JP7082021B2 - Polarizing film and its manufacturing method - Google Patents

Description

The present invention relates to a polarizing film in which a first resin layer, a polarizing element, an alignment film, and a second resin layer are laminated in this order, and a method for producing the same.

A polarizing film or the like is used in the flat panel display device (FPD). Such a polarizing film includes a polarizing element in which a dichroic dye such as iodine is oriented and adsorbed on a polyvinyl alcohol-based resin film, and a polarizing film obtained by applying a polymerizable liquid crystal compound on a substrate and polymerizing the film. The film is known. For example, Patent Document 1 discloses a polarizing film having a dye diffusion prevention layer on both sides of a polymer of a polymerizable liquid crystal compound and a polarizing element containing a dichroic dye.

Japanese Unexamined Patent Publication No. 2017-083843

However, according to the study of the present inventor, in such a polarizing film, the dye diffusion prevention layer (resin layer) is formed by a water-soluble resin having a polarity different from that of the hydrophobic polymerizable liquid crystal, so that each layer is formed. It was found that the compatibility of the interface is not sufficient and the adhesiveness may not be sufficient.

Therefore, an object of the present invention is to provide a polarizing film having excellent adhesion between layers and a method for producing the same.

As a result of diligent studies to solve the above problems, the present inventor has found that the first resin layer, the polarizing element, the alignment film, and the polarizing film in which the second resin layer is laminated in this order include the first resin layer and the polarizing element. , The alignment film, and the second resin layer are formed of a cured product of a composition containing a compound having a (meth) acryloyl group, respectively, to solve the above-mentioned problems, and have completed the present invention. That is, the present invention includes the following aspects.

[1] A polarizing film in which a first resin layer, a polarizing element, an alignment film, and a second resin layer are laminated in this order.
The first resin layer is a cured product of the first curable composition containing a (meth) acrylic compound.
The polarizing element is a cured product of a composition for forming a polarizing element containing a polymerizable liquid crystal compound having a (meth) acryloyl group and a dichroic dye.
The alignment film is a cured product of a composition for forming an alignment film containing a (meth) acrylic compound.
The second resin layer is a polarizing film which is a cured product of a second curable composition containing a (meth) acrylic compound.
[2] The polarizing film according to [1], wherein at least one of the first curable composition and the second curable composition contains a radical polymerization initiator.
[3] The polarizing film according to [1] or [2], wherein at least one of the first curable composition and the second curable composition contains a urethane (meth) acrylate compound as the (meth) acrylic compound.
[4] The polarizing film according to [3], wherein the urethane (meth) acrylate compound has a (meth) acryloyl group number of 15 × 10 ^-4 or more per unit molecular weight.
[5] The description according to any one of [1] to [4], wherein at least one of the first curable composition and the second curable composition contains a polyfunctional (meth) acrylate compound as the (meth) acrylic compound. Polarizing film.
[6] The polarizing film according to [5], wherein the polyfunctional (meth) acrylate compound has 6 or more (meth) acryloyl groups.
[7] The polyfunctional (meth) acrylate compound has a branched structure, and the number of atoms in the chain connecting the branch point closest to the (meth) acryloyl group in the branched structure and the (meth) acryloyl group is The polarizing film according to [5] or [6], which is 3 or less.
[8] The first curable composition is applied or superposed on the polarizing element surface of the laminate in which the second resin layer, the alignment film, and the polarizing element are laminated in this order, and the first curable composition is cured. The method for producing a polarizing film according to any one of [1] to [7], which comprises a step.
[9] The first curable composition formed on the release film is superposed on the polarizing element surface of the laminate in which the second resin layer, the alignment film, and the polarizing element are laminated in this order, and the release film is formed. By irradiating the active energy ray from the side to cure the first curable composition, a laminate in which the release film, the first resin layer, the polarizing element, the alignment film, and the second resin layer are laminated in this order is formed. The method for producing a polarizing film according to any one of [1] to [7], which comprises a step of peeling the release film from the laminate.

The polarizing film of the present invention has excellent adhesion between layers.

It is the schematic sectional drawing of the layer structure of the polarizing film with a front plate which is one aspect of this invention. It is the schematic sectional drawing of the layer structure of the polarizing plate with a front plate which is one aspect of this invention. It is the schematic sectional drawing of the layer structure of the polarizing film with a front plate which is one aspect of this invention. It is the schematic sectional drawing of the layer structure of the polarizing plate with a front plate which is one aspect of this invention.

[Polarizing film]
In the polarizing film of the present invention, a first resin layer, a polarizing element, an alignment film, and a second resin layer are laminated in this order. The first resin layer is a cured product of the first curable composition containing a (meth) acrylic compound, and the stator is for forming a polarizing element containing a polymerizable liquid crystal compound having a (meth) acryloyl group and a bicolor dye. The cured product of the composition, the alignment film is a cured product of the alignment film forming composition containing the (meth) acrylic compound, and the second resin layer is the cured product of the second curable composition containing the (meth) acrylic compound. It is a thing. As described above, the polarizing film of the present invention is composed of a cured product of a composition in which each layer contains a compound having a (meth) acryloyl group, that is, contains a polymer of a compound having a (meth) acryloyl group. Since it is configured, the compatibility between the interfaces of each layer is high, and excellent adhesion between layers can be exhibited.

<Polarizer>
The polarizing element contained in the polarizing film of the present invention is formed on the surface of the alignment film opposite to the second resin layer. The polarizing element is a cured product of a composition for forming a polarizing element, which comprises a polymerizable liquid crystal compound having a (meth) acryloyl group and a dichroic dye. In such a polarizing element, the dichroic dye is encapsulated in the polymerizable liquid crystal compound, and the polymerizable liquid crystal compound and the dichroic dye are polymerized and cured in an oriented state. However, polyvinyl is widely used in the past. Compared to a polarizing element in which a dichroic dye is adsorbed and oriented on an alcohol-based resin film, the dichroic dye is less likely to be retained by the polymer component, and the dichroic dye is transferred from the polarizing element to the first resin in a high temperature environment or the like. It tends to diffuse heat to the layer or the second resin layer, and the polarization performance tends to deteriorate over time. In particular, in order to improve the adhesion between the layers of the polarizing film, if a resin layer having good compatibility with the polymer of the polymerizable liquid crystal compound is simply selected, the phase of the dichroic dye contained in the polarizing element to the resin layer is selected. Since the solubility is also improved, the thermal diffusion of the dichroic dye tends to appear remarkably. In the present invention, since the first resin layer and the second resin layer are each composed of a cured product of a curable composition containing a (meth) acrylic compound, in addition to the adhesiveness in an embodiment capable of forming a crosslinked structure, the present invention It can also have excellent heat resistance, and can effectively suppress deterioration of the polarizing performance of the polarizing film even when exposed to a high temperature environment for a long time. In the present specification, the term "heat resistance" means that even if it is exposed to a high temperature environment for a long period of time, it exhibits a characteristic that a decrease in polarization performance, for example, a change in polarization degree or transmittance can be suppressed, and the heat resistance becomes high. Improving means less reduction or change in polarization performance.

In the polarizing film of the present invention, the polymerizable liquid crystal compound (hereinafter, may be referred to as “polymerizable liquid crystal compound (A)”) contained in the composition for forming a substituent is a liquid crystal having at least one (meth) acryloyl group. It is a compound, and is preferably a liquid crystal compound having two or more (meth) acryloyl groups from the viewpoint of improving the adhesion and heat resistance of the polarizing film. Further, the polymerizable liquid crystal compound (A) may contain a polymerizable group other than the (meth) acryloyl group. A polymerizable group is a group that can participate in a polymerization reaction by an active radical, an acid, or the like generated from a polymerization initiator. Examples of the polymerizable group other than the (meth) acryloyl group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an oxylanyl group, an oxetanyl group and the like. In the present invention, from the viewpoint of adhesion and heat resistance of the polarizing film, the polymerizable group of the polymerizable liquid crystal compound (A) is preferably composed of a (meth) acryloyl group, and is preferably composed of a (meth) acryloyloxy group. It is more preferable that it is.

In the present invention, the polymerizable liquid crystal compound (A) is preferably a compound exhibiting smectic liquid crystal properties. By using a polymerizable liquid crystal compound exhibiting smectic liquid crystal properties, it is possible to form a polarizing element having a high degree of orientation order. The liquid crystal state indicated by the polymerizable liquid crystal compound (A) is a smectic phase (smetic liquid crystal state), and from the viewpoint of achieving a higher degree of orientation order, it is more likely to be a higher-order smectic phase (higher-order smectic liquid crystal state). preferable. Here, the higher-order smectic phase includes a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, a smectic K phase, and a smectic L phase. This means that among these, the smectic B phase, the smectic F phase and the smectic I phase are more preferable. The liquid crystal property may be a thermotropic liquid crystal or a lyotropic liquid crystal, but the thermotropic liquid crystal is preferable in that precise film thickness control is possible. Further, the polymerizable liquid crystal compound (A) may be a monomer, but may be an oligomer or a polymer in which a polymerizable group is polymerized.

The polymerizable liquid crystal compound (A) is not particularly limited as long as it is a liquid crystal compound having at least one (meth) acryloyl group, and known polymerizable liquid crystal compounds can be used. preferable. Examples of such a polymerizable liquid crystal compound include a compound represented by the following formula (A1) (hereinafter, may be referred to as “polymerizable liquid crystal compound (A1)”).
U ¹ -V ¹ -W ^1- (X ¹ -Y ^1- ) _n -X ² -W ² -V ² -U ² (A1)
[In formula (A1),
X ¹ and X ² independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein the divalent aromatic group or a divalent alicyclic hydrocarbon is used. Even if the hydrogen atom contained in the group is substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group. Often, the carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom or a sulfur atom or a nitrogen atom. However, at least one of X ¹ and X ² is a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent.
Y ¹ is a single bond or divalent linking group.
n is 1 to 3, and when n is 2 or more, a plurality of X ^1s may be the same or different from each other. X ² may be the same as or different from any or all of the plurality of X ¹ . Further, when n is 2 or more, the plurality of Y ^1s may be the same or different from each other. From the viewpoint of liquid crystallinity, n is preferably 2 or more.
U ¹ represents a hydrogen atom or a (meth) acryloyloxy group.
U ² represents a (meth) acryloyloxy group.
W ¹ and W ² are single-bonded or divalent linking groups independently of each other.
V ¹ and V ² represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent independently of each other, and -CH _2- constituting the alkanediyl group is -O-, It may be replaced with -CO-, -S- or NH-. ]

In the polymerizable liquid crystal compound (A1), X ¹ and X ² are independent of each other and preferably have a 1,4-phenylene group or a substituent which may have a substituent. It is a good cyclohexane-1,4-diyl group, and at least one of X ¹ and X ² has a 1,4-phenylene group which may have a substituent, or a substituent. It is also a good cyclohexane-1,4-diyl group, preferably a trans-cyclohexane-1,4-diyl group. The substituents arbitrarily possessed by the 1,4-phenylene group which may have a substituent or the cyclohexane-1,4-diyl group which may have a substituent include a methyl group and an ethyl. Examples thereof include an alkyl group having 1 to 4 carbon atoms such as a group and a butyl group, a cyano group and a halogen atom such as a chlorine atom and a fluorine atom. It is preferably unsubstituted.

Further, the polymerizable liquid crystal compound (A1) has the formula (A1-1) in the formula (A1).
-(X ¹ -Y ^1- ) _n -X ^2- (A1-1)
[In the formula, X ¹ , Y ¹ , X ² and n have the same meanings as described above. ]
[Hereinafter referred to as a partial structure (A1-1). ] Has an asymmetrical structure, which is preferable in that smectic liquid crystallinity is easily exhibited.
As the polymerizable liquid crystal compound (A1) having an asymmetric structure in the partial structure (A1-1), for example, the polymerizable liquid crystal compound (A1) in which n is 1 and one X ¹ and X ² have different structures from each other. ). Further, n is 2, two Y ^1s are compounds having the same structure as each other, two X ^1s have the same structure as each other, and one X ² has a different structure from these two X ^1s . The polymerizable liquid crystal compound (A1), X ¹ bonded to W ¹ of the two X ¹ , has a different structure from the other X ¹ and X ² , and the other X ¹ and X ² have the same structure. Also mentioned is a polymerizable liquid crystal compound (A1). Further, polymerization in which n is 3 and three Y ^1s have the same structure as each other, and any one of the three X ^1s and one X ² has a different structure from all the other three. The sex liquid crystal compound (A1) can be mentioned.

Y ¹ is -CH ₂ CH _2- , -CH ₂ O-, -CH ₂ CH ₂ O-, -COO-, -OCOO-, single bond, -N = N-, -CR ^a = CR ^b- , -C≡C-, -CR ^a = N- or CO-NR ^a -is preferable. R ^a and R ^b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is more preferable that Y ¹ is -CH ₂ CH _2- , -COO- or a single bond, and when a plurality of Y ^1s are present, Y ¹ that binds to X ² is -CH ₂ CH _2- or CH. It is more preferably ₂ O-. When X ¹ and X ² all have the same structure, it is preferable that two or more Y ^1s having different bonding methods are present. When there are a plurality of Y ^1s having different bonding methods from each other, the structure is asymmetrical, so that smectic liquid crystallinity tends to be easily exhibited.

U ² is a (meth) acryloyloxy group. U ¹ is a hydrogen atom or a (meth) acryloyloxy group, preferably a (meth) acryloyloxy group. From the viewpoint of improving the adhesion between the layers of the polarizing film and improving the heat resistance, it is preferable that both U ¹ and U ² are (meth) acryloyloxy groups. The (meth) acryloyloxy group may be in a polymerized state or a non-polymerized state, but is preferably in a non-polymerized state.

The alkanediyl group represented by V ¹ and V ² includes a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group and a 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 Examples include groups and icosan-1,20-diyl groups. V ¹ and V ² are preferably an alkanediyl group having 2 to 12 carbon atoms, and more preferably an alkanediyl group having 6 to 12 carbon atoms.

Examples of the substituent arbitrarily contained in the alkanediyl group include a cyano group and a halogen atom, and the alkanediyl group is preferably unsubstituted and is an unsubstituted linear alkanediyl group. Is more preferable.

W ¹ and W ² are independent of each other, preferably single bond, —O—, —S—, —COO— or OCOO—, and more preferably single bond or O—.

The polymerizable liquid crystal compound (A) is not particularly limited as long as it is a polymerizable liquid crystal compound having at least one (meth) acryloyl group, and a known polymerizable liquid crystal compound can be used, but it exhibits smectic liquid crystal property. As a structure that tends to exhibit smectic liquid crystallinity, it is preferable to have an asymmetric molecular structure in the molecular structure, and specifically, it has the following partial structures (Aa) to (Ai). It is more preferable that the polymerizable liquid crystal compound is a polymerizable liquid crystal compound exhibiting smectic liquid crystal property. It is more preferable to have a partial structure of (A), (Ab) or (Ac) from the viewpoint of easily exhibiting higher-order smectic liquid crystal properties. In the following (Aa) to (Ai), * represents a bond (single bond).

Specific examples of the polymerizable liquid crystal compound (A) include compounds represented by the formulas (A-1) to (A-25). When the polymerizable liquid crystal compound (A) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans form.

Among these, formula (A-2), formula (A-3), formula (A-4), formula (A-5), formula (A-6), formula (A-7), formula (A-). 8), at least one selected from the group consisting of compounds represented by formula (A-13), formula (A-14), formula (A-15), formula (A-16) and formula (A-17). Seeds are preferred. As the polymerizable liquid crystal compound (A), one type may be used alone, or two or more types may be used in combination.

The polymerizable liquid crystal compound (A) is described in, for example, Lub et al., Recl. Trav. Chim. It can be produced by a known method described in Pays-Bas, 115, 321-328 (1996), Japanese Patent No. 4719156, and the like.

In the present invention, the composition for forming a substituent may contain a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (A), but from the viewpoint of obtaining a polarizing element having a high degree of orientation order, a polarizing element is formed. The ratio of the polymerizable liquid crystal compound (A) to the total mass of the total polymerizable liquid crystal compound contained in the composition is preferably 51% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass. % Or more.

Further, when the composition for forming a substituent contains two or more kinds of polymerizable liquid crystal compounds (A), at least one of them may be a polymerizable liquid crystal compound (A1), and all of them may be a polymerizable liquid crystal compound. It may be (A1). By combining a plurality of polymerizable liquid crystal compounds, the liquid crystal property may be temporarily maintained even at a temperature equal to or lower than the liquid crystal-crystal phase transition temperature.

The content of the polymerizable liquid crystal compound in the polarizing element forming composition is preferably 40 to 99.9% by mass, more preferably 60 to 99% by mass, based on the solid content of the polarizing element forming composition. Yes, more preferably 70-99% by mass. When the content of the polymerizable liquid crystal compound is within the above range, the orientation of the polymerizable liquid crystal compound tends to be high. In the present specification, the solid content means the total amount of the components excluding the solvent from the composition for forming a substituent.

In the present invention, the composition for forming a splitter that forms a splitter comprises a dichroic dye. Here, the dichroic dye means a dye having a property that the absorbance in the major axis direction and the absorbance in the minor axis direction of the molecule are different. The dichroic dye that can be used in the present invention is not particularly limited as long as it has the above-mentioned properties, and may be a dye or a pigment. Further, two or more kinds of dyes or pigments may be used in combination, or dyes and pigments may be used in combination. Further, the dichroic dye may have a polymerizable property or a liquid crystal property.

The dichroic dye preferably has a maximum absorption wavelength (λ _MAX ) in the range of 300 to 700 nm. Examples of such dichroic dyes include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes, anthraquinone dyes and the like.

Examples of the azo dye include a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye, a stilbene azo dye and the like, and a bisazo dye and a trisazo dye are preferable, and for example, a compound represented by the formula (I) (hereinafter, "compound"). (I) ”).
K ¹ (-N = N-K ² ) _p -N = N-K ³ (I)
[In the formula (I), K ¹ and K ³ may have a phenyl group which may have a substituent, a naphthyl group which may have a substituent or a substituent, which may be independent of each other. Represents a good monovalent heterocyclic group. K ² is a p-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, or a divalent heterocycle which may have a substituent. Represents a group. p represents an integer of 1 to 4. When p is an integer of 2 or more, the plurality of K ^2s may be the same or different from each other. The -N = N-bond may be replaced with the -C = C-, -COO-, -NHCO-, and -N = CH-bond within the range showing absorption in the visible region. ]

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

As a substituent optionally contained in the phenyl group, naphthyl group and ^monovalent heterocyclic group in K1 and K3 ^, and the p ^- phenylene group, naphthalene-1,4-diyl group and divalent heterocyclic group in K2. Is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms having a polymerizable group, an alkenyl group having 1 to 4 carbon atoms; and an alkenyl group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, and a butoxy group. Alkoxy group; alkoxy group having 1 to 20 carbon atoms having a polymerizable group; alkyl fluoride group having 1 to 4 carbon atoms such as trifluoromethyl group; cyano group; nitro group; halogen atom; amino group, diethylamino group, pyrrolidino Substituent or unsubstituted amino group such as a group (A substituted amino group is an amino group having one or two alkyl groups having 1 to 6 carbon atoms and one alkyl group having a polymerizable group having 1 to 6 carbon atoms. Alternatively, it means an amino group having two, or an amino group in which two substituted alkyl groups are bonded to each other to form an alcandiyl group having 2 to 8 carbon atoms. The unsubstituted amino group is -NH ₂ ). And so on. Examples of the polymerizable group include an acryloyl group, a metaacryloyl group, an acryloyloxy group, and a metaacryloyloxy group.

［式（Ｉ－１）～（Ｉ－８）中、
Ｂ^１～Ｂ^３０は、互いに独立して、水素原子、炭素数１～６のアルキル基、炭素数１～６のアルケニル基、炭素数１～４のアルコキシ基、シアノ基、ニトロ基、置換又は無置換のアミノ基（置換アミノ基及び無置換アミノ基の定義は前記のとおり）、塩素原子又はトリフルオロメチル基を表わす。
ｎ１～ｎ４は、互いに独立に０～３の整数を表わす。
ｎ１が２以上である場合、複数のＢ^２は互いに同一でも異なっていてもよく、
ｎ２が２以上である場合、複数のＢ^６は互いに同一でも異なっていてもよく、
ｎ３が２以上である場合、複数のＢ^９は互いに同一でも異なっていてもよく、
ｎ４が２以上である場合、複数のＢ^１４は互いに同一でも異なっていてもよい。］ Among the compounds (I), compounds represented by any of the following formulas (I-1) to (I-6) are preferable.

[In formulas (I-1) to (I-8),
B ¹ to B ³⁰ are independent of each other, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a nitro group, a substituent or the like. Represents an unsubstituted amino group (the definition of a substituted amino group and an unsubstituted amino group is as described above), a chlorine atom or a trifluoromethyl group.
n1 to n4 represent integers of 0 to 3 independently of each other.
When n1 is ² or more, a plurality of B2s may be the same or different from each other.
When n2 is 2 or more, the plurality of ^B6s may be the same or different from each other.
When n3 is 2 or more, a plurality of ^B9s may be the same or different from each other.
When n4 is 2 or more, the plurality of B ^14s may be the same or different from each other. ]

［式（Ｉ－９）中、
Ｒ^１～Ｒ^８は、互いに独立して、水素原子、－Ｒ^ｘ、－ＮＨ_２、－ＮＨＲ^ｘ、－ＮＲ^ｘ _２、－ＳＲ^ｘ又はハロゲン原子を表わす。
Ｒ^ｘは、炭素数１～４のアルキル基又は炭素数６～１２のアリール基を表わす。］ As the anthraquinone dye, a compound represented by the formula (I-9) is preferable.

[In formula (I-9),
R ¹ to R ⁸ independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]

［式（Ｉ－８）中、
Ｒ^９～Ｒ^１５は、互いに独立して、水素原子、－Ｒ^ｘ、－ＮＨ_２、－ＮＨＲ^ｘ、－ＮＲ^ｘ _２、－ＳＲ^ｘ又はハロゲン原子を表わす。
Ｒ^ｘは、炭素数１～４のアルキル基又は炭素数６～１２のアリール基を表わす。］ As the oxazone dye, a compound represented by the formula (I-10) is preferable.

[In formula (I-8),
R ⁹ to R ¹⁵ independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]

［式（Ｉ－１１）中、
Ｒ^１６～Ｒ^２３は、互いに独立して、水素原子、－Ｒ^ｘ、－ＮＨ_２、－ＮＨＲ^ｘ、－ＮＲ^ｘ _２、－ＳＲ^ｘ又はハロゲン原子を表わす。
Ｒ^ｘは、炭素数１～４のアルキル基又は炭素数６～１２のアリール基を表わす。］
式（Ｉ－９）、式（Ｉ－１０）及び式（Ｉ－１１）において、Ｒ^ｘの炭素数１～６のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基及びヘキシル基等が挙げられ、炭素数６～１２のアリール基としては、フェニル基、トルイル基、キシリル基及びナフチル基等が挙げられる。 As the acridine dye, a compound represented by the formula (I-11) is preferable.

[In formula (I-11),
R ¹⁶ to R ²³ independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]
In the formula (I-9), the formula (I-10) and the formula (I-11), the alkyl group having 1 to 6 carbon atoms of ^Rx includes a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group. And a hexyl group and the like, and examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a toluyl group, a xylyl group and a naphthyl group.

［式（Ｉ－１２）中、
Ｄ^１及びＤ^２は、互いに独立に、式（Ｉ－１２ａ）～式（Ｉ－１２ｄ）のいずれかで表される基を表わす。

ｎ５は１～３の整数を表わす。］

［式（Ｉ－１３）中、
Ｄ^３及びＤ^４は、互いに独立に、式（Ｉ－１３ａ）～式（１－１３ｈ）のいずれかで表される基を表わす。

ｎ６は１～３の整数を表わす。］ As the cyanine dye, a compound represented by the formula (I-12) and a compound represented by the formula (I-13) are preferable.

[In formula (I-12),
D ¹ and D ² represent a group represented by any of the formulas (I-12a) to (I-12d) independently of each other.

n5 represents an integer of 1 to 3. ]

[In formula (I-13),
D ³ and D ⁴ represent groups represented by any of the formulas (I-13a) to (1-13h) independently of each other.

n6 represents an integer of 1 to 3. ]

Among these dichroic dyes, the azo dye has high linearity and is suitable for producing a polarizing element having excellent polarizing performance. Even if it is diffused to, the influence on its optical characteristics becomes large. Even in such a polarizing element, in the present invention, since the first resin layer and the second resin layer are each composed of a cured product of a curable composition containing a (meth) acrylic compound, two colors are used in a preferred embodiment. The diffusion of the sex dye (particularly heat diffusion) can be effectively suppressed, and the deterioration of the polarization performance can be effectively suppressed. Therefore, in one embodiment of the present invention, the dichroic dye contained in the composition for forming a polarizing element that forms a polarizing element is preferably an azo dye.

In the present invention, the weight average molecular weight of the dichroic dye is usually 300 to 2000, preferably 400 to 1000. When the weight average molecular weight of the dichroic dye is not more than the above upper limit, the dichroic dye existing in the state of being encapsulated in the polymerizable liquid crystal compound in the polarizing element is easily moved, and moves out of the polarizing element in a high temperature environment or the like. It becomes easy to spread. Even in such a case, in the present invention, since the first resin layer and the second resin layer are each composed of a cured product of a curable composition containing a (meth) acrylic compound, they are dichroic in a preferred embodiment. Diffusion of dye (particularly heat diffusion) can be effectively suppressed, and deterioration of polarization performance can be effectively suppressed.

In one embodiment of the present invention, it is preferable that the dichroic dye contained in the composition for forming a polarizing element that forms a polarizing element is hydrophobic. When the dichroic dye is hydrophobic, the compatibility between the dichroic dye and the polymerizable liquid crystal compound is improved, the dichroic dye and the polymerizable liquid crystal compound form a uniform phase state, and the degree of orientation order is high. It is possible to obtain a ligand having the above. In the present invention, the hydrophobic dichroic dye means a dye having a solubility of 1 g or less in 100 g of water at 25 ° C.

The content of the dichroic dye in the composition for forming a polarizing element can be appropriately determined depending on the type of the dichroic dye to be used and the like, but is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. It is 50 parts by mass, more preferably 0.1 to 20 parts by mass, and further preferably 0.1 to 12 parts by mass. When the content of the dichroic dye is within the above range, the orientation of the polymerizable liquid crystal compound is not easily disturbed, and a substituent having a high degree of orientation order can be obtained.

In the present invention, the composition for forming a substituent for forming a substituent may contain a polymerization initiator. The polymerization initiator is a compound that can initiate the polymerization reaction of the polymerizable liquid crystal compound, and the photopolymerization initiator is preferable in that the polymerization reaction can be initiated under lower temperature conditions. Specific examples thereof include photopolymerization initiators capable of generating active radicals or acids by the action of light, and among them, photopolymerization initiators that generate radicals by the action of light are preferable. The polymerization initiator can be used alone or in combination of two or more.

A known photopolymerization initiator can be used as the photopolymerization initiator. For example, as the photopolymerization initiator that generates an active radical, a self-cleaving type photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator can be used. There is.
Self-cleaving benzoin compounds, acetophenone compounds, hydroxyacetophenone compounds, α-aminoacetophenone compounds, oxime ester compounds, acylphosphine oxide compounds, azo compounds, etc. are used as self-cleaving photopolymerization initiators. Can be used. Further, as a hydrogen abstraction type photopolymerization initiator, a hydrogen abstraction type benzophenone compound, a benzoin ether compound, a benzyl ketal compound, a dibenzosverone compound, an anthraquinone compound, a xanthone compound, a thioxanthone compound, and a halogenoacetophenone compound. Compounds, dialkoxyacetophenone-based compounds, halogenobis imidazole-based compounds, halogenotriazine-based compounds, triazine-based compounds and the like can be used.

As the photopolymerization initiator that generates an acid, an iodonium salt, a sulfonium salt, or the like can be used.

Among these, the reaction at a low temperature is preferable from the viewpoint of preventing the dissolution of the dye, and the self-cleaving photopolymerization initiator is preferable from the viewpoint of the reaction efficiency at a low temperature, and in particular, an acetophenone-based compound, a hydroxyacetophenone-based compound, and α-aminoacetophenone. System compounds and oxime ester compounds are preferable.

Specific examples of the photopolymerization initiator include the following.
Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether;
2-Hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1- [4- (2- (2-) Hydroxyacetophenone such as hydroxyethoxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenylketone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one oligomers Phenyl compound;
Α-Aminoacetophenone such as 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1-one, etc. System compounds;
1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Il]-, 1- (O-acetyloxime) and other oxime ester compounds;
Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide;
Benzophenone, o-Methyl benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone and 2,4 Benzophenone compounds such as 6-trimethylbenzophenone;
Dialkoxyacetophenone compounds such as diethoxyacetophenone;
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- (fran-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 and other triazine compounds. The photopolymerization initiator may be appropriately selected from the above-mentioned photopolymerization initiator in relation to the polymerizable liquid crystal compound contained in the composition for forming a substituent.

Further, a commercially available photopolymerization initiator may be used. Commercially available polymerization initiators include Irgacure (registered trademark) 907, 184, 651, 819, 250, and 369, 379, 127, 754, OXE01, OXE02, OXE03 (manufactured by BASF); Omnirad BCIM, Resin. 1001M, Esacure KIP160 (IDM Resins B.V.); Sakeol® BZ, Z, and BEE (Seiko Kagaku Co., Ltd.); kayacure® BP100, and UVI-6992 (Dow). (Made by Chemical Co., Ltd.); Adeka Polymer SP-152, N-1717, N-1919, SP-170, Adeka Arkuru's NCI-831, Adeka Arkuru's NCI-930 (manufactured by ADEKA Co., Ltd.); TAZ-A, And TAZ-PP (manufactured by Nippon Sibel Hegner Co., Ltd.); and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.); and the like.

The content of the polymerization initiator in the composition for forming a substituent for forming a polarizing element is preferably 1 to 10 parts by mass, and more preferably 1 to 8 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. Parts, more preferably 2 to 8 parts by mass, and particularly preferably 4 to 8 parts by mass. When the content of the polymerization initiator is within the above range, the polymerization reaction of the polymerizable liquid crystal compound can be carried out without significantly disturbing the orientation of the polymerizable liquid crystal compound.

Further, the polymerization rate of the polymerizable liquid crystal compound in the present invention is preferably 60% or more, more preferably 65% or more, still more preferably 70% or more, from the viewpoint of line contamination during production and handling.

The composition for forming a polarizing element may further contain a photosensitizer. By using a photosensitizer, the polymerization reaction of the polymerizable liquid crystal compound can be further promoted. Photosensitizers include xanthone compounds such as xanthone, thioxanthone (eg, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, etc.); anthracene, alkoxy group-containing anthracene (eg, dibutoxyanthracene, etc.); Examples thereof include phenothiazine and rubrene. The photosensitizer can be used alone or in combination of two or more.

When the composition for forming a polarizing element contains a photosensitizer, the content thereof may be appropriately determined according to the type and amount of the polymerization initiator and the polymerizable liquid crystal compound, but the content thereof is 100 parts by mass of the polymerizable liquid crystal compound. On the other hand, 0.1 to 30 parts by mass is preferable, 0.5 to 10 parts by mass is more preferable, and 0.5 to 8 parts by mass is further preferable.

Further, the composition for forming a substituent may contain a leveling agent. The leveling agent has a function of adjusting the fluidity of the polarizing element forming composition and making the coating film obtained by applying the polarizing element forming composition flatter, and specifically, has a surface activity. Agents are mentioned. As the leveling agent, at least one selected from the group consisting of a leveling agent containing a polyacrylate compound as a main component and a leveling agent containing a fluorine atom-containing compound as a main component is preferable. The leveling agent can be used alone or in combination of two or more.

Examples of the leveling agent containing a polyacrylate compound as a main component include "BYK-350", "BYK-352", "BYK-353", "BYK-354", "BYK-355", and "BYK-358N". , "BYK-361N", "BYK-380", "BYK-381" and "BYK-392" (BYK Chemie).

Examples of the leveling agent containing a fluorine atom-containing compound as a main component include “Megafuck (registered trademark) R-08”, “R-30”, “R-90”, “F-410”, and the same. "F-411", "F-443", "F-445", "F-470", "F-471", "F-477", "F-479", "F-479" F-482 "and" F-483 "(DIC Co., Ltd.);" Surflon (registered trademark) S-381 "," S-382 "," S-383 "," S-393 ", "SC-101", "SC-105", "KH-40" and "SA-100" (AGC Seimi Chemical Co., Ltd.); "E1830", "E5844" (Daikin Fine Chemical Laboratory Co., Ltd.) "Ftop EF301", "Ftop EF303", "Ftop EF351" and "Ftop EF352" (Mitsubishi Materials Electronics Chemical Co., Ltd.) can be mentioned.

When the composition for forming a polarizing element contains a leveling agent, the content thereof is preferably 0.05 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. .. When the content of the leveling agent is within the above range, the polymerizable liquid crystal compound is likely to be horizontally oriented, unevenness is less likely to occur, and a smoother polarizing element tends to be obtained.

The composition for forming a polarizing element may contain additives other than the photosensitizer and the leveling agent. Examples of other additives include antioxidants, mold release agents, stabilizers, colorants such as brewing agents, flame retardants and lubricants. When the composition for forming a substituent contains other additives, the content of the other additives shall be more than 0% and 20% by mass or less with respect to the solid content of the composition for forming a substituent. Is more preferable, and more preferably more than 0% and 10% by mass or less.

The polarizing element forming composition can be produced by a conventionally known method for preparing a polarizing element forming composition, and is usually a polymerizable liquid crystal compound and a dichroic dye, and if necessary, a polymerization initiator and the above. It can be prepared by mixing and stirring additives and the like. Further, since a compound exhibiting smectic liquid crystal property generally has a high viscosity, a solvent is added to the polarizing element forming composition from the viewpoint of improving the coatability of the polarizing element forming composition and facilitating the formation of the polarizing element. The viscosity may be adjusted according to the above.

The solvent used in the composition for forming a polarizing element can be appropriately selected depending on the solubility of the polymerizable liquid crystal compound and the dichroic dye to be used. Specifically, for example, alcohol solvents such as water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone. , Ester solvents such as propylene glycol methyl ether acetate and ethyl lactate, ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methylamylketone and methylisobutylketone, aliphatic hydrocarbon solvents such as pentane, hexane and heptane, toluene. , Aromatic hydrocarbon solvents such as xylene, nitrile solvents such as acetonitrile, ether solvents such as tetrahydrofuran and dimethoxyethane, and chlorinated hydrocarbon solvents such as chloroform and chlorobenzene. These solvents can be used alone or in combination of two or more. The content of the solvent is preferably 100 to 1900 parts by mass, more preferably 150 to 900 parts by mass, and further preferably 180 to 600 parts by mass with respect to 100 parts by mass of the solid content of the composition for forming a polarizing element. It is a department.

In the polarizing film of the present invention, the polarizing element is preferably a polarizing element having a high degree of orientation order. A Bragg peak derived from a higher-order structure such as a hexatic phase or a crystal phase can be obtained by a polarizing element having a high degree of orientation order in X-ray diffraction measurement. The Bragg peak means a peak derived from the plane periodic structure of molecular orientation. Therefore, it is preferable that the polarizing element constituting the polarizing film of the present invention shows a Bragg peak in the X-ray diffraction measurement. That is, in the polarizing element constituting the polarizing film of the present invention, it is preferable that the polymerizable liquid crystal compound or a polymer thereof is oriented so that the polarizing element shows a Bragg peak in the X-ray diffraction measurement, and the light is emitted. It is more preferable to have a "horizontal orientation" in which the molecules of the polymerizable liquid crystal compound are oriented in the absorption direction. In the present invention, a splitter having a plane period interval of molecular orientation of 3.0 to 6.0 Å is preferable. A high degree of orientation order indicating a Bragg peak can be realized by controlling the type of the polymerizable liquid crystal compound used, the type and amount of the dichroic dye, the type and amount of the polymerization initiator, and the like.

In one embodiment of the present invention, the substituent forms a coating film of the composition for forming a polarizing element on the alignment film, removes the solvent from the coating film, and the polymerizable liquid crystal compound undergoes a phase transition to the liquid phase. It can be obtained by a method including phase transition of the polymerizable liquid crystal compound to the smectic phase by raising the temperature to a temperature higher than the temperature and then lowering the temperature, and polymerizing the polymerizable liquid crystal compound while maintaining the smectic phase. ..

As a method of applying the composition for forming a polarizing element to an alignment film or the like, a coating method such as a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, an applicator method, or a flexo method is used for printing. Known methods such as a method can be mentioned.

Next, a dry coating film is formed by removing the solvent by drying or the like under the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the composition for forming a substituent does not polymerize. Examples of the drying method include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.

Further, in order to make the polymerizable liquid crystal compound undergo a phase transition to the liquid phase, the temperature is raised to a temperature higher than the temperature at which the polymerizable liquid crystal compound undergoes a phase transition to the liquid phase, and then the temperature is lowered to bring the polymerizable liquid crystal compound into a smectic phase (smectic liquid crystal state). Make a phase transition. Such a phase transition may be performed after removing the solvent in the coating film, or may be performed at the same time as removing the solvent.

By polymerizing the polymerizable liquid crystal compound while maintaining the smectic liquid crystal state of the polymerizable liquid crystal compound, a substituent is formed as a cured layer of the composition for forming a substituent. The photopolymerization method is preferable as the polymerization method. In photopolymerization, the light irradiating the dry coating film includes the type of the polymerizable liquid crystal compound contained in the dry coating film (particularly, the type of the polymerizable group of the polymerizable liquid crystal compound), the type of the polymerization initiator, and the type of the polymerization initiator. It is appropriately selected according to the amount thereof and the like. Specific examples thereof include one or more types of active energy rays and active electron beams selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α rays, β rays and γ rays. Among them, ultraviolet light is preferable because it is easy to control the progress of the polymerization reaction and it is possible to use a photopolymerization apparatus widely used in the art, so that photopolymerization can be performed by ultraviolet light. It is preferable to select the type of the polymerizable liquid crystal compound or the polymerization initiator contained in the composition for forming a substituent. Further, at the time of polymerization, the polymerization temperature can be controlled by irradiating light while cooling the dry coating film by an appropriate cooling means. At the time of photopolymerization, a patterned polarizing element can also be obtained by masking or developing.

Examples of the light source of the active energy ray include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excima laser, and a wavelength range. Examples thereof include LED light sources that emit light of 380 to 440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, and the like.

The ultraviolet irradiation intensity is usually 10 to 3,000 mW / cm ² . The ultraviolet irradiation intensity is preferably the intensity in the wavelength region effective for activating the polymerization initiator. The time for irradiating with light is usually 0.1 seconds to 10 minutes, preferably 1 second to 5 minutes, more preferably 5 seconds to 3 minutes, and even more preferably 10 seconds to 1 minute. When irradiated once or multiple times with such an ultraviolet irradiation intensity, the integrated light intensity is 10 to 3,000 mJ / cm ² , preferably 50 to 2,000 mJ / cm ² , and more preferably 100 to 1,000 mJ / cm. It is ² .

By performing photopolymerization, the polymerizable liquid crystal compound is polymerized while maintaining the liquid crystal state of the smectic phase, preferably the higher-order smectic phase, and a substituent is formed. The polarizing element obtained by polymerizing the polymerizable liquid crystal compound while maintaining the liquid crystal state of the smectic phase is obtained from the conventional host guest type polarizing film, that is, the liquid crystal state of the nematic phase due to the action of the dichroic dye. There is an advantage that the polarization performance is high as compared with the polarizing element. Further, there is an advantage that the strength is excellent as compared with the one coated only with the dichroic dye or the lyotropic liquid crystal.

The thickness of the polarizing element can be appropriately selected depending on the display device to be applied, and is preferably a film of 0.1 to 5 μm, more preferably 0.3 to 4 μm, and further preferably 0.5 to 3 μm. be. When the film thickness of the polarizing element is equal to or more than the above lower limit, it is easy to prevent the necessary light absorption from being obtained, and when it is equal to or less than the above upper limit, orientation defects occur due to a decrease in the alignment regular force due to the alignment film. Is easy to suppress. The substituent, the polarizing plate, the alignment film, the first resin layer and the second resin layer can be measured by a laser microscope or a film thickness meter, respectively.

<Alignment film>
The alignment film contained in the polarizing film of the present invention is formed on the surface of the polarizing element opposite to the first resin layer. The alignment film has an orientation-regulating force that orients the polymerizable liquid crystal compound in a desired direction. The alignment film preferably has solvent resistance that does not dissolve when the composition for forming a polarizing film is applied, and has heat resistance in heat treatment for removing the solvent and aligning the polymerizable liquid crystal compound. In the present invention, the alignment film is a cured product of a composition for forming an alignment film containing a (meth) acrylic compound, and has excellent adhesion at the interface with the polarizing element and the interface with the second resin layer. The alignment film in the present invention is preferably a photoalignment film formed by curing the alignment film forming composition by polarization (preferably polarized UV) from the viewpoint of improving adhesion and heat resistance.

The (meth) acrylic compound represents a compound having at least one (meth) acryloyl group, and the (meth) acrylic compound may be a monomer, an oligomer or a polymer. When it is an oligomer or a polymer, the double bond of the (meth) acryloyl group may be polymerized. The (meth) acrylic compound contained in the composition for forming a photoalignment film preferably has a photoreactive group in addition to the (meth) acryloyl group.

A photoreactive group is a group that produces a liquid crystal alignment ability when irradiated with light. Specific examples thereof include groups involved in photoreactions that are the origin of liquid crystal alignment ability such as molecular orientation induction or isomerization reaction, dimerization reaction, photocrosslinking reaction or photodecomposition reaction generated by light irradiation. Of these, groups involved in the dimerization reaction or the photocrosslinking reaction are preferable because they have excellent orientation. As the photoreactive group, an unsaturated bond, particularly a group having a double bond is preferable, and a carbon-carbon double bond (C = C bond), a carbon-nitrogen double bond (C = N bond), and a nitrogen-nitrogen double bond are preferable. A group having at least one selected from the group consisting of a double bond (N = N bond) and a carbon-oxygen double bond (C = O bond) is particularly preferable.

Examples of the photoreactive group having a C = C bond include a vinyl group, a polyene group, a stilbene group, a stillvazol group, a stillvazolium group, a chalcone group, a cinnamoyl group and the like. Examples of the photoreactive group having a C = N bond include a group having a structure such as an aromatic Schiff base and an 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, a formazan group, and a group having an azoxybenzene structure. Examples of the photoreactive group having a C = O bond include a benzophenone group, a coumarin group, an anthraquinone group, a maleimide group and the like. These groups may have substituents such as an alkyl group, an alkoxy group, an allyl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group and an alkyl halide group.

Above all, a photoreactive group involved in the photodimerization reaction is preferable, and a photoalignment film having a relatively small amount of polarization irradiation required for photoalignment and excellent thermal stability and temporal stability can be easily obtained. A cinnamoyl group and a chalcone group are preferable. As the (meth) acrylic oligomer or polymer contained in the composition for forming a photoalignment film, those having a cinnamoyl group such that the terminal portion of the oligomer or polymer side chain has a cinnamoyl acid structure is particularly preferable.

In one embodiment of the present invention, the photoalignment film is formed by applying a composition for forming a photoalignment film containing a (meth) acrylic compound and a solvent onto a second resin layer and irradiating the second resin layer with polarized light (preferably polarized UV). Obtained by doing. Examples of the solvent contained in the composition for forming a photoalignment film include the same solvents as those exemplified above as the solvent that can be used when forming the polarizing element, and are appropriately used depending on the solubility of the (meth) acrylic compound. You can choose.

The content of the (meth) acrylic compound in the composition for forming a photoalignment film can be appropriately adjusted depending on the type of the (meth) acrylic compound and the thickness of the target photoalignment film, but the mass of the composition for forming a photoalignment film. On the other hand, it is preferably at least 0.2% by mass, more preferably in the range of 0.3 to 10% by mass. The composition for forming a photoalignment film may contain a polymer material such as polyvinyl alcohol or polyimide or a photosensitizer as long as the characteristics of the photoalignment film are not significantly impaired.

As a method of applying the composition for forming a photoalignment film on the second resin layer and a method of removing the solvent from the applied composition for forming a photoalignment film, the composition for forming a substituent is applied to the alignment film. Examples of the method for removing the solvent and the method for removing the solvent include the methods exemplified above.

The polarization irradiation is performed by directly irradiating the composition for forming a photoalignment film coated on the second resin layer with the polarized UV removed, and irradiating the polarized light from the second resin layer side to obtain the polarized light. It may be in the form of transmitting and irradiating. Further, it is particularly preferable that the polarized light is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably in the wavelength range in which the photoreactive group and / or the (meth) acryloyl group of the (meth) acrylic compound can absorb light energy. Specifically, UV (ultraviolet rays) having a wavelength in the range of 250 to 400 nm is particularly preferable. Examples of the light source used for the polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, ultraviolet light lasers such as KrF and ArF, and high-pressure mercury lamps, ultra-high pressure mercury lamps and metal halide lamps. preferable. Among these, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp are preferable because they have a high emission intensity of ultraviolet rays having a wavelength of 313 nm. Polarized UV can be irradiated by irradiating the light from the light source through an appropriate polarizing element. As such a polarizing element, a polarizing filter, a polarizing prism such as Gran Thomson or Gran Tailor, or a wire grid type polarizing element can be used.

If masking is performed during rubbing or polarization irradiation, it is possible to form a plurality of regions (patterns) in which the directions of liquid crystal orientation are different.

The thickness of the alignment film is preferably 10 to 5000 nm, more preferably 10 to 1000 nm, and even more preferably 30 to 300 nm. When the thickness of the alignment film is within the above range, the alignment regular force can be exerted while exhibiting good adhesion at the interface with the polarizing element or the interface with the second resin layer, and the polarizing element can be highly ordered. Can be formed.

<First resin layer and second resin layer>
The first resin layer contained in the polarizing film of the present invention is a cured product of the first curable composition containing a (meth) acrylic compound, and is formed on a surface opposite to the alignment film side of the substituent. .. In the present invention, since both the first resin layer and the substituent are formed of a compound having a (meth) acryloyl group, the compatibility between the layers is high, and the (meth) acrylic compound contained in the first curable composition. And the polymerizable liquid crystal compound having a (meth) acryloyl group contained in the polarizing element can form a crosslinked structure, so that excellent adhesion at the layer interface can be exhibited.
The second resin layer contained in the polarizing film of the present invention is a cured product of the second curable composition containing a (meth) acrylic compound, and is formed on the surface of the alignment film opposite to the polarizing element side. .. In the present invention, since both the second resin layer and the alignment film are formed of a compound having a (meth) acryloyl group, the compatibility between the layers is high, and the (meth) acrylic compound contained in the second curable composition. And the (meth) acrylic compound contained in the alignment film can form a crosslinked structure, so that excellent adhesion at the layer interface can be exhibited.

The (meth) acrylic compound contained in the first curable composition and the second curable composition is a compound having at least one (meth) acryloyl group, and may be a monomer, an oligomer or a polymer. Examples of the (meth) acrylic compound include (meth) acrylate compounds such as monofunctional (meth) acrylate compounds and polyfunctional (meth) acrylate compounds; and urethane (meth) acrylate compounds such as polyfunctional urethane (meth) acrylate compounds; Epoxy (meth) acrylate compounds such as polyfunctional epoxy (meth) acrylate compounds; carboxyl group-modified epoxy (meth) acrylate compounds, polyester (meth) acrylate compounds and the like can be mentioned. These can be used alone or in combination of two or more. Among these, a polyfunctional (meth) acrylate compound or a urethane (meth) acrylate compound is preferable, and a polyfunctional (meth) acrylate compound and a urethane (meth) are preferable from the viewpoint of easily improving the adhesion, heat resistance and flexibility of the polarizing film. ) It is more preferable to combine with acrylate. The first curable composition (first resin layer) and the second curable composition (second resin layer) may have the same composition or different compositions, but have adhesiveness, heat resistance, and bending. The same composition is preferable from the viewpoint of easily improving the properties. In the present specification, the flexibility means a property that can suppress the occurrence of cracks and the like when the polarizing film is bent.

In one embodiment of the present invention, at least one of the first curable composition and the second curable composition contains a polyfunctional (meth) acrylate compound as the (meth) acrylic compound. This aspect is advantageous from the viewpoint of adhesion, heat resistance and flexibility of the polarizing film.

A polyfunctional (meth) acrylate compound means a compound having two or more (meth) acryloyloxy groups in the molecule, for example, a bifunctional (meth) acryloyloxy group having two (meth) acryloyloxy groups in the molecule. Examples thereof include a meta) acrylate monomer, a trifunctional or higher (meth) acrylate monomer having three or more (meth) acryloyloxy groups in the molecule, and the like. In addition, in this specification, the term "(meth) acrylate" means "acrylate" or "methacrylate", and the term "(meth) acryloyl" also means "acryloyl" or "methacryloyl".

As the polyfunctional (meth) acrylate compound, one kind or two or more kinds of polyfunctional (meth) acrylate compounds may be contained. Further, when two or more kinds of polyfunctional (meth) acrylate compounds are contained, the number of (meth) acryloyloxy groups may be the same or different between the respective polyfunctional (meth) acrylate compounds.

Examples of the bifunctional (meth) acrylate monomer include ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di. Alkylene glycol di (meth) acrylates such as (meth) acrylates, 1,9-nonanediol di (meth) acrylates and neopentyl glycol di (meth) acrylates; diethylene glycol di (meth) acrylates, triethylene glycol di (meth) acrylates. , Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate and other polyoxyalkylene glycols. Di (meth) acrylate; Di (meth) acrylate of halogen-substituted alkylene glycol such as tetrafluoroethylene glycol di (meth) acrylate; trimethylolpropane di (meth) acrylate, ditrimethylolpropane di (meth) acrylate, pentaerythritol di ( Di (meth) acrylate of an aliphatic polyol such as meta) acrylate; hydrogenated dicyclopentadiene or tricyclodecandi such as hydrogenated dicyclopentadienyldi (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate. Di (meth) acrylate of alkanol; di (meth) acrylate of dioxane glycol or dioxan dialkanol such as 1,3-dioxane-2,5-diyldi (meth) acrylate [also known as dioxane glycol di (meth) acrylate]; bisphenol Di (meth) acrylate of alkylene oxide adduct of bisphenol A or bisphenol F such as A ethylene oxide adduct diacrylate, bisphenol F ethylene oxide adduct diacrylate; acrylic acid adduct of bisphenol A diglycidyl ether, bisphenol F Epoxydi (meth) acrylate of bisphenol A or bisphenol F such as acrylic acid adduct of diglycidyl ether; silicone di (meth) acrylate; di (meth) acrylate of hydroxypivalic acid neopentyl glycol ester; 2,2-bis [4 -(Meta) Acryloyloxyethoxyethoxyphenyl Le] Propane; 2,2-bis [4- (meth) acryloyloxyethoxyethoxycyclohexyl] propane; 2- (2-hydroxy-1,1-dimethylethyl) -5-ethyl-5-hydroxymethyl-1,3 -Dioxane] di (meth) acrylate; tris (hydroxyethyl) isocyanurate di (meth) acrylate and the like can be mentioned.

The trifunctional (meth) acrylate monomer is a monomer having three (meth) acryloyloxy groups in the molecule, and examples thereof include glycerintri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane. Propanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate and acid anhydride reactants, caprolactone-modified trimethylolpropanetri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate , Ethyleneoxide-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified pentaerythritol tri (meth) acrylate, isocyanurate tri. (Meta) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride reaction product, ethylene oxide-modified pentaerythritol tri (meth) acrylate and acid anhydride reaction product, propylene oxide-modified pentaerythritol tri (meth) ) Examples thereof include a reaction product of acrylate and acid anhydride.

The tetrafunctional (meth) acrylate monomer is a monomer having four (meth) acryloyloxy groups in the molecule, and examples thereof include ditrimethylol propanetetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and di. Pentaerythritol tetra (meth) acrylate, tripentaerythritol tetra (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, ethylene oxide-modified pentaerythritol tetra (meth) acrylate, ethylene Examples thereof include oxide-modified tripentaerythritol tetra (meth) acrylate, propylene oxide-modified pentaerythritol tetra (meth) acrylate, and propylene oxide-modified tripentaerythritol tetra (meth) acrylate.

Examples of the pentafunctional (meth) acrylate monomer include dipentaerythritol penta (meth) acrylate, tripentaerythritol penta (meth) acrylate, a reaction product of dipentaerythritol penta (meth) acrylate and an acid anhydride, and a caprolactone-modified dipenta. Elythritol penta (meth) acrylate, caprolactone-modified tripenta erythritol penta (meth) acrylate, ethylene oxide-modified dipenta erythritol penta (meth) acrylate, ethylene oxide-modified tripenta erythritol penta (meth) acrylate, propylene oxide-modified dipenta erythritol penta ( Meta) acrylate, propylene oxide-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride reaction product, ethylene oxide-modified dipentaerythritol penta (meth) acrylate and acid anhydride Examples thereof include a reaction product of propylene oxide-modified dipentaerythritol penta (meth) acrylate and an acid anhydride.

Examples of the hexafunctional (meth) acrylate monomer include dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and caprolactone-modified tripentaerythritol hexa (meth) acrylate. , Ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified tripentaerythritol hexa (meth) acrylate, propylene oxide-modified dipentaerythritol hexa (meth) acrylate, propylene oxide-modified tripentaerythritol hexa (meth) acrylate, etc. Can be mentioned.

Examples of the 7-functional (meth) acrylate monomer include tripentaerythritol hepta (meth) acrylate, a reaction product of tripentaerythritol hepta (meth) acrylate and an acid anhydride, caprolactone-modified tripentaerythritol hepta (meth) acrylate, and caprolactone-modified. Reaction product of tripentaerythritol hepta (meth) acrylate and acid anhydride, ethylene oxide-modified tripentaerythritol hepta (meth) acrylate, reaction product of ethylene oxide-modified tripentaerythritol hepta (meth) acrylate and acid anhydride, propylene Examples thereof include an oxide-modified tripentaerythritol hepta (meth) acrylate and a reaction product of a propylene oxide-modified tripentaerythritol hepta (meth) acrylate and an acid anhydride.

The octafunctional (meth) acrylate monomer is a monomer having eight (meth) acryloyloxy groups in the molecule, and examples thereof include tripentaerythritol octa (meth) acrylate and caprolactone-modified tripentaerythritol octa (meth). Examples thereof include acrylate, ethylene oxide-modified tripentaerythritol octa (meth) acrylate, and propylene oxide-modified tripentaerythritol octa (meth) acrylate. These polyfunctional (meth) acrylate compounds can be used alone or in combination of two or more.

The number of (meth) acryloyl groups in the polyfunctional (meth) acrylate compound is preferably 6 or more, more preferably 7 or more, still more preferably 8 or more. When the number of (meth) acryloyl groups in the polyfunctional (meth) acrylate compound is at least the above lower limit, the crosslink density of the first resin layer or the second resin layer is increased, and the heat resistance of the polarizing film is likely to be improved. .. Further, the upper limit of the number of (meth) acryloyl groups is usually 20 or less.

The polyfunctional (meth) acrylate compound can adjust the cross-linking density of the first resin layer or the second resin layer by controlling the molecular weight between the cross-linking points and the number of cross-linking points of the compound. More specifically, the smaller the molecular weight between the cross-linking points, the higher the cross-linking density, and the larger the number of cross-linking points, the denser the cross-linking density, and the heat resistance of the polarizing film can be improved.

In one embodiment of the present invention, from the viewpoint of controlling the crosslink density and improving the heat resistance, the polyfunctional (meth) acrylate compound has a branched structure and is the closest to the (meth) acryloyl group in the branched structure. The number of atoms in the chain (sometimes referred to as a linking chain) connecting the point and the (meth) acryloyl group is preferably 3 or less, and more preferably 2 or less. When the number of atoms is not more than the above upper limit, the crosslink density of the first resin layer or the second resin layer becomes large, and it is easy to improve the heat resistance of the polarizing film. Here, when there are a plurality of the connecting chains, it is sufficient that at least one connecting chain satisfies the above range of atomic numbers, and from the viewpoint of improving heat resistance, all the connecting chains satisfy the above range of atomic numbers. Is preferable.

Among the polyfunctional (meth) acrylate compounds, dipentaerythritol hexa (meth) acrylate and tripentaerythritol octa (meth) acrylate are preferable from the viewpoint of heat resistance of the polarizing film.

In the first curable composition or the second curable composition, the content of the polyfunctional (meth) acrylate compound is preferably 50 parts by mass or more, more preferably 50 parts by mass, based on 100 parts by mass of the solid content of the curable composition. Is 60 parts by mass or more, more preferably 70 parts by mass or more, preferably 100 parts by mass or less, more preferably 95 parts by mass or less, still more preferably 90 parts by mass or less. When the content of the polyfunctional (meth) acrylate compound is in the above range, it is easy to improve the adhesion, heat resistance and flexibility between the layers of the polarizing film. In the present specification, the solid content of the curable composition means the total amount of the components excluding the solvent from the curable composition when the solvent is contained in the curable composition.

In one embodiment of the present invention, at least one of the first curable composition and the second curable composition preferably contains a urethane (meth) acrylate compound as the (meth) acrylic compound. This aspect is advantageous from the viewpoint of adhesion, heat resistance and flexibility of the polarizing film.

The urethane (meth) acrylate compound generally means a reaction product of an isocyanate compound, a polyol compound and a (meth) acrylate compound, and is a polyfunctional urethane (meth) acrylate having two or more (meth) acryloyloxy groups in the molecule. It is preferably a compound. Since the polyfunctional urethane (meth) acrylate compound can form a crosslinked structure, it is advantageous from the viewpoint of heat resistance of the polarizing film and can impart appropriate toughness. Therefore, it may be possible to increase the flexibility of the polarizing film and improve the resistance to deformation due to bending or the like.

From the viewpoint of heat resistance, the polyfunctional urethane (meth) acrylate compound preferably has 3 or less functional groups, and more preferably 2 functional groups. Further, from the viewpoint of achieving both heat resistance and flexibility, the number of functional groups is preferably 2 to 5.

The weight average molecular weight (Mw) of the urethane (meth) acrylate compound is preferably 300 or more, more preferably 400 or more, preferably 10,000 or less, more preferably 7,000 or less, still more preferably 7,000 or less in terms of polystyrene. It is 5,000 or less, particularly preferably 3,000 or less. When the Mw of the urethane (meth) acrylate compound is in the above range, the adhesion and heat resistance are likely to be improved. The weight average molecular weight (Mw) can be measured by, for example, gel permeation chromatography (GPC).

The urethane (meth) acrylate compound preferably has a (meth) acryloyl group number of 15 × 10 ^-4 or more, more preferably 20 × 10 ^-4 or more, and 30 × 10 ^-4 or more per unit molecular weight. It is more preferable to have 40 × 10 ^-4 or more, and it is particularly preferable to have 40 × 10 -4 or more. When the number of (meth) acryloyl groups per unit molecular weight is at least the above lower limit, the heat resistance and adhesion of the polarizing film can be more easily improved. Further, the upper limit of the number of (meth) acryloyl groups per unit molecular weight is usually 20 or less. The number of (meth) acryloyl groups per unit molecular weight can be calculated by the formula: number of (meth) acryloyl groups / weight average molecular weight (Mw) of the urethane (meth) acrylate compound.

When the first curable composition or the second curable composition contains a urethane (meth) acrylate compound, the content of the urethane (meth) acrylate compound is preferably 100 parts by mass with respect to the solid content of the curable composition. Is 10 parts by mass or more, more preferably 30 parts by mass or more, and preferably 100 parts by mass or less. When the content of the urethane (meth) acrylate compound is within the above range, the adhesion, heat resistance and flexibility of the polarizing film are likely to be improved.

When the first curable composition or the second curable composition contains a polyfunctional (meth) acrylate compound and a urethane (meth) acrylate compound, the polyfunctional (meth) acrylate compound and the urethane (meth) acrylate compound are mixed. It is preferably contained in a ratio of 95: 5 to 50:50, more preferably 90:10 to 70:30 (polyfunctional (meth) acrylate compound: urethane (meth) acrylate compound, mass ratio). By containing the polyfunctional (meth) acrylate compound and the urethane (meth) acrylate compound in the above-mentioned compounding ratio, it is easy to improve the adhesion, heat resistance and flexibility of the polarizing film.

The first curable composition or the second curable composition may contain a monofunctional (meth) acrylate compound, if necessary. The monofunctional (meth) acrylate compound may be a monomer, an oligomer or a polymer, and among these, a monofunctional (meth) acrylate monomer can be preferably used. Examples of monofunctional (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl (meth) acrylate. 2-Ethylhexyl (meth) acrylate, isononyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) ) Acrylate, 2-Hydroxy-3-phenoxypropyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, ethylcarbitol (meth) acrylate, 2-phenoxyethyl (meth) acrylate, Phenoxypolyethylene glycol (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 2-carboxyethyl (meth) acrylate, 1- [2- (meth) acryloyloxyethyl] phthalic acid, 1- [2- (Meta) acryloyloxyethyl] hexahydrophthalic acid, 1- [2- (meth) acryloyloxyethyl] succinic acid and 4- [2- (meth) acryloyloxyethyl] trimerit, tetrahydrofurfuryl (meth) ) Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate acid and the like. The monofunctional (meth) acrylate monomer can be used alone or in combination of two or more.

When the first curable composition or the second curable composition contains a monofunctional (meth) acrylate compound, the content of the monofunctional (meth) acrylate compound is the content of the monofunctional (meth) acrylate compound with respect to 100 parts by mass of the solid content of the curable composition. It is preferably 0 parts by mass or more, more preferably 20 parts by mass or more, and preferably 50 parts by mass or less. When the content of the monofunctional (meth) acrylate compound is in the above range, the coatability is improved from the viewpoint of adjusting the viscosity of the curable composition.

At least one of the first curable composition and the second curable composition preferably contains a radical polymerization initiator from the viewpoint of improving curability, and the first curable composition and the second curable composition. It is more preferred that both contain a radical polymerization initiator. The radical polymerization initiator is not particularly limited as long as it can initiate curing of the curable compound by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and specific examples thereof include acetophenone. 3-Methylacetophenone, benzyldimethylketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane Acetphenone-based initiators such as -1-one and 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzophenone-based initiators such as benzophenone, 4-chlorobenzophenone and 4,4'-diaminobenzophenone; 2 , 2-Dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone and other alkylphenone-based initiators; benzophenone-based initiators such as benzoinpropyl ether and benzoinethyl ether; 4- Thioxanthone-based initiators such as isopropylthioxanthone; acylphosphine oxide-based initiators such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; and other examples include xanthone, fluorenone, camphorquinone, benzaldehyde, and anthraquinone. These radical polymerization initiators can be used alone or in combination of two or more.

When the first curable composition or the second curable composition contains a radical polymerization initiator, the content of the radical polymerization initiator is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the solid content of the curable compound. Parts, more preferably 2 to 8 parts by mass. When the content of the radical polymerization initiator is at least the above lower limit, the polymerization initiation ability is sufficiently expressed and the curability is improved. On the other hand, when the content of the polymerization initiator is not more than the above upper limit, the radical polymerization initiator is less likely to remain, and it becomes easier to suppress a decrease in visible light transmittance and the like.

The first curable composition or the second curable composition may be an additive other than the radical polymerization initiator, for example, an ultraviolet absorber, an antistatic agent, a stabilizer, an antioxidant, a colorant, if necessary. , Surface conditioners and the like may be included. Other additives can be used alone or in combination of two or more. The content of the other additives is preferably about 0.1 to 20% by mass with respect to the mass of the solid content of the curable composition.

The first curable composition or the second curable composition can be prepared by mixing and stirring the (meth) acrylic compound and, if necessary, additives and the like. Further, in order to improve the coatability, the viscosity may be adjusted by adding a solvent to the first curable composition or the second curable composition.

The solvent may be any one that can dissolve the components constituting the first curable composition or the second curable composition, and for example, aliphatic hydrocarbons such as hexane and octane; aromatics such as toluene and xylene. Hydrocarbons; alcohols such as ethanol, 1-propanol, isopropanol and 1-butanol; ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate and isobutyl acetate; ethylene glycol monomethyl ether and ethylene glycol mono Glycol ethers such as ethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether; esterified glycol ethers such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate should be appropriately selected and used. Can be done. These solvents can be used alone or in combination of two or more. The type and content of the solvent are appropriately selected depending on the type and content, shape, coating method, thickness of the resin layer, and the like of the components contained in the first curable composition or the second curable composition. For example, the content of the solvent is preferably 3 to 1000 parts by mass, more preferably 5 to 100 parts by mass, and further preferably 7 to 50 parts by mass with respect to 100 parts by mass of the solid content of the curable composition.

In one embodiment of the present invention, the first resin layer is obtained by applying the first curable composition on a polarizing element or a release film and curing the composition. The second resin layer is obtained by applying a second curable composition on a base material, a release film or an alignment film and curing the composition.

Examples of the coating method of the first curable composition or the second curable composition include the coating method exemplified in the section of <polarizer>. Further, it is preferable that the curable composition is cured by irradiating it with active energy rays to polymerize a polymerizable component such as a (meth) acrylic compound contained in the composition. The active energy ray is appropriately selected depending on the type of the polymerizable component such as the (meth) acrylic compound, the type of the radical polymerization initiator, the amount thereof, and the like. Specific examples thereof include one or more types of active energy rays selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α rays, β rays and γ rays. Among them, ultraviolet light is preferable because it is easy to control the progress of the polymerization reaction and it is possible to use a photopolymerization apparatus widely used in the art. Examples of the light source of the active energy ray include the light source exemplified in the section of <polarizer>. As the ultraviolet irradiation intensity, irradiation time, and integrated light amount, the range of the ultraviolet irradiation intensity, irradiation time, and integrated light amount exemplified in the section of <polarizer> may be appropriately used.

The thicknesses of the first resin layer and the second resin layer are preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and even more preferably 0.3 to 3 μm, respectively. When the thickness of the first resin layer or the second resin layer is within the above range, it is easy to improve the adhesion between the first resin layer and the polarizing element and the adhesion between the second resin layer and the alignment film. In addition, it is easy to effectively suppress the diffusion of the dichroic dye contained in the polarizing element, and it is easy to increase the heat resistance.

<Polarizing film>
As described above, the polarizing film of the present invention has excellent adhesion between layers. Further, since the polarizing film is also excellent in heat resistance, it is possible to effectively suppress the diffusion of the dichroic dye contained in the polarizing element even in a high temperature environment and suppress the deterioration of the polarizing performance. Further, in a preferred embodiment, excellent flexibility can be exhibited in addition to adhesion and heat resistance. Therefore, the polarizing film can be suitably used for display devices such as organic EL display devices and touch panel display devices.

The method for producing the polarizing film of the present invention is not particularly limited as long as the first resin layer, the polarizing element, the alignment film, and the second resin layer can be laminated in this order, but for example, a second resin layer is formed and the second resin layer is formed. An alignment film is formed on the alignment film, and a polarizing element is formed on the alignment film to obtain a laminate in which the second resin layer, the alignment film, and the polarizing element are laminated in this order. Examples thereof include a method including a step of applying or superimposing the first curable composition and curing the first curable composition.

In a preferred embodiment of the present invention, the polarizing film of the present invention is a first curable composition on a polarizing element surface of a laminate in which a second resin layer, an alignment film, and a polarizing element are laminated on a release film. Is applied, and the first curable composition is cured by irradiating it with active energy rays from the first curable composition side to cure the release film, the second resin layer, the alignment film, the polarizing element, and the first resin. A laminate having layers in this order is obtained, and the laminate is manufactured by a method including a step of peeling a release film from the laminate.

In a preferred embodiment of the present invention, the polarizing film of the present invention is a laminate in which a first curable composition formed on a release film, a second resin layer, an alignment film, and a polarizing element are laminated in this order. The release film, the first resin layer, the polarizing element, the alignment film, and the second It is produced by a method including a step of obtaining a laminated body in which resin layers are laminated in this order and peeling a release film from the laminated body.

In the polarizing film of the present invention, the first resin layer, the polarizing element, the alignment film, and the second resin layer may be laminated in this order, and the polarizing element side of the first resin layer is not impaired as long as the effect of the present invention is not impaired. A functional layer may be contained in the surface on the opposite side of the surface, the surface on the side opposite to the alignment film side of the second resin layer, or between the layers. Examples of the functional layer include an ultraviolet absorbing layer, a hard coat layer, a primer layer, a gas barrier layer, a hue adjusting layer, a refractive index adjusting layer, an antireflection layer, an antistatic layer, an adhesive layer, and an adhesive layer. These functional layers can be used alone or in combination of two or more.

[Polarizer]
The polarizing film of the present invention may be combined with a retardation film to form a polarizing plate. That is, the polarizing plate in the present invention includes the polarizing film and the retardation film. The retardation film may be laminated on the surface of the first resin layer or the second resin layer of the polarizing film, for example, via an adhesive layer or an adhesive layer. It is preferable to stack the slow axis (optical axis) of the retardation film and the absorption axis of the polarizing film (polarizer) so as to be substantially at 45 °. By laminating the slow axis (optical axis) of the retardation film and the absorption axis of the polarizing film (polarizer) so as to be substantially 45 °, the function as an elliptical polarizing plate can be obtained. It should be noted that substantially 45 ° is usually in the range of 45 ± 5 °.

In the polarizing plate, the retardation film is described by the following formula (X):
100 ≤ Re (550) ≤ 180 (X)
[In the equation, Re (550) represents the in-plane retardation value at a wavelength of 550 nm]
It is preferable to satisfy. When the retardation film has the in-plane retardation value represented by the above (X), it functions as a so-called λ / 4 plate. The formula (X) is preferably 100 nm ≦ Re (550) ≦ 180 nm, and more preferably 120 nm ≦ Re (550) ≦ 160 nm.

Further, the retardation film has the following formula (Y) :.
Re (450) / Re (550) <1 (Y)
[In the equation, Re (450) and Re (550) represent in-plane retardation values at wavelengths of 450 nm and 550 nm, respectively].
It is preferable to satisfy. The retardation film satisfying the above formula (Y) has so-called reverse wavelength dispersibility and exhibits excellent polarization performance. The value of Re (450) / Re (550) is preferably 0.93 or less, more preferably 0.88 or less, still more preferably 0.86 or less, preferably 0.80 or more, and more preferably 0. It is 82 or more.

The retardation film may be a stretched film that imparts a retardation by stretching a polymer, but from the viewpoint of thinning the polarizing plate, a polymerizable liquid crystal composition containing a polymer of a polymerizable liquid crystal compound ( Hereinafter, it is preferably composed of the polymerizable liquid crystal composition (B)). In the retardation film, the polymerizable liquid crystal compound is usually polymerized in an oriented state. The polymerizable liquid crystal compound (hereinafter, also referred to as “polymerizable liquid crystal compound (B)”) that forms a retardation film means a liquid crystal compound having a polymerizable functional group, particularly a photopolymerizable functional group. The photopolymerizable functional group refers to a group that can participate in the polymerization reaction by active radicals, acids, etc. generated from the photopolymerization initiator. Examples of the photopolymerizable functional 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 oxylanyl group, an oxetanyl group and the like. Of these, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxylanyl group and an oxetanyl group are preferable, and an acryloyloxy group is more preferable. The liquid crystal property may be a thermotropic liquid crystal or a lyotropic liquid crystal, and the phase-ordered structure may be a nematic liquid crystal or a smectic liquid crystal. As the polymerizable liquid crystal compound, only one kind may be used, or two or more kinds may be used in combination.

Examples of the polymerizable liquid crystal compound (B) include compounds satisfying all of the following (a) to (d) from the viewpoint of facilitating film formation and imparting retardation represented by the above formula (Y). ..

(A) A compound having a thermotropic liquid crystal property;
(A) The polymerizable liquid crystal compound has π electrons in the long axis direction (a).
(C) It has π electrons in the direction [intersection direction (b)] that intersects the major axis direction (a).
(D) A polymerizable liquid crystal compound defined by the following formula (i), where the total number of π electrons existing in the long axis direction (a) is N (πa) and the total molecular weight existing in the long axis direction is N (Aa). Π electron density in the long axis direction (a) of
D (πa) = N (πa) / N (Aa) (i)
The polymerizable liquid crystal compound defined by the following formula (ii), where the total number of π electrons existing in the crossing direction (b) is N (πb) and the total molecular weight existing in the crossing direction (b) is N (Ab). Π electron density in the crossing direction (b) of
D (πb) = N (πb) / N (Ab) (ii)
And,
0 ≦ [D (πa) / D (πb)] ≦ 1
[That is, the π electron density in the crossing direction (b) is larger than the π electron density in the major axis direction (a)].
The polymerizable liquid crystal compound (B) satisfying all of the above (a) to (d) is, for example, applied onto an alignment film formed by a rubbing treatment and heated to a temperature equal to or higher than the phase transition temperature to form a nematic phase. It is possible to do. In the nematic phase formed by orienting the polymerizable liquid crystal compound (B), the polymerizable liquid crystal compound is usually oriented so that the major axis directions are parallel to each other, and this major axis direction is the orientation direction of the nematic phase. Will be.

で表される化合物が挙げられる。前記式（ＩＩ）で表される化合物は単独又は２種以上組合せて使用できる。 The polymerizable liquid crystal compound (B) having the above-mentioned characteristics generally exhibits reverse wavelength dispersibility. Specifically, as a compound satisfying the above-mentioned characteristics (a) to (d), for example, the following formula (II):

Examples thereof include compounds represented by. The compound represented by the formula (II) can be used alone or in combination of two or more.

In formula (II), Ar represents a divalent aromatic group which may have a substituent. The aromatic group referred to here is a group having a cyclic structure having flatness, and the number of π electrons of the cyclic structure is [4n + 2] according to Hückel's rule. Here, n represents an integer. When a ring structure is formed by including heteroatoms such as —N = and —S—, the case where the Hückel's rule is satisfied including the uncovalent bond electron pair on these heteroatoms and the aromaticity is included is also included. The divalent aromatic group preferably contains at least one of a nitrogen atom, an oxygen atom and a sulfur atom.

In formula (II), G ¹ and G ² independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, respectively. Here, the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and carbon. It may be substituted with an alkoxy group, a cyano group or a nitro group having the number 1 to 4, and the carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group is an oxygen atom or a sulfur atom. Alternatively, it may be substituted with a nitrogen atom.

In formula (II), L ¹ , L ² , B ¹ and B ² are independently single-bonded or divalent linking groups, respectively.

In formula (II), k and l each independently represent an integer of 0 to 3, and satisfy the relationship of 1 ≦ k + l. Here, when 2 ≦ k + l, B ¹ and B ² , G ¹ and G ² may be the same or different from each other.

In formula (II), E ¹ and E ² each independently represent an alkanediyl group having 1 to 17 carbon atoms, where the hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom. , -CH _2- contained in the alkanediyl group may be substituted with -O-, -S-, -Si-. P ¹ and P ² independently represent a polymerizable group or a hydrogen atom, and at least one is a polymerizable group.

In formula (II), G ¹ and G ² may be independently substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, respectively 1. A 1,4-cyclohexanediyl group which may be substituted with at least one substituent selected from the group consisting of a 4-phenylenediyl group, a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably methyl. It is a 1,4-phenylenediyl group substituted with a group, an unsubstituted 1,4-phenylenediyl group, or an unsubstituted 1,4-trans-cyclohexanediyl group, and particularly preferably an unsubstituted 1,4-. It is a phenylenediyl group or an unsubstituted 1,4-trans-cyclohexanediyl group. Further, it is preferable that at least one of a plurality of G ¹ and G ² is a divalent alicyclic hydrocarbon group, and at least one of G ¹ and G ² bonded to L ¹ or L ² is at least one. More preferably, it is a divalent alicyclic hydrocarbon group.

In formula (II), L ¹ and L ² are independent of each other, preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a1 OR ^a2- , -R ^a3 COOR. ^a4- , -R ^a5 OCOR ^a6- , R ^a7 OC = OOR ^a8- , -N = N-, -CR ^c = CR ^d- , or C≡C-. Here, R ^a1 to R ^a8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, and R ^c and R ^d represent an alkyl group or a hydrogen atom having 1 to 4 carbon atoms. L ¹ and L ² are independently, more preferably single bonds, -OR ^a2-1- , -CH _2- , -CH ₂ CH _2- , ^{-COOR a4-1-} , or OCOR ^a6-1- , respectively. .. Here, R ^a2-1 , R ^a4-1 , and R ^a6-1 independently represent either single bond, -CH _2- , or -CH ₂ CH _2- . L ¹ and L ² are independent, more preferably single bond, —O—, —CH ₂ CH ₂ −, −COO−, —COOCH ₂ CH ₂₋ , or OCO−, respectively.

In a preferred embodiment of the present invention, at least one of G ¹ and G ² in formula (II) is a divalent alicyclic hydrocarbon group, wherein the divalent alicyclic hydrocarbon group is used. , A polymerizable liquid crystal compound bonded by a divalent aromatic group Ar which may have a substituent and L ¹ and / or L ² which is -COO- is used.

In formula (II), B ¹ and B ² are independent of each other, preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a9 OR ^a10- , -R ^a11 COOR. ^a12- , -R ^a13 OCOR ^a14- , or R ^a15 OC = OOR ^a16- . Here, R ^a9 to R ^a16 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms. B ¹ and B ² are independent, more preferably single bonds, -OR ^a10-1- , -CH _2- , -CH ₂ CH _2- , ^{-COOR a12-1-} , or OCOR ^a14-1- . .. Here, R ^a10-1 , R ^a12-1 , and R ^a14-1 independently represent either single bond, -CH _2- , or -CH ₂ CH _2- . B ¹ and B ² are independent, more preferably single bond, -O-, -CH ₂ CH _2- , -COO-, -COOCH ₂ CH _2- , -OCO-, or OCOCH ₂ CH _2- . ..

In formula (II), k and l are preferably in the range of 2 ≦ k + l ≦ 6, preferably k + l = 4, and more preferably k = 2 and l = 2 from the viewpoint of expressing reverse wavelength dispersibility. preferable. It is more preferable that k = 2 and l = 2 because the symmetrical structure is obtained.

In the formula (II), E ¹ and E ² are each independently preferably an alkanediyl group having 1 to 17 carbon atoms, and more preferably an alkanediyl group having 4 to 12 carbon atoms.

In the formula (II), examples of the polymerizable group represented by P ¹ or P ² include an epoxy group, a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group and an acryloyloxy group. , Methacloyloxy group, oxylanyl group, oxetanyl group and the like. Among these, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxylanyl group and an oxetanyl group are preferable, and an acryloyloxy group is more preferable.

In formula (II), Ar has at least one selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle which may have a substituent, and an electron-withdrawing group. Is preferable. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring and the like, and a benzene ring and a naphthalene ring are preferable. Examples of the aromatic heterocycle include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a triazine ring, a pyrrolin ring, an imidazole ring, and a pyrazole ring. , Thiazole ring, benzothiazole ring, thienothiazole ring, oxazole ring, benzoxazole ring, phenanthroline ring and the like. Among these, it is preferable to have a thiazole ring, a benzothiazole ring, or a benzofuran ring, and it is more preferable to have a benzothiazole group. When Ar contains a nitrogen atom, the nitrogen atom preferably has π electrons.

In the formula (II), the total number of _π electrons contained in the divalent aromatic group represented by Ar is preferably 8 or more, more preferably 10 or more, still more preferably 14 or more, and particularly. It is preferably 16 or more. Further, it is preferably 30 or less, more preferably 26 or less, and further preferably 24 or less.

Examples of the aromatic group represented by Ar include groups of the following formulas (Ar-1) to (Ar-23).

In the formulas (Ar-1) to (Ar-23), the * mark represents the connecting portion, and Z ⁰ , Z ¹ and Z ² are independently hydrogen atoms, halogen atoms, and alkyl having 1 to 12 carbon atoms. Group, cyano group, nitro group, alkylsulfinyl group having 1 to 12 carbon atoms, alkylsulfonyl group having 1 to 12 carbon atoms, carboxyl group, fluoroalkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 6 carbon atoms, Alkylthio group with 1 to 12 carbon atoms, N-alkylamino group with 1 to 12 carbon atoms, N, N-dialkylamino group with 2 to 12 carbon atoms, N-alkylsulfamoyl group with 1 to 12 carbon atoms or carbon Represents an N, N-dialkylsulfamoyl group of numbers 2-12.

In equations (Ar-1) to (Ar-23), ^Q1 and ^Q2 are independently -CR 2'R3'-, -S-, ^{-NH-, -NR 2' - ,} -, respectively. It represents CO- or O-, and R ^2'and R ^{3'independently} represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the formulas (Ar-1) to (Ar-23), J ¹ and J ² independently represent a carbon atom or a nitrogen atom, respectively.

In formulas (Ar- ¹ ) to (Ar-23), Y1 ^, Y2 and Y3 ^each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may be substituted.

In the formulas (Ar-1) to (Ar-23), W ¹ and W ² independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0 to 6.

Examples of the aromatic hydrocarbon group in Y ¹ , Y ² and Y ³ include an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and a biphenyl group, and a phenyl group. , A naphthyl group is preferable, and a phenyl group is more preferable. The aromatic heterocyclic group has 4 to 20 carbon atoms including at least one heteroatom such as a nitrogen atom such as a frill group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group and a benzothiazolyl group, an oxygen atom and a sulfur atom. Examples thereof include an aromatic heterocyclic group, and a frill group, a thienyl group, a pyridinyl group, a thiazolyl group and a benzothiazolyl group are preferable.

Y ¹ and Y ² may be independently substituted polycyclic aromatic hydrocarbon groups or polycyclic aromatic heterocyclic groups, respectively. The polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring assembly. The polycyclic aromatic heterocyclic group refers to a fused polycyclic aromatic heterocyclic group or a group derived from an aromatic ring assembly.

In formulas (Ar-1) to (Ar-23), Z ⁰ , Z ¹ and Z ² are independently hydrogen atom, halogen atom, alkyl group having 1 to 12 carbon atoms, cyano group and nitro group, respectively. It is preferably an alkoxy group having 1 to 12 carbon atoms, Z ⁰ is more preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a cyano group, and Z ¹ and Z ² are a hydrogen atom, a fluorine atom, and chlorine. Atomic, methyl and cyano groups are more preferred.

In the formulas (Ar-1) to (Ar-23), ^Q1 and ^Q2 are preferably -NH-, -S-, -NR 2'-, and ^-O- , and ^R2'is preferably a hydrogen atom. .. Of these, -S-, -O-, and -NH- are particularly preferable.

Among the formulas (Ar-1) to (Ar-23), the formulas (Ar-6) and (Ar-7) are preferable from the viewpoint of molecular stability.

In formulas (Ar-17) to (Ar-23), Y ¹ may form an aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z ⁰ . Examples of the aromatic heterocyclic group include those described above as the aromatic heterocycle that Ar may have. For example, a pyrrol ring, an imidazole ring, a pyrrolidine ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and an indole. Examples thereof include a ring, a quinoline ring, an isoquinoline ring, a purine ring, and a pyrrolidine ring. This aromatic heterocyclic group may have a substituent. Further, Y ¹ may be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group which may be substituted as described above, together with the nitrogen atom to which the Y 1 is bonded and Z ⁰ . For example, a benzofuran ring, a benzothiazole ring, a benzoxazole ring and the like can be mentioned. The compound represented by the formula (II) can be produced, for example, according to the method described in JP-A-2010-31223.

The content of the polymerizable liquid crystal compound (B) in the polymerizable liquid crystal composition (B) constituting the retardation film is, for example, 70 to 99 with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition (B). It is .5 parts by mass, preferably 80 to 99 parts by mass, and more preferably 90 to 98 parts by mass. When the content is within the above range, the orientation of the retardation film tends to be high. Here, the solid content means the total amount of the components excluding the volatile components such as the solvent from the polymerizable liquid crystal composition (B).

The polymerizable liquid crystal composition (B) may contain a polymerization initiator for initiating the polymerization reaction of the polymerizable liquid crystal compound (B). The polymerization initiator may be appropriately selected from those conventionally used in the art and may be a thermal polymerization initiator or a photopolymerization initiator, but under lower temperature conditions. A photopolymerization initiator is preferable because it can initiate a polymerization reaction. Preferred examples of the photopolymerization initiator that can be used in the composition for forming a substituent include those similar to those exemplified above. Further, the polymerizable liquid crystal composition (B) may contain a photosensitizer, a leveling agent, an additive exemplified as an additive contained in the composition for forming a polarizing element, and the like, if necessary. .. Examples of the photosensitizer and the leveling agent include those similar to those exemplified above as those that can be used in the composition for forming a substituent.

The polymerizable liquid crystal composition (B) is prepared, for example, by mixing and stirring the polymerizable liquid crystal compound (B) and, if necessary, a polymerization initiator, an additive and the like. Further, in order to improve the coatability, a solvent may be added to the polymerizable liquid crystal composition (B) to adjust the viscosity. Examples of the solvent include the solvents exemplified above as the solvent contained in the composition for forming a substituent.

For the retardation film, the polymerizable liquid crystal composition (B) is applied onto a substrate or an alignment film, the solvent is removed by drying, and the polymerizable liquid crystal compound (B) in the obtained coating film is heated and / / Alternatively, it can be obtained by curing with an active energy ray. Examples of the alignment film include those similar to those exemplified above as those that can be used when producing the polarizing element of the present invention.

The solvent used for the composition for forming a retardation film, the method for applying the composition for forming a retardation film, the curing conditions using active energy rays, and the like are all the same as those that can be adopted in the method for producing a polarizing element of the present invention. Things can be mentioned.

The thickness of the retardation film can be appropriately selected depending on the display device to be applied, but is preferably 0.1 to 10 μm, more preferably 1 to 5 μm from the viewpoint of thinning and flexibility. It is more preferably 1 to 3 μm.

The polarizing plate in the present invention may include a polarizing film, a retardation film, and a layer other than the pressure-sensitive adhesive layer or the adhesive layer, for example, a protective film. In a preferred embodiment, in the polarizing plate of the present invention, a polarizing film and a retardation film are bonded to each other via an adhesive layer or an adhesive layer.

The thickness of the polarizing plate of the present invention is preferably 1 to 100 μm, more preferably 2 to 70 μm, and even more preferably 3 to 60 μm from the viewpoint of flexibility and visibility of the display device.

The polarizing film or polarizing plate of the present invention may include a front plate. FIG. 1 shows a schematic cross-sectional view of the layer structure of the polarizing film with a front plate in one embodiment of the present invention. In the polarizing film 1 with a front plate, the front plate 3 is formed on the first resin layer 4 of the polarizing film 2. In the polarizing film 2, the first resin layer 4, the polarizing element 5, the alignment film 6, and the second resin layer 7 are laminated in this order from the front plate 3 side. The polarizing film 1 with a front plate can be provided with a front plate to impart surface hardness and light resistance. The polarizing film 1 with a front plate may have an adhesive layer or an adhesive layer formed between the front plate 3 and the first resin layer 4.

FIG. 2 shows a schematic cross-sectional view of the layer structure of the polarizing plate with a front plate in one embodiment of the present invention. In the polarizing plate 8 with a front plate, the front plate 3 is formed on the polarizing plate 9. In the polarizing plate 9, the first resin layer 4, the polarizing element 5, the alignment film 6, the second resin layer 7, and the retardation film 10 are laminated in this order from the front plate 3 side. The polarizing plate 8 with a front plate can be provided with a front plate to impart surface hardness and light resistance. In the polarizing plate 8 with a front plate, an adhesive layer or an adhesive layer is formed between the front plate 3 and the first resin layer 4 and / or between the second resin layer 7 and the retardation film 10. It may have been done. In addition, in FIGS. 1 and 2, the dimensions and ratios of each layer are appropriately different in order to make the drawings easier to see.

FIG. 3 shows a schematic cross-sectional view of the layer structure of the polarizing film with a front plate according to another embodiment of the present invention. In the polarizing film 11 with a front plate, the front plate 3 is formed on the second resin layer 7 of the polarizing film 2. In the polarizing film 2, the second resin layer 7, the alignment film 6, the polarizing element 5, and the first resin layer 4 are laminated in this order from the front plate 3 side. The polarizing film 11 with a front plate can be provided with a front plate to impart surface hardness and light resistance. The polarizing film 11 with a front plate may have an adhesive layer or an adhesive layer formed between the front plate 3 and the second resin layer 7.

FIG. 4 shows a schematic cross-sectional view of the layer structure of the polarizing plate with a front plate according to another embodiment of the present invention. In the polarizing plate 12 with a front plate, the front plate 3 is formed on the polarizing plate 13. In the polarizing plate 13, the second resin layer 7, the alignment film 6, the polarizing element 5, the first resin layer 4, and the retardation film 10 are laminated in this order from the front plate 3 side. The polarizing plate 13 with a front plate can be provided with a front plate to impart surface hardness and light resistance. In the polarizing plate 13 with a front plate, an adhesive layer or an adhesive layer is formed between the front plate 3 and the second resin layer 7 and / or between the first resin layer 4 and the retardation film 10. It may have been done. In FIGS. 3 and 4, the dimensions and ratios of the layers are appropriately different in order to make the drawings easier to see.

<Display device>
The polarizing film of the present invention or the polarizing plate can be applied to a display device. The display device can be obtained, for example, by adhering the polarizing film of the present invention or the polarizing plate to the surface of the display device via an adhesive layer or an adhesive layer. The display device is a device having a display mechanism, and includes a light emitting element or a light emitting device as a light emitting source. Display devices include liquid crystal display devices, organic electroluminescence (EL) display devices, inorganic electroluminescence (EL) display devices, touch panel display devices, electron emission display devices (electric field emission display devices (FED, etc.), surface electric field emission display devices). (SED)), electronic paper (display device using electronic ink or electrophoretic element), plasma display device, projection type display device (grating light valve (GLV) display device, display device having a digital micromirror device (DMD)). Etc.) and piezoelectric ceramic displays and the like. The liquid crystal display device includes any of a transmissive liquid crystal display device, a semi-transmissive liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, a projection type liquid crystal display device, and the like. These display devices may be display devices that display two-dimensional images, or may be stereoscopic display devices that display three-dimensional images. In particular, as the display device of the present invention, an organic EL display device and a touch panel display device are preferable, and an organic EL display device is particularly preferable.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these examples. Hereinafter, the amounts used, the parts representing the contents and% are based on mass unless otherwise specified.

<Evaluation of adhesion>
The surface of the second resin layer of the polarizing film obtained in Examples and Comparative Examples is attached to glass via a pressure-sensitive adhesive, and cellophane tape is attached to the surface of the first resin layer opposite to the glass surface. A peeling test was conducted to evaluate the adhesion of the polarizing film. The case where the peeling phenomenon could be confirmed inside the polarizing film was evaluated as "x", and the case where the peeling phenomenon could not be confirmed was evaluated as "○".

<Evaluation of heat resistance>
The degree of polarization Py and the simple substance transmittance Ty of the polarizing films obtained in Examples and Comparative Examples were measured as follows. A device in which a folder with a polarizing element is set in a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation) for the transmittance (Ta) in the transmission axis direction and the transmittance (Tb) in the absorption axis direction in the wavelength range of 380 nm to 780 nm. Was measured by the double beam method. The folder was equipped with a mesh that cuts the amount of light by 50% on the reference side.
Using the following equations (Equation 1) and (Equation 2), the single transmittance and the degree of polarization at each wavelength are calculated, and the luminosity factor is corrected by the 2 degree field (C light source) of JIS Z 8701. The single transmittance (Ty) and the luminosity factor correction polarization degree (Py) were calculated.
Elemental transmittance Ty (%) = (Ta + Tb) / 2 (Equation 1)
Degree of polarization Py (%) = (Ta-Tb) / (Ta + Tb) x 100 (Equation 2)

After heating the polarizing films obtained in Examples and Comparative Examples at 85 ° C. for 240 hours, the degree of polarization Py and the single transmittance Ty of the polarizing film were measured again, and the amount of change in Py before and after the heat resistance test ΔPy (=). The Py after the heat resistance test-Py before the heat resistance test) and the amount of change in Ty before and after the heat resistance test ΔTy (= Ty after the heat resistance test-Ty before the heat resistance test) were calculated.

<Evaluation of flexibility>
The flexibility was evaluated as follows using the paint general test method-flexibility (cylindrical mandrel method) described in JIS-K-5600-5-1.
The polarizing films obtained in Examples and Comparative Examples were cut into 25 mm × 200 mm squares, and the cut film was cut at a temperature of 25 ° C. using a cylindrical mandrel method bending resistance tester type II (manufactured by TP Giken Co., Ltd.). Under the condition of a relative humidity of 55% RH, a bending test was performed by winding a mandrel rod having a diameter of 4 mm (bending radius R = 2 mm) with the cured layer of the first resin layer forming composition on the outside. Using the film after the test, the film was visually checked with illuminated transmitted light in a dark room environment, and when the crack occurrence status was observed, the cracks were marked as "x" and the cracks were not visible. It was judged as "○".

<Film thickness of each layer>
The thicknesses of the splitter, the alignment film, the first resin layer and the second resin layer were measured with a laser microscope (OLS3000 manufactured by Olympus Corporation).

[Manufacturing Examples 1 to 9]
<Preparation of Compositions (A) to (I) for Forming Resin Layer>
The components shown in Table 1 were mixed and stirred at 50 ° C. for 4 hours to obtain the resin layer forming compositions (A) to (I), respectively.

[Manufacturing Example 10]
<Preparation of composition (J) for forming a resin layer>
The following components were mixed and stirred at 23 ° C. for 4 hours to obtain a resin layer forming composition (J).
(Component of composition (J) for forming a resin layer)
・ Celoxide 2021P: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Dycel Chemical Co., Ltd.) 70 parts ・ 2-ethylhexyl glycidyl ether 30 parts ・ CPI-100P: Triarylsulfonium hexafluorophosphate 50% propylene carbonate solution (manufactured by San-Apro Co., Ltd.) 2.5 parts, SH710: Silicone-based leveling agent (manufactured by Toray Dow Corning Co., Ltd.) 0.25 parts

[Manufacturing Example 11]
<Preparation of composition (K) for forming a resin layer>
The following components were mixed and stirred at 23 ° C. for 4 hours to obtain a resin layer forming composition (K).
(Component of composition (K) for forming a resin layer)
・ Celoxide 2021P: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Chemical Co., Ltd.) 32.5 parts ・ EHPE3150: 2,2-bis (hydroxymethyl) -1-butanol 1 , 2-Epoxy-4- (2-oxylanyl) cyclohexane adduct (manufactured by Daicel Chemical Co., Ltd.) 17.5 parts ・ OXT-221: Bis (3-ethyl-3-oxetanylmethyl) ether (Toa Synthetic Co., Ltd.) 50 parts ・ CPI-100P: 50% solution of triarylsulfonium hexafluorophosphate in propylene carbonate (manufactured by San Apro Co., Ltd.) 2.5 parts ・ SH710: Silicone leveling agent (manufactured by Toray Dow Corning Co., Ltd.) 0 .25 copies

[Manufacturing Example 12]
<Preparation of composition (L) for forming a resin layer>
Acetoacetylated modified polyvinyl alcohol-based resin (Gosefimer Z200, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., saponification degree: 98.5 mol% or more) is dissolved in pure water by stirring at 90 ° C. for 4 hours. An aqueous solution having a concentration of 5% by weight was prepared. The above polyvinyl alcohol-based resin aqueous solution and a 10% by weight aqueous solution of sodium glyoxylate are mixed so that the solid content weight ratio of the acetacetyl group-modified polyvinyl alcohol-based resin: sodium glyoxylate is 1: 0.1, and further water is added. The composition (L) for forming a resin layer was prepared by diluting with pure water so that the solid content weight ratio of the polyvinyl alcohol-based resin to 100 parts was 3.0 parts.

Each component in Table 1 is shown below.
Polyfunctional acrylate monomer (1): Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., "NK ester A-DPH"), the branch point closest to the (meth) acryloyl group in the branched structure, and the (meth). ) The number of atoms in the chain connecting the acryloyl group is 2.

Polyfunctional acrylate monomer (2): Ethylene oxide (6 pieces) dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., "NK ester A-DPH-6E"), for the (meth) acryloyl group in the branched structure The number of atoms in the chain connecting the nearest branch point and the (meth) acryloyl group is 5.

Polyfunctional acrylate monomer (3): Ethylene oxide (12 pieces) dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., "NK ester A-DPH-12E"), for the (meth) acryloyl group in the branched structure The number of atoms in the chain connecting the nearest branch point and the (meth) acryloyl group is eight.

Polyfunctional acrylate monomer (4): tripentaerythritol octaacrylate (manufactured by Koei Chemical Industry Co., Ltd., "TPEA"), the branch point closest to the (meth) acryloyl group in the branched structure, and the (meth) acryloyl group. The number of atoms in the chain to be connected is two.

Urethane acrylate polymer (1): Urethane acrylate (manufactured by Daicel Ornex Co., Ltd., "Evecryl 4858"), number of functional groups is 2, weight average molecular weight Mw is 450 ^, number of functional groups per unit molecular weight is 44.4 × 10- ⁴ .

Urethane acrylate polymer (2): Urethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., "Shikou UV-7650"), the number of functional groups is 4 to 5, the weight average molecular weight Mw is 2300, and the number of functional groups per unit molecular weight is 19. It is 6.6 × 10 ^-4 .

Radical Polymerization Initiator (1): Phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide (BASF, "Irgacure 819")
Radical Polymerization Initiator (2): 1-Hydroxycyclohexylphenyl ketone (BASF, "Irgacure 184")
Radical Polymerization Initiator (3): 2- [4- (Methylthio) Benzoyl] -2- (4-morpholinyl) Propane (BASF, "Irgacure 907")

Solvent (1): Methyl ethyl ketone

・二色性色素：
アゾ色素；

・光重合開始剤：
２－ジメチルアミノ－２－ベンジル－１－（４－モルホリノフェニル）ブタン－１－オン（イルガキュア３６９；チバ・スペシャルティ・ケミカルズ(株)製） ６部
・レベリング剤：
ポリアクリレート化合物（ＢＹＫ－３６１Ｎ；ＢＹＫ－Ｃｈｅｍｉｅ社製） １．２部
・溶剤：
ｏ－キシレン ４００部 [Manufacturing Example 13]
<Preparation of composition for forming a polarizing film>
The following components were mixed and stirred at 80 ° C. for 1 hour to obtain a composition for forming a polarizing film. As the dichroic dye, the azo dye described in Examples of JP2013-101328A was used.
-Polymerizable liquid crystal compound:

・ Dichroic pigment:
Azo dye;

-Photopolymerization initiator:
2-Dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1-one (Irgacure 369; manufactured by Ciba Specialty Chemicals Co., Ltd.) 6 parts ・ Leveling agent:
Polyacrylate compound (BYK-361N; manufactured by BYK-Chemie) 1.2 parts ・ Solvent:
400 copies of o-xylene

[Example 1]
(1) Preparation of Second Resin Layer The release-treated surface of the release-treated polyethylene terephthalate film (SP-PLR382050 manufactured by Lintec Co., Ltd.) (release film) is subjected to corona treatment and then has second curability. As a composition, the resin layer forming composition (A) is applied by a bar coating method (# 2 30 mm / s), and an exposure amount of 500 mJ is used using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Denki Co., Ltd.). By irradiating the coating layer of the composition for forming a resin layer with ultraviolet rays of / cm ² (based on 365 nm), a release film with a resin layer having a second resin layer formed on the surface of the release film was obtained. The thickness of the second resin layer was 1.5 μm.

・溶剤：
ｏ－キシレン ９８部 (2) Preparation of a photo-alignment film (i) Preparation of a composition for forming a photo-alignment film By mixing the following components described in JP2013-033249 and stirring the obtained mixture at 80 ° C. for 1 hour. A composition for forming a photoalignment film was obtained.
-Photo-oriented polymer:

·solvent:
98 copies of o-xylene

(Ii) Formation of Photo-Alignment Film Next, after corona treatment is applied to the surface of the second resin layer of the release film with a resin layer, a composition for forming a photo-alignment film is applied and dried at 120 ° C. A dry film was obtained. The dried film was irradiated with polarized UV to form a photoalignment film, and a laminate A having a release film, a second resin layer, and a photoalignment film in this order was obtained. The polarized UV treatment was carried out using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio, Inc.) under the condition that the intensity measured at a wavelength of 365 nm was 100 mJ. The thickness of the photoalignment film was 100 nm.

(3) Preparation of Polarizer A composition for forming a polarizing film is applied to the surface of the photoalignment film of the laminate A obtained as described above by the bar coating method (# 9 30 mm / s), and dried at 120 ° C. The polymerizable liquid crystal compound was phase-transferred to the liquid phase by heating and drying in an oven for 1 minute, and then cooled to room temperature to phase-transfer the polymerizable liquid crystal compound to the smectic liquid crystal state. Next, using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Denki Co., Ltd.), the layer formed from the composition for forming a polarizing film is irradiated with ultraviolet rays having an exposure amount of 1000 mJ / cm ² (365 nm standard). Thereby, the polymerizable liquid crystal compound contained in the dry film was polymerized while maintaining the smectic liquid crystal state of the polymerizable liquid crystal compound, and a substituent (polarizing film) was formed from the dry film. The thickness of the stator was 2.3 μm. In this way, a laminate B having a release film, a second resin layer, a photoalignment film, and a polarizing element was obtained in this order. As a result of the same X-ray diffraction measurement using the X-ray diffractometer X'Pert PRO MPD (manufactured by Spectris Co., Ltd.) for this polarizing element, the peak half-value width (FWHM) was around 2θ = 20.2 °. ) = A sharp diffraction peak (Bragg peak) of about 0.17 ° was obtained. The ordered period (d) obtained from the peak position was about 4.4 Å, and it was confirmed that a structure reflecting the higher-order smectic phase was formed.

(4) Preparation of First Resin Layer After corona treatment is applied to the surface of the polarizing element of the laminate B obtained as described above, the resin layer forming composition (A) is used as the first curable composition. Reapply by the bar coat method (# 2 30 mm / s), and use a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Denki Co., Ltd.) to apply ultraviolet rays with an exposure of 500 mJ / cm ² (365 nm standard) to the resin. By irradiating the coating layer of the layer-forming composition, a laminate C having a release film, a second resin layer, a photoalignment film, a polarizing element, and a first resin layer was obtained in this order. Then, the release film was peeled off to obtain a polarizing film having a second resin layer, a photoalignment film, a polarizing element, and a first resin layer in this order. The thickness of the first resin layer was 1.5 μm.

[Examples 1 to 9 (Example 9 is a reference example) and Comparative Examples 1 and 2]
As shown in Table 2, the same as in Example 1 except that the resin layer forming compositions (B) to (K) were used instead of the resin layer forming composition (A), respectively. The polarizing films of Examples 1 to 9 and Comparative Examples 1 and 2 were obtained.

[Comparative Example 3]
(1) Preparation of Second Resin Layer The release-treated surface of the release-treated polyethylene terephthalate film (SP-PLR382050 manufactured by Lintec Co., Ltd.) (release film) is subjected to corona treatment and then has second curability. A second resin layer was formed on the surface of the release film by applying the resin layer forming composition (L) as the composition by the bar coating method (# 30 30 mm / s) and drying at 100 ° C. for 1 minute. A release film with a resin layer was obtained. The thickness of the second resin layer was 1.5 μm.

(2) Preparation of Photo-Alignment Film Next, after corona treatment is applied to the surface of the second resin layer of the release film with a resin layer, a composition for forming a photo-alignment film is applied and dried at 120 ° C. A dry film was obtained. The dried film was irradiated with polarized UV to form a photoalignment film, and a laminate K having a release film, a second resin layer, and a photoalignment film in this order was obtained. The polarized UV treatment was carried out using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio, Inc.) under the condition that the intensity measured at a wavelength of 365 nm was 100 mJ. The thickness of the photoalignment film was 100 nm.

(3) Preparation of Polarizer A composition for forming a polarizing film is applied to the surface of the photoalignment film of the laminate K obtained as described above by the bar coating method (# 9 30 mm / s), and dried at 120 ° C. The polymerizable liquid crystal compound was phase-transferred to the liquid phase by heating and drying in an oven for 1 minute, and then cooled to room temperature to phase-transfer the polymerizable liquid crystal compound to the smectic liquid crystal state. Next, using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Denki Co., Ltd.), the layer formed from the composition for forming a polarizing film is irradiated with ultraviolet rays having an exposure amount of 1000 mJ / cm ² (365 nm standard). Thereby, the polymerizable liquid crystal compound contained in the dry film was polymerized while maintaining the smectic liquid crystal state of the polymerizable liquid crystal compound, and a substituent (polarizing film) was formed from the dry film. The thickness of the stator was 2.3 μm. In this way, a laminate L having a release film, a second resin layer, a photoalignment film, and a polarizing element was obtained in this order.

(4) Preparation of First Resin Layer After corona treatment is applied to the surface of the polarizing element of the laminate L obtained as described above, the resin layer forming composition (L) is used as the first curable composition. It is reapplied by the bar coating method (# 30 30 mm / s) and dried at 100 ° C. for 1 minute to have a release film, a second resin layer, a photoalignment film, a polarizing element, and a first resin layer in this order. A laminate M was obtained. Then, the release film was peeled off to obtain a polarizing film having a second resin layer, a photoalignment film, a polarizing element, and a first resin layer in this order. The thickness of the first resin layer was 1.5 μm.

The polarizing films obtained in Examples 1 to 9 and Comparative Examples 1 to 3 were evaluated for adhesion and heat resistance. The results are shown in Table 2.

Flexibility was evaluated for the polarizing films obtained in Examples 5 and 8. As a result, no cracks occurred in both, and the evaluation was ◯.

As shown in Table 2, the polarizing films obtained in Examples 1 to 9 and Comparative Examples 1 to 3 had an adhesion evaluation result of ◯, and it was confirmed that the adhesion between layers was excellent. It was also confirmed that ΔTy and ΔPy, which are the amounts of change in Ty and Py before and after the heat resistance test, were close to 0, and the heat resistance was excellent. On the other hand, the polarizing films obtained in Comparative Examples 1 to 3 have an adhesion evaluation result of x, and are inferior in adhesion.
Further, it was found that the polarizing films obtained in Examples 5 and 8 had a flexibility evaluation of ◯, and had excellent flexibility in addition to adhesion and heat resistance.

1,11 ... Polarizing film with front plate,
2 ... Polarizing film 3 ... Front plate 4 ... First resin layer 5 ... Polarizer 6 ... Alignment film 7 ... Second resin layer 8, 12 ... Polarizing plate with front plate 9, 13 ... Polarizing plate 10 ... Phase difference film

Claims (7)

A polarizing film in which a first resin layer, a polarizing element, an alignment film, and a second resin layer are laminated adjacent to each other in this order.
The first resin layer is a cured product of the first curable composition containing a (meth) acrylic compound.
The polarizing element is a cured product of a composition for forming a polarizing element containing a polymerizable liquid crystal compound having a (meth) acryloyl group and a dichroic dye.
The alignment film is a cured product of a composition for forming an alignment film containing a (meth) acrylic compound.
The second resin layer is a cured product of the second curable composition containing a (meth) acrylic compound.
At least one of the first curable composition and the second curable composition is a polarizing film containing a urethane (meth) acrylate compound and a polyfunctional (meth) acrylate compound as the (meth) acrylic compound . The polarizing film according to claim 1, wherein at least one of the first curable composition and the second curable composition contains a radical polymerization initiator. The polarizing film according to claim 1 or 2 , wherein the urethane (meth) acrylate compound has a (meth) acryloyl group number of 15 × 10 ^-4 or more per unit molecular weight. The polarizing film according to any one of claims 1 to 3, wherein the polyfunctional (meth) acrylate compound has 6 or more (meth) acryloyl groups. The polyfunctional (meth) acrylate compound has a branched structure, and the number of atoms in the chain connecting the (meth) acryloyl group closest to the (meth) acryloyl group in the branched structure is 3 or less. The polarizing film according to any one of claims 1 to 4 . It includes a step of applying or superimposing the first curable composition on the polarizing element surface of the laminate in which the second resin layer, the alignment film, and the polarizing element are laminated in this order, and curing the first curable composition. , The method for producing a polarizing film according to any one of claims 1 to 5 . The first curable composition formed on the release film and the polarizing element surface of the laminate in which the second resin layer, the alignment film, and the polarizing element are laminated in this order are overlapped and activated from the release film side. By irradiating the first curable composition with energy rays to cure the first curable composition, a laminate in which the release film, the first resin layer, the polarizing element, the alignment film, and the second resin layer are laminated in this order is obtained. The method for producing a polarizing film according to any one of claims 1 to 5 , which comprises a step of peeling the release film from the laminate.

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