TWI449971B - Elliptical polarizer, process of producing the polarizer and liquid crystal display device equipped with the polarizer - Google Patents
Elliptical polarizer, process of producing the polarizer and liquid crystal display device equipped with the polarizer Download PDFInfo
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- TWI449971B TWI449971B TW097132050A TW97132050A TWI449971B TW I449971 B TWI449971 B TW I449971B TW 097132050 A TW097132050 A TW 097132050A TW 97132050 A TW97132050 A TW 97132050A TW I449971 B TWI449971 B TW I449971B
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- liquid crystal
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3016—Polarising elements involving passive liquid crystal elements
-
- 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
- G02B5/305—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 including organic materials, e.g. polymeric layers
-
- 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
- G02F1/133634—Birefringent elements, e.g. for optical compensation the refractive index Nz perpendicular to the element surface being different from in-plane refractive indices Nx and Ny, e.g. biaxial or with normal optical axis
-
- 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
- G02F1/133633—Birefringent elements, e.g. for optical compensation using mesogenic materials
-
- 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
- G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
- G02F2413/01—Number of plates being 1
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
Description
本發明係關於由將垂直配向構造固定化的液晶層構成之橢圓偏光板及其製造方法,亦關於使用該橢圓偏光板的液晶顯示裝置。The present invention relates to an elliptically polarizing plate comprising a liquid crystal layer in which a vertical alignment structure is fixed, and a method of manufacturing the same, and a liquid crystal display device using the elliptically polarizing plate.
相位差膜係就使用於液晶顯示裝置的畫質提升等方面,扮演著工業性的重要角色。相位差膜大致可區分為:由塑膠薄膜延伸而成者、以及使液晶配向而成者。因為後者具有可實現多樣化折射率構造的潛力,因而具有更受矚目的價值。The retardation film system plays an important role in industrial use in terms of image quality improvement of liquid crystal display devices. The retardation film can be roughly classified into a plastic film extending and a liquid crystal alignment. Because the latter has the potential to achieve a diverse refractive index configuration, it has a more attractive value.
例如在膜厚方向具較大折射率的薄膜,被認為對液晶顯示裝置的視角改善具有效性,而利用液晶的垂直配向被認為係成為此種薄膜的捷徑。液晶分子的垂直配向係液晶的長軸分子方向相對基板,實質的朝垂直方向排列。垂直配向已知係如液晶顯示裝置般,在2片玻璃基板中裝入液晶並施加電場而獲得,但頗難將此種配向狀態形成薄膜,且習知報告所指出的方法尚有問題。例如在使主鏈型高分子液晶垂直配向之後,再經玻璃固定化便可獲得薄膜(專利文獻1~3)。但是,在垂直配向中,因為高分子將朝膜厚方向排列,因而推測在面內方向上容易發生龜裂情況的問題,但是在該等報告中就利用交聯進行材料強化等對策均無論及。在專利文獻4中有指出藉由將側鏈型液晶的垂直配向施行玻璃化而固定化,但判斷若欲達上述主鏈型高分子液晶以上的強度,尚有問題。For example, a film having a large refractive index in the film thickness direction is considered to be effective for improving the viewing angle of the liquid crystal display device, and the vertical alignment using the liquid crystal is considered to be a shortcut for such a film. The vertical alignment of the liquid crystal molecules is such that the long-axis molecular direction of the liquid crystal is aligned with respect to the substrate in a substantially vertical direction. The vertical alignment is known as a liquid crystal display device in which liquid crystal is charged in two glass substrates and an electric field is applied, but it is difficult to form such a alignment state into a thin film, and the method pointed out by the conventional report is problematic. For example, after the main chain type polymer liquid crystal is vertically aligned, the film is obtained by fixing the glass (Patent Documents 1 to 3). However, in the vertical alignment, since the polymer is aligned in the film thickness direction, it is presumed that the crack is likely to occur in the in-plane direction. However, in these reports, measures such as material strengthening by crosslinking are used. . In Patent Document 4, it is pointed out that the vertical alignment of the side chain type liquid crystal is immobilized by vitrification, but it is determined that there is a problem in that the strength of the main chain type polymer liquid crystal or more is required.
另一方面,亦有報告指出在側鏈型液晶高分子中添加聚合性低分子液晶(專利文獻5~6),但因為低分子液晶係屬於單獨進行聚合,因而側鏈型液晶高分子的強度補強有極限限制。專利文獻7中,使用對側鏈型液晶高分子導入諸如:自由基聚合性基、或者諸如乙烯醚基、環氧基之類的陽離子聚合性基之材料。但是,一般因為自由基聚合受氧抑制,因而恐導致聚合不足,且若採設備性地將氧去除,則導致裝置趨於龐大。因為乙烯醚基、環氧基並不會受氧抑制的影響,因而雖就此點而言將具優勢,然,會有乙烯醚基的醚鍵結呈不穩定而容易開裂的問題,且環氧基導入於液晶材料中較為繁雜,況且當施行交聯處理時頗難獲得高聚合度。此外,為能獲得垂直配向,便在液晶材料中導入大量的非液晶性構造單位,但有殘留呈現穩定液晶性的疑點。如上述,習知垂直配向性薄膜的製造尚殘留有問題。On the other hand, it has been reported that a polymerizable low molecular liquid crystal is added to a side chain type liquid crystal polymer (Patent Documents 5 to 6). However, since the low molecular liquid crystal system is polymerized alone, the strength of the side chain type liquid crystal polymer is obtained. Reinforcement has limit limits. In Patent Document 7, a material such as a radical polymerizable group or a cationically polymerizable group such as a vinyl ether group or an epoxy group is introduced into the side chain type liquid crystal polymer. However, in general, radical polymerization is inhibited by oxygen, which may result in insufficient polymerization, and if equipment is used to remove oxygen, the apparatus tends to be bulky. Since the vinyl ether group and the epoxy group are not affected by the inhibition of oxygen, although it is advantageous in this point, there is a problem that the ether bond of the vinyl ether group is unstable and easily cracked, and epoxy The introduction of a group into a liquid crystal material is complicated, and it is difficult to obtain a high degree of polymerization when a crosslinking treatment is performed. Further, in order to obtain the vertical alignment, a large amount of non-liquid crystalline structural units are introduced into the liquid crystal material, but there is a concern that the residual liquid crystallinity is retained. As described above, there has been a problem in the manufacture of a conventional vertical alignment film.
[專利文獻1]日本專利第2853064號公報[Patent Document 1] Japanese Patent No. 2853064
[專利文獻2]日本專利第3018120號公報[Patent Document 2] Japanese Patent No. 3018120
[專利文獻3]日本專利第3078948號公報[Patent Document 3] Japanese Patent No. 3078948
[專利文獻4]日本專利特開2002-174725號公報[Patent Document 4] Japanese Patent Laid-Open Publication No. 2002-174725
[專利文獻5]日本專利特開2002-333524號公報[Patent Document 5] Japanese Patent Laid-Open Publication No. 2002-333524
[專利文獻6]日本專利特開2002-333642號公報[Patent Document 6] Japanese Patent Laid-Open Publication No. 2002-333642
[專利文獻7]日本專利特開2003-2927號公報[Patent Document 7] Japanese Patent Laid-Open Publication No. 2003-2927
本發明之目的在於提供具有將垂直配向構造固定化的液晶層,藉由將層構造簡單化,而抑制厚度,且若組裝於液晶顯示裝置中,不僅視角獲改良,就連對比亦獲改善的橢圓偏光板,以及其製造方法,暨使用其之液晶顯示裝置。An object of the present invention is to provide a liquid crystal layer having a vertical alignment structure, which is thickened by simplification of a layer structure, and if incorporated in a liquid crystal display device, not only the viewing angle is improved, but also the contrast is improved. An elliptically polarizing plate, and a method of manufacturing the same, and a liquid crystal display device using the same.
本發明者等為解決上述問題,經深入鑽研的結果,發現藉由以下所示橢圓偏光板、其製造方法及使用其之液晶顯示裝置,便可達成上述目的,遂完成本發明。In order to solve the above problems, the inventors of the present invention have found out that the above object can be attained by the elliptically polarizing plate shown below, a method for producing the same, and a liquid crystal display device using the same, and the present invention has been completed.
即,第1發明的橢圓偏光板,係至少由:使呈正單軸性的液晶性組成物在液晶狀態下施行垂直配向後,再將該配向固定化的垂直配向液晶層;具有相位差功能的相位差膜;以及具有僅偏光元件單面利用透光性保護膜施行保護之積層構造的直線偏光板;所構成之橢圓偏光板;其中,具有下述(A)或(B)中任一項積層構造:In other words, the elliptically polarizing plate according to the first aspect of the invention is a vertical alignment liquid crystal layer in which the liquid crystal composition having a positive uniaxiality is vertically aligned in a liquid crystal state, and then the alignment is fixed, and has a phase difference function. a retardation film; and a linear polarizing plate having a laminated structure in which only one surface of the polarizing element is protected by a light-transmitting protective film; and an elliptically polarizing plate comprising the following (A) or (B); Laminated construction:
(A)透光性保護膜/偏光元件/相位差膜/垂直配向液晶層;(A) light transmissive protective film / polarizing element / retardation film / vertical alignment liquid crystal layer;
(B)透光性保護膜/偏光元件/垂直配向液晶層/相位差膜。(B) Translucent protective film / polarizing element / vertical alignment liquid crystal layer / retardation film.
第2發明係如第1發明所記載的橢圓偏光板,其中,上述垂直配向液晶層係將含有具氧雜環丁烷基之側鏈型液晶性高分子化合物的液晶性組成物,在液晶狀態下施行垂直配向後,使上述氧雜環丁烷基產生反應,而將上述垂直配向固定化的垂直配向液晶層。The elliptically polarizing plate according to the first aspect of the invention, wherein the vertical alignment liquid crystal layer contains a liquid crystalline composition containing a side chain type liquid crystalline polymer compound having an oxetane group, and is in a liquid crystal state. After the vertical alignment is performed, the oxetane group is reacted to form the vertically aligned liquid crystal layer fixed in the vertical alignment.
第3發明係如第1或2發明所記載的橢圓偏光板,其中,上述垂直配向液晶層係滿足以下[1]及[2]:The elliptically polarizing plate according to the first or second aspect of the invention, wherein the vertical alignment liquid crystal layer satisfies the following [1] and [2]:
[1]0nm≦Re1≦20nm[1]0nm≦Re1≦20nm
[2]-500nm≦Rth1≦-30nm[2]-500nm≦Rth1≦-30nm
(其中,Re1係指上述垂直配向液晶層面內的延遲值;Rth1係指上述垂直配向液晶層厚度方向的延遲值。上述Re1及Rth1分別係Re1=(Nx1-Ny1)×d1[nm]、Rth1=(Nx1-Nz1)×d1[nm]。此外,d1係指上述垂直配向液晶層的厚度,Nx1及Ny1係指上述垂直配向液晶層面內的主折射率,Nz1係指厚度方向的主折射率,且Nz1>Nx1≧Ny1。)(Re1 is the retardation value in the vertical alignment liquid crystal layer; Rth1 is the retardation value in the thickness direction of the vertical alignment liquid crystal layer. Re1 and Rth1 are Re1 = (Nx1 - Ny1) × d1 [nm], Rth1, respectively. = (Nx1 - Nz1) × d1 [nm]. Further, d1 is the thickness of the above-mentioned vertical alignment liquid crystal layer, Nx1 and Ny1 are the main refractive indices in the vertical alignment liquid crystal layer, and Nz1 is the main refractive index in the thickness direction. And Nz1>Nx1≧Ny1.)
第4發明係如第1~3發明所記載的橢圓偏光板,其中,上述相位差膜係滿足以下[3]及[4]:The elliptically polarizing plate according to the first to third aspects of the invention, wherein the retardation film satisfies the following [3] and [4]:
[3]20nm≦Re2≦200nm[3]20nm≦Re2≦200nm
[4]0nm≦Rth2≦30nm[4]0nm≦Rth2≦30nm
(其中,Re2係指相位差膜面內的延遲值;Rth2係指上述相位差膜厚度方向的延遲值。上述Re2及Rth2分別係指Re2=(Nx2-Ny2)×d2[nm]、Rth2=(Nx2-Nz2)×d2[nm]。此外,d2係指上述相位差膜的厚度,Nx2及Ny2係指上述相位差膜面內的主折射率,Nz2係指厚度方向的主折射率,且Nx2>Ny2≧Nz2。)(Re2 refers to the retardation value in the plane of the retardation film; Rth2 refers to the retardation value in the thickness direction of the retardation film. Re2 and Rth2 refer to Re2=(Nx2-Ny2)×d2[nm] and Rth2=, respectively. (Nx2-Nz2) × d2 [nm], d2 is the thickness of the retardation film, Nx2 and Ny2 are the principal refractive indices in the plane of the retardation film, and Nz2 is the principal refractive index in the thickness direction, and Nx2>Ny2≧Nz2.)
第5發明係如第1~4發明所記載的橢圓偏光板,係由至少1片以上的光學薄膜積層而成。According to a fifth aspect of the invention, the elliptically polarizing plate according to the first to fourth aspects of the invention is obtained by laminating at least one or more optical films.
第6發明係如第1~5發明所記載的橢圓偏光板,其中,上述透光性保護膜係三醋酸纖維素、或環烯烴系聚合物。The elliptically polarizing plate according to the first aspect of the invention, wherein the translucent protective film is a cellulose triacetate or a cycloolefin polymer.
第7發明係如第1~6發明所記載的橢圓偏光板,其中,總膜厚係175μm以內。The elliptically polarizing plate according to the first to sixth aspects of the invention, wherein the total thickness is 175 μm or less.
第8發明的橢圓偏光板之製造方法,係至少經由下述各步驟:The method for producing an elliptically polarizing plate according to the eighth aspect of the invention is at least the following steps:
(1)將透光性保護膜經由接著劑層1而與偏光元件相黏合,獲得由透光性保護膜/接著劑層1/偏光元件構成積層體(I)的第1步驟;(1) The light-transmitting protective film is bonded to the polarizing element via the adhesive layer 1 to obtain a first step of forming the laminated body (I) from the light-transmitting protective film/adhesive layer 1/polarizing element;
(2)在相位差膜上形成呈現正單軸性的液晶性組成物之層,將該層施行垂直配向之後,再形成將配向固定化的垂直配向液晶層,獲得由相位差膜/垂直配向液晶層構成積層體(II)的第2步驟;以及(2) forming a layer of a liquid crystal composition exhibiting a positive uniaxiality on the retardation film, and performing vertical alignment of the layer, and then forming a vertical alignment liquid crystal layer to which the alignment is fixed, thereby obtaining a retardation film/vertical alignment The liquid crystal layer constitutes the second step of the layered body (II);
(3)將上述積層體(II)的相位差膜側經由接著劑層2,與上述積層體(I)的偏光元件側相黏合,而獲得由透光性保護膜/接著劑層1/偏光元件/接著劑層2/相位差膜/垂直配向液晶層構成橢圓偏光板的第3步驟。(3) The retardation film side of the laminated body (II) is bonded to the polarizing element side of the laminated body (I) via the adhesive layer 2 to obtain a light-transmitting protective film/adhesive layer 1/polarized light. The third step of forming the elliptically polarizing plate by the element/adhesive layer 2/phase difference film/vertical alignment liquid crystal layer.
第9發明的橢圓偏光板之製造方法,係至少經由下述各步驟:The method for producing an elliptically polarizing plate according to the ninth invention is at least via the following steps:
(1)將透光性保護膜經由接著劑層1而與偏光元件相黏合,而獲得由透光性保護膜/接著劑層1/偏光元件構成積層體(I)的第1步驟;(1) a step of bonding a light-transmitting protective film to a polarizing element via an adhesive layer 1 to obtain a laminated body (I) comprising a light-transmitting protective film/adhesive layer 1/polarizing element;
(2)在相位差膜上形成呈現正單軸性的液晶性組成物之層,將該層施行垂直配向之後,再形成將配向固定化的垂直配向液晶層,獲得由相位差膜/垂直配向液晶層構成積層體(II)的第2步驟;以及(2) forming a layer of a liquid crystal composition exhibiting a positive uniaxiality on the retardation film, and performing vertical alignment of the layer, and then forming a vertical alignment liquid crystal layer to which the alignment is fixed, thereby obtaining a retardation film/vertical alignment The liquid crystal layer constitutes the second step of the layered body (II);
(3)將上述積層體(II)的垂直配向液晶相側,經由接著劑層2,與上述積層體(I)的偏光元件側相黏合,獲得由透光性保護膜/接著劑層1/偏光元件/接著劑層2/垂直配向液晶層/相位差膜構成橢圓偏光板的第3步驟。(3) The vertical alignment of the layered product (II) is directed to the liquid crystal phase side, and is bonded to the polarizing element side of the layered product (I) via the adhesive layer 2 to obtain a light-transmitting protective film/adhesive layer 1/ The polarizing element/adhesive layer 2/vertical alignment liquid crystal layer/retardation film constitutes the third step of the elliptically polarizing plate.
第10發明的橢圓偏光板之製造方法,係至少經由下述各步驟:The method for producing an elliptically polarizing plate according to a tenth aspect of the invention is at least the following steps:
(1)將透光性保護膜經由接著劑層1而與偏光元件相黏合,獲得由透光性保護膜/接著劑層1/偏光元件構成積層體(I)的第1步驟;(1) The light-transmitting protective film is bonded to the polarizing element via the adhesive layer 1 to obtain a first step of forming the laminated body (I) from the light-transmitting protective film/adhesive layer 1/polarizing element;
(2)在配向基板上形成呈現正單軸性的液晶性組成物之層,將該層施行垂直配向之後,再形成將配向固定化的垂直配向液晶層,獲得由配向基板/垂直配向液晶層構成積層體(III)的第2步驟;(2) forming a layer of a liquid crystal composition exhibiting a positive uniaxiality on the alignment substrate, and then vertically aligning the layer, and then forming a vertical alignment liquid crystal layer to which the alignment is fixed, thereby obtaining an alignment substrate/vertical alignment liquid crystal layer The second step of constituting the layered body (III);
(3)將上述積層體(III)的垂直配向液晶層側經由接著劑層2,與相位差膜相黏合之後,再將配向基板剝離而將垂直配向液晶層轉印於相位差膜上,獲得由相位差膜/接著劑層2/垂直配向液晶層構成積層體(IV)的第3步驟;以及(3) The vertical alignment liquid crystal layer side of the laminate (III) is bonded to the retardation film via the adhesive layer 2, and then the alignment substrate is peeled off, and the vertical alignment liquid crystal layer is transferred onto the retardation film to obtain a third step of forming the layered body (IV) from the retardation film/adhesive layer 2/vertical alignment liquid crystal layer;
(4)將上述積層體(IV)的相位差膜側經由接著劑層3,與上述積層體(I)的偏光元件側相黏合,獲得由透光性保護膜/接著劑層1/偏光元件/接著劑層3/相位差膜/接著劑層2/垂直配向液晶層構成橢圓偏光板的第4步驟。(4) The retardation film side of the layered product (IV) is bonded to the polarizing element side of the layered product (I) via the adhesive layer 3 to obtain a light-transmitting protective film/adhesive layer 1/polarizing element. / The adhesive layer 3 / retardation film / adhesive layer 2 / vertical alignment liquid crystal layer constitutes the fourth step of the elliptically polarizing plate.
第11發明的橢圓偏光板之製造方法,係至少經由下述各步驟:The method for producing an elliptically polarizing plate according to the eleventh aspect of the invention is at least the following steps:
(1)將透光性保護膜經由接著劑層1而與偏光元件相黏合,獲得由透光性保護膜/接著劑層1/偏光元件構成積層體(I)的第1步驟;(1) The light-transmitting protective film is bonded to the polarizing element via the adhesive layer 1 to obtain a first step of forming the laminated body (I) from the light-transmitting protective film/adhesive layer 1/polarizing element;
(2)在配向基板上形成呈現正單軸性的液晶性組成物之層,將該層施行垂直配向之後,再形成將配向固定化的垂直配向液晶層,獲得由配向基板/垂直配向液晶層構成積層體(III)的第2步驟;(2) forming a layer of a liquid crystal composition exhibiting a positive uniaxiality on the alignment substrate, and then vertically aligning the layer, and then forming a vertical alignment liquid crystal layer to which the alignment is fixed, thereby obtaining an alignment substrate/vertical alignment liquid crystal layer The second step of constituting the layered body (III);
(3)將上述積層體(III)的垂直配向液晶層側經由接著劑層2,而與相位差膜相黏合之後,再將配向基板剝離而將垂直配向液晶層轉印於相位差膜上,獲得由相位差膜/接著劑層2/垂直配向液晶層構成積層體(IV)的第3步驟;以及(3) After the vertical alignment liquid crystal layer side of the layered product (III) is bonded to the retardation film via the adhesive layer 2, the alignment substrate is peeled off, and the vertical alignment liquid crystal layer is transferred onto the retardation film. Obtaining a third step of forming the laminate (IV) from the retardation film/adhesive layer 2/vertical alignment liquid crystal layer;
(4)將上述積層體(IV)的垂直配向液晶層側經由接著劑層3,而與上述積層體(A)的偏光元件側相黏合,獲得由透光性保護膜/接著劑層1/偏光元件/接著劑層3/垂直配向液晶層/接著劑層2/相位差膜構成橢圓偏光板的第4步驟。(4) The vertical alignment liquid crystal layer side of the laminate (IV) is bonded to the polarizing element side of the laminate (A) via the adhesive layer 3 to obtain a light-transmitting protective film/adhesive layer 1/ The polarizing element/adhesive layer 3/vertical alignment liquid crystal layer/adhesive layer 2/retardation film constitutes the fourth step of the elliptically polarizing plate.
第12發明的液晶顯示裝置,係在液晶單元至少單側的面上,配置第1~7發明所記載的橢圓偏光板。In the liquid crystal display device of the twelfth aspect of the invention, the elliptically polarizing plates described in the first to seventh aspects of the invention are disposed on at least one surface of the liquid crystal cell.
第13發明係如第12發明所記載的液晶顯示裝置,其中,上述液晶單元係VA液晶單元或IPS液晶單元。The liquid crystal display device according to the twelfth aspect, wherein the liquid crystal cell is a VA liquid crystal cell or an IPS liquid crystal cell.
使用垂直配向液晶層的本發明橢圓偏光板,特別係當配置於垂直配向型液晶顯示裝置的情況,不僅可放大視角,且該垂直配向型液晶顯示裝置可明亮顯示,全方位均可進行高對比的顯示。The elliptically polarizing plate of the present invention using a vertical alignment liquid crystal layer, in particular, when disposed in a vertical alignment type liquid crystal display device, can not only enlarge the viewing angle, but the vertical alignment type liquid crystal display device can display brightly and can perform high contrast in all directions. Display.
以下,針對本發明進行詳細說明。Hereinafter, the present invention will be described in detail.
針對本發明的橢圓偏光板進行說明。The elliptically polarizing plate of the present invention will be described.
本發明的橢圓偏光板係至少由:使至少呈正單軸性的液晶性組成物在液晶狀態中施行垂直配向後,再將該配向固定化的垂直配向液晶層;具有相位差功能的相位差膜;以及具有僅偏光元件單面利用透光性保護膜施行保護之積層構造的直線偏光板構成。本發明中,在獲得將垂直配向固定化的垂直配向液晶層之際,使在相位差膜上、配向基板上、或配向基板上的配向膜上所形成液晶性組成物層進行垂直配向後,視需要經光照射及/或加熱處理後再進行冷卻,而將該配向狀態固定化便可製得。液晶性組成物所使用的液晶材料係在屬於能進行垂直配向的正單軸性液晶材料之前提下,將可為由低分子液晶化合物、液晶性高分子化合物、或該等的混合物所構成之材料。The elliptically polarizing plate of the present invention is at least a vertical alignment liquid crystal layer in which a liquid crystal composition having at least a positive uniaxiality is vertically aligned in a liquid crystal state, and then the alignment is fixed; a retardation film having a phase difference function And a linear polarizing plate having a laminated structure in which only one surface of the polarizing element is protected by a light-transmitting protective film. In the present invention, when the vertical alignment liquid crystal layer to which the vertical alignment is fixed is obtained, the liquid crystal composition layer formed on the alignment film on the retardation film, the alignment substrate, or the alignment substrate is vertically aligned. It can be obtained by fixing the alignment state by cooling with light and/or heat treatment as needed. The liquid crystal material used for the liquid crystal composition may be formed of a low molecular liquid crystal compound, a liquid crystalline polymer compound, or a mixture thereof before being added to a positive uniaxial liquid crystal material capable of vertical alignment. material.
上述低分子液晶化合物因為鍵結著經利用光或熱會進行反應之反應性基的化合物,可輕易地將配向固定化,而屬較佳狀態。反應性基最好為例如:乙烯基、(甲基)丙烯醯基、乙烯氧基、氧雜環丙烷基、氧雜環丁烷基、吖丙啶基等,依照反應條件等尚可使用其他反應性基,例如:異氰酸酯基、羥基、胺基、酸酐基、羧基等。The above-mentioned low molecular liquid crystal compound can be easily immobilized by bonding a compound which reacts with a reactive group which is reacted by light or heat, and is preferable. The reactive group is preferably, for example, a vinyl group, a (meth)acrylonitrile group, a vinyloxy group, an oxiranyl group, an oxetanyl group or an aziridine group, and other conditions may be used depending on the reaction conditions and the like. The reactive group is, for example, an isocyanate group, a hydroxyl group, an amine group, an acid anhydride group, a carboxyl group or the like.
上述液晶性高分子化合物係有主鏈型液晶性高分子化合物與側鏈型液晶性高分子化合物,可使用任一者。The liquid crystalline polymer compound may be a main chain type liquid crystalline polymer compound or a side chain type liquid crystalline polymer compound, and any of them may be used.
主鏈型液晶性高分子化合物係可舉例如:聚酯、聚酯醯亞胺、聚醯胺、聚碳酸酯等。其中,就從合成容易度、配向性、玻璃轉移點等觀點而言,最好為液晶性聚酯。The main chain type liquid crystalline polymer compound may, for example, be polyester, polyester quinone, polyamine or polycarbonate. Among them, from the viewpoints of ease of synthesis, orientation, glass transition point, and the like, a liquid crystalline polyester is preferable.
側鏈型液晶性高分子化合物係可舉例如:聚(甲基)丙烯酸酯、聚丙二酸酯、聚矽氧烷等。該等液晶性高分子化合物最好鍵結著上述反應性基者。其中,最好為鍵結著依下述一般式(1)所示反應性基的聚(甲基)丙烯酸酯。The side chain type liquid crystalline polymer compound may, for example, be a poly(meth)acrylate, a polymalonate or a polyoxyalkylene. It is preferable that these liquid crystalline polymer compounds are bonded to the above reactive group. Among them, a poly(meth)acrylate having a reactive group represented by the following general formula (1) is preferably bonded.
式(1)中,R3 分別係指獨立的氫或甲基;R4 分別係指獨立的氫、甲基、乙基、丁基、己基、辛基、壬基、癸基、十二烷基、甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、癸氧基、十二烷氧基、氰基、溴基、氯基、氟基或羧基;R5 分別係指獨立的氫、甲基或乙基;R6 係指碳數1至24的烴基;L2 分別係指獨立的單鍵、-O-、-O-CO-、-CO-O-、-CH=CH-或-C≡C-;p係指1至10的整數;q係指0至10的整數;a、b、c、d、e及f係指聚合物中的各單元莫耳比(a+b+c+d+e+f=1.0,但,不可以c+d+e=0)。In the formula (1), R 3 means independently hydrogen or methyl, respectively; R 4 means independently hydrogen, methyl, ethyl, butyl, hexyl, octyl, decyl, decyl, dodecane, respectively. Base, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy, dodecyloxy, cyano, bromo, Chlorine, fluorine or carboxyl; R 5 means independently hydrogen, methyl or ethyl; R 6 means a hydrocarbon group of 1 to 24; L 2 means an independent single bond, -O-, - O-CO-, -CO-O-, -CH=CH- or -C≡C-; p means an integer from 1 to 10; q means an integer from 0 to 10; a, b, c, d, e And f means the molar ratio of each unit in the polymer (a+b+c+d+e+f=1.0, but c+d+e=0).
構成式(1)所示側鏈型液晶性高分子化合物的各成分莫耳比,係a+b+c+d+e+f=1.0、不可為c+d+e=0,且必需呈液晶性。在滿足該要件的前提下,各成分的莫耳比可為任意,最好如下:The molar ratio of each component of the side chain type liquid crystalline polymer compound represented by the formula (1) is a+b+c+d+e+f=1.0, and cannot be c+d+e=0, and must be Liquid crystal. Under the premise of satisfying the requirements, the molar ratio of each component can be arbitrary, preferably as follows:
a:最好0~0.80、尤以0.05~0.50為佳a: preferably 0~0.80, especially 0.05~0.50
b:最好0~0.90、尤以0.10~0.70為佳b: preferably 0~0.90, especially 0.10~0.70
c:最好0~0.50、尤以0.10~0.30為佳c: preferably 0~0.50, especially 0.10~0.30
d:最好0~0.50、尤以0.10~0.30為佳d: preferably 0~0.50, especially 0.10~0.30
e:最好0~0.50、尤以0.10~0.30為佳e: preferably 0~0.50, especially 0.10~0.30
f:最好0~0.30、尤以0.01~0.10為佳f: preferably 0~0.30, especially 0.01~0.10
該等聚(甲基)丙烯酸酯中的各成分係滿足上述條件之前提下,並不必一定要所有的6種成分均存在。若超越該等範圍外,因為液晶性嫌不足、或欠缺氧雜環丁烷基的反應性,因而最好避免。It is not necessary to have all of the six components present before the respective components in the poly(meth) acrylate satisfy the above conditions. If it exceeds these ranges, it is preferably avoided because the liquid crystallinity is insufficient or the reactivity of the oxetane group is insufficient.
再者,R4 最好為例如:氫、甲基、丁基、甲氧基、氰基、溴基、氟基等,尤以氫、甲氧基或氰基為佳,L2 最好為例如:單鍵、-O-、-O-CO-或-CO-O-,R6 最好為碳數2、3、4、6、8或18的烴基。Further, R 4 is preferably, for example, hydrogen, methyl, butyl, methoxy, cyano, bromo, or fluoro, etc., particularly preferably hydrogen, methoxy or cyano, and L 2 is preferably For example, a single bond, -O-, -O-CO- or -CO-O-, R 6 is preferably a hydrocarbon group having 2, 3, 4, 6, 8, or 18 carbon atoms.
再者,一般式(1)所示側鏈型液晶性高分子化合物,係利用各成分a~f的莫耳比、配向形態而使複折射率變化,當採向列配向時的複折射率,最好為0.001~0.300,尤以0.05~0.25為佳。In addition, the side chain type liquid crystalline polymer compound represented by the general formula (1) changes the complex refractive index by the molar ratio and the alignment form of each component a to f, and the complex refractive index when the alignment is employed. Preferably, it is 0.001 to 0.300, especially 0.05 to 0.25.
符合上述側鏈型液晶性高分子化合物各成分的各個(甲基)丙烯酸化合物,利用普通的有機化學合成方法便可獲得。具有氧雜環丁烷基的(甲基)丙烯酸化合物,例如利用威廉森(Williamson)的醚合成、或者使用縮合劑的酯合成等手段,而將具有氧雜環丁烷基的部位、與具有(甲基)丙烯基的部位相鍵結,便可合成具有氧雜環丁烷基與(甲基)丙烯基等二種反應性官能基之具有氧雜環丁烷基的(甲基)丙烯酸化合物。Each (meth)acrylic compound which satisfies each component of the above-mentioned side chain type liquid crystalline polymer compound can be obtained by an ordinary organic chemical synthesis method. The (meth)acrylic compound having an oxetane group, for example, by using an ether synthesis of Williamson or an ester synthesis using a condensing agent, and having a site having an oxetane group and having The (meth)acrylic group is bonded to a (meth)acrylic acid having an oxetanyl group having two reactive functional groups such as an oxetane group and a (meth)acryl group. Compound.
上述側鏈型液晶性高分子化合物係將符合各成分且依上述方法等所獲得各個(甲基)丙烯酸化合物的(甲基)丙烯基,利用自由基聚合或陰離子聚合進行共聚合,便可輕易地合成。聚合條件並無特別的限制,可採用通常的條件。The side chain type liquid crystalline polymer compound can be easily copolymerized by radical polymerization or anionic polymerization by using a (meth)acryl group of each (meth)acrylic acid compound obtained by the above method in accordance with each component. Synthetic. The polymerization conditions are not particularly limited, and usual conditions can be employed.
自由基聚合的例子,係有如:將符合各成分的(甲基)丙烯酸化合物溶解於諸如二甲基甲醯胺(DMF)、二乙二醇二甲醚等溶劑中,並以諸如2,2’-偶氮雙異丁腈(AIBN)、過氧化二苯甲醯(BPO)等為起始劑,且在60~120℃下進行數小時反應的方法。此外,為能穩定地呈現液晶相,諸如以溴化銅(I)/2,2’-聯二吡啶系、或2,2,6,6-四甲基哌啶氧化物‧自由基(TEMPO)系等為起始劑,並施行活性自由基聚合,而施行分子量分佈控制的方法亦屬有效。該等自由基聚合必需在脫氧條件下實施。Examples of the radical polymerization are, for example, dissolving a (meth)acrylic compound conforming to each component in a solvent such as dimethylformamide (DMF) or diethylene glycol dimethyl ether, and such as 2, 2 A method in which an azo-isoisobutyronitrile (AIBN) or a benzamidine peroxide (BPO) is used as a starter and is reacted at 60 to 120 ° C for several hours. Further, in order to stably exhibit a liquid crystal phase, such as copper(I)/2,2'-bipyridine, or 2,2,6,6-tetramethylpiperidine oxide ‧ free radical (TEMPO) The system is the initiator and the living radical polymerization is carried out, and the method of controlling the molecular weight distribution is also effective. These free radical polymerizations must be carried out under deoxygenated conditions.
陰離子聚合的例子,係有如將符合各成分的(甲基)丙烯酸化合物溶解於諸如四氫呋喃(THF)等溶劑中,並以諸如有機鋰化合物、有機鈉化合物、格林尼亞試劑等強鹼為起始劑而進行反應的方法。此外,藉由將起始劑、反應溫度最佳化,以進行活性陰離子聚合,且亦對分子量分佈進行控制。該等陰離子聚合必需在脫水且脫氧條件下實施。An example of anionic polymerization is to dissolve a (meth)acrylic compound conforming to each component in a solvent such as tetrahydrofuran (THF), and start with a strong base such as an organolithium compound, an organic sodium compound, or a Grignard reagent. The method of carrying out the reaction. Further, living anion polymerization is carried out by optimizing the initiator and the reaction temperature, and the molecular weight distribution is also controlled. These anionic polymerizations must be carried out under dehydration and deoxygenation conditions.
側鏈型液晶性高分子化合物的重量平均分子量最好為1,000~200,000,尤以3,000~50,000為佳。若超出該範圍外,則有強度嫌不足、或配向性惡化的情況,因而最好避免。The weight average molecular weight of the side chain type liquid crystalline polymer compound is preferably from 1,000 to 200,000, particularly preferably from 3,000 to 50,000. If it is outside this range, there is a case where the strength is insufficient or the alignment property is deteriorated, so it is preferable to avoid it.
本發明中,由上述低分子液晶化合物、液晶性高分子化合物、或該等的混合物所構成之液晶材料或液晶性組成物,最好含有下述一般式(2)所示二氧雜環丁烷化合物。In the present invention, the liquid crystal material or the liquid crystal composition comprising the low molecular liquid crystal compound, the liquid crystalline polymer compound, or the mixture thereof preferably contains the dioxetane represented by the following general formula (2). Alkane compound.
式(2)中,R7 分別係指獨立的氫、甲基或乙基;L3 分別係指獨立的單鍵或-(CH2 )n-(n係1~12的整數);X1 分別係指獨立的單鍵、-O-、-O-CO-、或-CO-O-;M1 係指式(3)或式(4)所示中任一者,而式(3)及式(4)中的P1 分別係指獨立且從式(5)中選擇的基;P2 係指從式(6)中選擇的基;L4 分別係指獨立的單鍵、-CH=CH-、-C≡C-、-O-、-O-CO-、或-CO-O-。In the formula (2), R 7 means independently hydrogen, methyl or ethyl; respectively; L 3 means an independent single bond or -(CH 2 )n- (n is an integer of 1 to 12); X 1 Respectively means an independent single bond, -O-, -O-CO-, or -CO-O-; M 1 means any one of formula (3) or formula (4), and formula (3) And P 1 in the formula (4) means a group independently selected from the formula (5); P 2 means a group selected from the formula (6); and L 4 means an independent single bond, -CH, respectively. =CH-, -C≡C-, -O-, -O-CO-, or -CO-O-.
-P1 -L4 -P2 -L4 -P1 - (3)-P 1 -L 4 -P 2 -L 4 -P 1 - (3)
-P1 -L4 -P1 - (4)-P 1 -L 4 -P 1 - (4)
式(5)及式(6)中,Et係指乙基,iPr係指異丙基,nBu係指正丁基,tBu係指第三丁基。In the formulae (5) and (6), Et means ethyl, iPr means isopropyl, nBu means n-butyl, and tBu means tributyl.
更具體而言,從M1 基觀之,將左右的氧雜環丁烷基相鍵結的連接基係可互異(非對稱型)、亦可相同(對稱型),特別係亦有2個L3 為不同的情況、或因其他連接基的構造導致無法呈現液晶性的情況,在使用上並無限制。More specifically, from the viewpoint of M 1 , the linking groups to which the left and right oxetanyl groups are bonded may be different (asymmetric) or the same (symmetrical), and in particular, 2 The case where L 3 is different or the liquid crystal property cannot be exhibited due to the structure of other link groups is not limited in use.
一般式(2)所示化合物係就從M1 、L3 及X1 的組合觀之,將可例示多種化合物,最好可舉例如下述化合物:The compound represented by the general formula (2) is exemplified by a combination of M 1 , L 3 and X 1 , and various compounds can be exemplified, and preferably, for example, the following compounds are used:
該等化合物係可依照有機化學中的普通合成方法便可合成,且合成方法並無特別的限制。These compounds can be synthesized in accordance with ordinary synthetic methods in organic chemistry, and the synthesis method is not particularly limited.
在合成之時,因為氧雜環丁烷基係具有陽離子聚合性,因而在強酸性條件下,判斷將產生諸如聚合、開環等副反應,因而必需選擇反應條件。另外,氧雜環丁烷基在相較於屬於類似陽離子聚合性官能基的氧雜環丙烷基等之下,前者引發副反應的可能性較低。此外,亦可使類似的醇、酚、羧酸等各種化合物逐次進行反應,亦可考慮活用適當的保護基。At the time of the synthesis, since the oxetane group has cationic polymerizability, it is judged that under a strong acidic condition, side reactions such as polymerization and ring opening will occur, and it is necessary to select reaction conditions. Further, the oxetane group is less likely to cause a side reaction than the oxirane group or the like which is a cationically polymerizable functional group. Further, various compounds such as an alcohol, a phenol, a carboxylic acid, and the like may be successively reacted, and an appropriate protecting group may be considered.
更具體的合成方法,係可舉例如:以羥基苯甲酸為起始化合物,並依照威廉森的醚合成法等使氧雜環丁烷基鍵結,接著,再使所獲得化合物與適用本發明的二醇,利用諸如酸氯化法、或依羰二醯亞胺施行的縮合法等進行鍵結之方法;或者相反的預先將羥基苯甲酸的羥基利用適當保護基進行保護,經與適用本發明的二醇進行縮合後,再使保護基脫離,而形成具有適當氧雜環丁烷基的化合物(氧雜環丁烷化合物),例如使鹵烷基氧雜環丁烷等與羥基進行反應的方法等。More specific synthetic methods include, for example, hydroxybenzoic acid as a starting compound, and an oxetane linkage according to Williamson's ether synthesis method, etc., and then the obtained compound is applied to the present invention. a diol which is bonded by a condensation method such as an acid chlorination method or a carbodiimide or the like, or a hydroxy group of a hydroxybenzoic acid is protected in advance by a suitable protecting group. After the diol of the invention is condensed, the protecting group is removed to form a compound having an appropriate oxetane group (oxetane compound), for example, a haloalkyl oxetane or the like is reacted with a hydroxyl group. Method etc.
氧雜環丁烷化合物與羥基的反應係只要依照所使用化合物的形態、反應性,而選擇適合的反應條件便可,通常反應溫度係選擇-20℃~180℃,最好10℃~150℃,反應時間係選擇10分~48小時,最好30分~24小時。若超出該等範圍外,反應無法充分地進行、或產生副反應,因而最好避免。此外,二者的混合比例係羥基每1當量,最好設定為氧雜環丁烷化合物0.8~1.2當量。The reaction system of the oxetane compound and the hydroxyl group may be selected according to the form and reactivity of the compound to be used, and the reaction temperature is usually -20 ° C to 180 ° C, preferably 10 ° C to 150 ° C. The reaction time is selected from 10 minutes to 48 hours, preferably from 30 minutes to 24 hours. If it exceeds these ranges, the reaction does not proceed sufficiently or a side reaction occurs, and thus it is preferable to avoid it. Further, the mixing ratio of the two is preferably 1 to 1 equivalent of the hydroxyl group, and is preferably 0.8 to 1.2 equivalents of the oxetane compound.
本發明所使用的液晶材料中,除上述低分子液晶化合物、液晶性高分子化合物之外,在不損及液晶性之前提下,尚可含有能混合的各種化合物。可含有的化合物係可舉例如:具有諸如氧雜環丁烷基、環氧基、乙烯氧基等陽離子聚合性官能基的化合物;具有薄膜形成能力的各種高分子物質;呈現液晶性的各種低分子液晶性化合物或高分子液晶性化合物等。當將上述側鏈型液晶性高分子化合物使用為組成物的情況,整體組成物中所佔的上述側鏈型液晶性高分子化合物比例係達10質量%以上,最好達30質量%以上,尤以50質量%以上為佳。若側鏈型液晶性高分子化合物的含有量未滿10質量%,則薄膜形成能力嫌不足、組成物中所佔的聚合性基濃度降低、聚合後的機械強度嫌不足,因而最好避免。The liquid crystal material used in the present invention may contain various compounds which can be mixed, in addition to the above-mentioned low molecular liquid crystal compound and liquid crystalline polymer compound, without being damaged by liquid crystallinity. The compound which may be contained is, for example, a compound having a cationically polymerizable functional group such as an oxetane group, an epoxy group or a vinyloxy group; various polymer materials having a film forming ability; and various low liquid crystal properties. A molecular liquid crystal compound or a polymer liquid crystal compound. When the side chain type liquid crystalline polymer compound is used as a composition, the proportion of the side chain type liquid crystalline polymer compound in the entire composition is 10% by mass or more, preferably 30% by mass or more. Especially preferably 50% by mass or more. When the content of the side chain type liquid crystalline polymer compound is less than 10% by mass, the film forming ability is insufficient, the polymerizable group concentration in the composition is lowered, and the mechanical strength after polymerization is insufficient, so that it is preferably avoided.
再者,上述液晶材料係經配向處理後,例如當所具有的反應性基係氧雜環丁烷基之情況,則藉由進行陽離子聚合而交聯,便可將該液晶狀態固定化。因而,液晶材料中,最好含有利用諸如光、熱等外部刺激而會產生陽離子的光陽離子產生劑及/或熱陽離子產生劑。此外,視需要亦可併用各種增感劑。Further, after the liquid crystal material is subjected to an alignment treatment, for example, in the case of a reactive oxetane group having a reactive group, the liquid crystal state can be immobilized by crosslinking by cationic polymerization. Therefore, it is preferable that the liquid crystal material contains a photocation generator and/or a thermal cation generator which generate cations by external stimuli such as light or heat. Further, various sensitizers may be used in combination as needed.
所謂「光陽離子產生劑」係指利用適當波長光的照射便會產生陽離子的化合物,可例示如有機鋶鹽系、錪鹽系、鏻鹽系等。該等化合物的離子對最好使用銻鹽、磷酸酯、硼酸鹽等。具體的化合物係可舉例如:Ar3 S+SbF6 - 、Ar3 P+ BF4 - 、Ar2 I+PF6 - (其中,Ar係指苯基或取代苯基)等。此外,尚可使用例如:磺酸酯類、三類、重氮甲烷類、β-酮碸、亞胺基磺酸酯、苯偶姻磺酸酯等。The term "photocation generating agent" refers to a compound which generates a cation by irradiation with light of a suitable wavelength, and examples thereof include an organic phosphonium salt system, an onium salt system, and an onium salt system. As the ion pair of these compounds, a phosphonium salt, a phosphate ester, a borate or the like is preferably used. Specific examples of the compound include Ar 3 S+SbF 6 - , Ar 3 P + BF 4 - , Ar 2 I+PF 6 - (wherein Ar is a phenyl group or a substituted phenyl group). In addition, it is also possible to use, for example, sulfonate esters, three Classes, diazomethanes, β-ketooximes, imidosulfonates, benzoin sulfonates, and the like.
所謂「熱陽離子產生劑」係指利用加熱至適當溫度便能產生陽離子的化合物,可舉例如:苄基鋶鹽類、苄基銨鹽類、苄基吡啶鎓鹽類、苄基鏻鹽類、肼鹽類、羧酸酯類、磺酸酯類、胺基醯亞胺類、五氯化銻-氯乙醯錯合物、二芳香基錪鹽-二苄氧基銅、鹵化硼-三級胺加成物等。The "thermal cation generating agent" refers to a compound which generates a cation by heating to a suitable temperature, and examples thereof include a benzyl sulfonium salt, a benzyl ammonium salt, a benzyl pyridinium salt, and a benzyl sulfonium salt. Bismuth salts, carboxylic acid esters, sulfonates, amine quinones, antimony pentachloride-chloroacetamidine complex, diaryl sulfonium salt - dibenzyloxy copper, boron halide - tertiary Amine adducts, etc.
該等陽離子產生劑對液晶材料中的添加量,係隨構成所使用液晶性高分子化合物的液晶原部分與間隙子部分之構造、以及氧雜環丁烷基當量、液晶配向條件等因素而異,並無法一概言之,但相對液晶性高分子化合物,通常將設定在100質量ppm~20質量%,最好1000質量ppm~10質量%,尤以0.2質量%~7質量%範圍內為佳。當較少於100質量ppm的情況,所產生的陽離子量不足,恐有無法進行聚合的可能性,反之,若多於20質量%的情況,配向液晶層中所殘存陽離子產生劑的分解殘存物等增加,而有導致耐光性等惡化的可能性,因而最好避免。The amount of the cation generating agent to be added to the liquid crystal material varies depending on the structure of the liquid crystal original portion and the spacer portion of the liquid crystalline polymer compound to be used, the oxetane group equivalent, and the liquid crystal alignment condition. It is not possible to generalize, but it is usually set to be in the range of 100 ppm by mass to 20% by mass, preferably 1,000 ppm by mass to 10% by mass, particularly preferably 0.2% by mass to 7% by mass, based on the liquid crystalline polymer compound. . When the amount is less than 100 ppm by mass, the amount of the generated cation is insufficient, and there is a possibility that the polymerization may not be carried out. On the other hand, if it is more than 20% by mass, the decomposition residue of the cation generating agent remaining in the alignment liquid crystal layer may be contained. If it increases, there is a possibility that the light resistance is deteriorated, so it is best to avoid it.
其次,針對配向基板進行說明。Next, the alignment substrate will be described.
當將相位差膜使用為配向基板的情況,雖亦有即便相位差膜仍可直接對液晶材料具有垂直配向能力者,但是若非屬此情況時,視需要最好施行後述配向處理(配向膜形成、摩擦處理等)。When the retardation film is used as the alignment substrate, even if the retardation film can directly have a vertical alignment ability to the liquid crystal material, if it is not the case, it is preferable to carry out the alignment treatment described later (alignment film formation). , friction treatment, etc.).
除相位差膜以外的配向基板,首要最好屬於具有平滑平面者,可舉例如由有機高分子材料構成的薄膜或薄片、或者諸如玻璃板、金屬板等。就從成本、連續生產性的觀點,最好使用由有機高分子構成的材料。有機高分子材料的例子,係可舉例由諸如:聚乙烯醇、聚醯亞胺、聚氧化二甲苯、聚苯硫、聚碸、聚醚酮、聚醚醚酮、聚芳香酯、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯系聚合物;二醋酸纖維素、三醋酸纖維素等纖維素系聚合物;聚碳酸酯系聚合物、聚甲基丙烯酸甲酯等丙烯酸系聚合物等等透明聚合物構成的薄膜。此外,尚可舉例由諸如:聚苯乙烯、丙烯腈‧苯乙烯共聚物等苯乙烯系聚合物;聚乙烯、聚丙烯、乙烯‧丙烯共聚物等烯烴系聚合物;聚環烯烴、氯乙烯系聚合物、尼龍、芳香族聚醯胺等醯胺系聚合物等等透明聚合物構成的薄膜。該等亦可為摻合物。The alignment substrate other than the retardation film preferably has a smooth plane, and may be, for example, a film or sheet made of an organic polymer material, or a glass plate, a metal plate or the like. From the viewpoint of cost and continuous productivity, it is preferable to use a material composed of an organic polymer. Examples of the organic polymer material may be exemplified by, for example, polyvinyl alcohol, polyimide, polyoxyxylene, polyphenylene sulfide, polyfluorene, polyether ketone, polyetheretherketone, polyarylester, polyparaphenylene. A polyester-based polymer such as ethylene dicarboxylate or polyethylene naphthalate; a cellulose-based polymer such as cellulose diacetate or cellulose triacetate; a polycarbonate polymer, polymethyl methacrylate, etc. A film composed of a transparent polymer such as an acrylic polymer. Further, examples thereof include styrene polymers such as polystyrene, acrylonitrile ‧ styrene copolymer; olefin polymers such as polyethylene, polypropylene, ethylene ‧ propylene copolymer; polycycloolefin, vinyl chloride A film composed of a transparent polymer such as a phthalamide polymer such as a polymer, a nylon or an aromatic polyamine. These may also be blends.
為能使用前述液晶材料,穩定地獲得垂直配向,構成該等基板的材料最好具有長鏈(通常碳數4以上,最好8以上)烷基或氟化烴基,或者基板表面設有含該等基的化合物層。另外,該等有機高分子材料係可單獨使用為基板,亦可在其他基板上形成薄膜。In order to stably obtain the vertical alignment using the liquid crystal material, the material constituting the substrates preferably has a long chain (usually a carbon number of 4 or more, preferably 8 or more) alkyl group or a fluorinated hydrocarbon group, or the substrate surface is provided with the An equivalent compound layer. Further, the organic polymer materials may be used alone as a substrate, or may be formed on other substrates.
針對具有長鏈(通常碳數4以上,最好8以上)烷基或氟化烴基之化合物層(配向膜)的形成步驟,進行說明。The step of forming a compound layer (alignment film) having a long chain (usually a carbon number of 4 or more, preferably 8 or more) of an alkyl group or a fluorinated hydrocarbon group will be described.
形成配向膜的材料係就從配向膜厚與表面性的控制觀點,最好依溶液狀態施行塗佈。該溶液係可使用能溶解該材料的溶劑適當實施。例如調製烷基改質聚乙烯醇(PVA)溶液的溶劑,係在屬於能溶解該PVA的溶劑之前提下,其餘並無特別的限制,通常可使用例如:水、或者甲醇、乙醇、異丙醇等低級醇、或者該等的混合物。The material forming the alignment film is preferably applied in a solution state from the viewpoint of controlling the film thickness and surface properties. This solution can be suitably carried out using a solvent capable of dissolving the material. For example, a solvent for preparing an alkyl modified polyvinyl alcohol (PVA) solution is taken up before being a solvent capable of dissolving the PVA, and the rest is not particularly limited, and usually, for example, water, or methanol, ethanol, or isopropyl alcohol can be used. A lower alcohol such as an alcohol or a mixture thereof.
另外,尚可添加在溶解時不會對塗佈、液晶配向造成不良影響的各種添加劑。此外,為能促進溶解亦可施行加溫。Further, various additives which do not adversely affect coating and liquid crystal alignment at the time of dissolution can be added. In addition, heating can be performed to promote dissolution.
為能在基材上形成配向膜而所使用的塗佈方式並無特別的限制,特別係就大面積配向膜的塗佈方法,可舉例如:使用柔軟樹脂版的橡膠版輪轉印刷方式、分配器方式、凹版塗佈方式、微凹版方式、網版印刷方式、刮刀塗佈方式、模頭塗佈方式等。該等之中,最好為凹版塗佈方式、刮刀塗佈方式、模頭塗佈方式。The coating method to be used for forming the alignment film on the substrate is not particularly limited, and in particular, a coating method for the large-area alignment film may be, for example, a rubber plate rotary printing method using a soft resin plate, and distribution. Device method, gravure coating method, micro gravure method, screen printing method, blade coating method, die coating method, and the like. Among these, a gravure coating method, a blade coating method, and a die coating method are preferable.
所塗佈的配向膜視需要施行乾燥。乾燥溫度通常就PVA的情況,雖就耐熱性有所限制,但依目的亦可在其以上。一般係設定為50℃~180℃,最好80℃~160℃。此外,乾燥時間亦無特別的限制,通常設定為10秒~60分鐘,最好1分~30分。被乾燥膜與乾燥風的相對移動速度係依相對風速計最好為60m/min~1200m/min。The coated alignment film is dried as needed. The drying temperature is usually in the case of PVA, although the heat resistance is limited, but it may be above the purpose. Generally, it is set to 50 ° C ~ 180 ° C, preferably 80 ° C ~ 160 ° C. In addition, the drying time is not particularly limited, and is usually set to 10 seconds to 60 minutes, preferably 1 minute to 30 minutes. The relative movement speed of the dried film and the dry wind is preferably from 60 m/min to 1200 m/min in terms of the relative anemometer.
在液晶領域中,一般係採取利用布等對基板朝一定方向施行擦拭的摩擦處理,但因為本發明所使用的垂直配向液晶層,係屬於基本上不會產生面內非等向性的配向構造,因而未必一定要施行摩擦處理。然而,為能抑制在將液晶材料施行塗佈時發生彈撥情形的觀點,最好施行輕摩擦處理。規範摩擦條件的重要設定值係周速比。該比值係指在將摩擦布捲繞於輥上並進行旋轉之情況下,對基板施行擦拭時,布移動速度與基板移動速度的比。本發明中,所謂「輕摩擦處理」通常係指周速比50以下,最好25以下,尤以10以下為佳。當周速比大於50時,摩擦效果過於強大,導致液晶材料無法完全呈垂直配向,恐有成為從垂直方向朝面內方向傾倒之配向的可能性。In the field of liquid crystals, rubbing treatment in which a substrate is wiped in a certain direction by a cloth or the like is generally employed. However, the vertical alignment liquid crystal layer used in the present invention is an alignment structure which does not substantially generate in-plane anisotropy. Therefore, it is not necessary to perform a rubbing treatment. However, in order to suppress the occurrence of plucking when the liquid crystal material is applied, it is preferable to perform a light rubbing treatment. The important set value for standardizing friction conditions is the weekly speed ratio. This ratio refers to the ratio of the cloth moving speed to the substrate moving speed when the substrate is wiped while the rubbing cloth is wound around the roll and rotated. In the present invention, the "light rubbing treatment" generally means a peripheral speed ratio of 50 or less, preferably 25 or less, particularly preferably 10 or less. When the peripheral speed ratio is greater than 50, the friction effect is too strong, and the liquid crystal material cannot be completely vertically aligned, and there is a possibility that the alignment is tilted from the vertical direction to the in-plane direction.
其次,針對本發明所使用垂直配向液晶層的製造方法進行說明。液晶層的製造方法並不僅侷限於該等,例如可將前述液晶材料在相位差膜或配向基板上展開,並使該液晶材料配向後,再藉由施行光照射及/或加熱處理,而將該配向狀態固定化便可製得。Next, a method of manufacturing the vertical alignment liquid crystal layer used in the present invention will be described. The method for manufacturing the liquid crystal layer is not limited to these. For example, the liquid crystal material may be spread on the retardation film or the alignment substrate, and the liquid crystal material may be aligned, and then subjected to light irradiation and/or heat treatment. The alignment state can be obtained by immobilization.
將液晶材料在相位差膜或配向基板上展開而形成液晶材料層的方法,係有如:將液晶材料依熔融狀態直接塗佈於配向基板上的方法,或者將液晶材料的溶液塗佈於配向基板上之後,再將塗膜乾燥且將溶劑餾除的方法。A method of forming a liquid crystal material layer by developing a liquid crystal material on a retardation film or an alignment substrate, such as a method of directly applying a liquid crystal material to a alignment substrate in a molten state, or applying a solution of a liquid crystal material to an alignment substrate After the above, the coating film is dried and the solvent is distilled off.
相關溶液調製時所使用的溶劑,係在能將本發明液晶材料溶解,且可依適當條件施行餾除的溶劑之前提下,其餘並無特別限制,一般最好使用例如:丙酮、甲乙酮、異佛爾酮、環己酮等酮類;丁氧基乙醇、己氧基乙醇、甲氧基-2-丙醇等醚醇類;乙二醇二甲醚、二乙二醇二甲醚等二醇醚類;醋酸乙酯、乳酸乙酯、γ-丁內酯等酯類;酚、氯酚等酚類;N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮等醯胺類;氯仿、四氯乙烷、二氯苯等鹵系等,或者該等的混合類。此外,為能在配向基板上形成均勻塗膜,亦可將諸如界面活性劑、消泡劑、均塗劑、著色劑等添加於溶液中。The solvent to be used in the preparation of the relevant solution is prepared before the solvent which can dissolve the liquid crystal material of the present invention and can be distilled off under appropriate conditions, and the rest is not particularly limited, and it is generally preferred to use, for example, acetone, methyl ethyl ketone or the like. Ketones such as phorone and cyclohexanone; ether alcohols such as butoxyethanol, hexyloxyethanol and methoxy-2-propanol; ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc. Alcohol ethers; esters such as ethyl acetate, ethyl lactate, γ-butyrolactone; phenols such as phenol and chlorophenol; N,N-dimethylformamide, N,N-dimethylacetamide And guanamine such as N-methylpyrrolidone; halogen such as chloroform, tetrachloroethane or dichlorobenzene; or a mixture of these. Further, in order to form a uniform coating film on the alignment substrate, a surfactant such as a surfactant, an antifoaming agent, a leveling agent, a coloring agent or the like may be added to the solution.
再者,為能使前述液晶性高分子化合物配向的固定化趨於容易順行,尚可添加諸如:1分子內具有與液晶性高分子化合物所鍵結之可聚合基為具有相同反應性之基2個以上的低分子化合物(不管液晶性或非液晶性均可)、或者能提升黏合性的各種化合物。In addition, in order to facilitate the aligning of the alignment of the liquid crystalline polymer compound, it is possible to add, for example, a polymerizable group bonded to a liquid crystalline polymer compound in one molecule to have the same reactivity. Two or more kinds of low molecular compounds (whether liquid crystal or non-liquid crystalline), or various compounds capable of improving adhesion.
不管直接將液晶性組成物施行塗佈的方法、或者將溶液施行塗佈的方法,相關塗佈方法均係在屬於能確保塗膜均勻性之方法的前提下,其餘並無特別的限制,可採用周知方法。例如:旋塗法、模頭塗佈法、淋幕塗佈法、浸塗法、滾筒塗佈法等。Regardless of the method of directly applying the liquid crystal composition or the method of applying the solution, the relevant coating method is based on the method of ensuring the uniformity of the coating film, and the rest is not particularly limited. A well-known method is employed. For example, a spin coating method, a die coating method, a curtain coating method, a dip coating method, a roll coating method, and the like.
將液晶性組成物的溶液施行塗佈之方法,最好在塗佈後,加入為將溶劑除去的乾燥步驟。該乾燥步驟係在屬於能維持塗膜均勻性之方法的前提下,其餘並無特別的限制,可採用周知方法。例如:加熱器(爐)、熱風吹抵等方法。In the method of applying a solution of the liquid crystal composition, it is preferred to add a drying step for removing the solvent after coating. The drying step is based on a method capable of maintaining the uniformity of the coating film, and the rest is not particularly limited, and a known method can be employed. For example: heater (furnace), hot air blowing, etc.
液晶層的膜厚係依存於液晶單元的方式、與各種光學參數,因而無法一概而言,通常設定為0.2μm~10μm,最好0.3μm~5μm,尤以0.5μm~2μm為佳。若膜厚薄於0.2μm時,恐有無法獲得充分地視角改良或輝度提升效果之可能性。反之,若超過10μm,恐有液晶顯示裝置會發生不必要著色等情況。The thickness of the liquid crystal layer depends on the liquid crystal cell and various optical parameters. Therefore, it is usually not particularly limited, and is usually 0.2 μm to 10 μm, preferably 0.3 μm to 5 μm, and particularly preferably 0.5 μm to 2 μm. When the film thickness is thinner than 0.2 μm, there is a possibility that a sufficient viewing angle improvement or brightness enhancement effect may not be obtained. On the other hand, if it exceeds 10 μm, there is a fear that unnecessary coloring may occur in the liquid crystal display device.
接著,將在配向基板上所形成的液晶性組成物層,利用熱處理等方法形成液晶配向,再利用光照射及/或加熱處理施行硬化而呈固定化。最初的熱處理係藉由加熱至所使用液晶性組成物的液晶相顯現溫度範圍,便可利用該液晶性組成物原本便擁有的自我配向能力使液晶配向。熱處理的條件係依照所使用液晶性組成物的液晶相行為溫度(轉移溫度),而有不同的最佳條件與極限值,因而並無法一概而言,通常設定在10~250℃,最好30℃~160℃範圍內,該液晶性組成物之玻璃轉移點(Tg)以上的溫度,尤以最好為依較Tg高出達10℃以上的溫度施行熱處理為佳。若過於低溫,恐有液晶配向無法充分進行的可能性,反之,若在高溫中,恐有對液晶性組成物中的陽離子聚合性反應基、或配向基板造成不良影響的可能性。此外,相關熱處理時間,通常設定在3秒~30分,最好10秒~20分範圍內。若短於3秒的熱處理時間,恐有液晶配向未能充分完成的可能性,反之,若超過30分鐘的熱處理時間,因為生產性將惡化,因而不管何種情況均最好避免。Next, the liquid crystal composition layer formed on the alignment substrate is formed into a liquid crystal alignment by a heat treatment or the like, and then cured by light irradiation and/or heat treatment to be immobilized. The initial heat treatment is performed by heating to the liquid crystal phase display temperature range of the liquid crystal composition to be used, whereby the liquid crystal composition can be aligned by the self-alignment ability originally possessed by the liquid crystal composition. The heat treatment conditions are based on the liquid crystal phase behavior temperature (transfer temperature) of the liquid crystal composition used, and have different optimum conditions and limit values, and thus cannot be generally set, and are usually set at 10 to 250 ° C, preferably 30 In the range of °C to 160 °C, the temperature above the glass transition point (Tg) of the liquid crystal composition is preferably preferably a heat treatment at a temperature higher than 10 ° C and higher than Tg. If the temperature is too low, there is a possibility that the liquid crystal alignment cannot be sufficiently performed. On the other hand, if it is at a high temperature, there is a possibility that the cationically polymerizable reactive group or the alignment substrate in the liquid crystal composition may be adversely affected. In addition, the relevant heat treatment time is usually set within a range of 3 seconds to 30 minutes, preferably 10 seconds to 20 minutes. If the heat treatment time is shorter than 3 seconds, there is a possibility that the liquid crystal alignment is not sufficiently completed. On the other hand, if the heat treatment time exceeds 30 minutes, since productivity is deteriorated, it is preferable to avoid it in any case.
利用對該液晶性組成物層施行熱處理等方法而形成液晶配向之後,在保持著液晶配向狀態下,藉由使液晶性組成物與該組成物中的氧雜環丁烷基產生反應而硬化。硬化步驟目的在於:使已完成的液晶配向利用硬化(交聯)反應,而將液晶配向狀態固定化,便改質為堅固的膜。After the liquid crystal alignment is formed by a method such as heat treatment on the liquid crystal composition layer, the liquid crystal composition is cured by reacting the liquid crystal composition with the oxetane group in the composition while maintaining the liquid crystal alignment state. The purpose of the hardening step is to use a hardening (crosslinking) reaction for the completed liquid crystal alignment, and to fix the liquid crystal alignment state to be a solid film.
因為本發明所使用的液晶性組成物係具有聚合性的氧雜環丁烷基,因而如前述在其進行聚合(交聯)時最好使用陽離子聚合起始劑(陽離子產生劑)。此外,聚合起始劑係相較於使用熱陽離子產生劑之下,最好使用光陽離子產生劑。Since the liquid crystalline composition used in the present invention has a polymerizable oxetane group, a cationic polymerization initiator (cation generator) is preferably used in the polymerization (crosslinking) as described above. Further, it is preferred to use a photocationic generator in comparison with the use of a thermal cation generator in the polymerization initiator.
當使用光陽離子產生劑的情況,若在光陽離子產生劑添加後,截至為施行液晶配向用的熱處理為止的步驟均在暗條件(光陽離子產生劑不會解離程度的光阻隔條件)下實施的話,液晶性組成物截至配向階段為止均不會硬化,具有充分的流動性,俾可施行液晶配向。然後,藉由照射會發出適當波長光之光源的光,產生陽離子,而使液晶組成物層硬化。When a photocationic cation generating agent is used, if the photothermal cation generating agent is added, the steps up to the heat treatment for liquid crystal alignment are carried out under dark conditions (light blocking conditions in which the photocation generating agent does not dissociate). The liquid crystal composition does not harden until the alignment stage, and has sufficient fluidity, so that liquid crystal alignment can be performed. Then, the liquid crystal composition layer is hardened by irradiating light of a light source that emits light of a suitable wavelength to generate a cation.
光照射的方法係照射在所使用光陽離子產生劑的吸收波長區域中具有光譜之諸如金屬鹵素燈、高壓水銀燈、低壓水銀燈、氙燈、弧光燈、雷射等光源的光,便將使光陽離子產生劑開裂。每1平方公分的照射量係依積分照射量計,通常設定為1~2000mJ,最好10~1000mJ範圍內。但,諸如光陽離子產生劑的吸收區域與光源光譜有明顯差異的情況、或者液晶性組成物本身便具有吸收來自光源光之吸收能力的情況等,便不在此限。該等情況下,亦可採行混合使用諸如:適當光增感劑、吸收波長不同的2種以上光陽離子產生劑等方法。The method of light irradiation is to irradiate light having a spectrum such as a metal halide lamp, a high pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, an arc lamp, a laser or the like in an absorption wavelength region of the photocation generator used, and the photocation will be generated. The agent is cracked. The irradiation amount per square centimeter is usually set to be in the range of 1 to 2000 mJ, preferably 10 to 1000 mJ, based on the integral irradiation amount. However, the case where the absorption region of the photocation generator is significantly different from the spectrum of the light source, or the liquid crystal composition itself has the ability to absorb the absorption light from the light source, is not limited thereto. In these cases, a method of mixing, for example, a suitable photosensitizer or two or more photocation generators having different absorption wavelengths may be employed.
光照射時的溫度必需設定為該液晶性組成物成為液晶配向的溫度範圍。此外,為能充分獲得硬化效果,最好依該液晶性組成物的Tg以上溫度施行光照射。The temperature at the time of light irradiation must be set to a temperature range in which the liquid crystal composition becomes a liquid crystal alignment. Further, in order to sufficiently obtain the hardening effect, it is preferred to perform light irradiation at a temperature higher than Tg of the liquid crystal composition.
藉由以上步驟所製得液晶性組成物層成為充分堅固的膜。具體而言,利用硬化反應使液晶原進行三維式鍵結,相較於硬化前之下,不僅將提升耐熱性(液晶配向保持的上限溫度),即使相關耐刮傷性、耐磨耗性、耐龜裂性等機械強度亦可大幅提升。The liquid crystal composition layer obtained by the above steps became a sufficiently strong film. Specifically, the liquid crystal element is three-dimensionally bonded by the hardening reaction, and the heat resistance (the upper limit temperature of the liquid crystal alignment retention) is improved not only before and after the curing, but also related to scratch resistance and wear resistance. The mechanical strength such as crack resistance can be greatly improved.
另外,配向基板係光學性非屬等向性,或者所獲得液晶薄膜在最終目標的使用波長區域中呈不透明,或者當配向基板膜厚過厚,但在實際使用上並不造成阻礙等問題的情況下,在形成於配向基板上的形態中,將目標所使用波長區域中部會造成阻礙的基板、或具有相位差功能的延伸薄膜上之形態亦均可使用。轉印方法係可採用周知方法。例如日本專例特開平4-57017號公報、特開平5-333313號公報所記載,將液晶薄膜層隔著黏著劑或接著劑,積層著不同於配向基板的基板之後,再從該積層體上將配向基板剝離,而僅轉印液晶層的方法等。Further, the alignment substrate is optically non-isotropic, or the obtained liquid crystal film is opaque in the final target wavelength region, or when the alignment substrate film thickness is too thick, but the practical use does not cause hindrance and the like. In other cases, in the form formed on the alignment substrate, a substrate on the middle of the wavelength region to be used for the target or a form on the stretched film having a phase difference function can be used. The transfer method can employ a well-known method. In the liquid crystal film layer, a substrate different from the alignment substrate is laminated on the liquid crystal film layer via an adhesive or an adhesive, and then from the laminate, as described in JP-A-H05-333313. A method of peeling off the alignment substrate, and transferring only the liquid crystal layer.
轉印時所使用的黏合劑或接著劑,係只要屬於光學等級的話便可,其餘並無特別的限制,可使用諸如:丙烯酸系、環氧系、胺基甲酸乙酯系等一般常使用的物質。The adhesive or the adhesive to be used for the transfer may be an optical grade, and the rest is not particularly limited, and those commonly used such as acrylic, epoxy, and urethane may be used. substance.
依如上述所獲得的垂直配向液晶層,係該液晶層的光學相位差藉由依傾斜垂直入射的角度施行測定便可定量化。垂直配向液晶層的情況,該相位差值係相對垂直入射呈對稱性。光學相位差的測定係可利用數種方法,例如可利用自動複折射測定裝置(王子計測機器(股)製)及偏光顯微鏡。該垂直配向液晶層係在正交偏光之偏光元件間將觀看到黑色。依此施行垂直配向性的評估。According to the vertical alignment liquid crystal layer obtained as described above, the optical phase difference of the liquid crystal layer can be quantified by performing measurement at an obliquely perpendicular incidence angle. In the case of a vertically aligned liquid crystal layer, the phase difference is symmetrical with respect to normal incidence. There are several methods for measuring the optical phase difference, and for example, an automatic birefringence measuring device (manufactured by Oji Scientific Instruments Co., Ltd.) and a polarizing microscope can be used. The vertical alignment liquid crystal layer will be black between the polarized elements that are orthogonally polarized. Based on this, an evaluation of vertical alignment is performed.
本發明所使用的垂直配向液晶層,係當將液晶層厚度設為d1,將液晶層面內的主折射率設為Nx1與Ny1,將厚度方向的主折射率設為Nz1,且Nz1>Nx1≧Ny1的情況,面內的延遲值(Re1=(Nx1-Ny1)×d1[nm])及厚度方向的延遲值(Rth1=(Nx1-Nz1)×d1[nm]),最好滿足下式[1]與[2]:The vertical alignment liquid crystal layer used in the present invention has a liquid crystal layer thickness of d1, a main refractive index in the liquid crystal layer of Nx1 and Ny1, a main refractive index in the thickness direction of Nz1, and Nz1>Nx1≧. In the case of Ny1, the in-plane retardation value (Re1=(Nx1-Ny1)×d1[nm]) and the retardation value in the thickness direction (Rth1=(Nx1-Nz1)×d1[nm]) preferably satisfy the following formula [ 1] and [2]:
[1]0nm≦Re1≦20nm[1]0nm≦Re1≦20nm
[2]-500nm≦Rth1≦-30nm[2]-500nm≦Rth1≦-30nm
因為垂直配向液晶層光學參數的Re1值、Rth1值,依存於液晶顯示裝置的方式與各種光學參數,因而不能一概言之,相對於550nm單色光,面內的延遲值(Re1),通常控制在0nm~20nm,最好0nm~10nm,尤以0nm~5nm範圍內為佳,且厚度方向的延遲值(Rth1),通常控制在-500nm~-30nm,最好-400nm~-50nm,尤以-400nm~-100nm為佳。Since the Re1 value and the Rth1 value of the optical parameters of the vertical alignment liquid crystal layer depend on the mode of the liquid crystal display device and various optical parameters, it cannot be said in general, and the in-plane retardation value (Re1) is usually controlled with respect to the 550 nm monochromatic light. In the range of 0 nm to 20 nm, preferably 0 nm to 10 nm, particularly preferably in the range of 0 nm to 5 nm, and the retardation value (Rth1) in the thickness direction is usually controlled at -500 nm to -30 nm, preferably -400 nm to -50 nm, especially -400nm~-100nm is preferred.
藉由將上述Re1值與Rth1值設定在上述範圍內,液晶顯示裝置的視角改良薄膜,便可一邊施行液晶顯示的色調校正,一邊擴大視角。當Re1值大於20nm的情況,因較大的正面相位差值之影響,恐有導致液晶顯示裝置的正面特性惡化的可能性。此外,當Rth1值大於-30nm或小於-500nm的情況,恐有無法獲得充分的視角改良效果或斜向觀看時產生不必要著色的可能性。By setting the Re1 value and the Rth1 value within the above range, the viewing angle improving film of the liquid crystal display device can expand the viewing angle while performing tone correction of the liquid crystal display. When the Re1 value is larger than 20 nm, there is a possibility that the front characteristics of the liquid crystal display device are deteriorated due to the influence of a large front surface difference value. Further, when the Rth1 value is larger than -30 nm or smaller than -500 nm, there is a fear that a sufficient viewing angle improvement effect or a possibility of unnecessary coloring when obliquely viewing is not obtained.
再者,垂直配向液晶層最好滿足下述[5]所示條件:Further, the vertical alignment liquid crystal layer preferably satisfies the conditions shown in the following [5]:
[5]-0.5≦Δn≦-0.0005(Δn=Nx1-Nz1)[5]-0.5≦Δn≦-0.0005(Δn=Nx1-Nz1)
另外,就從生產性提升、含垂直配向液晶層的橢圓偏光板薄型化之觀點,尤以-0.2≦Δn≦-0.005為佳。Further, in view of the improvement in productivity and the thinning of the elliptically polarizing plate including the vertical alignment liquid crystal layer, it is preferable to use -0.2 ≦ Δn ≦ - 0.005.
即使取代垂直配向液晶層,將厚度方向具有正單軸性的光學非等向性元件改為使用延伸薄膜,因為在厚度方向的延伸仍有極限限制,因而無法將厚度方向的相位差控制於廣範圍內。此外,雖亦有使用藉由熱收縮膜,使長條薄膜進行熱收縮而朝厚度方向延伸的手法,但依厚度方向的複折射率0.003以下所獲得薄膜的厚度係50~100μm左右,厚度較原本長條薄膜增加,而頗難因應隨液晶顯示裝置薄型化要求所衍生對橢圓偏光板整體薄膜化的要求。Even if the vertical alignment liquid crystal layer is replaced, the optical anisotropic element having a positive uniaxiality in the thickness direction is changed to the use of the extension film, since there is still a limit in the extension in the thickness direction, and thus the phase difference in the thickness direction cannot be controlled widely. Within the scope. Further, although a method in which a long film is thermally contracted by a heat shrinkable film and extends in the thickness direction is used, the thickness of the film obtained by a complex refractive index of 0.003 or less in the thickness direction is about 50 to 100 μm, and the thickness is relatively small. The original long strip film has increased, and it is difficult to meet the requirements for the overall thinning of the elliptically polarizing plate due to the thinning requirements of the liquid crystal display device.
橢圓偏光板的膜厚就從近年薄型化要求的觀點,最好在175μm以下,尤以150μm以下為佳。The film thickness of the elliptically polarizing plate is preferably 175 μm or less, and particularly preferably 150 μm or less, from the viewpoint of the demand for thinning in recent years.
構成本發明橢圓偏光板的直線偏光板係僅在偏光元件的單側設有透光性保護膜。所使用的偏光元件並無特別的限制,可使用各種物質,可舉例如:使在諸如聚乙烯醇系薄膜、部分縮甲醛化聚乙烯醇系薄膜、乙烯‧醋酸乙烯酯共聚物系部分皂化薄膜等親水性高分子薄膜上,吸附著諸如碘、二色性染料等二色性物質,並施行單軸延伸的物質,或者聚乙烯醇的脫水處理物、聚氯乙烯的脫鹽酸處理物等多烯系配向薄膜等等。該等之中,最好使用將聚乙烯醇系薄膜施行延伸,並吸附二色性材料(碘、染料)且施行配向者。偏光元件的厚度並無特別的限制,一般係5~80μm左右。The linear polarizing plate constituting the elliptically polarizing plate of the present invention is provided with a light-transmitting protective film only on one side of the polarizing element. The polarizing element to be used is not particularly limited, and various materials can be used, and for example, a partially saponified film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or an ethylene vinyl acetate copolymer system can be used. On the hydrophilic polymer film, a dichroic substance such as iodine or a dichroic dye is adsorbed, and a uniaxially stretched substance or a dehydrated material of polyvinyl alcohol or a dehydrochlorinated product of polyvinyl chloride is adsorbed. An olefinic alignment film or the like. Among these, it is preferable to use a polyvinyl alcohol-based film to stretch and adsorb a dichroic material (iodine or dye) and to perform alignment. The thickness of the polarizing element is not particularly limited, and is generally about 5 to 80 μm.
將聚乙烯醇系薄膜利用碘施行染色並施行單軸延伸的偏光元件,例如將聚乙烯醇浸漬於碘水溶液中而染色,再藉由延伸為原長的3~7倍便可進行製作。視需要,亦可浸漬於諸如硼酸、碘化鉀等的水溶液中。此外,視需要,亦可在施行染色之前,便將聚乙烯醇系薄膜浸漬於水中而施行水洗。藉由將聚乙烯醇系薄膜施行水洗,除可將聚乙烯醇系薄膜表面髒污與防結塊劑施行洗淨之外,亦可藉由使聚乙烯醇系薄膜膨潤,而防止染色斑點等不均勻現象的效果。延伸係可在經利用碘施行染色後才實施,亦可一邊施行染色一邊施行延伸,且亦可一邊施行延伸,一邊利用碘施行染色。即使在諸如硼酸、碘化鉀等的水溶液中、或水浴中仍可施行延伸。The polyvinyl alcohol-based film is dyed by iodine and subjected to uniaxially extending polarizing elements. For example, polyvinyl alcohol is immersed in an aqueous iodine solution and dyed, and then produced by stretching 3 to 7 times the original length. If necessary, it may be immersed in an aqueous solution such as boric acid, potassium iodide or the like. Further, if necessary, the polyvinyl alcohol-based film may be immersed in water and subjected to water washing before dyeing. By washing the polyvinyl alcohol-based film with water, the surface of the polyvinyl alcohol-based film can be cleaned and the anti-caking agent can be washed, and the polyvinyl alcohol-based film can be swollen to prevent stain spots and the like. The effect of unevenness. The extension system can be carried out after dyeing with iodine, or can be performed while performing dyeing, and can be dyed with iodine while performing stretching. The extension can be carried out even in an aqueous solution such as boric acid, potassium iodide or the like, or in a water bath.
在上述偏光元件單側所設置的透光性保護薄膜,最好屬於透明性、機械強度、熱穩定性、水分遮蔽性及等向性等均優越者。上述透光性保護薄膜的材料係可舉例如:聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯系聚合物;二醋酸纖維素、三醋酸纖維素等纖維素系聚合物;聚甲基丙烯酸甲酯等丙烯酸系聚合物;聚苯乙烯、丙烯腈˙苯乙烯共聚物(AS樹脂)等苯乙烯系聚合物;聚碳酸酯系聚合物等。此外,形成透光性保護膜的聚合物例,尚可舉例如:聚乙烯、聚丙烯、乙烯˙丙烯共聚物等聚烯烴系聚合物;環烯烴系聚合物;氯乙烯系聚合物;尼龍、芳香族聚醯胺等醯胺系聚合物;醯亞胺系聚合物、碸系聚合物、聚醚碸系聚合物、聚醚醚酮系聚合物、聚苯硫系聚合物、乙烯醇系聚合物、偏二氯乙烯系聚合物、乙烯縮丁醛系聚合物、芳香酯系聚合物、聚甲醛系聚合物、環氧系聚合物、或上述聚合物的摻合物等。另外,尚可舉例將諸如:丙烯酸系、胺基甲酸乙酯系、丙烯酸胺甲酸乙酯系、環氧系、聚矽氧系等熱硬化型或紫外線硬化型樹脂等,施行薄膜化者等等。透光性保護膜的厚度,一般係設定在100μm以下,最好1~80μm。特以5~50μm為佳。The light-transmitting protective film provided on one side of the polarizing element is preferably superior in transparency, mechanical strength, thermal stability, moisture shielding property, and isotropic property. The material of the light-transmitting protective film may, for example, be a polyester-based polymer such as polyethylene terephthalate or polyethylene naphthalate; or cellulose-based polymerization such as cellulose diacetate or cellulose triacetate. An acrylic polymer such as polymethyl methacrylate; a styrene polymer such as polystyrene or acrylonitrile styrene copolymer (AS resin); or a polycarbonate polymer. Further, examples of the polymer forming the light-transmitting protective film include polyolefin-based polymers such as polyethylene, polypropylene, and ethylene-propylene copolymer; cycloolefin polymers; vinyl chloride polymers; and nylon. A guanamine-based polymer such as an aromatic polyamine; a ruthenium-based polymer, a fluorene-based polymer, a polyether fluorene-based polymer, a polyetheretherketone-based polymer, a polyphenylene-sulfur-based polymer, or a vinyl alcohol-based polymerization A vinylidene chloride polymer, an ethylene butyral polymer, an aromatic ester polymer, a polyoxymethylene polymer, an epoxy polymer, or a blend of the above polymers. Further, for example, a thermosetting type or an ultraviolet curing type resin such as an acrylic type, an urethane type, an urethane type urethane type, an epoxy type or a polyoxymethylene type, etc. . The thickness of the light-transmitting protective film is generally set to 100 μm or less, preferably 1 to 80 μm. It is preferably 5~50μm.
透光性保護膜係就從偏光特性、耐久性等觀點,最好為三醋酸纖維素等纖維素系聚合物、或環烯烴系聚合物。The light-transmitting protective film is preferably a cellulose-based polymer such as cellulose triacetate or a cycloolefin-based polymer from the viewpoints of polarization characteristics, durability, and the like.
上述偏光元件與透光性保護膜,通常經由黏著劑、接著劑等而密接。The polarizing element and the light-transmitting protective film are usually adhered to each other via an adhesive, an adhesive, or the like.
黏著劑、接著劑係可例示如:聚乙烯醇系、明膠系、乙烯系乳膠系、水系聚胺基甲酸酯、水系聚酯等。Examples of the adhesive and the adhesive agent include polyvinyl alcohol type, gelatin type, ethylene type latex type, aqueous polyurethane, and aqueous polyester.
上述透光性保護膜係可使用硬塗層,或在以抗反射處理、抗黏、擴散或防眩為目的而施行處理過的物質。The above-mentioned light-transmitting protective film may be a hard coat layer or a substance treated for the purpose of anti-reflection treatment, anti-sticking, diffusion or anti-glare.
硬塗處理係在偏光板表面防刮傷等目的下實施,例如將由諸如丙烯酸系、聚矽氧系等適當紫外線硬化型樹脂,所形成的硬度與平滑特性等均優越的硬化皮膜,附加於保護膜表面的方式等便可形成。抗反射處理係在偏光板表面的外光抗反射之目的下實施,可依照習知的抗反射膜等形成便可達成。此外,抗黏處理係在防止與鄰接層發生密接之目的下實施。The hard coat treatment is carried out for the purpose of preventing scratches on the surface of the polarizing plate, and for example, a hardened film which is excellent in hardness and smoothness by a suitable ultraviolet curable resin such as acrylic or polyoxygen is added to the protective film. A film surface or the like can be formed. The antireflection treatment is carried out for the purpose of external light antireflection on the surface of the polarizing plate, and can be achieved by forming a conventional antireflection film or the like. Further, the anti-adhesive treatment is carried out for the purpose of preventing adhesion to an adjacent layer.
再者,防眩處理係在防止偏光板表面將外光反射,而阻礙偏光板穿透光檢視等目的下實施,例如利用砂磨方式或壓花加工方式施行粗面化方式、或調配入透明微粒子的方式等適當方式,藉由對保護膜表面賦予細微凹凸構造便可形成。上述表面細微凹凸構造的形成中所含有之微粒子,係可使用由諸如平均粒徑0.5~50μm的二氧化矽、氧化鋁、二氧化鈦、氧化鋯、氧化錫、氧化銦、氧化鎘、氧化銻等所構成且具有導電性的無機系微粒子,或由交聯或未交聯聚合物等所構成的有機系微粒子等透明微粒子。形成表面細微凹凸構造的情況,微粒子的使用量係相對於形成表面細微凹凸構造的透明樹脂100重量份,一般將使用2~50重量份左右,最好5~25重量份。防眩層亦可兼具將偏光板穿透光擴散而擴大視角等之用的擴散層(視角擴大功能等)。Further, the anti-glare treatment is performed by preventing the external light from being reflected on the surface of the polarizing plate and preventing the polarizing plate from penetrating the light, for example, by sanding or embossing, or by blending into a transparent method. An appropriate method such as a method of applying fine particles can be formed by imparting a fine concavo-convex structure to the surface of the protective film. The fine particles contained in the formation of the fine uneven structure on the surface may be made of, for example, ceria, alumina, titania, zirconia, tin oxide, indium oxide, cadmium oxide, or cerium oxide having an average particle diameter of 0.5 to 50 μm. Inorganic fine particles having conductivity and conductivity, or transparent fine particles such as organic fine particles composed of a crosslinked or uncrosslinked polymer. In the case where the surface fine uneven structure is formed, the amount of the fine particles used is generally from 2 to 50 parts by weight, preferably from 5 to 25 parts by weight, per 100 parts by weight of the transparent resin forming the surface fine uneven structure. The anti-glare layer may also have a diffusion layer (a viewing angle expansion function or the like) for diffusing the polarizing plate through the light to expand the viewing angle or the like.
另外,上述抗反射層、抗黏層、擴散層、防眩層等係除可設置於該保護膜上之外,尚可依在透光性保護膜之外,另外設置的光學層形式設置。Further, the anti-reflection layer, the anti-adhesion layer, the diffusion layer, the anti-glare layer, and the like may be provided on the protective film, and may be provided in addition to the light-transmitting protective film and additionally provided in the form of an optical layer.
其次,針對具有相位差功能的相位差膜進行說明。Next, a retardation film having a phase difference function will be described.
該相位差膜係只要具有所需相位差功能的話便可,例如:將聚合物薄膜施行單軸延伸或雙軸延伸者、或朝厚度方向(Z軸)施行配向處理者、或經將呈液晶性的材料施行塗佈/配向的配向薄膜等。The retardation film may have a desired phase difference function, for example, a uniaxially stretched or biaxially stretched polymer film, or an alignment processor in the thickness direction (Z axis), or a liquid crystal The material is applied to a coating/alignment alignment film or the like.
具有相位差功能的相位差膜,最好滿足下式[3]及[4]:A retardation film having a phase difference function preferably satisfies the following formulas [3] and [4]:
[3]20nm≦Re2≦200nm[3]20nm≦Re2≦200nm
[4]0nm≦Rth2≦30nm[4]0nm≦Rth2≦30nm
其中,Re2係指相位差膜面內的延遲值;Rth2係指上述相位差膜厚度方向的延遲值。上述Re2及Rth2分別係為Re2=(Nx2-Ny2)×d2[nm]、Rth2=(Nx2-Nz2)×d2[nm]。此外,d2係指上述相位差膜的厚度,Nx2及Ny2係指上述相位差膜面內的主折射率,Nz2係指厚度方向的主折射率,且Nx2>Ny2≧Nz2。Here, Re2 means a retardation value in the plane of the retardation film; and Rth2 means a retardation value in the thickness direction of the retardation film. Re2 and Rth2 are respectively Re2=(Nx2-Ny2)×d2[nm], and Rth2=(Nx2-Nz2)×d2[nm]. Further, d2 means the thickness of the retardation film, Nx2 and Ny2 means the main refractive index in the plane of the retardation film, and Nz2 means the main refractive index in the thickness direction, and Nx2>Ny2≧Nz2.
因為相位差膜光學參數的Re2值、Rth2值,依存於液晶顯示裝置的方式與各種光學參數,因而不能一概言之,相對於550nm單色光,面內的延遲值(Re2),通常控制在20nm~200nm,最好30nm~180nm,尤以50nm~160nm範圍內為佳,且厚度方向的延遲值(Rth2),通常控制在0nm~30nm,最好0nm~25nm,尤以0nm~15nm為佳。Since the Re2 value and the Rth2 value of the retardation film optical parameter depend on the mode of the liquid crystal display device and various optical parameters, it cannot be said in general, and the in-plane retardation value (Re2) is usually controlled in relation to the 550 nm monochromatic light. 20nm~200nm, preferably 30nm~180nm, especially in the range of 50nm~160nm, and the retardation value (Rth2) in the thickness direction is usually controlled from 0nm to 30nm, preferably 0nm~25nm, especially 0nm~15nm. .
藉由將上述Re2值與Rth2值設定在上述範圍內,液晶顯示裝置的視角改良薄膜,便可一邊施行液晶顯示的色調校正,一邊擴大視角。當Re2值小於20nm、或大於200nm的情況,因受面內相位差值的影響,恐有導致液晶顯示元件的正面特性惡化之可能性。此外,當Rth2值小於0nm、或大於30nm的情況,恐有無法獲得充分的視角改良效果、或斜向觀看時將發生不必要著色情形的可能性。By setting the Re2 value and the Rth2 value within the above range, the viewing angle improving film of the liquid crystal display device can expand the viewing angle while performing tone correction of the liquid crystal display. When the Re2 value is less than 20 nm or more than 200 nm, there is a possibility that the front surface characteristics of the liquid crystal display element are deteriorated due to the influence of the in-plane retardation value. Further, when the Rth2 value is less than 0 nm or more than 30 nm, there is a possibility that a sufficient viewing angle improvement effect or a case where unnecessary coloring occurs in oblique viewing may not be obtained.
上述相位差膜最好係利用將由適當聚合物所構成薄膜施行單軸或雙軸延伸處理的手法,或者利用如日本專利特開平5-157911號公報所揭示,依熱收縮膜使長條薄膜的寬度方向進行熱收縮,而在厚度方向上呈現較大相位差的手法所製得複折射薄膜,上述原料係可舉例如由有機高分子材料構成的薄膜或薄片。例如由諸如:聚乙烯醇、聚醯亞胺、聚氧化二甲苯、聚碸、聚醚酮、聚醚醚酮、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯系聚合物二醋酸纖維素;三醋酸纖維素等纖維素系聚合物;聚碳酸酯系聚合物、聚甲基丙烯酸甲酯等丙烯酸系聚合物等等透明聚合物構成的薄膜。此外,尚可舉例由諸如:聚苯乙烯、丙烯腈˙苯乙烯共聚物等苯乙烯系聚合物;聚乙烯、聚丙烯、聚環烯烴、乙烯˙丙烯共聚物等烯烴系聚合物;氯乙烯系聚合物;尼龍、芳香族聚醯胺等醯胺系聚合物等等透明聚合物構成的薄膜。另外,尚可舉例由諸如:偏二氯乙烯系聚合物、乙烯縮丁醛系聚合物、芳香酯系聚合物、聚甲醛系聚合物、環氧系聚合物、上述聚合物的摻合物等透明聚合物所構成薄膜等。該等之中,光學薄膜將建議使用諸如:三醋酸纖維素、聚碳酸酯、聚環烯烴等塑膠薄膜。有機高分子材料的薄膜特別以使用諸如:ZEONOR(商品名,日本ZEON(股)製)、ZEONEX(商品名,日本ZEON(股)製)、Arton(商品名,JSR(股)製)等,由具有降烯結構之聚合物物質所構成塑膠薄膜為佳。The retardation film is preferably a method of performing uniaxial or biaxial stretching treatment of a film composed of a suitable polymer, or a film of a long film according to a heat shrinkable film as disclosed in Japanese Laid-Open Patent Publication No. Hei 5-157911. A birefringent film is obtained by heat-shrinking in the width direction and exhibiting a large phase difference in the thickness direction, and the material is, for example, a film or sheet made of an organic polymer material. For example, polyesters such as polyvinyl alcohol, polyimide, polyoxyxylene, polyfluorene, polyether ketone, polyetheretherketone, polyethylene terephthalate, polyethylene naphthalate, and the like A film composed of a polymer such as cellulose diacetate; a cellulose polymer such as cellulose triacetate; a transparent polymer such as a polycarbonate polymer or an acrylic polymer such as polymethyl methacrylate. Further, examples thereof include styrene polymers such as polystyrene and acrylonitrile styrene copolymer; olefin polymers such as polyethylene, polypropylene, polycycloolefin, and ethylene propylene copolymer; and vinyl chloride. A film composed of a transparent polymer such as a nylon, an aromatic polyamide or the like. Further, examples thereof include a vinylidene chloride-based polymer, an ethylene butyral-based polymer, an aromatic ester-based polymer, a polyoxymethylene-based polymer, an epoxy-based polymer, a blend of the above polymers, and the like. A film made of a transparent polymer or the like. Among these, optical films will be recommended to use plastic films such as cellulose triacetate, polycarbonate, and polycycloolefin. For the film of the organic polymer material, for example, ZEONOR (trade name, manufactured by Japan ZEON Co., Ltd.), ZEONEX (trade name, manufactured by Japan ZEON Co., Ltd.), Arton (trade name, manufactured by JSR Co., Ltd.), and the like are used. By having a drop A plastic film composed of a polymer material of an olefin structure is preferred.
依延伸等所獲得相位差膜的膜厚,如上述,依存於Re2、Rth2,但通常設定為5μm~100μm,最好10μm~80μm。The film thickness of the retardation film obtained by stretching or the like depends on Re2 and Rth2 as described above, but is usually set to 5 μm to 100 μm, preferably 10 μm to 80 μm.
由諸如液晶聚合物等液晶材料所構成配向薄膜,係可舉例如:將呈現均勻且單一區域的向列配向性,且可輕易將配向狀態固定化的液晶性高分子,在基板上、或經塗佈配向膜的基板上施行熱處理,而形成均勻、單一區域向列構造之後,再施行冷卻,而在不損及液晶狀態的配向之情況下施行固定化所製得配向薄膜;或者在上述液晶性高分子中調配入光聚合性液晶化合物而形成液晶性組成物,並在基板上、或經塗佈配向膜的基板上施行塗佈/配向,再施行聚合的配向薄膜。The alignment film composed of a liquid crystal material such as a liquid crystal polymer may, for example, be a liquid crystalline polymer which exhibits a nematic alignment property which is uniform and a single region, and which can be easily fixed in an alignment state, on a substrate or via Applying a heat treatment on the substrate on which the alignment film is applied to form a uniform, single-region nematic structure, and then performing cooling to form an alignment film obtained by immobilization without damaging the alignment of the liquid crystal state; or The photopolymerizable liquid crystal compound is blended into a polymer to form a liquid crystal composition, and an alignment film which is subjected to polymerization is applied to a substrate or a substrate on which an alignment film is applied.
其次,針對可對本發明橢圓偏光板進行積層的光學薄膜進行說明。Next, an optical film which can laminate the elliptically polarizing plate of the present invention will be described.
上述光學薄膜係可為正單軸光學非等向性層、亦可為負單軸光學非等向性層,此外亦可為雙軸光學非等向性層。The optical film may be a positive uniaxial optical anisotropic layer, a negative uniaxial optical anisotropic layer, or a biaxial optical anisotropic layer.
當將面內方向設為x方向、y方向,而將厚度方向設為z方向的情況,正單軸性光學非等向性元件係折射率具有nx>ny=nz的關係。此外,正雙軸性光學非等向性元件係折射率具有nx>nz>ny的關係。負單軸性光學非等向性元件係折射率具有nx=ny>nz的關係。負雙軸性光學非等向性元件具有nx>ny>nz的關係。When the in-plane direction is the x direction and the y direction, and the thickness direction is the z direction, the positive uniaxial optical anisotropic element has a refractive index of nx>ny=nz. Further, the positive biaxial optical anisotropic element has a refractive index having a relationship of nx>nz>ny. The negative uniaxial optical anisotropic element has a refractive index of nx=ny>nz. The negative biaxial optical anisotropic element has a relationship of nx>ny>nz.
當雙軸性係依NZ係數=(nx-nz)/(nx-ny)定義時,便可分類為:NZ>1係負雙軸、NZ=1係正單軸、NZ<1係正雙軸。When the biaxial system is defined by the NZ coefficient = (nx-nz) / (nx-ny), it can be classified into: NZ>1 system negative biaxial, NZ=1 system positive uniaxial, NZ<1 system positive double axis.
因為正單軸光學非等向性層係具有上述相位差功能的相位差膜,因而若延遲值在下述範圍內適當選定便可。Since the positive uniaxial optical anisotropic layer has a retardation film having the above-described phase difference function, the retardation value can be appropriately selected within the following range.
該薄膜面內的延遲Re係20nm~500nm,最好50nm~300nm。若超出該範圍外,當適用於液晶顯示裝置時的視角改良等效果較欠缺,因而最好避免。另外,Re係如同前述就具有相位差功能的相位差膜中所定義式子。The retardation Re in the plane of the film is 20 nm to 500 nm, preferably 50 nm to 300 nm. If it is outside this range, the effect of improving the viewing angle when applied to a liquid crystal display device is lacking, and thus it is preferable to avoid it. Further, Re is a formula defined in a retardation film having a phase difference function as described above.
具有負單軸光學非等向性層的光學薄膜並無特別的限制,因為非液晶材料係耐熱性、耐藥性、透明性均優越,且亦富剛性,因而最好為例如:纖維素三丙烯酸酯、ZEONEX、ZEONOR(均屬日本ZEON(股)製)、Arton(JSR(股)製)之類的聚烯烴類;聚醯胺、聚醯亞胺、聚酯、聚醚酮、聚芳香醚酮、聚醯胺醯亞胺、聚酯醯亞胺等聚合物。該等聚合物均可單獨使用一種,亦可使用如聚芳香醚酮與聚醯胺的混合物之類,2種以上具有不同官能基的混合物。此種聚合物中,就從高透明性、高配向性的觀點,最好為聚醯亞胺。聚醯亞胺最好例如面內配向性高、且可溶於有機溶劑中的聚醯亞胺。例如日本專利特表2000-511296號公報所揭示9,9-雙(胺基芳香基)茀與芳香族四羧酸二酐的縮合聚合生成物,具體係可使用含有1以上由下式(7)所示重複單位的聚合物。The optical film having a negative uniaxial optical anisotropic layer is not particularly limited since the non-liquid crystal material is excellent in heat resistance, chemical resistance, transparency, and also rigid, and thus is preferably, for example, cellulose three. Acrylate, ZEONEX, ZEONOR (all manufactured by Japan ZEON Co., Ltd.), polyolefins such as Arton (made by JSR); polyamine, polyimine, polyester, polyether ketone, poly aromatic A polymer such as an ether ketone, a polyamidoximine or a polyester quinone. These polymers may be used singly or in the form of a mixture of two or more kinds of functional groups such as a mixture of a poly(aryl ether ketone) and a polyamidamine. Among such polymers, polyiminoimide is preferred from the viewpoint of high transparency and high alignment. The polyimine is preferably, for example, a polyimine which has high in-plane orientation and is soluble in an organic solvent. For example, a condensation polymerization product of 9,9-bis(aminoaryl)fluorene and an aromatic tetracarboxylic dianhydride disclosed in Japanese Patent Laid-Open Publication No. 2000-511296, specifically, may contain one or more of the following formula (7). ) The repeating unit of the polymer shown.
上式(7)中,R3 ~R6 係指從氫、鹵、苯基、依1~4個鹵原子或C1 ~10 烷基進行取代的苯基及C1 ~10 烷基所構成群組中分別獨立選擇的至少一種取代基。最好R3 ~R6 係從鹵、苯基、依1~4個鹵原子或C1 ~10 烷基進行取代的苯基及C1 ~10 烷基所構成群組中分別獨立選擇的至少一種取代基。In the above formula (7), R 3 to R 6 are each a hydrogen group, a halogen group, a phenyl group, a phenyl group substituted by 1 to 4 halogen atoms or a C 1 10 alkyl group, and a C 1 10 alkyl group. At least one substituent independently selected in the group. Preferably, R 3 to R 6 are independently independently selected from the group consisting of a halogen, a phenyl group, a phenyl group substituted with 1 to 4 halogen atoms or a C 1 10 alkyl group, and a C 1 10 alkyl group. A substituent.
上式(7)中,Z係例如C6 ~20 的4價芳香族基,最好係均苯四羧基、多環式芳香族基、多環式芳香族基的衍生物或依下式(8)所示基:In the above formula (7), a Z-based tetravalent aromatic group such as C 6 to 20 is preferably a pyromellicyl group, a polycyclic aromatic group or a polycyclic aromatic group derivative or a derivative according to the following formula ( 8) The base shown:
上式(8)中,Z’係例如:共價鍵、C(R7 )2 基、CO基、O原子、S原子、SO2 基、Si(C2 H5 )2 基或NR8 基,當複數的情況,分別係可為相同或互異。此外,w係指1至10的整數。R7 係指各自獨立的氫或C(R9 )3 。R8 係指氫、碳原子數1~約20的烷基、或C6 ~20 芳香基,當複數的情況,分別係可為相同或互異。R9 係指各自獨立的氫、氟或氯。In the above formula (8), Z' is, for example, a covalent bond, a C(R 7 ) 2 group, a CO group, an O atom, an S atom, a SO 2 group, a Si(C 2 H 5 ) 2 group or an NR 8 group. In the case of plurals, they may be the same or different. Further, w means an integer of 1 to 10. Means R 7 are each independently hydrogen or C (R 9) 3. R 8 means hydrogen, an alkyl group having 1 to 20 carbon atoms, or a C 6 to 20 aromatic group, and when plural, they may be the same or different from each other. R 9 means independently hydrogen, fluorine or chlorine.
再者,液晶材料係可舉例由諸如:膽固醇型液晶性聚合物等液晶材料構成的膽固醇型配向薄膜;將膽固醇型配向層利用薄膜進行支撐者;以及圓盤型液晶層等。首先,膽固醇型配向薄膜最好係適當選擇諸如熱處理等手法,而使薄膜法線方向上存在膽固醇型螺旋軸的均勻平面配向物,且選擇反射波長λs最好在300nm以下。Further, the liquid crystal material may, for example, be a cholesteric alignment film composed of a liquid crystal material such as a cholesteric liquid crystalline polymer; a cholesteric alignment layer supported by a film; and a disk-shaped liquid crystal layer. First, it is preferable that the cholesteric alignment film is appropriately selected such as a heat treatment to have a uniform planar alignment of the cholesteric helical axis in the normal direction of the film, and the selective reflection wavelength λs is preferably 300 nm or less.
再者,實現膽固醇型配向的材料並不僅侷限於液晶性聚合物,尚可使用諸如:具有能依單體實現膽固醇型配向之聚合性基的液晶單體分子、或者具有聚合性基的液晶性單體與對掌化合物的混合物等。尚可採行將該等材料利用適當選擇諸如熱處理等手法施行膽固醇型配向後,再將聚合性基利用諸如熱、光等適當手段施行硬化,而將膽固醇型配向固定化。Further, the material for realizing the cholesteric alignment is not limited to the liquid crystalline polymer, and liquid crystal monomer molecules having a polymerizable group capable of achieving a cholesteric alignment depending on a monomer or liquid crystal having a polymerizable group can be used. a mixture of a monomer and a palm compound, and the like. It is also possible to carry out the cholesteric alignment by a suitable method such as heat treatment, and then harden the polymerizable group by an appropriate means such as heat or light to immobilize the cholesteric type.
再者,形成負單軸性光學非等向性層之除上述以外的液晶材料,尚可使用經水平配向的聚合性圓盤型液晶化合物。Further, in addition to the liquid crystal material other than the above, which forms a negative uniaxial optical anisotropic layer, a horizontally aligned polymerizable discotic liquid crystal compound can be used.
當將具有上述負單軸光學非等向性層的光學薄膜厚度設為d3、將該光學非等向性層面內的主折射率設為Nx3及Ny3、將厚度方向的主折射率設為Nz3、且Nx3≧Ny3>Nz3時,面內的延遲值(Re3=(Nx3-Ny3)×d3[nm])最好為0nm~20nm,厚度方向的延遲值(Rth3=(Nx3-Nz3)×d3[nm])最好為50nm~500nm。When the thickness of the optical film having the negative uniaxial optical anisotropic layer is d3, the main refractive index in the optical anisotropic layer is Nx3 and Ny3, and the main refractive index in the thickness direction is Nz3. When Nx3≧Ny3>Nz3, the in-plane retardation value (Re3=(Nx3-Ny3)×d3[nm]) is preferably 0 nm to 20 nm, and the retardation value in the thickness direction (Rth3=(Nx3-Nz3)×d3) [nm]) is preferably 50 nm to 500 nm.
因為具有負單軸光學非等向性光學薄膜的光學參數Re3值、Rth3值,依存於液晶顯示裝置的方式與各種光學參數,因而不能一概言之,相對於550nm單色光,面內的延遲值(Re3),通常控制在0nm~20nm,最好0nm~10nm,尤以0nm~5nm範圍內為佳,且厚度方向的延遲值(Rth3),通常控制在50nm~500nm,最好80nm~400nm,尤以100nm~300nm範圍內為佳。Since the optical parameter Re3 value and Rth3 value of the negative uniaxial optical anisotropic optical film depend on the mode of the liquid crystal display device and various optical parameters, it cannot be said in general, and the in-plane retardation with respect to the 550 nm monochromatic light. The value (Re3) is usually controlled at 0 nm to 20 nm, preferably 0 nm to 10 nm, preferably in the range of 0 nm to 5 nm, and the retardation value (Rth3) in the thickness direction is usually controlled at 50 nm to 500 nm, preferably 80 nm to 400 nm. Especially in the range of 100 nm to 300 nm.
藉由將上述Re3值與Rth3值設定在上述範圍內,液晶顯示裝置的視角改良薄膜,便可一邊施行液晶顯示的色調校正,一邊擴大視角。當Re3值大於20nm的情況,因較大的正面相位差值之影響,恐有導致液晶顯示元件的正面特性惡化之可能性。此外,當Rth3值小於50nm、或大於500nm的情況,恐有無法獲得充分的視角改良效果、或斜向觀看時產生不必要著色情形的可能性。By setting the Re3 value and the Rth3 value within the above range, the viewing angle improving film of the liquid crystal display device can expand the viewing angle while performing tone correction of the liquid crystal display. When the Re3 value is larger than 20 nm, there is a possibility that the front characteristics of the liquid crystal display element are deteriorated due to the influence of a large front surface difference value. Further, when the Rth3 value is less than 50 nm or more than 500 nm, there is a fear that a sufficient viewing angle improvement effect or a possibility of unnecessary coloring in oblique viewing may not be obtained.
其次,針對本發明橢圓偏光板之製造方法進行說明。Next, a method of manufacturing the elliptically polarizing plate of the present invention will be described.
本發明的橢圓偏光板係由:具有僅偏光元件單面利用透光性保護膜施行保護之積層構造的直線偏光板、具有相位差功能的相位差膜、以及垂直配向液晶層構成,此外視需要組裝前述光學薄膜,且分別利用黏著劑層或接著劑層(以稱「黏/接著劑層」)相互貼合便可製得。此外,亦可採行將在配向基板上所形成的垂直配向液晶層,利用黏/接著劑層貼附於上述直線偏光板、或相位差膜、或光學薄膜上之後,再將配向基板剝離,僅將垂直配向液晶層轉印於直線偏光板、或相位差膜、或光學薄膜上的手法施行積層。The elliptically polarizing plate of the present invention comprises a linear polarizing plate having a laminated structure in which only one surface of the polarizing element is protected by a translucent protective film, a retardation film having a phase difference function, and a vertical alignment liquid crystal layer, and further, if necessary The optical film is assembled and bonded to each other by an adhesive layer or an adhesive layer (referred to as a "adhesive/adhesive layer"). Further, the vertical alignment liquid crystal layer formed on the alignment substrate may be applied to the linear polarizing plate, the retardation film, or the optical film by the adhesive/adhesive layer, and then the alignment substrate may be peeled off. The laminate is applied only by a method in which the vertical alignment liquid crystal layer is transferred onto a linear polarizing plate, a retardation film, or an optical film.
具體的製造方法係可例示如以下的[1]~[4]方法:另外,以下的記載中,「/」係指層的界面。The specific manufacturing method is exemplified by the following methods [1] to [4]: In the following description, "/" refers to the interface of the layer.
[1]橢圓偏光板之製造方法,特徵在於至少經由下述步驟:[1] A method of manufacturing an elliptically polarizing plate, characterized by at least the following steps:
(1)將透光性保護膜經由接著劑層1而與偏光元件相黏合,獲得由透光性保護膜/接著劑層1/偏光元件構成積層體(I)(直線偏光板)的第1步驟;(1) The light-transmitting protective film is bonded to the polarizing element via the adhesive layer 1, and the first layer (I) (linear polarizing plate) composed of the light-transmitting protective film/adhesive layer 1/polarizing element is obtained. step;
(2)在相位差膜上形成呈現正單軸性的液晶性組成物之層,將該層施行垂直配向之後,再形成將配向固定化的垂直配向液晶層,便獲得由相位差膜/垂直配向液晶層構成積層體(II)的第2步驟;以及(2) forming a layer of a liquid crystal composition exhibiting positive uniaxiality on the retardation film, and performing vertical alignment of the layer, and then forming a vertical alignment liquid crystal layer to which the alignment is fixed, thereby obtaining a retardation film/vertical a second step of aligning the liquid crystal layer to form the layered body (II);
(3)將上述積層體(II)的相位差膜側,經由接著劑層2而與上述積層體(I)的偏光元件側相黏合,便獲得由透光性保護膜/接著劑層1/偏光元件/接著劑層2/相位差膜/垂直配向液晶層構成橢圓偏光板的第3步驟。(3) The retardation film side of the laminate (II) is bonded to the polarizing element side of the laminate (I) via the adhesive layer 2, whereby a light-transmitting protective film/adhesive layer 1/1 is obtained. The polarizing element/adhesive layer 2/phase difference film/vertical alignment liquid crystal layer constitutes the third step of the elliptically polarizing plate.
[2]橢圓偏光板之製造方法,特徵在於至少經由下述步驟:[2] A method of manufacturing an elliptically polarizing plate, characterized by at least the following steps:
(1)將透光性保護膜經由接著劑層1而與偏光元件相黏合,獲得由透光性保護膜/接著劑層1/偏光元件構成積層體(I)(直線偏光板)的第1步驟;(1) The light-transmitting protective film is bonded to the polarizing element via the adhesive layer 1, and the first layer (I) (linear polarizing plate) composed of the light-transmitting protective film/adhesive layer 1/polarizing element is obtained. step;
(2)在相位差膜上形成呈現正單軸性的液晶性組成物之層,將該層施行垂直配向之後,再形成將配向固定化的垂直配向液晶層,便獲得由相位差膜/垂直配向液晶層構成積層體(II)的第2步驟;以及(2) forming a layer of a liquid crystal composition exhibiting positive uniaxiality on the retardation film, and performing vertical alignment of the layer, and then forming a vertical alignment liquid crystal layer to which the alignment is fixed, thereby obtaining a retardation film/vertical a second step of aligning the liquid crystal layer to form the layered body (II);
(3)將上述積層體(II)的垂直配向液晶相側,經由接著劑層2而與上述積層體(I)的偏光元件側相黏合,便獲得由透光性保護膜/接著劑層1/偏光元件/接著劑層2/垂直配向液晶層/相位差膜構成橢圓偏光板的第3步驟。(3) The vertical alignment of the layered product (II) to the liquid crystal phase side is bonded to the polarizing element side of the layered product (I) via the adhesive layer 2, whereby the light-transmitting protective film/adhesive layer 1 is obtained. / Polarizing element / adhesive layer 2 / vertical alignment liquid crystal layer / retardation film constitutes the third step of the elliptically polarizing plate.
[3]橢圓偏光板之製造方法,特徵在於至少經由下述步驟:[3] A method of manufacturing an elliptically polarizing plate, characterized by at least the following steps:
(1)將透光性保護膜經由接著劑層1而與偏光元件相黏合,便獲得由透光性保護膜/接著劑層1/偏光元件構成積層體(I)(直線偏光板)的第1步驟;(1) The light-transmitting protective film is bonded to the polarizing element via the adhesive layer 1, and the laminated body (I) (linear polarizing plate) comprising the light-transmitting protective film/adhesive layer 1/polarizing element is obtained. 1 step;
(2)在配向基板上形成呈現正單軸性的液晶性組成物之層,將該層施行垂直配向之後,再形成將配向固定化的垂直配向液晶層,便獲得由配向基板/垂直配向液晶層構成積層體(III)的第2步驟;(2) forming a layer of a liquid crystal composition exhibiting a positive uniaxiality on the alignment substrate, and then vertically aligning the layer, and then forming a vertical alignment liquid crystal layer to which the alignment is fixed, thereby obtaining an alignment substrate/vertical alignment liquid crystal The second step of forming the layered body (III);
(3)將上述積層體(III)的垂直配向液晶層側,經由接著劑層2而與相位差膜相黏合後,再將配向基板剝離而將垂直配向液晶層轉印於相位差膜上,便獲得由相位差膜/接著劑層2/垂直配向液晶層構成積層體(IV)的第3步驟;以及(3) The vertical alignment of the layered product (III) on the liquid crystal layer side is bonded to the retardation film via the adhesive layer 2, and then the alignment substrate is peeled off, and the vertical alignment liquid crystal layer is transferred onto the retardation film. The third step of forming the laminate (IV) from the retardation film/adhesive layer 2/vertical alignment liquid crystal layer;
(4)將上述積層體(IV)的相位差膜側,經由接著劑層3而與上述積層體(I)的偏光元件側相黏合,便獲得由透光性保護膜/接著劑層1/偏光元件/接著劑層3/相位差膜/接著劑層2/垂直配向液晶層構成橢圓偏光板的第4步驟。(4) The retardation film side of the layered product (IV) is bonded to the polarizing element side of the layered product (I) via the adhesive layer 3 to obtain a light-transmitting protective film/adhesive layer 1/ The polarizing element/adhesive layer 3/retardation film/adhesive layer 2/vertical alignment liquid crystal layer constitutes the fourth step of the elliptically polarizing plate.
[4]橢圓偏光板之製造方法,特徵在於至少經由下述步驟:[4] A method of manufacturing an elliptically polarizing plate, characterized by at least the following steps:
(1)將透光性保護膜經由接著劑層1而與偏光元件相黏合,獲得由透光性保護膜/接著劑層1/偏光元件構成積層體(I)(直線偏光板)的第1步驟;(1) The light-transmitting protective film is bonded to the polarizing element via the adhesive layer 1, and the first layer (I) (linear polarizing plate) composed of the light-transmitting protective film/adhesive layer 1/polarizing element is obtained. step;
(2)在配向基板上形成呈現正單軸性的液晶性組成物之層,將該層施行垂直配向之後,再形成將配向固定化的垂直配向液晶層,便獲得由配向基板/垂直配向液晶層構成積層體(III)的第2步驟;(2) forming a layer of a liquid crystal composition exhibiting a positive uniaxiality on the alignment substrate, and then vertically aligning the layer, and then forming a vertical alignment liquid crystal layer to which the alignment is fixed, thereby obtaining an alignment substrate/vertical alignment liquid crystal The second step of forming the layered body (III);
(3)將上述積層體(III)的垂直配向液晶層側,經由接著劑層2而與相位差膜相黏合後,再將配向基板剝離而將垂直配向液晶層轉印於相位差膜上,便獲得由相位差膜/接著劑層2/垂直配向液晶層構成積層體(IV)的第3步驟;以及(3) The vertical alignment of the layered product (III) on the liquid crystal layer side is bonded to the retardation film via the adhesive layer 2, and then the alignment substrate is peeled off, and the vertical alignment liquid crystal layer is transferred onto the retardation film. The third step of forming the laminate (IV) from the retardation film/adhesive layer 2/vertical alignment liquid crystal layer;
(4)將上述積層體(IV)的垂直配向液晶層側,經由接著劑層3而與上述積層體(I)的偏光元件側相黏合,便獲得由透光性保護膜/接著劑層1/偏光元件/接著劑層3/垂直配向液晶層/接著劑層2/相位差膜構成橢圓偏光板的第4步驟。(4) The vertical alignment of the layered product (IV) on the side of the liquid crystal layer is bonded to the polarizing element side of the layered product (I) via the adhesive layer 3, whereby the light-transmitting protective film/adhesive layer 1 is obtained. / Polarizing element / adhesive layer 3 / vertical alignment liquid crystal layer / adhesive layer 2 / retardation film constitutes the fourth step of the elliptically polarizing plate.
再者,直線偏光板、相位差膜、或光學薄膜的積層方法,最好使用例如:使用後述黏/接著劑層直接將二者進行積層的手法;將對光學薄膜賦予液晶配向能力,呈現均勻且單一區域液晶配向性,且可輕易將該配向狀態固定化的液晶性高分子等施行塗佈等手段而進行設置的手法;將在薄膜基板上所設置液晶性高分子、或含有該等的組成物,使用後述黏著劑或接著劑,轉印於其他的直線偏光板或薄膜上的手法等。Further, in the method of laminating a linear polarizing plate, a retardation film, or an optical film, it is preferable to use, for example, a method of directly laminating the two using an adhesive/adhesive layer described later; And a liquid crystal polymer having a single-region liquid crystal alignment property, which can be easily applied by applying a liquid crystal polymer or the like which is fixed in an alignment state, and a liquid crystal polymer provided on the film substrate or containing the same The composition is transferred to another linear polarizing plate or film using an adhesive or an adhesive described later.
形成在直線偏光板、垂直配向液晶層、各光學非等向性層的積層或轉印時所使用黏/接著劑層的黏著劑或接著劑,係在光學性具等向性且呈透明之前提下,其餘並無特別的限制。可將例如:丙烯酸系聚合物、聚矽氧系聚合物、聚酯、聚胺基甲酸酯、聚醯胺、聚醚、氟系、橡膠系等聚合物適當地選擇使用為基底聚合物。在該等黏/接著劑中,為調整塗佈性、黏合性、剝離性等,尚可添加各種添加劑,例如:界面活性劑、消泡劑、增黏劑、黏著性賦予劑、均塗劑。此外,亦可使用具有經利用光、電子束、熱等外部刺激而產生反應並聚合或交聯之反應性物;或者氟系、橡膠系等。該等之中,特別以使用諸如丙烯酸系黏著劑之類,光學透明性優異,呈現適度濕潤性、凝聚性、黏合性的黏著特性,同時耐候性、耐熱性等亦均優越的物質為佳。An adhesive or an adhesive which is formed on a linear polarizing plate, a vertically aligned liquid crystal layer, or an optical anisotropic layer, or an adhesive/adhesive layer used for transfer, before the optical isotropic and transparent There are no special restrictions on the rest. For example, a polymer such as an acrylic polymer, a polyoxymethylene polymer, a polyester, a polyurethane, a polyamide, a polyether, a fluorine, or a rubber may be appropriately selected and used as a base polymer. In the adhesion/adhesive agent, various additives such as a surfactant, an antifoaming agent, a tackifier, an adhesion imparting agent, and a leveling agent may be added in order to adjust coatability, adhesion, peelability, and the like. . Further, a reactive substance which is reacted or polymerized by external stimulation such as light, electron beam or heat; or a fluorine-based or rubber-based one may be used. Among these, in particular, it is preferable to use an adhesive such as an acrylic adhesive which is excellent in optical transparency, exhibits appropriate wettability, cohesiveness, and adhesive properties, and is excellent in weather resistance and heat resistance.
本發明所使用的直線偏光板係在單側設有透光性保護膜,通常因為直線偏光板係組裝於液晶顯示裝置中,且透光性保護膜層將成為最外層,因而透光性保護膜為能達偏光元件保護,如前述,最好使用透明性、機械強度、熱穩定性、水分遮蔽性、等向性等均優越者。另一方面,雖無設置透光性保護膜的偏光元件側、或者垂直配向液晶層、相位差膜等並非屬於最外層,但是亦可使黏/接著劑具有防止(保護)各種加工時所發生的刮傷情況、或者緩和因加工/熱所造成變形等而衍生之應力的功能。此外,黏/接著劑層並非每1層均屬必要,亦可複數層積層。The linear polarizing plate used in the present invention is provided with a light-transmitting protective film on one side, and generally, since the linear polarizing plate is assembled in a liquid crystal display device, and the light-transmitting protective film layer is the outermost layer, the light-transmitting protection is provided. The film is capable of achieving protection of the polarizing element, and as described above, it is preferable to use transparency, mechanical strength, thermal stability, moisture shielding property, isotropic property, and the like. On the other hand, the polarizing element side where the light-transmitting protective film is not provided, or the vertical alignment liquid crystal layer or the retardation film does not belong to the outermost layer, but the adhesive/adhesive agent can also be prevented (protected) from occurring during various processes. The scratching condition, or the function of relieving the stress derived from the deformation caused by the processing/heat. In addition, the adhesive/adhesive layer is not necessary for each layer, and may be laminated in multiple layers.
黏/接著劑層的形成係可依適當方式實施。此例子係有如:調製在由諸如甲苯、醋酸乙酯等適當溶劑的單獨物或混合物所構成溶劑中,溶解或分散著基底聚合物或其組成物的10~40質量%左右之黏/接著劑溶液,再將其依照諸如澆塗方式、塗佈方式等適當的展開方式,直接附設於上述直線偏光板、相位差膜、液晶層、光學非等向性層上的方式;或者根據上述在分離器上形成黏/接著劑層,再將其移轉於上述直線偏光板、相位差膜、液晶層、光學非等向性層上的方式等。此外,在黏/接著劑層中尚可含有例如天然物或合成物的樹脂類,特別係例如由:黏著性賦予樹脂、玻璃纖維、玻璃珠、金屬粉、其他的無機粉末等所構成填充劑、顏料、著色劑、抗氧化劑等,添加於黏/接著劑中的添加劑。此外,亦可為含有微粒子而呈光擴散性的黏/接著劑層等。The formation of the adhesive/adhesive layer can be carried out in a suitable manner. This example is, for example, prepared by dissolving or dispersing a binder/adhesive of about 10 to 40% by mass of the base polymer or a composition thereof in a solvent composed of a single substance or a mixture of a suitable solvent such as toluene or ethyl acetate. a solution, which is directly attached to the linear polarizing plate, the retardation film, the liquid crystal layer, or the optical anisotropic layer in a suitable expansion manner such as a coating method or a coating method; or is separated according to the above A bonding/adhesive layer is formed on the device, and then transferred to the linear polarizing plate, the retardation film, the liquid crystal layer, and the optical anisotropic layer. Further, a resin such as a natural product or a composition may be contained in the adhesive/adhesive layer, and in particular, a filler composed of, for example, an adhesive-imparting resin, glass fiber, glass beads, metal powder, or other inorganic powder may be used. , pigments, colorants, antioxidants, etc., additives added to the adhesive/adhesive. Further, it may be a layer of a binder/adhesive agent which is light-diffusing due to the inclusion of fine particles.
黏/接著劑層的厚度係在能將所貼附的構件黏貼且可維持充分密接力之前提下,並無就膜厚有特別的限制,可依照黏/接著劑的特性、以及所黏/接著的構件而適當選定。因為強烈要求減少橢圓偏光板總厚,因而黏/接著劑的厚度係越薄越好,通常設為2~80μm,最好5~50μm,尤以5~40μm為佳。若超出該範圍外,發生黏合力嫌不足、積層時或橢圓偏光板保存時將從端部滲出等情況,因而最好避免。The thickness of the adhesive/adhesive layer is removed before the attached member can be adhered and sufficient adhesion can be maintained, and there is no particular limitation on the film thickness, depending on the characteristics of the adhesive/adhesive agent, and the adhesion/adhesion/ The following components are appropriately selected. Since it is strongly required to reduce the total thickness of the elliptically polarizing plate, the thickness of the adhesive/adhesive agent is as thin as possible, and is usually 2 to 80 μm, preferably 5 to 50 μm, particularly preferably 5 to 40 μm. If it is outside this range, it is preferable to avoid the occurrence of insufficient adhesion, delamination from the end when laminating or storage of the elliptically polarizing plate.
另外,當將垂直配向液晶層經由黏/接著劑層,轉印於上述直線偏光板、相位差膜或光學薄膜上之時,為使轉印能趨於容易,便可適當使用如下述(一)~(七)的製程:Further, when the vertical alignment liquid crystal layer is transferred onto the linear polarizing plate, the retardation film or the optical film via the adhesive/adhesive layer, in order to facilitate the transfer energy, the following can be suitably used (1) )~(7) Process:
(一)將在配向基板上所形成且液晶配向經固定化的垂直配向液晶層,經由接著劑層1,直接貼附於直線偏光板、相位差膜或光學薄膜上,再將配向基板剝離,而將垂直配向液晶層轉印於直線偏光板、相位差膜或光學薄膜上。(1) a vertical alignment liquid crystal layer formed on the alignment substrate and fixed by the liquid crystal alignment, directly attached to the linear polarizing plate, the retardation film or the optical film via the adhesive layer 1, and then the alignment substrate is peeled off. The vertical alignment liquid crystal layer is transferred onto a linear polarizing plate, a retardation film or an optical film.
(二)將在配向基板上所形成且液晶配向經固定化的垂直配向液晶層,經由接著劑層1而與再剝離性基板1相黏合後,再將配向基板剝離,而將垂直配向液晶層轉印於再剝離性基板1上,便製得由再剝離性基板1/接著劑層1/垂直配向液晶層構成的中間體1,再經由接著劑層2而與再剝離性基板2相黏合後,將再剝離性基板1剝離,便製得由接著劑層1/垂直配向液晶層/接著劑層2/再剝離性基板2構成的中間體2,再於接著劑層1側黏貼著無設離形膜的無載媒糊後,將離形膜剝離,再貼附於適當的直線偏光板、相位差膜或光學薄膜上,將再剝離性基板2剝離。(2) The vertical alignment liquid crystal layer formed on the alignment substrate and fixed by the liquid crystal alignment is bonded to the re-peelable substrate 1 via the adhesive layer 1, and then the alignment substrate is peeled off to vertically align the liquid crystal layer. After being transferred onto the re-peelable substrate 1, an intermediate 1 composed of a re-peelable substrate 1 / an adhesive layer 1 / a vertical alignment liquid crystal layer is obtained, and then bonded to the re-peelable substrate 2 via the adhesive layer 2 Thereafter, the releasable substrate 1 is peeled off to obtain an intermediate 2 composed of an adhesive layer 1/vertical alignment liquid crystal layer/adhesive layer 2/removable substrate 2, and then adhered to the adhesive layer 1 side. After the carrier-free paste of the film is formed, the release film is peeled off and attached to an appropriate linear polarizing plate, retardation film or optical film to peel off the re-peelable substrate 2.
(三)將在配向基板上所形成且液晶配向經固定化的垂直配向液晶層,經由接著劑層1而與再剝離性基板1相黏合後,將配向基板剝離而將垂直配向液晶層轉印於再剝離性基板1上,便製得由再剝離性基板1/接著劑層1/垂直配向液晶層構成的中間體1,再經由接著劑層2而與再剝離性基板2相黏合後,將再剝離性基板1剝離,便製得由接著劑層1/垂直配向液晶層/接著劑層2/再剝離性基板2構成的中間體2,更在接著劑層1側黏貼著無設離形膜的無載媒糊(黏著劑)後,將再剝離性基板2剝離,而製得由離形膜/黏著劑層/接著劑層1/垂直配向液晶層/接著劑層2構成的中間體3,更在接著劑層2側亦黏貼著無設離形膜的無載媒糊,而製得由離形膜/黏著劑層/接著劑層1/垂直配向液晶層/接著劑層2/黏著劑層/離形膜構成的中間體4,將離形膜剝離,再貼附於直線偏光板、相位差膜或光學薄膜上。(3) The vertical alignment liquid crystal layer formed on the alignment substrate and fixed by the liquid crystal alignment is bonded to the re-peelable substrate 1 via the adhesive layer 1, and then the alignment substrate is peeled off to transfer the vertical alignment liquid crystal layer On the re-peelable substrate 1, an intermediate 1 composed of a re-peelable substrate 1 / an adhesive layer 1 / a vertical alignment liquid crystal layer is obtained, and after bonding to the re-peelable substrate 2 via the adhesive layer 2, The re-peelable substrate 1 is peeled off to obtain an intermediate 2 composed of an adhesive layer 1 / a vertical alignment liquid crystal layer / an adhesive layer 2 / a re-peelable substrate 2, and is further adhered to the adhesive layer 1 side. After the carrier-free paste (adhesive) of the film, the releasable substrate 2 is peeled off, and the intermediate layer composed of the release film/adhesive layer/adhesive layer 1/vertical alignment liquid crystal layer/adhesive layer 2 is obtained. On the side of the adhesive layer 2, the unsupported dielectric paste without the release film is also adhered, and the release film/adhesive layer/adhesive layer 1/vertical alignment liquid crystal layer/adhesive layer 2 is obtained. /Adhesive layer / intermediate film composed of a release film, the release film is peeled off, and then attached to a linear polarizing plate, a retardation film or optical Film.
再者,藉由在接著劑中添適當加諸如表面改質劑等添加劑,便可減輕當將再剝離性基板與垂直配向液晶層相貼附時的二者間之密接力,且可維持再剝離性基板與接著劑層間之密接力,藉此便可在再剝離性基板側貼附著接著劑層之情況下施行剝離。此時所使用的表面改質劑係所產生的作用(例如界面活性劑等)不對產品的光學缺陷檢查性或剝離性造成不良影響之範疇內便可,就種類、添加量均無特別的限制。當依照此種手法而將垂直配向液晶層轉印於上述直線偏光板、相位差膜或光學薄膜上之際,為使轉印趨於容易,可適當使用如下述(四)~(七)的製程。Furthermore, by adding an additive such as a surface modifier to the adhesive, the adhesion between the re-peelable substrate and the vertical alignment liquid crystal layer can be reduced, and the adhesion can be maintained. By the adhesive force between the peelable substrate and the adhesive layer, peeling can be performed in the case where the adhesive layer is adhered to the side of the re-peelable substrate. The effect of the surface modifier used at this time (for example, a surfactant, etc.) does not adversely affect the optical defect inspection property or peelability of the product, and there is no particular limitation on the type and amount of addition. . When the vertical alignment liquid crystal layer is transferred onto the linear polarizing plate, the retardation film or the optical film in accordance with such a method, in order to facilitate the transfer, the following (4) to (7) can be suitably used. Process.
(四)將在配向基板上所形成且液晶配向經固定化的垂直配向液晶層,經由接著劑層1而與再剝離性基板1相黏合後,將配向基板剝離,而將垂直配向液晶層轉印於再剝離性基板1上,便製得由再剝離性基板1/接著劑層1/垂直配向液晶層構成的中間體1,更經由接著劑層2而與再剝離性基板2相黏合後,將再剝離性基板1剝離,便製得由接著劑層1/垂直配向液晶層/接著劑層2/再剝離性基板2構成的中間體2,更在接著劑層1側黏貼著無設離形膜的無載媒糊後,將離形膜剝離,並貼附於適當的直線偏光板、相位差膜或光學薄膜上,再於貼附著接著劑層2的狀態下將再剝離性基板2剝離。(4) The vertical alignment liquid crystal layer formed on the alignment substrate and fixed by the liquid crystal alignment is bonded to the re-peelable substrate 1 via the adhesive layer 1, and then the alignment substrate is peeled off, and the vertical alignment liquid crystal layer is transferred. On the re-peelable substrate 1, an intermediate 1 composed of a re-peelable substrate 1 / an adhesive layer 1 / a vertical alignment liquid crystal layer is obtained, and after bonding to the re-peelable substrate 2 via the adhesive layer 2 The peelable substrate 1 is peeled off, and the intermediate 2 composed of the adhesive layer 1/vertical alignment liquid crystal layer/adhesive layer 2/releasable substrate 2 is obtained, and the adhesive layer 1 is adhered to the adhesive layer 1 side. After the carrier film is free of the carrier paste, the release film is peeled off and attached to a suitable linear polarizing plate, retardation film or optical film, and the re-peelable substrate is attached with the adhesive layer 2 attached thereto. 2 peeling.
(五)將在配向基板上所形成且液晶配向經固定化的垂直配向液晶層,經由接著劑層1而與再剝離性基板1相黏合後,將配向基板剝離,將垂直配向液晶層轉印於再剝離性基板1上,便製得由再剝離性基板1/接著劑層1/垂直配向液晶層構成的中間體1,更經由接著劑層2而與再剝離性基板2相黏合後,將再剝離性基板1剝離,而製得由接著劑層1/垂直配向液晶層/接著劑層2/再剝離性基板2構成的中間體2,更在接著劑層1側黏貼著無設離形膜的無載媒糊後,便在貼附著接著劑層2之狀態下將再剝離性基板2剝離,便製得由離形膜/黏著劑層/接著劑層1/垂直配向液晶層構成的中間體5,更在垂直配向液晶層側亦黏貼著無設離形膜的無載媒糊,便製得由離形膜/黏著劑層/接著劑層1/垂直配向液晶層/接著劑層2/黏著劑層/離形膜構成的中間體6,將離形膜剝離,再貼附於適當的直線偏光板、相位差膜或光學薄膜上。(5) The vertical alignment liquid crystal layer formed on the alignment substrate and fixed by the liquid crystal alignment is bonded to the re-peelable substrate 1 via the adhesive layer 1, and then the alignment substrate is peeled off, and the vertical alignment liquid crystal layer is transferred. On the re-peelable substrate 1, an intermediate 1 composed of a re-peelable substrate 1 / an adhesive layer 1 / a vertical alignment liquid crystal layer is obtained, and after bonding to the re-peelable substrate 2 via the adhesive layer 2, The re-peelable substrate 1 is peeled off to obtain an intermediate 2 composed of an adhesive layer 1 / a vertical alignment liquid crystal layer / an adhesive layer 2 / a re-peelable substrate 2, and is further adhered to the adhesive layer 1 side. After the carrier-free paste of the film is formed, the re-peelable substrate 2 is peeled off with the adhesive layer 2 attached thereto, thereby producing a film of the release film/adhesive layer/adhesive layer 1/vertical alignment liquid crystal layer. The intermediate 5, which is also adhered to the side of the vertical alignment liquid crystal layer and adhered to the unsupported film without the release film, is obtained by the release film/adhesive layer/adhesive layer 1/vertical alignment liquid crystal layer/adhesive agent. Intermediate 2 composed of layer 2/adhesive layer/release film, peeling off the release film and attaching it to the appropriate linear deviation On a light plate, retardation film or optical film.
(六)將在配向基板上所形成且液晶配向經固定化的垂直配向液晶層,經由接著劑層1而與再剝離性基板1相黏合後,將配向基板剝離,便將垂直配向液晶層轉印於再剝離性基板1上,便製得由再剝離性基板1/接著劑層1/垂直配向液晶層構成的中間體1,更經由接著劑層2而與再剝離性基板2相黏合後,將再剝離性基板2剝離,便製得由再剝離性基板1/接著劑層1/垂直配向液晶層/接著劑層2構成的中間體2,更在接著劑層2側黏貼著無設離形膜的無載媒糊後,將離形膜剝離,再貼附於適當的直線偏光板、相位差膜或光學薄膜上,再於貼附著接著劑層1之狀態下將再剝離性基板1剝離。(6) The vertical alignment liquid crystal layer formed on the alignment substrate and fixed by the liquid crystal alignment is bonded to the re-peelable substrate 1 via the adhesive layer 1, and then the alignment substrate is peeled off, and the vertical alignment liquid crystal layer is transferred. On the re-peelable substrate 1, an intermediate 1 composed of a re-peelable substrate 1 / an adhesive layer 1 / a vertical alignment liquid crystal layer is obtained, and after bonding to the re-peelable substrate 2 via the adhesive layer 2 The peelable substrate 2 is peeled off, and the intermediate 2 composed of the re-peelable substrate 1 / the adhesive layer 1 / the vertical alignment liquid crystal layer / the adhesive layer 2 is obtained, and the adhesive layer 2 is adhered to the adhesive layer 2 side. After the carrier film is free of the carrier paste, the release film is peeled off, and then attached to a suitable linear polarizing plate, retardation film or optical film, and the re-peelable substrate is attached with the adhesive layer 1 attached thereto. 1 peeling.
(七)將在配向基板上所形成且液晶配向經固定化的垂直配向液晶層,經由接著劑層1而與再剝離性基板1相黏合後,將配向基板剝離,便將垂直配向液晶層轉印於再剝離性基板1上,便製得由再剝離性基板1/接著劑層1/垂直配向液晶層構成的中間體1,更經由接著劑層2而與再剝離性基板2相黏合後,將再剝離性基板2剝離,便製得由再剝離性基板1/接著劑層1/垂直配向液晶層/接著劑層2構成的中間體2,更在接著劑層2側黏貼著無設離形膜的無載媒糊後,在貼附著接著劑層1之狀態下將再剝離性基板1剝離,便製得由垂直配向液晶層/接著劑層2/黏著劑層/離形膜構成的中間體7,更在垂直配向液晶層側亦黏貼著無設離形膜的無載媒糊,便製得由離形膜/黏著劑層/垂直配向液晶層/接著劑層2/黏著劑層/離形膜構成的中間體8,將離形膜剝離,並貼附於適當的直線偏光板、相位差膜或光學薄膜上。(7) The vertical alignment liquid crystal layer formed on the alignment substrate and fixed by the liquid crystal alignment is bonded to the re-peelable substrate 1 via the adhesive layer 1, and then the alignment substrate is peeled off, and the vertical alignment liquid crystal layer is transferred. On the re-peelable substrate 1, an intermediate 1 composed of a re-peelable substrate 1 / an adhesive layer 1 / a vertical alignment liquid crystal layer is obtained, and after bonding to the re-peelable substrate 2 via the adhesive layer 2 The peelable substrate 2 is peeled off, and the intermediate 2 composed of the re-peelable substrate 1 / the adhesive layer 1 / the vertical alignment liquid crystal layer / the adhesive layer 2 is obtained, and the adhesive layer 2 is adhered to the adhesive layer 2 side. After the carrier film of the release film is removed, the re-peelable substrate 1 is peeled off in the state in which the adhesive layer 1 is adhered, and the vertical alignment liquid crystal layer/adhesive layer 2/adhesive layer/release film is formed. The intermediate 7 is also adhered to the side of the vertical alignment liquid crystal layer, and the non-carrier paste without the release film is adhered to obtain the release film/adhesive layer/vertical alignment liquid crystal layer/adhesive layer 2/adhesive agent. Intermediate 8 composed of a layer/release film, peeling off the release film and attaching it to a suitable linear polarizing plate, phase Difference film or the optical film.
再者,在將垂直配向液晶層經由黏/接著劑層,轉印於上述直線偏光板、相位差膜或光學薄膜上之際,不僅垂直配向液晶層表面,就連其他所黏‧接著的構件表面亦施行表面處理,可提升與黏/接著劑層間之密接性。表面處理的手段並無特別的限制,可適當採用諸如:能維持上述液晶層表面透明性的電暈放電處理、濺鍍處理、低壓UV照射、電漿處理等表面處理法。該等表面處理法中最好為電暈放電處理。Further, when the vertical alignment liquid crystal layer is transferred onto the linear polarizing plate, the retardation film or the optical film via the adhesive/adhesive layer, not only the surface of the liquid crystal layer but also the other components are adhered to the surface of the liquid crystal layer. The surface is also surface treated to improve adhesion to the adhesive/adhesive layer. The means for the surface treatment is not particularly limited, and a surface treatment such as corona discharge treatment, sputtering treatment, low-pressure UV irradiation, or plasma treatment which can maintain the surface transparency of the liquid crystal layer can be suitably employed. Preferably, the surface treatment method is a corona discharge treatment.
上述再剝離性基板係可使用例如:聚乙烯、聚丙烯、聚(4-甲基戊烯-1)樹脂等烯烴系樹脂;聚醯胺、聚醯亞胺、聚醯胺醯亞胺、聚醚醯亞胺、聚醚酮、聚醚醚酮、聚醚碸、聚酮硫醚、聚碸、聚苯乙烯、聚芳基硫醚、聚二苯醚、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚芳香酯、聚縮醛、單軸延伸聚酯、聚碳酸酯、聚乙烯醇、聚甲基丙烯酸甲酯、聚芳香酯、非晶質聚烯烴、降烯系樹脂、三醋酸纖維素、或環氧樹脂等的薄膜。As the re-peelable substrate, for example, an olefin-based resin such as polyethylene, polypropylene, or poly(4-methylpentene-1) resin; polyamine, polyimine, polyamidimide, or poly Ether quinone imine, polyether ketone, polyether ether ketone, polyether oxime, polyketone sulfide, polyfluorene, polystyrene, polyaryl sulfide, polydiphenyl ether, polyethylene terephthalate, Polybutylene terephthalate, polyarylate, polyacetal, uniaxially stretched polyester, polycarbonate, polyvinyl alcohol, polymethyl methacrylate, polyaryl ester, amorphous polyolefin, drop A film of an olefin resin, cellulose triacetate, or an epoxy resin.
特別係就光學缺陷檢查性優異、透明性、且光學性等向性的薄膜,將可例示如:聚(4-甲基戊烯-1)、聚甲基丙烯酸甲酯、聚苯乙烯、聚碳酸酯、聚醚碸、聚芳香酯、非晶質聚烯烴、降烯系樹脂、三醋酸纖維素、或環氧樹脂等各種薄膜。In particular, a film having excellent optical defect inspection property, transparency, and optical isotropic property, for example, poly(4-methylpentene-1), polymethyl methacrylate, polystyrene, poly Carbonate, polyether oxime, polyaryl ester, amorphous polyolefin, drop Various films such as an olefin resin, cellulose triacetate, or epoxy resin.
該等塑膠薄膜中,為能維持著適度的再剝離性,可預先在表面上施行聚矽氧等的塗佈,或預先形成有機薄膜或無機薄膜。此外,在同樣目的下,亦可對塑膠薄膜表面施行諸如皂化處理等化學處理、或者如電暈處理之類的物理性處理。In the plastic film, in order to maintain moderate removability, coating of polyfluorene or the like may be performed on the surface in advance, or an organic film or an inorganic film may be formed in advance. Further, for the same purpose, the surface of the plastic film may be subjected to a chemical treatment such as saponification treatment or a physical treatment such as corona treatment.
再者,為調整再剝離性基板的剝離性,在上述塑膠薄膜中亦可含有滑劑、表面改質劑。上述滑劑係在不致對光學缺陷的檢查性、剝離性造成不良影響之範疇內,就種類、添加量並無特別的限制。滑劑的具體例係可舉例如:細微二氧化矽、細微氧化鋁等,添加量的指標係依使再剝離性基板的霧值通常在50%以下,最好30%以下便可。若添加量過少,則無法顯現出添加效果,反之,當過多的情況,光學缺陷的檢查性惡化,因而最好避免。Further, in order to adjust the releasability of the re-peelable substrate, a slip agent or a surface modifier may be contained in the plastic film. The above-mentioned slip agent is not particularly limited in terms of the type and amount of addition, insofar as it does not adversely affect the inspectability and peelability of optical defects. Specific examples of the lubricant include, for example, fine cerium oxide and fine alumina. The amount of the additive is usually such that the haze value of the re-peelable substrate is usually 50% or less, preferably 30% or less. If the amount added is too small, the effect of addition cannot be exhibited. Conversely, when the amount is too large, the inspection property of the optical defect is deteriorated, and thus it is preferable to avoid it.
再者,視需要尚可含有其他周知的各種添加劑,例如:抗結塊劑、抗氧化劑、抗靜電劑、熱穩定劑、耐衝擊性改良劑等。Further, various other well-known additives such as an anti-caking agent, an antioxidant, an antistatic agent, a heat stabilizer, an impact resistance improver, and the like may be contained as needed.
相關再剝離性基板的剝離力,即使由相同材料製得的再剝離性基板,仍將因製造方法、表面狀態、以其與所使用接著劑間之濕潤性等因素而有所差異,因而並無法一概定之,但就與接著劑間之界面處的剝離力(180°剝離、剝離速度30cm/分、室溫下測定),通常最好設定為0.38~12N/m,尤以0.38~8.0N/m為佳。當剝離力低於此值時,在將配向基板上的液晶物質層與再剝離性基板相黏合後,當將配向基板剝離時,剝離力過低,浮現於再剝離性基板上導致所需的面上無法獲得良好的剝離狀態,造成液晶物質層對再剝離性基板的轉印不足,反之,當剝離力過高時,當將再剝離性基板剝離之際,會發生液晶物質層遭破壞、或在與所需層間之界面處無法剝離等情況,因而最好避免。The peeling force of the related re-peelable substrate, even if the re-peelable substrate made of the same material differs depending on factors such as the production method, the surface state, and the wettability between the adhesive and the adhesive to be used, It is impossible to determine it, but the peeling force at the interface with the adhesive (180° peeling, peeling speed 30cm/min, measured at room temperature) is usually set to 0.38~12N/m, especially 0.38~8.0N. /m is better. When the peeling force is lower than this value, after the liquid crystal material layer on the alignment substrate is bonded to the re-peelable substrate, when the alignment substrate is peeled off, the peeling force is too low to appear on the re-peelable substrate, resulting in a desired A good peeling state cannot be obtained on the surface, resulting in insufficient transfer of the liquid crystal material layer to the re-peelable substrate. Conversely, when the peeling force is too high, when the re-peelable substrate is peeled off, the liquid crystal material layer is destroyed. Or it is not possible to peel off at the interface with the desired layer, so it is best to avoid it.
再者,再剝離性基板的厚度亦會有對剝離性造成影響的情況,最好設為16~100μm,尤以25~50μm為佳。若厚度過厚,則剝離點不穩定,恐有導致剝離性惡化的可能性,反之,若過薄,因為無法保持薄膜的機械強度,所以在製造中恐有會發生諸如撕裂等故障的可能性。Further, the thickness of the re-peelable substrate may also affect the peelability, and is preferably 16 to 100 μm, particularly preferably 25 to 50 μm. If the thickness is too thick, the peeling point is unstable, and the peeling property may be deteriorated. On the other hand, if it is too thin, since the mechanical strength of the film cannot be maintained, there is a fear that a failure such as tearing may occur in the manufacturing. Sex.
再者,亦可將垂直配向液晶層在未經由黏/接著劑層之情況下,將前述液晶材料在上述直線偏光板、相位差膜或光學薄膜上展開,並使該液晶材料配向後,再利用光照射及/或加熱處理,便將該配向狀態固定化而進行製造。視需要,亦可在上述直線偏光板、相位差膜或光學薄膜上設置前述配向膜之後,再將前述液晶材料展開,並將該液晶材料配向後,再利用光照射及/或加熱處理,而將該配向狀態固定化便可製得。Furthermore, the liquid crystal material may be spread on the linear polarizing plate, the retardation film or the optical film without passing through the adhesive/adhesive layer, and the liquid crystal material may be aligned, and then the liquid crystal material may be aligned. By using light irradiation and/or heat treatment, the alignment state is fixed and manufactured. If necessary, after the alignment film is provided on the linear polarizing plate, the retardation film or the optical film, the liquid crystal material may be developed, and the liquid crystal material may be aligned, and then irradiated with light and/or heat. This alignment state can be obtained by fixing it.
本發明的橢圓偏光板係由:直線偏光板、將垂直配向固定化的垂直配向液晶層、及具有相位差功能的相位差膜所構成橢圓偏光板,視需要亦可經積層著光學薄膜的橢圓偏光板,可舉例如下述(1)~(6)的構成。The elliptically polarizing plate of the present invention comprises an elliptically polarizing plate comprising a linear polarizing plate, a vertical alignment liquid crystal layer fixed in a vertical alignment, and a retardation film having a phase difference function, and an elliptical layer in which an optical film is laminated as needed. The polarizing plate may have, for example, the following configurations (1) to (6).
另外,以下的記載中,「/」如前述係指層的界面,而黏/接著劑層係省略。In the following description, "/" is the interface of the above-mentioned finger layer, and the adhesive/adhesive layer is omitted.
(1)直線偏光板/具有相位差功能的相位差膜/垂直配向液晶層/在薄膜面內具有相位差的正單軸性光學非等向性層/在膜厚方向具有相位差的負單軸性光學非等向性層(1) Linear polarizing plate / retardation film with phase difference function / vertical alignment liquid crystal layer / positive uniaxial optical anisotropic layer having phase difference in film surface / negative single sheet having phase difference in film thickness direction Axial optical anisotropic layer
(2)直線偏光板/具有相位差功能的相位差膜/垂直配向液晶層/負雙軸性光學非等向性層(2) Linear polarizing plate / phase difference film with phase difference function / vertical alignment liquid crystal layer / negative biaxial optical anisotropic layer
(3)直線偏光板/具有相位差功能的相位差膜/垂直配向液晶層/在薄膜面內具有相位差的正單軸性光學非等向性層(3) Linear polarizing plate/phase difference film with phase difference function/vertical alignment liquid crystal layer/positive uniaxial optical anisotropic layer having phase difference in film surface
(4)直線偏光板/垂直配向液晶層/具有相位差功能的相位差膜/在薄膜面內具有相位差的正單軸性光學非等向性層/在膜厚方向具有相位差的負單軸性光學非等向性層(4) Linear polarizing plate/vertical alignment liquid crystal layer/phase difference film having phase difference function/positive uniaxial optical anisotropic layer having phase difference in film surface/reduced sheet having phase difference in film thickness direction Axial optical anisotropic layer
(5)直線偏光板/垂直配向液晶層/具有相位差功能的相位差膜/負雙軸性光學非等向性層(5) Linear polarizer/vertical alignment liquid crystal layer/phase difference film with phase difference function/negative biaxial optical anisotropic layer
(6)直線偏光板/垂直配向液晶層/具有相位差功能的相位差膜/在薄膜面內具有相位差的正單軸性光學非等向性層(6) Linear polarizer/vertical alignment liquid crystal layer/phase difference film with phase difference function/positive uniaxial optical anisotropic layer with phase difference in film surface
在製作配置有本發明橢圓偏光板的液晶顯示裝置時,視需要亦可追加設置諸如光擴散層、光控制薄膜、導光板、稜鏡片等構件。When a liquid crystal display device in which the elliptically polarizing plate of the present invention is disposed is produced, members such as a light diffusion layer, a light control film, a light guide plate, and a cymbal sheet may be additionally provided as needed.
使用本發明橢圓偏光板的液晶顯示裝置,係可舉例如以下(7)~(14)的構造:The liquid crystal display device using the elliptically polarizing plate of the present invention may have the following structures (7) to (14):
(7)直線偏光板/具有相位差功能的相位差膜/將垂直配向固定化的垂直配向液晶層/在薄膜面內具有相位差的正單軸性光學非等向性層/在膜厚方向具有相位差的負單軸性光學非等向性層/液晶單元/在薄膜面內具有相位差的正單軸性光學非等向性層/偏光板/背光源(7) Linear polarizing plate / retardation film having phase difference function / vertical alignment liquid crystal layer to which vertical alignment is fixed / positive uniaxial optical anisotropic layer having phase difference in film surface / in film thickness direction Negative uniaxial optical anisotropic layer/liquid crystal cell with phase difference / positive uniaxial optical anisotropic layer/polarizer/backlight with phase difference in film plane
(8)直線偏光板/具有相位差功能的相位差膜/將垂直配向固定化的垂直配向液晶層/在薄膜面內具有相位差的正單軸性光學非等向性層/在膜厚方向具有相位差的負單軸性光學具方性層/液晶單元/在膜厚方向具有相位差的負單軸性光學非等向性層/在薄膜面內具有相位差的正單軸性光學非等向性層/偏光板/背光源(8) Linear polarizing plate/phase difference film having phase difference function/vertical alignment liquid crystal layer to which vertical alignment is fixed/positive uniaxial optical anisotropic layer having phase difference in film surface/in film thickness direction Negative uniaxial optical square layer/liquid crystal cell having phase difference / negative uniaxial optical anisotropic layer having phase difference in film thickness direction / positive uniaxial optical non-phase difference in film plane Isotropic layer / polarizer / backlight
(9)直線偏光板/具有相位差功能的相位差膜/將垂直配向固定化的垂直配向液晶層/在薄膜面內具有相位差的正單軸性光學非等向性層/液晶單元/在膜厚方向具有相位差的負單軸性光學非等向性層/在薄膜面內具有相位差的正單軸性光學非等向性層/偏光板/背光源(9) Linear polarizing plate / retardation film having phase difference function / vertical alignment liquid crystal layer to which vertical alignment is fixed / positive uniaxial optical anisotropic layer / liquid crystal cell having phase difference in film surface / Negative uniaxial optical anisotropic layer with phase difference in film thickness direction / positive uniaxial optical anisotropic layer/polarizer/backlight with phase difference in film surface
(10)直線偏光板/具有相位差功能的相位差膜/將垂直配向固定化的垂直配向液晶層/負雙軸性光學非等向性層/液晶單元/在薄膜面內具有相位差的正單軸性光學非等向性層/偏光板/背光源(10) Linear polarizing plate / retardation film with phase difference function / Vertical alignment liquid crystal layer / negative biaxial optical anisotropic layer / liquid crystal cell with vertical alignment fixed / positive phase difference in film surface Uniaxial optical anisotropic layer / polarizer / backlight
(11)直線偏光板/具有相位差功能的相位差膜/將垂直配向固定化的垂直配向液晶層/負雙軸性光學非等向性層/液晶單元/負雙軸性光學非等向性層/偏光板/背光源(11) Linear polarizing plate / retardation film with phase difference function / vertical alignment liquid crystal layer / negative biaxial optical anisotropic layer / liquid crystal cell / negative biaxial optical anisotropy Layer/polarizer/backlight
(12)直線偏光板/具有相位差功能的相位差膜/將垂直配向固定化的垂直配向液晶層/在薄膜面內具有相位差的正單軸性光學非等向性層/液晶單元/負雙軸性光學非等向性層/偏光板/背光源(12) Linear polarizing plate / retardation film with phase difference function / Vertical alignment liquid crystal layer for vertical alignment / Positive uniaxial optical anisotropic layer / liquid crystal cell / negative with phase difference in film surface Biaxial optical anisotropic layer / polarizer / backlight
(13)直線偏光板/具有相位差功能的相位差膜/將垂直配向固定化的垂直配向液晶層/液晶單元/偏光板/背光源(13) Linear polarizing plate / retardation film with phase difference function / vertical alignment liquid crystal layer / liquid crystal cell / polarizing plate / backlight which is fixed by vertical alignment
(14)直線偏光板/將垂直配向固定化的垂直配向液晶層/具有相位差功能的相位差膜/液晶單元/偏光板/背光源(14) Linear polarizing plate / Vertical alignment liquid crystal layer to which vertical alignment is fixed / Phase difference film / Liquid crystal cell / polarizing plate / backlight with phase difference function
再者,上述(1)~(6)所記載的正單軸性光學非等向性層光學非等向性層及負雙軸性光學非等向性層、(7)~(9)的液晶單元、或與負單軸性光學非等向性層相鄰接的在薄膜面內具有相位差的正單軸性光學非等向性層、以及(10)~(12)的負雙軸性光學非等向性層,最好係面內呈現1/4波長的相位差。Further, the positive uniaxial optical anisotropic layer optical anisotropic layer and the negative biaxial optical anisotropic layer described in the above (1) to (6), and (7) to (9) a liquid crystal cell, or a positive uniaxial optical anisotropic layer having a phase difference in a film plane adjacent to a negative uniaxial optical anisotropic layer, and a negative biaxial axis of (10) to (12) The optically anisotropic layer preferably exhibits a phase difference of 1/4 wavelength in the plane.
呈現1/4波長相位差的較佳上述各光學非等向性層面內的延遲值(Re),相對波長550nm光係在100nm~180nm、最好120nm~160nm、尤以130nm~150nm範圍內為佳。當超出上述範圍外時,在與偏光板組合時將無法獲得充分的圓偏光性,恐有從正面觀看時會發生顯示特性降低的可能性。Preferably, the retardation value (Re) in each of the above optical anisotropy layers is 1/4 wavelength phase difference, and the relative wavelength 550 nm light is in the range of 100 nm to 180 nm, preferably 120 nm to 160 nm, particularly 130 nm to 150 nm. good. When it is outside the above range, sufficient circular polarization cannot be obtained when combined with a polarizing plate, and there is a possibility that display characteristics may be lowered when viewed from the front.
再者,當將上述(2)、(5)、(10)~(12)的負雙軸性光學非等向性層厚度設為d4、將面內的主折射率設為Nx4、Ny4、將厚度方向的折射率設為Nz4,且Nx4>Ny4>Nz4時,厚度方向的延遲值(Rth4=(Nx4-Nz4)×d4[nm]),有必需設定為依補償垂直配向型液晶單元厚度方向的相位差而發揮視角補償效果的條件。所以,雖依垂直配向型液晶單元厚度方向的相位差值而異,但將設定在50nm~600nm、最好100nm~400nm、尤以200nm~300nm範圍內為佳。若超出上述範圍外之時,無法獲得充分的視角改良效果,或從斜向觀看時恐有發生不必要著色的可能性。In addition, the thickness of the negative biaxial optical anisotropic layer of the above (2), (5), (10) to (12) is d4, and the principal refractive index in the plane is Nx4 or Ny4. When the refractive index in the thickness direction is Nz4 and Nx4>Ny4>Nz4, the retardation value in the thickness direction (Rth4=(Nx4-Nz4)×d4[nm]) must be set to compensate for the thickness of the vertical alignment type liquid crystal cell. The condition of the viewing angle compensation effect is exerted by the phase difference of the directions. Therefore, although the phase difference in the thickness direction of the vertical alignment type liquid crystal cell varies, it is preferably set in the range of 50 nm to 600 nm, preferably 100 nm to 400 nm, particularly preferably 200 nm to 300 nm. If it is outside the above range, a sufficient angle of view improvement effect cannot be obtained, or there is a possibility that unnecessary coloring may occur when viewed from an oblique direction.
本發明所使用的液晶單元並無特別的限制,可舉例如:穿透式、反射式、半穿透式各種液晶單元。就液晶單元若舉依液晶配向所構成的模式為例,則可舉例如:TN型、STN型、VA(vertical alignment,垂直配向)型、MVA(multi-domain vertical alignment,多象限垂直配向)型、OCB(optically compensated bend,光學補償彎曲)型、ECB(electrically controlled biriefringence,電控雙折射)型、HAN(hybrid-aligned nematic,複合配向向列)型、IPS(in-plane switching,橫向電場切換)、雙穩態向列(Bistable Nematic)型、ASM(Axially Symmetric Aligned Microcell,軸對稱對齊)型、半色調灰階型、強介電性液晶、利用反強介電性液晶的顯示方式等。The liquid crystal cell used in the present invention is not particularly limited, and examples thereof include a penetrating, reflective, and transflective liquid crystal cell. The liquid crystal cell is exemplified by a mode in which liquid crystal alignment is performed, and examples thereof include a TN type, an STN type, a VA (vertical alignment) type, and a MVA (multi-domain vertical alignment) type. OCB (optically compensated bend) type, ECB (electrically controlled biriefringence) type, HAN (hybrid-aligned nematic) type, IPS (in-plane switching) ), Bistable Nematic type, ASM (Axially Symmetric Aligned Microcell) type, halftone gray scale type, ferroelectric liquid crystal, display method using anti-strong dielectric liquid crystal, and the like.
構成液晶單元的透明基板係在屬於將構成液晶層且呈現液晶性的材料,朝特定配向方向施行配向之前提下,其餘並無特別的限制。具體係可使用例如:基板本身便具有使液晶配向性質的透明基板;或者將基板本體雖欠缺配向能力但卻設有具有使液晶配向性質之配向膜等的透明基板等等任何基板。此外,液晶單元的電極係可使用諸如ITO等周知物。電極通常係可設置於液晶層所鄰接的透明基板面上,當使用設有配向膜的基板時,可設置於基板與配向膜之間。The transparent substrate constituting the liquid crystal cell is removed from the material which constitutes the liquid crystal layer and exhibits liquid crystallinity, and is disposed before being aligned in a specific alignment direction, and is not particularly limited. Specifically, for example, a transparent substrate having a liquid crystal alignment property may be used as the substrate itself, or a substrate such as a transparent substrate having an alignment film or the like having a liquid crystal alignment property may be provided without the alignment ability of the substrate body. Further, the electrode system of the liquid crystal cell can use a known thing such as ITO. The electrode may be disposed on the surface of the transparent substrate adjacent to the liquid crystal layer, and may be disposed between the substrate and the alignment film when the substrate provided with the alignment film is used.
相關該液晶配向,可使用單元面內具有單一方向性者,亦可使用配向經分割的液晶顯示元件等。此外,若就對液晶單元施加電壓的方法而言,則可舉例如利用使用ITO電極等的被動式、或使用TFT(薄膜電晶體)電極、TFD(薄膜二極體)電極等的主動式等等施行驅動的液晶顯示元件。In the liquid crystal alignment, a single directionality in the unit plane can be used, and a liquid crystal display element which is divided by alignment can be used. In addition, a method of applying a voltage to the liquid crystal cell may be, for example, a passive type using an ITO electrode or the like, or an active type using a TFT (Thin Film Transistor) electrode, a TFD (Thin Film Diode) electrode, or the like. A liquid crystal display element is driven.
將可形成在液晶單元的單側或雙側配置著偏光板、光學薄膜的液晶顯示裝置,或者照明系統係使用背光源或反射板等的適當液晶顯示裝置。此情況,光學薄膜係可配置於液晶單元的單側或雙側。當在雙側設置偏光板、光學薄膜的情況,該等係可為相同物,亦可為不同物。此外,當形成液晶顯示裝置之際,可將例如擴散板、防眩層、抗反射膜、保護板、稜鏡陣列、透鏡陣列薄片、光擴散板、背光源等適當零件,在適當位置上配置1層或2層以上。A liquid crystal display device in which a polarizing plate or an optical film is disposed on one side or both sides of a liquid crystal cell, or a suitable liquid crystal display device such as a backlight or a reflecting plate can be used. In this case, the optical film can be disposed on one side or both sides of the liquid crystal cell. When the polarizing plate or the optical film is provided on both sides, the lines may be the same or different. Further, when a liquid crystal display device is formed, suitable components such as a diffusion plate, an antiglare layer, an antireflection film, a protective plate, a ruthenium array, a lens array sheet, a light diffusion plate, and a backlight can be disposed at appropriate positions. 1 or more layers.
再者,藉由將上述液晶單元的其中一基板設為具有反射功能區域、與具有穿透功能區域的基板,便可形成半穿透反射式液晶顯示元件。Further, by forming one of the substrates of the liquid crystal cell as a reflective functional region and a substrate having a penetrating functional region, a transflective liquid crystal display device can be formed.
半穿透反射式液晶顯示元件所使用的半穿透反射性電極中所含具有反射功能的區域(以下稱「反射層」),並無特別的限制,可例示:鋁、銀、金、鉻、白金等金屬、或含該等的合金;氧化鎂等氧化物;介電質的多層膜、呈現選擇反射的液晶、或該等的組合等。該等反射層係可為平面,且亦可為曲面。此外,反射層係可為經施行加工為凹凸形狀等表面形狀,而具有擴散反射性者;或兼具液晶單元觀察者側之背後側的該電極基板上電極者;或者該等的組合。The region having a reflection function (hereinafter referred to as "reflection layer") included in the transflective reflector used for the transflective liquid crystal display device is not particularly limited, and examples thereof include aluminum, silver, gold, and chromium. a metal such as platinum, or an alloy containing the same; an oxide such as magnesium oxide; a multilayer film of a dielectric material; a liquid crystal exhibiting selective reflection; or a combination thereof. The reflective layers can be planar and can also be curved. Further, the reflective layer may be a surface having a surface shape such as a concavo-convex shape and having a diffuse reflectance; or an electrode on the back side of the liquid crystal cell observer side; or a combination thereof.
本發明的液晶顯示裝置係除上述構成構件之外,尚可附設其他構成構件。例如藉由將彩色濾光片附設於本發明液晶顯示裝置上,便可製得可施行色純度較高之多彩或全彩顯示的彩色液晶顯示裝置。In the liquid crystal display device of the present invention, in addition to the above-described constituent members, other constituent members may be attached. For example, by attaching a color filter to the liquid crystal display device of the present invention, a color liquid crystal display device capable of performing color or full color display with high color purity can be obtained.
以下利用實施例針對本發明進行具體的說明,惟本發明並不僅侷限於該等。The present invention will be specifically described below by way of examples, but the invention is not limited thereto.
另外,實施例所使用的各測定方法係如下:In addition, each measurement method used in the examples is as follows:
將化合物溶解於重氫化氯仿中,並利用400MHZ的1 H-NMR(Variant公司製INOVA-400)施行測定。The compound was dissolved in dihydrochloroform and measured by 1 H-NMR (INOVA-400, manufactured by Variant) of 400 MHz.
將化合物溶解四氫呋喃中,利用Tosoh公司製8020GPC系統,將TSK-GEL SuperH1000、SuperH2000、SuperH3000、SuperH4000串聯連接,且溶出液係使用四氫呋喃施行測定。分子量的較正係使用聚苯乙烯標樣。The compound was dissolved in tetrahydrofuran, and TSK-GEL SuperH1000, SuperH2000, SuperH3000, and SuperH4000 were connected in series using an 8020 GPC system manufactured by Tosoh Corporation, and the eluate was measured using tetrahydrofuran. The correction of the molecular weight uses polystyrene standards.
利用Olympus光學公司製BH2偏光顯微鏡觀察液晶的配向狀態。The alignment state of the liquid crystal was observed using a BH2 polarizing microscope manufactured by Olympus Optics Co., Ltd.
使用王子計測機器公司製自動複折射計KOBRA21ADH。The automatic complex refractometer KOBRA21ADH manufactured by Oji Scientific Co., Ltd. was used.
擷取液晶層之後,使用微分式掃描熱量計(DSC、Perkin Elmer公司製DSC-7),依升溫速度20℃/min施行測定。After the liquid crystal layer was taken, it was measured using a differential scanning calorimeter (DSC, DSC-7 manufactured by Perkin Elmer Co., Ltd.) at a temperature elevation rate of 20 ° C/min.
利用ELDIM公司製EzContrast實施液晶顯示裝置的視角測定,而獲得等對比曲線。The viewing angle measurement of the liquid crystal display device was carried out by using EzContrast manufactured by ELDIM Co., Ltd., and an iso-contrast curve was obtained.
將三醋酸纖維素(TAC)薄膜(40μm、FUJIFILM公司製)在室溫下,於2質量%的氫氧化鉀水溶液中浸漬5分鐘而施行皂化處理,在流水中施行洗淨後便乾燥。在經延伸的聚乙烯醇上吸附著碘而獲得偏光元件,在該偏光元件其中一面上,使用接著劑層1為丙烯酸系接著劑,貼合著經皂化的TAC薄膜,便製得積層體1(TAC薄膜/接著劑層1/偏光元件)。A cellulose triacetate (TAC) film (40 μm, manufactured by FUJIFILM Co., Ltd.) was immersed in a 2% by mass aqueous potassium hydroxide solution at room temperature for 5 minutes to carry out saponification treatment, and then washed in running water and then dried. A polarizing element is obtained by adsorbing iodine on the stretched polyvinyl alcohol, and a layered body 1 is obtained by laminating a saponified TAC film on one surface of the polarizing element using an adhesive layer 1 as an acrylic adhesive. (TAC film/adhesive layer 1/polarizing element).
利用自由基共聚合,合成下式(9)所示側鏈型液晶性高分子化合物。依GPC所測得分子量,若依聚苯乙烯換算,數量平均分子量Mn=8000、重量平均分子量Mw=15000。另外,式(9)所示係依嵌段聚合物的構造記載,並表示單體的結構比。The side chain type liquid crystalline polymer compound represented by the following formula (9) is synthesized by radical copolymerization. The molecular weight measured by GPC is, in terms of polystyrene, the number average molecular weight Mn = 8000 and the weight average molecular weight Mw = 15000. Further, the formula (9) is described based on the structure of the block polymer, and represents the structural ratio of the monomer.
經式(9)所示側鏈型液晶性高分子化合物10.0g溶解於90ml的環己酮中,並在暗處添加三烯丙基鋶六氟銻鹽50%碳酸丙烯酯溶液(Aldrich公司製、試劑)1.0g後,並利用孔徑0.45μm聚四氟乙烯製過濾器施行過濾,便調製得液晶性組成物的溶液。10.0 g of the side chain type liquid crystalline polymer compound represented by the formula (9) was dissolved in 90 ml of cyclohexanone, and a triallyl hexafluoroantimony salt 50% propylene carbonate solution (manufactured by Aldrich Co., Ltd.) was added in the dark. After 1.0 g of the reagent and the filter were filtered through a filter made of a polytetrafluoroethylene having a pore size of 0.45 μm, a solution of the liquid crystal composition was prepared.
配向基板係依如下述進行調製。在寬650mm、厚38μm的長條聚對苯二甲酸乙二酯(PET)薄膜(TORAY(股)製)上,狹縫式塗佈機連續的將烷基改質聚乙烯醇(PVA、KURARAY(股)製、MP-203)之5質量%溶液(溶劑係水與異丙醇依質量比1:1的混合溶劑)施行塗佈,經乾燥,再依130℃施行加熱處理,便獲得PVA層厚1.2μm的配向基板薄膜1。The alignment substrate is prepared as follows. On a strip of polyethylene terephthalate (PET) film (manufactured by TORAY) with a width of 650 mm and a thickness of 38 μm, the slit coater continuously reforms the alkyl group of polyvinyl alcohol (PVA, KURARAY). A 5 mass% solution of a (method) system and MP-203) (a solvent mixture of solvent water and isopropyl alcohol according to a mass ratio of 1:1) was applied, dried, and then subjected to heat treatment at 130 ° C to obtain PVA. The alignment substrate film 1 having a layer thickness of 1.2 μm.
其次,將PVA層利用嫘縈摩擦布施行摩擦。摩擦時的周速比(摩擦布移動速度/基板薄膜移動速度)係設為4。Next, the PVA layer was rubbed with a rubbing rubbing cloth. The peripheral speed ratio (friction cloth moving speed / substrate film moving speed) at the time of rubbing was set to 4.
在依此所獲得配向基板上,將依上述所獲得液晶性組成物的溶液,使用狹縫式塗佈機連續的施行塗佈,經乾燥後,施行130℃×10分鐘加熱處理,而使液晶性組成物層垂直配向。接著,一邊密接於經加熱至60℃的金屬滾筒,一邊從上方利用高壓水銀燈照射600mJ/cm2 的紫外光(UV)(係指依365nm所測得光量)照射,而使液晶性組成物硬化,便獲得積層體2(PET薄膜/PVA層/垂直配向液晶層)。On the alignment substrate obtained as described above, the solution of the liquid crystal composition obtained as described above was continuously applied by a slit coater, dried, and then subjected to heat treatment at 130 ° C for 10 minutes to form a liquid crystal. The composition layer is vertically aligned. Next, while adhering to a metal roll heated to 60 ° C, the liquid crystal composition was hardened by irradiating ultraviolet light (UV) (which is measured by 365 nm) at 600 mJ/cm 2 from above with a high-pressure mercury lamp. Then, a laminate 2 (PET film/PVA layer/vertical alignment liquid crystal layer) was obtained.
為施行所獲得垂直配向液晶層的光學參數測定,便製作積層體3。The laminate 3 is produced for the measurement of the optical parameters of the vertically aligned liquid crystal layer obtained.
因為配向基板所使用的PET薄膜係具有較大複折射,因而頗難依積層體2形態施行垂直配向液晶層的光學參數(Re、Rth等)測定,所以便在三醋酸纖維素(TAC)薄膜上,依如下述轉印垂直配向液晶層。Since the PET film used for the alignment substrate has a large birefringence, it is difficult to measure the optical parameters (Re, Rth, etc.) of the vertically aligned liquid crystal layer in the form of the laminate 2, so that the cellulose triacetate (TAC) film is formed. The vertical alignment liquid crystal layer is transferred as follows.
即,在PET薄膜上的光學異方元件上,將依紫外線硬化型接著劑依厚5μm的方式施行塗佈,並利用TAC薄膜(厚40μm)施行積層,再從TAC薄膜側施行紫外線照射,而使接著劑硬化後,便將PVA層及PET薄膜剝離,便獲得積層體3(垂直配向液晶層/接著劑層2/TAC薄膜)。In other words, on the optical element on the PET film, the ultraviolet curable adhesive was applied in a thickness of 5 μm, and laminated on a TAC film (thickness: 40 μm), and ultraviolet light was applied from the TAC film side. After the adhesive is cured, the PVA layer and the PET film are peeled off to obtain a laminate 3 (vertical alignment liquid crystal layer/adhesive layer 2/TAC film).
若將所獲得積層體3在偏光顯微鏡下進行觀察,得知屬於將無錯向的單一區域均勻配向,且從錐光鏡觀察中得知,屬於具有正單軸性折射率構造的垂直配向。使用KOBRA21ADH所測得積層體3的面內方向延遲值(Re)係0.5nm,厚度方向的延遲值(Rth)係-140nm。另外,因為所使用的TAC薄膜單體係負單軸性,且Re係-0.5nm、Rth係+40nm,因而預估單獨垂直配向液晶層的Re係0nm、且Rth係-100nm。When the obtained laminated body 3 was observed under a polarizing microscope, it was found that the single region having no misdirection was uniformly aligned, and it was found from the observation of the conoscope that it was a vertical alignment having a positive uniaxial refractive index structure. The in-plane retardation value (Re) of the laminated body 3 measured by KOBRA21ADH was 0.5 nm, and the retardation value (Rth) in the thickness direction was -140 nm. Further, since the TAC film used in the single system has negative uniaxiality, and Re is -0.5 nm and Rth is +40 nm, it is estimated that Re is 0 nm and Rth is -100 nm in the vertical alignment liquid crystal layer alone.
再者,僅擷取積層體3的垂直配向液晶層部分,使用DSC施行玻璃轉移點測定,結果Tg係100℃。此外,垂直配向液晶層表面的鉛筆硬度係2H程度,將可獲得充分堅固的膜。Further, only the portion of the vertical alignment liquid crystal layer of the laminate 3 was taken, and the glass transition point was measured by DSC, and as a result, Tg was 100 °C. Further, the pencil hardness of the surface of the vertical alignment liquid crystal layer is about 2H, and a sufficiently strong film can be obtained.
將面內具有相位差的相位差膜(WR、帝人(股)製),依230℃施行縱單軸延伸,便獲得具有負雙軸性的薄膜1。面內的相位差係140nm。a retardation film having a phase difference in the plane ( WR, Teijin Co., Ltd., which performs longitudinal uniaxial stretching at 230 ° C, obtains a film 1 having negative biaxiality. The phase difference in the plane is 140 nm.
對薄膜1施行電暈放電處理(250W‧min/m2 ),並經由黏著劑,在偏光元件的雙側貼附著經使用等向性保護膜為TAC薄膜進行保護的偏光板,而獲得橢圓偏光板A(薄膜1/黏著劑層/TAC薄膜/黏著劑層/偏光元件/黏著劑層/TAC薄膜)。橢圓偏光板A的膜厚係190μm。The film 1 was subjected to corona discharge treatment (250 W ‧ min/m 2 ), and a polarizing plate protected by a TAC film using an isotropic protective film was attached to both sides of the polarizing element via an adhesive to obtain elliptically polarized light. Plate A (film 1 / adhesive layer / TAC film / adhesive layer / polarizing element / adhesive layer / TAC film). The film thickness of the elliptically polarizing plate A was 190 μm.
對面內相位差140nm、膜厚方向的相位差0nm之相位差膜(ZEONOR薄膜、日本ZEON(股)製),利用嫘縈布施行摩擦處理,並將依參考例1所獲得液晶性組成物的溶液,使用狹縫式塗佈機施行連續性塗佈,經乾燥後,施行130℃×10分鐘加熱處理,便使液晶性組成物層垂直配向。接著,一邊密接於經加熱至60℃的金屬滾筒,一邊從上方利用高壓水銀燈照射600mJ/cm2 紫外光(UV)(係指依365nm所測得光量)照射,而使液晶性組成物硬化,便獲得積層體4(ZEONOR薄膜/垂直配向液晶層)。A retardation film (ZEONOR film, manufactured by Nippon Zeon Co., Ltd.) having a phase difference of 140 nm in the in-plane direction and a phase difference of 0 nm in the film thickness direction was subjected to rubbing treatment using a rubbing cloth, and the liquid crystal composition obtained in Reference Example 1 was obtained. The solution was subjected to continuous coating using a slit coater, and after drying, it was subjected to heat treatment at 130 ° C for 10 minutes to vertically align the liquid crystal composition layer. Next, while adhering to a metal roll heated to 60° C., a high-pressure mercury lamp was used to irradiate 600 mJ/cm 2 of ultraviolet light (UV) (the amount of light measured by 365 nm) from above, and the liquid crystal composition was cured. A laminate 4 (ZEONOR film/vertical alignment liquid crystal layer) is obtained.
對積層體4的ZEONOR薄膜側施行電暈放電處理(250W‧min/m2 ),經由黏著劑貼附著屬於直線偏光板的積層體1,便獲得本發明的橢圓偏光板1(TAC薄膜/接著劑層1/偏光元件/黏著劑層/ZEONOR薄膜/垂直配向液晶層)。Purposes corona ZEONOR film 4 side of the laminate discharge treatment (250W‧min / m 2), is attached via the adhesive paste laminate belonging linear polarizers 1, it is obtained an elliptically polarizing plate of the present invention (the TAC film / Next Agent layer 1 / polarizing element / adhesive layer / ZEONOR film / vertical alignment liquid crystal layer).
對積層體4的垂直配向液晶層側施行電暈放電處理(250W‧min/m2 ),經由黏著劑貼附著屬於直線偏光板的積層體1,便獲得本發明的橢圓偏光板2(TAC薄膜/接著劑層1/偏光元件/黏著劑層/垂直配向液晶層/ZEONOR薄膜)。橢圓偏光板2的膜厚係126μm。The corona discharge treatment (250 W ‧ min/m 2 ) was applied to the side of the vertical alignment liquid crystal layer of the laminated body 4, and the laminated body 1 belonging to the linear polarizing plate was attached via an adhesive to obtain the elliptically polarizing plate 2 of the present invention (TAC film). / adhesive layer 1 / polarizing element / adhesive layer / vertical alignment liquid crystal layer / ZEONOR film). The film thickness of the elliptically polarizing plate 2 was 126 μm.
在面內相位差140nm、膜厚方向的相位差0nm之相位差膜(ZEONOR薄膜、日本ZEON(股)製)上,將烷基改質聚乙烯醇(PVA、KURARAY(股)製、MP-203)的5質量%溶液(溶劑係水與異丙醇依質量比1:1的混合溶劑),使用狹縫式塗佈機施行塗佈,經乾燥,再依130℃施行加熱處理,便獲得PVA層厚1.2μm的配向基板薄膜2。Alkyl-modified polyvinyl alcohol (PVA, KURARAY Co., Ltd., MP-) was obtained on a retardation film (ZEONOR film, manufactured by ZEON Co., Ltd.) having a phase difference of 140 nm in the in-plane phase and a phase difference of 0 nm in the film thickness direction. a 5% by mass solution of 203) (a solvent mixture of solvent-based water and isopropyl alcohol in a mass ratio of 1:1), which was applied by a slit coater, dried, and then subjected to heat treatment at 130 ° C to obtain The alignment substrate film 2 having a PVA layer thickness of 1.2 μm.
對上述配向基板薄膜2上,將依參考例1所獲得液晶性組成物的溶液,使用狹縫式塗佈機施行連續式塗佈,經乾燥後,在施行130℃×10分鐘加熱處理,便使液晶性組成物層垂直配向。接著,一邊密接於經加熱至60℃的金屬滾筒,一邊從上方利用高壓水銀燈照射600mJ/cm2 的紫外光(UV)(係指依365nm所測得光量)照射,而使液晶性組成物硬化,便獲得積層體5(ZEONOR薄膜/PVA層/垂直配向液晶層)。On the alignment substrate film 2, the solution of the liquid crystal composition obtained in Reference Example 1 was subjected to continuous coating using a slit coater, dried, and then subjected to heat treatment at 130 ° C for 10 minutes. The liquid crystal composition layer is vertically aligned. Next, while adhering to a metal roll heated to 60 ° C, the liquid crystal composition was hardened by irradiating ultraviolet light (UV) (which is measured by 365 nm) at 600 mJ/cm 2 from above with a high-pressure mercury lamp. Then, a laminate 5 (ZEONOR film/PVA layer/vertical alignment liquid crystal layer) is obtained.
對積層體5的垂直配向液晶層側施行電暈放電處理(250W‧min/m2 ),經由黏著劑貼附著屬於直線偏光板的積層體1,便獲得本發明的橢圓偏光板3(TAC薄膜/接著劑層1/偏光元件/黏著劑層/垂直配向液晶層/PVA層/ZEONOR薄膜)。The corona discharge treatment (250 W ‧ min/m 2 ) was applied to the side of the vertical alignment liquid crystal layer of the laminated body 5, and the laminated body 1 belonging to the linear polarizing plate was attached via an adhesive to obtain the elliptically polarizing plate 3 of the present invention (TAC film). / adhesive layer 1 / polarizing element / adhesive layer / vertical alignment liquid crystal layer / PVA layer / ZEONOR film).
在積層體2的垂直配向液晶層上,將市售UV硬化型接著劑(UV-3400、東亞合成(股)製)使用為接著劑層3,並塗佈成5μm厚狀態,再利用面內相位差140nm、膜厚方向的相位差0nm之相位差膜(ZEONOR薄膜、日本ZEON(股)製)進行積層,並從ZEONOR薄膜側施行紫外線照射,而使接著劑層3硬化後,在貼附著PVA層的狀態下將PET薄膜剝離,便獲得積層體6(ZEONOR薄膜/接著劑層3/垂直配向液晶層)。A commercially available UV-curable adhesive (UV-3400, manufactured by Toagosei Co., Ltd.) was used as the adhesive layer 3 on the vertical alignment liquid crystal layer of the laminate 2, and was applied in a 5 μm thick state, and then in-plane. A retardation film (ZEONOR film, manufactured by Nippon Zeon Co., Ltd.) having a phase difference of 140 nm and a phase difference of 0 nm in the film thickness direction is laminated, and ultraviolet rays are applied from the ZEONOR film side to cure the adhesive layer 3, and then adhered thereto. The PET film was peeled off in the state of the PVA layer to obtain a laminate 6 (ZEONOR film/adhesive layer 3/vertical alignment liquid crystal layer).
對積層體6的ZEONOR薄膜側施行電暈放電處理(250W‧min/m2 ),經由黏著劑貼附著屬於直線偏光板的積層體1,便獲得本發明的橢圓偏光板4(TAC薄膜/接著劑層1/偏光元件/黏著劑層/ZEONOR薄膜/接著劑層3/垂直配向液晶層)。Purposes corona ZEONOR film side of the laminate 6 discharge treatment (250W‧min / m 2), is attached via the adhesive paste laminate belonging linear polarizers 1, to obtain the elliptically polarizing plate of the present invention, it is 4 (TAC film / Next Agent layer 1 / polarizing element / adhesive layer / ZEONOR film / adhesive layer 3 / vertical alignment liquid crystal layer).
對積層體6的垂直配向液晶層側施行電暈放電處理(250W‧min/m2 ),經由黏著劑貼附著屬於直線偏光板的積層體1,便獲得本發明的橢圓偏光板5(TAC薄膜/接著劑層1/偏光元件/黏著劑層/垂直配向液晶層/接著劑層3/ZEONOR薄膜)。The corona discharge treatment (250 W ‧ min/m 2 ) was applied to the side of the vertical alignment liquid crystal layer of the laminated body 6, and the laminated body 1 belonging to the linear polarizing plate was attached via an adhesive to obtain the elliptically polarizing plate 5 of the present invention (TAC film). / adhesive layer 1 / polarizing element / adhesive layer / vertical alignment liquid crystal layer / adhesive layer 3 / ZEONOR film).
對薄膜1施行電暈放電處理(250W‧min/m2 ),經由黏著劑而與橢圓偏光板4的垂直配向液晶層側相黏貼,便獲得橢圓偏光板6(TAC薄膜/接著劑層1/偏光元件/黏著劑層/ZEONOR薄膜/接著劑層3/垂直配向液晶層/黏著劑層/薄膜1)。橢圓偏光板6的膜厚係172μm。1 for the purposes of the film to corona discharge treatment (250W‧min / m 2), via an adhesive applicators relative vertical alignment of the elliptical polarizing plate to the liquid crystal layer 4 side, then obtain an elliptically polarizing plate 6 (TAC film / adhesive layer 1 / Polarizing element/adhesive layer/ZEONOR film/adhesive layer 3/vertical alignment liquid crystal layer/adhesive layer/film 1). The film thickness of the elliptically polarizing plate 6 was 172 μm.
對依照背光源、背光源側偏光板、IPS型液晶單元、及視認側偏光板的順序配置之市售IPS型液晶電視,如圖1所示,取代視認側偏光板改為配置本發明的橢圓偏光板2。依此的話,相較於未使用本橢圓偏光板2的情況下,得知視角將擴大,即使從斜向仍可獲得良好的影像。另外,對比的視角依存性係如圖2所示。該圖中,粗黑線係指對比達100以上的區域。此外,同心圓係指20度間隔的視角(以下亦同)。For the commercially available IPS type liquid crystal televisions arranged in the order of the backlight, the backlight side polarizing plate, the IPS type liquid crystal unit, and the viewing side polarizing plate, as shown in FIG. 1, instead of the viewing side polarizing plate, the ellipse of the present invention is replaced. Polarizing plate 2. In this case, as compared with the case where the elliptically polarizing plate 2 is not used, it is known that the viewing angle is enlarged, and a good image can be obtained even from the oblique direction. In addition, the comparative perspective dependence is shown in Figure 2. In the figure, a thick black line refers to an area where the contrast is more than 100. In addition, concentric circles refer to a viewing angle of 20 degrees (the same applies hereinafter).
對依照背光源、背光源側偏光板、IPS型液晶單元、及視認側偏光板的順序配置之市售VA型液晶電視,如圖3所示,取代視認側偏光板改為配置本發明的橢圓偏光板6,並取代背光源側偏光板改為配置依參考例2所獲得橢圓偏光板A。依此的話,相較於未使用本橢圓偏光板6的情況下,得知視角擴大,即使從斜向仍可獲得良好的影像。對比的視角依存性係如圖4所示。For a commercially available VA type liquid crystal television arranged in the order of a backlight, a backlight side polarizing plate, an IPS type liquid crystal cell, and a viewing side polarizing plate, as shown in FIG. 3, instead of the viewing side polarizing plate, the ellipse of the present invention is replaced. The polarizing plate 6 was replaced with the elliptically polarizing plate A obtained in Reference Example 2 instead of the backlight side polarizing plate. In this case, as compared with the case where the elliptically polarizing plate 6 is not used, it is known that the angle of view is enlarged, and a good image can be obtained even from the oblique direction. The contrast dependence dependence is shown in Figure 4.
在積層體2的垂直配向液晶層上,將市售UV硬化型接著劑(UV-3400、東亞合成(股)製)使用為接著劑層4,並塗佈成厚5μm狀態,再利用PET薄膜進行積層,且從PET薄膜側施行紫外線照射,經使接著劑層4硬化後,便在貼附著PVA層的狀態下,將與PVA層相鄰側的PET薄膜剝離,便獲得積層體7(PET薄膜/接著劑層4/垂直配向液晶層)。On the vertical alignment liquid crystal layer of the laminate 2, a commercially available UV-curable adhesive (UV-3400, manufactured by Toagosei Co., Ltd.) was used as the adhesive layer 4, and was applied in a thickness of 5 μm, and then a PET film was used. After laminating, the ultraviolet ray is irradiated from the PET film side, and after the adhesive layer 4 is cured, the PET film adjacent to the PVA layer is peeled off while the PVA layer is attached, and the laminated body 7 is obtained. Film/Binder Layer 4/Vertical Alignment Liquid Crystal Layer).
此外,在積層體7的垂直配向液晶層側上,將市售UV硬化型接著劑(UV-3400、東亞合成(股)製)使用為接著劑層5,並塗佈成厚5μm狀態,再利用TAC薄膜進行積層,並從TAC薄膜側施行紫外線照射,而使接著劑層5硬化後,再將PET薄膜剝離,便獲得積層體8(接著劑層4/垂直配向液晶層/接著劑層5/TAC薄膜)。Further, on the side of the vertical alignment liquid crystal layer of the laminated body 7, a commercially available UV-curable adhesive (UV-3400, manufactured by Toagos Corporation) was used as the adhesive layer 5, and was applied in a state of 5 μm thick, and then The layered body 8 was obtained by laminating the TAC film and irradiating the TAC film side with ultraviolet rays, and then peeling the PET film, thereby obtaining the layered body 8 (the adhesive layer 4 / the vertical alignment liquid crystal layer / the adhesive layer 5) /TAC film).
對積層體8的接著劑層4側施行電暈放電處理(250W‧min/m2 ),經由黏著劑貼附著屬於直線偏光板的積層體1之後,再將TAC薄膜剝離,便獲得橢圓偏光板B(TAC薄膜/接著劑層1/偏光元件/黏著劑層/接著劑層4/垂直配向液晶層/接著劑層4)。Corona discharge treatment (250 W ‧ min/m 2 ) was applied to the adhesive layer 4 side of the laminated body 8 , and the laminated body 1 belonging to the linear polarizing plate was attached via an adhesive, and then the TAC film was peeled off to obtain an elliptically polarizing plate. B (TAC film/adhesive layer 1/polarizing element/adhesive layer/adhesive layer 4/vertical alignment liquid crystal layer/adhesive layer 4).
對依照背光源、背光源側偏光板、IPS型液晶單元、及視認側偏光板的順序配置之市售IPS型液晶電視,如圖5所示,取代視認側偏光板改為配置橢圓偏光板B。依此的話,相較於使用橢圓偏光板2的情況下,視角變狹窄。對比的視角依存性係如圖6所示。For the commercially available IPS type liquid crystal televisions arranged in the order of the backlight, the backlight side polarizing plate, the IPS type liquid crystal unit, and the viewing side polarizing plate, as shown in FIG. 5, instead of the viewing side polarizing plate, the elliptical polarizing plate B is replaced. . In this case, the viewing angle becomes narrower than in the case of using the elliptically polarizing plate 2. The contrast dependence is shown in Figure 6.
對面內相位差140nm、膜厚方向的相位差0nm之相位差膜(ZEONOR薄膜、日本ZEON(股)製)施行電暈放電處理(250W‧min/m2 ),經由黏著劑貼附著屬於直線偏光板的積層體1,便獲得橢圓偏光板C(TAC薄膜/接著劑層1/偏光元件/黏著劑層/ZEONOR薄膜)。Retardation, thickness direction retardation of 140nm in-plane retardation film 0nm (the ZEONOR film, by ZEON Japan (shares)) was performed to corona discharge treatment (250W‧min / m 2), the adhesive paste is attached via linear polarization belongs The laminated body 1 of the board was obtained as an elliptically polarizing plate C (TAC film/adhesive layer 1 / polarizing element / adhesive layer / ZEONOR film).
在比較例1的IPS型液晶顯示裝置製作中,除取代橢圓偏光板B改為配置橢圓偏光板C之外,其餘均同樣的實施。如同比較例1般,相較於使用橢圓偏光板2的情況下,視角變狹窄。對比的視角依存性係如圖7所示。In the production of the IPS type liquid crystal display device of Comparative Example 1, the same procedure was carried out except that the ellipsoidal polarizing plate B was replaced with the elliptically polarizing plate C. As in Comparative Example 1, the viewing angle was narrower than in the case of using the elliptically polarizing plate 2. The contrast dependence is shown in Figure 7.
對依照背光源、背光源側偏光板、IPS型液晶單元、及視認側偏光板的順序配置之市售IPS型液晶電視,如圖5所示,取代視認側偏光板改為配置依參考例2所獲得橢圓偏光板A。依此的話,相較於使用橢圓偏光板2的情況下,視角變狹窄,且橢圓偏光板A的總膜厚較厚,因而對模組的組裝、黏貼較為困難。For the commercially available IPS type liquid crystal televisions arranged in the order of the backlight, the backlight side polarizing plate, the IPS type liquid crystal unit, and the viewing side polarizing plate, as shown in FIG. 5, instead of the viewing side polarizing plate, the configuration is changed according to Reference Example 2. The elliptically polarizing plate A was obtained. In this case, the viewing angle becomes narrower than when the elliptically polarizing plate 2 is used, and the total thickness of the elliptically polarizing plate A is thick, so that assembly and adhesion of the module are difficult.
圖1為依實施例5所製得IPS型液晶顯示裝置的層構造示意剖視圖。1 is a schematic cross-sectional view showing a layer structure of an IPS type liquid crystal display device produced in Example 5.
圖2為依實施例5所製得IPS型液晶顯示裝置的對比之視角依存性圖。2 is a perspective dependence view of a comparison of an IPS type liquid crystal display device produced in Example 5.
圖3為依實施例6所製得VA型液晶顯示裝置的層構造示意剖視圖。Fig. 3 is a schematic cross-sectional view showing the layer structure of a VA liquid crystal display device produced in Example 6.
圖4為依實施例6所製得VA型液晶顯示裝置的對比之視角依存性圖。Fig. 4 is a view showing the dependence of the comparison of the VA type liquid crystal display device produced in the sixth embodiment.
圖5為依比較例1所製得IPS型液晶顯示裝置的層構造示意剖視圖。Fig. 5 is a schematic cross-sectional view showing the layer structure of an IPS type liquid crystal display device produced in Comparative Example 1.
圖6為依比較例1所製得IPS型液晶顯示裝置的對比之視角依存性圖。Fig. 6 is a view showing the dependence of the comparison of the IPS type liquid crystal display device produced in Comparative Example 1.
圖7為依比較例2所製得IPS型液晶顯示裝置的對比之視角依存性圖。Fig. 7 is a view showing the dependence of the comparison of the IPS type liquid crystal display device produced in Comparative Example 2.
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US9360707B2 (en) | 2011-12-19 | 2016-06-07 | Konica Minolta, Inc. | IPS mode liquid crystal display device |
JP5956276B2 (en) * | 2012-08-06 | 2016-07-27 | 株式会社クラレ | Manufacturing method of polarizing film |
JP2015079230A (en) | 2013-09-10 | 2015-04-23 | 住友化学株式会社 | Manufacturing method for laminate |
JP7165491B2 (en) * | 2017-02-23 | 2022-11-04 | 住友化学株式会社 | Optical film and its manufacturing method |
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TW200628859A (en) * | 2004-12-27 | 2006-08-16 | Dainippon Ink & Chemicals | Optical film, elliptically polarizing plate, circularly polarizing plate, liquid crystal display element, and method of producing optical film |
TW200643487A (en) * | 2005-02-25 | 2006-12-16 | Nitto Denko Corp | Method of producing elliptically polarizing plate and image display using the elliptically polarizing plate |
EP1850155A1 (en) * | 2005-02-08 | 2007-10-31 | Nippon Oil Corporation | Homeotropically oriented liquid-crystal film, optical film comprising the same, and image display |
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JP2006195424A (en) * | 2004-12-14 | 2006-07-27 | Nitto Denko Corp | Elliptical polarization plate, manufacturing method thereof and image display device using elliptical polarization plate |
JP2006337575A (en) * | 2005-05-31 | 2006-12-14 | Nippon Oil Corp | Homeotropically oriented liquid-crystal film, and device using the same |
JP2007017637A (en) * | 2005-07-06 | 2007-01-25 | Nippon Oil Corp | Laminated optical retardation plate, method for producing the same, luminance-improving film, and image display device |
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2007
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2008
- 2008-08-18 WO PCT/JP2008/065060 patent/WO2009028429A1/en active Application Filing
- 2008-08-18 KR KR1020107006144A patent/KR20100057654A/en not_active Application Discontinuation
- 2008-08-18 CN CN200880101710A patent/CN101772718A/en active Pending
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TW200628859A (en) * | 2004-12-27 | 2006-08-16 | Dainippon Ink & Chemicals | Optical film, elliptically polarizing plate, circularly polarizing plate, liquid crystal display element, and method of producing optical film |
EP1850155A1 (en) * | 2005-02-08 | 2007-10-31 | Nippon Oil Corporation | Homeotropically oriented liquid-crystal film, optical film comprising the same, and image display |
TW200643487A (en) * | 2005-02-25 | 2006-12-16 | Nitto Denko Corp | Method of producing elliptically polarizing plate and image display using the elliptically polarizing plate |
Also Published As
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CN101772718A (en) | 2010-07-07 |
WO2009028429A1 (en) | 2009-03-05 |
TW200918967A (en) | 2009-05-01 |
KR20100057654A (en) | 2010-05-31 |
JP2009053292A (en) | 2009-03-12 |
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