Two-liquid polymerizable liquid crystal composition

Abstract

Provided are a polymerizable liquid crystal composition capable of obtaining a liquid crystal cured film having good optical properties even after long-term storage, a storage method for the composition, a production method for the composition, and a production method for a liquid crystal cured film. A two-liquid type polymerizable liquid crystal composition composed of an A agent containing a reactive additive having a polymerizable group and an active hydrogen reactive group in a molecule and a solvent, and a B agent containing a polymerizable liquid crystal compound and a solvent.

Description

TECHNICAL FIELD

[0001] The present application relates to a two-liquid type polymerizable liquid crystal composition, a storage method thereof, a production method of the polymerizable liquid crystal composition, and a production method of a liquid crystal cured film. BACKGROUND

[0002] In recent years, along with the thinning of image display devices, optical films such as a polarizing plate and a phase difference plate using a polarizing film having a liquid crystal cured layer obtained by applying a polymerizable liquid crystal compound on a substrate or an alignment film and curing it in an aligned state have been developed. In the production of such optical films, from the viewpoints of film formability and handleability, etc., generally, the polymerizable liquid crystal compound is applied on a substrate or an alignment film in the form of a polymerizable liquid crystal composition liquid obtained by dissolving the polymerizable liquid crystal compound in a solvent, etc. It is known that in the case of producing an optical film by applying a composition on a substrate or an alignment film, if the adhesion between the substrate or the alignment film and the resulting optical film is high, peeling during processing, etc. does not occur, and thus a high-quality optical film is easily obtained, and therefore it is preferable, and a composition having a property of being able to provide an optical film having high adhesion has been proposed (Patent Document 1).

[0003] PRIOR ART DOCUMENTS

[0004] PATENT DOCUMENTS

[0005] Patent Document 1: Japanese Patent No. 6019591 SUMMARY

[0006] PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] However, it has been found that there is a problem that if the above composition is formed into a liquid crystal cured film after long-term storage, orientation defects occur, and good orientation properties are not necessarily obtained. Therefore, an object of the present application is to provide a polymerizable liquid crystal composition capable of obtaining a liquid crystal cured film having good optical properties even after long-term storage, a storage method thereof, a production method of the composition, and a production method of a liquid crystal cured film.

[0008] MEANS FOR SOLVING THE PROBLEMS

[0009] The present inventors have repeatedly conducted detailed studies in order to solve the aforementioned problems, and as a result, have achieved the present application. That is, the present application includes the following preferred modes.

[0010] 〔1〕 A two-liquid type polymerizable liquid crystal composition composed of an A agent containing a reactive additive having a polymerizable group and an active hydrogen reactive group in a molecule and a solvent, and a B agent containing a polymerizable liquid crystal compound and a solvent, the value of Ra represented by the following formula (1) of the solvent in the aforementioned A agent satisfies Ra > 37.0.

[0011] [Math. 1]

[0012] Ra = {4 x (δ D(w) - δ D(S) ) 2 + (δ P(W) - δ P(S) ) 2 + (δ H(W) - δ H(S) ) 2} 0.5 …(1)

[0013] [In the formula, δ D(W) represents a dispersion term of the Hansen solubility parameter of water, δ D(S) represents a dispersion term of the Hansen solubility parameter of the whole solvent based on a weighted average of the solvents, δ P(W) represents a polarity term of the Hansen solubility parameter of water, δ P(S) represents a polarity term of the Hansen solubility parameter of the whole solvent based on a weighted average of the solvents, δ H(W) represents a hydrogen bonding term of the Hansen solubility parameter of water, and δ H(S) represents a hydrogen bonding term of the Hansen solubility parameter of the whole solvent based on a weighted average of the solvents]

[0014] [2] The two-liquid type polymerizable liquid crystal composition according to [1], wherein the value of Ra represented by the above formula (1) of the solvent in the above B agent satisfies Ra < 37.0.

[0015] [3] The two-liquid type polymerizable liquid crystal composition according to [1] or [2], wherein the amount of the above reactive additive contained in the above A agent is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the above polymerizable liquid crystal compound.

[0016] [4] A storage method of the two-liquid type polymerizable liquid crystal composition according to any one of [1] to [3], wherein the above A agent and B agent are stored separately.

[0017] [5] The storage method according to [4], wherein the above A agent is stored in a plastic container or a metal container.

[0018] [6] The storage method according to [4] or [5], wherein the above A agent is stored under a dry non-reactive gas atmosphere.

[0019] [7] A method for producing a polymerizable liquid crystal composition, comprising a step of mixing the above A agent and B agent which constitute the two-liquid type polymerizable liquid crystal composition according to any one of [1] to [3].

[0020] [8] A method for producing a liquid crystal cured film, comprising the following steps:

[0021] a step of forming an alignment film on a substrate;

[0022] a step of mixing the aforementioned A agent and B agent which constitute the two-component polymerizable liquid crystal composition described in any one of [1] to [3] to obtain a polymerizable liquid crystal composition;

[0023] a step of applying the aforementioned mixed polymerizable liquid crystal composition on the aforementioned alignment film to obtain a coated film; and

[0024] a step of curing the aforementioned coated film.

[0025] Effects of the Invention

[0026] According to the present application, it is possible to provide a polymerizable liquid crystal composition which can obtain a liquid crystal cured film having good optical properties even after long-term storage, a storage method thereof, a production method of the composition, and a production method of a liquid crystal cured film. Furthermore, the liquid crystal cured film obtained from the polymerizable liquid crystal composition of the present application has high adhesion and excellent appearance. DETAILED DESCRIPTION

[0027] Hereinafter, the embodiments of the present application will be described in detail. Note that the scope of the present application is not limited to the embodiments described hereinafter, and various modifications can be made without departing from the spirit of the present application.

[0028] The two-component polymerizable liquid crystal composition of the present application is composed of an A agent containing a reactive additive having a polymerizable group and an active hydrogen reactive group in a molecule and a solvent, and a B agent containing a polymerizable liquid crystal compound and a solvent, and the value of Ra represented by the following formula (1) of the solvent in the aforementioned A agent satisfies Ra > 37.0.

[0029] [mathematical formula 2]

[0030] Ra = {4 x (δ D(W) - δ D(S) ) 2 + (δ P(W) - δ P(S) ) 2 + (δ H(W) - δ H(S) ) 2} 0.5 … (1)

[0031] [in the formula, δ D(W) represents a dispersion term of the Hansen solubility parameter of water, δ D(S) represents a dispersion term of the Hansen solubility parameter of the solvent as a whole based on the weighted average of the solvents, δ P(W) represents a polarity term of the Hansen solubility parameter of water, and δ P(S)Polar term of Hansen solubility parameter of solvent as a whole based on a weighted average of solvents H(W) Hydrogen bonding term of Hansen solubility parameter of water, δ H(S) Hydrogen bonding term of Hansen solubility parameter of solvent as a whole based on a weighted average of solvents

[0032] The two-liquid type polymerizable liquid crystal composition of the present application is essential to include a reactive additive and a polymerizable liquid crystal compound, and a solvent in which they are dissolved, and each of the above-mentioned reactive additive and polymerizable liquid crystal compound is separately compounded in an A agent and a B agent.

[0033] The A agent

[0034] The reactive additive

[0035] The reactive additive contained in the A agent has a polymerizable group, which means a group participating in polymerization. The polymerizable group can be, for example, a carbon-carbon unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond, and specifically, for example, a vinyl group, a (meth)acrylic acid group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxiranyl group, an oxetanyl group, and the like.

[0036] The reactive additive contained in the A agent has an active hydrogen reactive group, which means a group reactive to a group containing an active hydrogen such as a carboxyl group (-COOH), a hydroxyl group (-OH), an amino group (-NH2), and the like, and an epoxy group, a glycidyl group, an oxazoline group, a carbodiimide group, an aziridine group, an imide group, an isocyanate group, an isothiocyanate group, a maleic anhydride group, an alkoxysilyl group, and the like are representative examples thereof. In the reactive additive, it is preferable that at least two active hydrogen reactive groups be present, and in this case, the plurality of active hydrogen reactive groups can be the same or different.

[0037] The number of the polymerizable group and the active hydrogen reactive group possessed by the reactive additive is usually 1 to 20 each, and preferably 1 to 10 each.

[0038] In one preferable embodiment, the reactive additive preferably contains a vinyl group and / or a (meth)acrylic acid group as the polymerizable group, and preferably contains at least one group selected from the group consisting of an epoxy group, a glycidyl group, an isocyanate group, and an alkoxysilyl group as the active hydrogen reactive group, and more preferably a reactive additive having an acrylic acid group and an isocyanate group or a reactive additive having an acrylic acid group and an alkoxysilyl group.

[0039] As specific examples of the reactive additive, there are, for example, compounds having a (meth)acrylic group and an epoxy group such as methacryloyloxy glycidyl ether, acryloyloxy glycidyl ether, and the like; compounds having a (meth)acrylic group and an oxetanyl group such as oxetanyl acrylate, oxetanyl methacrylate, and the like; compounds having a (meth)acrylic group and a lactone group such as lactone acrylate, lactone methacrylate, and the like; compounds having a vinyl group and an oxazoline group such as vinyl oxazoline, isopropenyl oxazoline, and the like; compounds having a (meth)acrylic group and an isocyanate group such as isocyanatomethyl acrylate, isocyanatomethyl methacrylate, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, and the like; oligomers of compounds having a (meth)acrylic group and an alkoxysilyl group such as 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, and the like. In addition, there are, for example, compounds having a vinyl group, a vinylidene group, and an anhydride such as methacrylic anhydride, acrylic anhydride, maleic anhydride, and vinyl maleic anhydride, and the like. Among these, methacryloyloxy glycidyl ether, acryloyloxy glycidyl ether, isocyanatomethyl acrylate, isocyanatomethyl methacrylate, vinyl oxazoline, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 3-acryloyloxypropyltrimethoxysilane, and the above-mentioned oligomers are preferred, and isocyanatomethyl acrylate, 2-isocyanatoethyl acrylate, 3-acryloyloxypropyltrimethoxysilane, and the above-mentioned oligomers are particularly preferred.

[0040] As the reactive additive, a commercially available product can be used as it is, or a commercially available product can be purified as needed and used.

[0041] As the commercially available product, for example, Laromer (registered trademark) PR9000 (manufactured by BASF Corporation), Karenz AOI (registered trademark) (manufactured by Showa Denko K.K.), KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like can be mentioned.

[0042] Relative to 100 parts by mass of the polymerizable liquid crystal compound described later, the amount of the aforementioned reactive additive contained in Agent A is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 1.5 parts by mass or more, even more preferably 2 parts by mass or more, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, even more preferably 6 parts by mass or less, even more preferably 4 parts by mass or less. If the amount of the aforementioned reactive additive is above or below the aforementioned lower limit and below the aforementioned upper limit, the orientation of the liquid crystal cured film manufactured from the two-component polymerizable liquid crystal composition of the present invention will not be impaired, and the adhesion will be easily improved. The reactive additive can be used alone or in combination of two or more. When two or more reactive additives are used, the amount of the aforementioned reactive additive indicates their total amount.

[0043] [Solvent]

[0044] The value of Ra of the solvent contained in agent A, expressed by the following formula (1), satisfies Ra > 37.0.

[0045] [Mathematical Expression 3]

[0046] Ra={4×(δ D(W) -δ D(S) ) 2 +(δ P(W) -δ P(S) ) 2 +(δ H(W) -δ H(S) ) 2} 0.5 …(1)

[0047] [In the formula, δ D(W) The dispersion term representing the Hansen solubility parameter of water, δ D(S) The dispersion term, δ, represents the overall Hansen solubility parameter of the solvent based on a solvent-weighted average. P(W) The polarity term representing the Hansen solubility parameter of water, δ P(S) The polarity term δ represents the overall Hansen solubility parameter of the solvent, based on a solvent-weighted average. H(W) The hydrogen bonding term, δ, represents the Hansen solubility parameter of water. H(S) [The hydrogen bonding term represents the overall Hansen solubility parameter based on a solvent-weighted average.]

[0048] The dispersion term of the overall Hansen solubility parameter of the solvent based on the weighted average of the solvents can be obtained by the following equation (1-1) based on the dispersion term of the Hansen solubility parameter of each solvent contained in Agent A and the volume fraction of each solvent.

[0049] [Mathematical Expression 4]

[0050] δ D(S) =δD(S1) ×c S1 +δ D(S2) ×c S2 +…(1-1)

[0051] [In formula (1-1), δ D(S1) represents a dispersion term of the Hansen solubility parameter of solvent 1 contained in the A agent, c S1 represents a volume fraction of solvent 1 contained in the A agent, δ D(S2) represents a dispersion term of the Hansen solubility parameter of solvent 2 contained in the A agent, c S2 represents a volume fraction of solvent 2 contained in the A agent]

[0052] Likewise, the polarity term and the hydrogen bond term of the Hansen solubility parameter of the solvent as a whole based on the weighted average of the solvents can be obtained by the following formulae (1-2) and (1-3).

[0053] [mathematical formula 5]

[0054] δ P(S) = δ P(S1) × c S1 + δ P(S2) × c S2 +…(1-2)

[0055] [In formula (1-2), δ P(S1) represents a polarity term of the Hansen solubility parameter of solvent 1 contained in the A agent, c S1 represents a volume fraction of solvent 1 contained in the A agent, δ P(S2) represents a polarity term of the Hansen solubility parameter of solvent 2 contained in the A agent, c S2 represents a volume fraction of solvent 2 contained in the A agent]

[0056] [mathematical formula 6]

[0057] δ H(S) = δ H(S1) × c S1 + δ H(S2) × c S2 +…(1-3)

[0058] [In formula (1-3), δ H(S1) represents a hydrogen bond term of the Hansen solubility parameter of solvent 1 contained in the A agent, c S1 represents a volume fraction of solvent 1 contained in the A agent, δ H(S2) represents a hydrogen bond term of the Hansen solubility parameter of solvent 2 contained in the A agent, c S2 represents a volume fraction of solvent 2 contained in the A agent]

[0059] δ D , δ Pand δ H The Ra of the solvent contained in the A agent represented by the aforementioned formula (1) is preferably 37.3 or greater, more preferably 37.5 or greater, further preferably 38.0 or greater, and further more preferably 39.0 or greater. When the Ra of the solvent contained in the A agent represented by the aforementioned formula (1) satisfies the above values, a liquid crystal cured film excellent in orientation is easily obtained even after long-term storage. In addition, the adhesion and appearance of the liquid crystal cured film are also good even after long-term storage. The Ra of the solvent contained in the A agent represented by the aforementioned formula (1) is usually 45.0 or less.

[0060] The Ra of the solvent contained in the A agent represented by the aforementioned formula (1) is preferably 37.3 or greater, more preferably 37.5 or greater, further preferably 38.0 or greater, and further more preferably 39.0 or greater. When the Ra of the solvent contained in the A agent represented by the aforementioned formula (1) satisfies the above values, a liquid crystal cured film excellent in orientation is easily obtained even after long-term storage. In addition, the adhesion and appearance of the liquid crystal cured film are also good even after long-term storage. The Ra of the solvent contained in the A agent represented by the aforementioned formula (1) is usually 45.0 or less.

[0061] As specific examples of the solvent contained in the A agent, for example, there are mentioned alcoholic solvents such as methanol, ethanol, butanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve, 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-chlorine aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicyclic hydrocarbon solvents such as cyclohexane; non-chlorine aromatic hydrocarbon solvents such as toluene, anisole, mesitylene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran, dioxane and dimethoxyethane; chlorine solvents such as dichloromethane, dichloroethane, chlorotoluene, chloroform, chlorobenzene and dichlorobenzene; sulfoxide solvents such as dimethyl sulfoxide; amide solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone; heterocyclic solvents such as pyridine; and the like. Among the above, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, methyl isobutyl ketone, pentane, hexane, heptane, cyclohexane, toluene, anisole, mesitylene, xylene, dichloroethane, chlorotoluene, chloroform, chlorobenzene, dichlorobenzene and pyridine are particularly preferable.

[0062] The solvent can be used alone or in combination of two or more. In the case of using two or more in combination, it is not denied that a solvent having Ra ≤ 37.0 is contained, and as described above, it is only required that the Ra of the entire solvent satisfies Ra > 37.0. However, it is preferable that each Ra of all the solvents contained in the A agent satisfies Ra > 37.0.

[0063] The content of the solvent in the A agent is preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 60% by mass or more, and is 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 all components contained in the A agent. If the content of the solvent in the A agent is within the above lower limit and the above upper limit, it is easy to uniformly dissolve the solid components such as the reactive additive having a high viscosity, and in the manufacturing method of the liquid crystal cured film described later, a uniform coating film can be formed, and thus a liquid crystal cured film having a good appearance can be easily obtained.

[0064] The A agent can be prepared by mixing the aforementioned reactive additive, the aforementioned solvent, and the optional components described later as occasion demands. The mixing method, temperature, and time, and the like are not particularly limited, and can be appropriately selected depending on the kind and amount of the components contained in the A agent.

[0065] The viscosity (25°C) of the A agent is preferably 0.1 to 15 mPa-s, and more preferably 0.1 to 10 mPa-s. If the viscosity of the A agent is within the aforementioned range, the handling property is excellent, and it is easy to make the subsequent mixing with the B agent easy.

[0066] As described above, in the two-liquid type polymerizable liquid crystal composition of the present application, the aforementioned reactive additive is separately compounded in the A agent, and the polymerizable liquid crystal compound described later is compounded in the B agent. Therefore, the A agent substantially does not contain the polymerizable liquid crystal compound described later. By "substantially does not contain the polymerizable liquid crystal compound", it means that the content of the polymerizable liquid crystal compound in the A agent is preferably less than 0.5 parts by mass, more preferably less than 0.1 parts by mass, and further preferably less than 0.05 parts by mass, relative to 100 parts by mass of the reactive additive. It is preferable that the content of the polymerizable liquid crystal compound in the A agent is 0 parts by mass.

[0067]

[0068] 〔Polymerizable liquid crystal compound〕

[0069] The B agent of the two-liquid type polymerizable liquid crystal composition of the present application contains a polymerizable liquid crystal compound. The polymerizable liquid crystal compound is a compound having a polymerizable group and exhibiting a liquid crystal state, and as the polymerizable liquid crystal compound, for example, a polymerizable liquid crystal compound known in the field of phase difference films in the past can be used. The polymerizable group refers to a group participating in the polymerization reaction of the polymerizable liquid crystal compound, and is preferably a photopolymerizable group. Here, the photopolymerizable group refers to a group capable of participating in the polymerization reaction with active radicals, acids, or the like generated from a light polymerization initiator described later. As the polymerizable group, a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxiranyl group, an oxetanyl group, or the like can be given. Among them, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group, and an oxetanyl group are preferable, and an acryloyloxy group is more preferable. The liquid crystallinity can be thermotropic liquid crystal or lyotropic liquid crystal.

[0070] In the present application, the liquid crystallinity exhibited by the polymerizable liquid crystal compound can be thermotropic liquid crystal or lyotropic liquid crystal, but from the aspect of being able to perform precise film thickness control, thermotropic liquid crystal is preferable. In addition, as the phase order structure in thermotropic liquid crystal, nematic liquid crystal or smectic liquid crystal can be given. As the polymerizable liquid crystal compound, one kind alone can be used, or two or more kinds can be used in combination.

[0071] The polymerizable liquid crystal compound can be a compound whose homopolymer exhibits positive wavelength dispersion, or a compound exhibiting reverse wavelength dispersion. As the compound exhibiting positive wavelength dispersion, for example, a compound described in Japanese Patent Application Publication No. 2010-31223, Japanese Patent Application Publication No. 2010-270108, Japanese Patent Application Publication No. 2011-6360, and Japanese Patent Application Publication No. 2011-207765 can be used.

[0072] 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 mesogenic structure in a T shape or an H shape is preferable, from the viewpoint of being able to obtain stronger dispersion, a T shape liquid crystal is more preferable, and as the structure of the T shape liquid crystal, a compound having the following (1) to (4) is preferable.

[0073] (1) is a compound capable of forming a nematic phase;

[0074] (2) has a π electron in the long axis direction (a) of the polymerizable liquid crystal compound.

[0075] (3) has a π electron in the direction intersecting the long axis direction (a) [intersecting direction (b)].

[0076] (4) the π electron density of the long axis direction (a) of the polymerizable liquid crystal compound is defined by the following formula (i) by setting the total of the π electrons present in the long axis direction (a) as N(πa) and the total of the molecular weights present in the long axis direction as N(Aa):

[0077] D(πa) = N(πa) / N(Aa) (i), and

[0078] the π electron density of the cross direction (b) of the polymerizable liquid crystal compound is defined by the following formula (ii) by setting the total of the π electrons present in the cross direction (b) as N(πb) and the total of the molecular weights present in the cross direction (b) as N(Ab):

[0079] D(πb) = N(πb) / N(Ab) (ii)

[0080] there is a relationship of 0 ≤ [D(πa) / D(πb)] ≤ 1 (i.e., the π electron density of the cross direction (b) is greater than the π electron density of the long axis direction (a)).

[0081] Note that for the polymerizable liquid crystal compound satisfying all of the above (1) to (4), a nematic phase can be formed by coating on an alignment film and heating to above the phase transition temperature. In the nematic phase formed by the alignment of the polymerizable liquid crystal compound, the long axis direction of the polymerizable liquid crystal compound is generally aligned in parallel with each other, and this long axis direction becomes the alignment direction of the nematic phase.

[0082] As such a compound, specifically, for example, a compound represented by the following formula (A1) can be mentioned.

[0083] [Chemical Formula 1]

[0084]

[0085] In formula (A1), Ar represents a divalent group having an aromatic group which can have a substituent. Here, the aromatic group can have, for example, 2 or more Ar groups exemplified as (Ar-1) to (Ar-23) described later. It is preferable that at least 1 or more of a nitrogen atom, an oxygen atom, and a sulfur atom be included in the aromatic group. The aromatic group included in the divalent group Ar can be 1 or 2 or more. In the case where 2 or more aromatic groups are included in the divalent group Ar, the 2 or more aromatic groups can be bonded to each other by a single bond, a divalent bonding group such as -CO-O-, -O-, or the like.

[0086] G 1 and G 2Each independently represents a divalent aromatic group or a divalent alicyclic hydrocarbon group. Here, a hydrogen atom included in the divalent aromatic group or the divalent alicyclic hydrocarbon group can 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, and a carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group can be replaced with an oxygen atom, a sulfur atom, or a nitrogen atom.

[0087] L 1 and L 2 , B 1 and B 2 Each independently is a single bond or a divalent linking group.

[0088] k, l each independently represent an integer of 0 to 3, satisfying a relationship of 1 ≤ k + l. Here, in the case of 2 ≤ k + l, B 1 and B 2 , G 1 and G 2 Each can be the same as or different from each other.

[0089] E 1 and E 2 Each independently represents an alkane diyl group having 1 to 17 carbon atoms, and here, more preferably an alkane diyl group having 4 to 12 carbon atoms. In addition, a hydrogen atom included in the alkane diyl group can be substituted with a halogen atom, and -CH2- included in the alkane diyl group can be replaced with -O-, -S-, -COO-, and in the case of having a plurality of -O-, -S-, -COO-, they are not adjacent to each other.

[0090] P 1 and P 2 Each independently represents a polymerizable group or a hydrogen atom, and at least one of P 1 and P 2 is a polymerizable group.

[0091] G 1 and G 2 Each independently is preferably a 1,4-phenylenediyl group which can 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, a 1,4-cyclohexanediyl group which can 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, more preferably a 1,4-phenylenediyl group substituted with a methyl group, an unsubstituted 1,4-phenylenediyl group, or an unsubstituted 1,4-trans-cyclohexanediyl group, and particularly preferably an unsubstituted 1,4-phenylenediyl group or an unsubstituted 1,4-trans-cyclohexanediyl group.

[0092] In addition, it is preferable that a plurality of G1 at least one of G 2 and G 1 is a divalent alicyclic hydrocarbon group, and further preferably, G 2 bonded to L 1 and G 2 is a divalent alicyclic hydrocarbon group.

[0093] L 1 and L 2 are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R a1 COOR a2 -, -R a3 COOR a4 -, -R a5 OCOR a6 -, R a7 OC=OOR a8 -, -N=N-, -CR c =CR d -, or -C=C-. Here, R a1 to R a8 each independently represent a single bond, or an alkylene group having 1 to 4 carbon atoms, and R c and R d represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. L 1 and L 2 are each independently more preferably a single bond, -OR a2-1 -, -CH2-, -CH2CH2-, -COOR a4-1 -, or OCOR a6-1 -. Here, R a2-1 , R a4-1 , and R a6-1 each independently represent any one of a single bond, -CH2-, and -CH2CH2-. L 1 and L 2 are each independently further preferably a single bond, -O-, -CH2CH2-, -COO-, -COOCH2CH2-, or -OCO-.

[0094] B 1 and B 2 are each independently preferably 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, Ra9 ~R a16 Each independently represents a single bond, or an alkylene group having 1 to 4 carbon atoms.B 1 and B 2 Each independently is more preferably a single bond, -OR a10-1 -, -CH2-, -CH2CH2-, -COOR a12 -1 -, or -OCOR a14-1 -. Here, R a10-1 , R a12-1 , R a14-1 Each independently represents any one of a single bond, -CH2-, -CH2CH2-.B 1 and B 2 Each independently is further preferably a single bond, -O-, -CH2CH2-, -COO-, -COOCH2CH2-, -OCO-, or -OCOCH2CH2-.

[0095] From the viewpoint of exhibiting reverse wavelength dispersion, k and l are preferably in the range of 2 < k + l < 6, preferably k + l = 4, more preferably k = 2 and l = 2. If k = 2 and l = 2, it becomes a symmetric structure, and thus is preferred.

[0096] E 1 and E 2 Each independently is preferably an alkandiyl group having 1 to 17 carbon atoms, more preferably an alkandiyl group having 4 to 12 carbon atoms.

[0097] As the polymerizable group represented by P 1 or P 2 , an epoxy group, a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyl group, a methacryloyl group, an oxiranyl group, and an oxetanyl group, etc. can be given. It is preferred that at least one of P 1 or P 2 be an acryloyl group or a methacryloyl group, more preferably both of P 1 and P 2 be an acryloyl group or a methacryloyl group, further preferably be an acryloyl group.

[0098] Ar preferably has at least one selected from the group consisting of an aromatic hydrocarbon ring which can have a substituent, an aromatic heterocyclic ring which can have a substituent, and an electron-withdrawing group. As the aromatic hydrocarbon ring, for example, a benzene ring, a naphthalene ring, an anthracene ring, and the like can be given, and a benzene ring and a naphthalene ring are preferred. As the aromatic heterocyclic ring, a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a triazine ring, a pyrroline ring, an imidazole ring, a pyrazole ring, a thiazole ring, a benzothiazole ring, a thienothiazole ring, an oxazole ring, a benzoxazole ring, a phenanthroline ring, and the like can be given. Among them, a thiazole ring, a benzothiazole ring, or a benzofuran ring is preferred, and a benzothiazole group is further preferred. In the case where Ar includes a nitrogen atom, the nitrogen atom preferably has a π electron.

[0099] In formula (A1), the total number N of π electrons included in Ar π Preferably, it is 8 or more, more preferably 10 or more, further preferably 14 or more, and particularly preferably 16 or more.

[0100] Further, it is preferably 32 or less, more preferably 30 or less, further preferably 26 or less, and particularly preferably 24 or less.

[0101] As the aromatic group represented by Ar, for example, the following groups can be given.

[0102] [Chemical Formula 2]

[0103]

[0104] In formulae (Ar-1) to (Ar-23), the symbol * represents a bonding site, Z 0 , Z 1 , and Z 2 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 12 carbon atoms, an alkylsulfonyl group having 1 to 12 carbon atoms, a carboxyl group, a fluoroalkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, an N-alkylamino group having 1 to 12 carbon atoms, an N,N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 12 carbon atoms, or an N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms. Further, Z 0 , Z 1 , and Z 2 may include a polymerizable group.

[0105] Q 1 , and Q 2 each independently represents -CR 1’ R 2’ -, -S-, -NH-, -NR 1’-, -CO- or -O-, R 1’ and R 2’ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0106] J 1 and J 2 each independently represents a carbon atom, or a nitrogen atom.

[0107] Y 1 , Y 2 and Y 3 each independently represents an optionally substituted aromatic hydrocarbon group or an aromatic heterocyclic group.

[0108] W 1 and W 2 each independently represents a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0 to 6.

[0109] As the aromatic hydrocarbon group in Y 1 , Y 2 and Y 3 , there can be mentioned a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group and the like aromatic hydrocarbon groups having 6 to 20 carbon atoms, and a phenyl group, a naphthyl group are preferred, and a phenyl group is more preferred. As the aromatic heterocyclic group, there can be mentioned a furyl group, a pyrrolyl group, a thienyl group, a pyridyl group, a thiazolyl group, a benzothiazolyl group and the like aromatic heterocyclic groups having 4 to 20 carbon atoms which contain at least one hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, and a furyl group, a thienyl group, a pyridyl group, a thiazolyl group, a benzothiazolyl group are preferred.

[0110] Y 1 , Y 2 and Y 3 each independently can be an optionally substituted polycyclic ring system aromatic hydrocarbon group or a polycyclic ring system aromatic heterocyclic group. The polycyclic ring system aromatic hydrocarbon group means a fused polycyclic ring system aromatic hydrocarbon group, or a group from a collection of aromatic rings. The polycyclic ring system aromatic heterocyclic group means a fused polycyclic ring system aromatic heterocyclic group, or a group from a collection of aromatic rings.

[0111] Z 0 , Z 1 and Z 2 each independently is preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, an alkoxy group having 1 to 12 carbon atoms, Z 0 is further preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, Z 1 and Z 2 is further preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a cyano group. In addition, Z 0 , Z 1 and Z 2 may contain a polymerizable group.

[0112] Q 1 and Q 2 Preferred types are -NH-, -S-, and -NR. 1’ -、-O-,R 1’ Hydrogen atoms are preferred. Among them, -S-, -O-, and -NH- are particularly preferred.

[0113] Of the formulas (Ar-1) to (Ar-23), formulas (Ar-6) and (Ar-7) are preferred from the viewpoint of molecular stability.

[0114] In equations (Ar-16) to (Ar-23), Y 1 It can bond with the nitrogen atom and Z 0 Together, they form an aromatic heterocyclic group. Examples of aromatic heterocyclic groups include those described above that can be present in Ar, such as pyrrole rings, imidazole rings, pyrrolidine rings, pyrrololine rings, pyridine rings, pyrazine rings, pyrimidine rings, indole rings, quinoline rings, isoquinoline rings, purine rings, and pyrrolidine rings. This aromatic heterocyclic group may have substituents. Additionally, Y... 1 It can bond with the nitrogen atom and Z 0 Together, these are the aforementioned substituted polycyclic aromatic hydrocarbon groups or polycyclic aromatic heterocyclic groups. Examples include benzofuran rings, benzothiazole rings, and benzoxazole rings.

[0115] The amount of the aforementioned polymeric liquid crystal compound contained in the two-component polymeric 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 even more 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 even more preferably 95 parts by mass or less, relative to 100 parts by mass of the solid component in agent B. When the content of the polymeric liquid crystal compound is at or above the aforementioned lower limit or below the aforementioned upper limit, it is advantageous from the viewpoint of the orientation of the resulting liquid crystal cured film. Here, the term "solid component" refers to the total amount of components obtained by removing the solvent from the components in agent B.

[0116] [Solvent]

[0117] The value of Ra represented by the aforementioned formula (1) of the solvent contained in the B agent preferably satisfies Ra≤ 37.0. When the value of Ra represented by the aforementioned formula (1) of the solvent contained in the B agent satisfies Ra≤ 37.0, it is easy to make the dissolution of the polymerizable liquid crystal compound easy. The lower limit value of Ra represented by the aforementioned formula (1) of the solvent contained in the B agent is usually 20.0. Such a solvent is not particularly limited, but it is preferable that the solvent be one that is inactive to the polymerizable liquid crystal compound and can completely dissolve the compound. The solvent contained in the B agent can be used alone or two or more kinds can be used in combination. In the case of using two or more kinds in combination, the same solvent as that used in the A agent can be contained.

[0118] The content of the solvent in the B agent is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, with respect to the total mass of the components contained in the B agent, and is preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 88% by mass or less. If the content of the solvent in the B agent is the above lower limit value or more and the above upper limit value or less, it is easy to uniformly dissolve the aforementioned polymerizable liquid crystal compound, and in the manufacturing method of the liquid crystal cured film described later, a uniform coating film can be formed, so that a liquid crystal cured film with a good appearance is easily obtained.

[0119] As specific examples of such a solvent, for example, there are alcohol-based solvents such as methanol, ethanol, butanol, ethylene glycol, isopropanol, propylene glycol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, cyclohexanol, and phenol; ester-based 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-based solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, and methyl isobutyl ketone; non-chlorine-based aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; alicyclic hydrocarbon solvents such as cyclohexane; non-chlorine-based aromatic hydrocarbon solvents such as toluene, anisole, mesitylene, and xylene; nitrile-based solvents such as acetonitrile; ether-based solvents such as tetrahydrofuran, dioxane, and dimethoxyethane; chlorine-based solvents such as dichloromethane, dichloroethane, chlorotoluene, chloroform, chlorobenzene, and dichlorobenzene; sulfoxide solvents such as dimethyl sulfoxide; amide solvents such as dimethylformamide and dimethylacetamide; heterocyclic solvents such as pyridine; and the like. These organic solvents can be used alone or in combination with a plurality of kinds.

[0120] As described above, in the two-pack type polymerizable liquid crystal composition of the present application, the aforementioned reactive additive is separately compounded in the A agent, and the aforementioned polymerizable liquid crystal compound is compounded in the B agent. Therefore, the B agent substantially does not contain the aforementioned reactive additive. By "substantially does not contain the reactive additive", it means that the content of the reactive additive in the B agent is preferably less than 0.5 parts by mass, more preferably less than 0.1 parts by mass, and further preferably less than 0.05 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. It is preferable that the content of the reactive additive in the B agent is 0 parts by mass.

[0121] The B agent can be prepared by mixing the aforementioned polymerizable liquid crystal compound, the aforementioned solvent, and the aforementioned optional components as the case requires. The mixing method, temperature, and time, and the like are not particularly limited, and can be appropriately selected depending on the kind and amount of the components contained in the B agent.

[0122] The viscosity of the B agent (25°C) is preferably 0.1 to 15 mPa-s, and more preferably 0.1 to 10 mPa-s. If the viscosity of the B agent is within the aforementioned range, the workability is excellent, and it is easy to make the subsequent mixing with the A agent easy.

[0123] The two-pack type polymerizable liquid crystal composition of the present application can contain a polymerization initiator, a sensitizer, a polymerization inhibitor, a leveling agent, and the like as optional components in addition to the aforementioned components.

[0124] 〔Polymerization initiator〕

[0125] The two-pack type polymerizable liquid crystal composition of the present application can contain a polymerization initiator. The polymerization initiator is a compound capable of initiating the polymerization reaction of the polymerizable liquid crystal compound and the like. As the polymerization initiator, a photopolymerization initiator that generates an active radical by the action of light is preferable. One or both of the A agent and the B agent constituting the two-pack type polymerizable liquid crystal composition of the present application can contain a polymerization initiator.

[0126] As the polymerization initiator, from the viewpoint of not depending on the phase state of the thermotropic liquid crystal, a photopolymerization initiator that generates an active radical by the action of light is preferable.

[0127] The photopolymerization initiator is a compound that can initiate the polymerization of the polymerizable liquid crystal compound, and a known photopolymerization initiator can be used. Specifically, a photopolymerization initiator that generates a reactive radical or an acid by the action of light can be mentioned, and a photopolymerization initiator that generates a radical by the action of light is preferred. The photopolymerization initiator can be used alone or in combination with two or more. The photopolymerization initiator can sufficiently utilize the energy emitted from the light source, and is excellent in productivity, and therefore, a photopolymerization initiator having a maximum absorption wavelength of 300 to 400 nm is preferred, and a photopolymerization initiator having a maximum absorption wavelength of 300 to 380 nm is more preferred, and an α-phenylethanone-based photopolymerization initiator, an oxime-based photopolymerization initiator is preferred.

[0128] As the photopolymerization initiator, a known photopolymerization initiator can be used. For example, as a photopolymerization initiator that generates a reactive radical, a self-cleavage type benzoin-based compound, a phenylethanone-based compound, a hydroxyphenylethanone-based compound, an α-aminophenylethanone-based compound, an oxime ester-based compound, an acyloxyphosphine-based compound, an azo-based compound, and the like can be used. As a hydrogen abstraction type photopolymerization initiator, a benzophenone-based compound, an alkylphenone-based compound, a benzoin ether-based compound, a benzil ketals-based compound, a dibenzosuberenone-based compound, an anthraquinone-based compound, a xanthone-based compound, a thioxanthone-based compound, a halogenated phenylethanone-based compound, a dialkoxyphenylethanone-based compound, a halogenated bisimidazole-based compound, a halogenated triazine-based compound, a triazine-based compound, and the like can be used. As a photopolymerization initiator that generates an acid, an iodonium salt, a sulfonium salt, and the like can be used. From the viewpoint of excellent reaction efficiency at low temperature, a self-cleavage type photopolymerization initiator is preferred, and a phenylethanone-based compound, a hydroxyphenylethanone-based compound, an α-aminophenylethanone-based compound, an oxime ester-based compound is particularly preferred.

[0129] As the benzoin-based compound, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like can be mentioned.

[0130] As the phenylethanone-based compound, for example, a dialkoxyphenylethanone-based compound such as diethoxyphenylethanone; a hydroxyphenylethanone-based compound such as an oligomer of 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-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl-1-〔4-(1-methylethenyl)phenyl〕propane-1-one; an α-aminophenylethanone-based compound such as 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butane-1-one; and the like can be mentioned.

[0131] As oxime ester compounds, for example, 1-[4-(phenylsulfanyl)phenyl-1,2-octanedione 2-(O-benzoyloxime)], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime), and the like can be given.

[0132] As acyl phosphine oxide compounds, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and the like can be given.

[0133] As benzophenone compounds, for example, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone, and the like can be given.

[0134] As alkyl phenone compounds, for example, diethoxyphenyl ethanone, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)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-hydroxycyclohexyl phenyl ketone, and an oligomer of 2-hydroxy-2-methyl-1-[4-(1-methylethenyl)phenyl]propane-1-one, and the like can be given.

[0135] As triazine compounds, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, and the like can be given.

[0136] As the polymerization initiator, a commercially available polymerization initiator can be used. As the commercially available polymerization initiator, Irgacure (registered trademark) 907, 184, 651, 819, 250, and 369 (manufactured by Ciba Specialty Chemicals Inc.); SEIKUOL (registered trademark) BZ, Z, and BEE (manufactured by Seiko Chemicals Inc.); kayacure (registered trademark) BP100 and UVI-6992 (manufactured by Dow Chemical Company); ADEKA OPTOMER SP-152 and SP-170 (manufactured by ADEKA Corporation); TAZ-A and TAZ-PP (manufactured by Nihon Siber Hegner K.K.); and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.); and the like can be given. The polymerization initiator can be one kind, or two or more kinds of polymerization initiators can be mixed according to the light source of the light.

[0137] The content of the polymerization initiator can be appropriately adjusted according to the kind of the polymerizable liquid crystalline compound and the amount thereof, and is usually 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the content of the polymerizable liquid crystalline compound. If the content of the polymerization initiator is within the above range, the reaction of the polymerizable group sufficiently proceeds, and the alignment of the polymerizable liquid crystalline compound is not easily disturbed.

[0138] 〔Sensitizer〕

[0139] The two-liquid type polymerizable liquid crystalline composition of the present application can contain a sensitizer. One or both of the A agent or the B agent constituting the two-liquid type polymerizable liquid crystalline composition of the present application can contain a sensitizer.

[0140] As the sensitizer, a photosensitizer is preferred. As the sensitizer, for example, xanthone compounds such as xanthone and thioxanthone (for example, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and the like); anthracene compounds such as anthracene and alkoxy-containing anthracene (for example, dibutoxyanthracene, and the like); and the like can be given.

[0141] The content of the aforementioned sensitizer is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and further preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the content of the polymerizable liquid crystalline compound. If the content of the sensitizer is within the aforementioned range, the polymerization reaction of the polymerizable liquid crystalline compound is easily promoted.

[0142] 〔Polymerization inhibitor〕

[0143] From the viewpoint of stably performing the polymerization reaction of the two-liquid type polymerizable liquid crystal composition of the present application, the aforementioned composition can contain a polymerization inhibitor. One or both of the A agent or the B agent constituting the two-liquid type polymerizable liquid crystal composition of the present application can contain a polymerization inhibitor. The degree of progress of the polymerization reaction can be controlled using a polymerization inhibitor.

[0144] As the aforementioned polymerization inhibitor, for example, p-dihydroxybenzene, p-dihydroxybenzene containing an alkoxy group, catechol containing an alkoxy group (for example, butylcatechol, etc.), pyrogallol, 2,2,6,6-tetramethylpiperidine-1-oxyl radical, and the like radical scavengers; thiophenols; β-naphthylamines and β-naphthols, and the like can be given.

[0145] In the case where the two-liquid type polymerizable liquid crystal composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and further preferably 0.5 to 8 parts by mass, relative to 100 parts by mass of the content of the polymerizable liquid crystal compound. If the content of the polymerization inhibitor is within the aforementioned range, the polymerization is easily performed without disturbing the orientation of the polymerizable liquid crystal.

[0146] 〔Leveling agent〕

[0147] The two-liquid type polymerizable liquid crystal composition of the present application can contain a leveling agent. The leveling agent is a substance having a function of adjusting the flowability of the composition and making the film obtained by coating the composition more flat, and for example, a surfactant can be given. One or both of the A agent or the B agent constituting the two-liquid type polymerizable liquid crystal composition of the present application can contain a leveling agent.

[0148] As the leveling agent, for example, organic-modified silicone oil-based, polyacrylate-based, and perfluoroalkyl-based leveling agents can be mentioned. Specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all of which are manufactured by Dow Corning Toray Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (all of which are manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all of which are manufactured by Mitsubishi Chemical (Japan) Co., Ltd.), fluorinert (registered trademark) FC-72, fluorinert FC-40, fluorinert FC-43, fluorinert FC-3283 (all of which are manufactured by Sumitomo 3M Ltd.), MEGAFACE (registered trademark) R-08, MEGAFACE R-30, MEGAFACE R-90, MEGAFACE F-410, MEGAFACE F-411, MEGAFACE F-443, MEGAFACE F-445, MEGAFACE F-470, MEGAFACE F-477, MEGAFACE F-479, MEGAFACE F-482, MEGAFACE F-483 (all of which are manufactured by DIC Corp.), F-top (trade name) EF301, F-top EF303, F-top EF351, F-top EF352 (all of which are 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 of which are manufactured by AGC Seimi Chemical Co., Ltd.), trade name E1830, trade name E5844 (manufactured by Daikin Fine Chemical Kenkyusho, K.K.), BM-1000, BM-1100, BYK-352, BYK-353, and BYK-361N (all of which are trade names: manufactured by BM Chemie Co.), and the like can be mentioned.Among them, polyacrylate-based leveling agents and perfluoroalkyl-based leveling agents are preferred.

[0149] When the two-component polymerizable liquid crystal composition of the present application contains a leveling agent, the content of the leveling agent is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 5 parts by mass, and further preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. If the content of the leveling agent is within the above range, there is a tendency that the polymerizable liquid crystal is easily horizontally oriented, and the obtained liquid crystal cured film becomes smoother, and thus it is preferred. Note that two or more kinds of leveling agents can be contained.

[0150] <Storage method>

[0151] When the two-component polymerizable liquid crystal composition of the present application is stored, the A agent and the B agent are stored separately. The storage separately includes, for example, a method in which the A agent and the B agent are stored in two separate containers, or a method in which the A agent and the B agent are stored in one container having a partition in the middle so that the two agents do not mix during storage. In the present application, the method in which the A agent and the B agent are stored in two separate containers is preferred.

[0152] As the container for storing the A agent, a plastic container, a metal container, and a glass container can be used, and a plastic container or a metal container is preferred. If the container for storing the A agent is a plastic container or a metal container, the occurrence of side reactions of the reactive additive in the A agent is less likely to occur, and thus it is preferred. As the material of the plastic container, for example, polypropylene, polyethylene, a norbornene-based polymer, polystyrene, polyamide, poly(4-methyl-1-pentene), an acrylic resin, polyvinyl alcohol, an acrylonitrile-butadiene-styrene copolymer, polymethacrylate, polyacrylate, cellulose ester, polycarbonate, polyethylene terephthalate, polysulfone, polyethersulfone, polyether ketone, polyethylene naphthalate, polyphenylene sulfide, polyphenylene ether, a cyclic polyolefin such as a cyclic olefin polymer or a cyclic olefin copolymer, a polyolefin such as an amorphous polyarylate, a polyester, Teflon, or the like can be used, but the present application is not limited to these. As the material of the metal container, for example, steel such as SUS, tinned iron, aluminum, or the like can be used, but the present application is not limited to these. When the container for storing the A agent is a plastic container, a plastic container having light-shielding properties (for example, a brown plastic container) is preferred from the viewpoint that the container is less likely to be affected by ultraviolet rays or the like that can cause deterioration of the composition. Alternatively, the outer surface of the container can be coated.

[0153] As the container for storing the B agent, there is no particular limitation, and as the material of the container, for example, plastic, metal, glass, or the like can be used. As with the above, the container for storing the B agent is preferably a container having light-shielding properties.

[0154] The shape of the container in which the A agent and the B agent are stored is not particularly limited. For example, a hexahedral shape such as a one-gallon can, a plastic can, a pail can, a bucket, and a cylindrical shape can be mentioned. In addition, the capacity of the A agent and the B agent is not particularly limited, and the desired amount can be stored in the container.

[0155] In the case of storing the A agent, the A agent is preferably stored in a dry inactive gas atmosphere. In the present specification, the dry gas generally refers to a gas having a dew point of -50°C or lower, and the inactive gas refers to a gas having low reactivity such as nitrogen, argon, and helium. The storage in a dry inactive gas atmosphere includes, for example, a method in which the gas phase portion in the storage container is filled with a dry inactive gas and then sealed, and a method in which the storage container itself is stored in a space filled with a dry inactive gas. By storing in a dry inactive gas atmosphere, the side reaction of the active hydrogen reactive group possessed by the reactive additive in the A agent with moisture in the surrounding atmosphere can be prevented, and thus the adhesion of the liquid crystal cured film obtained from the two-liquid type polymerizable liquid crystal composition of the present application can be easily improved. In addition, the optical properties after long-term storage can also be easily improved.

[0156] The atmosphere in the case of storing the B agent is not particularly limited, but storage in a dry inactive gas atmosphere is preferred.

[0157] The filling amount of the A agent and the B agent with respect to the capacity of the container in which they are stored is not particularly limited, and the filling amount of the A agent and the B agent is usually 30% or more, preferably 50% or more, and usually 90% or less from the viewpoint of the ease of operation at the time of mixing.

[0158] The temperature at which the A agent and the B agent are stored is not particularly limited, but if the temperature is too high, the polymerization reaction of the polymerizable liquid crystal compound can be initiated, and if the temperature is too low, the solid component in the A agent and the B agent can be precipitated. Therefore, the storage temperature is usually 0 to 50°C, preferably 10 to 40°C, and further preferably 15 to 35°C.

[0159] If the A agent and the B agent are stored in a mixed state for about 3 to 6 months, it can be difficult to produce a liquid crystal cured film having good optical properties. The two-liquid type polymerizable liquid crystal composition of the present application is advantageous in that a liquid crystal cured film having good optical properties can be obtained even after long-term storage. The period during which the A agent and the B agent are stored is not particularly limited, and is usually 3 years or less.

[0160] For the two-pack type polymerizable liquid crystal composition of the present application, by separately storing the reactive additive and the polymerizable liquid crystal compound as described above, a liquid crystal cured film having good optical properties can be obtained even after long-term storage. In this regard, according to the research of the present inventors, it was found that in the two-pack type polymerizable liquid crystal composition, when the solvent contained in the reactive additive satisfies Ra > 37.0, the molecular orientation of the polymerizable liquid crystal compound, which is a cause of deterioration of the optical properties of the liquid crystal cured film after long-term storage, is not easily disturbed, and a liquid crystal cured film having good optical properties can be obtained, and in addition, the adhesion and appearance of the liquid crystal cured film are also excellent.

[0161] <Method for producing polymerizable liquid crystal composition>

[0162] In the present application, the polymerizable liquid crystal composition can be obtained by mixing the A agent and the B agent that constitute the two-pack type polymerizable liquid crystal composition. Note that in the present specification, the "two-pack type polymerizable liquid crystal composition" refers to a composition in which the A agent and the B agent that constitute the two-pack type polymerizable liquid crystal composition are in a state of being separated from each other, and a composition in which the A agent and the B agent are in a state of being mixed is referred to as a "polymerizable liquid crystal composition".

[0163] The timing at which the A agent and the B agent of the two-pack type polymerizable liquid crystal composition of the present application are mixed is not particularly limited, and can be appropriately determined depending on the kind and amount of the reactive additive contained in the A agent and the solvent contained in the B agent, the mixing conditions, and the environment, as long as the reaction between the reactive additive in the A agent and the moisture possibly contained in the solvent in the B agent does not proceed to a certain extent.

[0164] The method for mixing the A agent and the B agent is not particularly limited, and known mixing methods can be used. For example, a method in which mixing is performed using a mixing device having stirring blades such as a planetary mixer or a kneader, and a method in which static mixing is performed using a static mixer can be mentioned.

[0165] The surrounding temperature at the time of mixing the A agent and the B agent is not particularly limited, and the mixing is preferably performed at a temperature of 0 to 50°C, more preferably 15 to 40°C, and further preferably 20 to 35°C. The humidity (relative humidity) is also not particularly limited, but is preferably 30 to 60% RH, and more preferably 40 to 55% RH. In addition, the mixing is usually performed under normal pressure (atmospheric pressure).

[0166] The time for which the mixing is performed is also not particularly limited, and can be appropriately adjusted depending on the kind and amount of the components contained in the two-pack type polymerizable liquid crystal composition. The mixing time is usually 0.5 to 12 hours, and is preferably 0.5 to 6 hours.

[0167] <Method for producing liquid crystal cured film>

[0168] The method for producing the liquid crystal cured film of the present application includes the following steps:

[0169] a step of forming an alignment film on a substrate;

[0170] a step of mixing an A agent and a B agent which constitute the two-liquid type polymerizable liquid crystal composition of the present application to obtain a polymerizable liquid crystal composition;

[0171] a step of coating the aforementioned mixed polymerizable liquid crystal composition on the aforementioned alignment film to obtain a coated film; and

[0172] a step of curing the aforementioned coated film.

[0173] [Substrate]

[0174] As the substrate used in the formation of the liquid crystal cured film, a glass substrate and a plastic substrate can be mentioned. From the viewpoint of being able to perform roll-to-roll processing and having high productivity, the plastic substrate is more preferable than the glass substrate. As the plastic constituting the plastic substrate, for example, polyolefins such as polyethylene, polypropylene, norbornene-based polymers, cyclic olefin-based resins, polyvinyl alcohol, polyethylene terephthalate, polymethacrylate, polyacrylate, cellulose esters such as cellulose triacetate, cellulose diacetate, and cellulose acetate propionate, polyethylene naphthalate, polycarbonate, polysulfone, polyethersulfone, polyether ketone, polyphenylene sulfide, and polyphenylene ether, and the like can be mentioned.

[0175] As commercially available cellulose ester substrates, "Fujitac Film" (manufactured by Fuji Photo Film Co., Ltd.), "KC8UX2M", "KC8UY", and "KC4UY" (all manufactured by Konica Minolta Opto Co., Ltd.), and the like can be mentioned.

[0176] As commercially available cyclic olefin resins, "Topas" (registered trademark) (manufactured by Ticona Corporation (Germany)), "Arton" (registered trademark) (manufactured by JSR Corporation), "ZEONOR" (registered trademark), "ZEONEX" (registered trademark) (both manufactured by ZEON Corporation, Japan), and "APEL" (registered trademark) (manufactured by Mitsui Chemicals, Inc.) can be given. Such a cyclic olefin resin can be subjected to film formation by a known means such as a solvent casting method or a melt extrusion method, thereby producing a substrate. A commercially available cyclic olefin resin substrate can also be used. As commercially available cyclic olefin resin substrates, "Esushina" (registered trademark), "SCA40" (registered trademark) (both manufactured by Shikoku Chemicals Corporation), "Zeonor Film" (registered trademark) (manufactured by Optes Corporation), and "Arton Film" (registered trademark) (manufactured by JSR Corporation) can be given.

[0177] The thickness of the substrate is more preferably thinner from the viewpoint of quality as a degree of operability, but if it is too thin, there is a tendency that the strength decreases and the processability deteriorates. The thickness of the substrate is usually 5 to 300 μm, and preferably 20 to 200 μm.

[0178] [Alignment film]

[0179] In the present application, the alignment film is a film formed of a high molecular compound, and has an alignment controlling ability to align the polymerizable liquid crystal compound in a desired direction.

[0180] The alignment film makes the liquid crystal alignment of the polymerizable liquid crystal compound easy. The state of the liquid crystal alignment such as horizontal alignment, vertical alignment, hybrid alignment, and oblique alignment varies depending on the properties of the alignment film and the polymerizable liquid crystal compound, and the combination thereof can be arbitrarily selected. For example, when the alignment film is a material that exhibits horizontal alignment as the alignment controlling ability, the polymerizable liquid crystal compound can form horizontal alignment or hybrid alignment, and when it is a material that exhibits vertical alignment, the polymerizable liquid crystal compound can form vertical alignment or oblique alignment. The expressions of horizontal, vertical, and the like indicate the direction of the long axis of the aligned polymerizable liquid crystal compound with the liquid crystal cured film plane as a reference. The so-called horizontal alignment is alignment in which the long axis of the aligned polymerizable liquid crystal compound is in a direction parallel to the liquid crystal cured film plane. The so-called "parallel" herein means an angle of 0° ± 20° with respect to the liquid crystal cured film plane. The so-called vertical alignment is alignment in which the long axis of the aligned polymerizable liquid crystal compound is in a direction perpendicular to the liquid crystal cured film plane.

[0181] The so-called vertical herein means 90° ± 20° with respect to the liquid crystal cured film plane.

[0182] Regarding orientation control, when the alignment film is formed from an orientation polymer, it can be arbitrarily adjusted by surface state and friction conditions; when it is formed from a photo-oriented polymer, it can be arbitrarily adjusted by polarized light irradiation conditions, etc. Furthermore, liquid crystal orientation can also be controlled by selecting the surface tension, liquid crystal properties, and other physical properties of the polymerizable liquid crystal compound.

[0183] As an alignment film, it is preferable to have an alignment film that is insoluble in the solvent used to form a liquid crystal curing film on the alignment film, and has heat resistance for solvent removal and heat treatment for liquid crystal alignment. Examples of alignment films include alignment films formed from alignment polymers, photoalignment films, groove alignment films, and stretched films stretched along the alignment direction, with photoalignment films being preferred.

[0184] The thickness of the alignment film is typically 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.

[0185] Examples of oriented polymers include polyamides with intramolecular amide bonds, gelatin-like polymers, polyimides with intramolecular imide bonds and their hydrolysates such as polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylates. Among these, polyvinyl alcohol is preferred.

[0186] These orientation polymers can be used alone or in combination of two or more.

[0187] Oriented films formed from oriented polymers can typically be obtained by coating a composition (hereinafter also referred to as "oriented polymer composition") made by dissolving the oriented polymer in a solvent onto a substrate and removing the solvent, or by coating the oriented polymer composition onto a substrate, removing the solvent, and then rubbing (friction method).

[0188] Examples of solvents mentioned above include water; alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, methyl cellosolve, butyl cellosolve, 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 pentyl 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; chlorinated hydrocarbon solvents such as chloroform and chlorobenzene; and so on. These solvents can be used alone or in combination of two or more.

[0189] The concentration of the alignment polymer in the alignment polymer composition can be within a range in which the alignment polymer can be completely dissolved in the solvent, and is preferably 0.1 to 20% by mass, and more preferably 0.1 to 10% by mass, with respect to the solid content of the solution.

[0190] As the alignment polymer composition, a commercially available alignment film material can also be used directly. As the commercially available alignment film material, SUNEVER (registered trademark) (manufactured by Nissan Chemical Industries, Ltd.) or OPTMER (registered trademark) (manufactured by JSR Corporation), and the like can be given.

[0191] As the method of applying the alignment polymer composition to the substrate, known methods such as a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, a coater method, and a printing method such as a flexographic method can be given.

[0192] In a case where the alignment film of the present application is manufactured by a continuous manufacturing method in a roll-to-roll (R2R) form, as the application method, a gravure coating method, a die coating method, or a printing method such as a flexographic method is generally used.

[0193] By removing the solvent included in the alignment polymer composition, a dried coating film of the alignment polymer can be formed. As the method of removing the solvent, a natural drying method, an air-drying method, a heating drying method, a reduced-pressure drying method, and the like can be given.

[0194] As the method of performing rubbing, a method in which a film of the alignment polymer formed on the surface of the substrate by applying the alignment polymer composition to the substrate and performing annealing is brought into contact with a rubbing roller on which a rubbing cloth is wound and which is rotating can be given.

[0195] The photoalignment film is generally formed from a polymer, an oligomer, or a monomer having a photoreactive group.

[0196] In a case where the polymerizable liquid crystal is continuously formed, from the viewpoint of solvent resistance and the like, a polymer having a molecular weight of 5000 or more is preferable, and from the viewpoint of affinity, in a case where the polymerizable liquid crystal is a (meth)acryl group, an acrylic polymer is preferable. The photoalignment film can be obtained by applying a composition (hereinafter, also referred to as a “photoalignment film-forming composition”) including a polymer, an oligomer, or a monomer having a photoreactive group and a solvent to a substrate, drying and removing the solvent, and then irradiating polarized light (preferably, polarized UV light).

[0197] From the aspect that the direction of the alignment control force can be arbitrarily controlled by selecting the polarization direction of the irradiated polarized light, the photoalignment film is more preferable.

[0198] The so-called photoreactive group is a group that generates liquid crystal alignment ability by irradiation of light. Specifically, it is a group that undergoes orientation induction or isomerization reaction, dimerization reaction, photocrosslinking reaction, or photodecomposition reaction of a molecule that is generated by irradiation of light, such as a photoreaction that becomes the origin of liquid crystal alignment ability. Among these photoreactive groups, from the aspect of excellent alignment properties, a photoreactive group that undergoes dimerization reaction or photocrosslinking reaction is preferable. As the photoreactive group that can undergo the above reaction, a group having an unsaturated bond, particularly a double bond, is preferable, and a group having at least one selected from the group consisting of carbon-carbon double bond (C=C bond), carbon-nitrogen double bond (C=N bond), nitrogen-nitrogen double bond (N=N bond), and carbon-oxygen double bond (C=O bond) is more preferable.

[0199] As the photoreactive group having a C=C bond, for example, a vinyl group, a polyene group, a stilbenyl group, a stilbazole group, a stilbazolium group, a chalcone group, and a cinnamoyl group, etc. can be given. As the photoreactive group having a C=N bond, a group having a structure of an aromatic Schiff base, an aromatic hydrazone, etc. can be given. As the photoreactive group having a N=N bond, a group having an azobenzene group, an azonaphthalene group, an aromatic heterocyclic azo group, a bisazo group, a formazan group, etc., and a group having an azobenzene oxide as a basic structure can be given. As the photoreactive group having a C=O bond, a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group, etc. can be given.

[0200] These groups can have substituents such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, and a halogenated alkyl group.

[0201] As the solvent of the photoalignment film-forming composition, a solvent that dissolves the polymer and the monomer having a photoreactive group is preferable, and as the solvent, for example, the solvents listed as the solvent of the aforementioned alignment polymer composition, etc. can be given.

[0202] The content of the polymer or the monomer having a photoreactive group with respect to the photoalignment film-forming composition can be appropriately adjusted depending on the kind of the polymer or the monomer having a photoreactive group and the thickness of the photoalignment film to be produced, but it is preferably set to 0.2% by mass or more, and particularly preferably in the range of 0.3 to 10% by mass. In addition, a high molecular material such as polyvinyl alcohol, polyimide, and a photosensitizer can be contained within the range that does not significantly impair the characteristics of the photoalignment film.

[0203] As the method of applying the photoalignment film-forming composition to the diffusion-preventing layer, the same method as the method of applying the alignment polymer composition to the diffusion-preventing layer can be given. As the method of removing the solvent from the applied photoalignment film-forming composition, for example, the same method as the method of removing the solvent from the alignment polymer composition can be given.

[0204] In order to irradiate polarized light, it is possible to directly irradiate polarized light to the product obtained by removing the solvent from the light orientation film-forming composition applied to the substrate, or it is possible to irradiate polarized light by irradiating polarized light from the substrate and allowing the polarized light to pass through. In addition, it is particularly preferable that the polarized light be substantially parallel light. The wavelength of the polarized light to be irradiated is preferably a wavelength in a region in which the light energy can be absorbed by the light-reactive group of the polymer or monomer having a light-reactive group. Specifically, it is particularly preferable that the wavelength be in the range of 250 to 400 nm of UV (ultraviolet light). As the light source used in the polarized light irradiation, a xenon lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, KrF, ArF, or the like can be used, and it is more preferable to use a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, or a metal halide lamp. These lamps have a large emission intensity of ultraviolet light at a wavelength of 313 nm, and thus are preferable. It is possible to allow the light from the aforementioned light source to pass through a suitable polarizing plate and then to irradiate the light, thereby irradiating polarized light. As the polarizing plate, a polarizing filter, a polarizing prism such as a Glan-Thomson or a Glan-Taylor, or a wire grid-type polarizing plate can be used.

[0205] Note that, if masking is performed while rubbing or polarized light irradiation is performed, it is also possible to form a plurality of regions (patterns) in which the liquid crystal orientation direction is different.

[0206] A groove orientation film is a film having a concave-convex pattern or a plurality of grooves (slots) on the film surface. In a case where a plurality of linear grooves are arranged at equal intervals on the film, liquid crystal molecules are oriented in a direction along the slots.

[0207] As a method for obtaining a groove orientation film, a method in which a photosensitive polyimide film surface is exposed through a mask for exposure having a pattern shape, and then developed and rinsed to form a concave-convex pattern, a method in which a layer of a UV-curable resin before curing is formed on a plate-like original having slots on the surface, the resin layer is transferred to a substrate, and then cured, a method in which a roll-shaped original having a plurality of slots is pressed against a film of a UV-curable resin before curing formed on a substrate, a concave-convex pattern is formed, and then cured, and the like can be given. Specifically, a method described in Japanese Patent Application Publication No. H6-34976 and Japanese Patent Application Publication No. 2011-242743, and the like can be given.

[0208] In order to obtain an orientation with little orientation disorder, the width of the convex portion of the groove orientation film is preferably 0.05 to 5 μm, the width of the concave portion is preferably 0.1 to 5 μm, and the depth of the concave-convex step is preferably 2 μm or less, and preferably 0.01 to 1 μm or less.

[0209] 〔Liquid crystal cured film〕

[0210] <Coating of the polymerizable liquid crystal composition>

[0211] The liquid crystal cured film can be formed by coating the mixed polymerizable liquid crystal composition on the above-mentioned substrate or alignment film. As a method of coating the polymerizable liquid crystal composition on the substrate, an extrusion coating method, a direct gravure coating method, an inverse gravure coating method, a CAP coating method, a slit coating method, a microgravure method, a die coating method, an inkjet method, and the like can be given. In addition, a method of coating using a coating machine such as a dip coater, a bar coater, a spin coater, and the like can also be given. Among them, in the case of continuous coating in a roll to roll form, a coating method based on the microgravure method, the inkjet method, the slit coating method, or the die coating method is preferred, and in the case of coating on a single substrate such as glass, a spin coating method having high uniformity is preferred. In the case of coating in a roll to roll form, an alignment film can also be formed by coating a composition for forming a photoalignment film or the like on the substrate, and the polymerizable liquid crystal composition can be further continuously coated on the obtained alignment film.

[0212] <Drying of the polymerizable liquid crystal composition>

[0213] As a drying method for removing the solvent contained in the polymerizable liquid crystal composition, for example, a natural drying method, an air-drying method, a heating drying method, a reduced pressure drying method, and a method combining them can be given. Among them, a natural drying method or a heating drying method is preferred. The drying temperature is preferably in the range of 0 to 200°C, more preferably in the range of 20 to 150°C, and further preferably in the range of 50 to 130°C. The drying time is preferably in the range of 10 seconds to 20 minutes, and more preferably in the range of 30 seconds to 10 minutes. The composition for forming a photoalignment film and the alignment polymer composition can also be dried in the same manner.

[0214] <Polymerization of the polymerizable liquid crystal compound>

[0215] As a method of causing the polymerizable liquid crystal compound to polymerize, photopolymerization is preferable. The photopolymerization can be performed by irradiating a laminate obtained by coating a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound on a substrate or an alignment film with active energy rays. As the active energy rays for the irradiation, one or more kinds of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays can be appropriately selected depending on the kind of the polymerizable liquid crystal compound contained in the dried film (particularly, the kind of the photopolymerizable functional group possessed by the polymerizable liquid crystal compound), the kind of the photopolymerization initiator in the case where the photopolymerization initiator is contained, and the amount thereof. Specifically, visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays can be mentioned. Among them, from the viewpoint of easy control of the progress of the polymerization reaction and the viewpoint that a device widely used in the field can be used as a photopolymerization device, ultraviolet light is preferable, and the kind of the polymerizable liquid crystal compound is preferably selected in such a manner that photopolymerization can be performed with ultraviolet light.

[0216] As the light source of the aforementioned active energy rays, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excimer laser, an LED light source that emits light in the wavelength range of 380 to 440 nm, a chemical lamp, a black light, a microwave-excited mercury lamp, a metal halide lamp, and the like can be mentioned.

[0217] The ultraviolet irradiation intensity is usually 10 mW / cm 2 to 3,000 mW / cm 2 The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for the activation of the cationic polymerization initiator or the radical polymerization initiator. The time for which the light is irradiated is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, and further preferably 0.1 seconds to 1 minute. When the ultraviolet irradiation is performed once or a plurality of times with such an ultraviolet irradiation intensity, the cumulative light amount is 10 mJ / cm 2 to 3,000 mJ / cm 2 , preferably 50 mJ / cm 2 to 2,000 mJ / cm 2 , more preferably 100 mJ / cm 2 to 1,000 mJ / cm 2 . When the cumulative light amount is less than this range, the curing of the polymerizable liquid crystal compound sometimes becomes insufficient, and good transferability is not obtained. On the contrary, when the cumulative light amount is more than this range, the optical film containing the optically anisotropic layer sometimes becomes colored.

[0218] Example

[0219] The present application will be described more specifically below by way of examples. Note that, unless otherwise specified, "%" and "parts" in the examples refer to mass % and mass parts, respectively. Also, the δ D(W) of water was 15.5, the δ P(W) of water was 16.0, the δ H(W) of water was 42.3.

[0220] <Example 1>

[0221] Preparation of the composition for forming a photo-alignment film

[0222] The following ingredients described in Japanese Patent Application Publication No. 2013-033249 were mixed, and the resulting mixture was stirred at 80°C for 1 hour, thereby obtaining a composition for forming a photo-alignment film.

[0223] Photo-alignment polymer:

[0224]

[0225] Preparation of the A agent

[0226] The following ingredients were mixed, and stirred at 25°C for 1 hour, thereby obtaining an A agent (1). Note that the δ D(S) of cyclopentanone was 17.9, the δ P(S) of cyclopentanone was 11.9, the δ H(S) of cyclopentanone was 5.2.

[0227] Reactive additive: LAROMER PR9000 (manufactured by BASF Japan Ltd.) 5.0 parts

[0228] (hereinafter also referred to as PR9000)

[0229] Solvent: cyclopentanone (Ra: 37.6) 70 parts

[0230] The prepared A agent (1) was charged into a SUS can, the gas phase portion was replaced with dry nitrogen, and the can was sealed.

[0231] Preparation of the B agent

[0232] The following ingredients were mixed, and stirred at 80°C for 1 hour, thereby obtaining a B agent (1). The δ D(S) of N-methylpyrrolidone (NMP) was 18.0, the δ P(S) of N-methylpyrrolidone (NMP) was 12.3, the δ H(S) of N-methylpyrrolidone (NMP) was 7.2.

[0233] Polymerizable liquid crystal compound (mixture):

[0234]

[0235]

[0236] Polymerization initiator: 2-dimethylamino-2-benzyl-l-(4-morpholinophenyl)butane-l-one

[0237] (Irgacure 369; manufactured by Ciba Specialty Chemicals Inc.) 6 parts

[0238] Leveling agent: polyacrylate compound (BYK-361N; manufactured by BYK-Chemie Co.) 0.075 parts

[0239] Solvent: cyclopentanone 370 parts

[0240] N-methylpyrrolidone 274 parts

[0241] (Ra of the solvent as a whole: 36.8)

[0242] The prepared B agent (1) was charged into a SUS-made can, the vapor phase portion was replaced with dry nitrogen, and the can was sealed.

[0243] <Method for producing liquid crystal cured film>

[0244] (1) Formation of photo-alignment film

[0245] A cycloolefin polymer (COP) film (Zeonor Film (registered trademark) "ZF-14" manufactured by ZEON Corporation, film thickness 23 μm) was used as a substrate, and after the film surface was subjected to corona treatment, the above-mentioned composition for forming a photo-alignment film was applied thereto, and dried at 80°C to obtain a dried coating film. A photo-alignment film was formed by irradiating polarized UV light onto the dried coating film, and a film with a photo-alignment film was obtained. The polarized UV light treatment was performed using a UV irradiation device (SPOT CURE SP-7; manufactured by USHIO INC.) under conditions where the intensity measured at a wavelength of 365 nm was 100 mJ / cm 2 The film with a photo-alignment film was obtained as described above.

[0246] (2) Formation of liquid crystal cured film

[0247] After the preparation of the A agent (1) and the B agent (1), after the storage for 3 months at 25°C or after the storage for 6 months, the A agent (1) and the B agent (1) were mixed, and stirred at 25°C for 1 hour, whereby the polymerizable liquid crystal composition (1) was obtained. Immediately after the aforementioned polymerizable liquid crystal composition (1) was obtained, the aforementioned polymerizable liquid crystal composition (1) was coated on the film with the photo-alignment film obtained above by a bar coater method, and then, dried by heating in a drying oven at 120°C for 1 minute, whereby the solvent was sufficiently removed. Subsequently, ultraviolet rays with an exposure amount of 1000 mJ / cm 2 (365 nm as a reference) were irradiated to the layer formed of the polymerizable liquid crystal composition (1), whereby the liquid crystal cured film (1) was formed.

[0248] <Orientation Evaluation>

[0249] The obtained liquid crystal cured film was observed at a magnification of 400 times using a polarizing microscope (BX51, manufactured by Olympus Corporation). The case where the orientation was good was noted as O, the case where the orientation was slightly visible was noted as Δ, and the case where the orientation was insufficient, such as the case where the orientation was visible on the surface, was noted as X.

[0250] <Adhesion Evaluation>

[0251] A 25-mm-wide Cellotape (manufactured by NICHIBAN) was attached to the surface and the back of the obtained liquid crystal cured film (1), and 90° peeling tests were performed on the surface and the back, respectively. The case where no peeling occurred was noted as O, the case where peeling occurred only in a part of the test site was noted as Δ, and the case where peeling occurred on the entire test site was noted as X.

[0252] <Appearance Evaluation>

[0253] The obtained liquid crystal cured film (1) was confirmed by visual observation, and the presence or absence of foreign matter was confirmed. The case where no foreign matter was confirmed by visual observation was noted as O, the case where a little foreign matter was confirmed was noted as Δ, and the case where a large amount of foreign matter was confirmed was noted as X.

[0254] <Examples 2 and 3>

[0255] The A agent was stored in a container as described in the table, and otherwise, the same operations as in Example 1 were performed, whereby the polymerizable liquid crystal compositions (2) and (3) and the liquid crystal cured films (2) and (3) were obtained. The orientation, the adhesion, and the appearance of the obtained liquid crystal cured films were evaluated by performing the same operations as in Example 1.

[0256] <Example 4>

[0257] The gas phase part of the container storing the A agent was made to be air, and otherwise, the same operation as in Example 1 was performed to obtain a polymerizable liquid crystal composition (4) and a liquid crystal cured film (4). The obtained liquid crystal cured film was evaluated for orientation, adhesion, and appearance, in the same manner as in Example 1.

[0258] <Example 5>

[0259] The following compound was used as the reactive additive, and otherwise, the same operation as in Example 1 was performed to obtain a polymerizable liquid crystal composition (5) and a liquid crystal cured film (5). The obtained liquid crystal cured film (5) was evaluated for orientation, adhesion, and appearance, in the same manner as in Example 1.

[0260] Reactive additive: Karenz AOI (Showa Denko K.K.) 5.0 parts

[0261] <Example 6>

[0262] The following compound was used as the reactive additive, and otherwise, the same operation as in Example 1 was performed to obtain a polymerizable liquid crystal composition (6) and a liquid crystal cured film (6). The obtained liquid crystal cured film was evaluated for orientation, adhesion, and appearance, in the same manner as in Example 1.

[0263] Reactive additive: KBM-5103 (Shin-Etsu Chemical Co., Ltd.) 2.0 parts

[0264] <Example 7>

[0265] The solvent of the A agent was made to be chloroform 70 parts by mass, and the solvent of the (B) agent was made to be NMP 644 parts by mass, and otherwise, the same operation as in Example 1 was performed to obtain a polymerizable liquid crystal composition (7) and a liquid crystal cured film (7). Note that the δ D(S) of chloroform was 17.8, the δ P(S) was 3.1, and the δ H(S) was 5.7, and Ra was 39.1. The obtained liquid crystal cured film was evaluated for orientation, adhesion, and appearance, in the same manner as in Example 1.

[0266] <Example 8>

[0267] The solvent of the A agent was made to be anisole 70 parts by mass, and the solvent of the (B) agent was made to be NMP 644 parts by mass, and otherwise, the same operation as in Example 1 was performed to obtain a polymerizable liquid crystal composition (8) and a liquid crystal cured film (8). Note that the δ D(S) of anisole was 17.8, the δ P(S) was 4.4, and the δ H(S) was 6.9, and Ra was 37.5. The obtained liquid crystal cured film was evaluated for orientation, adhesion, and appearance, in the same manner as in Example 1.

[0268] <Example 9>

[0269] The polymerizable liquid crystal compound was LC242 (manufactured by BASF Japan Ltd.), and the solvent for agent B was 644 parts by mass of NMP. Otherwise, the same procedure as in Example 1 was followed to obtain the polymerizable liquid crystal composition (9) and the liquid crystal cured film (9). The orientation, adhesion, and appearance of the obtained liquid crystal cured film were evaluated in the same manner as in Example 1.

[0270] <Example 10>

[0271] The polymerizable liquid crystal compound was LC242 (manufactured by BASF Japan Ltd.), and the solvent for agent B was a mixture of 370 parts by mass of cyclopentanone and 274 parts by mass of propylene glycol monomethyl ether acetate (PGMEA). Otherwise, the procedure was the same as in Example 1 to obtain the polymerizable liquid crystal composition (10) and the liquid crystal cured film (10). It should be noted that the δ of PGMEA... D(S) It is 15.6, δ P(S) It is 5.6, δ H(S) The Ra value was 9.8, and the overall Ra value of the solvent in agent B 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.

[0272] <Comparative Example 1>

[0273] After preparing agent (A) and agent (B) in the same manner as in Example 1, the two liquids were mixed by stirring at 25°C for 1 hour in an SUS container. After mixing the two liquids, they were sealed under dry nitrogen and stored at 25°C for 3 or 6 months before coating. The orientation, adhesion, and appearance of the obtained liquid crystal cured film were evaluated in the same manner as in Example 1.

[0274] <Comparative Example 2>

[0275] Without using reactive additives, agent (B) was prepared in the same manner as in Comparative Example 1. It was sealed under dry nitrogen and stored at 25°C for 3 or 6 months before being coated. The orientation, adhesion, and appearance of the obtained liquid crystal cured film were evaluated in the same manner as in Example 1.

[0276] <Comparative Examples 3 and 4>

[0277] The reactive additive was changed as described in the table, and otherwise, the (A) agent and the (B) agent were prepared in the same manner as in Comparative Example 1, and then the two liquids were mixed by stirring at 25°C for 1 hour in a SUS-made tank. After mixing the two liquids, the tank was sealed under dry nitrogen, and after storage at 25°C for 3 months or 6 months, the coating was performed, and the obtained liquid crystal cured film was evaluated for orientation, adhesion, and appearance in the same manner as in Example 1.

[0278] [Comparative Example 5]

[0279] The (A) agent and the (B) agent were prepared in the same manner as in Example 10, and then the two liquids were mixed by stirring at 25°C for 1 hour in a SUS-made tank. After mixing the two liquids, the tank was sealed under dry nitrogen, and after storage at 25°C for 3 months or 6 months, the coating was performed, and the obtained liquid crystal cured film was evaluated for orientation, adhesion, and appearance in the same manner as in Example 1.

[0280] [Table 1]

[0281]

[0282] With the compositions of Examples 1 to 10, even if the preparation is followed by mixing and coating after storage for 3 months or after storage for 6 months, a liquid crystal cured film having good optical properties, high adhesion, and excellent appearance can be obtained. On the other hand, it was found that Comparative Examples 1 and 3 to 5, which were stored after mixing the two liquids, resulted in liquid crystal cured films having poor orientation and appearance, and Comparative Example 2, which did not contain a reactive additive, resulted in a liquid crystal cured film having poor adhesion.

Claims

1. A storage method for a two-liquid polymerizable liquid crystal composition composed of an A agent containing a reactive additive having a polymerizable group and an active hydrogen reactive group in a molecule and a solvent, and a B agent containing a polymerizable liquid crystal compound and a solvent, wherein a value of Ra represented by the following formula (1) of the solvent in the A agent satisfies Ra > 37.0, [Mathematical formula 1] Ra = 100 - (100 - 37.0) x (mass of the solvent in the A agent) / (mass of the solvent in the B agent), and the A agent and the B agent are stored separately at a storage temperature of 0 to 50°C.

2. The storage method according to claim 1, wherein the A agent is stored in a dry atmosphere of a non-reactive gas. In formula (1), δ D（W） represents the dispersive term of the Hansen solubility parameter of water, δ D（S） represents the dispersive term of the Hansen solubility parameter of the solvent as a whole based on a 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 solvent as a whole based on a weighted average of the solvents, δ H（W） represents the hydrogen bonding term of the Hansen solubility parameter of water, δ H（S） represents the hydrogen bonding term of the Hansen solubility parameter of the solvent as a whole based on a weighted average of the solvents, wherein 3. The storage method according to claim 1 or 2, wherein a value of Ra represented by the formula (1) of the solvent in the B agent satisfies Ra < 37.

0.

4. The storage method according to any one of claims 1 to 3, wherein the amount of the reactive additive contained in the A agent is 0.5 to 10 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound.

2. The preservation method of claim 1, wherein, 5. A manufacturing method for a polymerizable liquid crystal composition, comprising a step of mixing the A agent and the B agent constituting a two-liquid polymerizable liquid crystal composition stored by the storage method according to any one of claims 1 to 4.

3. The preservation method of claim 1 or 2, wherein, 6. A manufacturing method for a liquid crystal cured film, comprising the following steps: a step of forming an alignment film on a substrate; a step of mixing the A agent and the B agent constituting a two-liquid polymerizable liquid crystal composition stored by the storage method according to any one of claims 1 to 4 to obtain a polymerizable liquid crystal composition; a step of applying the mixed polymerizable liquid crystal composition on the alignment film to obtain a coating film; and a step of curing the coating film.

4. The preservation method of claim 1 or 2, wherein, ​ ​ ​ ​ ​ ​ ​

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