WO2020138045A1 - Film optique et dispositif d'affichage souple - Google Patents

Film optique et dispositif d'affichage souple Download PDF

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Publication number
WO2020138045A1
WO2020138045A1 PCT/JP2019/050541 JP2019050541W WO2020138045A1 WO 2020138045 A1 WO2020138045 A1 WO 2020138045A1 JP 2019050541 W JP2019050541 W JP 2019050541W WO 2020138045 A1 WO2020138045 A1 WO 2020138045A1
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WIPO (PCT)
Prior art keywords
formula
group
structural unit
represented
optical film
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Application number
PCT/JP2019/050541
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English (en)
Japanese (ja)
Inventor
紘子 杉山
皓史 宮本
池内　淳一
建太朗 増井
金　成民
ボラム 片
Original Assignee
住友化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority claimed from JP2019213442A external-priority patent/JP2021084941A/ja
Priority claimed from JP2019218189A external-priority patent/JP7365211B2/ja
Priority claimed from JP2019218184A external-priority patent/JP2020125454A/ja
Priority claimed from JP2019218259A external-priority patent/JP2020109154A/ja
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to KR1020217023795A priority Critical patent/KR20210110648A/ko
Priority to CN201980085975.XA priority patent/CN113227210A/zh
Publication of WO2020138045A1 publication Critical patent/WO2020138045A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/14—Polyamide-imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
    • 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
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to an optical film containing a polyamide-imide resin and a flexible display device including the optical film.
  • display devices such as liquid crystal display devices and organic EL display devices are widely used in various applications such as mobile phones and smart watches as well as televisions.
  • glass has been used as the front plate of such a display device.
  • glass has high transparency and can exhibit high hardness depending on the type, it is extremely rigid and easily broken, so that it is difficult to use it as a front plate material of a flexible display device.
  • the optical film used as the front plate material of a flexible display device is required to have a high appearance quality so that the color is evenly viewed from all viewing angles on the entire surface when applied to the display device.
  • the manufacturing equipment is cleaned with alcohol such as ethanol in the production process.
  • the residual alcohol in the manufacturing equipment may come into contact with the optical film, which may deteriorate the appearance quality of the optical film.
  • the user may wipe the surface with a cleaning agent containing an alcohol component for the purpose of cleaning the surface.
  • the appearance quality of the optical film may deteriorate depending on the contact state with the optical film.
  • an object of the present invention is to provide an optical film in which the appearance quality of the optical film is not impaired even when contacted with alcohol.
  • the present inventors have included a polyamide-imide resin having at least a specific constitutional unit, and have L * a * b * colorimetry in reflected light measurement before and after contact with alcohol.
  • the present invention has been completed by finding that an optical film having a change amount of brightness based on the system within a predetermined range has high appearance quality even after contact with alcohol.
  • R a independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and R a is The contained hydrogen atoms may be independently substituted with a halogen atom, n represents an integer of 0 to 2, * Represents a bond, R * represents a bond when Y is represented by formula (1), and represents R a when Z is represented by formula (1)] At least selected from the group consisting of the structural unit (a1) represented by the formula (a1) and Z in the formula (b) as a structural unit derived from the dicarboxylic acid compound, the structural unit (b1) represented by the formula (1).
  • the polyamide-imide-based resin has the following formula (2) as a constitutional unit derived from a dicarboxylic acid compound:
  • Z 1 represents a divalent aromatic group which is a monocyclic aromatic ring or a condensed polycyclic aromatic ring which may have a substituent, and * represents a bond.
  • X 1 represents a divalent aromatic group which may have a substituent, R c independently of each other represent a hydrogen atom or a bond, and * represents a bond.
  • the optical film as described in any of [1] to [4] above, which contains the structural unit (c1) represented by: [6] X 1 in formula (3) is formula (4):
  • R b independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and included in R b.
  • the hydrogen atoms may be independently substituted with a halogen atom, r is independently of each other an integer of 1 to 4, and * is a bond.
  • Z in the formula (b) as a constitutional unit derived from a dicarboxylic acid compound is represented by the formula (5):
  • Ar 1's each independently represent a divalent aromatic group which may have a substituent
  • V is a single bond, —O—, a diphenylmethylene group, a linear, branched or alicyclic divalent hydrocarbon group having 1 to 12 carbon atoms, —SO 2 —, —S—, —CO -Or-N(R 12 )-, wherein the hydrogen atoms contained in the hydrocarbon group may be independently substituted with a halogen atom, and R 12 is a hydrogen atom or a halogen atom.
  • Ar 2's each independently represent a trivalent aromatic group which may have a substituent, s represents an integer of 0 to 2, Ar 1, V and * are as defined for formula (5) Ar 1, V and in *, however, V and Ar 1 which s there are a plurality in the case of 2, respectively, was identical to one another Or they may be different, but V in the formula (6) is not a single bond]
  • the optical film as described in any one of [1] to [6] above, further including at least one structural unit selected from the group consisting of structural units (a2) represented by: [8] Equation (5) and Equation (6) are given by Equation (7):
  • R 1 is, independently of one another, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group or an aryl group having 6 to 12 carbon atoms having 1 to 12 carbon atoms, the R 1
  • the hydrogen atoms contained may be independently substituted with a halogen atom
  • R * represents R 1 or a bond
  • V is a single bond, —O—, a diphenylmethylene group, a linear, branched or alicyclic divalent hydrocarbon group having 1 to 12 carbon atoms, —SO 2 —, —S—, —CO -Or-N(R 12 )-, wherein the hydrogen atoms contained in the hydrocarbon group may be independently substituted with a halogen atom
  • R 12 is a hydrogen atom or a halogen atom.
  • the optical film of the present invention has high appearance quality that is not damaged by contact with alcohol.
  • optical film comprises a structural unit represented by formula (a) derived from a tetracarboxylic acid compound, a structural unit represented by formula (b) derived from a dicarboxylic acid compound, and a formula derived from a diamine compound.
  • R a independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and R a is The contained hydrogen atoms may be independently substituted with a halogen atom, n represents an integer of 0 to 2, * Represents a bond, R * represents a bond when Y is represented by formula (1), and represents R a when Z is represented by formula (1)] At least selected from the group consisting of the structural unit (a1) represented by the formula (a1) and Z in the formula (b) as a structural unit derived from the dicarboxylic acid compound, the structural unit (b1) represented by the formula (1).
  • the optical film of the present invention has a lightness L 1 * based on the L * a * b * colorimetric system in the reflected light measurement of the optical film and an L of the optical film after contact with ethanol for 40 minutes in the color difference measurement of the surface.
  • the absolute value ⁇ L * of the difference from the lightness L 2 * based on the * a * b * color system is 0.5 or less.
  • ⁇ L * exceeds 0.5, the appearance quality of the optical film is impaired by contact with ethanol.
  • ⁇ L * is preferably 0.3 or less, more preferably 0.2 or less, still more preferably 0.1 or less, and usually 0 or more, from the viewpoint of easily improving the appearance quality.
  • ⁇ L * is the absolute value of the difference between the lightness L 1 * in the reflected light measurement of the optical film of the present invention and the lightness L 2 * of the optical film after the optical film of the present invention was brought into contact with ethanol for 40 minutes. is there.
  • a method of bringing the optical film into contact with ethanol for 40 minutes a method of dropping ethanol onto the optical film, covering it with a cover glass, and maintaining the state where the optical film and ethanol are in contact with each other for 40 minutes is used. Specifically, the method described in the examples can be mentioned.
  • the lightness L * value based on the L * a * b * colorimetric system in the reflected light measurement can be measured by using a spectrocolorimeter under the conditions described in Examples, for example.
  • a method of setting ⁇ L * within the above range a method for producing an optical film using a polyamideimide resin described later, a film-forming solvent, a film drying condition, and a temperature are adjusted to adjust the amount of the solvent in the film. And a method of providing a protective layer.
  • ⁇ L * When adjusting ⁇ L * within the above range by adjusting the film-forming solvent, the drying conditions of the film, and the temperature to adjust the amount of solvent in the film, depending on the type of solvent, for example, By adjusting the amount of solvent in the film to 0.1% or more and 1.0% or less, ⁇ L * can be adjusted to a desired range. Further, when the [Delta] L * by a method of providing a protective layer is adjusted within the above range, by providing a protective layer of hard coating or the like to impart chemical resistance to the optical film, the [Delta] L * in the range of the Can be adjusted.
  • Y in the formula (a) is a structural unit (a1) represented by the formula (1) and Z in the formula (b) is represented by the formula (1).
  • the structure represented by the formula (1) is included in the polyamide-imide resin.
  • the structure represented by the formula (1) is a structure having high rigidity, and the skeleton of the polyamideimide resin contains a part having rigidity. As a result, it is thought that surprisingly, it becomes easier to improve the alcohol resistance of the obtained optical film and prevent the appearance quality of the optical film from being reduced by contact with alcohol.
  • a high appearance quality of the optical film is achieved.
  • the optical film is used as the front plate of the display device, the surrounding background is reflected on the optical film.
  • the background reflected on the optical film is visually recognized from various angles.
  • the reflected background is partially unclearly visually recognized, the user feels a sense of discomfort, and it is considered that the quality of the product is reduced.
  • such an appearance quality is, for example, a quality evaluated by the method described in the embodiment, and specifically, it is said that the reflected background is clearly visible without being partially blurred. It is quality.
  • Such appearance quality is easy to clearly determine, especially when the background is black.
  • ⁇ L * is the reflected light from the surface of the optical film. Shows how much changes were caused by contact with ethanol. Therefore, even if the change due to contact with ethanol is slight by visual observation, or even if almost no visual change is observed, when ⁇ L * is more than 0.5, the reflected light is slightly changed, so that the optical film is particularly suitable for flexible display. It is considered that when incorporated into a lens, etc., a white portion may appear depending on the angle, and the appearance quality of the optical film may be impaired.
  • the lightness L * value based on the L * a * b * color system in the reflected light measurement of the optical film of the present invention is preferably 5 or less, more preferably 3 or less, still more preferably 2.5 or less, and preferably It is 0 or more, more preferably 0.1 or more, and further preferably 0.2 or more.
  • the L * value is within the above range, the visibility becomes good when used as an optical film.
  • the absolute value ⁇ b * is preferably 0.1 or less, more preferably 0.08 or less, still more preferably 0.05 or less, and usually 0 or more.
  • ⁇ b * is the absolute value of the difference between b 1 * and b 2 * .
  • the method of bringing the optical film into contact with ethanol for 40 minutes is not particularly limited, and examples thereof include the method described in Examples.
  • the b * value based on the L * a * b * color system in the reflected light measurement can be measured by using the spectroscopic colorimetric property, for example, under the conditions described in the examples.
  • the amount of solvent in the film is adjusted by adjusting the method for producing an optical film using a polyamideimide-based resin described below, the film-forming solvent, the film drying conditions, and the temperature. And a method of providing a protective layer.
  • ⁇ b * is within the above range, the tint of the reflected light is likely to be uniform, and it is considered that the appearance quality is likely to be further improved.
  • the b * value based on the L * a * b * color system in the reflected light measurement of the optical film of the present invention is preferably 2 or less, more preferably 1 or less, still more preferably 0.5 or less, and preferably ⁇ It is 2 or more, more preferably -1 or more, and further preferably -0.5 or more.
  • the reflected light has no yellowish or bluish color and the appearance tends to be improved when used as an optical film.
  • the a * value based on the L * a * b * color system in the reflected light measurement of the optical film of the present invention is preferably 2 or less, more preferably 1 or less, still more preferably 0.5 or less, and preferably ⁇ It is 2 or more, more preferably -1 or more, and further preferably -0.5 or more.
  • the reflected light has no reddish or greenish color and the appearance tends to be improved when used as an optical film.
  • the content of the polyamideimide resin in the optical film is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, and further preferably 50 parts by mass with respect to 100 parts by mass of the optical film. It is at least 9 parts by mass, preferably at most 99.5 parts by mass, more preferably at most 95 parts by mass.
  • the content of the polyamideimide resin is within the above range, the appearance quality, optical characteristics, elastic modulus and total light transmittance of the optical film can be easily improved.
  • the thickness of the optical film of the present invention is preferably 25 ⁇ m or more, more preferably 30 ⁇ m or more, further preferably 35 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, still more preferably 60 ⁇ m or less. It may be a combination of upper and lower limits. When the thickness of the optical film is within the above range, the appearance quality and optical characteristics of the optical film can be easily improved.
  • the thickness of the optical film can be measured using a micrometer, for example, the method described in the examples.
  • the yellowness (hereinafter sometimes referred to as YI value) of the optical film of the present invention is preferably 7 or less, more preferably 4 or less, usually -5 or more, preferably -2 or more.
  • YI value of the optical film is less than or equal to the above upper limit, the transparency is good, and when used for the front plate of the display device, it is possible to contribute to high visibility.
  • the elastic modulus of the optical film of the present invention is preferably 5.2 GPa or more, more preferably 5.5 GPa or more, still more preferably 5.8 GPa or more, and even more, from the viewpoint of easily preventing wrinkles, scratches, and the like of the optical film. It is preferably 6.0 GPa or more, particularly preferably 6.2 GPa or more, particularly preferably 6.4 GPa or more, and usually 100 GPa or less.
  • the elastic modulus can be measured by using a tensile tester (distance between chucks: 50 mm, pulling speed: 10 mm/min), and can be measured, for example, by the method described in Examples.
  • the total light transmittance of the optical film of the present invention is preferably 80% or higher, more preferably 85% or higher, even more preferably 88% or higher, even more preferably 89% or higher, and particularly preferably 90% or higher. It is 100% or less.
  • the total light transmittance is not less than the above lower limit, it is easy to improve the visibility when the optical film is incorporated into a display device, particularly as a front plate. Since the optical film of the present invention usually exhibits a high total light transmittance, for example, as compared with the case of using a film having a low transmittance, the emission intensity of a display element or the like required to obtain constant brightness is suppressed. It becomes possible. Therefore, power consumption can be reduced.
  • the optical film of the present invention when the optical film of the present invention is incorporated into a display device, bright display tends to be obtained even if the light amount of the backlight is reduced, which can contribute to energy saving.
  • the total light transmittance can be measured by using a haze computer in accordance with JIS K 7361-1:1997, for example.
  • the total light transmittance may be the total light transmittance in the range of the thickness of the optical film described below.
  • the optical film having excellent optical properties means that the total light transmittance is high and/or the haze is low.
  • the haze of the optical film of the present invention is preferably 5% or less, more preferably 4% or less, even more preferably 3% or less, even more preferably 2.5% or less, particularly preferably 2% or less, and particularly preferably It is 1% or less, particularly preferably 0.8% or less, particularly preferably 0.5% or less, and usually 0.01% or more.
  • the haze of the optical film is equal to or less than the above upper limit, the visibility is likely to be enhanced when the optical film is incorporated into a display device, particularly as a front plate.
  • the haze can be measured using a haze computer according to JIS K 7136:2000.
  • the pencil hardness of at least one surface of the optical film of the present invention is preferably HB or higher, more preferably F or higher.
  • the pencil hardness can be measured according to JIS K 5600-5-4:1999.
  • the optical film of the present invention comprises a structural unit represented by formula (a) derived from a tetracarboxylic acid compound, a structural unit represented by formula (b) derived from a dicarboxylic acid compound, and a formula derived from a diamine compound.
  • a polyamide-imide resin having at least the following: in the polyamide-imide resin, Y in the formula (a) as a constitutional unit derived from the tetracarboxylic acid compound is represented by the formula (1):
  • R a independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and R a is The contained hydrogen atoms may be independently substituted with a halogen atom, n represents an integer of 0 to 2, * Represents a bond, R * represents a bond when Y is represented by formula (1), and represents R a when Z is represented by formula (1)] At least selected from the group consisting of the structural unit (a1) represented by the formula (a1) and Z in the formula (b) as a structural unit derived from the dicarboxylic acid compound, the structural unit (b1) represented by the formula (1).
  • constitutional unit represented by the formula (a) derived from the tetracarboxylic acid compound is also referred to as “constitutional unit (a)”
  • constitutional unit represented by the formula (b) derived from the dicarboxylic acid compound is represented by
  • constitutional unit (b) is also referred to
  • constitutional unit represented by the formula (c) derived from the diamine compound is also referred to as the "constitutional unit (c)”.
  • the polyamide-imide resin usually has a plurality of constituent units (a), a plurality of constituent units (b) and a plurality of constituent units (c), and optionally a plurality of other constituent units.
  • Y in the formula (a) as the structural unit (a) derived from the tetracarboxylic acid compound in the polyamideimide resin contained in the optical film of the present invention is represented by the formula (1).
  • Constaining the structural unit (a1) means that at least a part of the structural units (a) in the plurality of structural units (a) included in the polyamide-imide-based resin, Y in the formula (a) is represented by the formula (1). It means that it is the structural unit (a1).
  • the polyamide-imide-based resin contained in the optical film of the present invention is a structural unit (b1) in which Z in the formula (b) is a structural unit (b1) derived from a dicarboxylic acid compound (b1). ) Is included in the plurality of structural units (b) of the polyamide-imide resin, at least a part of the structural units (b) is a structural unit in which Z in the formula (b) is represented by the formula (1). (B1) is meant.
  • the above statements also apply to other similar statements herein.
  • the bonds in the formulas (a) to (c) are bonds that bond to adjacent structural units.
  • the polyamide-imide resin has at least the structural unit (a), the structural unit (b) and the structural unit (c), wherein the structural unit (a) and the diamine compound derived from the tetracarboxylic acid compound.
  • the structural unit (c) derived from is usually a compound of formula (D):
  • Z and X each independently represent a divalent organic group, and * represents a bond
  • the moiety having Y and four carbonyl groups in the formula (D) corresponds to the structural unit (a) derived from the tetracarboxylic acid compound, and the moiety having Z and two carbonyl groups in the formula (E) is It corresponds to the structural unit (b) derived from the dicarboxylic acid compound, and the moiety having X and the amino group in the formulas (D) and (E) corresponds to the structural unit (c) derived from the diamine compound.
  • X which represents a divalent organic group, has one bond bonded to the amino group.
  • the bond represented by * which is bonded to the adjacent constitutional unit is an amino group moiety in formula (D) or formula (E). Bind to. Therefore, it can be said that the portion having X and the amino group in the formulas (D) and (E) is a portion corresponding to the structural unit (c) derived from the diamine compound.
  • the polyamideimide-based resin includes a structural unit (a1) in which Y in the formula (a) as a structural unit (a) derived from a tetracarboxylic acid compound is represented by the formula (1), and a dicarboxylic acid.
  • Z in the formula (b) as the structural unit (b) derived from the compound includes at least one structural unit selected from the group consisting of the structural unit (b1) represented by the formula (1).
  • the polyamide-imide-based resin contained in the optical film of the present invention comprises Y as a structural unit (D) represented by the formula (1) and Z as a structural unit (E) represented by the formula (1). It has at least one constitutional unit selected from the group.
  • * in Formula (D) and Formula (E) represents a bond which couple
  • the polyamide-imide resin has a structural unit (a) derived from a tetracarboxylic acid compound, a structural unit (b) derived from a dicarboxylic acid compound, and a structural unit (c) derived from a diamine compound.
  • a structural unit (a) derived from a tetracarboxylic acid compound a structural unit (b) derived from a dicarboxylic acid compound
  • a structural unit (c) derived from a diamine compound derived from a diamine compound.
  • the polyamide-imide resin may further have a structural unit derived from a monomer other than the above.
  • the polyamide-imide resin is a structural unit (a) derived from one kind or two or more kinds of tetracarboxylic acid compounds, and a structural unit derived from one kind or two or more kinds of dicarboxylic acid compounds ( b) and at least a structural unit (c) derived from one or more kinds of diamine compounds, provided that at least a part of the structural unit (a) contains the structural unit (a1), or At least part of the unit (b) contains the structural unit (b1), or at least part of the structural unit (a) contains the structural unit (a1) and at least part of the structural unit (b) is structural. Including the unit (b1).
  • Y in the formula (a) as a constitutional unit derived from the tetracarboxylic acid compound is represented by the formula (1):
  • R a independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and R a is The contained hydrogen atoms may be independently substituted with a halogen atom, n represents an integer of 0 to 2, * Represents a bond, R * represents a bond when Y is represented by formula (1), and represents R a when Z is represented by formula (1)] At least selected from the group consisting of the structural unit (a1) represented by the formula (a1) and Z in the formula (b) as a structural unit derived from the dicarboxylic acid compound, the structural unit (b1) represented by the formula (1).
  • Y in the formula (a) may have one type of structural unit (a1) represented by the formula (1), or the formula (a Y in) may have two or more types of structural units (a1) represented by formula (1), and Z in formula (b) is one type represented by formula (1). It may have a structural unit (b1), Y in the formula (b) may have two or more types of structural units (b1) represented by the formula (1), or these You may have both.
  • Y in the formula (a) is represented by the formula (1) as a constitutional unit derived from the tetracarboxylic acid compound. It is preferable to include at least one structural unit (a1).
  • R a in the formula (1) independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and included in R a .
  • the hydrogen atoms represented may, independently of one another, be substituted by halogen atoms.
  • it is easy to increase the rigidity of the structure represented by the formula (1) it is easy to impart rigidity to the skeleton of the polyamide-imide resin, the appearance quality of the optical film of the present invention, total light transmission.
  • R a is independently of each other, preferably a hydrogen atom, a halogen atom-free alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or 6 carbon atoms.
  • R a is independently of each other, preferably a hydrogen atom, a halogen atom-free alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or 6 carbon atoms.
  • To 12 aryl groups more preferably C1 to C12 alkyl groups containing no hydrogen or halogen atoms, even more preferably C1 to C6 alkyl groups containing no hydrogen or halogen atoms, and even more preferably It represents a hydrogen atom or a halogen atom-free alkyl group having 1 to 3 carbon atoms, particularly preferably a hydrogen atom.
  • alkyl group having 1 to 12 carbon atoms examples include a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms.
  • linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-group.
  • alkyl group having 1 to 12 carbon atoms may be a linear alkyl group, a branched alkyl group, or an alicyclic alkyl group containing an alicyclic hydrocarbon structure.
  • the alkyl group having 1 to 12 carbon atoms preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 1 to 3 carbon atoms.
  • At least one hydrogen atom of the alkyl group having 1 to 12 carbon atoms is independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a carboxyl group. It may be a group substituted with.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the alkyl group having 1 to 12 carbon atoms is substituted with a substituent containing a carbon atom (for example, an alkyl group having 1 to 4 carbon atoms)
  • the number of carbon atoms contained in the substituent is It is not included in the number of carbon atoms of the alkyl group of the numbers 1 to 12.
  • the above-mentioned group in which an alkyl group having 1 to 12 carbon atoms is substituted with an alkyl group having 1 to 4 carbon atoms has an alkyl group having 1 to 12 carbon atoms as a main chain and at least one hydrogen atom of the alkyl group Is a group substituted with an alkyl group having 1 to 4 carbon atoms.
  • the total number of carbon atoms in the alkyl group may exceed 12.
  • a group in which an alkyl group having 1 to 12 carbon atoms is substituted with an alkyl group having 1 to 4 carbon atoms has 1 to 12 carbon atoms. It is a group included in the definition of a branched alkyl group.
  • alkoxy group having 1 to 12 carbon atoms examples include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, n-butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group. , Heptyloxy group, octyloxy group, nonyloxy group and decyloxy group.
  • the alkyl group portion and/or alkylene group portion in the alkoxy group having 1 to 12 carbon atoms may be linear, branched, or alicyclic.
  • the alkoxy group having 1 to 12 carbon atoms preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 1 to 3 carbon atoms.
  • at least one hydrogen atom is independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a carboxyl group. It may be a group substituted with.
  • the halogen atom include the atoms described above.
  • the alkoxy group having 1 to 12 carbon atoms is substituted with a substituent containing a carbon atom
  • the number of carbon atoms contained in the substituent is equal to the carbon number of the alkoxy group having 1 to 12 carbon atoms. exclude.
  • aryl group having 6 to 12 carbon atoms examples include phenyl group, tolyl group, xylyl group, naphthyl group, biphenyl group and the like.
  • the aryl group having 6 to 12 carbon atoms preferably has 6 or 10 or 12 carbon atoms.
  • at least one hydrogen atom is independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a carboxyl group. It may be a group substituted with.
  • the halogen atom include the atoms described above.
  • the number of carbon atoms contained in the substituent is smaller than that of the aryl group having 6 to 12 carbon atoms. exclude.
  • the hydrogen atoms contained in R a may be independently substituted with a halogen atom.
  • halogen atom include the atoms described above.
  • n represents an integer of 0 to 2
  • n is preferably 0 or 1, from the viewpoint of easily increasing the total light transmittance and elastic modulus of the optical film obtained by using the polyamideimide resin. It is more preferably 0.
  • Y in the formula (a) is represented by the formula (1)
  • * and R * in the formula (1) are moieties derived from a carboxyl group in a structural unit derived from a tetracarboxylic acid compound (for example, (Imido group portion) represents a bond to be bonded.
  • the tetracarboxylic acid compound means a compound having four carboxyl groups, a carboxylic acid halide of the compound, a carboxylic acid ester, and a carboxylic acid dianhydride in which two adjacent carboxyl groups are dehydrated and condensed.
  • the compound may be a compound selected from the group consisting of, and the tetracarboxylic acid compound is preferably tetracarboxylic dianhydride from the viewpoint of ease of polymerization during synthesis.
  • the tetracarboxylic acid compound in which Y in the formula (a) gives the structural unit (a1) represented by the formula (1) can be represented by the formula (8) when the tetracarboxylic acid compound is a tetracarboxylic dianhydride. :
  • the dicarboxylic acid compound may be a compound having two carboxyl groups, a carboxylic acid halide and/or a carboxylic acid ester of the compound.
  • the dicarboxylic acid compound in which Z in the formula (b) gives the structural unit (b1) represented by the formula (1) is, for example, when the dicarboxylic acid compound is dicarboxylic acid chloride, the formula (12):
  • R a and n are as defined in the formula (1)] It is represented by.
  • Y in the formula (a) is the structural unit (a1) represented by the formula (1) and Z in the formula (b) is the formula (1).
  • the total amount of the constituent units (b1) is preferably 2 to 45 mol%, more preferably 5 to 40%, and further preferably 10 to 40 mol% based on all the constituent units contained in the polyamide-imide resin. It is particularly preferably 15 to 35 mol %.
  • the total amount of the structural unit (a1) and the structural unit (b1) is at most the above upper limit, the total light transmittance of the optical film can be easily improved.
  • all structural units contained in the polyamide-imide resin represent all monomer units contained in the polyamide-imide resin.
  • the amounts of the structural unit (a1), the structural unit (b1) and all the structural units contained in the polyamide-imide resin can be measured using, for example, 1 H-NMR, or calculated from the charging ratio of the raw materials.
  • the total amount of the structural unit (a1) and the structural unit (b1) does not mean that both the structural unit (a1) and the structural unit (b1) are contained in the polyamide-imide resin, and in the invention, at least one of the structural unit (a1) and the structural unit (b1) may be contained in the polyamide-imide resin.
  • the polyamide-imide resin contained in the optical film may include at least the structural unit (a1) from the viewpoint of easily increasing the appearance quality, total light transmittance and elastic modulus of the optical film of the present invention. preferable.
  • the amount of the structural unit (a1) is a polyamide-imide-based resin. It is preferably 2 to 45 mol %, more preferably 5 to 40 mol %, further preferably 10 to 40 mol %, and particularly preferably 15 to 35 mol %, based on the total constitutional units contained in the resin.
  • the amount of the structural unit (a1) is at least the above lower limit, it is easy to improve the appearance quality and elastic modulus of the optical film.
  • the amount of the structural unit (a1) is at most the above upper limit, it is easy to improve the total light transmittance of the optical film.
  • the amounts of the structural unit (a1), the structural unit (b1) and all the structural units contained in the polyamide-imide resin can be measured using, for example, 1 H-NMR, or calculated from the charging ratio of the raw materials. You can also be measured using, for example, 1 H-NMR, or calculated from the charging ratio of the raw materials. You can also be measured using, for example, 1 H-NMR, or calculated from the charging ratio of the raw materials. You can also be measured using, for example, 1 H-NMR, or calculated from the charging ratio of the raw materials. You can also be measured using, for example, 1 H-NMR, or calculated from the charging ratio of the raw materials. You can also be measured using, for example, 1 H-NMR, or calculated from the charging ratio of the raw materials. You can also be measured using, for example, 1 H-NMR, or calculated from the charging ratio of the raw materials. You can
  • Formula (1) is preferably formula (1'):
  • the polyamide-imide-based resin contained in the optical film of the present invention comprises a structural unit (a1) in which Y in the formula (a) is represented by the formula (1).
  • Y in the formula (a) is represented by the formula (1).
  • it has at least a structural unit (b) derived from a dicarboxylic acid compound and a structural unit (c) derived from a diamine compound.
  • the polyamide-imide resin in this embodiment may have one type of structural unit (b), or may have two or more types of structural unit (b).
  • the polyamide-imide resin may have one type of structural unit (c), or may have two or more types of structural unit (c).
  • it may further have a structural unit derived from a tetracarboxylic acid compound different from the structural unit (a1), and the structural units (a) to (c) such as a structural unit derived from a tricarboxylic acid compound are It may have different further building blocks.
  • the polyamide-imide-based resin contained in the optical film of the present invention comprises a structural unit (b1) represented by the formula (1) in which Z in the formula (b) is a polyamide-imide-based resin.
  • Z in the formula (b) is a polyamide-imide-based resin.
  • it has at least a structural unit (a) derived from a tetracarboxylic acid compound and a structural unit (c) derived from a diamine compound.
  • the polyamide-imide-based resin in this embodiment may have one type of structural unit (a) or may have two or more types of structural unit (a).
  • the polyamide-imide resin may have one type of structural unit (c), or may have two or more types of structural unit (c).
  • a structural unit derived from a dicarboxylic acid compound different from the structural unit (b1) may further have a structural unit derived from a dicarboxylic acid compound different from the structural unit (b1), and is different from the structural units (a) to (c) such as a structural unit derived from a tricarboxylic acid compound.
  • You may have an additional structural unit.
  • the amount of the structural unit (b) derived from the dicarboxylic acid compound is preferably 5 to 70 mol% based on all the structural units contained in the polyamide-imide resin. , More preferably 10 to 65%, further preferably 20 to 60% by mole.
  • the amount of the structural unit (b) is at least the above lower limit, the solubility of the resin in the solvent is likely to be increased, and the stability of the varnish is easily increased. Further, when the amount of the structural unit (b) is at most the above upper limit, the elastic modulus can be easily increased.
  • the polyamide-imide-based resin includes the structural unit (b1) as the structural unit (b) derived from the dicarboxylic acid compound
  • the above range does not include the structural unit (b1) and other structural units (b1). It is preferable that the total amount of the structural units derived from the dicarboxylic acid (for example, the structural units (b2) and (b3) described later) be within the above range.
  • the amount of the structural unit (c) derived from the diamine compound is such that the structural unit (a) derived from the tetracarboxylic acid compound and the structural unit (d) derived from the dicarboxylic acid compound (
  • the total amount of b) is 100 mol %, preferably 95 to 105 mol %, more preferably 97 to 103 mol %, further preferably 98 to 102 mol %, and particularly preferably 99 to 101 mol %. is there.
  • the amount of the structural unit (c) is out of the above range, the molecular weight is hard to increase, and the stability of the varnish is likely to decrease.
  • the polyamide-imide resin has the formula (b) as the structural unit (b) derived from the dicarboxylic acid compound:
  • Z represents a divalent organic group and * represents a bond] It has a structural unit represented by.
  • * in the formula (b) is a bond which is connected to the structural unit (c) derived from the diamine compound, which is usually adjacent to the structural unit derived from the dicarboxylic acid compound in the polyamide-imide resin.
  • the structural unit (b) forms, for example, an amide bond represented by the above formula (E).
  • Z in the formula (b) is a divalent organic group, and preferably Z may be substituted with a hydrocarbon group having 1 to 8 carbon atoms or a fluorine-substituted hydrocarbon group having 1 to 8 carbon atoms
  • a divalent organic group having 4 to 40 carbon atoms more preferably a cyclic group which may be substituted with a hydrocarbon group having 1 to 8 carbon atoms or a fluorine-substituted hydrocarbon group having 1 to 8 carbon atoms. It is a divalent organic group having a structure and having 4 to 40 carbon atoms.
  • the cyclic structure include an alicyclic structure, an aromatic ring structure, and a heterocyclic structure.
  • Examples of the bond of the group represented by are a divalent organic group in which two non-adjacent two are replaced by hydrogen atoms and a divalent chain hydrocarbon group having 6 or less carbon atoms, and the heterocyclic structure of Z is A divalent organic group having a thiophene ring skeleton is exemplified.
  • a divalent organic group in which two non-adjacent bonds among the bonds of the groups represented by the formulas (20) to (27) are replaced by hydrogen atoms, and A divalent organic group having a thiophene ring skeleton is preferable, and the formula (20′), formula (21′), formula (22′), formula (23′), formula (24′), formula (25′), formula (26'), formula (27'), formula (28') and formula (29'):
  • a divalent organic group represented by is more preferable.
  • the hydrogen atom on the ring in formulas (20) to (29) and formulas (20′) to (29′) is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or It may be substituted with an aryl group having 6 to 12 carbon atoms (the hydrogen atom in these groups may be substituted with a halogen atom (preferably a fluorine atom)).
  • the structural unit (b) contained in the polyamide-imide resin may contain one kind of organic group as Z, or may contain two or more kinds of organic groups.
  • W 1 is a single bond, -O -, - CH 2 - , - CH 2 -CH 2 -, - CH (CH 3) -, - C (CH 3) 2 -, - C (CF 3) 2 -, - Ar 3 -, - SO 2 -, - CO -, - O-Ar 3 -O -, - Ar 3 -O-Ar 3 -, - Ar 3 -CH 2 -Ar 3 - , —Ar 3 —C(CH 3 ) 2 —Ar 3 — or —Ar 3 —SO 2 —Ar 3 —.
  • Ar 3 represents an arylene group having 6 to 20 carbon atoms in which a hydrogen atom may be replaced by a fluorine atom, and a specific example thereof is a phenylene group. When multiple Ar 3's are present, Ar 3's may be the same or different.
  • the polyamide-imide resin is a structural unit (b), and Z is a structural unit represented by any of the above formulas (20′) to (29′) (hereinafter, “structural units (b20′) to (b29).
  • structural units (b20′) to (b29) hereinafter, “structural units (b20′) to (b29).
  • the polyamide-imide-based resin has the following formula (d1):
  • R 24 is as defined in the formula (2-i) described later, R 25 represents R 24 or —C( ⁇ O)-*, and * represents a bond]
  • a structural unit represented by also referred to as “structural unit (d1)” below
  • structural unit (d1) specifically, a structural unit in which R 24 and R 25 are both hydrogen atoms, R 24 is both a hydrogen atom, and R 25 is —C( ⁇ O)—*.
  • the structural unit etc. to represent are mentioned.
  • the dicarboxylic acid compound that gives the structural unit (b) is not particularly limited as long as it is a compound having two carbonyl groups, and for example, the compound represented by the formula (b′):
  • Z represents a divalent organic group
  • R 31 and R 32 are, independently of each other, a hydroxyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and an n-butoxy group.
  • Group, sec-butoxy group, tert-butoxy group or chlorine atom The compound represented by
  • the structural unit (c) derived from the diamine compound of the polyamide-imide resin has the formula (c):
  • X represents a divalent organic group
  • R c independently represents a hydrogen atom or a bond
  • * represents a bond
  • the structural unit (c) represented by the formula (c) is usually a structural unit (a) derived from a tetracarboxylic acid compound or a structural unit (b) derived from a dicarboxylic acid compound in a polyamideimide resin. And is usually adjacent to, and forms, for example, an imide bond represented by the above formula (D) or an amide bond represented by the above formula (E).
  • R c's each independently represent a hydrogen atom or a bond.
  • R c represents a bond and an adjacent tetracarboxylic acid is bonded, as is clear from the formula (D).
  • R c represents a hydrogen atom, as is clear from the formula (E). ..
  • X in the formula (c) represents a divalent organic group, preferably a C4 to C40 divalent organic group, and more preferably a C4 to C40 divalent organic group having a cyclic structure. ..
  • the cyclic structure include an alicyclic structure, an aromatic ring structure, and a heterocyclic structure.
  • the organic group, the hydrogen atom in the organic group may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group, in which case, the carbon number of the hydrocarbon group and the fluorine-substituted hydrocarbon group is preferably Is 1 to 8.
  • the structural unit (c) contained in the polyamide-imide resin may contain one type of divalent organic group as X, or two or more types of divalent organic groups. May be included.
  • the diamine compound providing the structural unit (c) is not particularly limited as long as it is a compound having two amino groups, and for example, the compound represented by the formula (c′):
  • a tetracarboxylic acid compound for example, a compound represented by the formula (8)
  • a structural unit represented by the formula (1) and a formula (c′) Reaction with the diamine compound represented by formula (10):
  • R a and n are as defined for R a and n in formula (1)
  • X is as defined for X in the formula (c)
  • * represents a bond Represents]
  • a structural unit represented by is formed. Further, for example, when the dicarboxylic acid compound represented by the formula (b′) and the diamine compound represented by the formula (c′) react with each other, the formula (11):
  • the polyamide-imide resin has a constitution derived from a dicarboxylic acid compound in addition to at least one constitutional unit selected from the group consisting of the constitutional unit (a1) and the constitutional unit (b1).
  • the formula (2) As the unit (b), the formula (2):
  • Z 1 represents a divalent aromatic group which may have a substituent and is a monocyclic aromatic ring or a condensed polycyclic aromatic ring, and * represents a bond.
  • the structural unit (b2) represented by The polyamide-imide resin usually has a plurality of structural units (b) represented by the formula (b). In this aspect, at least a part of the plurality of structural units (b) may be the structural unit (b2) represented by the formula (2).
  • the polyamide-imide resin in the present invention may have one type of structural unit (b2) as the structural unit (b), or may have two or more types of structural unit (b2). Or may have a structural unit (b) other than the structural unit (b2).
  • Z 1 in the formula (2) represents a divalent aromatic group which may have a substituent.
  • the divalent aromatic group is a group in which two hydrogen atoms of a monocyclic aromatic ring or a condensed polycyclic aromatic ring are replaced with a bond.
  • the divalent aromatic group may include an aromatic ring in which a ring (monocycle or condensed polycycle) is formed only by carbon atoms, or a heterocycle in which a ring is formed by including atoms other than carbon atoms. It may contain an aromatic ring. Examples of atoms other than carbon atoms include nitrogen atoms, sulfur atoms and oxygen atoms.
  • the total number of carbon atoms and atoms other than carbon atoms forming the aromatic ring is not particularly limited, but is preferably 5 to 18, more preferably 5 to 14, further preferably 5 to 13, and particularly preferably 5 to 12. Is.
  • Examples of the monocyclic aromatic ring include benzene, furan, pyrrole, thiophene, pyridine, imidazole, pyrazole, oxazole, thiazole and imidazoline.
  • condensed polycyclic aromatic ring examples include naphthalene, anthracene, phenanthrene, indole, benzothiazole, benzoxazole, benzimidazole and the like.
  • the divalent aromatic group which may have a substituent is preferably two hydrogen atoms of an aromatic hydrocarbon ring.
  • a group in which an atom is replaced by a bond more preferably a group in which two hydrogen atoms of benzene, biphenyl, terphenyl or quaterphenyl are replaced by a bond, and more preferably two hydrogen atoms of benzene or biphenyl are bonded.
  • the divalent aromatic group represented by Z 1 in formula (2) may have a substituent.
  • substituents include (i) an alkyl group having 1 to 12 carbon atoms, (ii) an alkoxy group having 1 to 12 carbon atoms, (iii) an aryl group having 6 to 12 carbon atoms, and (iv) having 6 to 12 carbon atoms. 12 aryloxy groups and at least one group selected from the group consisting of (v) hydroxyl groups.
  • the hydrogen atoms contained in the above substituents are independently substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a carboxyl group. Good.
  • the substituents (i) to (v) and the hydrogen atoms contained in the substituents (i) to (v) are independently a halogen atom or a carbon number. It may have at least one substituent selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a group further substituted with a carboxyl group, It may not have a substituent.
  • the divalent aromatic group represented by Z 1 in the formula (2) preferably has no substituent.
  • Examples of the aryloxy group having 6 to 12 carbon atoms include phenoxy group, tolyloxy group, xylyloxy group, naphthyloxy group and biphenyloxy group.
  • the aryloxy group having 6 to 12 carbon atoms preferably has 6 or 10 or 12 carbon atoms.
  • at least one hydrogen atom is independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a carboxyl group. It may be a group substituted with a group.
  • Examples of the halogen atom include the atoms described above.
  • the number of carbon atoms contained in the substituent is the same as that of the aryloxy group having 6 to 12 carbon atoms. Not included in.
  • the polyamide-imide-based resin contains a structural unit (b2) represented by the formula (2) as a structural unit (b) derived from a dicarboxylic acid compound.
  • the ratio of the structural unit (b2) represented by the formula (2) when the total of the structural units (b) contained in the polyamide-imide resin is 100 mol %.
  • the contents of the structural unit (b) and the structural unit (b2) can be measured, for example, using 1 H-NMR, or can be calculated from the charging ratio of the raw materials.
  • the polyamide-imide resin contains a structural unit (b2) in addition to at least one structural unit selected from the group consisting of the structural unit (a1) and the structural unit (b1) above,
  • the structural unit (b2) represented by the formula (2) is more preferably the following formula (2-i):
  • R 24 is, independently of each other, a hydrogen atom, (i) an alkyl group having 1 to 12 carbon atoms, (ii) an alkoxy group having 1 to 12 carbon atoms, and (iii) having 6 carbon atoms.
  • aryl group (iv) aryloxy group having 6 to 12 carbon atoms or (v) hydroxyl group, and the hydrogen atom contained in R 24 may be substituted with a halogen atom, preferably a hydrogen atom , * Represents a bond] It is represented by.
  • the polyamide-imide resin has a structural unit represented by the formula (2-i) (hereinafter also referred to as “structural unit (b2-i)”).
  • the polyamide-imide-based resin further has a structural unit (d1) represented by the above formula (d1) in addition to the above structural unit (b2-i). It is preferable from the viewpoint that the film-forming property is easily improved and the uniformity of the obtained optical film is easily improved.
  • the polyamide-imide resin has a structural unit derived from a diamine compound represented by the formula (3):
  • X 1 represents a divalent aromatic group which may have a substituent, R c independently of each other represent a hydrogen atom or a bond, and * represents a bond.
  • the structural unit (c1) represented by The polyamide-imide resin usually has a plurality of structural units (c) represented by the formula (c). In this aspect, at least a part of the plurality of structural units (c) may be the structural unit (c1) represented by the formula (3).
  • the polyamide-imide resin contained in the optical film of the present invention may have one type of structural unit (c1) as the structural unit (c), or two or more types of structural unit (c1). Or may have a structural unit (c) other than the structural unit (c1).
  • X 1 in the formula (3) represents a divalent aromatic group which may have a substituent.
  • the divalent aromatic group is a group in which two hydrogen atoms of a monocyclic aromatic ring, a condensed polycyclic aromatic ring or a ring-assembled aromatic ring are replaced by a bond.
  • the divalent aromatic group may include an aromatic ring in which a ring (monocycle, condensed polycycle or ring assembly) is formed only by carbon atoms, or a ring formed by including an atom other than carbon atoms.
  • the heteroaromatic ring may be included. Examples of atoms other than carbon atoms include nitrogen atoms, sulfur atoms and oxygen atoms.
  • the total number of carbon atoms and atoms other than carbon atoms forming the aromatic ring is not particularly limited, but is preferably 5 to 18, more preferably 5 to 14, further preferably 5 to 13, and particularly preferably 5 to 12. Is.
  • Examples of the monocyclic aromatic ring and the condensed polycyclic aromatic ring include the examples described above for Z 1 in formula (2).
  • Examples of the ring-assembled aromatic ring include a structure in which two or more monocyclic aromatic rings and/or fused polycyclic aromatic rings are linked by a single bond, and examples thereof include monocyclic aromatic rings.
  • a group in which two or more of the rings described above as examples of the aromatic ring or the condensed polycyclic aromatic ring are linked by a single bond for example, biphenyl, terphenyl, quaterphenyl, binaphthyl, 1-phenylnaphthalene, 2-phenyl Examples thereof include naphthalene and bipyridine.
  • the divalent aromatic group which may have a substituent may preferably have a substituent.
  • a group in which two hydrogen atoms of an aromatic hydrocarbon ring are replaced by bonds, more preferably two hydrogen atoms of benzene, biphenyl, terphenyl or quaterphenyl which may have a substituent are replaced by bonds.
  • the divalent aromatic group represented by X 1 in formula (3) may have a substituent.
  • substituents include an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a halogeno group, and a hydrogen atom contained therein is a halogen atom. Substituted groups are mentioned.
  • alkyl group having 1 to 12 carbon atoms examples include:
  • the alkoxy group having 1 to 6 carbon atoms, the aryl group having 6 to 12 carbon atoms, and the group in which a hydrogen atom contained in these is substituted with a halogen atom examples include:
  • the divalent aromatic group represented by Z 1 in (2) may have, (i) an alkyl group having 1 to 12 carbon atoms, (ii) an alkoxy group having 1 to 12 carbon atoms, and (iii) )
  • the groups described for the aryl group having 6 to 12 carbon atoms can be mentioned.
  • the halogeno group examples include a fluoro group, a chloro group, a bromo group and an iodo group.
  • the substituent which the divalent aromatic group represented by X 1 in the formula (3) may have is a halogen group or a C 1-12 carbon atom in which a hydrogen atom may be substituted with a halogen atom.
  • An alkyl group is preferable, and a methyl group, a fluoro group, a chloro group or a trifluoromethyl group is more preferable.
  • X 1 in the formula (3) is preferably from the viewpoint of easily increasing the total light transmittance and elastic modulus as well as the appearance quality of the optical film, and from the viewpoint of easily increasing the stability of the varnish.
  • R b independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and included in R b.
  • the hydrogen atoms may be independently substituted with a halogen atom, r is independently of each other an integer of 1 to 4, and * is a bond.
  • R b in the formula (4) independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and hydrogen contained in R b.
  • the atoms may, independently of one another, be substituted by halogen atoms.
  • Examples of the alkyl group having 1 to 6 carbon atoms, the aryl group having 6 to 12 carbon atoms, and the alkoxy group having 1 to 6 carbon atoms include a divalent aromatic group represented by X 1 in the formula (3).
  • substituent that may be included include the groups exemplified above.
  • R b in the formula (4) is preferably an alkyl group having 1 to 6 carbon atoms, which is substituted with a halogen atom, more preferably a fluoroalkyl group having 1 to 6 carbon atoms, and further preferably a per alkyl group having 1 to 6 carbon atoms.
  • r's each independently represent an integer of 1 to 4, preferably 1 to 3, and more preferably 1 to 2 from the viewpoint of easily improving the total light transmittance and elastic modulus of the optical film. , Particularly preferably an integer of 1.
  • the formula (4) is the formula (4'):
  • R 16 to R 23 each independently represent a hydrogen atom or a fluoroalkyl group having 1 to 6 carbon atoms, provided that at least one of R 16 to R 19 and R 20 At least one of to R 23 represents a fluoroalkyl group having 1 to 6 carbon atoms, and * represents a bond.
  • R 18 and R 20 represent a fluoroalkyl group having 1 to 6 carbon atoms in the formula (4′), It is further preferred that R 18 and R 20 represent a fluoroalkyl group having 1 to 6 carbon atoms, and R 16 , R 17 , R 19 , R 21 , R 22 and R 23 represent a hydrogen atom.
  • the fluoroalkyl group having 1 to 6 carbon atoms is preferably a perfluoroalkyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkyl group having 1 to 4 carbon atoms, and further preferably trifluoromethyl.
  • the formula (4') is the formula (4":
  • [* in formula (4") represents a bond] It is represented by.
  • R 18 and R 20 in the formula (4′) represent a trifluoromethyl group
  • R 16 , R 17 , R 19 , R 21 , R 22 and R 23 represent hydrogen atoms.
  • R 16 , R 17 , R 19 , R 21 , R 22 and R 23 represent hydrogen atoms.
  • the polyamide-imide resin contains a structural unit (c1) represented by formula (3) as a structural unit (c) derived from a diamine compound, in addition to the appearance quality of the optical film, the total light transmittance And from the viewpoint of easily improving the elastic modulus and the stability of the varnish, the composition represented by the formula (3) when the total of the constituent units (c) contained in the polyamide-imide resin is 100 mol %.
  • the proportion of the unit (c1) is preferably 50 to 98 mol%, more preferably 60 to 95 mol%, and further preferably 70 to 94 mol%.
  • a part of the structural unit (c) contained in the polyamide-imide resin may be the structural unit (c1), or all of the structural unit (c) may be the structural unit (c1), but an optical film From the viewpoint of easily improving the total light transmittance and the elastic modulus as well as the stability of the varnish together with the appearance quality of, part of the structural unit (c) contained in the polyamide-imide resin is the structural unit (c1). It is preferable to have.
  • the contents of the structural unit (c) and the structural unit (c1) can be measured using, for example, 1 H-NMR, or can be calculated from the raw material charging ratio.
  • the polyamide-imide resin contained in the optical film of the present invention is derived from a tetracarboxylic acid compound from the viewpoint of easily improving the total light transmittance and the elastic modulus together with the appearance quality of the optical film and easily increasing the stability of the varnish.
  • Y in the formula (a) includes the structural unit (a1) represented by the formula (1), and as the structural unit derived from the dicarboxylic acid compound, the structural unit (b1) represented by the formula (2). And a structural unit (c1) represented by the formula (3) as a structural unit derived from the diamine compound.
  • Z in the formula (b) is represented by the formula (5):
  • Ar 1's each independently represent a divalent aromatic group which may have a substituent
  • V is a single bond, —O—, a diphenylmethylene group, a linear, branched or alicyclic divalent hydrocarbon group having 1 to 12 carbon atoms, —SO 2 —, —S—, —CO -Or-N(R 12 )-, wherein the hydrogen atoms contained in the hydrocarbon group may be independently substituted with a halogen atom, and R 12 is a hydrogen atom or a halogen atom.
  • Ar 2's each independently represent a trivalent aromatic group which may have a substituent, s represents an integer of 0 to 2, Ar 1, V and * are as defined for formula (5) Ar 1, V and in *, however, V and Ar 1 which s there are a plurality in the case of 2, respectively, was identical to one another Or they may be different, but V in the formula (6) is not a single bond]
  • at least one constitutional unit selected from the group consisting of constitutional units represented by a structural unit represented by formula (5) in which Z in the formula (b) that may be contained as a structural unit derived from a dicarboxylic acid compound is also referred to as a “structural unit (b3)”, and a diamine compound
  • the constitutional unit represented by the formula (5) is also referred to as “constitutional unit (c2)” and is included as a constitutional unit derived from the tetracarboxylic acid compound.
  • the constitutional unit in which Y in the formula (a) to be obtained is represented by the formula (6) is also referred to as “constitutional unit (a2)”.
  • the polyamide-imide resin contained in the optical film of the present invention contains at least one structural unit (preferably the structural unit (a1)) selected from the group consisting of the structural unit (a1) and the structural unit (b1).
  • the composition further includes at least one structural unit selected from the group consisting of the structural unit (b3), the structural unit (c2) and the structural unit (a2).
  • the structural unit in addition to the constitutional unit represented by the formula (1), at least one selected from the group consisting of the constitutional unit represented by the formula (5) and the constitutional unit represented by the formula (6).
  • the structural unit will be included in the polyamide-imide resin.
  • the structural unit (b3) is included as the structural unit (b), the structural unit (c2) is included as the structural unit (c), and the structural unit (a2) is included as the structural unit (a).
  • the polyamide-imide-based resin includes the structural unit (b3) as the structural unit (b)
  • the resin may include the structural unit (b1) or the structural unit (b2)
  • the structural units (b1) and (b2) may be contained, or the structural units (b1) and (b2) may not be contained.
  • the polyamide-imide resin contains the structural unit (c2) as the structural unit (c)
  • the resin may or may not include the structural unit (c1).
  • the constitutional unit represented by the formula (5) and the constitutional unit represented by the formula (6) are a single bond (provided that V in the formula (6) is not a single bond), —O—, diphenylmethylene.
  • the polyamide-imide-based resin further includes the highly flexible structure as described above, it becomes easy to reduce the interaction between the molecules of the polyamide-imide-based resin. As a result, it is easy to improve the optical characteristics of the optical film containing the polyamide-imide resin. In addition, the stability of the polyamide-imide resin in the varnish state is easily improved.
  • Z in formula (b) is a structural unit (b2) derived from a dicarboxylic acid compound represented by formula (5), and X in formula (c) is represented by formula (5).
  • the total amount of the constitutional unit (b2), the constitutional unit (c2) and the constitutional unit (a2) is preferably 1 to 25 mol% based on all constitutional units contained in the polyamide-imide resin.
  • the total amount of the structural unit (b2), the structural unit (c2) and the structural unit (a2) does not mean that the polyamide-imide resin has all of these three types of structural units.
  • the polyamide-imide resin may have at least one structural unit selected from the group consisting of structural unit (b2), structural unit (c2) and structural unit (a2).
  • the Y in the formula (a) contained in the polyamide-imide resin is the structural unit (a1) and the formula (b) represented by the formula (1).
  • Z is preferably 0.01 to 1.0 mol, more preferably 0.02 to 0.50 mol, when the total amount of the structural units (b1) represented by formula (1) is 1 mol. , And more preferably 0.05 to 0.20 mol.
  • the above total molar amount does not mean that the polyamide-imide resin has all of these constituent units.
  • Ar 1 in the formulas (5) and (6) represents a divalent aromatic group which may have a substituent.
  • the divalent aromatic group is a group in which two hydrogen atoms of a monocyclic aromatic ring, a condensed polycyclic aromatic ring or a ring-assembled aromatic ring are replaced by a bond.
  • the divalent aromatic group may include an aromatic ring in which a ring (monocycle, condensed polycycle or ring assembly) is formed only by carbon atoms, or a ring formed by including an atom other than carbon atoms.
  • the heteroaromatic ring may be included. Examples of atoms other than carbon atoms include nitrogen atoms, sulfur atoms and oxygen atoms.
  • the total number of carbon atoms and atoms other than carbon atoms forming the aromatic ring is not particularly limited, but is preferably 5 to 18, more preferably 5 to 14, further preferably 5 to 13, and particularly preferably 5 to 12. Is.
  • Examples of the monocyclic aromatic ring, the condensed polycyclic aromatic ring, and the ring-assembled aromatic ring include the examples described above for Z 1 in the formula (2).
  • the divalent aromatic group which may have a substituent is preferably two hydrogen atoms of the aromatic hydrocarbon ring.
  • the divalent aromatic group represented by Ar 1 in formulas (5) and (6) may have a substituent.
  • substituents include (i) an alkyl group having 1 to 12 carbon atoms, (ii) an alkoxy group having 1 to 12 carbon atoms, (iii) an aryl group having 6 to 12 carbon atoms, and (iv) having 6 to 12 carbon atoms. And an aryloxy group having 12 carbon atoms, a (v) carbonyl group having 1 to 12 carbon atoms, (vi) an oxycarbonyl group having 1 to 12 carbon atoms, or (vii) a halogeno group.
  • the hydrogen atoms contained in the above substituents are independently substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a carboxyl group.
  • a halogen atom an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a group further substituted with a carboxyl group, or has a substituent. You don't have to. From the viewpoint of easy production of an optical film having a high elastic modulus, it is preferable that the divalent aromatic group represented by Ar 1 in Formula (5) and Formula (6) does not have a substituent.
  • R d include (i) the group described for the alkyl group having 1 to 12 carbons, and R e includes (i) at least one hydrogen atom of the group described for the alkyl group having 1 to 12 carbons. And a divalent alkylene group having 1 to 12 carbon atoms in which is replaced by a bond.
  • At least one hydrogen atom independently of each other is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a carboxyl group. It may be a group substituted with.
  • the halogen atom include the atoms described above.
  • the carbonyl group having 1 to 12 carbon atoms is substituted with a substituent containing a carbon atom, the number of carbon atoms contained in the substituent is equal to the carbon number of the carbonyl group having 1 to 12 carbon atoms. exclude.
  • the oxycarbonyl group having 1 to 12 carbon atoms is *-CO-OR d , *-R e -CO-OR d , *-O-CO-R d , or -R e-. It is a group represented by O—CO—R d .
  • R d include (i) the group described for the alkyl group having 1 to 12 carbons, and R e includes (i) at least one hydrogen atom of the group described for the alkyl group having 1 to 12 carbons. And a divalent alkylene group having 1 to 12 carbon atoms in which is replaced by a bond.
  • At least one hydrogen atom independently of one another is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a carboxyl group. It may be a group substituted with a group.
  • the halogen atom include the atoms described above.
  • the oxycarbonyl group having 1 to 12 carbon atoms is substituted with a substituent containing a carbon atom
  • the number of carbon atoms contained in the substituent is the number of carbon atoms of the oxycarbonyl group having 1 to 12 carbon atoms. Not included in.
  • Examples of the (vii) halogeno group include a fluoro group, a chloro group, a bromo group and an iodo group.
  • Ar 2 in the formula (6) represents a trivalent aromatic group which may have a substituent.
  • the trivalent aromatic group is a group in which three hydrogen atoms of a monocyclic aromatic ring, a condensed polycyclic aromatic ring or a ring-assembled aromatic ring are replaced by bonds.
  • the trivalent aromatic group may include an aromatic ring in which a ring (monocycle, condensed polycycle or ring assembly) is formed only by carbon atoms, or a ring formed by including an atom other than carbon atoms.
  • the heteroaromatic ring may be included. Examples of atoms other than carbon atoms include nitrogen atoms, sulfur atoms and oxygen atoms.
  • the total number of carbon atoms and atoms other than carbon atoms forming the aromatic ring is not particularly limited, but is preferably 5 to 18, more preferably 5 to 14, further preferably 5 to 13, and particularly preferably 5 to 12. Is.
  • Examples of the monocyclic aromatic ring, condensed polycyclic aromatic ring or ring-assembled aromatic ring in the trivalent aromatic group include those described for Ar 1 above.
  • Examples of the substituent that the trivalent aromatic group may have include the substituents described above for Ar 1 , and the preferable descriptions described for Ar 1 also apply to Ar 2 .
  • the trivalent aromatic group which may have a substituent is preferably three hydrogen atoms of the aromatic hydrocarbon ring. Is a group in which three hydrogen atoms of benzene, biphenyl, terphenyl or quaterphenyl are replaced by a bond, and more preferably three hydrogen atoms of benzene or biphenyl are a bond. Is the group replaced by.
  • a plurality of Ar 1 s may be the same or different from each other.
  • a plurality of Ar 2 s present in the formula (6) may be the same or different from each other.
  • M in the formula (5) represents an integer of 1 to 3, and is preferably 1 or 2, and more preferably 1 from the viewpoint of improving the elastic modulus and ensuring the solubility in varnish.
  • * In Formula (5) represents a bond.
  • S in the formula (6) represents an integer of 0 to 2, and is preferably 0 or 1, and more preferably 0 from the viewpoint of ensuring solubility in varnish and high transmittance.
  • * In Formula (6) represents a bond.
  • V in the formulas (5) and (6) is a single bond (however, V in the formula (6) is not a single bond), —O—, a diphenylmethylene group, a straight chain having 1 to 12 carbon atoms, Represents a branched or alicyclic divalent hydrocarbon group, —SO 2 —, —S—, —CO— or —N(R 12 )—, wherein the hydrogen atom contained in the hydrocarbon group May independently of each other be substituted with a halogen atom, and R 12 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom.
  • Examples of the linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms include the groups described for the alkyl group having 1 to 12 carbon atoms of R a in formula (1).
  • the linear, branched or alicyclic divalent hydrocarbon group having 1 to 12 carbon atoms is a straight chain having 1 to 12 carbon atoms.
  • Examples of the linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and sec-butyl group.
  • the divalent hydrocarbon group having 1 to 12 carbon atoms may be a linear alkylene group, a branched alkylene group, or an alicyclic alkylene group containing an alicyclic hydrocarbon structure.
  • the divalent hydrocarbon group having 1 to 12 carbon atoms preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 1 to 3 carbon atoms.
  • the divalent hydrocarbon group having 1 to 12 carbon atoms may be a group in which at least one hydrogen atom is independently substituted with a halogen atom.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • R 1 is, independently of one another, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group or an aryl group having 6 to 12 carbon atoms having 1 to 12 carbon atoms, the R 1
  • the contained hydrogen atoms may be independently substituted with a halogen atom
  • R * represents R 1 or a bond
  • V is a single bond (however, V in the formula (6) is not a single bond)
  • —O— a diphenylmethylene group, a linear, branched or alicyclic divalent group having 1 to 12 carbon atoms.
  • R 12 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom.
  • the polyamide-imide-based resin has a constitutional unit derived from a diamine compound, wherein X in the formula (c) is a constitutional unit (c2) represented by the formula (5) or the formula (7).
  • X in the formula (c) is a constitutional unit (c2) represented by the formula (5) or the formula (7).
  • Y in the formula (a) further contains a constitutional unit (a2) represented by the formula (6) or (7)
  • the formula (5 ), V in the formulas (6) and (7) is preferably from the viewpoints of appearance quality of the optical film, elastic modulus, total light transmittance, surface hardness and flex resistance, and stability of the varnish.
  • diphenylmethylene group linear, branched or alicyclic divalent hydrocarbon group having 1 to 12 carbon atoms, -SO 2 -, -S-, -CO- or -N(R 12 )-, more preferably —O—, a diphenylmethylene group, a linear, branched or alicyclic divalent hydrocarbon group having 1 to 12 carbon atoms, or a carbon atom having 1 to 12 carbon atoms.
  • It represents a group in which a hydrogen atom contained in a divalent hydrocarbon group is replaced by a halogen atom, and more preferably a divalent hydrocarbon group having 1 to 12 carbon atoms or a divalent hydrocarbon group having 1 to 12 carbon atoms. It represents a group in which a hydrogen atom contained in a hydrogen group is substituted with a halogen atom.
  • V in the formulas (5), (6) and (7) is more preferably at least one of linear, branched or alicyclic alkylene groups having 1 to 12 carbon atoms.
  • a group (preferably a perfluoroalkylene group having 1 to 12 carbon atoms, particularly preferably a ditrifluoromethylmethylene group) in which all hydrogen atoms of the alicyclic alkylene group are substituted with halogen atoms (preferably fluorine atoms). ..
  • formula (7) is preferably formula (7'):
  • the polyamide-imide resin contains a structural unit (b3) represented by the formula (5) in the formula (b) as a structural unit derived from the dicarboxylic acid compound, the formula (5) is represented by the formula (7). Is more preferable, and formula (7) is more preferably represented by formula (7′′).
  • the polyamide-imide resin has the above structural unit (a1), structural unit (b) and structural unit (c), and Y in the formula (a) is represented by the formula (6). It has a structural unit (a2) derived from a tetracarboxylic acid compound represented by.
  • the amount of the structural unit (a2) is preferably 1 to 25 mol%, more preferably 2 to 20 mol%, further preferably 3 to 15 mol, based on all the structural units contained in the polyamide-imide resin. %.
  • the amount of the structural unit (a2) is within the above range, the appearance quality of the optical film is easily improved, the stability of the varnish is easily improved, and the processability and the total light transmittance of the optical film are easily improved.
  • the polyamide-imide resin has the above-mentioned structural unit (a1) and structural unit (b), and further has the formula (c) as the structural unit (c) derived from the diamine compound.
  • X in () has a structural unit (c2) represented by formula (5).
  • at least a part of the structural units (c2) in the plurality of structural units (c) present in the polyamide-imide resin may be the structural unit (c2).
  • the amount of the structural unit (c2) is such that all structural units included in the polyamide-imide resin are contained.
  • the amount is preferably 1 to 25 mol %, more preferably 2 to 20 mol %, and further preferably 3 to 15 mol %.
  • the amount of the structural unit (c2) is within the above range, the stability of the varnish is easily improved, and the processability and the total light transmittance of the optical film are easily improved.
  • the polyamide-imide resin is a structural unit (b3) in which Z in the formula (b) is a structural unit derived from a dicarboxylic acid compound and is represented by the formula (5) or (7).
  • V in the formulas (5) and (7) is preferably from the viewpoint of the elastic modulus of the optical film, the total light transmittance, the surface hardness and the bending resistance, and the stability of the varnish, Hydrogen contained in O-, diphenylmethylene group, linear, branched or alicyclic divalent hydrocarbon group having 1 to 12 carbon atoms, or divalent hydrocarbon group having 1 to 12 carbon atoms It represents a group in which an atom is substituted with a halogen atom, and more preferably represents -O-.
  • formula (5) is preferably formula (9):
  • R 4 to R 11 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
  • the hydrogen atoms contained in R 4 to R 11 may be independently substituted with a halogen atom, m is an integer from 1 to 4, * Represents a bond] It is represented by.
  • R 4 to R 11 in the formula (9) each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms
  • the hydrogen atoms contained in R 4 to R 11 may be independently substituted with a halogen atom.
  • the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and 2-methyl- group.
  • Examples thereof include a butyl group, a 3-methylbutyl group, a 2-ethyl-propyl group, and an n-hexyl group.
  • Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group and cyclohexyloxy group.
  • Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, tolyl group, xylyl group, naphthyl group and biphenyl group.
  • R 4 to R 11 each independently represent preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or 1 to 3 carbon atoms. Represents an alkyl group, more preferably represents a hydrogen atom.
  • the hydrogen atoms contained in R 4 to R 11 may be independently substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • M in the formula (9) is an integer of 1 to 4, and when m is within this range, the bending resistance and elastic modulus of the optical film tend to be good. Further, m in the formula (9) is preferably an integer in the range of 1 to 3, more preferably 1 to 2 and even more preferably 1. When m is within this range, it is easy to improve the appearance quality, bending resistance and elastic modulus of the optical film.
  • the polyamide-imide-based resin in the present invention has a structural unit (b) derived from a dicarboxylic acid compound, in which Z in the formula (b) has a structural unit represented by the formula (9), the polyamide-imide-based resin is Z in the formula (b) may have one type or two or more types of structural units represented by the formula (9).
  • formula (9) is preferably formula (7′′):
  • the structural unit (b) derived from the dicarboxylic acid compound Z in the formula (b) is represented by the formula (5), the formula (7), the formula (9), or the formula (7′′).
  • the ratio of the structural unit (b3) is preferably 1 mol% or more, more preferably 2 when the amount of all the structural units contained in the polyamide-imide resin is 100 mol %. Mol% or more, more preferably 3 mol% or more, particularly preferably 4 mol% or more, preferably 45 mol% or less, more preferably 35 mol% or less, further preferably 25 mol% or less, particularly preferably 15 mol% or less.
  • the proportion of the structural unit (b3) is at least the above lower limit, the appearance quality, surface hardness and flex resistance of the optical film are likely to be increased, and when the proportion is at most the above upper limit. It is easy to suppress the increase in viscosity of the resin-containing varnish and improve the processability of the film.
  • the content of these constitutional units can be measured using, for example, 1 H-NMR, or the raw material charging ratio can be increased. It can also be calculated from
  • the polyamide-imide resin is a structural unit (b) derived from a dicarboxylic acid compound, wherein Z in formula (b) is represented by formula (5), formula (7), formula (9) or
  • Z in formula (b) is represented by formula (5), formula (7), formula (9) or
  • the structural unit (b3) represented by the formula (7′′) is included, it is preferably 5 mol% or more, more preferably 8 mol% or more, still more preferably 10 mol% or more, and particularly preferably 10 mol% or more in the structural unit (b). It is preferable that the content of the structural unit (b3) is 12 mol% or more, and when the amount of the structural unit (b3) is in the above range, the surface hardness of the optical film is easily increased, and the bending resistance and the elastic modulus are increased.
  • the structural unit (b) derived from the dicarboxylic acid compound contained in the polyamideimide resin preferably 90 mol% or less, more preferably 70 mol% or less, further preferably 50 mol% or less, particularly It is preferable that 30 mol% or less is the structural unit (b3).
  • the polyamide-imide resin contained in the optical film of the present invention has the above-mentioned structural unit (a1), and also has the above-mentioned amount of the structural unit (b3) as the structural unit (b) derived from the dicarboxylic acid compound. It is preferable to include the above structural unit (b2) as the other structural unit (b).
  • Y in the formula (a) is a structural unit (a1) represented by the formula (1), a structural unit (b) represented by the formula (b), and a structural unit (c) represented by the formula (c).
  • At least, or -Y in formula (a) is a structural unit (a1) represented by formula (1)
  • Z in formula (b) is a structural unit (b1) represented by formula (1)
  • formula (c) At least a structural unit (c) represented by
  • the optical film of the present invention examples include the following resins: (I) a polyamide-imide resin containing at least the structural unit (a1), the structural unit (b1) in which Z in the formula (b) is represented by the formula (2), and the structural unit (c); (Ii) Structural unit (a1), a divalent organic compound in which Z in the formula (b) is a bond represented by the formula (20) to the formula (29) in which two nonadjacent bonds are replaced by hydrogen atoms.
  • a polyamide-imide resin containing a structural unit selected from the group consisting of structural units (c2) represented by (X) A polyamide-imide resin containing the structural unit (a1) in place of the structural unit (a1) in each of the above polyamide-imide resins and the structural unit (b1).
  • the polyamide-imide resin has the formula (a Y in () has a structural unit (c1) and a structural unit (b2) in addition to the structural unit (a1) represented by the formula (1), or structural units (a2), (b3) and ( It is preferable to have at least one of c2), and Y in the formula (a) has the structural units (c1) and (b2) in addition to the structural unit (a1) represented by the formula (1), Further, it is more preferable to have at least one of the structural units (a2), (b3) and (c2).
  • the polyamide-imide resin When the polyamide-imide resin has at least one of the structural units (a2), (b3) and (c2), it preferably has at least the structural unit (c2).
  • the polyamide-imide resin of the present invention has not only the structural unit (a1) and the structural unit (c) but also any one of the structural units (b20′) to (b29′) and the structural unit (d1). Is preferred, and it is more preferred to have the structural unit (b1) and the structural unit (d1).
  • the structural unit (a), the structural unit (b) and the structural unit (c) have the imide bond represented by the above formula (D) and the above
  • a structure containing an amide bond represented by the formula (E) may be formed, in addition to the structures represented by (D) and (E), for example, a structural unit (a) and a structural unit (c) May be contained to form a structure represented by the formula (30), and the constitutional unit (d) and the constitutional unit (c) different from the constitutional units (a) to (c) may be represented by the formula (31 ) May be contained by forming a structural unit represented by
  • Y 1 is a tetravalent organic group, preferably a tetravalent organic group in which a hydrogen atom in the organic group may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. is there.
  • Y 1 may be, for example, a constitutional unit represented by the formula (1).
  • the polyamide-imide-based resin may include a plurality of types of Y 1 , and the plurality of types of Y 1 may be the same or different from each other.
  • Y 2 is a trivalent organic group, preferably a trivalent organic group in which a hydrogen atom in the organic group may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. is there.
  • the polyamide-imide-based resin may include a plurality of types of Y 2 , and the plurality of types of Y 2 may be the same or different from each other.
  • X 2 and X 3 are independently of each other a divalent organic group, preferably a hydrocarbon group in which a hydrogen atom in the organic group is substituted or a fluorine-substituted hydrocarbon group. Is an organic group which may be substituted with.
  • Examples of X 2 and X 3 include the group described as X in the formula (c) and the group described as X′ in the formula (2).
  • the polyamide-imide resin has a structure represented by the formula (D) composed of a structural unit (a) derived from a tetracarboxylic acid compound and a structural unit (c) derived from a diamine compound. Units, structural units (b) derived from a dicarboxylic acid compound and structural units (c) derived from a diamine compound, and a structural unit represented by the formula (E), and optionally a structural unit represented by the formula (30). And/or a structural unit represented by the formula (31).
  • the structural units represented by the formulas (D) and (E) are represented by the formula (D ) And formula (E), and optionally, based on the total of constitutional units represented by formula (30) and formula (31), preferably 80 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more. It is contained in an amount of not less than 100% by mol, usually not more than 100% by mol.
  • the above ratio can be measured, for example, using 1 H-NMR, or can be calculated from the charging ratio of raw materials.
  • the polystyrene-equivalent weight average molecular weight of the polyamide-imide-based resin contained in the optical film of the present invention is easy to improve the stability of the varnish, and from the viewpoint of easily increasing the optical properties, elastic modulus, surface hardness and flex resistance of the optical film. It is preferably 200,000 or more, more preferably 250,000 or more, further preferably 300,000 or more, and particularly preferably 350,000 or more. Further, the weight average molecular weight is preferably 1,000,000 or less, more preferably from the viewpoint of easily improving the solubility of the polyamideimide resin in a solvent and easily improving the stretchability and processability of the optical film. It is 800,000 or less, more preferably 700,000 or less, and particularly preferably 600,000 or less.
  • the weight average molecular weight can be determined by, for example, GPC measurement and standard polystyrene conversion, and may be calculated by the method described in Examples, for example.
  • the imidization ratio of the polyamide-imide resin is preferably 90% or higher, more preferably 93% or higher, even more preferably 96% or higher, and usually 100% or lower. From the viewpoint of easily improving the optical characteristics of the optical film, it is preferable that the imidization ratio is not less than the above lower limit.
  • the imidization ratio indicates the ratio of the molar amount of imide bonds in the polyamideimide-based resin to the double value of the molar amount of the structural unit derived from the tetracarboxylic acid compound in the polyamideimide-based resin.
  • the polyamide-imide-based resin contains a tricarboxylic acid compound
  • the value of twice the molar amount of the constitutional unit derived from the tetracarboxylic acid compound in the polyamide-imide-based resin and the constitutional unit derived from the tricarboxylic acid compound The ratio of the molar amount of the imide bond in the polyamide-imide resin to the total of the molar amount is shown.
  • the imidization ratio can be determined by IR method, NMR method, or the like.
  • the content of halogen atoms in the polyamideimide resin is preferably 1 to 40% by mass, more preferably 5 to 40% by mass, and further preferably 5 to 30% by mass, based on the mass of the polyamideimide resin.
  • the content of halogen atoms is at least the above lower limit, the elastic modulus, surface hardness, transparency and visibility of the optical film can be more easily improved.
  • the content of halogen atoms is at most the above upper limit, the resin will be easily synthesized.
  • the polyamideimide-based resin contained in the optical film of the present invention can be produced using a tetracarboxylic acid compound, a dicarboxylic acid compound and a diamine compound as main raw materials.
  • the polyamide-imide resin is a structural unit derived from a tetracarboxylic acid compound, wherein Y in the formula (a) is a structural unit (a1) represented by the formula (1) and a structural unit derived from a dicarboxylic acid compound.
  • Z in the formula (b) above includes at least one constitutional unit selected from the group consisting of the constitutional unit (b1) represented by the formula (1). Therefore, at least one compound selected from the group consisting of a tetracarboxylic acid compound having a structure represented by formula (1) and a dicarboxylic acid compound having a structure represented by formula (1) is used as a raw material. ..
  • Examples of the tetracarboxylic acid compound used for producing the resin include a tetracarboxylic acid compound in which Y in the formula (a) gives a structural unit (a1) represented by the formula (1), for example, an aromatic tetracarboxylic acid dicarboxylic acid.
  • An aromatic tetracarboxylic acid compound such as an anhydride can be used.
  • One type of tetracarboxylic acid compound may be used, or two or more types may be used in combination.
  • the tetracarboxylic acid compound may be a tetracarboxylic acid compound analog such as an acid chloride compound in addition to the dianhydride.
  • the compound represented by the above formula (8) may be mentioned.
  • the tetracarboxylic acid compound used for producing the resin is a compound represented by the above formula (8) (tetracarboxylic dianhydride), for example, 3,3′,4,4′-biphenyltetracarboxylic dianhydride. Thing (BPDA) is mentioned.
  • tetracarboxylic acid compounds used in the production of resins include 4,4′-oxydiphthalic acid dianhydride, 2,2′,3,3′-benzophenone tetracarboxylic acid dianhydride and 2,2′.
  • Examples of monocyclic aromatic tetracarboxylic dianhydrides include 1,2,4,5-benzenetetracarboxylic dianhydride (pyromellitic dianhydride (PMDA)), which is a condensed polycondensate.
  • Examples of the cyclic aromatic tetracarboxylic dianhydride include 2,3,6,7-naphthalene tetracarboxylic dianhydride.
  • the tetracarboxylic acid compound is preferably 4,4′-oxydiphthalic acid dianhydride, 3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride, 2,2′,3,3′.
  • Anhydride 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,2',3,3'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyl Phenyl)methane dianhydride, 4,4′-(p-phenylenedioxy)diphthalic dianhydride and 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA). These may be used alone or in combination of two or more.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • PMDA 1,2,4,5-benzenetetracarboxylic dianhydride
  • 3,3′,4,4′-biphenyltetracarboxylic acid is used as a tetracarboxylic acid compound used for producing a resin.
  • dianhydride which is 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 4,4′-(hexafluoroisopropylidene)diphthalic dianhydride.
  • 6FDA is also preferable to use the product (6FDA).
  • dicarboxylic acid compound used in the production of the polyamide-imide resin examples include aromatic dicarboxylic acids, aliphatic dicarboxylic acids and their related acid chloride compounds, and acid anhydrides.
  • One type of dicarboxylic acid compound may be used, or two or more types may be used in combination.
  • Examples of the dicarboxylic acid compound used in the production of the polyamideimide-based resin such that Z in the formula (b) gives the structural unit (b1) represented by the formula (1) include ring-assembled aromatic dicarboxylic acid compounds. Can be mentioned.
  • Examples of the dicarboxylic acid compound used for producing the resin include the compound represented by the above formula (12) (dicarboxylic acid chloride), for example, 3,3′,4,4′-biphenyldicarboxylic acid chloride (BPDC). ..
  • dicarboxylic acid compound terephthalic acid, isophthalic acid, 4,4′-oxybisbenzoic acid or their acid chloride compounds are preferably used.
  • other dicarboxylic acid compounds may be used. Specific examples of other dicarboxylic acid compounds include isophthalic acid; naphthalenedicarboxylic acid; 4,4'-biphenyldicarboxylic acid; 3,3'-biphenyldicarboxylic acid; chain hydrocarbon dicarboxylic acids having 8 or less carbon atoms.
  • Acid compounds and compounds in which two benzoic acids are linked by a single bond, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —SO 2 — or phenylene group, and their compounds Acid chloride compounds may be mentioned.
  • 4,4′-oxybis(benzoyl chloride) and terephthaloyl chloride are preferable, and 4,4′-oxybis(benzoyl chloride) and terephthaloyl chloride are more preferably used in combination.
  • the diamine compound used for producing the polyamide-imide resin examples include aromatic diamines.
  • the "aromatic diamine” represents a diamine in which an amino group is directly bonded to an aromatic ring, and may have an aliphatic group or another substituent in a part of its structure.
  • the aromatic ring may be a monocyclic ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring and a fluorene ring, but are not limited thereto. Of these, a benzene ring is preferable.
  • aromatic diamines examples include p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, m-xylylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene, and 2,6-diaminonaphthalene.
  • An aromatic diamine having one aromatic ring 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′- Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4 -Aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl] Propane, 2,2-bis[4-
  • the aromatic diamine is preferably 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone.
  • an aliphatic diamine may be further used in addition to the aromatic diamine.
  • "aliphatic diamine” represents a diamine in which an amino group is directly bonded to an aliphatic group, and an aromatic ring or other substituent may be included in a part of its structure.
  • Examples of aliphatic diamines include acyclic aliphatic diamines such as hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, norbornanediamine and 4,4′.
  • -Cyclic aliphatic diamines such as diaminodicyclohexylmethane and the like.
  • the polyamide-imide resin in the range that does not impair the various physical properties of the optical laminate, in addition to the tetracarboxylic acid compound, tetracarboxylic acid and tricarboxylic acid and those anhydrides and derivatives thereof are further reacted. It may be.
  • tetracarboxylic acid examples include a water adduct of an anhydride of the above tetracarboxylic acid compound.
  • tricarboxylic acid compound examples include aromatic tricarboxylic acids, aliphatic tricarboxylic acids, and related acid chloride compounds, acid anhydrides, and the like, and two or more kinds may be used in combination. Specific examples include 1,3,5-benzenetricarboxylic acid or its acid chloride compound, 1,2,4-benzenetricarboxylic acid anhydride; 2,3,6-naphthalenetricarboxylic acid-2,3-anhydride; Phthalic anhydride and benzoic acid are linked by a single bond, —O—, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —SO 2 — or phenylene group.
  • the amount of each of the diamine compound, the tetracarboxylic acid compound and the dicarboxylic acid compound used can be appropriately selected according to the desired ratio of each constitutional unit of the polyamideimide resin.
  • the method for producing a polyamide-imide resin is not particularly limited as long as the above-mentioned polyamide-imide resin can be obtained, but from the viewpoint of easily increasing the appearance quality of the optical film, the elastic modulus and the total light transmittance, a diamine compound and a tetracarboxylic acid.
  • a production method of reacting a compound and a dicarboxylic acid compound preferably a production method of dividing and adding a dicarboxylic acid compound to produce a polyamideimide resin, and reacting a diamine compound and a tetracarboxylic acid compound to form an intermediate
  • the method includes a step (I) of producing a body (A) and a step (II) of reacting the intermediate (A) with a dicarboxylic acid compound, and in the step (II), the dicarboxylic acid compound is dividedly added. More preferably, the polyamide-imide resin is produced by the method.
  • the polyamide-imide resin is preferably a resin produced by a production method in which a diamine compound, a tetracarboxylic acid compound, and a dicarboxylic acid compound are reacted, and a dicarboxylic acid compound is added in a divided manner.
  • a production method comprising a step (I) of reacting a compound with a tetracarboxylic acid compound to produce an intermediate (A), and a step (II) of reacting the intermediate (A) with a dicarboxylic acid compound.
  • the resin produced by the production method in which the dicarboxylic acid compound is dividedly added is more preferable.
  • the reaction temperature is not particularly limited, but may be, for example, 5 to 200° C., preferably 5 to 100° C., more preferably 5 to 50° C., and further preferably 5° C. to room temperature (about 25° C.).
  • the reaction time may be, for example, 1 minute to 72 hours, preferably 10 minutes to 24 hours.
  • the reaction may be carried out in air or in an inert gas atmosphere such as nitrogen or argon with stirring, and may be carried out under normal pressure, under pressure or under reduced pressure. In a preferred embodiment, it is carried out under normal pressure and/or the above-mentioned inert gas atmosphere while stirring.
  • step (I) the diamine compound and the tetracarboxylic acid compound react to produce an intermediate (A), that is, a polyamic acid. Therefore, the intermediate (A) has at least a structural unit derived from a diamine compound and a structural unit derived from a tetracarboxylic acid compound.
  • step (II) it is preferable to react the intermediate (A) with the dicarboxylic acid compound, and to add the dicarboxylic acid compound in portions.
  • the dicarboxylic acid compound is dividedly added to the reaction solution obtained in the step (I) to react the intermediate (A) with the dicarboxylic acid compound. It is easy to adjust the molecular weight of the polyamide-imide resin within the above preferable range by adding the dicarboxylic acid compound in portions instead of adding it all at once.
  • the divided addition means that the dicarboxylic acid compound to be added is added in several divided portions, more specifically, the dicarboxylic acid to be added is divided into specific amounts, which are separated by a predetermined interval or a predetermined time. Means to add. Since the predetermined interval or predetermined time includes a very short interval or time, the divided addition also includes continuous addition or continuous feed.
  • the number of divisions when the dicarboxylic acid compound is dividedly added can be appropriately selected depending on the reaction scale, the kind of the raw material, etc., and is preferably 2 to 20 times, more preferably 3 to 10 times, and further preferably 3 times. ⁇ 6 times. It is considered that when the number of divisions is within the above range, the structure is likely to be optimal for increasing the elastic modulus while maintaining the transmittance of the optical film. Further, it is considered that the weight average molecular weight of the polyamide-imide resin can be easily adjusted to the above preferable range.
  • the dicarboxylic acid compound may be divided and added in an equal amount, or may be divided and added in an uneven amount.
  • the time between each addition (hereinafter sometimes referred to as an addition interval) may be the same or different.
  • the term referred to as divided addition means that the total amount of all dicarboxylic acid compounds is divided and added, and the method of dividing each dicarboxylic acid compound is not particularly limited.
  • each dicarboxylic acid compound may be added separately or collectively or in a divided manner, each dicarboxylic acid compound may be added in a divided manner together, or a combination thereof may be used.
  • the weight average molecular weight of the polyamide resin is preferably 10% or more, more preferably 15% or more, based on the weight average molecular weight of the obtained polyamide resin, and the dicarboxylic acid compound to be added.
  • the dicarboxylic acid compound is preferably added in an amount of 1 to 40 mol %, more preferably 2 to 25 mol %, based on the total molar amount of
  • the reaction temperature in step (II) is not particularly limited, but may be, for example, 5 to 200° C., preferably 5 to 100° C., more preferably 5 to 50° C., and further preferably 5 to room temperature (about 25° C.). ..
  • the reaction may be carried out in air or in an atmosphere of an inert gas such as nitrogen or argon with stirring, and may be carried out under normal pressure, under pressure or under reduced pressure. In a preferred embodiment, the step (II) is carried out under normal pressure and/or the inert gas atmosphere while stirring.
  • the mixture is stirred for a predetermined time and reacted to obtain a polyamideimide precursor.
  • the polyamide-imide precursor can be isolated by, for example, adding a large amount of water or the like to a reaction liquid containing the polyamide-imide precursor to precipitate the polyamide-imide precursor, and performing filtration, concentration, drying, or the like.
  • the intermediate (A) reacts with the dicarboxylic acid compound to obtain a polyamideimide precursor.
  • the polyamideimide precursor refers to a polyamideimide before imidization (before ring closure) that has at least a structural unit derived from a diamine compound, a structural unit derived from a tetracarboxylic acid, and a structural unit derived from a dicarboxylic acid compound.
  • the reaction temperature of the diamine compound, the tetracarboxylic acid compound and the dicarboxylic acid compound is not particularly limited, but is, for example, 5 to 350°C, preferably 5 to 200°C, more preferably 5 to 100°C.
  • the reaction time is not particularly limited, it is, for example, about 30 minutes to 10 hours.
  • the reaction may be performed under an inert atmosphere or reduced pressure. In a preferred embodiment, the reaction is carried out under normal pressure and/or an inert gas atmosphere with stirring. In addition, the reaction is preferably carried out in a solvent inert to the reaction.
  • the solvent is not particularly limited as long as it does not affect the reaction, and for example, water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, Alcohol solvents such as 2-butoxyethanol and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, ⁇ -butyrolactone, ⁇ -valerolactone, propylene glycol methyl ether acetate and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, heptane; alicyclic
  • the method for producing a polyamide-imide resin may further include a step (III) of imidizing a polyamide-imide precursor in the presence of an imidization catalyst.
  • a step (III) of imidizing a polyamide-imide precursor in the presence of an imidization catalyst By subjecting the polyamide-imide precursor obtained in the step (II) to the step (III), a constituent unit portion having a polyamic acid structure in the constituent unit of the polyamide-imide precursor is imidized (ring closed), and the formula ( It is possible to obtain a polyamide-imide resin containing the structural unit represented by 1) and the structural unit represented by the formula (2).
  • imidization catalyst examples include aliphatic amines such as tripropylamine, dibutylpropylamine, and ethyldibutylamine; N-ethylpiperidine, N-propylpiperidine, N-butylpyrrolidine, N-butylpiperidine, and N-propylhexahydro.
  • Alicyclic amine (monocyclic) such as azepine; azabicyclo[2.2.1]heptane, azabicyclo[3.2.1]octane, azabicyclo[2.2.2]octane, and azabicyclo[3.2.
  • Alicyclic amine such as nonane; and pyridine, 2-methylpyridine (2-picoline), 3-methylpyridine (3-picoline), 4-methylpyridine (4-picoline), 2- Ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2,4-dimethylpyridine, 2,4,6-trimethylpyridine, 3,4-cyclopentenopyridine, 5,6,7,8-tetrahydroisoquinoline, and Aromatic amines such as isoquinoline may be mentioned. From the viewpoint of facilitating the imidization reaction, it is preferable to use an acid anhydride together with the imidization catalyst.
  • Examples of the acid anhydride include conventional acid anhydrides used in imidization reaction, and specific examples thereof include aliphatic acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, and aromatics such as phthalic acid. Examples thereof include acid anhydrides.
  • the polyamide-imide resin may be isolated (separated and purified) by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization and column chromatography, or a separation means combining these.
  • separation means such as filtration, concentration, extraction, crystallization, recrystallization and column chromatography, or a separation means combining these.
  • a large amount of alcohol such as methanol is added to a reaction liquid containing a polyamide-imide resin to precipitate the resin, which can be isolated by concentration, filtration and drying.
  • the optical film of the present invention may contain at least one kind of filler in addition to the above polyamide-imide resin.
  • the filler include organic particles and inorganic particles, and preferably inorganic particles.
  • the inorganic particles silica, zirconia, alumina, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, metal oxide particles such as cerium oxide, magnesium fluoride, sodium fluoride, etc.
  • Metal fluoride particles and the like, and among these, from the viewpoint of increasing the elastic modulus and/or tear strength of the optical film and easily improving the impact resistance preferably silica particles, zirconia particles, and alumina particles. , And more preferably silica particles.
  • These fillers can be used alone or in combination of two or more.
  • the average primary particle diameter of the filler is 1 nm or more, more preferably 5 nm or more, even more preferably 10 nm or more, even more preferably 15 nm or more, particularly preferably 20 nm or more, preferably 100 nm or less, more preferably Is 90 nm or less, more preferably 80 nm or less, even more preferably 70 nm or less, particularly preferably 60 nm or less, particularly preferably 50 nm or less, particularly preferably 40 nm or less.
  • the average primary particle diameter of the filler can be measured by the BET method.
  • the average primary particle size may be measured by image analysis with a transmission electron microscope or a scanning electron microscope.
  • the content of the filler is usually 0.1 part by mass or more, preferably 1 part by mass or more, and more preferably 100 parts by mass of the optical film. It is 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, particularly preferably 30 parts by mass or more, and preferably 60 parts by mass or less.
  • the content of the filler is at least the above lower limit, the elastic modulus of the obtained optical film can be easily improved.
  • the content of the filler is not more than the above upper limit, the optical characteristics of the optical film are likely to be improved.
  • the optical film of the present invention may include at least one UV absorber.
  • the ultraviolet absorber can be appropriately selected from those usually used as an ultraviolet absorber in the field of resin materials.
  • the ultraviolet absorber may include a compound that absorbs light having a wavelength of 400 nm or less.
  • Examples of the ultraviolet absorber include at least one compound selected from the group consisting of benzophenone compounds, salicylate compounds, benzotriazole compounds, and triazine compounds.
  • the ultraviolet absorbers can be used alone or in combination of two or more kinds. Since the optical film contains the ultraviolet absorber, the deterioration of the resin is suppressed, so that the visibility can be enhanced when the optical film of the present invention is applied to a display device or the like.
  • system compound refers to a derivative of the compound to which the “system compound” is attached.
  • benzophenone-based compound refers to a compound having benzophenone as a base skeleton and a substituent bonded to benzophenone.
  • the content of the ultraviolet absorber is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 10 parts by mass with respect to the mass of the polyamideimide resin contained in the optical film.
  • the amount is 1 to 8 parts by mass, more preferably 2 to 7 parts by mass.
  • the content of the ultraviolet absorber is at least the above lower limit, it is easy to improve the ultraviolet absorptivity.
  • the content of the ultraviolet absorber is not more than the above upper limit, decomposition of the ultraviolet absorber due to heat during manufacturing of the base material can be suppressed, optical characteristics can be easily improved, and haze, for example, can be easily reduced.
  • the optical film of the present invention may further contain an additive other than the filler and the ultraviolet absorber.
  • additives include, for example, antioxidants, release agents, stabilizers, coloring agents such as bluing agents, flame retardants, pH adjusters, silica dispersants, lubricants, thickeners, and leveling agents. Can be mentioned.
  • their content is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 15 parts by mass, and still more preferably 0.1 to 10 parts by mass based on the mass of the optical film. It may be 10 parts by mass.
  • the method for producing the optical film of the present invention is not particularly limited, and for example, the following steps: (A) A varnish preparing step of preparing a polyamideimide resin varnish containing at least the polyamideimide resin and a solvent, Manufacturing including an optical film forming step of (b) applying a varnish to a support material to form a coating film, and (c) drying the applied liquid (coating film) to form an optical film It can be a method.
  • a polyamide-imide resin is dissolved in a solvent, and if necessary, additives such as the filler and the ultraviolet absorber are added and mixed by stirring to prepare a varnish.
  • additives such as the filler and the ultraviolet absorber are added and mixed by stirring to prepare a varnish.
  • silica particles are used as a filler, a dispersion of a silica sol containing silica particles may be added to the resin with a solvent capable of dissolving the resin, for example, a silica sol obtained by substituting with a solvent used for preparing a varnish described below. ..
  • the solvent used for preparing the varnish is not particularly limited as long as it can dissolve the resin.
  • the solvent include amide solvents such as N,N-dimethylacetamide and N,N-dimethylformamide; lactone solvents such as ⁇ -butyrolactone (GBL) and ⁇ -valerolactone; dimethyl sulfone, dimethyl sulfoxide, sulfolane and the like. And a carbonate-based solvent such as ethylene carbonate and propylene carbonate; and a combination thereof (mixed solvent).
  • amide solvents or lactone solvents are preferable, and lactone solvents are more preferable.
  • a lactone solvent is used, a film having high optical properties tends to be obtained.
  • the varnish may contain water, an alcohol solvent, a ketone solvent, an acyclic ester solvent, an ether solvent, or the like.
  • the solid content concentration of the polyamide-imide resin varnish is preferably 1 to 25% by mass, more preferably 5 to 20% by mass, further preferably 5 to 15% by mass, from the viewpoint of easily increasing the stability of the polyamideimide-based resin varnish. Is.
  • the concentration of the solvent in the polyamide-imide resin varnish of the present invention is preferably 75 to 99% by mass based on the total amount of the polyamide-imide resin varnish, from the viewpoint of easily increasing the stability of the polyamide-imide resin varnish. It is preferably 80 to 95% by mass, more preferably 85 to 95% by mass.
  • a varnish is coated on the support material by a known coating method to form a coating film.
  • a known coating method for example, wire bar coating method, reverse coating, roll coating method such as gravure coating, die coating method, comma coating method, lip coating method, spin coating method, screen coating method, fountain coating method, dipping method, A spray method, a spout molding method and the like can be mentioned.
  • the optical film can be formed by drying the coating film and peeling it from the support material. You may provide the process of drying an optical film further after peeling.
  • the coating film can be dried usually at a temperature of 50 to 350°C. If necessary, the coating film may be dried under an inert atmosphere or a reduced pressure condition.
  • the support material examples include a SUS plate if it is a metal system, a PET film, a PEN film, a polyamide resin film, a polyimide resin film, a cycloolefin polymer (COP) film, an acrylic film if it is a resin system.
  • a PET film, a COP film and the like are preferable from the viewpoint of excellent smoothness and heat resistance, and further, a PET film is more preferable from the viewpoint of adhesion to an optical film and cost.
  • optical film of the present invention is not particularly limited and may be used for various purposes.
  • the optical film of the present invention may be a single layer as described above, or may be a laminate, the optical film of the present invention may be used as it is, or a laminate with another film. May be used as.
  • the optical film is a laminated body, all the layers laminated on one side or both sides of the optical film are collectively referred to as an optical film.
  • One or more functional layers may be laminated on at least one surface of the optical film of the present invention.
  • the functional layer include an ultraviolet absorbing layer, a hard coat layer, a primer layer, a gas barrier layer, an adhesive layer, a hue adjusting layer and a refractive index adjusting layer.
  • the functional layer may be used alone or in combination of two or more kinds.
  • the ultraviolet absorbing layer is a layer having a function of absorbing ultraviolet rays, and for example, a main material selected from a transparent resin of an ultraviolet curable type, a transparent resin of an electron beam curable type, and a transparent resin of a thermosetting type, and the main material It is composed of dispersed ultraviolet absorbers.
  • a hard coat layer may be provided on at least one surface of the optical film of the present invention.
  • the thickness of the hard coat layer is not particularly limited and may be, for example, 2 to 100 ⁇ m. When the thickness of the hard coat layer is within the above range, sufficient scratch resistance can be ensured, bending resistance is unlikely to decrease, and a problem of curling due to curing shrinkage tends not to occur. ..
  • the hard coat layer can be formed by curing a hard coat composition containing a reactive material capable of forming a crosslinked structure by irradiation with active energy rays or application of heat energy, and irradiation with active energy rays is preferable.
  • Active energy rays are defined as energy rays capable of decomposing compounds that generate active species to generate active species, such as visible light, ultraviolet rays, infrared rays, X-rays, ⁇ rays, ⁇ rays, ⁇ rays and electron rays. And the like, and preferably ultraviolet rays.
  • the hard coat composition contains at least one polymer of a radically polymerizable compound and a cationically polymerizable compound.
  • the radical polymerizable compound is a compound having a radical polymerizable group.
  • the radical polymerizable group contained in the radical polymerizable compound may be any functional group capable of causing a radical polymerization reaction, and examples thereof include a group containing a carbon-carbon unsaturated double bond, and specifically, a vinyl group. And (meth)acryloyl group.
  • the radical-polymerizable compound has two or more radical-polymerizable groups, these radical-polymerizable groups may be the same or different.
  • the number of radically polymerizable groups contained in one molecule of the radically polymerizable compound is preferably 2 or more from the viewpoint of improving the hardness of the hard coat layer.
  • the radically polymerizable compound is preferably a compound having a (meth)acryloyl group. Specifically, 2 to 6 (meth)acryloyl groups are included in one molecule.
  • Thousands of oligomers may be mentioned, preferably one or more selected from epoxy (meth)acrylate, urethane (meth)acrylate and polyester (meth)acrylate.
  • the cationically polymerizable compound is a compound having a cationically polymerizable group such as an epoxy group, an oxetanyl group and a vinyl ether group.
  • 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.
  • a compound having at least one of an epoxy group and an oxetanyl group as a cationically polymerizable group is preferable.
  • a cyclic ether group such as an epoxy group or an oxetanyl group is preferable from the viewpoint that the shrinkage accompanying the polymerization reaction is small.
  • compounds having an epoxy group among 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 radically polymerizable compound. There is an advantage that.
  • the oxetanyl group of the cyclic ether group tends to have a higher degree of polymerization than the epoxy group, accelerates the network formation rate obtained from the cationically polymerizable compound of the obtained hard coat layer, and is mixed with the radically polymerizable compound. Even in the area to be filled, there is an advantage that an independent network is formed without leaving unreacted monomer in the film.
  • the hard coat composition may further include a polymerization initiator.
  • the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, radical and cationic polymerization initiators, etc., which are appropriately selected and used. These polymerization initiators are decomposed by at least one of irradiation with active energy rays and heating to generate radicals or cations to promote radical polymerization and cation polymerization.
  • the radical polymerization initiator may be any one that can release a substance that initiates radical polymerization by at least one of irradiation with active energy rays and heating.
  • thermal radical polymerization initiators examples include hydrogen peroxide, organic peroxides such as perbenzoic acid, and azo compounds such as azobisbutyronitrile.
  • active energy ray radical polymerization initiator a Type 1 type radical polymerization initiator that produces a radical by decomposition of a molecule and a Type 2 type radical polymerization initiator that produces a radical by a hydrogen abstraction type reaction coexisting with a tertiary amine Yes, they are used alone or in combination. Any cationic polymerization initiator may be used as long as it can release a substance that initiates cationic polymerization by irradiation with active energy rays and/or heating.
  • an aromatic iodonium salt an aromatic sulfonium salt, a cyclopentadienyl iron(II) complex or the like can be used. These can initiate cationic polymerization either by irradiation with active energy rays or by heating, or both, depending on the difference in structure.
  • the polymerization initiator may preferably be contained in an amount of 0.1 to 10% by mass based on 100% by mass of the entire hard coat composition.
  • content of the polymerization initiator is in the above range, curing can be sufficiently advanced, and the mechanical properties and adhesion of the finally obtained coating film can be set in a good range, and Poor adhesion due to curing shrinkage, cracking and curling tend to occur less easily.
  • the hard coat composition may further include one or more selected from the group consisting of a solvent and an additive.
  • the solvent is a solvent that can dissolve or disperse the polymerizable compound and the polymerization initiator, if the solvent is known as a solvent of the hard coat composition of the present technical field, does not impair the effects of the present invention Can be used in a range.
  • the additive may further include inorganic particles, a leveling agent, a stabilizer, a surfactant, an antistatic agent, a lubricant, an antifouling agent, and the like.
  • the adhesive layer is a layer having an adhesive function and has a function of adhering the optical film to another member.
  • a commonly known material can be used as the material for forming the adhesive layer.
  • a thermosetting resin composition or a photocurable resin composition can be used.
  • the resin composition can be polymerized and cured by supplying energy afterwards.
  • the adhesive layer may be a layer called pressure sensitive adhesive (Pressure Sensitive Adhesive, PSA) that is attached to an object by pressing.
  • PSA Pressure Sensitive Adhesive
  • the pressure-sensitive adhesive may be an adhesive that is "a substance that has adhesiveness at room temperature and that adheres to an adherend with a light pressure" (JIS K 6800), or "a protective film (microcapsule) for specific components. ), and a capsule type adhesive which is an adhesive (JIS K6800) capable of maintaining stability until the coating is broken by an appropriate means (pressure, heat, etc.).
  • the hue adjusting layer is a layer having a function of adjusting hue, and is a layer capable of adjusting the laminate including the optical film to a desired hue.
  • the hue adjustment layer is, for example, a layer containing a resin and a colorant.
  • the colorant include titanium oxide, zinc oxide, rouge, titanium oxide-based calcined pigment, ultramarine blue, cobalt aluminate, and inorganic pigments such as carbon black; azo-based compounds, quinacridone-based compounds, anthraquinone-based compounds, Organic pigments such as perylene compounds, isoindolinone compounds, phthalocyanine compounds, quinophthalone compounds, slene compounds, and diketopyrrolopyrrole compounds; extender pigments such as barium sulfate and calcium carbonate; and basic dyes, Examples include acid dyes and mordant dyes.
  • the refractive index adjusting layer is a layer having a refractive index adjusting function, for example, a layer having a refractive index different from that of the optical film and capable of imparting a predetermined refractive index to the optical laminate.
  • the refractive index adjusting layer may be, for example, a resin layer containing an appropriately selected resin and optionally a pigment, or a metal thin film.
  • the pigment for adjusting the refractive index include silicon oxide, aluminum oxide, antimony oxide, tin oxide, titanium oxide, zirconium oxide and tantalum oxide.
  • the average primary particle diameter of the pigment may be 0.1 ⁇ m or less.
  • the metal used for the refractive index adjusting layer include metals such as titanium oxide, tantalum oxide, zirconium oxide, zinc oxide, tin oxide, silicon oxide, indium oxide, titanium oxynitride, titanium nitride, silicon oxynitride, and silicon nitride. An oxide or a metal nitride is mentioned.
  • the optical film of the present invention may be a single layer or a laminate, for example, the optical film produced as described above may be used as it is, or a laminate with another film. May be used as.
  • the optical film may have a protective film on at least one surface, in other words, one surface or both surfaces.
  • the protective film may be laminated on the surface of the optical film side or the surface of the functional layer side, and is laminated on both the optical film side and the functional layer side. May be.
  • the protective film may be laminated on one surface of the functional layer side or on both surfaces of the functional layer side.
  • the protective film is a film for temporarily protecting the surface of the optical film or the functional layer, and is not particularly limited as long as it is a peelable film capable of protecting the surface of the optical film or the functional layer.
  • the protective film examples include polyester resin films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin resin films such as polyethylene and polypropylene films; acrylic resin films; polyolefin resin films, polyethylene. It is preferably selected from the group consisting of terephthalate resin films and acrylic resin films.
  • each protective film may be the same or different.
  • the thickness of the protective film is not particularly limited, but is usually 10 to 120 ⁇ m, preferably 15 to 110 ⁇ m, more preferably 20 to 100 ⁇ m.
  • the thickness of each protective film may be the same or different.
  • the optical film of the present invention is useful as a front plate of a display device, particularly as a front plate of a flexible display device (hereinafter sometimes referred to as a window film).
  • the flexible display device has, for example, a flexible functional layer and an optical film that is superposed on the flexible functional layer and functions as a front plate. That is, the front plate of the flexible display device is arranged on the visible side above the flexible functional layer. This front plate has a function of protecting the flexible functional layer.
  • Examples of display devices include TVs, smartphones, mobile phones, car navigations, tablet PCs, portable game consoles, electronic paper, indicators, bulletin boards, watches, and wearable devices such as smart watches.
  • Examples of the flexible display device include all display devices having flexible characteristics, and preferably, among them, a foldable display device and a rollable display device which are preferably foldable.
  • the present invention also provides a flexible display device comprising the optical film of the present invention.
  • the optical film of the present invention is preferably used as a front plate in a flexible display device, and the front plate is sometimes referred to as a window film.
  • the flexible display device includes a flexible display device laminate and an organic EL display panel, and the flexible display device laminate is arranged on the viewing side of the organic EL display panel and is configured to be bendable.
  • the laminate for a flexible display device may contain a window film, a polarizing plate (preferably a circularly polarizing plate) and a touch sensor, and the order of laminating them is arbitrary, but the window film, the polarizing plate, It is preferable that the touch sensor or the window film, the touch sensor, and the polarizing plate are laminated in this order.
  • the presence of the polarizing plate on the viewing side of the touch sensor is preferable because the pattern of the touch sensor is less visible and the visibility of the display image is improved.
  • Each member can be laminated using an adhesive, a pressure-sensitive adhesive or the like. Further, a light-shielding pattern formed on at least one surface of any one of the window film, the polarizing plate, and the touch sensor may be provided.
  • the flexible display device of the present invention may further include a polarizing plate, preferably a circularly polarizing plate.
  • the circularly polarizing plate is a functional layer having a function of transmitting only the right circularly polarized light component or the left circularly polarized light component by laminating a ⁇ /4 retardation plate on a linearly polarizing plate. For example, by converting the external light into right circularly polarized light and blocking the external light reflected by the organic EL panel to become left circularly polarized light, and transmitting only the luminescent component of the organic EL, the influence of reflected light is suppressed and the image is displayed. It is used to make it easier to see.
  • the absorption axis of the linear polarizing plate and the slow axis of the ⁇ /4 retardation plate are theoretically required to be 45°, but they are practically 45 ⁇ 10°.
  • the linearly polarizing plate and the ⁇ /4 retardation plate are not necessarily required to be laminated adjacent to each other as long as the relationship between the absorption axis and the slow axis satisfies the above range. It is preferable to achieve perfect circularly polarized light at all wavelengths, but this is not necessary in practice, so the circularly polarizing plate in the present invention also includes an elliptically polarizing plate. It is also preferable to further laminate a ⁇ /4 retardation film on the visible side of the linearly polarizing plate to make the emitted light circularly polarized light to improve the visibility in the state of wearing polarized sunglasses.
  • the linearly polarizing plate is a functional layer having a function of transmitting light oscillating in the transmission axis direction but blocking polarized light of an oscillating component perpendicular thereto.
  • the linear polarizing plate may be configured to include a linear polarizer alone or a linear polarizer and a protective film attached to at least one surface thereof.
  • the thickness of the linear polarizing plate may be 200 ⁇ m or less, preferably 0.5 to 100 ⁇ m. When the thickness is in the above range, the flexibility tends to be difficult to decrease.
  • the linear polarizer may be a film-type polarizer manufactured by dyeing and stretching a polyvinyl alcohol (PVA) film.
  • a dichroic dye such as iodine is adsorbed on a PVA-based film oriented by stretching or is stretched in a state of being adsorbed on PVA, whereby the dichroic dye is oriented and exhibits polarization performance.
  • the production of the film-type polarizer may further include steps such as swelling, crosslinking with boric acid, washing with an aqueous solution, and drying.
  • the stretching and dyeing steps may be performed on the PVA film alone, or may be performed in a state of being laminated with another film such as polyethylene terephthalate.
  • the thickness of the PVA-based film used is preferably 10 to 100 ⁇ m, and the stretching ratio is preferably 2 to 10 times.
  • a liquid crystal coating type polarizer formed by coating a liquid crystal polarizing composition may be used.
  • the liquid crystal polarizing composition may include a liquid crystal compound and a dichroic dye compound.
  • the liquid crystalline compound is only required to have a property of exhibiting a liquid crystal state, and particularly preferably has a higher order alignment state such as a smectic phase because high polarization performance can be exhibited. It is also preferable that the liquid crystal compound has a polymerizable functional group.
  • the dichroic dye is a dye that is aligned with the liquid crystal compound and exhibits dichroism, and the dichroic dye itself may have liquid crystallinity or has a polymerizable functional group. You can also Any of the compounds in the liquid crystal polarizing composition has a polymerizable functional group.
  • the liquid crystal polarizing composition may further include an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a cross-linking agent, a silane coupling agent and the like.
  • the liquid crystal polarizing layer is manufactured by applying a liquid crystal polarizing composition on the alignment film to form a liquid crystal polarizing layer.
  • the liquid crystal polarizing layer can be formed thinner than a film type polarizer.
  • the thickness of the liquid crystal polarizing layer may be preferably 0.5 to 10 ⁇ m, more preferably 1 to 5 ⁇ m.
  • the alignment film can be produced, for example, by applying the composition for forming an alignment film on a substrate and imparting the alignment property by rubbing, irradiation of polarized light, or the like.
  • the composition for forming an alignment film may contain a solvent, a cross-linking agent, an initiator, a dispersant, a leveling agent, a silane coupling agent and the like in addition to the alignment agent.
  • the alignment agent for example, polyvinyl alcohols, polyacrylates, polyamic acids, and polyimides can be used.
  • an aligning agent containing a cinnamate group When photo-alignment is applied, it is preferable to use an aligning agent containing a cinnamate group.
  • the weight average molecular weight of the polymer used as the aligning agent may be about 10,000 to 1,000,000.
  • the thickness of the alignment film is preferably 5 to 10,000 nm, more preferably 10 to 500 nm, from the viewpoint of the alignment regulating force.
  • the liquid crystal polarizing layer can be peeled from the base material and transferred to be laminated, or the base material can be laminated as it is. It is also preferable that the base material plays a role as a transparent base material of a protective film, a retardation plate, or a window.
  • the protective film may be any transparent polymer film, and the materials and additives used for the transparent substrate can be used. Cellulose type films, olefin type films, acrylic type films and polyester type films are preferable. It may be a coating type protective film obtained by applying and curing a cationically curable composition such as an epoxy resin or a radical curable composition such as an acrylate. If necessary, plasticizers, ultraviolet absorbers, infrared absorbers, colorants such as pigments and dyes, optical brighteners, dispersants, heat stabilizers, light stabilizers, antistatic agents, antioxidants, lubricants, solvents, etc. May be included.
  • the thickness of the protective film may be 200 ⁇ m or less, preferably 1 to 100 ⁇ m. When the thickness of the protective film is within the above range, the flexibility of the protective film does not easily deteriorate.
  • the protective film can also serve as the transparent base material of the window.
  • the ⁇ /4 retardation plate is a film that gives a ⁇ /4 retardation in a direction orthogonal to the traveling direction of incident light (in-plane direction of the film).
  • the ⁇ /4 retardation plate may be a stretchable retardation plate produced by stretching a polymer film such as a cellulose-based film, an olefin-based film, or a polycarbonate-based film.
  • retarder, plasticizer, ultraviolet absorber, infrared absorber, colorant such as pigment or dye, fluorescent brightening agent, dispersant, heat stabilizer, light stabilizer, antistatic agent, antioxidant. , A lubricant, a solvent, etc. may be contained.
  • the thickness of the stretchable retardation plate may be 200 ⁇ m or less, preferably 1 to 100 ⁇ m. When the thickness is in the above range, the flexibility of the film tends to be less likely to decrease.
  • another example of the ⁇ /4 retardation plate may be a liquid crystal coating type retardation plate formed by applying a liquid crystal composition.
  • the liquid crystal composition contains a liquid crystal compound having a property of exhibiting a liquid crystal state such as nematic, cholesteric, or smectic. Any compound in the liquid crystal composition, including the liquid crystal compound, has a polymerizable functional group.
  • the liquid crystal coated retardation plate may further contain an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a cross-linking agent, a silane coupling agent and the like.
  • the liquid crystal coating type retardation plate can be manufactured by coating and curing the liquid crystal composition on the alignment film to form the liquid crystal retardation layer as in the case of the liquid crystal polarizing layer.
  • the liquid crystal coating type retardation plate can be formed thinner than the stretched type retardation plate.
  • the thickness of the liquid crystal polarizing layer may be usually 0.5 to 10 ⁇ m, preferably 1 to 5 ⁇ m.
  • the liquid crystal coating type retardation plate can be peeled from the base material and transferred to be laminated, or the base material can be laminated as it is. It is also preferable that the base material plays a role as a transparent base material of a protective film, a retardation plate, or a window.
  • phase difference of ⁇ /4 cannot be achieved in the entire visible light region, an in-plane phase difference of 100 to 180 nm, preferably 130, which is ⁇ /4 near 560 nm where the visibility is high. Often designed to be ⁇ 150 nm. It is preferable to use an inverse dispersion ⁇ /4 retardation plate using a material having a birefringence wavelength dispersion characteristic opposite to the usual one because the visibility can be improved.
  • the positive C plate may be a liquid crystal coating type retardation plate or a stretching type retardation plate.
  • the retardation in the thickness direction is usually ⁇ 200 to ⁇ 20 nm, preferably ⁇ 140 to ⁇ 40 nm.
  • the flexible display device of the present invention may further include a touch sensor.
  • the touch sensor is used as an input means.
  • various types such as a resistance film type, a surface acoustic wave type, an infrared type, an electromagnetic induction type, and a capacitance type have been proposed, and any type may be used. Of these, the capacitance method is preferable.
  • the capacitive touch sensor is divided into an active region and a non-active region located outside the active region.
  • the active area is a corresponding area which is a display area where the screen is displayed on the display panel, is an area where the user's touch is sensed, and the inactive area is a non-display area where the screen is not displayed on the display device.
  • the touch sensor includes a substrate having flexible characteristics; a sensing pattern formed in an active region of the substrate; formed in an inactive region of the substrate and connected to an external driving circuit through the sensing pattern and a pad unit. Each sensing line can be included.
  • the substrate having flexible characteristics the same material as the transparent substrate for the window can be used.
  • the toughness of the substrate of the touch sensor is preferably 2,000 MPa% or more from the viewpoint of suppressing cracks in the touch sensor. More preferably, the toughness may be 2,000 to 30,000 MPa%.
  • the toughness is defined as the area under the curve to the breaking point in a stress (MPa)-strain (%) curve (Stress-strain curve) obtained through a tensile test of a polymer material.
  • the sensing pattern may include a first pattern formed in the first direction and a second pattern formed in the second direction.
  • the first pattern and the second pattern are arranged in different directions.
  • the first pattern and the second pattern are formed on the same layer, and the respective patterns must be electrically connected in order to detect a touched point.
  • the first pattern has a structure in which the unit patterns are connected to each other through a joint, but the second pattern has a structure in which the unit patterns are separated from each other in an island shape.
  • a separate bridge electrode is required to make the connection.
  • a known transparent electrode material can be applied to the sensing pattern.
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • ZnO zinc oxide
  • IZTO indium zinc tin oxide
  • IGZO indium gallium zinc oxide
  • CTO cadmium tin oxide
  • PEDOT poly(3,4-ethylenedioxythiophene)
  • carbon nanotube carbon nanotube
  • graphene metal wire, and the like, and these may be used alone or in combination of two or more.
  • ITO can be used.
  • the metal used for the metal wire is not particularly limited, and examples thereof include silver, gold, aluminum, copper, iron, nickel, titanium, selenium, and chromium. These may be used alone or in combination of two or more.
  • the bridge electrode may be formed on the sensing layer via an insulating layer, and the bridge electrode may be formed on the substrate, and the insulating layer and the sensing pattern may be formed on the bridge electrode.
  • the bridge electrode may be formed of the same material as the sensing pattern, and may be formed of a metal such as molybdenum, silver, aluminum, copper, palladium, gold, platinum, zinc, tin, titanium, or an alloy of two or more of these. You can also do it. Since the first pattern and the second pattern must be electrically insulated, an insulating layer is formed between the sensing pattern and the bridge electrode. The insulating layer may be formed only between the joint of the first pattern and the bridge electrode, or may be formed in the structure of the layer covering the sensing pattern.
  • the bridge electrode can connect the second pattern through a contact hole formed in the insulating layer.
  • the touch sensor has a difference in transmittance between a pattern area where a pattern is formed and a non-pattern area where the pattern is not formed, specifically, a light transmittance induced by a difference in refractive index in these areas.
  • An optical adjustment layer may be further included between the substrate and the electrode as a means for appropriately compensating the difference, and the optical adjustment layer may include an inorganic insulating material or an organic insulating material.
  • the optical adjustment layer may be formed by coating a photocurable composition containing a photocurable organic binder and a solvent on a substrate.
  • the photocurable composition may further include inorganic particles.
  • the inorganic particles can increase the refractive index of the optical adjustment layer.
  • the photocurable organic binder may include, for example, a copolymer of each monomer such as an acrylate-based monomer, a styrene-based monomer, and a carboxylic acid-based monomer.
  • the photocurable organic binder may be, for example, a copolymer containing different repeating units such as an epoxy group-containing repeating unit, an acrylate repeating unit, and a carboxylic acid repeating unit.
  • the inorganic particles can include, for example, zirconia particles, titania particles, alumina particles, and the like.
  • the photocurable composition may further include various additives such as a photopolymerization initiator, a polymerizable monomer, and a curing aid.
  • Each layer such as a window, a polarizing plate, a touch sensor, etc. forming the laminated body for a flexible display device, and a film member such as a linear polarizing plate, a ⁇ /4 retardation plate, etc. constituting each layer, are bonded by an adhesive.
  • a water-based adhesive an organic solvent-based adhesive, a solvent-free adhesive, a solid adhesive, a solvent volatilization type adhesive, a water-based solvent volatilization type adhesive, a moisture-curable adhesive, a heat-curable adhesive, Anaerobic curable adhesives, active energy ray curable adhesives, hardener mixed adhesives, hot melt adhesives, pressure sensitive adhesives, pressure sensitive adhesives, rewet adhesives, etc. are widely used. Things can be used. Of these, water-based solvent volatilizing adhesives, active energy ray-curing adhesives, and pressure-sensitive adhesives are often used.
  • the thickness of the adhesive layer can be appropriately adjusted according to the required adhesive strength and the like, and is, for example, 0.01 to 500 ⁇ m, preferably 0.1 to 300 ⁇ m.
  • a plurality of adhesive layers may be present in the laminate for a flexible display device, but the thickness of each and the type of adhesive used may be the same or different.
  • polyvinyl alcohol-based polymer As the water-based solvent volatilizing adhesive, polyvinyl alcohol-based polymer, water-soluble polymer such as starch, water-dispersed polymer such as ethylene-vinyl acetate emulsion, styrene-butadiene emulsion can be used as the main polymer.
  • a cross-linking agent a silane compound, an ionic compound, a cross-linking catalyst, an antioxidant, a dye, a pigment, an inorganic filler, an organic solvent and the like may be added.
  • the water-based solvent volatile adhesive may be injected between the adhered layers to bond the adhered layers and then dried to impart adhesiveness.
  • the thickness of the adhesive layer when the water-based solvent volatilizing adhesive is used may be 0.01 to 10 ⁇ m, preferably 0.1 to 1 ⁇ m.
  • the thickness of each layer and the type of the adhesive may be the same or different.
  • the active energy ray-curable adhesive can be formed by curing an active energy ray-curable composition containing a reactive material that irradiates an active energy ray to form an adhesive layer.
  • the active energy ray-curable composition can contain at least one polymer of a radically polymerizable compound and a cationically polymerizable compound similar to the hard coat composition.
  • the radical-polymerizable compound is the same as the hard coat composition, and the same kind as the hard coat composition can be used.
  • As the radically polymerizable compound used in the adhesive layer a compound having an acryloyl group is preferable. It is also preferable to include a monofunctional compound in order to reduce the viscosity of the adhesive composition.
  • the cationically polymerizable compound is the same as that used in the hard coat composition, and the same kind as the hard coat composition can be used.
  • an epoxy compound is more preferable. It is also preferable to include a monofunctional compound as a reactive diluent to reduce the viscosity of the adhesive composition.
  • the active energy ray composition may further contain a polymerization initiator. Examples of the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, radical and cationic polymerization initiators, etc., which can be appropriately selected and used.
  • These polymerization initiators are decomposed by at least one of irradiation with active energy rays and heating to generate radicals or cations to promote radical polymerization and cation polymerization.
  • an initiator capable of initiating radical polymerization and/or cationic polymerization by irradiation with active energy rays can be used.
  • the active energy ray-curable composition is further an ion scavenger, an antioxidant, a chain transfer agent, an adhesion promoter, a thermoplastic resin, a filler, a flow viscosity modifier, a plasticizer, a defoaming agent solvent, an additive, a solvent. Can be included.
  • the active energy ray-curable composition is applied to either or both of the adherend layers and then laminated, and activated through either adherent layer or both adherent layers. It can be adhered by irradiating it with an energy ray and curing it.
  • the thickness of the adhesive layer when the active energy ray-curable adhesive is used may be 0.01 to 20 ⁇ m, preferably 0.1 to 10 ⁇ m.
  • the thickness of each layer and the type of adhesive used may be the same or different.
  • the pressure-sensitive adhesive may be classified into an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, etc. depending on the base polymer, and any of these may be used.
  • the adhesive may contain a crosslinking agent, a silane compound, an ionic compound, a crosslinking catalyst, an antioxidant, a tackifier, a plasticizer, a dye, a pigment, an inorganic filler, and the like.
  • Each component constituting the pressure-sensitive adhesive is dissolved and dispersed in a solvent to obtain a pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition is applied onto a substrate and then dried to form a pressure-sensitive adhesive layer or an adhesive layer.
  • the adhesive layer may be directly formed, or may be separately formed on a substrate and transferred. It is also preferable to use a release film to cover the adhesive surface before adhesion.
  • the thickness of the adhesive layer may be 1 to 500 ⁇ m, preferably 2 to 300 ⁇ m.
  • the thickness of each layer and the type of pressure-sensitive adhesive used may be the same or different.
  • the light shielding pattern may be applied as at least a part of a bezel or a housing of the flexible display device.
  • the visibility of the image is improved by hiding the wiring arranged at the peripheral portion of the flexible display device by the light-shielding pattern and making it difficult to see.
  • the light-shielding pattern may be in the form of a single layer or multiple layers.
  • the color of the light-shielding pattern is not particularly limited, and may have various colors such as black, white and metallic colors.
  • the light-shielding pattern can be formed of a pigment for realizing color and a polymer such as acrylic resin, ester resin, epoxy resin, polyurethane, or silicone. These may be used alone or as a mixture of two or more kinds.
  • the light-shielding pattern can be formed by various methods such as printing, lithography and inkjet.
  • the thickness of the light-shielding pattern is usually 1 to 100 ⁇ m, preferably 2 to 50 ⁇ m. Further, it is also preferable to provide a shape such as an inclination in the thickness direction of the light shielding pattern.
  • the weight average molecular weight of the acrylic acid ester polymer contained in the obtained solution was 1,800,000. 100 parts by mass of the acrylic ester polymer obtained in the above step (solid content conversion value; the same applies hereinafter), and trimethylolpropane-modified tolylene diisocyanate (manufactured by Tosoh Corp., trade name "Coronate ( (Registered trademark) L”) 0.30 part by mass and 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM403”) 0.30 part by mass as a silane coupling agent.
  • a coating solution of the pressure-sensitive adhesive composition was obtained.
  • the release treatment surface (release layer surface) of a separator (SP-PLR382190 manufactured by Lintec Co., Ltd.) was coated with the coating solution with an applicator so that the thickness after drying was 25 ⁇ m, and then at 100° C.
  • another separator (SP-PLR381031 manufactured by Lintec Co., Ltd.) is attached to the surface of the adhesive layer opposite to the surface on which the separator is attached, and the adhesive layer with a double-sided separator is attached. Obtained.
  • the pressure-sensitive adhesive layer is formed on the black acrylic plate by bonding only the pressure-sensitive adhesive layer to the black acrylic plate, and the examples and The polyamide-imide resin film obtained in Comparative Example was laminated to obtain a laminate (solvent resistance evaluation sample) in which a black acrylic plate, a pressure-sensitive adhesive layer, and an optical film were laminated in this order.
  • the total light transmittance of the optical film was measured by a fully automatic direct reading haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd. according to JIS K 7105:1981.
  • the haze of the optical film was measured by a fully automatic direct reading haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd. according to JIS K 7105:1981.
  • the thickness of the optical film was measured using an ABS Digimatic Indicator (“ID-C112BS” manufactured by Mitutoyo Corporation).
  • ⁇ The surface of the optical film is visually recognized to be uniformly black at all viewing angles other than the angle at which the fluorescent lamp is reflected.
  • ⁇ The surface of the optical film is visually recognized as black at almost all viewing angles other than the angle at which the fluorescent lamp is reflected, but there is a slight angle at which part of the surface is viewed as white.
  • X In addition to the angle at which the fluorescent lamp is reflected, there are many angles at which a part of the surface of the optical film is visually recognized due to scattering of reflected light, or there is an angle at which the entire surface is visually recognized as white.
  • OBBC 4,4′-oxybis(benzoyl chloride)
  • TPC terephthalic acid chloride
  • 105.53 mol% of acetic anhydride to TFMB was added to the flask and stirred for 15 minutes, then 35.17 mol% of 4-picoline was added to TFMB, and the temperature of the reaction vessel was raised to 70° C., and further 3 After stirring for a time, a reaction solution was obtained.
  • the obtained reaction liquid was cooled to room temperature, put into a large amount of methanol in a filament form, the deposited precipitate was taken out, immersed in methanol for 6 hours, and washed with methanol. Next, the precipitate was dried under reduced pressure at 78° C. to obtain a polyamideimide resin (1).
  • the weight average molecular weight of the polyamide-imide resin (1) was 336,000.
  • BPDA 3,3′,4,4′-biphenyltetracarboxylic dianhydride
  • TPC was added to TFMB in an amount of 22.70 mol% and stirred for 10 minutes, and TPC was added to 22.70 mol% in TFMB and stirred for 20 minutes. did. Thereafter, the same amount of DMAc as the initially added DMAc was added, TPC was added to 5.06 mol% with respect to TFMB, and the mixture was stirred for 2 hours. Then, 50.51 mol% of diisopropylethylamine and 4-picoline to TFMB and 530.39 mol% of acetic anhydride to TFMB were added to the flask, and the mixture was stirred for 30 minutes, and then the internal temperature was raised to 70°C.
  • the mixture was stirred for 3 hours to obtain a reaction solution.
  • the obtained reaction liquid was cooled to room temperature, put into a large amount of methanol in a filament form, the deposited precipitate was taken out, immersed in methanol for 6 hours, and washed with methanol. Next, the precipitate was dried under reduced pressure at 60° C. to obtain a polyamideimide resin (3).
  • the weight average molecular weight of the polyamide-imide resin (3) was 461,000.
  • TPC was added to TFMB in an amount of 30.60 mol% and OBBC was added to TFMB in an amount of 5.67 mol%, and the mixture was stirred for 10 minutes. Further, TPC was added to TFMB in an amount of 30.60 mol %, OBBC was then added to TFMB in an amount of 5.67 mol %, and the mixture was stirred for 20 minutes. Thereafter, the same amount of DMAc as the initially added DMAc was added, TPC was added so as to be 6.81 mol% with respect to TFMB, and the mixture was stirred for 2 hours.
  • ⁇ Comparative Example 1> Manufacture of optical film
  • the polyamide-imide resin (1) obtained in Synthesis Example 1 and DMAc were mixed in such an amount that the content ratio of the polyamide-imide resin in the resin composition was 11.0% by mass.
  • the obtained resin composition was applied onto a smooth surface of a polyester substrate (manufactured by Toyobo Co., Ltd., trade name "A4100") using an applicator so that the thickness of the self-supporting film was 55 ⁇ m, and the temperature was 50° C. After drying for 30 minutes and then at 140° C. for 15 minutes, the obtained coating film was peeled from the polyester base material to obtain a self-supporting film.
  • the self-supporting film was fixed to a metal frame and further dried in the air at 200° C. for 40 minutes to obtain a polyamideimide resin film (1) having a thickness of 50 ⁇ m.
  • Example 1 The polyamide-imide resin (2) obtained in Synthesis Example 2 and DMAc were mixed in such an amount that the content ratio of the polyamide-imide resin in the resin composition was 6.5% by mass. The same operation as in Comparative Example 1 was performed to obtain a polyamideimide resin film (2).
  • Example 2 The polyamide-imide resin (3) obtained in Synthesis Example 3 and DMAc were mixed in an amount such that the content ratio of the polyamide-imide resin in the resin composition was 6.5% by mass. The same operation as in Comparative Example 1 was performed to obtain a polyamideimide resin film (3).
  • Example 3 The polyamide-imide resin (4) obtained in Synthesis Example 3 and DMAc were mixed in such an amount that the content ratio of the polyamide-imide resin in the resin composition was 8.5% by mass. The same operation as in Comparative Example 1 was performed to obtain a polyamideimide resin film (4).
  • the polyamide-imide resin films (1) to (4) obtained as described above were evaluated for total light transmittance, haze, solvent resistance test, and appearance quality. The results obtained are shown in Table 1.

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Abstract

La présente invention concerne un film optique ayant une excellente qualité d'apparence, la qualité d'apparence du film optique n'étant pas dégradée lors du contact avec de l'alcool. Le film optique comprend une résine de polyamide-imide qui contient au moins : un motif structurel dérivé d'un composé acide tétracarboxylique et représenté par la formule (a) ; un motif structurel dérivé d'un composé acide dicarboxylique et représenté par la formule (b) ; et un motif structurel dérivé d'un composé diamine et représenté par la formule (c) [dans la formule (a), Y représente un groupe organique tétravalent ; dans la formule (b), Z représente un groupe organique divalent ; dans la formule (c), X est un groupe organique divalent ; Rc, indépendamment l'un de l'autre, représente un atome d'hydrogène ou une liaison ; et * représente une liaison]. La résine de polyamide-imide comprend au moins un motif structurel sélectionné dans le groupe constitué d'un motif structurel (a1) et d'un motif structurel (b1). Le motif structurel (a1) est représenté par la formule (a) comme motif structurel dérivé d'un composé acide tétracarboxylique, où Y est représenté par la formule (1) [dans la formule (1), Ra, indépendamment l'un de l'autre, représente un atome d'hydrogène, un groupe alkyle en C1 à C12, un groupe alcoxy en C1 à C12 ou un groupe aryle en C6 à C12 ; les atomes d'hydrogène compris dans Ra, indépendamment l'un de l'autre, peuvent être substitués par des atomes d'halogène ; n représente un nombre entier d'une valeur de 0 à 2 ; * représente une liaison ; R* représente une liaison si Y est représenté par la formule (1), et représente Ra si Z est représenté par la formule (1)]. Le motif structurel (b1) est représenté par la formule (b) comme motif structurel dérivé d'un composé acide dicarboxylique, où Z est représenté par la formule (1). La valeur absolue de la différence ΔL* entre la luminosité L1 * du film optique, la luminosité L1 * étant obtenue en mesurant la lumière réfléchie et basée sur le système de couleurs L*a*b*, et la luminosité L2 ＊ du film optique qui a été en contact avec l'éthanol durant 40 minutes, la luminosité L2 ＊ étant obtenue en mesurant la différence de couleur de surface et basée sur le système de couleurs L*a*b*, n'est pas supérieure à 0,5.
PCT/JP2019/050541 2018-12-28 2019-12-24 Film optique et dispositif d'affichage souple WO2020138045A1 (fr)

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