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WO2019225517A1 - Procédé de production de produit stratifié - Google Patents

Procédé de production de produit stratifié Download PDF

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Publication number
WO2019225517A1
WO2019225517A1 PCT/JP2019/019791 JP2019019791W WO2019225517A1 WO 2019225517 A1 WO2019225517 A1 WO 2019225517A1 JP 2019019791 W JP2019019791 W JP 2019019791W WO 2019225517 A1 WO2019225517 A1 WO 2019225517A1
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Prior art keywords
film
mass
group
coating
coating film
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Japanese (ja)
Inventor
諭司 國安
洋平 濱地
靖和 桑山
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Fujifilm Corp
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Fujifilm Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the present disclosure relates to a method for manufacturing a laminate.
  • a polarizing element used in a liquid crystal display device is generally manufactured by further providing a polarizing film on an alignment film.
  • Discloses a technique for forming a polarizing layer from a second dry film by polymerizing a conductive smectic liquid crystal compound see, for example, JP-A-2017-102479).
  • the polarizing film on the alignment film is, for example, a coating liquid containing a liquid crystal compound, a dichroic compound such as a dichroic dye, and a solvent that dissolves the liquid crystal compound and the dichroic compound (hereinafter, a coating for forming a polarizing film).
  • a coating liquid containing a liquid crystal compound, a dichroic compound such as a dichroic dye, and a solvent that dissolves the liquid crystal compound and the dichroic compound hereinafter, a coating for forming a polarizing film.
  • a coating for forming a polarizing film Also referred to as a liquid
  • the liquid crystal compounds are aligned side by side on the alignment film, and the dichroic compounds are aligned side by side along with the aligned liquid crystal compounds.
  • Dichroic compounds tend to be crystallized while having the property of being relatively easy to line up.
  • the coating liquid for forming a polarizing film containing a dichroic compound may be crystallized due to a slight change in composition due to a change in temperature of the coating liquid or solvent volatilization.
  • the solid content concentration is often less than 7% by mass.
  • the dichroic compounds are aggregated and overlapped with each other even when trying to align the dichroic compound well at the molecular level. Disorders of dichroic compounds may occur. When the arrangement of the dichroic compounds is disturbed, there arises a problem that haze increases and transparency as a polarizing element is significantly impaired.
  • the problem to be solved by one embodiment of the present invention is to provide a method for producing a laminate that can produce a laminate having a low haze.
  • ⁇ 1> a step of applying a coating liquid containing a liquid crystalline polymer, a dichroic compound, and a solvent that dissolves the liquid crystalline polymer and the dichroic compound on the alignment film to form a coating film; Reducing the solvent from the coating, Have The method for producing a laminate, wherein in the step of reducing the solvent from the coating film, the solid content change rate from 7 mass% to 15 mass% of the solid content concentration in the coating film is 1.6 mass% / second or more.
  • ⁇ 2> In the step of reducing the solvent from the coating film, at least part of the solid content concentration in the coating film is from 7% by mass to 15% by mass, and the film surface temperature of the coating film is maintained at 30 ° C. or higher.
  • ⁇ 3> The method for producing a laminate according to ⁇ 1> or ⁇ 2>, wherein the solvent in the coating solution contains an organic solvent having a boiling point of 80 ° C. or lower.
  • ⁇ 4> The method for producing a laminate according to ⁇ 3>, wherein the organic solvent having a boiling point of 80 ° C. or less is 30% by mass or more based on the total amount of the solvent.
  • ⁇ 5> The method for producing a laminate according to ⁇ 3> or ⁇ 4>, wherein the organic solvent having a boiling point of 80 ° C. or less is contained in an amount of 50% by mass or more based on the total amount of the solvent.
  • ⁇ 6> The method for producing a laminate according to any one of ⁇ 1> to ⁇ 5>, wherein the solid content concentration of the coating liquid is 1% by mass or more and less than 7% by mass.
  • a method for manufacturing a laminate that can produce a laminate having a low haze.
  • FIG. 1 is a schematic configuration diagram illustrating a schematic configuration example of a manufacturing apparatus for manufacturing a laminate.
  • FIG. 2 is a schematic configuration diagram illustrating another schematic configuration example of a manufacturing apparatus for manufacturing a laminated body.
  • FIG. 3 is a schematic cross-sectional view showing a schematic configuration of the alignment film forming portion.
  • FIG. 4 is a schematic diagram schematically showing a polarizing film.
  • FIG. 5 is a schematic cross-sectional view showing a schematic configuration of the polarizing film forming unit.
  • FIG. 6 is a diagram illustrating an example of a change in solid content concentration of a coating film with time.
  • FIG. 7 is a schematic diagram schematically showing the state of the dried coating film after cooling after drying.
  • process is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
  • numerical ranges indicated using “to” indicate ranges including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • an upper limit value or a lower limit value described in a numerical range may be replaced with an upper limit value or a lower limit value in another numerical range.
  • the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • the manufacturing method of the laminated body of this indication is a coating liquid containing a liquid crystalline polymer, a dichroic compound, and a solvent that dissolves the liquid crystalline polymer and the dichroic compound (that is, a coating liquid for forming a polarizing film).
  • a coating film forming process On the alignment film to form a coating film (hereinafter also referred to as a coating film forming process) and a process for reducing the solvent from the coating film (hereinafter also referred to as a drying process).
  • the step of reducing the solvent from the film that is, the drying step
  • the solid content change rate from 7% by mass to 15% by mass of the solid content concentration in the coating film is 1.6% by mass / second or more. It is a manufacturing method.
  • the aspect which further provided other processes other than the coating-film formation process and the drying process may be sufficient as the manufacturing method of the laminated body of this indication.
  • symbol described in several drawing is the same, it points out the same object.
  • haze refers to the state of being cloudy white.
  • the haze is a value measured according to JIS K 7136: 2000 “How to determine the haze of a transparent material” in Japanese Industrial Standard (JIS), and a haze meter (for example, Nippon Denshoku Industries Co., Ltd.). NDH2000 manufactured by the same company).
  • a method of forming a polarizing film on an alignment film a method of applying a polarizing film forming coating solution and drying it is known.
  • a coating film containing a liquid crystalline polymer, a dichroic compound, and a solvent that dissolves the liquid crystalline polymer and the dichroic compound is formed.
  • the polarizing film is formed by drying the formed coating film.
  • the liquid crystal compounds are aligned side by side in response to the alignment surface of the alignment film, and the dichroic compounds are aligned side by side along with the aligned liquid crystal compounds.
  • the dichroic compound may be disordered as a result of aggregation and overlapping.
  • the haze increases, and the transparency as the polarizing element tends to be significantly impaired.
  • a coating film formed by a coating solution for forming a polarizing film containing a liquid crystalline polymer, a dichroic compound, and a solvent that dissolves the dichroic compound has a solid content concentration of 7% by mass or more.
  • crystallization of the component tends to occur. This is because when the solid content concentration is 7% by mass or more, the intermolecular distance of the solid content approaches, and in particular, aggregation (for example, crystallization) of the dichroic compound is likely to occur.
  • the viscosity of the coating film becomes high, so that the movement of the dichroic compound in the coating film is restricted, and aggregation (for example, dichroism) This is less likely to occur due to crystallization of the compound.
  • a specific solid content concentration region in the drying process that is, a solid content concentration region of 7% by mass to 15% by mass is an aggregation of dichroic compounds (for example, dichroic compound concentration). It was found that this is a region where crystallization is likely to occur. Therefore, the inventors suppress the aggregation of the dichroic compound by increasing the time for changing the solid content concentration of the coating film from 7% by mass to 15% by mass (that is, by increasing the drying time). I found out that
  • a method for producing a laminate of the present disclosure includes a coating liquid containing a liquid crystalline polymer, a dichroic compound, and a solvent that dissolves the liquid crystalline polymer and the dichroic compound.
  • the method for manufacturing a laminate of the present disclosure it is possible to obtain a laminate in which a decrease in haze due to aggregation of components such as a dichroic compound is suppressed.
  • a polarizing element described in JP-A-2017-102479 described above, it is presumed that the above aggregation (for example, due to crystallization of a dichroic compound) is likely to occur, and the haze is low. It is considered difficult to produce a suppressed laminate.
  • a manufacturing apparatus 100 illustrated in FIG. 1 includes a long base material 11 in the longitudinal direction, and includes an alignment film forming unit 42 and a polarizing film forming unit 43 in order from the upstream side in the transport direction Dc of the base material 11. Yes.
  • the alignment film 13 is formed on the base material 11 in the alignment film formation unit 42, and the liquid crystalline polymer is formed on the alignment film 13 formed in the next polarizing film formation unit 43.
  • a coating liquid that is, a polarizing film forming coating liquid
  • a coating liquid that is, a polarizing film forming coating liquid
  • a solvent that dissolves the dichroic compound to form a coating film
  • a polarizing film 14 is formed.
  • a solid content change rate from 7 mass% of solid content concentration in a coating film to 15 mass% is 1.6 mass% / second or more in a drying process.
  • the manufacturing method of the laminated body of the present disclosure includes a first protective layer forming unit 41 and a second protective layer forming unit 44 in addition to the alignment film forming unit 42 and the polarizing film forming unit 43.
  • 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 polarizing film forming unit 43 forms the polarizing film 14 on the alignment film 13 on the first protective layer 12.
  • the second protective layer forming unit 44 forms the second protective layer 15 on the polarizing film 14.
  • each of the above-described units moves while conveying the long base material 11 in the longitudinal direction using a conveyance mechanism (such as a conveyance roller and a conveyance roller driving mechanism) (not shown).
  • the laminated body 10 is manufactured by forming a film or a layer on the substrate 11 that is present.
  • the laminated body may be manufactured in a long shape as in the above-described manufacturing apparatus, or the obtained long laminated body is cut, although not illustrated. It may be manufactured in a sheet shape. Moreover, the manufacturing method of the laminated body of this indication may manufacture the laminated body of sheet
  • a coating liquid containing a liquid crystalline polymer, a dichroic compound, a liquid crystalline polymer and a solvent that dissolves the dichroic compound that is, a polarizing film forming coating liquid, hereinafter simply applied.
  • a liquid is applied onto the alignment film to form a coating film.
  • the coating film formed by applying the coating liquid for forming a polarizing film becomes a polarizing film through a drying process described later.
  • the solid content concentration (also referred to as solid content amount) of the polarizing film forming coating solution used in this step is preferably less than 7% by mass from the viewpoint of suppressing crystallization of components such as a dichroic compound. In it, 6.5 mass% or less is more preferable, and 6 mass% or less is still more preferable.
  • the lower limit of the solid content concentration of the coating solution is not particularly limited, but is preferably 1% by mass or more from the viewpoint of increasing the solid content concentration and ease of application. From the above, it is preferable that the solid content concentration of the polarizing film forming coating solution used in this step is, for example, 1% by mass or more and less than 7% by mass.
  • the temperature of the coating liquid for forming a polarizing film applied in this step is preferably in the range of 30 ° C. or higher and 50 ° C. or lower.
  • the solid surface concentration in the coating film is at least partly between 7% by mass and 15% by mass, and the film surface temperature of the coating film is 25. It is preferable to keep the temperature at or higher (preferably 30 ° C. or higher). Therefore, after the temperature of the coating liquid is set to 25 ° C. or higher (preferably 30 ° C.
  • the coating liquid is separated from the coating device where the temperature is controlled, and then, for example, heat exchange with the base material or solvent It is suitable for effectively maintaining the temperature of the coating film at 25 ° C. or more, since the temperature decrease of the coating film caused by the cooling action by the heat of vaporization at the time of volatilization is suppressed. Moreover, when the temperature of the coating solution is 50 ° C. or less, it is advantageous in that foaming (that is, boiling) of the coating solution is suppressed. Among the above, the temperature of the coating liquid for forming a polarizing film applied in this step is more preferably in the range of 35 ° C. or higher and 40 ° C. or lower for the same reason as described above.
  • the temperature of the coating liquid for forming a polarizing film to be applied refers to the temperature of the coating liquid present at a site in the coating apparatus that is in contact immediately before leaving the coating apparatus.
  • this corresponds to the temperature of the coating liquid present in the die immediately before leaving the die.
  • the temperature of the polarizing film forming coating solution can be measured by a conventional method using a thermometer capable of measuring the solution temperature.
  • the coating liquid for forming a polarizing film contains a liquid crystalline polymer, a dichroic compound, a solvent that dissolves the liquid crystalline polymer and the dichroic compound.
  • the coating liquid for forming a polarizing film can contain other components such as an interface improver and an additive as necessary.
  • the coating liquid for forming a polarizing film in the present disclosure contains at least one liquid crystalline polymer.
  • the liquid crystalline polymer is a polymer having a mesogenic group in the main chain or side chain, and has a flexible main chain 22 and a side chain 24 having a mesogenic group 23 as shown in FIG. 21 is preferred.
  • the mesogenic group 23 is aligned along a certain direction (X direction in FIG. 4) by the alignment film in the process of forming the polarizing film, and the main chain 22 is perpendicular to the X direction ( The orientation is in the Y direction in FIG. Then, as shown in FIG.
  • the liquid crystalline polymer 21 is arranged in a ladder shape or a network shape, and preferably, at least in part, one or two or more dichroic compounds are formed by a main chain and a mesogenic group.
  • a void 26 including the associated aggregate 32 is formed.
  • liquid crystalline polymer examples include a thermotropic liquid crystalline polymer described in JP2011-237513A, a polymer having thermotropic liquid crystal described in JP2016-4055A, and the like.
  • the liquid crystalline polymer may have a crosslinkable group (for example, acryloyl group, methacryloyl group, etc.) at the terminal.
  • a liquid crystalline polymer having thermotropic properties and crystallinity is preferable.
  • the liquid crystalline polymer having a thermotropic property is a high-molecular liquid crystal compound that exhibits a transition to a liquid crystal phase due to a temperature change.
  • the liquid crystalline polymer may exhibit either a nematic phase or a smectic phase, and preferably exhibits at least a nematic phase from the viewpoint of increasing the degree of alignment of the polarizing film and making it difficult to observe haze.
  • the temperature range showing the nematic phase is preferably room temperature (that is, 23 ° C.) to 200 ° C., and more preferably 50 ° C. to 150 ° C. from the viewpoint of handleability and production suitability.
  • a liquid crystalline polymer having crystallinity is a polymer that exhibits a transition to a crystalline layer due to a temperature change.
  • the liquid crystalline polymer having crystallinity may exhibit a glass transition in addition to the transition to the crystal layer.
  • a liquid crystalline polymer is a liquid crystal compound having a transition from a crystal phase to a liquid crystal phase when heated (there may be a glass transition in the middle), or a crystal phase when the temperature is lowered after being brought into a liquid crystal state by heating. It is preferably a liquid crystal compound having a transition to (which may have a glass transition in the middle).
  • the presence or absence of crystallinity of the liquid crystalline polymer is evaluated as follows. Two polarizers of an optical microscope (for example, ECLIPSE E600 POL manufactured by Nikon) are arranged so as to be orthogonal to each other, and a sample stage is set between the two polarizers. Then, a small amount of the liquid crystalline polymer is placed on the slide glass, and the slide glass is set on the hot stage placed on the sample table. While observing the state of the sample, the temperature of the hot stage is raised to a temperature at which the liquid crystalline polymer exhibits liquid crystallinity to bring the liquid crystalline polymer into a liquid crystal state.
  • an optical microscope for example, ECLIPSE E600 POL manufactured by Nikon
  • the behavior of the liquid crystal phase transition is observed while gradually decreasing the temperature of the hot stage, and the temperature of the liquid crystal phase transition is recorded.
  • the liquid crystalline polymer exhibits a plurality of liquid crystal phases (for example, a nematic phase and a smectic phase)
  • all the transition temperatures are recorded.
  • a liquid crystal polymer sample is placed in an aluminum pan, covered, and set on a differential scanning calorimeter (ie, DSC) (where an empty aluminum pan is used as a reference). After heating to a temperature at which the liquid crystalline polymer measured above exhibits a liquid crystal phase, the temperature is maintained for 1 minute.
  • DSC differential scanning calorimeter
  • the method for obtaining a liquid crystalline polymer having crystallinity is not particularly limited, and for example, a liquid crystalline polymer containing a structural unit represented by the following formula (1) (also referred to as structural unit (1) in the present disclosure). Among them, a method using a preferred embodiment in the liquid crystalline polymer containing the structural unit (1) is more preferable.
  • the crystallization temperature of the liquid crystalline polymer is preferably 0 ° C. or higher and lower than 150 ° C., more preferably 0 ° C. or higher and 120 ° C. or lower, still more preferably 15 ° C. or higher and lower than 120 ° C., 15 ° C. It is particularly preferably 95 ° C. or lower.
  • the crystallization temperature of the liquid crystalline polymer is preferably less than 150 ° C. from the viewpoint of reducing haze.
  • the crystallization temperature is obtained from the temperature of the exothermic peak due to crystallization in DSC.
  • the liquid crystalline polymer is preferably a liquid crystalline polymer containing a structural unit represented by the following formula (1) (that is, the structural unit (1)).
  • P1 represents the main chain of the structural unit
  • L1 represents a single bond or a divalent linking group
  • SP1 represents a spacer group
  • M1 represents a mesogenic group
  • T1 represents a terminal group.
  • main chain of the structural unit represented by P1 include groups represented by the following formulas (P1-A) to (P1-D).
  • Group represented by the following formula (P1-A) is preferred from the standpoint of properties and easy handling.
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 represents an alkyl group.
  • the group represented by the formula (P1-A) is preferably a unit by a partial structure of poly (meth) acrylate obtained by polymerizing (meth) acrylate.
  • the group represented by the formula (P1-B) is preferably an ethylene glycol unit obtained by polymerizing ethylene glycol.
  • the group represented by the formula (P1-C) is preferably a propylene glycol unit obtained by polymerizing propylene glycol.
  • the group represented by the formula (P1-D) is preferably a siloxane unit of a polysiloxane obtained by condensation polymerization of silanol.
  • Examples of the divalent linking group represented by L1 include —C (O) O—, —OC (O) —, —O—, —S—, —C (O) NR 3 —, —NR 3 C (O). -, -SO 2- , -NR 3 R 4- and the like.
  • R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent (for example, a substituent W described later).
  • P1 is a group represented by the formula (P1-A)
  • L1 is preferably a group represented by —C (O) O—.
  • P1 is a group represented by the formulas (P1-B) to (P1-D)
  • L1 is preferably a single bond.
  • the spacer group represented by SP1 is at least one selected from the group consisting of an oxyethylene structure, an oxypropylene structure, a polysiloxane structure, and an fluorinated alkylene structure for reasons such as easy liquid crystallinity and availability of raw materials. It preferably includes a seed structure.
  • the oxyethylene structure represented by SP1 is preferably a group represented by * — (CH 2 —CH 2 O) n1 — *.
  • n1 represents an integer of 1 to 20, and * represents a bonding position with L1 or M1 in the formula (1).
  • n1 is preferably an integer of 2 to 10, more preferably an integer of 2 to 4, and most preferably 3.
  • the oxypropylene structure represented by SP1 is preferably a group represented by * — (CH (CH 3 ) —CH 2 O) n2 — *.
  • n2 represents an integer of 1 to 3
  • * represents a bonding position with L1 or M1 in the formula (1).
  • the polysiloxane structure represented by SP1 is preferably a group represented by * — (Si (CH 3 ) 2 —O) n3 — *.
  • n3 represents an integer of 6 to 10
  • * represents a bonding position with L1 or M1 in the formula (1).
  • the fluorinated alkylene structure represented by SP1 is preferably a group represented by * — (CF 2 —CF 2 ) n4 — *.
  • n4 represents an integer of 6 to 10
  • * represents a bonding position with L1 or M1 in the formula (1).
  • the mesogenic group represented by M1 is a group showing the main skeleton of liquid crystal molecules that contribute to liquid crystal formation.
  • the liquid crystal molecules exhibit liquid crystallinity that is an intermediate state between the crystalline state and the isotropic liquid state (ie, mesophase).
  • mesogenic group There is no particular limitation on the mesogenic group.
  • “Flushage Kristall in Tablen II” VEB Deutsche Verlag fur Grundstoff Industry, Leipzig, 1984, pp. 7-16) Reference can be made to the liquid crystal handbook (Maruzen, published in 2000), especially the description in Chapter 3.
  • the mesogenic group for example, a group having at least one cyclic structure selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group, and an alicyclic group is preferable.
  • the mesogenic group preferably has an aromatic hydrocarbon group, more preferably has 2 to 4 aromatic hydrocarbon groups, and still more preferably has 3 aromatic hydrocarbon groups.
  • the mesogenic group is preferably a group represented by the following formula (M1-A) or formula (M1-B) from the viewpoints of liquid crystallinity expression, adjustment of liquid crystal phase transition temperature, raw material availability, and synthesis suitability. And a group represented by the formula (M1-B) is more preferable.
  • A1 is a divalent group selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group, and an alicyclic group. These divalent groups may be substituted with a substituent such as an alkyl group, a fluorinated alkyl group, an alkoxy group, or a substituent W described later.
  • the divalent group represented by A1 is preferably a 4-membered to 6-membered ring.
  • the divalent group represented by A1 may be monocyclic or condensed. * Represents a bonding position with SP1 or T1 in the formula (1).
  • Examples of the divalent aromatic hydrocarbon group represented by A1 include a phenylene group, a naphthylene group, a fluorene-diyl group, an anthracene-diyl group, a tetracene-diyl group, and the like. From the viewpoint of properties, a phenylene group or a naphthylene group is preferable, and a phenylene group is more preferable.
  • the divalent heterocyclic group represented by A1 may be either aromatic or non-aromatic, and is preferably an aromatic heterocyclic group from the viewpoint of further improving the degree of orientation.
  • Examples of atoms other than carbon constituting the aromatic heterocyclic group include a nitrogen atom, a sulfur atom, and an oxygen atom.
  • the aromatic heterocyclic group has a plurality of atoms constituting a ring other than carbon, these may be the same or different.
  • aromatic heterocyclic group examples include pyridylene group (pyridine-diyl group), pyridazine-diyl group, imidazole-diyl group, thienylene (thiophene-diyl group), quinolylene group (quinoline-diyl group), isoquinolylene group ( Isoquinoline-diyl group), oxazole-diyl group, thiazole-diyl group, oxadiazole-diyl group, benzothiazol-diyl group, benzothiadiazole-diyl group, phthalimido-diyl group, thienothiazole-diyl group, thiazolothiazole- Examples thereof include a diyl group, a thienothiophene-diyl group, and a thienoxazole-diyl group.
  • divalent alicyclic group represented by A1 examples include a cyclopentylene group and a cyclohexylene group.
  • a1 represents an integer of 1 to 10.
  • the plurality of A1 may be the same or different.
  • A2 and A3 each independently represent a divalent group selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group, and an alicyclic group. Specific examples and preferred embodiments of A2 and A3 are the same as those of A1 in the formula (M1-A), and thus description thereof is omitted.
  • a2 represents an integer of 1 to 10, and when a2 is 2 or more, the plurality of A2 may be the same or different, and the plurality of LA1 are They may be the same or different.
  • a2 is preferably an integer of 2 or more, and more preferably 2.
  • LA1 represents a divalent linking group
  • each of the plurality of LA1 independently represents a single bond or a divalent linking group
  • At least one of LA1 in the above represents a divalent linking group.
  • a2 it is preferable that one of the two LA1s is a divalent linking group and the other is a single bond.
  • the divalent linking group represented by LA1 includes —O—, — (CH 2 ) g —, — (CF 2 ) g —, —Si (CH 3 ) 2 —, — (Si (CH 3 ) 2 O).
  • LA1 may be a group obtained by combining two or more of the above groups. Among these, LA1 is preferably —C (O) O—.
  • M1 include the following structures, for example.
  • “Ac” represents an acetyl group.
  • Examples of the (meth) acryloyloxy group-containing group include, for example, -LA (L represents a single bond or a linking group. Specific examples of the linking group are the same as those of L1 and SP1 described above.
  • A represents (meth) Group represented by acryloyloxy group).
  • T1 is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and further preferably a methoxy group.
  • the terminal group may be further substituted with a group exemplified above or a polymerizable group described in JP 2010-244038 A.
  • the number of atoms in the main chain of T1 is preferably 1-20, more preferably 1-15, still more preferably 1-10, and particularly preferably 1-7. When the number of atoms in the main chain of T1 is 20 or less, the degree of orientation of the polarizing film is further improved.
  • the “main chain” in T1 means the longest molecular chain bonded to M1, and hydrogen atoms and branched carbon atoms are not included in the number of atoms in the main chain of T1. For example, when T1 is an n-butyl group, the number of atoms in the main chain is 4, and when T1 is a sec-butyl group, the number of atoms in the main chain is 3.
  • the content of the structural unit (1) is preferably 20% by mass to 100% by mass, more preferably 30% by mass to 99.9% by mass with respect to 100% by mass of all the structural units of the liquid crystalline polymer, and 40% by mass. % To 99.0% by mass is more preferable.
  • the structural unit (1) may be an embodiment in which two or more structural units are included in addition to an embodiment in which the liquid crystalline polymer is included alone. Especially, the aspect in which a liquid crystalline polymer contains 2 types of structural units (1) is preferable.
  • one of the structural units (1) (also referred to as structural unit A) has an alkoxy group as the terminal group represented by T1, and the other (structural unit B).
  • the terminal group represented by T1 is preferably a group other than an alkoxy group.
  • the terminal group represented by T1 in the structural unit B is preferably an alkoxycarbonyl group, a cyano group, or a (meth) acryloyloxy group-containing group, and more preferably an alkoxycarbonyl group or a cyano group.
  • the ratio (A / B; mass basis) of the content of the structural unit A to the content of the structural unit B in the liquid crystalline polymer is preferably 50/50 to 95/5, and preferably 60/40 to 93. / 7 is more preferable, and 70/30 to 90/10 is still more preferable.
  • the weight average molecular weight (Mw) of the liquid crystalline polymer is preferably 1,000 to 500,000, and more preferably 2,000 to 300,000.
  • the weight average molecular weight (Mw) of the liquid crystalline polymer is preferably 10,000 or more, and more preferably 10,000 to 300,000.
  • the weight average molecular weight (Mw) of the liquid crystalline polymer is preferably less than 10,000, and more preferably 2,000 or more and less than 10,000.
  • the weight average molecular weight is a value measured by the gel permeation chromatograph (GPC) method under the following conditions.
  • Solvent eluent
  • N-methylpyrrolidone Device name TOSOH HLC-8220GPC
  • Substituent W The substituent W in the present disclosure will be described below.
  • the substituent W include a halogen atom, an alkyl group (including a tert-butyl group, a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group).
  • a liquid crystalline polymer may be used individually by 1 type, and may use 2 or more types together. There is no restriction
  • the coating liquid for forming a polarizing film in the present disclosure contains at least one dichroic compound.
  • a dichroic compound is a compound having a so-called dichroism, and is a compound that produces a difference in the absorption intensity of each linearly polarized light when irradiated with two linearly polarized lights having different polarization directions by 90 °.
  • the dichroic compound preferably has a property (so-called associative property) in which two or more are bonded in a regular arrangement by intermolecular force under specific conditions.
  • the dichroic compound 31 when the liquid crystalline polymer traps (that is, traps) the dichroic compound 31 having two or more associative properties in the gap 26 as shown in FIG. 4, the dichroic compound 31 is formed in the process of forming the polarizing film. Associate to form an aggregate 32 and align. In addition, at least one of the dichroic compound 31 trapped in the gap 26 and the aggregate 32 of the dichroic compound 31 is oriented in the same direction as the mesogenic group 23.
  • dichroic compounds examples include visible light absorbing substances (also called dichroic dyes), luminescent substances (fluorescent substances, phosphorescent substances, etc.), ultraviolet absorbing substances, infrared absorbing substances, nonlinear optical substances, carbon nanotubes, inorganic substances (for example, A conventionally known dichroic compound can be used for the coating liquid for forming a polarizing film in the present disclosure.
  • Examples of the dichroic compound include paragraphs [0067] to [0071] of JP 2013-228706 A, paragraphs [0008] to [0026] of JP 2013-227532 A, and JP 2013-209367 A.
  • Paragraphs [0009] to [0017] Paragraphs [0051] to [0065] of JP 2013-37353 A, Paragraphs [0049] to [0073] of JP 2012-63387 A, JP 11-305036 A.
  • the dichroic compound may have a crosslinkable group.
  • the crosslinkable group include (meth) acryloyl group, epoxy group, oxetanyl group, styryl group and the like, and (meth) acryloyl group is preferable.
  • dichroic compound examples are shown below, but the dichroic compound in the present disclosure is not limited to the following compound examples.
  • Two or more dichroic compounds may be used in combination, for example, at least one dichroic compound having a maximum absorption wavelength in the wavelength range of 370 nm to 550 nm and a maximum absorption wavelength in the wavelength range of 500 nm to 700 nm. It is preferable that at least one dichroic compound having a combination is used.
  • a dichroic compound may be used individually by 1 type, and may use 2 or more types together. There is no restriction
  • the coating liquid for forming a polarizing film in the present disclosure contains at least one solvent that dissolves at least the liquid crystalline polymer and the dichroic compound.
  • the solvent examples include ketone solvents (eg, acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.), ether solvents (eg, dioxane, tetrahydrofuran (THF), cyclopentyl methyl ether, etc.), fat Aromatic hydrocarbon solvents (eg, n-hexane, etc.), alicyclic hydrocarbon solvents (eg, cyclohexane, etc.), aromatic hydrocarbon solvents (eg, benzene, toluene, xylene, trimethylbenzene, etc.), halogenated Carbon solvents (eg, dichloromethane, trichloromethane (chloroform), dichloroethane, dichlorobenzene, chlorotoluene, etc.), ester solvents (eg, methyl acetate, ethyl acetate, butyl acetate
  • the solvent may be used alone or in combination of two or more.
  • the polarizing film forming coating solution in the present disclosure preferably includes an organic solvent having a boiling point of 80 ° C. or lower as a solvent.
  • the “boiling point” in the present disclosure refers to the “boiling point” under 1 atm (101,325 Pa).
  • the solid content change rate from 7 mass% to 15 mass% of the solid content concentration (solid content) is 1.6 mass% / second or more.
  • the organic solvent having a boiling point of 80 ° C. or lower the lower limit of the boiling point is 50 ° C. or higher from the viewpoint of easy adjustment of the drying rate of the coating film and easy avoidance of boiling of the coating solution. It is preferable that Specific examples of organic solvents having a boiling point of 80 ° C.
  • tetrahydrofuran (boiling point: 66 ° C.), acetone (boiling point: 56 ° C.), ethyl methyl ketone (boiling point: 80 ° C.), n-hexane (boiling point): 69 ° C.
  • Benzene (boiling point: 80 ° C), dichloromethane (boiling point: 40 ° C), trichloromethane (boiling point: 61 ° C), 1,1-dichloroethane (boiling point: 57 ° C), methyl acetate (boiling point: 57 ° C), ethyl acetate (Boiling point: 77 ° C.), ethanol (boiling point: 78 ° C.) and the like.
  • the organic solvent having a boiling point of 80 ° C. or lower an ether solvent is preferable from the viewpoint of the solubility of the dichroic compound, and tetrahydrofuran is particularly preferable.
  • the organic solvent having a boiling point of 80 ° C. or lower is preferably contained in an amount of 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more based on the total amount of the solvent. Further, the content of the organic solvent having a boiling point of 80 ° C. or less is advantageously 90% by mass or less based on the total amount of the solvent from the viewpoint of suppressing the brushing (that is, whitening) of the coating film. Further, the content of the organic solvent having a boiling point of 80 ° C. or less is more preferably 80% by mass or less, still more preferably 70% by mass or less, and particularly preferably 60% by mass or less with respect to the total amount of the solvent.
  • the content of the solvent in the coating liquid for forming a polarizing film is preferably 93% by mass to 99.5% by mass, more preferably 93% by mass to 99% by mass, and more preferably 93% by mass with respect to the total mass of the coating liquid. More preferably, it is -97 mass%.
  • the coating liquid for forming a polarizing film in the present disclosure contains an interface improver.
  • the interface improver By including the interface improver, the surface smoothness of the coating film is improved and the degree of orientation is improved, or the occurrence of unevenness and unevenness is suppressed, and the improvement of the uniformity of the in-plane orientation is expected.
  • the interface improver those that orient liquid crystal polymers are preferable.
  • the content of the interface improving agent is 100 parts by mass in total of the liquid crystalline polymer and the dichroic compound in the coating liquid for forming a polarizing film. 0.001 to 5 parts by mass is preferable, and 0.01 to 3 parts by mass is more preferable.
  • the coating liquid can contain components other than those described above. Examples of other components include a polymerization initiator and various additives.
  • the compound (namely, photoinitiator) which has photosensitivity is preferable.
  • the photopolymerization initiator is not particularly limited, and examples thereof include ⁇ -carbonyl compounds (specifically, compounds described in US Pat. No. 2,367,661 or US Pat. No. 2,367,670), acyloin ethers (specific examples). Specifically, compounds described in US Pat. No. 2,448,828), ⁇ -hydrocarbon-substituted aromatic acyloin compounds (specifically, compounds described in US Pat. No. 2,722,512), polynuclear quinone compounds (specific examples) Specifically, compounds described in US Pat. No. 3,046,127 or US Pat. No.
  • IGM Resins B.I. V. Omnirad series for example, Omnirad 184, Omnirad 907, Omnirad 369, Omnirad 651, Omnirad 819, etc., all of which correspond to BASF's former Irgacur series, etc.), BASFur, etc. Can be mentioned.
  • the content of the polymerization initiator in the coating solution is a total of 100 masses of the liquid crystalline polymer and the dichroic compound in the coating solution for forming a polarizing film.
  • Part by weight is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 15 parts by weight.
  • the alignment film forming part 42 in FIG. 1 will be described.
  • the alignment film forming part 42 includes a coating film forming part 61, a drying part 62, and a light irradiation part 63.
  • the coating film forming unit 61 is formed on the substrate 11 (the first protective layer 12 provided on the substrate 11 when the manufacturing apparatus 102 shown in FIG. 2 is used), for example, with an azo compound as a photoisomerization compound.
  • a coating film 67 is formed by applying a photoisomerization coating liquid (also referred to as an alignment film forming coating liquid) 66 containing an azo compound solvent.
  • the photoisomerization coating solution 66 is a solution in which an azo compound is dissolved in a solvent.
  • the drying unit 62 reduces the solvent from the coating film 67 by heating, blowing, natural drying, or a combination of these methods, and drying the coating film 67, thereby forming the photoisomerized film 68 that is a dry coating film. Form long.
  • the light irradiation unit 63 provided downstream of the drying unit 62 in the transport direction Dc is for forming the alignment film 13.
  • the light irradiation unit 63 includes a plurality of light sources 71 and a polarizer unit 72.
  • a plurality of light sources 71 are provided in a state aligned in the depth direction of FIG. 3, and the plurality of light sources 71 extend in the depth direction of FIG. 3 with the light emission surface facing the conveyance path of the base material 11.
  • the support member 73 is supported.
  • the light source unit 76 includes a light source 71, a support member 73, a chamber 74, a cover glass 75, and the like.
  • the light source 71 may be an LED (light emitting diode). LEDs generate less heat than metal halide lamps and mercury lamps. Therefore, deformation of the polarizer unit 72 is further suppressed even when continuous irradiation is performed, that is, when irradiation is performed for a long time. As a result, an alignment film having a highly uniform alignment degree in the longitudinal direction is obtained.
  • the polarizer unit 72 is disposed between the light source 71 and the transport path.
  • the polarizer unit 72 includes a reflective polarizer, and makes light emitted from the light source 71 linearly polarized light.
  • the photoisomerization film 68 being conveyed formed on the substrate 11 passes through the light irradiation unit 63, so that linearly polarized light is irradiated to the photoisomerization film 68.
  • the azo compound contained in the photoisomerization film 68 is photoisomerized and aligned, and the alignment film 13 is generated.
  • the azo compound is isomerized from a trans form to a cis form.
  • the alignment film can be formed as described above.
  • the formed alignment film can make the alignment degree in the polarizing film laminated on the alignment film uniform in the longitudinal direction.
  • the polarizing film forming unit 43 includes a coating film forming unit 91, a drying unit 92, and a temperature management unit 93.
  • a polarizing film forming coating solution 94 containing a liquid crystalline polymer, a dichroic compound, and a solvent for dissolving the liquid crystalline polymer and the dichroic compound is continuously applied thereon.
  • the coating film 96 for forming a polarizing film on the alignment film is formed.
  • the drying of the coating film will be described in detail in the section of the drying process below.
  • the coating liquid 94 for forming a polarizing film is in a state in which a liquid crystalline polymer and a dichroic compound are dissolved in a solvent.
  • a coating film is formed on the alignment film using the polarizing film forming coating solution.
  • the thickness of the coating film formed on the alignment film can be 1 ⁇ m to 50 ⁇ m and is preferably in the range of 10 ⁇ m to 30 ⁇ m.
  • the drying process in the present disclosure reduces the solvent from the coating film formed in the coating film forming process.
  • the solid content change rate from 7% by mass to 15% by mass of the solid content concentration (solid content amount) in the coating film is 1.6% by mass / second or more (this condition is appropriately changed to “ It will be described as “condition A”). That is, the coating film is dried within a specific time at a solid content concentration at which components such as a dichroic compound are easily crystallized.
  • a drying process starts after coating, but when the solid content concentration of the coating film becomes 7% by mass or more by drying, the intermolecular distance of the components Therefore, aggregation (for example, crystallization) of components such as a dichroic compound tends to occur, and haze tends to occur.
  • the solid content concentration of the coating film exceeds 15% by mass in the drying step after coating, the viscosity of the coating film increases, and the behavior of components such as a dichroic compound in the coating film is limited, and aggregation ( For example, crystallization is less likely to occur. Therefore, in the drying process, the solid content change rate between the solid content concentration in the coating film of 7% by mass and the solid content concentration of 15% by mass is set to 1.6% by mass / second or more (ie, Condition A is satisfied).
  • FIG. 6 shows an example of a change in solid content concentration (Nv. Unit: mass%) of the coating film with time (t, unit: second).
  • the elapsed time from the time when the solid concentration reaches 7 mass% (t1 in FIG. 6) to the time when it reaches 15 mass% (t2 in FIG. 6) may be 5 seconds or less.
  • the solid content change rate from the time when the solid content concentration reaches 7% by mass (t1 in FIG. 6) to the time when the solid content concentration reaches 15% by mass (t2 in FIG. 6) changes, for example, in a polygonal line in multiple stages. Alternatively, it may be changed in a curved line sequentially.
  • the solid content change rate is not limited. It may be determined as appropriate according to the composition of the material, the limitation of the drying process, and the like. Specifically, as in the two examples shown by the dotted line in FIG. 6, before the time when the solid content concentration of the coating film reached 7% by mass (t1 in FIG. 6), or 15% by mass.
  • the solid content change rate after the time (t2 in FIG. 6) at which the value reaches the point may be lower than the solid content change rate from “t1” to “t2”, or may be the same.
  • the solid content change rate before the time when the solid content concentration of the coating film reached 7% by mass (ie, t1) and the time after the time when the solid content concentration of the coating film reached 15% by mass (ie, t2) may be the same or different.
  • the solid content change rate in Condition A is 1.6% by mass / second or more, but the larger the value, the better, and 2.0% by mass / second or more is preferable.
  • the solid content concentration in the coating film is measured by measuring the optical thickness of the film from the point of application to the dry film using an infrared spectral interference film thickness meter SI-T80 manufactured by Keyence. Can be done online. Specifically, first, the optical thickness of the film from the point of application to the dry film is measured. Next, the thickness of the dried film (that is, dry film) is measured with a contact-type thickness meter. The dry film thickness measured with a contact thickness gauge is corrected by dividing by the optical thickness. Based on the corrected value, the thickness of the wet film (that is, the coating film) is calculated from the optical thickness. Then, the solvent amount is obtained from the thickness of the wet film (that is, the coating film) at the measurement point. And the solvent mass is calculated
  • a method in which the solid content change rate from 7% by mass to 15% by mass of the solid content concentration (that is, the solid content amount) in the coating film is 1.6% by mass / second or more (that is, the condition A is satisfied)
  • the method for) is not particularly limited, and can be appropriately selected from methods for increasing the removal rate of the solvent in the coating film.
  • a method for increasing the removal speed of the solvent in the coating film a method such as applying a gas such as air to the coating film to increase the removal speed of the solvent in the coating film, inhaling the air around the coating film, Examples thereof include a method for increasing the removal rate of the solvent therein, heating the coating film to increase the removal rate of the solvent in the coating film, and the like.
  • a blowing method of applying a gas such as air from a slit-shaped or rectangular outlet As a method of increasing the removal rate of the solvent in the coating film by applying a gas such as air to the coating film, a blowing method of applying a gas such as air from a slit-shaped or rectangular outlet.
  • a gas having a wind speed of 1.0 m / s or more When using a slit-shaped outlet, it is preferable to apply a gas having a wind speed of 1.0 m / s or more to the coating film.
  • a rectangular blower outlet it is preferable to apply gas with a wind speed of 0.5 m / s or more to the coating film.
  • concentration of a coating film is a part between 7 mass% to 15 mass%, or It may be all or a part or all of the solid content concentration from application to 15% by mass.
  • gas such as air
  • a method of inhaling air around the coating film and increasing the removal rate of the solvent in the coating film there is a method of inhaling at least air around the coating film using an air suction device.
  • an air suction device For example, when inhaling air from a rectangular intake port by an intake device, it is preferable to inhale at a wind speed of 0.5 m / s or more with respect to the coating film.
  • the solid content concentration of the coating film may be a part or all of between 7% by mass and 15% by mass. Part or all of the solid content concentration up to 15% by mass may be applied. Note that inhalation may be continued even after the solid content concentration exceeds 15 mass% after application.
  • the film surface temperature of the coating film it is preferable to keep the film surface temperature of the coating film at 25 ° C. or higher, and at 28 ° C. or higher, at least in part between the solid content concentration in the coating film of 7% by mass to 15% by mass. Is preferable, and it is still more preferable to maintain at 30 degreeC or more.
  • the film surface temperature of the coating film is a value measured using a radiation thermometer whose emissivity is calibrated with a temperature value measured with a non-contact thermometer.
  • the measurement is performed in a state where there is no reflector within 10 cm from the surface on the opposite side (back side) to the measurement surface.
  • the method for maintaining the film surface temperature of the coating film at 25 ° C. or higher is not particularly limited, and as described above, in addition to the method for adjusting the temperature of the coating liquid for forming the polarizing film, the coating film It can be appropriately selected from methods for raising the film surface temperature of the film.
  • the method is not limited to the method in which the film surface of the coating film is directly heated to set the film surface temperature to 25 ° C. or higher, but the exposed surface is heated from the side opposite to the film surface exposed through the coating film. And a method of heating the inside of the film to raise the film surface temperature to 25 ° C. or higher.
  • the solid content concentration of the coating film from the coating is 15 mass. It is preferable that the film surface temperature of the coating film be maintained at 25 ° C. or higher by setting the temperature of the base material to 30 ° C. or higher while it is not more than%. That is, a coating film is formed on a substrate having a temperature of 30 ° C. or higher. Thereby, the liquid temperature fall of the coating liquid which occurs when the coating liquid contacts the alignment film or after the contact is suppressed, and the film surface temperature of the coating film is easily kept at 25 ° C. or more.
  • “from application” means the time after the application of the application liquid to the alignment film is started. The same applies to the following.
  • the temperature of the substrate can be obtained by measuring the temperature of the surface of the substrate opposite to the side where the alignment film is disposed. Specifically, it can be performed by a method in which a thermocouple is brought into contact with the surface of the substrate opposite to the side on which the alignment film is disposed, a method in which measurement is performed using a non-contact type thermometer, or the like.
  • a base material that has been heated to 30 ° C. or higher in advance may be used, or the transported base material may be heated before application. You may adjust temperature to 30 degreeC or more.
  • the gas having a temperature of 30 ° C. or higher is opposite to the coating film forming surface of the alignment film while the solid content concentration of the coating film is 15% by mass or less after coating. It is preferable to keep the film surface temperature at 25 ° C. or higher by applying to the side surface.
  • a gas having a temperature of 30 ° C. or higher is allowed to flow on the opposite side of the substrate on which the alignment film is disposed (that is, on the opposite side of the alignment film to the coating surface).
  • the film surface temperature is preferably kept at 25 ° C. or higher.
  • Inert gas such as air and nitrogen gas, etc. can be used.
  • a method of applying a gas having a temperature of 30 ° C. or higher to the substrate for example, a method using a warm air heater may be mentioned.
  • the film surface temperature of the coating film is 15% by mass or less after coating, it is preferable to keep the film surface temperature at 25 ° C. or higher by passing the coating film through a region where the ambient temperature is 30 ° C. or higher.
  • the components in the coating film are likely to be crystallized, so that the coating film is passed through an atmosphere heated to 30 ° C. or higher. Is preferred. Thereby, since the atmosphere of 30 ° C. or higher is in direct contact with the film surface, the film surface temperature is easily maintained at 25 ° C. or higher.
  • atmospheric temperature suitably according to the conveyance distance of the area
  • the upper limit of atmospheric temperature can be, for example, 80 ° C. or less, preferably 50 ° C. or less, and more preferably 45 ° C. or less.
  • Examples of the region where the atmospheric temperature is 30 ° C. or higher include a drying chamber or a drying zone in which the temperature of the internal air atmosphere is adjusted to 30 ° C. or higher.
  • a method for adjusting the atmospheric temperature to 30 ° C. or higher a method of supplying air or the like heated to 30 ° C. or higher to a drying chamber or a drying zone, and an atmosphere inside the drying chamber or drying zone are added using a heater. The method of heating etc. are mentioned.
  • the film surface temperature is also preferable to keep the film surface temperature at 25 ° C. or higher by applying radiant heat to the coating film with an infrared heater while the solid content concentration of the coating film is 15% by mass or less after coating.
  • an infrared heater commercially available products can be appropriately selected and used.
  • the drying step in the method for producing a laminate according to the present disclosure when the solid content concentration of the coating film is in a specific range (that is, a range of 7% by mass or more and 15% by mass or less) as described above, the film surface of the coating film
  • a specific range that is, a range of 7% by mass or more and 15% by mass or less
  • the drying temperature when the solid content concentration of the coating film is not in a specific region can be in the range of 30 ° C to 200 ° C.
  • the drying time after the solid content concentration of the coating exceeds 15% by mass is not particularly limited, and is preferably 0.1 minute to 10 minutes, more preferably 0.2 minutes to 5 minutes. is there.
  • FIGS. 1, 5, and 7. An example of the drying process in the present disclosure will be described with reference to FIGS. 1, 5, and 7.
  • a coating film is dried.
  • a solvent is reduced from the coating film 96 by the method of heating, ventilation, intake air, or a combination of these methods.
  • solid content change rate from 7 mass% of solid content concentration (solid content amount) in a coating film after the time of application
  • the temperature management unit 93 in the polarizing film forming unit 43 raises the temperature of the dry coating 97 (that is, the intermediate laminate 110 having the dry coating 97) that is a coating with reduced solvent.
  • the dried coating film 97 is aged by lowering the temperature or maintaining a specific temperature range.
  • the temperature management unit 93 is responsible for temperature management, the orientation of the liquid crystalline polymer and the dichroic compound in the dry coating film 97 is more precisely adjusted.
  • the polarizing film 14 having a function as a polarizer is obtained.
  • the solvent may remain in the dry coating film at the end of the drying process.
  • the dried coating film 97 When the dried coating film 97 is cooled after being dried as described above, the liquid crystalline polymer 21 is solidified while the mesogenic group 23 approaches a regular alignment state according to the alignment film 13 more strictly as shown in FIG. As a result, the air gap 26 becomes clearer.
  • 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 polarizing film as a whole.
  • the mesogenic groups 23 of the liquid crystalline polymer 21 gradually obtain some mobility while maintaining the alignment state of the liquid crystalline polymer 21 and the dichroic compound 31 in general (FIG. 7).
  • the mesogenic group 23 follows the alignment film better.
  • the dichroic compound becomes mobile when the association promotion temperature is reached beyond the crystallization temperature, but the other dichroic compounds in the same void 26 are not removed without removing the void 26 formed by the mesogenic group or the like. The probability of contact with a sex compound increases.
  • the association of the dichroic compounds proceeds in each void 26, and the degree of orientation of the dried coating film 97 is further improved as shown in FIG.
  • the 1st protective layer formation part 41 is provided before the above-mentioned coating-film formation process and a drying process, and the above-mentioned coating-film formation
  • the 2nd protective layer formation part 44 is provided after a process and a drying process.
  • the 1st protective layer formation part 41 is provided with the coating-film formation part and drying part which are not shown in figure, for example.
  • the coating film forming unit continuously coats a coating solution in which, for example, polyvinyl alcohol (PVA) is dissolved in a solvent on the substrate 11 moving in the transport direction Dc to form a coating film.
  • PVA polyvinyl alcohol
  • the drying unit reduces the solvent from the coating film by heating, blowing, natural drying, or a combination of these methods, and dries the coating film to form the first protective layer on the substrate 11.
  • the 2nd protective layer formation part 44 is provided with the coating-film formation part and drying part which are not shown in figure, for example.
  • the coating film forming part is a material for forming the second protective layer, and a coating liquid containing an epoxy monomer polymer and a solvent for dissolving the epoxy monomer polymer on the polarizing film. Apply to form a coating film.
  • a drying part reduces a solvent from a coating film by the method of heating, ventilation, natural drying, or these methods, and dries a coating film, and forms a 2nd protective layer on a polarizing film.
  • the laminated body in this indication (for example, laminated body 10 in Drawing 1 and Drawing 2) can be produced.
  • the laminate in the present disclosure preferably includes a substrate, an alignment film provided on the substrate, and a polarizing film provided on the alignment film.
  • the laminate in the present disclosure may further have a ⁇ / 4 plate on the polarizing film.
  • the laminate in the present disclosure may further have a barrier layer between the polarizing film and the ⁇ / 4 plate. Since the polarizing film is as described above, the description thereof is omitted.
  • each layer in the laminate in the present disclosure will be described.
  • Base material As a base material, it can select suitably, For example, glass and a polymer film are mentioned.
  • the light transmittance of the substrate is preferably 80% or more.
  • a polymer film When a polymer film is used as the substrate, it is preferable to use an optically isotropic polymer film.
  • the base material include polyester base materials (polyethylene terephthalate, polyethylene naphthalate films or sheets), cellulose base materials (diacetyl cellulose, triacetyl cellulose (TAC) films or sheets), polycarbonate base materials, and the like.
  • Poly (meth) acrylic base materials (polymethyl methacrylate film or sheet), polystyrene base materials (polystyrene, acrylonitrile styrene copolymer film or sheet), olefin base materials (polyethylene, polypropylene, cyclic or Polyolefin or ethylene propylene copolymer film or sheet having a norbornene structure), polyamide base material (polyvinyl chloride, nylon, aromatic polyamide film or sheet) G), polyimide base material, polysulfone base material, polyether sulfone base material, polyether ether ketone base material, polyphenylene sulfide base material, vinyl alcohol base material, polyvinylidene chloride base material, polyvinyl butyral base Examples thereof include a base material, a transparent base material such as a poly (meth) acrylate base material, a polyoxymethylene base material, and an epoxy resin base material, or a base material made of a blend poly
  • JP-A-2002-22294 can also be applied.
  • the substrate described in paragraph [0013] of JP-A-2002-22294 can also be applied.
  • the substrate described in paragraph [0013] of JP-A-2002-22294 can also be applied.
  • the substrate described in paragraph [0013] of JP-A-2002-22294 can also be applied.
  • the substrate described in paragraph [0013] of JP-A-2002-22294 can also be applied.
  • a polymer which is easy to express birefringence such as a conventionally known polycarbonate and polysulfone
  • the one whose expression is lowered by modifying the molecule described in International Publication No. 2000/26705 should be used. You can also.
  • the alignment film is a film for aligning a liquid crystalline polymer.
  • a rubbing treatment of an organic compound (preferably a polymer) on the film surface, oblique deposition of an inorganic compound, formation of a layer having a microgroove, or Langmuir Blodget It can be formed by means such as accumulation of organic compounds (eg, ⁇ -tricosanoic acid, dioctadecylmethylammonium chloride, or methyl stearate) by the method (LB film).
  • an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known.
  • an alignment film formed by light irradiation that is, a photo-alignment film
  • a photo-alignment film is preferable.
  • Rubbing treatment alignment film examples of the polymer material used for the alignment film formed by rubbing treatment include polyvinyl alcohol or a derivative thereof, polyimide or a derivative thereof.
  • the thickness of the rubbing-treated alignment film is preferably 0.01 ⁇ m to 10 ⁇ m, and more preferably 0.01 ⁇ m to 1 ⁇ m.
  • Photo-alignment film examples include, for example, JP-A-2006-285197, JP-A-2007-76839, JP-A-2007-138138, JP 2007-94071, JP 2007-121721, JP 2007-140465, JP 2007-156439, JP 2007-133184, JP 2009-109831, JP 3883848. Or an azo compound described in Japanese Patent No. 4151746, an aromatic ester compound described in Japanese Patent Application Laid-Open No. 2002-229039, Japanese Patent Application Laid-Open No. 2002-265541, or Japanese Patent Application Laid-Open No.
  • the photo-alignment film can be produced by irradiating a film formed using the above-described photo-alignment material (that is, a photoisomerization film) with linearly polarized light or non-polarized light. Irradiation with linearly polarized light or non-polarized light is an operation for causing a photoreaction in the photoalignment material.
  • the wavelength of light varies depending on the photo-alignment material and is not particularly limited as long as it is a wavelength necessary for the photoreaction.
  • the peak wavelength of light used for light irradiation is preferably 200 nm to 700 nm, and more preferably ultraviolet light having a peak wavelength of light of 400 nm or less.
  • Examples of the light source used for light irradiation include lamps (for example, tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps, and carbon arc lamps), laser light sources (for example, semiconductor lasers, helium neon). Laser, argon ion laser, helium cadmium laser, YAG (yttrium, aluminum, garnet) laser, etc.), light emitting diode, and cathode ray tube.
  • lamps for example, tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps, and carbon arc lamps
  • laser light sources for example, semiconductor lasers, helium neon.
  • light emitting diode and cathode ray tube.
  • a method using a polarizing plate for example, an iodine polarizing plate, a dichroic material polarizing plate, a wire grid polarizing plate, etc.
  • a prism system element for example, a Glan-Thompson prism
  • a Brewster angle is used.
  • a method using light emitted from a laser light source having polarized light is used.
  • light irradiation may be performed by a method of irradiating light from the upper surface or the back surface to the alignment film from the vertical or oblique direction to the alignment film surface.
  • the incident angle of light varies depending on the photo-alignment material, but is preferably 0 ° to 90 ° (that is, vertical), and more preferably 40 ° to 90 °.
  • non-polarized light it is preferable to irradiate the alignment film with non-polarized light obliquely.
  • the incident angle is preferably 10 ° to 80 °, more preferably 20 ° to 60 °, and still more preferably 30 ° to 50 °.
  • the light irradiation time is preferably 1 minute to 60 minutes, and more preferably 1 minute to 10 minutes.
  • the ⁇ / 4 plate is a plate having a ⁇ / 4 function, and specifically, a plate having a function of converting linearly polarized light having a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light).
  • a stretched polymer film, a retardation film having an optically anisotropic layer having a ⁇ / 4 function on a support, and the like can be mentioned.
  • a broadband ⁇ / 4 plate in which a ⁇ / 4 plate and a ⁇ / 2 plate are laminated can be cited.
  • the ⁇ / 4 plate and the polarizing film may be provided in contact with each other, or another layer may be provided between the ⁇ / 4 plate and the polarizing film.
  • the other layer include a pressure-sensitive adhesive layer or an adhesive layer for ensuring adhesion, or a barrier layer.
  • barrier layer When the laminated body in this indication has a barrier layer, it is preferred that the barrier layer is provided between the polarizing film and the ⁇ / 4 plate. In addition, when it has other layers (for example, adhesion layer or adhesive layer) other than a barrier layer between a polarizing film and (lambda) / 4 board, a barrier layer is between a polarizing film and other layers, for example. Can be provided.
  • the barrier layer is also called a gas barrier layer or an oxygen barrier layer, and has a function of protecting the polarizing film from a gas such as oxygen in the atmosphere and moisture, or a compound contained in an adjacent layer.
  • the barrier layer for example, paragraphs [0014] to [0054] of JP-A-2014-159124, paragraphs [0042] to [0075] of JP-A-2017-121721, paragraph of JP-A-2017-115076 [0045] to [0054], paragraphs [0010] to [0061] of JP 2012-213938 A, paragraphs [0021] to [0031] of JP 2005-169994 A, and the like can be referred to.
  • the display element provided in the image display device is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (sometimes abbreviated as “EL”) display panel, and a plasma display panel.
  • a liquid crystal cell or an organic EL display panel is preferable. That is, as the image display device, a liquid crystal display device using a liquid crystal cell as a display element and an organic EL display device using an organic EL display panel as a display element are preferable.
  • liquid crystal display device As an example of the liquid crystal display device which is an example of the image display device, an embodiment having a polarizing film and a liquid crystal cell is preferably mentioned, and more preferably, a laminate (provided not having a ⁇ / 4 plate) and a liquid crystal cell in the present disclosure.
  • a liquid crystal display device having the aspect provided with the laminated body in this indication as a polarizing element of a front side among the polarizing elements provided in the both sides of a liquid crystal cell is preferable, and the aspect provided with the laminated body in this indication as a polarizing element of a front side and a rear side Is more preferable.
  • the liquid crystal cell used in the liquid crystal display device is preferably in a VA (Vertical Alignment) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic) mode. It is not limited to these.
  • a TN mode liquid crystal cell rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and are twisted and aligned at 60 to 120 °.
  • a TN mode liquid crystal cell is most frequently used as a color TFT (Thin Film Transistor) liquid crystal display device, and is described in many documents.
  • a VA mode liquid crystal cell rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied.
  • the VA mode liquid crystal cell includes: (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). In addition to 176625, see (2) Liquid crystal cell (SID97, Digest of tech. Papers 28 (1997) 845) in which the VA mode is multi-domained (in MVA mode) for widening the viewing angle.
  • a liquid crystal cell in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Preliminary collections 58-59 of the Japan Liquid Crystal Society) (See 1998)), and (4) SURVIVAL mode liquid crystal cells (see the presentation at LCD International 98).
  • any of a PVA (Patterned Vertical Alignment) type, a photo-alignment type (Optical Alignment), and a PSA (Polymer-Stained Alignment) may be used. Details of the modes are described in JP-A-2006-215326 and JP-T-2008-538819.
  • JP-A-10-54982, JP-A-11-202323, and JP-A-9-292522 are methods for reducing leakage light at the time of black display in an oblique direction and improving a viewing angle by using an optical compensation sheet. No. 11-133408, No. 11-305217, No. 10-307291, and the like.
  • Organic EL display device As an organic EL display device which is an example of an image display device, for example, an aspect having a polarizing film, a ⁇ / 4 plate, and an organic EL display panel in this order from the viewing side is preferable, and more preferably. From the viewing side, the laminated body in the present disclosure having a ⁇ / 4 plate and the organic EL display panel are arranged in this order. In this case, the laminated body has a base material, an alignment film, a polarizing film, a barrier layer provided as necessary, and a ⁇ / 4 plate arranged in this order from the viewing side.
  • the organic EL display panel is a display panel using an organic EL element in which an organic light emitting layer (that is, an organic electroluminescence layer) is sandwiched between electrodes (that is, between a cathode and an anode).
  • an organic light emitting layer that is, an organic electroluminescence layer
  • electrodes that is, between a cathode and an anode.
  • the weight average molecular weight is a value measured by the gel permeation chromatograph (GPC) method under the aforementioned conditions.
  • Example 1 As a substrate, a long triacetyl cellulose (TAC) film having a thickness of 40 ⁇ m was prepared. The TAC film was loaded into the production apparatus shown in FIG. 2, and a laminate was produced as follows.
  • TAC triacetyl cellulose
  • a first protective layer-forming coating solution having the following composition was prepared, and the first protective layer-forming coating solution was applied onto a TAC film and dried to form a first protective layer having a dry thickness of 1.3 ⁇ m.
  • an alignment film forming coating solution having the following composition was prepared, and the alignment film forming coating solution was applied onto the first protective layer and dried to form a photoisomerized film. Thereafter, the photoisomerized film is irradiated with linearly polarized ultraviolet rays (illuminance: 4.5 mW, irradiation amount: 500 mJ / cm 2 ) using a polarized ultraviolet exposure apparatus, and azobenzene is photoisomerized and oriented. An alignment film having a thickness of 0.3 ⁇ m was formed.
  • Photo-alignment material having the following structure: 0.3 part by mass 2-butoxyethanol: 41.6 parts by mass Dipropylene glycol monomethyl ether: 41.6 parts by mass Pure water: 16.5 parts by mass
  • a polarizing film forming coating solution having the following composition was prepared, and the polarizing film forming coating liquid adjusted to 27 ° C. was applied onto the alignment film with a die coater, and the coating film having a liquid film thickness of 5.1 ⁇ m. Formed. Thereafter, air with a wind speed of 1.1 m / s was applied with a slit nozzle to dry the coating film.
  • the solid content concentration of the coating film was measured from the start of application of the coating liquid, the time required for the solid content concentration from 7% by mass to 15% by mass was 5 seconds, and the solid content change rate was 1.6% by mass / second. It turns out that.
  • the film surface temperature of the coating film whose solid content concentration is 7 mass% to 15 mass% was measured, it was maintained at 31 degreeC. After the solid content concentration exceeded 15% by mass, the coating film was heated to raise the film surface temperature to 140 ° C. and held for 30 seconds, and then the heating was stopped to cool the coating film to room temperature. In this way, a polarizing film was formed on the alignment film.
  • the measurement of the solid content concentration of the coating film was performed using an infrared spectral interference film thickness meter (SI-T80, manufactured by Keyence Corporation). Was measured online, and the thickness of the dried film (ie, dry film) was further measured with a contact-type thickness meter. The thickness of the measured dry film was divided by the optical thickness, and the thickness of the coating film (that is, the wet film) was calculated from the optical thickness to obtain the amount of solvent at the measurement point. Solvent mass was calculated
  • the film surface temperature of the coating film was measured using a radiation thermometer (FT-H10 Keyence Co., Ltd.) whose emissivity was calibrated with the temperature value measured with a non-contact type thermometer.
  • Liquid crystalline polymer L1 below: 4.011 parts by mass (weight average molecular weight: 13,300, structural unit (1) and structural unit (2) in the molecule 80:20 [(1) :( 2); mass) Ratio].)
  • the following dichroic compound D1 0.792 parts by mass
  • the following dichroic compound D2 0.963 parts by mass
  • the following interface improver F2 0.087 parts by mass
  • the following interface improver F3 0.073 parts by mass
  • the following interface modifier F4 0.073 parts by mass Tetrahydrofuran (organic solvent having a boiling point of 80 ° C. or lower): 37.6004 parts by mass Cyclopentanone: 56.4006 parts by mass
  • a coating solution for forming a second protective layer having the following composition was prepared, and the coating solution for forming the second protective layer was applied onto the polarizing film and dried to form a second protective layer having a dry thickness of 0.7 ⁇ m. .
  • the laminate produced above was measured using a haze meter (NDH2000) manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K 7136: 2000 “How to determine haze of plastic and transparent material”.
  • the haze value is a practically acceptable range of 1.0% or less.
  • Example 2 In Example 1, the speed of air from the slit nozzle was 1.7 m / s, the time required for the solid content concentration from 7% by mass to 15% by mass was 3 seconds, and the solid content change rate was 2.7% by mass.
  • a laminate was prepared in the same manner as in Example 1 except that it was set to / sec, and the same measurement and evaluation were performed. The results of measurement and evaluation are shown in Table 1.
  • Example 3 In Example 1, a laminate was prepared in the same manner as in Example 1 except that the film surface temperature of the coating film having a solid content concentration of 7% by mass to 15% by mass was 25 ° C., and the same measurement and evaluation Went. The results of measurement and evaluation are shown in Table 1.
  • Example 4 In Example 1, the amount of tetrahydrofuran (an organic solvent having a boiling point of 80 ° C. or lower) in the composition of the polarizing film forming coating solution was 42.0005 parts by mass, and the amount of cyclopentanone was also 42.0005 parts by mass. Produced the laminated body similarly to Example 1, and performed the same measurement and evaluation. The results of measurement and evaluation are shown in Table 1.
  • Example 5 In Example 1, the air around the formed coating film was sucked in at a wind speed of 0.6 m / s from a rectangular intake port, and the coating film was dried, as in Example 1, A laminate was prepared and subjected to the same measurement and evaluation. The results of measurement and evaluation are shown in Table 1. In the drying process, when the solid content concentration of the coating film was measured from the start of application of the coating solution, the time required for the solid content concentration from 7 mass% to 15 mass% was 5 seconds, and the solid content change rate was 1.6. It was found to be mass% / second.
  • Example 1 air having a wind speed of 0.8 m / s was applied by a slit nozzle, the time required for the solid content concentration from 7% by mass to 15% by mass was 6 seconds, and the solid content change rate was 1.3% by mass.
  • a laminate was prepared in the same manner as in Example 1 except that the rate was% / second, and the same measurement and evaluation were performed. The results of measurement and evaluation are shown in Table 1.
  • the laminated body in this indication can be used as a polarizing element (polarizing plate), for example, and is suitable as a linear polarizing plate or a circularly polarizing plate, for example.
  • polarizing plate polarizing plate
  • the laminate in the present disclosure does not have an optically anisotropic layer such as a ⁇ / 4 plate
  • the laminate in the present disclosure can be used as a linear polarizing plate.
  • the laminated body in this indication has (lambda) / 4 board
  • the laminated body in this indication can be used as a circularly-polarizing plate.

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  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
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Abstract

L'invention concerne un procédé de production d'un produit stratifié, le procédé comprenant : une étape dans laquelle un fluide de revêtement, comprenant un polymère à cristaux liquides, un composé dichroïque, et un solvant dans lequel sont dissous le polymère à cristaux liquides et le composé dichroïque, est appliqué sur un film d'alignement pour former un film de revêtement ; et une étape dans laquelle le solvant est éliminé du film de revêtement. Dans l'étape d'élimination du solvant contenu dans le film de revêtement, le film de revêtement présente une variation de la teneur en extrait sec d'une concentration en extrait sec de 7 % en masse à une concentration en extrait sec de 15 % en masse qui est supérieure ou égale à 1,6 % en masse/sec.
PCT/JP2019/019791 2018-05-23 2019-05-17 Procédé de production de produit stratifié Ceased WO2019225517A1 (fr)

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JP2005520668A (ja) * 2001-07-09 2005-07-14 プラスティック ロジック リミテッド 溶液に影響される整列
JP2005257922A (ja) * 2004-03-10 2005-09-22 Fuji Photo Film Co Ltd 光学補償シート及びその製造方法
JP2007332260A (ja) * 2006-06-14 2007-12-27 Dainippon Printing Co Ltd 液晶組成物、カラーフィルタ及び液晶表示装置
JP2008224968A (ja) * 2007-03-12 2008-09-25 Fujifilm Corp 光学補償フィルムの製造方法及び光学補償フィルム
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