more preferably 5 or less.
  • the yellowness (YI value) is determined according to JIS K7373-2006 by using an ultraviolet-visible near-infrared spectrophotometer (for example, JASCO Corporation V-7100), and by a spectrocolorimetric method.
  • a two-degree field tristimulus values X, Y, and Z in the XYZ color system are obtained based on transmittance measured at 1 nm intervals in a range of 250 nm to 800 nm, and the X, Y, It can be calculated from the value of Z by the following formula.
  • YI 100 (1.2769X ⁇ 1.0592Z) / Y It should be noted that, from the measurement value of yellowness of a certain thickness, the yellowness of different thicknesses is calculated for each transmittance at each wavelength measured at 5 nm intervals between 380 nm and 780 nm of a sample with a specific thickness. Similarly to the light transmittance, a converted value of each transmittance at each wavelength of different thickness can be obtained according to Lambert Beer's law, and can be calculated and used based on it.
  • the polyimide film of the present disclosure has a yellow color calculated in accordance with JIS K7373-2006 because yellowish coloring is suppressed, light transmittance is improved, and the polyimide film can be suitably used as a glass substitute material.
  • the value obtained by dividing the degree (YI value) by the film thickness ( ⁇ m) is preferably 0.10 or less, more preferably 0.04 or less, and 0.03 More preferably, it is as follows.
  • the value obtained by dividing the yellowness (YI value) by the film thickness ( ⁇ m) is the second decimal place according to the rule B of JIS Z8401: 1999. Rounded value.
  • the polyimide film of this indication has a humidity expansion coefficient of 10.0 ppm /% RH or less. Since it is a polyimide film with a low humidity expansion coefficient, it is not easily affected by humidity, and even under high humidity environments, it is suppressed that bending resistance is impaired by deformation due to moisture absorption. Resistance is improved.
  • the humidity expansion coefficient is preferably 9.0 ppm /% RH or less, more preferably 8.0 ppm /% RH or less, still more preferably 7.5 ppm /% RH or less, It is more preferably 6.5 ppm /% RH or less, and even more preferably 3.0 ppm /% RH or less.
  • the humidity expansion coefficient of the polyimide film can be measured by the following method.
  • the test piece of polyimide film cut out to 5 mm ⁇ 20 mm is sufficiently dried, and the test piece is set so that the distance between chucks is 15 mm and the tensile load in the long side direction is 5 g.
  • the temperature is fixed at 25 ° C, the humidity is changed to 15% RH, 20% RH, and 50% RH, and the average elongation per humidity of 1% is calculated from the elongation amount of the test pieces of humidity 20% RH and 50% RH.
  • the calculation formula is as follows.
  • Humidity expansion coefficient (ppm /% RH) (X ⁇ 10 6 ) / (Y ⁇ Z)
  • X Value obtained by subtracting the test piece length at 20% RH from the test piece length at 50% RH
  • Y Humidity change amount when changing from 20% RH to 50% RH (50-20 (% RH ))
  • Test piece length when Z 20% RH
  • steam TMA / S 8227A1 manufactured by Rigaku Corporation can be used. The elongation of the test piece is always monitored, recorded every second, and measured according to the following procedure. In the following measurement, that the length of the test piece is constant means that the change in the sample length for 30 minutes is 0.1 ⁇ m or less. 1.
  • the thickness of the polyimide film test piece is although not particularly limited, it is preferably in the range of 5 ⁇ m to 200 ⁇ m, more preferably in the range of 10 ⁇ m to 150 ⁇ m, and still more preferably in the range of 15 ⁇ m to 100 ⁇ m.
  • the polyimide contained in the polyimide film contains an aromatic ring, and (i) a fluorine atom, and (ii) an alkylene group in which the aromatic rings may be substituted with a sulfonyl group or fluorine.
  • the diamine residue has a silicon atom in the main chain
  • the main chain has a silicon atom in the total amount of the diamine residues.
  • polyimide having a specific structure in which the content ratio of the diamine residue is 50 mol% or less, and a specific temperature range of the peak of the tan ⁇ curve, the specific total light transmittance, the specific yellowness,
  • Polyimide film having the specific humidity expansion coefficient By using the polyimide film having the specific humidity expansion coefficient, it is possible to provide a resin film having excellent transparency and improved bending resistance under a high humidity environment.
  • the present inventors paid attention to polyimide among resins.
  • Polyimide is known to have excellent heat resistance due to its chemical structure.
  • the polyimide film forms an ordered structure in which the arrangement of molecular chains inside is constant, and it is considered that it can have a resilience from a bent state to a flat state at room temperature. .
  • polyimide in a high-humidity environment, polyimide is prone to deteriorate from its folded state, especially when the film is bent for a long time, and may be creased and not return flat. confirmed.
  • polyimide absorbs moisture, so that the absorbed moisture acts like a plasticizer and the film is easily plastically deformed, so it is difficult to restore even if the bending force is removed. Is done.
  • the inventors of the present invention indicate that the polyimide film containing the specific polyimide and having the specific characteristics has excellent transparency and excellent bending resistance even in a high humidity environment. I found it.
  • the specific polyimide includes an aromatic ring, and (i) a fluorine atom, and (ii) an alkylene group in which the aromatic rings may be substituted with a sulfonyl group or fluorine.
  • the transparency is improved, and when the diamine residue does not have a silicon atom or has a silicon atom, it has a silicon atom in the main chain.
  • the diamine residue is 50 mol% or less of the total amount of diamine residues and the peak of the tan ⁇ curve is in a specific temperature range, the deterioration of bending resistance is suppressed, and further the humidity of the polyimide film Since the expansion coefficient is 10.0 ppm /% RH or less, it is hardly affected by humidity, so it has excellent transparency and excellent bending even in high humidity environments. It is believed to have the sex.
  • the content of the diamine residue having a silicon atom is too large, or when the peak of the tan ⁇ curve exists in a low temperature range such as less than 150 ° C., the mobility of the polyimide molecules in the polyimide film increases and plastic deformation occurs.
  • the bending resistance is likely to deteriorate.
  • the humidity expansion coefficient of the polyimide film exceeds 10.0 ppm /% RH, even if the bending resistance in a dry environment such as a humidity of 20% RH or less is good, the influence of moisture absorption is large. The bending resistance at the end will deteriorate. This is because a polyimide film with a high humidity expansion coefficient expands in a high-temperature and high-humidity environment, and the interaction between the molecular chains becomes dilute, so that the bent part is easily plastically deformed when taking a bent shape. It is guessed.
  • the polyimide film which concerns on this indication contains the polyimide which has a structure represented by the said General formula (1), and has the said specific characteristic. As long as the effects of the present disclosure are not impaired, other components may be contained or other configurations may be included.
  • a polyimide is obtained by reacting a tetracarboxylic acid component and a diamine component. It is preferable to obtain imidization by obtaining a polyamic acid by polymerization of a tetracarboxylic acid component and a diamine component.
  • the imidization may be performed by thermal imidization or chemical imidization. Moreover, it can also manufacture by the method which used thermal imidation and chemical imidization together.
  • the polyimide film according to the present disclosure contains a polyimide having a structure represented by the general formula (1).
  • the tetracarboxylic acid residue means a residue obtained by removing four carboxyl groups from tetracarboxylic acid, and represents the same structure as a residue obtained by removing acid dianhydride structure from tetracarboxylic dianhydride.
  • a diamine residue means the residue remove
  • the polyimide having the structure represented by the general formula (1) contains an aromatic ring, and (i) a fluorine atom, and (ii) the aromatic rings are substituted with a sulfonyl group or fluorine. And at least one selected from the group consisting of a structure linked by an alkylene group which may be formed.
  • the polyimide having the structure represented by the general formula (1) includes at least one selected from a tetracarboxylic acid residue having an aromatic ring and a diamine residue having an aromatic ring, so that the molecular skeleton becomes rigid.
  • the rigid aromatic ring skeleton tends to increase the absorption wavelength to a long wavelength, and tends to decrease the transmittance in the visible light region.
  • a fluorine atom is contained in the polyimide
  • the light transmission is improved because the electronic state in the polyimide skeleton can be hardly transferred.
  • a structure in which aromatic rings are linked to each other by an alkylene group that may be substituted with a sulfonyl group or fluorine is included in polyimide, the charge transfer in the skeleton can be prevented by breaking the ⁇ -electron conjugation in the polyimide skeleton.
  • the light transmittance improves from the point which can be inhibited.
  • a polyimide containing a fluorine atom is preferably used from the viewpoint of improving light transmittance and improving surface hardness.
  • the alkylene group which may be substituted with fluorine improves the bending resistance in a high humidity environment.
  • the alkylene group preferably has 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms, from the viewpoint of improving bending resistance in a high humidity environment.
  • the polyimide having the structure represented by the general formula (1) is an aliphatic hydrocarbon group having 4 or more carbon atoms or an amide group in the main chain or side chain from the viewpoint of bending resistance in a high humidity environment.
  • the total amount of R 1 and R 2 is 100 mol%, it is preferably less than 20 mol%, more preferably 5 mol% or less, and even more preferably 0 mol%. preferable.
  • Tetracarboxylic acid residue and diamine having at least one selected from the group consisting of an aliphatic hydrocarbon group having 4 or more carbon atoms, an amide group, an alkoxy group, and a carboxy group, and containing neither a silicon atom nor a fluorine atom
  • the humidity expansion coefficient tends to increase.
  • both R 1 and R 2 is a silicon atom and a fluorine atom in the general formula (1)
  • the total number of carbon atoms of the aliphatic hydrocarbon group possessed by R 1 and R 2 in the general formula (1) is preferably 7 or less, more preferably 6 or less. More preferably, it is as follows.
  • R 1 and R 2 do not contain any of a silicon atom and a fluorine atom, from the viewpoint of bending resistance in a high humidity environment, R 1 and R 2 does not include any of the silicon atoms and fluorine atoms, and the proportion of the repeating unit total number of carbon atoms of the aliphatic hydrocarbon group having R 1 and R 2 exceeds the upper limit, 10 mole% It is preferably less than 5 mol%, more preferably 5 mol% or less, and even more preferably 0 mol%.
  • the tetracarboxylic acid residue in R 1 of the general formula (1) is not particularly limited, but the acid dianhydride structure is removed from a tetracarboxylic dianhydride having no silicon atom and having an aromatic ring. A residue is preferable from the viewpoint of surface hardness.
  • tetracarboxylic dianhydrides having no silicon atom and having an aromatic ring include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2, 2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) Ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicar
  • the tetracarboxylic acid residue in R 1 of the general formula (1) is, among other things, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride residue from the viewpoint of light transmittance, bending resistance and surface hardness.
  • R 2 in the general formula (1) represents a divalent group which is a diamine residue, and the content ratio of the diamine residue having a silicon atom in the main chain in the total amount of R 2 is 50 mol% or less.
  • the diamine residue in R 2 is a divalent group that 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.
  • the content ratio of the diamine residue having one or two silicon atoms in the main chain is 50 mol% or less, which is excellent in bending resistance in a high humidity environment, and has surface hardness and It is preferable from the viewpoint of excellent compatibility.
  • the diamine residues having no silicon atom a diamine residue having no silicon atom and having an aromatic ring is preferable from the viewpoint of surface hardness.
  • the diamine residue having no aromatic atom and no silicon atom can be a residue obtained by removing two amino groups from a diamine having no silicon atom and an aromatic ring.
  • Examples of the diamine having no aromatic atom and having an aromatic ring include 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 2,2-bis (4-aminophenyl) propane, 2, 2-bis (4-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'-diaminodiphenylmethan
  • the diamine residue having no silicon atom in R 2 of the general formula (1) includes (i) a fluorine atom and (ii) an aromatic ring from the viewpoint of light transmittance, bending resistance and surface hardness.
  • the diamine residue having no silicon atom in R 2 of the general formula (1) is, among others, (i) a fluorine atom, and (ii) an alkylene group in which aromatic rings are substituted with a sulfonyl group or fluorine.
  • R 3 and R 4 each independently represents a hydrogen atom, an alkyl group, or a perfluoroalkyl group.
  • the alkyl group in R 3 and R 4 in the general formula (2) preferably has 1 or more and 3 or less carbon atoms, and preferably 1 or more and 2 or less carbon atoms from the viewpoint of improving bending resistance under high humidity. It is more preferable that
  • the diamine residue having no silicon atom in R 2 of the general formula (1) is 4,4′-diaminodiphenyl from the viewpoints of light transmittance, bending resistance, surface hardness, and low hygroscopicity.
  • the total of these suitable residues is preferably 50 mol% or more, more preferably 65 mol% or more, in total 100 mol% of diamine residues having no silicon atom, Furthermore, it is preferable to contain 80 mol% or more.
  • R 2 is a diamine residue having no silicon atom.
  • the divalent group which is at least 1 type chosen from these is represented,
  • the case where the main chain contains the diamine residue which has a hexafluoro isopropylidene skeleton is mentioned.
  • the diamine residue having a hexafluoroisopropylidene skeleton in the main chain preferably includes a structure in which aromatic rings are linked with 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 1 selected from diamine residue having no silicon atom
  • a diamine residue which represents a divalent group which is a seed and does not have the silicon atom is mainly composed of one molecule in terms of light transmittance, bending resistance, surface hardness, and low hygroscopicity. It is more preferable that the chain contains a diamine residue having a hexafluoroisopropylidene skeleton in the chain and a ratio of fluorine atoms to carbon atoms (number%) of 30% or more. And a diamine residue containing a structure in which aromatic rings are connected by an oxy group, and the ratio (number%) of fluorine atoms to carbon atoms is 30% or more. Preferred.
  • diamine residue having no silicon atom when R 2 in the general formula (1) does not contain a diamine residue having a silicon atom in the main chain include 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-hexafluoropropane residue, 2,2-bis [4- (4-aminophenoxy) phenyl]- 1,1,1,3,3,3-hexafluoropropane residue, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoro Propane and 2,2-bis (4-aminophenyl) hexafluo It is preferably one or more diamine residues selected from the group consisting of
  • R 2 in the general formula (1) does not contain a diamine residue having a silicon atom in the main chain
  • the total of diamine residues having no silicon atom is preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more.
  • the diamine residue having a silicon atom in the main chain can be a residue obtained by removing two amino groups from a diamine having a silicon atom in the main chain.
  • the diamine represented by the following general formula (A) is mentioned, for example.
  • each L is independently a direct bond or —O— bond, and each R 10 may independently have a substituent and contains an oxygen atom or a nitrogen atom.
  • R 11 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and each R 11 independently has a substituent and may contain an oxygen atom or a nitrogen atom. Represents a divalent hydrocarbon group having a number of 1 or more and 20 or less, k is a number of 0 to 200.
  • Plural L, R 10 and R 11 may be the same or different.
  • Examples of the monovalent hydrocarbon group represented by R 10 include an alkyl group having 1 to 20 carbon atoms, an aryl group, and combinations thereof.
  • 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. 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, hexyl group and the like.
  • the cyclic alkyl group is preferably a cycloalkyl group having 3 to 10 carbon atoms, and specific examples 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 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.
  • Examples of the hydrocarbon group that 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 between a divalent hydrocarbon group described later and the monovalent hydrocarbon group. And a group bonded with at least one bond (—NH—).
  • the substituent that the monovalent hydrocarbon group represented by R 10 may have is not particularly limited as long as the effects of the present disclosure are not impaired. For example, a halogen atom such as a fluorine atom or a chlorine atom And a hydroxyl group.
  • 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 compatibility between improvement in bending resistance and surface hardness.
  • the alkyl group having 1 to 3 carbon atoms is more preferably a methyl group
  • the aryl group having 6 to 10 carbon atoms is more preferably a phenyl group.
  • Examples of the divalent hydrocarbon group represented by R 11 include an alkylene group having 1 to 20 carbon atoms, an arylene group, and a combination thereof.
  • 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 to 20 carbon atoms is preferably an alkylene group having 1 to 10 carbon atoms.
  • a linear chain such as a methylene group, an ethylene group, various propylene groups, various butylene groups, or a cyclohexylene group.
  • a combination of a linear or branched alkylene group and a cyclic alkylene group are examples of the divalent hydrocarbon group represented by R 11.
  • the arylene group is preferably an arylene group having 6 to 12 carbon atoms, and examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, and the like. May be.
  • the divalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom the divalent hydrocarbon groups may be ether bonds, carbonyl bonds, ester bonds, amide bonds, and imino bonds (—NH—).
  • a group bonded with at least one is exemplified.
  • the substituent that the divalent hydrocarbon group represented by R 11 may have is the same as the substituent that the monovalent hydrocarbon group represented by R 10 may have. 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 compatibility between improvement in bending resistance and surface hardness. Preferably, it is more preferably an alkylene group having 2 to 4 carbon atoms.
  • K is a number from 0 to 200.
  • the average of k is preferably 0 or more and 6 or less, and preferably 0 or more and 4 or less, from the viewpoint of adhesion to the functional layer and suppression of interference fringes, and the compatibility between improvement in bending resistance and surface hardness. It is preferable. Among these, k is preferably 0 or 1.
  • a diamine residue having a silicon atom in the main chain has one or two silicon atoms in the main chain.
  • a diamine residue is preferred.
  • the glass transition temperature tends to be lowered even when added in a smaller amount, and the bending resistance and surface hardness may be deteriorated.
  • each L is independently a direct bond or —O— bond
  • each R 10 independently has a substituent.
  • And represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an oxygen atom or a nitrogen atom
  • each R 11 may independently have a substituent
  • 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 the same or different.
  • the molecular weight of the diamine residue having a silicon atom in the main chain is preferably 3000 or less and 2000 or less from the viewpoint of imparting bending resistance while suppressing molecular mobility and compatibility of surface hardness. It is preferably 1000 or less, more preferably 800 or less, even more preferably 500 or less, and particularly preferably 300 or less. Furthermore, the molecular weight of the diamine residue having one or two silicon atoms in the main chain is preferably 1000 or less, more preferably 800 or less, even more preferably 500 or less, and 300 or less. It is particularly preferred that The molecular weight of the diamine residue is calculated by subtracting the molecular weight (32) of two amino groups (—NH 2 ) from the molecular weight of the diamine.
  • the diamine residues having a silicon atom in the main chain can be used alone or in admixture of two or more.
  • the polyimide which has a structure represented by the said General formula (1) is a diamine residue in which the diamine residue which has a silicon atom in the principal chain in R ⁇ 2 > in the said General formula (1) has two silicon atoms. It is preferable from the viewpoint of light transmittance, bending resistance and surface hardness. Further, 1,3-bis (3-aminopropyl) tetramethyldisiloxane residue, 1,3-bis (4- Aminobutyl) tetramethyldisiloxane, 1,3-bis (5-aminopentyl) tetramethyldisiloxane, and the like are preferable from the viewpoints of availability and compatibility between light transmittance and surface hardness.
  • R 2 of the general formula (1) contains a diamine residue having a silicon atom in the main chain
  • the content ratio of the diamine residue having a silicon atom in the main chain in the total amount of R 2 is 50 mol%.
  • it is not particularly limited as long as it is below, from the viewpoint of bending resistance, it is preferably 2.5 mol% or more, preferably 2.5 mol% or more and 45 mol% or less, preferably 3 mol% or more and 40 mol%. % Or less is more preferable.
  • R 2 in the general formula (1) is a diamine residue having no silicon atom because of surface hardness and bending resistance in a high humidity environment.
  • a diamine residue having one or two silicon atoms in the main chain is preferred.
  • the total amount (100 mol%) of R 2 is the remainder (100% -x%) of the mol% (x mol%) of the diamine residue having one or two silicon atoms in the main chain. It is preferable that mol% or more and 97.5 mol% or less is a diamine residue which does not have a silicon atom.
  • the polyimide having the structure represented by the general formula (1) from the viewpoint of improving the surface hardness, and the sum of the total amount of the total amount and R 2 of R 1 in the general formula (1) is 100 mol%
  • the total of the tetracarboxylic acid residue having an aromatic ring and the diamine residue having an aromatic ring is preferably 50 mol% or more, more preferably 60 mol% or more, and 75 mol% or more. Even more preferably.
  • the polyimide having the structure represented by the general formula (1) has a tetracarboxylic acid residue of R 1 and a silicon atom of R 2 from the viewpoint of surface hardness and light transmittance and bending resistance. It is preferable that at least one of the diamine residues not having an aromatic ring and a fluorine atom, and further, both the tetracarboxylic acid residue of R 1 and the diamine residue not having a silicon atom of R 2 are It preferably contains an aromatic ring and a fluorine atom.
  • the polyimide having the structure represented by the general formula (1) is the sum of the total amount of R 1 and the total amount of R 2 in the general formula (1) from the viewpoint of surface hardness, light transmittance, and bending resistance.
  • the total of the tetracarboxylic acid residue having an aromatic ring and fluorine atom and the diamine residue having an aromatic ring and fluorine atom is preferably 50 mol% or more, and 60 mol% More preferably, it is more preferably 75 mol% or more.
  • the fluorine atom content of the polyimide having the structure represented by the general formula (1) is the ratio of the number of fluorine atoms (F) and the number of carbon atoms (C) measured on the polyimide surface by X-ray photoelectron spectroscopy (F / C) is preferably 0.01 or more, more preferably 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.
  • it is preferably 0.8 or less.
  • the said ratio by the measurement of X-ray photoelectron spectroscopy can be calculated
  • the polyimide having the structure represented by the general formula (1) is a polyimide in which 50% or more of the hydrogen atoms bonded to the carbon atoms contained in the polyimide are hydrogen atoms directly bonded to the aromatic ring. However, it is preferably used from the viewpoint of improving light transmittance and improving surface hardness and bending resistance.
  • the ratio of the hydrogen atoms (number) directly bonded to the aromatic ring in the total hydrogen atoms (number) bonded to the carbon atoms contained in the polyimide is preferably 60% or more, more preferably 70% or more. It is more preferable.
  • the film is stretched at, for example, 200 ° C. or higher even after a heating step in the atmosphere. Even if it performs, it is preferable from the point which has little change of an optical characteristic, especially a total light transmittance and yellowness YI value, and the suppression of a bending tolerance.
  • polyimide is a polyimide in which 50% or more of the hydrogen atoms bonded to the carbon atoms contained in the polyimide are hydrogen atoms directly bonded to the aromatic ring, the chemical structure of the polyimide changes due to low reactivity with oxygen.
  • Polyimide film uses its high heat resistance and is often used in devices that require processing steps involving heating, but more than 50% of the hydrogen atoms bonded to the carbon atoms contained in the polyimide are in the aromatic ring.
  • polyimide which is a hydrogen atom that is directly bonded, there is no need to carry out these subsequent processes in an inert atmosphere in order to maintain transparency, so that the cost of equipment costs and atmospheric control can be suppressed. There is.
  • the ratio of the hydrogen atoms (number) directly bonded to the aromatic ring in the total hydrogen atoms (number) bonded to the carbon atoms contained in the polyimide is determined by high-performance liquid chromatography or gas chromatography mass of the polyimide decomposition product. It can be determined using an analyzer and NMR. For example, the sample is decomposed with an alkaline aqueous solution or supercritical methanol, and the resulting decomposition product is separated by high performance liquid chromatography, and a qualitative analysis of each separated peak is performed by a gas chromatograph mass spectrometer, NMR, etc.
  • the ratio of hydrogen atoms (numbers) directly bonded to the aromatic ring in the total hydrogen atoms (numbers) contained in the polyimide can be determined by performing determination using high performance liquid chromatography.
  • n represents the number of repeating units and is 1 or more.
  • the number of repeating units n in the polyimide is not particularly limited as long as it is appropriately selected according to the structure so as to exhibit a preferable glass transition temperature to be described later.
  • the average number of repeating units is usually 10 to 2000, and more preferably 15 to 1000.
  • the polyimide used for this indication may have a structure different from the structure represented by the said General formula (1) in the one part.
  • the structure represented by the general formula (1) is preferably 95% or more of the total number of repeating units of the polyimide, more preferably 98% or more, and 100%. Even more preferably.
  • Examples of the structure different from the structure represented by the general formula (1) include a structure having no aromatic ring and a polyamide structure.
  • 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 content ratio of each repeating unit in the polyimide, and the content ratio (mol%) of each tetracarboxylic acid residue or each diamine residue can be determined from the molecular weight of the charge at the time of polyimide production.
  • the content ratio (mol%) of each tetracarboxylic acid residue and each diamine residue in the polyimide is the same as the above, with respect to the decomposition product of polyimide obtained by decomposition with an alkaline aqueous solution or supercritical methanol.
  • the polyimide film of the present disclosure may further contain additives as necessary in addition to the polyimide.
  • additives include inorganic particles, a silica filler for facilitating winding, and a surfactant that improves film-forming properties and defoaming properties.
  • the polyimide film of the present disclosure is excellent in bending resistance under a high humidity environment, when the static bending test is performed according to the following static bending test method, the internal angle measured in the test is 120 ° or more. It is preferable that the angle is 125 ° or more.
  • Static bending test method A polyimide film test piece cut out to 15 mm ⁇ 40 mm is bent at a position of half of the long side, and both ends of the long side of the test piece sandwich a metal piece (100 mm ⁇ 30 mm ⁇ 6 mm) having a thickness of 6 mm from the upper and lower surfaces.
  • test piece Placed between glass plates (100 mm x 100 mm x 0.7 mm) from above and below with the tape fixed so that the overlap between the top and bottom surfaces of the test piece and the metal piece is 10 mm each.
  • the test piece is fixed in a bent state with an inner diameter of 6 mm.
  • a dummy test piece is sandwiched between the metal piece and the glass plate where there is no test piece, and is fixed with tape so that the glass plate is parallel.
  • the test piece thus fixed in a bent state is left to stand for 24 hours in an environment of 60 ° C. and 90% relative humidity (RH), and then the glass plate and fixing tape are removed, and the test piece is attached to the test piece. Release this force. Thereafter, one end of the test piece is fixed, and the internal angle of the test piece 30 minutes after the force applied to the test piece is released is measured.
  • the polyimide film of the present disclosure is superior in bending resistance, in the static bending test method, instead of an environment of 60 ° C. and 90% relative humidity (RH), 70 ° C. and 20% relative humidity (RH). ) Except under the following environment, when a static bending test similar to the static bending test method is performed, it is preferable that the inner angle measured in the test is 120 ° or more.
  • the polyimide film of the present disclosure has an internal angle measured by a static bending test performed in an environment of 60 ° C. and 90% relative humidity (RH), 70 ° C., from the point of bending resistance in a high humidity environment.
  • the absolute value of the difference from the internal angle measured by a static bending test performed in an environment of 20% relative humidity (RH) or less is preferably 10 ° or less, more preferably 7 ° or less. It is still more preferable that it is below °.
  • the polyimide film of the present disclosure has a tensile elastic modulus at 25 ° C. measured from a test piece of 15 mm ⁇ 40 mm in accordance with JIS K7127, a tensile speed of 8 mm / min, and a distance between chucks of 20 mm, in terms of surface hardness. It is preferably 1.8 GPa or more, and may be 5.0 GPa or less from the viewpoint of bending resistance. From the viewpoint of bending resistance and surface hardness, it is preferably 2.0 GPa or more and 4.0 GPa or less, and more preferably 2.0 GPa or more and 3.5 GPa or less.
  • the tensile elastic modulus was determined by cutting a test piece having a width of 15 mm ⁇ a length of 40 mm from a polyimide film using a tensile tester (for example, Shimadzu Corporation: Autograph AG-X 1N, load cell: SBL-1KN) at 25 ° C.
  • the tensile speed can be 8 mm / min, and the distance between chucks can be 20 mm.
  • the polyimide film for obtaining the tensile modulus of elasticity preferably has a thickness of 55 ⁇ m ⁇ 5 ⁇ m.
  • the polyimide film of the present disclosure preferably has a birefringence in the thickness direction at the wavelength of 590 nm of 0.040 or less, preferably 0.020 or less, from the viewpoint of reducing optical distortion. Is preferably .015 or less, more preferably 0.010 or less, and even more preferably less than 0.008.
  • the polyimide film of the present disclosure is used as a display surface material, the deterioration in display quality of the display can be suppressed when the optical distortion of the polyimide film of the present disclosure is reduced.
  • the birefringence of the thickness direction in the said wavelength 590nm of the polyimide film of this indication can be calculated
  • the thickness direction retardation value (Rth) of the polyimide film is measured with a light of 25 ° C. and a wavelength of 590 nm using a phase difference measuring apparatus (for example, product name “KOBRA-WR” manufactured by Oji Scientific Instruments). To do.
  • a phase difference value at 0 degree incidence and a phase difference value at an incidence angle of 40 degrees are measured, and the thickness direction retardation value Rth is calculated from these phase difference values.
  • the retardation value at an oblique incidence of 40 degrees is measured by making light having a wavelength of 590 nm incident on the retardation film from a direction inclined by 40 degrees from the normal line of the retardation film.
  • the birefringence in the thickness direction of the polyimide film can be determined by substituting it into the formula: Rth / d.
  • Said d represents the film thickness (nm) of a polyimide film.
  • the thickness direction retardation value is nx the refractive index 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 in the film plane (film surface).
  • Rth [nm] ⁇ (nx + ny) / 2 ⁇ nz ⁇ ⁇ d, where ny is the refractive index in the direction in which the refractive index in the inner direction is the minimum) and nz is the refractive index in the thickness direction of the film.
  • the pencil hardness may be 6B or more, but from the viewpoint of surface hardness, it is preferably 2B or more, more preferably B or more, and more preferably HB or more. Further preferred.
  • the pencil hardness of the polyimide film is determined by JIS K5600-5-4 using a test pencil specified by JIS-S-6006 after conditioning the sample for 2 hours at a temperature of 25 ° C. and a relative humidity of 60%. (1999), a pencil hardness test (0.98 N load) is performed on the film surface, and the highest pencil hardness that does not cause scratches can be evaluated.
  • the testing machine for example, a pencil scratch coating film hardness testing machine manufactured by Toyo Seiki Co., Ltd. can be used.
  • the haze value of the polyimide film of the present disclosure is preferably 2.0 or less, more preferably 1.5 or less, and even more preferably 1.0 or less, from the viewpoint of light transmittance. It is preferable that the haze value can 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 according to JIS K-7105, for example, a haze meter HM150 manufactured by Murakami Color Research Laboratory.
  • the thickness of the polyimide film of the present disclosure may be appropriately selected depending on the use, but from the viewpoint of strength, it is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, and even more preferably 10 ⁇ m or more. It is preferable that On the other hand, from the viewpoint of bending resistance, the thickness of the polyimide film is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and even more preferably 100 ⁇ m or less.
  • the polyimide film of the present disclosure may be subjected to a surface treatment such as a saponification treatment, a glow discharge treatment, a corona discharge treatment, an ultraviolet treatment, or a flame treatment.
  • a surface treatment such as a saponification treatment, a glow discharge treatment, a corona discharge treatment, an ultraviolet treatment, or a flame treatment.
  • Production method of polyimide film As a production method of the polyimide film of the present disclosure, for example, as a first production method, And at least one selected from the group consisting of (i) a fluorine atom, and (ii) a structure in which aromatic rings are connected to each other by a sulfonyl group or an alkylene group optionally substituted with fluorine.
  • a step of preparing a polyimide precursor resin composition containing a polyimide precursor having a structure represented by the following general formula (1 ′) and an organic solvent (hereinafter referred to as a polyimide precursor resin composition preparation step) )When, 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 process); The process of imidating the said polyimide precursor by heating (henceforth an imidation process) and the manufacturing method of the polyimide film containing are mentioned.
  • the stretching step the 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 (hereinafter referred to as the stretching step).
  • the stretching step the 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.
  • Polyimide precursor resin composition preparation step The polyimide precursor resin composition prepared in the first production method includes an aromatic ring, and (i) a fluorine atom, and (ii) aromatic rings.
  • the polyimide precursor of the present disclosure suitable for manufacturing the polyimide film or the polyimide of the present disclosure includes an aromatic ring, and (ii) a fluorine atom, and (ii) the aromatic rings are sulfonyl group or fluorine.
  • the polyimide precursor having the structure represented by the general formula (1 ′) includes a tetracarboxylic acid component that becomes a tetracarboxylic acid residue in R 1 of the general formula (1 ′), and the general formula (1 ′).
  • a polyamic acid obtained in the R 2 by polymerization of a diamine residues become diamine component.
  • 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 has a number average molecular weight of preferably 10,000 or more, more preferably 20,000 or more, even more preferably 30,000 or more, from the viewpoint of strength and bending resistance when it is used as a film. It is especially preferable that it is 50000 or more. On the other hand, if the number average molecular weight is too large, the viscosity becomes high and the workability such as filtration may be reduced, and therefore it is preferably 10000000 or less, and more preferably 500000 or less.
  • the number average molecular weight of the polyimide precursor can be determined by NMR (for example, AVANCE III manufactured by BRUKER). For example, a polyimide precursor solution is applied to a glass plate and dried at 100 ° C.
  • the number average molecular weight can be calculated from the peak intensity ratio of hydrogen atoms.
  • the polyimide precursor has a weight average molecular weight of preferably 20000 or more, more preferably 30000 or more, and more preferably 40000 or more from the viewpoint of strength and bending resistance when formed into a film. More preferably, it is particularly preferably 80000 or more. On the other hand, when the weight average molecular weight is too large, the viscosity becomes high and the workability such as filtration may be reduced, and therefore it is preferably 10000000 or less, and more preferably 500000 or less.
  • the weight average molecular weight of the polyimide precursor can be measured by gel permeation chromatography (GPC).
  • the polyimide precursor was made into an N-methylpyrrolidone (NMP) solution having a concentration of 0.5% by weight, and the developing solvent was a 10 mmol% LiBr-NMP solution having a water content of 500 ppm or less.
  • NMP N-methylpyrrolidone
  • the developing solvent was a 10 mmol% LiBr-NMP solution having a water content of 500 ppm or less.
  • HLC-8120 column used: GPC LF-804 manufactured by SHODEX, measurement is performed under the conditions of a sample injection amount of 50 ⁇ L, a solvent flow rate of 0.5 mL / min, and 40 ° C.
  • the weight average molecular weight is determined based on a polystyrene standard sample having the same concentration as the sample.
  • the polyimide precursor solution is obtained by reacting the above tetracarboxylic dianhydride and the above diamine in a solvent.
  • the solvent used for the synthesis of the polyimide precursor is not particularly limited as long as it can dissolve the above-described tetracarboxylic dianhydride and diamine.
  • an aprotic polar solvent or a water-soluble alcohol solvent is used.
  • an 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.
  • an organic solvent containing a nitrogen atom among which N, N-dimethylacetamide, N— It is preferable to use methyl-2-pyrrolidone or a combination thereof.
  • the organic solvent is a solvent containing carbon atoms.
  • an acid dianhydride may be added to a mixed solution of two or more diamines to synthesize polyamic acid. More than one kind of diamine component may be added to the reaction solution step by step at an appropriate molar ratio, and the sequence in which each raw material is incorporated into the polymer chain may be controlled to some extent. For example, an acid dianhydride having a molar ratio of 0.5 equivalent of a diamine having a silicon atom in the main chain is charged into a reaction solution in which a diamine having a silicon atom in the main chain is dissolved, and reacted.
  • Amidic acid in which a diamine having a silicon atom in the main chain was reacted at both ends of the anhydride was synthesized, and all or part of the remaining diamine was added thereto, and acid dianhydride was added to polymerize the polyamic acid. Also good.
  • a diamine having a silicon atom in the main chain is introduced into the polyamic acid in a linked form via one acid dianhydride. Polymerization of the polyamic acid by such a method is preferable because the positional relationship of the amic acid having a silicon atom in the main chain is specified to some extent, and it is easy to obtain a film having excellent bending resistance while maintaining the surface hardness.
  • Y / X may be 0.9 or more and 1.1 or less. Preferably, it is 0.95 or more and 1.05 or less, more preferably 0.97 or more and 1.03 or less, and particularly preferably 0.99 or more and 1.01 or less. By setting it as such a range, the molecular weight (polymerization degree) of the polyamic acid obtained can be adjusted moderately.
  • the procedure of the polymerization reaction can be appropriately selected from known methods and is not particularly limited.
  • the polyimide precursor solution obtained by the synthesis reaction may be used as it is, and other components may be mixed there if necessary.
  • the solvent of the polyimide precursor solution is dried and dissolved in another solvent. It may be used.
  • the viscosity of the polyimide precursor solution at 25 ° C. is preferably 500 cps or more and 200,000 cps or less from the viewpoint of forming a uniform coating film and a polyimide film.
  • the viscosity of the polyimide precursor solution can be measured at 25 ° C. using a viscometer (for example, TVE-22HT, Toki Sangyo Co., Ltd.).
  • the said polyimide precursor solution may be used and the additive may be contained as needed.
  • the additive include inorganic particles, silica filler for facilitating winding, a surfactant for improving film forming property and defoaming property, and the like described in the above polyimide film. Similar ones can be used.
  • the organic solvent used in the polyimide precursor resin composition is not particularly limited as long as the polyimide precursor can be dissolved.
  • nitrogen atoms such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone
  • Organic solvent: ⁇ -butyrolactone or the like can be used, and among them, it is preferable to use an organic solvent containing a nitrogen atom for the reasons described above.
  • Content of the said polyimide precursor in the said polyimide precursor resin composition is 50 mass% or more in solid content of a resin composition from the point which forms the polyimide film which has a uniform coating film and the intensity
  • it is preferably 60% by mass or more, and the upper limit may be appropriately adjusted depending on the components contained.
  • 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 a polyimide film.
  • it is 99% by mass or less.
  • the polyimide precursor resin composition preferably has a moisture content of 1000 ppm or less from the viewpoint of improving the storage stability of the polyimide precursor resin composition and improving the productivity. If the polyimide precursor resin composition contains a large amount of moisture, the polyimide precursor may be easily decomposed.
  • the water content of the polyimide precursor resin composition can be determined using a Karl Fischer moisture meter (for example, a trace moisture measuring device CA-200, manufactured by Mitsubishi Chemical Corporation). As described above, in order to control the water content to 1000 ppm or less, it is preferable to dehydrate the organic solvent to be used or use a water whose amount is controlled and handle it in an environment with a humidity of 5% or less.
  • the viscosity of the polyimide precursor resin composition at 25 ° C. is preferably 500 cps or more and 200,000 cps or less from the viewpoint of forming a uniform coating film and a polyimide film.
  • the viscosity of the polyimide precursor resin composition can be measured using a viscometer (for example, TVE-22HT, Toki Sangyo Co., Ltd.) at 25 ° C. and a sample amount of 0.8 mL.
  • the support used has a smooth surface and heat resistance.
  • the material is not particularly limited as long as the material is resistant and solvent resistant.
  • an inorganic material such as a glass plate, a metal plate having a mirror-finished surface, and the like can be given.
  • the shape of the support is selected depending on the coating method, and may be, for example, a plate shape, a drum shape, a belt shape, a sheet shape that can be wound around a roll, or the like.
  • the application means is not particularly limited as long as it can be applied at a desired film thickness, and for example, a known one such as a die coater, comma coater, roll coater, gravure coater, curtain coater, spray coater, lip coater or the like can be used. . Application may be performed by a single-wafer coating apparatus or a roll-to-roll coating apparatus.
  • the solvent in the coating film is dried at a temperature of 150 ° C. or lower, preferably 30 ° C. or higher and 120 ° C. or lower until the coating film is tack-free.
  • the drying time may be appropriately adjusted according to the film thickness of the polyimide precursor resin coating film, the type of solvent, the drying temperature, etc., but is usually 30 seconds to 240 minutes, preferably 1 minute to 180 minutes, more preferably. Is preferably 90 seconds to 120 minutes.
  • an upper limit it is unpreferable from the surface of the production efficiency of a polyimide film.
  • the value is below the lower limit, the appearance of the resulting polyimide film may be affected by rapid solvent drying.
  • the method for drying the solvent is not particularly limited as long as the solvent can be dried at the above temperature.
  • an oven, a drying furnace, a hot plate, infrared heating, or the like can be used.
  • the atmosphere during drying of the solvent is preferably an inert gas atmosphere.
  • the inert gas atmosphere is preferably a nitrogen atmosphere, the oxygen concentration is preferably 500 ppm or less, more preferably 100 ppm or less, and most preferably 50 ppm or less.
  • heat treatment is performed in the atmosphere, the film may be oxidized and colored, or the performance may deteriorate.
  • the said 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, and the said polyimide precursor resin after an extending process
  • the imidization temperature may be appropriately selected according to the structure of the polyimide precursor.
  • the temperature rise start temperature is preferably 30 ° C. or higher, more preferably 100 ° C. or higher.
  • the temperature rise end temperature is preferably 250 ° C. or higher.
  • the rate of temperature increase is preferably selected as appropriate depending on the film thickness of the polyimide film to be obtained.
  • the film thickness of the polyimide film is thick, it is preferable to decrease the temperature increase rate. From the viewpoint of the production efficiency of the polyimide film, it is preferably 5 ° C./min or more, 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, more preferably 30 ° C./min or less. It is preferable to set the temperature increase rate from the viewpoint that the appearance defect and strength reduction of the film can be suppressed, and the whitening associated with the imidization reaction can be controlled, and the light transmittance is improved.
  • the temperature increase may be continuous or stepwise, but it is preferable to make it continuous from the viewpoint of controlling the appearance of the film, suppressing the strength reduction, and controlling the whitening associated with the imidization reaction. Moreover, in the above-mentioned whole temperature range, the temperature rising rate may be constant or may be changed in the middle.
  • the atmosphere at the time of temperature increase in imidation is preferably an 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 even more preferably 100 ppm or less.
  • the film may be oxidized and colored, or the performance may deteriorate.
  • 50% or more of the hydrogen atoms bonded to the carbon atoms contained in the polyimide are hydrogen atoms directly bonded to the aromatic ring, there is little influence of oxygen on the optical properties, and an inert gas atmosphere is not used.
  • a polyimide having a high light transmittance can be obtained.
  • the heating method for imidation is not particularly limited as long as the temperature can be raised at the above temperature.
  • an oven, a heating furnace, infrared heating, electromagnetic induction heating, or the like can be used.
  • the imidation ratio of a polyimide precursor shall be 50% or more before an extending process. Even if the imidization rate is 50% or more before the stretching step, the film is stretched after the step, and then heated at a higher temperature for a certain period of time to perform imidization. Whitening is suppressed.
  • the imidization rate is 80% or more in the imidization step before the stretching step, and the reaction is allowed to proceed to 90% or more, and further to 100%. Is preferred.
  • the imidation rate can be measured by analyzing the spectrum by infrared measurement (IR).
  • reaction In order to obtain a final polyimide film, it is preferable to proceed the reaction to 90% or more, further 95% or more, and further 100%. In order to allow the reaction to proceed to 90% or more, more preferably 100%, it is preferable to hold at a temperature rising end temperature for a certain period of time. Minutes are preferred.
  • the first production method includes a stretching process of stretching at least one of the polyimide precursor resin coating film and a post-imidation coating film obtained by imidizing the polyimide precursor resin coating film. It may be. When it has the said extending
  • the heating temperature during stretching is preferably in the range of glass transition temperature ⁇ 50 ° C. of the polyimide or polyimide precursor, and preferably in the range of 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 stretching is relaxed by the temperature, and there is a possibility that sufficient orientation cannot be obtained.
  • the stretching step may be performed simultaneously with the imidization step. Stretching the film after imidization after imidation rate of 80% or more, further 90% or more, even more 95% or more, and particularly substantially 100% imidation improves the surface hardness of the polyimide film. It is preferable from the point.
  • the draw ratio of the polyimide film is preferably from 101% to 10,000%, more preferably from 101% to 500%. By stretching in the above range, the surface hardness of the obtained polyimide film can be further improved.
  • the method for fixing the polyimide film during stretching is not particularly limited, and is selected according to the type of stretching apparatus. Moreover, there is no restriction
  • the polyimide film may be stretched only in one direction (longitudinal stretching or lateral stretching), or may be stretched in two directions by simultaneous biaxial stretching, sequential biaxial stretching, oblique stretching, or the like.
  • the first production method is preferable from the viewpoint of easily reducing the birefringence of the polyimide film.
  • a polyimide film having a birefringence in the thickness direction at a wavelength of 590 nm of 0.020 or less and further 0.010 or less can be suitably formed.
  • a manufacturing method of the polyimide film of this indication as a 2nd manufacturing method, And at least one selected from the group consisting of (i) a fluorine atom, and (ii) a structure in which aromatic rings are connected to each other by a sulfonyl group or an alkylene group optionally substituted with fluorine.
  • a step of preparing a polyimide resin composition containing a polyimide having a structure represented by the general formula (1) and an organic solvent hereinafter referred to as a polyimide resin composition preparation step
  • the polyimide resin composition is applied to a support, the solvent is dried, and a polyimide resin coating film is formed (hereinafter referred to as a polyimide resin coating film forming process).
  • a polyimide resin composition containing an additive can also be suitably used.
  • the polyimide having the structure represented by the general formula (1) including one has a solvent solubility such that 5% by mass or more dissolves in an organic solvent at 25 ° C.
  • the production method is preferably used. Can do.
  • the polyimide having the solvent solubility described above can be selected and used from among the same polyimides described for the polyimide film.
  • a method for imidization it is preferable to use chemical imidation performed using a chemical imidizing agent instead of heat dehydration for the dehydration ring-closing reaction of the polyimide precursor.
  • 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.
  • Examples of the acid anhydride are not limited to acetic anhydride, and propionic acid anhydride, n-butyric acid anhydride, benzoic acid anhydride, trifluoroacetic acid anhydride, and the like, but are not particularly limited.
  • a tertiary amine such as pyridine or ⁇ -picolinic acid may be used in combination.
  • the optical properties particularly the yellowness (YI value) are reduced.
  • reaction liquid reacted from the precursor to the polyimide is not cast as it is, It is preferable to form the film after purification by reprecipitation or the like, and removing components other than polyimide to 100 ppm or less of the total weight of the polyimide.
  • the organic solvent used in the reaction solution for chemical imidization of the polyimide precursor for example, those described in the polyimide precursor resin composition preparation step in the first manufacturing method Similar ones can be used.
  • the organic solvent used when redissolving the polyimide purified from the reaction solution 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-propyl acetate, normal-pentyl acetate, cyclohexanol, cyclohexanone, 1.4-Dioxane, tetrach
  • the polyimide resin composition may contain an additive as necessary.
  • an additive the thing similar to what was demonstrated in the said polyimide precursor resin composition preparation process in a said 1st manufacturing method can be used.
  • the said 2nd manufacturing method as a method of making the water content of the said polyimide resin composition into 1000 ppm or less, it is the same as the method demonstrated in the said polyimide precursor resin composition preparation process in the said 1st manufacturing method. The method can be used.
  • the support and the coating method are the same as those described in the polyimide precursor resin coating film forming step of the first manufacturing method. be able to.
  • the drying temperature is preferably 80 ° C. or higher and 150 ° C. or lower under normal pressure. It is preferable that the pressure be in the range of 10 ° C. to 100 ° C. under reduced pressure.
  • the second manufacturing method may have a stretching process of stretching the polyimide resin coating film after the polyimide resin coating film forming process.
  • the said extending process can be made to be the same as that of the extending process in the said 1st manufacturing method.
  • the second production method is preferable from the viewpoint of easily reducing the yellowness (YI value) of the polyimide film.
  • the second production method it is possible to suitably form a polyimide film having a value obtained by dividing the yellowness calculated in accordance with JIS K7373-2006 by the film thickness ( ⁇ m) of 0.04 or less. is there.
  • polyimide film of the present disclosure is not particularly limited, and can be used as a member such as a base material or a surface material for which a glass product such as a thin plate glass has been conventionally used. Since the polyimide film of the present disclosure is excellent in transparency and bending resistance, it can be suitably used as a surface material for a display, and in particular, can be suitably used as a surface material for a flexible display and can be folded. It can be suitably used as a surface material for use.
  • the polyimide film of the present disclosure is specifically a flexible panel used for, for example, a thin and bent flexible type organic EL display, a portable terminal such as a smartphone or a wristwatch type terminal, a display device inside a car, a wristwatch, or the like. It can use suitably for etc.
  • the polyimide film of the present disclosure includes a member for an image display device such as a liquid crystal display device and an organic EL display device, a member for a touch panel, a flexible printed circuit board, a surface protection film and a substrate material for a solar cell panel, an optical waveguide, etc.
  • the present invention can also be applied to other members, other semiconductor-related members and the like.
  • the laminate of the present disclosure is a laminate having the above-described polyimide film of the present disclosure and a hard coat layer containing at least one polymer of a radical polymerizable compound and a cationic polymerizable compound. Since the laminate of the present disclosure uses the polyimide film of the present disclosure described above, it has excellent transparency, improved bending resistance under high humidity, and further has a hard coat layer, The hardness is further improved.
  • Hard coat layer used in the laminate of the present disclosure contains at least one polymer of a radical polymerizable compound and a cationic polymerizable compound.
  • the radical polymerizable compound is a compound having a radical polymerizable group.
  • the radical polymerizable group possessed by the radical 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. Specific examples include a vinyl group and a (meth) acryloyl group.
  • these radical polymerizable groups may be the same or different from each other.
  • the number of radical polymerizable groups contained in one molecule of the radical polymerizable compound is preferably 2 or more, and more preferably 3 or more from the viewpoint of improving the hardness of the hard coat layer.
  • a compound having a (meth) acryloyl group is preferable from the viewpoint of high reactivity, and a polyfunctional acrylate monomer having 2 to 6 (meth) acryloyl groups in one molecule;
  • (meth) acryloyl represents each of acryloyl and methacryloyl
  • (meth) acrylate represents each of acrylate and methacrylate.
  • radical 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), trimethylolpropane tri (meth) acrylate, tri Methylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaeryth Polyol polyacrylates such as lithol tetra (meth) acrylate, dipentaerythritol penta (meth)
  • the cationic polymerizable compound is a compound having a cationic polymerizable group.
  • the cationic polymerizable group possessed by the cationic 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 cationic polymerizable groups may be the same or different from each other.
  • the number of cationically polymerizable groups contained in one molecule of the cationically polymerizable compound is preferably 2 or more, and more preferably 3 or more from the viewpoint of improving the hardness of the hard coat layer.
  • the cationic polymerizable compound is preferably a compound having at least one of an epoxy group and an oxetanyl group as the cationic polymerizable group, from the viewpoint of adhesion of the hard coat layer and light transmittance and surface hardness.
  • a compound having two or more of at least one of an epoxy group and an oxetanyl group in one molecule is more preferable.
  • Cyclic ether groups such as epoxy groups and oxetanyl groups are preferred from the viewpoint of small shrinkage accompanying the polymerization reaction.
  • compounds having an epoxy group among the cyclic ether groups are easily available as compounds having various structures, do not adversely affect the durability of the obtained hard coat layer, and easily control the compatibility with the radical polymerizable compound.
  • the oxetanyl group has a high degree of polymerization and low toxicity compared to the epoxy group.
  • a cationically polymerizable compound having an epoxy group for example, a polyglycidyl ether of a polyhydric alcohol having an alicyclic ring, a cyclohexene ring or a cyclopentene ring-containing compound may be used with an appropriate oxidizing agent such as hydrogen peroxide or peracid.
  • Alicyclic epoxy resin obtained by epoxidation polyglycidyl ether of aliphatic polyhydric alcohol or alkylene oxide adduct thereof, polyglycidyl ester of aliphatic long-chain polybasic acid, homopolymer of glycidyl (meth) acrylate, Aliphatic epoxy resins such as copolymers; glycidyl produced by reaction of bisphenols such as bisphenol A, bisphenol F and hydrogenated bisphenol A, or derivatives thereof such as alkylene oxide adducts and caprolactone adducts, and epichlorohydrin Ether, and novolac epoxy resins such as a and glycidyl ether type epoxy resins derived from bisphenols are exemplified.
  • alicyclic epoxy resin examples include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (UVR-6105, UVR-6107, UVR-6110), bis-3,4-epoxycyclohexylmethyl adipate. (UVR-6128) (The product names in parentheses are manufactured by Dow Chemical.)
  • Examples of the glycidyl ether type epoxy resin include sorbitol polyglycidyl ether (Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-614B, Denacol EX-622), Polyglycerol polyglycidyl ether (Denacol EX).
  • epoxy resins include trade names such as Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 828EL, Epicoat 828XA, Epicoat 834, Epicoat 801, Epicoat 801P, Epicoat 802, Epicoat 815, Epicoat 815XA, Epicoat 816A, Epicoat 819, Epicoat 834X90, Epicoat 1001B80, Epicoat 1001X70, Epicoat 1001X75, Epicoat 1001T75, Epicoat 806, Epicoat 806P, Epicoat 807, Epicoat 152, Epicoat 154, Epicoat 871, Epicoat 191P, Epicoat YX310, Epicoat DX255, Epicoat YX8000, Etc. (above product name, Turbocharger bread epoxy resin) and the like.
  • Examples of the cationically polymerizable compound having an oxetanyl group include 3-ethyl-3-hydroxymethyloxetane (OXT-101) and 1,4-bis-3-ethyloxetane-3-ylmethoxymethylbenzene (OXT-121).
  • At least one polymer of the radical polymerizable compound and the cationic polymerizable compound contained in the hard coat layer used in the present disclosure is, for example, the radical polymerizable compound or the cationic polymerizable compound. It can be obtained by adding a polymerization initiator to at least one kind, if necessary, and carrying out 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 cationic polymerization.
  • the radical polymerization initiator may be any substance that can release a substance that initiates radical polymerization by light irradiation and / or heating.
  • photo radical polymerization initiators include imidazole derivatives, bisimidazole derivatives, N-aryl glycine derivatives, organic azide compounds, titanocenes, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, thioxanthone derivatives, and the like.
  • Irgacure 907 Irgacure 379, Irgacure 819, Irgacure 127, Irgacure 500, Irgacure 754, Irgacure 250, Irgacure 1800, Irgacure 1870 manufactured by Ciba Japan Co., Ltd. , Irgacure OXE01, DAROCUR TPO, DAROCUR1173, Japan Siber Hegner Co., Ltd.
  • the cationic polymerization initiator should just be able to discharge
  • the cationic polymerization initiator include sulfonic acid ester, imide sulfonate, dialkyl-4-hydroxysulfonium salt, arylsulfonic acid-p-nitrobenzyl ester, silanol-aluminum complex, ( ⁇ 6 -benzene) ( ⁇ 5 -cyclopentadidiene).
  • Enyl) iron (II) and the like and more specific examples include, but are not limited to, benzoin tosylate, 2,5-dinitrobenzyl tosylate, N-tosiphthalimide and the like.
  • radical polymerization initiators that can be used as cationic polymerization initiators include aromatic iodonium salts, aromatic sulfonium salts, aromatic diazonium salts, aromatic phosphonium salts, triazine compounds, iron arene complexes, and the like.
  • iodonium chloride such as diphenyliodonium, ditolyliodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bromide, borofluoride, hexafluorophosphate salt, hexafluoro Iodonium salts such as antimonate salts, chlorides of sulfonium such as triphenylsulfonium, 4-tert-butyltriphenylsulfonium, tris (4-methylphenyl) sulfonium, bromide, borofluoride, 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, 2,4,6-sub
  • the hard coat layer used in the present disclosure is, if necessary, an antistatic agent, an antiglare agent, an antifouling agent, inorganic or organic fine particles for improving hardness, You may contain additives, such as a leveling agent and various sensitizers.
  • the radically polymerizable compound and the cationically polymerizable compound contained in the hard coat layer used in the present disclosure are a Fourier transform infrared spectrophotometer (FTIR), a pyrolysis gas chromatograph (GC) -MS) and polymer decomposition products can be analyzed using a combination of high performance liquid chromatography, gas chromatograph mass spectrometer, NMR, elemental analysis, XPS / ESCA, TOF-SIMS and the like.
  • FTIR Fourier transform infrared spectrophotometer
  • GC pyrolysis gas chromatograph
  • polymer decomposition products can be analyzed using a combination of high performance liquid chromatography, gas chromatograph mass spectrometer, NMR, elemental analysis, XPS / ESCA, TOF-SIMS and the like.
  • the laminate of the present disclosure is not particularly limited as long as it has the polyimide film and the hard coat layer, and the hard coat layer is laminated on one surface side of the polyimide film.
  • the hard coat layer may be laminated on both sides of the polyimide film.
  • the laminated body of this indication is for the range which does not impair the effect of this indication other than the said polyimide film and the said hard coat layer, for example, for improving the adhesiveness of the said polyimide film and the said hard coat layer.
  • Other layers such as a primer layer may be included, and the polyimide film and the hard coat layer may be laminated via another layer such as a primer layer.
  • the total thickness of the laminate of the present disclosure may be appropriately selected depending on the application, but is preferably 10 ⁇ m or more, and more preferably 40 ⁇ m or more from the viewpoint of strength. On the other hand, from the viewpoint of bending resistance, it 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.
  • the pencil hardness on the hard coat layer side surface is preferably H or more, more preferably 2H or more, and even more preferably 3H or more.
  • the pencil hardness of the laminate of the present disclosure can be measured in the same manner except that the load is 9.8 N in the method for measuring the pencil hardness of the polyimide film.
  • the total light transmittance measured in accordance with JIS K7361-1 is preferably 85% or more, more preferably 88% or more, and still more preferably 90% or more. Is preferred.
  • the total light transmittance of the laminate of the present disclosure can be measured in the same manner as the total light transmittance of the polyimide film measured according to JIS K7361-1.
  • the yellowness (YI value) calculated in accordance with JIS K7373-2006 is preferably 20 or less, more preferably 12 or less, and more preferably 10 or less. More preferred is 5 or less. Further, the laminate of the present disclosure has a yellow color calculated in accordance with JIS K7373-2006 because yellowish coloring is suppressed, light transmittance is improved, and it can be suitably used as a glass substitute material.
  • 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 0.04 or less, and 0.03 More preferably, it is as follows.
  • the yellowness (YI value) of the laminate of the present disclosure can be measured in the same manner as the yellowness (YI value) calculated based on JIS K7373-2006 of the polyimide film.
  • the haze value of the laminate of the present disclosure is preferably 10 or less, more preferably 8 or less, and even more preferably 5 or less from the viewpoint of light transmittance.
  • the haze value of the laminate of the present disclosure 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 disclosure is preferably 0.040 or less, preferably 0.020 or less, preferably 0.015 or less, and It is preferably 010 or less, and more preferably less than 0.008.
  • the birefringence of the laminate of the present disclosure can be measured in the same manner as the birefringence in the thickness direction at a wavelength of 590 nm of the polyimide film.
  • Manufacturing method of laminated body As a manufacturing method of the laminated body of the present disclosure, for example, Forming a coating film of a hard coat layer forming composition containing at least one of a radical polymerizable compound and a cationic polymerizable compound on at least one surface of the polyimide film of the present disclosure; And a step of 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 radical polymerizable compound, cationic polymerizable compound, polymerization initiator and additive contained in the hard coat layer forming composition can be the same as those described in the hard coat layer.
  • the solvent can be appropriately selected from known solvents.
  • the hard coat layer forming composition is publicly known on at least one surface of the polyimide film.
  • coating means is mentioned.
  • the application means is not particularly limited as long as it is a method that 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 solvent is removed by drying the coating film of the curable resin composition for a hard coat layer as necessary.
  • drying method include reduced-pressure drying or heat drying, and a method combining these drying methods.
  • ultraviolet rays For light irradiation, ultraviolet rays, visible light, electron beams, ionizing radiation, etc. are mainly used.
  • ultraviolet curing ultraviolet rays emitted from light such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp are used.
  • the irradiation amount of the energy ray source is about 50 to 5000 mJ / cm 2 as an integrated exposure amount at an ultraviolet wavelength of 365 nm.
  • the treatment When heating, the treatment is usually performed at a temperature of 40 ° C. or higher and 120 ° C. or lower. Moreover, you may react by leaving it to stand for 24 hours or more at room temperature (25 degreeC).
  • the surface material for display of this indication is the polyimide film of this indication mentioned above, or the layered product of this indication.
  • the display surface material of the present disclosure is arranged and used so as to be positioned on the surface of various displays.
  • the display surface material of the present disclosure like the polyimide film of the present disclosure and the laminate of the present disclosure described above, is excellent in transparency and improved in bending resistance under high humidity, and is particularly suitable for flexible displays. It can be used suitably.
  • the display surface material of the present disclosure can be used for various known displays and is not particularly limited.
  • the display surface material can be used for the display described in the application of the polyimide film of the present disclosure.
  • positioning on the surface of a display may be the surface by the side of a polyimide film, or a hard-coat layer It may be the side surface.
  • position the surface material for a display of this indication so that the surface by the side of a hard-coat layer may become a surface of the front side more.
  • the display surface material of the present disclosure may have a fingerprint adhesion preventing layer on the outermost surface.
  • the method for disposing the display surface material of the present disclosure on the surface of the display is not particularly limited, and examples thereof include a method through an adhesive layer.
  • the adhesive layer a conventionally known adhesive layer that can be used for adhesion of a display surface material can be used.
  • the weight average molecular weight of the polyimide precursor was developed by making the polyimide precursor a 0.5% by weight N-methylpyrrolidone (NMP) solution, filtering the solution through a syringe filter (pore diameter: 0.45 ⁇ m), and developing the polyimide precursor.
  • NMP N-methylpyrrolidone
  • As a solvent a 10 mmol% LiBr-NMP solution having a water content of 500 ppm or less was used, and a GPC apparatus (manufactured by Tosoh Corporation, HLC-8120, column used: SHODEX GPC LF-804) was used. The measurement was performed under the conditions of 40 ° C./min.
  • 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, 3,070) was used as a conversion value with respect to standard polystyrene measured. 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 using a viscometer (for example, TVE-22HT, Toki Sangyo Co., Ltd.) at 25 ° C. with a sample amount of 0.8 mL.
  • NMP N-methylpyrrolidone
  • the solution was filtered through a syringe filter (pore size: 0.45 ⁇ m), a 30 mmol% LiBr-NMP solution having a water content of 500 ppm or less was used as a developing solvent, and a GPC apparatus (manufactured by Tosoh Corporation, HLC-8120, detector: differential) Refractive index (RID) detector, column used: two SHODEX GPC LF-804s connected in series), sample injection 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 the same as the polystyrene standard sample (weight average molecular weight: 364,700, 204,000, 103,500, 44,360,27,500, 13,030, 6,300, 3, 070) was used as a conversion value with respect to standard polystyrene measured.
  • 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 using a viscometer (eg, TVE-22HT, Toki Sangyo Co., Ltd.) at 25 ° C. and a sample amount of 0.8 mL.
  • a viscometer eg, TVE-22HT, Toki Sangyo Co., Ltd.
  • ⁇ Thickness measurement method> The film thickness of a total of five points at the four corners and the center of the polyimide film test piece cut out to a size of 10 cm ⁇ 10 cm was measured using a digital linear gauge (manufactured by Ozaki Mfg. Co., Ltd., model PDN12 digital gauge). was defined as the film thickness of the polyimide film.
  • the humidity expansion coefficient was measured using a steam TMA / S 8227A1 manufactured by Rigaku Corporation.
  • the polyimide film test piece cut out to 5 mm ⁇ 20 mm was dried at 120 ° C. for 10 minutes, and then the test piece was set so that the distance between chucks was 15 mm and the tensile load in the long side direction was 5 g.
  • the temperature is fixed at 25 ° C, the humidity is changed to 15% RH, 20% RH, and 50% RH, and the average elongation per humidity of 1% is calculated from the elongation amount of the test pieces of humidity 20% RH and 50% RH.
  • the calculation formula is as follows.
  • Humidity expansion coefficient (ppm /% RH) (X ⁇ 10 6 ) / (Y ⁇ Z)
  • X Value obtained by subtracting the test piece length at 20% RH from the test piece length at 50% RH
  • Y Humidity change amount when changing from 20% RH to 50% RH (50-20 (% RH ))
  • Test piece length at Z 20% RH Further, the elongation of the test piece was constantly monitored, recorded every second, and measured by the following procedure. In the following measurement, that the length of the test piece is constant means that the change in the test length for 30 minutes is 0.1 ⁇ m or less. 1. Hold for 30 minutes or more after the environment of the specimen is stable at 15% RH and the specimen length is constant and no longer changes.
  • Total light transmittance> Based on JIS K7361-1, it was measured with a haze meter (HM150, manufactured by Murakami Color Research Laboratory).
  • YI value (yellowness)>
  • the YI value is determined according to JIS K7373-2006 using an ultraviolet-visible near-infrared spectrophotometer (JASCO Corporation V-7100), by spectrocolorimetric method, using auxiliary illuminant C, and 2 degree field of view.
  • the tristimulus values X, Y, Z in the XYZ color system are obtained based on the transmittance measured in the range of 250 nm to 800 nm at 1 nm intervals, and the following formula is obtained from the X, Y, Z values. Calculated.
  • YI 100 (1.2769X ⁇ 1.0592Z) / Y
  • the metal piece 2 on which the test piece 1 was fixed was sandwiched between glass plates (100 mm ⁇ 100 mm ⁇ 0.7 mm) 3a and 3b from above and below, and the test piece 1 was fixed in a state of being bent with an inner diameter of 6 mm.
  • dummy test pieces 4a and 4b were sandwiched between portions of the metal piece 2 where the test piece 1 was not provided, and fixed with tape so that the glass plates 3a and 3b were parallel.
  • the test piece fixed in a bent state in this manner was left to stand for 24 hours in an environment of 60 ° C. and 90% relative humidity (RH) or in an environment of 70 ° C. and 20% relative humidity (RH) or less.
  • the glass plate and the test piece fixing tape were removed, and the force applied to the test piece was released. 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.
  • An inner angle of 120 ° or more was evaluated as A, and an inner angle of less than 120 ° was evaluated as B.
  • the inner angle is 180 °.
  • ⁇ Tensile modulus> A polyimide film test piece cut out to 15 mm ⁇ 40 mm was conditioned for 2 hours under the conditions of a temperature of 25 ° C. and a relative humidity of 60%. The tensile elastic modulus at 25 ° C. was measured. A tensile tester (manufactured by Shimadzu Corporation: Autograph AG-X 1N, load cell: SBL-1KN) was used.
  • ⁇ Tan ⁇ curve> The polyimide films of Examples 1 to 3 and Comparative Examples 1 to 3 were deformed by using a dynamic viscoelasticity measuring device DVA-225 (IT Measurement Control Co., Ltd.) with a measurement range of ⁇ 70 ° C. or more and 400 ° C. or less.
  • DVA-225 I Measurement Control Co., Ltd.
  • a dynamic viscoelasticity measuring device RSA-G2 (TA Instruments Japan Co., Ltd.) was used, and the measurement range was ⁇ 150 ° C. or higher and 490 ° C.
  • Tensile is selected as the deformation mode, and the dynamic viscoelasticity measurement is performed with a frequency of 1 Hz, a heating rate of 5 ° C./min, a sample width of 5 mm, and a distance between chucks of 20 mm.
  • E '') / storage elastic modulus (E ')) curve was obtained, and the temperature at the peak apex was determined.
  • the measurement conditions of the apparatus were set as follows.
  • ⁇ 2 ° C. RH 30 to 50% was sampled to a 10 cm square or more, and the center of the film was further removed with a razor or a scalpel.
  • a cutting tool having a slit with a width of 5 mm a product cut into a width of 5 mm ⁇ length of 50 mm (so that the sample length was 20 mm at the time of chucking) was used.
  • the width was measured using a caliper and the average value measured three times at different positions was recorded. At this time, when a part of the width measurement had a fluctuation range of 3% or more of the average value, the sample was not used.
  • the value measured by the film thickness measurement method was used for the thickness of the polyimide film.
  • Pencil hardness is determined by adjusting the measured sample for 2 hours under the conditions of a temperature of 25 ° C. and a relative humidity of 60%, and then using a test pencil specified by JIS-S-6006 using a pencil scratch film hardness made by Toyo Seiki Co., Ltd. A pencil hardness test (0.98 N load) specified in JIS K5600-5-4 (1999) was performed on the film surface using a thickness tester, and the highest pencil hardness without scratches was evaluated.
  • Synthesis Example 2 In the procedure of Synthesis Example 1, the reaction was performed so that the molar ratio of TFMB to AprMMOS (TFMB: AprTMOS) was 81:19, whereby a polyimide precursor solution 2 was obtained.
  • the viscosity at 25 ° C. of polyimide precursor solution 2 (solid content: 25% by weight) was 10180 cps, and the weight average molecular weight of polyimide precursor 2 measured by GPC was 109000.
  • the polyimide precursor solution 3 (solid content 20% by weight) in which the polyimide precursor 3 was dissolved was synthesized.
  • the viscosity of the polyimide precursor solution 3 (solid content 20% by weight) at 25 ° C. was 5560 cps, and the weight average molecular weight of the polyimide precursor 3 measured by GPC was 310000.
  • the molar ratio (TFMB: DATA) of TFMB and DATA used for the comparative polyimide precursor 2 was 80:20.
  • the viscosity of the comparative polyimide precursor solution 2 (solid content 20% by weight) at 25 ° C. was 27490 cps, and the weight average molecular weight of the comparative polyimide precursor 2 measured by GPC was 175000.
  • a comparative polyimide precursor solution 3 (solid content of 30% by weight) in which the comparative polyimide precursor 3 was dissolved was synthesized by gradually adding it into several times.
  • the viscosity at 25 ° C. of the comparative polyimide precursor solution 3 (solid content 30% by weight) was 4500 cps, and the weight average molecular weight of the comparative polyimide precursor 3 measured by GPC was 82,000.
  • Examples 1 to 3, Comparative Examples 1 to 3 Using the polyimide precursor solutions 1 to 3 and the comparative polyimide precursor solutions 1 to 3, the following steps (1) to (3) were performed to prepare polyimide films having thicknesses shown in Table 1, respectively.
  • Each polyimide precursor solution was applied on glass and dried in a circulating oven at 120 ° C. for 10 minutes.
  • the temperature was raised to 350 ° C. at a rate of temperature rise of 10 ° C./min, held for 1 hour, and then cooled to room temperature.
  • Each polyimide film was evaluated using the evaluation method. The evaluation results are shown in Table 1.
  • the tan ⁇ curve of the polyimide film of Example 2 is shown in FIG. In the measurement of the polyimide film of Example 2, a correct value was not obtained because the test piece melted in the temperature range of 350 ° C. or higher.
  • Table 1 shows that the polyimide films of Examples 1 to 3 corresponding to the polyimide film of the present disclosure are resin films having excellent transparency and improved bending resistance in a high humidity environment. In contrast, the polyimide films of Comparative Examples 1 to 3 were inferior in bending resistance in a high humidity environment. Moreover, the polyimide film of Comparative Example 1 had high yellowness (YI value) and was inferior in transparency.
  • Synthesis Example 4 By the procedure of Synthesis Example 1, the reaction was carried out so that the molar ratio of TFMB to AprMMOS (TFMB: AprTMOS) was 97.5: 2.5 to obtain polyimide precursor solution 4.
  • the viscosity at 25 ° C. of the polyimide precursor solution 4 (solid content 25% by weight) was 48900 cps, and the weight average molecular weight of the polyimide precursor 4 measured by GPC was 156400.
  • Example 4 In Example 1, a polyimide film having a thickness shown in Table 4 was produced in the same manner as in Example 1 except that the polyimide precursor solution 4 was used instead of the polyimide precursor solution 1. About the obtained polyimide film, it evaluated using the said evaluation method. The evaluation results are shown in Table 4.
  • Example 5 Preparation of polyimide (chemical imidization) A 1 L separable flask was charged with a solution in which dehydrated dimethylacetamide (466 g) and 1,3-bis (3-aminopropyl) tetramethyldisiloxane (AprTMOS) (1.31 g) were dissolved. 4,4 ′-(Hexafluoroisopropylidene) diphthalic anhydride (6FDA) (1.17 g) was gradually added to a temperature controlled at 30 ° C. so that the temperature rise was 2 ° C. or less. The mixture was stirred for 30 minutes with a mechanical stirrer.
  • dehydrated dimethylacetamide (466 g) and 1,3-bis (3-aminopropyl) tetramethyldisiloxane (AprTMOS) (1.31 g) were dissolved.
  • EprTMOS 1,3-bis (3-aminopropyl) tetramethyldisiloxane
  • Example 6 (1) Preparation of polyimide (chemical imidization)
  • the polyimide 6 of Example 6 was obtained in the same manner as in Example 5 except that the polyimide precursor solution 1 prepared in the same manner as in Synthesis Example 1 was used instead of the polyimide precursor solution 5. It was.
  • Table 3 shows the weight average molecular weight of polyimide 6 measured by GPC.
  • Example 5 (2) Manufacture of polyimide film
  • polyimide 6 instead of polyimide 5, polyimide 6 was used, and the solid content concentration was adjusted so as to be the concentration shown in Table 3.
  • the polyimide solution 6 shown in 3 was obtained.
  • Table 3 shows the viscosity of the polyimide solution 6 at 25 ° C.
  • a polyimide film of Example 6 was obtained in the same manner as in Example 5 except that the polyimide solution 6 was used instead of the polyimide solution 5 in Example 5.
  • Example 7 Preparation of polyimide (chemical imidization) A 5 L separable flask was charged with a solution in which dehydrated dimethylacetamide (250 g) and 1,3-bis (3-aminopropyl) tetramethyldisiloxane (AprTMOS) (4.14 g) were dissolved. 4,4 ′-(Hexafluoroisopropylidene) diphthalic anhydride (6FDA) (3.70 g) was gradually added to a temperature controlled at 30 ° C. so that the temperature rise was 2 ° C. or less. The mixture was stirred for 30 minutes with a mechanical stirrer.
  • AprTMOS 1,3-bis (3-aminopropyl) tetramethyldisiloxane
  • 6FDA 4,4 ′-(Hexafluoroisopropylidene) diphthalic anhydride
  • polyimide precursor solution 7 Under a nitrogen atmosphere, pyridine (26.3 g) as a catalyst and acetic anhydride (34.0 g) were added to the polyimide precursor solution 7 lowered to room temperature, and the mixture was stirred for 24 hours at room temperature to synthesize a polyimide solution.
  • the obtained polyimide solution (350 g) was put into a 5 L separable flask, butyl acetate (237 g) was added and stirred until uniform, and then methanol (1761 g) was gradually added to obtain a white slurry. The slurry was filtered and washed 5 times with methanol to obtain polyimide 7.
  • the weight average molecular weight of polyimide 7 measured by GPC was 230000.
  • Example 5 (2) Manufacture of polyimide film
  • polyimide 7 was used, and the solid content concentration was adjusted so as to be the concentration shown in Table 3.
  • the polyimide solution 7 shown in 3 was obtained.
  • Table 3 shows the viscosity of the polyimide solution 7 at 25 ° C.
  • a polyimide film of Example 7 was obtained in the same manner as in Example 5 except that the polyimide solution 7 was used instead of the polyimide solution 5 in Example 5.
  • Example 8 Preparation of polyimide (chemical imidization) A 1 L separable flask was charged with a solution in which dehydrated dimethylacetamide (105 g) and 1,3-bis (3-aminopropyl) tetramethyldisiloxane (AprTMOS) (11.81 g) were dissolved. 4,4 ′-(Hexafluoroisopropylidene) diphthalic anhydride (6FDA) (10.32 g) was gradually added to the temperature controlled at 30 ° C. so that the temperature rise was 2 ° C. or less. The mixture was stirred for 30 minutes with a mechanical stirrer.
  • dehydrated dimethylacetamide 105 g
  • AminTMOS 1,3-bis (3-aminopropyl) tetramethyldisiloxane
  • 6FDA 4,4 ′-(Hexafluoroisopropylidene) diphthalic anhydride
  • pyridine (0.39 g) as a catalyst and acetic anhydride (47.7 g) were added to the polyimide precursor solution 8 lowered to room temperature, and the mixture was stirred at room temperature for 24 hours to synthesize a polyimide solution.
  • butyl acetate (362 g) was added and stirred until uniform, then methanol (3000 g) was gradually added to obtain a white slurry.
  • the slurry was filtered and washed 10 times with methanol to obtain polyimide 8.
  • the weight average molecular weight of the polyimide measured by GPC was 78720.
  • Example 5 (2) Manufacture of polyimide film
  • polyimide 8 was used, and the solid content concentration was adjusted so as to be the concentration shown in Table 3.
  • the polyimide solution 8 shown in 3 was obtained.
  • Table 3 shows the viscosity of the polyimide solution 8 at 25 ° C.
  • a polyimide film of Example 8 was obtained in the same manner as in Example 5 except that the polyimide solution 8 was used instead of the polyimide solution 5 in Example 5.
  • the polyimide films of Examples 5 to 8 were evaluated using the above evaluation method. The evaluation results are shown in Table 4.
  • Table 4 shows that the polyimide films of Examples 4 to 8 corresponding to the polyimide film of the present disclosure are resin films having excellent transparency and improved bending resistance under a high humidity environment.
  • Example 9 10 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone (BASF, Irgacure 184) is added to 100 parts by weight of pentaerythritol triacrylate to a 40% by weight methyl isobutyl ketone solution of pentaerythritol triacrylate.
  • a resin composition for a coat layer was prepared.
  • the polyimide film of Example 1 was cut out to 10 cm ⁇ 10 cm, the hard coat layer resin composition was applied to the side not touching the glass plate during film production, and ultraviolet rays were exposed to 200 mJ / cm 2 under a nitrogen stream.
  • the hard coat layer which is a cured film having a thickness of 10 ⁇ m was formed by irradiating with an amount, and a laminate was produced.

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Abstract

L'invention concerne un film de polyimide qui comprend un polyimide présentant la structure représentée par la formule générale (1), le polyimide comprenant des cycles aromatiques et contenant au moins un atome ou une structure choisi dans le groupe constitué (i) d'un atome de fluor et (ii) de structures comprenant chacune des cycles aromatiques liés l'un à l'autre par un groupe sulfonyle ou un groupe alkylène éventuellement substitué par du fluor. Le polyimide donne une courbe tanδ, qui est une valeur obtenue par division du module de perte par le module de stockage, la courbe tanδ présentant un sommet de pic uniquement dans la plage de températures de 150 °C et plus. Le film de polyimide présente une transmittance lumineuse totale, telle que déterminée conformément à la norme JIS K 7361-1, égale ou supérieure à 85 %, un jaunissement, tel que calculé conformément à la norme JIS K7373-2006, égal ou inférieur à 12 et un coefficient d'expansion d'humidité égal ou inférieur à 10,0 ppm/% HR. (Dans la formule générale (1), les symboles sont tels que définis dans la description.)
PCT/JP2018/014168 2017-04-10 2018-04-02 Film de polyimide, produit stratifié et matériau de surface pour unité d'affichage WO2018190179A1 (fr)

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WO2023101005A1 (fr) * 2021-12-03 2023-06-08 住友化学株式会社 Film et résine de type polyimide
JP7480581B2 (ja) 2019-05-28 2024-05-10 東洋紡株式会社 ポリエステルフィルムとその用途

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JPH09302225A (ja) * 1996-03-14 1997-11-25 Toshiba Corp ポリイミド前駆体組成物、ポリイミド膜の形成方法、電子部品および液晶素子
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JP7480581B2 (ja) 2019-05-28 2024-05-10 東洋紡株式会社 ポリエステルフィルムとその用途
WO2023101005A1 (fr) * 2021-12-03 2023-06-08 住友化学株式会社 Film et résine de type polyimide

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