TW202231474A - Hard coating film, method for producing same, and image display device - Google Patents

Hard coating film, method for producing same, and image display device Download PDF

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TW202231474A
TW202231474A TW110139216A TW110139216A TW202231474A TW 202231474 A TW202231474 A TW 202231474A TW 110139216 A TW110139216 A TW 110139216A TW 110139216 A TW110139216 A TW 110139216A TW 202231474 A TW202231474 A TW 202231474A
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hard coat
polyimide
film
bis
ultraviolet absorber
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小川紘平
片山敬介
後裕之
石黒文康
杉山智史
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日商鐘化股份有限公司
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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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • 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
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    • 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

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract

This hard coating film (10) is provided with a hard coating layer (2) on at least one surface of a base material film (1). The base material film is a polyimide film that contains a polyimide resin; and the hard coating layer is formed of a cured product of a photo curable resin composition. Since both of the hard coating layer and the polyimide film contain an ultraviolet absorbent, the hard coating film has high hardness and excellent light resistance. This hard coating film is applicable to a surface protective material that is arranged on the viewing-side surface of an image display panel, or the like.

Description

硬塗膜及其製造方法、以及圖像顯示裝置Hard coat film, method for producing the same, and image display device

本發明係關於一種於透明聚醯亞胺膜之至少一面具備硬塗層之硬塗膜及其製造方法、以及具備該硬塗膜之圖像顯示裝置。The present invention relates to a hard coat film provided with a hard coat layer on at least one side of a transparent polyimide film, a method for producing the same, and an image display device provided with the hard coat film.

隨著移動終端設備之薄型化及輕量化之進展，以智慧型手機為代表之終端設備得到廣泛地普及。近年來，關於兼顧畫面之大型化及便攜性之方法，提出了搭載有軟性顯示器，尤其是搭載有使用了可撓性基板之有機EL(Electroluminescence，電致發光)面板之可摺疊式移動終端設備。With the progress of thinner and lighter mobile terminal equipment, the terminal equipment represented by smart phones has been widely popularized. In recent years, as a method of taking into account the enlargement of the screen and the portability, a foldable mobile terminal device equipped with a flexible display, especially an organic EL (Electroluminescence) panel using a flexible substrate has been proposed. .

於軟性裝置中，不僅顯示器基板需要具有可撓性，覆蓋窗等之表面保護材料亦需要具有可撓性，而提出使用透明性、表面硬度、及彎曲耐久性優異之於聚醯亞胺膜之表面設置硬塗層而成之硬塗膜(例如專利文獻1及專利文獻2)。據專利文獻1中揭示，藉由使用包含反應性胺基甲酸酯丙烯酸酯、自由基光聚合起始劑及紫外線吸收劑之光硬化性樹脂組合物而形成硬塗層。 [先前技術文獻] [專利文獻] In a flexible device, not only the display substrate needs to be flexible, but also the surface protection material of the cover window, etc. It is proposed to use a polyimide film with excellent transparency, surface hardness, and bending durability. A hard coat film formed by providing a hard coat layer on the surface (for example, Patent Document 1 and Patent Document 2). As disclosed in Patent Document 1, a hard coat layer is formed by using a photocurable resin composition containing a reactive urethane acrylate, a radical photopolymerization initiator, and an ultraviolet absorber. [Prior Art Literature] [Patent Literature]

[專利文獻1]日本專利特開2017-226712號公報 [專利文獻2]國際公開第2020/040209號 [Patent Document 1] Japanese Patent Laid-Open No. 2017-226712 [Patent Document 2] International Publication No. 2020/040209

[發明所欲解決之問題][Problems to be Solved by Invention]

顯示裝置之表面保護材料由於位於最外層，故而容易暴露於外界光中。因此，對於用作表面保護材料之硬塗膜而言，需要即使在暴露於紫外線等時，光學特性、機械強度之變化亦較小，且亦具有較高之耐光性。 [解決問題之技術手段] Since the surface protection material of the display device is located in the outermost layer, it is easily exposed to external light. Therefore, for a hard coat film used as a surface protective material, even when exposed to ultraviolet rays or the like, changes in optical properties and mechanical strength are small, and it is required to have high light resistance. [Technical means to solve problems]

本發明之一形態為於基材膜之至少一面設置硬塗層而成之硬塗膜。基材膜為包含聚醯亞胺樹脂之聚醯亞胺膜，硬塗層包含光硬化性樹脂組合物之硬化物。硬塗層及聚醯亞胺膜各自含有紫外線吸收劑。One aspect of the present invention is a hard coat film formed by providing a hard coat layer on at least one side of a base film. The base film is a polyimide film including a polyimide resin, and the hard coat layer includes a cured product of the photocurable resin composition. The hard coat layer and the polyimide film each contain an ultraviolet absorber.

作為聚醯亞胺膜及硬塗層中所包含之紫外線吸收劑，較佳為苯并***化合物或三𠯤化合物。聚醯亞胺膜中之紫外線吸收劑之含量較佳為0.1～4.5重量%。硬塗層中之紫外線吸收劑之含量較佳為0.1～4.5重量%。The ultraviolet absorber contained in the polyimide film and the hard coat layer is preferably a benzotriazole compound or a trisulfuric compound. 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.

硬塗層之厚度例如為0.5～100 μm。聚醯亞胺膜之厚度例如為5～100 μm。The thickness of the hard coat layer is, for example, 0.5 to 100 μm. The thickness of the polyimide film is, for example, 5 to 100 μm.

聚醯亞胺膜之聚醯亞胺樹脂較佳為可溶於二氯甲烷。例如，藉由將包含可溶於二氯甲烷之聚醯亞胺樹脂及紫外線吸收劑之溶液塗佈於基材上並去除溶劑，能夠獲得包含紫外線吸收劑之聚醯亞胺膜。藉由於該聚醯亞胺膜之表面塗佈包含光硬化性樹脂及光聚合起始劑之光硬化性樹脂組合物(硬塗組合物)並進行光硬化，能夠製作於聚醯亞胺膜之表面具備硬塗層之硬塗膜。The polyimide resin of the polyimide film is preferably soluble in dichloromethane. For example, a polyimide film containing an ultraviolet absorber can be obtained by coating a solution containing a dichloromethane-soluble polyimide resin and an ultraviolet absorber on a substrate and removing the solvent. By coating the surface of the polyimide film with a photocurable resin composition (hard coating composition) containing a photocurable resin and a photopolymerization initiator, and photocuring, it can be produced in the polyimide film. A hard coat with a hard coat on the surface.

硬塗組合物亦可為陽離子光聚合性。作為具有陽離子光聚合性之光硬化性樹脂之一例，可例舉具有環氧基之聚矽氧烷化合物。硬塗組合物例如含有：具有陽離子光聚合性之光硬化性樹脂、陽離子光聚合起始劑(光酸產生劑)及紫外線吸收劑。The hard coating composition may also be cationic photopolymerizable. As an example of the photocurable resin which has cationic photopolymerizability, the polysiloxane compound which has an epoxy group is mentioned. The hard coating composition contains, for example, a photocurable resin having cationic photopolymerizability, a cationic photopolymerization initiator (photoacid generator), and an ultraviolet absorber.

硬塗膜例如可於圖像顯示裝置中用作配置於圖像顯示面板之視認側表面之表面保護材料。圖像顯示裝置亦可為能夠彎折者。 [發明之效果] The hard coat film can be used, for example, as a surface protection material disposed on the viewable side surface of an image display panel in an image display device. The image display device may also be bendable. [Effect of invention]

藉由使硬塗膜於聚醯亞胺膜及硬塗層兩者中包含紫外線吸收劑，而使得聚醯亞胺之光劣化得到抑制，因此即使在暴露於紫外線等時，光學特性、機械強度之變化亦較小，且耐光性亦優異。By making the hard coat film contain an ultraviolet absorber in both the polyimide film and the hard coat layer, the photo-deterioration of the polyimide is suppressed, so even when exposed to ultraviolet rays, etc., the optical properties and mechanical strength are improved. The change is also small, and the light resistance is also excellent.

圖1係硬塗膜10之剖視圖，該硬塗膜10係於聚醯亞胺膜1之一主面設置硬塗層2而成。藉由於作為膜基材之聚醯亞胺膜1之主面塗佈硬塗組合物並使其硬化，而形成硬塗層2。硬塗層可僅設置於聚醯亞胺膜之一主面，亦可設置於聚醯亞胺膜之雙面。FIG. 1 is a cross-sectional view of a hard coating film 10 formed by providing a hard coating layer 2 on one main surface of a polyimide film 1 . The hard coat layer 2 is formed by coating and curing the hard coat composition on the main surface of the polyimide film 1 serving as the film base material. The hard coat layer can be provided only on one main surface of the polyimide film, and can also be provided on both sides of the polyimide film.

聚醯亞胺膜1及硬塗層2均包含紫外線吸收劑。藉由使聚醯亞胺膜及硬塗層兩者包含紫外線吸收劑，而使得耐光性提昇，即使長時間暴露於紫外線中後，硬塗膜之黃變亦往往得到抑制。Both the polyimide film 1 and the hard coat layer 2 contain an ultraviolet absorber. By including the ultraviolet absorber in both the polyimide film and the hard coat layer, the light resistance is improved, and the yellowing of the hard coat film tends to be suppressed even after prolonged exposure to ultraviolet rays.

作為聚醯亞胺膜及硬塗層中所包含之紫外線吸收劑，可例舉：三𠯤系紫外線吸收劑、苯并***系紫外線吸收劑、二苯甲酮系紫外線吸收劑、氰基丙烯酸酯系紫外線吸收劑、羥基苯甲酸酯系紫外線吸收劑等。其中，出於可見光之吸收較少且可獲得良好之耐光性之方面考慮，較佳為苯并***系紫外線吸收劑及三𠯤系紫外線吸收劑。Examples of the ultraviolet absorber contained in the polyimide film and the hard coat layer include tris-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and cyanoacrylic acid. Ester-based UV absorbers, hydroxybenzoate-based UV absorbers, and the like. Among them, a benzotriazole-based ultraviolet absorber and a trisulfan-based ultraviolet absorber are preferred from the viewpoint of less visible light absorption and favorable light resistance.

作為苯并***系紫外線吸收劑之具體例，可例舉：2-(2H-苯并***-2-基)-4,6-雙(1-甲基-1-苯基乙基)苯酚(ADEKA製造之「Adekastab LA-24」)、2-(2H-苯并***-2-基)-4-(1,1,3,3-四甲基丁基)苯酚(ADEKA製造之「Adekastab LA-29」)、2,2'-亞甲基雙[6-(2H-苯并***-2-基)-4-(1,1,3,3-四甲基丁基)苯酚](ADEKA製造之「Adekastab LA-31G」及「Adekastab LA-31RG」)、2-(2H-苯并***-2-基)-對甲酚(ADEKA製造之「Adekastab LA-32」)、2-(2H-苯并***-2-基)-6-十二烷基-4-甲基苯酚(BASF製造之「TINUVIN571」)、2-(2H-苯并***-2-基)-對甲酚(BASF製造之「TINUVIN P」)、2-(2-羥基-5-第三丁基苯基)-2H-苯并***(BASF製造之「TINUVIN PS」)、2-(2H-苯并***-2-基)-4-6-雙(1-甲基-1-苯基乙基)苯酚(BASF製造之「TINUVIN 234」)、2-[5-氯(2H)-苯并***-2-基]-4-甲基-6-(第三丁基)苯酚(BASF製造之「TINUVIN 326」)、2-(2H-苯并***-2-基)-4,6-二-第三戊基苯酚(BASF製造之「TINUVIN 328」)、2-(2H-苯并***-2-基)-4-(1,1,3,3-四甲基丁基)苯酚(BASF製造之「TINUVIN 329」)、2-(2H-苯并***-2-基)-4,6-雙(1-甲基-1-苯基乙基)苯酚(BASF製造之「TINUVIN 900」)、2-(2H-苯并***-2-基)-6-(1-甲基-1-苯基乙基)-4-(1,1,3,3-四甲基丁基)苯酚(BASF製造之「TINUVIN 928」)、2-[2-羥基-3-(3,4,5,6-四氫鄰苯二甲醯亞胺-甲基)-5-甲基苯基]苯并***(住友化學製造之「Sumisorb250」)等。Specific examples of benzotriazole-based ultraviolet absorbers include 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl) Phenol (“Adekastab LA-24” manufactured by ADEKA), 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (manufactured by ADEKA "Adekastab LA-29"), 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl) Phenol] (“Adekastab LA-31G” and “Adekastab LA-31RG” manufactured by ADEKA), 2-(2H-benzotriazol-2-yl)-p-cresol (“Adekastab LA-32” manufactured by ADEKA) , 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol (“TINUVIN571” manufactured by BASF), 2-(2H-benzotriazol-2-yl )-p-cresol (“TINUVIN P” manufactured by BASF), 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole (“TINUVIN PS” manufactured by BASF), 2- (2H-benzotriazol-2-yl)-4-6-bis(1-methyl-1-phenylethyl)phenol (“TINUVIN 234” manufactured by BASF), 2-[5-chloro (2H )-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol (“TINUVIN 326” manufactured by BASF), 2-(2H-benzotriazol-2-yl) -4,6-Di-tert-pentylphenol ("TINUVIN 328" manufactured by BASF), 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethyl) butyl)phenol (“TINUVIN 329” manufactured by BASF), 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol ( "TINUVIN 900" manufactured by BASF, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3 -Tetramethylbutyl)phenol ("TINUVIN 928" manufactured by BASF), 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimide-methyl)- 5-methylphenyl]benzotriazole (“Sumisorb 250” manufactured by Sumitomo Chemical) and the like.

作為三𠯤系紫外線吸收劑之具體例，可例舉：2-(4,6-二苯基-1,3,5-三𠯤-2-基)-5-[2-(2-乙基己醯氧基)乙氧基]-苯酚(ADEKA製造之「Adekastab LA-46」)、2,4,6-三(2-羥基-4-己氧基-3-甲基苯基)-1,3,5-三𠯤(ADEKA製造之「Adekastab LA-F70」)、2-(4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤-2-基)-5-羥基苯基與[(烷氧基)甲基]環氧乙烷之反應產物(BASF製造之「TINUVIN 400」)、2-(2,4-二羥基苯基)-4,6-雙-(2,4-二甲基苯基)-1,3,5-三𠯤與縮水甘油酸(2-乙基己基)酯之反應產物(BASF製造之「TINUVIN 405」)、(2,4-雙[2-羥基-4-丁氧基苯基]-6-(2,4-二丁氧基苯基)-1,3,5-三𠯤(BASF製造之「TINUVIN 460」)、2-(2-羥基-4-[1-辛氧基羰基乙氧基]苯基)-4,6-雙(4-苯基苯基)-1,3,5-三𠯤(BASF製造之「TINUVIN 479」)、2-(4,6-二苯基-1,3,5-三𠯤-2-基)-5-[(己基)氧基]-苯酚(BASF製造之「TINUVIN 577」)、雙乙基己氧基苯酚甲氧基苯基三𠯤(BASF製造之「Tinosorb S」)等。As a specific example of the tris(2)-based ultraviolet absorber, 2-(4,6-diphenyl-1,3,5-tris(2-yl)-5-[2-(2-ethyl) Hexyloxy)ethoxy]-phenol (“Adekastab LA-46” manufactured by ADEKA), 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1 ,3,5-Tris("Adekastab LA-F70" manufactured by ADEKA), 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-tris-2- yl)-5-hydroxyphenyl and [(alkoxy)methyl]oxirane ("TINUVIN 400" manufactured by BASF), 2-(2,4-dihydroxyphenyl)-4, Reaction product of 6-bis-(2,4-dimethylphenyl)-1,3,5-tri(2-ethylhexyl) glycidate ("TINUVIN 405" manufactured by BASF), ( 2,4-Bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-tris("TINUVIN 460" manufactured by BASF) ), 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-tris𠯤(BASF "TINUVIN 479" manufactured by BASF, 2-(4,6-diphenyl-1,3,5-tri(2-yl)-5-[(hexyl)oxy]-phenol ("TINUVIN manufactured by BASF) 577"), bisethylhexyloxyphenol methoxyphenyl tris("Tinosorb S" manufactured by BASF), etc.

以下，依序對聚醯亞胺膜及硬塗層之較佳形態進行說明。再者，除非另有說明，否則本說明書中例示之化合物等可單獨使用，亦可併用(併存)2種以上。Hereinafter, preferable forms of the polyimide film and the hard coat layer will be sequentially described. In addition, unless otherwise specified, the compounds and the like exemplified in this specification may be used alone or in combination (coexistence) of two or more.

[聚醯亞胺膜] ＜聚醯亞胺之組成＞ 聚醯亞胺膜1包含聚醯亞胺樹脂。聚醯亞胺係通常藉由對利用四羧酸二酐(以下，有時僅記載為「酸二酐」)與二胺反應所獲得之聚醯胺酸進行脫水環化而獲得。即，聚醯亞胺具有源自酸二酐之結構及源自二胺之結構。 [Polyimide film] ＜Composition of polyimide＞ The polyimide film 1 contains a polyimide resin. The polyimide is usually obtained by dehydrating and cyclizing a polyimide obtained by reacting a tetracarboxylic dianhydride (hereinafter, simply referred to as "acid dianhydride") and a diamine. That is, the polyimide has a structure derived from an acid dianhydride and a structure derived from a diamine.

於透明聚醯亞胺膜之製作中，較佳為採用如下方法：將使聚醯亞胺樹脂溶解於有機溶劑中而成之溶液塗佈於基板上，藉由加熱將溶劑乾燥去除(溶液澆鑄法)。因此，聚醯亞胺較佳為透明，並且可溶於有機溶劑。就聚醯亞胺膜之生產性之觀點而言，於溶液澆鑄法中，較佳為使用二氯甲烷等低沸點溶劑。因此，聚醯亞胺樹脂較佳為可溶於二氯甲烷。In the production of the transparent polyimide film, the following method is preferably used: a solution obtained by dissolving the polyimide resin in an organic solvent is applied to the substrate, and the solvent is dried and removed by heating (solution casting). Law). Therefore, the polyimide is preferably transparent and soluble in organic solvents. From the viewpoint of the productivity of the polyimide film, in the solution casting method, it is preferable to use a low-boiling point solvent such as dichloromethane. Therefore, the polyimide resin is preferably soluble in methylene chloride.

作為可溶於二氯甲烷之聚醯亞胺之一例，可例舉如下聚醯亞胺，其包含作為酸二酐成分之通式(1)所表示之四羧酸二酐及具有環丁烷結構之四羧酸二酐，且包含作為二胺成分之氟烷基取代聯苯胺。As an example of the dichloromethane-soluble polyimide, a polyimide containing tetracarboxylic dianhydride represented by the general formula (1) as an acid dianhydride component and a cyclobutane The tetracarboxylic dianhydride of the structure contains fluoroalkyl-substituted benzidine as a diamine component.

Figure 02_image001
Figure 02_image001

於通式(1)中，n為1或2。R 1～R 4分別獨立地為氫原子、氟原子、碳原子數1～20之烷基或氟烷基，R 1～R 4中之至少1個為碳原子數1～20之烷基或氟烷基。 In the general formula (1), n is 1 or 2. R 1 to R 4 are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms or a fluoroalkyl group, and at least one of R 1 to R 4 is an alkyl group having 1 to 20 carbon atoms or Fluoroalkyl.

作為聚醯亞胺之組成之一例，可例舉如下組成：包含相對於二胺成分總量100莫耳%為40莫耳%以上100莫耳%以下之氟烷基取代聯苯胺，且包含相對於酸二酐成分總量100莫耳%為40莫耳%以上85莫耳%以下之具有式(1)所表示之酯結構之酸二酐、及15莫耳%以上60莫耳%以下之具有環丁烷結構之酸二酐。As an example of the composition of the polyimide, a composition containing 40 mol % or more and 100 mol % or less of fluoroalkyl-substituted benzidine with respect to 100 mol % of the total amount of diamine components, and a relatively Acid dianhydrides having an ester structure represented by formula (1), and 15 mol% or more and 60 mol% or less, based on 100 mol% of the total acid dianhydride components. Acid dianhydride with cyclobutane structure.

(具有酯結構之酸二酐) 上述通式(1)所表示之化合物為具有酯結構之酸二酐。作為R 1～R 4為烷基或氟烷基之情形時之烷基的例，可例舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、環丁基、正戊基、異戊基、新戊基、環戊基、正己基、環己基等。作為氟烷基，可例舉：單氟甲基、二氟甲基、三氟甲基、五氟乙基等。 (Acid dianhydride having an ester structure) The compound represented by the above general formula (1) is an acid dianhydride having an ester structure. Examples of the alkyl group when R 1 to R 4 are an alkyl group or a fluoroalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary Butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl, etc. As a fluoroalkyl group, a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, etc. are mentioned.

出於能夠獲得對二氯甲烷表現出較高溶解性之聚醯亞胺之方面考慮，通式(1)所表示之化合物中，較佳為下述式(2)所表示之雙(1,3-二側氧基-1,3-二氫異苯并呋喃-5-羧酸)-2,2',3,3',5,5'-六甲基聯苯-4,4'二基酯(TAHMBP)。Among the compounds represented by the general formula (1), bis(1, 3-Di-oxy-1,3-dihydroisobenzofuran-5-carboxylic acid)-2,2',3,3',5,5'-hexamethylbiphenyl-4,4'diphenyl base ester (TAHMBP).

Figure 02_image003
Figure 02_image003

(具有環丁烷結構之酸二酐) 作為具有環丁烷結構之酸二酐之具體例，可例舉：1,2,3,4-環丁烷四羧酸二酐、1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,4-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-四甲基-1,2,3,4-環丁烷四羧酸二酐、1,3-二丙基-1,2,3,4-環丁烷四羧酸二酐、1,4-二丙基-1,2,3,4-環丁烷四羧酸二酐、環丁烷-1,2:3,4-雙(四亞甲基)-1,2,3,4-四羧酸二酐等。其中，較佳為1,2,3,4-環丁烷四羧酸二酐(CBDA)。 (acid dianhydride with cyclobutane structure) Specific examples of the acid dianhydride having a cyclobutane structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, 1,4-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2 ,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dipropyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,4-dipropyl-1,2 , 3,4-cyclobutane tetracarboxylic dianhydride, cyclobutane-1,2:3,4-bis(tetramethylene)-1,2,3,4-tetracarboxylic dianhydride, etc. Among them, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) is preferred.

(氟烷基取代聯苯胺) 作為氟烷基取代聯苯胺之具體例，可例舉：2-氟聯苯胺、3-氟聯苯胺、2,3-二氟聯苯胺、2,5-二氟聯苯胺、2,6-二氟聯苯胺、2,3,5-三氟聯苯胺、2,3,6-三氟聯苯胺、2,3,5,6-四氟聯苯胺、2,2'-二氟聯苯胺、3,3'-二氟聯苯胺、2,3'-二氟聯苯胺、2,2',3-三氟聯苯胺、2,3,3'-三氟聯苯胺、2,2',5-三氟聯苯胺、2,2',6-三氟聯苯胺、2,3',5-三氟聯苯胺、2,3',6,-三氟聯苯胺、2,2',3,3'-四氟聯苯胺、2,2',5,5'-四氟聯苯胺、2,2',6,6'-四氟聯苯胺、2,2',3,3',6,6'-六氟聯苯胺、2,2',3,3',5,5',6,6'-八氟聯苯胺、2-(三氟甲基)聯苯胺、3-(三氟甲基)聯苯胺、2,3-雙(三氟甲基)聯苯胺、2,5-雙(三氟甲基)聯苯胺、2,6-雙(三氟甲基)聯苯胺、2,3,5-三(三氟甲基)聯苯胺、2,3,6-三(三氟甲基)聯苯胺、2,3,5,6-四(三氟甲基)聯苯胺、2,2'-雙(三氟甲基)聯苯胺、3,3'-雙(三氟甲基)聯苯胺、2,3'-雙(三氟甲基)聯苯胺、2,2',3-雙(三氟甲基)聯苯胺、2,3,3'-三(三氟甲基)聯苯胺、2,2',5-三(三氟甲基)聯苯胺、2,2',6-三(三氟甲基)聯苯胺、2,3',5-三(三氟甲基)聯苯胺、2,3',6,-三(三氟甲基)聯苯胺、2,2',3,3'-四(三氟甲基)聯苯胺、2,2',5,5'-四(三氟甲基)聯苯胺、2,2',6,6'-四(三氟甲基)聯苯胺等。 (Fluoroalkyl substituted benzidine) Specific examples of fluoroalkyl-substituted benzidine include 2-fluorobenzidine, 3-fluorobenzidine, 2,3-difluorobenzidine, 2,5-difluorobenzidine, 2,6-difluorobenzidine Fluorobenzidine, 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-trifluorobenzidine, 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-(trifluoromethyl) ) benzidine, 2,3-bis(trifluoromethyl)benzidine, 2,5-bis(trifluoromethyl)benzidine, 2,6-bis(trifluoromethyl)benzidine, 2,3, 5-Tris(trifluoromethyl)benzidine, 2,3,6-Tris(trifluoromethyl)benzidine, 2,3,5,6-Tetrakis(trifluoromethyl)benzidine, 2,2' -Bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,3'-bis(trifluoromethyl)benzidine, 2,2',3-bis( Trifluoromethyl)benzidine, 2,3,3'-tris(trifluoromethyl)benzidine, 2,2',5-tris(trifluoromethyl)benzidine, 2,2',6-tris (Trifluoromethyl)benzidine, 2,3',5-tris(trifluoromethyl)benzidine, 2,3',6,-tris(trifluoromethyl)benzidine, 2,2',3 ,3'-tetrakis(trifluoromethyl)benzidine, 2,2',5,5'-tetrakis(trifluoromethyl)benzidine, 2,2',6,6'-tetrakis(trifluoromethyl) ) benzidine, etc.

其中，較佳為於聯苯骨架之2位具有氟烷基之氟烷基取代聯苯胺，更佳為2,2'-雙(三氟甲基)聯苯胺。藉由於聯苯骨架之2位具有氟烷基，聯苯骨架之芳香族環因氟烷基之位阻而發生扭曲，再加之氟烷基之拉電子性，而使得著色減少。Among them, fluoroalkyl-substituted benzidine having a fluoroalkyl group at the 2-position of the biphenyl skeleton is preferred, and 2,2'-bis(trifluoromethyl)benzidine is more preferred. Since the 2-position of the biphenyl skeleton has a fluoroalkyl group, the aromatic ring of the biphenyl skeleton is distorted by the steric hindrance of the fluoroalkyl group, and the electron-withdrawing property of the fluoroalkyl group is added, so that the coloring is reduced.

(其他酸二酐及二胺) 聚醯亞胺可於無損其於二氯甲烷等低沸點溶劑中之溶解性，且無損透明性及機械強度之範圍內，亦可包含除上述以外之酸二酐成分及二胺成分。 (Other acid dianhydrides and diamines) The polyimide may contain an acid dianhydride component and a diamine component other than the above, within the range that does not impair its solubility in low-boiling point solvents such as methylene chloride, and does not impair transparency and mechanical strength.

作為能夠併用之酸二酐成分之例，可例舉：均苯四甲酸二酐、2,2-雙(3,4-二羧基苯基)-1,1,1,3,3,3-六氟丙烷酸二酐、3,3',4,4'-聯苯四羧酸二酐、9,9-雙(3,4-二羧基苯基)茀二酐、乙烯四羧酸二酐、丁烷四羧酸二酐、1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐、1,2,4,5-環己烷四羧酸二酐、4,4'-氧二鄰苯二甲酸二酐、1,1'-雙環己烷-3,3',4,4'-四羧酸-3,4:3',4'-二酐、3,3',4,4'-二苯甲酮四羧酸二酐、2,2',3,3'-二苯甲酮四羧酸二酐、2,2-雙(3,4-二羧基苯基)丙烷二酐、2,2-雙(2,3-二羧基苯基)丙烷二酐、雙(3,4-二羧基苯基)醚二酐、雙(3,4-二羧基苯基)碸二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、雙(2,3-二羧基苯基)甲烷二酐、雙(3,4-二羧基苯基)甲烷二酐、1,3-雙[(3,4-二羧基)苯甲醯基]苯二酐、1,4-雙[(3,4-二羧基)苯甲醯基]苯二酐、2,2-雙{4-[4-(1,2-二羧基)苯氧基]苯基}丙烷二酐、2,2-雙{4-[3-(1,2-二羧基)苯氧基]苯基}丙烷二酐、雙{4-[4-(1,2-二羧基)苯氧基]苯基}酮二酐、雙{4-[3-(1,2-二羧基)苯氧基]苯基}酮二酐、4,4'-雙[4-(1,2-二羧基)苯氧基]聯苯二酐、4,4'-雙[3-(1,2-二羧基)苯氧基]聯苯二酐、雙{4-[4-(1,2-二羧基)苯氧基]苯基}酮二酐、雙{4-[3-(1,2-二羧基)苯氧基]苯基}酮二酐、雙{4-[4-(1,2-二羧基)苯氧基]苯基}碸二酐、雙{4-[3-(1,2-二羧基)苯氧基]苯基}碸二酐、雙{4-[4-(1,2-二羧基)苯氧基]苯基}硫醚二酐、雙{4-[3-(1,2-二羧基)苯氧基]苯基}硫醚二酐、2,2-雙{4-[3-(1,2-二羧基)苯氧基]苯基}-1,1,1,3,3,3-丙烷二酐、2,3,6,7-萘四羧酸二酐、1,4,5,8-萘四羧酸二酐、1,2,5,6-萘四羧酸二酐、1,2,3,4-苯四羧酸二酐、3,4,9,10-二萘嵌苯四羧酸二酐、2,3,6,7-蒽四羧酸二酐、1,2,7,8-菲四羧酸二酐等。As an example of the acid dianhydride component which can be used together, pyromellitic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3- Hexafluoropropane dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)indium dianhydride, ethylene tetracarboxylic dianhydride , butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5 -Cyclohexanetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 1,1'-bicyclohexane-3,3',4,4'-tetracarboxylic acid-3,4 : 3',4'-dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)ether Dianhydride, bis(3,4-dicarboxyphenyl) stilbene dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane Dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 1,3-bis[(3,4-dicarboxy)benzyl]phthalic anhydride, 1,4-bis[(3, 4-Dicarboxy)benzyl]phthalic anhydride, 2,2-bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}propane dianhydride, 2,2-bis{ 4-[3-(1,2-Dicarboxy)phenoxy]phenyl}propane dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}ketone dianhydride, Bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}ketone dianhydride, 4,4'-bis[4-(1,2-dicarboxy)phenoxy]biphenyldi Anhydride, 4,4'-bis[3-(1,2-dicarboxy)phenoxy]biphenyl dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl} Ketone dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}ketone dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]benzene bis-{4-[3-(1,2-dicarboxy)phenoxy]phenyl} bis-{4-[4-(1,2-dicarboxy)phenoxy ]phenyl}thioether dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}thioether dianhydride, 2,2-bis{4-[3-(1, 2-Dicarboxy)phenoxy]phenyl}-1,1,1,3,3,3-propane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylene Benzenetetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride, etc.

作為能夠併用之二胺之例，可例舉：對苯二胺、間苯二胺、鄰苯二胺、3,3'-二胺基二苯醚、3,4'-二胺基二苯醚、4,4'-二胺基二苯醚、3,3'-二胺基二苯硫醚、3,4'-二胺基二苯硫醚、4,4'-二胺基二苯硫醚、3,3'-二胺基二苯基碸、3,4'-二胺基二苯基碸、4,4'-二胺基二苯基碸、9,9-雙(4-胺基苯基)茀、3,3'-二胺基二苯甲酮、4,4'-二胺基二苯甲酮、3,4'-二胺基二苯甲酮、3,3'-二胺基二苯甲烷、4,4'-二胺基二苯甲烷、3,4'-二胺基二苯甲烷、2,2-二(3-胺基苯基)丙烷、2,2-二(4-胺基苯基)丙烷、2-(3-胺基苯基)-2-(4-胺基苯基)丙烷、1,1-二(3-胺基苯基)-1-苯乙烷、1,1-二(4-胺基苯基)-1-苯乙烷、1-(3-胺基苯基)-1-(4-胺基苯基)-1-苯乙烷、1,3-雙(3-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(3-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯甲醯基)苯、1,3-雙(4-胺基苯甲醯基)苯、1,4-雙(3-胺基苯甲醯基)苯、1,4-雙(4-胺基苯甲醯基)苯、1,3-雙(3-胺基-α,α-二甲基苄基)苯、1,3-雙(4-胺基-α,α-二甲基苄基)苯、1,4-雙(3-胺基-α,α-二甲基苄基)苯、1,4-雙(4-胺基-α,α-二甲基苄基)苯、2,6-雙(3-胺基苯氧基)苯甲腈、2,6-雙(3-胺基苯氧基)吡啶、4,4'-雙(3-胺基苯氧基)聯苯、4,4'-雙(4-胺基苯氧基)聯苯、雙[4-(3-胺基苯氧基)苯基]酮、雙[4-(4-胺基苯氧基)苯基]酮、雙[4-(3-胺基苯氧基)苯基]硫醚、雙[4-(4-胺基苯氧基)苯基]硫醚、雙[4-(3-胺基苯氧基)苯基]碸、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]醚、雙[4-(4-胺基苯氧基)苯基]醚、2,2-雙[4-(3-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、1,3-雙[4-(3-胺基苯氧基)苯甲醯基]苯、1,3-雙[4-(4-胺基苯氧基)苯甲醯基]苯、1,4-雙[4-(3-胺基苯氧基)苯甲醯基]苯、1,4-雙[4-(4-胺基苯氧基)苯甲醯基]苯、1,3-雙[4-(3-胺基苯氧基)-α,α-二甲基苄基]苯、1,3-雙[4-(4-胺基苯氧基)-α,α-二甲基苄基]苯、1,4-雙[4-(3-胺基苯氧基)-α,α-二甲基苄基]苯、1,4-雙[4-(4-胺基苯氧基)-α,α-二甲基苄基]苯、4,4'-雙[4-(4-胺基苯氧基)苯甲醯基]二苯醚、4,4'-雙[4-(4-胺基-α,α-二甲基苄基)苯氧基]二苯甲酮、4,4'-雙[4-(4-胺基-α,α-二甲基苄基)苯氧基]二苯基碸、4,4'-雙[4-(4-胺基苯氧基)苯氧基]二苯基碸、3,3'-二胺基-4,4'-二苯氧基二苯甲酮、3,3'-二胺基-4,4'-二聯苯氧基二苯甲酮、3,3'-二胺基-4-苯氧基二苯甲酮、3,3'-二胺基-4-聯苯氧基二苯甲酮、6,6'-雙(3-胺基苯氧基)-3,3,3',3'-四甲基-1,1'-螺二茚、6,6'-雙(4-胺基苯氧基)-3,3,3',3'-四甲基-1,1'-螺二茚、1,3-雙(3-胺基丙基)四甲基二矽氧烷、1,3-雙(4-胺基丁基)四甲基二矽氧烷、α,ω-雙(3-胺基丙基)聚二甲基矽氧烷、α,ω-雙(3-胺基丁基)聚二甲基矽氧烷、雙(胺基甲基)醚、雙(2-胺基乙基)醚、雙(3-胺基丙基)醚、雙(2-胺基甲氧基)乙基]醚、雙[2-(2-胺基乙氧基)乙基]醚、雙[2-(3-胺基丙氧基)乙基]醚、1,2-雙(胺基甲氧基)乙烷、1,2-雙(2-胺基乙氧基)乙烷、1,2-雙[2-(胺基甲氧基)乙氧基]乙烷、1,2-雙[2-(2-胺基乙氧基)乙氧基]乙烷、乙二醇雙(3-胺基丙基)醚、二乙二醇雙(3-胺基丙基)醚、三乙二醇雙(3-胺基丙基)醚、乙二胺、1,3-丙二胺、1,4-丁二胺、1,5-戊二胺、1,6-己二胺、1,7-庚二胺、1,8-辛二胺、1,9-壬二胺、1,10-癸二胺、1,11-十一烷二胺、1,12-十二烷二胺、1,2-環己二胺、1,3-環己二胺、1,4-環己二胺、反式-1,4-環己二胺、1,2-二(2-胺基乙基)環己烷、1,3-二(2-胺基乙基)環己烷、1,4-二(2-胺基乙基)環己烷、雙(4-胺基環乙基)甲烷、2,6-雙(胺基甲基)雙環[2.2.1]庚烷、2,5-雙(胺基甲基)雙環[2.2.1]庚烷、1,4-二胺基-2-氟苯、1,4-二胺基-2,3-二氟苯、1,4-二胺基-2,5-二氟苯、1,4-二胺基-2,6-二氟苯、1,4-二胺基-2,3,5-三氟苯、1,4-二胺基-2,3,5,6-四氟苯、1,4-二胺基-2-(三氟甲基)苯、1,4-二胺基-2,3-雙(三氟甲基)苯、1,4-二胺基-2,5-雙(三氟甲基)苯、1,4-二胺基-2,6-雙(三氟甲基)苯、1,4-二胺基-2,3,5-三(三氟甲基)苯、1,4-二胺基-2,3,5,6-四(三氟甲基)苯。Examples of diamines that can be used together include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3'-diaminodiphenyl ether, and 3,4'-diaminodiphenyl Ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl Thioether, 3,3'-diaminodiphenyl sine, 3,4'-diamino diphenyl sine, 4,4'-diamino diphenyl sine, 9,9-bis(4- Aminophenyl) phenyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3' -Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2 -Bis(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, 1,1-bis(3-aminophenyl)-1 -Phenylethane, 1,1-bis(4-aminophenyl)-1-phenylethane, 1-(3-aminophenyl)-1-(4-aminophenyl)-1-benzene Ethane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene , 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminobenzyl)benzene, 1,3-bis(4-aminobenzyl)benzene , 1,4-bis(3-aminobenzyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(3-amino-α,α- Dimethylbenzyl)benzene, 1,3-bis(4-amino-α,α-dimethylbenzyl)benzene, 1,4-bis(3-amino-α,α-dimethylbenzyl) phenyl)benzene, 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene, 2,6-bis(3-aminophenoxy)benzonitrile, 2,6-bis (3-aminophenoxy)pyridine, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4 -(3-Aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]sulfur ether, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]thiane, bis[4-(4-aminophenoxy) bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, 2,2-bis[4 -(3-Aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis[4-(3-amino) Phenoxy)benzyl]benzene, 1,3-bis[4-(4-aminophenoxy)benzyl]benzene, 1,4-bis[4-(3-aminophenoxy) base)benzyl]benzene, 1,4-bis[4-(4-aminophenoxy)benzyl]benzene, 1,3-bis[4-(3-aminophenoxy) -α,α-Dimethylbenzyl]benzene, 1,3-bis[4-(4-aminophenoxy)-α,α-dimethyl Benzyl]benzene, 1,4-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-aminophenoxy) base)-α,α-dimethylbenzyl]benzene, 4,4'-bis[4-(4-aminophenoxy)benzyl]diphenyl ether, 4,4'-bis[4 -(4-Amino-α,α-dimethylbenzyl)phenoxy]benzophenone, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl ) phenoxy] diphenyl selenium, 4,4'-bis[4-(4-aminophenoxy) phenoxy] diphenyl sine, 3,3'-diamino-4,4' -Diphenoxybenzophenone, 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxydiphenyl ketone, 3,3'-diamino-4-biphenoxybenzophenone, 6,6'-bis(3-aminophenoxy)-3,3,3',3'-tetra Methyl-1,1'-spirobiindene, 6,6'-bis(4-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindene , 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane, α,ω-bis(3 -aminopropyl) dimethiconol, α,ω-bis(3-aminobutyl)dimethiconol, bis(aminomethyl)ether, bis(2-amino) ethyl) ether, bis(3-aminopropyl) ether, bis(2-aminomethoxy)ethyl]ether, bis[2-(2-aminoethoxy)ethyl]ether, bis(2-aminoethoxy)ethyl]ether [2-(3-Aminopropoxy)ethyl]ether, 1,2-bis(aminomethoxy)ethane, 1,2-bis(2-aminoethoxy)ethane, 1 ,2-bis[2-(aminomethoxy)ethoxy]ethane, 1,2-bis[2-(2-aminoethoxy)ethoxy]ethane, ethylene glycol bis( 3-aminopropyl) ether, diethylene glycol bis(3-aminopropyl) ether, triethylene glycol bis(3-aminopropyl) ether, ethylenediamine, 1,3-propanediamine , 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1 ,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine Hexanediamine, trans-1,4-cyclohexanediamine, 1,2-bis(2-aminoethyl)cyclohexane, 1,3-bis(2-aminoethyl)cyclohexane, 1,4-bis(2-aminoethyl)cyclohexane, bis(4-aminocycloethyl)methane, 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane, 2 ,5-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,4-diamino-2-fluorobenzene, 1,4-diamino-2,3-difluorobenzene, 1,4-diamino-2,3-difluorobenzene 4-Diamino-2,5-difluorobenzene, 1,4-diamino-2,6-difluorobenzene, 1,4-diamino-2,3,5-trifluorobenzene, 1, 4-Diamino-2,3,5,6-tetrafluorobenzene, 1,4-diamino-2-(trifluoromethyl)benzene, 1,4- Diamino-2,3-bis(trifluoromethyl)benzene, 1,4-diamino-2,5-bis(trifluoromethyl)benzene, 1,4-diamino-2,6- Bis(trifluoromethyl)benzene, 1,4-diamino-2,3,5-tris(trifluoromethyl)benzene, 1,4-diamino-2,3,5,6-tetra( trifluoromethyl)benzene.

(聚醯亞胺之組成之具體例) 如上所述，一實施方式之聚醯亞胺包含作為酸二酐成分之具有通式(1)所表示之酯結構之酸二酐及具有環丁烷結構之酸二酐，且包含作為二胺成分之氟烷基取代聯苯胺。 (Specific example of composition of polyimide) As described above, the polyimide of one embodiment includes, as acid dianhydride components, an acid dianhydride having an ester structure represented by the general formula (1) and an acid dianhydride having a cyclobutane structure, and a diamine Fluoroalkyl substituted benzidine as the ingredient.

至於通式(1)所表示之酸二酐之量，相對於酸二酐成分總量100莫耳%，較佳為40～85莫耳%，更佳為45～80莫耳%，進而較佳為50～70莫耳%。藉由設為該範圍，能夠獲得對二氯甲烷等低沸點溶劑表現出較高溶解性並且具有優異之機械強度之聚醯亞胺。如上所述，通式(1)所表示之酸二酐中，特佳為式(2)所表示之TAHMBP。As for the amount of the acid dianhydride represented by the general formula (1), it is preferably 40 to 85 mol %, more preferably 45 to 80 mol %, and more preferably 100 mol % of the total amount of acid dianhydride components. Preferably, it is 50-70 mol%. By setting it as this range, the polyimide which shows high solubility to low-boiling-point solvents, such as methylene chloride, and has 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 preferred.

至於具有環丁烷結構之酸二酐之量，相對於酸二酐成分總量100莫耳%，較佳為15～60莫耳%，更佳為20～55莫耳%，進而較佳為25～50莫耳%。藉由設為該範圍，能夠獲得對二氯甲烷等低沸點溶劑具有溶解性，同時著色較少且機械強度優異之聚醯亞胺。如上所述，具有環丁烷結構之酸二酐中，特佳為1,2,3,4-環丁烷四羧酸二酐(CBDA)。As for the amount of the acid dianhydride having a cyclobutane structure, it is preferably 15-60 mol%, more preferably 20-55 mol%, and more preferably 100 mol% of the total acid dianhydride component 25 to 50 mol%. By setting it as this range, it is possible to obtain a polyimide which is soluble in low-boiling point solvents such as dichloromethane, has less coloration, and is excellent in mechanical strength. As described above, among the acid dianhydrides having a cyclobutane structure, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) is particularly preferred.

於併用除通式(1)所表示之酸二酐及具有環丁烷結構之酸二酐以外之酸二酐之情形時，其量相對於酸二酐成分總量100莫耳%，較佳為45莫耳%以下，更佳為30莫耳%以下。就獲得溶解性、透明性及機械強度優異之聚醯亞胺之觀點而言，作為併用之酸二酐之較佳例，可例舉：3,3',4,4'-聯苯四羧酸二酐(s-BPDA)、4,4'-氧二鄰苯二甲酸二酐(s-ODPA)、2,2-雙(3,4-二羧基苯基)-1,1,1,3,3,3-六氟丙烷二酐(6FDA)等。When an acid dianhydride other than the acid dianhydride represented by the general formula (1) and the acid dianhydride having a cyclobutane structure is used in combination, the amount thereof is preferably 100 mol % relative to the total amount of the acid dianhydride components. It is 45 mol% or less, more preferably 30 mol% or less. From the viewpoint of obtaining polyimide excellent in solubility, transparency and mechanical strength, as a preferable example of the acid dianhydride used in combination, 3,3',4,4'-biphenyltetracarboxyl Acid dianhydride (s-BPDA), 4,4'-oxydiphthalic acid dianhydride (s-ODPA), 2,2-bis(3,4-dicarboxyphenyl)-1,1,1, 3,3,3-hexafluoropropane dianhydride (6FDA), etc.

至於氟烷基取代聯苯胺之量，相對於二胺成分總量100莫耳%，較佳為40莫耳%以上，更佳為60莫耳%以上，進而較佳為70莫耳%以上。藉由設為該範圍，能夠無損機械強度而獲得透明性及溶解性優異之聚醯亞胺。如上所述，氟烷基取代聯苯胺中，較佳為2,2'-雙(三氟甲基)聯苯胺(TFMB)。The amount of fluoroalkyl-substituted benzidine is preferably 40 mol % or more, more preferably 60 mol % or more, and further preferably 70 mol % or more relative to 100 mol % of the total amount of diamine components. By setting it as this range, the polyimide excellent in transparency and solubility can be obtained without sacrificing mechanical strength. As described above, among the fluoroalkyl-substituted benzidines, 2,2'-bis(trifluoromethyl)benzidine (TFMB) is preferred.

於併用除氟烷基取代聯苯胺以外之二胺之情形時，其量相對於二胺成分總量100莫耳%，較佳為60莫耳%以下，更佳為40%以下，進而較佳為30莫耳%以下。就聚醯亞胺之透明性及溶解性之觀點而言，較佳為併用TFMB等氟烷基取代聯苯胺與3,3'-二胺基二苯基碸(3,3'-DDS)或4,4'-二胺基二苯基碸(3,3'-DDS)。相對於二胺成分總量100莫耳%，二胺基二苯基碸之量較佳為5～40莫耳%，更佳為10～30莫耳%。When a diamine other than fluoroalkyl-substituted benzidine is used in combination, the amount is preferably 60 mol % or less, more preferably 40 mol % or less, more preferably 100 mol % of the total amount of the diamine component. is 30 mol% or less. From the viewpoints of transparency and solubility of polyimide, it is preferable to use fluoroalkyl-substituted benzidine such as TFMB together with 3,3'-diaminodiphenyldiphenyl (3,3'-DDS) or 4,4'-Diaminodiphenylene (3,3'-DDS). The amount of diaminodiphenyl sulfone is preferably 5 to 40 mol %, more preferably 10 to 30 mol %, relative to 100 mol % of the total amount of the diamine component.

如上所述，聚醯亞胺較佳為包含作為酸二酐成分之40～85莫耳%之TAHMBP及15～60莫耳%之CBDA，且包含作為二胺成分之40～100莫耳%之TFMB者。進而，就提昇於溶劑中之溶解性及膜之透明性之觀點而言，較佳為包含作為二胺成分的5～40莫耳%之二胺基二苯基碸(3,3'-DDS或/及4,4'-DDS)，還可包含作為酸二酐之6FDA、s-BPDA、s-ODPA等。As described above, 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 a diamine component. TFMB person. Furthermore, from the viewpoint of improving the solubility in a solvent and the transparency of the film, it is preferable to contain 5 to 40 mol % of diaminodiphenyl sulfone (3,3'-DDS) as a diamine component or/and 4,4'-DDS), 6FDA, s-BPDA, s-ODPA, etc. can also be included as acid dianhydrides.

＜聚醯亞胺樹脂之製作＞ 聚醯亞胺樹脂之製造方法並無特別限定，較佳為如下方法：使二胺與酸二酐於溶劑中反應而製備作為聚醯亞胺前驅物之聚醯胺酸，藉由聚醯胺酸之脫水環化而進行醯亞胺化。例如，藉由向聚醯胺酸溶液中添加醯亞胺化觸媒及脫水劑，對聚醯胺酸進行脫水閉環，可獲得聚醯亞胺溶液。將聚醯亞胺溶液與聚醯亞胺之貧溶劑加以混合，使聚醯亞胺樹脂析出，並進行固液分離，藉此可獲得聚醯亞胺樹脂。 ＜Production of Polyimide Resin＞ The production method of the polyimide resin is not particularly limited, but the method is preferably the following: reacting a diamine and an acid dianhydride in a solvent to prepare a polyimide precursor as a polyimide precursor; Acid dehydration cyclization for imidization. For example, a polyimide solution can be obtained by adding an imidization catalyst and a dehydrating agent to a polyimide solution to dehydrate and ring-close the polyimide. The polyimide resin is obtained by mixing the polyimide solution and the poor solvent of polyimide to precipitate the polyimide resin and perform solid-liquid separation.

(聚醯胺酸之合成) 藉由使酸二酐與二胺於溶劑中反應，可獲得聚醯胺酸溶液。酸二酐及二胺較佳為使用實質上等莫耳量。即，酸二酐成分與二胺之莫耳比較佳為處於95：105～105：95之範圍內。 (Synthesis of Polyamide) A polyamic acid solution can be obtained by reacting an acid dianhydride and a diamine in a solvent. The acid dianhydride and the diamine are preferably used in substantially equimolar amounts. That is, the molar ratio of the acid dianhydride component and the diamine is preferably in the range of 95:105 to 105:95.

於酸二酐與二胺之聚合中，能夠使用之有機溶劑並無特別限定，只要可以使酸二酐及二胺、以及作為聚合產物之聚醯胺酸溶解即可。作為有機溶劑之具體例，可例舉：甲基脲、N,N-二甲基乙基脲等脲系溶劑；二甲基亞碸、二苯基碸、四甲基碸等碸系溶劑；N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、N,N'-二乙基乙醯胺、N-甲基-2-吡咯啶酮、γ-丁內酯、六甲基磷酸三醯胺等醯胺系溶劑；氯仿、二氯甲烷等鹵化烷基系溶劑；苯、甲苯等芳香族烴系溶劑、四氫呋喃、1,3-二氧戊環、1,4-二㗁烷、二甲醚、二***、對甲酚甲醚等醚系溶劑。其中，出於聚合反應性及聚醯胺酸之溶解性優異之方面考慮，較佳為N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、或N-甲基吡咯啶酮。In the polymerization of the acid dianhydride and the diamine, the organic solvent that can be used is not particularly limited, as long as the acid dianhydride and the diamine and the polyamide acid which is the polymerization product can be dissolved. Specific examples of organic solvents include: urea-based solvents such as methyl urea and N,N-dimethylethyl urea; N,N-dimethylacetamide, N,N-dimethylformamide, N,N'-diethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone , amide-based solvents such as triamide hexamethylphosphate; halogenated alkyl-based solvents such as chloroform and dichloromethane; aromatic hydrocarbon-based solvents such as benzene and toluene, tetrahydrofuran, 1,3-dioxolane, 1,4 - Ether-based solvents such as diethyl ether, dimethyl ether, diethyl ether, and p-cresol methyl ether. Among them, N,N-dimethylacetamide, N,N-dimethylformamide, or N-methylacetamide are preferred in view of excellent polymerization reactivity and solubility of polyamides Pyrrolidone.

酸二酐與二胺之聚合中之反應溫度並無特別限定，較佳為0℃以上80℃以下，更佳為20℃以上45℃以下。藉由設為0℃以上，往往能夠抑制反應速度之下降，藉由設為80℃以下，往往能夠抑制酸二酐之開環所導致之聚合度之下降等。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, more preferably 20°C or higher and 45°C or lower. By setting it as 0 degreeC or more, the fall of a reaction rate may be suppressed, and by setting it as 80 degreeC or less, the fall of the polymerization degree by the ring-opening of an acid dianhydride may be suppressed, etc.

(醯亞胺化) 藉由聚醯胺酸之脫水環化，可獲得聚醯亞胺。至於溶液中之醯亞胺化，適宜採用化學醯亞胺化法，即向聚醯胺酸溶液中添加脫水劑及醯亞胺化觸媒等。亦可對聚醯胺酸溶液進行加熱以促進醯亞胺化之進行。 (imidization) Polyimide can be obtained by dehydration cyclization of polyamide. As for imidization in solution, chemical imidization method is suitable, that is, adding a dehydrating agent and imidization catalyst to the polyimide solution. The polyamic acid solution can also be heated to promote the imidization.

作為醯亞胺化觸媒，可使用三級胺。作為三級胺，較佳為雜環式三級胺。作為雜環式三級胺之具體例，可例舉吡啶、甲基吡啶、喹啉、異喹啉等。脫水劑可使用羧酸酐，具體而言，可例舉乙酸酐、丙酸酐、正丁酸酐、苯甲酸酐、三氟乙酸酐等。As the imidization catalyst, tertiary amines can be used. The tertiary amine is preferably a heterocyclic tertiary amine. Specific examples of the heterocyclic tertiary amine include pyridine, picoline, quinoline, isoquinoline, and the like. Carboxylic anhydride can be used as a dehydrating agent, and acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, trifluoroacetic anhydride, etc. are mentioned specifically,.

至於醯亞胺化觸媒之添加量，相對於聚醯胺酸之胺基，較佳為0.5～5.0倍莫耳當量，更佳為0.7～2.5倍莫耳當量，進而較佳為0.8～2.0倍莫耳當量。至於脫水劑之添加量，相對於聚醯胺酸之胺基，較佳為0.5～10.0倍莫耳當量，更佳為0.7～5.0倍莫耳當量，進而較佳為0.8～3.0倍莫耳當量。As for the addition amount of the imidization catalyst, it is preferably 0.5 to 5.0 times the molar equivalent, more preferably 0.7 to 2.5 times the molar equivalent, more preferably 0.8 to 2.0 times the molar equivalent relative to the amine group of the polyamide acid. Molar equivalent. The addition amount of the dehydrating agent is preferably 0.5 to 10.0 times the molar equivalent, more preferably 0.7 to 5.0 times the molar equivalent, and more preferably 0.8 to 3.0 times the molar equivalent relative to the amine group of the polyamide acid. .

(聚醯亞胺樹脂之析出) 較佳為自藉由聚醯胺酸之醯亞胺化所獲得之聚醯亞胺溶液使聚醯亞胺樹脂以固形物之形式析出。藉由將聚醯亞胺溶液與貧溶劑加以混合，而使得聚醯亞胺樹脂析出。貧溶劑較佳為聚醯亞胺樹脂之貧溶劑，且與溶解有聚醯亞胺樹脂之溶劑混合，可例舉水、醇類等。作為醇類，可例舉甲醇、乙醇、異丙醇、乙二醇、三乙二醇、2-丁醇、2-己醇、環戊醇、環己醇、苯酚、第三丁醇等。出於聚醯亞胺不易產生開環等方面考慮，較佳為異丙醇、2-丁醇、2-戊醇、苯酚、環戊醇、環己醇、第三丁醇等醇，特佳為異丙醇。 (Precipitation of Polyimide Resin) Preferably, the polyimide resin is precipitated as a solid from the polyimide solution obtained by the imidization of the polyimide. The polyimide resin is precipitated by mixing the polyimide solution with the poor solvent. The poor solvent is preferably a poor solvent of the polyimide resin, and is mixed with the solvent in which the polyimide resin is dissolved, and examples thereof include water, alcohols, and the like. Examples of alcohols include methanol, ethanol, isopropanol, ethylene glycol, triethylene glycol, 2-butanol, 2-hexanol, cyclopentanol, cyclohexanol, phenol, tertiary butanol, and the like. Considering that polyimide is not easy to produce ring-opening, etc., preferably alcohols such as isopropanol, 2-butanol, 2-pentanol, phenol, cyclopentanol, cyclohexanol, tertiary butanol, especially preferred is isopropanol.

＜聚醯亞胺膜之製作＞ 將使聚醯亞胺樹脂溶解於有機溶劑中而成之聚醯亞胺溶液(製膜用塗料)塗佈於基材上，並將溶劑乾燥去除，藉此能夠製造聚醯亞胺膜。作為使聚醯亞胺樹脂溶解之有機溶劑，只要能夠使上述聚醯亞胺樹脂溶解即可，可根據聚醯亞胺樹脂之用途來適宜選擇，但較佳為二氯甲烷、乙酸甲酯、四氫呋喃、丙酮、及1,3-二氧戊環等低沸點溶劑，出於沸點較低且溶劑之乾燥去除較為容易之方面考慮，特佳為二氯甲烷。藉由以如上方式調整酸二酐成分及二胺成分之組成比，可獲得對二氯甲烷等低沸點溶劑亦表現出較高溶解性之聚醯亞胺。 ＜Production of Polyimide Film＞ A polyimide film can be produced by applying a polyimide solution (coating material for film formation) obtained by dissolving a polyimide resin in an organic solvent on a substrate, and drying the solvent to remove the solvent. As the organic solvent for dissolving the polyimide resin, as long as it can dissolve the above-mentioned polyimide resin, it can be appropriately selected according to the application of the polyimide resin, but methylene chloride, methyl acetate, Low-boiling point solvents such as tetrahydrofuran, acetone, and 1,3-dioxolane are particularly preferred to be dichloromethane from the viewpoint of low boiling point and easy drying and removal of the solvent. By adjusting the composition ratio of the acid dianhydride component and the diamine component as described above, a polyimide having high solubility even in low-boiling point solvents such as dichloromethane can be obtained.

至於聚醯亞胺溶液之固形物成分濃度，根據聚醯亞胺之分子量、膜之厚度或製膜環境等來適宜設定即可。固形物成分濃度較佳為5～30重量%，更佳為6～20重量%。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.

(紫外線吸收劑) 如上所述，聚醯亞胺膜包含紫外線吸收劑。於包含紫外線吸收劑之聚醯亞胺之製作中，較佳為使聚醯亞胺溶液含有紫外線吸收劑。如上所述，作為紫外線吸收劑，出於可見光之吸收較少且可獲得良好之耐光性之方面考慮，較佳為苯并***系紫外線吸收劑及三𠯤系紫外線吸收劑。尤其是就抑制由溶劑之乾燥時之加熱引起的紫外線吸收劑之揮發之觀點而言，聚醯亞胺溶液較佳為包含三𠯤系紫外線吸收劑。聚醯亞胺溶液(及聚醯亞胺膜)亦可包含三𠯤系紫外線吸收劑及苯并***系紫外線吸收劑。 (UV absorber) As mentioned above, the polyimide film contains an ultraviolet absorber. In the production of the polyimide containing the ultraviolet absorber, it is preferable that the polyimide solution contains the ultraviolet absorber. As described above, as the ultraviolet absorber, a benzotriazole-based ultraviolet absorber and a trisulfan-based ultraviolet absorber are preferred from the viewpoints of less visible light absorption and favorable light resistance. In particular, from the viewpoint of suppressing volatilization of the ultraviolet absorber by heating during drying of the solvent, the polyimide solution preferably contains a tris-based ultraviolet absorber. The polyimide solution (and the polyimide film) may also contain tris-based UV absorbers and benzotriazole-based UV absorbers.

用作聚醯亞胺之酸二酐成分之通式(1)之酸二酐為苯酚與偏苯三甲酸酐之酯，容易因紫外線而發生光劣化。推測其原因在於，在結構方面容易發生光弗里斯重排等重排反應。藉由使聚醯亞胺膜包含紫外線吸收劑，入射至聚醯亞胺膜之紫外線被紫外線吸收劑吸收，因此往往聚醯亞胺不易受紫外線影響，從而光劣化所導致之著色(黃變)得到抑制。The acid dianhydride of the general formula (1) used as the acid dianhydride component of the polyimide is an ester of phenol and trimellitic acid anhydride, and is liable to photodegrade by ultraviolet rays. The reason for this is presumed to be that rearrangement reactions such as photofrisian rearrangement easily occur in terms of structure. By making the polyimide film contain an ultraviolet absorber, the ultraviolet rays incident on the polyimide film are absorbed by the ultraviolet absorber, so that the polyimide is often not easily affected by ultraviolet rays, resulting in coloring (yellowing) caused by light deterioration. be suppressed.

就抑制聚醯亞胺之光劣化之觀點而言，相對於總固形物成分100重量份，聚醯亞胺溶液中之紫外線吸收劑之量較佳為0.1重量份以上，更佳為0.3重量份以上，亦可為0.5重量份以上、0.7重量份以上或1重量份以上。紫外線吸收劑之量越多，越可以抑制聚醯亞胺之光劣化。另一方面，於紫外線吸收劑之量過多之情形時，由於紫外線吸收劑不會與聚醯亞胺充分相容，故而有時聚醯亞胺膜發生白濁、或紫外線吸收劑滲出至表面。因此，相對於總固形物成分100重量份，聚醯亞胺溶液中之紫外線吸收劑之量較佳為4.5重量份以下，更佳為4重量份以下，亦可為3.5重量份以下或3重量份以下。From the viewpoint of suppressing photodegradation of polyimide, 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 relative to 100 parts by weight of the total solid content More than 0.5 weight part or more, 0.7 weight part or more, or 1 weight part or more may be sufficient. The more the amount of the ultraviolet absorber, the more the photodegradation of the polyimide can be suppressed. On the other hand, when the amount of the ultraviolet absorber is too large, since the ultraviolet absorber is not sufficiently compatible with the polyimide, the polyimide film may become cloudy or the ultraviolet absorber may ooze out to the surface. Therefore, with respect to 100 parts by weight of the total solid content, 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 may also be 3.5 parts by weight or less or 3 parts by weight copies or less.

於聚醯亞胺含有通式(1)所表示之酸二酐成分之情形時，不易在抑制膜之白濁或紫外線吸收劑之滲出之同時充分抑制聚醯亞胺之光劣化。因此，較佳為如後所述，藉由使設置於聚醯亞胺膜1之表面之硬塗層2含有紫外線吸收劑而使其具有紫外線遮蔽性，從而減少到達聚醯亞胺膜1之紫外線之量。When the polyimide contains the acid dianhydride component represented by the general formula (1), it is difficult to sufficiently suppress the photodegradation of the polyimide while suppressing the cloudiness of the film or the bleed-out of the ultraviolet absorber. Therefore, as 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 have ultraviolet shielding properties, thereby reducing the amount of UV rays reaching the polyimide film 1. amount of UV light.

(添加劑) 聚醯亞胺溶液亦可包含除聚醯亞胺樹脂及紫外線吸收劑以外之樹脂成分或添加劑。作為添加劑，可例舉交聯劑、染料、界面活性劑、調平劑、塑化劑、微粒子等。相對於聚醯亞胺樹脂組合物之固形物成分100重量份，聚醯亞胺樹脂之含量較佳為60重量份以上，更佳為70重量份以上，進而較佳為80重量份以上。 (additive) The polyimide solution may also contain resin components or additives other than the polyimide resin and the ultraviolet absorber. As an additive, a crosslinking agent, a dye, a surfactant, a leveling agent, a plasticizer, a fine particle, etc. are mentioned. The content of the polyimide resin is preferably 60 parts by weight or more, more preferably 70 parts by weight or more, and still more preferably 80 parts by weight or more with respect to 100 parts by weight of the solid content of the polyimide resin composition.

作為上述染料之具體例，可例舉蒽醌系化合物、酞菁系化合物、靛藍系化合物等。其中，就耐熱性之觀點而言，較佳為蒽醌系。至於其使用量，例如以聚醯亞胺樹脂為基準，可為0.1～100 ppm左右、亦可為1～90 ppm、10～80 ppm或20～70 ppm。藉由包含染料，能夠調整聚醯亞胺膜之色調。聚醯亞胺及紫外線吸收劑因吸收可見光之短波長區域之光而略呈黃色，但可藉由添加作為上藍劑發揮功能之染料來中和色相。至於上藍劑，可適宜使用公知者，作為市售產品，可例舉「MACROLEX Blue RR」、「Sumiplast Violet B」、「Sumiplast Violet OR」、「Plast Blue8580」、「Plast Blue8590」、「Plast Violet8840」等。As a specific example of the said dye, an anthraquinone type compound, a phthalocyanine type compound, an indigo type compound, etc. are mentioned. Among them, from the viewpoint of heat resistance, anthraquinone-based ones are preferred. As for the usage amount, for example, based on the polyimide resin, it may be about 0.1 to 100 ppm, or may be 1 to 90 ppm, 10 to 80 ppm, or 20 to 70 ppm. By including a dye, the color tone of the polyimide film can be adjusted. Polyimide and UV absorbers have a slightly yellow color due to the absorption of light in the short wavelength region of visible light, but the hue can be neutralized by adding a dye that functions as a bluing agent. As the bluing agent, a known one can be suitably used, and examples of commercially available products include "MACROLEX Blue RR", "Sumiplast Violet B", "Sumiplast Violet OR", "Plast Blue8580", "Plast Blue8590", and "Plast Violet8840" "Wait.

(塗佈及乾燥) 作為將聚醯亞胺溶液塗佈於基材之方法，可使用公知方法，例如可藉由棒式塗佈機或缺角輪塗佈機進行塗佈。作為塗佈聚醯亞胺溶液之基材，可使用玻璃基板、SUS(Steel Use Stainless，日本不鏽鋼標準)等金屬基板、金屬滾筒、金屬帶、塑膠膜等。就提昇生產性之觀點而言，較佳為使用金屬滾筒、金屬帶等環形支持體或長條塑膠膜等作為支持體，並以卷對卷之方式製造膜。於使用塑膠膜作為支持體之情形時，適宜選擇不會溶解於製膜塗料之溶劑之材料即可，作為塑膠材料，可使用聚對苯二甲酸乙二酯、聚碳酸酯、聚丙烯酸酯、聚萘二甲酸乙二酯等。 (coating and drying) As a method of applying a polyimide solution to a substrate, a known method can be used, for example, it can be applied by a bar coater or a notch coater. As the base material for coating the polyimide solution, a glass substrate, a metal substrate such as SUS (Steel Use Stainless, Japan Stainless Steel Standard), a metal roller, a metal tape, a plastic film, and the like can be used. From the viewpoint of improving productivity, it is preferable to use an annular support such as a metal roll and a metal belt, or a long plastic film as a support, and to manufacture the film in a roll-to-roll manner. In the case of using a plastic film as a support, a material that will not dissolve in the solvent of the film-forming coating can be appropriately selected. As the plastic material, polyethylene terephthalate, polycarbonate, polyacrylate, polyethylene naphthalate, etc.

較佳為於溶劑之乾燥時進行加熱。加熱溫度並無特別限定，就抑制聚醯亞胺膜之著色及紫外線吸收劑之揮發之觀點而言，較佳為200℃以下，更佳為180℃以下。於對溶劑進行乾燥時，亦可階段性地提昇加熱溫度。亦可於減壓下對溶劑進行乾燥。使用可溶於二氯甲烷之聚醯亞胺樹脂，並以二氯甲烷作為溶劑來製備聚醯亞胺溶液，藉此即使以200℃以下之加熱亦能夠容易地減少殘存溶劑，並可抑制著色及紫外線吸收劑之揮發。聚醯亞胺膜之殘存溶劑量(相對於膜之質量而言，膜中所包含之溶劑之質量)較佳為1.5%以下，更佳為1.0%以下。若殘存溶劑量處於該範圍內，則有聚醯亞胺膜之機械強度提昇之傾向。Preferably, heating is performed while the solvent is being dried. The heating temperature is not particularly limited, but from the viewpoint of suppressing the coloration of the polyimide film and the volatilization of the ultraviolet absorber, it is preferably 200°C or lower, more preferably 180°C or lower. When drying the solvent, the heating temperature may be increased stepwise. The solvent can also be dried under reduced pressure. Using a polyimide resin soluble in dichloromethane and using dichloromethane as a solvent to prepare a polyimide solution, the residual solvent can be easily reduced and coloring can be suppressed even when heated below 200°C And the volatilization of UV absorbers. The residual solvent content of the polyimide film (the mass of the solvent contained in the film relative to the mass of the film) is preferably 1.5% or less, more preferably 1.0% or less. When the residual solvent amount is within this range, the mechanical strength of the polyimide film tends to increase.

聚醯亞胺膜之厚度並無特別限定，根據用途適宜設定即可。聚醯亞胺膜之厚度例如為5～100 μm左右。就兼顧機械強度及透明性之觀點而言，聚醯亞胺膜之厚度較佳為30 μm以上，更佳為35 μm以上，進而較佳為40 μm以上。尤其是於用於顯示器之覆蓋窗等需要強度之用途的情形時，聚醯亞胺膜之厚度較佳為40 μm以上。聚醯亞胺膜之厚度較佳為90 μm以下，更佳為85 μm以下。The thickness of the polyimide film is not particularly limited, and may be appropriately set according to the application. The thickness of the polyimide film is, for example, about 5 to 100 μm. From the viewpoint of taking both mechanical strength and transparency into consideration, the thickness of the polyimide film is preferably 30 μm or more, more preferably 35 μm or more, and still more preferably 40 μm or more. In particular, when used in applications requiring strength, such as a cover window of a display, the thickness of the polyimide film is preferably 40 μm or more. The thickness of the polyimide film is preferably 90 μm or less, more preferably 85 μm or less.

就防止因卷對卷搬送時與捲筒之接觸或捲取時膜彼此之接觸所導致的膜損傷之觀點而言，形成硬塗層之前之聚醯亞胺膜之鉛筆硬度較佳為HB以上，更佳為F以上。The pencil hardness of the polyimide film before the formation of the hard coat layer is preferably HB or more from the viewpoint of preventing damage to the film due to contact with the reel during roll-to-roll transfer or contact between the films during winding , more preferably F or more.

[硬塗層] 藉由於聚醯亞胺膜1上塗佈硬塗組合物並進行光硬化，而形成硬塗層2。硬塗組合物包含光硬化性樹脂及光聚合起始劑。即，硬塗層係包含作為光硬化性樹脂組合物之硬塗組合物之硬化物的硬化樹脂層。藉由於硬塗組合物中包含紫外線吸收劑，而形成包含紫外線吸收劑之硬塗層。 [Hard coat] The hard coat layer 2 is formed by applying the hard coat composition on the polyimide film 1 and photohardening. The hard coating composition contains a photocurable resin and a photopolymerization initiator. That is, the hard-coat layer contains the hardened resin layer which is the hardened|cured material of the hard-coat composition of a photocurable resin composition. The hard coat layer containing the ultraviolet absorber is formed by including the ultraviolet absorber in the hard coat composition.

＜硬塗組合物＞  硬塗組合物之光硬化性樹脂為具有2個以上之光聚合性官能基之多官能化合物。多官能化合物可為單體或低聚物。光聚合性官能基可為自由基聚合性或陽離子聚合性。作為自由基聚合性官能基，可例舉乙烯基、(甲基)丙烯醯基等具有乙烯性不飽和雙鍵之官能基。作為陽離子聚合性官能基，可例舉環氧基、氧雜環丁基等環狀醚基。<Hard coat composition> The photocurable resin of the hard coat composition is a polyfunctional compound having two or more photopolymerizable functional groups. Multifunctional compounds can be monomers or oligomers. The photopolymerizable functional group may be radically polymerizable or cationically polymerizable. As a radically polymerizable functional group, the functional group which has an ethylenically unsaturated double bond, such as a vinyl group and a (meth)acryloyl group, is mentioned. As a cationically polymerizable functional group, a cyclic ether group, such as an epoxy group and an oxetanyl group, is mentioned.

其中，出於能夠利用陽離子光聚合進行硬化，且硬化收縮較小之方面考慮，作為光硬化性樹脂之光聚合性官能基，較佳為環氧基及氧雜環丁基。作為包含環氧基之陽離子光聚合性官能基，可例舉縮水甘油基及脂環式環氧基。其中，出於陽離子光聚合之反應性較高之方面考慮，較佳為脂環式環氧基。Among them, epoxy groups and oxetanyl groups are preferable as the photopolymerizable functional groups of the photocurable resin from the viewpoint of being able to be cured by cationic photopolymerization and having a small curing shrinkage. As a cationic photopolymerizable functional group containing an epoxy group, a glycidyl group and an alicyclic epoxy group are mentioned. Among them, an alicyclic epoxy group is preferable from the viewpoint of high reactivity of cationic photopolymerization.

如上所述，由於硬塗組合物包含紫外線吸收劑，故而有時在利用紫外線照射進行光硬化時，作為激發光之紫外線被紫外線吸收劑吸收，而導致硬化不良(阻礙硬化)。作為自由基光聚合反應之活性種之光自由基由於壽命較短，故而於硬化反應過程中需要持續照射紫外線，容易受到紫外線吸收劑之阻害硬化之影響。As described above, since the hard coating composition contains an ultraviolet absorber, when photocuring by ultraviolet irradiation, ultraviolet rays as excitation light are absorbed by the ultraviolet absorber, resulting in poor curing (resistance of curing). As the active species of the radical photopolymerization reaction, the photoradical has a short lifespan, so it is necessary to continuously irradiate ultraviolet rays during the curing reaction, which is easily affected by the inhibition and curing of the ultraviolet absorber.

另一方面，陽離子光聚合反應之活性種為藉由光照射所產生之酸，相較於光自由基，活性種之壽命更長，即使於光照射後，硬化反應亦會長時間地進行。因此，相較於自由基光聚合，陽離子光聚合不易受到紫外線吸收劑之影響，即使於硬塗組合物包含紫外線吸收劑之情形下，亦不易產生硬化不良。因此，硬塗組合物較佳為包含具有環氧基等陽離子光聚合性官能基之光硬化性樹脂、陽離子光聚合起始劑(光酸產生劑)、及紫外線吸收劑之陽離子光聚合性組合物。On the other hand, the active species of the cationic photopolymerization reaction is an acid generated by light irradiation. Compared with light radicals, the active species have a longer lifespan, and the curing reaction proceeds for a long time even after light irradiation. Therefore, compared with the radical photopolymerization, the cationic photopolymerization is less susceptible to the influence of the ultraviolet absorber, and even in the case where the hard coating composition contains the ultraviolet absorber, the curing failure is not easily caused. Therefore, the hard coating composition is preferably a cationic photopolymerizable combination comprising a photocurable resin having a cationic photopolymerizable functional group such as an epoxy group, a cationic photopolymerization initiator (photoacid generator), and an ultraviolet absorber thing.

作為陽離子光聚合性硬塗組合物之例，可例舉WO2018/096729號、WO2014/204010號、日本專利特開2017-8142號公報等所揭示之包含具有環氧基之聚矽氧烷化合物之組合物。Examples of the cationic photopolymerizable hard coating composition include those disclosed in WO2018/096729, WO2014/204010, Japanese Patent Laid-Open No. 2017-8142, etc., which include a polysiloxane compound having an epoxy group. combination.

(作為光硬化性樹脂之聚矽氧烷化合物)  具有陽離子光聚合性之聚矽氧烷化合物具有環氧基作為陽離子光聚合性官能基。環氧基較佳為脂環式環氧基，其中較佳為3,4-環氧基環己基。(Polysiloxane compound as photocurable resin) The polysiloxane compound having cationic photopolymerizability has an epoxy group as a cationic photopolymerizable functional group. The epoxy group is preferably an alicyclic epoxy group, and among them, a 3,4-epoxycyclohexyl group is preferable.

具有脂環式環氧基之聚矽氧烷化合物例如可藉由(A)具有脂環式環氧基之矽烷化合物之縮合；或(B)於1個分子中具有與SiH基之反應性之碳-碳雙鍵及脂環式環氧基之化合物(例如乙烯基環氧環己烷)與於1個分子中至少具有2個SiH基之聚矽氧烷化合物的矽氫化反應而獲得。出於能夠獲得於1個分子中具有多個脂環式環氧基之網狀結構之聚矽氧烷化合物的方面考慮，聚矽氧烷化合物較佳為藉由上述(A)之方法所形成。The polysiloxane compound having an alicyclic epoxy group can be obtained, for example, by (A) condensation of a silane compound having an alicyclic epoxy group; or (B) a compound having reactivity with a SiH group in one molecule. It is obtained by the hydrosilation reaction of a compound of carbon-carbon double bond and alicyclic epoxy group (eg vinyl epoxycyclohexane) and a polysiloxane compound having at least 2 SiH groups in one molecule. The polysiloxane compound is preferably formed by the method of the above (A) from the viewpoint that a polysiloxane compound having a network structure having a plurality of alicyclic epoxy groups in one molecule can be obtained. .

作為成為上述(A)之縮合反應之原料之矽烷化合物，可例舉下述通式(3)所表示之化合物。 Y-R 5-(Si(OR 6) xR 7 3 － x)          (3) As a silane compound used as a raw material of the condensation reaction of said (A), the compound represented by following general formula (3) is mentioned. YR 5 -(Si(OR 6 ) x R 7 3 - x ) (3)

通式(3)中，Y為脂環式環氧基，R 5為碳數1～10之伸烷基。R 6為氫原子、選自碳數1～10之烷基、碳數6～25之芳基及碳數7～12之烷基之一價烴基。R 7為氫原子或碳數1～10之烷基。x為1～3之整數。於x為2以上之情形時，複數個R 6可相同亦可不同。於(3－x)為2以上之情形時，複數個R 7可相同亦可不同。 In the general formula (3), Y is an alicyclic epoxy group, and R 5 is an alkylene group having 1 to 10 carbon atoms. R 6 is a hydrogen atom, a monovalent hydrocarbon group selected from the group consisting of 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 1-3. When x is 2 or more, a plurality of R 6 may be the same or different. When (3-x) is 2 or more, a plurality of R 7 may be the same or different.

如上所述，作為脂環式環氧基Y，較佳為3,4-環氧基環己基。伸烷基R 5可為直鏈狀或具有分支，較佳為直鏈伸烷基，較佳為碳數1～5之直鏈伸烷基，特佳為伸乙基。即，與Si鍵結之取代基Y-R 5-較佳為β-(3,4-環氧環己基)乙基。 As described above, the alicyclic epoxy group Y is preferably a 3,4-epoxycyclohexyl group. The alkylene group R 5 may be straight-chain or branched, and is preferably a straight-chain alkylene, preferably a straight-chain alkylene having 1 to 5 carbon atoms, and particularly preferably an ethylidene. That is, the substituent YR 5 - bonded to Si is preferably β-(3,4-epoxycyclohexyl)ethyl.

作為R 6之具體例，可例舉氫原子、甲基、乙基、丙基、丁基、戊基、己基、辛基、壬基、癸基、苯基、甲苯基、二甲苯基、萘基、苄基、及苯乙基。就提昇聚矽氧烷化合物之陽離子光聚合時之脂環式環氧基之反應性的觀點而言，R 6較佳為碳數1～4之烷基，特佳為乙基或丙基。 Specific examples of R 6 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, a phenyl group, a tolyl group, a xylyl group, and a naphthalene group. , benzyl, and phenethyl. From the viewpoint of improving the reactivity of the alicyclic epoxy group during the cationic photopolymerization of the polysiloxane compound, R 6 is preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably an ethyl group or a propyl group.

作為R 7之具體例，可例舉氫原子、甲基、乙基、丙基、丁基、戊基、己基、辛基、壬基、癸基等。就促進矽烷化合物之縮合之觀點而言，R 7較佳為碳數1～3之烷基，特佳為甲基。 As a specific example of R< 7 >, 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, etc. are mentioned. From the viewpoint of accelerating the condensation of the silane compound, R 7 is preferably an alkyl group having 1 to 3 carbon atoms, particularly preferably a methyl group.

就形成網狀聚矽氧烷化合物、及增加聚矽氧烷化合物中所包含之脂環式環氧基之數量而提高硬化膜之硬度的觀點而言，通式(3)中之x較佳為2或3。為了對藉由縮合所獲得之聚矽氧烷化合物之分子量進行調整等，亦可併用x為2或3之矽烷化合物與x為1之矽烷化合物。From the viewpoint of forming a network polysiloxane compound and increasing the number of alicyclic epoxy groups contained in the polysiloxane compound to increase the hardness of the cured film, x in the general formula (3) is preferred 2 or 3. In order to adjust the molecular weight of the polysiloxane compound obtained by condensation, etc., the silane compound in which x is 2 or 3 and the silane compound in which x is 1 may be used in combination.

作為通式(3)所表示之矽烷化合物之具體例，可例舉：β-(3,4-環氧環己基)乙基三甲氧基矽烷、β-(3,4-環氧環己基)乙基甲基二甲氧基矽烷、β-(3,4-環氧環己基)乙基二甲基甲氧基矽烷、γ-(3,4-環氧環己基)丙基三甲氧基矽烷、γ-(3,4-環氧環己基)丙基甲基二甲氧基矽烷、γ-(3,4-環氧環己基)丙基二甲基甲氧基矽烷等。Specific examples of the silane compound represented by the general formula (3) include β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl) Ethylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyldimethylmethoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane , γ-(3,4-epoxycyclohexyl)propylmethyldimethoxysilane, γ-(3,4-epoxycyclohexyl)propyldimethylmethoxysilane, etc.

藉由上述矽烷化合物之Si-OR 6部分之反應，形成Si-O-Si鍵而生成聚矽氧烷化合物。環氧基環己基等脂環式環氧化物之親電子反應性較高，親核反應性較低。因此，就抑制環氧基之開環之觀點而言，較佳為於中性或鹼性條件下實施反應。 By the reaction of the Si-OR 6 moiety of the silane compound described above, Si-O-Si bonds are formed to generate the polysiloxane compound. Alicyclic epoxides such as epoxycyclohexyl have higher electrophilic reactivity and lower 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.

作為用於使反應系呈鹼性之鹼性化合物，可例舉氫氧化鈉、氫氧化鋰、氫氧化鎂等鹼金屬或鹼土類金屬之氫氧化物、及胺類。若於形成硬塗層(光硬化反應)時存在鹼性化合物，則有時由陽離子光聚合起始劑(光酸產生劑)產生之酸被鹼性化合物淬滅，而阻礙脂環式環氧基之陽離子光聚合反應。因此，用於形成聚矽氧烷化合物之鹼性化合物較佳為藉由揮發能夠去除。又，就抑制聚矽氧烷化合物之環氧基之開環之觀點而言，鹼性化合物較佳為親核性較低。因此，作為鹼性化合物，較佳為三級胺，其中，較佳為三乙胺、二乙基甲胺、三丙胺、甲基二異丙胺、二異丙基乙胺等沸點為30～160℃之三級胺。Examples of the basic compound for making the reaction system alkaline include hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, lithium hydroxide, and magnesium hydroxide, and amines. When a basic compound is present in the formation of the hard coat layer (photohardening reaction), the acid generated by the cationic photopolymerization initiator (photoacid generator) may be quenched by the basic compound, and the alicyclic epoxy resin may be inhibited. based cationic photopolymerization. Therefore, the basic compound used to form the polysiloxane compound is preferably removable by volatilization. Moreover, from the viewpoint of suppressing ring-opening of the epoxy group of the polysiloxane compound, the basic compound is preferably low in nucleophilicity. Therefore, as the basic compound, tertiary amines are preferred, and among them, triethylamine, diethylmethylamine, tripropylamine, methyldiisopropylamine, diisopropylethylamine, and the like are preferred and have a boiling point of 30 to 160 ℃ of tertiary amines.

就提昇硬化膜之硬度之觀點而言，藉由矽烷化合物之縮合所獲得之聚矽氧烷化合物之重量平均分子量較佳為500以上。又，就抑制聚矽氧烷化合物之揮發之觀點而言，聚矽氧烷化合物之重量平均分子量亦較佳為500以上。另一方面，若分子量過大，則有時因與其他組合物之相容性下降等而產生白濁。因此，聚矽氧烷化合物之重量平均分子量較佳為20000以下。聚矽氧烷化合物之重量平均分子量更佳為1000～18000，更佳為1500～16000，進而較佳為2000～14000，特佳為2800～12000。From the viewpoint of improving the hardness of the cured film, the weight average molecular weight of the polysiloxane compound obtained by condensation of the silane compound is preferably 500 or more. Moreover, from the viewpoint of suppressing volatilization of the polysiloxane compound, the weight average molecular weight of the polysiloxane compound is also preferably 500 or more. On the other hand, when the molecular weight is too large, white turbidity may occur due to decreased compatibility with other compositions. Therefore, the weight average molecular weight of the polysiloxane compound is preferably 20,000 or less. The weight average molecular weight of the polysiloxane compound is more preferably 1000-18000, more preferably 1500-16000, still more preferably 2000-14000, particularly preferably 2800-12000.

聚矽氧烷化合物較佳為於1個分子中具有複數個脂環式環氧基。聚矽氧烷化合物之1個分子中所包含之脂環式環氧基之數量越大，往往光硬化時之交聯密度變得越高，從而越為提高硬化膜之機械強度。聚矽氧烷化合物之1個分子中之脂環式環氧基之數量較佳為3個以上，更佳為4個以上，進而較佳為5個以上。另一方面，若1個分子中所包含之脂環式環氧基之數變得過大，則硬化時無助於分子間之交聯之官能基的比率有時增加。因此，聚矽氧烷化合物之1個分子中之脂環式環氧基之數量較佳為100個以下，更佳為80個以下，進而較佳為70個以下，特佳為60個以下。The polysiloxane compound preferably has a plurality of alicyclic epoxy groups in one molecule. The larger the number of alicyclic epoxy groups contained in one molecule of the polysiloxane compound, the higher the crosslinking density at the time of photocuring, and the more improved the mechanical strength of the cured film. The number of alicyclic epoxy groups in one molecule of the polysiloxane compound is preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more. On the other hand, when the number of the alicyclic epoxy group contained in one molecule becomes too large, the ratio of the functional group which does not contribute to the crosslinking between molecules at the time of hardening 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, still more preferably 70 or less, and particularly preferably 60 or less.

就提高交聯點密度，而提昇硬化物之硬度及耐擦傷性之觀點而言，藉由通式(3)所表示之矽烷化合物之縮合所獲得之聚矽氧烷化合物較佳為脂環式環氧基之殘存率較高者。縮合物(聚矽氧烷化合物)之脂環式環氧基之莫耳數相對於矽烷化合物所具有之脂環式環氧基之莫耳數的比率較佳為20%以上，更佳為40%以上，進而較佳為60%以上。The polysiloxane compound obtained by condensation of the silane compound represented by the general formula (3) is preferably an alicyclic compound from the viewpoint of increasing the crosslinking point density and increasing the hardness and scratch resistance of the cured product. The residual rate of epoxy group is higher. The ratio of the molar number of the alicyclic epoxy group in the condensate (polysiloxane compound) to the molar number of the alicyclic epoxy group in the silane compound is preferably 20% or more, more preferably 40 % or more, more preferably 60% or more.

就抑制光硬化時之副反應之觀點及硬化物之硬度之觀點而言，較佳為聚矽氧烷化合物中矽烷化合物每個單元所殘存之OR 6基之數量較小。聚矽氧烷化合物中每個Si原子之OR 6基之數量為2個以下。每個Si原子之OR 6基之數量平均較佳為1.5個以下，更佳為1.0個以下。就硬化物之耐彎曲性之觀點而言，聚矽氧烷化合物中每個Si原子之OR 6基之數量平均可以為0.01個以上、0.05個以上、或0.3個以上。 From the viewpoint of suppressing side reactions during photohardening and from the viewpoint of hardness of the cured product, it is preferable that the number of OR 6 groups remaining per unit of the silane compound in the polysiloxane compound is small. The number of OR 6 groups per Si atom in the polysiloxane compound is 2 or less. The number of OR 6 groups per Si atom is preferably 1.5 or less on average, more preferably 1.0 or less. From the viewpoint of bending resistance of the cured product, the number of OR 6 groups per Si atom in the polysiloxane compound may be 0.01 or more, 0.05 or more, or 0.3 or more on average.

於藉由矽烷化合物之縮合獲得聚矽氧烷化合物之情形時，除具有脂環式環氧基之矽烷化合物外，亦可使用不具有脂環式環氧基之矽烷化合物。不具有脂環式環氧基之矽烷化合物例如由下述通式(4)表示。 R 8-Si(OR 6) 3(4) When a polysiloxane compound is obtained by condensation of a silane compound, in addition to a silane compound having an alicyclic epoxy group, a silane compound not having an alicyclic epoxy group can also be used. The silane compound not having an alicyclic epoxy group is represented by, for example, the following general formula (4). R 8 -Si(OR 6 ) 3 (4)

通式(4)之R 8為選自由碳數1～10之經取代或未經取代之烷基、烯基、及取代芳基組成之群且不具有脂環式環氧基之一價基。於R 8為經取代之烷基之情形時，作為取代基，可例舉縮水甘油基、硫醇基、胺基、(甲基)丙烯醯基、苯基、環己基、鹵素等。通式(4)之R 6與通式(3)中之R 6相同。 R 8 in the general formula (4) is selected from the group consisting of substituted or unsubstituted alkyl groups, alkenyl groups, and substituted aryl groups having 1 to 10 carbon atoms, and does not have a valent group of an alicyclic epoxy group . When R 8 is a substituted alkyl group, the substituent may, for example, be a glycidyl group, a thiol group, an amino group, a (meth)acryloyl group, a phenyl group, a cyclohexyl group, a halogen or the like. R 6 in the general formula (4) is the same as R 6 in the general formula (3).

如上所述，就提昇硬化膜之機械強度之觀點而言，聚矽氧烷化合物之1個分子中所包含之脂環式環氧基之數量越大越好。因此，藉由矽烷化合物之反應所獲得之聚矽氧烷化合物較佳為於不具有脂環式環氧基之矽烷化合物(通式(4)所表示之化合物)相對於具有脂環式環氧基之矽烷化合物(通式(3)所表示之化合物)之莫耳比為2以下的條件下進行縮合所獲得者。通式(4)所表示之化合物相對於通式(3)所表示之化合物之莫耳比較佳為1以下，更佳為0.6以下，進而較佳為0.4以下，特佳為0.2以下。通式(4)所表示之化合物相對於通式(3)所表示之化合物之莫耳比亦可為0。As described above, from the viewpoint of improving the mechanical strength of the cured film, the larger the number of alicyclic epoxy groups contained in one molecule of the polysiloxane compound, the better. Therefore, the polysiloxane compound obtained by the reaction of the silane compound is preferably a silane compound having no alicyclic epoxy group (a compound represented by the general formula (4)) having an alicyclic epoxy group. The silane compound (the compound represented by the general formula (3)) of the radical 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, still more preferably 0.4 or less, and particularly preferably 0.2 or less. The molar ratio of the compound represented by the general formula (4) to the compound represented by the general formula (3) may be 0.

就形成機械強度優異之硬塗層之觀點而言，相對於固形物成分之合計100重量份，硬塗組合物中之上述聚矽氧烷化合物之含量較佳為40重量份以上，更佳為50重量份以上，進而較佳為60重量份以上。From the viewpoint of forming a hard coat layer excellent in mechanical strength, the content of the above-mentioned polysiloxane compound in the hard coat composition is preferably 40 parts by weight or more, more preferably 100 parts by weight of the total solid content. 50 parts by weight or more, more preferably 60 parts by weight or more.

(陽離子光聚合起始劑) 陽離子光聚合性之硬塗組合物較佳為包含陽離子光聚合起始劑。陽離子光聚合起始劑為藉由照射活性能量線而產生酸之化合物(光酸產生劑)。藉由自光酸產生劑生成之酸，使得上述聚矽氧烷化合物之脂環式環氧基發生反應，形成分子間交聯，從而硬塗材料硬化。 (cationic photopolymerization initiator) The cationic photopolymerizable hard coat composition preferably contains a cationic photopolymerization initiator. The cationic photopolymerization initiator is a compound (photoacid generator) that generates an acid by irradiating active energy rays. The alicyclic epoxy group of the above-mentioned polysiloxane compound is reacted by the acid generated from the photoacid generator to form intermolecular cross-linking, so that the hard coating material is hardened.

作為光酸產生劑，可例舉甲苯磺酸或四氟化硼等強酸；鋶鹽、銨鹽、鏻鹽、錪鹽、硒鹽等鎓鹽類；鐵-芳烴錯合物類；矽烷醇-金屬螯合複合物類；二碸類、二磺醯重氮甲烷類、二磺醯甲烷類、磺醯基苯甲醯基甲烷類、醯亞胺磺酸鹽類、安息香磺酸鹽類等磺酸衍生物；有機鹵素化合物類等。Examples of photoacid generators include strong acids such as toluenesulfonic acid and boron tetrafluoride; onium salts such as perium salts, ammonium salts, phosphonium salts, iodonium salts, and selenium salts; iron-aromatic complexes; silanol- Metal chelate complexes; sulfonic acid such as dioxanes, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzylmethanes, sulfonimide sulfonates, benzoin sulfonates, etc. Acid derivatives; organic halogen compounds, etc.

上述光酸產生劑中，出於在含有具有脂環式環氧基之聚矽氧烷化合物之硬塗組合物中之穩定性較高的方面考慮，較佳為芳香族鋶鹽或芳香族錪鹽。其中，出於容易獲得光硬化較快且與聚醯亞胺膜之密接性優異之硬塗層之方面考慮，芳香族鋶鹽或芳香族錪鹽之抗衡陰離子較佳為氟磷酸鹽系陰離子、氟銻酸鹽系陰離子、或氟硼酸鹽系陰離子。尤其是抗衡陰離子較佳為氟磷酸鹽系陰離子或氟銻酸鹽系陰離子。作為此種光酸產生劑之具體例，可例舉：二苯基(4-苯硫基苯基)鋶-六氟磷酸鹽、六氟磷酸鹽之一部分或全部氟原子被取代為全氟烷基之六氟磷酸鹽衍生物、二苯基(4-苯硫基苯基)鋶-六氟銻酸鹽等。Among the above-mentioned photoacid generators, from the viewpoint of high stability in a hard coating composition containing a polysiloxane compound having an alicyclic epoxy group, an aromatic perylene salt or an aromatic iodonium is preferred Salt. Among them, the counter anion of the aromatic periconium salt or the aromatic iodonium salt is preferably a fluorophosphate-based anion, Fluoroantimonate-based anions, or fluoroborate-based anions. In particular, the counter anion is preferably a fluorophosphate-based anion or a fluoroantimonate-based anion. Specific examples of such photoacid generators include diphenyl(4-phenylthiophenyl) perfluoro-hexafluorophosphate, and a part or all of fluorine atoms of hexafluorophosphate substituted with perfluoroalkane. Base hexafluorophosphate derivatives, diphenyl (4-phenylthiophenyl) perylene-hexafluoroantimonate, etc.

至於硬塗組合物中之陽離子光聚合起始劑之含量，相對於上述聚矽氧烷化合物100重量份，較佳為0.05～10重量份，更佳為0.1～5重量份。The content of the cationic photopolymerization initiator in the hard coating composition is preferably 0.05-10 parts by weight, more preferably 0.1-5 parts by weight, relative to 100 parts by weight of the polysiloxane compound.

(紫外線吸收劑) 藉由使硬塗組合物含有紫外線吸收劑而形成含有紫外線吸收劑之硬塗層。如上所述，作為紫外線吸收劑，出於可見光之吸收較少且可獲得良好之耐光性之方面考慮，較佳為苯并***系紫外線吸收劑及三𠯤系紫外線吸收劑。尤其是苯并***系紫外線吸收劑由於UVA(Ultraviolet A，紫外線A段)區域(波長320～400 nm)之吸光係數較大，且能夠有效抑制由聚醯亞胺之光重排反應引起之劣化，故而硬塗層(硬塗組合物)較佳為包含苯并***系紫外線吸收劑。 (UV absorber) The hard coat layer containing an ultraviolet absorber is formed by making the hard coat composition contain the ultraviolet absorber. As described above, as the ultraviolet absorber, a benzotriazole-based ultraviolet absorber and a trisulfan-based ultraviolet absorber are preferred from the viewpoints of less visible light absorption and favorable light resistance. In particular, the benzotriazole-based ultraviolet absorber has a large absorption coefficient in the UVA (Ultraviolet A, ultraviolet A segment) region (wavelength 320-400 nm), and can effectively inhibit the photorearrangement reaction caused by polyimide. Since it deteriorates, it is preferable that a hard-coat layer (hard-coat composition) contains a benzotriazole type ultraviolet absorber.

如上所述，於聚醯亞胺膜之製作中，在溶劑之乾燥去除等過程中需要高溫加熱，因此，聚醯亞胺膜較佳為包含耐熱性優異之三𠯤系紫外線吸收劑。若於包含三𠯤系紫外線吸收劑之聚醯亞胺膜1上形成有包含苯并***系紫外線吸收劑之硬塗層2，則寬範圍波長範圍之紫外線被吸收，故而能夠有效率地抑制聚醯亞胺之光劣化。As described above, in the production of the polyimide film, high temperature heating is required in the process of drying and removing the solvent, and therefore, the polyimide film preferably contains a three-series ultraviolet absorber with excellent heat resistance. When the hard coat layer 2 containing the benzotriazole-based ultraviolet absorber is formed on the polyimide film 1 containing the tris-based ultraviolet absorber, ultraviolet rays in a wide wavelength range are absorbed, so that it is possible to effectively suppress the Photodegradation of polyimide.

就提昇硬塗層之紫外線吸收性(遮蔽性)，減少到達聚醯亞胺膜之紫外線之量之觀點而言，相對於總固形物成分100重量份，硬塗組合物中之紫外線吸收劑之量較佳為0.1重量份以上，更佳為0.3重量份以上，亦可為0.5重量份以上、0.7重量份以上或1重量份以上。紫外線吸收劑之量越多，往往越能夠提昇硬塗層之紫外線遮蔽性。另一方面，於紫外線吸收劑之量過多之情形時，在硬塗組合物之光硬化過程中被紫外線吸收劑吸收之紫外線之量較多，即使為陽離子光聚合性硬塗組合物，亦有時光硬化不夠充分，而導致硬塗膜之機械強度(表面硬度)不足。因此，相對於總固形物成分100重量份，硬塗組合物中之紫外線吸收劑之量較佳為4.5重量份以下，更佳為4重量份以下，亦可為3.5重量份以下或3重量份以下。From the viewpoint of improving the ultraviolet absorbency (shielding property) of the hard coat layer and reducing the amount of ultraviolet rays reaching the polyimide film, the amount of the ultraviolet absorber in the hard coat composition is 100 parts by weight relative to the total solid content. The amount is preferably 0.1 part by weight or more, more preferably 0.3 part by weight or more, and may be 0.5 part by weight or more, 0.7 part by weight or more, or 1 part by weight or more. The higher the amount of UV absorber, the better the UV shielding properties of the hard coat layer tend to be. On the other hand, when the amount of the ultraviolet absorber is too large, the amount of ultraviolet rays absorbed by the ultraviolet absorber during the photohardening process of the hard coating composition is large, even if it is a cationic photopolymerizable hard coating composition. Light hardening is insufficient, resulting in insufficient mechanical strength (surface hardness) of the hard coat film. Therefore, with respect to 100 parts by weight of the total solid content, the amount of the ultraviolet absorber in the hard coating composition is preferably 4.5 parts by weight or less, more preferably 4 parts by weight or less, and may also be 3.5 parts by weight or less or 3 parts by weight the following.

(溶劑) 硬塗組合物可為無溶劑型亦可包含溶劑。於包含溶劑之情形時，較佳為不會使聚醯亞胺膜溶解者。另一方面，藉由使用具有會使聚醯亞胺膜膨潤程度之溶解性之溶劑，有時使得聚醯亞胺膜基材1與硬塗層2之密接性提昇。至於硬塗組合物中之溶劑之量，相對於硬化性樹脂(聚矽氧烷化合物)100重量份，較佳為500重量份以下，更佳為300重量份以下，進而較佳為100重量份以下。 (solvent) The hardcoat composition may be solvent-free or may contain a solvent. When a solvent is included, it is preferable that the polyimide film is not dissolved. On the other hand, the adhesiveness between the polyimide film substrate 1 and the hard coat layer 2 may be improved by using a solvent having a degree of solubility to swell the polyimide film. The amount of the solvent in the hard coating composition is preferably 500 parts by weight or less, more preferably 300 parts by weight or less, and still more preferably 100 parts by weight relative to 100 parts by weight of the curable resin (polysiloxane compound). the following.

(反應性稀釋劑) 硬塗組合物亦可包含反應性稀釋劑。作為反應性稀釋劑之例，例如可使用除上述聚矽氧烷化合物以外之陽離子聚合性化合物。作為聚合之反應性稀釋劑，可例舉具有環氧基、乙烯醚基、氧雜環丁基、及烷氧基矽烷基等官能基之化合物。 (reactive diluent) The hardcoat composition may also contain reactive diluents. As an example of a reactive diluent, a cationically polymerizable compound other than the above-mentioned polysiloxane compound can be used, for example. As the reactive diluent for polymerization, compounds having functional groups such as epoxy groups, vinyl ether groups, oxetanyl groups, and alkoxysilyl groups can be exemplified.

(光敏劑) 出於提昇陽離子光聚合起始劑(光酸產生劑)之感光性等目的，硬塗組合物亦可包含光敏劑。關於光敏劑，由於更有效率的是能夠吸收光酸產生劑本身無法吸收之波長區域之光者，故而較佳為光敏劑與光酸產生劑之吸收波長區域之重疊較少。作為光敏劑，可例舉蒽衍生物、二苯甲酮衍生物、9-氧硫𠮿

Figure 110139216-001
衍生物、蒽醌衍生物、安息香衍生物等。 (Photosensitizer) The hard coating composition may also contain a photosensitizer for the purpose of enhancing the sensitivity of the cationic photopolymerization initiator (photoacid generator). As for the photosensitizer, since it is more efficient to absorb light in a wavelength region that the photoacid generator itself cannot absorb, it is preferable that the absorption wavelength region of the photosensitizer and the photoacid generator overlap less. Examples of the photosensitizer include anthracene derivatives, benzophenone derivatives, 9-oxothiocyanate
Figure 110139216-001
Derivatives, Anthraquinone Derivatives, Benzoin Derivatives, etc.

(粒子) 硬塗組合物亦可包含粒子以調整表面硬度或耐彎曲性等膜特性、抑制硬化收縮等。作為粒子，適宜選擇使用有機粒子、無機粒子、有機無機複合粒子等即可。作為有機粒子之材料，可例舉聚(甲基)丙烯酸烷基酯、交聯聚(甲基)丙烯酸烷基酯、交聯苯乙烯、尼龍、矽酮、交聯矽酮、交聯胺基甲酸酯、交聯丁二烯等。作為無機粒子之材料，可例舉氧化矽、氧化鈦、氧化鋁、氧化錫、氧化鋯、氧化鋅、氧化銻等金屬氧化物；氮化矽、氮化硼等金屬氮化物；碳酸鈣、磷酸氫鈣、磷酸鈣、磷酸鋁等金屬鹽等。作為有機無機複合填料，可例舉於有機粒子之表面形成有無機物層者、於無機粒子之表面形成有有機物層或有機微粒子者。 (particle) The hard coating composition may also contain particles to adjust film properties such as surface hardness and bending resistance, to suppress shrinkage on curing, and the like. As the particles, organic particles, inorganic particles, organic-inorganic composite particles, etc. may be appropriately selected and used. As the material of the organic particles, poly(meth)acrylate, cross-linked poly(meth)acrylate, cross-linked styrene, nylon, silicone, cross-linked silicone, cross-linked amine group can be exemplified Formate, cross-linked butadiene, etc. Examples of materials of inorganic particles include metal oxides such as silicon oxide, titanium oxide, aluminum oxide, tin oxide, zirconium oxide, zinc oxide, and antimony oxide; metal nitrides such as silicon nitride and boron nitride; calcium carbonate, phosphoric acid, etc. Metal salts such as calcium hydrogen, calcium phosphate, aluminum phosphate, etc. As an organic-inorganic composite filler, the thing which formed the inorganic substance layer on the surface of an organic particle, and the thing which formed the organic substance layer or organic fine particle on the surface of an inorganic particle can be mentioned.

粒子之平均粒徑例如為5 nm～10 μm左右。就提昇硬塗層之透明性之觀點而言，平均粒徑較佳為1000 nm以下，更佳為500 nm以下，進而較佳為300 nm以下，特佳為100 nm以下。粒徑可藉由雷射繞射/散射式粒徑分佈測定裝置來測定，將以體積為基準之中值粒徑作為平均粒徑。The average particle diameter of the particles is, for example, about 5 nm to 10 μm. From the viewpoint of improving the transparency of the hard coat layer, the average particle size is preferably 1000 nm or less, more preferably 500 nm or less, still more preferably 300 nm or less, and particularly preferably 100 nm or less. The particle size can be measured by a laser diffraction/scattering particle size distribution analyzer, and the median particle size based on the volume is used as the average particle size.

粒子亦可經表面修飾。藉由對粒子進行表面修飾，粒子之分散性呈提昇傾向。又，於藉由能夠與環氧基反應之聚合性官能基對粒子表面進行修飾之情形時，粒子表面之官能基與上述聚矽氧烷化合物之環氧基反應而形成化學交聯，因此可期待提昇膜強度。The particles can also be surface modified. By surface modification of the particles, the dispersibility of the particles tends to be improved. In addition, when the particle surface is modified with a polymerizable functional group capable of reacting with an epoxy group, the functional group on the particle surface reacts with the epoxy group of the above-mentioned polysiloxane compound to form chemical crosslinking, so that it is possible to Looking forward to improving the film strength.

(添加劑) 硬塗組合物亦可包含無機顏料、有機顏料、表面調整劑、表面改質劑、塑化劑、分散劑、濕潤劑、增黏劑、消泡劑等添加劑。又，硬塗組合物亦可包含除上述聚矽氧烷化合物以外之熱塑性、熱硬化性或光硬化性之樹脂材料。 (additive) The hard coating composition may also contain additives such as inorganic pigments, organic pigments, surface modifiers, surface modifiers, plasticizers, dispersants, wetting agents, tackifiers, and defoaming agents. Further, the hard coating composition may contain thermoplastic, thermosetting or photocurable resin materials other than the above-mentioned polysiloxane compound.

如上所述，硬塗組合物除作為硬化性樹脂之聚矽氧烷化合物以外，亦可包含光聚合起始劑及紫外線吸收劑，亦可進而包含作為固形物成分(不揮發分)之反應性稀釋劑、光敏劑、粒子及其他添加劑。就形成機械強度優異之硬塗層之觀點而言，相對於固形物成分之合計100重量份，硬塗組合物中之上述聚矽氧烷化合物之含量較佳為40重量份以上，更佳為50重量份以上，進而較佳為60重量份以上。As described above, in addition to the polysiloxane compound as a curable resin, the hard coating composition may contain a photopolymerization initiator and an ultraviolet absorber, and may further contain a reactivity as a solid content (nonvolatile matter). Diluents, photosensitizers, particles and other additives. From the viewpoint of forming a hard coat layer excellent in mechanical strength, the content of the above-mentioned polysiloxane compound in the hard coat composition is preferably 40 parts by weight or more, more preferably 100 parts by weight of the total solid content. 50 parts by weight or more, more preferably 60 parts by weight or more.

＜硬塗層之形成＞ 於聚醯亞胺膜上塗佈硬塗組合物，視需要將溶劑乾燥去除後，照射紫外線等活性能量線而使硬塗組合物硬化，藉此能夠獲得聚醯亞胺膜1上設置有硬塗層2之硬塗膜。 <Formation of hard coat layer> The hard coating composition is coated on the polyimide film, and if necessary, the solvent is dried and removed, and then the hard coating composition is cured by irradiating active energy rays such as ultraviolet rays. Hard coat for Coating 2.

光硬化時之活性能量線之累計照射量例如為50～10000 mJ/cm 2左右，根據聚合起始劑之種類及調配量、硬塗層之厚度等設定即可。硬化溫度並無特別限定，通常為100℃以下。 The cumulative irradiation dose of active energy rays during photocuring is, for example, about 50 to 10,000 mJ/cm 2 , and can be set according to the type and amount of the polymerization initiator, the thickness of the hard coat layer, and the like. The hardening temperature is not particularly limited, but is usually 100°C or lower.

硬塗層之厚度較佳為0.5 μm以上，更佳為2 μm以上，進而較佳為3 μm以上，最佳為5 μm以上。硬塗層之厚度較佳為100 μm以下，更佳為80 μm以下。若硬塗層之厚度小於0.5 μm，則有時無法充分提昇表面硬度等機械特性。另一方面，若硬塗層之厚度大於100 μm，則有時透明性或耐彎曲性下降。The thickness of the hard coat layer is preferably 0.5 μm or more, more preferably 2 μm or more, still more preferably 3 μm or more, and most preferably 5 μm or more. The thickness of the hard coat layer is preferably 100 μm or less, more preferably 80 μm or less. When the thickness of the hard coat layer is less than 0.5 μm, mechanical properties such as surface hardness may not be sufficiently improved. On the other hand, when the thickness of a hard-coat layer exceeds 100 micrometers, transparency and bending resistance may fall.

[硬塗膜之特性] 硬塗膜之全光線透過率較佳為80%以上，更佳為85%以上，進而較佳為88%以上。硬塗膜之霧度較佳為1.5%以下，更佳為0.9%以下，進而較佳為0.7%以下，特佳為0.5%以下。 [Characteristics of hard coat film] The total light transmittance of the hard coat film is preferably 80% or more, more preferably 85% or more, and 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, still more preferably 0.7% or less, and particularly preferably 0.5% or less.

硬塗膜之黃度(YI)較佳為10以下，更佳為6以下，進而較佳為5以下，亦可為4以下、3.5以下、3.0以下或2.5以下。The yellowness (YI) of the hard coat film is preferably 10 or less, more preferably 6 or less, still more preferably 5 or less, and may be 4 or less, 3.5 or less, 3.0 or less, or 2.5 or less.

如上所述，本發明之硬塗膜之聚醯亞胺膜1及硬塗層2兩者均包含紫外線吸收劑。因此，於外界光自硬塗層2側入射時，紫外線被硬塗層2吸收(遮蔽)，到達聚醯亞胺膜1之紫外線量較少，且到達聚醯亞胺膜1之紫外線被聚醯亞胺膜1中所包含之紫外線吸收劑吸收。因此，聚醯亞胺膜1之聚醯亞胺樹脂不易受到紫外線影響，由光劣化引起之變色(黃度之增加)得到抑制。As described above, both the polyimide film 1 and the hard coat layer 2 of the hard coat film of the present invention contain an ultraviolet absorber. Therefore, when external light is incident from the side of the hard coat layer 2, the ultraviolet rays are absorbed (shielded) by the hard coat layer 2, the amount of ultraviolet rays reaching the polyimide film 1 is small, and the ultraviolet rays reaching the polyimide film 1 are polymerized The ultraviolet absorber contained in the imide film 1 absorbs. Therefore, the polyimide resin of the polyimide film 1 is less susceptible to ultraviolet rays, and discoloration (increase in yellowness) due to light deterioration is suppressed.

聚醯亞胺膜中之紫外線吸收劑之含量較佳為0.1～4.5重量%，更佳為0.3～4重量%，進而較佳為0.5～3.5重量%，亦可為0.7～3重量%或1.0～2.5重量%。硬塗層中之紫外線吸收劑之含量較佳為0.1～4.5重量%，更佳為0.3～4重量%，進而較佳為0.5～3.5重量%，亦可為0.7～3重量%或1.0～2.5重量%。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 may also be 0.7 to 3% by weight or 1.0% by weight ~2.5 wt%. 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 may also be 0.7 to 3% by weight or 1.0 to 2.5% by weight weight%.

於放射照度500 W/m 2、黑面板溫度63℃之條件下自形成有硬塗層之面側照射紫外線48小時，此時之硬塗膜之黃度之增大量ΔYI較佳為6以下，更佳為5以下，亦可為4.5以下或4.0以下。 Under the conditions of irradiance of 500 W/m 2 and black panel temperature of 63°C, ultraviolet rays are irradiated from the side on which the hard coat layer is formed for 48 hours. At this time, the increase ΔYI of the yellowness of the hard coat layer is preferably 6 or less, More preferably, it is 5 or less, and may be 4.5 or less or 4.0 or less.

硬塗膜之形成有硬塗層之面之鉛筆硬度較佳為HB以上，更佳為H以上，進而較佳為2 H以上，特佳為3 H以上，亦可為4 H以上。硬塗膜之拉伸彈性模數較佳為3.5 GPa以上，更佳為4.0 GPa以上，進而較佳為5.0 GPa以上。The pencil hardness of the surface on which the hard coat layer is formed of the hard coat film is preferably HB or more, more preferably H or more, still more preferably 2 H or more, particularly preferably 3 H or more, and may be 4 H or more. The tensile modulus of elasticity of the hard coat film is preferably 3.5 GPa or more, more preferably 4.0 GPa or more, and still more preferably 5.0 GPa or more.

[硬塗膜之應用] 硬塗膜亦可於硬塗層2上或聚醯亞胺膜1之未形成硬塗層之面設置有各種功能層。作為功能層，可例舉抗反射層、防眩層、抗靜電層、透明電極等。又，亦可於硬塗膜附設透明黏著劑層。 [Application of hard coating film] The hard coat film may be provided with various functional layers on the hard coat layer 2 or the surface of the polyimide film 1 on which the hard coat layer is not formed. As a functional layer, an antireflection layer, an antiglare layer, an antistatic layer, a transparent electrode, etc. are mentioned. Moreover, you may attach a transparent adhesive layer to a hard coat film.

本發明之硬塗膜由於透明性較高且機械強度優異，故而適宜用於配置於圖像顯示面板之視認側表面之覆蓋窗、顯示器用透明基板、觸控面板用透明基板、及太陽電池用基板等。本發明之硬塗膜除透明性及機械強度優異以外，耐彎曲性亦優異，且耐光性較高，因此尤其是適宜用作配置於曲面顯示器或可彎折顯示器之視認側表面之覆蓋窗。 [實施例] Since the hard coat film of the present invention has high transparency and excellent mechanical strength, it is suitable for use in cover windows arranged on the visible side surface of image display panels, transparent substrates for displays, transparent substrates for touch panels, and solar cells substrate, etc. In addition to excellent transparency and mechanical strength, the hard coat film of the present invention is also excellent in bending resistance and high in light resistance, so it is particularly suitable for use as a cover window disposed on the viewing side surface of a curved display or a foldable display. [Example]

以下，基於實施例及比較例對本發明進一步具體地進行說明，但本發明並不限定於下述實施例。Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[透明聚醯亞胺膜之製作] (聚醯亞胺樹脂之製備) 向反應容器中投入作為二胺之2,2'-雙(三氟甲基)聯苯胺(TFMB)44.2 g(138.1 mmol)及3,3'-二胺基二苯基碸(3,3-DDS)3.8 g(15.3 mmol)，作為四羧酸二酐之雙(1,3-二側氧基-1,3-二氫異苯并呋喃-5-羧酸)-2,2',3,3',5,5'-六甲基聯苯-4,4'二基(TAHMBP)47.4 g(76.7 mmol)、1,2,3,4-環丁烷四羧酸二酐(CBDA)9.0 g(46.0 mmol)、及4,4'-氧二鄰苯二甲酸二酐(ODA)9.5 g(30.7 mmol)，以及作為溶劑之N,N-二甲基甲醯胺800 g，於氮氣氛圍下攪拌12小時，而獲得聚醯胺酸溶液。 [Manufacture of transparent polyimide film] (Preparation of Polyimide Resin) 44.2 g (138.1 mmol) of 2,2'-bis(trifluoromethyl)benzidine (TFMB) and 3,3'-diaminodiphenyl (3,3- DDS) 3.8 g (15.3 mmol), as bis(1,3-dioxy-1,3-dihydroisobenzofuran-5-carboxylic acid)-2,2',3 of tetracarboxylic dianhydride ,3',5,5'-hexamethylbiphenyl-4,4'diyl (TAHMBP) 47.4 g (76.7 mmol), 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) 9.0 g (46.0 mmol), 9.5 g (30.7 mmol) of 4,4'-oxydiphthalic dianhydride (ODA), and 800 g of N,N-dimethylformamide as a solvent, under nitrogen The mixture was stirred under the atmosphere for 12 hours to obtain a polyamic acid solution.

向上述聚醯胺酸溶液中添加作為醯亞胺化觸媒之吡啶36.4 g(460 mmol)及乙酸酐(7.0 g(460 mmol)，於90℃下攪拌4小時。一面攪拌冷卻至室溫之溶液，一面添加2-丙醇(IPA)2000 g，使用桐山漏斗進行吸引過濾。用1000 g之IPA對所獲得之固體清洗6次後，於溫度設定為120℃之真空烘箱內乾燥8小時，而獲得白色之聚醯亞胺樹脂。該聚醯亞胺樹脂之單體組成為TFMB/3,3'-DDS//TAHMBP/CBDA/ODA＝90/10//50/30/20(莫耳比)。To the above-mentioned polyamic acid solution, pyridine 36.4 g (460 mmol) and acetic anhydride (7.0 g (460 mmol) were added as imidization catalysts, and the mixture was stirred at 90° C. for 4 hours. The mixture was cooled to room temperature while stirring. Solution, add 2-propanol (IPA) 2000 g on one side, use Kiriyama funnel to carry out suction filtration.After cleaning 6 times to the obtained solid with the IPA of 1000 g, be set to be dried 8 hours in the vacuum oven of 120 ℃ in temperature, And obtain white polyimide resin. The monomer composition of this polyimide resin is TFMB/3,3'-DDS//TAHMBP/CBDA/ODA=90/10//50/30/20 (molar Compare).

(聚醯亞胺膜之製作) 使上述聚醯亞胺樹脂100重量份、以及表1所示之紫外線吸收劑(UVA)及上藍劑(有本化學工業製造之「PlastBlue 8590」)溶解於二氯甲烷中，而獲得固形物成分濃度為10重量%之聚醯亞胺溶液。再者，於比較例1、5、6中，未添加紫外線吸收劑。於比較例4、6中，未添加上藍劑。 (Fabrication of Polyimide Film) A solid substance was obtained by dissolving 100 parts by weight of the above-mentioned polyimide resin, as well as the ultraviolet absorber (UVA) and the bluing agent (“PlastBlue 8590” manufactured by Honken Chemical Industry Co., Ltd.) shown in Table 1 in methylene chloride. A polyimide solution with a component concentration of 10% by weight. In addition, in Comparative Examples 1, 5, and 6, no ultraviolet absorber was added. In Comparative Examples 4 and 6, the blueing agent was not added.

使用棒式塗佈機將上述聚醯亞胺溶液塗佈於無鹼玻璃，於大氣氛圍下，在40℃下加熱60分鐘，在80℃下加熱30分鐘，在150℃下加熱30分鐘，在170℃下加熱30分鐘，在200℃下加熱60分鐘，而去除溶劑，獲得厚度為50 μm之透明聚醯亞胺膜。The above-mentioned polyimide solution was coated on alkali-free glass using a bar coater, heated at 40°C for 60 minutes, 80°C for 30 minutes, and 150°C for 30 minutes in the atmosphere, and then heated at 150°C for 30 minutes. After heating at 170° C. for 30 minutes and 200° C. for 60 minutes, the solvent was removed to obtain a transparent polyimide film with a thickness of 50 μm.

[硬塗膜之製作] (倍半矽氧烷化合物之合成) 向安裝有溫度計、攪拌裝置及回流冷卻管之反應容器中添加2-(3,4-環氧環己基)乙基三甲氧基矽烷(邁圖高新材料公司製造之「SILQUEST A-186」)66.5 g(270 mmol)及1-甲氧基-2-丙醇(PGME)16.5 g，均勻地進行攪拌。使氯化鎂0.039 g(0.405 mmol)溶解於水9.7 g(539 mmol)及甲醇5.8 g中，將所獲得之溶液歷時5分鐘滴加至上述混合液中，攪拌至均勻。然後，升溫至80℃，一面攪拌一面進行6小時縮聚反應。反應結束後，使用旋轉蒸發器進行減壓去揮發及濃縮，去除縮合物中之甲醇及水，而獲得倍半矽氧烷化合物。 [Production of hard coating film] (Synthesis of Silsesquioxane Compounds) Add 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane ("SILQUEST A-186" manufactured by Momentive High-tech Materials Co., Ltd.) 66.5 to the reaction vessel equipped with thermometer, stirring device and reflux cooling tube g (270 mmol) and 16.5 g of 1-methoxy-2-propanol (PGME) were uniformly stirred. 0.039 g (0.405 mmol) of magnesium chloride was dissolved in 9.7 g (539 mmol) of water and 5.8 g of methanol, and the obtained solution was added dropwise to the above mixed solution over 5 minutes, and stirred until uniform. Then, the temperature was raised to 80°C, and a polycondensation reaction was performed for 6 hours while stirring. After the completion of the reaction, a rotary evaporator was used for de-volatization and concentration under reduced pressure to remove methanol and water in the condensate to obtain a silsesquioxane compound.

(硬塗組合物之製備) 按照表1所示之調配量向上述倍半矽氧烷化合物100重量份中添加作為光酸產生劑(陽離子光聚合起始劑)之二苯基(4-苯硫基苯基)-SbF 6鹽之碳酸丙二酯50%溶液(San-Apro製造之「CPI-101A」)及紫外線吸收劑(UVA)，而製備硬塗組合物。再者，於比較例4及比較例6中，僅添加光酸產生劑，而不添加紫外線吸收劑。 (Preparation of Hard Coating Composition) Diphenyl (4-benzene) as a photoacid generator (cationic photopolymerization initiator) was added to 100 parts by weight of the above-mentioned silsesquioxane compound in the amount shown in Table 1. A 50% solution of thiophenyl)-SbF 6 salt in propylene carbonate ("CPI-101A" manufactured by San-Apro) and an ultraviolet absorber (UVA) were used to prepare a hard coating composition. In addition, in the comparative example 4 and the comparative example 6, only the photoacid generator was added, and the ultraviolet absorber was not added.

(硬塗層之形成) 使用棒式塗佈機，以硬塗組合物硬化後之厚度達到50 μm之方式將硬塗組合物塗佈於厚度為50 μm之透明聚醯亞胺基材之主面，於120℃下加熱10分鐘。使用高壓水銀燈以波長365 nm之累計光量達到1000 mJ/cm 2之方式照射紫外線後，於80℃下加熱2小時而使硬塗組合物硬化，而獲得於聚醯亞胺膜基材上具備硬塗(HC)層之硬塗膜。於實施例2、比較例5及比較例6中，於透明聚醯亞胺膜基材之雙面形成厚度為50 μm之硬塗(HC)層。於比較例1～4中，未形成硬塗層。 (Formation of hard coat layer) Using a bar coater, the hard coat composition was coated on the main part of a transparent polyimide substrate with a thickness of 50 μm so that the thickness of the hard coat composition after hardening reached 50 μm surface, heated at 120 ° C for 10 minutes. After irradiating ultraviolet rays with a high-pressure mercury lamp in such a way that the cumulative light intensity at a wavelength of 365 nm reaches 1000 mJ/cm 2 , the hard coating composition is cured by heating at 80° C. for 2 hours, and a polyimide film substrate with hard coating is obtained. Hard coat film for coating (HC) layer. In Example 2, Comparative Example 5 and Comparative Example 6, a hard coat (HC) layer with a thickness of 50 μm was formed on both sides of the transparent polyimide film substrate. In Comparative Examples 1 to 4, the hard coat layer was not formed.

[硬塗膜之評估] 對於實施例及比較例之硬塗膜(比較例1～4中之未形成有硬塗層之聚醯亞胺膜)，實施以下評估。 [Evaluation of hard coat film] The following evaluation was implemented about the hard coat film of an Example and a comparative example (the polyimide film in which a hard coat layer was not formed in Comparative Examples 1-4).

(外觀) 藉由目視觀察硬塗膜，結果發現，於比較例4中觀察到白濁。使用Suga Test Instruments製造之霧度計「HZ-V3」，藉由JIS K7361-1中記載之方法測定比較例4之硬塗膜之霧度，結果為41.0%。再者，實施例1～8之硬塗膜之霧度均未達0.5%。 (Exterior) When the hard coat film was visually observed, it was found that in Comparative Example 4, cloudiness was observed. The haze of the hard coat film of Comparative Example 4 was measured by the method described in JIS K7361-1 using a haze meter "HZ-V3" manufactured by Suga Test Instruments, and found to be 41.0%. Furthermore, the haze of the hard coat films of Examples 1 to 8 was less than 0.5%.

比較例8及比較例9之硬塗膜於膜表面產生了皺褶。因此，於比較例8、9中，未實施後續評估。The hard coat films of Comparative Example 8 and Comparative Example 9 had wrinkles on the film surface. Therefore, in Comparative Examples 8 and 9, subsequent evaluation was not performed.

(黃度) 將膜切成3 cm見方之尺寸，使用分光測色計(Suga Test Instruments製造之「SC-P」)測定黃度(YI)。然後，使用褪色試驗機(Suga Test Instruments製造之「U48-HB」)於放射照度500 W/m 2、黑面板溫度63℃之條件下自膜之單面(實施例1、3～8及比較例7～9中之形成有硬塗層之面)照射48小時之紫外線。測定照射紫外線後之膜之黃度，根據照射前之黃度YI 0及照射後之黃度YI 1，按照下式算出照射前後之黃度之變化量ΔYI。 ΔYI＝YI 1－YI 0 (Yellowness) The film was cut into a size of 3 cm square, and the yellowness (YI) was measured using a spectrophotometer (“SC-P” manufactured by Suga Test Instruments). Then, using a fading tester (“U48-HB” manufactured by Suga Test Instruments), under the conditions of irradiance of 500 W/m 2 and black panel temperature of 63° C. from one side of the film (Examples 1, 3 to 8 and comparisons The surface on which the hard coat layer was formed in Examples 7 to 9) was irradiated with ultraviolet rays for 48 hours. The yellowness of the film after irradiation with ultraviolet rays was measured, and from the yellowness YI 0 before irradiation and the yellowness YI 1 after irradiation, the amount of change in yellowness ΔYI before and after irradiation was calculated according to the following formula. ΔYI=YI 1 -YI 0

(鉛筆硬度) 藉由JIS K-5600-5-4鉛筆劃痕試驗測定膜之鉛筆硬度。於實施例1、3～8及比較例7～9中，對形成有硬塗層之面之鉛筆硬度進行評估。 (Pencil Hardness) The pencil hardness of the film was measured by JIS K-5600-5-4 pencil scratch test. In Examples 1, 3 to 8, and Comparative Examples 7 to 9, the pencil hardness of the surface on which the hard coat layer was formed was evaluated.

將實施例及比較例中之聚醯亞胺膜之添加劑之種類及含量、硬塗層之形成面、硬塗組合物之光酸產生劑之添加量、硬塗組合物之紫外線吸收劑之種類及含量、以及膜之評估結果示於表1。The types and contents of the additives of the polyimide films in the Examples and Comparative Examples, the surface of the hard coat layer, the amount of the photoacid generator added in the hard coat composition, and the type of the ultraviolet absorber in the hard coat composition were compared. and content, and the evaluation results of the film are shown in Table 1.

於表1中，紫外線吸收劑(UVA)採用以下簡稱。 LA-31RG：ADEKA製造之「Adekastab LA-31RG」：2,2'-亞甲基雙[6-(2H-苯并***-2-基)-4-(1,1,3,3-四甲基丁基)苯酚] LA-F70：ADEKA製造之「Adekastab LA-F70」：2,4,6-三(2-羥基-4-己氧基-3-甲基苯基)-1,3,5-三𠯤 Tin 326：BASF製造之「Tinvin 326」；2-[5-氯(2H)-苯并***-2-基]-4-甲基-6-(第三丁基)苯酚 LA-29：ADEKA製造之「Adekastab LA-29」；2-(2H-苯并***-2-基)-4-(1,1,3,3-四甲基丁基)苯酚 LA-32：ADEKA製造之「Adekastab LA-32」；2-(2H-苯并***-2-基)-對甲酚 LA-24：ADEKA製造之「Adekastab LA-24」；2-(2H-苯并***-2-基)-4,6-雙(1-甲基-1-苯基乙基)苯酚 In Table 1, the following abbreviations are used for the ultraviolet absorber (UVA). LA-31RG: "Adekastab LA-31RG" manufactured by ADEKA: 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3- tetramethylbutyl)phenol] LA-F70: "Adekastab LA-F70" manufactured by ADEKA: 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-tris𠯤 Tin 326: "Tinvin 326" manufactured by BASF; 2-[5-Chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol LA-29: "Adekastab LA-29" manufactured by ADEKA; 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol LA-32: "Adekastab LA-32" manufactured by ADEKA; 2-(2H-benzotriazol-2-yl)-p-cresol LA-24: "Adekastab LA-24" manufactured by ADEKA; 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol

[表1]    實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 實施例 6 實施例 7 實施例 8 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 比較例7 比較例8 比較例9 PI膜添加劑 UVA LA-31RG - - 2 2 2 2 2 2 - - 2 - - - 2 2 2 LA-F70 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 - 0.8 0.8 5 - - 0.8 0.8 0.8 上藍劑 40 40 40 40 40 40 40 40 40 40 40 - 40 - 40 40 40    形成面 單面 雙面 單面 單面 單面 單面 單面 單面 無 無 無 無 雙面 雙面 單面 單面 單面 HC層 光酸產生劑 1 1 2 2 2 2 2 2             1 1 2 2 2 UVA Tin 326 0.5 0.5 - - - - - - - - - - - LA-29 - - 1.5 3 - - - - - 0.5 - 5 - LA-32 - - - - 1.5 3 - - - - - - 5 LA-24 - - - - - - 1.5 3 - - - - - HC膜 外觀 良好 良好 良好 良好 良好 良好 良好 良好 良好 良好 良好 白濁 良好 良好 良好 皺褶 皺褶 YI 0 3.0 2.0    2.7 2.6 2.9 2.6 2.8 2:24 2.0 2.2 3.3 N.D. 1.8 2.2 2.8 N.D. N.D. YI 1 6.0 7.0    8.1 6.9 8.1 7.2 6.9 5.9 17.3 13.2 13.2 12.8 9.2 10.1 ∆YI 3.0 5.0    5.4 4.3 5.2 4.5 4.1 2.8 15.3 11.0 9.9 11.0 7.0 7.3 鉛筆硬度 3 H 3 H 6 H 5 H 5 H 4 H 5 H 5 H 2 H H 2 H F 3 H 3 H 6 H       [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 PI film additives UVA LA-31RG - - 2 2 2 2 2 2 - - 2 - - - 2 2 2 LA-F70 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 - 0.8 0.8 5 - - 0.8 0.8 0.8 bluing agent 40 40 40 40 40 40 40 40 40 40 40 - 40 - 40 40 40 forming surface one-sided double sided one-sided one-sided one-sided one-sided one-sided one-sided none none none none double sided double sided one-sided one-sided one-sided HC layer photoacid generator 1 1 2 2 2 2 2 2 1 1 2 2 2 UVA Tin 326 0.5 0.5 - - - - - - - - - - - LA-29 - - 1.5 3 - - - - - 0.5 - 5 - LA-32 - - - - 1.5 3 - - - - - - 5 LA-24 - - - - - - 1.5 3 - - - - - HC membrane Exterior good good good good good good good good good good good cloudy good good good folds folds YI 0 3.0 2.0 2.7 2.6 2.9 2.6 2.8 2:24 2.0 2.2 3.3 ND 1.8 2.2 2.8 ND ND YI 1 6.0 7.0 8.1 6.9 8.1 7.2 6.9 5.9 17.3 13.2 13.2 12.8 9.2 10.1 ΔYI 3.0 5.0 5.4 4.3 5.2 4.5 4.1 2.8 15.3 11.0 9.9 11.0 7.0 7.3 pencil hardness 3H 3H 6H 5H 5H 4H 5H 5H 2H H 2H F 3H 3H 6H

如表1所示，可知，於聚醯亞胺膜及硬塗層兩者中均包含紫外線吸收劑之硬塗膜藉由形成有硬塗層而表現出較高之鉛筆硬度，並且褪色試驗之光照射後之ΔYI較小且耐光性優異。As shown in Table 1, it can be seen that the hard coat film containing the ultraviolet absorber in both the polyimide film and the hard coat layer exhibited higher pencil hardness by forming the hard coat layer, and the fading test showed a higher pencil hardness. The ΔYI after light irradiation was small and the light resistance was excellent.

由實施例3、4之對比，實施例5、6之對比，及實施例7、8之對比可知，硬塗層中所包含之紫外線吸收劑之量越多，ΔYI往往越小。另一方面，於相對於硬塗組合物之樹脂分100重量份調配有5重量份之紫外線吸收劑之比較例8、9中，在硬化後之硬塗層表面觀察到褶皺。認為該褶皺之原因在於紫外線吸收劑之量較多而導致硬化不充分。From the comparison of Examples 3 and 4, the comparison of Examples 5 and 6, and the comparison of Examples 7 and 8, it can be seen that the more the amount of UV absorber contained in the hard coat layer, the smaller ΔYI tends to be. On the other hand, in Comparative Examples 8 and 9 in which 5 parts by weight of the ultraviolet absorber was blended with respect to 100 parts by weight of the resin of the hard coat composition, wrinkles were observed on the surface of the hard coat layer after curing. The cause of the wrinkles is considered to be insufficient curing due to a large amount of the ultraviolet absorber.

於未設置有硬塗層之比較例1～4中，相較於實施例，膜之鉛筆硬度較低，且硬度不足。又，聚醯亞胺膜無論有無紫外線吸收劑，ΔYI均較大，耐光性均不足。於相對於聚醯亞胺樹脂100重量份調配有5重量份之紫外線吸收劑之比較例4中，由於相容性不足，故而觀察到明顯之白濁。In Comparative Examples 1 to 4 in which the hard coat layer was not provided, the pencil hardness of the film was lower and the hardness was insufficient as compared with the Examples. In addition, regardless of the presence or absence of the ultraviolet absorber, the polyimide film had large ΔYI and insufficient light resistance. In Comparative Example 4 in which 5 parts by weight of the ultraviolet absorber was blended with respect to 100 parts by weight of the polyimide resin, since the compatibility was insufficient, a clear cloudiness was observed.

於聚醯亞胺膜及硬塗層均不包含紫外線吸收劑之比較例5中，ΔYI較大且耐光性不足。僅在硬塗層中調配有紫外線吸收劑之比較例6、僅在聚醯亞胺膜中調配有紫外線吸收劑之比較例7與比較例5相比，雖然ΔYI較小，但耐光性不足。In Comparative Example 5 in which neither the polyimide film nor the hard coat layer contained an ultraviolet absorber, ΔYI was large and light resistance was insufficient. Compared with Comparative Example 5, Comparative Example 6 in which only the ultraviolet absorber was prepared in the hard coat layer and in Comparative Example 7 in which only the ultraviolet absorber was prepared in the polyimide film, although ΔYI was small, the light resistance was insufficient.

由以上結果可知，藉由使聚醯亞胺膜及硬塗層兩者包含紫外線吸收劑，可獲得透明性、耐光性及表面硬度優異之硬塗膜。From the above results, it was found that a hard coat film excellent in transparency, light resistance, and surface hardness can be obtained by including an ultraviolet absorber in both the polyimide film and the hard coat layer.

1:聚醯亞胺膜 2:硬塗層 10:硬塗膜 1: Polyimide film 2: Hard coating 10: Hard coating

圖1係表示硬塗膜之構成例之剖視圖。FIG. 1 is a cross-sectional view showing a configuration example of a hard coat film.

1:聚醯亞胺膜 1: Polyimide film

2:硬塗層 2: Hard coating

10:硬塗膜 10: Hard coating

Claims (12)

一種硬塗膜，其係具備基材膜及設置於上述基材膜之至少一面之硬塗層者， 上述基材膜為包含聚醯亞胺樹脂之聚醯亞胺膜， 上述硬塗層包含光硬化性樹脂組合物之硬化物， 上述硬塗層及上述聚醯亞胺膜各自含有紫外線吸收劑。 A hard coat film comprising a base film and a hard coat layer provided on at least one side of the base film, The above-mentioned base film is a polyimide film comprising a polyimide resin, The above-mentioned hard coat layer contains a cured product of the photocurable resin composition, The said hard coat layer and the said polyimide film each contain an ultraviolet absorber. 如請求項1之硬塗膜，其中 上述聚醯亞胺樹脂包含作為二胺成分之氟烷基取代聯苯胺，且包含作為四羧酸二酐成分之具有式(1)所表示之酯結構之酸二酐及具有環丁烷結構之酸二酐， 上述氟烷基取代聯苯胺相對於二胺總量100莫耳%為40莫耳%以上100莫耳%以下， 上述具有式(1)所表示之酯結構之酸二酐相對於四羧酸二酐成分總量100莫耳%為40莫耳%以上85莫耳%以下，上述具有環丁烷結構之酸二酐相對於四羧酸二酐成分總量100莫耳%為15莫耳%以上60莫耳%以下，
Figure 03_image005
式(1)中，n為1或2，R 1～R 4分別獨立地為氫原子、碳原子數1～20之烷基或氟烷基，R 1～R 4中之至少1個為碳原子數1～20之烷基或氟烷基。 The hard coat film according to claim 1, wherein the polyimide resin contains fluoroalkyl-substituted benzidine as a diamine component, and contains as a tetracarboxylic dianhydride component a compound having an ester structure represented by formula (1) Acid dianhydride and acid dianhydride having a cyclobutane structure, the above-mentioned fluoroalkyl-substituted benzidine is 40 mol% or more and 100 mol% or less relative to the total amount of diamines in 100 mol%, and the above has formula (1) The acid dianhydride of the indicated ester structure is 40 mol % or more and 85 mol % or less relative to the total 100 mol % of the tetracarboxylic dianhydride components, and the above-mentioned acid dianhydride having a cyclobutane structure is relative to the tetracarboxylic acid di The total amount of anhydride components in 100 mol% is more than 15 mol% and less than 60 mol%,
Figure 03_image005
In formula (1), n is 1 or 2, R 1 to R 4 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a fluoroalkyl group, and at least one of R 1 to R 4 is a carbon An alkyl group or a fluoroalkyl group having 1 to 20 atoms. 如請求項1或2之硬塗膜，其中上述硬塗層包含具有環氧基之聚矽氧烷化合物之硬化物。The hard coat film according to claim 1 or 2, wherein the hard coat layer comprises a cured product of a polysiloxane compound having an epoxy group. 如請求項1至3中任一項之硬塗膜，其中上述紫外線吸收劑為苯并***化合物或三𠯤化合物。The hard coat film according to any one of claims 1 to 3, wherein the above-mentioned ultraviolet absorber is a benzotriazole compound or a triazole compound. 如請求項1至4中任一項之硬塗膜，其中上述聚醯亞胺膜中之紫外線吸收劑之含量為0.1～4.5重量%。The hard coat film according to any one of claims 1 to 4, wherein the content of the ultraviolet absorber in the polyimide film is 0.1 to 4.5% by weight. 如請求項1至5中任一項之硬塗膜，其中上述硬塗層中之紫外線吸收劑之含量為0.1～4.5重量%。The hard coat film according to any one of claims 1 to 5, wherein the content of the ultraviolet absorber in the hard coat layer is 0.1 to 4.5% by weight. 如請求項1至6中任一項之硬塗膜，其中上述硬塗層之厚度為0.5～100 μm。The hard coat film according to any one of claims 1 to 6, wherein the thickness of the hard coat layer is 0.5-100 μm. 如請求項1至7中任一項之硬塗膜，其中上述聚醯亞胺膜之厚度為5～100 μm。The hard coat film according to any one of claims 1 to 7, wherein the thickness of the polyimide film is 5-100 μm. 一種硬塗膜之製造方法，其係如請求項1至8中任一項之硬塗膜之製造方法，該製造方法中， 將包含聚醯亞胺樹脂及紫外線吸收劑之二氯甲烷溶液塗佈於基材上，去除溶劑，藉此製作包含紫外線吸收劑之聚醯亞胺膜， 於上述聚醯亞胺膜之表面塗佈包含光硬化性樹脂及光聚合起始劑之光硬化性樹脂組合物，進行光硬化，藉此形成硬塗層。 A method for producing a hard coat film, which is the method for producing a hard coat film according to any one of claims 1 to 8, wherein, The dichloromethane solution containing the polyimide resin and the ultraviolet absorber is coated on the substrate, and the solvent is removed, thereby producing the polyimide film containing the ultraviolet absorber, A hard-coat layer is formed by apply|coating the photocurable resin composition containing a photocurable resin and a photopolymerization initiator on the surface of the said polyimide film, and carrying out photohardening. 如請求項9之硬塗膜之製造方法，其中上述光硬化性樹脂為具有環氧基之聚矽氧烷化合物，上述光聚合起始劑為陽離子光聚合起始劑。The method for producing a hard coat film according to claim 9, wherein the photocurable resin is a polysiloxane compound having an epoxy group, and the photopolymerization initiator is a cationic photopolymerization initiator. 一種圖像顯示裝置，其於圖像顯示面板之視認側表面具備如請求項1至8中任一項之硬塗膜。An image display device provided with the hard coat film according to any one of Claims 1 to 8 on a viewable side surface of an image display panel. 如請求項11之圖像顯示裝置，其能夠彎折。The image display device of claim 11 can be bent.
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