WO2019171877A1 - Procédé de fabrication d'un corps stratifié - Google Patents

Procédé de fabrication d'un corps stratifié Download PDF

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Publication number
WO2019171877A1
WO2019171877A1 PCT/JP2019/004546 JP2019004546W WO2019171877A1 WO 2019171877 A1 WO2019171877 A1 WO 2019171877A1 JP 2019004546 W JP2019004546 W JP 2019004546W WO 2019171877 A1 WO2019171877 A1 WO 2019171877A1
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Prior art keywords
temperature
coating film
liquid crystalline
dichroic compound
compound
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PCT/JP2019/004546
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English (en)
Japanese (ja)
Inventor
洋平 ▲濱▼地
小堂　厚司
靖和 桑山
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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 KR1020207021330A priority Critical patent/KR102445631B1/ko
Priority to JP2020504878A priority patent/JP6741899B2/ja
Publication of WO2019171877A1 publication Critical patent/WO2019171877A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid

Definitions

  • the present invention relates to a method for manufacturing a laminate.
  • Patent Document 1 A polarizing plate using a dichroic dye instead of polyvinyl alcohol (PVA) dyed with iodine for the purpose of improving heat resistance and moisture resistance is also known (Patent Document 2).
  • PVA polyvinyl alcohol
  • a polarizing film which is an optical film containing a dichroic dye, is formed on an alignment film.
  • the polarizing film is formed from a coating solution in which a dichroic dye and a polymerizable liquid crystal compound (polymerizable liquid crystal compound) are dissolved in a solvent.
  • the coating liquid is applied onto the alignment film and the formed coating film is polymerized at a temperature lower than the phase transition temperature of the polymerizable liquid crystal compound, the polymerizable liquid crystal compound is not polymerized. Dry with.
  • the dried coating film is heated above the nematic transition temperature of the polymerizable liquid crystal compound, and then cooled to a temperature at which a smectic phase liquid crystal state is obtained.
  • Patent Document 2 forms an alignment layer, which is an optical film containing a dichroic dye, on an alignment film.
  • a liquid crystalline dichroic dye is used as the dichroic dye.
  • a coating solution in which the liquid crystalline dichroic dye is dissolved in a solvent is applied onto the alignment film, and the solvent is removed from the formed coating film.
  • the orientation is fixed by heating the coating film to a temperature at which the liquid crystalline dichroic dye exhibits a liquid crystal state, and then the orientation is fixed by cooling.
  • Patent Document 2 must use a liquid crystalline dichroic dye, but the manufacturing method of Patent Document 1 has an advantage in that it is not necessary to use a liquid crystalline dichroic dye. However, according to the manufacturing method of Patent Document 1, the orientation of the optical film may be insufficient.
  • an object of the present invention is to provide a method for producing a laminate including an optical film with improved orientation.
  • the method for producing a laminate of the present invention includes a coating film forming step, a drying step, a first heating step, a cooling step, and a second heating step.
  • the coating film forming step forms a coating film by applying a coating liquid containing a liquid crystalline compound, a dichroic compound, and a solvent that dissolves the liquid crystalline compound and the dichroic compound on the alignment film. .
  • the drying process reduces the solvent from the coating.
  • a 1st heating process heats the coating film in which the solvent decreased, and makes it 1st temperature higher than melting
  • the coating film that has undergone the first heating step is cooled to a second temperature that is lower than the crystallization temperature of the dichroic compound and lower than the crystallization temperature of the liquid crystalline compound.
  • a 2nd heating process heats the coating film which passed through the cooling process, and makes it the 3rd temperature lower than the nematic transition temperature of a liquid crystalline compound.
  • the third temperature is preferably a temperature not lower than the association promotion temperature range that promotes the association of the dichroic compound.
  • the third temperature is preferably higher than at least the crystallization temperature of the liquid crystalline compound.
  • the third temperature is preferably lower than the crystallization temperature of the dichroic compound.
  • the coating film that has undergone the cooling step is preferably heated at a heating rate of 0.1 ° C./second or more and 3.0 ° C./second or less.
  • the second heating step it is preferable to maintain the third temperature T3 for 1 second or longer.
  • a laminate comprising an optical film with improved orientation can be produced.
  • the laminated body 10 manufactured by this invention is a polarizing plate which arranges incident light into specific polarized light, for example.
  • the laminate 10 includes a base material 11, a first protective layer 12 laminated on the base material 11, an alignment film 13 laminated on the first protective layer 12, and a coating optical film 14 laminated on the alignment film 13. And a second protective layer 15 laminated on the coated optical film 14.
  • the substrate 11 is not particularly limited as long as it does not change when forming the coated optical film 14 or the like.
  • the substrate 11 may be a polyester polymer such as polyethylene terephthalate or polyethylene naphthalate, diacetyl cellulose, or Cellulose polymer such as triacetyl cellulose (TAC), polycarbonate polymer, acrylic polymer such as polymethyl methacrylate, styrene polymer such as polystyrene or acrylonitrile styrene copolymer, polyethylene, polypropylene, cyclic or norbornene structure Olefin polymers such as polyolefin and ethylene propylene copolymers, vinyl chloride polymers, amide polymers such as nylon or aromatic polyamide, imide polymers Sulfone polymers, polyethersulfone polymers, polyetheretherketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers,
  • the first protective layer 12 protects the alignment film 13 and the coating optical film 14 from water (including water vapor) and / or oxygen that permeates the base material 11.
  • the 1st protective layer 12 is polyvinyl alcohol (PVA), and shields the water etc. which permeate
  • PVA polyvinyl alcohol
  • the 1st protective layer 12 can be abbreviate
  • the alignment film 13 regulates the alignment of the liquid crystalline compound contained in the coating optical film 14 under specific conditions.
  • the alignment film 13 contains an azo compound, and this azo compound is a photo-alignment film that is isomerized by irradiation with ultraviolet rays or the like polarized in a specific direction and aligned along a specific direction.
  • the azo compound any of a monomer, an oligomer, and a polymer can be used.
  • azobenzene that is a monomer is used.
  • cinnamate may be used.
  • the coated optical film 14 is contained by rubbing the surface of the substrate 11, the first protective layer 12, or other film provided on the first protective layer 12.
  • the orientation of the liquid crystal compound to be controlled can be regulated.
  • the coated optical film 14 has a function as a polarizer in the laminate 10.
  • the coating optical film 14 is an optical film formed by coating, and contains a liquid crystalline compound and at least one dichroic compound 31.
  • the liquid crystalline polymer 21 (see FIG. 2) is used as the liquid crystalline compound.
  • the liquid crystalline polymer 21 is a polymer having a mesogenic group in the main chain or side chain.
  • a thermotropic liquid crystalline polymer described in JP2011-237513A or a polymer having thermotropic liquid crystal described in JP2016-4055A can be used.
  • the liquid crystalline polymer 21 may have a crosslinkable group (for example, acryloyl group and methacryloyl group) at the terminal.
  • other liquid crystalline compounds such as a liquid crystalline monomer or a liquid crystalline polymer different from the liquid crystalline polymer 21 can be used instead of or together with the liquid crystalline polymer 21.
  • the liquid crystalline polymer 21 contained in the coating optical film 14 is a so-called side chain type, and includes a flexible main chain 22 and a side chain 24 having a mesogenic group 23.
  • the mesogenic group 23 is generally aligned along a predetermined direction (hereinafter referred to as X direction) by the alignment film 13 in the manufacturing process.
  • the main chain 22 is generally oriented in a direction perpendicular to the X direction (hereinafter referred to as the Y direction).
  • the liquid crystalline polymer 21 of the coating optical film 14 is arranged in a ladder shape or a network shape, and at least partially includes the one or more dichroic compounds 31 by the main chain 22 and the mesogenic group 23.
  • the dichroic compound 31 is a compound having so-called dichroism, and there is a difference in the absorption intensity of each linearly polarized light when irradiated with two linearly polarized light having different polarization directions by 90 degrees.
  • the dichroic compound 31 contained in the coating optical film 14 has the above-mentioned dichroism, and the property that two or more are bonded in a regular arrangement by intermolecular force under specific conditions ( So-called association). Therefore, when the liquid crystalline polymer 21 traps (captures) the dichroic compound 31 having two or more associative properties in the void 26, these dichroic compounds 31 associate to form an aggregate 32 in the manufacturing process.
  • the orientation is roughly aligned.
  • the orientation of the dichroic compound 31 and / or the aggregate 32 of the dichroic compound 31 trapped in the void 26 is generally regulated in the same direction as the mesogenic group 23.
  • Examples of the dichroic compound 31 include paragraphs [0067] to [0071] in JP 2013-228706 A, paragraphs [0008] to [0026] in JP 2013-227532 A, and JP 2013-209367 A. [0008] to [0015] paragraphs of the publication, paragraphs [0045] to [0058] of JP 2013-14883 A, paragraphs [0012] to [0029] of JP 2013-109090 A, JP 2013-101328 A Paragraphs [0009] to [0017], JP-A-2013-37353, paragraphs [0051] to [0065], JP-A-2012-63387, paragraphs [0049] to [0073], JP-A-11- [0016] to [0018] paragraphs of Japanese Patent No.
  • the second protective layer 15 protects the coated optical film 14 from water or the like.
  • the second protective layer 15 is formed of an acrylic polymer, an acrylate monomer polymer, an epoxy monomer polymer, or a cyclic olefin polymer (COP) or a cyclic olefin copolymer (COC). Not limited to.
  • the dichroic compound 31 and / or the aggregate 32 absorbs polarized light in the X direction with respect to light incident from the substrate 11 side or the second protective layer 15 side, Moreover, since it transmits polarized light in the Y direction, it functions as a polarizing plate. Further, the coating optical film 14 having a function as a polarizer can be formed very thin, and the orientation of the dichroic compound 31 is aligned with high accuracy in the coating optical film 14.
  • permeability is made higher than the polarizing plate (henceforth an iodine addition PVA polarizing plate) which uses the PVA which added iodine for the laminated body 10 (especially, the transmittance
  • the degree of polarization is higher than that of the iodine-added PVA polarizing plate.
  • the coating optical film 14 can be formed thinner than the iodine-added PVA polarizing plate. As a result, the entire laminate 10 is thinner than the iodine-added PVA polarizing plate, and is equal to or higher than the iodine-added PVA polarizing plate. It has durability (heat resistance or moisture resistance).
  • the laminate 10 is manufactured using, for example, a manufacturing apparatus 40 shown in FIG.
  • the laminate 10 is manufactured in a long shape, but may be manufactured in a sheet shape by cutting the obtained long laminate 10.
  • the manufacturing apparatus 40 includes a first protective layer forming unit 41, an alignment film forming unit 42, a coating optical film forming unit 43, and a second protective layer forming unit 44 in order from the upstream side in the transport direction of the long base material 11.
  • the first protective layer forming unit 41 forms the first protective layer 12 on the substrate 11.
  • the alignment film forming unit 42 forms the alignment film 13 on the first protective layer 12.
  • the coating optical film forming unit 43 forms the coating optical film 14 on the alignment film 13.
  • the second protective layer forming unit 44 forms the second protective layer 15 on the coated optical film 14.
  • the manufacturing apparatus 40 uses the transport mechanism (transport roller, transport roller drive mechanism, and the like) (not shown) to transport the base material 11 in the longitudinal direction, and the respective units sequentially stack the films or layers to form the laminate 10. obtain.
  • symbol Dc is attached
  • the first protective layer forming unit 41 includes a coating film forming unit 51 and a drying unit 52.
  • the coating film forming unit 51 applies a coating solution 53 in which PVA is dissolved in a solvent on the base material 11 moving in the transport direction Dc to form a coating film 54.
  • the drying section 52 forms the first protective layer 12 on the substrate 11 by reducing the solvent from the coating film 54 by heating, blowing, natural drying and / or other methods, and drying the coating film 54. To do.
  • the alignment film forming unit 42 includes a coating film forming unit 61, a drying unit 62, and a light irradiation unit 63.
  • the coating film forming unit 61 applies a coating solution 66 in which an azo compound is dissolved in a solvent on the first protective layer 12 to form a coating film 67.
  • the drying unit 62 reduces the solvent from the coating film 67 by heating, blowing, natural drying, and / or other methods, and drying the coating film 67, thereby forming the dried coating film 68 on the first protective layer 12.
  • the light irradiation unit 63 irradiates the dried coating film 68 with ultraviolet polarized light.
  • the dried coating film 68 isomerizes the azo compound in accordance with the polarization direction of the ultraviolet rays to form the alignment film 13.
  • the coating optical film forming unit 43 includes a coating film forming unit 91, a drying unit 92, and a temperature management unit 93.
  • the coating film forming unit 91 applies a coating liquid 94 containing the liquid crystalline polymer 21, the dichroic compound 31, and a solvent for dissolving the liquid crystalline polymer 21 and the dichroic compound 31 on the alignment film 13.
  • the coating film 96 is formed (coating film formation process).
  • the coating liquid 94 of this example is in a state where the liquid crystalline polymer 21 and the dichroic compound 31 are dissolved in a solvent.
  • the drying unit 92 reduces the solvent from the coating film 96 by heating, blowing, natural drying, and / or other methods, and the coating film 96 is dried, thereby forming the dried coating film 97 on the alignment film 13.
  • the temperature management unit 93 ripens the dried coating 97 by raising the temperature of the dried coating 97, which is a coating with a reduced solvent, and lowering the temperature, and / or maintaining a specific temperature range.
  • the temperature management performed by the temperature management unit 93 the orientation of the liquid crystalline polymer 21 and the dichroic compound 31 is more precisely adjusted in the dry coating film 97.
  • the dried coating film 97 becomes the coated optical film 14 having a function as a polarizer.
  • the solvent may remain in the dry coating 97, and a small amount remains in this example.
  • the temperature management unit 93 includes a first heating unit 101, a first cooling unit 102, a second heating unit 103, and a second cooling unit 104, and the temperature control shown in FIG. Manage the temperature according to the profile.
  • 1st heating part 101 heats intermediate layered product 110 conveyed from drying part 92, and makes it specific temperature from the temperature at the time of conveying from drying part 92 (for example, normal temperature To).
  • the first heating unit 101 performs at least a first heating step P1 that heats at least the dry coating film 97 to a first temperature T1 that is higher than the melting point Tm of the dichroic compound 31.
  • the melting point Tm of the dichroic compound 31 is usually higher than the nematic transition temperature Tne of the liquid crystalline polymer 21. For this reason, when the 1st heating part 101 makes the dry coating film 97 1st temperature T1, it will exceed the nematic transition temperature Tne of the liquid crystalline polymer 21 automatically.
  • the first temperature T1 is a temperature higher than the nematic transition temperature Tne of the liquid crystalline polymer 21. That is, the first temperature T1 is at least higher than the melting point Tm of the dichroic compound 31 and higher than the nematic transition temperature Tne of the liquid crystalline polymer 21.
  • the first temperature T1 needs to be lower than the melting point (not shown) of the liquid crystalline polymer 21.
  • the melting point of the liquid crystalline polymer 21 is exceeded, the dried coating film 97 is melted and the film state cannot be maintained. As a result, the coated optical film 14 cannot be formed from the dried coating film 97.
  • the first temperature T1 is a temperature at which the substrate 11, the first protective layer 12, or the alignment film 13 is damaged (for example, melting, deformation, or alteration (the alignment film 13 loses the direction of isomerization).
  • the first temperature T1 is a temperature at which the liquid crystalline polymer 21 exhibits a nematic phase.
  • the first heating step P1 preferably includes a temperature raising step P1a and a temperature maintaining step P1b.
  • the temperature raising step P1a is a step in which a practical temperature rise change up to the first temperature T1 is generated and the dry coating film 97 having a temperature lower than the first temperature T1 is first raised to the first temperature T1.
  • the temperature maintenance process P1b is a process of maintaining the dry coating film 97 that has reached the first temperature T1 at the first temperature T1.
  • the reason why the dry coating film 97 is set to the first temperature T1 is that the liquid crystalline polymer 21 and the dichroic compound 31 are compatible by making the liquid crystalline polymer 21 into a nematic phase and melting the dichroic compound 31. It is for making it into a state. Therefore, if this state can be created, the specific temperature rise profile when the dry coating film 97 is set to the first temperature T1 is arbitrary. For example, in the temperature profile of FIG.
  • the temperature raising step P1a linearly raises the temperature of the dry coating film 97 at a constant rate of temperature rise from the elapsed time t1 to the elapsed time t2, but the temperature raising step P1a
  • the temperature may be raised stepwise up to one temperature T1 or along a curve of an arbitrary shape.
  • the first temperature T1 is almost completely maintained from the elapsed time t2 to the elapsed time t3, but it is only necessary to maintain a temperature equal to or higher than the first temperature T1. That is, “maintaining the first temperature T1” means “maintaining a temperature higher than the melting point Tm of the dichroic compound 31 and higher than the nematic transition temperature Tne of the liquid crystalline polymer 21”.
  • the actual liquid crystal polymer 21 exhibits a nematic phase in the entire dry coating film 97, and is a practical requirement for realizing a state in which the liquid crystal polymer 21 and the dichroic compound 31 are compatible. It is sufficient to maintain the first temperature T1 for a long time.
  • the time for maintaining the first temperature T1 depends on the material of each part constituting the liquid crystalline polymer 21, the dichroic compound 31, and the other intermediate laminate 110, and is, for example, about several seconds to several tens of seconds.
  • the time is preferably from 19 seconds to 19 seconds, more preferably from 15 seconds to 15 seconds, and particularly preferably from 9 seconds to 11 seconds.
  • the time for maintaining the first temperature T1 is 10 seconds.
  • the first heating unit 101 heats the dry coating film 97, in the state where the temperature of the dry coating film 97 is lower than the nematic transition temperature Tne of the liquid crystalline polymer 21, as shown in FIG.
  • the liquid crystalline polymer 21 and the dichroic compound 31 are solidified in a state of being arranged almost randomly. Thereafter, when the dry coating film 97 reaches the first temperature T1, as shown in FIG. 10, the liquid crystalline polymer 21 increases the fluidity to exhibit a nematic phase, and is aligned approximately in accordance with the alignment film 13.
  • the dichroic compound 31 melts and is compatible with the liquid crystalline polymer 21, but the liquid crystalline polymer 21 has an orientation generally in accordance with the alignment film 13. Therefore, as a result, it becomes easy to gather between the mesogenic groups 23.
  • the first cooling unit 102 cools the dried coating film 97 that has undergone the first heating step P1, and changes the first temperature T1 to a second temperature T2 that is lower than at least the crystallization temperature Tc of the dichroic compound 31. Cooling process P2 (cooling process) is performed. More preferably, the second temperature T2 is a temperature lower than the crystallization temperature Tc of the dichroic compound 31 and lower than the crystallization temperature Ts of the liquid crystalline polymer 21. In the present embodiment, the second temperature T2 is a temperature lower than the crystallization temperature Tc of the dichroic compound 31 and lower than the crystallization temperature Ts of the liquid crystalline polymer 21.
  • the crystallization temperature Tc of the dichroic compound 31 is usually lower than the nematic transition temperature Tne of the liquid crystalline polymer 21. For this reason, when the 1st cooling part 102 makes the dry paint film 97 2nd temperature T2, it is automatically lower than the nematic transition temperature Tne of the liquid crystalline polymer 21. In general, since the crystallization temperature Ts of the liquid crystalline polymer 21 is lower than the crystallization temperature Tc of the dichroic compound 31, the first cooling unit 102 is in the process of setting the dry coating film 97 to the second temperature T2. The dichroic compound 31 is crystallized before the liquid crystalline polymer 21.
  • the second temperature T2 is a temperature lower than at least the crystallization temperature Tc of the dichroic compound 31. That is, the second temperature T2 needs to be at least lower than the crystallization temperature Tc of the dichroic compound 31, but is not necessarily lower than the crystallization temperature Ts of the liquid crystalline polymer 21.
  • the liquid crystalline polymer 21 includes one or a plurality of dichroic compounds 31 in the voids 26 formed as a result of regular alignment according to the alignment film 13, and dichroism. This is because the compound 31 only needs to be able to suppress movement such as movement or rotation while maintaining a substantially constant orientation in the constant gap 26 formed by the liquid crystalline polymer 21.
  • the first cooling step P2 is a step of rapidly cooling the dried coating film 97. For this reason, in the first cooling step P2, the dried coating film 97 is cooled at a cooling rate equal to or higher than a predetermined cooling rate, or the dried coating film 97 is cooled within a predetermined time from the first temperature T1 to the second temperature T2. To do.
  • the cooling rate is a rate of temperature decrease that lowers (ie, decreases) the temperature. For example, the cooling rate of 3 ° C./second means that the temperature is lowered by 3 ° C. per second.
  • the first cooling step P2 is performed by dry coating at a cooling rate (hereinafter referred to as a predetermined cooling rate) of at least 1 ° C./second or more, more preferably 3 ° C./second or more, particularly preferably 5 ° C./second or more.
  • a predetermined cooling rate of at least 1 ° C./second or more, more preferably 3 ° C./second or more, particularly preferably 5 ° C./second or more.
  • the membrane 97 is cooled.
  • the dichroic compound 31 is crystallized at the crystallization temperature Tc. More practically, the dichroic compound 31 is in a predetermined temperature range (hereinafter, Crystallization occurs in the crystallization temperature range.
  • the upper limit temperature of the crystallization temperature range (that is, the temperature at which crystallization of the dichroic compound 31 starts during cooling) is “Tc1”, and the lower limit temperature of the crystallization temperature range (that is, the crystal of the dichroic compound 31)
  • Tc1 the temperature at which crystallization of the dichroic compound 31
  • Tc2 the temperature at which crystallization is completed
  • the predetermined cooling rate is a so-called average rate. For this reason, it may include time for cooling at a cooling rate lower than a predetermined cooling rate in a part of the process of cooling the dry coating film 97.
  • the cooling rate averaged in any one of the temperature sections may be a predetermined cooling rate.
  • the cooling rate in the first cooling step P2 it is preferable to cool as fast as possible if each part of the intermediate
  • the dry coating film 97 is applied from the first temperature T1 to the second temperature T2, within 0.01 seconds to 110 seconds, preferably within 0.01 seconds to 40 seconds, more preferably The dried coating film 97 is cooled within 0.01 seconds to 25 seconds, particularly preferably within 0.01 seconds to 10 seconds. More practically, the time required to reach at least the upper limit temperature Tc1 of the crystallization temperature range and the lower limit temperature Tc2 of the crystallization temperature range may be 0.01 seconds or more and 40 seconds or less. The time is more preferably from 01 seconds to 20 seconds, and particularly preferably from 0.01 seconds to 10 seconds.
  • the dry coating film 97 can be cooled at least within the predetermined cooling rate or within the predetermined time, and the dry coating film 97 is cooled within the predetermined cooling rate and within the predetermined time. It is preferable.
  • a specific cooling profile in the first cooling step P2 is arbitrary. For example, in FIG. 8, in the first cooling step P2, the temperature of the dry coating film 97 is linearly decreased at a constant cooling rate from the elapsed time t3 to the elapsed time t4, but the first cooling step P2 is performed at the second temperature. The temperature may be lowered stepwise up to T2 or along a curve of an arbitrary shape.
  • the first cooling step P2 may include a part of the time period during which the temperature of the dry coating film 97 does not decrease (maintain a constant temperature, etc.).
  • the 1st cooling process P2 may have the time slot
  • the lowest temperature reached in the first cooling step P2 is the second temperature T2.
  • the first cooling process P2 is the next process of the first heating process P1. That is, after the first heating step P1 and before the start of the first cooling step P2, the first step without the step with the temperature change of the dry coating 97 and the other step with the change in the state of the dry coating 97 are not performed.
  • the first cooling step P2 is performed immediately after the heating step P1.
  • the liquid crystalline polymer 21 is solidified while the mesogenic group 23 approaches the regular alignment state according to the alignment film 13 more accurately as shown in FIG.
  • the air gap 26 is further clarified.
  • the dichroic compound 31 follows the alignment direction of the mesogenic groups 23 in the voids 26 and is solidified while maintaining a substantially constant alignment state, and is in a phase-separated state with respect to the liquid crystalline polymer 21.
  • the dried coating film 97 has a function as a uniform polarizer as a whole.
  • the dichroic compound 31 trapped in the void 26 destroys the void 26 or is bonded to another void 26, for example.
  • the reason why the crystallization is performed while maintaining the arrangement order according to the voids 26 formed by the mesogenic groups 23 and the like without crystal growth with random orientation is because the dried coating film 97 is rapidly cooled in the first cooling step P2. It is. Further, in the first cooling step P2, the liquid crystalline polymer 21 is solidified while the mesogenic group 23 approaches the regular alignment state according to the alignment film 13 more accurately. It is because it cools quickly.
  • the 2nd heating part 103 performs the 2nd heating process P3 which heats the dry paint film 97 which passed through the 1st cooling process P2, and makes it the 3rd temperature T3.
  • the third temperature T3 is at least lower than the nematic transition temperature Tne of the liquid crystalline polymer 21. Further, the third temperature T3 is preferably lower than the crystallization temperature Tc of the dichroic compound 31.
  • the crystallization temperature Ts of the liquid crystalline polymer 21 is lower than the nematic transition temperature Tne, and the third temperature T3 is at least higher than the crystallization temperature Ts of the liquid crystalline polymer 21.
  • the third temperature T3 is a temperature in the temperature range where the association of the dichroic compound 31 is promoted (hereinafter referred to as the association promotion temperature range) RT or higher. Therefore, the second heating step P3 promotes the association of the plurality of dichroic compounds 31 included in one void 26 formed by the liquid crystalline polymer 21.
  • association-accelerating temperature range RT is X 1 ° C. or more X 2 ° C. or less, and the meeting promotes temperature range RT or higher, at least X 1 ° C. or higher, X 1 ° C. or more X 2 ° C. below the temperature
  • the temperature may be X 2 ° C or higher.
  • the second heating step P3 preferably includes a temperature raising step P3a and a temperature maintaining step P3b.
  • the temperature raising step P3a is a step in which a practical temperature increase up to the third temperature T3 is generated, and the dry coating film 97 is first heated to the third temperature T3.
  • the temperature maintaining step P3b is a step of maintaining the dry coating film 97 that has reached the third temperature T3 at the third temperature T3.
  • the reason why the dry coating film 97 is set to the third temperature T3 is to promote the association of the dichroic compound 31, and therefore the specific temperature rise profile when the dry coating film 97 is set to the third temperature T3 is arbitrary. It is.
  • the temperature raising step P3a linearly raises the temperature of the dry coating film 97 at a constant rate of temperature rise from the elapsed time t5 to the elapsed time t6.
  • the temperature can be raised stepwise up to 3 temperatures T3 or along a curve of an arbitrary shape.
  • the second heating step P3 it is preferable to heat the dried coating film 97 that has undergone the first cooling step P2 at a predetermined heating rate (hereinafter referred to as a predetermined heating rate).
  • the heating rate is a rate of temperature increase that raises the temperature (that is, increases the temperature).
  • a heating rate of 3 ° C./second means that the temperature is increased by 3 ° C. per second.
  • the predetermined heating rate is, for example, 0.1 ° C./second or more and 3.0 ° C./second or less, and more preferably 0.5 ° C./second or more and 2.0 ° C./second or less. Since it takes time for the dichroic compound 31 to form the association body 32, if the heating rate is high, a sufficient association body cannot be formed, and the degree of orientation decreases. Further, when the heating rate is slow, the process length becomes long and the process load increases.
  • the predetermined heating rate is a so-called average rate. For this reason, in the part of the process which heats the dry coating film 97 which passed through the 1st cooling process P2, the time heated at the heating rate outside the range of the predetermined heating rate may be included.
  • the heating rate averaged in the temperature raising step P3a may be a predetermined heating rate.
  • the temperature maintaining step P3b schematically maintains the third temperature T3 almost completely from the elapsed time t6 to the elapsed time t7, but it is only necessary to maintain at least a temperature higher than the association promotion temperature range RT. That is, “maintaining the third temperature T3” means maintaining a temperature not lower than the association promotion temperature range RT. Therefore, the temperature maintaining process P3b does not need to strictly maintain a specific temperature (the third temperature T3 set as a target for temperature increase), and there may be a temperature change of the dry coating film also in the temperature maintaining process P3b. .
  • the liquid crystal polymer 21 does not break the alignment state according to the alignment film 13 and the association of the dichroic compound 31 is substantially completed in the entire dry coating film 97. It is only necessary to maintain the third temperature T3 for a long time.
  • the second heating step P3 is performed in the temperature maintaining step P3b and / or the temperature raising step P3a, depending on the liquid crystal polymer 21, the dichroic compound 31, and other materials constituting the intermediate laminate 110.
  • the third temperature T3 is preferably maintained continuously or intermittently for at least 1 second or more, and more preferably maintained for 3 seconds or more.
  • the mesogenic group 23 of the liquid crystalline polymer 21 is gradually maintained while generally maintaining the alignment state of the liquid crystalline polymer 21 and the dichroic compound 31 (see FIG. 11). Gain some mobility. As a result, the mesogenic group 23 follows the alignment film 13 better. Further, the dichroic compound 31 obtains mobility when the crystallization temperature Tc exceeds the crystallization temperature Tc and becomes a temperature equal to or higher than the association promotion temperature range RT, but the gap 26 formed by the mesogenic group 23 and the like is not removed and the same. The probability of contact with another dichroic compound 31 in the void 26 is increased. As a result, the association of the dichroic compound 31 proceeds in each gap 26, and the degree of orientation of the dried coating film 97 is improved (see FIG. 2).
  • the second cooling unit 104 performs a second cooling step P4 that cools the dried coating film 97 that has undergone the second heating step P3 naturally or actively by blowing air or the like.
  • the dried coating film 97 is brought to a temperature such as room temperature To or room temperature, for example.
  • the dried coating film 97 that has undergone the second cooling step P4 becomes the coated optical film 14 having a high degree of orientation while maintaining a good polarizer state with improved polarization degree (see FIG. 6).
  • the first heating unit 101, the first cooling unit 102, the second heating unit 103, and the second cooling unit 104 constituting the temperature management unit 93 are, for example, a conveyance roller with a temperature adjustment function as shown in FIG. (Hereinafter referred to as a temperature control roller) 116 and a temperature control unit 117.
  • the temperature control roller 116 adjusts the temperature of the contact surface with the intermediate laminate 110 by passing oil or the like whose temperature has been adjusted by the temperature control unit 117 inside.
  • the temperature control roller 116 is a drive roller having a rotation control unit in the present embodiment.
  • the temperature control roller 116 may be a driven roller that rotates by contact with the conveyed intermediate laminate 110.
  • the contact area of the intermediate laminate 110 with respect to the peripheral surface of the temperature control roller 116 is increased by sucking the atmosphere below the paper surface of FIG. I am letting.
  • middle laminated body 110 can be heated or cooled more rapidly and uniformly.
  • the second protective layer forming unit 44 includes a coating film forming unit 121 and a drying unit 122.
  • the coating film forming unit 121 applies a coating liquid 126 containing an epoxy monomer polymer that is a material of the second protective layer 15 and a solvent that dissolves the epoxy monomer polymer onto the coating optical film 14.
  • Application is performed to form a coating film 127.
  • the drying unit 122 reduces the solvent from the coating film 127 by heating, blowing, natural drying, and / or other methods, and the coating film 127 is dried, so that the second protective layer 15 is formed on the coated optical film 14. Form. Thereby, the laminated body 10 is completed.
  • the manufacturing apparatus 41 includes the liquid crystalline polymer 21 and the dichroic compound 31, and when forming the coating optical film 14 that expresses the function as a polarizer by the orientation of the dichroic compound 31, Since the 1st heating process P1 and the 1st cooling process P2 are performed, the laminated body 10 which has the coating optical film 14 with high orientation degree and the coating optical film 14 with high orientation degree can be obtained.
  • the dichroic compound 31 has an associative property
  • the coating optical film 14 and the laminated body in which the dichroic compound 31 forms the associated body 32 and the degree of orientation is further improved by performing the second heating step P3. 10 is obtained.
  • the coating optical film 14 is formed by using the liquid crystalline polymer 21 and one type of dichroic compound 31, but the coating optical film 14 has two or more types.
  • the dichroic compound 31 can be contained.
  • the dichroic compound 31 has different wavelength bands of light to be absorbed depending on the type, when the coating optical film 14 contains two or more types of dichroic compounds 31, only one type of dichroic compound 31 is used.
  • the wavelength band in which the laminate 10 functions as a polarizing plate can be made wider than in the case.
  • at least one type contains the dichroic compound 31 that mainly absorbs the green wavelength band. It is particularly preferable that the dichroic compound 31 that absorbs the green wavelength band has association properties. This is because green has higher visibility than blue or red.
  • the coating optical film 14 contains two or more kinds of dichroic compounds 31, it is preferable that at least one kind contains the dichroic compounds 31 having associative properties. This is because the degree of orientation is particularly easily improved by promoting the association by performing the second heating step P3. However, even when the coating optical film 14 contains only one type or a plurality of types of dichroic compounds 31 that do not have associative properties, the dichroism is obtained through the first heating step P1 and the first cooling step P2. The compound 31 can obtain a certain orientation. Even when the coating optical film 14 contains only one or a plurality of types of dichroic compounds 31 having no associative properties, the orientation degree of the liquid crystalline polymer 21 is improved by performing the second heating step P3. Therefore, the degree of orientation of the dichroic compound 31 is improved following the improvement of the degree of orientation of the liquid crystalline polymer 21.
  • the first temperature T1 is set to a temperature higher than the maximum value of the melting point Tm of the dichroic compound 31. This is because all the dichroic compounds 31 are melted.
  • the second temperature T2 is set to a temperature lower than at least the minimum value of the crystallization temperature Tc of the dichroic compound 31. This is because all the dichroic compounds 31 are solidified to suppress motility.
  • the second temperature is lower than the crystallization temperature Ts of the liquid crystalline polymer 21.
  • the third temperature is set to a value lower than the lowest value of the crystallization temperature Tc of the associative dichroic compound 31 and lower than the nematic transition temperature Tne of the liquid crystalline polymer 21. Set T3. This is because the dichroic compound 31 having all the associative properties is given motility and the association is promoted with the positional restriction in the void 26 being imposed.
  • the cooling conditions in the first cooling step P2 were changed to the conditions shown in Table 1, and the stacked body 10 of the example and the stacked body of the comparative example were manufactured.
  • the laminated body 10 of each example and the laminated body of each comparative example have the same manufacturing conditions and configuration other than the conditions shown in Table 1.
  • the substrate 11 is formed of a TAC film
  • the first protective layer 12 is formed of PVA
  • the alignment film 13 is a photo-alignment film using azobenzene
  • the second protective layer 15 is an epoxy-based film. It is a monomer polymer.
  • the liquid crystalline polymer 21 used for the coating optical film 14 is L1 below.
  • the liquid crystalline polymer 21 of L1 is composed of a repeating unit represented by (1) and a repeating unit represented by (2).
  • the liquid crystalline polymer 21 of the following L1 has a nematic transition temperature Tne of about 97 ° C. and a crystallization temperature Ts of about 67 ° C.
  • the dichroic compound 31 used for the coating optical film 14 is D1 below.
  • the following dichroic compound 31 of D1 has a melting point Tm of about 140 ° C. and a crystallization temperature Tc of about 85 ° C.
  • the heating rate in the second heating step P3 is about 2.0 ° C./second, and the heating time is at least 1 second.
  • the association promotion temperature range RT of the dichroic compound 31 shown in D1 below is about 50 ° C. or higher and about 80 ° C. or lower.
  • the parentheses () written in the “presence / absence of maintenance step” column of Table 1 is the time during which the first temperature T1 was maintained.
  • the laminated body 10 of an Example and the laminated body of a comparative example were evaluated using the orientation degree by the following method.
  • ⁇ Measurement method of orientation degree> The second protective layer 15 was peeled from the obtained laminate 10. Then, in a state where a linear polarizer is inserted on the light source side of an optical microscope (manufactured by Nikon Corporation, product name “ECLIPSE E600 POL”), “laminate with the second protective layer 15 peeled off” on the sample base in the examples and comparative examples
  • the body 10 was set, the absorbance in the wavelength region of 400 to 700 nm was measured using a multi-channel spectrometer (product name“ QE65000 ”manufactured by Ocean Optics), and the degree of orientation was calculated by the following formula.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Laminated Bodies (AREA)

Abstract

Procédé de fabrication d'un corps stratifié pourvu d'un film optique présentant une orientation améliorée. Lors d'une première étape de chauffage (P1), un film de revêtement sec (97) qui comprend un polymère à cristaux liquides (21) et un composé dichroïque (31) est chauffé, amenant le film de revêtement sec (97) à une première température (T1) qui est supérieure au point de fusion du composé dichroïque. Lors d'une première étape de refroidissement (P2), le film de revêtement sec (97) est refroidi, amenant le film de revêtement sec (97) à une deuxième température (T2) qui est inférieure à la température de cristallisation (Tc) du composé dichroïque (31) et inférieure à la température de cristallisation (Ts) du polymère à cristaux liquides (21). Lors d'une seconde étape de chauffage (P3), le film de revêtement sec (97), ayant traversé la première étape de refroidissement (P2), est chauffé, amenant le film de revêtement sec (97) à une troisième température (T3) qui est inférieure à la température de transition nématique (Tne) du polymère à cristaux liquides (21).
PCT/JP2019/004546 2018-03-06 2019-02-08 Procédé de fabrication d'un corps stratifié WO2019171877A1 (fr)

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WO2017090668A1 (fr) * 2015-11-24 2017-06-01 富士フイルム株式会社 Composé colorant dichroïque, composition de colorant dichroïque, film anisotrope absorbant la lumière, élément polarisant et dispositif d'affichage d'image
WO2017154907A1 (fr) * 2016-03-08 2017-09-14 富士フイルム株式会社 Composition colorée, film anisotrope d'absorption de lumière, stratifié et dispositif d'affichage d'image
WO2017195833A1 (fr) * 2016-05-12 2017-11-16 富士フイルム株式会社 Composition colorée, composé colorant dichroïque, film d'anisotropie par absorption de lumière, produit stratifié, et dispositif d'affichage d'image

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WO2017090668A1 (fr) * 2015-11-24 2017-06-01 富士フイルム株式会社 Composé colorant dichroïque, composition de colorant dichroïque, film anisotrope absorbant la lumière, élément polarisant et dispositif d'affichage d'image
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WO2017195833A1 (fr) * 2016-05-12 2017-11-16 富士フイルム株式会社 Composition colorée, composé colorant dichroïque, film d'anisotropie par absorption de lumière, produit stratifié, et dispositif d'affichage d'image

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