KR20230058048A - Composition for forming a two-component polarizing film - Google Patents

Abstract

[PROBLEMS] To provide a composition for forming a polarizing film, a storage method thereof, a method for producing the composition, and a method for producing a polarizing film, capable of obtaining a polarizing film having good optical performance even after long-term storage.
[Solution Means] A reactive additive having a polymerizable group and an active hydrogen reactive group in a molecule and agent A containing a solvent, and agent B containing a dichroic dye and a solvent, wherein the dichroic dye is an azo dye having an amine structure A composition for forming a two-component polarizing film comprising:

Description

Composition for forming a two-component polarizing film

The present invention relates to a composition for forming a two-component polarizing film and a storage method thereof, a method for preparing the composition for forming a polarizing film, and a method for manufacturing a polarizing film.

In recent years, with the thinning of image display devices, optical films such as polarizing plates and retardation plates using a polarizing film having a liquid crystal cured layer obtained by applying a polymerizable liquid crystal compound on a substrate or an alignment film and curing it in an aligned state have been developed. there is. In the manufacture of such an optical film, from the viewpoint of film formability and handling, the polymerizable liquid crystal compound is usually a composition for forming a polarizing film in which the polymerizable liquid crystal compound is dissolved in a solvent or the like, and is applied onto a substrate or an alignment film. do. In the case of producing an optical film by applying the composition on a base material or alignment film, if the adhesion between the base material or alignment film and the obtained optical film is higher, peeling during processing does not occur, so that a high-quality optical film can be obtained. Since it is easy, it is known that it is preferable, and a composition provided with the characteristics of imparting a highly adhesive optical film has been proposed (Patent Document 1).

Japanese Unexamined Patent Publication No. 2017-83843

However, it has been found that when a polarizing film is formed after storing such a composition for a long period of time, there is a problem that good optical performance is not always obtained. Accordingly, an object of the present invention is to provide a composition for forming a polarizing film, a storage method thereof, a method for producing the composition, and a method for producing a polarizing film, capable of obtaining a polarizing film having good optical performance even after long-term storage.

The inventors of the present invention have reached the present invention as a result of repeated examinations in detail in order to solve the above problems. That is, the present invention includes the following preferred aspects.

[1] Consists of agent A containing a reactive additive having a polymerizable group and active hydrogen reactive group in a molecule and a solvent, and agent B containing a dichroic dye and a solvent, wherein the dichroic dye contains an azo dye having an amine structure A composition for forming a two-component polarizing film.

[2] The composition for forming a two-component polarizing film according to [1], further containing a polymerizable liquid crystal compound.

[3] The composition for forming a two-component polarizing film according to [1] or [2], wherein the moisture content of the solvent contained in the agent A is less than 300 ppm.

[4] The composition for forming a two-component polarizing film according to [2] or [3], wherein the amount of the reactive additive contained in the agent A is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymerizable liquid crystal compound. .

[5] The method for storing the composition for forming a two-component polarizing film according to any one of [1] to [4], wherein the agent A and the agent B are separately stored.

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

[7] The storage method according to [5] or [6], wherein the agent A is stored under a dry inert gas atmosphere.

[8] Agent A containing a solvent and a reactive additive having a polymerizable group and an active hydrogen reactive group in the molecule constituting the composition for forming a two-component polarizing film according to any one of [1] to [4], and an amine structure A method for producing a composition for forming a polarizing film, comprising a step of mixing a dichroic dye containing an azo dye having and agent B containing a solvent.

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

[1] Constituting the composition for forming a two-component polarizing film according to any one of [4], A agent containing a reactive additive having a polymerizable group and an active hydrogen reactive group in the molecule and a solvent, and an azo having an amine structure A step of mixing a dichroic dye containing a dye and agent B containing a solvent to obtain a composition for forming a polarizing film;

a step of applying the mixed composition for forming a polarizing film onto the alignment film to obtain a coating film; and

Process of curing the coating film

A method for producing a polarizing film comprising a.

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

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail. In addition, the scope of the present invention is not limited to the embodiment described here, and various changes can be made without departing from the gist of the present invention.

The composition for forming a two-component polarizing film of the present invention contains agent A containing a solvent and a reactive additive having a polymerizable group and an active hydrogen reactive group in a molecule, a dichromatic pigment containing an azo pigment having an amine structure, and a solvent. It is composed of B zeros.

The composition for forming a two-component type polarizing film of the present invention contains a reactive additive, an azo dye having an amine structure, and a solvent dissolving them as essential components, and the reactive additive is added in agent A, and the azo dye having an amine structure is added to B Mixed separately from each other.

<A agent>

[Reactive additive]

A reactive additive generally refers to a substance added to a composition for forming a polarizing film in order to improve the adhesion of the polarizing film. The polymerizable group of the reactive additive contained in agent A means a group involved in polymerization reaction. The polymerizable group may be, for example, a carbon-carbon unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond, and specifically, for example, a vinyl group, a (meth)acrylic group, a vinyloxy group, 1-chloro A vinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, oxetanyl group, etc. are mentioned.

The active hydrogen reactive group of the reactive additive contained in agent A means a group having reactivity to a group having an active hydrogen such as a carboxy group (-COOH), a hydroxyl group (-OH), an amino group (-NH ₂ ), and an epoxy group, a glycol group A cydyl group, an oxazolyl group, a carbodiimide group, an aziridinyl group, an imide group, an isocyanate group, a thioisocyanate group, a maleic anhydride group, an alkoxysilyl group and the like are representative examples thereof. In the reactive additive, it is preferable that at least two active hydrogen reactive groups exist, and in this case, a plurality of active hydrogen reactive groups may be the same or different.

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

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

Specific examples of the reactive additive include compounds having a (meth)acrylic group and an epoxy group, such as methacryloyloxyglycidyl ether and acryloyloxyglycidyl ether; compounds having a (meth)acrylic group and an oxetanyl group, such as oxetane acrylate and oxetane methacrylate; compounds having a (meth)acrylic group and a lactone group, such as lactone acrylate and lactone methacrylate; compounds having a vinyl group and an oxazolyl group, such as vinyloxazoline and isopropenyloxazoline; compounds having a (meth)acrylic group and an isocyanate group, such as isocyanatomethyl acrylate, isocyanatomethyl methacrylate, 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate; and oligomers of compounds having a (meth)acrylic group and an alkoxysilyl group, such as 3-acryloyloxypropyltrimethoxysilane and 3-methacryloyloxypropylmethyldimethoxysilane. Moreover, the compound etc. which have a vinyl group, a vinylene group, and an acid anhydride, such as methacrylic anhydride, acrylic anhydride, maleic anhydride, and vinyl maleic anhydride, are mentioned. Among them, methacryloyloxyglycidyl ether, acryloyloxyglycidyl ether, isocyanatomethyl acrylate, isocyanatomethyl methacrylate, vinyloxazoline, 2-isocyanatoethyl acrylate, 2- Isocyanatoethyl methacrylate, 3-acryloyloxypropyltrimethoxysilane and the above oligomers are preferred, isocyanatomethyl acrylate, 2-isocyanatoethyl acrylate, 3-acryloyloxypropyl Trimethoxysilane and the aforementioned oligomers are particularly preferred.

As a reactive additive, a commercial item can be used as it is or after being purified as needed.

Commercially available products include, for example, Laromer (registered trademark) PR9000 (manufactured by BASF), Karenz AOI (registered trademark) (manufactured by Showa Denko Co., Ltd.), KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. can be heard

The amount of the reactive additive contained in agent A is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, still more preferably 1.5 parts by mass or more, and even more, based on 100 parts by mass of the polymerizable liquid crystal compound described later. It is 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, and still more preferably 5 parts by mass or less. When the amount of the reactive additive is equal to or greater than the lower limit and equal to or less than the upper limit, the adhesion of the polarizing film prepared from the composition for forming a two-component polarizing film according to the present invention is not impaired, and adhesion is easily improved. A reactive additive may be used independently and may be used in combination of 2 or more type. In the case of using two or more types of reactive additives, the amount of the reactive additives represents the total amount.

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

[solvent]

The moisture 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, still more preferably less than 150 ppm, and particularly preferably less than 100 ppm. When the moisture content of the solvent contained in agent A is less than the above upper limit, the reaction between the active hydrogen-reactive group of the reactive additive and water is difficult to occur, so that the adhesion of the polarizing film is easily improved even after long-term storage, and a polarizing film having an excellent appearance is obtained. easy. The lower limit of the moisture content of the solvent contained in agent A is 0 ppm. The moisture content of the solvent contained in agent A can be controlled within the above range by, for example, distilling the solvent together with a drying agent under an inert gas or coexisting with a molecular sieve or the like for a certain period of time. A commercially available dehydration solvent can also be used. The water content of the solvent contained in the agent A can be obtained using, for example, a Karl Fischer titration apparatus.

Specific examples of such a solvent include, for example, methanol, ethanol, butanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, cyclohexanol, and phenol. alcohol solvents such as; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, and methyl isobutyl ketone; non-chlorine aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicyclic hydrocarbon solvents such as cyclohexane; non-chlorine aromatic hydrocarbon solvents such as toluene, anisole, trimethylbenzene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran, dioxane and dimethoxyethane; chlorine solvents such as dichloromethane, dichloroethane, chlorotoluene, chloroform, chlorobenzene and dichlorobenzene; Sulfoxide solvents, such as dimethyl sulfoxide; amide solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone; Heterocyclic solvents, such as pyridine, etc. are mentioned. These organic solvents may be used individually or may be used in combination of multiple types. Among these organic solvents, ketone solvents, non-chlorine aliphatic hydrocarbon solvents, non-chlorine aromatic hydrocarbon solvents and chlorine solvents are preferred.

A solvent may be used independently and may be used in combination of 2 or more type. When two or more types of solvents are used in combination, the water content of the entire solvent used is preferably less than 300 ppm, but when a solvent with a water content of 300 ppm or more is contained, the water content of the entire solvent is preferably less than 300 ppm.

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

Agent A can be prepared by mixing the reactive additive, the solvent, and optional components described later as appropriate. Conditions such as mixing method, temperature and time are not particularly limited and can be appropriately selected according to the type and amount of components contained in agent A.

The agent A has a viscosity (25°C) of preferably 0.1 to 15 mPa·s, more preferably 0.1 to 10 mPa·s. When the viscosity of agent A is within the above range, handling properties are excellent, and mixing with agent B thereafter becomes easy.

As described above, in the composition for forming a two-component polarizing film of the present invention, the reactive additive is mixed separately in agent A and an azo dye having an amine structure described later in agent B, respectively. Therefore, agent A does not contain substantially the azo dye which has an amine structure mentioned later. "Substantially does not contain an azo dye having an amine structure" means that the content of the azo dye having an amine structure in agent A is preferably less than 0.5 parts by mass, more preferably 0.1 parts by mass relative to 100 parts by mass of the reactive additive. part, more preferably less than 0.05 part by mass. Preferably, content of the azo dye which has an amine structure in agent A is 0 mass part.

<Part B>

[two-color pigment]

The dichroic dye contained in agent B contains an azo dye having an amine structure. In the present invention, the amine structure is, specifically, the following formula (1A)

[Formula 1]

[In the formula, A ^a1 and A ^a2 are each independently 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, or a halogen atom. an alkylcarbonyl group of 1 to 21 carbon atoms, an alkylcarbonyloxy group of 1 to 21 carbon atoms which may have a halogen atom, an alkylsulfonyl group of 1 to 20 carbon atoms which may have a halogen atom, or a carbon atom of 6 to 60 which may have a halogen atom 20 represents an arylsulfonyl group, or represents a nitrogen-containing heterocycle such as a pyrrolidine ring in which A ^a1 and A ^a2 are bonded to each other and together with the nitrogen atom to which they are bonded. * represents a bonding hand.]

The group represented by can be mentioned.

The dichroic dye having an amine structure is, for example, the following general formula (1)

[Formula 2]

[Wherein, A ¹ and A ³ are each independently a phenyl group which may have a substituent, a naphthyl group which may have a substituent, a benzoic acid phenyl ester group which may have a substituent, or a monovalent heterocyclic group which may have a substituent indicate A ² is a 1,4-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, a 4,4′-stilbenzylene group which may have a substituent, or a 2 which may have a substituent represents a valent heterocyclic group. However, at least one of A ¹ to A ³ has an amine structure represented by the formula (1A) as a substituent. p represents an integer of 0 to 4, and when p is an integer of 2 or greater, a plurality of A ² may be the same or different.]

The pigment represented by can be mentioned.

Examples of the monovalent heterocyclic group include groups obtained by removing one hydrogen atom from heterocyclic compounds such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzoimidazole, oxazole and benzooxazole. Examples of the divalent heterocyclic group include groups obtained by removing two hydrogen atoms from the above heterocyclic compounds.

Phenyl group, naphthyl group, benzoic acid phenyl ester group, and monovalent heterocyclic group for A ¹ and A ³ , and 1,4-phenylene group, naphthalene-1,4-diyl group, 4,4' for A ² - As a substituent other than the amine structure represented by Formula (1A) which a stilbenylene group and a bivalent heterocyclic group have arbitrarily, it is an alkyl group of 1-6 carbon atoms; alkoxy groups having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group and a butoxy group; C1-C6 fluorinated alkyl groups, such as a trifluoromethyl group; cyano group; nitro group; halogen atoms, etc.; can be heard Moreover, as a specific example of a C1-C6 alkyl group, a methyl group, an ethyl group, a butyl group, a hexyl group, etc. are mentioned.

Among the dichroic dyes represented by Formula (1), compounds represented by the following formulas (1-1) to (1-8), respectively, are preferable.

[Formula 3]

[In formulas (1-1) to (1-8),

at least one of B ¹ to B ³ , at least one of B ⁴ to B ⁷ , at least one of B ⁸ to B ¹⁰ , at least one of B ¹¹ to B ¹² , at least one of B ¹³ to B ¹⁶ ; At least one of B ¹⁷ to B ²⁰ , at least one of B ²¹ to B ²⁵ , and at least one of B ²⁶ to B ³⁰ are substituents of the amine structure represented by the formula (1A). B ¹ to B ³⁰ other than substituents of the amine structure represented by the above formula (1A) are each independently a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, a cyano group, a nitro group, or a halogen atom. or a trifluoromethyl group.

n1-n4 represent the integer of 0-3 mutually independently.

When n1 is 2 or more, a plurality of B ² may be the same as or different from each other;

When n2 is 2 or more, a plurality of B ⁶ may be the same as or different from each other;

When n3 is 2 or more, a plurality of B ⁹ may be the same as or different from each other;

When n4 is 2 or more, a plurality of B ¹⁴ may be the same or different.]

The content of the azo dye having an amine structure contained in the agent B is preferably usually 1 part by mass or more, preferably 60 parts by mass or less, more preferably 60 parts by mass or less, based on 100 parts by mass of the polymerizable liquid crystal compound described later. is 20 parts by mass or less, more preferably 15 parts by mass or less. When the content of the dichroic dye having an amine structure is less than the lower limit, light absorption becomes insufficient and sufficient polarization performance cannot be obtained, and when the content exceeds the upper limit, alignment of the polymerizable liquid crystal may be inhibited. The azo dye which has an amine structure may be used independently, and may be used in combination of 2 or more type. When using the azo dye which has 2 or more types of amine structures, content of the azo dye which has an amine structure shows the total amount.

When the composition for forming a two-component polarizing film of the present invention does not contain a polymerizable liquid crystal compound described later, the amount of the azo dye having an amine structure contained in agent B is the total dichromatic dye contained in agent A and agent B 3 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and generally 100 parts by mass or less, preferably 90 parts by mass or less, and more preferably 85 parts by mass or less. .

[solvent]

The solvent contained in agent B is not particularly limited, but is preferably a solvent that is inactive to the azo dye having an amine structure and can completely dissolve the dye. Moreover, it is preferable that it is a solvent with high compatibility with the solvent used for A agent from the point of using agent A and agent B mixed, and the same solvent may be sufficient as it. Moreover, the solvent contained in agent B may be used independently or may be used in mixture of 2 or more types.

The content of the solvent in agent B is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, still more preferably 70 to 85% by mass with respect to the total mass of components contained in agent B. When the content of the solvent in the agent B is within the above range, the dichroic dye is easily dissolved uniformly, and a uniform coating film can be formed in the method for producing a polarizing film described later, so that a polarizing film with a good appearance is easy to obtain.

Specific examples of such a solvent include, for example, methanol, ethanol, butanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, cyclohexanol, and phenol. alcohol solvents such as; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, and methyl isobutyl ketone; non-chlorine aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicyclic hydrocarbon solvents such as cyclohexane; non-chlorine aromatic hydrocarbon solvents such as toluene, anisole, trimethylbenzene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran, dioxane and dimethoxyethane; chlorine solvents such as dichloromethane, dichloroethane, chlorotoluene, chloroform, chlorobenzene and dichlorobenzene; Sulfoxide solvents, such as dimethyl sulfoxide; amide solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone; Heterocyclic solvents, such as pyridine, etc. are mentioned. These organic solvents may be used individually or may be used in combination of multiple types.

As described above, in the composition for forming a two-component polarizing film of the present invention, the reactive additive is separately blended in agent A and the azo dye having an amine structure in agent B, respectively. Therefore, agent B does not contain the said reactive additive substantially. "Substantially contains no reactive additive" means that the content of the reactive additive in the agent B is preferably less than 0.5 parts by mass, more preferably less than 0.1 parts by mass, and further preferably less than 0.1 parts by mass with respect to 100 parts by mass of the azo dye having an amine structure. Preferably it means less than 0.05 mass part. Preferably, the content of the reactive additive in agent B is 0 parts by mass.

[Polymerizable liquid crystal compound]

The composition for forming a two-component polarizing film of the present invention preferably further contains a polymerizable liquid crystal compound. The polymerizable liquid crystal compound may be contained in either liquid A or liquid B constituting the composition for forming a two-component polarizing film of the present invention.

A polymerizable liquid crystal compound is a compound that has a polymerizable group and exhibits a liquid crystal state. The polymerizable group means a group involved in the polymerization reaction of the polymerizable liquid crystal compound, and it is preferably a photopolymerizable group. Here, the photopolymerizable group refers to a group that can participate in a polymerization reaction by an active radical or an acid generated from a photopolymerization initiator described later. Examples of the polymerizable group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxiranyl group, and an oxetanyl group. . Especially, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group, and an oxetanyl group are preferable, and an acryloyloxy group is more preferable. The liquid crystal may be a thermotropic liquid crystal or a lyotropic liquid crystal.

The polymerizable liquid crystal compound may 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 the present 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, and more preferably a thermotropic liquid crystal compound exhibiting a higher order smectic liquid crystal phase. It is a liquid crystal compound. Among them, 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 A thermotropic liquid crystal compound exhibiting an L phase is more preferred, and a thermotropic liquid crystal compound exhibiting a smectic B phase, a smectic F phase or a smectic I phase is further preferred. If the liquid crystal phase formed by the polymerizable liquid crystal compound is these higher order smectic phases, a polarizing film with higher polarization performance can be produced. In addition, such a polarizing film with high polarization performance is one in which a Bragg peak derived from a higher order structure such as a hexatic phase or a crystal phase is obtained in X-ray diffraction measurement. The Bragg peak is a peak derived from the periodic structure of molecular orientation, and a film having a periodic interval of 3 to 6 Å can be obtained.

As an example of the polymerizable liquid crystal compound, for example, the following formula (2)

[In Formula (2), X ¹ 1 , X ² , and X ³ each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein the divalent aromatic group or divalent alicyclic hydrocarbon group The hydrogen atom contained may be substituted with a halogen atom, an alkyl group of 1 to 4 carbon atoms, a fluoroalkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, a cyano group or a nitro group, and the divalent aromatic group or 2 A carbon atom constituting the valent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom. However, at least one of X ¹ , X ² , X ³ is a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent. Moreover, n is 1-3, and when n is 2 or more, X ^<1> may be respectively different. As for n from a viewpoint of liquid crystal expression, 1 or 2 is preferable.

Y ¹ , Y ² , W ¹ and W ² are each independently a single bond or a divalent linking group.

V ¹ and V ² each independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - constituting the alkanediyl group is -O-, -CO-, -S - or NH- may be substituted.

U ¹ and U ² each independently represent a polymerizable group or a hydrogen atom, and at least one is a polymerizable group.]

The compound represented by (Hereinafter, it may be called compound (2).), etc. are mentioned. The said polymeric liquid crystal may be used independently and may be used in combination of 2 or more type.

In compound (2), at least one of X, X ² and X ³ is a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent. In particular, X ¹ or X ³ is preferably a cyclohexane-1,4-diyl group which may have a substituent, and the cyclohexane-1,4-diyl group is a trans-cyclohexane-1,4-diyl group It is more preferable to be As the substituent optionally included in the 1,4-phenylene group which may have a substituent or the cyclohexane-1,4-diyl group which may have a substituent, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a butyl group; Halogen atoms, such as a furnace group and a chlorine atom and a fluorine atom, are mentioned. It is preferably unsubstituted. Moreover, when ^Y1 and ^Y2 have the same structure, it is preferable that at least 1 of ^X1 , ^X2, and ^X3 has a different structure. When at least one of X ¹ , X ² and X ³ has a different asymmetric structure, smectic liquid crystal tends to be easily expressed.

Y ¹ and Y ² are, independently of each other, a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -CH ₂ CH ₂ O-, -COO-, -OCO-, -N=N-, - CR ^a =CR ^b -, -C≡C- or -CR ^a =N- is preferable, and R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Y ¹ and Y ² are more preferably -CH ₂ CH ₂ -, -COO-, -OCO-, -N=N- or a single bond. Further, when all of X ¹ , X ² and X ³ have the same structure, it is preferable that Y ¹ and Y ² have mutually different bonding methods. When Y ¹ and Y ² are bonded in different ways, an asymmetric structure is formed, and thus smectic liquid crystal tends to be easily expressed.

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

Examples of the alkanediyl group having 1 to 20 carbon atoms represented by V ¹ and V ² include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, and a butane-1,4-diyl group. , pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1 ,14-diyl group and icosane-1,20-diyl group, etc. are mentioned. V ¹ and V ² are preferably a C2-C12 alkanediyl group, more preferably a linear C6-C12 alkanediyl group. Crystallinity is improved by using a linear C6-C12 alkanediyl group, and there exists a tendency for smectic liquid crystalline to be easily expressed.

Examples of the substituent optionally possessed by the alkanediyl group having 1 to 20 carbon atoms, which may have a substituent, include a cyano group and a halogen atom such as a chlorine atom and a fluorine atom. The alkanediyl group is preferably unsubstituted, It is more preferable that it is an unsubstituted and linear alkanediyl group.

U ¹ and U ² are preferably both polymerizable groups, and more preferably both are photopolymerizable groups. A polymerizable liquid crystal compound having a photopolymerizable group is advantageous in that a polymer can be formed in a state in which the liquid crystal has a higher degree of order because it can polymerize under lower temperature conditions than a thermally polymerizable group.

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

The polymerizable liquid crystal compound (2) is not particularly limited as long as it is a polymerizable liquid crystal compound that has at least one polymerizable group and exhibits smectic liquid crystallinity, and a known polymerizable liquid crystal compound can be used, but exhibits smectic liquid crystallinity. As the structure that is easily produced, those having an asymmetrical molecular structure are preferable in the molecular structure, and specifically, a polymerizable liquid crystal compound having a partial structure of (A-a) to (A-i) below and showing smectic liquid crystallinity. is more preferable. It is more preferable to have a partial structure of (A-a) or (A-b) or (A-c) from the viewpoint of easy to exhibit higher order smectic liquid crystal. Here, in the drawing, * indicates a bonding hand.

[Formula 4]

As a specific example of the compound represented by Formula (2), the compound represented by Formula (2-1) - Formula (2-23), etc. are mentioned. When the compound represented by Formula (2) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably trans.

[Formula 5]

[Formula 6]

[Formula 7]

Among the compounds represented by formula (2), formulas (2-2), (2-3), (2-4), (2-6), (2-7), (2-8), (2-13) ), at least one selected from the group consisting of compounds represented by (2-14) and (2-15), respectively, is preferred. As a polymeric liquid crystal compound, you may use individually by 1 type, and may use it in combination of 2 or more type.

The compound represented by Formula (2) can be used individually or in combination. Moreover, when combining 2 or more types of polymeric liquid crystal compounds, it is preferable that at least 1 type is a compound represented by Formula (2), and it is more preferable that 2 or more types are compounds represented by Formula (2). The mixing ratio in the case of combining two types of polymerizable liquid crystal compounds is usually 1:99 to 50:50, preferably 5:95 to 50:50, more preferably 10:90 to 50:50 is (mass ratio). When a polymerizable liquid crystal compound having one polymerizable group and a polymerizable liquid crystal compound having two polymerizable groups are combined, the mixing ratio (polymerizable liquid crystal compound having one polymerizable group: polymerizable liquid crystal compound having two polymerizable groups) ) is usually 1:99 to 50:50, preferably 5:95 to 50:50, and more preferably 10:90 to 50:50 (mass ratio).

The compound represented by Formula (2) is Lub et al. Recl. Trav. Chim. It can be produced by a known method described in Pays-Bas, 115, 321-328 (1996) or Japanese Patent No. 4719156.

When the composition for forming a two-component polarizing film is contained in agent B, the amount of the polymerizable liquid crystal compound contained in the composition for forming a two-component polarizing film of the present invention is preferably 40% of the total solid content in agent B. It is mass % or more, more preferably 60 mass % or more, still more preferably 70 mass % or more, and is preferably 99.9 mass % or less, more preferably 99 mass % or less. When the content of the polymerizable liquid crystal compound is equal to or greater than the lower limit and equal to or less than the upper limit, the orientation tends to increase. Here, the solid content refers to the total amount of components obtained by removing the solvent from the composition for forming a polarizing film.

Agent B can be prepared by mixing the azo dye having an amine structure, the solvent, and optional components to be described later depending on the case. Conditions such as mixing method, temperature and time are not particularly limited, and can be appropriately selected according to the type and amount of components contained in agent B.

The viscosity (25°C) of agent B is preferably from 0.1 to 15 mPa·s, more preferably from 0.1 to 10 mPa·s. When the viscosity of agent B is within the above range, handling properties are excellent, and subsequent mixing with agent A becomes easy.

The composition for forming a two-component polarizing film of the present invention may contain, in addition to the above components, arbitrary components such as a polymerization initiator, a sensitizer, a polymerization inhibitor, a leveling agent, and a dichromatic dye other than an azo dye having an amine structure. .

[Polymerization initiator]

The composition for forming a two-component polarizing film of the present invention may contain a polymerization initiator. A polymerization initiator is a compound capable of initiating a polymerization reaction such as a polymerizable liquid crystal compound. As the polymerization initiator, a photopolymerization initiator that generates active radicals by the action of light is preferable.

One or both of agent A or agent B constituting the composition for forming a two-component polarizing film of the present invention may contain a polymerization initiator, but when agent A contains a polymerization initiator, the polymerization initiator is a compound having no amine structure It is desirable to be

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

As the photopolymerization initiator, a known photopolymerization initiator can be used as long as it is a compound capable of initiating a polymerization reaction of a polymerizable liquid crystal compound. Specifically, photopolymerization initiators capable of generating active radicals or acids by the action of light are exemplified, and among these, photopolymerization initiators capable of generating radicals by the action of light are preferable. A photoinitiator can be used individually or in combination of 2 or more types.

As the photopolymerization initiator, a known photopolymerization initiator can be used. For example, as the photopolymerization initiator that generates active radicals, self-cleavage type benzoin-based compounds, acetophenone-based compounds, hydroxyacetophenone-based compounds, α-aminoacetophenone-based compounds, oxime ester-based compounds, acylphosphine oxide-based compounds, azo-based compounds, etc. can be used, and hydrogen drawing type benzophenone-based compounds, alkylphenone-based compounds, benzoin ether-based compounds, benzyl Ketal-based compounds, dibenzosberone-based compounds, anthraquinone-based compounds, xanthone-based compounds, thioxanthone-based compounds, halogenoacetophenone-based compounds, dialkoxyacetophenone-based compounds, halogenobisimidazole-based compounds, halo Genotriazine-based compounds, triazine-based compounds and the like can be used. As the photopolymerization initiator that generates an acid, iodonium salts, sulfonium salts, and the like can be used. From the viewpoint of excellent reaction efficiency at low temperatures, self-cleavage type photopolymerization initiators are preferred, and acetophenone-based compounds, hydroxyacetophenone-based compounds, α-aminoacetophenone-based compounds, and oxime ester-based compounds are particularly preferred.

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

As an acetophenone type compound, For example, dialkoxy acetophenone type compounds, such as diethoxy acetophenone; 2-Hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1-[4 -(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane- hydroxyacetophenone-based compounds such as 1-one oligomers; 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one, etc. α-aminoacetophenone-based compounds of , and the like are exemplified.

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

Examples of acylphosphine oxide-based compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

Examples of the benzophenone compound include benzophenone, o-benzoylmethyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra( tert-butyl peroxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone; and the like.

As an alkylphenone compound, for example, diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1- one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone and 2-hydroxy-2-methyl- Oligomers of 1-[4-(1-methylvinyl)phenyl]propan-1-one, etc. are mentioned.

As a triazine compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)- 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2 -methylphenyl)ethenyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5 - Triazine etc. are mentioned.

What is commercially available as a polymerization initiator can be used. Examples of commercially available polymerization initiators include Irgacure (registered trademark) 907, 184, 651, 819, 250 and 369 (manufactured by Ciba Specialty Chemicals Co., Ltd.); Sakeall (registered trademark) BZ, Z and BEE (manufactured by Seko Chemical Co., Ltd.); Kayacure (registered trademark) BP100 and UVI-6992 (manufactured by Dow Chemical Co., Ltd.); Adeka Optomer SP-152 and SP-170 (manufactured by ADEKA Corporation); TAZ-A and TAZ-PP (manufactured by Nippon Shiba Hegner Co., Ltd.); And TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.); etc. can be mentioned. One type of polymerization initiator may be used, or a plurality of polymerization initiators of two or more types may be mixed according to the light source of light.

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

[sensitizer]

When the composition for forming a two-component polarizing film of the present invention contains a polymerizable liquid crystal compound, the composition may contain a sensitizer. One or both of agent A or agent B constituting the composition for forming a two-component polarizing film of the present invention may contain a sensitizer, but when agent A contains a sensitizer, the sensitizer is a compound having no amine structure It is desirable to be As a sensitizer, a photosensitizer is preferable. Examples of the sensitizer include xanthone compounds such as xanthone and thioxanthone (eg, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, etc.); anthracene compounds such as anthracene and anthracene containing an alkoxy group (eg, dibutoxyanthracene); phenothiazine and rubrene; and the like.

The content of the sensitizer is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 10 parts by mass, still more preferably from 0.5 to 8 parts by mass, based on 100 parts by mass of the polymerizable liquid crystal compound. When the content of the sensitizer is within the above range, the polymerization reaction of the polymerizable liquid crystal compound is easily promoted.

[Polymerization inhibitor]

When the composition for forming a two-component polarizing film of the present invention contains a polymerizable liquid crystal compound, the composition may contain a polymerization inhibitor from the viewpoint of stably advancing the polymerization reaction. Either or both of agent A or agent B constituting the composition for forming a two-component polarizing film of the present invention may contain a polymerization inhibitor, but when agent A contains a polymerization inhibitor, the polymerization inhibitor is It is preferable that it is a compound which does not have. The progression of the polymerization reaction can be controlled by the polymerization inhibitor.

Examples of the polymerization inhibitor include hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (eg, butyl catechol, etc.), pyrogallol, 2,2,6,6-tetramethyl-1- radical scavengers such as piperidinyloxy radical; Thiophenols; β-naphthylamines and β-naphthols; and the like.

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 30 parts by mass, based on 100 parts by mass of the polymerizable liquid crystal compound. 10 parts by mass, more preferably 0.5 to 8 parts by mass. When the content of the polymerization inhibitor is within the above range, it is easy to perform polymerization without disturbing the alignment of the polymerizable liquid crystal.

[Leveling agent]

The composition for forming a two-component polarizing film of the present invention may contain a leveling agent. The leveling agent has a function of adjusting the fluidity of the composition and making the film obtained by applying the composition more flat, and examples thereof include surfactant. One or both of agent A or agent B constituting the composition for forming a two-component polarizing film of the present invention may contain a leveling agent, but when agent A contains a leveling agent, the leveling agent is a compound having no amine structure It is desirable to be

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

When the composition for forming a two-component polarizing film of the present invention contains a leveling agent, it is preferably from 0.01 to 5 parts by mass, more preferably from 0.05 to 3 parts by mass, based on the total solid content of the composition for forming a two-component polarizing film. . When the content of the leveling agent is within the above range, it is easy to horizontally align the polymerizable liquid crystal when the polymerizable liquid crystal compound is contained, and the obtained polarizing film tends to be smoother. When the content of the leveling agent exceeds the above range, unevenness tends to occur in the resulting polarizing film. Moreover, you may contain 2 or more types of leveling agents.

[Dichromatic dyes other than azo dyes having an amine structure]

The composition for forming a two-component polarizing film of the present invention may contain a dichroic dye other than an azo dye having an amine structure. As such a dichroic dye, those having an absorption maximum wavelength (λMAX) in the range of 300 to 700 nm are preferable, and examples thereof include azo dyes, anthraquinone dyes, oxazine dyes, acridine dyes having no amine structure, cyanine pigments, naphthalene pigments, and the like. Dichromatic dyes other than azo dyes having an amine structure may be used alone or in combination of two or more.

As an azo dye which does not have an amine structure, what does not contain an amine structure as a substituent of A1-A3 in Formula (1) mentioned above is mentioned, for example.

As an anthraquinone dye, Formula (1-9)

[Formula 8]

[Wherein, R ¹ to R ⁸ independently represent a hydrogen atom, -Rx, -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom, and R ^x has 1 to 10 carbon atoms. represents an alkyl group of 4 or an aryl group having 6 to 12 carbon atoms]

The compound represented by is preferable.

As an oxazine pigment, formula (1-10)

[Formula 9]

[Wherein, R ⁹ to R ¹⁵ each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom, and R ^x has 1 carbon atom represents an alkyl group of to 4 or an aryl group of 6 to 12 carbon atoms]

The compound represented by is preferable.

As an acridine dye, Formula (1-11)

[Formula 10]

[Wherein, R ¹⁶ to R ²³ each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom, and R ^x has 1 carbon atom represents an alkyl group of to 4 or an aryl group of 6 to 12 carbon atoms]

The compound represented by is preferable.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^x in the formulas (1-9), (1-10) and (1-11) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and Hexyl group etc. are mentioned, A phenyl group, a toluyl group, a xylyl group, a naphthyl group etc. are mentioned as a C6-C12 aryl group.

As a cyanine pigment, formula (1-12)

[Formula 11]

[Wherein, D ¹ and D ² are each independently represented by formulas (1-12a) to (1-12d)

[Formula 12]

represents a group represented by any of the above, and n5 represents an integer of 1 to 3]

A compound represented by and formula (1-13)

[Formula 13]

[wherein, D ³ and D ⁴ are each independently represented by formulas (2-13a) to (2-13h)

[Formula 14]

represents a group represented by any of the above, and n6 represents an integer of 1 to 3]

The compound represented by is preferable.

When using a combination of the azo dye having the above-mentioned amine structure and a dichroic dye other than the azo dye having the amine structure, the total content of all dichroic dyes is usually based on 100 parts by mass of the content of the polymerizable liquid crystal compound. It is 1-60 mass parts, Preferably it is 1-20 mass parts, More preferably, it is 1-15 mass parts. When the total content of the dichroic dye is within the above range, it can be polymerized without disturbing the orientation of the polymerizable liquid crystal compound. When the content of the dichroic dye is too small, light absorption becomes insufficient and sufficient polarization performance cannot be obtained. Therefore, the content of the dichroic dye can also be determined within the range in which the polymerizable liquid crystal compound can maintain the liquid crystal state.

＜How to store＞

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

Storing them separately means, for example, storing agent A and agent B in two independent containers, or storing agent A and agent B in one container with a partition between them and not mixing the two agents during storage. and the like. In this invention, the aspect which stores agent A and agent B in two independent containers is preferable.

The container for storing agent A includes a plastic container, a metal container, and a glass container, and a plastic container or a metal container is preferable. It is preferable that the container for storing agent A is a plastic container or a metal container because side reactions of reactive additives in agent A do not occur easily. Examples of materials for plastic containers include polypropylene, polyethylene, norbornene-based polymers, polystyrene, polyamides, poly(4-methylpentene-1), acrylic resins, polyvinyl alcohol, and acrylonitrile-butadiene-styrene. Copolymer, polymethacrylic acid ester, polyacrylic acid ester, cellulose ester, polycarbonate, polyethylene terephthalate, polysulfone, polyethersulfone, polyether ketone, polyethylene naphthalate, polyphenylene sulfide, polyphenylene oxide, cyclic cyclic polyolefins such as olefin polymers or cyclic olefin copolymers, polyolefins such as amorphous polyarylates, polyesters, and Teflon; but are not limited thereto. Examples of the material of the metal container include steel such as SUS, tin plate, and aluminum, but are not limited thereto. When the container for storing agent A is a plastic container, it is preferably a plastic container (for example, a brown plastic container) having light-shielding properties because it is not easily affected by ultraviolet rays that can cause deterioration of the composition. desirable. Moreover, you may apply coating etc. to the outer surface of a container.

The container for storing agent B is not particularly limited, and examples of the material of the container include plastic, metal, and glass. It is preferable that the container which stores agent B is a container with light-shielding property similarly to the above.

The shape of the container for storing agent A and agent B is not particularly limited. For example, hexahedral shapes, such as a one-piece can and poly tank, and cylindrical shapes, such as a pail can and a paint can, etc. are mentioned. Also, the capacity of agent A and agent B is not particularly limited, and a desired amount can be stored in a container.

When storing agent A, agent A is preferably stored under a dry inert gas atmosphere. In this specification, the dry gas generally refers to a gas having a dew point of -50°C or less, and the inert gas refers to a gas with low reactivity such as nitrogen, argon, or helium, for example. Storage under a dry inert gas atmosphere includes, for example, an aspect in which the vapor phase in the storage container is filled with dry inert gas and then sealed and stored, and an aspect in which the storage container itself is stored in a space filled with dry inert gas. By storing in a dry inert gas atmosphere, the side reaction of the active hydrogen reactor with the reactive additive in the agent A, such as moisture in the ambient atmosphere, can be avoided, so that the adhesion of the polarizing film obtained from the composition for forming a two-component polarizing film of the present invention is easily improved. In addition, the optical performance after long-term storage tends to be good.

Although the atmosphere in the case of storing agent B is not specifically limited, It is preferable to store under a dry inert gas atmosphere.

The filling amount of agent A and agent B relative to the capacity of the storage container is not particularly limited, but the filling amount of agent A and agent B is usually 30% or more, preferably 50% or more of the storage container capacity. From the viewpoint of ease, it is usually 90% or less.

The temperature at which agent A and agent B are stored is not particularly limited, but if the temperature is too high, a polymerization reaction of the polymerizable liquid crystal compound may be initiated, and if the temperature is too low, there is a possibility that solids in agent A and agent B may be precipitated. Therefore, the storage temperature is usually 0 to 50°C, preferably 10 to 40°C, and more preferably 15 to 35°C.

If agent A and agent B are mixed and stored for about 3 months, it may be difficult to produce a polarizing film having good optical performance. The composition for forming a two-component polarizing film of the present invention is advantageous in that a polarizing film having good optical performance can be obtained even after such long-term storage (for example, 3 months or more). The storage period for agent A and agent B is not particularly limited, but is usually within 3 years.

In the composition for forming a two-component polarizing film of the present invention, a polarizing film having good optical performance even after long-term storage can be obtained by separately storing the dichroic dye containing the reactive additive and the azo dye having an amine structure as described above. As a result of the present inventors' study on this, in a polarizing film obtained from a composition for forming a polarizing film in which a reactive additive and an azo dye having an amine structure among dichroic dyes are stored together for a certain period of time (for example, 3 months), in the polarizing film It was found that the molecular orientation of the liquid crystal compound tends to be disturbed (that is, the liquid crystal compound does not align in one direction), and thus the optical properties of the obtained polarizing film tend to deteriorate.

<Method for producing composition for forming polarizing film>

In the present invention, the composition for forming a polarizing film can be obtained by mixing agent A and agent B constituting the composition for forming a two-component polarizing film. In the present specification, "composition for forming a two-component polarizing film" refers to a composition in which agent A and agent B constituting the composition for forming a two-component polarizing film are separately separated, and agent A and agent B are mixed. The composition in this state is referred to as "the composition for forming a polarizing film".

The timing of mixing agent A and agent B in the composition for forming a two-component polarizing film of the present invention is not limited as long as the reaction between the reactive additive and the azo dye having an amine structure does not progress, and the reactive additive contained And what is necessary is just to decide suitably according to the kind and quantity of an azo dye which has an amine structure, mixing conditions, environment, etc.

A method of mixing agent A and agent B is not particularly limited, and a known mixing method can be used. For example, a method of mixing using a mixing device having stirring blades such as a planetary mixer or a kneader mixer, or a method of static mixing using a static mixer or the like can be cited.

The ambient temperature when mixing agent A and agent B is not particularly limited, but is preferably 0 to 50°C, more preferably 15 to 40°C, still more preferably 20 to 35°C. Humidity (relative humidity) is also not particularly limited, but is preferably 30 to 60%RH, more preferably 40 to 55%RH. In addition, mixing is normally performed under normal pressure (atmospheric pressure).

The mixing time is also not particularly limited, and can be appropriately adjusted according to the type and amount of components contained in the composition for forming a two-component polarizing film. The mixing time is usually 0.5 to 12 hours, preferably 0.5 to 6 hours.

<Method for producing polarizing film>

The manufacturing method of the polarizing film of the present invention,

A step of forming an alignment film on a substrate;

Agent A containing a reactive additive having a polymerizable group and an active hydrogen reactive group in a molecule and a solvent constituting the composition for forming a two-component polarizing film of the present invention, a dichromatic dye containing an azo dye having an amine structure, and a solvent A step of mixing the contained agent B to obtain a composition for forming a polarizing film;

a step of applying the mixed composition for forming a polarizing film onto the alignment film to obtain a coating film; and

Process of curing the coating film

includes

[write]

A glass substrate and a plastic substrate are mentioned as a substrate used for formation of a polarizing film. A plastic substrate is more preferable than a glass substrate in terms of roll-to-roll processing and high productivity. Examples of the plastic constituting the plastic substrate include polyolefins such as polyethylene, polypropylene, and norbornene polymers; Cyclic olefin resin; polyvinyl alcohol; polyethylene terephthalate; Polymethacrylic acid ester; polyacrylic acid ester; cellulose esters such as triacetyl cellulose, diacetyl cellulose and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyether ketone; polyphenylene sulfide and polyphenylene oxide; Plastics, such as these, are mentioned.

Examples of commercially available cellulose ester substrates include "Fujitak Film" (manufactured by Fuji Photo Film Co., Ltd.); "KC8UX2M", "KC8UY", and "KC4UY" (above, manufactured by Konica Minolta Opto Co., Ltd.), etc. are mentioned.

Commercially available cyclic olefin resins include “Topas” (registered trademark) (manufactured by Ticona (Germany)), “Aton” (registered trademark) (manufactured by JSR Corporation), and “ZEONOR” (registered trademark). ), "ZEONEX" (registered trademark) (above, manufactured by Nippon Zeon Co., Ltd.) and "APEL" (registered trademark) (manufactured by Mitsui Chemicals Co., Ltd.). Such a cyclic olefin resin can be formed into a film by a known means such as a solvent casting method or a melt extrusion method to be used as a base material. A commercially available cyclic olefin resin base material can also be used. Examples of commercially available cyclic olefin resin substrates include "S-Sina" (registered trademark), "SCA40" (registered trademark) (above, manufactured by Sekisui Chemical Industry Co., Ltd.), and "Zeonoa Film" (registered trademark) (optional). Tess Co., Ltd.) and "Aton Film" (registered trademark) (JSR Co., Ltd.).

A polarizing plate is obtained from the polarizing film and substrate of the present invention. The thickness of the base material is preferably thinner in terms of a mass capable of practical handling, but when it is too thin, the strength tends to decrease and workability tends to be inferior. The thickness of the substrate is usually 5 to 300 μm, preferably 20 to 200 μm. In addition, since it is possible to apply only the polarizing film of the present invention by peeling off the base material and transferring the polymer of the polymerizable liquid crystal compound containing the dichromatic dye, a new thinning effect is obtained.

[Alignment layer]

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

The alignment film facilitates liquid crystal orientation of the polymerizable liquid crystal compound. The state of liquid crystal alignment, such as horizontal alignment, vertical alignment, hybrid alignment, and oblique alignment, changes depending on the properties of the alignment film and polymerizable liquid crystal compound, and the combination thereof can be arbitrarily selected. For example, if the alignment film is a material that exhibits horizontal alignment as an alignment regulating force, the polymerizable liquid crystal compound can form horizontal alignment or hybrid alignment, and if it is a material that exhibits vertical alignment, the polymerizable liquid crystal compound can be vertically aligned or tilted. alignment can be formed. Expressions such as horizontal and vertical indicate the direction of the major axis of the aligned polymerizable liquid crystal when the plane of the polarizing film is taken as a reference. The horizontal alignment is an alignment having a long axis of the aligned polymerizable liquid crystal in a direction parallel to the plane of the polarizing film. "Parallel" as used herein means an angle of 0° ± 20° with respect to the plane of the polarizing film. Vertical alignment means having the long axis of the polymerizable liquid crystal aligned in a direction perpendicular to the plane of the polarizing film. Perpendicularity here means the thing of 90 degrees ± 20 degrees with respect to the plane of a polarizing film.

The orientation control force can be arbitrarily adjusted depending on the surface state and rubbing conditions when the alignment film is formed of an orientation polymer, and can be arbitrarily adjusted depending on polarized light irradiation conditions and the like when the alignment film is formed of a photo-alignment polymer. . Moreover, the liquid crystal orientation can also be controlled by selecting physical properties, such as surface tension and liquid crystallinity, of a polymerizable liquid crystal compound.

As the alignment film, it is preferable to be insoluble in the solvent used when forming the polarizing film on the alignment film, and to have heat resistance in removal of the solvent or heat treatment for alignment of liquid crystals. Examples of the alignment film include an alignment film made of an alignable polymer, a photo-alignment film, a groove alignment film, and a stretched film stretched in an orientation direction, and a photo-alignment film is preferable.

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

Examples of the orienting polymer include polyamides or gelatins having an amide bond in the molecule, polyimide having an imide bond in the molecule, and polyamic acid as a hydrolyzate thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, and polyoxa. sol, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylic acid esters. Especially, polyvinyl alcohol is preferable.

These orienting polymers may be used alone or in combination of two or more.

An alignment film made of an orienting polymer is usually obtained by applying a composition in which an orienting polymer is dissolved in a solvent (hereinafter, also referred to as “orienting polymer composition”) to a substrate, removing the solvent, or applying an orienting polymer composition to a substrate, It is obtained by removing a solvent and carrying out rubbing (rubbing method).

As said solvent, Water; alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, 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 amyl ketone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; aromatic hydrocarbon solvents such as toluene and xylene, nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorine-substituted hydrocarbon solvents such as chloroform and chlorobenzene; etc. can be mentioned. These solvents may be used alone or in combination of two or more.

The concentration of the oriented polymer in the oriented polymer composition may be within a range in which the oriented polymer can be completely dissolved in the solvent, but is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass in terms of solid content with respect to the solution.

As the orientation polymer composition, you may use a commercially available orientation film material as it is. Examples of commercially available alignment film materials include SunEver (registered trademark) (manufactured by Nissan Chemical Industries, Ltd.) and Optimer (registered trademark) (manufactured by JSR Corporation).

As a method of applying the orientation polymer composition to a substrate, a known coating method such as a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, and an applicator method, or a printing method such as a flexographic method way can be

When the alignment film of the present invention is produced by a roll-to-roll continuous production method, a printing method such as a gravure coating method, a die coating method, or a flexo method is usually employed as the coating method.

By removing the solvent contained in the orientation polymer composition, a dry coating film of the orientation polymer is formed. As a method for removing the solvent, a natural drying method, an air drying method, a heating drying method, a vacuum drying method, and the like are exemplified.

As a method of rubbing, a method in which a rubbing cloth is wound and a rotating rubbing roll is applied to a base material with an orientable polymer composition and an oriented polymer composition is applied and annealed to contact a film of an oriented polymer formed on the surface of the base material.

The photo-alignment layer is usually made of a polymer, oligomer, or monomer having a photoreactive group.

When the polymerizable liquid crystal is formed continuously, a polymer having a molecular weight of 5000 or more is preferable from the viewpoint of solvent resistance and the like, and when the polymerizable liquid crystal is a (meth)acryloyl group from the viewpoint of affinity, an acrylic polymer is preferable. The photo-alignment film is obtained by applying a composition containing a polymer, oligomer or monomer having a photoreactive group and a solvent (hereinafter, also referred to as "composition for forming a photo-alignment film") to a substrate, drying and removing the solvent, and then polarizing light (preferably, polarizing light). UV) is obtained by irradiation.

The photo-alignment film is more preferable in that the direction of the alignment regulating force can be arbitrarily controlled by selecting the polarization direction of the polarized light to be irradiated.

A photoreactive group means group which generates liquid-crystal orientation ability by irradiating light. Specifically, it is to generate a photoreaction that is the origin of the liquid crystal alignment ability, such as orientation induction of molecules or an isomerization reaction, a dimerization reaction, a photocrosslinking reaction, or a photolysis reaction generated by irradiation with light. Among the photoreactive groups, those that undergo a dimerization reaction or a photocrosslinking reaction are preferable in terms of excellent orientation properties. As the photoreactive group capable of generating the above reaction, those having an unsaturated bond, particularly a double bond are preferable, and carbon-carbon double bonds (C=C bonds), carbon-nitrogen double bonds (C=N bonds), A group having at least one selected from the group consisting of a nitrogen-nitrogen double bond (N=N bond) and a carbon-oxygen double bond (C=O bond) is more preferable.

Examples of the photoreactive group having a C=C bond include a vinyl group, a polyene group, a stilbene group, a stilbazole group, a stilbazolium group, a chalcone group, and a cinnamoyl group. Examples of the photoreactive group having a C=N bond include groups having structures such as aromatic Schiff base and aromatic hydrazone. Examples of the photoreactive group having an N = N bond include an azobenzene group, an azonaphthalene group, an aromatic heterocyclic azo group, a bisazo group, and a formazan group, as well as those having azoxybenzene as a basic structure. A benzophenone group, a coumarin group, an anthraquinone group, a maleimide group, etc. are mentioned as a photoreactive group which has a C=O bond.

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

As the solvent for the composition for forming a photo-alignment layer, it is preferable to dissolve a polymer and a monomer having a photoreactive group, and examples of the solvent include the solvents mentioned as the solvent for the orientation polymer composition described above.

The content of the polymer or monomer having a photoreactive group in the composition for forming a photo-alignment layer can be appropriately adjusted depending on the type of the polymer or monomer having the photo-reactive group or the thickness of the photo-alignment layer to be produced, but it is set to 0.2% by mass or more. It is preferable, and the range of 0.3-10 mass % is especially preferable. In addition, a polymer material such as polyvinyl alcohol or polyimide or a photosensitizer may be contained within a range in which the characteristics of the photo-alignment layer are not significantly impaired.

As a method of applying the composition for forming a photo-alignment layer to the diffusion barrier layer, the same method as the method of applying the orientation polymer composition to the diffusion barrier layer may be exemplified. As a method of removing the solvent from the applied composition for forming a photo-alignment layer, the same method as the method of removing the solvent from the orienting polymer composition can be exemplified.

In order to irradiate polarized light, the composition for forming a photo-alignment layer applied on a substrate may be irradiated directly with the solvent removed, or the polarized light may be irradiated from the substrate and the polarized light transmitted therethrough. Moreover, it is especially preferable that the polarized light is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably in a wavelength range in which the photoreactive group of a polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) in a wavelength range of 250 to 400 nm is particularly preferred. Examples of light sources used for the polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, ultraviolet lasers such as KrF and ArF, and high-pressure mercury lamps, ultra-high pressure mercury lamps, and metal halide lamps. is more preferable. These lamps are preferable because the emission intensity of ultraviolet light with a wavelength of 313 nm is high. Polarized light can be irradiated by irradiating light from the light source through an appropriate polarizer. As such a polarizer, a polarization filter, a polarization prism such as Glenn Thomson or Glenn Taylor, or a wire grid type polarizer can be used.

Moreover, if masking is performed when rubbing or polarized light irradiation is performed, a plurality of regions (patterns) in which the directions of liquid crystal alignment are different can also be formed.

A groove alignment film is a film having a concavo-convex pattern or a plurality of grooves (grooves) on the surface of the film. When liquid crystal molecules are placed in a film having a plurality of linear grooves arranged at equal intervals, the liquid crystal molecules are aligned in a direction along the grooves.

As a method of obtaining a groove alignment film, a method of forming a concavo-convex pattern by performing development and rinse treatment after exposure through an exposure mask having a pattern-shaped slit on the surface of the photosensitive polyimide film, a plate-shaped master having grooves on the surface , a method of forming a layer of UV curable resin before curing, transferring the resin layer to a substrate and then curing it, and pressing a roll-shaped disk having a plurality of grooves onto the film of UV curable resin formed on the substrate before curing, and concavo-convex and a method of forming and then curing. Specifically, the method of Unexamined-Japanese-Patent No. 6-34976 and Unexamined-Japanese-Patent No. 2011-242743 etc. are mentioned.

In order to obtain an alignment with little orientation disturbance, the width of the convex portion of the groove alignment film is preferably 0.05 to 5 μm, the width of the concave portion is preferably 0.1 to 5 μm, and the depth of the level difference of the concavo-convex portion is preferably 2 μm or less , preferably 0.01 to 1 μm or less.

[Polarizing film]

On the alignment film obtained as described above, the composition for forming a polarizing film is applied to form a coating film, and then the solvent contained in the composition for forming a polarizing film is removed under conditions in which the polymerizable liquid crystal is not polymerized, thereby forming a substrate surface A dry coating film of the composition for forming a polarizing film is formed thereon. As a method for removing the solvent, for example, a natural drying method, an air drying method, a heat drying method, and a reduced pressure drying method are exemplified.

Polymerization by heating the dry coating film to align the polymerizable liquid crystal compound contained in the dry coating film in a liquid crystal orientation, particularly in a smectic phase state, and then irradiating energy to the dry coating film while maintaining this liquid crystal orientation It polymerizes a sexual liquid crystal compound. In the case where the composition for forming a polarizing film contains a polymerization initiator, it is preferable to irradiate energy under conditions in which the polymerization initiator is activated. When the polymerization initiator is a photopolymerization initiator, the energy is preferably light. The light to be irradiated is appropriately selected according to the type of polymerization initiator contained in the dry coating film or the type of polymerizable liquid crystal (particularly, the type of polymerizable group of the polymerizable liquid crystal compound) and the amount thereof.

Examples of such light include light selected from the group consisting of visible light, ultraviolet light, and laser light, active electron beams, and the like. Ultraviolet light is preferable in terms of being able to use what is widely used. Therefore, it is preferable to select the types of the polymerizable liquid crystal compound and polymerization initiator contained in the composition for forming a polarizing film so that they can be polymerized by ultraviolet light. Moreover, when superposing|polymerizing, it is preferable to control the polymerization temperature by cooling the said dry coating film by an appropriate cooling means with ultraviolet light irradiation. By such cooling, if the polymerizable liquid crystal compound is polymerized at a lower temperature, a polarizing film can be suitably produced even if a substrate having low heat resistance is used.

[Example]

Hereinafter, the present invention will be described in more detail by examples. In addition, "%" and "part" in the example mean mass % and mass part, respectively, unless otherwise specified.

<Example 1>

[Preparation of Composition for Forming Photo Alignment Layer]

The composition for photo-alignment film formation was obtained by mixing the following components of Unexamined-Japanese-Patent No. 2013-033249, and stirring the obtained mixture at 80 degreeC for 1 hour.

[Preparation of agent A]

Agent A (1) was obtained by mixing the following components and stirring at 25°C for 1 hour. In addition, the moisture content of ortho-xylene used as a solvent was <100 ppm.

The prepared agent A (1) was placed in a tube made of SUS, the vapor phase was substituted with dry nitrogen, and sealed.

[Preparation of Agent B]

Agent B (1) was obtained by mixing the following components and stirring at 80°C for 1 hour. The azo dye described in the Example of Unexamined-Japanese-Patent No. 2013-101328 was used for the dichromatic dye. In addition, the moisture content of ortho-xylene used as a solvent was <100 ppm.

The prepared agent B (1) was placed in a tube made of SUS, the vapor phase was substituted with dry nitrogen, and sealed.

<Method for producing polarizing film>

(1) Formation of photo-alignment layer

A triacetyl cellulose film (KC8UX2M, manufactured by Konica Minolta Co., Ltd.) was used as a base material, and after corona treatment was applied to the surface of the film, the composition for forming a photo-alignment film was applied and dried at 120°C to obtain a dry coating film. Polarized UV was irradiated on this dry coating film, the photo-alignment film was formed, and the film with a photo-alignment film was obtained. The polarization UV treatment was performed using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Electric Co., Ltd.) under the condition that the intensity measured at a wavelength of 365 nm was 100 mJ/cm 2 . In this way, a film with a photo-alignment layer was obtained.

(2) Formation of polarizing film

After preparation of agent A (1) and agent B (1) and storage at 25°C for 3 months, agent A (1) and agent B (1) were mixed and stirred at 25°C for 1 hour to form a polarizing film. Composition (1) was obtained.

Immediately after obtaining the composition for forming a polarizing film (1), the composition for forming a polarizing film (1) was applied onto the film with a photo-alignment film obtained above by a bar coating method, and then, in a drying oven at 120°C, 1 After sufficiently removing the solvent by heating and drying for a minute, the polymerizable liquid crystal compound was phase-transformed into a smectic liquid crystal state by cooling to room temperature. Then, using a UV irradiation device (Unicure VB-15201BY-A; manufactured by Ushio Electric Co., Ltd.), the layer formed of the composition (1) for forming a polarizing film was irradiated with ultraviolet light at an exposure amount of 1000 mJ/cm 2 (based on 365 nm), thereby , The polymerizable liquid crystal compound contained in the dry coating film was polymerized while maintaining the smectic liquid crystal state of the polymerizable liquid crystal compound, and the polarizing film 1 was formed from the dried coating film. It was 2.3 micrometers as a result of measuring the film thickness of this polarizing film 1 with the laser microscope (OLS3000 by Olympus Corporation). What was obtained in this way is a polarizer (polarizing film laminate) containing a polarizing film and a base material. As a result of performing X-ray diffraction measurement on this polarizing film 1 using an X-ray diffractometer X'Pert PRO MPD (manufactured by Spectris Co., Ltd.), the peak half-width at half maximum (FWHM) = about 0.17 at 2θ = 20.2°. A sharp diffraction peak (Bragg peak) of ° was obtained. Moreover, the same result was obtained also in the case of incidence from the direction perpendicular to the rubbing. The order period (d) obtained from the peak position was about 4.4 Å, and it was confirmed that a structure reflecting a higher order smectic phase was formed.

<Measurement of moisture content>

The water content of the solvent was measured by a coulometric titration method using a Karl Fischer water content meter (MKC-710M manufactured by Kyoto Electric Industry Co., Ltd.).

<Measurement of polarization degree Py and single transmittance Ty>

The polarization degree Py and single transmittance Ty of the polarizing film 1 were measured as follows. The transmittance (Ta1) in the transmission axis direction and the transmittance (Tb2) in the absorption axis direction in the wavelength range of 380 nm to 780 nm were set in a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation) with a polarizer attached folder. was measured by the double beam method. In that folder, a mesh that cuts the amount of light by 50% was provided on the reference side.

Using the following equations (Equation 1) and (Equation 2), the single transmittance and polarization degree at each wavelength are calculated, and further, visibility correction is performed by a 2-degree field of view (C light source) of JIS Z 8701, and visibility correction is performed. The single transmittance (Ty) and visibility corrected polarization degree (Py) were calculated. As a result, Ty = 42% and Py = 98%, showing high performance derived from highly oriented smectic liquid crystals.

<Evaluation of adhesion>

A 25 mm wide cello tape (manufactured by Nichiban) was attached to the front and back surfaces of the obtained polarizing film 1, respectively, and a 90° peel test was conducted on each of the front and back surfaces. A case in which peeling did not occur was rated as ○, a case in which peeling occurred at only a part of the test point was marked as △, and a case where peeling occurred at the entire test point was marked as ×.

<Evaluation of appearance>

The obtained polarizing film (1) was visually confirmed to confirm the presence or absence of foreign matter. A case in which no foreign material was visually confirmed was rated as ○, a case where a small amount of foreign material was confirmed was evaluated as △, and a case where a large amount of foreign material was observed was evaluated as ×.

<Examples 2 and 3>

Except having changed the storage container of agent A as described in the table, it carried out similarly to Example 1, and obtained the composition for polarizing film formation (2)-(3) and polarizing film (2)-(3). Py, Ty, adhesiveness, and external appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

<Example 4>

A composition for forming a polarizing film (4) and a polarizing film (4) were obtained in the same manner as in Example 1 except that air was used as the gaseous portion of the container for storing agent A. Py, Ty, adhesiveness, and external appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

<Example 5>

A composition for forming a polarizing film (5) and a polarizing film (5) were obtained in the same manner as in Example 1 except for using the following compounds as reactive additives. Py, Ty, adhesion, and appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

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

<Example 6>

A composition for forming a polarizing film (6) and a polarizing film (6) were obtained in the same manner as in Example 1 except for using the following compounds as reactive additives. Py, Ty, adhesiveness, and external appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

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

<Examples 7 and 8>

Except having used the solvent of agent A as described in the table, it was carried out similarly to Example 1, and the polarizing film-forming composition (7)-(8) and polarizing film (7)-(8) were obtained. In addition, the moisture content of toluene used was <100 ppm, and the moisture content of anisole was 250 ppm. Py, Ty, adhesion, and appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

<Examples 9 to 12>

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

<Example 13>

A composition for forming a polarizing film (13) and a polarizing film (13) were obtained in the same manner as in Example 1 except that the addition amount of the dichroic dye was changed as described in the table. Py, Ty, adhesiveness, and external appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

<Example 14>

Polarized light in the same manner as in Example 1 except that the dichroic dye represented by (1-2) was added to agent A and the dichroic dye represented by (1-1) and (1-3) was added to agent B. A composition for film formation (14) and a polarizing film (14) were obtained. Py, Ty, adhesiveness, and external appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

<Comparative Example 1>

After preparing agent A and agent B in the same manner as in Example 1, the two liquids were stirred and mixed at 25°C for 1 hour in a SUS tube. After mixing the two liquids, it was sealed under dry nitrogen, and coated after storage at 25°C for 3 months, and Py, Ty, adhesion, and appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

<Comparative Example 2>

A composition for forming a polarizing film was prepared in the same manner as in Comparative Example 1 except that no reactive additive was used, sealed under dry nitrogen, and coated after storage at 25 ° C. for 3 months. Py, Ty, adhesion, The external appearance was evaluated in the same manner as in Example 1.

<Comparative Examples 3 and 4>

After preparing agent A and agent B in the same manner as in Comparative Example 1 except that the reactive additive was changed as described in the table, the two liquids were mixed by stirring at 25°C for 1 hour in a SUS tube. After mixing the two liquids, it was sealed under dry nitrogen, and coated after storage at 25°C for 3 months, and Py, Ty, adhesion, and appearance of the obtained polarizing film were evaluated in the same manner as in Example 1.

<Comparative Example 5>

Py, Ty, adhesion, and appearance of the polarizing film obtained in the same manner as in Example 1 were evaluated in the same manner as in Example 1 except that the dichromatic dye was added to agent A and the dichromatic dye was removed from agent B.

From the compositions of Examples 1 to 14 in which the reactive additive and the dichromatic dye containing the azo dye having an amine structure were separately stored, even if coating was performed after storage for 3 months after preparing the second agent, good optical properties and high A polarizing film having adhesiveness and excellent appearance can be obtained. On the other hand, Comparative Examples 1, 3 and 4 in which the dichromatic dye containing the azo dye having the reactive additive and the amine structure was mixed and stored for 3 months, and the dichromatic dye containing the reactive additive and the azo dye having the amine structure were the same. In the composition of Comparative Example 5 contained in the agent, a polarizing film was obtained that was inferior in all of optical properties, adhesiveness and appearance. It can be seen that the polarizing film obtained from the composition of Comparative Example 2 containing no reactive additive is inferior in adhesion.

Claims (9)

A reactive additive having a polymerizable group and an active hydrogen reactive group in a molecule and agent A containing a solvent, and agent B containing a dichroic dye and a solvent, wherein the dichroic dye contains an azo dye having an amine structure. A composition for forming a liquid polarizing film. According to claim 1,
A composition for forming a two-component polarizing film, further containing a polymerizable liquid crystal compound. According to claim 1 or 2,
A composition for forming a two-component polarizing film, wherein the solvent contained in the agent A has a water content of less than 300 ppm. According to claim 2 or 3,
The composition for forming a two-component polarizing film, wherein the amount of the reactive additive contained in the agent A is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymerizable liquid crystal compound. A method for storing the composition for forming a two-component polarizing film according to any one of claims 1 to 4, wherein the agent A and the agent B are separately stored. According to claim 5,
A storage method comprising storing the agent A in a plastic container or a metal container. According to claim 5 or 6,
The storage method which stores the said agent A under dry inert gas atmosphere. An agent A containing a solvent and a reactive additive having a polymerizable group and an active hydrogen reactive group in the molecule constituting the composition for forming a two-component polarizing film according to any one of claims 1 to 4, and having an amine structure. A method for producing a composition for forming a polarizing film, comprising a step of mixing a dichroic dye containing an azo dye and agent B containing a solvent. A step of forming an alignment film on a substrate;
An agent A containing a solvent and a reactive additive having a polymerizable group and an active hydrogen reactive group in the molecule constituting the composition for forming a two-component polarizing film according to any one of claims 1 to 4, and having an amine structure. A step of mixing a dichroic dye containing an azo dye and agent B containing a solvent to obtain a composition for forming a polarizing film;
a step of applying the mixed composition for forming a polarizing film onto the alignment film to obtain a coating film; and
A method for producing a polarizing film, including a step of curing the coating film.