WO2014156981A1 - 位相差フィルムの製造方法 - Google Patents

位相差フィルムの製造方法 Download PDF

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Publication number
WO2014156981A1
WO2014156981A1 PCT/JP2014/057819 JP2014057819W WO2014156981A1 WO 2014156981 A1 WO2014156981 A1 WO 2014156981A1 JP 2014057819 W JP2014057819 W JP 2014057819W WO 2014156981 A1 WO2014156981 A1 WO 2014156981A1
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Prior art keywords
film
support
coating film
alignment
liquid crystal
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PCT/JP2014/057819
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English (en)
French (fr)
Japanese (ja)
Inventor
広敏 安藤
和宏 沖
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富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to KR1020157026853A priority Critical patent/KR101745235B1/ko
Priority to CN201480019223.0A priority patent/CN105074516A/zh
Priority to JP2015508424A priority patent/JP6146935B2/ja
Publication of WO2014156981A1 publication Critical patent/WO2014156981A1/ja

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements

Definitions

  • the present invention relates to a method for producing a retardation film having an optically anisotropic layer in which a liquid crystal compound is aligned.
  • liquid crystal display devices In recent years, the use of liquid crystal display devices is rapidly advancing and is used in mobile phones, personal computer monitors, televisions, liquid crystal projectors, and the like.
  • a liquid crystal display device has a display mode such as a TN (Twisted Nematic) mode, a VA (Vertical Alignment) mode, an IPS (In-Plane Switching) mode, an OCB (Optically ens Compensatory Bend) mode, and an ECB (Electrically Controlled Birefringence) mode.
  • TN Transmission Nematic
  • VA Very Alignment
  • IPS In-Plane Switching
  • OCB Optically ens Compensatory Bend
  • ECB Electrically Controlled Birefringence
  • a TFT (Thin Film Transistor) -LCD As such a liquid crystal display device, a TFT (Thin Film Transistor) -LCD is generally known.
  • TFT Thin Film Transistor
  • IPS mode liquid crystal display device
  • the IPS mode is often adopted as a display for a tablet PC or the like, and the brightness of the screen is greatly improved. For this reason, a slight light leakage in the diagonal direction at the time of black display, which has not been regarded as a problem in the past, has become apparent as a cause of a decrease in display quality.
  • Patent Document 1 discloses that a coating liquid in which a rod-like polymerizable liquid crystal compound is dissolved in an organic solvent is applied onto a support having an intermediate layer, and the coating liquid is dried. A method for forming an optically anisotropic layer by heating the coating solution and irradiating the heated coating solution with actinic radiation to cure it is described.
  • Patent Document 2 a blocking layer and an intermediate layer are formed on a support, a coating liquid containing a liquid crystal compound is applied thereon, and the temperature of the coating liquid is increased to a phase transition temperature or higher. And a method of forming an optically anisotropic layer through a drying, heat treatment, and curing step that is maintained below the phase transition temperature.
  • an intermediate layer is often provided on the support and a liquid crystal phase is formed on the intermediate layer in many cases. This is because the intermediate layer has a function of aligning the liquid crystal and a function of preventing the support composition component from diffusing into the liquid crystal film.
  • liquid crystal vertical alignment film is directly formed on the support without using the intermediate layer, it is necessary to perform a special surface treatment such as a rubbing treatment or a plasma treatment on the surface of the support.
  • This surface treatment may cause an increase in manufacturing cost and a decrease in quality due to contamination with dust and the like.
  • an optically anisotropic layer also referred to as a liquid crystal layer
  • the adhesiveness adheresive force
  • the problem of peeling off of the layer became apparent. It is considered that the lack of adhesion occurs because there is no factor for bonding the support and the liquid crystal layer.
  • the present invention has been made in consideration of such problems, and provides a method for producing a retardation film with improved adhesion between a support and an optically anisotropic layer and less liquid crystal alignment failure. With the goal.
  • a method for producing a retardation film includes a step of preparing a belt-like support containing a plasticizer and / or an optical property adjusting agent, and a rod-like polymerizable liquid crystal on a continuously running support.
  • a drying process for fixing the position of the alignment control agent and the alignment auxiliary agent and forming a coating film in which the solvent is impregnated into the support by 0.3 ⁇ m or more, and the internal temperature of the coating film is the alignment control agent A heat treatment step of heating the coating film for 25 seconds or more so that the alignment auxiliary agent is moved to the surface of the coating film, and after the heat treatment step, the internal temperature of the coating film is set to the position of the alignment control agent and the alignment auxiliary agent.
  • Cooling process for cooling to a fixed temperature and after the cooling process 3 is irradiated to the coating film of the residual solvent ratio of less than mass% with active radiation to cure the coating, including a curing step of forming an optically anisotropic layer.
  • the solvent contained in the raw material liquid has a solubility parameter SP value within a range of ⁇ 2 [(J / cm 3 ) 1/2 ] with respect to the solubility parameter SP value of the support material.
  • the raw material liquid contains a plurality of other solvents in addition to the solvent that dissolves and swells the support.
  • the drying step includes a step of drying the film at a drying rate of 0.1 [g / m 2 ⁇ sec] or less.
  • the support is a cellulosic film.
  • the adhesiveness between the support and the optically anisotropic layer is improved, and a retardation film with few liquid crystal alignment defects can be produced.
  • FIG. 1 is a schematic configuration diagram of a retardation film manufacturing facility.
  • FIG. 2A is an explanatory diagram showing the action of a liquid crystal compound, an alignment controller, and an alignment aid.
  • FIG. 2B is an explanatory diagram showing the action of the liquid crystal compound, the alignment controller, and the alignment aid.
  • FIG. 2C is an explanatory diagram showing the action of the liquid crystal compound, the alignment control agent, and the alignment aid.
  • FIG. 2D is an explanatory diagram showing the action of the liquid crystal compound, the alignment controller, and the alignment aid.
  • FIG. 3 is a table showing the results of the examples.
  • FIG. 4 is a table showing the results of the examples.
  • the method for producing a retardation film includes a step of preparing a belt-like support containing a plasticizer and / or an optical property adjusting agent, and a rod-like polymerizable liquid crystal compound and alignment control on the continuously running support.
  • a raw material solution in which an agent and an alignment aid are dissolved in a solvent for dissolving or swelling the support to form a film By applying a raw material solution in which an agent and an alignment aid are dissolved in a solvent for dissolving or swelling the support to form a film, and by drying the film applied on the support, A drying process for forming a coating film in which the position of the control agent and the alignment aid is fixed and the solvent is soaked in the support by 0.3 ⁇ m or more, and the internal temperature of the coating film is the alignment control agent and the alignment aid.
  • a raw material liquid containing a polymerizable liquid crystal compound, an alignment controller, and an alignment aid is prepared using a solvent that dissolves or swells the support. .
  • a solvent that dissolves or swells the support the solvent soaks into the support during the drying step, and a region where the support and the membrane are mixed is formed.
  • the adhesiveness between the support and the optically anisotropic layer can be improved by irradiating with active rays and curing.
  • the penetration thickness 0.3 ⁇ m or more is impregnated so as to adhere more firmly.
  • an optically anisotropic layer is formed with a raw material solution containing a solvent that dissolves or swells the support
  • a plasticizer and / or an optical property adjuster that are components in the support are mixed in the optically anisotropic layer.
  • the orientation of the coating film (liquid crystal film) after the drying step is hindered by the plasticizer and / or optical property modifier, and in particular, the support / optical anisotropy in which there are many plasticizers and / or optical property modifiers. Alignment at the interface portion of the film is hindered and alignment defects may occur.
  • a heat treatment step is provided after the drying step to raise the temperature of the coating film and lower the viscosity.
  • the liquid crystal compound in the coating film moves to make the coating film non-aligned, and the alignment control agent and the alignment aid are diffused to the coating film / air interface.
  • the temperature of the coating film is lowered in the cooling step before irradiation with actinic radiation to increase the viscosity.
  • the liquid crystal compound is reoriented while the movement of the liquid crystal compound in the coating film is moderated, and the diffusion of the alignment control agent and the alignment aid is stopped. It was found that an optically anisotropic layer (liquid crystal phase) free from alignment defects can be formed by curing the coating film by irradiation with active rays in this state.
  • the alignment control agent plays a role of vertically aligning the liquid crystal compound and greatly contributes to the alignment on the support interface side.
  • the orientation control agent contributes to the orientation on the air interface side, but the orientation regulating force is weak. Supporting this is an additive called an alignment aid.
  • the alignment auxiliary agent plays a role of bringing the alignment control agent to the air interface side and unevenly distributing it.
  • the alignment control agent moved to the air interface side contributes to the vertical alignment of the liquid crystal compound at the air interface. It is desirable to use a surfactant as an alignment aid.
  • the coating film is dried and fixed before the alignment control agent and the alignment aid diffuse to the air interface side.
  • the orientation control agent and the alignment aid diffuse again by reducing the viscosity of the coating film.
  • the liquid crystal compound is vertically aligned due to the effect of the alignment control agent, but the alignment is partially inhibited at the interface portion of the support / coating film.
  • the alignment of the liquid crystal compound in the coating film is once brought into the non-aligned state including the interface portion of the support / coating film in which the alignment inhibition has occurred.
  • the liquid crystal compound is re-orientated by cooling before irradiation with actinic radiation.
  • the alignment regulating force on the air interface side is strengthened, thereby supporting the alignment of the interface portion of the support / coating film. It is estimated that the orientation is improved as a whole.
  • the heat treatment temperature needs to be a temperature at which the liquid crystal becomes non-aligned and the fixed alignment control agent and alignment aid diffuse again.
  • the heat treatment time is set to 25 seconds or more, it is possible to secure the time necessary for breaking the alignment inhibition at the interface part of the support / coating film, and the alignment control agent and the alignment aid are sufficiently diffused to the air interface. Time can be secured. As a result, the alignment of the liquid crystal compound is improved.
  • the cooling temperature needs to be a temperature at which the liquid crystal is aligned again and the alignment control agent and alignment aid are fixed again.
  • the support is preferably a resin film that is optically transparent and has birefringence.
  • Engineeringly transparent means having a transmittance of 60% or more, and a transmittance of 80% or more is more preferable.
  • Rth ((n x ⁇ n y ) / 2 ⁇ n z ) ⁇ d (N z : refractive index in the thickness direction)
  • Both Re and Rth are preferably 0 to 150 nm, particularly preferably 70 to 120 nm.
  • the support is made of cellulose film (cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, etc.), polyester film, polycarbonate film, polyester film (polyethylene terephthalate), polyethylene film, polypropylene film, polychlorinated film.
  • the film include a polyvinyl film, a polyvinyl alcohol film, a polymethyl methacrylate film, an acrylic film, and a norbornene film.
  • a cellulose ester film is desirable as such a material.
  • the support includes a plasticizer for imparting desired physical performance and / or an optical property adjusting agent for imparting desired optical performance.
  • the plasticizer is not particularly limited, and preferred examples include phthalate ester, phosphate ester, and resin acid.
  • the optical property modifier is not particularly limited, and preferred examples thereof include optical compounds such as aromatic ring-containing compounds containing nitrogen compounds, liquid crystal compounds, and anisotropically shaped compounds as disclosed in JP-A-2012-234094. Examples include compounds having large anisotropy.
  • the rod-like liquid crystal compound contained in the optically anisotropic layer is, for example, a rod-like nematic liquid crystal compound.
  • rod-like nematic liquid crystal compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, and alkoxy-substituted phenylpyrimidines.
  • Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. Not only low-molecular liquid crystal compounds but also high-molecular liquid crystal compounds can be used.
  • the polymerizable liquid crystal compound can be obtained by introducing a polymerizable group into the liquid crystal compound.
  • the polymerizable group include an unsaturated polymerizable group, an epoxy group, and an aziridinyl group, preferably an unsaturated polymerizable group, and particularly preferably an ethylenically unsaturated polymerizable group.
  • the polymerizable group can be introduced into the molecule of the liquid crystal compound by various methods.
  • the number of polymerizable groups possessed by the polymerizable liquid crystal compound is preferably 1 to 6, more preferably 1 to 3.
  • Examples of polymerizable liquid crystal compounds include Makromol. Chem., 190, 2255 (1989), Advanced Materials, 5, 107 (1993), US Pat. No.
  • the amount of the polymerizable liquid crystal compound contained in the raw material liquid is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, and particularly preferably 25 to 35% by mass. .
  • the alignment control agent plays a role of vertically aligning the liquid crystal compound, and contributes to the alignment of the liquid crystal compound on the intermediate film interface side. That is, the molecules of the liquid crystal compound are substantially vertically aligned by the alignment control agent.
  • the alignment control agent can align the molecules of the liquid crystal compound substantially vertically.
  • Preferable examples include compounds represented by the following general formula. You may contain 2 or more types selected from these.
  • a rod-like structure for vertically aligning the liquid crystal compound that is, the main chain is somewhat long
  • a material having a hydrophilic group that easily binds to the intermediate film and the alignment aid are considered preferable.
  • the —N—C 2 H 6 moiety in the following chemical formula (Chemical Formula 1) is considered to be related to the function of the orientation control agent.
  • R represents an alkoxy group having 1 to 30 carbon atoms, more preferably an alkoxy group having 1 to 20 carbon atoms, and still more preferably an alkoxy group having 1 to 15 carbon atoms.
  • one or more CH 2 and two or more CH 2 not adjacent to each other in the alkoxy group are —O—, —S—, —OCO—, —COO—, —NRa—, —NRaCO—, —CONRa—, It may be substituted with —NRaSO 2 — or —SO 2 NRa—.
  • Ra represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • the amount of the orientation control agent used is preferably 0.001 to 1% by mass, more preferably 0.005 to 0.5% by mass, and more preferably 0.01 to 0.1% by mass of the solid content of the raw material liquid. It is particularly preferable that the content is% by mass.
  • the alignment auxiliary agent plays a role of bringing the alignment control agent to the air interface side to be unevenly distributed, and contributes to the vertical alignment of the liquid crystal compound at the air interface.
  • the above-mentioned alignment control agent contributes to the alignment on the air interface side but does not have a strong alignment regulating force.
  • the alignment aid supports alignment on the air interface side. It is desirable to use a surfactant as an alignment aid.
  • the alignment aid is not particularly limited to this.
  • the alignment auxiliary agent includes a group containing F having poor compatibility with the liquid crystal compound, a hydrophilic group for bonding with the alignment control agent, It is considered preferable to have For example, in chemical formulas 2 and 3 (general formulas (I) and (II)), the group containing F corresponds to the left group, and the hydrophilic group corresponds to the right -COOR- moiety. These are considered to be related to the function of the alignment aid.
  • R represents an alkoxy group having 1 to 30 carbon atoms, more preferably an alkoxy group having 1 to 20 carbon atoms, and still more preferably an alkoxy group having 1 to 15 carbon atoms.
  • a and b represent ratios contained in the compound.
  • the amount of the alignment aid used is preferably 0.001 to 1% by mass, more preferably 0.005 to 0.5% by mass, based on the liquid crystal compound (solid content in the case of a raw material liquid).
  • the content is preferably 0.01 to 0.1% by mass.
  • solvent has a property of dissolving the liquid crystal compound and dissolving or swelling the support.
  • solvents that dissolve or swell cellulose ester include methyl ethyl ketone, acetone, methyl acetate, ethyl acetate, methylene chloride, ethylene chloride, tetrachloroethane, trichloroethane, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.
  • a plurality of solvents that dissolve or swell the support can also be combined.
  • the swelling means a state in which the volume of the polymer substance such as a resin is expanded by maintaining the solid state shape of the polymer substance, and the solvent molecules having a relatively low molecular weight enter the gap between the polymer substances and penetrate.
  • a polymer film having a thickness of 0.1 mm is immersed in a solvent for 10 minutes and the thickness is increased by 1% or more.
  • the thickness can be measured with a film thickness tester (Anritsu KB601).
  • Dissolution means a state in which a polymer chain surrounded by solvent molecules is separated and dispersed in a solvent.
  • a polymer film of 50 mm ⁇ 50 mm ⁇ 0.1 mm is immersed in a solvent for 10 minutes. This means that the film weight decreases by 0.1% or more before and after immersion.
  • the weight can be measured with an electronic balance (XS104 manufactured by Mettler-Toredo).
  • solvents are preferable, for example, for controlling dissolution and swelling of the support.
  • solvents there are alcohols (ethanol, methanol, n-butanol, i-propyl alcohol, n-propyl alcohol, etc.), hydrocarbons (xylene, toluene, etc.) and the like.
  • the raw material liquid may contain a plurality of other solvents in addition to the solvent that dissolves or swells the support.
  • the solvent contained in the raw material liquid preferably has a solubility parameter SP value in a range of ⁇ 2 (J / cm 3 ) 1/2 with respect to the solubility parameter SP value of the support material.
  • a solubility parameter SP value in a range of ⁇ 2 (J / cm 3 ) 1/2 with respect to the solubility parameter SP value of the support material.
  • the adhesion between the optically anisotropic layer and the support can be improved.
  • the raw material liquid preferably contains a polymerization initiator.
  • the polymerization initiator to be used is preferably a photopolymerization initiator that can start the polymerization reaction by ultraviolet irradiation.
  • photopolymerization initiators include ⁇ -carbonyl compounds (described in US Pat. No. 2,367,661 and US Pat. No. 2,367,670), acyloin ethers (described in US Pat. No. 2,448,828), ⁇ -hydrocarbons.
  • a substituted aromatic acyloin compound (described in US Pat. No.
  • the amount of the photopolymerization initiator used is preferably 0.1 to 20% by mass, more preferably 1 to 8% by mass, based on the solid content of the second raw material liquid.
  • the raw material liquid is prepared as a coating liquid in which a liquid crystal compound, an alignment controller, and an alignment aid are dissolved in a solvent.
  • a photopolymerization initiator it is preferable to add to the raw material liquid.
  • the coating liquid is applied to the surface of the intermediate film.
  • a coating method it can be performed by various methods such as a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method.
  • FIG. 1 shows an example of a retardation film manufacturing facility according to the present embodiment.
  • a method for producing a retardation film using this production equipment includes a coating process for applying a raw material liquid on a belt-like support, a drying process for drying the coating film, and a heat treatment for heat-treating the coating film after drying. And a curing step of forming an optically anisotropic layer by irradiating the coating film with actinic radiation and curing after the heat treatment. Manufacturing equipment and each process are explained.
  • the retardation film manufacturing facility 10 includes a delivery device 12 that sends out a support W, a coating head 14 that coats the raw material liquid, a backup roller 16 that holds the support W, and a decompression chamber 18 on the upstream side of the coating head 14. And a drying device 20, a heat treatment device 22, a cooling device 24, an actinic radiation irradiation device 26, a temperature control roller 28, and a winding device 30.
  • the belt-like support W has a roll shape wound around a winding core.
  • the roll-shaped support W is continuously run using the delivery device 12.
  • the delivery device 12 includes a roller (not shown) on which a roll-shaped support W wound around a winding core can be installed. By rotating this roller, the belt-like support W is continuously conveyed to a coating device or the like.
  • the raw material liquid is applied onto the continuously-supported belt-like support W using an application device.
  • a coating device a general coating device can be used without limitation.
  • the backup roller 16 that holds the belt-like support W that is continuously conveyed
  • the coating head 14 that coats the raw material liquid on the belt-like support W wrapped by the backup roller 16, and the raw material from the coating head 14
  • the flow rate of the first raw material liquid supplied from the coating head 14 is adjusted by the pump so that the required film thickness is obtained.
  • the degree of decompression of the decompression chamber 18 is adjusted by a decompression pump.
  • the gap with the backup roller 16 is adjusted to be narrow, and the beads are stably formed.
  • (C) The drying process which dries the film
  • a general drying apparatus can be used without limitation.
  • a convection drying method using hot air, a radiation drying method using radiant heat such as infrared rays, or the like can be used.
  • hot air drying of the coating film is controlled by adjusting the temperature and air volume of the hot air.
  • a slit nozzle (a nozzle having a slit-like opening shape in the width direction of a belt-like support), a punching nozzle (a porous flat plate nozzle), or the like can be used.
  • the coating film is dried until the coating film reaches a drying point.
  • the drying point refers to a point in the drying process in which the film surface temperature of the coating film is the same as the temperature of the drying air near the coating film, and the evaporation of the solvent from the coating film reaches an equilibrium state.
  • the coating film viscosity at this time is 5000 mPa ⁇ s or more.
  • the viscosity of the coating film can be measured with a vibration viscometer (SV-10, manufactured by A & D) by quickly scraping off the coating film on the support that has reached the drying point and putting it in a medicine bottle.
  • the solvent contained in the raw material liquid is soaked into the support W by 0.3 ⁇ m or more. Thereby, the area
  • the solubility of the solvent with respect to the support body W can be controlled by controlling the drying speed in the drying step.
  • the drying speed 0.1 [g / m 2 ⁇ sec] or less, the adhesion performance is further improved, which is more preferable.
  • the amount of the solvent soaked into the support can be increased and the adhesion can be improved.
  • the positions of the alignment control agent and the alignment aid are fixed.
  • a heat treatment apparatus 22 is provided to heat-treat the coating film of the belt-like support W having the coating film dried in the drying process. Heat for at least 25 seconds to reach a temperature at which the alignment control agent and alignment aid diffuse to the surface of the coating.
  • the temperature of the coating film is preferably in the range of 90 to 120 ° C.
  • the heat treatment apparatus 22 can use a general heating apparatus without limitation.
  • a convection drying method using hot air or a radiation drying method using radiant heat such as infrared rays is used.
  • hot air When hot air is used, drying of the coating film is controlled by adjusting the temperature and air volume of the hot air.
  • a slit nozzle a nozzle having a slit-like opening shape in the width direction of a belt-like support
  • a punching nozzle a porous flat plate nozzle
  • the heat treatment step can be continuously provided without leaving the drying step.
  • the band-shaped support W having the coating film heat-treated in the heat treatment process is subjected to the actinic radiation in the curing process by the cooling device 24 in the cooling process.
  • the temperature is adjusted to an appropriate level for irradiation.
  • a convection cooling method using cooling air is generally used. When cooling air is used, the temperature of the coating film is controlled by adjusting the temperature and air volume of the cooling air.
  • a slit nozzle (a nozzle having a slit-like opening shape in the width direction of a belt-like support), a punching nozzle (a porous flat plate nozzle), or the like can be used.
  • a cooling device may not be installed when an appropriate coating film temperature is obtained without providing a cooling step. The cooling temperature is set so that the liquid crystal compound is aligned again and the positions of the alignment control agent and the alignment aid are fixed.
  • the active film irradiation device 26 is used to irradiate the coating active ray cooled in the cooling step to cure the coating.
  • an ultraviolet irradiation device or the like is used as the active ray irradiation device 26.
  • the irradiation intensity and irradiation amount of ultraviolet rays are adjusted to adjust the degree of curing of the coating film.
  • the irradiation intensity is preferably 10 ⁇ 1000mW / cm 2, more preferably 100 ⁇ 400mW / cm 2.
  • total irradiation amount is desirably 10 ⁇ 1000mJ / cm 2, and more preferably 20 ⁇ 200mJ / cm 2.
  • the oxygen concentration in the atmosphere around the coating film when irradiated with actinic radiation may be lowered to adjust the degree of curing of the coating film, and is preferably 50 to 1000 ppm.
  • the residual solvent ratio of the coating film is set to less than 3 mass%. If the ratio of the residual solvent in the film is 3% by mass or more, the residual solvent in the film inhibits the alignment and the subsequent crosslinking reaction by irradiation with active rays, resulting in poor alignment and a decrease in film strength.
  • the coating film temperature before irradiation with actinic radiation can be adjusted by an arbitrary method, and for example, it can be adjusted by wrapping a belt-like support on the temperature control roller 28. 5 to 80 ° C. is desirable, and 20 to 50 ° C. is more preferable.
  • the winding device 30 includes a roller (not shown) on which a winding core can be installed, and continuously winds the belt-like support W by rotating the roller.
  • FIG. 2A shows a state in which a film is formed by applying a raw material liquid containing a liquid crystal compound, an alignment controller, and an alignment aid on the support in the application step. All the materials of the liquid crystal compound, the alignment control agent, and the alignment aid are arranged non-oriented.
  • FIG. 2B shows a state in which the film is dried in the drying process.
  • some liquid crystal compounds are aligned in the vertical direction by the alignment control agent.
  • the liquid crystal compound is vertically aligned by the alignment control agent diffused to the air interface side by the alignment aid.
  • the diffusion of the alignment control agent and the alignment aid stops.
  • some liquid crystal compounds are not aligned in the vertical direction.
  • the solvent is soaked in the support by 0.3 ⁇ m or more.
  • FIG. 2C shows a state in which the coating film is heated in the heat treatment step.
  • the viscosity of the coating film becomes low, and the alignment control agent and the alignment aid diffuse to the air interface side. Further, the alignment of the liquid crystal compound is lost, and the liquid crystal compound is randomly arranged.
  • FIG. 2D shows a state in which the active ray is irradiated through the cooling process.
  • the liquid crystal compound is aligned again.
  • the alignment control agent and the alignment aid are moved to the air interface side at that time, the alignment regulating force for the liquid crystal compound on the air interface side is strengthened.
  • the orientation of the interface portion of the support / optically anisotropic layer is supported, and the orientation of the liquid crystal compound of the optically anisotropic layer is presumed to be improved as a whole.
  • Fujitac TD40UZ which is a commercially available cellulose triacetate film (TAC) manufactured by FUJIFILM Corporation, was prepared.
  • TAC time-of-flight secondary ion mass spectrometer
  • molecular ions derived from the support and additives support component: C 5 H 5 O 2 + , a plasticizer component; C 14 H 15 O 6 (derived from a phthalate ester), an optical developer component: C 24 H 25 N 6 (derived from a nitrogen compound) were detected.
  • Polymeric liquid crystal compound (liquid crystal phase-isotropic phase transition temperature is differential scanning calorimetry) comprising 80% by mass of a compound represented by the following chemical formula (Chemical formula 4) and 20% by mass of the following compound represented by the following chemical formula (Chemical formula 5).
  • the prepared raw material liquid was supplied to the slit die of the manufacturing equipment shown in FIG. 1 and applied onto the film.
  • the solvent of the film was dried in a drying process to form a coating film. Specifically, it was dried with hot air at 55 ° C. until it reached the drying point to form a coating film.
  • the coating film temperature and the film surface temperature of the belt-like support were measured by installing a non-contact thermometer (IT2-80, manufactured by Keyence Corporation).
  • the temperature of the coating film is cooled to a temperature at which the polymerizable liquid crystal compound is oriented again and the alignment controller and the alignment aid are fixed, and the temperature before ultraviolet irradiation is set to the temperature described in the table. Then, UV irradiation with an integrated light amount of 300 mJ / cm 2 was performed with a high-pressure mercury lamp in an atmosphere with an oxygen concentration of 300 ppm.
  • Example 1-10 and Comparative Example 1-11 were produced.
  • the drying speed was controlled by adjusting the temperature of the drying process and the solvent gas concentration.
  • the drying speed of the coating film is calculated from the solid content concentration immediately after the drying process, and the solid content concentration after the drying process is obtained by sampling the film after the drying process and using a vacuum drying apparatus (DP22 manufactured by Yamato Kagaku). It calculated from the mass before and behind removing. The mass was measured with an electronic balance (XS104 manufactured by Mettler-Toredo).
  • the residual solvent ratio after the heat treatment step was calculated from the mass before and after removing the solvent with a vacuum dryer (DP22 manufactured by Yamato Kagaku) after sampling the film after the heat treatment step, similarly to the drying speed.
  • the mass was measured with an electronic balance (XS104 manufactured by Mettler-Toredo).
  • the thickness of the solvent soaked into the support is measured by cutting a section of the sample that has undergone the active irradiation step with a focused ion beam (FIB) and observing it with a scanning electron microscope (SEM). It was. (The FIB and SEM were evaluated using the FEI Helios400S with which the device is integrated.) ⁇ Evaluation of orientation defects> The obtained film was sandwiched between crossed Nicol polarizers, and the presence or absence of a cloudy portion observed due to alignment defects was visually observed.
  • FIB focused ion beam
  • SEM scanning electron microscope
  • Example 1-10 evaluation of C or higher was performed for adhesion, and evaluation of alignment defect was B or higher.
  • Example 3 since the penetration thickness was 1.5 ⁇ m, the evaluation was A regarding the adhesion.
  • the penetration thickness of Example 8 was 0.5 ⁇ m, the evaluation for adhesion was C.
  • Example 1-3, 6, and 8-10 which satisfy the conditions of 100 ° C. and 60 seconds in the heat treatment process, the evaluation for the alignment defect was A. It is considered that the alignment control agent and the alignment aid are diffused on the surface of the coating film.
  • the evaluation was B for the alignment defects. It is considered that the diffusion between the alignment control agent and the alignment aid was small compared to Examples 1-3, 6, and 8-10.
  • Example 7 was 83 ° C. lower than the liquid crystal phase-isotropic phase transition temperature. Evaluation was B.
  • Comparative Example 2 PET was used as the support and MEK was used as the solvent. Since it was 0.1 micrometer, evaluation was D regarding adhesiveness.
  • the liquid crystal phase-isotropic phase transition temperature was ⁇ 1 ° C.
  • the diffusion of the alignment control agent and the alignment auxiliary agent was not sufficient
  • the evaluation for the alignment defect was C.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Liquid Crystal (AREA)
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JP2016206236A (ja) * 2015-04-15 2016-12-08 大日本印刷株式会社 光学フィルム
WO2021033639A1 (ja) * 2019-08-16 2021-02-25 富士フイルム株式会社 光学フィルムの製造方法
WO2021167075A1 (ja) * 2020-02-20 2021-08-26 富士フイルム株式会社 光学積層体、偏光板、画像表示装置
WO2022176884A1 (ja) * 2021-02-16 2022-08-25 富士フイルム株式会社 光学フィルムの製造方法

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