TWI734849B - Optical film and image display device - Google Patents

Optical film and image display device Download PDF

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TWI734849B
TWI734849B TW106135143A TW106135143A TWI734849B TW I734849 B TWI734849 B TW I734849B TW 106135143 A TW106135143 A TW 106135143A TW 106135143 A TW106135143 A TW 106135143A TW I734849 B TWI734849 B TW I734849B
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layer
optical film
resin
film
resin layer
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TW106135143A
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TW201827231A (en
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磯嶋征一
小林篤弘
橋本裕介
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日商大日本印刷股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Laminated Bodies (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

若根據本發明之一態樣，則可提供一種光學膜10，該光學膜10為使用於影像顯示裝置之可折疊的透光性光學膜10，該光學膜10具備有基材11與樹脂層12，該樹脂層12為於基材11之一面11A側自基材11側從第1層依序積層至第n層(n為3以上之整數)的多層構造，樹脂層12中之第1層~第n層各層的壓痕硬度從第1層至第n層依序變大。 According to one aspect of the present invention, an optical film 10 can be provided. The optical film 10 is a foldable translucent optical film 10 used in an image display device. The optical film 10 includes a substrate 11 and a resin layer. 12. The resin layer 12 has a multilayer structure in which one surface 11A of the substrate 11 is laminated from the first layer to the nth layer (n is an integer greater than or equal to 3) in sequence from the substrate 11 side. The first resin layer 12 is The indentation hardness of each layer from the first layer to the nth layer increases sequentially from the first layer to the nth layer.

Description

光學膜及影像顯示裝置 Optical film and image display device

本案主張先申請之日本申請案：特願2016-203116(申請日：2016年10月14日)之優先權，藉由援引其揭示內容整體來作為本說明書之一部份。 This case claims the priority of Japanese application filed first: Japanese Patent Application 2016-203116 (application date: October 14, 2016), and the entire disclosure is cited as a part of this specification.

本發明係關於一種光學膜及影像顯示裝置。 The invention relates to an optical film and an image display device.

自以往智慧型手機或平板終端等影像顯示裝置即眾所周知，目前正進行可折疊之影像顯示裝置的開發。通常，智慧型手機或平板終端等會被蓋玻璃覆蓋，但玻璃通常硬度高，無法彎曲，因此當將蓋玻璃使用於影像顯示裝置之情形時，若想要折疊，則發生破裂之可能性高。因此，對於可折疊之影像顯示裝置，正研究使用具備可彎曲之基材與樹脂層的可折疊之光學膜來代替蓋玻璃(例如，參照日本特開2016-125063號公報)。 Image display devices such as smartphones or tablet terminals are well known from the past, and foldable image display devices are currently being developed. Generally, smart phones or tablet terminals are covered by cover glass, but the glass is usually hard and cannot be bent. Therefore, when the cover glass is used in an image display device, if it is to be folded, the possibility of breakage is high. . Therefore, for foldable image display devices, research is underway to use a foldable optical film with a bendable substrate and a resin layer to replace the cover glass (for example, refer to Japanese Patent Application Laid-Open No. 2016-125063).

對於此種使用於可折疊之影像顯示裝置的光學膜，要求優異之折疊性、鉛筆硬度及耐撞擊性。對於耐撞擊性，由於有時在施加撞擊於光學膜之表面時，光學膜之表面會產生凹陷，又有時於影像顯示裝置中較光學膜存在於更內部之構件(例如，有機發光二極體面板等顯示面板)會受到損傷，因此，要求當施加撞擊於光學膜之表面時，膜表面之凹陷受到抑制，且較光學膜存在於影像顯示裝置之更內部的構件不會受到損傷的耐撞擊性。 For such optical films used in foldable image display devices, excellent foldability, pencil hardness, and impact resistance are required. As for impact resistance, sometimes when the impact is applied to the surface of the optical film, the surface of the optical film will produce depressions, and sometimes in the image display device, there are more internal components (for example, organic light-emitting diodes) than the optical film. Display panels such as body panels will be damaged. Therefore, it is required that when an impact is applied to the surface of the optical film, the dents on the surface of the film are suppressed, and the optical film is more resistant to damage to the internal components of the image display device. Impact.

另一方面，若以樹脂層成為內側之方式將光學膜折疊，則會有樹脂層表面發生皺折或細微裂縫(裂紋)之虞。因此，對於光學膜，進一步要求優異之彎曲性。這裡的皺折，係指當光學膜經折疊時於光學膜之彎曲部觀察到 之皺折，而非光學膜經折疊然後再次使光學膜回復成平坦狀時所觀察到之皺折。 On the other hand, if the optical film is folded so that the resin layer becomes the inside, wrinkles or fine cracks (cracks) may occur on the surface of the resin layer. Therefore, optical films are further required to have excellent flexibility. The wrinkle here refers to the wrinkle observed in the curved part of the optical film when the optical film is folded, and the wrinkle observed when the non-optical film is folded and then the optical film is restored to a flat shape again.

並且，如智慧型手機或平板終端此類之影像顯示裝置，與大型電視不同，由於有時也會放入衣服之口袋或袋子，故此種影像顯示裝置之顯示面有時也會受到放入口袋或袋子內之其他物品等的摩擦。因此，對於光學膜，進一步要求優異之耐擦傷性。 In addition, image display devices such as smart phones or tablet terminals are different from large TVs. Because they are sometimes put into clothing pockets or bags, the display surface of such image display devices may also be put into pockets. Or friction with other items in the bag. Therefore, optical films are further required to have excellent scratch resistance.

然而，除了優異之折疊性、優異之鉛筆硬度及優異之耐撞擊性外，現況亦尚無法得到具有優異之彎曲性及優異之耐擦傷性的光學膜。 However, in addition to excellent foldability, excellent pencil hardness, and excellent impact resistance, an optical film with excellent flexibility and excellent scratch resistance has not yet been obtained.

本發明係為了解決上述問題而完成者。亦即，目的在於提供一種具有優異之折疊性、優異之鉛筆硬度、優異之耐撞擊性、優異之彎曲性及優異之耐擦傷性的可折疊之光學膜，及具備該光學膜之影像顯示裝置。 The present invention was completed in order to solve the above-mentioned problems. That is, the purpose is to provide a foldable optical film with excellent foldability, excellent pencil hardness, excellent impact resistance, excellent flexibility, and excellent scratch resistance, and an image display device with the optical film .

本發明人等經對上述課題不斷潛心研究後，結果發現若將樹脂層積層3層以上，且將樹脂層之壓痕硬度朝光學膜之表面側慢慢地提高，則可得到優異之折疊性、優異之鉛筆硬度、優異之耐撞擊性、優異之彎曲性及優異之耐擦傷性。本發明係基於此種見解而完成者。 After intensive research on the above subject, the inventors found that if three or more resin layers are laminated and the indentation hardness of the resin layer is gradually increased toward the surface of the optical film, excellent foldability can be obtained. , Excellent pencil hardness, excellent impact resistance, excellent bendability and excellent scratch resistance. The present invention was completed based on this knowledge.

若根據本發明之一態樣，則提供一種光學膜，該光學膜為使用於影像顯示裝置之可折疊的透光性光學膜，具備從第1層依序積層至第n層(n為3以上之整數)之多層構造的樹脂層，前述樹脂層中之前述第1層~前述第n層各層的壓痕硬度從前述第1層至前述第n層依序變大。 According to one aspect of the present invention, an optical film is provided. The optical film is a foldable light-transmitting optical film used in an image display device. In the resin layer of the multilayer structure of the above integer), the indentation hardness of each of the first layer to the nth layer in the resin layer increases sequentially from the first layer to the nth layer.

於上述光學膜，可進一步具備有設置於前述樹脂層之前述第1層側的基材。 The optical film may further include a substrate provided on the first layer side of the resin layer.

於上述光學膜，n可為3，於前述樹脂層中，前述第1層之壓痕硬度可為1MPa以上100MPa以下，第2層之壓痕硬度可為10MPa以上500MPa以下，第3層之壓痕硬度可為100MPa以上1000MPa以下。 In the above-mentioned optical film, n can be 3. In the aforementioned resin layer, the indentation hardness of the first layer can be 1 MPa or more and 100 MPa or less, the indentation hardness of the second layer can be 10 MPa or more and 500 MPa or less. The trace hardness can be above 100 MPa and below 1000 MPa.

於上述光學膜，n可為4，於前述樹脂層中，前述第1層之壓痕硬 度可為1MPa以上100MPa以下，第2層之壓痕硬度可為10MPa以上300MPa以下，第3層之壓痕硬度可為50MPa以上500MPa以下，第4層之壓痕硬度可為100MPa以上1000MPa以下。 In the above-mentioned optical film, n can be 4. In the aforementioned resin layer, the indentation hardness of the first layer can be 1 MPa or more and 100 MPa or less, and the indentation hardness of the second layer can be 10 MPa or more and 300 MPa or less. The indentation hardness can be from 50MPa to 500MPa, and the indentation hardness of the fourth layer can be from 100MPa to 1000MPa.

於上述光學膜，前述光學膜之楊氏係數可為3GPa以上。 In the above-mentioned optical film, the Young's coefficient of the above-mentioned optical film may be 3 GPa or more.

於上述光學膜，前述光學膜之黃色指數可為15以下。 In the above-mentioned optical film, the yellow index of the above-mentioned optical film may be 15 or less.

對於上述光學膜，以前述第1層較前述n層更位於鈉玻璃板側之方式將前述光學膜放置在厚度0.7mm之鈉玻璃板上，從高度30cm之位置使重量100g及直徑30mm之鐵球掉落至前述樹脂層之前述第n層的表面，於此情形時，較佳於前述第n層之表面不會產生凹陷，且於前述鈉玻璃板不會產生裂縫。 For the above optical film, place the optical film on a soda glass plate with a thickness of 0.7mm in such a way that the first layer is located on the side of the soda glass plate with a thickness of 0.7mm. The ball falls on the surface of the nth layer of the resin layer. In this case, it is preferable that no depression is generated on the surface of the nth layer and no cracks are generated on the soda glass plate.

對於上述光學膜，對前述樹脂層之前述第n層表面進行使用鋼絲絨施加1kg/cm2之負載且同時往返摩擦10次的抗鋼絲絨測試，於此情形時，較佳於前述第n層之表面皆確認不到裂縫及損傷。 For the above-mentioned optical film, the surface of the nth layer of the resin layer is subjected to a steel wool resistance test using steel wool to apply a load of 1 kg/cm 2 and rubbing 10 times at the same time. In this case, it is better than the nth layer No cracks and damage can be confirmed on the surface.

於上述光學膜，以前述光學膜相對向之邊部的間隔成為6mm之方式於25℃反覆進行10萬次180°折疊測試，於此情形時，較佳不會產生裂縫或斷裂。 For the optical film, the 180° folding test is repeated 100,000 times at 25°C so that the distance between the opposing edges of the optical film becomes 6mm. In this case, it is preferable that no cracks or breaks occur.

於上述光學膜，前述基材可為由聚醯亞胺系樹脂、聚醯胺系樹脂或此等之混合物構成之基材。 In the above-mentioned optical film, the aforementioned substrate may be a substrate composed of a polyimide-based resin, a polyamide-based resin, or a mixture of these.

若根據本發明之其他態樣，則可提供一種影像顯示裝置，該影像顯示裝置為可折疊之影像顯示裝置，其特徵在於：具備顯示面板與較前述顯示面板更配置於觀察者側之上述光學膜，前述光學膜之前述樹脂層中的前述第n層較前述第1層更位於觀察者側。 According to other aspects of the present invention, an image display device can be provided. The image display device is a foldable image display device, and is characterized in that it has a display panel and the above-mentioned optical device that is more disposed on the observer side than the aforementioned display panel. Film, the n-th layer in the resin layer of the optical film is located on the observer side more than the first layer.

於上述影像顯示裝置，前述顯示面板可為有機發光二極體面板。 In the aforementioned image display device, the aforementioned display panel may be an organic light emitting diode panel.

若根據本發明之一態樣，則可提供一種具有優異之折疊性、優異之鉛筆硬度、優異之耐撞擊性、優異之彎曲性及優異之耐擦傷性的可折疊之光學膜。又，若根據本發明之其他態樣，則可提供一種具備此種光學膜之影像顯 示裝置。 According to one aspect of the present invention, a foldable optical film with excellent foldability, excellent pencil hardness, excellent impact resistance, excellent flexibility, and excellent scratch resistance can be provided. Furthermore, according to other aspects of the present invention, an image display device with such an optical film can be provided.

10，20，60，80‧‧‧光學膜 10, 20, 60, 80‧‧‧Optical film

10A，12A，20A，21A，60A，61A，80A，81A‧‧‧表面 10A, 12A, 20A, 21A, 60A, 61A, 80A, 81A‧‧‧surface

11‧‧‧基材 11‧‧‧Substrate

12，21，61，81‧‧‧樹脂層 12, 21, 61, 81‧‧‧Resin layer

12B，21B，61B，81B‧‧‧第1層 12B, 21B, 61B, 81B‧‧‧The first floor

12C，21C，61C，81C‧‧‧第2層 12C, 21C, 61C, 81C‧‧‧The second floor

12D，21D，61D，81D‧‧‧第3層 12D, 21D, 61D, 81D‧‧‧3rd floor

21E，81E‧‧‧第4層 21E, 81E‧‧‧4th floor

30，90‧‧‧影像顯示裝置 30，90‧‧‧Video display device

33‧‧‧顯示面板 33‧‧‧Display Panel

圖1為第1實施形態之光學膜的概略構成圖。 Fig. 1 is a schematic configuration diagram of the optical film of the first embodiment.

圖2係示意地表示折疊測試狀態之圖。 Fig. 2 is a diagram schematically showing the folding test state.

圖3係第1實施形態之其他光學膜的概略構成圖。 Fig. 3 is a schematic configuration diagram of another optical film of the first embodiment.

圖4係第1實施形態之影像顯示裝置的概略構成圖。 Fig. 4 is a schematic configuration diagram of the video display device of the first embodiment.

圖5係第2實施形態之附離型膜之光學膜的概略構成圖。 Fig. 5 is a schematic configuration diagram of an optical film with a release film of the second embodiment.

圖6係第2實施形態之其他附離型膜之光學膜的概略構成圖。 Fig. 6 is a schematic configuration diagram of another optical film with a release film according to the second embodiment.

圖7係第2實施形態之影像顯示裝置的概略構成圖。 Fig. 7 is a schematic configuration diagram of an image display device of the second embodiment.

[第1實施形態] [First Embodiment]

以下，一邊參照圖式，一邊說明本發明之第1實施形態的光學膜及影像顯示裝置。於本說明書中，「膜」、「片」等用語僅是基於稱呼之不同，而非用以區分彼此。因此，例如，「膜」會以亦包含也被稱為片之類的構件的意義來使用。圖1為本實施形態之光學膜的概略構成圖，圖2為示意地表示折疊測試狀態之圖，圖3為本實施形態之其他光學膜的概略構成圖。 Hereinafter, the optical film and the image display device of the first embodiment of the present invention will be described with reference to the drawings. In this manual, terms such as "membrane" and "sheet" are only based on the difference of titles, not to distinguish each other. Therefore, for example, "membrane" is used in the sense that it also includes members such as sheets. Fig. 1 is a schematic configuration diagram of the optical film of the embodiment, Fig. 2 is a diagram schematically showing a folding test state, and Fig. 3 is a schematic configuration diagram of another optical film of the embodiment.

<<<光學膜>>> <<<Optical Film>>>

圖1所示之光學膜10被使用於影像顯示裝置，可折疊且具有透光性。本說明書中之「透光性」，意指使光透射之性質，例如包含總光線透射率為50%以上，較佳為70%以上，更佳為80%以上，尤佳為90%以上。所謂透光性，並不一定要是透明，亦可為半透明。 The optical film 10 shown in FIG. 1 is used in an image display device, is foldable and has light transmittance. The "transmittance" in this specification refers to the property of transmitting light, for example, including the total light transmittance of 50% or more, preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more. The so-called light transmittance does not have to be transparent, but may be translucent.

圖1所示之光學膜10，具備有基材11與樹脂層12，該樹脂層12係於基材11之一面11A側自基材11側從第1層依序積層至第n層(n為3以上之整數) 的多層構造。另，光學膜10雖然具備有基材11，但是如於第2實施形態說明般，光學膜亦可不具備基材。 The optical film 10 shown in FIG. 1 includes a substrate 11 and a resin layer 12, and the resin layer 12 is laminated on one surface 11A side of the substrate 11 from the first layer to the nth layer (n Is an integer of 3 or more) multilayer structure. In addition, although the optical film 10 is equipped with the base material 11, as demonstrated in 2nd Embodiment, the optical film may not have a base material.

光學膜10之表面10A成為樹脂層12之表面12A。於光學膜10中，如後述般由於樹脂層12之第3層12D成為最上層，因此，光學膜10之表面10A成為第3層12D之表面。另，於本說明書中，由於光學膜之表面係作為意指光學膜單側之表面者來使用，因此，為了與光學膜之表面區分，而將光學膜表面的相反側之面稱為背面。光學膜10之背面10B成為基材11之一面11A的相反側面亦即另一面11B。 The surface 10A of the optical film 10 becomes the surface 12A of the resin layer 12. In the optical film 10, since the third layer 12D of the resin layer 12 becomes the uppermost layer as described later, the surface 10A of the optical film 10 becomes the surface of the third layer 12D. In addition, in this specification, since the surface of the optical film is used as meaning the surface of one side of the optical film, in order to distinguish it from the surface of the optical film, the surface on the opposite side of the optical film surface is referred to as the back surface. The back surface 10B of the optical film 10 becomes the opposite side surface of the one surface 11A of the base material 11, that is, the other surface 11B.

光學膜10雖然能夠折疊，但具體而言，較佳即使是對光學膜10反覆進行過10萬次下文說明之折疊測試的情形時，於光學膜亦不會產生裂縫或斷裂，更佳即使是經反覆進行過20萬次折疊測試的情形時，於光學膜10亦不會產生裂縫或斷裂，再更佳即使是經反覆進行過100萬次的情形時，於光學膜亦不會產生裂縫或斷裂。若當對光學膜10反覆進行過10萬次折疊測試之情形時，於光學膜10產生裂縫等，則光學膜10之折疊性不足夠。折疊測試可以將光學膜10折疊成使樹脂層12成為內側之方式來進行，又，亦可以將光學膜10折疊成使樹脂層12成為外側之方式來進行，但無論是何種情形，皆較佳於光學膜不會產生裂縫或斷裂。 Although the optical film 10 can be folded, specifically, it is preferable that even if the optical film 10 is repeatedly subjected to the folding test described below 100,000 times, the optical film will not be cracked or broken, and even more preferably After repeated 200,000 times of folding test, the optical film 10 will not crack or break, and even better, even after repeated 1 million times, there will be no cracks or cracks in the optical film. fracture. If the optical film 10 is repeatedly subjected to 100,000 times of folding tests, and cracks or the like are generated in the optical film 10, the foldability of the optical film 10 is insufficient. The folding test can be carried out by folding the optical film 10 so that the resin layer 12 becomes the inner side, and it can also be carried out by folding the optical film 10 so that the resin layer 12 becomes the outer side, but in any case, it is better. Better than the optical film will not crack or break.

當於光學膜10之一面側透過黏著層或接著層設置有偏光板等其他之膜的情形時，將其他之膜與黏著層或接著層一起剝離後，進行折疊測試。其他之膜的剝離，例如可以下述方式進行。首先，將其他之膜透過黏著層或接著層附著於光學膜而成的積層體浸於80℃之溫水10秒，然後取出，冷卻至室溫左右。反覆進行數次此動作後，將切刀之刀尖刺入認為是光學膜與其他之膜的界面的部位，形成開端，慢慢地將其剝下，藉此可將黏著層或接著層及其他之膜剝離。另，即使具有此種剝離步驟，對於折疊測試之結果亦不會有重大影響。 When the adhesive layer or adhesive layer is provided with other films such as a polarizing plate on one side of the optical film 10, the other films are peeled off together with the adhesive layer or adhesive layer, and then a folding test is performed. The peeling of other films can be performed, for example, in the following manner. First, the laminate formed by attaching other films to the optical film through the adhesive layer or the adhesive layer is immersed in warm water at 80°C for 10 seconds, then taken out and cooled to about room temperature. After repeating this action several times, pierce the tip of the cutter into the part that is believed to be the interface between the optical film and other films to form a start, and then slowly peel it off, so that the adhesive layer or adhesive layer and Other films peeled off. In addition, even with such a peeling step, it will not have a significant impact on the results of the folding test.

折疊測試係以下述方式進行。如圖2(A)所示，於折疊測試中，首先將切成30mm×100mm大小之光學膜10的邊部10C與和邊部10C相對向之邊部10D用平行配置之固定部15分別加以固定。又，如圖2(A)所示，固定部15可於水平方向滑動。 The folding test was performed in the following manner. As shown in Figure 2(A), in the folding test, first, the side 10C of the optical film 10 cut into a size of 30mm×100mm and the side 10D facing the side 10C are respectively attached to the fixed portion 15 arranged in parallel. fixed. Moreover, as shown in FIG. 2(A), the fixed portion 15 can slide in the horizontal direction.

接著，如圖2(B)所示，以互相接近之方式移動固定部15，使光學膜10折疊變形，並且如圖2(C)所示，使固定部15移動至光學膜10受到固定部15固定之相對向的2個邊部之間隔成為6mm之位置後，使固定部15向反方向移動，消除光學膜10之變形。 Next, as shown in FIG. 2(B), move the fixed portion 15 to approach each other to fold and deform the optical film 10, and move the fixed portion 15 to the fixed portion of the optical film 10 as shown in FIG. 2(C) When the distance between the two opposite sides of the fixed 15 becomes 6 mm, the fixed portion 15 is moved in the opposite direction to eliminate the deformation of the optical film 10.

如圖2(A)~(C)所示，可藉由移動固定部15，來使光學膜10作180°折疊。又，以光學膜10之彎曲部10E不會超出固定部15之下端的方式進行折疊測試，且將固定部15最接近時之間隔控制在6mm，藉此可使光學膜10相對向之2個邊部的間隔為6mm。此情形時，將彎曲部10E之外徑視為6mm。另，光學膜10之厚度由於為遠小於固定部15之間隔(6mm)的值，故可將光學膜10之折疊測試結果視為不會受到因光學膜10厚度之不同所造成的影響。 As shown in Fig. 2(A)~(C), the optical film 10 can be folded by 180° by moving the fixing part 15. In addition, the folding test is performed so that the curved portion 10E of the optical film 10 does not extend beyond the lower end of the fixed portion 15, and the interval when the fixed portion 15 is closest to each other is controlled to 6mm, so that the two optical films 10 can face each other The edge spacing is 6mm. In this case, the outer diameter of the curved portion 10E is regarded as 6 mm. In addition, since the thickness of the optical film 10 is much smaller than the interval (6 mm) of the fixing portion 15, the folding test result of the optical film 10 can be regarded as not being affected by the difference in the thickness of the optical film 10.

關於光學膜10，當將切成100mm×100mm大小之光學膜10以第1層較第n層更位於鈉玻璃板側之方式放置在厚度0.7mm之鈉玻璃板上，從高度30cm之位置使重量100g、直徑30mm之鐵球掉落在樹脂層12第n層之表面的情形時，較佳於第n層之表面不會產生凹陷，且於鈉玻璃板不會產生裂縫。 Regarding the optical film 10, when the optical film 10 cut into a size of 100mm×100mm is placed on a soda glass plate with a thickness of 0.7mm in such a way that the first layer is located on the side of the soda glass plate than the nth layer, it is used from a height of 30cm. When an iron ball weighing 100 g and having a diameter of 30 mm falls on the surface of the nth layer of the resin layer 12, it is preferable that no dents are formed on the surface of the nth layer, and no cracks are formed on the soda glass plate.

光學膜10之表面10A(樹脂層12之表面12A)於以JIS K5600-5-4：1999規定之鉛筆硬度測試中測量時的硬度(鉛筆硬度)較佳為3H以上，更佳為5H，再更佳為6H以上。鉛筆硬度測試係藉由下述方式進行：對切成50mm×100mm大小之光學膜的表面使用鉛筆硬度測試機(製品名「鉛筆抓刮塗膜硬度測試機(電動式)」，東洋精機製作所股份有限公司製)，對鉛筆(製品名「uni」，三菱鉛筆股份有限公司製)施加750g之負載，且同時以1mm/秒之移動 速度使鉛筆移動。使鉛筆硬度為於鉛筆硬度測試中光學膜表面沒有發生損傷之最高硬度。另，於測量鉛筆硬度時，雖使用複數根硬度不同之鉛筆來進行，但每1根鉛筆會進行5次鉛筆硬度測試，當5次之中有4次以上光學膜表面沒有發生損傷之情形時，判斷此硬度之鉛筆不會對光學膜表面造成損傷。上述損傷係指於螢光燈下對進行過鉛筆硬度測試之光學膜的表面進行透射觀察所目視辨認到者。 The hardness (pencil hardness) of the surface 10A of the optical film 10 (the surface 12A of the resin layer 12) when measured in the pencil hardness test specified in JIS K5600-5-4: 1999 is preferably 3H or more, more preferably 5H, and More preferably, it is 6H or more. The pencil hardness test is performed by using a pencil hardness tester (product name "Pencil scratch coating film hardness tester (electric type)", Toyo Seiki Seisakusho Co., Ltd. Co., Ltd.), apply a load of 750g to the pencil (product name "uni", manufactured by Mitsubishi Pencil Co., Ltd.), and at the same time move the pencil at a movement speed of 1mm/sec. Make the pencil hardness the highest hardness at which no damage occurs on the surface of the optical film in the pencil hardness test. In addition, when measuring the pencil hardness, although multiple pencils with different hardness are used, each pencil will be tested for 5 times. When the optical film surface is not damaged 4 times out of 5 times , It is judged that the pencil with this hardness will not damage the surface of the optical film. The above-mentioned damage refers to what is visually recognized by the transmission observation of the surface of the optical film that has undergone a pencil hardness test under a fluorescent lamp.

於對光學膜10以樹脂層12成為內側且光學膜10相對向之2個邊部的間隔成為6mm的方式進行使樹脂層12側之面折疊180°的彎曲性測試時，較佳於光學膜10之彎曲部觀察不到皺折，又於使光學膜回復至平坦狀之狀態下，較佳於光學膜10觀察不到細微之裂紋。於彎曲性測試，與折疊測試同樣地(參照圖2(C))係用固定部15分別將切成30mm×100mm大小之光學膜10相對向的邊部加以固定來進行。皺折之確認則是在將樹脂層12側之面折疊180°的狀態下，於螢光燈下藉由目視來確認。又，細微之裂紋由於是無法以目視確認之類的裂紋，故以光學顯微鏡(製品名「VHX-5000」，其恩斯公司製)觀察。 When the optical film 10 is subjected to a bending test in which the resin layer 12 side is folded 180° so that the resin layer 12 is inside and the distance between the two opposing sides of the optical film 10 is 6 mm, it is preferable to the optical film No wrinkles are observed at the bent portion of 10, and when the optical film is restored to a flat state, it is preferable that no fine cracks are observed in the optical film 10. In the bendability test, similar to the folding test (see FIG. 2(C)), the opposing sides of the optical film 10 cut into a size of 30 mm×100 mm were fixed by the fixing portion 15 respectively. The confirmation of wrinkles is confirmed by visual inspection under a fluorescent lamp in a state where the surface of the resin layer 12 side is folded 180°. In addition, since the fine cracks are cracks that cannot be visually confirmed, they were observed with an optical microscope (product name "VHX-5000", manufactured by Chines Co., Ltd.).

關於光學膜10，對樹脂層12之第n層表面進行使用#0000號之鋼絲絨(製品名「bonstar」，日本鋼絲絨公司製)施加1kg/cm2之負載且同時往返摩擦10次的耐擦傷性測試，於此情形時，較佳於第n層之表面皆確認不到裂縫及損傷。耐擦傷性測試係使用切成50mm×100mm大小之光學膜，且於用日絆公司製之Cellotape(註冊商標)將光學膜以沒有彎折或皺折之方式固定在玻璃板上使第n層成為上側的狀態下進行。 Regarding the optical film 10, the surface of the n-th layer of the resin layer 12 is made of #0000 steel wool (product name "bonstar", manufactured by Japan Steel Wool Co.), applying a load of 1 kg/cm 2 and at the same time reciprocating rubbing 10 times. In the abrasion test, in this case, it is preferable that no cracks and damage are confirmed on the surface of the nth layer. The scratch resistance test is to use an optical film cut into a size of 50mm×100mm, and use the Cellotape (registered trademark) manufactured by Nisshin Co., Ltd. to fix the optical film on the glass plate without bending or crease to make the nth layer Proceed in the upper state.

光學膜10之楊氏係數較佳為3GPa以上。若光學膜10之楊氏係數未達3GPa，則會有光學膜硬度不足之虞。光學膜10之楊氏係數係以下述方式求得。首先，將從光學膜10切下成規定大小(例如，2mm×150mm)之樣品的兩端以樣品之長邊方向成為拉伸方向的方式固定於附在Tensilon萬能測試機(製品名 「RTC-1310A」，Orientec公司製)之夾頭用治具等，使用上述Tensilon萬能測試機，將樣品以測試速度25mm/分拉伸時樣品之伸長量與負載之測量值換算成應變與應力，求出連接應變為0.5%時之應力與應變為1%時之應力的直線其斜率，藉此求出楊氏係數。使楊氏係數為測量3次所得到之值的算術平均值。光學膜10之楊氏係數的上限更佳為7GPa以下。 The Young's coefficient of the optical film 10 is preferably 3 GPa or more. If the Young's coefficient of the optical film 10 is less than 3 GPa, the hardness of the optical film may be insufficient. The Young's coefficient of the optical film 10 is obtained in the following manner. First, both ends of a sample cut from the optical film 10 into a predetermined size (for example, 2mm×150mm) are fixed to the Tensilon universal testing machine (product name "RTC- 1310A", manufactured by Orientec), use the Tensilon universal testing machine, and convert the elongation and load measurement values of the sample into strain and stress when the sample is stretched at a test speed of 25mm/min. The slope of the straight line connecting the stress when the strain is 0.5% and the stress when the strain is 1% is used to obtain the Young's coefficient. Let the Young's coefficient be the arithmetic mean of the values obtained by the three measurements. The upper limit of the Young's coefficient of the optical film 10 is more preferably 7 GPa or less.

又，當於光學膜10之一面側透過黏著層或接著層設置有偏光板等其他之膜的情形時，藉由與上述同樣之方法將其他之膜與黏著層或接著層一起剝離後，測量楊氏係數。另，即使有此種剝離步驟，對楊氏係數之測量亦不會有重大影響。 In addition, when the adhesive layer or adhesive layer is provided with other films such as a polarizing plate on one side of the optical film 10, the other films are peeled off together with the adhesive layer or adhesive layer by the same method as above, and then the measurement Young's coefficient. In addition, even if there is such a peeling step, it will not have a significant impact on the measurement of Young's coefficient.

光學膜10之黃色指數(YI)較佳為15以下。若光學膜10之YI超過15，則光學膜會明顯帶有黄色，而有無法適用於要求透明性的用途之虞。黃色指數(YI)係以下述方式算出之值：使用分光光度計(製品名「UV-3100PC」，島津製作所公司製，光源：鎢絲燈及氘燈)，從對切成50mm×100mm大小之光學膜所測得之值依據JIS Z8722：2009記載之算式計算色度三色值X、Y、Z，然後從三色值X、Y、Z依據ASTM D1925：1962記載之算式算出黃色指數。上述黃色指數(YI)係對1片光學膜測量3次，為測量3次所得到之值的算術平均值。光學膜10之黃色指數(YI)的上限更佳為10以下。 The yellow index (YI) of the optical film 10 is preferably 15 or less. If the YI of the optical film 10 exceeds 15, the optical film will be obviously yellowish, and may not be suitable for applications requiring transparency. The yellow index (YI) is a value calculated in the following way: using a spectrophotometer (product name "UV-3100PC", manufactured by Shimadzu Corporation, light source: tungsten lamp and deuterium lamp), cut into a 50mm×100mm size The measured value of the optical film is calculated according to the formula described in JIS Z8722:2009 to calculate the chromaticity tristimulus values X, Y, and Z, and then the yellow index is calculated from the tristimulus values X, Y, and Z according to the formula described in ASTM D1925:1962. The above-mentioned yellow index (YI) is measured 3 times for one optical film, and is the arithmetic average of the values obtained by the 3 times of measurement. The upper limit of the yellow index (YI) of the optical film 10 is more preferably 10 or less.

又，當於光學膜10之一面側透過黏著層或接著層設置有偏光板等其他之膜的情形時，藉由與上述同樣之方法將其他之膜與黏著層或接著層一起剝離後，測量黃色指數(YI)。另，即使具有此種剝離步驟，對黃色指數(YI)之測量亦不會有重大影響。 In addition, when the adhesive layer or adhesive layer is provided with other films such as a polarizing plate on one side of the optical film 10, the other films are peeled off together with the adhesive layer or adhesive layer by the same method as above, and then the measurement Yellow Index (YI). In addition, even with such a peeling step, it will not have a significant impact on the measurement of the yellow index (YI).

為了調整光學膜10之黃色指數(YI)，例如亦可使基材11或樹脂層12含有為黄色之補色的藍色色素。即使是因使用聚醯亞胺基材作為基材而有帶黄色之問題此類的情形，藉由使基材11或樹脂層12含有藍色色素，可降低光 學膜之黃色指數(YI)。 In order to adjust the yellow index (YI) of the optical film 10, for example, the base material 11 or the resin layer 12 may contain a blue pigment which is a complementary color of yellow. Even in cases where the polyimide substrate is used as the substrate and there is a problem of yellowing, the yellow index (YI) of the optical film can be lowered by making the substrate 11 or the resin layer 12 contain a blue pigment.

作為上述藍色色素，可為顏料或染料之任一者，例如當光學膜10使用於有機發光二極體顯示裝置之情形時，較佳兼具耐光性或耐熱性。作為上述藍色色素，多環系有機顏料或金屬錯合物有機顏料等相較於染料之分子分散，由於因紫外線所造成之分子斷裂的程度小，耐光性格外優異，因此較適於要求耐光性等之用途，更具體而言，較佳可舉酞青素系有機顏料等。惟，顏料由於是粒子分散於溶劑，故會因粒子散射而減損透明性，因此，較佳使顏料分散體之粒度在瑞立散射區域。另一方面，當重視光學膜之透明性的情形時，作為上述藍色色素，較佳使用對溶劑是作分子分散的染料。 The blue pigment may be either a pigment or a dye. For example, when the optical film 10 is used in an organic light emitting diode display device, it is preferable to have both light resistance and heat resistance. As the above-mentioned blue pigments, polycyclic organic pigments or metal complex organic pigments are more suitable for the requirement of light resistance due to the smaller degree of molecular breakage caused by ultraviolet rays and excellent light resistance compared to the molecular dispersion of dyes. For purposes such as sex, more specifically, phthalocyanin-based organic pigments and the like are preferred. However, since the pigment is particles dispersed in the solvent, the transparency will be reduced due to particle scattering. Therefore, it is better to make the particle size of the pigment dispersion in the Rayleigh scattering region. On the other hand, when the transparency of the optical film is important, it is preferable to use a dye that is molecularly dispersed in a solvent as the blue pigment.

光學膜10之波長380nm之光的透射率較佳為8%以下。若光學膜之上述透射率超過8%，則當將光學膜使用於移動終端機之情形時，會有偏光元件受到紫外線曝曬而變得容易劣化之虞。上述透射率可使用分光光度計(製品名「UV-3100PC」，島津製作所公司製，光源：鎢絲燈及氘燈)進行測量。上述透射率係對切成50mm×100mm大小之光學膜測量3次，為測量3次所得到之值的算術平均值。光學膜10之上述透射率的上限更佳為5%。另，光學膜10之上述透射率可藉由調整樹脂層12中之後述紫外線吸收劑的添加量等來達成。 The transmittance of light with a wavelength of 380 nm of the optical film 10 is preferably 8% or less. If the above-mentioned transmittance of the optical film exceeds 8%, when the optical film is used in a mobile terminal, the polarizing element may be exposed to ultraviolet rays and may be easily degraded. The above-mentioned transmittance can be measured using a spectrophotometer (product name "UV-3100PC", manufactured by Shimadzu Corporation, light source: tungsten lamp and deuterium lamp). The above-mentioned transmittance is measured 3 times for an optical film cut into a size of 50mm×100mm, and is the arithmetic mean of the values obtained from the 3 measurements. The upper limit of the transmittance of the optical film 10 is more preferably 5%. In addition, the above-mentioned transmittance of the optical film 10 can be achieved by adjusting the addition amount of an ultraviolet absorber described later in the resin layer 12 and the like.

光學膜10之霧度(haze)值(總霧度值)較佳為2.5%以下。若光學膜之上述霧度值超過2.5%，則當將光學膜使用於移動終端機之情形時，會有影像顯示面白化之虞。上述霧度值更佳為1.5%以下，再更佳為1.0%以下。另，光學膜10之上述霧度值可藉由調整樹脂層12中之後述紫外線吸收劑的添加量等來達成。 The haze value (total haze value) of the optical film 10 is preferably 2.5% or less. If the above-mentioned haze value of the optical film exceeds 2.5%, when the optical film is used in a mobile terminal, the image display surface may be whitened. The above-mentioned haze value is more preferably 1.5% or less, and still more preferably 1.0% or less. In addition, the above-mentioned haze value of the optical film 10 can be achieved by adjusting the addition amount of the ultraviolet absorber described later in the resin layer 12, and the like.

上述霧度值可使用霧度計(製品名「HM-150」，村上色彩技術研究所製)藉由依照JIS K7136：2000之方法來測量。上述霧度值係於切成50mm×100mm大小後，在沒有捲曲或皺且無指紋或灰塵等之狀態下將光學膜之 表面側設置成非光源側，對1片光學膜測量3次，將測量3次所得到之值的算術平均值作為霧度值。本說明書中之「測量3次」，並非指對相同場所測量3次，而是指測量不同之3個部位。於光學膜10，目視之表面10A為平坦，且樹脂層12亦為平坦，又膜厚之變動亦在±10%之範圍內。因此，認為藉由在切下之光學膜不同的3個部位測量霧度值，而可得到大致光學膜之面內整體之霧度值的平均值。霧度值之變動即使測量對象長達1m×3000m或為5吋智慧型手機左右之大小，皆在±10%以內。另，當無法將光學膜切成上述大小之情形時，例如，HM-150由於測量時之入口開口為20mm

Figure 106135143-A0202-12-0010-41
，故需要直徑在21mm以上之類的樣品大小。因此，亦可將光學膜適當切成22mm×22mm以上之大小。當光學膜之尺寸小的情形時，於光點不偏離之範圍慢慢地移動，或改變角度等使測量點為3個部位。 The above-mentioned haze value can be measured using a haze meter (product name "HM-150", manufactured by Murakami Color Research Institute) by a method in accordance with JIS K7136:2000. The above haze value is after cutting into a size of 50mm×100mm, setting the surface side of the optical film to the non-light source side without curls or wrinkles, fingerprints or dust, etc., and measure one optical film three times. The arithmetic mean of the values obtained by the three measurements is taken as the haze value. The "measurement 3 times" in this manual does not mean the measurement of 3 times in the same place, but the measurement of 3 different parts. In the optical film 10, the visual surface 10A is flat, and the resin layer 12 is also flat, and the variation of the film thickness is also within the range of ±10%. Therefore, it is considered that by measuring the haze value at three different locations of the cut optical film, the average value of the haze value of the entire in-plane of the optical film can be obtained. The change in haze value is within ±10% even if the measuring object is 1m×3000m or about the size of a 5-inch smart phone. In addition, when the optical film cannot be cut to the above-mentioned size, for example, HM-150 has an entrance opening of 20mm during measurement.
Figure 106135143-A0202-12-0010-41
, So a sample size of 21mm or more is required. Therefore, the optical film can also be appropriately cut into a size of 22mm×22mm or more. When the size of the optical film is small, move slowly within the range where the light spot does not deviate, or change the angle so that the measurement points are three places.

又，當於光學膜10之一面側透過黏著層或接著層設置有偏光板等其他之膜的情形時，藉由與上述同樣之方法將其他之膜與黏著層或接著層一起剝離後，測量霧度值。另，即使具有此種剝離步驟，對於霧度值之測量亦不會有重大影響。 In addition, when the adhesive layer or adhesive layer is provided with other films such as a polarizing plate on one side of the optical film 10, the other films are peeled off together with the adhesive layer or adhesive layer by the same method as above, and then the measurement Haze value. In addition, even with such a peeling step, it will not have a significant impact on the measurement of the haze value.

近年來，積極採用發光二極體(Light Emitting Diode)作為個人電腦或平板終端等影像顯示裝置之背光光源，但此發光二極體會強烈發出被稱為藍光之光。此藍光據說為波長380~495nm之光，具有接近紫外線之性質，具有很強之能量，因此不會於角膜或水晶體被吸收，到達視網膜，因而造成視網膜損傷、眼睛疲勞、影響睡眠等。因此，當將光學膜應用於影像顯示裝置之情形時，較佳在不會對顯示畫面之色調造成影響下，成為藍光遮蔽性優異者。因此，從遮蔽藍光之觀點而言，光學膜10較佳於波長380nm之分光穿透率未達1%，於波長410nm之分光穿透率未達10%，於波長440nm之分光穿透率在70%以上。其原因在於若上述於波長380nm之分光穿透率在1%以上，或於波長410nm之分光穿透率在10%以上，則有時會無法消除因藍光所造成之問題，若於波長440nm 之分光穿透率未達70%，則會對使用光學膜之影像顯示裝置其顯示畫面的色調造成影響。光學膜10可充分吸收藍光波長中波長410nm以下之波長區域的光，另一方面充分透射波長440nm以上之光，而在不會對顯示畫面之色調造成影響下，展現優異之藍光遮蔽性。又，當將此種藍光遮蔽性優異之光學膜10作為影像顯示裝置應用於有機發光二極體(OLED)顯示裝置的情形時，可有效地抑制有機發光二極體元件之劣化。 In recent years, Light Emitting Diodes have been actively used as the backlight source of image display devices such as personal computers or tablet terminals. However, the light emitting diodes strongly emit light called blue light. This blue light is said to be light with a wavelength of 380~495nm, which is close to ultraviolet and has strong energy. Therefore, it will not be absorbed by the cornea or lens and reach the retina, causing retinal damage, eye fatigue, and affecting sleep. Therefore, when the optical film is applied to an image display device, it is preferable to have an excellent blue light shielding property without affecting the hue of the display screen. Therefore, from the viewpoint of shielding blue light, the optical film 10 preferably has a spectral transmittance of less than 1% at a wavelength of 380nm, a spectral transmittance of less than 10% at a wavelength of 410nm, and a spectral transmittance of less than 10% at a wavelength of 440nm. More than 70%. The reason is that if the above-mentioned spectral transmittance at a wavelength of 380nm is above 1%, or the spectral transmittance at a wavelength of 410nm is above 10%, sometimes the problem caused by blue light cannot be eliminated. If the spectral transmittance is less than 70%, it will affect the color tone of the display screen of the image display device using the optical film. The optical film 10 can fully absorb light in the wavelength region below 410 nm in the blue wavelength, on the other hand, it can fully transmit light above 440 nm, and exhibits excellent blue light shielding properties without affecting the color tone of the display screen. In addition, when such an optical film 10 with excellent blue light shielding properties is applied to an organic light emitting diode (OLED) display device as an image display device, the deterioration of the organic light emitting diode device can be effectively suppressed.

光學膜10之透光率較佳為至波長380nm為止幾乎為0%，光的透射從波長410nm慢慢地變大，光的透射於波長440nm附近急遽變大。具體而言，例如較佳於波長410nm至440nm之間分光穿透率呈S型曲線變化。上述於波長380nm之分光穿透率更佳未達0.5%，再更佳為未達0.2%，於波長410nm之分光穿透率更佳未達7%，更佳未達5%，於波長440nm之分光穿透率更佳為75%以上，再更佳為80%以上。另，光學膜10較佳於波長420nm之分光穿透率未達50%。藉由滿足此種分光穿透率之關係，光學膜10於波長440nm附近透射率會急遽提升，可在不會對顯示畫面之色調造成影響下得到極優異之藍光遮蔽性。 The light transmittance of the optical film 10 is preferably almost 0% up to a wavelength of 380 nm. The light transmission gradually increases from a wavelength of 410 nm, and the light transmission rapidly increases near a wavelength of 440 nm. Specifically, for example, it is preferable that the spectral transmittance changes in an S-shaped curve between the wavelengths of 410 nm to 440 nm. The above-mentioned spectral transmittance at a wavelength of 380nm is preferably less than 0.5%, still more preferably less than 0.2%, and the spectral transmittance at a wavelength of 410nm is preferably less than 7%, and more preferably less than 5%, at a wavelength of 440nm The spectral transmittance is more preferably 75% or more, and even more preferably 80% or more. In addition, the optical film 10 preferably has a spectral transmittance of less than 50% at a wavelength of 420 nm. By satisfying this relationship of the spectral transmittance, the transmittance of the optical film 10 at a wavelength of 440 nm can be drastically increased, and excellent blue light shielding properties can be obtained without affecting the color tone of the display screen.

光學膜10於波長380nm之分光穿透率更佳未達0.1%，於波長410nm之分光穿透率更佳未達7%，於波長440nm之分光穿透率更佳為80%以上。 The optical film 10 preferably has a spectral transmittance of less than 0.1% at a wavelength of 380 nm, preferably has a spectral transmittance of less than 7% at a wavelength of 410 nm, and more preferably has a spectral transmittance of more than 80% at a wavelength of 440 nm.

光學膜10使用最小平方法所得到之波長415~435nm範圍的穿透譜之斜率a較佳為a>2.0。若上述斜率a為2.0以下，則有時會於藍光之光波長區域例如波長415~435nm之波長區域中無法充分將光濾除，藍光濾除效果變弱。又，亦考量到過度濾除藍光之光波長區域(波長415~435nm)的可能性，當該情形時，有時很可能會發生下述等不良情形：於影像顯示裝置之背光或發光波長區域(例如，OLED之來自波長430nm的發光)發生干涉，色調變差。上述斜率a例如可使用能夠以0.5%大小測量之分光計(製品名「UV-2450」，島津製作所公司製)，在415~435nm間，於前後1nm之間測量最低5點份量之透射率數據， 藉此來算出。 The slope a of the transmission spectrum of the optical film 10 in the wavelength range of 415 to 435 nm obtained by the least square method is preferably a>2.0. If the above-mentioned slope a is 2.0 or less, the light may not be sufficiently filtered out in the light wavelength region of blue light, such as the wavelength region of 415 to 435 nm, and the blue light filtering effect may be weakened. In addition, the possibility of excessively filtering out the blue light wavelength region (wavelength 415~435nm) is also considered. In this case, the following undesirable situations may sometimes occur: in the backlight or light-emitting wavelength region of the image display device (For example, the light emitted from OLED with a wavelength of 430nm) interferes, and the color tone deteriorates. For the above slope a, for example, a spectrometer (product name "UV-2450", manufactured by Shimadzu Corporation) that can measure the size of 0.5% can be used to measure the transmittance data of the lowest 5 points between 415 and 435 nm and between 1 nm before and after. , Use this to calculate.

光學膜10之藍光遮蔽率較佳為40%以上。若藍光遮蔽率未達40%，則有時上述起因於藍光之問題會無法充分獲得消除。上述藍光遮蔽率例如係藉由JIS T7333：2005算出之值。另，此種藍光遮蔽率，例如可藉由樹脂層12含有後述之芝麻酚型苯并***系單體來達成。 The blue light shielding rate of the optical film 10 is preferably 40% or more. If the blue light shielding rate is less than 40%, sometimes the above-mentioned problems caused by blue light cannot be fully eliminated. The above-mentioned blue light shielding rate is a value calculated by, for example, JIS T7333:2005. In addition, such a blue light shielding rate can be achieved, for example, when the resin layer 12 contains a sesamol-type benzotriazole-based monomer described later.

光學膜10之用途並無特別限定，作為光學膜10之用途，例如可列舉：智慧型手機、平板終端、個人電腦(PC)、穿戴式終端、電子看板、電視、汽車導航等影像顯示裝置。又，光學膜10亦適於車載用途。作為上述各影像顯示裝置之形態，亦適於需要可折疊、可捲曲等可撓性之用途。 The use of the optical film 10 is not particularly limited. Examples of the use of the optical film 10 include: smart phones, tablet terminals, personal computers (PCs), wearable terminals, electronic signage, televisions, car navigation and other image display devices. In addition, the optical film 10 is also suitable for in-vehicle use. As the form of each of the above-mentioned image display devices, it is also suitable for applications requiring flexibility such as foldability and rollability.

光學膜10可被切成想要之大小，但亦可為捲筒狀。當光學膜10被切成想要之大小的情形時，光學膜之大小並無特別限制，可根據影像顯示裝置顯示面之大小作適當決定。具體而言，光學膜10之大小例如可為2.8吋以上500吋以下。本說明書中之「吋」，當光學膜為四方形之情形時意指對角線之長度，為圓形之情形時則意指直徑，而為楕圓形之情形時，則意指短徑與長徑之和的平均值。這裡，當光學膜為四方形之情形時，關於求得上述之吋時的光學膜其長寬比，若作為影像顯示裝置之顯示畫面沒有問題，則並無特別限定。例如可列舉長：寬=1：1、4：3、16：10、16：9、2：1等。惟於尤其富有設計性之車載用途或電子看板，並不限定於此種長寬比。又，當光學膜10之尺寸大的情形時，從任意位置切成A5尺寸(148mm×210mm)後，再切成各測量項目之大小。 The optical film 10 can be cut into a desired size, but it can also be in a roll shape. When the optical film 10 is cut into a desired size, the size of the optical film is not particularly limited, and can be appropriately determined according to the size of the display surface of the image display device. Specifically, the size of the optical film 10 may be 2.8 inches or more and 500 inches or less, for example. "Inch" in this manual means the length of the diagonal when the optical film is square, the diameter when it is round, and the short diameter when it is elliptical. The average value of the sum of the long diameter. Here, when the optical film is a square shape, the aspect ratio of the optical film when the above-mentioned time is obtained is not particularly limited as long as there is no problem as the display screen of the image display device. For example, length:width=1:1, 4:3, 16:10, 16:9, 2:1, etc. can be listed. However, especially for the design of in-vehicle use or electronic signage, it is not limited to this aspect ratio. Moreover, when the size of the optical film 10 is large, it is cut into A5 size (148mm×210mm) from an arbitrary position, and then cut into the size of each measurement item.

影像顯示裝置中之光學膜10的配置部位，亦可為影像顯示裝置之內部，但較佳為影像顯示裝置之表面附近。當使用於影像顯示裝置之表面附近的情形時，光學膜10係作為用以代替蓋玻璃之覆蓋膜用。 The location of the optical film 10 in the image display device may also be inside the image display device, but is preferably near the surface of the image display device. When used near the surface of an image display device, the optical film 10 is used as a cover film instead of cover glass.

<<基材>> <<Substrate>>

基材11為具有透光性之基材。基材11之厚度較佳為10μm以上100μm以下。 若基材之厚度未達10μm，則光學膜之捲曲會變大，且硬度亦會不足，而有鉛筆硬度無法在3H以上之虞，並且，當以捲對捲(Roll to Roll)製造光學膜之情形時，由於會變得容易產生皺折，而有導致外觀惡化之虞。另一方面，若基材之厚度超過100μm，則光學膜之折疊性能將會不足，有時無法滿足後述之折疊測試的要件，又，光學膜會變重，於輕量化方面上並不佳。基材之厚度係使用掃描型電子顯微鏡(SEM)，拍攝基材之剖面，於該剖面之影像測量20處基材之厚度，將該20處厚度之算術平均值作為基材之厚度。基材11之下限更佳為25μm以上，基材11之上限更佳為80μm以下。 The substrate 11 is a substrate with translucency. The thickness of the substrate 11 is preferably 10 μm or more and 100 μm or less. If the thickness of the substrate is less than 10μm, the curl of the optical film will increase, and the hardness will be insufficient, and there is a possibility that the pencil hardness cannot be above 3H, and when the optical film is manufactured by roll to roll (Roll to Roll) In this case, since it becomes easy to produce wrinkles, the appearance may deteriorate. On the other hand, if the thickness of the substrate exceeds 100 μm, the folding performance of the optical film will be insufficient, and the requirements of the folding test described below may not be met. In addition, the optical film will become heavy, which is not good in terms of weight reduction. The thickness of the substrate was taken by using a scanning electron microscope (SEM) to take a cross-section of the substrate. The thickness of the substrate was measured at 20 locations on the image of the cross-section, and the arithmetic average of the thickness of the 20 locations was taken as the thickness of the substrate. The lower limit of the substrate 11 is more preferably 25 μm or more, and the upper limit of the substrate 11 is more preferably 80 μm or less.

作為基材11之構成材料，例如可列舉：聚醯亞胺系樹脂、聚醯胺-亞醯胺系樹脂、聚醯胺系樹脂、聚酯系樹脂(例如，聚對酞酸乙二酯或聚萘二甲酸乙二酯(polyethylene naphthalate))等樹脂。此等之中，從不僅在折疊測試中不易發生裂縫或斷裂，且亦具有優異之硬度及透明性，又，耐熱性亦優異，亦可藉由燒製進一步賦予優異之硬度及透明性的觀點而言，較佳為聚醯亞胺系樹脂、聚醯胺系樹脂或此等之混合物。 As the constituent material of the substrate 11, for example, polyimide resin, polyimide-imide resin, polyimide resin, polyester resin (for example, polyethylene terephthalate or Polyethylene naphthalate (polyethylene naphthalate) and other resins. Among these, from the viewpoint that not only is it not easy to crack or break in the folding test, but also has excellent hardness and transparency, and also has excellent heat resistance, and can be further imparted with excellent hardness and transparency by firing In particular, it is preferably a polyimide-based resin, a polyimide-based resin, or a mixture of these.

聚醯亞胺系樹脂係藉由使四羧酸成分與二胺成分反應而得者。較佳藉由四羧酸成分與二胺成分之聚合得到聚醯胺酸然後進行醯亞胺化。醯亞胺化可以熱醯亞胺化來進行，亦可以化學醯亞胺化來進行。又，亦可以合併使用有熱醯亞胺化與化學醯亞胺化之方法來製造。聚醯亞胺系樹脂可為脂肪族之聚醯亞胺系樹脂，但較佳為含有芳香族環之芳香族系聚醯亞胺樹脂。芳香族系聚醯亞胺樹脂為於四羧酸成分及二胺成分之至少一者含有芳香族環者。 The polyimide resin is obtained by reacting a tetracarboxylic acid component and a diamine component. Preferably, the polyamide acid is obtained by polymerization of the tetracarboxylic acid component and the diamine component and then undergoes imidization. The imidization can be performed by thermal imidization or chemical imidization. In addition, it can also be produced by a combination of thermal imidization and chemical imidization. The polyimide resin may be an aliphatic polyimine resin, but is preferably an aromatic polyimide resin containing an aromatic ring. The aromatic polyimide resin contains an aromatic ring in at least one of the tetracarboxylic acid component and the diamine component.

作為四羧酸成分之具體例，適用四羧酸二酐，可列舉：環己烷四羧酸二酐、環戊烷四羧酸二酐、二環己烷-3,4,3’,4’-四羧酸二酐、焦蜜石酸二酐、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、2,2-雙(3,4-二羧基苯基)丙 烷二酐、2,2-雙(2,3-二羧基苯基)丙烷二酐、雙(3,4-二羧基苯基)醚二酐、雙(3,4-二羧基苯基)碸二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、雙(2,3-二羧基苯基)甲烷二酐、雙(3,4-二羧基苯基)甲烷二酐、2,2-雙(3,4-二羧基苯基)-1,1,1,3,3,3-六氟丙烷二酐、2,2-雙(2,3-二羧基苯基)-1,1,1,3,3,3-六氟丙烷二酐、1,3-雙[(3,4-二羧基)苯甲醯基]苯二酐、1,4-雙[(3,4-二羧基)苯甲醯基]苯二酐、2,2-雙{4-[4-(1,2-二羧基)苯氧基]苯基}丙烷二酐、2,2-雙{4-[3-(1,2-二羧基)苯氧基]苯基}丙烷二酐、雙{4-[4-(1,2-二羧基)苯氧基]苯基}酮二酐、雙{4-[3-(1,2-二羧基)苯氧基]苯基}酮二酐、4,4’-雙[4-(1,2-二羧基)苯氧基]聯苯二酐、4,4’-雙[3-(1,2-二羧基)苯氧基]聯苯二酐、雙{4-[4-(1,2-二羧基)苯氧基]苯基}酮二酐、雙{4-[3-(1,2-二羧基)苯氧基]苯基}酮二酐、雙{4-[4-(1,2-二羧基)苯氧基]苯基}碸二酐、雙{4-[3-(1,2-二羧基)苯氧基]苯基}碸二酐、雙{4-[4-(1,2-二羧基)苯氧基]苯基}硫化物二酐、雙{4-[3-(1,2-二羧基)苯氧基]苯基}硫化物二酐、4,4’-(六氟亞異丙基)二酞酸酐、3,4’-(六氟亞異丙基)二酞酸酐、3,3’-(六氟亞異丙基)二酞酸酐、2,3,6,7-萘四羧酸二酐、1,4,5,8-萘四羧酸二酐、1,2,5,6-萘四羧酸二酐、1,2,3,4-苯四羧酸二酐、3,4,9,10-苝四羧酸二酐、2,3,6,7-蒽四羧酸二酐、1,2,7,8-菲四羧酸二酐等。此等可單獨使用，亦可混合2種以上使用。 As a specific example of the tetracarboxylic acid component, tetracarboxylic dianhydride is applicable, including: cyclohexane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, dicyclohexane-3,4,3',4 '-Tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetra Carboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4 -Dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4- Dicarboxyphenyl) dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4- Dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis(2 ,3-Dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis[(3,4-dicarboxy)benzoyl]phthalic anhydride, 1,4-bis[(3,4-dicarboxy)benzoyl]phthalic anhydride, 2,2-bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}propane Dianhydride, 2,2-bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}propane dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy Yl]phenyl}ketone dianhydride, bis{4-[3-(1,2-dicarboxyl)phenoxy]phenyl}ketone dianhydride, 4,4'-bis[4-(1,2-di Carboxy)phenoxy]biphthalic anhydride, 4,4'-bis[3-(1,2-dicarboxy)phenoxy]biphthalic anhydride, bis{4-[4-(1,2-di Carboxy)phenoxy]phenyl}ketone dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}ketone dianhydride, bis{4-[4-(1,2 -Dicarboxyl)phenoxy]phenyl}sulfuric anhydride, bis{4-[3-(1,2-dicarboxyl)phenoxy]phenyl}phenyl}sulfuric anhydride, bis{4-[4-(1 ,2-Dicarboxyl)phenoxy]phenyl}sulfide dianhydride, bis{4-[3-(1,2-dicarboxyl)phenoxy]phenyl}sulfide dianhydride, 4,4'- (Hexafluoroisopropylidene) diphthalic anhydride, 3,4'-(hexafluoroisopropylidene) diphthalic anhydride, 3,3'-(hexafluoroisopropylidene) diphthalic anhydride, 2,3, 6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzene Tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride Wait. These can be used alone, or two or more of them can be mixed and used.

作為二胺成分之具體例，可使用對伸苯基二胺、間伸苯基二胺、鄰伸苯基二胺、3,3’-二胺基二苯基醚、3,4’-二胺基二苯基醚、4,4’-二胺基二苯基醚、3,3’-二胺基二苯基硫化物、3,4’-二胺基二苯基硫化物、4,4’-二胺基二苯基硫化物、3,3’-二胺基二苯基碸、3,4’-二胺基二苯基碸、4,4’-二胺基二苯基碸、3,3’-二胺基二苯甲酮、4,4’-二胺基二苯甲酮、3,4’-二胺基二苯甲酮、4,4’-二胺基苯甲醯胺苯、3,3’-二胺基二苯基甲烷、4,4’-二胺基二苯基甲烷、 3,4’-二胺基二苯基甲烷、2,2-二(3-胺基苯基)丙烷、2,2-二(4-胺基苯基)丙烷、2-(3-胺基苯基)-2-(4-胺基苯基)丙烷、2,2-二(3-胺基苯基)-1,1,1,3,3,3-六氟丙烷、2,2-二(4-胺基苯基)-1,1,1,3,3,3-六氟丙烷、2-(3-胺基苯基)-2-(4-胺基苯基)-1,1,1,3,3,3-六氟丙烷、1,1-二(3-胺基苯基)-1-苯基乙烷、1,1-二(4-胺基苯基)-1-苯基乙烷、1-(3-胺基苯基)-1-(4-胺基苯基)-1-苯基乙烷、1,3-雙(3-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(3-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯甲醯基)苯、1,3-雙(4-胺基苯甲醯基)苯、1,4-雙(3-胺基苯甲醯基)苯、1,4-雙(4-胺基苯甲醯基)苯、1,3-雙(3-胺基-α,α-二甲基苄基)苯、1,3-雙(4-胺基-α,α-二甲基苄基)苯、1,4-雙(3-胺基-α,α-二甲基苄基)苯、1,4-雙(4-胺基-α,α-二甲基苄基)苯、1,3-雙(3-胺基-α,α-二三氟甲基苄基)苯、1,3-雙(4-胺基-α,α-二三氟甲基苄基)苯、1,4-雙(3-胺基-α,α-二三氟甲基苄基)苯、1,4-雙(4-胺基-α,α-二三氟甲基苄基)苯、2,6-雙(3-胺基苯氧基)苄腈、2,6-雙(3-胺基苯氧基)吡啶、N,N’-雙(4-胺基苯基)對苯二甲醯胺(terephthalamide)、9,9-雙(4-胺基苯基)茀、2,2’-二甲基-4,4’-二胺基聯苯、2,2’-二三氟甲基-4,4’-二胺基聯苯、3,3’-二氯-4,4’-二胺基聯苯、3,3’-二甲氧基-4,4’-二胺基聯苯、3,3’-二甲基-4,4’-二胺基聯苯、4,4’-雙(3-胺基苯氧基)聯苯、4,4’-雙(4-胺基苯氧基)聯苯、雙[4-(3-胺基苯氧基)苯基]酮、雙[4-(4-胺基苯氧基)苯基]酮、雙[4-(3-胺基苯氧基)苯基]硫化物、雙[4-(4-胺基苯氧基)苯基]硫化物、雙[4-(3-胺基苯氧基)苯基]碸、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]醚、雙[4-(4-胺基苯氧基)苯基]醚、2,2-雙[4-(3-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[3-(3-胺基苯氧基) 苯基]-1,1,1,3,3,3-六氟丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷、1,3-雙[4-(3-胺基苯氧基)苯甲醯基]苯、1,3-雙[4-(4-胺基苯氧基)苯甲醯基]苯、1,4-雙[4-(3-胺基苯氧基)苯甲醯基]苯、1,4-雙[4-(4-胺基苯氧基)苯甲醯基]苯、1,3-雙[4-(3-胺基苯氧基)-α,α-二甲基苄基]苯、1,3-雙[4-(4-胺基苯氧基)-α,α-二甲基苄基]苯、1,4-雙[4-(3-胺基苯氧基)-α,α-二甲基苄基]苯、1,4-雙[4-(4-胺基苯氧基)-α,α-二甲基苄基]苯、4,4’-雙[4-(4-胺基苯氧基)苯甲醯基]二苯基醚、4,4’-雙[4-(4-胺基-α,α-二甲基苄基)苯氧基]二苯甲酮、4,4’-雙[4-(4-胺基-α,α-二甲基苄基)苯氧基]二苯基碸、4,4’-雙[4-(4-胺基苯氧基)苯氧基]二苯基碸、3,3’-二胺基-4,4’-二苯氧基二苯甲酮、3,3’-二胺基-4,4’-二聯苯氧基二苯甲酮、3,3’-二胺基-4-苯氧基二苯甲酮、3,3’-二胺基-4-聯苯氧基二苯甲酮、6,6’-雙(3-胺基苯氧基)-3,3,3’,3’-四甲基-1,1’-螺聯二氫茚(spirobiindan)、6,6’-雙(4-胺基苯氧基)-3,3,3’,3’-四甲基-1,1’-螺聯二氫茚、1,3-雙(3-胺丙基)四甲基二矽氧烷、1,3-雙(4-胺丁基)四甲基二矽氧烷、α,ω-雙(3-胺丙基)聚二甲基矽氧烷、α,ω-雙(3-胺丁基)聚二甲基矽氧烷、雙(胺甲基)醚、雙(2-胺乙基)醚、雙(3-胺丙基)醚、雙(2-胺基甲氧基)乙基]醚、雙[2-(2-胺基乙氧基)乙基]醚、雙[2-(3-胺基丙氧基)乙基]醚、反式-環己烷二胺、反式-1,4-雙亞甲基(bismethylene)環己烷二胺、2,6-雙(胺甲基)雙環[2,2,1]庚烷、2,5-雙(胺甲基)雙環[2,2,1]庚烷，又，亦可使用上述二胺之芳香族環上一部份或者全部之氫原子經選自氟基、甲基、甲氧基、三氟甲基或三氟甲氧基中之取代基取代的二胺。此等可單獨使用，亦可混合2種以上使用。 As specific examples of the diamine component, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diamine can be used Amino diphenyl ether, 4,4'-diamino diphenyl ether, 3,3'-diamino diphenyl sulfide, 3,4'-diamino diphenyl sulfide, 4, 4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide , 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone Aminobenzene, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-bis(3 -Aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, 2,2- Bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3, 3-hexafluoropropane, 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 1,1-bis( 3-aminophenyl)-1-phenylethane, 1,1-bis(4-aminophenyl)-1-phenylethane, 1-(3-aminophenyl)-1-( 4-aminophenyl)-1-phenylethane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4 -Bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3- Bis(4-aminobenzyl)benzene, 1,4-bis(3-aminobenzyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3 -Bis(3-amino-α,α-dimethylbenzyl)benzene, 1,3-bis(4-amino-α,α-dimethylbenzyl)benzene, 1,4-bis(3 -Amino-α,α-dimethylbenzyl)benzene, 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene, 1,3-bis(3-amino- α,α-Ditrifluoromethylbenzyl)benzene, 1,3-bis(4-amino-α,α-ditrifluoromethylbenzyl)benzene, 1,4-bis(3-amino- α,α-Ditrifluoromethylbenzyl)benzene, 1,4-bis(4-amino-α,α-ditrifluoromethylbenzyl)benzene, 2,6-bis(3-aminobenzene) Oxy)benzonitrile, 2,6-bis(3-aminophenoxy)pyridine, N,N'-bis(4-aminophenyl)terephthalamide, 9,9- Bis (4-aminophenyl) sulfonium, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-ditrifluoromethyl-4,4'-diamino Biphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl -4,4'-diaminobiphenyl, 4,4'- Bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]ketone, double [4-(4-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)benzene Group] sulfide, bis[4-(3-aminophenoxy)phenyl] ash, bis[4-(4-aminophenoxy)phenyl] ash, bis[4-(3-amino) Phenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2 ,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3, 3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 1,3-bis [4-(3-Aminophenoxy)benzyl]benzene, 1,3-bis[4-(4-aminophenoxy)benzyl]benzene, 1,4-bis[4 -(3-Aminophenoxy)benzyl]benzene, 1,4-bis[4-(4-aminophenoxy)benzyl]benzene, 1,3-bis[4-( 3-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene , 1,4-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-aminophenoxy)-α ,α-Dimethylbenzyl]benzene, 4,4'-bis[4-(4-aminophenoxy)benzyl]diphenyl ether, 4,4'-bis[4-(4 -Amino-α,α-dimethylbenzyl)phenoxy]benzophenone, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy Diphenyl sulfide, 4,4'-bis[4-(4-aminophenoxy)phenoxy] diphenyl sulfide, 3,3'-diamino-4,4'-diphenyl Oxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 6,6'-bis(3-aminophenoxy)-3,3,3',3'-tetramethyl- 1,1'-spirobiindan, 6,6'-bis(4-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spiro Indene, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane, α,ω-bis (3-Aminopropyl) polydimethylsiloxane, α,ω-bis(3-aminobutyl)polydimethylsiloxane, bis(aminomethyl)ether, bis(2-aminoethyl) ) Ether, bis(3-aminopropyl) ether, bis(2-aminomethoxy)ethyl]ether, bis[2-(2-aminoethoxy)ethyl]ether, bis[2- (3-Aminopropoxy)ethyl)ether, trans-cyclohexanediamine, trans-1,4-bis Methyl (bismethylene) cyclohexane diamine, 2,6-bis(aminomethyl)bicyclo[2,2,1]heptane, 2,5-bis(aminomethyl)bicyclo[2,2,1] Heptane, in addition, one part or all of the hydrogen atoms on the aromatic ring of the above-mentioned diamine may be substituted by a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group or a trifluoromethoxy group. Group-substituted diamines. These can be used alone, or two or more of them can be mixed and used.

從提升透光性且提升剛性之方面上，作為聚醯亞胺系樹脂，較佳為下述之聚醯亞胺系樹脂：含有芳香族環且含有選自由(i)氟原子、(ii)脂肪 族環及(iii)切斷芳香族環彼此之電子共軛的連結基團組成之群中的至少1者；更佳為含有(i)與(iii)之至少1者的聚醯亞胺系樹脂。若聚醯亞胺系樹脂含有芳香族環，則配向性會提高，剛性會提升，但有因芳香族環之吸收波長而導致透射率下降的傾向。當聚醯亞胺系樹脂含有(i)氟原子之情形時，由於可使聚醯亞胺骨架內之電子狀態變得電荷難以移動，故透光性會提升。又，當聚醯亞胺系樹脂含有(ii)脂肪族環之情形時，因藉由截斷聚醯亞胺骨架內之π電子的共軛而可阻礙骨架內之電荷的移動，故透光性會提升。並且，當聚醯亞胺系樹脂含有(iii)切斷芳香族環彼此之電子共軛的連結基團之情形時，因藉由截斷聚醯亞胺骨架內之π電子的共軛而可阻礙骨架內之電荷的移動，故透光性會提升。作為此種切斷芳香族環彼此之電子共軛的連結基團，例如可列舉：醚鍵、硫醚鍵、羰基鍵、硫羰基鍵、醯胺鍵、磺醯基鍵及亞磺醯基鍵以及可經氟取代之伸烷基(alkylene group)等2價連結基團。 In terms of improving light transmittance and improving rigidity, as the polyimide resin, the following polyimide resin is preferred: containing an aromatic ring and containing fluorine atoms selected from (i) fluorine atoms, (ii) Aliphatic ring and (iii) at least one of the group consisting of a linking group that cuts off the electronic conjugation of aromatic rings; more preferably a polyimide containing at least one of (i) and (iii) Department resin. If the polyimide-based resin contains an aromatic ring, the alignment property will increase and the rigidity will increase, but the transmittance tends to decrease due to the absorption wavelength of the aromatic ring. When the polyimide-based resin contains (i) fluorine atoms, since the electronic state in the polyimide skeleton can be made difficult for electric charges to move, the light transmittance is improved. In addition, when the polyimide-based resin contains (ii) aliphatic ring, because the conjugate of the π electrons in the polyimide skeleton is blocked, the movement of the electric charge in the skeleton is blocked, so the light transmittance Will improve. In addition, when the polyimide-based resin contains (iii) a linking group that cuts off the electronic conjugation of the aromatic rings, it can be blocked by cutting off the conjugation of the π electrons in the polyimide skeleton. The movement of the electric charge in the framework increases the light transmittance. Examples of such linking groups that cut the electronic conjugation of aromatic rings include ether bonds, thioether bonds, carbonyl bonds, thiocarbonyl bonds, amide bonds, sulfonyl bonds, and sulfinyl bonds. And divalent linking groups such as alkylene groups that can be substituted with fluorine.

此等之中，從提升透光性且提升剛性之方面，較佳使用含有芳香族環且含有氟原子之聚醯亞胺系樹脂。關於含有氟原子之聚醯亞胺系樹脂中的氟原子含有比例，藉由X射線光電子光譜法測量聚醯亞胺系樹脂表面而得到的氟原子數(F)與碳原子數(C)之比率(F/C)較佳為0.01以上，更佳為0.05以上。另一方面，若氟原子之含有比例過高，則有聚醯亞胺系樹脂原本之耐熱性等下降之虞，因此，前述氟原子數(F)與碳原子數(C)之比率(F/C)較佳為1以下，更佳為0.8以下。這裡，藉由X射線光電子光譜法(XPS)之測量所得到的上述比率，可從使用X射線光電子能譜儀(例如，Thermo Scientific公司Theta Probe)測量之各原子的原子%之值求得。 Among these, it is preferable to use a polyimide-based resin containing an aromatic ring and a fluorine atom in terms of improving light transmittance and improving rigidity. Regarding the fluorine atom content ratio in the polyimide resin containing fluorine atoms, the number of fluorine atoms (F) and the number of carbon atoms (C) obtained by measuring the surface of the polyimide resin by X-ray photoelectron spectroscopy The ratio (F/C) is preferably 0.01 or more, more preferably 0.05 or more. On the other hand, if the content ratio of fluorine atoms is too high, the original heat resistance of the polyimide resin may decrease. Therefore, the ratio of the number of fluorine atoms (F) to the number of carbon atoms (C) (F /C) is preferably 1 or less, more preferably 0.8 or less. Here, the above-mentioned ratio obtained by X-ray photoelectron spectroscopy (XPS) measurement can be obtained from the atomic% value of each atom measured using an X-ray photoelectron spectrometer (for example, Theta Probe from Thermo Scientific).

又，從提升透光性且提升剛性之方面，較佳使用下述之聚醯亞胺系樹脂：鍵結於聚醯亞胺系樹脂所含之碳原子的氫原子之70%以上為直接鍵結於芳香族環的氫原子。鍵結於聚醯亞胺系樹脂所含之碳原子的全部氫原子(個 數)中直接鍵結於芳香族環之氫原子(個數)的比例，更佳為80%以上，再更佳為85%以上。當鍵結於聚醯亞胺所含之碳原子的氫原子之70%以上為直接鍵結於芳香族環的氫原子之情形時，即使經過在大氣中之加熱步驟，例如即使於200℃以上進行延伸，光學特性尤其是總光線透射率或黃色指數(YI)之變化亦少，故較佳。當鍵結於聚醯亞胺系樹脂所含之碳原子的氫原子之70%以上為直接鍵結於芳香族環的氫原子之情形時，由於與氧的反應性低，故推斷聚醯亞胺系樹脂之化學構造不易起變化。關於由聚醯亞胺系樹脂構成之基材，雖然利用其高耐熱性而大多使用於需要伴隨加熱之加工步驟的元件等，但當鍵結於聚醯亞胺系樹脂所含之碳原子的氫原子之70%以上為直接鍵結於芳香族環的氫原子之情形時，由於無須為了維持透明性而在非活性環境下實施此等後續步驟，因此，具有可抑制花費於設備成本或環境控制之費用的優點。這裡，鍵結於聚醯亞胺系樹脂所含之碳原子的全部氫原子(個數)中直接鍵結於芳香族環之氫原子(個數)的比例，可對聚醯亞胺之分解物使用高效液相層析術、氣相層析質譜儀及NMR求得。例如，可藉由鹼性水溶液或超臨界甲醇將樣品分解，將得到之分解物以高效液相層析術分離，使用氣相層析質譜儀及NMR等進行該經分離之各波峰的定性分析，使用高效液相層析術進行定量，藉此可求得聚醯亞胺所含之全部氫原子(個數)中直接鍵結於芳香族環的氫原子(個數)之比例。 In addition, in terms of improving light transmittance and improving rigidity, it is preferable to use the following polyimide resin: 70% or more of the hydrogen atoms bonded to the carbon atoms contained in the polyimide resin are direct bonds A hydrogen atom attached to an aromatic ring. The proportion of hydrogen atoms (number) directly bonded to the aromatic ring among all the hydrogen atoms (number) bonded to the carbon atoms contained in the polyimide resin is more preferably 80% or more, and even more preferably It is more than 85%. When more than 70% of the hydrogen atoms bonded to the carbon atoms contained in the polyimide are hydrogen atoms directly bonded to the aromatic ring, even after a heating step in the atmosphere, for example, even at 200°C or higher For stretching, the change in optical properties, especially total light transmittance or yellow index (YI) is also small, so it is better. When more than 70% of the hydrogen atoms bonded to the carbon atoms contained in the polyimide resin are hydrogen atoms directly bonded to the aromatic ring, the reactivity with oxygen is low, so it is inferred that the polyimide resin The chemical structure of amine resin is not easy to change. Regarding substrates made of polyimide resins, although they are mostly used for elements that require processing steps accompanied by heating due to their high heat resistance, they are bonded to the carbon atoms contained in the polyimide resins. When more than 70% of the hydrogen atoms are directly bonded to the hydrogen atoms of the aromatic ring, since there is no need to perform these subsequent steps in an inactive environment in order to maintain transparency, it is possible to reduce the cost of equipment or the environment. The advantages of cost control. Here, among all the hydrogen atoms (number) bonded to the carbon atoms contained in the polyimide resin, the ratio of the hydrogen atoms (number) directly bonded to the aromatic ring can be used to decompose the polyimide The substance was obtained by high performance liquid chromatography, gas chromatography mass spectrometer and NMR. For example, the sample can be decomposed by alkaline aqueous solution or supercritical methanol, the resulting decomposed product can be separated by high performance liquid chromatography, and the separated peaks can be qualitatively analyzed using gas chromatography mass spectrometer and NMR. Using high performance liquid chromatography for quantification, the ratio of hydrogen atoms (number) directly bonded to the aromatic ring among all the hydrogen atoms (number) contained in polyimine can be obtained.

又，從提升透光性且提升剛性之方面，作為聚醯亞胺系樹脂，其中，較佳具有選自由下述通式(1)及下述通式(3)表示之構造組成之群中的1種構造。 In addition, from the viewpoint of improving light transmittance and improving rigidity, the polyimide resin preferably has a structure selected from the group consisting of the following general formula (1) and the following general formula (3) 1 structure.

Figure 106135143-A0202-12-0019-1
Figure 106135143-A0202-12-0019-1

於上述通式(1)中，R1表示為四羧酸殘基之4價基，R2表示選自由反式-環己烷二胺殘基、反式-1,4-雙亞甲基環己烷二胺殘基、4,4’-二胺基二苯基碸殘基、3,4’-二胺基二苯基碸殘基及下述通式(2)表示之2價基組成之群中的至少1種2價基。n表示重複單元數，為1以上。本說明書中，「四羧酸殘基」係指從四羧酸經去除4個羧基而得之殘基，表示與從四羧酸二酐經去除酸二酐構造而得之殘基相同的構造。又，「二胺殘基」係指從二胺經去除2個胺基而得之殘基。 In the above general formula (1), R 1 is a tetravalent group of a tetracarboxylic acid residue, and R 2 is selected from the group consisting of trans-cyclohexanediamine residue and trans-1,4-bismethylene Cyclohexanediamine residue, 4,4'-diaminodiphenyl sulfonate residue, 3,4'-diaminodiphenyl sulfonate residue and the divalent group represented by the following general formula (2) At least one divalent group in the group of composition. n represents the number of repeating units and is 1 or more. In this specification, "tetracarboxylic acid residue" refers to a residue obtained by removing 4 carboxyl groups from tetracarboxylic acid, and represents the same structure as a residue obtained by removing acid dianhydride from tetracarboxylic dianhydride . In addition, "diamine residue" refers to a residue obtained by removing two amine groups from diamine.

Figure 106135143-A0202-12-0019-2
Figure 106135143-A0202-12-0019-2

於上述通式(2)中，R3及R4各自獨立地表示氫原子、烷基或全氟烷基。 In the above general formula (2), R 3 and R 4 each independently represent a hydrogen atom, an alkyl group, or a perfluoroalkyl group.

Figure 106135143-A0202-12-0019-3
Figure 106135143-A0202-12-0019-3

於上述通式(3)中，R5表示選自由環己烷四羧酸殘基、環戊烷四羧酸殘基、二環己烷-3,4,3’,4’-四羧酸殘基及4,4’-(六氟亞異丙基)二酞酸殘基組成之群中的至少1種4價基，R6表示為二胺殘基之2價基。n’表示重複單 元數，為1以上。 In the above general formula (3), R 5 represents selected from cyclohexane tetracarboxylic acid residue, cyclopentane tetracarboxylic acid residue, dicyclohexane-3,4,3',4'-tetracarboxylic acid At least one tetravalent group in the group consisting of residues and 4,4'-(hexafluoroisopropylidene) diphthalic acid residues, and R 6 represents a divalent group of diamine residues. n'represents the number of repeating units and is 1 or more.

於上述通式(1)中之R1為四羧酸殘基，可為從如前述例示之四羧酸二酐經去除酸二酐構造而得之殘基。作為上述通式(1)中之R1，其中，從提升透光性且提升剛性之方面，較佳包含選自由4,4’-(六氟亞異丙基)二酞酸殘基、3,3’,4,4’-聯苯四羧酸殘基、焦蜜石酸殘基、2,3’,3,4’-聯苯四羧酸殘基、3,3’,4,4’-二苯甲酮四羧酸殘基、3,3’,4,4’-二苯基碸四羧酸殘基、4,4’-氧二酞酸殘基、環己烷四羧酸殘基及環戊烷四羧酸殘基組成之群中的至少1種，更佳包含選自由4,4’-(六氟亞異丙基)二酞酸殘基、4,4’-氧二酞酸殘基及3,3’,4,4’-二苯基碸四羧酸殘基組成之群中的至少1種。 R 1 in the above general formula (1) is a tetracarboxylic acid residue, which may be a residue obtained by removing the acid dianhydride structure from the tetracarboxylic dianhydride as exemplified above. As R 1 in the above general formula (1), it preferably contains 4,4'-(hexafluoroisopropylidene) diphthalic acid residues, 3 ,3',4,4'-biphenyltetracarboxylic acid residue, pyromellitic acid residue, 2,3',3,4'-biphenyltetracarboxylic acid residue, 3,3',4,4 '-Benzophenone tetracarboxylic acid residue, 3,3',4,4'-diphenyl tetracarboxylic acid residue, 4,4'-oxodiphthalic acid residue, cyclohexane tetracarboxylic acid residue Residues and at least one of the group consisting of cyclopentanetetracarboxylic acid residues, and more preferably include 4,4'-(hexafluoroisopropylidene) diphthalic acid residues, 4,4'-oxygen At least one of the group consisting of diphthalic acid residues and 3,3',4,4'-diphenyl tetracarboxylic acid residues.

較佳於R1中含有合計50莫耳%以上之此等合適之殘基，更佳含有70莫耳%以上，再更佳含有90莫耳%以上。 Preferably, R 1 contains more than 50 mol% of these suitable residues in total, more preferably contains more than 70 mol%, and still more preferably contains more than 90 mol%.

又，亦較佳將選自由3,3’,4,4’-聯苯四羧酸殘基、3,3’,4,4’-二苯甲酮四羧酸殘基及焦蜜石酸殘基組成之群中至少1種之類適於提升剛直性的四羧酸殘基群(群組A)與選自由4,4’-(六氟亞異丙基)二酞酸殘基、2,3’,3,4’-聯苯四羧酸殘基、3,3’,4,4’-二苯基碸四羧酸殘基、4,4’-氧二酞酸殘基、環己烷四羧酸殘基及環戊烷四羧酸殘基組成之群中至少1種之類適於提升透明性的四羧酸殘基群(群組B)加以混合使用作為R1。 Moreover, it is also preferably selected from 3,3',4,4'-biphenyltetracarboxylic acid residues, 3,3',4,4'-benzophenonetetracarboxylic acid residues and pyromellitic acid At least one of the group of residues, such as tetracarboxylic acid residues suitable for improving rigidity (group A) and selected from 4,4'-(hexafluoroisopropylidene) diphthalic acid residues, 2,3',3,4'-biphenyltetracarboxylic acid residue, 3,3',4,4'-diphenyl tetracarboxylic acid residue, 4,4'-oxydiphthalic acid residue, At least one tetracarboxylic acid residue group (group B) suitable for improving transparency, such as at least one of the group consisting of cyclohexane tetracarboxylic acid residue and cyclopentane tetracarboxylic acid residue, is mixed and used as R 1 .

於此情形時，關於前述適於提升剛直性之四羧酸殘基群(群組A)與適於提升透明性之四羧酸殘基群(群組B)的含有比率，較佳相對於適於提升透明性之四羧酸殘基群(群組B)1莫耳，前述適於提升剛直性之四羧酸殘基群(群組A)為0.05莫耳以上9莫耳以下，更佳為0.1莫耳以上5莫耳以下，再更佳為0.3莫耳以上4莫耳以下。 In this case, the content ratio of the aforementioned tetracarboxylic acid residue group (group A) suitable for improving rigidity and the tetracarboxylic acid residue group suitable for improving transparency (group B) is preferably relative to The tetracarboxylic acid residue group (group B) suitable for improving the transparency is 1 mol, and the aforementioned tetracarboxylic acid residue group (group A) suitable for improving the rigidity is 0.05 mol or more and 9 mol or less. Preferably, it is 0.1 mol or more and 5 mol or less, and more preferably 0.3 mol or more and 4 mol or less.

作為上述通式(1)中之R2，其中，從提升透光性且提升剛性之方面，較佳為選自由4,4’-二胺基二苯基碸殘基、3,4’-二胺基二苯基碸殘基及 上述通式(2)表示之2價基組成之群中的至少1種2價基，更佳為選自由4,4’-二胺基二苯基碸殘基、3,4’-二胺基二苯基碸殘基以及R3及R4為全氟烷基之上述通式(2)表示之2價基組成之群中的至少1種2價基。 As R 2 in the above general formula (1), among them, in terms of improving light transmittance and improving rigidity, it is preferably selected from 4,4'-diaminodiphenyl sulfonate residues, 3,4'- Diaminodiphenyl sulfide residues and at least one divalent group in the group consisting of the divalent group represented by the general formula (2), more preferably selected from 4,4'-diaminodiphenyl sulfide Residues, 3,4'-diaminodiphenyl sulfonate residues, and at least one divalent group consisting of divalent groups represented by the above general formula (2) in which R 3 and R 4 are perfluoroalkyl groups base.

作為上述通式(3)中之R5，其中，從提升透光性且提升剛性之方面，較佳包含4,4’-(六氟亞異丙基)二酞酸殘基、3,3’,4,4’-二苯基碸四羧酸殘基及氧二酞酸殘基。 As R 5 in the above general formula (3), it preferably contains 4,4'-(hexafluoroisopropylidene) diphthalic acid residues, 3,3 ',4,4'-Diphenyl tetracarboxylic acid residues and oxydiphthalic acid residues.

較佳於R5中含有50莫耳%以上之此等合適之殘基，更佳含有70莫耳%以上，再更佳含有90莫耳%以上。 R 5 preferably contains more than 50 mol% of these suitable residues, more preferably contains more than 70 mol%, and still more preferably contains more than 90 mol%.

上述通式(3)中之R6為二胺殘基，可為從如前述例示之二胺經去除2個胺基而得之殘基。作為上述通式(3)中之R6，其中，從提升透光性且提升剛性之方面，較佳包含選自由2,2’-雙(三氟甲基)聯苯胺殘基、雙[4-(4-胺基苯氧基)苯基]碸殘基、4,4’-二胺基二苯基碸殘基、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷殘基、雙[4-(3-胺基苯氧基)苯基]碸殘基、4,4’-二胺基-2,2’-雙(三氟甲基)二苯基醚殘基、1,4-雙[4-胺基-2-(三氟甲基)苯氧基]苯殘基、2,2-雙[4-(4-胺基-2-三氟甲基苯氧基)苯基]六氟丙烷殘基、4,4’-二胺基-2-(三氟甲基)二苯基醚殘基、4,4’-二胺基苯甲醯胺苯殘基、N,N’-雙(4-胺基苯基)對苯二甲醯胺殘基及9,9-雙(4-胺基苯基)茀殘基組成之群中的至少1種2價基，更佳包含選自由2,2’-雙(三氟甲基)聯苯胺殘基、雙[4-(4-胺基苯氧基)苯基]碸殘基及4,4’-二胺基二苯基碸殘基組成之群中的至少1種2價基。 R 6 in the above general formula (3) is a diamine residue, which may be a residue obtained by removing two amine groups from the diamine exemplified above. As R 6 in the above general formula (3), among them, from the aspects of improving light transmittance and improving rigidity, it preferably contains a residue selected from 2,2'-bis(trifluoromethyl)benzidine, bis[4 -(4-Aminophenoxy)phenyl) residues, 4,4'-diaminodiphenyl residues, 2,2-bis[4-(4-aminophenoxy)benzene Group] hexafluoropropane residue, bis[4-(3-aminophenoxy)phenyl] sulfonate residue, 4,4'-diamino-2,2'-bis(trifluoromethyl)di Phenyl ether residue, 1,4-bis[4-amino-2-(trifluoromethyl)phenoxy]benzene residue, 2,2-bis[4-(4-amino-2-tri (Fluoromethylphenoxy)phenyl)hexafluoropropane residue, 4,4'-diamino-2-(trifluoromethyl)diphenyl ether residue, 4,4'-diaminobenzyl Among the group consisting of aminobenzene residues, N,N'-bis(4-aminophenyl)p-phthalamide residues and 9,9-bis(4-aminophenyl) residues At least one divalent group, more preferably including 2,2'-bis(trifluoromethyl)benzidine residues, bis[4-(4-aminophenoxy)phenyl]sulfonate residues and 4 , At least one divalent group in the group consisting of 4'-diaminodiphenyl sulfide residues.

較佳於R6中含有合計50莫耳%以上之此等合適之殘基，更佳含有70莫耳%以上，再更佳含有90莫耳%以上。 Preferably, R 6 contains more than 50 mol% of these suitable residues in total, more preferably contains more than 70 mol%, and still more preferably contains more than 90 mol%.

又，亦較佳將選自由雙[4-(4-胺基苯氧基)苯基]碸殘基、4,4’-二胺基苯甲醯胺苯殘基、N,N’-雙(4-胺基苯基)對苯二甲醯胺殘基、對苯 二胺殘基、間苯二胺殘基及4,4’-二胺基二苯基甲烷殘基組成之群中至少1種之類適於提升剛直性的二胺殘基群(群組C)與選自由2,2’-雙(三氟甲基)聯苯胺殘基、4,4’-二胺基二苯基碸殘基、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷殘基、雙[4-(3-胺基苯氧基)苯基]碸殘基、4,4’-二胺基-2,2’-雙(三氟甲基)二苯基醚殘基、1,4-雙[4-胺基-2-(三氟甲基)苯氧基]苯殘基、2,2-雙[4-(4-胺基-2-三氟甲基苯氧基)苯基]六氟丙烷殘基、4,4’-二胺基-2-(三氟甲基)二苯基醚殘基及9,9-雙(4-胺基苯基)茀殘基組成之群中至少1種之類適於提升透明性的二胺殘基群(群組D)加以混合使用作為R6。 In addition, it is also preferred to be selected from the group consisting of bis[4-(4-aminophenoxy)phenyl] sulfide residues, 4,4'-diaminobenzamide residues, N,N'-bis (4-Aminophenyl) p-xylylenediamine residues, p-phenylenediamine residues, m-phenylenediamine residues and 4,4'-diaminodiphenylmethane residues at least 1 type of diamine residue group suitable for improving rigidity (group C) and selected from 2,2'-bis(trifluoromethyl)benzidine residues, 4,4'-diaminodiphenyl Residues, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane residues, bis[4-(3-aminophenoxy)phenyl] residues , 4,4'-diamino-2,2'-bis(trifluoromethyl)diphenyl ether residue, 1,4-bis[4-amino-2-(trifluoromethyl)phenoxy Yl]benzene residue, 2,2-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane residue, 4,4'-diamino-2- (Trifluoromethyl)diphenyl ether residues and 9,9-bis(4-aminophenyl) residues are at least one of the group consisting of diamine residues suitable for improving transparency ( Group D) is mixed and used as R 6 .

於此情形時，關於前述適於提升剛直性之二胺殘基群(群組C)與適於提升透明性之二胺殘基群(群組D)的含有比率，較佳相對於適於提升透明性之二胺殘基群(群組D)1莫耳，前述適於提升剛直性之二胺殘基群(群組C)為0.05莫耳以上9莫耳以下，更佳為0.1莫耳以上5莫耳以下，再更佳為0.3莫耳以上4莫耳以下。 In this case, the content ratio of the aforementioned diamine residue group suitable for improving rigidity (group C) and the diamine residue group suitable for improving transparency (group D) is preferably relative to The group of diamine residues (group D) for improving transparency is 1 mol, and the group of diamine residues (group C) suitable for improving rigidity is 0.05 mol or more and 9 mol or less, more preferably 0.1 mol It is 5 mol above the ear and less than 5 mol, more preferably 0.3 mol or more and 4 mol or less.

於上述通式(1)及上述通式(3)表示之構造中，n及n’分別獨立地表示重複單元數，為1以上。關於聚醯亞胺中之重複單元數n，根據構造作適當選擇以顯現出後述較佳之玻璃轉移溫度即可，並無特別限定。平均重複單元數通常為10~2000，更佳為15~1000。 In the structures represented by the above general formula (1) and the above general formula (3), n and n'each independently represent the number of repeating units, and are 1 or more. Regarding the number n of repeating units in the polyimide, it may be appropriately selected according to the structure so as to exhibit a preferable glass transition temperature described later, and it is not particularly limited. The average number of repeating units is usually 10 to 2000, more preferably 15 to 1000.

又，聚醯亞胺系樹脂其一部份亦可含有聚醯胺構造。作為可含有之聚醯胺構造，例如可列舉：如偏苯三甲酸酐(trimellitic anhydride)之類含有三羧酸殘基的聚醯胺-亞醯胺構造，或如對酞酸之類含有二羧酸殘基的聚醯胺構造。 In addition, a part of the polyimide-based resin may contain a polyimide structure. As the polyamide structure that can be contained, for example, a polyamide-imide structure containing tricarboxylic acid residues such as trimellitic anhydride (trimellitic anhydride), or a dicarboxylic acid structure containing dicarboxylic acid such as terephthalic acid Polyamide structure of acid residues.

聚醯亞胺系樹脂從耐熱性之方面，玻璃轉移溫度較佳為250℃以上，更佳為270℃以上。另一方面，從延伸容易性或降低烘烤溫度之方面，玻璃轉移溫度較佳為400℃以下，更佳為380℃以下。 In terms of heat resistance, the glass transition temperature of the polyimide resin is preferably 250°C or higher, more preferably 270°C or higher. On the other hand, the glass transition temperature is preferably 400°C or lower, more preferably 380°C or lower, in terms of ease of stretching or lowering the baking temperature.

具體而言，作為聚醯亞胺基材，例如可舉具有由下式表示之構造的化合物。下式中，n為重複單元，表示2以上之整數。 Specifically, as a polyimide substrate, for example, a compound having a structure represented by the following formula can be cited. In the following formula, n is a repeating unit and represents an integer of 2 or more.

Figure 106135143-A0202-12-0023-56
Figure 106135143-A0202-12-0023-56

Figure 106135143-A0202-12-0023-5
Figure 106135143-A0202-12-0023-5

Figure 106135143-A0202-12-0023-6
Figure 106135143-A0202-12-0023-6

Figure 106135143-A0202-12-0023-7
Figure 106135143-A0202-12-0023-7

Figure 106135143-A0202-12-0024-8
Figure 106135143-A0202-12-0024-8

Figure 106135143-A0202-12-0024-9
Figure 106135143-A0202-12-0024-9

Figure 106135143-A0202-12-0024-10
Figure 106135143-A0202-12-0024-10

Figure 106135143-A0202-12-0024-11
Figure 106135143-A0202-12-0024-11

Figure 106135143-A0202-12-0024-12
Figure 106135143-A0202-12-0024-12

Figure 106135143-A0202-12-0025-13
Figure 106135143-A0202-12-0025-13

Figure 106135143-A0202-12-0025-14
Figure 106135143-A0202-12-0025-14

Figure 106135143-A0202-12-0025-15
Figure 106135143-A0202-12-0025-15

Figure 106135143-A0202-12-0025-16
Figure 106135143-A0202-12-0025-16

Figure 106135143-A0202-12-0025-17
Figure 106135143-A0202-12-0025-17

Figure 106135143-A0202-12-0026-18
Figure 106135143-A0202-12-0026-18

Figure 106135143-A0202-12-0026-19
Figure 106135143-A0202-12-0026-19

Figure 106135143-A0202-12-0026-20
Figure 106135143-A0202-12-0026-20

聚醯胺系樹脂，不僅脂肪族聚醯胺，亦包含芳香族聚醯胺(聚芳醯胺)。作為聚醯胺系樹脂，一般而言為具有由下式(21)及(22)表示之骨架者，作為上述聚醯胺系樹脂，例如可舉由下式(23)表示之化合物。另，下式中，n為重複單元，表示2以上之整數。 Polyamide resins include not only aliphatic polyamides but also aromatic polyamides (polyaramides). The polyamide-based resin generally has a skeleton represented by the following formulas (21) and (22). Examples of the polyamide-based resin include compounds represented by the following formula (23). In addition, in the following formula, n is a repeating unit and represents an integer of 2 or more.

Figure 106135143-A0202-12-0026-21
Figure 106135143-A0202-12-0026-21

Figure 106135143-A0202-12-0026-22
Figure 106135143-A0202-12-0026-22

Figure 106135143-A0202-12-0027-23
Figure 106135143-A0202-12-0027-23

上述由式(4)~(20)及(23)表示之聚醯亞胺系樹脂或聚醯胺系樹脂可使用市售者。作為由上述聚醯亞胺系樹脂構成之基材的市售品，例如可舉三菱瓦斯化學公司製之Neopulim等，作為由上述聚醯胺系樹脂構成之基材的市售品，則例如可舉東麗公司製之Mictron等。 Commercially available polyimide resins or polyimide resins represented by the above formulas (4) to (20) and (23) can be used. As a commercially available product of a substrate composed of the above-mentioned polyimide-based resin, for example, Neopulim manufactured by Mitsubishi Gas Chemical Co., Ltd., etc. can be cited, and as a commercially available product of a substrate composed of the above-mentioned polyimide-based resin, for example, For example, Mictron manufactured by Toray Corporation, etc.

又，上述由式(4)~(20)及(23)表示之聚醯亞胺系樹脂或聚醯胺系樹脂，可使用藉由周知方法合成者。例如，上述由式(4)表示之聚醯亞胺膜的合成方法記載於日本特開2009-132091，具體而言，可藉由使下式(21)表示之4,4’-六氟亞丙基雙酞酸二酐(hexafluoro propylidene bisphthalic dianhydride)(FPA)與2,2’-雙(三氟甲基)-4,4’-二胺基聯苯(TFDB)反應而得。 In addition, the polyimide-based resin or polyimide-based resin represented by the above formulas (4) to (20) and (23) can be synthesized by a known method. For example, the method for synthesizing the polyimide film represented by formula (4) is described in Japanese Patent Application Publication No. 2009-132091. Specifically, 4,4'-hexafluoroethylene represented by the following formula (21) Propyl diphthalic acid dianhydride (hexafluoro propylidene bisphthalic dianhydride) (FPA) and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFDB) are reacted.

Figure 106135143-A0202-12-0027-24
Figure 106135143-A0202-12-0027-24

上述聚醯亞胺系樹脂或聚醯胺系樹脂之重量平均分子量較佳為3000以上50萬以下之範圍，更佳為5000~30萬之範圍，再更佳為1萬以上20萬以下之範圍。若重量平均分子量未達3000，則有時會無法得到足夠之強度，若超過50萬，則由於黏度會上升，溶解性會下降，因而有時無法得到表面平滑且膜厚均一之基材。另，於本說明書中，「重量平均分子量」係指藉由凝膠滲透層析術(GPC)測得之聚苯乙烯換算值。 The weight average molecular weight of the polyimide resin or polyimide resin is preferably in the range of 3,000 to 500,000, more preferably in the range of 5,000 to 300,000, and still more preferably in the range of 10,000 to 200,000. . If the weight average molecular weight is less than 3,000, sufficient strength may not be obtained. If it exceeds 500,000, the viscosity will increase and the solubility will decrease, so a substrate with a smooth surface and a uniform film thickness may not be obtained. In addition, in this specification, "weight average molecular weight" refers to a polystyrene conversion value measured by gel permeation chromatography (GPC).

上述聚醯亞胺系樹脂及聚醯胺系樹脂之中，由於具有優異之透明 性，因此較佳為具有不易發生電荷於分子內或分子間移動之構造的聚醯亞胺基材或聚醯胺系樹脂，具體而言，可列舉：上述式(4)~(11)等之氟化聚醯亞胺膜、上述式(13)~(15)等具有脂環構造之聚醯亞胺系樹脂、上述式(23)等具有鹵基(halogen group)之聚醯胺系樹脂。 Among the above-mentioned polyimide-based resins and polyimide-based resins, since they have excellent transparency, they are preferably polyimide substrates or polyimide substrates having a structure that does not easily cause electric charge to move within or between molecules Amine-based resins, specifically, include: fluorinated polyimide films such as the above formulas (4) to (11), and polyimide resins having an alicyclic structure such as the above formulas (13) to (15) Resins, polyamide resins having halogen groups such as the above formula (23).

又，於上述式(4)~(11)等之氟化聚醯亞胺系樹脂，由於具有經氟化之構造，因此具有高耐熱性，於製造由聚醯亞胺系樹脂構成之基材時亦不會因熱而著色，故具有優異之透明性。 In addition, the fluorinated polyimide-based resins of the above formulas (4) to (11) have a fluorinated structure and therefore have high heat resistance, and are used in the manufacture of substrates made of polyimide-based resins. It will not be colored due to heat, so it has excellent transparency.

從可使樹脂層12之表面12A以JIS K5600-5-4：1999規定的鉛筆硬度測試(負載：750g，速度：1mm/秒)條件測得之硬度在3H以上的觀點而言，基材11較佳使用由上述式(4)~(11)等表示之氟化聚醯亞胺系樹脂構成的基材或由上述式(23)等具有鹵基之聚醯胺系樹脂構成的基材。其中，由於可使上述鉛筆硬度為3H以上極優異之硬度，因此，更佳使用由上述式(4)表示之聚醯亞胺系樹脂構成的基材。 From the viewpoint of making the surface 12A of the resin layer 12 have a hardness of 3H or more under the pencil hardness test (load: 750g, speed: 1mm/sec) specified in JIS K5600-5-4:1999, the substrate 11 It is preferable to use a substrate composed of a fluorinated polyimide resin represented by the above formulas (4) to (11) or the like or a substrate composed of a polyimide resin having a halogen group such as the above formula (23). Among them, since the pencil hardness can be made 3H or higher, which is extremely excellent hardness, it is more preferable to use a base material composed of a polyimide-based resin represented by the above formula (4).

作為聚酯系樹脂，例如可舉將聚對酞酸乙二酯、聚對酞酸丙二酯(polypropylene terephthalate)、聚對酞酸丁二酯(polybutylene terephthalate)、聚萘二甲酸乙二酯之至少1種作為構成成分的樹脂等。 Examples of polyester resins include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. At least one kind of resin etc. as a constituent component.

<<樹脂層>> <<Resin layer>>

樹脂層12係從第1層積層至第n層(n為3以上之整數)之多層構造者。從第1層至第n層當然主要為由樹脂構成之層，除了樹脂之外，亦可含有粒子或添加劑等。 The resin layer 12 has a multilayer structure from the first layer to the nth layer (n is an integer of 3 or more). The first layer to the nth layer are of course mainly layers composed of resin, and in addition to resin, particles or additives may be contained.

樹脂層12中之第1層~第n層各層的壓痕硬度，依序從第1層至第n層變大。亦即，於樹脂層12中，當使第1層、第2層、...、第n層之壓痕硬度分別為HIT1、HIT2、...、HITn時，滿足以下之關係式(A)。 The indentation hardness of each layer of the first layer to the nth layer in the resin layer 12 increases from the first layer to the nth layer in order. That is, in the resin layer 12, when the indentation hardness of the first layer, the second layer,..., and the nth layer are respectively H IT1 , H IT2 ,..., H ITn , the following relationship is satisfied Formula (A).

HIT1<HIT2<...<HITn...(A) H IT1 <H IT2 <...<H ITn ...(A)

具體而言，樹脂層12由於呈自基材11側從第1層12B依序積層至第3層12D的多層構造，因此，第1層12B、第2層12C、第3層12D各層之壓痕硬度依序從第1層12B至第3層12D變大。亦即，當使第1層12B、第2層12C及第3層12D之壓痕硬度分別為HIT1、HIT2、HIT3時，滿足以下之關係式(B)。 Specifically, the resin layer 12 has a multilayer structure in which the first layer 12B is sequentially stacked from the substrate 11 side to the third layer 12D. Therefore, the pressure of each layer of the first layer 12B, the second layer 12C, and the third layer 12D The mark hardness increases sequentially from the first layer 12B to the third layer 12D. That is, when the indentation hardness of the first layer 12B, the second layer 12C, and the third layer 12D are set to H IT1 , H IT2 , and H IT3 , the following relational expression (B) is satisfied.

HIT1<HIT2<HIT3...(B) H IT1 <H IT2 <H IT3 ... (B)

於本說明書中，「壓痕硬度」係指藉由以奈米壓痕法進行之硬度測量，將壓頭壓入各樹脂層100nm時之硬度。藉由上述奈米壓痕法進行之壓痕硬度測量，係使用海思創(HYSITRON)公司製之「TI950 TriboIndenter」進行。具體而言，首先製作藉由埋置樹脂埋置切成1mm×10mm之光學膜而成的團塊，藉由一般切片製作方法從該團塊切下沒有孔洞等之均勻的厚度70nm以上100nm以下之切片。切片之製作，可使用「Ultramicrotome EM UC7」(Leica Microsystems股份有限公司)等。然後，將被切下此沒有孔洞等之均勻的切片剩下的團塊作為測量樣品。接著，於此種測量樣品中藉由切下上述切片而得到的各樹脂層之剖面中央，以最大負載40μN、速度10μN/s壓入作為上述壓頭之Berkovich壓頭(三角錐)約100nm，保持一定，進行殘留應力緩和後，將負載卸除，測量緩和後之最大負載，使用該最大負載(Pmax(μN))及壓頭與試樣(各層)之接觸投影面積(Ap(nm2))，藉由Pmax/Ap算出壓痕硬度。使壓痕硬度為測量10次之值的算術平均值。 In this manual, "indentation hardness" refers to the hardness when the indenter is pressed into each resin layer by 100nm by hardness measurement by nanoindentation. The indentation hardness measurement performed by the above-mentioned nanoindentation method is performed using the "TI950 TriboIndenter" manufactured by HYSITRON. Specifically, first, an agglomerate formed by embedding an optical film of 1mm×10mm by embedding with resin is produced, and a uniform thickness of 70nm to 100nm without holes is cut from the agglomerate by a general slicing method.的片。 The slice. For the production of slices, "Ultramicrotome EM UC7" (Leica Microsystems Co., Ltd.) can be used. Then, the mass left over from this uniform slice without holes or the like is used as a measurement sample. Next, in this measurement sample, the center of the cross section of each resin layer obtained by cutting the above-mentioned sections is pressed into the Berkovich indenter (triangular pyramid) as the above-mentioned indenter at a maximum load of 40 μN and a speed of 10 μN/s for approximately 100 nm, Keep it constant, after the residual stress is relaxed, remove the load, measure the relaxed maximum load, use the maximum load (P max (μN)) and the contact projection area between the indenter and the sample (each layer) (A p (nm) 2 )), calculate the indentation hardness by P max /A p. Let the indentation hardness be the arithmetic average of the values measured 10 times.

於光學膜10，樹脂層12由於係由第1層12B、第2層12C、及第3層12D構成，因此雖然上述n為3，但上述第n層之n若為3以上，並無特別限定。上述n之上限從生產性之觀點而言，較佳為10以下。 In the optical film 10, since the resin layer 12 is composed of the first layer 12B, the second layer 12C, and the third layer 12D, although the above n is 3, if the n of the nth layer is 3 or more, there is no particular limited. From the viewpoint of productivity, the upper limit of n is preferably 10 or less.

當樹脂層12為3層構造之情形時，第1層12B、第2層12C、第3層12D各層之壓痕硬度若滿足上述關係式(B)，則並無特別限定，第1層12B之壓痕硬度較佳為1MPa以上100MPa以下，第2層12C之壓痕硬度較佳為10MPa以上 500MPa以下，第3層12D之壓痕硬度較佳為100MPa以上1000MPa以下。若第1層之壓痕硬度為1MPa以上，則可更加提升鉛筆硬度，又若第1層之壓痕硬度為100MPa以下，則可更加提升耐撞擊性。若第2層之壓痕硬度為10MPa以上，則在折疊光學膜時樹脂層會更加不易發生裂縫，又若第2層之壓痕硬度為500MPa以下，則在折疊光學膜時樹脂層會更加不易發生皺折。若第3層之壓痕硬度為100MPa以上，則可更加提升耐擦傷性，又若第3層之壓痕硬度為1000MPa以下，則在折疊光學膜時樹脂層會更加不易發生裂縫。 When the resin layer 12 has a three-layer structure, the indentation hardness of each layer of the first layer 12B, the second layer 12C, and the third layer 12D is not particularly limited as long as the above-mentioned relational formula (B) is satisfied. The first layer 12B The indentation hardness is preferably 1 MPa or more and 100 MPa or less, the indentation hardness of the second layer 12C is preferably 10 MPa or more and 500 MPa or less, and the indentation hardness of the third layer 12D is preferably 100 MPa or more and 1000 MPa or less. If the indentation hardness of the first layer is 1 MPa or more, the pencil hardness can be further improved, and if the indentation hardness of the first layer is 100 MPa or less, the impact resistance can be further improved. If the indentation hardness of the second layer is 10MPa or more, the resin layer will be more difficult to crack when the optical film is folded, and if the indentation hardness of the second layer is 500MPa or less, the resin layer will be more difficult to fold the optical film Wrinkles occur. If the indentation hardness of the third layer is 100 MPa or more, the scratch resistance can be improved, and if the indentation hardness of the third layer is 1000 MPa or less, the resin layer will be less prone to cracks when the optical film is folded.

<第1層> <Level 1>

第1層12B為第1層12B至第3層12D中具有最低壓痕硬度之層，主要具有提升鉛筆硬度及耐撞擊性之功能。第1層12B之膜厚較佳為50μm以上300μm以下。若第1層之膜厚為50μm以上，則可更加提升樹脂層之硬度，又若為300μm以下，則膜厚不會過厚，適於薄型化，且加工性亦為良好。關於第1層12B之膜厚，係使用掃描型電子顯微鏡(SEM)，拍攝第1層12B之剖面，於該剖面之影像中測量20處第1層12B之膜厚，將該20處之膜厚的算術平均值作為第1層12B之膜厚。第1層12B之下限更佳依序為80μm以上、100μm以上、150μm以上(數值越大越佳)，第1層12B之上限則更佳依序為250μm以下、220μm以下、200μm以下(數值越小越佳)。 The first layer 12B is the layer with the lowest indentation hardness among the first layer 12B to the third layer 12D, and mainly has the functions of improving pencil hardness and impact resistance. The film thickness of the first layer 12B is preferably 50 μm or more and 300 μm or less. If the film thickness of the first layer is 50 μm or more, the hardness of the resin layer can be further increased, and if it is 300 μm or less, the film thickness will not be too thick, it is suitable for thinning, and the workability is also good. Regarding the film thickness of the first layer 12B, a scanning electron microscope (SEM) was used to photograph a cross section of the first layer 12B, and the film thickness of the first layer 12B at 20 locations was measured in the image of the cross section. The arithmetic average of the thicknesses is used as the film thickness of the first layer 12B. The lower limit of the first layer 12B is more preferably 80 μm or more, 100 μm or more, and 150 μm or more (the larger the value is, the better), and the upper limit of the first layer 12B is more preferably 250 μm or less, 220 μm or less, and 200 μm or less (the smaller the value is) The better).

關於上述第1層之膜厚，係使用掃描型電子顯微鏡(SEM)，拍攝第1層之剖面，於該剖面之影像中測量20處第1層之膜厚，將該20處之膜厚的算術平均值作為第1層之膜厚。將具體之剖面照片的拍攝方法記載於下。首先製作藉由埋置樹脂埋置切成1mm×10mm之光學膜而成的團塊，藉由一般切片製作方法從該團塊切下沒有孔洞等之均勻的厚度70nm以上100nm以下之切片。切片之製作，可使用「Ultramicrotome EM UC7」(Leica Microsystems股份有限公司)等。然後，將被切下此沒有孔洞等之均勻的切片剩下的團塊作為測量樣品。然 後，使用掃描型電子顯微鏡(SEM)(製品名「S-4800」，日立全球先端科技公司製)，拍攝測量樣品之剖面照片。於使用上述S-4800拍攝剖面照片時，將檢測器設為「SE」，加速電壓設為「5kV」，射出電流設為「10μA」，進行剖面觀察。關於倍率，係一邊調節焦點，對對比度及亮度觀察是否可辨別各層，一邊以100~10萬倍作適當調節。另，於使用上述S-4800拍攝剖面照片時，可進一步將光圈設為「束監測器孔徑3」，物鏡孔徑設為「3」，且W.D.設為「8mm」。當測量第1層之膜厚時，於觀察剖面的時候，儘可能地可明確觀察到第1層與其他層(例如第2層)之界面對比度一事變得很重要。假如當對比度不足而難以看見此界面之情形時，由於若實施四氧化鋨、四氧化釕、磷鎢酸等染色處理，則會變得容易看見有機層間之界面，因此，亦可進行染色處理。又，界面之對比度有時會在高倍率下較難察覺。當該情形時，亦以低倍率同時作觀察。例如以2.5萬倍與5萬倍，或5萬倍與10萬倍等高低之兩種倍率觀察，以兩倍率求出上述之算術平均值，並進一步將該平均值作為第1層膜厚之值。 Regarding the film thickness of the above-mentioned first layer, a scanning electron microscope (SEM) was used to take a cross-section of the first layer, and the film thickness of the first layer was measured at 20 locations in the image of the cross-section. The arithmetic average is used as the film thickness of the first layer. The specific method of taking the cross-sectional photos is described below. First, an agglomerate formed by embedding an optical film of 1mm×10mm by embedding resin is produced, and a slice with a uniform thickness of 70 nm to 100 nm without holes is cut from the agglomerate by a general slicing method. For the production of slices, "Ultramicrotome EM UC7" (Leica Microsystems Co., Ltd.) can be used. Then, the mass left over from this uniform slice without holes or the like is used as a measurement sample. Then, a scanning electron microscope (SEM) (product name "S-4800", manufactured by Hitachi Global Advanced Technologies) was used to take a cross-sectional photograph of the measured sample. When using the above-mentioned S-4800 to take cross-sectional photos, set the detector to "SE", the acceleration voltage to "5kV", and the emission current to "10μA" to observe the cross-section. Regarding the magnification, while adjusting the focus and observing whether the layers can be distinguished by contrast and brightness, the magnification is adjusted appropriately from 100 to 100,000 times. In addition, when using the above-mentioned S-4800 to take cross-sectional photos, the aperture can be further set to "beam monitor aperture 3", objective lens aperture to "3", and W.D. to "8mm". When measuring the film thickness of the first layer, when observing the cross section, it becomes important to clearly observe the interface contrast between the first layer and other layers (for example, the second layer) as much as possible. If the contrast is insufficient and it is difficult to see the interface, the interface between the organic layers will become easier to be seen if dyeing treatments such as osmium tetroxide, ruthenium tetroxide, phosphotungstic acid, etc. are carried out. Therefore, dyeing treatment can also be performed. In addition, the contrast of the interface may be difficult to detect under high magnification. When this is the case, also observe at the same time at a low magnification. For example, observe at two magnifications of 25,000 times and 50,000 times, or 50,000 times and 100,000 times, and calculate the above-mentioned arithmetic average at twice the rate, and further use the average as the first layer thickness value.

構成第1層12B之樹脂若為第1層12B之壓痕硬度低於第2層12C之壓痕硬度之類的樹脂，則並無特別限定。作為此種樹脂，例如可列舉：胺酯(urethane)系樹脂、環氧系樹脂、聚矽氧系樹脂等。此等之中，胺酯系樹脂由於靱性優異，因此從得到優異之折疊性能的觀點及得到鉛筆硬度為3H以上之優異硬度的觀點而言，較佳為胺酯系樹脂。另，樹脂層12除了胺酯系樹脂或環氧系樹脂等之外，亦可含有橡膠或熱塑性彈性物。 The resin constituting the first layer 12B is not particularly limited as long as the indentation hardness of the first layer 12B is lower than the indentation hardness of the second layer 12C. Examples of such resins include urethane resins, epoxy resins, and silicone resins. Among these, the urethane-based resin is excellent in turbidity, and therefore, from the viewpoint of obtaining excellent folding performance and obtaining an excellent hardness with a pencil hardness of 3H or more, a urethane-based resin is preferable. In addition, the resin layer 12 may contain rubber or thermoplastic elastomer in addition to urethane-based resin, epoxy-based resin, and the like.

胺酯系樹脂為具有胺酯鍵之樹脂。作為胺酯系樹脂，可列舉：游離輻射硬化性胺酯系樹脂組成物之硬化物或熱硬化性胺酯系樹脂組成物之硬化物等。此等之中，從可得到耐擦傷性及高硬度，且硬化速度亦快，量產性優異的觀點而言，較佳為游離輻射硬化性胺酯系樹脂組成物之硬化物。 The urethane-based resin is a resin having an urethane bond. Examples of the urethane resin include a cured product of an ionizing radiation-curable urethane resin composition or a cured product of a thermosetting urethane resin composition. Among these, a cured product of an ionizing radiation-curable urethane-based resin composition is preferred from the viewpoint that it can obtain scratch resistance and high hardness, has a fast curing speed, and is excellent in mass productivity.

游離輻射硬化性胺酯系樹脂組成物含有胺酯(甲基)丙烯酸酯， 熱硬化性胺酯系樹脂組成物則含有多元醇(polyol)化合物與異氰酸酯化合物。胺酯(甲基)丙烯酸酯、多元醇化合物及異氰酸酯化合物可為單體、寡聚物及預聚合物之任一者。另，「胺酯(甲基)丙烯酸酯」意指包含「胺酯丙烯酸酯」及「胺酯甲基丙烯酸酯」兩者。 The ionizing radiation curable urethane-based resin composition contains urethane (meth)acrylate, and the thermosetting urethane-based resin composition contains a polyol compound and an isocyanate compound. The urethane (meth)acrylate, polyol compound, and isocyanate compound may be any of monomers, oligomers, and prepolymers. In addition, "urethane (meth)acrylate" means to include both "urethane acrylate" and "urethane methacrylate".

胺酯(甲基)丙烯酸酯中之(甲基)丙烯醯基的數目(官能基數)較佳為2以上6以下。若胺酯(甲基)丙烯酸酯中之(甲基)丙烯醯基的數目未達2，則會有鉛筆硬度變低之虞，又若超過6，則會有下述之虞：硬化收縮變大，光學膜捲曲，又於彎折時樹脂層會有裂紋。胺酯(甲基)丙烯酸酯中之(甲基)丙烯醯基數目的上限更佳為3以下。另，「(甲基)丙烯醯基」意指「丙烯醯基」及「甲基丙烯醯基」兩者。 The number of (meth)acrylic groups (the number of functional groups) in the urethane (meth)acrylate is preferably 2 or more and 6 or less. If the number of (meth)acrylic groups in the urethane (meth)acrylate is less than 2, the pencil hardness may decrease, and if it exceeds 6, the following may occur: Hardening shrinkage Large, the optical film is curled, and the resin layer will crack when it is bent. The upper limit of the number of (meth)acrylic groups in the urethane (meth)acrylate is more preferably 3 or less. In addition, "(meth)acryloyl" means both "acryloyl" and "methacryloyl".

胺酯(甲基)丙烯酸酯之重量平均分子量並無特別限定，較佳為1500以上20000以下。若胺酯(甲基)丙烯酸酯之重量平均分子量未達1500，則會有耐撞擊性下降之虞，又若超過20000，則會有游離輻射硬化性胺酯系樹脂組成物之黏度上升，塗布性惡化之虞。胺酯(甲基)丙烯酸酯之重量平均分子量的下限更佳為2000以上，上限更佳為15000以下。 The weight average molecular weight of the urethane (meth)acrylate is not particularly limited, but it is preferably 1,500 or more and 20,000 or less. If the weight average molecular weight of the urethane (meth)acrylate is less than 1500, the impact resistance may decrease, and if it exceeds 20,000, the viscosity of the ionizing radiation-curable urethane resin composition may increase. The risk of sexual deterioration. The lower limit of the weight average molecular weight of the urethane (meth)acrylate is more preferably 2,000 or more, and the upper limit is more preferably 15,000 or less.

又，作為具有來自胺酯(甲基)丙烯酸酯之構造的重複單元，例如可列舉：由下述通式(25)、(26)、(27)或(28)表示之構造等。 Moreover, as a repeating unit which has a structure derived from an amine ester (meth)acrylate, the structure represented by the following general formula (25), (26), (27), or (28) etc. is mentioned, for example.

Figure 106135143-A0202-12-0032-27
Figure 106135143-A0202-12-0032-27

上述通式(25)中，R7表示支鏈狀烷基，R8表示支鏈狀烷基或飽和環狀脂肪族基，R9表示氫原子或甲基，R10表示氫原子、甲基或乙基，m表示0以上之整數，x表示0~3之整數。 In the above general formula (25), R 7 represents a branched alkyl group, R 8 represents a branched alkyl group or a saturated cyclic aliphatic group, R 9 represents a hydrogen atom or a methyl group, and R 10 represents a hydrogen atom, a methyl group Or ethyl, m represents an integer of 0 or more, and x represents an integer of 0 to 3.

Figure 106135143-A0202-12-0033-28
Figure 106135143-A0202-12-0033-28

上述通式(26)中，R7表示支鏈狀烷基，R8表示支鏈狀烷基或飽和環狀脂肪族基，R9表示氫原子或甲基，R10表示氫原子、甲基或乙基，n表示1以上之整數，x表示0~3之整數。 In the above general formula (26), R 7 represents a branched alkyl group, R 8 represents a branched alkyl group or a saturated cyclic aliphatic group, R 9 represents a hydrogen atom or a methyl group, and R 10 represents a hydrogen atom, a methyl group. Or ethyl, n represents an integer of 1 or more, and x represents an integer of 0-3.

Figure 106135143-A0202-12-0033-29
Figure 106135143-A0202-12-0033-29

上述通式(27)中，R7表示支鏈狀烷基，R8表示支鏈狀烷基或飽和環狀脂肪族基，R9表示氫原子或甲基，R10表示氫原子、甲基或乙基，m表示0以上之整數，x表示0~3之整數。 In the above general formula (27), R 7 represents a branched alkyl group, R 8 represents a branched alkyl group or a saturated cyclic aliphatic group, R 9 represents a hydrogen atom or a methyl group, and R 10 represents a hydrogen atom, a methyl group. Or ethyl, m represents an integer of 0 or more, and x represents an integer of 0 to 3.

Figure 106135143-A0202-12-0033-30
Figure 106135143-A0202-12-0033-30

上述通式(28)中，R7表示支鏈狀烷基，R8表示支鏈狀烷基或飽和環狀脂肪族基，R9表示氫原子或甲基，R10表示氫原子、甲基或乙基，n表示1以上之整數，x表示0~3之整數。 In the above general formula (28), R 7 represents a branched alkyl group, R 8 represents a branched alkyl group or a saturated cyclic aliphatic group, R 9 represents a hydrogen atom or a methyl group, and R 10 represents a hydrogen atom, a methyl group. Or ethyl, n represents an integer of 1 or more, and x represents an integer of 0-3.

另，關於構成第1層12B等之樹脂係由何種構造之高分子鏈(重複單元)形成，例如可用熱分解GC-MS及FT-IR分析第1層12B等來判斷。尤其是熱分解GC-MS由於可檢測第1層12B等所含之單體單元作為單體成分，故有用。 Regarding the structure of the polymer chain (repeating unit) of the resin system constituting the first layer 12B, etc., it can be determined by, for example, thermal decomposition GC-MS and FT-IR analysis of the first layer 12B. In particular, thermal decomposition GC-MS is useful because it can detect monomer units contained in the first layer 12B and the like as monomer components.

第1層12B若壓痕硬度低於第2層12C之壓痕硬度，則亦可含有紫外線吸收劑、分光穿透率調整劑等。 If the indentation hardness of the first layer 12B is lower than the indentation hardness of the second layer 12C, it may contain an ultraviolet absorber, a spectral transmittance adjuster, and the like.

<紫外線吸收劑> <Ultraviolet Absorber>

光學膜尤其適用於可折疊之智慧型手機或平板終端之類的移動終端機，但此種移動終端機多在戶外使用，因此會有較光學膜更靠近顯示元件側配置之偏光元件受到紫外線曝曬而容易劣化的問題。然而，第1層由於配置於偏光元件之顯示畫面側，故若第1層含有紫外吸收劑，則可適合地防止因偏光元件受到紫外線曝曬而造成之劣化。另，上述紫外線吸收劑(UVA)亦可含有於基材11或第2層~第n層之至少任一層。此情形時，紫外線吸收劑(UVA)亦可不含有於第1層12B。 Optical film is especially suitable for mobile terminals such as foldable smartphones or tablet terminals. However, such mobile terminals are mostly used outdoors, so there will be polarizing elements placed closer to the display element side than optical films that are exposed to ultraviolet rays. And the problem of easy degradation. However, since the first layer is disposed on the display screen side of the polarizing element, if the first layer contains an ultraviolet absorber, it can suitably prevent the polarizing element from being degraded due to UV exposure. In addition, the aforementioned ultraviolet absorber (UVA) may be contained in at least any one of the base material 11 or the second layer to the nth layer. In this case, the ultraviolet absorber (UVA) may not be contained in the first layer 12B.

作為紫外線吸收劑，例如可列舉：三

Figure 106135143-A0202-12-0034-42
系紫外線吸收劑、二苯甲酮系紫外線吸收劑及苯并***系紫外線吸收劑等。 As the ultraviolet absorber, for example, three
Figure 106135143-A0202-12-0034-42
UV absorbers, benzophenone UV absorbers, benzotriazole UV absorbers, etc.

作為上述三

Figure 106135143-A0202-12-0034-43
系紫外線吸收劑，例如可列舉：2-(2-羥基-4-[1-辛氧基羰基乙氧基]苯基)-4,6-雙(4-苯基苯基)-1,3,5-三
Figure 106135143-A0202-12-0034-44
、2-[4-[(2-羥基-3-十二氧丙基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三
Figure 106135143-A0202-12-0034-45
、2,4-雙[2-羥基-4-丁氧基苯基]-6-(2,4-二丁氧基苯基)-1,3,5-三
Figure 106135143-A0202-12-0034-46
、2-[4-[(2-羥基-3-三癸氧基丙基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三
Figure 106135143-A0202-12-0034-47
及2-[4-[(2-羥基-3-(2’-乙基)己基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三
Figure 106135143-A0202-12-0034-48
等。作為市售之三
Figure 106135143-A0202-12-0034-49
系紫外線吸收劑，例如可列舉：TINUVIN460、TINUVIN477(皆為BASF公司製)，LA-46(艾迪科公司製)等。 As the above three
Figure 106135143-A0202-12-0034-43
UV absorbers, such as 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3 ,5-three
Figure 106135143-A0202-12-0034-44
, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1, 3,5-Three
Figure 106135143-A0202-12-0034-45
, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-tri
Figure 106135143-A0202-12-0034-46
, 2-[4-[(2-hydroxy-3-tridecoxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-three
Figure 106135143-A0202-12-0034-47
And 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) -1,3,5-three
Figure 106135143-A0202-12-0034-48
Wait. As the third commercially available
Figure 106135143-A0202-12-0034-49
The ultraviolet absorber includes, for example, TINUVIN460, TINUVIN477 (all manufactured by BASF Corporation), LA-46 (manufactured by Adike Corporation), and the like.

作為上述二苯甲酮系紫外線吸收劑，例如可列舉：2-羥基二苯甲酮、2,4-二羥基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基二苯甲酮、2,2’,4,4’-四羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、羥基甲氧基二苯甲酮碸酸及其三水合物(trihydrate)、羥基甲氧基二苯甲酮碸酸鈉等。作為市售之二苯甲酮系紫外線吸收劑，例如可舉CHMASSORB81/FL(BASF公司製)等。 Examples of the aforementioned benzophenone-based ultraviolet absorbers include 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy Benzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, hydroxymethoxybenzophenone acid and its three Trihydrate, sodium hydroxymethoxybenzophenone and so on. Examples of commercially available benzophenone-based ultraviolet absorbers include CHMASSORB81/FL (manufactured by BASF Corporation).

作為上述苯并***系紫外線吸收劑，例如可列舉：2-乙基己基 -3-[3-三級丁基-4-羥基-5-(5-氯基-2H-苯并***-2-基)苯基]丙酸酯、2-(2H-苯并***-2-基)-6-(直鏈及側鏈十二基)-4-甲苯酚、2-[5-氯(2H)-苯并***-2-基]-4-甲基-6-(三級丁基)苯酚、2-(2H-苯并***-2-基)-4,6-二-三級戊基苯酚、2-(2’-羥基-5’-甲基苯基)苯并***、2-(2’-羥基-3’,5’-二-三級丁基苯基)苯并***、2-(2’-羥基-3’-三級丁基-5’-甲基苯基)苯并***、2-(2’-羥基-3’,5’-二-三級丁基苯基)-5-氯苯并***、2-(2’-羥基-3’-(3”,4”,5”,6”-四氫酞醯亞胺甲基)-5’-甲基苯基)苯并***、2,2-亞甲基(methylene)雙(4-(1,1,3,3-四甲基丁基)-6-(2H-苯并***-2-基)苯酚)及2-(2’-羥基-3'-三級丁基-5'-甲基苯基)-5-氯苯并***等。作為市售之苯并***系紫外線吸收劑，例如可列舉：KEMISORB71D、KEMISORB79(皆為凱米布羅化成公司製)，JF-80、JAST-500(皆為城北化學公司製)，ULS-1933D(一方公司製)，RUVA-93(大塚化學公司製)等。 Examples of the above-mentioned benzotriazole-based ultraviolet absorbers include 2-ethylhexyl-3-[3-tertiarybutyl-4-hydroxy-5-(5-chloro-2H-benzotriazole- 2-yl)phenyl]propionate, 2-(2H-benzotriazol-2-yl)-6-(linear and side-chain dodecyl)-4-cresol, 2-[5-chloro (2H)-benzotriazol-2-yl)-4-methyl-6-(tertiary butyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-di- Tertiary amylphenol, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tertiary butylphenyl) Benzotriazole, 2-(2'-hydroxy-3'-tertiary butyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di- Tertiary butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-(3",4",5",6"-tetrahydrophthaliminomethyl)- 5'-methylphenyl)benzotriazole, 2,2-methylene bis(4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzo Triazol-2-yl)phenol) and 2-(2'-hydroxy- 3' -tertiarybutyl- 5' -methylphenyl)-5-chlorobenzotriazole, etc. As commercially available benzotriazole-based ultraviolet absorbers, for example, KEMISORB71D, KEMISORB79 (all manufactured by Kemibro Chemical Co., Ltd.), JF-80, JAST-500 (all manufactured by Chengbei Chemical Co., Ltd.), ULS- 1933D (manufactured by Yifang Corporation), RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.), etc.

關於紫外線吸收劑，其中，適用三

Figure 106135143-A0202-12-0035-50
系紫外線吸收劑、苯并***系紫外線吸收劑。紫外線吸收劑以與構成樹脂層之樹脂成分的溶解性較高為佳，又，以上述之耐久折疊測試後的滲出(bleed out)較少為佳。紫外線吸收劑較佳經聚合物化或寡聚物化。作為紫外線吸收劑較佳為具有苯并***、三
Figure 106135143-A0202-12-0035-51
、二苯甲酮骨架之聚合物或寡聚物，具體而言，較佳為使具有苯并***或二苯甲酮骨架之(甲基)丙烯酸酯與甲基丙烯酸甲酯(MMA)以任意比率熱共聚合而成者。另，當將光學膜應用於有機發光二極體(OLED)顯示裝置之情形時，紫外線吸收劑亦可發揮保護OLED免受紫外線傷害之作用。 Regarding ultraviolet absorbers, three of them are applicable
Figure 106135143-A0202-12-0035-50
It is a UV absorber and a benzotriazole UV absorber. The ultraviolet absorber preferably has a higher solubility with the resin component constituting the resin layer, and it is also better to have less bleed out after the aforementioned durable folding test. The ultraviolet absorber is preferably polymerized or oligomerized. As the ultraviolet absorber, it is preferable to have benzotriazole, triazole
Figure 106135143-A0202-12-0035-51
, A polymer or oligomer with a benzophenone skeleton, specifically, it is preferable to use a (meth)acrylate having a benzotriazole or benzophenone skeleton with methyl methacrylate (MMA) Any ratio of thermal copolymerization. In addition, when the optical film is applied to an organic light emitting diode (OLED) display device, the ultraviolet absorber can also play a role in protecting the OLED from ultraviolet rays.

紫外線吸收劑之含量並無特別限定，較佳相對於第1層用組成物之固形物成分100質量份，為1質量份以上6質量份以下。若未達1質量份，則有時會無法充分得到使第1層含有上述紫外線吸收劑之效果，若超過6質量份，則 有時會於第1層產生顯著之著色或強度下降。上述紫外線吸收劑含量之更佳下限為2質量份以上，更佳上限為5質量份以下。 The content of the ultraviolet absorber is not particularly limited, but it is preferably 1 part by mass or more and 6 parts by mass or less with respect to 100 parts by mass of the solid content of the composition for the first layer. If the amount is less than 1 part by mass, the effect of containing the ultraviolet absorber in the first layer may not be sufficiently obtained, and if it exceeds 6 parts by mass, the first layer may be markedly colored or the strength may decrease. The lower limit of the content of the ultraviolet absorber is more preferably 2 parts by mass or more, and the upper limit is more preferably 5 parts by mass or less.

<分光穿透率調整劑> <Spectral transmittance adjuster>

分光穿透率調整劑係調整光學膜之分光穿透率者。當使第1層例如含有下述通式(29)表示之芝麻酚型苯并***系單體的情形時，可正好滿足上述之分光穿透率。 The spectral transmittance adjusting agent is one that adjusts the spectral transmittance of the optical film. When the first layer contains, for example, a sesamol type benzotriazole-based monomer represented by the following general formula (29), the above-mentioned spectral transmittance can be just satisfied.

Figure 106135143-A0202-12-0036-31
Figure 106135143-A0202-12-0036-31

式中，R11表示氫原子或甲基。R12表示碳數1~6之直鏈狀或支鏈狀伸烷基或碳數1~6之直鏈狀或支鏈狀氧伸烷基(oxyalkylene)。 In the formula, R 11 represents a hydrogen atom or a methyl group. R 12 represents a linear or branched alkylene group with 1 to 6 carbons or a linear or branched oxyalkylene group with 1 to 6 carbons.

上述之芝麻酚型苯并***系單體並無特別限制，具體之物質名稱可列舉：2-[2-(6-羥基苯并[1,3]1,3-二氧呃(dioxole)-5-基)-2H-苯并***-5-基]乙基甲基丙烯酸酯、2-[2-(6-羥基苯并[1,3]1,3-二氧呃-5-基)-2H-苯并***-5-基]乙基丙烯酸酯、3-[2-(6-羥基苯并[1,3]1,3-二氧呃-5-基)-2H-苯并***-5-基]丙基甲基丙烯酸酯、3-[2-(6-羥基苯并[1,3]1,3-二氧呃-5-基)-2H-苯并***-5-基]丙基丙烯酸酯、4-[2-(6-羥基苯并[1,3]1,3-二氧呃-5-基)-2H-苯并***-5-基]丁基甲基丙烯酸酯、4-[2-(6-羥基苯并[1,3]1,3-二氧呃-5-基)-2H-苯并***-5-基]丁基丙烯酸酯、2-[2-(6-羥基苯并[1,3]1,3-二氧呃-5-基)-2H-苯并***-5-基氧基]乙基甲基丙烯酸酯、2-[2-(6-羥基苯并[1,3]1,3-二氧呃-5-基)-2H-苯并***-5-基氧基]乙基丙烯酸酯、2-[3-{2-(6-羥基苯并[1,3]1,3-二氧呃-5-基)-2H-苯并***-5-基}丙醯基氧基]乙基甲基丙烯酸酯、2-[3-{2-(6-羥基苯并[1,3]1,3-二氧呃-5-基)-2H-苯并***-5- 基}丙醯基氧基]乙基丙烯酸酯、4-[3-{2-(6-羥基苯并[1,3]1,3-二氧呃-5-基)-2H-苯并***-5-基}丙醯基氧基]丁基甲基丙烯酸酯、4-[3-{2-(6-羥基苯并[1,3]1,3-二氧呃-5-基)-2H-苯并***-5-基}丙醯基氧基]丁基丙烯酸酯、2-[3-{2-(6-羥基苯并[1,3]1,3-二氧呃-5-基)-2H-苯并***-5-基}丙醯基氧基]乙基甲基丙烯酸酯、2-[3-{2-(6-羥基苯并[1,3]1,3-二氧呃-5-基)-2H-苯并***-5-基}丙醯基氧基]乙基丙烯酸酯、2-(甲基丙烯醯氧基(methacryloyloxy))乙基2-(6-羥基苯并[1,3]1,3-二氧呃-5-基)-2H-苯并***-5羧酸酯、2-(丙烯醯氧基(acryloyloxy))乙基2-(6-羥基苯并[1,3]1,3-二氧呃-5-基)-2H-苯并***-5-羧酸酯、4-(甲基丙烯醯氧基)丁基2-(6-羥基苯并[1,3]1,3-二氧呃-5-基)-2H-苯并***-5-羧酸酯、4-(丙烯醯氧基)丁基2-(6-羥基苯并[1,3]1,3-二氧呃-5-基)-2H-苯并***-5-羧酸酯等。又，此等芝麻酚型苯并***系單體可使用1種，又亦可使用2種以上。 The above-mentioned sesamol-type benzotriazole monomers are not particularly limited. Specific substance names can include: 2-[2-(6-hydroxybenzo[1,3]1,3-dioxole) -5-yl)-2H-benzotriazol-5-yl]ethyl methacrylate, 2-[2-(6-hydroxybenzo[1,3]1,3-dioxer-5- Yl)-2H-benzotriazol-5-yl]ethyl acrylate, 3-[2-(6-hydroxybenzo[1,3]1,3-dioxer-5-yl)-2H- Benzotriazol-5-yl]propyl methacrylate, 3-[2-(6-hydroxybenzo[1,3]1,3-dioxer-5-yl)-2H-benzotri Azol-5-yl]propyl acrylate, 4-[2-(6-hydroxybenzo[1,3]1,3-dioxoer-5-yl)-2H-benzotriazol-5-yl ] Butyl methacrylate, 4-[2-(6-hydroxybenzo[1,3]1,3-dioxoer-5-yl)-2H-benzotriazol-5-yl]butyl acrylate , 2-[2-(6-Hydroxybenzo[1,3]1,3-dioxoer-5-yl)-2H-benzotriazol-5-yloxy]ethyl methacrylate, 2-[2-(6-Hydroxybenzo[1,3]1,3-dioxoer-5-yl)-2H-benzotriazol-5-yloxy]ethyl acrylate, 2-[ 3-{2-(6-Hydroxybenzo[1,3]1,3-dioxoer-5-yl)-2H-benzotriazol-5-yl}propanyloxy]ethylmethyl Acrylate, 2-[3-{2-(6-hydroxybenzo[1,3]1,3-dioxoer-5-yl)-2H-benzotriazol-5-yl}propanyloxy Yl]ethyl acrylate, 4-[3-{2-(6-hydroxybenzo[1,3]1,3-dioxoer-5-yl)-2H-benzotriazol-5-yl} Propyloxy]butyl methacrylate, 4-[3-{2-(6-hydroxybenzo[1,3]1,3-dioxer-5-yl)-2H-benzotriazole- 5-yl}propanyloxy]butyl acrylate, 2-[3-{2-(6-hydroxybenzo[1,3]1,3-dioxoer-5-yl)-2H-benzene N-triazol-5-yl}propanyloxy]ethyl methacrylate, 2-[3-{2-(6-hydroxybenzo[1,3]1,3-dioxer-5- Group)-2H-benzotriazol-5-yl}propanyloxy]ethyl acrylate, 2-(methacryloyloxy)ethyl 2-(6-hydroxybenzo[1 ,3] 1,3-dioxoer-5-yl)-2H-benzotriazole-5 carboxylate, 2-(acryloyloxy)ethyl 2-(6-hydroxybenzo[ 1,3]1,3-dioxoer-5-yl)-2H-benzotriazole-5-carboxylate, 4-(methacryloxy)butyl 2-(6-hydroxybenzo [1,3] 1,3-dioxoer-5-yl)-2H-benzotriazole-5-carboxylate, 4-(propenyloxy)butyl 2-(6-Hydroxybenzo[1,3]1,3-dioxoer-5-yl)-2H-benzotriazole-5-carboxylate and the like. In addition, these sesamol-type benzotriazole-based monomers may be used singly, or two or more kinds may be used.

上述芝麻酚型苯并***系單體雖可含有於第1層12B，但亦可含有於第1層~第n層之至少任一層，滿足上述分光穿透率之要件。例如可舉下述之構成等：在第1層以僅可達成於波長380nm之分光穿透率的方式含有上述芝麻酚型苯并***系單體，其他層以可達成於波長410nm及波長440nm之分光穿透率之條件的方式含有上述芝麻酚型苯并***系單體。 Although the above-mentioned sesamol-type benzotriazole-based monomer may be contained in the first layer 12B, it may be contained in at least any one of the first layer to the n-th layer and satisfy the requirements of the above-mentioned spectral transmittance. For example, the following composition can be mentioned: the first layer contains the above-mentioned sesamol-type benzotriazole-based monomer so that the spectral transmittance can only be achieved at a wavelength of 380nm, and the other layers can be achieved at a wavelength of 410nm and a wavelength The method of the condition of the spectral transmittance of 440 nm contains the above-mentioned sesamol-type benzotriazole-based monomer.

當上述芝麻酚型苯并***系單體含有於第1層12B之情形時，例如，上述芝麻酚型苯并***系單體較佳於第1層12B層中含有15~30質量%。藉由在此種範圍含有芝麻酚型苯并***系單體，而可滿足上述之分光穿透率。另，上述芝麻酚型苯并***系單體可於第1層12B中與構成第1層12B之樹脂成分反應而一體地含有，亦可不與構成第1層12B之樹脂成分反應，單獨地含有。 When the above-mentioned sesamol-type benzotriazole-based monomer is contained in the first layer 12B, for example, the above-mentioned sesamol-type benzotriazole-based monomer preferably contains 15-30% by mass in the first layer 12B. . By containing the sesamol-type benzotriazole-based monomer in this range, the above-mentioned spectral transmittance can be satisfied. In addition, the above-mentioned sesamol-type benzotriazole-based monomer may react with the resin component constituting the first layer 12B in the first layer 12B to be contained integrally, or may not react with the resin component constituting the first layer 12B, and may be separately contained. contain.

<第2層> <Level 2>

第2層12C為具有第1層12B與第3層12D之間的壓痕硬度之層，主要具有提升彎曲性及耐擦傷性之功能。第2層12C之膜厚較佳為1μm以上50μm以下。若第2層之膜厚為1μm以上，則當折疊光學膜時會更難以發生樹脂層之皺折，又若為50μm以下，則當折疊光學膜時會更難以發生樹脂層之裂縫。第2層12C之膜厚係藉由與第1層12B之膜厚同樣的方法求得。第2層12C之下限更佳依序為3μm以上、5μm以上、7μm以上(數值越大越佳)，第2層12C之上限更佳依序為30μm以下、25μm以下、20μm以下(數值越小越佳)。 The second layer 12C is a layer having the indentation hardness between the first layer 12B and the third layer 12D, and mainly has the function of improving the bendability and scratch resistance. The film thickness of the second layer 12C is preferably 1 μm or more and 50 μm or less. If the thickness of the second layer is 1 μm or more, it will be more difficult for the resin layer to wrinkle when the optical film is folded, and if it is 50 μm or less, it will be more difficult for the resin layer to crack when the optical film is folded. The film thickness of the second layer 12C is obtained by the same method as the film thickness of the first layer 12B. The lower limit of the second layer 12C is more preferably 3 μm or more, 5 μm or more, and 7 μm or more (the larger the value is, the better), and the upper limit of the second layer 12C is more preferably 30 μm or less, 25 μm or less, and 20 μm or less (the smaller the value, the better good).

關於構成第2層12C之材料，若第2層12C之壓痕硬度高於第1層12B之壓痕硬度，則並無特別限定。於第2層12C，例如可將無機粒子及/或有機粒子添加於第1層12B欄所說明之樹脂，藉此使壓痕硬度高於第1層12B，又，除了胺酯(甲基)丙烯酸酯之外，亦可添加壓痕硬度會變高之類的游離輻射聚合性化合物，藉此使壓痕硬度高於第1層12B。 Regarding the material constituting the second layer 12C, if the indentation hardness of the second layer 12C is higher than the indentation hardness of the first layer 12B, there is no particular limitation. In the second layer 12C, for example, inorganic particles and/or organic particles can be added to the resin described in the column of the first layer 12B, thereby making the indentation hardness higher than that of the first layer 12B, except for urethane (methyl) In addition to acrylate, an ionizing radiation polymerizable compound that increases the indentation hardness can also be added to make the indentation hardness higher than that of the first layer 12B.

(無機粒子) (Inorganic particles)

無機粒子為提高第2層12C之壓痕硬度的成分。作為無機粒子，例如可列舉：二氧化矽(SiO2)粒子、氧化鋁粒子、二氧化鈦粒子、氧化錫粒子、摻銻氧化錫(簡稱：ATO)粒子、氧化鋅粒子等無機氧化物粒子。此等之中，從更加提高硬度之觀點而言，較佳為二氧化矽粒子。作為二氧化矽粒子，可列舉：球形二氧化矽粒子或變形二氧化矽粒子，此等之中，較佳為變形二氧化矽粒子。本說明書中之「球形粒子」，例如意指球狀、橢圓球狀等粒子，「變形粒子」則意指馬鈴薯狀之表面具有任意凹凸之形狀的粒子。上述變形粒子由於其表面積較球狀粒子大，因此藉由含有此種變形粒子，與上述樹脂之接觸面積會變大，可使樹脂層12之鉛筆硬度更加優異。第2層12C所含之二氧化矽粒子是否為變形二氧化矽粒子，可藉由用穿透式電子顯微鏡(TEM)或掃描穿透式電子顯微鏡(STEM)觀察第2層12C之剖面來加以確認。當使用球形二氧化矽粒子之情形時，球形二 氧化矽粒子之粒徑越小，透光性功能層之硬度會越高。相對於此，變形二氧化矽粒子即使沒有小至市售之最小粒徑的球形二氧化矽粒子之程度，亦可達成與此球形二氧化矽粒子同等之硬度。 The inorganic particles are components that increase the indentation hardness of the second layer 12C. Examples of the inorganic particles include inorganic oxide particles such as silicon dioxide (SiO 2 ) particles, aluminum oxide particles, titanium dioxide particles, tin oxide particles, antimony-doped tin oxide (abbreviation: ATO) particles, and zinc oxide particles. Among these, from the viewpoint of further improving the hardness, silica particles are preferred. Examples of the silica particles include spherical silica particles and deformed silica particles. Among these, deformed silica particles are preferred. "Spherical particle" in this specification means, for example, spherical, elliptical, spherical, and other particles, and "deformed particle" means a potato-like particle with any irregularities on the surface. Since the surface area of the deformed particles is larger than that of the spherical particles, by containing such deformed particles, the contact area with the resin becomes larger, and the pencil hardness of the resin layer 12 can be made more excellent. Whether the silicon dioxide particles contained in the second layer 12C are deformed silicon dioxide particles can be determined by observing the cross-section of the second layer 12C with a transmission electron microscope (TEM) or scanning transmission electron microscope (STEM) confirm. When using spherical silica particles, the smaller the particle size of the spherical silica particles, the higher the hardness of the light-transmitting functional layer. In contrast, the deformed silica particles can achieve the same hardness as the spherical silica particles even if they are not as small as the smallest commercially available spherical silica particles.

二氧化矽粒子之平均一次粒徑較佳為1nm以上100nm以下。當二氧化矽粒子為變形二氧化矽粒子之情形時，關於變形二氧化矽粒子之平均一次粒徑，係從使用穿透式電子顯微鏡(TEM)或掃描穿透式電子顯微鏡(STEM)拍攝得到之透光性功能層剖面的影像測量粒子外圍之2點間距離的最大值(長徑)與最小值(短徑)，加以平均求得粒徑，將20個粒子之粒徑的算術平均值作為該變形二氧化矽粒子之平均一次粒徑。又，當二氧化矽粒子為球形二氧化矽粒子之情形時，關於球形二氧化矽粒子之平均粒徑，係從使用穿透式電子顯微鏡(TEM)或掃描穿透式電子顯微鏡(STEM)拍攝得到之粒子剖面的影像測量20個粒子之粒徑，將20個粒子之粒徑的算術平均值作為該球形二氧化矽粒子之平均粒徑。 The average primary particle size of the silicon dioxide particles is preferably 1 nm or more and 100 nm or less. When the silica particles are deformed silica particles, the average primary particle size of the deformed silica particles is obtained by using a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM) The image of the translucent functional layer profile measures the maximum (longer axis) and minimum (shorter axis) of the distance between two points on the periphery of the particle, and averages it to obtain the particle size, and calculates the arithmetic average of the particle size of 20 particles As the average primary particle size of the deformed silica particles. In addition, when the silica particles are spherical silica particles, the average particle size of the spherical silica particles is taken from using a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM) The obtained particle cross-section image measures the particle diameters of 20 particles, and the arithmetic average of the particle diameters of the 20 particles is taken as the average particle diameter of the spherical silica particles.

第2層12C中之無機粒子的含量較佳為20質量%以上70質量%以下。若無機粒子的含量未達20質量%，則會難以確保足夠之硬度，又若無機粒子的含量超過70質量%，則填充率會過度上升，無機粒子與樹脂成分之密接性惡化，反而使第2層之硬度下降。 The content of the inorganic particles in the second layer 12C is preferably 20% by mass or more and 70% by mass or less. If the content of inorganic particles is less than 20% by mass, it will be difficult to ensure sufficient hardness. If the content of inorganic particles exceeds 70% by mass, the filling rate will increase excessively, and the adhesion between the inorganic particles and the resin component will deteriorate, and the The hardness of the second layer is decreased.

作為無機粒子，較佳使用表面具有光聚合性官能基之無機粒子(反應性無機粒子)。此種表面具有光聚合性官能基之無機粒子，可藉由用矽烷偶合劑等對無機粒子進行表面處理來製作。作為用矽烷偶合劑處理無機粒子表面之方法，可列舉：對無機粒子噴灑矽烷偶合劑之乾式法，或使無機粒子分散於溶劑後將矽烷偶合劑加入使之反應的濕式法等。 As the inorganic particles, inorganic particles (reactive inorganic particles) having a photopolymerizable functional group on the surface are preferably used. Such inorganic particles having a photopolymerizable functional group on the surface can be produced by subjecting the inorganic particles to surface treatment with a silane coupling agent or the like. As a method of treating the surface of inorganic particles with a silane coupling agent, a dry method in which a silane coupling agent is sprayed on the inorganic particles, or a wet method in which the inorganic particles are dispersed in a solvent and then added with a silane coupling agent for reaction can be mentioned.

(有機粒子) (Organic particles)

有機粒子亦為提高第2層12C之壓痕硬度的成分。作為有機粒子，例如可舉 塑膠珠粒。作為塑膠珠粒，具體例可列舉：聚苯乙烯珠粒、三聚氰胺樹脂珠粒、丙烯酸珠粒、丙烯酸-苯乙烯珠粒、聚矽氧珠粒、苯胍

Figure 106135143-A0202-12-0040-52
(benzoguanamine)珠粒、苯胍
Figure 106135143-A0202-12-0040-53
-甲醛縮合珠粒、聚碳酸酯珠粒、聚乙烯珠粒等。 Organic particles are also components that increase the indentation hardness of the second layer 12C. Examples of organic particles include plastic beads. As the plastic beads, specific examples include: polystyrene beads, melamine resin beads, acrylic beads, acrylic-styrene beads, silicone beads, benzoguanidine
Figure 106135143-A0202-12-0040-52
(benzoguanamine) beads, benzoguanamine
Figure 106135143-A0202-12-0040-53
-Formaldehyde condensation beads, polycarbonate beads, polyethylene beads, etc.

(游離輻射聚合性化合物) (Ionizing radiation polymerizable compound)

游離輻射聚合性化合物亦為提高第2層12C之壓痕硬度的成分。游離輻射聚合性化合物係與胺酯(甲基)丙烯酸酯混合後使用。作為此種可提高壓痕硬度之類的游離輻射聚合性化合物，例如可列舉：2-羥基乙基(甲基)丙烯酸酯、2一羥基丙基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯等含有羥基之單體，或乙二醇二(甲基)丙烯酸酯、二伸乙甘醇二(甲基)丙烯酸酯、三伸甘醇二(甲基)丙烯酸酯、三縮四乙二醇(tetraethylene glycol)二(甲基)丙烯酸酯、伸丁二醇二(甲基)丙烯酸酯、三羥甲丙烷三(甲基)丙烯酸酯、三羥甲乙烷三(甲基)丙烯酸酯、新戊四醇二(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇四(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、甘油(甲基)丙烯酸酯等(甲基)丙烯酸酯單體。 The ionizing radiation polymerizable compound is also a component that increases the indentation hardness of the second layer 12C. The ionizing radiation polymerizable compound is used after being mixed with urethane (meth)acrylate. Examples of such ionizing radiation polymerizable compounds that can increase indentation hardness include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-ethylhexyl (Meth) acrylate and other monomers containing hydroxyl, or ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, Tetraethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate Base) acrylate, neopentaerythritol di(meth)acrylate, neopentaerythritol tri(meth)acrylate, neopentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate ) (Meth)acrylate monomers such as acrylate, dineopentaerythritol hexa(meth)acrylate, and glycerol (meth)acrylate.

<第3層> <Level 3>

第3層12D為第1層12B至第3層12D之中具有最高壓痕硬度的層，主要具有提升耐擦傷性之功能。第3層12D之膜厚較佳為0.05μm以上5μm以下。若第3層之膜厚為0.05μm以上，則可更加提升耐擦傷性，又若為5μm以下，則在折疊光學膜時樹脂層會更加不易發生裂縫。第3層12D之膜厚係藉由與第1層12B之膜厚同樣的方法求得。第3層12D之下限更佳依序為0.1μm以上、0.5μm以上、0.8μm以上(數值越大越佳)，第3層12D之上限更佳依序為3μm以下、2μm以下、1μm以下(數值越小越佳)。 The third layer 12D is the layer with the highest indentation hardness among the first layer 12B to the third layer 12D, and mainly has the function of improving the scratch resistance. The film thickness of the third layer 12D is preferably 0.05 μm or more and 5 μm or less. If the film thickness of the third layer is 0.05 μm or more, the scratch resistance can be further improved, and if it is 5 μm or less, the resin layer will be less prone to cracks when the optical film is folded. The film thickness of the third layer 12D is obtained by the same method as the film thickness of the first layer 12B. The lower limit of the third layer 12D is more preferably 0.1 μm or more, 0.5 μm or more, 0.8 μm or more (the larger the value is, the better), and the upper limit of the third layer 12D is more preferably 3 μm or less, 2 μm or less, 1 μm or less (numerical value The smaller the better).

關於構成第3層12D之材料，若第3層12D之壓痕硬度高於第2層 12C之壓痕硬度，則並無特別限定。於第3層12D，可不使用第1層12B欄所說明之樹脂，而使用第2層12C欄說明之游離輻射聚合性化合物，藉此使壓痕硬度高於第2層12C。又，第3層12D可進一步含有溶劑乾燥型樹脂或抗污劑。 Regarding the material constituting the third layer 12D, if the indentation hardness of the third layer 12D is higher than the indentation hardness of the second layer 12C, there is no particular limitation. For the third layer 12D, the resin described in the column of the first layer 12B may not be used, but the ionizing radiation polymerizable compound described in the column of the second layer 12C may be used to make the indentation hardness higher than that of the second layer 12C. In addition, the third layer 12D may further contain a solvent drying resin or an antifouling agent.

(溶劑乾燥型樹脂) (Solvent drying resin)

溶劑乾燥型樹脂為熱塑性樹脂等僅使塗布時為了調整固形物成分而添加之溶劑乾燥就會成為被膜之類的樹脂。當添加有溶劑乾燥型樹脂之情形時，可於形成第3層12D時，有效防止塗液塗布面之被膜缺陷。溶劑乾燥型樹脂並無特別限定，一般而言可使用熱塑性樹脂。 Solvent-drying resins are resins such as thermoplastic resins that are only dried to adjust the solid content of the solvent added at the time of coating to become a film or the like. When a solvent-dried resin is added, it can effectively prevent coating defects on the coating surface of the coating liquid when forming the third layer 12D. The solvent-drying resin is not particularly limited, and generally a thermoplastic resin can be used.

作為熱塑性樹脂，例如可列舉：苯乙烯系樹脂、(甲基)丙烯酸系樹脂、乙酸乙烯酯系樹脂、乙烯醚系樹脂、含鹵素樹脂、脂環式烯烴系樹脂、聚碳酸酯系樹脂、聚酯系樹脂、聚醯胺系樹脂、纖維素衍生物、聚矽氧系樹脂及橡膠或彈性物等。 Examples of thermoplastic resins include styrene resins, (meth)acrylic resins, vinyl acetate resins, vinyl ether resins, halogen-containing resins, alicyclic olefin resins, polycarbonate resins, and polycarbonate resins. Ester resins, polyamide resins, cellulose derivatives, silicone resins, rubbers or elastomers, etc.

(抗污劑) (Antifouling agent)

關於抗污劑，雖可於第3層12D均勻地分散有抗污劑，但從以少量添加量即可得到足夠之抗污性且抑制第3層12D之強度下降的觀點而言，較佳局部地含有於第3層12D之表面側。作為使抗污劑局部存在於第3層12D之表面側的方法，例如可列舉下述方法等：於形成第3層12D時，使用後述之第3樹脂組成物形成塗膜，於使塗膜乾燥、硬化前，加熱塗膜，降低塗膜所含之樹脂成分的黏度，藉此提升流動性，使抗污劑局部存在於第3層12D之表面側的方法，或選定表面張力低之抗污劑來使用，於使塗膜乾燥時在不施加熱下使抗污劑浮在塗膜表面，然後使塗膜硬化，藉此使上述抗污劑局部存在於第3層12D之最表面側的方法。 Regarding the antifouling agent, although the antifouling agent can be uniformly dispersed in the third layer 12D, it is preferable from the viewpoint of obtaining sufficient antifouling properties with a small amount of addition and suppressing the decrease in the strength of the third layer 12D Partially contained on the surface side of the third layer 12D. As a method for localizing the antifouling agent on the surface side of the third layer 12D, for example, the following method can be cited: when forming the third layer 12D, a coating film is formed using a third resin composition described later, and the coating film Before drying and curing, heat the coating film to reduce the viscosity of the resin component contained in the coating film, thereby improving fluidity and making the antifouling agent locally exist on the surface side of the third layer 12D, or selecting a low surface tension antifouling agent When the coating film is dried, the antifouling agent is floated on the surface of the coating film without applying heat, and then the coating film is hardened, so that the antifouling agent is locally present on the outermost surface of the third layer 12D Methods.

抗污劑並無特別限定，例如可列舉：聚矽氧系抗污劑、氟系抗污劑、聚矽氧系及氟系抗污劑，可分別單獨使用，亦可混合使用。又，抗污劑亦可為丙烯酸系抗污劑。 The antifouling agent is not particularly limited, and examples thereof include polysiloxane-based antifouling agents, fluorine-based antifouling agents, polysiloxane-based and fluorine-based antifouling agents, which may be used alone or in combination. In addition, the antifouling agent may also be an acrylic antifouling agent.

作為抗污劑之含量，較佳相對於上述之樹脂成分100質量份，為0.01~3.0重量份。若未達0.01重量份，則有時會無法對第3層賦予足夠之抗污性能，又，若超過3.0重量份，則有第3層之硬度下降之虞。 The content of the antifouling agent is preferably 0.01 to 3.0 parts by weight relative to 100 parts by weight of the above-mentioned resin component. If it is less than 0.01 parts by weight, the third layer may not be able to provide sufficient antifouling performance, and if it exceeds 3.0 parts by weight, the hardness of the third layer may decrease.

抗污劑為下述之化合物：重量平均分子量較佳為5000以下，又為了改善抗污性能之耐久性，較佳使反應性官能基為1個以上，更佳具有2個以上。其中，藉由使用具有2個以上之反應性官能基的抗污劑，可賦予優異之耐擦傷性。 The antifouling agent is the following compound: the weight average molecular weight is preferably 5000 or less, and in order to improve the durability of the antifouling performance, it is preferable to have one or more reactive functional groups, more preferably two or more. Among them, by using an antifouling agent having two or more reactive functional groups, excellent scratch resistance can be imparted.

當抗污劑不具有反應性官能基之情形時，無論是光學膜為捲筒狀之情形或為片狀之情形，有時於重疊時抗污劑會轉移至光學膜背面，而若想要將其他層貼合或塗布於光學膜背面，則會發生其他層之剝落，並且，有時會因進行複數次折疊測試而容易剝落。 When the antifouling agent does not have reactive functional groups, no matter if the optical film is in the form of a roll or in the form of a sheet, sometimes the antifouling agent will transfer to the back of the optical film when it is overlapped. Laminating or coating other layers on the back of the optical film may cause peeling of other layers, and may easily peel off due to multiple folding tests.

並且，具有上述反應性官能基之抗污劑，抗污性能之性能持續性(耐久性)良好，其中，含有上述氟系抗污劑之樹脂層，指紋不易附著(不明顯)，擦拭性亦良好。並且，由於可降低樹脂層用組成物塗布時之表面張力，因此，整平性佳，所形成之樹脂層的外觀良好。 In addition, the antifouling agent with the above-mentioned reactive functional group has good performance durability (durability) of antifouling performance. Among them, the resin layer containing the above-mentioned fluorine-based antifouling agent does not easily adhere to fingerprints (not obvious), and the wipeability is also good. In addition, since the surface tension during coating of the composition for the resin layer can be reduced, the leveling property is good, and the appearance of the formed resin layer is good.

含有聚矽氧系抗污劑之樹脂層，滑移性佳，耐鋼絲絨性良好。裝載有樹脂層含有此種聚矽氧系抗污劑之光學膜的觸感測器，由於用手指或筆等接觸時之滑移佳，故觸感好。又，指紋亦不易附著於樹脂層(不明顯)，擦拭性亦良好。並且，由於可降低樹脂層用組成物塗布時之表面張力，因此，整平性佳，所形成之樹脂層的外觀良好。 The resin layer containing polysiloxane antifouling agent has good slippage and steel wool resistance. A touch sensor equipped with a resin layer containing an optical film containing such a polysilicone antifouling agent has a good touch due to its good slippage when touched with a finger or a pen. In addition, fingerprints are also difficult to adhere to the resin layer (not noticeable), and the wiping properties are also good. In addition, since the surface tension during coating of the composition for the resin layer can be reduced, the leveling property is good, and the appearance of the formed resin layer is good.

作為聚矽氧系抗污劑之市售品，例如可列舉：SUA1900L10(新中村化學公司製)，SUA1900L6(新中村化學公司製)，Ebecryl1360(大賽璐氰特公司製)，UT3971(日本合成公司製)，BYKUV3500(BYK公司製)，BYKUV3510(BYK公司製)，BYKUV3570(BYK公司製)，X22-164E、X22-174BX、X22-2426、KBM503.KBM5103(信越化學公司製)，TEGO- RAD2250、TEGO-RAD2300、TEGO-RAD2200N、TEGO-RAD2010、TEGO-RAD2500、TEGO-RAD2600、TEGO-RAD2700(Evonik Japan公司製)，MEGAFACE RS854(迪愛生公司製)等。 Examples of commercially available products of the polysiloxane-based antifouling agent include: SUA1900L10 (manufactured by Shinnakamura Chemical Co., Ltd.), SUA1900L6 (manufactured by Shinnakamura Chemical Co., Ltd.), Ebecryl1360 (manufactured by Daicel Cytotech Co., Ltd.), and UT3971 (Nippon Gosei Co., Ltd.) System), BYKUV3500 (manufactured by BYK), BYKUV3510 (manufactured by BYK), BYKUV3570 (manufactured by BYK), X22-164E, X22-174BX, X22-2426, KBM503.KBM5103 (manufactured by Shin-Etsu Chemical Co.), TEGO-RAD2250, TEGO-RAD2300, TEGO-RAD2200N, TEGO-RAD2010, TEGO-RAD2500, TEGO-RAD2600, TEGO-RAD2700 (manufactured by Evonik Japan), MEGAFACE RS854 (manufactured by Di Aisheng), etc.

作為氟系抗污劑之市售品，例如可列舉：Optool DAC、Optool DSX(大金工業公司製)，MEGAFACE RS71、MEGAFACE RS74(迪愛生公司製)，LINC152EPA、LINC151EPA、LINC182UA(共榮社化學公司製)，ftergent 650A、ftergent 601AD、ftergent 602等。 Commercial products of the fluorine-based antifouling agent include, for example, Optool DAC, Optool DSX (manufactured by Daikin Industrial Co., Ltd.), MEGAFACE RS71, MEGAFACE RS74 (manufactured by Dyson Co., Ltd.), LINC152EPA, LINC151EPA, and LINC182UA (Kyoeisha Chemical Co., Ltd.) Company system), ftergent 650A, ftergent 601AD, ftergent 602, etc.

作為是氟系且是聚矽氧系並具有反應性官能基之抗污劑的市售品，例如可列舉：MEGAFACE RS851、MEGAFACE RS852、MEGAFACE RS853、MEGAFACE RS854(迪愛生公司製)，OPSTAR TU2225、OPSTAR TU2224(JSR公司製)，X71-1203M(信越化學公司製)等。 Commercially available antifouling agents that are fluorine-based and silicone-based and have reactive functional groups include, for example, MEGAFACE RS851, MEGAFACE RS852, MEGAFACE RS853, MEGAFACE RS854 (manufactured by Di Aisheng), OPSTAR TU2225, OPSTAR TU2224 (manufactured by JSR Corporation), X71-1203M (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

<<<其他之光學膜>>> <<<Other Optical Films>>>

圖1所示之光學膜10雖然樹脂層12為3層構造，但亦可為4層構造。具體而言，光學膜如圖3所示，亦可為具備有基材11與樹脂層21之光學膜20，該樹脂層21呈第1層21B至第4層21E自基材11側依序積層於基材11之一面11A側的4層構造。光學膜20之表面20A成為樹脂層21之表面21A(第4層21E之表面)。光學膜20之物性等由於與光學膜10之物性等相同，因此這裡省略說明。光學膜20之基材11由於與光學膜10之基材11相同，因此省略說明。 Although the resin layer 12 of the optical film 10 shown in FIG. 1 has a three-layer structure, it may have a four-layer structure. Specifically, as shown in FIG. 3, the optical film may also be an optical film 20 provided with a substrate 11 and a resin layer 21. The resin layer 21 is formed from the first layer 21B to the fourth layer 21E in order from the substrate 11 side. A four-layer structure laminated on the side of one surface 11A of the base material 11. The surface 20A of the optical film 20 becomes the surface 21A of the resin layer 21 (the surface of the fourth layer 21E). Since the physical properties and the like of the optical film 20 are the same as the physical properties and the like of the optical film 10, the description is omitted here. Since the base material 11 of the optical film 20 is the same as the base material 11 of the optical film 10, description is abbreviate|omitted.

<<樹脂層>> <<Resin layer>>

於樹脂層21，第1層21B、第2層21C、第3層21D、第4層21E各層之壓痕硬度從第1層21B至第4層21E依序變大。亦即，於使第1層21B、第2層21C、第3層21D及第4層21E之壓痕硬度分別為HIT1、HIT2、HIT3及HIT4時，滿足上述關係式(A)。亦即，樹脂層21滿足下述關係式(C)。 In the resin layer 21, the indentation hardness of each layer of the first layer 21B, the second layer 21C, the third layer 21D, and the fourth layer 21E sequentially increases from the first layer 21B to the fourth layer 21E. That is, in the first layer 21B, the second layer 2 21C, the second layer 3 21D 21E layer 4 of the indentation hardness was IT4 when H IT1, H IT2, H IT3 and H, satisfying the above relation (A) . That is, the resin layer 21 satisfies the following relational expression (C).

HIT1<HIT2<HIT3<HIT4...(C) H IT1 <H IT2 <H IT3 <H IT4 ... (C)

於樹脂層21，第1層21B、第2層21C、第3層21D、第4層21E各層之壓痕硬度若滿足上述關係式(C)，則並無特別限定，較佳為第1層21B之壓痕硬度在1MPa以上100MPa以下，第2層21C之壓痕硬度在10MPa以上300MPa以下，第3層21D之壓痕硬度在50MPa以上500MPa以下，第4層21E之壓痕硬度在100MPa以上1000MPa以下。若第1層之壓痕硬度在1MPa以上，則可更加提升鉛筆硬度，又若第1層之壓痕硬度在100MPa以下，則可更加提升耐撞擊性。若第2層之壓痕硬度在10MPa以上，則在折疊光學膜時樹脂層會更加不易發生裂縫，又若第2層之壓痕硬度在300MPa以下，則在折疊光學膜時樹脂層會更加不易發生皺折。若第3層之壓痕硬度在50MPa以上，則在折疊光學膜時樹脂層會更加不易發生裂縫，又若第3層之壓痕硬度在500MPa以下，則在折疊光學膜時樹脂層會更加不易發生皺折。若第4層之壓痕硬度在100MPa以上，則可更加提升耐擦傷性，又若第4層之壓痕硬度在1000MPa以下，則在折疊光學膜時樹脂層會更加不易發生裂縫。 In the resin layer 21, the indentation hardness of each layer of the first layer 21B, the second layer 21C, the third layer 21D, and the fourth layer 21E is not particularly limited as long as the above-mentioned relational formula (C) is satisfied, and the first layer is preferred The indentation hardness of 21B is above 1 MPa and 100 MPa, the indentation hardness of the second layer 21C is above 10 MPa and below 300 MPa, the indentation hardness of the third layer 21D is above 50 MPa and below 500 MPa, and the indentation hardness of the fourth layer 21E is above 100 MPa. Below 1000MPa. If the indentation hardness of the first layer is above 1 MPa, the pencil hardness can be further improved, and if the indentation hardness of the first layer is below 100 MPa, the impact resistance can be further improved. If the indentation hardness of the second layer is more than 10MPa, the resin layer will be less likely to crack when the optical film is folded, and if the indentation hardness of the second layer is below 300MPa, the resin layer will be more difficult to fold the optical film Wrinkles occur. If the indentation hardness of the third layer is above 50MPa, the resin layer will be less likely to crack when the optical film is folded, and if the indentation hardness of the third layer is below 500MPa, the resin layer will be more difficult to fold the optical film Wrinkles occur. If the indentation hardness of the fourth layer is above 100 MPa, the scratch resistance can be further improved. If the indentation hardness of the fourth layer is below 1000 MPa, the resin layer will be less prone to cracks when the optical film is folded.

<第1層> <Level 1>

第1層21B之膜厚較佳為50μm以上300μm以下。若第1層之膜厚為50μm以上，則可更加提升樹脂層之硬度，又若為300μm以下，則膜厚不會過厚，適於薄型化，且加工性亦良好。第1層21B之膜厚係藉由與第1層12B之膜厚同樣的方法測量。第1層21B之下限更佳依序為80μm以上、100μm以上、150μm以上(數值越大越佳)，第1層21B之上限更佳依序為250μm以下、220μm以下、200μm以下(數值越小越佳)。第1層21B由於可由與第1層12B同樣之樹脂形成，因此這裡省略說明。 The film thickness of the first layer 21B is preferably 50 μm or more and 300 μm or less. If the film thickness of the first layer is 50 μm or more, the hardness of the resin layer can be further increased, and if it is 300 μm or less, the film thickness will not be too thick, which is suitable for thinning and has good workability. The film thickness of the first layer 21B is measured by the same method as the film thickness of the first layer 12B. The lower limit of the first layer 21B is more preferably 80 μm or more, 100 μm or more, and 150 μm or more (the larger the value is, the better), and the upper limit of the first layer 21B is more preferably 250 μm or less, 220 μm or less, and 200 μm or less (the smaller the value, the more good). Since the first layer 21B can be formed of the same resin as the first layer 12B, the description is omitted here.

<第2層及第3層> <2nd and 3rd floors>

第2層21C及第3層21D之膜厚分別較佳為1μm以上50μm以下。若第2層及第3層之膜厚為1μm以上，則在折疊光學膜時樹脂層會更加不易發生皺折，又若為 50μm以下，則在折疊光學膜時樹脂層會更加不易發生裂縫。第2層21C及第3層21D之膜厚係藉由與第1層12B之膜厚同樣的方法求得。第2層21C及第3層21D之膜厚的下限分別更佳依序為3μm以上、5μm以上、7μm以上(數值越大越佳)，第2層21C及第3層21D之膜厚的上限分別更佳依序為40μm以下、30μm以下、20μm以下(數值越小越佳)。第2層21C可藉由在如第2層12C欄說明之例如第1層12B欄說明的樹脂添加無機粒子及/或有機粒子形成。第3層21D可使用含有胺酯(甲基)丙烯酸酯與壓痕硬度會變高之類的游離輻射聚合性化合物的樹脂層用組成物形成。 The film thicknesses of the second layer 21C and the third layer 21D are preferably 1 μm or more and 50 μm or less. If the thickness of the second and third layers is 1 μm or more, the resin layer will be less likely to wrinkle when the optical film is folded, and if it is 50 μm or less, the resin layer will be less likely to crack when the optical film is folded. The film thicknesses of the second layer 21C and the third layer 21D are obtained by the same method as the film thickness of the first layer 12B. The lower limits of the film thickness of the second layer 21C and the third layer 21D are more preferably 3 μm or more, 5 μm or more, and 7 μm or more, respectively (the larger the value, the better), and the upper limits of the film thickness of the second layer 21C and the third layer 21D are respectively More preferably, it is 40 μm or less, 30 μm or less, and 20 μm or less in order (the smaller the value, the better). The second layer 21C can be formed by adding inorganic particles and/or organic particles to the resin described in the column of the second layer 12C, for example, the resin described in the column of the first layer 12B. The third layer 21D can be formed using a composition for a resin layer containing a urethane (meth)acrylate and an ionizing radiation polymerizable compound that increases indentation hardness.

<第4層> <Level 4>

第4層21E之膜厚較佳為0.05μm以上5μm以下。若第4層之膜厚為0.05μm以上，則可更加提升耐擦傷性，又若為5μm以下，則在折疊光學膜時樹脂層會更加不易發生裂縫。第4層21E之膜厚係藉由與第1層12B之膜厚同樣的方法求得。第4層21E之下限更佳依序為0.1μm以上、0.5μm以上、0.8μm以上(數值越大越佳)，第4層21E之上限更佳依序為3μm以下、2μm以下、1μm以下。第4層21E可由第3層12D欄說明之游離輻射聚合性化合物形成。 The film thickness of the fourth layer 21E is preferably 0.05 μm or more and 5 μm or less. If the film thickness of the fourth layer is 0.05 μm or more, the scratch resistance can be further improved, and if it is 5 μm or less, the resin layer will be less prone to cracks when the optical film is folded. The film thickness of the fourth layer 21E is obtained by the same method as the film thickness of the first layer 12B. The lower limit of the fourth layer 21E is more preferably 0.1 μm or more, 0.5 μm or more, and 0.8 μm or more (the larger the value is, the better), and the upper limit of the fourth layer 21E is more preferably 3 μm or less, 2 μm or less, and 1 μm or less in this order. The fourth layer 21E may be formed of the ionizing radiation polymerizable compound described in the column of the third layer 12D.

<<<光學膜之製造方法>>> <<<Method of manufacturing optical film>>>

光學膜10可根據構成第1層12B至第3層12D之樹脂的種類用各種方法製作。例如當第1層12B及第2層12C為由胺酯系樹脂構成之層的情形時，可用下述方式製作。首先藉由棒式塗布機(bar coater)等塗布裝置將第1樹脂組成物塗布於基材11之一面11A上，形成第1樹脂組成物之塗膜。 The optical film 10 can be produced by various methods according to the kind of resin constituting the first layer 12B to the third layer 12D. For example, when the first layer 12B and the second layer 12C are layers composed of a urethane-based resin, they can be produced in the following manner. First, the first resin composition is coated on one surface 11A of the substrate 11 by a coating device such as a bar coater to form a coating film of the first resin composition.

<第1樹脂組成物> <First resin composition>

第1樹脂層用組成物含有胺酯(甲基)丙烯酸酯或多元醇化合物與異氰酸酯化合物。第1樹脂組成物另外視需要亦可含有紫外線吸收劑、分光穿透率調整劑、整平劑、溶劑、聚合起始劑。 The composition for the first resin layer contains a urethane (meth)acrylate or a polyol compound and an isocyanate compound. The first resin composition may also contain an ultraviolet absorber, a spectral transmittance adjuster, a leveling agent, a solvent, and a polymerization initiator as necessary.

第1樹脂組成物之總固形物成分較佳為25~95%。若低於25%，則會有殘存殘留溶劑，或產生白化之虞。若超過95%，則有時第1層用組成物之黏度會變高，塗布性下降而於表面出現不均勻或條紋。上述固形物成分更佳為30~90%。 The total solid content of the first resin composition is preferably 25 to 95%. If it is less than 25%, residual solvents may remain, or whitening may occur. If it exceeds 95%, the viscosity of the composition for the first layer may increase, coating properties may decrease, and unevenness or streaks may appear on the surface. The above solid content is more preferably 30 to 90%.

(溶劑) (Solvent)

作為上述溶劑，可列舉：醇(例如甲醇、乙醇、丙醇、異丙醇、正丁醇、二級丁醇、三級丁醇、苄醇、PGME、乙二醇，二丙酮醇)、酮(例如丙酮、甲基乙基酮、甲基異丁基酮、環戊酮、環己酮、庚酮、二異丁酮、二乙酮、二丙酮醇)、酯(乙酸甲酯、乙酸乙酯、乙酸丁酯、乙酸丙酯、乙酸異丙酯、甲酸甲酯、PGMEA)、脂肪族烴(例如己烷、環己烷)、鹵化烴(例如二氯甲烷、氯仿、四氯化碳)、芳香族烴(例如苯、甲苯、二甲苯)、醯胺(例如二甲基甲醯胺、二甲基乙醯胺、正甲基吡咯啶酮)、醚(例如二***、二

Figure 106135143-A0202-12-0046-54
烷、四氫呋喃)、醚醇(例如1-甲氧基-2-丙醇)、碳酸酯(碳酸二甲酯、碳酸二乙酯、碳酸乙甲酯)等。此等之溶劑可單獨使用，亦可合併使用2種以上。其中，作為上述溶劑，於使胺酯(甲基)丙烯酸酯等成分以及其他添加劑溶解或者分散而可合適地塗布上述第1樹脂組成物的方面，較佳為甲基異丁基酮、甲基乙基酮。 Examples of the above-mentioned solvents include alcohols (for example, methanol, ethanol, propanol, isopropanol, n-butanol, secondary butanol, tertiary butanol, benzyl alcohol, PGME, ethylene glycol, diacetone alcohol), ketones (E.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, heptanone, diisobutyl ketone, diethyl ketone, diacetone alcohol), esters (methyl acetate, ethyl acetate Ester, butyl acetate, propyl acetate, isopropyl acetate, methyl formate, PGMEA), aliphatic hydrocarbons (e.g. hexane, cyclohexane), halogenated hydrocarbons (e.g. dichloromethane, chloroform, carbon tetrachloride) , Aromatic hydrocarbons (e.g. benzene, toluene, xylene), amides (e.g. dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (e.g. diethyl ether, two
Figure 106135143-A0202-12-0046-54
Alkanes, tetrahydrofuran), ether alcohols (e.g. 1-methoxy-2-propanol), carbonates (dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate), etc. These solvents can be used alone, or two or more of them can be used in combination. Among them, the solvent is preferably methyl isobutyl ketone, methyl isobutyl ketone, and methyl isobutyl ketone in terms of dissolving or dispersing components such as urethane (meth)acrylate and other additives to appropriately coat the first resin composition. Ethyl ketone.

(聚合起始劑) (Polymerization initiator)

聚合起始劑為下述之成分：會因受到照射游離輻射或熱而分解，產生自由基使聚合性化合物之聚合(交聯)開始或進行。 The polymerization initiator is a component that decomposes by exposure to ionizing radiation or heat, and generates free radicals to start or proceed the polymerization (crosslinking) of the polymerizable compound.

聚合起始劑若可因照射游離輻射或熱而釋放出使自由基聚合開始之物質，則並無特別限定。作為聚合起始劑，並無特別限定，可使用周知者，具體例例如可列舉：苯乙酮類、二苯甲酮類、米氏苯甲醯基苯甲酸酯(Michler-Benzoyl benzoate)、α-戊基肟酯(α-amyloxime ester)、9-氧硫

Figure 106135143-A0202-12-0046-55
(thioxanthone)類、丙醯苯類、二苯乙二酮類、安息香類、醯基氧化膦 (acylphosphine oxide)類。又，較佳混合光敏劑使用，作為其具體例，例如可列舉：正丁胺、三乙胺、聚正丁基膦等。 The polymerization initiator is not particularly limited as long as it can release a substance that initiates radical polymerization by irradiation with ionizing radiation or heat. The polymerization initiator is not particularly limited, and well-known ones can be used. Specific examples include, for example, acetophenones, benzophenones, Michler-Benzoyl benzoate, α-amyloxime ester, 9-oxysulfur
Figure 106135143-A0202-12-0046-55
(thioxanthone), acetonitrile, diphenylethylenedione, benzoin, acylphosphine oxide (acylphosphine oxide). In addition, it is preferable to use a mixed photosensitizer, and specific examples thereof include n-butylamine, triethylamine, poly-n-butylphosphine, and the like.

於形成第1樹脂組成物之塗膜後進行乾燥，然後照射游離輻射或加熱，使第1樹脂組成物之塗膜半硬化(half cure)。本說明書中之「半硬化」，係指若照射游離輻射或加熱則硬化實質上會進行之意。惟，於此階段亦可使第1樹脂組成物之塗膜完全硬化(full cure)。本說明書中之「完全硬化」，係指即使再照射游離輻射或加熱，硬化實質上亦不會進行之意。 After forming the coating film of the first resin composition, it is dried, and then irradiated with ionizing radiation or heating to half cure the coating film of the first resin composition. "Semi-curing" in this manual means that curing will proceed substantially if irradiated with ionizing radiation or heating. However, it is also possible to fully cure the coating film of the first resin composition at this stage. "Complete curing" in this manual means that even if it is irradiated with ionizing radiation or heated, curing will not proceed substantially.

於使第1樹脂組成物之塗膜半硬化後，藉由棒式塗布機等塗布裝置將第2樹脂組成物塗布於經半硬化之第1樹脂組成物的塗膜上，形成第2樹脂組成物之塗膜。 After the coating film of the first resin composition is semi-cured, the second resin composition is coated on the coating film of the semi-cured first resin composition by a coating device such as a bar coater to form the second resin composition The coating film of the thing.

<第2樹脂組成物> <Second resin composition>

第2樹脂組成物含有胺酯(甲基)丙烯酸酯與無機粒子及/或有機粒子或者上述游離輻射聚合性化合物。第2樹脂組成物另外視需要亦可含有紫外線吸收劑、分光穿透率調整劑、整平劑、溶劑、聚合起始劑。 The second resin composition contains urethane (meth)acrylate and inorganic particles and/or organic particles or the above-mentioned ionizing radiation polymerizable compound. The second resin composition may also contain an ultraviolet absorber, a spectral transmittance adjuster, a leveling agent, a solvent, and a polymerization initiator as necessary.

於形成第2樹脂組成物之塗膜後進行乾燥，然後照射游離輻射，使第2樹脂組成物之塗膜半硬化(half cure)。惟，於此階段，亦可使第1樹脂組成物之塗膜完全硬化(full cure)。 After forming the coating film of the second resin composition, it is dried and then irradiated with ionizing radiation to half cure the coating film of the second resin composition. However, at this stage, the coating film of the first resin composition can also be fully cured.

於使第2樹脂組成物之塗膜半硬化後，藉由棒式塗布機等塗布裝置將第3樹脂組成物塗布於經半硬化之第2樹脂組成物的塗膜上，形成第3樹脂組成物之塗膜。 After the coating film of the second resin composition is semi-cured, the third resin composition is coated on the coating film of the semi-cured second resin composition by a coating device such as a bar coater to form the third resin composition The coating film of the thing.

<第3樹脂組成物> <3rd resin composition>

第3樹脂組成物含有上述游離輻射聚合性化合物。第3樹脂組成物另外視需要亦可含有溶劑乾燥型樹脂、抗污劑、紫外線吸收劑、分光穿透率調整劑、整平劑、溶劑、聚合起始劑。 The third resin composition contains the above-mentioned ionizing radiation polymerizable compound. The third resin composition may also contain a solvent drying resin, an antifouling agent, an ultraviolet absorber, a spectral transmittance adjuster, a leveling agent, a solvent, and a polymerization initiator, if necessary.

於形成第3樹脂組成物之塗膜後進行乾燥，然後照射游離輻射，使第3層用組成物之塗膜完全硬化(full cure)。藉此而得到於基材11之一面11A側具備依序積層有第1層12B、第2層12C及第3層12D之樹脂層12的光學膜10。 After the coating film of the third resin composition is formed, it is dried and then irradiated with ionizing radiation to fully cure the coating film of the third layer composition. Thereby, the optical film 10 provided with the resin layer 12 which laminated|stacked the 1st layer 12B, the 2nd layer 12C, and the 3rd layer 12D on the side of the one surface 11A of the base material 11 in this order is obtained.

當使樹脂層為由較柔軟之樹脂層構成之單層構造的情形時，雖然可得到優異之折疊性、耐撞擊性及鉛筆硬度，但是由於樹脂層較柔軟，故有無法得到優異之耐擦傷性之虞。為了得到優異之耐擦傷性，必須使樹脂層之表面變硬達某程度。惟，若使樹脂層表面過硬，則會有無法得到優異之折疊性或耐撞擊性之虞。又，當使樹脂層為較柔軟之第1層與堅硬之第2層的2層構造之情形時，雖然可得到優異之折疊性、耐撞擊性及優異之鉛筆硬度，但是由於在較柔軟之第1層上形成有堅硬之第2層，因此在將光學膜折疊成180°時，會有下述之虞：於樹脂層產生細微裂紋，且若進行耐擦傷性測試，則鋼絲絨會下沈至第2層，第2層裂開。並且，當使樹脂層為由第1層與較第1層柔軟之第2層與較第1層及第2層堅硬之第3層構成的3層構造之情形時，雖然可得到優異之折疊性、耐撞擊性及優異之鉛筆硬度，但是於將光學膜折疊成180°時，會有下述之虞：於樹脂層產生皺折或細微裂紋，且若進行耐擦傷性測試，則鋼絲絨會下沈至第3層，第3層裂開。根據此種見解，本發明人等發現為了得到優異之折疊性、優異之鉛筆硬度、優異之耐撞擊性、優異之彎曲性及優異之耐擦傷性皆滿足的光學膜，而必須使樹脂層為3層以上之構造，且使硬度從第1層至第n層慢慢地變高。若根據本實施形態，則由於樹脂層為3層以上之構造，且第1層~第n層各層之壓痕硬度從第1層至第n層依序變大，亦即滿足上述關係式(A)，因此可得到優異之折疊性、優異之鉛筆硬度、優異之耐撞擊性、優異之彎曲性及優異之耐擦傷性。 When the resin layer is a single-layer structure composed of a relatively soft resin layer, although excellent foldability, impact resistance and pencil hardness can be obtained, the resin layer is relatively soft, so excellent scratch resistance cannot be obtained. The fear of sex. In order to obtain excellent scratch resistance, the surface of the resin layer must be hardened to a certain degree. However, if the surface of the resin layer is made too hard, there is a risk that excellent foldability or impact resistance may not be obtained. In addition, when the resin layer has a two-layer structure of a softer first layer and a harder second layer, although excellent foldability, impact resistance and excellent pencil hardness can be obtained, it is due to the softer layer. A hard second layer is formed on the first layer. Therefore, when the optical film is folded to 180°, there is a risk of the following: fine cracks will occur in the resin layer, and if the scratch resistance test is performed, the steel wool will fall After sinking to the second layer, the second layer cracked. In addition, when the resin layer has a three-layer structure consisting of a first layer and a second layer that is softer than the first layer, and a third layer that is harder than the first and second layers, excellent folding can be obtained. Resistance, impact resistance and excellent pencil hardness, but when the optical film is folded to 180°, there will be the following risks: wrinkles or micro cracks in the resin layer, and if the scratch resistance test is performed, steel wool It will sink to the 3rd floor, and the 3rd floor will crack. Based on this knowledge, the present inventors found that in order to obtain an optical film that satisfies excellent foldability, excellent pencil hardness, excellent impact resistance, excellent flexibility, and excellent scratch resistance, the resin layer must be The structure is more than 3 layers, and the hardness gradually increases from the first layer to the nth layer. According to this embodiment, since the resin layer has a structure of three or more layers, and the indentation hardness of each layer of the first layer to the nth layer increases sequentially from the first layer to the nth layer, that is, the above relationship is satisfied ( A) Therefore, excellent foldability, excellent pencil hardness, excellent impact resistance, excellent bendability and excellent scratch resistance can be obtained.

<<<影像顯示裝置>>> <<<Image display device>>>

光學膜10可裝入可折疊之影像顯示裝置使用。圖4為本實施形態之影像顯示裝置的概略構成圖。如圖4所示，影像顯示裝置30朝向觀察者側主要依序積層有 收藏電池等之箱體31、保護膜32、顯示面板33、觸感測器34、圓偏光板35及光學膜10。於顯示面板33與觸感測器34之間、觸感測器34與圓偏光板35之間、圓偏光板35與光學膜10之間，例如配置有光學透明膠黏劑(Optical Clear Adhesive，OCA)等透光性接著層36，此等構件係藉由透光性接著層36互相固定。本說明書中之「接著層」係包含黏著層之概念。又，於光學膜10之背面10B的一部份，設置有黑色層37。 The optical film 10 can be used in a foldable image display device. Fig. 4 is a schematic configuration diagram of the image display device of this embodiment. As shown in FIG. 4, the image display device 30 is mainly laminated with a box 31 for storing batteries and the like, a protective film 32, a display panel 33, a touch sensor 34, a circular polarizing plate 35, and an optical film 10 in this order toward the viewer. Between the display panel 33 and the touch sensor 34, between the touch sensor 34 and the circular polarizing plate 35, between the circular polarizing plate 35 and the optical film 10, for example, an optical clear adhesive (Optical Clear Adhesive, OCA) and other light-transmitting adhesive layers 36, and these components are fixed to each other by the light-transmitting adhesive layer 36. The "adhesive layer" in this manual includes the concept of an adhesive layer. In addition, a black layer 37 is provided on a part of the back surface 10B of the optical film 10.

光學膜10係配置成樹脂層12較基材11更靠近觀察者側。於影像顯示裝置30，光學膜10之樹脂層12的表面12A構成影像顯示裝置30之表面30A。 The optical film 10 is arranged so that the resin layer 12 is closer to the observer side than the base material 11. In the image display device 30, the surface 12A of the resin layer 12 of the optical film 10 constitutes the surface 30A of the image display device 30.

於影像顯示裝置30，顯示面板33為含有有機發光二極體等之有機發光二極體面板。觸感測器34較圓偏光板35更靠近配置於顯示面板33側，亦可配置於圓偏光板35與光學膜10之間。又，觸感測器34可為整合(on-cell)式或內嵌(in-cell)式。 In the image display device 30, the display panel 33 is an organic light-emitting diode panel containing organic light-emitting diodes and the like. The touch sensor 34 is arranged closer to the display panel 33 than the circular polarizing plate 35, and may also be arranged between the circular polarizing plate 35 and the optical film 10. In addition, the touch sensor 34 may be of an on-cell type or an in-cell type.

[第2實施形態] [Second Embodiment]

以下，一邊參照圖式，一邊說明本發明之第2實施形態的光學膜及影像顯示裝置。圖5為本實施形態之附離型膜之光學膜的概略構成圖，圖6為本實施形態之其他附離型膜之光學膜的概略構成圖。 Hereinafter, the optical film and the image display device of the second embodiment of the present invention will be described with reference to the drawings. Fig. 5 is a schematic configuration diagram of an optical film with a release film according to this embodiment, and Fig. 6 is a schematic configuration diagram of another optical film with a release film according to the embodiment.

<<<附離型膜之光學膜>>> <<<Optical film with release film>>>

圖5所示之附離型膜之光學膜50依序具備有離型膜51、光學膜60及離型膜52。光學膜60具備有樹脂層61，該樹脂層61為從第1層積層至第n層(n為3以上之整數)之多層構造。 The optical film with release film 50 shown in FIG. 5 includes a release film 51, an optical film 60, and a release film 52 in this order. The optical film 60 is provided with the resin layer 61 which has a multilayer structure from the 1st laminated layer to the nth layer (n is an integer of 3 or more).

<<離型膜>> <<Release film>>

離型膜51、52可從光學膜60剝離。作為離型膜51、52，並無特別限定，較佳為剝離時之剝離力在0.01N/25mm以上0.5N/25mm以下之膜。若剝離力在0.01N/25mm以上，則由於離型膜51、52與光學膜60之密接力大，因此可抑制 離型膜51、52產生部分剝落。又，若剝離力在0.5N/25mm以下，則可輕易從光學膜60將離型膜51、52剝離。作為離型膜51、52，從處理容易、可確保某程度之透明性的觀點而言，可使用將聚乙烯系樹脂、聚丙烯系樹脂、聚苯乙烯系樹脂、聚對酞酸乙二酯系樹脂等成形而得之膜。離型膜可僅為1片之膜，又亦可為基材膜上具備有黏著層之積層膜。作為離型膜，例如可列舉：聚乙烯膜表面形成有黏著層之SUNYTECT(註冊商標，山櫻化研股份有限公司製)、聚對酞酸乙二酯膜表面形成有黏著層之E-MASK(註冊商標，日東電工公司製)、聚對酞酸乙二酯膜表面形成有黏著層之MASTACK(註冊商標，藤森工業股份有限公司製)等市售品。 The release films 51 and 52 can be peeled from the optical film 60. The release films 51 and 52 are not particularly limited, but preferably a film having a peeling force of 0.01 N/25 mm or more and 0.5 N/25 mm or less. If the peeling force is 0.01N/25mm or more, since the adhesion force between the release films 51 and 52 and the optical film 60 is large, the release films 51 and 52 can be prevented from being partially peeled off. In addition, if the peeling force is 0.5 N/25 mm or less, the release films 51 and 52 can be easily peeled from the optical film 60. As the release films 51, 52, from the viewpoint of easy handling and a certain degree of transparency, polyethylene resin, polypropylene resin, polystyrene resin, polyethylene terephthalate can be used. It is a film obtained by molding a resin or the like. The release film can be only one film, or it can be a laminate film with an adhesive layer on the base film. As the release film, for example, SUNYTECT (registered trademark, manufactured by Yamasakura Kaken Co., Ltd.) with an adhesive layer formed on the surface of a polyethylene film, and E-MASK with an adhesive layer formed on the surface of a polyethylene terephthalate film (Registered trademark, manufactured by Nitto Denko Corporation), MASTACK (registered trademark, manufactured by Fujimori Kogyo Co., Ltd.) and other commercially available products with an adhesive layer formed on the surface of the polyethylene terephthalate film.

<<光學膜>> <<Optical Film>>

圖5所示之光學膜60與光學膜10同樣地被使用於影像顯示裝置，可折疊且具有透光性，但不具備基材，此點與光學膜10不同。另，離型膜51、52由於最後會從光學膜60剝離，因此並不被視為基材。 The optical film 60 shown in FIG. 5 is used in an image display device in the same way as the optical film 10, is foldable and has light transmittance, but does not have a base material, which is different from the optical film 10 in this point. In addition, since the release films 51 and 52 are finally peeled from the optical film 60, they are not regarded as base materials.

光學膜60之表面60A成為樹脂層61之表面61A。於光學膜60，如後述般由於樹脂層61之第3層61D成為最上層，因此，光學膜60之表面60A成為第3層61D之表面。光學膜60之背面60B則成為第1層61B中第2層61C側面之相反側面。 The surface 60A of the optical film 60 becomes the surface 61A of the resin layer 61. In the optical film 60, since the third layer 61D of the resin layer 61 becomes the uppermost layer as described later, the surface 60A of the optical film 60 becomes the surface of the third layer 61D. The back 60B of the optical film 60 becomes the opposite side of the side of the second layer 61C in the first layer 61B.

光學膜60之物性等與光學膜10之物性等相同。惟，光學膜60之物性，係於從附離型膜之光學膜50將兩離型膜51，52剝離後之狀態下測量。 The physical properties and the like of the optical film 60 are the same as the physical properties and the like of the optical film 10. However, the physical properties of the optical film 60 are measured in a state where the two release films 51 and 52 are peeled from the optical film 50 with a release film.

<<樹脂層>> <<Resin layer>>

樹脂層61為從第1層積層至第n層(n為3以上之整數)之多層構造。第1層至第n層當然為主要由樹脂構成之層，但除了樹脂之外，亦可含有粒子或添加劑等。 The resin layer 61 has a multilayer structure from the first layer to the nth layer (n is an integer of 3 or more). Of course, the first to nth layers are layers mainly composed of resin, but in addition to resin, particles or additives may be contained.

樹脂層61中之第1層~第n層各層的壓痕硬度，從第1層至第n層依序變大。亦即，於樹脂層61，亦滿足上述關係式(A)。 The indentation hardness of each layer of the first layer to the nth layer in the resin layer 61 increases sequentially from the first layer to the nth layer. That is, the resin layer 61 also satisfies the above-mentioned relational expression (A).

具體而言，樹脂層61由於為依序從第1層61B積層至第3層61D之多層構造，因此，第1層61B、第2層61C、第3層61D各層之壓痕硬度從第1層61B至第3層61D依序變大。亦即，於使第1層61B、第2層61C及第3層61D之壓痕硬度分別為HIT1、HIT2、HIT3時，滿足上述關係式(B)。 Specifically, since the resin layer 61 has a multilayer structure in which the first layer 61B is sequentially laminated to the third layer 61D, the indentation hardness of each layer of the first layer 61B, the second layer 61C, and the third layer 61D is from the first layer 61B to the third layer 61D. The layer 61B to the third layer 61D sequentially become larger. That is, when the indentation hardness of the first layer 61B, the second layer 61C, and the third layer 61D are H IT1 , H IT2 , and H IT3 , respectively, the above-mentioned relational expression (B) is satisfied.

於光學膜60，樹脂層61由於由第1層61B、第2層61C、及第3層61D構成，因此上述n為3，但上述第n層之n若為3以上的話，則並無特別限定。上述n之上限從生產性之觀點而言，較佳為10以下。 In the optical film 60, since the resin layer 61 is composed of the first layer 61B, the second layer 61C, and the third layer 61D, the above n is 3, but if the n of the nth layer is 3 or more, there is nothing special. limited. From the viewpoint of productivity, the upper limit of n is preferably 10 or less.

當樹脂層61為3層構造之情形時，第1層61B、第2層61C、第3層61D各層之壓痕硬度若滿足上述關係式(B)，則並無特別限定，基於與第1實施形態所述之理由同樣之理由，第1層61B之壓痕硬度較佳為1MPa以上100MPa以下，第2層61C之壓痕硬度較佳為10MPa以上500MPa以下，第3層61D之壓痕硬度較佳為100MPa以上1000MPa以下。 When the resin layer 61 has a three-layer structure, the indentation hardness of each layer of the first layer 61B, the second layer 61C, and the third layer 61D is not particularly limited if it satisfies the above-mentioned relational formula (B). For the same reasons as described in the embodiment, the indentation hardness of the first layer 61B is preferably 1 MPa or more and 100 MPa or less, the indentation hardness of the second layer 61C is preferably 10 MPa or more and 500 MPa or less, and the indentation hardness of the third layer 61D Preferably it is 100 MPa or more and 1000 MPa or less.

<第1層~第3層> <1st floor~3rd floor>

由於第1層61B與第1層12B相同，第2層61C與第2層12C相同，第3層61D與第3層12D相同，因此這裡省略說明。 Since the first layer 61B is the same as the first layer 12B, the second layer 61C is the same as the second layer 12C, and the third layer 61D is the same as the third layer 12D, the description is omitted here.

<<<其他之附離型膜之光學膜>>> <<<Other optical films with release film>>>

圖6所示之附離型膜之光學膜70依序具備有離型膜51、光學膜80及離型膜52。 The optical film with release film 70 shown in FIG. 6 includes a release film 51, an optical film 80, and a release film 52 in this order.

<<光學膜>> <<Optical Film>>

圖6所示之光學膜80具備有樹脂層81，該樹脂層81為依序從第1層81B積層至第4層81E之4層構造。光學膜80之表面80A成為樹脂層81之表面81A(第4層81E之表面)。光學膜80之背面80B則成為第1層81B中第2層81C側面之相反側面。 另，於圖6中，賦予與圖5相同符號之構件由於與圖5中表示之構件相同，因此省略說明。 The optical film 80 shown in FIG. 6 is provided with the resin layer 81, and this resin layer 81 has a 4-layer structure laminated|stacked sequentially from the 1st layer 81B to the 4th layer 81E. The surface 80A of the optical film 80 becomes the surface 81A of the resin layer 81 (the surface of the fourth layer 81E). The back surface 80B of the optical film 80 becomes the opposite side of the side surface of the second layer 81C in the first layer 81B. In addition, in FIG. 6, the members assigned the same reference numerals as those in FIG. 5 are the same as the members shown in FIG. 5, so the description is omitted.

光學膜80之物性等與光學膜10之物性等相同。惟，光學膜80之物性，係於從附離型膜之光學膜70將兩離型膜51、52剝離後之狀態下測量。 The physical properties and the like of the optical film 80 are the same as the physical properties and the like of the optical film 10. However, the physical properties of the optical film 80 are measured in a state where the two release films 51 and 52 are peeled off from the optical film 70 with a release film.

<<樹脂層>> <<Resin layer>>

於樹脂層81，第1層81B、第2層81C、第3層81D、第4層81E各層之壓痕硬度從第1層81B至第4層81E依序變大。亦即，於使第1層81B、第2層81C、第3層81D及第4層81E之壓痕硬度分別為HIT1、HIT2、HIT3及HIT4時，滿足上述關係式(A)，具體而言滿足上述關係式(C)。 In the resin layer 81, the indentation hardness of each layer of the first layer 81B, the second layer 81C, the third layer 81D, and the fourth layer 81E sequentially increases from the first layer 81B to the fourth layer 81E. That is, in the first layer 81B, 81C Layer 2, Layer 3 81D 81E and second layer 4 of the indentation hardness was IT4 when H IT1, H IT2, H IT3 and H, satisfying the above relation (A) , Specifically satisfies the above-mentioned relational expression (C).

於樹脂層81，若第1層81B、第2層81C、第3層81D、第4層81E各層之壓痕硬度滿足上述關係式(C)，則並無特別限定，基於與第1實施形態所述之理由同樣之理由，第1層81B之壓痕硬度較佳為1MPa以上100MPa以下，第2層81C之壓痕硬度較佳為10MPa以上300MPa以下，第3層81D之壓痕硬度較佳為50MPa以上500MPa以下，第4層81E之壓痕硬度較佳為100MPa以上1000MPa以下。 In the resin layer 81, if the indentation hardness of each layer of the first layer 81B, the second layer 81C, the third layer 81D, and the fourth layer 81E satisfies the above-mentioned relational expression (C), there is no particular limitation. For the same reason, the indentation hardness of the first layer 81B is preferably 1 MPa or more and 100 MPa or less, the indentation hardness of the second layer 81C is preferably 10 MPa or more and 300 MPa or less, and the indentation hardness of the third layer 81D is better. It is 50 MPa or more and 500 MPa or less, and the indentation hardness of the fourth layer 81E is preferably 100 MPa or more and 1000 MPa or less.

<第1層~第4層> <1st floor~4th floor>

由於第1層81B與第1層21B相同，第2層81C與第2層21C相同，第3層81D與第3層21D相同，第4層81E與第4層21E相同，因此這裡省略說明。 The first layer 81B is the same as the first layer 21B, the second layer 81C is the same as the second layer 21C, the third layer 81D is the same as the third layer 21D, and the fourth layer 81E is the same as the fourth layer 21E, so the description is omitted here.

若根據本實施形態，則樹脂層為3層以上之構造，且第1層~第n層各層之壓痕硬度從第1層至第n層依序變大，亦即滿足上述關係式(A)，因此基於與第1實施形態所述之理由同樣之理由，可得到優異之折疊性、優異之鉛筆硬度、優異之耐撞擊性、優異之彎曲性及優異之耐擦傷性。 According to this embodiment, the resin layer has a structure of three or more layers, and the indentation hardness of each layer from the first layer to the nth layer increases sequentially from the first layer to the nth layer, that is, the above relational expression (A ), therefore, for the same reasons as those described in the first embodiment, excellent foldability, excellent pencil hardness, excellent impact resistance, excellent bendability, and excellent scratch resistance can be obtained.

<<<影像顯示裝置>>> <<<Image display device>>>

光學膜60可裝入可折疊之影像顯示裝置使用。圖7為本實施形態之影像顯示裝置的概略構成圖。如圖7所示，影像顯示裝置90朝向觀察者側主要依序積層有收藏電池等之箱體31、保護膜32、顯示面板33、觸感測器34、圓偏光板35、可 折疊之膜91及光學膜60。於顯示面板33與觸感測器34之間、觸感測器34與圓偏光板35之間、圓偏光板35與膜91之間，例如配置有光學透明膠黏劑(Optical Clear Adhesive，OCA)等之透光性接著層36，此等構件藉由透光性接著層36互相固定。又，於膜91背面之一部份，設置有黑色層37。 The optical film 60 can be used in a foldable image display device. Fig. 7 is a schematic configuration diagram of the image display device of this embodiment. As shown in FIG. 7, the image display device 90 is mainly laminated with a box 31 for storing batteries, etc., a protective film 32, a display panel 33, a touch sensor 34, a circular polarizer 35, and a foldable film in order toward the observer side. 91 and optical film 60. Between the display panel 33 and the touch sensor 34, between the touch sensor 34 and the circular polarizing plate 35, between the circular polarizing plate 35 and the film 91, for example, an optical clear adhesive (OCA) is disposed. ) And other light-transmitting adhesive layers 36, these components are fixed to each other by the light-transmitting adhesive layer 36. In addition, a black layer 37 is provided on a part of the back surface of the film 91.

光學膜60呈將離型膜51、52剝離後之狀態，透過透光性接著層36貼合於膜91。因此，光學膜60被配置成第3層61D較第1層61B更靠近觀察者側。於影像顯示裝置90，光學膜60之樹脂層61的表面61A構成影像顯示裝置90之表面90A。 The optical film 60 is in a state after the release films 51 and 52 are peeled off, and is bonded to the film 91 through the translucent adhesive layer 36. Therefore, the optical film 60 is arranged so that the third layer 61D is closer to the observer side than the first layer 61B. In the image display device 90, the surface 61A of the resin layer 61 of the optical film 60 constitutes the surface 90A of the image display device 90.

膜91為可折疊之膜。作為膜91，可舉由與基材11欄所說明之樹脂同樣之樹脂構成的膜。 The film 91 is a foldable film. As the film 91, a film made of the same resin as the resin described in the column of the base material 11 can be exemplified.

[實施例] [Example]

為了詳細說明本發明，以下舉實施例加以說明，但本發明並不限定於此等記載。 In order to explain the present invention in detail, examples are given below for description, but the present invention is not limited to these descriptions.

<樹脂層用組成物之製備> <Preparation of composition for resin layer>

首先，以成為下述所示之組成的方式摻合各成分，得到樹脂層用組成物。 First, each component is blended so that it may become a composition shown below, and the composition for resin layers is obtained.

(樹脂組成物1) (Resin composition 1)

‧胺酯丙烯酸酯(製品名「RUA-051」，亞細亞工業公司製，3官能)：90質量份 ‧Amino ester acrylate (product name "RUA-051", manufactured by Asia Industrial Co., Ltd., trifunctional): 90 parts by mass

‧苯氧基乙基丙烯酸酯(製品名「VISCOAT # 192」，大阪有機化學工業公司製)：10質量份 ‧Phenoxyethyl acrylate (product name "VISCOAT # 192", manufactured by Osaka Organic Chemical Industry Co., Ltd.): 10 parts by mass

‧聚合起始劑(1-羥基環己基苯基酮，製品名「Irgacure(註冊商標)184」，BASF日本公司製)：5質量份 ‧Polymerization initiator (1-hydroxycyclohexyl phenyl ketone, product name "Irgacure (registered trademark) 184", manufactured by BASF Japan): 5 parts by mass

‧甲基異丁基酮：10質量份 ‧Methyl isobutyl ketone: 10 parts by mass

(樹脂組成物2) (Resin composition 2)

‧胺酯丙烯酸酯(製品名「RUA-051」，亞細亞工業公司製，3官能)：90質量份 ‧Amino ester acrylate (product name "RUA-051", manufactured by Asia Industrial Co., Ltd., trifunctional): 90 parts by mass

‧苯氧基乙基丙烯酸酯(製品名「VISCOAT # 192」，大阪有機化學工業公司製)：10質量份 ‧Phenoxyethyl acrylate (product name "VISCOAT # 192", manufactured by Osaka Organic Chemical Industry Co., Ltd.): 10 parts by mass

‧變形二氧化矽微粒子(平均粒徑25nm，日揮觸媒化成公司製)：50質量份 ‧Deformed silica particles (average particle size 25nm, manufactured by Nikkei Catalytic Kasei Co., Ltd.): 50 parts by mass

‧聚合起始劑(1-羥基環己基苯基酮，製品名「Irgacure(註冊商標)184」，BASF日本公司製)：5質量份 ‧Polymerization initiator (1-hydroxycyclohexyl phenyl ketone, product name "Irgacure (registered trademark) 184", manufactured by BASF Japan): 5 parts by mass

‧甲基異丁基酮：100質量份 ‧Methyl isobutyl ketone: 100 parts by mass

(樹脂組成物3) (Resin composition 3)

‧胺酯丙烯酸酯(製品名「RUA-051」，亞細亞工業公司製，3官能)：90質量份 ‧Amino ester acrylate (product name "RUA-051", manufactured by Asia Industrial Co., Ltd., trifunctional): 90 parts by mass

‧苯氧基乙基丙烯酸酯(製品名「VISCOAT # 192」，大阪有機化學工業公司製)：10質量份 ‧Phenoxyethyl acrylate (product name "VISCOAT # 192", manufactured by Osaka Organic Chemical Industry Co., Ltd.): 10 parts by mass

‧二新戊四醇EO改質六丙烯酸酯(製品名「A-DPH-6E」，新中村化學工業公司製)：10質量份 ‧Dineopentylerythritol EO modified hexaacrylate (product name "A-DPH-6E", manufactured by Shinnakamura Chemical Industry Co., Ltd.): 10 parts by mass

‧聚合起始劑(1-羥基環己基苯基酮，製品名「Irgacure(註冊商標)184」，BASF日本公司製)：5質量份 ‧Polymerization initiator (1-hydroxycyclohexyl phenyl ketone, product name "Irgacure (registered trademark) 184", manufactured by BASF Japan): 5 parts by mass

‧甲基異丁基酮：100質量份 ‧Methyl isobutyl ketone: 100 parts by mass

(樹脂組成物4) (Resin composition 4)

‧胺酯丙烯酸酯(製品名「8UX-015A」，TAISEI FINE CHEMICAL公司製)：30質量份 ‧Amino ester acrylate (product name "8UX-015A", manufactured by TAISEI FINE CHEMICAL): 30 parts by mass

‧多官能丙烯酸酯聚合物(製品名「8KX-012C」，TAISEI FINE CHEMICAL公司製)：70質量份 ‧Multifunctional acrylate polymer (product name "8KX-012C", manufactured by TAISEI FINE CHEMICAL): 70 parts by mass

‧抗污劑(製品名「X-71-1203M」，信越化學工業公司製)：0.5質量份 ‧Antifouling agent (product name "X-71-1203M", manufactured by Shin-Etsu Chemical Co., Ltd.): 0.5 parts by mass

‧聚合起始劑(製品名「Irgacure(註冊商標)127」，BASF日本公司製)：5質量份 ‧Polymerization initiator (product name "Irgacure (registered trademark) 127", manufactured by BASF Japan): 5 parts by mass

‧甲基異丁基酮：200質量份 ‧Methyl isobutyl ketone: 200 parts by mass

<實施例1> <Example 1>

準備厚度30μm之聚醯亞胺基材(製品名「Neopulim」，三菱瓦斯化學公司製)作為基材，用棒式塗布機將樹脂組成物1塗布於聚醯亞胺基材之一面，形成塗膜。然後，對形成之塗膜以70℃加熱1分鐘，藉此使塗膜中之溶劑蒸發，使用紫外線照射裝置(Fusion UV System Japan公司製，光源H燈泡)，於空氣中以積分光量成為200mJ/cm2之方式照射紫外線，使塗膜半硬化。 A polyimide substrate (product name "Neopulim", manufactured by Mitsubishi Gas Chemical Co., Ltd.) with a thickness of 30 μm was prepared as a substrate, and the resin composition 1 was coated on one surface of the polyimide substrate with a bar coater to form a coating. membrane. Then, the formed coating film was heated at 70°C for 1 minute to evaporate the solvent in the coating film. Using an ultraviolet irradiation device (manufactured by Fusion UV System Japan, light source H bulb), the integrated light amount in the air became 200mJ/ Irradiate ultraviolet rays in cm 2 mode to semi-harden the coating film.

接著，用棒式塗布機將樹脂組成物2塗布於經半硬化之塗膜，形成塗膜。然後，對形成之塗膜以70℃加熱1分鐘，藉此使塗膜中之溶劑蒸發，使用紫外線照射裝置(Fusion UV System Japan公司製，光源H燈泡)，於空氣中以積分光量成為100mJ/cm2之方式照射紫外線，使塗膜半硬化。 Next, the resin composition 2 was applied to the semi-cured coating film with a bar coater to form a coating film. Then, the formed coating film was heated at 70°C for 1 minute to evaporate the solvent in the coating film. Using an ultraviolet irradiation device (manufactured by Fusion UV System Japan, light source H bulb), the integrated light amount in the air became 100mJ/ Irradiate ultraviolet rays in cm 2 mode to semi-harden the coating film.

接著，用棒式塗布機將樹脂組成物4塗布於經半硬化之塗膜，形成塗膜。然後，對形成之塗膜以70℃加熱1分鐘，藉此使塗膜中之溶劑蒸發，使用紫外線照射裝置(Fusion UV System Japan公司製，光源H燈泡)，於空氣中以積分光量成為600mJ/cm2之方式照射紫外線，使塗膜完全硬化。藉此，得到於聚醯亞胺基材之一面具有樹脂層的光學膜，該樹脂層為從聚醯亞胺基材側依序積層有膜厚為200μm之第1層、膜厚為20μm之第2層、膜厚為1μm之第3層的3層構造。 Next, the resin composition 4 was applied to the semi-cured coating film with a bar coater to form a coating film. Then, the formed coating film was heated at 70°C for 1 minute to evaporate the solvent in the coating film. Using an ultraviolet irradiation device (manufactured by Fusion UV System Japan, light source H bulb), the integrated light amount in the air became 600mJ/ Irradiate ultraviolet rays in cm 2 mode to completely harden the coating film. Thereby, an optical film having a resin layer on one surface of a polyimide substrate was obtained, and the resin layer was a first layer with a film thickness of 200 μm and a film thickness of 20 μm laminated in order from the side of the polyimide substrate. A three-layer structure with the second layer and the third layer with a thickness of 1 μm.

關於各層之膜厚，係使用掃描型電子顯微鏡(SEM)，對各層之剖面進行拍攝，於該剖面之影像中分別測量各層20處之膜厚，將該20處之膜厚的算術平均值作為該層之膜厚。具體之剖面照片的拍攝方法如下。首先，製 作藉由埋置樹脂埋置切成1mm×10mm之光學膜而成的團塊，藉由一般切片製作方法從該團塊切下沒有孔洞等之均勻的厚度70nm以上100nm以下之切片。切片之製作，係使用「Ultramicrotome EM UC7」(Leica Microsystems股份有限公司)等。接著，將被切下此沒有孔洞等之均勻的切片剩下的團塊作為測量樣品。然後，使用掃描型電子顯微鏡(SEM)(製品名「S-4800」，日立全球先端科技公司製)，拍攝測量樣品之剖面照片。於使用上述S-4800拍攝剖面照片時，將檢測器設為「SE」，加速電壓設為「5kV」，射出電流設為「10μA」，進行剖面觀察。關於倍率，係一邊調節焦點，對對比度及亮度觀察是否可辨別各層，一邊以100~10萬倍作適當調節。並且，將光圈設為「束監測器孔徑3」，物鏡孔徑設為「3」，且W.D.設為「8mm」。又，聚醯亞胺基材之厚度亦藉由與上述各層膜厚同樣之方法測量。又，於實施例2~5及比較例1~4，亦藉由與實施例1同樣之方式測量基材厚度或樹脂層膜厚。 Regarding the film thickness of each layer, a scanning electron microscope (SEM) was used to photograph the cross section of each layer. The film thickness of each layer at 20 locations was measured in the image of the cross section, and the arithmetic average of the film thicknesses at the 20 locations was taken as The film thickness of this layer. The specific method for taking the cross-sectional photos is as follows. First, an agglomerate formed by embedding an optical film of 1 mm × 10 mm by embedding resin is produced, and a uniform thickness of 70 nm or more and 100 nm or less without holes is cut from the agglomerate by a general slicing method. The production of slices uses "Ultramicrotome EM UC7" (Leica Microsystems Co., Ltd.), etc. Next, the mass left over from this uniform slice without holes or the like is used as a measurement sample. Then, use a scanning electron microscope (SEM) (product name "S-4800", manufactured by Hitachi Global Advanced Technology Co., Ltd.) to take a cross-sectional photograph of the measured sample. When using the above-mentioned S-4800 to take cross-sectional photos, set the detector to "SE", the acceleration voltage to "5kV", and the emission current to "10μA" to observe the cross-section. Regarding the magnification, while adjusting the focus and observing whether the layers can be distinguished by contrast and brightness, the magnification is adjusted appropriately from 100 to 100,000 times. Also, set the aperture to "beam monitor aperture 3", objective lens aperture to "3", and W.D. to "8mm". In addition, the thickness of the polyimide substrate was also measured by the same method as the above-mentioned film thickness of each layer. In addition, in Examples 2 to 5 and Comparative Examples 1 to 4, the thickness of the substrate or the thickness of the resin layer was also measured in the same manner as in Example 1.

<實施例2> <Example 2>

於實施例2中，除了使用樹脂組成物3代替樹脂組成物2來形成第2層以外，其餘皆以與實施例1同樣方式得到光學膜。 In Example 2, the optical film was obtained in the same manner as in Example 1, except that the resin composition 3 was used instead of the resin composition 2 to form the second layer.

<實施例3> <Example 3>

準備厚度30μm具有上述式(1)表示之聚醯亞胺骨架的聚醯亞胺基材作為基材，用棒式塗布機將樹脂組成物1塗布於聚醯亞胺基材之一面，形成塗膜。然後，對形成之塗膜以70℃加熱1分鐘，藉此使塗膜中之溶劑蒸發，使用紫外線照射裝置(Fusion UV System Japan公司製，光源H燈泡)，於空氣中以積分光量成為200mJ/cm2之方式照射紫外線，使塗膜半硬化。 A polyimide substrate with a thickness of 30 μm and a polyimide skeleton represented by the above formula (1) was prepared as a substrate, and the resin composition 1 was coated on one side of the polyimide substrate with a bar coater to form a coating membrane. Then, the formed coating film was heated at 70°C for 1 minute to evaporate the solvent in the coating film. Using an ultraviolet irradiation device (manufactured by Fusion UV System Japan, light source H bulb), the integrated light amount in the air became 200mJ/ Irradiate ultraviolet rays in cm 2 mode to semi-harden the coating film.

接著，用棒式塗布機將樹脂組成物2塗布於經半硬化之塗膜，形成塗膜。然後，對形成之塗膜以70℃加熱1分鐘，藉此使塗膜中之溶劑蒸發，使用紫外線照射裝置(Fusion UV System Japan公司製，光源H燈泡)，於空氣 中以積分光量成為100mJ/cm2之方式照射紫外線，使塗膜半硬化。 Next, the resin composition 2 was applied to the semi-cured coating film with a bar coater to form a coating film. Then, the formed coating film was heated at 70°C for 1 minute to evaporate the solvent in the coating film. Using an ultraviolet irradiation device (manufactured by Fusion UV System Japan, light source H bulb), the integrated light amount in the air became 100mJ/ Irradiate ultraviolet rays in cm 2 mode to semi-harden the coating film.

接著，用棒式塗布機將樹脂組成物3塗布於經半硬化之塗膜，形成塗膜。然後，對形成之塗膜以70℃加熱1分鐘，使塗膜中之溶劑蒸發，使用紫外線照射裝置(Fusion UV System Japan公司製，光源H燈泡)，於空氣中以積分光量成為100mJ/cm2之方式照射紫外線，使塗膜半硬化。 Next, the resin composition 3 was applied to the semi-cured coating film with a bar coater to form a coating film. Then, the formed coating film was heated at 70°C for 1 minute to evaporate the solvent in the coating film. Using an ultraviolet irradiation device (manufactured by Fusion UV System Japan, light source H bulb), the integrated light amount in the air became 100mJ/cm 2 The method irradiates ultraviolet rays to semi-harden the coating film.

接著，用棒式塗布機將樹脂組成物4塗布於經半硬化之塗膜，形成塗膜。然後，對形成之塗膜以70℃加熱1分鐘，藉此使塗膜中之溶劑蒸發，使用紫外線照射裝置(Fusion UV System Japan公司製，光源H燈泡)，於空氣中以積分光量成為600mJ/cm2之方式照射紫外線，使塗膜完全硬化。藉此，得到於聚醯亞胺基材之一面具有樹脂層的光學膜，該樹脂層為從聚醯亞胺基材側依序積層有膜厚為200μm之第1層、膜厚為20μm之第2層、膜厚為5μm之第3層、膜厚為1μm之第4層的4層構造。 Next, the resin composition 4 was applied to the semi-cured coating film with a bar coater to form a coating film. Then, the formed coating film was heated at 70°C for 1 minute to evaporate the solvent in the coating film. Using an ultraviolet irradiation device (manufactured by Fusion UV System Japan, light source H bulb), the integrated light amount in the air became 600mJ/ Irradiate ultraviolet rays in cm 2 mode to completely harden the coating film. Thereby, an optical film having a resin layer on one surface of a polyimide substrate was obtained, and the resin layer was a first layer with a film thickness of 200 μm and a film thickness of 20 μm laminated in order from the side of the polyimide substrate. A 4-layer structure of the second layer, the third layer with a thickness of 5 μm, and the fourth layer with a thickness of 1 μm.

<實施例4> <Example 4>

於實施例4中，除了使用厚度30μm具有上述式(22)表示之聚芳醯胺骨架的聚芳醯胺基材代替聚醯亞胺基材以外，其餘皆以與實施例1同樣方式得到光學膜。 In Example 4, except that a polyaramide substrate having a polyaramide skeleton represented by the above formula (22) with a thickness of 30 μm was used instead of the polyimide substrate, the optical fiber was obtained in the same manner as in Example 1. membrane.

<實施例5> <Example 5>

於實施例5，首先準備作為離型膜之厚度100μm經單面易接著處理過的聚對酞酸乙二酯(PET)膜(製品名「cosmoshine A4100」，東洋紡公司製)來代替聚醯亞胺基材，以與實施例1同樣之次序，依序將由樹脂組成物1之硬化物構成之膜厚為200μm的第1層、由樹脂組成物2之硬化物構成之膜厚為20μm的第2層、由樹脂組成物4之硬化物構成之膜厚為1μm的第3層形成於PET膜之未處理面。接著，將PET膜剝離，得到光學膜。然後，將作為離型膜之具有黏著層的聚乙烯膜(製品名「SUNYTECT(註冊商標)，山櫻化研股份有限公司製)分別貼合於光 學膜之第1層及第3層的表面，而得到附離型膜之光學膜。 In Example 5, firstly, a polyethylene terephthalate (PET) film (product name "cosmoshine A4100", manufactured by Toyobo Co., Ltd.), which was a release film with a thickness of 100 μm and was easily bonded on one side, was prepared instead of polyamide. For the amine substrate, in the same order as in Example 1, the first layer composed of the cured product of the resin composition 1 with a film thickness of 200 μm, and the second layer composed of the cured product of the resin composition 2 with a thickness of 20 μm were sequentially A two-layer, a third layer with a thickness of 1 μm composed of a cured product of the resin composition 4 was formed on the untreated surface of the PET film. Next, the PET film was peeled off to obtain an optical film. Then, a polyethylene film with an adhesive layer as a release film (product name "SUNYTECT (registered trademark), manufactured by Yamazakura Kaken Co., Ltd.) was attached to the surface of the first layer and the third layer of the optical film, respectively , And get the optical film with release film.

<比較例1> <Comparative Example 1>

於比較例1中，除了不形成樹脂層中之第2層及第3層，亦即使樹脂層為僅由第1層構成之單層構造以外，其餘皆以與實施例1同樣方式得到光學膜。 In Comparative Example 1, the optical film was obtained in the same manner as in Example 1, except that the second and third layers of the resin layer were not formed, and even if the resin layer had a single-layer structure consisting of only the first layer. .

<比較例2> <Comparative Example 2>

於比較例2中，除了不形成樹脂層中之第3層，亦即使樹脂層為第1層及第2層之2層構造以外，其餘皆以與實施例1同樣方式得到光學膜。 In Comparative Example 2, an optical film was obtained in the same manner as in Example 1, except that the third layer of the resin layer was not formed, and even if the resin layer had a two-layer structure of the first layer and the second layer.

<比較例3> <Comparative Example 3>

準備厚度30μm之聚醯亞胺基材(製品名「Neopulim」，三菱瓦斯化學公司製)作為基材，用棒式塗布機將樹脂組成物1塗布於聚醯亞胺基材之一面，形成塗膜。然後，對形成之塗膜以70℃加熱1分鐘，藉此使塗膜中之溶劑蒸發，使用紫外線照射裝置(Fusion UV System Japan公司製，光源H燈泡)，於空氣中以積分光量成為200mJ/cm2之方式照射紫外線，使塗膜半硬化。 A polyimide substrate (product name "Neopulim", manufactured by Mitsubishi Gas Chemical Co., Ltd.) with a thickness of 30 μm was prepared as a substrate, and the resin composition 1 was coated on one surface of the polyimide substrate with a bar coater to form a coating. membrane. Then, the formed coating film was heated at 70°C for 1 minute to evaporate the solvent in the coating film. Using an ultraviolet irradiation device (manufactured by Fusion UV System Japan, light source H bulb), the integrated light amount in the air became 200mJ/ Irradiate ultraviolet rays in cm 2 mode to semi-harden the coating film.

接著，用棒式塗布機將樹脂組成物4塗布於經半硬化之塗膜，形成塗膜。然後，對形成之塗膜以70℃加熱1分鐘，藉此使塗膜中之溶劑蒸發，使用紫外線照射裝置(Fusion UV System Japan公司製，光源H燈泡)，於空氣中以積分光量成為600mJ/cm2之方式照射紫外線，使塗膜完全硬化。藉此，得到於聚醯亞胺基材之一面具有樹脂層的光學膜，該樹脂層為從聚醯亞胺基材側依序積層有膜厚為200μm之第1層、膜厚為1μm之第2層的2層構造。 Next, the resin composition 4 was applied to the semi-cured coating film with a bar coater to form a coating film. Then, the formed coating film was heated at 70°C for 1 minute to evaporate the solvent in the coating film. Using an ultraviolet irradiation device (manufactured by Fusion UV System Japan, light source H bulb), the integrated light amount in the air became 600mJ/ Irradiate ultraviolet rays in cm 2 mode to completely harden the coating film. Thereby, an optical film having a resin layer on one side of a polyimide substrate was obtained, and the resin layer was a first layer with a film thickness of 200 μm and a film thickness of 1 μm laminated in order from the side of the polyimide substrate. The second floor is a two-layer structure.

<比較例4> <Comparative Example 4>

準備厚度30μm之聚醯亞胺基材(製品名「Neopulim」，三菱瓦斯化學公司製)作為基材，用棒式塗布機將樹脂組成物2塗布於聚醯亞胺基材之一面，形成塗膜。然後，對形成之塗膜以70℃加熱1分鐘，藉此使塗膜中之溶劑蒸發，使用紫外線照射裝置(Fusion UV System Japan公司製，光源H燈泡)，於空氣中以積分 光量成為200mJ/cm2之方式照射紫外線，使塗膜半硬化。 A polyimide substrate (product name "Neopulim", manufactured by Mitsubishi Gas Chemical Co., Ltd.) with a thickness of 30 μm was prepared as a substrate, and the resin composition 2 was coated on one surface of the polyimide substrate with a bar coater to form a coating. membrane. Then, the formed coating film was heated at 70°C for 1 minute to evaporate the solvent in the coating film. Using an ultraviolet irradiation device (manufactured by Fusion UV System Japan, light source H bulb), the integrated light amount in the air became 200mJ/ Irradiate ultraviolet rays in cm 2 mode to semi-harden the coating film.

接著，用棒式塗布機將樹脂組成物1塗布於經半硬化之塗膜，形成塗膜。然後，對形成之塗膜以70℃加熱1分鐘，藉此使塗膜中之溶劑蒸發，使用紫外線照射裝置(Fusion UV System Japan公司製，光源H燈泡)，於空氣中以積分光量成為200mJ/cm2之方式照射紫外線，使塗膜半硬化。 Next, the resin composition 1 was applied to the semi-cured coating film with a bar coater to form a coating film. Then, the formed coating film was heated at 70°C for 1 minute to evaporate the solvent in the coating film. Using an ultraviolet irradiation device (manufactured by Fusion UV System Japan, light source H bulb), the integrated light amount in the air became 200mJ/ Irradiate ultraviolet rays in cm 2 mode to semi-harden the coating film.

接著，用棒式塗布機將樹脂組成物4塗布於經半硬化之塗膜，形成塗膜。然後，對形成之塗膜以70℃加熱1分鐘，藉此使塗膜中之溶劑蒸發，使用紫外線照射裝置(Fusion UV System Japan公司製，光源H燈泡)，於空氣中以積分光量成為600mJ/cm2之方式照射紫外線，使塗膜完全硬化。藉此，得到於聚醯亞胺基材之一面具有樹脂層的光學膜，該樹脂層為從聚醯亞胺基材側依序積層有膜厚為20μm之第1層、膜厚為200μm之第2層、膜厚為1μm之第3層的3層構造。 Next, the resin composition 4 was applied to the semi-cured coating film with a bar coater to form a coating film. Then, the formed coating film was heated at 70°C for 1 minute to evaporate the solvent in the coating film. Using an ultraviolet irradiation device (manufactured by Fusion UV System Japan, light source H bulb), the integrated light amount in the air became 600mJ/ Irradiate ultraviolet rays in cm 2 mode to completely harden the coating film. Thereby, an optical film having a resin layer on one side of the polyimide substrate is obtained, and the resin layer is a first layer with a film thickness of 20 μm and a film thickness of 200 μm laminated in order from the side of the polyimide substrate. A three-layer structure with the second layer and the third layer with a thickness of 1 μm.

<壓痕硬度> <Indentation Hardness>

對實施例及比較例之光學膜，測量基材及樹脂層各層之壓痕硬度。具體而言，對實施例1~5及比較例1~4之光學膜，首先製作藉由埋置樹脂埋置切成1mm×10mm之光學膜而成的團塊，藉由一般切片製作方法從該團塊切下沒有孔洞等之均勻的厚度70nm以上100nm以下之切片。另一方面，對實施例5之光學膜，首先從附離型膜之光學膜將兩離型膜剝離，得到光學膜單體。接著，將光學膜切成1mm×10mm，製作藉由埋置樹脂埋置此大小之光學膜而成的團塊，藉由一般切片製作方法從該團塊切下沒有孔洞等之均勻的厚度70nm以上100nm以下之切片。切片之製作，係使用「Ultramicrotome EM UC7」(Leica Microsystems股份有限公司)等。接著， For the optical films of the Examples and Comparative Examples, the indentation hardness of each layer of the substrate and the resin layer was measured. Specifically, for the optical films of Examples 1 to 5 and Comparative Examples 1 to 4, first agglomerates formed by embedding resin and cutting into optical films of 1 mm×10 mm were produced, and then a general slicing method was used to prepare agglomerates The agglomerate is cut into slices with a uniform thickness of 70 nm or more and 100 nm or less without holes or the like. On the other hand, for the optical film of Example 5, first, the two release films were peeled off from the optical film with release film to obtain an optical film monomer. Next, the optical film was cut into 1mm×10mm, and a mass formed by embedding an optical film of this size with resin was produced, and a uniform thickness of 70nm without holes was cut from the mass by a general slicing method. Above and below 100nm slices. The production of slices uses "Ultramicrotome EM UC7" (Leica Microsystems Co., Ltd.), etc. Then,

將被切下此沒有孔洞等之均勻的切片剩下的團塊作為測量樣品。接著，於此種測量樣品中因被切下上述切片而得之基材及樹脂層各層的剖面中央，使用 海思創(HYSITRON)公司製之「TI950 TriboIndenter」，分別以最大負載40μN、速度10μN/s壓入Berkovich壓頭(三角錐)100nm，保持一定，進行殘留應力緩和後，將負載卸除，量測緩和後之最大負載，使用該最大負載Pmax(μN)及壓頭與試樣(各層)之接觸投影面積Ap(nm2)，藉由Pmax/Ap算出。將壓痕硬度設為經測量10次之值的算術平均值。 The mass left over from this uniform slice without holes or the like is used as the measurement sample. Then, in the center of the cross section of each layer of the base material and resin layer obtained by cutting the above-mentioned slices in this kind of measurement sample, the "TI950 TriboIndenter" manufactured by HYSITRON was used with a maximum load of 40μN and a speed of 10μN. /s Press into the Berkovich indenter (triangular cone) 100nm, keep it constant, after the residual stress is relaxed, remove the load, measure the relaxed maximum load, use the maximum load P max (μN) and the indenter and sample The projected contact area Ap (nm 2 ) of (each layer) is calculated by P max /A p. Set the indentation hardness to the arithmetic average of the values measured 10 times.

<彎曲性> <Flexibility>

對實施例及比較例之光學膜，進行彎曲性測試。具體而言，對實施例1~4及比較例1~4之光學膜，首先，將光學膜切成30mm×100mm之長方形，製作測量樣品。另一方面，對實施例5之光學膜，首先從附離型膜之光學膜將兩離型膜剝離，得到光學膜單體。接著，透過厚度25μm之光學黏著層(製品名「PANACLEAN(註冊商標)PD-S1」，汎納克公司製)將厚度30μm之聚醯亞胺膜(製品名「Neopulim」，三菱瓦斯化學公司製)貼合於光學膜之背面(第1層側之面)，形成積層體。接著，將此積層體切成30mm×100mm之長方形，得到測量樣品。接著，對測量樣品用固定部將測量樣品之短邊(30mm)側分別固定在耐久測試機(製品名「DLDMLH-FS」，湯淺系統機器公司製)，以相對向之2個邊部的間隔成為6mm(彎曲部之外徑6.0mm)的方式將測量樣品之樹脂層側之面折疊180°。於該狀態下，在螢光燈下，藉由目視觀察測量樣品之彎曲部是否產生皺折。然後，將樣品從固定部取下，於使樣品呈平坦狀之狀態下，用光學顯微鏡(製品名「VHX-5000」，其恩斯公司製)觀察彎曲部是否產生細微之裂紋。評價結果如下。 The optical films of the Examples and Comparative Examples were tested for flexibility. Specifically, with respect to the optical films of Examples 1 to 4 and Comparative Examples 1 to 4, first, the optical films were cut into 30 mm×100 mm rectangles to prepare measurement samples. On the other hand, for the optical film of Example 5, first, the two release films were peeled off from the optical film with release film to obtain an optical film monomer. Next, a polyimide film (product name "Neopulim", product name "Neopulim", product name "Mitsubishi Gas Chemical Co., Ltd." ) It is bonded to the back surface (the surface on the first layer side) of the optical film to form a laminate. Next, this laminate was cut into a rectangle of 30 mm×100 mm to obtain a measurement sample. Next, fix the short side (30mm) side of the measurement sample to the durability tester (product name "DLDMLH-FS", manufactured by Yuasa System Machinery Co., Ltd.) to the fixing part for the measurement sample, with an interval between the two opposite sides. Fold the surface of the resin layer side of the measurement sample by 180° so that it becomes 6mm (outer diameter of the bent portion 6.0mm). In this state, under a fluorescent lamp, visually observe whether the bending part of the sample is wrinkled. Then, the sample is removed from the fixed part, and in the state where the sample is flat, an optical microscope (product name "VHX-5000", manufactured by Chines Co., Ltd.) is used to observe whether there are fine cracks in the bent part. The evaluation results are as follows.

(皺折評價) (Wrinkle evaluation)

○：未觀察到皺折。 ○: No wrinkles are observed.

╳：觀察到皺折。 ╳: Wrinkles are observed.

(裂紋評價) (Crack evaluation)

○：未觀察到細微之裂紋。 ○: No fine cracks are observed.

╳：觀察到細微之裂紋。 ╳: Micro cracks are observed.

<耐擦傷性> <Scratch resistance>

對實施例及比較例之光學膜進行耐擦傷性測試。具體而言，對實施例1~4及比較例1~4之光學膜，首先將光學膜切成50mm×100mm大小，製作測量樣品。另一方面，對實施例5之光學膜，首先從附離型膜之光學膜將兩離型膜剝離，得到光學膜單體。接著，將光學膜切成50mm×100mm大小，製作測量樣品。得到測量樣品後，用日絆公司製之Cellotape(註冊商標)將測量樣品以沒有彎折或皺折之方式固定於玻璃板上使樹脂層成為上側。接著，對測量樣品之表面(樹脂層之表面)，進行使用#0000號之鋼絲絨(製品名「bonstar」，日本鋼絲絨公司製)施加1kg/cm2之負載且同時往返摩擦10次的耐擦傷性測試，觀察樹脂層表面是否確認到裂縫或損傷。評價結果如下。 The scratch resistance test was performed on the optical films of the examples and comparative examples. Specifically, for the optical films of Examples 1 to 4 and Comparative Examples 1 to 4, first, the optical films were cut into a size of 50 mm×100 mm to prepare measurement samples. On the other hand, for the optical film of Example 5, first, the two release films were peeled off from the optical film with release film to obtain an optical film monomer. Next, the optical film was cut into a size of 50 mm×100 mm to prepare a measurement sample. After the measurement sample is obtained, the measurement sample is fixed on the glass plate without bending or wrinkles using Cellotape (registered trademark) manufactured by Nisshin Corporation so that the resin layer becomes the upper side. Next, on the surface of the measurement sample (the surface of the resin layer), the steel wool #0000 (product name "bonstar", manufactured by Japan Steel Wool Co.) was used to apply a load of 1 kg/cm 2 and at the same time reciprocating rubbing 10 times. Scratch test to observe whether cracks or damage are confirmed on the surface of the resin layer. The evaluation results are as follows.

○：皆未觀察到裂縫及損傷。 ○: Cracks and damage are not observed at all.

╳：觀察到裂縫及損傷之任一者。 ╳: Any crack or damage is observed.

<折疊性> <Foldability>

對實施例及比較例之光學膜進行折疊測試，評價折疊性。具體而言，對實施例1~4及比較例1~4之光學膜，首先切成30mm×100mm之長方形製作測量樣品。另一方面，對實施例5之光學膜，首先從附離型膜之光學膜將兩離型膜剝離，得到光學膜單體。接著，透過厚度25μm之光學黏著層(製品名「PANACLEAN(註冊商標)PD-S1」，汎納克公司製)將聚醯亞胺膜(製品名「Neopulim」，三菱瓦斯化學公司製)貼合於光學膜之背面(第1層側之面)，形成積層體。接著，將此積層體切成30mm×100mm之長方形，製作測量樣品。製作測量樣品後，用固定部將測量樣品之短邊(30mm)側分別固定於耐久測試機(製品名「DLDMLH-FS」，湯淺系統機器公司製)，如圖2(C)所示，安裝成使相對向 之2個邊部的最小間隔成為6mm(彎曲部之外徑6.0mm)，進行10萬次將測量樣品之樹脂層側之面折疊180°的測試(折疊成使樹脂層成為內側，基材或聚醯亞胺膜成為外側之測試)，檢查彎曲部是否產生裂縫或斷裂。又，用實施例及比較例之光學膜以與上述同樣方式製作新的樣品，將該樣品以與上述同樣方式安裝於上述之耐久測試機，進行10萬次將測量樣品之基材側之面折疊180°的測試(折疊成使樹脂層成為外側，基材或聚醯亞胺膜成為內側之測試)，檢查彎曲部是否產生裂縫或斷裂。用以下之基準評價折疊測試之結果。 Folding tests were performed on the optical films of the examples and comparative examples to evaluate the foldability. Specifically, the optical films of Examples 1 to 4 and Comparative Examples 1 to 4 were first cut into 30 mm×100 mm rectangles to prepare measurement samples. On the other hand, for the optical film of Example 5, first, the two release films were peeled off from the optical film with release film to obtain an optical film monomer. Next, a polyimide film (product name "Neopulim", manufactured by Mitsubishi Gas Chemical Co., Ltd.) was pasted through an optical adhesive layer (product name "PANACLEAN (registered trademark) PD-S1", manufactured by Fannac Corporation) with a thickness of 25 μm On the back surface of the optical film (the surface on the first layer side), a laminate is formed. Next, this laminate was cut into a rectangle of 30 mm×100 mm to prepare a measurement sample. After making the measurement sample, fix the short side (30mm) side of the measurement sample to the durability tester (product name "DLDMLH-FS", manufactured by Yuasa System Machinery Co., Ltd.) with the fixing part, as shown in Figure 2(C), install Make the minimum distance between the two opposing sides 6mm (outer diameter of the bend is 6.0mm), and perform 100,000 times the test that the resin layer side of the measurement sample is folded 180° (folded so that the resin layer becomes the inner side , The substrate or polyimide film becomes the outside test), check whether there are cracks or breaks in the bent part. In addition, the optical films of the Examples and Comparative Examples were used to make new samples in the same manner as described above, and the samples were installed in the durability tester described above in the same manner as described above. Fold 180° test (folded so that the resin layer becomes the outer side and the base material or the polyimide film becomes the inner side) to check whether there are cracks or breaks in the bent part. Use the following benchmarks to evaluate the results of the folding test.

○：無論於任一折疊測試，彎曲部皆未產生裂縫或斷裂。 ○: No cracks or breaks occurred in the bent part regardless of any folding test.

╳：於其中一折疊測試，彎曲部產生了裂縫或斷裂。 ╳: In one of the folding tests, cracks or breaks occurred in the bending part.

<耐撞擊性> <Impact resistance>

對實施例及比較例之光學膜評價耐撞擊性。具體而言，對實施例1~4及比較例1~4之光學膜，首先將光學膜切成100mm×100mm大小，製作測量樣品。另一方面，對實施例5的附離型膜之光學膜，首先將兩離型膜剝離，而得到光學膜單體。接著，將光學膜切成100mm×100mm大小，製作測量樣品。製作測量樣品後，以第1層較第n層靠近鈉玻璃板側之方式將測量樣品放置於厚度0.7mm之鈉玻璃板上，從高度30cm之位置使重量100g、直徑30mm之鐵球掉落於光學膜之樹脂層的表面，進行此測試各3次。另，使鐵球掉落之位置每次都改變。接著，評價是否藉由目視在樹脂層表面確認到凹陷，且評價鈉玻璃板是否產生了裂縫。評價結果如下。 The optical films of the examples and comparative examples were evaluated for impact resistance. Specifically, for the optical films of Examples 1 to 4 and Comparative Examples 1 to 4, first, the optical films were cut into a size of 100 mm×100 mm to prepare measurement samples. On the other hand, with respect to the optical film with a release film of Example 5, the two release films were first peeled off to obtain an optical film monomer. Next, the optical film was cut into a size of 100 mm×100 mm to produce a measurement sample. After making the measurement sample, place the measurement sample on a soda glass plate with a thickness of 0.7mm in such a way that the first layer is closer to the side of the soda glass plate than the nth layer, and drop an iron ball with a weight of 100g and a diameter of 30mm from a height of 30cm. Perform this test 3 times on the surface of the resin layer of the optical film. In addition, the drop position of the iron ball is changed every time. Next, it was evaluated whether or not a dent was confirmed on the surface of the resin layer by visual observation, and whether a crack was generated in the soda glass plate was evaluated. The evaluation results are as follows.

(樹脂層表面之凹陷評價) (Evaluation of the depression on the surface of the resin layer)

◎：於從正面及斜面觀察樹脂層的此兩種情形，樹脂層之表面皆未確認到凹陷。 ◎: In both cases of observing the resin layer from the front surface and the oblique surface, no depression was confirmed on the surface of the resin layer.

○：從正面觀察樹脂層之情形時，樹脂層之表面未觀察到凹陷，但當從斜面觀察之情形時，樹脂層之表面確認到實用上沒有問題之程度的凹陷。 ○: When the resin layer is viewed from the front, no dents are observed on the surface of the resin layer, but when viewed from an oblique surface, the surface of the resin layer is confirmed to have dents to the extent that there are no practical problems.

╳：於從正面及斜面觀察樹脂層的此兩種情形，樹脂層之表面觀察到明顯的凹陷。 ╳: In the two cases of observing the resin layer from the front and the oblique surface, obvious depressions are observed on the surface of the resin layer.

(鈉玻璃之裂縫評價) (Crack evaluation of soda glass)

◎：鈉玻璃沒有裂開。 ◎: The soda glass is not cracked.

○：鈉玻璃雖有損傷，但沒有裂開。 ○: Although the soda glass is damaged, it is not cracked.

△：1~2次鈉玻璃產生裂縫。 △: Cracks occurred in the soda glass 1 to 2 times.

╳：3次鈉玻璃皆產生裂縫。 ╳: Cracks occurred in the three times soda glass.

<鉛筆硬度> <Pencil Hardness>

基於JIS K5600-5-4：1999分別測量實施例及比較例之光學膜表面(樹脂層表面)的鉛筆硬度。具體而言，對實施例1~4及比較例1~4之光學膜，首先切成50mm×100mm大小，製作測量樣品。另一方面，對實施例5之光學膜，首先從附離型膜之光學膜將兩離型膜剝離，得到光學膜單體。接著，將光學膜切成50mm×100mm大小製作測量樣品。製作測量樣品後，用日絆公司製之Cellotape(註冊商標)以沒有彎折或皺折之方式將測量樣品固定於厚度2mm之玻璃板上。接著，使用鉛筆硬度測試機(製品名「鉛筆抓刮塗膜硬度測試機(電動式)」，東洋精機製作所股份有限公司製)，將750g之負載施加於鉛筆(製品名「uni」，三菱鉛筆股份有限公司製)，且同時以速度1mm/秒移動鉛筆。使鉛筆硬度為鉛筆硬度測試中測量樣品之表面(樹脂層之表面)沒有發生損傷的最高硬度。另，於測量鉛筆硬度時，雖使用複數根硬度不同之鉛筆進行，但每1根鉛筆會進行5次鉛筆硬度測試，當5次之中有4次以上在螢光燈下對測量樣品表面進行透射觀察時沒有目視辨認到測量樣品表面有損傷之情形時，判斷此硬度之鉛筆不會對測量樣品表面造成損傷。 Based on JIS K5600-5-4:1999, the pencil hardness of the optical film surface (resin layer surface) of the Examples and Comparative Examples was measured respectively. Specifically, the optical films of Examples 1 to 4 and Comparative Examples 1 to 4 were first cut into a size of 50 mm×100 mm to prepare measurement samples. On the other hand, for the optical film of Example 5, first, the two release films were peeled off from the optical film with release film to obtain an optical film monomer. Next, the optical film was cut into a size of 50 mm×100 mm to produce a measurement sample. After the measurement sample is made, the measurement sample is fixed on a glass plate with a thickness of 2 mm using Cellotape (registered trademark) manufactured by Nisshin Co., Ltd. without bending or wrinkles. Next, using a pencil hardness tester (product name "Pencil scratch coating film hardness tester (electric type)", manufactured by Toyo Seiki Seisakusho Co., Ltd.), a load of 750 g is applied to the pencil (product name "uni", Mitsubishi Pencil Co., Ltd.), and at the same time move the pencil at a speed of 1 mm/sec. Make the pencil hardness the highest hardness at which the surface of the measured sample (the surface of the resin layer) is not damaged in the pencil hardness test. In addition, when measuring pencil hardness, although multiple pencils with different hardness are used, each pencil will be tested for 5 times. When the hardness of the test sample is measured more than 4 times out of the 5 times, the surface of the sample is measured under a fluorescent lamp. When there is no visual recognition of damage on the surface of the measurement sample during transmission observation, it is judged that the pencil with this hardness will not cause damage to the surface of the measurement sample.

以下，將結果示於表1及表2。 The results are shown in Table 1 and Table 2 below.

Figure 106135143-A0202-12-0064-32
Figure 106135143-A0202-12-0064-32

Figure 106135143-A0202-12-0064-33
Figure 106135143-A0202-12-0064-33

以下敘述結果。比較例1及2之光學膜，由於樹脂層為相對較柔軟的單層構造或2層構造，因此，於耐擦傷性測試中確認到裂縫或損傷。比較例3之光學膜，由於第2層硬度遠大於第1層，因此，於彎曲性測試中在折疊時發生裂紋，又於耐擦傷性測試中，鋼絲絨下沈至第2層，於第2層發生裂縫。比較例4之光學膜，雖然樹脂層為3層構造，但由於第2層較第1層柔軟，故於彎曲性測試中在折疊時發生皺折或裂紋，又於耐擦傷性測試中，鋼絲絨下沈至第3層，於第3層發生裂縫。 The results are described below. In the optical films of Comparative Examples 1 and 2, since the resin layer had a relatively soft single-layer structure or a two-layer structure, cracks or damage were confirmed in the scratch resistance test. In the optical film of Comparative Example 3, since the hardness of the second layer was much greater than that of the first layer, cracks occurred during folding in the bending test. In the scratch resistance test, the steel wool sank to the second layer. Cracks occurred on the 2nd floor. In the optical film of Comparative Example 4, although the resin layer has a three-layer structure, since the second layer is softer than the first layer, wrinkles or cracks occurred during folding in the bending test, and in the scratch resistance test, the steel The velvet sank to the third layer, and cracks occurred in the third layer.

相對於此，實施例1~5之光學膜，由於樹脂層為3層構造或4層構造，且從基材側或聚醯亞胺膜側至光學膜之表面側各層的壓痕硬度慢慢地變高，因此，於彎曲性測試中沒有發生皺折或細微之裂紋，又於耐擦傷性測試中 亦沒有發生裂縫或損傷。 In contrast, the optical films of Examples 1 to 5 have a three-layer structure or a four-layer structure for the resin layer, and the indentation hardness of each layer from the substrate side or polyimide film side to the surface side of the optical film gradually The ground becomes higher, so no wrinkles or micro cracks occurred in the bending test, and no cracks or damage occurred in the scratch resistance test.

實施例1~5之光學膜，耐撞擊性及折疊測試之結果亦良好，且鉛筆硬度亦高。 The optical films of Examples 1 to 5 have good impact resistance and folding test results, and the pencil hardness is also high.

又，對實施例1、3之光學膜，進行使用#0000號之鋼絲絨(製品名「bonstar」，日本鋼絲絨公司製)將1kg/cm2之負載施加於光學膜表面(樹脂層表面)且同時往返摩擦20次的耐擦傷測試後，結果於實施例1之光學膜確認到裂縫及損傷之任一者，但於實施例3之光學膜皆未觀察到裂縫及損傷。由此結果可確認實施例3之光學膜的耐擦傷性較實施例1之光學膜優異。 In addition, for the optical films of Examples 1 and 3, #0000 steel wool (product name "bonstar", manufactured by Japan Steel Wool Corporation) was used to apply a load of 1 kg/cm 2 to the surface of the optical film (resin layer surface) After the scratch resistance test of 20 times of reciprocating rubbing at the same time, as a result, any cracks and damages were confirmed in the optical film of Example 1, but no cracks and damages were observed in the optical film of Example 3. From this result, it can be confirmed that the scratch resistance of the optical film of Example 3 is superior to that of the optical film of Example 1.

又，對實施例1~4之光學膜測量楊氏係數後，結果楊氏係數皆為3GPa。關於楊氏係數之測量，首先將各光學膜切成2mm×150mm大小，得到樣品。接著，將此樣品之兩端以樣品之長邊方向成為拉伸方向的方式固定於附在Tensilon萬能測試機(製品名「RTC-1310A」，Orientec公司製)之夾頭用治具等，使用上述Tensilon萬能測試機，以測試速度25mm/分將樣品拉伸，將此時樣品之伸長量與負載的測量值換算成應變與應力，求出連接應變為0.5%時之應力與應變為1%時之應力的直線之斜率，藉此得到楊氏係數。使楊氏係數為測量3次所得到之值的算術平均值。 In addition, after measuring the Young's coefficients of the optical films of Examples 1 to 4, the Young's coefficients were all 3 GPa. Regarding the measurement of Young's coefficient, firstly, each optical film was cut into a size of 2mm×150mm to obtain a sample. Next, fix both ends of the sample to a fixture for the chuck attached to the Tensilon universal testing machine (product name "RTC-1310A", manufactured by Orientec) so that the longitudinal direction of the sample becomes the tensile direction, and use The aforementioned Tensilon universal testing machine stretches the sample at a test speed of 25mm/min. The measured value of the elongation and load of the sample at this time is converted into strain and stress, and the stress and strain when the connection strain is 0.5% are calculated as 1% The slope of the straight line of the stress at the time, thereby obtaining the Young's coefficient. Let the Young's coefficient be the arithmetic mean of the values obtained by the three measurements.

對實施例1~5之光學膜測量黃色指數(YI)後，結果實施例1~4為5，實施例5為1。黃色指數係以下述方式算出之值：使用分光光度計(製品名「UV-3100PC」，島津製作所公司製，光源：鎢絲燈及氘燈)，從對切成50mm×100mm大小之光學膜所測得之值依據JIS Z8722：2009記載之算式計算色度三色值X、Y、Z，然後從三色值X、Y、Z依據ASTM D1925：1962記載之算式算出黃色指數。黃色指數為測量3次所得到之值的算術平均值。 After measuring the yellow index (YI) of the optical films of Examples 1 to 5, the results of Examples 1 to 4 are 5, and that of Example 5 is 1. The yellow index is a value calculated as follows: using a spectrophotometer (product name "UV-3100PC", manufactured by Shimadzu Corporation, light source: tungsten lamp and deuterium lamp), from the optical film of 50mm×100mm size. The measured value is calculated according to the formula described in JIS Z8722:2009 to calculate the chromaticity tristimulus value X, Y, Z, and then from the tristimulus value X, Y, Z according to the formula described in ASTM D1925:1962 to calculate the yellow index. The yellow index is the arithmetic mean of the values obtained from 3 measurements.

Claims (14)

一種光學膜，為使用於影像顯示裝置之可折疊的透光性光學膜，具備從第1層依序積層至第3層之多層構造的樹脂層，該樹脂層中之該第1層~該第3層各層的壓痕硬度從該第1層至該第3層依序變大，於該樹脂層中，該第1層之壓痕硬度為1MPa以上100MPa以下，第2層之壓痕硬度為10MPa以上500MPa以下，第3層之壓痕硬度為100MPa以上1000MPa以下。 An optical film is a foldable translucent optical film used in an image display device. It has a resin layer with a multilayer structure from the first layer to the third layer. The first layer to the third layer of the resin layer The indentation hardness of each layer of the third layer increases sequentially from the first layer to the third layer. In the resin layer, the indentation hardness of the first layer is 1 MPa or more and 100 MPa or less, and the indentation hardness of the second layer It is 10MPa or more and 500MPa or less, and the indentation hardness of the third layer is 100MPa or more and 1000MPa or less. 如申請專利範圍第1項之光學膜，其中，以該第1層較該3層更位於鈉玻璃板側之方式將該光學膜放置在厚度0.7mm之鈉玻璃板上，從高度30cm之位置使重量100g及直徑30mm之鐵球掉落至該樹脂層之該第3層的表面，於此情形時，於該第3層之表面不會產生凹陷，且於該鈉玻璃板不會產生裂縫。 For example, the optical film of item 1 in the scope of the patent application, wherein the optical film is placed on a soda glass plate with a thickness of 0.7mm in a way that the first layer is located on the side of the soda glass plate than the three layers, from a height of 30cm Drop an iron ball with a weight of 100g and a diameter of 30mm on the surface of the third layer of the resin layer. In this case, no dents will occur on the surface of the third layer, and no cracks will occur on the soda glass plate . 如申請專利範圍第1項之光學膜，其中，對該樹脂層之該第3層表面進行使用鋼絲絨施加1kg/cm2之負載且同時往返摩擦10次的耐擦傷性測試，於此情形時，於該第3層之表面皆確認不到裂縫及損傷。 For example, the optical film of the first item in the scope of patent application, wherein the surface of the third layer of the resin layer is subjected to a scratch resistance test using steel wool to apply a load of 1 kg/cm 2 and rubbing 10 times at the same time, in this case , No cracks and damage were found on the surface of the third layer. 一種光學膜，為使用於影像顯示裝置之可折疊的透光性光學膜，具備從第1層依序積層至第4層之多層構造的樹脂層，該樹脂層中之該第1層~該第4層各層的壓痕硬度從該第1層至該第4層依序變大，於該樹脂層中，該第1層之壓痕硬度為1MPa以上100MPa以下，第2層之壓痕硬度為10MPa以上300MPa以下，第3層之壓痕硬度為50MPa以上500MPa以下，第4層之壓痕硬度為100MPa以上1000MPa以下。 An optical film is a foldable translucent optical film used in an image display device. It has a resin layer with a multilayer structure from the first layer to the fourth layer. The first layer of the resin layer~the The indentation hardness of each layer of the fourth layer increases sequentially from the first layer to the fourth layer. In the resin layer, the indentation hardness of the first layer is 1 MPa or more and 100 MPa or less, and the indentation hardness of the second layer The indentation hardness of the third layer is 50 MPa or more and 500 MPa or less, and the indentation hardness of the fourth layer is 100 MPa or more and 1000 MPa or less. 如申請專利範圍第4項之光學膜，其中，以該第1層較該4層更位於鈉玻璃板側之方式將該光學膜放置在厚度0.7mm之鈉玻璃板上，從高度30cm之位置使重量100g及直徑30mm之鐵球掉落至該樹脂層之該第4層的表面，於此情形時，於該第4層之表面不會產生凹陷，且於該鈉玻璃板不會產生裂縫。 For example, the optical film of item 4 in the scope of patent application, wherein the optical film is placed on a soda glass plate with a thickness of 0.7mm in such a way that the first layer is more on the side of the soda glass plate than the four layers, from a height of 30cm Drop an iron ball with a weight of 100g and a diameter of 30mm onto the surface of the fourth layer of the resin layer. In this case, no dents will occur on the surface of the fourth layer, and no cracks will occur on the soda glass plate . 如申請專利範圍第4項之光學膜，其中，對該樹脂層之該第4層表面進行使用鋼絲絨施加1kg/cm2之負載且同時往返摩擦10次的耐擦傷性測試，於此情形時，於該第4層之表面皆確認不到裂縫及損傷。 For example, the optical film of item 4 of the scope of patent application, wherein the surface of the fourth layer of the resin layer is subjected to a scratch resistance test using steel wool to apply a load of 1 kg/cm 2 and rubbing 10 times at the same time, in this case , No cracks and damage were found on the surface of the fourth layer. 如申請專利範圍第1或4項之光學膜，其進一步具備有設置於該樹脂層之該第1層側的基材。 For example, the optical film of item 1 or 4 of the scope of patent application further includes a base material provided on the first layer side of the resin layer. 如申請專利範圍第7項之光學膜，其中，該光學膜之楊氏係數為3GPa以上。 For example, the optical film of item 7 in the scope of patent application, wherein the Young's coefficient of the optical film is 3GPa or more. 如申請專利範圍第1或4項之光學膜，其中，該光學膜之黃色指數為15以下。 For example, the optical film of item 1 or 4 in the scope of patent application, wherein the yellow index of the optical film is 15 or less. 如申請專利範圍第1~6任一項之光學膜，其中，以該光學膜相對向之邊部的間隔成為6mm之方式於25℃反覆進行10萬次180°折疊測試，於此情形時，不會產生裂縫或斷裂。 For example, the optical film of any one of the first to sixth in the scope of patent application, in which the 180° folding test is repeated 100,000 times at 25°C so that the distance between the opposing edges of the optical film becomes 6mm. In this case, No cracks or breaks will occur. 如申請專利範圍第7項之光學膜，其中，該基材為由聚醯亞胺系樹脂、聚醯胺系樹脂或此等之混合物構成的基材。 For example, the optical film of item 7 of the scope of patent application, wherein the substrate is a substrate composed of a polyimide resin, a polyimide resin or a mixture of these. 一種影像顯示裝置，為可折疊之影像顯示裝置，具備顯示面板與較該顯示面板更配置於觀察者側之申請專利範圍第1項之光學膜，該 光學膜之該樹脂層中的該第3層較該第1層更位於觀察者側。 An image display device, which is a foldable image display device, is provided with a display panel and an optical film of item 1 of the scope of patent application that is more arranged on the observer side than the display panel. The third layer of the resin layer of the optical film is located more on the observer side than the first layer. 一種影像顯示裝置，為可折疊之影像顯示裝置，具備顯示面板與較該顯示面板更配置於觀察者側之申請專利範圍第4項之光學膜，該光學膜之該樹脂層中的該第4層較該第1層更位於觀察者側。 An image display device, which is a foldable image display device, is provided with a display panel and an optical film of item 4 in the scope of patent application that is more arranged on the observer side than the display panel, and the fourth in the resin layer of the optical film The layer is located more on the observer side than the first layer. 如申請專利範圍第12或13項之影像顯示裝置，其中，該顯示面板為有機發光二極體面板。 For example, the image display device of item 12 or 13 in the scope of patent application, wherein the display panel is an organic light emitting diode panel.
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