TW202022020A - Optical film having the image to be visually recognized with high sharpness without distortion - Google Patents
Optical film having the image to be visually recognized with high sharpness without distortion Download PDFInfo
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- 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
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- G—PHYSICS
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- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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- G02B1/14—Protective coatings, e.g. hard coatings
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- G—PHYSICS
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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Abstract
Description
本發明係關於一種用作可撓性顯示裝置之前面板等之光學膜、及具備該光學膜之可撓性顯示裝置。The present invention relates to an optical film used as a front panel of a flexible display device, etc., and a flexible display device provided with the optical film.
先前,一直使用玻璃作為太陽電池或圖像顯示裝置等之顯示構件之材料。然而,對於近年來之小型化、薄型化、輕量化及可撓化之要求,並不具有充分之材質。因此,作為玻璃之替代材料,對各種膜進行了研究。作為此種膜,例如有包含聚醯亞胺系樹脂之光學膜(例如專利文獻1)。 [先前技術文獻] [專利文獻]Previously, glass has been used as a material for display components such as solar cells or image display devices. However, for the recent requirements for miniaturization, thinning, weight reduction and flexibility, there are not enough materials. Therefore, as an alternative to glass, various films have been studied. As such a film, for example, there is an optical film containing a polyimide-based resin (for example, Patent Document 1). [Prior Technical Literature] [Patent Literature]
[專利文獻1]日本專利特開2009-215412號公報[Patent Document 1] Japanese Patent Laid-Open No. 2009-215412
[發明所欲解決之問題][Problems to be solved by the invention]
於將光學膜應用於可撓性顯示裝置之前面板等透明構件之情形時,有於圖像顯示面彎曲之狀態下顯示影像之情形,因此與非彎曲性圖像顯示面相比要求廣角方向之優異之視認性。然而,根據本發明者之研究,可知先前之包含聚醯亞胺系樹脂之光學膜有時無法充分地滿足該廣角方向之視認性。When an optical film is applied to a transparent member such as a front panel of a flexible display device, an image may be displayed in a state where the image display surface is curved. Therefore, it is required to be superior in the wide-angle direction compared with a non-flexible image display surface The visibility. However, according to the research of the present inventors, it is known that the conventional optical film containing polyimide-based resin sometimes cannot sufficiently satisfy the visibility in the wide-angle direction.
因此,本發明之目的在於提供一種廣角方向之視認性優異之光學膜、及具備該光學膜之可撓性顯示裝置。 [解決問題之技術手段]Therefore, the object of the present invention is to provide an optical film having excellent visibility in a wide-angle direction, and a flexible display device provided with the optical film. [Technical means to solve the problem]
本發明者為了解決上述問題而進行銳意研究,結果發現,於包含選自由聚醯亞胺系樹脂及聚醯胺系樹脂所組成之群中之至少1種樹脂之光學膜中,若散射光比率為規定範圍,則可解決上述問題,從而完成了本發明。即,本發明包含以下之態樣。In order to solve the above-mentioned problems, the inventors conducted intensive research and found that in an optical film containing at least one resin selected from the group consisting of polyimide resins and polyimide resins, if the scattered light ratio In order to specify the range, the above-mentioned problems can be solved, thereby completing the present invention. That is, the present invention includes the following aspects.
[1]一種光學膜,其 包含選自由聚醯亞胺系樹脂及聚醯胺系樹脂所組成之群中之至少1種樹脂,且滿足式(1): 0≦Ts≦0.35 (1) [式(1)中,Ts表示散射光比率(%),定義為Ts=Td/Tt×100,Td及Tt分別表示依據JIS K 7136所測得之擴散光透過率(%)及全光線透過率(%)]。 [2]如[1]所記載之光學膜,其於80℃下之拉伸彈性模數為4,000~9,000 MPa。 [3]如[1]或[2]所記載之光學膜,其於依據JIS K 5600-5-1之耐彎曲性試驗前後之上述散射光比率之差之絕對值ΔTs為0.15%以下。 [4]如[1]至[3]中任一項所記載之光學膜,其厚度為10~150 μm。 [5]如[1]至[4]中任一項所記載之光學膜,其中填料之含量相對於光學膜之質量為5質量%以下。 [6]如[1]至[5]中任一項所記載之光學膜,其於至少一面具有硬塗層。 [7]如[6]所記載之光學膜,其中上述硬塗層之厚度為3~30 μm。 [8]一種可撓性顯示裝置,其具備如[1]至[7]中任一項所記載之光學膜。 [9]如[8]所記載之可撓性顯示裝置,其進而具備觸控感測器。 [10]如[8]或[9]所記載之可撓性顯示裝置,其進而具備偏光板。 [發明之效果][1] An optical film, which It contains at least one resin selected from the group consisting of polyimide resins and polyimide resins, and satisfies formula (1): 0≦Ts≦0.35 (1) [In formula (1), Ts represents the scattered light ratio (%), defined as Ts=Td/Tt×100, Td and Tt respectively represent the diffuse light transmittance (%) and total light transmittance measured according to JIS K 7136 rate(%)]. [2] The optical film as described in [1], which has a tensile modulus of elasticity at 80°C of 4,000 to 9,000 MPa. [3] The optical film as described in [1] or [2], wherein the absolute value ΔTs of the difference between the scattered light ratios before and after the bending resistance test according to JIS K 5600-5-1 is 0.15% or less. [4] The optical film as described in any one of [1] to [3], which has a thickness of 10 to 150 μm. [5] The optical film as described in any one of [1] to [4], wherein the content of the filler is 5% by mass or less relative to the mass of the optical film. [6] The optical film according to any one of [1] to [5], which has a hard coat layer on at least one side. [7] The optical film according to [6], wherein the thickness of the hard coat layer is 3 to 30 μm. [8] A flexible display device comprising the optical film as described in any one of [1] to [7]. [9] The flexible display device as described in [8], which further includes a touch sensor. [10] The flexible display device as described in [8] or [9], which further includes a polarizing plate. [Effect of invention]
本發明之光學膜之廣角方向之視認性優異。The optical film of the present invention has excellent visibility in the wide-angle direction.
[光學膜] 本發明之光學膜包含選自由透明聚醯亞胺系樹脂及聚醯胺系樹脂所組成之群中之至少1種樹脂,且滿足式(1): 0≦Ts≦0.35 (1) [式(1)中,Ts表示散射光比率(%),定義為Ts=Td/Tt×100,Td及Tt分別表示依據JIS K 7136所測得之擴散光透過率(%)及全光線透過率(%)]。 再者,散射光比率可為下述光學膜之厚度範圍內之散射光比率。[Optical Film] The optical film of the present invention contains at least one resin selected from the group consisting of transparent polyimide resins and polyamide resins, and satisfies formula (1): 0≦Ts≦0.35 (1) [In formula (1), Ts represents the scattered light ratio (%), defined as Ts=Td/Tt×100, Td and Tt respectively represent the diffuse light transmittance (%) and total light transmittance measured according to JIS K 7136 rate(%)]. Furthermore, the scattered light ratio may be the scattered light ratio within the thickness range of the following optical film.
如式(1)所示,散射光比率(Ts)表示擴散光透過率(Td)相對於全光線透過率(Tt)之比率,Ts越小,擴散光之比率越小,光於光學膜表面及內部越不易散射。As shown in formula (1), the scattered light ratio (Ts) represents the ratio of the diffuse light transmittance (Td) to the total light transmittance (Tt). The smaller Ts, the smaller the ratio of diffuse light, and the light is on the surface of the optical film And the less easily scattered inside.
本發明之光學膜之散射光比率較小為0~0.35%,因此廣角方向之視認性優異。因此,於將本發明之光學膜應用於圖像顯示裝置之情形時,即便自傾斜方向觀察光學膜,亦可有效地抑制映於顯示部之影像產生變形、或該影像模糊之現象。本發明之光學膜由於具有此種特性,故而於應用於例如可撓性顯示器之情形時即便於圖像顯示面彎曲之狀態下顯示影像,亦可以較高之清晰度視認。本說明書中,所謂視認性意指目視觀察應用光學膜之圖像顯示裝置之顯示部時之可見容易性,例如表示可抑制映於顯示部之影像產生變形、或該影像模糊之現象的特性。又,本說明書中,所謂廣角方向,表示相對於光學膜平面之所有角度方向,尤其表示相對於光學膜平面之傾斜方向。The scattered light ratio of the optical film of the present invention is as small as 0-0.35%, so the visibility in the wide-angle direction is excellent. Therefore, when the optical film of the present invention is applied to an image display device, even if the optical film is viewed from an oblique direction, the image reflected on the display portion can be effectively prevented from being deformed or the image is blurred. Since the optical film of the present invention has such characteristics, when it is applied to a flexible display, even if an image is displayed in a state where the image display surface is curved, it can be visualized with higher definition. In this specification, the visibility refers to the ease of visibility when visually observing the display part of an image display device using an optical film, and for example, means the characteristic that can suppress the deformation of the image reflected on the display part or the phenomenon of blurring of the image. In addition, in this specification, the "wide-angle direction" refers to all angular directions with respect to the plane of the optical film, and particularly refers to the oblique direction with respect to the plane of the optical film.
式(1)中,擴散光透過率(Td)可依據JIS K 7136,使用分光測色計進行測定,例如可藉由實施例所記載之方法進行測定。又,全光線透過率(Tt)可依據JIS K 7136,使用測霧計進行測定,例如可藉由實施例所記載之方法進行測定。In the formula (1), the diffuse light transmittance (Td) can be measured using a spectrophotometer in accordance with JIS K 7136, for example, it can be measured by the method described in the examples. In addition, the total light transmittance (Tt) can be measured using a haze meter in accordance with JIS K 7136, for example, it can be measured by the method described in the examples.
於本發明之光學膜中,散射光比率較佳為0.30%以下,更佳為0.25%以下,進而較佳為0.20%以下,尤佳為0.15%以下,最佳為0.10%以下。若散射光比率為上述上限以下,則容易提高廣角方向之視認性。散射光比率之下限為0以上。再者,藉由適當調整光學膜之組成、例如構成光學膜中所含之樹脂之重複結構之種類或構成比、及光學膜中所含之紫外線吸收劑等添加劑之種類或含量等,光學膜之厚度,或光學膜之製造條件、例如清漆溶劑之種類、乾燥溫度、乾燥時間等,可調整為滿足式(1)。尤其於光學膜形成步驟中,若於下述乾燥條件進行,則容易調整為滿足式(1)。In the optical film of the present invention, the scattered light ratio is preferably 0.30% or less, more preferably 0.25% or less, further preferably 0.20% or less, particularly preferably 0.15% or less, and most preferably 0.10% or less. If the scattered light ratio is equal to or less than the above upper limit, the visibility in the wide-angle direction can be easily improved. The lower limit of the scattered light ratio is 0 or more. Furthermore, by appropriately adjusting the composition of the optical film, such as the type or composition ratio of the repetitive structure of the resin contained in the optical film, and the type or content of additives such as ultraviolet absorbers contained in the optical film, the optical film The thickness or the manufacturing conditions of the optical film, such as the type of varnish solvent, drying temperature, and drying time, can be adjusted to satisfy formula (1). Especially in the optical film forming step, if it is performed under the following drying conditions, it is easy to adjust to satisfy the formula (1).
於本發明之光學膜中,全光線透過率(Tt)較佳為80%以上,更佳為85%以上,進而較佳為88%以上,尤佳為90%以上。若全光線透過率為上述下限以上,則光學膜之透明性變得良好,於應用於圖像顯示裝置之情形時容易表現出優異之視認性。又,全光線透過率之上限通常為100%以下。再者,全光線透過率可為下述光學膜之厚度範圍內之全光線透過率(Tt)。若全光線透過率處於上述範圍,則例如於組入至顯示裝置時,有即便減少背光源之光量亦可獲得明亮之顯示之傾向,可有助於節能。In the optical film of the present invention, the total light transmittance (Tt) is preferably 80% or more, more preferably 85% or more, still more preferably 88% or more, and particularly preferably 90% or more. If the total light transmittance is more than the above lower limit, the transparency of the optical film becomes good, and it is easy to exhibit excellent visibility when applied to an image display device. In addition, the upper limit of the total light transmittance is usually 100% or less. Furthermore, the total light transmittance can be the total light transmittance (Tt) within the thickness range of the following optical film. If the total light transmittance is in the above range, for example, when incorporated into a display device, there is a tendency to obtain a bright display even if the amount of light from the backlight is reduced, which can contribute to energy saving.
於本發明之光學膜中,擴散光透過率(Td)較佳為0.35以下,更佳為0.30以下,進而較佳為0.25以下,尤佳為0.20以下。若擴散光透過率(Td)為上述上限以下,則擴散光之比率變小,容易提高廣角方向之視認性。又,擴散光透過率(Td)之下限通常為0.01以上。再者,擴散光透過率可為下述光學膜之厚度範圍內之擴散光透過率(Td)。In the optical film of the present invention, the diffuse light transmittance (Td) is preferably 0.35 or less, more preferably 0.30 or less, still more preferably 0.25 or less, and particularly preferably 0.20 or less. If the diffused light transmittance (Td) is equal to or less than the above upper limit, the ratio of diffused light becomes smaller, and the visibility in the wide-angle direction is easily improved. In addition, the lower limit of the diffuse light transmittance (Td) is usually 0.01 or more. Furthermore, the diffuse light transmittance may be the diffuse light transmittance (Td) within the thickness range of the following optical film.
於本發明之較佳實施態樣中,本發明之光學膜除廣角方向之優異之視認性以外,亦可具有優異之拉伸彈性模數。光學膜於80℃下之拉伸彈性模數較佳為4,000 MPa以上,更佳為4,500 MPa以上,尤佳為5,000 MPa以上,且較佳為9,000 MPa以下,更佳為8,500 MPa以下。若拉伸彈性模數為上述範圍內,則有光學膜不易產生凹陷缺陷並且容易表現出耐彎曲性之傾向。再者,光學膜之拉伸彈性模數可依據JIS K 7127使用拉伸試驗機進行測定,例如可藉由實施例所記載之方法進行測定。In a preferred embodiment of the present invention, the optical film of the present invention can also have an excellent tensile modulus in addition to excellent visibility in the wide-angle direction. The tensile elastic modulus of the optical film at 80° C. is preferably 4,000 MPa or more, more preferably 4,500 MPa or more, particularly preferably 5,000 MPa or more, and preferably 9,000 MPa or less, and more preferably 8,500 MPa or less. If the tensile modulus of elasticity is within the above range, the optical film tends to be less prone to dent defects and easily exhibit bending resistance. In addition, the tensile modulus of the optical film can be measured using a tensile tester in accordance with JIS K 7127, for example, it can be measured by the method described in the examples.
於本發明之較佳實施態樣中,本發明之光學膜之耐折性優異。於本發明之光學膜中,依據ASTM標準D2176-16之MIT耐折疲勞試驗中之耐折次數較佳為200,000次以上,更佳為300,000次以上,進而較佳為500,000次以上,尤佳為700,000次以上。若耐折次數為上述下限以上,則即便彎折亦不易產生龜裂或破裂等。再者,MIT耐折疲勞試驗可藉由例如實施例所記載之方法進行測定。In a preferred embodiment of the present invention, the optical film of the present invention has excellent folding resistance. In the optical film of the present invention, the number of folds in the MIT flex fatigue test according to ASTM standard D2176-16 is preferably 200,000 or more, more preferably 300,000 or more, further preferably 500,000 or more, and more preferably 700,000 times or more. If the number of times of bending resistance is more than the above-mentioned lower limit, cracks, cracks, etc. are less likely to occur even when bent. Furthermore, the MIT flexural fatigue test can be measured by, for example, the method described in the examples.
於本發明之較佳實施態樣中,本發明之光學膜之耐彎曲性優異。因此,即便重複彎曲,亦可維持光學特性。於本發明之光學膜中,依據JIS K 5600-5-1之耐彎曲性試驗前後之散射光比率之差之絕對值ΔTs(%)較佳為1.4%以下,更佳為1.2%以下,進而較佳為1.0%以下,進而更佳為0.5%以下,尤佳為0.1%以下,尤其更佳為0.05%以下,最佳為0.02%以下。若ΔTs為上述範圍,則於應用於可撓性顯示器等圖像顯示裝置之情形時,即便重複彎曲,亦容易維持廣角方向之優異之視認性。再者,耐彎曲性試驗可依據JIS K 5600-5-1,藉由彎曲試驗機進行測定,例如可藉由實施例所記載之方法進行測定。本說明書中,所謂光學特性,例如表示包含散射光比率、擴散光透過率、全光線透過率、黃度(YI)及霧度之可進行光學評估之特性,所謂「光學特性提高」,例如意指散射光比率變低、擴散光透過率變低、全光線透過率變高、黃度變低、或霧度變低等。In a preferred embodiment of the present invention, the optical film of the present invention has excellent bending resistance. Therefore, even if the bending is repeated, the optical characteristics can be maintained. In the optical film of the present invention, the absolute value ΔTs (%) of the difference in the scattered light ratio before and after the bending resistance test according to JIS K 5600-5-1 is preferably 1.4% or less, more preferably 1.2% or less, and further Preferably it is 1.0% or less, more preferably 0.5% or less, particularly preferably 0.1% or less, especially more preferably 0.05% or less, and most preferably 0.02% or less. If ΔTs is in the above range, when applied to an image display device such as a flexible display, it is easy to maintain excellent visibility in the wide-angle direction even if it is repeatedly bent. In addition, the bending resistance test can be measured by a bending tester in accordance with JIS K 5600-5-1, for example, it can be measured by the method described in the examples. In this specification, the so-called optical properties, for example, include scattered light ratio, diffuse light transmittance, total light transmittance, yellowness (YI), and haze that can be optically evaluated. The so-called "improvement of optical properties" means, for example, It means that the ratio of scattered light becomes lower, the diffuse light transmittance becomes lower, the total light transmittance becomes higher, the yellowness becomes lower, or the haze becomes lower.
於本發明之一實施態樣中,本發明之光學膜之霧度較佳為1.0%以下,更佳為0.5%以下,進而較佳為0.4%以下,尤佳為0.3%以下,最佳為0.2%以下。若光學膜之霧度為上述上限以下,則透明性變得良好,例如於應用於圖像顯示裝置之情形時容易表現出優異之視認性。又,霧度之下限通常為0.01%以上。再者,霧度可依據JIS K 7136:2000使用霧度電腦進行測定。In one embodiment of the present invention, the haze of the optical film of the present invention is preferably 1.0% or less, more preferably 0.5% or less, further preferably 0.4% or less, particularly preferably 0.3% or less, and most preferably Below 0.2%. If the haze of the optical film is less than or equal to the above upper limit, the transparency becomes good, and for example, when applied to an image display device, it is easy to exhibit excellent visibility. In addition, the lower limit of the haze is usually 0.01% or more. Furthermore, the haze can be measured using a haze computer in accordance with JIS K 7136:2000.
本發明之光學膜之黃度(YI)較佳為4.0以下,更佳為3.0以下,進而較佳為2.5以下,尤佳為2.0以下。若光學膜之黃度為上述上限以下,則透明性變得良好,例如於應用於圖像顯示裝置之情形時,容易表現出優異之視認性。又,黃度通常為-5以上,較佳為-2以上。再者,黃度(YI)可依據JIS K 7373:2006,使用紫外可見近紅外分光光度計進行對於300~800 nm之光之透過率測定,求出三刺激值(X、Y、Z),基於YI=100×(1.2769X-1.0592Z)/Y之式而算出。The yellowness (YI) of the optical film of the present invention is preferably 4.0 or less, more preferably 3.0 or less, still more preferably 2.5 or less, and particularly preferably 2.0 or less. If the yellowness of the optical film is less than the above upper limit, the transparency becomes good. For example, when it is applied to an image display device, it is easy to exhibit excellent visibility. In addition, the yellowness is usually -5 or higher, preferably -2 or higher. Furthermore, the yellowness (YI) can be measured in accordance with JIS K 7373: 2006, using an ultraviolet-visible-near-infrared spectrophotometer to measure the transmittance of light from 300 to 800 nm to obtain the tristimulus values (X, Y, Z), It is calculated based on the equation of YI=100×(1.2769X-1.0592Z)/Y.
本發明之光學膜之厚度係根據用途適當調整,較佳為10 μm以上,更佳為20 μm以上,進而較佳為25 μm以上,尤佳為30 μm以上,且較佳為150 μm以下,更佳為100 μm以下,進而較佳為85 μm以下。若光學膜之厚度為上述範圍,則就耐彎曲性及視認性之觀點而言有利。光學膜之厚度可利用膜厚計等進行測定,例如可藉由實施例所記載之方法進行測定。The thickness of the optical film of the present invention is appropriately adjusted according to the application, and is preferably 10 μm or more, more preferably 20 μm or more, still more preferably 25 μm or more, particularly preferably 30 μm or more, and preferably 150 μm or less, It is more preferably 100 μm or less, and still more preferably 85 μm or less. If the thickness of the optical film is in the above range, it is advantageous from the viewpoint of bending resistance and visibility. The thickness of an optical film can be measured with a film thickness meter etc., for example, it can measure by the method described in an Example.
<樹脂> 本發明之光學膜包含選自由聚醯亞胺系樹脂及聚醯胺系樹脂所組成之群中之至少1種樹脂。所謂聚醯亞胺系樹脂,表示選自由含有包含醯亞胺基之重複結構單元之樹脂(以下,有時稱為聚醯亞胺樹脂)、以及含有包含醯亞胺基及醯胺基兩者之重複結構單元之樹脂(以下,有時稱為聚醯胺醯亞胺樹脂)所組成之群中之至少1種樹脂。又,所謂聚醯胺系樹脂,表示含有包含醯胺基之重複結構單元之樹脂。<Resin> The optical film of the present invention includes at least one resin selected from the group consisting of polyimide resins and polyimide resins. The so-called polyimide-based resin refers to a resin selected from the group consisting of a repeating structural unit containing an imine group (hereinafter, sometimes referred to as polyimide resin), and a resin containing both an imide group and an amido group At least one type of resin in the group consisting of the resin of the repeating structural unit (hereinafter, sometimes referred to as polyimide resin). In addition, the term "polyamide-based resin" means a resin containing a repeating structural unit containing an amide group.
聚醯亞胺系樹脂較佳為具有式(10)所表示之重複結構單元。此處,G為4價有機基,A為2價有機基。聚醯亞胺系樹脂可包含G及/或A不同之2種以上之式(10)所表示之重複結構單元。 [化1] The polyimide resin preferably has a repeating structural unit represented by formula (10). Here, G is a tetravalent organic group, and A is a divalent organic group. The polyimide-based resin may include two or more repeating structural units represented by formula (10) different in G and/or A. [Chem 1]
聚醯亞胺系樹脂可於無損光學膜之各種物性之範圍內包含選自由式(11)、式(12)及式(13)所表示之重複結構單元所組成之群中之1種以上之重複結構單元。Polyimide-based resins can include at least one selected from the group consisting of repeating structural units represented by formula (11), formula (12) and formula (13) within the range of various physical properties of the non-destructive optical film. Repeating structural units.
[化2] [Chem 2]
式(10)及式(11)中,G及G1 分別獨立為4價有機基,較佳為可經烴基或經氟取代之烴基取代之有機基。作為G及G1 ,可例示式(20)、式(21)、式(22)、式(23)、式(24)、式(25)、式(26)、式(27)、式(28)或式(29)所表示之基以及4價之碳數6以下之鏈式烴基。就容易抑制光學膜之黃度(YI值)之方面而言,其中較佳為式(20)、式(21)、式(22)、式(23)、式(24)、式(25)、式(26)或式(27)所表示之基。In formula (10) and formula (11), G and G 1 are each independently a tetravalent organic group, preferably an organic group that can be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. As G and G 1 , formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), formula ( 28) or a group represented by formula (29) and a tetravalent chain hydrocarbon group with 6 or less carbon atoms. In terms of easily suppressing the yellowness (YI value) of the optical film, the formula (20), formula (21), formula (22), formula (23), formula (24), and formula (25) are preferred among them , Formula (26) or Formula (27).
[化3] [Chemical 3]
式(20)~式(29)中, ﹡表示鍵結鍵, Z表示單鍵、-O-、-CH2 -、-CH2 -CH2 -、-CH(CH3 )-、-C(CH3 )2 -、-C(CF3 )2 -、-Ar-、-SO2 -、-CO-、-O-Ar-O-、-Ar-O-Ar-、-Ar-CH2 -Ar-、-Ar-C(CH3 )2 -Ar-或-Ar-SO2 -Ar-。Ar表示可經氟原子取代之碳數6~20之伸芳基,作為具體例,可列舉伸苯基。In formulas (20) to (29), * represents a bonding bond, Z represents a single bond, -O-, -CH 2 -, -CH 2 -CH 2 -, -CH(CH 3 )-, -C( CH 3 ) 2 -, -C(CF 3 ) 2 -, -Ar-, -SO 2 -, -CO-, -O-Ar-O-, -Ar-O-Ar-, -Ar-CH 2- Ar-, -Ar-C(CH 3 ) 2 -Ar- or -Ar-SO 2 -Ar-. Ar represents an arylene group having 6 to 20 carbon atoms which may be substituted by a fluorine atom, and a specific example includes a phenylene group.
式(12)中,G2 為3價有機基,較佳為可經烴基或經氟取代之烴基取代之有機基。作為G2 ,可例示式(20)、式(21)、式(22)、式(23)、式(24)、式(25)、式(26)、式(27)、式(28)或式(29)所表示之基之鍵結鍵之任一個被取代為氫原子之基以及3價之碳數6以下之鏈式烴基。In the formula (12), G 2 is a trivalent organic group, preferably an organic group that can be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. As G 2 , formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), and formula (28) can be exemplified Or any one of the bonding bonds of the group represented by formula (29) is substituted with a hydrogen atom group and a trivalent chain hydrocarbon group with 6 or less carbon atoms.
式(13)中,G3 為2價有機基,較佳為可經烴基或經氟取代之烴基取代之有機基。作為G3 ,可例示式(20)、式(21)、式(22)、式(23)、式(24)、式(25)、式(26)、式(27)、式(28)或式(29)所表示之基之鍵結鍵中不鄰接之2個被取代為氫原子之基及碳數6以下之鏈式烴基。In the formula (13), G 3 is a divalent organic group, preferably an organic group that can be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. As G 3 , formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), and formula (28) can be exemplified Or two non-adjacent bonding bonds of the group represented by the formula (29) are substituted with hydrogen atoms and a chain hydrocarbon group with 6 or less carbon atoms.
式(10)~式(13)中,A、A1 、A2 及A3 分別獨立為2價有機基,較佳為可經烴基或經氟取代之烴基取代之有機基。作為A、A1 、A2 及A3 ,可例示:式(30)、式(31)、式(32)、式(33)、式(34)、式(35)、式(36)、式(37)或式(38)所表示之基;其等經甲基、氟基、氯基或三氟甲基取代之基;以及碳數6以下之鏈式烴基。In formulas (10) to (13), A, A 1 , A 2 and A 3 are each independently a divalent organic group, preferably an organic group that can be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. Examples of A, A 1 , A 2 and A 3 include : formula (30), formula (31), formula (32), formula (33), formula (34), formula (35), formula (36), A group represented by formula (37) or formula (38); a group substituted with a methyl group, a fluoro group, a chloro group, or a trifluoromethyl group; and a chain hydrocarbon group having 6 or less carbon atoms.
[化4] [Chem 4]
式(30)~式(38)中, ﹡表示鍵結鍵, Z1 、Z2 及Z3 分別獨立地表示單鍵、-O-、-CH2 -、-CH2 -CH2 -、-CH(CH3 )-、-C(CH3 )2 -、-C(CF3 )2 -、-SO2 -或-CO-。 一例為Z1 及Z3 為-O-,且Z2 為-CH2 -、-C(CH3 )2 -、-C(CF3 )2 -或-SO2 -。Z1 與Z2 對各環之鍵結位置、及Z2 與Z3 對各環之鍵結位置較佳為分別相對於各環為間位或對位。In formulas (30) to (38), * represents a bonding bond, Z 1 , Z 2 and Z 3 each independently represent a single bond, -O-, -CH 2 -, -CH 2 -CH 2 -,- CH(CH 3 )-, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -SO 2 -or -CO-. An example is that Z 1 and Z 3 are -O-, and Z 2 is -CH 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -or -SO 2 -. The bonding position of Z 1 and Z 2 to each ring, and the bonding position of Z 2 and Z 3 to each ring are preferably meta or para with respect to each ring.
聚醯亞胺系樹脂就容易提高視認性之觀點而言,較佳為至少具有式(10)所表示之重複結構單元及式(13)所表示之重複結構單元之聚醯胺醯亞胺樹脂。又,聚醯胺系樹脂較佳為至少具有式(13)所表示之重複結構單元。The polyimide-based resin is preferably a polyimide resin having at least a repeating structural unit represented by formula (10) and a repeating structural unit represented by formula (13) from the viewpoint of easily improving visibility . In addition, the polyamide resin preferably has at least a repeating structural unit represented by formula (13).
於本發明之一實施態樣中,聚醯亞胺系樹脂係使二胺及四羧酸化合物(醯氯化合物、四羧酸二酐等四羧酸化合物相關物)、以及視需要之二羧酸化合物(醯氯化合物等二羧酸化合物相關物)、三羧酸化合物(醯氯化合物、三羧酸酐等三羧酸化合物相關物)等進行反應(縮聚)而獲得之縮合型高分子。式(10)或式(11)所表示之重複結構單元通常自二胺及四羧酸化合物衍生。式(12)所表示之重複結構單元通常自二胺及三羧酸化合物衍生。式(13)所表示之重複結構單元通常自二胺及二羧酸化合物衍生。In one embodiment of the present invention, the polyimide-based resin is made of diamine and tetracarboxylic acid compounds (tetracarboxylic acid compound related products such as chlorine compounds and tetracarboxylic dianhydrides), and optionally dicarboxylic acid compounds Condensation-type polymers obtained by the reaction (condensation) of acid compounds (dicarboxylic acid compound related products such as chlorinated compounds), tricarboxylic acid compounds (tricarboxylic acid compound related products such as chlorinated chloride compounds and tricarboxylic anhydrides), etc. The repeating structural unit represented by formula (10) or formula (11) is usually derived from a diamine and a tetracarboxylic acid compound. The repeating structural unit represented by formula (12) is usually derived from diamine and tricarboxylic acid compounds. The repeating structural unit represented by the formula (13) is usually derived from a diamine and a dicarboxylic acid compound.
於本發明之一實施態樣中,聚醯胺系樹脂係使二胺與二羧酸化合物進行反應(縮聚)而獲得之縮合型高分子。即,式(13)所表示之重複結構單元通常自二胺及二羧酸化合物衍生。In one embodiment of the present invention, the polyamide resin is a condensation polymer obtained by reacting (condensation) a diamine and a dicarboxylic acid compound. That is, the repeating structural unit represented by formula (13) is usually derived from a diamine and a dicarboxylic acid compound.
作為四羧酸化合物,可列舉:芳香族四羧酸二酐等芳香族四羧酸化合物;及脂肪族四羧酸二酐等脂肪族四羧酸化合物。四羧酸化合物可單獨使用,亦可併用2種以上。四羧酸化合物除二酐以外,亦可為醯氯化合物等四羧酸化合物相關物。Examples of the tetracarboxylic acid compound include aromatic tetracarboxylic acid compounds such as aromatic tetracarboxylic dianhydride; and aliphatic tetracarboxylic acid compounds such as aliphatic tetracarboxylic dianhydride. The tetracarboxylic acid compound may be used alone or in combination of two or more kinds. In addition to the dianhydride, the tetracarboxylic acid compound may also be a tetracarboxylic acid compound related product such as a chlorine compound.
作為芳香族四羧酸二酐之具體例,可列舉:4,4'-氧二鄰苯二甲酸二酐、3,3',4,4'-二苯甲酮四羧酸二酐、2,2',3,3'-二苯甲酮四羧酸二酐、3,3',4,4'-聯苯四羧酸二酐、2,2',3,3'-聯苯四羧酸二酐、3,3',4,4'-二苯基碸四羧酸二酐、2,2-雙(3,4-二羧基苯基)丙烷二酐、2,2-雙(2,3-二羧基苯基)丙烷二酐、2,2-雙(3,4-二羧基苯氧基苯基)丙烷二酐、4,4'-(六氟亞異丙基)二鄰苯二甲酸二酐(6FDA)、1,2-雙(2,3-二羧基苯基)乙烷二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、1,2-雙(3,4-二羧基苯基)乙烷二酐、1,1-雙(3,4-二羧基苯基)乙烷二酐、雙(3,4-二羧基苯基)甲烷二酐、雙(2,3-二羧基苯基)甲烷二酐及4,4'-(對苯二氧基)二鄰苯二甲酸二酐及4,4'-(間苯二氧基)二鄰苯二甲酸二酐。該等可單獨使用或組合2種以上使用。Specific examples of aromatic tetracarboxylic dianhydrides include: 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2 ,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride Carboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis( 2,3-Dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenoxyphenyl)propane dianhydride, 4,4'-(hexafluoroisopropylidene) dio Phthalic acid dianhydride (6FDA), 1,2-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1 ,2-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl) Methane dianhydride, bis(2,3-dicarboxyphenyl) methane dianhydride and 4,4'-(terephthalic acid) diphthalic anhydride and 4,4'-(isophthalic acid) ) Diphthalic dianhydride. These can be used individually or in combination of 2 or more types.
作為脂肪族四羧酸二酐,可列舉環式或非環式之脂肪族四羧酸二酐。所謂環式脂肪族四羧酸二酐為具有脂環式烴結構之四羧酸二酐,作為其具體例,可列舉:1,2,4,5-環己烷四羧酸二酐、1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐等環烷烴四羧酸二酐、二環[2.2.2]-7-辛烯-2,3,5,6-四羧酸二酐、二環己基-3,3',4,4'-四羧酸二酐及該等之位置異構物。該等可單獨使用或組合2種以上使用。作為非環式脂肪族四羧酸二酐之具體例,可列舉1,2,3,4-丁烷四羧酸二酐、1,2,3,4-戊烷四羧酸二酐等,該等可單獨使用或組合2種以上使用。又,亦可組合環式脂肪族四羧酸二酐及非環式脂肪族四羧酸二酐使用。Examples of the aliphatic tetracarboxylic dianhydride include cyclic or acyclic aliphatic tetracarboxylic dianhydrides. The so-called cyclic aliphatic tetracarboxylic dianhydride is a tetracarboxylic dianhydride having an alicyclic hydrocarbon structure. Specific examples include: 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 1 , 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride and other cycloalkane tetracarboxylic dianhydrides, bicyclic [2.2.2]-7 -Octene-2,3,5,6-tetracarboxylic dianhydride, dicyclohexyl-3,3',4,4'-tetracarboxylic dianhydride and their positional isomers. These can be used individually or in combination of 2 or more types. Specific examples of acyclic aliphatic tetracarboxylic dianhydride include 1,2,3,4-butane tetracarboxylic dianhydride, 1,2,3,4-pentane tetracarboxylic dianhydride, etc. These can be used individually or in combination of 2 or more types. Moreover, it is also possible to use a combination of cyclic aliphatic tetracarboxylic dianhydride and acyclic aliphatic tetracarboxylic dianhydride.
於上述四羧酸二酐中,就容易提高視認性、彈性模數及耐彎曲性且容易降低著色性之觀點而言,較佳為1,2,4,5-環己烷四羧酸二酐、二環[2.2.2]-7-辛烯-2,3,5,6-四羧酸二酐及4,4'-(六氟亞異丙基)二鄰苯二甲酸二酐、以及該等之混合物。又,作為四羧酸,亦可使用上述四羧酸化合物之酐之水加成物。Among the above-mentioned tetracarboxylic dianhydrides, 1,2,4,5-cyclohexanetetracarboxylic dianhydride is preferred from the viewpoint of easy improvement in visibility, elastic modulus, and bending resistance, and easy reduction in colorability. Anhydride, bicyclo[2.2.2]-7-octene-2,3,5,6-tetracarboxylic dianhydride and 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride, And mixtures of these. Moreover, as the tetracarboxylic acid, the water adduct of the anhydride of the above-mentioned tetracarboxylic acid compound can also be used.
作為三羧酸化合物,可列舉芳香族三羧酸、脂肪族三羧酸及其等之相關之醯氯化合物、酸酐等,亦可併用2種以上。 作為具體例,可列舉:1,2,4-苯三羧酸之酐;2,3,6-萘三羧酸-2,3-酐;苯二甲酸酐與苯甲酸以單鍵、-CH2 -、-C(CH3 )2 -、-C(CF3 )2 -、-SO2 -或伸苯基連結而成之化合物。Examples of the tricarboxylic acid compound include aromatic tricarboxylic acids, aliphatic tricarboxylic acids, and related chlorinated compounds, acid anhydrides, and the like, and two or more of them may be used in combination. Specific examples include: 1,2,4-benzenetricarboxylic acid anhydride; 2,3,6-naphthalenetricarboxylic acid-2,3-anhydride; phthalic anhydride and benzoic acid have a single bond, -CH 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -SO 2 -or phenylene-linked compound.
作為二羧酸化合物,可列舉芳香族二羧酸、脂肪族二羧酸及其等之相關之醯氯化合物、酸酐等,亦可將其等併用2種以上。作為其等之具體例,可列舉:對苯二甲醯氯(Terephthaloyl Chloride(TPC));間苯二甲醯氯;萘二甲醯氯;4,4'-聯苯二甲醯氯;3,3'-聯苯二甲醯氯;4,4'-氧基雙(苯甲醯氯)(OBBC);碳數8以下之鏈式烴之二羧酸化合物及2個苯甲酸以單鍵、-CH2 -、-C(CH3 )2 -、-C(CF3 )2 -、-SO2 -或伸苯基連結而成之化合物。若使用該等二羧酸化合物,則就容易提高視認性、彈性模數及耐彎曲性且容易降低著色性之觀點而言較佳。Examples of the dicarboxylic acid compound include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and related chlorinated compounds, acid anhydrides, and the like, and two or more of them may be used in combination. Specific examples thereof include: Terephthaloyl Chloride (TPC); Meta-phthaloyl Chloride; Naphthalene Dimethyl Chloride; 4,4'-Biphenyl Dimethyl Chloride; 3 ,3'-Biphenyl Dimethyl Chloride; 4,4'-Oxybis(Benzyl Chloride) (OBBC); Dicarboxylic acid compound of chain hydrocarbon with carbon number less than 8 and 2 benzoic acid with single bond , -CH 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -SO 2 -or phenylene linking compound. If these dicarboxylic acid compounds are used, it is preferable from the viewpoint that visibility, elastic modulus, and bending resistance are easily improved, and colorability is easily reduced.
作為二胺,例如可列舉脂肪族二胺、芳香族二胺或該等之混合物。再者,於本實施形態中,所謂「芳香族二胺」表示胺基直接鍵結於芳香環之二胺,可於其結構之一部分包含脂肪族基或其他取代基。芳香環可為單環亦可為縮合環,可例示苯環、萘環、蒽環及茀環等,但並不限定於該等。於該等中,芳香環較佳為苯環。又,所謂「脂肪族二胺」表示胺基直接鍵結於脂肪族基之二胺,可於其結構之一部分包含芳香環或其他取代基。Examples of diamines include aliphatic diamines, aromatic diamines, or mixtures of these. Furthermore, in this embodiment, the so-called "aromatic diamine" means a diamine in which an amine group is directly bonded to an aromatic ring, and a part of its structure may include an aliphatic group or other substituents. The aromatic ring may be a monocyclic ring or a condensed ring, and a benzene ring, a naphthalene ring, an anthracene ring, and a sulphur ring may be exemplified, but it is not limited to these. Among them, the aromatic ring is preferably a benzene ring. In addition, the term "aliphatic diamine" refers to a diamine in which an amine group is directly bonded to an aliphatic group, and an aromatic ring or other substituents may be included in a part of the structure.
作為脂肪族二胺,例如可列舉:己二胺等非環式脂肪族二胺及1,3-雙(胺基甲基)環己烷、1,4-雙(胺基甲基)環己烷、降𦯉烷二胺、4,4'-二胺基二環己基甲烷等環式脂肪族二胺等。該等可單獨使用或組合2種以上使用。As aliphatic diamines, for example, acyclic aliphatic diamines such as hexamethylene diamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, etc. Cycloaliphatic diamines such as alkanes, noralkanediamines, 4,4'-diaminodicyclohexylmethane, etc. These can be used individually or in combination of 2 or more types.
作為芳香族二胺,例如可列舉:對苯二胺、間苯二胺、2,4-甲苯二胺、間苯二甲胺、對苯二甲胺、1,5-二胺基萘、2,6-二胺基萘等具有1個芳香環之芳香族二胺;4,4'-二胺基二苯基甲烷、4,4'-二胺基二苯基丙烷、4,4'-二胺基二苯醚、3,4'-二胺基二苯醚、3,3'-二胺基二苯醚、4,4'-二胺基二苯基碸、3,4'-二胺基二苯基碸、3,3'-二胺基二苯基碸、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、4,4'-二胺基二苯基碸、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]碸、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(3-胺基苯氧基)苯基]丙烷、2,2'-二甲基聯苯胺、2,2'-雙(三氟甲基)聯苯胺(2,2'-雙(三氟甲基)-4,4'-二胺基聯苯(TFMB))、4,4'-雙(4-胺基苯氧基)聯苯、9,9-雙(4-胺基苯基)茀、9,9-雙(4-胺基-3-甲基苯基)茀、9,9-雙(4-胺基-3-氯苯基)茀、9,9-雙(4-胺基-3-氟苯基)茀等具有2個以上芳香環之芳香族二胺。該等可單獨使用或組合2種以上使用。Examples of aromatic diamines include p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, m-xylylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene, 2 ,6-Diaminonaphthalene and other aromatic diamines with one aromatic ring; 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'- Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-di Amino diphenyl benzene, 3,3'-diamino diphenyl benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy) Benzene, 4,4'-diaminodiphenyl ash, bis[4-(4-aminophenoxy)phenyl] ash, bis[4-(3-aminophenoxy)phenyl] ash , 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2'- Dimethylbenzidine, 2,2'-bis(trifluoromethyl)benzidine (2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB)), 4 ,4'-bis(4-aminophenoxy)biphenyl, 9,9-bis(4-aminophenyl)pyridium, 9,9-bis(4-amino-3-methylphenyl) Tungsten, 9,9-bis(4-amino-3-chlorophenyl) tungsten, 9,9-bis(4-amino-3-fluorophenyl) tungsten, etc. with more than 2 aromatic rings amine. These can be used individually or in combination of 2 or more types.
於上述二胺中,就容易提高視認性、彈性模數及耐彎曲性且容易降低著色性之觀點而言,較佳為使用選自由具有聯苯結構之芳香族二胺所組成之群中之1種以上。進而較佳為使用選自由2,2'-二甲基聯苯胺、2,2'-雙(三氟甲基)聯苯胺、4,4'-雙(4-胺基苯氧基)聯苯及4,4'-二胺基二苯醚所組成之群中之1種以上,進而更佳為使用2,2'-雙(三氟甲基)聯苯胺。Among the above-mentioned diamines, it is preferable to use one selected from the group consisting of aromatic diamines having a biphenyl structure from the viewpoint of easily improving visibility, elastic modulus, and bending resistance and easily reducing colorability. More than one kind. More preferably, it is selected from 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)benzidine, 4,4'-bis(4-aminophenoxy)biphenyl And at least one of the group consisting of 4,4'-diaminodiphenyl ether, and it is more preferable to use 2,2'-bis(trifluoromethyl)benzidine.
聚醯亞胺系樹脂係於藉由利用慣用方法、例如攪拌等方法將上述二胺、四羧酸化合物、三羧酸化合物、二羧酸化合物等各原料進行混合後,使所獲得之中間物於醯亞胺化觸媒及視需要之脫水劑之存在下醯亞胺化而獲得。聚醯胺系樹脂係藉由利用慣用方法、例如攪拌等方法將上述二胺、二羧酸化合物等各原料混合而獲得。The polyimide-based resin is obtained by mixing the above-mentioned diamine, tetracarboxylic acid compound, tricarboxylic acid compound, dicarboxylic acid compound and other raw materials by conventional methods, such as stirring, etc., to obtain an intermediate It is obtained by imidization in the presence of an imidization catalyst and optionally a dehydrating agent. The polyamide-based resin is obtained by mixing each raw material such as the diamine and the dicarboxylic acid compound by a conventional method, for example, a method such as stirring.
作為醯亞胺化步驟中所使用之醯亞胺化觸媒,並無特別限定,例如可列舉:三丙胺、二丁基丙胺、乙基二丁胺等脂肪族胺;N-乙基哌啶、N-丙基哌啶、N-丁基吡咯啶、N-丁基哌啶、及N-丙基六氫氮呯等脂環式胺(單環式);氮雜雙環[2.2.1]庚烷、氮雜雙環[3.2.1]辛烷、氮雜二環[2.2.2]辛烷、及氮雜二環[3.2.2]壬烷等脂環式胺(多環式);以及2-甲基吡啶、3-甲基吡啶、4-甲基吡啶、2-乙基吡啶、3-乙基吡啶、4-乙基吡啶、2,4-二甲基吡啶、2,4,6-三甲基吡啶、3,4-環戊烯并吡啶、5,6,7,8-四氫異喹啉、及異喹啉等芳香族胺。There are no particular limitations on the imidization catalyst used in the imidization step, and examples include aliphatic amines such as tripropylamine, dibutylpropylamine, and ethyldibutylamine; N-ethylpiperidine , N-propylpiperidine, N-butylpyrrolidine, N-butylpiperidine, and N-propyl hexahydroazepine and other alicyclic amines (monocyclic); azabicyclo[2.2.1] Alicyclic amines (polycyclic) such as heptane, azabicyclo[3.2.1]octane, azabicyclo[2.2.2]octane, and azabicyclo[3.2.2]nonane; and 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2,4-lutidine, 2,4,6 -Aromatic amines such as trimethylpyridine, 3,4-cyclopentenopyridine, 5,6,7,8-tetrahydroisoquinoline, and isoquinoline.
作為醯亞胺化步驟中使用之脫水劑,並無特別限定,例如可列舉:乙酸酐、丙酸酐、異丁酸酐、特戊酸酐、丁酸酐、異戊酸酐等。The dehydrating agent used in the imidization step is not particularly limited, and examples thereof include acetic anhydride, propionic anhydride, isobutyric anhydride, pivalic anhydride, butyric anhydride, and isovaleric anhydride.
於各原料之混合及醯亞胺化步驟中,反應溫度並無特別限定,例如為15~350℃,較佳為20~100℃。反應時間亦無特別限定,例如為10分鐘~10小時左右。視需要可於惰性環境或減壓之條件下進行反應。又,反應可於溶劑中進行,作為溶劑,例如可列舉作為用於製備清漆之溶劑所例示者。於反應後,對聚醯亞胺系樹脂或聚醯胺系樹脂進行精製。作為精製方法,例如可列舉:於反應液中加入不良溶劑,藉由再沈澱法使樹脂析出,再進行乾燥,取出沈澱物,視需要利用甲醇等溶劑將沈澱物洗淨並使其乾燥之方法等。再者,聚醯亞胺系樹脂之製造亦可參照例如日本專利特開2006-199945號公報或日本專利特開2008-163107號公報所記載之製造方法。又,聚醯亞胺系樹脂亦可使用市售品,作為其具體例,可列舉三菱瓦斯化學股份有限公司製造之Neopulim(註冊商標)、河村產業股份有限公司製造之KPI-MX300F等。In the steps of mixing the raw materials and the imidization, the reaction temperature is not particularly limited, and is, for example, 15 to 350°C, preferably 20 to 100°C. The reaction time is also not particularly limited, and is, for example, about 10 minutes to 10 hours. If necessary, the reaction can be carried out under an inert environment or under reduced pressure. In addition, the reaction can be carried out in a solvent, and examples of the solvent include those exemplified as a solvent for preparing a varnish. After the reaction, the polyimide resin or polyimide resin is refined. As a purification method, for example, a method of adding a poor solvent to the reaction solution, precipitating the resin by a reprecipitation method, drying, taking out the precipitate, and washing the precipitate with a solvent such as methanol and drying if necessary Wait. In addition, the production of the polyimide-based resin can also refer to, for example, the production method described in Japanese Patent Laid-Open No. 2006-199945 or Japanese Patent Laid-Open No. 2008-163107. In addition, a commercially available product may also be used for the polyimide-based resin, and specific examples thereof include Neopulim (registered trademark) manufactured by Mitsubishi Gas Chemical Co., Ltd., KPI-MX300F manufactured by Kawamura Sangyo Co., Ltd., and the like.
於本發明之一實施態樣中,於聚醯胺醯亞胺樹脂中,式(13)所表示之結構單元之含量相對於式(10)所表示之結構單元1莫耳,較佳為0.1莫耳以上,更佳為0.5莫耳以上,進而較佳為1.0莫耳以上,尤佳為1.5莫耳以上,且較佳為6.0莫耳以下,更佳為5.0莫耳以下,進而較佳為4.5莫耳以下。若式(13)所表示之結構單元之含量為上述範圍,則容易提高廣角方向之視認性、彈性模數及耐彎曲性。In one embodiment of the present invention, in the polyimide imine resin, the content of the structural unit represented by formula (13) relative to 1 mol of the structural unit represented by formula (10) is preferably 0.1 Mol or more, more preferably 0.5 mol or more, still more preferably 1.0 mol or more, particularly preferably 1.5 mol or more, and preferably 6.0 mol or less, more preferably 5.0 mol or less, and still more preferably Below 4.5 mol. If the content of the structural unit represented by the formula (13) is in the above range, the visibility in the wide-angle direction, the elastic modulus, and the bending resistance are easily improved.
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200,000以上,更佳為250,000以上,進而較佳為300,000以上,且較佳為600,000以下,更佳為550,000以下,進而較佳為500,000。若聚醯亞胺系樹脂或聚醯胺系樹脂之重量平均分子量為上述下限以上,則容易提高光學膜之彈性模數及耐彎曲性。又,若該重量平均分子量為上述上限以下,則容易降低清漆之黏度,並且容易提高光學膜之延伸性及加工性。再者,重量平均分子量可進行凝膠滲透層析法(GPC)測定,藉由標準聚苯乙烯換算而求出,可藉由例如實施例所記載之方法而算出。The weight average molecular weight of the polyimide resin or polyimide resin is preferably 200,000 or more, more preferably 250,000 or more, still more preferably 300,000 or more, preferably 600,000 or less, more preferably 550,000 or less, and more Best is 500,000. If the weight average molecular weight of the polyimide-based resin or the polyimide-based resin is more than the above lower limit, it is easy to improve the elastic modulus and the bending resistance of the optical film. In addition, if the weight average molecular weight is less than or equal to the above upper limit, the viscosity of the varnish is easily reduced, and the elongation and processability of the optical film are easily improved. In addition, the weight average molecular weight can be measured by gel permeation chromatography (GPC), can be obtained by standard polystyrene conversion, and can be calculated by, for example, the method described in the examples.
於本發明之較佳一實施形態中,本發明之光學膜中所含之聚醯亞胺系樹脂或聚醯胺系樹脂可包含例如可藉由上述含氟取代基等導入之氟原子等鹵素原子。於聚醯亞胺系樹脂或聚醯胺系樹脂包含鹵素原子之情形時,容易提高光學膜之彈性模數且降低黃度(YI值)。若光學膜之彈性模數較高,則容易抑制該膜之損傷及褶皺等之產生,又,若光學膜之黃度較低,則容易提高該膜之透明性及視認性。鹵素原子較佳為氟原子。作為用於使聚醯亞胺系樹脂或聚醯胺系樹脂中含有氟原子之較佳之含氟取代基,例如可列舉氟基及三氟甲基。In a preferred embodiment of the present invention, the polyimide-based resin or polyimide-based resin contained in the optical film of the present invention may include, for example, halogen such as fluorine atoms that can be introduced by the above-mentioned fluorine-containing substituents. atom. When the polyimide resin or the polyimide resin contains halogen atoms, it is easy to increase the elastic modulus of the optical film and reduce the yellowness (YI value). If the elastic modulus of the optical film is high, it is easy to suppress the occurrence of damage and wrinkles of the film, and if the yellowness of the optical film is low, it is easy to improve the transparency and visibility of the film. The halogen atom is preferably a fluorine atom. As a preferable fluorine-containing substituent for making a polyimide resin or polyimide resin contain a fluorine atom, a fluorine group and a trifluoromethyl group are mentioned, for example.
聚醯亞胺系樹脂或聚醯胺系樹脂中之鹵素原子之含量以聚醯亞胺系樹脂或聚醯胺系樹脂之質量為基準,較佳為1~40質量%,更佳為5~40質量%,進而較佳為5~30質量%。若鹵素原子之含量為上述下限以上,則進一步提高光學膜之彈性模數,降低吸水率,進一步降低黃度(YI值),容易進一步提高透明性及視認性。若鹵素原子之含量為上述上限以下,則變得容易合成。The content of the halogen atom in the polyimide resin or polyimide resin is based on the mass of the polyimide resin or polyimide resin, preferably 1-40% by mass, more preferably 5~ 40% by mass, more preferably 5 to 30% by mass. If the content of halogen atoms is more than the above lower limit, the elastic modulus of the optical film is further increased, the water absorption rate is reduced, the yellowness (YI value) is further reduced, and transparency and visibility are easily improved. If the content of halogen atoms is equal to or less than the above upper limit, synthesis becomes easy.
光學膜中之聚醯亞胺系樹脂之醯亞胺化率較佳為90%以上,更佳為95%以上,進而較佳為98%以上。就容易提高光學膜之平坦性及廣角方向之視認性之觀點而言,醯亞胺化率較佳為上述下限以上。又,醯亞胺化率之上限為100%以下。再者,醯亞胺化率可藉由IR(Infrared Radiation,紅外線)法、NMR(nuclear magnetic resonance,核磁共振)法等求出,例如可藉由實施例所記載之方法求出。The imidization rate of the polyimide resin in the optical film is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more. From the viewpoint of easy improvement of the flatness of the optical film and the visibility in the wide-angle direction, the imidization rate is preferably at least the above lower limit. In addition, the upper limit of the imidization rate is 100% or less. Furthermore, the imidization rate can be obtained by IR (Infrared Radiation) method, NMR (nuclear magnetic resonance) method, etc., for example, by the method described in the examples.
於本發明之一實施形態中,光學膜中之聚醯亞胺系樹脂及/或聚醯胺系樹脂之含量相對於光學膜之質量,較佳為40質量%以上,更佳為50質量%以上,進而較佳為70質量%以上,尤佳為80質量%以上,最佳為90質量%以上。聚醯亞胺系樹脂及/或聚醯胺系樹脂之含量為上述下限以上就廣角方向之視認性、彈性模數及耐彎曲性之觀點而言有利。再者,光學膜中之聚醯亞胺系樹脂及/或聚醯胺系樹脂之含量相對於光學膜之質量通常為100質量%以下。In one embodiment of the present invention, the content of the polyimide resin and/or polyimide resin in the optical film relative to the mass of the optical film is preferably 40% by mass or more, more preferably 50% by mass Above, it is more preferably 70% by mass or more, more preferably 80% by mass or more, and most preferably 90% by mass or more. The content of the polyimide-based resin and/or the polyimide-based resin is more than the above lower limit from the viewpoint of visibility in the wide-angle direction, elastic modulus, and bending resistance. Furthermore, the content of the polyimide resin and/or the polyimide resin in the optical film is usually 100% by mass or less with respect to the mass of the optical film.
作為光學膜中所含之樹脂,可使用2種以上之聚醯亞胺系樹脂或2種以上之聚醯胺系樹脂,亦可組合聚醯亞胺系樹脂與聚醯胺系樹脂使用。 為了獲得散射光比率較低之光學膜,較佳為於下述塗佈步驟中,將具有特定之固形物成分濃度及黏度之清漆塗佈於基材而形成均勻之塗膜。於本發明之一實施態樣中,較佳為使用2種以上之聚醯亞胺系樹脂或聚醯胺系樹脂、例如2種以上之聚醯亞胺系樹脂、2種以上之聚醯胺系樹脂、或1種以上之聚醯亞胺系樹脂與1種以上之聚醯胺系樹脂之組合等,尤其更佳為使用具有互不相同之重量平均分子量之2種以上之聚醯亞胺系樹脂或聚醯胺系樹脂。於下述塗佈步驟中,若使此種樹脂包含於清漆中,則可將清漆之固形物成分濃度及黏度容易地調整為特定範圍,因此可形成均勻之塗膜,容易將所獲得之光學膜調整為滿足式(1)。As the resin contained in the optical film, two or more types of polyimide-based resins or two or more types of polyimide-based resins may be used, or a combination of polyimide-based resins and polyimide-based resins may be used. In order to obtain an optical film with a low scattered light ratio, it is preferable to coat a varnish with a specific solid content concentration and viscosity on the substrate in the following coating step to form a uniform coating film. In an embodiment of the present invention, it is preferable to use two or more types of polyimide resins or polyamide resins, for example, two or more types of polyimide resins, and two or more types of polyamide resins. Type resin, or a combination of one or more polyimide-based resins and one or more polyimide-based resins, etc. It is especially preferable to use two or more polyimides with different weight average molecular weights Series resin or polyamide resin. In the following coating steps, if this resin is included in the varnish, the solid content and viscosity of the varnish can be easily adjusted to a specific range, so a uniform coating film can be formed, and the obtained optical The film is adjusted to satisfy equation (1).
於本發明之較佳實施態樣中係具有互不相同之重量平均分子量之2種以上之聚醯亞胺系樹脂或聚醯胺系樹脂,且至少1種聚醯亞胺系樹脂或聚醯胺系樹脂之重量平均分子量為250,000~500,000,至少1種聚醯亞胺系樹脂或聚醯胺系樹脂之重量平均分子量為200,000~450,000。又,於本發明之更佳實施態樣中係具有互不相同之重量平均分子量之2種聚醯亞胺系樹脂或聚醯胺系樹脂,且一聚醯亞胺系樹脂或聚醯胺系樹脂之重量平均分子量為250,000~500,000,另一聚醯亞胺系樹脂或聚醯胺系樹脂之重量平均分子量為200,000~450,000。於下述塗佈步驟中,若使此種樹脂包含於清漆中,則可將清漆之固形物成分濃度及黏度容易地調整為特定範圍,因此可形成均勻之塗膜,容易將所獲得之光學膜調整為滿足式(1)。 又,一聚醯亞胺系樹脂或聚醯胺系樹脂與另一聚醯亞胺系樹脂或聚醯胺系樹脂之質量比率(前者/後者)可根據樹脂之種類或所需之清漆之固形物成分濃度及黏度等而適當選擇,例如可為5/95~95/5。In a preferred embodiment of the present invention, two or more polyimide resins or polyimide resins having mutually different weight average molecular weights, and at least one polyimide resin or polyimide resin The weight average molecular weight of the amine resin is 250,000 to 500,000, and the weight average molecular weight of at least one polyimide resin or polyamide resin is 200,000 to 450,000. Furthermore, in a more preferable embodiment of the present invention, there are two kinds of polyimide resins or polyamide resins having mutually different weight average molecular weights, and one polyimide resin or polyamide resin The weight average molecular weight of the resin is 250,000 to 500,000, and the weight average molecular weight of another polyimide resin or polyamide resin is 200,000 to 450,000. In the following coating steps, if this resin is included in the varnish, the solid content and viscosity of the varnish can be easily adjusted to a specific range, so a uniform coating film can be formed, and the obtained optical The film is adjusted to satisfy equation (1). In addition, the mass ratio of a polyimide resin or polyimide resin to another polyimide resin or polyimide resin (the former/the latter) can be based on the type of resin or the solid state of the varnish required The concentration and viscosity of the substance components are appropriately selected, for example, 5/95 to 95/5.
<添加劑> 本發明之光學膜可進而包含紫外線吸收劑。例如可列舉三𠯤系紫外線吸收劑、二苯甲酮系紫外線吸收劑、苯并三唑系紫外線吸收劑、苯甲酸酯系紫外線吸收劑、及氰基丙烯酸酯系紫外線吸收劑等。該等可單獨使用,亦可併用2種以上。作為較佳之市售之紫外線吸收劑,例如可列舉:Sumika Chemtex股份有限公司製造之Sumisorb(註冊商標)340、ADEKA股份有限公司製造之Adekastab(註冊商標)LA-31、及BASF Japan股份有限公司製造之TINUVIN(註冊商標)1577等。若含有紫外線吸收劑,則可抑制光學膜中之樹脂之劣化,因此容易提高光學膜之光學特性。紫外線吸收劑之含量相對於本發明之光學膜之質量,較佳為1~10質量%,更佳為3~6質量%。若紫外線吸收劑之含量為上述範圍,則容易進一步提高光學膜之光學特性。<Additives> The optical film of the present invention may further contain an ultraviolet absorber. For example, three-type ultraviolet absorbers, benzophenone-type ultraviolet absorbers, benzotriazole-type ultraviolet absorbers, benzoate-type ultraviolet absorbers, cyanoacrylate-type ultraviolet absorbers, and the like can be cited. These can be used individually or in combination of 2 or more types. As a preferable commercially available ultraviolet absorber, for example, Sumisorb (registered trademark) 340 manufactured by Sumika Chemtex Co., Ltd., Adekastab (registered trademark) LA-31 manufactured by ADEKA Co., Ltd., and BASF Japan Co., Ltd. The TINUVIN (registered trademark) 1577 and so on. If the ultraviolet absorber is contained, the deterioration of the resin in the optical film can be suppressed, so it is easy to improve the optical properties of the optical film. The content of the ultraviolet absorber is preferably 1-10% by mass, more preferably 3-6% by mass relative to the mass of the optical film of the present invention. If the content of the ultraviolet absorber is in the above range, it is easy to further improve the optical properties of the optical film.
本發明之光學膜可進而包含紫外線吸收劑以外之其他添加劑。作為此種其他添加劑,例如可列舉填料、增白劑、抗氧化劑、pH值調整劑及調平劑等。但,本發明之光學膜較佳為實質上不含填料(例如二氧化矽粒子)。具體而言,填料之含量相對於光學膜之質量,較佳為5質量%以下,更佳為3質量%以下,進而較佳為1質量%以下,尤佳為0.5質量%以下,最佳為0.1質量%以下。The optical film of the present invention may further contain other additives other than the ultraviolet absorber. Examples of such other additives include fillers, brighteners, antioxidants, pH adjusters, leveling agents, and the like. However, the optical film of the present invention is preferably substantially free of fillers (for example, silica particles). Specifically, the content of the filler relative to the mass of the optical film is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, particularly preferably 0.5% by mass or less, and most preferably 0.1% by mass or less.
本發明之光學膜之用途並無特別限定,可用於各種用途。本發明之光學膜可如上所述為單層,亦可為積層體,可直接使用本發明之光學膜,亦可進而以與其他膜之積層體之形式使用。再者,於光學膜為積層體之情形時,包含積層於光學膜之單面或兩面之所有層在內稱為光學膜。The use of the optical film of the present invention is not particularly limited, and can be used for various purposes. The optical film of the present invention may be a single layer as described above, or may be a laminate, and the optical film of the present invention may be used directly, or may be further used as a laminate with other films. In addition, when the optical film is a laminate, all layers including all layers laminated on one or both sides of the optical film are called optical films.
於本發明之光學膜為積層體之情形時,較佳為於光學膜之至少一面具有1個以上之功能層。作為功能層,例如可列舉紫外線吸收層、硬塗層、底塗層、阻氣層、黏著層、色相調整層、折射率調整層等。功能層可單獨使用或組合兩種以上使用。When the optical film of the present invention is a laminate, it is preferable to have one or more functional layers on at least one surface of the optical film. As the functional layer, for example, an ultraviolet absorbing layer, a hard coat layer, an undercoat layer, a gas barrier layer, an adhesion layer, a hue adjustment layer, a refractive index adjustment layer, etc. can be cited. The functional layer can be used alone or in combination of two or more.
紫外線吸收層係具有紫外線吸收功能之層,例如包括選自紫外線硬化型透明樹脂、電子束硬化型透明樹脂、及熱硬化型透明樹脂之主材、以及分散於該主材中之紫外線吸收劑。The ultraviolet absorbing layer is a layer having ultraviolet absorbing function, and includes, for example, a main material selected from ultraviolet curable transparent resin, electron beam curable transparent resin, and thermosetting transparent resin, and an ultraviolet absorber dispersed in the main material.
黏著層係具有黏著性功能之層,具有使光學膜接著於其他構件之功能。作為黏著層之形成材料,可使用通常已知者。例如可使用熱硬化性樹脂組合物或光硬化性樹脂組合物。於該情形時,可藉由事後供給能量而使熱硬化性樹脂組合物或光硬化性樹脂組合物高分子化且硬化。The adhesive layer is a layer with adhesive function, and has the function of bonding the optical film to other components. As the forming material of the adhesive layer, generally known ones can be used. For example, a thermosetting resin composition or a photocuring resin composition can be used. In this case, the thermosetting resin composition or the photocurable resin composition can be polymerized and cured by supplying energy afterwards.
黏著層可為稱為感壓型接著劑(Pressure Sensitive Adhesive,PSA)之藉由按壓而貼合於對象物之層。感壓型接著劑可為作為「於常溫下具有黏著性,以較輕之壓力便接著於被黏著材之物質」(JIS K 6800)之黏著劑,亦可為作為「將特定成分內置於保護覆膜(微膠囊),藉由適當之方法(壓力、熱等)在破壞覆膜之前可保持穩定性的接著劑」(JIS K 6800)的膠囊型接著劑。The adhesive layer may be a layer called Pressure Sensitive Adhesive (PSA) that adheres to an object by pressing. Pressure-sensitive adhesives can be used as "substances that have adhesiveness at room temperature and adhere to the material to be adhered with a lighter pressure" (JIS K 6800), and can also be used as an "incorporating specific ingredients into the protection The film (microcapsule) is a capsule-type adhesive agent that can maintain stability before breaking the film by an appropriate method (pressure, heat, etc.)" (JIS K 6800).
色相調整層係具有色相調整功能之層,且係可將光學積層體調整為目標之色相之層。色相調整層例如為含有樹脂及著色劑之層。作為該著色劑,例如可列舉:氧化鈦、氧化鋅、紅丹、氧鈦系煅燒顏料、群青、鋁酸鈷、及碳黑等無機顏料;偶氮系化合物、喹吖啶酮系化合物、蒽醌系化合物、苝系化合物、異吲哚啉酮系化合物、酞菁系化合物、喹酞酮系化合物、士林系化合物、及吡咯并吡咯二酮系化合物等有機顏料;硫酸鋇、及碳酸鈣等體質顏料;以及鹼性染料、酸性染料、及媒染染料等染料。The hue adjustment layer is a layer having a hue adjustment function, and is a layer that can adjust the optical laminate to the target hue. The hue adjusting layer is, for example, a layer containing resin and coloring agent. Examples of the colorant include inorganic pigments such as titanium oxide, zinc oxide, red lead, titanyl calcined pigments, ultramarine blue, cobalt aluminate, and carbon black; azo compounds, quinacridone compounds, anthracene Organic pigments such as quinone compounds, perylene compounds, isoindolinone compounds, phthalocyanine compounds, quinophthalone compounds, Shihlin compounds, and diketopyrrolopyrrole compounds; barium sulfate, and calcium carbonate Extender pigments; and dyes such as basic dyes, acid dyes, and mordant dyes.
折射率調整層係具有折射率調整功能之層,且係具有與例如單層光學膜不同之折射率且可對光學膜賦予規定之折射率之層。折射率調整層例如可為含有適當選擇之樹脂且視情形進而含有顏料之樹脂層,亦可為金屬薄膜。作為調整折射率之顏料,例如可列舉氧化矽、氧化鋁、氧化銻、氧化錫、氧化鈦、氧化鋯及氧化鉭。該顏料之平均一次粒徑可為0.1 μm以下。藉由將顏料之平均一次粒徑設為0.1 μm以下,可防止透過折射率調整層之光之亂反射,防止透明度之降低。作為用於折射率調整層之金屬,例如可列舉氧化鈦、氧化鉭、氧化鋯、氧化鋅、氧化錫、氧化矽、氧化銦、氮氧化鈦、氮化鈦、氮氧化矽、氮化矽等金屬氧化物或金屬氮化物。The refractive index adjustment layer is a layer having a refractive index adjustment function, and is a layer that has a refractive index different from, for example, a single-layer optical film and can give a predetermined refractive index to the optical film. The refractive index adjustment layer may be, for example, a resin layer containing appropriately selected resin and further containing a pigment as appropriate, or a metal thin film. Examples of pigments for adjusting the refractive index include silica, alumina, antimony oxide, tin oxide, titanium oxide, zirconium oxide, and tantalum oxide. The average primary particle size of the pigment may be 0.1 μm or less. By setting the average primary particle size of the pigment to 0.1 μm or less, the random reflection of the light passing through the refractive index adjustment layer can be prevented, and the decrease in transparency can be prevented. Examples of metals used for the refractive index adjustment layer include titanium oxide, tantalum oxide, zirconium oxide, zinc oxide, tin oxide, silicon oxide, indium oxide, titanium oxynitride, titanium nitride, silicon oxynitride, silicon nitride, etc. Metal oxide or metal nitride.
於本發明之較佳實施態樣中,光學膜於至少一面(單面或兩面)具有硬塗層。於在兩面具有硬塗層之情形時,2個硬塗層所包含之成分彼此可相同亦可不同。In a preferred embodiment of the present invention, the optical film has a hard coating on at least one side (single side or both sides). In the case of having hard coats on both sides, the components contained in the two hard coats may be the same or different from each other.
作為硬塗層,例如可列舉丙烯酸系、環氧系、胺基甲酸酯系、苄基氯系、乙烯基系等之公知硬塗層。於該等中,就抑制光學膜之廣角方向之視認性之降低且提高耐彎曲性之觀點而言,可較佳地使用丙烯酸系、胺基甲酸酯系、及其等之組合之硬塗層。硬塗層較佳為包含硬化性化合物之硬化性組合物之硬化物,且係藉由活性能量射線之照射,使該硬化性化合物聚合而形成。作為硬化性化合物,例如可列舉多官能(甲基)丙烯酸酯系化合物。所謂多官能(甲基)丙烯酸酯系化合物係指於分子中具有至少2個(甲基)丙烯醯基之化合物。Examples of the hard coat layer include known hard coat layers such as acrylic, epoxy, urethane, benzyl chloride, and vinyl. Among them, from the viewpoint of suppressing the decrease in the visibility of the optical film in the wide-angle direction and improving the bending resistance, a hard coat of acrylic, urethane, and combinations thereof can be preferably used Floor. The hard coat layer is preferably a cured product of a curable composition containing a curable compound, and is formed by polymerizing the curable compound by irradiation with active energy rays. As a curable compound, a polyfunctional (meth)acrylate type compound is mentioned, for example. The so-called polyfunctional (meth)acrylate compound refers to a compound having at least two (meth)acrylic groups in the molecule.
作為多官能(甲基)丙烯酸酯系化合物,例如為乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、四羥甲基甲烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、五甘油三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、異氰尿酸三((甲基)丙烯醯氧基乙基)酯;於磷腈化合物之磷腈環導入有(甲基)丙烯醯基之磷腈系(甲基)丙烯酸酯化合物;藉由分子中具有至少2個異氰酸基之多異氰酸酯與具有至少1個(甲基)丙烯醯基及羥基之多元醇化合物之反應所獲得之(甲基)丙烯酸胺基甲酸酯化合物;藉由分子中至少2個羧酸鹵化物與具有至少1個(甲基)丙烯醯基及羥基之多元醇化合物之反應所獲得之聚酯(甲基)丙烯酸酯化合物;以及上述各化合物之二聚物、三聚物等之類的低聚物等。該等化合物係分別單獨使用或混合2種以上使用。As the polyfunctional (meth)acrylate-based compound, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylic acid Ester, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate ) Acrylate, tetramethylolmethane tetra(meth)acrylate, pentaglycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate ) Acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, isocyanurate tri(( (Meth) acryloxyethyl) ester; a phosphazene-based (meth)acrylate compound with a (meth)acryloyl group introduced into the phosphazene ring of the phosphazene compound; by having at least 2 isoforms in the molecule A (meth)acrylate urethane compound obtained by the reaction of a polyisocyanate of a cyanate group and a polyol compound having at least one (meth)acrylic acid group and a hydroxyl group; by having at least two carboxylic acids in the molecule A polyester (meth)acrylate compound obtained by the reaction of a halide and a polyol compound having at least one (meth)acrylic acid group and a hydroxyl group; and the dimers, trimers, etc. of the above-mentioned compounds的oligomers and so on. These compounds are used individually or in mixture of two or more types.
於硬化性化合物中,除上述多官能(甲基)丙烯酸酯系化合物以外,可包含單官能(甲基)丙烯酸酯系化合物。作為單官能(甲基)丙烯酸酯系化合物,例如可列舉:(甲基)丙烯酸羥乙酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸羥丁酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、(甲基)丙烯酸縮水甘油酯等。該等化合物可單獨使用或混合2種以上使用。單官能(甲基)丙烯酸酯系化合物之含量於將硬化性組合物中所含之化合物之固形物成分設為100質量%時,較佳為10質量%以下。再者,於本說明書中,所謂固形物成分意指硬化性組合物中所含之除溶劑以外之所有成分。In addition to the above-mentioned polyfunctional (meth)acrylate-based compound, the curable compound may contain a monofunctional (meth)acrylate-based compound. As the monofunctional (meth)acrylate compound, for example, hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (methyl) ) Hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycidyl (meth)acrylate, etc. These compounds can be used alone or in mixture of two or more kinds. The content of the monofunctional (meth)acrylate compound is preferably 10% by mass or less when the solid content of the compound contained in the curable composition is 100% by mass. In addition, in this specification, the so-called solid content means all the components other than the solvent contained in the curable composition.
又,硬化性化合物亦可含有聚合性低聚物。藉由含有聚合性低聚物,可調整硬塗層之硬度。作為聚合性低聚物,可列舉:末端(甲基)丙烯酸酯聚甲基丙烯酸甲酯、末端苯乙烯聚(甲基)丙烯酸酯、末端(甲基)丙烯酸酯聚苯乙烯、末端(甲基)丙烯酸酯聚乙二醇、末端(甲基)丙烯酸酯丙烯腈-苯乙烯共聚物、末端(甲基)丙烯酸酯苯乙烯-(甲基)丙烯酸甲酯共聚物等巨單體。聚合性低聚物之含量於將硬化性組合物中所含之化合物之固形物成分設為100質量%時,較佳為5~50質量%。In addition, the curable compound may contain a polymerizable oligomer. By containing polymerizable oligomers, the hardness of the hard coat layer can be adjusted. Examples of polymerizable oligomers include: terminal (meth)acrylate polymethyl methacrylate, terminal styrene poly(meth)acrylate, terminal (meth)acrylate polystyrene, terminal (meth)acrylate ) Macromonomers such as acrylate polyethylene glycol, terminal (meth)acrylate acrylonitrile-styrene copolymer, terminal (meth)acrylate styrene-methyl (meth)acrylate copolymer. The content of the polymerizable oligomer is preferably 5 to 50% by mass when the solid content of the compound contained in the curable composition is 100% by mass.
形成硬塗層之硬化性組合物除多官能(甲基)丙烯酸酯系化合物及聚合性低聚物以外,亦可包含添加劑。作為添加劑,例如可列舉聚合起始劑、二氧化矽、調平劑、溶劑等。作為溶劑,例如可列舉甲基乙基酮、聚丙二醇單甲醚等。In addition to the polyfunctional (meth)acrylate compound and polymerizable oligomer, the curable composition forming the hard coat layer may also contain additives. Examples of additives include polymerization initiators, silica, leveling agents, and solvents. As a solvent, methyl ethyl ketone, polypropylene glycol monomethyl ether, etc. are mentioned, for example.
硬塗層之厚度就提高光學膜之硬度、耐彎曲性及視認性之觀點而言,較佳為3~30 μm,更佳為5~25 μm,進而較佳為5~20 μm。The thickness of the hard coat layer is preferably 3 to 30 μm, more preferably 5 to 25 μm, and still more preferably 5 to 20 μm from the viewpoint of improving the hardness, bending resistance, and visibility of the optical film.
於本發明之一實施態樣中,光學膜亦可於至少一面(單面或兩面)具有保護膜。例如於在光學膜之單面具有功能層之情形時,保護膜可積層於光學膜側之表面或功能層側之表面,亦可積層於光學膜側及功能層側這兩側。於在光學膜之兩面具有功能層之情形時,保護膜可積層於單側功能層側之表面,亦可積層於兩側功能層側之表面。保護膜係用以暫時保護光學膜或功能層之表面之膜,只要為可保護光學膜或功能層之表面且能夠剝離之膜,則並無特別限定。作為保護膜,例如可列舉:聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯等聚酯系樹脂膜;聚乙烯、聚丙烯膜等聚烯烴系樹脂膜、丙烯酸系樹脂膜等,較佳為選自由聚烯烴系樹脂膜、聚對苯二甲酸乙二酯系樹脂膜及丙烯酸系樹脂膜所組成之群。於光學膜具有2個保護膜之情形時,各保護膜可相同或不同。In an embodiment of the present invention, the optical film may also have a protective film on at least one side (single side or both sides). For example, when the optical film has a functional layer on one side, the protective film may be laminated on the surface on the optical film side or on the functional layer side, or on both the optical film side and the functional layer side. When there are functional layers on both sides of the optical film, the protective film can be laminated on the surface on the side of the functional layer on one side, or on the surface on the side of the functional layer on both sides. The protective film is a film for temporarily protecting the surface of the optical film or the functional layer, and it is not particularly limited as long as it can protect the surface of the optical film or the functional layer and can be peeled off. Examples of protective films include polyester resin films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin resin films such as polyethylene and polypropylene films. The resin film, acrylic resin film, etc. are preferably selected from the group consisting of polyolefin resin film, polyethylene terephthalate resin film, and acrylic resin film. When the optical film has two protective films, each protective film may be the same or different.
保護膜之厚度並無特別限定,通常為10~120 μm,較佳為15~110 μm,更佳為20~100 μm。於光學膜具有2個保護膜之情形時,各保護膜之厚度可相同亦可不同。The thickness of the protective film is not particularly limited, and is usually 10 to 120 μm, preferably 15 to 110 μm, and more preferably 20 to 100 μm. When the optical film has two protective films, the thickness of each protective film may be the same or different.
[光學膜之製造方法] 本發明之光學膜並無特別限定,例如可藉由包含以下步驟之方法而製造: (a)製備包含上述樹脂之液體(以下,有時記載為清漆)之步驟(清漆製備步驟); (b)將清漆塗佈於基材而形成塗膜之步驟(塗佈步驟);及 (c)使所塗佈之液體(塗膜)乾燥而形成光學膜之步驟(光學膜形成步驟)。[Method of manufacturing optical film] The optical film of the present invention is not particularly limited. For example, it can be manufactured by a method including the following steps: (a) A step of preparing a liquid containing the above resin (hereinafter, sometimes referred to as a varnish) (a varnish preparation step); (b) The step of applying varnish to the substrate to form a coating film (coating step); and (c) The step of drying the applied liquid (coating film) to form an optical film (optical film forming step).
於清漆製備步驟中,藉由將上述樹脂溶解於溶劑,且視需要添加上述紫外線吸收劑及上述其他添加劑並進行攪拌混合,而製備清漆。In the varnish preparation step, the varnish is prepared by dissolving the above-mentioned resin in a solvent, adding the above-mentioned ultraviolet absorber and the above-mentioned other additives as necessary, and stirring and mixing them to prepare a varnish.
用於製備清漆之溶劑只要能夠溶解上述樹脂,則無特別限定。作為該溶劑,例如可列舉:N,N-二甲基乙醯胺(DMAc)、N,N-二甲基甲醯胺等醯胺系溶劑;γ-丁內酯(GBL)、γ-戊內酯等內酯系溶劑;二甲基碸、二甲基亞碸、環丁碸等含硫系溶劑;碳酸乙二酯、碳酸丙二酯等碳酸酯系溶劑;及其等之組合(混合溶劑)。於該等中,較佳為醯胺系溶劑或內酯系溶劑。該等溶劑可單獨使用或組合兩種以上使用。又,清漆中可包含水、醇系溶劑、酮系溶劑、非環狀酯系溶劑、醚系溶劑等。清漆之固形物成分濃度較佳為1~25質量%,更佳為5~20質量%。The solvent used to prepare the varnish is not particularly limited as long as it can dissolve the above-mentioned resin. Examples of the solvent include: amide-based solvents such as N,N-dimethylacetamide (DMAc) and N,N-dimethylformamide; γ-butyrolactone (GBL), γ-pentyl Lactone-based solvents such as lactone; sulfur-containing solvents such as dimethyl sulfene, dimethyl sulfide, and cyclobutane; carbonate-based solvents such as ethylene carbonate and propylene carbonate; and combinations thereof (mixed Solvent). Among these, an amide-based solvent or a lactone-based solvent is preferable. These solvents can be used alone or in combination of two or more. In addition, the varnish may contain water, alcohol solvents, ketone solvents, acyclic ester solvents, ether solvents, and the like. The solid content concentration of the varnish is preferably 1 to 25% by mass, more preferably 5 to 20% by mass.
於塗佈步驟中,藉由公知之塗佈方法於基材上塗佈清漆而形成塗膜。作為公知之塗佈方法,例如可列舉:線棒塗佈法、反向塗佈、凹版塗佈等輥塗法、模嘴塗佈法、卡馬(comma)塗佈法、模唇塗佈法、旋轉塗佈法、網版塗佈法、噴注塗佈法、浸漬法、噴霧法、流涎成形法等。In the coating step, a varnish is coated on the substrate by a known coating method to form a coating film. As well-known coating methods, for example, roll coating methods such as wire bar coating, reverse coating, and gravure coating, die nozzle coating methods, comma coating methods, and die lip coating methods are mentioned. , Spin coating method, screen coating method, spray coating method, dipping method, spray method, casting method, etc.
作為基材之例,金屬系可列舉SUS(Steel Use Stainless,不鏽鋼)板,樹脂系可列舉PET(polyethylene terephthalate,聚對苯二甲酸乙二酯)膜、PEN(polyethylene naphthalate,聚萘二甲酸乙二酯)膜、其他聚醯亞胺系樹脂或聚醯胺系樹脂膜、環烯烴系聚合物(COP)膜、丙烯酸系膜等。其中,就平滑性、耐熱性優異之觀點而言,較佳為PET膜、COP膜等,進而就與光學膜之密接性及成本之觀點而言,更佳為PET膜。As an example of the base material, SUS (Steel Use Stainless, stainless steel) plate can be cited for metal, and PET (polyethylene terephthalate) film, PEN (polyethylene naphthalate, polyethylene naphthalate) for resin Diester) film, other polyimide resin or polyamide resin film, cycloolefin polymer (COP) film, acrylic film, etc. Among them, from the viewpoint of excellent smoothness and heat resistance, a PET film, a COP film, etc. are preferred, and further, from the viewpoint of adhesion to an optical film and cost, a PET film is more preferred.
於光學膜形成步驟中,對塗膜進行乾燥(稱為第1乾燥),自基材剝離後,對乾燥塗膜進一步進行乾燥(稱為第2乾燥或後烘烤處理),藉此形成光學膜。第1乾燥可視需要於惰性環境或減壓條件下實施。第1乾燥較佳為於相對較低溫下花費時間進行。若於相對較低溫下花費時間進行第1乾燥,則容易使所獲得之光學膜之散射光比率滿足式(1)。In the optical film forming step, the coating film is dried (referred to as the first drying), and after peeling from the substrate, the dried coating film is further dried (referred to as the second drying or post-baking treatment), thereby forming an optical membrane. The first drying may be carried out in an inert environment or under reduced pressure as needed. The first drying is preferably performed at a relatively low temperature and takes time. If it takes time to perform the first drying at a relatively low temperature, it is easy to make the scattered light ratio of the obtained optical film satisfy the formula (1).
此處,於工業上製造本發明之光學膜之情形時,與實驗室水準之製造環境相比,實際製造環境多數情況下不利於獲得較低之散射光比率Ts,其結果為,有難以提高光學膜之廣角視認性之情形。如上所述較佳為於相對較低溫下花費時間進行第1乾燥,但於實驗室水準下進行第1乾燥時,可於密閉之乾燥器內進行乾燥,因此相對不易產生因外部要因所致之光學膜之表面粗糙。與此相對,於工業上製造光學膜之情形時,例如於第1乾燥中需要對較廣之面積進行加熱,因此有時於加熱時亦使用送風裝置。其結果為,光學膜之表面狀態容易變得粗糙,難以降低光學膜之散射光比率Ts。Here, when the optical film of the present invention is manufactured industrially, compared with a laboratory-level manufacturing environment, the actual manufacturing environment is not conducive to obtaining a lower scattered light ratio Ts in most cases. As a result, it is difficult to improve The wide-angle visibility of the optical film. As mentioned above, it is better to spend time for the first drying at a relatively low temperature. However, when the first drying is performed at a laboratory level, the drying can be carried out in a closed dryer, so it is relatively difficult to cause external factors. The surface of the optical film is rough. On the other hand, when an optical film is manufactured industrially, for example, it is necessary to heat a wide area in the first drying. Therefore, an air blower may also be used during heating. As a result, the surface condition of the optical film tends to become rough, and it is difficult to reduce the scattered light ratio Ts of the optical film.
於藉由加熱進行乾燥之情形時,尤其考慮到工業上製造光學膜時之如上所述之外部要因,第1乾燥之溫度較佳為60~150℃,更佳為60~140℃,進而較佳為70~140℃。第1乾燥之時間較佳為1~60分鐘,更佳為5~40分鐘。尤其考慮到工業上製造光學膜時之如上所述之外部要因,較佳為於3階段以上之乾燥溫度條件下實施。多階段之條件可於各階段中,於相同或不同之溫度條件及/或乾燥時間下實施,例如可以3~10階段、較佳為3~8階段進行乾燥。若於3階段以上之多階段條件下實施第1乾燥,則所獲得之光學膜容易滿足式(1)。於3階段以上之多階段條件下之態樣中,較佳為第1乾燥之溫度分佈包含升溫及降溫。即,光學膜形成步驟中之第1乾燥條件更佳為溫度分佈包含升溫及降溫之3階段以上之加熱溫度條件。作為此種溫度分佈,若列舉4階段之情形為例,則第1乾燥之溫度依序為70~90℃(第1溫度)、90~120℃(第2溫度)、80~120℃(第3溫度)及80~100℃(第4溫度)。於該例中,第1乾燥之溫度自第1溫度升溫至第2溫度,繼而自第2溫度降溫至第3溫度,進而自第3溫度降溫至第4溫度。此處,第1乾燥之時間於各階段中例如為5~15分鐘。較佳為以乾燥塗膜之溶劑殘存量相對於乾燥塗膜之質量,較佳為5~15質量%,更佳為6~12質量%之方式實施第1乾燥。若溶劑殘存量為上述範圍,則乾燥塗膜自基材之剝離性變得良好,所獲得之光學膜容易滿足式(1)。In the case of drying by heating, the temperature of the first drying is preferably 60-150°C, more preferably 60-140°C, and particularly considering the external factors described above when manufacturing optical films in industry. It is preferably 70 to 140°C. The first drying time is preferably 1 to 60 minutes, more preferably 5 to 40 minutes. In particular, in consideration of the above-mentioned external factors when manufacturing optical films industrially, it is preferable to implement it under the drying temperature condition of three stages or more. Multi-stage conditions can be implemented in each stage under the same or different temperature conditions and/or drying time. For example, drying can be carried out in 3-10 stages, preferably 3-8 stages. If the first drying is performed under a multi-stage condition of three or more stages, the obtained optical film easily satisfies the formula (1). In the case of a multi-stage condition with three or more stages, it is preferable that the temperature distribution of the first drying includes heating and cooling. That is, the first drying condition in the optical film forming step is more preferably a heating temperature condition in which the temperature distribution includes three or more stages of temperature increase and temperature decrease. As such a temperature distribution, if a four-stage case is taken as an example, the temperature of the first drying is 70 to 90°C (first temperature), 90 to 120°C (second temperature), and 80 to 120°C (second temperature). 3 temperature) and 80 to 100°C (the fourth temperature). In this example, the temperature of the first drying is increased from the first temperature to the second temperature, then the temperature is decreased from the second temperature to the third temperature, and then the temperature is decreased from the third temperature to the fourth temperature. Here, the time for the first drying is, for example, 5 to 15 minutes in each stage. It is preferable to perform the first drying with the residual amount of the solvent of the dried coating film relative to the mass of the dried coating film, preferably 5 to 15% by mass, more preferably 6 to 12% by mass. If the residual amount of the solvent is in the above range, the peelability of the dry coating film from the substrate becomes good, and the obtained optical film easily satisfies the formula (1).
第2乾燥之溫度較佳為150~300℃,更佳為180~250℃,進而較佳為180~230℃。第2乾燥之時間較佳為10~60分鐘,更佳為30~50分鐘。The temperature of the second drying is preferably 150 to 300°C, more preferably 180 to 250°C, and still more preferably 180 to 230°C. The time for the second drying is preferably 10 to 60 minutes, more preferably 30 to 50 minutes.
第2乾燥可以單片式進行,於工業上製造之情形時,就製造效率之觀點而言,較佳為以輥-輥方式進行。於單片式中,較佳為於在面內方向上均勻地伸長之狀態下進行乾燥。 於輥-輥方式中,就光學膜容易滿足式(1)之觀點而言,較佳為使乾燥塗膜於在搬送方向上伸長之狀態下乾燥,搬送速度較佳為0.1~5 m/min,更佳為0.5~3 m/min,進而較佳為0.7~1.5 m/min。第2乾燥可於1階段或多階段之條件下實施,就光學膜容易滿足式(1)之觀點而言,較佳為於多階段之條件下實施。多階段之條件較佳為於各階段中,可以選自相同或不同之溫度條件、乾燥時間及熱風之風速之至少1種實施,例如可以2~10階段、較佳為3~8階段進行乾燥。又,於各階段中,熱風之風速就所獲得之光學膜容易滿足式(1)之觀點而言,較佳為5~20 m/min,更佳為10~15 m/min,進而較佳為11~14 m/min。The second drying may be performed in a single-piece type. In the case of industrial production, it is preferably performed by a roll-to-roll method from the viewpoint of production efficiency. In the single-piece type, it is preferable to perform drying in a state uniformly elongated in the in-plane direction. In the roll-to-roll method, from the viewpoint that the optical film easily satisfies the formula (1), it is preferable to dry the dry coating film in a state stretched in the conveying direction, and the conveying speed is preferably 0.1 to 5 m/min , More preferably 0.5 to 3 m/min, still more preferably 0.7 to 1.5 m/min. The second drying can be carried out under one-stage or multi-stage conditions. From the viewpoint that the optical film easily satisfies the formula (1), it is preferably carried out under multi-stage conditions. Multi-stage conditions are preferably implemented in each stage, which can be selected from at least one of the same or different temperature conditions, drying time and hot air speed. For example, drying can be carried out in 2-10 stages, preferably 3-8 stages. . In addition, in each stage, the wind speed of the hot air is preferably 5-20 m/min, more preferably 10-15 m/min, and still more preferably, from the viewpoint that the obtained optical film easily satisfies formula (1) It is 11~14 m/min.
於本發明之光學膜具備硬塗層之情形時,硬塗層例如可於光學膜之至少一面塗佈硬化性組合物而形成塗膜,對該塗膜照射高能量射線使塗膜硬化而形成。When the optical film of the present invention has a hard coat layer, the hard coat layer can be formed by applying a curable composition on at least one side of the optical film to form a coating film, and irradiating the coating film with high energy rays to harden the coating film. .
塗佈方法可列舉上述所例示之公知塗佈方法。硬化時之高能量射線(例如活性能量射線)之照射強度係根據硬化性組合物之組成適當決定,並無特別限定,較佳為對於聚合起始劑之活化有效之波長區域之照射。照射強度較佳為0.1~6,000 mW/cm2 ,更佳為10~1,000 mW/cm2 ,進而較佳為20~500 mW/cm2 。若照射強度為上述範圍內,則可確保適當之反應時間,可抑制因自光源輻射之熱及硬化反應時之放熱所致之樹脂之黃變或劣化。照射時間只要根據硬化性組合物之組成適當選擇即可,並無特別限制,以表示為上述照射強度與照射時間之積的累計光量較佳為10~10,000 mJ/cm2 ,更佳為50~1,000 mJ/cm2 ,進而較佳為80~500 mJ/cm2 之方式設定。若累計光量為上述範圍內,則可產生充分量之源自聚合起始劑之活性種而更確實地進行硬化反應,又,照射時間不會過長而可維持良好之生產性。又,藉由經過該範圍內之照射步驟,可進一步提高硬塗層之硬度,故有用。就提高硬塗層之平滑性,進一步提高光學膜之廣角方向之視認性之觀點而言,可列舉溶劑之種類、成分比、固形物成分濃度之最佳化及調平劑之添加等。Examples of the coating method include the well-known coating methods exemplified above. The irradiation intensity of high energy rays (for example, active energy rays) during curing is appropriately determined according to the composition of the curable composition, and is not particularly limited. It is preferably irradiation in a wavelength region effective for activation of the polymerization initiator. The irradiation intensity is preferably 0.1 to 6,000 mW/cm 2 , more preferably 10 to 1,000 mW/cm 2 , and still more preferably 20 to 500 mW/cm 2 . If the irradiation intensity is within the above range, an appropriate reaction time can be ensured, and yellowing or deterioration of the resin due to the heat radiated from the light source and the exothermic heat during the curing reaction can be suppressed. The irradiation time may be appropriately selected according to the composition of the curable composition and is not particularly limited. The cumulative light quantity expressed as the product of the irradiation intensity and the irradiation time is preferably 10 to 10,000 mJ/cm 2 , more preferably 50 to 1,000 mJ/cm 2 , and more preferably 80-500 mJ/cm 2 . If the cumulative amount of light is within the above range, a sufficient amount of active species derived from the polymerization initiator can be generated and the curing reaction can proceed more reliably, and the irradiation time is not too long and good productivity can be maintained. In addition, by going through the irradiation step within this range, the hardness of the hard coat layer can be further increased, which is useful. From the viewpoint of improving the smoothness of the hard coat layer and further improving the visibility of the optical film in the wide-angle direction, the type of solvent, the ratio of components, the optimization of the solid content concentration, and the addition of leveling agents can be cited.
[可撓性圖像顯示裝置] 本發明包含具備上述光學膜之可撓性顯示裝置。本發明之光學膜較佳為於可撓性圖像顯示裝置中用作前面板,該前面板有時被稱為視窗膜。該可撓性圖像顯示裝置包括可撓性圖像顯示裝置用積層體及有機EL(Electroluminescence,電致發光)顯示面板,且構成為,相對於有機EL顯示面板,於視認側配置可撓性圖像顯示裝置用積層體,且能夠彎折。作為可撓性圖像顯示裝置用積層體,可進而含有偏光板、較佳為圓偏光板、觸控感測器,其等之積層順序任意,但較佳為自視認側依序積層有視窗膜、偏光板、觸控感測器或視窗膜、觸控感測器、偏光板。若於較觸控感測器靠視認側存在偏光板,則不易視認到觸控感測器之圖案,顯示圖像之視認性變得良好,故而較佳。各構件可使用接著劑、黏著劑等積層。又,可具備形成於上述視窗膜、偏光板、觸控感測器之任一層之至少一面之遮光圖案。[Flexible Image Display Device] The present invention includes a flexible display device provided with the above-mentioned optical film. The optical film of the present invention is preferably used as a front panel in a flexible image display device, and the front panel is sometimes called a window film. The flexible image display device includes a laminate for a flexible image display device and an organic EL (Electroluminescence) display panel, and is configured such that the organic EL display panel is configured to be flexible on the viewing side A laminate for an image display device and can be bent. As a laminated body for a flexible image display device, it may further contain a polarizing plate, preferably a circular polarizing plate, and a touch sensor. The order of the layers is arbitrary, but it is preferable that windows are laminated in order from the viewing side Film, polarizing plate, touch sensor or window film, touch sensor, polarizing plate. If there is a polarizing plate on the side that is more visible than the touch sensor, the pattern of the touch sensor is not easily visible, and the visibility of the displayed image becomes better, which is better. Each member can be laminated using adhesives, adhesives, etc. In addition, it may be provided with a light-shielding pattern formed on at least one surface of any one of the above-mentioned window film, polarizer, and touch sensor.
[偏光板] 本發明之可撓性顯示裝置如上所述較佳為具備偏光板、尤其是圓偏光板。圓偏光板係藉由在直線偏光板積層λ/4相位差板而具有僅使右或左圓偏光成分透過之功能之功能層。例如用以將外界光轉換為右圓偏光而阻斷由有機EL面板反射而成為左圓偏光之外界光,僅使有機EL之發光成分透過,藉此抑制反射光之影響而容易看到圖像。為了達成圓偏光功能,直線偏光板之吸收軸與λ/4相位差板之遲相軸理論上必須為45°,但實際應用中為45±10°。直線偏光板與λ/4相位差板未必必須鄰接地積層,只要吸收軸與遲相軸之關係滿足上述範圍即可。雖然較佳為於全部波長下達成完全之圓偏光,但實際應用中未必必須如此,因此本發明之圓偏光板亦包含橢圓偏光板。亦較佳為藉由在直線偏光板之視認側進而積層λ/4相位差膜,使出射光成為圓偏光,而提高配戴有偏光太陽眼鏡之狀態下之視認性。[Polarizer] As described above, the flexible display device of the present invention preferably includes a polarizing plate, especially a circular polarizing plate. The circular polarizing plate is a functional layer that has the function of transmitting only the right or left circularly polarized light component by laminating a λ/4 phase difference plate on the linear polarizing plate. For example, it is used to convert external light into right circular polarized light and block the outer boundary light reflected by the organic EL panel to become left circular polarized light, and only transmit the luminous components of the organic EL, thereby suppressing the influence of reflected light and making it easier to see the image . In order to achieve the circular polarization function, the absorption axis of the linear polarizer and the late axis of the λ/4 retardation plate must theoretically be 45°, but in actual applications it is 45±10°. The linear polarizing plate and the λ/4 retardation plate do not necessarily have to be laminated adjacently, as long as the relationship between the absorption axis and the slow phase axis satisfies the above range. Although it is preferable to achieve complete circular polarization at all wavelengths, this is not necessarily the case in practical applications. Therefore, the circular polarization plate of the present invention also includes an elliptical polarization plate. It is also preferable to laminate a λ/4 retardation film on the visibility side of the linear polarizer to make the emitted light circularly polarized, thereby improving the visibility when wearing polarized sunglasses.
直線偏光板係具有使於透過軸方向上振動之光透過,但阻斷與其垂直之振動成分之偏光之功能的功能層。上述直線偏光板可為具備單獨之直線偏光元件或具備直線偏光元件及貼附於其至少一面之保護膜之構成。上述直線偏光板之厚度可為200 μm以下,較佳為0.5~100 μm。若直線偏光板之厚度處於上述範圍,則有直線偏光板之柔軟性不易降低之傾向。The linear polarizer is a functional layer that transmits light that vibrates in the direction of the transmission axis, but blocks the polarization of the vibration component perpendicular to it. The above-mentioned linear polarizing plate may be provided with a single linear polarizing element or with a linear polarizing element and a protective film attached to at least one surface thereof. The thickness of the linear polarizer may be 200 μm or less, preferably 0.5-100 μm. If the thickness of the linear polarizer is in the above range, the flexibility of the linear polarizer tends not to be easily reduced.
上述直線偏光元件亦可為藉由將聚乙烯醇(以下有時稱為PVA)系膜進行染色、延伸而製造之膜型偏光元件。使碘等二色性色素吸附於藉由延伸而配向之PVA系膜、或於吸附於PVA之狀態下延伸,藉此使二色性色素配向,發揮偏光性能。於上述膜型偏光元件之製造中,亦可另外具有膨潤、利用硼酸之交聯、利用水溶液之洗淨、乾燥等步驟。延伸或染色步驟可以PVA系膜單獨進行,亦可於與如聚對苯二甲酸乙二酯之其他膜積層之狀態下進行。所使用之PVA系膜之厚度較佳為10~100 μm,上述延伸倍率較佳為2~10倍。 進而,作為上述偏光元件之另一例,可列舉塗佈液晶偏光組合物所形成之液晶塗佈型偏光元件。上述液晶偏光組合物可包含液晶性化合物及二色性色素化合物。上述液晶性化合物只要具有顯示液晶狀態之性質即可,尤其若具有層列相等高次之配向狀態,則可發揮較高之偏光性能,故而較佳。又,液晶性化合物較佳為具有聚合性官能基。 上述二色性色素化合物係與上述液晶化合物一起配向而顯示二色性之色素,且可具有聚合性官能基,又,二色性色素自身可具有液晶性。 液晶偏光組合物中所含之化合物之任一者具有聚合性官能基。上述液晶偏光組合物可進而包含起始劑、溶劑、分散劑、調平劑、穩定劑、界面活性劑、交聯劑、矽烷偶合劑等。 上述液晶偏光層係藉由在配向膜上塗佈液晶偏光組合物而形成液晶偏光層而製造。液晶偏光層可形成為厚度薄於膜型偏光元件,其厚度較佳為0.5~10 μm,更佳為1~5 μm。The above-mentioned linear polarizing element may be a film-type polarizing element manufactured by dyeing and stretching a polyvinyl alcohol (hereinafter sometimes referred to as PVA) film. The dichroic dye such as iodine is adsorbed on the PVA-based film aligned by stretching, or stretched while adsorbing on the PVA, thereby aligning the dichroic dye and exhibiting polarization performance. In the manufacture of the above-mentioned film-type polarizing element, there may be additional steps such as swelling, cross-linking with boric acid, washing with aqueous solution, and drying. The stretching or dyeing step can be carried out with a PVA-based film alone or in the state of being laminated with other films such as polyethylene terephthalate. The thickness of the PVA-based film used is preferably 10-100 μm, and the above-mentioned stretching ratio is preferably 2-10 times. Furthermore, as another example of the above-mentioned polarizing element, a liquid crystal coating type polarizing element formed by applying a liquid crystal polarizing composition can be cited. The liquid crystal polarizing composition may contain a liquid crystal compound and a dichroic dye compound. The above-mentioned liquid crystalline compound only needs to have the property of displaying a liquid crystal state, especially if it has an alignment state of the order of the order of smectic alignment, it can exhibit higher polarization performance, so it is preferable. Moreover, it is preferable that the liquid crystal compound has a polymerizable functional group. The dichroic dye compound is a dye that is aligned with the liquid crystal compound to exhibit dichroism, and may have a polymerizable functional group, and the dichroic dye itself may have liquid crystallinity. Any of the compounds contained in the liquid crystal polarizing composition has a polymerizable functional group. The liquid crystal polarizing composition may further include a starter, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a crosslinking agent, a silane coupling agent, and the like. The above-mentioned liquid crystal polarizing layer is manufactured by coating a liquid crystal polarizing composition on an alignment film to form a liquid crystal polarizing layer. The liquid crystal polarizing layer can be formed to be thinner than the film-type polarizing element, and its thickness is preferably 0.5-10 μm, more preferably 1-5 μm.
上述配向膜係藉由例如在基材上塗佈配向膜形成組合物並利用摩擦、偏光照射等賦予配向性而製造。上述配向膜形成組合物包含配向劑,亦可進而包含溶劑、交聯劑、起始劑、分散劑、調平劑、矽烷偶合劑等。作為上述配向劑,例如可列舉聚乙烯醇類、聚丙烯酸酯類、聚醯胺酸類、聚醯亞胺類。於使用藉由偏光照射賦予配向性之配向劑之情形時,較佳為使用包含肉桂酸酯基之配向劑。用作上述配向劑之高分子之重量平均分子量例如為10,000~1,000,000左右。上述配向膜之厚度較佳為5~10,000 nm,就充分地表現出配向限制力之方面而言,更佳為10~500 nm。 上述液晶偏光層可自基材剝離再轉印而積層,亦可直接積層上述基材。上述基材亦較佳為擔負作為保護膜或相位差板、視窗膜之透明基材之作用。The above-mentioned alignment film is produced by, for example, coating an alignment film forming composition on a substrate and imparting alignment properties by rubbing, polarized light irradiation, or the like. The alignment film forming composition described above includes an alignment agent, and may further include a solvent, a crosslinking agent, an initiator, a dispersant, a leveling agent, a silane coupling agent, and the like. Examples of the aforementioned alignment agent include polyvinyl alcohols, polyacrylates, polyamides, and polyimines. In the case of using an alignment agent that imparts alignment properties by polarized light irradiation, it is preferable to use an alignment agent containing a cinnamate group. The weight average molecular weight of the polymer used as the above-mentioned alignment agent is, for example, about 10,000 to 1,000,000. The thickness of the alignment film is preferably 5 to 10,000 nm, and more preferably 10 to 500 nm in terms of sufficiently exhibiting the alignment restriction force. The liquid crystal polarizing layer may be peeled from the base material and then transferred and laminated, or the base material may be laminated directly. The above-mentioned base material is also preferably used as a transparent base material for protective film, phase difference plate, and window film.
作為上述保護膜,只要為透明高分子膜即可,可使用與用於上述視窗膜之透明基材之材料或添加劑相同者。又,亦可為塗佈環氧樹脂等陽離子硬化組合物或丙烯酸酯等自由基硬化組合物並進行硬化而獲得之塗佈型保護膜。該保護膜亦可視需要含有塑化劑、紫外線吸收劑、紅外線吸收劑、如顏料或染料之著色劑、螢光增白劑、分散劑、熱穩定劑、光穩定劑、抗靜電劑、抗氧化劑、潤滑劑、溶劑等。該保護膜之厚度較佳為200 μm以下,更佳為1~100 μm。若保護膜之厚度為上述範圍,則有該膜之柔軟性不易降低之傾向。The protective film may be a transparent polymer film, and the same materials or additives used for the transparent substrate of the window film can be used. In addition, it may be a coating type protective film obtained by applying and curing a cationic curing composition such as epoxy resin or a radical curing composition such as acrylate. The protective film may optionally contain plasticizers, ultraviolet absorbers, infrared absorbers, coloring agents such as pigments or dyes, fluorescent brighteners, dispersants, heat stabilizers, light stabilizers, antistatic agents, and antioxidants. , Lubricants, solvents, etc. The thickness of the protective film is preferably 200 μm or less, more preferably 1-100 μm. If the thickness of the protective film is in the above range, there is a tendency that the flexibility of the film is not easily reduced.
上述λ/4相位差板係對與入射光之行進方向正交之方向(膜之面內方向)賦予λ/4之相位差之膜。上述λ/4相位差板係藉由將纖維素系膜、烯烴系膜、聚碳酸酯系膜等高分子膜進行延伸而製造之延伸型相位差板。上述λ/4相位差板亦可視需要含有相位差調整劑、塑化劑、紫外線吸收劑、紅外線吸收劑、如顏料或染料之著色劑、螢光增白劑、分散劑、熱穩定劑、光穩定劑、抗靜電劑、抗氧化劑、潤滑劑、溶劑等。 上述延伸型相位差板之厚度較佳為200 μm以下,更佳為1~100 μm。若延伸型相位差板之厚度為上述範圍,則有該延伸型相位差板之柔軟性不易降低之傾向。 進而,作為上述λ/4相位差板之另一例,可列舉塗佈液晶組合物所形成之液晶塗佈型相位差板。 上述液晶組合物包含顯示向列型、膽固醇型、層列型等之液晶狀態之液晶性化合物。上述液晶性化合物具有聚合性官能基。 上述液晶組合物可進而包含起始劑、溶劑、分散劑、調平劑、穩定劑、界面活性劑、交聯劑、矽烷偶合劑等。 上述液晶塗佈型相位差板可與上述液晶偏光層同樣地,藉由將液晶組合物塗佈於基底上並進行硬化而形成液晶相位差層而製造。液晶塗佈型相位差板可形成為厚度薄於延伸型相位差板。上述液晶偏光層之厚度較佳為0.5~10 μm,更佳為1~5 μm。 上述液晶塗佈型相位差板可自基材剝離再轉印而積層,亦可直接積層上述基材。上述基材亦較佳為擔負作為保護膜或相位差板、視窗膜之透明基材之作用。The above-mentioned λ/4 retardation plate is a film that provides a λ/4 retardation in a direction orthogonal to the traveling direction of incident light (in-plane direction of the film). The above-mentioned λ/4 retardation plate is a stretched retardation plate manufactured by stretching a polymer film such as a cellulose-based film, an olefin-based film, and a polycarbonate-based film. The above-mentioned λ/4 retardation plate may optionally contain retardation adjusters, plasticizers, ultraviolet absorbers, infrared absorbers, coloring agents such as pigments or dyes, fluorescent brighteners, dispersants, heat stabilizers, light Stabilizers, antistatic agents, antioxidants, lubricants, solvents, etc. The thickness of the extended phase difference plate is preferably 200 μm or less, more preferably 1-100 μm. If the thickness of the extended phase difference plate is in the above range, the flexibility of the extended phase difference plate tends to be less likely to decrease. Furthermore, as another example of the aforementioned λ/4 retardation plate, a liquid crystal coating type retardation plate formed by applying a liquid crystal composition can be cited. The above-mentioned liquid crystal composition includes a liquid crystal compound showing a liquid crystal state such as nematic, cholesteric, and smectic. The above-mentioned liquid crystal compound has a polymerizable functional group. The above-mentioned liquid crystal composition may further include a starter, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a crosslinking agent, a silane coupling agent, and the like. The liquid crystal coating type retardation plate can be manufactured by applying a liquid crystal composition on a base and curing the liquid crystal retardation layer in the same manner as the liquid crystal polarizing layer. The liquid crystal coating type retardation plate can be formed to be thinner than the extension type retardation plate. The thickness of the liquid crystal polarizing layer is preferably 0.5 to 10 μm, more preferably 1 to 5 μm. The liquid crystal coating type retardation plate may be peeled from the base material and then transferred and laminated, or the base material may be directly laminated. The above-mentioned base material is also preferably used as a transparent base material for protective film, phase difference plate, and window film.
一般而言,多數材料顯示出波長越短則雙折射越大,波長越長則雙折射越小之雙折射。於該情形時,無法於全部可見光區域達成λ/4之相位差,因此以相對於視感度較高之560 nm附近成為λ/4之方式,將面內相位差設計為較佳為100~180 nm,更佳為130~150 nm。使用具有與通常相反之雙折射率波長分散特性之材料的逆分散λ/4相位差板於視認性良好之方面較佳。作為此種材料,例如延伸型相位差板可使用日本專利特開2007-232873號公報等所記載者,液晶塗佈型相位差板可使用日本專利特開2010-30979號公報等所記載者。 又,作為其他方法,亦已知有藉由與λ/2相位差板組合而獲得寬頻帶λ/4相位差板之技術(例如日本專利特開平10-90521號公報等)。λ/2相位差板亦藉由與λ/4相位差板相同之材料方法進行製造。延伸型相位差板與液晶塗佈型相位差板之組合為任意,但任一種均可藉由使用液晶塗佈型相位差板而減薄厚度。 對於上述圓偏光板,為了提高傾斜方向之視認性,已知有積層正C板之方法(例如日本專利特開2014-224837號公報等)。正C板可為液晶塗佈型相位差板,亦可為延伸型相位差板。該相位差板之厚度方向之相位差較佳為-200~-20 nm,更佳為-140~-40 nm。Generally speaking, most materials show birefringence that the shorter the wavelength, the greater the birefringence, and the longer the wavelength, the smaller the birefringence. In this case, the phase difference of λ/4 cannot be achieved in the entire visible light region. Therefore, the in-plane phase difference is preferably designed to be 100 to 180 in such a way that it becomes λ/4 in the vicinity of 560 nm, which has a higher visual sensitivity. nm, more preferably 130 to 150 nm. A reverse dispersion λ/4 retardation plate using a material having birefringence wavelength dispersion characteristics opposite to that of usual is preferable in terms of good visibility. As such a material, for example, the extension type retardation plate can use what is described in Japanese Patent Laid-Open No. 2007-232873, and the liquid crystal coating type retardation plate can use what is described in Japanese Patent Laid-Open No. 2010-30979. In addition, as another method, a technique of obtaining a wide-band λ/4 retardation plate by combining with a λ/2 retardation plate is also known (for example, Japanese Patent Laid-Open No. 10-90521 etc.). The λ/2 retardation plate is also manufactured by the same material method as the λ/4 retardation plate. The combination of the extension type retardation plate and the liquid crystal coating type retardation plate is arbitrary, but any of them can be thinned by using the liquid crystal coating type retardation plate. For the above circular polarizing plate, in order to improve the visibility in the oblique direction, a method of laminating positive C plates is known (for example, Japanese Patent Laid-Open No. 2014-224837 etc.). The positive C plate can be a liquid crystal coating type retardation plate or an extended type retardation plate. The retardation in the thickness direction of the retardation plate is preferably -200 to -20 nm, more preferably -140 to -40 nm.
[觸控感測器] 本發明之可撓性顯示裝置較佳為如上所述具備觸控感測器。觸控感測器用作輸入機構。作為觸控感測器,可列舉電阻膜方式、表面聲波方式、紅外線方式、電磁感應方式、靜電電容方式等各種樣式,較佳為靜電電容方式。 靜電電容方式觸控感測器劃分為活性區域及位於上述活性區域之外廓部之非活性區域。活性區域係與顯示面板上顯示畫面之區域(顯示部)對應之區域,且係感知使用者之觸控之區域,非活性區域係與顯示裝置中不顯示畫面之區域(非顯示部)對應之區域。觸控感測器可包含:具有可撓性之特性之基板、形成於上述基板之活性區域之感知圖案、以及形成於上述基板之非活性區域且用以經由上述感知圖案及焊墊部而與外部之驅動電路連接之各感測線。作為具有可撓性之特性之基板,可使用與上述視窗膜之透明基板相同之材料。[Touch Sensor] The flexible display device of the present invention preferably has a touch sensor as described above. The touch sensor is used as an input mechanism. As the touch sensor, various types such as a resistive film method, a surface acoustic wave method, an infrared method, an electromagnetic induction method, and an electrostatic capacitance method can be cited, and the electrostatic capacitance method is preferred. The capacitive touch sensor is divided into an active area and an inactive area located outside the active area. The active area is the area corresponding to the area on the display panel (display part) that senses the user's touch, and the inactive area corresponds to the area (non-display part) of the display device that does not display the picture area. The touch sensor may include: a substrate with flexible characteristics, a sensing pattern formed on the active area of the substrate, and an inactive area formed on the substrate and used to communicate with each other through the sensing pattern and the bonding pad. Each sensing line connected to the external drive circuit. As a substrate with flexible characteristics, the same material as the transparent substrate of the above-mentioned window film can be used.
上述感知圖案可具備形成於第1方向之第1圖案及形成於第2方向之第2圖案。第1圖案與第2圖案配置於互不相同之方向。第1圖案及第2圖案形成於同一層,為了感知被觸控之地點,必須將各圖案電性連接。第1圖案係複數個單位圖案經由接頭而相互連接之形態,第2圖案成為複數個單位圖案以島嶼形態相互分離之結構,因此為了將第2圖案電性連接,需要另外之橋接電極。用於第2圖案之連接之電極可應用周知之透明電極。作為該透明電極之素材,例如可列舉銦錫氧化物(ITO)、銦鋅氧化物(IZO)、鋅氧化物(ZnO)、銦鋅錫氧化物(IZTO)、銦鎵鋅氧化物(IGZO)、鎘錫氧化物(CTO)、PEDOT(poly(3,4-ethylenedioxythiophene),聚(3,4-乙二氧基噻吩))、奈米碳管(CNT)、石墨烯、金屬線等,較佳可列舉ITO。該等可單獨使用或混合2種以上使用。用於金屬線之金屬並無特別限定,例如可列舉銀、金、鋁、銅、鐵、鎳、鈦、碲、鉻等,該等可單獨使用或混合2種以上使用。 橋接電極可於感知圖案上部隔著絕緣層形成於上述絕緣層上部,可於基板上形成橋接電極,於其上形成絕緣層及感知圖案。上述橋接電極亦可由與感知圖案相同之素材形成,亦可由鉬、銀、鋁、銅、鈀、金、鉑、鋅、錫、鈦或該等中之2種以上之合金形成。 第1圖案與第2圖案必須電性絕緣,因此於感知圖案與橋接電極之間形成絕緣層。該絕緣層亦可僅形成於第1圖案之接頭與橋接電極之間,或作為覆蓋感知圖案整體之層形成。於覆蓋感知圖案整體之層之情形時,橋接電極可經由形成於絕緣層之接觸孔連接第2圖案。The aforementioned sensing pattern may include a first pattern formed in the first direction and a second pattern formed in the second direction. The first pattern and the second pattern are arranged in different directions. The first pattern and the second pattern are formed on the same layer. In order to sense the touched location, each pattern must be electrically connected. The first pattern is a form in which a plurality of unit patterns are connected to each other via a joint, and the second pattern is a structure in which a plurality of unit patterns are separated from each other in an island form. Therefore, in order to electrically connect the second pattern, another bridge electrode is required. The electrode used for the connection of the second pattern can be a well-known transparent electrode. Examples of materials for the transparent electrode include indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium zinc tin oxide (IZTO), and indium gallium zinc oxide (IGZO) , Cadmium tin oxide (CTO), PEDOT (poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxythiophene)), carbon nanotube (CNT), graphene, metal wire, etc. A good example is ITO. These can be used individually or in mixture of 2 or more types. The metal used for the metal wire is not particularly limited, and examples include silver, gold, aluminum, copper, iron, nickel, titanium, tellurium, chromium, etc., and these can be used alone or in combination of two or more. The bridge electrode can be formed on the upper part of the insulating layer via the insulating layer on the upper part of the sensing pattern, and the bridge electrode can be formed on the substrate, and the insulating layer and the sensing pattern can be formed thereon. The above-mentioned bridge electrode may also be formed of the same material as the sensing pattern, or may be formed of molybdenum, silver, aluminum, copper, palladium, gold, platinum, zinc, tin, titanium, or an alloy of two or more of these. The first pattern and the second pattern must be electrically insulated, so an insulating layer is formed between the sensing pattern and the bridge electrode. The insulating layer can also be formed only between the joints of the first pattern and the bridging electrodes, or as a layer covering the entire sensing pattern. In the case of covering the whole layer of the sensing pattern, the bridge electrode may be connected to the second pattern through the contact hole formed in the insulating layer.
上述觸控感測器可於基板與電極之間進而包含光學調節層作為用以適當地補償形成有感知圖案之圖案區域與未形成感知圖案之非圖案區域之間的透過率之差、具體而言由該等區域之折射率之差所誘發之光透過率之差的機構。該光學調節層可包含無機絕緣物質或有機絕緣物質。光學調節層可將包含光硬化性有機黏合劑及溶劑之光硬化組合物塗佈於基板上而形成。上述光硬化組合物可進而包含無機粒子。藉由上述無機粒子,可提高光學調節層之折射率。 上述光硬化性有機黏合劑可於無損本發明之效果之範圍內包含例如丙烯酸酯系單體、苯乙烯系單體、羧酸系單體等各單體之共聚物。上述光硬化性有機黏合劑亦可為包含例如含環氧基之重複單元、丙烯酸酯重複單元、羧酸重複單元等互不相同之各重複單元之共聚物。 作為上述無機粒子,例如可列舉氧化鋯粒子、氧化鈦粒子、氧化鋁粒子等。 上述光硬化組合物亦可進而包含光聚合起始劑、聚合性單體、硬化輔助劑等各添加劑。The above-mentioned touch sensor may further include an optical adjustment layer between the substrate and the electrode to appropriately compensate for the difference in transmittance between the pattern area where the sensing pattern is formed and the non-pattern area where the sensing pattern is not formed. It is the mechanism of the difference in light transmittance induced by the difference in refractive index of these areas. The optical adjustment layer may include an inorganic insulating material or an organic insulating material. The optical adjustment layer can be formed by coating a photocuring composition containing a photocuring organic adhesive and a solvent on a substrate. The aforementioned photocurable composition may further include inorganic particles. The above-mentioned inorganic particles can increase the refractive index of the optical adjustment layer. The above-mentioned photocurable organic adhesive may include copolymers of monomers such as acrylic ester monomers, styrene monomers, and carboxylic acid monomers within a range that does not impair the effects of the present invention. The above-mentioned photocurable organic adhesive may also be a copolymer containing different repeating units such as epoxy-containing repeating units, acrylate repeating units, carboxylic acid repeating units, and the like. Examples of the above-mentioned inorganic particles include zirconium oxide particles, titanium oxide particles, and aluminum oxide particles. The photocurable composition may further include various additives such as a photopolymerization initiator, a polymerizable monomer, and a curing auxiliary agent.
[接著層] 形成上述可撓性圖像顯示裝置用積層體之各層(視窗膜、圓偏光板、觸控感測器)以及構成各層之膜構件(直線偏光板、λ/4相位差板等)可藉由接著劑進行接合。作為該接著劑,可使用水系接著劑、水系溶劑揮散型接著劑、有機溶劑系、無溶劑系接著劑、固體接著劑、溶劑揮散型接著劑、濕氣硬化型接著劑、加熱硬化型接著劑、厭氧硬化型、活性能量射線硬化型接著劑、硬化劑混合型接著劑、熱熔融型接著劑、感壓型接著劑(黏著劑)、再濕型接著劑等通常使用之接著劑等,較佳可使用水系溶劑揮散型接著劑、活性能量射線硬化型接著劑、黏著劑。接著劑層之厚度可根據所要求之接著力等而適當調節,較佳為0.01~500 μm,更佳為0.1~300 μm。於上述可撓性圖像顯示裝置用積層體中存在複數個接著層,各者之厚度或種類可相同亦可不同。[Next layer] The layers (window film, circular polarizing plate, touch sensor) and the film members (linear polarizing plate, λ/4 phase difference plate, etc.) constituting each layer of the laminated body for the flexible image display device can be formed by Adhesive for bonding. As the adhesive, water-based adhesives, water-based solvent-volatile adhesives, organic solvents, solvent-free adhesives, solid adhesives, solvent-volatile adhesives, moisture-curing adhesives, and heat-curing adhesives can be used , Anaerobic curing type, active energy ray curing type adhesive, curing agent mixed type adhesive, hot melt type adhesive, pressure sensitive type adhesive (adhesive), rewetting type adhesive and other commonly used adhesives, etc., Preferably, a water-based solvent volatile adhesive, an active energy ray hardening adhesive, and an adhesive can be used. The thickness of the adhesive layer can be appropriately adjusted according to the required adhesive force, etc., preferably 0.01 to 500 μm, more preferably 0.1 to 300 μm. There are a plurality of adhesive layers in the above-mentioned laminate for flexible image display devices, and the thickness or type of each may be the same or different.
作為上述水系溶劑揮散型接著劑,可使用聚乙烯醇系聚合物、澱粉等水溶性聚合物、乙烯-乙酸乙烯酯系乳液、苯乙烯-丁二烯系乳液等水分散狀態之聚合物作為主劑聚合物。除上述主劑聚合物及水以外,亦可調配交聯劑、矽烷系化合物、離子性化合物、交聯觸媒、抗氧化劑、染料、顏料、無機填料、有機溶劑等。於藉由上述水系溶劑揮散型接著劑進行接著之情形時,可藉由在將上述水系溶劑揮散型接著劑注入至被接著層間而貼合被黏著層後進行乾燥而賦予接著性。於使用上述水系溶劑揮散型接著劑之情形時,該接著層之厚度較佳為0.01~10 μm,更佳為0.1~1 μm。於將上述水系溶劑揮散型接著劑用於複數層之情形時,各層之厚度或種類可相同亦可不同。As the above-mentioned aqueous solvent volatile adhesive, water-dispersed polymers such as polyvinyl alcohol-based polymers, starches, etc., ethylene-vinyl acetate emulsions, styrene-butadiene emulsions, and other water-dispersed polymers can be used as main components. Agent polymer. In addition to the above-mentioned main agent polymer and water, crosslinking agents, silane-based compounds, ionic compounds, crosslinking catalysts, antioxidants, dyes, pigments, inorganic fillers, organic solvents, etc. can also be formulated. In the case of bonding by the above-mentioned water-based solvent-volatile adhesive, the above-mentioned water-based solvent-volatile adhesive may be injected between layers to be bonded to bond the adhered layer, and then dried to impart adhesiveness. In the case of using the above-mentioned aqueous solvent volatile adhesive, the thickness of the adhesive layer is preferably 0.01-10 μm, more preferably 0.1-1 μm. When the above-mentioned water-based solvent-volatile adhesive is used for multiple layers, the thickness or type of each layer may be the same or different.
上述活性能量射線硬化型接著劑可藉由包含照射活性能量射線而形成接著劑層之反應性材料的活性能量射線硬化組合物之硬化而形成。上述活性能量射線硬化組合物可含有與硬塗組合物中所含者相同之自由基聚合性化合物及陽離子聚合性化合物之至少1種聚合物。上述自由基聚合性化合物可使用與硬塗組合物中之自由基聚合性化合物相同之化合物。 上述陽離子聚合性化合物可使用與硬塗組合物中之陽離子聚合性化合物相同之化合物。 作為用於活性能量射線硬化組合物之陽離子聚合性化合物,尤佳為環氧化合物。為了降低作為接著劑組合物之黏度,亦較佳為包含單官能化合物作為反應性稀釋劑。The active energy ray curable adhesive can be formed by curing an active energy ray curable composition containing a reactive material that forms an adhesive layer by irradiating active energy rays. The active energy ray hardening composition may contain at least one polymer of the same radical polymerizable compound and cation polymerizable compound as those contained in the hard coat composition. The radical polymerizable compound can be the same as the radical polymerizable compound in the hard coat composition. The above-mentioned cationically polymerizable compound can use the same compound as the cationically polymerizable compound in the hard coat composition. As the cationic polymerizable compound used in the active energy ray hardening composition, an epoxy compound is particularly preferred. In order to reduce the viscosity of the adhesive composition, it is also preferable to include a monofunctional compound as a reactive diluent.
為了降低黏度,活性能量射線組合物可包含單官能化合物。作為該單官能化合物,可列舉於1分子中具有1個(甲基)丙烯醯基之丙烯酸酯系單體,或於1分子中具有1個環氧基或氧雜環丁基之化合物、例如(甲基)丙烯酸縮水甘油酯等。 活性能量射線組合物可進而包含聚合起始劑。作為該聚合起始劑,可列舉自由基聚合起始劑、陽離子聚合起始劑、自由基及陽離子聚合起始劑等,該等可適當選擇使用。該等聚合起始劑係藉由活性能量射線照射及加熱之至少一種而分解,產生自由基或陽離子而使自由基聚合與陽離子聚合進行者。可使用硬塗組合物之記載中能夠藉由活性能量射線照射而使自由基聚合或陽離子聚合中之至少任一者開始之起始劑。 上述活性能量射線硬化組合物可進而包含離子捕捉劑、抗氧化劑、鏈轉移劑、密接賦予劑、熱塑性樹脂、填充劑、流動黏度調整劑、塑化劑、消泡劑溶劑、添加劑、溶劑。於藉由上述活性能量射線硬化型接著劑將2個被接著層接著之情形時,可藉由將上述活性能量射線硬化組合物塗佈於被接著層之任一者或兩者後進行貼合,對任一個被黏著層或兩個被接著層照射活性能量射線使其硬化而接著。於使用上述活性能量射線硬化型接著劑之情形時,該接著層之厚度較佳為0.01~20 μm,更佳為0.1~10 μm。於將上述活性能量射線硬化型接著劑用於複數個接著層形成之情形時,各層之厚度或種類可相同亦可不同。In order to reduce the viscosity, the active energy ray composition may include a monofunctional compound. Examples of the monofunctional compound include acrylate monomers having one (meth)acrylic acid group in one molecule, or compounds having one epoxy group or oxetanyl group in one molecule, such as (Meth) glycidyl acrylate and the like. The active energy ray composition may further include a polymerization initiator. Examples of the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, radical and cationic polymerization initiators, and the like, and these can be appropriately selected and used. These polymerization initiators are decomposed by at least one of active energy ray irradiation and heating to generate free radicals or cations to cause radical polymerization and cationic polymerization to proceed. In the description of the hard coating composition, an initiator capable of starting at least one of radical polymerization and cationic polymerization by active energy ray irradiation can be used. The active energy ray hardening composition may further include an ion scavenger, an antioxidant, a chain transfer agent, an adhesion imparting agent, a thermoplastic resin, a filler, a fluid viscosity adjuster, a plasticizer, a defoamer solvent, an additive, and a solvent. In the case where two adhesive layers are bonded by the active energy ray-curable adhesive, the active energy ray curing composition can be applied to either or both of the adhesive layers and then bonded , Irradiating active energy rays to any one of the adhered layers or two of the adhered layers to harden and adhere. In the case of using the active energy ray-curable adhesive, the thickness of the adhesive layer is preferably 0.01-20 μm, more preferably 0.1-10 μm. When the above-mentioned active energy ray-curable adhesive is used for the formation of a plurality of adhesive layers, the thickness or type of each layer may be the same or different.
作為上述黏著劑,對應於主劑聚合物,分類為丙烯酸系黏著劑、胺基甲酸酯系黏著劑、橡膠系黏著劑、聚矽氧系黏著劑等,可使用任一者。黏著劑中除主劑聚合物以外,亦可調配交聯劑、矽烷系化合物、離子性化合物、交聯觸媒、抗氧化劑、黏著賦予劑、塑化劑、染料、顏料、無機填料等。藉由使構成上述黏著劑之各成分溶解、分散於溶劑中而獲得黏著劑組合物,且將該黏著劑組合物塗佈於基材上後進行乾燥,而形成黏著劑層接著層。黏著層可直接形成,亦可轉印另外形成於基材者。為了覆蓋接著前之黏著面,亦較佳為使用脫模膜。於使用上述活性能量射線硬化型接著劑之情形時,該接著層之厚度較佳為0.1~500 μm,更佳為1~300 μm。於使用複數層上述黏著劑之情形時,各層之厚度或種類可相同亦可不同。The above-mentioned adhesives are classified into acrylic adhesives, urethane-based adhesives, rubber-based adhesives, silicone-based adhesives, etc. corresponding to the main agent polymer, and any of them can be used. In addition to the main agent polymer, the adhesive can also be formulated with cross-linking agents, silane-based compounds, ionic compounds, cross-linking catalysts, antioxidants, adhesion imparting agents, plasticizers, dyes, pigments, inorganic fillers, etc. The adhesive composition is obtained by dissolving and dispersing the components constituting the adhesive in a solvent, and the adhesive composition is applied on a substrate and then dried to form an adhesive layer followed by a layer. The adhesive layer can be formed directly, or it can be transferred on the substrate. In order to cover the adhesive surface before bonding, it is also preferable to use a release film. In the case of using the above-mentioned active energy ray-curable adhesive, the thickness of the adhesive layer is preferably 0.1 to 500 μm, more preferably 1 to 300 μm. When using multiple layers of the above-mentioned adhesive, the thickness or type of each layer may be the same or different.
[遮光圖案] 上述遮光圖案可用作上述可撓性圖像顯示裝置之邊框或外殼之至少一部分。藉由遮光圖案遮住配置於上述可撓性圖像顯示裝置之邊緣部之配線使之不易被視認到,藉此圖像之視認性提高。上述遮光圖案可為單層或多層之形態。遮光圖案之顏色並無特別限制,可為黑色、白色、金屬色等多樣之顏色。遮光圖案可由用以實現顏色之顏料、丙烯酸系樹脂、酯系樹脂、環氧系樹脂、聚胺基甲酸酯、聚矽氧等高分子形成。亦可以該等單獨或2種以上之混合物使用。上述遮光圖案可藉由印刷、微影術、噴墨等各種方法形成。遮光圖案之厚度較佳為1~100 μm,更佳為2~50 μm。又,亦較佳為對遮光圖案之厚度方向賦予傾斜等形狀。 [實施例][Shading Pattern] The light-shielding pattern can be used as at least a part of the frame or housing of the flexible image display device. By shielding the wiring arranged at the edge of the flexible image display device with the light-shielding pattern so that it is not easily visible, the visibility of the image is improved. The aforementioned light-shielding pattern may be in the form of a single layer or multiple layers. The color of the shading pattern is not particularly limited, and can be black, white, metallic and other colors. The light-shielding pattern can be formed by polymers such as pigments, acrylic resins, ester resins, epoxy resins, polyurethanes, and silicones for color realization. These can also be used alone or in a mixture of two or more. The light-shielding pattern can be formed by various methods such as printing, lithography, and inkjet. The thickness of the light shielding pattern is preferably 1-100 μm, more preferably 2-50 μm. Furthermore, it is also preferable to give a shape such as an inclination to the thickness direction of the light shielding pattern. [Example]
以下,藉由實施例更詳細地說明本發明。例中之「%」及「份」若無特別說明,則意指質量%及質量份。首先對評估方法進行說明。Hereinafter, the present invention will be explained in more detail with examples. Unless otherwise specified, the "%" and "parts" in the examples mean mass% and mass parts. First, the evaluation method is explained.
<重量平均分子量> 凝膠滲透層析法(GPC)測定係使用島津製作所股份有限公司製造之液相層析儀LC-10ATvp進行。 (1)預處理方法 於使製造例1~4中所獲得之聚醯亞胺系樹脂溶解於γ-丁內酯(GBL)中而製成20質量%溶液後,利用DMF溶析液稀釋至100倍,以0.45 μm膜濾器進行過濾,將所獲得者作為測定溶液。 (2)測定條件 管柱:TSKgel SuperAWM-H×2+SuperAW2500×1(6.0 mm I.D.×150 mm×3根) 溶析液:DMF(添加10 mmol之溴化鋰) 流量:0.6 mL/min 檢測器:RI檢測器 管柱溫度:40℃ 注入量:20 μL 分子量標準:標準聚苯乙烯<Weight average molecular weight> The gel permeation chromatography (GPC) measurement was performed using a liquid chromatograph LC-10ATvp manufactured by Shimadzu Corporation. (1) Pretreatment method After dissolving the polyimide resin obtained in Production Examples 1 to 4 in γ-butyrolactone (GBL) to make a 20% by mass solution, it was diluted 100 times with DMF eluent to 0.45 μm The membrane filter is filtered, and the obtained is used as the measurement solution. (2) Measurement conditions Column: TSKgel SuperAWM-H×2+SuperAW2500×1 (6.0 mm I.D.×150 mm×3) Eluent: DMF (add 10 mmol of lithium bromide) Flow rate: 0.6 mL/min Detector: RI detector Column temperature: 40℃ Injection volume: 20 μL Molecular weight standard: standard polystyrene
<醯亞胺化率> 醯亞胺化率係藉由1 H-NMR測定以如下方式求出。 (1)預處理方法 使製造例1~4中所獲得之聚醯亞胺系樹脂溶解於氘化二甲基亞碸(DMSO-d6 )中而製成2質量%溶液,將其作為測定試樣。 (2)測定條件 測定裝置:JEOL製造 400 MHz NMR裝置 JNM-ECZ400S/L1 標準物質:DMSO-d6 (2.5 ppm) 試樣溫度:室溫 累計次數:256次 緩和時間:5秒 (3)醯亞胺化率解析方法 (聚醯亞胺樹脂之醯亞胺化率) 於自包含聚醯亞胺樹脂之測定試樣獲得之1 H-NMR光譜中,將所觀測到之苯質子中源自於醯亞胺化前後未變化之結構之苯質子A之積分值設為IntA 。又,將所觀測到之源自聚醯亞胺樹脂中所殘存之醯胺酸結構之醯胺質子之積分值設為IntB 。自該等積分值並基於以下之式求出聚醯亞胺樹脂之醯亞胺化率。 醯亞胺化率(%)=100×(1-IntB /IntA )<The imidization rate> The imidization rate is determined by 1 H-NMR measurement as follows. (1) Pretreatment method The polyimide resin obtained in Production Examples 1 to 4 was dissolved in deuterated dimethyl sulfide (DMSO-d 6 ) to prepare a 2% by mass solution, which was used as the measurement Sample. (2) Measurement condition measuring device: 400 MHz NMR device JNM-ECZ400S/L1 manufactured by JEOL Standard material: DMSO-d 6 (2.5 ppm) Sample temperature: Room temperature Accumulated times: 256 times Relaxation time: 5 seconds (3) 醯Analysis method of imidization rate (Imidation rate of polyimide resin) In the 1 H-NMR spectrum obtained from a measurement sample containing polyimide resin, the observed benzene protons are derived from The integral value of the benzene proton A of the unchanged structure before and after imidization is set as Int A. In addition, the observed integral value of the amide proton derived from the amide acid structure remaining in the polyimide resin is set to Int B. From these integral values, the imidization rate of the polyimide resin was calculated based on the following formula. The imidization rate (%)=100×(1-Int B /Int A )
(聚醯胺醯亞胺樹脂之醯亞胺化率) 於自包含聚醯胺醯亞胺樹脂之測定試樣獲得之1 H-NMR光譜中,將所觀測到之苯質子中源自於醯亞胺化前後未變化之結構且不會受到源自聚醯胺醯亞胺樹脂中所殘存之醯胺酸結構之結構影響的苯質子C之積分值設為IntC 。又,將所觀測到之苯質子中源自於醯亞胺化前後未變化之結構,且會受到源自聚醯胺醯亞胺樹脂中所殘存之醯胺酸結構之結構影響的苯質子D之積分值設為IntD 。自所獲得之IntC 及IntD 並藉由以下之式求出β值。 β=IntD /IntC 其次,關於複數個聚醯胺醯亞胺樹脂,求出上述式之β值及上述式之聚醯亞胺樹脂之醯亞胺化率,自該等之結果獲得以下之相關式。 醯亞胺化率(%)=k×β+100 上述相關式中,k為常數。 將β代入至相關式中而獲得聚醯胺醯亞胺樹脂之醯亞胺化率(%)。(The imidization rate of polyamide imide resin) In the 1 H-NMR spectrum obtained from a measurement sample containing polyamide imide resin, the observed benzene protons are derived from acetamide The integral value of the benzene proton C, which has the unchanged structure before and after imidization and is not affected by the structure derived from the residual acid structure in the polyamide imide resin, is set to Int C. In addition, among the observed benzene protons, the benzene proton D is derived from the structure unchanged before and after the imidization and is affected by the structure derived from the residual acid structure in the polyimide resin. The integral value is set to Int D. From the obtained Int C and Int D , the β value is calculated by the following formula. β=Int D /Int C Next, for a plurality of polyimide resins, the β value of the above formula and the imidization rate of the polyimide resin of the above formula are obtained, and the following are obtained from the results The correlation formula. The imidization rate (%)=k×β+100 In the above correlation formula, k is a constant. Substitute β into the correlation formula to obtain the imidization rate (%) of the polyimide resin.
<散射光比率(Ts)> 針對實施例及比較例中所獲得之光學膜,依據JIS K 7136,藉由柯尼卡美能達股份有限公司製造之分光測色計CM3700A求出擴散光透過率(Td)(%)。又,依據JIS K 7136,藉由日本電色工業股份有限公司製造之測霧計NDH5000求出全光線透過率(Tt)(%)。將所獲得之Td及Tt代入至散射光比率(Ts)=Td/Tt×100之式中,算出光學膜之散射光比率(Ts)(%)。<Scattered light ratio (Ts)> With respect to the optical films obtained in the Examples and Comparative Examples, the diffuse light transmittance (Td) (%) was determined by a spectrophotometer CM3700A manufactured by Konica Minolta Co., Ltd. according to JIS K 7136. In addition, according to JIS K 7136, the total light transmittance (Tt) (%) is obtained by the haze meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd. Substitute the obtained Td and Tt into the equation of scattered light ratio (Ts)=Td/Tt×100 to calculate the scattered light ratio (Ts) (%) of the optical film.
<拉伸彈性模數> 實施例及比較例中所獲得之光學膜之拉伸彈性模數係依據JIS K 7127,使用電氣機械式萬能試驗機(英斯特朗公司製造),以溫度80℃、試驗速度5 m/min及荷重元5 kN進行拉伸試驗而測得。光學膜係於80℃之環境中靜置5分鐘後開始測定。<Tensile elastic modulus> The tensile elastic modulus of the optical films obtained in the examples and comparative examples is based on JIS K 7127, using an electromechanical universal testing machine (manufactured by Instron) at a temperature of 80°C and a test speed of 5 m/min And the load element is 5 kN to carry on the tensile test and measured. The optical film system was allowed to stand for 5 minutes in an environment of 80°C and then the measurement was started.
<耐彎曲性試驗> 依據JIS K 5600-5-1,藉由Yuasa system股份有限公司製造之小型桌上彎曲試驗機來實施耐彎曲性試驗(彎曲半徑R=1 mm、彎曲次數100次)。針對耐彎曲性試驗後之光學膜,以與上述<散射光比率(Ts)>之測定方法相同之方式測定耐彎曲性試驗後之散射光比率,算出耐彎曲性試驗前後之散射光比率之差之絕對值ΔTs。<Bending resistance test> According to JIS K 5600-5-1, the bending resistance test (bending radius R = 1 mm, bending times 100 times) was carried out with a small desktop bending tester manufactured by Yuasa System Co., Ltd. For the optical film after the bending resistance test, the scattered light ratio after the bending resistance test is measured in the same way as the measurement method of the above-mentioned <scattered light ratio (Ts)>, and the difference between the scattered light ratio before and after the bending resistance test is calculated The absolute value of ΔTs.
<耐折性> 依據ASTM標準D2176-16,以如下方式求出實施例及比較例中之光學膜之彎折次數。使用啞鈴切割機將該光學膜切割成15 mm×100 mm之短條狀。將所切割之光學膜設置於MIT耐折疲勞試驗機(「型號0530」,東洋精機製作所股份有限公司製造)本體,於試驗速度175 cpm、彎折角度135°、荷重0.75 kgf、彎折夾具之半徑R=1 mm之條件下,測定光學膜斷裂之前的向正背方向之往返彎折次數,將其設為彎折次數。<Folding resistance> According to ASTM standard D2176-16, the number of bending times of the optical films in the examples and comparative examples was calculated as follows. Use a dumbbell cutter to cut the optical film into short strips of 15 mm×100 mm. Set the cut optical film on the body of the MIT flexural fatigue testing machine ("Model 0530", manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a test speed of 175 cpm, a bending angle of 135°, a load of 0.75 kgf, and a bending jig. Under the condition of radius R=1 mm, the number of reciprocating bending in the front and back direction before the optical film is broken is measured, and this is the number of bending.
<黃度(YI值)> 使用日本分光股份有限公司製造之紫外可見近紅外分光光度計「V-670」測定實施例及比較例中所獲得之光學膜之黃度(Yellow Index:YI值)。於無樣品之狀態下進行背景測定後,將光學膜設置於樣品保持器,進行對於300~800 nm之光之透過率測定,求出三刺激值(X、Y、Z),基於下述式算出YI值。 YI=100×(1.2769X-1.0592Z)/Y<Yellowness (YI value)> The yellowness (Yellow Index: YI value) of the optical films obtained in the Examples and Comparative Examples was measured using an ultraviolet-visible-near-infrared spectrophotometer "V-670" manufactured by JASCO Corporation. After the background measurement is performed without the sample, the optical film is set in the sample holder, and the transmittance of light from 300 to 800 nm is measured to obtain the tristimulus value (X, Y, Z) based on the following formula Calculate the YI value. YI=100×(1.2769X-1.0592Z)/Y
<厚度> 針對實施例及比較例中所獲得之光學膜,使用測微計(Mitutoyo股份有限公司製造之「ID-C112XBS」)測定10點以上之光學膜之厚度,算出其平均值。將平均值作為光學膜之厚度。<Thickness> With respect to the optical films obtained in the examples and comparative examples, the thickness of the optical film at 10 points or more was measured using a micrometer ("ID-C112XBS" manufactured by Mitutoyo Co., Ltd.), and the average value was calculated. The average value is taken as the thickness of the optical film.
<視認性評估> 將實施例及比較例中所獲得之光學膜切割成10 cm見方。將相同尺寸(10 cm見方)之附黏著層之偏光板之MD方向與所切割之光學膜之MD方向對齊,於所切割之光學膜上貼合附黏著層之偏光板,製作評估用試樣。針對1個實施例及比較例之光學膜,分別製作2個評估用試樣。 將2個評估用試樣中一個評估用試樣以如下方式固定至台之上,即螢光燈位於評估用試樣平面之垂直方向上且上述螢光燈之長度方向相對於評估用試樣之MD方向成為水平。 觀察者自相對於評估用試樣平面之垂直方向傾斜30°之角度以目視觀察映於評估用試樣表面之螢光燈像。 將螢光燈之長度方向自水平變更為垂直,除此以外,以相同之方式將另一評估用試樣固定於台,觀察螢光燈像。 根據觀察結果並基於下述評估基準評估視認性。<Visibility evaluation> The optical films obtained in the examples and comparative examples were cut into 10 cm squares. Align the MD direction of the polarizer with the adhesive layer of the same size (10 cm square) with the MD direction of the cut optical film, and paste the polarizer with the adhesive layer on the cut optical film to make an evaluation sample . For the optical films of 1 Example and Comparative Example, two evaluation samples were prepared respectively. One of the two evaluation samples is fixed to the table in such a way that the fluorescent lamp is located in the vertical direction of the evaluation sample plane and the length direction of the fluorescent lamp is relative to the evaluation sample The MD direction becomes horizontal. The observer visually observes the fluorescent lamp image reflected on the surface of the evaluation sample from an angle of 30° inclined from the vertical direction to the plane of the evaluation sample. The length direction of the fluorescent lamp was changed from horizontal to vertical, except for this, another evaluation sample was fixed to the table in the same manner, and the fluorescent lamp image was observed. The visibility is evaluated based on the observation results and based on the following evaluation criteria.
(視認性之評估基準) ◎:幾乎未視認到螢光燈像之變形。 ○:可視認些許螢光燈像之變形。 △:視認到螢光燈像之變形。 ×:明確地視認到螢光燈像之變形。(Assessment criteria for visibility) ◎: The deformation of the fluorescent lamp image was hardly recognized. ○: Visually recognize the distortion of the fluorescent lamp image. △: Distortion of the fluorescent lamp image is visually recognized. ×: Deformation of the fluorescent lamp image is clearly recognized.
實施例及比較例中所獲得之光學膜於單面具有保護膜,但上述測定及評估係使用已剝離保護膜之狀態之光學膜來實施。The optical films obtained in the examples and comparative examples have a protective film on one side, but the above-mentioned measurement and evaluation are performed using the optical film in a state where the protective film has been peeled off.
[製造例1:聚醯亞胺樹脂(1)之製造] 準備安裝有二氧化矽凝膠管、攪拌裝置及溫度計之可分離式燒瓶與油浴。於該燒瓶內投入4,4'-(六氟亞異丙基)二鄰苯二甲酸酐(6FDA)75.6 g、及2,2'-雙(三氟甲基)-4,4'-二胺基聯苯(TFMB)54.5 g。對其一面以400 rpm攪拌一面加入N,N-二甲基乙醯胺(DMAc)530 g,並持續攪拌至燒瓶之內容物成為均勻之溶液。繼而,一面使用油浴將容器內溫度調整為20~30℃之範圍一面進一步繼續攪拌20小時,進行反應而生成聚醯胺酸。於30分鐘後,將攪拌速度變更為100 rpm。於攪拌20小時後,使反應系溫度恢復至室溫,加入DMAc 650 g而將聚合物濃度調整為10質量%。進而加入吡啶32.3 g、乙酸酐41.7 g,於室溫下攪拌10小時而進行醯亞胺化。自反應容器取出聚醯亞胺清漆。將所獲得之聚醯亞胺清漆滴加至甲醇中而進行再沈澱,將所獲得之粉體進行加熱乾燥而去除溶劑,獲得作為固形物成分之聚醯亞胺樹脂(1)。對所獲得之聚醯亞胺樹脂(1)進行GPC測定,結果重量平均分子量為350,000。又,聚醯亞胺樹脂(1)之醯亞胺化率為98.8%。[Production example 1: Production of polyimide resin (1)] Prepare a separable flask and oil bath equipped with silica gel tube, stirring device and thermometer. Put 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) 75.6 g, and 2,2'-bis(trifluoromethyl)-4,4'-di in the flask Aminodiphenyl (TFMB) 54.5 g. While stirring at 400 rpm, 530 g of N,N-dimethylacetamide (DMAc) was added, and stirring was continued until the contents of the flask became a homogeneous solution. Then, while adjusting the temperature in the container to a range of 20 to 30°C using an oil bath, stirring was continued for a further 20 hours, and the reaction proceeded to produce polyamide acid. After 30 minutes, the stirring speed was changed to 100 rpm. After stirring for 20 hours, the temperature of the reaction system was returned to room temperature, and 650 g of DMAc was added to adjust the polymer concentration to 10% by mass. Furthermore, 32.3 g of pyridine and 41.7 g of acetic anhydride were added, and the mixture was stirred at room temperature for 10 hours to carry out imidization. Take out the polyimide varnish from the reaction vessel. The obtained polyimide varnish was dropped into methanol for reprecipitation, and the obtained powder was heated and dried to remove the solvent to obtain a polyimide resin (1) as a solid component. GPC measurement of the obtained polyimide resin (1) showed that the weight average molecular weight was 350,000. In addition, the polyimide resin (1) had an imidization rate of 98.8%.
[製造例2:聚醯亞胺樹脂(2)之製造] 將反應時間變更為16小時,除此以外,以與製造例1相同之方式製造聚醯亞胺樹脂(2)。所獲得之聚醯亞胺樹脂(2)之重量平均分子量為280,000,醯亞胺化率為98.3%。[Production Example 2: Production of Polyimide Resin (2)] Except that the reaction time was changed to 16 hours, a polyimide resin (2) was produced in the same manner as in Production Example 1. The weight average molecular weight of the obtained polyimide resin (2) was 280,000, and the imidization rate was 98.3%.
[製造例3:聚醯胺醯亞胺樹脂(3)之製造] 於氮氣環境下,於具備攪拌葉之1 L可分離式燒瓶中加入TFMB 45 g(140.52 mmol)及DMAc 768.55 g,一面於室溫下攪拌一面使TFMB溶解於DMAc。其次,於燒瓶中添加6FDA 18.92 g(42.58 mmol),於室溫下攪拌3小時。其後,將4,4'-氧基雙(苯甲醯氯)(OBBC)4.19 g(14.19 mmol)、繼而將對苯二甲醯氯(TPC)17.29 g(85.16 mmol)加入至燒瓶中,於室溫下攪拌1小時。繼而,於燒瓶中加入4-甲基吡啶4.63 g(49.68 mmol)與乙酸酐13.04 g(127.75 mmol),於室溫下攪拌30分鐘後,使用油浴升溫至70℃,進而攪拌3小時,獲得反應液。 將所獲得之反應液冷卻至室溫,以線狀投入至大量甲醇中,取出所析出之沈澱物,利用甲醇浸漬6小時後,利用甲醇洗淨。其次,於100℃下進行沈澱物之減壓乾燥,獲得聚醯胺醯亞胺樹脂(1)。聚醯胺醯亞胺樹脂(1)之重量平均分子量為400,000,醯亞胺化率為98.1%。[Production Example 3: Production of Polyimide Resin (3)] In a nitrogen environment, add 45 g (140.52 mmol) of TFMB and 768.55 g of DMAc to a 1 L separable flask equipped with a stirring blade. While stirring at room temperature, dissolve TFMB in DMAc. Next, 18.92 g (42.58 mmol) of 6FDA was added to the flask, and the mixture was stirred at room temperature for 3 hours. Thereafter, 4.19 g (14.19 mmol) of 4,4'-oxybis(benzyl chloride) (OBBC), and then 17.29 g (85.16 mmol) of terephthalic acid chloride (TPC) were added to the flask, Stir at room temperature for 1 hour. Then, 4.63 g (49.68 mmol) of 4-picoline and 13.04 g (127.75 mmol) of acetic anhydride were added to the flask, and after stirring at room temperature for 30 minutes, the temperature was raised to 70°C using an oil bath, and then stirred for 3 hours to obtain The reaction solution. The obtained reaction solution was cooled to room temperature, and poured into a large amount of methanol in a linear fashion, and the deposited precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Next, the precipitate was dried under reduced pressure at 100°C to obtain a polyimide resin (1). The weight average molecular weight of the polyimide resin (1) is 400,000, and the imidization rate is 98.1%.
[製造例4:聚醯胺醯亞胺樹脂(4)之製造] 於氮氣環境下,於具備攪拌葉之1 L可分離式燒瓶中加入TFMB 45 g(140.52 mmol)及DMAc 768.55 g,一面於室溫下攪拌一面使TFMB溶解於DMAc。其次,於燒瓶中添加6FDA 19.01 g(42.79 mmol),於室溫下攪拌3小時。其後,將OBBC 4.21 g(14.26 mmol)、繼而將TPC 17.30 g(85.59 mmol)加入至燒瓶中,於室溫下攪拌1小時。繼而,於燒瓶中加入4-甲基吡啶4.63 g(49.68 mmol)及乙酸酐13.04 g(127.75 mmol),於室溫下攪拌30分鐘後,使用油浴升溫至70℃,進而攪拌3小時,獲得反應液。 將所獲得之反應液冷卻至室溫,以線狀投入至大量甲醇中,取出所析出之沈澱物,利用甲醇浸漬6小時後,利用甲醇洗淨。其次,於100℃下進行沈澱物之減壓乾燥,獲得聚醯胺醯亞胺樹脂(2)。所獲得之聚醯胺醯亞胺樹脂(2)之重量平均分子量為365,000,醯亞胺化率為98.3%。[Production Example 4: Production of polyimide resin (4)] In a nitrogen environment, add 45 g (140.52 mmol) of TFMB and 768.55 g of DMAc to a 1 L separable flask equipped with a stirring blade. While stirring at room temperature, dissolve TFMB in DMAc. Next, 19.01 g (42.79 mmol) of 6FDA was added to the flask and stirred at room temperature for 3 hours. Thereafter, 4.21 g (14.26 mmol) of OBBC, and 17.30 g (85.59 mmol) of TPC were added to the flask, and the mixture was stirred at room temperature for 1 hour. Then, 4.63 g (49.68 mmol) of 4-picoline and 13.04 g (127.75 mmol) of acetic anhydride were added to the flask, and after stirring at room temperature for 30 minutes, the temperature was raised to 70°C using an oil bath, and then stirred for 3 hours to obtain The reaction solution. The obtained reaction solution was cooled to room temperature, and poured into a large amount of methanol in a linear fashion, and the deposited precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Next, the precipitate was dried under reduced pressure at 100°C to obtain a polyamide imide resin (2). The weight average molecular weight of the obtained polyimide resin (2) was 365,000, and the imidization rate was 98.3%.
[製造例5:清漆(1)~清漆(3)之製造] 以表1所示之組成使聚醯亞胺系樹脂溶解於溶劑中,進而以相對於樹脂之質量為5.7質量%之方式添加Sumika Chemtex股份有限公司製造之Sumisorb 340(UVA)[2-(2-羥基-5-第三辛基苯基)苯并三唑]作為紫外線吸收劑,並攪拌至變得均勻,而獲得清漆(1)~清漆(3)。 再者,表1中,「溶劑」欄之值表示特定溶劑之質量相對於所有溶劑之總質量之比率(質量%)。「聚醯亞胺系樹脂」欄之值表示特定之聚醯亞胺系樹脂之質量相對於所有聚醯亞胺系樹脂之總質量之比率(質量%)。「聚醯亞胺系樹脂」欄之PI-1、PI-2、PAI-1及PAI-2分別表示聚醯亞胺樹脂(1)、聚醯亞胺樹脂(2)、聚醯胺醯亞胺樹脂(1)及聚醯胺醯亞胺樹脂(2)。「添加劑」欄之值表示添加劑之質量相對於樹脂之質量之比率(質量%)。「固形物成分濃度」欄之值表示溶劑以外之所有成分相對於清漆之質量之比率(質量%)。[Production Example 5: Production of varnish (1)-varnish (3)] The polyimide-based resin was dissolved in the solvent with the composition shown in Table 1, and Sumisorb 340 (UVA) manufactured by Sumika Chemtex Co., Ltd. was added at 5.7% by mass relative to the mass of the resin [2-(2 -Hydroxy-5-tertiary octylphenyl) benzotriazole] was used as an ultraviolet absorber, and stirred until it became uniform to obtain varnish (1) to varnish (3). Furthermore, in Table 1, the value in the "solvent" column represents the ratio (mass %) of the mass of the specific solvent to the total mass of all solvents. The value in the "polyimide resin" column represents the ratio (mass %) of the mass of a specific polyimide resin to the total mass of all polyimide resins. PI-1, PI-2, PAI-1, and PAI-2 in the "polyimide resin" column respectively represent polyimide resin (1), polyimide resin (2), polyimide resin Amine resin (1) and polyimide resin (2). The value in the "Additive" column represents the ratio (mass%) of the mass of the additive to the mass of the resin. The value in the "solid content concentration" column represents the ratio (mass%) of all components other than the solvent to the mass of the varnish.
[表1]
[實施例1:光學膜(1)之製造] 藉由流涎成形使清漆(1)於PET(聚對苯二甲酸乙二酯)膜(東洋紡股份有限公司製造之「A4100」,厚度188 μm,厚度分佈±2 μm)上形成塗膜。線速為0.4 m/min。藉由依序於70℃下加熱8分鐘、於100℃下加熱10分鐘、於90℃下加熱8分鐘及於80℃下加熱8分鐘,而使塗膜乾燥,自PET膜剝離塗膜。對於所獲得之原料膜1(寬度700 mm),使用利用夾子作為固持件之拉幅機式乾燥機(1~6室構成)去除溶劑,其後,於所乾燥之膜之單面貼合PET系保護膜,獲得厚度79 μm之光學膜1。原料膜1之乾燥更詳細而言,如下述般進行。將乾燥機內之溫度設定為200℃,以夾子固持寬度為25 mm、膜搬送速度為1.0 m/min、乾燥機入口之膜寬(夾子間距離)與乾燥爐出口之膜寬之比成為1.0之方式進行調整,且將拉幅機式乾燥機之各室中之風速以1室中成為13.5 m/秒、2室中成為13 m/秒、3~6室中成為11 m/秒之方式調整。使膜自夾子脫離後,將夾部切開,於該膜之單面貼合PET系保護膜,捲取於ABS(acrylonitrile-butadiene-styrene,丙烯腈-丁二烯-苯乙烯)製6英吋芯,而獲得光學膜1。[Example 1: Manufacturing of optical film (1)] The varnish (1) is formed into a coating film on a PET (polyethylene terephthalate) film ("A4100" manufactured by Toyobo Co., Ltd., thickness 188 μm, thickness distribution ±2 μm) by casting. The line speed is 0.4 m/min. By heating at 70°C for 8 minutes, heating at 100°C for 10 minutes, heating at 90°C for 8 minutes, and heating at 80°C for 8 minutes, the coating film is dried and peeled from the PET film. For the obtained raw film 1 (width 700 mm), a tenter dryer (consisting of 1 to 6 chambers) using a clip as a holding member was used to remove the solvent, and then PET was laminated on one side of the dried film The protective film is used to obtain optical film 1 with a thickness of 79 μm. In more detail, drying of the raw film 1 is performed as follows. Set the temperature in the dryer to 200°C, the clamp holding width is 25 mm, the film transport speed is 1.0 m/min, and the ratio of the film width at the entrance of the dryer (the distance between the clamps) to the film width at the exit of the drying oven is 1.0 Adjust the wind speed in each chamber of the tenter dryer to 13.5 m/sec in 1 chamber, 13 m/sec in 2 chambers, and 11 m/sec in 3-6 chambers Adjustment. After the film is detached from the clip, cut the clip part, attach a PET-based protective film to one side of the film, and roll it up in ABS (acrylonitrile-butadiene-styrene, acrylonitrile-butadiene-styrene) 6 inches Core, and the optical film 1 is obtained.
[實施例2:光學膜(2)之製造] 將清漆(1)變更為清漆(2),將線速自0.4 m/min變更為0.3 m/min,且對於塗膜之加熱條件,自依序於70℃下8分鐘、於100℃下10分鐘、於90℃下8分鐘及於80℃下8分鐘變更為依序於80℃下10分鐘、於100℃下10分鐘、於90℃下10分鐘及於80℃下10分鐘,除此以外,以與光學膜1之製造方法相同之方式製造厚度49 μm之光學膜2。[Example 2: Manufacturing of optical film (2)] Change the varnish (1) to varnish (2), change the line speed from 0.4 m/min to 0.3 m/min, and for the heating conditions of the coating film, follow the order of 8 minutes at 70°C and 10 at 100°C. Minutes, 8 minutes at 90°C and 8 minutes at 80°C changed to 10 minutes at 80°C, 10 minutes at 100°C, 10 minutes at 90°C, and 10 minutes at 80°C, except for that , The optical film 2 with a thickness of 49 μm is manufactured in the same manner as the manufacturing method of the optical film 1.
[實施例3:光學膜(3)之製造] 將清漆(1)變更為清漆(3),將線速自0.4 m/min變更為0.2 m/min,除此以外,以與光學膜1之製造方法相同之方式獲得厚度79 μm之光學膜3。[Example 3: Manufacturing of optical film (3)] The varnish (1) was changed to varnish (3), and the line speed was changed from 0.4 m/min to 0.2 m/min. Otherwise, the optical film 3 with a thickness of 79 μm was obtained in the same manner as the manufacturing method of the optical film 1 .
[實施例4:光學膜(4)之製造] 將清漆(1)變更為清漆(4),將線速自0.4 m/min變更為0.2 m/min,且將塗膜之加熱條件變更為如下,即依序於90℃下8分鐘、於100℃下10分鐘、於90℃下8分鐘及於80℃下8分鐘,除此以外,以與光學膜1之製造方法相同之方式獲得厚度79 μm之光學膜4。[Example 4: Manufacturing of optical film (4)] Change varnish (1) to varnish (4), change the line speed from 0.4 m/min to 0.2 m/min, and change the heating conditions of the coating film to the following, that is, at 90°C for 8 minutes and at 100 Except for 10 minutes at °C, 8 minutes at 90 °C, and 8 minutes at 80 °C, an optical film 4 with a thickness of 79 μm was obtained in the same manner as the manufacturing method of the optical film 1.
[比較例1] 準備聚醯亞胺膜(宇部興產股份有限公司製造之「UPILEX」,厚度50 μm)作為光學膜5。[Comparative Example 1] A polyimide film ("UPILEX" manufactured by Ube Industries Co., Ltd., thickness 50 μm) was prepared as the optical film 5.
將實施例1~4及比較例1中所獲得之光學膜之全光線透過率Tt(%)、擴散光透過率Td(%)、散射光比率Ts(%)、拉伸彈性模數(MPa)、耐彎曲性試驗前後之散射光比率之差之絕對值ΔTs(%)、YI、耐折性(次)及視認性評估之結果示於表2。The total light transmittance Tt (%), diffuse light transmittance Td (%), scattered light ratio Ts (%), and tensile modulus (MPa) of the optical films obtained in Examples 1 to 4 and Comparative Example 1 ), the absolute value of the difference of the scattered light ratio before and after the bending resistance test ΔTs (%), YI, folding resistance (times) and the results of the visibility evaluation are shown in Table 2.
[表2]
如表2所示,確認到散射光比率(Ts)為0~0.35%之範圍之實施例1~4之光學膜與散射光比率超過0.35%之比較例1之光學膜相比,視認性評估之結果較良好。又,亦確認到實施例1~4之光學膜具有優異之拉伸彈性模數及耐折性以及低黃度。因此,實施例1~4之光學膜之廣角方向之視認性優異,並且亦具有優異之拉伸彈性模數等。As shown in Table 2, it was confirmed that the optical films of Examples 1 to 4 in which the scattered light ratio (Ts) was in the range of 0 to 0.35% were compared with the optical film of Comparative Example 1 in which the scattered light ratio exceeded 0.35%. The result is relatively good. In addition, it was also confirmed that the optical films of Examples 1 to 4 had excellent tensile modulus of elasticity, folding resistance, and low yellowness. Therefore, the optical films of Examples 1 to 4 have excellent visibility in the wide-angle direction, and also have excellent tensile modulus and the like.
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CN110967780A (en) | 2020-04-07 |
KR20200037057A (en) | 2020-04-08 |
KR102108371B1 (en) | 2020-05-08 |
JP6670967B1 (en) | 2020-03-25 |
JP2020056990A (en) | 2020-04-09 |
KR20200051542A (en) | 2020-05-13 |
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