TW201936382A - Laminated body including a transparent resin film and a protective film - Google Patents

Laminated body including a transparent resin film and a protective film Download PDF

Info

Publication number
TW201936382A
TW201936382A TW108104357A TW108104357A TW201936382A TW 201936382 A TW201936382 A TW 201936382A TW 108104357 A TW108104357 A TW 108104357A TW 108104357 A TW108104357 A TW 108104357A TW 201936382 A TW201936382 A TW 201936382A
Authority
TW
Taiwan
Prior art keywords
resin film
transparent resin
film
protective film
laminated body
Prior art date
Application number
TW108104357A
Other languages
Chinese (zh)
Other versions
TWI791761B (en
Inventor
福井仁之
大松一喜
唐澤真義
岸田明子
Original Assignee
日商住友化學股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日商住友化學股份有限公司 filed Critical 日商住友化學股份有限公司
Publication of TW201936382A publication Critical patent/TW201936382A/en
Application granted granted Critical
Publication of TWI791761B publication Critical patent/TWI791761B/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent

Landscapes

  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

An object of the present invention is to provide a laminated body including a transparent resin film based on a polyimide polymer, which is less likely to generate bumps (orange peel) on the surface of the film, and has good appearance and visibility. The laminated body of the present invention includes a transparent resin film and a protective film, wherein the transparent resin film includes at least one selected from the group consisting of polyimide, polyamide, and polyamideimide, and a solvent, the protective film is bonded to at least one surface of the transparent resin film, and the arithmetic mean waviness Wa of the protective film surface in contact with the transparent resin film, that is calculated according to Equation (1) is 30 nm or less. [In Equation (1), Zw(x, y) represents the height of each point of surface bumps obtained by using a Gaussian filter having a cutoff value of 20 [mu]m and an amplitude transfer rate of 50% based on two-dimensional height data of the protective film surface, and lx, ly respectively represent the range of a measurement area in the x and y directions.].

Description

積層體Laminated body

本發明係關於一種積層體。The present invention relates to a laminated body.

近年來，隨著各種圖像顯示裝置之顯示器之薄型化、輕量化及可撓化等，作為代替先前所使用之玻璃之材料，廣泛使用基於聚醯亞胺或聚醯胺等高分子之透明樹脂膜。作為此種透明樹脂膜之製造方法之一，已知有澆鑄法(溶液流延法)。於澆鑄法中，通常將溶解於溶劑中之包含聚醯亞胺等高分子之清漆塗佈於支持基材上而進行製膜，將其自支持基材剝離後，藉由乾燥除去溶劑，藉此可連續地成形樹脂膜。於製膜之透明樹脂膜之表面適當積層可剝離之保護膜，謀求膜表面之保護(專利文獻1～3)。
[先前技術文獻]
[專利文獻]In recent years, with the reduction in thickness, weight, and flexibility of displays for various image display devices, transparent materials based on polymers such as polyimide or polyimide have been widely used as materials to replace glass used previously. Resin film. As one of the manufacturing methods of such a transparent resin film, the casting method (solution casting method) is known. In the casting method, a varnish containing a polymer such as polyimide, which is dissolved in a solvent, is usually coated on a supporting substrate to form a film. After peeling it off from the supporting substrate, the solvent is removed by drying, and This can continuously form a resin film. A peelable protective film is appropriately laminated on the surface of the transparent resin film to be formed to protect the film surface (Patent Documents 1 to 3).
[Prior technical literature]
[Patent Literature]

[專利文獻1]日本專利特開2010-208312號公報
[專利文獻2]日本專利特開2015-214122號公報
[專利文獻3]日本專利特開2016-87799號公報[Patent Document 1] Japanese Patent Laid-Open No. 2010-208312
[Patent Document 2] Japanese Patent Laid-Open No. 2015-214122
[Patent Document 3] Japanese Patent Laid-Open No. 2016-87799

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

於樹脂膜中存在溶劑之情形時，一般情況下，樹脂膜與保護膜之密接性變高。因此，存在如下情形：由於保護膜之表面凹凸被轉印至與保護膜貼合之透明樹脂膜之表面，故產生具有起伏之表面凹凸，其被稱為所謂之橘皮。尤其是於藉由澆鑄法等使用溶劑而製造之透明樹脂膜中，於連續之生產中，難以完全除去清漆中之溶劑而殘存一定程度量之溶劑，則於與保護膜貼合時，容易轉印保護膜之表面凹凸，從而變得容易產生表面凹凸。此種透明樹脂膜之表面凹凸不僅對於要求高透明性之透明樹脂膜而言是外觀上之缺陷，而且於用於各種圖像顯示裝置等顯示器之情形時，亦成為視認性惡化之原因。When a solvent is present in the resin film, in general, the adhesion between the resin film and the protective film becomes high. Therefore, there are cases where the surface unevenness of the protective film is transferred to the surface of the transparent resin film bonded to the protective film, so that the surface unevenness having undulations is generated, which is called so-called orange peel. Especially in a transparent resin film manufactured by using a solvent such as a casting method, it is difficult to completely remove the solvent in the varnish and to leave a certain amount of solvent in continuous production, and it is easy to transfer it when it is bonded to the protective film. The unevenness on the surface of the print protection film makes it easy to produce unevenness on the surface. The unevenness of the surface of such a transparent resin film is not only a defect in appearance for a transparent resin film that requires high transparency, but also causes deterioration in visibility when used in displays such as various image display devices.

因此，本發明之目的在於提供一種包含基於聚醯亞胺系高分子之透明樹脂膜積層體，其不易產生膜表面之凹凸、即橘皮，具有良好之外觀及視認性。
[解決問題之技術手段]Therefore, an object of the present invention is to provide a transparent resin film laminate comprising a polyimide-based polymer, which is less likely to cause unevenness on the surface of the film, that is, orange peel, and has good appearance and visibility.
[Technical means to solve the problem]

本發明者等人為解決上述問題而進行了銳意研究，結果完成本發明。即，本發明提供以下合適之態樣。
[1]一種積層體，其係包含透明樹脂膜與保護膜而成者，上述透明樹脂膜係包含選自由聚醯亞胺、聚醯胺及聚醯胺醯亞胺所組成之群中之至少1種及溶劑而成者，上述保護膜貼合於上述透明樹脂膜之至少一個面，且根據數式(1)而算出之與透明樹脂膜相接之保護膜表面之算術平均波紋度Wa為30 nm以下。
數式(1)：
[數1]

[數式(1)中，Zw(x，y)表示根據保護膜表面之二維高度資料，使用截止值為20 μm、振幅傳遞率為50%之高斯濾波器而獲得之表面起伏之各點之高度，lx 、ly 分別表示x、y方向之測定區域之範圍]
[2]如上述[1]中記載之積層體，其中透明樹脂膜之作為利用熱重-示差熱測定之自120℃至250℃之質量減少率而算出之殘留溶劑量S為0.001質量%以上。
[3]如上述[1]或[2]中記載之積層體，其中保護膜的定義為藉由測定溫度為140℃之凝膠滲透層析法進行測定而獲得之圖的Log M為2.82至3.32之面積相對於總面積之比率的低分子成分量W為0.4%以下。
[4]如上述[1]至[3]中任一項所記載之積層體，其中透明樹脂膜包含1種以上之溶劑，且該溶劑中沸點最高之溶劑之沸點為120～300℃。
[5]如上述[1]至[4]中任一項所記載之積層體，其中透明樹脂膜包含至少一種選自由N,N-二甲基乙醯胺、γ-丁內酯、N-甲基吡咯啶酮、環戊酮、乙酸丁酯及乙酸戊酯所組成之群中之溶劑。
[6]如上述[1]至[5]中任一項所記載之積層體，其中保護膜為聚烯烴系樹脂膜。
[發明之效果]The present inventors made earnest research in order to solve the above problems, and as a result, completed the present invention. That is, this invention provides the following suitable aspects.
[1] A laminate comprising a transparent resin film and a protective film, the transparent resin film comprising at least one selected from the group consisting of polyimide, polyimide, and polyimide For one type and solvent, the protective film is bonded to at least one surface of the transparent resin film, and the arithmetic average waviness Wa of the surface of the protective film that is in contact with the transparent resin film calculated according to formula (1) is Below 30 nm.
Equation (1):
[Number 1]

[In Equation (1), Zw (x, y) represents the points of the surface undulation obtained by using a Gaussian filter with a cutoff value of 20 μm and an amplitude transmission rate of 50% based on the two-dimensional height data of the surface of the protective film. Height, l x and l y respectively represent the range of the measurement area in the x and y directions]
[2] The laminated body as described in the above [1], wherein the amount of residual solvent S of the transparent resin film calculated as a mass reduction rate from 120 ° C to 250 ° C by thermogravimetric-differential thermal measurement is 0.001% by mass or more .
[3] The laminated body as described in the above [1] or [2], wherein the definition of the protective film is Log M of a graph obtained by measurement by gel permeation chromatography with a measurement temperature of 140 ° C of 2.82 to The amount of low molecular component W of the ratio of the area of 3.32 to the total area is 0.4% or less.
[4] The laminated body according to any one of the above [1] to [3], wherein the transparent resin film contains one or more solvents, and the solvent having the highest boiling point among the solvents has a boiling point of 120 to 300 ° C.
[5] The laminated body according to any one of the above [1] to [4], wherein the transparent resin film contains at least one selected from the group consisting of N, N-dimethylacetamide, γ-butyrolactone, and N- Solvent in the group consisting of methyl pyrrolidone, cyclopentanone, butyl acetate and pentyl acetate.
[6] The laminated body according to any one of the above [1] to [5], wherein the protective film is a polyolefin resin film.
[Effect of the invention]

根據本發明，可提供一種包含基於聚醯亞胺系高分子之透明樹脂膜的積層體，其不易產生膜表面之凹凸、即橘皮，並且亦不易產生白化，具有良好之外觀及視認性。According to the present invention, it is possible to provide a laminated body including a transparent resin film based on a polyimide-based polymer, which is less likely to cause unevenness on the surface of the film, that is, orange peel, and is also unlikely to be whitened, and has good appearance and visibility.

以下，對本發明之實施形態進行詳細說明。再者，本發明之範圍並不限定於此處說明之實施形態，可於並不損及本發明之主旨的範圍內進行各種變更。Hereinafter, embodiments of the present invention will be described in detail. In addition, the scope of the present invention is not limited to the embodiments described herein, and various changes can be made within a range that does not impair the gist of the present invention.

本發明之積層體包含透明樹脂膜及貼合於上述透明樹脂膜之至少一個面之保護膜而成，構成本發明之積層體之透明樹脂膜包含選自由聚醯亞胺、聚醯胺及聚醯胺醯亞胺所組成之群中之至少1種，且由包含選自由聚醯亞胺、聚醯胺及聚醯胺醯亞胺所組成之群中之至少1種之樹脂組合物形成。The laminated body of the present invention includes a transparent resin film and a protective film attached to at least one side of the transparent resin film. The transparent resin film constituting the laminated body of the present invention includes a member selected from the group consisting of polyimide, polyimide, and polyimide. At least one member of the group consisting of amidine and imine is formed of a resin composition including at least one member selected from the group consisting of polyamidoimide, polyamidoamine, and polyamidoimide.

於本說明書中，聚醯亞胺表示含有包含醯亞胺基之重複結構單元的聚合物，聚醯胺醯亞胺表示含有包含醯亞胺基之重複結構單元與包含醯胺基之重複結構單元之兩者的聚合物，聚醯胺表示含有包含醯胺基之重複結構單元之聚合物。聚醯亞胺系高分子表示包含選自聚醯亞胺及聚醯胺醯亞胺中之任一者以上之聚合物。In the present specification, polyfluorene imine means a polymer containing a repeating structural unit containing a fluorenimine group, and polyfluorene imine means a repeating structural unit containing a fluorenimine group and a repeating structural unit containing a fluorenimine group A polymer of both, polyamidoamine means a polymer containing a repeating structural unit containing a amido group. The polyimide-based polymer means a polymer including any one or more selected from polyimide and polyimide.

本實施形態之聚醯亞胺系高分子具有式(10)所表示之重複結構單元。此處，G表示四價有機基，A表示二價有機基。可包含G及/或A不同之2種以上之式(10)所表示之重複結構單元。又，本實施形態之聚醯亞胺系高分子可於並不損及所獲得之透明樹脂膜之各種物性之範圍內，包含式(11)、式(12)及式(13)之任一者所表示之重複結構單元之任一種以上。The polyimide-based polymer of this embodiment has a repeating structural unit represented by formula (10). Here, G represents a tetravalent organic group, and A represents a divalent organic group. The repeating structural unit represented by the formula (10) of two or more different G and / or A may be included. In addition, the polyimide-based polymer of this embodiment may include any one of formula (11), formula (12), and formula (13) within a range that does not impair the various physical properties of the obtained transparent resin film. Any one or more of the repeating structural units represented.

若聚醯亞胺系高分子之主要結構單元為式(10)所表示之重複結構單元，則就透明樹脂膜之強度及透明性之觀點而言較佳。於本實施形態之聚醯亞胺高分子中，式(10)所表示之重複結構單元相對於聚醯亞胺系高分子之全部重複結構單元而言較佳為40莫耳%以上，更佳為50莫耳%以上，進而較佳為70莫耳%以上，尤其更佳為90莫耳%以上，尤其進而更佳為98莫耳%以上。式(10)所表示之重複結構單元亦可為100莫耳%。If the main structural unit of the polyimide-based polymer is a repeating structural unit represented by formula (10), it is preferable from the viewpoint of the strength and transparency of the transparent resin film. In the polyfluorene imine polymer of this embodiment, the repeating structural unit represented by the formula (10) is preferably 40 mol% or more, and more preferably, the total repeating structural unit of the polyfluorene imide polymer. It is 50 mol% or more, more preferably 70 mol% or more, particularly preferably 90 mol% or more, and still more preferably 98 mol% or more. The repeating structural unit represented by formula (10) may also be 100 mol%.

[化1]
[Chemical 1]

G及G1 分別獨立地表示四價有機基，較佳為表示碳數為4～40之四價有機基。上述有機基可經烴基或經氟取代之烴基取代，於此情形時，烴基及經氟取代之烴基之碳數較佳為1～8。作為G及G1 ，可例示式(20)、式(21)、式(22)、式(23)、式(24)、式(25)、式(26)、式(27)、式(28)或式(29)所表示之基以及四價之碳數為6以下之鏈式烴基。式中之＊表示鍵結鍵，Z表示單鍵、-O-、-CH2 -、-CH2 -CH2 -、-CH(CH3 )-、-C(CH3 )2 -、-C(CF3 )2 -、-Ar-、-SO2 -、-CO-、-O-Ar-O-、-Ar-O-Ar-、-Ar-CH2 -Ar-、-Ar-C(CH3 )2 -Ar-或-Ar-SO2 -Ar-。Ar表示可經氟原子取代之碳數為6～20之伸芳基，具體例可列舉伸苯基。就容易抑制所獲得之透明樹脂膜之黃度之觀點而言，作為G及G1 ，較佳為可列舉式(20)、式(21)、式(22)、式(23)、式(24)、式(25)、式(26)或式(27)所表示之基。G and G 1 each independently represent a tetravalent organic group, preferably a tetravalent organic group having 4 to 40 carbon atoms. The organic group may be substituted with 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 to 8. Examples of G and G 1 include formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), and formula ( 28) or a group represented by formula (29) and a tetravalent chain hydrocarbon group having a carbon number of 6 or less. * In the formula represents a bonding bond, Z represents a single bond, -O-, -CH 2- , -CH 2 -CH 2- , -CH (CH 3 )-, -C (CH 3 ) 2- , -C (CF 3 ) 2- , -Ar-, -SO 2- , -CO-, -O-Ar-O-, -Ar-O-Ar-, -Ar-CH 2 -Ar-, -Ar-C ( CH 3 ) 2 -Ar- or -Ar-SO 2 -Ar-. Ar represents an arylene group having 6 to 20 carbon atoms which may be substituted by a fluorine atom, and specific examples thereof include a phenylene group. From the viewpoint of easily suppressing the yellowness of the obtained transparent resin film, as G and G 1 , preferably, formula (20), formula (21), formula (22), formula (23), formula ( 24), a base represented by formula (25), formula (26) or formula (27).

[化2]
[Chemical 2]

G2 表示三價有機基，較佳為表示碳數為4～40之三價有機基。上述有機基可經烴基或經氟取代之烴基取代，於此情形時，烴基及經氟取代之烴基之碳數較佳為1～8。作為G2 ，可例示式(20)、式(21)、式(22)、式(23)、式(24)、式(25)、式(26)、式(27)、式(28)或式(29)所表示之基之鍵結鍵之任一者取代為氫原子之基以及三價之碳數為6以下之鏈式烴基。式中之Z之例與關於G之記載中之Z之例相同。G 2 represents a trivalent organic group, and preferably a trivalent organic group having 4 to 40 carbon atoms. The organic group may be substituted with 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 to 8. Examples of G 2 include formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), and formula (28). Or any one of the bonds of the group represented by formula (29) is substituted with a hydrogen atom group and a trivalent chain hydrocarbon group having a carbon number of 6 or less. The example of Z in the formula is the same as the example of Z in the description about G.

G3 表示二價有機基，較佳為表示碳數為4～40之二價有機基。上述有機基可經烴基或經氟取代之烴基取代，於此情形時，烴基及經氟取代之烴基之碳數較佳為1～8。作為G3 ，可例示式(20)、式(21)、式(22)、式(23)、式(24)、式(25)、式(26)、式(27)、式(28)或式(29)所表示之基之鍵結鍵之中並不相鄰之兩者取代為氫原子之基及碳數為6以下之二價鏈式烴基。式中之Z之例與關於G之記載中之Z之例相同。G 3 represents a divalent organic group, and preferably represents a divalent organic group having 4 to 40 carbon atoms. The organic group may be substituted with 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 to 8. Examples of G 3 include formulae (20), (21), (22), (23), (24), (25), (26), (27), and (28). Or, in the bond of the group represented by formula (29), the two which are not adjacent to each other are substituted with a hydrogen atom and a divalent chain hydrocarbon group having a carbon number of 6 or less. The example of Z in the formula is the same as the example of Z in the description about G.

A、A1 、A2 及A3 均表示二價有機基，較佳為表示碳數為4～40之二價有機基。上述有機基可經烴基或經氟取代之碳數為1～8之烴基取代，於此情形時，烴基及經氟取代之烴基之碳數較佳為1～8。作為A、A1 、A2 及A3 ，分別可例示式(30)、式(31)、式(32)、式(33)、式(34)、式(35)、式(36)、式(37)或式(38)所表示之基；該等經甲基、氟基、氯基或三氟甲基之1種以上取代之基；及碳數為6以下之鏈式烴基。A, A 1 , A 2 and A 3 each represent a divalent organic group, and preferably a divalent organic group having 4 to 40 carbon atoms. The organic group may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group having 1 to 8 carbon atoms. In this case, the carbon number of the hydrocarbon group and the fluorine-substituted hydrocarbon group is preferably 1 to 8 carbon atoms. Examples of A, A 1 , A 2 and A 3 include Formula (30), Formula (31), Formula (32), Formula (33), Formula (34), Formula (35), Formula (36), A group represented by formula (37) or formula (38); those substituted with one or more of methyl, fluoro, chloro, or trifluoromethyl; and a chain hydrocarbon group having a carbon number of 6 or less.

式中之＊表示鍵結鍵，Z1 、Z2 及Z3 分別獨立地表示單鍵、-O-、-CH2 -、-CH2 -CH2 -、-CH(CH3 )-、-C(CH3 )2 -、-C(CF3 )2 -、-S-、-SO2 -、-CO-或-N( R2 )- 。此處，R2 表示可經鹵素原子取代之碳數為1～12之烴基。此處，R2 表示可經鹵素原子取代之碳數為1～12之烴基。Z1 與Z2 及Z2 與Z3 分別較佳為相對於各環而位於間位或對位。* In the formula represents a bonding bond, and Z 1 , Z 2 and Z 3 each independently represent a single bond, -O-, -CH 2- , -CH 2 -CH 2- , -CH (CH 3 )-,- C (CH 3 ) 2- , -C (CF 3 ) 2- , -S-, -SO 2- , -CO-, or -N ( R 2 )- . Here, R 2 represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Here, R 2 represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Z 1 and Z 2 and Z 2 and Z 3 are preferably located at meta or para positions with respect to each ring, respectively.

[化3]
[Chemical 3]

於本發明中，形成透明樹脂膜之樹脂組合物可包含聚醯胺。本實施形態之聚醯胺係以式(13)所表示之重複結構單元為主之聚合物。聚醯胺中之G3 及A3 之較佳例及具體例與聚醯亞胺系高分子中之G3 及A3 之較佳例及具體例相同。上述聚醯胺可包含G3 及/或A3 不同之2種以上之式(13)所表示之重複結構單元。In the present invention, the resin composition forming the transparent resin film may include polyamide. The polyamide according to this embodiment is a polymer mainly composed of a repeating structural unit represented by formula (13). In the preferred embodiment polyamide G 3, and A 3 and the specific examples of the polyimide-based polymer G 3 and A 3 are the same preferred embodiments and specific examples. The polyamidoamine may include a repeating structural unit represented by formula (13) of two or more different types of G 3 and / or A 3 .

聚醯亞胺系高分子例如可藉由二胺與四羧酸化合物(四羧酸二酐等)之縮聚而獲得，例如可根據日本專利特開2006-199945號公報或日本專利特開2008-163107號公報中記載之方法而進行合成。作為聚醯亞胺之市售品，可列舉三菱瓦斯化學股份有限公司製造之Neopulim(註冊商標)、河村產業股份有限公司製造之KPI-MX300F等。The polyfluorene-imide-based polymer can be obtained, for example, by polycondensation of a diamine and a tetracarboxylic acid compound (tetracarboxylic dianhydride, etc.), and can be obtained, for example, according to Japanese Patent Laid-Open No. 2006-199945 or Japanese Patent Laid-Open No. 2008- Synthesis was performed by the method described in Japanese Patent No. 163107. Examples of commercially available products of polyimide include Neopulim (registered trademark) manufactured by Mitsubishi Gas Chemical Co., Ltd. and KPI-MX300F manufactured by Kawamura Industry Co., Ltd.

作為用於聚醯亞胺系高分子之合成之四羧酸化合物，可列舉：芳香族四羧酸及其酐、較佳為其二酐等芳香族四羧酸化合物；及脂肪族四羧酸及其酐、較佳為其二酐等脂肪族四羧酸化合物等。四羧酸化合物除酐以外，亦可為四羧醯氯化合物等四羧酸化合物衍生物，該等可單獨使用或將2種以上組合使用。Examples of the tetracarboxylic acid compound used in the synthesis of polyfluorene-based polymers include aromatic tetracarboxylic acids and their anhydrides, preferably aromatic tetracarboxylic acids such as dianhydrides; and aliphatic tetracarboxylic acids. And its anhydride, preferably an aliphatic tetracarboxylic acid compound such as a dianhydride. The tetracarboxylic acid compound may be a tetracarboxylic acid compound derivative such as a tetracarboxylic phosphonium chloride compound in addition to the anhydride, and these may be used alone or in combination of two or more kinds.

作為芳香族四羧酸二酐之具體例，可列舉非縮合多環式之芳香族四羧酸二酐、單環式之芳香族四羧酸二酐及縮合多環式之芳香族四羧酸二酐。作為非縮合多環式之芳香族四羧酸二酐，可列舉：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、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)二鄰苯二甲酸二酐、4,4'-(間伸苯基二氧)二鄰苯二甲酸二酐。又，作為單環式之芳香族四羧酸二酐，可列舉1,2,4,5-苯四羧酸二酐，作為縮合多環式之芳香族四羧酸二酐，可列舉2,3,6,7-萘四羧酸二酐。Specific examples of the aromatic tetracarboxylic dianhydride include non-condensed polycyclic aromatic tetracarboxylic dianhydride, monocyclic aromatic tetracarboxylic dianhydride, and condensed polycyclic aromatic tetracarboxylic acid. Dianhydride. Examples of the non-condensed polycyclic aromatic tetracarboxylic dianhydride include 4,4'-oxydiphthalic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride Anhydride, 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'- Biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2 -Bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenoxyphenyl) propane dianhydride, 4,4 '-(hexafluoroisopropylidene) ) Diphthalic dianhydride (sometimes described 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-dicarboxyphenyl) ethane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, 4,4 '-(p-phenylene dioxy) diphthalic dianhydride, 4,4 '-(M-phenylene dioxy) diphthalic dianhydride. Examples of the monocyclic aromatic tetracarboxylic dianhydride include 1,2,4,5-benzenetetracarboxylic dianhydride, and examples of the condensed polycyclic aromatic tetracarboxylic dianhydride include 2, 3,6,7-naphthalenetetracarboxylic dianhydride.

該等中，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、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(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)二鄰苯二甲酸二酐及4,4'-(間伸苯基二氧)二鄰苯二甲酸二酐，更佳為可列舉：4,4'-氧二鄰苯二甲酸二酐、3,3',4,4'-聯苯四羧酸二酐、2,2',3,3'-聯苯四羧酸二酐、4,4'-(六氟亞異丙基)二鄰苯二甲酸二酐(6FDA)、雙(3,4-二羧基苯基)甲烷二酐及4,4'-(對伸苯基二氧)二鄰苯二甲酸二酐。該等可單獨使用或將2種以上組合使用。Among these, preferred are: 4,4'-oxydiphthalic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3, 3'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 3 , 3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyl Phenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenoxyphenyl) propane dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride ( 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-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis ( 2,3-dicarboxyphenyl) methane dianhydride, 4,4 '-(p-phenylene dioxy) diphthalic acid dianhydride, and 4,4'-(m-phenylene dioxy) diphthalic acid Dicarboxylic dianhydride, more preferably, 4,4'-oxydiphthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3, 3'-biphenyltetracarboxylic dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA), bis (3,4-dicarboxylic acid) Phenyl) methane dianhydride, and 4,4 '- (p-phenylene) diacetic phthalic dianhydride. These can be used individually or in combination of 2 or more types.

作為脂肪族四羧酸二酐，可列舉環式或非環式之脂肪族四羧酸二酐。環式脂肪族四羧酸二酐為具有脂環烴結構之四羧酸二酐，作為其具體例，可列舉：1,2,4,5-環己烷四羧酸二酐、1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐等環烷烴四羧酸二酐，二環[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、二環己基-3,3',4,4'-四羧酸二酐及該等之位置異構物。該等可單獨使用或將2種以上組合使用。作為非環式脂肪族四羧酸二酐之具體例，可列舉1,2,3,4-丁烷四羧酸二酐、1,2,3,4-戊烷四羧酸二酐等，該等可單獨使用或將2種以上組合使用。又，亦可將環式脂肪族四羧酸二酐及非環式脂肪族四羧酸二酐組合使用。Examples of the aliphatic tetracarboxylic dianhydride include a cyclic or acyclic aliphatic tetracarboxylic dianhydride. The cyclic aliphatic tetracarboxylic dianhydride is a tetracarboxylic dianhydride having an alicyclic hydrocarbon structure. Specific examples thereof include 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2 , 3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride and other cycloalkanetetracarboxylic dianhydrides, bicyclo [2.2.2] oct-7- Ene-2,3,5,6-tetracarboxylic dianhydride, dicyclohexyl-3,3 ', 4,4'-tetracarboxylic dianhydride and positional isomers thereof. These can be used individually or in combination of 2 or more types. Specific examples of the acyclic aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, etc., These can be used individually or in combination of 2 or more types. Further, a cyclic aliphatic tetracarboxylic dianhydride and an acyclic aliphatic tetracarboxylic dianhydride may be used in combination.

於四羧酸化合物之中，就容易提高透明樹脂膜之彈性模數、耐彎曲性及光學特性之觀點而言，較佳為可列舉上述脂環式四羧酸二酐或非縮合多環式之芳香族四羧酸二酐。作為更佳之具體例，可列舉：3,3',4,4'-聯苯四羧酸二酐、2,2',3,3'-聯苯四羧酸二酐、2,2-雙(3,4-二羧基苯基)丙烷二酐、4,4'-(六氟亞異丙基)二鄰苯二甲酸二酐(6FDA)。該等可單獨使用或將2種以上組合使用。Among the tetracarboxylic compounds, from the viewpoint of easily improving the elastic modulus, bending resistance, and optical characteristics of the transparent resin film, the above-mentioned alicyclic tetracarboxylic dianhydride or non-condensed polycyclic type is preferred. Aromatic tetracarboxylic dianhydride. More specific examples include 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, and 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA). These can be used individually or in combination of 2 or more types.

再者，本實施形態之聚醯亞胺系高分子亦可為於不損及所獲得之透明樹脂膜之各種物性之範圍內，除上述聚醯亞胺合成中所使用之四羧酸之酐以外，進一步使四羧酸、三羧酸及二羧酸以及其等之酐及衍生物反應而成者。In addition, the polyimide-based polymer of this embodiment may be an anhydride of tetracarboxylic acid used in the synthesis of the polyimide as long as it does not impair various physical properties of the obtained transparent resin film. In addition, those obtained by further reacting a tetracarboxylic acid, a tricarboxylic acid and a dicarboxylic acid, and their anhydrides and derivatives.

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相關之醯氯化合物、酸酐等，該等可併用2種以上。作為具體例，可列舉：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以單鍵、-CH2 -、-C(CH3 )2 -、-C(CF3 )2 -、-SO2 -或伸苯基連結而成之化合物。Examples of the tricarboxylic acid compound include aromatic tricarboxylic acid, aliphatic tricarboxylic acid, and related phosphonium compounds, acid anhydrides, and the like, and these may be used in combination of two or more kinds. Specific examples include: 1,2,4-benzenetricarboxylic anhydride; 2,3,6-naphthalenetricarboxylic acid-2,3-anhydride; phthalic anhydride and benzoic acid with a single bond,- Compounds in which CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -SO 2- , or phenylene are linked.

作為二羧酸化合物，可列舉芳香族二羧酸、脂肪族二羧酸及其等之相關之醯氯化合物、酸酐等，該等可併用2種以上。作為具體例，可列舉：對苯二甲酸；間苯二甲酸；萘二甲酸；4,4'-聯苯二羧酸；3,3'-聯苯二羧酸；碳數為8以下之鏈式烴之二羧酸化合物及2個苯甲酸骨架以單鍵、-O-、-CH2 -、-C(CH3 )2 -、-C(CF3 )2 -、-N(R9 )-、-C(=O)-、-SO2 -或伸苯基連結而成之化合物。該等可單獨使用或將2種以上組合使用。此處，R9 表示可經鹵素原子取代之碳數為1～12之烴基。Examples of the dicarboxylic acid compound include aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and related phosphonium compounds, acid anhydrides, and the like. These may be used in combination of two or more kinds. Specific examples include: terephthalic acid; isophthalic acid; naphthalenedicarboxylic acid; 4,4'-biphenyldicarboxylic acid; 3,3'-biphenyldicarboxylic acid; chains having a carbon number of 8 or less Dicarboxylic acid compounds of formula hydrocarbons and two benzoic acid skeletons with single bonds, -O-, -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -N (R 9 ) -, -C (= O)-, -SO 2 -or phenylene compounds. These can be used individually or in combination of 2 or more types. Here, R 9 represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom.

作為二羧酸化合物，較佳為對苯二甲酸；間苯二甲酸；4,4'-聯苯二羧酸；3,3'-聯苯二羧酸；及2個苯甲酸骨架以-CH2 -、-C(=O)-、-O-、-N(R9 )-、-SO2 -或伸苯基連結而成之化合物；更佳為對苯二甲酸；4,4'-聯苯二羧酸；及2個苯甲酸骨架以-O-、-N(R9 )-、-C(=O)-或-SO2 -連結而成之化合物。該等可單獨使用或將2種以上組合使用。As the dicarboxylic acid compound, terephthalic acid; isophthalic acid; 4,4'-biphenyldicarboxylic acid; 3,3'-biphenyldicarboxylic acid; and two benzoic acid skeletons with -CH 2- , -C (= O)-, -O-, -N (R 9 )-, -SO 2 -or phenylene compounds; more preferably terephthalic acid; 4,4'- Biphenyldicarboxylic acid; and a compound in which two benzoic acid skeletons are linked by -O-, -N (R 9 )-, -C (= O)-, or -SO 2- . These can be used individually or in combination of 2 or more types.

四羧酸化合物相對於四羧酸化合物、三羧酸化合物及二羧酸化合物之合計之比率較佳為40莫耳%以上，更佳為50莫耳%以上，進而較佳為70莫耳%以上，進而更佳為90莫耳%以上，尤其較佳為98莫耳%以上。The ratio of the tetracarboxylic acid compound to the total of the tetracarboxylic acid compound, the tricarboxylic acid compound, and the dicarboxylic acid compound is preferably 40 mol% or more, more preferably 50 mol% or more, and still more preferably 70 mol%. Above, and further more preferably 90 mol% or more, particularly preferably 98 mol% or more.

作為聚醯亞胺系高分子之合成中所使用之二胺，可列舉脂肪族二胺、芳香族二胺或其等之混合物。再者，於本實施形態中，「芳香族二胺」係表示胺基直接鍵結於芳香環上的二胺，其結構之一部分可包含脂肪族基或其他取代基。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，但並非限定於該等。於該等中，較佳為可列舉苯環。又「脂肪族二胺」係表示胺基直接鍵結於脂肪族基上之二胺，其結構之一部分可包含芳香環或其他取代基。Examples of the diamine used in the synthesis of the polyfluorene-imide-based polymer include an aliphatic diamine, an aromatic diamine, or a mixture thereof. In the present embodiment, the "aromatic diamine" refers to a diamine in which an amine group is directly bonded to an aromatic ring, and a part of the structure may include an aliphatic group or other substituents. The aromatic ring may be a monocyclic ring or a condensed ring, and examples thereof include, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring. Among these, a benzene ring is preferably mentioned. The "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.

作為脂肪族二胺之具體例，可列舉己二胺等非環式脂肪族二胺及1,3-雙(胺基甲基)環己烷、1,4-雙(胺基甲基)環己烷、降烷二胺、4,4'-二胺基二環己甲烷等環式脂肪族二胺等，該等可單獨使用或將2種以上組合使用。Specific examples of the aliphatic diamine include acyclic aliphatic diamines such as hexamethylene diamine, 1,3-bis (aminomethyl) cyclohexane, and 1,4-bis (aminomethyl) ring. Cyclic aliphatic diamines, such as hexane, norbornane diamine, 4,4'- diamino dicyclohexane methane, etc., These can be used individually or in combination of 2 or more types.

作為芳香族二胺之具體例，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'-二胺基二苯醚、3,4'-二胺基二苯醚、3,3'-二胺基二苯醚、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'-二胺基聯苯(有時記載為TFMB)、4,4'-雙(4-胺基苯氧基)聯苯、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。Specific examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, m-xylylenediamine, p-xylylenediamine, and 1,5-diaminonaphthalene , 2,6-diaminonaphthalene and other aromatic diamines with one aromatic ring, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'- Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylphosphonium, 3,4'-di Aminodiphenylphosphonium, 3,3'-diaminodiphenylphosphonium, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) Benzene, bis [4- (4-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] fluorene, 2,2-bis [4- (4-amine Phenylphenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2'-dimethylbenzidine, 2,2'-bis ( Trifluoromethyl) -4,4'-diaminobiphenyl (sometimes described as TFMB), 4,4'-bis (4-aminophenoxy) biphenyl, 9,9-bis (4- Aminophenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) fluorene, 9,9-bis (4-amino-3-chlorophenyl) fluorene, 9,9- An aromatic diamine having two or more aromatic rings such as bis (4-amino-3-fluorophenyl) fluorene. These can be used individually or in combination of 2 or more types.

作為芳香族二胺，較佳為4,4'-二胺基二苯甲烷、4,4'-二胺基二苯丙烷、4,4'-二胺基二苯醚、3,3'-二胺基二苯醚、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'-二胺基聯苯(TFMB)、4,4'-雙(4-胺基苯氧基)聯苯，更佳為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'-二胺基聯苯(TFMB)、4,4'-雙(4-胺基苯氧基)聯苯。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'- Diaminodiphenyl ether, 4,4'-diaminodiphenylphosphonium, 3,3'-diaminodiphenylphosphonium, 1,4-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] fluorene, 2,2-bis [4- (4-aminophenoxy ) Phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) Group) -4,4'-diaminobiphenyl (TFMB), 4,4'-bis (4-aminophenoxy) biphenyl, more preferably 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylphosphonium, 1,4-bis (4-aminophenoxy ) Benzene, bis [4- (4-aminophenoxy) phenyl] fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-dimethyl Benzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFMB), 4,4'-bis (4-aminophenoxy) biphenyl. These can be used individually or in combination of 2 or more types.

上述二胺亦可具有氟系取代基。作為氟系取代基，可列舉三氟甲基等碳數為1～5之全氟烷基及氟基。The diamine may have a fluorine-based substituent. Examples of the fluorine-based substituent include a perfluoroalkyl group having 1 to 5 carbon atoms, such as a trifluoromethyl group, and a fluoro group.

於上述二胺之中，就高透明性及低著色性之觀點而言，較佳為使用選自由具有聯苯結構之芳香族二胺所組成之群中之1種以上，作為具體例，較佳為使用選自由2,2'-二甲基聯苯胺、2,2'-雙(三氟甲基)-4,4'-二胺基聯苯(TFMB)及4,4'-雙(4-胺基苯氧基)聯苯所組成之群中之1種以上。更佳為具有聯苯結構及氟系取代基之二胺，作為具體例，更佳為使用2,2'-雙(三氟甲基)-4,4'-二胺基聯苯(TFMB)。Among the above diamines, from the viewpoint of high transparency and low coloring properties, it is preferable to use one or more members selected from the group consisting of aromatic diamines having a biphenyl structure. As specific examples, Preferably, a material selected from the group consisting of 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFMB), and 4,4'-bis ( One or more of the group consisting of 4-aminophenoxy) biphenyl. More preferably, it is a diamine having a biphenyl structure and a fluorine-based substituent. As a specific example, it is more preferable to use 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFMB). .

聚醯亞胺系高分子係由二胺與四羧酸化合物(包含醯氯化合物、四羧酸二酐等四羧酸化合物衍生物)縮聚而形成之包含式(10)所表示之重複結構單元之縮合型高分子。作為起始原料，除該等以外，進而亦存在使用三羧酸化合物(包含醯氯化合物、三羧酸酐等三羧酸化合物衍生物)及二羧酸化合物(包含醯氯化合物等衍生物)之情形。又，聚醯胺係由二胺與二羧酸化合物(包含醯氯化合物等衍生物)縮聚而形成之包含式(13)所表示之重複結構單元之縮合型高分子。The polyfluorene-based polymer is a repeating structural unit including a formula (10) formed by polycondensation of a diamine and a tetracarboxylic acid compound (including tetracarboxylic acid compound derivatives such as a fluorinated chlorine compound and a tetracarboxylic dianhydride). Condensation polymer. As starting materials, in addition to these, there are also those using tricarboxylic acid compounds (including derivatives of tricarboxylic acid compounds such as fluorenyl chloride compounds and tricarboxylic anhydrides) and dicarboxylic acid compounds (including derivatives of fluorinated chlorine compounds) situation. In addition, polyamidoamine is a condensation-type polymer containing a repeating structural unit represented by formula (13) formed by polycondensation of a diamine and a dicarboxylic acid compound (including a derivative such as a chlorinated compound).

式(10)及式(11)所表示之重複結構單元通常自二胺類及四羧酸化合物衍生而得。式(12)所表示之重複結構單元通常自二胺及三羧酸化合物衍生而得。式(13)所表示之重複結構單元通常自二胺及二羧酸化合物衍生而得。二胺、四羧酸化合物、三羧酸化合物及二羧酸化合物之具體例如上所述。The repeating structural units represented by formula (10) and formula (11) are usually derived from diamines and tetracarboxylic acid compounds. The repeating structural unit represented by formula (12) is usually derived from a diamine and a tricarboxylic acid compound. The repeating structural unit represented by formula (13) is usually derived from a diamine and a dicarboxylic acid compound. Specific examples of the diamine, tetracarboxylic acid compound, tricarboxylic acid compound, and dicarboxylic acid compound are as described above.

關於二胺與四羧酸化合物等羧酸化合物之莫耳比，相對於二胺1.00 mol，較佳為可於四羧酸為0.9 mol以上1.1 mol以下之範圍內進行適當調節。就為了表現高耐折性而較佳為所獲得之聚醯亞胺系高分子為高分子量之觀點而言，相對於二胺1.00 mol，四羧酸更佳為0.98 mol以上1.02 mol以下，進而較佳為0.99 mol以上1.01 mol以下。The molar ratio of a diamine to a carboxylic acid compound such as a tetracarboxylic acid compound is preferably adjusted within a range of 0.9 mol to 1.1 mol of the tetracarboxylic acid relative to 1.00 mol of the diamine. From the viewpoint that the obtained polyimide-based polymer preferably has a high molecular weight in order to exhibit high folding resistance, the tetracarboxylic acid is more preferably 0.98 mol or more and 1.02 mol or less relative to 1.00 mol of the diamine, and furthermore, It is preferably from 0.99 mol to 1.01 mol.

又，就抑制所獲得之透明樹脂膜之黃度之觀點而言，較佳為胺基占所獲得之高分子末端之比率較低，四羧酸化合物等羧酸化合物相對於二胺1.00 mol較佳為1.00 mol以上。From the viewpoint of suppressing the yellowness of the obtained transparent resin film, it is preferable that the ratio of the amine group to the obtained polymer terminal is low, and the carboxylic acid compound such as a tetracarboxylic acid compound is more than 1.00 mol of the diamine. It is preferably at least 1.00 mol.

對二胺及羧酸化合物(例如四羧酸化合物)之分子中之氟數進行調整，以聚醯亞胺系高分子之質量為基準而言，可將所獲得之聚醯亞胺系高分子中之氟量設為1質量%以上、5質量%以上、10質量%以上、20質量%以上。就存在氟之比率越高則原料費越變高之傾向之觀點而言，氟量之上限較佳為40質量%以下。氟系取代基可存在於二胺或羧酸化合物之任一者中，亦可存在於兩者中。存在藉由包含氟系取代基而尤其降低YI(Yellowness Index，黃度指數)值之情形。By adjusting the number of fluorines in the molecules of diamine and carboxylic acid compounds (such as tetracarboxylic acid compounds), based on the mass of the polyimide-based polymer, the obtained polyimide-based polymer can be adjusted. The amount of fluorine in it is 1 mass% or more, 5 mass% or more, 10 mass% or more, and 20 mass% or more. From the viewpoint that the higher the ratio of fluorine, the higher the raw material cost, the upper limit of the amount of fluorine is preferably 40% by mass or less. The fluorine-based substituent may be present in either the diamine or the carboxylic acid compound, or may be present in both. In particular, the YI (Yellowness Index) value may be reduced by including a fluorine-based substituent.

本實施形態之聚醯亞胺系高分子亦可為包含不同種類之複數個上述重複結構單元之共聚物。聚醯亞胺系高分子之標準聚苯乙烯換算之重量平均分子量通常為100,000～800,000。就若聚醯亞胺系高分子之重量平均分子量較大、則製膜時之彎曲性提高之觀點而言，較佳為200,000以上，更佳為300,000以上，進而較佳為350,000以上。又，就獲得適度之濃度及黏度之清漆，且存在製膜性提高之傾向之觀點而言，較佳為750,000以下，更佳為600,000以下，進而較佳為500,000以下。亦可混合使用重量平均分子量不同之聚醯亞胺系高分子。The polyimide-based polymer of the present embodiment may also be a copolymer including a plurality of the repeating structural units of different kinds. The standard polystyrene-equivalent weight average molecular weight of polyimide-based polymers is usually 100,000 to 800,000. From the viewpoint that the polyimide-based polymer has a large weight average molecular weight, the flexibility at the time of film formation is preferably 200,000 or more, more preferably 300,000 or more, and even more preferably 350,000 or more. From the viewpoint of obtaining a varnish having a suitable concentration and viscosity and a tendency to improve the film forming property, it is preferably 750,000 or less, more preferably 600,000 or less, and even more preferably 500,000 or less. Polyimide polymers having different weight average molecular weights may also be used in combination.

聚醯亞胺系高分子及聚醯胺藉由含有含氟取代基，膜化時之彈性模數提高，並且顯示出YI值降低之傾向。若膜之彈性模數較高，則存在抑制產生損傷及皺折等之傾向。就膜之透明性之觀點而言，較佳為聚醯亞胺系高分子及聚醯胺具有含氟取代基。作為含氟取代基之具體例，可列舉氟基及三氟甲基。The polyfluorene-based polymer and polyfluorene contain a fluorine-containing substituent, which increases the elastic modulus at the time of film formation, and shows a tendency that the YI value decreases. If the elastic modulus of the film is high, there is a tendency to suppress the occurrence of damage, wrinkles, and the like. From the viewpoint of the transparency of the film, it is preferred that the polyfluorene-based polymer and the polyfluorene have a fluorine-containing substituent. Specific examples of the fluorine-containing substituent include a fluoro group and a trifluoromethyl group.

聚醯亞胺系高分子及聚醯亞胺系高分子與聚醯胺之混合物中之氟原子之含量分別以聚醯亞胺系高分子之質量或聚醯亞胺系高分子之質量與聚醯胺之質量之合計為基準而言，較佳為1質量%以上40質量%以下，進而較佳為5質量%以上40質量%以下。若氟原子之含量為1質量%以上，則存在可進一步降低膜化時之YI值，進一步提高透明性之傾向。若氟原子之含量超過40質量%，則存在聚醯亞胺之高分子量化變困難之傾向。The content of fluorine atoms in the polyimide-based polymer and the mixture of the polyimide-based polymer and the polyimide is based on the mass of the polyimide-based polymer or the mass of the polyimide-based polymer and the polyimide, respectively. On the basis of the total mass of amidine, it is preferably from 1% by mass to 40% by mass, and more preferably from 5% by mass to 40% by mass. When the content of the fluorine atom is 1% by mass or more, there is a tendency that the YI value at the time of film formation can be further reduced, and the transparency can be further improved. When the content of the fluorine atom exceeds 40% by mass, there is a tendency that the molecular weight of the polyfluorene imine becomes difficult.

於本發明中，形成透明樹脂膜之樹脂組合物中之聚醯亞胺系高分子及/或聚醯胺之含量相對於樹脂組合物之固形物成分較佳為40質量%以上，更佳為50質量%以上，進而較佳為70質量%以上，亦可為100質量%。若聚醯亞胺系高分子及/或聚醯胺之含量為上述下限值以上，則透明樹脂膜之彎曲性良好。再者，所謂固形物成分係指自樹脂組合物除去溶劑後之成分之合計量。In the present invention, the content of the polyimide-based polymer and / or polyimide in the resin composition forming the transparent resin film is preferably 40% by mass or more, more preferably, based on the solid content of the resin composition. 50% by mass or more, more preferably 70% by mass or more, and 100% by mass may also be used. When the content of the polyfluorene-based polymer and / or polyamine is equal to or more than the above-mentioned lower limit value, the flexibility of the transparent resin film is good. The solid content means the total amount of the components after the solvent is removed from the resin composition.

於本發明中，形成透明樹脂膜之樹脂組合物除上述聚醯亞胺系高分子及/或聚醯胺以外，進而可含有無機粒子等無機材料。作為無機材料，可列舉：二氧化矽粒子、鈦粒子、氫氧化鋁、氧化鋯粒子、鈦酸鋇粒子等無機粒子；及原矽酸四乙酯等4級烷氧基矽烷等之矽化物。就清漆之穩定性、無機材料之分散性之觀點而言，較佳為二氧化矽粒子、氫氧化鋁、氧化鋯粒子，進而較佳為二氧化矽粒子。In the present invention, the resin composition forming the transparent resin film may contain an inorganic material such as inorganic particles in addition to the polyimide-based polymer and / or polyimide. Examples of the inorganic material include inorganic particles such as silicon dioxide particles, titanium particles, aluminum hydroxide, zirconia particles, and barium titanate particles; and silicides such as fourth-order alkoxysilanes such as tetraethyl orthosilicate. From the viewpoints of the stability of the varnish and the dispersibility of the inorganic material, silica particles, aluminum hydroxide, and zirconia particles are preferred, and silica particles are more preferred.

無機材料之粒子之平均一次粒徑較佳為1～200 nm，更佳為3～100 nm，進而較佳為5～50 nm，進而更佳為5～30 nm。若二氧化矽粒子之平均一次粒徑為100 nm以下，則存在透明性提高之傾向。若二氧化矽粒子之平均一次粒徑為10 nm以上，則存在由於二氧化矽粒子之凝聚力減弱，故而變得容易處理之傾向。The average primary particle diameter of the particles of the inorganic material is preferably 1 to 200 nm, more preferably 3 to 100 nm, still more preferably 5 to 50 nm, and even more preferably 5 to 30 nm. When the average primary particle diameter of the silicon dioxide particles is 100 nm or less, the transparency tends to be improved. When the average primary particle diameter of the silicon dioxide particles is 10 nm or more, the cohesive force of the silicon dioxide particles tends to be reduced, so that it tends to be easier to handle.

於本發明中，二氧化矽粒子可為使二氧化矽粒子分散於有機溶劑等中而成之二氧化矽溶膠，亦可使用藉由氣相法製造之二氧化矽微粒子粉末，但就容易處理之觀點而言，較佳為藉由液相法製造之二氧化矽溶膠。In the present invention, the silica particles may be silica dioxide sols obtained by dispersing silica particles in an organic solvent or the like, and silica dioxide fine particles produced by a gas phase method may also be used, but it is easy to handle From the viewpoint, a silica sol produced by a liquid phase method is preferred.

透明樹脂膜中之二氧化矽粒子之平均一次粒徑可藉由利用穿透式電子顯微鏡(TEM)所進行之觀察而求出。形成透明樹脂膜前之二氧化矽粒子之粒度分佈可藉由市售之雷射繞射式粒度分佈計求出。The average primary particle diameter of the silicon dioxide particles in the transparent resin film can be determined by observation with a transmission electron microscope (TEM). The particle size distribution of the silica particles before forming the transparent resin film can be obtained by a commercially available laser diffraction type particle size distribution meter.

於本發明中，樹脂組合物中之無機材料之含量係相對於樹脂組合物之固形物成分而言較佳為0質量%以上90質量%以下，更佳為10質量%以上60質量%以下，進而較佳為20質量%以上50質量%以下。若樹脂組合物中之無機材料之含量於上述範圍內，則存在容易兼具透明樹脂膜之透明性及機械強度之傾向。再者，固形物成分係指自樹脂組合物除去溶劑之成分之合計量。In the present invention, the content of the inorganic material in the resin composition is preferably 0% by mass or more and 90% by mass or less, more preferably 10% by mass or more and 60% by mass or less with respect to the solid content of the resin composition. It is more preferably 20% by mass or more and 50% by mass or less. When the content of the inorganic material in the resin composition is within the above range, there is a tendency that both the transparency and the mechanical strength of the transparent resin film are easily obtained. The solid content means the total amount of components from which the solvent is removed from the resin composition.

形成透明樹脂膜之樹脂組合物除以上說明之成分以外，可進而含有其他成分。作為其他成分，例如可列舉：抗氧化劑、脫模劑、光穩定劑、上藍劑、阻燃劑、潤滑劑及調平劑。The resin composition forming the transparent resin film may contain other components in addition to the components described above. Examples of the other components include an antioxidant, a release agent, a light stabilizer, a bluing agent, a flame retardant, a lubricant, and a leveling agent.

於本發明中，於樹脂組合物包含除聚醯亞胺系高分子等樹脂成分及無機材料以外之其他成分之情形時，其他成分之含量係相對於透明樹脂膜之總質量而言較佳為0%以上20質量%以下，更佳為0%以上10質量%以下。In the present invention, when the resin composition contains components other than resin components such as polyimide-based polymers and inorganic materials, the content of the other components is preferably relative to the total mass of the transparent resin film. 0% to 20% by mass, more preferably 0% to 10% by mass.

於本發明中，透明樹脂膜係例如可由樹脂清漆而製造，上述樹脂清漆可藉由如下方式而製備，亦即，於使選自上述四羧酸化合物、上述二胺及上述其他原料進行反應而獲得之聚醯亞胺系高分子及/或聚醯胺之反應液、視需要包含無機材料及其他成分之樹脂組合物中加入溶劑後進行混合及攪拌。於上述樹脂組合物或樹脂清漆中，亦可使用購入之聚醯亞胺系高分子等溶液或購入之固體聚醯亞胺系高分子等之溶液代替聚醯亞胺系高分子等反應液。In the present invention, the transparent resin film can be produced, for example, from a resin varnish. The resin varnish can be prepared by reacting a material selected from the tetracarboxylic acid compound, the diamine, and the other raw materials. The reaction solution of the obtained polyimide-based polymer and / or polyimide is added to a resin composition containing an inorganic material and other components, if necessary, and then mixed and stirred. In the above-mentioned resin composition or resin varnish, a solution such as a commercially available polyimide polymer or a solution of a purchased solid polyimide polymer may be used instead of a reaction solution such as a polyimide polymer.

作為可用以製備樹脂清漆之溶劑，可適當選擇能夠使聚醯亞胺系高分子等樹脂成分溶解或分散者。就樹脂成分之溶解性、塗佈性及乾燥性等觀點而言，較佳為具有120～300℃之沸點之有機溶劑，更佳為120～270℃，進而較佳為120～250℃，特佳為具有120～230℃之沸點之有機溶劑。作為此種有機溶劑，具體而言例如可列舉：N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮等醯胺系溶劑；γ-丁內酯、γ-戊內酯等內酯系溶劑；環己酮、環戊酮、甲基乙基酮等酮系溶劑；乙酸丁酯、乙酸戊酯等乙酸酯系溶劑；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等。其中，就對聚醯亞胺系高分子及聚醯胺之溶解性優異之觀點而言，較佳為選自由N,N-二甲基乙醯胺(沸點：165℃)、γ-丁內酯(沸點：204℃)、N-甲基吡咯啶酮(沸點：202℃)、環戊酮(沸點：131℃)、乙酸丁酯(沸點：126℃)及乙酸戊酯(沸點：149℃)所組成之群中之溶劑。作為溶劑，可單獨使用1種，亦可將2種以上組合使用。再者，於使用2種以上溶劑之情形時，較佳為選擇所使用之溶劑中沸點最高之溶劑之沸點處於上述範圍之溶劑之種類。As a solvent which can be used for preparing a resin varnish, those which can dissolve or disperse resin components, such as a polyimide-type polymer, can be selected suitably. From the viewpoints of the solubility, coating properties, and drying properties of the resin component, an organic solvent having a boiling point of 120 to 300 ° C is preferred, 120 to 270 ° C is more preferred, and 120 to 250 ° C is further preferred. An organic solvent having a boiling point of 120 to 230 ° C is preferred. Specific examples of such an organic solvent include: amine-based solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone; γ- Lactone solvents such as butyrolactone, γ-valerolactone; ketone solvents such as cyclohexanone, cyclopentanone, methyl ethyl ketone; acetate solvents such as butyl acetate, pentyl acetate; dimethyl Sulfur-containing solvents such as osmium, dimethyl fluorene, and cyclobutane; carbonate-based solvents such as ethylene carbonate and propylene carbonate. Among them, from the viewpoint of excellent solubility of polyfluorene-based polymers and polyfluorene, it is preferably selected from N, N-dimethylacetamide (boiling point: 165 ° C), γ-butane Ester (boiling point: 204 ° C), N-methylpyrrolidone (boiling point: 202 ° C), cyclopentanone (boiling point: 131 ° C), butyl acetate (boiling point: 126 ° C) and amyl acetate (boiling point: 149 ° C) ) The solvent in the group. As the solvent, one kind may be used alone, or two or more kinds may be used in combination. When two or more solvents are used, it is preferable to select the type of the solvent having the highest boiling point among the solvents used and having a boiling point in the above range.

溶劑之量以成為能夠進行樹脂清漆之操作的黏度之方式進行選擇即可，並無特別限制，例如相對於樹脂清漆總量而言，較佳為50～95質量%，更佳為70～95質量%，進而較佳為80～95質量%。The amount of the solvent may be selected in such a manner as to be a viscosity capable of operating the resin varnish, and is not particularly limited. For example, it is preferably 50 to 95% by mass, and more preferably 70 to 95% with respect to the total amount of the resin varnish. The mass% is more preferably 80 to 95 mass%.

又，至於構成本發明之積層體之透明樹脂膜中之溶劑之含量，作為利用熱重-示差熱測定之120℃至250℃之質量減少率而算出之殘留溶劑量S(質量%)較佳為20質量%以下，更佳為17質量%以下，進而較佳為15質量%以下。於透明樹脂膜中存在大量溶劑之情形時，將有容易產生透明樹脂膜之表面凹凸之傾向，且由於來自保護膜中含有之添加劑等之成分自溶劑中溶出，容易於與保護膜貼合之透明保護膜之表面出現白化。若透明樹脂膜中之殘留溶劑量S為上述上限值以下，則可抑制白化之發生，又，於可將獲得之透明樹脂膜形成為自支撐膜之方面亦較佳。殘留溶劑量S之下限值並無特別限定，於將聚醯亞胺系高分子或聚醯胺作為樹脂成分之透明樹脂膜之製造中，一般而言由於使用如上所述之具有超過100℃之沸點之高沸點溶劑，故於其製造過程中不易完全除去溶劑，因此通常為0.001質量%以上。In addition, as for the content of the solvent in the transparent resin film constituting the laminated body of the present invention, the residual solvent amount S (mass%) calculated as a mass reduction rate of 120 ° C to 250 ° C by thermogravimetric-differential thermal measurement is preferred. It is 20% by mass or less, more preferably 17% by mass or less, and even more preferably 15% by mass or less. When there is a large amount of solvent in the transparent resin film, the surface of the transparent resin film tends to be prone to unevenness, and since components such as additives contained in the protective film are dissolved from the solvent, it is easy to adhere to the protective film. Whitening appears on the surface of the transparent protective film. If the amount of residual solvent S in the transparent resin film is equal to or less than the above-mentioned upper limit value, the occurrence of whitening can be suppressed, and the transparent resin film obtained can also be formed as a self-supporting film. The lower limit of the residual solvent amount S is not particularly limited. Generally, in the production of a transparent resin film using a polyimide-based polymer or polyimide as a resin component, it has a temperature exceeding 100 ° C. as described above. The high-boiling-point solvent having a boiling point is not easy to completely remove the solvent during the manufacturing process, and therefore it is usually 0.001% by mass or more.

於本發明中，殘留溶劑量S係以如下方式算出之值：使用熱重-示差熱(TG-DTA)測定裝置進行，一面將作為測定對象之透明樹脂膜(試樣)以10℃/min之升溫速度自室溫升溫至120℃，於120℃保持5分鐘，藉此將吸附水除去，其後以10℃/min之升溫速度升溫(加熱)至400℃，一面進行測定，於測定之質量變化之結果中，根據數式(2)算出自120℃至250℃之質量減少率S(質量%)。
S(質量%)＝100－(W1/W0)×100 (2)
[數式(2)中，W0為於120℃保持5分鐘後之試樣之質量，W1為250℃之試樣之質量]。In the present invention, the residual solvent amount S is a value calculated as follows: It is performed using a thermogravimetric-differential thermal (TG-DTA) measuring device, and the transparent resin film (sample) as a measurement target is set at 10 ° C / min. The heating rate was raised from room temperature to 120 ° C, and held at 120 ° C for 5 minutes to remove the adsorbed water, and then the temperature was increased (heated) to 400 ° C at a heating rate of 10 ° C / min. As a result of the change, the mass reduction rate S (mass%) from 120 ° C to 250 ° C was calculated according to the formula (2).
S (mass%) = 100－ (W1 / W0) × 100 (2)
[In formula (2), W0 is the mass of the sample after being held at 120 ° C for 5 minutes, and W1 is the mass of the sample at 250 ° C].

殘留溶劑量S可藉由調整用以形成透明樹脂膜之樹脂清漆中所含之溶劑量、溶劑種類、由樹脂清漆製膜之塗膜之乾燥條件(乾燥溫度及時間、風速等)等而進行控制。The amount of residual solvent S can be adjusted by adjusting the amount of solvent contained in the resin varnish used to form the transparent resin film, the type of solvent, and the drying conditions (drying temperature and time, wind speed, etc.) of the coating film made of the resin varnish. control.

透明樹脂膜之厚度根據透明樹脂膜之用途等進行適當決定即可，通常為10～500 μm，較佳為15～200 μm，更佳為20～100 μm。若透明樹脂膜之厚度處於上述範圍內，則透明樹脂膜之彎曲性良好。The thickness of the transparent resin film may be appropriately determined depending on the application of the transparent resin film, etc., and is usually 10 to 500 μm, preferably 15 to 200 μm, and more preferably 20 to 100 μm. When the thickness of the transparent resin film is within the above range, the flexibility of the transparent resin film is good.

本發明之積層體包含貼合於上述透明樹脂膜上之保護膜。保護膜可僅貼合於透明樹脂膜之一個面，亦可貼合於兩個面。貼合於透明樹脂膜上之保護膜通常為用以暫時保護透明樹脂膜之表面之膜，只要為可保護透明樹脂膜之表面的可剝離之膜則無特別限定。例如，可列舉聚乙烯、聚丙烯膜等聚烯烴系樹脂膜等。於在透明樹脂膜之兩個面貼合保護膜之情形時，各面之保護膜可相互相同，亦可不同。The laminated body of the present invention includes a protective film adhered to the transparent resin film. The protective film may be attached to only one side of the transparent resin film, or may be attached to both sides. The protective film attached to the transparent resin film is usually a film for temporarily protecting the surface of the transparent resin film, and is not particularly limited as long as it is a peelable film that can protect the surface of the transparent resin film. Examples include polyolefin resin films such as polyethylene and polypropylene films. When a protective film is laminated on both sides of the transparent resin film, the protective films on each side may be the same as or different from each other.

於本發明之積層體中，與透明樹脂膜相接之保護膜表面之算術平均波紋度Wa為30 nm以下。算術平均波紋度Wa為表示起伏之高度方向之大小(振幅)之參數。於本發明中，係藉由干涉顯微鏡測定保護膜之表面形狀後，對測定資料進行傅立葉變換，自除去短波長成分(截止值：20 μm)而獲得之二維起伏波形求出的根據數式(1)算出之值。由於被視認為外觀不良之表面凹凸包含週期為數十μm之起伏，故干涉顯微鏡之測定區域之範圍於x方向、y方向上均為60 μm以上且100 μm以下。再者，詳細而言，根據下述實施例中記載之方法算出。In the laminated body of the present invention, the arithmetic average waviness Wa of the surface of the protective film in contact with the transparent resin film is 30 nm or less. The arithmetic mean waviness Wa is a parameter indicating the magnitude (amplitude) of the undulating height direction. In the present invention, after measuring the surface shape of the protective film by an interference microscope, the measurement data is Fourier transformed, and the two-dimensional undulating waveform obtained by removing the short-wavelength component (cutoff value: 20 μm) is based on the following formula: (1) Calculated value. The surface irregularities considered to be bad appearance include fluctuations with a period of several tens of μm, so the range of the measurement area of the interference microscope is 60 μm or more and 100 μm or less in the x direction and y direction. Furthermore, in detail, it calculated by the method described in the following Example.

數式(1)：
[數2]

[數式(1)中，Zw(x，y)表示根據保護膜表面之二維高度資料，使用截止值為20 μm、振幅傳遞率為50%之高斯濾波器而獲得之表面起伏之各點之高度，lx 、ly 分別表示x、y方向之測定區域之範圍]Equation (1):
[Number 2]

[In Equation (1), Zw (x, y) represents the points of the surface undulation obtained by using a Gaussian filter with a cutoff value of 20 μm and an amplitude transmission rate of 50% based on the two-dimensional height data of the surface of the protective film. Height, l x and l y respectively represent the range of the measurement area in the x and y directions]

若與透明樹脂膜相接之保護膜表面之算術平均波紋度Wa為30 nm以下，則於與包含殘留溶劑之透明樹脂膜貼合時，可抑制透明樹脂膜上之表面凹凸之產生。因此，於本發明中，保護膜之算術平均波紋度Wa較佳為29 nm以下，更佳為28 nm以下，進而較佳為27 nm以下。保護膜之算術平均波紋度Wa之下限值並無特別限制，通常為5 nm以上。If the arithmetic mean waviness Wa of the surface of the protective film that is in contact with the transparent resin film is 30 nm or less, the surface unevenness on the transparent resin film can be suppressed when the transparent resin film is bonded to the transparent resin film. Therefore, in the present invention, the arithmetic mean waviness Wa of the protective film is preferably 29 nm or less, more preferably 28 nm or less, and even more preferably 27 nm or less. The lower limit of the arithmetic mean waviness Wa of the protective film is not particularly limited, and is usually 5 nm or more.

保護膜之算術平均波紋度Wa可根據保護膜之成形時之製造條件(溫度、線速度、夾輥之表面起伏、夾持壓等)進行控制。例如，若降低成形溫度，則存在算術平均波紋度Wa變小之傾向，藉由提高線速度，或降低夾持壓，亦存在算術平均波紋度Wa變小之傾向。又，亦可根據成形後之保護膜之保管條件(溫度、濕度、保管時間)進行控制。於使用市售之保護膜之情形時，亦可藉由測定於與透明樹脂膜貼合之前使用之保護膜之算術平均波紋度Wa，篩選適當之保護膜。The arithmetic average waviness Wa of the protective film can be controlled according to the manufacturing conditions (temperature, linear velocity, surface undulation of the nip roller, nip pressure, etc.) when the protective film is formed. For example, if the molding temperature is lowered, the arithmetic mean waviness Wa tends to become smaller, and by increasing the linear velocity or the clamping pressure, the arithmetic mean waviness Wa also tends to become smaller. In addition, it can be controlled according to the storage conditions (temperature, humidity, storage time) of the formed protective film. When a commercially available protective film is used, an appropriate protective film can be selected by measuring the arithmetic average waviness Wa of the protective film used before lamination with a transparent resin film.

於本發明之積層體中，保護膜可包含基材膜與積層於其上之黏著劑層，黏著劑層例如由丙烯酸系黏著劑、環氧系黏著劑、胺基甲酸酯系黏著劑、聚矽氧系黏著劑等形成，但就能夠削減成本之觀點而言，較佳為聚烯烴系樹脂等具有自黏性之樹脂膜，具體而言，較佳為聚烯烴系樹脂膜。就容易獲取且廉價之觀點而言，更佳為聚丙烯系樹脂膜或聚乙烯系樹脂膜，進而較佳為聚乙烯系樹脂膜。又，作為聚乙烯系樹脂，例如可列舉高壓法低密度聚乙烯(LDPE)、直鏈狀短鏈分支聚乙烯(LLDPE)、中低壓法高密度聚乙烯(HDPE)、超低密度聚乙烯(VLDPE)等，作為與透明樹脂膜相鄰之面之樹脂，就與透明樹脂膜之接著性以及加工性之觀點而言，較佳為LLDPE。再者，於在透明樹脂膜之兩個面貼合保護膜之情形時，各面之保護膜可相互相同，亦可不同，但較佳為貼合於至少一個面之保護膜為聚烯烴系樹脂膜。In the laminated body of the present invention, the protective film may include a base film and an adhesive layer laminated thereon. The adhesive layer is, for example, an acrylic adhesive, an epoxy adhesive, a urethane adhesive, A polysiloxane adhesive is formed, but from the viewpoint of cost reduction, a resin film having self-adhesive properties such as a polyolefin resin is preferred, and a polyolefin resin film is specifically preferred. From the viewpoint of availability and inexpensiveness, a polypropylene-based resin film or a polyethylene-based resin film is more preferred, and a polyethylene-based resin film is more preferred. Examples of the polyethylene-based resin include high-pressure low-density polyethylene (LDPE), linear short-chain branched polyethylene (LLDPE), medium- and low-pressure high-density polyethylene (HDPE), and ultra-low-density polyethylene ( VLDPE) and the like, as the resin on the surface adjacent to the transparent resin film, LLDPE is preferred from the viewpoint of adhesiveness and processability to the transparent resin film. In addition, when a protective film is bonded to both sides of the transparent resin film, the protective films on each side may be the same as or different from each other, but it is preferable that the protective film bonded to at least one side is a polyolefin system. Resin film.

於透明樹脂膜中存在溶劑之情形時，由於溶劑中保護膜所含有之低分子成分溶出，故容易於與保護膜貼合之透明保護膜之表面出現白化。此處，於本發明中，保護膜所含有之「低分子成分」意指於依照下述條件，藉由測定溫度為140℃之凝膠滲透層析法進行測定而獲得之圖的Log M為2.82至3.32之範圍內檢測出之成分。
＜凝膠滲透層析法之測定條件＞
管柱：將1根PLgel Individual(5 μm，50Å，7.5 mm ID×30 cm，Agilent Technology製造)與2根TSKgel GMHHR -H(S)HT(7.5 mm ID×30 cm，Tosoh(股)製造)連接
流動相：向鄰二氯苯(和光，特級)添加0.1 w/V%之BHT(Butylated Hydroxy Toluene，二丁基羥基甲苯)後使用
流速：1 mL/min
管柱烘箱溫度：140℃
自動取樣器溫度：140℃
系統烘箱溫度：40℃
檢測：折射率檢測器(RID)
RID單元溫度：140℃
試樣溶液注入量：300 μL
GPC(Gel Permeation Chromatograph，凝膠滲透層析)管柱校準用標準物質溶液：Tosoh(股)製造之標準聚苯乙烯
再者，凝膠滲透層析法之更詳細之測定條件記載於下述實施例中。When a solvent is present in the transparent resin film, since the low-molecular component contained in the protective film in the solvent is dissolved out, it is easy to whiten the surface of the transparent protective film bonded to the protective film. Here, in the present invention, the "low molecular component" contained in the protective film means that the log M of the graph obtained by measurement by gel permeation chromatography with a measurement temperature of 140 ° C in accordance with the following conditions is Components detected in the range of 2.82 to 3.32.
＜ Measurement conditions of gel permeation chromatography ＞
Column: 1 PLgel Individual (5 μm, 50Å, 7.5 mm ID × 30 cm, manufactured by Agilent Technology) and 2 TSKgel GMH HR -H (S) HT (7.5 mm ID × 30 cm, manufactured by Tosoh) ) Connect the mobile phase: add 0.1 w / V% BHT (Butylated Hydroxy Toluene, dibutylhydroxytoluene) to o-dichlorobenzene (Wako, special grade). Flow rate: 1 mL / min
Column oven temperature: 140 ℃
Automatic sampler temperature: 140 ℃
System oven temperature: 40 ℃
Detection: refractive index detector (RID)
RID unit temperature: 140 ° C
Sample solution injection volume: 300 μL
GPC (Gel Permeation Chromatograph) column calibration standard solution: Standard polystyrene manufactured by Tosoh Co., Ltd. Further, the detailed measurement conditions of the gel permeation chromatography method are described below. Example.

認為上述低分子成分具體而言係來自保護膜中或於保護膜包含基材膜及積層於其上之黏著劑層之情形時黏著劑層中所含有之殘存單體、低聚物及添加劑或膜原料等之成分。作為保護膜所含有之低分子成分，例如可列舉來自成核劑、抗氧化劑、鹽酸吸收劑、耐熱穩定劑、光穩定劑、紫外線吸收劑、潤滑劑、抗黏連劑、抗靜電劑、阻燃劑、顏料、染料、分散劑、銅毒抑制劑、中和劑、發泡劑、塑化劑、氣泡抑制劑、交聯劑、過氧化物等流動性改良劑、焊接強度改良劑等之成分，作為積層於保護膜上之黏著劑層所含有之低分子成分，例如可列舉黏著賦予樹脂及來自軟化劑等之成分等。It is considered that the above-mentioned low-molecular component is specifically derived from the residual monomers, oligomers, and additives contained in the adhesive layer when the protective film contains the base film and the adhesive layer laminated on the protective film or Ingredients such as film materials. Examples of the low-molecular component contained in the protective film include nucleating agents, antioxidants, hydrochloric acid absorbers, heat-resistant stabilizers, light stabilizers, ultraviolet absorbers, lubricants, anti-blocking agents, antistatic agents, and inhibitors. Fuel improvers, pigments, dyes, dispersants, copper poison inhibitors, neutralizers, foaming agents, plasticizers, bubble inhibitors, crosslinkers, peroxides and other flow improvers, welding strength improvers, etc. The component is a low-molecular component contained in the adhesive layer laminated on the protective film, and examples thereof include an adhesive-imparting resin, a component derived from a softener, and the like.

於本發明中，關於保護膜所含有之低分子成分之含量，定義為依據上述凝膠滲透層析法之測定條件，藉由測定溫度為140℃之凝膠滲透層析法進行測定而獲得之圖的Log M為2.82至3.32之面積相對於總面積之比率的低分子成分量W(%)較佳為0.4%以下，更佳為0.38%以下，進而較佳為0.35%以下。若低分子成分量W為上述上限值以下，則不易發生保護膜所含有之低分子成分轉印至透明樹脂膜，作為用以保護光學用之透明樹脂膜表面之保護膜而言合適。又，低分子成分量W之下限值並無特別限定，但因於光學領域中所使用之保護膜一般而言含有來自如前文例示之添加劑或原料之低分子成分，故通常為0.001%以上。In the present invention, the content of the low-molecular component contained in the protective film is defined as a measurement obtained by gel permeation chromatography with a measurement temperature of 140 ° C. in accordance with the measurement conditions of the gel permeation chromatography described above. The low-molecular-weight component W (%) of the ratio of the area of Log M to the total area of 2.82 to 3.32 in the figure is preferably 0.4% or less, more preferably 0.38% or less, and still more preferably 0.35% or less. If the amount of the low molecular component W is equal to or less than the above-mentioned upper limit value, the low molecular component contained in the protective film is unlikely to be transferred to the transparent resin film, and it is suitable as a protective film for protecting the surface of the transparent resin film for optical use. The lower limit value of the low molecular component amount W is not particularly limited. However, since the protective film used in the optical field generally contains low molecular components derived from additives or raw materials as exemplified above, it is usually 0.001% or more. .

於本發明中，保護膜之算術平均波紋度Wa(nm)與低分子成分量W(%)之積(Wa×W)較佳為14以下，更佳為12以下，進而較佳為10以下。若Wa(nm)與低分子成分量W(%)之積為上述上限值以下，則因可抑制貼合有該保護膜之透明樹脂膜之表面凹凸之產生，並且可抑制白化，故可具有高透明性，成為外觀優異之積層體，且可適用於光學用途中。In the present invention, the product (Wa × W) of the arithmetic average waviness Wa (nm) and the low molecular weight W (%) of the protective film is preferably 14 or less, more preferably 12 or less, and even more preferably 10 or less. . If the product of Wa (nm) and the low molecular weight W (%) is equal to or less than the above-mentioned upper limit value, the occurrence of unevenness on the surface of the transparent resin film to which the protective film is bonded can be suppressed, and whitening can be suppressed. It has high transparency and is a laminated body with excellent appearance, and is suitable for optical applications.

保護膜之厚度並無特別限定，但就透明樹脂膜之保護之觀點而言，通常為10 μm以上，較佳為20 μm以上，更佳為25 μm以上。另一方面，就膜處理之觀點而言，較佳為300 μm以下。於在透明樹脂膜之兩個面貼合保護膜之情形時，各面之保護膜之厚度可相同，亦可不同。The thickness of the protective film is not particularly limited, but from the viewpoint of protection of the transparent resin film, it is usually 10 μm or more, preferably 20 μm or more, and more preferably 25 μm or more. On the other hand, from the viewpoint of film treatment, it is preferably 300 μm or less. When a protective film is laminated on both sides of the transparent resin film, the thickness of the protective film on each side may be the same or different.

本發明之積層體之抑制貼合有保護膜之透明樹脂膜表面之凹凸之產生及白化之效果優異。因此，構成本發明之積層體之透明樹脂膜之霧度較佳為1.0%以下，更佳為0.7%以下，進而較佳為0.5%以下。又，構成本發明之積層體之透明樹脂膜之全光線透過率較佳為85%以上，更佳為87%以上，進而較佳為90%以上。進而，構成本發明之積層體之透明樹脂膜之黃度較佳為3.0以下，更佳為2.5以下，進而較佳為2.2以下。若構成積層體之透明樹脂膜之霧度或全光線透過率處於上述範圍內，則成為適於要求高透明性之光學用途之積層體。而且，因自本發明之積層體剝離保護膜而使用之透明樹脂膜不易發生膜表面之凹凸或白化，且透明性優異，故若使用該透明樹脂膜，則例如與使用透過率低之透明樹脂膜之情形相比，容易確保一定之亮度，能夠抑制顯示元件等之發光強度。因此，可削減具有顯示元件等之顯示裝置之耗電。又，就透明樹脂膜之黃度較低，且著色得到抑制之觀點而言，本發明之積層體亦適於光學用途。再者，本發明中之「透明樹脂膜之白化」如下述實施例中所記載那樣，係可藉由照射光束3000流明之高亮度光而識別者，「白化」之產生未必對透明樹脂膜之霧度或全光線透過率產生直接影響。The laminated body of the present invention is excellent in suppressing the occurrence of unevenness and whitening of the surface of the transparent resin film to which the protective film is bonded. Therefore, the haze of the transparent resin film constituting the laminated body of the present invention is preferably 1.0% or less, more preferably 0.7% or less, and still more preferably 0.5% or less. The total light transmittance of the transparent resin film constituting the laminated body of the present invention is preferably 85% or more, more preferably 87% or more, and even more preferably 90% or more. Furthermore, the yellowness of the transparent resin film constituting the laminated body of the present invention is preferably 3.0 or less, more preferably 2.5 or less, and even more preferably 2.2 or less. If the haze or total light transmittance of the transparent resin film constituting the laminated body is within the above range, it will be a laminated body suitable for optical applications requiring high transparency. In addition, the transparent resin film used for peeling off the protective film from the laminated body of the present invention is less prone to unevenness or whitening of the film surface, and is excellent in transparency. Therefore, if the transparent resin film is used, for example, a transparent resin with low transmittance is used. Compared with the case of a film, it is easier to ensure a certain brightness, and it is possible to suppress the light emission intensity of a display element or the like. Therefore, power consumption of a display device having a display element or the like can be reduced. In addition, from the viewpoint that the yellowness of the transparent resin film is low and the coloring is suppressed, the laminated body of the present invention is also suitable for optical applications. Furthermore, the "whitening of the transparent resin film" in the present invention can be identified by irradiating a high-intensity light beam of 3000 lumens, as described in the following examples. The generation of "whitening" does not necessarily affect the transparency of the transparent resin film. Haze or total light transmission has a direct effect.

本發明之積層體可使用公知之方法及裝置/設備，藉由將透明樹脂膜與保護膜貼合而進行製造。具體而言，例如可藉由包含如下步驟之方法進行製造：
將樹脂清漆塗佈於支持基材上，上述樹脂清漆係將用以形成透明樹脂膜之樹脂組合物與溶劑加以混合及攪拌而獲得者；
藉由使所塗佈之樹脂清漆乾燥而將溶劑除去，於支持基材上形成透明樹脂膜之層；
於形成於支持基材上之透明樹脂膜的與支持基材為相反側之面貼合保護膜；及
自形成於支持基材上之透明樹脂膜之層剝離支持基材。The laminated body of this invention can be manufactured by bonding a transparent resin film and a protective film using a well-known method and apparatus / equipment. Specifically, for example, it can be manufactured by a method including the following steps:
The resin varnish is coated on a supporting substrate, and the resin varnish is obtained by mixing and stirring a resin composition for forming a transparent resin film and a solvent;
The solvent is removed by drying the applied resin varnish to form a layer of a transparent resin film on a supporting substrate;
A protective film is laminated on a surface of the transparent resin film formed on the supporting substrate on the side opposite to the supporting substrate; and the supporting substrate is peeled from the layer of the transparent resin film formed on the supporting substrate.

例如，於藉由以澆鑄法為代表之包含塗佈包含溶劑之樹脂清漆而進行製膜，其後藉由乾燥除去溶劑之步驟之方法連續地製造透明樹脂膜之情形時，不易藉由乾燥完全除去溶劑，多數情況下於透明樹脂膜中殘存有溶劑之狀態下用於下一步驟，由於存在一定程度之量之殘留溶劑，故於貼合保護膜時，容易於透明樹脂膜產生表面凹凸或白化。即便於此種情形時，藉由使用具有特定範圍之算術平均波紋度Wa之保護膜，又，藉由將透明樹脂膜中之殘留溶劑量或保護膜中之低分子成分量控制於特定範圍內，亦可有效抑制於貼合有保護膜之透明樹脂膜表面產生之凹凸或白化。For example, in the case of forming a film by applying a resin varnish containing a solvent including a casting method as a representative, and then continuously manufacturing a transparent resin film by a method of removing the solvent by drying, it is difficult to completely dry the film by drying. The solvent is removed, and in most cases, it is used in the next step in the state where the solvent remains in the transparent resin film. Since there is a certain amount of residual solvent, it is easy to cause surface unevenness or transparent surface of the transparent resin film when the protective film is bonded. Albino. That is, to facilitate such a situation, by using a protective film having an arithmetic average waviness Wa in a specific range, and by controlling the amount of residual solvent in the transparent resin film or the amount of low molecular components in the protective film within a specific range , Can also effectively suppress the unevenness or whitening on the surface of the transparent resin film with a protective film.

於藉由上述方法製造本發明之積層體之情形時，塗佈樹脂清漆之支持基材為膜狀基材，例如可為樹脂膜基材、鋼基材(例如SUS(Steel Use Stainless，日本不鏽鋼標準)帶)。作為樹脂膜基材，例如有聚對苯二甲酸乙二酯(PET)膜。支持基材之厚度並無特別限制，例如為10～500 μm，較佳為50～300 μm。When the laminated body of the present invention is manufactured by the above method, the supporting substrate coated with the resin varnish is a film-like substrate, for example, a resin film substrate, a steel substrate (such as SUS (Steel Use Stainless, Japanese stainless steel)). Standard) with). As a resin film base material, a polyethylene terephthalate (PET) film is mentioned, for example. The thickness of the supporting substrate is not particularly limited, and is, for example, 10 to 500 μm, and preferably 50 to 300 μm.

於塗膜之乾燥步驟中，為了使樹脂清漆中之溶劑處於所需範圍內，較佳為藉由乾燥除去溶劑。用以除去溶劑之乾燥可利用自然乾燥、通風乾燥、加熱乾燥或減壓乾燥及該等之組合進行。就生產效率等之觀點而言，較佳為加熱乾燥。乾燥條件根據所使用之溶劑之種類或膜中之溶劑含量等，於不損及透明樹脂膜之光學特性之範圍內適當決定即可。例如可於50～300℃、較佳為70～250℃之溫度下例如加熱5～100分鐘左右。In the drying step of the coating film, in order to make the solvent in the resin varnish within a desired range, it is preferable to remove the solvent by drying. The drying for removing the solvent may be performed by natural drying, air drying, heating drying or drying under reduced pressure, and a combination thereof. From the viewpoint of production efficiency and the like, heat drying is preferred. The drying conditions may be appropriately determined within a range that does not impair the optical characteristics of the transparent resin film according to the type of solvent used, the solvent content in the film, and the like. For example, it may be heated at a temperature of 50 to 300 ° C, preferably 70 to 250 ° C, for example, for about 5 to 100 minutes.

其次，將滿足上述式(1)之關係之低分子成分量之保護膜貼合於透明樹脂膜之與支持基材為相反側之面，獲得於支持基材上形成透明樹脂膜之層、進而於該透明樹脂膜之層上積層有保護膜之積層膜。其後，藉由自透明樹脂膜之層剝離支持基材，可獲得將保護膜貼合於透明樹脂膜之積層膜。又，可視需要將保護膜貼合於已剝離支持基材之透明樹脂膜之表面，進而亦可實施將所獲得之積層膜捲繞成卷狀之步驟、用以進而使已剝離支持基材之透明樹脂膜乾燥之乾燥步驟及/或用以提高膜之平滑性之整平面之步驟等。Next, a protective film with a low molecular component content that satisfies the relationship of the above formula (1) is bonded to the surface of the transparent resin film on the side opposite to the supporting substrate, and a layer forming a transparent resin film on the supporting substrate is obtained, and further, A laminated film having a protective film is laminated on the layer of the transparent resin film. Thereafter, by peeling the supporting substrate from the layer of the transparent resin film, a laminated film in which a protective film is bonded to the transparent resin film can be obtained. In addition, if necessary, a protective film is attached to the surface of the transparent resin film of the peeled support substrate, and a step of winding the obtained laminated film into a roll shape may be further performed to further make the peeled support substrate A drying step for drying the transparent resin film and / or a step for improving the smoothness of the film and the like.

本發明之積層體可抑制貼合有保護膜之透明樹脂膜之表面之凹凸之產生及白化，由於具有高透明性及良好之外觀，故可適當地用於各種圖像顯示裝置之顯示器等光學用途、尤其是可撓性顯示器之前面板(視窗膜)。作為圖像顯示裝置，可列舉：電視、智慧型手機、行動電話、汽車導航、平板PC(Personal Computer，個人電腦)、可攜式遊戲機、電子紙、指示器、公告板、鐘錶及智慧型表等可穿戴裝置等。作為可撓性顯示器，可列舉具有可撓性特性之圖像顯示裝置，例如：電視、智慧型手機、行動電話、汽車導航、平板PC、可攜式遊戲機、電子紙、指示器、公告板、鐘錶及可穿戴裝置等。
[實施例]The laminated body of the present invention can suppress the occurrence of unevenness and whitening of the surface of the transparent resin film to which a protective film is attached, and because it has high transparency and good appearance, it can be suitably used in optical displays such as various image display devices. Uses, especially flexible display front panel (window film). Examples of the image display device include a television, a smart phone, a mobile phone, a car navigation, a tablet PC (Personal Computer), a portable game machine, electronic paper, a pointer, a bulletin board, a clock, and a smart phone. Wearable devices such as watches. Examples of flexible displays include image display devices having flexible characteristics, such as televisions, smartphones, mobile phones, car navigation, tablet PCs, portable game consoles, electronic paper, indicators, and bulletin boards , Watches, and wearable devices.
[Example]

以下，藉由實施例進一步詳細地說明本發明。例中之「%」及「份」只要無特別記載，則為質量%及質量份。又，實施例及比較例中使用之保護膜之算術平均波紋度及低分子成分量、透明樹脂膜之殘留溶劑量、全光線透過率、霧度及黃度分別根據下述方法測定並算出。將結果示於表1。Hereinafter, the present invention will be described in more detail through examples. "%" And "part" in the examples are mass% and mass part unless otherwise noted. In addition, the arithmetic average waviness and the amount of low molecular components of the protective films used in the examples and comparative examples, the amount of residual solvent, the total light transmittance, haze, and yellowness of the transparent resin film were measured and calculated by the following methods, respectively. The results are shown in Table 1.

＜算術平均波紋度Wa之測定方法＞
(1)表面形狀之測定(干涉顯微鏡)
使用Ryoka Systems公司製造之Mircomap以5倍之倍率測定保護膜之表面形狀。所得之測定範圍為x方向93.59 μm、y方向70.25 μm。
(2)算術平均波紋度Wa之算出
根據獲得之表面形狀資料，使用Ryoka Systems公司製造之Mircomap附屬之軟體SX-Viewer，於臨界λc為20 μm、取樣值為3之條件下實施傅立葉變換，獲得算術平均波紋度Wa。<Method for measuring arithmetic mean waviness Wa>
(1) Measurement of surface shape (interference microscope)
The surface shape of the protective film was measured at a magnification of 5 times using Mircomap manufactured by Ryoka Systems. The obtained measurement range was 93.59 μm in the x direction and 70.25 μm in the y direction.
(2) Calculation of arithmetic average waviness Wa Based on the obtained surface shape data, the software SX-Viewer attached to Mircomap manufactured by Ryoka Systems was used to perform Fourier transform under the condition that the critical λc was 20 μm and the sampling value was 3 Arithmetic mean waviness Wa.

＜殘留溶劑量S之測定方法＞
熱重-示差熱(TG-DTA)測定
TG-DTA之測定裝置使用Hitachi High-Tech Science公司製造之TG/DTA6300。自所製作之透明聚醯亞胺系膜獲取約20 mg之試樣。一面將該試樣以10℃/min之升溫速度自室溫升溫至120℃，於120℃保持5分鐘後，以10℃/min之升溫速度升溫(加熱)至400℃，一面測定試樣之質量變化。圖1表示下述實施例1中所製作之透明聚醯亞胺系膜之TG-DTA測定結果。<Method for measuring residual solvent amount S>
Thermogravimetric-differential thermal (TG-DTA) determination
As a measuring device for TG-DTA, TG / DTA6300 manufactured by Hitachi High-Tech Science was used. A sample of about 20 mg was obtained from the prepared transparent polyimide film. The temperature of the sample was raised from room temperature to 120 ° C at a heating rate of 10 ° C / min. After being held at 120 ° C for 5 minutes, the sample was heated (heated) to 400 ° C at a heating rate of 10 ° C / min, and the mass of the sample was measured. Variety. FIG. 1 shows the TG-DTA measurement results of the transparent polyfluorene-imide-based film produced in Example 1 below.

自TG-DTA測定結果，根據數式(2)算出自120℃至250℃之質量減少率S(質量%)。
S(質量%)＝100－(W1/W0)×100 (2)
[數式(2)中，W0為於120℃下保持5分鐘後之試樣之質量，W1為250℃之試樣之質量]。
將所算出之質量減少率S作為透明樹脂膜中之殘留溶劑量S(質量%)。From the measurement results of TG-DTA, the mass reduction rate S (mass%) from 120 ° C to 250 ° C was calculated according to equation (2).
S (mass%) = 100－ (W1 / W0) × 100 (2)
[In formula (2), W0 is the mass of the sample after being held at 120 ° C for 5 minutes, and W1 is the mass of the sample at 250 ° C].
Let the calculated mass reduction rate S be the residual solvent amount S (% by mass) in the transparent resin film.

＜低分子成分量之測定方法＞
低分子成分量藉由凝膠滲透層析(GPC)法求出。GPC測定於下述條件下進行。低分子成分量藉由凝膠滲透層析(GPC)法求出。關於所獲得之層析圖，相對於聚苯乙烯換算分子量Log M，對來自試驗對象溶液與參照溶液之折射率差的電氣訊號值(強度Y)進行繪圖而獲得圖。關於該圖，將連結Log M為2.82及7.61之點的線規定為基準線。又，將藉由基準線修正之強度Y值成為負數之部分設為0。
(1)試樣溶液製備條件
溶劑：向鄰二氯苯(和光，特級)中添加0.1 w/V%之BHT(二丁基羥基甲苯)後使用
試樣溶液濃度：1 mg/mL
溶解用自動振盪器：DF-8020(Tosoh(股)製造)
溶解條件：將5 mg之試樣封入至1000目之SUS製金屬網袋中，將封入有試樣之金屬網袋放入至試管，其後向試管中加入5 mL之溶劑。其次，將藉由鋁箔蓋住之試管安放於DF-8020中，以60往返/分鐘之攪拌速度於140℃下攪拌120分鐘。＜ Method of measuring low molecular weight ＞
The amount of low-molecular components was determined by a gel permeation chromatography (GPC) method. The GPC measurement was performed under the following conditions. The amount of low-molecular components was determined by a gel permeation chromatography (GPC) method. The obtained chromatogram was obtained by plotting the electrical signal value (intensity Y) from the refractive index difference between the test target solution and the reference solution with respect to the polystyrene-equivalent molecular weight Log M. In this figure, a line connecting points where Log M is 2.82 and 7.61 is defined as a reference line. In addition, the portion where the intensity Y value corrected by the reference line becomes a negative number is set to 0.
(1) Preparation conditions for sample solution Solvent: Add 0.1 w / V% BHT (dibutyl hydroxytoluene) to o-dichlorobenzene (Wako, special grade). Concentration of sample solution: 1 mg / mL
Automatic oscillator for dissolution: DF-8020 (manufactured by Tosoh)
Dissolution conditions: 5 mg of the sample was sealed in a 1000 mesh SUS metal mesh bag, the metal mesh bag with the sample was placed in a test tube, and 5 mL of a solvent was added to the test tube. Next, the test tube covered with aluminum foil was placed in DF-8020, and stirred at 140 ° C for 120 minutes at a stirring speed of 60 rounds / minute.

(2)測定條件
(GPC裝置及軟體)
測定裝置：Tosoh(股)製造之HLC-8121 GPC/HT
測定軟體：GPC-8020 model II 資料收集 Version4.32(Tosoh(股)製造)
分析軟體：GPC-8020 model II 資料分析 Version4.32(Tosoh(股)製造)
(測定條件)
GPC管柱：將1根PLgel Individual (5 μm，50Å，7.5 mm ID×30 cm，Agilent Technology製造)與2根TSKgel GMHHR -H(S)HT (7.5 mm ID×30 cm，Tosoh(股)製造)連結
流動相：向鄰二氯苯(和光，特級)中添加0.1 w/V%之BHT後使用
流速：1 mL/min
管柱烘箱溫度：140℃
自動取樣器溫度：140℃
系統烘箱溫度：40℃
檢測：示差折射率檢測器(RID)
RID單元溫度：140℃
試樣溶液注入量：300 μL
GPC管柱校準用標準物質溶液：分別以如下表之質量稱取Tosoh(股)製造之標準聚苯乙烯，加入5 mL之鄰二氯苯(與流動相相同之組成)，於室溫下使其完全溶解而進行製備。(2) Measurement conditions
(GPC device and software)
Measuring device: HLC-8121 GPC / HT manufactured by Tosoh Co., Ltd.
Measurement software: GPC-8020 model II data collection version 4.32 (manufactured by Tosoh)
Analysis software: GPC-8020 model II data analysis version 4.32 (manufactured by Tosoh)
(Measurement conditions)
GPC column: 1 PLgel Individual (5 μm, 50Å, 7.5 mm ID × 30 cm, manufactured by Agilent Technology) and 2 TSKgel GMH HR -H (S) HT (7.5 mm ID × 30 cm, Tosoh) Manufacturing) Linking mobile phase: Add 0.1 w / V% BHT to o-dichlorobenzene (Wako, Premium). Flow rate: 1 mL / min
Column oven temperature: 140 ℃
Automatic sampler temperature: 140 ℃
System oven temperature: 40 ℃
Detection: differential refractive index detector (RID)
RID unit temperature: 140 ° C
Sample solution injection volume: 300 μL
Standard material solution for GPC column calibration: Weigh standard polystyrene manufactured by Tosoh (stock) according to the following table, add 5 mL of o-dichlorobenzene (same composition as mobile phase), and make it at room temperature. It was completely dissolved and prepared.

[表1]
[Table 1]

根據GPC測定結果，藉由數式(3)算出低分子成分量W(%)。
W(%)＝V0/V1 (3)
[數式(3)中，V0為由GPC測定獲得之圖中的Log M為2.82至3.32之面積，V1為圖整體之面積]。Based on the GPC measurement results, the low-molecular component amount W (%) was calculated by the formula (3).
W (%) = V0 / V1 (3)
[In Equation (3), V0 is an area where Log M in the graph obtained by GPC measurement is 2.82 to 3.32, and V1 is an area of the entire graph].

＜全光線透過率＞
透明樹脂膜之全光線透過率係依據JIS K7105：1981，藉由Suga Test Instruments(股)製造之全自動直讀霧度計HGM-2DP而測定。＜ Total light transmittance ＞
The total light transmittance of the transparent resin film was measured in accordance with JIS K7105: 1981 by a fully-automatic direct-reading haze meter HGM-2DP manufactured by Suga Test Instruments.

＜霧度＞
透明樹脂膜之霧度係依據JIS K7105：1981，藉由Suga Test Instruments(股)製造之全自動直讀霧度計HGM-2DP而測定。<Haze>
The haze of the transparent resin film was measured in accordance with JIS K7105: 1981 by a full-automatic direct-reading haze meter HGM-2DP manufactured by Suga Test Instruments.

＜黃度＞
透明樹脂膜之黃度係藉由使用紫外可見近紅外分光光度計(日本分光(股)製造之V-670)求出三刺激值(X，Y，Z)，並代入至計算式(4)中而算出。
黃度＝100×(1.2769X－1.0592Z)/Y (4)＜ Yellowness ＞
The yellowness of the transparent resin film was determined by using a UV-Vis near-infrared spectrophotometer (V-670 manufactured by JASCO Corporation) to calculate the tristimulus value (X, Y, Z), and substituted it into the calculation formula (4) To calculate.
Yellowness = 100 × (1.2769X－1.0592Z) / Y (4)

製造例1：透明聚醯亞胺系高分子之製備
準備於可分離式燒瓶安裝有矽膠管、攪拌裝置及溫度計之反應器及油浴。向該燒瓶內投入4,4'-(六氟亞異丙基)二鄰苯二甲酸酐(6FDA) 75.52 g及2,2'-雙(三氟甲基)-4,4'-二胺基聯苯(TFMB) 54.44 g。一面以400 rpm對其進行攪拌一面加入N,N-二甲基乙醯胺(DMAc) 519.84 g，繼續攪拌直至燒瓶之內容物成為均一之溶液。繼而，一面使用油浴將容器內溫度調整成為20～30℃之範圍，一面進而繼續攪拌20小時，使其反應而生成聚醯胺酸。30分鐘後，將攪拌速度變更為100 rpm。攪拌20小時後，將反應系溫度恢復至室溫，加入DMAc 649.8 g以將聚合物濃度調整成為10重量%。進而，加入吡啶32.27 g、無水乙酸41.65 g，於室溫下攪拌10小時而進行醯亞胺化。自反應容器中取出聚醯亞胺清漆。將所獲得之聚醯亞胺清漆滴加至甲醇中而進行再沈澱，對所獲得之粉體進行加熱乾燥而將溶劑除去，獲得作為固形物成分之透明聚醯亞胺系高分子。進行所獲得之聚醯亞胺系高分子之GPC測定，重量平均分子量為360,000。Production Example 1: Preparation of transparent polyfluorene-imide-based polymer A reactor and an oil bath equipped with a silicone tube, a stirring device, and a thermometer were prepared in a separable flask. 75.52 g of 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 2,2'-bis (trifluoromethyl) -4,4'-diamine were charged into the flask. Diphenyl (TFMB) 54.44 g. While stirring it at 400 rpm, N, N-dimethylacetamide (DMAc) 519.84 g was added, and stirring was continued until the contents of the flask became a homogeneous solution. Then, while the temperature in the container was adjusted to a range of 20 to 30 ° C. using an oil bath, stirring was continued for another 20 hours to cause the reaction to generate polyamic acid. After 30 minutes, the stirring speed was changed to 100 rpm. After stirring for 20 hours, the temperature of the reaction system was returned to room temperature, and 649.8 g of DMAc was added to adjust the polymer concentration to 10% by weight. Further, 32.27 g of pyridine and 41.65 g of anhydrous acetic acid were added, and the mixture was stirred at room temperature for 10 hours to carry out imidization. Take out polyimide varnish from the reaction vessel. The obtained polyimide varnish was dropped into methanol to perform reprecipitation, and the obtained powder was dried by heating to remove the solvent, thereby obtaining a transparent polyimide-based polymer as a solid component. GPC measurement of the obtained polyimide-based polymer was carried out, and the weight average molecular weight was 360,000.

製造例2：透明聚醯胺醯亞胺系高分子之製備
於氮氣氛圍下，向具備攪拌翼之1L可分離式燒瓶中加入TFMB 50 g(156.13 mmol)及DMAc 642.07 g，一面於室溫下攪拌一面使TFMB溶解於DMAc。其次，向燒瓶中添加6FDA 20.84 g(46.91 mmol)，於室溫下攪拌3小時。其後，將4,4'-氧基雙(苯甲醯氯) (OBBC) 9.23 g(31.27 mmol)加入至燒瓶中，其次將對苯二甲醯氯(TPC) 15.87 g (78.18 mmol)加入至燒瓶中，於室溫下攪拌1小時。其次，向燒瓶中加入4-甲基吡啶9.89 g (106.17 mmol)與無水乙酸14.37 g (140.73 mmol)，於室溫下攪拌30分鐘後，使用油浴升溫至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，以線狀投入至大量之甲醇中，取出析出之沈澱物，於甲醇中浸漬6小時後，藉由甲醇進行洗淨。其次，於100℃下進行沈澱物之減壓乾燥，獲得透明聚醯胺醯亞胺系高分子。進行所獲得之聚醯胺醯亞胺系高分子之GPC測定，重量平均分子量為420,000。Manufacturing Example 2: Preparation of transparent polyfluorene and imine-based polymers In a nitrogen atmosphere, TFMB 50 g (156.13 mmol) and DMAc 642.07 g were added to a 1 L separable flask equipped with a stirring wing, while being at room temperature Stir while dissolving TFMB in DMAc. Next, 20.84 g (46.91 mmol) of 6FDA was added to the flask, and the mixture was stirred at room temperature for 3 hours. Thereafter, 9.23 g (31.27 mmol) of 4,4'-oxybis (benzidine chloride) (OBBC) was added to the flask, followed by 15.87 g (78.18 mmol) of paraxylylene chloride (TPC) Into the flask, stir at room temperature for 1 hour. Next, 9.89 g (106.17 mmol) of 4-methylpyridine and 14.37 g (140.73 mmol) of anhydrous acetic acid were added to the flask, and after stirring at room temperature for 30 minutes, the temperature was raised to 70 ° C using an oil bath, followed by stirring for 3 hours to obtain The reaction solution.
The obtained reaction solution was cooled to room temperature, and was linearly poured into a large amount of methanol, and the deposited precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Next, the precipitate was dried under reduced pressure at 100 ° C to obtain a transparent polyamidamine / imine polymer. A GPC measurement of the obtained polyamidamine / imine-based polymer was performed, and the weight average molecular weight was 420,000.

製造例3：二氧化矽溶膠之製備
將藉由溶膠-凝膠法製作之BET(Brunauer-Emmett-Teller，布厄特)徑(藉由BET法測定之平均一次粒徑)為27 nm之非晶形二氧化矽溶膠作為原料，藉由溶劑置換製備γ-丁內酯(以下有時亦記為GBL)置換二氧化矽溶膠。藉由網眼為10 μm之膜濾器對所獲得之溶膠進行過濾，獲得GBL置換二氧化矽溶膠。所獲得之GBL置換二氧化矽溶膠之二氧化矽粒子均為30～32質量%。Manufacturing Example 3: Preparation of silica dioxide sol A BET (Brunauer-Emmett-Teller) diameter (average primary particle diameter measured by BET method) made by the sol-gel method was 27 nm. The crystalline silica sol was used as a raw material, and γ-butyrolactone (hereinafter sometimes referred to as GBL) was used to replace the silica sol by solvent substitution. The obtained sol was filtered through a membrane filter having a mesh of 10 μm to obtain a GBL-substituted silica dioxide sol. The silica particles of the GBL-substituted silica sol obtained were all 30 to 32% by mass.

實施例1：積層體之製作
將藉由上述製造例1獲得之透明聚醯亞胺系高分子以16.5%之濃度溶解於將γ-丁內酯(GBL)與DMAc以1：9混合而成之混合溶劑中，獲得樹脂清漆。藉由流延成形將所獲得之樹脂清漆塗佈於聚對苯二甲酸乙二酯(PET)膜基材(厚度為188 μm，東洋紡(股)製造)上而進行製膜。其後，藉由於50℃下加熱30分鐘、於140℃下加熱10分鐘而對塗膜進行乾燥，自塗膜剝離PET基材。其後，藉由於200℃下加熱12分鐘，獲得厚度約80 μm之透明聚醯亞胺系膜。所獲得之透明聚醯亞胺系膜之殘留溶劑量為1質量%。
其次，作為保護膜，準備Toray Film Products(股)製造之TORETEC(註冊商標)N-711(聚乙烯系保護膜)。上述保護膜之低分子成分量為0.33%。使用輥將其貼合至所製作之透明聚醯亞胺系膜，製作積層體。Example 1: Production of multilayer body The transparent polyfluorene-imide polymer obtained in the above Production Example 1 was dissolved at a concentration of 16.5% in a mixture of γ-butyrolactone (GBL) and DMAc at 1: 9 In a mixed solvent, a resin varnish is obtained. The obtained resin varnish was applied to a polyethylene terephthalate (PET) film substrate (thickness: 188 μm, manufactured by Toyobo Co., Ltd.) by casting to form a film. Thereafter, the coating film was dried by heating at 50 ° C. for 30 minutes and 140 ° C. for 10 minutes, and the PET substrate was peeled from the coating film. Thereafter, a transparent polyimide film having a thickness of about 80 μm was obtained by heating at 200 ° C. for 12 minutes. The residual solvent amount of the obtained transparent polyfluorene-imide-based film was 1% by mass.
Next, as a protective film, TORETEC (registered trademark) N-711 (polyethylene-based protective film) manufactured by Toray Film Products Co., Ltd. was prepared. The amount of the low-molecular component of the protective film was 0.33%. This was bonded to the produced transparent polyimide-based film using a roller to prepare a laminated body.

＜橘皮之評價＞
對所獲得之積層體之與保護膜貼合之透明聚醯亞胺系膜之表面狀態進行確認。自所獲得之積層體切出100 mm見方，於溫度23℃、相對濕度50%之環境中靜置10天。其後，剝離保護膜，於螢光燈下對曾貼合有保護膜之透明聚醯亞胺系膜之表面進行目視評價。將結果示於表2。＜ Evaluation of Orange Peel ＞
The surface state of the transparent polyfluorene-imide film laminated with the protective film of the obtained laminated body was confirmed. A 100 mm square was cut out of the obtained laminated body, and left to stand for 10 days in an environment of a temperature of 23 ° C and a relative humidity of 50%. After that, the protective film was peeled off, and the surface of the transparent polyimide-based film to which the protective film was pasted was visually evaluated under a fluorescent lamp. The results are shown in Table 2.

＜橘皮之評價基準＞
1：未視認到凹凸
2：較弱地視認到凹凸
3：稍微強烈地視認到凹凸
4：強烈地視認到凹凸＜ Evaluation Criteria for Orange Peel ＞
1: Unevenness is not recognized
2: Weakness is visually recognized
3: Slightly strong unevenness
4: Strong irregularity

＜白化之評價＞
對所獲得之透明聚醯亞胺系膜之白化進行確認。
將實施例1中製作之積層體切出100 mm見方，於溫度23℃、濕度50%之環境下靜置3天。其後，剝離貼合之保護膜，藉由潔淨廢料用布擦拭曾貼合有保護膜之透明聚醯亞胺系膜之表面。其後，使用POLARION公司製造之HID(High intensity Discharge，高壓氣體放電燈)可攜式探照燈PS-X1(光束3400流明)，根據下述評價基準對膜之外觀(白化)進行評價。將結果示於表2。＜ Evaluation of Albino ＞
The whitening of the obtained transparent polyimide-based film was confirmed.
The laminated body prepared in Example 1 was cut out to a size of 100 mm square, and left to stand for 3 days under the environment of a temperature of 23 ° C and a humidity of 50%. After that, the bonded protective film was peeled off, and the surface of the transparent polyimide-based film to which the protective film was bonded was wiped with a clean waste cloth with a cloth. Thereafter, the HID (High Intensity Discharge) portable searchlight PS-X1 (beam 3400 lumens) manufactured by POLARION was used to evaluate the appearance (whitening) of the film according to the following evaluation criteria. The results are shown in Table 2.

＜白化之評價基準＞
○：無法確認白化
×：可於聚醯亞胺系膜之表面確認到白化＜ Evaluation criteria for whitening ＞
○: Whitening cannot be confirmed ×: Whitening can be confirmed on the surface of the polyimide film

實施例2
將藉由製造例1而獲得之透明聚醯亞胺系高分子以16.5%之濃度溶解於將γ-丁內酯(GBL)與DMAc以1：9進行混合而成之混合溶劑中，獲得樹脂清漆。藉由流延成形將所獲得之樹脂清漆塗佈於聚對苯二甲酸乙二酯(PET)膜基材(厚度為188 μm，東洋紡(股)製造)上而進行製膜。其後，藉由於50℃下加熱30分鐘、於140℃下加熱10分鐘對塗膜進行乾燥，自塗膜剝離PET基材，獲得厚度約80 μm之透明聚醯亞胺系膜。所獲得之透明聚醯亞胺系膜之殘留溶劑量為10質量%。將其用作透明樹脂膜，除此以外藉由與實施例1相同之方法獲得積層體。藉由與實施例1相同之方法，對膜之外觀(橘皮、白化)及光學特性進行評價。將結果示於表2。Example 2
The transparent polyfluorene-imide polymer obtained in Production Example 1 was dissolved at a concentration of 16.5% in a mixed solvent obtained by mixing γ-butyrolactone (GBL) and DMAc at 1: 9 to obtain a resin. Varnish. The obtained resin varnish was applied to a polyethylene terephthalate (PET) film substrate (thickness: 188 μm, manufactured by Toyobo Co., Ltd.) by casting to form a film. Thereafter, the coating film was dried by heating at 50 ° C. for 30 minutes and at 140 ° C. for 10 minutes, and the PET substrate was peeled from the coating film to obtain a transparent polyimide-based film having a thickness of about 80 μm. The residual solvent amount of the obtained transparent polyfluorene-imide-based film was 10% by mass. A laminated body was obtained by the same method as in Example 1 except that this was used as a transparent resin film. By the same method as in Example 1, the appearance (orange peel, whitening) and optical characteristics of the film were evaluated. The results are shown in Table 2.

實施例3
保護膜使用聚丙烯系保護膜 Torayfan(註冊商標) BO25-MK01(Toray(股)製造，低分子成分量：0.04%)，除此以外藉由與實施例1相同之方法獲得積層體。藉由與實施例1相同之方法，對膜之外觀(橘皮、白化)及光學特性進行評價。將結果示於表2。Example 3
A laminated body was obtained by the same method as in Example 1 except that the protective film was a polypropylene-based protective film Torayfan (registered trademark) BO25-MK01 (manufactured by Toray (shares), low molecular weight: 0.04%). By the same method as in Example 1, the appearance (orange peel, whitening) and optical characteristics of the film were evaluated. The results are shown in Table 2.

實施例4
保護膜使用聚丙烯系保護膜 Torayfan(註冊商標) BO25-MK01(Toray(股)製造，低分子成分量：0.04%)，除此以外藉由與實施例2相同之方法獲得積層體。藉由與實施例1相同之方法，對膜之外觀(橘皮、白化)及光學特性進行評價。將結果示於表2。Example 4
A laminated film was obtained by the same method as in Example 2 except that a polypropylene-based protective film Torayfan (registered trademark) BO25-MK01 (manufactured by Toray (stock), low molecular weight: 0.04%) was used for the protective film. By the same method as in Example 1, the appearance (orange peel, whitening) and optical characteristics of the film were evaluated. The results are shown in Table 2.

實施例5
將藉由製造例2而獲得之透明聚醯胺醯亞胺系高分子以10%之濃度溶解於DMAc溶劑中，獲得樹脂清漆，除此以外藉由與實施例2相同之方法獲得積層體。藉由與實施例1相同之方法，對膜之外觀(橘皮、白化)及光學特性進行評價。將結果示於表2。Example 5
The transparent polyamidamine / imide-based polymer obtained in Production Example 2 was dissolved in a DMAc solvent at a concentration of 10% to obtain a resin varnish. A laminated body was obtained in the same manner as in Example 2 except that the resin varnish was obtained. By the same method as in Example 1, the appearance (orange peel, whitening) and optical characteristics of the film were evaluated. The results are shown in Table 2.

實施例6
將製造例2中獲得之透明聚醯胺醯亞胺系高分子溶解於GBL中，加入製造例3中所獲得之GBL置換二氧化矽溶膠而充分進行混合，藉此獲得表2中記載之組成的透明聚醯胺醯亞胺系高分子/二氧化矽粒子混合清漆(以下，有時稱為混合清漆)。此時，以聚醯胺醯亞胺系高分子/二氧化矽粒子濃度(相對於樹脂與二氧化矽粒子之總質量之濃度)成為10質量%而製備混合清漆。其後，藉由流延成形將所獲得之混合清漆塗佈於聚對苯二甲酸乙二酯(PET)膜基材(厚度為188 μm，東洋紡(股)製造(產品名：COSMOSHINE(註冊商標)A4100))上而進行製膜。其後，藉由於50℃下加熱30分鐘、於140℃下加熱10分鐘而對塗膜進行乾燥，自塗膜剝離PET基材，獲得厚度為50 μm之透明樹脂膜。所獲得之透明樹脂膜之殘留溶劑量為14質量%。將其用作透明樹脂膜，除此以外藉由與實施例1相同之方法獲得積層體。藉由與實施例1相同之方法，對膜之外觀(橘皮、白化)及光學特性進行評價。將結果示於表2。Example 6
The transparent polyamidamine / imine-based polymer obtained in Production Example 2 was dissolved in GBL, and the GBL-substituted silica dioxide sol obtained in Production Example 3 was added and mixed thoroughly to obtain the composition described in Table 2. Transparent polyimide / imine-based polymer / silica dioxide particle hybrid varnish (hereinafter, sometimes referred to as a hybrid varnish). At this time, a mixed varnish was prepared so that the concentration of the polyamidamine / imide-based polymer / silicon dioxide particles (the concentration relative to the total mass of the resin and the silicon dioxide particles) became 10% by mass. Thereafter, the obtained mixed varnish was applied to a polyethylene terephthalate (PET) film substrate (thickness: 188 μm) by cast molding (manufactured by Toyobo Co., Ltd. (product name: COMOSHINE (registered trademark) ) A4100)). Thereafter, the coating film was dried by heating at 50 ° C. for 30 minutes and at 140 ° C. for 10 minutes, and the PET substrate was peeled from the coating film to obtain a transparent resin film having a thickness of 50 μm. The residual solvent amount of the obtained transparent resin film was 14% by mass. A laminated body was obtained by the same method as in Example 1 except that this was used as a transparent resin film. By the same method as in Example 1, the appearance (orange peel, whitening) and optical characteristics of the film were evaluated. The results are shown in Table 2.

實施例7
保護膜使用聚丙烯系保護膜 Torayfan(註冊商標) BO25-MK01(Toray(股)製造，低分子成分量：0.04%)，除此以外藉由與實施例6相同之方法獲得積層體。藉由與實施例1相同之方法，對膜之外觀(橘皮、白化)及光學特性進行評價。將結果示於表2。Example 7
A laminated film was obtained in the same manner as in Example 6 except that the protective film was a polypropylene-based protective film Torayfan (registered trademark) BO25-MK01 (manufactured by Toray Co., Ltd., low molecular weight: 0.04%). By the same method as in Example 1, the appearance (orange peel, whitening) and optical characteristics of the film were evaluated. The results are shown in Table 2.

實施例8
將藉由製造例2而獲得之透明聚醯胺醯亞胺系高分子以12%之濃度溶解於DMAc溶劑中，獲得樹脂清漆，將塗膜之乾燥條件變更為於70℃下加熱30分鐘、於140℃下加熱15分鐘，除此以外藉由與實施例2相同之方法獲得積層體。藉由與實施例1相同之方法，對膜之外觀(橘皮、白化)及光學特性進行評價。將結果示於表2。Example 8
The transparent polyamidamine / imine-based polymer obtained in Production Example 2 was dissolved in a DMAc solvent at a concentration of 12% to obtain a resin varnish. The drying conditions of the coating film were changed to heating at 70 ° C for 30 minutes. A laminated body was obtained by the same method as in Example 2 except that it was heated at 140 ° C for 15 minutes. By the same method as in Example 1, the appearance (orange peel, whitening) and optical characteristics of the film were evaluated. The results are shown in Table 2.

實施例9
自塗膜剝離PET基材，其後於200℃下加熱14小時，除此以外藉由與實施例1相同之方法獲得積層體。所獲得之透明樹脂系膜之厚度為79 μm，殘留溶劑量為0.024質量%。藉由與實施例1相同之方法，對膜之外觀(白化)進行評價。將結果示於表2。Example 9
The PET substrate was peeled from the coating film, and thereafter heated at 200 ° C. for 14 hours. A laminated body was obtained in the same manner as in Example 1 except that the PET substrate was heated at 200 ° C. for 14 hours. The thickness of the obtained transparent resin-based film was 79 μm, and the amount of residual solvent was 0.024% by mass. The appearance (whitening) of the film was evaluated by the same method as in Example 1. The results are shown in Table 2.

比較例1
保護膜使用聚乙烯系保護膜 TORETEC(註冊商標) 7832C (Toray Film Products(股)製造，低分子成分量：0.48%)，除此以外藉由與實施例1相同之方法獲得積層體。藉由與實施例1相同之方法，對膜之外觀(橘皮、白化)及光學特性進行評價。將結果示於表2。Comparative Example 1
A laminated body was obtained by the same method as in Example 1 except that a polyethylene-based protective film TORETEC (registered trademark) 7832C (manufactured by Toray Film Products (stock), low molecular weight: 0.48%) was used for the protective film. By the same method as in Example 1, the appearance (orange peel, whitening) and optical characteristics of the film were evaluated. The results are shown in Table 2.

比較例2
保護膜使用聚乙烯系保護膜 TORETEC(註冊商標) 7832C (Toray Film Products(股)製造，低分子成分量：0.48%)，除此以外藉由與實施例2相同之方法獲得積層體。藉由與實施例1相同之方法，對膜之外觀(橘皮、白化)及光學特性進行評價。將結果示於表2。Comparative Example 2
A laminated body was obtained by the same method as in Example 2 except that a polyethylene-based protective film TORETEC (registered trademark) 7832C (manufactured by Toray Film Products (stock), low molecular weight: 0.48%) was used for the protective film. By the same method as in Example 1, the appearance (orange peel, whitening) and optical characteristics of the film were evaluated. The results are shown in Table 2.

比較例3
保護膜使用聚乙烯系保護膜 TORETEC(註冊商標) 7332K (Toray Film Products(股)製造，低分子成分量：0.50%)，除此以外藉由與實施例2相同之方法獲得積層體。藉由與實施例1相同之方法，對膜之外觀(橘皮、白化)及光學特性進行評價。將結果示於表2。Comparative Example 3
The protective film was a polyethylene-based protective film TORETEC (registered trademark) 7332K (manufactured by Toray Film Products, low molecular weight: 0.50%), and a laminated body was obtained by the same method as in Example 2. By the same method as in Example 1, the appearance (orange peel, whitening) and optical characteristics of the film were evaluated. The results are shown in Table 2.

比較例4
保護膜使用聚乙烯系保護膜 TORETEC(註冊商標) 7832C (Toray Film Products(股)製造，低分子成分量：0.48%)，除此以外藉由與實施例6相同之方法獲得積層體。藉由與實施例1相同之方法，對膜之外觀(橘皮、白化)及光學特性進行評價。將結果示於表2。Comparative Example 4
The protective film was a polyethylene-based protective film TORETEC (registered trademark) 7832C (manufactured by Toray Film Products, low molecular weight: 0.48%), and a laminated body was obtained by the same method as in Example 6. By the same method as in Example 1, the appearance (orange peel, whitening) and optical characteristics of the film were evaluated. The results are shown in Table 2.

[表2]
[Table 2]

圖1係表示實施例1中製作之透明聚醯亞胺系膜之TG-DTA(Thermogravimetric Analysis-Differential Thermal Analysis，熱重-示差熱)測定結果。FIG. 1 shows the measurement results of TG-DTA (Thermogravimetric Analysis-Differential Thermal Analysis) of the transparent polyfluorene-imide-based film produced in Example 1. FIG.

Claims (11)

一種積層體，其係包含透明樹脂膜與保護膜而成者，上述透明樹脂膜係包含選自由聚醯亞胺、聚醯胺及聚醯胺醯亞胺所組成之群中之至少1種及溶劑而成者，上述保護膜貼合於上述透明樹脂膜之至少一個面，且根據數式(1)而算出之與透明樹脂膜相接之保護膜表面之算術平均波紋度Wa為30 nm以下， 數式(1)： [數3] [數式(1)中，Zw(x，y)表示根據保護膜表面之二維高度資料，使用截止值為20 μm、振幅傳遞率為50%之高斯濾波器而獲得之表面起伏之各點之高度，lx 、ly 分別表示x、y方向之測定區域之範圍]。A laminated body comprising a transparent resin film and a protective film, the transparent resin film comprising at least one selected from the group consisting of polyimide, polyimide, and polyimide; and In the case of a solvent, the protective film is bonded to at least one surface of the transparent resin film, and the arithmetic mean waviness Wa of the surface of the protective film connected to the transparent resin film calculated according to formula (1) is 30 nm or less. , Equation (1): [Equation 3] [In Equation (1), Zw (x, y) represents the points of the surface undulation obtained by using a Gaussian filter with a cutoff value of 20 μm and an amplitude transmission rate of 50% based on the two-dimensional height data of the surface of the protective film. Height, l x and l y respectively represent the range of the measurement area in the x and y directions]. 如請求項1之積層體，其中透明樹脂膜之作為利用熱重-示差熱測定之自120℃至250℃之質量減少率而算出之殘留溶劑量S為0.001質量%以上。For example, the multilayer body according to claim 1, wherein the amount of residual solvent S of the transparent resin film calculated as a mass reduction rate from 120 ° C to 250 ° C by thermogravimetric-differential calorimetry is 0.001% by mass or more. 如請求項1之積層體，其中保護膜的定義為藉由測定溫度為140℃之凝膠滲透層析法進行測定而獲得之圖的Log M為2.82至3.32之面積相對於總面積之比率的低分子成分量W為0.4%以下。For example, the laminated body of claim 1, wherein the protective film is defined as a ratio of an area of Log M of 2.82 to 3.32 to a total area of a graph obtained by measurement by gel permeation chromatography at a measurement temperature of 140 ° C. The low molecular component amount W is 0.4% or less. 如請求項2之積層體，其中保護膜的定義為藉由測定溫度為140℃之凝膠滲透層析法進行測定而獲得之圖的Log M為2.82至3.32之面積相對於總面積之比率的低分子成分量W為0.4%以下。For example, the laminated body of claim 2, wherein the protective film is defined as a ratio of an area of Log M of 2.82 to 3.32 to a total area of a graph obtained by measurement by gel permeation chromatography at a measurement temperature of 140 ° C. The low molecular component amount W is 0.4% or less. 如請求項1至4中任一項之積層體，其中透明樹脂膜包含1種以上之溶劑，且該溶劑中沸點最高之溶劑之沸點為120～300℃。For example, the laminated body according to any one of claims 1 to 4, wherein the transparent resin film contains more than one solvent, and the solvent having the highest boiling point in the solvent has a boiling point of 120 to 300 ° C. 如請求項1至4中任一項之積層體，其中透明樹脂膜包含至少一種選自由N,N-二甲基乙醯胺、γ-丁內酯、N-甲基吡咯啶酮、環戊酮、乙酸丁酯及乙酸戊酯所組成之群中之溶劑。The laminated body according to any one of claims 1 to 4, wherein the transparent resin film contains at least one selected from the group consisting of N, N-dimethylacetamide, γ-butyrolactone, N-methylpyrrolidone, and cyclopentyl Solvent in a group consisting of ketone, butyl acetate and amyl acetate. 如請求項5之積層體，其中透明樹脂膜包含至少一種選自由N,N-二甲基乙醯胺、γ-丁內酯、N-甲基吡咯啶酮、環戊酮、乙酸丁酯及乙酸戊酯所組成之群中之溶劑。The laminated body according to claim 5, wherein the transparent resin film comprises at least one selected from the group consisting of N, N-dimethylacetamide, γ-butyrolactone, N-methylpyrrolidone, cyclopentanone, butyl acetate, and Solvent in the group consisting of amyl acetate. 如請求項1至4中任一項之積層體，其中保護膜為聚烯烴系樹脂膜。The laminated body according to any one of claims 1 to 4, wherein the protective film is a polyolefin-based resin film. 如請求項5之積層體，其中保護膜為聚烯烴系樹脂膜。The laminated body according to claim 5, wherein the protective film is a polyolefin resin film. 如請求項6之積層體，其中保護膜為聚烯烴系樹脂膜。The laminated body according to claim 6, wherein the protective film is a polyolefin resin film. 如請求項7之積層體，其中保護膜為聚烯烴系樹脂膜。The laminated body according to claim 7, wherein the protective film is a polyolefin resin film.
TW108104357A 2018-02-14 2019-02-11 laminate TWI791761B (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2018-024552 2018-02-14
JP2018024552 2018-02-14
JP2018123279A JP6400875B1 (en) 2018-02-14 2018-06-28 Laminate
JP2018-123279 2018-06-28

Publications (2)

Publication Number Publication Date
TW201936382A true TW201936382A (en) 2019-09-16
TWI791761B TWI791761B (en) 2023-02-11

Family

ID=63708729

Family Applications (1)

Application Number Title Priority Date Filing Date
TW108104357A TWI791761B (en) 2018-02-14 2019-02-11 laminate

Country Status (4)

Country Link
JP (2) JP6400875B1 (en)
KR (2) KR101989112B1 (en)
CN (1) CN110154475B (en)
TW (1) TWI791761B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6434186B1 (en) * 2018-05-08 2018-12-05 住友化学株式会社 Laminated body and method for producing the same

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2510939A1 (en) * 1981-08-07 1983-02-11 Oriol Jean Applying film covered labels to thermoplastic mouldings - using continuous film to position labels in mould cavity
JP2000009931A (en) * 1998-06-22 2000-01-14 Konica Corp Protective film for polarizer
JP4432544B2 (en) * 2004-03-09 2010-03-17 東レ株式会社 Hard-coated multilayer sheet, building material window glass using the same, and flat panel display
JP5519923B2 (en) * 2008-09-24 2014-06-11 積水化学工業株式会社 Surface protection film
JP5402254B2 (en) 2009-02-13 2014-01-29 東洋紡株式会社 Multilayer polyimide film
JP5352316B2 (en) * 2009-03-30 2013-11-27 富士フイルム株式会社 Light scattering film, polarizing plate, image display device, and transmissive / semi-transmissive liquid crystal display device
KR101258549B1 (en) * 2009-05-14 2013-05-02 가부시키가이샤 지로 코포레토 프란 Polarizer protection film, polarizing plate and liquid crystal display element
WO2013062996A1 (en) * 2011-10-24 2013-05-02 3M Innovative Properties Company Micro-structured optically clear adhesives
JP6261181B2 (en) * 2011-12-19 2018-01-17 日東電工株式会社 Carrier film and laminate for transparent conductive film
JP5932098B2 (en) * 2014-04-17 2016-06-08 日東電工株式会社 Transparent conductive film
JP6354310B2 (en) 2014-05-13 2018-07-11 東洋紡株式会社 Polyimide film for laminate formation
JP2016087799A (en) 2014-10-29 2016-05-23 東レ・デュポン株式会社 Long-sized laminate for high frequency circuit board, and method for manufacturing the same
WO2017006739A1 (en) * 2015-07-03 2017-01-12 三井金属鉱業株式会社 Roughened copper foil, copper-clad laminate and printed wiring board
JP6808401B2 (en) * 2015-08-31 2021-01-06 日鉄ケミカル＆マテリアル株式会社 Manufacturing method of polyimide substrate film with functional layer
JP6917187B2 (en) * 2016-05-10 2021-08-11 住友化学株式会社 Optical film and flexible devices using it

Also Published As

Publication number Publication date
CN110154475B (en) 2021-11-02
CN110154475A (en) 2019-08-23
TWI791761B (en) 2023-02-11
JP2019137032A (en) 2019-08-22
KR101989112B1 (en) 2019-06-13
JP2019137035A (en) 2019-08-22
KR20190098732A (en) 2019-08-22
JP6400875B1 (en) 2018-10-03

Similar Documents

Publication Publication Date Title
JP7134598B2 (en) Optical film, flexible device member provided with the same, and resin composition
TWI758399B (en) Optical film and method for producing optical film
JP6538259B1 (en) Laminate
JP7249732B2 (en) Optical film and method for producing optical film
TW201734132A (en) Polyamic acid, polyimide, polyamic acid solution, polyimide laminate, flexible device substrate, and method for producing them
TWI748038B (en) Polyamideimide resin and optical member containing the polyamideimide resin
JP2019151856A (en) Optical film and optical member using optical film
CN112601777B (en) Polyimide resin, polyimide varnish and polyimide film
JP7257901B2 (en) optical film
TW201922848A (en) Polyimide resin, polyimide varnish and polyimide film
JP2021042382A (en) Polyimide films and electronic devices
TW201940345A (en) Film roll which is less likely to cause uneven peeling when the protective film is peeled off, and which has good appearance and visibility
JP7172981B2 (en) BASE FILM FOR TRANSPARENT ELECTRODE AND METHOD FOR MANUFACTURING THE SAME
JP7053904B2 (en) Optical laminate and display device
JP2020164704A (en) Polyamic acid, polyamic acid solution, polyimide, polyimide film, laminate and flexible device, and method for manufacturing polyimide film
TW201400527A (en) High-transparency polyimide resin
TWI791761B (en) laminate
JP6846148B2 (en) Polyimide precursor solution and its production method, polyimide film production method and laminate production method
JP2019038916A (en) SOLUBLE TRANSPARENT POLYIMIDE POLYMERIZED IN γ-BUTYROLACTONE SOLVENT
JP2019085549A (en) Optical film
JP2020019935A (en) Manufacturing method of polyamide resin powder and polyamide resin composition