TWI893195B - Two-component polymerizable liquid crystal composition - Google Patents

Abstract

The present invention provides a polymerizable liquid crystal composition that can produce a liquid crystal cured film having good optical properties even after long-term storage, a storage method thereof, a method for producing the composition, and a method for producing the liquid crystal cured film. The two-component polymerizable liquid crystal composition of the present invention comprises an agent A and an agent B, wherein the agent A comprises a reactive additive having a polymerizable group and an active hydrogen-reactive group in the molecule and a solvent, and the agent B comprises a polymerizable liquid crystal compound and a solvent, and the Ra value of the solvent in the agent A as a whole, as expressed by the following formula (1), satisfies Ra>37.0. [Wherein, δ _D(W) represents the dispersion term of the Hansen solubility parameter of water, δ _D(S) represents the dispersion term of the Hansen solubility parameter of the entire solvent based on the weighted average of the solvents, δ _P(W) represents the polar term of the Hansen solubility parameter of water, δ _P(S) represents the polar term of the Hansen solubility parameter of the entire solvent based on the weighted average of the solvents, δ _H(W) represents the hydrogen bond term of the Hansen solubility parameter of water, and δ _H(S) represents the hydrogen bond term of the Hansen solubility parameter of the entire solvent based on the weighted average of the solvents]

Description

Two-component polymerizable liquid crystal composition

The present invention relates to a two-component polymerizable liquid crystal composition and a storage method thereof, a method for producing the polymerizable liquid crystal composition, and a method for producing a liquid crystal cured film.

In recent years, with the trend toward thinner image display devices, optical films such as polarizing plates and retardation plates using polarizing films have been developed. These films incorporate a cured liquid crystal layer, obtained by coating a polymerizable liquid crystal compound onto a substrate or alignment film and curing it in an aligned state. In the production of these optical films, from the perspectives of film-forming properties and operability, the polymerizable liquid crystal compound is typically coated onto the substrate or alignment film as a polymerizable liquid crystal composition, formed by dissolving the polymerizable liquid crystal compound in a solvent or the like. It is known that when manufacturing an optical film by coating a composition onto a substrate or an alignment film, it is better to have a higher degree of adhesion between the substrate or alignment film and the resulting optical film, as this prevents peeling during processing, thereby facilitating the production of a high-quality optical film. A composition having the property of providing an optical film with high adhesion has been proposed (Patent Document 1). [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent No. 6019591

[Identify the problem you want to solve]

However, it has been discovered that if this composition is stored for a long period of time to form a liquid crystal cured film, alignment defects may occur, and good alignment may not necessarily be achieved. Therefore, the purpose of the present invention is to provide a polymerizable liquid crystal composition that can produce a liquid crystal cured film with good optical properties even after long-term storage, a storage method thereof, a method for producing the composition, and a method for producing the liquid crystal cured film. [Technical Means for Solving the Problem]

The inventors of the present invention have repeatedly conducted detailed research to solve the above-mentioned problems and have finally completed the present invention. That is, the present invention includes the following preferred aspects. [1] A two-liquid polymerizable liquid crystal composition, which contains agent A and agent B, wherein agent A contains a reactive additive having a polymerizable group and an active hydrogen reactive group in the molecule and a solvent, and agent B contains a polymerizable liquid crystal compound and a solvent, and the solvent in the above-mentioned agent A is represented by the following formula (1): [Number 1] [Wherein, δ _D(W) represents the dispersion term of the Hansen solubility parameter of water, δ _D(S) represents the dispersion term of the Hansen solubility parameter of the entire solvent based on the weighted average of the solvents, δ _P(W) represents the polar term of the Hansen solubility parameter of water, δ _P(S) represents the polar term of the Hansen solubility parameter of the entire solvent based on the weighted average of the solvents, δ _H(W) represents the hydrogen bond term of the Hansen solubility parameter of water, and δ _H(S) represents the hydrogen bond term of the Hansen solubility parameter of the entire solvent based on the weighted average of the solvents] The value of Ra represented by satisfies Ra>37.0. [2] The two-component polymerizable liquid crystal composition of [1], wherein the value of Ra of the solvent in the above-mentioned agent B represented by the above-mentioned formula (1) satisfies Ra ≤ 37.0. [3] The two-component polymerizable liquid crystal composition of [1] or [2], wherein the amount of the above-mentioned reactive additive contained in the above-mentioned agent A is 0.5 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the above-mentioned polymerizable liquid crystal compound. [4] The storage method of any one of [1] to [3], wherein the above-mentioned agent A and agent B are stored separately. [5] The storage method of [4], wherein the above-mentioned agent A is stored in a plastic container or a metal container. [6] The storage method of [4] or [5], wherein the above-mentioned agent A is stored under a dry inert gas atmosphere. [7] A method for producing a polymerizable liquid crystal composition, comprising the step of mixing the agent A and the agent B constituting the two-component polymerizable liquid crystal composition as described in any one of [1] to [3]. [8] A method for producing a liquid crystal curing film, comprising: a step of forming an alignment film on a substrate; a step of mixing the agent A and the agent B constituting the two-component polymerizable liquid crystal composition as described in any one of [1] to [3] to obtain a polymerizable liquid crystal composition; a step of coating the mixed polymerizable liquid crystal composition on the alignment film to obtain a coating film; and a step of curing the coating film. [Effects of the Invention]

The present invention provides a polymerizable liquid crystal composition capable of producing a liquid crystal cured film with excellent optical properties even after long-term storage, a storage method thereof, a method for producing the composition, and a method for producing the liquid crystal cured film. Furthermore, the liquid crystal cured film obtained from the polymerizable liquid crystal composition of the present invention exhibits high adhesion and an excellent appearance.

The following describes the embodiments of the present invention in detail. However, the scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the spirit of the present invention.

The two-component polymerizable liquid crystal composition of the present invention comprises agent A and agent B, wherein agent A comprises a reactive additive having a polymerizable group and an active hydrogen reactive group in the molecule and a solvent, and agent B comprises a polymerizable liquid crystal compound and a solvent, and the solvent in agent A is represented by the following formula (1) [number 2] [Wherein, δ _D(W) represents the dispersion term of the Hansen solubility parameter of water, δ _D(S) represents the dispersion term of the Hansen solubility parameter of the entire solvent based on the weighted average of the solvents, δ _P(W) represents the polar term of the Hansen solubility parameter of water, δ _P(S) represents the polar term of the Hansen solubility parameter of the entire solvent based on the weighted average of the solvents, δ _H(W) represents the hydrogen bond term of the Hansen solubility parameter of water, and δ _H(S) represents the hydrogen bond term of the Hansen solubility parameter of the entire solvent based on the weighted average of the solvents] The value of Ra represented by satisfies Ra>37.0.

The two-component polymerizable liquid crystal composition of the present invention includes a reactive additive, a polymerizable liquid crystal compound, and a solvent for dissolving the same as essential components. The reactive additive and the polymerizable liquid crystal compound are separately mixed into agent A and agent B, respectively.

<Agent A> [Reactive Additive] Reactive additives generally refer to substances added to polymerizable liquid crystal compositions to improve the adhesion of liquid crystal cured films. The polymerizable groups contained in the reactive additives in Agent A are groups that participate in the polymerization reaction. These polymerizable groups can be carbon-carbon unsaturated bonds, such as carbon-carbon double bonds or carbon-carbon triple bonds. Specific examples include vinyl, (meth)acrylic, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, oxirane, and cyclobutylene.

The active hydrogen-reactive groups contained in the reactive additives in Agent A refer to groups reactive toward groups having active hydrogen atoms, such as carboxyl (-COOH), hydroxyl (-OH), and amino (-NH ₂ ). Representative examples include epoxy groups, glycidyl groups, oxazolyl groups, carbodiimide groups, aziridine groups, amide groups, isocyanate groups, thioisocyanate groups, maleic anhydride groups, and alkoxysilyl groups. Preferably, the reactive additive contains at least two active hydrogen-reactive groups. In this case, the multiple active hydrogen-reactive groups may be the same or different.

The number of polymerizable groups and active hydrogen-reactive groups possessed by the reactive additive is usually 1 to 20, preferably 1 to 10, respectively.

In a preferred embodiment, the reactive additive preferably comprises a vinyl group and/or a (meth)acrylic group as a polymerizable group, preferably comprises at least one group selected from the group consisting of an epoxy group, a glycidyl group, an isocyanate group, and an alkoxysilyl group as an active hydrogen-reactive group, and more preferably comprises a reactive additive having an acrylic group and an isocyanate group, or a reactive additive having an acrylic group and an alkoxysilyl group.

Specific examples of reactive additives include: compounds having a (meth)acrylic acid group and an epoxy group, such as methacryloyloxyglycidyl ether or acryloxyglycidyl ether; compounds having a (meth)acrylic acid group and an oxycyclobutyl group, such as oxycyclobutane acrylate or oxycyclobutane methacrylate; compounds having a (meth)acrylic acid group and a lactone group, such as lactone acrylate or lactone methacrylate; vinyl oxazoline or isoacryloyloxyglycidyl ether; Compounds containing a vinyl group and an oxazolyl group, such as oxazoline; compounds containing a (meth)acrylate group and an isocyanate group, such as isocyanatomethyl acrylate, isocyanatomethyl methacrylate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate; oligomers of compounds containing a (meth)acrylate group and an alkoxysilyl group, such as 3-acryloyloxypropyltrimethoxysilane and 3-methacryloyloxypropylmethyldimethoxysilane. Further examples include compounds containing a vinyl group or a vinylidene group and an acid anhydride, such as methacrylic anhydride, acrylic anhydride, maleic anhydride, and vinylmaleic anhydride. Among them, preferred are methacryloyloxyglycidyl ether, acryloyloxyglycidyl ether, isocyanatomethyl acrylate, isocyanatomethyl methacrylate, vinyl oxazoline, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 3-acryloyloxypropyltrimethoxysilane, and oligomers thereof; particularly preferred are isocyanatomethyl acrylate, 2-isocyanatoethyl acrylate, 3-acryloyloxypropyltrimethoxysilane, and oligomers thereof.

Reactive additives can be used directly from commercial products or after purification as needed. Commercially available products include, for example, Laromer (registered trademark) PR9000 (manufactured by BASF), Karenz AOI (registered trademark) (manufactured by Showa Denko Co., Ltd.), and KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.).

The amount of the reactive additive contained in Agent A is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 1.5 parts by mass or more, further preferably 2 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, further preferably 6 parts by mass or less, further preferably 4 parts by mass or less, relative to 100 parts by mass of the polymerizable liquid crystal compound described below. When the amount of the reactive additive is above the lower limit and below the upper limit, it is easy to improve the adhesion of the liquid crystal cured film produced from the two-component polymerizable liquid crystal composition of the present invention without impairing the alignment properties. The reactive additive may be used alone or in combination of two or more. When two or more reactive additives are used, the amount of the reactive additives mentioned above represents their total amount.

[Solvent] The solvent contained in Agent A has a Ra value expressed by the following formula (1) that satisfies Ra>37.0. [Number 3] [Wherein, δ _D(W) represents the dispersion term of the Hansen solubility parameter of water, δ _D(S) represents the dispersion term of the Hansen solubility parameter of the entire solvent based on the weighted average of the solvents, δ _P(W) represents the polar term of the Hansen solubility parameter of water, δ _P(S) represents the polar term of the Hansen solubility parameter of the entire solvent based on the weighted average of the solvents, δ _H(W) represents the hydrogen bond term of the Hansen solubility parameter of water, and δ _H(S) represents the hydrogen bond term of the Hansen solubility parameter of the entire solvent based on the weighted average of the solvents] The dispersion term of the Hansen solubility parameter of the entire solvent based on the weighted average of the solvents can be calculated from the dispersion term of the Hansen solubility parameter of each solvent contained in agent A and the volume fraction of each solvent according to the following formula (1-1). [Equation 4] [In formula (1-1), δ _D(S1) represents the dispersion term of the Hansen solubility parameter of solvent 1 contained in agent A, c _S1 represents the volume fraction of solvent 1 contained in agent A, δ _D(S2) represents the dispersion term of the Hansen solubility parameter of solvent 2 contained in agent A, and c _S2 represents the volume fraction of solvent 2 contained in agent A]

Similarly, the polar term and hydrogen bond term of the Hansen solubility parameter of the entire solvent based on the weighted average of the solvent can be calculated according to the following equations (1-2) and (1-3). [Equation 5] [In formula (1-2), δ _P(S1) represents the polar term of the Hansen solubility parameter of solvent 1 contained in agent A, c _S1 represents the volume fraction of solvent 1 contained in agent A, δ _P(S2) represents the polar term of the Hansen solubility parameter of solvent 2 contained in agent A, and c _S2 represents the volume fraction of solvent 2 contained in agent A] [Equation 6] [In formula (1-3), δ _H(S1) represents the hydrogen bonding term of the Hansen solubility parameter of solvent 1 contained in agent A, c _S1 represents the volume fraction of solvent 1 contained in agent A, δ _H(S2) represents the hydrogen bonding term of the Hansen solubility parameter of solvent 2 contained in agent A, and c _S2 represents the volume fraction of solvent 2 contained in agent A.] δ _D , δ _P , and δ _H of each solvent can be calculated using, for example, the book "Hansen Solubility Parameters: A user's handbook, Second Edition", Hansen, Charles (2007) or the software: HSPiP.

When the Ra of the solvent contained in the A agent expressed by the above formula (1) does not satisfy Ra>37.0, it is difficult to obtain a liquid crystal cured film with excellent alignment after long-term storage. The Ra of the solvent contained in the A agent expressed by the above formula (1) is preferably 37.3 or more, more preferably 37.5 or more, further preferably 38.0 or more, further preferably 39.0 or more. When the Ra of the solvent contained in the A agent expressed by the above formula (1) satisfies the above values, a liquid crystal cured film with excellent alignment can be easily obtained after long-term storage. In addition, the adhesion and appearance of the liquid crystal cured film after long-term storage also become good. The Ra of the solvent contained in the A agent expressed by the above formula (1) is usually 45.0 or less.

Specific examples of the solvent contained in agent A include: alcohol solvents such as methanol, ethanol, butanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl solvent, butyl solvent, propylene glycol monomethyl ether, cyclohexanol, and phenol; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, and methyl isobutyl ketone; non-chlorinated solvents such as pentane, hexane, and heptane; Aliphatic hydrocarbon solvents; alicyclic hydrocarbon solvents such as cyclohexane; non-chlorinated aromatic hydrocarbon solvents such as toluene, anisole, trimethylbenzene, and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran, dioxane, and dimethoxyethane; chlorinated solvents such as dichloromethane, dichloroethane, chlorotoluene, chloroform, chlorobenzene, and dichlorobenzene; sulfoxide solvents such as dimethylsulfoxide; amide solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone; heterocyclic solvents such as pyridine, etc. Among the above, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, methyl isobutyl ketone, pentane, hexane, heptane, cyclohexane, toluene, anisole, trimethylbenzene, xylene, dichloroethane, chlorotoluene, chloroform, chlorobenzene, dichlorobenzene and pyridine are particularly preferred.

Solvents may be used singly or in combination. Combining two or more solvents does not preclude the inclusion of solvents with an Ra ≤ 37.0, as long as the overall Ra of the solvents satisfies Ra > 37.0 as described above. However, it is preferred that the Ra of each solvent in Agent A satisfies Ra > 37.0.

The content of the solvent in Agent A is preferably 50% by mass or more, more preferably 55% by mass or more, further preferably 60% by mass or more, and preferably 99% by mass or less, more preferably 98% by mass or less, and further preferably 97% by mass or less, relative to the total mass of the components contained in Agent A. When the content of the solvent in Agent A is above the lower limit and below the upper limit, relatively high-viscosity solid components such as reactive additives can be easily dissolved uniformly, enabling formation of a uniform coating film in the following method for producing a liquid crystal cured film, thereby easily obtaining a liquid crystal cured film with a good appearance.

Agent A can be prepared by mixing the reactive additives, the solvent, and optionally the following optional ingredients. The mixing method, temperature, and time are not particularly limited and can be appropriately selected based on the types and amounts of the ingredients in Agent A.

The viscosity of Agent A (at 25°C) is preferably 0.1-15 mPa·s, more preferably 0.1-10 mPa·s. If the viscosity of Agent A is within this range, it will be easy to handle and subsequently mix with Agent B.

As described above, the two-component polymerizable liquid crystal composition of the present invention separately comprises the aforementioned reactive additives blended into Agent A and the following polymerizable liquid crystal compounds blended into Agent B. Therefore, Agent A substantially contains no polymerizable liquid crystal compounds. "Substantially containing no polymerizable liquid crystal compounds" means that the content of the polymerizable liquid crystal compounds in Agent A is preferably less than 0.5 parts by mass, more preferably less than 0.1 parts by mass, and even more preferably less than 0.05 parts by mass, per 100 parts by mass of the reactive additives. Preferably, the content of the polymerizable liquid crystal compounds in Agent A is 0 parts by mass.

<Agent B> [Polymerizable Liquid Crystal Compound] Agent B of the two-component polymerizable liquid crystal composition of the present invention comprises a polymerizable liquid crystal compound. A polymerizable liquid crystal compound is a compound having a polymerizable group and exhibiting a liquid crystal state. For example, such a polymerizable liquid crystal compound can be used in the field of phase difference films. The polymerizable group refers to a group that participates in the polymerization reaction of the polymerizable liquid crystal compound, preferably a photopolymerizable group. Here, the photopolymerizable group refers to a group that can participate in the polymerization reaction via an active free radical or acid generated by the photopolymerization initiator described below. Examples of the polymerizable group include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloyloxy, oxirane, and cyclobutylene. Among them, preferred are acryloxy, methacryloxy, vinyloxy, ethyleneoxy, and cyclobutyloxy, with acryloxy being more preferred. The liquid crystal properties may be thermotropic or hydrotropic.

In the present invention, the liquid crystal properties exhibited by the polymerizable liquid crystal compound can be either thermotropic or hydrotropic. Thermotropic liquid crystals are preferred because they allow for control of the thickness of dense films. Furthermore, the phase order structure of the thermotropic liquid crystal can be either nematic or smectic. The polymerizable liquid crystal compound can be used singly or in combination.

Regarding this polymerizable liquid crystal compound, its homopolymer may exhibit positive wavelength dispersion or negative wavelength dispersion. As compounds exhibiting positive wavelength dispersion, for example, compounds described in Japanese Patent Publication No. 2010-31223, Japanese Patent Publication No. 2010-270108, Japanese Patent Publication No. 2011-6360, and Japanese Patent Publication No. 2011-207765 can be used.

In the case where the polymerizable liquid crystal compound is a compound exhibiting reverse dispersion, from the viewpoint of exhibiting reverse wavelength dispersion, a liquid crystal having a T-type or H-type mesogen structure is preferred. From the viewpoint of obtaining stronger dispersion, a T-type liquid crystal is more preferred. As the structure of the T-type liquid crystal, a compound having the following characteristics (1) to (4) is preferred. (1) A compound capable of forming a nematic phase; (2) Having π electrons in the long axis direction (a) of the polymerizable liquid crystal compound; (3) Having π electrons in a direction intersecting the long axis direction (a) [cross direction (b)]. (4) Let the total number of π electrons existing in the long axis direction (a) be N(πa), let the total number of molecular weights existing in the long axis direction be N(Aa), and the π electron density in the long axis direction (a) of the polymerizable liquid crystal compound be defined by the following formula (i): D(πa)＝N(πa)/N(Aa) (i) and let the total number of π electrons existing in the cross direction (b) be N(πb), let the total number of molecular weights existing in the cross direction (b) be N(Ab), and the π electron density in the cross direction (b) of the polymerizable liquid crystal compound be defined by the following formula (ii): D(πb)＝N(πb)/N(Ab) (ii) be in the relationship of 0≦[D(πa)/D(πb)]≦1 [that is, the π electron density in the cross direction (b) is greater than the π electron density in the long axis direction (a)]. Furthermore, a polymerizable liquid crystal compound that satisfies all of the characteristics of (1) to (4) above can be coated on an alignment film and heated to a temperature above the phase transition temperature to form a nematic phase. The nematic phase formed by the alignment of the polymerizable liquid crystal compound is usually aligned in such a way that the long axis directions of the polymerizable liquid crystal compound are parallel to each other, and the long axis direction becomes the alignment direction of the nematic phase. As such a compound, specifically, for example, a compound represented by the following formula (A1) can be cited. [Chemical 1]

In formula (A1), Ar represents a divalent group having an aromatic group which may have a substituent. The aromatic group herein may, for example, have two or more Ar groups as exemplified in (Ar-1) to (Ar-23) below. Preferably, the aromatic group contains at least one of a nitrogen atom, an oxygen atom, and a sulfur atom. The number of aromatic groups contained in the divalent group Ar may be one or more. When the number of aromatic groups contained in the divalent group Ar is two or more, the two or more aromatic groups may be bonded to each other using a single bond, -CO-O-, -O- or other divalent bonding groups. ^G1 and ^G2 each independently represent a divalent aromatic group or a divalent alicyclic alkyl group. Here, a hydrogen atom contained in the divalent aromatic group or divalent alicyclic alkyl group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. The carbon atoms constituting the divalent aromatic group or divalent alicyclic alkyl group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom. ^L1 and ^L2 , ^B1 and ^B2 each independently represent a single bond or a divalent linking group. k and l each independently represent an integer from 0 to 3, and satisfy the relationship 1 ≤ k + l. Here, when 2 ≤ k + l, ^B1 and ^B2 , ^G1 and G2 ^each may be the same or different. ^E1 and ^E2 each independently represent an alkanediyl group having 1 to 17 carbon atoms, preferably an alkanediyl group having 4 to 12 carbon atoms. Furthermore, a hydrogen atom contained in an alkanediyl group may be substituted with a halogen atom, _{and -CH2-} contained in the alkanediyl group may be substituted with -O-, -S-, or -COO-. In the case of multiple -O-, -S-, or -COO- groups, they are not adjacent to each other. ^P1 and ^P2 each independently represent a polymerizing group or a hydrogen atom, and at least one of ^P1 and ^P2 is a polymerizing group.

^G1 and ^G2 are each independently preferably a 1,4-phenylene group which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, or a 1,4-cyclohexanediyl group which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms. 1,4-phenylene group substituted with a methyl group is more preferred, unsubstituted 1,4-phenylene group or unsubstituted 1,4-trans-cyclohexanediyl group is more preferred, and unsubstituted 1,4-phenylene group or unsubstituted 1,4-trans-cyclohexanediyl group is particularly preferred. Furthermore, it is preferred that at least one of the multiple G ¹ and G ² groups is a divalent alicyclic alkyl group, and it is even more preferred that at least one of the G ¹ and G ² groups bonded to L ¹ or L ² is a divalent alicyclic alkyl group.

^L1 and ^L2 are each preferably independently a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -Ra1COORa2-, -Ra3COORa4-, ^{-Ra5OCORa6- ,} Ra7OC=OORa8- ^{, -N} =N-, ^-CRc = ^{CRd- ,} or -C≡C- ^. Here, ^{Ra1 - Ra8} are each independently a single bond or an alkylene group having 1 to 4 carbon atoms, and ^Rc and ^Rd are each a C1-4 alkyl group or a hydrogen _atom . ^L1 and ^L2 are each more preferably independently a single bond, ^-ORa2-1- _{, -CH2-} , ^-CH2CH2- , ^-COORa4-1- , or ^OCORa6-1- . Here, ^Ra2-1 , ^Ra4-1 , and ^Ra6-1 each independently represent a single bond, _-CH2- , _{or -CH2CH2-} . ^L1 and ^L2 each independently represent preferably a single bond, -O-, _{-CH2CH2- ,} -COO- _{, -COOCH2CH2-} , or -OCO-.

^B1 and ^B2 are each preferably independently a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a9 OR ^a10 -, -R ^a11 COOR ^a12 -, -R ^a13 OCOR ^a14 -, or R ^a15 OC=OOR ^a16 -. Here, R ^a9 to R ^a16 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms. ^B1 and ^B2 are each more preferably independently a single bond, -OR ^a10-1 -, -CH ₂ -, -CH ₂ CH ₂ -, -COOR ^a12-1 -, or -OCOR ^a14-1 -. Here, R ^a10-1 , R ^a12-1 , and R ^a14-1 each independently represent a single bond, -CH ₂ -, or -CH ₂ CH ₂ -. ^B1 and ^B2 are each independently and preferably a single bond, -O- _{, -CH2CH2-} , _-COO- , _-COOCH2CH2- , _-OCO- or _-OCOCH2CH2- .

From the perspective of reverse wavelength dispersion, k and l are preferably within the range of 2 ≤ k + l ≤ 6, with k + l = 4 being more preferred, and k = 2 and l = 2 being more preferred. k = 2 and l = 2 are preferred, as they result in a symmetrical structure. ^E1 and ^E2 are each preferably an alkanediyl group having 1 to 17 carbon atoms, more preferably an alkanediyl group having 4 to 12 carbon atoms.

Examples of the polymerizable group represented by ^P1 or ^P2 include epoxy, vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryl, methacryl, oxirane, and cyclobutyl. Preferably, at least one of ^P1 or ^P2 is acryl or methacryl, more preferably, both ^P1 and ^P2 are acryl or methacryl, and even more preferably, acryl.

Ar preferably has at least one member selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocyclic ring which may have a substituent, and an electron-withdrawing group. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring; preferably, a benzene ring or a naphthalene ring. Examples of the aromatic heterocyclic ring include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrrolidine ring, a pyrimidine ring, a triazole ring, a trilium ring, a pyrroline ring, an imidazole ring, a pyrazole ring, a thiazole ring, a benzothiazole ring, a thienothiazole ring, a thiazole ring, a benzothiazole ring, and a phenanthroline ring. Among these, a thiazole ring, a benzothiazole ring, or a benzofuran ring is preferred, and a benzothiazolyl group is further preferred. Furthermore, when Ar contains a nitrogen atom, the nitrogen atom preferably has π electrons.

In formula (A1), the total number _Nπ of π electrons contained in Ar is preferably 8 or more, more preferably 10 or more, further preferably 14 or more, and particularly preferably 16 or more. It is preferably 32 or less, more preferably 30 or less, further preferably 26 or less, and particularly preferably 24 or less.

Examples of the aromatic group represented by Ar include the following groups.

[Chemistry 2]

In formulas (Ar-1) to (Ar-23), the symbol * represents a linking moiety, and Z ⁰ , Z ¹ , and Z ² each independently represent a hydrogen atom, a halogen atom, a C 1-12 alkyl group, a cyano group, a nitro group, a C 1-12 alkylsulfinyl group, a C 1-12 alkylsulfonyl group, a C 1-12 fluoroalkyl group, a C 1-12 alkoxy group, a C 1-12 alkylthio group, a C 1-12 N-alkylamino group, a C 2-12 N,N-dialkylamino group, a C 1-12 N-alkylaminesulfonyl group, or a C 2-12 N,N-dialkylaminesulfonyl group. Furthermore, Z ⁰ , Z ¹ , and Z ² may also include a polymerizable group.

Q ¹ and Q ² each independently represent -CR ^1' R ^2' -, -S-, -NH-, -NR ^1' -, -CO-, or -O-, and R ^1' and R ^2' each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

J ¹ and J ² each independently represent a carbon atom or a nitrogen atom.

Y ¹ , Y ² and Y ³ each independently represent an aromatic alkyl group or an aromatic heterocyclic group which may be substituted.

^W1 and ^W2 each independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer from 0 to 6.

Examples of aromatic alkyl groups in Y ¹ , Y ² , and Y ³ include aromatic alkyl groups having 6 to 20 carbon atoms, such as phenyl, naphthyl, anthracenyl, phenanthrenyl, and biphenyl. Phenyl and naphthyl are preferred, and phenyl is even more preferred. Examples of aromatic heterocyclic groups include aromatic heterocyclic groups having 4 to 20 carbon atoms, such as furyl, pyrrolyl, thienyl, pyridyl, thiazolyl, and benzothiazolyl, which contain at least one heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom. Furyl, thienyl, pyridyl, thiazolyl, and benzothiazolyl are preferred.

Y ¹ , Y ² , and Y ³ may each independently represent an optionally substituted polycyclic aromatic alkyl group or a polycyclic aromatic heterocyclic group. A polycyclic aromatic alkyl group refers to a condensed polycyclic aromatic alkyl group or a group derived from an aggregate of aromatic rings. A polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from an aggregate of aromatic rings.

^Z₀ , ^Z₁ , and ^Z₂ are preferably each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, or an alkoxy group having 1 to 12 carbon atoms. ^Z₀ is further preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cyano group. ^Z₁ and ^Z₂ are further preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a cyano group. Furthermore, ^Z₀ , ^Z₁ , and ^Z₂ may also contain a polymerizable group.

Q ¹ and Q ² are preferably -NH-, -S-, -NR ^1'- , or -O-, and R ^1' is preferably a hydrogen atom. Among them, -S-, -O-, and -NH- are particularly preferred.

Among formulae (Ar-1) to (Ar-23), formulae (Ar-6) and (Ar-7) are preferred from the viewpoint of molecular stability.

In formulas (Ar-16) to (Ar-23), ^Y1 may form an aromatic heterocyclic group together with the nitrogen atom to which it is bonded and ^Z0 . Examples of the aromatic heterocyclic group include those described above as aromatic heterocyclic rings that Ar may have, such as a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, a pyrrolidine ring, a pyrimidine ring, an indole ring, a quinoline ring, an isoquinoline ring, a purine ring, and a pyrrolidinyl ring. The aromatic heterocyclic group may also have a substituent. Furthermore, ^Y1 may form a polycyclic aromatic alkyl group or a polycyclic aromatic heterocyclic group that may be substituted as described above together with the nitrogen atom to which it is bonded and ^Z0 . For example, a benzofuran ring, a benzothiazole ring, a benzoxazole ring and the like can be exemplified.

The amount of the polymerizable liquid crystal compound contained in the two-component polymerizable liquid crystal composition of the present invention is preferably 70 parts by mass or more, preferably 80 parts by mass or more, more preferably 85 parts by mass or more, and further preferably 90 parts by mass or more, for example, 99.5 parts by mass or less, preferably 99 parts by mass or less, more preferably 98 parts by mass or less, and further preferably 95 parts by mass or less, relative to 100 parts by mass of the solid content in Agent B. If the content of the polymerizable liquid crystal compound is above the lower limit and below the upper limit, it is advantageous from the perspective of the alignment properties of the resulting liquid crystal cured film. Here, the so-called solid content refers to the total amount of the components remaining after removing the solvent from the components in Agent B.

[Solvent] The solvent contained in the B agent preferably has a Ra value expressed by the above formula (1) that satisfies Ra ≤ 37.0. When the Ra value of the solvent contained in the B agent expressed by the above formula (1) satisfies Ra ≤ 37.0, the polymerizable liquid crystal compound is easily dissolved. The lower limit of the Ra value of the solvent contained in the B agent expressed by the above formula (1) is usually 20.0. There is no particular limitation on the solvent, but it is preferably a solvent that is inert to the polymerizable liquid crystal compound and can completely dissolve the compound. The solvent contained in the B agent may be used alone or in combination of two or more. When two or more solvents are used in combination, the same solvent as that used in the A agent may also be included.

The content of the solvent in Agent B is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 88% by mass or less, relative to the total mass of the components contained in Agent B. When the content of the solvent in Agent B is above the lower limit and below the upper limit, the polymerizable liquid crystal compound is easily dissolved uniformly, enabling formation of a uniform coating film in the following method for producing a liquid crystal cured film, thereby easily obtaining a liquid crystal cured film with a good appearance.

Specific examples of such solvents include: alcohol solvents such as methanol, ethanol, butanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl solvent, butyl solvent, propylene glycol monomethyl ether, cyclohexanol, and phenol; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, and methyl isobutyl ketone; Non-chlorinated aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; alicyclic hydrocarbon solvents such as cyclohexane; non-chlorinated aromatic hydrocarbon solvents such as toluene, anisole, trimethylbenzene, and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran, dioxane, and dimethoxyethane; chlorinated solvents such as dichloromethane, dichloroethane, chlorotoluene, chloroform, chlorobenzene, and dichlorobenzene; sulfoxide solvents such as dimethylsulfoxide; amide solvents such as dimethylformamide and dimethylacetamide; heterocyclic solvents such as pyridine, etc. These organic solvents may be used alone or in combination.

As described above, the two-component polymerizable liquid crystal composition of the present invention separately comprises the reactive additives described above in Agent A and the polymerizable liquid crystal compound described above in Agent B. Therefore, Agent B contains substantially no reactive additives. The phrase "substantially no reactive additives" means that the content of the reactive additives in Agent B is preferably less than 0.5 parts by mass, more preferably less than 0.1 parts by mass, and even more preferably less than 0.05 parts by mass, per 100 parts by mass of the polymerizable liquid crystal compound. Preferably, the content of the reactive additives in Agent B is 0 parts by mass.

Agent B can be prepared by mixing the polymerizable liquid crystal compound, the solvent, and, if appropriate, any of the following components. The mixing method, temperature, and time are not particularly limited and can be appropriately selected based on the types and amounts of the components contained in Agent B.

The viscosity of Agent B (at 25°C) is preferably 0.1-15 mPa·s, more preferably 0.1-10 mPa·s. If the viscosity of Agent B is within this range, it will be easy to handle and subsequently mix with Agent A.

The two-component polymerizable liquid crystal composition of the present invention may contain, in addition to the above-mentioned components, any components such as a polymerization initiator, a sensitizer, a polymerization inhibitor, and a leveler.

[Polymerization Initiator] The two-component polymerizable liquid crystal composition of the present invention may contain a polymerization initiator. A polymerization initiator is a compound that can initiate the polymerization reaction of a polymerizable liquid crystal compound. Preferred polymerization initiators are photopolymerization initiators that generate reactive free radicals under the action of light. A polymerization initiator may be contained in either Agent A or Agent B, or both, of the two-component polymerizable liquid crystal composition of the present invention.

From the perspective of being independent of the phase state of the thermotropic liquid crystal, photopolymerization initiators that generate reactive free radicals upon exposure to light are preferred. Known photopolymerization initiators can be used as long as they are compounds capable of initiating the polymerization reaction of the polymerizable liquid crystal compound. Specifically, examples include those that generate reactive free radicals or acids upon exposure to light. Of these, those that generate free radicals upon exposure to light are preferred. Photopolymerization initiators may be used alone or in combination of two or more. Photopolymerization initiators can fully utilize the energy emitted by the light source and have excellent productivity. Therefore, the maximum absorption wavelength is preferably 300 nm to 400 nm, more preferably 300 nm to 380 nm. Among them, α-acetophenone-based polymerization initiators and oxime-based photopolymerization initiators are preferred. As the photopolymerization initiator, a known photopolymerization initiator can be used. For example, as a photopolymerization initiator that generates active free radicals, self-cleavable benzoin compounds, acetophenone compounds, hydroxyacetophenone compounds, α-aminoacetophenone compounds, oxime ester compounds, acylphosphine oxide compounds, azo compounds, etc. can be used. Dehydrogenated benzophenone compounds, alkylphenone compounds, benzoin ether compounds, benzoyl ketone compounds, dibenzocycloheptanone compounds, anthraquinone compounds, thiophenone compounds, 9-oxosulfuronium compounds can be used. Examples of suitable photopolymerization initiators include halogenated acetophenone compounds, dialkoxyacetophenone compounds, halogenated bisimidazole compounds, halogenated triphosphonium compounds, and triphosphonium compounds. Acid-generating photopolymerization initiators include iodonium salts and coronium salts. From the perspective of excellent reaction efficiency at low temperatures, self-cleavable photopolymerization initiators are preferred, with acetophenone compounds, hydroxyacetophenone compounds, α-aminoacetophenone compounds, and oxime ester compounds being particularly preferred.

Examples of the benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the acetophenone-based compounds include dialkoxyacetophenone-based compounds such as diethoxyacetophenone; hydroxyacetophenone-based compounds such as 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1-one; and α-aminoacetophenone-based compounds such as 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one and 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butane-1-one.

Examples of oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyl oxime)], ethyl ketone, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime) compounds.

Examples of the acylphosphine oxide-based compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzyl)phenylphosphine oxide.

Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone.

Examples of the alkylphenone-based compound include diethoxyacetophenone, 2-methyl-2-oxolinyl-1-(4-methylthiophenyl)propane-1-one, 2-benzyl-2-dimethylamino-1-(4-oxolinylphenyl)butane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1-one.

Examples of the trioxane compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-trioxane, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-trioxane, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-trioxane, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-trioxane, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)- )vinyl]-1,3,5-trisinol, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-trisinol, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-trisinol and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-trisinol, etc.

Commercially available polymerization initiators can be used. Examples include Irgacure (registered trademark) 907, 184, 651, 819, 250, and 369 (manufactured by Ciba Specialty Chemicals Co., Ltd.); Seikuol (registered trademark) BZ, Z, and BEE (manufactured by Seiko Chemicals Co., Ltd.); Kayacure (registered trademark) BP100 and UVI-6992 (manufactured by The Dow Chemical Company); Adeka Optomer SP-152 and SP-170 (manufactured by Adeka Co., Ltd.); TAZ-A and TAZ-PP (manufactured by Nihon Siber Hegner Co., Ltd.); and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.). The polymerization initiator may be a single type or a mixture of two or more types, depending on the light source.

The content of the polymerization initiator can be appropriately adjusted according to the type and amount of the polymerizable liquid crystal compound. It is typically 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 15 parts by mass, per 100 parts by mass of the polymerizable liquid crystal compound. If the polymerization initiator content is within this range, the reaction of the polymerizable groups proceeds sufficiently and the alignment of the polymerizable liquid crystal compound is less likely to be disrupted.

[Sensitizer] The two-component polymerizable liquid crystal composition of the present invention may also contain a sensitizer. A sensitizer may be contained in either Agent A or Agent B, or both of the two-component polymerizable liquid crystal composition of the present invention. A photosensitizer is preferably a photosensitizer. Examples of such sensitizers include thiophene and 9-oxothiophene. Ketone compounds such as 2,4-diethyl 9-oxothiophene , 2-isopropyl 9-oxosulfonium anthracene and anthracene containing alkoxy groups (such as dibutoxyanthracene, etc.); anthracene compounds such as phenanthrene and rubrene, etc.

The sensitizer content is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. When the sensitizer content is within this range, the polymerization reaction of the polymerizable liquid crystal compound is readily promoted.

[Polymerization Inhibitor] To ensure stable polymerization, the two-component polymerizable liquid crystal composition of the present invention may contain a polymerization inhibitor. The polymerization inhibitor may be contained in either Agent A or Agent B, or both, of the two-component polymerizable liquid crystal composition of the present invention. The polymerization inhibitor can be used to control the progress of the polymerization reaction.

Examples of the polymerization inhibitor include free radical scavengers such as hydroquinone, alkoxy-containing hydroquinone, alkoxy-containing o-catechol (e.g., butyl o-catechol), o-catechol, and 2,2,6,6-tetramethyl-1-piperidinyloxy free radical; thiophenols; β-naphthylamines; and β-naphthols.

When the two-component polymerizable liquid crystal composition contains a polymerization inhibitor, the amount of the polymerization inhibitor is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 0.5 to 8 parts by mass, per 100 parts by mass of the polymerizable liquid crystal compound. When the polymerization inhibitor content is within this range, polymerization is facilitated without disrupting the alignment of the polymerizable liquid crystal.

[Leveling Agent] The two-component polymerizable liquid crystal composition of the present invention may also contain a leveling agent. A leveling agent, for example, adjusts the fluidity of the composition, thereby making the resulting film smoother. A leveling agent may be included in either Agent A or Agent B of the two-component polymerizable liquid crystal composition of the present invention, or in both.

Examples of leveling agents include organically modified silicone oil-based, polyacrylate-based, and perfluoroalkyl-based leveling agents. Specifically, the following can be cited: DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all manufactured by Toray Dow Corning Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all manufactured by Momentive Performance Materials Co., Ltd. Fluorinert (registered trademark) FC-72, Fluorinert FC-40, Fluorinert FC-43, Fluorinert FC-3283 (all manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) R-08, Megafac R-30, Megafac R-90, Megafac F-410, Megafac F-411, Megafac F-443, Megafac F-445, Megafac F-470, Megafac F-477, Megafac F-479, Megafac F-482, Megafac F-483 (all manufactured by DIC Co., Ltd.), Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-105, KH-40, SA-100 (all manufactured by AGC Seimi Chemical Co., Ltd.), E1830 and E5844 (manufactured by Daikin Fine Chemicals Laboratories Co., Ltd.), BM-1000, BM-1100, BYK-352, BYK-353, and BYK-361N (all manufactured by BM Chemie Co., Ltd.). Among these, polyacrylate-based leveling agents and perfluoroalkyl-based leveling agents are preferred.

When the two-component polymerizable liquid crystal composition of the present invention contains a leveling agent, the amount is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. Leveling agent content within this range is preferred because it facilitates horizontal alignment of the polymerizable liquid crystals and tends to produce a smoother cured liquid crystal film. Furthermore, two or more leveling agents may be included.

<Storage Method> When storing the two-component polymerizable liquid crystal composition of the present invention, Agent A and Agent B are stored separately. Separate storage may include, for example, storing Agent A and Agent B in two separate containers, or storing Agent A and Agent B in a single container with a partition between them to prevent mixing during storage. In the present invention, storing Agent A and Agent B in two separate containers is preferred.

Examples of containers for storing Agent A include plastic containers, metal containers, and glass containers, with plastic containers or metal containers being preferred. Plastic containers or metal containers are preferred because they are less likely to cause side reactions with reactive additives in Agent A. Examples of materials for plastic containers include, but are not limited to, polypropylene, polyethylene, norolefin polymers, polystyrene, polyamide, poly(4-methylpentene-1), acrylic resins, polyvinyl alcohol, acrylonitrile-butadiene-styrene copolymers, polymethacrylates, polyacrylates, cellulose esters, polycarbonates, polyethylene terephthalate, polysulfones, polyethersulfones, polyetherketones, polyethylene naphthalate, polyphenylene sulfide, polyphenylene ether, cyclic polyolefins such as cyclic olefin polymers or cyclic olefin copolymers, polyolefins such as amorphous polyarylates, polyesters, and Teflon. Examples of materials for metal containers include, but are not limited to, steel such as SUS, tinplate, and aluminum. When the container for Agent A is a plastic container, a light-shielding plastic container (e.g., a brown plastic container) is preferred to protect it from ultraviolet rays, which may degrade the composition. Alternatively, the exterior of the container may be coated.

The container for storing agent B is not particularly limited, and examples of the material of the container include plastic, metal, glass, etc. As described above, the container for storing agent B is preferably a light-shielding container.

The shape of the container for storing Agent A and Agent B is not particularly limited. Examples include hexahedral shapes such as cans and polyethylene cans, and cylindrical shapes such as steel cans and paint brush barrels. Furthermore, the capacity of Agent A and Agent B is not particularly limited; the required amount can be stored in the container.

When storing Agent A, it is preferably stored under a dry, inert gas atmosphere. In this specification, dry gas generally refers to a gas with a dew point below -50°C. Inert gases include, for example, low-reactivity gases such as nitrogen, argon, and helium. Examples of storage under a dry, inert gas atmosphere include: sealing the storage container after filling the gas phase with dry, inert gas; or storing the storage container itself in a space filled with dry, inert gas. By storing the composition in a dry, inert atmosphere, side reactions between moisture and the active hydrogen groups in the reactive additive in Agent A can be avoided. This improves the adhesion of the liquid crystal cured film obtained from the two-component polymerizable liquid crystal composition of the present invention and enhances the optical properties after long-term storage.

The environment in which Agent B is stored is not particularly limited, but it is preferably stored in a dry inert gas atmosphere.

The amount of Agent A and Agent B to be filled relative to the storage container capacity is not particularly limited. However, the amount of Agent A and Agent B to be filled is generally 30% or more of the storage container capacity, preferably 50% or more. From the perspective of ease of operation during mixing, it is generally 90% or less.

There is no particular limit to the storage temperature of Agent A and Agent B. If the temperature is too high, the polymerization reaction of the polymerizable liquid crystal compound may begin. If the temperature is too low, the solid components in Agent A and Agent B may precipitate. Therefore, the storage temperature is generally 0-50°C, preferably 10-40°C, and more preferably 15-35°C.

If Agent A and Agent B are stored for approximately three to six months after mixing, it can sometimes be difficult to produce a liquid crystal cured film with good optical properties. The two-component polymerizable liquid crystal composition of the present invention can produce a liquid crystal cured film with good optical properties even after long-term storage, which is advantageous in this regard. There is no specific storage period for Agent A and Agent B, but it is generally within three years.

The two-component polymerizable liquid crystal composition of the present invention, by storing the reactive additive and the polymerizable liquid crystal compound separately as described above, can produce a liquid crystal cured film with excellent optical properties even after long-term storage. Research conducted by the inventors of this invention has revealed that in a two-component polymerizable liquid crystal composition, when the solvent included in the reactive additive satisfies Ra > 37.0, molecular alignment disturbances of the polymerizable liquid crystal compound, which can deteriorate the optical properties of the liquid crystal cured film after long-term storage, are less likely to occur. This results in a liquid crystal cured film with excellent optical properties, as well as superior adhesion and appearance.

<Method for Producing a Polymerizable Liquid Crystal Composition> In the present invention, a polymerizable liquid crystal composition can be obtained by mixing Agent A and Agent B, which constitute a two-part polymerizable liquid crystal composition. In this specification, the term "two-part polymerizable liquid crystal composition" refers to a composition in which Agent A and Agent B, which constitute the two-part polymerizable liquid crystal composition, are stored separately. The composition in which Agent A and Agent B are mixed is referred to as the "polymerizable liquid crystal composition."

The timing for mixing Agent A and Agent B of the two-component polymerizable liquid crystal composition of the present invention is not limited, as long as the reactive additive in Agent A and the water in the solvent that may be included in Agent B do not react. The timing can be appropriately determined according to the type and amount of the reactive additive and the solvent in Agent B, the mixing conditions, and the environment.

The method for mixing Agent A and Agent B is not particularly limited, and a known mixing method may be used. For example, a method of mixing using a mixing device with a stirring blade, such as a planetary mixer or a concoction agitator, or a static mixing method, such as a static mixer, may be used.

The ambient temperature during mixing of Agent A and Agent B is not particularly limited, but is preferably 0-50°C, more preferably 15-40°C, and even more preferably 20-35°C. The relative humidity (RH) is also not particularly limited, but is preferably 30-60% RH, more preferably 40-55% RH. Mixing is typically carried out under normal pressure (atmospheric pressure).

The mixing time is not particularly limited and can be adjusted appropriately based on the types and amounts of the components in the two-component polymerizable liquid crystal composition. The mixing time is typically 0.5 to 12 hours, preferably 0.5 to 6 hours.

<Method for Producing a Liquid Crystal Cured Film> The method for producing a liquid crystal cured film of the present invention comprises: forming an alignment film on a substrate; mixing Agent A and Agent B, which constitute the two-component polymerizable liquid crystal composition of the present invention, to obtain a polymerizable liquid crystal composition; coating the mixed polymerizable liquid crystal composition on the alignment film to obtain a coating film; and curing the coating film.

[Substrate] Substrates used to form liquid crystal cured films include glass and plastic substrates. Plastic substrates are preferred over glass substrates due to their roll-to-roll processing and high productivity. Examples of plastics that constitute plastic substrates include polyolefins such as polyethylene, polypropylene, and norethene polymers; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate; polyacrylate; cellulose esters such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; polyphenylene sulfide and polyphenylene ether.

Examples of commercially available cellulose ester substrates include Fujitac Film (manufactured by Fujifilm Co., Ltd.), KC8UX2M, KC8UY, and KC4UY (all manufactured by Konica Minolta Opto Co., Ltd.), etc.

Examples of commercially available cyclic olefin resins include "Topas" (registered trademark) (manufactured by Ticona Corporation (wholly owned subsidiary)), "ARTON" (registered trademark) (manufactured by JSR Corporation), "ZEONOR" (registered trademark), "ZEONEX" (registered trademark) (all manufactured by ZEON Corporation of Japan), and "APEL" (registered trademark) (manufactured by Mitsui Chemicals, Inc.). These cyclic olefin resins can be formed into films to form substrates using known methods such as solvent casting and melt extrusion. Commercially available cyclic olefin resin substrates can also be used. Examples of commercially available cyclic olefin resin substrates include: "S-SINA" (registered trademark), "SCA40" (registered trademark) (all manufactured by Sekisui Chemical Co., Ltd.), "ZEONOR FILM" (registered trademark) (manufactured by Optronics Co., Ltd.), and "ARTON Film" (registered trademark) (manufactured by JSR Co., Ltd.).

The thickness of the substrate is preferably thinner to ensure practical handling. However, if it is too thin, the strength will decrease and the workability will deteriorate. The thickness of the substrate is generally 5-300 μm, preferably 20-200 μm.

[Alignment Film] In the present invention, the alignment film is a film composed of a polymer compound that has the ability to regulate the alignment of polymerizable liquid crystal compounds in a desired direction.

The alignment film facilitates the liquid crystal alignment of the polymerizable liquid crystal compound. The states of liquid crystal alignment, such as horizontal alignment, vertical alignment, mixed alignment, and tilted alignment, vary according to the properties of the alignment film and the polymerizable liquid crystal compound, and their combination can be selected arbitrarily. For example, if the alignment film is a material that exhibits horizontal alignment as an alignment regulating force, the polymerizable liquid crystal compound can form a horizontal alignment or a mixed alignment. If it is a material that exhibits vertical alignment, the polymerizable liquid crystal compound can form a vertical alignment or a tilted alignment. Expressions such as horizontal and vertical indicate the direction of the long axis of the aligned polymerizable liquid crystal when the plane of the liquid crystal curing film is used as a reference. The so-called horizontal alignment is an alignment in which the long axis of the aligned polymerizable liquid crystal is in a direction parallel to the plane of the liquid crystal curing film. The term "parallel" here means an angle of 0°±20° relative to the plane of the liquid crystal curing film. Vertical alignment means the long axis of the polymerized liquid crystal is aligned perpendicular to the plane of the liquid crystal curing film. Vertical here means 90°±20° relative to the plane of the liquid crystal curing film.

Regarding alignment control, when the alignment film is made of an aligning polymer, it can be adjusted arbitrarily by adjusting the surface conditions or rubbing conditions. When it is made of a photoaligning polymer, it can be adjusted arbitrarily by adjusting polarized light irradiation conditions, etc. Furthermore, liquid crystal alignment can be controlled by selecting physical properties such as surface tension and liquid crystallinity of the polymerizable liquid crystal compound.

The alignment film is preferably insoluble in the solvent used to form the liquid crystal cured film on the alignment film and has sufficient heat resistance for solvent removal and heat treatment for liquid crystal alignment. Examples of alignment films include those made of aligning polymers, photoalignment films, groove alignment films, and stretch films extending along the alignment direction. Photoalignment films are preferred.

The thickness of the alignment film is generally in the range of 10 to 10,000 nm, preferably in the range of 10 to 1,000 nm, and more preferably in the range of 50 to 300 nm.

Examples of aligning polymers include polyamides or gelatins containing amide bonds within their molecules, polyimides containing imide bonds within their molecules and their hydrolyzates, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylates. Among these, polyvinyl alcohol is preferred. These aligning polymers may be used alone or in combination of two or more.

An alignment film composed of an alignment polymer is typically obtained by applying a composition obtained by dissolving the alignment polymer in a solvent (hereinafter referred to as the "alignment polymer composition") to a substrate and removing the solvent; or by applying the alignment polymer composition to a substrate, removing the solvent, and rubbing the substrate (rubbing method).

Examples of the solvent include water; alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl solvent, butyl solvent, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorine-substituted hydrocarbon solvents such as chloroform and chlorobenzene, and the like. These solvents may be used alone or in combination of two or more.

The concentration of the alignment polymer in the alignment polymer composition may be within a range where the alignment polymer can be completely dissolved in the solvent, and is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, based on the solid content of the solution.

As the alignment polymer composition, a commercially available alignment film material may be used directly. Examples of commercially available alignment film materials include Sunever (registered trademark) (manufactured by Nissan Chemical Industries, Ltd.) and Optomer (registered trademark) (manufactured by JSR Corporation).

Examples of methods for applying the alignment polymer composition to a substrate include known methods such as rotary coating, extrusion coating, gravure coating, die-nozzle coating, rod coating, and applicator coating, as well as printing methods such as flexographic coating. When the alignment film of the present invention is produced by a roll-to-roll continuous production process, the coating method typically employs a printing method such as gravure coating, die-nozzle coating, or flexographic coating.

The solvent contained in the alignment polymer composition is removed to form a dry coating of the alignment polymer. Examples of solvent removal methods include natural drying, ventilation drying, heat drying, and reduced pressure drying.

As a rubbing method, there can be exemplified a method in which an alignment polymer film formed on the surface of a substrate by coating an alignment polymer composition on the substrate and annealing the coating is brought into contact with a rotating rubbing roller wound with a rubbing cloth.

The photo-alignment film usually contains polymers and oligomers or monomers having photoreactive groups. In the case of continuously forming polymerizable liquid crystals, from the perspective of solvent resistance, etc., a polymer with a molecular weight of 5000 or more is preferred. From the perspective of affinity, when the polymerizable liquid crystal is a (meth)acrylic group, an acrylic polymer is preferred. The photo-alignment film is obtained by applying a composition comprising a polymer, oligomer or monomer having a photoreactive group and a solvent (hereinafter also referred to as a "photo-alignment film forming composition") to a substrate, drying and removing the solvent, and then irradiating with polarized light (preferably polarized UV). The photo-alignment film can arbitrarily control the direction of the alignment regulating force by selecting the polarization direction of the irradiated polarized light, which is more preferable in this respect.

Photoreactive groups are groups that induce liquid crystal alignment upon exposure to light. Specifically, they induce photoreactions such as molecular alignment induction, isomerization, dimerization, photocrosslinking, or photodecomposition, which are the origins of liquid crystal alignment. Among these photoreactive groups, those that induce dimerization or photocrosslinking are preferred for superior alignment properties. The photoreactive group capable of producing the above reaction preferably has an unsaturated bond, especially a double bond, and more preferably has at least one group selected from the group consisting of a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), a nitrogen-nitrogen double bond (N=N bond), and a carbon-oxygen double bond (C=O bond).

Examples of photoreactive groups having a C=C bond include vinyl, polyenyl, stilbene, styrylpyridine, styrylpyridinium, chalcone, and cinnamyl groups. Examples of photoreactive groups having a C=N bond include aromatic Schiff base groups and groups having aromatic hydrazone structures. Examples of photoreactive groups having an N=N bond include azophenyl, azonaphthyl, aromatic heterocyclic azo groups, bisazo groups, and formyl groups having oxyazobenzene as a basic structure. Examples of photoreactive groups having a C=O bond include benzophenone, coumarin, anthraquinone, and cis-butylenediimide groups. These groups may have substituents such as alkyl groups, alkoxy groups, aryl groups, allyloxy groups, cyano groups, alkoxycarbonyl groups, hydroxyl groups, sulfonic acid groups, and halogenated alkyl groups.

The solvent of the photo-alignment film-forming composition is preferably one that dissolves polymers and monomers having photoreactive groups. Examples of such solvents include those listed above as the solvent for the alignment polymer composition.

The content of the polymer or monomer having a photoreactive group relative to the photo-alignment film-forming composition can be appropriately adjusted based on the type of polymer or monomer having a photoreactive group and the thickness of the desired photo-alignment film. It is preferably set to 0.2% by mass or greater, and more preferably within the range of 0.3% to 10% by mass. Alternatively, a polymer material such as polyvinyl alcohol or polyimide, or a photosensitizer, may be included within a range that does not significantly degrade the properties of the photo-alignment film.

The method for applying the photo-alignment film-forming composition to the anti-diffusion layer can be the same as the method for applying the aligning polymer composition to the anti-diffusion layer. The method for removing the solvent from the applied photo-alignment film-forming composition can be the same as the method for removing the solvent from the aligning polymer composition.

Polarized light irradiation can be performed directly from the photo-alignment film-forming composition coated on the substrate after removing the solvent, or by irradiating the substrate with polarized light and allowing the polarized light to pass through. The polarized light is preferably substantially parallel. The wavelength of the polarized light is preferably within the wavelength range where the photoreactive groups of the polymer or monomer containing the photoreactive groups can absorb light energy. Specifically, ultraviolet light (UV) with a wavelength of 250 to 400 nm is particularly preferred. Examples of light sources used for polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and ultraviolet lasers such as KrF and ArF. High-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are particularly preferred. These lamps are particularly preferred due to their high intensity of ultraviolet light at a wavelength of 313 nm. Polarized light can be irradiated by passing light from these light sources through an appropriate polarizing element. Examples of polarizing elements include polarizing filters, polarizing prisms such as Glenn-Thompson and Glenn-Taylor, or wire-grid polarizing elements.

Furthermore, if masking is performed during rubbing or polarized light irradiation, multiple regions (patterns) with different liquid crystal alignment directions can also be formed.

Groove alignment films have a concave-convex pattern or multiple grooves on their surface. When liquid crystal molecules are placed on a film with multiple linear grooves arranged at equal intervals, the liquid crystal molecules align along the grooves.

Examples of methods for obtaining a groove alignment film include: exposing a photosensitive polyimide film surface through an exposure mask with narrow slits in the pattern shape, followed by development and rinsing to form a relief pattern; forming a layer of uncured UV-curable resin on a plate-shaped disc having grooves on its surface, transferring the resin layer to a substrate, and then curing it; and pressing a roller-shaped disc having multiple grooves against a film of uncured UV-curable resin formed on a substrate to form relief patterns, followed by curing. Specifically, examples include the methods described in Japanese Patent Application Publication Nos. 6-34976 and 2011-242743.

In order to obtain an alignment with less misalignment, the width of the convex portion of the trench alignment film is preferably 0.05-5 μm, the width of the concave portion is preferably 0.1-5 μm, and the step depth of the concave-convex is preferably less than 2 μm, and more preferably less than 0.01-1 μm.

[Liquid Crystal Cured Film] <Deposition of the Polymerizable Liquid Crystal Composition> The mixed polymerizable liquid crystal composition is applied to the substrate or alignment film to form a liquid crystal cured film. Examples of methods for applying the polymerizable liquid crystal composition to the substrate include extrusion coating, direct gravure coating, reverse gravure coating, CAP coating, slit coating, micro-gravure coating, die-die coating, and inkjet coating. Alternatively, coating may be performed using a coating machine such as a dip coater, rod coater, or rotary coater. When applying the coating continuously in a roll-to-roll manner, coating methods based on microgravure, inkjet, slit coating, or die-die coating are preferred. When applying the coating to a single substrate such as glass, rotary coating is preferred due to its high uniformity. In roll-to-roll coating, it is also possible to coat the substrate with a photo-alignment film-forming composition to form an alignment film, and then continuously apply the polymerizable liquid crystal composition onto the resulting alignment film.

<Drying of the Polymerizable Liquid Crystal Composition> Examples of drying methods for removing the solvent contained in the polymerizable liquid crystal composition include natural drying, ventilation drying, heat drying, reduced pressure drying, and combinations thereof. Natural drying or heat drying are preferred. The drying temperature is preferably in the range of 0-200°C, more preferably 20-150°C, and even more preferably 50-130°C. The drying time is preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes. The photo-alignment film-forming composition and the aligning polymer composition can also be dried in the same manner.

<Polymerization of Polymerizable Liquid Crystal Compounds> Photopolymerization is preferred as a method for polymerizing polymerizable liquid crystal compounds. Photopolymerization is performed by irradiating a layer of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound coated on a substrate or an alignment film with active energy rays. The active energy rays irradiated are appropriately selected based on the type of polymerizable liquid crystal compound contained in the dried film (particularly the type of photopolymerizable functional groups possessed by the polymerizable liquid crystal compound), the type of photopolymerization initiator if one is present, and the amount thereof. Specifically, one or more light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays can be used. Among these, ultraviolet light is preferred because it allows for easy control of the polymerization reaction and can be used as a photopolymerization device by a wide range of users in this field. It is also preferred to select the type of polymerizable liquid crystal compound so that it can be photopolymerized by ultraviolet light.

Examples of light sources for the active energy rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten lamps, gallium lamps, excimer lasers, LED (light-emitting diode) light sources emitting light in the wavelength range of 380 to 440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, and metal halide lamps.

The UV irradiation intensity is typically 10 to 3,000 mW/cm ² . The UV irradiation intensity is preferably within the wavelength range effective for activating the photopolymerization initiator. The irradiation time is typically 0.1 second to 10 minutes, preferably 0.1 second to 5 minutes, more preferably 0.1 second to 3 minutes, and even more preferably 0.1 second to 1 minute. If irradiation is performed once or multiple times at this UV irradiation intensity, the cumulative amount of light is 10 to 3,000 mJ/cm ² , preferably 50 to 2,000 mJ/cm ² , and more preferably 100 to 1,000 mJ/cm ² . If the cumulative amount of light is below this range, the curing of the polymerizable liquid crystal compound becomes insufficient, and good transferability may not be achieved. On the contrary, when the accumulated light intensity is above this range, the optical film including the optically anisotropic layer may be colored. [Example]

The present invention is further described below using examples. Unless otherwise specified, "%" and "parts" in the examples refer to mass % and mass parts, respectively. Furthermore, the δ _{D (W)} of water is 15.5, the δ _{P (W)} is 16.0, and the δ _{H (W)} is 42.3.

<Example 1> [Preparation of a composition for forming a photo-alignment film] The following components described in Japanese Patent Application Laid-Open No. 2013-033249 were mixed, and the resulting mixture was stirred at 80° C. for 1 hour to obtain a composition for forming a photo-alignment film.

[Preparation of Agent A] The following ingredients were mixed and stirred at 25°C for 1 hour to obtain Agent A (1). The δ _D(S) of cyclopentanone was 17.9, δ _P(S) was 11.9, and δ _H(S) was 5.2. The prepared A agent (1) was placed in a SUS can, and the gas phase was replaced with dry nitrogen and then sealed.

[Preparation of Agent B] The following ingredients were mixed and stirred at 80°C for 1 hour to obtain Agent B (1). The δ _D(S) of N-methylpyrrolidone (NMP) was 18.0, δ _P(S) was 12.3, and δ _H(S) was 7.2. The prepared B agent (1) was placed in a SUS can, and the gas phase was replaced with dry nitrogen and then sealed.

<Method for producing a liquid crystal cured film> (1) Formation of a photo-aligned film A cycloolefin polymer (COP) film (Zeonor Film (registered trademark) "ZF-14" manufactured by ZEON Co., Ltd., Japan, with a film thickness of 23 μm) is used as a substrate. After applying a corona treatment to the film surface, the above-mentioned photo-aligned film forming composition is applied and dried at 80°C to obtain a dry coating. Polarized UV is irradiated on the dry coating to form a photo-aligned film, thereby obtaining a film with a photo-aligned film. The polarized UV treatment is performed using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Electric Co., Ltd.) under the condition of an intensity of 100 mJ/ ^cm2 measured at a wavelength of 365 nm. In this way, a film with a photo-aligned film is obtained.

(2) Formation of liquid crystal cured film: After preparing agent A (1) and agent B (1), they are stored at 25°C for 3 months or 6 months, and then agent A (1) and agent B (1) are mixed and stirred at 25°C for 1 hour to obtain a polymerizable liquid crystal composition (1). Immediately after obtaining the polymerizable liquid crystal composition (1), the polymerizable liquid crystal composition (1) is applied to the obtained photo-alignment film by a rod coating method, and then heated and dried in a drying oven at 120°C for 1 minute to fully remove the solvent. Then, a high-pressure mercury lamp (Unicure VB-15201BY-A; manufactured by Nishiwei Electric Co., Ltd.) was used to irradiate the layer formed by the polymerizable liquid crystal composition (1) with ultraviolet rays at an exposure dose of 1000 mJ/ ^cm2 (365 nm reference), thereby forming a liquid crystal cured film (1).

<Evaluation of Alignment> The obtained liquid crystal cured films were observed at 400x magnification using a polarizing microscope (BX51, manufactured by Olympus Corporation). Good alignment was evaluated as ○, slight misalignment was evaluated as △, and insufficient alignment, such as surface misalignment, was evaluated as ×.

<Evaluation of Adhesion> 25 mm wide Sellotape (manufactured by Nichiban) was attached to the front and back of the obtained liquid crystal cured film (1), and a 90° peeling test was performed on the front and back. The evaluation was 0 if no peeling occurred, △ if only part of the test area peeled off, and × if the entire test area peeled off.

<Appearance Evaluation> The obtained liquid crystal cured film (1) was visually inspected for the presence of foreign matter. A film with no foreign matter observed was evaluated as 0, a film with slightly observed foreign matter was evaluated as △, and a film with a large amount of foreign matter was evaluated as ×.

<Examples 2 and 3> Except that the storage container for Agent A was set as shown in the table, polymerizable liquid crystal compositions (2) and (3) and liquid crystal cured films (2) and (3) were obtained in the same manner as in Example 1. The alignment, adhesion, and appearance of the obtained liquid crystal cured films were evaluated in the same manner as in Example 1.

<Example 4> Except that the gas phase of the container storing Agent A was set to air, a polymerizable liquid crystal composition (4) and a liquid crystal cured film (4) were obtained in the same manner as in Example 1. The orientation, adhesion, and appearance of the obtained liquid crystal cured film were evaluated in the same manner as in Example 1.

<Example 5> A polymerizable liquid crystal composition (5) and a liquid crystal cured film (5) were obtained in the same manner as in Example 1 except that the following compound was used as a reactive additive. The orientation, adhesion, and appearance of the obtained liquid crystal cured film (5) were evaluated in the same manner as in Example 1. Reactive additive: Karenz AOI (manufactured by Showa Denko Co., Ltd.) 5.0 parts

<Example 6> A polymerizable liquid crystal composition (6) and a liquid crystal cured film (6) were obtained in the same manner as in Example 1 except that the following compound was used as a reactive additive. The orientation, adhesion, and appearance of the obtained liquid crystal cured film were evaluated in the same manner as in Example 1. Reactive additive: KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) 2.0 parts

<Example 7> A polymerizable liquid crystal composition (7) and a liquid crystal cured film (7) were obtained in the same manner as in Example 1, except that the solvent of agent A was set to 70 parts by mass of chloroform and the solvent of agent (B) was set to 644 parts by mass of NMP. Furthermore, the chloroform δ _D(S) was 17.8, δ _P(S) was 3.1, δ _H(S) was 5.7, and Ra was 39.1. The alignment, adhesion, and appearance of the obtained liquid crystal cured film were evaluated in the same manner as in Example 1.

<Example 8> A polymerizable liquid crystal composition (8) and a liquid crystal cured film (8) were obtained in the same manner as in Example 1, except that the solvent of agent A was set to 70 parts by mass of anisole and the solvent of agent (B) was set to 644 parts by mass of NMP. Furthermore, the δ _D(S) of anisole was 17.8, the δ _P(S) was 4.4, the δ _H(S) was 6.9, and the Ra was 37.5. The alignment, adhesion, and appearance of the obtained liquid crystal cured film were evaluated in the same manner as in Example 1.

<Example 9> A polymerizable liquid crystal composition (9) and a liquid crystal cured film (9) were obtained in the same manner as in Example 1, except that the polymerizable liquid crystal compound was LC242 (manufactured by BASF Japan Co., Ltd.) and the solvent of Agent B was 644 parts by mass of NMP. The alignment, adhesion, and appearance of the obtained liquid crystal cured film were evaluated in the same manner as in Example 1.

<Example 10> A polymerizable liquid crystal composition (10) and a liquid crystal cured film (10) were obtained in the same manner as in Example 1, except that the polymerizable liquid crystal compound was set to LC242 (manufactured by BASF JAPAN Co., Ltd.) and the solvent of agent B was set to a mixed solvent of 370 parts by mass of cyclopentanone and 274 parts by mass of propylene glycol monomethyl ether acetate (PGMEA). Furthermore, the δ _D(S) of PGMEA was 15.6, the δ _P(S) was 5.6, and the δ _H(S) was 9.8, and the Ra of the solvent in agent B as a whole was 35.9. The orientation, adhesion, and appearance of the obtained liquid crystal cured film were evaluated in the same manner as in Example 1.

Comparative Example 1 Agent (A) and agent (B) were prepared in the same manner as in Example 1. The two liquids were stirred in a SUS container at 25°C for one hour to mix. After mixing, the container was sealed under dry nitrogen and stored at 25°C for three or six months before coating. The resulting liquid crystal cured films were evaluated for alignment, adhesion, and appearance in the same manner as in Example 1.

Comparative Example 2 Agent (B) was prepared in the same manner as in Comparative Example 1, except that no reactive additive was used. The mixture was sealed under dry nitrogen and stored at 25°C for 3 or 6 months before coating. The resulting liquid crystal cured films were evaluated for alignment, adhesion, and appearance in the same manner as in Example 1.

Comparative Examples 3 and 4 Agent (A) and Agent (B) were prepared in the same manner as in Comparative Example 1, except that the reactive additives were changed to those described in the table. The two liquids were then stirred and mixed in a SUS container at 25°C for one hour. After mixing, the container was sealed under dry nitrogen and stored at 25°C for three or six months before coating. The resulting liquid crystal cured films were evaluated for alignment, adhesion, and appearance in the same manner as in Example 1.

Comparative Example 5 Agent (A) and Agent (B) were prepared in the same manner as in Example 10. The two liquids were stirred in a SUS container at 25°C for one hour to mix. After mixing, the container was sealed under dry nitrogen and stored at 25°C for three or six months before coating. The resulting liquid crystal cured films were evaluated for alignment, adhesion, and appearance in the same manner as in Example 1.

[Table 1] Agent A Agent B Storage method Result of coating after 3 months of storage Result of coating after 6 months of storage Reactive additives solvent Ra polymerizable liquid crystals solvent Ra Mixing sequence of two liquids Storage container A-agent gas phase part Orientation Tightness Appearance Orientation Tightness Appearance Example 1 PR9000 5 mass parts Cyclopentanone 37.6 (C-1) 75 parts by mass (C-2) 25 parts by mass Cyclopentanone/NMP 36.8 Store separately and mix before use SUS tank dry nitrogen ○ ○ ○ ○ ○ ○ Example 2 PR9000 5 mass parts Cyclopentanone 37.6 (C-1) 75 parts by mass (C-2) 25 parts by mass Cyclopentanone/NMP 36.8 Store separately and mix before use Brown plastic bottle dry nitrogen ○ ○ ○ ○ ○ ○ Example 3 PR9000 5 mass parts Cyclopentanone 37.6 (C-1) 75 parts by mass (C-2) 25 parts by mass Cyclopentanone/NMP 36.8 Store separately and mix before use Brown glass bottle dry nitrogen ○ △ ○ ○ × ○ Example 4 PR9000 5 mass parts Cyclopentanone 37.6 (C-1) 75 parts by mass (C-2) 25 parts by mass Cyclopentanone/NMP 36.8 Store separately and mix before use SUS tank air ○ ○ ○ △ △ △ Example 5 Karenz AOI 5 quality parts Cyclopentanone 37.6 (C-1) 75 parts by mass (C-2) 25 parts by mass Cyclopentanone/NMP 36.8 Store separately and mix before use SUS tank dry nitrogen ○ ○ ○ ○ ○ ○ Example 6 KBM-5103 2 mass parts Cyclopentanone 37.6 (C-1) 75 parts by mass (C-2) 25 parts by mass Cyclopentanone/NMP 36.8 Store separately and mix before use SUS tank dry nitrogen ○ ○ ○ ○ ○ ○ Example 7 PR9000 5 mass parts Chloroform 39.1 (C-1) 75 parts by mass (C-2) 25 parts by mass NMP 35.7 Store separately and mix before use SUS tank dry nitrogen ○ ○ ○ ○ ○ ○ Example 8 PR9000 5 mass parts Anisole 37.5 (C-1) 75 parts by mass (C-2) 25 parts by mass NMP 35.7 Store separately and mix before use SUS tank dry nitrogen ○ △ ○ ○ × ○ Example 9 PR9000 5 mass parts Cyclopentanone 37.6 LC242 100 mass parts NMP 35.7 Store separately and mix before use SUS tank dry nitrogen ○ ○ ○ ○ ○ ○ Example 10 PR9000 5 mass parts Cyclopentanone 37.6 LC242 100 mass parts Cyclopentanone/PGMEA 35.9 Store separately and mix before use SUS tank dry nitrogen ○ ○ ○ ○ ○ ○ Comparative example 1 PR9000 5 mass parts Cyclopentanone 37.6 (C-1) 75 parts by mass (C-2) 25 parts by mass Cyclopentanone/NMP 36.8 Storage after mixing SUS tank dry nitrogen × × × × × × Comparative example 2 without - - (C-1) 75 parts by mass (C-2) 25 parts by mass Cyclopentanone/NMP 36.8 - SUS tank dry nitrogen ○ ×× ○ ○ ×× ○ Comparative example 3 Karenz AOI 5 quality parts Cyclopentanone 37.6 (C-1) 75 parts by mass (C-2) 25 parts by mass Cyclopentanone/NMP 36.8 Storage after mixing SUS tank dry nitrogen × × × × × × Comparative example 4 KBM-5103 2 mass parts Cyclopentanone 37.6 (C-1) 75 parts by mass (C-2) 25 parts by mass Cyclopentanone/NMP 36.8 Storage after mixing SUS tank dry nitrogen × × × × × × Comparative example 5 PR9000 5 mass parts Cyclopentanone 37.6 LC242 100 mass parts Cyclopentanone/PGMEA 35.9 Storage after mixing SUS tank dry nitrogen △ × △ △ × △

It was found that the compositions of Examples 1-10, even when mixed and then coated after three or six months of storage, produced cured liquid crystal films with excellent optical properties, high adhesion, and an outstanding appearance. On the other hand, Comparative Examples 1 and 3-5, which mixed and stored two liquids, produced cured liquid crystal films with poor alignment and appearance. Comparative Example 2, which did not include a reactive additive, produced a cured liquid crystal film with poor adhesion.

Claims (5)

A method for storing a two-component polymerizable liquid crystal composition comprising an agent A and an agent B, wherein the agent A and the agent B are stored separately at a storage temperature of 0 to 50° C., and the agent A is stored in a plastic container or a metal container under a dry inert gas atmosphere. The agent A comprises a reactive additive having a polymerizable group and an active hydrogen-reactive group in the molecule and a solvent, and the agent B comprises a polymerizable liquid crystal compound and a solvent, wherein the solvent in the agent A has an Ra value expressed by the following formula (1) that satisfies Ra>37.0. [Figure 1] [Wherein, δ _D(W) represents the dispersion term of the Hansen solubility parameter of water, δ _D(S) represents the dispersion term of the Hansen solubility parameter of the entire solvent based on the weighted average of the solvents, δ _P(W) represents the polar term of the Hansen solubility parameter of water, δ _P(S) represents the polar term of the Hansen solubility parameter of the entire solvent based on the weighted average of the solvents, δ _H(W) represents the hydrogen bond term of the Hansen solubility parameter of water, and δ _H(S) represents the hydrogen bond term of the Hansen solubility parameter of the entire solvent based on the weighted average of the solvents]. The method for storing a two-component polymerizable liquid crystal composition according to claim 1, wherein the value of Ra of the solvent in the above-mentioned agent B expressed by the above-mentioned formula (1) satisfies Ra≦37.0. The storage method of a two-component polymerizable liquid crystal composition according to claim 1 or 2, wherein the amount of the reactive additive contained in the agent A is 0.5 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the polymerizable liquid crystal compound. A method for producing a polymerizable liquid crystal composition comprises mixing the agent A and the agent B stored by the method for storing a two-component polymerizable liquid crystal composition according to any one of claims 1 to 3. A method for producing a liquid crystal cured film comprises: forming an alignment film on a substrate; mixing agent A and agent B stored using the method for storing a two-component polymerizable liquid crystal composition according to any one of claims 1 to 3 to obtain a polymerizable liquid crystal composition; coating the mixed polymerizable liquid crystal composition on the alignment film to obtain a coating film; and curing the coating film.