WO2022085735A1 - ハードコートフィルムおよびその製造方法、ならびに画像表示装置 - Google Patents

ハードコートフィルムおよびその製造方法、ならびに画像表示装置 Download PDF

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WO2022085735A1
WO2022085735A1 PCT/JP2021/038815 JP2021038815W WO2022085735A1 WO 2022085735 A1 WO2022085735 A1 WO 2022085735A1 JP 2021038815 W JP2021038815 W JP 2021038815W WO 2022085735 A1 WO2022085735 A1 WO 2022085735A1
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hard coat
film
polyimide
bis
ultraviolet absorber
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PCT/JP2021/038815
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English (en)
French (fr)
Japanese (ja)
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紘平 小川
敬介 片山
裕之 後
文康 石黒
智史 杉山
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株式会社カネカ
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Priority to CN202180072077.8A priority Critical patent/CN116419848A/zh
Priority to JP2022557588A priority patent/JPWO2022085735A1/ja
Priority to KR1020237014945A priority patent/KR20230092933A/ko
Publication of WO2022085735A1 publication Critical patent/WO2022085735A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • 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 a hard coat film having a hard coat layer on at least one surface of the transparent polyimide film, a method for manufacturing the same, and an image display device provided with the hard coat film.
  • Patent Document 1 discloses that a hard coat layer is formed by using a photocurable resin composition containing a reactive urethane acrylate, a photoradical polymerization initiator and an ultraviolet absorber.
  • the surface protective material of the display device is located in the outermost layer, it is easily exposed to external light. Therefore, the hard coat film used as a surface protective material is required to have high light resistance with little change in optical characteristics and mechanical strength even when exposed to ultraviolet rays or the like.
  • One aspect of the present invention is a hard-coated film in which a hard-coat layer is provided on at least one surface of the base film.
  • the base film is a polyimide film containing a polyimide resin, and the hard coat layer is made of a cured product of a photocurable resin composition.
  • Each of the hardcoat layer and the polyimide film contains an ultraviolet absorber.
  • the ultraviolet absorber contained in the polyimide film and the hard coat layer a benzotriazole compound or a triazine compound is preferable.
  • the content of the ultraviolet absorber in the polyimide film is preferably 0.1 to 4.5% by weight.
  • the content of the ultraviolet absorber in the hard coat layer is preferably 0.1 to 4.5% by weight.
  • the thickness of the hard coat layer is, for example, 0.5 to 100 ⁇ m.
  • the thickness of the polyimide film is, for example, 5 to 100 ⁇ m.
  • the polyimide resin of the polyimide film is preferably soluble in dichloromethane.
  • a polyimide film containing an ultraviolet absorber can be obtained by applying a solution containing a polyimide resin soluble in dichloromethane and an ultraviolet absorber onto a substrate and removing the solvent.
  • a photocurable resin composition (hard coat composition) containing a photocurable resin and a photopolymerization initiator is applied to the surface of the polyimide film and photocured to provide a hard coat layer on the surface of the polyimide film.
  • a hard coat film can be produced.
  • the hardcoat composition may be photocationically polymerizable.
  • An example of a photocurable resin having photocationic polymerizable properties is a polysiloxane compound having an epoxy group.
  • the hard coat composition contains, for example, a photocurable resin having photocationic polymerizable properties, a photocationic polymerization initiator (photoacid generator), and an ultraviolet absorber.
  • the hard coat film can be used as a surface protective material arranged on the visible side surface of the image display panel, for example, in an image display device.
  • the image display device may be bendable.
  • the hard coat film contains an ultraviolet absorber in both the polyimide film and the hard coat layer, photodegradation of the polyimide is suppressed, so that the optical characteristics and mechanical strength change even when exposed to ultraviolet rays or the like. It is small and has excellent light resistance.
  • FIG. 1 is a cross-sectional view of a hard coat film 10 provided with a hard coat layer 2 on one main surface of the polyimide film 1.
  • the hard coat layer 2 is formed by applying the hard coat composition to the main surface of the polyimide film 1 as a film base material and curing it.
  • the hard coat layer may be provided only on one main surface of the polyimide film, or may be provided on both sides of the polyimide film.
  • Both the polyimide film 1 and the hard coat layer 2 contain an ultraviolet absorber. Since both the polyimide film and the hard coat layer contain an ultraviolet absorber, the light resistance is improved, and the yellowing of the hard coat film tends to be suppressed even after long-term exposure to ultraviolet rays.
  • Examples of the ultraviolet absorber contained in the polyimide film and the hard coat layer include triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, hydroxybenzoate-based ultraviolet absorbers, and the like. Be done. Among them, a benzotriazole-based ultraviolet absorber and a triazine-based ultraviolet absorber are preferable because they absorb less visible light and can obtain good light resistance.
  • benzotriazole-based ultraviolet absorber examples include 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (ADEKA "Adecastab LA-24”). ), 2- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol ("Adecastab LA-29” manufactured by ADEKA), 2,2'-methylenebis [6 -(2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] (ADEKA "Adecastab LA-31G” and “Adecastab LA-31RG”), 2- ( 2H-benzotriazole-2-yl) -p-cresol (ADEKA "Adecastab LA-32”), 2- (2H-benzotriazole-2-yl) -6-dodecyl-4-methylphenol (BASF "TINUVIN571”) ”),
  • triazine-based ultraviolet absorber examples include 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] -phenol.
  • the compounds exemplified in this specification may be used alone or in combination (coexistence) of two or more.
  • the polyimide film 1 contains a polyimide resin.
  • Polyimide is generally obtained by dehydration cyclization of a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride (hereinafter, may be simply referred to as "acid dianhydride”) with a diamine. That is, the polyimide has an acid dianhydride-derived structure and a diamine-derived structure.
  • a method in which a solution of a polyimide resin dissolved in an organic solvent is applied onto a substrate and the solvent is dried and removed by heating is preferably adopted. Therefore, in addition to being transparent, polyimide is preferably soluble in organic solvents. From the viewpoint of productivity of the polyimide film, it is preferable to use a low boiling point such as dichloromethane for the solution casting method. Therefore, the polyimide resin is preferably soluble in dichloromethane.
  • the acid dianhydride component includes a tetracarboxylic acid dianhydride represented by the general formula (1) and a tetracarboxylic acid dianhydride having a cyclobutane structure, and as a diamine component.
  • Polyimides containing fluoroalkyl substituted benzidine can be mentioned.
  • n is 1 or 2.
  • R 1 to R 4 are independently hydrogen atoms, fluorine atoms, alkyl groups having 1 to 20 carbon atoms or fluoroalkyl groups, and at least one of R 1 to R 4 has 1 to 1 carbon atoms. 20 alkyl or fluoroalkyl groups.
  • the fluoroalkyl-substituted benzidine is contained in an amount of 40 mol% or more and 100 mol% or less with respect to 100 mol% of the total amount of the diamine component, and the formula (1) is used with respect to 100 mol% of the total amount of the acid dianhydride component.
  • examples thereof include an acid dianhydride having an ester structure represented by 40 mol% or more and 85 mol% or less, and an acid dianhydride having a cyclobutane structure containing 15 mol% or more and 60 mol% or less.
  • the compound represented by the above general formula (1) is an acid dianhydride having an ester structure.
  • R 1 to R 4 are an alkyl group or a fluoroalkyl group
  • examples of the alkyl group when R 1 to R 4 are an alkyl group or a fluoroalkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a t-butyl group. Cyclobutyl group, n-pentyl group, isopentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group and the like can be mentioned.
  • Examples of the fluoroalkyl group include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group and the
  • the bis (1,3-dioxo-1,3-dihydroiso) represented by the following formula (2) Benzofuran-5-carboxylic acid) -2,2', 3,3', 5,5'-hexamethylbiphenyl-4,4'diyl (TAHMBP) is preferred.
  • acid dianhydride having a cyclobutane structure Specific examples of the acid dianhydride having a cyclobutane structure include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and 1,3-dimethyl-1,2-2,3,4-cyclobutanetetracarboxylic acid dianhydride.
  • CBDA 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride
  • fluoroalkyl substituted benzidine fluoroalkyl substituted benzidine
  • fluoroalkyl substituted benzidine include 2-fluorobenzidine, 3-fluorobenzidine, 2,3-difluorobenzidine, 2,5-difluorobenzidine, 2,6-difluorobenzidine, and 2,3,5-trifluorobenzidine.
  • 2,3,6-trifluorobenzidine 2,3,5,6-tetrafluorobenzidine, 2,2'-difluorobenzidine, 3,3'-difluorobenzidine, 2,3'-difluorobenzidine, 2,2 ', 3-trifluorobenzidine, 2,3,3'-trifluorobenzidine, 2,2', 5-trifluorobenzidine, 2,2', 6-trifluorobenzidine, 2,3', 5-trifluoro Benzidine, 2,3', 6,-trifluorobenzidine, 2,2', 3,3'-tetrafluorobenzidine, 2,2', 5,5'-tetrafluorobenzidine, 2,2', 6,6 '-Tetrafluorobenzidine, 2,2', 3,3', 6,6'-hexafluorobenzidine, 2,2', 3,3', 5,5', 6,6'-octafluorobenzidine, 2 -(Trifluoromethyl) benzidine, 3- (trifluoro
  • a fluoroalkyl-substituted benzidine having a fluoroalkyl group at the 2-position of the biphenyl skeleton is preferable, and 2,2'-bis (trifluoromethyl) benzidine is more preferable.
  • the aromatic ring of the biphenyl skeleton is twisted due to steric hindrance of the fluoroalkyl group, and coloring is reduced due to the electron attractiveness of the fluoroalkyl group.
  • the polyimide may contain an acid dianhydride component and a diamine component other than the above, as long as the solubility in a low boiling point solvent such as dichloromethane is not impaired and the transparency and mechanical strength are not impaired.
  • acid dianhydride components that can be used in combination are pyromellitic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane.
  • diamines examples include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3, 3'-Diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl Sulfon, 9,9-bis (4-aminophenyl) fluorene, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone
  • the polyimide of one embodiment contains, as an acid dianhydride component, an acid dianhydride having an ester structure represented by the general formula (1) and an acid dianhydride having a cyclobutane structure, and as a diamine component.
  • an acid dianhydride component an acid dianhydride having an ester structure represented by the general formula (1) and an acid dianhydride having a cyclobutane structure, and as a diamine component.
  • fluoroalkyl substituted benzidine includes fluoroalkyl substituted benzidine.
  • the amount of the acid dianhydride represented by the general formula (1) is preferably 40 to 85 mol%, more preferably 45 to 80 mol%, and 50 to 70 with respect to 100 mol% of the total amount of the acid dianhydride component. Mol% is more preferred. Within this range, a polyimide showing high solubility in a low boiling point solvent such as dichloromethane and having excellent mechanical strength can be obtained. As described above, among the acid dianhydrides represented by the general formula (1), TAHMBP represented by the formula (2) is particularly preferable.
  • the amount of acid dianhydride having a cyclobutane structure is preferably 15 to 60 mol%, more preferably 20 to 55 mol%, still more preferably 25 to 50 mol%, based on 100 mol% of the total amount of acid dianhydride components. .. Within this range, a polyimide having solubility in a low boiling point solvent such as dichloromethane, less coloring, and excellent mechanical strength can be obtained. As described above, among the acid dianhydrides having a cyclobutane structure, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride (CBDA) is particularly preferable.
  • CBDA 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride
  • the amount thereof is based on 100 mol% of the total amount of the acid dianhydride component. 45 mol% or less is preferable, and 30 mol% or less is more preferable. From the viewpoint of obtaining a polyimide having excellent solubility, transparency and mechanical strength, preferred examples of the acid dianhydride used in combination are 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride (s-BPDA).
  • s-BPDA 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride
  • s-ODPA 4,4'-oxydiphthalic acid dianhydride
  • 6FDA 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropanedianhydride
  • the amount of the fluoroalkyl-substituted benzidine is preferably 40 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, based on 100 mol% of the total diamine component. Within this range, a polyimide having excellent transparency and solubility can be obtained without impairing the mechanical strength. As mentioned above, among the fluoroalkyl-substituted benzidines, 2,2'-bis (trifluoromethyl) benzidine (TFMB) is particularly preferable.
  • TFMB 2,2'-bis (trifluoromethyl) benzidine
  • the amount thereof is preferably 60 mol% or less, more preferably 40% or less, still more preferably 30 mol% or less, based on 100 mol% of the total amount of the diamine component.
  • fluoroalkyl substituted benzidine such as TFMB and 3,3'-diaminodiphenyl sulfone (3,3'-DDS) or 4,4'-diaminodiphenyl sulfone (3,3') -It is preferable to use DDS) together.
  • the amount of diaminodiphenyl sulfone with respect to 100 mol% of the total amount of the diamine component is preferably 5 to 40 mol%, more preferably 10 to 30 mol%.
  • the polyimide preferably contains 40 to 85 mol% of TAHMBP and 15 to 60 mol% of CBDA as an acid dianhydride component, and 40 to 100 mol% of TFMB as a diamine component. Further, from the viewpoint of improving the solubility in a solvent and the transparency of the film, 5 to 40 mol% of diaminodiphenyl sulfone (3,3'-DDS and / and 4,4'-DDS) is contained as a diamine component. Is preferable, and 6FDA, s-BPDA, s-ODPA and the like may be contained as the acid dianhydride.
  • the method for producing the polyimide resin is not particularly limited, but a method in which a diamine and an acid dianhydride are reacted in a solvent to prepare a polyamic acid as a polyimide precursor and imidized by dehydration cyclization of the polyamic acid is preferable.
  • a polyimide solution can be obtained by adding an imidization catalyst and a dehydrating agent to the polyamic acid solution to dehydrate and close the polyamic acid.
  • a polyimide resin can be obtained by mixing a polyimide solution and a poor solvent of polyimide to precipitate a polyimide resin and then solid-liquid separation.
  • a polyamic acid solution is obtained by reacting the acid dianhydride with the diamine in a solvent. It is preferable to use substantially equal molar amounts of acid dianhydride and diamine. That is, the molar ratio of the acid dianhydride component to the diamine is preferably in the range of 95: 105 to 105: 95.
  • the organic solvent that can be used is not particularly limited, and the acid dianhydride and diamine, and the polyamic acid that is a polymerization product may be dissolved.
  • the organic solvent include urea-based solvents such as methyl urea, N, N-dimethylethyl urea; and sulfone-based solvents such as dimethyl sulfoxide, diphenyl sulfone, and tetramethyl sulfone; N, N-dimethylacetamide, N, N-.
  • Amid solvents such as dimethylformamide, N, N'-diethylacetamide, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, hexamethylphosphate triamide; alkyl halide solvents such as chloroform and dichloromethane; benzene, toluene and the like.
  • alkyl halide solvents such as chloroform and dichloromethane
  • benzene, toluene and the like examples thereof include aromatic hydrocarbon solvents, ether solvents such as tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, dimethyl ether, diethyl ether, and p-cresol methyl ether.
  • N, N-dimethylacetamide, N, N-dimethylformamide, or N-methylpyrrolidone is preferable because of its excellent polymerization reactivity and solubility of polyamic acid.
  • the reaction temperature in the polymerization of acid dianhydride and diamine is not particularly limited, but is preferably 0 ° C. or higher and 80 ° C. or lower, and more preferably 20 ° C. or higher and 45 ° C. or lower.
  • the temperature is 0 ° C. or higher, the decrease in the reaction rate is suppressed, and when the temperature is 80 ° C. or lower, the decrease in the degree of polymerization due to ring-opening of the acid dianhydride tends to be suppressed.
  • Polyimide is obtained by dehydration cyclization of polyamic acid.
  • a chemical imidization method in which a dehydrating agent, an imidization catalyst, or the like is added to the polyamic acid solution is suitable.
  • the polyamic acid solution may be heated to accelerate the progress of imidization.
  • a tertiary amine is used as the imidization catalyst.
  • a heterocyclic tertiary amine is preferable.
  • Specific examples of the heterocyclic tertiary amine include pyridine, picoline, quinoline, isoquinoline and the like.
  • carboxylic acid anhydride is used, and specific examples thereof include acetic anhydride, propionic acid anhydride, n-butyric acid anhydride, benzoic acid anhydride, and trifluoroacetic anhydride.
  • the amount of the imidization catalyst added is preferably 0.5 to 5.0 times the molar equivalent, more preferably 0.7 to 2.5 times the molar equivalent, and 0.8 to 2. A 0-fold molar equivalent is more preferred.
  • the amount of the dehydrating agent added is preferably 0.5 to 10.0 times the molar equivalent, more preferably 0.7 to 5.0 times the molar equivalent, and 0.8 to 3.0 times the amide group of the polyamic acid. Double molar equivalents are more preferred.
  • the poor solvent is a poor solvent of the polyimide resin, preferably one that is mixed with a solvent in which the polyimide resin is dissolved, and examples thereof include water and alcohols.
  • alcohols include methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, triethylene glycol, 2-butyl alcohol, 2-hexyl alcohol, cyclopentyl alcohol, cyclohexyl alcohol, phenol, t-butyl alcohol and the like.
  • Alcohols such as isopropyl alcohol, 2-butyl alcohol, 2-pentyl alcohol, phenol, cyclopentyl alcohol, cyclohexyl alcohol, and t-butyl alcohol are preferable, and isopropyl alcohol is particularly preferable, because ring opening of the polyimide is unlikely to occur.
  • a polyimide film can be produced by applying a polyimide solution (a dope for film formation) in which a polyimide resin is dissolved in an organic solvent onto a substrate and drying and removing the solvent.
  • the organic solvent for dissolving the polyimide resin may be any solvent as long as it is soluble and soluble in the above-mentioned polyimide resin, and may be appropriately selected depending on the intended use of the polyimide resin.
  • a low boiling point solvent such as, 3-dioxolane is preferable, and dichloromethane is particularly preferable because the boiling point is low and the solvent can be easily removed by drying.
  • the solid content concentration of the polyimide solution may be appropriately set according to the molecular weight of the polyimide, the thickness of the film, the film forming environment, and the like.
  • the solid content concentration is preferably 5 to 30% by weight, more preferably 6 to 20% by weight.
  • the polyimide film contains an ultraviolet absorber.
  • the ultraviolet absorber a benzotriazole-based ultraviolet absorber and a triazine-based ultraviolet absorber are preferable because they absorb less visible light and can obtain good light resistance.
  • the polyimide solution preferably contains a triazine-based ultraviolet absorber.
  • the polyimide solution (and the polyimide film) may contain a triazine-based ultraviolet absorber and a benzotriazole-based ultraviolet absorber.
  • the acid dianhydride of the general formula (1) used as the acid dianhydride component of polyimide is an ester of phenol and trimellitic anhydride, and is easily deteriorated by light due to ultraviolet rays. It is presumed that this is because rearrangement reactions such as optical Fries rearrangement are likely to occur due to the structure. Since the polyimide film contains an ultraviolet absorber, the ultraviolet rays incident on the polyimide film are absorbed by the ultraviolet absorber, so that the polyimide is not easily affected by the ultraviolet rays and tends to suppress coloring (yellowing) due to light deterioration. be.
  • the amount of the ultraviolet absorber in the polyimide solution is preferably 0.1 part by weight or more, more preferably 0.3 part by weight or more, and 0 part by weight with respect to 100 parts by weight of the total solid content. It may be .5 parts by weight or more, 0.7 parts by weight or more, or 1 part by weight or more.
  • the larger the amount of the ultraviolet absorber the more the photodegradation of the polyimide tends to be suppressed.
  • the amount of the ultraviolet absorber is excessively large, the ultraviolet absorber may not be sufficiently compatible with the polyimide, which may cause the polyimide film to become cloudy or bleed out of the ultraviolet absorber to the surface.
  • the amount of the ultraviolet absorber in the polyimide solution is preferably 4.5 parts by weight or less, more preferably 4 parts by weight or less, and 3.5 parts by weight or less or 3 parts by weight or less with respect to 100 parts by weight of the total solid content. May be.
  • the polyimide contains the acid dianhydride component represented by the general formula (1), it is easy to sufficiently suppress the photodegradation of the polyimide while suppressing the white turbidity of the film and the bleed-out of the ultraviolet absorber. is not. Therefore, as will be described later, it is preferable that the hard coat layer 2 provided on the surface of the polyimide film 1 contains an ultraviolet absorber to provide ultraviolet shielding properties and reduce the amount of ultraviolet rays reaching the polyimide film 1. ..
  • the polyimide solution may contain resin components and additives other than the polyimide resin and the ultraviolet absorber.
  • the additive include a cross-linking agent, a dye, a surfactant, a leveling agent, a plasticizer, fine particles and the like.
  • the content of the polyimide resin with respect to 100 parts by weight of the solid content of the polyimide resin composition is preferably 60 parts by weight or more, more preferably 70 parts by weight or more, still more preferably 80 parts by weight or more.
  • the above dyes include anthraquinone compounds, phthalocyanine compounds, indigo compounds and the like.
  • the anthraquinone type is preferable from the viewpoint of heat resistance.
  • the amount used is, for example, about 0.1 to 100 ppm based on the polyimide resin, and may be 1 to 90 ppm, 10 to 80 ppm, or 20 to 70 ppm.
  • the color tone of the polyimide film can be adjusted.
  • the polyimide and the ultraviolet absorber are slightly colored yellow because they absorb light in the short wavelength region of visible light, but the hue can be neutralized by adding a dye that functions as a brewing agent.
  • bluing agent known ones can be appropriately used, and commercially available products such as "Macrolex Blue RR”, “Sumiplast Violet B”, “Sumiplast Violet OR”, “Plast Blue8580”, “Plast Blue8590”, and “Plast” can be used as appropriate. "Bluelet 8840” and the like.
  • a method of applying the polyimide solution to the substrate a known method can be used, and for example, it can be applied by a bar coater or a comma coater.
  • a glass substrate, a metal substrate such as SUS, a metal drum, a metal belt, a plastic film, or the like can be used as the base material to which the polyimide solution is applied.
  • a material that does not dissolve in the solvent of the film-forming dope may be appropriately selected, and as the plastic material, polyethylene terephthalate, polycarbonate, polyacrylate, polyethylene naphthalate or the like is used.
  • the heating temperature is not particularly limited, but is preferably 200 ° C. or lower, more preferably 180 ° C. or lower, from the viewpoint of suppressing the coloring of the polyimide film and the volatilization of the ultraviolet absorber.
  • the heating temperature may be gradually increased.
  • the solvent may be dried under reduced pressure.
  • the residual solvent amount of the polyimide film (mass of the solvent contained in the film with respect to the mass of the film) is preferably 1.5% or less, more preferably 1.0% or less. When the amount of residual solvent is in this range, the mechanical strength of the polyimide film tends to be improved.
  • the thickness of the polyimide film is not particularly limited and may be appropriately set according to the intended use.
  • the thickness of the polyimide film is, for example, about 5 to 100 ⁇ m. From the viewpoint of achieving both mechanical strength and transparency, the thickness of the polyimide film is preferably 30 ⁇ m or more, more preferably 35 ⁇ m or more, still more preferably 40 ⁇ m or more. In particular, when used for applications requiring strength such as a cover window of a display, the thickness of the polyimide film is preferably 40 ⁇ m or more.
  • the thickness of the polyimide film is preferably 90 ⁇ m or less, more preferably 85 ⁇ m or less.
  • the pencil hardness of the polyimide film before forming the hard coat layer is preferably HB or higher. F or more is more preferable.
  • the hard coat layer 2 is formed by applying the hard coat composition on the polyimide film 1 and photo-curing it.
  • the hardcourt composition contains a photocurable resin and a photopolymerization initiator. That is, the hard coat layer is a cured resin layer made of a cured product of the hard coat composition which is a photocurable resin composition.
  • a hardcoat layer containing the UV absorber is formed.
  • the photocurable resin of the hardcoat composition is a polyfunctional compound having two or more photopolymerizable functional groups.
  • the polyfunctional compound may be a monomer or an oligomer.
  • the photopolymerizable functional group may be radically polymerizable or cationically polymerizable.
  • Examples of the radically polymerizable functional group include functional groups having an ethylenically unsaturated double bond such as a vinyl group and a (meth) acryloyl group.
  • Examples of the cationically polymerizable functional group include a cyclic ether group such as an epoxy group and an oxetane group.
  • an epoxy group and an oxetane group are preferable as the photopolymerizable functional group of the photocurable resin because it can be cured by photocationic polymerization and the curing shrinkage is small.
  • the photocationically polymerizable functional group containing an epoxy group include a glycidyl group and an alicyclic epoxy group. Of these, an alicyclic epoxy group is preferable because of its high reactivity with photocationic polymerization.
  • the hard coat composition contains an ultraviolet absorber
  • ultraviolet rays as excitation light may be absorbed by the ultraviolet absorber during photocuring by irradiation with ultraviolet rays, which may cause curing failure (curing inhibition).
  • photoradicals which are active species of photoradical polymerization reactions, have a short life, they need to be continuously irradiated with ultraviolet rays during the curing reaction, and are easily affected by curing inhibition by ultraviolet absorbers.
  • the active species of the photocationic polymerization reaction is an acid generated by light irradiation, and the life of the active species is longer than that of photoradicals, and the curing reaction proceeds for a long time even after light irradiation. Therefore, the photocationic polymerization is less susceptible to the influence of the ultraviolet absorber than the photoradical polymerization, and even when the hard coat composition contains the ultraviolet absorber, curing failure is less likely to occur. Therefore, the hard coat composition is a photocationic polymerizable composition containing a photocurable resin having a photocationically polymerizable functional group such as an epoxy group, a photocationic polymerization initiator (photoacid generator), and an ultraviolet absorber. It is preferable to have.
  • photocationically polymerizable hard coat composition examples include compositions containing polysiloxane compounds having an epoxy group disclosed in WO2018 / 096729, WO2014 / 204010, JP-A-2017-8142 and the like. Be done.
  • the polysiloxane compound having photocationic polymerizable has an epoxy group as a photocationically polymerizable functional group.
  • the epoxy group is preferably an alicyclic epoxy group, and among them, a 3,4-epoxycyclohexyl group is preferable.
  • the polysiloxane compound having an alicyclic epoxy group is, for example, (A) condensation of a silane compound having an alicyclic epoxy group; or (B) a carbon-carbon double having a reactivity with a SiH group in one molecule. It is obtained by a hydrosilylation reaction between a compound having a bond and an alicyclic epoxy group (for example, vinylcyclohexene oxide) and a polysiloxane compound having at least two SiH groups in one molecule. Since a polysiloxane compound having a network structure having a large number of alicyclic epoxy groups in one molecule can be obtained, the polysiloxane compound is preferably formed by the method (A) above.
  • Examples of the silane compound used as a raw material for the condensation reaction of the above (A) include a compound represented by the following general formula (3). Y-R 5- (Si (OR 6 ) x R 7 3-x ) ... (3)
  • Y is an alicyclic epoxy group
  • R5 is an alkylene group having 1 to 10 carbon atoms.
  • R 6 is a monovalent hydrocarbon group selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an alkyl group having 7 to 12 carbon atoms.
  • R 7 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • x is an integer of 1 to 3. When x is 2 or more, the plurality of R 6s may be the same or different. When (3-x) is 2 or more, the plurality of R 7s may be the same or different.
  • the alicyclic epoxy group Y is preferably a 3,4-epoxycyclohexyl group.
  • the alkylene group R 5 may be linear or has branches, but a linear alkylene group is preferable, a linear alkylene having 1 to 5 carbon atoms is preferable, and ethylene is particularly preferable. That is, the substituent Y-R5 - bonded to Si is preferably ⁇ - (3,4-epoxycyclohexyl) ethyl.
  • R 6 examples include hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, phenyl group, tolyl group, xylyl group and naphthyl group. Examples thereof include a benzyl group and a phenethyl group. From the viewpoint of enhancing the reactivity of the alicyclic epoxy group during photocationic polymerization of the polysiloxane compound, R6 is preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably an ethyl group or a propyl group.
  • R 7 examples include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, a decyl group and the like.
  • R7 is preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.
  • x in the general formula (3) is preferably 2 or 3.
  • a silane compound having x of 2 or 3 and a silane compound having x of 1 may be used in combination for the purpose of adjusting the molecular weight of the polysiloxane compound obtained by condensation.
  • silane compound represented by the general formula (3) examples include ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, and ⁇ - ( 3,4-Epoxycyclohexyl) ethyldimethylmethoxysilane, ⁇ - (3,4-epoxycyclohexyl) propyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) propylmethyldimethoxysilane, ⁇ - (3,4-epoxy) Cyclohexyl) propyldimethylmethoxysilane and the like can be mentioned.
  • a Si—O—Si bond is formed to form a polysiloxane compound.
  • Alicyclic epoxides such as epoxycyclohexyl groups have high electrophilic reactivity and low nucleophilic reactivity. Therefore, from the viewpoint of suppressing the ring-opening of the epoxy group, it is preferable to carry out the reaction under neutral or basic conditions.
  • Examples of the basic compound used to make the reaction system basic include alkali metals such as sodium hydroxide, lithium hydroxide and magnesium hydroxide, hydroxides of alkaline earth metals, and amines.
  • alkali metals such as sodium hydroxide, lithium hydroxide and magnesium hydroxide
  • hydroxides of alkaline earth metals and amines.
  • the basic compound used for forming the polysiloxane compound is preferably one that can be removed by volatilization.
  • the basic compound preferably has low nucleophilicity. Therefore, as the basic compound, a tertiary amine is preferable, and among them, a tertiary amine having a boiling point of 30 to 160 ° C. such as triethylamine, diethylmethylamine, tripropylamine, methyldiisopropylamine and diisopropylethylamine is preferable.
  • the weight average molecular weight of the polysiloxane compound obtained by condensing the silane compound is preferably 500 or more. Further, from the viewpoint of suppressing the volatilization of the polysiloxane compound, the weight average molecular weight of the polysiloxane compound is preferably 500 or more. On the other hand, if the molecular weight is excessively large, cloudiness may occur due to a decrease in compatibility with other compositions. Therefore, the weight average molecular weight of the polysiloxane compound is preferably 20000 or less. The weight average molecular weight of the polysiloxane compound is more preferably 1000 to 18000, more preferably 1500 to 16000, still more preferably 2000 to 14000, and particularly preferably 2800 to 12000.
  • the polysiloxane compound preferably has a plurality of alicyclic epoxy groups in one molecule.
  • the number of alicyclic epoxy groups in one molecule of the polysiloxane compound is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more.
  • the number of alicyclic epoxy groups contained in one molecule becomes excessively large, the proportion of functional groups that do not contribute to cross-linking between molecules during curing may increase. Therefore, the number of alicyclic epoxy groups in one molecule of the polysiloxane compound is preferably 100 or less, more preferably 80 or less, further preferably 70 or less, and particularly preferably 60 or less.
  • the polysiloxane compound obtained by the condensation of the silane compound represented by the general formula (3) has the residual ratio of the alicyclic epoxy group. Is preferable.
  • the ratio of the number of moles of the alicyclic epoxy group of the condensate (polysiloxane compound) to the number of moles of the alicyclic epoxy group contained in the silane compound is preferably 20% or more, more preferably 40% or more, and more preferably 60% or more. Is even more preferable.
  • the number of OR 6 groups remaining per silane compound unit in the polysiloxane compound is small.
  • the number of OR 6 groups per Si atom in the polysiloxane compound is 2 or less.
  • the average number of OR 6 units per Si atom is preferably 1.5 or less, and more preferably 1.0 or less.
  • the number of OR 6 units per Si atom in the polysiloxane compound may be 0.01 or more, 0.05 or more, or 0.3 or more on average.
  • a silane compound having no alicyclic epoxy group may be used in addition to the silane compound having an alicyclic epoxy group.
  • the silane compound having no alicyclic epoxy group is represented by, for example, the following general formula (4). R 8 -Si (OR 6 ) 3 ... (4)
  • R 8 of the general formula (4) is selected from the group consisting of substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, alkenyl groups, and substituted aryl groups, and is monovalent without an alicyclic epoxy group. It is a group.
  • R 8 is an alkyl group having a substituent
  • examples of the substituent include a glycidyl group, a thiol group, an amino group, a (meth) acryloyl group, a phenyl group, a cyclohexyl group, a halogen and the like.
  • R 6 in the general formula (4) is the same as R 6 in the general formula (3).
  • the polysiloxane compound obtained by the reaction of the silane compound is a silane compound having no alicyclic epoxy group (general formula) as opposed to a silane compound having an alicyclic epoxy group (compound represented by the general formula (3)).
  • the compound represented by (4) is preferably condensed under the condition that the molar ratio is 2 or less.
  • the molar ratio of the compound represented by the general formula (4) to the compound represented by the general formula (3) is preferably 1 or less, more preferably 0.6 or less, further preferably 0.4 or less, and 0.2. The following are particularly preferred.
  • the molar ratio of the compound represented by the general formula (4) to the compound represented by the general formula (3) may be 0.
  • the content of the polysiloxane compound in the hardcoat composition is preferably 40 parts by weight or more, preferably 50 parts by weight or more, based on 100 parts by weight of the total solid content. More preferably, 60 parts by weight or more is further preferable.
  • the photocationically polymerizable hard coat composition preferably contains a photocationic polymerization initiator.
  • the photocationic polymerization initiator is a compound (photoacid generator) that generates an acid by irradiation with active energy rays. The acid generated from the photoacid generator reacts with the alicyclic epoxy group of the polysiloxane compound to form intermolecular crosslinks and cure the hard coat material.
  • the photoacid generator examples include strong acids such as toluene sulfonic acid or boron tetrafluoride; onium salts such as sulfonium salt, ammonium salt, phosphonium salt, iodonium salt and selenium salt; iron-allene complexes; silanol-metal chelate complexes.
  • Sulfonic acid derivatives such as disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imidesulfonates, benzoinsulfonates; organic halogen compounds and the like.
  • aromatic sulfonium salts or aromatic iodonium salts are preferable because they have high stability in a hard coat composition containing a polysiloxane compound having an alicyclic epoxy group.
  • the counter anion of the aromatic sulfonium salt or the aromatic iodonium salt is a fluoroborate anion or a fluoroantimonate anion.
  • fluoroborate anions are preferred.
  • a fluorophosphate anion or a fluoroantimonate anion is preferable.
  • Such a photoacid generator include diphenyl (4-phenylthiophenyl) sulfonium hexafluorophosphate and hexafluoro, in which a part or all of the fluorine atom of hexafluorophosphate is substituted with a perfluoroalkyl group.
  • Phenylfate derivatives, diphenyl (4-phenylthiophenyl) sulfonium / hexafluoroantimonate and the like can be mentioned.
  • the content of the photocationic polymerization initiator in the hard coat composition is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the above polysiloxane compound.
  • UV absorber When the hard coat composition contains an ultraviolet absorber, a hard coat layer containing the ultraviolet absorber is formed.
  • a benzotriazole-based ultraviolet absorber and a triazine-based ultraviolet absorber are preferable because they absorb less visible light and can obtain good light resistance.
  • the benzotriazole-based ultraviolet absorber has a large absorption coefficient in the UVA region (wavelength 320 to 400 nm) and can effectively suppress deterioration due to the phototransfer reaction of polyimide. Therefore, the hard coat layer (hard coat composition) can be used. It is preferable to contain a benzotriazole-based ultraviolet absorber.
  • the polyimide film preferably contains a triazine-based ultraviolet absorber having excellent heat resistance. If the hard coat layer 2 containing a benzotriazole ultraviolet absorber is formed on the polyimide film 1 containing a triazine-based ultraviolet absorber, ultraviolet rays in a wide wavelength range are absorbed, so that the light deterioration of the polyimide is efficient. Can be suppressed.
  • the amount of the ultraviolet absorber in the hard coat composition is based on 100 parts by weight of the total solid content. 0.1 part by weight or more is preferable, 0.3 part by weight or more is more preferable, and 0.5 part by weight or more, 0.7 part by weight or more, or 1 part by weight or more may be used. The larger the amount of the UV absorber, the higher the UV shielding property of the hard coat layer tends to be.
  • the amount of the ultraviolet absorber in the hard coat composition is preferably 4.5 parts by weight or less, more preferably 4 parts by weight or less, and 3.5 parts by weight or less or 3 parts by weight, based on 100 parts by weight of the total solid content. It may be less than or equal to a part.
  • the hardcourt composition may be a solvent-free type or may contain a solvent. When a solvent is contained, it is preferable that the polyimide film is not dissolved. On the other hand, by using a solvent having a solubility enough to swell the polyimide film, the adhesion between the polyimide film base material 1 and the hard coat layer 2 may be improved.
  • the amount of the solvent in the hardcoat composition is preferably 500 parts by weight or less, more preferably 300 parts by weight or less, still more preferably 100 parts by weight or less, based on 100 parts by weight of the curable resin (polysiloxane compound).
  • the hardcourt composition may contain a reactive diluent.
  • a reactive diluent for example, a cationically polymerizable compound other than the above-mentioned polysiloxane compound is used.
  • the reactive diluent for the polymerization include compounds having a functional group such as an epoxy group, a vinyl ether group, an oxetane group, and an alkoxysilyl group.
  • the hard coat composition may contain a photosensitizer for the purpose of improving the photosensitivity of the photocationic polymerization initiator (photoacid generator).
  • a photosensitizer those capable of absorbing light in a wavelength range that cannot be absorbed by the photoacid generator itself are more efficient, and therefore, those having less overlap with the absorption wavelength range of the photoacid generator are preferable.
  • the photosensitizer include anthracene derivatives, benzophenone derivatives, thioxanthone derivatives, anthraquinone derivatives, benzoin derivatives and the like.
  • the hardcoat composition may contain particles for the purpose of adjusting film properties such as surface hardness and bending resistance, suppressing curing shrinkage, and the like.
  • particles organic particles, inorganic particles, organic-inorganic composite particles and the like may be appropriately selected and used.
  • the material of the organic particles include poly (meth) acrylic acid alkyl ester, crosslinked poly (meth) acrylic acid alkyl ester, crosslinked styrene, nylon, silicone, crosslinked silicone, crosslinked urethane, and crosslinked butadiene.
  • metal oxides such as silica, titania, alumina, tin oxide, zirconia, zinc oxide and antimony oxide; metal nitrogenous products such as silicon nitride and boron nitride; calcium carbonate, calcium hydrogen phosphate and calcium phosphate, Examples thereof include metal salts such as aluminum phosphate.
  • organic-inorganic composite filler include those having an inorganic layer formed on the surface of organic particles and those having an organic layer or organic fine particles formed on the surface of the inorganic particles.
  • the average particle size of the particles is, for example, about 5 nm to 10 ⁇ m. From the viewpoint of enhancing the transparency of the hard coat layer, the average particle size is preferably 1000 nm or less, more preferably 500 nm or less, further preferably 300 nm or less, and particularly preferably 100 nm or less.
  • the particle size can be measured by a laser diffraction / scattering type particle size distribution measuring device, and the volume-based median size is used as the average particle size.
  • the particles may be surface-modified.
  • the surface modification of the particles tends to improve the dispersibility of the particles.
  • the functional group on the particle surface reacts with the epoxy group of the above polysiloxane compound to form a chemical crosslink. Improvement of film strength can be expected.
  • the hardcoat composition may contain additives such as inorganic pigments, organic pigments, surface modifiers, surface modifiers, plasticizers, dispersants, wetting agents, thickeners and defoaming agents. Further, the hard coat composition may contain a thermoplastic, thermosetting or photocurable resin material other than the above-mentioned polysiloxane compound.
  • the hard coat composition contains a photopolymerization initiator and an ultraviolet absorber in addition to the polysiloxane compound as a curable resin, and further, as a solid content (nonvolatile content), a reactive diluent and a photosensitizer. , Particles and other additives may be included.
  • the content of the polysiloxane compound in the hardcoat composition is preferably 40 parts by weight or more, preferably 50 parts by weight or more, based on 100 parts by weight of the total solid content. Is more preferable, and 60 parts by weight or more is further preferable.
  • a hard coat composition is applied onto the polyimide film, the solvent is dried and removed as necessary, and then the hard coat composition is cured by irradiating it with active energy rays such as ultraviolet rays to cure the hard coat composition on the polyimide film 1.
  • active energy rays such as ultraviolet rays
  • the integrated irradiation amount of the active energy rays at the time of photocuring is, for example, about 50 to 10000 mJ / cm 2 , and may be set according to the type and blending amount of the polymerization initiator, the thickness of the hard coat layer, and the like.
  • the curing temperature is not particularly limited, but is usually 100 ° C. or lower.
  • the thickness of the hard coat layer is preferably 0.5 ⁇ m or more, more preferably 2 ⁇ m or more, further preferably 3 ⁇ m or more, and most preferably 5 ⁇ m or more.
  • the thickness of the hard coat layer is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less. If the thickness of the hard coat layer is smaller than 0.5 ⁇ m, it may not be possible to sufficiently improve mechanical properties such as surface hardness. On the other hand, if the thickness of the hard coat layer is larger than 100 ⁇ m, the transparency and bending resistance may decrease.
  • the total light transmittance of the hard coat film is preferably 80% or more, more preferably 85% or more, still more preferably 88% or more.
  • the haze of the hard coat film is preferably 1.5% or less, more preferably 0.9% or less, further preferably 0.7% or less, and particularly preferably 0.5% or less.
  • the yellowness (YI) of the hard coat film is preferably 10 or less, more preferably 6 or less, further preferably 5 or less, and may be 4 or less, 3.5 or less, 3.0 or less, or 2.5 or less. ..
  • both the polyimide film 1 and the hard coat layer 2 contain an ultraviolet absorber. Therefore, when external light is incident from the hard coat layer 2 side, the hard coat layer 2 absorbs (shields) the ultraviolet rays, the amount of the ultraviolet rays reaching the polyimide film 1 is small, and the ultraviolet rays reaching the polyimide film 1 are generated. It is absorbed by the ultraviolet absorber contained in the polyimide film 1. Therefore, the polyimide resin of the polyimide film 1 is not easily affected by ultraviolet rays, and discoloration (increase in yellowness) due to photodegradation is suppressed.
  • the content of the ultraviolet absorber in the polyimide film is preferably 0.1 to 4.5% by weight, more preferably 0.3 to 4% by weight, further preferably 0.5 to 3.5% by weight, and 0.7. It may be up to 3% by weight or 1.0 to 2.5% by weight.
  • the content of the ultraviolet absorber in the hard coat layer is preferably 0.1 to 4.5% by weight, more preferably 0.3 to 4% by weight, further preferably 0.5 to 3.5% by weight, and 0. It may be 7 to 3% by weight or 1.0 to 2.5% by weight.
  • the amount of increase in yellowness of the hardcoat film when irradiated with ultraviolet rays for 48 hours under the conditions of an irradiance of 500 W / m 2 and a black panel temperature of 63 ° C. from the hardcoat layer forming surface side is preferably 6 or less, preferably 5 or less. Is more preferable, and may be 4.5 or less or 4.0 or less.
  • the pencil hardness of the hard coat layer forming surface of the hard coat film is preferably HB or higher, more preferably H or higher, further preferably 2H or higher, particularly preferably 3H or higher, and may be 4H or higher.
  • the tensile elastic modulus of the hard-coated film is preferably 3.5 GPa or more, more preferably 4.0 GPa or more, and even more preferably 5.0 GPa or more.
  • various functional layers may be provided on the hard coat layer 2 or on the non-formed surface of the hard coat layer of the polyimide film 1.
  • the functional layer include an antireflection layer, an antiglare layer, an antistatic layer, a transparent electrode and the like.
  • the hard coat film may be provided with a transparent adhesive layer.
  • the hard coat film of the present invention Since the hard coat film of the present invention has high transparency and excellent mechanical strength, it can be used for a cover window arranged on the visible side surface of an image display panel, a transparent substrate for a display, a transparent substrate for a touch panel, a substrate for a solar cell, and the like. It is preferably used. Since the hard coat film of the present invention has excellent bending resistance and light resistance in addition to transparency and mechanical strength, it is a cover placed on the visible side surface of a curved display or a bendable display in particular. It can be suitably used as a window.
  • the above polyimide solution is applied to non-alkali glass using a bar coater, and in an air atmosphere, 40 ° C. for 60 minutes, 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, 170 ° C. for 30 minutes, 200 ° C.
  • the solvent was removed by heating for 60 minutes with a transparent polyimide film having a thickness of 50 ⁇ m.
  • the hardcourt composition was applied to the main surface of a transparent polyimide substrate having a thickness of 50 ⁇ m using a bar coater so that the thickness after curing was 50 ⁇ m, and heated at 120 ° C. for 10 minutes. Using a high-pressure mercury lamp, ultraviolet rays are irradiated so that the integrated light amount at a wavelength of 365 nm is 1000 mJ / cm 2 , and then heated at 80 ° C. for 2 hours to cure the hard coat composition and hard on the polyimide film substrate. A hardcourt film with a coat (HC) layer was obtained. In Example 2, Comparative Example 5 and Comparative Example 6, a hard coat (HC) layer having a thickness of 50 ⁇ m was formed on both surfaces of the transparent polyimide film substrate. In Comparative Examples 1 to 4, the hard coat layer was not formed.
  • Comparative Example 8 and Comparative Example 9 had wrinkles on the film surface. Therefore, in Comparative Examples 8 and 9, the subsequent evaluation was not carried out.
  • the film was cut into a size of 3 cm square, and the yellowness (YI) was measured using a spectrocolorimeter (“SC-P” manufactured by Suga Test Instruments Co., Ltd.). Then, using a fade meter (“U48-HB” manufactured by Suga Testing Machine), one side of the film (Examples 1 and 3 to 8 and Comparative Examples 7 to 9) under the conditions of an irradiance of 500 W / m 2 and a black panel temperature of 63 ° C. , The hard coat layer forming surface) was irradiated with ultraviolet rays for 48 hours.
  • SC-P spectrocolorimeter
  • U48-HB manufactured by Suga Testing Machine
  • the pencil hardness of the film was measured by the JIS K-5600-5-4 pencil scratch test. In Examples 1 and 3 to 8 and Comparative Examples 7 to 9, the pencil hardness of the hard coat layer forming surface was evaluated.
  • UVA ultraviolet absorbers
  • LA-31RG "ADEKA STAB LA-31RG” manufactured by ADEKA: 2,2'-methylenebis [6- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol]
  • LA-F70 ADEKA
  • ADEKA STUB LA-F70 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine Tin 326: BASF "Tinvin 326” 2- [5-Chloro (2H) -benzotriazole-2-yl] -4-methyl-6- (tert-butyl) phenol
  • LA-29 "ADEKA STAB LA-29” manufactured by ADEKA; 2- (2H-) Benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol
  • LA-32 "ADEKA STAB LA-32” manufactured by ADEKA;
  • the hard coat film containing an ultraviolet absorber in both the polyimide film and the hard coat layer shows high pencil hardness due to the formation of the hard coat layer, and ⁇ YI after light irradiation by a fade test. It can be seen that the size is small and the light resistance is excellent.
  • Comparative Example 5 in which neither the polyimide film nor the hard coat layer contained an ultraviolet absorber, ⁇ YI was large and the light resistance was insufficient.
  • Comparative Example 6 in which the ultraviolet absorber was blended only in the hard coat layer and Comparative Example 7 in which the UV absorber was blended only in the polyimide film, ⁇ YI was smaller than that of Comparative Example 5, but the light resistance was insufficient. ..
  • a hard coat film having excellent transparency, light resistance and surface hardness can be obtained by including an ultraviolet absorber in both the polyimide film and the hard coat layer.

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JP2018134865A (ja) * 2017-02-22 2018-08-30 住友化学株式会社 積層体
JP2019147923A (ja) * 2018-02-28 2019-09-05 日鉄ケミカル＆マテリアル株式会社 シロキサン系硬化性樹脂組成物から成るハードコーティング液を用いた積層体
WO2020004236A1 (ja) * 2018-06-28 2020-01-02 株式会社カネカ ポリイミド樹脂およびその製造方法、ならびにポリイミドフィルムおよびその製造方法
JP2020164771A (ja) * 2019-03-31 2020-10-08 株式会社カネカ ポリイミドフィルムおよびその製造方法

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JP2017226712A (ja) 2014-11-10 2017-12-28 住友化学株式会社 光硬化性樹脂組成物およびこれを用いる硬化膜の製造方法
JP6931526B2 (ja) * 2016-11-25 2021-09-08 株式会社ダイセル ハードコートフィルム
CN112639038B (zh) 2018-08-24 2022-07-15 株式会社钟化 硬涂组合物、带硬涂层的聚酰亚胺薄膜及其制造方法、及图像显示装置
JP7246999B2 (ja) * 2019-03-31 2023-03-28 株式会社カネカ ポリイミドフィルムおよびその製造方法

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JP2018134865A (ja) * 2017-02-22 2018-08-30 住友化学株式会社 積層体
JP2019147923A (ja) * 2018-02-28 2019-09-05 日鉄ケミカル＆マテリアル株式会社 シロキサン系硬化性樹脂組成物から成るハードコーティング液を用いた積層体
WO2020004236A1 (ja) * 2018-06-28 2020-01-02 株式会社カネカ ポリイミド樹脂およびその製造方法、ならびにポリイミドフィルムおよびその製造方法
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