TWI444676B - Polarizing plate and liquid crystal display device using the same - Google Patents

Polarizing plate and liquid crystal display device using the same Download PDF

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TWI444676B
TWI444676B TW096150182A TW96150182A TWI444676B TW I444676 B TWI444676 B TW I444676B TW 096150182 A TW096150182 A TW 096150182A TW 96150182 A TW96150182 A TW 96150182A TW I444676 B TWI444676 B TW I444676B
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polarizing plate
film
liquid crystal
cellulose acetate
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TW096150182A
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TW200841053A (en
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Minoru Wada
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Fujifilm Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)

Description

偏光板及使用它之液晶顯示裝置Polarizing plate and liquid crystal display device using same

本發明係關於偏光板及使用它之液晶顯示裝置，更詳細來說，係關於因熱等的變形所致的漏光等難以產生、且設置有黏著劑層及光學補償薄片之偏光板，及使用該偏光板、且影像顯示品格高的液晶顯示裝置。The present invention relates to a polarizing plate and a liquid crystal display device using the same, and more particularly to a polarizing plate which is difficult to generate light leakage due to deformation such as heat, and which is provided with an adhesive layer and an optical compensation sheet, and is used. The polarizing plate and the image display device have a high quality liquid crystal display device.

液晶顯示裝置係具有偏光板與液晶胞。現在主流的TN模式之TFT液晶顯示裝置係在偏光板與液晶胞之間配置光學補償薄片(相位差薄膜)，而實現顯示品格高的液晶顯示裝置。然而，在嚴苛的使用條件下，相位差薄膜中會因熱等的變形而在液晶顯示裝置的端部產生無法預期的相位差，而在根據該相位差的液晶顯示裝置黑顯示時，會有框狀的漏光(在液晶顯示裝置的端部中透射率的提昇)產生之情形。The liquid crystal display device has a polarizing plate and a liquid crystal cell. In the mainstream TN mode TFT liquid crystal display device, an optical compensation sheet (phase difference film) is disposed between the polarizing plate and the liquid crystal cell, thereby realizing a liquid crystal display device having a high display quality. However, under severe use conditions, an unpredictable phase difference occurs at the end of the liquid crystal display device due to deformation of heat or the like in the retardation film, and when the liquid crystal display device according to the phase difference is black, There is a case where a frame-shaped light leakage (increased transmittance in the end portion of the liquid crystal display device) occurs.

專利文獻1係提案一種光學補償板，其特徵係在相位差薄膜設置黏著層，其相位差薄膜的光彈性係數(m2 /N)與前述黏著層的彈性係數(N/m2 )之積(Y)係滿足Y≦1.2×10-5 ，以做為相位差特性難以變化之光學補償板。又，專利文獻2係提案一種偏光板保護層的線膨張係數與黏著劑層的彈性係數之積係為1.0×10-5 (℃-1 ．MPa)以下之規定的偏光板，以做為緩和漏光現象之偏光板。又，專利文獻3係提案一種偏光板保護層的光彈性係數與黏著劑層的彈性係數之積係為8.0×10-12 (m2 /N．MPa)以下之偏光板，以做為於面內不均難以發生之偏光板。Patent Document 1 proposes an optical compensation plate characterized in that an adhesive layer is provided on the retardation film, and the product of the photoelastic coefficient (m 2 /N) of the retardation film and the elastic coefficient (N/m 2 ) of the adhesive layer is set. (Y) satisfies Y≦1.2×10 -5 as an optical compensation plate whose phase difference characteristics are difficult to change. Further, Patent Document 2 proposes a polarizing plate having a linear expansion coefficient of a protective layer of a polarizing plate and an elastic modulus of an adhesive layer of 1.0 × 10 -5 (° C -1 .MPa) or less, as a mitigation. A polarizing plate for light leakage. Further, Patent Document 3 proposes a polarizing plate in which the product of the photoelastic coefficient of the protective layer of the polarizing plate and the elastic modulus of the adhesive layer is 8.0 × 10 -12 (m 2 / N·MPa) or less. A polarizing plate in which unevenness is difficult to occur.

【專利文獻1】特開2001-264538號公報 【專利文獻2】特開2002-122739號公報 【專利文獻3】特開2002-122740號公報[Patent Document 1] JP-A-2001-264538 [Patent Document 2] JP-A-2002-122739 [Patent Document 3] JP-A-2002-122740

然而，最近液晶顯示裝置的使用環境係變得多樣化，且其中所組裝之偏光板亦在耐久性之點方面要求更為優異之性能。However, recently, the environment in which liquid crystal display devices are used has become diverse, and the polarizing plates assembled therein have required more excellent performance in terms of durability.

因此，本發明的目的係提供因熱等的變形(strain)之漏光難以產生、耐久性優異之偏光板，及使用該偏光板且影像顯示品格高之液晶顯示裝置。又，本發明的另一目的係提供一種新穎的偏光板用黏著劑。Therefore, an object of the present invention is to provide a polarizing plate which is less likely to cause light leakage due to strain such as heat, and which is excellent in durability, and a liquid crystal display device which uses the polarizing plate and has high image display quality. Further, another object of the present invention is to provide a novel adhesive for a polarizing plate.

本發明人等係針對施加熱之液晶面板(觀察因顯著的熱不均所引起的漏光之加熱處理，例如在60C乾燥的乾燥機中施加靜置17小時，隨後取出等的處理之液晶面板等)專心一意檢討漏光現象，其結果得知藉由加熱等，不僅在偏光板間所配置的光學補償薄片會產生相位差，且存在於偏光板間之黏著劑層亦會產生相位差的知見。基於該知見，進一步檢討的結果，可得知在黏著劑層所發生之相位差係取決於黏著劑層的光彈性係數，且在上述光學補償薄片中係於增大產生的相位差之方向而產生的，因此，得知係取決於黏著劑層的光彈性係數，且增大了因上述熱不均所引起的漏光量。又，又已知因上述熱不均所引起的漏光量係取決於上述光學補償薄片的彈性係數。The inventors of the present invention are directed to a liquid crystal panel to which heat is applied (a heat treatment for observing light leakage due to significant thermal unevenness, for example, a liquid crystal panel which is left to stand for 17 hours in a 60 C dry dryer, and then taken out, etc.) In the meantime, it is known that the light leakage phenomenon is observed in the optical compensation sheet disposed between the polarizing plates by heating or the like, and the phase difference between the adhesive layers existing between the polarizing plates is also known. Based on this knowledge, as a result of further review, it is found that the phase difference occurring in the adhesive layer depends on the photoelastic coefficient of the adhesive layer, and is in the direction of increasing the phase difference generated in the optical compensation sheet. What is produced, therefore, is known to depend on the photoelastic coefficient of the adhesive layer and to increase the amount of light leakage caused by the aforementioned thermal unevenness. Further, it is also known that the amount of light leakage caused by the above-described thermal unevenness depends on the elastic modulus of the above-described optical compensation sheet.

基於此等知見而進行進一步檢討，其結果發現黏著劑層的光彈性係數及光學補償薄片的彈性係數，係與漏光之間有著特定的關係性，發現當黏著劑層的光彈性係數及光學補償薄片的彈性係數滿足規定的關係時，可提供一種前述漏光的問題係為解決、且具有優異性能之偏光板，進而完成本發明。Based on these findings, a further review was conducted. The results show that the photoelastic coefficient of the adhesive layer and the elastic coefficient of the optical compensation sheet have a specific relationship with the light leakage, and the photoelastic coefficient and optical compensation of the adhesive layer are found. When the elastic modulus of the sheet satisfies a predetermined relationship, it is possible to provide a polarizing plate which is a solution to the problem of light leakage and which has excellent performance, and further completes the present invention.

即，上述解決課題之手段係如以下所示。That is, the means for solving the above problems are as follows.

[1]一種偏光板，其特徵係至少具有偏光膜、黏著劑層、與光學補償薄片之偏光板，前述黏著劑層的光彈性係數為Cn(1/Pa)、前述光學補償薄片的彈性係數為E(Pa)時，下述式之值Y的絕對值為6.0×10-4 以下： Y=-7.0×105 ×Cn+4.3×10-13 ×E-1.34×10-3 。[1] A polarizing plate characterized by comprising at least a polarizing film, an adhesive layer, and a polarizing plate with an optical compensation sheet, wherein a photoelastic coefficient of the adhesive layer is Cn (1/Pa), and an elastic coefficient of the optical compensation sheet. In the case of E (Pa), the absolute value of the value Y of the following formula is 6.0 × 10 -4 or less: Y = -7.0 × 10 5 × Cn + 4.3 × 10 -13 × E - 1.34 × 10 -3 .

[2]如[1]之偏光板，其中前述黏著劑層係包含丙烯酸系黏著劑。[2] The polarizing plate of [1], wherein the adhesive layer comprises an acrylic adhesive.

[3]如[2]之偏光板，其中前述丙烯酸系黏著劑係含有同元聚合物的光彈性係數為正之單體的至少一種之聚合物。[3] The polarizing plate according to [2], wherein the acrylic pressure-sensitive adhesive contains at least one polymer of a homopolymer having a positive photoelastic coefficient.

[4]如[2]或[3]之偏光板，其中前述丙烯酸系黏著劑係包含下述通式(I)所示單體的至少一種之聚合物： [4] The polarizing plate according to [2] or [3] wherein the acrylic adhesive is a polymer comprising at least one of the monomers represented by the following formula (I):

式中，R1 係表示氫原子或甲基；R2 係表示氫原子或取代基；R3 及R4 係分別表示氫原子或取代基；m係表示0以上 的整數，n係表示0~5的整數，m及n係各自為2以上的整數時，複數個的R2 、R3 及R4 係分別可為相同或是不同。In the formula, R 1 represents a hydrogen atom or a methyl group; R 2 represents a hydrogen atom or a substituent; R 3 and R 4 each represent a hydrogen atom or a substituent; m represents an integer of 0 or more, and n represents 0 to 0; When an integer of 5, m and n are each an integer of 2 or more, a plurality of R 2 , R 3 and R 4 may be the same or different.

[5]如[1]~[4]項中任一項之偏光板，其中前述光學補償薄片的光彈性係數為50×10-12 (1/Pa)以下。[5] The polarizing plate according to any one of [1] to [4] wherein the optical compensation sheet has a photoelastic coefficient of 50 × 10 -12 (1/Pa) or less.

[6]如[1]~[5]項中任一項之偏光板，其中前述黏著劑層係配置於最外側，且剝離紙係貼附於該黏著劑層的表面。[6] The polarizing plate according to any one of [1] to [5] wherein the adhesive layer is disposed on the outermost side, and the release paper is attached to the surface of the adhesive layer.

[7]一種液晶顯示裝置，其特徵係至少含有液晶胞、與如[1]~[5]項中任一項之偏光板。[7] A liquid crystal display device comprising at least a liquid crystal cell and a polarizing plate according to any one of [1] to [5].

[8]如[7]之液晶顯示裝置，其中前述液晶胞的基板表面與偏光板之黏著劑層的表面係接觸而配置的。[8] The liquid crystal display device according to [7], wherein the surface of the substrate of the liquid crystal cell is disposed in contact with the surface of the adhesive layer of the polarizing plate.

[9]一種偏光板用丙烯酸系黏著劑，其特徵係含有下述通式(I)所示單體的至少一種之聚合物 [9] An acrylic adhesive for a polarizing plate, characterized by comprising at least one polymer of a monomer represented by the following formula (I)

式中，R1 係表示氫原子或甲基；R2 係表示氫原子或取代基；R3 及R4 係分別表示氫原子或取代基；m係表示0以上的整數，n係表示0~5的整數，m及n係各自為2以上的整數時，複數個的R2 、R3 及R4 係分別可為相同或是不同。In the formula, R 1 represents a hydrogen atom or a methyl group; R 2 represents a hydrogen atom or a substituent; R 3 and R 4 each represent a hydrogen atom or a substituent; m represents an integer of 0 or more, and n represents 0 to 0; When an integer of 5, m and n are each an integer of 2 or more, a plurality of R 2 , R 3 and R 4 may be the same or different.

[10]如[2]之偏光板，其中前述丙烯酸系黏著劑係含有由同元聚合物的光彈性係數為正之單體所衍生的至少一種重複單位之共聚物。[10] The polarizing plate of [2], wherein the acrylic adhesive comprises a copolymer of at least one repeating unit derived from a monomer having a positive photoelastic coefficient of a homopolymer.

[11]如[10]之偏光板，其中前述共聚物係含有選自於由芳香族系的丙烯酸酯單體及芳香族系的甲基丙烯酸酯單 體的至少一種所衍生之重複單位的共聚物。[11] The polarizing plate according to [10], wherein the copolymer contains a methacrylate selected from an aromatic acrylate monomer and an aromatic methacrylate. a copolymer of at least one of the repeating units derived from the body.

[12]如[10]或[11]之偏光板，其中前述共聚物係含有由下述通式(I)所示單體的至少一種所衍生之重複單位的共聚物： [12] The polarizing plate according to [10] or [11] wherein the copolymer contains a copolymer of a repeating unit derived from at least one of the monomers represented by the following formula (I):

式中，R1 係表示氫原子或甲基；R2 係表示氫原子或取代基；R3 及R4 係分別表示氫原子或取代基；m係表示0以上的整數，n係表示0~5的整數，m及n係各自為2以上的整數時，複數個的R2 、R3 及R4 係分別可為相同或是不同。In the formula, R 1 represents a hydrogen atom or a methyl group; R 2 represents a hydrogen atom or a substituent; R 3 and R 4 each represent a hydrogen atom or a substituent; m represents an integer of 0 or more, and n represents 0 to 0; When an integer of 5, m and n are each an integer of 2 or more, a plurality of R 2 , R 3 and R 4 may be the same or different.

[13]如[10]~[12]項中任一項之偏光板，其中前述光學補償薄片的光彈性係數為50×10-12 (1/Pa)以下。[13] The polarizing plate according to any one of [10], wherein the optical compensation sheet has a photoelastic coefficient of 50 × 10 -12 (1/Pa) or less.

[14]一種液晶顯示裝置，其特徵係至少含有液晶胞、與如[9]~[13]項中任一項之偏光板。[14] A liquid crystal display device comprising at least a liquid crystal cell and a polarizing plate according to any one of [9] to [13].

[15]如[14]之液晶顯示裝置，其中前述液晶胞的基板表面與偏光板之黏著劑層的表面係接觸而配置的。[15] The liquid crystal display device according to [14], wherein the surface of the substrate of the liquid crystal cell is disposed in contact with the surface of the adhesive layer of the polarizing plate.

[16]一種偏光板用丙烯酸系黏著劑，其特徵係包含具有從下述通式(I)所示單體的至少一種所衍生之重複單位的共聚物： [16] An acrylic adhesive for a polarizing plate, characterized by comprising a copolymer having a repeating unit derived from at least one of the monomers represented by the following formula (I):

式中，R1 係表示氫原子或甲基；R2 係表示氫原子或取代基；R3 及R4 係分別表示氫原子或取代基；m係表示0以上的整數，n係表示0~5的整數，m及n係各自為2以上的整數時，複數個的R2 、R3 及R4 係分別可為相同或是不同。In the formula, R 1 represents a hydrogen atom or a methyl group; R 2 represents a hydrogen atom or a substituent; R 3 and R 4 each represent a hydrogen atom or a substituent; m represents an integer of 0 or more, and n represents 0 to 0; When an integer of 5, m and n are each an integer of 2 or more, a plurality of R 2 , R 3 and R 4 may be the same or different.

根據本發明，可提供一種能解決在嚴苛的使用環境中所產生的漏光問題、起具有優異性能之偏光板，及使用它之液晶顯示裝置。According to the present invention, it is possible to provide a polarizing plate which can solve the problem of light leakage generated in a severe use environment, and which has excellent performance, and a liquid crystal display device using the same.

(實施發明之形態)(Formation of the invention)

以下，詳細說明本發明。另外，本說明書中「~」係以含有其前後所記載之數值當作下限值及上限值之意而使用。 首先，說明本發明的偏光板。Hereinafter, the present invention will be described in detail. In the present specification, "~" is used in the sense that the numerical values described before and after are used as the lower limit and the upper limit. First, the polarizing plate of the present invention will be described.

[偏光板][Polarizer]

本發明係關一種偏光板，其係至少含有偏光層、黏著劑層及光學補償薄片之偏光板，其中前述黏著劑層的光彈性係數設為Cn(1/Pa)、前述光學補償薄片的彈性係數設為E(Pa)時，下述式之值Y的絕對值為6.0×10-5 以下之偏光板。The present invention relates to a polarizing plate which is a polarizing plate comprising at least a polarizing layer, an adhesive layer and an optical compensation sheet, wherein the photoelastic coefficient of the adhesive layer is set to Cn (1/Pa), and the elasticity of the optical compensation sheet is When the coefficient is E (Pa), the absolute value of the value Y of the following formula is a polarizing plate of 6.0 × 10 -5 or less.

Y=-7.0×105 ×Cn+4.3×10-13 ×E-1.34×10-3 Y=-7.0×10 5 ×Cn+4.3×10 -13 ×E-1.34×10 -3

關於Y絕對值的最小值方面係沒有特別地限制，在0~6.0×10-5 範圍中的任一者均可表現出本發明之效果。本發明的偏光板中，在對液晶顯示裝置施加熱等之情形下，偏光板的構件、具體而言黏著劑層與光學補償薄片係組合 成適合於打消了彼等所發生之相位差，其結果，上述式所定義之Y的絕對值係為在6.0×10-5 以下。因此，經熱不均後偏光特性等的光學特性沒有變動，且耐久性優異。因而，具有本發明偏光板之液晶顯示裝置係即使在高溫下等的嚴苛的使用狀況中，於黑顯示時在框狀中透射率提昇係受到了抑制，漏光難以產生，且顯示品格優異。The minimum value of the absolute value of Y is not particularly limited, and any of the ranges of 0 to 6.0 × 10 -5 can exhibit the effects of the present invention. In the polarizing plate of the present invention, in the case where heat or the like is applied to the liquid crystal display device, the members of the polarizing plate, specifically, the adhesive layer and the optical compensation sheet are combined to cancel the phase difference which occurs therebetween, and As a result, the absolute value of Y defined by the above formula is 6.0 × 10 -5 or less. Therefore, the optical characteristics such as the polarization characteristics after heat unevenness do not change, and the durability is excellent. Therefore, in the liquid crystal display device having the polarizing plate of the present invention, even in a severe use condition such as high temperature, the transmittance improvement in the frame shape during black display is suppressed, light leakage is hard to occur, and the display quality is excellent.

第1圖中係表示本發明偏光板之一例的剖面模式圖。第1圖所示之偏光板係具有依序積層黏著劑層1、光學補償薄片2、偏光膜3、保護層4之構造。組裝至液晶顯示裝置之際係藉由黏著劑層1，貼附至其他構件，例如液晶胞的基板表面。又，如第2圖所示的樣子，亦可在黏著劑層1的表面配置剝離紙5，以進行保管及搬送等。保護膜係以使用光透射率為80%以上之一般聚合物薄膜為佳。較宜係使用乙酸纖維素薄膜做為該聚合物薄膜。關於乙酸纖維素薄膜，可使用與後述的光學補償薄片或其支持體之例相同者。Fig. 1 is a schematic cross-sectional view showing an example of a polarizing plate of the present invention. The polarizing plate shown in Fig. 1 has a structure in which an adhesive layer 1, an optical compensation sheet 2, a polarizing film 3, and a protective layer 4 are sequentially laminated. When assembled to the liquid crystal display device, it is attached to other members such as the surface of the substrate of the liquid crystal cell by the adhesive layer 1. Further, as shown in Fig. 2, the release paper 5 may be placed on the surface of the adhesive layer 1 for storage, transportation, and the like. The protective film is preferably a general polymer film having a light transmittance of 80% or more. It is preferred to use a cellulose acetate film as the polymer film. As the cellulose acetate film, the same as the example of the optical compensation sheet or the support described later can be used.

另外，第1圖及第2圖的構成均表示光學補償薄片2係有偏光膜3的保護層之構成，惟在光學補償薄片2與偏光膜3之間亦可以另一方式，配置由與保護層4同樣的材料所構成的保護層。In addition, the configurations of the first and second drawings each show that the optical compensation sheet 2 has a protective layer of the polarizing film 3, but another arrangement between the optical compensation sheet 2 and the polarizing film 3 may be disposed and protected. Layer 4 is a protective layer of the same material.

《偏光膜》Polarized film

使用於本發明偏光板之偏光膜係可為碘系偏光膜、使用二色性染料之染料系偏光膜、及多烯系偏光膜中任一者。碘系偏光膜及染料系偏光膜係使用一般的聚乙烯醇系薄膜來製造。製造方法係可應用以往習知的方法，可舉例 如上述專利文獻1中記載的方法。The polarizing film used in the polarizing plate of the present invention may be any of an iodine-based polarizing film, a dye-based polarizing film using a dichroic dye, and a polyene-based polarizing film. The iodine-based polarizing film and the dye-based polarizing film are produced using a general polyvinyl alcohol-based film. The manufacturing method can be applied to conventional methods, and can be exemplified The method described in the above Patent Document 1.

《黏著劑層》Adhesive Layer

本發明之偏光板所具有的黏著劑層，係為了滿足上述條件，其光彈性係數為正者為佳。前述黏著劑層係含有至少一種的黏著劑，且藉由至少接觸其他構件而對該構件具有黏著能力之某層。用於該黏著劑層形成之黏著劑(亦能包含稱為黏合劑者)只要所形成之黏著劑層滿足前述Y值之條件，則沒有特別地限制而可以使用。黏著劑的原料係以橡膠系黏著劑、丙烯酸系黏著劑、矽系黏著劑、胺甲酸酯系黏著劑、聚醚系黏著劑、及聚酯系黏著劑等的感壓系之黏著劑為佳。The adhesive layer of the polarizing plate of the present invention preferably has a photoelastic coefficient in order to satisfy the above conditions. The aforementioned adhesive layer contains at least one adhesive and a layer having adhesive ability to the member by at least contacting other members. The adhesive for forming the adhesive layer (which may also include a binder) may be used without particular limitation as long as the adhesive layer formed satisfies the aforementioned Y value. The adhesive is made of a pressure-sensitive adhesive such as a rubber-based adhesive, an acrylic adhesive, an enamel adhesive, an urethane-based adhesive, a polyether adhesive, or a polyester adhesive. good.

丙烯酸系黏著劑的情形中，可做為在其原料聚合物之丙烯酸系聚合物中所使用之單體，係可使用各種(甲基)丙烯酸酯[(甲基)丙烯酸酯係為總稱丙烯酸酯及甲基丙烯酸酯之表現，以下附有(甲基)之化合物名係有同樣的意味]。做為該(甲基)丙烯酸酯之具體例係可舉例如(甲基)丙烯酸甲基、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯等，此等係可單獨或組合而使用。又，為了賦予所得之丙烯酸系聚合物極性，亦可少量使用(甲基)丙烯酸來取代部分的前述(甲基)丙烯酸酯。再者，亦可併用做為交聯性單體之(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸2-羥基乙酯、正羥甲基(甲基)丙烯醯胺等。可進一步根據所所期望的，在不損及(甲基)丙烯酸酯聚合物的黏著特性之程度，併用其他可共聚合的單體，例如乙酸乙烯酯、苯乙烯等而得到。In the case of an acrylic adhesive, it can be used as a monomer used in the acrylic polymer of the base polymer, and various (meth) acrylates [(meth) acrylates are collectively referred to as acrylates). And the performance of methacrylate, the following compound name with (methyl) has the same meaning]. Specific examples of the (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Esters and the like, these may be used singly or in combination. Further, in order to impart polarity to the obtained acrylic polymer, a part of the (meth) acrylate may be replaced with a small amount of (meth)acrylic acid. Further, it may be used in combination as a crosslinkable monomer, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, or n-hydroxymethyl(meth)acrylamide. Further, it can be obtained according to the desired degree of adhesion of the copolymerizable monomer, such as vinyl acetate, styrene or the like, without impairing the adhesive properties of the (meth) acrylate polymer.

橡膠系黏著劑的原料聚合物係可舉例如天然橡膠、異戊二烯系橡膠、苯乙烯-丁二烯系橡膠、再生橡膠、聚異丁烯系橡膠，以及苯乙烯-異戊二烯-苯乙烯系橡膠、苯乙烯-丁二烯-苯乙烯系橡膠等。Examples of the raw material polymer of the rubber-based adhesive include natural rubber, isoprene-based rubber, styrene-butadiene rubber, recycled rubber, polyisobutylene rubber, and styrene-isoprene-styrene. Rubber, styrene-butadiene-styrene rubber, and the like.

矽系黏著劑的原料聚合物係可舉例如二甲基聚矽氧烷、二苯基聚矽氧烷等。The raw material polymer of the oxime-based adhesive may, for example, be dimethylpolysiloxane or diphenylpolysiloxane.

聚醚系黏著劑的原料聚合物係可舉例如聚乙烯基乙基醚、聚乙烯基丁基醚、聚乙烯基異丁基醚等。The base polymer of the polyether adhesive may, for example, be polyvinyl ethyl ether, polyvinyl butyl ether or polyvinyl isobutyl ether.

前述黏著劑層的光彈性係數Cn係越大越好，Cn為正者為較佳。關於光彈性係數的上限係沒有特別地限制，惟現存的材料中，一般認為最大值約為1000×10-12 (1/Pa)。但是，經組合之光學補償薄片的彈性係數係即使黏著劑層的Cn為負的，亦滿足上述式所定義之Y在規定條件之範圍，當然能得到本發明之效果。The photoelastic coefficient Cn of the adhesive layer is preferably as large as possible, and Cn is preferred. The upper limit of the photoelastic coefficient is not particularly limited, but among the existing materials, the maximum value is generally considered to be about 1000 × 10 -12 (1/Pa). However, the elastic modulus of the combined optical compensation sheet is such that, even if the Cn of the adhesive layer is negative, and the Y defined by the above formula satisfies the range of the predetermined condition, the effect of the present invention can of course be obtained.

另外，現在富士軟片(股)製WV薄膜的光學補償薄片中所使用的黏著劑層(Sanritz公司製PET-W(S))之光彈性係數Cn，測定的結果為-750×10-12 (1/Pa)，為負的。In addition, the photoelastic coefficient Cn of the adhesive layer (PET-W(S) manufactured by Sanritz Co., Ltd.) used in the optical compensation sheet of the WV film manufactured by Fujifilm Co., Ltd. is -750×10 -12 (the result of measurement is -750×10 -12 ) 1/Pa), negative.

使前述黏著劑層的光彈性係數符合所期望之值，係有選擇做為黏著劑中所使用的主劑之聚合物的方法。除此以外，亦可考慮以下之方法，惟不限定於該方法。其中一者係調節樹脂分子自身的光學各向異性、亦即調節固有雙折射之方法，其係為有效的手段。可做為調節固有雙折射之方法係如在「光學用透明樹脂」(技術情報協會(2001年刊))的第20頁中，所述之(1)分子構造的改質、(2)無規共聚合法、(3)合金化法，此等的方法在本發明中亦可加以應用。The photoelastic coefficient of the above-mentioned adhesive layer is made to meet a desired value, and a method of selecting a polymer as a main component used in the adhesive is selected. In addition to the above, the following methods are also conceivable, but are not limited to this method. One of them is an effective means for adjusting the optical anisotropy of the resin molecule itself, that is, the method of adjusting the intrinsic birefringence. The method of adjusting the intrinsic birefringence is as described in the "Optical Resin for Optical" (Technical Information Association (2001)", page 20, (1) Modification of molecular structure, (2) Randomization. Copolymerization, (3) alloying, and the like can also be applied in the present invention.

此外，如成形加工，(2003年)，第15卷，第3號，第196頁中所述般，較宜係亦可使用各向異性低分子的塗布液法。Further, as described in Forming, (2003), Vol. 15, No. 3, p. 196, an anisotropic low molecular coating liquid method can also be used.

又，SCIENCE,(2003),VOL301,p812中所揭示的，特佳係可使用各向異性無機粒子塗布液法。Further, as disclosed in SCIENCE, (2003), VOL 301, p812, an anisotropic inorganic particle coating liquid method can be used.

又，為使黏著劑層的光彈性係數符合所期望之值，亦可調整黏著劑中所使用之聚合物的分子量、調整原料的混合比。Further, in order to make the photoelastic coefficient of the adhesive layer conform to a desired value, the molecular weight of the polymer used in the adhesive can be adjusted, and the mixing ratio of the raw materials can be adjusted.

在丙烯酸系之黏著劑的情形中，現在經常使用的大部分者係具有負的光彈性係數，且其絕對值係大到約800×10-12 (1/Pa)程度。本發明人等係為了使光彈性係數的絶對值較小，而發現使用做為黏著劑使用之原料聚合物、同元聚合物的光彈性係數為正之單體的聚合物、亦即該單體的同元聚合物及共聚物中的任一者為佳。例如，聚甲基丙烯酸甲酯的光彈性係數之值係為-3.8×1012 (1/Pa)。另一方面，聚甲基丙烯酸苄酯、聚丙烯酸苄酯、聚甲基丙烯酸苯酯的光彈性係數之值係大概為+40×1012 ~+50×1012 (1/Pa)。顯示正光彈性係數之同元聚合物的單體，係例如以包含從選自於甲基丙烯酸苄酯、苄基丙烯酸酯及甲基丙烯酸苯酯，以及丙烯酸苯氧基烷基(例如，丙烯酸苯氧基甲基、丙烯酸苯氧基丙基、丙烯酸苯氧基丁基等)等芳香族系的丙烯酸酯及芳香族系之甲基丙烯酸酯的至少一種單體所衍生之重複單位、的同元聚合物及共聚物為佳。In the case of acrylic adhesives, most of the ones that are often used now have a negative photoelastic coefficient and have an absolute value as large as about 800 x 10 -12 (1/Pa). In order to make the absolute value of the photoelastic coefficient small, the present inventors have found that a polymer which uses a raw material polymer as an adhesive and a homopolymer of a homopolymer having a positive photoelastic coefficient, that is, the monomer Any of the homopolymers and copolymers is preferred. For example, the value of the photoelastic coefficient of polymethyl methacrylate is -3.8 x 10 12 (1/Pa). On the other hand, the values of the photoelastic coefficients of benzyl polymethyl methacrylate, benzyl polyacrylate, and polyphenyl methacrylate are approximately +40 × 10 12 to + 50 × 10 12 (1/Pa). A monomer exhibiting a positive photoelastic coefficient of a homopolymer, for example, comprising a benzyloxy group selected from benzyl methacrylate, benzyl acrylate, and phenyl methacrylate, and a phenoxyalkyl acrylate (for example, benzo acrylate) Repeating unit derived from at least one monomer of an aromatic acrylate such as oxymethyl group, phenoxypropyl acrylate or phenoxy butyl acrylate or an aromatic methacrylate Polymers and copolymers are preferred.

根據以上的觀點，例如前述黏著劑層係包含具有聚合主要為含有下述通式(I)所示化合物的聚合性組成物所得之聚合物(同元聚合物或共聚物)之丙烯酸系黏著劑者為佳。From the above viewpoints, for example, the above-mentioned adhesive layer contains an acrylic adhesive having a polymer (homopolymer or copolymer) obtained by polymerizing a polymerizable composition mainly containing a compound represented by the following formula (I). It is better.

式中，R1 係表示氫原子或甲基，R2 係表示氫原子或取代基。R3 及R4 係分別表示氫原子或取代基。m係表示0以上的整數，n係表示0~5的整數。m及n係各自為2以上的整數時，複數個的R2 、R3 及R4 係可相同或不同。In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents a hydrogen atom or a substituent. R 3 and R 4 each represent a hydrogen atom or a substituent. m represents an integer of 0 or more, and n represents an integer of 0-5. When m and n each are an integer of 2 or more, a plurality of R 2 , R 3 and R 4 may be the same or different.

說明前述通式(I)。The above formula (I) will be described.

通式(I)中，R1 係表示氫原子或甲基，較佳為甲基。In the formula (I), R 1 represents a hydrogen atom or a methyl group, preferably a methyl group.

又，R2 係表示氫原子或取代基。做為取代基之例係可舉例如下述取代基群T。Further, R 2 represents a hydrogen atom or a substituent. As an example of a substituent, the following substituent group T is mentioned, for example.

(取代基群T)(substituent group T)

可做為取代基者係可舉例如：鹵素原子(例如，氟原子、氯原子、溴原子、碘原子)、烷基(較佳為碳數1~30的烷基，例如甲基、乙基、正丙基、異丙基、第三丁基、正辛基、2-乙基己基)、環烷基(較佳係碳數3~30的取代或無取代之環烷基，例如環己基、環戊基、4-正十二烷基環己基)、二環烷基(較佳係碳數5~30的取代或無取代之二環烷基、亦即自碳數5~30的二環鏈烷去掉一個氫原子之一價基。例如，二環[1.2.2]庚烷-2-基、二環[2.2.2]辛烷-3-基)、鏈烯基(較佳為碳數2~30的取代或無取代之鏈烯基，例如乙烯基、烯丙基)、環鏈烯基(較佳係碳數3~30的取代或無取代之環鏈烯基、亦即自碳數3~30的環鏈烯去掉一個氫原子之一價基。例如，2-環戊烯-1-基、2-環己烯-1-基)、二 環鏈烯基(取代或無取代之二環鏈烯基、較佳為碳數5~30的取代或無取代之二環鏈烯基、亦即具有一個雙鍵之二環鏈烯中去掉一個氫原子之一價基。例如，二環[2.2.1]庚-2-烯-1-基、二環[2.2.2]辛-2-烯-4-基)、炔基(較佳係碳數2~30的取代或無取代之炔基，例如乙炔基、炔丙基)、芳基(較佳為碳數6~30的取代或無取代之芳基，例如苯基、對甲苯基、萘基)、雜環基(較佳為自5或6員的取代或無取代之芳香族或非芳香族的雜環化合物去掉一個氫原子之一價基，更佳為碳數3~30的5或6員之芳香族雜環基。例如，2-呋喃基、2-噻吩基、2-嘧啶基、2-苯并噻唑基)、氰基、羥基、硝基、羧基、烷氧基(較佳係碳數1~30的取代或無取代之烷氧基，例如甲氧基、乙氧基、異丙氧基、第三丙氧基、正辛氧基、2-甲氧基乙氧基)、芳氧基(較佳係碳數6~30的取代或無取代之芳氧基，例如苯氧基、2-甲基苯氧基、4-第三丁基苯氧基、3-硝基苯氧基、2-十四烷醯基胺基苯氧基)、矽烷氧基(較佳係碳數3~20的矽烷氧基，例如三甲基矽烷氧基、第三丁基二甲基矽烷氧基)、雜環氧基(較佳係碳數2~30的取代或無取代之雜環氧基、1-苯基四唑-5-氧基、2-四氫化吡喃基氧基)、醯氧基(較佳為甲醯氧基、碳數2~30的取代或無取代之烷基羰氧基、碳數6~30的取代或無取代之芳基羰氧基，例如甲醯氧基、乙醯氧基、三甲基乙醯基氧基、硬脂醯氧基、苯甲醯氧基、對甲氧基苯基羰氧基)、胺甲醯氧基(較佳係碳數1~30的取代或無取代之胺甲醯氧基，例如N,N-二甲基胺甲醯氧基、N,N-二乙基胺甲醯氧基、味啉代羰氧基、N,N-二-正辛基胺基羰氧基、 N-正辛基胺甲醯氧基)、烷氧基羰氧基(較佳係碳數2~30的取代或無取代之烷氧基羰氧基，例如甲氧基羰氧基、乙氧基羰氧基、第三丙氧基羰氧基、正辛基羰氧基)、芳氧基羰氧基(較佳係碳數7~30的取代或無取代之芳氧基羰氧基，例如苯氧基羰氧基、對甲氧基苯氧基羰氧基、對正十六烷氧基苯氧基羰氧基)、胺基(較佳係胺基、碳數1~30的取代或無取代之烷基胺基、碳數6~30的取代或無取代之苯胺基，例如胺基、甲基胺基、二甲基胺基、苯胺基、N-甲基-苯胺基、二苯基胺基)、醯胺基(較佳係甲醯胺基、碳數1~30的取代或無取代之烷基羰基胺基、碳數6~30的取代或無取代之芳基羰基胺基，例如甲醯胺基、乙醯胺基、三甲基乙醯基胺基、月桂醯胺基、苯甲醯基胺基)、胺基羰基胺基(較佳係碳數1~30的取代或無取代之胺基羰基胺基，例如胺甲醯基胺基、N,N-二甲基胺基羰基胺基、N,N-二乙基胺基羰基胺基、味啉代羰基胺基)、烷氧基羰基胺基(較佳為碳數2~30的取代或無取代之烷氧基羰基胺基，例如甲氧基羰基胺基、乙氧基羰基胺基、第三丙氧基羰基胺基、正十八烷氧基羰基胺基、N-甲基-甲氧基羰基胺基)、芳氧基羰基胺基(較佳係碳數7~30的取代或無取代之芳氧基羰基胺基，例如苯氧基羰基胺基、對氯基苯氧基羰基胺基、間正辛氧基苯氧基羰基胺基)、胺磺醯基胺基(較佳係碳數0~30的取代或無取代之胺磺醯基胺基，例如胺磺醯基胺基、N,N-二甲基胺基磺醯基胺基、N-正辛基胺基磺醯基胺基)、烷基及芳基磺醯基胺基(較佳為碳數1~30的取代或無取代之烷基磺醯基胺基、碳數6~30的取代或無取代之芳基磺醯基胺 基，例如甲基磺醯基胺基、丁基磺醯基胺基、苯基磺醯基胺基、2,3,5-三氯基苯基磺醯基胺基、對甲基苯基磺醯基胺基)、氫硫基、烷硫基(較佳係碳數1~30的取代或無取代之烷硫基，例如甲硫基、乙硫基、正十六烷硫基)、芳硫基(較佳為碳數6~30的取代或無取代之芳硫基，例如苯硫基、對氯基苯硫基、間甲氧基苯硫基)、雜環硫基(較佳為碳數2~30的取代或無取代之雜環硫基，例如2-苯并噻唑硫基、1-苯基四唑-5-硫基)、胺磺醯基(較佳為碳數0~30的取代或無取代之胺磺醯基，例如N-乙基胺磺醯基、N-(3-十二烷氧基丙基)胺磺醯基、N,N-二甲基胺磺醯基、N-乙醯胺磺醯基、N-苯甲醯基胺磺醯基、N-(N'-苯基胺甲醯基)胺磺醯基)、磺酸基、烷基及芳基亞磺醯基(較佳係碳數1~30的取代或無取代之烷基亞磺醯基、6~30的取代或無取代之芳基亞磺醯基，例如甲基亞磺醯基、乙基亞磺醯基、苯基亞磺醯基、對甲基苯基亞磺醯基)、烷基及芳基磺醯基(較佳係碳數1~30的取代或無取代之烷基磺醯基、6~30的取代或無取代之芳基磺醯基，例如甲基磺醯基、乙基磺醯基、苯基磺醯基、對甲基苯基磺醯基)、醯基(較佳為甲醯基、碳數2~30的取代或無取代之烷基羰基、碳數7~30的取代或無取代之芳基羰基，例如乙醯基、三甲基乙醯基苯甲醯基)、芳氧基羰基(較佳係碳數7~30的取代或無取代之芳氧基羰基，例如苯氧基羰基、o-氯基苯氧基羰基、間硝基苯氧基羰基、對第三丁基苯氧基羰基)、烷氧基羰基(較佳係碳數2~30的取代或無取代之烷氧基羰基，例如甲氧基羰基、乙氧基羰基、第三丙氧基羰基、正十八烷氧基羰基)、 胺甲醯基(較佳係碳數1~30的取代或無取代之胺甲醯基，例如胺甲醯基、N-甲基胺甲醯基、N,N-二甲基胺甲醯基、N,N-二-正辛基胺甲醯基、N-(甲基磺醯基)胺甲醯基)、芳基及雜環偶氮基(較佳為碳數6~30的取代或無取代之芳基偶氮基、碳數3~30的取代或無取代之雜環偶氮基，例如苯基偶氮基、對氯基苯基偶氮基、5-乙硫基-1,3,4-噻二唑-2-基偶氮基)、醯亞胺基(較佳係N-琥珀醯亞胺基、N-磷苯二甲醯亞胺基)、膦基(較佳係碳數2~30的取代或無取代之膦基，例如二甲基膦基、二苯基膦基、甲基苯氧基膦基)、氧膦基(較佳係碳數2~30的取代或無取代之氧膦基，例如氧膦基、二辛氧基氧膦基、二乙氧基氧膦基)、氧膦氧基(較佳係碳數2~30的取代或無取代之氧膦氧基，例如二苯氧基氧膦氧基、二辛氧基氧膦氧基)、氧膦基胺基(較佳係碳數2~30的取代或無取代之氧膦基胺基，例如二甲氧基氧膦基胺基、二甲基胺基氧膦基胺基)、矽烷基(較佳係碳數3~30的取代或無取代之矽烷基，例如三甲基矽烷基、第三丁基二甲基矽烷、苯基二甲基矽烷基)等的取代基。The substituent may be, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom) or an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms such as a methyl group or an ethyl group). , n-propyl, isopropyl, tert-butyl, n-octyl, 2-ethylhexyl), cycloalkyl (preferably a substituted or unsubstituted cycloalkyl group having a carbon number of 3 to 30, such as cyclohexyl , cyclopentyl, 4-n-dodecylcyclohexyl), bicycloalkyl (preferably a substituted or unsubstituted dicycloalkyl group having a carbon number of 5 to 30, that is, a carbon number of 5 to 30 The cycloalkane removes one of the valent groups of one hydrogen atom, for example, a bicyclo[1.2.2]heptan-2-yl, a bicyclo[2.2.2]oct-3-yl group, an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group, an allyl group, or a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, A valent group of one hydrogen atom is removed from a cycloalkane having a carbon number of 3 to 30. For example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), a cycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicyclic alkenyl group having 5 to 30 carbon atoms, that is, a bicyclic olefin having one double bond is removed a valence group of a hydrogen atom, for example, bicyclo[2.2.1]hept-2-en-1-yl, bicyclo[2.2.2]oct-2-en-4-yl), alkynyl (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group, a propargyl group, an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group or a p-tolyl group) , naphthyl), heterocyclic group (preferably a substituted or unsubstituted aromatic or non-aromatic heterocyclic compound derived from 5 or 6 members, one valent group of one hydrogen atom is removed, more preferably 3 to 30 carbon atoms A 5- or 6-membered aromatic heterocyclic group. For example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano, hydroxy, nitro, carboxy, alkoxy (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, third propoxy, n-octyloxy, 2-methoxyB Oxyl), aryloxy (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2- Phenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecylideneaminophenphenoxy group, decyloxy group (preferably having a carbon number of 3-20) a decyloxy group such as a trimethyldecyloxy group, a tert-butyldimethyl decyloxy group, a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1 Phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), anthracenyloxy (preferably a methyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as methyl methoxy, ethoxylated, trimethyl ethyloxy, stearyloxy, benzyl methoxy, Methoxyphenylcarbonyloxy), amine methyl methoxy (preferably a substituted or unsubstituted amine methyl methoxy group having 1 to 30 carbon atoms, such as N,N-dimethylamine methyl methoxy group, N,N-diethylamine methyl methoxy, morpholinocarbonyloxy, N,N-di-n-octylaminocarbonyloxy, N-n-octylamine methyl methoxy), alkoxycarbonyloxy (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy group, ethoxy group) a carbonyloxy group, a third propoxycarbonyloxy group, an n-octylcarbonyloxy group, an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, For example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, n-hexadecyloxyphenoxycarbonyloxy), amine (preferably amine, carbon number 1 to 30 substitution) Or an unsubstituted alkylamino group, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as an amine group, a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, or a second group. Phenylamino), decylamino (preferably methionine, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamine having 6 to 30 carbon atoms a group such as a carbenamide, an etidinyl group, a trimethylethenylamine group, a laurylamine group, a benzhydrylamino group, an amine carbonylamino group (preferably having a carbon number of 1 to 30) Substituted or unsubstituted aminocarbonylamino group, for example, an aminomethylamino group, N,N-dimethylaminocarbonyl a group, a N,N-diethylaminocarbonylamino group, a morpholinocarbonylamino group, an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms) , for example, methoxycarbonylamino, ethoxycarbonylamino, third propoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxy a carbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m-octyloxybenzene Oxycarbonylamino), sulfonylamino (preferably a substituted or unsubstituted sulfonylamino group having a carbon number of 0 to 30, such as an aminesulfonylamino group, N,N-dimethyl group Aminosulfonylamino, N-n-octylaminosulfonylamino), alkyl and arylsulfonylamino (preferably substituted or unsubstituted alkyl sulfonate having 1 to 30 carbon atoms) Mercaptoamine group, substituted or unsubstituted arylsulfonylamine having 6 to 30 carbon atoms Base, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonate a mercaptoamine group, a thiol group, an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), aromatic a sulfur group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, such as a phenylthio group, a p-chlorophenylthio group, a m-methoxyphenylthio group) or a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as a 2-benzothiazolylthio group, a 1-phenyltetrazole-5-thio group, an amine sulfonyl group (preferably having a carbon number of 0~) A substituted or unsubstituted sulfonyl group of 30, such as N-ethylamine sulfonyl, N-(3-dodecyloxypropyl)amine sulfonyl, N,N-dimethylamine sulfonate , N-acetamide sulfonyl, N-benzhydrylsulfonyl, N-(N'-phenylaminecarbamyl)amine sulfonyl), sulfonic acid, alkyl and aryl A sulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group of 6 to 30, such as methylsulfinyl, Ethyl sulfin a group, a phenylsulfinyl group, a p-methylphenylsulfinyl group, an alkyl group and an arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, 6 ~30 substituted or unsubstituted arylsulfonyl, for example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), mercapto (preferably A) a mercapto group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as an ethylidene group or a trimethylethyl benzhydryl group, An aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, a m-nitrophenoxycarbonyl group, and a third Butylphenoxycarbonyl), alkoxycarbonyl (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a third propoxycarbonyl group, N-octadecyloxycarbonyl), Aminomethyl thiol (preferably a substituted or unsubstituted amine carbenyl group having 1 to 30 carbon atoms, such as an amine methyl sulfonyl group, an N-methyl amine methyl fluorenyl group, and an N,N-dimethylamine fluorenyl group. , N,N-di-n-octylamine methyl sulfhydryl, N-(methylsulfonyl)amine carbaryl, aryl and heterocyclic azo (preferably a carbon number 6 to 30 substitution or An unsubstituted arylazo group, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, such as a phenylazo group, a p-chlorophenylazo group, a 5-ethylthio group-1, 3,4-thiadiazol-2-ylazo), quinone imine (preferably N-succinimide, N-phosphophthalimido), phosphino (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group, or a phosphinyl group (preferably having a carbon number of 2 to 30) Or an unsubstituted phosphinyl group, such as a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group, a phosphinyloxy group (preferably a substituted or unsubstituted oxygen having a carbon number of 2 to 30) a phosphino group, such as a diphenoxy phosphinyloxy group, a dioctyloxyphosphinyloxy group, a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, E.g. a phosphinylamino group, a dimethylaminophosphinylamino group, a decyl group (preferably a substituted or unsubstituted alkylene group having a carbon number of 3 to 30, such as a trimethyldecyl group, a tert-butyl group A substituent such as dimethyl decane or phenyl dimethyl decyl group.

又，上述的取代基之中，具有氫原子者亦可以進一步將其去掉，而以上述之基來加以取代。像這樣的官能基之例係舉例如烷基羰基胺基磺醯基、芳基羰基胺基磺醯基、烷基磺醯基胺基羰基、芳基磺醯基胺基羰基。其具體例係舉例如甲基磺醯基胺基羰基、對甲基苯基磺醯基胺基羰基、乙醯胺基磺醯基、苯甲醯基胺基磺醯基。Further, among the above substituents, those having a hydrogen atom may be further removed and substituted with the above groups. Examples of the functional group such as this are exemplified by an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Specific examples thereof include, for example, a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an ethenylsulfonyl group, and a benzhydrylaminosulfonyl group.

又，取代基為二者以上之情形，其係可為相同或是不同。又，在可能之情形中，亦可互相鍵結以形成環。Further, in the case where the substituent is two or more, the system may be the same or different. Also, where possible, they may be bonded to each other to form a loop.

通式(I)中，n係表示0~5的整數。n係以0以上3以下為佳、0或1為較佳、0為最佳。n為2以上的整數之情形中，複數個的R2 係可相同或不同。In the formula (I), n represents an integer of 0 to 5. n is preferably 0 or more and 3 or less, 0 or 1 is preferred, and 0 is most preferred. In the case where n is an integer of 2 or more, a plurality of R 2 systems may be the same or different.

R3 及R4 係分別表示氫原子或取代基。該取代基係可自前述取代基群T中加以選擇。較佳係R3 及R4 中任一者為氫原子。R 3 and R 4 each represent a hydrogen atom or a substituent. The substituent may be selected from the aforementioned substituent group T. Preferably, any of R 3 and R 4 is a hydrogen atom.

通式(I)中，m係表示0以上的整數，0以上3以下為佳，0或1為較佳。In the formula (I), m represents an integer of 0 or more, preferably 0 or more and 3 or less, and 0 or 1 is preferable.

通式(I)所示之化合物係以甲基丙烯酸苄酯、苄基丙烯酸酯、苯基丙烯酸酯、甲基丙烯酸苯酯為佳、甲基丙烯酸苄酯、甲基丙烯酸苯酯為較佳。The compound represented by the formula (I) is preferably benzyl methacrylate, benzyl acrylate, phenyl acrylate or phenyl methacrylate, preferably benzyl methacrylate or phenyl methacrylate.

前述黏著劑層的形成方法係沒有特別地限制，一般係在表面、例如光學補償薄片的表面，塗布含有黏著劑之溶液、乾燥而形成之方法。又，黏著劑層係亦可利用使用形成於暫時支持體(離型薄片)表面之轉印材料，並將黏著劑層轉印至表面、例如光學補償薄片的表面而形成之方法。The method for forming the pressure-sensitive adhesive layer is not particularly limited, and is generally formed by applying a solution containing an adhesive to a surface, for example, an optical compensation sheet, and drying it. Further, the adhesive layer may be formed by using a transfer material formed on the surface of the temporary support (release sheet) and transferring the adhesive layer to the surface, for example, the surface of the optical compensation sheet.

黏著劑層的厚度係沒有特別地限制，以乾燥膜厚為10~40μm程度者為佳。The thickness of the adhesive layer is not particularly limited, and it is preferably a dry film thickness of 10 to 40 μm.

又，在為了形成前述黏著劑層所使用之塗布液等的組成物中，亦可含有前述黏著劑以及交聯劑。該交聯劑係舉例如聚異氰酸酯化合物、聚胺化合物、三聚氰胺樹脂、脲樹脂、環氧樹脂等。再者，前述組成物中可視其需要、在不脫離本發明目的之範圍內，亦可各適宜地使用以往習知的黏著賦予劑、可塑劑、充填劑、抗氧化劑、紫外線吸收劑等。Moreover, the adhesive agent and the crosslinking agent may be contained in the composition of the coating liquid or the like used to form the pressure-sensitive adhesive layer. The crosslinking agent is, for example, a polyisocyanate compound, a polyamine compound, a melamine resin, a urea resin, an epoxy resin or the like. In addition, as the above-mentioned composition, it is possible to use conventionally known adhesion-imparting agents, plasticizers, fillers, antioxidants, ultraviolet absorbers, and the like, as appropriate, without departing from the object of the present invention.

《光學補償薄片》Optical Compensation Sheet

本發明的偏光板係具有光學補償薄片。當將前述偏光板組裝至液晶顯示裝置之際，光學補償薄片係組裝至位於偏光層與液晶胞之間的位置者為佳。前述光學補償薄片係依照與所組裝黏著劑層之光彈性係數的關係，使其彈性係數滿足前述Y值之條件即可。製作光學補償薄片之際不過度所小材料的選擇幅度，可從一般的材料製造之點而言，光學補償薄片的彈性係數係以5×108 Pa~1×1010 Pa者為佳、1×109 Pa~5×109 Pa者為較佳。The polarizing plate of the present invention has an optical compensation sheet. When the polarizing plate is assembled to the liquid crystal display device, it is preferable that the optical compensation sheet is assembled to a position between the polarizing layer and the liquid crystal cell. The optical compensation sheet may be such that the elastic modulus satisfies the Y value in accordance with the relationship between the photoelastic coefficient of the assembled adhesive layer. When the optical compensation sheet is produced, the selection range of the small material is not excessive, and the elastic modulus of the optical compensation sheet is preferably 5×10 8 Pa to 1×10 10 Pa from the point of general material manufacture, 1 It is preferred that ×10 9 Pa~5×10 9 Pa.

另外，關於光學補償薄片的光彈性係數係沒有特別地限制，以50×10-12 (1/Pa)以下者為佳。Further, the photoelastic coefficient of the optical compensation sheet is not particularly limited, and is preferably 50 × 10 -12 (1/Pa) or less.

關於前述光學補償薄片的材料係沒有特別地限制。例如，可為三乙醯纖維素或降烯類的聚合物等的聚合物薄膜，或可使用在透明支持體上具有由液晶組成物所構成之光學各向異性層的積層薄膜。前述光學補償薄片或前述光學補償薄片為積層薄膜之情形中，前述光學各向異性層的透明支持體(以下，稱為「光學補償薄片等」)係亦可為聚合物薄膜。較佳係使用光透射率為80%以上之聚合物薄膜。構成該聚合物薄膜的聚合物之例中，包含纖維素酯(例如：乙酸纖維素、二乙酸纖維素、三乙酸纖維素(三乙醯纖維素))、聚烯烴(例如：降烯系聚合物)、聚碳酸酯及聚碸。亦可使用市售的聚合物(降烯系聚合物係有ARTON(JSR製)、ZEONOR(日本ZEON製)等)。The material of the aforementioned optical compensation sheet is not particularly limited. For example, it can be triethyl cellulose or drop A polymer film such as a polymer of an olefin or a laminated film having an optically anisotropic layer composed of a liquid crystal composition on a transparent support can be used. In the case where the optical compensation sheet or the optical compensation sheet is a laminated film, the transparent support of the optically anisotropic layer (hereinafter referred to as "optical compensation sheet or the like") may be a polymer film. It is preferred to use a polymer film having a light transmittance of 80% or more. Examples of the polymer constituting the polymer film include cellulose esters (for example, cellulose acetate, cellulose diacetate, cellulose triacetate (triacetyl cellulose)), and polyolefins (for example, Ethylene polymer), polycarbonate and polyfluorene. Commercially available polymers can also be used The olefin polymer is ARTON (made by JSR), ZEONOR (made by Japan ZEON), and the like.

上述聚合物薄膜係主要是以三乙醯纖維素或降烯所構成之薄膜者為佳。本說明書中「主要是」係意味著上述 聚合物在高分子薄膜中，以質量比例為50%以上者。其中，纖維素酯尤其為佳、纖維素的低級脂肪酸酯為較佳。低級脂肪酸係意味著碳原子數為6以下之脂肪酸。碳原子數係以2(乙酸纖維素)、3(丙酸纖維素)或4(丁酸纖維素)為佳。乙酸纖維素為特佳。可使用乙酸丙酸纖維素或乙酸丁酸纖維素般的混合脂肪酸酯。纖維素的低級脂肪酸酯係以乙酸纖維素為最佳。The above polymer film is mainly made of triacetyl cellulose or A film composed of an ene is preferred. In the present specification, "mainly" means that the polymer is 50% by mass or more in the polymer film. Among them, cellulose esters are particularly preferred, and lower fatty acid esters of cellulose are preferred. The lower fatty acid means a fatty acid having 6 or less carbon atoms. The number of carbon atoms is preferably 2 (cellulose acetate), 3 (cellulose propionate) or 4 (cellulose butyrate). Cellulose acetate is particularly preferred. A mixed fatty acid ester such as cellulose acetate propionate or cellulose acetate butyrate can be used. The lower fatty acid ester of cellulose is preferably cellulose acetate.

乙酸纖維素的乙醯化度係以55.0~62.5%為佳、59.0~61.5%為較佳。乙醯化度係意味著纖維素每單位質量的鍵結乙酸量。乙醯化度係按照ASTM D-817-91(乙酸纖維素等的試驗法)中乙醯化度的測定及計算。The degree of acetylation of cellulose acetate is preferably 55.0 to 62.5%, preferably 59.0 to 61.5%. The degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation is measured and calculated according to ASTM D-817-91 (test method for cellulose acetate, etc.).

乙酸纖維素(亦稱為乙醯纖維素)的黏度平均聚合度(DP)係以250以上為佳、290以上為較佳。The cellulose acetate (also referred to as acetyl cellulose) has a viscosity average degree of polymerization (DP) of preferably 250 or more and 290 or more.

又，使用於本發明之纖維素酯(乙酸纖維素)係藉由凝膠滲透層析法之Mw/Mn(Mw為質量平均分子量、Mn為數量平均分子量)分子量分布狹窄為適宜。具體的Mw/Mn之值係以1.0~1.7的範圍為佳、1.3~1.65的範圍為較佳、1.4~1.6的範圍為最佳。Further, the cellulose ester (cellulose acetate) used in the present invention is preferably a molecular weight distribution of Mw/Mn (Mw is a mass average molecular weight and Mn is a number average molecular weight) by gel permeation chromatography. The specific value of Mw/Mn is preferably in the range of 1.0 to 1.7, preferably in the range of 1.3 to 1.65, and preferably in the range of 1.4 to 1.6.

一般，乙酸纖維素之2,3,6的羥基並非依全體取代度的各1/3來均等地分配的，6位羥基的取代度係有變小的傾向。本發明中，乙酸纖維素之6位羥基的取代度係比2,3位多者為佳。相對於全體的取代度，6位的羥基係以30%以上之乙醯基來加以取代為佳、再者為31%以上、特別是以32%以上為佳。再者，乙酸纖維素之6位乙醯基的取代度為0.88以上為佳。6位羥基係除了乙醯基以外，亦可以 碳數3以上醯基之丙醯基、丁醯基、戊醯基、苯甲醯基、丙烯醯基等來加以取代者，且可使用於前述光學補償薄片等的製作。各位置的取代度之測定係可藉由NMR而求得。又，以特開平11-5851號公報的段落號碼0043~0044中記載的合成例1、段落號碼0048~0049中記載的合成例2、以及段落號碼0051~0052中記載的合成例3之方法所得到之乙酸纖維素，係可使用於前述光學補償薄片等的製作。In general, the hydroxyl groups of 2, 3, and 6 of cellulose acetate are not uniformly distributed in 1/3 of the total degree of substitution, and the degree of substitution of the hydroxyl group at the 6-position tends to be small. In the present invention, the degree of substitution of the hydroxyl group at the 6-position of cellulose acetate is preferably more than 2 or 3. The hydroxyl group at the 6-position is preferably substituted with 30% or more of the ethyl group for the entire degree of substitution, and more preferably 31% or more, particularly preferably 32% or more. Further, the degree of substitution of the ethyl ketone group at the 6-position of the cellulose acetate is preferably 0.88 or more. The 6-hydroxyl group can be used in addition to the ethyl ketone group. The acrylonitrile group, the butyl group, the pentamidine group, the benzamidine group, the acryl fluorenyl group or the like having a carbon number of 3 or more is substituted, and can be used for the production of the optical compensation sheet or the like. The degree of substitution at each position can be determined by NMR. Further, in the synthesis example 1 described in the paragraphs 0043 to 0044 of the Japanese Patent Publication No. 11-5851, the synthesis example 2 described in the paragraph numbers 0048 to 0049, and the method of the synthesis example 3 described in the paragraph numbers 0051 to 0052 The obtained cellulose acetate can be used for the production of the aforementioned optical compensation sheet or the like.

(遲滯值上昇劑)(hysteresis value riser)

乙酸纖維素薄膜做為光學補償薄片等使用之情形中，為調整其遲滯值，使用具有至少二個芳香族環之芳香族化合物來當作遲滯值上昇劑為適宜。芳香族化合物係相對於乙酸纖維素100質量份，以0.01~20質量份的範圍來使用者為佳、以0.05~15質量份的範圍來使用為較佳、以0.1~10質量份的範圍來使用為更佳。亦可併用二種以上之芳香族化合物。芳香族化合物的芳香族環中，除了芳香族烴環以外，還包含芳香族性雜環。In the case where the cellulose acetate film is used as an optical compensation sheet or the like, in order to adjust the hysteresis value, it is preferable to use an aromatic compound having at least two aromatic rings as a hysteresis value increasing agent. The aromatic compound is preferably used in an amount of 0.01 to 20 parts by mass, more preferably 0.05 to 15 parts by mass, and preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the cellulose acetate. Use is better. Two or more aromatic compounds may also be used in combination. The aromatic ring of the aromatic compound contains an aromatic hetero ring in addition to the aromatic hydrocarbon ring.

芳香族烴環係以6員環(亦即苯環)為特佳。芳香族性雜環係一般為不飽和雜環。芳香族性雜環係以5員環、6員環或7員環為佳、5員環或6員環為較佳。芳香族性雜環一般係具有最多的雙鍵。可做為雜原子者係以氮原子、氧原子及硫原子為佳、氮原子為特佳。芳香族性雜環之例中係包含呋喃環、噻吩環、吡咯環、唑環、異唑環、噻唑環、異噻唑環、咪唑環、吡唑環、呋呫環、***環、吡喃環、吡啶環、嗒環、嘧啶環、吡環及1,3,5-三環。可做為芳香族環者係以苯環、呋喃環、噻吩環、吡咯 環、唑環、噻唑環、咪唑環、***環、吡啶環、嘧啶環、吡環及1,3,5-三環為佳，苯環及1,3,5-三環為更佳。芳香族化合物係具有至少一個1,3,5-三環為特佳。The aromatic hydrocarbon ring system is particularly preferred as a 6-membered ring (i.e., a benzene ring). The aromatic heterocyclic ring is generally an unsaturated heterocyclic ring. The aromatic heterocyclic ring is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, and a 5-membered ring or a 6-membered ring is preferred. Aromatic heterocycles generally have the most double bonds. A nitrogen atom, an oxygen atom and a sulfur atom are preferred as the hetero atom, and a nitrogen atom is particularly preferred. Examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, a pyrrole ring, Oxazole ring, different Oxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazan ring, triazole ring, pyran ring, pyridine ring, hydrazine Ring, pyrimidine ring, pyridyl Ring and 1,3,5-three ring. It can be used as an aromatic ring with a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, Oxazole ring, thiazole ring, imidazole ring, triazole ring, pyridine ring, pyrimidine ring, pyridyl Ring and 1,3,5-three Ring is preferred, benzene ring and 1,3,5-three The ring is better. The aromatic compound has at least one 1,3,5-three The ring is especially good.

芳香族化合物具有之芳香族環的數目係以2~20為佳、2~12為較佳、2~8為更佳、2~6為最佳。二個芳香族環的鍵結關係係可分類成(a)形成縮合環之情形、(b)以單鍵直接鍵結之情形、及(c)透過連結基而鍵結之情形(因為是芳香族環，故無法形成螺鍵)。鍵結關係可為(a)~(c)中任一者。The number of aromatic rings of the aromatic compound is preferably 2 to 20, 2 to 12 is preferred, 2 to 8 is more preferred, and 2 to 6 is most preferred. The bonding relationship of the two aromatic rings can be classified into (a) a case where a condensed ring is formed, (b) a case where a single bond is directly bonded, and (c) a case where a bond is bonded through a linking group (because it is aroma) The family ring is unable to form a screw key). The bond relationship can be any of (a) to (c).

(a)的縮合環(二個以上的芳香族環之縮合環)之例中係包含茚環、萘環、甘菊環、茀環、菲環、蒽環、苊環、稠四苯環、芘環、吲哚環、異吲哚環、苯并呋喃環、苯并噻吩環、吲哚環、苯并唑環、苯并噻唑環、苯并咪唑環、苯并***環、嘌呤環、吲唑環、色烯環、喹啉環、異喹啉環、喹環、喹唑啉環、噌啉環、喹喏啉環、呔環、喋啶環、咔唑環、吖啶環、菲啶環、 環、吩環、吩噻環、吩噻環、吩 及噻蒽環。以萘環、甘菊環、吲哚環、苯并唑環、苯并噻唑環、苯并咪唑環、苯并***環及喹啉環為佳。Examples of the condensed ring (a condensed ring of two or more aromatic rings) of (a) include an anthracene ring, a naphthalene ring, a chamomile ring, an anthracene ring, a phenanthrene ring, an anthracene ring, an anthracene ring, a condensed tetraphenyl ring, and an anthracene ring. , anthracene ring, isoindole ring, benzofuran ring, benzothiophene ring, anthracene Ring, benzo Oxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring, anthracene ring, indazole ring, chromene ring, quinoline ring, isoquinoline ring, quin Ring, quinazoline ring, porphyrin ring, quinoxaline ring, hydrazine Ring, acridine ring, carbazole ring, acridine ring, phenanthridine ring, Ring, pheno Ring, phenothiazine Ring, phenothiazine Ring, pheno And thiazide ring. Naphthalene ring, chamomile ring, anthracene ring, benzo The azole ring, the benzothiazole ring, the benzimidazole ring, the benzotriazole ring and the quinoline ring are preferred.

(b)的單鍵係在二個芳香族環之碳原子間鍵結為佳。可以二個以上之單鍵來鍵結二個芳香族環，也可以在二個芳香族環之間形成脂肪族環或非芳香族性雜環。The single bond of (b) is preferably bonded between the carbon atoms of the two aromatic rings. Two or more single bonds may be bonded to the two aromatic rings, or an aliphatic ring or a non-aromatic heterocyclic ring may be formed between the two aromatic rings.

(c)的連結基係以與二個芳香族環之碳原子鍵結為適宜。連結基係以伸烷基、伸烯基、伸炔基、-CO-、-O-、-NH-、-S-或彼等之組合為佳。由組合所成的連結基之例係如以下所示。另外，以下連結基之例的左右關係即使相反了也可 以。The linking group of (c) is preferably bonded to a carbon atom of two aromatic rings. The linking group is preferably an alkyl group, an alkenyl group, an alkynyl group, a -CO-, -O-, -NH-, -S- or a combination thereof. Examples of the linking group formed by the combination are as follows. In addition, the left-right relationship of the following examples of the link base can be reversed even if it is reversed. To.

c1:-CO-O- c2:-CO-NH- c3：-伸烷基-O- c4:-NH-CO-NH- c5:-NH-CO-O- c6:-O-CO-O- c7:-O-伸烷基-O- c8:-CO-伸烯基- c9:-CO-伸烯基-NH- c10:-CO-伸烯基-O- c11：-伸烷基-CO-O-伸烷基-O-CO-伸烷基- c12:-O-伸烷基-CO-O-伸烷基-O-CO-伸烷基-O- c13:-O-CO-伸烷基-CO-O- c14:-NH-CO-伸烯基- c15:-O-CO-伸烯基-C1:-CO-O- C2:-CO-NH- C3:-alkylene-O- C4:-NH-CO-NH- C5:-NH-CO-O- C6:-O-CO-O- C7:-O-alkylene-O- C8: -CO-alkenyl- C9: -CO-alkenyl-NH- C10: -CO-Extend alkenyl-O- C11:-alkyl-CO-O-alkylene-O-CO-alkylene- C12:-O-alkylene-CO-O-alkylene-O-CO-alkylene-O- C13:-O-CO-alkylene-CO-O- C14: -NH-CO-alkenyl- C15: -O-CO-alkenyl-

芳香族環及連結基係亦可具有取代基。取代基之例係包含鹵素原子(F、Cl、Br、I)、羥基、羧基、氰基、胺基、硝基、磺酸基、胺甲醯基、胺磺醯基、脲、烷基、鏈烯基、炔基、脂肪族醯基、脂肪族醯氧基、烷氧基、烷氧基羰基、烷氧基羰基胺基、烷硫基、烷基磺醯基、脂肪族醯胺基、脂肪族磺胺基、脂肪族取代胺基、脂肪族取代胺甲醯基、脂肪族取代胺磺醯基、脂肪族取代脲基及非芳香族性雜環基。The aromatic ring and the linking group may have a substituent. Examples of the substituent include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, a cyano group, an amine group, a nitro group, a sulfonic acid group, an amine carbaryl group, an amine sulfonyl group, a urea group, an alkyl group, Alkenyl, alkynyl, aliphatic fluorenyl, aliphatic decyloxy, alkoxy, alkoxycarbonyl, alkoxycarbonylamino, alkylthio, alkylsulfonyl, aliphatic guanylamine, An aliphatic sulfonamide group, an aliphatic substituted amine group, an aliphatic substituted amine carbenyl group, an aliphatic substituted amine sulfonyl group, an aliphatic substituted ureido group, and a non-aromatic heterocyclic group.

另外，本說明書中，氫原子為氫原子以外的原子所取 代之情形中的該氫原子以外之原子，為了方便起見亦可做為取代基來處理。In addition, in the present specification, a hydrogen atom is taken by an atom other than a hydrogen atom. The atom other than the hydrogen atom in the case of substitution may be treated as a substituent for the sake of convenience.

烷基的碳原子數係以1~8為佳。鏈狀烷基比環狀烷基者為佳、以直鏈狀烷基為特佳。烷基亦可更含有取代基(例如：羥基、羧基、烷氧基、烷基取代胺基)。烷基的(包含取代烷基)例子中包含甲基、乙基、正丁基、正己基、2-羥基乙基、4-羧基丁基、2-甲氧基乙基及2-二乙基胺基乙基。The alkyl group preferably has 1 to 8 carbon atoms. The chain alkyl group is preferably a cyclic alkyl group, and particularly preferably a linear alkyl group. The alkyl group may further contain a substituent (for example, a hydroxyl group, a carboxyl group, an alkoxy group, or an alkyl group-substituted amine group). Examples of the alkyl group (including a substituted alkyl group) include methyl, ethyl, n-butyl, n-hexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl and 2-diethyl. Aminoethyl.

鏈烯基的碳原子數係以2~8為佳。鏈狀鏈烯基比環狀鏈烯基者為佳、以直鏈狀鏈烯基為特佳。鏈烯基係亦可更含有取代基。鏈烯基之例中係包含乙烯基、烯丙基及1-己烯基。炔基的碳原子數係以2~8為佳。鏈狀炔基比環狀炔基者為佳、以直鏈狀炔基為特佳。炔基係亦可更含有取代基。炔基之例係包含乙炔基、1-丁炔基及1-己炔基。The number of carbon atoms of the alkenyl group is preferably from 2 to 8. The chain alkenyl group is preferred to the cyclic alkenyl group, and the linear alkenyl group is particularly preferred. The alkenyl group may further contain a substituent. Examples of alkenyl groups include vinyl, allyl and 1-hexenyl. The alkynyl group preferably has 2 to 8 carbon atoms. The chain alkynyl group is preferred to the cyclic alkynyl group, and the linear alkynyl group is particularly preferred. The alkynyl group may further contain a substituent. Examples of alkynyl groups include ethynyl, 1-butynyl and 1-hexynyl.

脂肪族醯基的碳原子數係以1~10為佳。脂肪族醯基之例係包含乙醯基、丙醯基及丁醯基。The number of carbon atoms of the aliphatic sulfhydryl group is preferably from 1 to 10. Examples of the aliphatic thiol group include an ethyl group, a propyl group, and a butyl group.

脂肪族醯氧基的碳原子數係以1~10為佳。脂肪族醯氧基之例係包含乙醯氧基。The aliphatic methoxy group has preferably 1 to 10 carbon atoms. An example of an aliphatic methoxy group includes an ethoxy group.

烷氧基的碳原子數係以1~8為佳。烷氧基係亦可更含有取代基(例如：烷氧基)。烷氧基的(包括取代烷氧基)例係包含甲氧基、乙氧基、丙氧基及甲氧基乙氧基。The alkoxy group preferably has 1 to 8 carbon atoms. The alkoxy group may further contain a substituent (for example, an alkoxy group). Examples of alkoxy groups (including substituted alkoxy groups) include methoxy, ethoxy, propoxy and methoxyethoxy groups.

烷氧基羰基的碳原子數係以2~10為佳。烷氧基羰基之例係包含甲氧基羰基及乙氧基羰基。The alkoxycarbonyl group preferably has 2 to 10 carbon atoms. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

烷氧基羰基胺基的碳原子數係以2~10為佳。烷氧基羰基胺基之例係包含甲氧基羰基胺基及乙氧基羰基胺基。The alkoxycarbonylamino group preferably has 2 to 10 carbon atoms. Examples of the alkoxycarbonylamino group include a methoxycarbonylamino group and an ethoxycarbonylamino group.

烷硫基的碳原子數係以1~12為佳。烷硫基之例係包含 甲硫基、乙硫基及辛硫基。The alkylthio group has preferably 1 to 12 carbon atoms. Examples of alkylthio groups Methylthio, ethylthio and octylthio.

烷基磺醯基的碳原子數係以1~8為佳。烷基磺醯基之例係包含甲烷磺醯基及乙烷磺醯基。The alkylsulfonyl group preferably has 1 to 8 carbon atoms. Examples of the alkylsulfonyl group include a methanesulfonyl group and an ethanesulfonyl group.

脂肪族醯胺基的碳原子數係以1~10為佳。脂肪族醯胺基之例係包含乙醯胺。The aliphatic guanamine group preferably has 1 to 10 carbon atoms. An example of an aliphatic guanamine group comprises acetamide.

脂肪族磺胺基的碳原子數係以1~8為佳。脂肪族磺胺基之例係包含甲磺胺基、丁磺胺基及正辛磺胺基。The aliphatic sulfonamide group preferably has 1 to 8 carbon atoms. Examples of the aliphatic sulfonamide group include a methanesulfonyl group, a butylsulfonyl group, and a n-octylsulfonyl group.

脂肪族取代胺基的碳原子數係以1~10為佳。脂肪族取代胺基之例係包含二甲基胺基、二乙基胺基及2-羧基乙基胺基。The number of carbon atoms of the aliphatic substituted amine group is preferably from 1 to 10. Examples of the aliphatic substituted amine group include a dimethylamino group, a diethylamino group, and a 2-carboxyethylamino group.

脂肪族取代胺甲醯基的碳原子數係以2~10為佳。脂肪族取代胺甲醯基之例係包含甲基胺甲醯基及二乙基胺甲醯基。The aliphatic substituted amine carbenyl group preferably has 2 to 10 carbon atoms. Examples of the aliphatic substituted amine carbenyl group include methylamine carbaryl and diethylamine fluorenyl.

脂肪族取代胺磺醯基的碳原子數係以1~8為佳。脂肪族取代胺磺醯基之例係包含甲基胺磺醯基及二乙基胺磺醯基。The number of carbon atoms of the aliphatic substituted amine sulfonyl group is preferably from 1 to 8. Examples of the aliphatic substituted amine sulfonyl group include a methylamine sulfonyl group and a diethylamine sulfonyl group.

脂肪族取代脲基的碳原子數係以2~10為佳。脂肪族取代脲基之例係包含甲基脲。The number of carbon atoms of the aliphatic substituted ureido group is preferably from 2 to 10. An example of an aliphatic substituted urea group is methyl urea.

非芳香族性雜環基之例係包含1-哌啶基及味啉代基。Examples of the non-aromatic heterocyclic group include a 1-piperidinyl group and a gustoyl group.

遲滯值上昇劑的分子量係以300~800為佳。遲滯值上昇劑的具體例可舉例如特開2000-111914號公報、同2000-275434號公報、國際公開第00/065384號手冊中記載的化合物。The molecular weight of the hysteresis rising agent is preferably from 300 to 800. Specific examples of the hysteresis value-increasing agent include the compounds described in JP-A-2000-111914, JP-A-2000-275434, and International Publication No. 00/065384.

(乙酸纖維素薄膜的製造)(Manufacture of cellulose acetate film)

接著，就乙酸纖維素薄膜的製造方法詳細描述。製造 上述乙酸纖維素薄膜之方法及設備係使用供給乙酸纖維素薄膜製造用之以往習知的溶液流延製膜方法及溶液流延製膜裝置。Next, a method of producing a cellulose acetate film will be described in detail. Manufacturing The method and apparatus for the cellulose acetate film are conventional solution casting film forming methods and solution casting film forming apparatuses for producing a cellulose acetate film.

其中，尤以藉由溶液流延法來製造乙酸纖維素薄膜為適宜。溶液流延法係使用乙酸纖維素溶解於有機溶媒之溶液(塗布液)來製造薄膜。有機溶媒係以包含自碳原子數為3~12的醚、碳原子數為3~12的酮、碳原子數為3~12的酯及碳原子數為1~6的鹵化烴中所選出的溶媒為適宜。醚、酮及酯係亦可含有環狀構造。具有二個以上之醚、酮及酯的官能基(亦即、-O-、-CO-及-COO-)中任一者的化合物係亦可做為有機溶媒來使用。有機溶媒如係亦可具有如醇性羥基的的其他官能基。具有二種以上官能基之有機溶媒時，其碳原子數只要在具有任一官能基之化合物的規定範圍內即可。Among them, a cellulose acetate film is preferably produced by a solution casting method. The solution casting method uses a solution (coating liquid) in which cellulose acetate is dissolved in an organic solvent to produce a film. The organic solvent is selected from the group consisting of an ether having 3 to 12 carbon atoms, a ketone having 3 to 12 carbon atoms, an ester having 3 to 12 carbon atoms, and a halogenated hydrocarbon having 1 to 6 carbon atoms. The solvent is suitable. The ether, ketone and ester system may also have a cyclic structure. A compound having two or more functional groups of an ether, a ketone, and an ester (that is, -O-, -CO-, and -COO-) can also be used as an organic solvent. The organic solvent may also have other functional groups such as an alcoholic hydroxyl group. When an organic solvent having two or more functional groups is used, the number of carbon atoms may be within a predetermined range of the compound having any functional group.

碳原子數為3~12的醚類之例係包含二異丙基醚、二甲氧基甲烷、二甲氧基乙烷、1,4-二烷、1,3-二氧戊環、四氫呋喃、苯甲醚及苯***。Examples of ethers having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, and 1,4-two. Alkane, 1,3-dioxolane, tetrahydrofuran, anisole and phenylethyl ether.

碳原子數為3~12的酮類之例係包含丙酮、甲基乙基酮、二乙基酮、二異丁基酮、環己酮及甲基環己酮。Examples of the ketone having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone, and methylcyclohexanone.

碳原子數為3~12的酯類之例係包含乙基甲酸酯、丙基甲酸酯、戊基甲酸酯、甲基乙酸酯、乙基乙酸酯及戊基乙酸酯。Examples of the ester having 3 to 12 carbon atoms include ethyl formate, propyl formate, amylformate, methyl acetate, ethyl acetate, and pentyl acetate.

具有二種以上官能基的有機溶媒之例係包含2-乙氧基乙基乙酸酯、2-甲氧基乙醇及2-丙氧基乙醇。Examples of the organic solvent having two or more functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol, and 2-propoxyethanol.

鹵化烴的碳原子數係以1或2為佳、1為最佳。鹵化 烴的鹵素係以氯為佳。鹵化烴的氫原子取代鹵素之比例係以25~75莫耳%為佳、30~70莫耳%為較佳、35~65莫耳%為更佳、40~60莫耳%為最佳。二氯甲烷為典型的鹵化烴。The number of carbon atoms of the halogenated hydrocarbon is preferably 1 or 2, and 1 is most preferred. Halogenation The halogen of the hydrocarbon is preferably chlorine. The ratio of the halogen atom of the halogenated hydrocarbon to the halogen is preferably 25 to 75 mol%, preferably 30 to 70 mol%, more preferably 35 to 65 mol%, and most preferably 40 to 60 mol%. Dichloromethane is a typical halogenated hydrocarbon.

亦可混合二種以上之有機溶媒來使用。Two or more organic solvents may be mixed and used.

可利用一般的方法來調製乙酸纖維素溶液。此處的一般方法係意味著在0℃以上的溫度(常溫或高溫)中來進行處理。溶液的調製係可使用在一般的溶液流延法中的塗布液之調製方法及裝置而實施。另外，一般方法之情形係以使用鹵化烴(特別是二氯甲烷)來做為有機溶媒為適宜。乙酸纖維素的量係調整成在所得之乙酸纖維素溶液中含有10~40質量%者為佳、含10~30質量%為較佳。有機溶媒(主溶媒)中亦可添加後述之任意添加劑。溶液係可藉由在常溫(0~40℃)下，攪拌乙酸纖維素與有機溶媒而調製。高濃度的溶液係亦可在加壓及加熱條件下進行攪拌。具體而言，將乙酸纖維素與有機溶媒投入加壓容器中密閉，於加壓下溶媒的常溫在沸點以上，且溶媒係一邊在未沸騰之範圍下加熱溫度、一邊攪拌。加熱溫度係通常為40℃以上、較佳為60~200℃、更佳為80~110℃。A general method can be used to prepare a cellulose acetate solution. The general method herein means that the treatment is carried out at a temperature of 0 ° C or higher (normal temperature or high temperature). The preparation of the solution can be carried out by using a method and apparatus for preparing a coating liquid in a general solution casting method. Further, in the case of the general method, it is suitable to use a halogenated hydrocarbon (particularly dichloromethane) as an organic solvent. The amount of cellulose acetate is preferably adjusted to be 10 to 40% by mass in the obtained cellulose acetate solution, and preferably 10 to 30% by mass. Any additive described later may be added to the organic solvent (main solvent). The solution can be prepared by stirring cellulose acetate and an organic solvent at normal temperature (0 to 40 ° C). The high concentration solution can also be stirred under pressure and heating. Specifically, the cellulose acetate and the organic solvent are placed in a pressure vessel and sealed, and the normal temperature of the solvent under pressure is above the boiling point, and the solvent is stirred while heating the temperature in a range of not boiling. The heating temperature is usually 40 ° C or higher, preferably 60 to 200 ° C, more preferably 80 to 110 ° C.

各成分係可預先粗混合之後再投入容器。又，可依序投入至容器內。容器係有可攪拌之構成為適宜。可注入氮氣等的惰性氣體以加壓容器。又，亦可利用因加熱所引起的溶媒之蒸氣壓上昇。或，亦可在密閉容器後，於壓力下添加各成分。進行加熱之情形，從容器的外部來進行加熱為適宜。例如，可使用套箱式(jacket type)的加熱裝置。又，亦可藉由在容器的外部設置、配管板狀加熱器，使液 體循環，來加熱容器整體。以在容器內部設置攪拌葉片且使用它來進行攪拌為適宜。攪拌葉片係長達至容器壁的附近者為佳。為了更新容器壁的液膜，攪拌葉片的末端設置刮取葉片為適宜。容器係亦可設置壓力計、溫度計等的計器類。能在容器內使各成分溶解於溶劑中。將所調製的塗布液從冷却後容器取出，或亦可在取出之後，利用熱交換器等使其冷却。Each component can be coarsely mixed beforehand and then put into a container. Moreover, it can be put into the container in order. It is suitable that the container has a stirrable configuration. An inert gas such as nitrogen gas may be injected to pressurize the container. Further, it is also possible to use a vapor pressure increase of the solvent due to heating. Alternatively, each component may be added under pressure after the container is sealed. In the case of heating, heating from the outside of the container is suitable. For example, a jacket type heating device can be used. Further, it is also possible to provide a liquid by providing a plate-shaped heater on the outside of the container. Body circulation to heat the entire container. It is suitable to provide a stirring blade inside the container and use it for stirring. It is preferred that the agitating blade system is as long as it is near the wall of the container. In order to renew the liquid film of the container wall, it is suitable to provide a scraping blade at the end of the stirring blade. The container may be provided with a gauge such as a pressure gauge or a thermometer. The components can be dissolved in a solvent in a container. The prepared coating liquid is taken out from the container after cooling, or may be cooled by a heat exchanger or the like after being taken out.

亦可藉由冷却溶解法來調製溶液。冷却溶解法係即使在以一邊的溶解方法難以溶解之有機溶媒中，亦可使乙酸纖維素溶解。另外，以一般的溶解方法可溶解乙酸纖維素之溶媒，亦可在冷却溶解法時得到所謂迅速均勻的溶液之效果而為佳。冷却溶解法一般係在一開始時，於室溫下、有機溶媒中一邊攪拌乙酸纖維素、一邊緩緩的添加。乙酸纖維素的量係調整成在該混合物中含有10~40質量%為適宜。乙酸纖維素的量係以10~30質量%為較佳。再者，混合物中亦可添加後述的任意添加劑。The solution can also be prepared by a cooling dissolution method. The cooling dissolution method can dissolve cellulose acetate even in an organic solvent which is difficult to dissolve by a dissolution method on one side. Further, the solvent of cellulose acetate can be dissolved by a general dissolution method, and the effect of a so-called rapid and uniform solution can be obtained in the case of a cooling dissolution method. The cooling and dissolving method is generally carried out at the beginning, while stirring the cellulose acetate at room temperature in an organic solvent. The amount of cellulose acetate is adjusted so as to be contained in the mixture in an amount of 10 to 40% by mass. The amount of cellulose acetate is preferably 10 to 30% by mass. Further, any additives described later may be added to the mixture.

接著，將混合物冷卻至-100~-10℃(較佳為-80~-10℃、更佳為-50~-20℃、最佳為-50~-30℃)。冷却係可在例如乾冰．甲醇浴(-75℃)、經冷却之二甘醇溶液(-30~-20℃)中來實施。如此冷却時，乙酸纖維素與有機溶媒的混合物係為固化。冷却速度係以4℃/分以上為佳、8℃/分以上為更佳、12℃/分以上為最佳。冷却速度係越快越好，惟10000℃/秒為理論的上限，1000℃/秒為技術的上限，而100℃/秒為實用的上限。另外，冷却速度係以自開始冷却至最終的冷却溫度時的時間，除以開始冷却時的溫度與最終的冷 却溫度之差的值。Next, the mixture is cooled to -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to -20 ° C, most preferably -50 to -30 ° C). The cooling system can be, for example, dry ice. It was carried out in a methanol bath (-75 ° C) and a cooled diethylene glycol solution (-30 to -20 ° C). When cooled as such, the mixture of cellulose acetate and the organic solvent is cured. The cooling rate is preferably 4 ° C / min or more, more preferably 8 ° C / min or more, and most preferably 12 ° C / min or more. The faster the cooling rate, the better, but 10000 ° C / sec is the theoretical upper limit, 1000 ° C / sec is the upper limit of the technology, and 100 ° C / sec is the practical upper limit. In addition, the cooling rate is the time from the start of cooling to the final cooling temperature, divided by the temperature at which cooling begins and the final cold. But the value of the difference in temperature.

再者，將其加溫至0~200℃(較佳為0~150℃、更佳為0~120℃、最佳為0~50℃)時，乙酸纖維素係溶解於有機溶媒中。昇溫係不僅可放置在室溫中、亦可在溫浴中來進行加溫。加溫速度係以4℃/分以上為佳、8℃/分以上為更佳、12℃/分以上為最佳。加溫速度係越快越好，惟10000℃/秒為理論的上限，1000℃/秒為技術的上限，而100℃/秒為實用的上限。另外，加溫速度係以開始加溫至最終的加溫溫度的時間，除以開始加溫時的溫度與最終的加溫溫度之差的值。如以上進行可得到均勻的溶液。另外，溶解不充分之情形亦可重複冷却、加溫的操作。溶解是否充分係藉由目視來觀察溶液的外觀而加以判斷。Further, when it is heated to 0 to 200 ° C (preferably 0 to 150 ° C, more preferably 0 to 120 ° C, most preferably 0 to 50 ° C), cellulose acetate is dissolved in an organic solvent. The temperature rise system can be placed not only at room temperature but also in a warm bath for warming. The heating rate is preferably 4 ° C / min or more, more preferably 8 ° C / min or more, and most preferably 12 ° C / min or more. The faster the heating rate, the better, but 10000 ° C / sec is the theoretical upper limit, 1000 ° C / sec is the upper limit of the technology, and 100 ° C / sec is the practical upper limit. Further, the heating rate is a value obtained by starting the heating to the final heating temperature, divided by the difference between the temperature at the start of heating and the final heating temperature. A uniform solution can be obtained as described above. In addition, in the case where the dissolution is insufficient, the cooling and heating operations may be repeated. Whether or not the dissolution is sufficient is judged by visually observing the appearance of the solution.

在冷却溶解法中，為了避免冷却時因結露所引起的水分混入，使用密閉容器係為所期望的。又，冷却加溫操作中，冷却時加壓、加溫時減壓時，可縮短溶解時間。為了實施加壓及減壓，所以使用耐壓性容器係為所期望的。In the cooling and dissolving method, in order to avoid moisture intrusion due to condensation during cooling, it is desirable to use a closed container. Further, in the cooling and heating operation, when the pressure is increased during cooling and the pressure is reduced during heating, the dissolution time can be shortened. In order to carry out pressurization and pressure reduction, it is desirable to use a pressure resistant container.

另外，例如將藉由冷却溶解法使乙醯化度為60.9%、黏度平均聚合度為299的乙酸纖維素溶解於甲基乙酸酯中之20質量%的溶液，藉由示差掃瞄熱量測定(DSC)時，在33℃附近係存在溶膠狀態與凝膠狀態的疑似相轉移點，且該溫度以下成為均勻的凝膠狀態。因此，該溶液係必須在疑似相轉移溫度以上、較佳為凝膠相轉移溫度+10℃程度的溫度下保持。但是，該疑似相轉移溫度係因乙酸纖維素的乙醯化度、黏度平均聚合度、溶液濃度或使用的有機溶媒而有所不同。Further, for example, a solution of 20% by mass of cellulose acetate having a degree of acetylation of 60.9% and a viscosity average degree of polymerization of 299 dissolved in methyl acetate by a cooling dissolution method is determined by differential scanning calorimetry In the case of (DSC), a suspected phase transition point between the sol state and the gel state exists in the vicinity of 33 ° C, and the temperature becomes a uniform gel state below this temperature. Therefore, the solution must be maintained at a temperature above the suspected phase transition temperature, preferably at a gel phase transition temperature of +10 °C. However, the suspected phase transition temperature differs depending on the degree of acetylation of cellulose acetate, the average degree of polymerization of the viscosity, the concentration of the solution, or the organic solvent used.

如前述所述的，較佳係由所調製的乙酸纖維素溶液(塗布液)藉由溶液流延法來調製乙酸纖維素薄膜。做為光學補償薄片的支持體而使用之乙酸纖維素的製造情形中，較佳係在塗布液中添加前述的遲滯值上昇劑。將塗布液於滾筒或輸送帶上流延，且使溶媒蒸發以形成薄膜。流延前的塗布液係調整成固體成分量為18~35%之濃度為適宜。滾筒或輸送帶的表面係預先加工成鏡面狀態為適宜。關於在溶液流延法中的流延及乾燥方法，係在美國專利第2336310號、同2367603號、同2492078號、同2492977號、同2492978號、同2607704號、同2739069號、同2739070號、英國專利第640731號、同736892號的各說明書、特公昭45-4554號、同49-5614號、特開昭60-176834號、同60-203430號、同62-115035號的各公報有記載。塗布液係在表面溫度為10℃以下之滾筒或輸送帶上進行流延為適宜。自流延開始吹拂2秒以上的風來進行乾燥為適宜。將所得之薄膜從滾筒或輸送帶剝離下來，然後以100至160℃改變連續溫度之高溫風進行乾燥，亦可使得殘留溶劑蒸發。以上的方法係記載於特公平5-17844號公報，根據該方法，可縮短從流延至剝離下來的時間而為佳。由於實施該方法，所以在流延時滾筒或輸送帶的表面溫度中係必須凝膠化塗布液。As described above, it is preferred to prepare a cellulose acetate film by a solution casting method from the prepared cellulose acetate solution (coating liquid). In the case of producing cellulose acetate used as a support for an optical compensation sheet, it is preferred to add the above-described hysteresis value increasing agent to the coating liquid. The coating liquid is cast on a drum or a conveyor belt, and the solvent is evaporated to form a film. It is preferable that the coating liquid before casting is adjusted to have a solid content of 18 to 35%. It is preferable that the surface of the drum or the conveyor belt is previously processed into a mirror surface state. The method for casting and drying in the solution casting method is disclosed in U.S. Patent No. 2336310, No. 2367603, No. 2492720, No. 2492977, No. 2492978, No. 2607704, Same No. 2739069, and No. 2739070. British Patent No. 640731, the same as No. 736892, Japanese Patent Publication No. 45-4554, No. 49-5614, JP-A-60-176834, and No. 60-203430, the same as No. 62-115035 . The coating liquid is preferably cast on a drum or a conveyor belt having a surface temperature of 10 ° C or less. It is suitable to dry by blowing the wind for 2 seconds or more from the start of casting. The obtained film is peeled off from a drum or a conveyor belt, and then dried at a high temperature of 100 to 160 ° C at a continuous temperature to evaporate the residual solvent. The above method is described in Japanese Patent Publication No. 5-17844, and according to this method, the time from casting to peeling can be shortened. Due to the implementation of this method, it is necessary to gel the coating liquid in the surface temperature of the flow delay drum or the conveyor belt.

亦可使用經調整的乙酸纖維素溶液(塗布液)進行二層以上的流延使其薄膜化。該情形中，較佳係藉由溶液流延法來製作乙酸纖維素薄膜。將塗布液流延至滾筒或輸送帶上，並使溶媒蒸發以形成薄膜。流延前的塗布液較佳係調 整成固體成分量為10~40%範圍之濃度。滾筒或輸送帶的表面預先加工成鏡面狀態為適宜。It is also possible to carry out casting of two or more layers using an adjusted cellulose acetate solution (coating liquid) to form a film. In this case, a cellulose acetate film is preferably produced by a solution casting method. The coating liquid is cast onto a drum or a conveyor belt, and the solvent is evaporated to form a film. The coating liquid before casting is preferably adjusted The solid content is in the range of 10 to 40%. It is preferable that the surface of the drum or the conveyor belt is previously processed into a mirror surface state.

流延二層以上複數個的乙酸纖維素液時，亦可流延複數個的乙酸纖維素溶液，且在支持體的進行方向設置設置間隔所所準備的複數個的流延口，一邊分別流延、積層含有乙酸纖維素之溶液、一邊製作薄膜。例如，可使用特開昭61-158414號、特開平1-122419號、及、特開平11-198285號的各公報中記載的方法。又，藉由從2個流延口來流延乙酸纖維素溶液亦可使其薄膜化。例如，可使用特公昭60-27562號、特開昭61-94724號、特開昭61-947245號、特開昭61-104813號、特開昭61-158413號、及特開平6-134933號的各公報中記載的方法。又，亦可使用特開昭56-162617號公報中所記載的，以低黏度的乙酸纖維素溶液包圍高黏度乙酸纖維素溶液的流動，同時擠壓出其高、低黏度之乙酸纖維素溶液的乙酸纖維素薄膜之流延方法。When a plurality of cellulose acetate liquids of two or more layers are cast, a plurality of cellulose acetate solutions may be cast, and a plurality of casting openings prepared at intervals in the direction in which the support is disposed may be separately flowed. A thin film is formed by laminating and laminating a solution containing cellulose acetate. For example, the methods described in each of the publications of JP-A-61-158414, JP-A-11-22419, and JP-A-11-198285 can be used. Further, the cellulose acetate solution can be cast from two casting openings to form a thin film. For example, specials No. 60-27562, JP-A-61-94724, JP-A-61-947245, JP-A-61-104813, JP-A-61-158413, and JP-A-6-134933 The methods described in each of the bulletins. Further, it is also possible to use a low-viscosity cellulose acetate solution to surround the flow of the high-viscosity cellulose acetate solution, and to extrude the high- and low-viscosity cellulose acetate solution, as described in JP-A-56-162617. A casting method of a cellulose acetate film.

又，亦可使用二個的流延口，藉由從第一流延口剝離成形於支持體之薄膜，且在與支持體面相接之側進行第二次的流延，以可製作薄膜。可舉例如特公昭44-20235號公報中記載的方法。流延的乙酸纖維素溶液係可使用相同的溶液，亦可使用不同的乙酸纖維素溶液。為了令複數個的乙酸纖維素層具有機能，只要將對應於該機能之乙酸纖維素溶液從各個流延口擠壓出來即可。此外，亦可使乙酸纖維素溶液與其他的機能層(例如，黏合層、染料層、抗靜電層、防光暈層、紫外線吸收層、偏光層等)同時進行流延。Further, two kinds of casting openings may be used, and the film formed on the support may be peeled off from the first casting opening, and the second casting may be performed on the side in contact with the support surface to form a film. For example, the method described in Japanese Patent Publication No. Sho 44-20235 can be cited. The same cellulose acetate solution can be used for the cast cellulose acetate solution, and different cellulose acetate solutions can also be used. In order to make the plurality of cellulose acetate layers functional, it is only necessary to extrude the cellulose acetate solution corresponding to the function from the respective casting openings. Further, the cellulose acetate solution may be simultaneously cast with other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, an ultraviolet absorbing layer, a polarizing layer, etc.).

以往的單層液中，為了形成必要的薄膜厚度，必須擠壓高濃度且高黏度的乙酸纖維素溶液。此時，乙酸纖維素溶液的安定性變差且固形物產生，而形成了凹凸不平故障，平面性變得不良之問題增多。該問題之解決方法係藉由將複數個的乙酸纖維素溶液從流延口進行流延，可同時將高黏度的溶液擠壓至支持體上，不僅可製作平面性良化且優異面狀之薄膜，藉由使用濃厚的乙酸纖維素溶液可達成乾燥負荷的低減化，而能藉以提高薄膜的生產速度。In the conventional single-layer liquid, in order to form a necessary film thickness, it is necessary to press a cellulose acetate solution having a high concentration and a high viscosity. At this time, the stability of the cellulose acetate solution is deteriorated and the solid matter is generated, and unevenness is formed, and the problem of poor planarity is increased. The solution to this problem is to cast a plurality of cellulose acetate solutions from the casting opening, and simultaneously squeeze the high-viscosity solution onto the support, thereby not only producing flatness and excellent surface. The film can achieve a low reduction in drying load by using a thick cellulose acetate solution, thereby increasing the production speed of the film.

(添加劑)(additive)

為了改良機械的物性，較佳係在乙酸纖維素薄膜中添加聚酯胺甲酸酯。又，聚酯胺甲酸酯係為下述通式(1)所示之聚酯二醇與二異氰酸酯之反應物為佳，再者以可溶於二氯甲烷為佳。In order to improve the physical properties of the machine, it is preferred to add a polyester urethane ester to the cellulose acetate film. Further, the polyester urethane is preferably a reaction product of a polyester diol represented by the following formula (1) and a diisocyanate, and further preferably soluble in dichloromethane.

通式(1): H-(-O-(CH2 )p OOC-(CH2 )m CO)n O-(CH2 )p OHGeneral formula (1): H-(-O-(CH 2 ) p OOC-(CH 2 ) m CO) n O-(CH 2 ) p OH

通式(1)中，p係表示2~4的整數；m係表示2~4的整數；n係表示1~100的整數。In the formula (1), p is an integer of 2 to 4; m is an integer of 2 to 4; and n is an integer of 1 to 100.

進一步詳細描述時，其構成聚酯係為乙二醇、1,3-丙二醇、或1,4-丁二醇之二醇成分，如琥珀酸、戊二酸之二元酸(dibasic acid)成分、或由己二酸所構成之兩末端具有羥基之聚酯，其聚合度n係在1~100的範圍。其最適合的聚合度係根據所使用之二醇及二元酸的種類而有若干差異，聚酯的分子量係為1000~4500的範圍為特佳。When described in further detail, the polyester is a glycol component of ethylene glycol, 1,3-propanediol, or 1,4-butanediol, such as dibasic acid component of succinic acid or glutaric acid. Or a polyester having a hydroxyl group at both ends composed of adipic acid, and the degree of polymerization n is in the range of 1 to 100. The most suitable degree of polymerization differs depending on the type of the diol and the dibasic acid to be used, and the molecular weight of the polyester is particularly preferably in the range of from 1,000 to 4,500.

二氯甲烷可溶的聚酯胺甲酸酯樹脂係藉由通式(1)的聚酯與二異氰酸酯之反應而得到，具有下述通式(2)所示之 重複單位的化合物。The dichloromethane-soluble polyester urethane resin is obtained by a reaction of a polyester of the formula (1) with a diisocyanate, and has the following formula (2). Repeat the unit of the compound.

通式(2): -CONH-R-NHCO-(O-(CH2 )p OOC-(CH2 )m CO)n O-(CH2 )p O)-General formula (2): -CONH-R-NHCO-(O-(CH 2 ) p OOC-(CH 2 ) m CO) n O-(CH 2 ) p O)-

通式(2)中，p係表示2~4的整數；m係表示2~4的整數；n係表示1~100的整數；R係表示2價的原子團殘基。2價的原子團殘基之例係可舉例如下式所述者。In the formula (2), p is an integer of 2 to 4; m is an integer of 2 to 4; n is an integer of 1 to 100; and R is a divalent atomic residue. Examples of the divalent radical residue can be exemplified by the following formula.

可做為聚胺甲酸酯化合物中所使用的二異氰酸酯成分之例者，舉例如伸乙基二異氰酸酯、三亞甲基二異氰酸酯、四亞甲基二異氰酸酯、六亞甲基二異氰酸酯等為代表之聚亞甲基二異氰酸酯(通式：OCN(CH2 )p NCO(p表示2~8的整數))、對伸苯基二異氰酸酯、甲苯基二異氰酸酯、p,p'-二苯基甲烷二異氰酸酯、1,5-伸萘基二異氰酸酯等的芳香族二異氰酸酯、及、間伸二甲苯基二異氰酸酯等，惟不必受限於此等。此等之中，尤以甲苯基二異氰酸酯、間伸二甲苯基二異氰酸酯、及四亞甲基二異氰酸酯由於入手容易，比較的安定且操作也容易，然後聚胺甲酸酯化之情形中與乙酸纖維素之相溶性優異之故而為佳。Examples of the diisocyanate component used in the polyurethane compound may, for example, be ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate or hexamethylene diisocyanate. Polymethylene diisocyanate (formula: OCN(CH 2 ) p NCO (p represents an integer of 2-8)), p-phenylene diisocyanate, tolyl diisocyanate, p,p'-diphenylmethane An aromatic diisocyanate such as a diisocyanate or a 1,5-anaphthyl diisocyanate, or an exo-dimethylphenyl diisocyanate, etc., is not necessarily limited thereto. Among these, in particular, tolyl diisocyanate, meta-xylylene diisocyanate, and tetramethylene diisocyanate are easy to start, relatively stable and easy to handle, and then in the case of polyurethaneization with acetic acid. It is preferred that cellulose has excellent compatibility.

聚酯胺甲酸酯樹脂的分子量係以在2,000~50,000的範圍為佳，可按照成分聚酯類或此等的連結基團之二異氰 酸酯成分的種類或分子量等而做適宜選定。聚酯胺甲酸酯樹脂的分子量係從提昇乙酸纖維素薄膜的機械物性及對於乙酸纖維素的相溶性之點而言，以5,000~15,000的範圍為更佳。二氯甲烷可溶性聚酯胺甲酸酯的合成係記由混合通式(1)所示之聚酯二醇與二異氰酸酯，且在攪拌下進行加熱可更容易得到。通式(1)所示之聚酯二醇藉由相當之二元酸或其烷基酯類與二醇類之聚酯化反應或由酯交換反應所引起之熱溶融縮合法、或此等酸之醯氯與二醇類的界面縮合法中任一者之方法，適當調整成末端基為羥基而可容易地合成。The molecular weight of the polyester urethane resin is preferably in the range of 2,000 to 50,000, and may be diisocyanate according to the component polyester or a linking group thereof. The type, molecular weight, and the like of the acid ester component are appropriately selected. The molecular weight of the polyester urethane resin is preferably in the range of 5,000 to 15,000 from the viewpoint of improving the mechanical properties of the cellulose acetate film and the compatibility with cellulose acetate. The synthesis of the methylene chloride-soluble polyester urethane is carried out by mixing the polyester diol represented by the general formula (1) with a diisocyanate, and heating can be more easily obtained by stirring. a polyester diol represented by the formula (1) by a polyesterification reaction of a dibasic acid or an alkyl ester thereof with a diol or a thermal fusion condensation method caused by a transesterification reaction, or the like The method of any of the interfacial condensation methods of the acid ruthenium chloride and the diol can be easily synthesized by appropriately adjusting the terminal group to a hydroxyl group.

本發明中所使用的二氯甲烷可溶性聚酯胺甲酸酯樹脂係以與乙醯化度58%以上之乙酸纖維素有非常相溶性為宜。一般係認為會因樹脂的構造而有若干的相異，惟聚酯胺甲酸酯的分子量為10,000以下之情形，相對於乙酸纖維素100質量份，即使聚酯胺甲酸酯200質量份亦為相溶。The methylene chloride-soluble polyester urethane resin used in the present invention is preferably compatible with cellulose acetate having a degree of acetylation of 58% or more. Generally, it is considered that there are some differences depending on the structure of the resin, but the molecular weight of the polyester urethane is 10,000 or less, and even 200 parts by mass of the polyester urethane relative to 100 parts by mass of the cellulose acetate. For compatibility.

因此，將聚酯胺甲酸酯樹脂與乙酸纖維素混合，而改善其皮膜的機械物性之情形中，聚酯胺甲酸酯樹脂的含量只要依照胺甲酸酯樹脂的種類、分子量、所期望的機械物性而適當決定即可。而在保持乙酸纖維素的特性直接來改善機械物性之情形中，相對於乙酸纖維素，聚酯胺甲酸酯樹脂係含有10~50質量%為適宜。又，該聚酯胺甲酸酯樹脂係係在至少到達180℃之前是安定且不會熱分解的。該二氯甲烷可溶性的聚酯胺甲酸酯類對於特別是58%以上之乙醯化度的乙酸纖維素有非常大的相溶性為佳。因此，混合兩者以進行製膜時，能得到極佳且透明度高的薄膜。而 且，此等的聚酯胺甲酸酯類係由於其平均分子量高，所以與以往的低分子可塑劑不同，即使在高溫下也幾乎沒有揮發性。因此，藉由此等的混合物而製膜所得之皮膜係在隨後的加工中，以往的可塑劑中所見的可塑劑揮發、或因移行所引起的不合適少。Therefore, in the case where the polyester urethane resin is mixed with cellulose acetate to improve the mechanical properties of the film, the content of the polyester urethane resin is as long as it depends on the type, molecular weight, and desired of the urethane resin. The mechanical properties can be appropriately determined. In the case where the properties of the cellulose acetate are maintained to directly improve the mechanical properties, the polyester urethane resin is preferably contained in an amount of 10 to 50% by mass based on the cellulose acetate. Further, the polyester urethane resin system is stable and does not thermally decompose before it reaches at least 180 °C. The methylene chloride-soluble polyester urethane preferably has a very large compatibility with cellulose acetate having a degree of acetylation of 58% or more. Therefore, when both are mixed to form a film, an excellent film having high transparency can be obtained. and Moreover, since these polyester urethane types are high in average molecular weight, unlike the conventional low molecular plasticizer, there is almost no volatility even at a high temperature. Therefore, the film obtained by the film formation by the above-mentioned mixture is in the subsequent processing, and the plasticizer seen in the conventional plasticizer volatilizes or is less suitable due to migration.

藉由將聚酯胺甲酸酯添加至乙酸纖維素薄膜，使得於高溫及低溫中的耐折強度及拉伸強度大、薄膜不易破裂而為佳。By adding the polyester urethane film to the cellulose acetate film, the folding strength and the tensile strength at high temperature and low temperature are large, and the film is not easily broken.

以往，為提高皮膜的耐折強度或拉伸強度，係使用低分子可塑劑。該方法在常溫、高濕狀態中係有某程度的效果，但是在低溫、高濕狀態中則皮膜的柔軟性消失，未必能得到滿足的結果。再者，當常識改善因低分子可塑劑所引起的機械性質時，可塑劑的添加量以及如拉伸強度般的機械性質一般係顯著地下降。在將二氯甲烷可溶性聚酯胺甲酸酯樹脂添加至乙酸纖維素之情形，一般係認為降低了樹脂的添加量以及若干的拉伸強度，與添加低分子可塑劑之情形比較，明顯地強度的降低低下減少，而得到與無添加之情形大致上同等的耐折強度大之強韌薄膜。Conventionally, in order to improve the folding strength or tensile strength of a film, a low molecular plasticizer is used. This method has a certain effect in a normal temperature and a high-humidity state. However, in a low-temperature and high-humidity state, the softness of the film disappears, and a satisfactory result may not necessarily be obtained. Furthermore, when common sense improves the mechanical properties caused by low molecular plasticizers, the amount of plasticizer added and the mechanical properties such as tensile strength generally decrease significantly. In the case where a dichloromethane-soluble polyester urethane resin is added to cellulose acetate, it is generally considered that the amount of addition of the resin and a certain tensile strength are lowered, and the strength is remarkably compared with the case of adding a low-molecular plasticizer. The reduction is lowered, and a tough film having a high folding strength which is substantially equivalent to the case of no addition is obtained.

再者，藉由混合聚酯胺甲酸酯，可防止於低溫、高濕中可塑劑的移行。為此，可得到薄膜相互並無黏著，且有非常的柔軟性，沒有皺折或刷不開等問題之透明且有光澤的薄膜。Further, by mixing the polyester urethane, the migration of the plasticizer in low temperature and high humidity can be prevented. For this reason, it is possible to obtain a transparent and glossy film in which the films are not adhered to each other and have a very high flexibility without wrinkles or brushing.

為了改良機械的物性，乙酸纖維素薄膜中可使用以下的可塑劑以取代上述的聚酯胺甲酸酯、或與聚酯胺甲酸酯併用。In order to improve the physical properties of the machine, the following plasticizer may be used in the cellulose acetate film in place of or in combination with the polyester urethane.

可塑劑係使用磷酸酯或碳酸酯。磷酸酯之例係包含磷酸三苯酯(TPP)及磷酸三甲苯酚酯(TCP)。碳酸酯係以苯二甲酸酯及檸檬酸酯為代表。苯二甲酸酯之例係包含二甲基丁酸酯(DMP)、二乙基丁酸酯(DEP)、二丁基丁酸酯(DBP)、二辛基丁酸酯(DOP)、二苯基丁酸酯(DPP)及二乙基己基丁酸酯(DEHP)。檸檬酸酯之例係包含O-乙醯檸檬酸三乙基(OACTE)及O-乙醯檸檬酸三丁基(OACTB)。其他的碳酸酯之例係包含油酸丁酯、蓖麻醇酸甲基乙醯、癸二酸二丁酯、各種的偏苯三酸酯。較佳係使用苯二甲酸酯系可塑劑(DMP、DEP、DBP、DOP、DPP、DEHP)。以DEP及DPP為特佳。可塑劑的添加量係為纖維素酯之量的0.1~25質量%為佳、1~20質量%為更佳、3~15質量%為最佳。The plasticizer uses a phosphate or a carbonate. Examples of phosphates include triphenyl phosphate (TPP) and tricresyl phosphate (TCP). Carbonates are represented by phthalates and citrates. Examples of phthalates include dimethyl butyrate (DMP), diethyl butyrate (DEP), dibutyl butyrate (DBP), dioctyl butyrate (DOP), and Phenylbutyrate (DPP) and diethylhexylbutyrate (DEHP). Examples of citrate esters include O-ethyl citrate triethyl (OACTE) and O-acetonitrile tributyl citrate (OACTB). Examples of other carbonates include butyl oleate, ricinoleic acid methyl ethyl hydrazine, dibutyl sebacate, and various trimellitic acid esters. A phthalate-based plasticizer (DMP, DEP, DBP, DOP, DPP, DEHP) is preferably used. It is especially good for DEP and DPP. The amount of the plasticizer to be added is preferably from 0.1 to 25% by mass, more preferably from 1 to 20% by mass, still more preferably from 3 to 15% by mass, based on the amount of the cellulose ester.

乙酸纖維素薄膜中可添加惡化防止劑(例如：抗氧化劑、過氧化物分解劑、自由基抑制劑、金屬惰性化劑、酸捕獲劑、胺)。關於惡化防止劑係在特開平3-199201號、同5-1907073號、同5-194789號、同5-271471號、同6-107854號的各公報中有記載。惡化防止劑的添加量係為所調製溶液(塗布液)的0.01~1質量%為佳、0.01~0.2質量%為較佳。添加量低於0.01質量%時，惡化防止劑的效果係幾乎觀察不到。添加量超過1質量%時，係有觀察到惡化防止劑往薄膜表面的滲移(滲出)之情形。特佳的惡化防止劑之例係可舉例如丁基化羥基甲苯(BHT)、三苄基胺(TBA)。A deterioration preventing agent (for example, an antioxidant, a peroxide decomposing agent, a radical inhibitor, a metal inerting agent, an acid trapping agent, an amine) may be added to the cellulose acetate film. The deterioration prevention agent is described in each of the publications of Japanese Patent Publication No. Hei 3-199201, No. 5-1907073, No. 5-194749, No. 5-271471, and No. 6-107054. The amount of the deterioration preventing agent to be added is preferably 0.01 to 1% by mass, preferably 0.01 to 0.2% by mass, based on the prepared solution (coating liquid). When the amount added is less than 0.01% by mass, the effect of the deterioration preventing agent is hardly observed. When the amount added exceeds 1% by mass, it is observed that the deterioration preventing agent migrates (bleeds out) to the surface of the film. Examples of the particularly preferable deterioration preventing agent include butylated hydroxytoluene (BHT) and tribenzylamine (TBA).

(雙軸延伸)(biaxial extension)

為了減低假設的變形，乙酸纖維素薄膜係進行延伸處 理為適宜。藉由進行延伸，因可減低延伸方向的假設變形，且為了於面內全部的方向減低了變形，以進行雙軸延伸為較佳。雙軸延伸係有同時雙軸延伸法與逐次雙軸延伸法，從連續製造之觀點以逐次雙軸延伸方法為佳，流延塗布液之後由輸送帶或滾筒將薄膜剝離下來，使其往寬度方向(長度方向)延伸之後，再往長度方向(寬度方向)延伸。往寬度方向延伸之方法係記載於例如特開昭62-115035號、特開平4-152125號、同4-284211號、同4-298310號、同11-48271號等的各公報。In order to reduce the assumed deformation, the cellulose acetate film is extended. Reasonable. By performing the stretching, it is preferable to reduce the assumed deformation in the extending direction and to reduce the deformation in all directions in the plane to perform biaxial stretching. The biaxial extension system has a simultaneous biaxial stretching method and a sequential biaxial stretching method. From the viewpoint of continuous manufacturing, a sequential biaxial stretching method is preferred, and after the casting liquid is cast, the film is peeled off by a conveyor belt or a roller to make it width. After extending in the direction (longitudinal direction), it extends in the longitudinal direction (width direction). The method of extending in the width direction is disclosed in, for example, JP-A-62-115035, JP-A-4-152125, No. 4-284211, No. 4-298310, and No. 11-48271.

薄膜的延伸係在常溫或加熱條件下實施。加熱溫度係為薄膜的玻璃轉移溫度以下為佳。薄膜係可在乾燥中的處理來進行延伸，於溶媒殘存之情形為特別有效。往長度方向延伸之情形，係例如調節薄膜搬送輥的速度、加速薄膜的捲取速度使其比薄膜的剝離速度要快的方式來延伸薄膜。往寬度方向延伸之情形，薄膜的寬度係一邊以拉幅機保持、一邊來搬送，可藉由緩緩地擴大拉幅機的寬度來延伸薄膜。在薄膜的乾燥後，亦可使用延伸機來進行延伸(較佳為使用長型延伸機之單軸延伸)。薄膜的延伸倍率(相對於原來的長度因延伸所增加部分的比率)係以5~50%的範圍為佳、10~40%的範圍為較佳、15~35%的範圍為最佳。The extension of the film is carried out under normal temperature or heating conditions. The heating temperature is preferably at least the glass transition temperature of the film. The film can be stretched by treatment in a dry state, and is particularly effective in the case where the solvent remains. In the case of extending in the longitudinal direction, for example, the speed of the film transport roller is adjusted, and the take-up speed of the film is accelerated to make the film faster than the peeling speed of the film. In the case of extending in the width direction, the width of the film is carried while being held by the tenter, and the film can be stretched by gradually expanding the width of the tenter. After the film has been dried, an extension can also be used for stretching (preferably using a uniaxial extension of a long stretcher). The stretching ratio of the film (the ratio of the portion to which the elongation is increased relative to the original length) is preferably in the range of 5 to 50%, preferably in the range of 10 to 40%, and preferably in the range of 15 to 35%.

從此等流延後至乾燥之步驟係可在空氣雰圍氣下、亦可在氮氣等的惰性氣體雰圍氣下。本發明中所使用之乙酸纖維素薄膜的製造中所使用的捲取機係一般所使用的即可，可利用固定張力法、固定扭矩法、錐形張力法、內部應力一定的程序張力控制法等的捲取方法來進行捲取。The steps from the casting to the drying may be carried out under an air atmosphere or an inert gas atmosphere such as nitrogen. The coiler used in the production of the cellulose acetate film used in the present invention may be generally used, and a fixed tension method, a fixed torque method, a cone tension method, or a program tension control method with a constant internal stress may be used. The method of winding is used for the winding.

(乙酸纖維素薄膜的表面處理)(surface treatment of cellulose acetate film)

乙酸纖維素薄膜較佳係施加表面處理。具體的方法係可舉例如電暈放電處理、輝光放電處理、火焰處理、酸處理、鹼處理或紫外線照射處理。又，如特開平7-333433號公報中所記載的，亦可設置下塗層。從確保薄膜的平面性之觀點而言，在此等處理中乙酸纖維素薄膜的溫度為Tg(玻璃轉移溫度)以下、具體而言為150℃以下為適宜。The cellulose acetate film is preferably subjected to a surface treatment. Specific methods include, for example, corona discharge treatment, glow discharge treatment, flame treatment, acid treatment, alkali treatment, or ultraviolet irradiation treatment. Further, as described in Japanese Laid-Open Patent Publication No. Hei 7-333433, an undercoat layer may be provided. From the viewpoint of ensuring the planarity of the film, the temperature of the cellulose acetate film in these treatments is preferably not more than Tg (glass transition temperature), specifically 150 ° C or less.

乙酸纖維素薄膜做為偏光板之透明保護膜使用之情形中，從與偏光膜的黏著性之觀點而言，進行酸處理或鹼處理、亦即對於乙酸纖維素實施皂化處理為特佳。表面能量為55mN/m以上為佳，60mN/m以上、75mN/m以下為更佳。In the case where the cellulose acetate film is used as a transparent protective film for a polarizing plate, it is particularly preferable to carry out an acid treatment or an alkali treatment, that is, a saponification treatment with cellulose acetate from the viewpoint of adhesion to the polarizing film. The surface energy is preferably 55 mN/m or more, more preferably 60 mN/m or more and 75 mN/m or less.

以下，係照例具體說明鹼性皂化處理。乙酸纖維素薄膜的鹼性皂化處理係將薄膜表面浸漬於鹼性溶液之後，嚄酸性溶液中和、水洗並乾燥之週期來進行為適宜。鹼性溶液可舉例如氫氧化鉀溶液、氫氧化鈉溶液，氫氧化離子之規定濃度係以0.1~3.0莫耳/L的範圍為佳、0.5~2.0莫耳/L的範圍為更佳。鹼性溶液溫度係以在室溫~90℃的範圍為佳、40~70℃的範圍為更佳。Hereinafter, the alkaline saponification treatment will be specifically described as an example. The alkaline saponification treatment of the cellulose acetate film is carried out by immersing the surface of the film in an alkaline solution, neutralizing the acidic solution, washing with water, and drying. The alkaline solution may, for example, be a potassium hydroxide solution or a sodium hydroxide solution, and the predetermined concentration of the hydroxide ion is preferably in the range of 0.1 to 3.0 mol/L, more preferably in the range of 0.5 to 2.0 mol/L. The temperature of the alkaline solution is preferably in the range of room temperature to 90 ° C, more preferably in the range of 40 to 70 ° C.

固體的表面能量可藉由如「浸潤的基礎與應用」(REALIZE公司1989.12.10發行)中記載的接觸角法、濕潤熱法、及吸附法而求得。本發明之乙酸纖維素薄膜的情形係以使用接觸角法為適宜。具體而言，將表面能量已知之2種溶液滴下至乙酸纖維素薄膜，在液滴的表面與薄膜表面的交點中，以拉伸液滴之切線與薄膜表面所形成的角，將含有液滴之方位角定義為接觸角，藉由計算以算出薄膜 的表面能量。The surface energy of the solid can be obtained by a contact angle method, a wet heat method, and an adsorption method as described in "Basic and Application of Wetting" (issued by REALIZE Co., Ltd., 1989.12.10). The case of the cellulose acetate film of the present invention is preferably a contact angle method. Specifically, two kinds of solutions having known surface energies are dropped onto the cellulose acetate film, and at the intersection of the surface of the droplet and the surface of the film, the angle formed by the tangent of the stretched droplet and the surface of the film will contain droplets. The azimuth is defined as the contact angle, which is calculated by calculation to calculate the film. Surface energy.

上述支持體的厚度係為10~200μm為佳、20~150μm為更佳。The thickness of the support is preferably from 10 to 200 μm, more preferably from 20 to 150 μm.

如上所述，光學補償薄片係可為在由聚合物薄膜所構成之支持體上，形成由含有液晶性化合物之液晶組成物所形成之光學各向異性層而製作的積層薄膜。亦可在支持體上形成配向膜，且在該配向膜上形成光學各向異性層。如此，在本說明書中如「支持體上」等的表現係除了直接設置於支持體等者以外，亦包含隔著配向膜等的其他層而設置之情形的意思。As described above, the optical compensation sheet may be a laminated film produced by forming an optically anisotropic layer formed of a liquid crystal composition containing a liquid crystalline compound on a support composed of a polymer film. An alignment film may also be formed on the support, and an optically anisotropic layer is formed on the alignment film. In this regard, the expression "on the support" or the like in the present specification means that it is provided separately from the support or the like, and is also provided by interposing another layer such as an alignment film.

(光學各向異性層)(optical anisotropic layer)

前述光學各向異性層係在支持體之聚合物薄膜上，直接或隔著配向膜等的其他層而形成的。前述光學各向異性層係由含有至少一種聚合性液晶性化合物之硬化性組成物所形成者為佳。例如，前述光學各向異性層係可藉由將含有液晶性化合物及視需要的聚合性起始劑、或任意成分之塗布液，塗布至配向膜之上以形成所期望之配向狀態後，進行聚合反應，並將液晶性化合物的分子固定成其配向狀態而可形成。The optically anisotropic layer is formed on the polymer film of the support directly or via another layer such as an alignment film. The optically anisotropic layer is preferably formed of a curable composition containing at least one polymerizable liquid crystal compound. For example, the optically anisotropic layer can be formed by applying a liquid crystal compound, optionally a polymerizable initiator, or a coating liquid of an optional component onto an alignment film to form a desired alignment state. The polymerization reaction can be carried out by fixing the molecules of the liquid crystalline compound to their aligned state.

塗布液的調製中使用之溶媒係以使用有機溶媒為佳。有機溶媒之例係包含醯胺(例如：N,N-二甲基甲醯胺)、亞碸(例如：二甲亞碸)、雜環化合物(例如：吡啶)、烴(例如，苯、己烷)、烷基鹵(例如：氯仿、二氯甲烷、四氯乙烷)、酯(例如：乙酸甲基、乙酸丁酯)、酮(例如：丙酮、甲基乙基酮)、醚(例如：四氫呋喃、1,2-二甲氧基乙烷)。以烷基 鹵及酮為佳。可併用二種以上之有機溶媒。塗布液的塗布係可依照習知的方法(例如：金屬棒材塗布法、擠壓塗布法、直接照相凹版塗布法、逆照相凹版塗布法、模頭塗布法)來實施。The solvent used in the preparation of the coating liquid is preferably an organic solvent. Examples of the organic solvent include decylamine (for example, N,N-dimethylformamide), hydrazine (for example, dimethyl hydrazine), heterocyclic compound (for example, pyridine), and hydrocarbon (for example, benzene, hexyl). Alkanes, alkyl halides (eg chloroform, dichloromethane, tetrachloroethane), esters (eg methyl acetate, butyl acetate), ketones (eg acetone, methyl ethyl ketone), ethers (eg : tetrahydrofuran, 1,2-dimethoxyethane). Alkyl Halogen and ketone are preferred. Two or more organic solvents may be used in combination. The coating of the coating liquid can be carried out in accordance with a conventional method (for example, a metal bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, or a die coating method).

前述光學各向異性層的厚度係以0.1~20μm為佳、0.5~15μm為較佳、1~10μm為更佳。The thickness of the optically anisotropic layer is preferably 0.1 to 20 μm, more preferably 0.5 to 15 μm, still more preferably 1 to 10 μm.

前述液晶性化合物係可為棒狀液晶性化合物及圓盤狀液晶性化合物中任一者。特佳係使用圓盤狀液晶性化合物。The liquid crystal compound may be any one of a rod-like liquid crystal compound and a discotic liquid crystal compound. Particularly preferred is a discotic liquid crystalline compound.

(棒狀液晶性化合物)(rod-like liquid crystalline compound)

棒狀液晶性化合物係使用甲亞胺類、氧化偶氮類、氰基聯苯類、氰基苯基酯類、安息香酸酯類、環己烷碳酸苯基酯類、氰基苯基環己烷類、氰基取代苯基嘧啶類、烷氧基取代苯基嘧啶類、苯基二烷類、二苯基乙炔類及鏈烯基環己基苄腈類為佳。另外，棒狀液晶性化合物中亦可含有金屬錯合物。The rod-like liquid crystal compound uses methylimine, oxidized azo, cyanobiphenyl, cyanophenyl ester, benzoic acid ester, phenylcyclohexane carbonate, and cyanophenylcyclohexane. Alkanes, cyano substituted phenyl pyrimidines, alkoxy substituted phenyl pyrimidines, phenyl two Alkane, diphenylacetylene and alkenylcyclohexylbenzonitrile are preferred. Further, the rod-like liquid crystalline compound may also contain a metal complex.

關於棒狀液晶性化合物係在日本化學會編「季刊化學總說第22卷液晶的化學」(1994)的第4章、第7章及第11章、及日本學術振興會第142委員會編「液晶裝置手冊」的第3章中有記載。棒狀液晶性化合物的雙折射率係在0.001~0.7的範圍為適宜。棒狀液晶性化合物係為了固定其配向狀態，必須具有聚合性基。聚合性基(Q)之例係如以下所示。The rod-like liquid crystal compound is edited in Chapters 4, 7 and 11 of the "Chemicals of the Quarterly Chemistry, Vol. 22, Liquid Crystal Chemistry" (1994) and the 142th Committee of the Japan Society for the Promotion of Science. It is described in Chapter 3 of the Handbook of Liquid Crystal Devices. The birefringence coefficient of the rod-like liquid crystal compound is preferably in the range of 0.001 to 0.7. The rod-like liquid crystalline compound is required to have a polymerizable group in order to fix its alignment state. Examples of the polymerizable group (Q) are as follows.

聚合性基(Q)係以不飽和聚合性基(Q1~Q7)、環氧基(Q8)或吖丙啶基(Q9)為佳、不飽和聚合性基為更佳、乙烯性不飽和聚合性基(Q1~Q6)為最佳。棒狀液晶性化合物係具有對於短軸方向大致上成對稱之分子構造為適宜。為此，棒狀分子構造的兩端具有聚合性基為適宜。以下，係表示棒狀液晶性化合物之例。The polymerizable group (Q) is preferably an unsaturated polymerizable group (Q1 to Q7), an epoxy group (Q8) or an aziridine group (Q9), and an unsaturated polymerizable group is more preferable, and an ethylenically unsaturated polymerization is preferred. The base (Q1~Q6) is the best. The rod-like liquid crystal compound is preferably a molecular structure which is substantially symmetrical with respect to the minor axis direction. For this reason, it is preferred that both ends of the rod-like molecular structure have a polymerizable group. Hereinafter, an example of a rod-like liquid crystalline compound is shown.

光學各向異性層係將含有棒狀液晶性化合物或後述之聚合性起始劑、或以往習知的任意添加劑(例如：可塑劑、單體、界面活性劑、纖維素酯、1,3,5-三化合物、對掌劑)之液晶組成物(塗布液)，塗布至配向膜之上，藉由聚合反應，固定液晶性化合物的配向而可形成。The optically anisotropic layer contains a rod-like liquid crystal compound or a polymerizable initiator described later, or any conventionally known additives (for example, a plasticizer, a monomer, a surfactant, a cellulose ester, 1, 3, 5-three The liquid crystal composition (coating liquid) of the compound and the palm powder is applied onto the alignment film, and can be formed by fixing the alignment of the liquid crystal compound by a polymerization reaction.

(圓盤狀液晶性化合物)(disc liquid crystal compound)

圓盤狀(碟型)液晶性化合物之例係可舉例如：C.Destrade等人的研究報告、Mol.Cryst.71卷、第111頁(1981年)所記載的苯衍生物、C.Destrade等人的研究報告、Mol.Cryst.122卷、第141頁(1985年)、Physics lett,A,78卷、第82頁(1990)所記載的三亞蘊衍生物、B.Kohne等人的研究報告、Angew.Chem.96卷、第70頁(1984年)所記載的環己烷衍生物及J.M.Lehn等人的研究報告、J.Chem.Commun.,第1794頁(1985年)、J.Zhang等人的研究報告、J.Am.Chem.Soc.116卷、第2655頁(1994年)所記載的吖冠系或苯基乙炔系大環等。再者，可做為圓盤 狀液晶性化合物者，一般此等係當作分子中心的母核，以直鏈的烷基或烷氧基、取代苯甲醯氧基等做為其直鏈，呈現包含成放射線狀取代之構造者的液晶性。但是，分子本身具有負的單軸性，只要可賦予固定的配向即可，不需限定於此等。Examples of the disc-shaped (disc type) liquid crystal compound include, for example, a research report by C. Destrade et al., a benzene derivative described in Mol. Cryst. 71, page 111 (1981), and C. Destrade. Research Report by M., Mol. Cryst. 122, p. 141 (1985), Physics Lett, A, Vol. 78, p. 82 (1990), B. Kohne et al. Report, Angew. Chem., Vol. 96, p. 70 (1984), cyclohexane derivatives and JMLehn et al., J. Chem. Commun., p. 1794 (1985), J. The research report of Zhang et al., J. Am. Chem. Soc. 116, p. 2655 (1994), the 吖 crown or phenyl acetylene macrocycle. Furthermore, it can be used as a disc In the case of a liquid crystal compound, generally, these are regarded as a mother nucleus of a molecular center, and a linear alkyl group, an alkoxy group, a substituted benzyl methoxy group or the like is used as a linear chain, and a structure including a radial substitution is exhibited. Liquidity of the person. However, the molecule itself has a negative uniaxiality as long as it can impart a fixed alignment, and is not limited thereto.

為了使圓盤狀液晶性化合物的分子藉由聚合而固定，使圓盤狀液晶性化合物分子的圓盤狀芯與做為取代基之聚合性基結合為佳。但是，聚合性基直接與圓盤狀芯鍵結時，難以在聚合反應中保持配向狀態。因而在圓盤狀芯與聚合性基之間導入連結基。因此，具有聚合性基之圓盤狀液晶性化合物係以下述通式(3)所示之化合物為佳。In order to fix the molecules of the discotic liquid crystalline compound by polymerization, it is preferred to combine the disc-shaped core of the discotic liquid crystalline compound molecule with a polymerizable group as a substituent. However, when the polymerizable group is directly bonded to the disk-shaped core, it is difficult to maintain the alignment state in the polymerization reaction. Therefore, a linking group is introduced between the disc-shaped core and the polymerizable group. Therefore, the discotic liquid crystalline compound having a polymerizable group is preferably a compound represented by the following formula (3).

通式(3): D(-L-P)n General formula (3): D(-LP) n

通式(3)中，D為圓盤狀芯；L為二價的連結基，P為聚合性基，且n為4~12的整數。通式(3)之例係如以下所示。以下的各例中，LP(或PL)係意味著二價的連結基(L)與聚合性基(P)之組合。In the formula (3), D is a disc-shaped core; L is a divalent linking group, P is a polymerizable group, and n is an integer of 4 to 12. Examples of the general formula (3) are as follows. In each of the following examples, LP (or PL) means a combination of a divalent linking group (L) and a polymerizable group (P).

通式(3)中，二價的連結基(L)係以選自於伸烷基、伸烯基、伸芳基、-CO-、-NH-、-O-、-S-及彼等組合所構成群組之二價連結基為佳。二價的連結基(L)係以組合至少兩個 選自於伸烷基、伸芳基、-CO-、-NH-、-O-及-S-所構成群組之二價基的二價連結基為較佳。二價的連結基(L)係以組合至少兩個選自於伸烷基、伸芳基、-CO-及-O-所構成群組之二價基的二價連結基為最佳。伸烷基的碳原子數係以1~12為佳。伸烯基的碳原子數係以2~12為佳。伸芳基的碳原子數係以6~10為佳。In the formula (3), the divalent linking group (L) is selected from the group consisting of an alkyl group, an alkenyl group, an extended aryl group, -CO-, -NH-, -O-, -S-, and the like. It is preferred to combine the divalent linking groups of the group formed. Bivalent linking group (L) is combined with at least two A divalent linking group selected from the group consisting of an alkyl group, an aryl group, a -CO-, -NH-, -O-, and -S- is preferably a divalent linking group. The divalent linking group (L) is preferably a divalent linking group which combines at least two divalent groups selected from the group consisting of an alkyl group, an extended aryl group, and -CO- and -O-. The number of carbon atoms of the alkyl group is preferably from 1 to 12. The number of carbon atoms in the alkenyl group is preferably from 2 to 12. The number of carbon atoms of the aryl group is preferably from 6 to 10.

二價的連結基(L)之例係如以下所示。左側係與圓盤狀芯(D)鍵結，右側係與聚合性基(P)鍵結。AL係意味著伸烷基或伸烯基、AR係意味著伸芳基。另外，伸烷基、伸烯基及伸芳基亦可具有取代基(例如：烷基)。Examples of the divalent linking group (L) are as follows. The left side is bonded to the disc-shaped core (D), and the right side is bonded to the polymerizable group (P). AL means an alkyl group or an alkenyl group, and an AR type means an aryl group. Further, the alkylene group, the extended alkenyl group and the extended aryl group may have a substituent (for example, an alkyl group).

L1:-AL-CO-O-AL- L2:-AL-CO-O-AL-O- L3:-AL-CO-O-AL-O-AL- L4:-AL-CO-O-AL-O-CO- L5:-CO-AR-O-AL- L6:-CO-AR-O-AL-O- L7:-CO-AR-O-AL-O-CO- L8:-CO-NH-AL- L9:-NH-AL-O- L10:-NH-AL-O-CO- L11:-O-AL- L12:-O-AL-O- L13:-O-AL-O-CO- L14:-O-AL-O-CO-NH-AL- L15:-O-AL-S-AL- L16:-O-CO-AR-O-AL-CO- L17:-O-CO-AR-O-AL-O-CO- L18:-O-CO-AR-O-AL-O-AL-O-CO- L19:-O-CO-AR-O-AL-O-AL-O-AL-O-CO- L20:-S-AL- L21:-S-AL-O- L22:-S-AL-O-CO- L23:-S-AL-S-AL- L24:-S-AR-AL-L1:-AL-CO-O-AL- L2:-AL-CO-O-AL-O- L3:-AL-CO-O-AL-O-AL- L4:-AL-CO-O-AL-O-CO- L5:-CO-AR-O-AL- L6:-CO-AR-O-AL-O- L7:-CO-AR-O-AL-O-CO- L8:-CO-NH-AL- L9:-NH-AL-O- L10:-NH-AL-O-CO- L11:-O-AL- L12:-O-AL-O- L13:-O-AL-O-CO- L14:-O-AL-O-CO-NH-AL- L15:-O-AL-S-AL- L16:-O-CO-AR-O-AL-CO- L17:-O-CO-AR-O-AL-O-CO- L18:-O-CO-AR-O-AL-O-AL-O-CO- L19:-O-CO-AR-O-AL-O-AL-O-AL-O-CO- L20:-S-AL- L21:-S-AL-O- L22:-S-AL-O-CO- L23:-S-AL-S-AL- L24:-S-AR-AL-

通式(3)的聚合性基(P)可依照聚合反應的種類而決定。聚合性基(P)之例係如以下所示。The polymerizable group (P) of the formula (3) can be determined depending on the type of the polymerization reaction. Examples of the polymerizable group (P) are as follows.

聚合性基(P)係以不飽和聚合性基(P1、P2、P3、P7、P8、P15、P16、P17)或環氧基(P6、P18)為佳、不飽和聚合性基為較佳、乙烯性不飽和聚合性基(P1、P7、P8、P15、P16、P17)為更佳。The polymerizable group (P) is preferably an unsaturated polymerizable group (P1, P2, P3, P7, P8, P15, P16 or P17) or an epoxy group (P6 or P18), and an unsaturated polymerizable group is preferred. Further, an ethylenically unsaturated polymerizable group (P1, P7, P8, P15, P16, P17) is more preferable.

通式(3)中，如上述般，n為4~12的整數。具體的數字係可依照圓盤狀芯(D)的種類而決定。另外，複數個的L與P的組合係可不同，相同為佳。In the general formula (3), as described above, n is an integer of 4 to 12. The specific number can be determined according to the type of the disc-shaped core (D). In addition, a plurality of combinations of L and P may be different, and the same is preferred.

使用圓盤狀液晶性化合物之情形，光學各向異性層係具有負的雙折射之層，而圓盤狀構造單位之面對於乙酸纖維素薄膜表面為傾斜的，且圓盤狀構造單位之面與乙酸纖維素薄膜表面所形成之角度係向光學各向異性層的深度方向變化為適宜。In the case of using a discotic liquid crystalline compound, the optically anisotropic layer has a layer of negative birefringence, and the face of the disc-shaped structural unit is inclined to the surface of the cellulose acetate film, and the surface of the disc-shaped structural unit The angle formed with the surface of the cellulose acetate film is suitably changed to the depth direction of the optically anisotropic layer.

圓盤狀構造單位之面的角度(傾斜角)一般係在光學各向異性層的深度方向且從支持體的面增加距離的同時增加或減少。傾斜角係與距離的增加同時增加為佳。再者，傾斜角的變化係包含連續的增加、連續的減少、間歇的增加、間歇的減少、連續的增加與連續的減少之變化，或可包含增加及減少之間歇的變化。間歇的變化係包含在厚度方向的途中傾斜角沒有變化之區域。傾斜角亦可包含傾斜角沒有變化的區域，亦可全體的增加或減少。再者，傾斜角係連續地進行變化為佳。The angle (inclination angle) of the face of the disc-shaped structural unit is generally increased or decreased while increasing the distance from the surface of the support by the depth direction of the optically anisotropic layer. It is preferable that the inclination angle is increased simultaneously with the increase in the distance. Further, the change in the tilt angle includes a continuous increase, a continuous decrease, an intermittent increase, an intermittent decrease, a continuous increase, and a continuous decrease, or may include an increase and decrease in the intermittent change. The intermittent change includes an area where the inclination angle does not change in the middle of the thickness direction. The tilt angle may also include an area where the tilt angle does not change, and may be increased or decreased as a whole. Further, it is preferable that the inclination angle is continuously changed.

在支持體側之圓盤狀單位的傾斜角一般係可藉由選擇圓盤狀液晶性化合物或配向膜的材料、或可藉由選擇摩擦處理方法而進行調整。又，表面側(與支持體為相反側)的圓盤狀單位之傾斜角，一般係藉由選擇圓盤狀液晶性化合物或與圓盤狀液晶性化合物一同使用的其他化合物來進行調整。與圓盤狀液晶性化合物一同使用的化合物之例子可舉例如可塑劑、界面活性劑、聚合性單體及聚合物等以往眾所周知的化合物。傾斜角之變化程度亦可藉由與上述相 同的選擇而調整。The inclination angle of the disk-shaped unit on the side of the support can be generally adjusted by selecting a material of the discotic liquid crystalline compound or the alignment film, or by selecting a rubbing treatment method. Further, the inclination angle of the disk-shaped unit on the surface side (opposite to the support) is generally adjusted by selecting a discotic liquid crystalline compound or another compound used together with the discotic liquid crystalline compound. Examples of the compound to be used together with the discotic liquid crystalline compound include conventionally known compounds such as a plasticizer, a surfactant, a polymerizable monomer, and a polymer. The degree of change in the tilt angle can also be achieved by the above Adjust with the same choice.

可做為與圓盤狀液晶性化合物一同使用的可塑劑、界面活性劑及聚合性單體者，只要係與圓盤狀液晶性化合物具有相溶性、可給予圓盤狀液晶性化合物之傾斜角的變化、或不阻礙配向之任一化合物均可使用。此等之中，尤以聚合性單體(例如：具有乙烯基、乙烯氧基、丙烯醯基及甲基丙烯醯基之化合物)為佳。上述化合物之添加量相對於圓盤狀液晶性化合物，一般係在1~50質量%的範圍、在5~30質量%的範圍為適宜。It can be used as a plasticizer, a surfactant, and a polymerizable monomer which are used together with a discotic liquid crystalline compound, and can be given a tilt angle of a discotic liquid crystalline compound as long as it is compatible with a discotic liquid crystalline compound. Any compound that changes, or does not hinder alignment, can be used. Among these, a polymerizable monomer (for example, a compound having a vinyl group, a vinyloxy group, an acryloyl group and a methacryl group) is preferred. The amount of the compound to be added is generally in the range of 1 to 50% by mass, and preferably in the range of 5 to 30% by mass based on the discotic liquid crystalline compound.

與圓盤狀液晶性化合物一同使用的聚合物只要與圓盤狀液晶性化合物具有相溶性、能賦予圓盤狀液晶性化合物傾斜角之變化之任一聚合物均可使用。聚合物之例係可舉例如纖維素酯。纖維素酯之較佳例係可舉例如乙酸纖維素、乙酸丙酸纖維素、羥基丙基纖維素及乙酸丁酸纖維素。為了不阻礙圓盤狀液晶性化合物的配向，上述聚合物之添加量相對於圓盤狀液晶性化合物，一般係在0.1~10質量%的範圍、0.1~8質量%的範圍為較佳、0.1~5質量%的範圍為更佳。Any polymer which is compatible with the discotic liquid crystalline compound and which can impart a change in the tilt angle of the discotic liquid crystalline compound can be used as long as it is compatible with the discotic liquid crystalline compound. Examples of the polymer include, for example, cellulose esters. Preferred examples of the cellulose ester include cellulose acetate, cellulose acetate propionate, hydroxypropyl cellulose, and cellulose acetate butyrate. In order to prevent the alignment of the discotic liquid crystalline compound, the amount of the polymer added is generally in the range of 0.1 to 10% by mass, preferably 0.1 to 8% by mass, based on the discotic liquid crystalline compound. A range of ~5 mass% is more preferable.

前述光學各向異性層係可使用圓盤狀液晶性化合物，例如可如以下所述而製作。藉由將圓盤狀液晶性化合物及其他的化合物溶解於溶劑之溶液塗布至配向膜上、乾燥，接著加熱至碟型向列相形成溫度，隨後維持配向狀態(碟型向列相)並冷却而可得到。或，上述光學各向異性層係可藉由將液晶性化合物及其他的化合物(此外，例如聚合性單體、光聚合起始劑)溶解於溶劑之溶液塗布至配向膜上、乾 燥，接著加熱至碟型-向列相形成溫度之後使其聚合(藉由UV光的照射等)，然後冷却而可得到。前述光學各向異性層的形成中所使用的圓盤狀液晶性化合物之碟型向列液晶相-固相轉移溫度係以70~300℃為佳、特別是70~170℃為佳。As the optically anisotropic layer, a discotic liquid crystalline compound can be used, and for example, it can be produced as described below. Applying a solution in which a discotic liquid crystalline compound and other compounds are dissolved in a solvent to an alignment film, drying, and then heating to a dish-type nematic phase formation temperature, and then maintaining the alignment state (disc nematic phase) and cooling And available. Alternatively, the optically anisotropic layer can be applied to the alignment film by a solution in which a liquid crystal compound and other compounds (including, for example, a polymerizable monomer or a photopolymerization initiator) are dissolved in a solvent, and dried. Drying is followed by heating to a dish-type nematic phase to form a temperature, then polymerizing it (by irradiation with UV light, etc.), followed by cooling to obtain. The disc-type nematic liquid crystal phase-solid phase transfer temperature of the discotic liquid crystalline compound used for the formation of the optically anisotropic layer is preferably 70 to 300 ° C, particularly preferably 70 to 170 ° C.

(液晶性化合物的配向狀態之固定)(Fixed state of alignment of liquid crystal compound)

在本發明中，因為液晶性化合物具有聚合性基，而可維持固定經配向的液晶性化合物之配向狀態，藉此使光學各向異性層的配向性固定。固定化係藉由聚合反應而實施為適宜。聚合反應係包含使用熱聚合起始劑之熱聚合反應與使用光聚合起始劑之光聚合反應。以光聚合反應為佳。In the present invention, since the liquid crystalline compound has a polymerizable group, the alignment state of the fixed alignment liquid crystal compound can be maintained, whereby the alignment of the optically anisotropic layer is fixed. The immobilization is suitably carried out by a polymerization reaction. The polymerization reaction involves a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. Photopolymerization is preferred.

光聚合起始劑之例係包含α-羰基化合物(美國專利第2367661號、同2367670號的各說明書記載)、偶姻醚(美國專利第2448828號說明書記載)、α-烴取代芳香族偶姻化合物(美國專利第2722512號說明書記載)、多核醌化合物(美國專利第3046127號、同2951758號的各說明書記載)、三芳基咪唑二聚物與對胺基苯基酮的組合(美國專利第3549367號說明書記載)、吖啶及吩化合物(特開昭60-105667號公報、美國專利第4239850號說明書記載)及二唑化合物(美國專利第4212970號說明書記載)。Examples of the photopolymerization initiator include an α-carbonyl compound (described in each specification of U.S. Patent No. 2,276,661 and No. 2,367,670), an acetoin (described in the specification of U.S. Patent No. 2,448,828), and an α-hydrocarbon-substituted aromatic auxin. A compound (described in the specification of U.S. Patent No. 2,725,512), a polynuclear ruthenium compound (described in each specification of U.S. Patent No. 3,046, 127, and 2,591, 758), a combination of a triaryl imidazole dimer and a p-aminophenyl ketone (U.S. Patent No. 3,549,367) No. Description), acridine and pheno a compound (described in JP-A-60-105667, US Pat. No. 4,239,850) and The oxadiazole compound (described in the specification of U.S. Patent No. 4,212,970).

光聚合起始劑的使用量係為塗布液固體成分之0.01~20質量%的範圍為佳、0.5~5質量%的範圍為更佳。The amount of the photopolymerization initiator to be used is preferably in the range of 0.01 to 20% by mass of the solid content of the coating liquid, and more preferably in the range of 0.5 to 5% by mass.

為聚合液晶性化合物的光照射係以使用紫外線為適宜。照射能量係在20mJ/cm2 ~50J/cm2 的範圍為佳、20~5000mJ/cm2 的範圍為較佳、100~800mJ/cm2 的範圍為 更佳。It is suitable to use ultraviolet rays for light irradiation of a liquid crystal compound. The irradiation energy is preferably in the range of 20 mJ/cm 2 to 50 J/cm 2 , more preferably in the range of 20 to 5,000 mJ/cm 2 , and still more preferably in the range of 100 to 800 mJ/cm 2 .

又，為了促進光聚合反應，亦可在加熱條件下實施光照射。保護層亦可設置在光學各向異性層之上。如以上所述般，可藉由在乙酸纖維素薄膜上設置光學各向異性層，以製作光學補償薄片。Further, in order to promote the photopolymerization reaction, light irradiation may be carried out under heating. The protective layer may also be disposed on the optically anisotropic layer. As described above, an optically anisotropic sheet can be produced by providing an optically anisotropic layer on a cellulose acetate film.

(配向膜)(alignment film)

前述光學各向異性層係可利用配向膜而形成。配向膜係具有使在光學各向異性層的製作中所使用之液晶性化合物的分子，於固定方向配向之功能。另外，使液晶性化合物的分子配向之後，只要最後固定其配向狀態即可，配向膜即完成其任務，光學補償薄片本身並非特別必須之物，所以光學補償薄片的層構成上不是必要的構成要素。因此，一旦於配向膜上使液晶化合物的分子配向，隨後固定配向狀態且形成光學各向異性層之後，僅將配向膜上的光學各向異性層轉印至乙酸纖維素薄膜等的支持體上，以製作由沒有配向膜的支持體與光學各向異性層所構成之光學補償薄片係為可能的。The optically anisotropic layer can be formed using an alignment film. The alignment film has a function of aligning molecules of a liquid crystal compound used in the production of an optically anisotropic layer in a fixed direction. Further, after the molecules of the liquid crystal compound are aligned, as long as the alignment state is finally fixed, the alignment film accomplishes its task, and the optical compensation sheet itself is not particularly necessary, so that the layer composition of the optical compensation sheet is not an essential component. . Therefore, once the molecules of the liquid crystal compound are aligned on the alignment film, and then the alignment state is fixed and the optically anisotropic layer is formed, only the optically anisotropic layer on the alignment film is transferred onto the support of the cellulose acetate film or the like. It is possible to fabricate an optical compensation sheet composed of a support having no alignment film and an optically anisotropic layer.

配向膜係具有規定液晶性化合物的配向方向之功能。配向膜係可以有機化合物(較佳為聚合物)的摩擦處理、無機化合物的斜方蒸鍍、具有密紋之層的形成，或由藍米爾‧布羅傑特(Langmuir Blodgett)法(LB膜)之有機化合物(例如：ω-二十三烷酸、二-十八烷甲基氯化銨、硬脂酸甲酯)的累積的手段來進行設置。再者，藉由賦予電場、賦予磁場或光照射，以產生配向功能之配向膜亦為已知。The alignment film has a function of defining an alignment direction of the liquid crystal compound. The alignment film may be a rubbing treatment of an organic compound (preferably a polymer), an oblique vapor deposition of an inorganic compound, a formation of a dense layer, or a Langmuir Blodgett method (LB film). The organic compound (for example, ω-tetracosanoic acid, di-octadecylmethylammonium chloride, methyl stearate) is accumulated by means of accumulation. Further, an alignment film which imparts an alignment function by imparting an electric field, imparting a magnetic field or light is also known.

配向膜較佳係藉由摩擦處理聚合物而形成。聚乙烯醇 為較佳的聚合物。疏水性基鍵結之改質聚乙烯醇為特佳。配向膜亦可由一種的聚合物所形成的，藉由摩擦處理由經交聯之二種聚合物所成之層而形成的為較佳。至少一種的聚合物係可使用其本身可交聯之聚合物、或藉由交聯劑經交聯之聚合物中的任一者為適宜。配向膜係具有官能基之聚合物或於聚合物中導入官能基者，藉由光、熱、PH變化等，使其在聚合物間反應而形成；或，可使用反應活性高的化合物之交聯劑，且在聚合物間導入來自交聯劑之結合基，並藉由在聚合物間進行交聯而可形成。The alignment film is preferably formed by rubbing the polymer. Polyvinyl alcohol It is a preferred polymer. Hydrophobic-bonded modified polyvinyl alcohol is particularly preferred. The alignment film may also be formed of a polymer which is preferably formed by rubbing a layer formed of two kinds of crosslinked polymers. The at least one polymer may be any one of a polymer which is crosslinkable by itself or a polymer which is crosslinked by a crosslinking agent. The alignment film is a polymer having a functional group or a functional group introduced into the polymer, and is formed by reacting between polymers by light, heat, pH change or the like; or, a compound having a high reactivity can be used. A crosslinking agent is introduced, and a binding group derived from a crosslinking agent is introduced between the polymers, and can be formed by crosslinking between the polymers.

像這樣的交聯係可藉由將含有上述聚合物或聚合物與交聯劑之混合物的配向膜塗布液塗布至乙酸纖維素薄膜上之後，進行加熱等而實施。為了確保光學補償薄片的耐久性之故，從將配向膜塗設至乙酸纖維素薄膜上之後，到得到光學補償薄片中的任一階段，進行交聯之處理均可。考慮到形成於配向膜上由液晶性化合物所成之層(光學各向異性層)的配向性時，亦可在使液晶性化合物配向之後，進行充分的交聯。配向膜的交聯一般係藉由將配向膜塗布液塗布至乙酸纖維素薄膜上，且加熱乾燥而實施。該塗布液的加熱溫度設定較低，且於形成後述的光學各向異性層之際，在加熱處理的階段對配向膜進行充分的交聯為適宜。Such a cross-linking can be carried out by applying an alignment film coating liquid containing the above polymer or a mixture of a polymer and a crosslinking agent to a cellulose acetate film, followed by heating or the like. In order to ensure the durability of the optical compensation sheet, the treatment may be carried out by applying the alignment film to the cellulose acetate film and then to the optical compensation sheet at any stage. In consideration of the alignment property of the layer (optical anisotropic layer) formed of the liquid crystal compound formed on the alignment film, sufficient crosslinking can be performed after the liquid crystal compound is aligned. Crosslinking of the alignment film is generally carried out by applying an alignment film coating liquid onto a cellulose acetate film and drying it by heating. The heating temperature of the coating liquid is set to be low, and when the optically anisotropic layer to be described later is formed, it is preferable to sufficiently crosslink the alignment film at the stage of the heat treatment.

配向膜中所使用的聚合物係可使用其本身可交聯的聚合物或藉由交聯劑而交聯的聚合物中之任一者。當然亦可為兩者之聚合物。聚合物之例係可舉例如聚甲基丙烯酸甲酯、丙烯酸/甲基丙烯酸共聚物、苯乙烯/順丁烯二醯亞胺共聚物、聚乙烯醇及改質聚乙烯醇、聚(N-羥甲基丙烯醯 胺)、苯乙烯/乙烯基甲苯共聚物、氯基磺化聚乙烯、硝基纖維素、聚氯乙烯、氯化聚烯烴、聚酯、聚醯亞胺、乙酸乙烯酯/氯化乙烯基共聚物、乙烯/乙酸乙烯酯共聚物、羧基甲基纖維素、聚乙烯、聚丙烯、及聚碳酸酯等的聚合物、明膠及矽烷偶合劑等的化合物。較佳的聚合物之例係舉例如聚(N-羥甲基丙烯醯胺)、羧基甲基纖維素、明膠、聚乙烯醇及改質聚乙烯醇等的水溶性聚合物。較宜係使用明膠、聚乙烯醇及改質聚乙烯醇，較佳則使用聚乙烯醇及改質聚乙烯醇。又，併用兩種聚合度不同的聚乙烯醇或改質聚乙烯醇為最佳。The polymer used in the alignment film may be either a polymer which is crosslinkable by itself or a polymer which is crosslinked by a crosslinking agent. Of course, it can also be a polymer of both. Examples of the polymer include, for example, polymethyl methacrylate, acrylic acid/methacrylic acid copolymer, styrene/methylene iodide copolymer, polyvinyl alcohol, and modified polyvinyl alcohol, poly(N- Hydroxymethyl propylene oxime Amine), styrene/vinyl toluene copolymer, chlorosulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimine, vinyl acetate/vinyl chloride copolymerization Compounds such as polymers, ethylene/vinyl acetate copolymers, carboxymethyl cellulose, polyethylene, polypropylene, and polycarbonate, gelatin, and decane coupling agents. Preferred examples of the polymer include water-soluble polymers such as poly(N-methylol acrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol. It is preferred to use gelatin, polyvinyl alcohol and modified polyvinyl alcohol, preferably polyvinyl alcohol and modified polyvinyl alcohol. Further, it is preferred to use two kinds of polyvinyl alcohol or modified polyvinyl alcohol having different degrees of polymerization.

聚乙烯醇之例係可舉例如皂化度在70~100%的範圍內的聚乙烯醇。一般係皂化度在80~100%的範圍、85~95%的範圍為更佳。又，聚乙烯醇的聚合度係在100~3000的範圍為適宜。改質聚乙烯醇之例係可舉例如經由共聚合改質、鏈移動所引起的改質、或嵌段聚合所引起的改質之聚乙烯醇等。共聚合改質之情形中改質基之例係可舉例如COONa、Si(OH)3 、N(CH3 )3 ．Cl、C9 H19 COO、SO3 、Na、C12 H25 等。進行鏈移動所引起的改質時的改質基之例係舉例如COONa、SH、C12 H25 等。又，進行嵌段聚合所引起的改質時的改質基之例係舉例如COOH、CONH2 、C6 H5 等。此等之中，尤以皂化度在80~100%的範圍之未改質或改質聚乙烯醇為佳。又，皂化度在85~95%的範圍之未改質聚乙烯醇及改質聚乙烯醇為更佳。Examples of the polyvinyl alcohol include polyvinyl alcohol having a degree of saponification in the range of 70 to 100%. Generally, the degree of saponification is preferably in the range of 80 to 100% and in the range of 85 to 95%. Further, the degree of polymerization of the polyvinyl alcohol is preferably in the range of from 100 to 3,000. Examples of the modified polyvinyl alcohol include, for example, reforming by copolymerization, chain shifting, or modification of polyvinyl alcohol by block polymerization. Examples of the modified base in the case of copolymerization modification include, for example, COONa, Si(OH) 3 , and N(CH 3 ) 3 . Cl, C 9 H 19 COO, SO 3 , Na, C 12 H 25 and the like. Examples of the modified base at the time of upgrading caused by chain movement are, for example, COONa, SH, C 12 H 25 and the like. Further, examples of the modified base at the time of upgrading by block polymerization include, for example, COOH, CONH 2 , and C 6 H 5 . Among these, it is preferable to use an unmodified or modified polyvinyl alcohol having a degree of saponification in the range of 80 to 100%. Further, unmodified polyvinyl alcohol and modified polyvinyl alcohol having a degree of saponification in the range of 85 to 95% are more preferable.

可做為改質聚乙烯醇者，特別是使用藉由下述通式所示之化合物所改質之聚乙烯醇的改質物為適宜。該改質聚 乙烯醇在以下係記載為特定的改質聚乙烯醇。It can be used as a modified polyvinyl alcohol, and in particular, a modified product of polyvinyl alcohol modified by a compound represented by the following formula is suitable. The modified poly Vinyl alcohol is described below as a specific modified polyvinyl alcohol.

式中，R1 係表示烷基、丙烯醯基烷基、甲基丙烯醯基烷基、或環氧烷基；W係表示鹵素原子、烷基、或烷氧基；X係表示用以形成活性酯、酸酐、或醯基鹵所必要的原子群；p係表示0或1；而且n係表示0~4的整數。上述特定的改質聚乙烯醇係進一步為來自下述通式所示化合物之聚乙烯醇的改質物為佳。In the formula, R 1 represents an alkyl group, an alkyl decylalkyl group, a methacryl alkyl group, or an alkylene oxide group; W represents a halogen atom, an alkyl group, or an alkoxy group; and X represents a formation An atomic group necessary for an active ester, an acid anhydride, or a mercapto halide; p is 0 or 1; and n is an integer of 0 to 4. The above-mentioned specific modified polyvinyl alcohol is further preferably a modified product of polyvinyl alcohol derived from a compound represented by the following formula.

式中，X1 係表示用以形成活性酯、酸酐、或醯基鹵之必要原子群，且m係表示2~24的整數。In the formula, X 1 represents an essential atomic group for forming an active ester, an acid anhydride or a mercapto halide, and m represents an integer of 2 to 24.

為了使與由此等通式所表示之化合物進行反應而使用的聚乙烯醇，可舉例如前述的、未改質之聚乙烯醇，及經共聚合改質者、亦即藉由鏈移動而改質的、由嵌段聚合所引起的改質等的聚乙烯醇之改質物。特定改質聚乙烯醇之較佳例係詳細記載於特開平9-152509號公報。此等聚合物的合成方法、可見吸收光譜測定、及改質基導入率的決定方法等係詳細記載於特開平8-338913號公報。The polyvinyl alcohol used for the reaction with the compound represented by the above formula may, for example, be an unmodified polyvinyl alcohol as described above, and a copolymerized modifier, that is, by chain movement. Modified modified polyvinyl alcohol such as modified by block polymerization. A preferred embodiment of the specific modified polyvinyl alcohol is described in detail in Japanese Laid-Open Patent Publication No. Hei 9-152509. The method for synthesizing these polymers, the measurement of the visible absorption spectrum, and the method for determining the rate of introduction of the modified base are described in detail in JP-A-8-338913.

交聯劑之例係可舉例如藉由活性化醛類、正羥甲基化合物、二烷衍生物、羧基而作用的化合物、活性乙烯基化合物、活性鹵素化合物、異唑類、及二醛澱粉等。醛類之例係可舉例如甲醛、乙二醛、及戊二醛。N-羥甲基化合物之例係可舉例如二羥甲基脲及羥甲基二甲基海因。二烷衍生物之例係可舉例如2,3-二羥基二烷。藉由活性化羧基而作用的化合物之例係可舉例如碳鎓、2-萘磺酸酯、1,1-吡咯烷代-1-氯基吡咯烷鎓、及1-啉代羰基-3-(磺酸酯胺基甲基)。活性乙烯基化合物之例係可舉例如1,3,5-三丙烯醯基-六氫化-s-三、雙(乙烯基碸)甲烷、及N,N'-亞甲基雙-[β-(乙烯基磺醯基)丙醯胺]。然後，活性鹵素化合物之例係可舉例如2,4-二氯基-6-羥基-s-三。此等係可單獨或組合使用。使等與上述水溶性聚合物、特別是聚乙烯醇及改質聚乙烯醇(亦包含上述特定的改質物)併用之情形為佳。考慮到生產性時，較佳係使用反應活性高的醛類、尤其是使用戊二醛。Examples of the crosslinking agent include, for example, an activated aldehyde, a normal methylol compound, and two Alkane derivative, a compound acting as a carboxyl group, a reactive vinyl compound, an active halogen compound, or a different Azole, and dialdehyde starch. Examples of the aldehydes include formaldehyde, glyoxal, and glutaraldehyde. Examples of the N-methylol compound include, for example, dimethylol urea and hydroxymethyldimethylhydantoin. two Examples of the alkane derivative may, for example, be 2,3-dihydroxy alkyl. Examples of the compound which acts by activating a carboxyl group include, for example, carbonium, 2-naphthalenesulfonate, 1,1-pyrrolidino-1-chloropyrrolidinium, and 1- Oxocarbonyl-3- (sulfonate aminomethyl). Examples of the reactive vinyl compound are, for example, 1,3,5-triacrylinyl-hexahydro-s-three. , bis(vinyl anthracene) methane, and N,N'-methylenebis-[β-(vinylsulfonyl)propanamide]. Then, examples of the active halogen compound include, for example, 2,4-dichloro-6-hydroxy-s-three. . These systems can be used alone or in combination. It is preferred to use the above water-soluble polymer, particularly polyvinyl alcohol and modified polyvinyl alcohol (including the above-mentioned specific modified product) in combination. In view of productivity, it is preferred to use a highly reactive aldehyde, especially glutaraldehyde.

交聯劑對於聚合物之添加量係沒有特別地限制。耐濕性係在多添加交聯劑時會有良化的傾向。然而，交聯劑係在相對於聚合物，添加50質量%以上之情形中，做為配向膜之配向能係為降低。因此，交聯劑對於聚合物之添加量係在0.1~20質量%的範圍為佳、0.5~15質量%的範圍為更佳。配向膜即使在交聯反應結束後，亦含有某程度未經反應之交聯劑，惟該交聯劑的量係以在配向膜中為1.0質量%以下為佳、0.5質量%以下為較佳。配向膜中未反應之交聯劑的量在上述的範圍時，使用於液晶顯示裝置之情形、長期使用、或在高溫高濕之雰圍氣下經長時間放置之情形，沒有產生網狀物，且得到充分的耐久性而為佳。The amount of the crosslinking agent added to the polymer is not particularly limited. Moisture resistance tends to be favorable when a plurality of crosslinking agents are added. However, in the case where the crosslinking agent is added in an amount of 50% by mass or more based on the polymer, the alignment energy of the alignment film is lowered. Therefore, the amount of the crosslinking agent added to the polymer is preferably in the range of 0.1 to 20% by mass, more preferably 0.5 to 15% by mass. The alignment film contains a certain amount of unreacted crosslinking agent even after completion of the crosslinking reaction, and the amount of the crosslinking agent is preferably 1.0% by mass or less, and preferably 0.5% by mass or less in the alignment film. . When the amount of the unreacted crosslinking agent in the alignment film is in the above range, it is used in the case of a liquid crystal display device, long-term use, or long-term use under a high-temperature and high-humidity atmosphere, and no mesh is generated. It is preferable to obtain sufficient durability.

配向膜係可藉由將含有上述聚合物之溶液、或含有上述聚合物與交聯劑之溶液，塗布至乙酸纖維素薄膜上後，加熱乾燥(使其交聯)、且摩擦處理而可形成。交聯反應係 可在將塗布液塗布至乙酸纖維素薄膜上之後的任意時期來進行。而且，使用聚乙烯醇等的水溶性聚合物做為配向膜形成材料之情形中，用於製作該塗布液之溶媒係為有消泡作用之甲醇等的有機溶媒、或為有機溶媒與水的混合溶媒為適宜。使用甲醇做為有機溶媒之情形下，其比率以質量比一般係水：甲醇為0:100~99:1，0:100~91:9為較佳。藉此，抑制泡的產生，配向膜、甚至光學各向異性層的表面缺陷係為顯著地減少。The alignment film can be formed by applying a solution containing the above polymer or a solution containing the above polymer and a crosslinking agent to a cellulose acetate film, followed by heat drying (crosslinking) and rubbing treatment. . Cross-linking reaction system It can be carried out at any time after the coating liquid is applied onto the cellulose acetate film. Further, in the case where a water-soluble polymer such as polyvinyl alcohol is used as the alignment film forming material, the solvent for producing the coating liquid is an organic solvent such as methanol having a defoaming effect, or an organic solvent and water. A mixed solvent is suitable. In the case where methanol is used as the organic solvent, the ratio is preferably 0:100 to 99:1 and 0:100 to 91:9 in terms of mass ratio of normal water: methanol. Thereby, the generation of bubbles is suppressed, and the surface defects of the alignment film and even the optically anisotropic layer are remarkably reduced.

塗布方法係可舉例如旋轉塗布法、浸漬塗布法、簾塗法、擠塑塗布法、棒塗法及E型塗布法。其中，尤以E型塗布法為特佳。The coating method may, for example, be a spin coating method, a dip coating method, a curtain coating method, an extrusion coating method, a bar coating method, or an E-type coating method. Among them, the E-type coating method is particularly preferable.

配向膜的膜厚係在0.1~10μm的範圍為適宜。加熱乾燥係可在加熱溫度為20~110℃的範圍來進行。為形成充分的交聯，加熱溫度係以在60~100℃的範圍為佳、80~100℃的範圍為適宜。乾燥時間係可在1分～36小時來進行。 較佳為5~30分鐘。pH亦可設定成最適合於所使用之交聯劑的數值為佳，在使用戊二醛之情形係以在pH4.5~5.5的範圍為佳、在pH5為特佳。The film thickness of the alignment film is preferably in the range of 0.1 to 10 μm. The heating and drying system can be carried out at a heating temperature of 20 to 110 °C. In order to form sufficient cross-linking, the heating temperature is preferably in the range of 60 to 100 ° C and preferably in the range of 80 to 100 ° C. The drying time can be carried out in 1 minute to 36 hours. It is preferably 5 to 30 minutes. The pH may be preferably set to a value most suitable for the crosslinking agent to be used, and in the case of using glutaraldehyde, it is preferably in the range of pH 4.5 to 5.5, and particularly preferably in pH 5.

摩擦處理係可利用廣泛做為液晶顯示裝置之液晶配向處理步驟所採用的處理方法。即，配向膜的表面係可藉由使用紙或紗布、毛毯、橡膠或耐綸、聚酯纖維等朝固定方向擦拭，以得到配向之方法。一般而言，長度及粗細度為均勻的纖維係可藉由使用平均植毛的布等進行數次左右摩擦而實施。The rubbing treatment system can utilize a processing method widely used as a liquid crystal alignment processing step of a liquid crystal display device. That is, the surface of the alignment film can be wiped in a fixed direction by using paper or gauze, felt, rubber or nylon, polyester fiber or the like to obtain a alignment method. In general, a fiber system in which the length and the thickness are uniform can be carried out by rubbing the cloth with an average of a few hairs or the like several times.

光學補償薄片的光學特性係可依照本發明偏光板所使 用的液晶顯示裝置模式、或依照液晶胞的Δn．d等而予以最適化。前述光學補償薄片係只由聚合物薄膜所構成之情形，可藉由調整聚合物薄膜的延伸條件或於薄膜中添加遲滯值調整劑等，而形成較宜的光學特性。又，前述光學補償薄片係為由聚合物薄膜所成之支持體、與由液晶組成物所成之光學各向異性層的積層薄膜時，藉由在形成光學各向異性層之際調整液晶性分子的配向，可賦予所期望的光學特性。前述光學補償薄片為前述積層薄膜的態樣中，支持體之聚合物薄膜係可為光學性各向異性並有助於光學補償，或可為光學性各向同性而無助於光學補償。The optical characteristics of the optical compensation sheet can be made in accordance with the polarizing plate of the present invention. The liquid crystal display device mode used, or according to the Δn of the liquid crystal cell. d and so on to optimize. In the case where the optical compensation sheet is composed of only a polymer film, it is possible to form an optimum optical characteristic by adjusting the stretching condition of the polymer film or adding a hysteresis value adjusting agent to the film. Further, when the optical compensation sheet is a laminated film made of a polymer film and an optically anisotropic layer formed of a liquid crystal composition, the liquid crystal property is adjusted by forming an optically anisotropic layer. The alignment of the molecules imparts the desired optical properties. In the aspect in which the optical compensation sheet is the laminated film, the polymer film of the support may be optically anisotropic and contribute to optical compensation, or may be optically isotropic without contributing to optical compensation.

《保護層》"The protective layer"

本發明的偏光板係可具有保護偏光層之保護層。保護層係以聚合物薄膜者為佳。做為保護層所使用的聚合物薄膜之例子，係與做為光學補償薄片等所使用的聚合物薄膜之例子相同。The polarizing plate of the present invention may have a protective layer that protects the polarizing layer. The protective layer is preferably a polymer film. Examples of the polymer film used as the protective layer are the same as those of the polymer film used as the optical compensation sheet or the like.

《剝離紙》Stripping paper

本發明的偏光板係為前述黏著劑層配置在最外側之態樣時，在黏著劑層的表面黏貼剝離紙以提供保管及搬送者為佳。將前述偏光板組裝至液晶顯示裝置之際，將剝離紙剝離下來所露出的黏著劑層之表面，係可與液晶顯示裝置之其他構件、例如與液晶胞之基板表面相接觸而黏貼。In the polarizing plate of the present invention, when the pressure-sensitive adhesive layer is disposed on the outermost side, it is preferable to adhere the release paper to the surface of the pressure-sensitive adhesive layer to provide storage and transportation. When the polarizing plate is assembled to a liquid crystal display device, the surface of the adhesive layer exposed by peeling off the release paper can be adhered to and contact with other members of the liquid crystal display device, for example, the surface of the substrate of the liquid crystal cell.

[液晶顯示裝置][Liquid Crystal Display Device]

本發明的偏光板係有利於使用在液晶顯示裝置、特別是透過型液晶顯示裝置中。本發明液晶顯示裝置之一態樣 係特徵為由在液晶胞及其兩側所配置之二片偏光板所構成，且其一方或雙方係為本發明的偏光板。The polarizing plate of the present invention is advantageously used in a liquid crystal display device, particularly a transmissive liquid crystal display device. One aspect of the liquid crystal display device of the present invention The system is characterized in that two polarizing plates are disposed on the liquid crystal cell and on both sides thereof, and one or both of them are the polarizing plates of the present invention.

液晶胞一般係在二片的電極基板之間載持液晶之構成。TN模式的液晶胞係在無施加電壓時棒狀液晶性分子為實質上水平配向，以及在60~120∘時為に扭曲配向。TN模式的液晶胞係大多數利用做為彩色TFT液晶顯示裝置，且於多數的文獻中有記載。The liquid crystal cell generally has a configuration in which liquid crystal is carried between two electrode substrates. In the TN mode, the liquid crystal cell is substantially horizontally aligned when no voltage is applied, and is twisted and aligned at 60 to 120 Å. The TN mode liquid crystal cell system is mostly used as a color TFT liquid crystal display device, and is described in most documents.

又本發明的偏光板係除了TN模式的液晶胞以外，亦可利用於OCB(Optically Compensatory Bend，光學補償彎曲)、VA(Vertically Aligned，垂直配向)、IPS(In Plane Switching，面內扭轉)等的液晶顯示裝置。亦即，本發明的液晶顯示裝置係可適用於TN模式、OCB、VA、IPS等。Further, the polarizing plate of the present invention can be used for OCB (Optically Compensatory Bend, VA (Vertically Aligned), IPS (In Plane Switching), etc., in addition to the liquid crystal cell of the TN mode. Liquid crystal display device. That is, the liquid crystal display device of the present invention can be applied to TN mode, OCB, VA, IPS, and the like.

【實施例】[Examples]

以下，係列舉實施例等來詳細說明本發明，惟本發明並不受限於此等實施例。Hereinafter, the invention will be described in detail by way of examples and the like, but the invention is not limited thereto.

[實施例1][Example 1]

(乙酸纖維素薄膜的製作) 將下述的組成物投入攪拌槽內，一邊加熱、一邊攪拌，溶解各成分，以調製乙酸纖維素溶液。(Production of cellulose acetate film) The following composition was placed in a stirring tank, and while stirring, the components were dissolved to prepare a cellulose acetate solution.

＜乙酸纖維素溶液組成＞ <cellulose acetate solution composition>

在另一個攪拌槽中，投入下述的遲滯值上昇劑16質量份、二氯甲烷80質量份及甲醇20質量份，一邊加熱、一邊攪拌，以調製遲滯值上昇劑溶液。將遲滯值上昇劑溶液22質量份與乙酸纖維素溶液477質量份混合、充分攪拌以調製塗布液。遲滯值上昇劑的添加量相對於乙酸纖維素100質量份係為3.0質量份。In the other agitation tank, 16 parts by mass of the hysteresis-increasing agent, 80 parts by mass of dichloromethane, and 20 parts by mass of methanol were placed, and the mixture was stirred while heating to prepare a hysteresis-increasing agent solution. 22 parts by mass of the hysteresis value rising agent solution and 477 parts by mass of the cellulose acetate solution were mixed and stirred sufficiently to prepare a coating liquid. The amount of the hysteresis value-increasing agent added was 3.0 parts by mass based on 100 parts by mass of the cellulose acetate.

使用輸送帶流延機以流延所得之塗布液。將殘留溶劑量為40質量%的薄膜從輸送帶剝下來，一邊吹拂120℃的熱風，往搬送方向施加101%的拉拔且搬送，並以拉幅機往寬度方向展寬(擴幅)3%且使其乾燥。接著將拉幅機夾鉗取下後，以140℃的熱風乾燥薄膜20分鐘，以製造殘留溶劑量為0.3質量%的乙酸纖維素薄膜(厚度：107μm)。A conveyor belt casting machine was used to cast the resulting coating liquid. The film having a residual solvent amount of 40% by mass was peeled off from the conveyor belt, and hot air of 120 ° C was blown, 101% of drawing was carried out in the conveyance direction, and conveyed, and stretched in the width direction by the tenter (expanded) by 3%. And make it dry. After the tenter clip was removed, the film was dried with hot air at 140 ° C for 20 minutes to produce a cellulose acetate film (thickness: 107 μm) having a residual solvent amount of 0.3% by mass.

將所製作的乙酸纖維素薄膜浸漬於2.0N的氫氧化鉀溶液(25℃)中2分鐘後，以硫酸中和，用純水來水洗、乾燥，以進行皂化處理。The produced cellulose acetate film was immersed in a 2.0 N potassium hydroxide solution (25 ° C) for 2 minutes, neutralized with sulfuric acid, washed with pure water, and dried to carry out a saponification treatment.

(配向膜的形成)(Formation of alignment film)

在所製作的乙酸纖維素薄膜上，以#14的金屬棒材塗布機塗布下述組成之塗布液成24ml/m2 。用60℃的溫風乾燥60秒，然後再以90℃的溫風乾燥150秒。接著，在與 乙酸纖維素薄膜的長度方向成平行的方向，對所形成的膜實施摩擦處理。On the produced cellulose acetate film, a coating liquid having the following composition was applied by a #14 metal bar coater to 24 ml/m 2 . It was dried by a warm air of 60 ° C for 60 seconds, and then dried by a warm air of 90 ° C for 150 seconds. Next, the formed film was subjected to a rubbing treatment in a direction parallel to the longitudinal direction of the cellulose acetate film.

＜配向膜塗布液組成＞ <Alignment film coating liquid composition>

(光學各向異性層的形成．光學補償薄片的製作) 在配向膜上，將下述的圓盤狀(液晶性)化合物91.0g、環氧乙烷變成三羥甲基丙烷三丙烯酸酯(V#360、大阪有機化學(股)製)9.0g、乙酸丁酸纖維素(CAB551-0.2、伊士曼化學公司製)2.0g、乙酸丁酸纖維素(CAB531-1、伊士曼化學公司製)0.5g、光聚合起始劑(Irgacure 907、Ciba Geigy 公司製)3.0g、增感劑(Kayacure DETX、日本化藥(股)製)1.0g溶解於207g的甲基乙基酮之塗布液，以#3.6的金屬棒塗布成6.2cc/m2 。將其在130℃的恆溫區域加熱2分鐘，使圓盤狀化合物配向。接著，於60℃的雰圍氣下，使用120W/cm高壓水銀燈照射1分鐘UV，以使得圓盤狀化合物聚合。隨後，放冷至室溫。如此，形成光學各向異性 層以製作光學補償薄片1。(Formation of Optically Anisotropic Layer. Preparation of Optically Compensating Sheet) On the alignment film, 91.0 g of the following disc-shaped (liquid crystal) compound and ethylene oxide were changed to trimethylolpropane triacrylate (V). #360, Osaka Organic Chemical Co., Ltd.) 9.0g, cellulose acetate butyrate (CAB551-0.2, manufactured by Eastman Chemical Co., Ltd.) 2.0g, cellulose acetate butyrate (CAB531-1, manufactured by Eastman Chemical Co., Ltd.) 0.5 g, a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy Co., Ltd.), 3.0 g, a sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.), 1.0 g of a coating liquid dissolved in 207 g of methyl ethyl ketone It was coated with a metal rod of #3.6 to 6.2 cc/m 2 . This was heated in a constant temperature region of 130 ° C for 2 minutes to align the discotic compound. Next, UV was irradiated for 1 minute using a 120 W/cm high-pressure mercury lamp under an atmosphere of 60 ° C to polymerize the disk-shaped compound. Then, let cool to room temperature. Thus, an optically anisotropic layer was formed to fabricate the optical compensation sheet 1.

光學補償薄片1的彈性係數係以TENSILON(股)東洋精機製作所製)測定時，為3.89×109 Pa。又，光學補償薄片1的光彈性係數係以日本分光公司製橢圓偏振光測定器M-150測定時，為13×10-12 (1/Pa)。The elastic modulus of the optical compensation sheet 1 was 3.89 × 10 9 Pa when measured by TENSILON (manufactured by Toyo Seiki Seisakusho Co., Ltd.). In addition, the photoelastic coefficient of the optical compensation sheet 1 is 13 × 10 -12 (1/Pa) when measured by the ellipsometry meter M-150 manufactured by JASCO Corporation.

(偏光板的製作) 使碘吸附至延伸的聚乙烯醇薄膜來製作偏光膜，使用聚乙烯醇系黏合劑，對如以上方式所製作之光學補償薄片進行上述記載之皂化處理後，將乙酸纖維素薄膜貼附至偏光膜單側的表面使其在偏光膜的側面。偏光膜的透過軸與乙酸纖維素薄膜的遅相軸係配置成平行。對於市售的三乙酸纖維素薄膜(厚度80μm、FUJITAC TD80UF、富士軟片(股)製)進行皂化處理，並使用聚乙烯醇系黏合劑，將其貼附至偏光膜相反側之表面當作透明保護膜。(production of polarizing plate) The iodine is adsorbed to the stretched polyvinyl alcohol film to prepare a polarizing film, and the optically compensated sheet produced as described above is subjected to the saponification treatment described above using a polyvinyl alcohol-based adhesive, and then the cellulose acetate film is attached to the polarized light. The surface on one side of the film is placed on the side of the polarizing film. The transmission axis of the polarizing film is arranged in parallel with the 遅 phase axis of the cellulose acetate film. A commercially available cellulose triacetate film (thickness: 80 μm, FUJITAC TD80UF, manufactured by Fujifilm Co., Ltd.) was subjected to saponification treatment, and a polyvinyl alcohol-based adhesive was used, and the surface of the opposite side of the polarizing film was attached as a transparent surface. Protective film.

將NR(白縐片(pale crepe))60質量份、SBR(B/S=71/29)30質量份、聚異丁烯10質量份、多萜烯樹脂(軟化點115℃)60質量份、加氫松香甘油酯10質量份、抗氧化劑(2,6-二-第三丁基-4-甲酚)2質量份溶解於正己烷使其固體成分為20%，以調製黏著劑漿液。在如前述所製作的透 明保護層、偏光膜及光學補償薄片1之積層體的光學各向異性層面，塗布前述的黏著劑漿液使其乾燥後的黏著劑層的厚度為30μm，以形成黏著劑層。60 parts by mass of NR (pale crepe), 30 parts by mass of SBR (B/S = 71/29), 10 parts by mass of polyisobutylene, and 60 parts by mass of polyterpene resin (softening point: 115 ° C), plus 10 parts by mass of a hydrogen rosin glyceride and 2 parts by mass of an antioxidant (2,6-di-t-butyl-4-methylphenol) were dissolved in n-hexane to have a solid content of 20% to prepare an adhesive slurry. Made in the above The optically anisotropic layer of the laminate of the protective layer, the polarizing film, and the optical compensation sheet 1 was coated with the above-mentioned adhesive slurry to have a thickness of 30 μm after drying to form an adhesive layer.

將剝離紙黏合至前述黏著劑層的表面。如此這樣以製作與第2圖相同構成之偏光板。The release paper is bonded to the surface of the aforementioned adhesive layer. In this way, a polarizing plate having the same configuration as that of Fig. 2 was produced.

所形成之黏著劑層的光彈性係數係以日本分光公司製橢圓偏振光測定器M-150測定時，為200×10-12 (1/Pa)。The photoelastic coefficient of the formed adhesive layer was 200 × 10 -12 (1/Pa) when measured by ellipsometry M-150 manufactured by JASCO Corporation.

因此，該偏光板的Y值為1.9×10-4 。Therefore, the Y value of the polarizing plate is 1.9 × 10 -4 .

(偏光板的評價) 將從如以上般所製作的2片偏光板將剝離紙分別除去、露出的黏著劑層，各黏貼一片於石英玻璃板的兩面。為了使2片偏光板之透過軸成正交，另外配置成與玻璃端的線成45度的角度。(evaluation of polarizing plate) The adhesive layers which were respectively removed from the release paper from the two polarizing plates produced as described above were adhered to each surface of the quartz glass plate. In order to make the transmission axes of the two polarizing plates orthogonal, they are additionally arranged at an angle of 45 degrees with the line of the glass end.

將前述偏光板貼附於兩面之玻璃板在60℃乾燥的乾燥機內靜置17小時，隨後取出，在1小時後放置於SAMSUNG公司製螢幕Syncmaster 172X之背光上，於暗室以目視來觀察全面黑顯示狀態並評價漏光。其結果，大致上觀察不到在偏光板周圍的漏光。又，在TOPCON TECHNOHOUS(股)製的輝度計BM-5A中測量輝度分布，並測定漏光量。其結果，最大漏光的透射率為0.02%。The polarizing plate was attached to both sides of the glass plate and allowed to stand in a dryer dried at 60 ° C for 17 hours, and then taken out, and placed on the backlight of the SAMSUNG company's screen Syncmaster 172X 1 hour later, and visually observed in the dark room. Black shows the status and evaluates the light leakage. As a result, light leakage around the polarizing plate was hardly observed. Further, the luminance distribution was measured in a luminance meter BM-5A manufactured by TOPCON TECHNOHOUS Co., Ltd., and the amount of light leakage was measured. As a result, the transmittance of the maximum light leakage was 0.02%.

[實施例2][Embodiment 2]

(乙酸纖維素薄膜的製作) 將下述的組成物投入攪拌槽內，一邊加熱、一邊攪拌，溶解各成分，以調製乙酸纖維素溶液。(Production of cellulose acetate film) The following composition was placed in a stirring tank, and while stirring, the components were dissolved to prepare a cellulose acetate solution.

＜乙酸纖維素溶液組成＞ <cellulose acetate solution composition>

在另一攪拌槽中，投入實施例1中所使用的遲滯值上昇劑16質量份、二氯甲烷80質量份及甲醇20質量份，一邊加熱、一邊攪拌，以調製遲滯值上昇劑溶液。於乙酸纖維素溶液477質量份中混合遲滯值上昇劑溶液22質量份，充分攪拌以調製塗布液。遲滯值上昇劑的添加量係相對於乙酸纖維素100質量份為3.0質量份。In a separate agitation tank, 16 parts by mass of the hysteresis value increasing agent used in Example 1, 80 parts by mass of dichloromethane, and 20 parts by mass of methanol were charged, and while stirring, the hysteresis value rising agent solution was prepared. 22 parts by mass of the hysteresis value rising agent solution was mixed with 477 parts by mass of the cellulose acetate solution, and the mixture was sufficiently stirred to prepare a coating liquid. The addition amount of the hysteresis value rising agent is 3.0 parts by mass based on 100 parts by mass of the cellulose acetate.

使用輸送帶流延機流延所得之塗布液。將殘留溶劑量為40質量%的薄膜從輸送帶剝下來，一邊吹拂120℃的熱風，往搬送方向施加101%的拉拔且搬送，並以拉幅機往寬度方向展寬(擴幅)3%且使其乾燥。接著將拉幅機夾鉗取下後，以140℃的熱風乾燥薄膜20分鐘，以製造殘留溶劑量為0.3質量%的乙酸纖維素薄膜(厚度：107μm)。The resulting coating liquid was cast using a conveyor belt casting machine. The film having a residual solvent amount of 40% by mass was peeled off from the conveyor belt, and hot air of 120 ° C was blown, 101% of drawing was carried out in the conveyance direction, and conveyed, and stretched in the width direction by the tenter (expanded) by 3%. And make it dry. After the tenter clip was removed, the film was dried with hot air at 140 ° C for 20 minutes to produce a cellulose acetate film (thickness: 107 μm) having a residual solvent amount of 0.3% by mass.

將所製作之乙酸纖維素薄膜浸漬於2.0N的氫氧化鉀溶液(25℃)2分鐘後，以硫酸中和，用純水加以水洗、乾燥，以進行皂化處理。The produced cellulose acetate film was immersed in a 2.0 N potassium hydroxide solution (25 ° C) for 2 minutes, neutralized with sulfuric acid, washed with pure water, and dried to carry out a saponification treatment.

在所製作的乙酸纖維素薄膜上，以與實施例1同樣的方式，形成配向膜、光學各向異性層，以製作光學補償薄片2。光學補償薄片2的彈性係數以TENSILON(股)東洋精機製作所製)測定時為4.5×109 Pa。又，光學補償薄片2的光彈性係數以日本分光公司製橢圓偏振光測定器M-150測 定時為13×10-12 (1/Pa)。An alignment film and an optically anisotropic layer were formed on the produced cellulose acetate film in the same manner as in Example 1 to produce an optical compensation sheet 2. The elastic modulus of the optical compensation sheet 2 was 4.5 × 10 9 Pa when measured by TENSILON (manufactured by Toyo Seiki Seisakusho Co., Ltd.). In addition, the photoelastic coefficient of the optical compensation sheet 2 was 13 × 10 -12 (1/Pa) when measured by the ellipsometry meter M-150 manufactured by JASCO Corporation.

除了以光學補償薄片2取代光學補償薄片1以外，以與實施例1同樣的方式，製作與第1圖同樣構成之偏光板。該偏光板之黏著劑層的光彈性係數以日本分光公司製橢圓偏振光測定器M-150測定時為200×10-12 (1/Pa)。A polarizing plate having the same configuration as that of Fig. 1 was produced in the same manner as in Example 1 except that the optical compensation sheet 2 was replaced with the optical compensation sheet 2. The photoelastic coefficient of the adhesive layer of the polarizing plate was 200 × 10 -12 (1/Pa) when measured by an ellipsometry meter M-150 manufactured by JASCO Corporation.

因此，該偏光板的Y值為4.6×10-4 。Therefore, the Y value of the polarizing plate is 4.6 × 10 -4 .

(評價) 以與實施例1同樣的方式，將所製作的2片偏光板各貼附1片在石英玻璃板的兩面上。使其配置成2片偏光板的透過軸成正交、又與玻璃端的線成45度的角度。(Evaluation) In the same manner as in the first embodiment, one of the two polarizing plates produced was attached to each of the two faces of the quartz glass plate. The transmission axes of the two polarizing plates are arranged to be orthogonal and at an angle of 45 degrees to the line of the glass end.

以與實施例1同樣的方式，將兩面貼附偏光板之玻璃板放入60℃乾燥的乾燥機17小時取出後，評價於暗室以目視方式觀察全面黑顯示狀態的漏光。其結果，在偏光板周邊幾乎觀察不到漏光。又，在輝度計測量輝度分布以測定漏光量。其結果最大漏光的透射率為0.05%。In the same manner as in Example 1, the glass plate to which the polarizing plates were attached was placed in a dryer dried at 60 ° C for 17 hours, and then the light leakage in the dark state was visually observed in the dark room. As a result, almost no light leakage was observed around the polarizing plate. Further, the luminance distribution was measured by a luminance meter to measure the amount of light leakage. As a result, the transmittance of the maximum light leakage was 0.05%.

[實施例3][Example 3]

(黏著劑漿液的調製) NR(白縐片)60質量份、SBR(B/S=71/29)40質量份、聚異丁烯10質量份、多萜烯樹脂(軟化點115℃)60質量份、加氫松香甘油酯10質量份、抗氧化劑(2,6-二-第三丁基-4-甲酚)2質量份溶解於正己烷使其固體成分為20%，以調製黏著劑漿液。(modulation of adhesive slurry) 60 parts by mass of NR (white plate), 40 parts by mass of SBR (B/S = 71/29), 10 parts by mass of polyisobutylene, 60 parts by mass of polyterpene resin (softening point 115 ° C), hydrogenated rosin glyceride 10 2 parts by mass of an antioxidant (2,6-di-t-butyl-4-methylphenol) was dissolved in n-hexane to have a solid content of 20% to prepare an adhesive slurry.

除了使用該黏著劑漿液以形成黏著劑層以外，以與實施例1同樣的方法，製作與第2圖相同構成之偏光板。A polarizing plate having the same configuration as that of Fig. 2 was produced in the same manner as in Example 1 except that the adhesive slurry was used to form an adhesive layer.

所形成之黏著劑層的光彈性係數以日本分光公司製橢 圓偏振光測定器M-150測定時為100×10-12 (1/Pa)。The photoelastic coefficient of the formed adhesive layer was 100 × 10 -12 (1/Pa) as measured by ellipsometry M-150 manufactured by JASCO Corporation.

因此，該偏光板的Y值為2.6×10-4 。Therefore, the Y value of the polarizing plate is 2.6 × 10 -4 .

(評價) 以與實施例1同樣的方式，將所製作的2片偏光板各貼附1片在石英玻璃板的兩面上。使其配置成2片偏光板的透過軸成正交、又與玻璃端的線成45度的角度。(Evaluation) In the same manner as in the first embodiment, one of the two polarizing plates produced was attached to each of the two faces of the quartz glass plate. The transmission axes of the two polarizing plates are arranged to be orthogonal and at an angle of 45 degrees to the line of the glass end.

以與實施例1同樣的方式，將兩面貼附偏光板之玻璃板放入60℃乾燥的乾燥機17小時取出後，評價於暗室以目視方式觀察全面黑顯示狀態的漏光。其結果，在偏光板周邊幾乎觀察不到漏光。又，在輝度計測量輝度分布以測定漏光量。其結果最大漏光的透射率為0.03%。In the same manner as in Example 1, the glass plate to which the polarizing plates were attached was placed in a dryer dried at 60 ° C for 17 hours, and then the light leakage in the dark state was visually observed in the dark room. As a result, almost no light leakage was observed around the polarizing plate. Further, the luminance distribution was measured by a luminance meter to measure the amount of light leakage. As a result, the transmittance of the maximum light leakage was 0.03%.

[實施例4][Example 4]

除了在黏著劑層的形成中，使用與實施例3中所調製者為相同組成之黏著劑漿液以外，以與實施例2同樣的方式，製作與第2圖相同構成之偏光板。A polarizing plate having the same configuration as that of Fig. 2 was produced in the same manner as in Example 2 except that the adhesive slurry having the same composition as that prepared in Example 3 was used in the formation of the adhesive layer.

所形成之黏著劑層的光彈性係數以日本分光公司製橢圓偏振光測定器M-150測定時為100×10-12 (1/Pa)。The photoelastic coefficient of the formed adhesive layer was 100 × 10 -12 (1/Pa) as measured by ellipsometry M-150 manufactured by JASCO Corporation.

因此，該偏光板的Y值為5.3×10-4 。Therefore, the Y value of the polarizing plate is 5.3 × 10 -4 .

(評價) 以與實施例1同樣的方式，將所製作的2片偏光板各貼附1片在石英玻璃板的兩面上。使其配置成2片偏光板的透過軸成正交、又與玻璃端的線成45度的角度。(Evaluation) In the same manner as in the first embodiment, one of the two polarizing plates produced was attached to each of the two faces of the quartz glass plate. The transmission axes of the two polarizing plates are arranged to be orthogonal and at an angle of 45 degrees to the line of the glass end.

以與實施例1同樣的方式，將兩面貼附偏光板之玻璃板放入60℃乾燥的乾燥機17小時取出後，評價於暗室以目視方式觀察全面黑顯示狀態的漏光。其結果，在偏光板 周邊幾乎觀察不到漏光。又，在輝度計測量輝度分布以測定漏光量。其結果最大漏光的透射率為0.05%。In the same manner as in Example 1, the glass plate to which the polarizing plates were attached was placed in a dryer dried at 60 ° C for 17 hours, and then the light leakage in the dark state was visually observed in the dark room. The result is in the polarizing plate Almost no light leakage was observed around the perimeter. Further, the luminance distribution was measured by a luminance meter to measure the amount of light leakage. As a result, the transmittance of the maximum light leakage was 0.05%.

[實施例5][Example 5]

[黏著層的形成] 依照以下方法來調製黏著劑漿液。另外，所使用物質的略語係如以下所述。[Formation of adhesive layer] The adhesive slurry was prepared in the following manner. In addition, abbreviations of the substances used are as follows.

BA：丙烯酸正丁酯 MA：甲基丙烯酸酯 AA：丙烯酸 2-HEMA：甲基丙烯酸羥基乙酯 BZMA：甲基丙烯酸苄酯 PHMA：甲基丙烯酸苯酯 AIBN：偶氮雙異丁腈 EA(EAc)：乙酸乙酯BA: n-butyl acrylate MA: methacrylate AA: Acrylic 2-HEMA: hydroxyethyl methacrylate BZMA: benzyl methacrylate PHMA: phenyl methacrylate AIBN: azobisisobutyronitrile EA (EAc): ethyl acetate

在設置共聚物的製造氮氣為回流且容易調節溫度用的冷却裝置之1000cc反應器中，投入以丙烯酸正丁酯(BA)49.5質量份、丙烯酸(AA)3質量份、(甲基)丙烯酸2-羥基乙酯(2-HEMA)0.5質量份、甲基丙烯酸苄酯(BZMA)100質量份所構成之單體的混合物。然後，投入做為溶劑之乙酸乙酯(EA)100質量份。接著，為了將氧去除至系統外，以氮氣清洗20分鐘，且維持在65℃使其均勻之後，將反應起始劑之偶氮雙異丁睛(AIBN)0.03質量份投入稀釋成50%濃度之乙酸乙酯中，使其反應10小時以得到最終丙烯酸系聚合物。In a 1000 cc reactor in which a cooling device for producing a copolymer is a nitrogen gas which is refluxed and easily adjusted in temperature, 49.5 parts by mass of n-butyl acrylate (BA), 3 parts by mass of acrylic acid (AA), and (meth)acrylic acid 2 are charged. a mixture of 0.5 parts by mass of hydroxyethyl ester (2-HEMA) and 100 parts by mass of benzyl methacrylate (BZMA). Then, 100 parts by mass of ethyl acetate (EA) as a solvent was charged. Next, in order to remove oxygen to the outside of the system, purge with nitrogen for 20 minutes, and maintain it at 65 ° C to make it uniform, 0.03 parts by mass of azobisisobutyroside (AIBN) of the reaction initiator was diluted into 50% concentration. The reaction was carried out for 10 hours in ethyl acetate to obtain a final acrylic polymer.

將藉由前述共聚合過程所得之丙烯酸系聚合物溶液 (約50%固體成分)進一步的混合。接著，將異氰酸酯系交聯劑之三羥甲基丙烷的甲苯基二異氰酸酯加成物(TDI-1)1.2質量份投入各乙酸乙酯溶液中稀釋成10質量%，考慮到塗布性而稀釋成適合的濃度並均勻地混合，以得到黏著劑漿液。An acrylic polymer solution obtained by the aforementioned copolymerization process (about 50% solids) further mixed. Then, 1.2 parts by mass of a tolyl diisocyanate adduct (TDI-1) of trimethylolpropane of an isocyanate-based crosslinking agent was added to each ethyl acetate solution and diluted to 10% by mass, and diluted into a coating property in consideration of coatability. The concentration is suitably mixed and uniformly mixed to obtain an adhesive slurry.

除了使用上述所調製之黏著劑漿液以形成黏著劑層以外，以與實施例2同樣的方法，來製作與第2圖相同構成之偏光板。A polarizing plate having the same configuration as that of Fig. 2 was produced in the same manner as in Example 2 except that the above-described adhesive slurry was used to form an adhesive layer.

所形成之黏著劑層的光彈性係數以日本分光公司製橢圓偏振光測定器M-150測定時為10×10-12 (1/Pa)。The photoelastic coefficient of the formed adhesive layer was 10 × 10 -12 (1/Pa) as measured by ellipsometry M-150 manufactured by JASCO Corporation.

因此，該偏光板的Y值為5.9×10-4 。Therefore, the Y value of the polarizing plate is 5.9 × 10 -4 .

(評價) 以與實施例1同樣的方式，將所製作的2片偏光板各貼附1片在石英玻璃板的兩面上。使其配置成2片偏光板的透過軸成正交、又與玻璃端的線成45度的角度。(Evaluation) In the same manner as in the first embodiment, one of the two polarizing plates produced was attached to each of the two faces of the quartz glass plate. The transmission axes of the two polarizing plates are arranged to be orthogonal and at an angle of 45 degrees to the line of the glass end.

以與實施例1同樣的方式，將兩面貼附偏光板之玻璃板放入60℃乾燥的乾燥機17小時取出後，評價於暗室以目視方式觀察全面黑顯示狀態的漏光。其結果，在偏光板周邊幾乎觀察不到漏光。又，在輝度計測量輝度分布以測定漏光量。其結果最大漏光的透射率為0.055%。In the same manner as in Example 1, the glass plate to which the polarizing plates were attached was placed in a dryer dried at 60 ° C for 17 hours, and then the light leakage in the dark state was visually observed in the dark room. As a result, almost no light leakage was observed around the polarizing plate. Further, the luminance distribution was measured by a luminance meter to measure the amount of light leakage. As a result, the transmittance of the maximum light leakage was 0.055%.

[實施例6][Embodiment 6]

除了使用與實施例5中所調製者為相同組成之黏著劑漿液以形成黏著劑層以外，以與實施例1同樣的方式，得到與第2圖相同構成之偏光板。A polarizing plate having the same configuration as that of Fig. 2 was obtained in the same manner as in Example 1 except that an adhesive slurry having the same composition as that prepared in Example 5 was used to form an adhesive layer.

以上之黏著劑層的光彈性係數以日本分光公司製橢圓 偏振光測定器M-150測定時為10×10-12 (1/Pa)。The photoelastic coefficient of the above adhesive layer was 10 × 10 -12 (1/Pa) as measured by ellipsometry M-150 manufactured by JASCO Corporation.

因此，該偏光板的Y值為3.3×10-4 。Therefore, the Y value of the polarizing plate is 3.3 × 10 -4 .

(評價) 以與實施例1同樣的方式，將所製作的2片偏光板各貼附1片在石英玻璃板的兩面上。使其配置成2片偏光板的透過軸成正交、又與玻璃端的線成45度的角度。(Evaluation) In the same manner as in the first embodiment, one of the two polarizing plates produced was attached to each of the two faces of the quartz glass plate. The transmission axes of the two polarizing plates are arranged to be orthogonal and at an angle of 45 degrees to the line of the glass end.

以與實施例1同樣的方式，將兩面貼附偏光板之玻璃板放入60℃乾燥的乾燥機17小時取出後，評價於暗室以目視方式觀察全面黑顯示狀態的漏光。其結果，在偏光板周邊幾乎觀察不到漏光。又，在輝度計測量輝度分布以測定漏光量。其結果最大漏光的透射率為0.04%。In the same manner as in Example 1, the glass plate to which the polarizing plates were attached was placed in a dryer dried at 60 ° C for 17 hours, and then the light leakage in the dark state was visually observed in the dark room. As a result, almost no light leakage was observed around the polarizing plate. Further, the luminance distribution was measured by a luminance meter to measure the amount of light leakage. As a result, the transmittance of the maximum light leakage was 0.04%.

[實施例7][Embodiment 7]

[黏著層的形成] 依照以下方法以調製黏著劑漿液。另外，所使用物質的略語係如以下所述。[Formation of adhesive layer] The adhesive slurry was prepared according to the following method. In addition, abbreviations of the substances used are as follows.

BA：丙烯酸正丁酯 MA：甲基丙烯酸酯 AA：丙烯酸 2-HEMA：甲基丙烯酸羥基乙酯 BZMA：甲基丙烯酸苄酯 PHMA：甲基丙烯酸苯酯 AIBN：偶氮雙異丁腈 EA(EAc)：乙酸乙酯BA: n-butyl acrylate MA: methacrylate AA: Acrylic 2-HEMA: hydroxyethyl methacrylate BZMA: benzyl methacrylate PHMA: phenyl methacrylate AIBN: azobisisobutyronitrile EA (EAc): ethyl acetate

在設置共聚物的製造氮氣為回流且容易調節溫度用的冷却裝置之1000cc反應器中，投入由丙烯酸正丁酯 (BA)49.5質量份、丙烯酸(AA)3質量份、(甲基)丙烯酸2-羥基乙酯(2-HEMA)0.5質量份、甲基丙烯酸苯酯(PHMA)95質量份所構成之單體的混合物。然後，投入做為溶劑之乙酸乙酯(EA)100質量份。接著，為了將氧去除至系統外，以氮氣清洗20分鐘，且維持在65℃使其均勻之後，將反應起始劑之偶氮雙異丁腈(AIBN)0.03質量份投入稀釋成50%濃度之乙酸乙酯中，使其反應10小時以得到最終丙烯酸系聚合物。In a 1000 cc reactor in which a cooling device for supplying a nitrogen gas to reflux and easily adjusting the temperature is set, n-butyl acrylate is introduced. (BA) 49.5 parts by mass, 3 parts by mass of acrylic acid (AA), 0.5 parts by mass of 2-hydroxyethyl (meth)acrylate (2-HEMA), and 95 parts by mass of phenyl methacrylate (PHMA) mixture. Then, 100 parts by mass of ethyl acetate (EA) as a solvent was charged. Next, in order to remove oxygen to the outside of the system, purge with nitrogen for 20 minutes, and maintain it at 65 ° C to make it uniform, 0.03 parts by mass of the azobisisobutyronitrile (AIBN) of the reaction initiator was diluted and diluted to 50% concentration. The reaction was carried out for 10 hours in ethyl acetate to obtain a final acrylic polymer.

將藉由前述共聚合過程所得之丙烯酸系聚合物溶液(約50%固體成分)進一步的混合。接著，將異氰酸酯系交聯劑之三羥甲基丙烷的甲苯基二異氰酸酯加成物(TDI-1)1.2質量份投入各乙酸乙酯溶液中稀釋成10質量%，考慮到塗布性而稀釋成適合的濃度並均勻地混合，以得到黏著劑漿液。The acrylic polymer solution (about 50% solid content) obtained by the aforementioned copolymerization process was further mixed. Then, 1.2 parts by mass of a tolyl diisocyanate adduct (TDI-1) of trimethylolpropane of an isocyanate-based crosslinking agent was added to each ethyl acetate solution and diluted to 10% by mass, and diluted into a coating property in consideration of coatability. The concentration is suitably mixed and uniformly mixed to obtain an adhesive slurry.

除了使用上述中調製之黏著劑漿液以形成黏著劑層以外，以與實施例1同樣的方法，製作與第2圖相同構成之偏光板。A polarizing plate having the same configuration as that of Fig. 2 was produced in the same manner as in Example 1 except that the adhesive slurry prepared in the above was used to form an adhesive layer.

所形成之黏著劑層的光彈性係數以日本分光公司製橢圓偏振光測定器M-150測定時為10×10-12 (1/Pa)。The photoelastic coefficient of the formed adhesive layer was 10 × 10 -12 (1/Pa) as measured by ellipsometry M-150 manufactured by JASCO Corporation.

因此，該偏光板的Y值為3.3×10-4 。Therefore, the Y value of the polarizing plate is 3.3 × 10 -4 .

(評價) 以與實施例1同樣的方式，將所製作的2片偏光板各貼附1片在石英玻璃板的兩面上。使其配置成2片偏光板的透過軸成正交、又與玻璃端的線成45度的角度。(Evaluation) In the same manner as in the first embodiment, one of the two polarizing plates produced was attached to each of the two faces of the quartz glass plate. The transmission axes of the two polarizing plates are arranged to be orthogonal and at an angle of 45 degrees to the line of the glass end.

以與實施例1同樣的方式，將兩面貼附偏光板之玻璃 板放入60℃乾燥的乾燥機17小時取出後，評價於暗室以目視方式觀察全面黑顯示狀態的漏光。其結果，在偏光板周邊幾乎觀察不到漏光。又，在輝度計測量輝度分布以測定漏光量。其結果最大漏光的透射率為0.035%。The glass on both sides of the polarizing plate was attached in the same manner as in the first embodiment. After the plate was taken out in a dryer dried at 60 ° C for 17 hours, it was evaluated in a dark room to visually observe light leakage in a state of full black display. As a result, almost no light leakage was observed around the polarizing plate. Further, the luminance distribution was measured by a luminance meter to measure the amount of light leakage. As a result, the transmittance of the maximum light leakage was 0.035%.

[比較例][Comparative example]

除了在光學各向異性層面貼合做為黏著劑層之Sanritz公司製黏著劑層PE第三S(W)(膜厚：30μm)以外，與實施例同樣地得到比較用偏光板。A comparative polarizing plate was obtained in the same manner as in the Example except that the adhesive layer PE third S (W) (film thickness: 30 μm) made of Sanritz Co., Ltd. as an adhesive layer was bonded to the optically anisotropic layer.

該黏著劑層的光彈性係數以日本分光公司製橢圓偏振光測定器M-150測定時為-750×10-12 (1/Pa)。The photoelastic coefficient of the adhesive layer was -750 × 10 -12 (1/Pa) when measured by ellipsometry M-150 manufactured by JASCO Corporation.

因此，該偏光板的Y值為8.6×10-4 。Therefore, the Y value of the polarizing plate is 8.6 × 10 -4 .

(評價) 以與實施例1同樣的方式，將所製作的2片偏光板各貼附1片在石英玻璃板的兩面上。使其配置成2片偏光板的透過軸成正交、又與玻璃端的線成45度的角度。(Evaluation) In the same manner as in the first embodiment, one of the two polarizing plates produced was attached to each of the two faces of the quartz glass plate. The transmission axes of the two polarizing plates are arranged to be orthogonal and at an angle of 45 degrees to the line of the glass end.

以與實施例1同樣的方式，將兩面貼附偏光板之玻璃板放入60℃乾燥的乾燥機17小時取出後，評價於暗室以目視方式觀察全面黑顯示狀態的漏光。其結果，在偏光板周邊觀察到了漏光。又，在輝度計測量輝度分布以測定漏光量。其結果最大漏光的透射率為0.1%。In the same manner as in Example 1, the glass plate to which the polarizing plates were attached was placed in a dryer dried at 60 ° C for 17 hours, and then the light leakage in the dark state was visually observed in the dark room. As a result, light leakage was observed around the polarizing plate. Further, the luminance distribution was measured by a luminance meter to measure the amount of light leakage. As a result, the transmittance of the maximum light leakage was 0.1%.

組合使用各種黏著劑所形成的顯示各種光彈性係數之黏著劑層，與彈性係數為5.0×109 、4.0×109 及3.0×109 Pa的光學補償薄片，製作各種與上述實施例相同構成之偏光板，藉由與上述實施例相同的評價法，測定因熱不均所引起的漏光量。所測定的漏光量對於黏著劑層的光彈性係數 所繪圖之圖表表示於第3圖，及所測定之漏光量對於偏光板Y的絕對值所繪圖之圖表表示於第4圖。另外，第3圖的縱軸係表示因熱不均所引起的漏光光量，漏光量的數值放大100倍極為透射率(%)。An adhesive layer which exhibits various photoelastic coefficients formed by using various adhesives in combination, and an optical compensation sheet having elastic coefficients of 5.0×10 9 , 4.0×10 9 and 3.0×10 9 Pa are used in the same manner as in the above embodiment. The polarizing plate was measured for the amount of light leakage due to heat unevenness by the same evaluation method as in the above embodiment. The graph of the measured light leakage amount plotted against the photoelastic coefficient of the adhesive layer is shown in Fig. 3, and the graph of the measured light leakage amount plotted against the absolute value of the polarizing plate Y is shown in Fig. 4. In addition, the vertical axis of Fig. 3 indicates the amount of light leakage due to thermal unevenness, and the numerical value of the light leakage amount is amplified by 100 times the maximum transmittance (%).

本發明人等已知只要上述漏光量(第3圖及第4圖的縱軸值)為0.0006以下、亦即漏光的透射率為0.06%以下即可，因上述熱不均所引起的漏光即大致上為肉眼所觀察不到，而可達成上述目的。The inventors of the present invention have known that the light leakage amount (the vertical axis value of FIGS. 3 and 4) is 0.0006 or less, that is, the light leakage transmittance is 0.06% or less, and the light leakage caused by the above-described thermal unevenness is This is generally not observed by the naked eye, and the above object can be achieved.

又第5圖中，係表示實施例及比較例之偏光板的Y值對於黏著劑層的光彈性係數所繪圖之圖表。實施例1~7中偏光板任一者的Y值係均低於0.0006，即使使用與實施例1、3、6及7相等的光學補償薄片1，比較例之偏光板的Y值亦超過0.0006。其結果，如上所述，實施例中任一漏光量(透射率)均低於0.06%，但比較例則高於0.06%。In the fifth drawing, the graphs showing the Y values of the polarizing plates of the examples and the comparative examples with respect to the photoelastic coefficient of the adhesive layer are shown. The Y values of any of the polarizing plates of Examples 1 to 7 were all less than 0.0006, and even when the optical compensation sheets 1 equivalent to Examples 1, 3, 6 and 7 were used, the Y value of the polarizing plate of the comparative example exceeded 0.0006. . As a result, as described above, the light leakage amount (transmittance) in any of the examples was less than 0.06%, but the comparative example was higher than 0.06%.

從以上實施例及比較例的結果、以及第3圖及第4圖所示之結果，具備偏光板Y的絕對值為0.0006以下之本發明偏光板的液晶顯示裝置，係明顯地減低了因熱不均所引起的漏光。From the results of the above examples and comparative examples, and the results shown in the third and fourth figures, the liquid crystal display device of the polarizing plate of the present invention having the absolute value of the polarizing plate Y of 0.0006 or less significantly reduces the heat generation. Light leakage caused by unevenness.

1‧‧‧黏著劑層1‧‧‧Adhesive layer

2‧‧‧光學補償薄片2‧‧‧Optical compensation sheet

3‧‧‧偏光膜3‧‧‧ polarizing film

4‧‧‧保護層4‧‧‧Protective layer

5‧‧‧剝離紙5‧‧‧ peeling paper

第1圖係本發明偏光板之一例的剖面模式圖。Fig. 1 is a schematic cross-sectional view showing an example of a polarizing plate of the present invention.

第2圖係本發明偏光板之另一例的剖面模式圖。Fig. 2 is a schematic cross-sectional view showing another example of the polarizing plate of the present invention.

第3圖係關於彈性係數為5×109 Pa、4×109 Pa、3×109 Pa之各光學補償薄片、與各種光彈性係數之黏著劑層所組合之偏光板的漏光光量，對於黏著劑層的光彈性係數所做繪圖之圖表。Fig. 3 is a graph showing the amount of light leakage of a polarizing plate combined with an optical adhesive sheet having a modulus of elasticity of 5 × 10 9 Pa, 4 × 10 9 Pa, and 3 × 10 9 Pa, and an adhesive layer of various photoelastic coefficients. A chart of the plot of the photoelastic coefficient of the adhesive layer.

第4圖係漏光量對於偏光板之Y的絕對值所做繪圖之圖表。Fig. 4 is a graph plotting the amount of light leakage for the absolute value of Y of the polarizing plate.

第5圖係實施例及比較例之偏光板的Y值對於黏著劑層的光彈性係數所做繪圖之圖表。Fig. 5 is a graph showing the Y value of the polarizing plate of the examples and the comparative examples for the photoelastic coefficient of the adhesive layer.

1‧‧‧黏著劑層1‧‧‧Adhesive layer

2‧‧‧光學補償薄片2‧‧‧Optical compensation sheet

3‧‧‧偏光膜3‧‧‧ polarizing film

4‧‧‧保護層4‧‧‧Protective layer

Claims (15)

一種偏光板，其特徵係至少具有偏光膜、黏著劑層、與光學補償薄片之偏光板，前述黏著劑層的光彈性係數為Cn(1/Pa)、前述光學補償薄片的彈性係數為E(Pa)時，下述式之值Y的絶對值為6.0×10-4 以下：Y=-7.0×105 ×Cn+4.3×10-13 ×E-1.34×10-3 。A polarizing plate characterized by having at least a polarizing film, an adhesive layer, and a polarizing plate with an optical compensation sheet; the photoelastic coefficient of the adhesive layer is Cn (1/Pa), and the elastic coefficient of the optical compensation sheet is E ( In the case of Pa), the absolute value of the value Y of the following formula is 6.0 × 10 -4 or less: Y = -7.0 × 10 5 × Cn + 4.3 × 10 -13 × E - 1.34 × 10 -3 . 如申請專利範圍第1項之偏光板，其中前述黏著劑層係包含丙烯酸系黏著劑。 The polarizing plate of claim 1, wherein the adhesive layer comprises an acrylic adhesive. 如申請專利範圍第2項之偏光板，其中前述丙烯酸系黏著劑係含有同元聚合物的光彈性係數為正之單體的至少一種聚合物。 The polarizing plate of claim 2, wherein the acrylic adhesive contains at least one polymer of a homopolymer having a positive photoelastic coefficient. 如申請專利範圍第2或3項之偏光板，其中前述丙烯酸系黏著劑係包含下述通式(I)所示單體的至少一種聚合物： 式中，R1 係表示氫原子或甲基；R2 係表示氫原子或取代基；R3 及R4 係分別表示氫原子或取代基；m係表示0以上的整數，n係表示0~5的整數，m及n係各自為2以上的整數時，複數個的R2 、R3 及R4 係分別可為相同或是不同。The polarizing plate of claim 2, wherein the acrylic adhesive comprises at least one polymer of a monomer represented by the following formula (I): In the formula, R 1 represents a hydrogen atom or a methyl group; R 2 represents a hydrogen atom or a substituent; R 3 and R 4 each represent a hydrogen atom or a substituent; m represents an integer of 0 or more, and n represents 0 to 0; When an integer of 5, m and n are each an integer of 2 or more, a plurality of R 2 , R 3 and R 4 may be the same or different. 如申請專利範圍第1至3項中任一項之偏光板，其中前 述光學補償薄片的光彈性係數為50×10-12 (1/Pa)以下。The polarizing plate according to any one of claims 1 to 3, wherein the optical compensation sheet has a photoelastic coefficient of 50 × 10 -12 (1/Pa) or less. 如申請專利範圍第4項之偏光板，其中前述光學補償薄片的光彈性係數為50×10-12 (1/Pa)以下。The polarizing plate of claim 4, wherein the optical compensation sheet has a photoelastic coefficient of 50 × 10 -12 (1/Pa) or less. 一種液晶顯示裝置，其特徵係至少含有液晶胞、與如申請專利範圍第1至6項中任一項之偏光板。 A liquid crystal display device characterized by comprising at least a liquid crystal cell, and a polarizing plate according to any one of claims 1 to 6. 如申請專利範圍第7項之液晶顯示裝置，其中前述液晶胞的基板表面與偏光板之黏著劑層的表面係接觸而配置。 The liquid crystal display device of claim 7, wherein the surface of the substrate of the liquid crystal cell is placed in contact with the surface of the adhesive layer of the polarizing plate. 如申請專利範圍第2項之偏光板，其中前述丙烯酸系黏著劑係含有由同元聚合物的光彈性係數為正之單體所衍生的至少一種重複單位之共聚物。 The polarizing plate of claim 2, wherein the acrylic adhesive comprises a copolymer of at least one repeating unit derived from a monomer having a positive photoelastic coefficient of a homopolymer. 如申請專利範圍第9項之偏光板，其中前述共聚物係含有選自於由芳香族系的丙烯酸酯單體及芳香族系的甲基丙烯酸酯單體的至少一種所衍生之重複單位的共聚物。 The polarizing plate of claim 9, wherein the copolymer contains a copolymer selected from a repeating unit derived from at least one of an aromatic acrylate monomer and an aromatic methacrylate monomer. Things. 如申請專利範圍第9或10項之偏光板，其中前述共聚物係含有由下述通式(I)所示單體的至少一種所衍生之重複單位的共聚物： 式中，R1 係表示氫原子或甲基；R2 係表示氫原子或取代基；R3 及R4 係分別表示氫原子或取代基；m係表示0以上的整數，n係表示0~5的整數，m及n係各自為2以上的 整數時，複數個的R2 、R3 及R4 係分別可為相同或是不同。The polarizing plate of claim 9 or 10, wherein the copolymer contains a copolymer of a repeating unit derived from at least one of the monomers represented by the following formula (I): In the formula, R 1 represents a hydrogen atom or a methyl group; R 2 represents a hydrogen atom or a substituent; R 3 and R 4 each represent a hydrogen atom or a substituent; m represents an integer of 0 or more, and n represents 0 to 0; When an integer of 5, m and n are each an integer of 2 or more, a plurality of R 2 , R 3 and R 4 may be the same or different. 如申請專利範圍第9或10項之偏光板，其中前述光學補償薄片的光彈性係數為50×10-12 (1/Pa)以下。The polarizing plate of claim 9 or 10, wherein the optical compensation sheet has a photoelastic coefficient of 50 × 10 -12 (1/Pa) or less. 如申請專利範圍第11項之偏光板，其中前述光學補償薄片的光彈性係數為50×10-12 (1/Pa)以下。The polarizing plate of claim 11, wherein the optical compensation sheet has a photoelastic coefficient of 50 × 10 -12 (1/Pa) or less. 一種液晶顯示裝置，其特徵係至少含有液晶胞與如申請專利範圍第9至13項中任一項之偏光板。 A liquid crystal display device characterized by comprising at least a liquid crystal cell and a polarizing plate according to any one of claims 9 to 13. 如申請專利範圍第14項之液晶顯示裝置，其中前述液晶胞的基板表面與偏光板之黏著劑層的表面係接觸而配置的。The liquid crystal display device of claim 14, wherein the surface of the substrate of the liquid crystal cell is disposed in contact with the surface of the adhesive layer of the polarizing plate.
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