Composition for forming a two-liquid type polarizing film

Abstract

To provide a polarizing film-forming composition which allows for producing a polarizing film that offers good optical performance even after prolonged storage, and to provide a storage method therefor, manufacturing method therefor, and a method of manufacturing a polarizing film.SOLUTION: A two-component composition for forming a polarizing film is provided, comprising: an agent A containing a reactive additive having a polymerizable group and an active hydrogen reactive group in a molecule thereof, and a solvent; and an agent B containing a dichroic dye and a solvent, where the dichroic dye contains an azo dye having an amine structure.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a two-liquid type composition for forming a polarizing film and a method for storing the same, a method for producing a composition for forming a polarizing film, and a method for producing a polarizing film. [Background technology]

[0002] In recent years, with the trend toward thinner image display devices, optical films such as polarizing plates and retardation plates have been developed that use a polarizing film having a liquid crystal cured layer obtained by applying a polymerizable liquid crystal compound onto a substrate or an alignment film and curing the compound in an aligned state. In the manufacture of such optical films, from the viewpoints of film formability and ease of handling, the polymerizable liquid crystal compound is usually applied onto the substrate or alignment film as a composition for forming a polarizing film in which the polymerizable liquid crystal compound is dissolved in a solvent or the like. When an optical film is manufactured by applying a composition onto a substrate or alignment film, it is known that it is preferable to have higher adhesion between the substrate or alignment film and the resulting optical film, since peeling during processing does not occur, and therefore a high-quality optical film is easily obtained, and a composition having the property of providing an optical film with high adhesion has been proposed (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2017-83843 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, it has been found that when such a composition is stored for a long period of time and then used to form a polarizing film, good optical performance is not necessarily obtained. Therefore, an object of the present invention is to provide a composition for forming a polarizing film, a method for storing the same, a method for producing the composition, and a method for producing a polarizing film, which are capable of producing a polarizing film having good optical performance even after long-term storage. [Means for solving the problem]

[0005] The present inventors conducted extensive research to solve the above problems and arrived at the present invention. That is, the present invention includes the following preferred embodiments. [1] A two-liquid type composition for forming a polarizing film, comprising: a component A including a reactive additive having a polymerizable group and an active hydrogen-reactive group in the molecule, and a solvent; and a component B including a dichroic dye and a solvent, wherein the dichroic dye includes an azo dye having an amine structure. [2] The two-liquid type polarizing film-forming composition according to [1], further comprising a polymerizable liquid crystal compound. [3] The two-liquid type composition for forming a polarizing film according to [1] or [2], wherein the water content of the solvent contained in the agent A is less than 300 ppm. [4] The two-liquid type composition for forming a polarizing film according to [2] or [3], wherein the amount of the reactive additive contained in the agent A is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymerizable liquid crystal compound. [5] The method for storing the two-part composition for forming a polarizing film according to any one of [1] to [4], wherein the agent A and the agent B are stored separately. [6] The storage method according to [5], wherein the agent A is stored in a plastic or metal container. [7] The storage method according to [5] or [6], wherein the agent A is stored under a dry inert gas atmosphere. [8] A method for producing a composition for forming a polarizing film, comprising a step of mixing a component A, which constitutes the two-component composition for forming a polarizing film according to any one of [1] to [4], and which contains a reactive additive having a polymerizable group and an active hydrogen-reactive group in its molecule and a solvent, with a component B, which contains a dichroic dye including an azo dye having an amine structure and a solvent. [9] forming an alignment film on a substrate; A step of obtaining a polarizing film-forming composition by mixing an A component, which comprises the reactive additive having a polymerizable group and an active hydrogen-reactive group in the molecule and a solvent, with a B component, which comprises a dichroic dye including an azo dye having an amine structure and a solvent, and which constitutes the two-liquid type polarizing film-forming composition according to any one of [1] to [4]; A step of applying the composition for forming a polarizing film after mixing onto the alignment film to obtain a coating film, and A step of curing the coating film A method for producing a polarizing film, comprising the above steps.

Advantages of the Invention

[0006] According to the present invention, it is possible to provide a composition for forming a polarizing film, a storage method thereof, a method for producing the composition, and a method for producing a polarizing film, which can obtain a polarizing film having good optical performance even after long-term storage. Furthermore, the polarizing film obtained from the composition for forming a polarizing film of the present invention has high adhesion and an excellent appearance.

Embodiments for Carrying Out the Invention

[0007] Hereinafter, embodiments of the present invention will be described in detail. It should be noted that the scope of the present invention is not limited to the embodiments described here, and various modifications can be made without departing from the spirit of the present invention.

[0008] The two-component composition for forming a polarizing film of the present invention is composed of Agent A containing a reactive additive having a polymerizable group and an active hydrogen-reactive group in the molecule and a solvent, and Agent B containing a dichroic dye containing an azo dye having an amine structure and a solvent.

[0009] The two-component composition for forming a polarizing film of the present invention contains a reactive additive, an azo dye having an amine structure, and a solvent for dissolving them as essential components, and the reactive additive is separately formulated in Agent A and the azo dye having an amine structure is separately formulated in Agent B.

[0010] <Agent A> 〔Reactive Additive〕 The reactive additive generally refers to a substance added to a composition for forming a polarizing film in order to improve the adhesion of the polarizing film. The polymerizable group of the reactive additive contained in the agent A means a group involved in a polymerization reaction. The polymerizable group may be, for example, a carbon-carbon unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond, and specific examples thereof include a vinyl group, a (meth)acrylic group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxiranyl group, and an oxetanyl group.

[0011] The active hydrogen reactive group possessed by the reactive additive contained in the A agent means a group reactive to a group having active hydrogen such as a carboxy group (-COOH), a hydroxyl group (-OH), an amino group (-NH2), etc., and representative examples thereof include an epoxy group, a glycidyl group, an oxazolyl group, a carbodiimide group, an aziridinyl group, an imide group, an isocyanate group, a thioisocyanate group, a maleic anhydride group, an alkoxysilyl group, etc. In the reactive additive, it is preferable that at least two active hydrogen reactive groups are present, and in this case, the multiple active hydrogen reactive groups present may be the same or different.

[0012] The reactive additive has usually 1 to 20 polymerizable groups and active hydrogen reactive groups, and preferably 1 to 10 polymerizable groups and active hydrogen reactive groups.

[0013] In a preferred embodiment, the reactive additive preferably contains a vinyl group and / or a (meth)acrylic 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 is more preferably a reactive additive having an acrylic group and an isocyanate group or a reactive additive having an acrylic group and an alkoxysilyl group.

[0014] Specific examples of reactive additives include compounds having a (meth)acrylic group and an epoxy group, such as methacryloyloxyglycidyl ether and acryloyloxyglycidyl ether; compounds having a (meth)acrylic group and an oxetanyl group, such as oxetane acrylate and oxetane methacrylate; compounds having a (meth)acrylic group and a lactone group, such as lactone acrylate and lactone methacrylate; compounds having a vinyl group and an oxazolyl group, such as vinyl oxazoline and isopropenyl oxazoline; compounds having a (meth)acrylic group and an isocyanate group, such as isocyanatomethyl acrylate, isocyanatomethyl methacrylate, 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate; and oligomers of compounds having a (meth)acrylic group and an alkoxysilyl group, such as 3-acryloyloxypropyltrimethoxysilane and 3-methacryloyloxypropylmethyldimethoxysilane. Further, compounds having a vinyl group or vinylene group and an acid anhydride, such as methacrylic anhydride, acrylic anhydride, maleic anhydride, and vinyl maleic anhydride, can be mentioned. Among them, methacryloyloxyglycidyl ether, acryloyloxyglycidyl ether, isocyanatomethyl acrylate, isocyanatomethyl methacrylate, vinyloxazoline, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 3-acryloyloxypropyltrimethoxysilane, and the above oligomers are preferred, and isocyanatomethyl acrylate, 2-isocyanatoethyl acrylate, 3-acryloyloxypropyltrimethoxysilane, and the above oligomers are particularly preferred.

[0015] The reactive additive may be a commercially available product, either as is or after purification as necessary. Examples of commercially available products include Laromer (registered trademark) PR9000 (manufactured by BASF), Karenz AOI (registered trademark) (manufactured by Showa Denko K.K.), and KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0016] The amount of the reactive additive contained in the 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, and is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, even more preferably 6 parts by mass or less, and even more preferably 5 parts by mass or less, based on 100 parts by mass of the polymerizable liquid crystal compound described below. When the amount of the reactive additive is the lower limit or more and the upper limit or less, the alignment of the polarizing film produced from the two-liquid type polarizing film forming composition of the present invention is not impaired, and the adhesion is likely to be improved. The reactive additive may be used alone or in combination of two or more kinds. When two or more kinds of reactive additives are used, the amount of the reactive additives refers to the total amount.

[0017] When the two-liquid type polarizing film-forming composition of the present invention does not contain a polymerizable liquid crystal compound described below, the amount of the reactive additive contained in Agent A is 2 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 15 parts by mass or more, relative to 100 parts by mass of the total of all dichroic dyes contained in Agents A and B, and is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 80 parts by mass or less.

[0018] 〔solvent〕 The water content of the solvent contained in the A agent is preferably less than 300 ppm, more preferably less than 250 ppm, even more preferably less than 200 ppm, even more preferably less than 150 ppm, and particularly preferably less than 100 ppm. When the water content of the solvent contained in the A agent is less than the upper limit, the active hydrogen reactive group of the reactive additive is unlikely to react with water, so that the adhesion of the polarizing film is easily improved even after long-term storage, and a polarizing film having excellent appearance is easily obtained. The lower limit of the water content of the solvent contained in the A agent is 0 ppm. The water content of the solvent contained in the A agent can be controlled within the above range, for example, by distilling the solvent together with a drying agent under an inert gas, or by coexisting with a molecular sieve or the like for a certain period of time. A commercially available dehydrated solvent can also be used. The water content of the solvent contained in the A agent can be determined, for example, by using a Karl Fischer titration device.

[0019] Specific examples of such solvents include alcohol-based solvents such as methanol, ethanol, butanol, ethylene glycol, isopropyl alcohol, 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; pentane, hexafluorophenyl ether, methyl ethyl ketone, and methyl isobutyl ketone; Examples of the organic solvent include non-chlorinated aliphatic hydrocarbon solvents such as benzene and heptane; alicyclic hydrocarbon solvents such as cyclohexane; non-chlorinated aromatic hydrocarbon solvents such as toluene, anisole, trimethylbenzene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran, dioxane and dimethoxyethane; chlorinated solvents such as dichloromethane, dichloroethane, chlorotoluene, chloroform, chlorobenzene and dichlorobenzene; sulfoxide solvents such as dimethyl sulfoxide; amide solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone; and heterocyclic solvents such as pyridine. These organic solvents may be used alone or in combination. Among these organic solvents, ketone solvents, non-chlorinated aliphatic hydrocarbon solvents, non-chlorinated aromatic hydrocarbon solvents and chlorinated solvents are preferred.

[0020] The solvent may be used alone or in combination of two or more. When two or more solvents are used in combination, it is preferable that all the solvents used have a water content of less than 300 ppm, but when a solvent having a water content of 300 ppm or more is included, it is preferable that the water content of the entire solvent is less than 300 ppm.

[0021] The content of the solvent in Agent A is preferably 50 to 99% by mass, more preferably 55 to 98% by mass, and still more preferably 60 to 97% by mass with respect to the total mass of all components contained in Agent A. When the content of the solvent in Agent A is within the above range, it is easy to uniformly dissolve solid components with relatively high viscosity such as reactive additives, and in the method for producing a polarizing film described later, a uniform coating film can be formed, so it is easy to obtain a polarizing film with good appearance.

[0022] Agent A can be prepared by mixing the reactive additive, the solvent, and optionally any components described later. Conditions such as the mixing method, temperature, and time are not particularly limited and can be appropriately selected according to the types and amounts of the components contained in Agent A.

[0023] The viscosity of Agent A (25°C) is preferably 0.1 to 15 mPa·s, more preferably 0.1 to 10 mPa·s. When the viscosity of Agent A is within the above range, it has excellent handleability and is likely to be easily mixed with Agent B later.

[0024] As described above, in the two-component type polarizing film-forming composition of the present invention, the reactive additive is separately blended in Agent A, and an azo dye having an amine structure described later is blended in Agent B. Therefore, Agent A substantially does not contain an azo dye having an amine structure. "Substantially does not contain an azo dye having an amine structure" means that the content of the azo dye having an amine structure in Agent A is preferably less than 0.5 part by mass, more preferably less than 0.1 part by mass, and still more preferably less than 0.05 part by mass with respect to 100 parts by mass of the reactive additive. Preferably, the content of the azo dye having an amine structure in Agent A is 0 part by mass.

[0025] <Agent B> [Dichroic dye] The dichroic dye contained in Agent B contains an azo dye having an amine structure. In the present invention, the amine structure specifically refers to the following formula (1A) [Chemical formula] [In the formula, A a1 and Aa2 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a halogen atom, an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom, an alkylcarbonyl group having 1 to 21 carbon atoms which may have a halogen atom, an alkylcarbonyloxy group having 1 to 21 carbon atoms which may have a halogen atom, an alkylsulfonyl group having 1 to 20 carbon atoms which may have a halogen atom, or an arylsulfonyl group having 6 to 20 carbon atoms which may have a halogen atom, or A a1 and A a2 and are bonded to each other, and together with the nitrogen atom to which they are bonded, form a nitrogen-containing heterocycle such as a pyrrolidine ring. * represents a bond.] Examples of the group include a group represented by the following formula:

[0026] The dichroic dye having an amine structure is, for example, represented by the following general formula (1): [ka] [In the formula, A 1 and A 3 A each independently represents a phenyl group which may have a substituent, a naphthyl group which may have a substituent, a phenyl benzoate group which may have a substituent, or a monovalent heterocyclic group which may have a substituent. 2 represents an optionally substituted 1,4-phenylene group, an optionally substituted naphthalene-1,4-diyl group, an optionally substituted 4,4'-stilbenylene group, or an optionally substituted divalent heterocyclic group, provided that A 1 ~A 3 At least one of the A has an amine structure represented by the above formula (1A) as a substituent. p represents an integer of 0 to 4, and when p is an integer of 2 or more, a plurality of A 2 may be the same or different. Examples of the dyes include those represented by the following formula:

[0027] Examples of the monovalent heterocyclic group include groups in which one hydrogen atom has been removed from a heterocyclic compound such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole, and benzoxazole. Examples of the divalent heterocyclic group include groups in which two hydrogen atoms have been removed from the above heterocyclic compounds.

[0028] A 1 and A 3 Phenyl, naphthyl, benzoic acid phenyl ester and monovalent heterocyclic groups in 2 In the above, examples of the substituent other than the amine structure represented by formula (1A) that the 1,4-phenylene group, naphthalene-1,4-diyl group, 4,4'-stilbenylene group, and divalent heterocyclic group may optionally have include alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and butoxy groups, fluorinated alkyl groups having 1 to 6 carbon atoms such as trifluoromethyl groups, cyano groups, nitro groups, and halogen atoms. Specific examples of the alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, butyl, and hexyl groups.

[0029] Among the dichroic dyes represented by formula (1), the compounds represented by the following formulas (1-1) to (1-8) are preferred.

[0030] [ka]

[0031] [In formulas (1-1) to (1-8), B 1 ~B 3 At least one of B 4 ~B 7 At least one of B 8 ~B 10 At least one of B 11 ~B 12 At least one of B 13 ~B 16 At least one of B 17 ~B 20 At least one of B21 ~B 25 At least one of the following, and B 26 ~B 30 At least one of the B is a substituent of the amine structure represented by the formula (1A). 1 ~B 30 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, a nitro group, a halogen atom, or a trifluoromethyl group. n1 to n4 each independently represent an integer of 0 to 3. If n1 is 2 or more, multiple B 2 may be the same or different, If n2 is 2 or more, multiple B 6 may be the same or different, If n3 is 2 or more, multiple B 9 may be the same or different, If n4 is 2 or more, multiple B 14 may be the same or different.]

[0032] The content of the azo dye having an amine structure contained in the B agent is preferably 1 part by mass or more, preferably 60 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, relative to 100 parts by mass of the polymerizable liquid crystal compound described later. If the content of the dichroic dye having an amine structure is less than the lower limit, the light absorption becomes insufficient and sufficient polarization performance cannot be obtained, and if it exceeds the upper limit, the alignment of the polymerizable liquid crystal may be hindered. The azo dye having an amine structure may be used alone or in combination of two or more kinds. When two or more kinds of azo dyes having an amine structure are used, the content of the azo dyes having an amine structure represents the total amount.

[0033] When the two-liquid type polarizing film-forming composition of the present invention does not contain a polymerizable liquid crystal compound described below, the amount of the azo dye having an amine structure contained in the agent B is 3 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, based on the total amount of the dichroic dyes contained in the agents A and B, and is generally 100 parts by mass or less, preferably 90 parts by mass or less, and more preferably 85 parts by mass or less.

[0034] 〔solvent〕 The solvent contained in the agent B is not particularly limited, but is preferably a solvent that is inactive to an azo dye having an amine structure and can completely dissolve the dye. Since the agent A and the agent B are used in a mixed state, the solvent is preferably highly compatible with the solvent used in the agent A, and may be the same solvent. The solvent contained in the agent B may be used alone or in a mixed state of two or more.

[0035] The content of the solvent in agent B is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and further preferably 70 to 85% by mass, based on the total mass of the components contained in agent B. When the content of the solvent in agent B is within the above range, the dichroic dye is easily dissolved uniformly, and a uniform coating film can be formed in the method for producing a polarizing film described below, making it easy to obtain a polarizing film with good appearance.

[0036] Specific examples of such solvents include alcohol-based solvents such as methanol, ethanol, butanol, ethylene glycol, isopropyl alcohol, 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; pentane, hexafluorophenyl ether, methyl ethyl ketone, and methyl isobutyl ketone; Examples of the organic solvent include non-chlorinated aliphatic hydrocarbon solvents such as benzene and heptane; alicyclic hydrocarbon solvents such as cyclohexane; non-chlorinated aromatic hydrocarbon solvents such as toluene, anisole, trimethylbenzene 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, dimethylacetamide, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone; and heterocyclic solvents such as pyridine. These organic solvents may be used alone or in combination of two or more kinds.

[0037] As described above, in the two-liquid polarizing film-forming composition of the present invention, the reactive additive is separately blended in agent A, and the azo dye having an amine structure is separately blended in agent B. Therefore, agent B does not substantially contain the reactive additive. "Substantially does not contain a reactive additive" means that the content of the reactive additive in agent B is preferably less than 0.5 parts by mass, more preferably less than 0.1 parts by mass, and even more preferably less than 0.05 parts by mass, relative to 100 parts by mass of the azo dye having an amine structure. Preferably, the content of the reactive additive in agent B is 0 parts by mass.

[0038] [Polymerizable liquid crystal compound] The two-liquid type polarizing film-forming composition of the present invention preferably further contains a polymerizable liquid crystal compound. The polymerizable liquid crystal compound may be contained in either Liquid A or Liquid B constituting the two-liquid type polarizing film-forming composition of the present invention.

[0039] The polymerizable liquid crystal compound is a compound having a polymerizable group and exhibiting a liquid crystal state. The polymerizable group means a group involved in the polymerization reaction of the polymerizable liquid crystal compound, and is preferably a photopolymerizable group. Here, the photopolymerizable group means a group that can be involved in the polymerization reaction by an active radical or an acid generated from a photopolymerization initiator described later. Examples of the polymerizable group include 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, and an oxetanyl group. Among them, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group, and an oxetanyl group are preferred, and an acryloyloxy group is more preferred. The liquid crystal property may be a thermotropic liquid crystal or a lyotropic liquid crystal.

[0040] The polymerizable liquid crystal compound may be a thermotropic liquid crystal compound exhibiting a nematic liquid crystal phase, or may be a thermotropic liquid crystal compound exhibiting a smectic liquid crystal phase. In the present invention, the polymerizable liquid crystal compound is preferably a thermotropic liquid crystal compound exhibiting a smectic liquid crystal phase, more preferably a thermotropic liquid crystal compound exhibiting a high-order smectic liquid crystal phase, from the viewpoint of obtaining higher polarization characteristics. Among them, a thermotropic liquid crystal compound exhibiting a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, a smectic K phase, or a smectic L phase is more preferable, and a thermotropic liquid crystal compound exhibiting a smectic B phase, a smectic F phase, or a smectic I phase is even more preferable. When the liquid crystal phase formed by the polymerizable liquid crystal compound is one of these high-order smectic phases, a polarizing film with higher polarization performance can be produced. Furthermore, such a polarizing film with high polarizing performance exhibits Bragg peaks derived from higher-order structures such as hexatic and crystalline phases in X-ray diffraction measurements. The Bragg peaks are peaks derived from the periodic structure of molecular orientation, and a film with a periodic interval of 3 to 6 Å can be obtained.

[0041] Examples of the polymerizable liquid crystal compound include a compound represented by the following formula (2): U 1 -V 1 -W 1 -(X 1 -Y 1 ) n -X 2 -Y 2 -X 3 -W 2 -V 2 -U 2 (2) [In formula (2), X 1 , X 2 , X 3each independently represents a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein a hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, and a carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom. 1 , X 2 , X 3 At least one of the groups is a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent. In addition, n is 1 to 3, and when n is 2 or more, X 1 From the viewpoint of liquid crystallinity, n is preferably 1 or 2. Y 1 , Y 2 , W 1 and W 2 are each independently a single bond or a divalent linking group. V 1 and V 2 each independently represents an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH2- constituting the alkanediyl group may be replaced by -O-, -CO-, -S- or NH-. U 1 and U 2 each independently represents a polymerizable group or a hydrogen atom, and at least one of them is a polymerizable group. (hereinafter, may be referred to as compound (2)). The polymerizable liquid crystal may be used alone or in combination of two or more kinds.

[0042] In compound (2), X 1 , X 2 , X 3 At least one of X is an optionally substituted 1,4-phenylene group or an optionally substituted cyclohexane-1,4-diyl group. 1 Or X 3is preferably a cyclohexane-1,4-diyl group which may have a substituent, and the cyclohexane-1,4-diyl group is more preferably a trans-cyclohexane-1,4-diyl group. Examples of the optional substituent of the 1,4-phenylene group which may have a substituent or the cyclohexane-1,4-diyl group which may have a substituent include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a butyl group, a cyano group, and a halogen atom such as a chlorine atom or a fluorine atom. It is preferably unsubstituted. Also, Y 1 and Y 2 If X is the same structure, 1 , X 2 and X 3 It is preferable that at least one of X has a different structure. 1 , X 2 and X 3 When at least one of the above has a different asymmetric structure, smectic liquid crystallinity tends to be easily exhibited.

[0043] Y 1 and Y 2 are each independently a single bond, -CH2CH2-, -CH2O-, -CH2CH2O-, -COO-, -OCO-, -N=N-, -CR a =CR b -, -C≡C- or -CR a =N- is preferred, R a and R b each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 1 and Y 2 is more preferably -CH2CH2-, -COO-, -OCO-, -N=N- or a single bond. 1 , X 2 and X 3 If all have the same structure, Y 1 and Y 2 It is preferable that Y are different from each other in the bonding mode. 1 and Y 2 When the bonding modes are different from each other, the structure becomes asymmetric, and smectic liquid crystallinity tends to be easily exhibited.

[0044] W 1 and W 2 are preferably, independently of each other, a single bond, -O-, -S-, -COO- or -OCO-, and more preferably, are, independently of each other, a single bond or -O-.

[0045] V 1 and V 2 Examples of the alkanediyl group having 1 to 20 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a decane-1,10-diyl group, a tetradecane-1,14-diyl group, and an icosane-1,20-diyl group. 1 and V 2 is preferably an alkanediyl group having 2 to 12 carbon atoms, and more preferably a linear alkanediyl group having 6 to 12 carbon atoms. By using a linear alkanediyl group having 6 to 12 carbon atoms, crystallinity is improved and smectic liquid crystallinity tends to be easily exhibited. Examples of the substituent that the optionally substituted alkanediyl group having 1 to 20 carbon atoms may have include a cyano group and a halogen atom such as a chlorine atom or a fluorine atom. The alkanediyl group is preferably unsubstituted, and more preferably an unsubstituted and linear alkanediyl group.

[0046] U 1 and U 2 Preferably, both of are polymerizable groups, and more preferably, both are photopolymerizable groups. A polymerizable liquid crystal compound having a photopolymerizable group can be polymerized under a lower temperature condition than a thermally polymerizable group, and is therefore advantageous in that the liquid crystal can form a polymer in a state with a higher degree of order.

[0047] U 1 and U 2The polymerizable groups represented by may be different from each other, but are preferably the same. Examples of the polymerizable group include vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, and oxetanyl group. Among them, acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group, and oxetanyl group are preferred, and methacryloyloxy group or acryloyloxy group is more preferred. In addition, the polymerizable group may be in a polymerized state or an unpolymerized state, but is preferably in an unpolymerized state.

[0048] The polymerizable liquid crystal compound (2) is not particularly limited as long as it has at least one polymerizable group and exhibits smectic liquid crystallinity, and known polymerizable liquid crystal compounds can be used, but as a structure that is likely to exhibit smectic liquid crystallinity, it is preferable that the molecular structure has an asymmetric molecular structure, and more specifically, it is more preferable that the polymerizable liquid crystal compound has the following partial structures (Aa) to (Ai) and exhibits smectic liquid crystallinity. From the viewpoint of easily exhibiting high-order smectic liquid crystallinity, it is more preferable that the polymerizable liquid crystal compound has the partial structure (Aa), (Ab), or (Ac). Here, * in the figure indicates a bond.

[0049] [ka]

[0050] Specific examples of the compound represented by formula (2) include compounds represented by formulas (2-1) to (2-23). ​​When the compound represented by formula (2) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans isomer.

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] Among the compounds represented by formula (2), at least one selected from the group consisting of compounds represented by formulas (2-2), (2-3), (2-4), (2-6), (2-7), (2-8), (2-13), (2-14) and (2-15) is preferred. As the polymerizable liquid crystal compound, one type may be used alone, or two or more types may be used in combination.

[0055] The compound represented by formula (2) can be used alone or in combination. When two or more kinds of polymerizable liquid crystal compounds are combined, it is preferable that at least one of them is a compound represented by formula (2), and it is more preferable that two or more kinds of them are compounds represented by formula (2). When two kinds of polymerizable liquid crystal compounds are combined, the mixing ratio is usually 1:99 to 50:50, preferably 5:95 to 50:50, and more preferably 10:90 to 50:50 (mass ratio). When a polymerizable liquid crystal compound having one polymerizable group and a polymerizable liquid crystal compound having two polymerizable groups are combined, the mixing ratio (polymerizable liquid crystal compound having one polymerizable group:polymerizable liquid crystal compound having two polymerizable groups) is usually 1:99 to 50:50, preferably 5:95 to 50:50, and more preferably 10:90 to 50:50 (mass ratio).

[0056] The compound represented by formula (2) can be produced by a known method, for example, as described in Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996) or Japanese Patent No. 4719156.

[0057] When the two-liquid type polarizing film forming composition of the present invention is contained in agent B, the amount of the polymerizable liquid crystal compound contained therein is preferably 40% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and preferably 99.9% by mass or less, more preferably 99% by mass or less, of the total solid content in agent B. When the content of the polymerizable liquid crystal compound is equal to or more than the lower limit and equal to or less than the upper limit, the alignment tends to be high. Here, the solid content refers to the total amount of components excluding the solvent from the polarizing film forming composition.

[0058] The agent B can be prepared by mixing the azo dye having an amine structure, the solvent, and any optional components described below. The mixing conditions, such as the mixing method, temperature, and time, are not particularly limited and can be appropriately selected depending on the types and amounts of the components contained in the agent B.

[0059] The viscosity (25° C.) of agent B is preferably 0.1 to 15 mPa·s, and more preferably 0.1 to 10 mPa·s. When the viscosity of agent B is within the above range, it is easy to handle and tends to be easily mixed with agent A thereafter.

[0060] The two-liquid type polarizing film-forming composition of the present invention may contain any optional components such as a polymerization initiator, a sensitizer, a polymerization inhibitor, a leveling agent, and a dichroic dye other than an azo dye having an amine structure, in addition to the above-mentioned components.

[0061] [Polymerization initiator] The two-liquid type polarizing film forming composition of the present invention may contain a polymerization initiator. The polymerization initiator is a compound capable of initiating a polymerization reaction of a polymerizable liquid crystal compound, etc. As the polymerization initiator, a photopolymerization initiator that generates active radicals by the action of light is preferable.

[0062] Either or both of the components A and B constituting the two-component type polarizing film-forming composition of the present invention may contain a polymerization initiator. When the component A contains a polymerization initiator, the polymerization initiator is preferably a compound not having an amine structure.

[0063] As the polymerization initiator, a photopolymerization initiator that generates active radicals by the action of light is preferred from the viewpoint of not being dependent on the phase state of the thermotropic liquid crystal. The photopolymerization initiator may be any known photopolymerization initiator as long as it is a compound capable of initiating the polymerization reaction of the polymerizable liquid crystal compound.Specific examples of the photopolymerization initiator include photopolymerization initiators capable of generating active radicals or acids under the action of light, and among these, photopolymerization initiators that generate radicals under the action of light are preferred.The photopolymerization initiators may be used alone or in combination of two or more. As the photopolymerization initiator, a known photopolymerization initiator can be used. For example, as a photopolymerization initiator that generates an active radical, a self-cleavage type benzoin compound, acetophenone compound, hydroxyacetophenone compound, α-aminoacetophenone compound, oxime ester compound, acylphosphine oxide compound, azo compound, etc. can be used, and a hydrogen abstraction type benzophenone compound, alkylphenone compound, benzoin ether compound, benzyl ketal compound, dibenzosuberone compound, anthraquinone compound, xanthone compound, thioxanthone compound, halogenoacetophenone compound, dialkoxyacetophenone compound, halogenobisimidazole compound, halogenotriazine compound, triazine compound, etc. can be used. As a photopolymerization initiator that generates an acid, an iodonium salt and a sulfonium salt can be used. From the viewpoint of excellent reaction efficiency at low temperatures, self-cleavage type photopolymerization initiators are preferred, and in particular, acetophenone-based compounds, hydroxyacetophenone-based compounds, α-aminoacetophenone-based compounds, and oxime ester-based compounds are preferred.

[0064] Examples of the benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0065] Examples of acetophenone compounds include dialkoxyacetophenone compounds such as diethoxyacetophenone; hydroxyacetophenone compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one; and α-aminoacetophenone compounds such as 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one and 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one.

[0066] Examples of oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), and the like.

[0067] Examples of the acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0068] Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone.

[0069] Examples of alkylphenone compounds include diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one.

[0070] Examples of triazine compounds include 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, and 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine. 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

[0071] Commercially available polymerization initiators can be used. Commercially available polymerization initiators include Irgacure (registered trademark) 907, 184, 651, 819, 250 and 369 (manufactured by Chiba Specialty Chemicals Co., Ltd.); Seikuol (registered trademark) BZ, Z and BEE (manufactured by Seiko Chemical Co., Ltd.); Kayacure (registered trademark) BP100 and UVI-6992 (manufactured by Dow Chemical Co., Ltd.); Adeka Optomer SP-152 and SP-170 (manufactured by ADEKA Corporation); TAZ-A and TAZ-PP (manufactured by Nippon SiberHegner Co., Ltd.); and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.). The polymerization initiator may be one type, or two or more types of polymerization initiators may be mixed according to the light source.

[0072] The content of the polymerization initiator can be appropriately adjusted depending on the type and amount of the polymerizable liquid crystal compound, but is usually 0.1 to 30 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. When the content of the polymerization initiator is within the above range, polymerization is easily performed without disturbing the alignment of the polymerizable liquid crystal.

[0073] [Sensitizer] When the two-liquid type polarizing film forming composition of the present invention contains a polymerizable liquid crystal compound, the composition may contain a sensitizer. One or both of the A and B components constituting the two-liquid type polarizing film forming composition of the present invention may contain a sensitizer, but when the A component contains a sensitizer, the sensitizer is preferably a compound that does not have an amine structure. The sensitizer is preferably a photosensitizer. Examples of the sensitizer include xanthone compounds such as xanthone and thioxanthone (e.g., 2,4-diethylthioxanthone, 2-isopropylthioxanthone, etc.); anthracene compounds such as anthracene and an alkoxy group-containing anthracene (e.g., dibutoxyanthracene, etc.); phenothiazine, rubrene, etc.

[0074] The content of the sensitizer 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 polymerizable liquid crystal compound. When the content of the sensitizer is within the above range, the polymerization reaction of the polymerizable liquid crystal compound is easily promoted.

[0075] [Polymerization inhibitor] When the two-liquid type polarizing film forming composition of the present invention contains a polymerizable liquid crystal compound, the composition may contain a polymerization inhibitor from the viewpoint of stably progressing the polymerization reaction. Either or both of the components A and B constituting the two-liquid type polarizing film forming composition of the present invention may contain a polymerization inhibitor, but when the component A contains a polymerization inhibitor, it is preferable that the polymerization inhibitor is a compound that does not have an amine structure. The polymerization inhibitor can control the degree of progress of the polymerization reaction.

[0076] Examples of the polymerization inhibitor include radical scavengers such as hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (e.g., butylcatechol, etc.), pyrogallol, and 2,2,6,6-tetramethyl-1-piperidinyloxy radical; thiophenols; β-naphthylamines, and β-naphthols.

[0077] When the two-liquid type polarizing film-forming 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 polymerizable liquid crystal compound. When the content of the polymerization inhibitor is within the above range, polymerization is easily carried out without disturbing the alignment of the polymerizable liquid crystal.

[0078] [Leveling Agent] The two-liquid type polarizing film-forming composition of the present invention may contain a leveling agent. The leveling agent has a function of adjusting the fluidity of the composition and making the film obtained by applying the composition flatter, and an example of such a leveling agent is a surfactant. Either or both of the components A and B constituting the two-liquid type polarizing film-forming composition of the present invention may contain a leveling agent, but when the component A contains a leveling agent, the leveling agent is preferably a compound not having an amine structure.

[0079] Examples of the leveling agent include organic modified silicone oil-based, polyacrylate-based and perfluoroalkyl-based leveling agents. Specific examples include DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all manufactured by Toray Dow Corning Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all manufactured by Momentive Performance Materials Co., Ltd.). Japan LLC), Fluorinert (registered trademark) FC-72, FC-40, FC-43, FC-3283 (all manufactured by Sumitomo 3M Limited), Megafac (registered trademark) R-08, R-30, R-90, F-410, F-411, F-443, F-445, F-470, F-477, F-479, F-482, F-483 (all manufactured by DIC Corporation), F-top (trade name) EF301, EF303, EF351, EF352 (all manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S-381, S-382, S-383, S-393, SC-101, SC-105, KH-40, SA-100 (all manufactured by AGC Seimi Chemical Co., Ltd.), trade names E1830, E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.), BM-1000, BM-1100, BYK-352, BYK-353 and BYK-361N (all trade names: manufactured by BM Chemie Co., Ltd.), etc. Among them, polyacrylate-based leveling agents and perfluoroalkyl-based leveling agents are preferred.

[0080] When the two-liquid type polarizing film forming composition of the present invention contains a leveling agent, the amount is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, based on the total solid content of the two-liquid type polarizing film forming composition. When the content of the leveling agent is within the above range, when a polymerizable liquid crystal compound is contained, the polymerizable liquid crystal is easily horizontally aligned, and the obtained polarizing film tends to be smoother. When the content of the leveling agent exceeds the above range, the obtained polarizing film tends to be easily uneven. Note that two or more kinds of leveling agents may be contained.

[0081] [Dichroic dyes other than azo dyes having an amine structure] The two-liquid polarizing film-forming composition of the present invention may contain a dichroic dye other than the azo dye having an amine structure. Such a dichroic dye preferably has a maximum absorption wavelength (λMAX) in the range of 300 to 700 nm, and examples thereof include azo dyes not having an amine structure, anthraquinone dyes, oxazine dyes, acridine dyes, cyanine dyes, naphthalene dyes, and the like. The dichroic dyes other than the azo dye having an amine structure may be used alone or in combination of two or more kinds.

[0082] As an azo dye having no amine structure, for example, A 1 ~A 3 The substituent of the formula (I) does not contain an amine structure.

[0083] The anthraquinone dye may be represented by the formula (1-9): [ka] [In the formula, R 1 ~R 8 are each independently a hydrogen atom, -R x , -NH2, -NHR x , -NR x 2, -SR x or a halogen atom, R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. Preferred is a compound represented by the following formula:

[0084] The oxazine dye may be represented by the formula (1-10): [ka] [In the formula, R 9 ~R 15 are each independently a hydrogen atom, -R x , -NH2, -NHR x , -NR x 2, -SR x or a halogen atom, R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. Preferred is a compound represented by the following formula:

[0085] The acridine dye may be represented by the formula (1-11): [ka] [In the formula, R 16 ~R 23 are each independently a hydrogen atom, -R x , -NH2, -NHR x , -NR x 2, -SR x or a halogen atom, R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. Preferred is a compound represented by the following formula:

[0086] R in formula (1-9), formula (1-10) and formula (1-11) x Examples of the alkyl group having 1 to 4 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a toluyl group, a xylyl group, and a naphthyl group.

[0087] As the cyanine dye, there may be mentioned a dye represented by the formula (1-12): [ka] [In the formula, D 1 and D. 2are each independently represented by formula (1-12a) to formula (1-12d) [ka] and n5 represents an integer of 1 to 3. and compounds represented by formula (1-13) [ka] [In the formula, D 3 and D. 4 are independently represented by formula (2-13a) to formula (2-13h) [ka] and n6 represents an integer of 1 to 3. Preferred is a compound represented by the following formula:

[0088] When the above-mentioned azo dye having an amine structure and a dichroic dye other than the azo dye having an amine structure are used in combination, the total content of all dichroic dyes is usually 1 to 60 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 polymerizable liquid crystal compound. If the total content of the dichroic dyes is within the above range, the polymerizable liquid crystal compound can be polymerized without disturbing its alignment. If the content of the dichroic dye is too small, the light absorption becomes insufficient and sufficient polarization performance cannot be obtained, and if the content is too large, the alignment of the polymerizable liquid crystal compound may be hindered. Therefore, the content of the dichroic dye can be determined within a range in which the polymerizable liquid crystal compound can maintain a liquid crystal state.

[0089] <Storage method> When storing the two-liquid type polarizing film-forming composition of the present invention, the agent A and the agent B are stored separately. For example, the agent A and the agent B are stored in two independent containers, respectively, or the agent A and the agent B are stored in one container having a partition therebetween so that the two agents do not mix during storage. In the present invention, the agent A and the agent B are preferably stored in two independent containers.

[0090] Examples of the container for storing the agent A include plastic containers, metal containers, and glass containers, and it is preferable that the container for storing the agent A is a plastic container or a metal container. If the container for storing the agent A is a plastic container or a metal container, it is preferable because side reactions of the reactive additives in the agent A are unlikely to occur. Examples of the material of the plastic container include, but are not limited to, polypropylene, polyethylene, norbornene-based polymers, polystyrene, polyamide, poly(4-methylpentene-1), acrylic resin, polyvinyl alcohol, acrylonitrile-butadiene-styrene copolymer, polymethacrylic acid ester, polyacrylic acid ester, cellulose ester, polycarbonate, polyethylene terephthalate, polysulfone, polyethersulfone, polyetherketone, polyethylene naphthalate, polyphenylene sulfide, polyphenylene oxide, cyclic polyolefins such as cyclic olefin polymers or cyclic olefin copolymers, polyolefins such as amorphous polyarylate, polyester, Teflon, etc. Examples of the material of the metal container include, but are not limited to, steel such as SUS, tinplate, aluminum, etc. When the container for storing the agent A is a plastic container, it is preferable that the container is a light-shielding plastic container (for example, a brown plastic container) since it is less susceptible to the effects of ultraviolet rays, etc., which may cause deterioration of the composition. In addition, the outer surface of the container may be coated.

[0091] The container for storing the agent B is not particularly limited, and examples of the material of the container include plastic, metal, glass, etc. The container for storing the agent B is preferably a light-shielding container as described above.

[0092] The shape of the container for storing the agent A and the agent B is not particularly limited. For example, it may be a hexahedral shape such as a 18L can or a plastic tank, or a cylindrical shape such as a pail or a hanging can. The capacity of the agent A and the agent B is also not particularly limited, and a desired amount can be stored in the container.

[0093] When storing the agent A, it is preferable to store the agent A under a dry inert gas atmosphere. In this specification, the dry gas generally refers to a gas having a dew point of -50°C or less, and the inert gas refers to a gas having low reactivity, such as nitrogen, argon, or helium. Examples of storing the agent A under a dry inert gas atmosphere include a mode in which the gas phase in a storage container is filled with a dry inert gas and then sealed for storage, and a mode in which the storage container itself is stored in a space filled with a dry inert gas. By storing the agent A under a dry inert gas atmosphere, side reactions between moisture in the surrounding atmosphere and the active hydrogen reactive groups of the reactive additive in the agent A can be avoided, so that the adhesion of the polarizing film obtained from the two-liquid polarizing film-forming composition of the present invention is easily increased, and the optical performance after long-term storage is easily improved.

[0094] The atmosphere in which agent B is stored is not particularly limited, but it is preferable to store it in a dry inert gas atmosphere.

[0095] The filling amounts of agents A and B relative to the volume of a container for storage are not particularly limited, but the filling amounts of agents A and B are usually 30% or more, and preferably 50% or more, of the volume of the storage container, and from the viewpoint of ease of handling during mixing, are usually 90% or less.

[0096] The temperature at which agents A and B are stored is not particularly limited. However, if the temperature is too high, a polymerization reaction of the polymerizable liquid crystal compound may be initiated, whereas if the temperature is too low, the solid content in agents A and B may precipitate. Therefore, the storage temperature is usually 0 to 50°C, preferably 10 to 40°C, and more preferably 15 to 35°C.

[0097] If the components A and B are stored in a mixed state for about three months, it may be difficult to produce a polarizing film having good optical performance. The two-liquid type polarizing film-forming composition of the present invention is advantageous in that a polarizing film having good optical performance can be obtained even after such long-term storage (e.g., three months or more). The storage period of the components A and B is not particularly limited, but is usually within three years.

[0098] The two-liquid type polarizing film-forming composition of the present invention can obtain a polarizing film having good optical performance even after long-term storage by separately storing the reactive additive and the dichroic dye containing an azo dye having an amine structure as described above. As a result of the inventors' investigation into this matter, they found that in a polarizing film obtained from a polarizing film-forming composition in which a reactive additive and, among dichroic dyes, an azo dye having an amine structure are stored together for a certain period of time (e.g., 3 months), the molecular orientation of the liquid crystal compound in the polarizing film is easily disturbed (i.e., the liquid crystal compound is no longer aligned in one direction), and the optical properties of the obtained polarizing film tend to be deteriorated.

[0099] <Method of manufacturing the composition for forming a polarizing film> In the present invention, the composition for forming a polarizing film can be obtained by mixing the components A and B constituting the two-liquid type composition for forming a polarizing film. In this specification, the term "two-liquid type composition for forming a polarizing film" refers to a composition in which the components A and B constituting the two-liquid type composition for forming a polarizing film are in a separate state, and a composition in which the components A and B are in a mixed state is referred to as the "composition for forming a polarizing film."

[0100] The timing of mixing the components A and B of the two-component polarizing film-forming composition of the present invention is not limited as long as the timing is within a period during which the reaction between the reactive additive and the azo dye having an amine structure does not proceed, and may be appropriately determined depending on the types and amounts of the reactive additive and the azo dye having an amine structure contained therein, the mixing conditions, the environment, etc.

[0101] The method for mixing the components A and B is not particularly limited, and any known mixing method can be used. For example, a mixing method using a mixing device having stirring blades such as a planetary mixer or a kneader mixer, or a static mixing method using a static mixer or the like can be used.

[0102] The ambient temperature when mixing the A and B components is not particularly limited, but is preferably 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. The mixing is usually carried out under normal pressure (atmospheric pressure).

[0103] The mixing time is not particularly limited and can be appropriately adjusted depending on the types and amounts of the components contained in the two-liquid type polarizing film-forming composition. The mixing time is usually 0.5 to 12 hours, preferably 0.5 to 6 hours.

[0104] <Method of manufacturing polarizing film> The method for producing the polarizing film of the present invention comprises the steps of: A step of forming an alignment film on a substrate; A step of mixing an A component, which comprises a reactive additive having a polymerizable group and an active hydrogen-reactive group in the molecule and a solvent, with a B component, which comprises a dichroic dye including an azo dye having an amine structure and a solvent, to obtain a polarizing film-forming composition; A step of applying the mixed composition for forming a polarizing film onto the alignment film to obtain a coating film; and A step of curing the coating film Includes.

[0105] [Base material] The substrate used for forming the polarizing film includes a glass substrate and a plastic substrate. A plastic substrate is preferable to a glass substrate because it can be processed by roll-to-roll processing and has high productivity. Examples of plastics constituting the plastic substrate include polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid esters; polyacrylic acid esters; cellulose esters such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyether sulfone; polyether ketone; polyphenylene sulfide, and polyphenylene oxide.

[0106] Examples of commercially available cellulose ester substrates include "FUJITAC FILM" (manufactured by Fuji Photo Film Co., Ltd.); "KC8UX2M", "KC8UY" and "KC4UY" (all manufactured by Konica Minolta Opto, Inc.).

[0107] Examples of commercially available cyclic olefin resins include "Topas" (registered trademark) (manufactured by Ticona, Germany), "Arton" (registered trademark) (manufactured by JSR Corporation), "ZEONOR" (registered trademark), "ZEONEX" (registered trademark) (all manufactured by Zeon Corporation), and "Apel" (registered trademark) (manufactured by Mitsui Chemicals, Inc.). Such cyclic olefin resins can be formed into a film by known means such as a solvent casting method or a melt extrusion method to form a substrate. Commercially available cyclic olefin resin substrates can also be used. Examples of commercially available cyclic olefin resin substrates include "S-Cina" (registered trademark), "SCA40" (registered trademark) (all manufactured by Sekisui Chemical Co., Ltd.), "ZEONOR Film" (registered trademark) (manufactured by Optes Co., Ltd.), and "Arton Film" (registered trademark) (manufactured by JSR Corporation).

[0108] A polarizing plate can be obtained from the polarizing film of the present invention and a substrate. The substrate is preferably thin in terms of the mass that can be practically handled, but if it is too thin, the strength decreases and the processability tends to be poor. The thickness of the substrate is usually 5 to 300 μm, and preferably 20 to 200 μm. In addition, since it is possible to apply only the polarizing film of the present invention by peeling off the substrate and transferring the polymer of the polymerizable liquid crystal compound containing a dichroic dye, a further thinning effect can be obtained.

[0109] [Alignment film] In the present invention, the alignment film is a film made of a polymer compound, and has an alignment regulating force for aligning a polymerizable liquid crystal compound in a desired direction.

[0110] The alignment film facilitates the alignment of the polymerizable liquid crystal compound. The state of liquid crystal alignment, such as horizontal alignment, vertical alignment, hybrid alignment, and tilt alignment, varies depending on the properties of the alignment film and the polymerizable liquid crystal compound, and the combination can be selected arbitrarily. For example, if the alignment film is a material that exerts horizontal alignment as an alignment control force, the polymerizable liquid crystal compound can form a horizontal alignment or a hybrid alignment, and if the alignment film is a material that exerts vertical alignment, the polymerizable liquid crystal compound can form a vertical alignment or a tilt alignment. The expressions horizontal, vertical, and the like indicate the direction of the long axis of the aligned polymerizable liquid crystal when the polarizing film plane is used as a reference. Horizontal alignment is an alignment in which the long axis of the aligned polymerizable liquid crystal is parallel to the polarizing film plane. Here, "parallel" means an angle of 0°±20° with respect to the polarizing film plane. Vertical alignment is an alignment in which the long axis of the aligned polymerizable liquid crystal is perpendicular to the polarizing film plane. Here, vertical means 90°±20° with respect to the polarizing film plane.

[0111] When the alignment film is made of an alignment polymer, the alignment regulating force can be arbitrarily adjusted by the surface state or rubbing conditions, and when it is made of a photoalignment polymer, the alignment regulating force can be arbitrarily adjusted by the polarized light irradiation conditions, etc. In addition, the liquid crystal alignment can be controlled by selecting the physical properties, such as the surface tension and liquid crystallinity, of the polymerizable liquid crystal compound.

[0112] The alignment film is preferably insoluble in a solvent used when forming a polarizing film on the alignment film, and has heat resistance in a heat treatment for removing the solvent and for orienting the liquid crystal. Examples of the alignment film include an alignment film made of an orienting polymer, a photoalignment film, a groove alignment film, and a stretched film stretched in the alignment direction, and is preferably a photoalignment film.

[0113] The thickness of the alignment film is usually in the range of 10 to 5000 nm, preferably in the range of 10 to 1000 nm, and more preferably in the range of 30 to 300 nm.

[0114] Examples of the oriented polymer include polyamides and gelatins having an amide bond in the molecule, polyimides having an imide bond in the molecule, and their hydrolyzates such as polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylic acid esters. Among these, polyvinyl alcohol is preferred. These oriented polymers may be used alone or in combination of two or more.

[0115] An alignment film made of an alignment polymer is usually obtained by applying a composition in which an alignment polymer is dissolved in a solvent (hereinafter also referred to as an "alignment polymer composition") to a substrate and removing the solvent, or by applying an alignment polymer composition to a substrate, removing the solvent, and rubbing the substrate (rubbing method).

[0116] Examples of the solvent include water; alcohol-based solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ester-based solvents such as 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; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; aromatic hydrocarbon solvents such as toluene and xylene, and nitrile-based solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; and chlorine-substituted hydrocarbon solvents such as chloroform and chlorobenzene. These solvents may be used alone or in combination of two or more.

[0117] The concentration of the orienting polymer in the orienting polymer composition may be within a range in which the orienting polymer can be completely dissolved in the solvent, and is preferably 0.1 to 20 mass %, more preferably 0.1 to 10 mass %, calculated as solid content relative to the solution.

[0118] As the oriented polymer composition, a commercially available alignment film material may be used as it is. Examples of commercially available alignment film materials include Sunever (registered trademark) (manufactured by Nissan Chemical Industries, Ltd.) and Optomer (registered trademark) (manufactured by JSR Corporation).

[0119] Examples of a method for applying the oriented polymer composition to a substrate include known methods such as spin coating, extrusion, gravure coating, die coating, bar coating, and applicator methods, and printing methods such as flexography. When the oriented film of the present invention is produced by a roll-to-roll continuous production method, the coating method usually employs a printing method such as gravure coating, die coating, or flexography.

[0120] The solvent contained in the oriented polymer composition is removed to form a dry coating film of the oriented polymer. Methods for removing the solvent include natural drying, forced air drying, heat drying, and reduced pressure drying.

[0121] An example of a rubbing method is to bring an oriented polymer film formed on the surface of a substrate by applying an oriented polymer composition to the substrate and annealing the composition into contact with a rotating rubbing roll wrapped with a rubbing cloth.

[0122] The photo-alignment film is usually made of a polymer, oligomer or monomer having a photoreactive group. When polymerizable liquid crystal is continuously formed, a polymer having a molecular weight of 5000 or more is preferred from the viewpoint of solvent resistance, and when the polymerizable liquid crystal is a (meth)acryloyl group, an acrylic polymer is preferred from the viewpoint of affinity. The photo-alignment film is obtained by applying a composition containing a polymer, oligomer or monomer having a photoreactive group and a solvent (hereinafter also referred to as a "photo-alignment film forming composition") to a substrate, drying and removing the solvent, and then irradiating with polarized light (preferably polarized UV). The photo-alignment film is more preferable in that the direction of the alignment regulating force can be arbitrarily controlled by selecting the polarization direction of the irradiated polarized light.

[0123] The photoreactive group refers to a group that generates liquid crystal alignment ability by irradiation with light. Specifically, it is a group that generates a photoreaction that is the origin of liquid crystal alignment ability, such as molecular alignment induction or isomerization reaction, dimerization reaction, photocrosslinking reaction, or photodecomposition reaction, which occurs by irradiation with light. Among the photoreactive groups, those that cause a dimerization reaction or a photocrosslinking reaction are preferred in terms of excellent alignment ability. As the photoreactive group that can generate the above-mentioned reaction, those having an unsaturated bond, particularly a double bond, are preferred, and groups having at least one selected from the group consisting of a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), a nitrogen-nitrogen double bond (N=N bond), and a carbon-oxygen double bond (C=O bond) are more preferred.

[0124] Examples of photoreactive groups having a C=C bond include vinyl groups, polyene groups, stilbene groups, stilbazolyl groups, stilbazolium groups, chalcone groups, and cinnamoyl groups. Examples of photoreactive groups having a C=N bond include groups having structures such as aromatic Schiff bases and aromatic hydrazones. Examples of photoreactive groups having an N=N bond include azobenzene groups, azonaphthalene groups, aromatic heterocyclic azo groups, bisazo groups, and formazan groups, as well as groups having an azoxybenzene as a basic structure. Examples of photoreactive groups having a C=O bond include benzophenone groups, coumarin groups, anthraquinone groups, and maleimide groups. These groups may have substituents such as alkyl groups, alkoxy groups, aryl groups, allyloxy groups, cyano groups, alkoxycarbonyl groups, hydroxyl groups, sulfonic acid groups, and halogenated alkyl groups.

[0125] The solvent for the composition for forming a photo-alignment film is preferably one that dissolves the polymer and monomer having a photoreactive group, and examples of the solvent include the solvents exemplified above as the solvent for the alignment polymer composition.

[0126] The content of the polymer or monomer having a photoreactive group in the composition for forming a photo-alignment film can be appropriately adjusted depending on the type of the polymer or monomer having a photoreactive group and the thickness of the photo-alignment film to be produced, but is preferably 0.2 mass% or more, and more preferably in the range of 0.3 to 10 mass%. In addition, polymer materials such as polyvinyl alcohol and polyimide and photosensitizers may be contained within a range that does not significantly impair the properties of the photo-alignment film.

[0127] The method for applying the composition for forming a photo-alignment film to the diffusion prevention layer may be the same as the method for applying the orientation polymer composition to the diffusion prevention layer. The method for removing the solvent from the applied composition for forming a photo-alignment film may be the same as the method for removing the solvent from the orientation polymer composition.

[0128] The polarized light may be irradiated directly onto the composition for forming a photo-aligned film coated on a substrate from which the solvent has been removed, or may be irradiated from the substrate and then transmitted through the substrate. In addition, it is particularly preferable that the polarized light is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably in a wavelength range in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) having a wavelength of 250 to 400 nm is particularly preferable. Examples of light sources used for the polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and ultraviolet lasers such as KrF and ArF, and high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are more preferable. These lamps are preferable because they have a high emission intensity of ultraviolet light with a wavelength of 313 nm. The light from the light source can be irradiated through an appropriate polarizer to irradiate the polarized light. As such a polarizer, a polarizing filter, a polarizing prism such as Glan-Thompson or Glan-Taylor, or a wire grid type polarizer can be used.

[0129] If masking is performed during rubbing or polarized light irradiation, a plurality of regions (patterns) in which the liquid crystal alignment directions are different can be formed.

[0130] A groove alignment film is a film that has a concave-convex pattern or multiple grooves on the film surface. When liquid crystal molecules are placed on a film that has multiple equally spaced linear grooves, the liquid crystal molecules are oriented in the direction along the grooves.

[0131] Methods for obtaining a groove alignment film include a method of forming a concave-convex pattern by exposing a photosensitive polyimide film surface through an exposure mask having slits in a pattern shape, developing and rinsing the film, forming a layer of UV-curable resin before curing on a plate-shaped master having grooves on the surface, transferring the resin layer to a substrate and curing the resin, and pressing a roll-shaped master having a plurality of grooves against a film of UV-curable resin before curing formed on a substrate to form concave-convex patterns, followed by curing the film, etc. Specific examples of the method include the methods described in JP-A-6-34976 and JP-A-2011-242743.

[0132] In order to obtain an alignment with little alignment disturbance, the width of the convex parts of the groove alignment film is preferably 0.05 to 5 μm, the width of the concave parts is preferably 0.1 to 5 μm, and the depth of the unevenness is preferably 2 μm or less, more preferably 0.01 to 1 μm or less.

[0133] [Polarizing film] The composition for forming a polarizing film is applied onto the alignment film obtained as described above to form a coating film, and then the solvent contained in the composition for forming a polarizing film is removed under conditions in which the polymerizable liquid crystal is not polymerized, thereby forming a dry coating film of the composition for forming a polarizing film on the surface of the substrate. Examples of methods for removing the solvent include natural drying, ventilation drying, heat drying, and reduced pressure drying.

[0134] The dried coating film is heated or the like to orient the polymerizable liquid crystal compound contained in the dried coating film into a liquid crystal orientation, particularly into a smectic phase state, and then the polymerizable liquid crystal compound is polymerized by irradiating the dried coating film with energy while maintaining the liquid crystal orientation. When the polarizing film-forming composition contains a polymerization initiator, it is preferable to irradiate with energy under conditions that activate the polymerization initiator. When the polymerization initiator is a photopolymerization initiator, the energy is preferably light. The light to be irradiated is appropriately selected depending on the type of polymerization initiator contained in the dried coating film, or the type and amount of polymerizable liquid crystal (particularly, the type of polymerizable group possessed by the polymerizable liquid crystal compound).

[0135] Examples of such light include light selected from the group consisting of visible light, ultraviolet light, and laser light, and active electron beams. Among them, ultraviolet light is preferred because it is easy to control the progress of the polymerization reaction and because polymerization equipment widely used in the field can be used. Therefore, it is preferable to select the types of polymerizable liquid crystal compound and polymerization initiator contained in the composition for forming a polarizing film so that the composition can be polymerized by ultraviolet light. In addition, when polymerizing the composition, it is preferable to control the polymerization temperature by cooling the dried coating film with an appropriate cooling means together with the irradiation of ultraviolet light. If the polymerizable liquid crystal compound is polymerized at a lower temperature by such cooling, a polarizing film can be appropriately produced even if a substrate having low heat resistance is used. EXAMPLES

[0136] The present invention will now be described in more detail with reference to the following examples. In the examples, "%" and "parts" mean "% by mass" and "parts by mass", respectively, unless otherwise specified.

[0137] <Example 1> [Preparation of composition for forming photoalignment film] The following components described in JP 2013-033249 A were mixed, and the resulting mixture was stirred at 80° C. for 1 hour to obtain a composition for forming a photoalignment film. JPEG0007603396000015.jpg37139

[0138] [Preparation of agent A] The following components were mixed and stirred at 25° C. for 1 hour to obtain Agent A (1). The water content of orthoxylene used as the solvent was <100 ppm. JPEG0007603396000016.jpg21143The prepared agent A (1) was placed in a stainless steel can, and the gas phase was replaced with dry nitrogen and sealed.

[0139] [Preparation of agent B] The following components were mixed and stirred at 80° C. for 1 hour to obtain agent B (1). The dichroic dye used was the azo dye described in the examples of JP 2013-101328 A. The water content of the orthoxylene used as the solvent was <100 ppm. The prepared B agent (1) was placed in a stainless steel can, the gas phase of which was replaced with dry nitrogen, and the can was sealed.

[0140] <How to make a polarizing film> (1) Formation of photo-alignment film A triacetyl cellulose film (KC8UX2M, manufactured by Konica Minolta, Inc.) was used as the substrate, and the film surface was subjected to a corona treatment, after which the composition for forming a photo-alignment film was applied and dried at 120°C to obtain a dry coating film. Polarized UV was irradiated onto this dry coating film to form a photo-alignment film, and a film with a photo-alignment film was obtained. The polarized UV treatment was carried out using a UV irradiation device (SPOT CURE SP-7, manufactured by Ushio Inc.) with an intensity of 100 mJ / cm2 measured at a wavelength of 365 nm. 2 In this manner, a film with a photo-alignment film was obtained.

[0141] (2) Formation of polarizing film After preparing the A agent (1) and the B agent (1), they were stored at 25°C for 3 months, and then the A agent (1) and the B agent (1) were mixed and stirred at 25°C for 1 hour to obtain a composition for forming a polarizing film (1). Immediately after obtaining the composition for forming a polarizing film (1), the composition for forming a polarizing film (1) was applied by a bar coating method onto the film with the photoalignment film obtained above, and then the film was heated and dried in a drying oven at 120°C for 1 minute to thoroughly remove the solvent, and then cooled to room temperature to cause a phase transition of the polymerizable liquid crystal compound to a smectic liquid crystal state. Next, a UV irradiation device (Unicure VB-15201BY-A; manufactured by Ushio Inc.) was used to apply an exposure dose of 1000 mJ / cm2. 2By irradiating a layer formed from the polarizing film-forming composition (1) with ultraviolet light of 365 nm (standard wavelength), the polymerizable liquid crystal compound contained in the dried coating film was polymerized while maintaining the smectic liquid crystal state of the polymerizable liquid crystal compound, and a polarizing film (1) was formed from the dried coating film. The thickness of the polarizing film (1) was measured with a laser microscope (OLS3000 manufactured by Olympus Corporation) and found to be 2.3 μm. Thus, a polarizer (polarizing film laminate) containing a polarizing film and a substrate was obtained. X-ray diffraction measurement was performed on the polarizing film (1) using an X-ray diffraction device X'Pert PRO MPD (manufactured by Spectris Inc.). As a result, a sharp diffraction peak (Bragg peak) with a peak half-width (FWHM) of about 0.17° was obtained near 2θ=20.2°. Similar results were also obtained with incidence perpendicular to the rubbing direction. The order period (d) calculated from the peak position was about 4.4 Å, and it was confirmed that a structure reflecting a high-order smectic phase was formed.

[0142] <Moisture content measurement> The water content of the solvent was measured by coulometric titration using a Karl Fischer moisture meter (MKC-710M, manufactured by Kyoto Electronics Manufacturing Co., Ltd.).

[0143] <Measurement of polarization degree Py and single unit transmittance Ty> The polarization degree Py and single transmittance Ty of the polarizing film (1) were measured as follows. The transmittance (Ta1) in the transmission axis direction and the transmittance (Tb2) in the absorption axis direction in the wavelength range of 380 nm to 780 nm were measured by the double beam method using a spectrophotometer (Shimadzu Corporation UV-3150) equipped with a folder with a polarizer. The reference side of the folder was equipped with a mesh that cuts the amount of light by 50%. Using the following formulas (Formula 1) and (Formula 2), the single transmittance and the degree of polarization at each wavelength were calculated, and then luminosity correction was performed using a 2-degree visual field (C light source) according to JIS Z 8701 to calculate the luminosity-corrected single transmittance (Ty) and luminosity-corrected degree of polarization (Py). As a result, Ty=42% and Py=98%, indicating high performance derived from the highly aligned smectic liquid crystal. Single transmittance Ty(%)= (Ta1+Tb2) / 2 (Equation 1) Degree of polarization Py(%)= (Ta1-Tb2) / (Ta1+Tb2)×100 (Equation 2)

[0144] <Evaluation of Adhesion> A 25 mm wide cellophane tape (manufactured by Nichiban) was attached to the front and back of the obtained polarizing film (1), and a 90° peel test was performed on the front and back of each film. The film was rated as ◯ when no peeling occurred, △ when peeling occurred only in a part of the test area, and × when peeling occurred over the entire test area.

[0145] <Appearance evaluation> The polarizing film (1) thus obtained was visually inspected for the presence or absence of foreign matter. The film was rated ◯ when no foreign matter was found, △ when some foreign matter was found, and × when many foreign matter was found.

[0146] <Examples 2 and 3> Except for using a storage container for the agent A as shown in the table, polarizing film-forming compositions (2) and (3) and polarizing films (2) and (3) were obtained in the same manner as in Example 1. The Py, Ty, adhesion, and appearance of the obtained polarizing films were evaluated in the same manner as in Example 1.

[0147] <Example 4> A polarizing film-forming composition (4) and a polarizing film (4) were obtained in the same manner as in Example 1, except that the gas phase of the container storing the agent A was air. The Py, Ty, adhesion, and appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

[0148] <Example 5> A polarizing film-forming composition (5) and a polarizing film (5) were obtained in the same manner as in Example 1, except that the following compound was used as a reactive additive. The Py, Ty, adhesion, and appearance of the obtained polarizing film were evaluated in the same manner as in Example 1. Reactive additive: Karenz AOI (Showa Denko K.K.) 2.0 parts

[0149] <Example 6> A polarizing film-forming composition (6) and a polarizing film (6) were obtained in the same manner as in Example 1, except that the following compound was used as a reactive additive. The Py, Ty, adhesion, and appearance of the obtained polarizing film were evaluated in the same manner as in Example 1. Reactive additive: KBM-5103 (Shin-Etsu Chemical Co., Ltd.) 5.0 parts

[0150] <Examples 7 and 8> Polarizing film-forming compositions (7) and (8) and polarizing films (7) and (8) were obtained in the same manner as in Example 1, except that the solvent for agent A was as shown in the table. The water content of the toluene used was <100 ppm, and the water content of the anisole was 250 ppm. The Py, Ty, adhesion, and appearance of the obtained polarizing films were evaluated in the same manner as in Example 1.

[0151] <Examples 9 to 12> Polarizing film-forming compositions (9) to (12) and polarizing films (9) to (12) were obtained in the same manner as in Example 1, except that the solvent for agent B was as shown in the table. The water content of each solvent used was dipropylene glycol dimethyl ether: 800 ppm, diethylene glycol monomethyl ether acetate: 1000 ppm, γ-butyrolactone (GBL): 300 ppm, and isophorone: 800 ppm. The Py, Ty, adhesion, and appearance of the obtained polarizing films were evaluated in the same manner as in Example 1.

[0152] <Example 13> Except for the amount of the dichroic dye added being as shown in the table, a polarizing film-forming composition (13) and a polarizing film (13) were obtained in the same manner as in Example 1. The Py, Ty, adhesion, and appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

[0153] <Example 14> A polarizing film-forming composition (14) and a polarizing film (14) were obtained in the same manner as in Example 1, except that the dichroic dye represented by (1-2) was added to the agent A, and the dichroic dyes represented by (1-1) and (1-3) were added to the agent B. The Py, Ty, adhesion, and appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

[0154] <Comparative Example 1> After preparing agents A and B in the same manner as in Example 1, the two liquids were mixed in a SUS can by stirring for 1 hour at 25° C. After mixing the two liquids, the can was sealed under dry nitrogen and stored at 25° C. for 3 months, after which coating was performed. The Py, Ty, adhesion, and appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

[0155] <Comparative Example 2> A composition for forming a polarizing film was prepared in the same manner as in Comparative Example 1 except that no reactive additive was used, and the composition was sealed under dry nitrogen and stored at 25°C for 3 months, after which coating was performed. The Py, Ty, adhesion, and appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

[0156] <Comparative Examples 3 and 4> Agents A and B were prepared in the same manner as in Comparative Example 1, except that the reactive additives were changed as shown in the table, and then the two liquids were mixed by stirring in a SUS can at 25° C. for 1 hour. After mixing the two liquids, the can was sealed under dry nitrogen and stored at 25° C. for 3 months, after which coating was performed. The Py, Ty, adhesion, and appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

[0157] <Comparative Example 5> The polarizing film obtained in the same manner as in Example 1, except that the dichroic dye was added to the agent A and that the dichroic dye was omitted from the agent B, was evaluated for Py, Ty, adhesion, and appearance in the same manner as in Example 1.

[0158] [Table 1]

[0159] From the compositions of Examples 1 to 14 in which the reactive additive and the dichroic dye containing the azo dye having an amine structure were stored separately, a polarizing film having good optical properties, high adhesion and excellent appearance could be obtained even when coating was performed after storing for three months after preparing the second agent. On the other hand, from the compositions of Comparative Examples 1, 3 and 4 in which the reactive additive and the dichroic dye containing the azo dye having an amine structure were mixed and then stored for three months, and Comparative Example 5 in which the reactive additive and the dichroic dye containing the azo dye having an amine structure were contained in the same agent, a polarizing film having poor optical properties, adhesion and appearance was obtained. It can be seen that the polarizing film obtained from the composition of Comparative Example 2, which does not contain a reactive additive, has poor adhesion.

Claims

1. A method for storing a two-liquid type composition for forming a polarizing film, the composition comprising an A component containing a reactive additive having a polymerizable group and an active hydrogen-reactive group in the molecule and a solvent, and a B component containing a dichroic dye, a polymerizable liquid crystal compound and a solvent, the dichroic dye including an azo dye having an amine structure, the method comprising the steps of: The A and B components are stored separately at a storage temperature of 0 to 50°C. The agent A is stored in a plastic or metal container under a dry inert gas atmosphere. Storage method.

2. 2. The method according to claim 1, wherein the water content of the solvent contained in the agent A is less than 300 ppm.

3. 3. A method for producing a composition for forming a polarizing film, comprising: mixing a component A, which constitutes the two-component type composition for forming a polarizing film stored by the storage method according to claim 1 or 2, and which contains a reactive additive having a polymerizable group and an active hydrogen-reactive group in the molecule and a solvent, with a component B, which contains a dichroic dye including an azo dye having an amine structure, a polymerizable liquid crystal compound, and a solvent.

4. A step of forming an alignment film on a substrate; a step of mixing an A component, which comprises the reactive additive having a polymerizable group and an active hydrogen-reactive group in the molecule and a solvent, with a B component, which comprises a dichroic dye including an azo dye having an amine structure, a polymerizable liquid crystal compound, and a solvent, constituting the two-liquid type polarizing film-forming composition stored by the storage method according to claim 1 or 2, to obtain a polarizing film-forming composition; A step of applying the mixed composition for forming a polarizing film onto the alignment film to obtain a coating film; and A step of curing the coating film A method for producing a polarizing film, comprising the steps of:

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