WO2004010173A1 - Polarizing film producing apparatus and method, and liquid crystal cell and its manufacturing method - Google Patents

Polarizing film producing apparatus and method, and liquid crystal cell and its manufacturing method Download PDF

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Publication number
WO2004010173A1
WO2004010173A1 PCT/JP2003/009090 JP0309090W WO2004010173A1 WO 2004010173 A1 WO2004010173 A1 WO 2004010173A1 JP 0309090 W JP0309090 W JP 0309090W WO 2004010173 A1 WO2004010173 A1 WO 2004010173A1
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WO
WIPO (PCT)
Prior art keywords
polarizing film
liquid crystal
substrate
producing
polarizing
Prior art date
Application number
PCT/JP2003/009090
Other languages
French (fr)
Japanese (ja)
Inventor
Yoshihide Ishibasi
Honggi Bae
Shinya Ohmura
Hiroko Iwashige
Osamu Yamashita
Powei Sung
Original Assignee
Nakan Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2002214206A external-priority patent/JP4020723B2/en
Priority claimed from JP2003036057A external-priority patent/JP2004246092A/en
Priority claimed from JP2003058067A external-priority patent/JP2004271560A/en
Application filed by Nakan Corporation filed Critical Nakan Corporation
Priority to AU2003281592A priority Critical patent/AU2003281592A1/en
Publication of WO2004010173A1 publication Critical patent/WO2004010173A1/en

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    • 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
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528Polarisers

Definitions

  • the present invention relates to a method for manufacturing a liquid crystal display, and particularly to a manufacturing apparatus and a manufacturing method of a polarizing film to which a technique of forming a polarizing film by applying an ink of a dichroic dye is applied, and a liquid crystal cell and a liquid crystal cell are manufactured. It relates to the manufacturing method. Background art
  • the present invention requires the production and attachment of a polarizing plate, which has conventionally required a lot of time and labor, by applying the technology of forming a polarizing film by applying a dichroic dye ink.
  • the first object is to provide an apparatus for manufacturing an LCD polarizing film.
  • the supermolecular complex composed of the dichroic dye is subjected to a shearing force to orient in a certain direction, and the dye molecules are regularly arranged (crystallized). Occurs.
  • the oriented supramolecular complex should be arranged parallel to the substrate. In general, it is normal to be slightly more or less deviated from this ideal arrangement.
  • the supramolecular complex originally has the property of aligning the major axis of the supramolecular complex in a specific direction, but the arrangement direction of the supramolecular complex depends on the surface condition of the substrate.
  • the surface tension of the supramolecular composite When the surface tension of the supramolecular composite is smaller than the critical surface tension of the substrate surface, the surface tension is changed by the magnitude of the surface tension acting between the substrate and the elastic strain energy related to the arrangement of the supramolecular composite. Due to the large force acting between the surface and the supramolecular complex, the supramolecular complex wets the surface and spreads on the substrate surface, and the supramolecular complex is arranged in parallel to the substrate.
  • the surface tension of the supramolecular complex is greater than the critical surface tension of the substrate surface, the force acting between the supramolecular complex rather than the force acting between the substrate surface and the supramolecular complex Is large, the supramolecular complex does not spread on the surface but becomes spherical, and the supramolecular complex is arranged perpendicular to the substrate.
  • the supramolecular composites are arranged in a state where the elastic strain energy is minimized, that is, the supramolecular composites are arranged in a direction in which the supramolecular composites are not subjected to elastic strain.
  • the supramolecular complex is parallel to the substrate depends on the surface condition of the substrate, but the effect of moisture and gas adsorbed on the substrate surface and the effective critical surface due to the contact of the supramolecular complex with the substrate The magnitude of the tension changes, and the relationship between the magnitude of the surface tension and the orientation of the supramolecular complex does not always hold.
  • the state of the elastic strain energy on the surface of the substrate varies slightly depending on the LCD manufacturer.
  • the supramolecular composite applied to the substrate surface cannot obtain a uniform orientation, and deviates from the ideal arrangement.
  • the substrate surface In order to obtain uniform orientation, it is necessary to provide the substrate surface with anisotropic orientation by some method. Therefore, in the present invention, when applying the technique of forming a polarizing film by applying a dichroic dye ink, the substrate surface is provided with orientation anisotropy, so that the uniform arrangement of the polymer complex is achieved.
  • the second objective is to obtain a state.
  • the conventional polarizing plate since the conventional polarizing plate is located on the outermost surface of the LCD, it greatly affects the display quality of the entire display, moisture resistance, heat resistance, etc. I was
  • the present invention provides a new liquid crystal for reducing the influence on the display quality, moisture resistance, heat resistance, etc. of a polarizing plate when applying the technology of forming a polarizing film by applying a dichroic dye ink.
  • the third purpose is to propose a cell and its manufacturing process. Disclosure of the invention
  • the present invention is configured as follows.
  • the polarizing film manufacturing apparatus of the present invention uses an aqueous solution of a dichroic dye that forms a concentration transition type liquid crystal as an ink, and applies this ink to a plate having a large number of fine grooves along the printing direction.
  • the above purpose is achieved by forming a polarizing film by transferring a thin film from a printing plate to a substrate to form a polarizing film.
  • the chemical formula of the dichroic dye is
  • the chemical formula of the dichroic dye is
  • the chemical formula of the dichroic dye is
  • a dashed convex portion is raised in the fine groove to form a concave portion and a convex portion of the groove, and the adjacent convex portion faces the discontinuous portion of the dashed convex portion.
  • the phases are alternately shifted.
  • the projection is formed in a raindrop shape in a plan view.
  • the projection is formed in a bar shape in plan view.
  • a pretreatment step is provided in the step of applying the liquid, and the substrate surface is subjected to an orientation treatment in the pretreatment step.
  • the orientation treatment is a mechanical treatment in which the shape of the substrate surface is deformed to form a large number of fine grooves in one direction.
  • the alignment treatment is a chemical treatment for imparting alignment anisotropy to an alignment layer formed by applying a chemical to a substrate surface.
  • the means for imparting the orientation anisotropy is rubbing in the case of a dry method and an air knife in the case of a wet method.
  • the chemical is a dilute aqueous solution of a nonionic (nonionic) surfactant.
  • the chemical agent is a dilute aqueous solution of hydrophilic polyethylene glycol (PEG).
  • PEG hydrophilic polyethylene glycol
  • the chemical agent is a hydrophobic linear fatty acid.
  • the chemical is a dilute aqueous solution of an organic silane coupling agent.
  • liquid crystal cell of the present invention is characterized in that a polarizing film in which a dichroic dye forming a concentration transition type liquid crystal is oriented in a certain direction is printed directly or indirectly on the inside of the cell. I do.
  • the method for manufacturing a liquid crystal cell of the present invention includes a patterning step of forming a transparent electrode on a washed substrate, an alignment processing step of applying and firing and rubbing an alignment film on the substrate, and a spacer. Spray and paste two substrates together A substrate laminating step, a panel dividing step of dividing the bonded substrate into panels of a predetermined size, a liquid crystal injecting step of injecting a liquid crystal material into the panel, and a polarizing plate attached to both sides of the cell that has passed the panel inspection.
  • a polarizing film printing / stabilizing step of printing and stabilizing a polarizing film on the substrate surface by printing and stabilizing is provided before the alignment treatment step. It is characterized in that the plate attaching step is not required.
  • the pattern of the alignment film applied on the polarizing film is used as a resist to etch the polarizing film other than the display region. It is characterized by.
  • the coated polarizing film is dried, and then the polarizing film is stabilized with an aqueous BaCl 2 solution (8 to 20 wt%). It is characterized.
  • FIG. 1 is a schematic diagram of an apparatus for manufacturing a polarizing film embodying the present invention.
  • FIG. 2 is a diagram showing an example of display colors and molecular structural formulas of a dichroic dye.
  • FIG. 3 is a schematic diagram of a supermolecular complex.
  • FIG. 4 is a diagram showing an alignment state of liquid crystal molecules of a dichroic dye.
  • FIG. 5 is a diagram showing an example of a pattern of fine grooves.
  • Figure 6 is a schematic diagram of the mechanical processing.
  • Figure 7 is a conceptual diagram of the chemical treatment.
  • FIG. 8 is an explanatory diagram of the coating direction and the rubbing direction.
  • FIG. 9 is an explanatory diagram of a coating direction and a substrate installation direction.
  • FIG. 8 is an explanatory diagram of the coating direction and the rubbing direction.
  • FIG. 10 is a sectional view of a liquid crystal cell embodying the present invention.
  • FIG. 11 is a process flow of a liquid crystal cell manufacturing method according to the present invention.
  • FIG. 12 is a process plan view and a process cross-sectional view of a method for manufacturing a liquid crystal cell embodying the present invention.
  • FIG. 1 shows a schematic view of a polarizing film manufacturing apparatus embodying the present invention.
  • the polarizing film manufacturing equipment uses an aqueous solution of a dichroic dye developed by Optiva in the United States as an ink, and prints this ink on a glass-plastic substrate using an ordinary flexographic printing machine to form the polarizing film. Make it.
  • a plate 1 having a number of fine grooves a along the printing direction is mounted on a plate cylinder 2, and ink is dripped from a dispenser 3 in parallel with the rotating plate 1 and spread with a blade 4.
  • the dichroic dye in the liquid crystal state is pushed into the fine grooves a.
  • FIG. 2 shows an example of the display colors and molecular structural formulas of the dichroic dye.
  • dichroic dyes used in the polarizing film of the present invention. Here, three representative types are shown.
  • Dichroic dyes have a significantly different electron density in the molecule between the vertical and horizontal directions, and have a slender molecular structure like a liquid crystal molecule.
  • I can see the formula molecule, is around having a hydrophilic - S 0 3 - is to have a water-soluble with a good UNA functional groups.
  • These dyes can be used alone to form a polarizing film, but are generally used as a mixture. As can be seen from the figure, there are many double bonds, which contribute to light absorption and indicate the properties of a dye.
  • Ink is an aqueous solution of these dyes. As the concentration of the dye increases, the hydrophobic part, that is, the plane part, grows and piles up, and lyotropic (concentration transition) Shape) The liquid crystal is formed and becomes sticky.
  • FIG. 3 shows a schematic diagram thereof.
  • the -SO 3 — group is located outside this stick and is in contact with water. It is said that the ratio between the stick width and length (aspect ratio) is as high as 150: 1. The reason for this ratio is thought to be that the equilibrium state is maintained at the stable point where the energy is the lowest due to the interaction between water, the hydrophilic group and the hydrophobic group. The supramolecular complex increases in viscosity at higher concentrations and becomes a polycrystalline phase.
  • liquid crystals are aligned when subjected to shear forces. Therefore, when this liquid crystal supramolecular composite is printed by the polarizing film manufacturing apparatus of the present invention, it is arranged in the printing direction, and as shown in FIG. As shown in Fig. 4 (b), as the solvent dries and the solvent (in this case, water) evaporates, it is regularly arranged and crystallized to form a thin film.
  • FIG. 5 shows an example of a pattern of the fine grooves.
  • the fine grooves a are formed by applying a photo resist to the surface of the plate 1 and projecting the dashed convex portions b by pattern exposure and etching to form concave and convex portions of the grooves. At this time, the phases of the adjacent convex portions b are alternately shifted so that the adjacent convex portions b face the discontinuous portion c of the broken-line convex portions b.
  • the depth of the microgroove a is 20 to 30 m, the interval between adjacent convex parts b is 120 to 500 ⁇ ra, discontinuous
  • the length of the connecting portion c is preferably 30 to 800 m.
  • the pattern in Fig. 5 (a) shows the projection b formed in the shape of a raindrop in a plan view.
  • the length of the short axis is 30 to 70 ⁇ , the length of the long axis is 100 to 1 000;
  • the taper angle of the tail is preferably 8 to 19 °.
  • the pattern shown in Fig. 5 (b) is one in which the convex part b is formed in a bar shape in plan view, and the length of the short axis is preferably 30 to 70 m, and the length of the long axis is preferably 100 to 1 000 ⁇ m. .
  • the method for manufacturing a polarizing film is to apply a coating solution containing a supramolecular complex in which dichroic dyes are spontaneously stacked in a stick form while applying a shearing force using a printing device or a coating device.
  • a pretreatment step is provided in the process, and the orientation of the surface of the glass substrate is treated in this pretreatment step, so that the arrangement state of the supramolecular complex composed of the dichroic dye when applied to the glass substrate is uniform. It is to make the molecular arrangement state.
  • the orientation treatment includes mechanical treatment to give directionality by applying a directional flaw corresponding to the size of the supramolecular complex to the glass substrate surface, and chemical treatment to give directionality to chemicals applied to the glass substrate surface. is there. .
  • Rubbing is used to give directionality to chemicals, and knives are used when wet.
  • Figure 6 shows a schematic diagram of the mechanical processing.
  • the rubbing equipment used in LCD manufacturing is used as is.
  • a cloth 8 such as rayon is wound around a roller 7 of a rubbing device, and a glass substrate 6 placed on a table 5 is moved in the direction opposite to the rotation direction of the roller 7 while rotating the roller ⁇ .
  • the surface of the glass substrate 6 is rubbed in a certain direction, and a large number of parallel and fine grooves are formed. If the interface has irregularities, the applied supramolecular composite is generally arranged in such a manner that the elastic strain energy is minimized, since no distortion can be obtained.
  • the orientation of the supramolecular complex can be aligned with the direction of the groove by the interaction between the groove and the supramolecular complex.
  • the orientation of the supramolecular composite is the same as the rubbing direction, regardless of the coating direction.
  • the rubbing treatment improves the polarization performance by up to about 20% compared to the conventional case without rubbing.
  • the polarizing film has various directions according to user's requirements, and it is necessary to orient the supramolecular composite obliquely with respect to the glass substrate 6 according to each requirement.
  • the table 5 when the table 5 is rotated, the table 5 may be tilted. In order to prevent the table 5 from being tilted, an accuracy of 0.01 mm or less is required. Costs.
  • the glass substrate 6 since the orientation of the supramolecular complex is aligned with the rubbing direction and the rubbing direction can be easily changed, the glass substrate 6 does not need to be inclined, and such a problem does not occur. .
  • Figure 7 shows a conceptual diagram of the chemical treatment.
  • the glass substrate 6 is cleaned by immersing the glass substrate 6 in a chemical solution or applying a chemical solution by showering or spraying, and providing directionality by air knife. And dry.
  • a household wet sponge may be rubbed with a cleanser and rinsed and then drained with an air knife.
  • an alcohol solution in which stearic acid is dissolved in alcohol is soaked in a cloth and dried, and the cloth is wound around a roller to rub the glass substrate 6.
  • a thin alignment layer of a chemical agent is formed on the surface of the glass substrate 6 by a chemical bond or an intermolecular force, and the alignment layer is provided with alignment anisotropy by air nip rubbing.
  • the supramolecular composite takes over the orientation of the orientation layer material formed on the surface of the glass substrate 6 and is arranged in a certain direction.
  • a nonionic surfactant is diluted 1000 times and applied to a cloth, and the surface of the glass substrate 6 is wiped with the cloth to apply an aqueous solution of the surfactant in a predetermined direction.
  • Surfactants consist of a hydrophobic part and a hydrophilic part, but hydrophilic polyethylene glycol (molecular weight 200 to 20,000) has the same effect as a surfactant.
  • Hydrophobic stearate is a solid, but when it is rubbed on a cloth, it has the same tendency as polypropylene and Teflon.
  • the same effect can be obtained by treating the glass substrate 6 with a solution of a silane coupling agent and then removing the solution with an air knife.
  • Rubbing the wet-processed glass substrate 6 also has the effect of giving directionality.
  • FIG. 10 is a sectional view of a liquid crystal cell embodying the present invention.
  • the figure shows an example of a simple matrix type LCD such as the STN type.
  • the liquid crystal cell sandwiched a thin layer of liquid crystal material 1 3 two inner transparent in order to electrodes of the glass substrate 6 9, S i 0 2 film 10, the polarizing film 1 1, an orientation film 12 are laminated, peripheral
  • the cell is hermetically sealed by circling a sealing material 14.
  • the polarizing film 11 uses an aqueous solution of a dichroic dye as an ink, and applies the ink to a plate having a large number of fine grooves along the printing direction to form a thin film. Is transferred and applied to form a film.
  • the liquid crystal molecules of the liquid crystal material 13 are in direct contact with the alignment film 12, and the cell gap corresponding to the thickness of the liquid crystal material 13 is controlled by the diameter of the spacer 15.
  • the aluminum component may be dissolved in the liquid crystal, which may cause a decrease in contrast and image quality.
  • a SiO 2 film 10 is formed between the transparent electrode 9 and the polarizing film 11 or between the glass substrate 6 and the transparent electrode 9, and the glass substrate 6 is undercoated. .
  • FIG. 11 shows a process flow of a method for manufacturing a liquid crystal cell according to the present invention.
  • FIG. 12 shows a process plan view and a process cross-sectional view of the method for manufacturing a liquid crystal cell.
  • an IT0 film is formed on a well-cleaned glass substrate 6 by an evaporation method or a sputtering method, and a resist material is applied thereon, and the mask pattern is exposed and etched. Then, the transparent electrode 9 is patterned, and then the resist material is removed. (Step 101).
  • the SiO 2 film 10 corresponding to the electrode pattern is applied on the transparent electrode 9 by printing (Step 102).
  • Step 103 a pretreatment is performed to better align the molecular orientation of the polarizing film 11 by, for example, rubbing the surface of the lower film with a cloth having a surfactant attached thereto.
  • the polarizing film 11 is printed using an ink that forms a polarizing film on the entire surface of the glass substrate 6, or is coated with another coating device that applies shearing force. And then dried (step 104).
  • a shear force is applied by a bar coater, a slot die, a plate, or the like to orient the molecules of the polarizing film 11 composed of the dichroic dye in a certain direction.
  • the temperature should be 23 ° C and the humidity should be higher than 60%.
  • the polarizing film 11 is stabilized, rinsed and dried (step 105). Since the solvent forming the polarizing film 11 is water, the solvent collapses when the film is dried and then comes into contact with water even after the film is dried. Therefore, after drying, stabilization is performed to make it insoluble in water.
  • Stabilization processes immersed 2-10 seconds polarizing film 1 1
  • the aqueous solution was Bac l 2 in an aqueous solution of 8 ⁇ 20wt%.
  • the glass substrate 6 coated with the polarizing film 11 is rinsed with pure water to remove excess BaCl 2 aqueous solution, and the pure water is cut off with an air knife, and the glass substrate 6 is washed at about 80 ° C to 120 ° C. By drying, the moisture of the glass substrate 6 is completely dried.
  • a thin film having a polarizing function can be formed on the entire surface of the glass substrate 6 in a state stabilized in water or the like.
  • Step 106 PI printing and curing are performed.
  • PI printing In PI printing, a polyimide solution diluted with an organic solvent is applied by a flexographic printing apparatus, and the pattern of the alignment film 12 is printed on the polarizing film 11.
  • the solvent is dried at a heating temperature of around 80 ° C, and then calcined to completely cure the polyimide.
  • etching, rinsing and drying are performed (step 107).
  • Etching is performed by immersing the glass substrate 6 in an aqueous solution of 0.2% (0.2 to 0.5%) of an alkaline solution and then shaking with pure water, so that the polarizing film where there is no alignment film 12 is formed. Dissolve and remove 1 1. This makes it possible to easily leave only the display area of the polarizing film 11. Even the stabilized polarizing film 11 is peeled off when it comes into contact with the aqueous alkali solution. At this time, the temperature of the chemical is desirably about 20 ° C to 25 ° C.
  • a rubbing process is performed to rub the alignment film 12 in a certain direction while rotating a roller around which a cloth such as a rayon is wound, so that the alignment directions of the liquid crystal molecules are aligned in a certain direction (step 108).
  • the polymer main chain of the alignment film polyimide is stretched in the rubbing direction by this treatment, and the liquid crystal molecules are arranged along the stretching direction.
  • a spacer 15 for controlling cell gap is sprayed on one glass substrate 6 (step 109).
  • a sealing material 14 for bonding and sealing the glass substrate 6 and the opposing glass substrate 6 integrally is applied to the other glass substrate 6 (step 110).
  • the glass substrate 6 to which the sealing material 14 has been applied and the glass substrate 6 to which the spacer 15 has been scattered are accurately overlapped and bonded by pressure bonding (step 11 1).
  • the glass substrate 6 occupied by the shells is tightened by a heating press until a predetermined cell gap is reached, and the sealing material 14 is heated and hardened (step 112).
  • the multi-panel glass substrate 6 is divided, for example, into individual panels of a predetermined size (step 113).
  • liquid crystal material 13 is injected into the panel, and the liquid crystal material 13, dust, dirt, and the like adhering to the panel after the injection port is sealed are washed (step 114).
  • step 115 appearance inspection such as foreign matter, scratches, defective separation, uneven color between polarizers, uneven cell gap, poor alignment, etc., presence or absence of black spots and white spots, presence / absence of various alignment defects, dot / line display
  • a lighting inspection for the presence or absence of a defect is performed (step 115).
  • the polarizing film manufacturing apparatus of the present invention uses the aqueous solution of the dichroic dye as the ink and prints this on the substrate to form the polarizing film.
  • the production and pasting work of the board becomes unnecessary, and the production efficiency of LCD is greatly improved.
  • the polarizing film is formed inside the glass substrate instead of outside as in the conventional case, the viewing angle is increased by the thickness of the glass substrate.
  • dyes such as iodine used in conventional polarizing plates have molecules arranged in a thread form and leak light when viewed from an oblique direction.
  • the dye used in the polarizing film of the present invention has a width of basic molecules. Since it is about twice as large as the benzene nucleus, there is little light leakage even when viewed from an angle, and the viewing angle is further widened.
  • a conventional polarizer is produced by stretching a film on which a dye is adsorbed, and this stretching effect is likely to return due to thermal vibration, and it is considered that the heat resistance is low.
  • molecules are the benzene nucleus and bone 'rating, Ba ++ and - since S 0 3 one is crosslinked force is strong, difficult broken by thermal vibrations, heat resistance is improved.
  • the arranging direction of the supramolecular complex takes various directions depending on the surface state of the substrate, but the method for manufacturing a polarizing film of the present invention provides an alignment anisotropy by performing an alignment treatment on the substrate surface in the pretreatment step. Therefore, the arrangement direction of the supramolecular complex applied to the substrate surface can be controlled to an ideal direction.
  • the polarization performance of the polarizing film was improved.
  • the polarization performance was improved by about 20%.
  • the polarization performance was reduced by about 50%.
  • the liquid crystal cell of the polarizing film of the present invention is formed by printing a polarizing film in which a dichroic dye is oriented in one direction by printing on the inside of the cell, the viewing angle is increased by the thickness of the glass substrate.
  • moisture resistance and heat resistance which are important characteristics for expanding the use of LCDs and maintaining display quality, are improved.

Abstract

An apparatus for producing a polarizing film of an LCD while dispensing with the production of a polarizing sheet and its bonding work conventionally requiring a long time and many man-hours. A polarizing film is produced by using an aqueous solution of a dichroic dye developed by Optiva, Inc., a USA-based company, as an ink and forming the polarizing film by printing with this ink on a glass or plastic substrate by means of a flexographic printing press. Referring to the drawing, a plate (1) having plural fine grooves extending in the printing direction is attached to a plate cylinder (2), the ink is dripped parallel to the rotating plate (1) from a dispenser (3), the dripped ink is spread with a blade (4), and the liquid-crystalline dichroic dye is squeezed into the fine grooves (a). Since the blade (4) is held with a small gap, out of contact with the plate (1). A thin film of the ink liquid is formed on the plate surface. When a glass substrate (6) secured to a table (5) passes directly below the plate cylinder (2), the thin film of the ink liquid is transferred from the plate (1) to the glass substrate (6), and the glass plate (6) is coated with the thin film.

Description

明 細 書  Specification
偏光膜の製造装置および製造方法ならぴに液晶セルと その製造方法 技術分野  Liquid crystal cell and manufacturing method for polarizing film manufacturing apparatus and manufacturing method
本発明は、 液晶ディ スプレイ の製造方法に係わり、 特に二色性染料の イ ンキを塗布して偏光膜を形成する技術を適用した偏光膜の製造装置お よび製造方法ならぴに,液晶セルとその製造方法に関する。 背景技術  The present invention relates to a method for manufacturing a liquid crystal display, and particularly to a manufacturing apparatus and a manufacturing method of a polarizing film to which a technique of forming a polarizing film by applying an ink of a dichroic dye is applied, and a liquid crystal cell and a liquid crystal cell are manufactured. It relates to the manufacturing method. Background art
従来、 液晶セルの両面に配置する偏光板は、 パネル検查を合格した液 晶セルの外側に接着剤を用いて貼り付けていた。  Conventionally, polarizing plates disposed on both sides of a liquid crystal cell have been attached to the outside of the liquid crystal cell that has passed panel inspection using an adhesive.
このため、 スクライバで分断した液晶セルの一つ一つに偏光板を貼り 合わせる必要があり 、 作業性が非常に悪かった。  For this reason, it was necessary to attach a polarizing plate to each of the liquid crystal cells divided by the scriber, and the workability was extremely poor.
また、 貼合せ時に位置決め精度や密着強度の確保、 気泡やダス ト混入 の防止、 静電気の発生防止などさまざまな対策を必要と し、 その後のェ 程で偏光板とパネルの密着性の強化や間に残存する気泡の除去などのた めにォー トク レーブ処理を行うなど、 その組立てに多く の時間と労力を 費やしていた。  In addition, various measures must be taken during lamination, such as ensuring positioning accuracy and adhesion strength, preventing air bubbles and dust from being mixed, and preventing the generation of static electricity. A lot of time and effort was spent on assembling the parts, such as performing autoclave treatment to remove air bubbles remaining in the tub.
そこで本発明は、 二色性染料のインキを塗布して偏光膜を形成する技 術を適用することによ り、 従来多く の時間と労力を費やしていた偏光板 の作製や貼り付け作業を必要と しない L C Dの偏光膜の製造装置を提供 することを第 1 目的とする。  Thus, the present invention requires the production and attachment of a polarizing plate, which has conventionally required a lot of time and labor, by applying the technology of forming a polarizing film by applying a dichroic dye ink. The first object is to provide an apparatus for manufacturing an LCD polarizing film.
また、 二色性染料のイ ンキを塗布するとき、 二色性染料からなる超分 子複合体は剪断力を受けて一定方向に配向し、 染料分子が規則的に並び (結晶化し) 偏光性能が生じる。 · 配向した超分子複合体は基板と平行に配列するのが理想であるが、 一 般的にはこの理想の配列から大なり 小なりずれているのが普通である。 超分子複合体は本来その超分子複合体の長軸方向を特定の方向に揃え る性質があるが、 超分子複合体の配列方向は基板の表面状態に依存し、 基板表面と超分子複合体の間に働く 表面張力の大き さや超分子複合体の 配列に関連する弾性歪みエネルギーの作用によって変化するからである, 超分子複合体の表面張力が基板表面の臨界表面張力よ り小さい場合は 基板表面と超分子複合体との間に働く 力が大きいため、 超分子複合体は 表面を濡ら して基板表面上に広がり 、 超分子複合体は基板に平行な配列 となる。 In addition, when an ink of a dichroic dye is applied, the supermolecular complex composed of the dichroic dye is subjected to a shearing force to orient in a certain direction, and the dye molecules are regularly arranged (crystallized). Occurs. · Ideally, the oriented supramolecular complex should be arranged parallel to the substrate. In general, it is normal to be slightly more or less deviated from this ideal arrangement. The supramolecular complex originally has the property of aligning the major axis of the supramolecular complex in a specific direction, but the arrangement direction of the supramolecular complex depends on the surface condition of the substrate. When the surface tension of the supramolecular composite is smaller than the critical surface tension of the substrate surface, the surface tension is changed by the magnitude of the surface tension acting between the substrate and the elastic strain energy related to the arrangement of the supramolecular composite. Due to the large force acting between the surface and the supramolecular complex, the supramolecular complex wets the surface and spreads on the substrate surface, and the supramolecular complex is arranged in parallel to the substrate.
逆に超分子複合体の表面張力が基板表面の臨界表面張力よ り 大きい場 合は、 基板表面と超分子複合体との間に働く 力よ り も超分子複合体の間 に働く 力の方が大きいため、超分子複合体は表面に広がらず球状になり 、 超分子複合体は基板に垂直な配列と なる。  Conversely, if the surface tension of the supramolecular complex is greater than the critical surface tension of the substrate surface, the force acting between the supramolecular complex rather than the force acting between the substrate surface and the supramolecular complex Is large, the supramolecular complex does not spread on the surface but becomes spherical, and the supramolecular complex is arranged perpendicular to the substrate.
また、 基板表面が滑らかでない場合は、 超分子複合体は弾性歪みエネ ルギ一が極小となる状態、 すなわち超分子複合体が弾性歪みを受けない 方向に配列する。  When the substrate surface is not smooth, the supramolecular composites are arranged in a state where the elastic strain energy is minimized, that is, the supramolecular composites are arranged in a direction in which the supramolecular composites are not subjected to elastic strain.
超分子複合体が基板と平行になるかどうかは基板の表面状態によるが 基板表面に吸着した水分やガスなどの影響や、 超分子複合体が基板と接 触する こ とで実効的な臨界表面張力の大き さが変化し、 表面張力の大小 と超分子複合体の配向の関係が必ずしも成立しなく なる。  Whether or not the supramolecular complex is parallel to the substrate depends on the surface condition of the substrate, but the effect of moisture and gas adsorbed on the substrate surface and the effective critical surface due to the contact of the supramolecular complex with the substrate The magnitude of the tension changes, and the relationship between the magnitude of the surface tension and the orientation of the supramolecular complex does not always hold.
また、 基板は LCD メーカによ り表面の弾性歪みエネルギーの状態が少 しずつ異なっている。  In addition, the state of the elastic strain energy on the surface of the substrate varies slightly depending on the LCD manufacturer.
このため、 基板表面に塗布された超分子複合体は均一な配向を得るこ とができず、 理想の配列からずれてしま う。  For this reason, the supramolecular composite applied to the substrate surface cannot obtain a uniform orientation, and deviates from the ideal arrangement.
均一な配向を得るためには、 何らかの方法で基板表面に配向異方性を もたせる必要がある。 そこで本発明は、 二色性染料のィンキを塗布して偏光膜を形成する技 術を適用する場合、 基板表面に配向異方性をもたせることによ り、 超分 子複合体の均一な配列状態が得られるよ う にするこ とを第 2 目的とする また、 従来の偏光板は LCDの最表面に配置されていたためディスプレ ィ全体の表示品位や耐湿性、 耐熱性などに大きな影響を与えていた。 In order to obtain uniform orientation, it is necessary to provide the substrate surface with anisotropic orientation by some method. Therefore, in the present invention, when applying the technique of forming a polarizing film by applying a dichroic dye ink, the substrate surface is provided with orientation anisotropy, so that the uniform arrangement of the polymer complex is achieved. The second objective is to obtain a state.In addition, since the conventional polarizing plate is located on the outermost surface of the LCD, it greatly affects the display quality of the entire display, moisture resistance, heat resistance, etc. I was
そこで本発明は、 二色性染料のインキを塗布して偏光膜を形成する技 術を適用する場合、 偏光板の表示品位や耐湿性、 耐熱性などに与える影 響を低減するための新しい液晶セルとその製造プロセスを提案するこ と を第 3 目的と.する。 発明の開示  Therefore, the present invention provides a new liquid crystal for reducing the influence on the display quality, moisture resistance, heat resistance, etc. of a polarizing plate when applying the technology of forming a polarizing film by applying a dichroic dye ink. The third purpose is to propose a cell and its manufacturing process. Disclosure of the invention
かかる目的を達成するために、 本発明は以下のよ う に構成した。  In order to achieve such an object, the present invention is configured as follows.
すなわち、 本発明の偏光膜の製造装置は、 濃度転移形液晶を形成する 二色性染料の水溶液をインキと して用い、 このインキを印刷方向に沿つ て多数の微細溝を有する版に塗布して薄膜を形成し、 しかしてこの薄膜 を版から基板に転写塗布して偏光膜を形成することによ り上記目的が達 成される。  That is, the polarizing film manufacturing apparatus of the present invention uses an aqueous solution of a dichroic dye that forms a concentration transition type liquid crystal as an ink, and applies this ink to a plate having a large number of fine grooves along the printing direction. The above purpose is achieved by forming a polarizing film by transferring a thin film from a printing plate to a substrate to form a polarizing film.
また、 好ましく は、 前記二色性染料の化学式を  Also preferably, the chemical formula of the dichroic dye is
Figure imgf000005_0001
とする。
Figure imgf000005_0001
And
また、 好ましく は、 前記二色性染料の化学式を  Also preferably, the chemical formula of the dichroic dye is
Figure imgf000006_0001
Figure imgf000006_0001
Figure imgf000006_0002
とする。
Figure imgf000006_0002
And
また、 好ましく は、 前記二色性染料の化学式を  Also preferably, the chemical formula of the dichroic dye is
Figure imgf000006_0003
Figure imgf000006_0003
Figure imgf000006_0004
とする。
Figure imgf000006_0004
And
また、 好ましく は、 前記微細溝に破線状の凸部を隆起して溝の凹部と 凸部を形成し、 この破線状の凸部の不連続部分に隣接凸部が臨むよ うに 隣接凸部の位相を交互にずら して配列する。 また、 好ま しく は、 前記凸部を平面視雨滴状に形成する。 Also, preferably, a dashed convex portion is raised in the fine groove to form a concave portion and a convex portion of the groove, and the adjacent convex portion faces the discontinuous portion of the dashed convex portion. The phases are alternately shifted. Preferably, the projection is formed in a raindrop shape in a plan view.
また、 好ま しく は、 前記凸部を平面視棒状に形成する。  Preferably, the projection is formed in a bar shape in plan view.
また、 本発明の偏光膜の製造方法は、 濃度転移形液晶を形成する二色 性染料のコーティング液を基板表面に剪断力を与えながら塗布して偏光 膜を製造する工程において、 前記コ ーティ ング液を塗布する工程に前処 理工程を設け、 この前処理工程において前記基板表面に配向処理を施す ことを特徴とする。  Further, in the method for producing a polarizing film of the present invention, in the step of producing a polarizing film by applying a coating solution of a dichroic dye for forming a concentration transition type liquid crystal while applying a shearing force to the substrate surface, A pretreatment step is provided in the step of applying the liquid, and the substrate surface is subjected to an orientation treatment in the pretreatment step.
また、 好ま しく は、 前記配向処理を、 基板表面の形状を変形させて一 定方向の微細溝を多数形成する機械処理とする。  Preferably, the orientation treatment is a mechanical treatment in which the shape of the substrate surface is deformed to form a large number of fine grooves in one direction.
また、 好ま しく は、 前記配向処理を、 基板表面に化学薬品を塗布して 形成した配向層に配向異方性を付与する化学処理とする。  Preferably, the alignment treatment is a chemical treatment for imparting alignment anisotropy to an alignment layer formed by applying a chemical to a substrate surface.
また、 好ま しく は、 前記配向異方性を付与する手段を乾式の場合はラ ビング、 湿式の場合はエアナイフとする。  Preferably, the means for imparting the orientation anisotropy is rubbing in the case of a dry method and an air knife in the case of a wet method.
また、 好ま しく は、 前記化学薬品をノニオン系 (非イオン系) 界面活 性剤の希薄水溶液とする。  Preferably, the chemical is a dilute aqueous solution of a nonionic (nonionic) surfactant.
また、 好ま しく は、 前記化学薬 を親水性のポリ エチレンダリ コール ( PEG) の希薄水溶液とする。  Preferably, the chemical agent is a dilute aqueous solution of hydrophilic polyethylene glycol (PEG).
また、 好ま しく は、 前記化学薬 を疎水性の直鎖脂肪酸とする。  Preferably, the chemical agent is a hydrophobic linear fatty acid.
また、 好ま しく は、 前記化学薬品を有機シランカップリ ング剤の希薄 水溶液とする。  Preferably, the chemical is a dilute aqueous solution of an organic silane coupling agent.
また、 本発明の液晶セルは、 濃度転移形液晶を形成する二色性染料を 一定の方向に配向させた偏光膜を直接または間接的にセルの内側に印刷 して形成するこ とを特徴とする。  Further, the liquid crystal cell of the present invention is characterized in that a polarizing film in which a dichroic dye forming a concentration transition type liquid crystal is oriented in a certain direction is printed directly or indirectly on the inside of the cell. I do.
また、 本発明の液晶セルの製造方法は、 洗浄した基板に透明電極を形 成するパターニング工程と、 この基板に配向膜を塗布して焼成 . ラ ビン グする配向処理工程と、 スぺーサを散布して 2枚の基板を貼り合わせる 基板貼合せ工程と、 貼り合わせた基板を所定サイズのパネルに分断する パネル分断工程と、 このパネルに液晶材料を注入する液晶注入工程と、 パネル検査に合格したセルの両面に偏光板を貼り付ける偏光板貼付けェ 程からなる液晶セルの組立て工程において、 前記配向処理工程の前に基 板面に偏光膜を印刷塗布して安定化させる偏光膜の印刷 · 安定化工程を 設け、 しかして前記偏光板貼付け工程を不要にすることを特徴とする。 In addition, the method for manufacturing a liquid crystal cell of the present invention includes a patterning step of forming a transparent electrode on a washed substrate, an alignment processing step of applying and firing and rubbing an alignment film on the substrate, and a spacer. Spray and paste two substrates together A substrate laminating step, a panel dividing step of dividing the bonded substrate into panels of a predetermined size, a liquid crystal injecting step of injecting a liquid crystal material into the panel, and a polarizing plate attached to both sides of the cell that has passed the panel inspection. In the step of assembling a liquid crystal cell comprising a polarizing plate attaching step, a polarizing film printing / stabilizing step of printing and stabilizing a polarizing film on the substrate surface by printing and stabilizing is provided before the alignment treatment step. It is characterized in that the plate attaching step is not required.
また、 本発明の液晶セルの製造方法は、 前記偏光膜を形成するプロセ スにおいて、 この偏光膜の上に塗布した配向膜のパターンをレジス トに して表示領域以外の偏光膜をエッチングすることを特徴とする。  Further, in the method for manufacturing a liquid crystal cell according to the present invention, in the process for forming the polarizing film, the pattern of the alignment film applied on the polarizing film is used as a resist to etch the polarizing film other than the display region. It is characterized by.
また、 本発明の液晶セルの製造方法は、 前記偏光膜を形成するプロセ スにおいて、 塗布された偏光膜を乾燥後、 BaCl 2水溶液 (8〜20wt % ) に て偏光膜を安定化させるこ とを特徴とする。 図面の簡単な説明 Further, in the method for manufacturing a liquid crystal cell according to the present invention, in the process for forming the polarizing film, the coated polarizing film is dried, and then the polarizing film is stabilized with an aqueous BaCl 2 solution (8 to 20 wt%). It is characterized. BRIEF DESCRIPTION OF THE FIGURES
図 1 は、本発明を実施した偏光膜の製造装置の模式図である。図 2は、 二色性染料の表示色と分子構造式の一例を示す図である。 図 3は、 超分 子複合体の模式図である。 図 4は、 二色性染料の液晶分子の配向状態を 示す図である。 図 5は、 微細溝のパターンの一例を示す図である。 図 6 は、 機械処理の模式図である。 図 7は、 化学処理の概念図である。 図 8 は、 コーティ ング方向とラビング方向の説明図である。 図 9は、 コーテ イ ング方向と基板の設置方向の説明図である。 図 10は、 本発明を実施し た液晶セルの断面図である。 図 1 1 は、 本発明を実施した液晶セルの製造 方法の工程フローである。 図 12は、 本発明を実施した液晶セルの製造方 法の工程平面図と工程断面図である。 発明を実施するための最良の形態 以下に図面を参照して、 本発明の実施の形態について説明する。 FIG. 1 is a schematic diagram of an apparatus for manufacturing a polarizing film embodying the present invention. FIG. 2 is a diagram showing an example of display colors and molecular structural formulas of a dichroic dye. FIG. 3 is a schematic diagram of a supermolecular complex. FIG. 4 is a diagram showing an alignment state of liquid crystal molecules of a dichroic dye. FIG. 5 is a diagram showing an example of a pattern of fine grooves. Figure 6 is a schematic diagram of the mechanical processing. Figure 7 is a conceptual diagram of the chemical treatment. FIG. 8 is an explanatory diagram of the coating direction and the rubbing direction. FIG. 9 is an explanatory diagram of a coating direction and a substrate installation direction. FIG. 10 is a sectional view of a liquid crystal cell embodying the present invention. FIG. 11 is a process flow of a liquid crystal cell manufacturing method according to the present invention. FIG. 12 is a process plan view and a process cross-sectional view of a method for manufacturing a liquid crystal cell embodying the present invention. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with reference to the drawings.
図 1 に、 本発明を実施した偏光膜の製造装置の模式図を示す。  FIG. 1 shows a schematic view of a polarizing film manufacturing apparatus embodying the present invention.
偏光膜の製造装置は、米国 Op t i va社の開発した二色性染料の水溶液を ィ ンキと して用い、 このインキを通常のフレキソ印刷装置でガラスゃプ ラスチック基板に印刷して偏光膜を作製する。  The polarizing film manufacturing equipment uses an aqueous solution of a dichroic dye developed by Optiva in the United States as an ink, and prints this ink on a glass-plastic substrate using an ordinary flexographic printing machine to form the polarizing film. Make it.
図において、 印刷方向に沿つて多数の微細溝 a を有する版 1 を版胴 2 に取り付け、 回転している版 1 と平行にデイ スペンサ 3からインキを滴 下してブ レー ド 4で塗り広げ、 液晶状態の二色性染料を微細溝 aに押し 込める。  In the figure, a plate 1 having a number of fine grooves a along the printing direction is mounted on a plate cylinder 2, and ink is dripped from a dispenser 3 in parallel with the rotating plate 1 and spread with a blade 4. The dichroic dye in the liquid crystal state is pushed into the fine grooves a.
このとき、 ブレー ド 4は版 1 に接することなく わずかなギャップを設 けて保持されているので、 版面にインキ液の薄膜が形成される。  At this time, since the blade 4 is held in contact with the plate 1 with a slight gap therebetween, a thin film of the ink liquid is formed on the plate surface.
そして、 テーブル 5上に固定されたガラス基板 6が版胴 2直下を通過 するときに、 このィンキ液の薄膜が版 1 からガラス基板 6 に転写塗布さ れる。  Then, when the glass substrate 6 fixed on the table 5 passes directly below the plate cylinder 2, a thin film of this ink is transferred and applied from the plate 1 to the glass substrate 6.
図 2に、 二色性染料の表示色と分子構造式の一例を示す。  FIG. 2 shows an example of the display colors and molecular structural formulas of the dichroic dye.
本発明の偏光膜に使用する二色性染料は 7種類程度あるが、 ここでは そのうちの代表的な 3種類を示す。  There are about seven types of dichroic dyes used in the polarizing film of the present invention. Here, three representative types are shown.
二色性染料は、 分子内の電子密度が縦と横では大き く異なり、 液晶分 子のよ うに細長い分子構造をしている。 分子構造式からわかるよ う に平 面長円状の分子で、 周囲には親水性を持つ- S 0 3—のよ うな官能基をつけ て水溶性を持たせている。 Dichroic dyes have a significantly different electron density in the molecule between the vertical and horizontal directions, and have a slender molecular structure like a liquid crystal molecule. In molecular structure from the jar to the flat surface length circular I can see the formula molecule, is around having a hydrophilic - S 0 3 - is to have a water-soluble with a good UNA functional groups.
これらの染料は、 単独で用いても偏光膜を作ることが可能であるが、 一般的には混合して用いられる。 図からわかるよ うに二重結合が数多く 存在し、 これが光の吸収に関与して染料と しての性質を示している。  These dyes can be used alone to form a polarizing film, but are generally used as a mixture. As can be seen from the figure, there are many double bonds, which contribute to light absorption and indicate the properties of a dye.
イ ンキはこれらの染料の水溶液で、染料の濃度が高く なると疎水部分、 すなわち平面部分が積重なり合って成長し、 リオトロ ピック (濃度転移 形) 液晶を形成してスティ ック状になる。 Ink is an aqueous solution of these dyes. As the concentration of the dye increases, the hydrophobic part, that is, the plane part, grows and piles up, and lyotropic (concentration transition) Shape) The liquid crystal is formed and becomes sticky.
このスティ ック状に積重なった液晶分子の凝集体を 「超分子複合体」 と呼び、 図 3にその模式図を示す。  The aggregate of liquid crystal molecules stacked in a stick shape is called a “supramolecular complex”, and FIG. 3 shows a schematic diagram thereof.
-SO 3—基はこのスティ ックの外側に位置し、 水と接している。 スティ ック幅と長さの比 (アスペク ト比) は 1ノ1 50 に及ぶといわれている。 この比を呈するのは、 水と親水基と疎水基の相互作用で最もエネルギ 一が低い安定なと ころで平衡状態を保っためと考えられる。 この超分子 複合体は濃度が更に高く なる と粘度を増し、 多結晶相となる。 The -SO 3 — group is located outside this stick and is in contact with water. It is said that the ratio between the stick width and length (aspect ratio) is as high as 150: 1. The reason for this ratio is thought to be that the equilibrium state is maintained at the stable point where the energy is the lowest due to the interaction between water, the hydrophilic group and the hydrophobic group. The supramolecular complex increases in viscosity at higher concentrations and becomes a polycrystalline phase.
液晶が剪断力を受ける と配向する ことはよ く 知られている。そのため、 この液晶の超分子複合体は本発明の偏光膜製造装置で印刷される と、 印 刷方向に並び、図 4 (a)に示すよ う に、最初は乱れた配列と考えられるが、 図 4 (b)に示すよ う に、 乾燥して溶剤 (この場合水) が蒸発するにつれよ り規則正しく配列し、 結晶化して薄膜になる。  It is well known that liquid crystals are aligned when subjected to shear forces. Therefore, when this liquid crystal supramolecular composite is printed by the polarizing film manufacturing apparatus of the present invention, it is arranged in the printing direction, and as shown in FIG. As shown in Fig. 4 (b), as the solvent dries and the solvent (in this case, water) evaporates, it is regularly arranged and crystallized to form a thin film.
このとき、印刷方向と垂直の面には 2重結合がひとつおきに存在する。 従って、 この方向に電界をもつ光はこの膜で吸収され、 透過する光は 印刷方向に電界をもつ偏光となる。  At this time, every other double bond exists on the plane perpendicular to the printing direction. Therefore, light having an electric field in this direction is absorbed by this film, and transmitted light becomes polarized light having an electric field in the printing direction.
乾燥が終わった結晶化薄膜は BaC l 2の水溶液で処理する と、 短時間で ひとつの分子の- S O 3 と他の分子の- SO 3 が 1個の Ba++ィオンと反応し、 架橋が起こる。 その結果、 水に溶けずに機械的な強度が増す。 これは、 その後の工程を容易にしている。 When drying is complete crystallization thin film is treated with an aqueous solution of Bac l 2, one of the molecules in a short time - SO 3 and other molecules - SO 3 reacts with one Ba ++ Ion, crosslinking Occur. The result is increased mechanical strength without dissolving in water. This facilitates subsequent steps.
図 5 に、 微細溝のパターンの一例を示す。  FIG. 5 shows an example of a pattern of the fine grooves.
微細溝 a は、 版 1 の表面にフォ ト レジス トを塗り 、 パターン露光とェ ツチングによ り破線状の凸部 b を隆起して溝の凹部と凸部を形成する。 このとき、 破線状の凸部 b の不連続部分 c に隣接凸部 bが臨むよ う に 隣接凸部 b の位相を交互にずら して配列する。  The fine grooves a are formed by applying a photo resist to the surface of the plate 1 and projecting the dashed convex portions b by pattern exposure and etching to form concave and convex portions of the grooves. At this time, the phases of the adjacent convex portions b are alternately shifted so that the adjacent convex portions b face the discontinuous portion c of the broken-line convex portions b.
微細溝 a の深さは 20〜30 m、 隣接凸部 b の間隔は 120〜500 μ ra、 不連 続部分 c の長さは 30〜800 mが好適である。 The depth of the microgroove a is 20 to 30 m, the interval between adjacent convex parts b is 120 to 500 μra, discontinuous The length of the connecting portion c is preferably 30 to 800 m.
図 5 ( a)のパターンは、 凸部 b を平面視雨滴状に形成したもので、 短軸 の長さは 30〜70 μ πι、 長軸の長さは 1 00〜 1 000 ;ii m、 尻尾の部分の先細り 角度は 8〜1 9 ° が好適である。  The pattern in Fig. 5 (a) shows the projection b formed in the shape of a raindrop in a plan view.The length of the short axis is 30 to 70 μπι, the length of the long axis is 100 to 1 000; The taper angle of the tail is preferably 8 to 19 °.
図 5 ( b )のパターンは、 凸部 b を平面視棒状に形成したもので、 短軸の 長さは 30〜70 m、 長軸の長さは 1 00〜 1 000 μ mが好適である。  The pattern shown in Fig. 5 (b) is one in which the convex part b is formed in a bar shape in plan view, and the length of the short axis is preferably 30 to 70 m, and the length of the long axis is preferably 100 to 1 000 μm. .
次に、 本発明を実施した偏光膜の製造方法について説明する。  Next, a method for manufacturing a polarizing film according to the present invention will be described.
偏光膜の製造方法は、 二色性染料がスティ ッ ク状に自発的に積み重な つた超分子複合体を含むコーティ ング液を印刷装置やコーティ ング装置 を用いて剪断力を与えながら塗布する工程に前処理工程を設け、 この前 処理工程においてガラス基板の表面に配向処理を施すことによ り、 ガラ ス基板に塗布したときの二色性染料からなる超分子複合体の配列状態を 均質な分子配列状態にするものである。  The method for manufacturing a polarizing film is to apply a coating solution containing a supramolecular complex in which dichroic dyes are spontaneously stacked in a stick form while applying a shearing force using a printing device or a coating device. A pretreatment step is provided in the process, and the orientation of the surface of the glass substrate is treated in this pretreatment step, so that the arrangement state of the supramolecular complex composed of the dichroic dye when applied to the glass substrate is uniform. It is to make the molecular arrangement state.
配向処理には、 超分子複合体の寸法に見合った方向性のあるキズをガ ラス基板表面につけて方向性を与える機械処理と、 ガラス基板表面につ けた化学薬品に方向性を与える化学処理がある。 .  The orientation treatment includes mechanical treatment to give directionality by applying a directional flaw corresponding to the size of the supramolecular complex to the glass substrate surface, and chemical treatment to give directionality to chemicals applied to the glass substrate surface. is there. .
化学薬品に方向性を与える手段は乾式の場合ラ ビング、 湿式の場合ェ ァナイフである。  Rubbing is used to give directionality to chemicals, and knives are used when wet.
図 6に、 機械処理の模式図を示す。  Figure 6 shows a schematic diagram of the mechanical processing.
機械処理は、 LCDの製造で使われているラビング装置をそのまま用い る。  For mechanical processing, the rubbing equipment used in LCD manufacturing is used as is.
図において、 ラビング装置のローラ 7にレーヨンなどの布 8を卷き付 け、 ローラ Ί を回転させながらテーブル 5に置かれたガラス基板 6 を口 ーラ 7 の回転方向と逆方向に移動させる。  In the figure, a cloth 8 such as rayon is wound around a roller 7 of a rubbing device, and a glass substrate 6 placed on a table 5 is moved in the direction opposite to the rotation direction of the roller 7 while rotating the roller Ί.
これによ り 、 ガラス基板 6の表面が一定方向に擦られて平行で細かな 多数の溝が形成される。 界面に凹凸がある場合は一般に無歪状態をとれないので、 塗布された 超分子複合体は弾性歪エネルギーが極小となるよ う に配列する。 As a result, the surface of the glass substrate 6 is rubbed in a certain direction, and a large number of parallel and fine grooves are formed. If the interface has irregularities, the applied supramolecular composite is generally arranged in such a manner that the elastic strain energy is minimized, since no distortion can be obtained.
その結果、 溝と超分子複合体の相互作用によ り 、 超分子複合体の配列 の方位を溝の方向に揃えるこ とができる。  As a result, the orientation of the supramolecular complex can be aligned with the direction of the groove by the interaction between the groove and the supramolecular complex.
そのため、 コーティ ング方向とラ ビング方向を変えても、 超分子複合 体の配向はコーティ ング方向に係わ り なく 、 ラ ビ.ング方向に一致する。  Therefore, even if the coating direction and the rubbing direction are changed, the orientation of the supramolecular composite is the same as the rubbing direction, regardless of the coating direction.
ラ ビング処理を施すと、 従来のラ ビングなしの場合に比べ、 偏光性能 が最大約 20%向上する。  The rubbing treatment improves the polarization performance by up to about 20% compared to the conventional case without rubbing.
実験の結果、 コーティ ング方向 Aと ラ ビング方向 Bの角度 Θ が小さい ほど偏光性能は向上.し、 図 8 (a)の Θ =0° (コーティ ング方向 Aと ラ ビン グ方向 Bがー致) では約 20%、 図 8(b)の Θ =15° では約 10%、 図 8(c) の Θ =30° では約 5%、 図 8 (d)の Θ =45° では約 5%それぞれアップする ことが分かった。  As a result of the experiment, the smaller the angle の between the coating direction A and the rubbing direction B, the better the polarization performance, and の = 0 ° in Fig. 8 (a) (the coating direction A and the rubbing direction B ) At about 20%, about 10% at Θ = 15 ° in Figure 8 (b), about 5% at Θ = 30 ° in Figure 8 (c), and about 5% at Θ = 45 ° in Figure 8 (d). It turns out that each improves.
偏光膜は、 ユーザの要求によってさまざまな方向があり、 それぞれの 要求に応じて超分子複合体をガラス基板 6 に対して斜めに配向させる必 要がある。  The polarizing film has various directions according to user's requirements, and it is necessary to orient the supramolecular composite obliquely with respect to the glass substrate 6 according to each requirement.
従来のラ ビングなしのコーティ ング方法では、 図 9 (a)に示すよ う に、 ガラス基板 6 に超分子複合体を斜めに配向させる場合、 コーティ ング方 向 Aを変える こ とはできないので、 テーブル 5 を回転してガラス基板 6 を斜めにする必要がある。  In the conventional coating method without rubbing, as shown in Fig. 9 (a), when the supramolecular composite is obliquely oriented on the glass substrate 6, the coating direction A cannot be changed. It is necessary to rotate the table 5 so that the glass substrate 6 is inclined.
ところが、 テーブル 5 を回転する とテーブル 5が傾く ことがあ り 、 テ 一プル 5が傾かないよ う にするためには 0.01mm以下の精度を必要とす るので、 テーブル 5の回転装置に多く の費用がかかる。  However, when the table 5 is rotated, the table 5 may be tilted. In order to prevent the table 5 from being tilted, an accuracy of 0.01 mm or less is required. Costs.
また、 図 9 (b)に示すよ う に、 ガラス基板 6 よ りテーブル 5 の方が大き い場合、ガラス基板 6 を斜めにして全面にコーティ ング液を塗布する と、 コーティ ング液がガラス基板 6からはみ出すので、 毎回テーブル 5 を洗 浄 · 乾燥しなければならなく なる。 Also, as shown in FIG. 9 (b), when the table 5 is larger than the glass substrate 6, the coating liquid is applied to the entire surface while the glass substrate 6 is slanted. Wash table 5 every time as it protrudes from 6. It must be purified and dried.
また、 図 9 (c)に示すよ う に、 ガラス基板 6 とテーブル 5が同じ大きさ の場合、 ガラス基板 6 を載せるテーブル 5 を斜めにしてコーティ ング液 を塗布する と、 幅方向で必要な液量が異なるので、 コーティ ング液の出 力調整が複雑になる。  Further, as shown in FIG. 9 (c), when the glass substrate 6 and the table 5 are the same size, if the coating liquid is applied while the table 5 on which the glass substrate 6 is placed is inclined, the necessary width is required in the width direction. Since the liquid volumes are different, the output adjustment of the coating liquid becomes complicated.
本発明のコーティ ング方法は、 超分子複合体の配向がラ ビング方向に —致し、 ラ ビング方向を変えるのは簡単なので、 ガラス基板 6 を斜めに する必要がなく 、 このよ うな問題は発生しない。  According to the coating method of the present invention, since the orientation of the supramolecular complex is aligned with the rubbing direction and the rubbing direction can be easily changed, the glass substrate 6 does not need to be inclined, and such a problem does not occur. .
機械処理の場合、 レーヨン系の布 8 でラビングする と、 超分子複合体 はすべて同様の分子配列状態を示す。 また、 布 8 の材質をレー ヨ ン、 ナ ィ ロン、 ポリ エステノレ、 ポリ エチレン、 ポリ プロ ピレン、 テフロンと変 化させる と、 極性等の違いによ り それぞれ異なった配向性能を示す。  In the case of mechanical treatment, when rubbed with rayon-based cloth 8, all supramolecular complexes show the same molecular arrangement state. In addition, when the material of the cloth 8 is changed to rayon, nylon, polyethylene, polyethylene, polypropylene, or Teflon, different orientation performances are exhibited depending on the polarity and the like.
このため、 コーティ ング液の組成の違いによって布 8 の材質を使い分 けるのが望ま しい。  For this reason, it is desirable to use different materials for the cloth 8 depending on the composition of the coating liquid.
図 7 に、 化学処理の概念図を示す。  Figure 7 shows a conceptual diagram of the chemical treatment.
化学処理は、 湿式と乾式の 2つの方式があり 、 湿式はガラス基板 6 を 薬液に浸したり、 シャ ワーやスプレーで薬液をかけたり してガラス基板 6 を洗浄し、 エアナイ フで方向性をつけて乾かす。  There are two types of chemical treatment, wet and dry.In the wet type, the glass substrate 6 is cleaned by immersing the glass substrate 6 in a chemical solution or applying a chemical solution by showering or spraying, and providing directionality by air knife. And dry.
このとき、 家庭用の研磨材付きスポンジで擦り 、 その後、 エアナイフ で水を切ってもよい。 .  At this time, it may be rubbed with a household abrasive sponge, and then drained with an air knife. .
あるいは、 家庭用の湿式スポンジにク レンザをつけて擦り 、 すすいだ 後、 エアナイ フで水を切ってもよい。  Alternatively, a household wet sponge may be rubbed with a cleanser and rinsed and then drained with an air knife.
乾式は、 例えばステア リ ン酸をアルコールに溶かしたアルコール溶液 を布にしみこませて乾燥し、 この布をローラに巻き付けてガラス基板 6 をラ ビングする。  In the dry method, for example, an alcohol solution in which stearic acid is dissolved in alcohol is soaked in a cloth and dried, and the cloth is wound around a roller to rub the glass substrate 6.
布には、 例えば医療用のガーゼやフェルトなど固い材質のものを用い る。 Use a cloth made of hard material such as gauze or felt for medical use. You.
これによ り、 ガラス基板 6の表面に化学結合または分子間力による化 学薬品の薄い配向層を形成し、 この配向層にエアナイ フゃラビングによ つて配向異方性を付与する。  As a result, a thin alignment layer of a chemical agent is formed on the surface of the glass substrate 6 by a chemical bond or an intermolecular force, and the alignment layer is provided with alignment anisotropy by air nip rubbing.
その結果、 超分子複合体はガラス基板 6の表面に形成した配向層材料 の配向性を引き継いで一定方向に配列する。  As a result, the supramolecular composite takes over the orientation of the orientation layer material formed on the surface of the glass substrate 6 and is arranged in a certain direction.
具体的にはノニオン系の界面活性剤を 1000倍に希釈して布につけ、こ の布でガラス基板 6表面を拭いて界面活性剤の水溶液を一定方向に塗布 する。  Specifically, a nonionic surfactant is diluted 1000 times and applied to a cloth, and the surface of the glass substrate 6 is wiped with the cloth to apply an aqueous solution of the surfactant in a predetermined direction.
この後、 乾いた布で同じ方向に拭き上げる と効果がある。  After this, it is effective to wipe up in the same direction with a dry cloth.
あるいは、 ガラス基板 6 を湿式洗浄してすすいだ後、 濡れたところに 上記界面活性剤を 50〜100Ppmにした液を塗布して水と置換し、その後ェ ァナイフで水を切る。 Alternatively, it rinsed the glass substrate 6 by wet cleaning, by applying a solution obtained by the surfactant 50 to 100 P pm replaced with water was wet, then cut the water E Anaifu.
この水を切ったときのエアの方向に剪断力を与えて塗布する と偏光性 能は向上する。  By applying a shearing force in the direction of the air when the water is drained, the polarization performance is improved.
界面活性剤は疎水性の部分と親水性の部分からなっているが、 親水性 のポリエチレングリ コール (分子量 200〜20000 ) は界面活性剤と同様の 効果がある。  Surfactants consist of a hydrophobic part and a hydrophilic part, but hydrophilic polyethylene glycol (molecular weight 200 to 20,000) has the same effect as a surfactant.
また、 疎水性のステアリ ン酸は固体であるが、 布につけてこすりつけ るとポリ プロ ピレン、 テフロンと同様の傾向がある。  Hydrophobic stearate is a solid, but when it is rubbed on a cloth, it has the same tendency as polypropylene and Teflon.
また、 シランカップリ ング剤の溶液でガラス基板 6 を処理した後、 ェ ァナイフで液を切ると同様の効果がある。  The same effect can be obtained by treating the glass substrate 6 with a solution of a silane coupling agent and then removing the solution with an air knife.
なお、 湿式で処理したガラス基板 6にラビングを施しても方向性を与 える効果がある。  Rubbing the wet-processed glass substrate 6 also has the effect of giving directionality.
図 1 0に、 本発明を実施した液晶セルの断面図を示す。  FIG. 10 is a sectional view of a liquid crystal cell embodying the present invention.
図では STN型などシンプルマ ト リ クス方式の LCDの例を示す。 液晶セルは、 2枚のガラス基板 6の内側に順番に透明電極 9、 S i 02膜 10、 偏光膜 1 1、 配向膜 12を積層して液晶材料 1 3 の薄層を挟み込み、 周 辺にシール材 14を巡らせてセルを気密封着する構成である。 The figure shows an example of a simple matrix type LCD such as the STN type. The liquid crystal cell sandwiched a thin layer of liquid crystal material 1 3 two inner transparent in order to electrodes of the glass substrate 6 9, S i 0 2 film 10, the polarizing film 1 1, an orientation film 12 are laminated, peripheral In this configuration, the cell is hermetically sealed by circling a sealing material 14.
偏光膜 1 1 は、 二色性染料の水溶液をィ ンキと して用い、 このィ ンキを 印刷方向に沿って多数の微細溝を有する版に塗布して薄膜を形成し、 こ の薄膜を版から転写塗布して成膜する。  The polarizing film 11 uses an aqueous solution of a dichroic dye as an ink, and applies the ink to a plate having a large number of fine grooves along the printing direction to form a thin film. Is transferred and applied to form a film.
液晶材料 13 の液晶分子は配向膜 12に直接接触し、液晶材料 13 の層厚 に相当するセルのギヤップはスぺーサ 15の直径で制御される。  The liquid crystal molecules of the liquid crystal material 13 are in direct contact with the alignment film 12, and the cell gap corresponding to the thickness of the liquid crystal material 13 is controlled by the diameter of the spacer 15.
ガラス基板 6にアル力 リガラスを用いるとそのアル力 リ成分が液晶中 に溶け出してコ ン ト ラス トの低下、 画質の劣化を招く こ とがある。  If aluminum glass is used for the glass substrate 6, the aluminum component may be dissolved in the liquid crystal, which may cause a decrease in contrast and image quality.
このため、 図に示すよ うに透明電極 9 と偏光膜 1 1 の間、 あるいはガラ ス基板 6 と透明電極 9 の間に S i 02膜 10 を形成してガラス基板 6 をアン ダーコ一 トする。 Therefore, as shown in the figure, a SiO 2 film 10 is formed between the transparent electrode 9 and the polarizing film 11 or between the glass substrate 6 and the transparent electrode 9, and the glass substrate 6 is undercoated. .
図 1 1 に、 本発明を実施した液晶セルの製造方法の工程フローを示す。 また、図 12に、液晶セルの製造方法の工程平面図と工程断面図を示す。 液晶セルは、 まず、 よく洗浄したガラス基板 6に蒸着法あるいはスパ ッタ法などによって IT0膜を成膜し、 その上にレジス ト材を塗布してマ スクのパターンを露光し、 エッチングを行って透明電極 9をパターニン グし、 その後でレジス ト材を除去する。 (工程 101 )。  FIG. 11 shows a process flow of a method for manufacturing a liquid crystal cell according to the present invention. FIG. 12 shows a process plan view and a process cross-sectional view of the method for manufacturing a liquid crystal cell. In the liquid crystal cell, first, an IT0 film is formed on a well-cleaned glass substrate 6 by an evaporation method or a sputtering method, and a resist material is applied thereon, and the mask pattern is exposed and etched. Then, the transparent electrode 9 is patterned, and then the resist material is removed. (Step 101).
洗浄後、 透明電極 9 の上に電極パターンに対応する S i 02膜 10を印刷 によ り塗布する (工程 102)。 After the cleaning, the SiO 2 film 10 corresponding to the electrode pattern is applied on the transparent electrode 9 by printing (Step 102).
次に、偏光膜 1 1を塗布する前に下膜の表面に界面活性剤をつけた布で ラビングするなどして偏光膜 1 1の分子配向をよ り よく配向させるため の前処理を行う (工程 103)。  Next, before applying the polarizing film 11, a pretreatment is performed to better align the molecular orientation of the polarizing film 11 by, for example, rubbing the surface of the lower film with a cloth having a surfactant attached thereto ( Step 103).
次に、 ガラス基板 6 の全面に偏光性を示す膜を形成するイ ンキを用い て偏光膜 1 1 を印刷したり、他の剪断力を与えるコーティ ング装置で塗布 して、 その後乾燥させる (工程 104)。 Next, the polarizing film 11 is printed using an ink that forms a polarizing film on the entire surface of the glass substrate 6, or is coated with another coating device that applies shearing force. And then dried (step 104).
偏光膜 1 1 を塗布する ときは、 バーコータ、 スロ ッ トダイ、 版などによ り剪断力をかけて偏光膜 1 1 の二色性染料からなる分子を一定方向に配 向させる。  When the polarizing film 11 is applied, a shear force is applied by a bar coater, a slot die, a plate, or the like to orient the molecules of the polarizing film 11 composed of the dichroic dye in a certain direction.
また、 塗布と乾燥を安定して行う ためには温度は 23°C、 湿度は 60%よ り高い方が望ま しい。  For stable application and drying, the temperature should be 23 ° C and the humidity should be higher than 60%.
その後、 偏光膜 1 1 の安定化を行い、 リ ンス、 乾燥させる (工程 105 )。 偏光膜 1 1 を形成するイ ンキは溶媒が水なので塗布工程後、膜が乾燥し ても水に接する と膜が崩れる。 その為に乾燥後水に溶けなくする為に安 定化処理を行う。  Thereafter, the polarizing film 11 is stabilized, rinsed and dried (step 105). Since the solvent forming the polarizing film 11 is water, the solvent collapses when the film is dried and then comes into contact with water even after the film is dried. Therefore, after drying, stabilization is performed to make it insoluble in water.
安定化処理は、 BaC l 2を 8〜20wt %の水溶液にして偏光膜 1 1 をその水 溶液に 2〜10秒間浸して処理する。その後純水で偏光膜 1 1が塗布された ガラス基板 6 をリ ンス させ、 余分な BaCl 2水溶液をなく し、 エアナイフ で純水を切って、 80°Cから 120°C位でガラス基板 6 を乾燥させる事によ り ガラス基板 6の水分を完全に乾燥させる。 この様な工程によ り ガラス 基板 6全面に偏光機能を持つ薄膜を水などに安定させた状態で形成でき る。 Stabilization processes immersed 2-10 seconds polarizing film 1 1 The aqueous solution was Bac l 2 in an aqueous solution of 8~20wt%. After that, the glass substrate 6 coated with the polarizing film 11 is rinsed with pure water to remove excess BaCl 2 aqueous solution, and the pure water is cut off with an air knife, and the glass substrate 6 is washed at about 80 ° C to 120 ° C. By drying, the moisture of the glass substrate 6 is completely dried. By such a process, a thin film having a polarizing function can be formed on the entire surface of the glass substrate 6 in a state stabilized in water or the like.
次に、 PI印刷と硬化を行う (工程 106)。  Next, PI printing and curing are performed (Step 106).
P I印刷は、 有機溶剤で希釈したポリ イ ミ ドの溶液をフ レキソ印刷装置 で塗布し、 偏光膜 1 1 の上に配向膜 12 のパターンを印刷する。  In PI printing, a polyimide solution diluted with an organic solvent is applied by a flexographic printing apparatus, and the pattern of the alignment film 12 is printed on the polarizing film 11.
硬化は、 80°C前後の加熱温度で溶剤を乾燥した後、 焼成してポリ イ ミ ドを完全に硬化させる。  For curing, the solvent is dried at a heating temperature of around 80 ° C, and then calcined to completely cure the polyimide.
次に、 エッチング、 リ ンス、 乾燥を行う (工程 107 )。  Next, etching, rinsing and drying are performed (step 107).
エッチングは、 0.数% (0. 2〜 0. 5 % ) のアル力 リ水溶液にガラス基板 6 を浸してから純水でシャ ヮする事によ り配向膜 12が無いと ころの偏光 膜 1 1 を溶かし出して除去する。 これによ り 、 簡単に偏光膜 1 1 の表示領域だけを残すこ とができる。 安定化された偏光膜 1 1 でもアルカ リ水溶液に接する事によ り剥され る。 この時の薬液の温度は 20°Cから 25°Cく らいが望ま しい。 Etching is performed by immersing the glass substrate 6 in an aqueous solution of 0.2% (0.2 to 0.5%) of an alkaline solution and then shaking with pure water, so that the polarizing film where there is no alignment film 12 is formed. Dissolve and remove 1 1. This makes it possible to easily leave only the display area of the polarizing film 11. Even the stabilized polarizing film 11 is peeled off when it comes into contact with the aqueous alkali solution. At this time, the temperature of the chemical is desirably about 20 ° C to 25 ° C.
次に、 レーョ ンなどの布を巻き付けたローラを回転させながら配向膜 12 を一定方向に擦るラ ビング処理を行い、 液晶分子の配向方位を一定方 向に揃える (工程 108 )。  Next, a rubbing process is performed to rub the alignment film 12 in a certain direction while rotating a roller around which a cloth such as a rayon is wound, so that the alignment directions of the liquid crystal molecules are aligned in a certain direction (step 108).
この処理で配向膜ポリイ ミ ドのポリ マー主鎖がラ ビング方向に延伸さ れ、 この延伸方向に沿って液晶分子が配列するものと考えられる。  It is considered that the polymer main chain of the alignment film polyimide is stretched in the rubbing direction by this treatment, and the liquid crystal molecules are arranged along the stretching direction.
次に、 一方のガラス基板 6 にセルギヤ ップを制御するためのスぺーサ 15 を散布する (工程 109)。  Next, a spacer 15 for controlling cell gap is sprayed on one glass substrate 6 (step 109).
次に、 ガラス基板 6 と対向ガラス基板 6 を一体に貼り合わせ · 封着す るためのシール材 14 を他方のガラス基板 6 に塗布する (工程 1 10 )。 次に、 シール材 14が塗布されたガラス基板 6 と スぺーサ 15が散布さ れたガラス基板 6 を精度よ く重ね合わせ、圧着貼り合わせる (工程 1 1 1 )。  Next, a sealing material 14 for bonding and sealing the glass substrate 6 and the opposing glass substrate 6 integrally is applied to the other glass substrate 6 (step 110). Next, the glass substrate 6 to which the sealing material 14 has been applied and the glass substrate 6 to which the spacer 15 has been scattered are accurately overlapped and bonded by pressure bonding (step 11 1).
次に、 貝占り合わせたガラス基板 6 を所定のセルギャ ップになるまで加 熱プレスで締め付け、 シール材 14を加熱硬化させる (工程 1 12 )。  Next, the glass substrate 6 occupied by the shells is tightened by a heating press until a predetermined cell gap is reached, and the sealing material 14 is heated and hardened (step 112).
次に、 多面取り のガラス基板 6 から所定サイズの個々 のパネルに分割 するなどの分断を行う (工程 1 13 )。  Next, the multi-panel glass substrate 6 is divided, for example, into individual panels of a predetermined size (step 113).
次に、 パネルに液晶材料 13 を注入し、 注入口封止後のパネルに付着し ている液晶材料 13やゴミ、 汚れなどを洗浄する (工程 1 14)。  Next, the liquid crystal material 13 is injected into the panel, and the liquid crystal material 13, dust, dirt, and the like adhering to the panel after the injection port is sealed are washed (step 114).
次に、 異物やキズ、 分断不良、 偏光子間での色むらやセルギャ ップむ ら、 配向不良などの外観検査や、 黒点や白点の有無、 各種配向欠陥の有 無、 点 · 線表示欠陥の有無などの点灯検査を行う (工程 1 15 )。  Next, appearance inspection such as foreign matter, scratches, defective separation, uneven color between polarizers, uneven cell gap, poor alignment, etc., presence or absence of black spots and white spots, presence / absence of various alignment defects, dot / line display A lighting inspection for the presence or absence of a defect is performed (step 115).
以上によ り液晶セルの組立が終了する。 産業上の利用可能性 以上説明したよ うに、 本発明の偏光膜の製造装置は、 二色性染料の水 溶液をインキと して用い、これを基板に印刷して偏光膜を形成するので、 従来のよ う な偏光板の作製や貼り付け作業が不要になり 、 L C Dの生産 効率が大幅に向上する。 また、 偏光膜が従来のよ うにガラス基板の外側 でなく内側に形成されるので、ガラス基板の厚みだけ視野角が広く なる。 Thus, the assembly of the liquid crystal cell is completed. Industrial applicability As described above, the polarizing film manufacturing apparatus of the present invention uses the aqueous solution of the dichroic dye as the ink and prints this on the substrate to form the polarizing film. The production and pasting work of the board becomes unnecessary, and the production efficiency of LCD is greatly improved. Also, since the polarizing film is formed inside the glass substrate instead of outside as in the conventional case, the viewing angle is increased by the thickness of the glass substrate.
また、 従来の偏光板に使用していたヨ ウ素などの染料は分子が糸状に 並んでいて斜めから見ると光が漏れるが、 本発明の偏光膜に使用する染 料は基本分子の幅がベンゼン核の 2倍前後あるので、 斜めから見ても光 の漏れが少なく 、 視野角がよ り一層広く なる。  In addition, dyes such as iodine used in conventional polarizing plates have molecules arranged in a thread form and leak light when viewed from an oblique direction. However, the dye used in the polarizing film of the present invention has a width of basic molecules. Since it is about twice as large as the benzene nucleus, there is little light leakage even when viewed from an angle, and the viewing angle is further widened.
また、 従来の偏光子は染料を吸着させたフィルムを引き伸ばして作製 するが、 この引き伸ばした効果が熱振動で戻ってしまいやすく、 耐熱性 は低いと考えられるが、 本発明の偏光膜は染料の分子がベンゼン核を骨 '格と し、 Ba++と- S 0 3一が架橋して結合力が強いので、熱振動では壊れ難く 、 耐熱性が向上する。 In addition, a conventional polarizer is produced by stretching a film on which a dye is adsorbed, and this stretching effect is likely to return due to thermal vibration, and it is considered that the heat resistance is low. molecules are the benzene nucleus and bone 'rating, Ba ++ and - since S 0 3 one is crosslinked force is strong, difficult broken by thermal vibrations, heat resistance is improved.
また、 超分子複合体の配列方向は基板の表面状態によってさまざまな 方位をとるが、 本発明の偏光膜の製造方法は、 前処理工程において基板 表面に配向処理を施して配向異方性をもたせるので、 基板表面に塗布し た超分子複合体の配列方向を理想の方位に制御することができる。  Also, the arranging direction of the supramolecular complex takes various directions depending on the surface state of the substrate, but the method for manufacturing a polarizing film of the present invention provides an alignment anisotropy by performing an alignment treatment on the substrate surface in the pretreatment step. Therefore, the arrangement direction of the supramolecular complex applied to the substrate surface can be controlled to an ideal direction.
これによ り、 偏光膜の偏光性能が向上し、 実際に配向処理を施した方 向に沿って超分子複合体を塗布した結果、 偏光性能は約 20%向上した。 一方、この方向と垂直に超分子複合体を塗布した結果、偏光性能は約 50% 低下した。  As a result, the polarization performance of the polarizing film was improved. As a result of applying the supramolecular composite in the direction in which the alignment treatment was actually performed, the polarization performance was improved by about 20%. On the other hand, when the supramolecular composite was applied perpendicular to this direction, the polarization performance was reduced by about 50%.
また、 本発明の偏光膜の液晶セルは、 二色性染料を一方向に配向させ た偏光膜をセルの内側に印刷して形成するので、 ガラス基板の厚みだけ 視野角が広く なる。  Further, since the liquid crystal cell of the polarizing film of the present invention is formed by printing a polarizing film in which a dichroic dye is oriented in one direction by printing on the inside of the cell, the viewing angle is increased by the thickness of the glass substrate.
また、 偏光膜がガラス基板で保護されるので、 偏光板にキズを付きに く くするためのハ ー ドコー ト処理や静電気の帯電防止処理なども不要に なる。 Also, since the polarizing film is protected by the glass substrate, scratches may be made on the polarizing plate. This eliminates the need for hard coating and static electricity prevention.
また、 LCDの用途拡大や表示品位を保つ上で重要な特性である耐湿性 や耐熱性が向上する。  In addition, moisture resistance and heat resistance, which are important characteristics for expanding the use of LCDs and maintaining display quality, are improved.

Claims

請求の範囲 The scope of the claims
1 . 濃度転移形液晶を形成する二色性染料の水溶液をィンキと して用 い、 1. An aqueous solution of a dichroic dye forming a concentration-transition liquid crystal is used as an ink,
このイ ンキを印刷方向に沿って多数の微細溝を有する版に塗布して薄 膜を形成し、  This ink is applied to a plate having a number of fine grooves along the printing direction to form a thin film,
しかしてこの薄膜を版から基板に転写塗布して偏光膜を形成すること を特徴とする偏光膜の製造装置。  An apparatus for manufacturing a polarizing film, wherein the thin film is transferred from the plate to a substrate to form a polarizing film.
2 . 前記二色性染料の化学式を 2. The chemical formula of the dichroic dye is
Figure imgf000020_0001
とする請求項 1記載の偏光膜の製造装置,
Figure imgf000020_0001
The polarizing film manufacturing apparatus according to claim 1,
3 . 前記二色性染料の化学式を 3. The chemical formula of the dichroic dye is
Figure imgf000020_0002
Figure imgf000020_0002
Figure imgf000020_0003
とする請求項 1記載の偏光膜の製造装置,
Figure imgf000020_0003
The polarizing film manufacturing apparatus according to claim 1,
4 . 前記二色性染料の化学式を 4. The chemical formula of the dichroic dye is
Figure imgf000021_0001
Figure imgf000021_0001
Figure imgf000021_0002
とする請求項 1記載の偏光膜の製造装置。
Figure imgf000021_0002
The polarizing film manufacturing apparatus according to claim 1, wherein
5 . 前記微細溝に破線状の凸部を隆起して溝の凹部と凸部を形成し、 この破線状の凸部の不連続部分に隣接凸部が臨むよ う に隣接凸部の位 相を交互にずらして配列することを特徴とする請求項 1記載の偏光膜の 製造装置。 5. A dashed convex portion is raised in the fine groove to form a concave portion and a convex portion of the groove, and the phase of the adjacent convex portion is set so that the adjacent convex portion faces the discontinuous portion of the broken line convex portion. 2. The apparatus for manufacturing a polarizing film according to claim 1, wherein the elements are alternately shifted.
6 . 前記凸部を平面視雨滴状に形成することを特徴とする請求項 5記 載の偏光膜の製造装置。  6. The apparatus for manufacturing a polarizing film according to claim 5, wherein the projection is formed in a raindrop shape in a plan view.
7 . 前記凸部を平面視棒状に形成することを特徴とする請求項 5記載 の偏光膜の製造装置。  7. The polarizing film manufacturing apparatus according to claim 5, wherein the projection is formed in a bar shape in a plan view.
8 . 濃度転移形液晶を形成する二色性染料のコ ーティ ング液を基板表 面に剪断力を与えながら塗布して偏光膜を製造する工程において、  8. In the step of producing a polarizing film by applying a coating solution of a dichroic dye forming a concentration transition type liquid crystal while applying a shearing force to the surface of the substrate,
前記コーティング液を塗布する工程に前処理工程を設け、  A pretreatment step is provided in the step of applying the coating liquid,
この前処理工程において前記基板表面に配向処理を施すことを特徴と する偏光膜の製造方法。  A method for producing a polarizing film, characterized in that an alignment treatment is performed on the substrate surface in the pretreatment step.
9 . 前記配向処理を、 基板表面の形状を変形させて一定方向の微細溝を多数形成する機械処 理とする請求項 8記載の偏光膜の製造方法。 9. The alignment treatment is 9. The method for producing a polarizing film according to claim 8, wherein a mechanical treatment is performed to deform the shape of the substrate surface to form a large number of fine grooves in a certain direction.
1 0 . 前記配向処理を、  10. The alignment treatment
基板表面に化学薬品を塗布して形成した配向層に配向異方性を付与す る化学処理とする請求項 8記載の偏光膜の製造方法。  9. The method for producing a polarizing film according to claim 8, wherein a chemical treatment is performed to impart an alignment anisotropy to an alignment layer formed by applying a chemical to the substrate surface.
1 1 . 前記配向異方性を付与する手段を乾式の場合はラビング、 湿式 の場合はエアナイフとする請求項 10記載の偏光膜の製造方法。  11. The method for producing a polarizing film according to claim 10, wherein the means for imparting orientation anisotropy is rubbing when dry, or air knife when wet.
1 2 . 前記化学薬品をノ ニオン系 (非イ オン系) 界面活性剤の希薄水 溶液とする請求項 10記載の偏光膜の製造方法。  12. The method for producing a polarizing film according to claim 10, wherein the chemical agent is a dilute aqueous solution of a nonionic (non-ionic) surfactant.
1 3 . 前記化学薬品を親水性のポ リ エチ レングリ コール (PEG) の希薄 水溶液とする請求項 10記載の偏光膜の製造方法。 13. The method for producing a polarizing film according to claim 10, wherein the chemical agent is a dilute aqueous solution of hydrophilic polyethylene glycol (PEG).
1 4 . 前記化学薬品を疎水.性の直鎖脂肪酸とする請求項 10記載の偏光 膜の製造方法。  14. The method for producing a polarizing film according to claim 10, wherein the chemical is a hydrophobic straight-chain fatty acid.
1 5 . 前記化学薬品を有機シラ ンカツプリ ング剤の希薄水溶液とする 請求項 10記載の偏光膜の製造方法。  15. The method for producing a polarizing film according to claim 10, wherein the chemical is a dilute aqueous solution of an organic silane coupling agent.
1 6 - 濃度転移形液晶を形成する二色性染料を一定の方向に配向させ た偏光膜を直接または間接的にセルの内側に印刷して形成するこ とを特 徴とする液晶セル。  16-Liquid crystal cell characterized by the fact that a dichroic dye that forms a concentration transition type liquid crystal is directly or indirectly printed on the inside of the cell with a polarizing film oriented in a certain direction.
1 7 . 洗浄した基板に透明電極を形成するパターユング工程と、  1 7. A patterning process for forming a transparent electrode on the washed substrate;
この基板に配向膜を塗布して焼成 · ラ ビングする配向処理工程と、 スぺーサを散布して 2枚の基板を貼り合わせる基板貼合せ工程と、 貼り合わせた基板を所定サイズのパネルに分断するパネル分断工程と、 このパネルに液晶材料を注入する液晶注入工程と、 An alignment process for applying an alignment film to the substrate, firing and rubbing; a substrate bonding process for applying a spacer to bond the two substrates; and dividing the bonded substrate into panels of a predetermined size. A liquid crystal material injection step of injecting a liquid crystal material into the panel;
パネル検査に合格したセルの両面に偏光板を貼り付ける偏光板貼付け 工程と、  A polarizing plate attaching process of attaching polarizing plates to both sides of the cell that has passed the panel inspection;
からなる液晶セルの組立て工程において、 前記配向処理工程の前に基板面に偏光膜を印刷塗布して安定化させる 偏光膜の印刷 · 安定化工程を設け、 In the assembly process of the liquid crystal cell consisting of Before the alignment treatment step, a polarizing film is printed and applied to the substrate surface to stabilize.
しかして前記偏光板貼付け工程を不要にするこ とを特徴とする液晶セ ルの製造方法。  Thus, a method for producing a liquid crystal cell, which eliminates the need for the polarizing plate attaching step.
1 8 . 前記偏光膜を形成するプロセスにおいて、  18. In the process of forming the polarizing film,
この偏光膜の上に塗布した配向膜のパターンをレジス トにして表示領 域以外の偏光膜をエッチングすることを特徴とする請求項 17記載の液 晶セルの製造方法。  18. The method for producing a liquid crystal cell according to claim 17, wherein the polarizing film other than the display area is etched using the pattern of the alignment film applied on the polarizing film as a resist.
1 9 . 前記偏光膜を形成するプロセスにおいて、  1 9. In the process of forming the polarizing film,
塗布された偏光膜を乾燥後、  After drying the applied polarizing film,
BaCl 2水溶液 (8〜20wt % ) にて偏光膜を安定化させることを特徴とす る請求項 17記載の液晶セルの製造方法。 Method for manufacturing a liquid crystal cell according to claim 17, wherein you, characterized in that to stabilize the polarization film at BaCl 2 aqueous solution (8~20wt%).
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