TW202031734A - Optical film and flexible display device - Google Patents

Optical film and flexible display device Download PDF

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TW202031734A
TW202031734A TW108147427A TW108147427A TW202031734A TW 202031734 A TW202031734 A TW 202031734A TW 108147427 A TW108147427 A TW 108147427A TW 108147427 A TW108147427 A TW 108147427A TW 202031734 A TW202031734 A TW 202031734A
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formula
structural unit
group
optical film
represented
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TW108147427A
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杉山紘子
宮本皓史
池内淳一
増井建太朗
金成民
片宝蓝
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日商住友化學股份有限公司
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Priority claimed from JP2019213442A external-priority patent/JP2021084941A/en
Priority claimed from JP2019218259A external-priority patent/JP2020109154A/en
Priority claimed from JP2019218189A external-priority patent/JP7365211B2/en
Priority claimed from JP2019218184A external-priority patent/JP2020125454A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/14—Polyamide-imides
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • 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

Provided is an optical film having excellent appearance quality, the appearance quality of the optical film not being degraded upon contact with alcohol. The optical film comprises a polyamide-imide resin that contains at least: a structural unit derived from a tetracarboxylic acid compound and represented by formula (a); a structural unit derived from a dicarboxylic acid compound and represented by formula (b); and a structural unit derived from a diamine compound and represented by formula (c) [in formula (a), Y represents a tetravalent organic group; in formula (b), Z represents a divalent organic group; in formula (c), X is a divalent organic group; Rc, independently of one another, represents a hydrogen atom or a bond; and * represents a bond]. The polyamide-imide resin includes at least one structural unit selected from the group consisting of a structural unit (a1) and a structural unit (b1). The structural unit (a1) is represented by formula (a) as the structural unit derived from a tetracarboxylic acid compound, where Y is represented by formula (1) [in formula (1), Ra, independently of one another, represents a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group or a C6-C12 aryl group; hydrogen atoms included in Ra, independently of one another, may be substituted with halogen atoms; n represents an integer of 0 to 2; * represents a bond; R* represents a bond if Y is represented by formula (1), and represents Ra if Z is represented by formula (1)]. The structural unit (b1) is represented by formula (b) as the structural unit derived from a dicarboxylic acid compound, where Z is represented by formula (1). The absolute value of the difference [Delta]L* between lightness L1 * of the optical film, the lightness L1 * being obtained by measuring reflected light and based on the L*a*b* color system, and lightness L2 * of the optical film that has been in contact with ethanol for 40 minutes, the lightness L2 * being obtained by measuring the surface color difference and based on the L*a*b* color system, is no more than 0.5.

Description

光學膜及可撓性顯示裝置Optical film and flexible display device

本發明係關於一種包含聚醯胺醯亞胺系樹脂之光學膜及具備該光學膜之可撓性顯示裝置。The present invention relates to an optical film containing polyamidoimide resin and a flexible display device provided with the optical film.

目前，液晶顯示裝置或有機EL(Electroluminescence，電致發光)顯示裝置等顯示裝置不僅廣泛用於電視，於行動電話或智能手錶等各種用途亦被廣泛應用。先前，一直使用玻璃作為此種顯示裝置之前面板。然而，玻璃其透明度較高，可視種類表現出高硬度，但另一方面，非常剛硬而容易斷裂，故而難以被用作可撓性顯示裝置之前面板材料。At present, display devices such as liquid crystal display devices or organic EL (Electroluminescence, electroluminescence) display devices are not only widely used in televisions, but also in various applications such as mobile phones and smart watches. Previously, glass has been used as the front panel of such display devices. However, glass has high transparency and exhibits high hardness depending on the type. On the other hand, it is very rigid and easy to break, so it is difficult to be used as a front panel material for flexible display devices.

因此，正在研究活用高分子材料作為代替玻璃之材料。包含高分子材料之前面板由於容易表現出可撓性特性，故而期待用於各種用途。作為具有柔軟性之高分子材料之一，例如正在研究使用聚醯胺醯亞胺系樹脂之光學膜(專利文獻1及2)。 [先前技術文獻] [專利文獻]Therefore, research is underway to use polymer materials as a substitute for glass. The front panel containing a polymer material is expected to be used in various applications because it easily exhibits flexibility. As one of the flexible polymer materials, for example, optical films using polyimide resins are being studied (Patent Documents 1 and 2). [Prior Technical Literature] [Patent Literature]

[專利文獻1]日本專利特表2015-521686號公報 [專利文獻2]日本專利特開2018-119132號公報[Patent Document 1] Japanese Patent Publication No. 2015-521686 [Patent Document 2] Japanese Patent Application Publication No. 2018-119132

[發明所欲解決之問題][The problem to be solved by the invention]

用作可撓性顯示裝置之前面板材料之光學膜於應用於顯示裝置時，要求於其整個面可自所有視認角度無色不均地均勻地視認之較高之外觀品質。另一方面，亦特別要求異物或缺陷較少。為了減少異物或缺陷，於生產步驟中，利用乙醇等醇對製造設備進行清掃。然而，例如於利用醇對導輥等製造設備進行清掃後，因殘留於製造設備之醇與光學膜接觸而導致存在光學膜之外觀品質降低之情形。進而，於組入有該光學膜之可撓性顯示裝置中，亦假定使用者為了使表面清潔化而使用包含醇成分之淨化劑擦拭表面之場面，視與包含醇成分之淨化劑之接觸狀況而光學膜之外觀品質可能會降低。When the optical film used as the front panel material of the flexible display device is applied to the display device, it is required to have a high appearance quality that can be uniformly recognized from all viewing angles without color unevenness. On the other hand, there are also special requirements for fewer foreign objects or defects. In order to reduce foreign matter or defects, in the production step, the manufacturing equipment is cleaned with alcohol such as ethanol. However, for example, after cleaning manufacturing equipment such as guide rollers with alcohol, the alcohol remaining in the manufacturing equipment contacts the optical film, which may cause the appearance quality of the optical film to decrease. Furthermore, in a flexible display device incorporating the optical film, it is also assumed that the user wipes the surface with a detergent containing alcohol in order to clean the surface, depending on the contact condition with the detergent containing alcohol The appearance quality of the optical film may be reduced.

因此，本發明之課題在於提供一種即便與醇接觸亦不會損害光學膜之外觀品質之光學膜。 [解決問題之技術手段]Therefore, the subject of the present invention is to provide an optical film that does not impair the appearance quality of the optical film even if it comes into contact with alcohol. [Technical means to solve the problem]

本發明者等人為了解決上述課題而努力進行研究，結果發現，包含至少具有特定結構單元之聚醯胺醯亞胺系樹脂且與醇接觸前後之反射光測定中之基於L＊ a＊ b＊ 表色系統之亮度之變化量為特定範圍內之光學膜與醇接觸後亦具有較高之外觀品質，從而完成本發明。The inventors of the present invention made efforts to solve the above-mentioned problems. As a result, they found that the reflected light measurement before and after contact with alcohol containing a polyamide imide resin having at least a specific structural unit is based on L * a * b * The amount of change in the brightness of the color system is that the optical film within a specific range has a higher appearance quality after being in contact with alcohol, thereby completing the present invention.

即，本發明包含以下較佳之態樣。 [1]一種光學膜，其係包含至少具有源自四羧酸化合物之式(a)所表示之結構單元、源自二羧酸化合物之式(b)所表示之結構單元、及源自二胺化合物之式(c)所表示之結構單元之聚醯胺醯亞胺系樹脂者： [化1]

Figure 02_image005
[式(a)中，Y表示四價有機基，式(b)中，Z表示二價有機基，式(c)中，X表示二價有機基，Rc 相互獨立地表示氫原子或鍵結鍵，＊表示鍵結鍵]； 該聚醯胺醯亞胺系樹脂包含選自由如下結構單元所組成之群中之至少1種結構單元：作為該源自四羧酸化合物之結構單元之式(a)中之Y係由式(1)所表示之結構單元(a1)及作為該源自二羧酸化合物之結構單元之式(b)中之Z係由式(1)所表示之結構單元(b1)； [化2]
Figure 02_image007
[式(1)中，Ra 相互獨立地表示氫原子、碳數1～12之烷基、碳數1～12之烷氧基或碳數6～12之芳基，Ra 中所包含之氫原子可相互獨立地被取代為鹵素原子， n表示0～2之整數， ＊表示鍵結鍵，R＊ 於Y係由式(1)所表示之情形時，表示鍵結鍵，於Z係由式(1)所表示之情形時，表示Ra ] 該光學膜之反射光測定中之基於L＊ a＊ b＊ 表色系統之亮度L1 ＊ 與於表面之色差測定中與乙醇接觸40分鐘後之該光學膜之基於L＊ a＊ b＊ 表色系統之亮度L2 ＊ 之差之絕對值ΔL＊ 為0.5以下。 [2]如上述[1]所記載之光學膜，其中反射光測定中之基於L＊ a＊ b＊ 表色系統之該光學膜之b1 ＊ 與和乙醇接觸40分鐘後之該光學膜之b2 ＊ 之差之絕對值Δb＊ 為0.1以下。 [3]如上述[1]或[2]所記載之光學膜，其中光學膜之厚度為25 μm以上且100 μm以下。 [4]如上述[1]～[3]中任一項所記載之光學膜，其中光學膜之霧度為5%以下。 [5]如上述[1]～[4]中任一項所記載之光學膜，其中聚醯胺醯亞胺系樹脂包含式(2)： [化3]
Figure 02_image009
[式(2)中，Z1 表示作為可具有取代基之單環式芳香族環或縮合多環式芳香族環之二價芳香族基，＊表示鍵結鍵] 所表示之結構單元(b2)作為源自二羧酸化合物之結構單元，且包含式(3)： [化4]
Figure 02_image011
[式(3)中，X1 表示可具有取代基之二價芳香族基，Rc 相互獨立地表示氫原子或鍵結鍵，＊表示鍵結鍵] 所表示之結構單元(c1)作為源自二胺化合物之結構單元。 [6]如上述[5]所記載之光學膜，其中式(3)中之X1 係由式(4)所表示： [化5]
Figure 02_image013
[式(4)中，Rb 相互獨立地表示碳數1～6之烷基、碳數6～12之芳基、或碳數1～6之烷氧基，Rb 中所包含之氫原子可相互獨立地被取代為鹵素原子，r相互獨立地表示1～4之整數，＊表示鍵結鍵]。 [7]如上述[1]～[6]中任一項所記載之光學膜，其中聚醯胺醯亞胺系樹脂包含選自由如下結構單元所組成之群中之至少1種結構單元：作為源自二羧酸化合物之結構單元之式(b)中之Z係由式(5)： [化6]
Figure 02_image015
[式(5)中，Ar1 相互獨立地表示可具有取代基之二價芳香族基， V表示單鍵、-O-、二苯基亞甲基、碳數1～12之直鏈狀、支鏈狀或脂環式之二價烴基、-SO2 -、-S-、-CO-或-N(R12 )-，此處，該烴基中所包含之氫原子可相互獨立地被取代為鹵素原子，R12 表示氫原子、或可經鹵素原子取代之碳數1～12之烷基， m表示1～3之整數，其中，於m為2或3之情形時所存在之複數個V可相互相同，亦可不同， ＊表示鍵結鍵] 所表示之結構單元(b3)、作為源自二胺化合物之結構單元之式(c)中之X係由式(5)所表示之結構單元(c2)、及作為源自四羧酸化合物之結構單元之式(a)中之Y係由式(6)： [化7]
Figure 02_image017
[式(6)中，Ar2 相互獨立地表示可具有取代基之三價芳香族基， s表示0～2之整數， Ar1 、V及＊如式(5)中之Ar1 、V及＊所定義，其中，於s為2之情形時所存在之複數個V及Ar1 可分別相互相同，亦可不同，其中式(6)中之V並非為單鍵] 所表示之結構單元(a2)。 [8]如上述[7]所記載之光學膜，其中式(5)及式(6)係由式(7)所表示： [化8]
Figure 02_image019
[式(7)中，R1 相互獨立地表示氫原子、碳數1～12之烷基、碳數1～12之烷氧基或碳數6～12之芳基，R1 中所包含之氫原子可相互獨立地被取代為鹵素原子， R＊ 表示R1 或鍵結鍵， ＊表示鍵結鍵， V表示單鍵、-O-、二苯基亞甲基、碳數1～12之直鏈狀、支鏈狀或脂環式之二價烴基、-SO2 -、-S-、-CO-或-N(R12 )-，此處，該烴基中所包含之氫原子可相互獨立地被取代為鹵素原子，R12 表示氫原子、或可經鹵素原子取代之碳數1～12之烷基，其中於式(6)係由式(7)所表示之情形時，V並非為單鍵]。 [9]如上述[8]所記載之光學膜，其中式(7)係由式(7')或式(7")所表示： [化9]
Figure 02_image021
[式(7')中，R＊ 表示氫原子或鍵結鍵，＊表示鍵結鍵] [化10]
Figure 02_image023
[式(7")中，＊表示鍵結鍵]。 [10]如上述[1]～[9]中任一項所記載之光學膜，其中式(1)係由式(1')所表示： [化11]
Figure 02_image025
[式(1')中，＊表示鍵結鍵，R＊ 於Y係由式(1)所表示之情形時，表示鍵結鍵，於Z係由式(1)所表示之情形時，表示氫原子]。 [11]如上述[1]～[10]中任一項所記載之光學膜，其係可撓性顯示裝置之前面板用之膜。 [12]一種可撓性顯示裝置，其具備如上述[1]～[11]中任一項所記載之光學膜。 [13]如上述[12]所記載之可撓性顯示裝置，其進而具備觸控感測器。 [14]如上述[12]或[13]所記載之可撓性顯示裝置，其進而具備偏光板。 [發明之效果]That is, the present invention includes the following preferable aspects. [1] An optical film comprising at least a structural unit represented by formula (a) derived from a tetracarboxylic acid compound, a structural unit represented by formula (b) derived from a dicarboxylic acid compound, and a structural unit derived from two The polyamide imine resin of the structural unit represented by the formula (c) of the amine compound: [化1]
Figure 02_image005
[In formula (a), Y represents a tetravalent organic group, in formula (b), Z represents a divalent organic group, in formula (c), X represents a divalent organic group, and R c independently represents a hydrogen atom or bond Bonding, * represents bonding bond]; The polyamide imine-based resin includes at least one structural unit selected from the group consisting of the following structural units: the formula as the structural unit derived from the tetracarboxylic acid compound (a) Y is a structural unit (a1) represented by formula (1) and Z in formula (b) as a structural unit derived from the dicarboxylic acid compound is a structure represented by formula (1) Unit (b1); [化2]
Figure 02_image007
[In the formula (1), R a each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, the alkoxy having 1 to 12 carbon atoms or the aryl group of 6 to 12, R a contained the Hydrogen atoms can be substituted with halogen atoms independently of each other, n represents an integer from 0 to 2, ＊ represents a bonding bond, and R ＊ when Y is represented by formula (1), represents a bonding bond, in Z system In the case represented by the formula (1), it is expressed as R a ] Based on L * a * b * brightness of the color system in the measurement of the reflected light of the optical film L 1 * and the surface color difference measurement is in contact with ethanol 40 The absolute value ΔL * of the difference between the brightness L 2 * of the optical film based on the L * a * b * color system after minutes is 0.5 or less. [2] The optical film as described in [1] above, wherein b 1 of the optical film based on the L * a * b * color system in the measurement of reflected light is the b 1 * of the optical film after being in contact with ethanol for 40 minutes The absolute value Δb * of the difference between b 2 * is 0.1 or less. [3] The optical film as described in [1] or [2] above, wherein the thickness of the optical film is 25 μm or more and 100 μm or less. [4] The optical film according to any one of [1] to [3] above, wherein the haze of the optical film is 5% or less. [5] The optical film as described in any one of [1] to [4] above, wherein the polyimide-imide-based resin includes the formula (2): [化3]
Figure 02_image009
[In formula (2), Z 1 represents a divalent aromatic group as a monocyclic aromatic ring or a condensed polycyclic aromatic ring which may have a substituent, * represents a bonding bond] The structural unit represented by (b2 ) Is a structural unit derived from a dicarboxylic acid compound and includes formula (3): [化4]
Figure 02_image011
[In formula (3), X 1 represents a divalent aromatic group that may have a substituent, R c independently represents a hydrogen atom or a bonding bond, and * represents a bonding bond] The structural unit (c1) represented as the source From the structural unit of the diamine compound. [6] The optical film described in the above [5], wherein X 1 in the formula (3) is represented by the formula (4): [化5]
Figure 02_image013
[In formula (4), R b independently represents an alkyl group having 1 to 6 carbons, an aryl group having 6 to 12 carbons, or an alkoxy group having 1 to 6 carbons, and the hydrogen atom contained in R b It can be substituted with a halogen atom independently of each other, and r independently represents an integer of 1 to 4, and * represents a bonding bond]. [7] The optical film as described in any one of [1] to [6] above, wherein the polyimide imine-based resin contains at least one structural unit selected from the group consisting of the following structural units: Z in the formula (b) derived from the structural unit of the dicarboxylic acid compound is derived from the formula (5): [化6]
Figure 02_image015
[In formula (5), Ar 1 independently represents a divalent aromatic group that may have a substituent, V represents a single bond, -O-, diphenylmethylene, a linear chain with 1 to 12 carbon atoms, A branched or alicyclic divalent hydrocarbon group, -SO 2 -, -S-, -CO- or -N(R 12 )-, where the hydrogen atoms contained in the hydrocarbon group can be substituted independently of each other It is a halogen atom, R 12 represents a hydrogen atom, or an alkyl group with 1 to 12 carbon atoms which can be substituted by a halogen atom, and m represents an integer of 1 to 3, where there are plural when m is 2 or 3 V may be the same or different from each other, * represents the structural unit (b3) represented by the bond], and X in the formula (c) as a structural unit derived from a diamine compound is represented by the formula (5) Structural unit (c2), and Y in formula (a) as a structural unit derived from tetracarboxylic acid compounds is derived from formula (6): [化7]
Figure 02_image017
[In formula (6), Ar 2 independently represents a trivalent aromatic group which may have a substituent, s represents an integer of 0-2, Ar 1 , V and * are as in the formula (5) Ar 1 , V and ＊Defined, where the plural V and Ar 1 existing when s is 2 may be the same or different from each other, and V in formula (6) is not a single bond] is the structural unit represented by ( a2). [8] The optical film as described in the above [7], wherein formula (5) and formula (6) are represented by formula (7): [化8]
Figure 02_image019
[In formula (7), R 1 independently represents a hydrogen atom, a C 1-12 alkyl group, a C 1-12 alkoxy group, or a C 6-12 aryl group, which is contained in R 1 Hydrogen atoms can be independently substituted with halogen atoms, R ＊ represents R 1 or a bonding bond, ＊represents a bonding bond, V represents a single bond, -O-, diphenylmethylene, carbon number 1-12 A linear, branched or alicyclic divalent hydrocarbon group, -SO 2 -, -S-, -CO-, or -N(R 12 )-, where the hydrogen atoms contained in the hydrocarbon group can interact with each other Is independently substituted with a halogen atom, R 12 represents a hydrogen atom, or an alkyl group with 1 to 12 carbons which can be substituted by a halogen atom, wherein when formula (6) is represented by formula (7), V is not Is a single key]. [9] The optical film as described in [8] above, wherein the formula (7) is represented by the formula (7') or the formula (7"): [化9]
Figure 02_image021
[In the formula (7'), R * represents a hydrogen atom or a bonding bond, and * represents a bonding bond] [化10]
Figure 02_image023
[In formula (7"), * represents a bonding bond]. [10] The optical film as described in any one of [1] to [9] above, wherein the formula (1) is represented by the formula (1') Means: [化11]
Figure 02_image025
When [In the formula (1 '), * represents a bonding bond, R * in the Y lines by the formula (1) when the case represented, the represented bond bond, the Z-line by the formula (1) When expressed, the expressed A hydrogen atom]. [11] The optical film described in any one of [1] to [10] above, which is a film for a front panel of a flexible display device. [12] A flexible display device comprising the optical film as described in any one of [1] to [11] above. [13] The flexible display device as described in [12] above, which further includes a touch sensor. [14] The flexible display device as described in [12] or [13] above, which further includes a polarizing plate. [Effects of Invention]

本發明之光學膜具有不會因與醇之接觸而受損之較高之外觀品質。The optical film of the present invention has high appearance quality that is not damaged by contact with alcohol.

以下，對本發明之實施形態詳細地進行說明。再者，本發明之範圍並不限定於此處說明之實施形態，可於不脫離本發明之主旨之範圍內進行各種變更。Hereinafter, embodiments of the present invention will be described in detail. Furthermore, the scope of the present invention is not limited to the embodiments described here, and various changes can be made without departing from the scope of the present invention.

[光學膜] 本發明之光學膜係包含至少具有源自四羧酸化合物之式(a)所表示之結構單元、源自二羧酸化合物之式(b)所表示之結構單元、及源自二胺化合物之式(c)所表示之結構單元之聚醯胺醯亞胺系樹脂者： [化12]

Figure 02_image027
[式(a)中，Y表示四價有機基，式(b)中，Z表示二價有機基，式(c)中，X表示二價有機基，Rc 相互獨立地表示氫原子或鍵結鍵，＊表示鍵結鍵] 該聚醯胺醯亞胺系樹脂包含選自由如下結構單元所組成之群中之至少1種結構單元：作為該源自四羧酸化合物之結構單元之式(a)中之Y係由式(1)： [化13]
Figure 02_image029
[式(1)中，Ra 相互獨立地表示氫原子、碳數1～12之烷基、碳數1～12之烷氧基或碳數6～12之芳基，Ra 中所包含之氫原子可相互獨立地被取代為鹵素原子， n表示0～2之整數， ＊表示鍵結鍵，R＊ 於Y係由式(1)所表示之情形時，表示鍵結鍵，於Z係由式(1)所表示之情形時，表示Ra ] 所表示之結構單元(a1)及作為該源自二羧酸化合物之結構單元之式(b)中之Z係由式(1)所表示之結構單元(b1)， 該光學膜之反射光測定中之基於L＊ a＊ b＊ 表色系統之亮度L1 ＊ 與於表面之色差測定中與乙醇接觸40分鐘後之該光學膜之基於L＊ a＊ b＊ 表色系統之亮度L2 ＊ 之差之絕對值ΔL＊ 為0.5以下。再者，於本說明書中，將式(a)中之Y係由式(1)所表示之結構單元亦稱為「結構單元(a1)」，將式(b)中之Z係由式(1)所表示之結構單元亦稱為「結構單元(b1)」。[Optical film] The optical film of the present invention includes at least a structural unit represented by formula (a) derived from a tetracarboxylic acid compound, a structural unit represented by formula (b) derived from a dicarboxylic acid compound, and The polyamide imine resin of the structural unit represented by the formula (c) of the diamine compound: [化12]
Figure 02_image027
[In formula (a), Y represents a tetravalent organic group, in formula (b), Z represents a divalent organic group, in formula (c), X represents a divalent organic group, and R c independently represents a hydrogen atom or bond Bonding, * represents bonding bond] The polyamidoimide-based resin contains at least one structural unit selected from the group consisting of the following structural units: formula (as the structural unit derived from the tetracarboxylic acid compound) a) Y in the formula (1): [化13]
Figure 02_image029
[In the formula (1), R a each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, the alkoxy having 1 to 12 carbon atoms or the aryl group of 6 to 12, R a contained the Hydrogen atoms can be substituted with halogen atoms independently of each other, n represents an integer from 0 to 2, ＊ represents a bonding bond, and R ＊ when Y is represented by formula (1), represents a bonding bond, in Z system In the case represented by the formula (1), the structural unit (a1) represented by R a ] and the Z in the formula (b) as the structural unit derived from the dicarboxylic acid compound are represented by the formula (1) The structural unit (b1) represented by the optical film based on L * a * b * the brightness of the color system L 1 * and the optical film after 40 minutes of contact with ethanol in the measurement of the color difference on the surface of the optical film The absolute value ΔL * of the difference between the brightness L 2 * based on the L * a * b * color system is 0.5 or less. Furthermore, in this specification, the structural unit represented by formula (1) where Y in formula (a) is also referred to as "structural unit (a1)", and Z in formula (b) is derived from formula ( 1) The structural unit shown is also called "structural unit (b1)".

關於本發明之光學膜，光學膜之反射光測定中之基於L＊ a＊ b＊ 表色系統之亮度L1 ＊ 與和乙醇接觸40分鐘後之該光學膜之基於L＊ a＊ b＊ 表色系統之亮度L2 ＊ 之差之絕對值ΔL＊ 為0.5以下。於ΔL＊ 超過0.5之情形時，因與乙醇接觸而導致光學膜之外觀品質受損。就進一步提高外觀品質之觀點而言，ΔL＊ 較佳為0.3以下，更佳為0.2以下，進而較佳為0.1以下，通常為0以上。再者，ΔL＊ 係本發明之光學膜之反射光測定中之亮度L1 ＊ 與使本發明之光學膜與乙醇接觸40分鐘後之光學膜之亮度L2 ＊ 之差之絕對值。作為使光學膜與乙醇接觸40分鐘之方法，使用對光學膜滴加乙醇，蓋上覆蓋玻璃，將光學膜與乙醇接觸之狀態維持40分鐘之方法。具體而言，可列舉實施例所記載之方法。又，反射光測定中之基於L＊ a＊ b＊ 表色系統之亮度L＊ 值可使用分光測色計於例如實施例所記載之條件下進行測定。作為將ΔL＊ 設為上述範圍內之方法，可列舉：使用下述聚醯胺醯亞胺系樹脂製造光學膜之方法，調整製膜溶劑、膜之乾燥條件、溫度來調整膜中之溶劑量之方法，設置保護層之方法等。再者，於藉由調整製膜溶劑、膜之乾燥條件、溫度來調整膜中之溶劑量而將ΔL＊ 調整為上述範圍內之情形時，雖亦視溶劑之種類而定，但例如可藉由將膜中之溶劑量調整為0.1%以上且1.0%以下而將ΔL＊ 調整為所需範圍。又，於藉由設置保護層之方法將ΔL＊ 調整為上述範圍內之情形時，可藉由於光學膜中設置賦予了耐化學品性之硬塗層等保護層而將ΔL＊ 調整為上述範圍內。Regarding the optical film of the present invention, the measurement of the reflected light of the optical film is based on L * a * b * The brightness of the color system is L 1 * The optical film is based on L * a * b * after being in contact with ethanol for 40 minutes The absolute value ΔL * of the difference between the luminance L 2 * of the color system is 0.5 or less. When ΔL * exceeds 0.5, the appearance quality of the optical film is impaired due to contact with ethanol. From the viewpoint of further improving the appearance quality, ΔL * is preferably 0.3 or less, more preferably 0.2 or less, still more preferably 0.1 or less, and usually 0 or more. Furthermore, ΔL * is the absolute value of the difference between the brightness L 1 * in the reflected light measurement of the optical film of the present invention and the brightness L 2 * of the optical film after contacting the optical film of the present invention with ethanol for 40 minutes. As a method of contacting the optical film with ethanol for 40 minutes, a method of adding ethanol to the optical film, covering with a cover glass, and maintaining the state of the optical film in contact with ethanol for 40 minutes is used. Specifically, the method described in the embodiment can be cited. In addition, the brightness L * value based on the L * a * b * color system in the reflected light measurement can be measured under the conditions described in the examples using a spectrophotometer. As a method of setting ΔL * within the above-mentioned range, there may be mentioned: a method of manufacturing an optical film using the following polyimide-based resin, adjusting the film-forming solvent, film drying conditions, and temperature to adjust the amount of solvent in the film The method of setting up the protective layer, etc. Furthermore, when adjusting the amount of solvent in the film by adjusting the film-forming solvent, the drying conditions of the film, and the temperature to adjust the ΔL * within the above range, although it depends on the type of solvent, for example, Adjust ΔL * to a desired range by adjusting the amount of solvent in the film to 0.1% or more and 1.0% or less. Further, when a protective layer by the method in the case where the ΔL * is adjusted within the above range, since the optical film is provided Keji impart hard coat protective layer of chemical resistance and the like to adjust the above range ΔL * Inside.

於本發明之光學膜中，聚醯胺醯亞胺系樹脂包含選自由如下結構單元所組成之群中之至少1種結構單元：式(a)中之Y係由式(1)所表示之結構單元(a1)及式(b)中之Z係由式(1)所表示之結構單元(b1)，藉此，式(1)所表示之結構包含於聚醯胺醯亞胺系樹脂中。式(1)所表示之結構係剛硬性較高之結構，聚醯胺醯亞胺系樹脂之骨架中包含具有剛硬性之部分。其結果令人驚訝，認為容易提高所獲得之光學膜之耐醇性，而容易防止光學膜之外觀品質因與醇之接觸而降低。並且，於含有上述聚醯胺醯亞胺系樹脂且ΔL＊ 為上述範圍內之情形時，可達成光學膜較高之外觀品質。此處，例如於將光學膜用作顯示裝置之前面板之情形時，周圍之背景映入光學膜。尤其是於在可撓性顯示裝置中使用光學膜之情形時，映入光學膜之背景可自各種角度被視認到。於所映入之背景例如局部未被清晰地視認到之情形時，認為使用者感到違和感而製品之高級感降低。再者，所謂此種外觀品質，例如係藉由實施例所記載之方法而評價之品質，具體而言，係所映入之背景不存在局部看起來模糊之情況而是被清晰地視認到之品質。該外觀品質尤其是於背景為黑色之情形時，容易明確地判斷。In the optical film of the present invention, the polyimide imine-based resin contains at least one structural unit selected from the group consisting of the following structural units: Y in formula (a) is represented by formula (1) Z in the structural unit (a1) and formula (b) is the structural unit (b1) represented by the formula (1), whereby the structure represented by the formula (1) is contained in the polyimide imine resin . The structure represented by the formula (1) is a relatively rigid structure, and the skeleton of the polyimide-based resin includes a rigid part. The result is surprising. It is believed that it is easy to improve the alcohol resistance of the obtained optical film, and it is easy to prevent the appearance quality of the optical film from being degraded due to contact with alcohol. In addition, when the above-mentioned polyamidoimide-based resin is contained and ΔL * is within the above-mentioned range, a higher appearance quality of the optical film can be achieved. Here, for example, when the optical film is used as the front panel of the display device, the surrounding background reflects the optical film. Especially when an optical film is used in a flexible display device, the background reflected in the optical film can be seen from various angles. When the reflected background, for example, a part of which is not clearly recognized, it is considered that the user feels a sense of inconsistency and the sense of quality of the product is reduced. Furthermore, the so-called appearance quality is, for example, the quality evaluated by the method described in the examples. Specifically, the reflected background does not appear to be blurred locally but is clearly recognized. quality. The appearance quality is easy to be clearly judged especially when the background is black.

於含有下述聚醯胺醯亞胺系樹脂且ΔL＊ 為0.5以下之本發明之光學膜中外觀品質得到提高之原因雖不明確，但於本發明中，ΔL＊ 表示光學膜表面之反射光因與乙醇接觸而發生何種程度之變化。因此，即便目視下因與乙醇接觸而產生之變化略小或幾乎視認不到，於ΔL＊ 超過0.5之情形時，因反射光略微變化，於將光學膜組入至尤其是可撓性顯示器等中時，亦會產生因角度而看起來呈白色之部分，從而認為存在光學膜之外觀品質受損之情形。Although the reason why the appearance quality is improved in the optical film of the present invention containing the following polyamide imine resin and having a ΔL * of 0.5 or less is not clear, in the present invention, ΔL * represents the reflected light on the surface of the optical film How much change occurs due to contact with ethanol. Therefore, even if the visual change caused by contact with ethanol is slightly small or almost unrecognizable, when ΔL * exceeds 0.5, the reflected light changes slightly, which is why the optical film is incorporated into particularly flexible displays. In the middle, there will also be parts that look white due to the angle, so that the appearance quality of the optical film may be impaired.

本發明之光學膜之反射光測定中之基於L＊ a＊ b＊ 表色系統之亮度L＊ 值較佳為5以下，更佳為3以下，進而較佳為2.5以下，較佳為0以上，更佳為0.1以上，進而較佳為0.2以上。若L＊ 值為上述範圍內，則於用作光學膜之情形時視認性變得良好。In the measurement of the reflected light of the optical film of the present invention, the value of the brightness L * based on the L * a * b * color system is preferably 5 or less, more preferably 3 or less, further preferably 2.5 or less, preferably 0 or more , More preferably 0.1 or more, and still more preferably 0.2 or more. If the L * value is in the above range, the visibility becomes good when used as an optical film.

本發明之光學膜之反射光測定中之基於L＊ a＊ b＊ 表色系統之該光學膜之b1 ＊ 與和乙醇接觸40分鐘後之該光學膜之b2 ＊ 之差之絕對值Δb＊ 較佳為0.1以下，更佳為0.08以下，進而較佳為0.05以下，通常為0以上。再者，Δb＊ 係b1 ＊ 與b2 ＊ 之差之絕對值。使光學膜與乙醇接觸40分鐘之方法並無特別限定，例如可列舉實施例所記載之方法。又，反射光測定中之基於L＊ a＊ b＊ 表色系統之b＊ 值可使用分光測色性並於例如實施例所記載之條件下進行測定。作為將Δb＊ 設為上述範圍內之方法，可列舉：使用下述聚醯胺醯亞胺系樹脂製造光學膜之方法、調整製膜溶劑、膜之乾燥條件、溫度來調整膜中之溶劑量之方法、設置保護層之方法等。於Δb＊ 為上述範圍內之情形時，認為反射光之色調容易變得均勻，故而更容易提高外觀品質。Absolute value Δb of the difference between b 1 * of the optical film based on L * a * b * and b 2 * of the optical film after contact with ethanol for 40 minutes in the measurement of reflected light of the optical film of the present invention * Preferably it is 0.1 or less, more preferably 0.08 or less, still more preferably 0.05 or less, and usually 0 or more. Furthermore, Δb * is the absolute value of the difference between b 1 * and b 2 * . The method of bringing the optical film into contact with ethanol for 40 minutes is not particularly limited, and for example, the method described in the examples can be cited. In addition, the b * value based on the L * a * b * colorimetric system in the reflected light measurement can be measured under the conditions described in the Examples using spectrophotometric properties. As a method of setting Δb * within the above-mentioned range, examples include: a method of manufacturing an optical film using the following polyimide-based resin, adjustment of the film-forming solvent, film drying conditions, and temperature to adjust the amount of solvent in the film The method of setting up the protective layer, etc. When Δb * is within the above range, it is considered that the color tone of the reflected light is likely to become uniform, and therefore it is easier to improve the appearance quality.

本發明之光學膜之反射光測定中之基於L＊ a＊ b＊ 表色系統之b＊ 值較佳為2以下，更佳為1以下，進而較佳為0.5以下，較佳為-2以上，更佳為-1以上，進而較佳為-0.5以上。若b＊ 值為上述範圍內，則反射光不存在黃色調、藍色調，於用作光學膜時有外觀變得良好之傾向。The b * value based on the L * a * b * color system in the reflected light measurement of the optical film of the present invention is preferably 2 or less, more preferably 1 or less, further preferably 0.5 or less, and preferably -2 or more , More preferably -1 or more, still more preferably -0.5 or more. If the b * value is in the above range, the reflected light does not have a yellow or blue hue, and the appearance tends to become good when used as an optical film.

本發明之光學膜之反射光測定中之基於L＊ a＊ b＊ 表色系統之a＊ 值較佳為2以下，更佳為1以下，進而較佳為0.5以下，較佳為-2以上，更佳為-1以上，進而較佳為-0.5以上。若a＊ 值為上述範圍內，則反射光不存在紅色調、綠色調，於用作光學膜時有外觀變得良好之傾向The a * value based on the L * a * b * color system in the reflected light measurement of the optical film of the present invention is preferably 2 or less, more preferably 1 or less, further preferably 0.5 or less, preferably -2 or more , More preferably -1 or more, still more preferably -0.5 or more. If the value of a * is in the above range, the reflected light does not have red or green hue, and the appearance tends to become better when used as an optical film

於本發明之一實施形態中，光學膜中之聚醯胺醯亞胺系樹脂之含量相對於光學膜100質量份，較佳為10質量份以上，更佳為30質量份以上，進而較佳為50質量份以上，較佳為99.5質量份以下，更佳為95質量份以下。若聚醯胺醯亞胺系樹脂之含量為上述範圍內，則容易提高光學膜之外觀品質、光學特性、彈性模數及全光線透過率。In one embodiment of the present invention, the content of the polyamidoimide resin in the optical film relative to 100 parts by mass of the optical film is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, and more preferably It is 50 parts by mass or more, preferably 99.5 parts by mass or less, and more preferably 95 parts by mass or less. If the content of the polyimide-based resin is within the above range, it is easy to improve the appearance quality, optical properties, elastic modulus, and total light transmittance of the optical film.

本發明之光學膜之厚度較佳為25 μm以上，更佳為30 μm以上，進而較佳為35 μm以上，較佳為100 μm以下，更佳為80 μm以下，進而較佳為60 μm以下，亦可為該等上限與下限之組合。若光學膜之厚度為上述範圍內，則更容易提高光學膜之外觀品質及光學特性。再者，光學膜之厚度可使用測微計進行測定，例如可藉由實施例所記載之方法進行測定。The thickness of the optical film of the present invention is preferably 25 μm or more, more preferably 30 μm or more, still more preferably 35 μm or more, preferably 100 μm or less, more preferably 80 μm or less, and still more preferably 60 μm or less , Can also be a combination of these upper and lower limits. If the thickness of the optical film is within the above range, it is easier to improve the appearance quality and optical properties of the optical film. Furthermore, the thickness of the optical film can be measured using a micrometer, for example, it can be measured by the method described in an Example.

本發明之光學膜之黃度(以下，有時稱為YI值)較佳為7以下，更佳為4以下，通常-5以上，較佳為-2以上。若光學膜之YI值為上述上限以下，則透明性變得良好，於用於顯示裝置之前面板之情形時，可有助於較高之視認性。再者，YI值可使用紫外可見近紅外分光光度計對300～800 nm之光進行透過率測定，求出3刺激值(X、Y、Z)，並基於YI＝100×(1.2769X－1.0592Z)/Y之式而算出。The yellowness (hereinafter, sometimes referred to as YI value) of the optical film of the present invention is preferably 7 or less, more preferably 4 or less, usually -5 or more, preferably -2 or more. If the YI value of the optical film is less than the above upper limit, the transparency becomes good, and when used in the front panel of a display device, it can contribute to higher visibility. Furthermore, the YI value can be measured by the ultraviolet-visible-near-infrared spectrophotometer for the transmittance of light from 300 to 800 nm to obtain 3 stimulus values (X, Y, Z), and based on YI=100×(1.2769X-1.0592 Z)/Y is calculated.

就容易防止光學膜之皺褶或損傷等之觀點而言，本發明之光學膜之彈性模數較佳為5.2 GPa以上，更佳為5.5 GPa以上，進而較佳為5.8 GPa以上，進而更佳為6.0 GPa以上，尤佳為6.2 GPa以上，更尤佳為6.4 GPa以上，通常為100 GPa以下。再者，彈性模數可使用拉伸試驗機(夾頭間距離50 mm、拉伸速度10 mm/min)進行測定，例如可藉由實施例所記載之方法進行測定。From the viewpoint of easy prevention of wrinkles or damage of the optical film, the elastic modulus of the optical film of the present invention is preferably 5.2 GPa or more, more preferably 5.5 GPa or more, further preferably 5.8 GPa or more, and even more preferably It is 6.0 GPa or more, more preferably 6.2 GPa or more, more preferably 6.4 GPa or more, and usually 100 GPa or less. In addition, the elastic modulus can be measured using a tensile testing machine (the distance between the chucks is 50 mm, the tensile speed is 10 mm/min), for example, it can be measured by the method described in the examples.

本發明之光學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，進而更佳為89%以上，尤佳為90%以上，通常為100%以下。若全光線透過率為上述下限以上，則於將光學膜用作尤其是前面板並組入至顯示裝置中時容易提高視認性。本發明之光學膜通常顯示出較高之全光線透過率，因此例如與使用透過率較低之膜之情形時相比，可抑制用以獲得一定亮度所需之顯示元件等之發光強度。因此，可削減耗電。例如，於將本發明之光學膜組入至顯示裝置之情形時，有即便減少背光裝置之光量亦可獲得明亮之顯示之傾向，可有助於節約能源。再者，全光線透過率例如可依據JIS K 7361-1：1997並使用霧度計進行測定。全光線透過率可為下述光學膜之厚度範圍內之全光線透過率。再者，於本說明書中，所謂光學膜之光學特性優異，意指全光線透過率較高及/或霧度較低。The total light transmittance of the optical film of the present invention is preferably 80% or more, more preferably 85% or more, still more preferably 88% or more, still more preferably 89% or more, particularly preferably 90% or more, usually 100 %the following. If the total light transmittance is more than the above lower limit, it is easy to improve the visibility when the optical film is used as a front panel in particular and incorporated in a display device. The optical film of the present invention generally exhibits a higher total light transmittance, and therefore, compared with the case of using a film with a lower transmittance, for example, the luminous intensity of display elements required to obtain a certain brightness can be suppressed. Therefore, power consumption can be reduced. For example, when the optical film of the present invention is incorporated into a display device, there is a tendency to obtain a bright display even if the amount of light of the backlight device is reduced, which can help to save energy. In addition, the total light transmittance can be measured using a haze meter in accordance with JIS K 7361-1:1997, for example. The total light transmittance can be the total light transmittance within the thickness range of the following optical film. Furthermore, in this specification, the so-called excellent optical properties of the optical film means high total light transmittance and/or low haze.

本發明之光學膜之霧度較佳為5%以下，更佳為4%以下，進而較佳為3%以下，進而更佳為2.5%以下，尤佳為2%以下，更尤佳為1%以下，進而尤佳為0.8%以下，特別較佳為0.5%以下，通常為0.01%以上。若光學膜之霧度為上述上限以下，則於將光學膜用作尤其是前面板並組入至顯示裝置時，容易提高視認性。再者，霧度可依據JIS K 7136：2000並使用霧度計進行測定。The haze of the optical film of the present invention is preferably 5% or less, more preferably 4% or less, still more preferably 3% or less, still more preferably 2.5% or less, particularly preferably 2% or less, even more preferably 1 % Or less, more preferably 0.8% or less, particularly preferably 0.5% or less, and usually 0.01% or more. If the haze of the optical film is below the above upper limit, when the optical film is used as a front panel in particular and incorporated into a display device, it is easy to improve visibility. In addition, the haze can be measured using a haze meter in accordance with JIS K 7136:2000.

本發明之光學膜之至少一面之鉛筆硬度較佳為HB以上，更佳為F以上。於光學膜之至少一面之鉛筆硬度為上述硬度以上之情形時，容易防止光學膜之該表面之損傷等。再者，鉛筆硬度可依據JIS K 5600-5-4：1999進行測定。The pencil hardness of at least one side of the optical film of the present invention is preferably HB or higher, more preferably F or higher. When the pencil hardness of at least one surface of the optical film is higher than the above-mentioned hardness, it is easy to prevent damage to the surface of the optical film. Furthermore, the pencil hardness can be measured in accordance with JIS K 5600-5-4:1999.

[聚醯胺醯亞胺系樹脂] 本發明之光學膜包含至少具有源自四羧酸化合物之式(a)所表示之結構單元、源自二羧酸化合物之式(b)所表示之結構單元、及源自二胺化合物之式(c)所表示之結構單元之聚醯胺醯亞胺系樹脂： [化14]

Figure 02_image031
[式(a)中，Y表示四價有機基，式(b)中，Z表示二價有機基，式(c)中，X表示二價有機基，Rc 相互獨立地表示氫原子或鍵結鍵，＊表示鍵結鍵] 該聚醯胺醯亞胺系樹脂包含選自由如下結構單元所組成之群中之至少1種結構單元：作為該源自四羧酸化合物之結構單元之式(a)中之Y係由式(1)： [化15]
Figure 02_image033
[式(1)中，Ra 相互獨立地表示氫原子、碳數1～12之烷基、碳數1～12之烷氧基或碳數6～12之芳基，Ra 中所包含之氫原子可相互獨立地被取代為鹵素原子， n表示0～2之整數， ＊表示鍵結鍵，R＊ 於Y係由式(1)所表示之情形時，表示鍵結鍵，於Z係由式(1)所表示之情形時，表示Ra ] 所表示之結構單元(a1)及作為該源自二羧酸化合物之結構單元之式(b)中之Z係由式(1)所表示之結構單元(b1)。於本說明書中，將源自四羧酸化合物之式(a)所表示之結構單元亦稱為「結構單元(a)」，將源自二羧酸化合物之式(b)所表示之結構單元亦稱為「結構單元(b)」，將源自二胺化合物之式(c)所表示之結構單元亦稱為「結構單元(c)」。[Polyamide imine resin] The optical film of the present invention contains at least a structural unit represented by formula (a) derived from a tetracarboxylic acid compound and a structure represented by formula (b) derived from a dicarboxylic acid compound The unit and the polyamide imine resin derived from the structural unit represented by the formula (c) of the diamine compound: [formation 14]
Figure 02_image031
[In formula (a), Y represents a tetravalent organic group, in formula (b), Z represents a divalent organic group, in formula (c), X represents a divalent organic group, and R c independently represents a hydrogen atom or bond Bonding, * represents bonding bond] The polyamidoimide-based resin contains at least one structural unit selected from the group consisting of the following structural units: formula (as the structural unit derived from the tetracarboxylic acid compound) a) where Y is derived from formula (1): [化15]
Figure 02_image033
[In the formula (1), R a each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, the alkoxy having 1 to 12 carbon atoms or the aryl group of 6 to 12, R a contained the Hydrogen atoms can be substituted with halogen atoms independently of each other, n represents an integer from 0 to 2, ＊ represents a bonding bond, and R ＊ when Y is represented by formula (1), represents a bonding bond, in Z system In the case represented by the formula (1), the structural unit (a1) represented by R a ] and the Z in the formula (b) as the structural unit derived from the dicarboxylic acid compound are represented by the formula (1) Indicates the structural unit (b1). In this specification, the structural unit represented by formula (a) derived from a tetracarboxylic acid compound is also referred to as "structural unit (a)", and the structural unit represented by formula (b) derived from a dicarboxylic acid compound Also called "structural unit (b)", the structural unit represented by formula (c) derived from a diamine compound is also called "structural unit (c)".

聚醯胺醯亞胺系樹脂通常具有複數個結構單元(a)、複數個結構單元(b)及複數個結構單元(c)、以及任意之複數個其他結構單元。於本說明書中，所謂本發明之光學膜中所包含之聚醯胺醯亞胺系樹脂包含作為源自四羧酸化合物之結構單元(a)之式(a)中之Y係由式(1)所表示之結構單元(a1)，係指於聚醯胺醯亞胺系樹脂所具有之複數個結構單元(a)中，至少一部分結構單元(a)為式(a)中之Y係由式(1)所表示之結構單元(a1)。又，所謂本發明之光學膜中所包含之聚醯胺醯亞胺系樹脂包含作為源自二羧酸化合物之結構單元(b)之式(b)中之Z係由式(1)所表示之結構單元(b1)，係指於聚醯胺醯亞胺系樹脂所具有之複數個結構單元(b)中，至少一部分結構單元(b)為式(b)中之Z係由式(1)所表示之結構單元(b1)。上述記載亦符合本說明書中之相同之其他記載。再者，式(a)～式(c)中之鍵結鍵係與相鄰之結構單元鍵結之鍵結鍵。The polyimide imine-based resin usually has a plurality of structural units (a), a plurality of structural units (b), and a plurality of structural units (c), and an arbitrary plurality of other structural units. In this specification, the so-called polyamide imide resin contained in the optical film of the present invention includes the Y in the formula (a) as the structural unit (a) derived from the tetracarboxylic acid compound is derived from the formula (1) The structural unit (a1) represented by) means that among the plural structural units (a) of the polyamide imide resin, at least a part of the structural unit (a) is the Y in the formula (a) Structural unit (a1) represented by formula (1). In addition, the so-called polyamide imine resin contained in the optical film of the present invention includes Z in the formula (b) as a structural unit (b) derived from a dicarboxylic acid compound is represented by the formula (1) The structural unit (b1) refers to the plurality of structural units (b) possessed by the polyamide imine resin, at least a part of the structural units (b) are in the formula (b) and the Z is derived from the formula (1) ) Represents the structural unit (b1). The above description also complies with the same other descriptions in this manual. Furthermore, the bonding bonds in formulas (a) to (c) are bonding bonds to adjacent structural units.

於本發明中，聚醯胺醯亞胺系樹脂至少具有結構單元(a)、結構單元(b)及結構單元(c)，此處，源自四羧酸化合物之結構單元(a)及源自二胺化合物之結構單元(c)通常形成式(D)： [化16]

Figure 02_image035
[式(D)中，Y表示四價有機基，X表示二價有機基，＊表示鍵結鍵] 所表示之醯亞胺鍵，且包含於聚醯胺醯亞胺系樹脂中，源自二羧酸化合物之結構單元(b)及源自二胺化合物之結構單元(c)形成式(E)： [化17]
Figure 02_image037
[式(E)中，Z及X相互獨立地表示二價有機基，＊表示鍵結鍵] 所表示之醯胺鍵，且包含於聚醯胺醯亞胺系樹脂中。再者，式(D)中之具有Y及4個羰基之部分相當於源自四羧酸化合物之結構單元(a)，式(E)中之具有Z及2個羰基之部分相當於源自二羧酸化合物之結構單元(b)，式(D)及式(E)中之具有X及胺基之部分相當於源自二胺化合物之結構單元(c)。再者，於式(D)及式(E)中之相當於源自二胺化合物之結構單元(c)之部分，表示二價有機基之X係一個鍵結鍵鍵結於胺基，另一個＊所表示之鍵結鍵鍵結於相鄰之結構單元。於式(D)及式(E)所表示之結構單元重複之情形時，鍵結於相鄰之結構單元之＊所表示之鍵結鍵鍵結於式(D)或式(E)中之胺基部分。因此，亦可謂式(D)及式(E)中之具有X及胺基之部分係相當於源自二胺化合物之結構單元(c)之部分。In the present invention, the polyimide-based resin has at least a structural unit (a), a structural unit (b), and a structural unit (c). Here, the structural unit (a) and the source derived from the tetracarboxylic acid compound The structural unit (c) from the diamine compound usually forms the formula (D): [化16]
Figure 02_image035
[In formula (D), Y represents a tetravalent organic group, X represents a divalent organic group, and * represents a bonding bond] The amide bond represented by it is contained in the polyamide-imide-based resin, derived from The structural unit (b) of the dicarboxylic acid compound and the structural unit (c) derived from the diamine compound form the formula (E): [化17]
Figure 02_image037
[In the formula (E), Z and X independently represent a divalent organic group, and * represents a bonding bond] The amide bond represented by it is contained in the polyimide-based resin. Furthermore, the part having Y and 4 carbonyl groups in formula (D) corresponds to the structural unit (a) derived from the tetracarboxylic acid compound, and the part having Z and 2 carbonyl groups in formula (E) corresponds to the part derived from The structural unit (b) of the dicarboxylic acid compound, the part having X and the amino group in the formula (D) and the formula (E) corresponds to the structural unit (c) derived from the diamine compound. Furthermore, in formula (D) and formula (E), the part corresponding to the structural unit (c) derived from the diamine compound indicates that X of the divalent organic group is bonded to the amine group by a bonding bond, and A bond represented by * is bonded to adjacent structural units. When the structural units represented by formula (D) and formula (E) are repeated, the bonding bond represented by * of the adjacent structural unit is bonded in formula (D) or formula (E) Amino moiety. Therefore, it can be said that the part having X and the amino group in the formula (D) and the formula (E) corresponds to the part derived from the structural unit (c) of the diamine compound.

於本發明中，聚醯胺醯亞胺系樹脂包含選自由如下結構單元所組成之群中之至少1種結構單元：作為源自四羧酸化合物之結構單元(a)之式(a)中之Y係由式(1)所表示之結構單元(a1)、及作為源自二羧酸化合物之結構單元(b)之式(b)中之Z係由式(1)所表示之結構單元(b1)。於該情形時，本發明之光學膜中所包含之聚醯胺醯亞胺系樹脂具有選自由Y係由式(1)所表示之結構單元(D)及Z係由式(1)所表示之結構單元(E)所組成之群中之至少1種結構單元。再者，式(D)及式(E)中之＊表示與相鄰之結構單元鍵結之鍵結鍵。In the present invention, the polyimide-based resin contains at least one structural unit selected from the group consisting of the following structural units: in formula (a) as the structural unit (a) derived from a tetracarboxylic acid compound Y is a structural unit (a1) represented by formula (1), and Z in formula (b) as a structural unit (b) derived from a dicarboxylic acid compound is a structural unit represented by formula (1) (b1). In this case, the polyamidoimide resin contained in the optical film of the present invention has a structural unit (D) selected from the group consisting of Y represented by formula (1) and Z is represented by formula (1) At least one structural unit in the group consisting of structural unit (E). Furthermore, * in formula (D) and formula (E) represents a bonding bond to an adjacent structural unit.

於本發明中，聚醯胺醯亞胺系樹脂只要具有源自四羧酸化合物之結構單元(a)、源自二羧酸化合物之結構單元(b)、及源自二胺化合物之結構單元(c)，且包含選自由作為結構單元(a)之至少一部分之結構單元(a1)及作為結構單元(b)之至少一部分之結構單元(b1)所組成之群中之至少1種結構單元，則該聚醯胺醯亞胺系樹脂亦可進而具有上述以外之源自其他單體之結構單元。具體而言，於本發明中，聚醯胺醯亞胺系樹脂至少具有1種或2種以上之源自四羧酸化合物之結構單元(a)、1種或2種以上之源自二羧酸化合物之結構單元(b)、及1種或2種以上之源自二胺化合物之結構單元(c)，其中，結構單元(a)之至少一部分包含結構單元(a1)或結構單元(b)之至少一部分包含結構單元(b1)或者結構單元(a)之至少一部分包含結構單元(a1)，且結構單元(b)之至少一部分包含結構單元(b1)。In the present invention, the polyimide-based resin only needs to have a structural unit (a) derived from a tetracarboxylic acid compound, a structural unit (b) derived from a dicarboxylic acid compound, and a structural unit derived from a diamine compound (c), and includes at least one structural unit selected from the group consisting of structural unit (a1) as at least a part of structural unit (a) and structural unit (b1) as at least a part of structural unit (b) , Then the polyimide imine resin may further have structural units derived from other monomers other than the above. Specifically, in the present invention, the polyimide resin has at least one or more structural units (a) derived from a tetracarboxylic acid compound, and one or two or more structural units derived from a dicarboxylic acid compound. The structural unit (b) of an acid compound, and one or more structural units (c) derived from diamine compounds, wherein at least a part of the structural unit (a) includes the structural unit (a1) or the structural unit (b) At least a part of) includes structural unit (b1) or at least a part of structural unit (a) includes structural unit (a1), and at least a part of structural unit (b) includes structural unit (b1).

聚醯胺醯亞胺系樹脂包含選自由如下結構單元所組成之群中之至少1種結構單元：作為源自四羧酸化合物之結構單元之式(a)中之Y係由式(1)： [化18]

Figure 02_image039
[式(1)中，Ra 相互獨立地表示氫原子、碳數1～12之烷基、碳數1～12之烷氧基或碳數6～12之芳基，Ra 中所包含之氫原子可相互獨立地被取代為鹵素原子， n表示0～2之整數， ＊表示鍵結鍵，R＊ 於Y係由式(1)所表示之情形時，表示鍵結鍵，於Z係由式(1)所表示之情形時，表示Ra ] 所表示之結構單元(a1)及作為該源自二羧酸化合物之結構單元之式(b)中之Z係由式(1)所表示之結構單元(b1)。本發明之光學膜中所包含之聚醯胺醯亞胺系樹脂可具有式(a)中之Y係由式(1)所表示之1種結構單元(a1)，亦可具有式(a)中之Y係由式(1)所表示之2種以上之結構單元(a1)，可具有式(b)中之Z係由式(1)所表示之1種結構單元(b1)，亦可具有式(b)中之Y係由式(1)所表示之2種以上之結構單元(b1)，亦可具有該等兩者。就更容易提高光學膜之外觀品質之觀點而言，本發明中之聚醯胺醯亞胺系樹脂較佳為至少包含式(a)中之Y係由式(1)所表示之至少1種結構單元(a1)作為源自四羧酸化合物之結構單元。The polyimide imine-based resin contains at least one structural unit selected from the group consisting of the following structural units: Y in formula (a) as a structural unit derived from a tetracarboxylic acid compound is derived from formula (1) : [化18]
Figure 02_image039
[In the formula (1), R a each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, the alkoxy having 1 to 12 carbon atoms or the aryl group of 6 to 12, R a contained the Hydrogen atoms can be substituted with halogen atoms independently of each other, n represents an integer from 0 to 2, ＊ represents a bonding bond, and R ＊ when Y is represented by formula (1), represents a bonding bond, in Z system In the case represented by the formula (1), the structural unit (a1) represented by R a ] and the Z in the formula (b) as the structural unit derived from the dicarboxylic acid compound are represented by the formula (1) Indicates the structural unit (b1). The polyimide-based resin contained in the optical film of the present invention may have one type of structural unit (a1) represented by formula (1) where Y in formula (a), or formula (a) Y in the formula (1) represents two or more structural units (a1), and Z in the formula (b) may have one structural unit (b1) represented by the formula (1), or There are two or more structural units (b1) in which Y in the formula (b) is represented by the formula (1), and may have both of them. From the viewpoint of making it easier to improve the appearance quality of the optical film, the polyimide-imide resin in the present invention preferably contains at least one of the Y in the formula (a) is represented by the formula (1) The structural unit (a1) is a structural unit derived from a tetracarboxylic acid compound.

式(1)中之Ra 相互獨立地表示氫原子、碳數1～12之烷基、碳數1～12之烷氧基或碳數6～12之芳基，Ra 中所包含之氫原子可相互獨立地被取代為鹵素原子。於本發明之較佳之一態樣中，就容易提高式(1)所表示之結構之剛硬性、容易對聚醯胺醯亞胺系樹脂之骨架賦予剛硬性、容易提高本發明之光學膜之外觀品質、全光線透過率及彈性模數之觀點而言，Ra 相互獨立較佳為表示氫原子、不包含鹵素原子之碳數1～12之烷基、碳數1～12之烷氧基或碳數6～12之芳基，更佳為表示氫原子或不包含鹵素原子之碳數1～12之烷基，進而較佳為表示氫原子或不包含鹵素原子之碳數1～6之烷基，進而更佳為表示氫原子或不包含鹵素原子之碳數1～3之烷基，尤佳為表示氫原子。R a in the formula (1) independently represents a hydrogen atom, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an aryl group having 6 to 12 carbons, and the hydrogen contained in R a Atoms can be substituted with halogen atoms independently of each other. In a preferred aspect of the present invention, it is easy to increase the rigidity of the structure represented by formula (1), it is easy to impart rigidity to the skeleton of the polyimide-imide resin, and it is easy to increase the rigidity of the optical film of the present invention. From the viewpoints of appearance quality, total light transmittance and elastic modulus, R a is independent of each other and preferably represents a hydrogen atom, an alkyl group with 1 to 12 carbons that does not contain a halogen atom, and an alkoxy group with 1 to 12 carbons. Or an aryl group having 6 to 12 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms that does not contain a halogen atom, and more preferably a hydrogen atom or an alkyl group containing 1 to 6 carbon atoms that does not contain a halogen atom The alkyl group more preferably represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which does not contain a halogen atom, and particularly preferably represents a hydrogen atom.

作為碳數1～12之烷基，可列舉碳數1～12之直鏈狀、支鏈狀或脂環式之烷基。作為碳數1～12之直鏈狀、支鏈狀或脂環式之烷基，例如可列舉：甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、2-甲基丁基、3-甲基丁基、2-乙基丙基、正己基、正庚基、正辛基、第三辛基、正壬基、正癸基、環戊基、環己基等。碳數1～12之烷基亦可為直鏈狀之烷基、支鏈狀之烷基、或包含脂環式烴結構之脂環式烷基。碳數1～12之烷基之碳數較佳為1～6，更佳為1～4，進而較佳為1～3。上述碳數1～12之烷基亦可為至少1個氫原子相互獨立地被取代為鹵素原子、碳數1～4之烷基、碳數1～4之烷氧基、羥基、或羧基之基。作為鹵素原子，可列舉：氟原子、氯原子、溴原子、碘原子。此處，於碳數1～12之烷基經包含碳原子之取代基(例如碳數1～4之烷基)取代之情形時，該取代基中所包含之碳原子數不包含於碳數1～12之烷基之碳數中。例如上述碳數1～12之烷基經碳數1～4之烷基取代之基係將碳數1～12之烷基作為主鏈且該烷基之至少1個氫原子被取代為碳數1～4之烷基之基。若成為主鏈之烷基部分之碳數為1～12，則作為烷基整體之碳數亦可超過12。再者，於作為烷基整體之碳原子數不超過12之基之情形時，碳數1～12之烷基經碳數1～4之烷基取代之基係亦包含於碳數1～12之支鏈狀之烷基之定義中之基。Examples of the alkyl group having 1 to 12 carbons include linear, branched, or alicyclic alkyl groups having 1 to 12 carbons. Examples of linear, branched or alicyclic alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and Tributyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 2-ethylpropyl, n-hexyl, n-heptyl, n-octyl, tertiary octyl, n-nonyl, n- Decyl, cyclopentyl, cyclohexyl, etc. The alkyl group having 1 to 12 carbon atoms may be a linear alkyl group, a branched chain alkyl group, or an alicyclic alkyl group containing an alicyclic hydrocarbon structure. The carbon number of the alkyl group having 1 to 12 carbons is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 3. The above-mentioned C1-C12 alkyl group may be one of at least one hydrogen atom independently substituted with a halogen atom, C1-C4 alkyl group, C1-C4 alkoxy group, hydroxyl group, or carboxyl group base. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Here, when an alkyl group having 1 to 12 carbon atoms is substituted with a substituent containing carbon atoms (for example, an alkyl group having 1 to 4 carbon atoms), the number of carbon atoms contained in the substituent is not included in the number of carbon atoms Among the carbon numbers of the alkyl group of 1-12. For example, the above-mentioned alkyl group having 1 to 12 carbon atoms is substituted with an alkyl group having 1 to 4 carbon atoms. The main chain is an alkyl group having 1 to 12 carbon atoms, and at least one hydrogen atom of the alkyl group is substituted with a carbon number. 1 to 4 alkyl groups. If the carbon number of the alkyl part of the main chain is 1-12, the carbon number of the entire alkyl group may exceed 12. Furthermore, in the case of a group with no more than 12 carbon atoms as the entire alkyl group, a group in which an alkyl group having 1 to 12 carbon atoms is substituted with an alkyl group having 1 to 4 carbon atoms is also included in the group having 1 to 12 carbon atoms. The group in the definition of branched alkyl.

作為碳數1～12之烷氧基，例如可列舉：甲氧基、乙氧基、丙氧基、異丙氧基、正丁氧基、異丁氧基、第三丁氧基、戊氧基、己氧基、環己氧基、庚氧基、辛氧基、壬氧基及癸氧基等。碳數1～12之烷氧基中之烷基部分及/或伸烷基部分可為直鏈狀、支鏈狀、或脂環式之任一者。碳數1～12之烷氧基之碳數較佳為1～6，更佳為1～4，進而較佳為1～3。上述碳數1～12之烷氧基亦可為至少1個氫原子相互獨立地被取代為鹵素原子、碳數1～4之烷基、碳數1～4之烷氧基、羥基、或羧基之基。作為鹵素原子，可列舉上述所記載之原子。此處，於碳數1～12之烷氧基經包含碳原子之取代基取代之情形時，該取代基中所包含之碳原子數不包含於碳數1～12之烷氧基之碳數中。Examples of alkoxy groups having 1 to 12 carbon atoms include: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, and pentoxy Group, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, nonyloxy and decyloxy, etc. The alkyl moiety and/or the alkylene moiety in the alkoxy group having 1 to 12 carbon atoms may be linear, branched, or alicyclic. The carbon number of the alkoxy group having 1 to 12 carbons is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 3. The above-mentioned alkoxy group having 1 to 12 carbon atoms may be at least one hydrogen atom independently substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a carboxyl group. The base. Examples of the halogen atom include the atoms described above. Here, when the alkoxy group having 1 to 12 carbon atoms is substituted with a substituent containing carbon atoms, the number of carbon atoms contained in the substituent is not included in the number of carbon atoms of the alkoxy group having 1 to 12 carbon atoms in.

作為碳數6～12之芳基，例如可列舉：苯基、甲苯基、二甲苯基、萘基、聯苯基等。碳數6～12之芳基之碳數較佳為6或10或12。上述碳數6～12之芳基亦可為至少1個氫原子相互獨立地被取代為鹵素原子、碳數1～4之烷基、碳數1～4之烷氧基、羥基、或羧基之基。作為鹵素原子，可列舉上述所記載之原子。此處，於碳數6～12之芳基經包含碳原子之取代基取代之情形時，該取代基中所包含之碳原子數不包含於碳數6～12之芳基之碳數中。Examples of aryl groups having 6 to 12 carbon atoms include phenyl, tolyl, xylyl, naphthyl, biphenyl and the like. The carbon number of the aryl group having 6 to 12 carbons is preferably 6 or 10 or 12. The above-mentioned aryl group having 6 to 12 carbons may be one of at least one hydrogen atom independently substituted with a halogen atom, an alkyl group having 1 to 4 carbons, an alkoxy group having 1 to 4 carbons, a hydroxyl group, or a carboxyl group. base. Examples of the halogen atom include the atoms described above. Here, when the aryl group having 6 to 12 carbon atoms is substituted with a substituent containing carbon atoms, the number of carbon atoms contained in the substituent is not included in the carbon number of the aryl group having 6 to 12 carbon atoms.

Ra 中所包含之氫原子可相互獨立地被取代為鹵素原子。作為鹵素原子，可列舉上述所記載之原子。Hydrogen atoms contained in the R a independently of each other be substituted with a halogen atom. Examples of the halogen atom include the atoms described above.

式(1)中之n表示0～2之整數，就容易提高使用聚醯胺醯亞胺系樹脂而獲得之光學膜之全光線透過率及彈性模數之觀點而言，n較佳為0或1，更佳為0。In formula (1), n represents an integer from 0 to 2. From the viewpoint of easily improving the total light transmittance and elastic modulus of an optical film obtained by using polyimide-imide resin, n is preferably 0 Or 1, more preferably 0.

於式(a)中之Y係由式(1)所表示之情形時，式(1)中之＊及R＊ 表示源自四羧酸化合物之結構單元中之與源自羧基之部分(例如醯亞胺基部分)鍵結之鍵結鍵。於本說明書中，所謂四羧酸化合物，可為選自由具有4個羧基之化合物、該化合物之羧酸鹵化物、羧酸酯、及相鄰之2個羧基經脫水縮合而成之羧酸二酐所組成之群中之化合物，就合成時之聚合容易度之觀點而言，四羧酸化合物較佳為四羧酸二酐。When Y in formula (a) is represented by formula (1), * and R * in formula (1) represent the part derived from the carboxyl group in the structural unit of the tetracarboxylic acid compound (for example (Amino moiety) bonding bond. In this specification, the so-called tetracarboxylic acid compound can be selected from a compound having 4 carboxyl groups, a carboxylic acid halide of the compound, a carboxylic acid ester, and two adjacent carboxyl groups formed by dehydration and condensation. Among the compounds in the group consisting of anhydrides, the tetracarboxylic acid compound is preferably tetracarboxylic dianhydride from the viewpoint of ease of polymerization during synthesis.

提供式(a)中之Y係由式(1)所表示之結構單元(a1)之四羧酸化合物例如於該四羧酸化合物為四羧酸二酐之情形時，係由式(8)所表示： [化19]

Figure 02_image041
[式(8)中，Ra 及n如式(1)中所定義]Provide a tetracarboxylic acid compound in which Y in the formula (a) is the structural unit (a1) represented by the formula (1), for example, when the tetracarboxylic acid compound is a tetracarboxylic dianhydride, it is derived from the formula (8) Represented: [化19]
Figure 02_image041
[In formula (8), R a and n are as defined in formula (1)]

於式(b)中之Z係由式(1)所表示之情形時，式(1)中之＊表示源自二羧酸化合物之結構單元中之與羰基碳鍵結之鍵結鍵。於本說明書中，所謂二羧酸化合物，可為具有2個羧基之化合物、該化合物之羧酸鹵化物及/或羧酸酯。When Z in the formula (b) is represented by the formula (1), * in the formula (1) represents the bond to the carbonyl carbon in the structural unit derived from the dicarboxylic acid compound. In this specification, the so-called dicarboxylic acid compound may be a compound having two carboxyl groups, a carboxylic acid halide and/or a carboxylic acid ester of the compound.

賦予式(b)中之Z係由式(1)所表示之結構單元(b1)之二羧酸化合物例如於該二羧酸化合物為二羧醯氯之情形時，係由式(12)所表示： [化20]

Figure 02_image043
[式(12)中，Ra 及n如式(1)中所定義]A dicarboxylic acid compound in which Z in formula (b) is the structural unit (b1) represented by formula (1), for example, when the dicarboxylic acid compound is dicarboxylic acid chloride, is represented by formula (12) Means: [化20]
Figure 02_image043
[In formula (12), R a and n are as defined in formula (1)]

於本發明之光學膜中所包含之聚醯胺醯亞胺系樹脂中，式(a)中之Y係由式(1)所表示之結構單元(a1)及式(b)中之Z係由式(1)所表示之結構單元(b1)之合計量基於聚醯胺醯亞胺系樹脂中所包含之總結構單元，較佳為2～45莫耳%，更佳為5～40%，進而較佳為10～40莫耳%，尤佳為15～35莫耳%。若結構單元(a1)及結構單元(b1)之合計量為上述下限以上，則容易提高光學膜之外觀品質及彈性模數。又，若結構單元(a1)及結構單元(b1)之合計量為上述上限以下，則容易提高光學膜之全光線透過率。此處，於本說明書中，所謂聚醯胺醯亞胺系樹脂中所包含之總結構單元，表示聚醯胺醯亞胺系樹脂中所包含之總單體單元。再者，聚醯胺醯亞胺系樹脂中所包含之結構單元(a1)、結構單元(b1)及總結構單元之量例如可使用1 H-NMR(nuclear magnetic resonance，核磁共振)進行測定或亦可根據原料之添加比算出。此處，所謂結構單元(a1)及結構單元(b1)之合計量，並非意指結構單元(a1)及結構單元(b1)之兩者均包含於聚醯胺醯亞胺系樹脂中，於本發明中，只要結構單元(a1)及結構單元(b1)之至少一者包含於聚醯胺醯亞胺系樹脂中即可。再者，於本發明中，就容易提高本發明之光學膜之外觀品質、全光線透過率及彈性模數之觀點而言，光學膜中所包含之聚醯胺醯亞胺系樹脂較佳為至少包含結構單元(a1)。In the polyamide imine resin contained in the optical film of the present invention, Y in formula (a) is a structural unit (a1) represented by formula (1) and Z in formula (b) The total amount of the structural unit (b1) represented by the formula (1) is based on the total structural unit contained in the polyimide-based resin, preferably 2 to 45 mol%, more preferably 5 to 40% , And more preferably 10-40 mol%, particularly preferably 15-35 mol%. If the total amount of the structural unit (a1) and the structural unit (b1) is more than the above lower limit, it is easy to improve the appearance quality and elastic modulus of the optical film. Moreover, if the total amount of the structural unit (a1) and the structural unit (b1) is equal to or less than the above upper limit, the total light transmittance of the optical film can be easily increased. Here, in this specification, the so-called total structural unit contained in the polyimide-based resin means the total monomer unit contained in the polyimide-based resin. Furthermore, the amount of structural unit (a1), structural unit (b1) and total structural unit contained in the polyimide-imide resin can be measured using 1 H-NMR (nuclear magnetic resonance) or It can also be calculated based on the addition ratio of raw materials. Here, the total amount of the structural unit (a1) and the structural unit (b1) does not mean that both of the structural unit (a1) and the structural unit (b1) are contained in the polyimide imine-based resin. In the present invention, as long as at least one of the structural unit (a1) and the structural unit (b1) is contained in the polyimide-based resin. Furthermore, in the present invention, from the viewpoint of easily improving the appearance quality, total light transmittance and elastic modulus of the optical film of the present invention, the polyimide-based resin contained in the optical film is preferably It contains at least the structural unit (a1).

於聚醯胺醯亞胺系樹脂包含式(a)中之Y係由式(1)所表示之結構單元(a1)之本發明之較佳之一態樣中，該結構單元(a1)之量基於聚醯胺醯亞胺系樹脂中所包含之總結構單元，較佳為2～45莫耳%，更佳為5～40%，進而較佳為10～40莫耳%，尤佳為15～35莫耳%。若結構單元(a1)之量為上述下限以上，則容易提高光學膜之外觀品質及彈性模數。又，若結構單元(a1)之量為上述上限以下，則容易提高光學膜之全光線透過率。再者，聚醯胺醯亞胺系樹脂中所包含之結構單元(a1)、結構單元(b1)及總結構單元之量例如可使用1 H-NMR進行測定或亦可根據原料之添加比而算出。In a preferred aspect of the present invention in which the polyamide imine-based resin contains the structural unit (a1) represented by the formula (1) where Y in the formula (a) is, the amount of the structural unit (a1) Based on the total structural units contained in the polyimide-based resin, it is preferably 2 to 45 mol%, more preferably 5 to 40%, further preferably 10 to 40 mol%, and particularly preferably 15 ~35 mol%. If the amount of the structural unit (a1) is more than the above lower limit, it is easy to improve the appearance quality and elastic modulus of the optical film. Moreover, if the amount of the structural unit (a1) is equal to or less than the above upper limit, it is easy to increase the total light transmittance of the optical film. Furthermore, the amount of structural unit (a1), structural unit (b1), and total structural unit contained in the polyimide-imide resin can be measured using 1 H-NMR or can also be determined according to the addition ratio of raw materials. Figure out.

式(1)較佳為由式(1')所表示： [化21]

Figure 02_image045
[式(1')中，＊表鍵結鍵，R＊ 於Y係由式(1)所表示之情形時，表示鍵結鍵，於Z係由式(1)所表示之情形時，表示氫原子] 再者，式(1')相當於式(1)中之Ra 為氫原子且n為0之結構。Formula (1) is preferably represented by formula (1'): [化21]
Figure 02_image045
[In the formula (1'), * represents a bonding bond, R * when Y is represented by formula (1), it represents a bonding bond, and when Z is represented by formula (1), it represents Hydrogen atom] Furthermore, formula (1') corresponds to a structure in which Ra in formula (1) is a hydrogen atom and n is 0.

於本發明之光學膜中所包含之聚醯胺醯亞胺系樹脂包含式(a)中之Y係由式(1)所表示之結構單元(a1)之較佳之一態樣中，該聚醯胺醯亞胺系樹脂除結構單元(a1)以外，至少具有源自二羧酸化合物之結構單元(b)、及源自二胺化合物之結構單元(c)。該態樣中之聚醯胺醯亞胺系樹脂可具有1種結構單元(b)，亦可具有2種以上之結構單元(b)。又，該聚醯胺醯亞胺系樹脂可具有1種結構單元(c)，亦可具有2種以上之結構單元(c)。又，可進而具有與結構單元(a1)不同之源自四羧酸化合物之結構單元，亦可具有源自三羧酸化合物之結構單元等與結構單元(a)～(c)不同之另外之結構單元。In a preferred aspect of the polyamide imine resin contained in the optical film of the present invention including the structural unit (a1) represented by the formula (1) in the formula (a), the polyamide In addition to the structural unit (a1), the amidoimine-based resin has at least a structural unit (b) derived from a dicarboxylic acid compound and a structural unit (c) derived from a diamine compound. The polyimide-based resin in this aspect may have one type of structural unit (b), or may have two or more types of structural unit (b). In addition, the polyimide-based resin may have one type of structural unit (c), or may have two or more types of structural unit (c). In addition, it may further have a structural unit derived from a tetracarboxylic acid compound different from the structural unit (a1), or a structural unit derived from a tricarboxylic acid compound, etc., which are different from the structural units (a) to (c) Structural units.

於本發明之光學膜中所包含之聚醯胺醯亞胺系樹脂包含式(b)中之Z係由式(1)所表示之結構單元(b1)之較佳之一態樣中，該聚醯胺醯亞胺系樹脂除結構單元(b1)以外，至少具有源自四羧酸化合物之結構單元(a)、及源自二胺化合物之結構單元(c)。該態樣中之聚醯胺醯亞胺系樹脂可具有1種結構單元(a)，亦可具有2種以上之結構單元(a)。又，該聚醯胺醯亞胺系樹脂可具有1種結構單元(c)，亦可具有2種以上之結構單元(c)。又，可進而具有與結構單元(b1)不同之源自二羧酸化合物之結構單元，亦可具有源自三羧酸化合物之結構單元等與結構單元(a)～(c)不同之另外之結構單元。The polyimide imine resin contained in the optical film of the present invention includes the Z in the formula (b) is a structural unit (b1) represented by the formula (1) in a preferred aspect, the poly In addition to the structural unit (b1), the amidoimine-based resin has at least a structural unit (a) derived from a tetracarboxylic acid compound and a structural unit (c) derived from a diamine compound. The polyimide imine resin in this aspect may have one type of structural unit (a), or may have two or more types of structural unit (a). In addition, the polyimide-based resin may have one type of structural unit (c), or may have two or more types of structural unit (c). In addition, it may further have a structural unit derived from a dicarboxylic acid compound different from the structural unit (b1), or a structural unit derived from a tricarboxylic acid compound, etc., which are different from the structural units (a) to (c) Structural units.

於本發明之光學膜中所包含之聚醯胺醯亞胺系樹脂中，源自二羧酸化合物之結構單元(b)之量基於聚醯胺醯亞胺系樹脂中所包含之總結構單元，較佳為5～70莫耳%，更佳為10～65%，進而較佳為20～60莫耳%。若結構單元(b)之量為上述下限以上，則容易提高樹脂對溶劑之溶解性，從而容易提高清漆之穩定性。又，若結構單元(b)之量為上述上限以下，則容易提高彈性模數。再者，於聚醯胺醯亞胺系樹脂包含結構單元(b1)作為源自二羧酸化合物之結構單元(b)之情形時，關於上述範圍，較佳為結構單元(b1)與並非為結構單元(b1)之源自其他二羧酸之結構單元(例如下述結構單元(b2)及(b3))之合計量為上述範圍內。In the polyamideimide resin contained in the optical film of the present invention, the amount of the structural unit (b) derived from the dicarboxylic acid compound is based on the total structural unit contained in the polyamideimine resin , Preferably 5 to 70 mol%, more preferably 10 to 65%, and still more preferably 20 to 60 mol%. If the amount of the structural unit (b) is more than the above lower limit, the solubility of the resin to the solvent is easily improved, and the stability of the varnish is easily improved. Moreover, if the amount of the structural unit (b) is less than or equal to the above upper limit, it is easy to increase the elastic modulus. Furthermore, when the polyimide imine-based resin contains the structural unit (b1) as the structural unit (b) derived from the dicarboxylic acid compound, with respect to the above range, the structural unit (b1) is preferred and not The total amount of the structural units derived from other dicarboxylic acids of the structural unit (b1) (for example, the structural units (b2) and (b3) below) is within the above range.

於本發明之光學膜中所包含之聚醯胺醯亞胺系樹脂中，源自二胺化合物之結構單元(c)之量於將源自四羧酸化合物之結構單元(a)及源自二羧酸化合物之結構單元(b)之合計量設為100莫耳%時，較佳為95～105莫耳%，更佳為97～103莫耳%，進而較佳為98～102莫耳%，尤佳為99～101莫耳%。若結構單元(c)之量為上述範圍外，則分子量難以上升，而清漆之穩定性容易降低。In the polyamide imine resin contained in the optical film of the present invention, the amount of the structural unit (c) derived from the diamine compound is greater than the amount of the structural unit (a) derived from the tetracarboxylic acid compound and When the total amount of the structural unit (b) of the dicarboxylic acid compound is 100 mol%, it is preferably 95-105 mol%, more preferably 97-103 mol%, and still more preferably 98-102 mol% %, particularly preferably 99 to 101 mole%. If the amount of the structural unit (c) is outside the above range, the molecular weight is unlikely to increase, and the stability of the varnish is likely to decrease.

於本發明中，聚醯胺醯亞胺系樹脂具有式(b)： [化22]

Figure 02_image047
[式(b)中，Z表示二價有機基，＊表示鍵結鍵] 所表示之結構單元作為源自二羧酸化合物之結構單元(b)。此處，式(b)中之＊係於聚醯胺醯亞胺系樹脂中通常與和源自二羧酸化合物之結構單元相鄰之源自二胺化合物之結構單元(c)連結之鍵結鍵。結構單元(b)例如形成上述式(E)所表示之醯胺鍵。In the present invention, the polyamide imine resin has the formula (b): [化22]
Figure 02_image047
[In the formula (b), Z represents a divalent organic group, and * represents a bonding bond] The structural unit represented is the structural unit (b) derived from the dicarboxylic acid compound. Here, the * in the formula (b) is the bond in the polyamide imine resin that is usually connected to the structural unit (c) derived from the diamine compound adjacent to the structural unit derived from the dicarboxylic acid compound Bond. The structural unit (b) forms, for example, an amide bond represented by the above formula (E).

式(b)中之Z為二價有機基，較佳為可經碳數1～8之烴基或經氟取代之碳數1～8之烴基取代之碳數4～40之二價有機基，更佳為可經碳數1～8之烴基或經氟取代之碳數1～8之烴基取代之具有環狀結構之碳數4～40之二價有機基。作為環狀結構，可列舉：脂環、芳香環、雜環結構。作為Z，可例示式(20)、式(21)、式(22)、式(23)、式(24)、式(25)、式(26)、式(27)、式(28)及式(29)： [化23]

Figure 02_image049
所表示之基之鍵結鍵中不相鄰之2個被取代為氫原子之二價有機基及碳數6以下之二價鏈式烴基，作為Z之雜環結構，可例示具有噻吩環骨架之二價有機基。就容易降低光學積層體之YI值之觀點而言，較佳為式(20)～式(27)所表示之基之鍵結鍵中之不相鄰之2個被取代為氫原子之二價有機基、及具有噻吩環骨架之二價有機基，更佳為式(20')、式(21')、式(22')、式(23')、式(24')、式(25')、式(26')、式(27')、式(28')及式(29')： [化24]
Figure 02_image051
所表示之二價有機基。再者，式(20)～式(29)及式(20')～式(29')中之環上之氫原子可被取代為碳數1～6之烷基、碳數1～6之烷氧基、或碳數6～12之芳基(該等基中之氫原子可被取代為鹵素原子(較佳為氟原子))。於本發明之一實施形態中，聚醯胺醯亞胺系樹脂中所包含之結構單元(b)可包含1種有機基作為Z，亦可包含2種以上之有機基作為Z。Z in the formula (b) is a divalent organic group, preferably a divalent organic group with 4 to 40 carbons which can be substituted by a hydrocarbon group with 1 to 8 carbons or a hydrocarbon group with 1 to 8 carbons substituted by fluorine, More preferably, it is a divalent organic group with a cyclic structure and a carbon number of 4-40 which can be substituted by a hydrocarbon group with 1 to 8 carbons or a hydrocarbon group with 1 to 8 carbons substituted by fluorine. Examples of the cyclic structure include alicyclic, aromatic, and heterocyclic structures. As Z, the formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), formula (28) and Formula (29): [化23]
Figure 02_image049
Two non-adjacent divalent organic groups substituted with hydrogen atoms and a divalent chain hydrocarbon group with a carbon number of 6 or less among the bonding bonds of the indicated groups. As the heterocyclic structure of Z, a thiophene ring skeleton can be exemplified The bivalent organic base. From the viewpoint of ease of lowering the YI value of the optical laminate, it is preferable that two non-adjacent bonds of the groups represented by formulas (20) to (27) are substituted with hydrogen atoms. The organic group and the divalent organic group having a thiophene ring skeleton are more preferably formula (20'), formula (21'), formula (22'), formula (23'), formula (24'), formula (25 '), formula (26'), formula (27'), formula (28') and formula (29'): [化24]
Figure 02_image051
The expressed divalent organic group. Furthermore, the hydrogen atoms on the rings in formulas (20) to (29) and formulas (20') to (29') can be substituted with alkyl groups with 1 to 6 carbons, and those with 1 to 6 carbons. An alkoxy group or an aryl group having 6 to 12 carbon atoms (the hydrogen atoms in these groups may be substituted with halogen atoms (preferably fluorine atoms)). In one embodiment of the present invention, the structural unit (b) contained in the polyimide-based resin may include one type of organic group as Z, and may also include two or more types of organic groups as Z.

式(20)～式(29)及式(20')～式(29')中， ＊表示鍵結鍵，W1 表示單鍵、-O-、-CH2 -、-CH2 -CH2 -、-CH(CH3 )-、-C(CH3 )2 -、-C(CF3 )2 -、-Ar3 -、-SO2 -、-CO-、-O-Ar3 -O-、-Ar3 -O-Ar3 -、-Ar3 -CH2 -Ar3 -、-Ar3 -C(CH3 )2 -Ar3 -或-Ar3 -SO2 -Ar3 -。Ar3 表示氫原子可被取代為氟原子之碳數6～20之伸芳基，可列舉伸苯基作為具體例。於Ar3 存在複數個之情形時，Ar3 可相互相同，亦可不同。In formula (20) to formula (29) and formula (20') to formula (29'), * represents a bonding bond, W 1 represents a single bond, -O-, -CH 2 -, -CH 2 -CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -Ar 3 -, -SO 2 -, -CO-, -O-Ar 3 -O- , -Ar 3 -O-Ar 3 -, -Ar 3 -CH 2 -Ar 3 -, -Ar 3 -C(CH 3 ) 2 -Ar 3 -or -Ar 3 -SO 2 -Ar 3 -. Ar 3 represents an arylene group having 6 to 20 carbon atoms in which a hydrogen atom can be substituted with a fluorine atom, and a phenylene group can be cited as a specific example. When Ar 3 in the presence of a plurality of situations, each Ar 3 may be the same, or different.

於聚醯胺醯亞胺系樹脂具有Z係由上述式(20')～式(29')之任一者所表示之結構單元(以下，亦稱作「結構單元(b20')～(b29')」)作為結構單元(b)之情形時，就容易提高包含該樹脂之清漆之成膜性、容易提高所獲得之光學膜之均勻性之觀點而言，較佳為聚醯胺醯亞胺系樹脂除結構單元(b')以外，亦具有下述式(d1)： [化25]

Figure 02_image053
[式(d1)中，R24 如下述式(2-i)中所定義，R25 表示R24 或-C(＝O)-＊，＊表示鍵結鍵] 所表示之結構單元(以下，亦稱作「結構單元(d1)」)。作為結構單元(d1)，具體而言，可列舉：R24 及R25 均為氫原子之結構單元、R24 均為氫原子且R25 表示-C(＝O)-＊之結構單元等。The polyimide imine resin has a Z-based structural unit represented by any of the above formula (20') to formula (29') (hereinafter, also referred to as "structural unit (b20') ~ (b29) ')”) In the case of the structural unit (b), from the viewpoint that it is easy to improve the film-forming properties of the varnish containing the resin and the uniformity of the obtained optical film, polyamide is preferred In addition to the structural unit (b'), the amine resin also has the following formula (d1): [化25]
Figure 02_image053
[In formula (d1), R 24 is as defined in the following formula (2-i), R 25 represents R 24 or -C(=O)-*, * represents a bonding bond] The structural unit represented by (hereinafter, Also called "structural unit (d1)"). Specific examples of the structural unit (d1) include structural units in which both R 24 and R 25 are hydrogen atoms, and structural units in which both R 24 and R 25 represent -C(=O)-*.

賦予結構單元(b)之二羧酸化合物只要為具有2個羰基之化合物即可，並無特別限定，例如可列舉式(b')所表示之化合物： [化26]

Figure 02_image055
[式(b')中，Z表示二價有機基，R31 及R32 相互獨立地表示羥基、甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第二丁氧基、第三丁氧基或氯原子]The dicarboxylic acid compound imparting the structural unit (b) is not particularly limited as long as it is a compound having two carbonyl groups. For example, a compound represented by the formula (b') may be mentioned: [formula 26]
Figure 02_image055
[In formula (b'), Z represents a divalent organic group, and R 31 and R 32 independently represent hydroxyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and Dibutoxy, tertiary butoxy or chlorine atom]

於本發明中，聚醯胺醯亞胺系樹脂之源自二胺化合物之結構單元(c)係由式(c)所表示： [化27]

Figure 02_image057
[式(c)中，X表示二價有機基，Rc 相互獨立地表示氫原子或鍵結鍵，＊表示鍵結鍵] 此處，式(c)所表示之結構單元(c)於聚醯胺醯亞胺系樹脂中，通常與源自四羧酸化合物之結構單元(a)或源自二羧酸化合物之結構單元(b)相鄰，且通常形成例如上述式(D)所表示之醯亞胺鍵或上述式(E)所表示之醯胺鍵。於結構單元(c)中，Rc 相互獨立地表示氫原子或鍵結鍵。於＊所表示之一個鍵結鍵鍵結於相鄰之源自四羧酸化合物之結構單元之情形時，根據式(D)亦清楚知道Rc 表示鍵結鍵，且鍵結於相鄰之源自四羧酸之結構單元。於結構單元(c)中，於＊所表示之一個鍵結鍵鍵結於相鄰之源自二羧酸化合物之結構單元之情形時，根據式(E)亦清楚知道Rc 表示氫原子。In the present invention, the structural unit (c) derived from the diamine compound of the polyamide imine resin is represented by the formula (c): [化27]
Figure 02_image057
[In formula (c), X represents a divalent organic group, R c independently represents a hydrogen atom or a bonding bond, * represents a bonding bond] Here, the structural unit (c) represented by formula (c) is In the amide imine resin, it is usually adjacent to the structural unit (a) derived from the tetracarboxylic acid compound or the structural unit (b) derived from the dicarboxylic acid compound, and is usually formed as represented by the above formula (D) The amide bond or the amide bond represented by the above formula (E). In the structural unit (c), R c independently represents a hydrogen atom or a bonding bond. When a bonding bond represented by * is bonded to an adjacent structural unit derived from a tetracarboxylic acid compound, it is also clear from formula (D) that R c represents a bonding bond and is bonded to an adjacent A structural unit derived from tetracarboxylic acid. In the structural unit (c), when a bonding bond represented by * is bonded to an adjacent structural unit derived from a dicarboxylic acid compound, it is also clear from the formula (E) that R c represents a hydrogen atom.

式(c)中之X表示二價有機基，較佳為碳數4～40之二價有機基，更佳為表示具有環狀結構之碳數4～40之二價有機基。作為環狀結構，可列舉：脂環、芳香環、雜環結構。關於上述有機基，有機基中之氫原子可經烴基或經氟取代之烴基取代，於該情形時，烴基及經氟取代之烴基之碳數較佳為1～8。於本發明之一實施形態中，聚醯胺醯亞胺系樹脂中所包含之結構單元(c)可包含1種二價有機基作為X，亦可包含2種以上之二價有機基作為X。X in the formula (c) represents a divalent organic group, preferably a divalent organic group having 4 to 40 carbons, more preferably a divalent organic group having 4 to 40 carbons having a cyclic structure. Examples of the cyclic structure include alicyclic, aromatic, and heterocyclic structures. Regarding the above-mentioned organic group, the hydrogen atom in the organic group may be substituted by a hydrocarbon group or a fluorine-substituted hydrocarbon group. In this case, the carbon number of the hydrocarbon group and the fluorine-substituted hydrocarbon group is preferably 1-8. In one embodiment of the present invention, the structural unit (c) contained in the polyimide-based resin may include one type of divalent organic group as X, and may also include two or more types of divalent organic groups as X .

提供結構單元(c)之二胺化合物只要為具有2個胺基之化合物，則並無特別限定，例如可列舉式(c')所表示之化合物： [化28]

Figure 02_image059
[式(c')中，X表示二價有機基]The diamine compound providing the structural unit (c) is not particularly limited as long as it is a compound having two amine groups. For example, a compound represented by the formula (c') can be cited: [化28]
Figure 02_image059
[In formula (c'), X represents a divalent organic group]

於本發明之光學膜中所包含之聚醯胺醯亞胺系樹脂中，若包含式(1)所表示之結構單元之四羧酸化合物(例如式(8)所表示之化合物)與例如式(c')所表示之二胺化合物反應，則形成式(10)所表示之結構單元： [化29]

Figure 02_image061
[式(10)中，Ra 及n如式(1)中之Ra 及n所定義，X如式(c)中之X所定義，＊表示鍵結鍵] 又，若例如式(b')所表示之二羧酸化合物與例如式(c')所表示之二胺化合物反應，則形成式(11)所表示之結構單元： [化30]
Figure 02_image063
[式(11)中，Z如式(b)中之Z所定義，X如式(c)中之X所定義，＊表示鍵結鍵]In the polyamide imine resin contained in the optical film of the present invention, if the tetracarboxylic acid compound (for example, the compound represented by the formula (8)) of the structural unit represented by formula (1) is contained in The reaction of the diamine compound represented by (c') forms the structural unit represented by formula (10): [化29]
Figure 02_image061
[In the formula (10), R a and n are as defined in formula R (1) in the a and n are as defined, in the X of formula (C) X defined * indicates bonding bond] Further, when, for example, of formula (b The dicarboxylic acid compound represented by') reacts with, for example, the diamine compound represented by formula (c') to form the structural unit represented by formula (11): [化30]
Figure 02_image063
[In formula (11), Z is defined as Z in formula (b), X is defined as X in formula (c), and * represents a bonding bond]

於本發明之較佳之一態樣中，聚醯胺醯亞胺系樹脂除選自由上述結構單元(a1)及結構單元(b1)所組成之群中之至少1種結構單元以外，亦包含式(2)： [化31]

Figure 02_image065
[式(2)中，Z1 表示可具有取代基之作為單環式芳香族環或縮合多環式芳香族環之二價芳香族基，＊表示鍵結鍵] 所表示之結構單元(b2)作為源自二羧酸化合物之結構單元(b)。聚醯胺醯亞胺系樹脂通常具有複數個式(b)所表示之結構單元(b)。於本態樣中，只要複數個結構單元(b)之至少一部分為式(2)所表示之結構單元(b2)即可。於該態樣中，本發明中之聚醯胺醯亞胺系樹脂可具有1種結構單元(b2)作為結構單元(b)，亦可具有2種以上之結構單元(b2)作為結構單元(b)，亦可具有結構單元(b2)以外之其他結構單元(b)。In a preferred aspect of the present invention, the polyimide imine-based resin includes at least one structural unit selected from the group consisting of the structural unit (a1) and the structural unit (b1), and also includes the formula (2): [化31]
Figure 02_image065
[In formula (2), Z 1 represents a divalent aromatic group that may have a substituent as a monocyclic aromatic ring or a condensed polycyclic aromatic ring, * represents a bonding bond] The structural unit represented by (b2 ) As a structural unit (b) derived from a dicarboxylic acid compound. The polyimide-based resin usually has a plurality of structural units (b) represented by the formula (b). In this aspect, as long as at least a part of a plurality of structural units (b) is a structural unit (b2) represented by formula (2). In this aspect, the polyimide imine resin in the present invention may have one type of structural unit (b2) as the structural unit (b), and may also have two or more types of structural units (b2) as the structural unit ( b), it may have other structural units (b) other than the structural unit (b2).

式(2)中之Z1 表示可具有取代基之二價芳香族基。二價芳香族基係單環式芳香族環或縮合多環式芳香族環之2個氫原子被取代為鍵結鍵之基。二價芳香族基可包含僅由碳原子形成環(單環或縮合多環)之芳香族環，亦可包含包括碳原子以外之原子而形成環之雜芳環。作為碳原子以外之原子，例如可列舉氮原子、硫原子及氧原子。形成芳香族環之碳原子及碳原子以外之原子之合計個數並無特別限定，較佳為5～18，更佳為5～14，進而較佳為5～13，尤佳為5～12。Z 1 in the formula (2) represents a divalent aromatic group which may have a substituent. The divalent aromatic group is a group in which two hydrogen atoms of a monocyclic aromatic ring or a condensed polycyclic aromatic ring are replaced with bonding bonds. The divalent aromatic group may include an aromatic ring (monocyclic or condensed polycyclic) formed only by carbon atoms, or may include a heteroaromatic ring including atoms other than carbon atoms to form a ring. Examples of atoms other than carbon atoms include nitrogen atoms, sulfur atoms, and oxygen atoms. The total number of carbon atoms and atoms other than carbon atoms forming the aromatic ring is not particularly limited, but is preferably 5-18, more preferably 5-14, still more preferably 5-13, and particularly preferably 5-12 .

作為單環式芳香族環，例如可列舉：苯、呋喃、吡咯、噻吩、吡啶、咪唑、吡唑、㗁唑、噻唑、咪唑啉等。Examples of the monocyclic aromatic ring include benzene, furan, pyrrole, thiophene, pyridine, imidazole, pyrazole, azole, thiazole, imidazoline, and the like.

作為縮合多環式芳香族環，例如可列舉：萘、蒽、菲、吲哚、苯并噻唑、苯并㗁唑、苯并咪唑等。Examples of the condensed polycyclic aromatic ring include naphthalene, anthracene, phenanthrene, indole, benzothiazole, benzoxazole, and benzimidazole.

就容易提高光學膜之外觀品質以及彈性模數及全光線透過率之觀點而言，可具有取代基之二價芳香族基較佳為芳香族烴環之2個氫原子被取代為鍵結鍵之基，更佳為苯、聯苯、聯三苯或聯四苯之2個氫原子被取代為鍵結鍵之基，進而較佳為苯或聯苯之2個氫原子被取代為鍵結鍵之基，尤佳為苯之2個氫原子被取代為鍵結鍵之基。From the viewpoint of easily improving the appearance quality, elastic modulus, and total light transmittance of the optical film, the divalent aromatic group that may have a substituent is preferably that the two hydrogen atoms of the aromatic hydrocarbon ring are substituted as bonding bonds More preferably, the two hydrogen atoms of benzene, biphenyl, terphenyl or bitetraphenyl are substituted as a bonding bond group, and more preferably, the two hydrogen atoms of benzene or biphenyl are substituted as a bond The group of the bond is particularly preferably the group in which the two hydrogen atoms of benzene are substituted for the bonding bond.

式(2)中之Z1 所表示之二價芳香族基亦可具有取代基。作為取代基，例如可列舉選自由(i)碳數1～12之烷基、(ii)碳數1～12之烷氧基、(iii)碳數6～12之芳基、(iv)碳數6～12之芳氧基、及(v)羥基所組成之群中之至少1種基。再者，上述取代基中所包含之氫原子可進而相互獨立地被取代為鹵素原子、碳數1～4之烷基、碳數1～4之烷氧基、羥基、或羧基。該二價芳香族基可具有選自由上述(i)～(v)之取代基、及上述(i)～(v)之取代基中所包含之氫原子進而相互獨立地被取代為鹵素原子、碳數1～4之烷基、碳數1～4之烷氧基、羥基、或羧基之基所組成之群中之至少1種取代基，亦可不具有取代基。就容易製造具有較高之彈性模數及之光學膜之觀點而言，式(2)中之Z1 所表示之二價芳香族基較佳為不具有取代基。The divalent aromatic group represented by Z 1 in formula (2) may have a substituent. Examples of the substituent include (i) alkyl groups having 1 to 12 carbons, (ii) alkoxy groups having 1 to 12 carbons, (iii) aryl groups having 6 to 12 carbons, and (iv) carbon At least one group in the group consisting of 6-12 aryloxy groups and (v) hydroxyl groups. Furthermore, the hydrogen atoms contained in the above substituents may be further independently substituted with halogen atoms, C1-C4 alkyl groups, C1-C4 alkoxy groups, hydroxyl groups, or carboxyl groups. The divalent aromatic group may have a hydrogen atom selected from the substituents (i) to (v) above and the hydrogen atoms contained in the substituents (i) to (v) above and are independently substituted with halogen atoms, At least one substituent in the group consisting of an alkyl group having 1 to 4 carbons, an alkoxy group having 1 to 4 carbons, a hydroxyl group, or a carboxyl group may not have a substituent. From the viewpoint of easy production of an optical film having a higher elastic modulus, the divalent aromatic group represented by Z 1 in formula (2) preferably has no substituent.

作為(i)碳數1～12之烷基、(ii)碳數1～12之烷氧基及(iii)碳數6～12之芳基，可列舉關於式(1)中之Ra 於上述所例示之基，與該等相關之較佳之記載亦同樣地與上述相符。As (i) an alkyl group having 1 to 12 carbons, (ii) an alkoxy group having 1 to 12 carbons, and (iii) an aryl group having 6 to 12 carbons, there may be mentioned R a in the formula (1) The bases exemplified above, and the related better descriptions are also consistent with the above.

作為(iv)碳數6～12之芳氧基，可列舉：苯氧基、甲苯氧基、二甲苯氧基、萘氧基、聯苯氧基等。碳數6～12之芳氧基之碳數較佳為6或10或12。上述碳數6～12之芳氧基亦可為至少1個氫原子相互獨立地被取代為鹵素原子、碳數1～4之烷基、碳數1～4之烷氧基、羥基、或羧基之基。作為鹵素原子，可列舉上述所記載之原子。此處，於碳數6～12之芳氧基經包含碳原子之取代基取代之情形時，該取代基中所包含之碳原子數不包含於碳數6～12之芳氧基之碳數中。(Iv) The aryloxy group having 6 to 12 carbon atoms includes a phenoxy group, a tolyloxy group, a xylyloxy group, a naphthyloxy group, and a biphenoxy group. The carbon number of the aryloxy group having 6 to 12 carbon atoms is preferably 6 or 10 or 12. The above-mentioned aryloxy group having 6 to 12 carbons may be at least one hydrogen atom independently substituted with a halogen atom, an alkyl group having 1 to 4 carbons, an alkoxy group having 1 to 4 carbons, a hydroxyl group, or a carboxyl group The base. Examples of the halogen atom include the atoms described above. Here, when the aryloxy group having 6 to 12 carbon atoms is substituted with a substituent containing carbon atoms, the number of carbon atoms contained in the substituent is not included in the number of carbon atoms of the aryloxy group having 6 to 12 carbon atoms in.

於聚醯胺醯亞胺系樹脂包含式(2)所表示之結構單元(b2)作為源自二羧酸化合物之結構單元(b)之本發明之較佳之一態樣中，就容易提高光學膜之外觀品質以及全光線透過率及彈性模數之觀點而言，於將聚醯胺醯亞胺系樹脂中所包含之結構單元(b)之合計設為100莫耳%時，式(2)所表示之結構單元(b2)之比率較佳為70～100莫耳%，更佳為80～100莫耳%，進而較佳為90～100莫耳%，亦可為聚醯胺醯亞胺系樹脂中所包含之結構單元(b)全部為結構單元(b2)。結構單元(b)及結構單元(b2)之含量例如可使用1 H-NMR進行測定或亦可根據原料之添加比算出。In a preferred aspect of the present invention in which the polyamide imine-based resin includes the structural unit (b2) represented by the formula (2) as the structural unit (b) derived from the dicarboxylic acid compound, it is easy to improve the optical From the viewpoint of the appearance quality of the film, the total light transmittance and the modulus of elasticity, when the total of the structural units (b) contained in the polyimide resin is set to 100 mol%, the formula (2 The ratio of the structural unit (b2) represented by) is preferably 70-100 mol%, more preferably 80-100 mol%, still more preferably 90-100 mol%, and may also be polyamide All the structural units (b) contained in the amine resin are structural units (b2). The content of the structural unit (b) and the structural unit (b2) can be measured, for example, using 1 H-NMR or can be calculated from the addition ratio of the raw materials.

於聚醯胺醯亞胺系樹脂除包含選自由上述結構單元(a1)及結構單元(b1)所組成之群中之至少1種結構單元以外亦包含結構單元(b2)之本發明之較佳之一態樣中，式(2)所表示之結構單元(b2)更佳為由下述式(2-i)所表示： [化32]

Figure 02_image067
[式(2-i)中，R24 相互獨立地表示氫原子、(i)碳數1～12之烷基、(ii)碳數1～12之烷氧基、(iii)碳數6～12之芳基、(iv)碳數6～12之芳氧基或(v)羥基，R24 中所包含之氫原子可被取代為鹵素原子，較佳為表示氫原子，＊表示鍵結鍵] 於該情形時，聚醯胺醯亞胺系樹脂具有式(2-i)所表示之結構單元(以下，亦稱為「結構單元(b2-i)」)。於該態樣中，就容易提高包含該樹脂之清漆之成膜性、容易提高所獲得之光學膜之均勻性之觀點而言，聚醯胺醯亞胺系樹脂較佳為除具有上述結構單元(b2-i)以外，亦進而具有上述式(d1)所表示之結構單元(d1)。In addition to at least one structural unit selected from the group consisting of the above-mentioned structural unit (a1) and structural unit (b1), the polyimide-imide-based resin also includes a structural unit (b2). In one aspect, the structural unit (b2) represented by formula (2) is more preferably represented by the following formula (2-i): [化32]
Figure 02_image067
[In formula (2-i), R 24 independently represents a hydrogen atom, (i) an alkyl group having 1 to 12 carbons, (ii) an alkoxy group having 1 to 12 carbons, and (iii) a carbon number of 6 to 12 aryl group, (iv) carbon 6-12 aryloxy group or (v) hydroxyl group, the hydrogen atom contained in R 24 can be substituted with a halogen atom, preferably a hydrogen atom, and * represents a bonding bond ] In this case, the polyimide-based resin has a structural unit represented by formula (2-i) (hereinafter, also referred to as "structural unit (b2-i)"). In this aspect, from the viewpoints of easily improving the film-forming properties of the varnish containing the resin and easily improving the uniformity of the obtained optical film, the polyimide-based resin preferably has the above-mentioned structural unit In addition to (b2-i), it also has a structural unit (d1) represented by the above formula (d1).

於本發明之較佳之一態樣中，聚醯胺醯亞胺系樹脂包含式(3)： [化33]

Figure 02_image069
[式(3)中，X1 表示可具有取代基之二價芳香族基，Rc 相互獨立地表示氫原子或鍵結鍵，＊表示鍵結鍵] 所表示之結構單元(c1)作為源自二胺化合物之結構單元。聚醯胺醯亞胺系樹脂通常具有式(c)所表示之複數個結構單元(c)。於本態樣中，只要複數個結構單元(c)之至少一部分為式(3)所表示之結構單元(c1)即可。於該態樣中，本發明之光學膜中所包含之聚醯胺醯亞胺系樹脂可具有1種結構單元(c1)作為結構單元(c)，亦可具有2種以上之結構單元(c1)作為結構單元(c)，亦可具有結構單元(c1)以外之其他結構單元(c)。In a preferred aspect of the present invention, the polyimide-imide-based resin includes formula (3): [化33]
Figure 02_image069
[In formula (3), X 1 represents a divalent aromatic group that may have a substituent, R c independently represents a hydrogen atom or a bonding bond, and * represents a bonding bond] The structural unit (c1) represented as the source From the structural unit of the diamine compound. The polyimide-based resin usually has a plurality of structural units (c) represented by the formula (c). In this aspect, it is sufficient that at least a part of the plurality of structural units (c) is the structural unit (c1) represented by formula (3). In this aspect, the polyamide imide resin contained in the optical film of the present invention may have one type of structural unit (c1) as the structural unit (c), or may have two or more types of structural unit (c1) ) As the structural unit (c), it may have another structural unit (c) other than the structural unit (c1).

式(3)中之X1 表示可具有取代基之二價芳香族基。二價芳香族基係單環式芳香族環、縮合多環式芳香族環或集合環芳香族環之2個氫原子被取代為鍵結鍵之基。二價芳香族基可包含僅由碳原子形成環(單環、縮合多環或集合環)之芳香族環，亦可包含包括碳原子以外之原子而形成環之雜芳環。作為碳原子以外之原子，例如可列舉氮原子、硫原子及氧原子。形成芳香族環之碳原子及碳原子以外之原子之合計個數並無特別限定，較佳為5～18，更佳為5～14，進而較佳為5～13，尤佳為5～12。作為單環式芳香族環及縮合多環式芳香族環之例，可列舉關於式(2)中之Z1 而於上述所記載之例。作為集合環芳香族環之例，可列舉2個以上之單環式芳香族環及/或縮合多環式芳香族環由單鍵連結之結構，作為其例，可列舉：作為單環式芳香族環或縮合多環式芳香族環之例而於上述記載之環之2個以上由單鍵連結之基、例如聯苯基、聯三苯、聯四苯、聯萘、1-苯基萘、2-苯基萘、聯吡啶等。X 1 in formula (3) represents a divalent aromatic group which may have a substituent. The divalent aromatic group is a group where two hydrogen atoms of a monocyclic aromatic ring, a condensed polycyclic aromatic ring, or an assembling aromatic ring are replaced with a bonding bond. The divalent aromatic group may include an aromatic ring (monocyclic, condensed polycyclic, or collective ring) formed only by carbon atoms, or may include a heteroaromatic ring including atoms other than carbon atoms to form a ring. Examples of atoms other than carbon atoms include nitrogen atoms, sulfur atoms, and oxygen atoms. The total number of carbon atoms and atoms other than carbon atoms forming the aromatic ring is not particularly limited, but is preferably 5-18, more preferably 5-14, still more preferably 5-13, and particularly preferably 5-12 . As examples of the monocyclic aromatic ring and the condensed polycyclic aromatic ring, the examples described above regarding Z 1 in the formula (2) can be cited. As an example of an assembling ring aromatic ring, two or more monocyclic aromatic rings and/or condensed polycyclic aromatic rings are connected by a single bond. As an example, one can cite: An example of a group ring or a condensed polycyclic aromatic ring. Two or more of the rings described above are connected by a single bond, such as biphenyl, terphenyl, bitetraphenyl, binaphthalene, 1-phenylnaphthalene , 2-phenylnaphthalene, bipyridine, etc.

就容易提高光學膜之外觀品質以及彈性模數及全光線透過率之觀點而言，可具有取代基之二價芳香族基較佳為可具有取代基之芳香族烴環之2個氫原子被取代為鍵結鍵之基，更佳為可具有取代基之苯、聯苯、聯三苯或聯四苯之2個氫原子被取代為鍵結鍵之基，進而較佳為可具有取代基之苯或聯苯之2個氫原子被取代為鍵結鍵之基，尤佳為可具有取代基之聯苯之2個氫原子被取代為鍵結鍵之基。From the viewpoint of easily improving the appearance quality, elastic modulus, and total light transmittance of the optical film, the divalent aromatic group that may have a substituent is preferably the two hydrogen atoms of the aromatic hydrocarbon ring that may have a substituent. A group substituted with a bonding bond, more preferably, two hydrogen atoms of benzene, biphenyl, terphenyl or bitetraphenyl, which may have a substituent, are substituted with a bonding bond group, and more preferably may have a substituent The two hydrogen atoms of benzene or biphenyl are substituted as a bonding bond group, and it is particularly preferred that the two hydrogen atoms of biphenyl which may have a substituent are substituted as a bonding bond group.

式(3)中之X1 所表示之二價芳香族基亦可具有取代基。作為取代基，例如可列舉：碳數1～12之烷基、碳數1～12之烷氧基、碳數6～12之芳基、及鹵素基、以及該等中所包含之氫原子被取代為鹵素原子之基。作為碳數1～12之烷基、碳數1～6之烷氧基、碳數6～12之芳基、及該等中所包含之氫原子被取代為鹵素原子之基之具體例，可列舉作為式(2)中之Z1 所表示之二價芳香族基可具有之取代基，關於(i)碳數1～12之烷基、(ii)碳數1～12之烷氧基、(iii)碳數6～12之芳基所記載之基。作為鹵素基，可列舉：氟基、氯基、溴基或碘基。The divalent aromatic group represented by X 1 in formula (3) may have a substituent. Examples of substituents include alkyl groups having 1 to 12 carbons, alkoxy groups having 1 to 12 carbons, aryl groups having 6 to 12 carbons, and halogen groups, and hydrogen atoms contained in these groups are Substitution is a group of halogen atoms. Specific examples of alkyl groups having 1 to 12 carbons, alkoxy groups having 1 to 6 carbons, aryl groups having 6 to 12 carbons, and groups in which hydrogen atoms contained in these groups are substituted with halogen atoms can be Listed as the substituents that the divalent aromatic group represented by Z 1 in formula (2) may have, (i) alkyl groups having 1 to 12 carbons, (ii) alkoxy groups having 1 to 12 carbons, (iii) The group described in the aryl group having 6 to 12 carbons. Examples of the halogen group include a fluoro group, a chloro group, a bromo group, or an iodo group.

作為式(3)中之X1 所表示之二價芳香族基可具有之取代基，較佳為鹵素基、或氫原子可被取代為鹵素原子之碳數1～12之烷基，更佳為甲基、氟基、氯基或三氟甲基。As the substituent that the divalent aromatic group represented by X 1 in the formula (3) may have, a halogen group or an alkyl group having 1 to 12 carbon atoms in which a hydrogen atom may be substituted with a halogen atom is more preferable It is methyl, fluoro, chloro or trifluoromethyl.

於本發明之較佳之一態樣中，就容易提高光學膜之外觀品質以及全光線透過率及彈性模數之觀點、及容易提高清漆之穩定性之觀點而言，式(3)中之X1 較佳為由式(4)所表示： [化34]

Figure 02_image071
[式(4)中，Rb 相互獨立地表示碳數1～6之烷基、碳數6～12之芳基、或碳數1～6之烷氧基，Rb 中所包含之氫原子可相互獨立地被取代為鹵素原子，r相互獨立地表示1～4之整數，＊表示鍵結鍵]In a preferred aspect of the present invention, from the viewpoints of easily improving the appearance quality, total light transmittance and elastic modulus of the optical film, and the viewpoint of easily improving the stability of the varnish, X in formula (3) 1 is preferably represented by formula (4): [化34]
Figure 02_image071
[In formula (4), R b independently represents an alkyl group having 1 to 6 carbons, an aryl group having 6 to 12 carbons, or an alkoxy group having 1 to 6 carbons, and the hydrogen atom contained in R b Can be substituted with halogen atoms independently of each other, r independently represents an integer from 1 to 4, and * represents a bonding bond]

式(4)中之Rb 相互獨立地表示碳數1～6之烷基、碳數6～12之芳基、或碳數1～6之烷氧基，Rb 中所包含之氫原子亦可相互獨立地被取代為鹵素原子。作為碳數1～6之烷基、碳數6～12之芳基、及碳數1～6之烷氧基，可列舉作為式(3)中之X1 所表示之二價芳香族基可具有之取代基而於上述所例示之基。式(4)中之Rb 較佳為經鹵素原子取代之碳數1～6之烷基，更佳為碳數1～6之氟烷基，進而較佳為碳數1～6之全氟烷基，進而更佳為碳數1～4之全氟烷基，尤佳為三氟甲基或五氟乙基，更尤佳為三氟甲基。R b in the formula (4) independently represents an alkyl group having 1 to 6 carbons, an aryl group having 6 to 12 carbons, or an alkoxy group having 1 to 6 carbons. The hydrogen atoms contained in R b also Can be substituted with halogen atoms independently of each other. Examples of alkyl groups having 1 to 6 carbons, aryl groups having 6 to 12 carbons, and alkoxy groups having 1 to 6 carbons include the divalent aromatic group represented by X 1 in formula (3). The substituents are those exemplified above. R b in the formula (4) is preferably an alkyl group having 1 to 6 carbon atoms substituted by a halogen atom, more preferably a fluoroalkyl group having 1 to 6 carbon atoms, and still more preferably a perfluoroalkyl group having 1 to 6 carbon atoms The alkyl group is more preferably a perfluoroalkyl group having 1 to 4 carbon atoms, particularly preferably a trifluoromethyl group or a pentafluoroethyl group, and more preferably a trifluoromethyl group.

式(4)中之r相互獨立地表示1～4之整數，就容易提高光學膜之全光線透過率及彈性模數之觀點而言，較佳為表示1～3、更佳為1～2、尤佳為1之整數。In the formula (4), r represents an integer of 1 to 4 independently of each other. From the viewpoint of easily improving the total light transmittance and elastic modulus of the optical film, it preferably represents 1 to 3, more preferably 1 to 2 , Is preferably an integer of 1.

於本發明之較佳之一態樣中，式(4)係由式(4')所表示： [化35]

Figure 02_image073
[式(4')中，R16 ～R23 相互獨立地表示氫原子或碳數1～6之氟烷基，其中，R16 ～R19 之至少1個及R20 ～R23 之至少1個表示碳數1～6之氟烷基，＊表示鍵結鍵] 就容易提高光學膜之外觀品質、彈性模數及全光線透過率之觀點而言，式(4')中，更佳為至少R18 及R20 表示碳數1～6之氟烷基，進而較佳為R18 及R20 表示碳數1～6之氟烷基且R16 、R17 、R19 、R21 、R22 及R23 表示氫原子。又，於上述態樣中，碳數1～6之氟烷基較佳為碳數1～6之全氟烷基，更佳為碳數1～4之全氟烷基，進而較佳為三氟甲基或五氟乙基，尤佳為三氟甲基。In a preferred aspect of the present invention, formula (4) is represented by formula (4'): [化35]
Figure 02_image073
[In formula (4'), R 16 to R 23 independently represent a hydrogen atom or a fluoroalkyl group having 1 to 6 carbon atoms, wherein at least one of R 16 to R 19 and at least one of R 20 to R 23 A represents a fluoroalkyl group with carbon number of 1 to 6, and * represents a bonding bond] From the viewpoint of easily improving the appearance quality, elastic modulus and total light transmittance of the optical film, the formula (4') is more preferably At least R 18 and R 20 represent a fluoroalkyl group having 1 to 6 carbon atoms, and more preferably R 18 and R 20 represent a fluoroalkyl group having 1 to 6 carbon atoms and R 16 , R 17 , R 19 , R 21 , R 22 and R 23 represent a hydrogen atom. Furthermore, in the above aspect, the fluoroalkyl group having 1 to 6 carbon atoms is preferably a perfluoroalkyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably three Fluoromethyl or pentafluoroethyl, particularly preferably trifluoromethyl.

於本發明之較佳之一態樣中，式(4')係由式(4")所表示： [化36]

Figure 02_image075
[式(4")中之＊表示鍵結鍵] 再者，式(4")相當於式(4')中之R18 及R20 表示三氟甲基且R16 、R17 、R19 、R21 、R22 及R23 表示氫原子之式。In a preferred aspect of the present invention, the formula (4') is represented by the formula (4"): [化36]
Figure 02_image075
[The * in the formula (4") represents the bonding bond] Furthermore, the formula (4") corresponds to the formula (4') where R 18 and R 20 represent trifluoromethyl and R 16 , R 17 , R 19 , R 21 , R 22 and R 23 represent the formula of a hydrogen atom.

於聚醯胺醯亞胺系樹脂包含式(3)所表示之結構單元(c1)作為源自二胺化合物之結構單元(c)之本發明之較佳之一態樣中，就容易提高光學膜之外觀品質以及全光線透過率及彈性模數、容易提高清漆之穩定性之觀點而言，於將聚醯胺醯亞胺系樹脂中所包含之結構單元(c)之合計設為100莫耳%時，式(3)所表示之結構單元(c1)之比率較佳為50～98莫耳%，更佳為60～95莫耳%，進而較佳為70～94莫耳%。可為聚醯胺醯亞胺系樹脂中所包含之結構單元(c)之一部分為結構單元(c1)，亦可為結構單元(c)全部為結構單元(c1)，就容易提高光學膜之外觀品質以及全光線透過率及彈性模數、容易提高清漆之穩定性之觀點而言，較佳為聚醯胺醯亞胺系樹脂中所包含之結構單元(c)之一部分為結構單元(c1)。再者，結構單元(c)及結構單元(c1)之含量例如可使用1 H-NMR進行測定或者亦可根據原料之添加比而算出。In a preferred aspect of the present invention in which the polyimide imine-based resin contains the structural unit (c1) represented by the formula (3) as the structural unit (c) derived from the diamine compound, it is easy to improve the optical film From the viewpoint of the appearance quality, total light transmittance and elastic modulus, and easy improvement of the stability of the varnish, the total of the structural units (c) contained in the polyimide resin is set to 100 mol %, the ratio of the structural unit (c1) represented by formula (3) is preferably 50-98 mol%, more preferably 60-95 mol%, and still more preferably 70-94 mol%. It can be that part of the structural unit (c) contained in the polyimide-imide resin is the structural unit (c1), or all of the structural unit (c) is the structural unit (c1), which can easily improve the optical film From the viewpoint of appearance quality, total light transmittance and elastic modulus, and easy improvement of the stability of the varnish, it is preferable that a part of the structural unit (c) contained in the polyimide resin is the structural unit (c1 ). In addition, the content of the structural unit (c) and the structural unit (c1) can be measured using 1 H-NMR, for example, or can be calculated based on the addition ratio of the raw materials.

就容易提高光學膜之外觀品質以及全光線透過率及彈性模數、容易提高清漆之穩定性之觀點而言，本發明之光學膜中所包含之聚醯胺醯亞胺系樹脂較佳為包含式(a)中之Y係由式(1)所表示之結構單元(a1)作為源自四羧酸化合物之結構單元，包含式(2)所表示之結構單元(b1)作為源自二羧酸化合物之結構單元，且包含式(3)所表示之結構單元(c1)作為源自二胺化合物之結構單元。From the viewpoints of easily improving the appearance quality, total light transmittance and elastic modulus of the optical film, and easily improving the stability of the varnish, the polyimide-based resin contained in the optical film of the present invention preferably contains Y in the formula (a) is the structural unit (a1) represented by the formula (1) as the structural unit derived from the tetracarboxylic acid compound, and includes the structural unit (b1) represented by the formula (2) as the structural unit derived from the dicarboxylic acid The structural unit of the acid compound, and includes the structural unit (c1) represented by the formula (3) as the structural unit derived from the diamine compound.

於本發明之較佳之一態樣中，聚醯胺醯亞胺系樹脂進而包含選自由如下結構單元所組成之群中之至少1種結構單元：式(b)中之Z係由式(5)： [化37]

Figure 02_image077
[式(5)中，Ar1 相互獨立地表示可具有取代基之二價芳香族基， V表示單鍵、-O-、二苯基亞甲基、碳數1～12之直鏈狀、支鏈狀或脂環式之二價烴基、-SO2 -、-S-、-CO-或-N(R12 )-，此處，該烴基中所包含之氫原子可相互獨立地被取代為鹵素原子，R12 表示氫原子、或可經鹵素原子取代之碳數1～12之烷基， m表示1～3之整數，其中，於m為2或3之情形時所存在之複數個V可相互相同，亦可不同， ＊表示鍵結鍵] 所表示之結構單元、式(c)中之X係由式(5)所表示之結構單元、及式(a)中之Y係由式(6)： [化38]
Figure 02_image079
[式(6)中，Ar2 相互獨立地表示可具有取代基之三價芳香族基， s表示0～2之整數， Ar1 、V及＊如式(5)中之Ar1 、V及＊所定義，其中，於s為2之情形時所存在之複數個V及Ar1 可分別相互相同，亦可不同，其中式(6)中之V並非為單鍵] 所表示之結構單元。再者，於本說明書中，將可作為源自二羧酸化合物之結構單元而包含之式(b)中之Z係由式(5)所表示之結構單元亦稱為「結構單元(b3)」，將可作為源自二胺化合物之結構單元而包含之式(c)中之X係由式(5)所表示之結構單元亦稱為「結構單元(c2)」，將可作為源自四羧酸化合物之結構單元而包含之式(a)中之Y係由式(6)所表示之結構單元亦稱為「結構單元(a2)」。本發明之光學膜中所包含之聚醯胺醯亞胺系樹脂至少具有選自由上述結構單元(a1)及結構單元(b1)所組成之群中之至少1種結構單元(較佳為結構單元(a1))，於較佳之一態樣中，進而包含選自由結構單元(b3)、結構單元(c2)及結構單元(a2)所組成之群中之至少1種結構單元。於該態樣中，除式(1)所表示之結構單元以外，選自由式(5)所表示之結構單元及式(6)所表示之結構單元所組成之群中之至少1種結構單元亦包含於聚醯胺醯亞胺系樹脂中。再者，結構單元(b3)係作為結構單元(b)而包含，結構單元(c2)係作為結構單元(c)而包含，結構單元(a2)係作為結構單元(a)而包含。於聚醯胺醯亞胺系樹脂包含結構單元(b3)作為結構單元(b)之情形時，該樹脂可包含結構單元(b1)，亦可包含結構單元(b2)，可包含結構單元(b1)及(b2)，亦可不包含結構單元(b1)及(b2)。又，於聚醯胺醯亞胺系樹脂包含結構單元(c2)作為結構單元(c)之情形時，該樹脂可包含結構單元(c1)，亦可不包含結構單元(c1)。In a preferred aspect of the present invention, the polyimide imine-based resin further comprises at least one structural unit selected from the group consisting of the following structural units: Z in formula (b) is derived from formula (5) ): [化37]
Figure 02_image077
[In formula (5), Ar 1 independently represents a divalent aromatic group that may have a substituent, V represents a single bond, -O-, diphenylmethylene, a linear chain with 1 to 12 carbon atoms, A branched or alicyclic divalent hydrocarbon group, -SO 2 -, -S-, -CO- or -N(R 12 )-, where the hydrogen atoms contained in the hydrocarbon group can be substituted independently of each other It is a halogen atom, R 12 represents a hydrogen atom, or an alkyl group with 1 to 12 carbon atoms which can be substituted by a halogen atom, and m represents an integer of 1 to 3, where there are plural when m is 2 or 3 V can be the same or different from each other, * represents the structural unit represented by the bonding bond], X in formula (c) is represented by the structural unit represented by formula (5), and Y in formula (a) is represented by Formula (6): [化38]
Figure 02_image079
[In formula (6), Ar 2 independently represents a trivalent aromatic group which may have a substituent, s represents an integer of 0-2, Ar 1 , V and * are as in the formula (5) Ar 1 , V and * Defined, where the plurality of V and Ar 1 existing when s is 2 may be the same as or different from each other, and V in formula (6) is not a single bond]. Furthermore, in this specification, the structural unit represented by formula (5) in formula (b) that can be included as a structural unit derived from a dicarboxylic acid compound is also referred to as "structural unit (b3) ", the structural unit represented by formula (5) in formula (c) that can be included as a structural unit derived from a diamine compound is also called "structural unit (c2)", which can be used as a structural unit derived from The structural unit of the tetracarboxylic acid compound and the Y in the formula (a) included in the structural unit represented by the formula (6) is also called "structural unit (a2)". The polyamide imine resin contained in the optical film of the present invention has at least one structural unit (preferably a structural unit) selected from the group consisting of the above-mentioned structural unit (a1) and structural unit (b1) (a1)), in a preferred aspect, further comprising at least one structural unit selected from the group consisting of structural unit (b3), structural unit (c2) and structural unit (a2). In this aspect, in addition to the structural unit represented by formula (1), at least one structural unit selected from the group consisting of the structural unit represented by formula (5) and the structural unit represented by formula (6) It is also included in polyimide-based resins. In addition, the structural unit (b3) is included as the structural unit (b), the structural unit (c2) is included as the structural unit (c), and the structural unit (a2) is included as the structural unit (a). When the polyimide imine-based resin includes the structural unit (b3) as the structural unit (b), the resin may include the structural unit (b1), may also include the structural unit (b2), and may include the structural unit (b1) ) And (b2) may not contain the structural units (b1) and (b2). In addition, when the polyimide-based resin includes the structural unit (c2) as the structural unit (c), the resin may include the structural unit (c1), or may not include the structural unit (c1).

此處，式(5)所表示之結構單元及式(6)所表示之結構單元由於包含表示單鍵(其中式(6)中之V並非為單鍵)、-O-、二苯基亞甲基、碳數1～12之直鏈狀、支鏈狀或脂環式之二價烴基、-SO2 -、-S-、-CO-或-N(R12 )-之二價連結基V，故而係柔軟性較高之結構。於聚醯胺醯亞胺系樹脂進而包含如上述之柔軟性較高之結構之情形時，容易降低聚醯胺醯亞胺系樹脂之分子間之相互作用。其結果為容易提高包含聚醯胺醯亞胺系樹脂之光學膜之光學特性。又，亦容易提高聚醯胺醯亞胺系樹脂之清漆之狀態下之穩定性。Here, the structural unit represented by the formula (5) and the structural unit represented by the formula (6) include a single bond (wherein V in the formula (6) is not a single bond), -O-, diphenylene A methyl group, a linear, branched or alicyclic divalent hydrocarbon group with 1 to 12 carbons, a divalent linking group of -SO 2 -, -S-, -CO- or -N(R 12 )- V, so it is a more flexible structure. When the polyimide-based resin further includes a structure with higher flexibility as described above, it is easy to reduce the intermolecular interaction of the polyimide-based resin. As a result, it is easy to improve the optical properties of the optical film containing the polyimide-based resin. In addition, it is easy to improve the stability of the varnish of the polyimide resin.

於聚醯胺醯亞胺系樹脂具有選自由如下結構單元所組成之群中之至少1種結構單元：式(b)中之Z係由式(5)所表示之源自二羧酸化合物之結構單元(b2)、式(c)中之X係由式(5)所表示之源自二胺化合物之結構單元(c2)、及式(a)中之Y係由式(6)所表示之源自四羧酸化合物之結構單元(a2)之情形時，結構單元(b2)、結構單元(c2)及結構單元(a2)之合計量基於聚醯胺醯亞胺系樹脂中所包含之總結構單元，較佳為1～25莫耳%，更佳為2～20莫耳%，進而較佳為3～15莫耳%。若該合計量為上述範圍內，則容易提高清漆之穩定性，容易提高光學膜之加工性及全光線透過率。再者，於該態樣中，所謂結構單元(b2)、結構單元(c2)及結構單元(a2)之合計量，並非意指聚醯胺醯亞胺系樹脂全部具有該等3種結構單元，聚醯胺醯亞胺系樹脂只要具有選自由結構單元(b2)、結構單元(c2)及結構單元(a2)所組成之群中之至少1種結構單元即可。 The polyamide imine resin has at least one structural unit selected from the group consisting of the following structural units: Z in formula (b) is derived from a dicarboxylic acid compound represented by formula (5) Structural unit (b2), X in formula (c) is represented by formula (5) derived from structural unit (c2) of diamine compound, and Y in formula (a) is represented by formula (6) In the case of the structural unit (a2) derived from the tetracarboxylic acid compound, the total amount of the structural unit (b2), the structural unit (c2) and the structural unit (a2) is based on the polyamide imine resin contained The total structural unit is preferably 1-25 mol%, more preferably 2-20 mol%, and still more preferably 3-15 mol%. If the total amount is within the above range, the stability of the varnish is easily improved, and the processability and total light transmittance of the optical film are easily improved. Furthermore, in this aspect, the so-called total amount of structural unit (b2), structural unit (c2) and structural unit (a2) does not mean that all polyimide-based resins have these three structural units The polyimide imine resin only needs to have at least one structural unit selected from the group consisting of structural unit (b2), structural unit (c2), and structural unit (a2).

又，於聚醯胺醯亞胺系樹脂具有選自由結構單元(b2)、結構單元(c2)、及結構單元(a2)所組成之群中之至少1種結構單元之情形時，結構單元(b2)、結構單元(c2)及結構單元(a2)之合計莫耳量於將聚醯胺醯亞胺系樹脂中所包含之式(a)中之Y係由式(1)所表示之結構單元(a1)及式(b)中之Z係由式(1)所表示之結構單元(b1)之合計量設為1莫耳時，較佳為0.01～1.0莫耳，更佳為0.02～0.50莫耳，進而較佳為0.05～0.20莫耳。若該合計莫耳量為上述下限以上，則容易提高對清漆之溶解性。又，若該合計莫耳量為上述上限以下，則容易提高彈性模數。再者，於該態樣中，上述合計莫耳量亦並非意指聚醯胺醯亞胺系樹脂全部具有該等結構單元。 Moreover, when the polyimide imine resin has at least one structural unit selected from the group consisting of structural unit (b2), structural unit (c2), and structural unit (a2), structural unit ( b2), the total molar amount of the structural unit (c2) and the structural unit (a2) is the structure represented by the formula (1) in the formula (a) contained in the polyimide imine resin When the total amount of Z in the unit (a1) and formula (b) is 1 mol of the structural unit (b1) represented by formula (1), it is preferably 0.01 to 1.0 mol, more preferably 0.02 to 0.50 mol, more preferably 0.05 to 0.20 mol. If the total molar amount is more than the above lower limit, it is easy to improve the solubility to varnish. Moreover, if the total molar amount is equal to or less than the above upper limit, it is easy to increase the elastic modulus. Furthermore, in this aspect, the above-mentioned total molar amount does not mean that all polyimide-based resins have these structural units.

式(5)及式(6)中之Ar1 表示可具有取代基之二價芳香族基。二價芳香族基係單環式芳香族環、縮合多環式芳香族環或集合環芳香族環之2個氫原子被取代為鍵結鍵之基。二價芳香族基可包含僅由碳原子形成環(單環、縮合多環或集合環)之芳香族環，亦可包含包括碳原子以外之原子而形成環之雜芳環。作為碳原子以外之原子，例如可列舉：氮原子、硫原子及氧原子。形成芳香族環之碳原子及碳原子以外之原子之合計個數並無特別限定，較佳為5～18，更佳為5～14，進而較佳為5～13，尤佳為5～12。作為單環式芳香族環、縮合多環式芳香族環及集合環芳香族環之例，可列舉關於式(2)中之Z1 而於上述所記載之例。Ar 1 in formula (5) and formula (6) represents a divalent aromatic group which may have a substituent. The divalent aromatic group is a group where two hydrogen atoms of a monocyclic aromatic ring, a condensed polycyclic aromatic ring, or an assembling aromatic ring are replaced with a bonding bond. The divalent aromatic group may include an aromatic ring (monocyclic, condensed polycyclic, or collective ring) formed only by carbon atoms, or may include a heteroaromatic ring including atoms other than carbon atoms to form a ring. Examples of atoms other than carbon atoms include nitrogen atoms, sulfur atoms, and oxygen atoms. The total number of carbon atoms and atoms other than carbon atoms forming the aromatic ring is not particularly limited, but is preferably 5-18, more preferably 5-14, still more preferably 5-13, and particularly preferably 5-12 . As an example of a monocyclic aromatic ring, a condensed polycyclic aromatic ring, and an aggregate ring aromatic ring, the example described above about Z 1 in formula (2) can be mentioned.

就容易提高光學膜之彈性模數及全光線透過率之觀點而言，可具有取代基之二價芳香族基較佳為芳香族烴環之2個氫原子被取代為鍵結鍵之基，更佳為苯、聯苯、聯三苯或聯四苯之2個氫原子被取代為鍵結鍵之基，進而較佳為苯或聯苯之2個氫原子被取代為鍵結鍵之基。From the standpoint of easily improving the elastic modulus and total light transmittance of the optical film, the divalent aromatic group that may have a substituent is preferably that the two hydrogen atoms of the aromatic hydrocarbon ring are substituted as a bonding bond group, More preferably, two hydrogen atoms of benzene, biphenyl, terphenyl or bitetraphenyl are substituted as a bonding bond group, and more preferably, two hydrogen atoms of benzene or biphenyl are substituted as a bonding bond group .

式(5)及式(6)中之Ar1 所表示之二價芳香族基可具有取代基。作為取代基，例如可列舉：(i)碳數1～12之烷基、(ii)碳數1～12之烷氧基、(iii)碳數6～12之芳基、(iv)碳數6～12之芳氧基、(v)碳數1～12之羰基、(vi)碳數1～12之氧羰基、或(vii)鹵素基。再者，上述取代基中所包含之氫原子亦可進而相互獨立地被取代為鹵素原子、碳數1～4之烷基、碳數1～4之烷氧基、羥基、或羧基。該二價芳香族基可具有至少1種上述(i)～(vii)之取代基、及上述(i)～(vii)之取代基中所包含之至少1個氫原子進而相互獨立地被取代為鹵素原子、碳數1～4之烷基、碳數1～4之烷氧基、羥基、或羧基之基，亦可不具有取代基。就製造具有較高之彈性模數之光學膜之觀點而言，式(5)及式(6)中之Ar1 所表示之二價芳香族基較佳為不具有取代基。The divalent aromatic group represented by Ar 1 in formula (5) and formula (6) may have a substituent. Examples of the substituent include: (i) alkyl having 1 to 12 carbons, (ii) alkoxy having 1 to 12 carbons, (iii) aryl having 6 to 12 carbons, and (iv) carbon number 6-12 aryloxy group, (v) carbonyl group with 1-12 carbons, (vi) oxycarbonyl group with 1-12 carbons, or (vii) halogen group. In addition, the hydrogen atoms contained in the above substituents may be further independently substituted with halogen atoms, C1-C4 alkyl groups, C1-C4 alkoxy groups, hydroxyl groups, or carboxyl groups. The divalent aromatic group may have at least one of the substituents of (i) to (vii) and at least one hydrogen atom contained in the substituents of (i) to (vii), which may be substituted independently of each other It is a halogen atom, an alkyl group having 1 to 4 carbons, an alkoxy group having 1 to 4 carbons, a hydroxyl group, or a carboxyl group, and may not have a substituent. From the viewpoint of manufacturing an optical film having a higher elastic modulus, the divalent aromatic group represented by Ar 1 in formula (5) and formula (6) preferably has no substituent.

作為(i)碳數1～12之烷基、(ii)碳數1～12之烷氧基及(iii)碳數6～12之芳基及(iv)碳數6～12之芳氧基，可列舉關於式(2)中之Z1 所表示之二價芳香族基可具有之取代基而於上述所例示之基。As (i) C1-C12 alkyl group, (ii) C1-C12 alkoxy group, (iii) C6-C12 aryl group and (iv) C6-C12 aryloxy group Examples include the groups exemplified above regarding the substituents that the divalent aromatic group represented by Z 1 in formula (2) may have.

(v)碳數1～12之羰基係由＊-CO-Rd 或＊-Re -CO-Rd 所表示之基。作為Rd ，可列舉關於(i)碳數1～12之烷基所記載之基，作為Re ，可列舉關於(i)碳數1～12之烷基所記載之基之至少1個氫原子被取代為鍵結鍵之碳數1～12之二價伸烷基。上述碳數1～12之羰基亦可為至少1個氫原子相互獨立地被取代為鹵素原子、碳數1～4之烷基、碳數1～4之烷氧基、羥基、或羧基之基。作為鹵素原子，可列舉上述所記載之原子。此處，於碳數1～12之羰基經包含碳原子之取代基取代之情形時，該取代基中所包含之碳原子數不包含於碳數1～12之羰基之碳數中。(v) The carbonyl group having 1 to 12 carbons is a group represented by *-CO-R d or *-R e -CO-R d . Examples of R d include the groups described for (i) alkyl groups having 1 to 12 carbons, and examples of R e include at least one hydrogen of the groups described for (i) alkyl groups having 1 to 12 carbons. The atom is substituted with a divalent alkylene group having 1 to 12 carbon atoms. The aforementioned carbonyl group with 1 to 12 carbons may be a group in which at least one hydrogen atom is independently substituted with a halogen atom, an alkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons, a hydroxyl group, or a carboxyl group. . Examples of the halogen atom include the atoms described above. Here, when the carbonyl group having 1 to 12 carbon atoms is substituted with a substituent containing carbon atoms, the number of carbon atoms contained in the substituent is not included in the number of carbon atoms in the carbonyl group having 1 to 12 carbon atoms.

(vi)碳數1～12之氧羰基係由＊-CO-O-Rd 、＊-Re -CO-O-Rd 、＊-O-CO-Rd 、或-Re -O-CO-Rd 所表示之基。作為Rd ，可列舉關於(i)碳數1～12之烷基所記載之基，作為Re ，可列舉關於(i)碳數1～12之烷基所記載之基之至少1個氫原子被取代為鍵結鍵之碳數1～12之二價伸烷基。上述碳數1～12之氧羰基亦可為至少1個氫原子相互獨立地被取代為鹵素原子、碳數1～4之烷基、碳數1～4之烷氧基、羥基、或羧基之基。作為鹵素原子，可列舉上述所記載之原子。此處，於碳數1～12之氧羰基經包含碳原子之取代基取代之情形時，該取代基中所包含之碳原子數不包含於碳數1～12之氧羰基之碳數中。(vi) The oxycarbonyl group with 1 to 12 carbons is composed of *-CO-OR d , *-R e -CO-OR d , *-O-CO-R d , or -R e -O-CO-R d The base expressed. Examples of R d include the groups described for (i) alkyl groups having 1 to 12 carbons, and examples of R e include at least one hydrogen of the groups described for (i) alkyl groups having 1 to 12 carbons. The atom is substituted with a divalent alkylene group having 1 to 12 carbon atoms. The above-mentioned oxycarbonyl group having 1 to 12 carbons may be one of at least one hydrogen atom independently substituted with a halogen atom, an alkyl group having 1 to 4 carbons, an alkoxy group having 1 to 4 carbons, a hydroxyl group, or a carboxyl group. base. Examples of the halogen atom include the atoms described above. Here, when the oxycarbonyl group having 1 to 12 carbon atoms is substituted with a substituent containing carbon atoms, the number of carbon atoms contained in the substituent is not included in the carbon number of the oxycarbonyl group having 1 to 12 carbon atoms.

作為(vii)鹵素基，可列舉：氟基、氯基、溴基或碘基。(Vii) The halogen group includes a fluoro group, a chloro group, a bromo group, or an iodo group.

式(6)中之Ar2 表示可具有取代基之三價芳香族基。三價芳香族基係單環式芳香族環、縮合多環式芳香族環或集合環芳香族環之3個氫原子被取代為鍵結鍵之基。三價芳香族基可包含僅由碳原子形成環(單環、縮合多環或集合環)之芳香族環，亦可包含包括碳原子以外之原子而形成環之雜芳環。作為碳原子以外之原子，例如可列舉：氮原子、硫原子及氧原子。形成芳香族環之碳原子及碳原子以外之原子之合計個數並無特別限定，較佳為5～18，更佳為5～14，進而較佳為5～13，尤佳為5～12。作為三價芳香族基中之單環式芳香族環、縮合多環式芳香族環或集合環芳香族環，可列舉關於上述Ar1 所記載者。作為三價芳香族基可具有之取代基，可列舉關於上述Ar1 所記載之取代基，關於Ar1 而記載之較佳之記載同樣地適合Ar2 。Ar 2 in formula (6) represents a trivalent aromatic group which may have a substituent. The trivalent aromatic group is a monocyclic aromatic ring, a condensed polycyclic aromatic ring, or a condensed polycyclic aromatic ring, and three hydrogen atoms are substituted into a bonding group. The trivalent aromatic group may include an aromatic ring (monocyclic, condensed polycyclic or collective ring) formed only by carbon atoms, and may include a heteroaromatic ring including atoms other than carbon atoms to form a ring. Examples of atoms other than carbon atoms include nitrogen atoms, sulfur atoms, and oxygen atoms. The total number of carbon atoms and atoms other than carbon atoms forming the aromatic ring is not particularly limited, but is preferably 5-18, more preferably 5-14, still more preferably 5-13, and particularly preferably 5-12 . As the monocyclic aromatic ring, the condensed polycyclic aromatic ring, or the condensed ring aromatic ring in the trivalent aromatic group, those described with respect to Ar 1 can be mentioned. Examples of the substituents that the trivalent aromatic group may have include the substituents described for Ar 1 above, and the preferable descriptions for Ar 1 are similarly applicable to Ar 2 .

就容易提高光學膜之外觀品質、彈性模數及全光線透過率之觀點而言，可具有取代基之三價芳香族基較佳為芳香族烴環之3個氫原子被取代為鍵結鍵之基，更佳為苯、聯苯、聯三苯或聯四苯之3個氫原子被取代為鍵結鍵之基，進而較佳為苯或聯苯之3個氫原子被取代為鍵結鍵之基。From the viewpoint of easily improving the appearance quality, elastic modulus, and total light transmittance of the optical film, the trivalent aromatic group that may have a substituent is preferably that the three hydrogen atoms of the aromatic hydrocarbon ring are substituted as bonding bonds More preferably, the three hydrogen atoms of benzene, biphenyl, terphenyl or bitetraphenyl are substituted as bonding bonds, and more preferably, the 3 hydrogen atoms of benzene or biphenyl are substituted as bonds The base of the key.

於式(5)中之m為1以上之情形及式(6)中之s為2之情形時所存在之複數個Ar1 可相互相同，亦可不同。又，式(6)中所存在之複數個Ar2 可相互相同，亦可不同。When m is 1 or more in formula (5) and when s is 2 in formula (6), the plurality of Ar 1 may be the same or different. In addition, the plurality of Ar 2 in the formula (6) may be the same or different from each other.

式(5)中之m表示1～3之整數。就提高彈性模數、確保對清漆之溶解性之觀點而言，較佳為1或2，更佳為1。式(5)中之＊表示鍵結鍵。M in formula (5) represents an integer of 1-3. From the viewpoint of improving the modulus of elasticity and ensuring the solubility to the varnish, 1 or 2 is preferable, and 1 is more preferable. The * in formula (5) represents a bonding bond.

式(6)中之s表示0～2之整數，就確保對清漆之溶解性、確保較高之透過率之觀點而言，較佳為0或1，更佳為0。式(6)中之＊表示鍵結鍵。In the formula (6), s represents an integer of 0-2. From the viewpoint of ensuring the solubility to the varnish and ensuring a higher transmittance, it is preferably 0 or 1, and more preferably 0. The * in formula (6) represents a bonding bond.

式(5)及式(6)中之V表示單鍵(其中式(6)中之V並非為單鍵)、-O-、二苯基亞甲基、碳數1～12之直鏈狀、支鏈狀或脂環式之二價烴基、-SO2 -、-S-、-CO-或-N(R12 )-，此處，該烴基中所包含之氫原子可相互獨立地被取代為鹵素原子，R12 表示氫原子、或可經鹵素原子取代之碳數1～12之烷基。作為碳數1～12之直鏈狀、支鏈狀或脂環式之烷基，可列舉關於式(1)中之Ra 之碳數1～12之烷基所記載之基。V in formula (5) and formula (6) represents a single bond (wherein V in formula (6) is not a single bond), -O-, diphenylmethylene, straight chain with carbon number 1-12 , Branched or alicyclic divalent hydrocarbon group, -SO 2 -, -S-, -CO- or -N(R 12 )-, where the hydrogen atoms contained in the hydrocarbon group can be mutually independently It is substituted by a halogen atom, and R 12 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may be substituted by a halogen atom. The carbon number of 1 to 12 linear, branched or alicyclic alkyl group of, include an alkyl group on the carbon number of R a formula (1) of the 1 to 12 described in the.

關於式(5)及式(6)中之V，作為碳數1～12之直鏈狀、支鏈狀或脂環式之二價烴基，可列舉碳數1～12之直鏈狀、支鏈狀或脂環式之烷基之至少1個氫原子被取代為鍵結鍵之基。再者，作為該碳數1～12之直鏈狀、支鏈狀或脂環式之烷基，例如可列舉：甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、2-甲基丁基、3-甲基丁基、2-乙基丙基、正己基、正庚基、正辛基、第三辛基、正壬基、正癸基、環戊基、環己基等。碳數1～12之二價烴基亦可為直鏈狀之伸烷基、支鏈狀之伸烷基、或包含脂環式烴結構之脂環式之伸烷基。碳數1～12之二價烴基之碳數較佳為1～6，更佳為1～4，進而較佳為1～3。上述碳數1～12之二價烴基亦可為至少1個氫原子相互獨立地被取代為鹵素原子之基。作為鹵素原子，可列舉：氟原子、氯原子、溴原子、碘原子。Regarding V in formula (5) and formula (6), as a linear, branched, or alicyclic divalent hydrocarbon group having 1 to 12 carbons, there can be exemplified linear and branched hydrocarbon groups having 1 to 12 carbons. At least one hydrogen atom of the chain or alicyclic alkyl group is substituted with a bonding group. Furthermore, examples of the linear, branched, or alicyclic alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, and second Butyl, tertiary butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 2-ethylpropyl, n-hexyl, n-heptyl, n-octyl, tertiary octyl, n Nonyl, n-decyl, cyclopentyl, cyclohexyl, etc. The divalent hydrocarbon group having 1 to 12 carbon atoms may also be a linear alkylene group, a branched chain alkylene group, or an alicyclic alkylene group containing an alicyclic hydrocarbon structure. The carbon number of the divalent hydrocarbon group having 1 to 12 carbons is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 3. The above-mentioned divalent hydrocarbon group having 1 to 12 carbon atoms may be a group in which at least one hydrogen atom is independently substituted with a halogen atom. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

於式(5)及式(6)中，於Ar1 、Ar2 及V分別存在複數個之情形時，該等可分別相互相同，亦可不同，但就容易合成聚醯胺醯亞胺系樹脂之觀點而言，較佳為所存在之複數個Ar1 相互相同、所存在之複數個Ar2 相互相同、及/或所存在之複數個V相互相同。In formulas (5) and (6), when there are plural Ar 1 , Ar 2 and V respectively, these may be the same as each other or different, but it is easy to synthesize the polyimide imine series From the viewpoint of the resin, it is preferable that the plurality of Ar 1 present are the same as each other, the plurality of Ar 2 present are the same as each other, and/or the plurality of V present are the same as each other.

於本發明之較佳之一態樣中，式(5)及式(6)較佳為由式(7)所表示： [化39]

Figure 02_image081
[式(7)中，R1 相互獨立地表示氫原子、碳數1～12之烷基、碳數1～12之烷氧基或碳數6～12之芳基，R1 中所包含之氫原子可相互獨立地被取代為鹵素原子， R＊ 表示R1 或鍵結鍵， ＊表示鍵結鍵， V表示單鍵(其中式(6)中之V並非為單鍵)、-O-、二苯基亞甲基、碳數1～12之直鏈狀、支鏈狀或脂環式之二價烴基、-SO2 -、-S-、-CO-或-N(R12 )-，此處，該烴基中所包含之氫原子可相互獨立地被取代為鹵素原子，R12 表示氫原子、或可經鹵素原子取代之碳數1～12之烷基] 再者，於式(5)係由式(7)所表示之情形時，式(7)中之鍵結鍵變成2個，故而R＊ 表示R1 。又，於式(6)係由式(7)所表示之情形時，式(7)中之鍵結鍵變成4個，故而R＊ 表示鍵結鍵。又，關於式(7)中之R1 ，與式(5)中之Ar1 及式(6)中之Ar2 可具有之取代基相關之記載同樣地符合，較佳之記載亦同樣地符合。又，關於式(7)中之V，與式(5)及式(6)中之V相關之記載亦同樣地符合。In a preferred aspect of the present invention, formula (5) and formula (6) are preferably represented by formula (7): [化39]
Figure 02_image081
[In formula (7), R 1 independently represents a hydrogen atom, a C 1-12 alkyl group, a C 1-12 alkoxy group, or a C 6-12 aryl group, which is contained in R 1 Hydrogen atoms can be substituted with halogen atoms independently of each other, R ＊ represents R 1 or bonding bond, ＊represents bonding bond, V represents a single bond (wherein V in formula (6) is not a single bond), -O- , Diphenylmethylene, straight-chain, branched-chain or alicyclic divalent hydrocarbon group with 1-12 carbons, -SO 2 -, -S-, -CO- or -N(R 12 )- Here, the hydrogen atoms contained in the hydrocarbon group may be independently substituted with halogen atoms, and R 12 represents a hydrogen atom or an alkyl group with 1 to 12 carbon atoms which may be substituted by a halogen atom] Furthermore, in the formula ( 5) In the case represented by the formula (7), the bonding bond in the formula (7) becomes two, so R * represents R 1 . Furthermore, when the formula (6) is represented by the formula (7), the bonding bond in the formula (7) becomes 4, so R * represents a bonding bond. Further, in the middle of about the formula (7) R 1, and the formula (5) in the Ar 1 and the formula (6) Ar 2 may have the substituent group associated the described similarly meet, preferably the described equally conform. In addition, regarding V in formula (7), the descriptions related to V in formulas (5) and (6) also conform in the same way.

於本發明之較佳之一態樣中，於聚醯胺醯亞胺系樹脂包含式(c)中之X係由式(5)或式(7)所表示之結構單元(c2)作為源自二胺化合物之結構單元之情形時或進而包含式(a)中之Y係由式(6)或式(7)所表示之結構單元(a2)作為源自四羧酸化合物之結構單元之情形時，就光學膜之外觀品質、彈性模數、全光線透過率、表面硬度及耐彎曲性之觀點及清漆之穩定性之觀點而言，式(5)、式(6)及式(7)中之V較佳為表示-O-、二苯基亞甲基、碳數1～12之直鏈狀、支鏈狀或脂環式之二價烴基、-SO2 -、-S-、-CO-或-N(R12 )-，更佳為表示-O-、二苯基亞甲基、碳數1～12之直鏈狀、支鏈狀或脂環式之二價烴基、或碳數1～12之二價烴基中所包含之氫原子被取代為鹵素原子之基，進而較佳為表示碳數1～12之二價烴基、或碳數1～12之二價烴基中所包含之氫原子被取代為鹵素原子之基。In a preferred aspect of the present invention, the polyimide imine resin contains the structural unit (c2) represented by the formula (5) or the formula (7) in the formula (c) as derived from In the case of the structural unit of the diamine compound, or when it further includes the structural unit (a2) represented by the formula (6) or the formula (7) in the formula (a) as the structural unit derived from the tetracarboxylic acid compound When considering the appearance quality, elastic modulus, total light transmittance, surface hardness and bending resistance of the optical film and the stability of the varnish, formula (5), formula (6) and formula (7) The V in it preferably represents -O-, diphenylmethylene, a linear, branched or alicyclic divalent hydrocarbon group with 1 to 12 carbons, -SO 2 -, -S-,- CO- or -N(R 12 )-, more preferably represents -O-, diphenylmethylene, a linear, branched or alicyclic divalent hydrocarbon group with 1 to 12 carbons, or carbon A group in which hydrogen atoms contained in a divalent hydrocarbon group of 1 to 12 is substituted with a halogen atom, and further preferably represents a divalent hydrocarbon group of 1 to 12 carbons or a divalent hydrocarbon group of 1 to 12 carbons The hydrogen atom is replaced with a halogen atom.

於該態樣中，式(5)、式(6)及式(7)中之V進而較佳為碳數1～12之直鏈狀、支鏈狀或脂環式之伸烷基之至少1個氫原子被取代為鹵素原子(較佳為氟原子)之基(較佳為碳數1～12之氟伸烷基)，進而更佳為碳數1～12之直鏈狀、支鏈狀或脂環式之伸烷基之所有氫原子被取代為鹵素原子(較佳為氟原子)之基(較佳為碳數1～12之全氟伸烷基，尤佳為二三氟甲基亞甲基)。In this aspect, V in formula (5), formula (6) and formula (7) is more preferably at least one of linear, branched or alicyclic alkylenes having 1 to 12 carbon atoms One hydrogen atom is substituted with a halogen atom (preferably a fluorine atom) (preferably a fluoroalkylene group with 1 to 12 carbons), and more preferably a straight chain or branched chain with 1 to 12 carbons All hydrogen atoms of the alicyclic or alicyclic alkylene groups are substituted with halogen atoms (preferably fluorine atoms) (preferably perfluoroalkylene groups with 1 to 12 carbon atoms, especially ditrifluoromethyl) Methylene).

於該態樣中，式(7)較佳為由式(7')或式(7")所表示： [化40]

Figure 02_image083
[式(7')中，R＊ 表示氫原子或鍵結鍵，＊表示鍵結鍵] [化41]
Figure 02_image085
[式(7")中，＊表示鍵結鍵]。 於聚醯胺醯亞胺系樹脂進而包含式(a)中之Y係由式(6)所表示之結構單元(a2)作為源自四羧酸化合物之結構單元之情形時及包含式(c)中之X係由式(5)所表示之結構單元(c2)作為源自二胺化合物之結構單元(c)之情形時，較佳為式(5)係由式(7)所表示，更佳為式(7)係由式(7')所表示。又，於聚醯胺醯亞胺系樹脂包含式(b)中之Z係由式(5)所表示之結構單元(b3)作為源自二羧酸化合物之結構單元之情形時，較佳為式(5)係由式(7)所表示，更佳為式(7)係由式(7")所表示。In this aspect, formula (7) is preferably represented by formula (7') or formula (7"): [化40]
Figure 02_image083
[In formula (7'), R * represents a hydrogen atom or a bonding bond, and * represents a bonding bond] [化41]
Figure 02_image085
[In the formula (7"), * represents a bonding bond]. The polyimide imine resin further includes the structural unit (a2) represented by the formula (6) in the formula (a) as derived from Y In the case of the structural unit of the tetracarboxylic acid compound and the structural unit (c2) represented by the formula (5) as the structural unit (c) derived from the diamine compound, the X in the formula (c) is more Preferably, the formula (5) is represented by the formula (7), and more preferably the formula (7) is represented by the formula (7'). In addition, the polyimide-based resin includes the formula (b) When Z is the structural unit (b3) represented by the formula (5) as the structural unit derived from the dicarboxylic acid compound, it is preferable that the formula (5) is represented by the formula (7), and more preferably the formula ( 7) is represented by formula (7").

於本發明之較佳之一態樣中，聚醯胺醯亞胺系樹脂具有上述結構單元(a1)、結構單元(b)及結構單元(c)，進而具有式(a)中之Y係由式(6)所表示之源自四羧酸化合物之結構單元(a2)。於該情形時，結構單元(a2)之量基於聚醯胺醯亞胺系樹脂中所包含之總結構單元，較佳為1～25莫耳%，更佳為2～20莫耳%，進而較佳為3～15莫耳%。若結構單元(a2)之量為上述範圍內，則容易提高光學膜之外觀品質，並且容易提高清漆之穩定性，而容易提高光學膜之加工性及全光線透過率。In a preferred aspect of the present invention, the polyimide imine resin has the above-mentioned structural unit (a1), structural unit (b) and structural unit (c), and further has the formula (a) where Y is composed of The structural unit (a2) derived from a tetracarboxylic acid compound represented by formula (6). In this case, the amount of structural unit (a2) is based on the total structural units contained in the polyimide-based resin, preferably 1-25 mol%, more preferably 2-20 mol%, and then Preferably it is 3-15 mol%. If the amount of the structural unit (a2) is within the above range, the appearance quality of the optical film is easily improved, the stability of the varnish is easily improved, and the processability and total light transmittance of the optical film are easily improved.

於本發明之另一較佳之一態樣中，聚醯胺醯亞胺系樹脂具有上述結構單元(a1)及結構單元(b)，進而，具有式(c)中之X係由式(5)所表示之結構單元(c2)作為源自二胺化合物之結構單元(c)。再者，於該態樣中，只要聚醯胺醯亞胺系樹脂中所存在之複數個結構單元(c)中至少一部分結構單元為結構單元(c2)即可。於聚醯胺醯亞胺系樹脂至少具有上述結構單元(a1)、結構單元(b)及結構單元(c2)之情形時，結構單元(c2)之量基於聚醯胺醯亞胺系樹脂中所包含之總結構單元，較佳為1～25莫耳%，更佳為2～20莫耳%，進而較佳為3～15莫耳%。若結構單元(c2)之量為上述範圍內，則容易提高清漆之穩定性，而容易提高光學膜之加工性及全光線透過率。In another preferred aspect of the present invention, the polyimide imine resin has the above-mentioned structural unit (a1) and structural unit (b), and further, the X in the formula (c) is derived from the formula (5) The structural unit (c2) represented by) is the structural unit (c) derived from the diamine compound. Furthermore, in this aspect, as long as at least some of the structural units (c) existing in the polyimide-based resin are structural units (c2). In the case where the polyimide-based resin has at least the above-mentioned structural unit (a1), structural unit (b) and structural unit (c2), the amount of the structural unit (c2) is based on the polyimide-imide resin The total structural unit contained is preferably 1-25 mol%, more preferably 2-20 mol%, and still more preferably 3-15 mol%. If the amount of the structural unit (c2) is within the above range, it is easy to improve the stability of the varnish, and it is easy to improve the processability and total light transmittance of the optical film.

於本發明之較佳之一態樣中，於聚醯胺醯亞胺系樹脂包含式(b)中之Z係由式(5)或式(7)所表示之結構單元(b3)作為源自二羧酸化合物之結構單元之情形時，就光學膜之彈性模數、全光線透過率、表面硬度及耐彎曲性之觀點及清漆之穩定性之觀點而言，式(5)及式(7)中之V較佳為表示-O-、二苯基亞甲基、碳數1～12之直鏈狀、支鏈狀或脂環式之二價烴基、或碳數1～12之二價烴基中所包含之氫原子被取代為鹵素原子之基，更佳為表示-O-。In a preferred aspect of the present invention, the polyimide imine resin contains the structural unit (b3) represented by the formula (5) or the formula (7) in the formula (b) as derived from In the case of the structural unit of the dicarboxylic acid compound, in terms of the elastic modulus, total light transmittance, surface hardness, and bending resistance of the optical film, and the stability of the varnish, formulas (5) and (7) V in) preferably represents -O-, diphenylmethylene, a linear, branched or alicyclic divalent hydrocarbon group with 1 to 12 carbons, or a divalent hydrocarbon group with 1 to 12 carbons The hydrogen atom contained in the hydrocarbon group is substituted with a halogen atom, and more preferably represents -O-.

於該態樣中，式(5)較佳為係由式(9)所表示： [化42]

Figure 02_image087
[式(9)中，R4 ～R11 相互獨立地表示氫原子、碳數1～6之烷基、碳數1～6之烷氧基、或碳數6～12之芳基，R4 ～R11 中所包含之氫原子可相互獨立地被取代為鹵素原子， m為1～4之整數， 式(5)及式(7)中之V表示鍵結鍵]In this aspect, formula (5) is preferably represented by formula (9): [化42]
Figure 02_image087
[In formula (9), R 4 to R 11 independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons, or an aryl group with 6 to 12 carbons, R 4 The hydrogen atoms contained in ~R 11 can be independently substituted with halogen atoms, m is an integer of 1 to 4, and V in formula (5) and formula (7) represents a bonding bond]

式(9)中之R4 ～R11 相互獨立地表示氫原子、碳數1～6之烷基、碳數1～6之烷氧基、或碳數6～12之芳基，R4 ～R11 中所包含之氫原子可相互獨立地被取代為鹵素原子。作為碳數1～6之烷基，例如可列舉：甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、2-甲基丁基、3-甲基丁基、2-乙基丙基、正己基等。作為碳數1～6之烷氧基，例如可列舉：甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基、第三丁氧基、戊氧基、己氧基、環己氧基等。作為碳數6～12之芳基，例如可列舉：苯基、甲苯基、二甲苯基、萘基、聯苯基等。就光學膜之表面硬度及柔軟性之觀點而言，R4 ～R11 相互獨立地較佳為表示氫原子或碳數1～6之烷基，更佳為表示氫原子或碳數1～3之烷基，進而較佳為表示氫原子。此處，R4 ～R11 中所包含之氫原子可相互獨立地被取代為鹵素原子。作為上述鹵素原子，可列舉：氟原子、氯原子、溴原子、碘原子等。R 4 to R 11 in formula (9) independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons, or an aryl group with 6 to 12 carbons, and R 4 to The hydrogen atoms contained in R 11 may be independently substituted with halogen atoms. Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, tertiary butyl, n-pentyl, and 2-methyl Butyl, 3-methylbutyl, 2-ethylpropyl, n-hexyl, etc. Examples of alkoxy groups having 1 to 6 carbon atoms include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tertiary butoxy, and pentoxy , Hexyloxy, cyclohexyloxy, etc. Examples of aryl groups having 6 to 12 carbon atoms include phenyl, tolyl, xylyl, naphthyl, biphenyl and the like. From the viewpoint of the surface hardness and flexibility of the optical film, R 4 to R 11 independently of each other preferably represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably represent a hydrogen atom or a carbon number of 1 to 3 The alkyl group further preferably represents a hydrogen atom. Here, the hydrogen atoms contained in R 4 to R 11 may be substituted with halogen atoms independently of each other. As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

式(9)中之m為1～4之整數，若m為該範圍內，則光學膜之耐彎曲性及彈性模數容易變得良好。又，式(9)中之m較佳為1～3之範圍之整數，更佳為1～2，進而較佳為1。若m為該範圍內，則容易提高光學膜之外觀品質、耐彎曲性及彈性模數。於本發明中之聚醯胺醯亞胺系樹脂具有式(b)中之Z係由式(9)所表示之結構單元作為源自二羧酸化合物之結構單元(b)之情形時，聚醯胺醯亞胺系樹脂可具有式(b)中之Z係由式(9)所表示之1種或2種以上之結構單元。In the formula (9), m is an integer of 1 to 4. If m is within this range, the bending resistance and elastic modulus of the optical film are likely to become good. Furthermore, m in formula (9) is preferably an integer in the range of 1 to 3, more preferably 1 to 2, and still more preferably 1. If m is in this range, it is easy to improve the appearance quality, bending resistance, and elastic modulus of the optical film. When the polyamide imine resin in the present invention has the Z in formula (b) and the structural unit represented by formula (9) as the structural unit (b) derived from the dicarboxylic acid compound, poly The amide imine-based resin may have one or two or more structural units represented by the formula (9) in Z in the formula (b).

於該態樣中，式(9)較佳為係由式(7")所表示： [化43]

Figure 02_image089
於該情形時，容易提高光學膜之外觀品質、表面硬度及耐彎曲性，容易降低YI值。In this aspect, formula (9) is preferably represented by formula (7"): [化43]
Figure 02_image089
In this case, it is easy to improve the appearance quality, surface hardness, and bending resistance of the optical film, and it is easy to reduce the YI value.

於聚醯胺醯亞胺樹脂包含式(b)中之Z係由式(5)、式(7)、式(9)或式(7")所表示之結構單元(b3)作為源自二羧酸化合物之結構單元(b)之情形時，於將聚醯胺醯亞胺系樹脂中所包含之總結構單元之量設為100莫耳%時，結構單元(b3)之比率較佳為1莫耳%以上，更佳為2莫耳%以上，進而較佳為3莫耳%以上，尤佳為4莫耳%以上，較佳為45莫耳%以下，更佳為35莫耳%以下，進而較佳為25莫耳%以下，尤佳為15莫耳%以下。若結構單元(b3)之比率為上述下限以上，則容易提高光學膜之外觀品質、表面硬度及耐彎曲性。又，若該比率為上述上限以下，則容易抑制含樹脂之清漆之黏度上升而提高膜之加工性。再者，該等結構單元之含量例如可使用1 H-NMR進行測定或亦可根據原料之添加比而算出。In the polyamide imine resin, the Z in the formula (b) is represented by the formula (5), formula (7), formula (9) or formula (7") as a structural unit (b3) derived from two In the case of the structural unit (b) of the carboxylic acid compound, the ratio of the structural unit (b3) is preferably when the amount of the total structural unit contained in the polyamidoimide-based resin is 100 mol% 1 mol% or more, more preferably 2 mol% or more, more preferably 3 mol% or more, particularly preferably 4 mol% or more, preferably 45 mol% or less, more preferably 35 mol% Hereinafter, it is more preferably 25 mol% or less, and particularly preferably 15 mol% or less. If the ratio of the structural unit (b3) is more than the above lower limit, the appearance quality, surface hardness, and bending resistance of the optical film are easily improved. In addition, if the ratio is less than the above upper limit, it is easy to suppress the increase in the viscosity of the resin-containing varnish and improve the processability of the film. Furthermore, the content of these structural units can be measured, for example, using 1 H-NMR or based on raw materials. Calculated by adding ratio.

於本發明之較佳之一實施形態中，於聚醯胺醯亞胺樹脂包含式(b)中之Z係由式(5)、式(7)、式(9)或式(7")所表示之結構單元(b3)作為源自二羧酸化合物之結構單元(b)之情形時，較佳為結構單元(b)中之較佳為5莫耳%以上、更佳為8莫耳%以上、進而較佳為10莫耳%以上、尤佳為12莫耳%以上為結構單元(b3)。若結構單元(b3)之量為上述範圍，則容易提高光學膜之表面硬度且容易提高耐彎曲性及彈性模數。又，較佳為聚醯胺醯亞胺系樹脂所具有之源自二羧酸化合物之結構單元(b)中之較佳為90莫耳%以下、更佳為70莫耳%以下、進而較佳為50莫耳%以下、尤佳為30莫耳%以下為結構單元(b3)。若結構單元(b3)之量為上述範圍，則容易抑制含樹脂之清漆之黏度上升而提高膜之加工性。本發明之光學膜中所包含之聚醯胺醯亞胺樹脂較佳為具有上述結構單元(a1)，並且包含上述量之結構單元(b3)作為源自二羧酸化合物之結構單元(b)，且具有上述結構單元(b2)作為其他結構單元(b)。In a preferred embodiment of the present invention, the polyamide imine resin containing formula (b) in Z is represented by formula (5), formula (7), formula (9) or formula (7") In the case where the structural unit (b3) shown is the structural unit (b) derived from a dicarboxylic acid compound, the structural unit (b) is preferably at least 5 mol%, more preferably 8 mol% The above, more preferably 10 mol% or more, and more preferably 12 mol% or more are the structural unit (b3). If the amount of the structural unit (b3) is in the above range, the surface hardness of the optical film is easily increased and the increase is easy Bending resistance and elastic modulus. In addition, the structural unit (b) derived from the dicarboxylic acid compound possessed by the polyamideimide-based resin is preferably 90 mol% or less, more preferably 70 mol% or less, more preferably 50 mol% or less, and particularly preferably 30 mol% or less are the structural unit (b3). If the amount of the structural unit (b3) is in the above range, it is easy to suppress the resin-containing varnish The viscosity increases to improve the processability of the film. The polyimide imine resin contained in the optical film of the present invention preferably has the above-mentioned structural unit (a1) and contains the above-mentioned amount of the structural unit (b3) as a source The structural unit (b) of the dicarboxylic acid compound has the aforementioned structural unit (b2) as the other structural unit (b).

如上所述，本發明之光學膜中所包含之聚醯胺醯亞胺系樹脂 ・至少包含選自由式(a)中之Y係由式(1)所表示之結構單元(a1)、式(b)所表示之結構單元(b)及式(c)所表示之結構單元(c)、 ・至少包含式(a)所表示之結構單元(a)、式(b)中之Z係由式(1)所表示之結構單元(b1)、及式(c)所表示之結構單元(c)、或 ・至少包含式(a)中之Y係由式(1)所表示之結構單元(a1)、式(b)中之Z係由式(1)所表示之結構單元(b1)、及式(c)所表示之結構單元(c)。As described above, the polyimide resin contained in the optical film of the present invention ・Contain at least the structural unit (a1) represented by the formula (1), the structural unit (b) represented by the formula (b), and the structural unit represented by the formula (c) selected from Y in the formula (a) c), ・Contain at least the structural unit (a) represented by the formula (a), the Z in the formula (b) is the structural unit (b1) represented by the formula (1), and the structural unit (c) represented by the formula (c) ),or ・Contain at least the structural unit (a1) represented by formula (1) in Y in formula (a), the structural unit (b1) represented by formula (1) in Z in formula (b), and formula ( c) The structural unit (c) indicated.

於本發明之較佳之態樣中，就容易提高清漆之穩定性、容易提高所獲得之光學膜之外觀品質、全光線透過率、彈性模數、表面硬度及耐彎曲性之觀點而言，作為本發明之光學膜中所包含之較佳之聚醯胺醯亞胺系樹脂，例如可列舉以下樹脂： (i)至少包含結構單元(a1)、式(b)中之Z係由式(2)所表示之結構單元(b1)、及結構單元(c)之聚醯胺醯亞胺樹脂、 (ii)至少包含結構單元(a1)、表示式(b)中之Z係由式(20)～式(29)所表示之基之鍵結鍵中不相鄰之2個被取代為氫原子之二價有機基、或具有噻吩環骨架之二價有機基之結構單元、以及結構單元(c)之聚醯胺醯亞胺樹脂、 (iii)至少包含結構單元(a1)、表示式(b)中之Z係由式(20')～式(29')所表示之二價有機基之結構單元(20b')～(b29')之至少1個、及結構單元(c)之聚醯胺醯亞胺樹脂、 (iv)至少包含結構單元(a1)、結構單元(20b')～(b29')之至少1個、結構單元(c)、及式(d1)所表示之結構單元(d1)之聚醯胺醯亞胺樹脂、 (v)至少包含結構單元(a1)、式(2-i)所表示之結構單元(b2-i)及結構單元(c)之聚醯胺醯亞胺樹脂、 (vi)至少包含結構單元(a1)、結構單元(b2-i)、結構單元(c)、及結構單元(d1)之聚醯胺醯亞胺樹脂、 (viii)上述各聚醯胺醯亞胺樹脂中之結構單元(c)至少包含式(c)中之X係由式(3)所表示之結構單元(c1)之聚醯胺醯亞胺樹脂、 (ix)於上述各聚醯胺醯亞胺樹脂中，包含選自由作為結構單元(a)之至少一部分之式(a)中之Y係由式(6)所表示之結構單元(a2)、作為結構單元(b)之至少一部分之式(b)中之Z係由式(5)所表示之結構單元(b3)、及作為結構單元(c)之至少一部分之式(c)中之X係由式(5)所表示之結構單元(c2)所組成之群中之結構單元之聚醯胺醯亞胺樹脂、 (x)於上述各聚醯胺醯亞胺樹脂中，包含結構單元(a)代替結構單元(a1)，並且包含結構單元(b1)之聚醯胺醯亞胺樹脂。In a preferred aspect of the present invention, from the viewpoints of easily improving the stability of the varnish, the appearance quality, total light transmittance, elastic modulus, surface hardness and bending resistance of the obtained optical film, The preferred polyamide-imide resin contained in the optical film of the present invention, for example, the following resins: (i) Polyamide resin containing at least structural unit (a1), Z in formula (b) is a structural unit (b1) represented by formula (2), and structural unit (c), (ii) Contain at least structural unit (a1), which means that Z in formula (b) is the group represented by formula (20) to formula (29). Two non-adjacent bonds are substituted with hydrogen atoms The divalent organic group, or the structural unit of the divalent organic group with the thiophene ring skeleton, and the polyamide imide resin of the structural unit (c), (iii) Structural units (20b') to (b29') containing at least the structural unit (a1), which means that Z in formula (b) is a divalent organic group represented by formula (20') to formula (29') ) At least 1 and the polyamide imide resin of structural unit (c), (iv) Polyamide containing at least structural unit (a1), structural unit (20b') to (b29'), structural unit (c), and structural unit (d1) represented by formula (d1) Imide resin, (v) Polyimide resin containing at least structural unit (a1), structural unit (b2-i) represented by formula (2-i) and structural unit (c), (vi) Polyimide resin containing at least structural unit (a1), structural unit (b2-i), structural unit (c), and structural unit (d1), (viii) The structural unit (c) in each of the above-mentioned polyimide resins contains at least the X in the formula (c) is a polyimide resin with the structural unit (c1) represented by the formula (3) , (ix) In each of the above-mentioned polyimide imine resins, a structural unit (a2) selected from the formula (a) as at least a part of the structural unit (a) is included in the formula (6), Z in formula (b) as at least a part of structural unit (b) is structural unit (b3) represented by formula (5), and X in formula (c) as at least a part of structural unit (c) The polyamide imine resin is a structural unit in the group consisting of the structural unit (c2) represented by formula (5), (x) In each of the above-mentioned polyimide resins, a polyimide resin containing the structural unit (a) instead of the structural unit (a1), and containing the structural unit (b1).

就容易提高聚醯胺醯亞胺系樹脂之清漆穩定性、容易提高所獲得之光學膜之外觀品質、全光線透過率、彈性模數、表面硬度及耐彎曲性之觀點而言，聚醯胺醯亞胺系樹脂較佳為除式(a)中之Y係由式(1)所表示之結構單元(a1)以外，亦具有結構單元(c1)及結構單元(b2)或具有結構單元(a2)、(b3)及(c2)之至少1個，更佳為除式(a)中之Y係由式(1)所表示之結構單元(a1)以外，亦具有結構單元(c1)及(b2)且具有結構單元(a2)、(b3)及(c2)之至少1個。又，於聚醯胺醯亞胺系樹脂具有結構單元(a2)、(b3)及(c2)之至少1個之情形時，較佳為至少具有結構單元(c2)。又，本發明之聚醯胺醯亞胺樹脂較佳為除結構單元(a1)及結構單元(c)以外，亦具有結構單元(b20')～(b29')之任一個，並且具有結構單元(d1)，更佳為亦具有結構單元(b2)，並且具有結構單元(d1)。From the standpoint of easily improving the varnish stability of polyimide resins, and easily improving the appearance quality, total light transmittance, elastic modulus, surface hardness and bending resistance of the obtained optical film, polyamide The imine-based resin preferably has a structural unit (c1) and a structural unit (b2) or a structural unit (a1) in addition to the Y in the formula (a) being the structural unit (a1) represented by the formula (1) At least one of a2), (b3) and (c2), more preferably, in addition to the structural unit (a1) represented by the formula (1) in Y in the formula (a), it also has the structural unit (c1) and (b2) and has at least one of the structural units (a2), (b3) and (c2). In addition, when the polyimide-based resin has at least one of the structural units (a2), (b3), and (c2), it preferably has at least the structural unit (c2). In addition, the polyamide imine resin of the present invention preferably has any one of the structural units (b20') to (b29') in addition to the structural unit (a1) and the structural unit (c), and has a structural unit (d1), it is more preferable that it also has a structural unit (b2), and has a structural unit (d1).

於本發明之光學膜中所包含之聚醯胺醯亞胺系樹脂中，結構單元(a)、結構單元(b)及結構單元(c)可形成包含上述式(D)所表示之醯亞胺鍵、及上述式(E)所表示之醯胺鍵之結構，除(D)及(E)所表示之結構以外，例如結構單元(a)及結構單元(c)亦可形成並包含式(30)所表示之結構，與結構單元(a)～(c)不同之結構單元(d)與結構單元(c)亦可形成並包含式(31)所表示之結構單元。 [化44]

Figure 02_image091
In the polyamide imine resin contained in the optical film of the present invention, the structural unit (a), the structural unit (b), and the structural unit (c) can be formed to include the above-mentioned formula (D). The structure of the amine bond and the amide bond represented by the above formula (E), in addition to the structures represented by (D) and (E), for example, the structural unit (a) and the structural unit (c) can also be formed and include the formula In the structure represented by (30), the structural unit (d) and the structural unit (c) different from the structural units (a) to (c) may also be formed and include the structural unit represented by the formula (31). [化44]
Figure 02_image091

於式(30)中，Y1 為四價有機基，較佳為有機基中之氫原子可被取代為烴基或經氟取代之烴基之四價有機基。Y1 例如亦可為式(1)所表示之結構單元。於本發明之一實施形態中，聚醯胺醯亞胺系樹脂可包含複數種Y1 ，複數種Y1 可相互相同，亦可不同。In formula (30), Y 1 is a tetravalent organic group, preferably a tetravalent organic group in which the hydrogen atom in the organic group can be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. Y 1 may also be a structural unit represented by formula (1), for example. In one embodiment of the present invention, the polyimide-based resin may include a plurality of Y 1 , and the plurality of Y 1 may be the same or different from each other.

於式(31)中，Y2 為三價有機基，較佳為有機基中之氫原子可被取代為烴基或經氟取代之烴基之三價有機基。於本發明之一實施形態中，聚醯胺醯亞胺系樹脂可包含複數種Y2 ，複數種Y2 可相互相同，亦可不同。In formula (31), Y 2 is a trivalent organic group, preferably a trivalent organic group in which the hydrogen atom in the organic group can be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. In one embodiment of the present invention, the polyimide-based resin may include multiple types of Y 2 , and the multiple types of Y 2 may be the same or different from each other.

於式(30)及式(31)中，X2 及X3 相互獨立地為二價有機基，較佳為有機基中之氫原子可被取代為烴基或經氟取代之烴基之有機基。作為X2 及X3 ，可例示作為式(c)中之X所記載之基、作為式(2)中之X'所記載之基。In formula (30) and formula (31), X 2 and X 3 are independently a divalent organic group, preferably an organic group in which the hydrogen atom in the organic group can be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. Examples of X 2 and X 3 include the group described as X in formula (c) and the group described as X'in formula (2).

於本發明之一實施形態中，聚醯胺醯亞胺系樹脂包含由源自四羧酸化合物之結構單元(a)及源自二胺化合物之結構單元(c)構成之式(D)所表示之結構單元、由源自二羧酸化合物之結構單元(b)及源自二胺化合物之結構單元(c)構成之式(E)所表示之結構單元、以及視情形包含式(30)所表示之結構單元、及/或式(31)所表示之結構單元。就容易提高光學膜之彈性模數、全光線透過率、光學特性、表面硬度之觀點而言，於上述聚醯胺醯亞胺系樹脂中，式(D)及式(E)所表示之結構單元基於式(D)及式(E)、以及視情形時之式(30)及式(31)所表示之結構單元之合計，包含較佳為80莫耳%以上、更佳為90莫耳%以上、進而較佳為95莫耳%以上，通常包含100莫耳%以下。再者，上述比率例如可使用1 H-NMR進行測定或亦可根據原料之添加比算出。In one embodiment of the present invention, the polyimide-based resin includes the formula (D) composed of a structural unit (a) derived from a tetracarboxylic acid compound and a structural unit (c) derived from a diamine compound. The structural unit represented, the structural unit represented by the formula (E) composed of the structural unit (b) derived from the dicarboxylic acid compound and the structural unit (c) derived from the diamine compound, and optionally including the formula (30) The structural unit represented by and/or the structural unit represented by formula (31). From the viewpoint of easily improving the elastic modulus, total light transmittance, optical properties, and surface hardness of the optical film, in the above-mentioned polyimide-imide resin, the structure represented by formula (D) and formula (E) The unit is based on the total of the structural units represented by formula (D) and formula (E), and as the case may be, formula (30) and formula (31), including preferably 80 mol% or more, more preferably 90 mol% % Or more, more preferably 95 mol% or more, and usually includes 100 mol% or less. In addition, the above-mentioned ratio can be measured using 1 H-NMR, or it can also be calculated from the addition ratio of raw materials.

就容易提高清漆之穩定性、容易提高光學膜之光學特性、彈性模數、表面硬度及耐彎曲性之觀點而言，本發明之光學膜中所包含之聚醯胺醯亞胺系樹脂之基於聚苯乙烯換算所得之重量平均分子量較佳為200,000以上，更佳為250,000以上，進而較佳為300,000以上，尤佳為350,000以上。又，就容易提高聚醯胺醯亞胺系樹脂對溶劑之溶解性，並且容易提高光學膜之延伸性及加工性之觀點而言，該重量平均分子量較佳為1,000,000以下，更佳為800,000以下，進而較佳為700,000以下，尤佳為600,000以下。重量平均分子量例如可進行GPC(gel permeation chromatograph，凝膠滲透層析)測定並藉由標準聚苯乙烯換算而求出，例如可藉由實施例所記載之方法而算出。From the viewpoints of easily improving the stability of the varnish and the optical properties, elastic modulus, surface hardness and bending resistance of the optical film, the polyimide-imide resin contained in the optical film of the present invention is based on The weight average molecular weight converted from polystyrene is preferably 200,000 or more, more preferably 250,000 or more, still more preferably 300,000 or more, and particularly preferably 350,000 or more. In addition, from the viewpoint of easily improving the solubility of the polyimide-based resin in solvents and easily improving the elongation and processability of the optical film, the weight average molecular weight is preferably 1,000,000 or less, more preferably 800,000 or less , More preferably 700,000 or less, and particularly preferably 600,000 or less. The weight average molecular weight can be obtained by, for example, GPC (gel permeation chromatograph) measurement and conversion from standard polystyrene, and can be calculated, for example, by the method described in the examples.

聚醯胺醯亞胺系樹脂之醯亞胺化率較佳為90%以上，更佳為93%以上，進而較佳為96%以上，通常為100%以下。就容易提高光學膜之光學特性之觀點而言，醯亞胺化率較佳為上述下限以上。醯亞胺化率表示聚醯胺醯亞胺系樹脂中之醯亞胺鍵之莫耳量相對於聚醯胺醯亞胺系樹脂中之源自四羧酸化合物之結構單元之莫耳量之2倍之值之比率。再者，於聚醯胺醯亞胺系樹脂包含三羧酸化合物之情形時，表示聚醯胺醯亞胺系樹脂中之醯亞胺鍵之莫耳量相對於聚醯胺醯亞胺系樹脂中之源自四羧酸化合物之結構單元之莫耳量之2倍之值與源自三羧酸化合物之結構單元之莫耳量之合計之比率。又，醯亞胺化率可藉由IR(Infrared Radiation，紅外光譜)法、NMR法等求出。The imidization rate of the polyimide-based resin is preferably 90% or more, more preferably 93% or more, still more preferably 96% or more, and usually 100% or less. From the viewpoint of easy improvement of the optical properties of the optical film, the imidization rate is preferably at least the above lower limit. The imidization rate represents the molar amount of the amide bond in the polyamide-imide resin relative to the molar amount of the structural unit derived from the tetracarboxylic acid compound in the polyamide-imide resin The ratio of 2 times the value. Furthermore, when the polyamide-imide-based resin contains a tricarboxylic acid compound, it means that the molar amount of the amide bond in the polyamide-imide-based resin is relative to the polyamide-imide-based resin The ratio of the value of twice the molar amount of the structural unit derived from the tetracarboxylic acid compound to the total molar amount of the structural unit derived from the tricarboxylic acid compound. In addition, the imidization rate can be determined by IR (Infrared Radiation) method, NMR method, or the like.

聚醯胺醯亞胺系樹脂中之鹵素原子之含量以聚醯胺醯亞胺系樹脂之質量為基準，較佳為1～40質量%，更佳為5～40質量%，進而較佳為5～30質量%。若鹵素原子之含量為上述下限以上，則更容易提高光學膜之彈性模數、表面硬度、透明性及視認性。若鹵素原子之含量為上述上限以下，則容易合成樹脂。The content of halogen atoms in the polyimide-based resin is based on the mass of the polyimide-based resin, preferably 1-40% by mass, more preferably 5-40% by mass, and still more preferably 5-30% by mass. If the content of halogen atoms is more than the above lower limit, it is easier to improve the elastic modulus, surface hardness, transparency, and visibility of the optical film. If the content of halogen atoms is less than the above upper limit, it is easy to synthesize resin.

[樹脂之製造方法] 本發明之光學膜中所包含之聚醯胺醯亞胺系樹脂可將四羧酸化合物、二羧酸化合物及二胺化合物作為主要原料而製造。此處，聚醯胺醯亞胺系樹脂包含選自由如下結構單元所組成之群中之至少1種結構單元：作為源自四羧酸化合物之結構單元之式(a)中之Y係由式(1)所表示之結構單元(a1)及作為源自二羧酸化合物之結構單元之式(b)中之Z係由式(1)所表示之結構單元(b1)。因此，作為原料，至少使用選自由包含式(1)所表示之結構之四羧酸化合物及包含式(1)所表示之結構之二羧酸化合物所組成之群中之至少1種化合物。[Manufacturing method of resin] The polyamidoimide-based resin contained in the optical film of the present invention can be produced using a tetracarboxylic acid compound, a dicarboxylic acid compound, and a diamine compound as main raw materials. Here, the polyimide imine-based resin includes at least one structural unit selected from the group consisting of the following structural units: Y in formula (a), which is a structural unit derived from a tetracarboxylic acid compound, is derived from the formula (1) The structural unit (a1) represented by (a1) and Z in the formula (b) as a structural unit derived from a dicarboxylic acid compound are the structural units (b1) represented by the formula (1). Therefore, as a raw material, at least one compound selected from the group consisting of a tetracarboxylic acid compound containing the structure represented by formula (1) and a dicarboxylic acid compound containing the structure represented by formula (1) is used.

作為用於製造樹脂之四羧酸化合物，可列舉如提供式(a)中之Y係由式(1)所表示之結構單元(a1)之四羧酸化合物、例如芳香族四羧酸二酐等芳香族四羧酸化合物。可使用1種四羧酸化合物，亦可將2種以上組合使用。四羧酸化合物除二酐以外，亦可為醯氯化合物等四羧酸化合物類似體。例如可列舉上述式(8)所表示之化合物。As the tetracarboxylic acid compound used in the production of resins, for example, the tetracarboxylic acid compound in which Y in the formula (a) is the structural unit (a1) represented by the formula (1), such as aromatic tetracarboxylic dianhydride And other aromatic tetracarboxylic acid compounds. One type of tetracarboxylic acid compound may be used, or two or more types may be used in combination. In addition to the dianhydride, the tetracarboxylic acid compound may be a tetracarboxylic acid compound analog such as a chlorine compound. For example, the compound represented by the said formula (8) is mentioned.

作為用於製造樹脂之四羧酸化合物，可列舉上述式(8)所表示之化合物(四羧酸二酐)、例如3,3',4,4'-聯苯四羧酸二酐(BPDA)。As the tetracarboxylic acid compound used in the production of resins, the compound represented by the above formula (8) (tetracarboxylic dianhydride), for example, 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA ).

又，作為用於製造樹脂之其他四羧酸化合物，可列舉：4,4'-氧二鄰苯二甲酸二酐、2,2',3,3'-二苯甲酮四羧酸二酐、2,2',3,3'-聯苯四羧酸二酐、3,3',4,4'-二苯基碸四羧酸二酐、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、2,2-雙(3,4-二羧基苯氧基苯基)丙烷二酐、4,4'-(六氟亞異丙基)二鄰苯二甲酸二酐(有時記載為6FDA)、1,2-雙(2,3-二羧基苯基)乙烷二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、1,2-雙(3,4-二羧基苯基)乙烷二酐、1,1-雙(3,4-二羧基苯基)乙烷二酐、雙(3,4-二羧基苯基)甲烷二酐、雙(2,3-二羧基苯基)甲烷二酐、4,4'-(對伸苯基二氧基)二鄰苯二甲酸二酐、4,4'-(間伸苯基二氧基)二鄰苯二甲酸二酐。又，作為單環式之芳香族四羧酸二酐，例如可列舉1,2,4,5-苯四羧酸二酐(均苯四甲酸二酐(PMDA))，作為縮合多環式之芳香族四羧酸二酐，例如可列舉2,3,6,7-萘四羧酸二酐。In addition, as other tetracarboxylic acid compounds used in the production of resins, 4,4'-oxydiphthalic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride can be cited , 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 2,2-bis(3,4-di Carboxyphenyl) propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenoxyphenyl)propane dianhydride, 4 ,4'-(hexafluoroisopropylidene)diphthalic dianhydride (sometimes recorded as 6FDA), 1,2-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1 -Bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,2-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxybenzene) Yl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 4,4'-(p-phenylenedioxy ) Diphthalic dianhydride, 4,4'-(m-phenylenedioxy) diphthalic dianhydride. Also, as the monocyclic aromatic tetracarboxylic dianhydride, for example, 1,2,4,5-benzenetetracarboxylic dianhydride (pyromellitic dianhydride (PMDA)) can be cited as one of the condensed polycyclic Examples of the aromatic tetracarboxylic dianhydride include 2,3,6,7-naphthalenetetracarboxylic dianhydride.

該等之中，作為四羧酸化合物，較佳為列舉：4,4'-氧二鄰苯二甲酸二酐、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、3,3',4,4'-聯苯四羧酸二酐(BPDA)、1,2,4,5-苯四羧酸二酐(PMDA)、2,2',3,3'-聯苯基四羧酸二酐、3,3',4,4'-二苯基碸四羧酸二酐、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、2,2-雙(3,4-二羧基苯氧基苯基)丙烷二酐、1,2-雙(2,3-二羧基苯基)乙烷二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、1,2-雙(3,4-二羧基苯基)乙烷二酐、1,1-雙(3,4-二羧基苯基)乙烷二酐、雙(3,4-二羧基苯基)甲烷二酐、雙(2,3-二羧基苯基)甲烷二酐、4,4'-(對伸苯基二氧基)二鄰苯二甲酸二酐及4,4'-(間伸苯基二氧基)二鄰苯二甲酸二酐；更佳為列舉：4,4'-氧二鄰苯二甲酸二酐、3,3',4,4'-聯苯四羧酸二酐(BPDA)、2,2',3,3'-聯苯基四羧酸二酐、雙(3,4-二羧基苯基)甲烷二酐、4,4'-(對伸苯基二氧基)二鄰苯二甲酸二酐及1,2,4,5-苯四羧酸二酐(PMDA)。該等可單獨使用或將2種以上組合使用。Among these, the tetracarboxylic acid compound preferably includes 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 1,2,4,5-benzene Tetracarboxylic dianhydride (PMDA), 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 2, 2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenoxy) Phenyl)propane dianhydride, 1,2-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1, 2-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane Dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 4,4'-(p-phenylenedioxy)diphthalic dianhydride and 4,4'-(m-phenylene) Dioxy)diphthalic dianhydride; more preferably listed: 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA ), 2,2',3,3'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 4,4'-(p-phenylene dioxy) Diphthalic dianhydride and 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA). These can be used individually or in combination of 2 or more types.

就光學膜之外觀品質、彈性模數、全光線透過率、表面硬度及耐彎曲性之觀點而言，作為用於製造樹脂之四羧酸化合物，較佳為使用3,3',4,4'-聯苯四羧酸二酐(BPDA)，亦較佳為使用3,3',4,4'-聯苯四羧酸二酐(BPDA)與4,4'-(六氟亞異丙基)二鄰苯二甲酸二酐(6FDA)。From the viewpoints of the appearance quality, elastic modulus, total light transmittance, surface hardness, and bending resistance of the optical film, as the tetracarboxylic acid compound used to make the resin, 3,3',4,4 are preferably used. '-Biphenyltetracarboxylic dianhydride (BPDA), it is also preferable to use 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 4,4'-(hexafluoroisopropylidene Base) diphthalic dianhydride (6FDA).

作為用於製造聚醯胺醯亞胺系樹脂之二羧酸化合物，可列舉：芳香族二羧酸、脂肪族二羧酸及其等之類似之醯氯化合物、酸酐等。可使用1種二羧酸化合物，亦可將2種以上組合使用。Examples of the dicarboxylic acid compound used for the production of the polyimide-based resin include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and similar chlorinated compounds and acid anhydrides. One type of dicarboxylic acid compound may be used, or two or more types may be used in combination.

作為用於製造聚醯胺醯亞胺系樹脂之如提供式(b)中之Z係由式(1)所表示之結構單元(b1)之二羧酸化合物，例如可列舉集合環芳香族二羧酸化合物。作為用於製造樹脂之二羧酸化合物，可列舉上述式(12)所表示之化合物(二羧醯氯)、例如3,3',4,4'-聯苯基二羧醯氯(BPDC)。As the dicarboxylic acid compound used for the production of polyimide imine resins such as providing the Z in the formula (b), the structural unit (b1) represented by the formula (1), for example, an assembling ring aromatic two Carboxylic acid compound. As the dicarboxylic acid compound used in the production of the resin, the compound represented by the above formula (12) (dicarboxylic acid chloride), for example, 3,3',4,4'-biphenyldicarboxylic acid chloride (BPDC) .

作為二羧酸化合物，較佳為使用對苯二甲酸、間苯二甲酸、4,4'-氧基二苯甲酸或其等之醯氯化合物。除對苯二甲酸或4,4'-氧基二苯甲酸或其等之醯氯化合物以外，亦可使用其他二羧酸化合物。作為其他二羧酸化合物，作為具體例，可列舉：間苯二甲酸；萘二甲酸；4,4'-聯苯基二羧酸；3,3'-聯苯基二羧酸；碳數8以下之鏈式烴之二羧酸化合物及2個苯甲酸經單鍵、-CH2 -、-C(CH3 )2 -、-C(CF3 )2 -、-SO2 -或伸苯基連結之化合物以及其等之醯氯化合物。作為具體例，較佳為4,4'-氧基雙(苯甲醯氯)、對苯二甲醯氯，進而較佳為將4,4'-氧基雙(苯甲醯氯)與對苯二甲醯氯組合使用。As the dicarboxylic acid compound, it is preferable to use terephthalic acid, isophthalic acid, 4,4'-oxydibenzoic acid, or chlorinated compounds thereof. In addition to terephthalic acid or 4,4'-oxydibenzoic acid or its chlorinated compounds, other dicarboxylic acid compounds may also be used. As other dicarboxylic acid compounds, specific examples include: isophthalic acid; naphthalenedicarboxylic acid; 4,4'-biphenyldicarboxylic acid; 3,3'-biphenyldicarboxylic acid; carbon number 8 The following chain hydrocarbon dicarboxylic acid compounds and 2 benzoic acids via single bond, -CH 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -SO 2 -or phenylene Linked compounds and other chlorinated compounds. As a specific example, 4,4'-oxybis(benzyl chloride) and terephthalate chloride are preferred, and 4,4'-oxybis(benzyl chloride) and p- Xylylenedimethacrylate is used in combination.

作為用於製造聚醯胺醯亞胺系樹脂之二胺化合物，例如可列舉芳香族二胺。再者，於本實施形態中，所謂「芳香族二胺」，表示胺基直接鍵結於芳香環之二胺，其結構之一部分亦可包含脂肪族基或其他取代基。該芳香環可為單環，亦可為縮合環，可例示苯環、萘環、蒽環及茀環等，但並不限定於該等。該等之中，較佳為苯環。Examples of the diamine compound used for the production of polyimide-based resins include aromatic diamines. Furthermore, in this embodiment, the so-called "aromatic diamine" means a diamine in which an amine group is directly bonded to an aromatic ring, and a part of its structure may also include an aliphatic group or other substituents. The aromatic ring may be a monocyclic ring or a condensed ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a sulphur ring. Among them, a benzene ring is preferred.

作為芳香族二胺，例如可列舉：對苯二胺、間苯二胺、2,4-甲苯二胺、間苯二甲胺、對苯二甲胺、1,5-二胺基萘、2,6-二胺基萘等具有1個芳香環之芳香族二胺、4,4'-二胺基二苯甲烷、4,4'-二胺基二苯丙烷、4,4'-二胺基二苯基醚、3,4'-二胺基二苯基醚、3,3'-二胺基二苯基醚、4,4'-二胺基二苯基碸、3,4'-二胺基二苯基碸、3,3'-二胺基二苯基碸、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]碸、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(3-胺基苯氧基)苯基]丙烷、2,2'-二甲基聯苯胺、2,2'-雙(三氟甲基)-4,4'-二胺基二苯基(有時記載為TFMB)、4,4'-雙(4-胺基苯氧基)聯苯基、9,9-雙(4-胺基苯基)茀、9,9-雙(4-胺基-3-甲基苯基)茀、9,9-雙(4-胺基-3-氯苯基)茀、9,9-雙(4-胺基-3-氟苯基)茀等具有2個以上之芳香環之芳香族二胺。該等可單獨使用或將2種以上組合使用。Examples of aromatic diamines include p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, m-xylylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene, 2 ,6-Diaminonaphthalene and other aromatic diamines with one aromatic ring, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diamine Diphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'- Diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy) ) Benzene, bis[4-(4-aminophenoxy)phenyl] ash, bis[4-(3-aminophenoxy)phenyl] ash, 2,2-bis[4-(4- Aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2'-dimethylbenzidine, 2,2'-bis (Trifluoromethyl)-4,4'-diaminodiphenyl (sometimes referred to as TFMB), 4,4'-bis(4-aminophenoxy)biphenyl, 9,9-bis (4-Aminophenyl) quince, 9,9-bis(4-amino-3-methylphenyl) quince, 9,9-bis(4-amino-3-chlorophenyl) quince, 9 , 9-bis(4-amino-3-fluorophenyl) pyridine and other aromatic diamines with more than two aromatic rings. These can be used individually or in combination of 2 or more types.

芳香族二胺較佳為4,4'-二胺基二苯甲烷、4,4'-二胺基二苯丙烷、4,4'-二胺基二苯基醚、3,3'-二胺基二苯基醚、4,4'-二胺基二苯基碸、3,3'-二胺基二苯基碸、1,4-雙(4-胺基苯氧基)苯、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]碸、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(3-胺基苯氧基)苯基]丙烷、2,2'-二甲基聯苯胺、2,2'-雙(三氟甲基)-4,4'-二胺基二苯基(TFMB)、4,4'-雙(4-胺基苯氧基)聯苯基、4,4'-(六氟亞丙基)二苯胺(6FDAM)，更佳為4,4'-二胺基二苯基甲烷、4,4'-二胺基二苯基丙烷、4,4'-二胺基二苯基醚、4,4'-二胺基二苯基碸、1,4-雙(4-胺基苯氧基)苯、雙[4-(4-胺基苯氧基)苯基]碸、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2'-二甲基聯苯胺、2,2'-雙(三氟甲基)-4,4'-二胺基二苯基(TFMB)、4,4'-雙(4-胺基苯氧基)聯苯基、4,4'-(六氟亞丙基)二苯胺(6FDAM)。該等可單獨使用或將2種以上組合使用。The aromatic diamine is preferably 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,3'-di Amino diphenyl ether, 4,4'-diaminodiphenyl sulfonate, 3,3'-diaminodiphenyl sulfonium, 1,4-bis(4-aminophenoxy)benzene, double [4-(4-Aminophenoxy)phenyl] ash, bis[4-(3-aminophenoxy)phenyl] ash, 2,2-bis[4-(4-aminophenoxy) Yl)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethane) Group)-4,4'-diaminodiphenyl (TFMB), 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-(hexafluoropropylene) two Aniline (6FDAM), more preferably 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4 '-Diaminodiphenyl ash, 1,4-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl] ash, 2,2-bis[ 4-(4-Aminophenoxy)phenyl)propane, 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl Group (TFMB), 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-(hexafluoropropylene)diphenylamine (6FDAM). These can be used individually or in combination of 2 or more types.

作為用於製造聚醯胺醯亞胺系樹脂之二胺化合物，除芳香族二胺以外，亦可進而使用脂肪族二胺。再者，所謂「脂肪族二胺」，表示胺基直接鍵結於脂肪族基之二胺，可於其結構之一部分包含芳香環或其他取代基。作為脂肪族二胺，例如可列舉：六亞甲基二胺等非環式脂肪族二胺、以及1,3-雙(胺基甲基)環己烷、1,4-雙(胺基甲基)環己烷、降𦯉烷二胺及4,4'-二胺基二環己甲烷等環式脂肪族二胺等。As the diamine compound used for the production of the polyimide-based resin, in addition to the aromatic diamine, an aliphatic diamine may be further used. Furthermore, the so-called "aliphatic diamine" refers to a diamine in which an amine group is directly bonded to an aliphatic group, and a part of its structure may include an aromatic ring or other substituents. As aliphatic diamines, for example, acyclic aliphatic diamines such as hexamethylene diamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl) (Base) cyclohexane, noralkanediamine and 4,4'-diaminodicyclohexylmethane and other cyclic aliphatic diamines.

上述二胺化合物之中，就容易提高光學膜之外觀品質、表面硬度、全光線透過率、彈性模數、柔軟性、彎曲耐受性、容易獲得低著色性之觀點而言，較佳為使用選自由具有聯苯基結構之芳香族二胺所組成之群中之1種以上。更佳為使用選自由2,2'-二甲基聯苯胺、2,2'-雙(三氟甲基)聯苯胺、4,4'-雙(4-胺基苯氧基)聯苯基及4,4'-二胺基二苯基醚、4,4'-(六氟亞丙基)二苯胺所組成之群中之1種以上，進而較佳為使用選自由2,2'-雙(三氟甲基)-4,4'-二胺基二苯基(TFMB)及4,4'-(六氟亞丙基)二苯胺(6FDAM)所組成之群中之1種以上。Among the above-mentioned diamine compounds, it is preferable to use from the viewpoints that the appearance quality, surface hardness, total light transmittance, elastic modulus, flexibility, bending resistance, and low colorability of the optical film can be easily improved. One or more selected from the group consisting of aromatic diamines having a biphenyl structure. More preferably, it is selected from 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)benzidine, 4,4'-bis(4-aminophenoxy)biphenyl And 4,4'-diaminodiphenyl ether, 4,4'-(hexafluoropropylene) diphenylamine at least one of the group consisting of, more preferably used selected from 2,2'- One or more of the group consisting of bis(trifluoromethyl)-4,4'-diaminodiphenyl (TFMB) and 4,4'-(hexafluoropropylene)diphenylamine (6FDAM).

再者，上述聚醯胺醯亞胺系樹脂亦可為於無損光學積層體之各種物性之範圍內，除上述四羧酸化合物以外，亦進而使四羧酸及三羧酸以及其等之酐及衍生物反應而成者。Furthermore, the above-mentioned polyamidoimide-based resin may be within a range that does not impair the various physical properties of the optical laminate. In addition to the above-mentioned tetracarboxylic acid compound, it is also possible to make tetracarboxylic acid, tricarboxylic acid and their anhydrides And derivatives from the reaction.

作為其他四羧酸，可列舉上述四羧酸化合物之酐之水加成體。Examples of other tetracarboxylic acids include water adducts of anhydrides of the aforementioned tetracarboxylic acid compounds.

作為三羧酸化合物，可列舉：芳香族三羧酸、脂肪族三羧酸及其等之類似之醯氯化合物、酸酐等；亦可將2種以上組合使用。作為具體例，可列舉：1,3,5-苯三羧酸或其醯氯化合物、1,2,4-苯三羧酸之酐；2,3,6-萘三羧酸-2,3-酐；鄰苯二甲酸酐與苯甲酸經單鍵、-O-、-CH2 -、-C(CH3 )2 -、-C(CF3 )2 -、-SO2 -或伸苯基連結之化合物。Examples of the tricarboxylic acid compound include aromatic tricarboxylic acids, aliphatic tricarboxylic acids, and similar chlorinated compounds, acid anhydrides, and the like; two or more of them may be used in combination. Specific examples include: 1,3,5-benzenetricarboxylic acid or its chlorinated compounds, anhydrides of 1,2,4-benzenetricarboxylic acid; 2,3,6-naphthalenetricarboxylic acid-2,3 -Anhydride; phthalic anhydride and benzoic acid via single bond, -O-, -CH 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -SO 2 -or phenylene Linked compound.

於樹脂之製造中，二胺化合物、四羧酸化合物及二羧酸化合物各自之使用量可根據所需之聚醯胺醯亞胺系樹脂之各結構單元之比率適當選擇。In the production of the resin, the amount of each of the diamine compound, the tetracarboxylic acid compound, and the dicarboxylic acid compound can be appropriately selected according to the required ratio of each structural unit of the polyamide imide resin.

聚醯胺醯亞胺系樹脂之製造方法只要可獲得上述聚醯胺醯亞胺系樹脂，則並無特別限定，就容易提高光學膜之外觀品質、彈性模數及全光線透過率之觀點而言，較佳為藉由使二胺化合物、四羧酸化合物及二羧酸化合物反應並且分批添加二羧酸化合物之製造方法製造聚醯胺醯亞胺系樹脂，更佳為藉由包含使二胺化合物與四羧酸化合物反應而生成中間物(A)之步驟(I)、及使該中間物(A)與二羧酸化合物反應之步驟(II)且於該步驟(II)中分批添加該二羧酸化合物之方法製造聚醯胺醯亞胺系樹脂。The method for producing polyimide-based resins is not particularly limited as long as the above-mentioned polyimide-based resins can be obtained, and it is easy to improve the appearance quality, elastic modulus, and total light transmittance of the optical film. In other words, it is preferable to produce a polyamide imide-based resin by a production method of reacting a diamine compound, a tetracarboxylic acid compound, and a dicarboxylic acid compound and adding the dicarboxylic acid compound in batches, and more preferably by containing The step (I) of reacting the diamine compound and the tetracarboxylic acid compound to produce the intermediate (A), and the step (II) of reacting the intermediate (A) with the dicarboxylic acid compound, and are separated in the step (II) The method of batch addition of the dicarboxylic acid compound produces a polyimide-based resin.

因此，聚醯胺醯亞胺系樹脂較佳為藉由使二胺化合物、四羧酸化合物及二羧酸化合物反應並且分批添加二羧酸化合物之製造方法而製造之樹脂，更佳為藉由包括使二胺化合物與四羧酸化合物反應而生成中間物(A)之步驟(I)、及使該中間物(A)與二羧酸化合物反應之步驟(II)並且於該步驟(II)中分批添加該二羧酸化合物之製造方法而製造之樹脂。Therefore, the polyimide imine-based resin is preferably a resin manufactured by a manufacturing method of reacting a diamine compound, a tetracarboxylic acid compound, and a dicarboxylic acid compound and adding the dicarboxylic acid compound in batches, more preferably by By including the step (I) of reacting the diamine compound and the tetracarboxylic acid compound to produce the intermediate (A), and the step (II) of reacting the intermediate (A) with the dicarboxylic acid compound, and in the step (II) ) A resin produced by adding the method of producing the dicarboxylic acid compound in batches.

於藉由包含上述步驟(I)及步驟(II)之製造方法製造聚醯胺醯亞胺系樹脂之情形時，使二胺化合物與四羧酸化合物反應而生成中間物(A)之步驟(I)之反應溫度並無特別限定，例如可為5～200℃、較佳為5～100℃、更佳為5～50℃、進而較佳為5℃～室溫(25℃左右)。反應時間例如可為1分鐘～72小時、較佳為10分鐘～24小時。又，反應可於空氣中或例如氮或氬等惰性氣體氛圍中一面攪拌一面進行，亦可於常壓下、加壓下或減壓下進行。較佳之實施形態係於常壓及/或上述惰性氣體氛圍下一面攪拌一面進行。In the case of producing a polyamidoimide-based resin by the production method including the above-mentioned step (I) and step (II), the step of reacting a diamine compound with a tetracarboxylic acid compound to produce an intermediate (A) ( The reaction temperature of I) is not particularly limited. For example, it may be 5 to 200°C, preferably 5 to 100°C, more preferably 5 to 50°C, and still more preferably 5°C to room temperature (about 25°C). The reaction time can be, for example, 1 minute to 72 hours, preferably 10 minutes to 24 hours. In addition, the reaction can be carried out while stirring in air or in an inert gas atmosphere such as nitrogen or argon, and can also be carried out under normal pressure, under pressure, or under reduced pressure. A preferred embodiment is to carry out while stirring under normal pressure and/or the above-mentioned inert gas atmosphere.

於步驟(I)中，二胺化合物與四羧酸化合物反應而生成中間物(A)、即聚醯胺酸。因此，中間物(A)至少具有源自二胺化合物之結構單元與源自四羧酸化合物之結構單元。In step (I), the diamine compound reacts with the tetracarboxylic acid compound to produce the intermediate (A), that is, polyamide acid. Therefore, the intermediate (A) has at least a structural unit derived from a diamine compound and a structural unit derived from a tetracarboxylic acid compound.

繼而，於步驟(II)中，使中間物(A)與二羧酸化合物反應，此處，較佳為分批添加該二羧酸化合物。向步驟(I)中所獲得之反應液中分批添加二羧酸化合物，使中間物(A)與二羧酸化合物反應。並非一次性添加二羧酸化合物，而是藉由分批添加，容易將聚醯胺醯亞胺系樹脂之分子量調整為上述較佳之範圍。再者，於本說明書中，所謂分批添加，意指將欲添加之二羧酸化合物分成幾次添加，更詳細而言，意指將欲添加之二羧酸分成特定量，並間隔特定間隔或特定時間分別添加。該特定間隔或特定時間亦包含非常短之間隔或時間，故而分批添加中亦包含連續添加或連續供料。Then, in step (II), the intermediate (A) is reacted with the dicarboxylic acid compound. Here, it is preferable to add the dicarboxylic acid compound in batches. The dicarboxylic acid compound is added in batches to the reaction liquid obtained in step (I), and the intermediate (A) is reacted with the dicarboxylic acid compound. Instead of adding the dicarboxylic acid compound at once, but by adding in batches, it is easy to adjust the molecular weight of the polyimide-based resin to the above-mentioned preferred range. Furthermore, in this specification, the so-called batch addition means that the dicarboxylic acid compound to be added is divided into several additions. In more detail, it means that the dicarboxylic acid to be added is divided into a specific amount with specific intervals. Or add separately at a specific time. The specific interval or specific time also includes a very short interval or time, so batch addition also includes continuous addition or continuous feeding.

於步驟(II)中，分批添加二羧酸化合物時之分批次數可根據反應尺度或原料之種類等適當選擇，較佳為2～20次，更佳為3～10次，進而較佳為3～6次。若分批次數為上述範圍，則認為容易維持光學膜之透過率，並且容易成為最適合提高彈性模數之結構。又，認為聚醯胺醯亞胺系樹脂之重量平均分子量亦容易調整為上述較佳之範圍。In step (II), the number of batches when adding the dicarboxylic acid compound in batches can be appropriately selected according to the reaction scale or the type of raw materials, etc., preferably 2-20 times, more preferably 3-10 times, and more preferably For 3 to 6 times. If the number of batches is in the above range, it is considered that it is easy to maintain the transmittance of the optical film, and it is likely to be the most suitable structure for increasing the elastic modulus. In addition, it is considered that the weight average molecular weight of the polyimide-based resin is also easily adjusted to the above-mentioned preferable range.

二羧酸化合物可以均等之量分批添加，亦可以不均等之量分批添加。各添加之間之時間(以下有時稱為添加間隔)可全部相同，亦可不同。又，於添加兩種以上之二羧酸化合物之情形時，稱為分批添加之用語意指分批添加所有二羧酸化合物之合計量，各二羧酸化合物之分批方法並無特別限定，例如可分別一次性或分批添加各二羧酸化合物，亦可將各二羧酸化合物一起分批添加，亦可為該等之組合。The dicarboxylic acid compound can be added in equal amounts in batches or in unequal amounts. The time between each addition (hereinafter sometimes referred to as the addition interval) may all be the same or different. In addition, when two or more dicarboxylic acid compounds are added, the term “batch addition” means that the total amount of all dicarboxylic acid compounds is added in batches. The batch method of each dicarboxylic acid compound is not particularly limited. For example, each dicarboxylic acid compound may be added at once or in batches, or each dicarboxylic acid compound may be added in batches together, or a combination of these.

於步驟(II)中，較佳為於聚醯胺系樹脂之重量平均分子量相對於所獲得之聚醯胺系樹脂之重量平均分子量達到較佳為10%以上、更佳為15%以上之時點，添加相對於欲添加之二羧酸化合物之總莫耳量較佳為1～40莫耳%、更佳為2～25莫耳%之二羧酸化合物。In step (II), it is preferable that the weight average molecular weight of the polyamide resin relative to the weight average molecular weight of the obtained polyamide resin reaches preferably 10% or more, more preferably 15% or more , The total molar amount of the dicarboxylic acid compound to be added is preferably 1-40 mol%, more preferably 2-25 mol% of the dicarboxylic acid compound.

步驟(II)之反應溫度並無特別限定，例如可為5～200℃，較佳為5～100℃，更佳為5～50℃，進而較佳為5～室溫(25℃左右)。又，反應可於空氣中或氮或氬等惰性氣體氛圍下一面攪拌一面進行，亦可於常壓下、加壓下或減壓下進行。較佳之態樣係於常壓及/或上述惰性氣體氛圍下一面攪拌一面進行步驟(II)。The reaction temperature of step (II) is not particularly limited, and may be, for example, 5 to 200°C, preferably 5 to 100°C, more preferably 5 to 50°C, and still more preferably 5 to room temperature (about 25°C). In addition, the reaction can be carried out in air or in an inert gas atmosphere such as nitrogen or argon while stirring, and can also be carried out under normal pressure, under pressure or under reduced pressure. A preferred aspect is to perform step (II) while stirring under normal pressure and/or the aforementioned inert gas atmosphere.

於步驟(II)中，於分批添加二羧酸化合物後，攪拌特定時間等進行反應，藉此獲得聚醯胺醯亞胺前驅物。再者，聚醯胺醯亞胺前驅物例如可藉由向包含聚醯胺醯亞胺前驅物之反應液中添加大量水等，使聚醯胺醯亞胺前驅物析出，並進行過濾、濃縮、乾燥等而單離。In step (II), after the dicarboxylic acid compound is added in batches, the reaction is carried out by stirring for a specific time, etc., thereby obtaining a polyamide imine precursor. Furthermore, the polyimide imine precursor can be precipitated by adding a large amount of water to the reaction solution containing the polyimide imine precursor, and then filtered and concentrated. , Dry and so on.

於步驟(II)中，中間物(A)與二羧酸化合物反應而獲得聚醯胺醯亞胺前驅物。因此，聚醯胺醯亞胺前驅物表示至少具有源自二胺化合物之結構單元、源自四羧酸之結構單元、及源自二羧酸化合物之結構單元的醯亞胺化前(閉環前)之聚醯胺醯亞胺。In step (II), the intermediate (A) is reacted with the dicarboxylic acid compound to obtain a polyimide imine precursor. Therefore, the polyimide imine precursor means that it has at least a structural unit derived from a diamine compound, a structural unit derived from a tetracarboxylic acid, and a structural unit derived from a dicarboxylic acid compound before the imidization (pre-ring closure) ) Of polyamide imine.

於樹脂之製造中，二胺化合物、四羧酸化合物及二羧酸化合物之反應溫度並無特別限定，例如為5～350℃，較佳為5～200℃，更佳為5～100℃。反應時間亦無特別限定，例如為30分鐘～10小時左右。可視需要於惰性氛圍或減壓之條件下進行反應。於較佳之態樣中，反應係於常壓及/或惰性氣體氛圍下一面攪拌一面進行。又，反應較佳為於對反應呈惰性之溶劑中進行。作為溶劑，只要不會對反應造成影響，則並無特別限定，例如可列舉：水、甲醇、乙醇、乙二醇、異丙醇、丙二醇、乙二醇甲醚、乙二醇丁醚、1-甲氧基-2-丙醇、2-丁氧基乙醇、丙二醇單甲醚等醇系溶劑；乙酸乙酯、乙酸丁酯、乙二醇甲醚乙酸酯、γ-丁內酯、γ-戊內酯、丙二醇甲醚乙酸酯、乳酸乙酯等酯系溶劑；丙酮、甲基乙基酮、環戊酮、環己酮、2-庚酮、甲基異丁基酮等酮系溶劑；戊烷、己烷、庚烷等脂肪族烴溶劑；乙基環己烷等脂環式烴溶劑；甲苯、二甲苯等芳香族烴溶劑；乙腈等腈系溶劑；四氫呋喃及二甲氧基乙烷等醚系溶劑；氯仿及氯苯等含氯溶劑；N,N-二甲基乙醯胺、N,N-二甲基甲醯胺等醯胺系溶劑；二甲基碸、二甲基亞碸、環丁碸等含硫系溶劑；碳酸乙二酯、碳酸丙二酯等碳酸酯系溶劑；及其等之組合(混合溶劑)等。該等之中，就溶解性之觀點而言，可較佳地使用醯胺系溶劑。In the production of the resin, the reaction temperature of the diamine compound, the tetracarboxylic acid compound, and the dicarboxylic acid compound is not particularly limited, and is, for example, 5 to 350°C, preferably 5 to 200°C, and more preferably 5 to 100°C. The reaction time is also not particularly limited, and is, for example, about 30 minutes to 10 hours. The reaction can be carried out in an inert atmosphere or under reduced pressure as needed. In a preferred aspect, the reaction is carried out while stirring under normal pressure and/or an inert gas atmosphere. Furthermore, the reaction is preferably carried out in a solvent inert to the reaction. The solvent is not particularly limited as long as it does not affect the reaction. For example, water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1 -Methoxy-2-propanol, 2-butoxyethanol, propylene glycol monomethyl ether and other alcoholic solvents; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, γ -Valerolactone, propylene glycol methyl ether acetate, ethyl lactate and other ester solvents; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl ketone and other ketones Solvents; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicyclic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; tetrahydrofuran and dimethoxy Ether solvents such as ethane; chlorine-containing solvents such as chloroform and chlorobenzene; amine-based solvents such as N,N-dimethylacetamide and N,N-dimethylformamide; dimethyl sulfide, dimethyl Sulfur-containing solvents such as trisulfide and cyclobutane; carbonate-based solvents such as ethylene carbonate and propylene carbonate; and combinations thereof (mixed solvents), etc. Among these, from the viewpoint of solubility, an amide-based solvent can be preferably used.

聚醯胺醯亞胺系樹脂之製造方法亦可進而包含於醯亞胺化觸媒之存在下使聚醯胺醯亞胺前驅物醯亞胺化之步驟(III)。藉由將步驟(II)中所獲得之聚醯胺醯亞胺前驅物供給至步驟(III)，聚醯胺醯亞胺前驅物之結構單元中具有聚醯胺酸結構之結構單元部分經醯亞胺化(經閉環)，可獲得包含式(1)所表示之結構單元與式(2)所表示之結構單元的聚醯胺醯亞胺系樹脂。作為醯亞胺化觸媒，例如可列舉：三丙基胺、二丁基丙基胺、乙基二丁基胺等脂肪族胺；N-乙基哌啶、N-丙基哌啶、N-丁基吡咯啶、N-丁基哌啶、及N-丙基六氫氮呯等脂環式胺(單環式)；氮雜雙環[2.2.1]庚烷、氮雜雙環[3.2.1]辛烷、氮雜雙環[2.2.2]辛烷、及氮雜雙環[3.2.2]壬烷等脂環式胺(多環式)；以及吡啶、2-甲基吡啶(2-皮考啉)、3-甲基吡啶(3-皮考啉)、4-甲基吡啶(4-皮考啉)、2-乙基吡啶、3-乙基吡啶、4-乙基吡啶、2,4-二甲基吡啶、2,4,6-三甲基吡啶、3,4-環戊烯并吡啶、5,6,7,8-四氫異喹啉、及異喹啉等芳香族胺。又，就容易促進醯亞胺化反應之觀點而言，較佳為一併使用醯亞胺化觸媒及酸酐。酸酐可列舉用於醯亞胺化反應之慣用之酸酐等，作為其具體例，可列舉：乙酸酐、丙酸酐、丁酸酐等脂肪族酸酐，鄰苯二甲酸等芳香族酸酐等。The manufacturing method of the polyimide-based resin may further include the step (III) of imidizing the polyimide imide precursor in the presence of the imidization catalyst. By supplying the polyamide imide precursor obtained in step (II) to step (III), the structural unit part of the polyamide imide precursor having the polyamide acid structure is passed through By imidization (through ring closure), a polyamidoimide resin containing the structural unit represented by formula (1) and the structural unit represented by formula (2) can be obtained. Examples of the imidization catalyst include: aliphatic amines such as tripropylamine, dibutylpropylamine, and ethyldibutylamine; N-ethylpiperidine, N-propylpiperidine, N -Alicyclic amines such as butylpyrrolidine, N-butylpiperidine, and N-propylhexahydroazepine (monocyclic); azabicyclo[2.2.1]heptane, azabicyclo[3.2. 1] Octane, azabicyclo[2.2.2]octane, and azabicyclo[3.2.2]nonane and other alicyclic amines (polycyclic); and pyridine, 2-picoline (2-pi Pyridine), 3-methylpyridine (3-picolin), 4-methylpyridine (4-picolin), 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2, Aromatic amines such as 4-lutidine, 2,4,6-trimethylpyridine, 3,4-cyclopentenopyridine, 5,6,7,8-tetrahydroisoquinoline, and isoquinoline . Moreover, from the viewpoint of facilitating the promotion of the imidization reaction, it is preferable to use the imidization catalyst and acid anhydride together. Examples of the acid anhydride include commonly used acid anhydrides used in the imidization reaction, and specific examples thereof include aliphatic anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride, and aromatic anhydrides such as phthalic acid.

聚醯胺醯亞胺系樹脂可藉由慣用之方法、例如過濾、濃縮、萃取、晶析、再結晶、管柱層析等分離方法或將該等組合之分離方法進行單離(分離精製)，於較佳之態樣中，可藉由向包含聚醯胺醯亞胺系樹脂之反應液中添加大量甲醇等醇，使樹脂析出並進行濃縮、過濾、乾燥等而單離。Polyamidoimine-based resins can be isolated (separation and purification) by conventional methods, such as separation methods such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination of separation methods. In a preferred aspect, a large amount of alcohol such as methanol can be added to the reaction liquid containing the polyimide-based resin to precipitate the resin and then be isolated by concentration, filtration, drying, etc.

＜填料＞ 本發明之光學膜除上述聚醯胺醯亞胺系樹脂以外，亦可包含至少1種填料。作為填料，例如可列舉有機粒子、無機粒子等，較佳為列舉無機粒子。作為無機粒子，可列舉：二氧化矽、氧化鋯、氧化鋁、二氧化鈦、氧化鋅、氧化鍺、氧化銦、氧化錫、銦錫氧化物、氧化銻、氧化鈰等金屬氧化物粒子、氟化鎂、氟化鈉等金屬氟化物粒子等；該等之中，就容易提高光學膜之彈性模數及/或撕裂強度而容易提高耐衝擊性之觀點而言，較佳為列舉二氧化矽粒子、氧化鋯粒子、氧化鋁粒子，更佳為列舉二氧化矽粒子。該等填料可單獨或將2種以上組合使用。＜Filling＞ The optical film of the present invention may contain at least one type of filler in addition to the above-mentioned polyimide-based resin. Examples of the filler include organic particles, inorganic particles, and the like, and preferably inorganic particles. Examples of inorganic particles include: metal oxide particles such as silicon dioxide, zirconium oxide, aluminum oxide, titanium dioxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide, and magnesium fluoride , Sodium fluoride and other metal fluoride particles; among these, in terms of easily improving the elastic modulus and/or tearing strength of the optical film and easily improving the impact resistance, it is preferable to cite silica particles , Zirconia particles, alumina particles, more preferably silica particles. These fillers can be used alone or in combination of two or more kinds.

填料、較佳為二氧化矽粒子之平均一次粒徑為1 nm以上，更佳為5 nm以上，進而較佳為10 nm以上，進而更佳為15 nm以上，尤佳為20 nm以上，較佳為100 nm以下，更佳為90 nm以下，進而較佳為80 nm以下，進而更佳為70 nm以下，尤佳為60 nm以下，更尤佳為50 nm以下，進而尤佳為40 nm以下。若二氧化矽粒子之平均一次粒徑為上述範圍內，則容易抑制二氧化矽粒子之凝聚而提高所獲得之光學膜之光學特性。填料之平均一次粒徑可藉由BET(Brunauer-Emmett-Teller，布厄特)法進行測定。再者，亦可藉由穿透式電子顯微鏡或掃描型電子顯微鏡之圖像解析測定平均一次粒徑。The filler, preferably silica particles, have an average primary particle size of 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more, still more preferably 15 nm or more, particularly preferably 20 nm or more, It is preferably 100 nm or less, more preferably 90 nm or less, still more preferably 80 nm or less, still more preferably 70 nm or less, particularly preferably 60 nm or less, more preferably 50 nm or less, and even more preferably 40 nm the following. If the average primary particle size of the silica particles is within the above range, it is easy to inhibit the aggregation of the silica particles and improve the optical properties of the obtained optical film. The average primary particle size of the filler can be measured by the BET (Brunauer-Emmett-Teller, Buert) method. Furthermore, the average primary particle size can also be measured by image analysis of a transmission electron microscope or a scanning electron microscope.

於本發明之光學膜含有填料、較佳為二氧化矽粒子之情形時，填料之含量相對於光學膜100質量份，通常為0.1質量份以上，較佳為1質量份以上，更佳為5質量份以上，進而較佳為10質量份以上，進而更佳為20質量份以上，尤佳為30質量份以上，較佳為60質量份以下。若填料之含量為上述下限以上，則容易提高所獲得之光學膜之彈性模數。又，若填料之含量為上述上限以下，則容易提高光學膜之光學特性。When the optical film of the present invention contains a filler, preferably silica particles, the content of the filler relative to 100 parts by mass of the optical film is usually 0.1 part by mass or more, preferably 1 part by mass or more, more preferably 5 Parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, particularly preferably 30 parts by mass or more, and preferably 60 parts by mass or less. If the content of the filler is more than the above lower limit, it is easy to increase the elastic modulus of the obtained optical film. In addition, if the content of the filler is less than or equal to the above upper limit, it is easy to improve the optical properties of the optical film.

＜紫外線吸收劑＞ 本發明之光學膜亦可包含至少1種紫外線吸收劑。紫外線吸收劑可自於樹脂材料之領域中通常用作紫外線吸收劑者中適當選擇。紫外線吸收劑可包含吸收400 nm以下之波長之光之化合物。作為紫外線吸收劑，例如可列舉選自由二苯甲酮系化合物、水楊酸酯系化合物、苯并三唑系化合物、及三𠯤系化合物所組成之群中之至少1種化合物。紫外線吸收劑可單獨或將兩種以上組合使用。藉由使光學膜含有紫外線吸收劑，樹脂之劣化得到抑制，故而於將本發明之光學膜應用於顯示裝置等之情形時可提高視認性。於本說明書中，所謂「系化合物」，係指附有該「系化合物」之化合物之衍生物。例如，所謂「二苯甲酮系化合物」，係指具有作為母體骨架之二苯甲酮及鍵結於二苯甲酮之取代基之化合物。＜Ultraviolet absorber＞ The optical film of the present invention may also contain at least one ultraviolet absorber. The ultraviolet absorber can be appropriately selected from those generally used as ultraviolet absorbers in the field of resin materials. The ultraviolet absorber may include a compound that absorbs light with a wavelength below 400 nm. Examples of the ultraviolet absorber include at least one compound selected from the group consisting of benzophenone-based compounds, salicylate-based compounds, benzotriazole-based compounds, and triazole-based compounds. The ultraviolet absorber can be used alone or in combination of two or more. By containing the ultraviolet absorber in the optical film, the degradation of the resin is suppressed, and therefore the visibility can be improved when the optical film of the present invention is applied to a display device or the like. In this specification, the "system compound" refers to a derivative of the compound to which the "system compound" is attached. For example, the so-called "benzophenone-based compound" refers to a compound having benzophenone as a parent skeleton and a substituent bonded to benzophenone.

於本發明之光學膜含有紫外線吸收劑之情形時，紫外線吸收劑之含量相對於光學膜中所包含之聚醯胺醯亞胺系樹脂之質量，較佳為0.01～10質量份，更佳為1～8質量份，進而較佳為2～7質量份。若紫外線吸收劑之含量為上述下限以上，則容易提高紫外線吸收性。若紫外線吸收劑之含量為上述上限以下，則可抑制因製造基材時之熱而導致之紫外線吸收劑之分解，從而容易提高光學特性、例如容易降低霧度。When the optical film of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber relative to the mass of the polyamide imine resin contained in the optical film is preferably 0.01-10 parts by mass, more preferably 1-8 parts by mass, more preferably 2-7 parts by mass. If the content of the ultraviolet absorber is more than the above lower limit, it is easy to improve the ultraviolet absorbability. If the content of the ultraviolet absorber is equal to or less than the above upper limit, the decomposition of the ultraviolet absorber due to heat during the production of the substrate can be suppressed, and the optical properties can be easily improved, for example, the haze can be easily reduced.

＜其他添加劑＞ 本發明之光學膜亦可進而含有填料、紫外線吸收劑以外之其他添加劑。作為其他添加劑，例如可列舉：抗氧化劑、脫模劑、穩定劑、上藍劑等著色劑、阻燃劑、pH值調整劑、二氧化矽分散劑、潤滑劑、增黏劑、及調平劑等。於含有其他添加劑之情形時，其含量相對於光學膜之質量，可較佳為0.001～20質量份、更佳為0.01～15質量份、進而較佳為0.1～10質量份。＜Other additives＞ The optical film of the present invention may further contain other additives other than fillers and ultraviolet absorbers. Examples of other additives include: antioxidants, mold release agents, stabilizers, bluing agents and other colorants, flame retardants, pH adjusters, silica dispersants, lubricants, tackifiers, and leveling agents剂 etc. When other additives are contained, the content thereof may be preferably 0.001 to 20 parts by mass, more preferably 0.01 to 15 parts by mass, and still more preferably 0.1 to 10 parts by mass relative to the mass of the optical film.

(光學膜之製造方法) 製造本發明之光學膜之方法並無特別限定，例如可為包含以下之步驟之製造方法： (a)製備至少包含上述聚醯胺醯亞胺系樹脂及溶劑之聚醯胺醯亞胺系樹脂清漆之清漆製備步驟、 (b)將清漆塗佈於支持材而形成塗膜之塗佈步驟、及 (c)使所塗佈之液體(塗膜)乾燥而形成光學膜之光學膜形成步驟(Method of manufacturing optical film) The method of manufacturing the optical film of the present invention is not particularly limited. For example, it may be a manufacturing method including the following steps: (a) A varnish preparation step for preparing a polyimide resin varnish containing at least the polyimide resin and a solvent, (b) The coating step of applying the varnish to the support material to form a coating film, and (c) The optical film forming step of drying the applied liquid (coating film) to form an optical film

於清漆製備步驟中，使聚醯胺醯亞胺系樹脂溶解於溶劑中，並視需要添加上述填料、紫外線吸收劑等添加劑後進行攪拌混合，藉此製備清漆。再者，於使用二氧化矽粒子作為填料之情形時，亦可將矽凝膠添加至樹脂中，該矽凝膠係利用可溶解上述樹脂之溶劑、例如下述清漆之製備所使用之溶劑，置換包含二氧化矽粒子之矽凝膠分散液而成者。In the varnish preparation step, the polyimide-based resin is dissolved in a solvent, and additives such as fillers and ultraviolet absorbers are added as needed, followed by stirring and mixing, thereby preparing a varnish. Furthermore, when silica particles are used as a filler, a silicone gel can also be added to the resin. The silicone gel uses a solvent that can dissolve the above-mentioned resin, such as the solvent used in the preparation of the following varnish. Replacement of silica gel dispersion containing silica particles.

用於製備清漆之溶劑只要可溶解上述樹脂，則並無特別限定。作為該溶劑，例如可列舉：N,N-二甲基乙醯胺、N,N-二甲基甲醯胺等醯胺系溶劑；γ-丁內酯(GBL)、γ-戊內酯等內酯系溶劑；二甲基碸、二甲基亞碸、環丁碸等含硫系溶劑；碳酸乙二酯、碳酸丙二酯等碳酸酯系溶劑；及其等之組合(混合溶劑)。該等之中，較佳為醯胺系溶劑或內酯系溶劑，進而較佳為內酯系溶劑。若使用內酯系溶劑，則有成為光學特性較高之膜之傾向。該等溶劑可單獨或將兩種以上組合使用。又，清漆中亦可包含水、醇系溶劑、酮系溶劑、非環狀酯系溶劑、醚系溶劑等。就容易提高聚醯胺醯亞胺系樹脂清漆之穩定性之觀點而言，聚醯胺醯亞胺系樹脂清漆中之固形物成分濃度較佳為1～25質量%，更佳為5～20質量%，進而較佳為5～15質量%。又，就容易提高聚醯胺醯亞胺系樹脂清漆之穩定性之觀點而言，本發明之聚醯胺醯亞胺系樹脂清漆中之溶劑之濃度基於聚醯胺醯亞胺系樹脂清漆之總量，較佳為75～99質量%，更佳為80～95質量%，進而較佳為85～95質量%。The solvent used to prepare the varnish is not particularly limited as long as it can dissolve the above-mentioned resin. Examples of the solvent include amine-based solvents such as N,N-dimethylacetamide and N,N-dimethylformamide; γ-butyrolactone (GBL), γ-valerolactone, etc. Lactone-based solvents; sulfur-containing solvents such as dimethyl sulfide, dimethyl sulfide, and cyclobutyl sulfide; carbonate-based solvents such as ethylene carbonate and propylene carbonate; and combinations thereof (mixed solvents). Among these, an amide-based solvent or a lactone-based solvent is preferred, and a lactone-based solvent is more preferred. If a lactone-based solvent is used, it tends to become a film with higher optical properties. These solvents can be used alone or in combination of two or more. In addition, the varnish may contain water, alcohol solvents, ketone solvents, acyclic ester solvents, ether solvents, and the like. From the viewpoint of easily improving the stability of the polyimide resin varnish, the solid content concentration in the polyimide resin varnish is preferably 1-25% by mass, more preferably 5-20 % By mass, more preferably 5 to 15% by mass. In addition, from the viewpoint of easily improving the stability of the polyimide resin varnish, the concentration of the solvent in the polyimide resin varnish of the present invention is based on the polyimide resin varnish. The total amount is preferably 75 to 99% by mass, more preferably 80 to 95% by mass, and still more preferably 85 to 95% by mass.

於塗佈步驟中，藉由公知之塗佈方法於支持材上塗佈清漆而形成塗膜。作為公知之塗佈方法，例如可列舉：線棒塗佈法、反向塗佈、凹版塗佈等輥塗法、模嘴塗佈法、卡馬塗佈法、模唇塗佈法、旋轉塗佈法、篩網塗佈法、噴注式塗佈法、浸漬法、噴霧法、流涎成形法等。In the coating step, a varnish is applied to the support by a known coating method to form a coating film. As well-known coating methods, for example, roll coating methods such as wire bar coating, reverse coating, and gravure coating, die nozzle coating method, kama coating method, die lip coating method, spin coating Cloth method, screen coating method, spray coating method, dipping method, spray method, casting method, etc.

於光學膜形成步驟中，可藉由使塗膜乾燥並自支持材剝離而形成光學膜。亦可於剝離後進而設置使光學膜乾燥之步驟。塗膜之乾燥通常可於50～350℃之溫度下進行。可視需要於惰性氛圍或減壓之條件下進行塗膜之乾燥。In the optical film forming step, the optical film can be formed by drying the coating film and peeling it from the support. It is also possible to further provide a step of drying the optical film after peeling. The drying of the coating film can usually be carried out at a temperature of 50 to 350°C. The coating film can be dried under inert atmosphere or reduced pressure as needed.

作為支持材之例，若為金屬系，則可列舉SUS(Steel Use Stainless，不鏽鋼)板，若為樹脂系，則可列舉：PET(Polyethylene terephthalate，聚對苯二甲酸乙二酯)膜、PEN(Polyethylene naphthalate，聚萘二甲酸乙二酯)膜、聚醯胺系樹脂膜、聚醯亞胺系樹脂膜、環烯烴系聚合物(COP)膜、丙烯酸系膜等。其中，就平滑性、耐熱性優異之觀點而言，較佳為PET膜、COP膜等，進而就與光學膜之密接性及成本之觀點而言，更佳為PET膜。As an example of the support material, if it is a metal-based, SUS (Steel Use Stainless) plate, if it is a resin-based, it can include: PET (Polyethylene terephthalate, polyethylene terephthalate) film, PEN (Polyethylene naphthalate, polyethylene naphthalate) film, polyamide resin film, polyimide resin film, cycloolefin polymer (COP) film, acrylic film, etc. Among them, from the viewpoint of excellent smoothness and heat resistance, a PET film, a COP film, etc. are preferred, and further, from the viewpoint of adhesion to an optical film and cost, a PET film is more preferred.

本發明之光學膜之用途並無特別限定，可用於各種用途。本發明之光學膜可如上所述般為單層，亦可為積層體，可直接使用本發明之光學膜，亦可進而作為與其他膜之積層體而使用。再者，於光學膜為積層體之情形時，將積層於光學膜之單面或兩面之所有層包含在內稱為光學膜。The use of the optical film of the present invention is not particularly limited, and can be used for various purposes. The optical film of the present invention may be a single layer as described above, or may be a laminate, and the optical film of the present invention may be used directly, or it may be used as a laminate with other films. Furthermore, when the optical film is a laminated body, all layers laminated on one or both sides of the optical film are referred to as an optical film.

(功能層) 亦可於本發明之光學膜之至少一面積層1層以上之功能層。作為功能層，例如可列舉：紫外線吸收層、硬塗層、底塗層、氣體阻隔層、黏著層、色相調整層、折射率調整層等。功能層可單獨或將兩種以上組合使用。(Functional layer) It can also be a functional layer of at least one area layer of the optical film of the present invention. As the functional layer, for example, an ultraviolet absorbing layer, a hard coat layer, an undercoat layer, a gas barrier layer, an adhesion layer, a hue adjustment layer, a refractive index adjustment layer, etc. may be mentioned. The functional layer can be used alone or in combination of two or more.

紫外線吸收層係具有紫外線吸收之功能之層，例如，係由選自紫外線硬化型之透明樹脂、電子束硬化型之透明樹脂、及熱硬化型之透明樹脂中之主材與分散於該主材中之紫外線吸收劑構成。The ultraviolet absorbing layer is a layer with ultraviolet absorbing function, for example, is composed of a main material selected from the group consisting of ultraviolet curable transparent resin, electron beam curable transparent resin, and thermosetting transparent resin and dispersed in the main material It is composed of UV absorbers.

亦可於本發明之光學膜之至少一面設置硬塗層。硬塗層之厚度並無特別限定，例如可為2～100 μm。若上述硬塗層之厚度處於上述範圍，則可確保充分之耐擦傷性，又，有耐彎曲性不易降低而不易產生因硬化收縮而導致產生捲曲之問題之傾向。 上述硬塗層可使包含可藉由活性能量線照射或熱能量賦予形成交聯結構之反應性材料硬塗組合物硬化而形成，較佳為藉由活性能量線照射而成者。活性能量線被定義為可將產生活性種之化合物分解而產生活性種之能量線，可列舉：可見光、紫外線、紅外線、X射線、α射線、β射線、γ射線及電子束等；較佳為列舉紫外線。上述硬塗組合物含有自由基聚合性化合物及陽離子聚合性化合物之至少1種聚合物。A hard coat layer can also be provided on at least one side of the optical film of the present invention. The thickness of the hard coat layer is not particularly limited, and may be, for example, 2 to 100 μm. If the thickness of the hard coat layer is in the above range, sufficient abrasion resistance can be ensured, and the bending resistance is unlikely to decrease, and the problem of curling due to hardening shrinkage tends to occur. The hard coat layer can be formed by curing a hard coat composition containing a reactive material that can form a cross-linked structure by irradiation with active energy rays or by applying thermal energy, and is preferably formed by irradiation with active energy rays. Active energy rays are defined as energy rays that can decompose compounds that produce active species to produce active species. Examples include visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, γ rays, and electron beams; preferably List ultraviolet rays. The above-mentioned hard coating composition contains at least one polymer of a radical polymerizable compound and a cation polymerizable compound.

上述自由基聚合性化合物係具有自由基聚合性基之化合物。作為上述自由基聚合性化合物所具有之自由基聚合性基，只要為可產生自由基聚合反應之官能基即可，可列舉包含碳‐碳不飽和雙鍵之基等，具體而言，可列舉：乙烯基、(甲基)丙烯醯基等。再者，於上述自由基聚合性化合物具有2個以上之自由基聚合性基之情形時，該等自由基聚合性基可分別相同，亦可不同。就提高硬塗層之硬度之方面而言，上述自由基聚合性化合物於1分子中所具有之自由基聚合性基之數量較佳為2以上。作為上述自由基聚合性化合物，就反應性之高度之方面而言，較佳為列舉具有(甲基)丙烯醯基之化合物，具體而言，可列舉：1分子中具有2～6個(甲基)丙烯醯基之被稱為多官能丙烯酸酯單體之化合物或被稱為(甲基)丙烯酸環氧酯、(甲基)丙烯酸胺基甲酸酯、聚酯(甲基)丙烯酸酯之分子內具有數個(甲基)丙烯醯基之分子量為數百至數千之低聚物；較佳為列舉選自(甲基)丙烯酸環氧酯、(甲基)丙烯酸胺基甲酸酯及聚酯(甲基)丙烯酸酯中之1種以上。The above-mentioned radically polymerizable compound is a compound having a radically polymerizable group. The radical polymerizable group possessed by the above radical polymerizable compound may be a functional group capable of generating a radical polymerization reaction. Examples include groups containing a carbon-carbon unsaturated double bond. Specifically, examples include : Vinyl, (meth)acrylic acid, etc. In addition, when the above-mentioned radically polymerizable compound has two or more radically polymerizable groups, the radically polymerizable groups may be the same or different. In terms of increasing the hardness of the hard coat layer, the number of radical polymerizable groups contained in one molecule of the radical polymerizable compound is preferably 2 or more. As the above-mentioned radically polymerizable compound, in terms of the high degree of reactivity, it is preferable to cite a compound having a (meth)acryloyl group. Specifically, for example, there are 2 to 6 (form) groups per molecule. ((Meth)acrylic acid ester) compound known as polyfunctional acrylate monomer or known as epoxy (meth)acrylate, (meth)acrylate urethane, polyester (meth)acrylate An oligomer with several (meth)acrylic acid groups in the molecule and a molecular weight of several hundred to several thousand; preferably selected from epoxy (meth)acrylate and (meth)acrylate urethane And one or more of polyester (meth)acrylates.

上述陽離子聚合性化合物係具有環氧基、氧雜環丁基、乙烯基醚基等陽離子聚合性基之化合物。就提高硬塗層之硬度之方面而言，上述陽離子聚合性化合物於1分子中所具有之陽離子聚合性基之數量較佳為2以上，更佳為3以上。The above-mentioned cationically polymerizable compound is a compound having a cationically polymerizable group such as an epoxy group, an oxetanyl group, and a vinyl ether group. In terms of increasing the hardness of the hard coat layer, the number of cationically polymerizable groups contained in the cationically polymerizable compound per molecule is preferably 2 or more, more preferably 3 or more.

又，作為上述陽離子聚合性化合物，其中，較佳為具有環氧基及氧雜環丁基之至少1種作為陽離子聚合性基之化合物。就聚合反應所伴有之收縮較小之方面而言，較佳為環氧基、氧雜環丁基等環狀醚基。又，具有環狀醚基中之環氧基之化合物具有容易獲得各種結構之化合物、不會對所獲得之硬塗層之耐久性造成不良影響、與自由基聚合性化合物之相溶性亦容易控制之優勢。又，環狀醚基中之氧雜環丁基具有如下等優勢：與環氧基相比聚合度容易提高，加快由所獲得之硬塗層之陽離子聚合性化合物獲得之網形成速度，即便於與自由基聚合性化合物混合存在之區域，亦不會使未反應之單體殘留於膜中而形成獨立之網。Furthermore, as the above-mentioned cationically polymerizable compound, a compound having at least one of an epoxy group and an oxetanyl group as a cationically polymerizable group is preferred. In terms of small shrinkage accompanying the polymerization reaction, cyclic ether groups such as epoxy groups and oxetanyl groups are preferred. In addition, the compound having the epoxy group in the cyclic ether group has a compound that is easy to obtain various structures, does not adversely affect the durability of the obtained hard coat layer, and the compatibility with the radical polymerizable compound is easy to control The advantage. In addition, the oxetanyl group in the cyclic ether group has the following advantages: the degree of polymerization is easily increased compared with the epoxy group, and the speed of network formation obtained from the cationically polymerizable compound of the hard coat layer is accelerated, even if The area mixed with the radical polymerizable compound will not leave unreacted monomer in the film and form an independent network.

作為具有環氧基之陽離子聚合性化合物，例如可列舉：藉由利用過氧化氫、過酸等適當之氧化劑使具有脂環族環之多元醇之聚縮水甘油醚或含環己烯環、環戊烯環之化合物環氧化而獲得之脂環族環氧樹脂；脂肪族多元醇或其環氧烷加成物之聚縮水甘油醚、脂肪族長鏈多元酸之聚縮水甘油酯、(甲基)丙烯酸縮水甘油酯之均聚物、共聚物等脂肪族環氧樹脂；藉由雙酚A、雙酚F或氫化雙酚A等雙酚類或其等之環氧烷加成體、己內酯加成體等衍生物與表氯醇之反應而製造之縮水甘油醚、及作為酚醛清漆環氧樹脂等且自雙酚類衍生之縮水甘油醚型環氧樹脂等。Examples of cationic polymerizable compounds having epoxy groups include: polyglycidyl ethers of polyhydric alcohols having an alicyclic ring or cyclohexene-containing rings and ring-containing compounds by using suitable oxidizing agents such as hydrogen peroxide and peracid. Alicyclic epoxy resin obtained by epoxidation of compound of pentene ring; polyglycidyl ether of aliphatic polyol or its alkylene oxide adduct, polyglycidyl ester of aliphatic long-chain polyacid, (methyl) Aliphatic epoxy resins such as homopolymers and copolymers of glycidyl acrylate; by bisphenols such as bisphenol A, bisphenol F or hydrogenated bisphenol A or their alkylene oxide adducts, caprolactone Glycidyl ether produced by the reaction of derivatives such as adduct and epichlorohydrin, and glycidyl ether type epoxy resin derived from bisphenols as novolac epoxy resins, etc.

上述硬塗組合物可進而包含聚合起始劑。作為聚合起始劑，可列舉：自由基聚合起始劑、陽離子聚合起始劑、自由基及陽離子聚合起始劑等；可適當選擇並使用。該等聚合起始劑藉由活性能量線照射及加熱之至少一種而被分解，產生自由基或陽離子後進行自由基聚合與陽離子聚合。 自由基聚合起始劑只要可藉由活性能量線照射及加熱之至少一種釋放使自由基聚合開始之物質即可。例如，作為熱自由基聚合起始劑，可列舉：過氧化氫、過苯甲酸等有機過氧化物、偶氮丁腈等偶氮化合物等。 作為活性能量線自由基聚合起始劑，有利用分子之分解生成自由基之Type1型自由基聚合起始劑、與三級胺共存並利用脫氫型反應生成自由基之Type2型自由基聚合起始劑，其等可單獨或併用使用。 陽離子聚合起始劑只要為可藉由活性能量線照射及加熱之至少一種釋放可使陽離子聚合開始之物質即可。作為陽離子聚合起始劑，可使用芳香族錪鹽、芳香族鋶鹽、環戊二烯基鐵(II)錯合物等。該等可根據結構之差異利用活性能量線照射或加熱之任一者或兩者開始陽離子聚合。The above-mentioned hard coating composition may further contain a polymerization initiator. Examples of the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, radical and cationic polymerization initiators, etc.; they can be appropriately selected and used. The polymerization initiators are decomposed by at least one of active energy ray irradiation and heating to generate free radicals or cations and then undergo radical polymerization and cationic polymerization. The radical polymerization initiator should just be a substance that can release radical polymerization by at least one of active energy ray irradiation and heating. For example, as a thermal radical polymerization initiator, organic peroxides, such as hydrogen peroxide and perbenzoic acid, azo compounds, such as azobutyronitrile, etc. are mentioned. As active energy ray radical polymerization initiators, there are Type1 radical polymerization initiators that use the decomposition of molecules to generate free radicals, and Type2 radical polymerization initiators that coexist with tertiary amines and generate free radicals by dehydrogenation reaction. The starting agent can be used alone or in combination. The cationic polymerization initiator may be a substance that can be released by at least one of active energy ray irradiation and heating to initiate cationic polymerization. As the cationic polymerization initiator, an aromatic iodonium salt, an aromatic sulfonium salt, a cyclopentadienyl iron (II) complex, and the like can be used. These can start cationic polymerization by either or both of active energy ray irradiation or heating according to the difference in structure.

上述聚合起始劑相對於上述硬塗組合物整體100質量%，可較佳為包含0.1～10質量%。若上述聚合起始劑之含量處於上述範圍，則可充分地進行硬化，可使最終獲得之塗膜之機械物性及密接力成為良好之範圍，又，有不易產生因硬化收縮而導致之接著力不良或破裂現象及捲曲現象。The polymerization initiator may preferably be contained in an amount of 0.1 to 10% by mass with respect to 100% by mass of the entire hard coating composition. If the content of the polymerization initiator is in the above range, the curing can be carried out sufficiently, and the mechanical properties and adhesion of the finally obtained coating film can be in a good range, and the adhesive force caused by curing shrinkage is not easily generated. Bad or cracked phenomenon and curling phenomenon.

上述硬塗組合物可進而包含選自由溶劑及添加劑所組成之群中之一種以上。上述溶劑只要為可使上述聚合性化合物及聚合起始劑溶解或分散且作為本技術領域之硬塗組合物之溶劑而被知之溶劑，則可於不損及本發明之效果之範圍內使用。上述添加劑可進而包含無機粒子、調平劑、穩定劑、界面活性劑、抗靜電劑、潤滑劑、防污劑等。 The above-mentioned hard coating composition may further include one or more selected from the group consisting of solvents and additives. As long as the above-mentioned solvent can dissolve or disperse the above-mentioned polymerizable compound and polymerization initiator and is known as a solvent for hard coat compositions in this technical field, it can be used within a range that does not impair the effects of the present invention. The above-mentioned additives may further include inorganic particles, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, and the like.

黏著層係具有黏著性之功能之層，具有使光學膜接著於其他構件之功能。作為黏著層之形成材料，可使用通常已知者。例如可使用熱硬化性樹脂組合物或光硬化性樹脂組合物。於該情形時，可藉由事後供給能量使樹脂組合物高分子化並硬化。The adhesive layer is a layer with adhesive function and has the function of adhering the optical film to other components. As the forming material of the adhesive layer, generally known ones can be used. For example, a thermosetting resin composition or a photocuring resin composition can be used. In this case, the resin composition can be polymerized and cured by supplying energy afterwards.

黏著層亦可為被稱為感壓型接著劑(Pressure Sensitive Adhesive，PSA)之藉由按壓貼附於對象物之層。感壓型接著劑可為作為「常溫下具有黏著性，且以較輕之壓力接著於被接著材之物質」(JIS K 6800)之黏著劑，亦可為作為「將特定成分內含於保護覆膜(微膠囊)中，並可於破壞覆膜之前藉由適當之方法(壓力、熱等)保持穩定性之接著劑」(JIS K 6800)之膠囊型接著劑。The adhesive layer may also be a layer which is called a pressure sensitive adhesive (PSA) and is attached to an object by pressing. Pressure-sensitive adhesives can be used as "substances that are adhesive at room temperature and adhere to the material to be bonded with a lighter pressure" (JIS K 6800), and can also be used as "incorporating specific ingredients in protection In the film (microcapsule), it is a capsule adhesive agent that can maintain stability by appropriate methods (pressure, heat, etc.) before breaking the film." (JIS K 6800) Capsule adhesive.

色相調整層係具有色相調整之功能之層，且係可將包含光學膜之積層體調整為目標色相之層。色相調整層例如係含有樹脂及著色劑之層。作為該著色劑，例如可列舉：氧化鈦、氧化鋅、紅丹、氧化鈦系焙燒顏料、群青、鋁酸鈷、及碳黑等無機顏料；偶氮系化合物、喹吖酮系化合物、蒽醌系化合物、苝系化合物、異吲哚啉酮系化合物、酞菁系化合物、喹酞酮系化合物、蒽系化合物、及吡咯并吡咯二酮系化合物等有機顏料；硫酸鋇、及碳酸鈣等體質顏料；以及鹼性染料、酸性染料、及媒染染料等染料。The hue adjustment layer is a layer with the function of hue adjustment, and is a layer that can adjust the layered body including the optical film to the target hue. The hue adjusting layer is, for example, a layer containing resin and coloring agent. Examples of the colorant include inorganic pigments such as titanium oxide, zinc oxide, red lead, titanium oxide-based calcined pigments, ultramarine blue, cobalt aluminate, and carbon black; azo-based compounds, quinacridone-based compounds, and anthraquinone Organic pigments such as compounds, perylene compounds, isoindolinone compounds, phthalocyanine compounds, quinophthalone compounds, anthracene compounds, and diketopyrrolopyrrole compounds; barium sulfate and calcium carbonate Pigments; and dyes such as basic dyes, acid dyes, and mordant dyes.

折射率調整層係具有折射率調整之功能之層，例如係具有與光學膜不同之折射率且可對光學積層體賦予特定折射率之層。折射率調整層例如可為含有適當選擇之樹脂、及視情形時進而含有顏料之樹脂層，亦可為金屬之薄膜。作為調整折射率之顏料，例如可列舉：氧化矽、氧化鋁、氧化銻、氧化錫、氧化鈦、氧化鋯及氧化鉭。該顏料之平均一次粒徑可為0.1 μm以下。藉由將顏料之平均一次粒徑設為0.1 μm以下，可防止透過折射率調整層之光之漫反射，從而防止透亮度降低。作為用於折射率調整層之金屬，例如可列舉：氧化鈦、氧化鉭、氧化鋯、氧化鋅、氧化錫、氧化矽、氧化銦、酸氮化鈦、氮化鈦、酸氮化矽、氮化矽等金屬氧化物或金屬氮化物。The refractive index adjustment layer is a layer having a refractive index adjustment function, for example, a layer that has a refractive index different from that of an optical film and can give a specific refractive index to the optical laminate. The refractive index adjustment layer may be, for example, a resin layer containing appropriately selected resin and pigments as appropriate, or a metal film. Examples of pigments that adjust the refractive index include silica, alumina, antimony oxide, tin oxide, titanium oxide, zirconium oxide, and tantalum oxide. The average primary particle size of the pigment may be 0.1 μm or less. By setting the average primary particle size of the pigment to 0.1 μm or less, the diffuse reflection of the light passing through the refractive index adjustment layer can be prevented, thereby preventing the decrease in transmittance. Examples of metals used for the refractive index adjustment layer include titanium oxide, tantalum oxide, zirconium oxide, zinc oxide, tin oxide, silicon oxide, indium oxide, acid titanium nitride, titanium nitride, acid silicon nitride, and nitrogen. Metal oxide or metal nitride such as silicide.

本發明之光學膜可為單層，亦可為積層體，例如可直接使用如上所述般製造之光學膜，亦可進而作為與其他膜之積層體使用。The optical film of the present invention may be a single layer or a laminate. For example, the optical film manufactured as described above may be used as it is, or it may be used as a laminate with other films.

於本發明之一實施形態中，光學膜亦可於至少一面、換言之單面或兩面具有保護膜。例如於在光學膜之單面具有功能層之情形時，保護膜可積層於光學膜側之表面或功能層側之表面，亦可積層於光學膜側與功能層側之兩者。於在光學膜之兩面具有功能層之情形時，保護膜可積層於其中一功能層側之表面，亦可積層於兩功能層側之表面。保護膜係用以暫時保護光學膜或功能層之表面之膜，只要為可保護光學膜或功能層之表面之可剝離之膜，則並無特別限定。作為保護膜，例如可列舉：聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯等聚酯系樹脂膜；聚乙烯、聚丙烯膜等聚烯烴系樹脂膜、丙烯酸系樹脂膜等；較佳為選自由聚烯烴系樹脂膜、聚對苯二甲酸乙二酯系樹脂膜及丙烯酸系樹脂膜所組成之群中。於光學膜具有2層保護膜之情形時，各保護膜可相同，亦可不同。In one embodiment of the present invention, the optical film may also have a protective film on at least one side, in other words, one side or both sides. For example, when the optical film has a functional layer on one side, the protective film may be laminated on the surface on the optical film side or the functional layer side, or on both the optical film side and the functional layer side. When there are functional layers on both sides of the optical film, the protective film can be laminated on the surface of one of the functional layers or on the surface of the two functional layers. The protective film is a film for temporarily protecting the surface of the optical film or the functional layer, and is not particularly limited as long as it is a peelable film that can protect the surface of the optical film or the functional layer. Examples of protective films include polyester resin films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin resin films such as polyethylene and polypropylene films. Resin film, acrylic resin film, etc.; preferably selected from the group consisting of polyolefin resin film, polyethylene terephthalate resin film, and acrylic resin film. When the optical film has two protective films, each protective film may be the same or different.

保護膜之厚度並無特別限定，通常為10～120 μm，較佳為15～110 μm，更佳為20～100 μm。於光學膜具有2層保護膜之情形時，各保護膜之厚度可相同，亦可不同。The thickness of the protective film is not particularly limited, and is usually 10 to 120 μm, preferably 15 to 110 μm, and more preferably 20 to 100 μm. When the optical film has two protective films, the thickness of each protective film may be the same or different.

於本發明之較佳之一實施形態中，本發明之光學膜有效用作顯示裝置之前面板、尤其是可撓性顯示裝置之前面板(以下，有時稱為視窗膜)。可撓性顯示裝置例如具有可撓性功能層、及與可撓性功能層重疊並作為前面板發揮功能之光學膜。即，可撓性顯示裝置之前面板配置於可撓性功能層之上之視認側。該前面板具有保護可撓性功能層之功能。In a preferred embodiment of the present invention, the optical film of the present invention is effectively used as a front panel of a display device, especially a front panel of a flexible display device (hereinafter, sometimes referred to as a window film). The flexible display device has, for example, a flexible functional layer and an optical film that overlaps the flexible functional layer and functions as a front panel. That is, the front panel of the flexible display device is arranged on the visible side of the flexible functional layer. The front panel has the function of protecting the flexible functional layer.

作為顯示裝置，可列舉：電視、智慧型手機、行動電話、汽車導航系統、平板PC、便攜式遊戲機、電子紙、指示器、掲示板、鐘錶、及智慧型手錶等可佩戴器件等。作為可撓性顯示裝置，可列舉具有可撓性特性之所有顯示裝置，其中較佳為可彎折之可摺疊顯示裝置或可可捲曲顯示裝置。Examples of display devices include wearable devices such as televisions, smart phones, mobile phones, car navigation systems, tablet PCs, portable game consoles, electronic paper, indicators, display boards, clocks, and smart watches. As the flexible display device, all display devices having flexibility characteristics can be cited, and among them, a bendable foldable display device or a cocoa rollable display device is preferred.

[可撓性顯示裝置] 本發明亦提供一種具備本發明之光學膜之可撓性顯示裝置。本發明之光學膜較佳為於可撓性顯示裝置中用作前面板，該前面板有時被稱為視窗膜。該可撓性顯示裝置包含可撓性顯示裝置用積層體、及有機EL顯示面板，相對於有機EL顯示面板於視認側配置有可撓性顯示裝置用積層體，且構成為可彎折。可撓性顯示裝置用積層體可包含視窗膜、偏光板(較佳為圓偏光板)、觸控感測器，其等之積層順序任意，較佳為自視認側起依序積層有視窗膜、偏光板、觸控感測器或視窗膜、觸控感測器、偏光板。若於觸控感測器之視認側存在偏光板，則觸控感測器之圖案不易被視認到而顯示圖像之視認性變得良好，因此較佳。各構件可使用接著劑、黏著劑等積層。又，可具備形成於上述視窗膜、偏光板、觸控感測器之任一層之至少一面之遮光圖案。[Flexible display device] The invention also provides a flexible display device equipped with the optical film of the invention. The optical film of the present invention is preferably used as a front panel in a flexible display device, and the front panel is sometimes called a window film. The flexible display device includes a laminate for a flexible display device and an organic EL display panel. The laminate for a flexible display device is arranged on the viewing side of the organic EL display panel and is configured to be bendable. The laminate for a flexible display device may include a window film, a polarizing plate (preferably a circular polarizing plate), a touch sensor, etc. in any order, preferably the window film is layered in order from the viewing side , Polarizing plate, touch sensor or window film, touch sensor, polarizing plate. If there is a polarizing plate on the visible side of the touch sensor, the pattern of the touch sensor is not easily visible and the visibility of the displayed image becomes good, which is better. Each member can be laminated using adhesives, adhesives, etc. In addition, it may be provided with a light-shielding pattern formed on at least one surface of any one of the above-mentioned window film, polarizer, and touch sensor.

[偏光板] 本發明之可撓性顯示裝置可進而具備偏光板、較佳為圓偏光板。圓偏光板係具有藉由於直線偏光板積層λ/4相位差板而僅使右旋圓偏振光成分或左旋圓偏振光成分透過之功能之功能層。例如係用以阻斷將外界光轉換成右旋圓偏振光後於有機EL面板反射而成為左旋圓偏振光之外界光，並僅使有機EL之發光成分透過，藉此抑制反射光之影響而使圖像容易看清。為了達成圓偏振光功能，直線偏光板之吸收軸與λ/4相位差板之遲相軸理論上必須為45°，實際使用上為45±10°。直線偏光板與λ/4相位差板未必必須相鄰地積層，只要吸收軸與遲相軸之關係滿足上述範圍即可。較佳為於總波長下達成完整之圓偏振光，但實際使用上未必必須如此，因此本發明中之圓偏光板亦包含橢圓偏光板。亦較佳為藉由於直線偏光板之視認側進而積層λ/4相位差膜，使出射光成為圓偏振光而提高佩戴偏光太陽眼鏡之狀態下之視認性。[Polarizer] The flexible display device of the present invention may further include a polarizing plate, preferably a circular polarizing plate. The circularly polarizing plate is a functional layer that has a function of transmitting only the right-handed circularly polarized light component or the left-handed circularly polarized light component by laminating a λ/4 retardation plate on the linear polarizer. For example, it is used to block the external light that is converted into right-handed circularly polarized light and then reflected on the organic EL panel to become left-handed circularly polarized light outer boundary light, and only transmits the luminous components of the organic EL, thereby suppressing the influence of reflected light. Make the image easy to see. In order to achieve the circularly polarized light function, the absorption axis of the linear polarizer and the slow axis of the λ/4 retardation plate must be 45° in theory, and 45±10° in actual use. The linear polarizing plate and the λ/4 retardation plate do not necessarily need to be laminated adjacently, as long as the relationship between the absorption axis and the slow phase axis satisfies the above range. It is preferable to achieve complete circularly polarized light under the total wavelength, but this is not necessarily the case in actual use. Therefore, the circular polarizer in the present invention also includes an elliptical polarizer. It is also preferable to laminate a λ/4 retardation film on the visibility side of the linear polarizer so that the emitted light becomes circularly polarized light to improve the visibility in the state of wearing polarized sunglasses.

直線偏光板係具有使於透過軸方向上振動之光通過而阻斷與其垂直之振動成分之偏振光之功能之功能層。上述直線偏光板亦可為單獨具備直線偏光元件或具備直線偏光元件及貼附於其至少一面之保護膜之構成。上述直線偏光板之厚度可為200 μm以下，較佳為0.5～100 μm。若厚度處於上述範圍，則有柔軟性不易降低之傾向。 上述直線偏光元件亦可為藉由對聚乙烯醇(PVA)系膜進行染色、延伸而製造之膜型偏光元件。藉由使碘等二色性色素吸附於藉由延伸而配向之PVA系膜或於吸附於PVA之狀態下延伸而使二色性色素配向，從而發揮偏光性能。於上述膜型偏光元件之製造中，亦可另外具有膨潤、藉由硼酸而進行之交聯、藉由水溶液而進行之洗淨、乾燥等步驟。延伸或染色步驟可由PVA系膜單獨進行，亦可於與如聚對苯二甲酸乙二酯之其他膜積層之狀態下進行。所使用之PVA系膜之厚度較佳為10～100 μm，延伸倍率較佳為2～10倍。 進而，作為上述偏光元件之另一例，亦可為塗佈液晶偏光組合物而形成之液晶塗佈型偏光元件。上述液晶偏光組合物可包含液晶性化合物及二色性色素化合物。上述液晶性化合物只要具有顯示液晶狀態之性質即可，尤其是若具有層列相等高次配向狀態，則可發揮較高之偏光性能，故而較佳。又，液晶性化合物亦較佳為具有聚合性官能基。The linear polarizer is a functional layer that has the function of passing light vibrating in the direction of the transmission axis and blocking the polarized light of the vibration component perpendicular to it. The above-mentioned linear polarizing plate may also be a structure having a linear polarizing element alone or a linear polarizing element and a protective film attached to at least one surface thereof. The thickness of the linear polarizing plate may be 200 μm or less, preferably 0.5-100 μm. If the thickness is in the above range, there is a tendency that flexibility is not easily reduced. The linear polarizing element may be a film-type polarizing element manufactured by dyeing and stretching a polyvinyl alcohol (PVA) film. By adsorbing dichroic dyes such as iodine to the PVA-based film aligned by stretching, or stretching while adsorbing on PVA, the dichroic dyes are aligned, thereby exhibiting polarization performance. In the manufacture of the above-mentioned film-type polarizing element, it may additionally have steps such as swelling, cross-linking by boric acid, washing by aqueous solution, and drying. The stretching or dyeing step can be performed by a PVA-based film alone, or in a state of being laminated with other films such as polyethylene terephthalate. The thickness of the PVA-based film used is preferably 10-100 μm, and the stretching ratio is preferably 2-10 times. Furthermore, as another example of the above-mentioned polarizing element, it may be a liquid crystal coating type polarizing element formed by coating a liquid crystal polarizing composition. The liquid crystal polarizing composition may include a liquid crystal compound and a dichroic dye compound. The above-mentioned liquid crystalline compound only needs to have the property of displaying a liquid crystal state, especially if it has a high-order alignment state equal to a smectic array, it can exhibit a higher polarization performance, so it is preferable. Moreover, it is also preferable that the liquid crystal compound has a polymerizable functional group.

上述二色性色素係與上述液晶化合物一起配向而顯示出二色性之色素，二色性色素自身可具有液晶性，亦可具有聚合性官能基。液晶偏光組合物中之任一化合物具有聚合性官能基。 上述液晶偏光組合物可進而包含起始劑、溶劑、分散劑、調平劑、穩定劑、界面活性劑、交聯劑、矽烷偶合劑等。 上述液晶偏光層係藉由於配向膜上塗佈液晶偏光組合物形成液晶偏光層而製造。 液晶偏光層與膜型偏光元件相比可將厚度形成為較薄。上述液晶偏光層之厚度可較佳為0.5～10 μm、更佳為1～5 μm。 上述配向膜例如可藉由於基材上塗佈配向膜形成組合物並藉由摩擦、偏光照射等賦予配向性而製造。上述配向膜形成組合物除配向劑以外，亦可包含溶劑、交聯劑、起始劑、分散劑、調平劑、矽烷偶合劑等。作為上述配向劑，例如可使用聚乙烯醇類、聚丙烯酸酯類、聚醯胺酸類、聚醯亞胺類。於應用光配向之情形時，較佳為使用包含肉桂酸酯基之配向劑。用作上述配向劑之高分子之重量平均分子量可為10,000～1,000,000左右。就配向限制力之觀點而言，上述配向膜之厚度較佳為5～10,000 nm，更佳為10～500 nm。上述液晶偏光層可自基材剝離後轉印並積層，亦可直接將上述基材積層。上述基材亦較佳為承擔作為保護膜或相位差板、視窗之透明基材之作用。The dichroic dye is a dye that is aligned with the liquid crystal compound to exhibit dichroism. The dichroic dye itself may have liquid crystallinity or may have a polymerizable functional group. Any compound in the liquid crystal polarizing composition has a polymerizable functional group. The above-mentioned liquid crystal polarizing composition may further include a starter, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a crosslinking agent, a silane coupling agent, and the like. The above-mentioned liquid crystal polarizing layer is manufactured by coating a liquid crystal polarizing composition on an alignment film to form a liquid crystal polarizing layer. The liquid crystal polarizing layer can be formed thinner than the film-type polarizing element. The thickness of the above-mentioned liquid crystal polarizing layer may preferably be 0.5-10 μm, more preferably 1-5 μm. The above-mentioned alignment film can be produced, for example, by coating an alignment film forming composition on a substrate and imparting alignment by rubbing, polarized light irradiation, or the like. In addition to the alignment agent, the alignment film forming composition may also include a solvent, a crosslinking agent, an initiator, a dispersant, a leveling agent, a silane coupling agent, and the like. As the above-mentioned alignment agent, for example, polyvinyl alcohols, polyacrylates, polyamides, and polyimines can be used. In the case of applying optical alignment, it is preferable to use an alignment agent containing a cinnamate group. The weight average molecular weight of the polymer used as the alignment agent can be about 10,000-1,000,000. From the viewpoint of the alignment restriction force, the thickness of the alignment film is preferably 5 to 10,000 nm, more preferably 10 to 500 nm. The liquid crystal polarizing layer may be separated from the base material and then transferred and laminated, or the base material may be directly laminated. The above-mentioned base material is also preferably used as a transparent base material for a protective film, a phase difference plate, and a window.

作為上述保護膜，只要為透明之高分子膜即可，可使用上述透明基材所使用之材料、添加劑。較佳為纖維素系膜、烯烴系膜、丙烯酸系膜、聚酯系膜。亦可為塗佈環氧樹脂等陽離子硬化組合物或丙烯酸酯等自由基硬化組合物並硬化而獲得之塗佈型之保護膜。亦可視需要包含塑化劑、紫外線吸收劑、紅外線吸收劑、顏料或染料之類之著色劑、螢光增白劑、分散劑、熱穩定劑、光穩定劑、抗靜電劑、抗氧化劑、潤滑劑、溶劑等。上述保護膜之厚度可為200 μm以下，較佳為1～100 μm。若上述保護膜之厚度處於上述範圍，則保護膜之柔軟性不易降低。保護膜亦可兼顧視窗之透明基材之作用。The protective film may be a transparent polymer film, and the materials and additives used for the transparent substrate may be used. Preferred are cellulose-based films, olefin-based films, acrylic-based films, and polyester-based films. It can also be a coating type protective film obtained by coating and curing a cationic curing composition such as epoxy resin or a radical curing composition such as acrylic ester. It can also contain plasticizers, ultraviolet absorbers, infrared absorbers, pigments or dyes, fluorescent whitening agents, dispersants, heat stabilizers, light stabilizers, antistatic agents, antioxidants, and lubricating agents as needed. Agent, solvent, etc. The thickness of the protective film can be 200 μm or less, preferably 1-100 μm. If the thickness of the protective film is in the above range, the flexibility of the protective film is not easily reduced. The protective film can also take into account the role of the transparent substrate of the window.

上述λ/4相位差板係對與入射光之行進方向正交之方向(膜之面內方向)賦予λ/4之相位差之膜。上述λ/4相位差板亦可為藉由使纖維素系膜、烯烴系膜、聚碳酸酯系膜等高分子膜延伸而製造之延伸型相位差板。亦可視需要包含相位差調整劑、塑化劑、紫外線吸收劑、紅外線吸收劑、顏料或染料之類之著色劑、螢光增白劑、分散劑、熱穩定劑、光穩定劑、抗靜電劑、抗氧化劑、潤滑劑、溶劑等。上述延伸型相位差板之厚度可為200 μm以下，較佳為1～100 μm。若厚度處於上述範圍，則有膜之柔軟性不易降低之傾向。 進而，作為上述λ/4相位差板之另一例，亦可為塗佈液晶組合物而形成之液晶塗佈型相位差板。上述液晶組合物包含具有顯示向列、膽固醇狀、層列等液晶狀態之性質之液晶性化合物。液晶組合物中之包含液晶性化合物之任一化合物具有聚合性官能基。上述液晶塗佈型相位差板可進而包含起始劑、溶劑、分散劑、調平劑、穩定劑、界面活性劑、交聯劑、矽烷偶合劑等。上述液晶塗佈型相位差板可與上述液晶偏光層中之記載同樣地藉由於配向膜上塗佈液晶組合物並進行硬化而形成液晶相位差層而製造。液晶塗佈型相位差板與延伸型相位差板相比可將厚度形成為較薄。上述液晶偏光層之厚度可通常為0.5～10 μm，較佳為1～5 μm。上述液晶塗佈型相位差板可自基材剝離並轉印後積層，亦可直接將上述基材積層。亦較佳為上述基材承擔作為保護膜或相位差板、視窗之透明基材之作用。The above-mentioned λ/4 retardation plate is a film that provides a λ/4 retardation in a direction orthogonal to the traveling direction of incident light (in-plane direction of the film). The above-mentioned λ/4 retardation plate may be a stretched retardation plate manufactured by stretching a polymer film such as a cellulose-based film, an olefin-based film, or a polycarbonate-based film. It can also contain phase difference adjusters, plasticizers, ultraviolet absorbers, infrared absorbers, pigments or dyes and other coloring agents, fluorescent whitening agents, dispersants, heat stabilizers, light stabilizers, and antistatic agents. , Antioxidants, lubricants, solvents, etc. The thickness of the extended phase difference plate may be 200 μm or less, preferably 1-100 μm. If the thickness is in the above range, there is a tendency that the flexibility of the film is not easily reduced. Furthermore, as another example of the above-mentioned λ/4 retardation plate, it may be a liquid crystal coating type retardation plate formed by applying a liquid crystal composition. The above-mentioned liquid crystal composition contains a liquid crystal compound having the property of displaying liquid crystal states such as nematic, cholesteric, smectic, and the like. Any compound containing a liquid crystal compound in the liquid crystal composition has a polymerizable functional group. The above-mentioned liquid crystal coating type retardation plate may further include a starter, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a crosslinking agent, a silane coupling agent, and the like. The liquid crystal coating type retardation plate can be manufactured by forming a liquid crystal retardation layer by applying and curing a liquid crystal composition on an alignment film in the same manner as described in the liquid crystal polarizing layer. The liquid crystal coating type retardation plate can be made thinner than the extension type retardation plate. The thickness of the above-mentioned liquid crystal polarizing layer may usually be 0.5-10 μm, preferably 1-5 μm. The liquid crystal coating type retardation plate may be peeled from the base material and laminated after transfer, or the base material may be laminated directly. It is also preferable that the above-mentioned substrate plays a role as a transparent substrate of a protective film, a phase difference plate, and a window.

一般而言，波長越短，雙折射越大，波長越長，顯示越小之雙折射之材料較多。於該情形時，由於無法於全可見光區域達成λ/4之相位差，故而以相對於可見度較高之560 nm附近成為λ/4之面內相位差成為100～180 nm、較佳為130～150 nm之方式設計之情況較多。藉由使用利用具有與通常相反之雙折射率波長色散特性之材料之逆色散λ/4相位差板可使視認性良好，因此較佳。作為此種材料，亦較佳為於延伸型相位差板之情形時使用日本專利特開2007-232873號公報等所記載者，於液晶塗佈型相位差板之情形時使用日本專利特開2010-30979號公報所記載者。 又，作為其他方法，亦已知有藉由與λ/2相位差板組合而獲得寬頻帶λ/4相位差板之技術(日本專利特開平10-90521號公報)。λ/2相位差板亦係利用與λ/4相位差板相同之材料方法製造。延伸型相位差板與液晶塗佈型相位差板之組合任意，但均因使用液晶塗佈型相位差板可使厚度變薄而較佳。 亦已知有為了提高斜方向之視認性而於上述圓偏光板積層正C平板之方法(日本專利特開2014-224837號公報)。正C平板可為液晶塗佈型相位差板，亦可為延伸型相位差板。厚度方向之相位差通常-200～-20 nm，較佳為-140～-40 nm。Generally speaking, the shorter the wavelength, the greater the birefringence, and the longer the wavelength, the more materials exhibiting the smaller the birefringence. In this case, since the phase difference of λ/4 cannot be achieved in the full visible light region, the in-plane phase difference of λ/4 becomes 100 to 180 nm, preferably 130 to 560 nm, where the visibility is higher. There are many cases of 150 nm design. It is preferable to use a reverse dispersion λ/4 retardation plate that uses a material having birefringence wavelength dispersion characteristics opposite to that of usual, which can provide good visibility. As such a material, it is also preferable to use the one described in Japanese Patent Laid-Open No. 2007-232873 in the case of an extended retardation plate, and to use Japanese Patent Laid-Open 2010 in the case of a liquid crystal coating type retardation plate. -30979 Bulletin. In addition, as another method, a technique of obtaining a wide-band λ/4 retardation plate by combining with a λ/2 retardation plate is also known (Japanese Patent Laid-Open No. 10-90521). The λ/2 retardation plate is also manufactured using the same material method as the λ/4 retardation plate. The combination of the extension type retardation plate and the liquid crystal coating type retardation plate is arbitrary, but it is preferable to use the liquid crystal coating type retardation plate to make the thickness thinner. There is also known a method of laminating a positive C flat plate on the above-mentioned circular polarizing plate in order to improve the visibility in the oblique direction (Japanese Patent Laid-Open No. 2014-224837). The positive C plate can be a liquid crystal coating type retardation plate or an extended type retardation plate. The phase difference in the thickness direction is usually -200 to -20 nm, preferably -140 to -40 nm.

[觸控感測器] 本發明之可撓性顯示裝置亦可進而具備觸控感測器。觸控感測器可用作輸入機構。作為觸控感測器，提出有電阻膜方式、表面彈性波方式、紅外線方式、電磁感應方式、靜電電容方式等各種樣式，可為任一方式。其中較佳為靜電電容方式。靜電電容方式觸控感測器被劃分為活性區域及位於上述活性區域之外廓部之非活性區域。活性區域係作為於顯示面板顯示畫面之顯示部之對應區域並且係感知使用者之觸碰之區域，非活性區域係作為不於顯示裝置顯示畫面之非顯示部之對應區域。觸控感測器可包含：基板，其具有可撓性之特性；感知圖案，其形成於上述基板之活性區域；及各感測線，其等形成於上述基板之非活性區域，且用以經由焊墊部將上述感知圖案與外部之驅動電路連接。作為具有可撓性之特性之基板，可使用與上述視窗之透明基板相同之材料。觸控感測器之基板就抑制觸控感測器之龜裂之方面而言，較佳為其韌性為2,000 MPa%以上者。更佳為韌性可為2,000～30,000 MPa%。此處，韌性被定義為於通過高分子材料之拉伸實驗而獲得之應力(MPa)-應變(%)曲線(Stress-straincurve)中達到破壞點之前之曲線之下部面積。[Touch Sensor] The flexible display device of the present invention may further include a touch sensor. The touch sensor can be used as an input mechanism. As a touch sensor, various styles such as a resistive film method, a surface elastic wave method, an infrared method, an electromagnetic induction method, and an electrostatic capacitance method are proposed, and any method may be adopted. Among them, the electrostatic capacitance method is preferred. The capacitive touch sensor is divided into an active area and an inactive area located outside the active area. The active area is the area corresponding to the display part of the display screen of the display panel and the area that senses the user's touch, and the inactive area is the corresponding area of the non-display part that does not display the picture on the display device. The touch sensor may include: a substrate, which has the characteristics of flexibility; a sensing pattern, which is formed on the active area of the substrate; and each sensing line, which is formed on the inactive area of the substrate, and is used to pass through The pad part connects the sensing pattern with an external driving circuit. As a substrate with flexible characteristics, the same material as the transparent substrate of the above-mentioned window can be used. In terms of suppressing cracks of the touch sensor, the substrate of the touch sensor is preferably one with a toughness of 2,000 MPa% or more. More preferably, the toughness may be 2,000 to 30,000 MPa%. Here, toughness is defined as the area under the curve before reaching the failure point in the stress (MPa)-strain (%) curve obtained through the tensile test of the polymer material.

上述感知圖案可具備形成於第1方向上之第1圖案及形成於第2方向上之第2圖案。第1圖案與第2圖案配置於互不相同之方向上。第1圖案及第2圖案形成於同一層，為了感知經觸碰之地點，必須將各圖案電性連接。第1圖案係各單位圖案經由接頭相互連接之形態，第2圖案係各單位圖案相互分離成島嶼形態之結構，因此為了將第2圖案電性連接，必需另外之橋接電極。感知圖案可應用周知之透明電極素材。例如可列舉：銦錫氧化物(ITO)、銦鋅氧化物(IZO)、鋅氧化物(ZnO)、銦鋅錫氧化物(IZTO)、銦鎵鋅氧化物(IGZO)、鎘錫氧化物(CTO)、PEDOT(poly(3,4-ethylenedioxythiophene)，聚(3,4-乙二氧基噻吩))、奈米碳管(CNT)、石墨烯、金屬線等、該等可單獨或將2種以上混合使用。較佳為可使用ITO。金屬線所使用之金屬並無特別限定，例如可列舉：銀、金、鋁、銅、鐵、鎳、鈦、硒、鉻等。該等可單獨或將2種以上混合使用。The aforementioned sensing pattern may include a first pattern formed in the first direction and a second pattern formed in the second direction. The first pattern and the second pattern are arranged in different directions. The first pattern and the second pattern are formed on the same layer. In order to sense the touched location, each pattern must be electrically connected. The first pattern is a form in which the unit patterns are connected to each other via a joint, and the second pattern is a structure in which the unit patterns are separated from each other into island shapes. Therefore, in order to electrically connect the second pattern, another bridge electrode is necessary. The sensing pattern can use well-known transparent electrode materials. Examples include: indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium zinc tin oxide (IZTO), indium gallium zinc oxide (IGZO), cadmium tin oxide ( CTO), PEDOT (poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxythiophene)), carbon nanotubes (CNT), graphene, metal wires, etc., these can be separated or combined Mixed use of the above. Preferably, ITO can be used. The metal used for the metal wire is not particularly limited, and examples thereof include silver, gold, aluminum, copper, iron, nickel, titanium, selenium, and chromium. These can be used individually or in mixture of 2 or more types.

橋接電極可於感知圖案上部經由絕緣層形成於上述絕緣層上部，且可於基板上形成橋接電極，並於其上形成絕緣層及感知圖案。上述橋接電極可利用與感知圖案相同之材料形成，亦可利用鉬、銀、鋁、銅、鈀、金、鉑、鋅、錫、鈦或該等中之2種以上之合金等金屬形成。第1圖案與第2圖案必須電性絕緣，因此於感知圖案與橋接電極之間形成有絕緣層。絕緣層亦可僅形成於第1圖案之接頭與橋接電極之間，亦可形成於覆蓋感知圖案之層之結構。於後者之情形時，橋接電極可經由形成於絕緣層之接觸孔連接第2圖案。上述觸控感測器可於基板與電極之間進而包含光學調節層作為用以適當補償透過率之差之機構，該透過率之差係形成有圖案之圖案區域與未形成圖案之非圖案區域間之透過率之差、具體而言因該等區域中之折射率之差而誘發之透光率之差；上述光學調節層可包含無機絕緣物質或有機絕緣物質。光學調節層可將包含光硬化性有機黏合劑及溶劑之光硬化組合物塗佈於基板上而形成。上述光硬化組合物可進而包含無機粒子。可藉由上述無機粒子使光學調節層之折射率上升。 上述光硬化性有機黏合劑例如可包含丙烯酸酯系單體、苯乙烯系單體、羧酸系單體等各單體之共聚物。上述光硬化性有機黏合劑例如亦可為包含含環氧基之重複單元、丙烯酸酯重複單元、羧酸重複單元等互不相同之各重複單元之共聚物。 上述無機粒子例如可包含氧化鋯粒子、二氧化鈦粒子、氧化鋁粒子等。上述光硬化組合物可進而包含光聚合起始劑、聚合性單體、硬化輔助劑等各添加劑。The bridge electrode can be formed on the upper part of the insulating layer through the insulating layer on the upper part of the sensing pattern, and the bridge electrode can be formed on the substrate, and the insulating layer and the sensing pattern can be formed thereon. The above-mentioned bridge electrode can be formed of the same material as the sensing pattern, or can be formed of metals such as molybdenum, silver, aluminum, copper, palladium, gold, platinum, zinc, tin, titanium, or an alloy of two or more of these. The first pattern and the second pattern must be electrically insulated, so an insulating layer is formed between the sensing pattern and the bridge electrode. The insulating layer can also be formed only between the joints of the first pattern and the bridging electrodes, or can be formed in the structure of the layer covering the sensing pattern. In the latter case, the bridge electrode can be connected to the second pattern via a contact hole formed in the insulating layer. The above-mentioned touch sensor may further include an optical adjustment layer between the substrate and the electrode as a mechanism for appropriately compensating for the difference in transmittance, which is the patterned area with the pattern and the non-patterned area with no pattern. The difference in transmittance between the regions, specifically the difference in light transmittance induced by the difference in refractive index in these regions; the optical adjustment layer may include an inorganic insulating material or an organic insulating material. The optical adjustment layer can be formed by coating a photocuring composition containing a photocuring organic binder and a solvent on a substrate. The above-mentioned photocurable composition may further contain inorganic particles. The refractive index of the optical adjustment layer can be increased by the above-mentioned inorganic particles. The photocurable organic adhesive may include, for example, copolymers of monomers such as acrylate monomers, styrene monomers, and carboxylic acid monomers. The photocurable organic adhesive may be, for example, a copolymer containing different repeating units such as epoxy-containing repeating units, acrylate repeating units, and carboxylic acid repeating units. The above-mentioned inorganic particles may include zirconia particles, titania particles, alumina particles, and the like, for example. The aforementioned photocurable composition may further contain various additives such as a photopolymerization initiator, a polymerizable monomer, and a curing auxiliary agent.

[接著層] 形成上述可撓性顯示裝置用積層體之視窗、偏光板、觸控感測器等各層、以及構成各層之直線偏光板、λ/4相位差板等膜構件可藉由接著劑接著。作為接著劑，可使用水系接著劑、有機溶劑系接著劑、無溶劑系接著劑、固體接著劑、溶劑揮散型接著劑、水系溶劑揮散型接著劑、濕氣硬化型接著劑、加熱硬化型接著劑、厭氧硬化型接著劑、活性能量線硬化型接著劑、硬化劑混合型接著劑、熱熔融型接著劑、感壓型接著劑、感壓型黏著劑、再濕型接著劑等通用使用者。其中，經常使用水系溶劑揮散型接著劑、活性能量線硬化型接著劑、黏著劑。接著層之厚度可根據所要求之接著力等適當調節，例如為0.01～500 μm，較佳為0.1～300 μm。接著層可於上述可撓性顯示裝置用積層體中存在複數層，但各層之厚度及所使用之接著劑之種類可相同，亦可不同。[Next layer] The windows, polarizers, touch sensors and other layers forming the laminated body for the flexible display device, as well as film members such as the linear polarizers and λ/4 phase difference plates constituting the layers, can be bonded by an adhesive. As the adhesive, water-based adhesives, organic solvent-based adhesives, solvent-free adhesives, solid adhesives, solvent-volatile adhesives, water-based solvent-volatile adhesives, moisture-curing adhesives, and heat-curing adhesives can be used For general use, such as anaerobic hardening adhesive, active energy ray hardening adhesive, hardener mixed adhesive, hot melt adhesive, pressure sensitive adhesive, pressure sensitive adhesive, remoisturizing adhesive, etc. By. Among them, water-based solvent volatile adhesives, active energy ray hardening adhesives, and adhesives are often used. The thickness of the subsequent layer can be appropriately adjusted according to the required adhesive force, etc., for example, 0.01-500 μm, preferably 0.1-300 μm. The adhesive layer may have multiple layers in the above-mentioned laminate for flexible display devices, but the thickness of each layer and the type of adhesive used may be the same or different.

作為上述水系溶劑揮散型接著劑，可使用聚乙烯醇系聚合物、澱粉等水溶性聚合物、乙烯-乙酸乙烯酯系乳膠、苯乙烯-丁二烯系乳膠等水分散狀態之聚合物作為主劑聚合物。除水、上述主劑聚合物以外，亦可調配交聯劑、矽烷系化合物、離子性化合物、交聯觸媒、抗氧化劑、染料、顏料、無機填料、有機溶劑等。於藉由上述水系溶劑揮散型接著劑接著之情形時，可藉由將上述水系溶劑揮散型接著劑注入至被接著層間而將被接著層貼合後進行乾燥，從而賦予接著性。使用上述水系溶劑揮散型接著劑之情形時之接著層之厚度可為0.01～10 μm，較佳為0.1～1 μm。於將上述水系溶劑揮散型接著劑用於形成複數層之情形時，各層之厚度及上述接著劑之種類可相同，亦可不同。As the above-mentioned water-based solvent-volatile adhesive, water-dispersed polymers such as polyvinyl alcohol-based polymers, starch, etc., ethylene-vinyl acetate-based latex, styrene-butadiene-based latex, and other water-dispersed polymers can be used as the main Agent polymer. In addition to water and the above-mentioned main agent polymer, crosslinking agents, silane compounds, ionic compounds, crosslinking catalysts, antioxidants, dyes, pigments, inorganic fillers, organic solvents, etc. can also be formulated. In the case of bonding by the above-mentioned water-based solvent-volatile adhesive, the above-mentioned water-based solvent-volatile adhesive may be injected between the layers to be bonded, and the bonded layers may be bonded and dried to impart adhesiveness. In the case of using the above-mentioned water-based solvent-volatile adhesive, the thickness of the adhesive layer may be 0.01-10 μm, preferably 0.1-1 μm. When the water-based solvent volatile adhesive is used to form multiple layers, the thickness of each layer and the type of the adhesive may be the same or different.

上述活性能量線硬化型接著劑可藉由照射活性能量線使包含形成接著劑層之反應性材料之活性能量線硬化組合物硬化而形成。上述活性能量線硬化組合物可含有與硬塗組合物相同之自由基聚合性化合物及陽離子聚合性化合物之至少1種聚合物。所謂上述自由基聚合性化合物，與硬塗組合物同樣，可使用與硬塗組合物相同種類者。作為用於接著層之自由基聚合性化合物，較佳為具有丙烯醯基之化合物。為了降低作為接著劑組合物之黏度，亦較佳為包含單官能之化合物。The active energy ray curable adhesive can be formed by irradiating active energy rays to harden an active energy ray curable composition containing a reactive material that forms the adhesive layer. The active energy ray hardening composition may contain at least one polymer of the same radical polymerizable compound and cation polymerizable compound as the hard coat composition. The above-mentioned radically polymerizable compound is the same as the hard coat composition, and the same type as the hard coat composition can be used. As the radical polymerizable compound used for the adhesive layer, a compound having an acrylic group is preferred. In order to reduce the viscosity of the adhesive composition, it is also preferable to include a monofunctional compound.

上述陽離子聚合性化合物與硬塗組合物同樣，可使用與硬塗組合物相同種類者。作為用於活性能量線硬化組合物之陽離子聚合性化合物，更佳為環氧化合物。為了降低接著劑組合物之黏度，亦較佳為包含單官能之化合物作為反應性稀釋劑。 活性能量線組合物中可進而包含聚合起始劑。作為聚合起始劑，為自由基聚合起始劑、陽離子聚合起始劑、自由基及陽離子聚合起始劑等，可適當選擇並使用。該等聚合起始劑係藉由活性能量線照射及加熱之至少一種而被分解，產生自由基或陽離子並使自由基聚合與陽離子聚合進行。可使用硬塗組合物之記載中可藉由活性能量線照射使自由基聚合或陽離子聚合中之至少一種開始之起始劑。The above-mentioned cationically polymerizable compound is the same as the hard coat composition, and the same type as the hard coat composition can be used. The cationic polymerizable compound used in the active energy ray hardening composition is more preferably an epoxy compound. In order to reduce the viscosity of the adhesive composition, it is also preferable to include a monofunctional compound as a reactive diluent. The active energy ray composition may further contain a polymerization initiator. As the polymerization initiator, there are radical polymerization initiators, cationic polymerization initiators, radical and cationic polymerization initiators, etc., which can be appropriately selected and used. The polymerization initiators are decomposed by at least one of active energy ray irradiation and heating to generate free radicals or cations and allow radical polymerization and cationic polymerization to proceed. In the description of the hard coating composition, an initiator that can initiate at least one of radical polymerization or cationic polymerization by active energy ray irradiation can be used.

上述活性能量線硬化組合物可進而包含離子捕捉劑、抗氧化劑、鏈轉移劑、密接賦予劑、熱塑性樹脂、填充劑、流化黏度調整劑、塑化劑、消泡劑溶劑、添加劑、溶劑。於藉由上述活性能量線硬化型接著劑接著之情形時，可藉由將上述活性能量線硬化組合物塗佈於被接著層之任一者或兩者後進行貼合，並通過任一被接著層或兩個被接著層照射活性能量線進行硬化而接著。使用上述活性能量線硬化型接著劑之情形時之接著層之厚度可為0.01～20 μm，較佳為0.1～10 μm。於將上述活性能量線硬化型接著劑用於形成複數層之情形時，各層之厚度及所使用之接著劑之種類可相同，亦可不同。The active energy ray hardening composition may further include an ion scavenger, an antioxidant, a chain transfer agent, an adhesion imparting agent, a thermoplastic resin, a filler, a fluidized viscosity adjuster, a plasticizer, a defoamer solvent, an additive, and a solvent. In the case of bonding by the active energy ray-curable adhesive, the active energy ray-curing composition can be applied to either or both of the layers to be adhered, and then bonded by either The next layer or two bonded layers are irradiated with active energy rays to be cured and then bonded. In the case of using the active energy ray-curable adhesive, the thickness of the adhesive layer may be 0.01-20 μm, preferably 0.1-10 μm. When the active energy ray-curable adhesive is used to form multiple layers, the thickness of each layer and the type of adhesive used may be the same or different.

作為上述黏著劑，亦可對應於主劑聚合物被分類成丙烯酸系黏著劑、胺基甲酸酯系黏著劑、橡膠系黏著劑、聚矽氧系黏著劑等並使用任一者。於黏著劑中，除主劑聚合物以外，亦可調配交聯劑、矽烷系化合物、離子性化合物、交聯觸媒、抗氧化劑、黏著賦予劑、塑化劑、染料、顏料、無機填料等。使構成上述黏著劑之各成分溶解、分散於溶劑中獲得黏著劑組合物，並將該黏著劑組合物塗佈於基材上後進行乾燥，藉此形成黏著層或接著層。黏著層可直接形成，亦可轉印另外形成於基材者。為了覆蓋接著前之黏著面，亦較佳為使用脫模膜。使用上述黏著劑之情形時之接著層之厚度可為1～500 μm，較佳為2～300 μm。於將上述黏著劑用於形成複數層之情形時，各層之厚度及所使用之黏著劑之種類可相同，亦可不同。As the above-mentioned adhesive, any one of acrylic adhesives, urethane-based adhesives, rubber-based adhesives, silicone-based adhesives, etc. may be classified in accordance with the main agent polymer and used. In the adhesive, in addition to the main agent polymer, crosslinking agents, silane compounds, ionic compounds, crosslinking catalysts, antioxidants, adhesion imparting agents, plasticizers, dyes, pigments, inorganic fillers, etc. can also be blended . The components constituting the adhesive are dissolved and dispersed in a solvent to obtain an adhesive composition, and the adhesive composition is coated on a substrate and dried to form an adhesive layer or an adhesive layer. The adhesive layer can be directly formed, or it can be transferred to a substrate formed separately. In order to cover the adhesive surface before bonding, it is also preferable to use a release film. In the case of using the above-mentioned adhesive, the thickness of the adhesive layer may be 1 to 500 μm, preferably 2 to 300 μm. When the above-mentioned adhesive is used to form multiple layers, the thickness of each layer and the type of adhesive used may be the same or different.

[遮光圖案] 上述遮光圖案可作為上述可撓性顯示裝置之邊框或外殼之至少一部分而應用。藉由遮光圖案掩蓋配置於上述可撓性顯示裝置之邊緣部之配線使之不易被視認到，藉此提高圖像之視認性。上述遮光圖案可為單層或複數層之形態。遮光圖案之顏色並無特別限制，可具有黑色、白色、金屬色等多種顏色。遮光圖案可由用以具體表現出顏色之顏料及丙烯酸系樹脂、酯系樹脂、環氧系樹脂、聚胺基甲酸酯、聚矽氧等高分子形成。該等可單獨使用或以2種以上之混合物使用。上述遮光圖案可利用印刷、微影術、噴墨等各種方法形成。遮光圖案之厚度通常為1～100 μm，較佳為2～50 μm。又，亦可於遮光圖案之厚度方向上賦予傾斜等形狀。 [實施例][Shading Pattern] The above-mentioned light-shielding pattern can be applied as at least a part of the frame or housing of the above-mentioned flexible display device. The wiring arranged at the edge of the flexible display device is covered by the light-shielding pattern so that it is not easily visible, thereby improving the visibility of the image. The aforementioned light-shielding pattern may be in the form of a single layer or multiple layers. The color of the shading pattern is not particularly limited, and can have multiple colors such as black, white, and metallic. The light-shielding pattern can be formed by pigments and polymers such as acrylic resins, ester resins, epoxy resins, polyurethanes, polysiloxanes, etc., to specifically express colors. These can be used alone or in a mixture of two or more kinds. The above-mentioned light-shielding pattern can be formed by various methods such as printing, lithography, and inkjet. The thickness of the light-shielding pattern is usually 1-100 μm, preferably 2-50 μm. In addition, a shape such as an inclination may be provided in the thickness direction of the light shielding pattern. [Example]

以下，藉由實施例對本發明進而詳細地進行說明。例中之「%」及「份」只要未特別說明，則意指質量%及質量份。首先，對評價方法進行說明。Hereinafter, the present invention will be further described in detail through examples. The "%" and "parts" in the examples mean mass% and parts by mass unless otherwise specified. First, the evaluation method will be described.

＜耐溶劑性評價用樣品之製作＞ 向具備攪拌機、溫度計、回流冷凝器、滴加裝置及氮氣導入管之反應容器中添加丙烯酸正丁酯 97.0質量份、丙烯酸 1.0質量份、丙烯酸2-羥基乙酯 0.5質量份、乙酸乙酯 200質量份、及2,2'-偶氮雙異丁腈 0.08質量份，利用氮氣置換上述反應容器內之空氣。於氮氣氛圍下一面攪拌，一面將反應溶液升溫至60℃，反應6小時後冷卻至室溫，合成丙烯酸酯聚合物。測定所獲得之溶液中所包含之丙烯酸酯聚合物之重量平均分子量，結果為1,800,000。 將上述步驟中所獲得之丙烯酸酯聚合物 100質量份(固形物成分換算值；以下相同)、作為異氰酸酯系交聯劑之三羥甲基丙烷改性甲苯二異氰酸酯(Tosoh(股)製造，商品名「Coronate(註冊商標)L」) 0.30質量份、及作為矽烷偶合劑之3-縮水甘油氧基丙基三甲氧基矽烷(信越化學工業(股)製造，商品名「KBM403」) 0.30質量份進行混合並充分地攪拌，利用乙酸乙酯進行稀釋，藉此獲得黏著劑組合物之塗佈溶液。 藉由敷料器於分隔件(Lintec(股)製造：SP-PLR382190)之脫模處理面(剝離層面)以乾燥後之厚度成為25 μm之方式塗佈上述塗佈溶液後，於100℃下乾燥1分鐘，並於黏著劑層之與貼合有分隔件之面相反之面貼合另1片分隔件(Lintec(股)製造：SP-PLR381031)，獲得兩面附有分隔件之黏著劑層。 自以上述方式獲得之兩面附有分隔件之黏著劑層僅將黏著劑層貼合於黑色丙烯酸板，藉此於黑色丙烯酸板上形成黏著劑層，於該黏著劑層上貼合實施例及比較例中所獲得之聚醯胺醯亞胺樹脂膜，獲得依序積層有黑色丙烯酸板、黏著劑層、及光學膜之積層體(耐溶劑性評價用樣品)。＜Preparation of samples for solvent resistance evaluation＞ Add 97.0 parts by mass of n-butyl acrylate, 1.0 part by mass of acrylic acid, 0.5 parts by mass of 2-hydroxyethyl acrylate, and 200 parts by mass of ethyl acetate to a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube. Parts, and 0.08 parts by mass of 2,2'-azobisisobutyronitrile, replacing the air in the reaction vessel with nitrogen. While stirring under a nitrogen atmosphere, the reaction solution was heated to 60° C., reacted for 6 hours, and then cooled to room temperature to synthesize acrylate polymer. The weight average molecular weight of the acrylate polymer contained in the obtained solution was measured, and the result was 1,800,000. 100 parts by mass of the acrylate polymer obtained in the above steps (solid content conversion value; the same below), as an isocyanate crosslinking agent, trimethylolpropane modified toluene diisocyanate (manufactured by Tosoh Co., Ltd., product Name "Coronate (registered trademark) L") 0.30 parts by mass, and 3-glycidoxypropyltrimethoxysilane as a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM403") 0.30 parts by mass Mix and stir thoroughly, and dilute with ethyl acetate to obtain a coating solution of the adhesive composition. Use an applicator to apply the coating solution on the release surface (peeling surface) of the separator (manufactured by Lintec (stock): SP-PLR382190) so that the thickness after drying becomes 25 μm, and then dry at 100°C For 1 minute, another separator (manufactured by Lintec (stock): SP-PLR381031) was attached to the side of the adhesive layer opposite to the side where the separator was attached to obtain an adhesive layer with separators attached to both sides. Only the adhesive layer is attached to the black acrylic plate from the adhesive layer with separators on both sides obtained in the above manner, thereby forming an adhesive layer on the black acrylic plate, and attaching the embodiment and the adhesive layer on the adhesive layer For the polyamide imide resin film obtained in the comparative example, a laminate (a sample for solvent resistance evaluation) in which a black acrylic plate, an adhesive layer, and an optical film were sequentially laminated was obtained.

＜耐溶劑性試驗＞ 於耐溶劑性評價用樣品之光學膜側之表面上滴加乙醇，蓋上覆蓋玻璃並放置40分鐘。其間，以維持膜始終與乙醇接觸之狀態之方式自覆蓋玻璃上觀察，於確認到乙醇之揮發、乾燥時，暫時移開覆蓋玻璃並再次滴加乙醇後，再次蓋上覆蓋玻璃。其後，移開覆蓋膜並於室溫下放置1小時以上而使膜乾燥。 ＜耐溶劑性試驗前後之光學特性之測定＞ 使用柯尼卡美能達(股)製造之分光測色計(CM3700A)於下述條件下對耐溶劑性試驗前後之光學膜之反射光測定中之L＊ 、a＊ 及b＊ 值進行評價。 ・光源：D光源 ・入射光：相對於光學膜自法線方向以角度2°進行照射 ・檢測模式：反射SCE ・目標遮罩：LAV遮罩(測定範圍：直徑8 mm)<Solvent resistance test> Ethanol was dripped on the surface of the optical film side of the sample for solvent resistance evaluation, covered with a cover glass, and left for 40 minutes. In the meantime, observe from the cover glass in such a way that the film is always in contact with ethanol. When the volatilization and drying of the ethanol are confirmed, the cover glass is temporarily removed and the ethanol is dropped again, and then the cover glass is covered again. After that, the cover film was removed and left at room temperature for 1 hour or more to dry the film. <Measurement of optical properties before and after the solvent resistance test> Using the spectrophotometer (CM3700A) manufactured by Konica Minolta Co., Ltd. to measure the reflected light of the optical film before and after the solvent resistance test under the following conditions L * , a *, and b * values were evaluated.・Light source: D light source ・Incident light: Irradiated at an angle of 2° from the normal direction of the optical film ・Detection mode: Reflected SCE ・Target mask: LAV mask (Measurement range: 8 mm in diameter)

(全光線透過率之測定) 光學膜之全光線透過率係依據JIS K 7105：1981並藉由Suga Test Instruments(股)製造之全自動直讀霧度計HGM-2DP進行測定。(Determination of total light transmittance) The total light transmittance of the optical film is measured in accordance with JIS K 7105:1981 and by the automatic direct reading haze meter HGM-2DP manufactured by Suga Test Instruments (stock).

(霧度之測定) 光學膜之霧度係依據JIS K 7105：1981並藉由Suga Test Instruments(股)製造之全自動直讀霧度計HGM-2DP進行測定。(Determination of Haze) The haze of the optical film is measured according to JIS K 7105:1981 and is measured by the automatic direct reading haze meter HGM-2DP manufactured by Suga Test Instruments (stock).

(彈性模數之測定) 使用啞鈴切割機將實施例及比較例中所獲得之光學膜切成10 mm×100 mm之短條狀，獲得試驗樣品。針對該試驗樣品之彈性模數，使用島津製作所(股)製造之Autograph AG-IS，於夾頭間距離50 mm、拉伸速度10 mm/min之條件下測定應力-變形曲線，並根據應力之5～20 MPa下之斜率算出光學膜之彈性模數(GPa)。(Determination of elastic modulus) A dumbbell cutter was used to cut the optical films obtained in the examples and comparative examples into short strips of 10 mm×100 mm to obtain test samples. For the elastic modulus of the test sample, the Autograph AG-IS manufactured by Shimadzu Corporation was used to measure the stress-deformation curve under the conditions of a distance between the chucks of 50 mm and a tensile speed of 10 mm/min. Calculate the elastic modulus (GPa) of the optical film with the slope under 5-20 MPa.

(厚度之測定) 針對實施例及比較例中所獲得之光學膜，使用ABS Digimatic Indicator((股) Mitutoyo製造，「ID-C112BS」)測定光學膜之厚度。(Measurement of thickness) For the optical films obtained in the Examples and Comparative Examples, the thickness of the optical films was measured using an ABS Digimatic Indicator (made by Mitutoyo, "ID-C112BS").

＜重量平均分子量之測定＞ 凝膠滲透層析(GPC)測定 (1)預處理方法 向樣品中以濃度成為2 mg/mL之方式添加DMF溶離液(10 mmol/L溴化鋰溶液)，於80℃下一面攪拌30分鐘，一面加熱，冷卻後利用0.45 μm薄膜過濾器進行過濾，將所得者作為測定溶液。 (2)測定條件 管柱：Tosoh(股)製造之TSKgel α-2500((7)直徑7.8 mm×300 mm)×1根、α-M((13)直徑7.8 mm×300 mm)×2根 溶離液：DMF(10 mmol/L之溴化鋰添加) 流量：1.0 mL/min 檢測器：RI檢測器 管柱溫度：40℃ 注入量：100 μL 分子量標準：標準聚苯乙烯＜Determination of weight average molecular weight＞ Gel Permeation Chromatography (GPC) determination (1) Pretreatment method Add DMF lysate (10 mmol/L lithium bromide solution) to the sample at a concentration of 2 mg/mL, stir at 80°C for 30 minutes while heating, and after cooling, filter with a 0.45 μm membrane filter. As the measurement solution. (2) Measurement conditions Tubular column: TSKgel α-2500 ((7) diameter 7.8 mm×300 mm) × 1 piece, α-M ((13) diameter 7.8 mm×300 mm) × 2 pieces manufactured by Tosoh (stock) Eluent: DMF (10 mmol/L lithium bromide addition) Flow rate: 1.0 mL/min Detector: RI detector Column temperature: 40℃ Injection volume: 100 μL Molecular weight standard: standard polystyrene

＜溶劑處理後之外觀品質之評價＞ 針對光學膜滴加乙醇，蓋上覆蓋玻璃並放置40分鐘。其間，以維持膜始終與乙醇接觸之狀態之方式自覆蓋玻璃上觀察，於確認到乙醇之揮發、乾燥時，暫時移開覆蓋玻璃，再次滴加乙醇後再次蓋上覆蓋玻璃。其後，移開覆蓋膜並於室溫下放置1小時以上而使膜乾燥。利用黏著劑層將所獲得之光學膜貼合於黑色板，於螢光燈之下一面改變視認角度，一面觀察乙醇所接觸之光學膜表面，並以以下之基準對外觀品質進行評價。 (外觀品質之評價) 〇：於螢光燈所映入之角度以外之所有視認角度，光學膜之表面均勻且呈黑色被視認到。 △：於螢光燈所映入之角度以外之幾乎所有視認角度，光學膜之表面呈黑色被視認到，但亦略微存在表面之一部分呈白色被視認到之角度。 ×：於螢光燈所映入之角度以外，大量存在因反射光之散射而導致光學膜之表面之一部分呈白色被視認到之角度或存在表面整體呈白色被視認到之角度。＜Evaluation of appearance quality after solvent treatment＞ Add ethanol dropwise to the optical film, cover with a cover glass and leave for 40 minutes. In the meantime, observe from the cover glass in such a way that the film is always in contact with ethanol. When the volatilization and drying of the ethanol are confirmed, the cover glass is temporarily removed, and ethanol is added again and then the cover glass is covered again. After that, the cover film was removed and left at room temperature for 1 hour or more to dry the film. The obtained optical film was attached to the black plate using the adhesive layer, and the viewing angle was changed under a fluorescent lamp, while the surface of the optical film contacted by ethanol was observed, and the appearance quality was evaluated based on the following criteria. (Evaluation of appearance quality) ○: At all viewing angles other than the angle reflected by the fluorescent lamp, the surface of the optical film is uniform and black is visible. △: In almost all viewing angles other than the angle reflected by the fluorescent lamp, the surface of the optical film is seen as black, but there is also a slight angle where a part of the surface is seen as white. ×: In addition to the angle reflected by the fluorescent lamp, there are a large number of angles at which a part of the surface of the optical film is white, or the whole surface is white, because of the scattering of the reflected light.

＜合成例1：聚醯胺醯亞胺樹脂(1)之製造＞ 於氮氣氛圍下向具備攪拌翼之可分離式燒瓶中以TFMB之固形物成分成為5.87質量%之方式添加2,2'-雙(三氟甲基)聯苯胺(TFMB)及N,N-二甲基乙醯胺(DMAc)，進而相對於TFMB添加30.16 mol%之4,4'-(六氟亞異丙基)二鄰苯二甲酸二酐(6FDA)，於室溫下一面攪拌，一面使TFMB與6FDA溶解於DMAc中。 繼而，向燒瓶中以相對於TFMB成為10.05 mol%之方式添加4,4'-氧基雙(苯甲醯氯)(OBBC)，以相對於TFMB成為60.30 mol%之方式添加對苯二甲醯氯(TPC)進行反應。 繼而，向燒瓶中相對於TFMB添加105.53 mol%之乙酸酐，並攪拌15分鐘後，相對於TFMB添加35.17mol%之4-甲基吡啶，將反應容器升溫至70℃，進而攪拌3小時，獲得反應液。 將所獲得之反應液冷卻至室溫，並呈線狀投入大量甲醇中，取出所析出之沈澱物，並於甲醇中浸漬6小時後，利用甲醇洗淨。繼而，於78℃下進行沈澱物之減壓乾燥，獲得聚醯胺醯亞胺樹脂(1)。聚醯胺醯亞胺樹脂(1)之重量平均分子量為336,000。<Synthesis example 1: Production of polyamide imine resin (1)> Add 2,2'-bis(trifluoromethyl)benzidine (TFMB) and N,N-diphenylamine (TFMB) to a separable flask equipped with a stirring blade under a nitrogen atmosphere so that the solid content of TFMB becomes 5.87% by mass. Methyl acetamide (DMAc), and then add 30.16 mol% of 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA) relative to TFMB, and stir at room temperature. Dissolve TFMB and 6FDA in DMAc. Then, 4,4'-oxybis(benzyl chloride) (OBBC) was added to the flask so that 10.05 mol% relative to TFMB, and terephthalate was added so that it became 60.30 mol% relative to TFMB. Chlorine (TPC) reacts. Then, 105.53 mol% of acetic anhydride relative to TFMB was added to the flask, and after stirring for 15 minutes, 35.17 mol% of 4-picoline relative to TFMB was added, and the reaction vessel was heated to 70°C and stirred for 3 hours to obtain The reaction solution. The obtained reaction solution was cooled to room temperature, and was linearly thrown into a large amount of methanol, and the deposited precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Then, the precipitate was dried under reduced pressure at 78°C to obtain a polyimide resin (1). The weight average molecular weight of the polyimide resin (1) is 336,000.

＜合成例2：聚醯胺醯亞胺樹脂(2)之製造＞ 於氮氣氛圍下向具備攪拌翼之可分離式燒瓶中以TFMB之固形物成分成為5.51質量%之方式添加TFMB及DMAc，進而相對於TFMB添加11.11 mol%之4,4'-(六氟亞丙基)二苯胺(6FDAM)，於室溫下一面攪拌，一面使TFMB與6FDAM溶解於DMAc中。繼而，向燒瓶中以相對於TFMB成為44.63 mol%之方式添加3,3',4,4'-聯苯四羧酸二酐(BPDA)，並於室溫下攪拌12小時。其後，冷卻至10℃後，以相對於TFMB成為30.13 mol%之方式添加TPC，並攪拌10分鐘，進而以相對於TFMB成為30.13 mol%之方式添加TPC，並攪拌20分鐘。其後，添加與首次添加之DMAc等量之DMAc，並以相對於TFMB成為6.70 mol%之方式添加TPC，攪拌2小時。繼而，向燒瓶中相對於TFMB分別添加67.04mol%之二異丙基乙基胺與4-甲基吡啶，相對於TFMB添加312.80 mol%之乙酸酐，並攪拌30分鐘後，將內溫升溫至70℃，進而攪拌3小時，獲得反應液。 將所獲得之反應液冷卻至室溫，並呈線狀投入大量甲醇中，取出所析出之沈澱物，於甲醇中浸漬6小時後，利用甲醇洗淨。繼而，於60℃下進行沈澱物之減壓乾燥，獲得聚醯胺醯亞胺樹脂(2)。聚醯胺醯亞胺樹脂(2)之重量平均分子量為556,000。<Synthesis Example 2: Production of polyamide imide resin (2)> Under a nitrogen atmosphere, TFMB and DMAc were added to a separable flask equipped with stirring wings so that the solid content of TFMB became 5.51% by mass, and 11.11 mol% of 4,4'-(hexafluoropropylene) was added to TFMB. Base) diphenylamine (6FDAM), stirring at room temperature, while dissolving TFMB and 6FDAM in DMAc. Then, 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was added to the flask so that it became 44.63 mol% with respect to TFMB, and stirred at room temperature for 12 hours. Then, after cooling to 10 degreeC, TPC was added so that it might become 30.13 mol% with respect to TFMB, and it stirred for 10 minutes, and TPC was added so that it might become 30.13 mol% with respect to TFMB, and it stirred for 20 minutes. After that, the same amount of DMAc as the DMAc added for the first time was added, and TPC was added so as to be 6.70 mol% with respect to TFMB, and stirred for 2 hours. Then, 67.04 mol% of diisopropylethylamine and 4-picoline were added to the flask with respect to TFMB, and 312.80 mol% of acetic anhydride was added to TFMB. After stirring for 30 minutes, the internal temperature was raised to At 70°C, it was further stirred for 3 hours to obtain a reaction liquid. The obtained reaction liquid was cooled to room temperature, and was linearly thrown into a large amount of methanol, and the deposited precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Then, the precipitate was dried under reduced pressure at 60°C to obtain a polyimide resin (2). The weight average molecular weight of the polyimide resin (2) is 556,000.

＜合成例3：聚醯胺醯亞胺樹脂(3)之製造＞ 於氮氣氛圍下向具備攪拌翼之可分離式燒瓶中以TFMB之固形物成分成為4.75質量%之方式添加TFMB及DMAc，進而相對於TFMB添加25.02 mol%之6FDAM，於室溫下一面攪拌，一面使TFMB與6FDAM溶解於DMAc中。繼而，向燒瓶中以相對於TFMB成為75.78 mol%之方式添加BPDA，並於室溫下攪拌16小時。其後，冷卻至10℃後，以相對於TFMB成為22.70 mol%之方式添加TPC，並攪拌10分鐘，進而，以相對於TFMB成為22.70 mol%之方式添加TPC，並攪拌20分鐘。其後，添加與首次添加之DMAc等量之DMAc，並以相對於TFMB成為5.06 mol%之方式添加TPC，並攪拌2小時。繼而，向燒瓶中相對於TFMB分別添加50.51 mol%之二異丙基乙基胺與4-甲基吡啶，相對於TFMB添加530.39 mol%之乙酸酐，攪拌30分鐘後，將內溫升溫至70℃，進而攪拌3小時，獲得反應液。 將所獲得之反應液冷卻至室溫，並呈絲狀投入大量甲醇中，取出所析出之沈澱物，並於甲醇中浸漬6小時後，利用甲醇洗淨。繼而，於60℃下進行沈澱物之減壓乾燥，獲得聚醯胺醯亞胺樹脂(3)。聚醯胺醯亞胺樹脂(3)之重量平均分子量為461,000。<Synthesis example 3: Production of polyamide imide resin (3)> Add TFMB and DMAc to a separable flask equipped with stirring wings under a nitrogen atmosphere so that the solid content of TFMB becomes 4.75% by mass, and then add 25.02 mol% of 6FDAM relative to TFMB, and stir at room temperature. Dissolve TFMB and 6FDAM in DMAc. Then, BPDA was added to the flask so that it might become 75.78 mol% with respect to TFMB, and it stirred at room temperature for 16 hours. Then, after cooling to 10 degreeC, TPC was added so that it might become 22.70 mol% with respect to TFMB, and it stirred for 10 minutes, and TPC was added so that it might become 22.70 mol% with respect to TFMB, and it stirred for 20 minutes. Thereafter, the same amount of DMAc as the DMAc added for the first time was added, and TPC was added so as to become 5.06 mol% with respect to TFMB, and stirred for 2 hours. Then, 50.51 mol% of diisopropylethylamine and 4-picoline were added to the flask with respect to TFMB, and 530.39 mol% of acetic anhydride was added to TFMB. After stirring for 30 minutes, the internal temperature was increased to 70. It was further stirred for 3 hours at °C to obtain a reaction liquid. The obtained reaction liquid was cooled to room temperature, and was thrown into a large amount of methanol in the form of filaments, and the deposited precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Then, the precipitate was dried under reduced pressure at 60°C to obtain a polyimide resin (3). The weight average molecular weight of the polyimide resin (3) is 461,000.

＜合成例4：聚醯胺醯亞胺樹脂(4)之製造＞ 於氮氣氛圍下向具備攪拌翼之可分離式燒瓶中以TFMB之固形物成分成為5.56質量%之方式添加TFMB及DMAc，進而相對於TFMB添加11.19 mol%之6FDAM，於室溫下一面攪拌，一面使TFMB與6FDAM溶解於DMAc中。繼而，向燒瓶中以相對於TFMB成為34.01 mol%之方式添加BPDA，並於室溫下攪拌16小時。其後，冷卻至10℃後，以相對於TFMB成為30.60 mol%之方式添加TPC，以相對於TFMB成為5.67 mol%之方式添加OBBC，並攪拌10分鐘。進而，以相對於TFMB成為30.60 mol%之方式添加TPC，繼而，相對於TFMB添加5.67 mol%之OBBC，並攪拌20分鐘。其後，添加與首次添加之DMAc等量之DMAc，並以相對於TFMB成為6.81 mol%之方式添加TPC，並攪拌2小時。繼而，向燒瓶中分別相對於TFMB添加79.35 mol%之二異丙基乙基胺與4-甲基吡啶，相對於TFMB添加238.14 mol%之乙酸酐，並攪拌30分鐘後，將內溫升溫至70℃，進而攪拌3小時，獲得反應液。 將所獲得之反應液冷卻至室溫，並呈線狀投入大量甲醇中，取出所析出之沈澱物，並於甲醇中浸漬6小時後，利用甲醇洗淨。繼而，於60℃下進行沈澱物之減壓乾燥，獲得聚醯胺醯亞胺樹脂(4)。聚醯胺醯亞胺樹脂(4)之重量平均分子量為360,000。<Synthesis example 4: Production of polyamide imide resin (4)> Add TFMB and DMAc to a separable flask equipped with a stirring wing under a nitrogen atmosphere so that the solid content of TFMB becomes 5.56% by mass, and then add 11.19 mol% of 6FDAM relative to TFMB, and stir at room temperature. Dissolve TFMB and 6FDAM in DMAc. Then, BPDA was added to the flask so that it might become 34.01 mol% with respect to TFMB, and it stirred at room temperature for 16 hours. Then, after cooling to 10 degreeC, TPC was added so that it might become 30.60 mol% with respect to TFMB, OBBC was added so that it might become 5.67 mol% with respect to TFMB, and it stirred for 10 minutes. Furthermore, TPC was added so that it might become 30.60 mol% with respect to TFMB, and 5.67 mol% of OBBC was added with respect to TFMB, and it stirred for 20 minutes. After that, the same amount of DMAc as the DMAc added for the first time was added, and TPC was added so as to be 6.81 mol% relative to TFMB, and stirred for 2 hours. Then, 79.35 mol% of diisopropylethylamine and 4-picoline were added to the flask with respect to TFMB, and 238.14 mol% of acetic anhydride was added to TFMB. After stirring for 30 minutes, the internal temperature was increased to At 70°C, it was further stirred for 3 hours to obtain a reaction liquid. The obtained reaction solution was cooled to room temperature, and was linearly thrown into a large amount of methanol, and the deposited precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Then, the precipitate was dried under reduced pressure at 60°C to obtain a polyimide resin (4). The weight average molecular weight of the polyimide resin (4) is 360,000.

＜比較例1＞ (光學膜之製造) 將合成例1中所獲得之聚醯胺醯亞胺樹脂(1)及DMAc以樹脂組合物中之聚醯胺醯亞胺樹脂之含有比率成為11.0質量%之量進行混合。使用敷料器將所獲得之樹脂組合物以自支撐膜之厚度成為55 μm之方式塗佈於聚酯基材(東洋紡織(股)製造，商品名「A4100」)之平滑面上，於50℃下乾燥30分鐘，繼而於140℃下乾燥15分鐘後，將所獲得之塗膜自聚酯基材剝離，獲得自支撐膜。將自支撐膜固定於模框，進而於大氣下於200℃下乾燥40分鐘，獲得厚度50 μm之聚醯胺醯亞胺樹脂膜(1)。<Comparative example 1> (Manufacturing of Optical Film) The polyamideimide resin (1) and DMAc obtained in Synthesis Example 1 were mixed so that the content ratio of the polyamideimide resin in the resin composition became 11.0% by mass. Use an applicator to apply the obtained resin composition to the smooth surface of a polyester substrate (manufactured by Toyobo Co., Ltd., trade name "A4100") so that the thickness of the self-supporting film becomes 55 μm, at 50°C After drying for 30 minutes and then drying at 140°C for 15 minutes, the obtained coating film was peeled from the polyester substrate to obtain a self-supporting film. The self-supporting film was fixed to the mold frame, and then dried in the atmosphere at 200° C. for 40 minutes to obtain a polyamide imide resin film (1) with a thickness of 50 μm.

＜實施例1＞ 將合成例2中所獲得之聚醯胺醯亞胺樹脂(2)及DMAc以樹脂組合物中之聚醯胺醯亞胺樹脂之含有比率成為6.5質量%之量進行混合。進行與比較例1相同之操作，獲得聚醯胺醯亞胺樹脂膜(2)。<Example 1> The polyamide imide resin (2) and DMAc obtained in Synthesis Example 2 were mixed so that the content ratio of the polyamide imide resin in the resin composition became 6.5% by mass. The same operation as in Comparative Example 1 was performed to obtain a polyimide resin film (2).

＜實施例2＞ 將合成例3中所獲得之聚醯胺醯亞胺樹脂(3)及DMAc以樹脂組合物中之聚醯胺醯亞胺樹脂之含有比率成為6.5質量%之量進行混合。進行與比較例1相同之操作，獲得聚醯胺醯亞胺樹脂膜(3)。<Example 2> The polyamide imide resin (3) and DMAc obtained in Synthesis Example 3 were mixed so that the content of the polyamide imide resin in the resin composition became 6.5% by mass. The same operation as in Comparative Example 1 was performed to obtain a polyimide resin film (3).

＜實施例3＞ 將合成例3中所獲得之聚醯胺醯亞胺樹脂(4)及DMAc以樹脂組合物中之聚醯胺醯亞胺樹脂之含有比率成為8.5質量%之量進行混合。進行與比較例1相同之操作，獲得聚醯胺醯亞胺樹脂膜(4)。<Example 3> The polyamide imide resin (4) and DMAc obtained in Synthesis Example 3 were mixed so that the content of the polyamide imide resin in the resin composition became 8.5% by mass. The same operation as in Comparative Example 1 was performed to obtain a polyimide resin film (4).

針對以如上方式獲得之聚醯胺醯亞胺樹脂膜(1)～(4)，進行全光線透過率、霧度、耐溶劑性試驗及外觀品質之評價。將所獲得之結果示於表1。For the polyimide resin films (1) to (4) obtained in the above manner, the total light transmittance, haze, solvent resistance test, and appearance quality were evaluated. The results obtained are shown in Table 1.

[表1]    比較例1 實施例1 實施例2 實施例3 樹脂之種類 PAI(l) PAI(2) PAI(3) PAI(4) 全光線透過率(%) 92 90 90 90 霧度(%) 0.3 0.4 0.7 0.3 耐溶劑性試驗 反射a* 試驗前 0.03 -0.14 -0.27 -0.16 試驗後 0.03 -0.04 -0.16 -0.12 變化量 -0.01 0.10 0.11 0.05 反射b* 試驗前 0.18 -0.49 -0.13 -0.10 試驗後 0.05 -0.44 -0.11 -0.18 變化量 0.13 0.05 0.02 0.08 反射L* 試驗前 1.45 2.18 2.09 1.86 試驗後 2.01 1.98 2.12 2.08 變化量 0.56 0.20 0.03 0.22 溶劑處理後之外觀品質 × 〇 〇 △ [Table 1] Comparative example 1 Example 1 Example 2 Example 3 Type of resin PAI(l) PAI(2) PAI(3) PAI(4) Total light transmittance (%) 92 90 90 90 Haze (%) 0.3 0.4 0.7 0.3 Solvent resistance test Reflection a* Before the test 0.03 -0.14 -0.27 -0.16 After the test 0.03 -0.04 -0.16 -0.12 Variation -0.01 0.10 0.11 0.05 Reflection b* Before the test 0.18 -0.49 -0.13 -0.10 After the test 0.05 -0.44 -0.11 -0.18 Variation 0.13 0.05 0.02 0.08 Reflection L* Before the test 1.45 2.18 2.09 1.86 After the test 2.01 1.98 2.12 2.08 Variation 0.56 0.20 0.03 0.22 Appearance quality after solvent treatment × 〇 〇 △

Claims (14)

一種光學膜，其係包含至少具有源自四羧酸化合物之式(a)所表示之結構單元、源自二羧酸化合物之式(b)所表示之結構單元、及源自二胺化合物之式(c)所表示之結構單元之聚醯胺醯亞胺系樹脂者： [化45]
Figure 03_image093
[式(a)中，Y表示四價有機基，式(b)中，Z表示二價有機基，式(c)中，X表示二價有機基，Rc 相互獨立地表示氫原子或鍵結鍵，＊表示鍵結鍵]； 該聚醯胺醯亞胺系樹脂包含選自由如下結構單元所組成之群中之至少1種結構單元：作為該源自四羧酸化合物之結構單元之式(a)中之Y係由式(1)所表示之結構單元(a1)及作為該源自二羧酸化合物之結構單元之式(b)中之Z係由式(1)所表示之結構單元(b1)； [化46]
Figure 03_image095
[式(1)中， Ra 相互獨立地表示氫原子、碳數1～12之烷基、碳數1～12之烷氧基或碳數6～12之芳基，Ra 中所包含之氫原子可相互獨立地被取代為鹵素原子， n表示0～2之整數， ＊表示鍵結鍵，R＊ 於Y係由式(1)所表示之情形時，表示鍵結鍵，於Z係由式(1)所表示之情形時，表示Ra ] 該光學膜之反射光測定中之基於L＊ a＊ b＊ 表色系統之亮度L1 ＊ 與和乙醇接觸40分鐘後之該光學膜之基於L＊ a＊ b＊ 表色系統之亮度L2 ＊ 之差之絕對值ΔL＊ 為0.5以下。An optical film containing at least a structural unit represented by formula (a) derived from a tetracarboxylic acid compound, a structural unit represented by formula (b) derived from a dicarboxylic acid compound, and a structural unit derived from a diamine compound The polyamide imine resin of the structural unit represented by formula (c): [化45]
Figure 03_image093
[In formula (a), Y represents a tetravalent organic group, in formula (b), Z represents a divalent organic group, in formula (c), X represents a divalent organic group, and R c independently represents a hydrogen atom or bond Bonding, * represents bonding bond]; The polyamide imine-based resin includes at least one structural unit selected from the group consisting of the following structural units: the formula as the structural unit derived from the tetracarboxylic acid compound (a) Y is a structural unit (a1) represented by formula (1) and Z in formula (b) as a structural unit derived from the dicarboxylic acid compound is a structure represented by formula (1) Unit (b1); [化46]
Figure 03_image095
[In the formula (1), R a each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, the alkoxy having 1 to 12 carbon atoms or the aryl group of 6 to 12, R a contained the Hydrogen atoms can be substituted with halogen atoms independently of each other, n represents an integer from 0 to 2, ＊ represents a bonding bond, and R ＊ when Y is represented by formula (1), represents a bonding bond, in Z system when the case where the formula (1) represented by the representing R a] reflected by the optical film of the optical film after the middle of the contact based on the luminance L * a * b * color system of L 1 * and ethanol 40 minutes light measurement The absolute value ΔL * of the difference between the brightness L 2 * based on the L * a * b * color system is 0.5 or less. 如請求項1之光學膜，其反射光測定中之基於L＊ a＊ b＊ 表色系統之該光學膜之b1 ＊ 與和乙醇接觸40分鐘後之該光學膜之b2 ＊ 之差之絕對值Δb＊ 為0.1以下。For the optical film of claim 1, the difference between the b 1 ＊ of the optical film based on the L * a * b ＊ color system and the b 2 * of the optical film after being in contact with ethanol for 40 minutes in the reflected light measurement The absolute value Δb * is 0.1 or less. 如請求項1或2之光學膜，其中光學膜之厚度為25 μm以上且100 μm以下。The optical film of claim 1 or 2, wherein the thickness of the optical film is 25 μm or more and 100 μm or less. 如請求項1至3中任一項之光學膜，其中光學膜之霧度為5%以下。The optical film of any one of claims 1 to 3, wherein the haze of the optical film is 5% or less. 如請求項1至4中任一項之光學膜，其中聚醯胺醯亞胺系樹脂包含式(2)所表示之結構單元(b2)作為源自二羧酸化合物之結構單元： [化47]
Figure 03_image097
[式(2)中，Z1 表示作為可具有取代基之單環式芳香族環或縮合多環式芳香族環之二價芳香族基，＊表示鍵結鍵] 且包含式(3)所表示之結構單元(c1)作為源自二胺化合物之結構單元： [化48]
Figure 03_image099
[式(3)中，X1 表示可具有取代基之二價芳香族基，Rc 相互獨立地表示氫原子或鍵結鍵，＊表示鍵結鍵]。The optical film according to any one of claims 1 to 4, wherein the polyimide imine-based resin contains the structural unit (b2) represented by formula (2) as the structural unit derived from the dicarboxylic acid compound: [化47] ]
Figure 03_image097
[In formula (2), Z 1 represents a divalent aromatic group as a monocyclic aromatic ring or a condensed polycyclic aromatic ring that may have a substituent, * represents a bonding bond] and includes the formula (3) The structural unit (c1) shown as a structural unit derived from a diamine compound: [化48]
Figure 03_image099
[In formula (3), X 1 represents a divalent aromatic group which may have a substituent, R c represents a hydrogen atom or a bonding bond independently of each other, and * represents a bonding bond]. 如請求項5之光學膜，其中式(3)中之X1 係由式(4)所表示： [化49]
Figure 03_image101
[式(4)中，Rb 相互獨立地表示碳數1～6之烷基、碳數6～12之芳基、或碳數1～6之烷氧基，Rb 中所包含之氫原子可相互獨立地被取代為鹵素原子，r相互獨立地表示1～4之整數，＊表示鍵結鍵]。Such as the optical film of claim 5, wherein X 1 in formula (3) is represented by formula (4): [化49]
Figure 03_image101
[In formula (4), R b independently represents an alkyl group having 1 to 6 carbons, an aryl group having 6 to 12 carbons, or an alkoxy group having 1 to 6 carbons, and the hydrogen atom contained in R b It can be substituted with a halogen atom independently of each other, and r independently represents an integer of 1 to 4, and * represents a bonding bond]. 如請求項1至6中任一項之光學膜，其中聚醯胺醯亞胺系樹脂進而包含選自由如下結構單元所組成之群中之至少1種結構單元：作為源自二羧酸化合物之結構單元之式(b)中之Z係由式(5)： [化50]
Figure 03_image103
[式(5)中，Ar1 相互獨立地表示可具有取代基之二價芳香族基， V表示單鍵、-O-、二苯基亞甲基、碳數1～12之直鏈狀、支鏈狀或脂環式之二價烴基、-SO2 -、-S-、-CO-或-N(R12 )-，此處，該烴基中所包含之氫原子可相互獨立地被取代為鹵素原子，R12 表示氫原子、或可經鹵素原子取代之碳數1～12之烷基， m表示1～3之整數，其中，於m為2或3之情形時所存在之複數個V可相互相同，亦可不同， ＊表示鍵結鍵] 所表示之結構單元(b3)、作為源自二胺化合物之結構單元之式(c)中之X係由式(5)所表示之結構單元(c2)、及作為源自四羧酸化合物之結構單元之式(a)中之Y係由式(6)： [化51]
Figure 03_image105
[式(6)中，Ar2 相互獨立地表示可具有取代基之三價芳香族基， s表示0～2之整數， Ar1 、V及＊如式(5)中之Ar1 、V及＊所定義，其中於s為2之情形時所存在之複數個V及Ar1 可分別相互相同，亦可不同，其中式(6)中之V並非為單鍵] 所表示之結構單元(a2)。The optical film according to any one of claims 1 to 6, wherein the polyamide imine-based resin further comprises at least one structural unit selected from the group consisting of the following structural units: as derived from a dicarboxylic acid compound The Z in the formula (b) of the structural unit is derived from the formula (5): [化50]
Figure 03_image103
[In formula (5), Ar 1 independently represents a divalent aromatic group that may have a substituent, V represents a single bond, -O-, diphenylmethylene, a linear chain with 1 to 12 carbon atoms, A branched or alicyclic divalent hydrocarbon group, -SO 2 -, -S-, -CO- or -N(R 12 )-, where the hydrogen atoms contained in the hydrocarbon group can be substituted independently of each other It is a halogen atom, R 12 represents a hydrogen atom, or an alkyl group with 1 to 12 carbon atoms which can be substituted by a halogen atom, and m represents an integer of 1 to 3, where there are plural when m is 2 or 3 V may be the same or different from each other, * represents the structural unit (b3) represented by the bond], and X in the formula (c) as a structural unit derived from a diamine compound is represented by the formula (5) Structural unit (c2), and Y in formula (a) as a structural unit derived from a tetracarboxylic acid compound is derived from formula (6): [化51]
Figure 03_image105
[In formula (6), Ar 2 independently represents a trivalent aromatic group which may have a substituent, s represents an integer of 0-2, Ar 1 , V and * are as in the formula (5) Ar 1 , V and ＊As defined, the plural V and Ar 1 existing when s is 2 may be the same or different from each other, wherein V in formula (6) is not a single bond] is the structural unit represented by (a2 ). 如請求項7之光學膜，其中式(5)及式(6)係由式(7)所表示： [化52]
Figure 03_image107
[式(7)中，R1 相互獨立地表示氫原子、碳數1～12之烷基、碳數1～12之烷氧基或碳數6～12之芳基，R1 中所包含之氫原子可相互獨立地被取代為鹵素原子， R＊ 表示R1 或鍵結鍵， ＊表示鍵結鍵， V表示單鍵、-O-、二苯基亞甲基、碳數1～12之直鏈狀、支鏈狀或脂環式之二價烴基、-SO2 -、-S-、-CO-或-N(R12 )-，此處，該烴基中所包含之氫原子可相互獨立地被取代為鹵素原子，R12 表示氫原子、或可經鹵素原子取代之碳數1～12之烷基，其中於式(6)係由式(7)所表示之情形時，V並非為單鍵]。Such as the optical film of claim 7, in which formula (5) and formula (6) are expressed by formula (7): [化52]
Figure 03_image107
[In formula (7), R 1 independently represents a hydrogen atom, a C 1-12 alkyl group, a C 1-12 alkoxy group, or a C 6-12 aryl group, which is contained in R 1 Hydrogen atoms can be independently substituted with halogen atoms, R ＊ represents R 1 or a bonding bond, ＊represents a bonding bond, V represents a single bond, -O-, diphenylmethylene, carbon number 1-12 A linear, branched or alicyclic divalent hydrocarbon group, -SO 2 -, -S-, -CO-, or -N(R 12 )-, where the hydrogen atoms contained in the hydrocarbon group can interact with each other Is independently substituted with a halogen atom, R 12 represents a hydrogen atom, or an alkyl group with 1 to 12 carbons which can be substituted by a halogen atom, wherein when formula (6) is represented by formula (7), V is not Is a single key]. 如請求項8之光學膜，其中式(7)係由式(7')或式(7")所表示： [化53]
Figure 03_image109
[式(7')中，R＊ 表示氫原子或鍵結鍵，＊表示鍵結鍵] [化54]
Figure 03_image111
[式(7")中，＊表示鍵結鍵]。Such as the optical film of claim 8, wherein formula (7) is expressed by formula (7') or formula (7"): [化53]
Figure 03_image109
[In formula (7'), R * represents a hydrogen atom or a bonding bond, and * represents a bonding bond] [化54]
Figure 03_image111
[In formula (7"), * represents a bonding bond]. 如請求項1至9中任一項之光學膜，其中式(1)係由式(1')所表示： [化55]
Figure 03_image113
[式(1')中，＊表示鍵結鍵，R＊ 於Y係由式(1)所表示之情形時，表示鍵結鍵，於Z係由式(1)所表示之情形時，表示氫原子]。Such as the optical film of any one of claims 1 to 9, wherein the formula (1) is represented by the formula (1'): [化55]
Figure 03_image113
When [In the formula (1 '), * represents a bonding bond, R * in the Y lines by the formula (1) when the case represented, the represented bond bond, the Z-line by the formula (1) When expressed, the expressed A hydrogen atom]. 如請求項1至10中任一項之光學膜，其係可撓性顯示裝置之前面板用之膜。The optical film of any one of claims 1 to 10 is a film for the front panel of a flexible display device. 一種可撓性顯示裝置，其具備如請求項1至11中任一項之光學膜。A flexible display device provided with the optical film according to any one of claims 1 to 11. 如請求項12之可撓性顯示裝置，其進而具備觸控感測器。For example, the flexible display device of claim 12 further includes a touch sensor. 如請求項12或13之可撓性顯示裝置，其進而具備偏光板。For example, the flexible display device of claim 12 or 13 further includes a polarizing plate.
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