WO2012173431A2 - Method for manufacturing a patterned phase retardation film - Google Patents

Method for manufacturing a patterned phase retardation film Download PDF

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Publication number
WO2012173431A2
WO2012173431A2 PCT/KR2012/004753 KR2012004753W WO2012173431A2 WO 2012173431 A2 WO2012173431 A2 WO 2012173431A2 KR 2012004753 W KR2012004753 W KR 2012004753W WO 2012173431 A2 WO2012173431 A2 WO 2012173431A2
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WO
WIPO (PCT)
Prior art keywords
alignment
orientation
manufacturing
rubbing
substrate
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PCT/KR2012/004753
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French (fr)
Korean (ko)
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WO2012173431A3 (en
Inventor
이성규
최진욱
김성민
이승희
이명훈
강신웅
정광운
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주식회사 동진쎄미켐
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Publication of WO2012173431A2 publication Critical patent/WO2012173431A2/en
Publication of WO2012173431A3 publication Critical patent/WO2012173431A3/en

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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3083Birefringent or phase retarding elements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/36Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/52Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56Aligning agents
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1337Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

  • the present invention relates to a method of manufacturing a patterned phase delay film, and more particularly, to a method of manufacturing a phase delay film and a patterned phase delay film capable of producing a patterned phase delay film by only one alignment process.
  • the liquid crystal display is a flat panel display which is widely used for various purposes.
  • various technological advances have been made in order for LCDs to function as screen displays in various fields, and the goal is to realize high quality images while maintaining the characteristics of light weight, thinness, and low power consumption.
  • Edo is also developing technology.
  • the liquid crystal display includes a twisted nematic (TN) liquid crystal display, a vertically aligned liquid crystal display (VA), an ln plane switching (IPS) liquid crystal display, and an OCB (Optically Compensated Bend) liquid crystal display depending on the arrangement and driving method of the liquid crystal.
  • TN twisted nematic
  • VA vertically aligned liquid crystal display
  • IPS ln plane switching
  • OCB Optically Compensated Bend
  • the liquid crystals initially form a predetermined array due to the influence of the alignment layer or the properties of the liquid crystal itself, but when the electric field is applied, the arrangement of the liquid crystals changes. Due to the optical anisotropy of the liquid crystals, polarization of light passing through the liquid crystals The image is displayed by changing the state depending on the arrangement state of the liquid crystal and making it appear as a difference in the amount of transmitted light using the polarizing plate.
  • phase delay occurs in light that has passed through the liquid crystal cell.
  • a phase delay film is used in parallel as a film for color compensation.
  • the phase delay film is optically colored by the STN-specific interference color (coloring) called blue mode or yellow mode caused by elliptical polarization.
  • coloring STN-specific interference color
  • TFT-LCD TFT-LCD
  • various phase delay films have been laminated for the purpose of expanding the viewing angle and improving the image quality, and have various phases of functions. Retardation films are required.
  • phase delay film As the manufacturing technique of the phase delay film, there are stretching techniques and alignment techniques, and in particular, alignment techniques are necessary to consider all of polarization, reflection, refraction, interference, diffraction, and scattering.
  • the orientation for determining the initial arrangement of the liquid crystal is mainly performed by rubbing the alignment film in a specific direction using a rubbing method.
  • the rubbing method is a mechanical method, it is difficult to precisely control the initial alignment state of the liquid crystal, and it is difficult to have different pretilt angles for each minute region.
  • the present invention proposes a method for manufacturing a patterned phase delay film by installing and performing secondary rubbing, but there is a disadvantage in that a process line is complicated and a boundary line between areas having different orientations may be unclear in patterning a mask. Moreover, each time an orientation process is added, the process speed is slowed down, which is the biggest cause of the decrease in productivity. This may cause the price of the product to rise.
  • the straightness of the boundary point of the pattern is excellent By confirming that it is possible to form a sophisticated pattern and simplify the process has been completed the present invention.
  • the present invention provides a method for producing a patterned phase delay film and a patterned phase delay film by a single alignment process.
  • the present invention comprises the steps of (a) forming different types of alignment agents to cross at regular intervals on the substrate; (b) forming an orientation on the substrate on which the alignment agent is printed; And (c) coating and curing the photocurable liquid crystal monomer composition on the alignment-formed substrate, and a patterned phase retardation film prepared by the method. To provide.
  • the pattern is significantly improved compared to a process using a conventional mask. It is possible to manufacture a precise phase delay film by showing the straightness of, and to produce a phase delay film patterned by only one orientation forming process, the manufacturing process is reduced by half compared to the prior art, simplifying the process and Excellent cost savings.
  • Example 1 shows an image obtained by observing a patterned phase delay film prepared in Example 1 with a polarization microscope.
  • Figure 2 shows the image observed by the polarizing microscope the pattern phase retardation film produced in Example 2.
  • Figure 3 shows an image of the pattern retardation film produced by Comparative Example 1 observed with a polarizing microscope.
  • the patterned phase delay film can be produced in a single alignment formation process using two types of alignment agents having different types of alignment agents. It was. Therefore, in one aspect, the present invention comprises the steps of: (a) forming different types of alignment agents on the substrate to be crossed at regular intervals; (b) forming an orientation on the substrate on which the alignment agent is printed; And (c) coating and curing the photocurable liquid crystal monomer composition on the substrate on which the alignment is formed. In order to manufacture a phase delay film having a desired pattern interval, it is required to form different types of alignment agents to cross at regular intervals in consideration of the pattern interval required in the phase delay film.
  • the interval at which the different types of alignment agents are formed may be characterized in that 40 to 1000, which should be able to be adjusted fluidly according to the interval of the pattern required in the completed patterned retardation film Because.
  • the patterned retardation film of the present invention is a liquid crystal display panel If mounted and used, it is necessary to adjust the pattern spacing of the phase delay film to match the image display line of the liquid crystal display panel.
  • the interval at which the alignment agent is formed for example, printed, may be preferably 180 to 220. When different types of alignment agents are crossed at regular intervals, it means that two types of alignment agents alternate alternately line by line and form a predetermined interval as manufactured in the embodiment of the present invention.
  • Inkjet printing is a method of printing by ejecting ink or by agglomerating ink
  • gravure printing is one of intaglio printing methods, and is a printing technique suitable for photo printing because it can express minute shades.
  • offset printing is a method that does not print directly on a printed matter from a plate, transfers it to a rubber blanket that acts as an intermediary, and then prints on paper
  • screen printing is a kind of hand print that does not use a large-scale machine. By attaching the material to the board and printing one by one. Also called silk screen, block print.
  • a printing technique capable of giving the same effect by using a technology capable of printing on a transparent substrate according to pattern spacing may be used.
  • the printing technique by using the printing technique to precisely print different types of alignment agents at regular intervals, it is possible to produce a patterned phase delay film having a precise and excellent straightness of the boundary point.
  • a rubbing process is a process of physically sweeping a board
  • the different aligning agents may be an aligning agent in which the alignment is formed in a direction perpendicular to the rubbing direction and an alignment agent in which the alignment is formed in parallel with the rubbing direction, respectively. It can be characterized.
  • the alignment agent is formed in parallel with the rubbing direction, polyimide, polyvinyl alcohol, polyamic acid, polyamide and polyoxyethylene It can be selected from the group consisting of, wherein the aligning agent to form the orientation in the direction perpendicular to the rubbing direction (polystylene) of the formula (1), CBDA-FDA PI (poly- (4,4 '-( 9,9-fluorenyl) diphenylene cyclobutanyltetracarboximide), C4-PMDA-PDA PI of formula 3 (poly ⁇ p-pheylene 3,6-bis [4- (n-butoxy) phenyloxy] pyromellitimide ⁇ , SBF-CBDA PI of formula 4 (poly (2,7- (9,9'-spirobifluorene cyclobutyltetracarboximide)), and SBF-6FDA of formula 5 (poly (2,7- (9,9'-spirobifluorene 4,4
  • the orientation formation in step (b) may be performed by a photoalignment process for forming orientation by irradiating light polarized in one direction.
  • the process is a non-contact process that can be oriented by only a light irradiation process, generally can be classified by photo-dimerization, photo-isomerization and photo-decomposition method. have.
  • the photolysis method has a principle of forming an alignment force by decomposing the polymer chain of the alignment layer using polarized light having a short wavelength of 300 nm or less.
  • the molecular structure of the photoalignment agent is deformed, and thus a uniform orientation is formed.
  • Light for optical alignment can be used for the ultraviolet polarized light of 10 to 200mW / cm 2.
  • the minimum light intensity for forming the photoalignment may vary depending on the molecular structure and photoinitiator of the photoalignment agent. That is, the minimum amount of light energy capable of modifying the molecular structure of the photoalignment agent or activating the photoinitiator may be referred to as the minimum light intensity for photoalignment.
  • the different alignment agents may each be an alignment agent in which the orientation is formed in parallel with the polarization direction of the irradiated light, and an alignment agent in which the orientation is formed in the direction orthogonal to the polarization direction of the irradiated light.
  • the alignment agent is formed in parallel with the polarization direction of the irradiated light, polyimide, polyamic acid, polynorbornene (p ynorbornene), phenylmaleimide copolymer, poly Azobenzene (polyazobenzene), Polyethyleneimide, polyvinyl alcohol, polyethylene, polystylene, polyphenylenephthalamide, polyester, polymethyl methacrylate and CBDA-FDA PI (poly- (4,4 '-(9,9-fluorenyl) diphenylene cyclobutanyltetracarboximide) may be selected from the group consisting of, the orientation is formed in a direction perpendicular to the polarization direction of the irradiated light
  • the alignment agent may be selected from the group consisting of CMPI (Chloromethylated polyimide) of Formula 6 and polyvinylcinamate (PVCi) of Formula 7, but is not limited thereto. If it is an aligning agent in which orientation is formed
  • CMP has the advantage of better solubility than the existing polyimide by replacing the chloromethyl group with the existing polyimide (P), and the boiling point of the solvent makes the process difficult during film curing
  • the light is irradiated with polarized UV light, the light causes anisotropic decomposition of the molecule, resulting in an anisotropic structure.
  • the liquid crystal is aligned.
  • pi has a high thermal stability compared to other photo-alignment material.
  • CMPI was prepared by dissolving 4,4'- (Hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 4,4'-diaminodiphenylether in NMP to polymerize, followed by chemical imidization using pyridine and acetic anhydride. ) After that, it can be obtained by chloromethylation method using chloromethyl methyl ether (CMME) and tin (IV) chloride.
  • 6FDA 4,4'- (Hexafluoroisopropylidene) diphthalic anhydride
  • CMME chloromethyl methyl ether
  • IV tin
  • PVCi is widely known as a material that is oriented in a direction orthogonal to the polarization direction of light when irradiated with polarized light as a photo-alignment material, but the photo-alignment mechanism is still controversial, and the content of cis / Examples are by trans isomerization and by the orientation of benzene groups in dimers. In spite of this controversy, the common point of claims about the photo alignment mechanism is that the alignment occurs due to the structural anisotropy in the alignment film and the interaction with the liquid crystal.
  • the PVCi can be obtained by substituting polyvinylalcohol (Polyvinylalcohol) with cinnamate group (cinnamate group) through etherification.
  • the substrate usable in the present invention is preferably a substrate having an optical transparency of more than 85%, PES (p is yether sulfone), Pl (polyimide), COP (cyclo olefin polymer), PET (polyethylene terephthalate), TAC (triacetyl) It may be characterized in that it is selected from the group consisting of cellulose), PC (poly carbonate) and glass.
  • PES p is yether sulfone
  • Pl polyimide
  • COP cyclo olefin polymer
  • PET polyethylene terephthalate
  • TAC triacetyl
  • the limited materials are materials generally available in the industry, and are not fixed conditions for materials that can be easily changed and used by those skilled in the art.
  • the phase paper pencil may be completed through a process of coating and curing the photocurable liquid crystal monomer composition.
  • a photocurable liquid crystal monomer (RM) is coated on a pattern oriented substrate and cured by ultraviolet rays or the like to form a photocurable liquid crystal monomer layer, wherein the photocurable liquid crystal monomer layer is formed of polarized light. This will delay the phase.
  • the patterned retardation film according to the present invention is different in the direction and size of the phase retardation according to the patterned portion, it is configured to alternately phase retardation direction / size at regular intervals.
  • the photocurable liquid crystal monomer composition is a liquid crystal compound having a polymerizable group, in particular, may have a functional group of an acrylic group, a vinyl ether group or an epoxide, the composition of the photocurable liquid crystal monomer composition is a crosslinking of the polymer
  • polymerizable mesogenic compounds having two or more polymerizable functional groups for example general male to direactive and / or nonpolar to polar compounds can be used in combination, and the alignment profile can be changed by changing their composition ratio. You can also change it.
  • the thickness of the photocurable liquid crystal monomer layer By adjusting the thickness of the photocurable liquid crystal monomer layer, it is possible to adjust the phase delay size, and when the magnitude of the phase delay is ⁇ / 4, the linearly polarized light may be changed into circularly polarized light.
  • [Lambda] is a sign indicating a wavelength of light whose phase is to be natural.
  • the phase retardation of the photocurable liquid crystal monomer is made by the refractive index of the long axis and the short axis in the molecular structure, and the difference is preferably 0.7 to 3.
  • the substrate since the substrate should be coated, it should be used in a certain amount in an organic solvent.
  • the photocurable liquid crystal monomer layer includes spin ⁇ comma, gravure, dip, slot die, silk screen, inkjet printing. It is possible to carry out by applying a known coating process such as).
  • spin coating the coating is first coated with a thickness of 0.5 to 5 using a method of first rotating for 20 to 25 seconds at 400 to 1000 rpm and rotating for 70 to 80 seconds at 2500 to 3500 rpm.
  • the curing process is performed by drying at 60 ° C. for 1 minute and irradiating with 20 mW / cm 2 ultraviolet rays for 1 minute. These conditions are different depending on the properties of the photocurable liquid crystal monomer material.
  • the alignment directions patterned at regular intervals are configured to be orthogonal to each other, and the photocurable liquid crystal monomer layer on the substrate is lambda / 4 phase
  • the prepared patterned phase delay film can convert linearly polarized light into left circularly polarized light and right circularly polarized light.
  • the phase retardation film thus prepared is mounted on a panel display that separates the left eye image and the right eye image, and polarized glasses separating the left circular polarization and the right circular polarization can realize 3D stereoscopic images.
  • two types of rubbing alignment agents having different orientation directions were printed at regular intervals, thereby preparing a phase delay film patterned by one rubbing process.
  • the polyimide is a ratio of 2% when the total mass ratio is 100 to a solution mixed with GBL (gamma-Butyrolactone), NMP (N-Methl-2-Pyrrolidone), and BC (2-Butoxyethanol) at 7: 2: 1 CBDA-FDA-PI was used by dissolving in GBL at a mass ratio of 2%.
  • GBL gamma-Butyrolactone
  • NMP N-Methl-2-Pyrrolidone
  • BC (2-Butoxyethanol
  • the rubbing process is carried out in an oblique direction on the applied stripe shape so that the Sc) lvent can be sufficiently fired. In other words, in the direction of 45 ° to the direction of the Machanical direction of the pi film.
  • the rubbing process was carried out under the conditions of a rubbing depth of 1 mm, a rotational speed of 600 rpm, a stage moving speed of 20 mm / sec.
  • Photocurable liquid crystal monomer (RMS-013C, on the alignment agent that proceeded the rubbing process Merck co. Ltd.) is coated on the entire surface, and the drying process is performed for 1 minute at 60 ° C so that the solvent can flow evenly, and the exposure process is performed for 1 minute at 20 mW / cm 2 (at 365 nm) to align the photocurable liquid crystal monomer. Allowed to settle on the altar.
  • the birefringence of the substrate was measured using the birefringence measuring device (REMS-100; Sesim co. Ltd), and the straightness characteristic of the width and the boundary point was confirmed through the polarization microscope. The experiment was repeated five times, and the measured results are shown in Table 1 below, and the photographs observed through the polarizing microscope are shown in FIG. 1.
  • the patterned phase delay film may be manufactured using only one rubbing alignment process. It was confirmed.
  • the width represents the average of the widths of the patterns of the phase-delay film prepared once, and the boundary points represent the degree of deviation from the straight line when viewed as a straight line between the patterns, and the birefringence value is
  • two types of photo-alignment agents having different orientation directions were printed at regular intervals, thereby preparing a phase delay film patterned by one photo-alignment process.
  • the birefringence of the substrate was measured using the birefringence measuring device (REMS-100; Sesim co. Ltd), and the straightness characteristics of the width and the boundary point were confirmed through the polarization microscope. The experiment was repeated five times, and the measured results are shown in Table 2 below, and the photographs observed through the polarizing microscope are shown in FIG. 2.
  • the patterned phase delay film could be produced by only one optical alignment process by printing the alignment agents aligned in parallel with the alignment agents aligned in the direction so as to cross at regular intervals.
  • the width represents the average of the widths of the patterns of the prepared phase delay film once, and the boundary points represent the degree of deviation from the straight line when viewed in a straight line between the patterns in units of m, and the birefringence value is It means the phase delay value for the incident light of 550nm.
  • the value of the pattern width was the average value and the standard deviation value to determine how far it was from the standard value 200 and the uniform value in the experiment that was five times, and the boundary point and the birefringence value were the average values of the five experiments. . Comparative Example 1
  • a PI film was prepared in a size of 5 cm X 5 cm, and the polyimide used in Example 1, which is an alignment agent exhibiting orientation characteristics parallel to the rubbing direction, was placed on the front surface.
  • the primary alignment was subjected to rubbing depth 1mm, rotational speed 600rpm, stage movement speed of 20mm / sec, and the opening was 200um and the non-opening was 150 width.
  • secondary rubbing was performed in the direction orthogonal to a primary rubbing direction. The widths of the openings and the non-openings of the mask do not coincide because the second rubbing does not give the entire surface of the non-openings due to the thickness of the mask during the second rubbing performed after the mask is placed. Therefore, the opening width of the mask should be made relatively wider than the width of the non-opening portion.
  • the width is the width of each pattern of the prepared phase delay film
  • the mean point is the average point
  • the boundary point is the degree of deviation from the straight line when the boundary point between patterns is viewed as a straight line.
  • the value of the pattern width was the mean value and the standard deviation value in order to confirm how far it was from the standard value 200 mi and the uniform value in five experiments, and the boundary point and the birefringence value were the average values of the five experiments.
  • Table 1, 2 and 3 in the case of the patterned phase delay film produced by the manufacturing method according to the present invention, it can be seen that the width of the pattern is formed more stably than the prior art, and the boundary point value In addition, it showed a much lower value than the prior art, it was confirmed that the straightness of the boundary point is significantly improved.
  • Example 1 shows a standard deviation of 6.2, it can be seen that the pattern width is formed very uniformly compared to the standard deviation of more than 40 of the comparative example.
  • the comparative example is shown to deviate more than 40im compared to the case shown in the following case, the straightness of the boundary point of the phase delay film of the present invention is also confirmed to be significantly improved compared to the prior art could.

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  • Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nonlinear Science (AREA)
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Abstract

The present invention relates to a method for manufacturing a patterned phase retardation film, and more particularly, to a method which involves printing different types of aligning agents such that the aligning agents can be crossed with each other so as to have a predetermined gap therebetween, so as to thereby manufacture a patterned phase retardation film using only a single alignment process. The present invention also relates to a patterned phase retardation film manufactured by the method. The method for manufacturing the patterned phase retardation film according to the present invention may enable the formation of different types of aligning agents, having different aligning properties, on a substrate by means of a printing technique, such that the aligning agents can be crossed with each other so as to have a predetermined gap therebetween. Thus, a pattern having significantly improved linearity as compared to those patterns produced through processes using an existing mask can be obtained to enable the manufacture of an elaborate phase retardation film. Furthermore, a patterned phase retardation film can be manufactured using just a single process for forming aligning properties, thus reducing the number of manufacturing processes to half that of conventional techniques, and providing excellent effects in terms of the simplification of processes and the resulting reduction in costs.

Description

【명세서】  【Specification】
【발명의 명칭】  [Name of invention]
패턴된 위상지연필름의 제조방법  Method of manufacturing patterned phase delay film
【기술분야]  Technical Field
본 발명은 패턴된 위상지연필름의 제조 방법에 관한 것으로, 더욱 상세하게는 1회의 배향 공정만으로도 패턴된 위상지연필름을 제조할 수 있는 위상지연필름의 제조 방법 및 패턴된 위상지연필름에 관한 것이다. 【배경기술】  The present invention relates to a method of manufacturing a patterned phase delay film, and more particularly, to a method of manufacturing a phase delay film and a patterned phase delay film capable of producing a patterned phase delay film by only one alignment process. Background Art
정보화 사회가 발전함에 따라표시장치에 대한 요구도 다양한 형태로 점증하고 있으며, 현재 다양한 종류의 평판 표시 장치가 개발되어 사용되고 있다. 그 중에서도 액정 표시 장치는 가장 다양한 용도로 널리 사용되는 평판 표시 장치이다. 이와 같이 액정표시장치가 여러 분야에서 화면 표시장치로서의 역할을 하기 위해 여러 가지 기술적인 발전이 이루어졌으며, 경량, 박형, 저 소비전력의 특징을 유지하면서도 고 품위화상을 얼마나 구현할 수 있는가를 목표에 두고 현재에도 기술 개발이 이루어지고 있다. 액정 표시 장치에는 액정의 배열 상태와 구동 방식에 따라 TN(Twisted Nematic) 액정 표시 장치 , VA(Vertically Aligned) 액정 표시 장치, IPS(ln Plane Switching) 액정 표시 장치, OCB(Optically Compensated Bend) 액정 표시 장치 등이 있다. 이들 액정 표시 장치들은 배향막의 영향이나 액정 자체의 성질에 의해 액정이 초기에 소정의 배열을 이루고 있다가 전계가 인가되면 액정의 배열이 바뀌게 되는데, 액정의 광학적 이방성으로 인해 액정을 통과하는 빛의 편광 상태가 액정의 배열 상태에 따라 달라지고 이를 편광판을 이용하여 투과 광량의 차이로 나타나도록 함으로써 화상을 표시한다.  As the information society develops, the demand for display devices is increasing in various forms, and various kinds of flat panel display devices have been developed and used. Among them, the liquid crystal display is a flat panel display which is widely used for various purposes. As such, various technological advances have been made in order for LCDs to function as screen displays in various fields, and the goal is to realize high quality images while maintaining the characteristics of light weight, thinness, and low power consumption. Edo is also developing technology. The liquid crystal display includes a twisted nematic (TN) liquid crystal display, a vertically aligned liquid crystal display (VA), an ln plane switching (IPS) liquid crystal display, and an OCB (Optically Compensated Bend) liquid crystal display depending on the arrangement and driving method of the liquid crystal. Etc. In these liquid crystal display devices, the liquid crystals initially form a predetermined array due to the influence of the alignment layer or the properties of the liquid crystal itself, but when the electric field is applied, the arrangement of the liquid crystals changes. Due to the optical anisotropy of the liquid crystals, polarization of light passing through the liquid crystals The image is displayed by changing the state depending on the arrangement state of the liquid crystal and making it appear as a difference in the amount of transmitted light using the polarizing plate.
복굴절성을 이용한 STN-LCD에서는 샐 자체에 복굴절성이 있기 때문에 액정 셀을 투과해 왔던 빛에 위상지연 (빛의 일그러짐)이 생긴다. 이 때문에 STN 패널에서는 위상지연 필름이 색 보상용 필름으로써 병행하여 사용되고 있다. 위상지연 필름은 타원 편광에 의해 생기는 blue mode 혹은 yellow mode라고 불리우는 STN 특유의 간섭색 (착색)을 광학적으로 색 보상하는 역할로써 당초 개발되어 왔으며, TFT-LCD의 경우 색 보상 필름으로써의 위상 필름은 불필요 하지만, 최근 들어 시야각의 확대나 화질 향상을 목적으로 각종 위상지연 필름이 적층되고 있고, 보다 다양한 기능의 위상지연 필름이 요구되고 있다. 또한, 3D 입체영상 재현 기술의 발전과 더불어 패턴된 위상지연 필름을 사용하여 좌안 영상과 우안 영상의 편광 방향을 다르게 만들어 주는 기술이 발전하고 있다. 위상지연 필름의 제조 기술로는 연신기술과 배향기술이 있으며, 특히 편광, 반사, 굴절, 간섭, 회절, 산란에 대하여 모두 고려하기 위해서는 배향기술이 필요하다. In the birefringent STN-LCD, since the cell itself is birefringent, phase delay (light distortion) occurs in light that has passed through the liquid crystal cell. For this reason, in a STN panel, a phase delay film is used in parallel as a film for color compensation. The phase delay film is optically colored by the STN-specific interference color (coloring) called blue mode or yellow mode caused by elliptical polarization. It was originally developed as a compensating role, and in the case of TFT-LCD, a phase film as a color compensating film is unnecessary, but in recent years, various phase delay films have been laminated for the purpose of expanding the viewing angle and improving the image quality, and have various phases of functions. Retardation films are required. In addition, with the development of 3D stereoscopic image reproduction technology, a technology for making polarization directions of left and right eyes different from each other by using a patterned phase delay film has been developed. As the manufacturing technique of the phase delay film, there are stretching techniques and alignment techniques, and in particular, alignment techniques are necessary to consider all of polarization, reflection, refraction, interference, diffraction, and scattering.
액정의 초기 배열을 결정하는 배향은 주로 러빙 (rubbing) 방법을 사용하여 배향막을 특정 방향으로 쓸어줌으로써 행한다. 그런데 러빙 방법은 기계적으로 이루어지는 방법이어서 액정의 초기 배향 상태를 정밀하게 조절하기가 어렵고, 미세한 영역별로 서로 다른 선경사각을 가지도록 하기가 어렵다. 이때, 기판의 배향막을 미소한 단위 영역마다 다른 방향을 나타내도록 배향시키기 위해서는 두 번의 배향 공정을 행하는 것이 일반적인데, 이와 같은 공정을 위하여 마스크가사용되고 있다.  The orientation for determining the initial arrangement of the liquid crystal is mainly performed by rubbing the alignment film in a specific direction using a rubbing method. However, since the rubbing method is a mechanical method, it is difficult to precisely control the initial alignment state of the liquid crystal, and it is difficult to have different pretilt angles for each minute region. At this time, in order to orient the alignment film of the substrate so as to show different directions for each minute unit region, it is common to perform two alignment processes, and a mask is used for such a process.
즉, 일본 등록 특허 제 2650205호에서는 먼저 한쪽 방향으로 러빙 공정을 실시한 뒤 마스크를 패턴된 형태로 도포하고 1차 러빙과 반대 방향으로 러빙을 실시하여 도포된 마스크에서 개구된 부분이 1차 배향 부분과 반대 방향으로 형성될 수 있는 기술을 제시하고 있으며, 이때, 1차 러빙 후 상층 배향막 층에 레지스트 (regist)를 도포하고 패턴을 갖는 형태로 빛을 조사하여 패턴으로 노광되는 레지스트 (regist)를 현상하면 이 현상액에 의하여 상층 측 배향층이 에칭 (etching)되고 하층 측 배향층은 노출되어지며 2차 러빙을 실시함으로써 1차 러빙과 다른 방향으로 배향된 배향막을 형성하였으나, 과정이 복잡하고 화학물질인 현상액을 사용함으로써 액정의 배향성능이 저하될 수 있는 문제점이 있으며, 마스크를 패턴된 형태로 부착하는 과정에서 정교하게 부착하기에 어려울 수 있는 단점이 있다.  That is, in Japanese Patent No. 2650205, first, a rubbing process is performed in one direction, and then the mask is applied in a patterned form, and then the rubbing is performed in a direction opposite to the first rubbing, so that the opened part of the applied mask has It proposes a technique that can be formed in the opposite direction, in this case, by applying a resist to the upper alignment layer layer after the first rubbing and irradiating light in the form of a pattern to develop a resist exposed in the pattern The developer was etched by the developer, the underlying layer was exposed, and second rubbing was performed to form an alignment film oriented in a direction different from the first rubbing. There is a problem that the alignment performance of the liquid crystal can be lowered by using a, and the fineness in the process of attaching the mask There is a disadvantage that may be difficult to attach.
또한, 일본 등록 특허 제 3596727호에서는 패턴된 제 1의 영역과 제 2의 영역에 있어서, 먼저 게 1의 영역을 마스크로 도포하고 계 2의 영역은 노출 시킨 후, 1차 러빙을 실시하고 마스크를 제거한 뒤, 복굴절 층을 설치하고 2차 러빙을 실시함으로써 패턴된 위상지연 필름을 제조하는 방법을 제시하였으나, 공정 단계가 복잡하고 마스크를 패턴함에 있어서 서로 배향이 다른 영역 간의 경계선이 불분명하게 형성될 수 있는 단점이 있다. 더욱이 배향 공정이 1회 추가될 때마다, 공정 속도는 느려지게 되고, 이는 생산성 하락의 가장 큰 원인이 된다. 이로 인해 제품의 가격이 상승하는 원인을 초래할 수 있다. In Japanese Patent No. 3596727, in the first and second patterned areas, first, the area of crab 1 is coated with a mask, and the area of area 2 is exposed, and then first rubbing is performed and the mask is applied. Remove the birefringence layer The present invention proposes a method for manufacturing a patterned phase delay film by installing and performing secondary rubbing, but there is a disadvantage in that a process line is complicated and a boundary line between areas having different orientations may be unclear in patterning a mask. Moreover, each time an orientation process is added, the process speed is slowed down, which is the biggest cause of the decrease in productivity. This may cause the price of the product to rise.
본 발명에서는 상기와 같은 문제점을 해결하기 위하여 서로 다른 종류의 배향제를 일정간격으로 교차되도록 프린팅하고, 1회 배향 공정을 통하여 패턴된 위상지연필름을 제조함으로써, 패턴의 경계 지점의 직진도가 우수하여 정교한 패턴의 형성이 가능하고 공정을 단순화시킬 수 있음을 확인하고 본 발명을 완성하게 되었다.  In the present invention, in order to solve the above problems by printing different types of alignment agents to cross at a predetermined interval, and by manufacturing a patterned phase delay film through a single alignment process, the straightness of the boundary point of the pattern is excellent By confirming that it is possible to form a sophisticated pattern and simplify the process has been completed the present invention.
【발명의 내용】  [Content of invention]
[해결하려는 과제】  Problem to be solved
본 발명은 1회 배향 공정에 의하여 패턴된 위상지연 필름을 제조하는 방법 및 패턴된 위상지연 필름을 제공하는 것이다.  The present invention provides a method for producing a patterned phase delay film and a patterned phase delay film by a single alignment process.
【과제의 해결 수단】  [Measures of problem]
본 발명은 (a) 기판 상에 서로 다른 종류의 배향제를 일정간격으로 교차되도록 형성하는 단계; (b) 상기 배향제가 프린팅된 기판에 배향성을 형성시키는 단계; 및 (c) 상기 배향성이 형성된 기판 상에 광 경화성 액정 단량체 조성물을 코팅하고 경화하는 단계를 포함하는 패턴된 위상지연필름 (patterned phase retardation film)의 제조방법 및 상기 방법으로 제조된 패턴된 위상지연필름을 제공한다.  The present invention comprises the steps of (a) forming different types of alignment agents to cross at regular intervals on the substrate; (b) forming an orientation on the substrate on which the alignment agent is printed; And (c) coating and curing the photocurable liquid crystal monomer composition on the alignment-formed substrate, and a patterned phase retardation film prepared by the method. To provide.
【발명의 효과】  【Effects of the Invention】
본 발명에 따른 패턴된 위상지연필름 제조방법은 서로 다른 배향성을 가지는 이종의 배향제를 프린팅 기술을 이용하여 일정간격으로 교차되도록 기판 상에 형성하므로, 기존의 마스크를 이용한 공정에 비하여 월등하게 향상된 패턴의 직진성을 나타내어 정교한 위상지연필름을 제조할 수 있고, 단 1회의 배향성 형성 공정으로 패턴된 위상지연필름의 제조가 가능하므로 종래 기술에 비하여 제조 공정이 반으로 줄어들어 공정의 간소화 및 그에 따른 비용 절감의 효과가 뛰어나다. In the method of manufacturing a patterned phase delay film according to the present invention, since different types of alignment agents having different orientations are formed on the substrate so as to intersect at regular intervals using a printing technique, the pattern is significantly improved compared to a process using a conventional mask. It is possible to manufacture a precise phase delay film by showing the straightness of, and to produce a phase delay film patterned by only one orientation forming process, the manufacturing process is reduced by half compared to the prior art, simplifying the process and Excellent cost savings.
【도면의 간단한 설명】  [Brief Description of Drawings]
도 1은 실시예 1에 의해 제작된 패턴 위상지연필름을 편광 현미경으로 관찰한 이.미지를 나타낸 것이다.  1 shows an image obtained by observing a patterned phase delay film prepared in Example 1 with a polarization microscope.
도 2는 실시예 2에 의해 제작된 패턴 위상지연필름을 편광 현미경으로 관찰한 이미지를 나타낸 것이다.  Figure 2 shows the image observed by the polarizing microscope the pattern phase retardation film produced in Example 2.
도 3은 비교예 1에 의해 제작된 패턴 위상지연필름을 편광 현미경으로 관찰한 이미지를 나타낸 것이다.  Figure 3 shows an image of the pattern retardation film produced by Comparative Example 1 observed with a polarizing microscope.
【발명을 실시하기 위한 구체적인 내용】  [Specific contents to carry out invention]
달리 정의되지 않는 한, 본 명세서에서 사용된 모든 기술적 및 과학적 용어들은 본 발명이 속하는 기술 분야에서 숙련된 전문가에 의해서 통상적으로 이해되는 것과 동일한 의미를 갖는다. 일반적으로, 본 명세서에서 사용된 명명법 및 이하에 기술하는 실험 방법은 본 기술 분야에서 잘 알려져 있고 통상적으로 사용되는 것이다.  Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein and the experimental methods described below are well known and commonly used in the art.
- 본 발명에서는 위상지연필름의 패턴을 형성하기 위하여 마스크를 사용하지 않고, 배향제의 종류가 서로 다른 2종의 배향제를 사용하여 1회의 배향성 형성 공정으로 패턴된 위상지연필름이 제조될 수 있도록 하였다. 따라서, 본 발명은 일 관점에서, (a) 기판 상에 서로 다른 종류의 배향제를 일정간격으로 교차되도록 형성하는 단계; (b) 상기 배향제가프린팅된 기판에 배향성을 형성시키는 단계; 및 (c) 상기 배향성이 형성된 기판 상에 광 경화성 액정 단량체 조성물을 코팅하고 경화하는 단계를 포함하는 패턴된 위상지연필름 (patterned phase retardation film)의 제조방법에 관한 것이다. 원하는 패턴 간격의 위상지연필름을 제조하기 위해서는 위상지연필름에서 요구되는 패턴의 간격을 고려하여 서로 다른 종류의 배향제를 일정간격으로 교차돠도록 형성하는 것이 요구된다. 본 발명에 있어서ᅳ 서로 다른 종류의 배향제가 형성되는 간격은 40 내지 1000 인 것을 특징으로 할 수 있으며, 이는 완성된 패턴된 위상지연필름에서 요구되는 패턴의 간격에 따라 유동적으로 간격을 조정할 수 있어야 하기 때문이다. 본 발명의 패턴된 위상지연필름이 액정 디스플레이 패널쎄 장착되어 사용된다면 액정 디스플레이 패널의 영상 표시 라인에 맞도록 위상지연필름의 패턴의 간격을 조절해야 할 것이다. 입체 영상을 구현하기 위한 패턴된 위상지연필름에 사용되기 위한 일 구현예로서, 본 발명에서 배향제가 형성, 예를 들어, 프린팅되는 간격은 바람직하게는 180 내지 220 가 될 수 있다. 서로 다른 종류의 배향제가 일정간격으로 교차된다는 것은 본 발명의 실시예에서 제조한 것과 같이 두 종의 배향제가 라인 별로 교대로 교차되며, 일정 간격을 이룬다는 것을 의미한다. In the present invention, without using a mask to form a pattern of the phase retardation film, the patterned phase delay film can be produced in a single alignment formation process using two types of alignment agents having different types of alignment agents. It was. Therefore, in one aspect, the present invention comprises the steps of: (a) forming different types of alignment agents on the substrate to be crossed at regular intervals; (b) forming an orientation on the substrate on which the alignment agent is printed; And (c) coating and curing the photocurable liquid crystal monomer composition on the substrate on which the alignment is formed. In order to manufacture a phase delay film having a desired pattern interval, it is required to form different types of alignment agents to cross at regular intervals in consideration of the pattern interval required in the phase delay film. In the present invention, the interval at which the different types of alignment agents are formed may be characterized in that 40 to 1000, which should be able to be adjusted fluidly according to the interval of the pattern required in the completed patterned retardation film Because. The patterned retardation film of the present invention is a liquid crystal display panel If mounted and used, it is necessary to adjust the pattern spacing of the phase delay film to match the image display line of the liquid crystal display panel. As one embodiment for use in the patterned phase delay film for realizing a stereoscopic image, in the present invention, the interval at which the alignment agent is formed, for example, printed, may be preferably 180 to 220. When different types of alignment agents are crossed at regular intervals, it means that two types of alignment agents alternate alternately line by line and form a predetermined interval as manufactured in the embodiment of the present invention.
서로 다른 종류의 배향제를 프린팅하는 기술은 잉크젯 (inkjet), 마이크로 그라비아 (micra-gravure), 오프셋 (offset), 스크린 (screen) 프린팅 등을 이용하는 것이 가능하다. 잉크젯 프린팅은 잉크를 분사하거나 잉크를 뭉쳐서 분사하는 인쇄하는 방법이며, 그라비아 프린팅은 요판 인쇄법 중 하나로, 미세한 농담을 표현할 수 있어 사진 인쇄에 적합한 프린팅 기법이다. 또한 오프셋 프린팅은 판에서 직접 피 인쇄물에 인쇄를 하지 않고, 중개 구실을 하는 고무 블탱킷에 일단 전사 인쇄한 다음, 용지에 인쇄하는 방법이고, 스크린 프린팅은 큰 규모의 기계를 쓰지 않는 핸드 프린트의 일종으로, 재료를 판자에 붙이고 한 장씩 프린트하는 것을 말한다. 실크 스크린, 불록 프린트라고도 한다. 이외에도 투명한 기판 위에 패턴 간격에 따라서 프린팅이 가능한 기술을 이용하여 동일한 효과를 부여할 수 있는 프린팅 기법을 사용할 수 있다. 본 발명에서는 이러한 프린팅 기법을 사용하여 서로 다른 종류의 배향제를 정교하게 일정 간격으로 프린팅함으로써, 경계지점의 직진성이 정교하고 우수한 패턴된 위상지연필름을 제조하는 것이 가능하도록 하였다.  Techniques for printing different kinds of alignment agents may use inkjet, microgravure, offset, screen printing and the like. Inkjet printing is a method of printing by ejecting ink or by agglomerating ink, and gravure printing is one of intaglio printing methods, and is a printing technique suitable for photo printing because it can express minute shades. In addition, offset printing is a method that does not print directly on a printed matter from a plate, transfers it to a rubber blanket that acts as an intermediary, and then prints on paper, and screen printing is a kind of hand print that does not use a large-scale machine. By attaching the material to the board and printing one by one. Also called silk screen, block print. In addition, a printing technique capable of giving the same effect by using a technology capable of printing on a transparent substrate according to pattern spacing may be used. In the present invention, by using the printing technique to precisely print different types of alignment agents at regular intervals, it is possible to produce a patterned phase delay film having a precise and excellent straightness of the boundary point.
서로 다른 종류의 배향제가 일정간격으로 프린팅 되어 있는 기판 상에 배향성을 형성하게 되면, 배향제마다 배향성의 방향이 다르게 형성되기 때문에, 일정간격으로 서로 다른 방향의 배향성이 교차되도록 형성되는 것이 가능하다. 이는 서로 다른 종류의 배향제가 동일한 방향의 배향성 형성 공정에 의하여 서로 다른 방향의 배향성이 형성된다는 점에 기인한다. 따라서, 일정간격으로 서로 직교인 배향성이 형성되도록 하고자 하는 경우, 서로 다른 종류의 배향제 중 일종의 배향제는 배향성 형성 방향과 평행하게 배향성이 형성되고, 다른 종의 배향제는 배향성 형성 방향과 직교 방향으로 배향성이 형성되도록 구성하는 것이 바람직할 것이다. When different types of alignment agents are formed on the substrate on which the alignment agents are printed at regular intervals, since the orientations of the alignment agents are differently formed for each of the alignment agents, it is possible to be formed such that the orientations in different directions cross at regular intervals. This is due to the fact that different kinds of alignment agents form alignment in different directions by an alignment forming process in the same direction. Therefore, when it is desired to form orthogonality perpendicular to each other at regular intervals, one type of alignment agent among different types of alignment agents may be parallel to the direction in which the alignment is formed. Orientation will be formed, and it will be preferable to comprise so that the other type of alignment agent may form orientation in the direction orthogonal to the orientation formation direction.
서로 다른 배향제의 종류는 배향성 형성 공정에 따라 달라지게 된다. 배향성을 형성시키기 위하여 러빙 (rubbing) 공정을 사용한다면, 그에 맞도록 러빙 배향제가 사용되어야 한다. 러빙 공정은 기판을 물리적으로 한쪽 방향으로 쓸어주어 배향성을 형성시키는 공정이다. 기판에 천이나 나일론과 같은 러빙 포가 직접적으로 접촉하여 배향 효과를 부여하는 방식이기 때문에, 접촉식 방식이 지닐 수 있는 정전기, 먼지 발생과 같은 문제가 발생할 수 있지만, 여타 비접촉식 (광배향, 이온빔 등) 방식과 비교하여 빠른 공정 속도를 나타낸다. 본 발명에 있어서, 배향성 형성 공정을 위하여 러빙 공정을 사용하는 경우, 상기 서로 다른 배향제는 각각 러빙 방향과 평행으로 배향성이 형성되는 배향제와 러빙 방향과 직교 방향으로 배향성이 형성되는 배향제로 되는 것을 특징으로 할 수 있다.  Different kinds of alignment agents will depend on the alignment forming process. If a rubbing process is used to form the orientation, then a rubbing alignment agent must be used accordingly. A rubbing process is a process of physically sweeping a board | substrate in one direction, and forming orientation. Since the rubbing cloth such as cloth or nylon comes into direct contact with the substrate to give an orientation effect, it may cause problems such as static electricity and dust generation that the contact method may have, but other non-contact types (photo-alignment, ion beam, etc.) It shows a faster process speed compared to the method. In the present invention, when the rubbing process is used for the orientation forming process, the different aligning agents may be an aligning agent in which the alignment is formed in a direction perpendicular to the rubbing direction and an alignment agent in which the alignment is formed in parallel with the rubbing direction, respectively. It can be characterized.
본 발명에 있어서, 러빙 방향과 평행으로 배향성이 형성되는 배향제는 폴리이미드 (polyimide), 폴리비닐알코올 (poly vinyl alcohol), 폴리아믹산 (polyamic acid), 폴리아미드 (polyamide) 및 폴리옥시에틸렌 (polyoxyethylene)으로 구성된 군에서 선택될 수 있으며, 러빙 방향과 직교 방향으로 배향성이 형성되는 배향제는 하기 화학식 1의 폴리스타일렌 (polystylene), 화학식 2의 CBDA-FDA PI (poly-(4,4'-(9,9- fluorenyl)diphenylene cyclobutanyltetracarboximide), 화학식 3의 C4-PMDA- PDA PI (poly{p-pheylene 3,6-bis[4-(n-butoxy)phenyloxy] pyromellitimide}, 화학식 4의 SBF-CBDA PI (poly(2,7-(9,9'-spirobifluorene cyclobutyltetracarboximide)), 및 화학식 5의 SBF-6FDA (poly(2,7-(9,9'- spirobifluorene 4,4'-(hexafluoroisopropylidene)diphthalimide))≤. 구성된 군에서 선택될 수 있으며, 이에 제한되지 않고 러빙 방향과 직교 방향으로 배향성이 형성되는 배향제라면 본 발명의 범위에 속한다고 할 것이다. 본 발명의 일 실시예에서는 CBDA-FDA PI를 사용하여 러빙 배향을 실시하는 경우 러빙 방향과 직교 방향으로 배향성이 형성되는 것을 확인할 수 있었다. 【화학식 1】
Figure imgf000009_0001
In the present invention, the alignment agent is formed in parallel with the rubbing direction, polyimide, polyvinyl alcohol, polyamic acid, polyamide and polyoxyethylene It can be selected from the group consisting of, wherein the aligning agent to form the orientation in the direction perpendicular to the rubbing direction (polystylene) of the formula (1), CBDA-FDA PI (poly- (4,4 '-( 9,9-fluorenyl) diphenylene cyclobutanyltetracarboximide), C4-PMDA-PDA PI of formula 3 (poly {p-pheylene 3,6-bis [4- (n-butoxy) phenyloxy] pyromellitimide}, SBF-CBDA PI of formula 4 (poly (2,7- (9,9'-spirobifluorene cyclobutyltetracarboximide)), and SBF-6FDA of formula 5 (poly (2,7- (9,9'-spirobifluorene 4,4 '-(hexafluoroisopropylidene) diphthalimide)) It can be selected from the group consisting of, not limited to this alignment agent is formed in the orientation perpendicular to the rubbing direction Intended to be within the scope of the invention. In one embodiment of the invention In the practice of the rubbing alignment with the FDA-PI CBDA at a rubbing direction and a direction orthogonal to it it was confirmed that the orientation is formed. [Formula 1]
Figure imgf000009_0001
【화학식 2】
Figure imgf000009_0002
[Formula 2]
Figure imgf000009_0002
【화학식 3]
Figure imgf000009_0003
[Formula 3]
Figure imgf000009_0003
【화학식 4】
Figure imgf000009_0004
[Formula 4]
Figure imgf000009_0004
【화학식 5】 [Formula 5]
Figure imgf000010_0001
본 발명에서 상기 (b) 단계의 배향성 형성은 앞에서 설명한 러빙 공정에 의한 것 이외에, 한쪽 방향으로 편광된 광을 조사하여 배향성을 형성시키는 광배향 공정에 의하여 이루어지는 것을 특징으로 할 수 있다. 상기 공정은 빛을 조사하는 공정만으로 배향을 시킬 수 있는 비접촉 방식의 공정으로서, 일반적으로 광중합 (photo-dimerization), 광이성질화 (photo- isomerization) 및 광분해 (photo-decomposition) 방식으로 분류할 수 있다. 특히 광분해 방식은 300 nm 이하의 단파장의 편광된 빛을 이용하여 배향막의 고분자 사슬을 분해시킴으로써, 배향력을 형성하는 원리를 갖는다. 즉 한쪽 방향으로 편광된 선편광의 빛을 광배향제에 조사하면, 광배향제의 분자구조가 변형되면서 일정한 배향성이 형성된다. 광 배향을 위한 광은 10 내지 200mW/cm2 로 편광된 ,자외선을 사용할 수 있다. 단, 광배향을 형성하기 위한 최소의 광 세기는 광배향제의 분자 구조와 광 개시제에 따라 달라질 수 있다. 즉, 광배향제의 분자 구조를 변형시키거나 광 개시제를 활성화할 수 있는 최소 광 에너지량이 광배향을 위한 최소 광 세기라 명명할 수 있다.
Figure imgf000010_0001
In the present invention, in addition to the rubbing process described above, the orientation formation in step (b) may be performed by a photoalignment process for forming orientation by irradiating light polarized in one direction. The process is a non-contact process that can be oriented by only a light irradiation process, generally can be classified by photo-dimerization, photo-isomerization and photo-decomposition method. have. In particular, the photolysis method has a principle of forming an alignment force by decomposing the polymer chain of the alignment layer using polarized light having a short wavelength of 300 nm or less. That is, when the light of linearly polarized light polarized in one direction is irradiated to the photoalignment agent, the molecular structure of the photoalignment agent is deformed, and thus a uniform orientation is formed. Light for optical alignment can be used for the ultraviolet polarized light of 10 to 200mW / cm 2. However, the minimum light intensity for forming the photoalignment may vary depending on the molecular structure and photoinitiator of the photoalignment agent. That is, the minimum amount of light energy capable of modifying the molecular structure of the photoalignment agent or activating the photoinitiator may be referred to as the minimum light intensity for photoalignment.
배향성을 형성하는 공정이 광 배향에 의하여 이루어지는 경우, 그에 맞도록 광배향제가 사용되.어야 한다. 본 발명에서, 서로 다른 배향제는 각각 조사되는 광의 편광 방향과 평행으로 배향성이 형성되는 배향제와, 조사되는 광의 편광 방향과 직교 방향으로 배향성이 형성되는 배향제로 될 수 있다. 상기 조사되는 광의 편광 방향과 평행으로 배향성이 형성되는 배향제는 폴리이미드 (polyimide), 폴리아믹에시드 (polyamic acid), 폴리노보넨 (p이 ynorbornene), 페닐말레이미드 공중합체 (phenylmaleimide copolymer), 플리아조벤젠 (polyazobenzene), 폴리에틸렌이민 (polyethyleneimide), 폴리비닐알콜 (polyvinyl alcohol), 폴리에틸렌 (pcilyethylene), 폴리스타일렌 (polystylene), 폴리페닐렌프탈아미드 (polyphenylenephthalamide), 폴리에스테르 (polyester), 폴리메틸 메타크릴레이트 (polymethyl methacrylate) 및 CBDA-FDA PI (poly- (4,4'-(9,9-fluorenyl)diphenylene cyclobutanyltetracarboximide)로 구성된 군에서 선택되는 것을 특징으로 할 수 있으며, 상기 조사되는 광의 편광 방향과 직교 방향으로 배향성이 형성되는 배향제는 하기 화학식 6의 CMPI (Chloromethylated polyimide) 및 화학식 7의 폴리비닐신나메이트 (polyvinylcinamate; PVCi)로 구성된 군에서 선택되는 것을 특징으로 할 수 있으나, 이에 제한되지 않고 조사되는 광의 편광 방향과 직교 방향으로 배향성이 형성되는 배향제라면 본 발명의 범위에 속한다고 할 것이다. If the process of forming the orientation is made by photo alignment, then a photoalignment agent should be used to suit it. In the present invention, the different alignment agents may each be an alignment agent in which the orientation is formed in parallel with the polarization direction of the irradiated light, and an alignment agent in which the orientation is formed in the direction orthogonal to the polarization direction of the irradiated light. The alignment agent is formed in parallel with the polarization direction of the irradiated light, polyimide, polyamic acid, polynorbornene (p ynorbornene), phenylmaleimide copolymer, poly Azobenzene (polyazobenzene), Polyethyleneimide, polyvinyl alcohol, polyethylene, polystylene, polyphenylenephthalamide, polyester, polymethyl methacrylate and CBDA-FDA PI (poly- (4,4 '-(9,9-fluorenyl) diphenylene cyclobutanyltetracarboximide) may be selected from the group consisting of, the orientation is formed in a direction perpendicular to the polarization direction of the irradiated light The alignment agent may be selected from the group consisting of CMPI (Chloromethylated polyimide) of Formula 6 and polyvinylcinamate (PVCi) of Formula 7, but is not limited thereto. If it is an aligning agent in which orientation is formed, it will be said to belong to the scope of the present invention.
【화학식 6】 ' [Formula 6] '
Figure imgf000011_0001
Figure imgf000011_0001
CMPᅵ는 기존의 폴리이미드 (P이 yimide; PI)에 클로로메틸 그룹 (chloromethyl group)을 치환 함으로써 기존의 폴리이미드보다 용해성이 좋은 장점을 갖고 있으며 용매의 끓는점이 높아 필름 경화 시 공정의 난이도가 쉬워지는 장점이 있으며, 편광된 UV를 조사해 주면 이 광에 의해서 분자가 비등방적인 분해를 일으키게 되고 생성된 비등방적인 구조로 인하여 액정 이 배향되 게 된다. 일반적으로 pi는 여타 광 배향재에 비하여 열적 안정성 이 높은 장점을 갖고 있다. CMPI는 4,4'- (Hexafluoroisopropylidene) diphthalic anhydride(6FDA) 와 4,4'- Diaminodiphenylether를 NMP에 녹여 중합한 후에 피 리딘 (pyridine)과 아세트산 무수물 (Acetic anhydride)을 사용하여 화학적 이미드화 (chemical imidization)를 한다. 그 후에 클로로메틸 메틸 에 테르 (chloromethyl methyl ether, CMME)와 염화제이주석 (tin(IV) chloride)을 사용하여 클로로 메틸화 반웅 (chloromethylation)을 통한 방법으로 수득할 수 있다. CMP has the advantage of better solubility than the existing polyimide by replacing the chloromethyl group with the existing polyimide (P), and the boiling point of the solvent makes the process difficult during film curing When the light is irradiated with polarized UV light, the light causes anisotropic decomposition of the molecule, resulting in an anisotropic structure. As a result, the liquid crystal is aligned. In general, pi has a high thermal stability compared to other photo-alignment material. CMPI was prepared by dissolving 4,4'- (Hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 4,4'-diaminodiphenylether in NMP to polymerize, followed by chemical imidization using pyridine and acetic anhydride. ) After that, it can be obtained by chloromethylation method using chloromethyl methyl ether (CMME) and tin (IV) chloride.
또한, PVCi는 광배향 재료로서 편광된 빛을 조사해주면 빛의 편광 방향과 직교한 방향으로 배향되는 재료로서 널리 알려져 있지만 광배향 메커 니즘은 아직도 논란이 되고 있으며, 그 내용은 광 조사로 인한 cis/trans isomerization에 의한 것과 이 량체 (dimer)에서의 벤젠 그룹 (benzene group)의 배향성 에 따른 것을 예로 들 수 있다. 이 러 한 논란에도 불구하고 광 배향 메커 니즘에 대한 주장들의 공통점은 배향막 내에서의 구조적 인 이방성과 액정과의 상호작용으로 인하여 배향이 일어난다는 것이다. 상기 PVCi는 폴리비닐알코을 (Polyvinylalcohol)에 신나메이트 그룹 (cinnamate group)을 에 테르화 반응 (etherification)을 통해 치환 함으로서 수득할 수 있다.  In addition, PVCi is widely known as a material that is oriented in a direction orthogonal to the polarization direction of light when irradiated with polarized light as a photo-alignment material, but the photo-alignment mechanism is still controversial, and the content of cis / Examples are by trans isomerization and by the orientation of benzene groups in dimers. In spite of this controversy, the common point of claims about the photo alignment mechanism is that the alignment occurs due to the structural anisotropy in the alignment film and the interaction with the liquid crystal. The PVCi can be obtained by substituting polyvinylalcohol (Polyvinylalcohol) with cinnamate group (cinnamate group) through etherification.
본 발명 에서 사용 가능한 기판은 85% 이상의 광학적 투명성을 지닌 기 재인 것 이 바람직하며, PES(p이 yether sulfone), Pl(polyimide), COP(cyclo olefin polymer), PET(polyethylene terephthalate), TAC(triacetyl cellulose), PC(poly carbonate) 및 유리로 구성된 군에서 선택되는 것을 특징으로 할 수 있다. 상기 한정된 재료들은 당해 업 계에서 일반적으로 사용 가능한 재료들이며, 당업자가 용이하게 변경하여 사용할 수 있는 재료에 대하여 고정 적 인 조건은 아니다.  The substrate usable in the present invention is preferably a substrate having an optical transparency of more than 85%, PES (p is yether sulfone), Pl (polyimide), COP (cyclo olefin polymer), PET (polyethylene terephthalate), TAC (triacetyl) It may be characterized in that it is selected from the group consisting of cellulose), PC (poly carbonate) and glass. The limited materials are materials generally available in the industry, and are not fixed conditions for materials that can be easily changed and used by those skilled in the art.
기판 상에 프린팅된 배향제에 패턴된 배향성 이 부여되면, 광경화성 액정 단량체 조성물을 코팅하여 경화시 키 는 공정을 통하여 위상지 연필름을 완성할 수 있다. 광경화성 액정 단량체 (reactive mesogen; RM)는 패턴 배향된 기판 위 에 코팅되고, 자외선 등에 의해서 경화되어 광 경화성 액정 단량체 층을 형성하며, 상기 광 경화성 액정 단량체 층은 편광된 빛의 위상을 지연시키는 역할을 하게 된다. 본 발명에 따른 패턴된 위상지연필름은 패턴된 부분에 따라 위상 지연의 방향 및 크기가 다르며, 일정 간격으로 교대로 위상 지연 방향 /크기가 다르도록 구성된다. When the patterned orientation is imparted to the alignment agent printed on the substrate, the phase paper pencil may be completed through a process of coating and curing the photocurable liquid crystal monomer composition. A photocurable liquid crystal monomer (RM) is coated on a pattern oriented substrate and cured by ultraviolet rays or the like to form a photocurable liquid crystal monomer layer, wherein the photocurable liquid crystal monomer layer is formed of polarized light. This will delay the phase. The patterned retardation film according to the present invention is different in the direction and size of the phase retardation according to the patterned portion, it is configured to alternately phase retardation direction / size at regular intervals.
본 발명에 있어서, 상기 광경화성 액정 단량체 조성물은 중합성기를 가지는 액정성 화합물로 특히, 아크릴기, 비닐에테르기 또는 에폭사이드의 관능기를 가질 수 있으며, 광경화성 액정 단량체 조성물의 조성흔합물은 중합체의 가교결합을 증가시키기 위해 2개 이상의 중합성 작용기, 예를 들면 일반웅성 대 이반응성 화합물 및 /또는 비극성 대 극성 화합물을 갖는 중합성 메소겐 화합물을 흔합하여 사용할 수 있고, 그들의 조성비를 변화시킴으로써 정렬 프로필을 변경시킬 수도 있다.  In the present invention, the photocurable liquid crystal monomer composition is a liquid crystal compound having a polymerizable group, in particular, may have a functional group of an acrylic group, a vinyl ether group or an epoxide, the composition of the photocurable liquid crystal monomer composition is a crosslinking of the polymer In order to increase the bond, polymerizable mesogenic compounds having two or more polymerizable functional groups, for example general male to direactive and / or nonpolar to polar compounds can be used in combination, and the alignment profile can be changed by changing their composition ratio. You can also change it.
광경화성 액정 단량체 층의 두께를 조절하면 위상 지연 크기를 조절하는 것이 가능하며, 위상지연의 크기가 λ/4인 경우 선편광을 원편광으로 바꾸어 줄 수 있다. 상기 λ는 위상이 자연될 광의 파장을 가리키는 부호이다. 광경화성 액정 단량체의 위상 지연은 분자 구조에 있어서, 장축과 단축의 굴절율에 의해 이루어지며, 그 차이가 0.7 내지 3 인 것이 바람직하다. 또한, 기재에 코팅을 실시해야 하기 때문에, 유기 용매에 일정량 흔합되어 사용되어야 한다. 상기 비율은 5~50%가 바람직하며, 코팅을 용이하기 하기 위한 비율일 뿐, 고정적인 값이 아님은 자명할 것이다. 본 발명에 있어서, 광경화성 액정 단량체 층은 스핀 (spin)ᅳ 콤마 (comma), 그라비아 (gravure), 딥 (dip), 슬롯 다이 (slot die), 실크 스크린 (silk screen), 잉크젯 프린팅 (inkjet printing) 등의 공지의 코팅 공정을 적용하여 수행할 수 있다. 스핀 코팅으로 공정을 진행하는 경우, 400 ~ 1000rpm으로 20 - 25초 동안 1차 회전시키고, 2500 - 3500rpm에서 70 - 80초 동안 회전시키는 방법을 이용하여 두께 0.5 ~ 5 로 코팅한다. 코팅 후 경화 공정은 60°C에서 1분 건조 한 후, 20mW/cm2의 자외선을 1분 동안 조사하여 이루어지며, 이러한 조건은 광경화성 액정 단량체 재료의 특성에 따라 각각 다르다. By adjusting the thickness of the photocurable liquid crystal monomer layer, it is possible to adjust the phase delay size, and when the magnitude of the phase delay is λ / 4, the linearly polarized light may be changed into circularly polarized light. [Lambda] is a sign indicating a wavelength of light whose phase is to be natural. The phase retardation of the photocurable liquid crystal monomer is made by the refractive index of the long axis and the short axis in the molecular structure, and the difference is preferably 0.7 to 3. In addition, since the substrate should be coated, it should be used in a certain amount in an organic solvent. The ratio is preferably 5 to 50% and is only a ratio for facilitating the coating, and it will be apparent that the ratio is not a fixed value. In the present invention, the photocurable liquid crystal monomer layer includes spin ᅳ comma, gravure, dip, slot die, silk screen, inkjet printing. It is possible to carry out by applying a known coating process such as). When the process is carried out by spin coating, the coating is first coated with a thickness of 0.5 to 5 using a method of first rotating for 20 to 25 seconds at 400 to 1000 rpm and rotating for 70 to 80 seconds at 2500 to 3500 rpm. After coating, the curing process is performed by drying at 60 ° C. for 1 minute and irradiating with 20 mW / cm 2 ultraviolet rays for 1 minute. These conditions are different depending on the properties of the photocurable liquid crystal monomer material.
본 발명에 있어서, 일정 간격으로 패턴된 배향 방향이 서로 직교를 이루도록 구성되고, 이러한 기판 위에 광 경화성 액정 단량체 층이 λ/4 위상 지연 효과를 가지도록 도포 및 경화되면, 제조된 패턴된 위상지연 필름은 선편광된 빛을 좌원편광과 우원편광으로 바꿀 수 있다. 이렇게 제조된 위상지연 필름을 좌안 화상과 우안 화상을 분리한 패널 디스플레이에 장착하고, 좌원편광과 우원편광을 분리하는 편광안경을 사용하면 3D 입체영상을 구현하는 것이 가능하다. 이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 예시하기 위한 것으로, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되지 않는 것은 당업계에서 통상의 지식을 가진 자에게 있어서 자명할 것이다. In the present invention, the alignment directions patterned at regular intervals are configured to be orthogonal to each other, and the photocurable liquid crystal monomer layer on the substrate is lambda / 4 phase When applied and cured to have a delay effect, the prepared patterned phase delay film can convert linearly polarized light into left circularly polarized light and right circularly polarized light. The phase retardation film thus prepared is mounted on a panel display that separates the left eye image and the right eye image, and polarized glasses separating the left circular polarization and the right circular polarization can realize 3D stereoscopic images. Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not to be construed as being limited by these examples.
【실시예 1】 Example 1
1회 러빙 공정을통한패턴된 위상지연필름 제조  Manufacture of patterned phase delay film through one rubbing process
본 실시예에서는 서로 다른 배향 방향성을 가지는 두 종류의 러빙 배향,제를 일정 간격으로 프린팅하여, 1회의 러빙 공정으로 패턴된 위상지연필름을 제조하고자 하였다.  In this embodiment, two types of rubbing alignment agents having different orientation directions were printed at regular intervals, thereby preparing a phase delay film patterned by one rubbing process.
PI 필름을 5cm X 5cm의 크기로 준비하고, polyimide와 CBDA-FDA PI의 두 종의 배향제를 inkjet printing 장비 (Inkjet Printer; Dimatix co. Ltd)를 이용하여 그 폭이 1:1의 비율이 될 수 있도특 200im의 간격으로 stripe 형태의 printing을 실시하였다. 상기 polyimide는 GBL(gamma-Butyrolactone), NMP(N-Methl-2-Pyrrolidone), BC(2-Butoxyethanol)을 7:2:1로 섞은 용액에 대하여 총합의 질량비를 100으로 하였을 때 2%의 비율로 용해시켜 사용하였으며, CBDA-FDA-PI는 GBL에 질량비 2%로 용해시켜 사용하였다. 상기 Sc)lvent가 층분히 소성될 수 있도록 20CTC에서 15분간 건조 과정을 실시한 후, 도포된 stripe 형태에 대하여 사선방향으로 러빙 공정을 실시한다 즉 상기 pi 필름의 Machanical direction의 방향에 대하여 45° 방향으로 실시하였으며, 상기 러빙 공정은 러빙 depth 1mm, 를 회전 속도 600rpm, 20mm/sec의 stage 이동 속도의 조건으로 실시하였다.  Prepare the PI film in the size of 5cm x 5cm, and use the inkjet printing equipment (Inkjet Printer; Dimatix co. Ltd) for the two types of alignment agents, polyimide and CBDA-FDA PI, so that the width is 1: 1. Stripe-type printing was performed at intervals of 200im. The polyimide is a ratio of 2% when the total mass ratio is 100 to a solution mixed with GBL (gamma-Butyrolactone), NMP (N-Methl-2-Pyrrolidone), and BC (2-Butoxyethanol) at 7: 2: 1 CBDA-FDA-PI was used by dissolving in GBL at a mass ratio of 2%. After 15 minutes of drying at 20CTC, the rubbing process is carried out in an oblique direction on the applied stripe shape so that the Sc) lvent can be sufficiently fired. In other words, in the direction of 45 ° to the direction of the Machanical direction of the pi film. The rubbing process was carried out under the conditions of a rubbing depth of 1 mm, a rotational speed of 600 rpm, a stage moving speed of 20 mm / sec.
러빙 공정을 진행한 배향제 위에 광경화성 액정 단량체 (RMS-013C, Merck co. Ltd.)을 전면에 코팅 후, solvent가 층분히 날아갈 수 있도록 60°C에서 1분간 건조 과정을 실시하고, 20mW/cm2(at 365nm)로 1분간 노광 공정을 실시하여 광경화성 액정 단량체가 배향제 위에서 고착화될 수 있도록 하였다. Photocurable liquid crystal monomer (RMS-013C, on the alignment agent that proceeded the rubbing process Merck co. Ltd.) is coated on the entire surface, and the drying process is performed for 1 minute at 60 ° C so that the solvent can flow evenly, and the exposure process is performed for 1 minute at 20 mW / cm 2 (at 365 nm) to align the photocurable liquid crystal monomer. Allowed to settle on the altar.
이렇게 하여 제조된 위상지연필름을 복굴절 측정 장비 (REMS-100; Sesim co. Ltd)를 통해 기재의 복굴절을 측정하였으며, 편광현미경을 통해 그 폭 및 경계 지점의 직진 특성을 확인할 수 있었다. 실험은 5회에 걸쳐 반복 실험을 진행하였으며, 이렇게 측정된 결과를 하기 표 1에 나타내었고, 편광현미경을 통하여 관찰한사진을 도 1에 나타내었다.  The birefringence of the substrate was measured using the birefringence measuring device (REMS-100; Sesim co. Ltd), and the straightness characteristic of the width and the boundary point was confirmed through the polarization microscope. The experiment was repeated five times, and the measured results are shown in Table 1 below, and the photographs observed through the polarizing microscope are shown in FIG. 1.
도 1에서 나타난 바와 같이, 러빙 방향에 대하여 직교 방향으로 배향되는 배향제와 평행하게 배향되는 배향제를 일정 간격으로 교차되도록 프린팅하여, 1회 러빙 배향공정 만으로도 패턴된 위상지연필름을 제조할 수 있음을 확인하였다.  As shown in FIG. 1, by printing the alignment agents aligned in parallel with the alignment agents orthogonal to the rubbing direction so as to cross at regular intervals, the patterned phase delay film may be manufactured using only one rubbing alignment process. It was confirmed.
【표 1Table 1
실시예 1에 의해 제작된 패턴된 위상지연필름의 패턴 폭, 경계지점 값 및 복굴절 크기 Pattern width, boundary value and birefringence size of the patterned retardation film produced by Example 1
Figure imgf000015_0001
Figure imgf000015_0001
상기 표 1에서 폭은 1회 제조된 위상지연필름의 각 패턴 폭의 평균을 나타낸 것이고, 경계 지점은 패턴간 경계 지점을 직선으로 보았을 때 직선으로부터 벗어난 정도를 단위로 나타낸 것이며, 복굴절 값은 In Table 1, the width represents the average of the widths of the patterns of the phase-delay film prepared once, and the boundary points represent the degree of deviation from the straight line when viewed as a straight line between the patterns, and the birefringence value is
550nm의 입사 광에 대한 위상지연 값을 의미한다. 패턴 폭의 .값은 5회에 걸친 실험에서 기준 값인 200 에서 얼마나 벗어나며 균일한 값을 가지는 지 * 확인하기 위하여 평균값 및 표준편차 값을 나타내었으며, 경계 지점 및 복굴절 값은 5회 실험의 평균값을 나타내었다. 【실시예 2】 It means the phase delay value for the incident light of 550nm. The pattern width .value is 5 times In the experiments, the mean value and standard deviation value were shown to determine how far the standard value was and the uniform value was 200. The boundary point and the birefringence value represented the mean values of five experiments. Example 2
1회 광배향공정을 통한 패턴된 위상지연필름 제조  Patterned Phase Delay Film Manufactured by One-Optical Orientation Process
본 실시예에서는 서로 다른 배향 방향성을 가지는 두 종류의 광배향제를 일정 간격으로 프린팅하여, 1회의 광배향 공정으로 패턴된 위상지연필름을 제조하고자 하였다.  In this embodiment, two types of photo-alignment agents having different orientation directions were printed at regular intervals, thereby preparing a phase delay film patterned by one photo-alignment process.
PI 필름을 5cm X 5cm의 크기로 준비하고, CBDA-FDA PI (p y-(4,4'-Prepare a PI film in the size of 5 cm X 5 cm, CBDA-FDA PI (p y- (4,4 ' -
(9,9-fluorenyl)diphenylene cydobutanyltertracarboximide)와 CMPI(9,9-fluorenyl) diphenylene cydobutanyltertracarboximide) and CMPI
(Chloromethylated P이 yimide)의 의 두 종의 배향제를 inkjet printing 장비 (Inkjet Printer; Dimatix co. Ltd)를 이용하여 그 폭이 1:1의 비율이 될 수 있도록 200 의 간격으로 stripe 형태의 printing을 실시하였다. 상기 CBDA- FDA-PI는 GBL에 질량비 2%로 용해시켜 사용하였으며, CMPI는 cycbhexanone에 질량비 2%로 용해시켜 사용하였다. Two types of aligning agents of (Chloromethylated P yimide) were used in inkjet printing equipment (Inkjet Printer; Dimatix co. Ltd) to print in stripe form at intervals of 200 so that the width could be 1: 1. Was carried out. The CBDA-FDA-PI was used by dissolving at 2% by mass in GBL, and CMPI was used by dissolving at 2% by mass in cycbhexanone.
S이 vent가 층분히 소성될 수 있도록 2CK C에서 15분간 건조 과정을 실시한 후, 도포된 stripe 형태에 대하여 빛의 편광 방향이 사선방향인 자외선을 30mW/cm2(at 254nm)의 세기로 5분 동안 노광하여 주었다. After 15 minutes of drying at 2CK C to allow the vent to be fired evenly, S for 5 minutes at 30mW / cm 2 (at 254nm) intensity of UV light with a diagonal polarization direction for the applied stripe shape. Exposed for a while.
노광하여 배향성이 형성된 상기 배향제 위에 RM (RMS-013C, Merck co. Ltd.)을 전면에 코팅 후, solvent가 충분히 날아갈 수 있도록 60°C에서 1분간 건조 과정을 실시하고, 20mW/cm2(at 365nm)로 1분간 노광 공정을 실시하여 RM이 배향제 위에서 고착화될 수 있도록 하였다. After the RM (RMS-013C, Merck co. Ltd.) was coated on the entire surface of the alignment agent exposed to the alignment property, a drying process was performed at 60 ° C. for 1 minute so that the solvent was sufficiently blown, and 20mW / cm 2 ( at 365 nm) to allow the RM to settle on the alignment agent.
이렇게 하여 제조된 위상 지연 기재를 복굴절 측정 장비 (REMS-100; Sesim co. Ltd)를 통해 기재의 복굴절을 측정하였으며, 편광현미경을 통해 그 폭 및 경계 지점의 직진 특성을 확인할 수 있었다. 실험은 5회에 걸쳐 반복 실험을 진행하였으며, 이렇게 측정된 결과를 하기 표 2에 나타내었고, 편광현미경을통하여 관찰한사진을 도 2에 나타내었다.  The birefringence of the substrate was measured using the birefringence measuring device (REMS-100; Sesim co. Ltd), and the straightness characteristics of the width and the boundary point were confirmed through the polarization microscope. The experiment was repeated five times, and the measured results are shown in Table 2 below, and the photographs observed through the polarizing microscope are shown in FIG. 2.
도 2에서 나타난 바와 같이, 조사되는 광의 편광 방향에 대하여 직교 방향으로 배향되는 배향제와 평행하게 배향되는 배향제를 일정 간격으로 교차되도록 프린팅하여, 1회의 광배향 공정 만으로도 패턴된 위상지연필름을 제조할 수 있음을 확인하였다. As shown in FIG. 2, perpendicular to the polarization direction of the irradiated light It was confirmed that the patterned phase delay film could be produced by only one optical alignment process by printing the alignment agents aligned in parallel with the alignment agents aligned in the direction so as to cross at regular intervals.
【표 2】  Table 2
실시예 2에 의해 제작된 패턴된 위상지연필름의 패턴 폭, 경계지점 값 및 복굴절 크기 Pattern width, boundary value and birefringence size of the patterned retardation film produced by Example 2
Figure imgf000017_0001
Figure imgf000017_0001
상기 표 2에서 폭은 1회 제조된 위상지연필름의 각 패턴 폭의 평균을 나타낸 것이고, 경계 지점은 패턴간 경계 지점을 직선으로 보았을 때 직선으로부터 벗어난 정도를 /m 단위로 나타낸 것이며, 복굴절 값은 550nm의 입사 광에 대한 위상지연 값을 의미한다. 패턴 폭의 값은 5회에 ¾친 실험에서 기준 값인 200 에서 얼마나 벗어나며 균일한 값을 가지는 지를 확인하기 위하여 평균값 및 표준편차 값을 나타내었으며, 경계 지점 및 복굴절 값은 5회 실험의 평균값을 나타내었다. [비교예 1]  In Table 2, the width represents the average of the widths of the patterns of the prepared phase delay film once, and the boundary points represent the degree of deviation from the straight line when viewed in a straight line between the patterns in units of m, and the birefringence value is It means the phase delay value for the incident light of 550nm. The value of the pattern width was the average value and the standard deviation value to determine how far it was from the standard value 200 and the uniform value in the experiment that was five times, and the boundary point and the birefringence value were the average values of the five experiments. . Comparative Example 1
종래기술에 의한 패턴된 위상지연필름의 제조  Preparation of patterned phase delay film according to the prior art
본 비교예에서는 종래 기술에 의한 패턴된 위상지연필름을 제조하여, 본 발명에 따른 제조방법에 의해 제조된 패턴된 위상지연필름과 비교하고자 하였다.  In this Comparative Example, a patterned phase delay film prepared according to the prior art was compared with a patterned phase delay film manufactured by the manufacturing method according to the present invention.
PI 필름을 5cm X 5cm의 크기로 준비하고, 러빙 방향에 평행하게 배향 특성을 나타내는 배향제인 실시예 1 에서 사용하였던 polyimide를 전면에  A PI film was prepared in a size of 5 cm X 5 cm, and the polyimide used in Example 1, which is an alignment agent exhibiting orientation characteristics parallel to the rubbing direction, was placed on the front surface.
1.5 코팅하고, 코팅된 배향막에 1차 러빙을 러빙 depth 1mm, 를 회전 속도 600rpm, 20mm/sec의 stage 이동 속도의 조건으로 실시한 후, 개구부가 200um, 비개구부가 150 의 폭을 가지며 stripe 형태로 패턴을 나타내는 50 m 두께의 러빙 마스크를 그 상부에 위치시킨 후, 1차 러빙 방향에 대해 직교 방향으로 2차 러빙을 실시하였다. 상기 마스크의 개구부와 비개구부의 폭이 일치하지 않는 것은 마스크를 위치시킨 후 실시하는 2차 러빙 시 마스크의 두께에 의해 2차 러빙이 비개구부의 전면에 효과를 부여하지 못하기 때문이다. 따라서, 상대적으로 마스크의 개구부 폭을 비개구부의 폭보다 더 넓게 제작해야 한다. 1.5 After coating, the primary alignment was subjected to rubbing depth 1mm, rotational speed 600rpm, stage movement speed of 20mm / sec, and the opening was 200um and the non-opening was 150 width. After placing the rubbing mask of 50 m thickness shown in the upper part, secondary rubbing was performed in the direction orthogonal to a primary rubbing direction. The widths of the openings and the non-openings of the mask do not coincide because the second rubbing does not give the entire surface of the non-openings due to the thickness of the mask during the second rubbing performed after the mask is placed. Therefore, the opening width of the mask should be made relatively wider than the width of the non-opening portion.
상기 러빙 배향된 배향제 위에 광경화성 액정 단량체 (RMS-013C, Photocurable liquid crystal monomer (RMS-013C, on the rubbing oriented alignment agent,
Merck co. Ltd.)를 전면에 코팅 후, sc)lvent가 층분히 날아갈 수 있도록 60°C에서 1분간 건조 과정을 실시하고, 20mW/cm2(at 365nm)로 1분간 노광 공정을 실시하여 RM이 배향제 위에서 고착화될 수 있도록 하였다. Merck co. Ltd.) is coated on the entire surface, and the drying process is performed at 60 ° C for 1 minute, and the exposure process is performed at 20mW / cm 2 (at 365nm) for 1 minute so that the sc) lvent can be blown away. It can be fixed in the stomach.
상기의 과정을 거쳐 제작한 패턴 위상차 필름의 폭, 경계 지점, 복굴절 값을 하기 표 3에 도표화하였으며, 실험은 5회에 걸쳐 반복 실험으로 진행되었다. 또한 편광 현미경 (BX51, Olympus co. Ltd) 으로 관찰한 결과를 도 3에 나타내었다.  The width, boundary point, and birefringence value of the pattern retardation film produced through the above process are plotted in Table 3 below, and the experiment was performed by repeated experiments five times. Moreover, the result observed with the polarization microscope (BX51, Olympus co. Ltd) is shown in FIG.
【표 3】  Table 3
비교예 1에 의해 제작된 패턴된 위상지연필름의 패턴 폭, 경계지점 값 및 복굴절 크기 Pattern width, boundary value and birefringence of the patterned retardation film produced by Comparative Example 1
Figure imgf000018_0001
Figure imgf000018_0001
상기 표 3에서 폭은 1회 제조된 위상지연필름의 각 패턴 폭의 평균을 나타낸 것이고, 경계 지점은 패턴간 경계 지점을 직선으로 보았올 때 직선으로부터 벗어난 정도를 단위로 나타낸 것이며, 복굴절 값은In Table 3, the width is the width of each pattern of the prepared phase delay film The mean point is the average point, and the boundary point is the degree of deviation from the straight line when the boundary point between patterns is viewed as a straight line.
550nm의 입사 광에 대한 위상지연 값을 의미한다. 패턴 폭의 값은 5회에 걸친 실험에서 기준 값인 200mi에서 얼마나 벗어나며 균일한 값을 가지는 지를 확인하기 위하여 평균값 및 표준편차 값을 나타내었으며, 경계 지점 및 복굴절 값은 5회 실험의 평균값을 나타내었다. 표 1, 2 및 3에서 나타낸 바와 같이, 본 발명에 따른 제조방법에 의하여 제조된 패턴된 위상지연필름의 경우 패턴의 폭이 종래기술에 비하여 매우 안정적으로 형성이 되는 것을 확인할 수 있으며, 경계지점 값 또한 종래기술보다 월등히 적은 값을 나타내어 경계 지점의 직진성이 월등히 향상된 것을 확인할 수 ¾었다. It means the phase delay value for the incident light of 550nm. The value of the pattern width was the mean value and the standard deviation value in order to confirm how far it was from the standard value 200 mi and the uniform value in five experiments, and the boundary point and the birefringence value were the average values of the five experiments. As shown in Table 1, 2 and 3, in the case of the patterned phase delay film produced by the manufacturing method according to the present invention, it can be seen that the width of the pattern is formed more stably than the prior art, and the boundary point value In addition, it showed a much lower value than the prior art, it was confirmed that the straightness of the boundary point is significantly improved.
구체적으로는, 200/m을 기준으로 한 패턴 폭에 대하여, 실시예와 비교예에서 모두 평균값은 200/im에서 크게 벗어나지 않는 수치를 나타내었지만, 표준 편차를 비교하여 볼 때, 실시예 1은 14.9, 실시예 2는 6.2의 표준 편차를 나타내어 비교예의 40이 넘는 표준편차와 비교하여 매우 균일하게 패턴 폭이 형성된 것을 확인할 수 있다. 또한, 경계 지점이 직전성에서 벗어난 정도를 보면 실시예의 경우 이하로 나타난 것에 비하여 비교예는 40im이 넘게 벗어난 것으로 나타나, 본 발명의 위상지연필름의 경계 지점의 직진성 역시 종래기술에 비하여 월등히 향상된 것을 확인할 수 있었다. 패턴 폭 및 경계지점은 선택적 위치에 프린팅되는 기술에 의해 좌우되므로, 상기 공정은 정교한 프린팅 기술을 이용하여 실시하는 것이 좋은 효과를 나타낸다는 것을 확인할 수 있었다. 이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서 이러한 구체적 기술은 단지 바람직한 실시태양일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점을 명백할 것이다. 따라서, 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.  Specifically, for the pattern width on the basis of 200 / m, the average value in both Examples and Comparative Examples did not deviate significantly from 200 / im, but when comparing the standard deviation, Example 1 was 14.9. , Example 2 shows a standard deviation of 6.2, it can be seen that the pattern width is formed very uniformly compared to the standard deviation of more than 40 of the comparative example. In addition, when the degree of the boundary point is out of the immediateness, the comparative example is shown to deviate more than 40im compared to the case shown in the following case, the straightness of the boundary point of the phase delay film of the present invention is also confirmed to be significantly improved compared to the prior art Could. Since the pattern width and the boundary point depend on the technique printed at the selective position, it can be seen that the process has a good effect by using a sophisticated printing technique. Having described the specific part of the present invention in detail, it is apparent to those skilled in the art that such a specific technology is merely a preferred embodiment, thereby not limiting the scope of the present invention. something to do. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims

【특허청구범위】  [Patent Claims]
【청구항 1】  [Claim 1]
다음의 단계를 포함하는 패턴된 위상지연필름 (patterned phase retardation film)의 제조방법 :  Method of producing a patterned phase retardation film comprising the following steps:
(a) 기판 상에 서로 다른 종류의 배향제를 일정간격으로 교차되도록 형성하는 단계;  (a) forming different types of alignment agents on the substrate so as to cross at regular intervals;
(b) 상기 배향제가 프린팅된 기판에 배향성을 형성시키는 단계; 및 (b) forming an orientation on the substrate on which the alignment agent is printed; And
(c) 상기 배향성이 형성된 기판 상에 광 경화성 액정 단량체 조성물을 코팅하고 경화하는 단계. (c) coating and curing the photocurable liquid crystal monomer composition on the alignment formed substrate.
【청구항 2】 1 [Claim 2] 1
제 1 항에 있어서, 상기 (b) 단계의 진행 후에, 서로 다른 종류의 배향제는서로 다른 방향의 배향성이 교차되도록 형성되는 제조방법. 【청구항 3】  The method according to claim 1, wherein after the step (b) is performed, different types of alignment agents are formed so that the orientations in different directions cross each other. [Claim 3]
제 1 항에 있어서, 상기 (b) 단계의 진행 후에, 서로 다^ 종류의 배향제는서로 직교인 배향성이 교차되도록 형성되는 제조방법 .  The method according to claim 1, wherein after the step (b) proceeds, different types of alignment agents are formed so as to intersect orthogonality with each other.
【청구항 4】 [Claim 4]
제 1 항에 있어서, 상기 (b) 단계의 배향성 형성은 기판을 한쪽 방향으로 러빙 (rubbing)하여 이루어지는 제조방법.  The method of claim 1, wherein the forming of the orientation in step (b) is performed by rubbing the substrate in one direction.
【청구항 5】 [Claim 5]
제 4 항에 있어서, 상기 서로 다른 배향제는 각각 러빙 방향과 평행으로 배향성이 형성되는 배향제와, 러빙 방향과 직교 방향으로 배향성이 형성되는 배향제로 되는 제조방법.  The manufacturing method according to claim 4, wherein the different alignment agents are each an alignment agent in which orientation is formed in parallel with a rubbing direction, and an alignment agent in which orientation is formed in a direction perpendicular to the rubbing direction.
[청구항 6】 [Claim 6]
제 5 항에 있어서, 상기 러빙 방향과 평행으로 배향성이 형성되는 배향제는 폴리 이미드 (p이 yimide), 폴리비닐알코올 (poly vinyl alcohol), 폴리아믹산 (polyamic acid), 폴리 아미드 (p yamide) 및 폴리옥시에틸렌 (p0|yoxyethylene)으로 구성된 군에서 선택되는 제조방법 . 【청구항 7】 According to claim 5, Orientation is formed in parallel with the rubbing direction The aligning agent is selected from the group consisting of polyimide, polyvinyl alcohol, polyamic acid, polyamide and polyoxyethylene (p 0 | yoxye thylene) Manufacturing method. [Claim 7]
제 5 항에 있어서, 상기 러 빙 방향과 직교 방향으로 배향성 이 형성되는 배향제는 폴리스타일렌 (polystylene), CB DA-FDA PI (poly-(4,4'-(9,9- fluorenyl)diphenylene cyclobutanyltetracarboximide), SBF-CBDA PI (poly(2,7- (9,9'-spirobifluorene cyclobutyltetracarboximide)), 및 SBF-6FDA (poly(2,7- (9,9'-spirobifluorene 4,4'-(hexafluoroisopropylidene)diphthalimide))≤. 구성된 군에서 선택되는 제조방법 .  The method of claim 5, wherein the alignment agent is formed in a direction perpendicular to the rubbing direction, polystylene (polystylene), CB DA-FDA PI (poly- (4,4 '-(9,9-fluorenyl) diphenylene cyclobutanyltetracarboximide ), SBF-CBDA PI (poly (2,7- (9,9'-spirobifluorene cyclobutyltetracarboximide)), and SBF-6FDA (poly (2,7- (9,9'-spirobifluorene 4,4 '-(hexafluoroisopropylidene) diphthalimide)) ≤.Production method selected from the group consisting of.
【청구항 8】 [Claim 8]
제 1 항에 있어서, 상기 (b) 단계의 배향성 형성은 한쪽 방향으로 편광된 광을 조사하여 이루어지는 제조방법 . 【청구항 9】  The method according to claim 1, wherein the orientation formation in step (b) is performed by irradiating light polarized in one direction. [Claim 9]
제 8 항에 있어서 , 상기 광은 10 내지 100mW/cm2 로 편광된 자외선인 것을 특징으로 하는 제조방법 . The method of claim 8, wherein the light is ultraviolet light polarized at 10 to 100 mW / cm 2 .
【청구^ 10】 [Billing ^ 1 0]
제 8 항에 있어서, 서로 다른 배향제는 각각 조사되는 광의 편광 방향과 평 행으로 배향성 이 형성되는 배향제와, 조사되는 광의 편광 방향과 직교 방향으로 배향성 이 형성되는 배향제로 되는 제조방법 .  The manufacturing method according to claim 8, wherein the different alignment agents are each an alignment agent in which the orientation is formed in parallel with the polarization direction of the irradiated light, and an alignment agent in which the orientation is formed in the direction orthogonal to the polarization direction of the irradiated light.
【청구항 1 1】 [Claim 1 11]
제 10 항에 있어서, 상기 조사되는 광의 편광 방향과 평 행으로 배향성 이 형성되는 배향제는 폴리 이미드 (polyimide), 폴리아믹에시드 (polyamic acid), 폴리노보넨 (polynorbomene), 페닐말레이미드 공중합처 Kphenylmaleimide copolymer), 폴리아조벤젠 (polyazobenzene), 폴리 에 틸렌이민 (p이 yethyleneimide), 플리비닐알콜 (p이 yvinyl alcohol), 폴리아미드 (polyimide), 폴리 에틸렌 (polyethylene), 폴리스타일렌 (polystylene), 폴리페닐렌프탈아미드 (polyphenylenephthalamide), 폴리에스테르 (polyester), 폴리 메틸 메타크릴레이트 (polymethyl methacrylate) 및 CBDA-FDA PI (poly- (4j4,-(9i9-fluorenyl)diphenylene cyclobutanyltetracarboximide)로 구성된 군에서 선택되는 제조방법 . The method of claim 10, wherein the alignment agent is formed in the direction parallel to the polarization direction of the irradiated light polyimide, polyamic acid, polynorbomene, phenylmaleimide Copolymer Kphenylmaleimide copolymer, polyazobenzene, polyethyleneimide, polyvinyl alcohol, polyimide, polyethylene, polystylene, Consists of polyphenylenephthalamide, polyester, polymethyl methacrylate and CBDA-FDA PI (poly- (4 j 4 , -(9 i 9-fluorenyl) diphenylene cyclobutanyltetracarboximide) Manufacturing method selected from the group.
【청구항 12】 [Claim 12]
제 10 항에 있어서, 상기 조사되는 광의 편광 방향과 직교 방향으로 배향성 이 형성되는 배향제는 CMPI (Chloromethylated polyimide) 또는 폴리비 닐신나메이트 (polyvinylcinamate)인 제조방법 .  The method of claim 10, wherein the alignment agent in which the alignment is formed in a direction orthogonal to the polarization direction of the irradiated light is CMPI (Chloromethylated polyimide) or polyvinylcinamate.
【청구항 13】 [Claim 13]
제 1 항에 있어서, 상기 서로 다른 배향제는 40 내지 l OO um의 간격으로 교차되도록 기판 상에 형성되는 제조방법 .  The method of claim 1, wherein the different alignment agents are formed on the substrate to intersect at intervals of 40 to 100 μm.
【청구항 14] [Claim 14]
제 1 항에 있어서 , 상기 기판은 PES(polyether sulfone), Pl(polyimide), COP(cyclo olefin polymer), PET(polyethylene terephthalate), TAC(triacetyl cellulose), PC(poly carbonate) 및 유리로 구성된 군에서 선택되는 제조방법 .  The method of claim 1, wherein the substrate is selected from the group consisting of polyether sulfone (PES), polyimide (PL), cyclo olefin polymer (COP), polyethylene terephthalate (PET), triacetyl cellulose (TAC), polycarbonate (PC), and glass. Manufacturing Method Selected
【청구항 15】 [Claim 15]
제 1 항에 있어서 , 상기 광경화성 액정 단량체 조성물은 아크릴기, 비닐에 테르기 또는 에폭사이드의 관능기를 가지는 액정성 화합물을 포함하는 제조방법 .  The method of claim 1, wherein the photocurable liquid crystal monomer composition comprises a liquid crystalline compound having a functional group of an acryl group, vinyl ether group, or epoxide.
【청구항 16】 [Claim 16]
계 1 항에 있어서 , 상기 (c) 단계의 광경화성 액정 단량체 조성물 코팅층은 λ/4의 위상을 지연시키는 제조방법 . The photocurable liquid crystal monomer composition according to claim 1, wherein the photocurable liquid crystal monomer composition of step (c) The coating layer is a manufacturing method for retarding the phase of λ / 4.
【청구항 17] [Claim 17]
제 1 항 내지 제 16 항 중 어느 한 항의 제조방법으로 제조되는 패턴된 위상지연필름.  A patterned phase delay film produced by the method of any one of claims 1 to 16.
PCT/KR2012/004753 2011-06-16 2012-06-15 Method for manufacturing a patterned phase retardation film WO2012173431A2 (en)

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KR100969148B1 (en) * 2003-05-30 2010-07-08 엘지디스플레이 주식회사 A method of fabricating retardation film using of polarized uv
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