JP2020023153A - Laminate - Google Patents

Abstract

To provide a stretchable laminate that, when stretched, neither shows a change in optical characteristics nor causes a poor appearance.SOLUTION: This stretchable laminate comprises a base material layer and a polarization layer, the base material having a moisture percentage of at most 5.0%, and satisfying formula (1): |E-E|/|E+E|≤0.25. [In the formula, Eand Erepresent a tensile elastic modulus in the absorption axis direction and in the transmission axis direction, respectively.]SELECTED DRAWING: None

Description

  The present invention relates to a laminate composed of a base material layer and a polarizing layer.

  Patent Document 1 proposes a stretchable display device. Patent Document 2 proposes a polarizing plate that can be subjected to hot bending.

Korean Published Patent No. 10-2016-0090977 Japanese Patent No. 5633228

  An object of the present invention is to provide a stretchable laminate that does not significantly change optical properties such as luminosity correction single transmittance and luminosity correction polarization degree even when stretched, and does not cause appearance defects such as haze and cracks. That is.

The present invention provides the following laminate.
[1] A stretchable laminate comprising a substrate layer and a polarizing layer, wherein the moisture content of the substrate layer is 5.0% or less, and satisfies the following formula (1). .
| E _A −E _T | / | E _A + E _T | ≦ 0.25 (1)
Wherein each of E _A and E _T, showing a tensile modulus in the absorption axis direction and the transmission axis direction]
[2] The laminate according to [1], wherein the total haze value is 3% or less.
[3] The laminate according to [1] or [2], wherein the thickness of the polarizing layer is 0.5 μm to 10 μm.
[4] The laminate according to any one of [1] to [3], wherein the polarizing layer is formed of a cured product of a polarizing layer forming composition including a polymerizable liquid crystal compound and a dichroic dye. body.
[5] The content according to any one of [1] to [4], wherein the content of the dichroic dye in the polarizing layer is 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. The laminate according to the above.
[6] The laminate according to any one of [1] to [5], further including an adhesive layer on the polarizing layer side.
[7] The laminate according to [6], having a retardation layer laminated via the pressure-sensitive adhesive layer.
[8] A display device, wherein the laminate according to any one of [1] to [7] is bonded to an image display element.

  According to one embodiment of the present invention, even when stretched, a stretchable laminate in which optical properties such as luminosity-corrected single transmittance and luminosity-corrected polarization degree do not significantly change, and appearance defects such as haze and cracks do not occur. Can be provided.

FIG. 1 is a schematic cross-sectional view of a laminate according to one embodiment of the present invention.

  Hereinafter, a laminated body according to one embodiment of the present invention (hereinafter, also simply referred to as a “laminated body”) will be described with reference to the drawings.

<Laminate>
FIG. 1 is a schematic cross-sectional view of a laminate according to one embodiment of the present invention. The laminate 10 is a stretchable laminate including a base material layer 11 and a polarizing layer 12. Stretchable means that when the laminate 10 is pulled in the direction of the absorption axis and / or the direction of the transmission axis, it can be stretched without breaking. The direction of the absorption axis refers to the case where the polymerizable liquid crystal compound is cured in a state where the dichroic dye and the polymerizable liquid crystal compound, which will be described later, constituting the polarizing layer 12 are horizontally aligned with respect to the surface of the base material layer. It refers to the orientation direction of the dichroic dye and the polymerizable liquid crystal compound when the dichroic dye is horizontally aligned with the substrate layer surface. The transmission axis direction refers to the case where the polymerizable liquid crystal compound is cured in a state where the dichroic dye and the polymerizable liquid crystal compound, which will be described later, constituting the polarizing layer 12 are horizontally aligned with respect to the base material layer surface, and indicates the liquid crystallinity. When the dichroic dye is horizontally oriented with respect to the substrate layer surface, it refers to a direction horizontal to the substrate layer surface and perpendicular to the orientation direction. The orientation state of the polarizing layer can be confirmed by observation with a polarizing microscope. A laminate sample is inserted in a direction of about 45 ° between crossed Nicols with a polarizing microscope, and observation is performed in a state of light leakage. When the liquid crystal molecules are vertically aligned, no light leakage occurs and a dark field state is observed. When the liquid crystal molecules are horizontally aligned, light leakage occurs and the light field state is observed.

  The laminate 10 may have elongation at break in both the absorption axis direction and the transmission axis direction of, for example, 5% or more. When the elongation at break in both the absorption axis direction and the transmission axis direction is 5% or more, sufficient stretchability tends to be easily obtained. The laminate 10 preferably has an elongation at break in the absorption axis direction and the transmission axis direction of preferably 5% to 20%, more preferably 5% to 15%. When the elongation at break in both the absorption axis direction and the transmission axis direction is 5% to 20%, sufficient stretchability is easily obtained, and a change in optical characteristics and appearance defects such as haze and cracks are less likely to occur. There is a tendency. The elongation at break in the absorption axis direction and the permeation axis direction is the elongation at the time when the laminate is broken in the tensile test when the laminate is pulled in the absorption axis direction or the permeation axis direction. For example, according to JIS K7161, UTM ( The measurement can be performed using Universal Testing Machine, Autograph AG-X, Shimadzu Corporation. As the elongation at break, a value at normal temperature (23 ° C.) can be adopted.

Laminate 10, when the tensile elastic modulus in the absorption axis direction and the transmission axis direction is respectively E _A and E _T, satisfies the following equation (1).
| E _A −E _T | / | E _A + E _T | ≦ 0.25 (1)
When the laminated body 10 does not satisfy the formula (1), when the laminated body 10 is pulled, there is a tendency that optical properties change, breakage, or appearance defects such as haze and cracks easily occur. . As a reason for this, it is presumed that the laminate has a certain degree of tensile elasticity isotropically, so that the optical properties of the laminate are maintained even when the laminate is stretched. There is no limitation to this estimation. The tensile modulus can be measured according to the measuring method described in the section of Examples described later. The lower limit of | E _A −E _T | / | E _A + E _T | may be, for example, 0.01. The value at normal temperature (temperature of 23 ° C.) can be adopted as the tensile modulus.

  The laminate 10 is adjusted to satisfy the formula (1), for example, by adjusting the thicknesses of the base layer 11, the polarizing layer 12, and the alignment layer, selecting a material to be used for the base layer, and dichroic properties for forming the polarizing layer. Selection of dyes and polymerizable liquid crystal compounds and adjustment of their composition ratio, selection of raw materials used for the composition for forming an alignment layer and adjustment of the composition ratio, conditions for forming a polarizing layer and an alignment layer, such as coating, drying and It can be produced by combining polymerization conditions and the like. In particular, since the tensile modulus of the laminate is related to the tensile modulus of the substrate layer, it is preferable to use a substrate layer having an elongation of 5% or more.

The laminate 10 preferably satisfies the following expression (2).
| E _A −E _T | / | E _A + E _T | ≦ 0.20 (2)

Both tensile modulus _{E A} and _{E T,} may be, for example 1MPa～30,000MPa, preferably 10MPa～20,000MPa, more preferably 50MPa～15,000MPa. If the tensile modulus _{E A} and _{E T} are 50MPa~15,000MPa both, it tends to be difficult to break even when stretched laminate 10.

  The laminated body 10 may have a total haze value of, for example, 3% or less. When the total haze value is 3% or less, it can be suitably used for a display device. The laminate 10 has a total haze value of preferably 2.8% or less, more preferably 2.5% or less. When the total haze value is 3% or less, when the laminate 10 is used for a display device, the visibility tends to be easily improved. The total haze value can be measured according to the method described in the section of Examples described later. On the other hand, the total haze value is usually 0.1% or more. The total haze value can be measured according to the measurement method described in the section of Examples below.

  In the laminate 10, the difference (ΔH) between the total haze values before and after stretching may be, for example, 1.5% or less, preferably 1.2% or less, and more preferably 1% or less. In a preferred embodiment, the laminate 10 may have a difference (ΔH) between the total haze value before stretching and after 5% stretching of, for example, 1.5% or less, preferably 1.2% or less, more preferably 1% or less. % Or less. In a more preferred embodiment, the laminate 10 may have a difference (ΔH) between the total haze values before and after the 10% stretching of, for example, 1.5% or less, preferably 1.2% or less, more preferably 1% or less.

The polarization performance of the laminate 10 can be measured using a spectrophotometer. For example, the transmittance (T1) in the transmission axis direction (perpendicular to the orientation) and the transmittance (T2) in the absorption axis direction (the same orientation) in the wavelength range of 380 nm to 780 nm, which is visible light, are measured by a polarizer. It can be measured by the double beam method using a device with a folder attached. The polarization performance in the visible light range is calculated by calculating the single transmittance and the degree of polarization at each wavelength using the following formulas (3) and (4), and further viewing with a 2-degree visual field (C light source) according to JIS Z8701. By performing the sensitivity correction, it is possible to calculate the visibility correction single transmittance (Ty) and the visibility correction polarization degree (Py).
Single transmittance (%) = (T1 + T2) / 2 Equation (3)
Degree of polarization (%) = (T1−T2) / (T1 + T2) × 100 Equation (4)

  The laminate 10 may have a visibility correction single transmittance of, for example, 30% or more, preferably 35% or more, and more preferably 38% or more. On the other hand, the laminated body 10 usually has a visibility correction single transmittance of 70% or less. The luminosity-corrected single transmittance can be measured according to the method described in the section of Examples described later.

  The laminate 10 may have, for example, a difference (ΔT) in luminosity-corrected single transmittance before and after stretching in the absorption axis direction and the transmission axis direction of 1.5% or less, and preferably 1.2% or less, for example. More preferably, it is 1% or less. In a preferred embodiment, the laminate 10 has a difference (ΔT) in luminosity-corrected single transmittance before stretching and after stretching by 5% in the absorption axis direction and the transmission axis direction, for example, of 1.5% or less, respectively. And preferably 1.2% or less, more preferably 1% or less. In a more preferred embodiment, the laminated body 10 has a difference (ΔT) in luminosity-corrected single transmittance value before stretching and after 10% stretching in the absorption axis direction and the transmission axis direction of, for example, 1.5% or less. And preferably 1.2% or less, more preferably 1% or less.

  The laminate 10 may have a visibility correction polarization degree of, for example, 80% or more, preferably 85% or more, and more preferably 90% or more. On the other hand, the laminate 10 has a visibility correction polarization degree of usually 100% or less, and may be 99.99% or less. The visibility correction polarization degree can be measured according to the method described in the section of Examples described later.

  In the laminate 10, the difference (ΔP) between the visibility correction polarization degrees before and after stretching in the absorption axis direction and the transmission axis direction may be, for example, not more than 3%, preferably not more than 2.5%, more preferably not more than 2.5%. 2% or less. In a preferred embodiment, the laminate 10 may have a difference (ΔP) in the visibility correction polarization degree before stretching and after stretching by 5% in the absorption axis direction and the transmission axis direction, for example, of 3% or less, respectively. Preferably it is 2.5% or less, more preferably 2% or less. In a more preferred embodiment, the difference (ΔP) in the luminosity correction polarization degree between before the stretching and after the 10% stretching in the absorption axis direction and the transmission axis direction may be, for example, 3% or less. , Preferably 2.5% or less, more preferably 2% or less.

  The thickness of the laminate 10 may be, for example, 25 μm to 1000 μm, preferably 30 μm to 500 μm, and more preferably 35 μm to 100 μm. When the thickness of the laminate 10 is 25 μm to 1000 μm, the display device tends to be thinner.

  Hereinafter, each layer constituting the laminate 10 will be described.

[Base material layer]
The base material layer 11 may be composed of, for example, a resin film, and may preferably be composed of a transparent resin film. The resin film may be a long roll-shaped resin film or a sheet-like resin film. A long roll-shaped resin film is preferable in that it can be manufactured continuously.

  Examples of the resin constituting the resin film include polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate; polyacrylate; triacetyl cellulose, diacetyl cellulose; Plastics such as cellulose esters such as cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyether sulfone; polyether ketone; polyphenylene sulfide; and polyphenylene oxide. Among them, cyclic olefin resins, cellulose esters and polyimides are preferred.

  Examples of typical commercially available cyclic olefin resins include “Topas” (registered trademark) (manufactured by Ticona (Germany)), “ARTON” (registered trademark) (manufactured by JSR Corporation), and “ZEONOR”. (Registered trademark), "ZEONEX" (registered trademark) (all manufactured by Zeon Corporation), "Apel" (registered trademark) (made by Mitsui Chemicals, Inc.) and the like. Such a cyclic olefin-based resin can be formed into a resin film by a known method such as a solvent casting method or a melt extrusion method. A commercially available cyclic olefin-based resin film can also be used. Examples of typical commercial products of the cyclic olefin-based resin film include “ESCINA” (registered trademark), “SCA40” (registered trademark) (all manufactured by Sekisui Chemical Co., Ltd.), and “ZEONOR FILM” (registered trademark) ( Optes Co., Ltd.) and "ARTON FILM" (registered trademark) (manufactured by JSR Corporation).

  Examples of typical commercially available resin films composed of cellulose ester include "Fujitac Film" (manufactured by Fuji Photo Film Co., Ltd.); "KC8UX2M", "KC8UY" and "KC4UY" (Konica Minolta Opto, Inc.) Manufactured by a company).

  The moisture content of the base material layer 11 is 5.0% or less, and preferably 3.0% or less. The moisture content of the base material layer 11 can be 0.0% or more. When the moisture content of the base material layer 11 is 5.0% or less, the uniformity of the alignment direction of the polymerizable liquid crystal and the dichroic dye tends to increase when the polarizing layer 12 is formed. In particular, when the laminate 10 is stretched, the unevenness of the optical properties is easily recognized, and even after the stretching, the polarizing layer can easily maintain good optical properties. The moisture content of the base material layer is measured by a method described in Examples described later.

  The thickness of the resin film is preferably thinner from the viewpoint of making the laminate 10 thinner, but if it is too thin, it tends to be difficult to secure impact resistance. The thickness of the resin film may be, for example, 10 to 200 μm, preferably 15 to 150 μm, and more preferably 20 to 100 μm.

  The base material layer 11 may have a hard coat layer, an antireflection layer, or an antistatic layer on at least one surface. In the base material layer 11, a hard coat layer, an antireflection layer, an antistatic layer, and the like may be formed only on the surface on which the polarizing layer 12 is not formed. In the base material layer 11, a hard coat layer, an antireflection layer, an antistatic layer, and the like may be formed only on the surface on which the polarizing layer 12 is formed. As the substrate layer 11, a window film described later can be used.

[Polarizing layer]
The polarizing layer 12 is a layer composed of a cured product of a composition containing one or more polymerizable liquid crystal compounds (hereinafter also referred to as polymerizable liquid crystal (a)) and a dichroic dye, or exhibits one or more liquid crystallinities. It is preferably a layer composed of a cured product of a composition containing a dichroic dye. When the polarizing layer 12 has polarization characteristics in the plane direction of the laminate 10, the dichroic dye and the polymerizable liquid crystal (a) cure the polymerizable liquid crystal (a) in a state of being horizontally aligned with the plane of the laminate 10. Alternatively, the dichroic dye exhibiting liquid crystallinity may be horizontally oriented with respect to the plane of the laminate 10, and when the polarizing layer 12 has polarization characteristics in the thickness direction of the laminate 10, When the polymerizable liquid crystal (a) is cured in a normal state in which the liquid crystal (a) is vertically aligned with the plane of the laminate 10 or the dichroic dye exhibiting liquid crystallinity is vertically aligned with the plane of the laminate 10 Good. The polarizing layer 12 is preferably a coating layer, for example, of a composition for forming a polarizing layer containing one or more polymerizable liquid crystals (a) and a dichroic dye [hereinafter also referred to as composition (A)]. It may be a cured product.

  The thickness of the polarizing layer 12 may be, for example, 0.5 to 10 μm, preferably 1 to 8 μm, and more preferably 1.5 to 5 μm.

  The polarizing layer 12 can be formed by, for example, applying the composition (A) on the base layer 11 or an alignment layer described below, and polymerizing the polymerizable liquid crystal (a) in the obtained coating film. .

(Polymerizable liquid crystal)
The polymerizable liquid crystal (a) is a compound having a polymerizable group and having liquid crystallinity. The polymerizable group means a group involved in a polymerization reaction, and is preferably a photopolymerizable group. Here, the photopolymerizable group refers to a group that can participate in a polymerization reaction by an active radical, an acid, or the like generated from a photopolymerization initiator described below. Examples of the polymerizable group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxiranyl group, and an oxetanyl group. Among them, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group and an oxetanyl group are preferred, and an acryloyloxy group is more preferred. The liquid crystal may be a thermotropic liquid crystal or a lyotropic liquid crystal, but when mixed with a dichroic dye described later, a thermotropic liquid crystal is preferable.

  When the polymerizable liquid crystal (a) is a thermotropic liquid crystal, it may be a thermotropic liquid crystal compound showing a nematic liquid crystal phase or a thermotropic liquid crystal compound showing a smectic liquid crystal phase. When a polarizing function is exhibited as a cured film by a polymerization reaction, the liquid crystal state of the polymerizable liquid crystal (a) is preferably a smectic phase, and a higher-order smectic phase is more preferable from the viewpoint of high performance. . Among them, a higher smectic liquid crystal compound forming a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, a smectic K phase or a smectic L phase is preferred. Higher order smectic liquid crystal compounds that form a smectic B phase, a smectic F phase or a smectic I phase are more preferable. When the liquid crystal phase formed by the polymerizable liquid crystal (a) is such a higher smectic phase, a polarizing layer having higher polarization performance can be manufactured. Further, such a polarizing layer having a high polarization performance can obtain a Bragg peak derived from a higher-order structure such as a hexatic phase or a crystal phase in X-ray diffraction measurement. The Bragg peak is a peak derived from a periodic structure of molecular orientation, and a film having a periodic interval of 3 to 6 ° can be obtained. The polarizing layer of the present invention preferably contains a polymer of the polymerizable liquid crystal (a) obtained by polymerizing the polymerizable liquid crystal (a) in a smectic phase, from the viewpoint of obtaining higher polarization characteristics.

  Specific examples of such a compound include a compound represented by the following formula (I) [hereinafter, also referred to as compound (I)]. The polymerizable liquid crystal (a) may be used alone or in combination of two or more.

U ¹ -V ¹ -W ¹ -X ¹ -Y ¹ -X ² -Y ² -X ³ -W ² -V ² -U ² (I)
[In the formula (A),
X ¹ , X ² and X ³ each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein the divalent aromatic group or the divalent alicyclic group The hydrogen atom contained in the hydrocarbon 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. The carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom. However, at least one of X ¹ , X ² and X ³ is a 1,4-phenylene group optionally having a substituent or a cyclohexane-1,4-diyl group optionally having a substituent. It is.
Y ¹ , Y ² , W ¹ and W ² are each independently a single bond or a divalent linking group.
V ¹ and V ² independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH _2- constituting the alkanediyl group is -O-,- It may be replaced by S- or -NH-.
U ¹ and U ² independently represent a polymerizable group or a hydrogen atom, at least one of which is a polymerizable group. ]

In the compound (I), at least one of X ¹ , X ² and X ³ is a 1,4-phenylene group which may have a substituent or a cyclohexane-1 which may have a substituent. , 4-diyl group. In particular, X ¹ and X ³ are preferably a cyclohexane-1,4-diyl group which may have a substituent, and the cyclohexane-1,4-diyl group is preferably trans-cyclohexane- More preferably, it is a 1,4-diyl group. When it contains a structure of a trans-cyclohexane-1,4-diyl group, smectic liquid crystallinity tends to be easily exhibited. Further, as a substituent optionally contained in the optionally substituted 1,4-phenylene group or cyclohexane-1,4-diyl group, a methyl group, Examples thereof include an alkyl group having 1 to 4 carbon atoms such as an ethyl group and a butyl group, a cyano group, and a halogen atom such as a chlorine atom and a fluorine atom. Preferably it is unsubstituted.

Y ¹ and ^{Y 2,} independently of one another, a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - COO -, - OCO -, - N = N -, - CR a = CR b -, - C≡C— or —CR ^a ＮN— is preferred, and R ^a and R ^b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Y ¹ and Y ² are more preferably —CH ₂ CH ₂ —, —COO—, —OCO— or a single bond, and all of X ¹ , X ² and X ³ represent a cyclohexane-1,4-diyl group. If not included, it is more preferable that Y ¹ and Y ² are different from each other. When Y ¹ and Y ² are different from each other, the smectic liquid crystal tends to be easily developed.

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

The alkanediyl group having 1 to 20 carbon atoms represented by V ¹ and ^{V 2,} methylene group, ethylene group, propane-1,3-diyl, butane-1,3-diyl group, butane-1,4 -Diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane -1,14-diyl group and icosane-1,20-diyl group. V ¹ and V ² are preferably an alkanediyl group having 2 to 12 carbon atoms, and more preferably a straight-chain alkanediyl group having 6 to 12 carbon atoms. By using a linear alkanediyl group having 6 to 12 carbon atoms, crystallinity is improved, and smectic liquid crystallinity tends to be easily exhibited.

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

Both U ¹ and U ² are preferably a polymerizable group, and more preferably both are photopolymerizable groups. Since a polymerizable liquid crystal compound having a photopolymerizable group can be polymerized under a lower temperature condition than a thermopolymerizable group, it is advantageous in that a liquid crystal can form a polymer with a higher degree of order.

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

  Examples of such a polymerizable liquid crystal compound include the following.

  Among the exemplified compounds, the formulas (1-2), (1-3), (1-4), (1-6), (1-7), (1-8), and (1-8) At least one selected from the group consisting of the compounds represented by (1-13), Formula (1-14) and Formula (1-15) is preferable.

(Dichroic dye)
The dichroic dye refers to a dye having a property that the absorbance in the major axis direction of the molecule is different from the absorbance in the minor axis direction. The dichroic dye preferably has the property of absorbing visible light, and more preferably has a maximum absorption wavelength (λMAX) in the range of 380 to 680 nm. Such dichroic dyes include, for example, acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes and anthraquinone dyes, among which azo dyes are preferred. Examples of the azo dye include a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye, and a stilbeneazo dye, and are preferably a bisazo dye and a trisazo dye. The dichroic dyes may be used alone or in combination, but in order to obtain absorption in the entire visible light range, it is preferable to combine three or more dichroic dyes, and it is more preferable to combine three or more azo dyes. preferable.

Examples of the azo dye include a compound represented by the formula (II) (hereinafter, also referred to as “compound (II)”).
T ¹ -A ¹ (−N = N−A ² ) _p− N = N−A ³ −T ² (II)
[In the formula (II),
A ^1, A ² and A ³ are each independently a 1,4-phenylene group which may have a substituent, a naphthalene-1,4-diyl group or a divalent group which may have a substituent Wherein T ¹ and T ² are an electron-withdrawing group or an electron-emitting group, and are located at substantially 180 ° with respect to the azo bond plane. p represents an integer of 0 to 4. When p is 2 or more, each A ² may be the same or different. The -N = N- bond may be replaced with a -C = C-, -COO-, -NHCO-, -N = CH- bond within a range showing absorption in the visible region. ]

Examples of the substituents that the 1,4-phenylene group, naphthalene-1,4-diyl group and divalent heterocyclic group optionally have in A ^1, A ² and A ³ include a methyl group, an ethyl group and a butyl group. C1-C4 alkyl group; C1-C4 alkoxy group such as methoxy group, ethoxy group and butoxy group; C1-C4 fluorinated alkyl group such as trifluoromethyl group; cyano group; A halogen atom such as a chlorine atom or a fluorine atom; a substituted or unsubstituted amino group such as an amino group, a diethylamino group and a pyrrolidino group (a substituted amino group is an amino group having one or two alkyl groups having 1 to 6 carbon atoms); Or an amino group in which two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 8 carbon atoms. Is H _2.) It can be mentioned. In addition, as a C1-C6 alkyl group, a methyl group, an ethyl group, a hexyl group, etc. are mentioned. Examples of the alkanediyl group having 2 to 8 carbon atoms include 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 and the like. For inclusion in a highly ordered liquid crystal structure such as a smectic liquid crystal, A ¹ and A ² and A ³ are unsubstituted or 1,4-phenylene groups in which hydrogen is substituted by a methyl group or a methoxy group, or divalent. Is preferable, and p is preferably 0 or 1. Above all, p is 1 and at least two of the three structures A ^1, A ² and A ³ are 1,4-phenylene groups in that both of the simplicity of molecular synthesis and high performance are obtained. More preferred.

Examples of the divalent heterocyclic group include groups obtained by removing two hydrogen atoms from quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole, and benzoxazole. When A ² is a divalent heterocyclic group, a structure in which the molecular bonding angle is substantially 180 ° is preferable. Specifically, benzothiazole, benzimidazole, and benzoxazole in which two 5-membered rings are fused The structure is more preferred.

T ¹ and T ² are an electron-withdrawing group or an electron-emitting group, and preferably have different structures. T ¹ is an electron-withdrawing group and a T ² electron-emitting group, or T ¹ is an electron-emitting group and a T ² electron-withdrawing group. Is more preferable. Specifically, T ¹ and T ² are each independently one of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms or An amino group having two amino groups, or an amino group in which two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 8 carbon atoms, or a trifluoromethyl group is preferable, and a highly ordered group such as a smectic liquid crystal is preferable. In order to be included in the liquid crystal structure, it is necessary that the structure has a smaller excluded volume of molecules. Therefore, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and 1 carbon atoms. An amino group having one or two alkyl groups of 6 to 6, or an amino group in which two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 8 carbon atoms is preferable.

Examples of such azo dyes include the following.

In the formulas (2-1) to (2-6),
B ^{1 to} B ²⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, a nitro group, a substituted or unsubstituted amino group (substituted amino group and The unsubstituted amino group is as defined above), a chlorine atom or a trifluoromethyl group. From the viewpoint of high polarization performance is ^{obtained, B 2, B 6, B} 9, B 14, B 18, B 19 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
n1 to n4 each independently represent an integer of 0 to 3.
If n1 is 2 or more, to each of a plurality of B ² may be the same or different,
When n2 is 2 or more, a plurality of B ⁶ may be the same or different,
When n3 is 2 or more, a plurality of B ⁹ may be the same or different,
When n4 is 2 or more, each of the plurality of B ¹⁴ may be the same or different.

  As the anthraquinone dye, a compound represented by the formula (2-7) is preferable.

[In the formula (2-7),
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.
^Rx represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]

  As the oxazine dye, a compound represented by the formula (2-8) is preferable.

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

  As the acridine dye, a compound represented by the formula (2-9) is preferable.

[In the formula (2-9),
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.
^Rx represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]

In the formulas (2-7), (2-8) and (2-9), the alkyl group having 1 to 4 carbon atoms represented by R ^x includes a methyl group, an ethyl group, a propyl group, and a butyl group. , A pentyl group and a hexyl group, and the aryl group having 6 to 12 carbon atoms includes a phenyl group, a toluyl group, a xylyl group, and a naphthyl group.

  As the cyanine dye, a compound represented by the formula (2-10) and a compound represented by the formula (2-11) are preferable.

ｎ５は１〜３の整数を表す。］ [In the formula (2-10),
D ¹ and D ² each independently represent a group represented by any of formulas (2-10a) to (2-10d).

n5 represents an integer of 1 to 3. ]

ｎ６は１〜３の整数を表す。］ [In the formula (2-11),
D ³ and D ⁴ each independently represent a group represented by any of formulas (2-11a) to (2-11h).

n6 represents an integer of 1 to 3. ]

  The content of the dichroic dye (in the case of including a plurality of types) is usually 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal (a) from the viewpoint of obtaining good light absorption characteristics. Parts, preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass. When the content of the dichroic dye is less than this range, light absorption becomes insufficient, and sufficient polarization performance cannot be obtained. When the content is more than this range, the alignment of liquid crystal molecules may be inhibited.

(Orientation layer)
The laminate 10 may have an alignment layer between the base layer 11 and the polarizing layer 12. The alignment layer has an alignment regulating force for aligning the polymerizable liquid crystal constituting the polarizing layer 12 formed on the base material layer 11 in a desired direction.

  The alignment layer facilitates liquid crystal alignment of the polymerizable liquid crystal. The state of liquid crystal alignment such as horizontal alignment, vertical alignment, hybrid alignment, and tilt alignment changes depending on the properties of the alignment layer and the polymerizable liquid crystal, and a combination thereof can be arbitrarily selected. For example, if the alignment layer is a material that develops horizontal alignment as an alignment regulating force, the polymerizable liquid crystal can form horizontal alignment or hybrid alignment, and if it is a material that develops vertical alignment, the polymerizable liquid crystal becomes vertical. An oriented or tilted orientation can be formed. Expressions such as horizontal and vertical indicate the direction of the major axis of the aligned polymerizable liquid crystal with respect to the plane of the polarizing layer 12. For example, vertical alignment means having the major axis of the polymerizable liquid crystal aligned in a direction perpendicular to the plane of the polarizing layer 12. Here, “perpendicular” means 90 ° ± 20 ° with respect to the plane of the polarizing layer 12.

  The alignment regulating force can be arbitrarily adjusted depending on the surface state and the rubbing condition when the alignment layer is formed from the alignment polymer, and the polarization irradiation condition when the alignment layer is formed from the photo alignment polymer. It can be arbitrarily adjusted by the above method. Further, by selecting physical properties such as surface tension and liquid crystallinity of the polymerizable liquid crystal, the liquid crystal alignment can be controlled.

  The alignment layer formed between the base material layer 11 and the polarizing layer 12 is insoluble in a solvent used when forming the polarizing layer 12 on the alignment layer, and is used for removing the solvent and aligning the liquid crystal. Having heat resistance in the heat treatment for the above is preferred. The alignment layer may be an alignment layer made of an alignment polymer, a photo alignment layer, a groove alignment layer, or the like. Above all, a photo-alignment layer is preferable in that the alignment direction can be easily controlled when applied to a long roll-shaped resin film.

  The thickness of the alignment layer may be, for example, in the range of 10 nm to 5000 nm, preferably in the range of 10 nm to 1000 nm, and more preferably 30 to 300 nm.

  Examples of the orientation polymer used in the orientation layer composed of the orientation polymer include polyamides and gelatins having an amide bond in the molecule, polyimides having an imide bond in the molecule, and polyamic acids, polyvinyl alcohol, and alkyls which are hydrolysates thereof. Modified polyvinyl alcohol, polyacrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, polyacrylic esters and the like can be mentioned. Among them, polyvinyl alcohol is preferable. These orientation polymers may be used alone or in combination of two or more.

  When forming an alignment layer composed of an oriented polymer on a base material layer composed of a resin film, the alignment layer composed of the oriented polymer is usually composed of a composition in which the oriented polymer is dissolved in a solvent (hereinafter, referred to as “orientation layer”). The polymer is also obtained by applying a polymer composition to a resin film and removing the solvent, or by applying an oriented polymer composition to the resin film, removing the solvent and rubbing (rubbing method).

  Examples of the solvent include water; alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve and 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, methyl amyl ketone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Aromatic hydrocarbon solvents such as xylene; nitrile solvents such as acetonitrile; tetrahydrofuran and dimethyl alcohol Ether solvents such as Kishietan; chloroform and chlorinated hydrocarbon solvents such as chlorobenzene; and the like. These solvents may be used alone or in combination of two or more.

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

  A commercially available material for forming an alignment layer may be used as it is as the alignment polymer composition. Examples of commercially available materials for forming an alignment layer include Sanever (registered trademark) (manufactured by Nissan Chemical Industries, Ltd.) and Optmer (registered trademark) (manufactured by JSR Corporation).

  As a method of applying the oriented polymer composition to the resin film, there are a coating method such as a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method and an applicator method, and a printing method such as a flexo method. And other known methods. When the polarizing plate of the present invention is manufactured by a roll-to-roll type continuous manufacturing method, a printing method such as a gravure coating method, a die coating method, or a flexo method is usually employed as the coating method.

  By removing the solvent contained in the oriented polymer composition, a dried film of the oriented polymer is formed. Examples of the method for removing the solvent include a natural drying method, a ventilation drying method, a heating drying method, and a reduced-pressure drying method.

  As a method of rubbing, a rubbing cloth is wound, and on a rotating rubbing roll, the oriented polymer composition formed on the resin film surface by applying the oriented polymer composition to the resin film and annealing it, There is a method of contacting.

  The photo-alignment layer is usually formed by applying a composition containing a polymer or a monomer having a photoreactive group and a solvent (hereinafter, also referred to as a “composition for forming a photo-alignment layer”) to a resin film, and applying polarized light (preferably, polarized light). UV). The photo-alignment layer is more preferable in that the direction of the alignment regulating force can be arbitrarily controlled by selecting the polarization direction of the polarized light to be irradiated.

  The photoreactive group refers to a group that generates liquid crystal alignment ability when irradiated with light. Specifically, it generates a photoreaction that is the origin of the liquid crystal alignment ability, such as an orientation-induced or isomerization reaction, dimerization reaction, photocrosslinking reaction, or photodecomposition reaction of molecules caused by irradiation with light. is there. Among the photoreactive groups, those that cause a dimerization reaction or a photocrosslinking reaction are preferable in terms of excellent orientation. As the photoreactive group capable of causing the above reaction, those having an unsaturated bond, particularly a double bond are preferable, and a carbon-carbon double bond (C = C bond) and a carbon-nitrogen double bond (C = N bond), a nitrogen-nitrogen double bond (N = N bond), and a group having at least one selected from the group consisting of a carbon-oxygen double bond (C = O bond).

  Examples of the photoreactive group having a C ＝ C bond include a vinyl group, a polyene group, a stilbene group, a stilbazol group, a stilbazolium group, a chalcone group, and a cinnamoyl group. A chalcone group and a cinnamoyl group are preferred from the viewpoint that the reactivity is easily controlled and the expression of the alignment regulating force at the time of photoalignment. Examples of the photoreactive group having a C ＝ N bond include groups 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 the like, and a group having azoxybenzene as a basic structure. Examples of the photoreactive group having a C ＝ O bond include a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group. These groups may have a substituent such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, and a halogenated alkyl group. Among them, a photoreactive group capable of causing a photodimerization reaction is preferable, and a cinnamoyl group and a chalcone group are required to have a relatively small amount of polarized light required for photoalignment, and a photoalignment layer excellent in thermal stability and stability over time. It is preferable because it can be easily obtained. Furthermore, as a polymer having a photoreactive group, a polymer having a cinnamoyl group such that the terminal of the side chain of the polymer has a cinnamic acid structure is particularly preferable.

［式（Ａ’）中、
ｎは、０または１を表す。
Ｘ^１は、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−Ｎ＝Ｎ−、−ＣＨ＝ＣＨ−または−ＣＨ_２−を表す。
Ｙ^１は、単結合または−Ｏ−を表す。
Ｒ^１およびＲ^２はそれぞれ独立に、水素原子、炭素数１〜４のアルキル基または炭素数１〜４のアルコキシ基を表す。
＊は、ポリマー主鎖に対する結合手を表す。］ Particularly preferred polymers having a photoreactive group include, for example, a compound represented by the formula (A ′), because the composition for forming a photo-alignment layer is easy to handle and an alignment layer having high durable alignment is easily obtained. (Hereinafter, also referred to as “polymer (A ′)” in some cases).

[In the formula (A '),
n represents 0 or 1.
X ¹ is a single bond, -O -, - COO -, - OCO -, - N = N -, - CH = CH- or -CH ₂ - represents a.
Y ¹ represents a single bond or —O—.
R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
* Represents a bond to the polymer main chain. ]

In the formula (A ′), when X ¹ is any ^one of a single bond, —O—, —COO—, —OCO—, —N ＝ N—, —C ＝ C—, and —CH ₂ —, the polymer (A ′) is particularly preferable because the production of (A ′) itself becomes easy.

In the formula (A ′), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a halogenated alkyl group, a halogenated alkoxy group, a cyano group, a nitro group, an alkyl group, an alkoxy group, an aryl group, an allyloxy group. , An alkoxycarbonyl group, a carboxyl group, a sulfonic acid group, an amino group or a hydroxy group, and the carboxyl group and the sulfonic acid group may form a salt with an alkali metal ion. Among these, R ¹ and R ² are more preferably each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group and a butyl group, and examples of the alkoxy group include a methoxy group, an ethoxy group and a butoxy group.

Although the main chain of the polymer (A ') is not particularly limited, a (meth) acrylate unit represented by the formula (M-1) or (M-2); a formula (M-3) or a formula (M- (Meth) acrylamide unit represented by 4); vinyl ether unit represented by formula (M-5) or (M-6); represented by formula (M-7) or (M-8) ( The polymer (A) has a main chain composed of a unit selected from the group consisting of a methyl) styrene unit and a vinyl ester unit represented by the formula (M-9) or (M-10). It is particularly preferable that the polymer (A ′) has a main chain composed of a unit selected from the group consisting of a (meth) acrylate unit and a (meth) acrylamide unit. Here, the “main chain of the polymer (A ′)” refers to the longest molecular chain among the molecular chains of the polymer (A ′).

  The unit represented by any one of the formulas (M-1) to (M-10) and the group represented by the formula (A ′) may be directly bonded, or may be bonded via an appropriate linking group. It may be. The linking group has a carbonyloxy group (ester bond), an oxygen atom (ether bond), an imide group, a carbonylimino group (amide bond), an iminocarbonylimino group (urethane bond), and a substituent. And a divalent aromatic hydrocarbon group which may have a substituent, and a divalent group obtained by combining these. Specific examples of the divalent aromatic hydrocarbon group which may have a substituent include a phenylene group, a 2-methoxy-1,4-phenylene group, a 3-methoxy-1,4-phenylene group, and a 2-ethoxy group. -1,4-phenylene group, 3-ethoxy-1,4-phenylene group, 2,3,5-trimethoxy-1,4-phenylene group and the like. Among these, the connecting group is preferably an aliphatic hydrocarbon group, and more preferably an alkanediyl group having 1 to 11 carbon atoms which may have a substituent. Examples of the alkanediyl group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, and an undecamethylene group. And these may be linear or branched. Further, such an alkanediyl group may have a substituent. The substituent is, for example, an alkoxy group having 1 to 4 carbon atoms.

［式（Ａ）中、
Ｘ^１、Ｙ^１、Ｒ^１、Ｒ^２およびｎは式（Ａ’）と同義であり、
Ｓ^１は、炭素数１〜１１のアルカンジイル基であり、

で表される構造は、式（Ｍ−１）〜式（Ｍ−１０）のいずれかで表される構造である。］ In other words, as the structural unit having a group represented by the formula (A ′), a structural unit represented by the formula (A) (hereinafter, sometimes also referred to as “structural unit (A)”, Is also referred to as “polymer (A)”).

[In the formula (A),
X ¹ , Y ¹ , R ¹ , R ² and n have the same meanings as in formula (A ′),
S ¹ is an alkanediyl group having 1 to 11 carbon atoms,

Is a structure represented by any of formulas (M-1) to (M-10). ]

The molecular weight of the polymer (A ′) or the polymer (A) is preferably in the range of 1 × 10 ³ to 1 × 10 ⁷ , for example, as a polystyrene-equivalent weight average molecular weight determined by a gel permeation method (GPC method). . However, when the molecular weight is too high, the solubility in a solvent is reduced, and it becomes difficult to prepare the composition for forming an alignment layer, and the sensitivity to light irradiation tends to decrease. Therefore, 1 × 10 ⁴ to 1 × range of 10 ⁶ is preferred.

［式（Ｂ）中、
ｍは、０または１を表す。
Ｓ^２は、炭素数１〜１１のアルカンジイル基を表す。

で表される構造は、式（Ｍ−１）〜式（Ｍ−１０）のいずれかで表される構造である。
Ｘ^２は、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−Ｎ＝Ｎ−、−ＣＨ＝ＣＨ−または−ＣＨ_２−を表す。
Ｙ^２は、単結合または−Ｏ−を表す。
Ｒ^３およびＲ^４はそれぞれ独立に、水素原子、炭素数１〜４のアルキル基または炭素数１〜４のアルコキシ基を表す。］ The polymer (A) may have, in addition to the structural unit (A), a structural unit represented by the formula (B) (hereinafter, sometimes also referred to as “structural unit (B)”).

[In the formula (B),
m represents 0 or 1.
S ² represents an alkanediyl group having 1 to 11 carbon atoms.

Is a structure represented by any of formulas (M-1) to (M-10).
X ² is a single bond, -O -, - COO -, - OCO -, - N = N -, - CH = CH- or -CH ₂ - represents a.
Y ² represents a single bond or —O—.
R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. ]

In the formula (B), specific examples of S ² are the same as the specific examples of S ^{1 in} the formula (A), and specific examples of the alkyl group and the alkoxy group of R ³ and R ⁴ are respectively represented by the formula (A) And the same as the specific examples of R ¹ and R ² in the above.

  When the molar fractions of the structural units (A) and (B) with respect to all structural units of the polymer (A) are p and q, respectively (p + q is 1), 0.25 <p ≦ 1 and It is preferable that the relationship of 0 ≦ q <0.75 is satisfied [here, the case where the polymer (A) has the structural unit (A) and p is 1 means that the polymer (A) has the structural unit (A )). In the polymer comprising the structural unit (A), the structural unit (A) may be one type or two or more types. ]. However, the polymer (A) has structural units other than the structural units (A) and (B) (hereinafter, also referred to as “other structural units” in some cases) as long as the alignment ability by light irradiation is not significantly impaired. It may be.

  The polymer (A) can be produced by (co) polymerizing a monomer for deriving the structural unit (A) and, if necessary, a monomer for deriving the structural unit (B) or another structural unit. The (co) polymerization usually employs an addition polymerization method, and examples of such addition polymerization include chain polymerization such as radical polymerization, anionic polymerization and cationic polymerization, and coordination polymerization. The polymerization conditions are set according to the type and amount of the monomer to be used, so that the above-mentioned preferable molecular weight of the polymer (A) is satisfied.

  As described above, the polymer (A) has been described in detail as a preferable polymer having a photoreactive group. However, the composition for forming an alignment layer includes a polymer having the photoreactive group (preferably, the polymer (A)). Is dissolved in a suitable solvent. Such a solvent can be appropriately selected within a range in which the polymer having the photoreactive group can be dissolved and a composition for forming an alignment layer having an appropriate viscosity can be obtained. Examples thereof include methanol, ethanol, ethylene glycol, and isopropyl alcohol. Alcohol solvents such as propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone or propylene glycol methyl ether acetate and ethyl lactate. Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; pentane Aliphatic hydrocarbon solvents such as hexane and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; N-methylpyrrolidone And amide solvents such as N, N-dimethylformamide, γ-butyrolactone and dimethylacetamide. These solvents may be used alone or in combination of two or more.

  The content of the polymer or monomer having a photoreactive group with respect to the composition for forming a photoalignment layer can be appropriately adjusted depending on the type of the polymer or monomer having the photoreactive group or the thickness of the photoalignment layer to be produced. Is preferably at least 0.2% by mass, and particularly preferably from 0.3 to 10% by mass. In addition, a polymer material such as polyvinyl alcohol or polyimide or a photosensitizer may be contained as long as the properties of the photo alignment layer are not significantly impaired.

  As a method for applying the composition for forming a photo-alignment layer to a resin film, the same method as the method for applying the above-described oriented polymer composition to a resin film can be used. The method for removing the solvent from the applied composition for forming a photo-alignment layer includes, for example, the same method as the method for removing the solvent from the oriented polymer composition.

  In order to irradiate polarized light, the composition for forming a photo-alignment layer applied on a resin film or the like is directly irradiated with polarized light after removing the solvent. May be transmitted. It is particularly preferable that the polarized light is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably in a wavelength region where the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) in the wavelength range of 250 to 400 nm is particularly preferred. Examples of the light source used for the polarized light irradiation include a xenon lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an ultraviolet laser such as KrF and ArF, and the like. preferable. These lamps are preferable because of their high emission intensity of ultraviolet light having a wavelength of 313 nm. Polarized light can be emitted by irradiating the light from the light source through an appropriate polarizer. As such a polarizer, a polarizing filter, a polarizing prism such as Glan-Thompson or Glan-Taylor, or a wire grid type polarizer can be used.

  Note that a plurality of regions (patterns) having different directions of liquid crystal alignment can be formed by performing masking when performing rubbing or irradiation with polarized light.

  The glove (groove) alignment layer is a film having an uneven pattern or a plurality of gloves (grooves) on the film surface. When liquid crystal molecules are placed on a film having a plurality of linear grubs arranged at equal intervals, the liquid crystal molecules are oriented in a direction along the grooves.

  As a method of obtaining the grub alignment layer, a method of forming an uneven pattern by performing exposure and development and rinsing treatment after exposure through an exposure mask having a pattern-shaped slit on the photosensitive polyimide film surface, a plate having grooves on the surface A method of forming a layer of a UV-curable resin before curing on a resin-shaped master, transferring the resin layer to a resin film and then curing, and a method of forming a layer of the UV-curable resin before curing formed on the resin film, A method of pressing a roll-shaped master having grooves of the above to form irregularities and then curing the same. Specific examples include the methods described in JP-A-6-34976 and JP-A-2011-242743.

  In order to obtain alignment with small alignment disorder, the width of the convex portion of the grub alignment layer is preferably 0.05 μm to 5 μm, and the width of the concave portion is preferably 0.1 μm to 5 μm. The depth is preferably 2 μm or less, and more preferably 0.01 μm to 1 μm.

(Other layers)
The laminate 10 may further have an adhesive layer on the polarizing layer 12 side. The pressure-sensitive adhesive layer is used for attaching the laminate 10 to an image display element, a window film, or a touch sensor of a display device, or used for laminating the retardation layer and the laminate. As the adhesive, (meth) acrylic adhesive, styrene adhesive, silicone adhesive, rubber adhesive, urethane adhesive, polyester adhesive, epoxy copolymer adhesive, etc. may be used. it can.

  The laminate 10 may have a retardation layer. Examples of the retardation layer include a λ / 4 plate, a λ / 2 plate, a positive C plate, an inverse wavelength dispersive λ / 4 plate, an inverse wavelength dispersive λ / 2 plate, and a combination thereof. The retardation layer can be produced from a composition containing a transparent resin film or a polymerizable liquid crystal compound forming the base layer. The retardation layer can be produced by applying a composition containing a polymerizable liquid crystal compound on an alignment film and curing the polymerizable liquid crystal compound. The retardation layer may be a layer containing a cured product of the polymerizable liquid crystal compound, and may be a layer further containing an alignment film and a substrate. For the production of the retardation layer, for example, a polymerizable liquid crystal compound exemplified in the above description of the polarizing layer 12, a polymerizable liquid crystal compound described in JP-A-2010-31223 or JP-A-2009-173893, or the like is used. Can be. The alignment film included in the retardation layer may be, for example, the alignment film exemplified in the description of the polarizing layer 12 described above. The base material included in the retardation layer may be, for example, the resin film exemplified in the description of the base material layer 11 described above. The retardation layer can be laminated via the above-mentioned pressure-sensitive adhesive layer.

  The laminate 10 may have a surface treatment layer (coating layer) such as a hard coat layer, an antiglare layer, an antireflection layer, an antistatic layer, and an antifouling layer.

  The laminate 10 may have a window film or a light-shielding pattern (bezel) disposed on the viewing side with respect to the polarizing layer 12. The window film includes a hard coat layer on at least one surface of the transparent base material layer. Window films are not rigid like the existing glass, but have flexible properties. The wiring of the display device can be hidden by the light-shielding pattern so that it is not visible to the user. The laminate 10 may be laminated on a touch sensor.

<Production method of laminate>
The polarizing layer 12 can be formed by applying the composition (A) on the base material layer 11 and, if present, the alignment layer. The composition (A) further includes a polymerization initiator, a leveling agent, and a solvent, in addition to the dichroic dye and the polymerizable liquid crystal compound, and may further include a photosensitizer, a polymerization inhibitor, a leveling agent, and the like.

(Polymerization initiator)
The polymerization initiator is a compound that can initiate a polymerization reaction of a polymerizable liquid crystal or the like. From the viewpoint that the polymerization initiator does not depend on the phase state of the thermotropic liquid crystal, a photopolymerization initiator that generates an active radical by the action of light is preferable.

  Examples of the polymerization initiator include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts and sulfonium salts.

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

  Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenylsulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) ) Benzophenone and 2,4,6-trimethylbenzophenone.

  Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl ) Butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethan-1-one, 2-hydroxy-2-methyl-1 -[4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1- ON oligomers and the like.

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

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 [2- (5-Methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1 , 3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl Methyl) 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Commercially available polymerization initiators can 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 Ciba Specialty Chemicals Co., Ltd.) Sake All (registered trademark) BZ, Z, and BEE (manufactured by Seiko Chemical Co., Ltd.); Kayacure (registered trademark) BP100, and UVI-6992 (manufactured by Dow Chemical Company); Adeka Optomer SP-152; N-1717, N-1919, SP-170, ADEKA ARKULS NCI-831, ADEKA ARKULS NCI-930 (manufactured by ADEKA Corporation); TAZ-A and TAZ-PP (manufactured by Nippon SiberHegner Co., Ltd.); TAZ-104 (Corporation Sum Chemical Co.); and the like. One type of polymerization initiator in the composition (A) may be used, or two or more types of polymerization initiators may be mixed according to a light source.

  The content of the polymerization initiator in the composition (A) can be appropriately adjusted depending on the type and the amount of the polymerizable liquid crystal, and is usually 0.1 to 30 based on 100 parts by mass of the polymerizable liquid crystal. Parts by mass, preferably 0.5 to 10 parts by mass, more preferably 0.5 to 8 parts by mass. When the content of the polymerization initiator is within the above range, polymerization can be performed without disturbing the alignment of the polymerizable liquid crystal.

(Sensitizer)
Composition (A) may contain a sensitizer. As the sensitizer, a photosensitizer is preferable. Examples of the sensitizer include xanthone compounds such as xanthone and thioxanthone (eg, 2,4-diethylthioxanthone, 2-isopropylthioxanthone); anthracenes such as anthracene and an alkoxy group-containing anthracene (eg, dibutoxyanthracene) Compounds: phenothiazine, rubrene and the like.

  When the composition (A) contains a sensitizer, the polymerization reaction of the polymerizable liquid crystal contained in the composition (A) can be further promoted. The amount of the sensitizer used is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal. Is more preferred.

(Polymerization inhibitor)
From the viewpoint of stably proceeding the polymerization reaction, the composition (A) may contain a polymerization inhibitor. The progress of the polymerization reaction of the polymerizable liquid crystal can be controlled by the polymerization inhibitor.

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

  When the composition (A) contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the polymerizable liquid crystal. It is 5 to 5 parts by mass, more preferably 0.5 to 3 parts by mass. When the content of the polymerization inhibitor is within the above range, polymerization can be performed without disturbing the alignment of the polymerizable liquid crystal.

(Leveling agent)
The composition (A) may contain a leveling agent. Leveling agents are additives having a function of adjusting the fluidity of the composition and making the film obtained by applying the composition more flat, and include, for example, organically modified silicone oils, polyacrylates, and perfluorocarbons. Alkyl-based leveling agents are exemplified. Specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all manufactured by Dow Corning Toray Co., Ltd.), KP321, KP323, KP324, KP326, KP340 KP341, X22-161A, KF6001 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all are all Momentive Performance Materials Japan GK) Fluorinert (registered trademark) FC-72, FC-40, FC-43, FC-3283 Manufactured by Sumitomo 3M Limited), Megafac (registered trademark) R-08, R-30, R-90, F-410, F-411, F-443, F-445, F-445 F-470, F-474, F-479, F-482, F-483 (all manufactured by DIC Corporation), F-top (trade name) EF301, EF303, EF351, EF352 (all manufactured by Mitsubishi Materials Electronic Chemicals, Inc.), Surflon (registered trademark) S-381, S-382, S-383, S-393, SC-101, SC-105, KH -40, SA-100 (all, manufactured by AGC Seimi Chemical Co., Ltd.), trade names E1830, E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100, BYK-352, BY -353 and BYK-361N (both trade name: BM Chemie Co., Ltd.), and the like. Among them, polyacrylate-based leveling agents and perfluoroalkyl-based leveling agents are preferred.

  When the composition (A) contains a leveling agent, it is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 100 parts by mass of the polymerizable liquid crystal. 0.1 to 3 parts by mass. When the content of the leveling agent is within the above range, the polymerizable liquid crystal can be easily horizontally aligned, and the obtained polarizing film tends to be smoother. If the content of the leveling agent with respect to the polymerizable liquid crystal exceeds the above range, the obtained polarizing film tends to have unevenness. The composition (A) may contain two or more types of leveling agents.

(solvent)
Composition (A) may contain a solvent. In general, since a polymerizable liquid crystal compound has a high viscosity, application to the composition (A) dissolved in a solvent is facilitated, and as a result, a polarizing film is often easily formed. The solvent is preferably a solvent that can completely dissolve the polymerizable liquid crystal compound, and is preferably a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound.

  Examples of the solvent include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether and propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone Or ester solvents such as propylene glycol methyl ether acetate and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; And aromatic hydrocarbon solvents such as xylene, and nitrile solvents such as acetonitrile; Ether solvents such as hydrofuran and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone And the like. These solvents may be used alone or in combination of two or more.

  The content of the solvent is preferably from 50 to 98% by mass based on the total amount of the composition (A). In other words, the content of the solid content in the composition (A) is preferably 2 to 50% by mass. When the content of the solid content is 50% by mass or less, the viscosity of the composition (A) decreases, and the thickness of the polarizing film becomes substantially uniform. Tend. Further, the content of the solid content can be determined in consideration of the thickness of the polarizing film to be manufactured.

(Reactive additive)
Composition (A) may include a reactive additive. As the reactive additive, those having a carbon-carbon unsaturated bond and an active hydrogen reactive group in the molecule are preferable. Here, the "active hydrogen reactive group" refers to groups which are reactive toward groups having active hydrogen such as carboxyl group (-COOH), a a hydroxyl group (-OH), a amino group (-NH ₂₎ And glycidyl group, oxazoline group, carbodiimide group, aziridine group, imide group, isocyanate group, thioisocyanate group, maleic anhydride group and the like are typical examples. The number of carbon-carbon unsaturated bonds and active hydrogen-reactive groups of the reactive additive is usually 1 to 20, preferably 1 to 10, respectively.

  The reactive additive preferably has at least two active hydrogen-reactive groups. In this case, the plurality of active hydrogen-reactive groups may be the same or different.

  The carbon-carbon unsaturated bond of the reactive additive may be a carbon-carbon double bond or a carbon-carbon triple bond, or a combination thereof, but is preferably a carbon-carbon double bond. Among them, the reactive additive preferably contains a carbon-carbon unsaturated bond as a vinyl group and / or a (meth) acryl group. Further, a reactive additive in which the active hydrogen reactive group is at least one selected from the group consisting of an epoxy group, a glycidyl group and an isocyanate group is preferable, and a reactive additive having an acryl group and an isocyanate group is more preferable. .

  Specific examples of the reactive additive include compounds having a (meth) acrylic group and an epoxy group, such as methacryloxyglycidyl ether and acryloxyglycidyl ether; (meth) acrylic groups, such as oxetane acrylate and oxetane methacrylate, and oxetane A compound having a (meth) acrylic group and a lactone group, such as lactone acrylate and lactone methacrylate; a compound having a vinyl group and an oxazoline group, such as vinyl oxazoline and isopropenyl oxazoline; isocyanatomethyl acrylate And oligomers of compounds having a (meth) acrylic group and an isocyanate group, such as isocyanatomethyl methacrylate, 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate. That. Further, compounds having a vinyl group or a vinylene group and an acid anhydride, such as methacrylic anhydride, acrylic anhydride, maleic anhydride and vinyl maleic anhydride, may be mentioned. Among them, methacryloxyglycidyl ether, acryloxyglycidyl ether, isocyanatomethyl acrylate, isocyanatomethyl methacrylate, vinyl oxazoline, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate and the above oligomers are preferable, and isocyanatomethyl acrylate, 2-isocyanatoethyl acrylate and the aforementioned oligomers are particularly preferred.

  Specifically, a compound represented by the following formula (Y) is preferable.

[In the formula (Y),
n represents an integer of 1 to 10, and R ^{1 ′} is a divalent aliphatic or alicyclic hydrocarbon group having 2 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 5 to 20 carbon atoms. Represents One of two R ^{2 ′ in} each repeating unit is —NH—, and the other is a group represented by> NC (＝ O) —R ^{3 ′} . R ^{3 ′} represents a hydroxyl group or a group having a carbon-carbon unsaturated bond.
Among R ^{3 ′} in the formula (Y), at least one R ^{3 ′} is a group having a carbon-carbon unsaturated bond. ]

  Among the reactive additives represented by the formula (Y), a compound represented by the following formula (YY) (hereinafter sometimes referred to as a compound (YY)) is particularly preferred (n is the same as described above). Meaning).

  As the compound (YY), a commercially available product can be used as it is or may be purified as necessary. Commercially available products include, for example, Laromer (registered trademark) LR-9000 (manufactured by BASF).

  When the composition (A) contains a reactive additive, the content of the reactive additive is usually 0.01 to 10 parts by mass, preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the polymerizable liquid crystal. To 5 parts by mass.

  Before the composition (A) is applied to the substrate layer, it is preferable that the moisture content of the substrate layer is adjusted. The moisture content of the base material layer can be 5.0% or less, and is preferably 3.0% or less. The moisture content of the base material layer 11 can be 0.0% or more. When the composition (A) is applied to the substrate layer having such a moisture content, the uniformity of the alignment direction of the polymerizable liquid crystal and the dichroic dye is increased. In particular, when the laminate 10 is stretched, the unevenness of the optical properties is easily recognized, and even after the stretching, the polarizing layer can easily maintain good optical properties. The moisture content of the base material layer is measured by a method described in Examples described later.

  The moisture content of the substrate layer is adjusted by heating or humidifying the substrate layer. Heating the base layer is also effective in adjusting the elastic modulus of the laminate. When heating the base material layer, the heating temperature can be 50 ° C. or more and 150 ° C. or less, and the heating time can be 1 minute or more and 10 minutes or less.

(Coating method)
The method for applying the composition (A) onto the base material layer 11 or the alignment layer includes extrusion coating, direct gravure coating, reverse gravure coating, CAP coating, slit coating, microgravure, and die coating. And an inkjet method. Further, a coating method using a coater such as a dip coater, a bar coater, and a spin coater may be used. Among them, a microgravure method, an ink-jet method, a slit coating method, and a die coating method are preferable for continuous application in a roll-to-roll format, and a uniform method for application to a sheet material such as glass. A spin coating method having high performance is preferred. When applying in a roll-to-roll format, an orientation polymer composition or a composition for forming a photo-alignment layer is applied to the base material layer 11 to form an orientation layer, and the composition (A) is further formed on the obtained orientation layer. ) Can be applied continuously.

(Drying method)
Examples of the drying method for removing the solvent contained in the composition (A) include natural drying, ventilation drying, heat drying, drying under reduced pressure, and a combination thereof. Above all, natural drying or heat drying is preferable. The drying temperature is preferably in the range of 0 to 200 ° C, more preferably in the range of 20 to 150 ° C, and still more preferably in the range of 50 to 130 ° C. The drying time is preferably from 10 seconds to 10 minutes, more preferably from 30 seconds to 5 minutes. The composition for forming a photo-alignment layer and the polymer composition for orientation can be similarly dried.

(Polymerization method)
As a method for polymerizing the polymerizable liquid crystal compound, photopolymerization is preferable. Photopolymerization is performed by irradiating the composition (A) containing the polymerizable liquid crystal compound applied on the base material layer 11 or the alignment layer with an active energy ray. The type of the polymerizable liquid crystal compound contained in the dried film (particularly, the type of the photopolymerizable functional group included in the polymerizable liquid crystal compound) as the active energy ray to be irradiated, and the photopolymerization initiator when the photopolymerization initiator is contained. Are appropriately selected in accordance with the types and the amounts thereof. Specifically, it includes at least one kind of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-ray, α-ray, β-ray, and γ-ray. Above all, ultraviolet light is preferable in that it is easy to control the progress of the polymerization reaction and that a photopolymerization apparatus that is widely used in this field can be used. It is preferable to select the type of the liquid crystal compound.

  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 ultra-high-pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excimer laser, and a wavelength range. LED light sources emitting 380 to 440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, and the like.

Ultraviolet irradiation intensity is ^{usually, 10mW / cm 2 ~3,000mW / cm} 2. The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activating a cationic polymerization initiator or a radical polymerization initiator. The time for irradiating light is usually 0.1 second to 10 minutes, preferably 0.1 second to 5 minutes, more preferably 0.1 second to 3 minutes, and further preferably 0.1 second. ~ 1 minute. When irradiation is performed once or more times with such ultraviolet irradiation intensity, the integrated light amount is 10 mJ / cm ^{2 to} 3,000 mJ / cm ² , preferably 50 mJ / cm ^{2 to} 2,000 mJ / cm ² , and more preferably 100 mJ / cm ² . / Cm ^{2 to} 1,000 mJ / cm ² . If the integrated light amount is below this range, the polymerizable liquid crystal compound will be insufficiently cured, and good transferability may not be obtained. Conversely, when the integrated light amount is more than this range, the optical film including the optically anisotropic layer may be colored.

<Display device>
The display device is not particularly limited, and examples thereof include an organic electroluminescence (organic EL) display device, an inorganic electroluminescence (inorganic EL) display device, a liquid crystal display device, a touch panel display device, and an electroluminescent display device. Since the display device of the present embodiment includes the stretchable laminate 10, it can be suitably used for a stretchable display device, and particularly, can be suitably used for an organic EL display device.

  Hereinafter, the present invention will be described in more detail with reference to examples. "%" And "parts" in the examples are% by mass and parts by mass unless otherwise specified.

[Tensile modulus]
The tensile modulus was measured in accordance with JIS K7161 using UTM (Universal Testing Machine, Autograph AG-X, Shimadzu Corporation) when stretched in the absorption axis direction and the transmission axis direction, respectively. The stretching conditions were as follows: room temperature (temperature 23 ° C.), speed 1.5 mm / min, width 40 mm, gauge length 50 mm.

[All haze values]
The total haze value of the laminate before and after stretching in each stretching direction and stretching ratio was measured using a haze meter (HM-150, Murakami Color Research Laboratory Co., Ltd.) in accordance with JIS K7136. did. The absolute value of the difference between the total haze values of the laminate before and after stretching at each stretching ratio was defined as ΔH.
The total haze value can be calculated by the following equation.
Total haze value (%) = scattered transmittance (%) / total light transmittance (%) × 100

[Visibility correction unit transmittance and visibility correction polarization degree]
Before and after stretching in each stretching direction and stretching ratio, the luminosity-corrected single transmittance and the luminosity-corrected polarization were measured with an ultraviolet-visible spectrophotometer (V7100, Japan) in accordance with JISZ8701. (Spectroscopy, Inc.). The absolute values of the difference between the luminosity-corrected single transmittance and the luminosity-corrected polarization degree of the laminate before and after stretching at each stretching ratio were defined as ΔT and ΔP, respectively.

[Moisture percentage of substrate layer]
The moisture content of the base material layer was calculated based on the following equation using MS-70, a heat-drying moisture meter manufactured by A & D Corporation. The size of the substrate layer when measuring the moisture content was 100 mm × 100 mm.
Moisture content of the base layer _{(%) = 100 × (W} A -W B -W P) / (W B -W 2)
_{W P} = W 1 -W ₂
W _A is the weight of the sample dish loaded with substrate layer.
W _B is a sample dish carrying the substrate layer was heated at 120 ° C., weighs when the time change of the moisture content became 0.02% / min or less.
W ₁ is the weight of the sample dish.
W ₂ is the sample pan was heated at 120 ° C., it weighs when the time change of the moisture content became 0.02% / min or less.
W _P reflects the surface moisture content of the sample dish.

[Appearance evaluation]
The laminate after stretching in each stretching direction and stretching ratio was visually evaluated for unevenness, cracks, haze, and the presence or absence of breakage.
：: no unevenness, no crack, no haze, and no breakage ×: no unevenness, no crack, haze, and no breakage XX: crack, breakage, or unevenness

[Polymerizable liquid crystal compound]
The polymerizable liquid crystal compound is a polymerizable liquid crystal compound represented by the formula (1-6) [hereinafter, also referred to as compound (1-6)] 75 parts and a polymerizable liquid crystal compound represented by the formula (1-7) [ Hereinafter, also referred to as compound (1-7)].

  Compound (1-6) and compound (1-7) are described in Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996).

As the dichroic dye, an azo dye described in Examples of JP-A-2013-101328 represented by the following formulas (2-1a), (2-1b), and (2-3a) was used.

[Composition for forming a polarizing layer]
The composition for forming a polarizing layer comprises 75 parts by weight of the compound (1-6), 25 parts by weight of the compound (1-7), and the above-mentioned formulas (2-1a), (2-1b) and (2) as dichroic dyes. -3a), 2.5 parts by weight of each of the azo dyes, 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one (Irgacure 369, manufactured by BASF Japan) as a polymerization initiator 6 parts by weight and 1.2 parts by weight of a polyacrylate compound (BYK-361N, manufactured by BYK-Chemie) as a leveling agent were mixed with 400 parts of toluene as a solvent, and the resulting mixture was stirred at 80 ° C. for 1 hour. Prepared.

ＧＰＣ測定より、得られたポリマー１の分子量は数平均分子量２８２００、Ｍｗ／Ｍｎ１．８２を示し、モノマー含有量は０．５％であった。 [Polymer 1]
Polymer 1 is a polymer having a photoreactive group consisting of the following structural units.

According to GPC measurement, the molecular weight of the obtained polymer 1 showed a number average molecular weight of 28,200 and Mw / Mn of 1.82, and the monomer content was 0.5%.

[Composition for forming alignment layer]
A solution in which polymer 1 was dissolved in cyclopentanone at a concentration of 5% by weight was used as a composition for forming an alignment layer.

[Example 1]
A substrate layer made of triacetyl cellulose (TAC) having a thickness of 25 μm was prepared. This base material layer was dried by heating at 120 ° C. for 5 minutes so that the water content was 2%. The composition for forming an alignment layer was applied on the base material layer by a bar coating method, and the coating film was dried at 80 ° C. for 1 minute. The thickness was 100 nm.

Then, using a UV irradiation apparatus (SPOT CURE SP-7, manufactured by Ushio Inc.), light having an integrated light amount of 100 mJ / cm ² measured at a wavelength of 365 nm was applied to a wire grid (UIS-27132 ##, Ushio Inc.). ) Was applied to the substrate to give an alignment property, thereby obtaining an alignment layer.

The composition for forming a polarizing layer was applied on the obtained alignment layer by a bar coating method. The coating film was dried by heating at 100 ° C. for 2 minutes, and then cooled to room temperature to obtain a dried film. The obtained film was irradiated with ultraviolet rays using a UV irradiation apparatus (SPOT CURE SP-7) so that the integrated light amount was 1200 mJ / cm ² (based on 365 nm) to obtain a polarizing layer having a thickness of 3 μm. . The resulting laminate was then measured each tensile modulus in the absorption axis direction and the transmission axis direction (E _A and E _T). The laminate, _{E T E A} is 3180MPa was 3900MPa. Before stretching, after stretching in the absorption axis direction at a stretching ratio of 5%, and after stretching in the transmission axis direction at a stretching ratio of 5%, the total haze value, luminosity correction single transmittance, luminosity correction The degree of polarization and appearance were evaluated. Table 1 shows the results. Stretching was performed using UTM. The stretching conditions were a speed of 1.5 mm / min, a width of 40 mm, and a gauge length of 50 mm at room temperature.

[Example 2]
A laminated body was produced in the same manner as in Example 1, except that the stretching ratio in the absorption axis direction and the stretching ratio in the transmission axis direction were each set to 10%.

[Example 3]
A laminate was produced in the same manner as in Example 1, except that the substrate layer made of triacetyl cellulose (TAC) was changed to a substrate layer made of polyethylene terephthalate (PET). The thickness of the substrate layer made of PET was 50 μm. The laminate, _{E T E A} is 4500MPa was 3,300 MPa.

[Example 4]
A laminate was produced in the same manner as in Example 3, except that the stretching ratio in the absorption axis direction and the stretching ratio in the transmission axis direction were each set to 10%.

[Comparative Example 1]
After dipping a polyvinyl alcohol film [Kuraray Co., Ltd. product name "Kuraray Vinylon VF-PE @ 3000"] having an average degree of polymerization of about 2400, a degree of saponification of 99.9 mol%, and a thickness of 30 [mu] m in pure water at 37 [deg.] C. Immersion in a 30 ° C. aqueous solution containing iodine and potassium iodide (iodine / potassium iodide / water (weight ratio) = 0.05 / 1.7 / 100).

It was immersed in a 58 ° C. aqueous solution containing potassium iodide and boric acid (potassium iodide / boric acid / water (weight ratio) = 12 / 3.2 / 100). The film was washed with pure water at 15 ° C and then dried at 80 ° C to obtain a polarizing layer having a thickness of about 12 µm in which iodine was adsorbed and oriented in polyvinyl alcohol. Stretching was performed mainly in the steps of iodine staining and boric acid treatment, and the total stretching ratio was 5.5 times. A base layer made of a 25 μm-thick TAC film (trade name “KC2UA” manufactured by Konica Minolta Co., Ltd.) is bonded to one surface of the obtained polarizing layer via an adhesive made of an aqueous solution of a polyvinyl alcohol-based resin. A polarizing plate was manufactured. The laminate, _{E T E A} is 8500MPa was 4950MPa.

The obtained laminated body was stretched at a stretching rate of 5% to the absorption axis direction, and the tensile modulus in each after a stretching rate of 5% to the transmission axis direction (E _A and E _T) were measured. Before stretching, after stretching in the absorption axis direction at a stretching ratio of 5%, and after stretching in the transmission axis direction at a stretching ratio of 5%, the total haze value, luminosity correction single transmittance, luminosity correction The degree of polarization and appearance were evaluated. Table 1 shows the results.

[Comparative Example 2]
In Comparative Example 1, a laminate was produced in the same manner as in Comparative Example 1, except that the stretching ratio in the absorption axis direction and the stretching ratio in the transmission axis direction were each set to 10%.

[Comparative Example 3]
A laminated body was produced in the same manner as in Comparative Example 1, except that a polyethylene terephthalate (PET) film (Toray Industries, Inc.) was used instead of the TAC film having a thickness of 25 μm. The thickness of the PET film was 38 μm. The laminate, _{E T E A} is 9900MPa was 5100MPa.

[Comparative Example 4]
A laminate was produced in the same manner as in Example 1, except that the substrate layer was not heated and dried.

  As shown in Table 1, the laminates of Examples 1 to 4 had a small difference between the total haze value, the visibility correction single transmittance and the visibility correction polarization degree before and after stretching, and were good after stretching. Appeared. On the other hand, in Comparative Example 1, the difference between the luminosity correction polarization degrees before and after stretching was large, and sufficient results were not obtained in the appearance evaluation after stretching. In Comparative Example 2, breakage occurred during stretching. In Comparative Example 3, all of the differences in the total haze value, the luminosity-corrected single transmittance, and the luminosity-correction polarization degree were large, and sufficient results were not obtained in the appearance evaluation. In Comparative Example 4, unevenness occurred in the polarizing layer, and the appearance was poor.

[Stretching test]
The laminates prepared in Examples 5 and 6 and Comparative Example 5 were subjected to reflectivity measurement, and then stretched at a rate of 2.5 mm / min at a rate of 2.5 mm / min using a UTM at a temperature of 60 ° C. and then stretched. While maintaining the state, the reflectance measurement and the appearance evaluation were performed. The measurement sample of each laminate had an initial stretching direction length of 50 mm and a width of 40 mm. A stretching test was performed for each of the cases where stretching was performed in the absorption axis direction (MD direction) and the transmission axis direction (TD direction).

The reflectance was measured by installing a sample for measurement and a reflector (aluminum plate, reflectance 97%) on a spectrophotometer (CM-2600d, manufactured by Konica Minolta, SCI mode) in this order. The absolute value Δ reflectance [%] of the difference between the reflectance [%] measured before stretching and the reflectance [%] measured while maintaining the stretched state was determined. Δ reflectance [%] can be obtained by the following equation.
Δ reflectance [%] = | Y (before stretching) −Y (stretched state) |
Y (before stretching) = Reflectance [%] measured before stretching
Y (stretched state) = Reflectance [%] measured while maintaining the stretched state

The appearance was evaluated visually for the presence or absence of unevenness, cracks, haze, and breakage.
：: no unevenness, no crack, no haze, and no breakage ×: no unevenness, no crack, haze, and no breakage XX: crack, breakage, or unevenness

[Production of coating type retardation layer with double-sided adhesive layer]
(Composition for forming alignment film)
5 parts by mass (weight average molecular weight: 30,000) of a photo-alignment material having a structure represented by the following formula and 95 parts by mass of cyclopentanone (solvent) are mixed, and the obtained mixture is heated at 80 ° C. for 1 hour. By stirring, a composition for forming an alignment film was obtained.

（重合性液晶化合物Ｂ）

重合性液晶化合物Ａは、特開２０１０−３１２２３号公報に記載された方法で製造した。また、重合性液晶化合物Ｂは、特開２００９−１７３８９３号公報に記載された方法に準じて製造した。 (Composition for forming retardation layer)
A leveling agent (F-556; manufactured by DIC Corporation) was added to 100 parts by mass of a mixture obtained by mixing the polymerizable liquid crystal compound A and the polymerizable liquid crystal compound B represented by the following formula at a mass ratio of 90:10. 0 parts by mass and 6 parts by mass of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one (Irgacure 369, manufactured by BASF Japan Ltd.) as a polymerization initiator were added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid concentration became 13%, and the mixture was stirred at 80 ° C. for 1 hour to obtain a composition for forming a retardation layer.
(Polymerizable liquid crystal compound A)

(Polymerizable liquid crystal compound B)

Polymerizable liquid crystal compound A was produced by the method described in JP-A-2010-31223. Further, the polymerizable liquid crystal compound B was produced according to the method described in JP-A-2009-173893.

(Production of a laminate composed of a substrate, an alignment film, and a cured layer of a polymerizable liquid crystal compound)
A 50 μm-thick cycloolefin-based resin film [ZF-14-50, manufactured by Zeon Corporation] was prepared as a substrate and subjected to corona treatment. The composition for forming an alignment film was applied to the surface subjected to the corona treatment using a bar coater. The coating film was dried at 80 ° C. for 1 minute. The dried coating film was irradiated with polarized UV at an axis angle of 45 ° using a polarized UV irradiator (trade name “SPOT CURE SP-9” of USHIO Inc.) to obtain an alignment film. The irradiation with the polarized UV was performed so that the integrated light amount at a wavelength of 313 nm was 100 mJ / cm ² .
Subsequently, the composition for forming a retardation layer was applied on the alignment film using a bar coater. The coating film was dried at 120 ° C. for 1 minute. Ultraviolet rays were applied to the dried coating film using a high-pressure mercury lamp (trade name of USHIO Inc .: “Unicure VB-15201BY-A”). The ultraviolet irradiation step was performed in a nitrogen atmosphere so that the integrated light amount at a wavelength of 365 nm was 400 mJ / cm ² . Immediately after the irradiation, as a cooling step, the cured film was put into an oven set at 5 ° C. for 20 seconds. Immediately after being removed from the oven, the ultraviolet irradiation step and the cooling step were performed again (that is, the total integrated light amount of the two ultraviolet irradiations was 800 mJ / cm ² ), and the base material, the alignment film, and the polymerizable liquid crystal were used. A laminate comprising a layer in which the compound was cured was obtained.

  The pressure-sensitive adhesive layer described later was laminated on the cured layer of the polymerizable liquid crystal compound in the produced laminate. Next, the base material was peeled off from the laminate, and the pressure-sensitive adhesive layer was similarly laminated on the surface that was peeled off and exposed. Thus, a coating type retardation layer with a double-sided pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive layer, a layer in which a polymerizable liquid crystal compound was cured, an alignment film, and a pressure-sensitive adhesive layer was prepared. The layer where the polymerizable liquid crystal compound was cured had a retardation value of λ / 4.

[Production of film type retardation layer with double-sided pressure-sensitive adhesive layer]
A Zeonor film (Nippon Zeon Co., Ltd., in-plane retardation value for light having a wavelength of λ = 550 nm: 138 nm), which is a film obtained by uniaxially stretching a cyclic olefin-based resin film, was prepared. The pressure-sensitive adhesive layers described below were laminated on both surfaces of the film.

(Adhesive layer)
70 parts by mass of butyl acrylate, 20 parts by mass of ethyl acrylate, 2.0 parts by mass of acrylic acid, and 0.2 parts by mass of a radical polymerization initiator (2,2′-azobisisobutyronitrile). The reaction was carried out at 55 ° C. while stirring under a nitrogen atmosphere to obtain an acrylic resin.

  Acrylic resin: 100 parts by mass, crosslinking agent ("Coronate L" manufactured by Tosoh Corporation): 0.7 parts by mass, silane coupling agent ("X-12-981" manufactured by Shin-Etsu Chemical Co., Ltd.): 0.5 parts by mass Parts were mixed. Ethyl acetate was added so that the total solid concentration became 10%, to obtain a pressure-sensitive adhesive composition.

  The resulting pressure-sensitive adhesive composition was applied to a release-treated surface of a release-treated polyethylene terephthalate film (thickness: 38 μm) using an applicator so that the thickness after drying was 25 μm. The coating layer was dried at 100 ° C. for 1 minute to obtain a film having an adhesive layer. Thereafter, another release-treated polyethylene terephthalate film (thickness: 38 μm) was bonded onto the pressure-sensitive adhesive layer. Then, it was cured for 7 days at a temperature of 23 ° C. and a relative humidity of 50% RH.

<Example 5>
The above-mentioned coating type retardation layer with a double-sided pressure-sensitive adhesive layer was bonded to the polarizing layer of the base material layer / polarizing layer laminate prepared in Example 1 via one pressure-sensitive adhesive layer. The slow axis of the layer where the polymerizable liquid crystal compound was cured was 45 degrees with respect to the absorption axis of the polarizing layer. In this way, a circularly polarizing plate comprising the substrate layer / polarizing layer / adhesive layer / coating type retardation plate / adhesive layer was produced. A stretching test was performed on the obtained circularly polarizing plate. Table 2 shows the results.

<Example 6>
The polarizing layer of the laminate composed of the base material layer / polarizing layer prepared in Example 1 and the above-mentioned film-type retardation layer were bonded together via an adhesive layer. The slow axis of the film type retardation layer was 45 degrees with respect to the absorption axis of the polarizing layer. In this way, a circularly polarizing plate composed of the substrate layer / polarizing layer / adhesive layer / film type retardation layer / adhesive layer was produced. A stretching test was performed on the obtained circularly polarizing plate. Table 2 shows the results.

<Comparative Example 5>
Substrate / polarizing layer / adhesive layer / coating type retardation layer / adhesive in the same manner as in Example 5, except that the laminate composed of the substrate layer / polarizing layer prepared in Comparative Example 4 was used. A circularly polarizing plate comprising an agent layer was produced. A stretching test was performed on the obtained circularly polarizing plate. Table 2 shows the results.

  10 laminated body, 11 base material layer, 12 polarizing layer.

Claims (8)

A stretchable laminate comprising a base layer and a polarizing layer,
The moisture content of the base material layer is 5.0% or less,
A laminate that satisfies the following formula (1).
| E _A −E _T | / | E _A + E _T | ≦ 0.25 (1)
Wherein each of E _A and E _T, showing a tensile modulus in the absorption axis direction and the transmission axis direction]   The laminate according to claim 1, wherein the total haze value is 3% or less.   The laminate according to claim 1, wherein the thickness of the polarizing layer is 0.5 μm to 10 μm.   The laminate according to any one of claims 1 to 3, wherein the polarizing layer is formed of a cured product of a polarizing layer forming composition including a polymerizable liquid crystal compound and a dichroic dye.   The laminate according to any one of claims 1 to 4, wherein the content of the dichroic dye in the polarizing layer is 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound.   The laminate according to any one of claims 1 to 5, further comprising a pressure-sensitive adhesive layer on the polarizing layer side.   The laminate according to claim 6, further comprising a retardation layer laminated via the pressure-sensitive adhesive layer.   A display device, wherein the laminate according to any one of claims 1 to 7 is bonded to an image display device.

Images