TW202033632A - Alignment film for transferring liquid crystal compound alignment layer - Google Patents
Alignment film for transferring liquid crystal compound alignment layer Download PDFInfo
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- TW202033632A TW202033632A TW108138545A TW108138545A TW202033632A TW 202033632 A TW202033632 A TW 202033632A TW 108138545 A TW108138545 A TW 108138545A TW 108138545 A TW108138545 A TW 108138545A TW 202033632 A TW202033632 A TW 202033632A
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- alignment
- film
- liquid crystal
- layer
- crystal compound
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3016—Polarising elements involving passive liquid crystal elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
- B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01M—TESTING STATIC OR DYNAMIC BALANCE OF MACHINES OR STRUCTURES; TESTING OF STRUCTURES OR APPARATUS, NOT OTHERWISE PROVIDED FOR
- G01M11/00—Testing of optical apparatus; Testing structures by optical methods not otherwise provided for
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
- G01N21/88—Investigating the presence of flaws or contamination
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/08—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of polarising materials
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pathology (AREA)
- Immunology (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Mechanical Engineering (AREA)
- Polarising Elements (AREA)
- Laminated Bodies (AREA)
- Liquid Crystal (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Investigating Materials By The Use Of Optical Means Adapted For Particular Applications (AREA)
Abstract
Description
本發明係關於用於轉印液晶化合物配向層之轉印用薄膜。更詳細而言,關於在製造積層有包含液晶化合物配向層的相位差層之圓偏光板等偏光板或相位差板時,或在製造具有包含液晶化合物配向層的偏光層之偏光板時等,所使用之用於轉印液晶化合物配向層之轉印用薄膜。The present invention relates to a transfer film for transferring an alignment layer of a liquid crystal compound. In more detail, when manufacturing polarizing plates or retardation plates such as a circular polarizing plate laminated with a phase difference layer including a liquid crystal compound alignment layer, or when manufacturing a polarizing plate having a polarizing layer including a liquid crystal compound alignment layer, etc., The used transfer film is used to transfer the liquid crystal compound alignment layer.
以往,於影像顯示裝置中,為了減低外來光的反射,在影像顯示面板之視聽者側的面板面上配置圓偏光板。此圓偏光板係藉由直線偏光板與λ/4等的相位差薄膜之積層體所構成,藉由直線偏光板將朝向影像顯示面板的面板面之外來光轉換成直線偏光,接著藉由λ/4等的相位差薄膜轉換成圓偏光。圓偏光所致的外來光係在影像顯示面板的表面進行反射時,偏光面的旋轉方向係逆轉,此反射光係相反地藉由λ/4等的相位差薄膜,轉換成被直線偏光板所遮光的方向之直線偏光,然後被直線偏光板所遮光,故抑制往外部之出射。如此地,圓偏光板係使用在偏光板上貼合有λ/4等的相位差薄膜者。Conventionally, in an image display device, in order to reduce the reflection of external light, a circularly polarizing plate is arranged on the panel surface of the viewer side of the image display panel. This circular polarizing plate is composed of a laminate of a linear polarizing plate and a retardation film such as λ/4. The linear polarizing plate converts the light facing outside the panel surface of the image display panel into linear polarized light, and then by λ The retardation film of /4 grade is converted into circularly polarized light. When the external light caused by circular polarization is reflected on the surface of the image display panel, the rotation direction of the polarizing surface is reversed, and the reflected light is converted by a retardation film such as λ/4 into a linear polarizer. The linearly polarized light in the shielding direction is then shielded by the linear polarizer, so it is suppressed to emit to the outside. In this manner, a circularly polarizing plate is used which has a retardation film such as λ/4 bonded to the polarizing plate.
作為相位差薄膜,使用環狀烯烴(參照專利文獻1)、聚碳酸酯(參照專利文獻2)、三乙醯纖維素的延伸薄膜(參照專利文獻3)等之單質的相位差薄膜。又,作為相位差薄膜,使用在透明薄膜上具有由液晶化合物所成的相位差層之積層體的相位差薄膜(參照專利文獻4、5)。記載於上述中設有由液晶化合物所成的相位差層時,即使轉印液晶化合物也良好。As the retardation film, simple retardation films such as cyclic olefin (see Patent Document 1), polycarbonate (see Patent Document 2), and a stretched film of triacetyl cellulose (see Patent Document 3) are used. In addition, as the retardation film, a retardation film having a laminate of a retardation layer made of a liquid crystal compound on a transparent film is used (see Patent Documents 4 and 5). It is described that when a retardation layer made of a liquid crystal compound is provided, it is good even if the liquid crystal compound is transferred.
又,由專利文獻6等已知藉由將由液晶化合物所成的相位差層轉印至透明薄膜而作成相位差薄膜之方法。亦已知藉由如此的轉印法,在透明薄膜上設置λ/4等之由液晶化合物所成的相位差層,成為λ/4薄膜之方法(參照專利文獻7、8)。In addition, a method of forming a retardation film by transferring a retardation layer made of a liquid crystal compound to a transparent film is known from Patent Document 6 and the like. It is also known that by such a transfer method, a retardation layer made of a liquid crystal compound such as λ/4 is provided on a transparent film to form a λ/4 film (see Patent Documents 7 and 8).
於此等的轉印法中,有介紹各式各樣者作為轉印用的基材,其中大多例示聚酯、三乙醯纖維素、環狀聚烯烴等的透明樹脂薄膜。三乙醯纖維素、環狀聚烯烴等之未延伸薄膜係無雙折射性,於能以將相位差層設置於薄膜基材之狀態下,檢査(評價)相位差層的狀態之點上較宜,但此等之薄膜係不僅高價,而且當將薄膜減薄時,機械強度差,未必是最合適者。Among these transfer methods, various ones have been introduced as substrates for transfer, and most of them exemplify transparent resin films such as polyester, triacetyl cellulose, and cyclic polyolefin. Unstretched films such as triacetyl cellulose and cyclic polyolefins have no birefringence. It is suitable for inspecting (evaluating) the state of the retardation layer when the retardation layer can be placed on the film substrate. However, these films are not only expensive, but also have poor mechanical strength when the film is thinned, which may not be the most suitable one.
另一方面,延伸薄膜雖然機械強度比未延伸薄膜優異,作為轉印用的薄膜基材較宜,但是由於具有雙折射性,故相位差層的評價係困難。特別地,雙軸延伸聚酯薄膜係比較便宜,且具有優異的機械強度、耐熱性,在此等之方面,作為轉印用的薄膜基材非常佳,但是聚酯薄膜由於具有大的雙折射性,故以在薄膜基材上積層有液晶化合物配向層(相位差層)之狀態,評價相位差層者係困難。On the other hand, a stretched film has better mechanical strength than an unstretched film and is suitable as a film substrate for transfer. However, since it has birefringence, it is difficult to evaluate the retardation layer. In particular, biaxially stretched polyester film is relatively inexpensive, and has excellent mechanical strength and heat resistance. In these respects, it is very good as a film substrate for transfer, but polyester film has a large birefringence. Therefore, it is difficult to evaluate the retardation layer in the state where the liquid crystal compound alignment layer (retardation layer) is laminated on the film substrate.
因此,於延伸薄膜中評價相位差層時,必須轉印至對象物(其它的透明樹脂薄膜、偏光板等)後進行評價,或剝離相位差層而僅以相位差層進行評價,或轉印至玻璃等而進行評價。轉印至對象物後進行評價之方法,當在相位差層具有問題時,亦包含正常品的偏光板等,必須作為非標準品處置,生產性差。剝離相位差層而進行評價之方法,有相位差層薄時無法評價之問題。又,於剝離而進行評價之方法或轉印至玻璃之方法中,變成樣本抽出評價,無法全量評價。Therefore, when evaluating the retardation layer in a stretched film, it is necessary to transfer to an object (other transparent resin films, polarizing plates, etc.) and then evaluate, or peel off the retardation layer and evaluate only the retardation layer, or transfer Evaluate to glass etc. In the method of evaluation after transfer to the object, when there is a problem in the retardation layer, it also includes normal polarizers, etc., which must be handled as non-standard products, and productivity is poor. The method of peeling off the retardation layer for evaluation has a problem that it cannot be evaluated when the retardation layer is thin. Moreover, in the method of peeling and evaluating or the method of transferring to glass, it becomes a sample extraction evaluation, and it is impossible to evaluate the whole quantity.
又,延伸薄膜雖然機械強度比未延伸薄膜優異,作為轉印用的薄膜基材較宜,但是常常發生所轉印的相位差層之配向方向不是符合設計之配向方向,經常發生與其偏離的問題。而且,若將如此之具有偏離設計的配向方向之相位差的偏光板使用於顯示器,則會發生漏光等之問題。特別地,雙軸延伸聚酯薄膜等之延伸聚酯薄膜係比較便宜,且具有優異的機械強度、耐熱性,於此等之點上作為轉印用的薄膜基材非常佳,但是於聚酯薄膜中,其配向方向之偏離及因此所造成的漏光之問題係特別顯著。In addition, although stretched film has better mechanical strength than unstretched film and is suitable as a film substrate for transfer, it often happens that the alignment direction of the transferred retardation layer is not in line with the design alignment direction, and the problem of deviation from it often occurs. . Moreover, if such a polarizing plate with a phase difference deviating from the designed alignment direction is used in a display, problems such as light leakage will occur. In particular, stretched polyester films such as biaxially stretched polyester films are relatively inexpensive and have excellent mechanical strength and heat resistance. In these points, they are very good as film substrates for transfer. In the film, the deviation of the alignment direction and the resulting light leakage problem are particularly significant.
再者,雙軸延伸聚酯薄膜等的聚酯薄膜係比較便宜,且具有優異的機械強度、耐熱性,於此等之點上作為轉印用的薄膜基材非常佳,但是若將聚酯薄膜使用作為轉印用的薄膜基材,則在其上形成相位差層(液晶化合物配向層)而製作積層體之步驟中,有薄膜之霧度上升或在薄膜中發生異物之問題。而且,由於如此上升的霧度或異物,在用於控制液晶化合物的配向之紫外線照射時偏光係紊亂,有無法成為符合設計的配向方向之問題。In addition, polyester films such as biaxially stretched polyester films are relatively inexpensive, and have excellent mechanical strength and heat resistance. In these points, they are very good as film substrates for transfer. The film is used as a film substrate for transfer, and a retardation layer (liquid crystal compound alignment layer) is formed thereon to produce a laminate. There are problems in that the haze of the film increases or foreign matter is generated in the film. In addition, due to the increased haze or foreign matter, the polarization system is disturbed during ultraviolet irradiation for controlling the alignment of the liquid crystal compound, and there is a problem that the alignment direction cannot be adapted to the design.
又,亦已知藉由將在轉印用薄膜上所積層之包含液晶化合物與二色性色素之偏光層(液晶化合物配向層)轉印至保護膜而製造偏光板之方法,但是此時亦有與上述同樣之問題 [先前技術文獻] [專利文獻]In addition, there is also known a method of manufacturing a polarizing plate by transferring a polarizing layer (liquid crystal compound alignment layer) composed of a liquid crystal compound and a dichroic dye layered on a transfer film to a protective film, but this is also Have the same problem as above [Prior Technical Literature] [Patent Literature]
[專利文獻1]日本特開2012-56322號公報 [專利文獻2]日本特開2004-144943號公報 [專利文獻3]日本特開2004-46166號公報 [專利文獻4]日本特開2006-243653號公報 [專利文獻5]日本特開2001-4837號公報 [專利文獻6]日本特開平4-57017號公報 [專利文獻7]日本特開2014-071381號公報 [專利文獻8]日本特開2017-146616號公報[Patent Document 1] JP 2012-56322 A [Patent Document 2] JP 2004-144943 A [Patent Document 3] JP 2004-46166 A [Patent Document 4] JP 2006-243653 A [Patent Document 5] Japanese Patent Application Publication No. 2001-4837 [Patent Document 6] Japanese Patent Application Laid-Open No. 4-57017 [Patent Document 7] JP 2014-071381 A [Patent Document 8] Japanese Patent Application Publication No. 2017-146616
[發明欲解決之課題][The problem to be solved by the invention]
本發明係以如此習知技術的問題為背景而完成者。即,本發明之第一目的在於提供一種轉印用薄膜,其係一邊使用便宜且機械強度優異的聚酯等延伸薄膜作為用於轉印液晶化合物配向層之轉印用薄膜,一邊即使為積層於轉印用薄膜上之狀態,也能評價在轉印用薄膜上所設置的液晶化合物配向層(相位差層或偏光層)之配向狀態等。The present invention was completed on the background of the problems of such conventional technologies. That is, the first object of the present invention is to provide a transfer film that uses a stretched film such as polyester, which is inexpensive and excellent in mechanical strength, as a transfer film for transferring the alignment layer of a liquid crystal compound. The state on the transfer film can also be evaluated for the alignment state of the liquid crystal compound alignment layer (phase difference layer or polarizing layer) provided on the transfer film.
本發明之第二目的在於提供一種轉印用薄膜,其係一邊使用便宜且機械強度優異的聚酯等延伸薄膜作為用於轉印液晶化合物配向層之轉印用薄膜,一邊可減低所轉印的液晶化合物配向層之配向方向的偏離之問題,以符合設計的配向轉印相位差層或偏光層,可防止顯示器的漏光之問題。The second object of the present invention is to provide a transfer film, which uses an inexpensive and excellent mechanical strength stretched film such as polyester as the transfer film for the transfer of the liquid crystal compound alignment layer, while reducing the amount of transfer The problem of the deviation of the alignment direction of the alignment layer of the liquid crystal compound, in accordance with the designed alignment transfer retardation layer or polarizing layer, can prevent the problem of light leakage of the display.
本發明之第三目的在於提供一種轉印用薄膜,其係一邊使用便宜且機械強度優異的聚酯等延伸薄膜作為用於轉印液晶化合物配向層之轉印用薄膜,一邊可有效果地防止在薄膜上形成相位差層或偏光層(液晶化合物配向層)之步驟中的薄膜之霧度上升或薄膜中之異物發生,形成符合設計的配向之相位差層或偏光層(液晶化合物配向層)。 [用以解決課題之手段]The third object of the present invention is to provide a transfer film which can effectively prevent the use of a stretched film such as polyester, which is inexpensive and excellent in mechanical strength, as the transfer film for transferring the alignment layer of liquid crystal compounds. In the step of forming a retardation layer or a polarizing layer (liquid crystal compound alignment layer) on the film, the haze of the film rises or foreign matter in the film occurs, forming a retardation layer or a polarizing layer (liquid crystal compound alignment layer) with the designed alignment . [Means to solve the problem]
本發明者為了達成第一目的而專心致力地檢討,結果發現作為配向薄膜,藉由使用即使在其配向方向與配向薄膜的流動方向或與流動方向正交的方向之間的角度成為最大的地方,也控制在特定的角度以下者,而不發生上述以往的問題,即使於配向薄膜上積層有液晶化合物配向層之狀態,也能良好地進行相位差相之評價。In order to achieve the first objective, the inventors intensively examined and found that as an alignment film, even when the angle between the alignment direction and the flow direction of the alignment film or the direction orthogonal to the flow direction becomes the largest , It is also controlled below a specific angle, without the above-mentioned conventional problems, even if the liquid crystal compound alignment layer is laminated on the alignment film, the phase difference can be evaluated well.
本發明者為了達成第二目的,檢討使用以往的延伸薄膜作為轉印用的薄膜基材時,所轉印的相位差層或偏光層之配向方向不成為符合設計之配向方向的原因。結果,發現由於在作為基材的延伸薄膜之上使液晶化合物配向而形成相位差層或偏光層時之熱處理,基材的延伸薄膜係進行某程度熱收縮,但由於此熱收縮的程度係在延伸薄膜的正交的二個方向中大不相同,故在熱收縮後的基材薄膜中發生畸變,而且此畸變係對於在基材薄膜之上所形成的相位差層或偏光層之配向方向造成不良影響,故相位差層或偏光層之配向方向係偏離符合設計之配向方向。然後,本發明者專心致力地檢討有效果地防止基材薄膜的此畸變之方法,結果發現作為基材薄膜的配向薄膜,即使在其流動方向(MD方向)、及與流動方向正交的方向(TD方向)、及之間,在薄膜的熱收縮率具有偏差,也可藉由使用將該差控制在特定範圍內者,而不發生上述以往的問題,可以符合設計的配向轉印相位差層或偏光層,不發生漏光之問題。In order to achieve the second objective, the inventors examined the reason why the alignment direction of the transferred retardation layer or the polarizing layer did not conform to the designed alignment direction when the conventional stretched film was used as the film substrate for transfer. As a result, it was found that due to the heat treatment when the phase difference layer or the polarizing layer is formed by aligning the liquid crystal compound on the stretched film as the base material, the stretched film of the base material undergoes a certain degree of heat shrinkage, but the degree of heat shrinkage is The two orthogonal directions of the stretched film are quite different, so distortion occurs in the substrate film after heat shrinkage, and this distortion is related to the alignment direction of the retardation layer or the polarizing layer formed on the substrate film Cause adverse effects, so the alignment direction of the retardation layer or the polarizing layer deviates from the alignment direction that conforms to the design. Then, the inventors intensively examined methods for effectively preventing this distortion of the substrate film, and found that the alignment film as the substrate film, even in the flow direction (MD direction) and the direction orthogonal to the flow direction (TD direction), and there is a deviation in the thermal shrinkage rate of the film, and the difference can also be controlled within a specific range by using the one that does not occur the above-mentioned previous problems, and can meet the designed alignment transfer retardation Layer or polarizing layer, no light leakage problem occurs.
本發明者為了達成第三目的,檢討使用以往的延伸薄膜作為轉印用的薄膜基材時,在薄膜上形成相位差層或偏光層(液晶化合物配向層)之步驟中薄膜之霧度上升或薄膜中異物發生之原因。其結果,發現構成聚酯薄膜的聚酯樹脂係必然地含有酯環狀三聚物(寡聚物)作為其在製造過程中的聚合時之反應的副產物,因此將聚酯薄膜使用作為轉印用的基材薄膜時,因在其上塗布液晶化合物及加熱而形成液晶化合物配向層(相位差層或偏光層)之步驟中的加熱處理,而此等之寡聚物析出至基材薄膜之表面,結果造成霧度上升或異物發生。然後,本發明者專心致力地檢討有效果地防止轉印用配向聚酯薄膜的加熱處理時之如此的霧度上升或異物發生效果之方法,結果發現藉由使用聚酯薄膜的寡聚物析出量經控制在特定範圍內者,不發生上述以往之問題,可形成符合設計的配向之相位差層或偏光層(液晶化合物配向層)。In order to achieve the third object, the inventors examined that when a conventional stretched film is used as a film substrate for transfer, the haze of the film increases or the haze of the film is increased during the step of forming a retardation layer or a polarizing layer (liquid crystal compound alignment layer) on the film The cause of foreign matter in the film. As a result, it was found that the polyester resin system constituting the polyester film inevitably contains an ester cyclic terpolymer (oligomer) as a by-product of the reaction during the polymerization during the manufacturing process. Therefore, the polyester film is used as a conversion product. When printing a substrate film, heat treatment in the step of forming a liquid crystal compound alignment layer (phase difference layer or polarizing layer) by coating liquid crystal compound on it and heating, and these oligomers are deposited on the substrate film As a result, the haze rises or foreign matter occurs. Then, the present inventors intensively examined methods to effectively prevent the increase in haze or the occurrence of foreign matter during the heat treatment of the alignment polyester film for transfer, and found that the oligomer precipitation by using the polyester film When the amount is controlled within a specific range, the above-mentioned previous problems will not occur, and a retardation layer or a polarizing layer (liquid crystal compound alignment layer) that conforms to the designed alignment can be formed.
即,用於達成第一目的之發明係具有以下(1)~(6)之構成。 (1)一種液晶化合物配向層轉印用配向薄膜,其係用於將液晶化合物配向層轉印至對象物之配向薄膜,其特徵為:配向薄膜的配向方向與配向薄膜的流動方向或與流動方向正交的方向之間的角度,係在薄膜的寬度方向中從各端部起在內側5cm的地點之兩端部、中央部及在中央部與兩端部之中間的中間部之5處所測定的值之中的最大值為14度以下。 (2)如(1)記載之液晶化合物配向層轉印用配向薄膜,其中配向薄膜在寬度方向的配向角之角度差為7度以下。 (3)如(1)或(2)記載之液晶化合物配向層轉印用配向薄膜,其中配向薄膜係聚酯薄膜。 (4)一種液晶化合物配向層轉印用積層體,其係積層有液晶化合物配向層與配向薄膜之積層體,其特徵為:配向薄膜係如(1)~(3)中任一項記載之配向薄膜。 (5)一種液晶化合物配向層積層偏光板之製造方法,其特徵為包含:貼合偏光板與如(4)記載之積層體的液晶化合物配向層面而形成中間積層體之步驟,及從中間積層體剝離配向薄膜之步驟。 (6)一種液晶化合物配向層轉印用積層體之檢査方法,其係檢查如(4)記載之積層體中的液晶化合物配向層之配向狀態之方法,其特徵為包含:將具有平行於配向薄膜的配向方向、或平行於與配向方向正交的方向、或平行於配向薄膜的流動方向、或平行於與流動方向正交的方向之電場振動方向的直線偏光,從積層體的配向薄膜面來照射,在液晶化合物配向層面側受光之步驟。That is, the invention for achieving the first object has the following constitutions (1) to (6). (1) An alignment film for transferring a liquid crystal compound alignment layer, which is an alignment film used to transfer a liquid crystal compound alignment layer to an object, and is characterized in that: the alignment direction of the alignment film and the flow direction of the alignment film or flow together The angle between the directions perpendicular to the direction of the film is the five positions of the two ends, the center, and the middle between the center and the two ends at a point 5cm inside from each end in the width direction of the film. The maximum value among the measured values is 14 degrees or less. (2) The alignment film for transferring an alignment layer of a liquid crystal compound as described in (1), wherein the angular difference of the alignment angle of the alignment film in the width direction is 7 degrees or less. (3) The alignment film for transferring an alignment layer of a liquid crystal compound as described in (1) or (2), wherein the alignment film is a polyester film. (4) A laminate for the transfer of a liquid crystal compound alignment layer, which is a laminate of a liquid crystal compound alignment layer and an alignment film, characterized in that the alignment film is as described in any one of (1) to (3) Alignment film. (5) A method for manufacturing a liquid crystal compound-aligned laminated polarizing plate, characterized by comprising: laminating the polarizing plate and the liquid crystal compound alignment layer of the laminated body as described in (4) to form an intermediate laminated body, and laminating from the intermediate layer The step of peeling off the alignment film. (6) An inspection method for a laminate for transfer of a liquid crystal compound alignment layer, which is a method for inspecting the alignment state of the liquid crystal compound alignment layer in the laminate as described in (4), which is characterized in that it includes: The alignment direction of the film, or parallel to the direction orthogonal to the alignment direction, or parallel to the flow direction of the alignment film, or parallel to the direction of the electric field vibration direction perpendicular to the flow direction, linearly polarized light from the alignment film surface of the laminate To irradiate and receive light on the side of the alignment layer of the liquid crystal compound.
用於達成第二目的之發明係具有以下(1)~(6)之構成。 (1)一種液晶化合物配向層轉印用配向薄膜,其係用於將液晶化合物配向層轉印至對象物之配向薄膜,其特徵為:配向薄膜在流動方向之150℃ 30分鐘的熱收縮率與配向薄膜在與流動方向正交的方向之150℃ 30分鐘的熱收縮率之差為4%以下。 (2)如(1)記載之液晶化合物配向層轉印用配向薄膜,其中相對於配向薄膜的流動方向而言在45度的方向之150℃ 30分鐘的熱收縮率與相對於配向薄膜的流動方向而言在135度的方向之150℃ 30分鐘的熱收縮率之差為4%以下。 (3)如(1)或(2)記載之液晶化合物配向層轉印用配向薄膜,其中配向薄膜係聚酯薄膜。 (4)一種液晶化合物配向層轉印用積層體,其係積層有液晶化合物配向層與配向薄膜之積層體,其特徵為:配向薄膜係如(1)~(3)中任一項記載之配向薄膜。 (5)一種液晶化合物配向層積層偏光板之製造方法,其特徵為包含:貼合偏光板與如(4)記載之積層體的液晶化合物配向層面而形成中間積層體之步驟,及從中間積層體剝離配向薄膜之步驟。 (6)一種液晶化合物配向層轉印用積層體之檢査方法,其係檢查如(4)記載之積層體中的液晶化合物配向層之配向狀態之方法,其特徵為包含:將具有平行於配向薄膜的配向方向、或平行於與配向方向正交的方向、或平行於配向薄膜的流動方向、或平行於與流動方向正交的方向之電場振動方向的直線偏光,從積層體的配向薄膜面來照射,在液晶化合物配向層面側受光之步驟。The invention for achieving the second object has the following constitutions (1) to (6). (1) An alignment film for transferring the alignment layer of a liquid crystal compound, which is an alignment film used to transfer the alignment layer of a liquid crystal compound to an object, characterized in that the alignment film has a heat shrinkage rate of 150°C for 30 minutes in the flow direction The difference in thermal shrinkage at 150°C for 30 minutes with the alignment film in the direction orthogonal to the flow direction is 4% or less. (2) The alignment film for transferring the alignment layer of a liquid crystal compound as described in (1), wherein the heat shrinkage rate at 150°C for 30 minutes at a direction of 45 degrees relative to the flow direction of the alignment film and the flow relative to the alignment film In terms of the direction, the difference in thermal shrinkage at 150°C for 30 minutes in the direction of 135 degrees is 4% or less. (3) The alignment film for transferring an alignment layer of a liquid crystal compound as described in (1) or (2), wherein the alignment film is a polyester film. (4) A laminate for the transfer of a liquid crystal compound alignment layer, which is a laminate of a liquid crystal compound alignment layer and an alignment film, characterized in that the alignment film is as described in any one of (1) to (3) Alignment film. (5) A method for manufacturing a liquid crystal compound-aligned laminated polarizing plate, characterized by comprising: laminating the polarizing plate and the liquid crystal compound alignment layer of the laminated body as described in (4) to form an intermediate laminated body, and laminating from the intermediate layer The step of peeling off the alignment film. (6) An inspection method for a laminate for transfer of a liquid crystal compound alignment layer, which is a method for inspecting the alignment state of the liquid crystal compound alignment layer in the laminate as described in (4), which is characterized in that it includes: The alignment direction of the film, or parallel to the direction orthogonal to the alignment direction, or parallel to the flow direction of the alignment film, or parallel to the direction of the electric field vibration direction perpendicular to the flow direction, linearly polarized light from the alignment film surface of the laminate To irradiate and receive light on the side of the alignment layer of the liquid crystal compound.
用於達成第三目的之發明係具有以下(1)~(6)之構成。 (1)一種液晶化合物配向層轉印用配向聚酯薄膜,其係用於將液晶化合物配向層轉印至對象物之配向聚酯薄膜,其特徵為:在150℃加熱90分鐘後的配向聚酯薄膜之脫模面的表面之酯環狀三聚物的析出量為1.0mg/m2 以下。 (2)如(1)記載之液晶化合物配向層轉印用配向聚酯薄膜,其中構成配向聚酯薄膜的脫模面側層之聚酯樹脂中的酯環狀三聚物之含量為0.7質量%以下。 (3)如(1)或(2)記載之液晶化合物配向層轉印用配向聚酯薄膜,其中在配向聚酯薄膜的脫模面,設置防止酯環狀三聚物之析出的塗層。 (4)一種液晶化合物配向層轉印用積層體,其係積層有液晶化合物配向層與配向聚酯薄膜之積層體,其特徵為:配向聚酯薄膜係如(1)~(3)中任一項記載之配向聚酯薄膜。 (5)一種液晶化合物配向層積層偏光板之製造方法,其特徵為包含:貼合偏光板與如(4)記載之積層體之液晶化合物配向層面而形成中間積層體之步驟,及從中間積層體剝離配向聚酯薄膜之步驟。 (6)一種液晶化合物配向層轉印用積層體之檢査方法,其係檢查如(4)記載之積層體中的液晶化合物配向層之配向狀態之方法,其特徵為包含:將具有平行於配向聚酯薄膜的配向方向、或平行於與配向方向正交的方向、或平行於配向聚酯薄膜的流動方向、或平行於與流動方向正交的方向之電場振動方向的直線偏光,從積層體的配向聚酯薄膜面來照射,在液晶化合物配向層面側受光之步驟。 [發明之效果]The invention for achieving the third object has the following constitutions (1) to (6). (1) An alignment polyester film for transferring the alignment layer of a liquid crystal compound, which is an alignment polyester film used to transfer the alignment layer of a liquid crystal compound to an object, and is characterized in that the alignment polyester film is heated at 150°C for 90 minutes. The precipitation amount of the ester cyclic trimer on the surface of the release surface of the ester film is 1.0 mg/m 2 or less. (2) The alignment polyester film for transferring the alignment layer of a liquid crystal compound as described in (1), wherein the content of the ester cyclic trimer in the polyester resin constituting the release surface side layer of the alignment polyester film is 0.7 mass %the following. (3) The alignment polyester film for transferring an alignment layer of a liquid crystal compound as described in (1) or (2), wherein a coating layer is provided on the release surface of the alignment polyester film to prevent the precipitation of the ester cyclic trimer. (4) A laminate for the transfer of a liquid crystal compound alignment layer, which is a laminate of a liquid crystal compound alignment layer and an alignment polyester film, characterized in that the alignment polyester film is any of (1) to (3) A documented orientation polyester film. (5) A method for manufacturing a liquid crystal compound-aligned laminated polarizing plate, characterized by comprising: bonding the polarizing plate and the liquid crystal compound alignment layer of the laminated body as described in (4) to form an intermediate laminated body, and laminating from the intermediate layer Steps to peel off the aligned polyester film. (6) An inspection method for a laminate for transfer of a liquid crystal compound alignment layer, which is a method for inspecting the alignment state of the liquid crystal compound alignment layer in the laminate as described in (4), which is characterized in that it includes: The alignment direction of the polyester film, or parallel to the direction orthogonal to the alignment direction, or parallel to the flow direction of the aligned polyester film, or parallel to the direction of the electric field vibration direction perpendicular to the flow direction, from the laminate The step of irradiating the alignment polyester film surface and receiving light on the alignment layer side of the liquid crystal compound. [Effects of Invention]
依照第一發明,可一邊使用便宜且機械強度優異的聚酯等延伸薄膜,一邊即使為在配向薄膜上積層有在配向薄膜上所設置的液晶化合物配向層(相位差層或偏光層)之配向狀態等之狀態,也可評價。According to the first invention, it is possible to use a stretched film such as polyester, which is inexpensive and excellent in mechanical strength, even if the alignment film is laminated with an alignment layer of a liquid crystal compound (phase difference layer or polarizing layer) provided on the alignment film. State and other conditions can also be evaluated.
依照第二發明,可一邊使用便宜且機械強度優異的聚酯等延伸薄膜,一邊以符合設計的配向,轉印相位差層或偏光層,可防止顯示器的漏光之問題。According to the second invention, it is possible to transfer the retardation layer or the polarizing layer in an alignment that matches the design while using a stretched film such as polyester that is inexpensive and excellent in mechanical strength, thereby preventing the problem of light leakage in the display.
依照第三發明,由於可一邊使用便宜且機械強度優異的聚酯等延伸薄膜,一邊有效果地防止薄膜之加熱處理時之霧度上升或異物發生,故可形成符合設計的配向之相位差層或偏光層(液晶化合物配向層)。According to the third invention, it is possible to effectively prevent the increase in haze and the occurrence of foreign matter during the heating process of the film while using a stretched film such as polyester, which is inexpensive and excellent in mechanical strength, so that a retardation layer with a design alignment can be formed Or polarizing layer (liquid crystal compound alignment layer).
[用以實施發明的形態][Form to implement the invention]
第一發明之配向薄膜係用於將液晶化合物配向層轉印至對象物(其它的透明樹脂薄膜、偏光板等)者,其特徵為:配向薄膜的配向方向與配向薄膜的流動方向或與流動方向正交的方向之間的角度,係在最大的地方為14度以下。The alignment film of the first invention is used to transfer the alignment layer of a liquid crystal compound to an object (other transparent resin films, polarizing plates, etc.), and is characterized by: the alignment direction of the alignment film and the flow direction of the alignment film or the flow direction The angle between the orthogonal directions is 14 degrees or less at the largest point.
第二發明之配向薄膜係用於將液晶化合物配向層轉印至對象物(其它的透明樹脂薄膜、偏光板等)者,其特徵為:配向薄膜在流動方向(MD方向)之150℃ 30分鐘的熱收縮率與配向薄膜在與流動方向正交的方向(TD方向)之150℃ 30分鐘的熱收縮率之差為4%以下。The alignment film of the second invention is used to transfer the alignment layer of a liquid crystal compound to an object (other transparent resin films, polarizing plates, etc.), and is characterized in that the alignment film is in the flow direction (MD direction) at 150°C for 30 minutes The difference between the thermal shrinkage rate of the oriented film and the thermal shrinkage rate of the alignment film in the direction orthogonal to the flow direction (TD direction) at 150°C for 30 minutes is 4% or less.
第三發明之配向聚酯薄膜係用於將液晶化合物配向層轉印至對象物(其它的透明樹脂薄膜、偏光板等)者,其特徵為:在150℃加熱90分鐘後之配向聚酯薄膜之脫模面的表面之酯環狀三聚物的析出量為1.0mg/m2 以下。還有,以下有將配向聚酯薄膜簡稱為配向薄膜的情形。又,於設有後述的寡聚物阻擋塗層、脫模層、平坦化塗層、易滑塗層、抗靜電塗層等時,有包含此等之層,而稱為配向聚酯薄膜或配向薄膜。The alignment polyester film of the third invention is used to transfer the alignment layer of the liquid crystal compound to an object (other transparent resin films, polarizing plates, etc.), characterized by: the alignment polyester film after heating at 150°C for 90 minutes The precipitation amount of the ester cyclic trimer on the surface of the release surface is 1.0 mg/m 2 or less. In the following, the aligned polyester film may be simply referred to as an aligned film. In addition, when the oligomer barrier coating, mold release layer, planarization coating, slippery coating, antistatic coating, etc. described later are provided, there are layers containing these, which are called oriented polyester film or Alignment film.
作為配向薄膜所用的樹脂,較佳為具有雙折射性者,更佳為聚酯、聚碳酸酯、聚苯乙烯、聚醯胺、聚丙烯、環狀聚烯烴、三乙醯纖維素,進一步較佳為聚酯,特佳為聚對苯二甲酸乙二酯。The resin used for the alignment film is preferably one having birefringence, more preferably polyester, polycarbonate, polystyrene, polyamide, polypropylene, cyclic polyolefin, triacetyl cellulose, and more preferably Polyester is preferred, and polyethylene terephthalate is particularly preferred.
配向薄膜係在構成上可為單層,也可為共擠出的複數層。複數層時,可舉出表層(脫模面之層A)/背面層(B)、或A/中間層(C)/A(脫模面之層與背面層相同)、A/C/B等之構成。The oriented film system can be a single layer or multiple co-extruded layers. In the case of multiple layers, the surface layer (layer A on the release surface)/back layer (B), or A/middle layer (C)/A (the layer on the release surface is the same as the back layer), A/C/B And so on.
將薄膜延伸時,可為單軸延伸、弱雙軸延伸(在雙軸方向中延伸,但其中一個方向為弱者)、雙軸延伸之任一者而無妨,但在寬度方向中能以寬廣的範圍使配向方向成固定之面,較佳為單軸延伸或弱雙軸延伸。弱雙軸延伸之情況較佳為將主配向方向設為後段之延伸方向。單軸延伸之情況係延伸方向可為薄膜製造的流動方向(縱向),也可為正交於其之方向(橫向)。 雙軸延伸之情況可為同時雙軸延伸,也可為逐次雙軸延伸。縱向之延伸較佳為藉由速度差的不同輥群所造成之延伸,橫向之延伸較佳為拉幅機延伸。When the film is stretched, it can be uniaxially stretched, weakly biaxially stretched (extending in the biaxial direction, but one of the directions is weak), and biaxially stretched. It does not matter, but it can be wide in the width direction. The range makes the alignment direction a fixed surface, preferably uniaxial extension or weak biaxial extension. In the case of weak biaxial extension, it is preferable to set the main alignment direction as the extension direction of the rear section. In the case of uniaxial extension, the extension direction can be the flow direction (longitudinal) of the film production, or the direction orthogonal to it (transverse). The condition of biaxial extension can be simultaneous biaxial extension or successive biaxial extension. The longitudinal extension is preferably the extension caused by different roller groups with different speeds, and the lateral extension is preferably the tenter extension.
轉印用配向薄膜係在工業上以捲繞有薄膜的捲筒供給。捲筒寬度之下限較佳為30cm,更佳為50cm,進一步較佳為70cm,特佳為90cm,最佳為100cm。捲筒寬度之上限較佳為5000cm,更佳為4000cm,進一步較佳為3000cm。The alignment film for transfer is industrially supplied in a roll on which the film is wound. The lower limit of the roll width is preferably 30 cm, more preferably 50 cm, further preferably 70 cm, particularly preferably 90 cm, and most preferably 100 cm. The upper limit of the roll width is preferably 5000 cm, more preferably 4000 cm, and still more preferably 3000 cm.
捲筒長度之下限較佳為100m,更佳為500m,進一步較佳為1000m。捲筒長度之上限較佳為100000m,更佳為50000m,進一步較佳為30000m。The lower limit of the length of the reel is preferably 100m, more preferably 500m, and still more preferably 1000m. The upper limit of the length of the reel is preferably 100,000 m, more preferably 50,000 m, and still more preferably 30,000 m.
一般而言,偏光鏡係使用將聚乙烯醇在薄膜的流動方向中延伸,使其吸收碘或有機系化合物的二色性色素者,偏光鏡的消光軸(吸收軸)係成為薄膜的流動方向。圓偏光板之情況係在作為相位差層,λ/4層的慢軸(配向方向)係對於消光軸呈45度地積層,或λ/4層與λ/2層係在斜方向(10~80度)中積層。又,液晶顯示器所用的光學補償層亦對於偏光鏡的消光軸,在斜方向中積層。Generally speaking, a polarizer is used to extend polyvinyl alcohol in the flow direction of the film to absorb iodine or dichroic pigments of organic compounds. The extinction axis (absorption axis) of the polarizer becomes the flow direction of the film . The case of the circular polarizer is the retardation layer. The slow axis (alignment direction) of the λ/4 layer is stacked at 45 degrees to the extinction axis, or the λ/4 layer and the λ/2 layer are stacked in an oblique direction (10~ 80 degrees) Middle Product Layer. In addition, the optical compensation layer used in the liquid crystal display is also laminated in an oblique direction with respect to the extinction axis of the polarizer.
因此,相位差層之配向狀態,例如可藉由將具有平行或垂直於薄膜的流動方向之振動方向的直線偏光從轉印用配向薄膜側照射至相位差層,將因相位差層變成橢圓偏光的光,通過用於使橢圓偏光返回直線偏光之受光側相位差板與在使因相位差板返回的直線偏光不通過之方向中所設置的受光側偏光板,以受光元件檢測而檢査(評價)。對於在轉印用配向薄膜上所設置的相位差層,當為符合設計的相位差及配向方向時,若成為直線偏光的通過受光側相位差板之光為消光狀態,則可知成為符合設計的相位差層。相反地,若是漏光,則可知偏離設計。Therefore, the alignment state of the retardation layer can be changed to elliptically polarized light by irradiating linearly polarized light with a vibration direction parallel or perpendicular to the flow direction of the film from the transfer alignment film side to the retardation layer. The light passes through the light-receiving side phase difference plate used to return the elliptical polarized light to the linear polarized light and the light-receiving side polarizing plate installed in the direction in which the linearly polarized light returned by the phase difference plate does not pass, and the light receiving element is used for inspection (evaluation ). Regarding the retardation layer provided on the alignment film for transfer, when the retardation and alignment direction conform to the design, if the linearly polarized light passing through the light-receiving side retardation plate is in the extinction state, it can be seen that it conforms to the design Phase difference layer. Conversely, if it is light leakage, it can be seen that it deviates from the design.
然而,當轉印用配向薄膜的配向方向從平行(MD)或垂直(TD)於配向薄膜的流動方向者偏離時,通過轉印用配向薄膜的直線偏光係變成橢圓偏光,發生漏光,相位差層的正確評價係變困難。本發明係藉由將該偏離抑制在最小限度,而使相位差層之正確的評價成為可能。However, when the alignment direction of the alignment film for transfer deviates from parallel (MD) or perpendicular (TD) to the flow direction of the alignment film, the linearly polarized light system passing through the alignment film for transfer becomes elliptically polarized light, causing light leakage and retardation The correct evaluation of layers becomes difficult. The present invention makes it possible to accurately evaluate the retardation layer by suppressing the deviation to the minimum.
本發明之轉印用配向薄膜的MD或TD與配向方向之間的角度(最大地方)之下限較佳為0度。又,本發明之轉印用配向薄膜的MD或TD與配向方向之間的角度之上限係最大值較佳為14度,更佳為7度,進一步較佳為5度,特佳為4度,最佳為3度。若超過上述,則會變難以進行相位差層(液晶化合物配向層)之配向狀態的評價。The lower limit of the angle (maximum place) between the MD or TD of the alignment film for transfer of the present invention and the alignment direction is preferably 0 degrees. In addition, the upper limit of the angle between the MD or TD of the alignment film for transfer of the present invention and the alignment direction is preferably 14 degrees, more preferably 7 degrees, further preferably 5 degrees, particularly preferably 4 degrees. , The best is 3 degrees. If it exceeds the above, it becomes difficult to evaluate the alignment state of the retardation layer (liquid crystal compound alignment layer).
本發明之轉印用配向薄膜在全寬度(寬度方向)之配向角的角度差之下限較佳為0度。又,本發明之轉印用配向薄膜在全寬度之配向角的角度差之上限較佳為7度,更佳為5度,進一步較佳為3度,特佳為2度。若超過上述,則在寬度方向中會變難以進行相位差層(液晶化合物配向層)之配向狀態的評價。The lower limit of the angle difference of the alignment angle in the full width (width direction) of the alignment film for transfer of the present invention is preferably 0 degrees. In addition, the upper limit of the angle difference of the alignment angle of the alignment film for transfer of the present invention in the full width is preferably 7 degrees, more preferably 5 degrees, further preferably 3 degrees, particularly preferably 2 degrees. If it exceeds the above, it becomes difficult to evaluate the alignment state of the retardation layer (liquid crystal compound alignment layer) in the width direction.
於拉幅機內在TD方向中延伸時,於延伸區或熱定型區中薄膜係收縮力作用於MD方向。雖然薄膜之端部係以夾具固定,但是由於中央部未固定,故在拉幅機出口發生弓形延遲產生的彎曲拱起現象(bowing phenomena)。此係成為配向方向的畸變。When stretching in the TD direction in the tenter, the film shrinkage force acts in the MD direction in the stretching zone or the heat setting zone. Although the ends of the film are fixed with clamps, because the central part is not fixed, bowing phenomena (bowing phenomena) caused by bow delays occur at the exit of the tenter. This system becomes the distortion of the alignment direction.
為了減低配向方向的畸變,達成上述特性,只要適宜調整延伸溫度、延伸倍率、延伸速度、熱定型溫度、鬆弛步驟之溫度、鬆弛步驟之倍率、各溫度之寬度方向的溫度分布等即可。In order to reduce the distortion in the alignment direction and achieve the above characteristics, it is sufficient to appropriately adjust the stretching temperature, stretching magnification, stretching speed, heat setting temperature, relaxation step temperature, relaxation step magnification, and temperature distribution in the width direction of each temperature.
又,當所製膜的薄膜在全寬度中配向方向不是規定範圍內時,較佳為採用所延伸的寬廣薄膜之中央部附近等成為上述特性範圍內之部分。又,由於若增強向單軸方向的配向,則有配向方向的畸變變小之傾向,故採用弱雙軸或單軸延伸薄膜者亦為較佳的方法。特別地,較佳為MD方向是主配向方向的弱雙軸或單軸延伸薄膜。In addition, when the alignment direction of the film to be formed is not within the specified range in the full width, it is preferable to use the portion near the center of the stretched wide film that falls within the above-mentioned characteristic range. In addition, if the alignment in the uniaxial direction is enhanced, the distortion in the alignment direction tends to be small, so a weak biaxial or uniaxially stretched film is also a preferable method. In particular, it is preferably a weakly biaxially or uniaxially stretched film whose MD direction is the main alignment direction.
再者,於本發明中,轉印用配向薄膜的配向方向與配向薄膜的流動方向或與流動方向正交的方向之角度,及薄膜的寬度方向之配向角的角度差,係如以下地決定。 首先,從捲筒拉出薄膜,在兩端部(從各端部起在內側5cm的地點)、中央部及在中央部與在兩端部之中間的中間部之5處,決定配向方向。在中央部與兩端部之中間的中間部係在將中央部與兩端部之間隔予以2等分之位置。還有,配向方向係當作使用分子配向計所求出的薄膜之慢軸方向。接著,調查薄膜全體之配向方向是接近流動方向(MD),還是接近寬度方向(TD)。然後,當薄膜全體之配向方向接近流動方向時,各自在上述5處,求出配向方向與薄膜的流動方向之間的角度,將成為最大角度之地方的值採用作為「配向薄膜的配向方向與配向薄膜的流動方向之間的角度」之最大值。另一方面,當薄膜全體之配向方向接近寬度方向時,各自在上述5處,求出配向方向與薄膜的流動方向正交之方向之間的角度,將成為最大的角度之地方的值採用作為「配向薄膜的配向方向與配向薄膜的流動方向正交之方向之間的角度」之最大值。 又,於上述5處所求出的角度之中,將最大值與最小值之間之差當作「薄膜在寬度方向之配向角的角度差」。 還有,角度係相對於長度方向或寬度方向,將在與前述最大值相同側具有配向方向時當作正值,相對於長度方向或寬度方向,將在相反側具有配向方向時當作負值,區別正・負,而評價最小值。Furthermore, in the present invention, the angle difference between the alignment direction of the alignment film for transfer and the flow direction of the alignment film or the direction orthogonal to the flow direction, and the angle difference between the alignment angle in the width direction of the film is determined as follows . First, pull out the film from the roll, and determine the orientation direction at 5 of the two ends (5 cm inside from each end), the center, and the middle between the center and the two ends. The middle part between the central part and the both ends is at a position where the interval between the central part and the both ends is halved. In addition, the orientation direction is regarded as the slow axis direction of the film obtained using a molecular orientation meter. Next, it was investigated whether the orientation direction of the entire film was close to the flow direction (MD) or the width direction (TD). Then, when the orientation direction of the entire film is close to the flow direction, calculate the angle between the orientation direction and the flow direction of the film at each of the above five points, and use the value at the point where the maximum angle becomes the "alignment direction of the alignment film and The maximum value of "the angle between the flow directions of the alignment film". On the other hand, when the alignment direction of the entire film is close to the width direction, find the angle between the alignment direction and the direction orthogonal to the flow direction of the film at each of the above five points, and use the value where the angle becomes the largest The maximum value of "the angle between the alignment direction of the alignment film and the direction orthogonal to the flow direction of the alignment film". In addition, among the angles obtained at the above 5 locations, the difference between the maximum value and the minimum value is regarded as the "angle difference of the alignment angle of the film in the width direction". In addition, the angle is regarded as a positive value with respect to the length direction or the width direction when it has an alignment direction on the same side as the aforementioned maximum value, and is regarded as a negative value when it has an alignment direction on the opposite side with respect to the length direction or the width direction. , Distinguish between positive and negative, and evaluate the minimum value.
本發明之轉印用配向薄膜的MD方向與TD方向之150℃ 30分鐘的熱收縮率差之下限較佳為0%。又,本發明之轉印用配向薄膜的MD方向與TD方向之150℃ 30分鐘的熱收縮率差之上限較佳為4%,更佳為3%,進一步較佳為2%,特佳為1.5%,最佳為1%。若超過上限則在液晶化合物之配向處理中需要高溫的情況或在積層複數的液晶化合物而溫度的經歷變多之情況中,液晶化合物之配向方向偏離設計,將偏光板利用於顯示器時有時會發生漏光等。The lower limit of the thermal shrinkage difference between the MD direction and the TD direction of the alignment film for transfer of the present invention at 150°C for 30 minutes is preferably 0%. In addition, the upper limit of the thermal shrinkage difference between the MD direction and the TD direction of the alignment film for transfer of the present invention at 150°C for 30 minutes is preferably 4%, more preferably 3%, further preferably 2%, and particularly preferably 1.5%, preferably 1%. If the upper limit is exceeded, the alignment process of the liquid crystal compound requires a high temperature, or when a plurality of liquid crystal compounds are laminated and the temperature experience increases, the alignment direction of the liquid crystal compound deviates from the design, and the polarizing plate may sometimes be used in the display. Light leakage, etc. occur.
本發明之轉印用配向薄膜的MD方向之150℃ 30分鐘的熱收縮率之下限較佳為-2%,更佳為-0.5%,進一步較佳為-0.1%,特佳為0%,最佳為0.01%。若小於上述,則現實上數值之達成可能變困難。又,本發明之轉印用配向薄膜的MD方向之150℃ 30分鐘的熱收縮率之上限較佳為4%,更佳為3%,進一步較佳為2.5%,特佳為2%,最佳為1.5%。若超過上述則會難以進行熱收縮率差之調整。又,平面性會變差,作業性會惡化。The lower limit of the thermal shrinkage rate at 150°C for 30 minutes in the MD direction of the alignment film for transfer of the present invention is preferably -2%, more preferably -0.5%, still more preferably -0.1%, particularly preferably 0%, The best is 0.01%. If it is less than the above, it may become difficult to achieve the value in reality. In addition, the upper limit of the thermal shrinkage rate at 150°C for 30 minutes in the MD direction of the alignment film for transfer of the present invention is preferably 4%, more preferably 3%, further preferably 2.5%, particularly preferably 2%, most preferably Preferably it is 1.5%. If it exceeds the above, it is difficult to adjust the difference in thermal shrinkage. In addition, the flatness will deteriorate and the workability will deteriorate.
本發明之轉印用配向薄膜的TD方向之150℃ 30分鐘的熱收縮率之下限較佳為-2%,更佳為-0.5%,進一步較佳為-0.1%,特佳為0%,最佳為0.01%。若小於上述,則現實上數值之達成可能變困難。又,本發明之轉印用配向薄膜的TD方向之150℃ 30分鐘的熱收縮率之上限較佳為4%,更佳為2.5%,進一步較佳為2%,特佳為1.5%,最佳為1%。若超過上述則會難以進行熱收縮率差之調整。又,平面性會變差,作業性會惡化。The lower limit of the thermal shrinkage rate at 150°C for 30 minutes in the TD direction of the alignment film for transfer of the present invention is preferably -2%, more preferably -0.5%, further preferably -0.1%, particularly preferably 0%, The best is 0.01%. If it is less than the above, it may become difficult to achieve the value in reality. In addition, the upper limit of the thermal shrinkage rate at 150°C for 30 minutes in the TD direction of the alignment film for transfer of the present invention is preferably 4%, more preferably 2.5%, still more preferably 2%, particularly preferably 1.5%, most preferably Best is 1%. If it exceeds the above, it is difficult to adjust the difference in thermal shrinkage. In addition, the flatness will deteriorate and the workability will deteriorate.
本發明之轉印用配向薄膜之相對於MD方向而言45度的方向與相對於MD方向而言135度的方向之150℃ 30分鐘的熱收縮率差之下限較佳為0%。若小於上述,則現實上數值之達成可能變困難。又,本發明之轉印用配向薄膜之相對於MD方向而言45度的方向與相對於MD方向而言135度的方向之150℃ 30分鐘的熱收縮率差之上限較佳為4%,更佳為3%,進一步較佳為2%,特佳為1.5%,最佳為1%。若脫離上述範圍則液晶化合物之配向方向偏離設計,將偏光板利用於顯示器時有時會發生漏光等。The lower limit of the thermal shrinkage difference between the direction of 45 degrees with respect to the MD direction and the direction of 135 degrees with respect to the MD direction of the alignment film for transfer of the present invention is preferably 0%. If it is less than the above, it may become difficult to achieve the value in reality. In addition, the upper limit of the thermal shrinkage difference at 150°C for 30 minutes in the direction of 45 degrees with respect to the MD direction and the direction of 135 degrees with respect to the MD direction of the alignment film for transfer of the present invention is preferably 4%. It is more preferably 3%, further preferably 2%, particularly preferably 1.5%, and most preferably 1%. If it is out of the above range, the alignment direction of the liquid crystal compound will deviate from the design, and light leakage may sometimes occur when the polarizing plate is used in a display.
薄膜之熱收縮特性係可藉由延伸溫度、延伸倍率、熱定型溫度、鬆弛步驟之倍率、鬆弛步驟之溫度等進行調節。又,在冷卻步驟中薄膜之表面溫度為100℃以上,從夾具釋放而捲取者亦較宜。從夾具之釋放係可為打開夾具之方法,也可為將經夾具保持的端部,以刀具等切離之方法。又,在離線進行加熱處理(退火處理)者亦為有效果的方法。The thermal shrinkage characteristics of the film can be adjusted by stretching temperature, stretching ratio, heat setting temperature, relaxation step ratio, relaxation step temperature, etc. In addition, the surface temperature of the film in the cooling step is 100°C or higher, and it is also suitable for the film to be released from the jig for winding. The release system from the clamp can be a method of opening the clamp, or a method of cutting away the end held by the clamp with a tool. In addition, it is also an effective method to perform heat treatment (annealing treatment) offline.
為了使本發明之轉印用配向薄膜之150℃ 30分鐘的熱收縮特性成為上述,轉印用配向薄膜之材料較佳為聚酯,特佳為聚對苯二甲酸乙二酯。In order to make the thermal shrinkage characteristic of the alignment film for transfer of the present invention at 150°C for 30 minutes as described above, the material of the alignment film for transfer is preferably polyester, and particularly preferably polyethylene terephthalate.
本發明之轉印用配向薄膜的95℃最大熱收縮率之下限較佳為0%,更佳為0.01%。若小於上述,則現實上數值之達成可能變困難。又,本發明之轉印用配向薄膜的95℃最大熱收縮率之上限較佳為2.5%,更佳為2%,進一步較佳為1.2%,特佳為1%,最佳為0.8%。若超過上述則將偏光板利用於顯示器時,有時會發生漏光等。The lower limit of the maximum thermal shrinkage at 95°C of the alignment film for transfer of the present invention is preferably 0%, more preferably 0.01%. If it is less than the above, it may become difficult to achieve the value in reality. Moreover, the upper limit of the maximum thermal shrinkage at 95°C of the alignment film for transfer of the present invention is preferably 2.5%, more preferably 2%, further preferably 1.2%, particularly preferably 1%, and most preferably 0.8%. If it exceeds the above, when a polarizing plate is used for a display, light leakage or the like may occur.
本發明之轉印用配向薄膜的最大熱收縮率方向與MD或TD方向之角度之下限較佳為0度。又,本發明之轉印用配向薄膜的最大熱收縮率方向與MD或TD方向之角度之上限較佳為20度,更佳為15度,進一步較佳為10度,特佳為7度,最佳為5度。若超過上述則液晶化合物之配向方向偏離設計,將偏光板利用於顯示器時有時會發生漏光等。The lower limit of the angle between the direction of maximum thermal shrinkage of the alignment film for transfer of the present invention and the MD or TD direction is preferably 0 degrees. In addition, the upper limit of the angle between the direction of maximum thermal shrinkage of the alignment film for transfer of the present invention and the MD or TD direction is preferably 20 degrees, more preferably 15 degrees, further preferably 10 degrees, particularly preferably 7 degrees, The best is 5 degrees. If it exceeds the above, the alignment direction of the liquid crystal compound deviates from the design, and light leakage may occur when the polarizing plate is used in a display.
本發明之轉印用配向薄膜之MD方向的彈性模數及TD方向的彈性模數之下限較佳為1GPa,更佳為2GPa。若小於上述,則在各步驟中伸長,會不成為符合設計之配向方向。又,本發明之轉印用配向薄膜之MD方向的彈性模數及TD方向的彈性模數之上限較佳為8GPa,更佳為7GPa。若超過上述則現實上數值之達成可能變困難。The lower limit of the elastic modulus in the MD direction and the elastic modulus in the TD direction of the alignment film for transfer of the present invention is preferably 1 GPa, more preferably 2 GPa. If it is smaller than the above, it will be stretched in each step and will not become the alignment direction that meets the design. In addition, the upper limit of the elastic modulus in the MD direction and the elastic modulus in the TD direction of the alignment film for transfer of the present invention is preferably 8 GPa, more preferably 7 GPa. If it exceeds the above, it may become difficult to achieve the value in reality.
於本發明之轉印用配向薄膜為聚對苯二甲酸乙二酯薄膜時,在150℃加熱90分鐘後的配向聚酯薄膜之脫模面的表面之酯環狀三聚物之析出量(以下稱為表面寡聚物析出量(150℃90min))之下限較佳為0mg/m2 ,更佳為0.01mg/m2 。若小於上述,則現實上數值之達成可能變困難。表面寡聚物析出量(150℃90min)之上限較佳為1mg/m2 ,更佳為0.7mg/m2 ,進一步較佳為0.5mg/m2 ,特佳為0.3mg/m2 。若超過上述則在將液晶化合物配向層予以複數積層時或在需要高溫下的配向處理時,霧度上升或發生異物,在紫外線照射的配向控制時偏光紊亂,會變成得不到符合設計的相位差層或偏光層。再者,於本發明中,配向薄膜的「脫模面」係意指於配向薄膜之表面中,意圖設置配向薄膜進行轉印的液晶化合物配向層之表面。設有寡聚物阻擋塗層、平坦化塗層或脫模層等時,只要在其上設置液晶化合物配向層,則此等寡聚物阻擋塗層、平坦化層或脫模層等之表面(與液晶化合物配向層相接之面)係配向薄膜的「脫模面」。When the alignment film for transfer of the present invention is a polyethylene terephthalate film, the precipitation amount of the ester cyclic trimer on the surface of the release surface of the alignment polyester film after heating at 150°C for 90 minutes ( Hereinafter, the lower limit of the precipitation amount of surface oligomers (150°C for 90 min)) is preferably 0 mg/m 2 , and more preferably 0.01 mg/m 2 . If it is less than the above, it may become difficult to achieve the value in reality. The amount of precipitated oligomer upper surface (150 ℃ 90min) of preferably 1mg / m 2, more preferably 0.7mg / m 2, more preferably 0.5mg / m 2, particularly preferably 0.3mg / m 2. If it exceeds the above, when multiple layers of liquid crystal compound alignment layers are laminated or when alignment processing at high temperature is required, the haze rises or foreign matter is generated, and the polarization is disturbed during alignment control by ultraviolet radiation, and the phase that conforms to the design cannot be obtained Differential layer or polarizing layer. Furthermore, in the present invention, the "release surface" of the alignment film refers to the surface of the alignment film, and the surface of the alignment layer of the liquid crystal compound on which the alignment film is intended for transfer. When an oligomer barrier coating, planarization coating, or mold release layer is provided, as long as the liquid crystal compound alignment layer is provided on it, the surface of these oligomer barrier coatings, planarization layers, or mold release layers (The surface in contact with the alignment layer of the liquid crystal compound) is the "release surface" of the alignment film.
為了降低表面寡聚物析出量,較佳為在轉印用配向薄膜之表面上設置能阻擋寡聚物(酯環狀三聚物)之析出的塗層(寡聚物阻擋塗層)。In order to reduce the amount of oligomers deposited on the surface, it is preferable to provide a coating (oligomer barrier coating) that can block the precipitation of oligomers (ester cyclic trimers) on the surface of the alignment film for transfer.
寡聚物阻擋塗層較佳包含50重量%以上的Tg為90℃以上的樹脂。作為如此的樹脂,較佳為三聚氰胺等的胺基樹脂、醇酸樹脂、聚苯乙烯、丙烯酸樹脂等。樹脂的Tg之上限較佳為200℃。The oligomer barrier coating preferably contains 50% by weight or more of a resin having a Tg of 90°C or more. As such a resin, amino resins, such as melamine, alkyd resin, polystyrene, acrylic resin, etc. are preferable. The upper limit of the Tg of the resin is preferably 200°C.
寡聚物阻擋塗層的厚度之下限較佳為0.01μm,更佳為0.03μm,進一步較佳為0.05μm。若小於上述,則會得不到充分的阻擋效果。寡聚物阻擋塗層的厚度之上限較佳為10μm,更佳為5μm,進一步較佳為2μm。若超過上述則效果有時會變飽和。The lower limit of the thickness of the oligomer barrier coating is preferably 0.01 μm, more preferably 0.03 μm, and still more preferably 0.05 μm. If it is less than the above, a sufficient barrier effect cannot be obtained. The upper limit of the thickness of the oligomer barrier coating is preferably 10 μm, more preferably 5 μm, and still more preferably 2 μm. If it exceeds the above, the effect may become saturated.
又,為了降低表面寡聚物析出量,亦較佳為降低構成轉印用配向薄膜的脫模面側層之聚酯樹脂中的寡聚物(酯環狀三聚物)之含量(以下稱為表層寡聚物含量)。表層寡聚物含量之下限較佳為0.3質量%,更佳為0.33質量%,進一步較佳為0.35質量%。若小於上述,則現實上數值之達成可能變困難。表層寡聚物含量之上限較佳為0.7質量%,更佳為0.6質量%,進一步較佳為0.5質量%。還有,於本發明中,配向薄膜之「脫模面側層」係意指在構成配向薄膜的聚酯之各層中,脫模面存在之層。此處,即使薄膜為單一層時,也有稱為脫模面側層之情況。此時,後述之背面側層與脫模面側層變成相同層。In addition, in order to reduce the amount of oligomers deposited on the surface, it is also preferable to reduce the content of oligomers (ester cyclic trimers) in the polyester resin constituting the release surface side layer of the alignment film for transfer (hereinafter referred to as Is the surface layer oligomer content). The lower limit of the content of the surface layer oligomer is preferably 0.3% by mass, more preferably 0.33% by mass, and still more preferably 0.35% by mass. If it is less than the above, it may become difficult to achieve the value in reality. The upper limit of the content of the surface layer oligomer is preferably 0.7% by mass, more preferably 0.6% by mass, and still more preferably 0.5% by mass. In addition, in the present invention, the "releasing surface side layer" of the alignment film means a layer in which the mold releasing surface exists in each layer of the polyester constituting the alignment film. Here, even when the film is a single layer, it may be called a release surface side layer. At this time, the back surface side layer and the release surface side layer described later become the same layer.
為了降低表層寡聚物含量,較佳為降低原料聚酯中的寡聚物含量。原料聚酯中的寡聚物含量之下限較佳為0.23質量%,更佳為0.25質量%,進一步較佳為0.27質量%。原料聚酯中的寡聚物含量之上限較佳為0.7質量%,更佳為0.6質量%,進一步較佳為0.5質量%。原料聚酯中的寡聚物含量係可藉由對於固相聚合等固體狀態的聚酯,以180℃以上熔點以下之溫度進行加熱處理而使其降低。亦較佳為使聚酯的觸媒失去活性。In order to reduce the oligomer content in the surface layer, it is preferable to reduce the oligomer content in the raw material polyester. The lower limit of the oligomer content in the raw material polyester is preferably 0.23% by mass, more preferably 0.25% by mass, and still more preferably 0.27% by mass. The upper limit of the oligomer content in the raw material polyester is preferably 0.7% by mass, more preferably 0.6% by mass, and still more preferably 0.5% by mass. The content of oligomers in the raw material polyester can be reduced by heating the polyester in a solid state such as solid-phase polymerization at a temperature above the melting point of 180°C. It is also preferable to deactivate the polyester catalyst.
又,為了降低表層寡聚物析出量,縮短製膜時的熔融時間者亦有效。In addition, in order to reduce the amount of oligomer precipitation in the surface layer, it is also effective to shorten the melting time during film formation.
於本發明之轉印用配向薄膜為聚酯薄膜時,構成薄膜的聚酯之極限黏度(IVf)之下限較佳為0.45dl/g,更佳為0.5dl/g,進一步較佳為0.53dl/g。若小於上述,則薄膜的耐衝擊性會有時變差。又,有製膜變難以進行,或厚度的均勻性變差之情況。IVf之上限較佳為0.9dl/g,更佳為0.8dl/g,進一步較佳為0.7dl/g。若超過上述則熱收縮率有時會變高。又,製膜有時會變難以進行。When the alignment film for transfer of the present invention is a polyester film, the lower limit of the limiting viscosity (IVf) of the polyester constituting the film is preferably 0.45dl/g, more preferably 0.5dl/g, and still more preferably 0.53dl /g. If it is less than the above, the impact resistance of the film sometimes deteriorates. In addition, film formation may become difficult, or the uniformity of thickness may deteriorate. The upper limit of IVf is preferably 0.9 dl/g, more preferably 0.8 dl/g, and still more preferably 0.7 dl/g. If it exceeds the above, the thermal shrinkage rate may increase. In addition, film formation sometimes becomes difficult.
本發明之轉印用配向薄膜的波長380nm之光線穿透率之下限較佳為0%。又,本發明之轉印用配向薄膜的波長380nm之光線穿透率之上限較佳為20%,更佳為15%,進一步較佳為10%,特佳為5%。若超過上限則在藉由照射偏光紫外線而成為特定之配向方向時,由於來自背面的反射而配向層或液晶化合物配向層的方向均勻性有時會變差。波長380nm之光線穿透率係可藉由添加UV吸收劑而成為範圍內。The lower limit of the light transmittance of the alignment film for transfer of the present invention at a wavelength of 380 nm is preferably 0%. In addition, the upper limit of the light transmittance of the alignment film for transfer of the present invention at a wavelength of 380 nm is preferably 20%, more preferably 15%, further preferably 10%, and particularly preferably 5%. If the upper limit is exceeded, when a specific alignment direction is irradiated with polarized ultraviolet rays, the direction uniformity of the alignment layer or the alignment layer of the liquid crystal compound may deteriorate due to reflection from the back surface. The light transmittance with a wavelength of 380nm can be brought into the range by adding a UV absorber.
本發明之轉印用配向薄膜的霧度之下限較佳為0.01%,更佳為0.1%。若小於上述,則現實上數值之達成可能變困難。又,本發明之轉印用配向薄膜的霧度之上限較佳為3%,更佳為2.5%,進一步較佳為2%,特佳為1.7%。若超過上述則在偏光UV照射時偏光係紊亂,會得不到符合設計的相位差層或偏光層。另外,於相位差層或偏光層之檢査時會因漫反射而發生漏光,有時變難以進行檢査。The lower limit of the haze of the alignment film for transfer of the present invention is preferably 0.01%, more preferably 0.1%. If it is less than the above, it may become difficult to achieve the value in reality. Furthermore, the upper limit of the haze of the alignment film for transfer of the present invention is preferably 3%, more preferably 2.5%, still more preferably 2%, particularly preferably 1.7%. If it exceeds the above, the polarization system is disturbed during the polarization UV irradiation, and a retardation layer or a polarizing layer conforming to the design cannot be obtained. In addition, when inspecting the retardation layer or the polarizing layer, light leakage occurs due to diffuse reflection, which may make inspection difficult.
本發明之轉印用配向薄膜之150℃加熱90分鐘後的霧度之下限係與上述同樣。The lower limit of the haze of the alignment film for transfer of the present invention after heating at 150°C for 90 minutes is the same as the above.
本發明之轉印用配向薄膜之150℃加熱90分鐘前後的霧度之變化量之下限較佳為0%。上限較佳為0.5%,更佳為0.4%,進一步較佳為0.3%。The lower limit of the haze change before and after heating at 150°C for 90 minutes of the alignment film for transfer of the present invention is preferably 0%. The upper limit is preferably 0.5%, more preferably 0.4%, and still more preferably 0.3%.
本發明之轉印用配向薄膜係慢軸方向的折射率nx-快軸方向的折射率ny之下限較佳為0.005,更佳為0.01,進一步較佳為0.02,特佳為0.03,最佳為0.04,最佳為0.05。若小於上述,則現實上數值之達成可能變困難。又,nx-ny之上限較佳為0.15,更佳為0.13,進一步較佳為0.12。若超過上述則現實上數值之達成可能變困難。特別地,於聚對苯二甲酸乙二酯薄膜之情況,nx-ny之值較佳為上述者。The lower limit of the refractive index nx in the slow axis direction-the refractive index ny in the fast axis direction of the alignment film for transfer of the present invention is preferably 0.005, more preferably 0.01, further preferably 0.02, particularly preferably 0.03, most preferably 0.04, preferably 0.05. If it is less than the above, it may become difficult to achieve the value in reality. In addition, the upper limit of nx-ny is preferably 0.15, more preferably 0.13, and still more preferably 0.12. If it exceeds the above, it may become difficult to achieve the value in reality. In particular, in the case of a polyethylene terephthalate film, the value of nx-ny is preferably the above-mentioned one.
於雙軸延伸之情況,nx-ny之下限較佳為0.005,更佳為0.01。若小於上述,則現實上數值之達成可能變困難。又,於雙軸延伸之情況,nx-ny之上限較佳為0.05,更佳為0.04,進一步較佳為0.03。若超過上述則現實上數值之達成可能變困難。In the case of biaxial extension, the lower limit of nx-ny is preferably 0.005, more preferably 0.01. If it is less than the above, it may become difficult to achieve the value in reality. Furthermore, in the case of biaxial stretching, the upper limit of nx-ny is preferably 0.05, more preferably 0.04, and still more preferably 0.03. If it exceeds the above, it may become difficult to achieve the value in reality.
於單軸延伸之情況,nx-ny之下限較佳為0.05,更佳為0.06。若小於上述,則單軸延伸之優點會變淡。又,於單軸延伸之情況,nx-ny之上限較佳為0.15,更佳為0.13。若超過上述則現實上數值之達成可能變困難。In the case of uniaxial extension, the lower limit of nx-ny is preferably 0.05, more preferably 0.06. If it is less than the above, the advantages of uniaxial extension will be diminished. Furthermore, in the case of uniaxial extension, the upper limit of nx-ny is preferably 0.15, and more preferably 0.13. If it exceeds the above, it may become difficult to achieve the value in reality.
本發明之轉印用配向薄膜的快軸方向之折射率(ny)之下限較佳為1.55,更佳為1.58,進一步較佳為1.57。又,本發明之轉印用配向薄膜的快軸方向之折射率(ny)之上限較佳為1.64,更佳為1.63,進一步較佳為1.62。The lower limit of the refractive index (ny) in the fast axis direction of the alignment film for transfer of the present invention is preferably 1.55, more preferably 1.58, and still more preferably 1.57. In addition, the upper limit of the refractive index (ny) in the fast axis direction of the alignment film for transfer of the present invention is preferably 1.64, more preferably 1.63, and still more preferably 1.62.
本發明之轉印用配向薄膜的慢軸方向之折射率(nx)之下限較佳為1.66,更佳為1.67,進一步較佳為1.68。又,本發明之轉印用配向薄膜的慢軸方向之折射率(nx)之上限較佳為1.75,更佳為1.73,進一步較佳為1.72,特佳為1.71。The lower limit of the refractive index (nx) in the slow axis direction of the alignment film for transfer of the present invention is preferably 1.66, more preferably 1.67, and still more preferably 1.68. In addition, the upper limit of the refractive index (nx) in the slow axis direction of the alignment film for transfer of the present invention is preferably 1.75, more preferably 1.73, still more preferably 1.72, and particularly preferably 1.71.
本發明之轉印用配向薄膜的抗靜電性(表面電阻)之下限較佳為1×105 Ω/□,更佳為1×106 Ω/□。即使小於上述也效果飽和,會得不到高於其之效果。又,本發明之轉印用配向薄膜的抗靜電性(表面電阻)之上限較佳為1×1013 Ω/□,更佳為1×1012 Ω/□,進一步較佳為1×1011 Ω/□。若超過上限則會發生靜電所致的排斥,或發生液晶化合物之配向方向的紊亂。抗靜電性(表面電阻)係可藉由在轉印用配向薄膜中混入抗靜電劑,在脫模層之下層或相反面設置抗靜電塗層,或在脫模層中添加抗靜電劑等,而成為上述範圍內。The lower limit of the antistatic property (surface resistance) of the alignment film for transfer of the present invention is preferably 1×10 5 Ω/□, more preferably 1×10 6 Ω/□. Even if it is less than the above, the effect is saturated, and the effect higher than it may not be obtained. In addition, the upper limit of the antistatic property (surface resistance) of the alignment film for transfer of the present invention is preferably 1×10 13 Ω/□, more preferably 1×10 12 Ω/□, and still more preferably 1×10 11 Ω/□. If the upper limit is exceeded, repulsion due to static electricity may occur, or the alignment direction of the liquid crystal compound may be disturbed. Antistatic properties (surface resistance) can be achieved by mixing antistatic agents in the alignment film for transfer, placing an antistatic coating on the lower or opposite side of the release layer, or adding an antistatic agent to the release layer. And become within the above range.
作為添加至抗靜電塗層或脫模層或轉印用配向薄膜的抗靜電劑,可舉出聚苯胺、聚噻吩等的導電性高分子、聚苯乙烯磺酸鹽等的離子性高分子、錫摻雜氧化銦、銻摻雜氧化錫等的導電性微粒子。Examples of the antistatic agent added to the antistatic coating, the release layer or the alignment film for transfer include conductive polymers such as polyaniline and polythiophene, ionic polymers such as polystyrene sulfonate, Conductive fine particles such as tin-doped indium oxide and antimony-doped tin oxide.
亦可在轉印用配向薄膜上設置脫模層。惟,當薄膜本身係與相位差層或配向層等轉印物之密著性低,即使不設置脫模層也有充分的脫模性時,亦可不設置脫模層。又,於密著性過低時,亦可對於表面進行電暈處理等而調整密著性。脫模層係可使用眾所周知的脫模劑而形成,可舉出醇酸樹脂、胺基樹脂、長鏈丙烯酸丙烯酸酯系、聚矽氧樹脂、氟樹脂當作較佳例。此等係可配合與轉印物的密著性而適宜選擇。A release layer can also be provided on the alignment film for transfer. However, when the film itself has low adhesion to the transfer material such as the retardation layer or the alignment layer and has sufficient release properties even if the release layer is not provided, the release layer may not be provided. In addition, when the adhesion is too low, the surface may be subjected to corona treatment or the like to adjust the adhesion. The release layer system can be formed using a well-known release agent, and preferable examples include alkyd resins, amino resins, long-chain acrylic acrylates, silicone resins, and fluororesins. These systems can be appropriately selected according to the adhesion to the transfer material.
再者,於本發明之轉印用配向薄膜中,亦可設置易接著層作為寡聚物阻擋塗層、抗靜電層及脫模層之下層。Furthermore, in the alignment film for transfer of the present invention, an easy bonding layer can also be provided as an oligomer barrier coating, an antistatic layer, and a lower layer of the release layer.
(脫模面粗糙度) 本發明之轉印用配向薄膜的脫模面(A層表面)較佳為平滑。(Roughness of release surface) The release surface (layer A surface) of the alignment film for transfer of the present invention is preferably smooth.
本發明之轉印用配向薄膜的脫模面之三次元算術平均粗糙度(SRa)之下限較佳為1nm,更佳為2nm。若小於上述,則現實上數值之達成可能變困難。又,本發明之轉印用配向薄膜的脫模面之SRa之上限較佳為30nm,更佳為25nm,進一步較佳為20nm,特佳為15nm,最佳為10nm。The lower limit of the three-dimensional arithmetic mean roughness (SRa) of the release surface of the alignment film for transfer of the present invention is preferably 1 nm, more preferably 2 nm. If it is less than the above, it may become difficult to achieve the value in reality. In addition, the upper limit of the SRa of the release surface of the alignment film for transfer of the present invention is preferably 30 nm, more preferably 25 nm, further preferably 20 nm, particularly preferably 15 nm, and most preferably 10 nm.
本發明之轉印用配向薄膜的脫模面之三次元十點平均粗糙度(SRz)之下限較佳為5nm,更佳為10nm,進一步較佳為13nm。又,本發明之轉印用配向薄膜的脫模面之SRz之上限較佳為200nm,更佳為150nm,進一步較佳為120nm,特佳為100nm,最佳為80nm。The lower limit of the three-dimensional ten-point average roughness (SRz) of the release surface of the alignment film for transfer of the present invention is preferably 5 nm, more preferably 10 nm, and further preferably 13 nm. Furthermore, the upper limit of SRz of the release surface of the alignment film for transfer of the present invention is preferably 200 nm, more preferably 150 nm, further preferably 120 nm, particularly preferably 100 nm, and most preferably 80 nm.
本發明之轉印用配向薄膜的脫模面之最大高度(SRy:脫模面最大山高度SRp+脫模面最大谷深度SRv)之下限較佳為10nm,更佳為15nm,進一步較佳為20nm。又,本發明之轉印用配向薄膜的脫模面之SRy之上限較佳為300nm,更佳為250nm,進一步較佳為150nm,特佳為120nm,最佳為100nm。The lower limit of the maximum height of the release surface of the alignment film for transfer of the present invention (SRy: maximum mountain height of the release surface SRp + maximum valley depth of the release surface SRv) is preferably 10 nm, more preferably 15 nm, and further preferably 20 nm . In addition, the upper limit of SRy of the release surface of the alignment film for transfer of the present invention is preferably 300 nm, more preferably 250 nm, still more preferably 150 nm, particularly preferably 120 nm, and most preferably 100 nm.
本發明之轉印用配向薄膜的脫模面之0.5μm以上的突起數之上限較佳為5個/m2 ,更佳為4個/m2 ,進一步較佳為3個/m2 ,特佳為2個/m2 ,最佳為1個/m2 。The upper limit of the number of protrusions of 0.5 μm or more on the release surface of the alignment film for transfer of the present invention is preferably 5/m 2 , more preferably 4/m 2 , still more preferably 3/m 2 , especially Preferably it is 2 pieces/m 2 , and most preferably is 1 piece/m 2 .
若脫模面的粗糙度超過上述,則在本發明之轉印用配向薄膜之上所形成的液晶化合物配向層之微少部分中,不成為符合設計之配向狀態或相位差,有發生針孔狀或傷痕狀的缺點之情況。茲認為此係原因為若是配向層,則在摩擦時凸部分的配向層係剝落,或凸部分的山腳部或凹部分之摩擦變不充分。又,茲認為原因為於脫模面層中包含粒子之情況,在摩擦時粒子脫落,損傷表面。另外,茲認為即使為摩擦配向層或光配向層,也當在設有配向層之狀態下捲取時,由於與背面層摩擦,而在凸部分之配向層中造成空孔,因壓力而配向紊亂等。茲認為原因為由於此等配向層之缺陷,當在配向層上設置液晶化合物配向層時,在其微少部分中不發生液晶化合物的配向。If the roughness of the release surface exceeds the above, the tiny part of the alignment layer of the liquid crystal compound formed on the alignment film for transfer of the present invention will not become the alignment state or phase difference that meets the design, and pinholes may occur. Or a scar-like defect. It is believed that the reason for this is that in the case of the alignment layer, the alignment layer of the convex part is peeled off during rubbing, or the friction of the foot of the convex part or the concave part becomes insufficient. In addition, it is believed that the reason is that particles are contained in the mold release surface layer, and the particles fall off during friction and damage the surface. In addition, it is believed that even if it is a rubbing alignment layer or a photo-alignment layer, when the alignment layer is provided, when the alignment layer is provided, pores are formed in the alignment layer of the convex portion due to friction with the back layer, and alignment is caused by pressure. Disorder etc. It is believed that the reason is due to the defects of these alignment layers. When the alignment layer of the liquid crystal compound is provided on the alignment layer, the alignment of the liquid crystal compound does not occur in a small portion of the alignment layer.
若認為亦原因為若是液晶化合物配向層,則在液晶化合物之塗布時,因在凸部分中液晶化合物配向層的厚度變薄,或在凹部分中厚度變薄等之理由,而得不到符合設計的相位差。If the reason is considered to be the liquid crystal compound alignment layer, when the liquid crystal compound is applied, the thickness of the liquid crystal compound alignment layer in the convex portion becomes thinner, or the thickness in the concave portion becomes thinner. Design phase difference.
為了使脫模面(A)之粗糙度成為上述範圍,當本發明之轉印用配向薄膜為延伸薄膜時,可舉出以下之方法。 ・使薄膜原材的脫模面側層(表層)不含粒子。 ・於薄膜原材的脫模面側層(表層)包含粒子時,成為粒徑小的粒子。 ・於薄膜原材的脫模面側層(表層)包含粒子時,設置平坦化塗層。In order to make the roughness of the release surface (A) into the above range, when the alignment film for transfer of the present invention is a stretched film, the following methods can be mentioned. ・The release side layer (surface layer) of the film raw material does not contain particles. ・When particles are contained in the release surface side layer (surface layer) of the film material, it becomes particles with a small particle size. ・When the release side layer (surface layer) of the film material contains particles, a flattening coating is provided.
又,於上述以外,使原料或製造步驟如以下地潔淨(clean)者亦重要。 ・對於聚合時的粒子漿體進行過濾。於碎片化前進行過濾。 ・使碎片化冷卻水成為潔淨者。使碎片搬運、製膜機投入之前的環境成為潔淨。 ・於製膜時,對於熔融樹脂進行過濾,去除凝聚粒子或異物。 ・對於塗劑進行過濾,去除異物。 ・於製膜、塗布、乾燥時,在潔淨環境下進行。In addition to the above, it is also important to make the raw materials or the manufacturing steps clean as follows. ・Filter the particle slurry during polymerization. Filter before fragmentation. ・Make the fragmented cooling water clean. Make the environment before chip transportation and film making machine clean. ・During film formation, the molten resin is filtered to remove aggregated particles or foreign matter. ・Filter the paint to remove foreign matter. ・During film forming, coating, and drying, proceed in a clean environment.
表層係為了平滑化,較佳為實質上不含粒子。所謂實質上不含粒子,就是意指粒子含量小於50ppm,較佳為小於30ppm。In order to smooth the surface layer, it is preferable that it contains substantially no particles. The term "substantially free of particles" means that the particle content is less than 50 ppm, preferably less than 30 ppm.
為了提高表面的滑動性,表層亦可含有粒子。含有粒子時,表層粒子含量之下限較佳為0ppm,更佳為50ppm,進一步較佳為100ppm。又,表層粒子含量之上限較佳為20000ppm,更佳為10000ppm,進一步較佳為8000ppm,特佳為6000ppm。若超過上限,則無法使表層的粗糙度成為在較佳的範圍內。In order to improve the sliding properties of the surface, the surface layer may contain particles. When particles are contained, the lower limit of the surface layer particle content is preferably 0 ppm, more preferably 50 ppm, and still more preferably 100 ppm. In addition, the upper limit of the content of surface layer particles is preferably 20000 ppm, more preferably 10000 ppm, still more preferably 8000 ppm, and particularly preferably 6000 ppm. If it exceeds the upper limit, the roughness of the surface layer cannot be brought within a preferable range.
表層粒徑之下限較佳為0.005μm,更佳為0.01μm,進一步較佳為0.02μm。又,表層粒徑之上限較佳為3μm,更佳為1μm,進一步較佳為0.5μm,特佳為0.3μm。若超過上限,則無法使表層的粗糙度成為在較佳的範圍內。The lower limit of the surface layer particle size is preferably 0.005 μm, more preferably 0.01 μm, and still more preferably 0.02 μm. Furthermore, the upper limit of the particle size of the surface layer is preferably 3 μm, more preferably 1 μm, still more preferably 0.5 μm, and particularly preferably 0.3 μm. If it exceeds the upper limit, the roughness of the surface layer cannot be brought within a preferable range.
即使表層不含粒子或為粒徑小的粒子時,也當其下層含有粒子時,有由於下層的粒子之影響而脫模面層的粗糙度變高之情況。如此的情況較佳為採取增大脫模面層的厚度,或設置不含粒子的下層(中間層)等之方法。Even if the surface layer does not contain particles or has particles with a small particle size, when the lower layer contains particles, the roughness of the release surface layer may increase due to the influence of the particles in the lower layer. In such a case, it is preferable to adopt methods such as increasing the thickness of the release surface layer or providing a lower layer (intermediate layer) that does not contain particles.
表層厚度之下限較佳為0.1μm,更佳為0.5μm,進一步較佳為1μm,特佳為3μm,最佳為5μm。又,相對於轉印用配向薄膜之總厚度,表層厚度之上限較佳為97%,更佳為95%,進一步較佳為90%。The lower limit of the thickness of the surface layer is preferably 0.1 μm, more preferably 0.5 μm, further preferably 1 μm, particularly preferably 3 μm, and most preferably 5 μm. In addition, the upper limit of the thickness of the surface layer relative to the total thickness of the alignment film for transfer is preferably 97%, more preferably 95%, and still more preferably 90%.
不含粒子的中間層係意指實質上不含粒子者,粒子之含量係小於50ppm,較佳為小於30ppm。相對於轉印用配向薄膜之總厚度,中間層之厚度之下限較佳為10%,更佳為20%,進一步較佳為30%。上限較佳為95%,更佳為90%。The particle-free intermediate layer means one that contains substantially no particles, and the content of the particles is less than 50 ppm, preferably less than 30 ppm. Relative to the total thickness of the alignment film for transfer, the lower limit of the thickness of the intermediate layer is preferably 10%, more preferably 20%, and still more preferably 30%. The upper limit is preferably 95%, more preferably 90%.
於轉印用配向薄膜的表層之粗糙度高時,亦可設置平坦化塗層。作為平坦化塗層所用的樹脂,可舉出聚酯、丙烯酸、聚胺基甲酸酯、聚苯乙烯、聚醯胺等一般作為塗劑的樹脂用者。亦較佳為使用三聚氰胺、異氰酸酯、環氧樹脂、唑啉化合物等之交聯劑。此等係可溶解或分散於有機溶劑或水中而成為塗劑,進行塗布、乾燥。或者,於丙烯酸之情況,可在無溶劑下塗布,以放射線使其硬化。平坦化塗層亦可為寡聚物阻擋塗層。以塗布設置脫模層時,亦可增厚脫模層本身。When the surface roughness of the alignment film for transfer is high, a planarization coating can also be provided. Examples of the resin used for the planarization coating include polyester, acrylic, polyurethane, polystyrene, polyamide, and other resins generally used as coating agents. It is also preferable to use melamine, isocyanate, epoxy resin, Crosslinking agent for oxazoline compounds. These systems can be dissolved or dispersed in organic solvents or water to become paints, which can be applied and dried. Or, in the case of acrylic, it can be coated without solvent and cured by radiation. The planarization coating can also be an oligomer barrier coating. When the release layer is provided by coating, the release layer itself can also be thickened.
表面平坦化塗層的厚度之下限較佳為0.01μm,更佳為0.1μm,進一步較佳為0.2μm,特佳為0.3μm。若小於上述,則平坦化的效果會變不充分。又,表面平坦化塗層的厚度之上限較佳為10μm,更佳為7μm,進一步較佳為5μm,特佳為3μm。即使超過上述,有時也得不到高於其之平坦化效果。The lower limit of the thickness of the surface flattening coating is preferably 0.01 μm, more preferably 0.1 μm, further preferably 0.2 μm, and particularly preferably 0.3 μm. If it is less than the above, the effect of flattening may become insufficient. In addition, the upper limit of the thickness of the surface flattening coating is preferably 10 μm, more preferably 7 μm, still more preferably 5 μm, particularly preferably 3 μm. Even if it exceeds the above, sometimes it is not possible to obtain a higher leveling effect.
平坦化塗層係在製膜過程中可線內塗布而設置,也可另外離線設置。The flattening coating can be applied in-line during the film forming process, or can be installed offline.
(背面側粗糙度) 又,縱然使本發明之轉印用配向薄膜的脫模面成為平滑,也有在液晶化合物配向層中發生缺點之情況。可知此係因為轉印用配向薄膜被捲取成捲筒狀,由於表面與背面接觸,故背面的粗糙度係轉印至表面(背面的凸部轉印至脫模層而形成凹部)。設有液晶化合物配向層的轉印用配向薄膜,係為了保護液晶化合物配向層,亦有貼合遮蔽薄膜而捲取之情況,但為了減低成本,亦大多直接捲取。如此地,茲認為於設有配向層之狀態下捲取時,配向層係因背面的凸部,而發生凹陷、空孔、配向層的配向紊亂等現象。又,茲認為於設置液晶化合物配向層之後,因背面之凸部,而在液晶化合物配向層中發生空孔、配向紊亂等現象。特別地,於捲芯部中壓力高,容易發生此等之現象。根據以上之知識見解,可知上述之缺點係可藉由使脫模面的相反面表面(背面)成為特定的粗糙度而防止。(Roughness on the back side) In addition, even if the release surface of the alignment film for transfer of the present invention is made smooth, defects may occur in the alignment layer of the liquid crystal compound. It can be seen that this is because the alignment film for transfer is wound into a roll, and since the surface is in contact with the back surface, the roughness of the back surface is transferred to the surface (convex portions on the back surface are transferred to the release layer to form concave portions). The alignment film for transfer provided with the alignment layer of the liquid crystal compound is used to protect the alignment layer of the liquid crystal compound. A masking film may be attached and wound, but in order to reduce costs, it is mostly directly wound. In this way, it is considered that when the alignment layer is provided with a state of being wound, the alignment layer is caused by depressions, voids, and alignment disorder of the alignment layer due to the convex portion on the back surface. In addition, it is believed that after the liquid crystal compound alignment layer is provided, voids and alignment disturbances occur in the liquid crystal compound alignment layer due to the protrusions on the back surface. In particular, the pressure in the core of the roll is high, and this phenomenon is prone to occur. Based on the above knowledge, it is known that the above-mentioned shortcomings can be prevented by making the surface (back surface) opposite to the mold release surface a specific roughness.
本發明之轉印用配向薄膜的背面之三次元算術平均粗糙度(SRa)之下限較佳為1nm,更佳為2nm,進一步較佳為3nm,特佳為4nm,最佳為5nm。又,本發明之轉印用配向薄膜的背面之SRa之上限較佳為50nm,更佳為45nm,進一步較佳為40nm。若超過上限則缺點有時會變多。The lower limit of the three-dimensional arithmetic mean roughness (SRa) of the back surface of the alignment film for transfer of the present invention is preferably 1 nm, more preferably 2 nm, further preferably 3 nm, particularly preferably 4 nm, and most preferably 5 nm. In addition, the upper limit of SRa on the back surface of the alignment film for transfer of the present invention is preferably 50 nm, more preferably 45 nm, and still more preferably 40 nm. If it exceeds the upper limit, the disadvantages sometimes increase.
本發明之轉印用配向薄膜的背面之三次元十點平均粗糙度(SRz)之下限較佳為7nm,更佳為10nm,進一步較佳為15nm,特佳為20nm,最佳為25nm。又,本發明之轉印用配向薄膜的背面之SRz之上限較佳為1500nm,更佳為1200nm,進一步較佳為1000nm,特佳為700nm,最佳為500nm。若超過上述則缺點有時會變多。The lower limit of the three-dimensional ten-point average roughness (SRz) of the back surface of the alignment film for transfer of the present invention is preferably 7 nm, more preferably 10 nm, further preferably 15 nm, particularly preferably 20 nm, and most preferably 25 nm. Furthermore, the upper limit of SRz on the back surface of the alignment film for transfer of the present invention is preferably 1500 nm, more preferably 1200 nm, further preferably 1000 nm, particularly preferably 700 nm, and most preferably 500 nm. If it exceeds the above, the disadvantages may increase.
本發明之轉印用配向薄膜的背面之最大高度(SRy:背面最大山高度SRp+背面最大其它深度SRv)之下限較佳為15nm,更佳為20nm,進一步較佳為25nm,特佳為30nm,最佳為40nm。又,本發明之轉印用配向薄膜的背面之最大高度SRy之上限較佳為2000nm,更佳為1500nm,進一步較佳為1200nm,特佳為1000nm,最佳為700nm。若超過上述則缺點有時會變多。The lower limit of the maximum height of the back surface of the alignment film for transfer of the present invention (SRy: maximum mountain height of back surface SRp + maximum other depth of back surface SRv) is preferably 15 nm, more preferably 20 nm, further preferably 25 nm, particularly preferably 30 nm, The best is 40nm. Furthermore, the upper limit of the maximum height SRy of the back surface of the alignment film for transfer of the present invention is preferably 2000 nm, more preferably 1500 nm, further preferably 1200 nm, particularly preferably 1000 nm, and most preferably 700 nm. If it exceeds the above, the disadvantages may increase.
本發明之轉印用配向薄膜的背面之2μm以上的突起之數之上限較佳為5個/m2 ,更佳為4個/m2 ,進一步較佳為3個/m2 ,特佳為2個/m2 ,最佳為1個/m2 。若超過上述則缺點有時會變多。The upper limit of the number of protrusions of 2 μm or more on the back surface of the alignment film for transfer of the present invention is preferably 5/m 2 , more preferably 4/m 2 , still more preferably 3/m 2 , particularly preferably 2 pieces/m 2 , preferably 1 piece/m 2 . If it exceeds the above, the disadvantages may increase.
若本發明之轉印用配向薄膜的背面之粗糙度小於上述範圍,則薄膜的滑動性變差,在薄膜的捲筒之搬運時、捲取時等會難以滑動或容易造成傷痕。又,若本發明之轉印用配向薄膜的背面之粗糙度超過上述,則上述之缺點變容易發生。If the roughness of the back surface of the alignment film for transfer of the present invention is less than the above range, the slidability of the film will be deteriorated, and it will be difficult to slide or scratch when the film roll is transported or wound. Moreover, if the roughness of the back surface of the alignment film for transfer of the present invention exceeds the above-mentioned, the above-mentioned disadvantages will easily occur.
為了使背面之粗糙度成為上述範圍,當本發明之轉印用配向薄膜為延伸薄膜時,可舉出以下之方法。 ・使薄膜原材的背面側層(背面層)成為包含特定粒子者。 ・使用在薄膜原材的中間層中包含粒子者,設為在背面層側(背面層)中不含粒子者而減薄厚度。 ・於薄膜原材的背面側層(背面層)之粗糙度大時,設置平坦化塗層。 ・於薄膜原材的背面側層(背面層)不含粒子時或粗糙度小時,設置易滑塗層(含粒子的塗層)。In order to make the roughness of the back surface within the above range, when the alignment film for transfer of the present invention is a stretched film, the following methods can be mentioned. ・Make the back side layer (back side layer) of the film raw material contain specific particles. ・Use the one that contains particles in the intermediate layer of the film raw material, and reduce the thickness by setting the one that does not contain particles in the back layer side (back layer). ・When the roughness of the back side layer (back layer) of the film material is large, a flattening coating is provided. ・When the back side layer (back layer) of the film material does not contain particles or the roughness is small, a slippery coating (particle-containing coating) is provided.
背面層粒徑之下限較佳為0.01μm,更佳為0.05μm,進一步較佳為0.1μm。若小於上述則滑動性變差,則有發生捲取不良之情況。又,背面層粒徑之上限較佳為5μm,更佳為3μm,進一步較佳為2μm。若超過上述則背面有時會變過粗。The lower limit of the particle size of the back layer is preferably 0.01 μm, more preferably 0.05 μm, and still more preferably 0.1 μm. If it is less than the above, the sliding properties will deteriorate, and the winding failure may occur. In addition, the upper limit of the particle size of the back layer is preferably 5 μm, more preferably 3 μm, and still more preferably 2 μm. If it exceeds the above, the back surface may become too thick.
於背面包含粒子時,較佳為50ppm,更佳為100ppm。若小於上述,則會得不到添加粒子所造成的滑動性效果。又,背面層粒子含量之上限較佳為10000ppm,更佳為7000ppm,進一步較佳為5000ppm。若超過上述則背面有時會變過粗。When particles are contained on the back surface, it is preferably 50 ppm, more preferably 100 ppm. If it is less than the above, the sliding effect due to the addition of particles cannot be obtained. In addition, the upper limit of the content of the back layer particles is preferably 10000 ppm, more preferably 7000 ppm, and still more preferably 5000 ppm. If it exceeds the above, the back surface may become too thick.
背面層厚度之下限較佳為0.1μm,更佳為0.5μm,進一步較佳為1μm,特佳為3μm,最佳為5μm。又,相對於轉印用配向薄膜之總厚度,背面層厚度之上限較佳為95%,更佳為90%,進一步較佳為85%。The lower limit of the thickness of the back layer is preferably 0.1 μm, more preferably 0.5 μm, further preferably 1 μm, particularly preferably 3 μm, and most preferably 5 μm. In addition, the upper limit of the thickness of the back layer relative to the total thickness of the alignment film for transfer is preferably 95%, more preferably 90%, and still more preferably 85%.
亦較佳為使中間層包含粒子,背面層不含粒子而減薄,控制背面的粗糙度。藉由採取如此的形態,可一邊防止粒子之脫落,一邊確保背面的粗糙度。It is also preferable that the middle layer contains particles and the back layer does not contain particles so as to be thinner to control the roughness of the back surface. By adopting such a form, it is possible to ensure the roughness of the back surface while preventing particles from falling off.
中間層的粒子之粒徑或添加量係與背面層的粒子同樣。此時之背面層的厚度之下限較佳為0.5μm,更佳為1μm,進一步較佳為2μm。厚度之上限較佳為30μm,更佳為25μm,進一步較佳為20μm。The particle size or addition amount of the particles in the middle layer is the same as that of the particles in the back layer. The lower limit of the thickness of the back layer at this time is preferably 0.5 μm, more preferably 1 μm, and still more preferably 2 μm. The upper limit of the thickness is preferably 30 μm, more preferably 25 μm, and still more preferably 20 μm.
原材薄膜的背面粗時,亦較佳為設置平坦化塗層。平坦化塗層係可同樣地使用在表面之平坦化塗層所列舉者。When the back surface of the raw material film is thick, it is also preferable to provide a flattening coating. The flattening coating can be the same as those listed in the flattening coating on the surface.
背面平坦化塗層的厚度之下限較佳為0.01μm,更佳為0.03μm,進一步較佳為0.05μm。若小於上述,則平坦化的效果會變小。又,背面平坦化塗層的厚度之上限較佳為10μm,更佳為5μm,進一步較佳為3μm。即使超過上述,平坦化的效果亦會飽和。The lower limit of the thickness of the back flattening coating is preferably 0.01 μm, more preferably 0.03 μm, and still more preferably 0.05 μm. If it is less than the above, the effect of flattening will be reduced. In addition, the upper limit of the thickness of the back surface flattening coating is preferably 10 μm, more preferably 5 μm, and still more preferably 3 μm. Even if it exceeds the above, the flattening effect will be saturated.
可將原材薄膜的背面側設為不含粒子者,在背面設置含有粒子的易滑塗層。又,於原材薄膜的背面之粗糙度小時,亦可設置易滑塗層。The back side of the raw material film can be made without particles, and a slippery coating containing particles can be provided on the back side. In addition, if the roughness of the back surface of the raw material film is small, a slippery coating can be provided.
背面易滑塗層的粒徑之下限較佳為0.01μm,更佳為0.05μm。若小於上述則會得不到易滑性。又,背面易滑塗層的粒徑之上限較佳為5μm,更佳為3μm,進一步較佳為2μm,特佳為1μm。若超過上述則背面的粗糙度有時會過高。The lower limit of the particle size of the back slippery coating is preferably 0.01 μm, more preferably 0.05 μm. If it is less than the above, slipperiness cannot be obtained. In addition, the upper limit of the particle size of the back slippery coating is preferably 5 μm, more preferably 3 μm, still more preferably 2 μm, particularly preferably 1 μm. If it exceeds the above, the roughness of the back surface may be too high.
背面易滑塗層的粒子含量之下限較佳為0.1質量%,更佳為0.5質量%,進一步較佳為1質量%,特佳為1.5質量%,最佳為2質量%。若小於上述則會得不到易滑性。又,背面易滑塗層的粒子含量之上限較佳為20質量%,更佳為15質量%,進一步較佳為10質量%。若超過上述則背面的粗糙度有時會過高。The lower limit of the particle content of the back slippery coating is preferably 0.1% by mass, more preferably 0.5% by mass, still more preferably 1% by mass, particularly preferably 1.5% by mass, and most preferably 2% by mass. If it is less than the above, slipperiness cannot be obtained. In addition, the upper limit of the particle content of the back slip coating layer is preferably 20% by mass, more preferably 15% by mass, and still more preferably 10% by mass. If it exceeds the above, the roughness of the back surface may be too high.
背面易滑塗層的厚度之下限較佳為0.01μm,更佳為0.03μm,進一步較佳為0.05μm。又,背面易滑塗層的厚度之上限較佳為10μm,更佳為5μm,進一步較佳為3μm,特佳為2μm,最佳為1μm。The lower limit of the thickness of the back slippery coating is preferably 0.01 μm, more preferably 0.03 μm, and still more preferably 0.05 μm. In addition, the upper limit of the thickness of the back slippery coating is preferably 10 μm, more preferably 5 μm, still more preferably 3 μm, particularly preferably 2 μm, and most preferably 1 μm.
(轉印用配向薄膜之製造方法) 以下,說明本發明之轉印用配向薄膜為延伸薄膜時的轉印用配向薄膜之製造方法。 進行MD延伸時,MD倍率之下限較佳為1.5倍。上限較佳為6倍,更佳為5.5倍,進一步較佳為5倍。又,進行TD延伸時,TD倍率之下限較佳為1.5倍。TD倍率之上限較佳為6倍,更佳為5.5倍,進一步較佳為5倍。(Method of manufacturing alignment film for transfer) Hereinafter, a method of manufacturing the alignment film for transfer when the alignment film for transfer of the present invention is a stretched film will be described. When MD stretching is performed, the lower limit of MD magnification is preferably 1.5 times. The upper limit is preferably 6 times, more preferably 5.5 times, and still more preferably 5 times. In addition, when performing TD stretching, the lower limit of the TD magnification is preferably 1.5 times. The upper limit of the TD magnification is preferably 6 times, more preferably 5.5 times, and still more preferably 5 times.
HS溫度之下限較佳為150℃,更佳為170℃。若小於上述則熱收縮率有時會不降低。又,HS溫度之上限較佳為240℃,更佳為230℃。若超過上限則有時會樹脂劣化。The lower limit of the HS temperature is preferably 150°C, more preferably 170°C. If it is less than the above, the thermal shrinkage rate may not decrease. Furthermore, the upper limit of the HS temperature is preferably 240°C, more preferably 230°C. If it exceeds the upper limit, the resin may deteriorate.
TD鬆弛率之下限較佳為0.1%,更佳為0.5%。若小於上述則熱收縮率有時會不下降。又,TD鬆弛率之上限較佳為8%,更佳為6%,進一步較佳為5%。若超過上述則會因鬆弛而平面性變差,厚度有時會變不均勻。The lower limit of the TD relaxation rate is preferably 0.1%, more preferably 0.5%. If it is less than the above, the thermal shrinkage rate may not decrease. In addition, the upper limit of the TD relaxation rate is preferably 8%, more preferably 6%, and still more preferably 5%. If it exceeds the above, the flatness deteriorates due to slack and the thickness may become uneven.
退火處理較佳為捲出薄膜,通過烘箱中而捲取之方法。The annealing treatment is preferably a method of rolling out the film and passing it in an oven.
退火溫度之下限較佳為80℃,更佳為90℃,進一步較佳為100℃。若小於上述則有時會得不到退火效果。又,退火溫度之上限較佳為200℃,更佳為180℃,進一步較佳為160℃。若超過上限則有時平面性會降低,或熱收縮會變高。The lower limit of the annealing temperature is preferably 80°C, more preferably 90°C, and still more preferably 100°C. If it is less than the above, the annealing effect may not be obtained. In addition, the upper limit of the annealing temperature is preferably 200°C, more preferably 180°C, and still more preferably 160°C. If it exceeds the upper limit, the flatness may decrease or the heat shrinkage may increase.
退火時間之下限較佳為5秒,更佳為10秒,進一步較佳為15秒。若小於上述則有時會得不到退火效果。又,退火時間之上限較佳為10分鐘,更佳為5分鐘,進一步較佳為3分鐘,特佳為1分鐘。若超過上限則不僅效果飽和,而且需要大的烘箱,生產性有時會變差。The lower limit of the annealing time is preferably 5 seconds, more preferably 10 seconds, and still more preferably 15 seconds. If it is less than the above, the annealing effect may not be obtained. In addition, the upper limit of the annealing time is preferably 10 minutes, more preferably 5 minutes, still more preferably 3 minutes, and particularly preferably 1 minute. If it exceeds the upper limit, not only the effect is saturated, but also a large oven is required, and productivity may deteriorate.
於退火處理中採用以捲出速度與捲取速度之圓周速度差來調節鬆弛率,調整捲取張力而調整鬆弛率等之方法。鬆弛率之下限較佳為0.5%。若小於上述則有時會得不到退火效果。又,鬆弛率之上限較佳為8%,更佳為6%,進一步較佳為5%。若超過上限則有時平面性會降低,或會發生捲取不良。In the annealing process, the method of adjusting the relaxation rate by the circumferential speed difference between the winding speed and the winding speed, and adjusting the winding tension to adjust the relaxation rate is adopted. The lower limit of the relaxation rate is preferably 0.5%. If it is less than the above, the annealing effect may not be obtained. In addition, the upper limit of the relaxation rate is preferably 8%, more preferably 6%, and still more preferably 5%. If the upper limit is exceeded, the flatness may decrease, or the winding failure may occur.
(液晶化合物配向層轉印用積層體) 接著,說明本發明之液晶化合物配向層轉印用積層體。 本發明之液晶化合物配向層轉印用積層體,具有積層有液晶化合物配向層與本發明之轉印用配向薄膜之構造。液晶化合物配向層必須塗布於轉印用配向薄膜上,使其配向。作為使其配向之方法,有對於液晶化合物配向層的下層(脫模面)進行摩擦處理等,賦予配向控制功能之方法,或在塗布液晶化合物後,照射偏光紫外線等,直接使液晶化合物配向之方法。(Laminate for transfer of liquid crystal compound alignment layer) Next, the laminate for transferring the liquid crystal compound alignment layer of the present invention will be described. The layered body for transfer of the liquid crystal compound alignment layer of the present invention has a structure in which the liquid crystal compound alignment layer and the alignment film for transfer of the present invention are laminated. The alignment layer of the liquid crystal compound must be coated on the alignment film for transfer to align it. As a method of alignment, there is a method of rubbing the lower layer (release surface) of the alignment layer of the liquid crystal compound to impart alignment control functions, or after coating the liquid crystal compound, irradiating polarized ultraviolet rays to directly align the liquid crystal compound. method.
(配向控制層) 又,亦較佳為在轉印用配向薄膜上設置配向控制層,在此配向控制層上設置液晶化合物配向層之方法。還有,於本發明中,不僅是液晶化合物配向層,有時合併配向控制層與液晶化合物配向層之總稱,亦稱為液晶化合物配向層。作為配向控制層,只要使液晶化合物配向層成為所欲的配向狀態,則可為任何樣式的配向控制層,但可舉出將樹脂的塗布膜摩擦處理後的摩擦處理配向控制層,或藉由偏光之光照射而使分子配向而產生配向功能之光配向控制層作為合適例。(Alignment control layer) Moreover, it is also preferable to provide an alignment control layer on the alignment film for transfer, and to provide an alignment layer of a liquid crystal compound on the alignment control layer. In addition, in the present invention, not only the alignment layer of the liquid crystal compound, but also the collective term for the alignment control layer and the alignment layer of the liquid crystal compound, which is also called the alignment layer of the liquid crystal compound. As the alignment control layer, any style of alignment control layer can be used as long as the alignment layer of the liquid crystal compound is brought into the desired alignment state, but it can be a rubbing treatment alignment control layer after rubbing a resin coating film, or by A suitable example is a photo-alignment control layer that irradiates the polarized light to align the molecules to produce the alignment function.
(摩擦處理配向控制層) 作為藉由摩擦處理形成的配向控制層中所用的聚合物材料,較宜使用聚乙烯醇及其衍生物、聚醯亞胺及其衍生物、丙烯酸樹脂、聚矽氧烷衍生物等。(Friction processing alignment control layer) As the polymer material used in the alignment control layer formed by rubbing treatment, polyvinyl alcohol and its derivatives, polyimide and its derivatives, acrylic resin, polysiloxane derivatives, etc. are preferably used.
以下,說明摩擦處理配向控制層之形成方法。首先,將包含上述聚合物材料之摩擦處理配向控制層塗布液塗布於配向薄膜的脫模面上後,進行加熱乾燥等,得到摩擦處理前的配向控制層。配向控制層塗布液亦可具有交聯劑。Hereinafter, the method of forming the rubbing alignment control layer will be described. First, after coating the rubbing treatment alignment control layer coating liquid containing the polymer material on the release surface of the alignment film, heating and drying etc. are performed to obtain the alignment control layer before rubbing treatment. The alignment control layer coating liquid may also have a crosslinking agent.
作為摩擦處理配向控制層塗布液之溶劑,只要是溶解聚合物材料者,則可無限制地使用。作為具體例,可舉出水、甲醇、乙醇、乙二醇、異丙醇、丙二醇、賽珞蘇等之醇;乙酸乙酯、乙酸丁酯、γ-丁內酯等之酯系溶劑;丙酮、甲基乙基酮、環戊酮、環己酮等之酮系溶劑;甲苯或二甲苯等之芳香族烴溶劑;四氫呋喃或二甲氧基乙烷等之醚系溶劑等。此等溶劑係可單獨使用,也可組合。As the solvent of the coating liquid for the rubbing treatment alignment control layer, any solvent can be used without limitation as long as it dissolves the polymer material. Specific examples include alcohols such as water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, and serosol; ester solvents such as ethyl acetate, butyl acetate, and γ-butyrolactone; acetone , Methyl ethyl ketone, cyclopentanone, cyclohexanone and other ketone solvents; toluene or xylene and other aromatic hydrocarbon solvents; tetrahydrofuran or dimethoxyethane and other ether solvents. These solvent systems can be used alone or in combination.
摩擦處理配向控制層塗布液之濃度係可按照聚合物之種類或所欲製造的配向控制層之厚度而適宜調節,但以固體成分濃度表示,較佳為0.2~20質量%,特佳為0.3~10質量%之範圍。作為塗布之方法,可採用凹版塗布法、模塗法、棒塗法及施用器法(applicator method)等之塗布法,或柔版法等之印刷法等眾所周知的方法。The concentration of the coating solution for the rubbing treatment alignment control layer can be appropriately adjusted according to the type of polymer or the thickness of the alignment control layer to be manufactured, but expressed in terms of the solid content concentration, preferably 0.2-20% by mass, particularly preferably 0.3 ~10% by mass. As the coating method, well-known methods such as gravure coating, die coating, bar coating, and applicator method, or printing methods such as flexographic method can be used.
加熱乾燥溫度亦取決於轉印用配向薄膜,但PET時較佳為30℃~170℃之範圍,更佳為50~150℃,進一步較佳為70~130℃。乾燥溫度低時,發生需增長乾燥時間之必要,有生產性差之情況。乾燥溫度過高時,轉印用配向薄膜因熱而伸長,或熱收縮變大,無法達成符合設計的光學功能,或有平面性變差之情況。加熱乾燥時間例如可為0.5~30分鐘,較佳為1~20分鐘,更佳為2~10分鐘。The heating and drying temperature also depends on the alignment film for transfer, but for PET, it is preferably in the range of 30°C to 170°C, more preferably 50 to 150°C, and still more preferably 70 to 130°C. When the drying temperature is low, it is necessary to increase the drying time, and the productivity may be poor. When the drying temperature is too high, the alignment film for transfer will be stretched due to heat, or the heat shrink will become greater, failing to achieve the optical function that meets the design, or the flatness may deteriorate. The heating and drying time can be, for example, 0.5 to 30 minutes, preferably 1 to 20 minutes, more preferably 2 to 10 minutes.
摩擦處理配向控制層之厚度較佳為0.01~10μm,更佳為0.05~5μm,特佳為0.1μm~1μm。The thickness of the rubbing alignment control layer is preferably 0.01-10 μm, more preferably 0.05-5 μm, particularly preferably 0.1 μm-1 μm.
接著,施予摩擦處理。摩擦處理一般可藉由紙或布在一定方向中摩擦聚合物層之表面而實施。一般而言,使用尼龍、聚酯、丙烯酸等之纖維的起毛布之摩擦輥,摩擦處理配向控制層表面。為了設置相對於長條狀薄膜之長度方向而言在斜的指定方向中配向的液晶化合物配向控制層,配向控制層的摩擦方向亦必須成為配合其之角度。角度之調整係可藉由調整摩擦輥與配向薄膜之角度、調整配向薄膜的搬運速度與輥的旋轉數而使其一致。Then, rubbing treatment is applied. The rubbing treatment can generally be implemented by rubbing the surface of the polymer layer with paper or cloth in a certain direction. Generally speaking, the surface of the alignment control layer is rubbed with a rubbing roller of a raised cloth made of nylon, polyester, acrylic and other fibers. In order to provide the alignment control layer of the liquid crystal compound that is aligned in an obliquely specified direction with respect to the longitudinal direction of the long film, the rubbing direction of the alignment control layer must also be an angle that matches it. The angle can be adjusted by adjusting the angle of the rubbing roller and the alignment film, adjusting the conveying speed of the alignment film and the number of rotations of the roller to make it consistent.
再者,亦可對於轉印用配向薄膜的脫模面直接進行摩擦處理,而使轉印用配向薄膜表面具有配向控制功能,此情況亦包含於本發明之技術範圍中。Furthermore, it is also possible to directly perform rubbing treatment on the release surface of the alignment film for transfer, so that the surface of the alignment film for transfer has an alignment control function, which is also included in the technical scope of the present invention.
(光配向控制層) 所謂的光配向控制層,就是指將包含具有光反應性基的聚合物或單體與溶劑之塗布液塗布於配向薄膜,藉由照射偏光,較佳為偏光紫外線,而賦予有配向管制力的配向膜者。所謂的光反應性基,就是指藉由光照射而產生液晶配向能力的基。具體而言,發生因照射光而產生的分子之配向誘發或如異構化反應、二聚化反應、光交聯反應或光分解反應之成為液晶配向能力的起源之光反應者。於該光反應性基之中,發生二聚化反應或光交聯反應者,係在配向性優異,保持液晶化合物配向層的層列液晶狀態之點上較宜。作為能發生如以上的反應之光反應性基,較佳為具有不飽和鍵,尤其雙鍵,特佳為具有選自由C=C鍵、C=N鍵、N=N鍵、C=O鍵所組成之群組的至少一個之基。(Optical alignment control layer) The so-called photo-alignment control layer refers to coating a coating liquid containing a polymer or monomer with a photoreactive group and a solvent on the alignment film, and by irradiating polarized light, preferably polarized ultraviolet light, to impart alignment control power Those who align the film. The so-called photoreactive group refers to a group that produces liquid crystal alignment ability by light irradiation. Specifically, the orientation induction of molecules generated by the irradiation of light occurs, or the photoreaction that becomes the origin of the alignment ability of the liquid crystal, such as an isomerization reaction, a dimerization reaction, a photocrosslinking reaction, or a photolysis reaction. Among the photoreactive groups, those that undergo a dimerization reaction or a photocrosslinking reaction are preferable in terms of excellent alignment and maintaining the smectic liquid crystal state of the alignment layer of the liquid crystal compound. The photoreactive group capable of reacting as above preferably has an unsaturated bond, especially a double bond, and particularly preferably has a bond selected from the group consisting of C=C bond, C=N bond, N=N bond, and C=O bond. The base of at least one of the formed group.
作為具有C=C鍵的光反應性基,例如可舉出乙烯基、多烯基、二苯乙烯基、苯乙烯基吡啶基、苯乙烯基吡啶鎓基、查耳酮基及桂皮醯基等。作為具有C=N鍵的光反應性基,可舉出具有芳香族希夫鹼及芳香族腙等結構之基。作為具有N=N鍵的光反應性基,可舉出具有偶氮苯基、偶氮萘基、芳香族雜環偶氮基、雙偶氮基及甲䐶基等或偶氮氧基苯作為基本結構者。作為具有C=O鍵的光反應性基,可舉出二苯基酮基、香豆素基、蒽醌基及馬來醯亞胺基等。此等之基亦可具有烷基、烷氧基、芳基、烯丙氧基、氰基、烷氧基羰基、羥基、磺酸基及鹵化烷基等之取代基。Examples of the photoreactive group having a C=C bond include vinyl, polyalkenyl, distyryl, styrylpyridyl, styrylpyridinium, chalcone, and cinnamyl, etc. . Examples of the photoreactive group having a C=N bond include groups having structures such as aromatic Schiff bases and aromatic hydrazones. Examples of the photoreactive group having N=N bond include azophenyl group, azonaphthyl group, aromatic heterocyclic azo group, bisazo group, methyl group, etc., or azooxybenzene as Basic structure. As a photoreactive group which has a C=O bond, a diphenyl ketone group, a coumarin group, an anthraquinone group, a maleimide group, etc. are mentioned. These groups may also have substituents such as alkyl, alkoxy, aryl, allyloxy, cyano, alkoxycarbonyl, hydroxy, sulfonic acid, and halogenated alkyl.
其中,較佳為能發生光二聚化反應的光反應性基,桂皮醯基及查耳酮基由於光配向所需要的偏光照射量為比較少,且容易得到熱安定性或隨著時間經過的安定性優異之光配向層而較宜。進一步來說,作為具有光反應性基的聚合物,特佳為該聚合物側鏈的末端部具有成為如桂皮酸結構的桂皮醯基者。作為主鏈之結構,可舉出聚醯亞胺、聚醯胺、(甲基)丙烯酸、聚酯等。Among them, the photoreactive group capable of photodimerization reaction is preferred, and the amount of polarized light irradiation required for photo-alignment of the cinnamon group and the chalcone group is relatively small, and it is easy to obtain the thermal stability or the time-lapse A photo-alignment layer with excellent stability is preferred. Furthermore, as a polymer having a photoreactive group, it is particularly preferable that the terminal portion of the side chain of the polymer has a cinnamyl group having a structure such as cinnamic acid. Examples of the structure of the main chain include polyimide, polyamide, (meth)acrylic acid, polyester, and the like.
作為具體的配向控制層,例如可舉出日本特開2006-285197號公報、日本特開2007-76839號公報、日本特開2007-138138號公報、日本特開2007-94071號公報、日本特開2007-121721號公報、日本特開2007-140465號公報、日本特開2007-156439號公報、日本特開2007-133184號公報、日本特開2009-109831號公報、日本特開2002-229039號公報、日本特開2002-265541號公報、日本特開2002-317013號公報、日本特表2003-520878號公報、日本特表2004-529220號公報、日本特開2013-33248號公報、日本特開2015-7702號公報、日本特開2015-129210號公報中記載之配向控制層。As specific alignment control layers, for example, Japanese Patent Application Publication No. 2006-285197, Japanese Patent Application Publication No. 2007-76839, Japanese Patent Application Publication No. 2007-138138, Japanese Patent Application Publication No. 2007-94071, Japanese Patent Application Publication No. 2007-121721, Japanese Patent Application Publication No. 2007-140465, Japanese Patent Application Publication No. 2007-156439, Japanese Patent Application Publication No. 2007-133184, Japanese Patent Application Publication No. 2009-109831, Japanese Patent Application Publication No. 2002-229039 , Japanese Patent Application Publication No. 2002-265541, Japanese Patent Application Publication No. 2002-317013, Japanese Patent Application Publication No. 2003-520878, Japanese Patent Application Publication No. 2004-529220, Japanese Patent Application Publication No. 2013-33248, Japanese Patent Application Publication 2015 -The alignment control layer described in No. 7702 and JP 2015-129210.
作為光配向控制層形成用塗布液之溶劑,只要是能溶解具有光反應性基的聚合物及單體者,則可無限制地使用。作為具體例,可例示在摩擦處理配向控制層之形成方法所列舉者。於光配向控制層形成用塗布液中,亦較佳為添加光聚合起始劑、聚合抑制劑、各種安定劑。又,亦可添加具有光反應性基的聚合物及單體以外的聚合物或不具有與光反應性基的單體能共聚合的光反應性基之單體。As the solvent of the coating liquid for forming the photo-alignment control layer, any solvent that can dissolve the polymer and monomer having a photoreactive group can be used without limitation. As a specific example, those exemplified in the formation method of the rubbing treatment alignment control layer can be exemplified. It is also preferable to add a photopolymerization initiator, a polymerization inhibitor, and various stabilizers to the coating liquid for forming a photo-alignment control layer. In addition, a polymer having a photoreactive group and a polymer other than a monomer or a monomer having no photoreactive group copolymerizable with a monomer having a photoreactive group may be added.
光配向控制層形成用塗布液之濃度、塗布方法、乾燥條件亦可例示在摩擦處理配向控制層之形成方法所列舉者。厚度亦與摩擦處理配向控制層的較佳厚度同樣。The concentration, coating method, and drying conditions of the coating solution for forming the photo-alignment control layer can also be exemplified in the rubbing treatment method for forming the alignment control layer. The thickness is also the same as the preferred thickness of the rubbing treatment alignment control layer.
偏光較佳為從配向前的光配向控制層面之方向來照射。對於轉印用配向薄膜的配向方向,使光配向控制層之配向方向成為平行或垂直時,亦可穿透轉印用配向薄膜而照射。The polarized light is preferably irradiated from the direction of the optical alignment control plane in the forward direction. Regarding the alignment direction of the alignment film for transfer, when the alignment direction of the photo-alignment control layer becomes parallel or vertical, it can also be irradiated through the alignment film for transfer.
偏光之波長較佳為具有光反應性基的聚合物或單體之光反應性基能吸收光能量之波長區域者。具體而言,較佳為波長250~400nm之範圍的紫外線。作為偏光的光源,可舉出氙燈、高壓水銀燈、超高壓水銀燈、金屬鹵化物燈、KrF、ArF等之紫外光雷射等,較佳為高壓水銀燈、超高壓水銀燈及金屬鹵化物燈。The wavelength of the polarized light is preferably in the wavelength region where the photoreactive group of the polymer or monomer having the photoreactive group can absorb light energy. Specifically, ultraviolet rays having a wavelength in the range of 250 to 400 nm are preferable. Examples of the polarized light source include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, KrF, ArF, and other ultraviolet lasers, and high-pressure mercury lamps, ultra-high pressure mercury lamps, and metal halide lamps are preferred.
偏光例如係藉由使來自前述光源的光通過偏光鏡而得。藉由調整前述偏光鏡的偏光角,可調整偏光的方向。前述偏光鏡可舉出偏光濾片或格蘭-湯姆森(Glan-Thompson)、格蘭-泰勒(Glan-Taylor)等之偏光稜鏡或線柵型之偏光鏡。偏光較佳為實質上平行光。Polarized light is obtained, for example, by passing light from the aforementioned light source through a polarizer. By adjusting the polarization angle of the aforementioned polarizer, the direction of the polarization can be adjusted. The aforementioned polarizer may include a polarizing filter or a polarizer of Glan-Thompson, Glan-Taylor, etc. or a wire grid type polarizer. The polarized light is preferably substantially parallel light.
藉由調整所照射的偏光之角度,可任意地調整光配向控制層之配向管制力的方向。By adjusting the angle of the irradiated polarized light, the direction of the alignment control force of the light alignment control layer can be adjusted arbitrarily.
照射強度雖然因聚合起始劑或樹脂(單體)之種類或量而不同,但例如以365nm基準,較佳為10~10000mJ/cm2 ,更佳為20~5000mJ/cm2 。Although the irradiation intensity differs depending on the type or amount of the polymerization initiator or resin (monomer), for example, based on 365 nm, it is preferably 10 to 10000 mJ/cm 2 , and more preferably 20 to 5000 mJ/cm 2 .
(液晶化合物配向層) 液晶化合物配向層只要是將液晶化合物配向者,則沒有特別的限制。作為具體例,可舉出包含液晶化合物與二色性色素之偏光膜(偏光鏡)、包含棒狀或圓盤狀液晶化合物之相位差層。(Liquid crystal compound alignment layer) The liquid crystal compound alignment layer is not particularly limited as long as it aligns the liquid crystal compound. Specific examples include a polarizing film (polarizer) containing a liquid crystal compound and a dichroic dye, and a retardation layer containing a rod-shaped or disc-shaped liquid crystal compound.
(偏光膜) 偏光膜具有僅使一方向的偏光通過之功能,包含二色性色素。(Polarizing film) The polarizing film has a function of passing polarized light in only one direction, and contains a dichroic dye.
(二色性色素) 所謂的二色性色素,就是指具有分子的長軸方向之吸光度與短軸方向之吸光度為不同性質的色素。(Dichroic pigment) The so-called dichroic pigments refer to pigments that have different properties between the absorbance in the long axis direction and the absorbance in the short axis direction of the molecule.
二色性色素較佳為在300~700nm之範圍中具有吸收極大波長(λMAX)者。如此的二色性色素例如可舉出吖啶色素、 色素、花青色素、萘色素、偶氮色素及蒽醌色素等,其中較佳為偶氮色素。偶氮色素可舉出單偶氮色素、雙偶氮色素、三偶氮色素、四偶氮色素及二苯乙烯偶氮色素等,較佳為雙偶氮色素及三偶氮色素。二色性色素係可單獨,也可組合,但為了調整色調(無彩色),較佳為組合2種以上。特佳為組合3種類以上。特別地,較佳為組合3種類以上的偶氮化合物。The dichroic dye is preferably one having an absorption maximum wavelength (λMAX) in the range of 300 to 700 nm. Examples of such dichroic dyes include acridine dyes, Among pigments, cyanine pigments, naphthalene pigments, azo pigments, anthraquinone pigments, etc., azo pigments are preferred. Examples of azo dyes include monoazo dyes, bisazo dyes, trisazo dyes, tetrasazo dyes, and stilbene azo dyes, and bisazo dyes and trisazo dyes are preferred. The dichroic dye system may be singly or in combination, but in order to adjust the hue (achromatic color), it is preferable to combine two or more kinds. Especially preferred is a combination of more than 3 types. In particular, it is preferable to combine three or more types of azo compounds.
作為較佳的偶氮化合物,可舉出日本特開2007-126628號公報、日本特開2010-168570號、日本特開2013-101328號、日本特開2013-210624號中記載之色素。As preferable azo compounds, the dyes described in Japanese Patent Application Publication No. 2007-126628, Japanese Patent Application Publication No. 2010-168570, Japanese Patent Application Publication No. 2013-101328, and Japanese Patent Application Publication No. 2013-210624 may be mentioned.
二色性色素亦較佳為導入至丙烯酸等聚合物之側鏈的二色性色素聚合物。作為此等二色性色素聚合物,可例示日本特開2016-4055號中列舉的聚合物、日本特開2014-206682號之[化6]~[化12]的化合物聚合而成之聚合物。The dichroic dye is also preferably a dichroic dye polymer introduced into the side chain of a polymer such as acrylic acid. Examples of such dichroic dye polymers include polymers listed in Japanese Patent Application Publication No. 2016-4055, and polymers obtained by polymerization of compounds from [Chemical Formula 6] to [Chemical Formula 12] in Japanese Patent Publication No. 2014-206682. .
偏光膜中的二色性色素之含量,從使二色性色素的配向成為良好之觀點來看,在偏光膜中較佳為0.1~30質量%,更佳為0.5~20質量%,進一步較佳為1.0~15質量%,特佳為2.0~10質量%。The content of the dichroic pigment in the polarizing film is preferably 0.1-30% by mass in the polarizing film, more preferably 0.5-20% by mass, and furthermore, from the viewpoint of making the alignment of the dichroic dye good. It is preferably 1.0 to 15% by mass, and particularly preferably 2.0 to 10% by mass.
於偏光膜中,為了提高膜強度或偏光度、膜均質性,較佳為進一步包含聚合性液晶化合物。再者,此處聚合性液晶化合物亦包含聚合後之物作為膜。In the polarizing film, in order to improve the film strength, polarization degree, and film homogeneity, it is preferable to further include a polymerizable liquid crystal compound. Furthermore, the polymerizable liquid crystal compound here also includes a polymerized product as a film.
(聚合性液晶化合物) 所謂的聚合性液晶化合物,就是具有聚合性基且顯示液晶性之化合物。 所謂的聚合性基,就是意指參與聚合反應之基,較佳為光聚合性基。此處,所謂的光聚合性基,就是指從後述的光聚合起始劑所發生的活性自由基或藉由酸等可進行聚合反應之基。作為聚合性基,可舉出乙烯基、乙烯氧基、1-氯乙烯基、異丙烯基、4-乙烯基苯基、丙烯醯氧基、甲基丙烯醯氧基、環氧乙烷基、氧雜環丁基等。其中,較佳為丙烯醯氧基、甲基丙烯醯氧基、乙烯氧基、環氧乙烷基及氧雜環丁基,更佳為丙烯醯氧基。顯示液晶性的化合物係可為熱致性液晶或溶致液晶,另外可舉出熱致液晶中的向列液晶或層列液晶。(Polymerizable liquid crystal compound) The so-called polymerizable liquid crystal compound is a compound that has a polymerizable group and exhibits liquid crystallinity. The so-called polymerizable group means a group that participates in a polymerization reaction, and a photopolymerizable group is preferred. Here, the so-called photopolymerizable group refers to a living radical generated from a photopolymerization initiator described later, or a group capable of polymerization reaction by acid or the like. Examples of the polymerizable group include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, ethylene oxide, Oxetanyl and so on. Among them, propyleneoxy group, methacryloxy group, ethyleneoxy group, oxirane group and oxetanyl group are preferred, and propyleneoxy group is more preferred. The compound system exhibiting liquid crystallinity may be a thermotropic liquid crystal or a lyotropic liquid crystal, and a nematic liquid crystal or a smectic liquid crystal in a thermotropic liquid crystal may be mentioned.
於得到更高的偏光特性之點上,聚合性液晶化合物較佳為層列液晶化合物,更佳為高次層列液晶化合物。若聚合性液晶化合物所形成的液晶相為高次層列相,則可製造配向秩序度更高的偏光膜。In order to obtain higher polarization characteristics, the polymerizable liquid crystal compound is preferably a smectic liquid crystal compound, and more preferably a higher order smectic liquid crystal compound. If the liquid crystal phase formed by the polymerizable liquid crystal compound is a higher order smectic phase, a polarizing film with a higher degree of alignment order can be produced.
作為具體的較佳聚合性液晶化合物,例如可舉出日本特開2002-308832號公報、日本特開2007-16207號公報、日本特開2015-163596號公報、日本特表2007-510946號公報、日本特開2013-114131號公報、WO2005/045485號公報、Lub等人的Recl. Trav. Chim. Pays-Bas, 115,321-328(1996)等中記載者。As specific preferred polymerizable liquid crystal compounds, for example, Japanese Patent Application Publication No. 2002-308832, Japanese Patent Application Publication No. 2007-16207, Japanese Patent Application Publication No. 2015-163596, Japanese Patent Application Publication No. 2007-510946, JP 2013-114131 A, WO2005/045485, Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996), etc. of Lub et al.
偏光膜中的聚合性液晶化合物之含有比例,從增高聚合性液晶化合物的配向性之觀點來看,較佳為偏光膜中的70~99.5質量%,更佳為75~99質量%,進一步較佳為80~97質量%,特佳為83~95質量%。The content ratio of the polymerizable liquid crystal compound in the polarizing film is preferably 70 to 99.5% by mass in the polarizing film, more preferably 75 to 99% by mass, and furthermore, from the viewpoint of increasing the orientation of the polymerizable liquid crystal compound. It is preferably 80 to 97% by mass, particularly preferably 83 to 95% by mass.
偏光膜係可塗布偏光膜組成物塗料而設置。偏光膜組成物塗料亦可包含溶劑、聚合起始劑、增感劑、聚合抑制劑、調平劑及聚合性非液晶化合物、交聯劑等。The polarizing film system can be provided by coating the polarizing film composition paint. The polarizing film composition coating material may also contain solvents, polymerization initiators, sensitizers, polymerization inhibitors, leveling agents, polymerizable non-liquid crystal compounds, crosslinking agents, and the like.
作為溶劑,較宜使用作為配向層塗布液之溶劑所列舉者。As the solvent, those listed as the solvent of the alignment layer coating liquid are preferably used.
聚合起始劑只要是使聚合性液晶化合物聚合者,則沒有限定,但較佳為因光產生活性自由基的光聚合起始劑。作為聚合起始劑,例如可舉出苯偶姻化合物、二苯基酮化合物、烷基苯酮化合物、醯基氧化膦化合物、三化合物、錪鎓鹽及鋶鹽等。The polymerization initiator is not limited as long as it polymerizes the polymerizable liquid crystal compound, but it is preferably a photopolymerization initiator that generates active radicals by light. As the polymerization initiator, for example, a benzoin compound, a diphenyl ketone compound, an alkyl phenone compound, an acyl phosphine oxide compound, three Compounds, iodonium salts and sulfonium salts, etc.
增感劑較佳為光增感劑。例如,可舉出呫噸酮化合物、蒽化合物、啡噻、紅螢烯等。The sensitizer is preferably a photosensitizer. For example, xanthone compounds, anthracene compounds, phenanthrene , Red fluorene, etc.
作為聚合抑制劑,可舉出氫醌類、兒茶酚類、硫酚類。Examples of polymerization inhibitors include hydroquinones, catechols, and thiophenols.
作為聚合性非液晶化合物,較佳為與聚合性液晶化合物共聚合者,例如,於聚合性液晶化合物具有(甲基)丙烯醯氧基時,可舉出(甲基)丙烯酸酯類。(甲基)丙烯酸酯類可為單官能,也可為多官能。藉由使用多官能的(甲基)丙烯酸酯類,可提高偏光膜的強度。使用聚合性非液晶化合物時,在偏光膜中較佳為1~15質量%,更佳為2~10質量%,特佳為3~7質量%。若超過15質量%,則有時偏光度會降低。The polymerizable non-liquid crystal compound is preferably one that is copolymerized with a polymerizable liquid crystal compound. For example, when the polymerizable liquid crystal compound has a (meth)acryloyloxy group, (meth)acrylates are mentioned. The (meth)acrylates may be monofunctional or polyfunctional. By using multifunctional (meth)acrylates, the strength of the polarizing film can be improved. When a polymerizable non-liquid crystal compound is used, it is preferably 1 to 15% by mass in the polarizing film, more preferably 2 to 10% by mass, and particularly preferably 3 to 7% by mass. If it exceeds 15% by mass, the degree of polarization may decrease.
作為交聯劑,可舉出能與聚合性液晶化合物、聚合性非液晶化合物的官能基反應之化合物,可舉出異氰酸酯化合物、三聚氰胺、環氧樹脂、唑啉化合物等。Examples of the crosslinking agent include compounds capable of reacting with the functional groups of polymerizable liquid crystal compounds and polymerizable non-liquid crystal compounds, including isocyanate compounds, melamine, epoxy resins, Oxazoline compounds and so on.
於將偏光膜組成物塗料直接塗布於轉印用配向薄膜上或配向控制層上後,視需要地藉由乾燥、加熱、硬化,而設置偏光膜。After coating the polarizing film composition coating directly on the alignment film for transfer or the alignment control layer, the polarizing film is set by drying, heating, and curing as necessary.
作為塗布方法,可採用凹版塗布法、模塗法、棒塗法及施用器法等之塗布法,或柔版法等之印刷法等眾所周知的方法。As the coating method, well-known methods such as coating methods such as gravure coating, die coating, bar coating, and applicator methods, or printing methods such as flexographic methods can be used.
塗布後的轉印用配向薄膜係被導引至溫風乾燥機、紅外線乾燥機等,在30~170℃、較佳在50~150℃、更佳在70~130℃被乾燥。乾燥時間較佳為0.5~30分鐘,更佳為1~20分鐘,進一步較佳為2~10分鐘。The coated alignment film for transfer is guided to a warm air dryer, infrared dryer, etc., and dried at 30 to 170°C, preferably 50 to 150°C, more preferably 70 to 130°C. The drying time is preferably 0.5 to 30 minutes, more preferably 1 to 20 minutes, and still more preferably 2 to 10 minutes.
加熱係可為了使偏光膜中的二色性色素及聚合性液晶化合物更強固地配向而進行。加熱溫度較佳為聚合性液晶化合物形成液晶相之溫度範圍。The heating system can be performed to align the dichroic dye and the polymerizable liquid crystal compound in the polarizing film more strongly. The heating temperature is preferably a temperature range where the polymerizable liquid crystal compound forms a liquid crystal phase.
於偏光膜組成物塗料中包含聚合性液晶化合物時,較佳為進行硬化。作為硬化方法,可舉出加熱及光照射,較佳為光照射。藉由硬化,可將二色性色素以配向之狀態固定。硬化較佳為以在聚合性液晶化合物中形成有液晶相之狀態進行,亦可在顯示液晶相的溫度下光照射而硬化。作為光照射的光,可舉出可見光、紫外光及雷射光。於容易操作之點上,較佳為紫外光。When a polymerizable liquid crystal compound is included in the polarizing film composition paint, it is preferably cured. Examples of the curing method include heating and light irradiation, and light irradiation is preferred. By hardening, the dichroic pigment can be fixed in an aligned state. The curing is preferably performed in a state where a liquid crystal phase is formed in the polymerizable liquid crystal compound, and it may be cured by light irradiation at a temperature at which the liquid crystal phase is displayed. Examples of the light to be irradiated include visible light, ultraviolet light, and laser light. In terms of easy operation, ultraviolet light is preferred.
照射強度雖然因聚合起始劑或樹脂(單體)之種類或量而不同,但例如以365nm基準,較佳為100~10000mJ/cm2 ,更佳為200~5000mJ/cm2 。Although the irradiation intensity varies with the type or amount of the polymerization initiator or resin (monomer), for example, based on 365 nm, it is preferably 100 to 10000 mJ/cm 2 , more preferably 200 to 5000 mJ/cm 2 .
偏光膜係藉由將偏光膜組成物塗料塗布配向控制層上,而色素沿著配向層之配向方向進行配向,結果變成具有特定方向的偏光穿透軸,但當不設置配向控制層而直接塗布於轉印用配向薄膜時,藉由照射偏光光線而使偏光膜形成用組成物硬化,亦可使偏光膜配向。此時,相對於轉印用配向薄膜的長條方向,照射所欲方向的偏光光線(例如,斜方向的偏光光線)。再者,較佳為其後藉由加熱處理使二色性色素強固地沿著高分子液晶之配向方向進行配向。The polarizing film is coated on the alignment control layer by coating the composition of the polarizing film, and the pigment is aligned along the alignment direction of the alignment layer, resulting in a polarization transmission axis with a specific direction, but when the alignment control layer is not provided, it is directly coated In the alignment film for transfer, the polarizing film forming composition is cured by irradiating polarized light, and the polarizing film can also be aligned. At this time, polarized light rays in a desired direction (for example, polarized light rays in an oblique direction) are irradiated with respect to the longitudinal direction of the alignment film for transfer. Furthermore, it is preferable that the dichroic dye is strongly aligned along the alignment direction of the polymer liquid crystal by heat treatment.
偏光膜之厚度為0.1~5μm,較佳為0.3~3μm,更佳為0.5~2μm。The thickness of the polarizing film is 0.1-5 μm, preferably 0.3-3 μm, more preferably 0.5-2 μm.
(相位差層) 相位差層係可舉出為了光學補償而設於液晶顯示裝置的偏光鏡與液晶胞之間,或以圓偏光板的λ/4層、λ/2層等為代表者。作為液晶化合物,可使用正或負的A板、正或負的C板、O板等配合目的之棒狀液晶化合物或圓盤狀液晶化合物等。(Retardation layer) Examples of the retardation layer system include those provided between the polarizer and the liquid crystal cell of the liquid crystal display device for optical compensation, or the λ/4 layer and λ/2 layer of the circular polarizing plate as a representative. As the liquid crystal compound, a positive or negative A plate, a positive or negative C plate, an O plate, and other rod-shaped liquid crystal compounds or disc-shaped liquid crystal compounds according to the purpose can be used.
相位差的程度係在作為液晶顯示裝置的光學補償使用時,按照液晶胞之類型、用於晶胞的液晶化合物之性質而適宜設定。例如,於TN方式時,較宜使用採用圓盤狀液晶的O板。於VA方式或IPS方式時,較宜使用採用棒狀液晶化合物或圓盤狀液晶化合物的C板(C-plate)或A板。又,於圓偏光板的λ/4相位差層、λ/2相位差層時,使用棒狀化合物,作為A板者較宜。此等之相位差層係不僅單層,而且也可組合成為複數之層使用。The degree of phase difference is appropriately set according to the type of liquid crystal cell and the properties of the liquid crystal compound used in the liquid crystal display device when used as an optical compensation of a liquid crystal display device. For example, in the TN mode, it is better to use an O plate that uses a disc-shaped liquid crystal. In the case of the VA method or the IPS method, it is preferable to use a C-plate or A plate using a rod-shaped liquid crystal compound or a disc-shaped liquid crystal compound. In addition, in the case of the λ/4 retardation layer and the λ/2 retardation layer of the circularly polarizing plate, a rod-shaped compound is used, and the A plate is suitable. These retardation layers are not only a single layer, but can also be combined into a plurality of layers.
作為此等之相位差層所用的液晶化合物,於能固定配向狀態之方面,較佳為具有雙鍵等的聚合性基之聚合性液晶化合物。As the liquid crystal compound used in these retardation layers, a polymerizable liquid crystal compound having a polymerizable group such as a double bond is preferable in that the alignment state can be fixed.
作為棒狀液晶化合物之例,可舉出日本特開2002-030042號公報、日本特開2004-204190號公報、日本特開2005-263789號公報、日本特開2007-119415號公報、日本特開2007-186430號公報及日本特開平11-513360號公報中記載之具有聚合性基的棒狀液晶化合物。 作為具體的化合物,可舉出: CH2 =CHCOO-(CH2 )m-O-Ph1-COO-Ph2-OCO-Ph1-O-(CH2 )n-OCO-CH=CH2 CH2 =CHCOO-(CH2 )m-O-Ph1-COO-NPh-OCO-Ph1-O-(CH2 )n-OCO-CH=CH2 CH2 =CHCOO-(CH2 )m-O-Ph1-COO-Ph2-OCH3 CH2 =CHCOO-(CH2 )m-O-Ph1-COO-Ph1-Ph1-CH2 CH(CH3 )C2 H5 式中,m、n為2~6之整數, Ph1、Ph2為1,4-苯基(Ph2係2位可為甲基), NPh為2,6-萘基。 此等之棒狀液晶化合物係已由BASF公司製作為LC242等市售,可利用彼等。Examples of rod-shaped liquid crystal compounds include Japanese Patent Application Publication No. 2002-030042, Japanese Patent Application Publication No. 2004-204190, Japanese Patent Application Publication No. 2005-263789, Japanese Patent Application Publication No. 2007-119415, and Japanese Patent Application Publication No. 2007-119415. A rod-shaped liquid crystal compound having a polymerizable group described in 2007-186430 and Japanese Patent Application Laid-Open No. 11-513360. As a specific compound, CH 2 =CHCOO-(CH 2 )mO-Ph1-COO-Ph2-OCO-Ph1-O-(CH 2 )n-OCO-CH=CH 2 CH 2 =CHCOO-( CH 2 )mO-Ph1-COO-NPh-OCO-Ph1-O-(CH 2 )n-OCO-CH=CH 2 CH 2 =CHCOO-(CH 2 )mO-Ph1-COO-Ph2-OCH 3 CH 2 =CHCOO-(CH 2 )mO-Ph1-COO-Ph1-Ph1-CH 2 CH(CH 3 )C 2 H 5 In the formula, m and n are integers from 2 to 6, and Ph1 and Ph2 are 1,4-benzene (Ph2 is a methyl group at the 2 position), and NPh is 2,6-naphthyl. These rod-shaped liquid crystal compounds have been produced by BASF Corporation as LC242 and other commercial products, and they can be used.
此等之棒狀液晶化合物係可以任意之比率組合複數種而使用。These rod-shaped liquid crystal compounds can be used in combination of plural kinds at any ratio.
又,作為圓盤狀液晶化合物,可舉出苯衍生物、三茚并苯衍生物、環己烷衍生物、氮雜冠(aza-crown)系、苯基乙炔系大環等日本特開2001-155866號公報中記載的各式各樣者,此等係可適用。 其中作為圓盤狀化合物,較宜使用下述通式(1)所示之具有聯伸三苯(triphylene)環的化合物。 式中,R1 ~R6 各自獨立地係氫、鹵素、烷基或-O-X所示的基(此處,X係烷基、醯基、烷氧基苄基、環氧基改質烷氧基苄基、丙烯醯氧基改質烷氧基苄基、丙烯醯氧基改質烷基)。R1 ~R6 較佳為下述通式(2)所示的丙烯醯氧基改質烷氧基苄基(此處,m為4~10)。 In addition, examples of discotic liquid crystal compounds include benzene derivatives, triindenacene derivatives, cyclohexane derivatives, aza-crown series, phenylacetylene series macrocycles, etc. Japanese Patent Laid-Open 2001 For all kinds of items described in Bulletin No. 155866, these systems are applicable. Among them, as the discotic compound, a compound having a triphylene ring represented by the following general formula (1) is preferably used. In the formula, R 1 to R 6 are each independently hydrogen, halogen, alkyl, or a group represented by -OX (here, X is an alkyl group, an acyl group, an alkoxy benzyl group, an epoxy group modified alkoxy group Benzyl, acryloxy modified alkoxy benzyl, acryloxy modified alkyl). R 1 to R 6 are preferably propyleneoxy-modified alkoxybenzyl groups represented by the following general formula (2) (here, m is 4 to 10).
相位差層係可塗布相位差層用組成物塗料而設置。相位差層用組成物塗料可包含溶劑、聚合起始劑、增感劑、聚合抑制劑、調平劑及聚合性非液晶化合物、交聯劑等。此等係可使用在配向控制層或液晶偏光鏡之部分所說明之物。The retardation layer can be provided by coating the composition paint for the retardation layer. The composition paint for the retardation layer may contain a solvent, a polymerization initiator, a sensitizer, a polymerization inhibitor, a leveling agent, a polymerizable non-liquid crystal compound, a crosslinking agent, and the like. These can be used as described in the alignment control layer or the liquid crystal polarizer.
將相位差層用組成物塗料塗布於配向薄膜的脫模面或配向控制層上後,藉由乾燥、加熱、硬化,而設置相位差層。After coating the composition paint for the retardation layer on the release surface or the alignment control layer of the alignment film, the retardation layer is provided by drying, heating, and curing.
此等之條件亦使用在配向控制層或液晶偏光鏡之部分所說明之條件作為較佳的條件。For these conditions, the conditions described in the alignment control layer or the liquid crystal polarizer are also used as preferable conditions.
有時可設置複數個相位差層,但此時可在1個轉印用配向薄膜上設置複數個相位差層,將此轉印至對象物,也可準備複數種的在1個轉印用配向薄膜上設有單一的相位差層者,將此等依序轉印至對象物。Sometimes multiple retardation layers can be provided, but in this case, multiple retardation layers can be provided on one alignment film for transfer and transfer this to the object. You can also prepare multiple retardation layers in one transfer Where a single retardation layer is provided on the alignment film, these are sequentially transferred to the object.
又,可將偏光層與相位差層設置在1個轉印用配向薄膜上,將此轉印至對象物。再者,有時在偏光鏡與相位差層之間設置保護層,或在相位差層之上或相位差層之間設置保護層之情況。此等保護層亦可與相位差層或偏光層一起設置在轉印用配向薄膜上,轉印至對象物。In addition, the polarizing layer and the retardation layer can be provided on one alignment film for transfer, and this can be transferred to the object. Furthermore, there are cases where a protective layer is provided between the polarizer and the retardation layer, or a protective layer is provided on or between the retardation layer. These protective layers may be provided on the alignment film for transfer together with the retardation layer or the polarizing layer, and transferred to the object.
作為保護層,可舉出透明樹脂之塗布層。作為透明樹脂,可為聚乙烯醇、乙烯-乙烯醇共聚物、聚酯、聚胺基甲酸酯、聚醯胺、聚苯乙烯、丙烯酸樹脂、環氧樹脂等,並沒有特別的限定。亦可於此等樹脂中添加交聯劑,成為交聯結構。又,亦可為使如硬塗的丙烯酸等之光硬化性組成物硬化者。另外,可將保護層設於配向薄膜上後,摩擦處理保護層,在其上不設置配向層,設置液晶化合物配向層。As the protective layer, a transparent resin coating layer can be cited. The transparent resin may be polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyester, polyurethane, polyamide, polystyrene, acrylic resin, epoxy resin, etc., and is not particularly limited. It is also possible to add a crosslinking agent to these resins to form a crosslinked structure. In addition, it may be one that hardens a photocurable composition such as hard-coated acrylic. In addition, after the protective layer is provided on the alignment film, the protective layer can be rubbed, and the alignment layer is not provided thereon, but an alignment layer of liquid crystal compound is provided.
(液晶化合物配向層積層偏光板之製造方法) 接著,說明本發明之液晶化合物配向層積層偏光板之製造方法。 本發明之液晶化合物配向層積層偏光板之製造方法包含:貼合偏光板與本發明之液晶化合物配向層轉印用積層體之液晶化合物配向層面而形成中間積層體之步驟,及從中間積層體剝離配向薄膜之步驟。 以下,說明將液晶化合物配向層用於圓偏光板的液晶化合物配向層之情況作為例子。於圓偏光板之情況,作為相位差層(於轉印用積層體中,稱為液晶化合物配向層),使用λ/4層。λ/4層之正面遲滯(retardation)較佳為100~180nm,更佳為120~150nm。僅用λ/4層作為圓偏光板時,λ/4層之配向軸(慢軸)與偏光鏡的穿透軸較佳為35~55度,更佳為40度~50度,進一步較佳為42~48度。與聚乙烯醇的延伸薄膜之偏光鏡組合使用時,由於偏光鏡的吸收軸一般成為長條偏光鏡薄膜的長度方向,故在長條的轉印用配向薄膜上設置λ/4層時,較佳為相對於長條的轉印用配向薄膜之長度方向,以成為上述範圍之方式使液晶化合物配向。還有,偏光鏡的穿透軸之角度與上述不同時,加上偏光鏡的穿透軸之角度,使成為如上述關係的液晶化合物配向。(Method of manufacturing liquid crystal compound alignment laminated polarizing plate) Next, the manufacturing method of the liquid crystal compound alignment laminated polarizing plate of the present invention will be described. The manufacturing method of the liquid crystal compound alignment laminated polarizing plate of the present invention includes: bonding the polarizing plate and the liquid crystal compound alignment layer of the liquid crystal compound alignment layer transfer laminate of the present invention to form an intermediate laminated body, and from the intermediate laminated body The step of peeling off the alignment film. Hereinafter, a case where the liquid crystal compound alignment layer is used for the liquid crystal compound alignment layer of the circular polarizing plate will be described as an example. In the case of a circularly polarizing plate, a λ/4 layer is used as the retardation layer (referred to as a liquid crystal compound alignment layer in a laminate for transfer). The frontal retardation of the λ/4 layer is preferably 100 to 180 nm, more preferably 120 to 150 nm. When only the λ/4 layer is used as the circular polarizer, the alignment axis (slow axis) of the λ/4 layer and the transmission axis of the polarizer are preferably 35 to 55 degrees, more preferably 40 degrees to 50 degrees, and more preferably It is 42 to 48 degrees. When used in combination with a polarizer of a stretched film of polyvinyl alcohol, since the absorption axis of the polarizer generally becomes the length direction of the long polarizer film, when the λ/4 layer is arranged on the long transfer alignment film, it is more It is preferable to align the liquid crystal compound with respect to the longitudinal direction of the long alignment film for transfer so as to be in the above range. In addition, when the angle of the transmission axis of the polarizer is different from the above, the angle of the transmission axis of the polarizer is added to make the alignment of the liquid crystal compound as described above.
藉由將積層有λ/4層與配向薄膜的轉印用積層體中之λ/4層轉印至偏光板,作成圓偏光板。具體而言,貼合偏光板與轉印用積層體之λ/4層面,形成中間積層體,從此中間積層體剝離配向薄膜。偏光板亦可在偏光鏡之兩面設置保護膜,但較佳為僅在單面設置保護膜。若為僅在單面設置保護膜之偏光板,則較佳為在保護膜之相反面(偏光鏡面)上貼合相位差層。若在兩面設置保護膜,則相位差層較佳為貼合於設想影像單元側之面。所謂的設想影像單元側之面,就是不進行低反射層、抗反射層、防眩層等一般在視覺辨認側所設置的表面加工之面。貼合相位差層之側的保護膜較佳為TAC、丙烯酸、COP等之無相位差的保護膜。The λ/4 layer in the transfer laminate in which the λ/4 layer and the alignment film are laminated is transferred to the polarizing plate to make a circular polarizing plate. Specifically, the λ/4 layer of the polarizing plate and the transfer laminate are bonded to form an intermediate laminate, and the alignment film is peeled from the intermediate laminate. The polarizer can also be provided with protective films on both sides of the polarizer, but it is preferable to provide a protective film on only one side. If it is a polarizing plate in which a protective film is provided on only one side, it is preferable to bond a retardation layer on the opposite surface (polarizer surface) of the protective film. If a protective film is provided on both sides, the retardation layer is preferably attached to the side of the assumed image unit. The so-called surface on the side of the assumed image unit is the surface on which the low-reflection layer, anti-reflection layer, anti-glare layer, etc., which are generally provided on the visually recognized side, are not processed. The protective film on the side where the retardation layer is bonded is preferably a protective film without retardation such as TAC, acrylic, or COP.
作為偏光鏡,可舉出單獨延伸PVA系薄膜而作成的偏光鏡,或在聚酯或聚丙烯等未延伸基材上塗布PVA,將連基材一起延伸而作成的偏光鏡轉印至偏光鏡保護膜者,或將包含液晶化合物與二色性色素的偏光鏡塗布於或轉印至偏光鏡保護膜者等,皆可較宜使用。Examples of the polarizer include a polarizer prepared by stretching a PVA-based film alone, or a non-stretched substrate such as polyester or polypropylene is coated with PVA, and the polarizer prepared by stretching the substrate together is transferred to the polarizer. Protective film, or a polarizer containing a liquid crystal compound and a dichroic dye is coated or transferred to a polarizer protective film, etc., can be preferably used.
作為貼附之方法,可使用接著劑、黏著劑等習知者。作為接著劑,較宜使用聚乙烯醇系接著劑、丙烯酸或環氧樹脂等之紫外線硬化型接著劑、環氧樹脂或異氰酸酯(胺基甲酸酯)等之熱硬化型接著劑。黏著劑可舉出丙烯酸或胺基甲酸酯系、橡膠系等之黏著劑。又,亦較佳為使用無丙烯酸基材的光學用透明黏著劑片。As a method of attaching, conventionally known adhesives and adhesives can be used. As the adhesive, it is preferable to use a polyvinyl alcohol-based adhesive, an ultraviolet curable adhesive such as acrylic or epoxy resin, and a thermosetting adhesive such as epoxy resin or isocyanate (urethane). Examples of the adhesive include acrylic, urethane, and rubber adhesives. Moreover, it is also preferable to use a transparent adhesive sheet for optics without an acrylic substrate.
使用轉印型者作為偏光鏡時,可將偏光鏡轉印至轉印用積層體的相位差層(液晶化合物配向層)上,然後將偏光鏡與相位差層轉印至對象物(偏光鏡保護膜)。When using a transfer type as a polarizer, the polarizer can be transferred to the retardation layer (liquid crystal compound alignment layer) of the transfer laminate, and then the polarizer and retardation layer can be transferred to the object (polarizer Protective film).
作為與設置相位差層之側相反側的偏光鏡保護膜,可使用TAC、丙烯酸、COP、聚碳酸酯、聚酯等一般已知者。其中較佳為TAC、丙烯酸、COP、聚酯。聚酯較佳為聚對苯二甲酸乙二酯。於聚酯之情況,較佳為面內遲滯100nm以下,尤其50nm以下的零遲滯薄膜,或3000nm~30000nm的高遲滯薄膜。As the polarizer protective film on the side opposite to the side where the retardation layer is provided, generally known ones such as TAC, acrylic, COP, polycarbonate, and polyester can be used. Among them, TAC, acrylic, COP, and polyester are preferred. The polyester is preferably polyethylene terephthalate. In the case of polyester, it is preferably a zero retardation film with an in-plane hysteresis of 100 nm or less, especially 50 nm or less, or a high hysteresis film of 3000 nm to 30000 nm.
使用高遲滯薄膜時,以防止戴上偏光太陽眼鏡觀看影像時的轉暗(black out)或著色為目的,偏光鏡的穿透軸與高遲滯薄膜的慢軸之角度較佳為30~60度之範圍,更佳為35~55度之範圍。為了減低用肉眼從角度淺的斜方向來觀察時的虹斑等,偏光鏡的穿透軸與高遲滯薄膜的慢軸之角度較佳設為10度以下,更佳設為7度以下,或較佳設為80~100度,更佳設為83~97度。When using a high-hysteresis film, to prevent black out or coloration when viewing images with polarized sunglasses, the angle between the penetration axis of the polarizer and the slow axis of the high-hysteresis film is preferably 30-60 degrees The range is more preferably 35 to 55 degrees. In order to reduce rainbow spots when viewed with the naked eye from a shallow oblique direction, the angle between the transmission axis of the polarizer and the slow axis of the high-hysteresis film is preferably set to 10 degrees or less, more preferably 7 degrees or less, or Preferably it is set to 80-100 degrees, More preferably, it is set to 83-97 degrees.
於相反側的偏光鏡保護膜上,亦可設置防眩層、抗反射層、低反射層、硬塗層等。On the polarizer protective film on the opposite side, an anti-glare layer, anti-reflection layer, low-reflection layer, hard coating, etc. can also be provided.
(複合相位差層) 以λ/4層單獨時,在可見光區域的寬廣範圍中有時不成為λ/4而發生著色之情況。因此,有組合λ/4層與λ/2層使用之情況。λ/2層之正面遲滯較佳為200~360nm,更佳為240~300nm。(Composite retardation layer) When the λ/4 layer is used alone, it may not become λ/4 in a wide range of the visible light region and may be colored. Therefore, there are cases where the λ/4 layer and the λ/2 layer are combined. The front hysteresis of the λ/2 layer is preferably 200-360 nm, more preferably 240-300 nm.
此時,較佳為合併λ/4層與λ/2層,配置成為如λ/4之角度。具體而言,λ/2層的配向軸(慢軸)與偏光鏡的穿透軸之角度(θ)較佳為5~20度,更佳為7度~17度。λ/2層的配向軸(慢軸)與λ/4的配向軸(慢軸)之角度較佳為2θ+45度±10度之範圍,更佳為2θ+45度±5度之範圍,進一步較佳為2θ+45度±3度之範圍。At this time, it is preferable to combine the λ/4 layer and the λ/2 layer and arrange them at an angle such as λ/4. Specifically, the angle (θ) between the alignment axis (slow axis) of the λ/2 layer and the transmission axis of the polarizer is preferably 5-20 degrees, more preferably 7-17 degrees. The angle between the alignment axis (slow axis) of the λ/2 layer and the alignment axis (slow axis) of the λ/4 layer is preferably within the range of 2θ+45°±10°, more preferably within the range of 2θ+45°±5°, More preferably, it is the range of 2θ+45°±3°.
此時,亦於與聚乙烯醇的延伸薄膜之偏光鏡組合使用之情況中,由於一般而言偏光鏡的吸收軸成為長條偏光鏡薄膜的長度方向,當將λ/2層或λ/4層設置於長條的轉印用配向薄膜時,較佳為相對於長條的轉印用配向薄膜之長度方向或長度的垂直方向,以成為上述範圍之方式使液晶化合物配向。再者,偏光鏡的穿透軸之角度與上述不同時,加上偏光鏡的穿透軸之角度,使成為如上述關係的液晶化合物配向。At this time, also in the case of combined use with a polarizer of a stretched film of polyvinyl alcohol, since generally the absorption axis of the polarizer becomes the length direction of the long polarizer film, when the λ/2 layer or λ/4 When the layer is provided on the long alignment film for transfer, it is preferable to align the liquid crystal compound with respect to the longitudinal direction or the vertical direction of the length of the long alignment film for transfer so as to be in the above range. Furthermore, when the angle of the transmission axis of the polarizer is different from the above, the angle of the transmission axis of the polarizer is added to make the alignment of the liquid crystal compound as described above.
作為此等方法或相位差層之例,可參考日本特開2008-149577號公報、日本特開2002-303722號公報、WO2006/100830號公報、日本特開2015-64418號公報等。As examples of these methods or retardation layers, Japanese Patent Application Publication No. 2008-149577, Japanese Patent Application Publication No. 2002-303722, WO2006/100830, Japanese Patent Application Publication No. 2015-64418, etc. can be referred to.
再者,為了減低從斜向觀看時的著色變化等,亦較佳的形態為在λ/4層之上設置C板層。C板層係配合λ/4層或λ/2層之特性,使用正或負的C板層。Furthermore, in order to reduce the color change when viewed from an oblique direction, it is also preferable to provide a C plate layer on the λ/4 layer. C plate layer is matched with the characteristics of λ/4 layer or λ/2 layer, using positive or negative C plate layer.
作為此等之積層方法,例如若為λ/4層與λ/2層之組合,則可採用以下等各式各樣之方法。 ・於偏光鏡上藉由轉印而設置λ/2層,更於其上藉由轉印而設置λ/4層。 ・於轉印用配向薄膜上依順序設置λ/4層與λ/2層,將其轉印至偏光鏡上。 ・於轉印用配向薄膜上依順序設λ/4層與λ/2層與偏光層,將其轉印至對象物。 ・於轉印用配向薄膜上依順序設λ/2層與偏光層,將其轉印至對象物,更於其上轉印λ/4層。As these layering methods, for example, if it is a combination of a λ/4 layer and a λ/2 layer, the following various methods can be used. ・A λ/2 layer is formed by transfer on the polarizer, and a λ/4 layer is formed on the polarizer by transfer. ・Place λ/4 layer and λ/2 layer in order on the alignment film for transfer and transfer it to the polarizer. ・Place λ/4 layer, λ/2 layer and polarizing layer on the alignment film for transfer in this order, and transfer it to the object. ・Place a λ/2 layer and a polarizing layer on the transfer alignment film in order, transfer them to the object, and transfer the λ/4 layer on top.
又,積層C板時,亦可採用於偏光鏡上所設置的λ/4層之上轉印C板層之方法,或於配向薄膜上設置C板層,更於其上設置λ/4層或λ/2層與λ/4層,將其轉印之方法等各式各樣的方法。In addition, when laminating C plates, the method of transferring the C plate layer on the λ/4 layer provided on the polarizer can also be used, or the C plate layer can be provided on the alignment film, and the λ/4 layer can be placed on it. Or λ/2 layer and λ/4 layer, the method of transferring them, etc. various methods.
如此所得之圓偏光板的厚度較佳為120μm以下,更佳為100μm以下,進一步較佳為90μm以下,特佳為80μm以下,最佳為70μm以下。The thickness of the circular polarizing plate thus obtained is preferably 120 μm or less, more preferably 100 μm or less, still more preferably 90 μm or less, particularly preferably 80 μm or less, and most preferably 70 μm or less.
(液晶化合物配向層轉印用積層體之檢査方法) 接著,說明本發明之液晶化合物配向層轉印用積層體之檢査方法。 本發明之液晶化合物配向層轉印用積層體之檢査方法包含:將具有平行於配向薄膜的配向方向、或平行於與配向方向正交的方向、或平行於配向薄膜的流動方向、或平行於與流動方向正交的方向之電場振動方向的直線偏光,從積層體的配向薄膜面來照射,在液晶化合物配向層面側受光之步驟,及檢查所受光的光之有無消光狀態之步驟。如此地,於本發明中,液晶化合物配向層轉印用積層體係即使液晶化合物配向層為相位差層,也可在積層於轉印用配向薄膜之狀態下,檢查其光學特性。(Inspection method of laminate for transfer of liquid crystal compound alignment layer) Next, the inspection method of the laminate for transferring the liquid crystal compound alignment layer of the present invention will be explained. The inspection method of the laminate for the transfer of the liquid crystal compound alignment layer of the present invention includes: setting the alignment direction parallel to the alignment film, or parallel to the direction orthogonal to the alignment direction, or parallel to the flow direction of the alignment film, or parallel to The step of irradiating linearly polarized light in the direction of electric field vibration in the direction orthogonal to the flow direction from the alignment film surface of the laminate, receiving light on the side of the alignment layer of the liquid crystal compound, and checking whether the received light is in a dull state. In this way, in the present invention, even if the liquid crystal compound alignment layer is a retardation layer, the laminated system for transferring the liquid crystal compound alignment layer can be laminated on the alignment film for transfer to inspect its optical properties.
為了檢查相位差層的光學狀態,對於轉印用配向薄膜的配向方向,照射平行或垂直的直線偏光,以設置於積層體之相反面的受光器檢測其偏光狀態之變化。對於轉印用配向薄膜的配向方向呈平行者較佳為-10~+10度,更佳為-7~7度,進一步較佳為-5~5度,特佳為-3~3度,最佳為-2~2度。對於轉印用配向薄膜的配向方向呈垂直者較佳為80~100度,更佳為83~97度,進一步較佳為85~95度,特佳為87~93度,最佳為88~92度。若超過上述範圍,則照射至相位差層的偏光或通過的偏光係受到基材的相位差之影響而紊亂,有無法正確地評價之情況。In order to check the optical state of the retardation layer, parallel or perpendicular linearly polarized light is irradiated to the alignment direction of the alignment film for transfer, and a photoreceptor installed on the opposite side of the laminate detects the change in the polarization state. The alignment direction of the alignment film for transfer is preferably from -10 to +10 degrees, more preferably from -7 to 7 degrees, further preferably from -5 to 5 degrees, particularly preferably from -3 to 3 degrees, The best is -2 to 2 degrees. The alignment direction of the alignment film for transfer is preferably 80-100 degrees, more preferably 83-97 degrees, still more preferably 85-95 degrees, particularly preferably 87-93 degrees, most preferably 88- 92 degrees. If it exceeds the above-mentioned range, the polarized light irradiated to the retardation layer or the polarized light system passing through is disturbed by the retardation of the base material, and it may not be accurately evaluated.
還有,亦可配合轉印用配向薄膜的配向方向,調整每次照射的直線偏光之角度,但檢査變繁雜。因此,所照射的直線偏光亦較佳為對於轉印用配向薄膜的流動方向呈平行或垂直地固定而檢査。此處,平行或垂直之範圍係與上述相同。In addition, it is also possible to adjust the angle of the linear polarization for each irradiation according to the alignment direction of the alignment film for transfer, but the inspection becomes complicated. Therefore, the irradiated linearly polarized light is also preferably fixed in parallel or perpendicular to the flow direction of the alignment film for transfer for inspection. Here, the parallel or perpendicular range is the same as above.
於受光器與液晶化合物配向層(相位差層)轉印用積層體(檢査對象薄膜)之間,較佳為設置偏光濾片。又,於液晶化合物配向層(相位差層)轉印用積層體與偏光濾片之間,較佳為設置相位差板,當將藉由液晶化合物配向層(相位差層)轉印用積層體之相位差層而成為橢圓偏光的光係符合設計的橢圓偏光時,該相位差板係用於將該橢圓偏光轉換成直線偏光。例如,藉由成為如此的構成,當相位差層為符合設計時,可知在受光器所檢測的光係消光狀態,但當有漏光時,可知相位差層係偏離設計。亦可設置複數種之設置的偏光濾片的角度或相位差板的角度・相位差為少許不同的受光器,檢測得知相位差層的相位差或配向方向係在哪個方向偏離多少。It is preferable to provide a polarizing filter between the light receiver and the layered body (test object film) for transferring the liquid crystal compound alignment layer (phase difference layer). In addition, it is preferable to provide a retardation plate between the liquid crystal compound alignment layer (retardation layer) transfer laminate and the polarizing filter, when the liquid crystal compound alignment layer (retardation layer) transfer laminate When the retardation layer becomes the elliptically polarized light system conforms to the designed elliptically polarized light, the retardation plate is used to convert the elliptically polarized light into linearly polarized light. For example, with such a configuration, when the retardation layer conforms to the design, it can be seen that the light system is in the extinction state detected by the light receiver, but when there is light leakage, it can be seen that the retardation layer is out of design. It is also possible to install a plurality of types of light receivers with slightly different angles of the polarizing filter or the angle and phase difference of the phase difference plate, and the phase difference or the alignment direction of the phase difference layer can be detected by which direction and how much it deviates.
(偏光層之檢査) 於液晶化合物配向層為偏光層時,藉由照射自然光(非偏光光線),將穿透的光透過偏光濾片而受光,可檢查偏光層。又,可藉由將透過偏光濾片成為直線偏光的光照射至轉印用積層體,接受穿透光的光而檢査。於此等之情況,當設於轉印用配向薄膜之偏光層不符合設計時,偏光濾片係設定在消光之角度。(Inspection of Polarizing Layer) When the liquid crystal compound alignment layer is a polarizing layer, the polarizing layer can be inspected by irradiating natural light (non-polarized light) to transmit the transmitted light through the polarizing filter and receiving light. In addition, the inspection can be performed by irradiating the light that has passed through the polarizing filter to become linearly polarized light to the transfer laminate, and receiving the light of the transmitted light. In these cases, when the polarizing layer provided on the alignment film for transfer does not conform to the design, the polarizing filter is set at the extinction angle.
再者,亦可設置複數種的偏光濾片的角度少許不同的受光器,檢測得知配向方向係在哪個方向偏離多少。Furthermore, it is also possible to install a plurality of types of light receivers with slightly different angles of the polarizing filters, and detect which direction the alignment direction deviates by how much.
又,於此等之情況,照射前述的自然光時,較佳為從轉印用配向薄膜面側來照射,照射後者的直線偏光時,較佳為從偏光層面來照射。 [實施例]In these cases, when irradiating the aforementioned natural light, it is preferable to irradiate from the surface of the transfer alignment film, and when irradiating the latter linearly polarized light, it is preferable to irradiate it from the polarized layer. [Example]
以下,參照實施例,更具體地說明本發明,惟本發明不限定於下述實施例,在能適合本發明的宗旨之範圍內,亦可加以適宜變更而實施,彼等皆包含於本發明之技術範圍中。還有,實施例中的物性之評價方法係如以下。Hereinafter, the present invention will be explained in more detail with reference to the embodiments. However, the present invention is not limited to the following embodiments. It can also be implemented with appropriate changes within the scope that can suit the purpose of the present invention. They are all included in the present invention. The technology range. In addition, the evaluation methods of physical properties in the examples are as follows.
(1)轉印用配向薄膜的配向方向與配向薄膜的流動方向或與流動方向正交的方向之角度、及薄膜的寬度方向之配向角的角度差 首先,將薄膜從捲筒拉出,在兩端部(從各端部起在內側5cm的地點)、中央部及在中央部與兩端部之中間的中間部之5處,決定配向方向。在中央部與兩端部之中間的中間部係在將中央部與兩端部之間隔予以2等分之位置。還有,配向方向係當作使用分子配向計(王子計測器股份有限公司製,MOA-6004型分子配向計)所求出的薄膜之慢軸方向。接著,調查薄膜全體之配向方向是接近流動方向(MD),還是接近寬度方向(TD)。然後,當薄膜全體之配向方向接近流動方向時,在各自上述5處,求出配向方向與薄膜的流動方向之間的角度,採用在最大角度之地方的值作為「配向薄膜的配向方向與配向薄膜的流動方向之間的角度」之最大值。另一方面,當薄膜全體之配向方向接近寬度方向時,在各自上述5處,求出配向方向與薄膜的流動方向正交之方向之間的角度,採用在最大的角度之地方的值作為「配向薄膜的配向方向與配向薄膜的流動方向正交之方向之間的角度」之最大值。 又,於上述5處所求出的角度之中,將最大值與最小值之間之差當作「薄膜在寬度方向之配向角的角度差」。 還有,角度係相對於長度方向或寬度方向,將在與前述最大值相同側具有配向方向時當作正值,相對於長度方向或寬度方向,將在相反側具有配向方向時當作負值,區別正・負,而評價最小值。(1) The angle difference between the alignment direction of the alignment film for transfer and the flow direction of the alignment film or the direction orthogonal to the flow direction, and the angle difference between the alignment angle of the film width direction First, the film is pulled out from the roll, and the orientation direction is determined at 5 of the two ends (a point 5 cm inside from each end), the center, and the middle between the center and both ends. The middle part between the central part and the both ends is at a position where the interval between the central part and the both ends is halved. In addition, the orientation direction is regarded as the slow axis direction of the film determined using a molecular orientation meter (MOA-6004 type molecular orientation meter manufactured by Oji Scientific Instruments Co., Ltd.). Next, it was investigated whether the orientation direction of the entire film was close to the flow direction (MD) or the width direction (TD). Then, when the alignment direction of the entire film is close to the flow direction, find the angle between the alignment direction and the flow direction of the film at each of the above five points, and use the value at the largest angle as the "alignment direction and alignment of the film The maximum value of the angle between the flow directions of the film. On the other hand, when the alignment direction of the entire film is close to the width direction, find the angle between the alignment direction and the direction orthogonal to the flow direction of the film at each of the above five points, and use the value at the largest angle as " The maximum value of the angle between the alignment direction of the alignment film and the direction orthogonal to the flow direction of the alignment film. In addition, among the angles obtained at the above 5 locations, the difference between the maximum value and the minimum value is regarded as the "angle difference of the alignment angle of the film in the width direction". In addition, the angle is regarded as a positive value with respect to the length direction or the width direction when it has an alignment direction on the same side as the aforementioned maximum value, and is regarded as a negative value when it has an alignment direction on the opposite side with respect to the length direction or the width direction. , Distinguish between positive and negative, and evaluate the minimum value.
(2)轉印用配向薄膜之折射率 以上述(1)所求出的慢軸方向與長邊成為平行之方式,切出4cm×2cm的長方形,當作測定用樣品。對於此樣品,藉由阿貝折射率計(ATAGO公司製,NAR-4T,測定波長589nm)求出正交的雙軸之折射率(慢軸方向之折射率:nx,快軸方向(與慢軸方向正交的方向)之折射率:ny)及厚度方向之折射率(nz)。(2) Refractive index of alignment film for transfer Cut out a rectangle of 4 cm×2 cm so that the slow axis direction and the long side determined in (1) above are parallel to each other, and use it as a sample for measurement. For this sample, an Abbe refractometer (manufactured by ATAGO, NAR-4T, measurement wavelength 589nm) was used to determine the refractive index of the orthogonal biaxial (refractive index in the slow axis direction: nx, the fast axis direction (and the slow axis) The refractive index in the direction perpendicular to the axis direction: ny) and the refractive index in the thickness direction (nz).
(3)轉印用配向薄膜之相對於MD方向、TD方向、MD方向而言45度的方向,或相對於MD方向而言135度的方向之150℃ 30分鐘的熱收縮率 依照JIS C 2318-1997 5.3.4(尺寸變化)進行測定。具體而言,在應測定的方向(相對於MD方向、TD方向、MD方向而言45度的方向、相對於MD方向而言135度的方向)中,從薄膜切出寬度10mm、長度250mm,將此樣品以200mm間隔附上兩個記號,於5gf之一定張力下,測定兩個記號之間的間隔(A)。接著,將薄膜置入150℃的環境中之烘箱,於無荷重下在150±3℃加熱處理30分鐘後,於5gf之一定張力下,測定兩個記號之間的間隔(B)。藉由以下之式求出熱收縮率。 熱收縮率(%)=(A-B)/A×100(3) The thermal shrinkage rate of the alignment film for transfer at a direction of 45 degrees relative to the MD, TD, and MD directions, or a direction of 135 degrees relative to the MD direction, at 150°C for 30 minutes Measured in accordance with JIS C 2318-1997 5.3.4 (dimension change). Specifically, in the direction to be measured (a direction of 45 degrees with respect to the MD, TD, and MD directions, and a direction of 135 degrees with respect to the MD direction), the film is cut out with a width of 10 mm and a length of 250 mm, Attach two marks to this sample at an interval of 200 mm, and measure the interval (A) between the two marks under a certain tension of 5 gf. Next, put the film in an oven in an environment of 150°C, heat treatment at 150±3°C for 30 minutes under no load, and measure the interval between the two marks (B) under a certain tension of 5gf. The heat shrinkage rate is obtained by the following formula. Heat shrinkage rate (%)=(A-B)/A×100
(4)95℃最大熱收縮率 將從切割捲筒(slit roll)的各切出部所切出的轉印用配向薄膜,切出成每邊21cm的正方形狀,在23℃、65%RH之環境下放置2小時以上。描繪以此薄膜的中央為中心的直徑80mm之圓,使用二次元影像測定機(MITUTOYO製QUICK IMAGE),將薄膜的流動方向當作0度,以1度間隔測定直徑。此處,將薄膜流動方向當作0度,在薄膜上面將順時針(右旋)設定為正的角度,將反時針(左旋)設定為負的角度。為了測定直徑,以-90度~89度之範圍測定,對於全部方向測定。接著,將此薄膜在95℃的熱水中加熱處理30分鐘後,在23℃、65%RH之環境中放置2小時以上。然後,與上述同樣地以1度間隔測定圓的直徑。將熱處理前之直徑當作Lo,將熱處理後的同方向之直徑當作L,依下述式,求出各方向的熱收縮率,將全部方向的熱收縮率之中最大的值當作最大熱收縮率。又,求出具有最大熱收縮率的方向與MD或TD之角度(值變小者)。 熱收縮率(%)=((L0 -L)/L0 )×100(4) The maximum thermal shrinkage rate at 95°C is to cut out the alignment film for transfer from each cut-out part of the slit roll into a square shape of 21cm on each side, at 23°C, 65%RH Put it in the environment for more than 2 hours. Draw a circle with a diameter of 80 mm centered on the center of the film. Using a two-dimensional image measuring machine (Quick Image manufactured by MITUTOYO), the flow direction of the film is regarded as 0 degree, and the diameter is measured at 1-degree intervals. Here, the flow direction of the film is regarded as 0 degrees, the clockwise (right-handed) angle on the film is set to a positive angle, and the counter-clockwise (left-handed) angle is set to a negative angle. In order to measure the diameter, it is measured in the range of -90 degrees to 89 degrees, for all directions. Next, after heat-treating the film in hot water at 95°C for 30 minutes, it was left in an environment of 23°C and 65% RH for more than 2 hours. Then, the diameter of the circle was measured at 1 degree intervals in the same manner as described above. Taking the diameter before heat treatment as Lo and the diameter after heat treatment in the same direction as L, calculate the heat shrinkage rate in each direction according to the following formula, and take the largest value among the heat shrinkage rates in all directions as the maximum Thermal shrinkage rate. In addition, the angle between the direction with the largest heat shrinkage rate and MD or TD (the one with the smaller value) is obtained. Thermal shrinkage (%)=((L 0 -L)/L 0 )×100
(5)彈性模數:依照JIS C-2318進行測定。樣品係從由中央部切割所得之切割捲筒的寬度方向之中央切出。(5) Elastic modulus: Measured in accordance with JIS C-2318. The sample is cut out from the center of the width direction of the cutting reel cut from the center.
(6)在波長380nm的光線穿透率 使用分光光度計(日立製作所製,U-3500型),將空氣層當作標準,測定轉印用配向薄膜之波長300~500nm區域的光線穿透率,求出在波長380nm的光線穿透率。(6) Light transmittance at a wavelength of 380nm Using a spectrophotometer (manufactured by Hitachi, U-3500 type), using the air layer as a standard, measure the light transmittance of the alignment film for transfer in the wavelength range of 300-500nm, and find the light transmittance at the wavelength of 380nm .
(7)固有黏度 將0.2g的樹脂試料溶解於苯酚/1,1,2,2-四氯乙烷(60/40(重量比))的混合溶劑50ml中,在30℃使用奧士華黏度計進行測定。還有,表面層A之試料係製作以A層單獨所擠出的薄膜樣品,將其當作試料。(7) Intrinsic viscosity A 0.2 g resin sample was dissolved in 50 ml of a mixed solvent of phenol/1,1,2,2-tetrachloroethane (60/40 (weight ratio)), and the measurement was carried out at 30°C using an Oswath viscometer. In addition, the sample of the surface layer A is a film sample extruded with the A layer alone, and this is used as the sample.
(8)漏光 於以使用黃色螢光體的白色LED作為光源的面發光光源之上,放置下側偏光板,於其上放置在轉印用配向薄膜上設有相位差層(液晶化合物配向層)之樣品積層體,使得偏光板的消光軸方向(吸收軸方向)與樣品積層體的長邊方向成為平行。更於其上,放置由環狀聚烯烴的延伸薄膜所成之λ/4薄膜,使得配向主軸與下側偏光板的消光軸成為45度的方向,於其上放置上側偏光板,使得上側偏光板的消光軸與下側偏光板的消光軸成為平行。於此狀態下觀察消光狀態。具體而言,於樣品積層體之中,用以下之基準評價最明亮的部分之消光狀態。還有,去除樣品積層體與λ/4薄膜,將下側偏光板與上側偏光板成為正交尼科耳之狀態的消光狀態當作消光狀態。 ◎:沒有明亮感處,全體為消光狀態。 ○:看到比消光狀態更稍微的穿透光。 △:看到穿透光,但能評價相位差狀態。 ×:穿透光多,難以評價相位差狀態。(8) Light leakage Place a lower polarizing plate on a surface emitting light source that uses a white LED with a yellow phosphor as the light source, and place it on the transfer alignment film with a phase difference layer (liquid crystal compound alignment layer). Body so that the extinction axis direction (absorption axis direction) of the polarizing plate is parallel to the longitudinal direction of the sample laminate. Furthermore, a λ/4 film made of a cyclic polyolefin stretched film is placed so that the alignment main axis and the extinction axis of the lower polarizing plate become 45 degrees, and the upper polarizing plate is placed on it to make the upper side polarized The extinction axis of the plate is parallel to the extinction axis of the lower polarizer. Observe the extinction state in this state. Specifically, among the sample laminates, the extinction state of the brightest part was evaluated using the following criteria. In addition, the sample laminate and the λ/4 film were removed, and the extinction state in which the lower polarizing plate and the upper polarizing plate were crossed Nicols was regarded as the extinction state. ◎: There is no bright feeling, and the whole is in a dull state. ○: Slightly transmitted light is seen than in the extinction state. △: The transmitted light is seen, but the phase difference state can be evaluated. ×: A lot of transmitted light makes it difficult to evaluate the phase difference state.
(9)亮度均勻性 於與上述(8)相同之狀態下,用以下之基準評價樣品積層體內的消光狀態之均勻性。還有,去除樣品積層體與λ/4薄膜,將下側偏光板與上側偏光板成為正交尼科耳之狀態的消光狀態當作消光狀態。 ◎:在樣品積層體全域中大致相同的亮度。 ○:亮度些微不同。 △:亮度差異小。 ×:亮度差異大。(9) Brightness uniformity In the same state as the above (8), the uniformity of the matting state in the sample laminate was evaluated using the following criteria. In addition, the sample laminate and the λ/4 film were removed, and the extinction state in which the lower polarizing plate and the upper polarizing plate were crossed Nicols was regarded as the extinction state. ⊚: The brightness is approximately the same in the entire sample laminate. ○: The brightness is slightly different. △: The brightness difference is small. ×: The brightness difference is large.
(10)相位差層之加熱配向方向偏離 將樣品積層體在烘箱中於120℃加熱處理20分鐘,於經冷卻至室溫的樣品積層體之相位差層面側,貼合市售的光學用黏著片,更將黏著片貼附於玻璃板後,剝離配向薄膜,而在玻璃板上轉印相位差層。於玻璃板上積層有相位差層之狀態下,在配置成正交尼科耳的偏光板之間,配置玻璃板/相位差層積層體,求出消光的方向。求出消光的方向與配向薄膜的長邊方向之角度差,將此角度差與45度之差當作加熱配向方向偏離,算出進行5次的值之平均值,用以下之基準進行評價。 ◎:1度以內。 ○:超過1度且為2度以下。 △:超過2度且為3度以下。 ×:超過3度。(10) The heating alignment direction of the retardation layer deviates The sample laminate was heated in an oven at 120°C for 20 minutes, and a commercially available optical adhesive sheet was attached to the retardation layer side of the sample laminate cooled to room temperature, and the adhesive sheet was attached to the glass plate After that, the alignment film was peeled off, and the retardation layer was transferred on the glass plate. In the state where the retardation layer is laminated on the glass plate, the glass plate/phase difference laminate is arranged between the polarizing plates arranged in crossed Nicols, and the direction of extinction is determined. The angular difference between the direction of extinction and the longitudinal direction of the alignment film was determined, the difference between the angular difference and 45 degrees was regarded as the deviation of the heating alignment direction, and the average value of the values performed 5 times was calculated and evaluated using the following criteria. ◎: Within 1 degree. ○: More than 1 degree and 2 degrees or less. △: More than 2 degrees and 3 degrees or less. ×: More than 3 degrees.
(11)酯環狀三聚物之含量 以切割刀削取構成聚酯薄膜的脫模面側層之聚酯樹脂,細細地冷凍粉碎。將0.1g的此經粉碎的樹脂溶解於六氟異丙醇(HFIP)/氯仿(2/3(容量比))之混合溶劑3ml中。於所得之溶液中加入20ml的氯仿,均勻地混合。於所得之混合液中加入10ml的甲醇,使線狀聚酯再沈澱。接著,過濾此混合液,以氯仿/甲醇(2/1(容量比))的混合溶劑30ml洗淨沈澱物,進一步過濾。以旋轉式蒸發器濃縮乾固所得之濾液。於濃縮乾固物中加入10ml的二甲基甲醯胺,成為酯環狀三聚物測定溶液,藉由液體層析法求出酯環狀三聚物之含量。 (測定條件) 裝置:L-7000(日立製作所製) 管柱:μ-Bondasphere C18 5μ 100埃 3.9mm×15cm (Waters製) 溶劑:洗提液A:2%乙酸/水(v/v) 洗提液B:乙腈 梯度B%:10→100%(0→55分鐘) 流速:0.8ml/分鐘 溫度:30℃ 檢測器:UV-258nm(11) Content of ester cyclic trimer The polyester resin that constitutes the release surface side layer of the polyester film is shaved with a cutting knife, and it is finely frozen and crushed. 0.1 g of this pulverized resin was dissolved in 3 ml of a mixed solvent of hexafluoroisopropanol (HFIP)/chloroform (2/3 (volume ratio)). Add 20 ml of chloroform to the resulting solution and mix uniformly. Add 10 ml of methanol to the resulting mixture to re-precipitate the linear polyester. Next, this mixed solution was filtered, and the precipitate was washed with 30 ml of a mixed solvent of chloroform/methanol (2/1 (volume ratio)) and further filtered. Concentrate the dried filtrate with a rotary evaporator. 10ml of dimethylformamide was added to the concentrated dry solid to form an ester cyclic trimer measurement solution, and the content of the ester cyclic trimer was determined by liquid chromatography. (Measurement conditions) Device: L-7000 (manufactured by Hitachi, Ltd.) Column: μ-Bondasphere C18 5μ 100 Angstroms 3.9mm×15cm (made by Waters) Solvent: eluent A: 2% acetic acid/water (v/v) Eluent B: Acetonitrile Gradient B%: 10→100% (0→55 minutes) Flow rate: 0.8ml/min Temperature: 30℃ Detector: UV-258nm
(12)薄膜的脫模面之表面的酯環狀三聚物之析出量 將聚酯薄膜切割成15cm×15cm,於烘箱中以150℃加熱90分鐘。然後,以脫模面成為上,將熱處理後的薄膜放置在15cm×15cm的不銹鋼板上,於其上載置在中央部開出10cm×10cm的孔之15cm×15cm的聚矽氧片(厚度5mm),更重疊與聚矽氧片相同形狀(厚度2mm)的不銹鋼板,以夾具固定住周邊部。接著,於中央的孔之中置入4ml的DMF(二甲基甲醯胺),放置3分鐘後,回收DMF。藉由液體層析法求出所回收的DMF中之酯環狀三聚物之量。將此值除以與DMF接觸的薄膜面積,當作薄膜的脫模面之表面的酯環狀三聚物之析出量(mg/m2 )。 (測定條件) 裝置:ACQUITY UPLC(Waters製) 管柱:BEH-C18 2.1×150mm(Waters製) 移動相:洗提液A:0.1%甲酸(v/v) 洗提液B:乙腈 梯度B%:10→98→98%(0→25→30分鐘) 流速:0.2ml/分鐘 管柱溫度:40℃ 檢測器:UV-258nm(12) Precipitation amount of ester cyclic trimer on the surface of the release surface of the film The polyester film was cut into 15 cm×15 cm, and heated in an oven at 150°C for 90 minutes. Then, place the heat-treated film on a 15cm×15cm stainless steel plate with the release surface as the top, and place a 15cm×15cm polysilicon sheet (thickness 5mm) with a 10cm×10cm hole in the center on it. ), and overlap the stainless steel plate with the same shape (thickness 2mm) as the polysilicon sheet, and fix the peripheral part with a clamp. Next, 4 ml of DMF (dimethylformamide) was placed in the center hole, and after leaving for 3 minutes, DMF was recovered. The amount of the ester cyclic trimer in the recovered DMF was determined by liquid chromatography. Divide this value by the area of the film in contact with DMF, and take it as the precipitation amount (mg/m 2 ) of the ester cyclic trimer on the surface of the release surface of the film. (Measurement conditions) Device: ACQUITY UPLC (manufactured by Waters) Column: BEH-C18 2.1×150mm (manufactured by Waters) Mobile phase: eluent A: 0.1% formic acid (v/v) eluent B: acetonitrile gradient B% :10→98→98% (0→25→30 minutes) Flow rate: 0.2ml/min Column temperature: 40℃ Detector: UV-258nm
(13)熱處理前後的霧度之增加量(Δ霧度)評價 從薄膜切出50mm×75mm見方,依據JIS K 7105「塑膠之光學的特性試驗方法」霧度(haze),測定熱處理前的初期霧度(加熱前霧度)。於測定器,使用日本電色工業公司製NDH-300A型濁度計。為了測定加熱後霧度,以不引入氣泡之方式,使用輥使保護膜(藤森工業製PC-T073)密著於試料薄膜片之加熱處理前未霧度評價之面(背面)。於貼附有保護膜之狀態下,將薄膜設置於經加熱至150℃的烘箱內,於90分鐘經過後取出薄膜。然後剝離保護膜,以與上述同樣之方法測定薄膜之霧度,得到加熱後霧度。將此加熱前後的霧度差當作Δ霧度。 Δ霧度(%)=(加熱後霧度)-(加熱前霧度)(13) Evaluation of the increase in haze before and after heat treatment (Δ haze) Cut a 50mm×75mm square from the film, and measure the initial haze before heat treatment (haze before heating) in accordance with JIS K 7105 "Testing Methods for Optical Properties of Plastics". As the measuring device, NDH-300A turbidity meter manufactured by Nippon Denshoku Kogyo Co., Ltd. was used. In order to measure the haze after heating, the protective film (PC-T073 manufactured by Fujimori Kogyo Co., Ltd.) was adhered to the side (back side) of the sample film sheet that had not been evaluated for haze before the heat treatment using a roller without introducing bubbles. With the protective film attached, set the film in an oven heated to 150°C, and take out the film after 90 minutes has passed. Then, the protective film was peeled off, and the haze of the film was measured by the same method as above to obtain the haze after heating. The difference in haze before and after heating is regarded as Δ haze. ΔHaze (%) = (Haze after heating)-(Haze before heating)
(14)聚酯薄膜之表面固有電阻值(Ω/sq) 根據JIS K 6911,使用表面固有電阻測定器(武田理研(股)公司製),於23℃、40%RH之環境下,以外加電壓500V,測定表面固有電阻值(Ω)。(14) Surface intrinsic resistance value of polyester film (Ω/sq) According to JIS K 6911, a surface specific resistance tester (manufactured by Takeda Riken Co., Ltd.) was used to measure the surface specific resistance (Ω) under an environment of 23°C and 40% RH with an external voltage of 500V.
(15)高速塗布適應性 於轉印用配向薄膜之非塗布面或寡聚物阻擋塗布面,以凹版塗布機塗布相位差層形成用溶液及使其乾燥。然後,觀察轉印用配向薄膜之捲芯附近(從開始起450m附近)的膜質之狀態,用以下之基準進行評價。 ○:均勻的塗膜。 ×:看到因靜電所致的排斥。(15) High-speed coating adaptability On the non-coated surface or oligomer barrier coating surface of the alignment film for transfer, the solution for forming the retardation layer is coated with a gravure coater and dried. Then, the state of the film quality in the vicinity of the core (around 450 m from the start) of the alignment film for transfer was observed, and the following criteria were used for evaluation. ○: Uniform coating film. ×: Repulsion due to static electricity is seen.
(16)三次元表面粗糙度SRa、SRz、SRy 使用觸針式三次元粗糙度計(SE-3AK,小阪研究所股份有限公司製),於針的半徑2μm、荷重30mg之條件下,在薄膜的長度方向中以截止值0.25mm,在測定長度1mm中,以針的進給速度0.1mm/秒進行測定,以2μm間距分割成500點,將各點的高度輸入三次元粗糙度解析裝置(SPA-11)。將與此同樣的操作,對於薄膜的寬度方向,以2μm間隔連續地進行150次,即於薄膜的寬度方向0.3mm中進行,將數據輸入解析裝置。接著,使用解析裝置,求出中心面平均粗糙度(SRa)、十點平均粗糙度(SRz)、最大高度(SRy)。(16) Three-dimensional surface roughness SRa, SRz, SRy Using a stylus type three-dimensional roughness meter (SE-3AK, manufactured by Kosaka Laboratory Co., Ltd.), under the conditions of a needle radius of 2 μm and a load of 30 mg, the length of the film is measured at a cut-off value of 0.25 mm in the length direction In 1mm, the needle is measured at a feed speed of 0.1mm/sec, divided into 500 points at a pitch of 2μm, and the height of each point is input to the three-dimensional roughness analyzer (SPA-11). The same operation was performed 150 times in the width direction of the film continuously at intervals of 2 μm, that is, in the width direction of the film 0.3 mm, and the data was input to the analysis device. Next, using an analysis device, the center surface average roughness (SRa), ten-point average roughness (SRz), and maximum height (SRy) were obtained.
(17)脫模面高低差0.5μm以上(脫模面)、2.0μm(背面)以上之突起數 在薄膜長度方向中,切出寬度100mm、長度100mm的試驗片,將此夾入2片偏光板之間而成為正交尼科耳狀態,設置於保持消光位置之狀態。於此狀態下使用NIKON萬能投影機V-12(測定條件:投影透鏡50倍,穿透照明光束切換旋鈕50倍,穿透光檢査),光進行穿透,檢測出能光亮般地看見之部分(傷痕、異物)的長徑為50μm以上者。將如此所檢測出的部分從試驗片中切取適當的大小,使用3次元形狀測定裝置(菱化系統公司製,Micromap TYPE550;測定條件:波長550nm、WAVE模式、物鏡10倍),對於薄膜面,從垂直方向來觀察、測定。此時,對於薄膜面,從垂直方向來觀察時,接近50μm以內的凹凸係當作相同的傷痕、異物,假想覆蓋該等之長方形,將此長方形的長度及寬度當作傷痕、異物之長度及寬度。關於該傷痕、異物,使用剖面映像(SURFACE PROFILE DISPLAY),定量缺點數。再者,測定係對於20片試驗片進行,換算成每1m2 的缺點數。於脫模面中計數高低差(最高處與低處之差)為0.5μm以上者的缺點數,背面係計數高低差2.0μm以上者的缺點數。(17) In the film length direction, cut out a test piece with a width of 100mm and a length of 100mm with the number of protrusions above 0.5μm (release surface) and 2.0μm (back surface), and sandwich this into two polarized sheets The plates are in a state of crossed Nicols, and they are set to maintain the extinction position. In this state, use the NIKON universal projector V-12 (measurement conditions: projection lens 50 times, penetration illumination beam switch knob 50 times, penetration light inspection), the light penetrates, and the brightly visible part is detected (Scars, foreign matter) whose major axis is 50 μm or more. The part detected in this way is cut into an appropriate size from the test piece, and a three-dimensional shape measuring device (manufactured by Ryoka Systems, Micromap TYPE550; measurement conditions: wavelength 550nm, WAVE mode, objective lens 10 times) is used. Observe and measure from the vertical direction. At this time, for the film surface, when viewed from the vertical direction, the unevenness within 50μm is regarded as the same scars and foreign objects. It is assumed to cover these rectangles, and the length and width of this rectangle are regarded as the length and the length of the scars and foreign objects. width. Regarding the flaws and foreign objects, the section map (SURFACE PROFILE DISPLAY) is used to quantify the number of defects. In addition, the measurement system was performed on 20 test pieces and converted into the number of defects per 1 m 2 . Count the number of defects of the height difference (the difference between the highest point and the low point) of 0.5 μm or more in the release surface, and count the number of defects of the height difference of 2.0 μm or more on the back surface.
<轉印用配向薄膜用聚酯樹脂之製造> (聚酯樹脂(PET(X-m))之製造) 將酯化反應槽升溫,於到達200℃之時間點,加入86.4質量份的對苯二甲酸及64.6質量份的乙二醇,一邊攪拌一邊加入作為觸媒之0.017質量份的三氧化銻、0.064質量份的乙酸鎂4水合物、0.16質量份的三乙胺。接著,進行加壓升溫,於錶壓0.34MPa、240℃之條件下進行加壓酯化反應後,使酯化反應槽回到常壓,添加0.014質量份的磷酸。再者,費15分鐘升溫至260℃,添加0.012質量份的磷酸三甲酯。接著,於15分鐘後,以高壓分散機進行分散處理,於15分鐘後,將所得之酯化反應生成物移送至聚縮合反應槽,於280℃、減壓下進行聚縮合反應。<Production of polyester resin for alignment film for transfer> (Production of polyester resin (PET(X-m))) The temperature of the esterification reaction tank was raised, and when it reached 200°C, 86.4 parts by mass of terephthalic acid and 64.6 parts by mass of ethylene glycol were added, and 0.017 parts by mass of antimony trioxide and 0.064 parts of antimony trioxide as a catalyst were added while stirring. Parts by mass of magnesium acetate tetrahydrate and 0.16 parts by mass of triethylamine. Next, the pressure was increased and the pressure was subjected to the esterification reaction under the conditions of a gauge pressure of 0.34 MPa and 240°C. The esterification reaction tank was returned to normal pressure, and 0.014 parts by mass of phosphoric acid was added. In addition, the temperature was raised to 260°C over 15 minutes, and 0.012 parts by mass of trimethyl phosphate was added. Then, after 15 minutes, the dispersion treatment was performed with a high-pressure disperser, and after 15 minutes, the obtained esterification reaction product was transferred to the polycondensation reaction tank, and the polycondensation reaction was performed at 280°C under reduced pressure.
於聚縮合反應結束後,以95%截止徑為5μm的Nasolon製過濾器進行過濾處理,從噴嘴擠出股束(strand)狀,使用已預先進行過濾處理(孔徑:1μm以下)的冷卻水,使其冷卻、固化,切割成丸粒狀,得到聚對苯二甲酸乙二酯樹脂(PET(X-m))。PET(X-m)之固有黏度為0.62dl/g,惰性粒子及內部析出粒子係實質上不含。After the completion of the polycondensation reaction, filtration is performed with a Nasolon filter with a 95% cut-off diameter of 5 μm, a strand shape is extruded from the nozzle, and cooling water that has been previously filtered (pore size: 1 μm or less) is used, It was cooled, solidified, and cut into pellets to obtain polyethylene terephthalate resin (PET (Xm)). The intrinsic viscosity of PET (X-m) is 0.62dl/g, and the inert particles and internally precipitated particles are substantially free.
(聚酯樹脂(PET(Y)之調製) 混合10質量份的經乾燥之紫外線吸收劑(2,2’-(1,4-伸苯基)雙(4H-3,1-苯并 -4-酮)與90質量份的PET(X-m)(固有黏度為0.62dl/g),使用混煉擠壓機,得到含有紫外線吸收劑之聚對苯二甲酸乙二酯樹脂(PET(Y))。(Preparation of polyester resin (PET(Y)) 10 parts by mass of dried ultraviolet absorber (2,2'-(1,4-phenylene) bis(4H-3,1-benzo -4-one) and 90 parts by mass of PET (Xm) (intrinsic viscosity of 0.62dl/g), using a kneading extruder to obtain a polyethylene terephthalate resin containing ultraviolet absorbers (PET (Y )).
(低寡聚物量聚酯(X-s)之製造) 於減壓下在160℃乾燥聚酯樹脂(PET(X-m)),接著,使含水量為15.3g/Nm3 之經調濕的氮氣以每小時300公升流通每1kg的粗製聚酯,於230℃進行12小時加熱處理。所得之聚酯的固有黏度為0.617dl/g,環狀三聚物之含量為0.29質量%。(Production of low oligomer content polyester (Xs)) The polyester resin (PET (Xm)) is dried at 160°C under reduced pressure, and then the humidity is adjusted to 15.3 g/Nm 3 of nitrogen Circulate 300 liters of crude polyester per kg per hour, and heat treatment at 230°C for 12 hours. The inherent viscosity of the obtained polyester was 0.617dl/g, and the content of the cyclic trimer was 0.29% by mass.
<易接著層成分之製造> (聚胺基甲酸酯樹脂D-1之製造) 用以下之程序製造以脂肪族系聚碳酸酯多元醇為構成成分之聚胺基甲酸酯樹脂D-1。於具備攪拌機、戴氏冷卻器、氮氣導入管、矽凝膠乾燥管及溫度計之4口燒瓶中,投入43.75質量份的4,4-二苯基甲烷二異氰酸酯、12.85質量份的二羥甲基丁酸、153.41質量份的數量平均分子量2000之聚六亞甲基碳酸酯二醇、0.03質量份的二月桂酸二丁錫及84.00質量份作為溶劑的丙酮,於氮氣環境下,在75℃攪拌3小時,確認反應液達到指定的胺當量。接著,將此反應液降溫到40℃為止後,添加8.77質量份的三乙胺,得到聚胺基甲酸酯預聚物溶液。接著,於具備能高速攪拌的均質分散機之反應容器中,添加450g的水,調整至25℃,一邊以2000min-1 攪拌混合,一邊添加聚胺基甲酸酯預聚物溶液而進行水分散。然後,於減壓下,藉由去除丙酮及水的一部分,而調製固體成分濃度35質量%的水溶性聚胺基甲酸酯樹脂(D-1)。所得之聚胺基甲酸酯樹脂(D-1)的玻璃轉移點溫度為-30℃。<Production of easy-adhesive layer components> (Production of polyurethane resin D-1) Use the following procedure to produce polyurethane resin D-1 with aliphatic polycarbonate polyol as its constituent . Put 43.75 parts by mass of 4,4-diphenylmethane diisocyanate and 12.85 parts by mass of dimethylol into a 4-necked flask equipped with a stirrer, Dai's cooler, nitrogen introduction tube, silicone gel drying tube, and thermometer. Butyric acid, 153.41 parts by mass of polyhexamethylene carbonate glycol with a number average molecular weight of 2000, 0.03 parts by mass of dibutyltin dilaurate, and 84.00 parts by mass of acetone as a solvent, stirred at 75°C in a nitrogen atmosphere After 3 hours, confirm that the reaction solution reaches the specified amine equivalent. Then, after cooling the reaction liquid to 40°C, 8.77 parts by mass of triethylamine was added to obtain a polyurethane prepolymer solution. Next, add 450 g of water to a reaction vessel equipped with a homogeneous disperser capable of high-speed stirring and adjust to 25°C, while stirring and mixing for 2000 min -1 , add the polyurethane prepolymer solution for water dispersion . Then, under reduced pressure, a water-soluble polyurethane resin (D-1) with a solid content concentration of 35% by mass was prepared by removing part of acetone and water. The glass transition point temperature of the obtained polyurethane resin (D-1) was -30°C.
(唑啉系交聯劑E-1之製造) 於具備溫度計、氮氣導入管、回流冷卻器、滴液漏斗及攪拌機之燒瓶中,投入作為水性介質之58質量份的離子交換水與58質量份的異丙醇之混合物及4質量份的聚合起始劑(2,2’-偶氮雙(2-甲脒基丙烷)・二鹽酸鹽)。另一方面,於滴液漏斗中,投入16質量份的作為具有唑啉基的聚合性不飽和單體之2-異丙烯基-2-唑啉、32質量份的甲氧基聚乙二醇丙烯酸酯(乙二醇的平均加成莫耳數:9莫耳,新中村化學製)及32質量份的甲基丙烯酸甲酯之混合物,於氮氣環境下,在70℃歷1小時滴下。滴下結束後,將反應溶液攪拌9小時,藉由冷卻而得到固體成分濃度40質量%之具有唑啉基的水溶性樹脂(E-1)。( (Production of oxazoline-based crosslinking agent E-1) In a flask equipped with a thermometer, a nitrogen introduction tube, a reflux cooler, a dropping funnel, and a stirrer, 58 parts by mass of ion exchange water and 58 parts by mass of the aqueous medium A mixture of isopropanol and 4 parts by mass of polymerization initiator (2,2'-azobis(2-carboxamidinopropane)·dihydrochloride). On the other hand, put 16 parts by mass in the dropping funnel as having The oxazoline-based polymerizable unsaturated monomer 2-isopropenyl-2- A mixture of oxazoline, 32 parts by mass of methoxy polyethylene glycol acrylate (average number of moles added to ethylene glycol: 9 mol, manufactured by Shinnakamura Chemical) and 32 parts by mass of methyl methacrylate, In a nitrogen atmosphere, drip at 70°C for 1 hour. After the dripping, the reaction solution was stirred for 9 hours and cooled to obtain a solid content of 40% by mass. Oxazoline-based water-soluble resin (E-1).
(易接著層用塗布液之調製) 混合下述之塗劑,作成易接著層用塗布液。 水 55.62質量% 異丙醇 30.00質量% 聚胺基甲酸酯樹脂(D-1) 11.29質量%唑啉系交聯劑(E-1) 2.26質量% 粒子 0.71質量% (平均粒徑40nm的矽溶膠,固體成分濃度40質量%) 粒子 0.07質量% (平均粒徑450nm的矽溶膠,固體成分濃度40質量%) 界面活性劑 0.05質量% (矽系、固體成分濃度100質量%) (固體成分濃度10質量%)(Preparation of coating liquid for easy-adhesive layer) The following coating agents were mixed to prepare a coating liquid for easy-adhesive layer. Water 55.62% by mass isopropanol 30.00% by mass Polyurethane resin (D-1) 11.29% by mass Oxazoline-based crosslinking agent (E-1) 2.26% by mass, 0.71% by mass of particles (silica sol with an average particle size of 40nm, solid content concentration of 40% by mass) 0.07% by mass of particles (silica sol with an average particle size of 450nm, solid content concentration 40% by mass) Surfactant 0.05% by mass (silicon-based, solid content concentration 100% by mass) (solid content concentration 10% by mass)
(轉印用配向薄膜捲筒1之製造) 作為轉印用配向薄膜的中間層用之原料,將90質量份的PET(X-m)樹脂丸粒與10質量份的含有紫外線吸收劑之PET(Y)樹脂丸粒在135℃減壓乾燥(1托)6小時後,供給至擠壓機2(中間層II層用)。又,作為轉印用配向薄膜的外層用之原料,藉由常見方法乾燥PET(X-m),供給至擠壓機1(外層(I層、III層)用),在285℃熔化。將此2種的聚合物各自以不銹鋼燒結體的濾材(標稱過濾精度10μm粒子95%截止)進行過濾,以2種3層匯流區塊(block)進行積層,從管口擠出片狀後,使用靜電施加澆鑄法,捲附於表面溫度30℃的澆鑄滾筒,進行冷卻固化,製作未延伸薄膜。此時,以I層、II層、III層的厚度之比成為10:80:10之方式,調整各擠壓機之吐出量。(Manufacture of alignment film roll 1 for transfer) As a raw material for the intermediate layer of the alignment film for transfer, 90 parts by mass of PET (Xm) resin pellets and 10 parts by mass of PET (Y) resin pellets containing ultraviolet absorbers were dried under reduced pressure at 135°C (1 After 6 hours, it was supplied to the extruder 2 (for the middle layer II). Also, as a raw material for the outer layer of the alignment film for transfer, PET (X-m) was dried by a common method, supplied to the extruder 1 (for outer layer (layer I, layer III)), and melted at 285°C. The two types of polymers are each filtered with a stainless steel sintered filter material (with a nominal filtration accuracy of 10μm particles 95% cut off), stacked with two types of three-layer confluent blocks, and extruded into a sheet form from the nozzle , Using the static application casting method, wrapped around a casting drum with a surface temperature of 30°C, cooled and solidified to produce an unstretched film. At this time, adjust the discharge amount of each extruder so that the ratio of the thickness of the I layer, the II layer, and the III layer becomes 10:80:10.
接著,藉由逆向輥法,於此未延伸PET薄膜之單面,以乾燥後的塗布量成為0.08g/m2 之方式塗布易接著用塗布液後,導引至乾燥機,在80℃乾燥20秒。Then, by the reverse roll method, the unstretched PET film is coated on one side of the non-stretched PET film so that the coating amount after drying becomes 0.08g/m 2 and the easy-to-adhesive coating liquid is applied to the dryer and dried at 80°C 20 seconds.
將此形成有塗布層的未延伸薄膜導引至拉幅延伸機,一邊以夾具抓住薄膜之端部,一邊導引至溫度125℃的熱風區,在寬度方向中延伸至4.0倍。接著,保持著在寬度方向中經延伸的寬度,於溫度210℃以10秒熱定型處理,更進行3.0%的鬆弛處理。然後,切斷經冷卻的薄膜之兩端部,以0.4kg/mm2 之張力捲取,得到薄膜厚度50μm的單軸配向PET薄膜(寬度1800cm,轉印用配向薄膜1)。 將所得之薄膜的中央部切割成50cm寬度,成為長度約500m的薄膜捲筒(切割薄膜1-c)。 從所得之薄膜的中央部切割右側50cm寬度,成為長度約500m的薄膜捲筒(1-r1)。 切割所得之薄膜的右側端部50cm寬度,成為長度約500m的薄膜捲筒(1-r2)。The unstretched film with the coating layer formed was guided to a tenter stretcher, and while gripping the end of the film with a clamp, it was guided to a hot air zone with a temperature of 125°C and stretched 4.0 times in the width direction. Then, while keeping the width stretched in the width direction, the heat-set treatment was performed at a temperature of 210°C for 10 seconds, and a relaxation treatment of 3.0% was further performed. Then, both ends of the cooled film were cut and wound with a tension of 0.4 kg/mm 2 to obtain a uniaxially oriented PET film with a film thickness of 50 μm (width 1800 cm, oriented film 1 for transfer). The center part of the obtained film was cut into a width of 50 cm to form a film roll (cut film 1-c) with a length of about 500 m. Cut a width of 50 cm on the right side from the center of the obtained film to form a film roll (1-r1) with a length of about 500 m. The cut film has a width of 50 cm at the right end and becomes a film roll (1-r2) with a length of about 500 m.
(轉印用配向薄膜捲筒2之製造) 除了使用經加熱的輥群及紅外線加熱器,將經由與轉印用配向薄膜1同樣之方法所製作的未延伸薄膜(易接著層塗布完畢)加熱至105℃,然後以具有圓周速度差的輥群,在行進方向中延伸3.3倍後,導引至溫度135℃的熱風區,在寬度方向中延伸3.5倍,將熱定型溫度設為225℃以外,以與轉印用配向薄膜1同樣之方法得到轉印用配向薄膜2。 將所得之薄膜的中央部切割成50cm寬度,成為長度約500m的薄膜捲筒(2-c)。 從所得之薄膜的中央部切割右側50cm寬度,成為長度約500m的薄膜捲筒(2-r1)。 切割所得之薄膜的右側一半之中央部50cm寬度,成為長度約500m的薄膜捲筒(2-r2)。 切割所得之薄膜的右側端部50cm寬度,成為長度約500m的薄膜捲筒(2-r3)。(Manufacturing of alignment film roll 2 for transfer) Except for using heated rolls and infrared heaters, the unstretched film (with the easy-adhesive layer coated) produced by the same method as the transfer alignment film 1 is heated to 105°C, and then used with a roll with a circumferential speed difference After the group is stretched 3.3 times in the traveling direction, it is guided to a hot air zone with a temperature of 135°C, and stretched 3.5 times in the width direction. The heat setting temperature is set to other than 225°C, and the same method as the alignment film 1 for transfer The alignment film 2 for transfer was obtained. The center part of the obtained film was cut into a width of 50 cm to form a film roll (2-c) with a length of about 500 m. From the center of the obtained film, a width of 50 cm was cut on the right side to form a film roll (2-r1) with a length of about 500 m. The cut film has a width of 50 cm in the center of the right half of the film and becomes a film roll (2-r2) with a length of about 500 m. The cut film has a width of 50 cm at the right end and becomes a film roll (2-r3) with a length of about 500 m.
(轉印用配向薄膜捲筒3-c之製造) 捲出薄膜捲筒1-c,使其通過130℃的加熱烘箱,進行捲取、退火處理,得到轉印用配向薄膜捲筒3-c。烘箱的通過時間為20秒。(Manufacturing of alignment film roll 3-c for transfer) The film roll 1-c was unwound and passed through a heating oven at 130° C. to undergo winding and annealing treatments to obtain an alignment film roll 3-c for transfer. The passage time of the oven is 20 seconds.
(轉印用配向薄膜捲筒4-c之製造) 除了如表1所示地改變鬆弛處理條件以外,與轉印用配向薄膜1同樣地進行,得到轉印用配向薄膜捲筒4-c。切割中央部分。(Manufacturing of alignment film roll 4-c for transfer) Except for changing the relaxation treatment conditions as shown in Table 1, the same procedure as in the alignment film 1 for transfer was carried out to obtain an alignment film roll 4-c for transfer. Cut the central part.
(轉印用配向薄膜捲筒5-c之製造) 除了如表1所示地改變熱定型溫度以外,與轉印用配向薄膜1同樣地進行,得到轉印用配向薄膜捲筒5-c。切割中央部分。(Manufacturing of Alignment Film Roll 5-c for Transfer) Except that the heat setting temperature was changed as shown in Table 1, the same procedure as in the alignment film 1 for transfer was carried out to obtain an alignment film roll 5-c for transfer. Cut the central part.
(轉印用配向薄膜捲筒6-c之製造) 除了如表1所示地改變寬度方向的延伸倍率以外,與轉印用配向薄膜1同樣地進行,得到轉印用配向薄膜捲筒6-c。切割中央部分。(Manufacture of alignment film roll 6-c for transfer) Except for changing the stretching magnification in the width direction as shown in Table 1, the same procedure was performed as in the alignment film 1 for transfer to obtain an alignment film roll 6-c for transfer. Cut the central part.
(轉印用配向薄膜捲筒7-c之製造) 對於轉印用配向薄膜捲筒6-c進行退火處理,得到轉印用配向薄膜捲筒7-c。(Manufacturing of alignment film roll 7-c for transfer) The alignment film roll 6-c for transfer is annealed to obtain an alignment film roll 7-c for transfer.
(轉印用配向薄膜捲筒8-c之製造) 使用經加熱的輥群及紅外線加熱器,將經由與轉印用配向薄膜1同樣之方法所製作的未延伸薄膜(易接著層塗布完畢)加熱至105℃,然後以具有圓周速度差的輥群,在行進方向中延伸2.0倍後,導引至溫度135℃的熱風區,在寬度方向中延伸4.0倍,以與轉印用配向薄膜1同樣之方法得到轉印用配向薄膜捲筒8-c。切割中央部分。(Manufacturing of alignment film roll 8-c for transfer) Using heated rollers and infrared heaters, heat the unstretched film (with the easy-adhesive layer coated) produced by the same method as the transfer alignment film 1 to 105°C, and then use a roller group with a difference in peripheral speed After extending 2.0 times in the traveling direction, it is guided to a hot air zone with a temperature of 135°C and extended 4.0 times in the width direction to obtain a transfer alignment film roll 8-c in the same way as the transfer alignment film 1 . Cut the central part.
(轉印用配向薄膜捲筒9-c之製造) 除了將熱定型溫度設為170℃,不進行鬆弛處理,以0.6kg/mm2 之張力捲取以外,與轉印用配向薄膜1同樣地,得到轉印用配向薄膜捲筒9-c。切割中央部分。(Manufacturing of oriented film roll 9-c for transfer) The same as oriented film 1 for transfer except that the heat setting temperature is set to 170°C, the relaxation treatment is not performed, and the tension is wound at 0.6 kg/mm 2 , Obtain an alignment film roll 9-c for transfer. Cut the central part.
(轉印用配向薄膜捲筒10-c之製造) 使用經加熱的輥群及紅外線加熱器,將經由與轉印用配向薄膜1同樣之方法所製作的未延伸薄膜(易接著層塗布完畢)加熱至105℃,然後以具有圓周速度差的輥群,在行進方向中延伸4.0倍後,於乾燥機內在溫度225℃處理10秒,利用圓周速度差進行3.0%的鬆弛處理,得到轉印用配向薄膜捲筒10-c。切割中央部分。 再者,於上述轉印用配向薄膜捲筒1~10-c中,使用未塗布易接著層之面(非易接著塗層面)作為脫模面。(Manufacturing of alignment film roll 10-c for transfer) Using heated rollers and infrared heaters, heat the unstretched film (with the easy-adhesive layer coated) produced by the same method as the transfer alignment film 1 to 105°C, and then use a roller group with a difference in peripheral speed After extending 4.0 times in the traveling direction, it was treated in a dryer at a temperature of 225°C for 10 seconds, and a 3.0% relaxation treatment was performed using the circumferential speed difference to obtain an alignment film roll 10-c for transfer. Cut the central part. Furthermore, in the above-mentioned alignment film rolls 1 to 10-c for transfer, the surface on which the easy-adhesion layer is not coated (the non-easy-adhesion coating surface) is used as the release surface.
(轉印用配向薄膜捲筒11-c之製造) 對於轉印用配向薄膜捲筒1(1-c)之非易接著塗布面,進行電暈處理,塗布下述寡聚物阻擋塗劑,於加熱烘箱中在150℃乾燥3分鐘,得到轉印用配向薄膜捲筒11-c。塗布層之厚度為150nm。 ・三聚氰胺交聯烷基改質醇酸樹脂(日立化成聚合物公司製:Tesfine 322:固體成分40%) 2.5份 ・對甲苯磺酸(日立化成聚合物公司製:Dryer 900) 0.025份 ・甲苯 50份 ・甲基乙基酮 47.2份 還有,使用寡聚物阻擋塗層面作為脫模面。(Manufacture of alignment film roll 11-c for transfer) For the non-adhesive coating surface of the alignment film roll 1(1-c) for transfer, corona treatment was performed, the following oligomer barrier coating agent was applied, and it was dried in a heating oven at 150°C for 3 minutes to obtain a transfer Use alignment film roll 11-c. The thickness of the coating layer is 150 nm. ・Melamine cross-linked alkyl modified alkyd resin (manufactured by Hitachi Chemical Polymers: Tesfine 322: 40% solid content) 2.5 copies ・P-toluenesulfonic acid (manufactured by Hitachi Chemical Polymers: Dryer 900) 0.025 parts ・Toluene 50 copies ・Methyl ethyl ketone 47.2 copies Also, the oligomer barrier coating surface is used as the release surface.
(轉印用配向薄膜捲筒12-c之製造) 除了代替單面的易接著層用塗布液,使用下述之塗劑(寡聚物阻擋塗劑),在另一面使用下述之塗劑且不含矽石粒子者以外,與轉印用配向薄膜1同樣地進行,得到轉印用配向薄膜捲筒12-c。切割中央部分。 ・六甲氧基羥甲基三聚氰胺 52質量% ・Epocros(日本觸媒股份有限公司製);唑啉基量7.7mmol/g 30質量% ・聚甘油聚環氧丙基醚 10質量% ・2-胺基-2-甲基丙醇鹽酸鹽 3質量% ・矽石粒子(平均粒徑0.07μm) 5質量% (溶劑:甲苯/MEK=1/1) 還有,使用不含矽石粒子的寡聚物阻擋塗層面作為脫模面。(Manufacturing of oriented film roll 12-c for transfer) Except for the coating solution for easy bonding layer on one side, the following coating agent (oligomer barrier coating) is used, and the following coating agent is used on the other side Except that the silica particles were not included, the same procedure was performed as in the alignment film 1 for transfer to obtain an alignment film roll 12-c for transfer. Cut the central part.・Hexamethoxymethylol melamine 52% by mass ・Epocros (manufactured by Nippon Shokubai Co., Ltd.); The amount of oxazoline groups 7.7mmol/g 30% by mass ・Polyglycerol polyglycidyl ether 10% by mass ・2-Amino-2-methylpropanol hydrochloride 3% by mass ・Silica particles (average particle size 0.07 μm) 5 mass% (solvent: toluene/MEK=1/1) In addition, the oligomer barrier coating surface without silica particles is used as the release surface.
(轉印用配向薄膜捲筒13-c之製造) 除了代替PET(X-m),使用PET(X-s)以外,與轉印用配向薄膜捲筒11-c同樣地進行,得到轉印用配向薄膜捲筒13-c。切割中央部分。 還有,使用寡聚物阻擋塗層面作為脫模面。(Manufacturing of alignment film roll 13-c for transfer) Except for using PET (X-s) instead of PET (X-m), the same procedure was performed as in the alignment film roll 11-c for transfer to obtain the alignment film roll 13-c for transfer. Cut the central part. Also, the oligomer barrier coating surface is used as the release surface.
(轉印用配向薄膜捲筒14-c之製造) 除了使用下述之塗劑作為易接著層用塗布液以外,與轉印用配向薄膜1同樣地進行,得到具有抗靜電能力的轉印用配向薄膜捲筒14-c。 水 16.70質量% 異丙醇 21.69質量% 山梨糖醇 5.00質量% 噻吩系樹脂 51.02質量% (STARCK公司製Bytron P AG,固體成分濃度1.2質量%) 聚胺基甲酸酯樹脂(D-1) 3.81質量%唑啉系交聯劑水溶液(E-1) 1.22質量% 粒子 0.70質量% (平均粒徑40nm的矽溶膠,固體成分濃度40質量%) 粒子 0.07質量% (平均粒徑450nm的矽溶膠,固體成分濃度40質量%) 界面活性劑 0.05質量% (矽系、固體成分濃度100質量%) (固體成分濃度10質量%) 還有,使用非易接著塗層面作為脫模面。(Manufacturing of Alignment Film Roll 14-c for Transfer) Except that the following coating agent is used as the coating liquid for the easy-to-bond layer, proceed in the same way as the alignment film 1 for transfer to obtain an antistatic film for transfer Alignment film roll 14-c. Water 16.70% by mass, 21.69% by mass of isopropanol, 5.00% by mass of Sorbitol, 51.02% by mass of thiophene resin (Bytron P AG manufactured by STARCK, with a solid content of 1.2% by mass) Polyurethane resin (D-1) 3.81 quality% Oxazoline-based crosslinking agent aqueous solution (E-1) 1.22% by mass, 0.70% by mass of particles (silica sol with an average particle size of 40nm, solid content 40% by mass) 0.07% by mass of particles (silica sol with an average particle size of 450nm, solid content Concentration 40% by mass) Surfactant 0.05% by mass (silicon-based, solid content concentration 100% by mass) (Solid content concentration 10% by mass) Also, the non-adhesive coating surface is used as the release surface.
(轉印用配向薄膜捲筒15-c之製造) 於轉印用配向薄膜捲筒1(1-c)之易接著塗布面,塗布Peltron C-4402(銻摻雜氧化錫粒子)經MEK成為固體成分濃度5%者,於加熱烘箱中在80℃乾燥3分鐘,設置厚度100nm的抗靜電塗層。另一方面,於非易接著塗布面,與轉印用配向薄膜11-c同樣地設置寡聚物阻擋塗層,得到具有抗靜電能力的轉印用配向薄膜捲筒15-c。 還有,使用寡聚物阻擋塗層面作為脫模面。(Manufacturing of alignment film roll 15-c for transfer) Coat Peltron C-4402 (antimony-doped tin oxide particles) on the easy-adhesive coating surface of the alignment film roll 1 (1-c) for transfer and MEK to a solid content concentration of 5%, in a heating oven at 80℃ Dry for 3 minutes and set an antistatic coating with a thickness of 100nm. On the other hand, on the non-easy-adhesion coating surface, an oligomer barrier coating is provided in the same manner as the alignment film 11-c for transfer to obtain an alignment film roll 15-c for transfer with antistatic ability. Also, the oligomer barrier coating surface is used as the release surface.
表1中顯示上述轉印用配向薄膜捲筒各自之製造條件與特性。
[表1]
實驗例1A (摩擦處理配向控制層之形成) 捲出轉印用配向薄膜捲筒1-c,切出長度30cm,於非易接著塗布面上,使用棒塗機塗布下述組成之摩擦處理配向控制層用塗料,在80℃乾燥5分鐘,形成厚度200nm之膜。接著,以捲繞有尼龍製的起毛布之摩擦輥處理所得之膜的表面,得到積層有摩擦處理配向控制層之轉印用配向薄膜。摩擦係以對於所切出的長方形之短邊成為45度之方式進行。 完全皂化型聚乙烯醇(重量平均分子量800) 2質量份 離子交換水 100質量份 界面活性劑 0.5質量份Experimental example 1A (Formation of rubbing processing alignment control layer) Take out the alignment film roll 1-c for transfer and cut it out to a length of 30cm. Use a bar coater to coat the rubbing treatment alignment control layer paint with the following composition on the non-adhesive coating surface, and dry it at 80°C for 5 minutes. A film with a thickness of 200 nm is formed. Next, the surface of the obtained film was treated with a rubbing roll wound with a raised cloth made of nylon to obtain an alignment film for transfer with a rubbing alignment control layer laminated. The friction is performed so that the short side of the cut rectangle becomes 45 degrees. Fully saponified polyvinyl alcohol (weight average molecular weight 800) 2 parts by mass Ion-exchanged water 100 parts by mass Surface active agent 0.5 parts by mass
接著,於施有摩擦處理之面上,藉由棒塗法塗布下述組成之相位差層(液晶化合物配向層)形成用溶液。在110℃乾燥3分鐘,照射紫外線而使其硬化,使作為相位差層(液晶化合物配向層)的λ/4層形成在轉印用配向薄膜1-c上,製造液晶化合物配向層轉印用積層體。 棒狀液晶化合物(BASF公司製的LC242) 75質量份 下述化合物 20質量份 三羥甲基丙烷三丙烯酸酯 5質量份 Irgacure 379 3質量份 界面活性劑 0.1質量份 甲基乙基酮 250質量份Next, a solution for forming a retardation layer (liquid crystal compound alignment layer) of the following composition was coated by a bar coating method on the rubbed surface. Drying at 110°C for 3 minutes, irradiating ultraviolet rays to harden, forming a λ/4 layer as a retardation layer (liquid crystal compound alignment layer) on the alignment film 1-c for transfer, manufacturing liquid crystal compound alignment layer transfer Layered body Rod-shaped liquid crystal compound (LC242 manufactured by BASF) 75 parts by mass of the following compound 20 parts by mass Trimethylolpropane triacrylate 5 parts by mass Irgacure 379 3 parts by mass Surfactant 0.1 parts by mass methyl ethyl ketone 250 parts by mass
實驗例2A、3A、6A~21A、實驗例2B 除了如表2所示地改變轉印用配向薄膜之種類以外,與實驗例1A同樣地,製造實驗例2A、3A、6A~21A、實驗例2B之液晶化合物配向層轉印用積層體。Experimental example 2A, 3A, 6A-21A, experimental example 2B Except that the type of the alignment film for transfer was changed as shown in Table 2, in the same manner as in Experimental Example 1A, laminates for transfer of the liquid crystal compound alignment layer of Experimental Examples 2A, 3A, 6A to 21A, and Experimental Example 2B were produced.
實驗例4A、5A、實驗例1B 從轉印用配向薄膜捲筒1-r2切出長度約30cm,從所切出的薄膜,以薄膜之配向軸與長邊的方向所成的角度成為6度、9度、15度之方式,將形狀調整成盡量大面積的長方形。除了使用此薄膜以外,與實驗例3A同樣地,製造實驗例4A、5A、實驗例1B之液晶化合物配向層轉印用積層體。Experimental example 4A, 5A, experimental example 1B Cut out the length of about 30cm from the alignment film roll 1-r2 for transfer, and cut out the film from the angle formed by the alignment axis of the film and the direction of the long side to be 6 degrees, 9 degrees, and 15 degrees. Adjust the shape to a rectangle as large as possible. Except for using this film, in the same manner as in Experimental Example 3A, laminates for transferring liquid crystal compound alignment layers of Experimental Examples 4A, 5A, and Experimental Example 1B were produced.
表2中顯示實驗例1A~21A、1B、2B之液晶化合物配向層轉印用積層體的評價結果。還有,表2之實驗例4A、5A、實驗例1B之「MD或TD與配向方向之角度(最大地方 度)」的項目之數值係表示長方形樣品的長邊與配向軸所成之角度。
[表2]
由表2清楚可知,滿足第一發明的要件之實驗例1A~21A係皆漏光為◎、○或△,在配向薄膜上積層有相位差層(液晶化合物配向層)之狀態下評價相位差者係可能,亮度均勻性亦優異。相對於其,配向薄膜的配向方向與配向薄膜的流動方向或與流動方向正交的方向之間的角度過大之實驗例1B及實驗例2B係皆漏光為×,在配向薄膜上積層有相位差層(液晶化合物配向層)之狀態下評價相位差狀態者係困難。It is clear from Table 2 that the experimental examples 1A-21A satisfying the requirements of the first invention all have light leakage of ◎, ○ or △, and the phase difference is evaluated in the state where the phase difference layer (liquid crystal compound alignment layer) is laminated on the alignment film The system is possible, and the brightness uniformity is also excellent. On the other hand, the angle between the alignment direction of the alignment film and the flow direction of the alignment film or the direction orthogonal to the flow direction is too large for the experimental example 1B and the experimental example 2B, the light leakage is ×, and there is a phase difference between the layers on the alignment film It is difficult to evaluate the phase difference state in the state of the layer (liquid crystal compound alignment layer).
又,由表2清楚可知,滿足第二發明的要件之實驗例1A~3A、6A~14A、16A~21A係皆相位差層的配向角度偏離為◎、○或△。相對於其,配向薄膜的流動方向(MD方向)與流動方向正交的方向(TD方向)之間的150℃熱收縮率之差過大之實驗例15A,係相位差層的配向角度偏離為×。於實驗例15A之情況,在下一步驟等進一步加熱時,或設置相位差層時的溫度等變高時,相位差層之配向方向係偏離,有無法在對象物設置符合設計的配向之相位差層之虞。In addition, as is clear from Table 2, experimental examples 1A to 3A, 6A to 14A, and 16A to 21A satisfying the requirements of the second invention all have the alignment angle deviation of the retardation layer as ⊚, ◯, or △. On the other hand, in Experimental Example 15A where the difference in thermal shrinkage at 150°C between the flow direction (MD direction) of the alignment film and the direction orthogonal to the flow direction (TD direction) is too large, the alignment angle of the retardation layer deviates as × . In the case of Experimental Example 15A, when further heating is performed in the next step, or when the temperature when the retardation layer is installed becomes high, the alignment direction of the retardation layer is deviated, and it is impossible to set the retardation in the object in accordance with the design. Layer of concern.
表3中顯示與實驗例1A比較之實驗例17A~21A的液晶化合物配向層轉印用積層體之寡聚物阻擋塗布的效果及抗靜電層的效果。
[表3]
由表3清楚可知,滿足第三發明的要件之實驗例17A~19A係皆Δ霧度(熱處理前後的霧度之增加量)小,充分地抑制熱處理所造成的霧度之增加。特別地,作為構成配向薄膜的聚酯樹脂,使用低寡聚物量的聚酯之實驗例19A,係表層寡聚物含量少,因此表面寡聚物析出量亦少,結果Δ霧度係比其它實施例顯著地小,極充分地抑制熱處理所造成的霧度之增加。相對於其,表面寡聚物析出量大之實驗例1A係Δ霧度大,因熱處理而霧度大幅增加。又,設有抗靜電塗層之實驗例21A及在易接著層中添加有抗靜電劑之實驗例20A,係與不進行那樣的實驗例1A相比,皆薄膜之表面電阻充分低,抗靜電性優異。It is clear from Table 3 that the experimental examples 17A to 19A satisfying the requirements of the third invention all have a small Δ haze (the increase in haze before and after heat treatment), which sufficiently suppresses the increase in haze caused by the heat treatment. In particular, in Experimental Example 19A, which uses a polyester with a low oligomer content as the polyester resin constituting the alignment film, the surface layer oligomer content is small, so the surface oligomer precipitation amount is also small. As a result, the Δ haze is higher The examples are remarkably small, and the increase in haze caused by the heat treatment is extremely suppressed. In contrast, the experimental example 1A in which the amount of surface oligomers was large was large in Δ haze, and the haze increased significantly due to heat treatment. In addition, the experimental example 21A provided with an antistatic coating and the experimental example 20A where an antistatic agent was added to the easy-to-bond layer are compared with the experimental example 1A which is not performed. The surface resistance of the film is sufficiently low and antistatic Excellent performance.
表4中顯示作為代表之實驗例1A的薄膜之表面粗糙度。還有,於相位差層之評價中,未看見針孔狀或傷痕狀之缺點。
[表4]
實驗例22A (作為液晶化合物配向層積層偏光板之具體例的圓偏光板之製造) 使用極限黏度0.63的聚對苯二甲酸乙二酯作為熱塑性樹脂基材,製造厚度100μm之未延伸薄膜,於此未延伸薄膜之單面上,塗布聚合度2400、皂化度99.9莫耳%的聚乙烯醇之水溶液及乾燥,形成PVA層。 在120℃於圓周速度不同的輥間,將所得之積層體在長度方向中延伸至2倍及捲取。接著,將所得之積層體以4%的硼酸水溶液進行30秒的處理後,以碘(0.2%)與碘化鉀(1%)之混合水溶液浸漬60秒而染色,接著以碘化鉀(3%)與硼酸(3%)之混合水溶液處理30秒。 再者,將此積層體在72℃的硼酸(4%)與碘化鉀(5%)混合水溶液中,在長度方向中進行單軸延伸,接著以4%碘化鉀水溶液洗淨,以氣刀去除水溶液後,在80℃的烘箱中乾燥,切割兩端部及捲取,得到寬度30cm、長度1000m之基材積層偏光鏡。合計的延伸倍率為6.5倍,偏光鏡之厚度為5μm。還有,厚度係於環氧樹脂中包埋基材積層偏光鏡,切出切片,以光學顯微鏡觀察而讀取。Experimental example 22A (Manufacturing of a circular polarizing plate as a specific example of a liquid crystal compound aligned laminated polarizing plate) Using polyethylene terephthalate with an ultimate viscosity of 0.63 as the thermoplastic resin substrate, an unstretched film with a thickness of 100 μm was produced. On one side of the unstretched film, a poly with a degree of polymerization of 2400 and a degree of saponification of 99.9 mol% was coated. An aqueous solution of vinyl alcohol and drying to form a PVA layer. At 120°C between rolls with different circumferential speeds, the resulting laminate was stretched twice in the length direction and wound up. Next, the resulting laminate was treated with a 4% boric acid aqueous solution for 30 seconds, and then immersed in a mixed aqueous solution of iodine (0.2%) and potassium iodide (1%) for 60 seconds for dyeing, followed by potassium iodide (3%) and boric acid (3%) mixed aqueous solution for 30 seconds. In addition, the laminate is stretched uniaxially in the longitudinal direction in a mixed aqueous solution of boric acid (4%) and potassium iodide (5%) at 72°C, then washed with a 4% potassium iodide aqueous solution, and then removed with an air knife. , Dried in an oven at 80°C, cut both ends and coiled to obtain a substrate laminated polarizer with a width of 30cm and a length of 1000m. The total extension magnification is 6.5 times, and the thickness of the polarizer is 5μm. In addition, the thickness is embedded in epoxy resin with a laminated polarizer of the substrate, cut out the slices, and read by observation with an optical microscope.
於超雙折射聚酯薄膜(Cosmoshine(R)SRF 厚度80μm 東洋紡公司製)上,使用紫外線硬化型接著劑,貼合上述基材積層偏光鏡的偏光鏡面後,剝離基材積層偏光鏡之基材。再者,於此偏光鏡面上積層市售的光學黏著劑片。剝離黏著劑片之脫模薄膜,貼合實驗例1A之液晶化合物配向層轉印用積層體的液晶化合物配向層面與黏著劑層,然後,剝離實驗例1A之積層體中的配向薄膜,得到圓偏光板。所得之圓偏光板具有高的抗反射功能。還有,Cosmoshine(R)SRF的慢軸與偏光鏡的消光軸係成為垂直,Cosmoshine(R)SRF的MD方向與實驗例1A的積層體中之配向薄膜的MD方向係成為平行。 [產業上利用之可能性]On a super-birefringent polyester film (Cosmoshine(R)SRF "80μm thickness" manufactured by Toyobo Co., Ltd.), use an ultraviolet-curing adhesive to bond the polarizer surface of the above-mentioned substrate laminated polarizer, and then peel off the substrate of the laminated polarizer. . Furthermore, a commercially available optical adhesive sheet is laminated on the surface of the polarizer. The release film of the adhesive sheet was peeled off, the liquid crystal compound alignment layer and the adhesive layer of the liquid crystal compound alignment layer transfer laminate of Experimental Example 1A were bonded together, and then the alignment film in the laminate of Experimental Example 1A was peeled off to obtain a circle Polarizing plate. The resulting circular polarizer has a high anti-reflection function. In addition, the slow axis of Cosmoshine(R)SRF is perpendicular to the extinction axis of the polarizer, and the MD direction of Cosmoshine(R)SRF is parallel to the MD direction of the alignment film in the laminate of Experimental Example 1A. [Possibility of Industrial Use]
本發明之液晶化合物配向層轉印用配向薄膜係可在配向薄膜上積層有液晶化合物配向層之狀態下,適當地評價設於上的液晶化合物配向層(相位差層或偏光層)之配向狀態等。又,本發明之液晶化合物配向層轉印用配向薄膜,係可一邊使用便宜且機械強度優異的聚酯等延伸薄膜,一邊以符合設計的配向,轉印相位差層或偏光層,可防止顯示器的漏光之問題。再者,本發明之液晶化合物配向層轉印用配向薄膜,由於可一邊使用便宜且機械強度優異的聚酯等延伸薄膜,一邊有效果地防止薄膜之加熱處理時的霧度上升或異物發生,故可形成符合設計的配向之相位差層或偏光層(液晶化合物配向層)。因此,依照本發明,可以高品質安定地製造圓偏光板等的相位差層積層偏光板。The alignment film for the transfer of the liquid crystal compound alignment layer of the present invention can appropriately evaluate the alignment state of the liquid crystal compound alignment layer (phase difference layer or polarizing layer) provided on the alignment film with the liquid crystal compound alignment layer laminated on the alignment film Wait. In addition, the alignment film for the transfer of the alignment layer of the liquid crystal compound of the present invention can be used to transfer the retardation layer or the polarizing layer with the alignment in accordance with the design while using a stretch film such as a polyester film that is inexpensive and excellent in mechanical strength. The problem of light leakage. Furthermore, the alignment film for the transfer of the alignment layer of the liquid crystal compound of the present invention can effectively prevent the increase in haze or the occurrence of foreign matter during the heat treatment of the film while using a stretched film such as polyester, which is inexpensive and excellent in mechanical strength. Therefore, it is possible to form a retardation layer or a polarizing layer (liquid crystal compound alignment layer) conforming to the designed alignment. Therefore, according to the present invention, a retardation laminated polarizing plate such as a circular polarizing plate can be manufactured with high quality and stability.
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TW108138546A TW202033339A (en) | 2018-10-26 | 2019-10-25 | Alignment film for transferring liquid crystal compound alignment layer |
TW108138545A TWI824046B (en) | 2018-10-26 | 2019-10-25 | Alignment film for transfer of liquid crystal compound alignment layer, laminate for transfer of liquid crystal compound alignment layer, manufacturing method of liquid crystal compound alignment layer laminated polarizing plate, and inspection method of laminate for transfer of liquid crystal compound alignment layer |
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CN112771422B (en) | 2023-10-24 |
CN112771423B (en) | 2023-10-27 |
CN112771423A (en) | 2021-05-07 |
KR20210082159A (en) | 2021-07-02 |
WO2020085307A1 (en) | 2020-04-30 |
JPWO2020085308A1 (en) | 2021-09-24 |
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CN112805136B (en) | 2023-06-20 |
KR20210082163A (en) | 2021-07-02 |
KR20210079273A (en) | 2021-06-29 |
WO2020085309A1 (en) | 2020-04-30 |
CN112789531B (en) | 2023-10-27 |
CN112805136A (en) | 2021-05-14 |
CN112771422A (en) | 2021-05-07 |
TW202033339A (en) | 2020-09-16 |
JPWO2020085309A1 (en) | 2021-09-24 |
JPWO2020085307A1 (en) | 2021-09-30 |
CN116804778A (en) | 2023-09-26 |
WO2020085310A1 (en) | 2020-04-30 |
JPWO2020085310A1 (en) | 2021-10-07 |
CN112789531A (en) | 2021-05-11 |
KR20210079272A (en) | 2021-06-29 |
JP7539036B2 (en) | 2024-08-23 |
TWI824046B (en) | 2023-12-01 |
WO2020085308A1 (en) | 2020-04-30 |
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