JP2016024369A - Water-resistant polarization film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-resistant polarization film that prevents a polarization layer from dissolving even under an environment in contact with water and also prevents its optical properties from changing.SOLUTION: A water-resistant polarization film according to the present invention comprises a polarization layer comprising an organic dye having an anionic group, an acyclic compound having a nitrogen atom, a siloxane compound having an amino group, and a siloxane compound having an epoxy group or isocyanate group.SELECTED DRAWING: None

Description

  The present invention relates to a water-resistant polarizing film having excellent durability.

  The polarizing film is an optical film having a function of transmitting specific linearly polarized light from polarized light or natural light. The polarizing film is used, for example, as a constituent member of a liquid crystal display device or a lens of polarized sunglasses.

Conventionally, Patent Document 1 discloses a water-resistant polarizing film having a polarizing layer containing an organic dye having an anionic group and an acyclic compound having 2 to 5 nitrogen atoms.
Even when the water-resistant polarizing film of Patent Document 1 is exposed to high temperature and high humidity such as 60 ° C. and 90% RH, the polarizing layer does not crack and has optical properties (transmittance and polarization degree). There is an advantage that the change is small.
Thus, although the water-resistant polarizing film of patent document 1 is excellent in durability in a high-humidity environment, there exists a problem that durability will fall when this film is immersed in water.
In general, an optical member such as a lens may be cleaned using an ultrasonic cleaner. However, when the water-resistant polarizing film is ultrasonically cleaned, the polarizing layer is dissolved or the optical characteristics are greatly deteriorated. There's a problem.

JP 2010-156937 A

  An object of the present invention is to provide a water-resistant polarizing film in which a polarizing layer is hardly dissolved even in an environment in contact with water, and further, optical properties are hardly changed.

  The water-resistant polarizing film of the present invention is a polarized light comprising an organic dye having an anionic group, an acyclic compound having a nitrogen atom, a siloxane compound having an amino group, and a siloxane compound having an epoxy group or an isocyanate group. Has a layer.

In a preferred water-resistant polarizing film of the present invention, the polarizing layer includes a plurality of aggregates in which the plurality of organic dyes are collected, and the siloxane compound having the amino group is bonded to the plurality of aggregates.
In a preferred water-resistant polarizing film of the present invention, the siloxane compound having an epoxy group or an isocyanate group is bonded to the siloxane compound having an amino group.
In a preferred water-resistant polarizing film of the present invention, the siloxane compound having an amino group is represented by the following general formula (3-1) or (3-2).

In General Formulas (3-1) and (3-2), R ¹ represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and R ² , R ^3, and R ⁴ are each independently Represents a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group, or a thiol group, and R ⁵ is interrupted by a substituted or unsubstituted divalent hydrocarbon group, or oxygen or nitrogen A hydrocarbon group, which is a substituted or unsubstituted divalent hydrocarbon group.

In a preferred water-resistant polarizing film of the present invention, the siloxane compound having an epoxy group contains a hydrolysis condensate of an epoxy silane coupling agent represented by the following general formula (6-1) or (6-2).
In a preferred water-resistant polarizing film of the present invention, the siloxane compound having an isocyanate group contains a hydrolysis condensate of an isocyanate silane coupling agent represented by the following general formula (7-1) or (7-2).

In general formulas (6-1), (6-2), (7-1), and (7-2), R ⁶ , R ^7, and R ⁸ are each independently a hydrogen atom, substituted or unsubstituted Represents a monovalent hydrocarbon group or a thiol group, and R ⁹ represents a substituted or unsubstituted divalent hydrocarbon group, or a hydrocarbon group interrupted with oxygen or nitrogen and substituted or unsubstituted. Represents a divalent hydrocarbon group. The EP groups of general formulas (6-1) and (6-2) represent epoxy groups including alicyclic groups.

In a preferred water-resistant polarizing film of the present invention, the acyclic compound has 2 to 5 cationic groups containing a nitrogen atom in the molecule.
In the preferable water-resistant polarizing film of the present invention, the organic dye contains an azo compound represented by the following general formula (1-3).

In General Formula (1-3), X represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms. Or a —SO ₃ M group, M represents a counter ion, R represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted acetyl group, a substituted or It represents an unsubstituted benzoyl group or a substituted or unsubstituted phenyl group.

  The water-resistant polarizing film of the present invention is hardly dissolved even when the polarizing layer is in contact with water, and its optical characteristics are hardly changed. In particular, the water-resistant polarizing film of the present invention can be suitably used as a constituent member of a lens such as sunglasses because the polarizing layer is difficult to dissolve in water even after ultrasonic cleaning.

Sectional drawing of the water-resistant polarizing film which concerns on one embodiment. FIG. 4 is a reference diagram schematically showing a bonding state of an association of an organic dye, an acyclic compound, a siloxane compound having an amino group, and a siloxane compound having an epoxy group or an isocyanate group in a polarizing layer.

The water-resistant polarizing film of the present invention and the production method thereof will be specifically described.
In the present specification, the notation “A to B” means “A to B”.
The water-resistant polarizing film of the present invention is a polarized light comprising an organic dye having an anionic group, an acyclic compound having a nitrogen atom, a siloxane compound having an amino group, and a siloxane compound having an epoxy group or an isocyanate group. Has a layer.
Usually, as shown in FIG. 1, the water-resistant polarizing film 1 includes the polarizing layer 2 and a base material 3 on which the polarizing layer 2 is laminated. But the water-resistant polarizing film of this invention may be comprised only from the polarizing layer (not shown). Moreover, the water-resistant polarizing film of the present invention may have other layers in addition to the base material and the polarizing layer.

[Organic dye having an anionic group]
The organic dye having an anionic group contained in the polarizing layer is not particularly limited as long as it is an organic compound exhibiting two-color absorption, but those having lyotropic liquid crystallinity are preferable.
The anionic group has a fixed anion group bonded to the skeleton of the organic dye, and usually a counter ion is bonded to the fixed anion group.
A part or all of the counter ion is substituted with a cationic species of an acyclic compound having a nitrogen atom.

Examples of the anionic group include a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a base thereof. The anionic group is preferably a sulfonate group or a sulfonate group, and more preferably a sulfonate group (—SO ₃ M group).

The number of anionic groups (substitution number) of the organic dye is not particularly limited, but is preferably 2 or more, more preferably 2 to 5, more preferably 2 to 4, Most preferably, it is 2 or 3.
An organic dye having two or more anionic groups has high affinity for an aqueous solvent. Therefore, the organic dye can be dissolved in an aqueous solvent, and a good coating solution can be easily prepared. A polarizing layer can be formed by using this coating liquid.
The anionic group forms a bonding point with an acyclic compound and a siloxane compound having an amino group when the polarizing layer is subjected to water resistance treatment.

The organic dye is a compound that can form a polarizing layer exhibiting absorption dichroism.
The polarizing layer is an optical film having a function of transmitting specific linearly polarized light from natural light or polarized light.
As the organic dye, for example, compounds described in JP 2007-126628 A, JP 2006-323377 A, and the like can be used.

  Further, when the organic dye has two or more anionic groups, the positions of the anionic groups are preferably not adjacent (not ortho positions), and the positions of the anionic groups are in the meta position. More preferably it is. The organic dye in which the anionic group is in the meta position reduces steric hindrance between the anionic groups. For this reason, a polarizing layer having a high degree of polarization can be obtained by linearly orienting the organic dye before and after the water resistance treatment.

  As the organic dye, for example, an azo compound represented by the following general formula (1-1) or general formula (1-2) is preferable.

  The azo compound represented by the general formula (1-1) or (1-2) has two or more anionic groups, and two anionic groups of the naphthyl group (formula A) are in the meta position. Are connected.

In the general formulas (1-1) and (1-2), Q ¹ represents a substituted or unsubstituted aryl group, Q ² represents a substituted or unsubstituted arylene group, and A represents an anionic group. M represents a counter ion of the anionic group, and R represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted acetyl group, a substituted or unsubstituted benzoyl group. Represents a group or a substituted or unsubstituted phenyl group, k represents an integer of 0 to 3, and 1 represents an integer of 0 to 3; However, k + l ≦ 5. In the present specification, “substituted or unsubstituted” means substituted with a substituent or not substituted with a substituent.

The aryl group or arylene group represented by Q ¹ or Q ² may have a substituent or may not have a substituent. Even when the aryl group or arylene group represented by Q ¹ or Q ² is substituted or unsubstituted, the azo compound of the general formula (1-1) or (1-2) exhibits absorption dichroism. .

When the aryl group or arylene group has a substituent, examples of the substituent include a halogeno group, a nitro group, a cyano group, a dihydroxypropyl group, a phenylamino group, —OM, —COOM, —SO ₃ M, carbon Examples thereof include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylamino group having 1 to 6 carbon atoms, and an acylamino group having 1 to 6 carbon atoms. Preferably, the substituent is an anionic group such as a nitro group or a —SO ₃ M group. M represents a counter ion.
In addition, when the alkyl group having 1 to 3 carbon atoms, the benzoyl group or the phenyl group of R in the general formulas (1-1) and (1-2) has a substituent, the substituent is the aryl group or arylene. Examples thereof are the same as the substituents exemplified for the group.

Examples of the aryl group include a phenyl group and a condensed ring group in which a benzene ring is condensed, such as a naphthyl group.
Examples of the arylene group include a phenylene group and a condensed ring group condensed with a benzene ring such as a naphthylene group.
Q ¹ in the general formulas (1-1) and (1-2) is preferably a phenyl group which may have a substituent, and more preferably a phenyl group having a substituent at the para position.
Q ^{2 in the} general formula (1-2) is preferably a naphthylene group that may have a substituent, and more preferably a 1,4-naphthylene group that may have a substituent.

  A in formulas (1-1) and (1-2) is, for example, a sulfonic acid group, a carboxyl group, a phosphoric acid group, or a base thereof, and preferably a sulfonic acid group or a sulfonic acid group. And more preferably a sulfonate group.

  M in the general formulas (1-1) and (1-2) is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or a metal ion. In addition, after performing the water resistance treatment to the polarizing layer containing the azo compound represented by the general formula (1-1) or (1-2), the general formula (1-1) or (1-2) M is a cationic species derived from a nitrogen atom of an acyclic compound or a siloxane compound having an amino group.

  R in the general formulas (1-1) and (1-2) is preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

  Furthermore, k in the general formulas (1-1) and (1-2) is preferably an integer of 0 to 2, and more preferably an integer of 0 to 1. L of general formula (1-1) and (1-2) becomes like this. Preferably it is an integer of 0-2, More preferably, it is an integer of 0-1.

  The organic dye is more preferably an azo compound represented by the following general formula (1-3).

In the general formula (1-3), X is a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted carbon atom having 1 to 4 carbon atoms. Represents an alkoxy group or a —SO ₃ M group.
R and M in the general formula (1-3) are the same as R and M in the general formula (1-1).
In addition, when the alkyl group having 1 to 4 carbon atoms or the alkoxy group having 1 to 4 carbon atoms of X in the general formula (1-3) has a substituent, the substituent is exemplified by the aryl group or the arylene group. Examples thereof are the same as those described above.

  X in the general formula (1-3) is preferably a hydrogen atom, a nitro group, or a cyano group, and more preferably a nitro group.

An organic dye such as the azo compound exhibits liquid crystallinity (lyotropic liquid crystallinity) in a state dissolved in a solvent. Specifically, the organic dye forms an aggregate in which a plurality of the organic dyes are collected when dissolved in a solvent. When the liquid containing the organic dye is cast in a predetermined direction, a shear stress is applied to the aggregate. As a result, it is possible to form a coating film in which the long axis of the aggregate is oriented in the casting direction or in a direction perpendicular to the casting direction. The obtained coating film exhibits good absorption dichroism because the organic dye is oriented in a predetermined direction.
In particular, in the azo compound represented by the general formula (1-3), two or more —SO ₃ M groups are not adjacent to each other. Therefore, the azo compound has a small steric hindrance between the —SO ₃ M groups. For this reason, since the azo compound is linearly oriented before and after the water resistance treatment, the use of the azo compound can form a polarizing layer having a high degree of polarization.

  The azo compounds represented by the general formulas (1-1) to (1-3) can be obtained by the following method, for example. A monoazo compound is obtained by diazotization and coupling reaction of an aniline derivative and a naphthalenesulfonic acid derivative by a conventional method. After the diazotization of this monoazo compound, this is subjected to a coupling reaction with an aminonaphthol disulfonic acid derivative.

[Acyclic compound having nitrogen atom]
The acyclic compound contained in the polarizing layer has a nitrogen atom.
The number of nitrogen atoms of the acyclic compound is not particularly limited. However, it is preferable that the number of nitrogen atoms of the acyclic compound is 2 or more because it is interposed between a plurality of organic dyes forming an aggregate and easily binds adjacent organic dyes at an appropriate bonding point. 2 to 5 is more preferable, 2 to 4 is more preferable, and 2 or 3 is most preferable.

The acyclic compound having a nitrogen atom (for example, an acyclic compound having 2 to 5 nitrogen atoms) may be linear or branched, but is preferably linear. By using a linear acyclic compound, a water-resistant polarizing film having more excellent durability can be obtained.
Although carbon number of the said acyclic compound is not specifically limited, For example, it is 1-30, Preferably it is 2-20, More preferably, it is 2-16.

Further, the nitrogen atom is preferably contained in a cationic group bonded to the acyclic compound. Examples of the cationic group include amino groups, guanidino groups, imino groups, ammonium bases, and salts thereof.
Examples of the salt include inorganic acid salts such as hydrochloride, sulfate, and phosphate; organic acid salts such as acetic acid, formic acid, and oxalic acid.
In these, as a cationic group, an amino group or its salt is preferable.
The acyclic compound is preferably a compound having 2 to 5 cationic groups containing the nitrogen atom, more preferably a compound having 2 to 4 cationic groups, and two or more cationic groups. A compound having three is more preferable.
The acyclic compound is preferably a compound in which a cationic group is bonded to at least both ends of the main chain.

  Examples of the acyclic compound having 2 to 5 nitrogen atoms include aliphatic diamines such as alkyl diamines or salts thereof; aliphatic triamines such as alkyl triamines or salts thereof; aliphatic tetraamines such as alkyl tetraamines; Examples thereof include aliphatic pentaamines such as alkyl pentaamines or salts thereof; aliphatic ether diamines such as alkyl ether diamines or salts thereof.

  Preferably, the acyclic compound is an aliphatic diamine having 2 to 16 carbon atoms or a salt thereof, and / or an aliphatic ether diamine having 2 to 16 carbon atoms or a salt thereof.

  Examples of the linear aliphatic diamine include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8 -Octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine and the like. Among these, straight chain having 2 to 8 carbon atoms such as 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine and the like. It is preferable to use the alkyldiamine.

  Examples of the branched aliphatic diamine include 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl-1,4-butanediamine, 1,2- Dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1,4-butanediamine, 2,3-dimethyl-1,4-butanediamine, 2- Examples thereof include methyl-1,5-pentanediamine and 3-methyl-1,5-pentanediamine.

Aliphatic triamines include diethylenetriamine, dipropylenetriamine, bis (hexamethylene) triamine, 1,2,4-butanetriamine, 1,2,5-pentanetriamine, 1,3,5-pentanetriamine, 1,2, Examples include 6-hexanetriamine and 1,4,7-heptanetriamine.
Examples of the aliphatic tetraamine include triethylenetetramine and tetraethylenetetramine.
Examples of the aliphatic pentaamine include tetraethylenepentamine.

  Examples of the linear aliphatic ether diamine having 2 to 8 carbon atoms include 2,2′-oxybis (ethylamine), 3,3′-oxybis (propylamine), and 1,2-bis (2-aminoethoxy). Examples include ethane.

  The acyclic compound can be used alone or in combination of two or more. Preferably, two or more different acyclic compounds are used, and more preferably two or more acyclic compounds having different carbon numbers are used. By using two or more acyclic compounds having different carbon numbers, aggregates having different intervals can be bound by the acyclic compound. Preferably, two or more acyclic compounds having different numbers of cationic groups are used, and more preferably, a 1 to 5 carbon acyclic compound having two cationic groups and three acyclic compounds. An acyclic compound having 6 to 16 carbon atoms having a cationic group is used in combination. By using two or more acyclic compounds having different cationic groups, it is possible to bind to the aggregate at more points of attachment.

[Siloxane compound having an amino group]
The siloxane compound having an amino group has a siloxane unit containing a siloxane bond and having an amino group as a main skeleton. Hereinafter, a siloxane compound having an amino group may be referred to as an “aminosiloxane compound”.
The aminosiloxane compound is generally represented by the following formula (2-1).

In Formula (2-1), Y represents OR ⁴ or hydrolyzable groups, ^{R 4} is the same as ^{R 4} in the general formula (3-1) described below, m is the number of repeating units represents, for example, m is an integer of 2 or more, preferably an integer of 3 to 100, ^{R 1} is the same as ^{R 1} of the general formula (3-1) described below, a wavy line, silicon and nitrogen Represents a linking group that connects the two.

The aminosiloxane compound is bonded to a plurality of aggregates of organic dyes. The aminosiloxane compound binds a plurality of aggregates and fixes the alignment state of the aggregates.
Examples of the aminosiloxane compound represented by the general formula (2-1) include those represented by the following general formula (2-2).

In the general formula (2-2), Y and m are the same as those in the general formula (2-1), and R ¹ , R ² , R ³ and R ⁵ are the general formula (3-1) described later. Are the same as R ¹ , R ² , R ³ and R ⁵ .

The aminosiloxane compound includes a hydrolysis condensate of an aminosilane coupling agent, and is preferably composed of a hydrolysis condensate of an aminosilane coupling agent.
An aminosilane coupling agent is a silane compound having at least one amino group in its molecule. The amino group of the aminosilane coupling agent is preferably one or two, and more preferably one.
In the present invention, it is preferable to use an aminosilane coupling agent represented by the following general formula (3-1) or (3-2).

In the general formulas (3-1) and (3-2), R ¹ represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and R ² , R ^3, and R ⁴ are respectively Independently, it represents a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group, or a thiol group, and R ⁵ is interrupted by a substituted or unsubstituted divalent hydrocarbon group, or oxygen or nitrogen. Represents a substituted or unsubstituted divalent hydrocarbon group. When the monovalent hydrocarbon group, divalent hydrocarbon group, divalent oxygen-containing hydrocarbon group or nitrogen-containing hydrocarbon group has a substituent, the substituent includes a halogeno group, a nitro group, and a cyano group. , An amino group, an alkoxy group having 1 to 6 carbon atoms, an alkylamino group having 1 to 6 carbon atoms, an acylamino group having 1 to 6 carbon atoms, and the like.

  Carbon number of the said monovalent hydrocarbon group is 1-30, Preferably it is 1-12, More preferably, it is 1-6. Examples of the monovalent hydrocarbon group include linear, branched or cyclic alkyl groups, alkenyl groups, or alkynyl groups; aryl groups; aralkyl groups, and the like. Specific examples of the monovalent hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group. Octyl group, decyl group, vinyl group, allyl group, propenyl group, phenyl group, tolyl group, benzyl group and the like.

Preferably, the monovalent hydrocarbon group is a linear or branched alkyl group, the same alkenyl group, or the same alkynyl group, and more preferably a linear or branched alkyl group.
Carbon number of the said linear or branched alkyl group is 1-30, for example, Preferably it is 1-12, More preferably, it is 1-6, More preferably, it is 1-4. Specific examples of the linear or branched alkyl group having 1 to 30 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group. Tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, etc. Can be mentioned.
Carbon number of the said linear or branched alkenyl group or linear or branched alkynyl group is each independently 2-30, for example, Preferably, it is 2-12, More preferably It is 2-6, More preferably, it is 2-4. Specific examples of the linear or branched alkenyl group having 2 to 30 carbon atoms include vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, Examples include 2-pentenyl group, 1-hexenyl group, 2-hexenyl group, 1-octenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, octadecenyl group and the like. Specific examples of the linear or branched alkynyl group having 2 to 30 carbon atoms include, for example, ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, noninyl group, decynyl group. Group, undecynyl group, dodecynyl group and the like.

  As the thiol group, for example, a thiol group having 0 to 20 carbon atoms is preferable, a thiol group having 0 to 10 carbon atoms is more preferable, and a thiol group having 0 to 5 carbon atoms is more preferable. Specific examples of the thiol group include a mercaptomethyl group, a mercaptoethyl group, a 4-mercaptocyclohexyl group, and a 4-mercaptophenyl group.

Carbon number of the said bivalent hydrocarbon group is 1-30, Preferably it is 1-12, More preferably, it is 1-6. Examples of the divalent hydrocarbon group include a linear or branched alkylene group, the same alkenylene group, and the same alkynylene group. Preferably, the divalent hydrocarbon group is a linear or branched alkylene group.
Carbon number of the said linear or branched alkylene group is 1-30, for example, Preferably, it is 1-12, More preferably, it is 1-6, More preferably, it is 1-4. Specific examples of the linear or branched alkylene group having 1 to 30 carbon atoms include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, Examples include decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group and the like.
Carbon number of the said linear or branched alkenylene group or linear or branched alkynylene group is each independently 2-30, for example, Preferably, it is 2-12, More preferably It is 2-6, More preferably, it is 2-4. Specific examples of the linear or branched alkenylene group having 2 to 30 carbon atoms include vinylene group, 1-propenylene group, 2-propenylene group, 1-butenylene group, 2-butenylene group, 1-pentenylene group, 2-pentenylene group, 1-hexenylene group, 2-hexenylene group, 1-octenylene group and the like can be mentioned. Specific examples of the linear or branched alkynylene group having 2 to 30 carbon atoms include, for example, ethynylene group, propynylene group, butynylene group, pentynylene group, hexynylene group, heptynylene group, octynylene group, noninylene group, and decynylene. Group, undecynylene group, dodecynylene group and the like.

The carbon number of the divalent hydrocarbon group (divalent oxygen-containing hydrocarbon group) interrupted with oxygen is 2 to 30, preferably 2 to 12, and more preferably 2 to 6.
Examples of the divalent oxygen-containing hydrocarbon group include a divalent ether group. The divalent ether group is represented by —R ^A —O—R ^B —, and R ^A and R ^B are each independently a linear or branched divalent hydrocarbon group.
The carbon number of the divalent hydrocarbon group (divalent nitrogen-containing hydrocarbon group) interrupted with nitrogen is 2 to 30, preferably 2 to 12, and more preferably 2 to 6.
The divalent nitrogen-containing hydrocarbon group is represented by, for example, —R ^A —NH—R ^B —, and R ^A and R ^B are each independently a linear or branched divalent divalent group. It is a hydrocarbon group.
Examples of the divalent hydrocarbon group represented by R ^A and R ^B include linear or branched alkylene groups, alkenylene groups, or alkynylene groups as exemplified above, but preferably , A linear or branched alkylene group.

  Specific examples of the aminosilane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropylmethyldiethoxy. Silane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropylmethyldiethoxysilane, [3- (methyl Amino) propyl] trimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl Trimethoxysilane, trime Carboxymethyl and the like [3- (phenylamino) propyl] silane. The aminosilane coupling agent can be used alone or in combination of two or more.

[Siloxane compound having an epoxy group or an isocyanate group]
The siloxane compound having an epoxy group has a siloxane unit containing a siloxane bond and having an epoxy group as a main skeleton.
The siloxane compound having an isocyanate group has a siloxane unit containing a siloxane bond and having an isocyanate group as a main skeleton.
Hereinafter, a siloxane compound having an epoxy group may be referred to as an “epoxysiloxane compound”, and a siloxane compound having an isocyanate group may be referred to as an “isocyanate siloxane compound”.
The polarizing layer only needs to contain at least one of an epoxy siloxane compound and an isocyanate siloxane compound, for example, an epoxy siloxane compound or an isocyanate siloxane compound, or both an epoxy siloxane compound and an isocyanate siloxane compound. It is included.
The epoxy siloxane compound is generally represented by the following formula (4-1), and the isocyanate siloxane compound is generally represented by the following formula (5-1).

In the general formula (4-1), the EP group represents an epoxy group including an alicyclic epoxy group. In the general formulas (4-1) and (5-1), Z represents OR ⁸ or a hydrolyzable group, n represents the number of repeating units, for example, n is an integer of 2 or more, preferably is an integer of 3 to 100, ^{R 8} is the same as ^{R 8} in the general formula (6-1) and (7-1) described below, a wavy line, linking group which links between the silicon and carbon or nitrogen Represents.

  As said EP group, the epoxy group of the structure of following Formula (a) or (b) is mentioned.

The epoxy siloxane compound or isocyanate siloxane compound is bonded to an aminosiloxane compound. The epoxy siloxane compound or the isocyanate siloxane compound stabilizes the aminosiloxane compound bonded to the aggregate and assists in fixing the alignment state of the aggregate.
As an epoxysiloxane compound represented by the said general formula (4-1), what is represented by the following general formula (4-2) is mentioned, for example, The isocyanate represented by the said general formula (5-1) As a siloxane compound, what is represented by the following general formula (5-2) is mentioned, for example.

In the general formulas (4-2) and (5-2), the EP group, Z and n are the same as those in the general formulas (4-1) and (5-1), and R ⁶ , R ⁷ and R ⁹ is the same as R ⁶ , R ⁷ and R ⁹ in the general formulas (6-1) and (7-1) described later.

The said epoxy siloxane compound contains the hydrolysis condensate of an epoxy silane coupling agent, Preferably it is comprised from the hydrolysis condensate of an epoxy silane coupling agent.
The said isocyanate siloxane compound contains the hydrolysis condensate of an isocyanate silane coupling agent, Preferably it is comprised from the hydrolysis condensate of an isocyanate silane coupling agent.
The epoxy silane coupling agent is a silane compound having at least one epoxy group in the molecule. The epoxy group possessed by the epoxy silane coupling agent is preferably one or two, and more preferably one.
The isocyanate silane coupling agent is a silane compound having at least one isocyanate group in the molecule. The isocyanate group possessed by the isocyanate silane coupling agent is preferably one or two, and more preferably one.
In the present invention, an epoxy silane coupling agent represented by the following general formula (6-1) or (6-2), or an isocyanate represented by the following general formula (7-1) or (7-2) It is preferable to use a silane coupling agent.

In the general formulas (6-1) and (6-2), the EP group represents an epoxy group including an alicyclic epoxy group.
In the general formulas (6-1), (6-2), (7-1) and (7-2), R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, substituted or unsubstituted Represents a monovalent hydrocarbon group or a thiol group, and R ⁹ is a substituted or unsubstituted divalent hydrocarbon group, or a hydrocarbon group interrupted with oxygen or nitrogen and substituted or unsubstituted Represents a divalent hydrocarbon group. When the monovalent hydrocarbon group, divalent hydrocarbon group or divalent oxygen-containing hydrocarbon or nitrogen-containing hydrocarbon group has a substituent, examples of the substituent include a halogeno group, a nitro group, a cyano group, Examples include an amino group, an alkoxy group having 1 to 6 carbon atoms, an alkylamino group having 1 to 6 carbon atoms, and an acylamino group having 1 to 6 carbon atoms.

The epoxysilane coupling agent preferably has a structure represented by any of the following general formulas (6-3), (6-4), (6-5), or (6-6).
In the general formulas (6-3) to (6-6), R ⁶ , R ⁷ , R ⁸ and R ⁹ are the same as those in the general formulas (6-1) and (6-2).

Carbon number of the said monovalent hydrocarbon group is 1-30, Preferably it is 1-12, More preferably, it is 1-6, More preferably, it is 1-4. Examples of the monovalent hydrocarbon group include linear, branched or cyclic alkyl groups, alkenyl groups, or alkynyl groups; aryl groups; aralkyl groups, and the like. Preferably, the monovalent hydrocarbon group is a linear or branched alkyl group, the same alkenyl group, or the same alkynyl group, and more preferably a linear or branched alkyl group. Specific examples of the monovalent hydrocarbon group include those exemplified in the general formula (3-1).
As the thiol group, for example, a thiol group having 0 to 20 carbon atoms is preferable, a thiol group having 0 to 10 carbon atoms is more preferable, and a thiol group having 0 to 5 carbon atoms is more preferable. Specific examples of the thiol group include those exemplified in the general formula (3-1).

Carbon number of the said bivalent hydrocarbon group is 1-30, Preferably it is 1-12, More preferably, it is 1-6, More preferably, it is 1-4. Examples of the divalent hydrocarbon group include a linear or branched alkylene group, the same alkenylene group, and the same alkynylene group. Preferably, the divalent hydrocarbon group is a linear or branched alkylene group. Specific examples of the divalent hydrocarbon group include those exemplified in the general formula (3-1).
The carbon number of the divalent hydrocarbon group (divalent oxygen-containing hydrocarbon group) interrupted with oxygen is 2 to 30, preferably 2 to 12, and more preferably 2 to 6. Examples of the divalent oxygen-containing hydrocarbon group include a divalent ether group. The divalent ether group is represented by —R ^A —O—R ^B —, and R ^A and R ^B are each independently a linear or branched divalent hydrocarbon group. The carbon number of the divalent hydrocarbon group (divalent nitrogen-containing hydrocarbon group) interrupted with nitrogen is 2 to 30, preferably 2 to 12, and more preferably 2 to 6. The divalent nitrogen-containing hydrocarbon group is represented by, for example, —R ^A —NH—R ^B —, and R ^A and R ^B are each independently a linear or branched divalent divalent group. It is a hydrocarbon group. Examples of the divalent hydrocarbon group represented by R ^A and R ^B include a linear or branched alkylene group, the same alkenylene group, or the same alkynylene group as exemplified above, Preferably, it is a linear or branched alkylene group.

Specific examples of the epoxysilane coupling agent represented by the general formula (6-3) or (6-4) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3 -Glycidoxypropyl tripropoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldipropoxysilane, etc. are mentioned. As specific examples of the epoxysilane coupling agent represented by the general formula (6-5) or (6-6),
Examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane. The epoxy silane coupling agent can be used alone or in combination of two or more.

  Specific examples of the isocyanate silane coupling agent include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, 3-isocyanatepropylmethyldiethoxysilane, and the like. An isocyanate silane coupling agent can be used alone or in combination of two or more.

The content of the acyclic compound in the polarizing layer is not particularly limited, but is preferably more than 0 and 20% by mass or less, more preferably 1% by mass to 20% by mass with respect to the total amount of the polarizing layer. is there.
Further, the content of the aminosiloxane compound (or aminosilane coupling agent) in the polarizing layer is not particularly limited, but is preferably 0 with respect to 100 parts by mass of the acyclic compound contained in the polarizing layer. More than 200 parts by mass, more preferably 5 parts by mass to 150 parts by mass, and even more preferably 7 parts by mass to 120 parts by mass. If the amount of the aminosiloxane compound is too small, the binding of the aggregate is not sufficient, and if the amount is too large, the amount of the siloxane compound relative to the organic dye is relatively large.
In addition, the content of the siloxane compound having an epoxy group or an isocyanate group (or an epoxy silane coupling agent or an isocyanate silane coupling agent) in the polarizing layer is not particularly limited, but is preferably included in the polarizing layer. It is more than 0 and 200 parts by mass or less, more preferably 5 parts by mass to 150 parts by mass, and more preferably 7 parts by mass to 120 parts by mass with respect to 100 parts by mass of the aminosiloxane compound. If the amount of the siloxane compound having an epoxy group or an isocyanate group is too small, the amino group cap of the aminosiloxane compound is not sufficient, and if the amount is too large, the amount of the siloxane compound having an epoxy group or an isocyanate group relative to the organic dye is relative. Too many.

  The polarizing layer contains other components in addition to the organic dye, acyclic compound, aminosiloxane compound and epoxysiloxane compound (or epoxysiloxane compound) as long as the effects of the present invention are not impaired. May be. Examples of the other components include other organic dyes (that is, organic dyes other than organic dyes having an anionic group), various additives, and arbitrary polymers.

[Various characteristics of water-resistant polarizing film]
The water-resistant polarizing film having the polarizing layer exhibits absorption dichroism in at least a part of wavelengths in the visible light region (wavelength 380 nm to 780 nm).
The transmittance of the water-resistant polarizing film having the polarizing layer is 38% or more, preferably 39% or more, and more preferably 40% or more.
The water-resistant polarizing film having the polarizing layer has a degree of polarization (degree of polarization determined from Y value corrected for visual sensitivity) of 98% or more, and preferably 99% or more.
The thickness of the polarizing layer is not particularly limited, but is preferably 0.1 μm to 10 μm. When the thickness of this polarizing layer is less than 1 μm, it is preferable to use it in a state of being laminated on a substrate as shown in FIG.

The water-resistant polarizing film of the present invention is hardly dissolved even when the polarizing layer is in contact with water, and its optical characteristics are hardly changed. In particular, as in the examples described later, the polarizing layer is not easily dissolved even by ultrasonic cleaning, and thus has excellent durability against water immersion accompanied by vibration.
It is presumed that the organic dye, the acyclic compound, the aminosiloxane compound, and the epoxysiloxane compound (or the isocyanatesiloxane compound) are present in the state shown in FIG. 2 in the polarizing layer.
FIG. 2 is a reference diagram schematically showing the state of each component in the polarizing layer. However, although FIG. 2 shows an epoxy siloxane compound, an isocyanate siloxane compound is the same in place of the epoxy siloxane compound.

  In FIG. 2, a plurality of organic dyes in the polarizing layer are gathered to form an aggregate, and the plurality of aggregates are oriented in a predetermined direction. The cationic group of the acyclic compound is electrostatically bonded to the anionic group of the organic dye of the aggregate, and the acyclic compound is interposed between the aggregates and binds adjacent aggregates. ing. Further, the amino group of the aminosiloxane compound is electrostatically bonded to the anionic group of the organic dye of the aggregate, and the aminosiloxane compound binds a plurality of aggregates. Since this aminosiloxane compound is a silane condensation polymer, it binds more aggregates than an acyclic compound. As described above, the acyclic compound and the aminosiloxane compound cooperate to bind a plurality of aggregates, thereby fixing the alignment state of the aggregates.

Further, not all amino groups of the aminosiloxane compound are bonded to the aggregate, and it is considered that the aminosiloxane compound has an unbonded amino group in the aggregate in the polarizing layer. The epoxy group of the epoxy siloxane compound (or the isocyanate group of the isocyanate siloxane compound) is covalently bonded to the non-aggregate amino group. The amino group has a large polarity (that is, a high hydrophilicity), but the non-associate amino group is capped by the epoxy siloxane compound (or isocyanate siloxane compound) bonded thereto. By such an epoxy siloxane compound (or isocyanate siloxane compound), the aminosiloxane compound that binds the aggregate is particularly stabilized against water. In addition, since the epoxy siloxane compound (or isocyanate siloxane compound) is also a silane condensation polymer, the epoxy siloxane compound assists in fixing the alignment state of a plurality of aggregates.
As for acyclic compounds, some cationic groups may not be bonded to the organic dye, but the epoxy group of the epoxy siloxane compound (isocyanate of the isocyanate siloxane compound) is added to the cationic group of the association bond. It is also conceivable that the group) is bonded and the epoxysiloxane compound (or isocyanatesiloxane compound) stabilizes the acyclic compound.
Since an acyclic compound, an aminosiloxane compound, and an epoxysiloxane compound (or an isocyanate siloxane compound) make a plurality of aggregates into a structure like a larger aggregate and thereby fix the orientation state of the aggregate, The polarizing layer is considered to have excellent durability against water.

[Method for producing water-resistant polarizing film]
The water-resistant polarizing film of the present invention can be produced, for example, through the following steps A to C, and further, after the step C, the following step D may be performed.
Process A: The process of forming the coating film containing an organic pigment | dye by apply | coating the coating liquid containing the organic pigment | dye which has anionic property on a base material.
Step B: A step of obtaining a polarizing layer by drying the coating film formed in Step A.
Step C: A step of bringing a treatment liquid containing an acyclic compound, an aminosilane coupling agent, and an epoxysilane coupling agent or an isocyanatesilane coupling agent into contact with one surface or both surfaces of the polarizing layer obtained in Step B (water resistance Processing).
Step D: A step of washing the polarizing layer in order to remove excess processing liquid adhering to the polarizing layer and the like.

(Process A)
In step A, a coating liquid containing an organic dye is applied onto a substrate to form a coating film. As the organic dye, the exemplified dyes are used, and an azo compound represented by the general formula (1-3) is preferably used. A coating liquid can be prepared by dissolving the organic dye in a suitable solvent.
In the coating solution, an organic dye forms an aggregate in the solution, and as a result, exhibits a liquid crystal phase. The liquid crystal phase is not particularly limited, and examples thereof include a nematic liquid crystal phase, a smectic liquid crystal phase, a cholesteric liquid crystal phase, and a hexagonal liquid crystal phase. The liquid crystal phase can be confirmed and identified by an optical pattern observed with a polarizing microscope.

  The solvent is not particularly limited, and a conventionally known solvent can be used. Preferably, a solvent in which the organic dye can be satisfactorily dissolved is used. By using a coating solution in which the organic dye is well dissolved, it is difficult for the organic dye to precipitate when the coating liquid is applied onto a substrate to form a film. Therefore, a polarizing layer having excellent transmittance can be obtained.

The solvent in which the organic dye can be dissolved well is, for example, an aqueous solvent.
Examples of the aqueous solvent include water, a hydrophilic solvent, a mixed solvent of water and a hydrophilic solvent, and the like. The hydrophilic solvent is a solvent that can be uniformly dissolved in water.
Examples of the hydrophilic solvent include alcohols such as methanol, ethanol, methyl alcohol and isopropyl alcohol; glycols such as ethylene glycol and diethylene glycol; cellosolves such as methyl cellosolve and ethyl cellosolve; ketones such as acetone and methyl ethyl ketone; acetic acid Examples include esters such as ethyl. Preferably, the solvent is water or a mixed solvent of water and a hydrophilic solvent.

The concentration of the organic dye in the coating liquid is preferably adjusted to a concentration showing a liquid crystal phase. Specifically, the concentration of the organic dye (the amount of the organic dye relative to the total amount of the coating liquid) is preferably 0.5% by mass to 50% by mass. In a part of such a concentration range, the coating liquid may exhibit a liquid crystal phase.
The pH of the coating solution is preferably adjusted to about pH 4-10, more preferably about pH 6-8.

Furthermore, an additive may be added to the coating liquid. Examples of additives include plasticizers, heat stabilizers, light stabilizers, lubricants, antioxidants, ultraviolet absorbers, flame retardants, colorants, antistatic agents, antibacterial agents, compatibilizers, cross-linking agents, and thickeners. Agents and the like. The concentration of the additive in the coating solution (the amount of the additive element relative to the total amount of the coating solution) is preferably more than 0 and 10% by mass or less. Further, a surfactant may be added to the coating liquid. The surfactant is added to improve the wettability and coatability of the coating liquid to the substrate surface. It is preferable to use a nonionic surfactant as the surfactant. The concentration of the surfactant in the coating solution (same as above) is preferably more than 0 and 5% by mass or less.
The method for preparing the coating liquid is not particularly limited. For example, the organic dye may be added to a container containing a solvent, or the solvent may be added to a container containing an organic dye.

A coating film can be formed by applying the coating liquid on a suitable substrate.
The substrate is used to uniformly develop the coating liquid. The type of the substrate is not particularly limited as long as it is suitable for this purpose. For example, a synthetic resin film (a film means a sheet including what is generally called a sheet), a glass plate, or the like can be used.
In a preferred embodiment, the substrate is a single polymer film. In another preferred embodiment, the substrate is a laminate comprising a polymer film. This laminate preferably further comprises an alignment layer on the polymer film.
Although it does not specifically limit as said polymer film, The film (for example, haze value 5% or less) excellent in transparency is preferable.
The thickness of the base material can be appropriately designed according to the strength and the like. From the viewpoint of reduction in thickness and weight, the thickness of the substrate is preferably 300 μm or less, more preferably 5 μm to 200 μm, and more preferably 10 μm to 100 μm.
When the substrate includes an alignment layer, the alignment layer can be formed by performing an alignment treatment on the substrate. Examples of the alignment treatment include mechanical alignment treatment such as rubbing treatment and chemical alignment treatment such as photo-alignment treatment.

A coating solution is applied on the substrate (preferably on the alignment layer of the substrate). The viscosity of the coating liquid at the time of application is preferably 0.1 mPa · s to 30 mPa · s, and more preferably 0.5 mPa · s to 3 mPa · s. However, the viscosity is a value measured by a rheometer (manufactured by Haake, product name: rheostress 600, measurement condition: double cone sensor shear rate 1000 (1 / s)).
Further, when the hydrophilicity of the coated surface of the base material (the surface of the base material to which the coating liquid is applied) is low, it is preferable to perform a hydrophilic treatment on the coated surface.
The hydrophilic treatment may be a dry treatment or a wet treatment. Examples of the dry treatment include discharge treatment such as corona treatment, plasma treatment or glow discharge treatment; flame treatment; ozone treatment; UV ozone treatment; ionizing active ray treatment such as ultraviolet treatment or electron beam treatment. Examples of the wet treatment include ultrasonic treatment using a solvent such as water and acetone, alkali treatment, anchor coat treatment, and the like. These processes may be performed independently or in combination of two or more.

  As a method for applying the coating liquid to the surface of the substrate, for example, an application method using an appropriate coater may be employed. Examples of the coater include a bar coater, a reverse roll coater, a forward rotation roll coater, a gravure coater, a rod coater, a slot die coater, a slot orifice coater, a curtain coater, and a fountain coater.

When a coating liquid in a liquid crystal phase is applied, shear stress is applied to the organic dye during the flow of the coating liquid. As a result, a coating film in which the organic dye is oriented in a predetermined direction can be formed.
In addition, although the said organic pigment | dye is orientated by the shear stress added at the time of casting of a coating liquid, it can replace with this or can use this together, and can also orientate an organic pigment | dye by another means.
Examples of the other means include, for example, a means for applying a coating liquid on a substrate subjected to an orientation treatment, and a magnetic field or an electric field applied after forming a coating film by applying the coating liquid on the substrate. The means to do is mentioned. Even if these other means are carried out alone, a coating film in which the organic dye is oriented in a predetermined direction can be formed.

(Process B)
In step B, the coating film formed in step A is dried.
The method for drying the coating film may be either natural drying or forced drying. For forced drying, for example, an air circulation type constant temperature oven in which hot air or cold air circulates, a heater using microwaves or far infrared rays, a roll heated for temperature control, a heated heat pipe roll, heated A drying means such as a metal belt can be used.
The drying temperature is equal to or lower than the isotropic phase transition temperature of the coating liquid, and it is preferable to gradually raise the temperature from a low temperature to a high temperature. Specifically, the drying temperature is preferably 10 ° C to 80 ° C, more preferably 20 ° C to 60 ° C. If it is this temperature range, a dry coating film with small thickness variation can be obtained.
The drying time can be appropriately selected depending on the drying temperature and the type of solvent. In order to obtain a dry coating film with small thickness variation, the drying time is, for example, 1 minute to 30 minutes, and preferably 1 minute to 10 minutes.

The coating film has a higher concentration in the process of drying, and the oriented organic dye is fixed. By fixing the orientation of the organic dye, absorption dichroism is produced. The obtained dry coating film is a polarizing layer.
The thickness of the obtained polarizing layer (dry coating film) is preferably 0.1 μm to 10 μm. The amount of residual solvent in the polarizing layer is preferably 1% by mass or less, more preferably 0.5% by mass or less, with respect to the total mass of the polarizing layer.

(Process C)
In step C, the surface of the polarizing layer obtained in step B (the surface opposite to the bonding surface of the base material) is coated with an acyclic compound, an aminosilane coupling agent, and an epoxysilane coupling agent or an isocyanatesilane coupling agent. A treatment solution containing

As the acyclic compound, aminosilane coupling agent, and epoxy silane coupling agent or isocyanate silane coupling agent, those exemplified above are used.
The treatment liquid is obtained by dissolving or dispersing an acyclic compound, an aminosilane coupling agent, and an epoxy silane coupling agent or an isocyanate silane coupling agent in a solvent. As the solvent, an aqueous solvent is preferably used. As the aqueous solvent, those exemplified in the column of the coating liquid can be used.

One treatment liquid in which the acyclic compound, aminosilane coupling agent, and epoxy silane coupling agent or isocyanate silane coupling agent are collectively dissolved in one solvent may be used, or a plurality of treatment liquids may be used. It may be divided into
For example, the treatment liquids divided into the following are listed as follows.
(1) One treatment liquid in which an acyclic compound, an aminosilane coupling agent, and an epoxysilane coupling agent or an isocyanatesilane coupling agent are collectively dissolved in a solvent.
(2) The first treatment liquid in which one selected from an acyclic compound, an aminosilane coupling agent, and an epoxysilane coupling agent or an isocyanatesilane coupling agent was dissolved in a solvent, and the above was not selected A second treatment solution in which two are dissolved in a solvent.
(3) A first treatment liquid in which an acyclic compound is dissolved in a solvent, a second treatment liquid in which an aminosilane coupling agent is dissolved in a solvent, and an epoxysilane coupling agent or an isocyanatesilane coupling agent. The 3rd processing liquid dissolved in.

  The concentration of the acyclic compound in the treatment liquid (amount of the acyclic compound relative to the total amount of the treatment liquid) can be appropriately set, but is preferably 5% by mass to 30% by mass. The concentration of the aminosilane coupling agent in the treatment liquid (same as above) can be set as appropriate, but is preferably 5% by mass to 30% by mass. Although the density | concentration (same as the above) of the epoxy silane coupling agent or isocyanate silane coupling agent in the said process liquid can be set suitably, Preferably it is 0.5 mass%-20 mass%.

By bringing the treatment liquid into contact with one or both surfaces of the polarizing layer obtained in Step B, a water-resistant polarizing layer having excellent durability can be obtained.
When the treatment liquid is divided into a plurality of parts, the plurality of treatment liquids are brought into contact with the polarizing layer simultaneously or sequentially.
The method for bringing the treatment liquid into contact with the polarizing layer is not particularly limited. Examples of the contact method include a method of applying a treatment liquid to the surface of the polarizing layer, a method of immersing the polarizing layer in the treatment liquid, and the like. The treatment liquid can be applied using various coaters or sprays. When these methods are employed, the surface of the polarizing layer is preferably washed with water or an arbitrary solvent and dried. The contact method is preferably a method of immersing the polarizing layer in the treatment liquid. According to this method, the treatment liquid can be reliably brought into contact with the entire polarizing layer. Further, according to this method, the treatment liquid easily penetrates into the polarizing layer, so that water resistance can be reliably imparted to the polarizing layer.

  The aminosilane coupling agent and the epoxy silane coupling agent or the isocyanate silane coupling agent are hydrolyzed with moisture in the treatment liquid or the polarizing layer to produce silanol, and the silanol is partially or wholly condensed. An aminosiloxane compound and an epoxysiloxane compound or an isocyanatesiloxane compound are formed in the polarizing layer.

(Process D)
In step D, the surface of the polarizing layer after the water resistance treatment is washed and / or dried.
Step D is performed in order to remove excess treatment liquid adhering to the water-resistant polarizing film obtained in Step C.
For example, the polarizing layer after the water resistance treatment may be washed with water and then dried. Further, the polarizing layer after the water resistance treatment may be simply dried.
Moreover, the manufacturing method of this invention may have another process other than the said process A-process D further.

[Use of water-resistant polarizing film]
The water-resistant polarizing film of the present invention can be used, for example, for lenses such as sunglasses, light control windows, image display devices, and the like.
Since the water-resistant polarizing film of the present invention has extremely excellent durability against water, it can be suitably used as a component member for lenses and light control windows. In particular, the water-resistant polarizing film can be suitably used for lenses such as sunglasses because it is difficult to dissolve even when subjected to ultrasonic cleaning and changes in optical properties are small.
Moreover, the water-resistant polarizing film of this invention can also be used as a polarizing plate by laminating | stacking a protective film on the one surface or both surfaces. When used as a polarizing plate, a retardation film may be further laminated on the water-resistant polarizing film.
The water-resistant polarizing film of the present invention can be used in a state where it is laminated on the substrate, or can be used after being peeled off from the substrate.

  The present invention will be described in detail with reference to examples and comparative examples. In addition, this invention is not limited only to the following Example.

[Example 1]
4-Nitroaniline and 8-amino-2-naphthalenesulfonic acid are prepared according to a conventional method (Toyo Hosoda, “Theoretical Manufacturing, Dye Chemistry, 5th Edition”, published on July 15, 1968, Technique Hall, pages 135-152. The monoazo compound was obtained by diazotization and coupling reaction by the above method. The obtained monoazo compound was diazotized by the above-mentioned conventional method and further subjected to a coupling reaction with 1-amino-8-naphthol-2,4-disulfonic acid lithium salt to obtain a crude product. This was salted out with lithium chloride to obtain an azo compound of the following structural formula (1-4).

The azo compound of the formula (1-4) was dissolved in ion exchange water to prepare a 4% by mass coating solution. When this coating solution was observed at room temperature (23 ° C.) according to the following method for observing a liquid crystal phase, the coating solution showed a nematic liquid crystal phase.
A bar coater (manufactured by BUSHMAN, product name “Mayer rot HS4”) is applied on a norbornene polymer film (manufactured by Nippon Zeon Co., Ltd., trade name “ZEONOR”) subjected to rubbing treatment and corona treatment. It was used and coated and allowed to dry naturally in a constant temperature room at 23 ° C. The obtained polarizing layer had a thickness of 0.3 μm.

On the other hand, in 91 parts by mass of ion-exchanged water, 9 parts by mass of an acyclic compound mixture (see below), 9 parts by mass of 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., trade name “KB-”) 903 ") and 9 parts by mass of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., trade name" KB-403 ") were prepared. The acyclic compound mixture is a mixture of 1,3-propanediamine hydrochloride, 1,2-ethylenediamine hydrochloride and bis (hexamethylene) triamine (all manufactured by Tokyo Chemical Industry Co., Ltd.), and its mass The ratio is 55:15:30.
The polarizing layer laminated on the polymer film was immersed in the treatment liquid for 2 seconds. Next, this was washed with water and then dried to prepare a polarizing film.

<Observation of liquid crystal phase>
A small amount of the coating solution was sandwiched between the two glass slides, and the liquid crystal phase was observed using a polarizing microscope (manufactured by Olympus Corporation, product name “OPTIPHOT-POL”).
<Measurement method of thickness of polarizing layer>
The thickness of the polarizing layer is determined by peeling a part of the polarizing layer from the polymer film and using the three-dimensional non-contact surface shape measurement system (product name “Micromap MM5200” manufactured by Ryoka System Co., Ltd.) The level difference with the polarizing layer was measured.

[Example 2]
A polarizing film was produced in the same manner as in Example 1 except that the amount of 3-glycidoxypropyltrimethoxysilane was changed to 4.5 parts by mass.
[Example 3]
A polarizing film was produced in the same manner as in Example 1 except that the amount of 3-glycidoxypropyltrimethoxysilane was changed to 2.7 parts by mass.
[Example 4]
A polarizing film was produced in the same manner as in Example 1 except that the amount of 3-glycidoxypropyltrimethoxysilane was changed to 0.9 parts by mass.

[Comparative Example 1]
A polarizing film was produced in the same manner as in Example 1 except that 3-glycidoxypropyltrimethoxysilane was not added.
[Comparative Example 2]
A polarizing film was produced in the same manner as in Example 1 except that 3-aminopropyltriethoxysilane was not added.
[Comparative Example 3]
A polarizing film was produced in the same manner as in Example 1 except that the mixture of acyclic compounds was not added.

[Water resistance test of polarizing layer]
The polarizing films of each Example and Comparative Example were each immersed in an ultrasonic cleaner (trade name “Bransonic Model 8800” manufactured by BRANSON, Inc.) containing water at 60 ° C. and ultrasonically cleaned for 5 minutes. After ultrasonic cleaning, the polarizing film was taken out and the state of the polarizing layer was confirmed. The results are shown in Table 1.
However, in Table 1, A was that the polarizing layer was not dissolved, B was that part of the polarizing layer was dissolved but most of it was not dissolved, and C was that of the polarizing layer. The whole was dissolved.

[Change test of transmittance and polarization degree of polarizing layer]
About each of the polarizing film (polarizing film obtained by being immersed in a process liquid and drying) of each Example and a comparative example, the single-piece | unit transmittance | permeability (Ts) and the polarization degree (P) were calculated | required with the following method.
Next, each of the polarizing films of each Example and Comparative Example was allowed to stand for 100 hours in an environment of 60 ° C. and 90% RH, and similarly, its single transmittance (Ts) and polarization degree (P). Asked. Table 1 shows changes in single transmittance (ΔTs) and changes in polarization degree (ΔP) before the test and after standing for 100 hours.
Change in single transmittance (ΔTs) = single transmittance after standing−single transmittance before test.
Change in polarization degree (ΔP) = polarization degree after standing−polarization degree before test.

<Measurement method of transmittance and polarization degree>
Using a spectrophotometer equipped with a Gram-Thomson polarizer (manufactured by JASCO Corporation, product name “V-7100”), linearly polarized light having a wavelength of 380 nm to 780 nm is incident on the polarizing layer, and a visibility correction coefficient for each wavelength. Were integrated to measure the average k ₁ and k ₂ in the wavelength region. By substituting these k ₁ and k ₂ into the following formulas 1 and 2, the single transmittance (Ts) and the degree of polarization (P) were determined.
Formula 1: Single transmittance = (k ₁ + k ₂ ) / 2
Formula 2: Polarization degree = (k ₁ −k ₂ ) / (k ₁ + k ₂ )
Incidentally, k ₁ represents a transmittance of the maximum transmittance direction of linearly polarized light, k ₂ represents a transmittance of a linearly polarized light in a direction perpendicular to the maximum transmittance direction.

[Evaluation]
From the comparison between each Example and Comparative Example 1, it can be seen that the change in transmittance is reduced by adding the epoxysilane coupling agent.
From the comparison between each Example and Comparative Example 2, it can be seen that the addition of the aminosilane coupling agent makes it difficult to dissolve in water.
From the comparison between each Example and Comparative Example 3, it can be seen that by adding an acyclic compound, an aminosilane coupling agent and an epoxysilane coupling agent, it is difficult to dissolve in water and the change in transmittance is small. .

  The water-resistant polarizing film of the present invention can be used as a constituent member of a lens such as polarized sunglasses or a constituent member of an image display device such as a liquid crystal display device.

Claims (8)

  A water-resistant polarizing film having a polarizing layer comprising an organic dye having an anionic group, an acyclic compound having a nitrogen atom, a siloxane compound having an amino group, and a siloxane compound having an epoxy group or an isocyanate group. The polarizing layer includes a plurality of aggregates in which a plurality of the organic dyes are collected,
The water-resistant polarizing film according to claim 1, wherein the siloxane compound having an amino group is bonded to a plurality of aggregates.   The water-resistant polarizing film according to claim 1 or 2, wherein the siloxane compound having an epoxy group or an isocyanate group is bonded to the siloxane compound having an amino group. The siloxane compound having an amino group includes a hydrolysis condensate of an aminosilane coupling agent represented by the following general formula (3-1) or (3-2). The water-resistant polarizing film as described.

R ¹ represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a substituted or unsubstituted monovalent carbon group. Represents a hydrogen group or a thiol group, and R ⁵ represents a substituted or unsubstituted divalent hydrocarbon group, or a hydrocarbon group interrupted with oxygen or nitrogen and substituted or unsubstituted divalent carbonization. Represents a hydrogen group. The siloxane compound having an epoxy group includes a hydrolysis condensate of an epoxy silane coupling agent represented by the following general formula (6-1) or (6-2). The water-resistant polarizing film described in 1.

R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group or a thiol group, and R ⁹ represents a substituted or unsubstituted divalent carbonization. A hydrogen group or a hydrocarbon group interrupted with oxygen or nitrogen, which is a substituted or unsubstituted divalent hydrocarbon group. The siloxane compound having an isocyanate group includes a hydrolysis condensate of an isocyanate silane coupling agent represented by the following general formula (7-1) or (7-2). The water-resistant polarizing film described in 1.

R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group or a thiol group, and R ⁹ represents a substituted or unsubstituted divalent carbonization. A hydrogen group or a hydrocarbon group interrupted with oxygen or nitrogen, which is a substituted or unsubstituted divalent hydrocarbon group.   The water-resistant polarizing film according to any one of claims 1 to 6, wherein the acyclic compound has 2 to 5 cationic groups containing a nitrogen atom in the molecule. The water-resistant polarizing film according to any one of claims 1 to 7, wherein the organic dye contains an azo compound represented by the following general formula (1-3).

X represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, or a —SO ₃ M group. M represents a counter ion, and R represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted acetyl group, a substituted or unsubstituted benzoyl group, or a substituted or unsubstituted group. Represents a substituted phenyl group.

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