TW202346089A - Optical laminate and display system - Google Patents
Optical laminate and display system Download PDFInfo
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- TW202346089A TW202346089A TW112109164A TW112109164A TW202346089A TW 202346089 A TW202346089 A TW 202346089A TW 112109164 A TW112109164 A TW 112109164A TW 112109164 A TW112109164 A TW 112109164A TW 202346089 A TW202346089 A TW 202346089A
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- adhesive layer
- adhesive
- optical
- optical laminate
- meth
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Images
Classifications
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- 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
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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
- G02F1/13363—Birefringent elements, e.g. for optical compensation
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- G—PHYSICS
- G02—OPTICS
- 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
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
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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
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
- H04N13/00—Stereoscopic video systems; Multi-view video systems; Details thereof
- H04N13/30—Image reproducers
- H04N13/332—Displays for viewing with the aid of special glasses or head-mounted displays [HMD]
- H04N13/344—Displays for viewing with the aid of special glasses or head-mounted displays [HMD] with head-mounted left-right displays
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
- H04N13/00—Stereoscopic video systems; Multi-view video systems; Details thereof
- H04N13/30—Image reproducers
- H04N13/346—Image reproducers using prisms or semi-transparent mirrors
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
- H04N5/00—Details of television systems
- H04N5/64—Constructional details of receivers, e.g. cabinets or dust covers
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
- H04N5/00—Details of television systems
- H04N5/66—Transforming electric information into light information
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
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- H—ELECTRICITY
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- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
- H05B33/24—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers of metallic reflective layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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Abstract
Description
本發明涉及光學積層體及使用該光學積層體之顯示系統。The present invention relates to an optical laminated body and a display system using the optical laminated body.
以液晶顯示裝置及電致發光(EL)顯示裝置(例如有機EL顯示裝置)為代表之影像顯示裝置急速普及。影像顯示裝置中，為了實現影像顯示、提高影像顯示之性能，一般係使用偏光構件、相位差構件等光學構件(例如參照專利文獻1)。Image display devices represented by liquid crystal display devices and electroluminescence (EL) display devices (such as organic EL display devices) are rapidly gaining popularity. In image display devices, in order to realize image display and improve image display performance, optical members such as polarizing members and phase difference members are generally used (for example, see Patent Document 1).
近年來，有開發出影像顯示裝置之新用途。例如，有開始將用以實現Virtual Reality(VR)之附顯示器之護目鏡(VR護目鏡)產品化。有檢討將VR護目鏡利用在各種情況下，因而相較於應用於以往之影像顯示裝置的光學積層體，對於在高溫及/或高濕環境等嚴酷環境下之穩定性這點有更高的要求。 先前技術文獻 專利文獻 In recent years, new uses for image display devices have been developed. For example, goggles with a display (VR goggles) for realizing Virtual Reality (VR) have begun to be commercialized. There are reviews for using VR goggles in various situations. Therefore, compared with optical laminates used in conventional image display devices, they have higher stability in harsh environments such as high temperature and/or high humidity environments. Require. Prior technical literature patent documents
專利文獻1：日本專利特開2021-103286號公報Patent Document 1: Japanese Patent Application Publication No. 2021-103286
發明欲解決之課題 本發明主要目的在於提供一種即便在嚴酷環境下光學特性仍穩定之光學積層體。 The problem to be solved by the invention The main object of the present invention is to provide an optical laminate with stable optical properties even under harsh environments.
用以解決課題之手段 [1]本發明實施形態之光學積層體，包含至少1個光學構件與至少1層黏著劑層；令上述光學積層體所含之上述黏著劑層之總數為N時，N/2以上之黏著劑層為滿足下述關係之黏著劑層A：從20℃升溫至30℃時之線膨脹係數α1與從30℃降溫至20℃時之線膨脹係數α2滿足0.8≦α1/α2≦1.2之關係。 [2]如上述[1]之光學積層體中，上述黏著劑層A之厚度亦可為1µm以上且15µm以下。 [3]如上述[1]或[2]之光學積層體之厚度亦可為100µm以上且300µm以下。 [4]如上述[1]至[3]中任一項之光學積層體，亦可依序具有第一黏著劑層、偏光構件、第二黏著劑層、第一相位差構件、第三黏著劑層及保護構件；並且選自上述第一、第二及第三黏著劑層中之2層以上亦可為上述黏著劑層A。 [5]如上述[4]之光學積層體中，上述第一相位差構件亦可包含λ/4構件。 [6]上述[4]或[5]之光學積層體中，上述保護構件亦可具有表面處理層。 [7]如上述[1]至[6]中任一項之光學積層體中，構成上述黏著劑層A之黏著劑組成物亦可包含具有150萬以上之重量平均分子量的(甲基)丙烯酸系聚合物。 [8]本發明實施形態之顯示系統包含如上述[1]至[7]中任一項之光學積層體。 [9]如上述[8]之顯示系統亦可具備：顯示元件，其具有顯示面，該顯示面會將顯示影像之光隔著偏光構件而朝前方射出；反射型偏光構件，配置於上述顯示元件之前方，且會反射從上述顯示元件射出之光；第一透鏡部，配置於上述顯示元件與上述反射型偏光構件之間的光路上；半反射鏡，配置於上述顯示元件與上述第一透鏡部之間，且該半反射鏡會將從上述顯示元件射出之光透射，並將上述反射型偏光構件所反射之光朝向上述反射型偏光構件反射；第1λ/4構件，配置於上述顯示元件與上述半反射鏡之間的光路上；及第2λ/4構件，配置於上述半反射鏡與上述反射型偏光構件之間的光路上；且如上述[5]之光學積層體亦可以使上述顯示元件與上述第1λ/4板設置成一體之方式，配置於上述半反射鏡之上述顯示元件側。 means to solve problems [1] The optical laminated body according to the embodiment of the present invention includes at least one optical member and at least one adhesive layer; when the total number of the above-mentioned adhesive layers contained in the above-mentioned optical laminated body is N, the adhesiveness of N/2 or more The adhesive layer is an adhesive layer A that satisfies the following relationship: the linear expansion coefficient α1 when the temperature rises from 20°C to 30°C and the linear expansion coefficient α2 when the temperature drops from 30°C to 20°C satisfies the relationship of 0.8≦α1/α2≦1.2 . [2] In the optical laminate of [1] above, the thickness of the adhesive layer A may be 1 μm or more and 15 μm or less. [3] The thickness of the optical laminate described in [1] or [2] above may be 100µm or more and 300µm or less. [4] The optical laminate according to any one of the above [1] to [3] may also have a first adhesive layer, a polarizing member, a second adhesive layer, a first phase difference member, and a third adhesive layer in this order. agent layer and protective member; and two or more layers selected from the above-mentioned first, second and third adhesive layers can also be the above-mentioned adhesive layer A. [5] In the optical laminate according to [4] above, the first phase difference member may include a λ/4 member. [6] In the optical laminate of [4] or [5] above, the protective member may have a surface treatment layer. [7] In the optical laminate according to any one of [1] to [6] above, the adhesive composition constituting the adhesive layer A may contain (meth)acrylic acid having a weight average molecular weight of 1.5 million or more. Polymer. [8] The display system according to the embodiment of the present invention includes the optical layered body according to any one of the above [1] to [7]. [9] The display system of [8] above may also include: a display element having a display surface that emits light of a displayed image forward through a polarizing member; and a reflective polarizing member disposed on the display in front of the element, and can reflect the light emitted from the above-mentioned display element; a first lens portion is arranged on the optical path between the above-mentioned display element and the above-mentioned reflective polarizing member; a half mirror is arranged between the above-mentioned display element and the above-mentioned first between the lens parts, and the half-mirror transmits the light emitted from the display element and reflects the light reflected by the reflective polarizing member toward the reflective polarizing member; the 1st λ/4 member is arranged on the display The optical path between the element and the above-mentioned half-reflecting mirror; and the 2λ/4 member is arranged on the optical path between the above-mentioned half-reflecting mirror and the above-mentioned reflective polarizing member; and the optical laminate as described in [5] above can also be used. The display element and the first λ/4 plate are integrated and arranged on the display element side of the half mirror.
發明效果 本發明實施形態中，係於光學積層體所含之黏著劑層的半數以上使用滿足下述關係之黏著劑層A：在20℃~30℃之範圍內升溫時之線膨脹係數α1與降溫時之線膨脹係數α2滿足0.8≦α1/α2≦1.2之關係。藉此，可獲得即使在嚴酷環境下光學特性仍穩定之光學積層體。 Invention effect In an embodiment of the present invention, an adhesive layer A that satisfies the following relationship is used for more than half of the adhesive layers contained in the optical laminate: the linear expansion coefficient α1 when the temperature rises in the range of 20°C to 30°C and the linear expansion coefficient α1 when the temperature drops. The linear expansion coefficient α2 satisfies the relationship of 0.8≦α1/α2≦1.2. This makes it possible to obtain an optical laminate with stable optical properties even under harsh environments.
以下參照圖式針對本發明實施形態進行說明，惟本發明不受該等實施形態所限。又，為了更明確說明圖式，相較於實施形態，有將各部分之寬度、厚度、形狀等示意顯示之情形，但僅為一例，非用以限定解釋本發明。又，本說明書中，表示數值範圍之「~」包含其上限及下限之數值；「(甲基)丙烯酸」意指「丙烯酸及/或甲基丙烯酸」。Embodiments of the present invention will be described below with reference to the drawings, but the present invention is not limited to these embodiments. In addition, in order to explain the drawings more clearly, the width, thickness, shape, etc. of each part may be schematically shown compared with the embodiment. However, this is only an example and is not intended to limit the interpretation of the present invention. In addition, in this specification, "~" indicating a numerical range includes the upper and lower limits thereof; "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid".
(用語及符號之定義) 本說明書中之用語及符號之定義如下。 (1)折射率(nx、ny、nz) 「nx」為面內折射率達最大之方向(亦即慢軸方向)的折射率，「ny」為在面內與慢軸正交之方向(亦即快軸方向)的折射率，而「nz」為厚度方向的折射率。 (2)面內相位差(Re) 「Re(λ)」係在23℃下以波長λnm之光測定之面內相位差。例如，「Re(550)」係於23℃下以波長550nm之光測定之面內相位差。Re(λ)可於令層(薄膜)之厚度為d(nm)時，藉由式：Re(λ)=(nx-ny)×d求出。 (3)厚度方向之相位差(Rth) 「Rth(λ)」係於23℃下以波長λnm之光測定之厚度方向之相位差。例如，「Rth(550)」係於23℃下以波長550nm之光測定之厚度方向之相位差。Rth(λ)可於令層(薄膜)厚度為d(nm)時，藉由式：Rth(λ)=(nx-nz)×d求出。 (4)Nz係數 Nz係數可藉由Nz=Rth/Re求出。 (5)角度 本說明書中提及角度時，該角度包含相對於基準方向往順時針方向及逆時針方向兩方向。因此，例如「45°」係往順時針方向45°或往逆時針方向45°。又，本說明書中，「大致平行」包含0°±10°之範圍內的情況，例如0°±5°、宜為0°±3°、較宜為0°±1°之範圍內；「大致正交」包含90°±10°之範圍內的情況，例如90°±5°、宜為90°±3°、較宜為90°±1°之範圍內。 (Definition of terms and symbols) The definitions of terms and symbols in this manual are as follows. (1)Refractive index (nx, ny, nz) "nx" is the refractive index in the direction where the in-plane refractive index reaches the maximum (that is, the slow axis direction), "ny" is the refractive index in the direction that is orthogonal to the slow axis in the plane (that is, the fast axis direction), and " nz" is the refractive index in the thickness direction. (2) In-plane phase difference (Re) "Re(λ)" is the in-plane phase difference measured with light of wavelength λnm at 23°C. For example, "Re(550)" is the in-plane phase difference measured using light with a wavelength of 550 nm at 23°C. Re(λ) can be calculated by the formula: Re(λ)=(nx-ny)×d when the thickness of the layer (thin film) is d(nm). (3) Phase difference in thickness direction (Rth) "Rth(λ)" is the phase difference in the thickness direction measured with light of wavelength λnm at 23°C. For example, "Rth(550)" is the phase difference in the thickness direction measured at 23°C using light with a wavelength of 550 nm. Rth(λ) can be calculated by the formula: Rth(λ)=(nx-nz)×d when the layer (film) thickness is d(nm). (4)Nz coefficient The Nz coefficient can be found by Nz=Rth/Re. (5)Angle When an angle is mentioned in this specification, the angle includes both clockwise and counterclockwise directions relative to the reference direction. So, for example, "45°" means 45° clockwise or 45° counterclockwise. In addition, in this specification, "approximately parallel" includes the situation within the range of 0°±10°, for example, 0°±5°, preferably 0°±3°, and more preferably within the range of 0°±1°; " "Approximately orthogonal" includes the situation within the range of 90°±10°, for example, 90°±5°, preferably 90°±3°, and more preferably within the range of 90°±1°.
A.光學積層體 本發明實施形態之光學積層體包含至少1個光學構件與至少1層黏著劑層。令上述光學積層體所含之黏著劑層之總數為N時，N/2以上之黏著劑層為滿足下述關係之黏著劑層A：從20℃升溫至30℃時之線膨脹係數α1與從30℃降溫至20℃時之線膨脹係數α2滿足0.8≦α1/α2≦1.2之關係。α1/α2小於0.8或大於1.2之黏著劑層有在升溫時與降溫時變形率之差大的傾向，從而反覆溫度變化會造成變形量變大，而有光學積層體之光學特性改變之情形，結果應用作為附顯示器之護目鏡的構成構件時，有對其顯示特性造成影響之情形。相對於此，藉由以預定比率以上使用滿足0.8≦α1/α2≦1.2之關係的黏著劑層，可抑制因黏著劑層之變形造成光學積層體之光學特性的變化。 A. Optical laminated body The optical laminate according to the embodiment of the present invention includes at least one optical member and at least one adhesive layer. When the total number of adhesive layers contained in the above-mentioned optical laminate is N, the adhesive layers above N/2 are adhesive layers A that satisfy the following relationship: linear expansion coefficient α1 when the temperature rises from 20°C to 30°C and The linear expansion coefficient α2 when cooling from 30℃ to 20℃ satisfies the relationship of 0.8≦α1/α2≦1.2. The adhesive layer with α1/α2 less than 0.8 or more than 1.2 tends to have a large difference in deformation rate between heating and cooling. Repeated temperature changes will cause the deformation to increase, and the optical properties of the optical laminate may change. As a result, When used as a component of goggles with a display, the display characteristics may be affected. On the other hand, by using an adhesive layer satisfying the relationship of 0.8≦α1/α2≦1.2 at a predetermined ratio or more, it is possible to suppress changes in the optical properties of the optical laminate due to deformation of the adhesive layer.
光學積層體所含之光學構件可舉例如吸收型偏光構件、反射型偏光構件、相位差構件等。Examples of the optical member included in the optical laminate include an absorptive polarizing member, a reflective polarizing member, a phase difference member, and the like.
光學積層體所含之黏著劑層的總數N為1以上，宜為2以上，較宜為3以上，且例如為6以下。在一實施形態中，光學積層體所含之黏著劑層的總數N為2以上且5以下，宜為3或4。光學積層體例如於最外層具有黏著劑層，且可透過該黏著劑層貼附於相鄰接之構件上。The total number N of adhesive layers contained in the optical laminate is 1 or more, preferably 2 or more, more preferably 3 or more, and for example, 6 or less. In one embodiment, the total number N of adhesive layers contained in the optical laminate is 2 or more and 5 or less, preferably 3 or 4. For example, the optical laminate has an adhesive layer on the outermost layer, and can be attached to adjacent members through the adhesive layer.
黏著劑層A之數量相對於光學積層體所含之黏著劑層的總數的比率為1/2以上，宜為2/3以上，較宜為3/4以上，亦可為1。The ratio of the number of adhesive layers A to the total number of adhesive layers contained in the optical laminate is 1/2 or more, preferably 2/3 or more, more preferably 3/4 or more, and may also be 1.
當然，因黏著劑層A之數量為整數，故黏著劑層之總數N為奇數時，黏著劑層A之數量為N/2以上且N以下之整數。具體上，N為3時，黏著劑層A之數量為2以上且3以下之整數，即2或3；N為4時，黏著劑層A之數量為2以上且4以下之整數，即2、3或4。此外，在本說明書中，係將滿足下述關係之黏著劑層全部稱為黏著劑層A：從20℃升溫至30℃時之線膨脹係數α1與從30℃降溫至20℃時之線膨脹係數α2滿足0.8≦α1/α2≦1.2之關係。因此，光學積層體所含之複數層黏著劑層為黏著劑層A時，該複數層黏著劑層只要滿足0.8≦α1/α2≦1.2之關係，便無須以具有相同組成之黏著劑組成物形成成相同厚度，亦可以具有不同組成之黏著劑組成物形成成相同或不同厚度。Of course, since the number of adhesive layers A is an integer, when the total number of adhesive layers N is an odd number, the number of adhesive layers A is an integer between N/2 and N. Specifically, when N is 3, the number of adhesive layers A is an integer from 2 to 3, that is, 2 or 3; when N is 4, the number of adhesive layers A is an integer from 2 to 4, that is, 2 , 3 or 4. In addition, in this specification, all adhesive layers that satisfy the following relationship are called adhesive layers A: linear expansion coefficient α1 when the temperature rises from 20°C to 30°C and linear expansion when the temperature drops from 30°C to 20°C. The coefficient α2 satisfies the relationship of 0.8≦α1/α2≦1.2. Therefore, when the plurality of adhesive layers contained in the optical laminate is adhesive layer A, as long as the plurality of adhesive layers satisfy the relationship of 0.8≦α1/α2≦1.2, they do not need to be formed from adhesive compositions with the same composition. The thicknesses may be the same, or adhesive compositions with different compositions may be formed into the same or different thicknesses.
光學積層體之厚度例如為100µm以上且300µm以下，宜為110µm以上且250µm以下，較宜為120µm以上且200µm以下。以所述整體厚度小的光學積層體來說，因黏著劑層之變形的影響大，故可適宜獲得本發明之效果，即藉由使用升溫時與降溫時變形率之差小的黏著劑層所帶來之效果。The thickness of the optical laminated body is, for example, 100 µm or more and 300 µm or less, preferably 110 µm or more and 250 µm or less, more preferably 120 µm or more and 200 µm or less. For the optical laminate with a small overall thickness, the effect of the deformation of the adhesive layer is large, so the effects of the present invention can be appropriately obtained by using an adhesive layer with a small difference in deformation rate between heating and cooling. The effects brought about.
在一實施形態中，黏著劑層A之厚度例如為1µm以上且15µm以下，宜為2µm以上且小於10µm，較宜為3µm以上且8µm以下。藉由使用升溫時與降溫時變形率之差小且厚度小的黏著劑層，可適宜獲得光學特性等之穩定性優異的光學積層體。In one embodiment, the thickness of the adhesive layer A is, for example, 1 µm or more and 15 µm or less, preferably 2 µm or more and less than 10 µm, more preferably 3 µm or more and 8 µm or less. By using an adhesive layer that has a small difference in deformation rate between heating and cooling and a small thickness, it is possible to suitably obtain an optical laminate with excellent stability such as optical properties.
以下，一邊參照圖式一邊具體說明本發明實施形態之光學積層體。Hereinafter, the optical laminated body according to the embodiment of the present invention will be described in detail with reference to the drawings.
A-1.實施形態1
圖1A係本發明一實施形態之光學積層體的概略截面圖。圖1A所示之光學積層體100a依序具有第一黏著劑層a1、偏光構件10、第二黏著劑層a2、第一相位差構件20、第三黏著劑層a3及保護構件30。具體而言，偏光構件10與第一相位差構件20係透過第二黏著劑層a2貼合，且第一相位差構件20與保護構件30係透過第三黏著劑層a3貼合。第一黏著劑層a1係用以與鄰接光學積層體100a本身之構件(例如構成附顯示器之護目鏡的其他構件)貼合的黏著劑層，其表面亦可在供於使用前之期間被剝離襯材保護著。光學積層體100a中，黏著劑層之總數為3，且其中2層以上為上述黏著劑層A。
A-1. Embodiment 1
FIG. 1A is a schematic cross-sectional view of an optical laminate according to an embodiment of the present invention. The optical laminated
光學積層體100a之厚度例如為100µm以上且300µm以下，宜為110µm以上且250µm以下，較宜為120µm以上且200µm以下。The thickness of the optical
＜黏著劑層＞
光學積層體100a具有合計3層之黏著劑層(第一黏著劑層a1、第二黏著劑層a2及第三黏著劑層a3)，且其中至少2層為黏著劑層A，宜全部為黏著劑層A。
＜Adhesive layer＞
The
3層黏著劑層中之2層為黏著劑層A時，第一黏著劑層a1及第二黏著劑層a2宜為黏著劑層A。將光學積層體應用於VR護目鏡時，將對溫度變化之形狀穩定性高之黏著劑層A配置於顯示元件及第一相位差構件20附近，藉此可適宜獲得本發明之效果。When two of the three adhesive layers are adhesive layers A, the first adhesive layer a1 and the second adhesive layer a2 are preferably adhesive layers A. When the optical laminate is applied to VR goggles, the effects of the present invention can be suitably obtained by arranging the adhesive layer A with high shape stability against temperature changes near the display element and the first
如上述，黏著劑層A從20℃升溫至30℃時的線膨脹係數α1與從30℃降溫至20℃時的線膨脹係數α2代表上係滿足0.8≦α1/α2≦1.2之關係，宜滿足0.85≦α1/α2≦1.15，較宜滿足0.9≦α1/α2≦1.1之關係。藉由使用所述黏著劑層A，可獲得即使在嚴酷環境下光學特性之穩定性仍優異之光學積層體。黏著劑層A之α1及α2各自只要可獲得本發明之效果則無限制，亦可為任意值。黏著劑層A之α1例如可為5.0×10 -4/℃以上且7.0×10 -4/℃以下。黏著劑層A之α2例如可為5.0×10 -4/℃以上且7.0×10 -4/℃以下，且例如可為6.0×10 -4/℃以上且7.0×10 -4/℃以下。 As mentioned above, the linear expansion coefficient α1 of the adhesive layer A when the temperature rises from 20°C to 30°C and the linear expansion coefficient α2 when the temperature drops from 30°C to 20°C satisfy the relationship of 0.8≦α1/α2≦1.2, which should be satisfied 0.85≦α1/α2≦1.15, it is better to satisfy the relationship of 0.9≦α1/α2≦1.1. By using the adhesive layer A, an optical laminate having excellent stability of optical properties even under harsh environments can be obtained. Each of α1 and α2 of the adhesive layer A is not limited as long as the effect of the present invention can be obtained, and may be any value. α1 of the adhesive layer A can be, for example, 5.0×10 -4 /°C or more and 7.0×10 -4 /°C or less. α2 of the adhesive layer A may be, for example, 5.0×10 -4 /°C or more and 7.0×10 -4 /°C or less, and may be, for example, 6.0×10 -4 /°C or more and 7.0×10 -4 /°C or less.
黏著劑層A從60℃升溫至70℃時的線膨脹係數β1與從70℃降溫至60℃時的線膨脹係數β2例如滿足1.0≦β1/β2≦1.5之關係，宜滿足1.05≦β1/β2≦1.45，較宜滿足1.1≦β1/β2≦1.4之關係。藉由使用所述黏著劑層，可獲得即使在嚴酷環境下光學特性之穩定性仍優異之光學積層體。黏著劑層A之β1及β2各自只要可獲得本發明之效果則無限制，亦可為任意值。黏著劑層A之β1例如可為8.0×10 -4/℃以上且9.0×10 -4/℃以下。黏著劑層A之β2例如可為6.0×10 -4/℃以上且7.0×10 -4/℃以下。 The linear expansion coefficient β1 of the adhesive layer A when the temperature rises from 60°C to 70°C and the linear expansion coefficient β2 when the temperature drops from 70°C to 60°C satisfy the relationship of 1.0≦β1/β2≦1.5, for example, and it is appropriate to satisfy the relationship of 1.05≦β1/β2 ≦1.45, it is better to satisfy the relationship of 1.1≦β1/β2≦1.4. By using the adhesive layer, an optical laminate having excellent stability of optical properties even under harsh environments can be obtained. Each of β1 and β2 of the adhesive layer A is not limited as long as the effect of the present invention can be obtained, and may be any value. β1 of the adhesive layer A can be, for example, 8.0×10 -4 /°C or more and 9.0×10 -4 /°C or less. β2 of the adhesive layer A can be, for example, 6.0×10 -4 /°C or more and 7.0×10 -4 /°C or less.
黏著劑層A在25℃下之儲存彈性模數例如為5×10 4Pa以上，宜為10×10 4Pa以上，較宜為12×10 4Pa以上，且例如為20×10 4Pa以下，宜為15×10 4Pa以下。藉由使用升溫時與降溫時之變形率之差小且具有所述儲存彈性模數之黏著劑層，則可獲得即便在嚴酷環境下光學特性之穩定性仍優異之光學積層體。儲存彈性模數例如可藉由使用動態黏彈性測定測定裝置(「Advanced Rheometric Expansion System(ARES)」，Rheometric Scientific公司製)之動態黏彈性測定(例如平行板(8.0mmφ)、扭轉模式、頻率範圍1Hz之測定條件)來求算。 The storage elastic modulus of the adhesive layer A at 25°C is, for example, 5×10 4 Pa or more, preferably 10×10 4 Pa or more, more preferably 12×10 4 Pa or more, and, for example, 20×10 4 Pa or less. , should be below 15×10 4 Pa. By using an adhesive layer that has a small difference in deformation rate between heating and cooling and has the storage elastic modulus, it is possible to obtain an optical laminate that has excellent stability in optical properties even under harsh environments. The elastic modulus can be stored, for example, by using a dynamic viscoelasticity measurement device ("Advanced Rheometric Expansion System (ARES)", manufactured by Rheometric Scientific) (e.g., parallel plate (8.0 mmφ), torsional mode, frequency range Calculate according to the measurement conditions of 1Hz).
黏著劑層A可藉由任意適當之黏著劑組成物形成。形成黏著劑層A之黏著劑組成物可列舉：丙烯酸系黏著劑組成物、橡膠系黏著劑組成物、聚矽氧系黏著劑組成物、聚酯系黏著劑組成物、胺甲酸酯系黏著劑組成物、環氧系黏著劑組成物及聚醚系黏著劑組成物。藉由調整形成黏著劑組成物之基底樹脂的單體的種類、數量、組合及摻混比、以及交聯劑的摻混量、反應溫度、反應時間等，可調製出具有符合目的之所期望特性的黏著劑組成物。黏著劑組成物之基底聚合物可單獨使用，亦可組合二種以上來使用。黏著劑層宜以包含(甲基)丙烯酸系聚合物作為基底聚合物之丙烯酸系黏著劑組成物構成。The adhesive layer A can be formed by any suitable adhesive composition. The adhesive compositions forming the adhesive layer A include: acrylic adhesive compositions, rubber adhesive compositions, silicone adhesive compositions, polyester adhesive compositions, and urethane adhesive compositions. agent composition, epoxy adhesive composition and polyether adhesive composition. By adjusting the type, quantity, combination and blending ratio of the monomers that form the base resin of the adhesive composition, as well as the blending amount of the cross-linking agent, reaction temperature, reaction time, etc., the desired adhesive composition can be prepared to suit the purpose. Characteristic adhesive composition. The base polymer of the adhesive composition can be used alone or in combination of two or more types. The adhesive layer is preferably composed of an acrylic adhesive composition containing a (meth)acrylic polymer as a base polymer.
在一實施形態中，構成上述(甲基)丙烯酸系聚合物之單體成分包含通式CH 2=C(R 1)COOR 2(惟，R 1為氫或甲基，R 2係碳數2~14、宜為碳數3~12、較宜為碳數4~9烷基)所示之(甲基)丙烯酸系單體作為主成分。 In one embodiment, the monomer components constituting the (meth)acrylic polymer include the general formula CH 2 =C(R 1 )COOR 2 (but R 1 is hydrogen or methyl, and R 2 has a carbon number of 2 ~14, preferably a (meth)acrylic monomer represented by a carbon number of 3 to 12, more preferably a carbon number of 4 to 9 alkyl group) as the main component.
通式CH 2=C(R 1)COOR 2所示之(甲基)丙烯酸系單體可列舉例如：(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸正十二酯、(甲基)丙烯酸異肉豆蔻酯)、(甲基)丙烯酸正十三酯、(甲基)丙烯酸正十四酯、(甲基)丙烯酸十八酯、(甲基)丙烯酸異十八酯、(甲基)丙烯酸苯氧乙酯等。其中，又可適宜使用(甲基)丙烯酸正丁酯、(甲基)丙烯酸2-乙基己酯等。通式CH 2=C(R 1)COOR 2所示之(甲基)丙烯酸系單體可單獨使用，亦可混合2種以上來使用。 Examples of the (meth)acrylic monomer represented by the general formula CH 2 =C(R 1 )COOR 2 include: (meth)ethyl acrylate, n-butyl (meth)acrylate, and di(meth)acrylate. Grade butyl ester, tertiary butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, ( Heptyl methacrylate, isopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, (meth) n-nonyl acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, isomyristyl (meth)acrylate Ester), n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, stearyl (meth)acrylate, isoctadecyl (meth)acrylate, phenoxyethyl (meth)acrylate Ester etc. Among these, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. can be suitably used. The (meth)acrylic monomer represented by the general formula CH 2 =C(R 1 )COOR 2 can be used alone, or two or more types can be mixed and used.
構成(甲基)丙烯酸系聚合物之單體成分中，通式CH 2=C(R 1)COOR 2所示之(甲基)丙烯酸系單體之含有比率例如為50重量%~98重量%，宜為60重量%~90重量%，較宜為70重量%~80重量%。 Among the monomer components constituting the (meth)acrylic polymer, the content ratio of the (meth)acrylic monomer represented by the general formula CH 2 =C(R 1 )COOR 2 is, for example, 50% by weight to 98% by weight. , preferably 60% to 90% by weight, more preferably 70% to 80% by weight.
構成(甲基)丙烯酸系聚合物之單體成分宜更包含含氮單體。上述單體成分中，含氮單體之含有比率例如為0.1重量%~35重量%，宜為3重量%~30重量%，較宜為5重量%~25重量%。含氮單體之含有比率若在上述範圍內，便可獲得在加熱環境下及/或高濕環境下之耐久性優異之黏著劑層。The monomer components constituting the (meth)acrylic polymer preferably further include nitrogen-containing monomers. Among the above monomer components, the content ratio of the nitrogen-containing monomer is, for example, 0.1% to 35% by weight, preferably 3% to 30% by weight, and more preferably 5% to 25% by weight. If the content ratio of the nitrogen-containing monomer is within the above range, an adhesive layer having excellent durability in a heated environment and/or a high-humidity environment can be obtained.
含氮單體係在單體結構中含有1個以上氮原子之聚合性單體，可適宜例示含醯亞胺基單體、含醯胺基單體等。其中，較宜為含醯胺基單體。上述單體成分中，含醯胺基單體之含有比率例如為3重量%~15重量%，宜為5重量%~10重量%。含氮單體可單獨使用，亦可混合2種以上來使用。The nitrogen-containing monomer system is a polymerizable monomer containing one or more nitrogen atoms in the monomer structure, and suitable examples include amide imine group-containing monomers, amide group-containing monomers, and the like. Among them, amide group-containing monomers are preferred. Among the above monomer components, the content ratio of the amide group-containing monomer is, for example, 3% to 15% by weight, preferably 5% to 10% by weight. The nitrogen-containing monomer can be used alone, or two or more types can be mixed and used.
含醯胺基單體可列舉：N-環己基馬來醯亞胺、N-苯基馬來醯亞胺、N-甲基馬來醯亞胺、N-乙基馬來醯亞胺、N-丙基馬來醯亞胺、N-異丙基馬來醯亞胺、N-丁基馬來醯亞胺、伊康醯亞胺等。Examples of amide group-containing monomers include: N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N -Propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, icosimide, etc.
含醯胺基單體可列舉：(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N,N-二乙基甲基丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-甲氧基甲基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺、(甲基)丙烯酸二甲基胺乙酯、(甲基)丙烯酸三級丁基胺乙酯、二丙酮(甲基)丙烯醯胺、N-乙烯基乙醯胺、N,N'-亞甲基雙(甲基)丙烯醯胺、N,N-二甲基胺丙基(甲基)丙烯醯胺、N-乙烯基己內醯胺等。Examples of amide group-containing monomers include: (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N -Diethylmethacrylamide, N-isopropyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide , N-butoxymethyl (meth)acrylamide, dimethylamine ethyl (meth)acrylate, tertiary butylamine ethyl (meth)acrylate, diacetone (meth)acrylamide , N-vinyl acetamide, N,N'-methylenebis(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N-vinylcaprolamide Amide etc.
其他含氮單體可舉含胺基單體、(甲基)丙烯腈、N-(甲基)丙烯醯基嗎福林、N-乙烯基-2-吡咯啶酮等。Examples of other nitrogen-containing monomers include amine group-containing monomers, (meth)acrylonitrile, N-(meth)acrylomorphine, N-vinyl-2-pyrrolidone, and the like.
單體成分可在不損及本發明效果之範圍內包含用以調整(甲基)丙烯酸系聚合物之玻璃轉移點或剝離性的其他聚合性單體。The monomer component may contain other polymerizable monomers for adjusting the glass transition point or peelability of the (meth)acrylic polymer within a range that does not impair the effects of the present invention.
其他聚合性單體可列舉例如含羧基單體、含磺酸基單體、含磷酸基單體、乙烯酯單體、芳香族乙烯基單體等，該等可有助於提升凝集力、耐熱性等。又可列舉例如含酸酐基單體、含羥基單體、含環氧基單體、乙烯基醚單體等，該等可有助於提升接著力，同時具有作為交聯化基點發揮功用之官能基。又例如可使用具有碳數1或碳數15以上之烷基的(甲基)丙烯酸系單體等。該等聚合性單體可單獨使用，亦可混合2種以上來使用。Examples of other polymerizable monomers include carboxyl group-containing monomers, sulfonic acid group-containing monomers, phosphate group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, etc., which can help improve cohesion and heat resistance. Sex etc. Examples include acid anhydride group-containing monomers, hydroxyl group-containing monomers, epoxy group-containing monomers, vinyl ether monomers, etc., which can help improve adhesion and have functions that function as cross-linking base points. base. As another example, a (meth)acrylic monomer having an alkyl group having a carbon number of 1 or a carbon number of 15 or more can be used. These polymerizable monomers may be used individually or in mixture of 2 or more types.
含羧基單體可列舉丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧乙酯、(甲基)丙烯酸羧戊酯、伊康酸、馬來酸、延胡索酸、巴豆酸等。其中，可適宜使用丙烯酸及甲基丙烯酸。Examples of carboxyl group-containing monomers include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like. Among them, acrylic acid and methacrylic acid can be suitably used.
含磺酸基單體可列舉苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等。Examples of sulfonic acid group-containing monomers include styrenesulfonic acid, allylsulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamide-2-methylpropanesulfonic acid, Sulfopropyl acrylate, (meth)acryloyloxynaphthalene sulfonic acid, etc.
含磷酸基單體可舉2-羥乙基丙烯醯基磷酸酯等。Examples of the phosphoric acid group-containing monomer include 2-hydroxyethylacrylyl phosphate.
乙烯酯單體可舉乙酸乙烯酯、丙酸乙烯酯、月桂酸乙烯酯、乙烯基吡咯啶酮等。Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, vinyl laurate, vinylpyrrolidone, and the like.
芳香族乙烯基單體可舉苯乙烯、氯苯乙烯、氯甲基苯乙烯、α-甲基苯乙烯等。Examples of aromatic vinyl monomers include styrene, chlorostyrene, chloromethylstyrene, α-methylstyrene, and the like.
含酸酐基單體可舉馬來酸酐、伊康酸酐等。Examples of acid anhydride group-containing monomers include maleic anhydride, itaconic anhydride, and the like.
含羥基單體可列舉：(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸6-羥己酯、(甲基)丙烯酸8-羥辛酯、(甲基)丙烯酸10-羥癸酯、(甲基)丙烯酸12-羥月桂酯、(4-羥甲基環己基)甲基丙烯酸酯、N-羥甲基(甲基)丙烯醯胺、N-羥基(甲基)丙烯醯胺、乙烯醇、烯丙醇、2-羥乙基乙烯基醚、4-羥丁基乙烯基醚、二乙二醇單乙烯基醚等。Examples of hydroxyl-containing monomers include: (2-hydroxyethylmeth)acrylate, 2-hydroxybutyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, and 4-hydroxybutyl(meth)acrylate. , 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethyl) cyclohexyl) methacrylate, N-hydroxymethyl (meth) acrylamide, N-hydroxy (meth) acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4 -Hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, etc.
含環氧基單體可舉環氧丙基(甲基)丙烯酸酯、烯丙基環氧丙基醚等。Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, allyl glycidyl ether, and the like.
乙烯基醚單體可舉甲基乙烯基醚、乙基乙烯基醚、異丁基乙烯基醚等。Examples of vinyl ether monomers include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and the like.
具有碳數1或碳數15以上之烷基的(甲基)丙烯酸系單體，可舉例如(甲基)丙烯酸甲酯、(甲基)丙烯酸十五酯、(甲基)丙烯酸十六酯等。Examples of the (meth)acrylic monomer having an alkyl group having a carbon number of 1 or 15 or more carbon atoms include methyl (meth)acrylate, pentadecyl (meth)acrylate, and cetyl (meth)acrylate. wait.
上述單體成分中，上述其他聚合性單體之含有比率例如為0.1重量%~10重量%，宜為0.2重量%~7重量%，較宜為0.5重量%~5重量%。In the above-mentioned monomer component, the content ratio of the above-mentioned other polymerizable monomers is, for example, 0.1 to 10% by weight, preferably 0.2 to 7% by weight, and more preferably 0.5 to 5% by weight.
並且，上述以外之可共聚單體可舉含有矽原子之矽烷系單體等。矽烷系單體可列舉：3-丙烯醯氧丙基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、4-乙烯基丁基三甲氧基矽烷、4-乙烯基丁基三乙氧基矽烷、8-乙烯基辛基三甲氧基矽烷、8-乙烯基辛基三乙氧基矽烷、10-甲基丙烯醯氧癸基三甲氧基矽烷、10-丙烯醯氧癸基三甲氧基矽烷、10-甲基丙烯醯氧癸基三乙氧基矽烷、10-丙烯醯氧癸基三乙氧基矽烷等。矽烷系單體可單獨使用，亦可混合2種以上來使用。Furthermore, examples of copolymerizable monomers other than the above include silane-based monomers containing silicon atoms. Silane-based monomers include: 3-propenyloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinyl Butyltriethoxysilane, 8-vinyloctyltrimethoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloxydecyltrimethoxysilane, 10-propyloxysilane Decyltrimethoxysilane, 10-methacryloxydecyltriethoxysilane, 10-acryloxydecyltriethoxysilane, etc. The silane-based monomer can be used alone, or two or more types can be mixed and used.
相對於(甲基)丙烯酸系聚合物100重量份，上述矽烷系單體之摻混量宜為0.1重量份~3重量份，較宜為0.5重量份~2重量份。使矽烷系單體共聚可適宜提高耐久性。The blending amount of the above silane monomer is preferably 0.1 to 3 parts by weight, more preferably 0.5 to 2 parts by weight relative to 100 parts by weight of the (meth)acrylic polymer. Copolymerizing silane-based monomers can suitably improve durability.
(甲基)丙烯酸系聚合物之重量平均分子量例如為60萬以上，宜為150萬以上，較宜為160萬以上，更宜為180萬以上。(甲基)丙烯酸系聚合物之重量平均分子量例如為300萬以下，宜為250萬以下。重量平均分子量若在上述範圍內，便滿足上述α1/α2之關係，而可適宜獲得耐久性及作業性優異之黏著劑層。此外，重量平均分子量係指利用GPC(凝膠滲透層析法；Gel Permeation Chromatography)測定，並藉由聚苯乙烯換算所算出之值。The weight average molecular weight of the (meth)acrylic polymer is, for example, 600,000 or more, preferably 1,500,000 or more, more preferably 1,600,000 or more, more preferably 1,800,000 or more. The weight average molecular weight of the (meth)acrylic polymer is, for example, 3 million or less, preferably 2.5 million or less. If the weight average molecular weight is within the above range, the above-mentioned α1/α2 relationship is satisfied, and an adhesive layer excellent in durability and workability can be suitably obtained. In addition, the weight average molecular weight refers to a value measured by GPC (Gel Permeation Chromatography) and calculated in terms of polystyrene.
由容易取得黏著性能之平衡來看，上述(甲基)丙烯酸系聚合物之玻璃轉移溫度(Tg)例如為-5℃以下，宜為-10℃以下。玻璃轉移溫度高於-5℃時，聚合物不易流動而對被黏體之濕潤變得不充分，有造成於層間發生膨脹的情形。此外，(甲基)丙烯酸系聚合物之玻璃轉移溫度(Tg)可藉由適當變更所用單體成分或組成比來調整至前述範圍內。From the viewpoint of easily achieving a balance of adhesive properties, the glass transition temperature (Tg) of the (meth)acrylic polymer is, for example, -5°C or lower, preferably -10°C or lower. When the glass transition temperature is higher than -5℃, the polymer will not flow easily and will not fully moisten the adherend, which may cause expansion between layers. In addition, the glass transition temperature (Tg) of the (meth)acrylic polymer can be adjusted to be within the aforementioned range by appropriately changing the monomer components or composition ratio used.
(甲基)丙烯酸系聚合物之製造可適當選擇溶液聚合、塊狀聚合、乳化聚合、各種自由基聚合等公知的製造方法。溶液聚合中，聚合溶劑可使用例如乙酸乙酯、甲苯等。關於具體之溶液聚合例，反應可於氮等非活性氣體氣流下，例如相對於單體總量100重量份添加偶氮雙異丁腈0.01~0.2重量份作為聚合引發劑，且通常在50~70℃左右進行8~30小時左右。所得(甲基)丙烯酸系聚合物亦可為無規共聚物、嵌段共聚物、接枝共聚物等任一者。The (meth)acrylic polymer can be produced by appropriately selecting known production methods such as solution polymerization, block polymerization, emulsion polymerization, and various radical polymerizations. In solution polymerization, for example, ethyl acetate, toluene, etc. can be used as the polymerization solvent. Regarding specific solution polymerization examples, the reaction can be carried out under an inert gas flow such as nitrogen. For example, 0.01 to 0.2 parts by weight of azobisisobutyronitrile is added as a polymerization initiator relative to 100 parts by weight of the total monomers, and usually at 50 to Process at about 70°C for about 8 to 30 hours. The obtained (meth)acrylic polymer may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.
在聚合中，可視需要適當選擇任意適當之聚合引發劑、鏈轉移劑、乳化劑等來使用。In the polymerization, any appropriate polymerization initiator, chain transfer agent, emulsifier, etc. may be appropriately selected and used as needed.
丙烯酸系黏著劑組成物包含(甲基)丙烯酸系聚合物作為基底聚合物，宜更包含過氧化物及異氰酸酯系交聯劑。The acrylic adhesive composition includes a (meth)acrylic polymer as a base polymer, and preferably further includes a peroxide and an isocyanate cross-linking agent.
過氧化物若為經加熱或光照射會產生自由基活性種而使黏著劑組成物之基底聚合物進行交聯者即可適當使用，但考慮到作業性或穩定性，宜使用1分鐘半衰期溫度在80℃~160℃之過氧化物，較宜使用在90℃~140℃之過氧化物。1分鐘半衰期溫度若過低，有在塗佈乾燥前之保存時便會進行反應，導致黏度變高而無法塗佈之情形；另一方面，1分鐘半衰期溫度若過高，有交聯反應時之溫度變高而發生副反應、且大量殘留未反應之過氧化物而隨時間進行交聯之情形。Peroxides can be used appropriately if they generate free radical active species upon heating or light irradiation to cross-link the base polymer of the adhesive composition. However, considering workability or stability, it is advisable to use a 1-minute half-life temperature. Peroxides that operate at 80℃~160℃ are more suitable to use peroxides that operate at 90℃~140℃. If the 1-minute half-life temperature is too low, the reaction may occur during storage before coating and drying, resulting in a high viscosity that cannot be applied. On the other hand, if the 1-minute half-life temperature is too high, cross-linking reactions may occur. When the temperature becomes high, side reactions occur, and a large amount of unreacted peroxide remains, causing cross-linking to occur over time.
過氧化物可列舉：二(2-乙基己基)過氧二碳酸酯(1分鐘半衰期溫度：90.6℃)、二(4-三級丁基環己基)過氧二碳酸酯(1分鐘半衰期溫度：92.1℃)、過氧二碳酸二-二級丁酯(1分鐘半衰期溫度：92.4℃)、過氧新癸酸三級丁酯(1分鐘半衰期溫度：103.5℃)、過氧化三甲基乙酸三級己酯(1分鐘半衰期溫度：109.1℃)、過氧化三甲基乙酸三級丁酯(1分鐘半衰期溫度：110.3℃)、二月桂醯基過氧化物(1分鐘半衰期溫度：116.4℃)、二正辛醯基過氧化物(1分鐘半衰期溫度：117.4℃)、1,1,3,3-四甲基丁基過氧基-2-乙基己酸酯(1分鐘半衰期溫度：124.3℃)、二(4-甲基苯甲醯基)過氧化物(1分鐘半衰期溫度：128.2℃)、二苯甲醯基過氧化物(1分鐘半衰期溫度：130.0℃)、過異丁酸三級丁酯(1分鐘半衰期溫度：136.1℃)、1,1-二(三級己基過氧基)環己烷(1分鐘半衰期溫度：149.2℃)等。其中，由交聯反應效率優異來看，宜可使用二(4-三級丁基環己基)過氧二碳酸酯(1分鐘半衰期溫度：92.1℃)、二月桂醯基過氧化物(1分鐘半衰期溫度：116.4℃)、二苯甲醯基過氧化物(1分鐘半衰期溫度：130.0℃)等。過氧化物可單獨使用，亦可混合2種以上來使用。Examples of peroxides include: di(2-ethylhexyl)peroxydicarbonate (half-life temperature in 1 minute: 90.6°C), di(4-tertiary butylcyclohexyl)peroxydicarbonate (half-life temperature in 1 minute) : 92.1℃), di-secondary butyl peroxydicarbonate (half-life temperature in 1 minute: 92.4℃), tertiary butyl peroxyneodecanoate (half-life temperature in 1 minute: 103.5℃), trimethylacetic acid peroxide Tertiary hexyl ester (1-minute half-life temperature: 109.1°C), tertiary butyl peroxytrimethylacetate (1-minute half-life temperature: 110.3°C), dilauryl peroxide (1-minute half-life temperature: 116.4°C) , di-n-octyl peroxide (half-life temperature in 1 minute: 117.4℃), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (half-life temperature in 1 minute: 124.3℃) , Bis(4-methylbenzoyl) peroxide (1-minute half-life temperature: 128.2°C), Diphenyl peroxide (1-minute half-life temperature: 130.0°C), tertiary butyl perisobutyric acid Ester (half-life temperature in 1 minute: 136.1°C), 1,1-di(tertiary hexylperoxy)cyclohexane (half-life temperature in 1 minute: 149.2°C), etc. Among them, due to the excellent cross-linking reaction efficiency, it is appropriate to use bis(4-tertiary butylcyclohexyl)peroxydicarbonate (half-life temperature of 1 minute: 92.1°C) and dilauryl peroxide (1 minute Half-life temperature: 116.4℃), benzyl peroxide (half-life temperature in 1 minute: 130.0℃), etc. Peroxide can be used alone, or two or more types can be mixed and used.
此外，過氧化物之半衰期係表示過氧化物之分解速度的指標，意指過氧化物之殘存量變成一半時的時間。有關用以在任意時間內達半衰期的分解溫度、及在任意溫度下的半衰期時間等，係記載於製造商目錄等之中，例如記載於日本油脂股份公司的「有機過氧化物型錄第9版(2003年5月)」等之中。In addition, the half-life of peroxide is an index indicating the decomposition rate of peroxide, and means the time required for the remaining amount of peroxide to become half. The decomposition temperature required to achieve the half-life within an arbitrary period of time, the half-life time at an arbitrary temperature, etc. are described in the manufacturer's catalog, for example, in "Organic Peroxide Catalog No. 9" of Nippon Oils and Fats Co., Ltd. Edition (May 2003)" and so on.
相對於(甲基)丙烯酸系聚合物100重量份，過氧化物之摻混量例如為0.02重量份~2重量份，宜為0.04重量份~1.5重量份，較宜為0.05重量份~1重量份。過氧化物之摻混量若在上述範圍內，便可獲得耐久性及接著性優異之黏著劑層。The blending amount of the peroxide is, for example, 0.02 to 2 parts by weight, preferably 0.04 to 1.5 parts by weight, more preferably 0.05 to 1 part by weight relative to 100 parts by weight of the (meth)acrylic polymer. share. If the blending amount of peroxide is within the above range, an adhesive layer with excellent durability and adhesion can be obtained.
異氰酸酯系交聯劑可舉二異氰酸甲苯酯、二異氰酸二甲苯酯等芳香族異氰酸酯、異佛酮二異氰酸酯等脂環族異氰酸酯、六亞甲基二異氰酸酯等脂肪族異氰酸酯等。異氰酸酯系交聯劑可單獨使用，亦可混合2種以上來使用。Examples of the isocyanate cross-linking agent include aromatic isocyanates such as toluene diisocyanate and xylylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate. The isocyanate-based cross-linking agent can be used alone, or two or more types can be mixed and used.
更具體而言，可列舉：伸丁基二異氰酸酯、六亞甲基二異氰酸酯等低級脂肪族聚異氰酸酯類、伸環戊基二異氰酸酯、伸環己基二異氰酸酯、異佛酮二異氰酸酯等脂環族異氰酸酯類、2,4-甲苯二異氰酸酯、4,4'-二苯甲烷二異氰酸酯、伸茬基二異氰酸酯、聚亞甲基聚苯基異氰酸酯等芳香族二異氰酸酯類、三羥甲丙烷/二異氰酸甲苯酯三聚物加成物(Nippon Polyurethane Industry Co.,Ltd.製，商品名Coronate L)、三羥甲丙烷/六亞甲基二異氰酸酯三聚物加成物(Nippon Polyurethane Industry Co.,Ltd.製，商品名Coronate HL)、六亞甲基二異氰酸酯的三聚異氰酸酯物(Nippon Polyurethane Industry Co.,Ltd.製，商品名Coronate HX)等異氰酸酯加成物、聚醚聚異氰酸酯、聚酯聚異氰酸酯、以及該等與各種多元醇之加成物、經以三聚異氰酸酯鍵、縮二脲鍵、脲甲酸酯鍵等多官能化之聚異氰酸酯等。More specifically, examples include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, and alicyclic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate. Isocyanates, 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, stubble diisocyanate, polymethylene polyphenyl isocyanate and other aromatic diisocyanates, trimethylolpropane/diisocyanate Toluene cyanate terpolymer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate L), trimethylolpropane/hexamethylene diisocyanate terpolymer adduct (Nippon Polyurethane Industry Co. Ltd., trade name Coronate HL), isocyanate adducts such as hexamethylene diisocyanate tripolyisocyanate (Nippon Polyurethane Industry Co., Ltd., trade name Coronate HX), polyether polyisocyanate, polyisocyanate Ester polyisocyanates, and their adducts with various polyols, polyisocyanates multi-functionalized with isocyanate bonds, biuret bonds, allophanate bonds, etc.
相對於(甲基)丙烯酸系聚合物100重量份，異氰酸酯系交聯劑之摻混量例如為0.02重量份~2重量份，宜為0.04重量份~1.5重量份，較宜為0.05重量份~1重量份。異氰酸酯系交聯劑之摻混量若在上述範圍內，便可獲得凝集力及接著性優異之黏著劑層。The blending amount of the isocyanate cross-linking agent is, for example, 0.02 to 2 parts by weight, preferably 0.04 to 1.5 parts by weight, more preferably 0.05 to 1.5 parts by weight relative to 100 parts by weight of the (meth)acrylic polymer. 1 part by weight. If the blending amount of the isocyanate cross-linking agent is within the above range, an adhesive layer with excellent cohesion and adhesion can be obtained.
交聯劑(過氧化物及異氰酸酯系交聯劑)之摻混量係調整成使經交聯之黏著劑層之凝膠分率成為例如45重量%~95重量%、宜為50重量%~90重量%、較宜為55重量%~85重量%。凝膠分率在上述範圍內之黏著劑層其耐久性及接著性優異。The blending amount of the cross-linking agent (peroxide and isocyanate cross-linking agent) is adjusted so that the gel fraction of the cross-linked adhesive layer becomes, for example, 45 to 95% by weight, preferably 50 to 50% by weight. 90% by weight, preferably 55% by weight to 85% by weight. An adhesive layer with a gel fraction within the above range has excellent durability and adhesion.
黏著劑層之凝膠分率(重量%)可為下述方式計算之值：將黏著劑層之乾燥重量W1(g)在約23℃下浸漬於乙酸乙酯中7天後，將上述黏著劑層之不溶解成分從乙酸乙酯中取出並測定乾燥後之重量W2(g)，以(W2/W1)×100計算而得之值。The gel fraction (% by weight) of the adhesive layer can be calculated as follows: after immersing the dry weight W1 (g) of the adhesive layer in ethyl acetate at about 23°C for 7 days, the above adhesive layer The insoluble components of the agent layer were taken out from the ethyl acetate and the weight W2 (g) after drying was measured, and the value was calculated as (W2/W1)×100.
藉由調整過氧化物及異氰酸酯系交聯劑之摻混量、交聯處理溫度、交聯處理時間等，可將上述凝膠分率調整至所期望之範圍內。By adjusting the blending amounts of peroxide and isocyanate cross-linking agents, cross-linking treatment temperature, cross-linking treatment time, etc., the above-mentioned gel fraction can be adjusted to a desired range.
交聯處理溫度或交聯處理時間宜設定成使黏著劑組成物中所含之過氧化物之分解量達50重量%以上，較宜設定成使其達60重量%以上，更宜設定成使其達70重量%以上。The cross-linking treatment temperature or cross-linking treatment time should be set so that the decomposition amount of the peroxide contained in the adhesive composition reaches 50% by weight or more, more preferably 60% by weight or more, and more preferably so that the It reaches more than 70% by weight.
例如，以交聯處理溫度為1分鐘半衰期溫度來說，在1分鐘內過氧化物之分解量為50重量%，在2分鐘內過氧化物之分解量為75重量%，從而必須為1分鐘以上之交聯處理時間。又，例如在交聯處理溫度下過氧化物之半衰期(半衰時間)若為30秒，便需要30秒以上之交聯處理時間，又例如在交聯處理溫度下過氧化物之半衰期(半衰時間)若為5分鐘，便需要5分鐘以上之交聯處理時間。For example, if the cross-linking treatment temperature is the half-life temperature of 1 minute, the decomposition amount of peroxide in 1 minute is 50% by weight, and the decomposition amount of peroxide in 2 minutes is 75% by weight, so it must be 1 minute. The above cross-linking processing time. Furthermore, for example, if the half-life (half-life time) of peroxide at the cross-linking treatment temperature is 30 seconds, a cross-linking treatment time of more than 30 seconds is required. If the decay time) is 5 minutes, more than 5 minutes of cross-linking processing time is required.
如此一來，依據使用之過氧化物，交聯處理溫度或交聯處理時間可藉由假設過氧化物呈一次方正比而從半衰期(半衰時間)以理論計算算出，且可適當調節添加量。另一方面，設為愈高溫，產生副反應之可能性便愈高，因此交聯處理溫度宜為170℃以下。In this way, depending on the peroxide used, the cross-linking treatment temperature or cross-linking treatment time can be theoretically calculated from the half-life (half-life time) by assuming that the peroxide is linearly proportional, and the amount of addition can be appropriately adjusted. . On the other hand, the higher the temperature, the higher the possibility of side reactions, so the cross-linking treatment temperature is preferably 170°C or lower.
交聯處理時間通常為0.2分鐘~20分鐘左右，宜為0.5分鐘~10分鐘左右。The cross-linking treatment time is usually about 0.2 minutes to 20 minutes, preferably about 0.5 minutes to 10 minutes.
交聯處理可在黏著劑層的乾燥步驟時之溫度下進行，也可以在乾燥步驟後另外設置交聯處理步驟來進行。The cross-linking treatment can be performed at the same temperature as the drying step of the adhesive layer, or an additional cross-linking step can be performed after the drying step.
黏著劑組成物中可為了提高接著力、耐久性而摻混矽烷耦合劑。矽烷耦合劑可列舉：3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、2-(3-4-環氧環己基)乙基三甲氧基矽烷等含環氧基之矽烷耦合劑；3-胺丙基三甲氧基矽烷、N-2-(胺乙基)-3-胺丙基甲基二甲氧基矽烷、3-三乙氧基矽基-N-(1,3-二甲基亞丁基)丙胺等含胺基之矽烷耦合劑；3-丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧丙基三乙氧基矽烷等含(甲基)丙烯醯基之矽烷耦合劑；3-異氰酸酯丙基三乙氧基矽烷等含異氰酸酯基之矽烷耦合劑等。矽烷耦合劑可單獨使用，亦可混合2種以上來使用。A silane coupling agent may be blended into the adhesive composition to improve adhesion and durability. Silane coupling agents include: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxy Silane, 2-(3-4-epoxycyclohexyl)ethyltrimethoxysilane and other silane coupling agents containing epoxy groups; 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)- 3-Aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine and other amine-containing silane coupling agents; 3-propylene oxide Silane coupling agents containing (meth)acrylyl groups such as methylpropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane; 3-isocyanatepropyltriethoxysilane and other silane coupling agents containing isocyanate groups Silane coupling agent, etc. The silane coupling agent can be used alone, or two or more types can be mixed and used.
相對於(甲基)丙烯酸系聚合物100重量份，矽烷耦合劑之摻混量例如為0.01重量份~1重量份，宜為0.02重量份~0.6重量份，較宜為0.05重量份~0.3重量份。The blending amount of the silane coupling agent is, for example, 0.01 to 1 part by weight, preferably 0.02 to 0.6 parts by weight, more preferably 0.05 to 0.3 parts by weight relative to 100 parts by weight of the (meth)acrylic polymer. share.
上述黏著劑組成物亦可視需要更包含有任意適當之添加劑。添加劑可列舉：界面活性劑、塑化劑、增黏劑、表面潤滑劑、調平劑、軟化劑、抗氧化劑、抗老化劑、光穩定劑、紫外線吸收劑、聚合抑制劑等。亦可在可控制之範圍內添加還原劑。The above-mentioned adhesive composition may also contain any appropriate additives if necessary. Additives can be listed: surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, etc. Reducing agents can also be added within a controllable range.
藉由使上述黏著劑組成物交聯可適宜獲得黏著劑層A。上述黏著劑組成物交聯而得之黏著劑層A在升溫時與降溫時之變形率的差小，且即便在已薄層化之情況下，在高溫高濕下之耐久性仍優異。黏著劑組成物可在塗佈於所期望之構件(在圖1A之構成中，為偏光構件、第一相位差構件或保護構件)之表面後進行交聯，亦可塗佈於剝離襯材等之支持體上並交聯後轉印至所期望之構件上。The adhesive layer A can be suitably obtained by crosslinking the adhesive composition. The difference in the deformation rate of the adhesive layer A obtained by cross-linking the above-mentioned adhesive composition is small when the temperature rises and when the temperature drops, and even when the layer is thinned, the durability under high temperature and high humidity is still excellent. The adhesive composition may be applied to the surface of a desired member (in the configuration of FIG. 1A , the polarizing member, the first retardation member, or the protective member) and then cross-linked, or may be applied to a release liner, etc. onto the support and cross-linked before being transferred to the desired component.
黏著劑層A之厚度如上述，例如為1µm以上且15µm以下，宜為2µm以上且小於10µm，較宜為3µm以上且8µm以下。The thickness of the adhesive layer A is as described above, for example, 1 µm or more and 15 µm or less, preferably 2 µm or more and less than 10 µm, more preferably 3 µm or more and 8 µm or less.
光學積層體可包含上述黏著劑層A以外之黏著劑層。所述黏著劑層亦可藉由任意適當之黏著劑組成物形成。形成黏著劑層A以外之黏著劑層的黏著劑組成物可列舉：丙烯酸系黏著劑組成物、橡膠系黏著劑組成物、聚矽氧系黏著劑組成物、聚酯系黏著劑組成物、胺甲酸酯系黏著劑組成物、環氧系黏著劑組成物及聚醚系黏著劑組成物。由透明性、耐熱性等優異來看，可適宜使用丙烯酸系黏著劑組成物。The optical laminate may include an adhesive layer other than the adhesive layer A described above. The adhesive layer can also be formed by any suitable adhesive composition. Adhesive compositions that form adhesive layers other than adhesive layer A include: acrylic adhesive compositions, rubber-based adhesive compositions, polysilicone-based adhesive compositions, polyester-based adhesive compositions, and amine-based adhesive compositions. Formate-based adhesive compositions, epoxy-based adhesive compositions and polyether-based adhesive compositions. Since it has excellent transparency, heat resistance, etc., an acrylic adhesive composition can be suitably used.
黏著劑層A以外之黏著劑層在25℃下之儲存彈性模數例如為5×10 4Pa以上，宜為10×10 4Pa以上，較宜為14×10 4Pa以上，且例如為20×10 4Pa以下，宜為15×10 4Pa以下。 The storage elastic modulus of the adhesive layer other than adhesive layer A at 25°C is, for example, 5×10 4 Pa or more, preferably 10×10 4 Pa or more, more preferably 14×10 4 Pa or more, and, for example, 20 ×10 4 Pa or less, preferably 15 × 10 4 Pa or less.
黏著劑層A以外之黏著劑層之厚度例如為12µm以上且100µm以下，宜為12µm以上且80µm以下。The thickness of the adhesive layer other than the adhesive layer A is, for example, 12 µm or more and 100 µm or less, preferably 12 µm or more and 80 µm or less.
＜偏光構件＞
偏光膜構件10代表上係包含含二色性物質之樹脂薄膜(有時稱為吸收型偏光膜)的吸收型偏光構件，可視需求於其單側或兩側進一步包含保護層。保護層代表上係透過任意適當之接著劑層貼合於吸收型偏光膜上。形成接著劑層之接著劑代表上可舉紫外線硬化型接著劑。
＜Polarizing member＞
The
偏光構件(吸收型偏光膜)之正交透射率(Tc)宜為0.5%以下，較宜為0.1%以下，更宜為0.05%以下。偏光構件(吸收型偏光膜)之單體透射率(Ts)例如為41.0%~45.0%，宜為42.0%以上。偏光構件(吸收型偏光膜)之偏光度(P)例如為99.0%~99.997%，宜為99.9%以上。The cross transmittance (Tc) of the polarizing member (absorptive polarizing film) is preferably 0.5% or less, more preferably 0.1% or less, and more preferably 0.05% or less. The single transmittance (Ts) of the polarizing member (absorptive polarizing film) is, for example, 41.0% to 45.0%, preferably 42.0% or more. The degree of polarization (P) of the polarizing member (absorptive polarizing film) is, for example, 99.0% to 99.997%, preferably 99.9% or more.
上述正交透射率、單體透射率及偏光度例如可使用紫外線可見光光譜光度計來測定。偏光度P可使用紫外線可見光光譜光度計測定單體透射率Ts、平行透射率Tp及正交透射率Tc，並從所得Tp及Tc利用下述式來求算。此外，Ts、Tp及Tc係以JIS Z8701之2度視野(C光源)進行測定並進行視感度校正後之Y值。 偏光度P(%)={(Tp-Tc)/(Tp+Tc)} 1 /2×100 The above-mentioned orthogonal transmittance, single transmittance, and polarization degree can be measured using an ultraviolet-visible light spectrophotometer, for example. The degree of polarization P can be measured using an ultraviolet-visible light spectrophotometer to measure the single transmittance Ts, the parallel transmittance Tp, and the orthogonal transmittance Tc, and calculate it from the obtained Tp and Tc using the following formula. In addition, Ts, Tp and Tc are Y values measured using the 2-degree field of view (C light source) of JIS Z8701 and corrected for visual sensitivity. Polarization P(%)={(Tp-Tc)/(Tp+Tc)} 1 /2 ×100
吸收型偏光膜之厚度例如為1µm以上且20µm以下，可為2µm以上且15µm以下，可為12µm以下，可為10µm以下，可為8µm以下，亦可為5µm以下。The thickness of the absorptive polarizing film may be, for example, 1 µm or more and 20 µm or less, 2 µm or more and 15 µm or less, 12 µm or less, 10 µm or less, 8 µm or less, or 5 µm or less.
上述吸收型偏光膜可由單層樹脂薄膜製作，亦可使用二層以上之積層體來製作。The above-mentioned absorptive polarizing film can be made of a single-layer resin film or a laminate of two or more layers.
由單層樹脂薄膜製作時，例如可藉由對聚乙烯醇(PVA)系薄膜、部分縮甲醛化PVA系薄膜、乙烯・乙酸乙烯酯共聚物系部分皂化薄膜等之親水性高分子薄膜，施行利用碘或二色性染料等之二色性物質進行之染色處理、延伸處理等，而獲得吸收型偏光膜。其中，宜為將PVA系薄膜用碘染色並進行單軸延伸所得之吸收型偏光膜。When made from a single-layer resin film, for example, hydrophilic polymer films such as polyvinyl alcohol (PVA)-based films, partially formalized PVA-based films, and ethylene vinyl acetate copolymer-based partially saponified films can be processed. Dyeing treatment, stretching treatment, etc. using dichroic substances such as iodine or dichroic dyes are used to obtain an absorptive polarizing film. Among them, an absorption-type polarizing film obtained by dyeing a PVA-based film with iodine and uniaxially stretching it is preferred.
上述利用碘進行之染色，例如可藉由將PVA系薄膜浸漬於碘水溶液中來進行。上述單軸延伸之延伸倍率宜為3~7倍。延伸可在染色處理後進行，亦可邊染色邊進行。又，亦可延伸後再染色。視需要，對PVA系薄膜施行膨潤處理、交聯處理、洗淨處理、乾燥處理等。The above-described dyeing with iodine can be performed, for example, by immersing a PVA-based film in an iodine aqueous solution. The extension ratio of the above-mentioned uniaxial extension is preferably 3 to 7 times. Extending can be done after dyeing or while dyeing. Also, it can be dyed after stretching. If necessary, the PVA film is subjected to swelling treatment, cross-linking treatment, washing treatment, drying treatment, etc.
作為使用上述二層以上之積層體來製作時的積層體，可列舉以下積層體：樹脂基材與積層於該樹脂基材之PVA系樹脂層(PVA系樹脂薄膜)的積層體；或者樹脂基材與塗佈形成於該樹脂基材之PVA系樹脂層的積層體。使用樹脂基材與塗佈形成於該樹脂基材之PVA系樹脂層的積層體而得之吸收型偏光膜，例如可藉由以下步驟來製作：將PVA系樹脂溶液塗佈於樹脂基材並使其乾燥，於樹脂基材上形成PVA系樹脂層，而獲得樹脂基材與PVA系樹脂層的積層體；及，將該積層體延伸及染色，而將PVA系樹脂層製成吸收型偏光膜。本實施形態中，宜於樹脂基材之單側形成含鹵化物與聚乙烯醇系樹脂之聚乙烯醇系樹脂層。延伸在代表上包含使積層體浸漬於硼酸水溶液中來延伸。並且視需求，延伸可更包含在硼酸水溶液中進行延伸前將積層體在高溫(例如95℃以上)下進行空中延伸。並且，在本實施形態中，宜將積層體供於乾燥收縮處理，該乾燥收縮處理係將積層體邊往長邊方向輸送邊加熱藉此使其於寬度方向收縮2%以上。代表上，本實施形態之製造方法包含對積層體依序施行空中輔助延伸處理、染色處理、水中延伸處理及乾燥收縮處理。藉由導入輔助延伸，即便是在將PVA塗佈於熱塑性樹脂上之情況下仍可提高PVA之結晶性，而可達成高光學特性。又，同時事先提高PVA之定向性，可在後續的染色步驟或延伸步驟中浸漬於水中時，防止PVA之定向性降低或溶解等問題，而可達成高光學特性。並且，將PVA系樹脂層浸漬於液體中時，相較於PVA系樹脂層不含鹵化物之情況，更可抑制聚乙烯醇分子之定向紊亂及定向性之降低。藉此，可提升經由染色處理及水中延伸處理等將積層體浸漬於液體中來進行的處理步驟而得之吸收型偏光膜的光學特性。並且，透過乾燥收縮處理使積層體於寬度方向收縮，可提升光學特性。所得樹脂基材/吸收型偏光膜之積層體可直接使用(即，可將樹脂基材作為吸收型偏光膜之保護層)，亦可於從樹脂基材/吸收型偏光膜之積層體剝離樹脂基材後的剝離面、或於與剝離面相反側的面積層符合目的之任意適當的保護層來使用。所述吸收型偏光膜之製造方法之詳細內容記載於例如日本專利特開2012-73580號公報、日本專利第6470455號中。本說明書中係引用該等公報整體之記載作為參考。Examples of the laminated body when produced using the above-mentioned two or more laminated bodies include the following laminated bodies: a laminated body of a resin base material and a PVA-based resin layer (PVA-based resin film) laminated on the resin base material; or a resin-based laminated body. A laminate consisting of a material and a PVA-based resin layer coated on the resin base material. An absorption-type polarizing film using a laminate of a resin base material and a PVA-based resin layer coated on the resin base material can be produced, for example, by the following steps: applying a PVA-based resin solution to the resin base material and dry it to form a PVA-based resin layer on the resin base material to obtain a laminated body of the resin base material and the PVA-based resin layer; and extend and dye the laminated body to make the PVA-based resin layer into an absorption-type polarized light membrane. In this embodiment, it is preferable to form a polyvinyl alcohol-based resin layer containing a halide and a polyvinyl alcohol-based resin on one side of the resin base material. Stretching typically includes immersing the laminate in a boric acid aqueous solution to stretch. And if necessary, stretching may further include stretching the laminate in the air at a high temperature (for example, above 95° C.) before stretching in a boric acid aqueous solution. Furthermore, in this embodiment, it is preferable to subject the laminated body to a drying and shrinking process in which the laminated body is heated while being conveyed in the longitudinal direction to shrink the laminated body by 2% or more in the width direction. Typically, the manufacturing method of this embodiment includes sequentially performing an air-assisted stretching process, a dyeing process, an underwater stretching process, and a drying shrinkage process on the laminate. By introducing auxiliary stretching, the crystallinity of PVA can be improved even when PVA is coated on thermoplastic resin, and high optical properties can be achieved. In addition, by improving the orientation of PVA in advance, it can prevent problems such as reduction in orientation or dissolution of PVA when immersed in water in the subsequent dyeing step or stretching step, thereby achieving high optical properties. In addition, when the PVA-based resin layer is immersed in a liquid, compared with the case where the PVA-based resin layer does not contain halides, the orientation disorder and decrease in orientation of polyvinyl alcohol molecules can be suppressed. Thereby, the optical characteristics of the absorptive polarizing film obtained by immersing the laminate in a liquid, such as dyeing treatment and water stretching treatment, can be improved. In addition, the optical properties can be improved by shrinking the laminate in the width direction through drying and shrinkage treatment. The obtained laminate of the resin base material/absorptive polarizing film can be used directly (that is, the resin base material can be used as a protective layer of the absorptive polarizing film), or the resin can be peeled off from the laminate of the resin base material/absorptive polarizing film. Use any suitable protective layer that meets the purpose on the peeling surface behind the base material or on the area opposite to the peeling surface. Details of the manufacturing method of the absorptive polarizing film are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580 and Japanese Patent No. 6470455. The entire description of these publications is cited in this specification as a reference.
保護層係以可作為吸收型偏光膜之保護層使用之任意適當的薄膜形成。作為成為該薄膜之主成分的材料之具體例，可列舉：聚降𦯉烯系等環烯烴(COP)系、聚對苯二甲酸乙二酯(PET)系等聚酯系、三醋酸纖維素(TAC)等纖維素系樹脂、聚碳酸酯(PC)系、(甲基)丙烯酸系、聚乙烯醇系、聚醯胺系、聚醯亞胺系、聚醚碸系、聚苯乙烯系、聚烯烴系及乙酸酯系等之透明樹脂。又，亦可舉(甲基)丙烯酸系、胺甲酸酯系、(甲基)丙烯酸胺甲酸酯系、環氧系、聚矽氧系等之熱硬化型樹脂或紫外線硬化型樹脂等。其他還可舉例如矽氧烷系聚合物等玻璃質系聚合物。又，亦可使用日本專利特開2001-343529號公報(WO01/37007)中記載之聚合物薄膜。作為該薄膜之材料，例如可使用含有於側鏈具有取代或非取代之醯亞胺基之熱塑性樹脂、及於側鏈具有取代或非取代之苯基以及腈基之熱塑性樹脂的樹脂組成物，可舉例如具有由異丁烯與N-甲基馬來醯亞胺構成之交替共聚物及丙烯腈-苯乙烯共聚物的樹脂組成物。該聚合物薄膜例如可為上述樹脂組成物之擠製成形物。樹脂薄膜之材料可單獨或組合來使用。The protective layer is formed of any appropriate film that can be used as a protective layer of the absorptive polarizing film. Specific examples of materials that serve as the main component of the film include cyclic olefin (COP) systems such as polynorphene-based systems, polyester systems such as polyethylene terephthalate (PET) systems, and cellulose triacetate. (TAC) and other cellulose-based resins, polycarbonate (PC)-based, (meth)acrylic-based, polyvinyl alcohol-based, polyamide-based, polyimide-based, polyetherether-based, polystyrene-based, Transparent resins such as polyolefin series and acetate series. Furthermore, thermosetting resins such as (meth)acrylic type, urethane type, (meth)acrylic urethane type, epoxy type, polysilicone type, etc., or ultraviolet curing type resins may also be mentioned. Other examples include glassy polymers such as siloxane polymers. In addition, the polymer film described in Japanese Patent Application Laid-Open No. 2001-343529 (WO01/37007) can also be used. As the material of the film, for example, a resin composition containing a thermoplastic resin having a substituted or unsubstituted acyl imine group in the side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and a nitrile group in the side chain can be used. Examples thereof include resin compositions having an alternating copolymer of isobutylene and N-methylmaleimide and an acrylonitrile-styrene copolymer. The polymer film may be, for example, an extruded product of the above-mentioned resin composition. The materials of the resin film can be used individually or in combination.
保護層之厚度代表上為100µm以下，例如為5µm~80µm，宜為10µm~50µm，較宜為15µm~35µm。The thickness of the protective layer is typically less than 100µm, for example, 5µm~80µm, preferably 10µm~50µm, more preferably 15µm~35µm.
＜第一相位差構件＞
第一相位差構件20包含第1λ/4構件20a。第1λ/4構件20a係配置成使偏光構件10(吸收型偏光膜)之吸收軸與第1λ/4構件20a之慢軸構成的角度宜成為40°~50°、較宜為42°~48°、例如約45°。
<First phase difference member>
The first
第1λ/4構件20a之面內相位差Re(550)例如為100nm~190nm，可為110nm~180nm，可為130nm~160nm，亦可為135nm~155nm。第1λ/4構件宜展現相位差值隨測定光之波長而變大的逆色散波長特性。第1λ/4構件之Re(450)/Re(550)例如為0.75以上且小於1，亦可為0.8以上且0.95以下。The in-plane phase difference Re(550) of the first λ/4
第1λ/4構件宜為折射率特性展現nx＞ny≧nz之關係。在此「ny=nz」不只ny與nz完全相同之情況，還包含實質上相同之情況。因此，在不損及本發明效果之範圍下可有成為ny＜nz之情形。第1λ/4構件之Nz係數宜為0.9~3，較宜為0.9~2.5，更宜為0.9~1.5，尤宜為0.9~1.3。The first λ/4 member should preferably exhibit the relationship nx>ny≧nz for its refractive index characteristics. Here "ny=nz" includes not only the case where ny and nz are exactly the same, but also the case where they are substantially the same. Therefore, ny<nz may be satisfied as long as the effect of the present invention is not impaired. The Nz coefficient of the first λ/4 member is preferably 0.9~3, more preferably 0.9~2.5, more preferably 0.9~1.5, especially 0.9~1.3.
第1λ/4構件係以可滿足上述特性之任意適當之材料形成。第1λ/4構件例如可為樹脂薄膜之延伸薄膜或液晶化合物之定向固化層。The first λ/4 member is formed of any suitable material that can satisfy the above characteristics. The first λ/4 member may be, for example, a stretched film of a resin film or a directionally solidified layer of a liquid crystal compound.
上述樹脂薄膜所含之樹脂可列舉：聚碳酸酯系樹脂、聚酯碳酸酯系樹脂、聚酯系樹脂、聚乙烯縮醛系樹脂、聚芳酯系樹脂、環狀烯烴系樹脂、纖維素系樹脂、聚乙烯醇系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚醚系樹脂、聚苯乙烯系樹脂、丙烯酸系樹脂等。該等樹脂可單獨使用，亦可組合來使用。組合方法可舉例如摻合、共聚。第1λ/4構件展現逆色散波長特性時，可適宜使用含聚碳酸酯系樹脂或聚酯碳酸酯系樹脂(以下有時僅稱為聚碳酸酯系樹脂)之樹脂薄膜。Examples of the resin contained in the above-mentioned resin film include polycarbonate resin, polyester carbonate resin, polyester resin, polyvinyl acetal resin, polyarylate resin, cyclic olefin resin, and cellulose resin. Resin, polyvinyl alcohol resin, polyamide resin, polyimide resin, polyether resin, polystyrene resin, acrylic resin, etc. These resins can be used individually or in combination. Examples of the combination method include blending and copolymerization. When the 1st λ/4 member exhibits reverse dispersion wavelength characteristics, a resin film containing polycarbonate resin or polyestercarbonate resin (hereinafter, may only be referred to as polycarbonate resin) can be suitably used.
上述聚碳酸酯系樹脂可使用任意適當之聚碳酸酯系樹脂。例如，聚碳酸酯系樹脂包含源自茀系二羥基化合物之結構單元、源自異山梨醇系二羥基化合物之結構單元及源自選自於由脂環式二醇、脂環式二甲醇、二、三或聚乙二醇、以及伸烷基二醇或螺甘油所構成群組中之至少1種二羥基化合物之結構單元。聚碳酸酯系樹脂宜包含源自茀系二羥基化合物之結構單元、源自異山梨醇系二羥基化合物之結構單元、源自脂環式二甲醇之結構單元以及/或是源自二、三或聚乙二醇之結構單元；更宜包含源自茀系二羥基化合物之結構單元、源自異山梨醇系二羥基化合物之結構單元及源自二、三或聚乙二醇之結構單元。聚碳酸酯系樹脂亦可視需要包含有源自其他二羥基化合物之結構單元。此外，可適宜用於第1λ/4構件之聚碳酸酯系樹脂及第1λ/4構件之形成方法的詳細內容，例如記載於日本專利特開2014-10291號公報、日本專利特開2014-26266號公報、日本專利特開2015-212816號公報、日本專利特表2015-212817號公報、日本專利特表2015-212818號公報中，本說明書即援用該等公報之記載作為參考。Any appropriate polycarbonate resin can be used as the polycarbonate resin. For example, the polycarbonate resin includes a structural unit derived from a fluorine-based dihydroxy compound, a structural unit derived from an isosorbide-based dihydroxy compound, and a structural unit derived from an alicyclic diol, an alicyclic dimethanol, The structural unit of at least one dihydroxy compound in the group consisting of di, tri or polyethylene glycol, and alkylene glycol or spiroglycerol. The polycarbonate resin preferably contains structural units derived from fluorine-based dihydroxy compounds, structural units derived from isosorbide-based dihydroxy compounds, structural units derived from alicyclic dimethanol, and/or derived from di- or tri-hydroxy compounds. Or structural units of polyethylene glycol; more preferably, it includes structural units derived from fluorine dihydroxy compounds, structural units derived from isosorbide dihydroxy compounds, and structural units derived from di, tri or polyethylene glycol. The polycarbonate resin may also contain structural units derived from other dihydroxy compounds if necessary. In addition, details of a polycarbonate-based resin suitably used for the first λ/4 member and a method for forming the first λ/4 member are described in, for example, Japanese Patent Laid-Open No. 2014-10291 and Japanese Patent Laid-Open No. 2014-26266 Publication No. 2015-212816, Japanese Patent Application Publication No. 2015-212817, and Japanese Patent Application Publication No. 2015-212818, the descriptions of these publications are incorporated into this specification as a reference.
以樹脂薄膜之延伸薄膜構成之第1λ/4構件的厚度例如為10µm~100µm，宜為10µm~70µm，較宜為20µm~60µm。The thickness of the first λ/4 member made of a stretched film of a resin film is, for example, 10µm~100µm, preferably 10µm~70µm, more preferably 20µm~60µm.
上述液晶化合物之定向固化層係液晶化合物在層內於預定方向定向且其定向狀態經固定之層。此外，「定向固化層」之概念包含如後述使液晶單體硬化而得之定向硬化層。以第1λ/4構件來說，代表上係棒狀液晶化合物沿第1λ/4構件之慢軸方向排列之狀態下定向(沿面定向)。棒狀液晶化合物可舉例如液晶聚合物及液晶單體。液晶化合物宜可聚合。液晶化合物若可聚合，便可使液晶化合物於定向後進行聚合，藉此固定液晶化合物的定向狀態。The orientation-solidified layer of the above-mentioned liquid crystal compound is a layer in which the liquid crystal compound is oriented in a predetermined direction within the layer and its orientation state is fixed. In addition, the concept of "directionally hardened layer" includes a directionally hardened layer obtained by hardening a liquid crystal monomer as described later. Taking the 1st λ/4 member as an example, it means that the rod-shaped liquid crystal compounds are aligned along the slow axis direction of the 1st λ/4 member and are oriented (along the surface). Examples of rod-shaped liquid crystal compounds include liquid crystal polymers and liquid crystal monomers. The liquid crystal compound is preferably polymerizable. If the liquid crystal compound is polymerizable, the liquid crystal compound can be polymerized after alignment, thereby fixing the alignment state of the liquid crystal compound.
上述液晶化合物之定向固化層(液晶定向固化層)可藉由下述方式來形成：對預定基材之表面施行定向處理，並於該表面塗敷含液晶化合物的塗敷液，使該液晶化合物於對應上述定向處理之方向定向，並固定該定向狀態。定向處理可採用任意適當之定向處理。具體上可舉機械性定向處理、物理性定向處理、化學性定向處理。機械性定向處理的具體例可舉磨擦處理、延伸處理。物理性定向處理的具體例可舉磁場定向處理、電場定向處理。化學性定向處理的具體例可舉斜向蒸鍍法、光定向處理。各種定向處理的處理條件可按目的採用任意適當之條件。The directionally solidified layer of the above-mentioned liquid crystal compound (liquid crystal directionally solidified layer) can be formed by subjecting the surface of a predetermined base material to an orientation treatment, and applying a coating liquid containing a liquid crystal compound to the surface, so that the liquid crystal compound Orient in the direction corresponding to the above orientation processing, and fix the orientation state. The directional treatment may employ any suitable directional treatment. Specifically, mechanical orientation treatment, physical orientation treatment, and chemical orientation treatment can be cited. Specific examples of mechanical orientation treatment include friction treatment and stretching treatment. Specific examples of physical orientation processing include magnetic field orientation processing and electric field orientation processing. Specific examples of chemical orientation treatment include oblique evaporation and photo-orientation treatment. The processing conditions for various targeted treatments can be any appropriate conditions depending on the purpose.
液晶化合物的定向可因應液晶化合物的種類在可展現液晶相之溫度下進行處理來進行。藉由進行所述溫度處理，液晶化合物會變為液晶狀態，而該液晶化合物會因應基材表面之定向處理方向而定向。The orientation of the liquid crystal compound can be carried out by treating the liquid crystal compound at a temperature that can exhibit a liquid crystal phase according to the type of the liquid crystal compound. By performing the temperature treatment, the liquid crystal compound will change into a liquid crystal state, and the liquid crystal compound will be oriented according to the direction of the orientation treatment on the surface of the substrate.
在一實施形態中，定向狀態之固定係藉由冷卻依上述方式定向之液晶化合物來進行。當液晶化合物為聚合性或交聯性時，定向狀態之固定係藉由對依上述方式定向之液晶化合物施行聚合處理或交聯處理來進行。In one embodiment, the alignment state is fixed by cooling the liquid crystal compound aligned in the above manner. When the liquid crystal compound is polymerizable or cross-linked, the alignment state is fixed by subjecting the liquid crystal compound oriented in the above manner to polymerization treatment or cross-linking treatment.
上述液晶化合物可使用任意適當之液晶聚合物及/或液晶單體。液晶聚合物及液晶單體各自可單獨使用，亦可組合。液晶化合物之具體例及液晶定向固化層之製作方法記載於例如日本專利特開2006-163343號公報、日本專利特開2006-178389號公報、國際公開第2018/123551號公報中。本說明書即援用該等公報之記載作為參考。Any appropriate liquid crystal polymer and/or liquid crystal monomer may be used as the above liquid crystal compound. The liquid crystal polymer and the liquid crystal monomer can each be used alone or in combination. Specific examples of the liquid crystal compound and methods of producing the liquid crystal alignment solidified layer are described in, for example, Japanese Patent Laid-Open No. 2006-163343, Japanese Patent Laid-Open No. 2006-178389, and International Publication No. 2018/123551. This manual refers to the records in these publications as a reference.
以液晶定向固化層構成之第1λ/4構件的厚度例如為1µm~10µm，宜為1µm~8µm，較宜為1µm~6µm，更宜為1µm~4µm。The thickness of the first λ/4 member composed of the liquid crystal orientation solidified layer is, for example, 1µm~10µm, preferably 1µm~8µm, more preferably 1µm~6µm, and more preferably 1µm~4µm.
＜保護構件＞
保護構件30代表上包含基材。基材可以任意適當之薄膜構成。作為構成基材之薄膜之主成分的材料可列舉例如：三醋酸纖維素(TAC)等之纖維素系樹脂、聚酯系、聚乙烯醇系、聚碳酸酯系、聚醯胺系、聚醯亞胺系、聚醚碸系、聚碸系、聚苯乙烯系、聚降𦯉烯系等之環烯烴系、聚烯烴系、(甲基)丙烯酸系及乙酸酯系等之樹脂。基材之厚度宜為5µm~80µm，較宜為10µm~40µm，更宜為15µm~35µm。
＜Protective components＞
The
保護構件宜具有基材與形成於基材上之表面處理層。表面處理層可位於光學積層體100a之最表面。表面處理層可具有任意適當之功能。表面處理層可舉例如硬塗層、抗反射層、抗黏層、防眩層。保護構件亦可具有2層以上表面處理層。The protective member preferably has a base material and a surface treatment layer formed on the base material. The surface treatment layer may be located on the outermost surface of the
抗反射層係為了防止外光等之反射而設置。抗反射層可舉例如氟樹脂層、含奈米粒子(代表上為中空奈米粒子，例如中空奈米二氧化矽粒子)之樹脂層、或具有奈米結構(例如蛾眼結構)之抗反射層。抗反射層之厚度宜為0.05µm~1µm。上述樹脂層之形成方法可舉例如溶膠凝膠法、使用異氰酸酯之熱硬化法、使用交聯性單體(例如多官能丙烯酸酯)與光聚合引發劑之游離輻射線硬化法(代表上為光硬化法)。The anti-reflection layer is provided to prevent reflection of external light, etc. Examples of the anti-reflective layer include a fluororesin layer, a resin layer containing nanoparticles (typically hollow nanoparticles, such as hollow nanosilica particles), or an anti-reflective layer having a nanostructure (such as a moth-eye structure). layer. The thickness of the anti-reflective layer should be 0.05µm~1µm. Examples of methods for forming the resin layer include a sol-gel method, a thermal curing method using isocyanate, and an ionizing radiation curing method using a crosslinkable monomer (such as a polyfunctional acrylate) and a photopolymerization initiator (typically, photopolymerization initiator). hardening method).
硬塗層宜具有充分之表面硬度、優異之機械強度及優異之光透射性。硬塗層可由任意適當之樹脂形成。硬塗層代表上係由紫外線硬化型樹脂形成。紫外線硬化型樹脂可舉例如聚酯系、丙烯酸系、胺甲酸酯系、醯胺系、聚矽氧系、環氧系。硬塗層之厚度例如為0.5µm以上，宜為1µm以上，且例如為20µm以下，宜為15µm以下。The hard coating layer should have sufficient surface hardness, excellent mechanical strength and excellent light transmittance. The hard coat layer can be formed of any suitable resin. The hard coat layer is made of ultraviolet curable resin. Examples of ultraviolet curable resins include polyester-based, acrylic-based, urethane-based, amide-based, polysilicone-based, and epoxy-based resins. The thickness of the hard coat layer is, for example, 0.5 μm or more, preferably 1 μm or more, and, for example, 20 μm or less, preferably 15 μm or less.
A-2.實施形態2
圖1B係本發明一實施形態之光學積層體的概略截面圖。圖1B所示之光學積層體100b依序具有：第一黏著劑層a1、偏光構件10、第二黏著劑層a2、包含第1λ/4構件20a之第一相位差構件20、第三黏著劑層a3及保護構件30；該光學積層體100b在下述這點與光學積層體100a不同：第一相位差構件20不僅包含第1λ/4構件20a且還包含有折射率特性可展現nz ＞nx=ny之關係的構件(所謂正C板)20b。偏光構件10之吸收軸與第1λ/4構件20a之慢軸構成之角度宜配置成40°~50°、較宜為42°~48°、例如約45°。
A-2.
第一相位差構件20具有第1λ/4構件20a與正C板20b之積層結構。具體而言，第1λ/4構件20a與正C板20b係透過接著層b1積層。如圖式例所示，第1λ/4構件20a宜較正C板20b位於更靠偏光構件10側，但該等之配置亦可相反。接著層b1代表上為黏著劑層或接著劑層。接著層b1為接著劑層時，光學積層體100b中之黏著劑層的總數為3，其中2層以上之黏著劑層為黏著劑層A，宜為3層全部為黏著劑層A。接著層b1為黏著劑層時，光學積層體100b中之黏著劑層的總數為4，此時亦為2層以上之黏著劑層為上述黏著劑層A，宜為3層以上、較宜為4層全部黏著劑層為黏著劑層A。接著劑層例如係以紫外線硬化型接著劑形成，其厚度例如為0.05µm~30µm。The first
光學積層體100b之厚度例如為100µm以上且300µm以下，宜為110µm以上且250µm以下，較宜為120µm以上且200µm以下。The thickness of the optical
關於黏著劑層、偏光構件、第1λ/4構件及保護構件如A-1項所記載。The adhesive layer, polarizing member, 1st λ/4 member and protective member are as described in item A-1.
＜正C板＞
正C板20b之厚度方向的相位差Rth(550)宜為-50nm~-300nm，較宜為-70nm~-250nm，更宜為-90nm~-200nm，尤宜為-100nm~-180nm。在此，「nx=ny」不僅包含nx與ny嚴格上相等之情況，還包含nx與ny實質上相等之情況。正C板之面內相位差Re(550)例如小於10nm。
＜Positive C board＞
The phase difference Rth (550) in the thickness direction of the
正C板可以任意適當之材料形成。正C板宜由含固定成垂面定向之液晶材料的薄膜構成。可使垂面定向的液晶材料(液晶化合物)可為液晶單體，亦可為液晶聚合物。所述液晶化合物及正C板之形成方法的具體例可舉日本專利特開2002-333642號公報之段落[0020]~[0028]中記載之液晶化合物及相位差層之形成方法。此時，正C板之厚度宜為0.5µm~5µm。The positive C plate can be formed of any suitable material. The positive C plate should be composed of a film containing liquid crystal material fixed in a vertical orientation. The liquid crystal material (liquid crystal compound) capable of vertical alignment can be a liquid crystal monomer or a liquid crystal polymer. Specific examples of the method of forming the liquid crystal compound and the positive C plate include the method of forming the liquid crystal compound and the retardation layer described in paragraphs [0020] to [0028] of Japanese Patent Application Laid-Open No. 2002-333642. At this time, the thickness of the positive C plate should be 0.5µm~5µm.
B.顯示系統
圖2係示意圖，顯示包含A項記載之光學積層體的顯示系統(附顯示器之護目鏡)之一例的概略構成。圖2(a)係示意圖示顯示系統2之主要構成要素之配置及形狀等，圖2(b)係示意圖，用以說明圖2(a)所示之顯示系統2為液晶顯示系統時之上述光學積層體之配置。
B.Display system
FIG. 2 is a schematic diagram showing the schematic structure of an example of a display system (goggles with a display) including the optical laminate described in item A. Figure 2(a) is a schematic diagram illustrating the arrangement and shape of the main components of the
如圖2(a)所示，顯示系統2具備有：顯示元件12、反射型偏光構件14、第一透鏡部16、半反射鏡18、第一相位差構件20、第二相位差構件22及第二透鏡部24。反射型偏光構件14係配置於顯示元件12’之顯示面12’側即前方，其可反射從顯示元件12射出之光。第一透鏡部16係配置於顯示元件12與反射型偏光構件14之間的光路上，半反射鏡18係配置於顯示元件12與第一透鏡部16之間。第一相位差構件20係配置於顯示元件12與半反射鏡18之間的光路上，第二相位差構件22係配置於半反射鏡18與反射型偏光構件14之間的光路上。雖未圖示，但顯示系統2可於反射型偏光構件14與第二透鏡部24之間更具備吸收型偏光構件。As shown in FIG. 2(a) , the
有時會將從半反射鏡起配置於前方之構成要素(圖式例中，為半反射鏡18、第一透鏡部16、第二相位差構件22、反射型偏光構件14及第二透鏡部24)統稱為透鏡部(透鏡部4)。In some cases, components are arranged in front from the half mirror (in the example of the figure, they are the
顯示元件12例如為液晶顯示器或有機EL顯示器，且具有用以顯示影像之顯示面12’。要從顯示面12’射出之光例如會通過顯示元件12可包含之偏光構件10後射出，成為第1直線偏光。The
第一相位差構件20包含第1λ/4構件，其可將入射第一相位差構件20之第1直線偏光轉換成第1圓偏光。第一相位差構件不包含第1λ/4構件以外之構件時，第一相位差構件便相當於第1λ/4構件。此外，在圖式例中，為了說明，而於第一相位差構件20與顯示元件12之間中介有空間，但如後述，本發明實施形態之顯示系統係藉由使用包含如A項記載之偏光構件與第一相位差構件(第1λ/4構件)之光學積層體，而將第一相位差構件20與顯示元件12設置成一體。The first
半反射鏡18會將從顯示元件12射出之光透射，並將反射型偏光構件14所反射之光朝反射型偏光構件14反射。半反射鏡18係設於第一透鏡部16上而成一體。The
第二相位差構件22包含第2λ/4構件，其可使在反射型偏光構件14及半反射鏡18反射之光透射反射型偏光構件14。第二相位差構件不包含第2λ/4構件以外之構件時，第二相位差構件便相當於第2λ/4構件。第二相位差構件22亦可設於第一透鏡部16上而成一體。The second
從第一相位差構件20所含之第1λ/4構件射出之第1圓偏光會通過半反射鏡18及第一透鏡部16，藉由第二相位差構件22所含之第2λ/4構件轉換成第2直線偏光。從第2λ/4構件射出之第2直線偏光不會透射反射型偏光構件14而朝半反射鏡18反射。此時，入射反射型偏光構件14之第2直線偏光的偏光方向係與反射型偏光構件14之反射軸同方向。因此，入射反射型偏光構件14之第2直線偏光會被反射型偏光構件14反射。The first circularly polarized light emitted from the 1st λ/4 member included in the first
被反射型偏光構件14反射之第2直線偏光藉由第二相位差構件22所含之第2λ/4構件轉換成第2圓偏光，而從第2λ/4構件射出之第2圓偏光係通過第一透鏡部16而被半反射鏡18反射。被半反射鏡18反射之第2圓偏光會通過第一透鏡部16，藉由第二相位差構件22所含之第2λ/4構件轉換成第3直線偏光。第3直線偏光會透射反射型偏光構件14。此時，入射反射型偏光構件14之第3直線偏光的偏光方向係與反射型偏光構件14之透射軸同方向。因此，入射反射型偏光構件14之第3直線偏光會透射反射型偏光構件14。The second linearly polarized light reflected by the reflective polarizing
如上述，顯示系統2亦可於反射型偏光構件14之前方(靠近眼睛側)包含有吸收型偏光構件(代表上為吸收型偏光薄膜)。反射型偏光構件14之反射軸與吸收型偏光構件之吸收軸可配置成互相大致平行，且反射型偏光構件之透射軸與吸收型偏光構件之透射軸可配置成互相大致平行。藉此，透射反射型偏光構件14之第3直線偏光可直接透射吸收型偏光構件。反射型偏光構件與吸收型偏光構件例如亦可透過接著層積層。As mentioned above, the
透射反射型偏光構件14之光會通過第二透鏡部24入射使用者之眼睛26。The light from the
例如，顯示元件12所含之偏光構件10之吸收軸與反射型偏光構件14之反射軸可配置成互相大致平行，亦可配置成大致正交。顯示元件12所含之偏光構件10之吸收軸與第一相位差構件20所含之第1λ/4構件之慢軸構成的角度例如為40°~50°，可為42°~48°，亦可為約45°。顯示元件12所含之偏光構件10之吸收軸與第二相位差構件22所含之第2λ/4構件之慢軸構成的角度例如為40°~50°，可為42°~48°，亦可為約45°。包含偏光構件10及第1λ/4構件之第一相位差構件20各自如A項所記載。For example, the absorption axis of the polarizing
第2λ/4構件之面內相位差Re(550)例如為100nm~190nm，可為110nm~180nm，可為130nm~160nm，亦可為135nm~155nm。第2λ/4構件宜展現相位差值隨測定光之波長而變大的逆色散波長特性。第2λ/4構件宜滿足Re(450)＜Re(550)＜Re(650)之關係。第2λ/4構件之Re(450)/Re(550)例如為0.75以上且小於1，亦可為0.8以上且0.95以下。The in-plane phase difference Re(550) of the 2nd λ/4 member is, for example, 100nm~190nm, 110nm~180nm, 130nm~160nm, or 135nm~155nm. The 2λ/4 member should preferably exhibit inverse dispersion wavelength characteristics in which the phase difference value increases with the wavelength of the measurement light. The 2λ/4 member should satisfy the relationship of Re(450)＜Re(550)＜Re(650). Re(450)/Re(550) of the second λ/4 member is, for example, 0.75 or more and less than 1, or may be 0.8 or more and 0.95 or less.
圖2(b)係顯示顯示系統2為液晶顯示系統時之光學積層體之配置。光學積層體100可適宜使用圖1A或圖1B中記載之光學積層體100a、100b。圖式例中，顯示元件12包含背光單元12a、背光側偏光構件12b、液晶單元12c及偏光構件10。背光側偏光構件12b與偏光構件10代表上係配置成使吸收軸方向互相大致正交，而與液晶單元12c一同構成液晶面板。光學積層體100係配置於半反射鏡18之顯示元件12側，在此，偏光構件10係透過黏著劑層a1貼合於液晶單元12c，又，第一相位差構件20(第1λ/4構件)係透過黏著劑層a2與偏光構件10貼合，結果成為顯示元件12與第一相位差構件20(第1λ/4構件)設置成一體之構成。又，藉由配置成具有表面處理層之保護構件30之該表面處理層成為最表面，可在半反射鏡18與第一相位差構件20(保護構件30)之間形成有空間之顯示系統獲得優異之抗反射效果。此外，圖式例之實施形態中，光學積層體100係貼合於液晶單元，而本發明實施形態之光學積層體亦可與有機EL面板一同構成有機EL顯示系統。此時，可於光學積層體100與有機EL面板之間配置包含第3λ/4構件之第三相位差構件。第三相位差構件亦可包含於本發明實施形態之光學積層體中。例如，本發明實施形態之光學積層體亦可透過接著層依序具有第三相位差構件、偏光構件、第一相位差構件及保護構件。具體而言，光學積層體可具有[黏著劑層/第三相位差構件/黏著劑層/偏光構件/黏著劑層/第一相位差構件/黏著劑層/保護構件]之構成，在該構成中可包含至少4層黏著劑層。黏著劑層之總數為4時，可於其中2層以上、宜3層或4層黏著劑層使用黏著劑層A。第3λ/4構件之面內相位差Re(550)例如為100nm~190nm，可為110nm~180nm，可為130nm~160nm，亦可為135nm~155nm。第3λ/4構件可應用與第1λ/4構件相同之說明。第三相位差構件可配置成使第3λ/4構件之慢軸與偏光構件10之吸收軸構成例如40°~50°、42°~48°或約45°之角度。FIG. 2(b) shows the arrangement of the optical laminate when the
實施例 以下，藉由實施例來具體說明本發明，惟本發明不受該等實施例所限。此外，厚度係藉由下述測定方法測定之值。 ＜厚度＞ 10µm以下的厚度係使用掃描型電子顯微鏡(日本電子公司製，製品名「JSM-7100F」)進行測定。大於10µm的厚度係使用數位測微器(Anritsu公司製，產品名「KC-351C」)進行測定。 ＜面內相位差＞ 使用王子計測器公司製「KOBRA-WPR」測定23℃下之面內相位差。 ＜線膨脹係數＞ 將黏著劑層(厚度1mm)切削成約5mm見方，並將所得者作為測定試料使用。將測定試料設置於測定裝置之試料台，按下述條件進行TMA測定。 ・測定裝置：SII NanoTechnology Inc.製「TMA/SS6000」 ・測定模式：壓縮膨脹法 ・測定荷重：9.8mN ・探針直徑：3.5mmφ(壓縮膨脹法) ・溫度過程：-60℃→210℃→-70℃→200℃ ・升溫/降溫速度：10℃/分鐘 ・測定氣體環境：N 2(流量：200ml/分鐘) ＜分子量之測定＞ (甲基)丙烯酸系聚合物之重量平均分子量係利用GPC(凝膠滲透層析法)測定且以聚苯乙烯換算來算出。 ・分析裝置：東曹(Tosoh)公司製，HLC-8120GPC ・數據處理裝置：東曹(Tosoh)公司製，GPC-8020 ・管柱：東曹(Tosoh)公司製，G7000HXL-H+GMHXL+GMHXL ・管柱尺寸；各7.8mmφ×30cm(合計90cm) ・流量：0.8ml/分鐘 ・注入試料濃度：約0.1重量% ・注入量：100µl ・管柱溫度：40℃ ・溶析液：四氫呋喃 ・檢測器：示差折射計(RI) EXAMPLES The present invention will be specifically described below through examples, but the present invention is not limited by these examples. In addition, the thickness is a value measured by the following measurement method. <Thickness> The thickness of 10 µm or less is measured using a scanning electron microscope (manufactured by JEOL Ltd., product name "JSM-7100F"). Thickness greater than 10µm is measured using a digital micrometer (manufactured by Anritsu Co., Ltd., product name "KC-351C"). <In-plane phase difference> The in-plane phase difference at 23°C was measured using "KOBRA-WPR" manufactured by Oji Instruments Co., Ltd. <Linear expansion coefficient> Cut the adhesive layer (thickness 1mm) into approximately 5mm square, and use the resultant as a measurement sample. The measurement sample was placed on the sample stage of the measurement device, and the TMA measurement was performed under the following conditions.・Measurement device: "TMA/SS6000" manufactured by SII NanoTechnology Inc. ・Measurement mode: compression expansion method ・Measurement load: 9.8mN ・Probe diameter: 3.5mmφ (compression expansion method) ・Temperature history: -60℃→210℃→ -70℃→200℃ ・Heating/cooling rate: 10℃/min ・Measurement gas environment: N 2 (Flow rate: 200ml/min) ＜Measurement of molecular weight＞The weight average molecular weight of (meth)acrylic polymer is determined by GPC (Gel permeation chromatography) was measured and calculated in terms of polystyrene.・Analysis device: HLC-8120GPC, made by Tosoh Corporation ・Data processing device: GPC-8020, made by Tosoh Corporation ・Pipe string: G7000HXL-H+GMHXL+GMHXL, made by Tosoh Corporation・Column size: 7.8mmφ×30cm each (90cm in total) ・Flow rate: 0.8ml/min ・Injection sample concentration: about 0.1% by weight ・Injection volume: 100µl ・Column temperature: 40℃ ・Eluent: tetrahydrofuran ・Detection Instrument: Differential Refractometer (RI)
[製造例1A：黏著劑層1之製作] ＜丙烯酸系聚合物1＞ 於具備攪拌葉片、溫度計、氮氣導入管、冷卻器之四口燒瓶中，饋入丙烯酸丁酯92重量份、N-丙烯醯基嗎福林(ACMO)5重量份、丙烯酸2.9重量份、丙烯酸2-羥乙酯0.1重量份、作為聚合引發劑之2,2-偶氮雙異丁腈0.1重量份、乙酸乙酯100重量份，一邊緩慢地攪拌一邊導入氮氣進行氮取代後，將燒瓶內的液溫保持在55℃附近進行8小時聚合反應，而調製出丙烯酸系聚合物1之溶液。丙烯酸系聚合物1之重量平均分子量為200萬。 [Manufacture Example 1A: Preparation of adhesive layer 1] ＜Acrylic polymer 1＞ Into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet pipe, and a cooler, 92 parts by weight of butyl acrylate, 5 parts by weight of N-acrylylmorphine (ACMO), 2.9 parts by weight of acrylic acid, and 2 parts by weight of acrylic acid - 0.1 part by weight of hydroxyethyl ester, 0.1 part by weight of 2,2-azobisisobutyronitrile as a polymerization initiator, and 100 parts by weight of ethyl acetate. After slowly stirring, nitrogen gas was introduced for nitrogen substitution, and then the contents in the flask were replaced. The liquid temperature was kept near 55° C., and polymerization reaction was performed for 8 hours to prepare a solution of acrylic polymer 1. The weight average molecular weight of acrylic polymer 1 is 2 million.
＜黏著劑溶液1＞ 相對於丙烯酸系聚合物1之溶液的固體成分100重量份，混合作為交聯劑之二苯甲醯基過氧化物(1分鐘半衰期：130℃)0.15重量份及二異氰酸甲苯酯之三羥甲丙烷加成物構成的聚異氰酸酯系交聯劑(Nippon Polyurethane Industry Co., Ltd.製，Coronate L)0.6重量份，而調製出丙烯酸系黏著劑溶液1。 ＜Adhesive solution 1＞ To 100 parts by weight of the solid content of the solution of the acrylic polymer 1, 0.15 parts by weight of benzyl peroxide (half-life of 1 minute: 130°C) as a cross-linking agent and toluene diisocyanate were mixed. An acrylic adhesive solution 1 was prepared by adding 0.6 parts by weight of a polyisocyanate cross-linking agent (Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) consisting of a hydroxymethylpropane adduct.
＜黏著劑層1＞ 將丙烯酸系黏著劑溶液1塗佈於經施行聚矽氧處理之聚對苯二甲酸乙二酯(PET)薄膜(Mitsubishi Polyester Film公司製，厚度：38µm)之單面，並在150℃下進行3分鐘乾燥、交聯處理，而形成乾燥後之厚度為5µm的黏著劑層1。 <Adhesive layer 1> The acrylic adhesive solution 1 was applied to one side of a silicone-treated polyethylene terephthalate (PET) film (manufactured by Mitsubishi Polyester Film Co., Ltd., thickness: 38µm), and the process was carried out at 150°C. Dry and cross-link for 3 minutes to form an adhesive layer 1 with a thickness of 5µm after drying.
[製造例1B：黏著劑層2之製作]
＜丙烯酸系聚合物2＞
於具備攪拌葉片、溫度計、氮氣導入管及冷卻器之四口燒瓶中，饋入含有丙烯酸丁酯94.9重量份、丙烯酸5重量份及丙烯酸2-羥乙酯0.1重量份之單體混合物。並相對於該單體混合物100重量份，將作為聚合引發劑之二苯甲醯基過氧化物0.3重量份與乙酸乙酯一同饋入，一邊緩慢地攪拌一邊導入氮氣將燒瓶內進行氮取代後，將燒瓶內之液溫保持在60℃進行7小時聚合反應。接著，於所得之反應液中添加乙酸乙酯調整成固體成分濃度30重量%，藉此獲得丙烯酸系聚合物2之溶液。丙烯酸系聚合物2之重量平均分子量為220萬。
[Manufacturing Example 1B: Preparation of adhesive layer 2]
＜
＜黏著劑溶液2＞
相對於丙烯酸系聚合物2之溶液的固體成分100重量份，混合聚異氰酸酯系交聯劑(三羥甲丙烷/二異氰酸甲苯酯加成物，Nippon Polyurethane Industry Co.,Ltd.製，Coronate L)0.6重量份及矽烷耦合劑(信越化學工業公司製，KBM403)0.075重量份，而調製出丙烯酸系黏著劑溶液2。
＜
＜黏著劑層2＞
將丙烯酸系黏著劑溶液2塗佈於經施行聚矽氧處理之聚對苯二甲酸乙二酯(PET)薄膜(Mitsubishi Polyester Film公司製，厚度：38µm)之單面，並在預定溫度下乾燥，而形成厚度12µm、15µm或20µm之黏著劑層2。
<
[製造例2：偏光薄膜1之製作] 將厚度30µm之聚乙烯醇(PVA)系樹脂薄膜(Kuraray公司製，製品名「PE3000」)的長條捲材，利用輥延伸機往長邊方向進行單軸延伸使其沿長邊方向成為5.9倍，並同時施以膨潤、染色、交聯、洗淨處理，最後施以乾燥處理，藉此製作出厚度12µm之吸收型偏光膜。 具體而言，膨潤處理係於20℃之純水中一邊進行處理一邊延伸成2.2倍。接著，染色處理係一邊於碘與碘化鉀之重量比為1：7之30℃的水溶液中進行處理一邊延伸成1.4倍，且該水溶液之碘濃度已調整成可使所得吸收型偏光膜之單體透射率成為45.0%。並且，交聯處理係採用二階段之交聯處理，第一階段之交聯處理係一邊於40℃的溶有硼酸與碘化鉀的水溶液中進行處理一邊延伸成1.2倍。第一階段之交聯處理的水溶液之硼酸含量為5.0重量%，碘化鉀含量係設為3.0重量%。第二階段之交聯處理係一邊於65℃的硼酸與碘化鉀的水溶液中進行處理一邊延伸成1.6倍。第二階段之交聯處理的水溶液之硼酸含量為4.3重量%，碘化鉀含量係設為5.0重量%。又，洗淨處理係以20℃之碘化鉀水溶液進行處理。洗淨處理之水溶液的碘化鉀含量係設為2.6重量%。最後，乾燥處理係於70℃下使其乾燥5分鐘而獲得吸收型偏光膜。 於所得吸收型偏光膜兩面透過紫外線硬化型接著劑貼合作為保護層之三醋酸纖維素(TAC)系樹脂薄膜(厚度：22µm)。具體而言，係塗敷成紫外線硬化型接著劑之總厚度成為約1µm，並使用輥軋機進行貼合。然後，從TAC薄膜側照射UV光線使接著劑硬化。 藉此，獲得具有[TAC薄膜(保護層)/吸收型偏光膜/TAC薄膜(保護層)]之構成的偏光薄膜1(厚度57µm)。 [Manufacture Example 2: Production of Polarizing Film 1] A long roll of polyvinyl alcohol (PVA)-based resin film (manufactured by Kuraray Co., Ltd., product name "PE3000") with a thickness of 30 µm is uniaxially stretched in the longitudinal direction using a roller stretching machine so that it becomes 5.9 in the longitudinal direction. times, and simultaneously undergo swelling, dyeing, cross-linking, cleaning, and finally drying to produce an absorptive polarizing film with a thickness of 12µm. Specifically, the swelling treatment was carried out in pure water at 20° C. while extending the film 2.2 times. Next, the dyeing treatment was carried out in an aqueous solution at 30° C. with a weight ratio of iodine and potassium iodide of 1:7, while extending to 1.4 times, and the iodine concentration of the aqueous solution was adjusted to a level that allows the monomer of the resulting absorption-type polarizing film to be The transmittance becomes 45.0%. Moreover, the cross-linking treatment adopts a two-stage cross-linking treatment. The first-stage cross-linking treatment is extended to 1.2 times while being treated in an aqueous solution of boric acid and potassium iodide dissolved at 40°C. The boric acid content of the aqueous solution of the first stage cross-linking treatment was 5.0% by weight, and the potassium iodide content was set to 3.0% by weight. The second stage of cross-linking treatment is performed in an aqueous solution of boric acid and potassium iodide at 65°C while extending to 1.6 times. The boric acid content of the aqueous solution for cross-linking treatment in the second stage is 4.3% by weight, and the potassium iodide content is set to 5.0% by weight. In addition, the cleaning treatment is performed with a potassium iodide aqueous solution at 20°C. The potassium iodide content of the aqueous solution for washing treatment was set to 2.6% by weight. Finally, the drying process was performed at 70° C. for 5 minutes to obtain an absorbing polarizing film. Tricellulose acetate (TAC)-based resin films (thickness: 22µm) as a protective layer were bonded to both sides of the resulting absorptive polarizing film through an ultraviolet curable adhesive. Specifically, the ultraviolet curable adhesive is applied so that the total thickness is about 1µm, and bonded using a roller. Then, UV light is irradiated from the TAC film side to harden the adhesive. Thereby, polarizing film 1 (thickness 57 μm) having the composition of [TAC film (protective layer)/absorptive polarizing film/TAC film (protective layer)] was obtained.
[製造例3：λ/4構件1之製作] 使用由2台具備有攪拌葉片及控制成100℃之回流冷卻器的直立式反應器構成之批次聚合裝置進行聚合。饋入雙[9-(2-苯氧基羰基乙基)茀-9-基]甲烷29.60質量份(0.046mol)、異山梨醇(ISB)29.21質量份(0.200mol)、螺甘油(SPG)42.28質量份(0.139mol)、碳酸二苯酯(DPC)63.77質量份(0.298mol)及作為觸媒的乙酸鈣一水合物1.19×10 -2質量份(6.78×10 -5mol)。將反應器內進行減壓氮取代後，以熱介質加溫，並於內溫達100℃之時間點開始攪拌。於升溫開始40分鐘後使內溫達到220℃，控制維持該溫度的同時開始減壓，在達到220℃後以90分鐘使其成為13.3kPa。將隨聚合反應副生成之苯酚蒸氣導入100℃之回流冷卻器，使苯酚蒸氣中所含些許量之單體成分返回反應器，並將未凝聚之苯酚蒸氣導入45℃的凝聚器中回收。將氮導入第1反應器暫時使其回復到大氣壓後，將第1反應器內之經寡聚化的反應液移至第2反應器。接著，開始進行第2反應器內的升溫及減壓，並以50分鐘使內溫成為240℃、壓力成為0.2kPa。然後，進行聚合直到達到預定之攪拌功率。在達到預定功率之時間點將氮導入反應器中使壓力回復，並將所生成之聚酯碳酸酯系樹脂擠出至水中，裁切束狀物而獲得丸粒。 [Production Example 3: Preparation of λ/4 member 1] Polymerization was performed using a batch polymerization apparatus consisting of two vertical reactors equipped with stirring blades and a reflux cooler controlled to 100°C. Feed in 29.60 parts by mass (0.046 mol) of bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane, 29.21 parts by mass (0.200 mol) of isosorbide (ISB), and spiroglycerol (SPG) 42.28 parts by mass (0.139 mol), 63.77 parts by mass (0.298 mol) of diphenyl carbonate (DPC) and 1.19×10 -2 parts by mass (6.78×10 -5 mol) of calcium acetate monohydrate as a catalyst. After the reactor was replaced with nitrogen under reduced pressure, it was heated with a heat medium, and stirring was started when the internal temperature reached 100°C. The internal temperature was brought to 220°C 40 minutes after the start of the temperature rise, and the pressure was reduced while maintaining the temperature. After reaching 220°C, it was adjusted to 13.3 kPa in 90 minutes. The phenol vapor generated by the polymerization reaction is introduced into the reflux cooler at 100°C, so that a small amount of monomer components contained in the phenol vapor is returned to the reactor, and the uncondensed phenol vapor is introduced into the condensator at 45°C for recovery. After introducing nitrogen into the first reactor and temporarily returning it to atmospheric pressure, the oligomerized reaction liquid in the first reactor is moved to the second reactor. Next, the temperature increase and pressure reduction in the second reactor were started, and the internal temperature was adjusted to 240° C. and the pressure to 0.2 kPa over 50 minutes. Then, polymerization is performed until a predetermined stirring power is reached. At the time point when the predetermined power is reached, nitrogen is introduced into the reactor to restore the pressure, the generated polyester carbonate resin is extruded into water, and the bundles are cut to obtain pellets.
將所得聚酯碳酸酯系樹脂(丸粒)在80℃下真空乾燥5小時後，使用具備單軸擠製機(東芝機械公司製，缸筒設定溫度：250℃)、T型模(寬200mm，設定溫度：250℃)、冷卻輥(設定溫度：120~130℃)及捲取機之薄膜製膜裝置，製作出厚度135µm之長條狀樹脂薄膜。將所得長條狀樹脂薄膜以延伸溫度143℃、延伸倍率2.8倍沿寬度方向延伸。藉此獲得厚度51µm之延伸薄膜(λ/4構件1)。λ/4構件1之Re(590)為143nm，Re(450)/Re(550)為0.86，Nz係數為1.12。The obtained polyester carbonate resin (pellets) was vacuum-dried at 80°C for 5 hours, and then used a single-screw extruder (manufactured by Toshiba Machine Co., Ltd., cylinder set temperature: 250°C) and a T-die (width 200mm). , set temperature: 250℃), cooling roller (set temperature: 120~130℃) and film forming device of the winding machine to produce a long resin film with a thickness of 135µm. The obtained long resin film was stretched in the width direction at a stretching temperature of 143°C and a stretching ratio of 2.8 times. Thus, a stretched film (λ/4 member 1) with a thickness of 51µm was obtained. Re(590) of λ/4 member 1 is 143nm, Re(450)/Re(550) is 0.86, and Nz coefficient is 1.12.
[製造例4：保護構件1之製作] 於具有內酯環結構之丙烯酸薄膜塗佈下述所示之硬塗層形成用材料，並使塗佈層乾燥而形成厚度0.5µm之硬塗層。接著，於硬塗層表面塗佈下述所示之抗反射層形成材料並在80℃下加熱1分鐘後，以高壓水銀燈對加熱後之塗佈層照射累積光量300mJ/cm 2之紫外線使塗佈層硬化，而形成厚度0.1µm之抗反射層。藉此，獲得具有[丙烯酸薄膜/硬塗層/抗反射層]之構成的保護構件1(厚度44µm)。 [Manufacture Example 4: Preparation of Protective Member 1] The following hard coat layer forming material was applied to an acrylic film having a lactone ring structure, and the coating layer was dried to form a hard coat layer with a thickness of 0.5 μm. Next, apply the anti-reflection layer forming material shown below on the surface of the hard coat layer and heat it at 80°C for 1 minute. Then, use a high-pressure mercury lamp to irradiate the heated coating layer with ultraviolet rays with a cumulative light intensity of 300 mJ/cm 2 to make the coating The cloth layer is hardened to form an anti-reflective layer with a thickness of 0.1µm. Thereby, the protective member 1 (thickness 44 µm) having the composition of [acrylic film/hard coat layer/anti-reflection layer] was obtained.
(硬塗層形成用材料) 於丙烯酸系樹脂原料(大日本油墨公司製，商品名：GRANDIC PC1071)中加入調平劑0.5重量%，並以乙酸乙酯稀釋成固體成分濃度成為50重量%，藉此調製出硬塗層形成用材料。此外，調平劑係以二甲基矽氧烷：羥丙基矽氧烷：6-異氰酸酯己基三聚異氰酸：脂肪族聚酯=6.3：1.0：2.2：1.0之莫耳比共聚而成的共聚物。 (Material for forming hard coat layer) A hard coating layer was prepared by adding 0.5% by weight of a leveling agent to an acrylic resin raw material (manufactured by Dainippon Ink Co., Ltd., trade name: GRANDIC PC1071) and diluting it with ethyl acetate to a solid concentration of 50% by weight. Use materials. In addition, the leveling agent is copolymerized with a molar ratio of dimethyl siloxane: hydroxypropyl siloxane: 6-isocyanate hexyl isocyanate: aliphatic polyester = 6.3: 1.0: 2.2: 1.0 of copolymers.
(抗反射層形成材料)
混合以新戊四醇三丙烯酸酯為主成分之多官能丙烯酸酯(大阪有機化學工業股份公司製，商品名「Viscoat #300」，固體成分100重量%)100重量份、中空奈米二氧化矽粒子(日揮觸媒化成工業股份公司製，商品名「THRULYA 5320」，固體成分20重量%，重量平均粒徑75nm)100重量份、實心奈米二氧化矽粒子(日產化學工業股份公司製，商品名「MEK-2140Z-AC」，固體成分30重量%，重量平均粒徑10nm)、含氟添加劑(信越化學工業股份公司製，商品名「KY-1203」，固體成分20重量%)12重量份及光聚合引發劑(BASF公司製，商品名「OMNIRAD907」，固體成分100重量%)3重量份。於該混合物中，添加以60：25：15重量比混合三級丁醇、甲基異丁基酮及丙二醇單甲基醚乙酸酯而成之混合溶劑作為稀釋溶劑，使整體之固體成分成為4重量%，並攪拌而調製出抗反射層形成材料。
(Anti-reflection layer forming material)
[實施例1] 於偏光薄膜1之其中一面按每個PET薄膜貼合黏著劑層1(厚度5µm)，並從PET薄膜將另一黏著劑層1(厚度5µm)轉印至另一面，再於其上貼合λ/4構件1。此時，係配置成使吸收型偏光膜之吸收軸與λ/4構件1之慢軸構成的角度成為45°。 接著，從PET薄膜將另一黏著劑層1(厚度5µm)轉印至λ/4構件1之表面，並於其上貼合保護構件1。此時，係貼合成使保護構件1之丙烯酸薄膜側表面在λ/4構件1側(換言之，使表面處理層成為最表面)。 依以上方式，而獲得具有[剝離襯材(PET薄膜)/黏著劑層1/偏光薄膜1/黏著劑層1/λ/4構件1/黏著劑層1/保護構件1]之構成的光學積層體。 [Example 1] Apply adhesive layer 1 (thickness 5µm) to each PET film on one side of polarizing film 1, transfer the other adhesive layer 1 (thickness 5µm) from the PET film to the other side, and then laminate on it. λ/4 member 1. At this time, the angle formed by the absorption axis of the absorptive polarizing film and the slow axis of the λ/4 member 1 becomes 45°. Next, another adhesive layer 1 (thickness 5 μm) is transferred from the PET film to the surface of the λ/4 member 1, and the protective member 1 is bonded on it. At this time, the acrylic film side surface of the protective member 1 is attached so that it is on the λ/4 member 1 side (in other words, the surface treatment layer becomes the outermost surface). In the above manner, an optical laminate having the composition of [release liner (PET film)/adhesive layer 1/polarizing film 1/adhesive layer 1/λ/4 member 1/adhesive layer 1/protective member 1] is obtained body.
[實施例2、比較例1-2]
除了將3層黏著劑層1中之1層以上變更成黏著劑層2外，以與實施例1相同方式而獲得光學積層體。將各光學積層體之構成顯示於表1。又，將黏著劑層1及2之線膨脹係數(N=2的平均值)顯示於表2。
[Example 2, Comparative Example 1-2]
An optical laminated body was obtained in the same manner as in Example 1, except that one or more of the three adhesive layers 1 were changed into
＜濕熱試驗＞ 從實施例及比較例所得之光學積層體剝離剝離襯材，並透過露出之黏著劑層貼合於玻璃板，而獲得試驗試樣。將試驗試樣放置於65℃90RH%之濕熱烘箱內240小時。測定光學積層體在試驗前、放置120小時或240小時後之面內相位差。面內相位差之測定係從烘箱取出試驗試樣，並從玻璃板側照射測定光來進行。將結果顯示於表1及圖3。此外，表1中，相位差變化表示光學積層體在試驗前之Re(590) before、與光學積層體在放置240小時後之Re(590) after的差(Re(590) before-Re(590) after)。 <Moist heat test> The release backing material was peeled off from the optical laminate obtained in Examples and Comparative Examples, and the exposed adhesive layer was bonded to a glass plate to obtain a test sample. Place the test sample in a humid heat oven at 65°C and 90RH% for 240 hours. The in-plane phase difference of the optical laminate was measured before the test and after being left for 120 hours or 240 hours. The in-plane phase difference is measured by taking out the test sample from the oven and irradiating the measurement light from the side of the glass plate. The results are shown in Table 1 and Figure 3. In addition, in Table 1, the phase difference change represents the difference between the Re(590) before of the optical laminate before the test and the Re(590) after of the optical laminate after being left for 240 hours (Re(590) before -Re(590 ) after ).
[表1] [Table 1]
[表2] [Table 2]
如表1及表2所示，實施例之光學積層體係合計3層黏著劑層中之2層以上之黏著劑層滿足0.8≦α1/α2≦1.2之關係者，從而在濕熱條件下之光學特性的穩定性優異。As shown in Table 1 and Table 2, in the optical laminate system of the embodiment, more than two adhesive layers out of a total of three adhesive layers satisfy the relationship of 0.8≦α1/α2≦1.2, so that the optical properties under hot and humid conditions are Excellent stability.
本發明不受上述實施形態所限，可進行各種變形。例如，可以實質上與上述實施形態所示構成相同之構成、可發揮相同作用效果之構成或可達成相同目的之構成作取代。The present invention is not limited to the above-described embodiment, and various modifications are possible. For example, it may be replaced by a structure that is substantially the same as that shown in the above-mentioned embodiment, a structure that can produce the same effects, or a structure that can achieve the same purpose.
產業上之可利用性 本發明實施形態之光學積層體例如可用於製造VR護目鏡等之附顯示器之護目鏡。 industrial availability The optical laminate according to the embodiment of the present invention can be used, for example, to manufacture goggles with a display such as VR goggles.
2:顯示系統
4:透鏡部
10:偏光構件
12:顯示元件
12':顯示面
12a:背光單元
12b:背光側偏光構件
12c:液晶單元
14:反射型偏光構件
16:第一透鏡部
18:半反射鏡
20:第一相位差構件
20a:第1λ/4構件
20b:正C板
22:第二相位差構件
24:第二透鏡部
26:使用者之眼睛
30:保護構件
100,100a,100b:光學積層體
a1:第一黏著劑層
a2:第二黏著劑層
a3:第三黏著劑層
b1:接著層
2:Display system
4: Lens department
10:Polarizing component
12:Display components
12':
圖1A係本發明一實施形態之光學積層體的概略剖面圖。 圖1B係本發明一實施形態之光學積層體的概略剖面圖。 圖2係顯示本發明一實施形態之顯示系統之概略構成的示意圖。 圖3係顯示實施例及比較例所得之光學積層體之濕熱試驗結果的圖。 FIG. 1A is a schematic cross-sectional view of an optical laminate according to an embodiment of the present invention. FIG. 1B is a schematic cross-sectional view of an optical laminate according to an embodiment of the present invention. FIG. 2 is a schematic diagram showing the schematic structure of a display system according to an embodiment of the present invention. FIG. 3 is a graph showing the results of the moist heat test of the optical laminates obtained in Examples and Comparative Examples.
2:顯示系統 2:Display system
4:透鏡部 4: Lens department
10:偏光構件 10:Polarizing component
12:顯示元件 12:Display components
12':顯示面 12':Display surface
12a:背光單元 12a: Backlight unit
12b:背光側偏光構件 12b: Backlight side polarizing component
12c:液晶單元 12c: LCD unit
14:反射型偏光構件 14: Reflective polarizing component
16:第一透鏡部 16: First lens part
18:半反射鏡 18: Half mirror
20:第一相位差構件 20: First phase difference member
22:第二相位差構件 22: Second phase difference member
24:第二透鏡部 24: Second lens unit
26:使用者之眼睛 26:User's Eyes
30:保護構件 30: Protective components
100:光學積層體 100: Optical laminated body
a1:第一黏著劑層 a1: first adhesive layer
a2:第二黏著劑層 a2: Second adhesive layer
a3:第三黏著劑層 a3: The third adhesive layer
Claims (9)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2022039285 | 2022-03-14 | ||
| JP2022-039286 | 2022-03-14 | ||
| JP2022-039285 | 2022-03-14 | ||
| JP2022039286 | 2022-03-14 | ||
| JP2022077633A JP7516456B2 (en) | 2022-05-10 | Display method | |
| JP2022-077676 | 2022-05-10 | ||
| JP2022-077677 | 2022-05-10 | ||
| JP2022-077634 | 2022-05-10 | ||
| JP2022077631A JP2023134316A (en) | 2022-03-14 | 2022-05-10 | Lens part, laminated body, display body, display body production method, and display method |
| JP2022077659A JP2023166841A (en) | 2022-05-10 | 2022-05-10 | Display system, display method, display body, and method for manufacturing display body |
| JP2022077658A JP2023166840A (en) | 2022-05-10 | 2022-05-10 | Display system, display method, display body, and method for manufacturing display body |
| JP2022-077633 | 2022-05-10 | ||
| JP2022-077658 | 2022-05-10 | ||
| JP2022077657A JP2023134317A (en) | 2022-03-14 | 2022-05-10 | Display system, display method, display body, and display body production method |
| JP2022077676A JP2023166851A (en) | 2022-05-10 | 2022-05-10 | Lens portion, laminate, display body, method for manufacturing display body, and display method |
| JP2022077678A JP2023166853A (en) | 2022-05-10 | 2022-05-10 | Lens portion, laminate, display body, method for manufacturing display body, and display method |
| JP2022077634A JP7516457B2 (en) | 2022-05-10 | Lens portion, laminate, display, manufacturing method of display, and display method | |
| JP2022-077657 | 2022-05-10 | ||
| JP2022077677A JP2023166852A (en) | 2022-05-10 | 2022-05-10 | Lens portion, laminate, display body, method for manufacturing display body, and display method |
| JP2022-077659 | 2022-05-10 | ||
| JP2022-077632 | 2022-05-10 | ||
| JP2022-077678 | 2022-05-10 | ||
| JP2022077632A JP7516455B2 (en) | 2022-05-10 | Lens portion, laminate, display, manufacturing method of display, and display method | |
| JP2022077679A JP7516458B2 (en) | 2022-05-10 | Lens portion, laminate, display, manufacturing method of display, and display method | |
| JP2022-077679 | 2022-05-10 | ||
| JP2022-077631 | 2022-05-10 | ||
| JP2022212221A JP2024095149A (en) | 2022-12-28 | Optical laminate and display system | |
| JP2022-212221 | 2022-12-28 |
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