TWI645020B - Manufacturing method of vertical alignment liquid crystal film - Google Patents

Manufacturing method of vertical alignment liquid crystal film Download PDF

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TWI645020B
TWI645020B TW107113321A TW107113321A TWI645020B TW I645020 B TWI645020 B TW I645020B TW 107113321 A TW107113321 A TW 107113321A TW 107113321 A TW107113321 A TW 107113321A TW I645020 B TWI645020 B TW I645020B
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liquid crystal
film
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film substrate
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TW201842169A (en
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鈴木暢
飯田敏行
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日商日東電工股份有限公司
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
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    • 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
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    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G—PHYSICS
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    • H05B33/00—Electroluminescent light sources
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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Abstract

本發明藉由在未設置垂直配向膜之膜基板上，塗佈含有側鏈型液晶聚合物及光聚合性液晶單體之液晶性組合物，使液晶聚合物及液晶單體於液晶狀態下進行垂直配向，並藉由光照射使液晶單體進行聚合或交聯，可獲得垂直配向液晶膜。本發明之側鏈型液晶聚合物具有含有液晶性片段側鏈之單體單元與含有非液晶性片段側鏈之單體單元。本發明較佳為使用延伸膜作為膜基板，將使液晶化合物配向時之加熱溫度設為特定範圍。 In the present invention, a liquid crystal composition containing a side chain liquid crystal polymer and a photopolymerizable liquid crystal monomer is coated on a film substrate without a vertical alignment film, so that the liquid crystal polymer and the liquid crystal monomer are carried out in a liquid crystal state. Vertical alignment and polymerization or cross-linking of liquid crystal monomers by light irradiation can obtain a vertical alignment liquid crystal film. The side chain liquid crystal polymer of the present invention has a monomer unit containing a liquid crystal segment side chain and a monomer unit containing a non-liquid crystal segment side chain. In the present invention, it is preferable to use an stretched film as a film substrate, and set the heating temperature when the liquid crystal compound is aligned to a specific range.

Description

垂直配向液晶膜之製造方法 Manufacturing method of vertical alignment liquid crystal film

本發明係關於一種垂直配向液晶膜及其製造方法。 The invention relates to a vertical alignment liquid crystal film and a manufacturing method thereof.

作為具有液晶顯示裝置之光學補償、有機EL(Electroluminescence，電致發光)元件之抗外界光反射等功能之光學膜，業界使用有液晶化合物沿特定方向進行配向之液晶膜。由於液晶化合物之配向膜之雙折射大於聚合物之延伸膜，故而有利於薄型化或輕量化。例如，關於具有正折射率各向異性之液晶分子沿基板面之法線方向(厚度方向)進行配向之垂直配向液晶膜，作為液晶分子之配向方向之厚度方向之折射率(異常光折射率)nz大於面內之折射率(尋常光折射率)nx及ny，可用作具有nz>nx=ny之折射率各向異性之正C板。 As an optical film having the functions of optical compensation of a liquid crystal display device and organic EL (Electroluminescence) elements' resistance to external light reflection, the industry uses a liquid crystal film in which liquid crystal compounds are aligned in a specific direction. Since the birefringence of the alignment film of the liquid crystal compound is larger than that of the stretched film of the polymer, it is advantageous for thinning or lightening. For example, regarding a vertically aligned liquid crystal film in which liquid crystal molecules having positive refractive index anisotropy are aligned along the normal direction (thickness direction) of the substrate surface, the refractive index (abnormal light refractive index) in the thickness direction of the alignment direction of the liquid crystal molecules nz is larger than the in-plane refractive index (ordinary light refractive index) nx and ny, and can be used as a positive C plate with refractive index anisotropy of nz> nx = ny.

自發地進行垂直配向之物質非常有限，通常藉由在具備垂直配向膜之基板上塗佈液晶化合物，而製作垂直配向液晶膜。專利文獻1揭示有包含特定之側鏈型液晶聚合物與光聚合性液晶單體之組合物於不具有垂直配向膜之基板上進行垂直配向。具體而言，將液晶性組合物塗佈於基板上，以液晶聚合物呈現液晶狀態之方式加熱後進行冷卻而使配向固定化，並藉由光照射使液晶單體進行聚合或交聯，藉此可獲得垂直配向液晶膜。 The substances that spontaneously perform vertical alignment are very limited. Usually, a vertical alignment liquid crystal film is produced by coating a liquid crystal compound on a substrate provided with a vertical alignment film. Patent Document 1 discloses that a composition containing a specific side chain liquid crystal polymer and a photopolymerizable liquid crystal monomer is vertically aligned on a substrate without a vertical alignment film. Specifically, the liquid crystal composition is coated on a substrate, and the liquid crystal polymer is heated in a liquid crystal state, and then cooled to fix the alignment, and the liquid crystal monomer is polymerized or crosslinked by light irradiation. This can obtain a vertical alignment liquid crystal film.

專利文獻1中記載有於降烯系膜等光學各向異性較小之膜上塗佈液晶性組合物而製作垂直配向液晶膜之方法、或將形成於具有光學各向異性之塑膠膜或金屬膜上之配向液晶膜轉印至光學各向異性較小之塑膠膜上之 方法。於專利文獻1中，作為實施例，記載有如下例：於降烯系聚合物膜或玻璃基板上塗佈液晶性組合物，加熱至130℃而使液晶配向，其後照射紫外線而製作垂直配向液晶膜。 Patent Document 1 describes A method for coating a liquid crystal composition on a film having a small optical anisotropy, such as an olefin film, to prepare a vertically aligned liquid crystal film, or transferring an aligned liquid crystal film formed on a plastic film or a metal film having optical anisotropy Method for plastic film with less optical anisotropy. In Patent Document 1, as an example, the following example is described: Yu Jiang A liquid crystal composition is applied to an olefin-based polymer film or a glass substrate, the liquid crystal is aligned by heating to 130 ° C, and then ultraviolet rays are irradiated to produce a vertically aligned liquid crystal film.

[先前技術文獻] [Prior technical literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利第4174192號 [Patent Document 1] Japanese Patent No. 4174192

隨著顯示器之高精細化或高亮度化，對顯示器用光學膜要求更高之面內均一性，且於液晶配向膜中，微小區域之配向缺陷被視為問題。若於偏光顯微鏡下觀察專利文獻1中所記載之垂直配向液晶膜，則觀察到由微小之配向缺陷所引起之局部之漏光。鑒於該課題，本發明之目的在於提供一種配向缺陷較少之垂直配向液晶膜。 With the high definition or high brightness of the display, higher in-plane uniformity is required for the optical film for the display, and in the liquid crystal alignment film, alignment defects of minute regions are regarded as a problem. When the vertical alignment liquid crystal film described in Patent Document 1 is observed under a polarizing microscope, local light leakage caused by minute alignment defects is observed. In view of this problem, an object of the present invention is to provide a vertically aligned liquid crystal film with fewer alignment defects.

鑒於上述而本發明者等人進行研究，結果發現，藉由調整供塗佈液晶性組合物之膜基板、或使液晶分子配向之條件等，可獲得配向缺陷較少之垂直配向液晶膜，從而完成本發明。 In view of the above, the present inventors conducted research, and found that, by adjusting a film substrate for coating a liquid crystal composition or conditions for aligning liquid crystal molecules, a vertically aligned liquid crystal film with fewer alignment defects can be obtained, thereby The present invention has been completed.

本發明係關於一種側鏈型液晶聚合物及光聚合性液晶化合物之聚合物進行垂直配向之垂直配向液晶膜及其製造方法。 The present invention relates to a vertical alignment liquid crystal film having a side chain liquid crystal polymer and a polymer of a photopolymerizable liquid crystal compound, and a method for manufacturing the same.

藉由在未設置垂直配向膜之膜基板之第一主面上塗佈含有側鏈型液晶聚合物及光聚合性液晶單體之液晶性組合物(塗佈步驟)、使液晶聚合物及液晶單體於液晶狀態下進行垂直配向(液晶配向步驟)、藉由光照射使液晶單體進行聚合或交聯(光聚合步驟)，而於膜基板上形成垂直配向液晶 膜。 A liquid crystal composition containing a side chain liquid crystal polymer and a photopolymerizable liquid crystal monomer is coated on a first main surface of a film substrate on which a vertical alignment film is not provided (coating step), and the liquid crystal polymer and the liquid crystal are coated. The monomers are aligned vertically in the liquid crystal state (liquid crystal alignment step), and the liquid crystal monomers are polymerized or cross-linked by light irradiation (photopolymerization step) to form vertically aligned liquid crystals on the film substrate. membrane.

側鏈型液晶聚合物較佳為具有含有液晶性片段側鏈之單體單元與含有非液晶性片段側鏈之單體單元者。液晶性組合物中之光聚合性液晶單體之含量較佳為側鏈型液晶聚合物之含量之1.1~10倍。 The side chain liquid crystal polymer is preferably one having a monomer unit containing a liquid crystal segment side chain and a monomer unit containing a non-liquid crystal segment side chain. The content of the photopolymerizable liquid crystal monomer in the liquid crystal composition is preferably 1.1 to 10 times the content of the side chain liquid crystal polymer.

液晶配向時之加熱溫度T(℃)與膜基板之面內雙折射△n較佳為滿足T≦100-3.5×103△n。藉由降低液晶配向時之加熱溫度，可獲得液晶之配向缺陷減少，而均一性較高之垂直配向液晶膜。 The heating temperature T (° C) during the liquid crystal alignment and the in-plane birefringence Δn of the film substrate preferably satisfy T ≦ 100-3.5 × 10 3 Δn. By lowering the heating temperature during liquid crystal alignment, a vertical alignment liquid crystal film with less alignment defects and higher uniformity can be obtained.

藉由第一主面(供塗佈液晶性組合物之面)使用平滑之膜基板，有配向缺陷減少之傾向。膜基板之第一主面之算術平均粗糙度較佳為3nm以下。作為算術平均粗糙度較小而平滑性優異之膜基板，較佳為使用延伸膜。延伸膜之面內延遲例如為10~500nm。於在延伸膜基板上塗佈液晶性組合物之情形時，存在基板之配向限制力阻礙液晶性組合物之垂直配向性之情形，但若如上所述般降低用於使液晶配向之加熱溫度，則可減少配向缺陷。 By using a smooth film substrate as the first main surface (the surface to which the liquid crystalline composition is applied), there is a tendency that alignment defects are reduced. The arithmetic mean roughness of the first main surface of the film substrate is preferably 3 nm or less. As a film substrate having a small arithmetic average roughness and excellent smoothness, it is preferable to use an stretched film. The in-plane retardation of the stretched film is, for example, 10 to 500 nm. When the liquid crystal composition is coated on the stretched film substrate, the alignment restriction force of the substrate may hinder the vertical alignment of the liquid crystal composition, but if the heating temperature for liquid crystal alignment is lowered as described above, It can reduce alignment defects.

膜基板亦可於第二主面具有易滑層。較佳為於膜基板之第一主面不設置易滑層。作為膜基板，例如可使用降烯系聚合物膜。 The film substrate may have an easy-slip layer on the second main surface. It is preferable that no slippery layer is provided on the first main surface of the film substrate. As the film substrate, for example, Ethylene polymer film.

垂直配向液晶膜較佳為至少一面之算術平均粗糙度為3nm以下。垂直配向液晶膜較佳為每1cm2之配向缺陷數為1個以下。 The vertical alignment liquid crystal film preferably has an arithmetic average roughness of at least one side of 3 nm or less. The number of alignment defects per 1 cm 2 of the vertical alignment liquid crystal film is preferably 1 or less.

根據本發明，可獲得微小之配向缺陷較少而面內均一性優異之垂直配向液晶膜。 According to the present invention, a vertical alignment liquid crystal film with few minute alignment defects and excellent in-plane uniformity can be obtained.

液晶配向膜係藉由在基板上塗佈液晶性組合物，並使其配向固定而 製作。 A liquid crystal alignment film is obtained by coating a substrate with a liquid crystal composition and fixing the alignment thereof. Production.

[液晶性組合物] [Liquid Crystal Composition]

垂直配向液晶膜之製作中所使用之液晶性組合物包含側鏈型液晶聚合物、及光聚合性液晶單體。 The liquid crystal composition used in the production of the vertical alignment liquid crystal film includes a side chain liquid crystal polymer and a photopolymerizable liquid crystal monomer.

<側鏈型液晶聚合物> <Side-chain liquid crystal polymer>

作為側鏈型液晶聚合物，可使用具有含有液晶性片段側鏈之單體單元與含有非液晶性片段側鏈之單體單元之共聚物。藉由聚合物於側鏈具有液晶性片段，於將液晶性組合物加熱至特定溫度時，聚合物進行垂直配向。又，藉由聚合物於側鏈具有非液晶性片段，使液晶性組合物中所含之光聚合性液晶單體與聚合物一起進行垂直配向之配向力起作用。藉由使液晶單體隨側鏈型液晶聚合物之配向而配向，並使該配向狀態固定，可獲得垂直配向液晶膜。 As the side chain liquid crystal polymer, a copolymer having a monomer unit containing a liquid crystal segment side chain and a monomer unit containing a non-liquid crystal segment side chain can be used. Since the polymer has a liquid crystal segment in a side chain, the polymer is vertically aligned when the liquid crystal composition is heated to a specific temperature. In addition, since the polymer has a non-liquid crystalline segment in the side chain, the photo-polymerizable liquid crystal monomer contained in the liquid crystalline composition and the polymer are aligned with the vertical alignment force. By aligning the liquid crystal monomer with the alignment of the side chain liquid crystal polymer and fixing the alignment state, a vertically aligned liquid crystal film can be obtained.

作為具有液晶性片段側鏈之單體，可列舉具有包含液晶原基之向列型液晶性之取代基之聚合性化合物。作為液晶原基，可列舉：聯苯基、苯基苯甲酸酯基、苯基環己烷基、氧化偶氮苯基、次甲基偶氮基、偶氮苯基、苯基嘧啶基、二苯基乙炔基、二苯基苯甲酸酯基、雙環己烷基、環己基苯基、聯三苯基等環狀結構。該等環狀單元之末端亦可具有氰基、烷基、烷氧基、鹵基等取代基。其中，作為液晶原基，較佳為具有聯苯基、苯基苯甲酸酯基者。 Examples of the monomer having a liquid crystal segment side chain include a polymerizable compound having a nematic liquid crystal substituent having a mesogen group. Examples of the mesogen include biphenyl, phenylbenzoate, phenylcyclohexane, azophenyloxy, methineazo, azophenyl, phenylpyrimidinyl, Ring structures such as diphenylethynyl, diphenylbenzoate, dicyclohexane, cyclohexylphenyl, and tritriphenyl. The ends of these cyclic units may have substituents such as cyano, alkyl, alkoxy, and halo. Among them, the mesogen is preferably one having a biphenyl group or a phenylbenzoate group.

作為具有非液晶性片段側鏈之單體，可列舉具有碳數7以上之長鏈烷基等直鏈狀之取代基之聚合性化合物。作為液晶性單體及非液晶性單體之聚合性官能基，例如可列舉(甲基)丙烯醯基。 Examples of the monomer having a non-liquid crystal segment side chain include a polymerizable compound having a linear substituent such as a long-chain alkyl group having 7 or more carbon atoms. Examples of the polymerizable functional group of the liquid crystalline monomer and the non-liquid crystalline monomer include (meth) acrylfluorenyl groups.

作為側鏈型液晶聚合物，可較佳地使用具有通式(I)所表示之液晶性 單體單元與通式(II)所表示之非液晶性單體單元之共聚物。 As the side chain liquid crystal polymer, liquid crystallinity having a general formula (I) can be preferably used. A copolymer of a monomer unit and a non-liquid crystalline monomer unit represented by general formula (II).

於式(I)中，R1為氫原子或甲基，R2為氰基、氟基、碳數1~6之烷基、或碳數1~6之烷氧基，X1為-CO2-或-OCO-。a為1~6之整數，b及c分別獨立地為1或2。 In formula (I), R 1 is a hydrogen atom or a methyl group, R 2 is a cyano group, a fluoro group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and X 1 is -CO 2 -or-OCO-. a is an integer from 1 to 6, and b and c are each independently 1 or 2.

於式(II)中，R3為氫原子或甲基，R4為碳數7~22之烷基、碳數1~22之氟烷基、或下述通式(III)所表示之基。 In formula (II), R 3 is a hydrogen atom or a methyl group, and R 4 is an alkyl group having 7 to 22 carbon atoms, a fluoroalkyl group having 1 to 22 carbon atoms, or a group represented by the following general formula (III) .

於式(III)中，R5為碳數1~5之烷基，d為1~6之整數。 In the formula (III), R 5 is an alkyl group having 1 to 5 carbon atoms, and d is an integer from 1 to 6.

側鏈型液晶聚合物中之液晶性單體單元與非液晶性單體單元之比率並無特別限定，於非液晶性單體單元之比率較少之情形時，存在伴隨側鏈型液晶聚合物之配向之光聚合性液晶化合物之配向變得不充分，光硬化後之液晶層之配向變得不均勻之情形。另一方面，於液晶性單體單元之比率較少之情形時，側鏈型液晶聚合物不易顯示出液晶單域配向性。因此，非液晶性單體相對於液晶性單體單元與非液晶性單體單元之合計之比率以莫耳比計較佳為0.01~0.8，更佳為0.1~0.6，進而較佳為0.15~0.5。就同時實 現液晶性組合物之成膜性與配向性之觀點而言，側鏈型液晶聚合物之重量平均分子量較佳為2000~100000左右，更佳為2500~50000左右。 The ratio of the liquid crystalline monomer unit to the non-liquid crystalline monomer unit in the side chain liquid crystal polymer is not particularly limited. When the ratio of the non-liquid crystalline monomer unit is small, there is a side chain liquid crystal polymer. The alignment of the aligned photopolymerizable liquid crystal compound becomes insufficient, and the alignment of the liquid crystal layer after photo-hardening becomes uneven. On the other hand, when the ratio of the liquid crystalline monomer units is small, the side chain liquid crystal polymer is unlikely to exhibit liquid crystal single-domain alignment. Therefore, the ratio of the non-liquid crystalline monomer to the total of the liquid crystalline monomer unit and the non-liquid crystalline monomer unit is preferably 0.01 to 0.8, more preferably 0.1 to 0.6, and still more preferably 0.15 to 0.5 in terms of molar ratios. . Just at the same time From the viewpoint of the film-forming property and the alignment property of the liquid crystal composition, the weight average molecular weight of the side chain liquid crystal polymer is preferably about 2,000 to 100,000, and more preferably about 2500 to 50,000.

側鏈型液晶聚合物可藉由各種公知之方法進行聚合。例如，於單體單元具有(甲基)丙烯醯基作為聚合性官能基之情形時，藉由利用光或熱之自由基聚合，可獲得具有液晶性片段及非液晶性片段之側鏈型液晶聚合物。 The side chain liquid crystal polymer can be polymerized by various known methods. For example, when the monomer unit has a (meth) acrylfluorenyl group as a polymerizable functional group, a side chain liquid crystal having a liquid crystal segment and a non-liquid crystal segment can be obtained by radical polymerization using light or heat polymer.

<光聚合性液晶化合物> <Photopolymerizable liquid crystal compound>

光聚合性液晶化合物(單體)於1分子中具有液晶原基與至少1個光聚合性官能基。作為液晶原基，可列舉上文作為側鏈型液晶聚合物之液晶性片段所述者。作為光聚合性官能基，可列舉：(甲基)丙烯醯基、環氧基、乙烯醚基等。其中，較佳為(甲基)丙烯醯基。 The photopolymerizable liquid crystal compound (monomer) has a mesogen group and at least one photopolymerizable functional group in one molecule. Examples of the mesogenic group include those described above as the liquid crystal segment of the side chain liquid crystal polymer. Examples of the photopolymerizable functional group include a (meth) acrylfluorenyl group, an epoxy group, and a vinyl ether group. Among these, (meth) acrylfluorenyl is preferred.

光聚合性液晶單體較佳為於1分子中具有2個以上之光聚合性官能基者。藉由使用包含2個以上之光聚合性官能基之液晶單體，而向光聚合後之液晶層中導入交聯結構，故而有垂直配向液晶膜之耐久性提高之傾向。 The photopolymerizable liquid crystal monomer is preferably one having two or more photopolymerizable functional groups in one molecule. By using a liquid crystal monomer containing two or more photopolymerizable functional groups and introducing a crosslinked structure into the liquid crystal layer after photopolymerization, the durability of the vertically aligned liquid crystal film tends to be improved.

作為於1分子中具有液晶原基與複數個(甲基)丙烯醯基之光聚合性液晶單體，例如可列舉下述通式(IV)所表示之化合物。 Examples of the photopolymerizable liquid crystal monomer having a mesogen and a plurality of (meth) acrylfluorenyl groups in one molecule include compounds represented by the following general formula (IV).

於式(IV)中，R為氫原子或甲基，A及D分別獨立地為1,4-伸苯基或1,4-伸環己基，B為1,4-伸苯基、1,4-伸環己基、4,4'-伸聯苯基或4,4'-伸聯環己基，Y及Z分別獨立地為-COO-、-OCO-或-O-。g及h分別獨立地為2~6之整數。 In formula (IV), R is a hydrogen atom or a methyl group, A and D are independently 1,4-phenylene or 1,4-cyclohexyl, and B is 1,4-phenylene, 1, 4-Cyclohexyl, 4,4'-biphenyl, or 4,4'-bicyclohexyl, and Y and Z are each independently -COO-, -OCO-, or -O-. g and h are each independently an integer of 2-6.

作為上述通式(IV)所表示之光聚合性液晶單體之市售品，可例示 BASF公司製造之「Paliocolor LC242」。 Examples of the commercially available photopolymerizable liquid crystal monomer represented by the general formula (IV) include: "Paliocolor LC242" manufactured by BASF.

<組成> <Composition>

液晶性組合物中之光聚合性液晶化合物(單體)與側鏈型液晶聚合物之比率並無特別限制。就獲得耐久性較高之垂直配向液晶膜之觀點而言，較佳為光聚合性液晶化合物之含量多於側鏈型液晶聚合物之含量。就獲得耐久性較高且配向均一性較高之垂直配向液晶膜之觀點而言，液晶性組合物中之光聚合性液晶化合物之含量(重量)較佳為側鏈型液晶聚合物之含量之1.5~15倍，更佳為2~10倍，進而較佳為2.5~6倍。 The ratio of the photopolymerizable liquid crystal compound (monomer) to the side chain liquid crystal polymer in the liquid crystal composition is not particularly limited. From the viewpoint of obtaining a vertically aligned liquid crystal film having high durability, the content of the photopolymerizable liquid crystal compound is preferably more than the content of the side chain liquid crystal polymer. From the viewpoint of obtaining a vertically aligned liquid crystal film with higher durability and higher alignment uniformity, the content (weight) of the photopolymerizable liquid crystal compound in the liquid crystal composition is preferably the content of the side chain liquid crystal polymer. 1.5 to 15 times, more preferably 2 to 10 times, and even more preferably 2.5 to 6 times.

為了促進利用光照射之光聚合性液晶化合物之硬化，液晶性組合物較佳為含有光聚合起始劑。作為光聚合起始劑，例如可例示：BASF公司製造之Irgacure 907、Irgacure 184、Irgacure 651、Irgacure 369等。關於液晶性組合物中之光聚合起始劑之含量，相對於光聚合性液晶化合物100重量份，通常為0.5~20重量份左右，較佳為3~15重量份左右，更佳為5~10重量份左右。 In order to promote hardening of the photopolymerizable liquid crystal compound by light irradiation, the liquid crystal composition preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include Irgacure 907, Irgacure 184, Irgacure 651, and Irgacure 369 manufactured by BASF. The content of the photopolymerization initiator in the liquid crystal composition is usually about 0.5 to 20 parts by weight, preferably about 3 to 15 parts by weight, and more preferably 5 to 100 parts by weight of the photopolymerizable liquid crystal compound. About 10 parts by weight.

藉由將側鏈型液晶聚合物、光聚合性液晶化合物及光聚合起始劑與溶劑混合，可製備液晶性組合物。溶劑只要係可溶解側鏈型液晶聚合物及光聚合性液晶化合物，且不會侵蝕膜基板(或侵蝕性較低)者，則並無特別限定，可列舉：氯仿、二氯甲烷、四氯化碳、二氯乙烷、四氯乙烷、三氯乙烯、四氯乙烯、氯苯、鄰二氯苯等鹵化烴類；苯酚、對氯苯酚等酚類；苯、甲苯、二甲苯、甲氧基苯、1,2-二甲氧基苯等芳香族烴類；丙酮、甲基乙基酮、甲基異丁基酮、環己酮、環戊酮、2-吡咯啶酮、N-甲基-2-吡咯啶酮等酮系溶劑；乙酸乙酯、乙酸丁酯等酯系溶劑；第三丁醇、甘油、乙二醇、三乙二醇、乙二醇單甲醚、二乙二醇二甲醚、丙二醇、二丙二 醇、2-甲基-2,4-戊二醇等醇系溶劑；二甲基甲醯胺、二甲基乙醯胺等醯胺系溶劑；乙腈、丁腈等腈系溶劑；二***、二丁醚、四氫呋喃等醚系溶劑；乙基賽路蘇、丁基賽路蘇等。液晶性組合物之濃度通常為3~50重量%左右，較佳為7~35重量%左右。 A liquid crystal composition can be prepared by mixing a side chain liquid crystal polymer, a photopolymerizable liquid crystal compound, and a photopolymerization initiator with a solvent. The solvent is not particularly limited as long as it dissolves the side chain liquid crystal polymer and the photopolymerizable liquid crystal compound and does not erode the film substrate (or has low erodibility), and examples thereof include chloroform, dichloromethane, and tetrachloride. Halogenated hydrocarbons such as carbonized carbon, dichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, o-dichlorobenzene; phenols such as phenol and p-chlorophenol; benzene, toluene, xylene, methyl chloride Aromatic hydrocarbons such as oxybenzene, 1,2-dimethoxybenzene; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-pyrrolidone, N- Ketone solvents such as methyl-2-pyrrolidone; ester solvents such as ethyl acetate and butyl acetate; tertiary butanol, glycerol, ethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, and diethyl ether Glycol dimethyl ether, propylene glycol, dipropylene glycol Alcohol solvents such as alcohols and 2-methyl-2,4-pentanediol; amine solvents such as dimethylformamide and dimethylacetamide; nitrile solvents such as acetonitrile and butyronitrile; diethyl ether, Ether solvents such as dibutyl ether and tetrahydrofuran; ethyl cyrus, butyl cyrus and the like. The concentration of the liquid crystal composition is usually about 3 to 50% by weight, and preferably about 7 to 35% by weight.

[膜基板] [Film substrate]

於本發明中，作為供塗佈液晶性組合物之基板，可使用未設置垂直配向膜之膜基板。如上所述，由於液晶性組合物中之側鏈型液晶聚合物藉由加熱而進行垂直配向，故而無需於基板上設置垂直配向膜。藉由使用膜基板，可藉由卷對卷實施自向基板上之液晶性組合物之塗佈至液晶單體之利用光聚合之硬化之一系列步驟，故而可提高垂直配向液晶膜之生產性。 In the present invention, as the substrate for applying the liquid crystal composition, a film substrate without a vertical alignment film can be used. As described above, since the side chain liquid crystal polymer in the liquid crystal composition is vertically aligned by heating, there is no need to provide a vertical alignment film on the substrate. By using a film substrate, a series of steps of applying a liquid crystal composition on a self-directed substrate to a liquid crystal monomer and curing by photopolymerization can be performed by a roll-to-roll process, so that the productivity of a vertically aligned liquid crystal film can be improved. .

膜基板具有第一主面及第二主面，且於第一主面上塗佈液晶性組合物。構成膜基板之樹脂材料只要不溶解於液晶性組合物之溶劑中，且具有用以使液晶性組合物配向之加熱時之耐熱性，則並無特別限制，可列舉：聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯；聚乙烯、聚丙烯等聚烯烴；降烯系聚合物等環狀聚烯烴；二乙醯纖維素、三乙醯纖維素等纖維素系聚合物；丙烯酸系聚合物；苯乙烯系聚合物；聚碳酸酯、聚醯胺、聚醯亞胺等。其中，就容易獲得成形時之流動性優異，且平滑性較高之膜之方面而言，尤佳為使用降烯系聚合物膜作為膜基板。就將垂直配向液晶膜轉印至其他基材等時之剝離性優異之方面而言，亦較佳為降烯系聚合物膜。作為降烯系聚合物，可列舉：日本Zeon製造之Zeonor、Zeonex、JSR製造之Arton等。 The film substrate has a first main surface and a second main surface, and the liquid crystal composition is coated on the first main surface. The resin material constituting the film substrate is not particularly limited as long as it does not dissolve in the solvent of the liquid crystal composition and has heat resistance during heating to align the liquid crystal composition. Examples include polyethylene terephthalate. Polyesters such as diesters and polyethylene naphthalates; polyolefins such as polyethylene and polypropylene; Cyclic polyolefins such as olefin polymers; Cellulose polymers such as diacetyl cellulose and triethyl cellulose; Acrylic polymers; Styrene polymers; Polycarbonate, Polyamine, Polyamide Amine, etc. Among them, in terms of easily obtaining a film which is excellent in fluidity at the time of molding and has high smoothness, it is particularly preferable to reduce the use. An olefin-based polymer film is used as a film substrate. It is also preferred that the vertical alignment liquid crystal film has excellent peelability when transferred to other substrates. Ethylene polymer film. As drop Examples of the olefin polymer include Zeonor manufactured by Zeon Japan, Zeonex, Arton manufactured by JSR, and the like.

作為膜基板，亦可使用延伸膜。藉由將膜進行延伸，使成膜時之模線等凹凸平滑化，故而有膜基板之平滑性提高，算術平均粗糙度Ra減小 之傾向。就表面之均一性較高之方面而言，尤佳為使用雙軸延伸膜作為膜基板。 As the film substrate, a stretched film may be used. By extending the film, the irregularities such as mold lines during film formation are smoothed, so the smoothness of the film substrate is improved, and the arithmetic average roughness Ra is reduced. The tendency. In terms of higher surface uniformity, it is particularly preferable to use a biaxially stretched film as the film substrate.

用作膜基板之延伸膜之面內延遲R0通常為10nm以上。於膜基板係具有10nm以上之面內延遲之延伸膜之情形時，構成膜之聚合物沿特定方向(遲相軸方向或進相軸方向)優先地進行配向，故而有使液晶分子進行水平配向之配向限制力容易起作用，而阻礙液晶性組合物之垂直配向之傾向。如於下文中所詳細說明般，藉由降低使液晶分子進行垂直配向時之加熱溫度，於使用延伸膜基板之情形時，亦可獲得配向缺陷較少之垂直配向液晶膜。 The in-plane retardation R 0 of the stretched film used as a film substrate is usually 10 nm or more. In the case where the film substrate is an extended film having an in-plane retardation of 10 nm or more, the polymers constituting the film are preferentially aligned in a specific direction (late phase axis direction or advance axis direction), so the liquid crystal molecules are aligned horizontally. The alignment restricting force tends to work, and hinders the vertical alignment of the liquid crystal composition. As described in detail below, by lowering the heating temperature when the liquid crystal molecules are aligned vertically, when a stretched film substrate is used, a vertically aligned liquid crystal film with fewer alignment defects can also be obtained.

若膜基板之面內延遲過大，則存在可減少配向缺陷之溫度較低，於該溫度範圍內難以使側鏈型液晶聚合物進行液晶相轉移之情形。因此，膜基板之面內延遲R0較佳為500nm以下，更佳為300nm以下，進而較佳為200nm以下。 If the in-plane retardation of the film substrate is too large, the temperature at which alignment defects can be reduced may be low, and it may be difficult to cause side-chain liquid crystal polymers to undergo liquid crystal phase transfer within this temperature range. Therefore, the in-plane retardation R 0 of the film substrate is preferably 500 nm or less, more preferably 300 nm or less, and even more preferably 200 nm or less.

膜基板之厚度並無特別限定，若考慮處理性等，則通常為10~200μm左右。延伸膜之面內雙折射△n(將面內延遲R0除以厚度而得之值)較佳為0.01以下，更佳為0.008以下，進而較佳為0.006以下。 The thickness of the film substrate is not particularly limited, and in consideration of handleability and the like, it is usually about 10 to 200 μm. The in-plane birefringence Δn (a value obtained by dividing the in-plane retardation R 0 by the thickness) of the stretched film is preferably 0.01 or less, more preferably 0.008 or less, and even more preferably 0.006 or less.

膜基板之第一主面之算術平均粗糙度Ra較佳為3nm以下，更佳為2nm以下，進而較佳為1.5nm以下。藉由在Ra較小而平滑性較高之膜基板面塗佈液晶性組合物，有垂直配向液晶膜之配向缺陷減少之傾向。如上所述，藉由將膜進行延伸，有膜之Ra變小之傾向。因此，藉由使用延伸膜基板，有垂直配向液晶膜之配向缺陷減少之傾向。 The arithmetic mean roughness Ra of the first main surface of the film substrate is preferably 3 nm or less, more preferably 2 nm or less, and even more preferably 1.5 nm or less. By coating a liquid crystal composition on the surface of a film substrate having a small Ra and a high smoothness, there is a tendency that the alignment defects of the vertically aligned liquid crystal film are reduced. As described above, by stretching the film, the Ra of the film tends to decrease. Therefore, by using the stretched film substrate, there is a tendency that the alignment defects of the vertically aligned liquid crystal film are reduced.

由於膜基板之第一主面之表面形狀被轉印至形成於其上之垂直配向液晶膜，故而垂直配向液晶膜之基板面之Ra與基板之第一主面之Ra大致 相等。因此，於使用第一主面之Ra為3nm以下之膜基板之情形時，多數情況下液晶配向膜之基板面之Ra亦成為3nm以下。又，有液晶性組合物之塗佈時之空氣面之Ra變得小於基板面之Ra之傾向。因此，若使用第一主面之Ra為3nm以下之膜基板，則多數情況下垂直配向液晶膜之兩面之算術平均粗糙度成為3nm以下。 Since the surface shape of the first main surface of the film substrate is transferred to the vertical alignment liquid crystal film formed thereon, the Ra of the substrate surface of the vertical alignment liquid crystal film and the Ra of the first main surface of the substrate are approximately equal. Therefore, when a film substrate having a Ra of the first main surface of 3 nm or less is used, Ra of the substrate surface of the liquid crystal alignment film also becomes 3 nm or less in many cases. In addition, Ra of the air surface at the time of application of the liquid crystal composition tends to be smaller than Ra of the substrate surface. Therefore, if a film substrate having a Ra of the first main surface of 3 nm or less is used, the arithmetic average roughness of both sides of the vertically aligned liquid crystal film in most cases becomes 3 nm or less.

為了將算術平均粗糙度設為上述範圍，膜基板較佳為於內部不含填料者。不含填料而表面之平滑性較高之膜由於滑動性較低，故而存在產生黏連，或產生卷對卷製程中之搬送不良或捲繞不良之情形。為了防止由高平滑性所引起之黏連或搬送不良等，可列舉於膜基板貼合滑動性較高之其他膜之方法、或於膜基板設置易滑層之方法。於膜基板貼合其他膜之情形時，就抑制由接著層等向第一主面(供塗佈液晶性組合物之面)之轉印所引起之不良情況(液晶之配向不良或光學缺陷等)之觀點而言，較佳為貼合於第二主面(與液晶性組合物之塗佈面相反之側之面)。其中，於卷對卷製程中，於膜基板之卷取時，附著於第二主面之黏著劑等轉移至第一主面，而有可能導致配向不良或光學之缺陷。 In order to set the arithmetic mean roughness to the above range, it is preferable that the film substrate does not contain a filler inside. Films that do not contain fillers and have high surface smoothness have low sliding properties, which may cause blocking, or may cause poor conveyance or poor winding during the roll-to-roll process. In order to prevent blocking or poor transportation due to high smoothness, a method of attaching another film having a high sliding property to the film substrate, or a method of providing an easy-slip layer on the film substrate can be cited. In the case where a film substrate is bonded to another film, it is possible to suppress defects (such as poor alignment of the liquid crystal or optical defects) caused by the transfer of an adhesive layer or the like to the first main surface (the surface on which the liquid crystal composition is applied). From the viewpoint of), it is preferably bonded to the second main surface (the surface opposite to the coating surface of the liquid crystalline composition). Among them, in the roll-to-roll manufacturing process, when the film substrate is rolled, the adhesive or the like attached to the second main surface is transferred to the first main surface, which may cause poor alignment or optical defects.

因此，較佳為藉由在膜基板之至少一面設置易滑層，而改善滑動性。作為易滑層，例如可列舉於聚酯、聚胺基甲酸酯等黏合劑中含有平均粒徑為100nm以下之微小填料者。就維持將垂直配向液晶膜轉印至其他基材等時之剝離性，且抑制自膜基板剝離時易滑層向垂直配向液晶膜之轉印等不良情況之觀點而言，膜基板較佳為於供塗佈液晶性組合物之面不具有易滑層。即，較佳為使用於第二主面具有易滑層，且於第一主面不具有易滑層之膜基板。 Therefore, it is preferable to improve the sliding property by providing an easy slip layer on at least one side of the film substrate. Examples of the slippery layer include those containing a fine filler having an average particle diameter of 100 nm or less in an adhesive such as polyester and polyurethane. From the viewpoint of maintaining the releasability when transferring the vertically-aligned liquid crystal film to other substrates, and suppressing the troubles such as the transfer of the easy-sliding layer to the vertically-aligned liquid crystal film when peeling from the film substrate, the film substrate is preferably There is no slippery layer on the surface to which the liquid crystal composition is applied. That is, it is preferably used for a film substrate having an easy-slip layer on the second main surface and not having an easy-slip layer on the first main surface.

[於膜基板上之垂直配向液晶膜之形成] [Formation of vertical alignment liquid crystal film on film substrate]

於膜基板上塗佈液晶性組合物，藉由加熱使液晶性聚合物成為液晶狀態，使液晶性分子進行垂直配向，其後進行冷卻而使配向固定化，並藉由光照射使液晶單體進行聚合或交聯，藉此可獲得垂直配向液晶膜。 A liquid crystal composition is coated on a film substrate, the liquid crystal polymer is brought into a liquid crystal state by heating, the liquid crystal molecules are aligned vertically, and then the alignment is fixed by cooling, and the liquid crystal monomer is irradiated with light. Polymerization or crosslinking is performed, whereby a vertically aligned liquid crystal film can be obtained.

於膜基板上塗佈液晶性組合物之方法並無特別限定，可採用旋轉塗佈、模嘴塗佈、接觸輥式塗佈、凹版塗佈、反向塗佈、噴塗、邁耶棒式塗佈、輥刀塗佈、氣刀塗佈等。於塗佈溶液後，去除溶劑，藉此於膜基板上形成液晶性組合物層。塗佈厚度較佳為以使溶劑乾燥後之液晶性組合物層之厚度(垂直配向液晶膜之厚度)成為0.5~5μm左右之方式加以調整。 The method for coating the liquid crystal composition on the film substrate is not particularly limited, and spin coating, die coating, contact roll coating, gravure coating, reverse coating, spray coating, and Meyer bar coating can be used. Cloth, roll knife coating, air knife coating, etc. After the solution is applied, the solvent is removed to form a liquid crystal composition layer on the film substrate. The coating thickness is preferably adjusted so that the thickness of the liquid crystalline composition layer (thickness of the vertical alignment liquid crystal film) after the solvent is dried becomes about 0.5 to 5 μm.

藉由對形成於膜基板上之液晶性組合物層進行加熱而成為液晶相，液晶性組合物進行垂直配向。加熱溫度並無特別限定，通常為40~200℃左右。若加熱溫度過低，則有向液晶相之轉移變得不充分之傾向，若加熱溫度過高，則有配向缺陷增加之傾向。因此，加熱溫度較佳為45~100℃，更佳為50~95℃，進而較佳為55~90℃。加熱時間只要以向液晶相之轉移變得充分之方式加以調整即可，通常為30秒~30分鐘左右。 The liquid crystal composition layer formed on the film substrate is heated to form a liquid crystal phase, and the liquid crystal composition is vertically aligned. The heating temperature is not particularly limited, but is usually about 40 to 200 ° C. If the heating temperature is too low, the transition to the liquid crystal phase tends to be insufficient, and if the heating temperature is too high, the alignment defects tend to increase. Therefore, the heating temperature is preferably 45 to 100 ° C, more preferably 50 to 95 ° C, and even more preferably 55 to 90 ° C. The heating time may be adjusted so that the transition to the liquid crystal phase becomes sufficient, and is usually about 30 seconds to 30 minutes.

於使用延伸膜基板之情形時，有伴隨加熱溫度之上升而由膜基板之分子配向所引起之水平配向限制力容易起作用，而垂直配向液晶膜之配向缺陷增大之傾向。因此，於使用延伸膜基板之情形時，較佳為於液晶性化合物轉移至液晶相之溫度範圍內之低溫下進行加熱。液晶配向時之加熱溫度T(℃)較佳為100-3.5×103△n以下。△n為延伸膜基板之面內雙折射。加熱溫度T更佳為100-4×103△n以下，進而較佳為100-4.5×103△n以下。又，加熱溫度T較佳為100-0.1R0以下，更佳為100-0.12R0以下，進而較佳為100-0.13R0以下。R0為延伸膜基板之面內延遲。 When a stretched film substrate is used, the horizontal alignment restricting force caused by the molecular alignment of the film substrate tends to act as the heating temperature increases, and the vertical alignment liquid crystal film tends to have increased alignment defects. Therefore, when the stretched film substrate is used, it is preferable to perform heating at a low temperature within a temperature range where the liquid crystal compound is transferred to the liquid crystal phase. The heating temperature T (° C) during liquid crystal alignment is preferably 100-3.5 × 10 3 Δn or less. Δn is the in-plane birefringence of the stretched film substrate. The heating temperature T is more preferably 100-4 × 10 3 Δn or less, and still more preferably 100-4.5 × 10 3 Δn or less. Further, the heating temperature T is preferably 100-0.1R 0 or less, more preferably 100-0.12R 0 or less, and further preferably 100-0.13R 0 or less. R 0 is the in-plane retardation of the stretched film substrate.

於對液晶性組合物層進行加熱後，冷卻至液晶聚合物之玻璃轉移溫 度以下之溫度，藉此使液晶性化合物之配向固定。冷卻方法並無特別限定，例如，只要自加熱氛圍中取出至室溫下即可。亦可進行空氣冷卻、水冷等強制冷卻。 After heating the liquid crystal composition layer, it is cooled to the glass transition temperature of the liquid crystal polymer. At a temperature of less than or equal to 50 ° C, the alignment of the liquid crystal compound is fixed. The cooling method is not particularly limited, and for example, it may be taken out from a heating atmosphere to room temperature. Forced cooling such as air cooling and water cooling are also available.

對垂直配向經固定之液晶性組合物層進行光照射，使光聚合性液晶化合物進行聚合或交聯，藉此使光聚合性液晶化合物之配向固定，垂直配向液晶膜之耐久性提高。作為所照射之光，只要選擇光聚合起始劑發生裂解之波長之光即可，通常可使用紫外線。為了促進光聚合反應，光照射較佳為於氮氣等惰性氣體氛圍下進行。 The vertical alignment fixed liquid crystal composition layer is irradiated with light to polymerize or crosslink the photopolymerizable liquid crystal compound, thereby fixing the alignment of the photopolymerizable liquid crystal compound and improving the durability of the vertical alignment liquid crystal film. As the light to be irradiated, light having a wavelength at which the photopolymerization initiator is cleaved may be selected, and usually ultraviolet rays may be used. In order to promote the photopolymerization reaction, light irradiation is preferably performed in an inert gas atmosphere such as nitrogen.

[垂直配向液晶膜之特性及用途] [Characteristics and uses of vertical alignment liquid crystal film]

藉由上述而獲得之垂直配向液晶膜係面內延遲大致為0(例如5nm以下，較佳為3nm以下)，且厚度方向延遲為負(具有nz>nx=ny之折射率各向異性)之正C板。垂直配向液晶膜之(nx-nz)與厚度之積所表示之厚度方向延遲Rt例如為-50~-500nm左右。 The in-plane retardation of the vertically aligned liquid crystal film obtained by the above is approximately 0 (for example, less than 5nm, preferably less than 3nm), and the retardation in the thickness direction is negative (having a refractive index anisotropy of nz> nx = ny). Positive C plate. The thickness direction retardation R t represented by the product of (nx-nz) and thickness of the vertical alignment liquid crystal film is, for example, about -50 to -500 nm.

垂直配向液晶膜於偏光顯微鏡下觀察到之漏光(配向不良)較佳為每1cm2為1個以下，更佳為0.7個以下，進而較佳為0.5個以下。配向不良數係以對膜面內之10個部位進行觀察所得之平均值之形式而求出。如上所述，藉由使用平滑性較高之延伸膜基板，且將使液晶配向時之加熱溫度設為特定範圍，可獲得配向缺陷較少之垂直配向液晶膜。 The light leakage (poor alignment) observed in the vertically aligned liquid crystal film under a polarizing microscope is preferably 1 or less per 1 cm 2 , more preferably 0.7 or less, and even more preferably 0.5 or less. The number of misalignments is determined as an average value obtained by observing 10 locations in the film surface. As described above, by using a stretched film substrate having high smoothness and setting the heating temperature during liquid crystal alignment to a specific range, a vertical alignment liquid crystal film with fewer alignment defects can be obtained.

垂直配向液晶膜可用作以視角補償等為目的之顯示器用光學膜。垂直配向液晶膜可於與膜基板積層之狀態下使用，亦可自膜基板剝離而使用。垂直配向液晶膜亦可自膜基板剝離，並與相位差膜、偏光板、玻璃等基材積層而使用。 The vertical alignment liquid crystal film can be used as an optical film for a display for the purpose of viewing angle compensation and the like. The vertical alignment liquid crystal film can be used in a state of being laminated with a film substrate, or can be used by being peeled from the film substrate. The vertical alignment liquid crystal film can also be peeled from the film substrate and laminated with a substrate such as a retardation film, a polarizing plate, and glass to be used.

[實施例] [Example]

以下，列舉垂直配向液晶膜之製作例更詳細地說明本發明，但本發明並不限定於下述例。 Hereinafter, the present invention will be described in more detail by making examples of the vertical alignment liquid crystal film, but the present invention is not limited to the following examples.

[液晶性組合物之製備] [Preparation of liquid crystal composition]

使下述化學式(為n=0.35，為了便於說明而利用嵌段聚合物體表示)之重量平均分子量5000之側鏈型液晶聚合物20重量份、顯示向列型液晶相之聚合性液晶化合物(BASF製造之「Paliocolor LC242」)80重量份、及光聚合起始劑(BASF製造之「Irgacure 907」)5重量份溶解於環戊酮400重量份中而製備液晶性組合物。 20 parts by weight of a side-chain liquid crystal polymer having a weight average molecular weight of 5000 and a nematic liquid crystal phase (BASF) having a weight average molecular weight of 5,000 and a chemical formula (n = 0.35, for convenience of explanation) 80 parts by weight of "Paliocolor LC242" manufactured and 5 parts by weight of a photopolymerization initiator ("Irgacure 907" manufactured by BASF) were dissolved in 400 parts by weight of cyclopentanone to prepare a liquid crystal composition.

[實驗例1] [Experimental Example 1]

利用棒式塗佈機，以乾燥後之厚度成為1μm之方式將上述液晶性組合物塗佈於未延伸之降烯系膜(日本Zeon製造之「Zeonor Film」、厚度：50μm、面內延遲：0nm、算術平均粗糙度：2.3nm)，於表1所示之溫度(50~100℃)下加熱2分鐘而使液晶配向。其後，冷卻至室溫而使配向固定，並於氮氣氛圍下照射700mJ/cm2之紫外線，使液晶單體進行光硬化，而製作液晶配向膜。 Using a bar coater, apply the above-mentioned liquid crystal composition to the unstretched film so that the thickness after drying becomes 1 μm. Ethylene-based film ("Zeonor Film" manufactured by Zeon, Japan, thickness: 50 μm, in-plane retardation: 0 nm, arithmetic mean roughness: 2.3 nm), heated at the temperature (50 to 100 ° C) shown in Table 1 for 2 minutes, and Align the liquid crystal. Thereafter, the alignment was fixed by cooling to room temperature, and 700 mJ / cm 2 of ultraviolet light was irradiated in a nitrogen atmosphere to light-harden the liquid crystal monomer to produce a liquid crystal alignment film.

[實驗例2] [Experimental Example 2]

於在一面具有易滑層之雙軸延伸降烯系膜(日本Zeon製造之「Zeonor Film」、厚度：52μm、面內延遲：50nm、未形成易滑層之面 之算術平均粗糙度：1.2nm)之未形成易滑層之面，塗佈上述液晶性組合物，以與實驗例1同樣之方式製作液晶配向膜。 Biaxial extension with slip layer on one side Ethylene-based film ("Zeonor Film" manufactured by Zeon, Japan, thickness: 52 μm, in-plane retardation: 50 nm, arithmetic average roughness of the surface where no slip layer is formed: 1.2 nm) The liquid crystal composition was produced in the same manner as in Experimental Example 1 to produce a liquid crystal alignment film.

[實驗例3] [Experimental Example 3]

於在一面具有易滑層之雙軸延伸降烯系膜(日本Zeon製造之「Zeonor Film」、厚度：33μm、面內延遲：135nm、未形成易滑層之面之算術平均粗糙度：1.0nm)之未形成易滑層之面，塗佈上述液晶性組合物，以與實驗例1同樣之方式製作液晶配向膜。 Biaxial extension with slip layer on one side Ethylene-based film ("Zeonor Film" manufactured by Zeon, Japan, thickness: 33 μm, in-plane retardation: 135 nm, arithmetic average roughness of the surface where no slip layer is formed: 1.0 nm) The liquid crystal composition was produced in the same manner as in Experimental Example 1 to produce a liquid crystal alignment film.

[實驗例4] [Experimental Example 4]

於在一面具有易滑層之雙軸延伸降烯系膜(日本Zeon製造之「Zeonor Film」、厚度：34μm、面內延遲：270nm、未形成易滑層之面之算術平均粗糙度：0.9nm)之未形成易滑層之面，塗佈上述液晶性組合物，以與實驗例1同樣之方式製作液晶配向膜。 Biaxial extension with slip layer on one side Ethylene-based film ("Zeonor Film" manufactured by Zeon, Japan, thickness: 34 μm, in-plane retardation: 270 nm, arithmetic average roughness of the surface where no slip layer is formed: 0.9 nm) The liquid crystal composition was produced in the same manner as in Experimental Example 1 to produce a liquid crystal alignment film.

[實驗例5] [Experimental Example 5]

於雙軸延伸聚對苯二甲酸乙二酯膜(三菱化學製造之「DIAFOILT 302」、厚度：75μm)上，塗佈上述液晶性組合物，以與實驗例1同樣之方式製作液晶配向膜。 The liquid crystal composition was coated on a biaxially stretched polyethylene terephthalate film ("DIAFOILT 302" manufactured by Mitsubishi Chemical Corporation, thickness: 75 µm), and a liquid crystal alignment film was produced in the same manner as in Experimental Example 1.

[實驗例6] [Experimental Example 6]

將使組成變更為側鏈型液晶聚合物50重量份、聚合性液晶化合物50重量份之液晶性組合物塗佈於與實驗例2中所使用者相同之雙軸延伸膜上，於80℃下加熱2分鐘後，進行冷卻及光硬化，而製作液晶配向膜。 A liquid crystal composition having a composition changed to 50 parts by weight of a side chain type liquid crystal polymer and 50 parts by weight of a polymerizable liquid crystal compound was coated on a biaxially stretched film the same as the user used in Experimental Example 2 at 80 ° C. After heating for 2 minutes, cooling and photo-hardening were performed to prepare a liquid crystal alignment film.

[評價] [Evaluation] (算術平均粗糙度) (Arithmetic average roughness)

根據使用掃描式探針顯微鏡(AFM)之1μm見方之AFM觀察圖像，求 出算術平均粗糙度。 Obtain an image from a 1 μm square AFM observation image using a scanning probe microscope (AFM). Find the arithmetic mean roughness.

(延遲) (delay)

延遲之測定係使用偏光相位差測定系統(Axometrics製造 製品名「AxoScan」)，於23℃之環境下，測定波長590nm之值。液晶配向膜之延遲之測定係使用於在表面設置有黏著劑之玻璃板之黏著劑附設面上轉印有液晶配向膜之樣品，測定面內延遲R0、及40°傾斜時之延遲，並根據該等測定值，將液晶配向膜之平均折射率設為1.52而算出厚度方向延遲Rt。 The retardation was measured using a polarized retardation measurement system (product name "AxoScan" manufactured by Axometrics) in a 23 ° C environment at a wavelength of 590 nm. The measurement of the retardation of the liquid crystal alignment film is a sample in which a liquid crystal alignment film is transferred on the adhesive attachment surface of a glass plate provided with an adhesive on the surface, and the in-plane retardation R 0 and the retardation at a tilt of 40 ° are measured, and Based on these measured values, the thickness-direction retardation R t was calculated by setting the average refractive index of the liquid crystal alignment film to 1.52.

(配向缺陷) (Alignment defect)

於表面設置有黏著劑之玻璃板之黏著劑附設面上，轉印液晶配向膜，並於正交偏光之偏光顯微鏡下觀察1cm2之區域，對局部之漏光之數量進行計數。每1個試樣於10個部位(合計10cm2)進行偏光顯微鏡觀察，將漏光之數量之平均設為每1cm2之配向缺陷數。將各實驗例中所獲得之液晶配向膜之每1cm2之配向缺陷數示於表1。 On the adhesive attachment surface of the glass plate provided with an adhesive on the surface, a liquid crystal alignment film is transferred, and an area of 1 cm 2 is observed under a polarizing microscope with crossed polarized light, and the number of local light leaks is counted. Polarized light microscope observation was performed at 10 locations (total 10 cm 2 ) per sample, and the average number of light leaks was set to the number of alignment defects per 1 cm 2 . Table 1 shows the number of alignment defects per 1 cm 2 of the liquid crystal alignment film obtained in each experimental example.

(耐久性試驗) (Durability test)

將實驗例2之加熱溫度80℃下製作之液晶配向膜、及實驗例6之液晶配向膜轉印至表面設置有黏著劑之5cm見方之玻璃板之黏著劑附設面上，進行100個循環之-40℃與85℃之熱循環。將熱循環試驗後之厚度方向延遲相對於熱循環試驗前之厚度方向延遲之值(相位差保持率)、以及熱循環試驗後之樣品之利用目測觀察確認到之龜裂之數量、及每1cm2之配向缺陷數示於表2。 The liquid crystal alignment film prepared at a heating temperature of 80 ° C. in Experimental Example 2 and the liquid crystal alignment film of Experimental Example 6 were transferred to an adhesive attachment surface of a 5 cm square glass plate with an adhesive on the surface, and 100 cycles were performed. Thermal cycling between -40 ° C and 85 ° C. The thickness direction retardation after the thermal cycle test relative to the thickness direction retardation before the thermal cycle test (phase difference retention ratio), and the number of cracks confirmed by visual observation of the sample after the thermal cycle test, and per 1 cm The number of alignment defects of 2 is shown in Table 2.

根據表2所示之結果可知，於實驗例2及實驗例6中，於熱循環試驗之前後均未確認到配向缺陷，液晶之垂直配向被固定。但是，於光聚合性液晶單體之含量較少之實驗例6中，於熱循環試驗後產生龜裂，與實驗例2相比相位差保持率降低。根據該結果可知，藉由提高液晶性組合物中之光聚合性液晶單體之比率，可獲得溫度循環耐久性較高之垂直配向液晶膜。 From the results shown in Table 2, it can be seen that in Experimental Example 2 and Experimental Example 6, no alignment defect was confirmed before and after the thermal cycle test, and the vertical alignment of the liquid crystal was fixed. However, in Experimental Example 6 in which the content of the photopolymerizable liquid crystal monomer was small, cracks occurred after the thermal cycle test, and the retardation retention ratio was lower than that in Experimental Example 2. From this result, it is understood that by increasing the ratio of the photopolymerizable liquid crystal monomer in the liquid crystal composition, a vertically aligned liquid crystal film having high temperature cycle durability can be obtained.

於使用面內雙折射較大之雙軸延伸PET膜之實驗例5中，於50~100℃之範圍之任一加熱溫度下每1cm2均確認到10個以上之配向缺陷。另一方面，於實驗例1~4中，與實驗例5相比配向缺陷較少，可見加熱溫度越低則配向缺陷數越減少之傾向。根據該等結果可知，藉由使用面內雙折射為特定範圍之膜基板，降低液晶配向時之加熱溫度，可獲得配向缺陷較少之 垂直配向液晶膜。 In Experimental Example 5 using a biaxially stretched PET film having a large in-plane birefringence, more than 10 alignment defects were confirmed per 1 cm 2 at any heating temperature ranging from 50 to 100 ° C. On the other hand, in Experimental Examples 1 to 4, there are fewer alignment defects than Experimental Example 5. It can be seen that the lower the heating temperature, the fewer the number of alignment defects. From these results, it can be seen that by using a film substrate having a specific range of in-plane birefringence and lowering the heating temperature during liquid crystal alignment, a vertically aligned liquid crystal film with fewer alignment defects can be obtained.

若對比實驗例1與實驗例2，則於溫度50~90℃之範圍中，實驗例2之配向缺陷減少。另一方面，於溫度95℃及100℃下，實驗例2之配向缺陷數增大。於使用面內延遲R0為50nm之延伸膜基板之實驗例2中，於90℃以下之溫度下與實驗例1相比配向缺陷減少，相對於此，於使用R0為135nm之延伸膜基板之實驗例3中，配向缺陷減少之溫度範圍為50~80℃，於使用R0為270nm之延伸膜基板之實驗例3中，配向缺陷減少之溫度範圍為50~70℃。 If Experimental Example 1 is compared with Experimental Example 2, the alignment defects in Experimental Example 2 are reduced in the temperature range of 50 to 90 ° C. On the other hand, at temperatures of 95 ° C and 100 ° C, the number of alignment defects in Experimental Example 2 increased. In Experimental Example 2 using an extended film substrate with an in-plane retardation R 0 of 50 nm, alignment defects were reduced at a temperature below 90 ° C. compared to Experimental Example 1. In contrast, an extended film substrate with R 0 of 135 nm was used. In Experimental Example 3, the temperature range for reducing alignment defects is 50 to 80 ° C. In Experimental Example 3 using an extended film substrate with R 0 at 270 nm, the temperature range for reducing alignment defects is 50 to 70 ° C.

由於實驗例2~4中所使用之膜基材之Ra相同，故而可謂延伸膜之R0越小，可減少配向缺陷之溫度範圍越寬。可認為其原因在於，伴隨R0之增大而構成膜基板之聚合物向特定方向之配向增大，因膜基板而使液晶分子進行水平配向之配向限制力容易起作用。 Since Ra of the film substrate used in Experimental Examples 2 to 4 is the same, it can be said that the smaller R 0 of the stretched film is, the wider the temperature range in which alignment defects can be reduced. This is considered to be because the alignment of the polymer constituting the film substrate in a specific direction increases with an increase in R 0 , and the alignment limiting force for horizontal alignment of the liquid crystal molecules due to the film substrate is likely to act.

根據以上之結果可知，藉由調整使液晶配向時之加熱溫度，可獲得配向缺陷較少之垂直配向液晶膜。又，可認為延伸膜基板之供塗佈液晶性組合物之面之Ra較小亦有助於配向缺陷之減少。 From the above results, it can be seen that by adjusting the heating temperature when the liquid crystal is aligned, a vertical alignment liquid crystal film with fewer alignment defects can be obtained. In addition, it is considered that the smaller Ra of the surface of the stretched film substrate on which the liquid crystal composition is applied also contributes to the reduction of alignment defects.

Claims (8)

一種垂直配向液晶膜之製造方法，其具有：塗佈步驟，其係於具有第一主面與第二主面且未設置垂直配向膜之膜基板之第一主面上，塗佈含有側鏈型液晶聚合物及光聚合性液晶單體之液晶性組合物；液晶配向步驟，其係使上述液晶聚合物及上述液晶單體於液晶狀態下進行垂直配向；及光聚合步驟，其係藉由光照射使上述液晶單體進行聚合或交聯；且上述側鏈型液晶聚合物具有含有液晶性片段側鏈之單體單元與含有非液晶性片段側鏈之單體單元，上述膜基板係具有10~500nm之面內延遲之延伸膜，上述液晶配向步驟中之加熱溫度T(℃)與上述膜基板之面內雙折射△n滿足T≦100-3.5×103△n。A method for manufacturing a vertically-aligned liquid crystal film, comprising: a coating step of coating on a first main surface of a film substrate having a first main surface and a second main surface without a vertical alignment film, and containing a side chain; Liquid crystal composition of a liquid crystal polymer and a photopolymerizable liquid crystal monomer; a liquid crystal alignment step that vertically aligns the liquid crystal polymer and the liquid crystal monomer in a liquid crystal state; and a photopolymerization step by The liquid crystal monomer is polymerized or cross-linked by light irradiation; and the side chain liquid crystal polymer has a monomer unit containing a liquid crystal segment side chain and a monomer unit containing a non-liquid crystal segment side chain. The film substrate has For an in-plane retardation stretched film having a thickness of 10 to 500 nm, the heating temperature T (° C) in the liquid crystal alignment step and the in-plane birefringence Δn of the film substrate satisfy T ≦ 100-3.5 × 10 3 Δn. 如請求項1之垂直配向液晶膜之製造方法，其中上述側鏈型液晶聚合物具有下述通式(I)所表示之液晶性單體單元與下述通式(II)所表示之非液晶性單體單元，[化2]R1及R3分別獨立地為氫原子或甲基，X1為-CO2-基或-OCO-基，R2為氰基、氟基、碳數1~6之烷基、或碳數1~6之烷氧基，a為1~6之整數，b及c分別獨立地為1或2，R4為碳數7~22之烷基、碳數1~22之氟烷基、或下述通式(III)所表示之基，R5為碳數1~5之烷基，d為1~6之整數。The method for manufacturing a vertically-aligned liquid crystal film according to claim 1, wherein the side chain liquid crystal polymer has a liquid crystalline monomer unit represented by the following general formula (I) and a non-liquid crystal represented by the following general formula (II) Sex monomer unit, [Chemical 2] R 1 and R 3 are each independently a hydrogen atom or a methyl group, X 1 is a -CO 2 -group or -OCO- group, and R 2 is a cyano group, a fluoro group, an alkyl group having 1 to 6 carbon atoms, or a carbon number 1 to 6 alkoxy groups, a is an integer of 1 to 6, b and c are independently 1 or 2, R 4 is an alkyl group having 7 to 22 carbon atoms, a fluoroalkyl group having 1 to 22 carbon atoms, or A group represented by the following general formula (III), R 5 is an alkyl group having 1 to 5 carbon atoms, and d is an integer from 1 to 6; 如請求項1或2之垂直配向液晶膜之製造方法，其中上述膜基板之第一主面之算術平均粗糙度為3nm以下。For example, the method for manufacturing a vertically aligned liquid crystal film according to claim 1 or 2, wherein the arithmetic average roughness of the first main surface of the film substrate is 3 nm or less. 如請求項1或2之垂直配向液晶膜之製造方法，其中上述膜基板於第二主面具有易滑層，且於第一主面不具有易滑層。For example, the method for manufacturing a vertically aligned liquid crystal film according to claim 1 or 2, wherein the film substrate has an easy-sliding layer on the second main surface and does not have an easy-sliding layer on the first main surface. 如請求項1或2之垂直配向液晶膜之製造方法，其中上述膜基板為降烯系聚合物膜。The method for manufacturing a vertically aligned liquid crystal film as claimed in item 1 or 2, wherein the above-mentioned film substrate is Ethylene polymer film. 如請求項1或2之垂直配向液晶膜之製造方法，其中上述液晶性組合物中，上述光聚合性液晶單體之含量為上述側鏈型液晶聚合物之含量之1.1~10倍。The method for manufacturing a vertically aligned liquid crystal film according to claim 1 or 2, wherein the content of the photopolymerizable liquid crystal monomer in the liquid crystal composition is 1.1 to 10 times the content of the side chain liquid crystal polymer. 如請求項1或2之垂直配向液晶膜之製造方法，其中上述膜基板為雙軸延伸膜。The method for manufacturing a vertically aligned liquid crystal film according to claim 1 or 2, wherein the film substrate is a biaxially stretched film. 如請求項1或2之垂直配向液晶膜之製造方法，其中上述液晶配向步驟中加熱溫度T為75℃以下。For example, the method for manufacturing a vertical alignment liquid crystal film according to claim 1 or 2, wherein the heating temperature T in the above liquid crystal alignment step is 75 ° C or lower.
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