TW202430938A - Multilayer body and organic EL display device - Google Patents

Abstract

The present invention provides a multilayer body that can suppress the generation of color tone when a display device displays black even when exposed to a humid and hot environment. The multilayer body of the present invention has a light absorption anisotropic layer obtained from a liquid crystal composition, a bonding layer, and a polarizing element in sequence. The polarizing element includes a polyvinyl alcohol resin, iodine, and boron. The light absorption anisotropic layer includes one or more dichroic pigments and satisfies the relationship of the following formulas (1) to (3). The liquid crystal composition includes a liquid crystal compound and a polymerization initiator, and the polymerization initiator is at least one of an oxime ester compound and an α-hydroxy ketone compound. Az＞(Ax＋Ay)/2       (1) 0.001≦Ax≦0.10    (2) Ax(z＝60°)/Ax≧2  (3) [In formulas (1) to (3), Ax, Ay, and Az are the absorbance of the light absorption anisotropic layer at the maximum wavelength within the wavelength range of 380 nm to 780 nm, and respectively represent the absorbance of linearly polarized light vibrating in the x-axis direction, y-axis direction, and z-axis direction. Ax (z = 60°) is the absorbance of the maximum absorption wavelength of the light absorption anisotropic layer, which represents the absorbance of linear polarized light vibrating in the x-axis direction when the light absorption anisotropic layer is rotated 60° with the y-axis as the rotation axis]

Description

Multilayer body and organic EL display device

The present invention relates to a multilayer body and an organic EL display device.

In known organic EL (electroluminescent) display devices, an optical film having a vertically aligned liquid crystal cured film containing a dichroic pigment is used in order to provide a function of preventing peeping or to reduce the hue difference between the front hue and the oblique hue of the luminescent color (for example, Patent Documents 1 and 2). [Prior Art Document] [Patent Document]

[Patent document 1] Japanese Patent Publication No. 2016-27387 [Patent document 2] Japanese Patent Publication No. 2020-76920

[The problem the invention is trying to solve]

Organic EL display devices are sometimes used as flexible display devices that can be bent or rolled up. In order to realize a display device with good flexibility, it is required to make the optical film used in the display device thinner. If the optical film having a vertically aligned liquid crystal cured film containing a dichroic pigment is made thinner, there is a case where a color tone is felt when the black display of the display device is exposed to a humid and hot environment.

The purpose of the present invention is to provide a laminate that can suppress the generation of color tones when the display device displays black even when exposed to a humid and hot environment, and an organic EL display device including the laminate. [Technical means for solving the problem]

The present invention provides the following laminate and organic EL display device. [1] A laminate having, in order, a light absorbing anisotropic layer obtained from a liquid crystal composition, a bonding layer, and a polarizing element, and the polarizing element comprises a polyvinyl alcohol resin, iodine, and boron, the light absorbing anisotropic layer comprises one or more dichroic pigments and satisfies the relationship of the following formulas (1) to (3), the liquid crystal composition comprises a liquid crystal compound and a polymerization initiator, the polymerization initiator is at least one of an oxime ester compound and an α-hydroxy ketone compound. Az＞(Ax＋Ay)/2         (1) 0.001≦Ax≦0.10      (2) Ax(z＝60°)/Ax≧2     (3) [In formulas (1) to (3), Ax, Ay, and Az are the absorbances of the above-mentioned light absorption anisotropic layer at the maximum wavelength within the wavelength range of 380 nm to 780 nm, and respectively represent the absorbances of linearly polarized light vibrating in the x-axis direction, y-axis direction, and z-axis direction. Ax(z=60°) is the absorbance of the above-mentioned absorption maximum wavelength of the above-mentioned light absorption anisotropic layer, which represents the absorbance of linearly polarized light vibrating in the x-axis direction when the above-mentioned light absorption anisotropic layer is rotated 60° about the y-axis. Here, the above-mentioned x-axis is an arbitrary direction in the plane of the above-mentioned light absorption anisotropic layer, the above-mentioned y-axis is a direction in the plane of the above-mentioned light absorption anisotropic layer that is orthogonal to the above-mentioned x-axis, the above-mentioned z-axis is a direction orthogonal to the above-mentioned x-axis and the above-mentioned y-axis] [2] The laminate as described in [1], wherein the thickness of the above-mentioned light absorption anisotropic layer is not less than 0.2 μm and not more than 3.5 μm. [3] The laminate as described in [1] or [2], further comprising a protective layer on the side of the light absorbing anisotropic layer opposite to the bonding layer. [4] The laminate as described in any one of [1] to [3], wherein the liquid crystal compound comprises a polymerizable liquid crystal compound. [5] The laminate as described in any one of [1] to [4], wherein the liquid crystal compound is a compound that forms a lamellar liquid crystal phase. [6] The laminate as described in any one of [1] to [5], wherein the dichroic dye is an azo compound. [7] A laminate as described in any one of [1] to [6], further comprising a phase difference layer satisfying the relationship of the following formulas (4) and (5) on the side of the polarizing element opposite to the side of the bonding layer, The phase difference layer is a cured layer of a polymerizable liquid crystal compound. 120 nm≦Re(550)≦160 nm (4) Re(450)/Re(550)≦1.00      (5) [In formula (4) and formula (5), Re(λ) represents the in-plane phase difference value of the above phase difference layer at wavelength λ[nm]] [8] A laminate as described in any one of [1] to [7], wherein the distance L1 between the surface of the above light absorption anisotropic layer on the above bonding layer side and the surface of the above polarizing element on the above bonding layer side is less than 20.0 μm. [9] A multilayer as described in any one of [1] to [8], further comprising a protective layer on the side of the light absorbing anisotropic layer opposite to the bonding layer, wherein the distance L2 between the surface of the protective layer opposite to the light absorbing anisotropic layer and the surface of the polarizing element opposite to the bonding layer is less than 85.0 μm. [10] An organic EL display device, wherein a multilayer as described in any one of [1] to [9] is laminated on a display element via an adhesive layer. [Effect of the invention]

According to the present invention, a multilayer body can be provided which can suppress the generation of color tone when a display device displays black even when exposed to a humid and hot environment.

Hereinafter, preferred embodiments of the multilayer body and the organic EL display device will be described with reference to the drawings.

FIG. 1 and FIG. 2 are cross-sectional views schematically showing a laminate of one embodiment of the present invention. As shown in FIG. 1 and FIG. 2, laminates 1 and 2 sequentially have a light absorbing anisotropic layer 11, a bonding layer 15, and a polarizing element 12. The light absorbing anisotropic layer 11 is obtained from a liquid crystal composition and contains one or more first dichroic pigments (dichroic pigments). The liquid crystal composition contains a liquid crystal compound and a polymerization initiator. The bonding layer 15 is at least one of an adhesive layer and a bonding agent layer, and may also contain an adhesive layer and a bonding agent layer. The polarizing element 12 contains a polyvinyl alcohol resin, iodine, and boron. The polarizing element 12 has iodine adsorbed and aligned on the polyvinyl alcohol resin layer and has a structure cross-linked by boron (cross-linked structure of borate). Preferably, in the laminates 1 and 2, the light absorbing anisotropic layer 11 is directly in contact with the bonding layer 15. Preferably, in the laminates 1 and 2, the bonding layer 15 is directly in contact with the polarizing element 12. The laminates 1 and 2 are usually arranged in such a way that the light absorbing anisotropic layer 11 is closer to the viewing side than the polarizing element 12.

As shown in FIG. 1 and FIG. 2 , the laminates 1 and 2 may also have a protective layer 21 on the side of the light absorbing anisotropic layer 11 opposite to the bonding layer 15. The light absorbing anisotropic layer 11 and the protective layer 21 may be laminated with a bonding layer (adhesive layer and/or bonding agent layer) interposed therebetween, or may be laminated directly in contact with each other. Alternatively, a first alignment layer for regulating the alignment of the liquid crystal compound in the liquid crystal composition may be provided between the light absorbing anisotropic layer 11 and the protective layer 21. When the laminates 1 and 2 have the first alignment layer, the first alignment layer and the light absorbing anisotropic layer 11 are usually in direct contact with each other.

The laminates 1 and 2 may also have protective films on both sides of the polarizing element 12 to protect the polarizing element 12. The protective film and the polarizing element may be directly in contact, or may be laminated with a bonding layer (adhesive layer and/or bonding agent layer) interposed therebetween. The laminates 1 and 2 preferably have a protective film on the side of the polarizing element 12 opposite to the bonding layer 15, and do not have a protective film on the bonding layer 15 side of the polarizing element 12.

As shown in Fig. 2, the laminate 2 may include a phase difference body 13 including one or more phase difference layers on the side of the polarizing element 12 opposite to the bonding layer 15. In the laminate 2, the polarizing element 12 and the phase difference body 13 may also constitute an anti-reflection film that functions as an elliptical polarizing plate.

The light absorption anisotropic layer 11 is a liquid crystal film obtained from a liquid crystal composition containing a liquid crystal compound. The liquid crystal film in this specification refers to a film obtained from a composition containing a liquid crystal compound. The liquid crystal film may contain a liquid crystal compound or a polymer of the liquid crystal compound. The polymer of the liquid crystal compound may or may not exhibit liquid crystal properties.

The liquid crystal composition used to form the light absorbing anisotropic layer 11 includes a liquid crystal compound and a polymerization initiator. The polymerization initiator is at least one of an oxime ester compound and an α-hydroxy ketone compound. The liquid crystal composition may include a second dichroic pigment that becomes the first dichroic pigment contained in the light absorbing anisotropic layer 11 as described below. The liquid crystal composition may include a polymerizable liquid crystal compound as the liquid crystal compound, and may also include a dichroic pigment having a polymerizable group as the second dichroic pigment. The polymerizable liquid crystal compound is a compound having a polymerizable group and having liquid crystal properties.

The light-absorbing anisotropic layer 11 includes one or more first dichroic pigments, and the light-absorbing anisotropic layer 11 satisfies the relationship of the following equations (1) to (3). Az＞(Ax＋Ay)/2       (1) 0.001≦Ax≦0.10    (2) Ax(z＝60°)/Ax≧2  (3) [In equations (1) to (3), Ax, Ay, and Az are the absorbances of the absorption maximum wavelength of the light-absorbing anisotropic layer 11 within the wavelength range of 380 nm to 780 nm, and respectively represent the absorbances of linearly polarized light vibrating in the x-axis direction, y-axis direction, and z-axis direction. Ax (z = 60°) is the absorbance of the above-mentioned absorption maximum wavelength of the light absorption anisotropic layer 11, which represents the absorbance of linear polarized light vibrating in the x-axis direction when the light absorption anisotropic layer 11 is rotated 60° with the y-axis as the rotation axis. Here, the x-axis is an arbitrary direction in the plane of the light absorption anisotropic layer 11, the y-axis is a direction in the plane of the light absorption anisotropic layer 11 that is orthogonal to the x-axis, and the z-axis is a direction orthogonal to the x-axis and the y-axis]

The first dichroic dye contained in the light absorption anisotropic layer 11 may be a non-polymerized dichroic dye or a polymer of a dichroic dye. The polymer of a dichroic dye may be a polymer of dichroic dyes having a polymerizable group or a polymer of a dichroic dye having a polymerizable group and a polymerizable liquid crystal compound.

Even when the laminates 1 and 2 are exposed to a humid and hot environment, the generation of tint during black display of the display device using the laminates 1 and 2 can be suppressed. The reason is presumed to be as follows. In the light absorbing anisotropic layer 11 obtained from a liquid crystal composition containing a polymerization initiator, a trace amount of polymerization initiator may remain. The trace amount of polymerization initiator remaining in the light absorbing anisotropic layer 11 may sometimes move to the polarizing element 12 adsorbed and aligned with iodine on the polyvinyl alcohol-based resin layer in a humid and hot environment. The light absorbing anisotropic layer 11 possessed by the laminates 1 and 2 is formed by a liquid crystal composition containing at least one of an oxime ester compound and an α-hydroxy ketone compound as a polymerization initiator. These compounds do not show alkalinity or acidity, so even if these compounds move from the light-absorbing anisotropic layer 11 to the polarizing element 12 in a humid and hot environment, it is difficult to promote the hydrolysis of the structure obtained by boron crosslinking (crosslinking structure of borate ester) contained in the polarizing element 12. Therefore, it is considered that iodine is difficult to be removed and it is difficult to cause the polarizing element 12 to discolor. It is speculated that in a display device using the multilayer bodies 1 and 2, the generation of color tones when performing black display in a humid and hot environment can be suppressed. On the other hand, compared with oxime ester compounds and α-hydroxy ketone compounds, amino ketone compounds known as polymerization initiators are easy to promote the hydrolysis of the crosslinking structure of borate ester contained in the polarizing element, so iodine is easy to be removed. As a result, it is speculated that the polarizing element is easily discolored, and a color tone is easily generated when the display device displays black in a humid and hot environment.

Furthermore, even when the laminates 1 and 2 are exposed to a hot and humid environment, the hue difference between the hue when viewed from the front and the hue when viewed from an oblique direction during white display of a display device using the laminates 1 and 2 can be suppressed.

In the laminates 1 and 2, the distance L1 between the surface of the light absorption anisotropic layer 11 on the bonding layer 15 side and the surface of the polarizing element 12 on the bonding layer 15 side is preferably less than 20.0 μm, or less than 18.0 μm, or less than 16.0 μm, or less than 10.0 μm, or less than 5.0 μm, or less than 1.0 μm, and is usually greater than 0.01 μm. Even when the distance L1 is within the above range, and the distance between the light absorbing anisotropic layer 11 and the polarizing element 12 in the stacking direction of the stacking bodies 1 and 2 is relatively small, the generation of color tone during black display of a display device using the stacking bodies 1 and 2 in a humid and hot environment can be suppressed by using the light absorbing anisotropic layer 11 obtained from a liquid crystal composition containing the above-mentioned polymerization initiator.

When the laminates 1 and 2 have a protective layer 21, the distance L2 between the surface of the protective layer 21 opposite to the light absorption anisotropic layer 11 and the surface of the polarizing element 12 opposite to the bonding layer 15 is preferably less than 85.0 μm, or less than 70.0 μm, or less than 60.0 μm, and is usually greater than 30.0 μm. Even when the stacked layers 1 and 2 are thin, as in the case where the distance L2 is within the above range, the generation of tint during black display of a display device using the stacked layers 1 and 2 in a humid and hot environment can be suppressed by using a light absorption anisotropic layer 11 obtained from a liquid crystal composition containing the above-mentioned polymerization initiator.

The following describes each layer of the laminates 1 and 2 in detail. (Light-absorbing anisotropic layer) The light-absorbing anisotropic layer 11 is a layer containing one or more first dichroic dyes and is obtained from a liquid crystal composition. The light-absorbing anisotropic layer 11 may also contain two or more first dichroic dyes. At least one of the first dichroic dyes contained in the light-absorbing anisotropic layer 11 is preferably an azo compound. The first dichroic dye and the liquid crystal compound contained in the liquid crystal composition are described below.

The light absorbing anisotropic layer 11 satisfies the relationship of the above formulas (1) to (3). It is believed that the light absorbing anisotropic layer 11 satisfying the relationship of the above formulas (1) to (3) has the absorption axis of the first dichroic pigment aligned in the lead vertical direction relative to its plane, so the light absorbing anisotropic layer 11 can effectively transmit light from the front direction and effectively absorb light from the oblique direction.

The absorbance Az in the z direction in the above formula (1) is measured by incident light from the side of the light absorbing anisotropic layer 11, so it is difficult to measure. Therefore, when the angle between the vibration plane of the linear polarized light as the measurement light and the x-y plane of the light absorbing anisotropic layer 11 is set to 90°, the x-y plane of the light absorbing anisotropic layer 11 is tilted 30° and 60° to the incident direction of the linear polarized light relative to the vibration plane, and the absorbance Az in the z direction can be estimated.

Specifically, the following method can be used for estimation. When the light absorption anisotropic layer 11 is rotated 30° and 60° with the y-axis as the rotation axis, the same linear polarized light as the linear polarized light for measuring Ax is incident, thereby measuring the absorbance Ax (z = 30°) and the absorbance Ax (z = 60°). Similarly, when the light absorption anisotropic layer 11 is rotated 30° and 60° with the x-axis as the rotation axis, the same linear polarized light as the linear polarized light for measuring Ay is incident, thereby measuring the absorbance Ay (z = 30°) and the absorbance Ay (z = 60°). At this time, if Ax(z＝30°)＜Ax(z＝60°) and Ay(z＝30°)＝Ay(z＝60°), then Ax(z＝30°)＜Ax(z＝60°)＜Ax(z＝90°)＝Az, and if Ay(z＝30°)＜Ay(z＝60°) and Ax(z＝30°)＝Ax(z＝60°), then Ay(z＝30°)＜Ay(z＝60°)＜Ay(z＝90°)＝Az, so it can be said that the relationship of formula (1) is necessarily satisfied. Here, Ax (z = 90°) is the absorbance measured by incident linearly polarized light identical to the linearly polarized light used to measure Ax, while the light absorption anisotropic layer 11 is rotated 90° about the y-axis. Ay (z = 90°) is the absorbance measured by incident linearly polarized light identical to the linearly polarized light used to measure Ax, while the light absorption anisotropic layer 11 is rotated 90° about the x-axis.

In particular, when the x-y plane of the light absorption anisotropic layer 11 does not have absorption anisotropy, that is, when Ax and Ay are equal, Ax(z＝30°)＝Ay(z＝30°) and Ax(z＝60°)＝Ay(z＝60°). Here, Ax(z＝30°)＝Ay(z＝30°)＝A(z＝30°), Ax(z＝60°)＝Ay(z＝60°)＝A(z＝60°), and Ax(z＝90°)＝Ay(z＝90°)＝A(z＝90°). In this way, if A(z＝30°)＜A(z＝60°), the relationship of A(z＝30°)＜A(z＝60°)＜A(z＝90°)＝Az is satisfied. Furthermore, if A(z＝30°)＞(Ax＋Ay)/2, then Az must satisfy equation (1).

It is preferred that Ax and Ay are the same value in the light absorption anisotropic layer 11. When Ax and Ay are different, the light absorption anisotropic layer 11 has absorption anisotropy in the plane, and when the multilayers 1 and 2 are applied to a display device, there is a tendency for the coloring on the front side to increase.

The absorbance Ax in the above formulas (1) to (3) can be measured by incident linear polarized light vibrating in the x-axis direction from the z-axis direction to the plane of the light absorbing anisotropic layer 11. The absorbance Ax means the absorbance in the front direction within the plane of the light absorbing anisotropic layer 11. It can be said that the smaller the value of the absorbance Ax, the better the alignment of the first dichroic dye in the vertical direction relative to the plane of the light absorbing anisotropic layer 11. Therefore, it can be said that the light absorbing anisotropic layer 11 that satisfies the relationship of the above formula (2) has the absorption axis of the first dichroic dye aligned with better accuracy in the vertical direction. When the absorbance Ax exceeds 0.10, the coloring of the light absorption anisotropic layer 11 in the front direction is enhanced, so there is a tendency for the front hue to deteriorate when it is combined with the phase difference layer described below and applied to an organic EL display device. Therefore, the absorbance Ax in formula (2) is preferably 0.001 or more and 0.07 or less, and more preferably 0.001 or more and 0.05 or less.

If the value of Ax(z＝60°)/Ax in the above formula (3) is less than 2, it is difficult to obtain good absorption anisotropy. Ax(z＝60°)/Ax is preferably 2.5 or more, more preferably 3.0 or more. Ax(z＝60°)/Ax is preferably 50 or less, more preferably 30 or less, and further preferably 20 or less.

The light absorbing anisotropic layer 11 satisfying the relationship of the above formulas (1) to (3) can be adjusted by, for example, the thickness of the light absorbing anisotropic layer 11, the conditions of the manufacturing steps of the light absorbing anisotropic layer 11 (described below), the type or content of the dichroic pigment and liquid crystal compound contained in the first composition used to obtain the light absorbing anisotropic layer 11, etc.

The thickness of the light absorption anisotropic layer 11 is preferably 0.2 μm to 3.5 μm, more preferably 0.5 μm to 3.3 μm, further preferably 0.5 μm to 3.0 μm, and particularly preferably 0.5 μm to 2.0 μm. If the thickness of the light absorption anisotropic layer 11 is reduced, the content of the first dichroic pigment increases in order to express the required optical characteristics, and the transmission characteristics in the front direction are easily reduced due to the unaligned first dichroic pigment. If the thickness is increased, the alignment of the liquid crystal compound and the first dichroic pigment is easily disturbed, so the transmission characteristics in the front direction are easily reduced. Furthermore, when a relatively hard layer such as an adhesive layer is laminated on the light absorbing anisotropic layer 11 as the laminating layer 15, the laminating layer 15 and the light absorbing anisotropic layer 11 tend to be more easily broken by aggregation as the thickness of the laminating layer 15 and the light absorbing anisotropic layer 11 increases. This kind of aggregation breakage tends to become significant when the light absorbing anisotropic layer 11 is made of a liquid crystal compound that forms a lamellar liquid crystal phase.

(First dichroic pigment) The light absorption anisotropic layer includes one or more first dichroic pigments. In this specification, the so-called dichroic pigment refers to a pigment having a property that the absorbance in the long axis direction of the molecule is different from the absorbance in the short axis direction of the molecule. As mentioned above, the first dichroic pigment can be exemplified by: unpolymerized dichroic pigments, and polymers obtained by polymerizing dichroic pigments having polymerizable groups alone or with polymerizable liquid crystal compounds. As the first dichroic pigment, it is preferred that it has the property of absorbing visible light, and it is more preferred that it has an absorption maximum wavelength (λmax) in the wavelength range of 380 to 680 nm.

Examples of such first dichroic pigments include acridine pigments, thiazo pigments, cyanine pigments, naphthalene pigments, azo pigments, and anthraquinone pigments, among which azo pigments are preferred. Examples of azo pigments include monoazo pigments, disazo pigments, triazo pigments, tetraazo pigments, and stilbene azo pigments, among which disazo pigments and triazo pigments are preferred. The dichroic pigments may be used alone or in combination of two or more, and preferably in combination of two or more according to the wavelength range in which the light absorption anisotropy is required in the light absorption anisotropy layer.

As the azo dye, for example, a compound represented by formula (I) can be cited. T ¹ -A ¹ (-N=NA ² ) _p -N=NA ³ -T ² (I) [In formula (I), A ¹ , A ² , and A ³ independently represent a 1,4-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, a benzoic acid phenyl ester group which may have a substituent, a 4,4'-stilbene group which may have a substituent, or a divalent heterocyclic group which may have a substituent, T ¹ and T ² represent an electron-withdrawing group or an electron-donating group, and T ¹ and T ² are located at positions substantially 180° relative to the azo bonding plane. p represents an integer of 0 to 4, and when p is 2 or more, each A ² may be the same or different. It is also possible to replace the -N=N- bond with -C=C-, -COO-, -NHCO-, or -N=CH- bonds within the range that shows absorption in the visible light region.]

The content of the first dichroic dye in the light absorbing anisotropic layer is preferably 0.1 to 30 parts by mass, and may be 0.5 to 20 parts by mass, 1 to 10 parts by mass, or 1 to 5 parts by mass, relative to 100 parts by mass of the light absorbing anisotropic layer. The content ratio of the first dichroic dye in the light absorbing anisotropic layer can be calculated as the ratio of the dichroic dye relative to 100 parts by mass of the solid component of the liquid crystal composition used to form the light absorbing anisotropic layer. When the light absorbing anisotropic layer includes two or more first dichroic dyes, the content of the first dichroic dye refers to the total amount of the two or more dichroic dyes. The so-called solid content of the liquid crystal composition, when the liquid crystal composition contains a solvent, refers to the total amount of components obtained by removing the solvent from the liquid crystal composition.

(Liquid crystal composition) The liquid crystal composition is used to obtain a light absorbing anisotropic layer. The light absorbing anisotropic layer can be formed by drying a coating layer formed by coating the liquid crystal composition on, for example, a first substrate layer. As described above, the liquid crystal composition includes a liquid crystal compound and a polymerization initiator. The liquid crystal composition may further include one or more second dichroic pigments. The second dichroic pigment becomes the first dichroic pigment contained in the light absorbing anisotropic layer 11.

The liquid crystal compound contained in the liquid crystal composition is used to align the second dichroic pigment through host-guest interaction. The liquid crystal compound can be a low molecular liquid crystal compound or a high molecular liquid crystal compound. The liquid crystal compound can also be a polymerizable liquid crystal compound. The above liquid crystal compound is preferably a compound that forms a stratigraphic liquid crystal layer.

A polymerizable liquid crystal compound is a compound having a polymerizable group and having liquid crystal properties. The polymerizable group inhibits the group participating in the polymerization reaction, preferably a photopolymerizable group. Here, the so-called photopolymerizable group refers to a group that can participate in the polymerization reaction by an active free radical or acid generated from the following photopolymerization initiator. Examples of the polymerizable group include: vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, oxirane, cyclobutyl, etc. Among them, acryloxy, methacryloxy, vinyloxy, oxirane, and cyclobutyl are preferred, and methacryloxy or acryloxy is more preferred. Regarding liquid crystal properties, it can be thermotropic liquid crystal or lyotropic liquid crystal. When mixed with the above-mentioned dichroic dye, thermotropic liquid crystal is preferred.

When the polymerizable liquid crystal compound 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 the polymerizable liquid crystal compound exhibits light absorption anisotropy as a liquid crystal cured film (liquid crystal film) through polymerization reaction, the liquid crystal state shown by the polymerizable liquid crystal compound is preferably a smectic phase, and if it is a higher-order smectic phase, it is even better from the perspective of high performance. Among them, a higher-order smectic liquid crystal compound that forms a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, a smectic K phase, or a smectic L phase is more preferred, and a higher-order smectic liquid crystal compound that forms a smectic B phase, a smectic F phase, or a smectic I phase is further preferred. If the liquid crystal phase formed by the polymerizable liquid crystal compound is such a higher order lamellar phase, a light absorption anisotropic layer with higher light absorption anisotropy can be produced. Such a light absorption anisotropic layer with higher light absorption anisotropy can obtain a Bragg peak from a higher order structure such as a hexagonal phase or a crystalline phase in X-ray diffraction measurement. The Bragg peak is a peak from the periodic structure of the molecular alignment, and the periodic interval of the light absorption anisotropic layer can be 3 to 6Å. From the perspective of obtaining higher light absorption anisotropy, it is better that the light absorption anisotropic layer includes a polymer of a polymerizable liquid crystal compound aligned in a lamellar phase.

The polymerizable liquid crystal compound may be a monomer, an oligomer formed by polymerizing a polymerizable group, or a polymer. As such a polymerizable liquid crystal compound, a known one may be used, for example, those described in Japanese Patent Laid-Open No. 2020-76920 and Japanese Patent No. 6728581.

When the liquid crystal compound is the above-mentioned polymer liquid crystal compound, a known liquid crystal compound can be used as the liquid crystal compound, and for example, the liquid crystal compound described in Japanese Patent Application Laid-Open No. 2011-237513 can be cited.

The liquid crystal compound may be used alone or in combination of two or more. The content of the liquid crystal compound is preferably 40 to 99.9 parts by mass, or 60 to 99 parts by mass, or 70 to 99 parts by mass, relative to 100 parts by mass of the solid component of the liquid crystal composition. If the content of the liquid crystal compound is within the above range, there is a tendency to improve the orientation of the liquid crystal compound when forming a light absorption anisotropic layer. When the liquid crystal composition contains two or more liquid crystal compounds, the content of the liquid crystal compound refers to the total amount of the two or more liquid crystal compounds.

The polymerization initiator contained in the liquid crystal composition is at least one of an oxime ester compound and an α-hydroxy ketone compound. The polymerization initiator is a compound that can start the polymerization reaction of polymerizable components such as a polymerizable liquid crystal compound, a dichroic pigment having a polymerizable group, or a non-liquid crystal compound having a polymerizable group (described below) contained in the liquid crystal composition. The polymerization initiator is preferably an oxime ester compound or an α-hydroxy ketone compound. The liquid crystal composition may also contain other polymerization initiators besides the oxime ester compound and the α-hydroxy ketone compound.

Examples of the oxime ester compound include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyl oxime)] (trade name: Irgacure OXE-01, manufactured by BASF), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(o-acetyl oxime) (trade name: Irgacure OXE-02, manufactured by BASF), methyl ketone, ethyl ketone, 1-[9-ethyl-6-(1,3-dioxacyclopentane, 4-(2-methoxyphenoxy)-9H-carbazole-3-yl]-, 1-(o-acetyl oxime) (trade name: ADEKA OPT-N-1919, manufactured by ADEKA Corporation), and the like.

Examples of the α-hydroxy ketone compound include 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propane-1-one (e.g., trade name: Irgacure 127, manufactured by BASF Corporation), 2-hydroxy-4'-hydroxyethoxy-2-methylpropiophenone (e.g., trade name: Irgacure 2959, manufactured by BASF Corporation), 1-hydroxy-cyclohexyl-phenyl-ketone (e.g., trade name: Irgacure 184, manufactured by BASF Corporation), and oligomers of 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropane-1-one (e.g., trade name: ESACURE ONE, manufactured by IGM Resins B.V. Corporation).

The content of the polymerization initiator in the liquid crystal composition can be appropriately adjusted according to the type and amount of the polymerizable component. When the polymerizable component in the liquid crystal composition is a polymerizable liquid crystal compound, the content 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 content of the polymerizable liquid crystal compound. If the content of the polymerization initiator is within the above range, polymerization can be performed without disrupting the alignment of the polymerizable liquid crystal compound.

As other polymerization initiators that may be contained in the liquid crystal composition, photopolymerization initiators or thermal polymerization initiators may be cited, and photopolymerization initiators are preferred. Photopolymerization initiators are polymerization initiators that generate active free radicals by the action of light. Specifically, photopolymerization initiators that can generate active free radicals or acids by the action of light may be cited, and photopolymerization initiators that generate free radicals by the action of light are preferred. Photopolymerization initiators may be used alone or in combination of two or more.

As photopolymerization initiators that can be used as other polymerization initiators and generate active free radicals, those that do not show acidity or alkalinity can be exemplified: Self-cleavage type benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, etc., and Hydrogen-absorbent type benzophenone compounds, phenylalanone compounds, benzoin ether compounds, benzoyl ketone compounds, dibenzocycloheptanone compounds, anthraquinone compounds, ketone compounds, halogenated acetophenone compounds, dialkoxyacetophenone compounds, etc.

The second dichroic dye contained in the liquid crystal composition may be the first dichroic dye contained in the light absorbing anisotropic layer. When the first dichroic dye contained in the light absorbing anisotropic layer is a polymer, it may be a dichroic dye having a polymerizable group for obtaining the first dichroic dye. As the second dichroic dye, the dyes exemplified as the first dichroic dye can be cited.

From the viewpoint of obtaining good light absorption characteristics, the content of the second dichroic pigment contained in the liquid crystal composition is usually 1 to 60 parts by mass, preferably 1 to 40 parts by mass, and more preferably 1 to 20 parts by mass relative to 100 parts by mass of the liquid crystal compound. If the content of the second dichroic pigment is less than the range, light absorption becomes insufficient and sufficient light absorption anisotropy cannot be obtained. If it is more than the range, there is a situation where the alignment of the liquid crystal molecules of the liquid crystal compound is suppressed. In the case where the liquid crystal composition contains two or more first dichroic pigments, the content of the second dichroic pigment refers to the total amount of the two or more dichroic pigments.

The liquid crystal composition may further include a solvent. Generally, the viscosity of the liquid crystal compound is relatively high, so the liquid crystal compound is dissolved in a solvent to prepare a liquid crystal composition including a solvent, thereby making it easier to coat the first substrate layer, and as a result, it is easy to form a light absorption anisotropic layer in most cases. As a solvent, it is preferably a solvent that can completely dissolve the liquid crystal compound, and it is also preferably a solvent that is inert to the polymerization reaction of the liquid crystal compound. Examples of the solvent include: alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; 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; chlorine-containing solvents such as chloroform and chlorobenzene; amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone, etc. These solvents may be used alone or in combination of two or more.

The content of the solvent in the liquid crystal composition is preferably 50-98% by weight relative to the total amount of the liquid crystal composition. In other words, the content of the solid component in the liquid crystal composition is preferably 2-50% by weight, and more preferably 5-30% by weight. If the content of the solid component is less than 50% by weight, the viscosity of the liquid crystal composition decreases, so it is easy to form the light absorption anisotropic layer with a roughly uniform thickness, and it is difficult to produce unevenness in the light absorption anisotropic layer. The content of the solid component can be determined by considering the thickness of the light absorption anisotropic layer to be manufactured.

The liquid crystal composition may further include additives such as non-liquid crystal compounds having polymerizable groups, leveling agents, antioxidants, photosensitizers, etc. When the liquid crystal composition is directly coated on the surface of the first substrate layer (when the first alignment layer is not used), the liquid crystal composition preferably further includes an alignment promoter.

A non-liquid crystal compound having a polymerizable group (hereinafter, sometimes referred to as a "non-liquid crystal compound") is a compound having a polymerizable group and not having liquid crystal properties. Examples of the polymerizable group possessed by the non-liquid crystal compound include: vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, (meth)acryloyl, (meth)acryloyloxy, ethylene oxide, cyclobutylene oxide, etc. Among them, preferred polymerizable groups are (meth)acryloyl, (meth)acryloyloxy, vinyloxy, ethylene oxide, and cyclobutylene oxide, more preferred polymerizable groups are (meth)acryloyl and (meth)acryloyloxy, and further preferred polymerizable groups are (meth)acryloyloxy. The polymerizable group in the non-liquid crystal compound may be one type or a combination of two or more types, and is preferably the same polymerizable group as that of the dichroic dye or the liquid crystal compound.

The number of polymerizable groups possessed by the non-liquid crystal compound is not particularly limited, and may be, for example, 1 to 20. From the viewpoint of making it easier to increase the film strength of the light absorption anisotropic layer, it is preferably 2 to 10, and more preferably 3 to 6. When the non-liquid crystal compound has two or more polymerizable groups, the polymerizable groups may be the same or different from each other.

Examples of non-liquid crystal compounds having a polymerizable group include monofunctional (meth)acrylates and multifunctional (meth)acrylates. Monofunctional acrylates and multifunctional acrylates as non-liquid crystal compounds having a polymerizable group are non-liquid crystals, and therefore preferably do not have a mesogen structure. Monofunctional acrylates and multifunctional acrylates may also contain a urethane structure, an amino structure, an epoxy structure, a glycol structure, and/or a polyester structure in the molecule.

The so-called leveling agent is an additive that has the function of adjusting the fluidity of the liquid crystal composition and making the film obtained by coating the liquid crystal composition flatter. As leveling agents, for example, organic modified polysilicone oil-based, polyacrylate-based, and perfluoroalkyl-based leveling agents can be cited. Among them, polyacrylate-based leveling agents and perfluoroalkyl-based leveling agents are preferred.

When the liquid crystal composition contains a leveling agent, the content is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of the liquid crystal compound. If the content of the leveling agent is within the above range, there is a tendency to easily align the liquid crystal compound and the resulting light absorption anisotropic layer becomes smoother. If the content of the leveling agent relative to the liquid crystal compound exceeds the above range, there is a tendency to easily produce unevenness in the resulting light absorption anisotropic layer. The liquid crystal composition may also contain two or more leveling agents.

The liquid crystal composition can be obtained by stirring a liquid crystal compound, a polymerization initiator, a second dichroic dye, a solvent, and additives such as a non-liquid crystal compound and a leveling agent.

As a method for obtaining a light-absorbing anisotropic layer using a liquid crystal composition, a method including the step of coating a liquid crystal composition on a first substrate layer can be cited. The above method may also include a step of drying the coating layer formed by coating the liquid crystal composition on the first substrate layer to remove a solvent, etc. In the case where the liquid crystal composition includes a polymerizable liquid crystal compound as a polymerizable component, the coating layer after the drying treatment is irradiated with active energy rays, etc. to polymerize the polymerizable liquid crystal compound, thereby forming a light-absorbing anisotropic layer as a cured layer of the polymerizable liquid crystal compound. The liquid crystal composition can be coated on the surface of the first substrate layer, and can also be coated on the surface of the first alignment layer formed on the surface of the first substrate layer.

Examples of methods for coating the liquid crystal composition on the first substrate layer include known methods such as spin coating, extrusion coating, gravure coating, die-nozzle coating, rod coating, and applicator coating, and printing methods such as flexographic printing.

It is preferred to dry the coating layer of the liquid crystal composition formed on the first substrate layer. When the liquid crystal composition contains a solvent, the solvent in the coating layer can be removed by drying the coating layer. As the drying method, a known method can be cited, and one or more methods of natural drying method, heating drying method, ventilation drying method, and pressure reduction drying method can be cited.

The drying conditions in the drying process can be appropriately determined according to the components contained in the liquid crystal composition. For example, the drying temperature in the drying process is 50°C to 150°C, or 60°C to 120°C. The drying time in the drying process is 15 seconds to 10 minutes, or 0.5 minutes to 5 minutes.

When heat treatment is performed during the drying process, the liquid crystal compound contained in the liquid crystal composition is heated to a temperature above the liquid crystal phase transition temperature at which the liquid crystal compound undergoes phase transition, thereby removing the solvent in the coating layer and aligning the liquid crystal compound. In this way, the liquid crystal compound can be aligned in a direction perpendicular to the surface of the light absorption anisotropic layer, and the dichroic pigment can also be aligned along with the alignment of the liquid crystal compound.

Alternatively, when the first alignment layer is disposed on the surface of the first substrate layer, the liquid crystal compound and the dichroic pigment in the coating layer can be aligned by the alignment regulating force of the first alignment layer.

When the liquid crystal composition includes a polymerizable liquid crystal compound, the coating layer formed on the first substrate layer is dried, and the polymerizable liquid crystal compound and the second dichroic dye are irradiated with active energy rays to polymerize and cure the polymerizable liquid crystal compound, thereby forming a light absorption anisotropic layer in which the liquid crystal compound and the first dichroic dye are aligned.

As a method for polymerizing a polymerizable liquid crystal compound, photopolymerization is preferred. Photopolymerization is performed by irradiating a layered structure comprising the following coating layer with active energy rays, wherein the coating layer is formed by coating a liquid crystal composition comprising a polymerizable liquid crystal compound on a first substrate layer or a first alignment layer. The active energy rays irradiated are appropriately selected according to the type of polymerizable liquid crystal compound contained in the coating layer (especially the type of photopolymerizable functional group possessed by the polymerizable liquid crystal compound), the type of photopolymerization initiator when a photopolymerization initiator is included, and the amount thereof. Specifically, one or more light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α rays, β rays, and γ rays can be cited. Among them, ultraviolet light is preferred in terms of ease of controlling the progress of the polymerization reaction and the fact that the photopolymerization device can be used by a wide range of users in this field, and it is preferred to select the type of polymerizable liquid crystal compound in a manner that allows photopolymerization by ultraviolet light.

Examples of the light source of 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, LED (Light Emitting Diode) light sources emitting light in the wavelength range of 380 to 440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, and metal halide lamps.

The intensity of ultraviolet irradiation is usually 10 mW/cm ² to 3,000 mW/cm ² . The intensity of ultraviolet irradiation is preferably an intensity in the wavelength region effective for the activation of cationic polymerization initiators or free radical polymerization initiators. The irradiation time is usually 0.1 second to 10 minutes, preferably 1 second to 5 minutes, more preferably 5 seconds to 3 minutes, and further preferably 10 seconds to 1 minute. If the ultraviolet irradiation intensity is used once or multiple times, the cumulative light amount is 10 mJ/cm ² to 3,000 mJ/cm ² , preferably 50 mJ/cm ² to 2,000 mJ/cm ² , and more preferably 100 mJ/cm ² to 1,000 mJ/cm ² . When the accumulated light quantity is below the range, the curing of the polymerizable liquid crystal compound may be insufficient, and good transferability may not be obtained when the light absorption anisotropic layer is transferred to the adherend. On the contrary, when the accumulated light quantity is above the range, the light absorption anisotropic layer may be colored.

The first alignment layer facilitates the liquid crystal alignment of the liquid crystal compound. The state of the liquid crystal alignment varies according to the properties of the first alignment layer and the liquid crystal compound, and their combination can be arbitrarily selected.

Regarding the alignment regulating force, when the first alignment layer is formed of an alignment polymer, it can be arbitrarily adjusted according to the surface state or rubbing conditions. When the first alignment layer is formed of a photoalignment polymer, the alignment regulating force can be arbitrarily adjusted according to polarized light irradiation conditions, etc. In addition, the liquid crystal alignment can also be controlled by selecting the physical properties such as the surface tension or liquid crystallinity of the liquid crystal compound.

The first alignment layer formed between the first substrate layer and the light absorbing anisotropic layer is preferably a layer that is insoluble in the solvent used when forming the light absorbing anisotropic layer on the first alignment layer and has heat resistance in the heat treatment for removing the solvent or aligning the liquid crystal. Examples of the first alignment layer include a polymer alignment layer including an aligning polymer, a photoalignment layer and a groove alignment layer, and a stretching film extending in the alignment direction. When applied to a long roll film, a photoalignment layer is preferred in terms of being able to easily control the alignment direction.

The thickness of the first alignment layer is generally 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.

As the alignment polymer used for the rubbing alignment layer, there can be cited: polyamide or gelatin having an amide bond in the molecule, polyimide having an imide bond in the molecule and polyamide acid as its hydrolyzate, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyazole, polyethyleneimine, polystyrene, polyvinyl pyrrolidone, polyacrylic acid and polyacrylates, etc. Among them, polyvinyl alcohol is preferred. These alignment polymers can be used alone or in combination of two or more.

As a rubbing method, the following method can be cited: a film of an alignment polymer formed on the surface of the first base layer by coating the alignment polymer composition on the first base layer and annealing the film is brought into contact with a rubbing roller wrapped with a rubbing cloth and rotating.

The photo-alignment layer includes a polymer or oligomer, or a monomer having a photoreactive group. The photo-alignment layer obtains the alignment regulating force by irradiating the coating layer formed by coating the composition for forming the photo-alignment layer on the first substrate layer with polarized light. By selecting the polarization direction of the irradiated polarized light, the direction of the alignment regulating force can be arbitrarily controlled. In this respect, the photo-alignment layer is more preferred.

The so-called photoreactive group refers to a group that generates the ability of liquid crystal alignment by irradiation with light. Specifically, it refers to a group that generates a photoreaction that is the origin of the ability of liquid crystal alignment, such as an isomerization reaction, a dimerization reaction, a photocrosslinking reaction, or a photodecomposition reaction, by inducing the alignment of molecules generated by irradiation with light. Among the photoreactive groups, the one that causes a dimerization reaction or a photocrosslinking reaction is preferred in terms of excellent alignment. As the photoreactive group capable of producing the above-mentioned reaction, it is preferred to have an unsaturated bond, especially a double bond, and it is more preferred to have at least one selected from the group consisting of a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), a nitrogen-nitrogen double bond (N=N bond), and a carbon-oxygen double bond (C=O bond).

As photoreactive groups having a C=C bond, for example, vinyl, polyene, stilbene, styrylpyridine, styrylpyridinium, chalcone, and cinnamyl groups can be cited. From the perspective of easy control of reactivity or the expression of alignment regulation during photoalignment, chalcone and cinnamyl groups are preferred. As photoreactive groups having a C=N bond, groups having structures such as aromatic Schiff bases and aromatic hydrazones can be cited. As photoreactive groups having an N=N bond, azophenyl, azonaphthyl, aromatic heterocyclic azo groups, bisazo groups, and formazan groups can be cited, or groups having oxyazobenzene as a basic structure can be cited. Examples of the photoreactive group having a C=O bond include a benzophenone group, a coumarin group, an anthraquinone group, and a cis-butylenediimide group. These groups may also have a substituent such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, and a halogenated alkyl group.

When irradiating with polarized light, the polarized light may be directly irradiated from the film surface of the coating layer of the composition used to form the photo-alignment layer, or may be irradiated from the side of the first substrate layer so that the polarized light is transmitted. In addition, the polarized light is preferably substantially parallel light. The wavelength of the polarized light irradiated is preferably in a wavelength region where the photoreactive group of the polymer or monomer having the photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) with a wavelength range of 250 to 400 nm is particularly preferred. As the light source used for the polarized light irradiation, there can be cited: xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, ultraviolet lasers such as KrF and ArF, etc., preferably high-pressure mercury lamps, ultra-high-pressure mercury lamps and metal halide lamps. The ultraviolet light of the wavelength of 313 nm of these lamps has a large luminous intensity, so it is preferred. Polarized light can be irradiated by passing the light from the above light sources through an appropriate polarizing element. As the polarizing element, a polarizing filter or a polarizing prism such as a Glen-Thompson prism or a Glen-Taylor prism or a wire grid type polarizing element can be used.

(First substrate layer) The first substrate layer is a substrate coated with a liquid crystal composition for obtaining a light absorbing anisotropic layer, and can support the light absorbing anisotropic layer. The first substrate layer can be used as a protective layer that the laminate can have. As the first substrate layer, a glass substrate or a film substrate can be cited, and a film substrate is preferred.

Examples of the resin constituting the film substrate include olefin resins such as polyethylene and polypropylene; cyclic olefin resins or cyclic olefin resins having a norbutylene structure; polyvinyl alcohol; polyethylene terephthalate; poly(meth)acrylate; cellulose ester resins such as triacetyl cellulose, diacetyl cellulose and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; polyphenylene sulfide; polyphenylene ether, etc. Among them, from the viewpoint of transparency when used for optical film applications, a film substrate selected from any one of triacetyl cellulose, cyclic olefin resins, polymethacrylate, and polyethylene terephthalate is more preferred. The so-called (meth)acrylate refers to at least one of acrylate and methacrylate. The same applies to the description of (meth)acryl, etc.

As the film substrate, a commercially available cellulose ester resin substrate may also be used. Examples of such cellulose ester resin substrates include: "Fujitac Film" (manufactured by Fuji Photo Film Co., Ltd.); "KC8UX2M", "KC8UY" and "KC4UY" (manufactured by Konica Minolta Opto Co., Ltd.).

As the cyclic olefin resin constituting the membrane substrate, a commercially available cyclic olefin resin may be used. Examples of such cyclic olefin resins include: "Topas" (registered trademark) (manufactured by Ticona (Germany)), "Artone" (registered trademark) (manufactured by JSR Co., Ltd.), "ZEONOR" (registered trademark), "ZEONEX" (registered trademark) (all manufactured by Nippon Zeon Co., Ltd.) and "APEL" (registered trademark) (manufactured by Mitsui Chemicals Co., Ltd.). These cyclic olefin resins can be used as a membrane substrate by forming a film using a known method such as a solvent casting method or a melt extrusion method.

As the film substrate, a commercially available cyclic olefin resin substrate may also be used. Examples of such cyclic olefin resin substrates include: "S-SINA" (registered trademark), "SCA40" (registered trademark) (both manufactured by Sekisui Chemical Co., Ltd.), "Zeonor Film" (registered trademark) (manufactured by Optes Co., Ltd.), and "Artone Film" (registered trademark) (manufactured by JSR Co., Ltd.).

When the above-mentioned film substrate is used as a protective layer that the laminate may have, in order to easily suppress the generation of color tone when the display device is displayed in a hot and humid environment, it is preferably a film substrate that is difficult for water vapor to pass through. The moisture permeability of the film substrate is preferably 500 g/ ^m2 /24 hours or less, more preferably 150 g/ ^m2 /24 hours or less, and further preferably 20 g/ ^m2 /24 hours or less. The lower limit of the moisture permeability of the film substrate is not particularly limited, and is usually 1 g/ ^m2 /24 hours or more, preferably 5 g/ ^m2 /24 hours or more. The moisture permeability of the film substrate is the moisture permeability at a temperature of 40°C and a relative humidity of 90%, and can be measured by the cup method specified in JIS Z 0208. An olefin resin film substrate can be preferably used as the film substrate with low moisture permeability.

As the first substrate layer, a film with a surface coating layer formed on one or both sides of a film substrate, a film with a protective film laminated on the surface of the film substrate opposite to the light absorption anisotropic layer, or a film with a surface coating layer formed on one surface of a film substrate and a protective film laminated on the other surface can be used.

Examples of the surface coating layer constituting the film with a surface coating layer include: a layer formed by coating a hard coating agent, a bonding composition or a coupling agent on the surface of a film substrate, a layer formed by coating a reactive monomer or a reactive polymer and then irradiating the reactive monomer or the reactive polymer with active energy rays to cause the reactive monomer or the reactive polymer to undergo graft polymerization, etc. As the film with a surface coating layer, for example, a hard coating film having a hard coating layer as a surface coating layer is preferred. When the first substrate layer is a hard coating film, a light absorbing anisotropic layer may be deposited on the side of the hard coating layer, or may be deposited on the side of the film substrate.

The hard coating layer is preferably a hardened material layer of a hardening composition containing an active energy ray hardening resin, and more preferably a hardened material layer of a composition containing an ultraviolet hardening resin. The hardening composition containing an ultraviolet hardening resin preferably contains a (meth)acrylic compound as a hardening component. The (meth)acrylic compound is a compound having at least one (meth)acryloyl group, and may be a monomer, an oligomer, or a polymer.

Examples of (meth)acrylic compounds include (meth)acrylate compounds such as monofunctional (meth)acrylate compounds and polyfunctional (meth)acrylate compounds; polyfunctional polyurethane (meth)acrylate compounds; polyfunctional epoxy (meth)acrylate compounds; carboxyl-modified epoxy (meth)acrylate compounds; polyester (meth)acrylate compounds, etc. One or more of these compounds may be used. Among these compounds, polyfunctional (meth)acrylate compounds or polyurethane (meth)acrylate compounds are preferred, and a combination of polyfunctional (meth)acrylate compounds and polyurethane (meth)acrylate compounds is more preferred.

The content of the multifunctional (meth)acrylate compound is preferably 50 to 100 parts by mass, more preferably 60 to 95 parts by mass, and further preferably 70 to 90 parts by mass, relative to 100 parts by mass of the solid component of the curable composition. In this specification, the solid component of the curable composition refers to the total amount of the components obtained by removing the solvent from the curable composition when the curable composition contains a solvent.

The curable composition may contain a polymerization initiator in addition to the curable component. Examples of the polymerization initiator include photopolymerization initiators and free radical polymerization initiators, and any known polymerization initiator may be used.

The curable composition can be cured by coating the film substrate and then irradiating the film substrate with active energy rays to polymerize the curable components such as the (meth)acrylic compound.

The hard coating layer preferably shows a value of 8B or harder in the pencil hardness test (measured by placing the first substrate layer on a glass plate) specified in JIS K 5600-5-4:1999 "General test methods for coatings - Part 5: Mechanical properties of coatings - Section 4: Scratch hardness (pencil method)", and may also show a value of 5B or harder.

The surface of the film substrate on the side where the surface coating layer such as the hard coating layer is formed may be coated with a release agent and subjected to a release treatment. The first substrate layer may be incorporated together with the light absorbing anisotropic layer when the light absorbing anisotropic layer is incorporated into the laminate, or may be peeled off and removed. By subjecting the surface of the film substrate to a release treatment as described above, the film substrate constituting the first substrate layer may be peeled off and removed when the light absorbing anisotropic layer is applied to a display device, and the surface coating layer and the light absorbing anisotropic layer may be incorporated.

The protective film constituting the film with the protective film can be releasably provided on the film substrate constituting the first substrate layer. The protective film may have a multilayer structure of a resin film and an adhesive layer, or may be a self-adhesive film including a resin film of a single layer structure. As the resin film used in the protective film having a multilayer structure, a film formed of the resin exemplified as the resin constituting the film substrate can be cited. As the self-adhesive film, a film using a polypropylene resin and a polyethylene resin can be cited. The protective film is usually removed after the light absorption anisotropic layer is applied to the display device.

The surface of the first substrate layer on which the light absorption anisotropic layer is to be formed may be subjected to surface treatment. Examples of the surface treatment method include a method of subjecting the surface of the film substrate to a corona treatment or a plasma treatment in an atmosphere ranging from vacuum to atmospheric pressure, a method of subjecting the surface to a laser treatment, a method of subjecting the surface to an ozone treatment, a method of subjecting the surface to a flame treatment, and a method of subjecting the surface of the first substrate layer to a saponification treatment.

The thickness of the first substrate layer is preferably thinner in terms of quality to enable practical handling, but if it is too thin, the strength tends to decrease and the workability tends to deteriorate. From this viewpoint, the thickness of the first substrate layer is preferably 30 μm to 150 μm, or 40 μm to 150 μm, or 50 μm to 140 μm, or 60 μm to 130 μm, or 70 μm to 120 μm.

(Protective layer) The protective layer can be laminated on the side of the light absorbing anisotropic layer opposite to the bonding layer side. The protective layer can be laminated directly in contact with the light absorbing anisotropic layer, can be laminated via the first alignment layer, or can be laminated via the bonding layer (adhesive layer and/or bonding agent layer). The protective layer can be formed using the material exemplified as the first substrate layer, or can be the first substrate layer.

In order to easily suppress the generation of tint when the display device is displayed in a black state in a hot and humid environment, it is preferred to reduce the moisture permeability of the protective layer. The transmittance of the protective layer is preferably 500 g/m ² /24 hours or less, more preferably 150 g/m ² /24 hours or less, and further preferably 20 g/m ² /24 hours or less. There is no particular lower limit for the moisture permeability of the protective layer, but it is usually 1 g/m ² /24 hours or more, and preferably 5 g/m ² /24 hours or more. The moisture permeability of the protective layer is the moisture permeability at a temperature of 40°C and a relative humidity of 90%, and can be measured by the cup method specified in JIS Z 0208.

(Polarizing element) The polarizing element has the property of allowing linear polarized light having a vibration plane orthogonal to the absorption axis to pass through when non-polarized light is incident. The polarizing element includes a polyvinyl alcohol resin, iodine, and boron. The polarizing element has iodine adsorbed and aligned on the polyvinyl alcohol resin layer and has a structure cross-linked by boron (cross-linked structure of borate ester).

The polarizing element can be obtained through the following steps: a step of uniaxially stretching a polyvinyl alcohol resin film (hereinafter, sometimes referred to as a "PVA film"), a step of dyeing the PVA film with iodine to adsorb the iodine, a step of treating the PVA film adsorbed with iodine with an aqueous boric acid solution, and a step of washing with water after treatment with an aqueous boric acid solution as needed.

The thickness of the polarizing element is usually 30 μm or less, preferably 18 μm or less, more preferably 15 μm or less, and further preferably 10 μm or less. The thickness is usually 1 μm or more, for example, 5 μm or more.

The uniaxial stretching of the PVA film can be performed before, during, or after dyeing with iodine. When the uniaxial stretching is performed after dyeing, the uniaxial stretching can be performed before or during the boric acid treatment. Of course, the uniaxial stretching can also be performed in multiple stages as shown here. The uniaxial stretching can be performed by the following methods: a method of performing uniaxial stretching in the film transport direction between rollers with different peripheral speeds, a method of performing uniaxial stretching in the film transport direction using hot rollers, a method of performing stretching in the width direction using a tenter, etc. The uniaxial stretching can be performed by dry stretching in the atmosphere, or by wet stretching in a state where the PVA film is swollen using a solvent such as water. The stretching ratio is usually about 3 to 8 times. Alternatively, an aqueous solution containing polyvinyl alcohol may be applied to a thermoplastic resin film and then dried, and then stretched together with the thermoplastic resin film by the above method.

The dyeing of the PVA film with iodine can be performed, for example, by immersing the PVA film in an aqueous solution containing iodine.

The polarizing element can also be obtained by the following steps: preparing a substrate film, applying a solution of a resin such as a polyvinyl alcohol resin on the substrate film, and removing the solvent to form a resin layer on the substrate film. Then, the amount of solvent such as water in the resin layer is adjusted as needed, and then the substrate film and the resin layer are uniaxially stretched, and then the resin layer is dyed with iodine so that the iodine is adsorbed and aligned on the resin layer. Then, the resin layer adsorbed and aligned with iodine is treated with an aqueous boric acid solution as needed, and then a washing step is performed to rinse off the aqueous boric acid solution. In this way, a resin layer adsorbed and aligned with iodine, that is, a polarizing element, is manufactured. The substrate film may be incorporated together with the polarizing element when the polarizing element is incorporated into the laminate, or may be peeled off and removed. When the substrate film is incorporated together with the polarizing element, the substrate film may be used as a protective film for the polarizing element. Examples of the substrate film include the thermoplastic resin film exemplified as the protective film used in the polarizing plate described below.

(Polarizing plate) Polarizing plate is a linear polarizing plate with a protective film on one or both sides of the polarizing element. The protective film can be a thermoplastic resin film. In order to improve the adhesion with the polarizing element, the thermoplastic resin film can be subjected to surface treatment (such as corona treatment, etc.), and a thin layer such as a primer layer (also called a primer layer) can be formed. The polarizing element and the protective film can be directly connected, or they can be laminated with a bonding layer (adhesive layer and/or adhesive layer) interposed therebetween.

Thermoplastic resins constituting the thermoplastic resin film are preferably transparent films, for example: cellulose resins such as triacetylcellulose; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polyether resins; polyester resins; polycarbonate resins; polyamide resins such as nylon or aromatic polyamide; polyimide resins; polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymer; cyclic polyolefin resins and cyclic polyolefin resins having a norbutylene structure (also called norbutylene resins); (meth)acrylic resins; polyarylate resins; polystyrene resins; polyvinyl alcohol resins, etc. Among them, the thermoplastic resin film is preferably a cyclic polyolefin resin film, a cellulose ester resin film, a polyester resin film or a (meth)acrylic resin film.

The protective film may also be a thermoplastic resin film having a hard coating layer formed on it. The hard coating layer may be formed on one side of the thermoplastic resin film or on both sides. By providing the hard coating layer, a thermoplastic resin film having improved hardness and scratch resistance may be produced. The hard coating layer is, for example, a hardening layer of an active energy ray-hardening resin, preferably a hardening layer of an ultraviolet-hardening resin. Examples of ultraviolet-hardening resins include: (meth) acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, epoxy resins, and the like. The hard coating layer may also contain additives in order to increase strength. The additive is not particularly limited, and examples thereof include inorganic microparticles, organic microparticles, or a mixture thereof.

The thickness of the protective film is preferably 5 μm to 150 μm, and may be 10 μm to 100 μm, or 10 μm to 80 μm.

(Phase difference body) The laminate 2 may also have a phase difference body 13 including one or more phase difference layers on the side of the polarizing element 12 opposite to the bonding layer 15. The phase difference body 13 preferably includes one or more phase difference layers having an in-plane phase difference, and may further include a phase difference layer having a phase difference in the thickness direction.

In the case where the polarizing element 12 and the phase difference body 13 in the laminate function as an antireflection film, from the viewpoint of highly achieving the antireflection function, it is preferred that a λ/4 phase difference layer having a λ/4 plate function (i.e., a phase difference function of π/2) having a full range of visible light is used as the phase difference layer having an in-plane phase difference contained in the phase difference body 13. The λ/4 phase difference layer is preferably a λ/4 phase difference layer with reverse wavelength dispersion. A combination of a phase difference layer having a λ/2 plate function with positive wavelength dispersion (λ/2 phase difference layer) and a λ/4 phase difference layer with positive wavelength dispersion can also be used as the phase difference layer having an in-plane phase difference.

When the polarizing element 12 and the phase difference body 13 function as antireflection films, from the viewpoint of compensating for the antireflection function in an oblique direction, the phase difference body may include a positive C plate as a phase difference layer having a phase difference in the thickness direction in addition to a phase difference layer having an in-plane phase difference.

When the phase difference body 13 includes a phase difference layer having an in-plane phase difference and a phase difference layer having a phase difference in the thickness direction, the lamination order thereof is not particularly limited, and the phase difference layer having an in-plane phase difference and the phase difference layer having a phase difference in the thickness direction may be included in order from the polarizing element 12 side, or vice versa. A bonding layer may also be provided between the phase difference layers constituting the phase difference body 13. The bonding layer is an adhesive layer and/or a bonding agent layer.

The phase difference body 13 is preferably a first phase difference layer (phase difference layer) that satisfies the relationship of the following formula (4) and formula (5). 120 nm ≦ Re (550) ≦ 160 nm (4) Re (450) / Re (550) ≦ 1.0        (5) [In formula (4) and formula (5), Re (λ) represents the in-plane phase difference value of the first phase difference layer at wavelength λ [nm]]

The Re(550) of the first phase difference layer may be 125 nm to 155 nm, 130 nm to 150 nm, or 135 nm to 145 nm. By making the Re(550) of the first phase difference layer within the above range, the first phase difference layer can better function as a λ/4 phase difference layer.

If "Re(450)/Re(550)" in the above formula (5) exceeds 1.0, when the first phase difference layer and the polarizing element 12 constitute an anti-reflection film (elliptical polarizer), the light leakage on the short wavelength side increases. "Re(450)/Re(550)" is preferably 0.7 to 1.0, more preferably 0.80 to 0.95, further preferably 0.80 to 0.92, and particularly preferably 0.82 to 0.88. When a polymerizable liquid crystal compound is used to obtain the first phase difference layer, the value of "Re(450)/Re(550)" can be arbitrarily adjusted by adjusting the mixing ratio of the polymerizable liquid crystal compound.

The Re(450) of the first retardation layer may be greater than or equal to 110 nm and less than or equal to 150 nm, may be greater than or equal to 115 nm and less than or equal to 140 nm, or may be greater than or equal to 120 nm and less than or equal to 130 nm.

The in-plane phase difference value of the first phase difference layer can be adjusted by the thickness of the first phase difference layer. The in-plane phase difference value is determined by the following formula. Re(λ)＝d1×Δn(λ) [wherein, Re(λ) represents the in-plane phase difference value of the first phase difference layer at wavelength λ[nm], d1 represents the thickness of the first phase difference layer, Δn(λ) represents the birefringence of the first phase difference layer at wavelength λ[nm]]

According to the above formula, it can be understood that in order to set the in-plane phase difference value (Re(λ)) of the first phase difference layer at a wavelength λ[nm] to a desired value, it is only necessary to adjust Δn(λ) and the thickness d1. The thickness of the first phase difference layer is preferably 0.5 μm to 5 μm, and more preferably 1 μm to 3 μm. The thickness can be measured by an interference film thickness gauge, a laser microscope or a stylus film thickness gauge. Furthermore, when a polymerizable liquid crystal compound is used to obtain the first phase difference layer, Δn(λ) depends on the molecular structure of the polymerizable liquid crystal compound.

As described above, the phase difference body may include a phase difference layer having a phase difference in the thickness direction (hereinafter, sometimes referred to as the "second phase difference layer"). The second phase difference layer is, for example, a positive C plate. The phase difference value Rth(550) in the thickness direction of the positive C plate at a wavelength of 550 nm is usually in the range of -170 nm to -10 nm, preferably -150 nm to -20 nm, and more preferably -100 nm to -40 nm. If the phase difference value in the thickness direction of the positive C plate is within this range, the anti-reflection properties in the oblique direction can be further improved when the phase difference body 13 and the polarizing element 12 constitute an anti-reflection film (elliptical polarizing plate). The phase difference value Rth(550) can be measured by a phase difference measuring device.

When the phase difference layer (first phase difference layer, second phase difference layer, etc.) constituting the phase difference body includes a liquid crystal film, the phase difference layer may be incorporated into the laminated body in a laminated state with a substrate layer (hereinafter referred to as the second substrate layer) supporting the phase difference layer. The phase difference layer and the substrate layer may be directly in contact.

The phase difference layer included in the phase difference body may be a stretched film or a liquid crystal film including a liquid crystal film, preferably a liquid crystal film.

When the phase difference layer is a stretched film, the stretched film may be a known one, and a resin film having a phase difference imparted thereto by uniaxial stretching or biaxial stretching may be used. As the resin film, cellulose films such as triacetylcellulose and diacetylcellulose, polyester films such as polyethylene terephthalate, polyethylene isophthalate and polybutylene terephthalate, acrylic resin films such as polymethyl (meth)acrylate and polyethyl (meth)acrylate, polycarbonate films, polyether sulfone films, polysulfone films, polyimide films, polyolefin films, polynorthene films, etc. may be used, but the invention is not limited thereto.

When the phase difference layer is a stretched film, the thickness of the phase difference layer is usually 5 μm to 200 μm, preferably 10 μm to 80 μm, and more preferably 40 μm to 40 μm.

When the phase difference layer is a liquid crystal film, the liquid crystal film may include a liquid crystal film formed by applying a composition including a compound having liquid crystallinity (hereinafter, sometimes referred to as "second composition") on a second substrate layer.

As the second substrate layer, those described in the first substrate layer can be cited. The second substrate layer can be peeled off and removed when incorporated into the laminate, and can also be used as a protective layer for the phase difference layer without being peeled off and removed. As a liquid crystal compound, a liquid crystal compound having a polymerizable group, especially a photopolymerizable group, that is, a polymerizable liquid crystal compound can be used. As a polymerizable liquid crystal compound, for example, a polymerizable liquid crystal compound previously known in the field of phase difference film can be used. The so-called photopolymerizable group refers to a group that can participate in the polymerization reaction through a reactive species generated from a photopolymerization initiator, such as an active free radical or an acid. As a photopolymerizable group, vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, ethylene oxide, cyclobutylene oxide, etc. can be cited. Among them, preferred are acryloxy, methacryloxy, vinyloxy, ethylene oxide and cyclobutylene, and more preferred is acryloxy. The liquid crystal may be thermotropic liquid crystal or liquid crystal. In terms of achieving dense film thickness control, thermotropic liquid crystal is preferred. In addition, as the phase order structure in the thermotropic liquid crystal, it may be nematic liquid crystal or smectic liquid crystal. In addition, it may be rod-shaped liquid crystal or disc-shaped liquid crystal. The polymerizable liquid crystal compound may be used alone or in combination of two or more.

In the case where the first phase difference layer (λ/4 phase difference layer) is a liquid crystal film comprising a liquid crystal cured film (liquid crystal film) formed by polymerizing and curing a polymerizable liquid crystal compound, it is preferably a liquid crystal film comprising a polymerizable liquid crystal compound oriented in a horizontal direction. As a polymerizable liquid crystal compound used to obtain the first phase difference layer, from the perspective of reverse wavelength dispersion, it is preferably a liquid crystal having a T-shaped or H-shaped mesogen structure that has birefringence in a direction perpendicular to the molecular long axis direction. From the perspective of obtaining a stronger dispersion, a T-shaped liquid crystal is more preferably used. As a structure of a T-shaped liquid crystal, specifically, for example, a compound represented by the following formula (II) can be cited. [Chemistry 1] [In formula (II), Ar represents a divalent aromatic group which may have a substituent. The divalent aromatic group preferably contains at least one of a nitrogen atom, an oxygen atom, and a sulfur atom. When there are two or more aromatic groups contained in the divalent group Ar, the two or more aromatic groups may be bonded to each other by a single bond, -CO-O-, -O- or other divalent bonding groups. ^G1 and ^G2 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. Here, the hydrogen atom contained in the divalent aromatic group or divalent alicyclic hydrocarbon group may be substituted by a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and the carbon atom constituting the divalent aromatic group or divalent alicyclic hydrocarbon group may be substituted by an oxygen atom, a sulfur atom or a nitrogen atom. L ¹ , L ² , B ¹ and B ² are each independently a single bond or a divalent linking group. k and l are each independently an integer of 0 to 3, satisfying the relationship of 1≦k+1. Here, when 2≦k+1, B ¹ and B ² , G ¹ and G ² may be the same or different from each other. ^E1 and ^E2 each independently represent an alkanediyl group having 1 to 17 carbon atoms, wherein the hydrogen atom contained in the alkanediyl group may be substituted by a halogen atom, and the _-CH2- contained in the alkanediyl group may be substituted by -O-, -S-, or -COO-. When there are plural -O-, -S-, or -COO-, they are not adjacent to each other. ^P1 and ^P2 each independently represent a polymerizable group or a hydrogen atom, and at least one of them is a polymerizable group.]

^G1 and ^G2 are each independently preferably 1,4-phenylenediyl which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, 1,4-cyclohexanediyl which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1,4-phenylenediyl substituted with methyl, unsubstituted 1,4-phenylenediyl, or unsubstituted 1,4-trans-cyclohexanediyl, and particularly preferably unsubstituted 1,4-phenylenediyl or unsubstituted 1,4-trans-cyclohexanediyl. Furthermore, it is preferred that at least one of a plurality of ^G1 and ^G2 is a divalent alicyclic hydrocarbon group, and it is more preferred that at least one of ^G1 and ^G2 bonded to ^L1 or ^L2 is a divalent alicyclic hydrocarbon group.

^L1 and ^L2 are each independently preferably ^a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, ^-S- , ^-Ra1OR2- , -Ra3COOR4-, -Ra5OCOR6-, Ra7OC= ^OOR8- , ^{-N=N-, -CRc=CRd-, or C≡C-. Here, Ra1 to Ra8 are each} independently a single bond, or an alkylene group ^{having 1} to 4 carbon atoms, and ^Rc and ^Rd are alkyl groups ^{having 1} to 4 carbon atoms or a hydrogen atom. ^L1 and ^L2 are each independently more preferably ^{a single} bond, ^{-ORa2-1- , -CH2-} _{, -CH2CH2- ,} ^{-COOR4-1- ,} or ^OCOR6-1- . Here, ^{Ra2-1 , Ra4-1 ,} and ^Ra6-1 independently represent ^{a single} bond, _-CH2- , or ^-CH2CH2- . ^L1 and ^L2 independently represent preferably a ^single bond, _{-O- , -CH2CH2-} , -COO- _{, -COOCH2CH2-} , or _OCO- .

^B1 and ^B2 are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a9 OR ^a10 -, -R ^a11 COOR ^a12 -, -R ^a13 OCOR ^a14 -, or R ^a15 OC=OOR ^a16 -. Here, R ^a9 to R ^a16 are each independently a single bond, or an alkylene group having 1 to 4 carbon atoms. ^B1 and ^B2 are each independently more preferably a single bond, -OR ^{a10 - 1} -, -CH ₂ -, -CH ₂ CH ₂ -, -COOR ^{a12 - 1} -, or OCOR ^{a14 - 1} -. Here, ^{Ra10-1 , Ra12-1 ,} and ^Ra14-1 each independently represent a ^single bond _, -CH2-, or ^-CH2CH2- . ^B1 and ^B2 each independently represent preferably a _single bond ^, _{-O- , -CH2CH2-} , -COO- ^, _-COOCH2CH2- , _-OCO- , _{or OCOCH2CH2-} .

From the viewpoint of inverse wavelength dispersion performance, k and l are preferably in the range of 2≦k+l≦6, preferably k+l=4, and more preferably k=2 and l=2. If k=2 and l=2, a symmetrical structure is obtained, which is preferred.

^E1 and ^E2 are each independently preferably an alkanediyl group having 1 to 17 carbon atoms, more preferably an alkanediyl group having 4 to 12 carbon atoms.

Examples of the polymerizable group represented by ^P1 or ^P2 include epoxy, vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, oxirane, and cyclobutylene. Among them, acryloxy, methacryloxy, vinyloxy, oxirane, and cyclobutylene are preferred, and acryloxy is more preferred.

Ar preferably has at least one selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocyclic ring which may have a substituent, and an electron withdrawing group. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring, and benzene ring and naphthalene ring are preferred. Examples of the aromatic heterocyclic ring include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrrolidine ring, a pyrimidine ring, a triazole ring, a trilazole ring, a pyrroline ring, an imidazole ring, a pyrazole ring, a thiazole ring, a benzothiazole ring, a thienothiazole ring, a thiazole ring, a benzothiazole ring, a benzothiazole ring, and a phenanthroline ring. Among them, it is preferred to have a thiazole ring, a benzothiazole ring, or a benzofuran ring, and it is further preferred to have a benzothiazolyl group. In addition, when a nitrogen atom is included in Ar, the nitrogen atom preferably has a π electron.

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

As the aromatic group represented by Ar, for example, the following groups can be preferably exemplified. [Chemistry 2] [In formulae (Ar-1) to (Ar-23), the symbol * represents a linking portion, and ^Z0 , ^Z1 , and ^Z2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 12 carbon atoms, an alkylsulfonyl group having 1 to 12 carbon atoms, a carboxyl group, a fluoroalkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, an N-alkylamino group having 1 to 12 carbon atoms, an N,N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylaminesulfonyl group having 1 to 12 carbon atoms, or an N,N-dialkylaminesulfonyl group having 2 to 12 carbon atoms. Q1 and ^Q2 each independently represent ^-CR2'R3'- , ^-S- , -NH-, ^-NR2'- , -CO- or O-, ^R2 ' and R3 ^' each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ^J1 and ^J2 each independently represent a carbon atom or a nitrogen atom. ^Y1 , ^Y2 and ^Y3 each independently represent an aromatic alkyl group or an aromatic heterocyclic group which may be substituted. ^W1 and ^W2 each independently represent a hydrogen atom, ^a cyano group, a methyl group or a halogen atom. m represents an integer of 0 to 6]

Examples of the aromatic alkyl group in Y ¹ , Y ² and Y ³ include aromatic alkyl groups having 6 to 20 carbon atoms, such as phenyl, naphthyl, anthracenyl, phenanthrenyl and biphenyl, preferably phenyl and naphthyl, and more preferably phenyl. Examples of the aromatic heterocyclic group include aromatic heterocyclic groups having 4 to 20 carbon atoms, such as furanyl, pyrrolyl, thienyl, pyridyl, thiazolyl and benzothiazolyl, which contain at least one hetero atom such as nitrogen, oxygen or sulfur, preferably furanyl, thienyl, pyridyl, thiazolyl and benzothiazolyl.

^Y1 , ^Y2 and ^Y3 may also be independently substituted polycyclic aromatic alkyl groups or polycyclic aromatic heterocyclic groups. Polycyclic aromatic alkyl groups refer to condensed polycyclic aromatic alkyl groups or groups derived from aromatic rings. Polycyclic aromatic heterocyclic groups refer to condensed polycyclic aromatic heterocyclic groups or groups derived from aromatic rings.

^Z0 , ^Z1 and ^Z2 are each independently preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, or an alkoxy group having 1 to 12 carbon atoms. ^Z0 is further preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cyano group. ^Z1 and ^Z2 are further preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a cyano group.

^Q1 and ^Q2 are preferably -NH-, -S-, ^-NR2'- , or -O-, and R2 ^' is preferably a hydrogen atom. Among them, -S-, -O-, or -NH- is particularly preferred.

Among the compounds represented by formulae (Ar-1) to (Ar-23), the compounds represented by formulae (Ar-6) and (Ar-7) are preferred from the viewpoint of molecular stability.

In the compounds represented by formulae (Ar-16) to (Ar-23), ^Y1 may form an aromatic heterocyclic group together with the nitrogen atom to which it is bonded and ^Z0 . Examples of the aromatic heterocyclic group include those mentioned above as the aromatic heterocyclic ring that Ar may have, such as: pyrrole ring, imidazole ring, pyrroline ring, pyridine ring, pyrrolidine ring, pyrimidine ring, indole ring, quinoline ring, isoquinoline ring, purine ring, pyrrolidinyl ring, etc. The aromatic heterocyclic group may have a substituent. In addition, ^Y1 may form the above-mentioned substituted polycyclic aromatic alkyl group or polycyclic aromatic heterocyclic group together with the nitrogen atom to which it is bonded and ^Z0 . For example, a benzofuran ring, a benzothiazole ring, a benzoxazole ring, etc. can be mentioned.

Among the polymerizable liquid crystal compounds, compounds with a maximum absorption wavelength of 300 to 400 nm are preferred. When a photopolymerization initiator is included in the second composition containing the polymerizable liquid crystal compound, there is a concern that the polymerization reaction and gelation of the polymerizable liquid crystal compound may proceed during long-term storage. However, if the maximum absorption wavelength of the polymerizable liquid crystal compound is 300 to 400 nm, even if it is exposed to ultraviolet light during storage, the generation of reactive species from the photopolymerization initiator and the polymerization reaction and gelation of the polymerizable liquid crystal compound caused by the reactive species can be effectively suppressed. Therefore, it becomes advantageous in terms of the long-term stability of the second composition, and the orientation and uniformity of the film thickness of the liquid crystal cured film contained in the first phase difference layer can be improved. Furthermore, the maximum absorption wavelength of the polymerizable liquid crystal compound can be measured in a solvent using an ultraviolet-visible spectrophotometer. The solvent is a solvent that can dissolve the polymerizable liquid crystal compound, and examples thereof include chloroform.

The content of the polymerizable liquid crystal compound in the second composition is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and further preferably 90 to 95 parts by mass, relative to 100 parts by mass of the solid components of the second composition. If the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the perspective of the orientation of the obtained liquid crystal cured film. Furthermore, in this specification, the so-called solid components of the polymerizable liquid crystal composition refer to all components obtained by removing volatile components such as organic solvents from the second composition.

The phase difference layer (first phase difference layer or second phase difference layer) of the liquid crystal film may include a second alignment layer in addition to the liquid crystal film. The second alignment layer can be selected according to the direction of aligning the liquid crystal compound, and may be a vertical alignment layer or a horizontal alignment layer. If the second alignment layer is a material that exhibits horizontal alignment as an alignment regulating force, the liquid crystal compound may form a horizontal alignment or a mixed alignment. If it is a material that exhibits vertical alignment, the liquid crystal compound may form a vertical alignment or a tilted alignment. Expressions such as horizontal and vertical indicate the direction of the long axis of the aligned liquid crystal compound when the plane of the phase difference layer is used as a reference. For example, the so-called vertical alignment refers to the long axis of the liquid crystal compound having an alignment direction perpendicular to the plane of the phase difference layer. Here, the term "vertical" means 90°±20° relative to the plane of the phase difference layer. As the second alignment layer, the one described in the first alignment layer can be cited.

The thickness of the liquid crystal film is preferably greater than 0.5 μm and less than 5 μm, and more preferably greater than 1 μm and less than 3 μm.

(Laminating layer) The laminating layer is at least one of an adhesive layer and a bonding agent layer, and may also include both an adhesive layer and a bonding agent layer. In the laminate 1, 2, in addition to the laminating layer 15 disposed between the light absorption anisotropic layer 11 and the polarizing element 12, a laminating layer for laminating each layer contained in the laminate 1, 2 may also be provided.

When the bonding layer is an adhesive layer, it is an adhesive layer formed using an adhesive composition. Adhesive compositions or reaction products of adhesive compositions that exhibit adhesion by attaching themselves to an adherend are called so-called pressure-sensitive adhesives. In addition, an adhesive layer formed using the active energy ray-curing adhesive composition described below can adjust the degree of crosslinking or adhesion by irradiating active energy rays.

As the adhesive composition, conventionally known adhesives with excellent optical transparency can be used without particular limitation. For example, acrylic polymers, urethane polymers, polysiloxane polymers, polyvinyl ethers, etc. can be used. Base polymer adhesive composition. Furthermore, the adhesive composition may be an active energy ray-curing adhesive composition, a thermosetting adhesive composition, or the like. Among these, an adhesive composition using an acrylic resin as a base polymer having excellent transparency, adhesive force, re-peelability (reworkability), weather resistance, heat resistance, etc. is preferred. The adhesive layer is preferably composed of a reaction product of an adhesive composition containing (meth)acrylic resin, a cross-linking agent, and a silane compound, and may also contain other components.

The adhesive composition used to form the adhesive layer may include, for example, base polymers such as acrylic polymers, urethane polymers, polysiloxane polymers, and polyvinyl ethers. The adhesive composition may also be an active energy ray-hardening adhesive, a thermosetting adhesive, or the like. Among them, an adhesive using a (meth)acrylic resin as a base polymer that is excellent in transparency, adhesion, re-peelability (reworkability), weather resistance, heat resistance, etc. is preferred. The adhesive layer is preferably composed of a reaction product of an adhesive containing (meth)acrylic resin, a cross-linking agent, and a silane compound, and may also contain other components.

The adhesive layer can also be formed using an active energy ray-curing adhesive. The active energy ray-curing adhesive can be formed by mixing a UV-curing compound such as a multifunctional acrylate into the above-mentioned adhesive composition to form an adhesive layer and then irradiating it with UV rays to cure it, thereby forming a harder adhesive layer. The active energy ray-curing adhesive has the property of being cured by being irradiated with energy rays such as ultraviolet rays or electron beams. The active energy ray-curing adhesive has the following properties: it has adhesiveness before being irradiated with energy rays, so it can be closely attached to the adherend and is cured by being irradiated with energy rays to adjust the adhesion.

The thickness of the adhesive layer is not particularly limited, and is usually 5 μm to 300 μm, or 10 μm to 250 μm, or 15 μm to 100 μm, or 20 μm to 50 μm.

When the bonding layer is an adhesive layer, the adhesive layer can be formed using an adhesive composition. As the adhesive composition used to form the adhesive layer, adhesives other than pressure-sensitive adhesives (adhesives) can be cited, such as water-based adhesives and active energy ray-curing adhesives.

As the water-based adhesive, for example, there can be mentioned an adhesive obtained by dissolving or dispersing polyvinyl alcohol resin in water. There is no particular limitation on the drying method when using the water-based adhesive, and for example, a method of drying using a hot air dryer or an infrared dryer can be adopted.

The bonding layer is preferably a layer formed of a resin composition containing a water-soluble polymer as a water-based adhesive (hereinafter, also referred to as a "resin composition containing a water-soluble polymer"). The polarity of the water-soluble polymer is very different from that of the dichroic pigment, so it can hinder the diffusion of the dichroic pigment contained in the light absorption anisotropic layer. As such a water-soluble polymer, for example: polyacrylamide polymers; vinyl alcohol polymers such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, (meth) acrylic acid or its anhydride-vinyl alcohol copolymer; carboxyvinyl polymers; polyvinyl pyrrolidone; starch; sodium alginate; polyethylene oxide polymers, etc. These polymers can be used alone or in combination of two or more.

When the laminating layer is a layer formed of a resin composition containing a water-soluble polymer, the content of the water-soluble polymer in the layer is preferably 75 mass % or more, more preferably 80 mass % or more, and further preferably 85 mass % or more.

In the case where the bonding layer is formed of a resin composition containing a water-soluble polymer, a crosslinking agent may be used to introduce a crosslinking structure in order to improve the compactness of the layer and enhance the diffusion prevention function of the dichroic pigment contained in the light absorption anisotropic layer. As such a crosslinking agent, in addition to water-soluble crosslinking agents such as glyoxylate plasma ion bonding crosslinking agents or epoxy crosslinking agents, hydrophobic crosslinking agents such as isocyanate crosslinking agents, polyaldehyde crosslinking agents such as glyoxal or glyoxal derivatives, and metal compound crosslinking agents such as zirconium chloride or titanium lactate can also be used for the purpose of imparting water resistance.

When a crosslinking agent is used to introduce a crosslinking structure into the laminating layer, the amount of the crosslinking agent added can be appropriately determined according to the type of the crosslinking agent used. For example, the amount can be 0.1 to 100 parts by mass, preferably 1 to 50 parts by mass, and more preferably 10 to 30 parts by mass relative to 100 parts by mass of the water-soluble polymer. By setting the content of the crosslinking agent to the above range, it is easy to make the laminating layer dense and easy to improve the diffusion prevention function of the dichroic pigment contained in the light absorption anisotropic layer.

The resin composition containing the water-soluble polymer that can form the adhesive layer is usually prepared in the form of a solution in which the water-soluble polymer is dissolved in a solvent. The solvent can be selected according to the water-soluble polymer used, and typically, water, alcohol, a mixture of water and alcohol, etc. can be cited, and water is preferred.

Examples of active energy ray-curing adhesives include solvent-free active energy ray-curing adhesives containing a curable compound that is cured by irradiation with active energy rays such as ultraviolet rays, visible light, electron beams, and X-rays. By using solvent-free active energy ray-curing adhesives, the adhesion between layers can be improved.

When the bonding layer is an adhesive layer, the thickness is preferably 0.05 μm or more, more preferably 0.1 μm or more, and preferably 10 μm or less, more preferably 5 μm or less, and further preferably 1 μm or less.

In the laminates 1 and 2, when the bonding layer 15 includes one adhesive layer and one adhesive layer, the adhesive layer, the adhesive layer, and the polarizing element 12 can be arranged in sequence from the light absorbing anisotropic layer 11 side, or the adhesive layer, the adhesive layer, and the polarizing element 12 can be arranged in sequence from the light absorbing anisotropic layer 11 side.

(Organic EL display device) The organic EL display device is a device in which the above-mentioned laminate is laminated on a display element via an adhesive layer. In the organic EL display device, the laminate is assembled in such a way that the light absorption anisotropic layer side becomes the visible side. As an adhesive layer, the adhesive layer described as a bonding layer can be cited. [Example]

The present invention is further specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. "%" and "parts" in the Examples and Comparative Examples are mass % and mass parts unless otherwise specified.

[Preparation of substrate layer] (Substrate layer (1): TAC film) As the substrate layer (1), a triacetyl cellulose (TAC) film (KC4UY-TAC, manufactured by Konica Minolta) was prepared. The thickness of the substrate layer (1) was 40 μm.

(Base layer (2): PET film) As the base layer (2), a polyethylene terephthalate (PET) film (Diafoil T140E25, manufactured by Mitsubishi Resin Co., Ltd.) was prepared. The thickness of the base layer (2) was 38 μm.

(Substrate layer (3): HC layer/COP film) 70 parts of multifunctional acrylate ("A-DPH-12E": manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 30 parts of urethane acrylate ("UV-7650B": manufactured by Nippon Chemical Industry Co., Ltd.), 3 parts of polymerization initiator ("NCI-730": manufactured by ADEKA Co., Ltd.), 2 parts of the compound represented by the following formula (UVA-04), and 34 parts of methyl ethyl ketone were mixed to prepare a hard coating layer forming composition containing an ultraviolet absorber. The compound represented by formula (UVA-04) was synthesized with reference to the description of Synthesis Example 4 of Japanese Patent Publication No. 2017-120430. [Chemistry 3]

Next, a single side of a COP film (G+, manufactured by Nippon Zeon) was subjected to a corona treatment, and a hard coating composition was applied by a bar coater to form a coating layer. Dry air at 100°C was passed through the coating layer on the COP film at a flow rate of 0.5 m/s for 90 seconds to evaporate the solvent, and ultraviolet rays were irradiated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) in such a manner that the accumulated light intensity became 400 mJ/ ^cm2 , forming a hard coating layer containing an ultraviolet absorber (hereinafter, sometimes referred to as "HC layer") with a thickness of 5 μm, thereby manufacturing a substrate layer (3). The substrate layer (3) has a layer structure of HC layer/COP film and has a thickness of 30 μm.

(Substrate layer (4): COP film) A cycloolefin polymer (COP) film (ZF-14-50, manufactured by Nippon Zeon Co., Ltd.) was prepared as the substrate layer (4). The thickness of the substrate layer (4) was 50 μm.

[Preparation of bonding layer] (Preparation of adhesive layer (1)) As the adhesive layer (1), prepare an acrylic pressure-sensitive adhesive (manufactured by LINTEC) with a thickness of 15 μm.

(Preparation of adhesive layer (2)) As the adhesive layer (2), prepare an acrylic pressure-sensitive adhesive (manufactured by LINTEC) with a thickness of 20 μm.

(Preparation of water-based adhesive) Add 3 parts of carboxyl-modified polyvinyl alcohol (Kuraray Poval KL318, manufactured by Kuraray) and 1.5 parts of water-soluble polyamide epoxy resin (Sumirez Resin 650 (aqueous solution with a solid content concentration of 30%), manufactured by Sumika Chemtex) to 100 parts of water to prepare a water-based adhesive.

[Preparation of polarizing plate] (Production of polarizing element) A polyvinyl alcohol resin film with an average degree of polymerization of about 2,400 and a saponification degree of 99.9 mol% or more and a thickness of 30 μm was immersed in pure water at a temperature of 30°C, and then immersed in an aqueous solution of iodine/potassium iodide/water with a weight ratio of 0.02/2/100 at a temperature of 30°C for iodine dyeing (iodine dyeing step). The polyvinyl alcohol resin film that has undergone the iodine dyeing step was immersed in an aqueous solution of potassium iodide/boric acid/water with a weight ratio of 12/5/100 at a temperature of 56.5°C for boric acid treatment (boric acid treatment step). After the boric acid treatment step, the polyvinyl alcohol resin film was washed with pure water at 8°C and dried at 65°C to obtain a polarizing element (thickness 12 μm after extension) with iodine adsorbed and aligned on the polyvinyl alcohol resin film and having a structure cross-linked by boron (cross-linked structure of borate). At this time, extension was performed in the iodine dyeing step and the boric acid treatment step. The total extension ratio in the extension was 5.3 times.

(Preparation of polarizing plate) The substrate layer (1) prepared as above is used as a protective film. The polarizing element prepared as above and the substrate layer (1) treated with saponification are bonded together using a roller with the above-mentioned water-based adhesive. Tension is applied to the bonded product while drying at 60°C for 2 minutes to obtain a polarizing plate having the substrate layer (1) on one side of the polarizing element. The polarizing plate has a layer structure of substrate layer (1)/adhesive layer/polarizing element.

The optical properties of the polarizing plate were measured using a spectrophotometer (V7100, JASCO Corporation) with the polarizing element surface of the polarizing plate as the incident surface. The results showed that the sensitivity-corrected single transmittance was 42.7% and the sensitivity-corrected polarization degree was 99.991%.

[Preparation of Phase Difference Layer] (Preparation of Phase Difference Layer (1)) 5 parts of a photo-alignment material having the structure shown below (weight average molecular weight: 30,000) and 95 parts of cyclopentanone (solvent) were mixed, and the resulting mixture was stirred at a temperature of 80°C for 1 hour to prepare a composition for forming a horizontal alignment layer. [Chemistry 4]

A polymerizable liquid crystal compound (1) and a polymerizable liquid crystal compound (2) having the structures shown below were prepared respectively. The polymerizable liquid crystal compound (1) was prepared according to the method described in Japanese Patent Publication No. 2010-31223. The polymerizable liquid crystal compound (2) was prepared according to the method described in Japanese Patent Publication No. 2009-173893. The polymerizable liquid crystal compound (1): [Chemical 5] Polymerizable liquid crystal compound (2): [Chemical 6]

1 mg of the polymerizable liquid crystal compound (1) was dissolved in 50 mL of tetrahydrofuran to obtain a solution. The obtained solution was placed in a measuring cell with an optical path length of 1 cm as a measuring sample. The measuring sample was placed in an ultraviolet-visible spectrophotometer (UV-2450, manufactured by Shimadzu Corporation) to measure the absorption spectrum. The wavelength of maximum absorbance was read from the obtained absorption spectrum. The result showed that the maximum absorption wavelength λmax in the wavelength range of 300 to 400 nm was 350 nm.

A polymerizable liquid crystal compound (1) and a polymerizable liquid crystal compound (2) were mixed at a mass ratio of 90:10 to obtain a mixture. 0.1 parts of a leveling agent (BYK-361N, manufactured by BM Chemie) and 6 parts of 2-dimethylamino-2-benzyl-1-(4-oxo-1-phenyl)butane-1-one (Irgacure (registered trademark) 369 (Irg369), manufactured by BASF JAPAN Co., Ltd.) as a photopolymerization initiator were added to 100 parts of the obtained mixture. Furthermore, N-methyl-2-pyrrolidone (NMP) was added in such a manner that the solid content concentration became 13%. The mixture was stirred at a temperature of 80°C for 1 hour to prepare a second composition for forming a liquid crystal film.

After the substrate layer (4) was subjected to corona treatment, the horizontal alignment layer-forming composition prepared above was applied using a rod coater, dried at 80°C for 1 minute, and exposed to polarized UV light using a polarized UV irradiation device (SPOT CURE SP-9, manufactured by Ushio Electric Co., Ltd.) at a wavelength of 313 nm and a cumulative light amount of 100 mJ/ ^cm2 to form a horizontal alignment layer. The thickness of the horizontal alignment layer was measured using an elliptical polarimeter and the result was 200 nm.

Next, the second composition prepared above was coated on the horizontal alignment layer using a bar coater, and after heating at 120°C for 60 seconds, a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Niuwei Electric Co., Ltd.) was used to irradiate ultraviolet rays (cumulative light quantity at a wavelength of 365 nm in a nitrogen atmosphere: 500 mJ/ ^cm2 ) from the surface coated with the second composition, thereby forming a liquid crystal film (liquid crystal cured film) as a cured layer of the polymerizable liquid crystal compound, thereby forming a phase difference layer (1) having a layer structure of a horizontal alignment layer and a liquid crystal cured film. In this way, a phase difference layer with a substrate having a layer structure of substrate layer (4)/phase difference layer (1) (horizontal alignment layer/liquid crystal cured film) is obtained.

After confirming that the base layer (4) has no phase difference, the in-plane phase difference values of the phase difference layer with the base at wavelengths of 450 nm and 550 nm were measured using a phase difference measuring device (KOBRA-WPR, manufactured by Oji Instruments Co., Ltd.), and the in-plane phase difference values Re(450) and Re(550) of the phase difference layer (1) at wavelengths of 450 nm and 550 nm were calculated. As a result, Re(550) of the phase difference layer (1) was 142 nm, Re(450) was 121 nm, and Re(450)/Re(550) was 0.85.

(Phase difference layer (2)) The unstretched film made of olefin-based resin with a glass transition temperature (Tg) of 125°C is subjected to transverse uniaxial stretching at a temperature of 128°C to obtain a phase difference layer (2). The uniaxial stretching is performed using a tenter-type stretching machine.

The in-plane phase difference values of the phase difference layer (2) at wavelengths of 450 nm and 550 nm were measured using a phase difference measuring device (KOBRA-WPR, manufactured by Oji Instruments Co., Ltd.), and the in-plane phase difference values Re(450) and Re(550) of the phase difference layer (2) at wavelengths of 450 nm and 550 nm were calculated. As a result, Re(550) of the phase difference layer (2) was 142 nm, Re(450) was 143 nm, and Re(450)/Re(550) was 1.01. The direction of the retardation axis of the phase difference layer (2) was a direction (stretching direction) at 90° relative to the length direction of the film.

[Example 1] (Preparation of Liquid Crystal Composition (1)) The following components were mixed and stirred at 80°C for 1 hour to obtain a liquid crystal composition (1). Polymerizable liquid crystal compound (3): 75 parts Polymerizable liquid crystal compound (4): 25 parts Dichroic pigment (1): 1 part Polymerization initiator (1) [oligomer of 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropane-1-one (Esacure ONE; α-hydroxy ketone compound), manufactured by IGM Resins B. V.]: 1.5 parts Non-liquid crystal compound having a polymerizable group (dipentaerythritol hexaacrylate (6-functional)): 1.5 parts Leveling agent (F-556, manufactured by DIC): 0.25 parts Solvent (o-xylene): 300 parts

The polymerizable liquid crystal compounds (3) and (4) have the structures shown below and were synthesized according to the method described in Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996). ・Polymerizable liquid crystal compound (3): [Chem. 7]・Polymerizable liquid crystal compound (4): [Chemistry 8]

The dichroic dye (1) uses an azo dye described in the example of Japanese Patent Publication No. 2013-101328 having the structure shown below. The maximum absorption wavelength of the dichroic dye (1) measured in a chloroform solution is 600 nm. ・Dichroic dye (1): [Chemical 9]

(Preparation of light-absorbing anisotropic layer (a) with substrate) The substrate layer (1) was cut into quadrilaterals and subjected to one corona treatment using a corona treatment device (AGF-B10, manufactured by Kasuga Electric Co., Ltd.) at an output of 0.3 kW and a treatment speed of 3 m/min. The liquid crystal composition (1) was applied to the corona treatment surface of the cut substrate layer (1) using a rod coater, and then dried in a drying oven set at 100°C for 1 minute. Then, a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Electric Co., Ltd.) was used to irradiate ultraviolet rays (wavelength: 365 nm in a nitrogen atmosphere, cumulative light quantity at a wavelength of 365 nm: 500 mJ/ ^cm2 ) to form a light-absorbing anisotropic layer (1) in which the polymerizable liquid crystal compound and the dichroic pigment are vertically aligned relative to the coating plane. Thus, a light-absorbing anisotropic layer (a) with a substrate having a layer structure of substrate layer (1)/light-absorbing anisotropic layer (1) was obtained.

(Preparation of laminate (1)) Using the above-prepared light absorption anisotropic layer with substrate (a), polarizing plate, and phase difference layer with substrate, the light absorption anisotropic layer (1) and the phase difference layer (1) are subjected to corona treatment, and the intermediate adhesive layer (1) is laminated to obtain a laminate (1). The laminate (1) has a layer structure of substrate layer (1)/light absorption anisotropic layer (1)/adhesive layer (1)/polarizing plate (polarizing element/substrate layer (1))/adhesive layer (1)/phase difference layer (1) (liquid crystal curing film/horizontal alignment layer)/substrate layer (4). In the laminate (1), the angle between the absorption axis of the polarizing element and the retardation axis of the phase difference layer (1) is 45°. The substrate layer (1) serves as a protective layer for the light absorption anisotropic layer (1), and the adhesive layer (1) between the light absorption anisotropic layer (1) and the polarizing plate serves as a bonding layer.

[Examples 2 and 3] (Preparation of light-absorbing anisotropic layers with substrates (b) and (c)) The thickness of the light-absorbing anisotropic layer is changed to the thickness shown in Table 1. In addition, according to the steps of preparing the light-absorbing anisotropic layer with substrate (a), a light-absorbing anisotropic layer with substrate (b) having a layer structure of substrate layer (1)/light-absorbing anisotropic layer (2) and a light-absorbing anisotropic layer with substrate (c) having a layer structure of substrate layer (1)/light-absorbing anisotropic layer (3) are obtained.

(Production of laminates (2) and (3)) Laminates (2) and (3) are obtained by following the steps of producing laminate (1), except that the light absorption anisotropic layer with substrate (a) is changed to the light absorption anisotropic layer with substrate (b) and the light absorption anisotropic layer with substrate (c). Laminate (2) has a layer structure of substrate layer (1)/light absorption anisotropic layer (2)/adhesive layer (1)/polarizing plate (polarizing element/substrate layer (1))/adhesive layer (1)/phase difference layer (1) (liquid crystal curing film/horizontal alignment layer)/substrate layer (4). The laminate (3) has a layer structure of substrate layer (1)/light absorption anisotropic layer (3)/adhesive layer (1)/polarizing plate (polarizing element/substrate layer (1))/adhesive layer (1)/phase difference layer (1) (liquid crystal cured film/horizontal alignment layer)/substrate layer (4).

[Example 4] (Preparation of Liquid Crystal Composition (2)) Except that 1.5 parts of the polymerization initiator (1) was replaced with 2.0 parts of the polymerization initiator (2) shown below, the liquid crystal composition (2) was obtained according to the preparation steps of the liquid crystal composition (1). Polymerization initiator (2) [Irgacure OXE-01 (oxime ester compound), manufactured by BASF]: 2.0 parts

(Preparation of a light-absorbing anisotropic layer with a substrate (d)) The liquid crystal composition (1) is changed to the liquid crystal composition (2), and in addition, the light-absorbing anisotropic layer with a substrate (a) is prepared in accordance with the steps of preparing the light-absorbing anisotropic layer with a substrate to obtain a light-absorbing anisotropic layer with a substrate (d) having a layer structure of substrate layer (1)/light-absorbing anisotropic layer (4).

(Preparation of laminate (4)) The light absorption anisotropic layer with substrate (a) is changed to the light absorption anisotropic layer with substrate (d), and the laminate (4) is obtained according to the steps of preparing laminate (1). The laminate (4) has a layer structure of substrate layer (1)/light absorption anisotropic layer (4)/adhesive layer (1)/polarizing plate (polarizing element/substrate layer (1))/adhesive layer (1)/phase difference layer (1) (liquid crystal curing film/horizontal alignment layer)/substrate layer (4).

[Examples 5 and 6] (Preparation of light-absorbing anisotropic layers (e) and (f) with substrates) The thickness of the light-absorbing anisotropic layer is changed to the thickness shown in Table 1. In addition, according to the steps of preparing the light-absorbing anisotropic layer (d) with substrates, a light-absorbing anisotropic layer (e) with substrates having a layer structure of substrate layer (1)/light-absorbing anisotropic layer (5) and a light-absorbing anisotropic layer (f) with substrates having a layer structure of substrate layer (1)/light-absorbing anisotropic layer (6) are obtained.

(Production of laminates (5) and (6)) The light absorption anisotropic layer with a substrate (a) is changed to a light absorption anisotropic layer with a substrate (e) and a light absorption anisotropic layer with a substrate (f), and laminates (5) and (6) are obtained according to the steps of producing laminate (4). Laminate (5) has a layer structure of substrate layer (1)/light absorption anisotropic layer (5)/adhesive layer (1)/polarizing plate (polarizing element/substrate layer (1))/adhesive layer (1)/phase difference layer (1) (liquid crystal curing film/horizontal alignment layer)/substrate layer (4). The laminate (6) has a layer structure of substrate layer (1)/light absorption anisotropic layer (6)/adhesive layer (1)/polarizing plate (polarizing element/substrate layer (1))/adhesive layer (1)/phase difference layer (1) (liquid crystal curing film/horizontal alignment layer)/substrate layer (4).

[Example 7] (Preparation of laminate (7)) The phase difference layer with a substrate is replaced with the phase difference layer (2), and the laminate (7) is obtained according to the steps of preparing the laminate (1). The laminate (7) has a layer structure of substrate layer (1)/light absorption anisotropic layer (1)/adhesive layer (1)/polarizing plate (polarizing element/substrate layer (1))/adhesive layer (1)/phase difference layer (2).

[Example 8] (Preparation of Liquid Crystal Composition (3)) Except that 1.5 parts of the polymerization initiator (1) was replaced with 3.0 parts of the polymerization initiator (3) shown below, the liquid crystal composition (3) was obtained according to the preparation steps of the liquid crystal composition (1). Polymerization initiator (3) [Irgacure 184 (α-hydroxy ketone compound), manufactured by BASF]: 3.0 parts

(Preparation of a light-absorbing anisotropic layer with a substrate (g)) The liquid crystal composition (1) is changed to the liquid crystal composition (3), and in addition, the light-absorbing anisotropic layer with a substrate (a) is prepared in accordance with the steps of preparing the light-absorbing anisotropic layer with a substrate to obtain a light-absorbing anisotropic layer with a substrate (g) having a layer structure of substrate layer (1)/light-absorbing anisotropic layer (7).

(Preparation of laminate (8)) The light absorption anisotropic layer with substrate (a) is changed to the light absorption anisotropic layer with substrate (g), and the laminate (8) is obtained according to the steps of preparing laminate (1). The laminate (8) has a layer structure of substrate layer (1)/light absorption anisotropic layer (7)/adhesive layer (1)/polarizing plate (polarizing element/substrate layer (1))/adhesive layer (1)/phase difference layer (1) (liquid crystal curing film/horizontal alignment layer)/substrate layer (4).

[Example 9] (Preparation of a composition for forming an alignment layer) 27.7 parts of propylene glycol monomethyl ether were added to 0.3 parts (solid content concentration 1.0%) of an alignment polymer Sunever (registered trademark) SE-610 (manufactured by Nissan Chemical Industries, Ltd.) to obtain a composition for forming an alignment layer. The solid content concentration of the alignment polymer is the solid content amount converted from the concentration stated in the delivery specification sheet.

(Preparation of anisotropic light-absorbing layer with substrate (h)) Using a corona treatment device (AGF-B10, manufactured by Kasuga Electric Co., Ltd.), the COP film surface of the substrate layer (3) was subjected to a corona treatment once at an output of 0.3 kW and a treatment speed of 3 m/min. After applying the alignment layer forming composition on the corona treated surface of the substrate layer (3) using a rod coater, it was dried in a drying oven set at 120°C for 1 minute to obtain an alignment layer.

The coating of the liquid crystal composition (2) on the substrate layer (1) is changed to coating the liquid crystal composition (2) on the alignment layer obtained above. In addition, according to the steps of preparing the light absorbing anisotropic layer with substrate (d), a light absorbing anisotropic layer with substrate (h) having a layer structure of substrate layer (3) (HC layer/COP film)/alignment layer/light absorbing anisotropic layer (4) is obtained.

(Preparation of laminate (9)) The light absorbing anisotropic layer (4) of the light absorbing anisotropic layer (h) with substrate prepared above is subjected to corona treatment. While applying tension to the light absorbing anisotropic layer (h) with substrate and the polarizing plate prepared above, the light absorbing anisotropic layer (4) side of the light absorbing anisotropic layer (h) with substrate and the polarizing element side of the polarizing plate are bonded together with a water-based adhesive and dried at 80°C for 2 minutes to form an adhesive layer (bonding layer). Thus, a laminated structure (x) of substrate layer (1)/light absorption anisotropic layer (4)/adhesive layer/polarizing plate (polarizing element/substrate layer (1)) is obtained. The phase difference layer (1) with the phase difference layer attached to the substrate is subjected to a corona treatment, and the phase difference layer (1) with the phase difference layer attached to the substrate is laminated on the polarizing plate side of the laminated structure (x) via the adhesive layer (1), thereby obtaining a laminate (9). The laminate (9) has a layer structure of substrate layer (3) (HC layer/COP film)/alignment layer/light absorption anisotropic layer (4)/adhesive layer/polarizing plate (polarizing element/substrate layer (1))/adhesive layer (1)/phase difference layer (1) (liquid crystal curing film/horizontal alignment layer)/substrate layer (4). The cross section of the laminate (9) was observed using a laser microscope to determine the thickness of the adhesive layer, which was 0.5 μm.

[Example 10] (Preparation of laminate (10)) The light absorption anisotropic layer with substrate (h) is changed to the light absorption anisotropic layer with substrate (a), and the laminate (10) is obtained according to the steps of preparing laminate (9). The laminate (10) has a layer structure of substrate layer (1)/light absorption anisotropic layer (1)/adhesive layer/polarizing plate (polarizing element/substrate layer (1))/adhesive layer (1)/phase difference layer (1) (liquid crystal curing film/horizontal alignment layer)/substrate layer (4).

[Example 11] (Preparation of laminate (11)) The light absorption anisotropic layer with substrate (h) is changed to the light absorption anisotropic layer with substrate (d), and the laminate (11) is obtained according to the steps of preparing laminate (9). The laminate (11) has a layer structure of substrate layer (1)/light absorption anisotropic layer (4)/adhesive layer/polarizing plate (polarizing element/substrate layer (1))/adhesive layer (1)/phase difference layer (1) (liquid crystal curing film/horizontal alignment layer)/substrate layer (4).

[Example 12] (Preparation of laminate (12)) The light absorbing anisotropic layer (a) with a substrate is prepared by the above-mentioned preparation steps, and the light absorbing anisotropic layer (1) is subjected to a corona treatment. A water-based adhesive is applied to the corona-treated surface of the light absorbing anisotropic layer (a) with a substrate using a rod coater, and then dried in a drying oven set at 80°C for 2 minutes to form an adhesive layer. Thereafter, the polarizing element side of the polarizing plate is bonded to the adhesive layer formed on the light absorbing anisotropic layer (a) with a substrate via the adhesive layer (1). Thus, a laminated structure (y) of substrate layer (1)/light absorption anisotropic layer (1)/adhesive layer/adhesive layer (1)/polarizing plate (polarizing element/substrate layer (1)) is obtained. The phase difference layer (1) of the phase difference layer attached to the substrate is subjected to a corona treatment, and the phase difference layer (1) of the phase difference layer attached to the substrate is laminated on the polarizing plate side of the laminated structure (y) via the adhesive layer (1), thereby obtaining a laminate (12). The laminate (12) has a layer structure of substrate layer (1)/light absorption anisotropic layer (1)/adhesive layer/adhesive layer (1)/polarizing plate (polarizing element/substrate layer (1))/adhesive layer (1)/phase difference layer (1) (liquid crystal curing film/horizontal alignment layer)/substrate layer (4). The cross section of the laminate (11) was observed using a laser microscope to determine the thickness of the adhesive layer, which was 0.5 μm.

[Example 13] (Preparation of laminate (13)) The light absorption anisotropic layer with substrate (a) is changed to the light absorption anisotropic layer with substrate (d), and the laminate (13) is obtained according to the steps of preparing laminate (12). The laminate (13) has a layer structure of substrate layer (1)/light absorption anisotropic layer (4)/adhesive layer/adhesive layer (1)/polarizing plate (polarizing element/substrate layer (1))/adhesive layer (1)/phase difference layer (1) (liquid crystal curing film/horizontal alignment layer)/substrate layer (4).

[Example 14] (Preparation of liquid crystal composition (4)) A liquid crystal composition (4) was obtained according to the steps for preparing the liquid crystal composition (1), except that 1 part of the dichroic dye (1) was replaced with 1 part of the dichroic dye (2). The dichroic dye (2) used was an azo dye described in the example of Japanese Patent Publication No. 2013-101328 having the structure shown below. The maximum absorption wavelength of the dichroic dye (2) measured in a chloroform solution was 488 nm. ・Dichroic dye (2): [Chemical 10]

(Preparation of light-absorbing anisotropic layer with substrate (i)) The liquid crystal composition (1) is changed to the liquid crystal composition (4), and in addition, the light-absorbing anisotropic layer with substrate (a) is prepared in accordance with the steps of preparing the light-absorbing anisotropic layer with substrate (i) having a layer structure of substrate layer (1)/light-absorbing anisotropic layer (8).

(Preparation of laminate (14)) The light absorption anisotropic layer with substrate (h) is changed to the light absorption anisotropic layer with substrate (i), and the laminate (14) is obtained according to the steps of preparing laminate (9). The laminate (14) has a layer structure of substrate layer (1)/light absorption anisotropic layer (8)/adhesive layer/polarizing plate (polarizing element/substrate layer (1))/adhesive layer (1)/phase difference layer (1) (liquid crystal curing film/horizontal alignment layer)/substrate layer (4).

[Example 15] (Preparation of liquid crystal composition (5)) A liquid crystal composition (5) was obtained according to the steps of preparing the liquid crystal composition (1), except that 1 part of the dichroic dye (1) was replaced with 1 part of the dichroic dye (3). The dichroic dye (3) used was an azo dye described in the example of Japanese Patent Publication No. 2013-101328 having the structure shown below. The maximum absorption wavelength of the dichroic dye (3) measured in a chloroform solution was 445 nm. ・Dichroic dye (3): [Chemical 11]

(Preparation of a light-absorbing anisotropic layer with a substrate (j)) The liquid crystal composition (1) is changed to the liquid crystal composition (5), and in addition, the light-absorbing anisotropic layer with a substrate (a) is prepared in accordance with the steps of preparing the light-absorbing anisotropic layer with a substrate, thereby obtaining a light-absorbing anisotropic layer with a substrate (j) having a layer structure of substrate layer (1)/light-absorbing anisotropic layer (9).

(Preparation of laminate (15)) The light absorption anisotropic layer with substrate (h) is changed to the light absorption anisotropic layer with substrate (j), and the laminate (15) is obtained according to the steps of preparing laminate (9). The laminate (15) has a layer structure of substrate layer (1)/light absorption anisotropic layer (9)/adhesive layer/polarizing plate (polarizing element/substrate layer (1))/adhesive layer (1)/phase difference layer (1) (liquid crystal curing film/horizontal alignment layer)/substrate layer (4).

[Example 16] (Preparation of liquid crystal composition (6)) The liquid crystal composition (6) is obtained by following the steps of preparing the liquid crystal composition (1) except that 1 part of the dichroic pigment (1) is replaced with 1 part of the dichroic pigment (1) and 2 parts of the dichroic pigment (2).

(Preparation of a light-absorbing anisotropic layer with a substrate (k)) The liquid crystal composition (1) is changed to the liquid crystal composition (6), and in addition, the light-absorbing anisotropic layer with a substrate (a) is prepared in accordance with the steps of preparing the light-absorbing anisotropic layer with a substrate to obtain a light-absorbing anisotropic layer with a substrate (k) having a layer structure of substrate layer (1)/light-absorbing anisotropic layer (10).

(Preparation of laminate (16)) The light absorption anisotropic layer with substrate (h) is changed to the light absorption anisotropic layer with substrate (k), and the laminate (16) is obtained according to the steps of preparing laminate (9). The laminate (16) has a layer structure of substrate layer (1)/light absorption anisotropic layer (10)/adhesive layer/polarizing plate (polarizing element/substrate layer (1))/adhesive layer (1)/phase difference layer (1) (liquid crystal curing film/horizontal alignment layer)/substrate layer (4).

[Comparative Example 1] (Preparation of Liquid Crystal Composition (7)) Liquid Crystal Composition (7) was obtained by following the steps of preparing Liquid Crystal Composition (1) except that the components were changed to the following. Polymerizable Liquid Crystal Compound (3): 75 parts Polymerizable Liquid Crystal Compound (4): 25 parts Dichroic Dye (1): 2.8 parts Polymerization Initiator (4) [Irgacure 369 (aminoketone compound), manufactured by BASF]: 6.0 parts Leveling Agent (BYK-361N (polyacrylate compound), manufactured by BYK-Chemie): 0.3 parts Solvent (o-xylene): 300 parts

(Preparation of anisotropic light-absorbing layer (m) with substrate) The substrate layer (2) was cut into quadrilaterals and subjected to one corona treatment at an output of 0.3 kW and a treatment speed of 3 m/min using a corona treatment device (AGF-B10, manufactured by Kasuga Electric Co., Ltd.). The alignment layer formation composition prepared above was applied to the corona treatment surface of the cut substrate layer (2) using a rod coater, and then dried in a drying oven set at 120°C for 1 minute to obtain an alignment layer.

The liquid crystal composition (7) was coated on the alignment layer using a bar coater and then dried in a drying oven set at 100°C for 1 minute. Subsequently, a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Niuwei Electric Co., Ltd.) was used to irradiate ultraviolet rays (under nitrogen atmosphere, wavelength: 365 nm, cumulative light quantity at wavelength 365 nm: 1000 mJ/ ^cm2 ) to form a light absorption anisotropic layer (11) in which the polymerizable liquid crystal compound and the dichroic pigment were aligned perpendicular to the coating plane. Thus, a light absorption anisotropic layer (m) with a substrate having a layer structure of substrate layer (2)/alignment layer/light absorption anisotropic layer (11) was obtained.

(Preparation of laminate (17)) Using the light absorbing anisotropic layer (m) with a substrate, the polarizing plate, and the phase difference layer with a substrate prepared as above, the light absorbing anisotropic layer (11) and the phase difference layer (1) are subjected to a corona treatment, and the intermediate adhesive layer (2) is laminated to obtain a laminate (17). The laminate (17) has a layer structure of substrate layer (2)/alignment layer/light absorption anisotropic layer (11)/adhesive layer (2)/polarizing plate (polarizing element/substrate layer (1))/adhesive layer (2)/phase difference layer (1) (liquid crystal cured film/horizontal alignment layer)/substrate layer (4). In the laminate (17), the angle between the absorption axis of the polarizing element and the retardation axis of the phase difference layer (1) is 45°.

[Comparative Example 2] (Preparation of anisotropic light-absorbing layer with substrate (n)) The thickness of the anisotropic light-absorbing layer was changed to the thickness shown in Table 3. In addition, the anisotropic light-absorbing layer with substrate (d) was prepared in accordance with the steps of preparing the anisotropic light-absorbing layer with substrate (n) having a layer structure of substrate layer (1)/anisotropic light-absorbing layer (12).

(Preparation of laminate (18)) The light absorption anisotropic layer with substrate (a) is changed to the light absorption anisotropic layer with substrate (n), and the laminate (18) is obtained according to the steps of preparing laminate (1). The laminate (18) has a layer structure of substrate layer (1)/light absorption anisotropic layer (12)/adhesive layer (1)/polarizing plate (polarizing element/substrate layer (1))/adhesive layer (1)/phase difference layer (1) (liquid crystal curing film/horizontal alignment layer)/substrate layer (4).

[Measurement of the phase transition temperature of polymerizable liquid crystal compounds] The polymerizable liquid crystal compound was heated on a glass substrate with an alignment layer formed thereon, and the phase transition temperature was confirmed by texture observation using a polarizing microscope (BX-51, manufactured by Olympus Corporation).

When the temperature of the polymerizable liquid crystal compound (3) is raised, the crystal phase presents a smectic A phase at 95°C, the phase transitions to a nematic phase at 111°C, and the phase transitions to an isotropic liquid phase at 113°C. It was confirmed that when the temperature is lowered, the phase transitions to a nematic phase at 112°C, the phase transitions to a smectic A phase at 110°C, and the phase transitions to a smectic B phase at 94°C.

The polymerizable liquid crystal compound (4) exhibited a smectic A phase from a crystalline phase at 81°C when the temperature was raised, phase-transferred to a nematic phase at 121°C, and phase-transferred to an isotropic liquid phase at 137°C. It was confirmed that when the temperature was lowered, the phase-transferred to a nematic phase at 133°C, the phase-transferred to a smectic A phase at 118°C, and the phase-transferred to a smectic B phase at 78°C.

For reference, the texture of thermotropic nematic liquid crystal LC242 and polymerizable liquid crystal compound (1) manufactured by BASF were observed in the same manner. These only showed a nematic phase, but no clear smectic phase.

[Measurement of absorbance of anisotropic light-absorbing layer] (Preparation of anisotropic light-absorbing layer) The substrate layer (1) is replaced with the substrate layer (4), and the anisotropic light-absorbing layer (1) is formed on the substrate layer (4) according to the steps for preparing the anisotropic light-absorbing layer (a) with a substrate. The side surface of the anisotropic light-absorbing layer (1) on the substrate layer (4) is bonded to a glass having a size of 4 cm × 4 cm and a thickness of 0.7 mm via the adhesive layer prepared above, to prepare a measurement sample (1). The liquid crystal composition (1) is replaced with the liquid crystal compositions (2) to (7), and the measurement samples (2) to (7) are prepared in the same manner as the preparation of the measurement sample (1).

(Measurement of absorbance) The sample prepared above was placed in an ultraviolet-visible spectrophotometer (UV-2450, manufactured by Shimadzu Corporation) to measure the absorbance. The absorbances Ax, Ay, Ax(z＝30°), Ax(z＝60°), Ay(z＝30°), and Ay(z＝60°) at the maximum absorption wavelength (λmax) in the wavelength range of 380 to 780 nm were measured. During the measurement, the sample was placed in the ultraviolet-visible spectrophotometer, and after correction was made so that the absorbance at a wavelength of 800 nm was 0, Ax was measured. Regarding Ax(z＝30°), Ax(z＝60°), Ay(z＝30°), and Ay(z＝60°), the measurement samples were set at a tilt of 30° or 60°, and the absorbance at a wavelength of 800 nm was corrected to be 0 before measurement. Ax and Ax(z＝60°) are as described in the above formulas (1) to (3). In addition, regarding Ay, Ax(z＝30°), Ay(z＝30°), and Ay(z＝60°), the method for estimating the absorbance Az in formula (1) was described. The results are shown in Tables 1 to 3.

The sufficiency of the relationship of the above formula (1) is determined in the following steps. The same linear polarization light as that used in the measurement of Ax is incident on the measurement sample while rotating it by 30° and 60° in a manner including the y-axis, thereby measuring Ax(z＝30°) and Ax(z＝60°). Similarly, the same linear polarization light as that used in the measurement of Ay is incident on the measurement sample while rotating it by 30° and 60° in a manner including the x-axis, thereby measuring Ay(z＝30°) and Ay(z＝60°). When there is no absorption anisotropy in the x-y plane, that is, when Ax and Ay are equal, Ax(z＝30°)＝Ay(z＝30°) and Ax(z＝60°)＝Ay(z＝60°), so Ax(z＝30°) and Ay(z＝30°) are set to A(z＝30°), Ax(z＝60°) and Ay(z＝60°) are set to A(z＝60), and Ax(z＝90°) and Ay(z＝90°) are set to A(z＝90). When the relationship A(z＝30°)＜A(z＝60°) is satisfied, the relationship A(z＝30°)＜A(z＝60°)＜A(z＝90°)＝Az is satisfied. Therefore, if A(z＝30°)＞(Ax＋Ay)/2 or A(z＝60°)＞(Ax＋Ay)/2, it is judged that the relationship of the above formula (2) is fully satisfied.

[Measurement of the thickness of the light-absorbing anisotropic layer] The thickness of the light-absorbing anisotropic layer was measured using an elliptical polarimeter (M-220 manufactured by JASCO Corporation). The results are shown in Tables 1 to 3.

[Appearance evaluation of laminated body (1)] (Appearance evaluation of laminated body at initial stage (1)) The substrate layer (4) of the laminated body produced in the examples and comparative examples other than Example 7 was peeled off, and the laminated body was bonded to alkali-free glass with a thickness of 0.7 mm via the adhesive layer (2) prepared as described above to produce an evaluation sample. The laminated body produced in Example 7 was directly bonded to alkali-free glass with a thickness of 0.7 mm via the adhesive layer (2) prepared as described above to produce an evaluation sample. The front glass and polarizing plate of the "Galaxy S5" manufactured by SAMSUNG were removed, and the display device was taken out. The evaluation sample was placed on the removed display device through water in a manner that the light absorption anisotropic layer side was closer to the viewing side than the polarizing element (in a manner that the alkali-free glass side of the evaluation sample became the display device side). Afterwards, the color tone of the reflected hue when viewed from the front direction was confirmed with the power of the display device turned OFF (during black display), and the evaluation was performed using the evaluation criteria shown below, which was used as the initial evaluation. The results are shown in Tables 1 to 3. <Evaluation Criteria> A: The color tone is almost not felt. B: The color tone is slightly felt. C: The color tone is felt. D: The color tone is felt and the reflectivity is felt to be particularly high.

(Appearance evaluation of laminated body after moisture and heat resistance test (1)) The above evaluation samples were placed in an environment with a temperature of 80°C and a relative humidity of 90%RH for 48 hours for moisture and heat resistance test. The evaluation samples after moisture and heat resistance test were evaluated by confirming the color tone of the reflected hue according to the steps and evaluation criteria described in the initial appearance evaluation of laminated body (1), and the evaluation was used as the evaluation after moisture and heat resistance test. The results are shown in Tables 1 to 3.

[Appearance evaluation of laminated body (2)] (Evaluation of appearance of laminated body in the initial stage (2)) The evaluation samples were placed on the display device according to the procedure described in the evaluation of appearance of laminated body in the initial stage (1). After that, the display device was powered on and the brightness was set to the maximum. The blue light cutoff function and color balance change were all turned off. When the white screen was displayed (the HTML color code #FFFFFF was displayed), the hue from the front and the hue from the diagonal direction were visually checked. The hue and hue difference in each direction at this time were evaluated according to the evaluation criteria shown below, and this was regarded as the initial evaluation. The results are shown in Tables 1 to 3. <Evaluation criteria> A: The hue difference was almost imperceptible. B: The hue from the front or from the diagonal direction is slightly felt, but the hue difference between the front and diagonal directions is not felt much. C: The hue difference is felt.

(Appearance evaluation of laminated body after moisture and heat resistance test (2)) Regarding the samples for evaluation of moisture and heat resistance test according to the procedure described in the appearance evaluation of laminated body after moisture and heat resistance test (1), the hue from the front and the hue from the oblique direction during white display were confirmed and evaluated according to the procedure and evaluation criteria described in the appearance evaluation of initial laminated body (2), and the evaluation was used as the evaluation after moisture and heat resistance test. The results are shown in Tables 1 to 3.

[Evaluation of film strength of light-absorbing anisotropic layer] The evaluation samples were prepared according to the procedure described in the initial evaluation of the appearance of the laminate (1) and cut with a cutter blade to form 10 × 10 pieces (a total of 100 pieces). Cellophane tape manufactured by Michelin was attached to the cut surface and then peeled off in a 90° direction. The evaluation was performed according to the evaluation criteria shown below as the evaluation of the film strength of the light-absorbing anisotropic layer. The results are shown in Tables 1 to 3. <Evaluation criteria> A: No damage to the light-absorbing anisotropic layer was observed. B: No damage was observed in the light absorption anisotropic layer in more than 50 of the 100 pieces. C: Damage was observed in the light absorption anisotropic layer in more than 51 of the 100 pieces.

[Table 1] Embodiment 1 2 3 4 5 6 Laminated body (1) (2) (3) (4) (5) (6) Distance L1[μm] 15.0 15.0 15.0 15.0 15.0 15.0 Distance L2[μm] 68.0 69.0 70.0 68.0 69.0 70.0 Protective layer Substrate layer (1) (1) (1) (1) (1) (1) Type TAC TAC TAC TAC TAC TAC Light absorbing anisotropic layer (1) (2) (3) (4) (5) (6) Liquid crystal composition (1) (1) (1) (2) (2) (2) Polymerization initiator (1) (1) (1) (2) (2) (2) Compound α-Hydroxy Ketone α-Hydroxy Ketone α-Hydroxy Ketone Oxime ester Oxime ester Oxime ester Thickness [μm] 1.0 2.0 3.0 1.0 2.0 3.0 Az＞(Ax＋Ay)/2 adequate adequate adequate adequate adequate adequate Ax 0.01 0.03 0.07 0.01 0.03 0.07 Ax(z＝60°) 0.13 0.27 0.36 0.12 0.28 0.32 Ax(z＝60°)/Ax＞2 adequate adequate adequate adequate adequate adequate Bonding layer Type Adhesive layer (1) Adhesive layer (1) Adhesive layer (1) Adhesive layer (1) Adhesive layer (1) Adhesive layer (1) Thickness [μm] 15.0 15.0 15.0 15.0 15.0 15.0 Phase difference layer (1) (1) (1) (1) (1) (1) Re(450)[nm] 121 121 121 121 121 121 Re(550)[nm] 142 142 142 142 142 142 Re(450)/Re(550) 0.85 0.85 0.85 0.85 0.85 0.85 Appearance evaluation (1) Early days A A A A A A After moisture and heat resistance test B B B B B B Appearance evaluation (2) Early days A A B A A B After moisture and heat resistance test B B B B B B Membrane strength A A B A A B

[Table 2] Embodiment 7 8 9 10 11 12 Laminated body (7) (8) (9) (10) (11) (12) Distance L1[μm] 15.0 15.0 0.5 0.5 0.5 15.5 Distance L2[μm] 68.0 68.0 43.5 53.5 53.5 68.5 Protective layer Substrate layer (1) (1) (3) (1) (1) (1) Type TAC TAC HC/COP TAC TAC TAC Light absorbing anisotropic layer (1) (7) (4) (1) (4) (1) Liquid crystal composition (1) (3) (2) (1) (2) (1) Polymerization initiator (1) (3) (2) (1) (2) (1) Compound α-Hydroxy Ketone α-Hydroxy Ketone Oxime ester α-Hydroxy Ketone Oxime ester α-Hydroxy Ketone Thickness [μm] 1.0 1.0 1.0 1.0 1.0 1.0 Az＞(Ax＋Ay)/2 adequate adequate adequate adequate adequate adequate Ax 0.01 0.01 0.01 0.01 0.01 0.01 Ax(z＝60°) 0.13 0.13 0.12 0.13 0.12 0.13 Ax(z＝60°)/Ax＞2 adequate adequate adequate adequate adequate adequate Bonding layer Type Adhesive layer (1) Adhesive layer (1) Next, the agent layer Next, the agent layer Next, the agent layer Adhesive layer (1) Thickness [μm] 15.0 15.0 0.5 0.5 0.5 0.5/15.0 Phase difference layer (2) (1) (1) (1) (1) (1) Re(450)[nm] 143 121 121 121 121 121 Re(550)[nm] 142 142 142 142 142 142 Re(450)/Re(550) 1.01 0.85 0.85 0.85 0.85 0.85 Appearance evaluation (1) Early days B A A A A A After moisture and heat resistance test B B A A A A Appearance evaluation (2) Early days A A A A A A After moisture and heat resistance test B B A A A A Membrane strength A A A A A A

[Table 3] Embodiment Comparison Example 13 14 15 16 1 2 Laminated body (13) (14) (15) (16) (17) (18) Distance L1[μm] 15.5 0.5 0.5 0.5 20.0 15.0 Distance L2[μm] 68.5 53.5 53.5 53.5 72.0 71.0 Protective layer Substrate layer (1) (1) (1) (1) (2) (1) Type TAC TAC TAC TAC PET TAC Light absorbing anisotropic layer (4) (8) (9) (10) (11) (12) Liquid crystal composition (2) (4) (5) (6) (7) (2) Polymerization initiator (2) (1) (1) (1) (4) (2) Compound Oxime ester α-Hydroxy Ketone α-Hydroxy Ketone α-Hydroxy Ketone Amine Ketone Oxime ester Thickness [μm] 1.0 1.0 1.0 1.0 2.0 4.0 Az＞(Ax＋Ay)/2 adequate adequate adequate adequate adequate adequate Ax 0.01 0.01 0.03 0.01 0.08 0.21 Ax(z＝60°) 0.12 0.11 0.07 0.16 0.86 0.62 Ax(z＝60°)/Ax＞2 adequate adequate adequate adequate adequate adequate Bonding layer Type Adhesive layer (1) Next, the agent layer Next, the agent layer Next, the agent layer Adhesive layer (2) Adhesive layer (1) Thickness [μm] 0.5/15.0 0.5 0.5 0.5 20.0 15.0 Phase difference layer (1) (1) (1) (1) (1) (1) Re(450)[nm] 121 121 121 121 121 121 Re(550)[nm] 142 142 142 142 142 142 Re(450)/Re(550) 0.85 0.85 0.85 0.85 0.85 0.85 Appearance evaluation (1) Early days A A A A A B After heat resistance test A A A A D C Appearance evaluation (2) Early days A B A A C C After moisture and heat resistance test A A A A C C Membrane strength A A A A C C

1: Laminated body 2: Laminated body 11: Light absorption anisotropy layer 12: Polarizing element 13: Phase difference body 15: Bonding layer 21: Protective layer L1: Distance L2: Distance

FIG1 is a cross-sectional view schematically showing a laminated body of one embodiment of the present invention. FIG2 is a cross-sectional view schematically showing a laminated body of another embodiment of the present invention.

1: Laminated body

11: Light absorption anisotropic layer

12: Polarizing element

15: Bonding layer

21: Protective layer

L1: Distance

L2: Distance

Claims (10)

A laminate having, in order, a light absorbing anisotropic layer, a bonding layer, and a polarizing element obtained from a liquid crystal composition, wherein the polarizing element comprises a polyvinyl alcohol resin, iodine, and boron, the light absorbing anisotropic layer comprises one or more dichroic pigments, and satisfies the following relationships (1) to (3), the liquid crystal composition comprises a liquid crystal compound and a polymerization initiator, the polymerization initiator is at least one of an oxime ester compound and an α-hydroxy ketone compound, Az＞(Ax＋Ay)/2       (1) 0.001≦Ax≦0.10    (2) Ax(z＝60°)/Ax≧2  (3) [In formulas (1) to (3), Ax, Ay, and Az are the absorbances of the maximum absorption wavelength of the above-mentioned light absorption anisotropic layer in the wavelength range of 380 nm to 780 nm, respectively representing the absorbances of linearly polarized light vibrating in the x-axis direction, y-axis direction, and z-axis direction, Ax(z＝60°) is the absorbance of the above-mentioned absorption maximum wavelength of the above-mentioned light absorption anisotropic layer, representing the absorbance of linearly polarized light vibrating in the x-axis direction when the above-mentioned light absorption anisotropic layer is rotated 60° with the y-axis as the rotation axis, Here, the above-mentioned x-axis is an arbitrary direction in the plane of the above-mentioned light absorption anisotropic layer, The above-mentioned y-axis is a direction in the plane of the above-mentioned light absorption anisotropic layer that is orthogonal to the above-mentioned x-axis, The z-axis is a direction orthogonal to the x-axis and the y-axis]. The multilayer body of claim 1, wherein the thickness of the light absorption anisotropic layer is greater than 0.2 μm and less than 3.5 μm. The multilayer structure of claim 1 further comprises a protective layer on the side of the light absorbing anisotropic layer opposite to the bonding layer. The laminate as claimed in claim 1, wherein the liquid crystal compound comprises a polymerizable liquid crystal compound. The laminate of claim 1, wherein the liquid crystal compound is a compound that forms a layered liquid crystal phase. The laminate of claim 1, wherein the dichroic pigment is an azo compound. The laminate as claimed in claim 1 further comprises a phase difference layer satisfying the relationship of the following formulas (4) and (5) on the side of the polarizing element opposite to the bonding layer side. The phase difference layer is a cured layer of a polymerizable liquid crystal compound. 120 nm ≦ Re (550) ≦ 160 nm (4) Re (450) / Re (550) ≦ 1.00      (5) [In formulas (4) and (5), Re (λ) represents the in-plane phase difference value of the phase difference layer at a wavelength of λ [nm]]. The multilayer structure of claim 1, wherein a distance L1 between a surface of the light absorbing anisotropic layer on the bonding layer side and a surface of the polarizing element on the bonding layer side is less than 20.0 μm. The multilayer body of claim 1 further has a protective layer on the side of the light absorbing anisotropic layer opposite to the bonding layer side, and the distance L2 between the surface of the protective layer opposite to the light absorbing anisotropic layer side and the surface of the polarizing element opposite to the bonding layer side is less than 85.0 μm. An organic EL display device comprises a laminate as claimed in any one of claims 1 to 9 being laminated on a display element via an adhesive layer.