TW202015900A - Laminated body - Google Patents

Abstract

Provided is a stretchable laminated body of which the optical characteristics do not change and the external appearance is not adversely affected even when the laminated body is stretched. A stretchable laminated body configured from a base material layer and a polarized layer, wherein the moisture percentage of the base material layer is 5.0% or less, and the laminated body satisfies formula (1). Formula (1): |EA - ET|/|EA + ET| ≤ 0.25 [In the formula, EA and ET indicate the tensile modulus of elasticity in the absorption-axis direction and the transmission-axis direction, respectively.].

Description

Laminate

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

In Patent Document 1, a display device that can be extended is proposed. In Patent Document 2, there is proposed a polarizing plate that can be bent by heat. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Korean Patent Publication No. 10-2016-0090977 [Patent Document 2] Japanese Patent No. 5633228

[Problems to be solved by the invention]

The object of the present invention is to provide a layered body that can be extended. Even when it is extended, the optical characteristics such as the transmittance of the visual acuity correction individual and the polarized degree of the visual acuity correction do not change significantly, and haze and turtle are not generated. Cracks and other poor appearance. [Technical means to solve the problem]

The present invention provides the layered product shown below. [1] A laminate that is a stretchable laminate including a base material layer and a polarizing layer, and has a moisture content of 5.0% or less, which satisfies the following formula (1). ｜E _A －E _T ｜/｜E _A +E _T ｜≦0.25 (1) [where E _A and E _T represent the tensile elastic modulus in the absorption axis direction and transmission axis direction, respectively] [2] If [ The laminated body described in 1] has a total haze value of 3% or less. [3] The laminate as described in [1], wherein the polarizing layer has a thickness of 0.5 μm to 10 μm. [4] The laminate according to [1], wherein the polarizing layer contains a cured product of a polarizing layer forming composition containing a polymerizable liquid crystal compound and a dichroic dye. [5] The laminate according to [1], wherein the content of the dichroic dye in the polarizing layer is 0.1 to 30 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. [6] The laminate as described in [1], which further has an adhesive layer on the polarizing layer side. [7] The laminate as described in [6], which has a retardation layer laminated through the adhesive layer. [8] A display device in which the laminate as described in any one of [1] to [7] is bonded to an image display element. [Effect of invention]

According to one aspect of the present invention, it is possible to provide a layered body that can be extended. Even when it is extended, the optical characteristics such as the transmittance of the visual acuity correction individual body or the polarized degree of the visual acuity correction do not change significantly and do not occur. Poor appearance such as haze or cracks.

Hereinafter, a layered body according to one aspect of the present invention (hereinafter also simply referred to as "layered body") will be described with reference to the drawings.

<Laminate> FIG. 1 shows a schematic cross-sectional view of a laminated body according to an aspect of the present invention. The layered body 10 is an extendable layered body composed of a base material layer 11 and a polarizing layer 12. The term "extendable" means that the laminate 10 can be extended without breaking when it is stretched in at least one of the absorption axis direction and the transmission axis direction. The direction of the absorption axis refers to the case where the polymerizable liquid crystal compound is hardened or the liquid crystal dichroism is exhibited when the following dichroic dye and the polymerizable liquid crystal compound constituting the polarizing layer 12 are horizontally aligned with respect to the substrate layer When the pigment is horizontally aligned with respect to the substrate layer, it refers to the alignment direction of the dichroic pigment and the polymerizable liquid crystal compound. The transmission axis direction refers to the case where the polymerizable liquid crystal compound is hardened or the liquid crystal dichroism is exhibited in a state where the following dichroic dye and the polymerizable liquid crystal compound constituting the polarizing layer 12 are horizontally aligned with respect to the substrate layer When the pigment is aligned horizontally with respect to the substrate level, it refers to a direction that is horizontal with respect to the substrate level and perpendicular to the alignment direction. The alignment state of the polarizing layer can be confirmed by observation with a polarizing microscope. Insert the laminate sample in the direction of about 45° between the polarizing microscope cross polarizers, and observe under light leakage. In the case of alignment in the vertical direction, the dark field is observed without light leakage, and in the case of horizontal alignment, light leakage is generated and observation is performed in the bright field.

Both the breaking elongation in the absorption axis direction and the transmission axis direction of the laminate 10 can be, for example, 5% or more. When the breaking elongation in the absorption axis direction and the transmission axis direction are both 5% or more, there is a tendency that sufficient extensibility tends to be obtained. The elongation at break in the absorption axis direction and the transmission axis direction of the laminate 10 is preferably 5% to 20%, and 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%, it is easy to obtain sufficient elongation, and it is difficult to cause changes in optical characteristics, or poor appearance such as haze and cracks. The tendency. The elongation at break in the direction of the absorption axis and the transmission axis is the elongation at break of the laminate when it is stretched in the direction of the absorption axis or the direction of the transmission axis in the tensile test, and can be based on JIS K 7161, for example, UTM (Universal Testing Machine, Autograph AG-X, Shimadzu Corporation). The breaking elongation can adopt the value at normal temperature (temperature 23℃).

The laminate 10 satisfies the following formula (1) when the tensile elastic modulus in the absorption axis direction and the transmission axis direction is E _A and E _T , respectively. ｜E _A －E _T ｜/｜E _A +E _T ｜≦0.25 (1) When the laminate 10 does not satisfy the formula (1), when the laminate 10 is stretched, there is a possibility that the optical characteristics may change or occur Broken, or tend to have poor appearance such as haze and cracks. For this reason, it is presumed that by making the laminate isotropically have a certain degree of tensile elastic modulus, the optical characteristics of the laminate are maintained even when the laminate is extended. However, the present invention is not limited by this presumption. The tensile elastic modulus can be measured according to the measurement method described in the column of the following examples. |E _A -E _T |/|E _A +E _T |The lower limit may be, for example, 0.01. The tensile modulus can be the value at normal temperature (temperature 23℃).

The laminate 10 can be manufactured by combining, for example, the thickness adjustment of the base material layer 11, the polarizing layer 12 and the alignment layer, the selection of materials for the base material layer, and the formation of polarized light in a manner satisfying the formula (1) Selection of the dichroic pigment or polymerizable liquid crystal compound of the layer or adjustment of the composition ratio thereof, selection of raw materials for the composition for forming the alignment layer and adjustment of the composition ratio, conditions for forming the polarizing layer and the alignment layer , For example, adjustment of coating conditions, drying conditions, polymerization conditions, etc. In particular, the tensile modulus of elasticity of the laminate is related to the tensile modulus of elasticity of the base material layer. Therefore, as the base material layer, it is preferable to use one having an elongation of 5% or more.

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

Both the tensile modulus of elasticity E _A and E _T can be, for example, 1 MPa to 30,000 MPa, preferably 10 MPa to 20,000 MPa, more preferably 50 MPa to 15,000 MPa, or 1,000 MPa to 7,000 MPa, or 1,000 MPa to 5,000 MPa. When the tensile and E _T are 50 MPa ~ 15,000 MPa case of elastic modulus E _A, also tends to be difficult to break down even when the situation to cause the laminate 10 extends.

The total haze value of the laminate 10 may be, for example, 3% or less. When the total haze value is 3% or less, it can be preferably used in a display device. The total haze value of the laminate 10 is preferably 2.8% or less, and 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, there is a tendency that the visibility is easily improved. The total haze value can be determined according to the method described in the column of the following examples. 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 column of the following examples.

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

The polarizing performance of the laminate 10 can be measured using a spectrophotometer. For example, a spectrophotometer can be installed with a polarizer holder, and the transmission axis direction (relative to the alignment of the dichroic pigment) can be measured within the range of 380 nm to 780 nm as the wavelength of visible light using the dual-beam method The direction perpendicular to the direction) the transmittance (T1) and the transmittance (T2) in the absorption axis direction (the same direction as the alignment direction of the dichroic dye). For the polarization performance in the visible light range, the following formulas (3) and (4) can be used to calculate the individual body transmittance and polarization at each wavelength, and then the visual sensitivity can be measured by the 2 degree field of view (C light source) of JIS Z 8701 The correction can thereby calculate the visual acuity correction individual body transmittance (Ty) and the visual acuity correction polarized degree (Py). Individual body transmittance (%) = (T1 + T2)/2 (3) Polarization (%) = (T1－T2)/(T1＋T2)×100 (4)

The visual sensitivity correction individual body transmittance of the laminate 10 may be, for example, 30% or more, preferably 35% or more, and more preferably 38% or more. On the other hand, the visual acuity correction individual body transmittance of the laminate 10 is usually 70% or less, preferably 48% or less, and more preferably 46% or less. The visual sensitivity correction individual body transmittance can be measured according to the method described in the column of the following examples.

The difference (ΔT) in the visual sensitivity correction individual body transmittance before and after the laminate 10 extends in the absorption axis direction and the transmission axis direction can be, for example, 1.5% or less, preferably 1.2% or less, and more preferably 1% or less. In a preferred embodiment, the difference in the visual acuity correction (ΔT) of the individual body before the extension of the laminate 10 and after the extension of 5% in the absorption axis direction and the transmission axis direction can be, for example, 1.5% or less. It is preferably 1.2% or less, and more preferably 1% or less. In a more preferred embodiment, the difference (ΔT) in the visual acuity correction individual body transmittance values before the extension of the laminate 10 and after the extension of 10% in the absorption axis direction and the transmission axis direction can be, for example, 1.5% or less, It is preferably 1.2% or less, and more preferably 1% or less.

The visual sensitivity correction polarization degree of the laminate 10 may be, for example, 80% or more, preferably 85% or more, and more preferably 90% or more. On the other hand, the visual sensitivity correction polarization degree of the laminate 10 is usually 100% or less, 99.99% or less, and 99.0% or less. The visual sensitivity correction polarization degree can be measured according to the method described in the column of the following examples.

The difference (ΔP) in visual sensitivity correction polarization degree before and after the laminate 10 extends in the absorption axis direction and the transmission axis direction can be, for example, 3% or less, preferably 2.5% or less, and more preferably 2% or less. In a preferred embodiment, the difference (ΔP) in visual acuity correction polarization (ΔP) between the extension of the laminate 10 before the extension and the extension of 5% in the absorption axis direction and the transmission axis direction can be, for example, 3% or less, preferably 2.5% or less, more preferably 2% or less. In a more preferred embodiment, the difference (ΔP) in visual acuity correction (ΔP) between the extension of the laminate 10 before the extension and the extension of 10% in the absorption axis direction and the transmission axis direction can 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, there is a tendency that the display device is easily made thin.

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

[Substrate layer] The base material layer 11 may be composed of, for example, a resin film, and preferably may be composed of a transparent resin film. The resin film may be an elongated roll-shaped resin film or a single-piece resin film. In terms of continuous production, a long rolled resin film is preferred.

Examples of the resin constituting the resin film include polyolefins such as polyethylene, polypropylene, and vinylene polymers; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; and polymethacrylic acid Ester; Polyacrylate; Cellulose esters such as triacetyl cellulose, diacetyl cellulose and cellulose acetate propionate; Polyethylene naphthalate; Polycarbonate; Poly satin; Polyether satin; Polyether ketone ; Polyphenylene sulfide; Polyphenylene oxide and other plastics. Among them, preferred are cyclic olefin resins, cellulose esters, and polyimide.

Typical examples of commercially available products of cyclic olefin resins include "Topas" (registered trademark) (manufactured by Ticona (Germany)), "ARTON" (registered trademark) (manufactured by JSR Corporation), "ZEONOR" (registered trademark), "ZEONEX" (registered trademark) (made by ZEON JAPAN Co., Ltd.) and "APEL" (registered trademark) (made by Mitsui Chemical Co., Ltd.), etc. Such a cyclic olefin 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 resin film can also be used. Typical examples of commercially available products of cyclic olefin resin films include "S-SINA" (registered trademark), "SCA40" (registered trademark) (the above is manufactured by Sekisui Chemical Industry Co., Ltd.), " "ZEONOR FILM" (registered trademark) (manufactured by Optes Co., Ltd.) and "ARTON FILM" (registered trademark) (manufactured by JSR Co., Ltd.), etc.

Examples of representative commercially available products of resin films composed of cellulose esters include: "Fujitac Film" (manufactured by Fuji Photo Film Co., Ltd.); "KC8UX2M", "KC8UY", and "KC4UY" (above Konica Minolta Opto Co., Ltd.), etc.

The moisture content of the base material layer 11 is 5.0% or less, preferably 3.0% or less. The moisture content of the substrate layer 11 may be 0.0% or more. When the moisture content of the base material layer 11 is 5.0% or less, when the polarizing layer 12 is formed, the uniformity of the alignment directions of the polymerizable liquid crystal compound and the dichroic dye tends to increase. In particular, when the laminate 10 is extended, it is easy to visually recognize the uneven optical characteristics even after the extension, it is easy to maintain the good optical characteristics of the polarizing layer. The moisture content of the base material layer is measured by the method described in the following examples.

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

The substrate layer 11 may have a hard coat layer, an anti-reflection layer, or an antistatic layer on at least one surface. The base material layer 11 may be formed with a hard coat layer, an anti-reflection layer, or an antistatic layer only on the surface on the side where the polarizing layer 12 is not formed. The base material layer 11 may form a hard coat layer, an anti-reflection layer, an antistatic layer, or the like only on the surface on the side where the polarizing layer 12 is formed. As the base material layer 11, the following window film can also be used.

[Polarizing layer] The polarizing layer 12 is preferably a layer composed of a cured product of a composition containing one or more polymerizable liquid crystal compounds [hereinafter also referred to as a polymerizable liquid crystal (a)] and a dichroic dye, or composed of one or more types A layer composed of a cured product of a composition of dichroic pigments showing liquid crystallinity. In the case where the polarizing layer 12 has the polarization characteristics in the plane direction of the laminate 10, as long as the dichroic dye and the polymerizable liquid crystal (a) are horizontally aligned with respect to the plane of the laminate 10, the polymerizable liquid crystal (a) is hardened , Or the dichroic dye showing liquid crystallinity may be aligned horizontally with respect to the plane of the laminate 10, when the polarizing layer 12 has the polarization characteristic in the thickness direction of the laminate 10, as long as the dichroic dye and the polymerizable liquid crystal (a) Normally, the polymerizable liquid crystal (a) is hardened in the normal state of being vertically aligned with respect to the plane of the laminate 10, or the dichroic dye exhibiting liquid crystallinity may be vertically aligned with respect to the plane of the laminate 10. The polarizing layer 12 is preferably a coating layer. For example, it may be a cured product of a polarizing layer forming composition [hereinafter also referred to as composition (A)] containing one or more polymerizable liquid crystals (a) and a dichroic dye.

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, for example, by applying the composition (A) on the base material layer 11 or the alignment layer described below, and polymerizing the polymerizable liquid crystal (a) in the resulting 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 participating in a polymerization reaction, and is preferably a photopolymerizable group. Here, the photopolymerizable group refers to a group that can participate in the polymerization reaction by active radicals or acids generated from the following photopolymerization initiator. Examples of the polymerizable group include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloyloxy, methacryloyloxy, ethylene oxide, Oxetane, etc. Among them, preferred are propenyl oxy, methacryl oxy, ethyleneoxy, oxirane and oxetanyl, and more preferred is propylene oxy. The liquid crystallinity may be a thermotropic liquid crystal or a liquid crystal, and when mixed with the following dichroic dye, it is preferably a thermotropic liquid crystal.

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 displayed by 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, it is more preferable to form smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase Or a higher order smectic liquid crystal compound of smectic L phase, and further preferably a higher order smectic liquid crystal compound forming smectic B phase, smectic F phase or smectic I phase. If the liquid crystal phase formed by the polymerizable liquid crystal (a) is the high-order smectic phase, a polarizing layer with higher polarization performance can be manufactured. In addition, the polarizing layer with such high polarizing performance can obtain the Bragg wave peak derived from the hexatic phase or the crystalline equivalent higher-order structure in the X-ray diffraction measurement. The Bragg wave peak is derived from the molecular structure of the periodic structure, and a membrane with a periodic interval of 3 to 6 Å can be obtained. From the viewpoint of obtaining higher polarizing characteristics, the polarizing layer of the present invention is preferably a polymer containing the polymerizable liquid crystal (a) polymerized in the smectic state of the polymerizable liquid crystal (a).

Specific examples of such compounds include compounds 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 formula (A), X ¹ , X ² and X ³ Each independently represents a divalent aromatic group or a divalent alicyclic hydrocarbon group. Here, the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with a halogen atom, a C 1-4 alkyl group, a C 1-4 fluoroalkyl group, C 1-4 alkoxy, cyano or nitro. 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. Among them, at least one of X ¹ , X ² and X ³ is 1,4-phenylene which may have a substituent or cyclohexane-1,4-diyl which may have a substituent. Y ¹ , Y ² , W ¹ and W ² are independently a single bond or a divalent linking group. V ¹ and V ² independently represent a C 1-20 alkanediyl group which may have a substituent. -CH ₂ -constituting the alkanediyl group may be substituted with -O-, -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 compound (I), at least one of X ¹ , X ² and X ³ is 1,4-phenylene which may have a substituent, or cyclohexane-1,4-diyl which may have a substituent . In particular, X ¹ and X ^{3 are} preferably cyclohexane-1,4-diyl which may have a substituent, and further preferably the cyclohexane-1,4-diyl is trans-cyclohexane- 1,4-diyl. When the compound (I) contains trans-cyclohexane-1,4-diyl group, there is a tendency that the smectic liquid crystal tends to be easily expressed. In addition, examples of the substituents optionally possessed by 1,4-phenylene which may have a substituent or cyclohexane-1,4-diyl which may have a substituent include carbons such as methyl, ethyl, and butyl. The halogen atom such as the alkyl group of 1 to 4, a cyano group, a chlorine atom, a fluorine atom, etc. 1,4-phenylene or cyclohexane-1,4-diyl is preferably unsubstituted.

Y ¹ and Y ^{2 are} preferably a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -COO-, -OCO-, -N=N-, -CR ^a =CR ^b -,- C≡C- or -CR ^a =N-, 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, in the case where X ¹ , X ² and X ³ do not include cyclohexane-1,4-diyl At this time, it is more preferable that Y ¹ and Y ² are different bonding methods. In the case where Y ¹ and Y ² are different from each other, there is a tendency for the smectic liquid crystal to be easily expressed.

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

Examples of C 1-20 alkanediyl represented by V ¹ and V ² include methylene, ethylidene, propane-1,3-diyl, butane-1,3-diyl, and butane Alkane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane Alkane-1,10-diyl, tetradecane-1,14-diyl, eicosane-1,20-diyl, etc. V ¹ and V ^{2 are} preferably C2-C12 alkanediyl groups, and more preferably linear C6-C12 alkanediyl groups. The linear dialkyl group having 6 to 12 carbon atoms tends to improve crystallinity and tend to express smectic liquid crystallinity.

Examples of the optional substituents of the C 1-20 alkanediyl group which may have a substituent include halogen atoms such as a cyano group, a chlorine atom, and a fluorine atom. The alkanediyl group is preferably unsubstituted, more preferably an unsubstituted and linear alkanediyl group.

U ¹ and U ^{2 are} preferably both polymerizable groups, and more preferably are both photopolymerizable groups. The polymerizable liquid crystal compound having a photopolymerizable group can be polymerized at a lower temperature than the polymerizable liquid crystal compound having a thermally polymerizable group, so that the polymer can be formed in a state where the order of liquid crystals is higher. Words are favorable.

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 vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloyloxy, methacryloyloxy, ethylene oxide, Oxetane, etc. Among them, preferred are acryloxy, methacryloxy, ethyleneoxy, oxirane and oxetanyl, and more preferably methacryloxy or propenyloxy.

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

[Chemical 1]

[Chem 2]

[Chemical 3]

[Chemical 4]

Among the above-mentioned compounds exemplified, it is preferably selected from the group consisting of formula (1-2), formula (1-3), formula (1-4), formula (1-6), formula (1-7), and formula ( 1-8), at least one of the group consisting of the compounds represented by formula (1-13), formula (1-14) and formula (1-15).

(Dichroic pigment) The dichroic pigment refers to a pigment that has a property that the absorbance in the long axis direction of the molecule is different from the absorbance in the short axis direction. The dichroic pigment preferably has a characteristic of absorbing visible light, and more preferably has an absorption maximum wavelength (λMAX) in the range of 380 to 680 nm. Examples of such dichroic dyes include acridine dyes, cyanine dyes, cyanine dyes, naphthalene dyes, azo dyes, and anthraquinone dyes. Among them, the dichroic dye is preferably an azo dye. Examples of azo dyes include monoazo dyes, disazo dyes, triazo dyes, tetraazo dyes, and stilbene dyes, and preferred are diazo dyes and triazo dyes. The dichroic pigments can be used alone or in combination. In order to obtain absorption in the entire range of visible light, it is preferable to use three or more dichroic pigments in combination, and it is more preferable to use three or more azo pigments in combination.

Examples of the azo dye include compounds represented by formula (II) (hereinafter sometimes referred to as "compound (II)"). T ¹ -A ¹ (-N=NA ² ) _p -N=NA ³ -T ² (II) [In formula (II), A ¹ and A ² and A ³ independently represent 1, which may have a substituent, 4-phenylene, naphthalene-1,4-diyl or a divalent heterocyclic group which may have a substituent. T ¹ and T ² are electron-withdrawing groups or electron-withdrawing groups, and are located at a position substantially 180° relative to the azo bonding plane. p represents an integer from 0 to 4. When p is 2 or more, each A ² may be the same or different. The -N=N- bond can be replaced by -C=C-, -COO-, -NHCO-, or -N=CH- bond within the range of showing absorption in the visible light region]

Examples of the substituents optionally possessed by 1,4-phenylene, naphthalene-1,4-diyl, and divalent heterocyclic groups in A ¹ , A ^2, and A ³ include methyl, ethyl, and butyl Alkyl groups with a carbon number of 1 to 4; alkoxy groups with a carbon number of 1 to 4 such as methoxy, ethoxy and butoxy; fluorinated alkyl groups with a carbon number of 1 to 4 such as trifluoromethyl; cyano Group; nitro group; halogen atom such as chlorine atom, fluorine atom; substituted or unsubstituted amine group such as amine group, diethylamino group and pyrrolidinyl group (so-called substituted amine group means having one or Two amine groups of C 1-6 alkyl groups or two substituted alkyl groups are bonded to each other to form an amine group of C 2-8 alkyl groups. The unsubstituted amine group is -NH ₂ ). In addition, examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, and hexyl. Examples of alkanediyl having 2 to 8 carbon atoms include ethylidene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, and pentane- 1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, etc. In order to be included in a high-order liquid crystal structure such as a smectic liquid crystal, A ¹ and A ² and A ^{3 are} preferably unsubstituted or hydrogen substituted with methyl or methoxy, 1,4-phenylene, or 2 Valence heterocyclic group, p is preferably 0 or 1. Among them, in terms of both simplicity of molecular synthesis and high performance, it is more preferable that p is 1, and at least two of the three structures of A ¹ and A ² and A ³ are 1,4- Phenylene.

Examples of the divalent heterocyclic group include a group obtained by removing two hydrogen atoms from quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole, and benzoxazole. In the case where A ² is a divalent heterocyclic group, it is preferable that the molecular bonding angle becomes substantially 180°, specifically, benzothiazole formed by condensation of two 5-membered rings, The structure of benzimidazole and benzimidazole.

T ¹ and T ² are electron-withdrawing groups or electron-withdrawing groups, preferably different structures from each other, and further preferably T ¹ is an electron-withdrawing group, T ² is a combination of electron-withdrawing groups, or T ¹ is an electron-withdrawing group , T ² is a combination of electron-pulling groups. Specifically, T ¹ and T ^{2 are} preferably independently alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, cyano group, nitro group, and having 1 or 2 carbon atoms. The amine group of the alkyl group of 6, or two substituted alkyl groups are bonded to each other to form an amine group of a C2-C8 alkyldiyl group, or trifluoromethyl group. In order to be included in a high-order liquid crystal structure such as a smectic liquid crystal, since it is necessary to exclude a structure with a small volume of molecules, T ¹ and T ^{2 are} preferably independently alkyl and carbon having 1 to 6 carbon atoms. The alkoxy group having 1 to 6 carbon atoms, the cyano group, the amine group having 1 or 2 alkyl groups having 1 to 6 carbon atoms, or two substituted alkyl groups are bonded to each other to form an alkyldiyl group having 2 to 8 carbon atoms Amine group.

Examples of such an azo dye include the following.

[Chem 5]

[化6]

In formulas (2-1) to (2-6), B ¹ to B ²⁰ 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, and a nitrate group Group, substituted or unsubstituted amine group (the definition of substituted amine group and unsubstituted amine group is as described above), chlorine atom or trifluoromethyl group. From the viewpoint of obtaining higher polarizing performance, B ² , B ⁶ , B ⁹ , B ¹⁴ , B ¹⁸ , and B ^{19 are} preferably hydrogen atoms or methyl groups, and more preferably hydrogen atoms. n1 to n4 independently represent integers of 0 to 3. When n1 is 2 or more, the plurality of B ² may be the same or different, when n2 is 2 or more, the plurality of B ⁶ may be the same, or different, when n3 is 2 or more The plurality of B ⁹ may be the same or different, and when n4 is 2 or more, the plurality of B ¹⁴ may be the same or different.

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

[化7]

[In 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. R ^x represents a C 1-4 alkyl group or a C 6-12 aryl group]

As the pigment, the compound represented by formula (2-8) is preferred.

[Chem 8]

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

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

[化9]

[In 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. R ^x represents a C 1-4 alkyl group or a C 6-12 aryl group]

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^x in formula (2-7), formula (2-8) and formula (2-9) include methyl, ethyl, propyl and butyl , Pentyl, hexyl and the like, and examples of the aryl group having 6 to 12 carbon atoms include phenyl, tolyl, xylyl and naphthyl.

As the cyanine pigment, compounds represented by formula (2-10) and compounds represented by formula (2-11) are preferred.

[化10]

[In formula (2-10), D ¹ and D ² independently represent a group represented by any one of formula (2-10a) to formula (2-10d).

n5表示1～3之整數][Chem 11]

n5 represents an integer from 1 to 3]

[化12]

[In formula (2-11), D ³ and D ⁴ independently represent a group represented by any one of formula (2-11a) to formula (2-11h).

n6表示1～3之整數][Chem 13]

n6 represents an integer from 1 to 3]

From the viewpoint of obtaining good light absorption characteristics, the content of the dichroic pigment (the total amount when plural types are included) is usually 0.1 to 30 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal (a) It is preferably 1-20 parts by mass, more preferably 2-15 parts by mass. If the content of the dichroic pigment is less than this range, the light absorption becomes insufficient, and sufficient polarizing performance cannot be obtained, and if it exceeds this range, the alignment of liquid crystal molecules may be hindered.

(Alignment layer) The laminate 10 may have an alignment layer between the base material layer 11 and the polarizing layer 12. The alignment layer has an alignment restricting force that allows the polymerizable liquid crystal constituting the polarizing layer 12 formed on the base material layer 11 to align the liquid crystal in a desired direction.

The alignment layer makes the liquid crystal alignment of the polymerizable liquid crystal easy. The state of liquid crystal alignment such as horizontal alignment, vertical alignment, mixed alignment, and inclined alignment varies according to the nature of the alignment layer and the polymerizable liquid crystal, and the combination can be arbitrarily selected. For example, if the alignment layer is a material that exhibits horizontal alignment as the alignment limiting force, the polymerizable liquid crystal can form horizontal alignment or mixed alignment, and if it is a material that exhibits vertical alignment, the polymerizable liquid crystal can form vertical alignment or tilted alignment. Expressions such as horizontal and vertical indicate the direction of the long axis of the aligned polymerizable liquid crystal when the plane of the polarizing layer 12 is used as a reference. For example, the vertical alignment refers to the long axis of the aligned polymerizable liquid crystal in a direction perpendicular to the plane of the polarizing layer 12. The vertical here means 90°±20° with respect to the plane of the polarizing layer 12.

Regarding the alignment limiting force, when the alignment layer is formed of an alignment polymer, it can be arbitrarily adjusted by the surface state or friction conditions, and when it is formed of a photo-alignment polymer, it can be adjusted by polarized light irradiation conditions, etc. Adjust freely. Also, the liquid crystal alignment can be controlled by selecting physical properties such as surface tension and liquid crystallinity of the polymerizable liquid crystal compound.

The alignment layer formed between the base material layer 11 and the polarizing layer 12 is preferably insoluble in the solvent used when forming the polarizing layer 12 on the alignment layer, and has heat treatment for removing the solvent or aligning the liquid crystal The heat resistance. The alignment layer may be an alignment layer including an alignment polymer, an optical alignment layer, a groove alignment layer, or the like. Among them, the light alignment layer is preferred in that the alignment direction can be easily controlled when applied to a long rolled 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 in the range of 30 to 300 nm.

Examples of the alignment polymer used in the alignment layer including the alignment polymer include polyamide or gelatin having an amide bond in the molecule, polyimide having an amide bond in the molecule, and As its hydrolysate, polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polypropylene amide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylic acid Acrylic esters, etc. Among them, the alignment polymer is preferably polyvinyl alcohol. These alignment polymers may be used alone or in combination of two or more.

In the case where an alignment layer containing an alignment polymer is formed on a substrate layer composed of a resin film, the alignment layer containing the alignment polymer is usually dissolved by dissolving the alignment polymer in a solvent by coating on the resin film The resulting composition (hereinafter also referred to as "aligned polymer composition") is removed by removing the solvent, or the alignment polymer composition is coated on the resin film, the solvent is removed and rubbed (friction 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, and ethyl alcohol Glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate and other ester solvents; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone and Ketone solvents such as methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane ; Hydrocarbon solvents such as chloroform and chlorobenzene substituted by chlorine, etc. These solvents may be used alone or in combination of two or more.

The concentration of the alignment polymer in the alignment polymer composition may be within a range where the alignment polymer can be completely dissolved in the solvent, and it is preferably 0.1 to 20 in terms of solid content relative to the solution The mass% is more preferably 0.1 to 10 mass %.

As the alignment polymer composition, a commercially available alignment layer forming material can be used directly. Examples of commercially available materials for forming the alignment layer include Sunever (registered trademark) (manufactured by Nissan Chemical Industry Co., Ltd.) and Optomer (registered trademark) (manufactured by JSR Corporation).

Examples of the method for applying the alignment polymer composition to the resin film include spin coating, extrusion, gravure coating, die coating, bar coating, and applicator methods. A well-known method such as a coating method or a printing method such as a flexographic printing method. In the case of manufacturing the layered product of the present invention by a continuous manufacturing method in a roll-to-roll format, the coating method generally uses a printing method such as a gravure coating method, a die coating method, or a flexographic printing method.

By removing the solvent contained in the alignment polymer composition, a dry coating of alignment polymer is formed. Examples of the method for removing the solvent include a natural drying method, an air drying method, a heating drying method, and a reduced pressure drying method.

Examples of the rubbing method include a method of bringing the film of the alignment polymer into contact with the rubbing roller. The friction roller is a roller rotatable with friction cloth.

The photo-alignment layer is usually formed by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter also referred to as a "composition for forming an photo-alignment layer") on a resin film and irradiating polarized light ( It is preferably obtained by polarized UV). The optical alignment layer can arbitrarily control the direction of the alignment limiting force by selecting the polarization direction of the irradiated polarized light, which is better in this respect.

The so-called photoreactive group refers to a group that generates liquid crystal alignment ability by irradiating light. Specifically, it refers to a photoreactor that becomes the origin of the alignment ability of liquid crystals such as alignment induction or isomerization reaction, dimerization reaction, photocrosslinking reaction, or photolysis reaction of molecules generated by irradiation of light. Among the photoreactive groups, those that cause dimerization reaction or photocrosslinking reaction are preferable in terms of excellent alignment. As the photoreactive group that can generate the reaction as described above, it is preferable to have an unsaturated bond, especially a double bond, and more preferably to have a carbon-carbon double bond (C=C bond) or a carbon-nitrogen double bond. The base of at least one of the group consisting of a bond (C=N bond), a nitrogen-nitrogen double bond (N=N bond), and a carbon-oxygen double bond (C=O bond).

Examples of the photoreactive group having a C=C bond include vinyl, polyalkenyl, stilbyl, styrylpyridyl, styrylazolium, chalcone and cinnamyl groups. Wait. From the viewpoint of easier control of reactivity or the performance of alignment limitation during optical alignment, chalcone and cinnamyl groups are preferred. Examples of the photoreactive group having a C=N bond include groups having structures such as aromatic Schiff bases and aromatic hydrazones. Examples of the photoreactive group having an N=N bond include azophenyl, azonaphthyl, aromatic heterocyclic azo, disazo, and mesityl, or oxyazobenzene as the basic Constructor. Examples of the photoreactive group having a C=O bond include a benzophenone group, a coumarin group, an anthraquinone group, a maleimide group, and the like. Such groups may have substituents such as alkyl groups, alkoxy groups, aryl groups, allyloxy groups, cyano groups, alkoxycarbonyl groups, hydroxyl groups, sulfonic acid groups, and halogenated alkyl groups. Among them, a photoreactive group that can generate a photodimerization reaction is preferred. The cinnamyl group and the chalcone group have a relatively small amount of polarized light irradiation required for photoalignment, and are easy to obtain thermal stability or stability over time. The optical alignment layer is preferred. As a polymer having a photoreactive group, it is particularly preferable that the terminal part of the side chain of the polymer has a cinnamic acid group and the cinnamic acid group has a cinnamic acid structure.

In terms of the ease of handling the above composition for forming an optical alignment layer and the ease of obtaining an alignment layer that achieves an alignment with high durability, particularly preferred polymers having a photoreactive group are, for example, side chains A polymer having a group represented by formula (A') (hereinafter also referred to as "polymer (A')" according to circumstances).

[式(A')中， n表示0或1。 X¹ 表示單鍵、-O-、-COO-、-OCO-、-N=N-、-CH=CH-或-CH₂ -。 Y¹ 表示單鍵或-O-。 R¹ 及R² 分別獨立地表示氫原子、碳數1～4之烷基或碳數1～4之烷氧基。 ＊表示相對於聚合物主鏈之鍵結鍵][化14]

[In formula (A'), n represents 0 or 1. X ¹ represents a single bond, -O-, -COO-, -OCO-, -N=N-, -CH=CH-, or -CH ₂ -. Y ¹ represents a single bond or -O-. R ¹ and R ² each independently represent a hydrogen atom, a C 1-4 alkyl group or a C 1-4 alkoxy group. ＊Indicating the bonding with respect to the polymer main chain]

In formula (A'), if X ¹ is any of a single bond, -O-, -COO-, -OCO-, -N=N-, -C=C-, and -CH ₂ -, then polymerize The manufacture of the object (A') itself becomes easy, so it is particularly preferable.

In formula (A'), R ¹ and R ² 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, and an allyl group Oxygen group, alkoxycarbonyl group, carboxyl group, sulfonic acid group, amine group or hydroxyl group, the carboxyl group and the sulfonic acid group can form salts with alkali metal ions. Among these, R ¹ and R ^{2 are more} preferably independently hydrogen atoms, alkyl groups having 1 to 4 carbon atoms or alkoxy groups having 1 to 4 carbon atoms. Examples of the alkyl group include methyl, ethyl, and butyl groups, and examples of the alkoxy group include methoxy, ethoxy, and butoxy groups.

The main chain of the polymer (A') is not particularly limited, and the polymer (A) preferably has a (meth)acrylate unit selected from the group consisting of formula (M-1) or formula (M-2); (Meth) acrylamide unit represented by formula (M-3) or formula (M-4); vinyl ether unit represented by formula (M-5) or formula (M-6); formula (M-7) ) Or a (methyl) styrene unit represented by formula (M-8), and a main chain consisting of a group consisting of a vinyl ester unit represented by formula (M-9) or formula (M-10), Among them, the polymer (A′) further preferably has a main chain composed of units selected from the group consisting of (meth)acrylate units and (meth)acrylamide units. In addition, the "main chain of the polymer (A')" here refers to the longest molecular chain among the molecular chains possessed by the polymer (A').

[化15]

The unit represented by any one of formula (M-1) to formula (M-10) and the group represented by formula (A′) may be directly bonded, or may be bonded via an appropriate linking group. Examples of the linking group include a carbonyloxy group (ester bond), an oxygen atom (ether bond), an amide imino group, a carbonylimino group (acylamine bond), and an iminocarbonylimino group (aminocarbamate) Bond), a divalent aliphatic hydrocarbon group which may have a substituent, 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: phenylene, 2-methoxy-1,4-phenylene, 3-methoxy-1,4-phenylene, 2 -Ethoxy-1,4-phenylene, 3-ethoxy-1,4-phenylene, 2,3,5-trimethoxy-1,4-phenylene, etc. Among these, the linking group is preferably an aliphatic hydrocarbon group, and further preferably a C1-C11 alkanediyl group which may have a substituent. In addition, examples of the alkanediyl group include methylene, ethylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, and nine. Methylene, decamethylene, undecylidene, etc. These can be straight chain or branched chain. In addition, the alkanediyl group may have a substituent. The substituent is, for example, an alkoxy group having 1 to 4 carbon atoms.

In other words, as the structural unit having the base represented by formula (A'), it is preferably represented by formula (A) (hereinafter also referred to as "structural unit (A)" according to circumstances, and will also include the structural unit (A ) Is called "Polymer (A)").

[式(A)中， X¹ 、Y¹ 、R¹ 、R² 及n係與式(A')表示相同含義， S¹ 為碳數1～11之烷二基，[Chem 16]

[In formula (A), X ¹ , Y ¹ , R ¹ , R ² and n are synonymous with formula (A'), S ¹ is an alkanediyl group having 1 to 11 carbon atoms,

所表示之結構為式(M-1)～式(M-10)之任一者所表示之結構][化17]

The structure represented is a structure represented by any one of formula (M-1) to formula (M-10)]

The molecular weight of the polymer (A') or polymer (A) is expressed in terms of weight average molecular weight in terms of polystyrene obtained by, for example, gel permeation chromatography (GPC method), preferably 1×10 ³ ～ 1×10 ⁷ range. Among them, if the molecular weight becomes too high, the solubility in the solvent decreases, making it difficult to prepare the composition for forming an alignment layer, or the sensitivity to light irradiation tends to decrease, so it is preferably 1×10 ⁴ to 1×10 ⁶ Scope.

In addition to the structural unit (A), the polymer (A) may have a structural unit represented by the formula (B) (hereinafter also referred to as "structural unit (B)" according to circumstances).

[式(B)中， m表示0或1。 S² 表示碳數1～11之烷二基。[Chemical 18]

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

所表示之結構為式(M-1)～式(M-10)之任一者所表示之結構。 X² 表示單鍵、-O-、-COO-、-OCO-、-N=N-、-CH=CH-或-CH₂ -。 Y² 表示單鍵或-O-。 R³ 及R⁴ 分別獨立地表示氫原子、碳數1～4之烷基或碳數1～4之烷氧基][Chem 19]

The structure represented is a structure represented by any one of formula (M-1) to formula (M-10). X ² represents a single bond, -O-, -COO-, -OCO-, -N=N-, -CH=CH- or -CH ₂ -. Y ² represents a single bond or -O-. R ³ and R ⁴ each independently represent a hydrogen atom, a C 1-4 alkyl group or a C 1-4 alkoxy group]

In formula (B), the specific examples of S ^{2 are} the same as the specific examples of S ¹ of formula (A), and the specific examples of the alkyl and alkoxy groups of R ³ and R ⁴ are respectively the same as those of formula (A) Specific examples of R ¹ and R ^{2 are} the same.

When the molar fractions of the structural unit (A) and the structural unit (B) with respect to all the structural units of the polymer (A) are set to p and q (p+q is 1), it is preferable to satisfy 0.25 <p≦1 and 0≦q<0.75 [the case where the polymer (A) has a structural unit (A) and p is 1 here means that the polymer (A) is composed of the structural unit (A) polymer. In the polymer composed of the structural unit (A), the structural unit (A) may be one kind, or two or more kinds]. Among them, the polymer (A) can have structural units other than the structural unit (A) and the structural unit (B) within the range that does not significantly damage the alignment ability generated by light irradiation (hereinafter also referred to as "other structure according to the situation unit").

The polymer (A) can be produced by polymerizing or copolymerizing monomers derived from the structural unit (A) and monomers derived from the structural unit (B) or other structural units as necessary. In this polymerization or copolymerization, an addition polymerization method is usually used. Examples of the 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 monomers used to satisfy the above-mentioned preferred molecular weight of the polymer (A).

In the above, the polymer (A) has been described in detail as the preferred polymer having a photoreactive group. The composition for forming an alignment layer is obtained by using the photoreactive group polymer (preferably The polymer (A)) is prepared by dissolving in an appropriate solvent. The solvent can dissolve the polymer having a photoreactive group, and can be appropriately selected within the range of the composition for forming an alignment layer having an appropriate viscosity. 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, and ethyl alcohol Glycol methyl ether acetate, γ-butyrolactone or propylene glycol methyl ether acetate and ethyl lactate and other ester solvents; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl alcohol Ketone solvents such as isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; Chlorinated solvents such as chloroform and chlorobenzene; amide solvents such as N-methylpyrrolidone, N,N-dimethylformamide, γ-butyrolactone, and dimethylacetamide. These solvents can be used alone or in combination.

The content of the polymer or monomer having a photoreactive group with respect to the composition for forming an optical alignment layer may be appropriate according to the type of the polymer or monomer having a photoreactive group or the thickness of the optical alignment layer to be manufactured The adjustment is preferably 0.2% by mass or more, and particularly preferably 0.3 to 10% by mass. In addition, polymer materials such as polyvinyl alcohol or polyimide or light sensitizers may be included within a range that does not significantly impair the characteristics of the optical alignment layer.

As a method of applying the composition for forming the optical alignment layer on the resin film, the same method as the method of applying the above-mentioned alignment polymer composition on the resin film may be mentioned. As a method of removing the solvent from the applied composition for forming the optical alignment layer, for example, the same method as the method of removing the solvent from the alignment polymer composition can be cited.

When polarizing light is irradiated, it may be a form in which polarized light is directly irradiated from the solvent for forming the composition for forming an optical alignment layer coated on a resin film or the like, or polarized light may be irradiated from the resin film side to transmit polarized light. The form of irradiation. In addition, the polarized light is preferably substantially parallel light. The wavelength of the polarized light to be irradiated is preferably a wavelength region in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) with a wavelength ranging from 250 nm to 400 nm is particularly preferred. Examples of the light source used for the polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, KrF, ArF and other ultraviolet lasers. More preferred are high-pressure mercury lamps, ultra-high pressure mercury lamps, and metal halide lamps. . These lamps are better because the luminous intensity of ultraviolet light with a wavelength of 313 nm is larger. Polarized light can be irradiated by irradiating light from the light source through an appropriate polarizing element. As the polarizing element, a polarizing filter, a polarizing element such as Glan-Thompson, Glan-Taylor, or a wire grid type polarizing element can be used.

Furthermore, if shielding is performed during rubbing or polarized light irradiation, a plurality of regions (patterns) with different liquid crystal alignment directions can also be formed.

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

As a method for obtaining the groove alignment layer, a method of forming a concave-convex pattern by exposing the surface of the photosensitive polyimide film through an exposure mask having a slit with a pattern shape, performing development and rinsing treatment; A method of forming a UV-curable resin layer before curing on a plate-shaped master with grooves on the surface, and moving the resin layer to a resin film for curing; and for the UV-curable resin before curing formed on the resin film The film is pressed against a roll-shaped master with a plurality of grooves to form irregularities, and then a method of curing is performed. Specifically, the methods described in Japanese Patent Laid-Open No. 6-34976 and Japanese Patent Laid-Open No. 2011-242743 can be cited.

In order to obtain alignment with less alignment disorder, the width of the convex portion of the trench alignment layer is preferably 0.05 μm to 5 μm, the width of the concave portion is preferably 0.1 μm to 5 μm, and the depth of the step difference of the concave and convex is preferably 2 μm Below, it is preferably 0.01 μm to 1 μm or less.

(Other layers) The laminated body 10 may further have an adhesive layer on the polarizing layer 12 side. The adhesive layer is used to bond the layered body 10 to the image display element, window film or touch sensor of the display device, or to layer the phase difference layer and the layered body. As the adhesive, (meth)acrylic adhesive, styrene adhesive, polysiloxane adhesive, rubber adhesive, urethane adhesive, polyester adhesive, epoxy can be used Copolymer adhesive, etc.

The laminate 10 may have a phase difference layer. Examples of the retardation layer include a λ/4 plate, a λ/2 plate, an anode C plate, an inverse wavelength dispersive λ/4 plate, an inverse wavelength dispersive λ/2 plate, and combinations thereof. Examples of the combination of retardation layers include a combination of a λ/4 plate and an anode C plate with reverse wavelength dispersion, and a combination of a λ/2 plate and a λ/4 plate. The retardation layer can be made of a transparent resin film forming the above-mentioned base material layer or a composition containing a polymerizable liquid crystal compound. The retardation layer can be produced by applying a composition containing a polymerizable liquid crystal compound on an alignment film, and hardening the polymerizable liquid crystal compound. The retardation layer may be a layer containing a cured product of a polymerizable liquid crystal compound, and may further be a layer containing an alignment film and a base material. In the production of the retardation layer, for example, the polymerizable liquid crystal compound exemplified in the description of the polarizing layer 12 described above, or the polymerizable liquid crystal described in Japanese Patent Laid-Open No. 2010-31223 or Japanese Patent Laid-Open No. 2009-173893 Compounds etc. 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 contained in the retardation layer may be, for example, the resin film exemplified in the description of the base material layer 11 described above. The phase difference layer can be laminated through the adhesive layer.

The laminate 10 may have a surface treatment layer (coating layer) such as a hard coat layer, an anti-glare layer, an anti-reflection layer, an anti-static layer, and an anti-fouling layer.

The laminate 10 may have a window film or a light-shielding pattern (frame) disposed on the viewing side of the polarizing layer 12 as a reference. The window film is formed by including a hard coat layer on at least one side of the transparent substrate layer. The window film is not as hard and straight as the existing glass, and has the characteristics of flexibility. The wiring of the display device can be hidden by the shading pattern so that it is not recognized by the user. The layered body 10 can be layered on the touch sensor.

<Manufacturing method of laminate> The polarizing layer 12 can be formed by coating the composition (A) on the base material layer 11 and coating the composition (A) on the alignment layer when there is an alignment layer. The composition (A) may further contain a polymerization initiator, a leveling agent, a solvent, a photosensitizer, a polymerization inhibitor, a leveling agent, and the like in addition to the dichroic dye and the polymerizable liquid crystal compound.

(Polymerization initiator) The polymerization initiator is a compound that can start a polymerization reaction of a polymerizable liquid crystal or the like. As the polymerization initiator, from the viewpoint of not depending on the phase state of the thermotropic liquid crystal, a photopolymerization initiator that generates active radicals by the action of light is preferred.

Examples of the polymerization initiator include a benzoin compound, a benzophenone compound, a benzophenone compound, an acylphosphine oxide compound, a triammonium compound, a thionium salt, and a manganese salt.

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

Examples of the benzophenone compound include benzophenone, methyl o-benzoyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide , 3,3',4,4'-tetra (third butyl peroxycarbonyl) benzophenone and 2,4,6-trimethyl benzophenone and so on.

Examples of the benzophenone compounds include diethoxyacetophenone, 2-methyl-2-𠰌olinyl-1-(4-methylthiophenyl)propane-1-one, and 2-benzyl -2-dimethylamino-1-(4-𠰌olinylphenyl)butane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1,2-di Phenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1 -Oligomers of hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1-one, etc.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, and the like.

Examples of tris compounds include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tris, 2,4-bis(trichloro Methyl)-6-(4-methoxynaphthyl)-1,3,5-tris, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)- 1,3,5-tris, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-tris, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-tris, 2,4-bis(trichloromethyl)-6 -[2-(4-Diethylamino-2-methylphenyl)vinyl]-1,3,5-tris and 2,4-bis(trichloromethyl)-6-[2-( 3,4-dimethoxyphenyl)vinyl]-1,3,5-tris, etc.

As the polymerization initiator, commercially available ones can be used. Examples of 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.) ; Seikuol (registered trademark) BZ, Z, and BEE (made by Seiko Chemical Co., Ltd.); Kayacure (registered trademark) BP100, and UVI-6992 (made by Dow Chemical Co., Ltd.); Adeka Optomer SP-152, N-1717 , N-1919, SP-170, Adeka Arkls NCI-831, Adeka Arkls NCI-930 (made by ADEKA Corporation); TAZ-A, and TAZ-PP (made by Nihon Siber Hegner Co., Ltd.); and TAZ-104 (Made by Sanhe Chemical Co., Ltd.) etc. The composition (A) may contain one kind of polymerization initiator, or may contain a plurality of plural kinds of polymerization initiators in combination with the light source.

The content of the polymerization initiator in the composition (A) can be appropriately adjusted according to the type and amount of the polymerizable liquid crystal. The content of the polymerization initiator is usually 0.1 to 30 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal. If the content of the polymerization initiator is within the above range, the polymerization can be carried out without disturbing the alignment of the polymerizable liquid crystal.

等𠮿酮化合物(例如2,4-二乙基-9-氧硫𠮿

、2-異丙基-9-氧硫𠮿

等)；蒽及含有烷氧基之蒽(例如二丁氧基蒽等)等蒽化合物；啡噻𠯤及紅螢烯等。(Sensitizer) The composition (A) may contain a sensitizer. As the sensitizer, a photosensitizer is preferred. As the sensitizer, for example, 𠮿one and 9-oxosulfur 𠮿

Etc. ketone compounds (e.g. 2,4-diethyl-9-oxythio) 𠮿

、2-isopropyl-9-oxysulfur 𠮿

Etc.); anthracene and anthracene containing alkoxy groups (such as dibutoxyanthracene, etc.); anthracene compounds;

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 use amount of the sensitizer is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and still more preferably 0.5 to 3 parts by mass relative to 100 parts by mass of the content of the polymerizable liquid crystal.

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

Examples of the polymerization inhibitors include hydroquinone, alkoxy-containing hydroquinone, alkoxy-containing catechol (for example, butyl catechol, etc.), pyrogallol, 2,2,6,6-Tetramethyl-1-piperidinyloxy radical and other free radical scavengers; thiophenols; β-naphthylamines and β-naphthols.

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

(Leveling agent) The composition (A) may contain a leveling agent. The so-called leveling agent refers to an additive that has the function of adjusting the fluidity of the composition and making the film obtained by coating the composition flatter. Examples of the leveling agent include organic-modified silicone-based, polyacrylate-based, and perfluoroalkyl-based leveling agents. Specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all of which are manufactured by Dow Corning Toray Co., Ltd.), KP321, KP323, KP324, KP326, KP340 , KP341, X22-161A, KF6001 (the above are all manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (the above are all by Momentive Performance Materials Japan Co., Ltd. Manufacturing), Fluorinert (registered trademark) FC-72, Fluorinert FC-40, Fluorinert FC-43, Fluorinert FC-3283 (the above are all manufactured by Sumitomo 3M), MEGAFAC (registered trademark) R-08, MEGAFAC R- 30, MEGAFAC R-90, MEGAFAC F-410, MEGAFAC F-411, MEGAFAC F-443, MEGAFAC F-445, MEGAFAC F-470, MEGAFAC F-477, MEGAFAC F-479, MEGAFAC F-482, MEGAFAC F-482 483 (above are all manufactured by DIC (share)), Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (above are all made by Mitsubishi Materials Electronic Chemicals (share)), Surflon (registered trademark) S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-105, KH-40, SA-100 (the above are all manufactured by AGC Seimi Chemical Co., Ltd.), trade name E1830, commodity Name E5844 (made by Daikin Chemical Research Institute), BM-1000, BM-1100, BYK-352, BYK-353 and BYK-361N (all are trade names, manufactured by BM Chemie), etc. Among them, polyacrylate leveling agents and perfluoroalkyl leveling agents are preferred.

When the composition (A) contains a leveling agent, the content of the leveling agent relative to the content of the polymerizable liquid crystal is 100 parts by mass, preferably 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass, and further It is preferably 0.1 to 3 parts by mass. If the content of the leveling agent is within the above range, the polymerizable liquid crystal is easily aligned horizontally, and the resulting polarizing layer tends to be smoother. If the content of the leveling agent with respect to the polymerizable liquid crystal exceeds the above range, the resulting polarizing layer tends to be uneven. Furthermore, the composition (A) may contain two or more leveling agents.

(Solvent) The composition (A) may contain a solvent. Generally, the viscosity of the polymerizable liquid crystal compound is high. Therefore, by making the composition (A) dissolved in a solvent, coating becomes easy, and as a result, a polarizing layer is easily formed in many cases. The solvent is preferably one that can completely dissolve the polymerizable liquid crystal compound, and preferably a solvent that is inactive 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, and ethylene glycol Alcohol methyl ether acetate, γ-butyrolactone or propylene glycol methyl ether acetate and ethyl lactate and other ester solvents; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl Ketone solvents such as isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chloroform And chlorobenzene and other chlorine-containing solvents; dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and other amides Solvent, etc. These solvents may be used alone or in combination of two or more.

The content of the solvent is preferably 50 to 98% by mass relative to 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. If the content of the solid component is 50% by mass or less, the viscosity of the composition (A) becomes low, so the thickness of the polarizing layer tends to become substantially uniform. As a result, the polarizing layer tends to be less prone to unevenness. In addition, the content of the solid component can be determined in consideration of the thickness of the polarizing layer to be manufactured.

(Reactive additive) The composition (A) may contain a reactive additive. As the reactive additive, those having a carbon-carbon unsaturated bond and an active hydrogen reactive group in the molecule are preferred. In addition, the "active hydrogen reactive group" here means a group reactive with a group having active hydrogen such as a carboxyl group (-COOH), a hydroxyl group (-OH), an amine group (-NH ₂ ), a glycidyl group , Oxazoline group, carbodiimide group, aziridine group, amide imide group, isocyanate group, thioisocyanate group, maleic anhydride group, etc. are representative examples. The number of carbon-carbon unsaturated bonds and active hydrogen reactive groups possessed by the reactive additive is usually 1 to 20, preferably 1 to 10, respectively.

Preferably, at least two active hydrogen reactive groups are present in the reactive additive. In this case, the presence of plural active hydrogen reactive groups may be the same or different.

The carbon-carbon unsaturated bond possessed by the reactive additive may be a carbon-carbon double bond or a carbon-carbon triple bond, or a combination thereof, and is preferably a carbon-carbon double bond. Among them, the reactive additive preferably contains a carbon-carbon unsaturated bond in the form of a vinyl group and/or (meth)acryloyl group. Furthermore, it is preferable that the active hydrogen reactive group is at least one reactive additive selected from the group consisting of epoxy groups, glycidyl groups, and isocyanate groups, and it is more preferable to have the reactivity of an acryl group and an isocyanate group. additive.

Specific examples of the reactive additives include compounds having a (meth)acryloyl group and an epoxy group such as methacryloyloxyglycidyl ether or acryloxyglycidyl ether; oxetane acrylate Compounds having (meth)acryloyl and oxetanyl groups such as esters or oxetanyl methacrylate; lactone acrylates or lactone methacrylates having (meth)acryloyl groups Compounds with lactone groups; compounds with vinyl and oxazoline groups such as vinyl oxazoline or isopropenyl oxazoline; isocyanate methyl acrylate, isocyanate methyl methacrylate, 2-isocyanate acrylate Oligomers of compounds having (meth)acryloyl and isocyanate groups such as ethyl ester and 2-isocyanatoethyl methacrylate. In addition, a compound having a vinyl group or a vinylidene 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 are preferred , 2-Isocyanatoethyl methacrylate and the above oligomers, particularly preferably isocyanatomethyl acrylate, 2-isocyanate ethyl acrylate and the above oligomers.

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

[化20]

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

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

[化21]

As the compound (YY), commercially available products can be used as they are, or they can be purified if necessary. Examples of commercially available products include 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 5 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal.

Before applying the composition (A) on the substrate layer, it is preferable to adjust the moisture content of the substrate layer. The moisture content of the base material layer may be 5.0% or less, preferably 3.0% or less. The moisture content of the substrate layer 11 may be 0.0% or more. When the composition (A) is coated on a substrate layer having such a moisture content, the uniformity of the alignment direction of the polymerizable liquid crystal and the dichroic dye improves. In particular, when the laminate 10 is extended, it is easy to visually recognize the uneven optical characteristics of the polarizing layer, even after the extension, it is easy to maintain the good optical characteristics of the polarizing layer. The moisture content of the base material layer is measured by the method described in the following examples.

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

(Coating method) Examples of the method for applying the composition (A) to the substrate layer 11 or the alignment layer include extrusion coating method, direct gravure coating method, reverse gravure coating method, CAP coating method, and slit Coating method, microgravure method, die coating method, inkjet method, etc. In addition, a method of coating using a coating machine such as a dip coater, a bar coater, or a spin coater can also be mentioned. Among them, in the case of continuous coating in a roll-to-roll format, it is preferable to use the coating method of micro gravure method, inkjet method, slit coating method, die coating method, etc. for coating on glass, etc. In the case of a monolithic body, a spin coating method with high uniformity is preferred. In the case of roll-to-roll coating, an alignment polymer composition, a composition for forming an optical alignment layer, etc. may be coated on the base layer 11 to form an alignment layer, and then continuous on the obtained alignment layer The composition (A) is coated.

(Drying method) Examples of the drying method for removing the solvent contained in the composition (A) include natural drying, air drying, heating drying, reduced-pressure drying, and methods combining these. Among them, natural drying or heat drying is preferred. 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 10 seconds to 10 minutes, and more preferably 30 seconds to 5 minutes. The composition for forming an optical alignment layer and the alignment polymer composition can also be dried in the same manner.

(Aggregation method) As a method of polymerizing the polymerizable liquid crystal compound, photopolymerization is preferred. The photopolymerization is performed by irradiating the active energy ray to the composition (A) containing the polymerizable liquid crystal compound applied on the base material layer 11 or the alignment layer. As the active energy ray to be irradiated, depending on the type of the polymerizable liquid crystal compound contained in the dry film (especially the type of photopolymerizable functional group possessed by the polymerizable liquid crystal compound), when the photopolymerization initiator is included The type of photopolymerization initiator and its equivalent amount are appropriately selected. Specifically, examples of the active energy rays include one or more kinds of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays. Among them, in terms of easy control of the progress of the polymerization reaction and the aspect that it can be used as a photopolymerization device in a wide range of users in the field, it is preferably ultraviolet light, and it is preferably carried out by ultraviolet light The method of photopolymerization selects the type of polymerizable liquid crystal compound.

Examples of the light source of the active energy rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten filament lamps, gallium lamps, excimer lasers, and emission wavelengths. LED light source, chemical lamp, black light lamp, microwave-excited mercury lamp, metal halide lamp, etc. with light in the range of 380-440 nm.

The ultraviolet irradiation intensity is usually 10 mW/cm ² to 3,000 mW/cm ² . The ultraviolet irradiation intensity is preferably the intensity of the wavelength region effective for the activation of the cationic polymerization initiator or the radical polymerization initiator. The time for irradiating light is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, and still more preferably 0.1 seconds to 1 minute. If this ultraviolet irradiation intensity is irradiated once or plural times, the cumulative light amount is, for example, 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 to 1,000 mJ/cm ² . When the cumulative light amount does not reach the lower limit, the curing of the polymerizable liquid crystal compound may become insufficient, and good transferability may not be obtained. Conversely, when the cumulative light amount exceeds the upper limit, the optical film including the optically anisotropic layer may be colored.

<Display device> The display device is not particularly limited, and examples include organic electroluminescence (organic EL) display devices, inorganic electroluminescence (inorganic EL) display devices, liquid crystal display devices, touch panel display devices, electroluminescence display devices, etc. . Since the display device of the embodiment of this embodiment has the extensible laminate 10, it can be preferably used for an extensible display device, and particularly preferably for an organic EL display device.

Hereinafter, the present invention will be described in further detail with examples. "%" and "parts" in the examples are mass% and mass parts unless otherwise specified. [Example]

[Tensile modulus of elasticity] The tensile modulus of elasticity is measured in accordance with JIS K7161, using UTM (Universal Testing Machine, Autograph AG-X, Shimadzu Corporation), when it extends in the absorption axis direction and the transmission axis direction, respectively. The extension conditions were set to normal temperature (temperature 23°C), speed 1.5 mm/min, width 40 mm, and gauge length 50 mm.

[Total haze value] Regarding the laminate before and after the extension in each extension direction and extension rate, the total haze value was measured using a haze meter (HM-150, Murakami Color Technology Research Institute Co., Ltd.) according to JIS K7136, respectively. The absolute value of the difference between the total haze values of the laminate before and after the extension at each elongation is defined as ΔH. Furthermore, the total haze value can be calculated by the following formula. Total haze value (%) = scattering transmittance (%) / total light transmittance (%) × 100

[Visual sensitivity correction individual body transmittance and visual sensitivity correction polarized degree] The laminated body before and after extending in each extending direction and elongation is measured for the visual acuity correction individual body transmittance and visual acuity according to JIS Z 8701 using an ultraviolet-visible spectrophotometer (V7100, Japan Spectroscopy Co., Ltd.) Correct the polarization. The absolute value of the difference between the transmittance of the laminated body before and after the extension at each elongation and the degree of polarization correction of the individual body transmittance and the correction of the polarization of the optical sensitivity is set to ΔT and ΔP, respectively.

[Moisture content of base material layer] The moisture content of the base material layer was calculated based on the following formula using MS-70, a heat-drying moisture meter manufactured by A&D Co., Ltd. The size of the substrate layer when measuring the moisture content is set to 100 mm×100 mm. Moisture content (%) of the substrate layer = 100 × (W _A- W _B- W _P )/(W _B- W ₂ ) W _P = W _1- W ₂ W _A is the sample on which the substrate layer is placed The weight of the dish. W _B is placed the base layer of the sample pan was heated at 120 ℃, time variation rate of the water becomes by weight of 0.02% / min or less. W ₁ is the weight of the sample dish. W ₂ is the weight when the sample dish is heated at 120°C and the time change of the moisture content becomes 0.02%/min or less. W _P reflecting surface of the water content of the sample dish.

[Appearance evaluation] The presence or absence of unevenness, cracks, haze, and breakage in the laminate after the extension in each extension direction and extension rate were visually evaluated. ○: No unevenness, no cracks, no haze, and no breakage ×: No unevenness, no cracks, haze, and no breakage ××: Cracks, breaks, or unevenness

[Polymeric liquid crystal compound] As the polymerizable liquid crystal compound, a polymerizable liquid crystal compound represented by formula (1-6) [hereinafter also referred to as compound (1-6)] 75 parts and a polymerizable liquid crystal compound represented by formula (1-7) [hereinafter also referred to as For compound (1-7)] 25 parts.

[化22]

[化23]

Compound (1-6) and Compound (1-7) were synthesized by the method described in Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996).

As the dichroic dye, the azo dye described in the examples of Japanese Patent Laid-Open No. 2013-101328 represented by the following formulas (2-1a), (2-1b), and (2-3a) is used.

[化24]

[化25]

[化26]

[Composition for Forming Polarizing Layer] The composition for forming a polarizing layer is composed of 75 parts of compound (1-6), 25 parts of compound (1-7), and the above formulas (2-1a), (2-1b), (2 -3a) 2.5 parts each of the azo pigments shown as 2-dimethylamino-2-benzyl-1-(4-𠰌olinylphenyl)butane-1-one (Irgacure) 369, manufactured by BASF JAPAN) 6 parts by weight, and 1.2 parts of a polyacrylate compound (BYK-361N, manufactured by BYK-Chemie) as a leveling agent were mixed with 400 parts of toluene in the solvent, and the resulting mixture was added at 80 It was prepared by stirring at ℃ for 1 hour.

[Polymer 1] The polymer 1 is a polymer having a photoreactive group including the following structural units.

根據GPC測定，顯示所得之聚合物1之分子量之數量平均分子量為28200、Mw/Mn為1.82，單體含量為0.5%。[化27]

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

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

[Example 1] A base layer containing triacetyl cellulose (TAC) with a thickness of 25 μm is prepared. The base material layer was heated and dried at 120° C. for 5 minutes to make the moisture content 2%. The composition for forming an alignment layer was coated on the base material layer by a bar coating method, and the coating film was dried at 80° C. for 1 minute. The thickness is 100 nm.

Then, using a UV irradiation device (SPOT CURE SP-7, manufactured by Niuwei Electric Co., Ltd.), the light having a cumulative light amount of 100 mJ/cm ² measured at a wavelength of 365 nm was irradiated through the wire grid (UIS-27132##, Polarized light made by Niuwei Electric Co., Ltd., thereby giving alignment performance and obtaining an alignment layer.

The composition for forming a polarizing layer is coated on the obtained alignment layer by a bar coating method. After the coating film was heated and dried at 100°C for 2 minutes, it was cooled to room temperature to obtain a dried film. Using a UV irradiation device (SPOT CURE SP-7), the resulting film was irradiated with ultraviolet rays so that the cumulative light amount became 1200 mJ/cm ² (based on 365 nm) to obtain a polarizing layer with a thickness of 3 μm. With respect to the obtained laminate, each tensile elastic modulus (E _A and E _T ) in the absorption axis direction and the transmission axis direction was measured. E _A of this laminate is 3180 MPa, and E _T is 3900 MPa. In addition, before the extension, after extending at an elongation of 5% in the direction of the absorption axis, and after extending at an extension of 5% in the direction of the transmission axis, the total haze value, visual acuity correction individual body transmittance, visual acuity correction polarized degree are evaluated And appearance. The results are shown in Table 1. The extension is performed using UTM. The extension conditions were set to normal temperature, speed 1.5 mm/min, width 40 mm, and gauge length 50 mm.

[Example 2] In Example 1, except that the elongation in the absorption axis direction and the elongation in the transmission axis direction were 10%, respectively, a laminate was produced in the same manner as in Example 1.

[Example 3] In Example 1, the base material layer containing triacetyl cellulose (TAC) was changed to a base material layer containing polyethylene terephthalate (PET), in addition to In Example 1, a laminate was produced in the same manner. The thickness of the substrate layer containing PET is 50 μm. E _A of this laminate is 4500 MPa, and E _T is 3300 MPa.

[Example 4] In Example 3, except that the elongation in the absorption axis direction and the elongation in the transmission axis direction were 10%, respectively, a laminate was produced in the same manner as in Example 3.

[Comparative Example 1] After immersing a polyvinyl alcohol film [trade name "Kuraray Vinylon VF-PE#3000" manufactured by Kuraray Co., Ltd.] with an average polymerization degree of about 2400, a saponification degree of 99.9 mol%, and a thickness of 30 μm in 37°C pure water, Immersed in an aqueous solution containing iodine and potassium iodide at 30°C (iodine/potassium iodide/water (weight ratio) = 0.05/1.7/100).

Immersed in a 58°C aqueous solution containing potassium iodide and boric acid (potassium iodide/boric acid/water (weight ratio) = 12/3.2/100). After the film was washed with pure water at 15°C, it was dried at 80°C to obtain a polarizing layer with a thickness of about 12 μm which had iodine adsorbed on polyvinyl alcohol. The extension is mainly performed by the steps of iodine dyeing and boric acid treatment, and the total extension magnification is 5.5 times. A substrate layer containing a TAC film (trade name "KC2UA" manufactured by Konica Minolta Co., Ltd.) with a thickness of 25 μm was bonded to one side of the obtained polarizing layer via an adhesive containing an aqueous solution of a polyvinyl alcohol-based resin. Polarizer. The laminate has an E _A of 8500 MPa and an E _T of 4950 MPa.

About the obtained layered product, respectively, after elongation of 5% in order to extend the absorption axis direction, and then to 5% elongation extending direction of the transmission axis measurement of the tensile modulus of elasticity (E _A and E _T). In addition, before the extension, after extending at an elongation of 5% in the direction of the absorption axis, and after extending at an extension of 5% in the direction of the transmission axis, the total haze value, visual acuity correction individual body transmittance, visual acuity correction polarized degree are evaluated And appearance. The results are shown in Table 1.

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

[Comparative Example 3] In Comparative Example 1, a polyethylene terephthalate (PET) film (Toray Co., Ltd.) was used instead of a TAC film with a thickness of 25 μm, except that it was the same as Comparative Example 1. Make a laminate. The thickness of the PET film is 38 μm. The laminate has an E _A of 9900 MPa and an E _T of 5100 MPa.

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

[Table 1]

As shown in Table 1, the difference between the total haze value before and after extension of the laminates of Examples 1-4, visual sensitivity correction individual body transmittance and visual sensitivity correction polarization degree is small, and after extension, it also shows good Exterior. On the other hand, in Comparative Example 1, the difference in visual sensitivity correction polarization before and after extension was large, and sufficient results were not obtained in the appearance evaluation after extension. In Comparative Example 2, breakage occurred during extension. In Comparative Example 3, the differences in total haze value, visual sensitivity correction individual body transmittance, and visual sensitivity correction polarized degree are 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.

[Extended test] Regarding the laminates produced in Examples 5, 6 and Comparative Example 5, after measuring the reflectance, using an UTM in an environment with a temperature of 60°C and a rate of elongation of 5% at a speed of 2.5 mm/min, the elongation was maintained, The reflectance measurement and appearance evaluation were performed. The initial length of the sample for measurement of each laminate is 50 mm in width and 40 mm in width. The extension test was performed when extending in the absorption axis direction (MD direction) and the transmission axis direction (TD direction), respectively.

The reflectance was measured by sequentially setting a measurement sample and a reflection plate (aluminum plate, reflectance 97%) with a spectrophotometer (CM-2600d, manufactured by Konica Minolta Co., Ltd., SCI mode). The absolute value Δreflectance [%] of the difference between the reflectance [%] measured before stretching and the reflectance [%] measured while maintaining the stretched state is obtained. The Δreflectance [%] can be obtained by the following formula. Δreflectivity [%] = | Y (before stretching)-Y (stretched state) | Y (before extension) = reflectance measured before extension [%] Y (extended state) = reflectivity measured while maintaining the extended state [%]

The appearance evaluation is based on visual evaluation of the presence or absence of unevenness, cracks, haze and breakage. ○: No unevenness, no cracks, no haze, and no breakage ×: No unevenness, no cracks, haze, and no breakage ××: Cracks, breaks, or unevenness

[Preparation of coated retardation layer with adhesive layer on both sides] (Composition for formation of 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) were mixed, and the resulting mixture was stirred at 80°C for 1 hour, by This obtains a composition for forming an alignment film.

[Chem 28]

(Composition for phase difference layer formation) A leveling agent (F-556; DIC Corporation) was added to 100 parts by mass of the 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. Manufacturing) 1.0 parts by mass, and 2-dimethylamino-2-benzyl-1-(4-𠰌olinylphenyl)butane-1-one (Irgacure 369, BASF JAPAN Co., Ltd. as a polymerization initiator Made by the company) 6 quality parts. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%, and stirred at 80°C for 1 hour, thereby obtaining a composition for forming a phase difference layer. (Polymer liquid crystal compound A)

(聚合性液晶化合物B)[Chem 29]

(Polymer liquid crystal compound B)

聚合性液晶化合物A係藉由日本專利特開2010-31223號公報中記載之方法而製造。又，聚合性液晶化合物B係依據日本專利特開2009-173893號公報中記載之方法而製造。[化30]

The polymerizable liquid crystal compound A is produced by the method described in Japanese Patent Laid-Open No. 2010-31223. In addition, the polymerizable liquid crystal compound B is manufactured according to the method described in Japanese Patent Laid-Open No. 2009-173893.

(Production of a laminate including a substrate, an alignment film, and a layer made by curing a polymerizable liquid crystal compound) As a substrate, prepare a 50 μm-thick cycloolefin resin film [ZF-14-50, ZEON JAPAN Co., Ltd. Co., Ltd.], implemented corona treatment. The composition for forming an alignment film was applied to the surface subjected to corona treatment using a bar coater. The coated film was dried at 80°C for 1 minute. Using a polarized UV irradiation device [trade name "SPOT CURE SP-9" of Niuwei Electric Co., Ltd.], the dried coating film was irradiated with polarized UV at an axis angle of 45° to obtain an alignment film. The irradiation of polarized UV is performed in such a manner that the cumulative light amount at a wavelength of 313 nm becomes 100 mJ/cm ² . Then, using a bar coater, the composition for forming a retardation layer was coated on the alignment film. The coated film was dried at 120°C for 1 minute. Use a high-pressure mercury lamp [trade name of Niuwei Electric Co., Ltd.: "Unicure VB-15201BY-A"] to irradiate the dried coating film with ultraviolet rays. The step of irradiating ultraviolet rays is performed under a nitrogen atmosphere in such a manner that the cumulative light amount at a wavelength of 365 nm becomes 400 mJ/cm ² . Immediately after irradiation, as a cooling step, the cured film was put into an oven set at 5°C for 20 seconds. Immediately after being taken out of the oven, the above ultraviolet irradiation step and cooling step were performed again (that is, the total cumulative light amount of the two ultraviolet irradiations was 800 mJ/cm ² ), to obtain the base material, the alignment film, and the hardening of the polymerizable liquid crystal compound A layered body of layers.

The following adhesive layer is laminated on the layer formed by curing the polymerizable liquid crystal compound in the produced laminate. Then, the base material was peeled off from the laminate, and the adhesive layer was also laminated on the exposed surface in the same manner. In this way, a coated retardation layer including an adhesive layer, a layer made by curing a polymerizable liquid crystal compound, an alignment film, and an adhesive layer on both sides of the adhesive layer is prepared. The layer hardened by the polymerizable liquid crystal compound has a retardation value of λ/4.

[Fabrication of film retardation layer with adhesive layer on both sides] ZEONOR FILM (ZEON JAPAN Co., Ltd., in-plane retardation value with respect to light of wavelength λ=550 nm: 138 nm) is prepared as a film obtained by uniaxially stretching a cyclic olefin resin film. The following adhesive layers were deposited on both sides of the film.

(Adhesive layer) While stirring under a nitrogen atmosphere, butyl acrylate: 70 parts by mass, ethyl acrylate: 20 parts by mass, acrylic acid: 2.0 parts by mass, and radical polymerization initiator (2,2'-azobisisobutyronitrile): 0.2 By mass part, while making it react at 55 degreeC etc., acrylic resin was obtained.

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 Industry Co., Ltd.): 0.5 parts by mass are mixed. Ethyl acetate was added so that the concentration of the entire solid content became 10% to obtain an adhesive composition.

Using an applicator, the obtained adhesive composition was applied to the release-treated surface of the polyethylene terephthalate film (thickness 38 μm) subjected to release treatment so that the thickness after drying became 25 μm. The coating layer was dried at 100°C for 1 minute to obtain a film with an adhesive layer. After that, another polyethylene terephthalate film (thickness 38 μm) that had undergone release treatment was attached to the adhesive layer. Thereafter, it was cured for 7 days under the conditions of a temperature of 23° C. and a relative humidity of 50% RH.

<Example 5> The above-mentioned coated retardation layer with an adhesive layer on both sides was bonded to the polarizing layer of the laminate including the base material layer/polarizing layer produced in Example 1 through one adhesive layer. The retardation axis of the layer formed by hardening the polymerizable liquid crystal compound is 45 degrees relative to the absorption axis of the polarizing layer. In this way, a circular polarizing plate including a base material layer/polarizing layer/adhesive layer/coated retardation plate/adhesive layer is produced. The obtained circular polarizing plate was subjected to an extension test. The results are shown in Table 2.

<Example 6> The polarizing layer of the laminate including the base material layer/polarizing layer produced in Example 1 and the above-mentioned film-type retardation layer were bonded via an adhesive layer. The retardation axis of the film-type retardation layer is 45 degrees relative to the absorption axis of the polarizing layer. In this way, a circular polarizing plate including the base material layer/polarizing layer/adhesive layer/film-type retardation layer/adhesive layer is produced. The obtained circular polarizing plate was subjected to an extension test. The results are shown in Table 2.

<Comparative Example 5> A laminate including a substrate/polarizing layer/adhesive layer/coated retardation layer/adhesive layer was produced in the same manner as in Example 5 except that the laminate including the substrate layer/polarizing layer produced in Comparative Example 4 was used. Round polarizer. The obtained circular polarizing plate was subjected to an extension test. The results are shown in Table 2.

[Table 2]

10: laminate 11: substrate layer 12: Polarizing layer

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

10: laminate

11: substrate layer

12: Polarizing layer

Claims (8)

A laminate comprising a base material layer and a polarizing layer that can be stretched, and the moisture content of the base material layer is 5.0% or less, which satisfies the following formula (1), |E _A -E _T |/| E _A +E _T |≦0.25 (1) [In the formula, E _A and E _T represent the tensile elastic modulus in the absorption axis direction and the transmission axis direction, respectively]. If the laminate of claim 1, its total haze value is less than 3%. The laminated body according to claim 1, wherein the thickness of the polarizing layer is 0.5 μm to 10 μm. The laminated body according to claim 1, wherein the polarizing layer contains a cured product of a polarizing layer forming composition containing a polymerizable liquid crystal compound and a dichroic dye. The laminate according to claim 1, 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 as claimed in claim 1, further has an adhesive layer on the polarizing layer side. The laminated body according to claim 6, which has a phase difference layer laminated through the above-mentioned adhesive layer. A display device that adheres the layered product according to any one of claims 1 to 7 to an image display element.

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