Composition for forming two-component polarizing film

Abstract

This invention provides a polarizing film forming composition that yields a polarizing film with good optical performance even after long-term storage, a method for storing the same composition, a method for manufacturing the composition, and a method for manufacturing the polarizing film. The two-component polarizing film forming composition comprises agent A, which includes a reactive additive having polymerizable groups and active hydrogen reactive groups within its molecule, and a solvent, and agent B, which includes a dichroic pigment and a solvent. The dichroic pigment includes an azo pigment having an amine structure.

Description

Technical Field

[0001] This invention relates to a composition for forming a two-component polarizing film and a method for storing the same, a method for manufacturing the composition for forming a polarizing film, and a method for manufacturing a polarizing film. Background Technology

[0002] In recent years, with the trend towards thinner image display devices, optical films such as polarizing plates and retardation plates using polarizing films have been developed. These polarizing films comprise a liquid crystal cured layer obtained by coating a polymeric liquid crystal compound onto a substrate or alignment film and curing it in an oriented state. In the manufacture of such optical films, from the viewpoint of film-forming properties and operability, the polymeric liquid crystal compound is typically coated onto the substrate or alignment film in the form of a polarizing film forming composition obtained by dissolving the polymeric liquid crystal compound in a solvent or the like. It is known that when an optical film is manufactured by coating a composition onto a substrate or alignment film, if the adhesion between the substrate or alignment film and the resulting optical film is high, peeling during processing will not occur, thus easily yielding a high-quality optical film. Therefore, a composition possessing the characteristic of providing a high-adhesion optical film has been proposed (Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2017-83843 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] However, the following problem has been found: if the above composition is formed into a polarizing film after long-term storage, good optical performance may not be obtained. Therefore, the object of the present invention is to provide a polarizing film forming composition that can produce a polarizing film with good optical performance even after long-term storage, a method for storing the same composition, a method for manufacturing the composition, and a method for manufacturing the polarizing film.

[0008] Methods for solving problems

[0009] The inventors of this application conducted repeated and detailed research to solve the aforementioned problems, resulting in this invention. Specifically, this invention includes the following preferred embodiments.

[0010] [1] A two-component polarizing film forming composition comprising an agent A containing a reactive additive having polymerizable groups and active hydrogen reactive groups within the molecule and a solvent, and an agent B containing a dichroic pigment and a solvent, wherein the dichroic pigment contains an azo pigment having an amine structure.

[0011] [2] The two-liquid polarizing film forming composition as described in [1] further comprises a polymerizable liquid crystal compound.

[0012] [3] The two-component polarizing film forming composition as described in [1] or [2], wherein the water content of the solvent contained in the aforementioned Agent A is less than 300 ppm.

[0013] [4] The two-component polarizing film forming composition as described in [2] or [3], wherein the amount of the aforementioned reactive additive contained in the aforementioned agent A is more than 0.5 parts by mass and less than 10 parts by mass relative to 100 parts by mass of the aforementioned polymeric liquid crystal compound.

[0014] [5] A method for storing the composition for forming a two-liquid polarizing film as described in any one of [1] to [4], wherein the aforementioned agent A and agent B are stored separately.

[0015] [6] The preservation method as described in [5], wherein the aforementioned Agent A is preserved in a plastic or metal container.

[0016] [7] The preservation method as described in [5] or [6], wherein the aforementioned Agent A is preserved in a dry, inactive gas atmosphere.

[0017] [8] A method for manufacturing a composition for forming a polarizing film, comprising a step of mixing the aforementioned agent A and agent B constituting any one of [1] to [4], wherein agent A comprises a reactive additive having polymerizable groups and active hydrogen reactive groups within the molecule and a solvent, and agent B comprises a dichroic pigment and a solvent, wherein the dichroic pigment comprises an azo pigment having an amine structure.

[0018] [9] A method for manufacturing a polarizing film, comprising the following steps:

[0019] The process of forming an alignment film on a substrate;

[0020] The step of mixing the aforementioned Agent A and Agent B to form the two-liquid polarizing film forming composition as described in any one of [1] to [4] to obtain the polarizing film forming composition, wherein Agent A includes a reactive additive having polymerizable groups and active hydrogen reactive groups in the molecule and a solvent, and Agent B includes a dichroic pigment and a solvent, wherein the dichroic pigment includes an azo pigment having an amine structure.

[0021] The process of coating the aforementioned mixed polarizing film forming composition onto the aforementioned alignment film to obtain a coating film; and

[0022] The process of curing the aforementioned coating.

[0023] Invention Effects

[0024] According to the present invention, there can be provided 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 can obtain a polarizing film having good optical properties even after long-term storage. In addition, the polarizing film obtained from the composition for forming a polarizing film of the present invention has high adhesion and excellent appearance. Detailed Embodiments

[0025] 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 herein, and various modifications can be made without departing from the gist of the present invention.

[0026] 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 and a solvent, and the dichroic dye contains an azo dye having an amine structure.

[0027] The two-component composition for forming a polarizing film of the present invention requires a reactive additive, an azo dye having an amine structure, and a solvent for dissolving them. The above reactive additive is separately incorporated into Agent A, and the azo dye having an amine structure is incorporated into Agent B.

[0028] <Agent A>

[0029] 〔Reactive Additive〕

[0030] A reactive additive is a substance that is usually added to a composition for forming a polarizing film to improve the adhesion of the polarizing film. The polymerizable group possessed by the reactive additive contained in Agent A is a group that participates in a polymerization reaction. Examples of the polymerizable group include carbon-carbon unsaturated bonds such as carbon-carbon double bonds or carbon-carbon triple bonds. Specifically, examples include vinyl, (meth)acrylic groups, vinyloxy, 1-chloroethenyl, isopropenyl, 4-vinylphenyl, acryloyloxy, methacryloyloxy, oxiranyl, oxetanyl, and the like.

[0031] The active hydrogen-reactive group possessed by the reactive additive contained in Agent A is a group that is reactive with a group containing active hydrogen such as a carboxyl group (-COOH), a hydroxyl group (-OH), or an amino group (-NH2). Representative examples include an epoxy group, a glycidyl group, an oxazolyl group, a carbodiimide group, an aziridinyl group, an imide group, an isocyanate group, an isothiocyanate group, a maleic anhydride group, an alkoxysilyl group, and the like. In the reactive additive, it is preferable that at least two active hydrogen-reactive groups are present. In this case, the multiple active hydrogen-reactive groups present may be the same or different.

[0032] The reactive additive typically has 1 to 20 polymerizable groups and 1 to 10 active hydrogen reactive groups, respectively.

[0033] In a preferred embodiment, the reactive additive preferably contains vinyl and / or (meth)acrylic groups as polymerizable groups, preferably contains at least one group selected from the group consisting of epoxy, glycidyl, isocyanate and alkoxysilyl groups as active hydrogen reactive groups, and more preferably is a reactive additive having acrylic and isocyanate groups or a reactive additive having acrylic and alkoxysilyl groups.

[0034] Specific examples of reactive additives include compounds such as methacryloyloxyglycidyl ether and acryloyloxyglycidyl ether, which have (meth)acrylic acid groups and epoxy groups; compounds such as oxetane acrylate and oxetane methacrylate, which have (meth)acrylic acid groups and oxetane butyl groups; compounds such as lactone acrylate and lactone methacrylate, which have (meth)acrylic acid groups and lactone groups; compounds such as vinyl oxazoline and isopropenyl oxazoline, which have vinyl and oxazolyl groups; compounds such as methyl isocyanate acrylate, methyl isocyanate methacrylate, ethyl 2-isocyanate acrylate and ethyl 2-isocyanate methacrylate, which have (meth)acrylic acid groups and isocyanate groups; and oligomers of compounds such as 3-acryloyloxypropyltrimethoxysilane and 3-methacryloyloxypropylmethyldimethoxysilane, which have (meth)acrylic acid groups and alkoxysilyl groups. In addition, compounds containing vinyl, vinylidene, and anhydride, such as methacrylic anhydride, acrylic anhydride, maleic anhydride, and vinyl maleic anhydride, can be cited as examples. Among these, methacryloyloxyglycidyl ether, acryloyloxyglycidyl ether, methyl isocyanate acrylate, methyl isocyanate methacrylate, vinyloxazoline, ethyl 2-isocyanate acrylate, ethyl 2-isocyanate methacrylate, 3-acryloyloxypropyltrimethoxysilane, and oligomers thereof are preferred, and methyl isocyanate acrylate, ethyl 2-isocyanate acrylate, 3-acryloyloxypropyltrimethoxysilane, and oligomers thereof are particularly preferred.

[0035] As a reactive additive, commercially available products can be used directly, or they can be purified as needed.

[0036] As commercially available products, examples include Laromer PR9000 (manufactured by BASF), Karenz AOI (manufactured by Showa Denko Co., Ltd.), and KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0037] Relative to 100 parts by mass of the polymerizable liquid crystal compound described later, the amount of the aforementioned reactive additive contained in Agent A is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 1.5 parts by mass or more, even more preferably 2 parts by mass or more, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, even more preferably 6 parts by mass or less, even more preferably 5 parts by mass or less. If the amount of the aforementioned reactive additive is above or below the aforementioned lower limit and below the aforementioned upper limit, the orientation of the polarizing film manufactured by the two-liquid polarizing film forming composition of the present invention will not be impaired, and the adhesion will be easily improved. The reactive additive can be used alone or in combination of two or more. When two or more reactive additives are used, the amount of the aforementioned reactive additive indicates their total amount.

[0038] When the two-component polarizing film forming composition of the present invention does not contain the polymerizable liquid crystal compound described later, the amount of the aforementioned reactive additive contained in agent A is 2 parts by mass or more, more preferably 5 parts by mass or more, further preferably 15 parts by mass or more, more preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and further preferably 80 parts by mass or less, relative to a total of 100 parts by mass of all dichroic pigments contained in agent A and agent B.

[0039] [Solvent]

[0040] The water content of the solvent contained in Agent A 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. If the water content of the solvent contained in Agent A is less than the aforementioned upper limit, the reaction between the active hydrogen reactive groups of the reactive additive and water is less likely to occur. Therefore, even after long-term storage, the adhesion of the polarizing film is easily improved, and a polarizing film with excellent appearance is easily obtained. The lower limit of the water content of the solvent contained in Agent A is 0 ppm. The water content of the solvent contained in Agent A can be controlled within the aforementioned range, for example, by distilling the solvent together with a desiccant under an inactive gas, or by coexisting with molecular sieves for a certain period of time. Commercially available dehydrating solvents can also be used. The water content of the solvent contained in Agent A can be determined, for example, using a Karl Fischer titration apparatus.

[0041] Specific examples of such solvents include alcohol solvents such as methanol, ethanol, butanol, ethylene glycol, isopropanol, propylene glycol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, cyclohexanol, and phenol; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl pentyl ketone, and methyl isobutyl ketone; and non-chlorinated lipid solvents such as pentane, hexane, and heptane. Aliphatic hydrocarbon solvents; alicyclic hydrocarbon solvents such as cyclohexane; non-chlorinated aromatic hydrocarbon solvents such as toluene, anisole, trimethylbenzene, and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran, dioxane, and dimethoxyethane; chlorinated solvents such as dichloromethane, dichloroethane, chlorotoluene, chloroform, chlorobenzene, and dichlorobenzene; sulfoxide solvents such as dimethyl sulfoxide; amide solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolinone; and heterocyclic solvents such as pyridine. These organic solvents can 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.

[0042] Solvents can be used alone or in combination of two or more. When using two or more solvents in combination, it is preferable that the total water content of all solvents used is less than 300 ppm. However, if the solvents include solvents with a water content of 300 ppm or more, it is preferable that the water content of the solvents as a whole is less than 300 ppm.

[0043] The solvent content in Agent A is preferably 50-99% by mass, more preferably 55-98% by mass, and even more preferably 60-97% by mass, relative to the total mass of all components contained in Agent A. If the solvent content in Agent A is within the above range, it is easy to uniformly dissolve solid components with high viscosity, such as reactive additives, and a uniform coating film can be formed in the polarizing film manufacturing method described later, thus easily obtaining a polarizing film with a good appearance.

[0044] Agent A can be prepared by mixing the aforementioned reactive additive, the aforementioned solvent, and, as appropriate, the optional components described below. There are no particular limitations on the mixing method, temperature, and time; these can be appropriately selected based on the type and amount of components contained in Agent A.

[0045] The viscosity (at 25°C) of agent A is preferably 0.1–15 mPa·s, more preferably 0.1–10 mPa·s. If the viscosity of agent A is within the aforementioned range, the workability is excellent, and it facilitates subsequent mixing with agent B.

[0046] As described above, in the two-liquid type polarizing film-forming composition of the present invention, the aforementioned reactive additive is separately incorporated into Agent A, and the azo dye having an amine structure described below is incorporated into Agent B. Therefore, Agent A substantially does not contain the azo dye having an amine structure described below. The phrase "substantially does not contain an azo dye having an amine structure" means that: with respect to 100 parts by mass of the reactive additive, 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. It is preferred that the content of the azo dye having an amine structure in Agent A is 0 part by mass.

[0047] <Agent B>

[0048] 〔Dichroic Dye〕

[0049] The dichroic dye contained in Agent B contains an azo dye having an amine structure. In the present invention, the amine structure specifically includes, for example, the group represented by the following formula (1A).

[0050] [Chemical Formula 1]

[0051]

[0052] [In the formula, A a1 and A a2 each independently represent 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 are bonded to each other and together with the nitrogen atom to which they are bonded represent a nitrogen-containing heterocyclic ring such as a pyrrolidine ring. * represents a connecting bond.]

[0053] Examples of the dichroic dye having an amine structure include, for example, the dye represented by the following general formula (1).

[0054] [Chemical Formula 2]

[0055] A 1 -N=N(-A 2 -N=N) p -A 3 (1)

[0056] [In the formula, A 1 and A 3Each can be represented independently as a phenyl group that may have a substituent, a naphthyl group that may have a substituent, a phenyl benzoate group that may have a substituent, or a monovalent heterocyclic group that may have a substituent. A 2 This indicates a 1,4-phenylene group that may have substituents, a naphth-1,4-diyl group that may have substituents, a 4,4'-indene group that may have substituents, or a divalent heterocyclic group that may have substituents. Wherein, A... 1 ~A 3 At least one of them has the amine structure shown in formula (1A) above as a substituent. p represents an integer from 0 to 4. When p is an integer greater than or equal to 2, multiple A 2 They can be the same or different.

[0057] Examples of monovalent heterocyclic groups include those obtained by removing one hydrogen atom from heterocyclic compounds such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole, and benzoxazole. Examples of divalent heterocyclic groups include those obtained by removing two hydrogen atoms from the aforementioned heterocyclic compounds.

[0058] As A 1 and A 3 The phenyl, naphthyl, phenyl benzoate ester group and monovalent heterocyclic group, as well as A 2 The 1,4-phenylene, naphth-1,4-diyl, 4,4'-indene, and divalent heterocyclic groups may optionally have substituents other than the amine structure shown in formula (1A), such as alkyl groups having 1 to 6 carbon atoms; alkoxy groups having 1 to 6 carbon atoms, such as methoxy, ethoxy, and butoxy; fluoroalkyl groups having 1 to 6 carbon atoms, such as trifluoromethyl; cyano; nitro; halogen atoms, etc. It should be noted that specific examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, butyl, and hexyl.

[0059] Among the dichroic pigments represented by formula (1), the compounds represented by formulas (1-1) to (1-8) are preferred.

[0060] [Chemical Formula 3]

[0061]

[0062] In equations (1-1) to (1-8),

[0063] B 1 ~B 3 At least one of them, B 4 ~B 7 At least one of them, B 8 ~B 10 At least one of them, B 11 ~B 12 At least one of them, B 13 ~B16 At least one of them, B 17 ~B 20 At least one of them, B 21 ~B 25 At least one of them, and B 26 ~B 30 At least one of the groups is a substituent of the amine structure represented by formula (1A) above. Other than the substituents of the amine structure represented by formula (1A), B... 1 ~B 30 Each of the following can be independently represented as 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.

[0064] n1 to n4 represent integers from 0 to 3 independently.

[0065] When n1 is 2 or more, multiple B 2 They can be the same or different.

[0066] When n² is greater than 2, multiple B 6 They can be the same or different.

[0067] When n3 is 2 or more, multiple B 9 They can be the same or different.

[0068] When n4 is 2 or more, multiple B 14 They can be the same or different.

[0069] Relative to 100 parts by mass of the polymerizable liquid crystal compound described later, the content of the aforementioned azo pigment with an amine structure in agent B 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. If the content of the aforementioned dichroic pigment with an amine structure is less than the aforementioned lower limit, light absorption becomes insufficient, and sufficient polarization performance is not obtained; if it is greater than the aforementioned upper limit, it may sometimes hinder the orientation of the polymerizable liquid crystal. The azo pigment with an amine structure can be used alone or in combination of two or more. When two or more azo pigments with an amine structure are used, the content of the azo pigment with an amine structure represents its total amount.

[0070] When the two-component polarizing film forming composition of the present invention does not contain the polymerizable liquid crystal compound described later, the amount of the aforementioned azo pigment with an amine structure contained in agent B is 3 parts by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, generally 100 parts by mass or less, preferably 90 parts by mass or less, and more preferably 85 parts by mass or less, relative to the total amount of dichroic pigment contained in agent A and agent B.

[0071] [Solvent]

[0072] The solvent contained in agent B is not particularly limited, but it is preferably a solvent that is inactive with azo pigments having an amine structure and can completely dissolve the pigment. Furthermore, from the perspective of using agent A and agent B in combination, a solvent with high compatibility with the solvent used in agent A is preferred, but the same solvent may also be used. Additionally, the solvent contained in agent B may be used alone or in combination of two or more types.

[0073] The solvent content in agent B is preferably 50-95% by mass, more preferably 60-90% by mass, and even more preferably 70-85% by mass, relative to the total mass of the components contained in agent B. If the solvent content in agent B is within the above range, the aforementioned dichroic pigment can be easily and uniformly dissolved, and a uniform coating film can be formed in the polarizing film manufacturing method described later, thus easily obtaining a polarizing film with a good appearance.

[0074] Specific examples of such solvents include alcohol solvents such as methanol, ethanol, butanol, ethylene glycol, isopropanol, propylene glycol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, cyclohexanol, and phenol; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl pentyl ketone, and methyl isobutyl ketone; and non-chlorinated lipid solvents such as pentane, hexane, and heptane. Aliphatic hydrocarbon solvents; alicyclic hydrocarbon solvents such as cyclohexane; non-chlorinated aromatic hydrocarbon solvents such as toluene, anisole, trimethylbenzene, and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran, dioxane, and dimethoxyethane; chlorinated solvents such as dichloromethane, dichloroethane, chlorotoluene, chloroform, chlorobenzene, and dichlorobenzene; sulfoxide solvents such as dimethyl sulfoxide; amide solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolinone; heterocyclic solvents such as pyridine, etc. These organic solvents can be used alone or in combination.

[0075] As described above, in the two-component polarizing film forming composition of the present invention, the aforementioned reactive additive is separately incorporated into agent A, and the aforementioned azo dye having an amine structure is separately incorporated into agent B. Therefore, agent B substantially does not contain the aforementioned reactive additive. "Substantially does not contain reactive additive" means that, relative to 100 parts by weight of the azo dye having an amine structure, the content of the reactive additive in agent B is preferably less than 0.5 parts by weight, more preferably less than 0.1 parts by weight, and even more preferably less than 0.05 parts by weight. Preferably, the content of the reactive additive in agent B is 0 parts by weight.

[0076] [Polymerizable liquid crystal compounds]

[0077] Preferably, the two-liquid polarizing film forming composition of the present invention further comprises a polymerizable liquid crystal compound. The aforementioned polymerizable liquid crystal compound may be included in either liquid A or liquid B constituting the two-liquid polarizing film forming composition of the present invention.

[0078] A polymerizable liquid crystal compound is a compound that possesses polymerizable groups and exhibits a liquid crystal state. The polymerizable group refers to a group that participates in the polymerization reaction of the polymerizable liquid crystal compound, preferably a photopolymerizable group. Here, the photopolymerizable group refers to a group that can participate in the polymerization reaction using active free radicals, acids, etc., generated by a photopolymerization initiator described later. Examples of polymerizable groups include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloyloxy, methacryloxy, oxetylpropyl, and oxetylbutyl. Acryloyloxy, methacryloxy, vinyloxy, oxetylpropyl, and oxetylbutyl are preferred, and acryloyloxy is more preferred. The liquid crystal properties can be thermotropic or lyotropic.

[0079] The polymerizable liquid crystal compound can be a thermotropic liquid crystal compound exhibiting a nematic liquid crystal phase or a thermotropic liquid crystal compound exhibiting a smectic liquid crystal phase. In this invention, from the viewpoint of obtaining higher polarization characteristics, 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 higher-order smectic liquid crystal phase. More preferably, it is a thermotropic liquid crystal compound exhibiting a smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase, or smectic L phase; even more preferably, it is a thermotropic liquid crystal compound exhibiting a smectic B phase, smectic F phase, or smectic I phase. If the liquid crystal phase formed by the polymerizable liquid crystal compound is one of these higher-order smectic phases, a polarizing film with higher polarization performance can be manufactured. Furthermore, such a polarizing film with high polarization performance can obtain Bragg peaks from higher-order structures such as hexagonal phases and crystalline phases in X-ray diffraction measurements. These Bragg peaks are peaks from periodic structures of molecular orientation, and the period interval can be obtained as... membrane.

[0080] Examples of such polymeric liquid crystal compounds include compounds represented by the following formula (2) (hereinafter sometimes referred to as compound (2)). These polymeric liquid crystals can be used alone or in combination of two or more.

[0081] U 1 -V 1 -W 1 -(X 1 -Y 1 ) n -X2 -Y 2 -X 3 -W 2 -V 2 -U 2 (2) [In equation (2), X 1 X 2 X 3 Each of these groups independently represents a divalent aromatic group or a divalent alicyclic hydrocarbon group. Here, the hydrogen atom in the divalent aromatic group or divalent alicyclic hydrocarbon group can be replaced by a halogen atom, an alkyl group with 1 to 4 carbon atoms, a fluoroalkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, a cyano group, or a nitro group. The carbon atom constituting the divalent aromatic group or divalent alicyclic hydrocarbon group can be replaced by an oxygen atom, a sulfur atom, or a nitrogen atom. Wherein, X 1 X 2 X 3 At least one of them is a 1,4-phenylene that may have substituents or a cyclohexane-1,4-diyl that may have substituents. Additionally, n is 1 to 3, and when n is 2 or more, X 1 Each can be different. From the viewpoint of exhibiting liquid crystal properties, n is preferably 1 or 2.

[0082] Y 1 Y 2 W 1 and W 2 Each group is a single bond or a divalent linker, independent of the others.

[0083] V 1 and V 2 Each of the above can independently represent an alkane diene with 1 to 20 carbon atoms that may have substituents, wherein the -CH2- constituting the alkane diene can be replaced by -O-, -CO-, -S- or NH-.

[0084] U 1 and U 2 Each of the following elements independently represents a polymeric group or a hydrogen atom, with at least one being a polymeric group.

[0085] In compound (2), X 1 X 2 X 3 At least one of them is a 1,4-phenylene that may have substituents, or a cyclohexane-1,4-diyl that may have substituents. In particular, X 1 or X 3Preferably, it is a cyclohexane-1,4-diyl group that may have substituents, and this cyclohexane-1,4-diyl group is more preferably trans-cyclohexane-1,4-diyl. Examples of substituents optionally present in the 1,4-phenylene group that may have substituents, or in the cyclohexane-1,4-diyl group that may have substituents, include alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, and butyl, cyano groups, and halogen atoms such as chlorine and fluorine atoms. Unsubstituted is preferred. Additionally, Y 1 and Y 2 Given the same structure, X is preferred. 1 X 2 and X 3 At least one of them is a different structure. In the case of X... 1 X 2 and X 3 When at least one of the components is a different asymmetric structure, there is a tendency for it to exhibit smectic liquid crystal properties.

[0086] Y 1 and Y 2 The preferred independent bonds are single bonds, -CH2CH2-, -CH2O-, -CH2CH2O-, -COO-, -OCO-, -N=N-, and -CR. a =CR b -、-C≡C- or -CR a =N-,R a and R b Each of the following groups independently represents an alkyl group having 1 to 4 hydrogen atoms or carbon atoms. 1 and Y 2 More preferably, it is -CH2CH2-, -COO-, -OCO-, -N=N-, or a single bond. Additionally, in X... 1 X 2 and X 3 When all structures are identical, Y is preferred. 1 and Y 2 Different bonding methods. In Y... 1 and Y 2 When the bonding methods are different, they become asymmetric structures, and therefore tend to exhibit smectic liquid crystal properties.

[0087] W 1 and W 2 The components are preferably single bonds, -O-, -S-, -COO-, or -OCO-, and more preferably single bonds or -O-.

[0088] As V 1 and V 2Examples of alkane dimethyl groups representing 1 to 20 carbon atoms include methylene, ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane-1,10-diyl, tetradecane-1,14-diyl, and eicosane-1,20-diyl. 1 and V 2 Preferably, it is an alkane diene with 2 to 12 carbon atoms, and more preferably a linear alkane diene with 6 to 12 carbon atoms. By making it a linear alkane diene with 6 to 12 carbon atoms, there is a tendency for increased crystallinity and easy manifestation of smectic liquid crystal properties.

[0089] Examples of substituents that may be optionally present in an alkane diene having 1 to 20 carbon atoms include cyano groups and halogen atoms such as chlorine and fluorine atoms. However, the alkane diene is preferably unsubstituted, and more preferably an unsubstituted alkane diene in the form of a straight chain.

[0090] U 1 and U 2 Preferably, all components are polymerizable groups, and more preferably, all components are photopolymerizable groups. Polymerizable liquid crystal compounds with photopolymerizable groups can polymerize at low temperatures compared to those with thermally polymerizable groups. Therefore, liquid crystals can form polymers in a more ordered state, which is advantageous.

[0091] U 1 and U 2 The polymerizable groups may differ from one another, but are preferably the same. Examples of polymerizable groups include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloyloxy, methacryloxy, oxetylpropyl, and oxetylbutyl. Among these, acryloyloxy, methacryloxy, vinyloxy, oxetylpropyl, and oxetylbutyl are preferred, and methacryloxy or acryloyloxy are more preferred. Furthermore, the polymerizable groups may be in a polymerized state or an unpolymerized state, but the unpolymerized state is preferred.

[0092] As for the polymeric liquid crystal compound (2), there are no particular limitations as long as it has at least one polymeric group and exhibits smectic liquid crystal properties. Known polymeric liquid crystal compounds can be used, but it is preferable to have a molecular structure with asymmetry in its molecular structure as a structure that easily exhibits smectic liquid crystal properties. Specifically, it is more preferable to be a polymeric liquid crystal compound having partial structures of (Aa) to (Ai) and exhibiting smectic liquid crystal properties. From the viewpoint of easily exhibiting higher-order smectic liquid crystal properties, it is more preferable to have partial structures of (Aa), (Ab), or (Ac). Here, in the figure, * indicates a connecting bond.

[0093] [Chemical Formula 4]

[0094]

[0095] Specific examples of compounds 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 the trans form.

[0096] [Chemical Formula 5]

[0097]

[0098] [Chemical Formula 6]

[0099]

[0100] [Chemical Formula 7]

[0101]

[0102] Of the compounds represented by formula (2), preferably at least one is 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). As a polymerizable liquid crystal compound, one type may be used alone, or two or more types may be used in combination.

[0103] The compound represented by formula (2) can be used alone or in combination. Furthermore, when combining two or more polymerizable liquid crystal compounds, it is preferable that at least one is a compound represented by formula (2), and more preferably two or more are compounds represented by formula (2). The mixing ratio when combining two polymerizable liquid crystal compounds is typically 1:99 to 50:50, preferably 5:95 to 50:50, and more preferably 10:90 to 50:50 (mass ratio). When combining a polymerizable liquid crystal compound having one polymeric group and a polymerizable liquid crystal compound having two polymeric groups, the mixing ratio (polymerizable liquid crystal compound having one polymeric group: polymerizable liquid crystal compound having two polymeric groups) is typically 1:99 to 50:50, preferably 5:95 to 50:50, and more preferably 10:90 to 50:50 (mass ratio).

[0104] The compound represented by formula (2) can be manufactured by known methods as described, for example, in Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996) or Japanese Patent No. 4719156.

[0105] Regarding the amount of the aforementioned polymeric liquid crystal compound contained in the two-liquid polarizing film forming composition of the present invention, when the aforementioned two-liquid polarizing film forming composition is contained in agent B, it is preferably 40% or more by mass, more preferably 60% or more by mass, further preferably 70% or more by mass, preferably 99.9% or less by mass, and more preferably 99% or less by mass of all solid components in agent B. If the content of the polymeric liquid crystal compound is above or below the aforementioned lower limit or below the aforementioned upper limit, there is a tendency for the orientation to become higher. Here, the term "solid component" refers to the total amount of components obtained by removing the solvent from the polarizing film forming composition.

[0106] Agent B can be prepared by mixing the aforementioned azo dye with an amine structure, the aforementioned solvent, and optional components described later, as appropriate. There are no particular limitations on the mixing method, temperature, and time; these can be appropriately selected based on the type and amount of components contained in Agent B.

[0107] The viscosity (at 25°C) of agent B is preferably 0.1–15 mPa·s, more preferably 0.1–10 mPa·s. If the viscosity of agent B is within the aforementioned range, the workability is excellent, and it facilitates subsequent mixing with agent A.

[0108] The two-component polarizing film forming composition of the present invention may, in addition to the components described above, include optional components such as polymerization initiators, sensitizers, polymerization inhibitors, leveling agents, and dichroic pigments other than azo pigments having an amine structure.

[0109] [Polymerization initiator]

[0110] The two-component polarizing film forming composition of the present invention may contain a polymerization initiator. A polymerization initiator is a compound capable of initiating polymerization reactions of polymerizable liquid crystal compounds, etc. Preferably, a photopolymerization initiator that generates active free radicals through the action of light is preferred.

[0111] One or both of Agent A or Agent B constituting the two-component polarizing film forming composition of the present invention may contain a polymerization initiator. When Agent A contains a polymerization initiator, the polymerization initiator is preferably a compound that does not have an amine structure.

[0112] From the viewpoint that polymerization initiators are independent of the phase state of thermotropic liquid crystals, photopolymerization initiators that generate active free radicals through the action of light are preferred.

[0113] The photopolymerization initiator can be any compound capable of initiating the polymerization reaction of a polymerizable liquid crystal compound; known photopolymerization initiators can be used. Specifically, photopolymerization initiators capable of generating active free radicals or acids through the action of light are examples, with photopolymerization initiators that generate free radicals through the action of light being preferred. Photopolymerization initiators can be used alone or in combination of two or more.

[0114] As photopolymerization initiators, known photopolymerization initiators can be used. For example, as photopolymerization initiators that generate active free radicals, self-cracking benzoin compounds, acetophenone compounds, hydroxyacetophenone compounds, α-aminoacetophenone compounds, oxime ester compounds, acylphosphine oxide compounds, azo compounds, etc., can be used. Hydrogen-abstracting compounds such as benzophenone compounds, alkylacetophenone compounds, benzoyl ether compounds, benzoin ketal compounds, dibenzocycloheptanone compounds, anthraquinone compounds, xanthonesone compounds, thioxanthonesone compounds, haloacetophenone compounds, dialkoxyacetophenone compounds, halodiimidazole compounds, halotriazine compounds, triazine compounds, etc., can be used. As photopolymerization initiators that generate acids, iodonium salts and sulfonium salts, etc., can be used. Considering the excellent reaction efficiency at low temperatures, self-destructive photopolymerization initiators are preferred, especially acetophenone compounds, hydroxyacetophenone compounds, α-aminoacetophenone compounds, and oxime ester compounds.

[0115] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0116] Examples of acetophenone compounds include, for example, diethoxyacetophenone and other diethoxyacetophenone compounds; oligomers of 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl one and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1-one and other hydroxyacetophenone compounds; and α-aminoacetophenone compounds such as 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one and 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butane-1-one.

[0117] Examples of oxime ester compounds include, for example, 1-[4-(phenylthio)phenyl-1,2-octanedione 2-(O-benzoyl oxime)], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] acetophenone-1-(O-acetyl oxime).

[0118] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyl diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0119] Examples of 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.

[0120] Examples of alkyl phenyl ketone compounds include, for example, diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1-one.

[0121] 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)] Vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

[0122] Commercially available polymerization initiators can be used as polymerization initiators. Examples of commercially available polymerization initiators include Irgacure (イルガキュア) 907, 184, 651, 819, 250 and 369 (manufactured by Ciba Specialty Chemicals Inc.); SEIKUOL (registered trademarks) BZ, Z and BEE (manufactured by Seiko Chemical Co., Ltd.); kayacure (カヤキュアー) BP100 and UVI-6992 (manufactured by Dow Chemical Company); ADEKA OPTOMER SP-152 and SP-170 (manufactured by ADEKA Co., Ltd.); TAZ-A and TAZ-PP (manufactured by Nihon Siber Hegner KK); and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.); etc. The polymerization initiator can be a single type, or it can be a mixture of two or more polymerization initiators depending on the light source.

[0123] The content of the polymerization initiator can be appropriately adjusted according to the type and amount of the polymerizable liquid crystal compound. It is typically 0.1 to 30 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound, preferably 0.5 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass. If the content of the polymerization initiator is within the above range, polymerization can be easily carried out without disturbing the orientation of the polymerizable liquid crystal.

[0124] [Sensitizer]

[0125] When the two-component polarizing film forming composition of the present invention contains a polymerizable liquid crystal compound, the aforementioned composition may contain a sensitizer. One or both of agent A or agent B constituting the two-component polarizing film forming composition of the present invention may contain a sensitizer. When agent A contains a sensitizer, the sensitizer is preferably a compound without an amine structure. As a sensitizer, a photosensitizer is preferred. Examples of such sensitizers include, for example, xanthoxanone compounds such as xanthoxanone and thioxanthone (e.g., 2,4-diethylthioxanthone, 2-isopropylthioxanthone); anthracene compounds such as anthracene and anthracene containing an alkoxy group (e.g., dibutoxyanthracene); phenothiazine and rubrene.

[0126] The content of the aforementioned sensitizer is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound, more preferably 0.5 to 10 parts by mass, and even more preferably 0.5 to 8 parts by mass. If the content of the sensitizer is within the aforementioned range, the polymerization reaction of the polymerizable liquid crystal compound is easily promoted.

[0127] [Polymerization inhibitor]

[0128] When the two-component polarizing film forming composition of the present invention contains a polymerizable liquid crystal compound, from the viewpoint of stabilizing the polymerization reaction, the aforementioned composition may contain a polymerization inhibitor. One or both of agent A or agent B constituting the two-component polarizing film forming composition of the present invention may contain a polymerization inhibitor. When agent A contains a polymerization inhibitor, the polymerization inhibitor is preferably a compound without an amine structure. The polymerization inhibitor can be used to control the extent of the polymerization reaction.

[0129] Examples of the aforementioned polymerization inhibitors include hydroquinone, hydroquinone containing an alkoxy group, catechol containing an alkoxy group (e.g., butyl catechol), pyrogallol, free radical scavengers such as 2,2,6,6-tetramethylpiperidine-1-oxy radical; thiophenols; β-naphthylamines and β-naphthols.

[0130] When the composition for forming a two-component polarizing film 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 even more preferably 0.5 to 8 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. If the content of the polymerization inhibitor is within the above range, polymerization can be easily carried out without disturbing the orientation of the polymerizable liquid crystal.

[0131] [Leveling agent]

[0132] The two-component polarizing film forming composition of the present invention may contain a leveling agent. A leveling agent is a substance that functions to adjust the flowability of the composition and make the film obtained by coating the composition flatter; for example, a surfactant. One or both of agent A or agent B constituting the two-component polarizing film forming composition of the present invention may contain a leveling agent. When agent A contains a leveling agent, the leveling agent is preferably a compound without an amine structure.

[0133] As leveling agents, examples include organically modified silicone oils, polyacrylates, and perfluoroalkyls. Specifically, examples include DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all manufactured by Dow Corning Toray 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 Advanced Materials Japan Contract Co., Ltd.), fluorinert (registered trademark) FC-72, and fluorinert. FC-40, fluorinert FC-43, fluorinert FC-3283 (all manufactured by Sumitomo 3M Ltd.), MEGAFACE (registered trademark) R-08, MEGAFACE R-30, MEGAFACE R-90, MEGAFACE F-410, MEGAFACE F-411, MEGAFACE F-443, MEGAFACE F-445, MEGAFACE F-470, MEGAFACE F-477, MEGAFACE F-479, MEGAFACE F-482, MEGAFACE F-483 (all manufactured by DIC Co., Ltd.), F-top (trade name) EF301, F-top EF303, F-top EF351, F-top EF352 (all manufactured by Mitsubishi Materials ElectronicChemicals). (Manufactured by Co., Ltd.), Surflon (registered trademark) S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-105, KH-40, SA-100 (all of the above are manufactured by AGC SeimiChemical Co., Ltd.), trade name E1830, trade name E5844 (manufactured by Daikin Fine Chemical Kenkyusho, KK), BM-1000, BM-1100, BYK-352, BYK-353 and BYK-361N (all trade name: manufactured by BM Chemie Co., Ltd.), etc.Among them, polyacrylate leveling agents and perfluoroalkyl leveling agents are preferred.

[0134] When the two-component 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, relative to the total solid components of the two-component polarizing film forming composition. If the leveling agent content is within the above range, there is a tendency that, when a polymerizable liquid crystal compound is included, the polymerizable liquid crystal is easily horizontally aligned, and the resulting polarizing film becomes smoother. If the leveling agent content exceeds the above range, there is a tendency that unevenness is easily generated in the resulting polarizing film. It should be noted that two or more leveling agents may be included.

[0135] [Dichroic pigments other than azo pigments with amine structures]

[0136] The two-component polarizing film forming composition of the present invention may contain dichroic pigments other than azo pigments having an amine structure. Preferably, such dichroic pigments are those having a maximum absorption wavelength (λMAX) in the range of 300 to 700 nm, and examples include azo pigments without an amine structure, anthraquinone pigments, oxazine pigments, acridine pigments, cyanine pigments, naphthalene pigments, and the like. The dichroic pigments other than azo pigments having an amine structure may be used alone or in combination of two or more.

[0137] As azo pigment that does not have an amine structure, examples include those in formula (1) mentioned above that do not contain an amine structure as A. 1 ~A 3 Compounds with substituents.

[0138] As an anthraquinone pigment, the preferred compound is one represented by formula (1-9).

[0139] [Chemical Formula 8]

[0140]

[0141] [In the formula, R] 1 ~R 8 Each can independently represent a hydrogen atom, -R x -NH2, -NHR x -NR x 2. -SR x Or halogen atoms, R x [Indicates an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms]

[0142] As an oxazine pigment, the preferred compound is one represented by formula (1-10).

[0143] [Chemical Formula 9]

[0144]

[0145] [In the formula, R] 9 ~R 15 Each can independently represent a hydrogen atom, -R x -NH2, -NHR x -NR x 2. -SR x Or halogen atoms, R x [Indicates an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms]

[0146] As an acridine dye, the preferred compound is one represented by formula (1-11).

[0147] [Chemical Formula 10]

[0148]

[0149] [In the formula, R] 16 ~R 23 Each can independently represent a hydrogen atom, -R x -NH2, -NHR x -NR x 2. -SR x Or halogen atoms, R x [Indicates an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms]

[0150] As in equations (1-9), (1-10), and (1-11), R x Examples of alkyl groups with 1 to 4 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl; examples of aryl groups with 6 to 12 carbon atoms include phenyl, tolyl, xylyl, and naphthyl.

[0151] As cyanin pigments, compounds represented by formulas (1-12) and (1-13) are preferred.

[0152] [Chemical Formula 11]

[0153]

[0154] [In the formula, D] 1 and D 2 The groups represented independently of any one of formulas (1-12a) to (1-12d)

[0155] [Chemical Formula 12]

[0156]

[0157] [n5 represents an integer from 1 to 3]

[0158] [Chemical Formula 13]

[0159]

[0160] [In the formula, D] 3 and D 4 The groups represented by any one of formulas (2-13a) to (2-13h) are independently represented.

[0161] [Chemical Formula 14]

[0162]

[0163] [n6 represents an integer from 1 to 3]

[0164] When the aforementioned azo pigment with an amine structure is used in combination with the dichroic pigment other than the azo pigment with an amine structure, the total content of all dichroic pigments is typically 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 pigments is within the above range, polymerization can be carried out without disturbing the orientation of the polymerizable liquid crystal compound. If the content of the dichroic pigments is too low, light absorption becomes insufficient, and sufficient polarization performance cannot be obtained; if it is too high, there is a concern that it may hinder the orientation of the polymerizable liquid crystal compound. Therefore, the content of the dichroic pigments can be determined within a range that allows the polymerizable liquid crystal compound to maintain its liquid crystal state.

[0165] <Saving Method>

[0166] When storing the two-component polarizing film forming composition of the present invention, agent A and agent B are stored separately.

[0167] Separate storage can be exemplified by storing reagent A and reagent B in two separate containers, or storing reagent A and reagent B in a single container with a partition in between to prevent mixing during storage. In this invention, storing reagent A and reagent B in two separate containers is preferred.

[0168] Examples of containers for storing Agent A include plastic containers, metal containers, and glass containers, with plastic or metal containers being preferred. If the container for storing Agent A is plastic or metal, side reactions of the reactive additives in Agent A are less likely to occur, making it a preferred choice. Examples of materials for plastic containers include, but are not limited to, polypropylene, polyethylene, norbornene polymers, polystyrene, polyamide, poly(4-methyl-1-pentene), acrylic resin, polyvinyl alcohol, acrylonitrile-butadiene-styrene copolymer, polymethacrylate, polyacrylate, cellulose ester, polycarbonate, polyethylene terephthalate, polysulfone, polyethersulfone, polyetherketone, polyethylene naphthalate, polyphenylene sulfide, polyphenylene ether, cyclic olefin polymers or cyclic olefin copolymers, amorphous polyarylates, polyester, Teflon, etc. Examples of materials for metal containers include, but are not limited to, steel such as SUS, tin-plated iron, aluminum, etc. When the container for storing Agent A is a plastic container, it is preferable to use a light-shielding plastic container (e.g., a brown plastic container) to minimize exposure to ultraviolet light or other substances that could degrade the composition. Alternatively, the outer surface of the container may be coated.

[0169] There are no particular limitations on the container used to store Agent B, and the material of the container can be, for example, plastic, metal, or glass. Similarly, the container for storing Agent B is preferably a light-proof container.

[0170] There are no particular restrictions on the shape of the containers used to store Agent A and Agent B. Examples include hexagonal shapes such as a small can, a plastic container, a pail can, and a cylindrical shape such as a bucket. Furthermore, there are no particular restrictions on the volume of Agent A and Agent B; the desired amount can be stored in the containers.

[0171] When storing Agent A, it is preferable to store it in a dry, inert gas atmosphere. In this specification, "dry gas" generally refers to a gas with a dew point below -50°C, and "inert gas" refers to gases with low reactivity, such as nitrogen, argon, and helium. Storage in a dry, inert gas atmosphere can be exemplified by filling the gas phase of the storage container with dry, inert gas and then sealing it, or storing the storage container itself in a space filled with dry, inert gas. By storing it in a dry, inert gas atmosphere, side reactions between moisture in the surrounding atmosphere and the active hydrogen reactive groups of the reactive additives in Agent A can be avoided. Therefore, the adhesion of the polarizing film obtained from the two-liquid polarizing film forming composition of the present invention is easily improved, and the optical performance tends to improve after long-term storage.

[0172] There are no particular limitations on the atmosphere in which Agent B is stored, but it is preferred to store it in a dry, inert gas atmosphere.

[0173] There is no particular limitation on the filling amount of Agent A and Agent B relative to the capacity of the storage container. The filling amount of Agent A and Agent B is usually 30% or more of the storage container capacity, preferably 50% or more, and usually 90% or less from the viewpoint of ease of operation during mixing.

[0174] There is no particular limitation on the storage temperature of Agent A and Agent B, but if the temperature is too high, it may trigger the polymerization reaction of the polymerizable liquid crystal compound. If the temperature is too low, the solid components in Agent A and Agent 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.

[0175] If the mixture of agents A and B is stored for about 3 months, it can sometimes be difficult to produce a polarizing film with good optical properties. The two-component polarizing film forming composition of the present invention is advantageous in that it can produce a polarizing film with good optical properties even after such a long storage period (e.g., more than 3 months). The storage period for agents A and B is not particularly limited, but is generally within 3 years.

[0176] For the two-liquid polarizing film forming composition of the present invention, by storing the reactive additive and the dichroic pigment containing an azo pigment having an amine structure separately as described above, a polarizing film with good optical properties can be obtained even after long-term storage. However, the inventors of this application have found that polarizing films obtained from polarizing film forming compositions that have been stored together with the reactive additive and, in particular, the azo pigment having an amine structure in the dichroic pigment for a certain period (e.g., 3 months) tend to exhibit the following tendency: the molecular orientation of the liquid crystal compounds in the polarizing film tends to become disordered (i.e., the liquid crystal compounds do not align in one direction), resulting in a decrease in the optical properties of the obtained polarizing film.

[0177] <Method for manufacturing composition for polarizing film formation>

[0178] In this invention, the polarizing film forming composition can be obtained by mixing agent A and agent B constituting a two-component polarizing film forming composition. It should be noted that, in this specification, the term "two-component polarizing film forming composition" refers to a composition in which agent A and agent B are in a separate state, while a composition in which agent A and agent B are mixed is referred to as a "polarizing film forming composition".

[0179] Regarding the timing of mixing agent A and agent B of the two-component polarizing film forming composition of the present invention, there is no limitation as long as the reaction between the reactive additive and the azo dye having an amine structure will not occur. It can be appropriately determined according to the type and amount of the reactive additive and the azo dye having an amine structure contained therein, the mixing conditions, and the environment.

[0180] There are no particular limitations on the method of mixing agent A and agent B; any known mixing method can be used. For example, methods such as mixing with mixing devices equipped with stirring blades, such as planetary mixers or kneading mixers, or static mixing methods such as using static mixers can be cited.

[0181] The ambient temperature during mixing of agent A and agent B is not particularly limited, but mixing is preferably carried out at a temperature of 0–50°C, more preferably 15–40°C, and even more preferably 20–35°C. Humidity (relative humidity) is not particularly limited, but is preferably 30–60% RH, more preferably 40–55% RH. Furthermore, mixing is generally carried out at normal atmospheric pressure.

[0182] There is no particular limitation on the mixing time, which can be adjusted appropriately according to the types and amounts of components contained in the two-component polarizing film forming composition. The mixing time is usually 0.5 to 12 hours, preferably 0.5 to 6 hours.

[0183] <Manufacturing Method of Polarizing Film>

[0184] The method for manufacturing the polarizing film of the present invention includes the following steps:

[0185] The process of forming an alignment film on a substrate;

[0186] The process of mixing agent A and agent B, which constitute the two-component polarizing film forming composition of the present invention, to obtain the polarizing film forming composition, wherein agent A includes a reactive additive having polymerizable groups and active hydrogen reactive groups within the molecule and a solvent, and agent B includes a dichroic pigment and a solvent, wherein the dichroic pigment includes an azo pigment having an amine structure.

[0187] The process of coating the aforementioned mixed polarizing film forming composition onto the aforementioned alignment film to obtain a coating film; and

[0188] The process of curing the aforementioned coating.

[0189] [Substrate]

[0190] Examples of substrates used in the formation of polarizing films include glass substrates and plastic substrates. Considering the ease of roll-to-roll processing and high productivity, plastic substrates are preferable to glass substrates. Examples of plastics constituting plastic substrates include, for example, polyolefins such as polyethylene, polypropylene, and norbornene polymers; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate; polyacrylates; cellulose esters such as cellulose triacetate, cellulose diacetate, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; polyphenylene sulfide and polyphenylene ether; and other plastics.

[0191] Examples of commercially available cellulose ester substrates include "Fujitac Film" (manufactured by Fuji Photo Film Co., Ltd.); "KC8UX2M", "KC8UY" and "KC4UY" (manufactured by Konica Minolta Opto Co., Ltd.).

[0192] Examples of commercially available cyclic olefin resins include "Topas" (registered trademark) (manufactured by Ticona GmbH (Germany), "Arton" (registered trademark) (manufactured by JSR Corporation), "ZEONOR" (registered trademark), "ZEONEX" (registered trademark) (manufactured by ZEON Corporation of Japan), and "APEL" (registered trademark) (manufactured by Mitsui Chemicals Co., Ltd.). Such cyclic olefin resins can be used to form films using known methods such as solvent casting and melt extrusion, thereby creating substrates. Commercially available cyclic olefin resin substrates can also be used. Examples of commercially available cyclic olefin resin substrates include "Esushina" (registered trademark), "SCA40" (registered trademark) (manufactured by Sekisui Chemicals Co., Ltd.), "ZeonorFilm" (registered trademark) (manufactured by Optes Co., Ltd.), and "Arton Film" (registered trademark) (manufactured by JSR Corporation).

[0193] A polarizing plate is obtained from the polarizing film and substrate of the present invention. Regarding the thickness of the substrate, a thinner substrate is preferred from the perspective of achieving usability in practical operation; however, if it is too thin, there is a tendency for reduced strength and poorer processability. The thickness of the substrate is typically 5–300 μm, preferably 20–200 μm. Furthermore, by peeling off the substrate and transferring a polymer containing a dichroic pigment to a polymerizable liquid crystal compound, only the polarizing film of the present invention can be applied, thus achieving a further thin-film effect.

[0194] [Orientation film]

[0195] In this invention, the alignment film is a film formed from a polymer compound, which has an orientation control force that enables the polymeric liquid crystal compound to be aligned in a desired direction.

[0196] Alignment films facilitate the alignment of polymeric liquid crystal compounds. The alignment states of liquid crystals, such as horizontal alignment, vertical alignment, mixed alignment, and tilted alignment, vary depending on the properties of the alignment film and the polymeric liquid crystal compound, and their combinations can be arbitrarily chosen. For example, when the alignment film is a material that acts as an alignment control force to achieve a horizontal alignment, the polymeric liquid crystal compound can achieve a horizontal or mixed alignment; when it is a material that achieves a vertical alignment, the polymeric liquid crystal compound can achieve a vertical or tilted alignment. The terms "horizontal," "vertical," etc., refer to the direction of the long axis of the aligned polymeric liquid crystal, with the polarizing film plane as a reference. Horizontal alignment refers to the alignment of the long axis of the aligned polymeric liquid crystal in a direction parallel to the polarizing film plane. Here, "parallel" means an angle of 0° ± 20° relative to the polarizing film plane. Vertical alignment refers to the alignment of the long axis of the aligned polymeric liquid crystal in a direction perpendicular to the polarizing film plane. Here, "vertical" means an angle of 90° ± 20° relative to the polarizing film plane.

[0197] Regarding orientation control, when the alignment film is formed from an orientation polymer, it can be arbitrarily adjusted by surface state and friction conditions; when it is formed from a photo-oriented polymer, it can be arbitrarily adjusted by polarized light irradiation conditions, etc. Furthermore, liquid crystal orientation can also be controlled by selecting the surface tension, liquid crystal properties, and other physical properties of the polymerizable liquid crystal compound.

[0198] As an alignment film, it is preferable to have an alignment film that is insoluble in the solvent used to form a polarizing film on the alignment film, and has heat resistance for solvent removal and heat treatment for liquid crystal alignment. Examples of alignment films include alignment films formed from alignment polymers, photo-alignment films, groove alignment films, and stretched films stretched along the alignment direction, with photo-alignment films being preferred.

[0199] The thickness of the alignment film is typically in the range of 10–5000 nm, preferably in the range of 10–1000 nm, and more preferably in the range of 30–300 nm.

[0200] Examples of oriented polymers include polyamides with intramolecular amide bonds, gelatin-like polymers, polyimides with intramolecular imide bonds and their hydrolysates such as polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylates. Among these, polyvinyl alcohol is preferred.

[0201] These orientation polymers can be used alone or in combination of two or more.

[0202] Oriented films formed from oriented polymers can typically be obtained by coating a composition (hereinafter also referred to as "oriented polymer composition") made by dissolving the oriented polymer in a solvent onto a substrate and removing the solvent, or by coating the oriented polymer composition onto a substrate, removing the solvent, and then rubbing (friction method).

[0203] Examples of solvents mentioned above include water; alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl pentyl ketone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorinated hydrocarbon solvents such as chloroform and chlorobenzene; and so on. These solvents can be used alone or in combination of two or more.

[0204] The concentration of the oriented polymer in the oriented polymer composition is only required to be within the range where the oriented polymer can be completely dissolved in the solvent. Relative to the solution, it is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass (based on solid content).

[0205] Commercially available orientation film materials can also be used directly as orientation polymer compositions. Examples of commercially available orientation film materials include SUNEVER (registered trademark) (manufactured by Nissan Chemical Industries, Ltd.) and OPTMER (registered trademark) (manufactured by JSR Corporation).

[0206] Methods for coating oriented polymer compositions onto a substrate include known methods such as spin coating, extrusion coating, gravure coating, die coating, bar coating, and applicator coating, as well as printing methods such as flexographic printing.

[0207] When the orientation film of the present invention is manufactured using a continuous manufacturing method in the form of roll-to-roll, the coating method typically employs a printing method such as gravure coating, die coating, or flexographic coating.

[0208] A dry coating film of the oriented polymer can be formed by removing the solvent contained in the oriented polymer composition. Examples of solvent removal methods include natural drying, ventilation drying, heating drying, and vacuum drying.

[0209] One method for performing friction is to bring a film of an oriented polymer, formed on the surface of a substrate by coating an oriented polymer composition onto a substrate and annealing it, into contact with a friction roller wound with a friction cloth and rotating.

[0210] Photo-aligned films are typically formed from polymers, oligomers, or monomers with photoreactive groups.

[0211] In the case of continuously forming a polymerizable liquid crystal, polymers with a molecular weight of 5000 or more are preferred from the viewpoint of solvent resistance, and acrylic polymers are preferred from the viewpoint of affinity, especially when the polymerizable liquid crystal is (meth)acryloyl. A photo-alignment film can be obtained by coating a composition (hereinafter also referred to as "composition for photo-alignment film formation") containing a polymer, oligomer or monomer having photoreactive groups, and a solvent onto a substrate, drying off the solvent, and then irradiating it with polarized light (preferably polarized UV light).

[0212] From the perspective that the direction of the orientation control force can be arbitrarily controlled by selecting the polarization direction of the irradiated polarized light, the photo-alignment film is more preferable.

[0213] A photoreactive group is a group that generates liquid crystal alignment ability through light irradiation. Specifically, it is a group that undergoes a light-induced molecular orientation induction or isomerization reaction, dimerization reaction, photocrosslinking reaction, or photodecomposition reaction, which is the origin of liquid crystal alignment ability. Among these photoreactive groups, those that undergo dimerization or photocrosslinking reactions are preferred from the perspective of excellent alignment. As a photoreactive group capable of undergoing such reactions, it is preferred to have a group having unsaturated bonds, especially double bonds, and more preferably a group having at least one selected from the group consisting of carbon-carbon double bonds (C=C bonds), carbon-nitrogen double bonds (C=N bonds), nitrogen-nitrogen double bonds (N=N bonds), and carbon-oxygen double bonds (C=O bonds).

[0214] Examples of photoreactive groups with C=C bonds include vinyl, polyenyl, stilbazole, stilbazole group, chalcone, and cinnamoyl groups. Examples of photoreactive groups with C=N bonds include groups with structures such as aromatic Schiff bases and aromatic hydrazones. Examples of photoreactive groups with N=N bonds include azophenyl, azonaphthyl, aromatic heterocyclic azo, diazo, and formazanyl groups, as well as groups with an azobenzene oxide as their basic structure. Examples of photoreactive groups with C=O bonds include benzophenone, coumarin, anthraquinone, and maleimide groups.

[0215] These groups may have substituents such as alkyl, alkoxy, aryl, allyloxy, cyano, alkoxycarbonyl, hydroxyl, sulfonic acid, and haloalkyl.

[0216] The solvent for the composition for forming a photo-oriented film is preferably a solvent that dissolves the polymer and monomer having photoreactive groups. Examples of such solvents include those listed as solvents for the aforementioned orientation polymer composition.

[0217] The content of the polymer or monomer having photoreactive groups relative to the composition for forming the photoalignment film can be appropriately adjusted according to the type of polymer or monomer having photoreactive groups and the thickness of the photoalignment film to be manufactured, but it is preferably set to 0.2% by mass or more, and particularly preferably in the range of 0.3% to 10% by mass. In addition, within a range that does not significantly impair the properties of the photoalignment film, polymeric materials such as polyvinyl alcohol and polyimide, and photosensitizers may be included.

[0218] As a method for coating the composition for forming a photo-alignment film onto the anti-diffusion layer, the same method as the method for coating an orientation polymer composition onto the anti-diffusion layer can be cited. As a method for removing the solvent from the coated composition for forming a photo-alignment film, for example, the same method as the method for removing the solvent from the orientation polymer composition can be cited.

[0219] To irradiate with polarized light, the product obtained by removing the solvent from the composition for forming a photo-alignment film coated on a substrate can be directly irradiated with polarized light, or the polarized light can be irradiated from the substrate and allowed to pass through. Furthermore, it is particularly preferable that the polarized light is substantially parallel light. The wavelength of the polarized light used for irradiation is preferably in the wavelength range where the photoreactive groups of the polymer or monomer having photoreactive groups can absorb light energy. Specifically, UV (ultraviolet light) in the wavelength range of 250–400 nm is particularly preferred. Examples of light sources used for this polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, KrF, ArF, and other ultraviolet lasers, with high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps being more preferred. These lamps are preferred because they emit ultraviolet light with a wavelength of 313 nm, which has a high luminous intensity. The light from the aforementioned light source can be passed through a suitable polarizer to irradiate the product, thereby irradiating with polarized light. As the polarizer, polarizing filters, polarizing prisms such as Glan-Thomson and Glan-Taylor, and wire grid-type polarizers can be used.

[0220] It should be noted that if masking is applied during rubbing or polarized light irradiation, multiple regions (patterns) with different liquid crystal orientations can also be formed.

[0221] A groove-aligned film is a film with raised or recessed patterns or multiple grooves (slots) on its surface. When liquid crystal molecules are placed on a film with multiple linear grooves arranged at equal intervals, the liquid crystal molecules are aligned along the direction of the grooves.

[0222] Methods for obtaining grooved oriented films include: exposing the surface of a photosensitive polyimide film through an exposure mask with a patterned slit, followed by development and rinsing to form a raised or recessed pattern; forming a layer of UV-curable resin before curing on a plate-shaped master with grooves on its surface, transferring the resin layer to a substrate, and then curing it; and pressing a roll-shaped master with multiple grooves against a film of UV-curable resin before curing formed on a substrate to form a raised or recessed pattern, followed by curing. Specifically, methods described in Japanese Patent Application Publication No. 6-34976 and Japanese Patent Application Publication No. 2011-242743 are examples.

[0223] To obtain an orientation with minimal orientation disorder, the width of the convex portion of the grooved orientation film is preferably 0.05–5 μm, the width of the concave portion is preferably 0.1–5 μm, and the depth of the step difference between the convex and concave portions is preferably less than 2 μm, and more preferably less than 0.01–1 μm.

[0224] 〔Polarizing film〕

[0225] The aforementioned polarizing film forming composition is coated onto the alignment film obtained as described above to form a coating film. Then, the solvent contained in the polarizing film forming composition is removed under conditions where the polymerizable liquid crystal will not polymerize, thereby forming a dried coating film of the polarizing film forming composition on the surface of the substrate. Examples of solvent removal methods include natural drying, ventilation drying, heating drying, and reduced pressure drying.

[0226] The aforementioned dried coating film is heated to align the polymeric liquid crystal compound contained in the film, particularly to a smectic state. While maintaining this liquid crystal orientation, energy is irradiated onto the dried coating film, thereby causing the polymeric liquid crystal compound to polymerize. When the composition for forming the polarizing film contains a polymerization initiator, energy that allows the polymerization initiator to be activated is preferred. When the polymerization initiator is a photopolymerization initiator, light is preferred. The irradiated light can be appropriately selected based on the type of polymerization initiator contained in the aforementioned dried coating film, or the type of polymeric liquid crystal (particularly the type and amount of polymeric groups possessed by the polymeric liquid crystal compound).

[0227] Examples of light sources include light selected from the group consisting of visible light, ultraviolet light, and laser light, as well as active electron beams. Among these, ultraviolet light is preferred from the perspective of easy control of the polymerization reaction and the ability to use widely used devices in the art for polymerization. Therefore, it is preferable to select the types of polymerizable liquid crystal compound and polymerization initiator contained in the polarizing film forming composition in advance in a manner that allows polymerization to be carried out using ultraviolet light. Furthermore, during polymerization, it is preferable to control the polymerization temperature by cooling the aforementioned dried coating film simultaneously with ultraviolet light irradiation using an appropriate cooling method. If the polymerizable liquid crystal compound is polymerized at a lower temperature through such cooling, a polarizing film can be appropriately manufactured even if a substrate with low heat resistance is used as the substrate.

[0228] Example

[0229] The present invention will be described in more detail below through examples. It should be noted that, unless otherwise specified, "%" and "parts" in the examples refer to mass % and mass parts, respectively.

[0230] <Example 1>

[0231] [Preparation of compositions for photo-alignment film formation]

[0232] The following components as disclosed in Japanese Patent Application Publication No. 2013-033249 are mixed, and the resulting mixture is stirred at 80°C for 1 hour to obtain a composition for photo-alignment film formation.

[0233] Photooriented polymers:

[0234]

[0235] Solvent: 98 parts o-xylene

[0236] [Preparation of Agent A]

[0237] The following components are mixed and stirred at 25°C for 1 hour to obtain Agent A (1). It should be noted that the water content of o-xylene used as a solvent is <100ppm.

[0238] Reactive additive: LAROMER PR9000 (manufactured by BASF Japan Ltd.) 2.0 parts

[0239] (Hereinafter also referred to as PR9000)

[0240] Solvent: 70 parts o-xylene

[0241] The prepared agent A (1) was loaded into an SUS container, the gas phase was replaced with dry nitrogen, and then sealed.

[0242] [Preparation of Agent B]

[0243] The following components were mixed and stirred at 80°C for 1 hour to obtain agent B (1). As a dichroic pigment, the azo pigment described in the examples of Japanese Patent Application Publication No. 2013-101328 was used. It should be noted that the o-xylene used as a solvent had a water content of <100 ppm.

[0244] Polymerizable liquid crystal compounds (mixtures):

[0245]

[0246] Dichroic pigments:

[0247]

[0248]

[0249] Polymerization initiator: 2-Dimethylamino-2-benzyl-1-(4-morpholinophenyl)butane-1-one

[0250] (Irgacure 369) (manufactured by Ciba Specialty Chemicals Inc.)

[0251] 6 copies

[0252] Leveling agent: Polyacrylate compound (BYK-361N; manufactured by BYK-Chemie)

[0253] 1.2 parts solvent: 330 parts o-xylene

[0254] The prepared agent B (1) was loaded into an SUS container, the gas phase was replaced with dry nitrogen, and then sealed.

[0255] <Method for manufacturing polarizing film>

[0256] (1) Formation of photo-alignment film

[0257] Using a cellulose triacetate membrane (KC8UX2M, manufactured by Konica Minolta Co., Ltd.) as a substrate, the membrane surface was corona treated, and then the above-mentioned composition for forming a photo-aligned film was coated on it. The coating was dried at 120°C to obtain a dried coating. Polarized UV light was then irradiated onto the dried coating to form a photo-aligned film, resulting in a film with the photo-aligned film. The polarized UV light treatment was performed using a UV irradiation device (SPOT CURE SP-7; manufactured by USHIO INC.) at an intensity of 100 mJ / cm² measured at a wavelength of 365 nm. 2 The process was carried out under the specified conditions. A film with a photo-aligned coating was obtained as described above.

[0258] (2) Formation of polarizing film

[0259] After preparing Agent A (1) and Agent B (1), they were stored at 25°C for 3 months. Then, Agent A (1) and Agent B (1) were mixed and stirred at 25°C for 1 hour to obtain the composition (1) for polarizing film formation.

[0260] After obtaining the aforementioned polarizing film forming composition (1), the composition (1) was coated onto the film with the photo-alignment film obtained above using a rod coating method. Then, it was heated and dried in a drying oven at 120°C for 1 minute to thoroughly remove the solvent. Afterward, it was cooled to room temperature to allow the polymerizable liquid crystal compound to transform into a smectic liquid crystal state. Next, an exposure of 1000 mJ / cm² was applied using a UV irradiation device (UniQure VB-15201BY-A; manufactured by USHIO INC.). 2 Ultraviolet light (based on 365 nm) is irradiated onto the layer formed by the polarizing film forming composition (1), thereby causing the polymerizable liquid crystal compound contained in the dried coating to polymerize while maintaining the smectic liquid crystal state of the aforementioned polymerizable liquid crystal compound, thus forming a polarizing film (1) from the dried coating. The film thickness of the polarizing film (1) was measured using a laser microscope (Olympus Corporation OLS3000), and the result was 2.3 μm. The product thus obtained is a polarizer (polarizing film laminate) comprising a polarizing film and a substrate. X-ray diffraction measurements were performed on the polarizing film (1) using an X-ray diffraction apparatus X'Pert PRO MPD (Spectris Corporation), and a sharp diffraction peak (Bragg peak) with a half-width (FWHM) of about 0.17° was obtained near 2θ = 20.2°. The same result was also obtained when incident from the direction perpendicular to the rubbing. The ordered period (d) determined from the peak position is approximately The formation of the structure reflects a higher-order smectic phase.

[0261] <Determination of Moisture Content>

[0262] The water content of the solvent was determined by electrostatic titration using a Karl Fischer moisture meter (Kyoto Electronics Industries, Ltd. MKC-710M).

[0263] <Determination of polarization Py and monomer transmittance Ty>

[0264] The polarization degree Py and monomer transmittance Ty of the polarizing film (1) were measured as described below. Within a wavelength range of 380 nm to 780 nm, a device was used, consisting of a folder with a polarizer mounted on a spectrophotometer (Shimadzu Corporation UV-3150), to measure the transmittance (Ta1) along the transmission axis and the transmittance (Tb2) along the absorption axis using a double-beam method. The folder had a screen on the reference side that cut off 50% of the light intensity.

[0265] Using the following equations (Equation 1) and (Equation 2), the monomer transmittance and polarization at each wavelength were calculated. Visibility correction was then performed using a 2-degree field of view (C light source) from JISZ 8701, and the visibility-corrected monomer transmittance (Ty) and visibility-corrected polarization (Py) were calculated. The results show high performance from a highly oriented smectic liquid crystal, with Ty = 42% and Py = 98%.

[0266] Monomer transmittance Ty (%) = (Ta1 + Tb2) / 2 (Equation 1)

[0267] Polarization degree Py(%)=(Ta1-Tb2) / (Ta1+Tb2)×100 (Formula 2)

[0268] <Evaluation of Fit>

[0269] A 25mm wide cellotape (made by NICHIBAN) was attached to the surface and back of the obtained polarizing film (1), and a 90° peel test was performed on the surface and back. No peeling was recorded as 0, peeling was recorded as △ when only part of the test area peeled, and peeling was recorded as × when the entire test area peeled.

[0270] <Appearance Evaluation>

[0271] The presence or absence of foreign matter was confirmed by visual inspection of the obtained polarizing film (1). Cases where no foreign matter was detected by visual inspection were recorded as 0, cases where a small amount of foreign matter was detected were recorded as △, and cases where a large amount of foreign matter was detected were recorded as ×.

[0272] <Examples 2 and 3>

[0273] The storage container for agent A was prepared as shown in the table. Otherwise, the process was the same as in Example 1 to obtain the polarizing film forming compositions (2) and (3) and the polarizing films (2) and (3). The Py, Ty, adhesion, and appearance of the obtained polarizing films were evaluated in the same manner as in Example 1.

[0274] <Example 4>

[0275] The gas phase of the container storing agent A was filled with air, and the process was otherwise carried out in the same manner as in Example 1 to obtain the composition (4) for forming a polarizing film and the polarizing film (4). The Py, Ty, adhesion, and appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

[0276] <Example 5>

[0277] The following compounds were used as reactive additives, and the procedure was otherwise followed as in Example 1 to obtain the polarizing film forming composition (5) and the polarizing film (5). The Py, Ty, adhesion, and appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

[0278] Reactive additive: Karenz AOI (manufactured by Showa Denko Co., Ltd.) 2.0 parts

[0279] <Example 6>

[0280] The following compounds were used as reactive additives, and the procedure was otherwise followed as in Example 1 to obtain the composition (6) for forming a polarizing film and the polarizing film (6). The Py, Ty, adhesion, and appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

[0281] Reactive additive: KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0 parts

[0282] <Examples 7 and 8>

[0283] The solvent for agent A was as described in the table, except that the procedure was the same as in Example 1, to obtain the polarizing film forming compositions (7) and (8) and the polarizing films (7) and (8). It should be noted that the toluene used had a water content of <100 ppm, and the anisole had a water content of 250 ppm. The Py, Ty, adhesion, and appearance of the obtained polarizing films were evaluated in the same manner as in Example 1.

[0284] <Examples 9-12>

[0285] The solvent for agent B was as listed in the table, except that the procedure was the same as in Example 1, to obtain the polarizing film forming compositions (9) to (12) and polarizing films (9) to (12). It should be noted that the water content of each solvent used was as follows: 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.

[0286] <Example 13>

[0287] The dichroic pigment was added in the amount specified in the table. Otherwise, the process was the same as in Example 1 to obtain the composition (13) for forming a polarizing film and the polarizing film (13). The Py, Ty, adhesion, and appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

[0288] <Example 14>

[0289] A dichroic pigment represented by (1-2) was added to agent A, and dichroic pigments represented by (1-1) and (1-3) were added to agent B. Otherwise, the process was the same as in Example 1 to obtain a composition (14) for forming a polarizing film and a polarizing film (14). The Py, Ty, adhesion, and appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

[0290] <Comparative Example 1>

[0291] After preparing Agent A and Agent B in the same manner as in Example 1, the two liquids were mixed by stirring at 25°C for 1 hour in an SUS container. After mixing the two liquids, the mixture was sealed under dry nitrogen and stored at 25°C for 3 months before coating. The Py, Ty, adhesion, and appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

[0292] <Comparative Example 2>

[0293] Without using reactive additives, the composition for forming a polarizing film was prepared in the same manner as in Comparative Example 1. It was sealed under dry nitrogen, stored at 25°C for 3 months, and then coated. The Py, Ty, adhesion, and appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

[0294] <Comparative Examples 3 and 4>

[0295] As described in the table, the reactive additives were changed. Otherwise, Agent A and Agent B were prepared in the same manner as in Comparative Example 1. The two liquids were then mixed in an SUS container by stirring at 25°C for 1 hour. After mixing, the two liquids were sealed under dry nitrogen and stored at 25°C for 3 months before coating. The Py, Ty, adhesion, and appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

[0296] <Comparative Example 5>

[0297] A dichroic pigment was added to agent A and removed from agent B. Otherwise, the polarizing film was obtained by operating in the same manner as in Example 1, and the polarizing film was evaluated for Py, Ty, adhesion, and appearance by operating in the same manner as in Example 1.

[0298] [Table 1]

[0299]

[0300] The compositions of Examples 1-14, in which the reactive additive and the dichroic pigment containing an azo dye with an amine structure were stored separately, yielded polarizing films with good optical properties, high adhesion, and excellent appearance even after being coated three months after preparation of the two agents. On the other hand, the compositions of Comparative Examples 1, 3, and 4, in which the reactive additive and the dichroic pigment containing an azo dye with an amine structure were mixed and stored for three months, and Comparative Example 5, in which the reactive additive and the dichroic pigment containing an azo dye with an amine structure were contained in the same reagent, yielded polarizing films with poor optical properties, adhesion, and appearance. It is evident that the polarizing film obtained from the composition of Comparative Example 2, which does not contain the reactive additive, has poor adhesion.

Claims

1. A two-liquid type polarizing film forming composition composed of an A agent and a B agent which are separately stored, the A agent contains a reactive additive having a polymerizable group and an active hydrogen reactive group in a molecule and a solvent, the B agent contains a dichroic dye and a solvent, the dichroic dye contains an azo dye having an amine structure.

2. The two-liquid type polarizing film forming composition according to claim 1, further containing a polymerizable liquid crystal compound.

3. The two-liquid type polarizing film forming composition according to claim 1 or 2, wherein The water content of the solvent contained in the A agent is less than 300 ppm.

4. The two-liquid type polarizing film forming composition according to claim 2, wherein The amount of the reactive additive contained in the A agent is 0.5 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the polymerizable liquid crystal compound.

5. The two-liquid type polarizing film forming composition according to claim 2, wherein The water content of the solvent contained in the A agent is less than 300 ppm, The amount of the reactive additive contained in the A agent is 0.5 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the polymerizable liquid crystal compound.

6. The storage method for the two-liquid type polarizing film forming composition according to any one of claims 1 to 5, wherein The A agent and the B agent are separately stored.

7. The preservation method of claim 6, wherein, The A agent is stored in a plastic container or a metal container.

8. The preservation method of claim 6 or 7, wherein, The A agent is stored under a dry non-reactive gas atmosphere.

9. A method for producing a polarizing film forming composition, comprising a step of mixing the A agent and the B agent which constitute the two-liquid type polarizing film forming composition according to any one of claims 1 to 5, the A agent containing a reactive additive having a polymerizable group and an active hydrogen reactive group in a molecule and a solvent, the B agent containing a dichroic dye and a solvent, the dichroic dye containing an azo dye having an amine structure.

10. A method for producing a polarizing film, comprising the following steps: a step of forming an alignment film on a substrate; a step of mixing the A agent and the B agent which constitute the two-liquid type polarizing film forming composition according to any one of claims 1 to 5, the A agent containing a reactive additive having a polymerizable group and an active hydrogen reactive group in a molecule and a solvent, the B agent containing a dichroic dye and a solvent, the dichroic dye containing an azo dye having an amine structure, to thereby obtain a polarizing film forming composition; a step of applying the mixed polarizing film forming composition on the alignment film to thereby obtain a coated film; and a step of curing the coated film.

10. A method for producing a polarizing film, comprising the following steps: a step of forming an alignment film on a substrate; a step of mixing the A agent and the B agent which constitute the two-liquid type polarizing film forming composition according to any one of claims 1 to 5, the A agent containing a reactive additive having a polymerizable group and an active hydrogen reactive group in a molecule and a solvent, the B agent containing a dichroic dye and a solvent, the dichroic dye containing an azo dye having an amine structure, to thereby obtain a polarizing film forming composition; a step of applying the mixed polarizing film forming composition on the alignment film to thereby obtain a coated film; and a step of curing the coated film.

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