KR20190118138A - Coating liquid containing liquid crystal capsule and functional film thereof - Google Patents

Abstract

The present invention relates to a coat liquid comprising a liquid crystal capsule covering a liquid crystal composition with a resin and an aqueous solution including at least one acrylamide monomer, and to a functional film produced by applying the same, drying, the same, irradiating UV, or the like to the same. The binder is required for using the liquid crystal capsule as a display element. Especially, the binder has a small influence on the electro-optical properties and has large voltage retention and high water resistance.

Description

Coated liquid containing liquid crystal capsule and functional film thereof

TECHNICAL FIELD This invention relates to the coating liquid containing a polymeric compound and a liquid crystal capsule, and the functional film formed by processing it. In particular, it is related with the coating liquid containing the functional film which exhibits an electro-optic effect by applying a voltage, and further has a large voltage retention, and the liquid crystal capsule which can form it. The coating liquid of this invention may be described as a coating liquid in the use which forms a functional film. The binder of this invention is a substance which adhere | attaches liquid crystal capsules, and is comprised from a polymeric component (also called resin).

Liquid crystal capsules having a structure in which a liquid crystal composition is contained in the hollow portion of the capsule are used as liquid crystal display elements, and in particular, use in a flexible display is expected (for example, Patent Document 1, Patent Document 2, Patent Document 3, Non Patent Literature 1).

Specifically, the liquid crystal display element which apply | coats the mixture containing a liquid crystal capsule and a binder to a comb-tooth type (lateral electric field) board | substrate using a bar coater etc., and drives only on one side board | substrate is known. Such a liquid crystal display element is driven using the Kerr effect.

When the liquid crystal capsule is used in a liquid crystal display element driven only on one side of the substrate, when the average particle diameter of the liquid crystal capsule exceeds the lower limit (about 380 nm) of the wavelength range of the visible light, the scattering of the visible light becomes large and black is difficult to display. Becomes difficult.

(Patent Document 1) Japanese Patent Laid-Open No. 8-67878 (Patent Document 2) Japanese Patent Publication 2010-211182 (Patent Document 3) Korean Registered Patent 1506328

(Non-Patent Document 1) Optics EXPRESS Vol. 21, No. 13 P15719-15727 (1 July 2013)

In order to use a liquid crystal capsule as a display element, a binder is required. In particular, a binder having a small influence on the electro-optical characteristics and having a large voltage retention and high water resistance is desired.

The present inventors formed by using the liquid crystal capsule which covered the liquid crystal composition (composition containing the liquid crystal material which consists of one or more liquid crystal compounds) with resin, and the aqueous solution containing at least 1 polymeric compound, and using it It has come to invent a functional membrane.

This invention includes the invention of the following aspects, for example.

First, it is a coating liquid which mixed the liquid crystal capsule which covered the liquid crystal composition with resin, and the aqueous solution containing 1 or 2 or more polymeric compound. Next, the coating liquid is coated on a substrate by a bar coater, a slit coater, or the like in a thin film form, and then vaporized with water, followed by polymerization by heating or heating such as UV.

According to the present invention, it is possible to obtain a functional film having a small influence on the optical properties, having a large voltage retention and high water resistance, and a coating liquid for forming the same.

1 is a structure of a comb electrode for applying a voltage to the functional film of the present invention.
2 is a measurement optical system for evaluation of optical properties of a functional film of the present invention.

The usage of the term in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "composition" and "element", respectively. "Liquid crystal display element" is a generic term for a liquid crystal display panel and a liquid crystal display module. A "liquid crystalline compound" is a generic term for a compound having a liquid crystal phase such as a nematic phase, a smetic phase, and a compound which does not have a liquid crystal phase but is mixed in the composition for the purpose of controlling properties such as temperature range, viscosity, and dielectric anisotropy of the nematic phase. to be. This compound has a six-membered ring such as, for example, 1,4-cyclo (cyclo) hexylene or 1,4-phenylene, and its molecular structure is rod like. "Liquid crystal capsule" is a material which covered the liquid crystal composition with a resin. A "polymerizable compound" is a compound used for the purpose of producing a polymer. Although a "polymerizable compound" is used together with a photoinitiator and irradiates UV etc. to it, it is common to radically polymerize, but it is not necessarily limited to the thing by radical photopolymerization. At least one compound selected from the group of compounds represented by formula (1) may be abbreviated as "compound (1)". "Compound (1)" means one compound or two or more compounds represented by Formula (1). The same applies to the compound represented by another formula. "At least one" with respect to "substituted" means that not only the position but also the number thereof may be selected without limitation. The numerical range displayed using "-" means the range which includes the numerical value described before and after as a lower limit and an upper limit.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. The ratio (content) of the liquid crystalline compound is expressed as a weight percentage (wt%) based on the weight of the liquid crystal composition. Additives, such as an optically active compound, antioxidant, a ultraviolet absorber, a pigment | dye, an antifoamer, a polymeric compound, a polymerization initiator, a polymerization inhibitor, and a polar compound, are added to this liquid crystal composition as needed. The ratio (addition amount) of the additive is expressed in weight percentage (% by weight) based on the weight of the liquid crystal composition in the same manner as the ratio of the liquid crystal compound. Weight parts per million (ppm) may be used. The proportion of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.

"Upper limit temperature" of the nematic phase may be abbreviated as "upper limit temperature". The "lower limit temperature of nematic phase" may be abbreviated as "lower limit temperature". "Large resistivity" means that the composition has a large resistivity in the initial stage not only at room temperature but also near the upper limit temperature of the nematic phase, and has a large resistivity not only at room temperature but also near the upper limit temperature of the nematic phase after long time use. Means that. "Large voltage retention" means that the device has a large voltage retention at the temperature close to the upper limit temperature of the nematic phase as well as room temperature in the initial stage, and a large voltage at temperatures close to the upper limit temperature of the nematic phase as well as room temperature after long time use. It means having retention rate.

The expression "at least one 'A' may be replaced with 'B'" means that the number of 'A' is arbitrary. When the number of 'A' is one, the position of 'A' is arbitrary, and even when the number of 'A' is two or more, their positions can be selected without limitation. This rule also applies to the expression "at least one 'A' is replaced by 'B'." The expression "at least one A may be substituted with B, C, or D" means that when any A is substituted by B, when any A is substituted by C and any A is substituted by D In this case, it is meant to include a case where a plurality of A is substituted with at least two of B, C, D. For example, alkyl where at least one -CH ₂ -may be substituted with -O- or -CH = CH- includes alkyl, alkenyl (alkenyl), alkoxy, alkoxyalkyl, alkoxyalkenyl, alkenyloxyalkyl Included. In addition, it is not preferable that two successive -CH ₂ -are replaced with -O- and become like -OO-.

In formula (1), when n is 2, two R ¹ are present. In this compound, two R ¹ may be the same or may be different from each other.

Alkyl is linear or branched, and does not contain cyclic alkyl. Straight chain alkyl is generally preferred over branched alkyl. These matters are also the same in terminal groups, such as alkoxy and alkenyl.

The present invention is as follows.

Item 1. A coating liquid containing a binder comprising a liquid crystal capsule in which a liquid crystal composition is covered with a resin and at least one polymerizable compound.

Item 2. The coating liquid according to item 1, wherein the polymerizable compound is an acrylamide compound or a methacrylamide compound.

Item 3. The coating liquid according to item 1 or 2, wherein the binder contains at least one compound represented by formula (1) as the first component and at least one compound represented by formula (2) as the second component. .

(In formula (1) and formula (2), R <^1> and R <^3> is respectively independently hydrogen or methyl; R <^2> is a single bond or C1-C20 alkylene, In this alkylene, And -CH _2- , which are not adjacent to each other, may be substituted with -O- or a group represented by formula (a); R ⁴ is a single bond or alkylene having 1 to 20 carbon atoms, and this alkylene In which any —CH ₂ — not adjacent to each other may be substituted with —O—; Z ¹ is —NH— or —O—; n is 1, 2, or 3,

In formula (a), R ⁵ is hydrogen or methyl)

Item 4. The binder according to item 3, wherein at least one compound in which all R ¹ in formula (1) is hydrogen as a first component and at least R ³ in formula (2) as a second component are hydrogen Coat liquid containing one compound.

Item 5. The coating liquid according to Item 3 or 4, wherein the ratio of the first component is in the range of 10 to 80% by weight, and the ratio of the second component is in the range of 20 to 80% by weight based on the weight of the binder.

Item 6. The binder according to any one of Items 3 to 5, wherein the binder contains at least one compound selected from the group of compounds represented by formulas (1-1) to (1-4) as a first component. , Coat liquid.

Item 7. The binder according to any one of items 3 to 6, wherein the binder contains at least one compound selected from the group of compounds represented by formulas (2-1) to (2-3) as a second component. , Coat liquid.

Item 8. The binder according to any one of items 3 to 7, wherein the binder is at least one selected from the group consisting of polyfunctional amines and polyfunctional thiols having two or more primary or secondary amines as a third component. A coating liquid further containing a compound.

Item 9. The binder further comprises at least one compound selected from the group of compounds represented by formulas (3-1) to (3-3) as a third component. Coat liquid to contain.

Item 10. The coating liquid according to Item 8 or 9, wherein the proportion of the third component is in the range of 0.1% by weight to 10% by weight based on the weight of the binder.

Item 11. The coating liquid according to any one of items 1 to 10, wherein a solid content concentration is 5% by weight or more based on the weight of the coating liquid.

Item 12. The coating liquid according to any one of items 1 to 11, wherein a weight ratio of the solid content of the liquid crystal capsule and the solid content of the binder is 5: 5 to 9: 1 based on the weight of the solid content of the coating liquid.

Item 13. The coating liquid according to any one of items 1 to 12, wherein a liquid crystal capsule covering the liquid crystal composition with a melamine resin is dispersed.

Item 14. The coating liquid according to any one of items 1 to 13, wherein the average particle diameter of the liquid crystal capsule is 10 nm to 380 nm.

Item 15. A functional film formed using the coating liquid according to any one of items 1 to 14.

Item 16. The functional film according to item 15, which is formed by making the coating liquid into a thin film form using a coating apparatus, volatilizing moisture by heating, and then polymerizing by irradiation with UV or the like.

Item 17. The functional film of item 15 or 16, wherein the film thickness is at least 0.5 μm.

Item 18. The functional film of any one of items 15 to 17, which expresses an optical change by applying a voltage.

1. Binder (Polymerizable Component)

Generally, although the obtained liquid crystal capsule is a state disperse | distributed to water, it is used in the solution state which added the binder etc. In addition, one or two or more binders may be sufficient. As a binder, water-soluble compounds, such as (meth) acrylamide (amide), PVA (polyvinyl (vinyl) alcohol), and melamine type which can be used as a capsule wall, can be used. In addition, emulsions such as vinyl chloride, vinyl acetate, acrylic or silicone dispersed in water may be used. If the contents in the liquid crystal capsule do not leak, replacement of the aqueous solvent in the dispersion can be carried out, and a compound dissolved in the solvent in which the substitution has been performed may be used as a binder. Furthermore, the binder can also be reacted in a subsequent step.

The binder of the present invention has at least one polymerizable compound, a polyfunctional polymerizable compound represented by at least one formula (1), and a monofunctional compound represented by at least one formula (2). It contains a polymeric compound of. If necessary, it may further contain at least one compound selected from the group consisting of a polyfunctional amine having two or more primary or secondary amines represented by the formula (3) and a polyfunctional thiol (thiol). .

In the functional film formed by using the binder of the present invention, the dispersibility of the liquid crystal capsule is good, the surface flatness of the film is good, the adhesion to the substrate is good, the water resistance after polymerization is good (water repellency is good and water is not absorbed). In order not to affect the electro-optical properties, it is preferable that the values of optical anisotropy and dielectric anisotropy are similar to those of the liquid crystal capsule, and have a large voltage retention.

In the binder of the present invention, in order to ensure the strength of the functional film, the first component is preferably 10 to 80% by weight, more preferably 20 to 80% by weight, particularly preferably 25 to 75% by weight.

In the binder of this invention, in order to improve adhesiveness with respect to a board | substrate, 20-80 weight% is preferable and, as for a 2nd component, 25-75 weight% is more preferable.

As a 1st component, the compound represented by following formula (1) is mentioned.

(In formula (1), R ¹ is independently hydrogen or methyl; R ² is a single bond or alkylene having 1 to 20 carbon atoms, and optionally -CH which is not adjacent to each other in this alkylene. ₂ -may be substituted with -O- or a group represented by formula (a); n is 1, 2 or 3; in formula (a), R ⁵ is hydrogen or methyl.)

However, when R <^2> is alkylene, it is not preferable that the terminal of this alkylene is substituted by the group represented by Formula (a), and it combines with neighboring NH, and becomes -NN-.

As a 1st component, the compound represented by following formula (1-1)-(1-4) is preferable among the compound represented by Formula (1).

It is preferable that at least one of a 1st component is a compound represented by Formula (1-1).

As a 2nd component, the compound represented by following formula (2) is mentioned.

(In Formula (2), R <^3> is hydrogen or methyl; R <^4> is single bond or C1-C20 alkylene, and arbitrary -CH <_{2> which} is not adjacent to each other in this alkylene. May be substituted with -O-; Z ¹ is -NH- or -O-.

However, when R <^4> is alkylene, it is unpreferable that the terminal of this alkylene is substituted by -O-, it combines with neighboring -OH, and becomes -OO-.

As a 2nd component, the compound represented by following formula (2-1)-(2-3) is preferable among the compound represented by Formula (2).

1-1. Crosslinking agent

In order to form a firm functional film, a third component, a crosslinking agent, can be used together with the binder. As a crosslinking agent, the polyfunctional amine and polyfunctional thiol which has two or more primary or secondary amines may be used independently, or may use multiple types together. When using as a crosslinking agent, it is preferable to have 2-6 amines or thiols, respectively.

The total content of the polyfunctional amine and the polyfunctional thiol having two or more primary or secondary amines is not particularly limited, but in order to improve the strength and water resistance of the functional membrane, the content is 0.1 wt% or more, compatibility and voltage. In order to maintain a maintenance rate etc., it is preferable that it is 10 weight% or less, and it is more preferable that it is 0.5-5 weight%.

1-1-1. Multifunctional amine

The polyfunctional amine having at least two primary or secondary amines is not particularly limited and may be a compound having two or more primary or secondary amines in the molecule. In addition, a polyfunctional amine may contain both the primary amine and the secondary amine.

As the polyfunctional amine having a primary amine, hexamethylenedi (di) amine and diethylene glycol (glycol) bis (3-aminopropyl) ether (ether) are preferable.

1-1-2. Multifunctional Thiol

The polyfunctional thiol is not particularly limited and may be a compound having two or more thiols in a molecule. As a polyfunctional thiol, 1, 6- hexane (hexane) dithiol is preferable.

As a 3rd component, the compound represented by Formula (3-1)-Formula (3-3) is mentioned.

1-2. Photopolymerization initiator

It is preferable that the photoinitiator used by this invention is water-soluble in order to function in the binder aqueous solution. Specifically, IRGACURE 2959, IRGACURE MBF, DAROCUR 1173, IRGACURE 754, etc. are preferable, and IRGACURE 2959 is especially preferable.

It is preferable that a suitable amount of photoinitiator is used in order to start superposition | polymerization. Based on the solid content weight of a coating liquid, 0.1-10 weight part is preferable and 0.5-7 weight part is more preferable. If it is this range, the remaining photoinitiator does not affect an electro-optical characteristic.

In this invention, solid content weight shows the weight of the component remove | excluding the weight of a volatile component from the weight of the whole liquid crystal capsule water dispersion liquid, a coating liquid, etc., The solid content weight of a liquid crystal capsule shows a volatile component (water content in liquid crystal capsule water dispersion liquid). ), And the solid content weight of the raw material of the binder is excluding volatile components (moisture) from the aqueous solution of the raw material (water dispersion) of the binder (including crosslinking agent, film forming agent, polymerization initiator, and additive). It is weight. In addition, the solid content concentration of a coating liquid volatilizes in the liquid-crystal capsule water dispersion liquid and the raw material aqueous solution (water dispersion liquid) (containing a crosslinking agent, a film forming agent, a polymerization initiator, and an additive) when the weight of the whole coating liquid is 100%. % By weight excluding component (moisture).

In the coating liquid of this invention, solid content concentration is 5 weight% or more from a viewpoint of film forming, and is 60 weight% or less from a storage stability of a coating liquid. More preferably, they are 10 weight% or more and 50 weight% or less, More preferably, they are 15 weight% or more and 40 weight% or less. If it is this range, the storage stability of a film forming and a coating liquid will be favorable.

2. Liquid Crystal Capsule

The liquid crystal capsule of the present invention comprises a liquid crystal composition containing a liquid crystal material, a surfactant, and a capsule wall, as disclosed in WO2016 / 035453A1 and the like. Specifically, the capsule wall is in the form of a closed curve, and the liquid crystal composition is disposed inside the capsule wall. In addition, hydrophobic portions of the surfactant are further disposed inside the capsule wall, and hydrophilic groups of the surfactant are disposed outside the capsule wall. Specific examples of the closed curved shape include spherical surfaces, elliptic spherical surfaces, and the like. The composition of the capsule wall is not particularly limited, but a polymer is preferred, and a melamine polymer is more preferred.

The liquid crystal material is a material composed of one or two or more liquid crystal compounds. In addition, the surfactant may be one compound or may be composed of a plurality of compounds.

50-90 weight% is preferable with respect to the whole amount of a liquid crystal capsule, and, as for content of the liquid crystal material in the liquid crystal capsule of this invention, 55-80 weight% is more preferable. If it is the range of the above-mentioned amount of inclusions, sufficient liquid crystal performance will be obtained, and the relative thickness of a capsule wall will become enough and it will not be destroyed easily.

It is preferable that it is 1-50 weight% with respect to a liquid crystal material, and, as for content of surfactant, 5-40 weight% is more preferable. It is preferable that it is 1-60 weight% with respect to a liquid crystal material, and, as for content of a capsule wall, 5-45 weight% is more preferable.

The average particle diameter of a liquid crystal capsule is 10-380 nm. From a viewpoint of display quality, 30-250 nm is preferable and, as for the average particle diameter of a liquid crystal capsule, 30-200 nm is more preferable. In addition, in this specification, an "average particle diameter" is the average value of the particle diameter measured 50 times by the light scattering method in 25 degreeC.

The liquid crystal composition can be used as an optically active composition by adding use as a composition having a nematic phase and an optically active compound.

2-1. Liquid crystal composition

The liquid crystal composition contains a liquid crystal material, and may optionally further include additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a dichroic dye, and the like.

The liquid crystal material contained in the liquid crystal composition is not particularly limited as long as it has good compatibility with the monomer and is poorly soluble in water. In addition, the liquid crystal composition containing a liquid crystal material may, for example, be a nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, a chiral nematic liquid crystal or the like. Among these, nematic liquid crystal is preferable.

It is preferable that a liquid crystal material contains the liquid crystal compound of a different characteristic. Specifically, it is preferable to have predetermined characteristics with respect to the upper limit temperature, viscosity, optical anisotropy, dielectric anisotropy, specific resistance, and the like of the nematic phase.

However, it is preferable that the ratio of the compound which has cyano from the viewpoint of a specific resistance or a voltage retention is less than 3 weight% with respect to the whole liquid crystal composition.

(One) Positive liquid crystal material contained in the liquid crystal composition

Positive liquid crystal compositions having a positive dielectric anisotropy mainly include a lower limit temperature of the nematic phase of about −10 ° C. or lower, an upper limit temperature of about 70 ° C. or higher, optical anisotropy in the range of about 0.20 to about 0.35, and a dielectric constant in the range of about 8 to about 40. Has anisotropy The element containing a liquid crystal composition has a large voltage retention. This composition is suitable for AM devices and is particularly suitable for transmissive AM devices.

It is preferable that a positive liquid crystal composition contains only a positive liquid crystal compound, and it is more preferable that a positive liquid crystal compound and a liquid crystal compound with dielectric constant anisotropy being zero or almost zero are included.

(2) Negative liquid crystal material contained in liquid crystal composition

Negative liquid crystal compositions having negative dielectric anisotropy have a lower limit temperature of the nematic phase of about −10 ° C. or lower, an upper limit temperature of about 70 ° C. or higher, optical anisotropy in the range of about 0.08 to about 0.35, and a range of about −2 to about −20. It has dielectric anisotropy. The element containing a liquid crystal composition has a large voltage retention. This composition is suitable for AM devices and is particularly suitable for transmissive AM devices.

It is preferable that a negative liquid crystal composition contains only a negative liquid crystal compound, and it is more preferable that a negative liquid crystal compound and the liquid crystal compound which dielectric constant anisotropy is zero or almost zero are included.

Particularly suitably, liquid crystal compositions used in liquid crystal capsules are specifically described in WO2015 / 162950A1, WO2016 / 063585A1, Japanese Patent Laid-Open No. 2017-222778 and the like.

2-2. Surfactants

The surfactant used in the preparation of the liquid crystal capsule is not particularly limited as long as it has a surface activity, but is preferably affinity for both the liquid crystal material and the surface of the capsule wall.

Surfactants that are affinity for both the liquid crystal material and the surface of the capsule wall are compounds which share hydrophobicity and hydrophilicity, such as glycerin, ethylene glycol, diethylene glycol, monoethyl ether, butanediol ( Butanediol), propylene glycol, propionic acid pentadiol, and the like, and the surfactants used in the manufacture of liquid crystal capsules include copolymers of electron donating monomers and maleic anhydride in radical polymerization and the like. Preference is given to using hydrolysates of polymers, copolymers of styrene (styrene) and maleic anhydride and similar polymers which may have substituents and copolymers of alkenyl and maleic anhydride and the like More preferably, the hydrolyzate of the polymer is used, and the valence of the styrene-maleic anhydride copolymer and similar polymers Seafood and 1-octadecene - to use a hydrolyzate of a similar polymer and a maleic anhydride copolymer and its especially preferred. In addition, hydrolysates of 2-ethylhexylvinylether-maleic anhydride copolymer and similar polymers can also be used.

1,000-500,000 are preferable and, as for the weight average molecular weight of surfactant of this invention, 5,000-50,000 are especially preferable. If it is this range, it will melt | dissolve in water sufficiently, a viscosity will rise and mixing will not become difficult.

2-3. Capsule wall

The monomers and prepolymers used in the production of liquid crystal capsules become the material of the capsule walls of the liquid crystal capsules. That is, by the in-situ polymerization method, the monomer and the prepolymer are polymerized to surround the liquid crystal composition, thereby forming a closed curved capsule wall. The monomer and the prepolymer are not particularly limited as long as they have a polymerization group.

As monomers or prepolymers used in the capsule wall in the production of liquid crystal capsules, for example, gelatin, amide resins, urethane (urethane) resins, silicone resins, phenol resins, urea (urea) resins, melamine resins, melamine-phenol resins, poly Ester resin, diallyl phthalate resin, an epoxy resin, etc. are mentioned. As the capsule wall used in the preparation of the liquid crystal capsule, it is preferable to use melamine resin or urea-formalin resin. More preferred capsule wall is melamine resin.

3. Other additives

When the coating liquid containing water is applied to a substrate such as glass with an electrode, since the surface tension of the coating liquid on the substrate is high, the substrate is splashed with a coating apparatus such as a bar coater or a slit coater. It may not be possible. In order to improve the applicability | paintability to a board | substrate, a surface regulator or a thickener can be used.

3-1. Surface conditioner

A surface modifier is added in order to lower the surface tension of a coating liquid and to improve applicability | paintability to a board | substrate, and surfactant or a leveling agent is used. In particular, additives which do not affect the electro-optical properties or voltage retention are preferable, and specifically, BYK-UV3530, BYK-348, BYK-381, BYK-3440, F-477, F-553, F-556, and the like. This is preferable, and BYK-UV3530, F-477, F-553 and BYK-348 are more preferable. As for content of an additive, 10 weight part or less is preferable in order to maintain 0.1 weight part or more, electro-optical characteristic, voltage retention, etc. in order to reduce surface tension with respect to the moisture of a coating liquid.

3-2. Thickener

A thickener is added in order to raise the viscosity of a coating liquid (relatively reduce the moisture concentration of a coating liquid), and a viscoelasticity modifier is used. In particular, additives which do not affect the electro-optical properties or voltage retention are preferable, and specifically, SN-thickener 601, SN-seeker 612, SN-seeker 612NC, SN-seeker 619, SN -Secner 621N, SN-Secner 621TF, SN-Secner 623N, SN-Secner 625N, SN-Secner 660T, SN-Secner 665T, SN-Secner 615, SN-Secner 617, SN-Sec Ner 618, SN-seeker 630, SN-seeker 634, SN-seeker 636 and SN-seeker 640 are preferred, and SN-seeker 612 is more preferred. As for content of an additive, 10 weight part or less is preferable in order to maintain 0.1 weight part or more, electro-optical characteristic, voltage retention, etc. in order to reduce surface tension with respect to the moisture of a coating liquid.

Preparation of a coating liquid is dripped the liquid crystal capsule little by little with respect to the stirring binder aqueous solution, for example. In order to disperse | distribute a liquid crystal capsule uniformly to a binder, the dropping speed is preferably 0.2 ml / sec or less, and the stirring time after dropping is preferably 20 minutes or more. After stirring, in order to remove the gas melt | dissolved in a process, it is preferable to perform the defoaming process by pressure_reduction | reduced_pressure or an ultrasonic wave.

The formation of the functional film is performed by coating the coating liquid in the form of a thin film on a substrate using a coating apparatus such as a bar coater or a slit coater (coating step), and heating it in a hot plate or a circulating thermostat to evaporate volatile components (mainly moisture). And drying (polymerization step) by irradiation or heating with UV or the like. It is preferable to determine the temperature and time of a drying process using apparatus, such as TG / DTA. When a solvent is water, a drying temperature of 50-100 degreeC and a drying time of 30 to 120 minutes are preferable in many cases. Since the polymerization strength and time of a polymerization process are influenced by a polymeric component, a crosslinking agent, and a polymerization initiator, it is preferable to determine using apparatuses, such as PhotoDSC. When irradiating UV etc., it is preferable to use the filter etc. which cut the spectrum of 350 nm or less in consideration of the damage to a liquid crystal material.

The weight ratio of the liquid crystal capsule and the binder in the functional film is preferably 50% or more, more preferably 70%, in order to obtain a large optical change by voltage application. On the other hand, in order to maintain the strength or flexibility of the functional film, the ratio of the binder is preferably 20% or more, more preferably 40%.

The film thickness of the functional film is 0.5 μm or more in order to obtain a sufficient optical change by applying a voltage when driving only one side of a substrate such as a comb-type (lateral electric field) substrate, thereby preventing a decrease in transmittance due to a region in which the voltage application effect is ineffective. In order to do so, 10 micrometers or less are preferable and 1-6 micrometers is more preferable.

Example

The present invention will be described in more detail with reference to the following examples. The present invention is not limited by these examples. The invention also includes mixtures of at least two of the compositions of the examples. The synthesized compound was identified by a method such as NMR analysis. The properties of the compound, the composition and the workpiece were measured by the method described below.

NMR analysis: DRX-500 manufactured by Bruker BioSpin KK was used for the measurement. ^In the measurement of ¹ H-NMR, the sample was dissolved in a deuterated solvent such as CDCl ₃ , and the measurement was performed under conditions of 500 MHz and 16 times of integration times at room temperature. Tetramethylsilane was used as internal standard. ^{In 19} F-NMR measurement, CFCl ₃ was used as an internal standard, and the integration was performed 24 times. In the description of the nuclear magnetic resonance spectrum, s is a singlet, d is a doublet, t is a triplet, q is a quartet, quin is a quintet, sex Denotes a sextet, m denotes multiplet, and br denotes a broad line.

Gas chromatographic analysis: The GC-14B type gas chromatograph by Shimadzu Corporation was used for the measurement. Carrier gas is helium (2 mL / min). The sample vaporization chamber was set to 280 degreeC, and the detector (FID) was set to 300 degreeC. Separation of component compounds is carried out by Agilent Technologies Inc. Capillary column DB-1 (30 m in length, 0.32 mm in inner diameter, 0.25 μm in film thickness; dimethylpolysiloxane (siloxane); nonpolar) for the fixed liquid phase was used. After maintaining this column at 200 degreeC for 2 minutes, it heated up to 280 degreeC at the speed of 5 degree-C / min. The sample was prepared in acetone solution (0.1% by weight), and then 1 μL of the sample was injected into the sample vaporization chamber. The recorder is C-R5A Chromatopac or its equivalent manufactured by Shimadzu Corporation. The obtained gas chromatogram showed the retention time of the peak corresponding to a component compound, and the area value of the peak.

Chloroform (form), hexane (hexane), etc. can also be used as a solvent for diluting a sample. To separate the component compounds, the following capillary column may be used. Agilent Technologies Inc. HP-1 (length 30m, inner diameter 0.32mm, film thickness 0.25μm) manufactured by Rtx-1 (length 30m, internal diameter 0.32mm, film thickness 0.25μm) manufactured by Restek Corporation, SGE International Pty. Ltd. BP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm). Capillary column CBP1-M50-025 (50 m in length, 0.25 mm in inner diameter, 0.25 micrometer in film thickness) by Shimadzu Corporation can be used for the purpose of preventing the superposition of a compound peak.

The ratio of the liquid crystalline compound contained in a composition can also be computed by the following method. The mixture of liquid crystalline compounds is detected by gas chromatograph (FID). The area ratio of the peaks in the gas chromatogram corresponds to the ratio (weight ratio) of the liquid crystalline compound. When the capillary column described above is used, the correction coefficient of each liquid crystalline compound may be regarded as one. Therefore, the ratio (weight%) of a liquid crystalline compound can be computed from the area ratio of a peak.

Measurement sample: When measuring the characteristic of a composition, the composition was used as a sample as it is. When measuring the characteristic of a compound, the sample for a measurement was prepared by mixing this compound (15 weight%) with a mother liquid crystal (85 weight%). The characteristic value of the compound was computed by the extrapolation method from the value obtained by the measurement. (Extrapolation) = {(measured value of sample) -0.85Х (measured value of mother liquid crystal)} / 0.15. In this ratio, when the smectic phase (or crystal) is precipitated at 25 ° C, the ratio of the compound and the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99% by weight. Changed to. By this extrapolation method, the upper limit temperature, optical anisotropy, viscosity, and dielectric anisotropy of the compound were determined.

The following mother liquid crystals were used. The proportions of the component compounds are expressed in weight percent.

Measurement method: The measurement of the characteristic was performed by the following method. Most of these methods are described in the JEITA standard (JEITA / ED-2521B) or modified by the Japan Electronics and Information Technology Industries Association (hereinafter referred to as JEITA). It was how. The thin film transistor (TFT) was not attached to the TN element used for the measurement.

(1) Upper limit temperature (NI; degreeC) of a nematic phase: The sample was put into the hotplate of the melting-point measuring apparatus provided with the polarizing microscope, and it heated at the speed of 1 degree-C / min. The temperature when a part of the sample changed into an isotropic liquid on the nematic phase was measured.

(2) Lower limit temperature of nematic phase (T _C ; ° C.): A sample having a nematic phase is placed in a glass bottle and placed in a freezer at 0 ° C., −10 ° C., −20 ° C., 30 ° C., and −40 ° C. After storage for 10 days, the liquid crystal phase was observed. For example, when the sample remained nematic phase at -20 ° _C and changed to crystal or smectic phase at -30 ° _C , T _C was described as <-20 ° C.

(3) Viscosity (bulk viscosity; eta; measured at 20 ° C; mPa · s): An E-type rotational viscometer manufactured by TOKYO KEIKI INC. Was used for the measurement.

(4) Viscosity (rotational viscosity; γ 1; measured at 20 ° C .; mPa · s): The measurement is performed by M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995) was followed. Samples were placed in a TN device with a twist angle of 0 ° and a gap (cell gap) of two glass substrates of 5 μm. The device was applied in steps of 0.5V in the range of 16V to 19.5V. After 0.2 seconds of no application, application was repeated under the conditions of only one square wave (square pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. The values of the rotational viscosities were obtained from these measurements and the formula (8) described on page 40 of the paper by M. Imai. The value of dielectric anisotropy required in this calculation was calculated | required by the method described below using the element which measured this rotational viscosity.

(5) Optical anisotropy (refractive anisotropy; Δn; measured at 25 ° C.): The measurement was performed by an Abbe refractometer having a polarizing plate attached to the eyepiece using light having a wavelength of 589 nm. After rubbing the surface of the main prism in one direction, the sample was dropped into the main prism. Refractive index (n ∥) was measured when the direction of polarization is parallel to the direction of rubbing. The refractive index (n⊥) was measured when the direction of polarization was perpendicular to the direction of rubbing. The value of optical anisotropy (Δn) was calculated from the formula of Δn = n ∥ n⊥. In the mode using the optical change by the Kerr effect, it is preferable that the product of optical anisotropy and dielectric anisotropy is larger, so that the optical anisotropy is as large as possible. Optical anisotropy becomes like this. Preferably it is the range of 0.20 to 0.35, More preferably, it is the range of 0.23 to 0.32.

(6) Dielectric constant anisotropy (Δε; measured at 25 ° C.): The sample was placed in a TN element having a gap (cell gap) of 9 glass sheets of 9 m and a twist angle of 80 degrees. A sine wave (10 V, 1 kHz) was applied to this element, and after 2 seconds, the dielectric constant (ε ∥ ) in the major axis direction of the liquid crystal molecules was measured. A sine wave (0.5 V, 1 kHz) was applied to this element, and after 2 seconds, the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured. The value of dielectric anisotropy was calculated from the formula of Δε = ε ∥ −ε⊥. It is preferable that the dielectric anisotropy be large in order to reduce the driving voltage. In particular, in a mode in which the electric field applied to the liquid crystal composition is limited by polymer stabilization or encapsulation, the driving voltage tends to be high, and thus the dielectric anisotropy is preferably as large as possible. In the mode using the optical change due to the Kerr effect, it is preferable that the product of the optical anisotropy and the dielectric anisotropy is larger, and the dielectric anisotropy is preferably as large as possible. The dielectric anisotropy is preferably in the range of 8 to 40, and more preferably in the range of 10 to 30.

(7) Threshold voltage (Vth; measured at 25 ° C; V): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. Samples were placed in a TN device in a normally white mode with a gap (cell gap) of two glass substrates of 0.45 / Δn (μm) and a twist angle of 80 degrees. The voltage (32 Hz, square wave) applied to the device was increased in steps of 0.02V from 0V to 10V. At this time, light was irradiated to the device in a direction perpendicular to the device, and the amount of light transmitted through the device was measured. A voltage-transmission curve having a transmittance of 100% was obtained when this light amount was maximized and a transmittance of 0% when this light amount was minimum. Threshold voltage was represented by the voltage when the transmittance | permeability became 90%.

(8) Elastic constant (K; measured at 25 ° C .; pN): The HP4284A LCR meter manufactured by YOKOGAWA HEWLETT PACKARD, LTD was used for the measurement. The sample was put into the horizontal orientation element whose spacing (cell gap) of two glass substrates is 20 micrometers. An electric charge of 0 to 20 volts was applied to the device, and the capacitance and the applied voltage were measured. The measured values of capacitance (C) and applied voltage (V) are fitted using the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), equation (2.98), equation (2.101) on page 75, and equation (2.99) The values of K11 and K33 were obtained. Next, K22 was calculated using the values of K11 and K33 obtained above in equation (3.18) on page 171 of the same. The elasticity constant K was represented by the average value of K11, K22, and K33 calculated | required in this way.

(9) Specific resistance (ρ; measured at 25 ° C; Ωcm): 1.0 mL of sample was injected into a container equipped with electrodes. DC voltage (10V) was applied to this container, and DC current after 10 second was measured. The specific resistance was calculated from the following equation. (Specific resistance) = {(voltage) x (capacitance of container)} / {(direct current) x (dielectric constant of vacuum)}.

(10) SEM (Scanning Electron Microscope) Observation: A liquid crystal capsule water dispersion was coated on a fine neutral paper or glass using a die coater, spin coater or bar coater, and a hot plate or dryer was used. A sample was prepared by evaporating water in the liquid crystal capsule aqueous dispersion. The sample was fixed to a sample stand for SEM observation with a conductive tape, and platinum was deposited using a sputtering device (manufactured by Hitachi High Technologies, Inc .: E-1045). This sample stage was attached to SEM (Hitachi High-Technologies Corporation. Make: SU-70). The sample was observed, changing acceleration voltage (0.5-1.0 kV), magnification (1k-50k), etc.

(11) Average particle diameter measurement of capsule: In the present invention, a dynamic light scattering particle size analyzer (NanoTrack UPA) manufactured by Nikkiso Co., Ltd. was used for the measurement. The sample which diluted the liquid-crystal capsule water dispersion liquid to the suitable density | concentration with ultrapure water was prepared, and the average particle diameter was measured at 25 degreeC.

(12-1) Setting of T ₀ and T ₁₀₀

As shown in Fig. 2, the optical system includes an LED light source 3 (B180-5600K manufactured by KLV Co., Ltd) and a polarizer (attached to a polarization microscope (eclipse LV100POL manufactured by Nikon). 4), the analyzer 6, the glass substrate 5 which has a comb electrode, and the optical measuring device 7, and the glass substrate 5 is a comb type electrode shown in FIG. It set so that the linear direction of (electrode 1, 2) might be 45 degrees with respect to each polarizing plate, and the incidence angle of the light source 3 might be perpendicular. The transmitted light is measured using the optical measuring device 7 (3298F manufactured by YOKOGAWA), and the transmitted light measured by cross nicol is set to 0% (T ₀ ) in transmittance and the transmitted light measured by para nicol is 100% (T ₁₀₀ ). It was.

(12-2) Measurement of V ₁₀ , T _min and T _max

A voltage (square wave (60 Hz)) was applied to a glass cell having a comb electrode on which a functional film was formed by an arbitrary waveform generator (33220A manufactured by Agilemt) and a bipolar power supply (HSA4051 manufactured by NF), and the transmittance rose to 10%. Was set to V ₁₀ (unit: V). In addition, the transmittance | permeability at the time of applying voltage of 0V was made into _{Tmin (} unit:%), and the transmittance | maximum which becomes the maximum was made into _Tmax (unit:%).

(13) Film thickness measurement (unit: μm)

The functional film was scraped off from a part of the glass cell having the comb electrode on which the functional film was formed, and the step was measured by a fine shape measuring device (alpha step IQ manufactured by KLA TENCOR Co., Ltd.) to determine the film thickness.

(14) Measurement of solid content concentration (unit:%)

Solid content concentration of the coating liquid containing a liquid crystal capsule and a binder was measured using the moisture meter (Shimadzu Seisakusho make MOC63u).

1. Preparation of Liquid Crystal Capsule A

An aqueous solution of 5.24 wt% styrene-maleic anhydride copolymer (molecular weight: about 350,000) (160 g) and ultrapure water (70 g) were placed in a stainless steel beaker and stirred with a homogenizer (IKAT25). The following liquid crystal composition 1 (40g) was thrown in there little by little, and it stirred for 3 minutes and emulsified. This emulsion (226.6 g) was added to NanoVator (YOSHIDA KIKAI CO., LTD .: NVL-ES008-D), and passed through an extrusion pressure of 150 MPa three times. (Step C) Then, it heated at 80 degreeC, melamine prepolymer (8.4g) was thrown in, stirring for 2 hours, stirring with the stirrer (HEIDON make: high-power general purpose stirrer BLh1200). After the reaction mixture was returned to room temperature, it was adjusted to pH 7 with a 10 wt% sodium hydroxide aqueous solution to obtain a liquid crystal capsule aqueous dispersion.

A sample obtained by diluting the liquid crystal capsule water dispersion liquid to an appropriate concentration with ultrapure water was prepared, and observed with a dynamic light scattering particle size analyzer (Nanotrak UPA) manufactured by Nikki Corporation, and found a liquid crystal capsule having an average particle diameter of about 200 nm. It became.

2. Preparation of Liquid Crystal Capsule B

A 13.6 wt% aqueous solution of styrene-maleic anhydride copolymer (molecular weight: approximately 5,500) (44.0 g) and ultrapure water (76.0 g) were placed in a stainless steel beaker and stirred with a homogenizer (IKAT25). The liquid crystal composition 1 (18g) was thrown in there little by little, and it stirred for 3 minutes and emulsified. This emulsion (126.5 g) was introduced into Star Burst (SUGINO MACHINE LIMITED: HJP-25001) and passed through three times at an extrusion pressure of 150 MPa. Then, it heated at 70 degreeC, melamine prepolymer (6.6g) was thrown in, stirring with the stirrer (HEIDON make: high-power general purpose stirrer BLh1200), and after stirring for 15 minutes, it heated up at 80 degreeC and stirred for 105 minutes. After the reaction mixture was returned to room temperature, it was adjusted to pH 7 with an aqueous 1.00 wt% ammonia solution to obtain a liquid crystal capsule aqueous dispersion.

A sample obtained by diluting the liquid crystal capsule water dispersion liquid to an appropriate concentration with ultrapure water was prepared, and observed with a dynamic light scattering particle size analyzer (Nanotrak UPA) manufactured by Nikki Corporation, and found a liquid crystal capsule having an average particle diameter of about 130 nm. It became.

3. Preparation of Liquid Crystal Capsule C

A 6.1 wt% 1-octadecene-maleic anhydride copolymer (molecular weight: about 36,000) aqueous solution (148.0 g) and ultrapure water (2.0 g) were placed in a stainless steel beaker and stirred with a homogenizer (IKAT25). Liquid-crystal composition 1 (27.8g) was thrown in there little by little, and it stirred for 3 minutes and emulsified. This emulsion (166.8 g) was introduced into a star burst (Sugino Machine, HJP-25001), and passed five times at an extrusion pressure of 150 MPa. Then, it heated at 70 degreeC, melamine prepolymer (11.1g) was thrown in, stirring with the stirrer (HEIDON make: high power general purpose stirrer BLh1200), stirred for 15 minutes, and it heated up at 80 degreeC, stirred for 105 minutes, and liquid crystal A capsule water dispersion was obtained.

A sample obtained by diluting the liquid crystal capsule water dispersion liquid to an appropriate concentration with ultrapure water was prepared, and observed with a dynamic light scattering particle size analyzer (Nanotrak UPA) manufactured by Nikki Corporation, and found a liquid crystal capsule having an average particle diameter of about 170 nm. It became.

Liquid Crystal Composition 1

3-HB (F) TB-2 5%

3-HB (F) TB-3 5%

3-HB (F) TB-4 5%

3-H2BTB-2 3%

3-H2BTB-3 3%

3-H2BTB-4 3%

3-BB (F, F) XB (F, F) -F 9%

3-BB (F) B (F, F) XB (F) -F 3%

3-BB (F) B (F, F) XB (F, F) -F 2%

4-BB (F) B (F, F) XB (F, F) -F 7%

5-BB (F) B (F, F) XB (F, F) -F 7%

3-BB (F, F) XB (F) B (F, F) -F 6%

3-BB (F) B (F, F) -F 3%

2-BTB-O1 7.8%

3-BTB-O1 7.8%

4-BTB-O1 7.8%

4-BTB-O2 7.8%

5-BTB-O1 7.8%

NI = 90.0 ° C .; Tc <-20 ° C; Δn = 0.246; Δε = 9.4; Vth = 1.88V; η = 42.7 mPas.

The symbol of the said compound follows the notation of Table A below.

4. Preparation of Coat Liquid

The composition of the coating liquid prepared in Table 1 is shown. The numerical value in a table | surface is the weight% of solid content of each component. A binder aqueous solution (or water dispersion) containing a compound represented by the formula (1-1) or the like is prepared, and the liquid crystal capsule aqueous dispersion liquid covering the liquid crystal composition 1 with a resin is stirred with a magnetic starr or the like to be uniformly dispersed in the binder aqueous solution. While mixing. This mixed solution was decompressed for the purpose of removing bubbles or gas in water (for example, decompression degree: 1 kPa, decompression time: 30 minutes). The photopolymerization initiator Irgacure 2959 was added 7 parts by weight based on the weight of the binder.

TABLE 1

Table 1 Composition of the coating liquid

5. Formation of Functional Membranes

The coating liquid shown in Table 1 was coated on the glass cell which has a comb electrode using the auto coater (K control coater by RK company) and the wire bar selected so that it might become a predetermined | prescribed film thickness. It was heated for 30 minutes with a hot plate (set temperature is 50 ° C) and water was removed. Polymerization reaction was performed to this glass cell by UV exposure (integrated light quantity of 1200 mJ in 365 nm) using a 350 nm or less cut filter in nitrogen atmosphere, and the functional film was formed.

6. Evaluation of Physical Properties of Functional Membranes

In Table 2, the evaluation result of the functional film formed in Examples 1-11 is shown.

TABLE 2

Table 2 Evaluation results of functional membrane

7. Preparation of Coat Liquid

The composition of the coating liquid prepared in Table 3 is shown. The numerical value in a table | surface is the weight% of solid content of each component. A binder aqueous solution (or water dispersion) containing a compound represented by formula (1-1) or the like is prepared, and the liquid crystal capsule aqueous dispersion liquid covering the liquid crystal composition with a resin is stirred with a magnetic starr or the like so as to be uniformly dispersed in the binder aqueous solution. Mixed. This mixed solution was decompressed for the purpose of removing bubbles or gas in water (for example, decompression degree: 1 kPa, decompression time: 30 minutes). In addition, the photoinitiator Irgacure 2959 added 3.5 weight part with respect to the weight of the binder, and 0.5 weight part of surface adjusting agent BYK-UV3530 was added with respect to water.

Table 3 Composition of the coating liquid Example
12 Example
13 Example
14 Example
15 Example
16 Example
17 Example
18 Liquid crystal capsule
A Liquid crystal capsule
B  50.0  70.0 Liquid crystal capsule
C  50.0  70.0  70.0  80.0  90.0 Formula (1-1)  30.0  30.0  18.0  18.0  12.0  6.0  18.0 Formula (1-2) Formula (1-3) Formula (1-4) Formula (2-1) Formula (2-2) Formula (2-3)  20.0  20.0  12.0  12.0  8.0  4.0  11.1 Formula (3-1)  0.9 Sum 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Solids concentration  30.0  30.0  30.0  30.0  28.8  26.4  22.7

8. Formation of Functional Membrane

The coating liquid shown in Table 3 was coated on the glass cell which has a comb electrode using the auto coater (K control coater by a RK company) and the wire bar selected so that it might become a predetermined | prescribed film thickness. It was heated for 30 minutes with a hot plate (set temperature is 60 ° C) and water was removed. Polymerization reaction was performed to this glass cell by UV exposure (integrated light quantity of 1200 mJ in 365 nm) using a 350 nm or less cut filter in nitrogen atmosphere, and the functional film was formed. In Example 18, the polymerization reaction was carried out by further heating for 3 hours on a hot plate (set temperature: 100 ° C) to form a functional film.

9. Evaluation of Physical Properties of Functional Membranes

In Table 4, the evaluation result of the functional film formed in Examples 12-18 is shown.

Table 4 Evaluation Results of Functional Membranes Example
12 Example
13 Example
14 Example
15 Example
16 Example
17 Example
18 Film thickness
[μm]  3.6  3.0  3.0  8.1  2.6  1.9  2.3 T _min
[%]  1.1  1.4  2.0  4.1  2.0  1.8  0.8 T _max
[%]  50  67  70  51  74  72  62 V ₁₀
[V]  73  55  43  48  42  40  77

By the binder of the present invention, a functional film in which the liquid crystal capsule was uniformly dispersed was prepared, and good optical properties were obtained by applying a voltage to the functional film.

This functional film is optically isotropic and can be used for the liquid crystal display element driven by the liquid crystal layer which is optically isotropic. Furthermore, it can be used for the element of the mode of IPS or FFS. The device has good optical properties.

1, 2... electrode
3... Light source
4… Polarizer
5... Glass cell
6... Analyzer (Analyzer)
7... Photodetector

Claims (18)

The coating liquid containing the binder which consists of a liquid crystal capsule which covered the liquid crystal composition with resin, and at least 1 polymeric compound. The method according to claim 1,
The coating liquid, wherein the polymerizable compound is an acrylamide compound or a methacrylamide compound. The method according to claim 1 or 2,
The said coating liquid contains the at least 1 compound represented by Formula (1) as a 1st component, and the at least 1 compound represented by Formula (2) as a 2nd component.

(In formula (1) and formula (2), R <^1> and R <^3> is respectively independently hydrogen or methyl; R <^2> is a single bond or C1-C20 alkylene, In this alkylene, And -CH _2- , which are not adjacent to each other, may be substituted with -O- or a group represented by formula (a); R ⁴ is a single bond or alkylene having 1 to 20 carbon atoms, and this alkylene In which any —CH ₂ — not adjacent to each other may be substituted with —O—; Z ¹ is —NH— or —O—; n is 1, 2, or 3,
In formula (a), R ⁵ is hydrogen or methyl) The method according to claim 3,
The binder contains at least one compound in which all R ¹ in formula (1) is hydrogen as the first component and at least one compound in which R ³ in formula (2) is hydrogen as the second component. Coat liquid to say. The method according to claim 3,
The coating liquid according to the weight of the binder, wherein the proportion of the first component is in the range of 10 to 80% by weight, and the proportion of the second component is in the range of 20 to 80% by weight. The method according to claim 3,
The coating liquid in which the said binder contains at least 1 compound chosen from the group of the compound represented by Formula (1-1)-Formula (1-4) as said 1st component.

The method according to claim 3,
The coating liquid wherein the binder contains at least one compound selected from the group of compounds represented by formulas (2-1) to (2-3) as the second component.

The method according to claim 3,
The coating liquid of the said binder further contains at least 1 compound chosen from the group which consists of a polyfunctional amine and a polyfunctional thiol which has two or more primary or secondary amines as a 3rd component. The method according to claim 3,
The coating liquid which the said binder further contains at least 1 compound chosen from the group of the compound represented by Formula (3-1)-Formula (3-3) as a 3rd component.

The method according to claim 8 or 9,
Based on the weight of the binder, the coating liquid, wherein the proportion of the third component is in the range of 0.1% by weight to 10% by weight. The method according to claim 1 or 2,
The coating liquid according to the weight of the coating liquid having a solid content concentration of 5% by weight or more. The method according to claim 1 or 2,
A coating liquid, wherein the weight ratio of solids of the liquid crystal capsule and solids of the binder is 5: 5 to 9: 1 based on the weight of solids of the coating liquid. The method according to claim 1 or 2,
The coating liquid in which the liquid crystal capsule which covered the liquid crystal composition with the melamine resin is disperse | distributed. The method according to claim 1 or 2,
The coating liquid whose average particle diameter of the said liquid crystal capsule is 10 nm-380 nm. The functional film formed using the coating liquid of Claim 1 or 2. The method according to claim 15,
A functional film formed by making a coating liquid into a thin film form using a coating apparatus, volatilizing moisture by heating, and then superposing | polymerizing by irradiation, such as UV. The method according to claim 15,
A functional membrane having a film thickness of at least 0.5 μm. The method according to claim 15,
The functional film which expresses an optical change by voltage application.

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