Stacked body and display device

Abstract

Provided is a laminate that is excellent in the effect of preventing peeping from an oblique direction and has excellent directional anisotropy in which the transmittance in the front direction is excellent and the light absorption characteristics in the oblique direction are reduced, and a display device including the laminate.

Description

Technical Field

[0001] The present invention relates to a laminate and a display device comprising the laminate. Background Technology

[0002] In applications such as mobile phones, laptops, and bank ATMs, there is a need for display devices that can prevent others from peeping. For example, Patent Document 1 proposes a light-absorbing anisotropic film that provides an anti-peeping effect.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2016-27387 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] However, in the light absorption anisotropic film described in Patent Document 1, there are differences in the absorption of light from the tilt direction. Therefore, anisotropy is generated depending on the viewing position, and the anti-peeping effect is not always sufficient, requiring further improvement in the anti-peeping effect.

[0008] Therefore, the object of the present invention is to provide a laminate with excellent transmittance in the front direction and reduced directional anisotropy of light absorption characteristics in the oblique direction, and excellent effect in preventing viewing from the oblique direction, as well as a display device comprising the laminate.

[0009] Methods for solving problems

[0010] The inventors of this application conducted in-depth research to solve the aforementioned problems and discovered that by configuring the laminated body in a specific way, the aforementioned problems could be solved, thereby completing the present invention. That is, the present invention includes the following preferred embodiments.

[0011] [1] A laminate, comprising sequentially anisotropic light-absorbing film, horizontally oriented retardation film i, a polarizer, and horizontally oriented retardation film ii,

[0012] The light-absorbing anisotropic film is a light-absorbing anisotropic film formed by curing a liquid crystal composition containing a dichroic pigment and a liquid crystal compound. When any position direction in the film surface is set as the x-axis, the direction orthogonal to the x-axis in the film surface is set as the y-axis, and the film thickness direction orthogonal to both the x-axis and y-axis is set as the z-axis, the light-absorbing anisotropic film satisfies the following equations (1) to (3):

[0013] Az>(Ax+Ay) / 2 (1)

[0014] Ax(z=60°) / Ax>5 (2)

[0015] Ay(z=60°) / Ay>5 (3)

[0016] In equations (1) to (3),

[0017] Ax, Ay, Az, Ax(z=60°), and Ay(z=60°) are all the absorbance at the wavelength of maximum absorption of the aforementioned dichroic pigments in the aforementioned anisotropic light absorption film.

[0018] Ax represents the absorbance of linearly polarized light vibrating along the x-axis.

[0019] Ay represents the absorbance of linearly polarized light vibrating along the y-axis.

[0020] Az represents the absorbance of linearly polarized light vibrating along the z-axis.

[0021] Ax (z = 60°) represents the absorbance of linearly polarized light vibrating along the x-axis when the aforementioned membrane is rotated 60° about the y-axis.

[0022] Ay(z=60°) represents the absorbance of linearly polarized light vibrating along the y-axis when the aforementioned membrane is rotated 60° about the x-axis.

[0023] The horizontally oriented phase difference film i satisfies the following equation (4):

[0024] 70nm≤Re i (550)≤170nm (4)

[0025] In equation (4), Re i (λ) represents the in-plane phase difference value of the horizontally oriented phase difference film i at wavelength λnm.

[0026] The horizontally oriented phase difference film ii satisfies the following equation (5):

[0027] 120nm≤Re ii (550)≤160nm (5)

[0028] In equation (5), Re ii (λ) represents the in-plane phase difference value of the horizontally oriented phase difference film ii at a wavelength of λnm.

[0029] [2] The laminate as described in [1], wherein the aforementioned horizontally oriented phase difference film ii satisfies the following equation (6):

[0030] Re ii (450) / Re ii (550)<1.00 (6)

[0031] In equation (6), Re ii (λ) has the same meaning as in equation (5) above.

[0032] The angle θ between the slow axis of the aforementioned horizontally oriented retardation film ii and the absorption axis of the polarizer. ii The range is defined by the following formula (7):

[0033] 15°≤|θ ii |≤75° (7).

[0034] [3] The laminate as described in [1] or [2], wherein the aforementioned horizontally oriented phase difference film i satisfies the following equation (8):

[0035] Re i (450) / Re i (550)≥1.00 (8)

[0036] In equation (8), Re i (λ) has the same meaning as in equation (4) above.

[0037] The angle θ between the slow axis of the aforementioned horizontally oriented retardation film i and the absorption axis of the polarizer. i The range is defined by the following formula (9):

[0038] 15°≤|θ i |≤75° (9).

[0039] [4] The laminate as described in any one of [1] to [3], wherein the aforementioned horizontally oriented phase difference film i and the polarizer are laminated by an adhesive.

[0040] [5] The laminate as described in any one of [1] to [4], wherein the aforementioned horizontally oriented phase difference film i is formed from a film that has been stretched at least in one direction.

[0041] [6] The laminate as described in any one of [1] to [5], wherein the aforementioned horizontally oriented phase difference film ii is formed from a cured polymeric liquid crystal composition comprising at least one polymeric liquid crystal compound.

[0042] [7] A laminate as described in any one of [1] to [6], wherein the liquid crystal compound contained in the aforementioned light-absorbing anisotropic film exhibits a smectic liquid crystal phase.

[0043] [8] The laminate as described in any one of [1] to [7], wherein a transparent protective film is further included on the surface of the aforementioned light-absorbing anisotropic film opposite to the horizontally oriented phase difference film i.

[0044] [9] The laminate as described in any one of [1] to [8] further comprises a vertically oriented phase difference film iii satisfying the following formula (10),

[0045] -100nm≤Rth iii (550)≤-20nm (10)

[0046] In equation (10), Rth iii (λ) represents the thickness phase difference value of the vertically oriented phase difference film iii at wavelength λnm.

[0047] The aforementioned vertically oriented phase retardation film iii is stacked between the aforementioned polarizer and the aforementioned horizontally oriented phase retardation film ii, or on the side of the aforementioned horizontally oriented phase retardation film ii opposite to the polarizer.

[0048]

[10] The laminate as described in any one of [1] to [9], wherein the aforementioned vertically oriented phase difference film iii satisfies the following equation (11):

[0049] Rth iii (450) / Rth iii (550)>1.00 (11)

[0050] In equation (11), Rth iii (λ) represents the thickness phase difference value of the vertically oriented phase difference film iii at wavelength λnm.

[0051]

[11] The laminate as described in

[10] , wherein the aforementioned vertically oriented phase difference film iii is formed from a cured polymeric liquid crystal composition comprising at least one polymeric liquid crystal compound.

[0052]

[12] An organic EL display device comprising any one of [1] to

[11] a laminate.

[0053] Invention Effects

[0054] According to the present invention, a laminate with excellent transmittance in the front direction and reduced directional anisotropy of light absorption characteristics in the oblique direction, and excellent effect of preventing viewing from the oblique direction, and a display device comprising the laminate, can be provided. Attached Figure Description

[0055] [ Figure 1 This diagram illustrates the X, Y, and Z axes of the light-absorbing anisotropic film included in the laminate of the present invention. Detailed Implementation

[0056] The embodiments of the present invention will now be described in detail. It should be noted that the scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the spirit of the present invention.

[0057] The laminate of the present invention comprises, in sequence, a light-absorbing anisotropic film, a horizontally oriented retardation film i, a polarizer, and a horizontally oriented retardation film ii. Hereinafter, the horizontally oriented retardation film i and the horizontally oriented retardation film ii will sometimes be collectively referred to as "horizontally oriented retardation film".

[0058] In this invention, for the light-absorbing anisotropic film, when any position or direction within the film surface is defined as the x-axis, the direction orthogonal to the x-axis within the film surface is defined as the y-axis, and the film thickness direction orthogonal to both the x-axis and y-axis is defined as the z-axis, the following equations (1) to (3) are satisfied:

[0059] Az>(Ax+Ay) / 2 (1)

[0060] Ax(z=60°) / Ax>5 (2)

[0061] Ay(z=60°) / Ay>5 (3)

[0062] In equations (1) to (3),

[0063] Ax, Ay, Az, Ax(z=60°), and Ay(z=60°) are all the absorbance at the wavelength of maximum absorption of the aforementioned dichroic pigments in the aforementioned anisotropic light absorption film.

[0064] Ax represents the absorbance of linearly polarized light vibrating along the x-axis.

[0065] Ay represents the absorbance of linearly polarized light vibrating along the y-axis.

[0066] Az represents the absorbance of linearly polarized light vibrating along the z-axis.

[0067] Ax (z = 60°) represents the absorbance of linearly polarized light vibrating along the x-axis when the aforementioned membrane is rotated 60° about the y-axis.

[0068] Ay(z=60°) represents the absorbance of linearly polarized light vibrating along the y-axis when the aforementioned membrane is rotated 60° about the x-axis.

[0069] The horizontally oriented phase difference film i satisfies the following equation (4):

[0070] 70nm≤Re i (550)≤170nm (4)

[0071] In equation (4), Re i(λ) represents the in-plane phase difference value of the horizontally oriented phase difference film i at wavelength λnm.

[0072] The horizontally oriented phase difference film ii satisfies the following equation (5):

[0073] 120nm≤Re ii (550)≤160nm (5)

[0074] In equation (5), Re ii (λ) represents the in-plane phase difference value of the horizontally oriented phase difference film ii at a wavelength of λnm.

[0075] In this invention, a horizontally oriented retardation film refers to a retardation film oriented horizontally relative to the film plane. The in-plane phase difference in the horizontally oriented retardation film p can be achieved through Re... p (λ) = (nxp(λ) - nyp(λ)) × dp to obtain (where nxp(λ) represents the principal refractive index at wavelength λnm in the plane of the horizontally oriented phase retardation film p, nyp(λ) represents the refractive index at wavelength λnm in the direction orthogonal to the direction of nxp in the same plane as nxp, and dp represents the film thickness of the horizontally oriented phase retardation film p).

[0076] In this invention, the in-plane phase difference Re of the horizontally oriented phase difference film i is... i (550) satisfies equation (4), and the in-plane phase difference Re of the horizontally oriented phase difference film ii ii (550) Satisfies equation (5), thereby easily reducing the directional anisotropy of light absorption characteristics in the tilt direction. Furthermore, especially when used on an organic EL panel, sufficient anti-reflective properties can be obtained. In addition, by sequentially including a light absorption anisotropy film, a horizontally oriented retardation film i, a polarizer, and a horizontally oriented retardation film ii, visual recognition from the front can be improved, and the directional anisotropy of light absorption characteristics in the tilt direction can be reduced, thus reducing visual recognition from the tilt direction. Regarding the laminate in this invention, the in-plane retardation, as described above, can be the same or different. In particular, by including two different horizontally oriented retardation films, the directional anisotropy of light absorption characteristics in the tilt direction can be further reduced when displayed on an organic EL panel, and properties that prevent reflection from external light can be obtained.

[0077] <Anisotropic light-absorbing film>

[0078] In this invention, the light-absorbing anisotropic film is formed from a cured liquid crystal composition comprising a dichroic pigment and a liquid crystal compound.

[0079] Regarding the aforementioned anisotropic light absorption film, if any direction within the film surface is defined as the x-axis, the direction orthogonal to the x-axis within the film surface is defined as the y-axis, and the film thickness direction orthogonal to both the x-axis and y-axis is defined as the z-axis (refer to...), Figure 1 ), satisfying the following equations (1) to (3):

[0080] Az>(Ax+Ay) / 2 (1)

[0081] Ax(z=60°) / Ax>5 (2)

[0082] Ay(z=60°) / Ay>5 (3).

[0083] Here, in equations (1) to (3), Ax, Ay, Az, Ax(z=60°) and Ay(z=60°) are all the absorbance of the dichroic pigment in the aforementioned anisotropic light absorption film at the wavelength of maximum absorption in the anisotropic light absorption film.

[0084] Ax represents the absorbance of linearly polarized light vibrating along the x-axis. Ax can be measured by incident linearly polarized light vibrating along the x-axis onto the film surface along the z-axis.

[0085] Ay represents the absorbance of linearly polarized light vibrating along the y-axis. Ay can be measured by incident linearly polarized light vibrating along the y-axis onto the film surface from the z-axis direction.

[0086] Az represents the absorbance of linearly polarized light vibrating along the z-axis. Az can be measured, for example, by incident linearly polarized light vibrating along the z-axis perpendicularly onto the side of the film in the xy-plane direction, i.e., when the film is set to the xy-plane, onto its side (thickness direction).

[0087] Ax(z=60°) represents the absorbance of linearly polarized light vibrating along the x-axis when the aforementioned membrane is rotated 60° about the y-axis. Ax(z=60°) can be measured by incidenting the same linearly polarized light as the linearly polarized light used to measure Ax with the aforementioned membrane rotated 60° about the y-axis. Here, the rotation of the membrane is performed by rotating the membrane in the state where Ax was measured 60° about the y-axis along the incident direction of the linearly polarized light.

[0088] Ay(z=60°) represents the absorbance of linearly polarized light vibrating along the y-axis when the aforementioned membrane is rotated 60° about the x-axis. Ay(z=60°) can be measured by incidenting the same linearly polarized light as the linearly polarized light used to measure Ay with the membrane rotated 60° about the x-axis. Here, the rotation of the membrane is performed by rotating the membrane in the state where Ay was measured 60° about the x-axis along the incident direction of the linearly polarized light.

[0089] The absorbance in the z direction in Equation (1) is difficult to measure because the light is incident from the side of the film. Therefore, when the angle between the vibration plane of the linearly polarized light, which is the measurement light, and the x-y plane of the film is 90°, the x-y plane of the film is tilted 30° and 60° along the incident direction of the linearly polarized light with respect to this vibration plane for measurement, whereby the absorbance in the Az direction can be calculated.

[0090] Specifically, the calculation can be performed using the following methods or the like.

[0091] In a state where the aforementioned film is rotated 30° and 60° about the y-axis, linearly polarized light identical to the linearly polarized light used to measure Ax is incident, whereby Ax(z = 30°) and Ax(z = 60°) are measured. Similarly, in a state where the aforementioned film is rotated 30° and 60° about the x-axis, linearly polarized light identical to the linearly polarized light used to measure Ay is incident, whereby Ay(z = 30) and Ay(z = 60) are measured.

[0092] 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. Therefore, Equation (1) is necessarily satisfied.

[0093] Particularly, in the case where 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°). Therefore, Ax(z = 30°) and Ay(z = 30°) can be denoted as A(z = 30°), and Ax(z = 60°) and Ay(z = 60°) can be denoted as A(z = 60°). That is, if A(z = 30°) < A(z = 60°), the relationship of A(z = 30°) < A(z = 60°) < A(z = 90°) = Az is satisfied. In addition, if A(z = 30°) > (Ax + Ay) / 2, then Az necessarily satisfies Equation (1).

[0094] In the present invention, the light absorption anisotropic film satisfies the above-mentioned Equations (2) and (3).

[0095] Regarding Ax(z = 60°) / Ax and Ay(z = 60°) / Ay, the larger their values, the more excellent the light absorption anisotropy is exhibited. Their values can be, for example, 50 or less, or can be 30 or less. Additionally, they can be 6 or more, or can be 8 or more.

[0096] Furthermore, the light-absorbing anisotropic film of the present invention preferably satisfies formulas (2') and (3'):

[0097] Ax(z=60°) / Ax>10 (2')

[0098] Ay(z=60°) / Ay>10 (3').

[0099] When a light-absorbing anisotropic film satisfies equations (1) to (3), it can be said that dichroic pigments have excellent absorption anisotropy, that is, excellent polarization performance. Utilizing this excellent property, light from the front direction can be effectively transmitted, and light from the tilted direction can be effectively absorbed.

[0100] It should be noted that when the light absorption anisotropic film contains two or more dichroic pigments with different maximum absorption wavelengths, the Az>(Ax+Ay) / 2, Ax(z=60°) / Ax, and Ay(z=60°) / Ay calculated based on the absorbance Ax, Ay, and Az at the maximum absorption wavelength of at least one of the dichroic pigments can satisfy the relationships in equations (1) to (3) above. From the perspective of effectively transmitting light from the front direction and effectively absorbing light from the oblique direction, and easily obtaining a higher anti-peeping effect, it is preferable to select dichroic pigments based on the absorbance Ax, Ay and Az at the maximum absorption wavelength of the dichroic pigments with maximum absorption wavelengths in the wavelength range of 500 to 600 nm, where Az>(Ax+Ay) / 2, Ax(z=60°) / Ax and Ay(z=60°) / Ay satisfy the relationships of the above equations (1) to (3). It is also preferable to select dichroic pigments based on the absorbance Ax, Ay and Az at the maximum absorption wavelength of each dichroic pigment contained in the light absorption anisotropic film, where Az>(Ax+Ay) / 2, Ax(z=60°) / Ax and Ay(z=60°) / Ay each satisfy the relationships of the above equations (1) to (3). It is particularly preferable to select dichroic pigments in a manner that satisfy the above equations (1) to (3) in a wide range of 350 to 700 nm.

[0101] The thickness of this anisotropic light-absorbing film is preferably 0.1–10 μm, more preferably 0.2–5 μm, even more preferably 0.2–3 μm or 0.5–5 μm, and particularly preferably 0.5–3 μm. If the thickness of the anisotropic light-absorbing film is within the aforementioned range, a decrease in light absorption in the tilt direction is less likely to occur, thus easily achieving good privacy protection properties. Furthermore, the orientation of the dichroic pigments is less likely to become disordered, thus easily improving transmittance in the front direction.

[0102] <Dichromatic pigments>

[0103] Dichroic pigments are pigments that have different absorbance along their long axis and short axis.

[0104] As a dichroic pigment, in anisotropic light absorption films, a dichroic pigment with a maximum absorption wavelength (λMAX) in the wavelength range of 300–700 nm is preferred, and a dichroic pigment with a maximum absorption wavelength in the wavelength range of 500–600 nm is more preferred. By having a maximum absorption wavelength in the wavelength range of 500–600 nm, which is highly visible to humans, it is possible to more effectively prevent peeping. That is, if a dichroic pigment with maximum absorption at a high visible wavelength is used, the amount of dichroic pigment used can be reduced, and the anisotropic light absorption film can be made thinner.

[0105] Examples of such dichroic pigments include acridine pigments, oxazine pigments, cyanin pigments, naphthalene pigments, azo pigments, and anthraquinone pigments, with azo pigments being preferred. Examples of azo pigments include monoazo pigments, diazo pigments, triazo pigments, tetraazo pigments, and succinylazo pigments, with diazo and triazo pigments being preferred. Dichroic pigments can be used individually or in combination. When polarization characteristics are required across the entire visible light spectrum, combinations of three or more dichroic pigments are preferred, and combinations of three or more azo pigments are more preferred.

[0106] When combining multiple dichroic pigments, it is preferable to include at least one dichroic pigment with a maximum absorption wavelength in the wavelength range of 500–600 nm in the light absorption anisotropic film. When combining two dichroic pigments, it is further preferable to include dichroic pigments with maximum absorption wavelengths in the ranges of 350–499 nm or 601–750 nm. When combining three dichroic pigments, it is preferable to include dichroic pigments with maximum absorption wavelengths in the ranges of 350–499 nm, 500–600 nm, and 601–750 nm, respectively. By combining dichroic pigments with such maximum absorption wavelengths, it is possible to more effectively prevent peeping.

[0107] As azo dyes, examples include compounds represented by formula (I) (hereinafter, sometimes referred to as "compound (I)").

[0108] A 1 (-N=NA) 2 ) p -N=NA 3 (I)

[0109] In formula (I),

[0110] A 1 and A 3Each can be represented independently as a phenyl group that may have substituents, a naphthyl group that may have substituents, or a monovalent heterocyclic group that may have substituents. A 2 This indicates a p-phenylene group that may have substituents, a naphth-1,4-diyl group that may have substituents, or a divalent heterocyclic group that may have substituents. p represents an integer from 1 to 4. When p is an integer greater than 2, multiple A groups... 2 They can be the same or different. Within the visible light absorption region, -N=N- bonds can be replaced by -C=C-, -COO-, -NHCO-, or -N=CH- bonds.

[0111] Examples of monovalent heterocyclic groups include those obtained by removing one hydrogen atom from heterocyclic compounds such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole, and benzoxazole. Examples of divalent heterocyclic groups include those obtained by removing two hydrogen atoms from the aforementioned heterocyclic compounds.

[0112] As A 1 and A 3 The phenyl, naphthyl and monovalent heterocyclic groups, and A 2 The substituents optionally present in the p-phenylene, naphthalene-1,4-diyl, and divalent heterocyclic groups can include alkyl groups with 1 to 20 carbon atoms, alkyl groups with 1 to 20 carbon atoms having polymerizable groups, alkenyl groups with 1 to 4 carbon atoms; alkoxy groups with 1 to 20 carbon atoms such as methoxy, ethoxy, and butoxy; alkoxy groups with 1 to 20 carbon atoms having polymerizable groups; fluoroalkyl groups with 1 to 4 carbon atoms such as trifluoromethyl; cyano; nitro; halogen atoms; substituted or unsubstituted amino groups such as amino, diethylamino, and pyrrolidinyl (substituted amino groups refer to amino groups having one or two alkyl groups with 1 to 6 carbon atoms, amino groups having one or two alkyl groups with 1 to 6 carbon atoms having polymerizable groups, or amino groups where two substituted alkyl groups are bonded together to form an alkane diene with 2 to 8 carbon atoms. Unsubstituted amino groups are -NH2). It should be noted that, as the aforementioned polymerizable group, examples include acryloyl, methacryloyl, acryloyloxy, and methacryloyloxy.

[0113] Of the compounds (I), those represented by any one of the following formulas (I-1) to (I-8) are preferred.

[0114] [Chemical Formula 1]

[0115]

[0116] [In formulas (I-1) to (I-8),

[0117] B 1 ~B 30Each of the following can be represented independently: a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a nitro group, a substituted or unsubstituted amino group (the definitions of substituted and unsubstituted amino groups are as described above), a chlorine atom, or a trifluoromethyl group.

[0118] n1 to n4 represent integers from 0 to 3 independently.

[0119] When n1 is 2 or more, multiple B 2 They can be the same or different.

[0120] When n² is 2 or more, multiple B 6 They can be the same or different.

[0121] When n3 is 2 or more, multiple B 9 They can be the same or different.

[0122] When n4 is 2 or more, multiple B 14 They can be the same or different.

[0123] The anthraquinone pigments mentioned above are preferably compounds represented by formula (I-9).

[0124] [Chemical Formula 2]

[0125]

[0126] In formula (I-9),

[0127] R 1 ~R 8 Each can independently represent a hydrogen atom, -R x -NH2, -NHR x -NR x 2. -SR x Or halogen atoms.

[0128] R x This refers to an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.

[0129] The preferred oxazine pigment is a compound represented by formula (I-10).

[0130] [Chemical Formula 3]

[0131]

[0132] In formula (I-10),

[0133] R 9 ~R 15 Each can independently represent a hydrogen atom, -R x-NH2, -NHR x -NR x 2. -SR x Or halogen atoms.

[0134] R x This refers to an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.

[0135] The preferred acridine dye is a compound represented by formula (I-11).

[0136] [Chemical Formula 4]

[0137]

[0138] In formula (I-11),

[0139] R 16 ~R 23 Each can independently represent a hydrogen atom, -R x -NH2, -NHR x -NR x 2. -SR x Or halogen atoms.

[0140] R x This refers to an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.

[0141] As in equations (I-9), (I-10), and (I-11), R x Examples of alkyl groups with 1 to 6 carbon atoms include methyl, ethyl, propyl, and butyl, while examples of aryl groups with 6 to 12 carbon atoms include phenyl, tolueneyl, xylyl, and naphthyl.

[0142] The preferred cyanin pigments are compounds represented by formula (I-12) and formula (I-13).

[0143] [Chemical Formula 5]

[0144]

[0145] In formula (I-12),

[0146] D 1 and D 2 The groups represented by any one of formulas (I-12a) to (I-12d) are independently represented.

[0147] [Chemical Formula 6]

[0148]

[0149] n5 represents an integer from 1 to 3.

[0150] [Chemical Formula 7]

[0151]

[0152] In formula (I-13),

[0153] D 3 and D 4 The groups represented by any one of formulas (I-13a) to (I-13h) are independently represented.

[0154] [Chemical Formula 8]

[0155]

[0156] n6 represents an integer from 1 to 3.

[0157] Regarding the content of the dichroic pigment in the liquid crystal composition forming the anisotropic light-absorbing film, from the viewpoint of ensuring good orientation of the dichroic pigment, it is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.1 parts by mass or more and 20 parts by mass or less, even more preferably 0.1 parts by mass or more and 10 parts by mass or less, and particularly preferably 0.1 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the solid component of the liquid crystal composition. If the content of the dichroic pigment is within this range, it is less likely to cause disorder in the liquid crystal orientation of the liquid crystal compound, and therefore it is preferred.

[0158] <Liquid Crystal Compounds>

[0159] In this invention, the liquid crystal composition forming the light-absorbing anisotropic film comprises a liquid crystal compound. From the perspective of film strength, a polymerizable liquid crystal compound is preferred as the aforementioned liquid crystal compound.

[0160] Polymerizable liquid crystal compounds are liquid crystal compounds having polymerizable groups. A polymerizable group refers to a group that can participate in a polymerization reaction. From the perspective of ease of manufacture, photopolymerizable groups are preferred. Here, a photopolymerizable group refers to a group that can participate in a polymerization reaction using reactive species generated by a photopolymerization initiator (described later), such as active free radicals or acids. Examples of photopolymerizable groups include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloyloxy, methacryloxy, epoxyethyl, and oxetyl. Among these, from the perspective of reactivity, acryloyloxy, methacryloxy, vinyloxy, epoxyethyl, and oxetyl are preferred, and acryloyloxy is more preferred.

[0161] Regarding the liquid crystal properties exhibited by the aforementioned liquid crystal compound, it can be either a thermotropic liquid crystal or a lyotropic liquid crystal, but from the perspective of enabling precise film thickness control, a thermotropic liquid crystal is preferred. Furthermore, the phase sequence structure in the thermotropic liquid crystal can be either a nematic liquid crystal or a smectic liquid crystal. Additionally, the polymeric liquid crystal compound exhibiting liquid crystal properties can be a monomer or an oligomer or polymer formed by polymerizing polymeric groups. Since the higher the degree of orientation order of the liquid crystal cured film, the larger the values ​​of Ax(z=60°) / Ax and Ay(z=60°) / Ay tend to be, compounds forming a smectic liquid crystal phase are preferred.

[0162] Among the liquid crystal properties exhibited by the aforementioned polymerizable liquid crystal compounds, higher-order smectic liquid crystal compounds that form smectic B, D, E, F, G, H, I, J, K, or L phases are more preferred, and higher-order smectic liquid crystal compounds that form smectic B, F, or I phases are even more preferred. If the liquid crystal phase formed by the polymerizable liquid crystal compound is one of these higher-order smectic phases, a liquid crystal cured film with higher orientation order can be manufactured, and high polarization performance can be easily obtained. Furthermore, such a highly oriented liquid crystal cured film yields Bragg peaks from higher-order structures such as hexagonal and crystalline phases in X-ray diffraction measurements. These Bragg peaks are peaks from the periodic structure of molecular orientation, and the period interval can be obtained as... The film. The polymeric liquid crystal compound can be used alone or in combination of two or more. In the case of the light absorption anisotropic film of the present invention, by including a polymeric liquid crystal compound polymerized in a smectic phase, the light absorption characteristics in the tilt direction are further improved, thus achieving a better privacy protection effect. In addition, the orientation of the dichroic pigment is not easily disordered, thus achieving better transmittance in the front direction.

[0163] Examples of polymerizable liquid crystal compounds include polymerizable liquid crystal compounds that exhibit positive wavelength dispersion, obtained by polymerizing the polymerizable liquid crystal compound alone in a state of orientation along a specific direction, and polymerizable liquid crystal compounds that exhibit reverse wavelength dispersion. In the light absorption anisotropic film of the present invention, either only one type of polymerizable liquid crystal compound may be used, or two polymerizable liquid crystal compounds may be used in combination.

[0164] As polymeric compounds exhibiting reverse wavelength dispersion, examples include compounds represented by the following formula (X).

[0165] [Chemical Formula 9]

[0166]

[0167] In formula (X), Ar represents a divalent group containing an aromatic group that may have substituents. The aromatic group referred to here is a group whose ring structure has [4n+2] π electrons according to Hückel's rule, such as the Ar group illustrated later in (Ar-1) to (Ar-23) which may have more than two π electrons via a divalent linker. Here, n represents an integer. In the case of a ring structure formed by including heteroatoms such as -N= and -S-, this also includes cases where the non-covalent electron pairs on these heteroatoms satisfy Hückel's rule and thus possess aromaticity. Preferably, the aromatic group contains at least one of nitrogen, oxygen, or sulfur atoms. The divalent group Ar may contain one or more aromatic groups. In the case of one aromatic group, the divalent group Ar may be a divalent aromatic group that may have substituents. When the divalent group Ar contains two or more aromatic groups, the two or more aromatic groups can be bonded to each other through single bonds, -CO-O-, -O- and other divalent bonding groups.

[0168] G 1 and G 2 Each of these groups independently represents 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 can be replaced by a halogen atom, an alkyl group with 1 to 4 carbon atoms, a fluoroalkyl group with 1 to 4 carbon atoms, an alkoxy group with 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 can be replaced by an oxygen atom, a sulfur atom, or a nitrogen atom.

[0169] L 1 L 2 B 1 and B 2 Each is an independent single bond or a divalent linker.

[0170] k and l each independently represent integers from 0 to 3, satisfying the relation 1 ≤ k + l. Here, in the case of 2 ≤ k + l, B 1 and B 2 G 1 and G 2 They can be the same as each other, or they can be different.

[0171] E 1 and E 2 Each can be independently represented as an alkane diene with 1 to 17 carbon atoms, and more preferably as an alkane diene with 4 to 12 carbon atoms. In addition, the hydrogen atoms contained in the alkane diene can be replaced by halogen atoms, and the -CH2- contained in the alkane diene can be replaced by -O-, -S-, -SiH2-, or -C(=O)-.

[0172] P 1and P 2 Each of the above represents a polymeric group or a hydrogen atom independently, with at least one being a polymeric group.

[0173] G 1 and G 2 Each of the following is preferably 1,4-phenylene diel, which can be substituted with at least one substituent selected from the group consisting of alkyl groups with 1 to 4 carbon atoms; or 1,4-cyclohexane diel, which can be substituted with at least one substituent selected from the group consisting of alkyl groups with 1 to 4 carbon atoms; more preferably methyl-substituted 1,4-phenylene diel, unsubstituted 1,4-phenylene diel, or unsubstituted 1,4-trans-cyclohexane diel; and particularly preferably unsubstituted 1,4-phenylene diel or unsubstituted 1,4-trans-cyclohexane diel.

[0174] In addition, it is preferable that there are multiple Gs. 1 and G 2 At least one of them is a divalent alicyclic hydrocarbon group, and more preferably it is with L 1 or L 2 bonded G 1 and G 2 At least one of them is a divalent alicyclic hydrocarbon group.

[0175] L 1 and L 2 Each is preferably a single bond, an alkylene group having 1 to 4 carbon atoms, or an -O-, -S-, or -R group. a1 OR a2 -、-R a3 COOR a4 -、-R a5 OCOR a6 -、-R a7 OC = OOR a8 -、-N=N-、-CR c =CR d -、or -C≡C-. Here, R a1 ~R a8 Each independently represents a single bond, or an alkylene group having 1 to 4 carbon atoms, R c and R d L represents an alkyl group or hydrogen atom with 1 to 4 carbon atoms. 1 and L 2 Each independently is more preferably a single bond, -OR a2-1 -、-CH2-、-CH2CH2-、-COOR a4-1 -、or-OCOR a6-1 -. Here, R a2-1 R a4-1 R a6-1Each can independently represent any one of a single bond, -CH2-, or -CH2CH2-. L 1 and L 2 Each of these can be further preferred independently as a single bond, -O-, -CH2CH2-, -COO-, -COOCH2CH2-, or -OCO-.

[0176] B 1 and B 2 Each is preferably a single bond, an alkylene group having 1 to 4 carbon atoms, or an -O-, -S-, or -R group. a9 OR a10 -、-R a11 COOR a12 -、-R a13 OCOR a14 - or -R a15 OC = OOR a16 -. Here, R a9 ~R a16 Each can independently represent a single bond or an alkylene group having 1 to 4 carbon atoms. B 1 and B 2 Each independently is more preferably a single bond, -OR a10-1 -、-CH2-、-CH2CH2-、-COOR a12 -1 -、or-OCOR a14-1 -. Here, R a10-1 R a12-1 R a14-1 Each can independently represent any one of a single bond, -CH2-, or -CH2CH2-. B 1 and B 2 Each of these can be further preferred independently as a single bond, -O-, -CH2CH2-, -COO-, -COOCH2CH2-, -OCO-, or -OCOCH2CH2-.

[0177] Regarding k and l, from the viewpoint of exhibiting inverse wavelength dispersion, the range of 2 ≤ k + l ≤ 6 is preferred, k + l = 4 is preferred, and k = 2 and l = 2 is more preferred. When k = 2 and l = 2, a symmetrical structure is formed, which is therefore preferred.

[0178] As P 1 or P 2 Examples of polymerizable groups include epoxy, vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloyloxy, methacryloyloxy, epoxyethyl, and oxetyl.

[0179] Among them, acryloyloxy, methacryloyloxy, vinyloxy, epoxyethyl and oxacyclobutyl are preferred, and acryloyloxy is more preferred.

[0180] Ar preferably has at least one selected from aromatic hydrocarbon rings that may have substituents, aromatic heterocycles that may have substituents, and electron-withdrawing groups. Examples of such aromatic hydrocarbon rings include benzene rings, naphthyl rings, and anthracene rings, with benzene rings and naphthyl rings being preferred. Examples of such aromatic heterocycles include furan rings, benzofuran rings, pyrrole rings, indole rings, thiophene rings, benzothiophene rings, pyridine rings, pyrazine rings, pyrimidine rings, triazole rings, triazine rings, pyrrolidine rings, imidazole rings, pyrazole rings, thiazole rings, benzothiazole rings, thienothiazole rings, oxazole rings, benzoxazole rings, and phenanthroline rings. Among these, a thiazole ring, a benzothiazole ring, or a benzofuran ring is preferred, and a benzothiazole group is even more preferred. Furthermore, when Ar contains a nitrogen atom, the nitrogen atom preferably has π electrons.

[0181] In formula (X), N represents the total number of π electrons contained in the divalent aromatic group represented by Ar. π Preferably, the value is 8 or more, more preferably 10 or more, even more preferably 14 or more, and particularly preferably 16 or more. Furthermore, it is preferably 30 or less, more preferably 26 or less, and even more preferably 24 or less.

[0182] Examples of aromatic groups represented by Ar include the following groups.

[0183] [Chemical Formula 10]

[0184]

[0185] In equations (Ar-1) to (Ar-23), the symbol * represents the connecting part, and Z 0 Z 1 and Z 2 Each of these groups independently represents a hydrogen atom, a halogen atom, an alkyl group (1-12 carbon atoms), a cyano group, a nitro group, an alkyl sulfinyl group (1-12 carbon atoms), an alkyl sulfonyl group (1-12 carbon atoms), a carboxyl group, a fluoroalkyl group (1-12 carbon atoms), an alkoxy group (1-12 carbon atoms), an alkyl thio group (1-12 carbon atoms), an N-alkylamino group (1-12 carbon atoms), an N,N-dialkylamino group (2-12 carbon atoms), an N-alkylaminosulfonyl group (1-12 carbon atoms), or an N,N-dialkylaminosulfonyl group (2-12 carbon atoms). Additionally, Z... 0 Z 1 and Z 2 It can contain polymeric groups.

[0186] Q 1 and Q 2 Each is represented independently - CR 2’ R 3’ -、-S-、-NH-、-NR 2’-、-CO- or O-、R 2’ and R 3’ Each can be independently represented as an alkyl group having 1 to 4 hydrogen atoms or carbon atoms.

[0187] J 1 and J 2 Each can be used to represent a carbon atom or a nitrogen atom independently.

[0188] Y 1 Y 2 and Y 3 Each can be independently represented as a substituted aromatic hydrocarbon group or an aromatic heterocyclic group.

[0189] W 1 and W 2 Each can independently represent a hydrogen atom, cyano group, methyl group, or halogen atom, and m represents an integer from 0 to 6.

[0190] As Y 1 Y 2 and Y 3 The aromatic hydrocarbon group in the compound can include phenyl, naphthyl, anthraceneyl, phenanthryl, biphenyl, and other aromatic hydrocarbon groups with 6 to 20 carbon atoms, with phenyl and naphthyl being preferred, and phenyl being more preferred. As aromatic heterocyclic groups, can include furanyl, pyrroleyl, thiopheneyl, pyridyl, thiazolyl, benzothiazolyl, and other aromatic heterocyclic groups with 4 to 20 carbon atoms containing at least one heteroatom such as a nitrogen atom, oxygen atom, or sulfur atom, with furanyl, thiopheneyl, pyridyl, thiazolyl, and benzothiazolyl being preferred.

[0191] Y 1 Y 2 and Y 3 Each can be independently a substituted polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group. A polycyclic aromatic hydrocarbon group refers to a fused polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring assembly. A polycyclic aromatic heterocyclic group refers to a fused polycyclic aromatic heterocyclic group or a group derived from an aromatic ring assembly.

[0192] Z 0 Z 1 and Z 2 Each of the following is preferably composed of 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. 0 Further preferred are hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, and cyano groups, Z. 1 and Z 2 Further preferred are hydrogen atoms, fluorine atoms, chlorine atoms, methyl groups, and cyano groups. Additionally, Z... 0 Z 1 and Z 2 It can contain polymeric groups.

[0193] Q 1 and Q 2 Preferred types are -NH-, -S-, and -NR. 2’ -、-O-,R 2’ Hydrogen atoms are preferred. Among them, -S-, -O-, and -NH- are particularly preferred.

[0194] From the perspective of molecular stability, formulas (Ar-6) and (Ar-7) are preferred among formulas (Ar-1) to (Ar-23).

[0195] In equations (Ar-16) to (Ar-23), Y 1 It can bond with the nitrogen atom and Z 0 Together, they form an aromatic heterocyclic group. Examples of aromatic heterocyclic groups include those described above that can be present in Ar, such as pyrrole rings, imidazole rings, pyrrololine rings, pyridine rings, pyrazine rings, pyrimidine rings, indole rings, quinoline rings, isoquinoline rings, purine rings, and pyrrolidine rings. This aromatic heterocyclic group may have substituents. Additionally, Y... 1 It can also be bonded to the nitrogen atom and Z. 0 Together, they form the aforementioned substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group. Examples include benzofuran ring, benzothiazole ring, and benzoxazole ring.

[0196] Furthermore, in this invention, as the polymeric liquid crystal compound for forming the light-absorbing anisotropic film, for example, a compound containing a group represented by the following formula (Y) (hereinafter also referred to as "polymeric liquid crystal compound (Y)") can be used. The polymeric liquid crystal compound (Y) tends to generally exhibit positive wavelength dispersion. The polymeric liquid crystal compound can be used alone or in combination of two or more.

[0197] P11-B11-E11-B12-A11-B13-(Y)

[0198] In formula (Y), P11 represents a polymerizable group.

[0199] A11 represents a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atoms contained in the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group may be replaced by halogen atoms, alkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, cyano groups or nitro groups, and the hydrogen atoms contained in the alkyl groups with 1 to 6 carbon atoms and the alkoxy groups with 1 to 6 carbon atoms may be replaced by fluorine atoms.

[0200] B11 represents -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR 16 -、-NR 16-CO-, -CO-, -CS-, or a single bond. R 16 It represents an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0201] B12 and B13 independently represent -C≡C-, -CH=CH-, -CH2-CH2-, -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-O-, -OC(=O)-O-, -CH=N-, -N=CH-, -N=N-, and -C(=O)-NR. 16 -、-NR 16 -C(=O)-, -OCH2-, -OCF2-, -CH2O-, -CF2O-, -CH=CH-C(=O)-O-, -OC(=O)-CH=CH- or single bond.

[0202] E11 represents an alkane dierium with 1 to 12 carbon atoms, where the hydrogen atom in the dierium can be replaced by an alkoxy group with 1 to 5 carbon atoms, and the hydrogen atom in the alkoxy group can be replaced by a halogen atom. Furthermore, the -CH2- group constituting the dierium can be replaced by -O- or -CO-.

[0203] The number of carbon atoms in the aromatic hydrocarbon group and alicyclic hydrocarbon group of A11 is preferably in the range of 3 to 18, more preferably in the range of 5 to 12, and particularly preferably 5 or 6. As A11, cyclohexane-1,4-diyl or 1,4-phenylene are preferred.

[0204] E11 is preferably a linear alkane diester with 1 to 12 carbon atoms. The -CH2- constituting this alkane diester can be replaced with -O-.

[0205] Specifically, examples include straight-chain alkane dimethyl groups with 1 to 12 carbon atoms, such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, and dodecane-1,12-diyl; and -CH2-CH2-O-CH2-CH2-, -CH2-CH2-O-CH2-CH2-O-CH2-CH2-, and -CH2-CH2-O-CH2-CH2-O-CH2-CH2-.

[0206] As B11, -O-, -S-, -CO-O-, and -O-CO- are preferred, with -CO-O- being more preferred.

[0207] As for B12 and B13, -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, and -OC(=O)-O- are preferred respectively, with -O- or -OC(=O)-O- being more preferred.

[0208] As for the polymerizable group represented by P11, considering its high polymerization reactivity, especially photopolymerization reactivity, it is preferred to be a free radical polymerizable group or a cationic polymerizable group. Considering the ease of operation and the ease of manufacturing the liquid crystal compound itself, the polymerizable group is preferably a group represented by the following formulas (P-11) to (P-15).

[0209] [Chemical Formula 11]

[0210]

[0211] In formulas (P-11) to (P-15),

[0212] R 17 ~R 21 Each can independently represent an alkyl group or a hydrogen atom having 1 to 6 carbon atoms.

[0213] As specific examples of the groups represented by formulas (P-11) to (P-15), the groups represented by formulas (P-16) to (P-20) can be cited below.

[0214] [Chemical Formula 12]

[0215]

[0216] P11 is preferably a group represented by formula (P-14) to formula (P-20), more preferably vinyl, p-stilbene, epoxy or oxobutyl.

[0217] The group represented by P11-B11- is further preferably acryloyloxy or methacryloyloxy.

[0218] Examples of polymerizable liquid crystal compounds (Y) include compounds represented by formulas (YI), (Y-II), (Y-III), (Y-IV), (YV), or (Y-VI).

[0219] P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-B16-E12-B17-P12(YI)

[0220] P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-F11(Y-II)

[0221] P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-E12-B17-P12(Y-III)

[0222] P11-B11-E11-B12-A11-B13-A12-B14-A13-F11(Y-IV)

[0223] P11-B11-E11-B12-A11-B13-A12-B14-E12-B17-P12(YV)

[0224] P11-B11-E11-B12-A11-B13-A12-F11(Y-VI)

[0225] (in the formula,

[0226] The meanings of A11, B11~B13, and P11 are the same as those in the above formula (Y).

[0227] A12 to A14 are each independently the same as A11, B14 to B16 are each independently the same as B12, B17 is the same as B11, E12 is the same as E11, and P12 is the same as P11.

[0228] F11 represents a hydrogen atom, an alkyl group with 1 to 13 carbon atoms, an alkoxy group with 1 to 13 carbon atoms, a cyano group, a nitro group, a trifluoromethyl group, a dimethylamino group, a hydroxyl group, a hydroxymethyl group, a formyl group, a sulfonyl group (-SO3H), a carboxyl group, an alkoxy carbonyl group with 1 to 10 carbon atoms, or a halogen atom. The -CH2- group constituting the alkyl or alkoxy group can be replaced with -O-.

[0229] Specific examples of polymerizable liquid crystal compounds (Y) include compounds containing polymerizable groups described in "3.8.6 Network (fully cross-linked type)" and "6.5.1 Liquid Crystal Materials b. Polymerizable Nematic Liquid Crystal Materials" of the Liquid Crystal Handbook (edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2000), as well as polymerizable liquid crystals described in Japanese Patent Application Publication Nos. 2010-31223, 2010-270108, 2011-6360, and 2011-207765.

[0230] Specific examples of polymerizable liquid crystal compounds (Y) include compounds represented by the following formulas (YI-1) to (YI-4), (Y-II-1) to (Y-II-4), (Y-III-1) to (Y-III-26), (Y-IV-1) to (Y-IV-26), (YV-1) to (YV-2), and (Y-VI-1) to (Y-VI-6).

[0231] It should be noted that in the following formulas, k1 and k2 each independently represent integers from 2 to 12. These polymerizable liquid crystal compounds (Y) are preferred from the perspective of ease of synthesis or ease of acquisition.

[0232] [Chemical Formula 13]

[0233]

[0234] [Chemical Formula 14]

[0235]

[0236] [Chemical Formula 15]

[0237]

[0238] [Chemical Formula 16]

[0239]

[0240] [Chemical Formula 17]

[0241]

[0242] [Chemical Formula 18]

[0243]

[0244] [Chemical Formula 19]

[0245]

[0246] [Chemical Formula 20]

[0247]

[0248] [Chemical Formula 21]

[0249]

[0250] [Chemical Formula 22]

[0251]

[0252] [Chemical Formula 23]

[0253]

[0254] Polymerizable liquid crystal compounds exhibiting smectic liquid crystal properties are liquid crystal compounds having at least one polymerizable group. From the viewpoint of improving the heat resistance of the light absorption anisotropic film, liquid crystal compounds having two or more polymerizable groups are preferred. Examples of polymerizable groups include (meth)acryloyloxy, vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, epoxyethyl, oxetyl, etc. Among these, (meth)acryloyloxy is preferred from the viewpoints of ease of manufacture, ease of improving the heat resistance of the light absorption anisotropic film, and ease of adjusting the adhesion between the light absorption anisotropic film and the substrate.

[0255] As polymeric liquid crystal compounds exhibiting smectic liquid crystal properties, examples include compounds represented by the following formula (Z) (hereinafter sometimes referred to as "polymeric liquid crystal compound (Z)").

[0256] [Chemical Formula 24]

[0257] U 1z -V 1z -W 1z -(X 1z -Y 1z -) nz -X 2z -W 2z -V 2z -U 2z (Z)

[0258] In formula (Z), X 1z and X 2z Each of these groups independently represents a divalent aromatic group or a divalent alicyclic hydrocarbon group. Here, the hydrogen atom in the divalent aromatic group or divalent alicyclic hydrocarbon group can be replaced by a halogen atom, an alkyl group with 1 to 4 carbon atoms, a fluoroalkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, a cyano group, or a nitro group. The carbon atoms constituting the divalent aromatic group or divalent alicyclic hydrocarbon group can be replaced by oxygen atoms, sulfur atoms, or nitrogen atoms. Wherein, X 1z and X 2z At least one of them is 1,4-phenylene or cyclohexane-1,4-diyl, which may have substituents.

[0259] Y 1z It is a single bond or a divalent linker.

[0260] When nz is 1 to 3, and nz is 2 or higher, multiple X 1z They can be the same or different. X 2z Can be used with multiple X1z Any one or all of them can be the same, or they can be different. Additionally, when nz is greater than 2, multiple Ys... 1z They can be the same or different. From the viewpoint of liquid crystal properties, nz is preferably 2 or higher.

[0261] U 1z It represents a hydrogen atom or (meth)acryloyloxy group.

[0262] U 2z It indicates a polymerizable group.

[0263] W 1z and W 2z Each group is a single bond or a divalent linker, independent of the others.

[0264] V 1z and V 2z Each of these groups independently represents an alkane diene with 1 to 20 carbon atoms that may have substituents, wherein the -CH2- group constituting the alkane diene can be replaced by -O-, -CO-, -S-, or -NH-.

[0265] In polymeric liquid crystal compound (Z), X 1z and X 2z Independently preferred are 1,4-phenylene, which may have substituents, or cyclohexane-1,4-diyl, which may have substituents, X 1z and X 2z At least one of them is a 1,4-phenylene that may have a substituent, or a cyclohexane-1,4-diyl that may have a substituent, preferably trans-cyclohexane-1,4-diyl. Examples of substituents optionally present in the 1,4-phenylene that may have a substituent, or the cyclohexane-1,4-diyl that may have a substituent, include alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, and butyl, cyano groups, and halogen atoms such as chlorine and fluorine atoms. Unsubstituted is preferred.

[0266] Furthermore, regarding the polymerizable liquid crystal compound (Z), from the perspective of easily exhibiting smectic liquid crystal properties, it is preferable that the portion shown in formula (Z1) in formula (Z) [hereinafter referred to as partial structure (Z1)] is an asymmetric structure.

[0267] -(X 1 -Y 1 -) n -X 2 -(Z1)

[0268] [In the formula, X] 1z Y 1z X 2z [and nz each have the same meaning as above]

[0269] As a polymeric liquid crystal compound (Z) with a partially asymmetric structure (Z1), examples include those with nz = 1 and 1 X. 1z With X 2z These are polymeric liquid crystal compounds (Z) with different structures from each other. Additionally, examples include: nz = 2 and 2 Y... 1z For the same structure, and 2 X 1z For the same structure, and 1 X 2z With these two X's 1z For polymeric liquid crystal compounds with different structures (Z); nz is 2 and 2 Y 1z For the same structure, and 2 X 1z In and W 1z bonded X 1z With another X 1z and X 2z For different structures, and another X 1z With X 2z The polymeric liquid crystal compounds (Z) are identical in structure to each other. Furthermore, examples include nz with 3 and 3 Y atoms. 1z They have the same structure and 3 X's 1z and 1 X 2z Any one of them is a polymeric liquid crystal compound (Z) with a different structure from all of the other three.

[0270] Y 1z Preferred bonds include -CH2CH2-, -CH2O-, -CH2CH2O-, -COO-, -OCOO-, single bonds, -N=N-, and -CR. az =CR bz -、-C≡C-、-CR az =N- or -CO-NR az -. R az and R bz Each of the following groups independently represents an alkyl group having 1 to 4 hydrogen atoms or carbon atoms. 1z More preferably, it is -CH2CH2-, -COO-, or a single bond, and multiple Y bonds exist. 1z In the case of X 2z Bonded Y 1z More preferably, it is -CH2CH2- or -CH2O-. X 1z and X 2z When all structures are identical, it is preferable to have two or more Y atoms with different bonding methods. 1z There exist multiple Ys with different bonding methods. 1z In this case, it becomes an asymmetric structure, and therefore tends to exhibit smectic liquid crystal properties.

[0271] U 2zThese are the aforementioned polymeric groups. U 1z It can be a hydrogen atom or a polymerizable group. Considering ease of manufacture, ease of improving the heat resistance of the anisotropic light absorption film, and ease of adjusting the adhesion between the anisotropic light absorption film and the substrate, the polymerizable group is preferably (meth)acryloyloxy. The polymerizable group can be in a polymerized state or an unpolymerized state, but is preferably in an unpolymerized state.

[0272] As V 1z and V 2z Examples of alkane diyl groups include methylene, ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane-1,10-diyl, tetradecane-1,14-diyl, and eicosane-1,20-diyl. 1z and V 2z Preferably, it is an alkane diester with 2 to 12 carbon atoms, and more preferably an alkane diester with 6 to 12 carbon atoms.

[0273] Examples of substituents that may be optionally present in the alkane dimethyl group include cyano groups and halogen atoms, but the alkane dimethyl group is preferably unsubstituted, and more preferably an unsubstituted straight-chain alkane dimethyl group.

[0274] W 1z and W 2z The components are preferably single bonds, -O-, -S-, -COO-, or -OCOO-, and more preferably single bonds or -O-.

[0275] The polymeric liquid crystal compound (Z) preferably has an asymmetric molecular structure, and more preferably, it is a polymeric liquid crystal compound having partial structures of (Aa) to (Ai). From the viewpoint of easily exhibiting higher-order smectic liquid crystal properties, partial structures of (Aa), (Ab), or (Ac) are more preferred. It should be noted that in (Aa) to (Ai) below, * indicates a connecting bond (single bond).

[0276] [Chemical Formula 25]

[0277]

[0278] As a polymerizable liquid crystal compound (Z), examples include compounds represented by formulas (A-1) to (A-25). When the polymerizable liquid crystal compound (Z) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably the trans form.

[0279] [Chemical Formula 26]

[0280]

[0281] [Chemical Formula 27]

[0282]

[0283] [Chemical Formula 28]

[0284]

[0285] [Chemical Formula 29]

[0286]

[0287] [Chemical Formula 30]

[0288]

[0289] Among them, at least one is preferably selected from the group consisting of compounds represented by formulas (A-2), (A-3), (A-4), (A-5), (A-6), (A-7), (A-8), (A-13), (A-14), (A-15), (A-16), and (A-17). As the polymerizable liquid crystal compound (Z), one can be used alone, or two or more can be used in combination. Furthermore, when combining two or more polymerizable liquid crystal compounds, at least one is preferably compound (Z), and more preferably two or more are compound (Z). By combining them, liquid crystal properties can sometimes be temporarily maintained even at temperatures below the liquid crystal-crystallization phase transition temperature. The mixing ratio when combining two polymerizable liquid crystal compounds is typically 1:99 to 50:50, preferably 5:95 to 50:50, and more preferably 10:90 to 50:50. When combining two polymerizable liquid crystal compounds, and only one of them is compound (Z), it is preferable to combine them in such a way that compound (Z) is in the higher proportion of the aforementioned mixing ratio.

[0290] Polymerizable liquid crystal compounds (Z) can be manufactured by known methods, for example, as described in Lub et al., Recl.Trav.Chim.Pays-Bas, 115, 321-328 (1996), or Japanese Patent No. 4719156.

[0291] The polymeric liquid crystal compound forming the anisotropic light-absorbing film is preferably a polymeric liquid crystal compound having a maximum absorption wavelength between 300 and 400 nm. When a photopolymerization initiator is included in the polymeric liquid crystal composition, polymerization and gelation of the polymeric liquid crystal compound may occur during long-term storage. However, if the maximum absorption wavelength of the polymeric liquid crystal compound is between 300 and 400 nm, the generation of reactive species originating from the photopolymerization initiator and the polymerization and gelation of the polymeric liquid crystal compound caused by these reactive species can be effectively suppressed even when exposed to ultraviolet light during storage. Therefore, this is advantageous from the perspective of the long-term stability of the composition containing the polymeric liquid crystal compound, and can improve the orientation and uniformity of the resulting liquid crystal cured film. It should be noted that the maximum absorption wavelength of the polymeric liquid crystal compound can be measured using a UV-Vis spectrophotometer in a solvent. This solvent is one that can dissolve the polymeric liquid crystal compound, such as chloroform.

[0292] Regarding the content ratio of the liquid crystal compound in the liquid crystal composition forming the light absorption anisotropic film, from the viewpoint of improving the orientation of the liquid crystal compound, it is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, more preferably 99.5 parts by mass or less, more preferably 99 parts by mass or less, further preferably 94 parts by mass or less, and even more preferably 90 parts by mass or less, relative to 100 parts by mass of the light absorption anisotropic film. The content ratio of the liquid crystal compound can be calculated in the form of the proportion of the liquid crystal compound relative to 100 parts by mass of the solid component of the liquid crystal composition forming the light absorption anisotropic film.

[0293] In a light-absorbing anisotropic film comprising a dichroic pigment and a liquid crystal compound, the dichroic pigment exists in a state encapsulated by a polymerizable liquid crystal compound. Preferably, the dichroic pigment and the polymerizable liquid crystal compound are oriented in a manner that has a high degree of order in the vertical direction of the light-absorbing anisotropic film. By aligning the polymerizable liquid crystal compound and the dichroic pigment in a manner that has a high degree of order, when assembling a laminate comprising this light-absorbing anisotropic film into an organic EL display device, there is a tendency for: excellent transmittance in the front direction, and reduced directional anisotropy of light absorption characteristics in the tilt direction, resulting in excellent protection against viewing from the tilt direction.

[0294] In this invention, the liquid crystal composition used to form a light-absorbing anisotropic film may contain components other than dichroic pigments and liquid crystal compounds. Examples of such components include polymerization initiators, leveling agents, solvents, antioxidants, and photosensitizers. Each of these components may be used individually or in combination of two or more.

[0295] <Polymerization initiator>

[0296] A polymerization initiator is a compound that can initiate polymerization reactions of polymerizable liquid crystal compounds, etc. As a polymerization initiator, a photopolymerization initiator that generates active free radicals through the action of light is preferred.

[0297] Examples of polymerization initiators include benzoin compounds, benzophenone compounds, alkyl benzophenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts, and matte salts.

[0298] Examples of benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone.

[0299] Examples of alkyl phenyl ketone compounds include, for example, diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1-one.

[0300] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyl diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0301] Examples of triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)] Vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

[0302] Commercially available polymerization initiators can be used as polymerization initiators. Examples of commercially available polymerization initiators include Irgacure (イルガキュア) 907, 184, 651, 819, 250 and 369 (BASF Corporation); SEIKUOL (Registered Trademark) BZ, Z and BEE (Seiko Chemical Co., Ltd.); kayacure (Registered Trademark) BP100 and VUI-6992 (Nippon Kayaku Co., Ltd.); ADEKA OPTOMER SP-152 and SP-170 (ADEKA Co., Ltd.); TAZ-A and TAZ-PP (DKSH Japan Co., Ltd.); and TAZ-104 (Sanwa Chemical Co., Ltd.), etc.

[0303] Regarding the content of the polymerization initiator, from the viewpoint that it is less likely to cause the orientation of the polymerizable liquid crystal compound to be disordered, it is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, more preferably 30 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less, relative to 100 parts by mass of the polymerizable liquid crystal compound.

[0304] Leveling agent

[0305] A leveling agent is a substance that adjusts the flowability of a liquid crystal composition and makes the anisotropic light absorption film flatter; examples include surfactants. Preferred leveling agents include those based on polyacrylate compounds and those based on compounds containing fluorine atoms.

[0306] Examples of leveling agents with polyacrylate compounds as the main component include BYK-350, BYK-352, BYK-353, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-380, BYK-381, and BYK-392 (BYK Chemie).

[0307] Examples of leveling agents whose main components are compounds containing fluorine atoms include MEGAFACE (registered trademark) R-08, R-30, R-90, F-410, F-411, F-443, F-445, F-470, F-471, F-477, F-479, F-482, and F-483 (DIC Corporation); Surflon (registered trademark) S-381, S-382, S-383, S-393, SC-101, SC-105, KH-40, and SA-100 (AGC Seimi Chemical Co., Ltd.); E1830 and E5844 (Daikin Industries, Ltd.); and EFTOPEF301, EF303, EF351, and EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd.).

[0308] The leveling agent content is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, more preferably 5 parts by mass or less, and more preferably 3 parts by mass or less, relative to 100 parts by mass of the liquid crystal compound. If the leveling agent content is within the aforementioned range, the resulting liquid crystal cured film tends to be smoother, which is therefore preferred. If the leveling agent content exceeds the aforementioned range relative to the liquid crystal compound, unevenness or horizontal orientation tends to occur in the resulting liquid crystal cured film, which is therefore not preferred. The light absorption anisotropic film may contain two or more leveling agents.

[0309] Solvent

[0310] As a solvent, a solvent that can completely dissolve the liquid crystal compound is preferred. Furthermore, if the liquid crystal compound is a polymerizable liquid crystal compound, a solvent that is inactive for the polymerization reaction is even more preferred.

[0311] Examples of solvents include 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, or propylene glycol methyl ether acetate and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; 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; and so on. These solvents can be used alone or in combination of two or more.

[0312] The solvent content is preferably 50 to 98% by mass relative to the total amount of the liquid crystal composition. In other words, the proportion of the light-absorbing anisotropic film component is preferably 2 to 50% by mass relative to the total amount of the liquid crystal composition.

[0313] If the solid component is less than 50% by mass relative to the total amount of the liquid crystal composition, the viscosity of the liquid crystal composition becomes lower, and therefore the thickness of the liquid crystal cured film becomes approximately uniform. Consequently, there is a tendency to avoid unevenness in the light absorption anisotropic film. Furthermore, the solid component can be determined taking into account the thickness of the light absorption anisotropic film to be manufactured.

[0314] Antioxidants

[0315] By combining antioxidants, the polymerization reaction of polymerizable liquid crystal compounds can be controlled. The antioxidants can be primary antioxidants selected from phenolic, amine, quinone, and nitroso antioxidants, or secondary antioxidants selected from phosphorus and sulfur antioxidants.

[0316] In order to polymerize the polymerizable liquid crystal compound without disrupting its orientation, the content of antioxidant is typically 0.01 to 10 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound, preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass.

[0317] Antioxidants can be used alone or in combination of two or more.

[0318] <Photosensitizer>

[0319] By using a photosensitizer, the sensitivity of the photopolymerization initiator can be increased. Examples of photosensitizers include xanthone, thioxanthone, and other xanthone derivatives; anthracene and anthracene derivatives with substituents such as alkyl ethers; phenothiazine; and rubrene. The photosensitizer can be used alone or in combination of two or more. The content of the photosensitizer is typically 0.01 to 10 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass.

[0320] The light-absorbing anisotropic film of the present invention can be manufactured, for example, by a method comprising the following steps:

[0321] The process of obtaining a liquid crystal composition by stirring a liquid crystal compound, a dichroic pigment, and additives such as solvents used as appropriate at a specified temperature.

[0322] The process of forming the coating film of the liquid crystal composition; and

[0323] The process of drying the aforementioned coating to form a dry coating film.

[0324] The temperature for stirring the liquid crystal compound, dichroic pigment, and additives such as solvents used as appropriate is typically 0–50°C, preferably 10–40°C. There are no particular limitations on the method of stirring; conventionally known methods can be used.

[0325] The formation of a coating film of a liquid crystal composition can be achieved, for example, by coating a substrate, an alignment film, or a horizontally aligned phase retardation film i described later.

[0326] Examples of substrates include glass substrates and membrane substrates, with resin membrane substrates being preferred from a processability point of view. Examples of resins constituting the membrane substrate include polyolefins such as polyethylene, polypropylene, and norbornene polymers; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate; polyacrylate; cellulose esters such as cellulose triacetate, cellulose diacetate, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; polyphenylene sulfide; and polyphenylene ether. Such resins can be used to form a film using known methods such as solvent casting and melt extrusion to create the substrate. The substrate surface can have a protective layer formed from acrylic resin, methacrylic resin, epoxy resin, oxetane resin, polyurethane resin, melamine resin, etc., and can also undergo surface treatments such as silicone treatment for release, corona treatment, and plasma treatment.

[0327] Commercially available products can be used as the base material. Examples of commercially available cellulose ester base materials include those manufactured by Fuji Photo Film Co., Ltd. (such as Fujitack Film); and those manufactured by KONICA MINOLTA Opto Co., Ltd. (such as "KC8UX2M", "KC8UY", and "KC4UY"). Examples of commercially available cyclic olefin resins include those manufactured by Ticona (Germany) (such as Topas (registered trademark)); those manufactured by JSR Co., Ltd. (such as ARTON (registered trademark)); those manufactured by Zeon Co., Ltd. (Japan) (such as ZEONOR (registered trademark) and ZEONEX (registered trademark)); and those manufactured by Mitsui Chemicals Co., Ltd. (such as Apel (registered trademark)). Commercially available cyclic olefin resin substrates can also be used. Examples of commercially available cyclic olefin resin substrates include those manufactured by Sekisui Chemicals Co., Ltd., such as "Escena (registered trademark)" and "SCA40 (registered trademark)"; those manufactured by OPTES Co., Ltd., such as "ZEONORFILM (registered trademark)"; and those manufactured by JSR Co., Ltd., such as "ARTONFILM (registered trademark)".

[0328] From the viewpoint of ease of peeling and operability of the substrate, the thickness of the substrate is usually 5 to 300 μm, preferably 10 to 150 μm.

[0329] Methods for coating liquid crystal compositions onto substrates include known methods such as spin coating, extrusion, gravure coating, die coating, squeegee coating, coater coating, and printing methods such as flexographic printing.

[0330] Next, the solvent is removed by drying or the like, thereby forming a dried coating film. Examples of drying methods include natural drying, ventilation drying, heating drying, and reduced pressure drying. At this time, by heating the coating film obtained from the liquid crystal composition, the solvent can be removed from the coating film while simultaneously orienting the liquid crystal compound perpendicularly to the coating film plane. The heating temperature of the coating film can be appropriately determined considering the liquid crystal compound used and the material of the substrate to which the coating film is to be formed, but a temperature above the liquid crystal phase transition temperature is required to transform the liquid crystal compound into a liquid crystal layer state. To remove the solvent contained in the liquid crystal composition while simultaneously achieving a perpendicularly oriented state for the liquid crystal compound, for example, the temperature can be heated to near or above the liquid crystal phase transition temperature (smectic phase transition temperature or nematic phase transition temperature) of the liquid crystal compound contained in the aforementioned liquid crystal composition.

[0331] It should be noted that the liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature stage, a differential scanning calorimeter (DSC), or a thermogravimetric differential calorimeter (TG-DTA). Furthermore, when two or more liquid crystal compounds are used in combination, the aforementioned phase transition temperature refers to the temperature measured using a mixture of liquid crystal compounds obtained by mixing all the liquid crystal compounds constituting the liquid crystal composition at the same ratio as the composition in the liquid crystal composition, in the same manner as when using a single liquid crystal compound. It should be noted that it is known that the liquid crystal phase transition temperature of the liquid crystal compound in the aforementioned liquid crystal composition is generally lower than the liquid crystal phase transition temperature of the liquid crystal compound monomer.

[0332] The heating time can be appropriately determined according to the heating temperature, the type of polymeric liquid crystal compound used, the type of solvent, its boiling point and amount, etc., and is usually 15 seconds to 10 minutes, preferably 0.5 to 5 minutes.

[0333] When a polymerizable liquid crystal compound is used as the liquid crystal compound, it is then polymerized in the obtained dried coating while maintaining its vertical orientation, thereby forming a light-absorbing anisotropic film. Examples of polymerization methods include thermal polymerization and photopolymerization, but photopolymerization is preferred from the viewpoint of easier control of the polymerization reaction. In photopolymerization, the light irradiating the dried coating is appropriately selected based on the type of photopolymerization initiator contained in the dried coating, the type of polymerizable liquid crystal compound (especially the type of polymerizable groups possessed by the polymerizable liquid crystal compound), and their amount. Specific examples include light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, alpha rays, beta rays, and gamma rays, as well as an active electron beam. From the perspective of easy control of the polymerization reaction and the availability of devices widely used in the field as photopolymerization apparatuses, ultraviolet light is preferred. It is even more preferable to pre-select the types of polymeric liquid crystal compounds and photopolymerization initiators contained in the polymeric liquid crystal composition (hereinafter, a composition containing a polymeric liquid crystal compound is sometimes referred to as a "polymeric liquid crystal composition") in a manner suitable for photopolymerization using ultraviolet light. Furthermore, during polymerization, the polymerization temperature can be controlled by simultaneously cooling the dried coating film using appropriate cooling methods and then irradiating it with light. If the polymerization of the polymeric liquid crystal compound is carried out at a lower temperature using such cooling methods, a suitable light-absorbing anisotropic film can be formed even if a material with low heat resistance is used as the substrate. Additionally, the polymerization reaction can be promoted by increasing the polymerization temperature, provided that adverse conditions caused by heat during light irradiation (such as deformation of the substrate due to heat) do not occur. During photopolymerization, a patterned light-absorbing anisotropic film can also be obtained by performing masking, development, or other processes.

[0334] Examples of light sources for the aforementioned 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 lamps, gallium lamps, excimer lasers, LED light sources emitting light in the wavelength range of 380–440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, and metal halide lamps.

[0335] Ultraviolet radiation intensity is typically 10–3,000 mW / cm². 2 The intensity of ultraviolet irradiation is preferably within the wavelength range effective for activating photopolymerization initiators. The irradiation time is typically 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, and even more preferably 0.1 seconds to 1 minute. When irradiated once or multiple times at such an intensity, the cumulative light intensity is 10 to 3,000 mJ / cm². 2 Preferably, it is 50–2,000 mJ / cm². 2 More preferably 100–1,000 mJ / cm 2 .

[0336] The thickness of the light-absorbing anisotropic film can be appropriately selected according to the display device to which it is applied, preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, further preferably 0.2 to 3 μm or 0.5 to 5 μm, and particularly preferably 0.5 to 3 μm. If the thickness of the light-absorbing anisotropic film is within the aforementioned range, the effect of eliminating the hue of the display when viewed from an oblique direction is easily improved, and in addition, the laminate can be made thinner. The thickness of the light-absorbing anisotropic film can be measured using, for example, a laser microscope or a stylus-type film thickness gauge.

[0337] In one embodiment of the present invention, a coating of a liquid crystal composition is formed on an alignment film. The alignment film has an alignment control force that aligns the liquid crystal compound in a desired direction. Sometimes, an alignment film having an alignment control force that aligns the liquid crystal compound in a horizontal direction is called a horizontal alignment film, and an alignment film having an alignment control force that aligns the liquid crystal compound in a vertical direction is called a vertical alignment film. The alignment control force can be arbitrarily adjusted by the type of alignment film, surface condition, friction conditions, etc., and when the alignment film is formed of a photo-alignable polymer, it can be arbitrarily adjusted by polarized light irradiation conditions, etc.

[0338] As an alignment film, it is preferable to have solvent resistance that prevents dissolution due to coating of the liquid crystal composition, and heat resistance for heat treatment of solvent removal and alignment of the liquid crystal compound (described later). Examples of alignment films include alignment films containing an alignment polymer, photoalignment films, groove alignment films with raised and recessed patterns or multiple grooves on the surface, and stretched films stretched along the alignment direction. From the viewpoint of the accuracy and quality of the alignment angle, photoalignment films are preferred.

[0339] Examples of oriented polymers include polyamides having intramolecular amide bonds, gelatin-like substances, polyimides having intramolecular imide bonds and their hydrolysates such as polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylates. Polyvinyl alcohol is preferred. Oriented polymers can be used alone or in combination of two or more.

[0340] Alignment films containing alignment polymers can typically be obtained by: coating a composition (hereinafter sometimes referred to as "alignment polymer composition") formed by dissolving the alignment polymer in a solvent onto a substrate, and then removing the solvent; or by coating the alignment polymer composition onto a substrate, removing the solvent, and then rubbing (rubbing method). Examples of solvents include those exemplified above as solvents that can be used in liquid crystal compositions.

[0341] Regarding the concentration of the oriented polymer in the oriented polymer composition, it is acceptable as long as the oriented polymer material can be completely dissolved in the solvent. Relative to the solution, it is preferably 0.1 to 20% in terms of solid content, and more preferably about 0.1 to 10%.

[0342] As an orientation polymer composition, commercially available orientation film materials can be used directly. Examples of commercially available orientation film materials include SUNEVER (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and OPTOMER (registered trademark, manufactured by JSR Corporation).

[0343] As a method for coating an oriented polymer composition onto a substrate, the same method as that exemplified as a method for coating a liquid crystal composition onto a substrate can be cited.

[0344] Methods for removing solvents contained in oriented polymer compositions include natural drying, ventilation drying, heating drying, and vacuum drying.

[0345] To impart orientation control force to the alignment film, a friction treatment (friction method) can be performed as needed. One method for imparting orientation control force using the friction method is to bring a film of an orientation polymer, formed on the surface of a substrate by coating an orientation polymer composition onto a substrate and annealing it, into contact with a friction roller wound with a friction cloth and rotating. If masking is applied during the friction treatment, multiple regions (patterns) with different orientation directions can also be formed in the alignment film.

[0346] Photoalignment films are typically obtained by coating a substrate with a composition (hereinafter also referred to as a "composition for photoalignment film formation") containing a polymer or monomer having photoreactive groups and a solvent, and then irradiating it with polarized light (preferably polarized UV light) after removing the solvent. In the case of photoalignment films, it is advantageous that the direction of the alignment control force can be arbitrarily controlled by selecting the polarization direction of the irradiated polarized light.

[0347] A photoreactive group refers to a group that generates liquid crystal alignment ability through light irradiation. Specifically, it can be a photoreactive group that participates in molecular orientation induction or isomerization reactions, dimerization reactions, photocrosslinking reactions, or photodecomposition reactions that occur through light irradiation, thus becoming the source of liquid crystal alignment ability. Among these, groups participating in dimerization reactions or photocrosslinking reactions are preferred from the perspective of excellent orientation. As a photoreactive group, it is preferred to have a group having unsaturated bonds, especially double bonds, and particularly preferred to have a group having at least one selected from the group consisting of carbon-carbon double bonds (C=C bonds), carbon-nitrogen double bonds (C=N bonds), nitrogen-nitrogen double bonds (N=N bonds), and carbon-oxygen double bonds (C=O bonds).

[0348] Examples of photoreactive groups with C=C bonds include vinyl, polyene, styrene, styrenezolium, styrenezolium, chalcone, and cinnamoyl.

[0349] Examples of photoreactive groups with C=N bonds include groups with structures such as aromatic Schiff bases and aromatic hydrazones. Examples of photoreactive groups with N=N bonds include azophenyl, azonaphthyl, aromatic heterocyclic azo, diazo, formazan, and groups with an azobenzene oxide structure. Examples of photoreactive groups with C=O bonds include benzophenone, coumarin, anthraquinone, and maleimide. These groups can have substituents such as alkyl, alkoxy, aryl, allyloxy, cyano, alkoxycarbonyl, hydroxyl, sulfonic acid, and haloalkyl.

[0350] Among these, photoreactive groups that participate in the photodimerization reaction are preferred. Considering that the amount of polarized light required for photoorientation is relatively small and that photoorientation films with excellent thermal and time stability are easily obtained, cinnamyl and chalcone groups are preferred. As polymers with photoreactive groups, polymers with cinnamyl groups at the ends of their side chains, forming a cinnamic acid structure, are particularly preferred.

[0351] By coating a photo-alignment film forming composition onto a substrate, a photo-alignment induction layer can be formed on the substrate. As a solvent included in the composition, the same solvents exemplified above as those used in liquid crystal compositions can be used, and the solvent can be appropriately selected based on the solubility of the polymer or monomer having photoreactive groups.

[0352] The content of the polymer or monomer with photoreactive groups in the composition for forming a photoalignment film can be appropriately adjusted according to the type of polymer or monomer and the thickness of the target photoalignment film. Preferably, it is at least 0.2% by mass, more preferably in the range of 0.3% to 10% by mass, relative to the mass of the composition for forming the photoalignment film. The composition for forming the photoalignment film may contain polymers such as polyvinyl alcohol and polyimide, and photosensitizers, within a range that does not significantly impair the properties of the photoalignment film.

[0353] As a method for coating a composition for forming a photo-aligned film onto a substrate, the same method as the method for coating an orientation polymer composition onto a substrate can be cited. As a method for removing solvent from the coated composition for forming a photo-aligned film, examples include natural drying, ventilation drying, heating drying, and reduced pressure drying.

[0354] To irradiate with polarized light, the product obtained by removing the solvent from the composition for forming a photo-alignment film coated on a substrate can be directly irradiated with polarized UV light, or polarized light can be irradiated from the substrate side, allowing the polarized light to pass through. Furthermore, this polarized light is particularly preferably substantially parallel light. The wavelength of the irradiated polarized light should be within the wavelength range where the photoreactive groups of the polymer or monomer having photoreactive groups can absorb light energy. Specifically, UV (ultraviolet) light in the wavelength range of 250–400 nm is particularly preferred. Examples of light sources for this polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, KrF, ArF, and other ultraviolet lasers, with high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps being more preferred. Among these, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are preferred due to the high luminous intensity of ultraviolet light at a wavelength of 313 nm. By passing the light from the aforementioned light source through a suitable polarizer, polarized UV light can be irradiated. As the polarizer, polarizing filters, polarizing prisms such as Glan-Thompson and Glan-Taylor, and wire grid type polarizers can be used.

[0355] It should be noted that if the area is shielded during rubbing or polarized light irradiation, multiple regions (patterns) with different liquid crystal orientations can also be formed.

[0356] A groove-aligned film is a film with raised or recessed patterns or multiple grooves on its surface. When a liquid crystal compound is coated on a film having multiple linear grooves arranged at equal intervals, the liquid crystal molecules are aligned along the direction of the grooves.

[0357] Methods for obtaining grooved oriented films include: exposing the surface of a photosensitive polyimide film through an exposure mask with a patterned slit, followed by development and rinsing to form a raised or recessed pattern; forming a layer of UV-curable resin before curing on a plate-shaped master with grooves on its surface, transferring the formed resin layer to a substrate, and then curing it; and pressing a roll-shaped master with multiple grooves onto a film of UV-curable resin before curing formed on a substrate to form a raised or recessed pattern, and then curing it; and so on.

[0358] In addition to the aforementioned oriented polymers, materials that exhibit orientation control forces that orient liquid crystal compounds in a direction perpendicular to the coating plane can also be used as materials for orientation control. These include fluorinated polymers such as perfluoroalkyl groups, silane compounds, and polysiloxane compounds obtained through their condensation reactions.

[0359] When using silane compounds as materials for forming alignment films, from the viewpoint of easily reducing surface tension and improving adhesion to layers adjacent to the alignment film, compounds containing Si and C elements in their constituent elements are preferred, and silane compounds are thus preferred. Using silane compounds can improve orientation control. These silane compounds can be used alone, in combination of two or more, or mixed with other materials.

[0360] The thickness of the alignment film (an alignment film containing an alignment polymer or a photoalignment film) is typically in the range of 10 to 10,000 nm, preferably in the range of 10 to 1,000 nm, more preferably below 10 to 500 nm, even more preferably in the range of 10 to 300 nm, and particularly preferably in the range of 50 to 250 nm.

[0361] In another aspect of the present invention, the coating of the liquid crystal composition can be formed directly on a substrate without an alignment film. In this aspect, the liquid crystal composition for forming the light-absorbing anisotropic film typically includes an alignment promoter. In the present invention, an alignment promoter refers to a material that promotes the liquid crystal compound to align in the desired direction. Examples of alignment promoters for promoting the alignment of the liquid crystal compound include ionic compounds formed from non-metallic atoms and non-ionic silane compounds. The liquid crystal composition for forming the light-absorbing anisotropic film preferably includes at least one of an ionic compound formed from non-metallic atoms and a non-ionic silane compound, and more preferably includes both an ionic compound formed from non-metallic atoms and a non-ionic silane compound.

[0362] When the liquid crystal composition forming the light-absorbing anisotropic film contains an ionic compound formed from non-metallic atoms, in the dried coating formed on the substrate by the light-absorbing anisotropic film forming composition, there exists a tendency for the liquid crystal compound to be oriented vertically relative to the substrate surface within the dried coating due to electrostatic interactions, exhibiting a vertical orientation control force on the liquid crystal compound. Thus, the vertical orientation of the liquid crystal compound can be maintained to form a cured liquid crystal film.

[0363] Examples of onion salts formed from non-metallic atoms include quaternary ammonium salts, tertiary sulfonium salts, and quaternary phosphonium salts with positively charged nitrogen atoms. Among these onion salts, quaternary onion salts are preferred from the viewpoint of further improving the vertical orientation of the liquid crystal compound, and quaternary phosphonium salts or quaternary ammonium salts are more preferred from the viewpoint of improving availability and mass production. Onion salts may have two or more quaternary onion salt sites within the molecule, and may also be oligomers or polymers.

[0364] The molecular weight of the ionic compound is preferably 100 to 10,000. If the molecular weight is within this range, it is easier to improve the vertical orientation of the liquid crystal compound while ensuring the coatability of the liquid crystal composition. More preferably, the molecular weight of the ionic compound is 5,000 or less, and even more preferably 3,000 or less.

[0365] Examples of cationic components for ionic compounds include inorganic and organic cations. Among these, organic cations are preferred from the viewpoint of minimizing orientation defects in polymerizable liquid crystal compounds. Examples of organic cations include imidazolium cations, pyridinium cations, ammonium cations, sulfonium cations, and phosphonium cations.

[0366] Ionic compounds typically possess counterions. Examples of counterions that serve as the cation component include inorganic and organic anions. Organic anions are preferred from the perspective of minimizing orientation defects in liquid crystal compounds. It should be noted that the cation and anion do not necessarily correspond one-to-one.

[0367] When the liquid crystal composition forming the light-absorbing anisotropic film contains an ionic compound, its content relative to the solid component of the liquid crystal composition is generally preferably 0.01 to 5% by mass, more preferably 0.05 to 4% by mass, and even more preferably 0.1 to 3% by mass. If the content of the ionic compound is within the above range, good coatability of the liquid crystal composition can be maintained, and the vertical orientation of the liquid crystal compound can be effectively promoted.

[0368] When a liquid crystal composition forming an anisotropic light absorption film contains a nonionic silane compound, the following tendency exists: the nonionic silane compound reduces the surface tension of the liquid crystal composition; in a dried coating film formed on a substrate by the composition for forming anisotropic light absorption films, the presence of the nonionic silane compound on the side of the dried coating film opposite to the substrate enhances the vertical orientation control of the liquid crystal compound; and within the dried coating film, the liquid crystal compound is oriented vertically relative to the substrate surface. Therefore, a liquid crystal cured film can be formed while maintaining the vertical orientation of the liquid crystal compound.

[0369] Nonionic silane compounds are nonionic compounds that contain the element Si. Examples of nonionic silane compounds include, for example, silicon polymers such as polysilanes, silicone resins such as silicone oils and organosilicon resins, as well as organosilicon oligomers, organic and inorganic silane compounds such as silsesquioxanes and alkoxysilanes (more specifically, silane coupling agents, etc.), and silane-containing compounds described in the section on leveling agents.

[0370] When the liquid crystal composition forming the light-absorbing anisotropic film contains a nonionic silane compound, its content relative to the solid component of the liquid crystal composition is generally preferably 0.01% to 5% by mass, more preferably 0.05% to 4% by mass, and even more preferably 0.1% to 3% by mass. If the content of the nonionic silane compound is within the aforementioned range, good coatability of the liquid crystal composition can be maintained, and the vertical alignment of the liquid crystal compound can be effectively promoted.

[0371] By including both an ionic compound and a nonionic silane compound in the liquid crystal composition for forming anisotropic light absorption films, the vertical alignment of the liquid crystal compound is easily further promoted in the dried coating formed on the substrate by the composition for forming anisotropic light absorption films, thanks to the electrostatic interaction from the ionic compound and the surface tension reduction effect from the nonionic silane compound. This allows for the formation of a liquid crystal cured film while maintaining a more precise vertical alignment of the liquid crystal compound.

[0372] <Horizontal orientation phase difference film>

[0373] In this invention, the horizontally oriented retardation film may be, for example, a stretched film or a cured product of a polymeric liquid crystal composition containing a polymeric liquid crystal compound, or a cured product formed by curing the polymeric liquid crystal compound in a state of horizontal orientation relative to the plane of the retardation film (hereinafter also referred to as "horizontally oriented liquid crystal cured film").

[0374] <Horizontal orientation phase difference film i>

[0375] The horizontally oriented phase difference film i (hereinafter, sometimes simply referred to as "film i") in this invention satisfies the following equation (4) as described above:

[0376] 70nm≤Re i (550)≤170nm (4)

[0377] In equation (4), Re i (λ) represents the in-plane phase difference value of the horizontally oriented phase difference film i at wavelength λnm.

[0378] Regarding the laminate of the present invention, due to the in-plane phase difference Re of the horizontally oriented phase difference film i i (550) Within the range of Equation (4), therefore, when applied to an organic EL display device, the transmittance in the front direction is excellent, and the directional anisotropy of the light absorption characteristics in the tilt direction is reduced, which prevents viewing from the tilt direction. Furthermore, when viewing the organic EL display device through polarized sunglasses, the visual recognition in the front direction is excellent.

[0379] In-plane phase difference Re i (550) More preferably, Re ≤ 80nm i Within the range of (550)≤160nm, it is further preferred to be within the range of 90nm≤Re i Within the range of (550)≤150nm, for example, it can also be 90nm≤Rei(550)≤130nm. Regarding the in-plane phase difference Re of film i... i(550) In this regard, the above-mentioned range can be adjusted appropriately by, for example, the thickness of membrane i; the type and / or amount of additives contained in membrane i; and the manufacturing conditions of membrane i. The in-plane phase difference Re of membrane i i (550) The phase difference can be measured using a phase difference measuring device, for example, by using the method described in the embodiments described later.

[0380] Furthermore, regarding the laminate of the present invention, due to the maximum absorption wavelength λ of the light-absorbing anisotropic film... MAX The following relationship (A) between the in-plane phase difference Rei(λ) of the horizontally oriented phase difference film i at that wavelength and the following equation is in the range of 0.6 to 2.0. Therefore, when applied to organic EL display devices, it is particularly possible to reduce the directional anisotropy of light absorption characteristics in the tilt direction. This range is preferably 0.7 to 1.8, and more preferably 0.8 to 1.5.

[0381] (λMAX / 4) / (Rei(λ))(A)

[0382] Maximum absorption wavelength λ of anisotropic optical absorption films MAX For example, a spectrophotometer can be used to measure it.

[0383] The aforementioned horizontally oriented phase difference film i preferably satisfies the following equation (8):

[0384] Re i (450) / Re i (550)≥1.00 (8)

[0385] In equation (8), Re i (λ) has the same meaning as in equation (4) above.

[0386] The angle θ between the slow axis of the aforementioned horizontally oriented retardation film i and the absorption axis of the polarizer. i The preferred range is as follows (9):

[0387] 15°≤|θ i |≤75° (9).

[0388] When film i satisfies the above equation (8), film i exhibits a so-called positive wavelength dispersion, where the in-plane phase difference at short wavelengths is greater than the in-plane phase difference at long wavelengths. Regarding the laminate of the present invention, when film i satisfies the above equation (8), when applied to an organic EL display device, it exhibits excellent transmittance in the front direction and reduces the directional anisotropy of light absorption characteristics in the tilt direction, easily improving the effect of preventing viewing from the tilt direction. Furthermore, it also provides excellent visual recognition when viewed from the front through polarized sunglasses. The Re i (450) / Rei (550) More preferably, it is 1.01 or higher, and even more preferably, it is 1.03 or higher. The Re of membrane i i (450) / Re i The upper limit of (550) is not particularly limited, for example, it is 5.0 or less, preferably 2.0 or less, and more preferably 1.3 or less. It should be noted that Re i (450) can be compared with the aforementioned Re i (550) Adjust in the same way, and in addition, the same method can be used to determine.

[0389] When film i satisfies the above equation (9), it can become a so-called 1 / 4 wavelength plate (λ / 4 plate) capable of converting linearly polarized light into circularly polarized light. When film i satisfies the above equation (9), the laminate of the present invention exhibits excellent transmittance in the frontal direction and reduces the directional anisotropy of light absorption characteristics in the tilt direction, easily further improving the effect of preventing peeping from the tilt direction. |θ i |More preferably, 25°≤|θ i Within the range of | ≤ 65°, it is further preferred to be within the range of 35° ≤ |θ i Within the range of ≤55°, the angle θ between the slow axis of film i and the absorption axis of the polarizer. i The above range can be adjusted by, for example, adjusting the bonding angle, aligning the slow axis of film i or the absorption axis of polarizer with a predetermined angle during manufacturing, and bonding in a roll-to-roll manner.

[0390] In this invention, the horizontally oriented retardation film i can be a stretched film or a film formed from a composition containing a liquid crystal compound, but is preferably a film stretched at least in one direction. If film i is a film stretched at least in one direction, the laminate of this invention, when applied to an organic EL display device, exhibits excellent transmittance in the front direction and reduces the directional anisotropy of light absorption characteristics in the tilt direction, easily further improving the effect of preventing viewing from the tilt direction. Furthermore, there is a tendency for the laminate of this invention to have improved thermal stability, dimensional stability, and mechanical strength.

[0391] The membrane being stretched at least in one direction is not particularly limited, but from the viewpoint of dimensional stability and heat resistance, a membrane with a glass transition temperature (Tg) of 80–200°C is preferred. Examples include polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; polyvinyl fluoride, polyvinylidene fluoride, and polyethylene fluoride. Fluorinated polyolefin resins such as fluoride; polyester resins such as polyethylene naphthalate, polyethylene terephthalate, polyethylene butylene terephthalate, and polyethylene terephthalate / isophthalate copolymer; polyamides such as nylon 6 and nylon 6,6; vinyl polymers such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, and vinylon; cellulose resins such as cellulose triacetate, cellulose diacetate, and celluloid; (meth)acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, and polybutyl acrylate; and films composed of polystyrene, polycarbonate, polyarylate, and polyimide. From the viewpoint of dimensional stability, films containing vinyl polymers, (meth)acrylic resins, or polyolefin resins are preferred, and films containing cycloolefin resins are more preferred. The glass transition temperature can be measured, for example, using DSC (differential scanning calorimetry).

[0392] As a film formed from a composition containing a liquid crystal compound, it can be obtained from the same material as film ii described later, such as a cured product of a polymeric liquid crystal composition containing at least one polymeric liquid crystal compound.

[0393] In this invention, film i can be a single layer or multiple layers. For example, a multilayer film i can be obtained by stacking a film formed from a composition containing a liquid crystal compound onto a substrate.

[0394] A horizontally oriented retardation film i can be manufactured, for example, by a method including the following steps:

[0395] The process of molding the above-mentioned resin, optionally containing additives such as antioxidants and ultraviolet absorbers, into a film; and

[0396] The process of stretching the above-mentioned membrane.

[0397] Known methods for molding resin into a film include melt extrusion, thermoforming, injection molding, and solvent casting.

[0398] Methods for stretching a membrane include, for example, uniaxial stretching or biaxial stretching.

[0399] Examples of stretching directions include the mechanical travel direction (MD) of the unstretched film, a direction orthogonal to it (TD), and a direction oblique to the mechanical travel direction (MD). Uniaxial stretching can be performed between rollers with different circumferential speeds, or using heated rollers. Biaxial stretching can be performed simultaneously along two stretching directions, or sequentially along other directions after stretching in a specified direction. The stretching process can be performed by, for example, using two or more pairs of clamping rollers with a higher circumferential speed at the exit side, stretching along the long side direction (mechanical travel direction: MD), or by holding both ends of the unstretched film with clamps and extending it along a direction orthogonal to the mechanical travel direction (TD). Additionally, as a method for stretching in an oblique direction, examples include: preparing a film roll obtained by winding a long film into a roll, continuously unwinding the film from the roll, conveying the unwound film, and stretching it along its longitudinal direction and in an oblique direction at a desired angle while heating it. The stretch ratio is typically 3 to 8 times. It should be noted that the stretch ratio in biaxial stretching refers to the stretch ratio in the direction with the larger stretch ratio.

[0400] For the horizontally oriented phase difference film i, surface treatments known in the art, such as plasma treatment, corona treatment, ozone treatment, and ultraviolet irradiation treatment, can be performed before and after the aforementioned stretching treatment.

[0401] From the viewpoint of achieving thinner laminates and improving flexibility, the thickness of the horizontally oriented retardation film i is typically 200 μm or less, preferably 100 μm or less, and more preferably 50 μm or less. Furthermore, there is no particular limitation on the lower limit of the thickness of the horizontally oriented retardation film i, but if it is too thin, the strength may decrease; therefore, it is typically 5 μm or more.

[0402] The aforementioned horizontally oriented retardation film, which is stretched at least in one direction, can use commercially available films. Examples of commercially available cyclic olefin resins include, for instance, cyclic olefin resins manufactured by Ticona (Germany) such as "Topas" (registered trademark); cyclic olefin resins manufactured by JSR Corporation such as "ARTON" (registered trademark); cyclic olefin resins manufactured by Zeon Corporation of Japan such as "ZEONOR" (registered trademark) and "ZEONEX" (registered trademark); and cyclic olefin resins manufactured by Mitsui Chemicals Corporation such as "Apel" (registered trademark). Commercially available cyclic olefin resin substrates can also be used. Examples of commercially available cyclic olefin resin substrates include those manufactured by Sekisui Chemicals Co., Ltd., such as "Escena" and "SCA40"; those manufactured by OPTES Co., Ltd., such as "ZEONORFILM"; and those manufactured by JSR Co., Ltd., such as "ARTONFILM". Additionally, examples of commercially available cellulose ester substrates include those manufactured by Fuji Photo Film Co., Ltd., such as "Fujitack Film"; and those manufactured by KONICA MINOLTA Opto Co., Ltd., such as "KC8UX2M", "KC8UY", and "KC4UY".

[0403] In one embodiment of the present invention, the horizontally aligned retardation film i is preferably adjacent to the aforementioned light-absorbing anisotropic film. The horizontally aligned retardation film i can be laminated via, for example, an adhesive layer or a bonding agent layer. Alternatively, a liquid crystal composition for forming the light-absorbing anisotropic film can be directly coated onto the horizontally aligned retardation film i via the aforementioned alignment film.

[0404] <Horizontal Orientation Phase Difference Film ii>

[0405] The horizontally oriented phase difference film ii (hereinafter, sometimes simply referred to as "film ii") in this invention satisfies the following equation (5) as described above:

[0406] 120nm≤Re ii (550)≤160nm (5)

[0407] In equation (5), Re ii (λ) represents the in-plane phase difference value of the horizontally oriented phase difference film ii at a wavelength of λnm.

[0408] Regarding the laminate of the present invention, if the in-plane phase difference Re of the horizontally oriented phase difference film ii is... ii(550) Within the range of equation (5), when applied to an organic EL display device, there is a tendency to reduce reflection from the front direction during black display and coloration during reflection, and there is a tendency for excellent transmittance in the front direction and reduced directional anisotropy of light absorption characteristics in the tilt direction, resulting in excellent prevention of viewing from the tilt direction. In-plane phase difference Re ii (550) More preferably, Re is within 130nm ≤ i Within the range of (550)≤150nm, it is further preferred to be within the range of 135nm≤Re i Within the range of (550)≤145nm, the in-plane phase difference Re of film ii is... ii The adjustment and measurement methods for (550) are the same as those described in the in-plane phase difference of membrane i.

[0409] The horizontally oriented phase difference film ii preferably satisfies the following equation (6):

[0410] Re ii (450) / Re ii (550)<1.00 (6)

[0411] In equation (6), Re ii (λ) has the same meaning as in equation (5) above.

[0412] The angle θ between the slow axis of the horizontally oriented retardation film II and the absorption axis of the polarizer. ii The preferred range is as follows (7):

[0413] 15°≤|θ ii |≤75° (7).

[0414] When film ii satisfies the above formula (6), film ii exhibits a so-called inverse wavelength dispersion, where the in-plane phase difference at short wavelengths is smaller than the in-plane phase difference at long wavelengths. When the laminate of the present invention, including the aforementioned film ii, is applied to an organic EL display device, it exhibits excellent transmittance in the front direction and reduces the directional anisotropy of light absorption characteristics in the tilt direction, easily improving the effect of preventing viewing from the tilt direction. Furthermore, it tends to reduce frontal reflection and coloration during black display when assembled into an organic EL display device. The Re ii (450) / Re ii (550) More preferably 0.90 or less, and even more preferably 0.85 or less. The Re of membrane ii ii (450) / Re ii The lower limit of (550) is not specifically limited, for example, above 0.1. It should be noted that the Re of membrane ii... ii (450) and Re ii(550) can interact with the Re of membrane i i (450) and Re i (550) Adjust in the same way, and in addition, the same method can be used to determine.

[0415] When film ii satisfies the above equation (7), it can become a so-called 1 / 4 wavelength plate (λ / 4 plate) capable of converting linearly polarized light into circularly polarized light. When film ii satisfies the above equation (7), when the laminate containing film ii is applied to an organic EL display device, there is a tendency to reduce reflection from the front direction and coloration during reflection, excellent transmittance in the front direction, and reduced directional anisotropy of light absorption characteristics in the tilt direction, which easily further improves the effect of preventing viewing from the tilt direction. |θ ii |More preferably, 25°≤|θ ii Within the range of | ≤ 65°, it is further preferred to be within the range of 35° ≤ |θ ii Within the range of ≤55°, the angle θ between the slow axis of film ii and the absorption axis of the polarizer. ii The angle θ between the slow axis of film i and the absorption axis of the polarizer can be used. i The same method can be used for adjustment, and the same method can also be used for measurement.

[0416] The horizontally oriented retardation film ii can be a stretched film or a film formed from a composition containing a liquid crystal compound, but is preferably formed from a cured polymeric liquid crystal composition containing at least one polymeric liquid crystal compound. Regarding the laminate of the present invention, if film ii is a film formed from a cured polymeric liquid crystal composition containing at least one polymeric liquid crystal compound, when applied to an organic EL display device, it tends to reduce reflection from the front direction and coloration during reflection, exhibits excellent transmittance in the front direction, and reduces the directional anisotropy of light absorption characteristics in the tilt direction, easily further improving the effect of preventing viewing from the tilt direction. Furthermore, the laminate containing film ii tends to have an increased front reflection hue.

[0417] It should be noted that, in this invention, the aforementioned horizontally oriented phase retardation film i is preferably a film that has been stretched at least in one direction, and the aforementioned horizontally oriented phase retardation film ii is formed from a cured product of a polymeric liquid crystal composition containing at least one polymeric liquid crystal compound. However, for example, the aforementioned films i and ii may both be films that have been stretched at least in one direction, and the aforementioned films i and ii may both be films formed from a cured product of a polymeric liquid crystal composition.

[0418] In this invention, the film ii can be a single layer or multiple layers. For example, a multilayer film ii can be obtained by stacking a film formed from a composition containing a liquid crystal compound onto a substrate.

[0419] As the polymerizable liquid crystal compound, the same compound that can be included in the aforementioned anisotropic light absorption film can be used, wherein a compound exhibiting reverse wavelength dispersion is preferred, for example, the compound represented by the above formula (X) is preferred.

[0420] Regarding the content of the polymeric liquid crystal compound in the polymeric liquid crystal composition used to form the horizontally aligned retardation film ii, it 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 even more preferably 90 to 95 parts by mass, relative to 100 parts by mass of the solid component of the polymeric liquid crystal composition. When the content of the polymeric liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the resulting cured liquid crystal film.

[0421] The polymeric liquid crystal composition used to form the horizontally aligned phase difference film ii may include, in addition to the polymeric liquid crystal compound, additives such as solvents, photopolymerization initiators, leveling agents, antioxidants, and photosensitizers. Examples of these components include those exemplified above as components that may be included in the light-absorbing anisotropic film; each component may be used individually or in combination of two or more.

[0422] If the horizontally oriented phase retardation film ii is a stretched film, it can be manufactured in the same manner as film i described above.

[0423] A horizontally oriented retardation film ii can be manufactured, for example, by a method including the following steps:

[0424] The process of obtaining a polymeric liquid crystal composition by stirring a polymeric liquid crystal compound and additives such as solvents used as appropriate at a specified temperature.

[0425] The process of coating a polymeric liquid crystal composition onto a substrate or an alignment film to obtain a coating film;

[0426] The process of drying the aforementioned coating to form a dried coating film; and,

[0427] The process of forming a horizontally oriented liquid crystal curing film by irradiating a dry coating with active energy rays.

[0428] The formation of a coating film of a polymeric liquid crystal composition can be achieved, for example, by coating the polymeric liquid crystal composition onto a substrate or an alignment film. The substrate that can be used here is the same substrate exemplified above as a substrate that can be used to manufacture anisotropic light-absorbing films.

[0429] The alignment film can be appropriately selected from materials having a horizontal alignment control force that orients the polymeric liquid crystal compound in the horizontal direction relative to the coating plane. The alignment control force can be arbitrarily adjusted by the type of alignment layer, surface condition, friction conditions, etc., and in the case of a photo-alignable polymer, it can be arbitrarily adjusted by polarized light irradiation conditions, etc. Examples of such materials include, for instance, the alignment polymers described above that can be used to manufacture anisotropic light-absorbing films. A horizontally aligned film can be obtained by coating a composition containing such a material and a solvent (e.g., the solvent exemplified in anisotropic light-absorbing films) onto a substrate, removing the solvent, and then heating the coated film. From a quality perspective, a photo-alignable film is preferred as a horizontally aligned film.

[0430] Next, the solvent is removed by drying, thereby forming a dried coating film. Examples of drying methods include natural drying, ventilation drying, heating drying, and reduced pressure drying. From a productivity perspective, heating drying is preferred, and the heating temperature is preferably high enough to remove the solvent and above the phase transition temperature of the polymerizable liquid crystal compound. Examples of steps and conditions in this process are the same as those used in methods for manufacturing anisotropic light-absorbing films.

[0431] The obtained dried coating is irradiated with active energy rays (more specifically, ultraviolet light, etc.) to polymerize the polymeric liquid crystal compound while maintaining its horizontal orientation relative to the coating plane, thereby forming a horizontally oriented liquid crystal cured film. As a polymerization method, methods similar to those used in the manufacture of light-absorbing anisotropic films can be cited.

[0432] The thickness of the horizontally oriented retardation film ii is preferably 0.1 to 3 μm, more preferably 0.2 to 2 μm. If the thickness of film ii is within the aforementioned range, the transmittance in the front direction is excellent, and the anti-reflection performance is also excellent. In addition, the laminate can be made thinner.

[0433] For the horizontally oriented phase difference film ii, its surface can be subjected to surface treatments known in the art, such as plasma treatment, corona treatment, ozone treatment, and ultraviolet irradiation treatment.

[0434] In one embodiment of the invention, the horizontally aligned retardation film ii and the side of the polarizer opposite to the horizontally aligned retardation film i (described later) are adjacent. The horizontally aligned retardation film ii can be laminated, for example, by directly coating a polymeric liquid crystal composition onto the side of the polarizer opposite to the horizontally aligned retardation film i. Alternatively, lamination can be performed via an adhesive layer or bonding agent layer. Alternatively, the substrate and / or the alignment film can be peeled off after lamination, leaving only the horizontally aligned retardation film i laminated.

[0435] In another embodiment of the invention, the horizontally oriented retardation film ii may also be adjacent to a vertically oriented retardation film iii, which may be further included in the laminate. In this case, the horizontally oriented retardation film ii may also be laminated by directly coating a polymeric liquid crystal composition onto, for example, the vertically oriented retardation film iii. Alternatively, lamination may be performed via an adhesive layer or a bonding agent layer.

[0436] Polarizing film

[0437] Examples of polarizers include, for example, a stretched film that adsorbs a pigment with anisotropic absorption properties, and a film comprising a film coated with a pigment with anisotropic absorption properties. Examples of pigments with anisotropic absorption properties include, for example, dichroic pigments.

[0438] A stretched film adsorbed with anisotropic pigments is typically manufactured by clamping a polarizer with a transparent protective film via an adhesive on at least one side of the polarizer, which is manufactured by the following steps: uniaxial stretching of a polyvinyl alcohol (PVA) resin film; dyeing the PVA resin film with a dichroic pigment to adsorb the dichroic pigment; treating the PVA resin film adsorbed with the dichroic pigment with an aqueous boric acid solution; and washing with water after treatment with the aqueous boric acid solution.

[0439] Polyvinyl alcohol-based resins can be obtained by saponifying polyvinyl acetate-based resins. Besides polyvinyl acetate as a homopolymer of vinyl acetate, copolymers of vinyl acetate with other monomers that can be copolymerized with it can also be used as polyvinyl acetate-based resins. Examples of other monomers that can be copolymerized with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides containing ammonium groups.

[0440] The degree of saponification of polyvinyl alcohol (PVA) resins is typically around 85–100 mol%, preferably 98 mol% or higher. PVA resins can be modified; for example, aldehyde-modified PVA formal or PVA acetal can be used. The degree of polymerization of PVA resins is typically around 1,000–10,000, preferably in the range of 1,500–5,000.

[0441] Films made from such polyvinyl alcohol (PVA) resins can be used as preforms for polarizing films. There are no particular limitations on the method for preparing the PVA film; known methods can be used. The thickness of the PVA preform can be, for example, around 10–150 μm.

[0442] Uniaxial stretching of polyvinyl alcohol (PVA) resin films can be performed before, during, or after dyeing with dichroic pigments. When uniaxial stretching is performed after dyeing, it can be done before or during boric acid treatment. Alternatively, uniaxial stretching can be performed at multiple stages. Uniaxial stretching can be performed between rollers with different circumferential speeds or using heated rollers. Furthermore, uniaxial stretching can be dry stretching performed in the atmosphere or wet stretching performed while the PVA resin film is swollen with a solvent. The stretching ratio is typically around 3 to 8 times.

[0443] The dyeing of polyvinyl alcohol-based resin films based on dichroic pigments can be carried out, for example, by impregnating the polyvinyl alcohol-based resin film in an aqueous solution containing dichroic pigments.

[0444] Specifically, iodine and dichroic organic dyes can be used as dichroic pigments. Examples of dichroic organic dyes include dichroic direct dyes formed from diazo compounds such as Direct Red 39, and dichroic direct dyes formed from compounds such as triazo and tetraazo. For polyvinyl alcohol-based resin films, it is preferable to pre-treat them by immersion in water before dyeing.

[0445] When using iodine as a dichroic pigment, the dyeing method is usually carried out by impregnating a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide.

[0446] The iodine content in this aqueous solution is typically about 0.01 to 1 part by weight relative to 100 parts by weight of water. Additionally, the potassium iodide content is typically about 0.5 to 20 parts by weight relative to 100 parts by weight of water. The temperature of the aqueous solution used for staining is typically about 20 to 40°C. Furthermore, the immersion time (staining time) in this aqueous solution is typically about 20 to 1,800 seconds.

[0447] On the other hand, when using dichroic organic dyes as dichroic pigments, a dyeing method can usually be adopted by impregnating a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye.

[0448] The content of dichroic organic dye in this aqueous solution is typically 1 × 10⁻⁶ parts by weight of water. -4 Approximately 10 parts by weight, preferably 1×10 -3 ~1 part by weight, more preferably 1×10 -3 ~1×10 -2Parts by weight. This aqueous solution may contain inorganic salts such as sodium sulfate as dyeing auxiliaries. The temperature of the aqueous solution of dichroic dyes used for dyeing is usually around 20–80°C. In addition, the immersion time (dyeing time) in this aqueous solution is usually around 10–1,800 seconds.

[0449] Boric acid treatment following dyeing with dichroic pigments is typically carried out by immersing the dyed polyvinyl alcohol-based resin film in an aqueous boric acid solution. The boric acid content in this aqueous solution is typically about 2 to 15 parts by weight relative to 100 parts by weight of water, preferably 5 to 12 parts by weight. When iodine is used as the dichroic pigment, the aqueous boric acid solution preferably contains potassium iodide, typically at a content of about 0.1 to 15 parts by weight relative to 100 parts by weight of water, preferably 5 to 12 parts by weight. The immersion time in the aqueous boric acid solution is typically about 60 to 1,200 seconds, preferably 150 to 600 seconds, more preferably 200 to 400 seconds. The temperature for boric acid treatment is typically above 50°C, preferably 50 to 85°C, more preferably 60 to 80°C.

[0450] Typically, boric acid-treated polyvinyl alcohol (PVA) resin membranes can be washed with water. This washing process can be performed, for example, by immersing the boric acid-treated PVA resin membrane in water. The water temperature during the washing process is usually around 5–40°C.

[0451] In addition, the soaking time is usually around 1 to 120 seconds.

[0452] The polarizer can be dried after washing to obtain a polarizing film. Drying can be performed using, for example, a hot air dryer or a far-infrared heater. The drying temperature is typically around 30–100°C, preferably 50–80°C. The drying time is typically around 60–600 seconds, preferably 120–600 seconds. Through drying, the moisture content of the polarizer can be reduced to a practical level. Its moisture content is typically around 5–20% by mass, preferably 8–15% by weight. If the moisture content is within the above range, a polarizer with moderate flexibility and excellent thermal stability can be obtained.

[0453] The thickness of the polarizer obtained by the above method is preferably 5 to 40 μm. It is usually 20 μm or less, preferably 5 μm or less, and more preferably 0.5 to 3 μm.

[0454] Examples of films made by coating with anisotropic pigments include films made by coating a composition containing a dichroic pigment having liquid crystal properties, or a composition containing a dichroic pigment and a polymerizable liquid crystal.

[0455] The thinner the film coated with an anisotropic pigment, the better; however, if it is too thin, there is a tendency for reduced strength and poor processability. The thickness of the film is typically 20 μm or less, preferably 5 μm or less, and more preferably 0.5 to 3 μm.

[0456] Specifically, the film described in Japanese Patent Application Publication No. 2012-33249, etc., is an example of a film coated with an anisotropic pigment.

[0457] In the laminate of the present invention, the aforementioned polarizer and the aforementioned horizontally oriented phase difference film i are preferably laminated by an adhesive or bonding agent (hereinafter, adhesives and bonding agents are sometimes referred to together as "adhesive bonding agents").

[0458] Examples of adhesives include pressure-sensitive adhesives, drying-curing adhesives, and chemically reactive adhesives. Examples of chemically reactive adhesives include, for instance, adhesives that cure under active energy radiation.

[0459] Pressure-sensitive adhesives typically contain polymers and may also contain solvents. Examples of polymers include acrylic polymers, silicone polymers, polyesters, polyurethanes, or polyethers. Among these, acrylic adhesives containing acrylic polymers are preferred due to their excellent optical transparency, moderate wetting properties, cohesive strength, and excellent adhesion. Furthermore, they exhibit high weather resistance and heat resistance, and are less prone to warping or peeling under heating or humidifying conditions.

[0460] As an acrylic polymer, preferred are (meth)acrylates with alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, or butyl, and copolymers formed with (meth)acrylate monomers having functional groups, such as (meth)acrylic acid or hydroxyethyl (meth)acrylate.

[0461] Pressure-sensitive adhesives containing such copolymers exhibit excellent adhesion and can be easily removed from the substrate without leaving residue, thus being preferred. The glass transition temperature of the acrylic polymer is preferably 25°C or lower, more preferably 0°C or lower. The mass-average molecular weight of such acrylic polymers is preferably 100,000 or higher.

[0462] As a solvent, the solvents described above in <Anisotropic Films for Light Absorption> can also be used. Pressure-sensitive adhesives may contain light-diffusing agents. Light-diffusing agents are additives that impart light-diffusing properties to the adhesive; any particle having a refractive index different from that of the polymer contained in the adhesive is acceptable. Examples of light-diffusing agents include particles formed from inorganic compounds and particles formed from organic compounds (polymers). Most polymers contained in the adhesive as an active ingredient, including acrylic polymers, have a refractive index of approximately 1.4 to 1.6; therefore, it is preferable to appropriately select light-diffusing agents with a refractive index of 1.2 to 1.8. The refractive index difference between the polymer contained in the adhesive as an active ingredient and the light-diffusing agent is typically 0.01 or more, and preferably 0.01 to 0.2 from the viewpoint of brightness and display performance of the display device. The particles used as light-diffusing agents are preferably spherical particles and nearly monodisperse particles, more preferably particles with an average particle size of 2 to 6 μm. The refractive index can be measured using the conventional minimum deviation angle method or an Abbe refractometer.

[0463] Examples of particles formed from inorganic compounds include alumina (refractive index 1.76) and silicon dioxide (refractive index 1.45). Examples of particles formed from organic compounds (polymers) include melamine beads (refractive index 1.57), polymethyl methacrylate beads (refractive index 1.49), methyl methacrylate / styrene copolymer resin beads (refractive index 1.50–1.59), polycarbonate beads (refractive index 1.55), polyethylene beads (refractive index 1.53), polystyrene beads (refractive index 1.6), polyvinyl chloride beads (refractive index 1.46), and silicone resin beads (refractive index 1.46). The content of the light diffusing agent is typically 3–30 parts by mass relative to 100 parts by mass of the polymer.

[0464] The thickness of the pressure-sensitive adhesive can be determined based on its adhesion strength, etc., and is therefore not particularly limited, typically ranging from 1 μm to 40 μm. Considering processability, durability, etc., this thickness is preferably 3 μm to 25 μm, more preferably 5 μm to 20 μm. By making the adhesive layer formed by the adhesive 5 μm to 20 μm thick, the brightness of the display device can be maintained when viewed from the front, and smudges or blurring of the displayed image are less likely to occur.

[0465] Dry-curing adhesives may contain solvents. Examples of dry-curing adhesives include compositions containing polymers or polyurethane resins as main components, which are monomers having proton functional groups such as hydroxyl, carboxyl, or amino groups and olefinic unsaturated groups, and further contain crosslinking agents or curing compounds such as polyaldehydes, epoxy compounds, epoxy resins, melamine compounds, zirconium oxide compounds, and zinc compounds. Examples of polymers containing monomers having proton functional groups such as hydroxyl, carboxyl, or amino groups and olefinic unsaturated groups include ethylene-maleic acid copolymers, itaconic acid copolymers, acrylic acid copolymers, acrylamide copolymers, saponified polyvinyl acetate, and polyvinyl alcohol resins.

[0466] Examples of polyvinyl alcohol (PVA)-based resins include polyvinyl alcohol, partially saponified PVA, fully saponified PVA, carboxyl-modified PVA, acetyl-modified PVA, hydroxymethyl-modified PVA, and amino-modified PVA. The content of PVA-based resin in an aqueous adhesive is typically 1 to 10 parts by weight relative to 100 parts by weight of water, preferably 1 to 5 parts by weight.

[0467] Examples of polyurethane resins include polyester-based ion-crosslinked polymer polyurethane resins.

[0468] The polyester-based ion-crosslinked polymer polyurethane resin referred to here is a polyurethane resin with a polyester backbone, in which a small amount of ionic components (hydrophilic components) are introduced. This ion-crosslinked polymer polyurethane resin emulsifies in water to form an emulsion without the use of an emulsifier, thus enabling the production of water-based adhesives. When using polyester-based ion-crosslinked polymer polyurethane resin, it is effective to use a water-soluble epoxy compound as a crosslinking agent.

[0469] Examples of epoxy resins include polyamide epoxy resins obtained by reacting epichlorohydrin with polyamide polyamines obtained by reacting polyalkylene polyamines such as diethylenetriamine or triethylenetetramine with dicarboxylic acids such as adipic acid. Commercially available examples of such polyamide epoxy resins include "Sumirez resin (registered trademark) 650" and "Sumirezresin 675" (manufactured by Sumika Chemtex Co., Ltd.), and "WS-525" (manufactured by PMC Corporation of Japan). When incorporating epoxy resin, the amount added is typically 1 to 100 parts by weight, preferably 1 to 50 parts by weight, relative to 100 parts by weight of polyvinyl alcohol-based resin.

[0470] The thickness of the adhesive layer formed by the dry-curing adhesive is typically 0.001–5 μm, preferably 0.01–2 μm, and more preferably 0.01–0.5 μm. If the adhesive layer formed by the dry-curing adhesive is too thick, it is prone to having a poor appearance.

[0471] Active energy radiation-cured adhesives may contain solvents. Active energy radiation-cured adhesives are adhesives that cure upon exposure to active energy radiation. Examples of active energy radiation-cured adhesives include cationic polymerizable adhesives containing epoxy compounds and cationic polymerization initiators; free radical polymerizable adhesives containing acrylic curing components and free radical polymerization initiators; adhesives containing both cationic polymerizable curing components such as epoxy compounds and free radical polymerizable curing components such as acrylic compounds, and further containing both cationic polymerization initiators and free radical polymerization initiators; and adhesives that do not contain these polymerization initiators but can be cured by electron beam irradiation.

[0472] Preferably, the adhesives are either radioactively cured adhesives with free radical polymerization properties containing an acrylic curing component and a photoradical polymerization initiator, or radioactively cured adhesives with cationic polymerization properties containing an epoxy compound and a photocationic polymerization initiator. Examples of acrylic curing components include methyl methacrylate, hydroxyethyl methacrylate, and other methacrylates and methacrylic acid. Radioactively cured adhesives containing epoxy compounds may also contain compounds other than epoxy compounds. Examples of compounds other than epoxy compounds include oxetane compounds and acrylic compounds.

[0473] Examples of photoradical polymerization initiators and photocationic polymerization initiators include the aforementioned photoradical polymerization initiators and photocationic polymerization initiators. The content of the radical polymerization initiator and the cationic polymerization initiator is typically 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, relative to 100 parts by weight of the active energy ray-cured adhesive.

[0474] Active energy ray-cured adhesives may also contain ion traps, antioxidants, chain transfer agents, tackifiers, thermoplastic resins, fillers, flow modifiers, plasticizers, and defoamers.

[0475] In this specification, "active energy rays" are defined as energy rays capable of decomposing compounds that can produce active species to generate active species. Examples of such active energy rays include visible light, ultraviolet light, infrared light, X-rays, alpha rays, beta rays, gamma rays, and electron beams, with ultraviolet light and electron beams being preferred. The preferred ultraviolet irradiation conditions are the same as those for the polymerization of the aforementioned polymerizable liquid crystal compounds.

[0476] Preferably, the laminate of the present invention further includes a transparent protective film on the side of the aforementioned anisotropic light-absorbing film opposite to the horizontally oriented phase difference film i. By including the transparent protective film in the laminate of the present invention, dimensional changes, cracks, and fissures caused by heat and / or humidity in the anisotropic light-absorbing film or other layers can be prevented. In addition, it can prevent deterioration when exposed to ultraviolet light, etc., and can prevent damage and deterioration of the surface of the anisotropic light-absorbing film during storage and transportation.

[0477] As a transparent protective film, a transparent film that allows light, especially visible light, to pass through is preferred, and a film that has a transmittance of 80% or more for light in the wavelength range of 380 to 780 nm is even more preferred. As a transparent protective film, for example, the same film exemplified above as a resin substrate that can be used to manufacture anisotropic light-absorbing films can be preferably used.

[0478] The thickness of the transparent protective film is preferably 3 to 20 μm, more preferably 5 to 15 μm. If the thickness of the transparent protective film is within the aforementioned range, the surface of the light-absorbing anisotropic film can be adequately protected. In addition, it becomes possible to achieve a thinner laminate.

[0479] A transparent protective film can be laminated onto a light-absorbing anisotropic film via an adhesive. The adhesives exemplified above can also be used as applicable adhesives.

[0480] <Vertical Orientation Phase Difference Film iii>

[0481] The laminate of the present invention preferably further comprises a vertically oriented phase retardation film iii (hereinafter, sometimes simply referred to as "film iii").

[0482] In this invention, a vertically oriented retardation film refers to a retardation film oriented in a vertical direction relative to the film plane. Examples of vertically oriented retardation films include stretch films, cured products of polymeric liquid crystal compositions containing polymeric liquid crystal compounds, and cured products formed by curing polymeric liquid crystal compounds in a state of vertical orientation relative to the retardation film plane (hereinafter also referred to as "vertically oriented liquid crystal cured films").

[0483] The vertically oriented phase difference film iii satisfies the following equation (10):

[0484] -100nm≤Rth iii (550)≤-20nm (10),

[0485] The preferred option further satisfies equation (11):

[0486] Rth iii (450) / Rth iii(550)>1.00 (11)

[0487] In equations (10) and (11), Rth iii (λ) represents the thickness phase difference value of the vertically oriented phase difference film iii at wavelength λnm.

[0488] Here, the thickness phase difference Rth iii (λ) is Rth iii (λ)=((nx iii (λ)+ny iii (λ)) / 2-nz iii (λ))×d iii (Here, in the formula, nx) iii (λ) represents the in-plane principal refractive index of the vertically oriented phase retardation film iii at wavelength λnm, ny iii (λ) represents the expression at wavelength λnm, which is related to nx. iii (λ) Refractive index in the orthogonal directions in the plane, nz iii (λ) represents the refractive index in the thickness direction of the vertically oriented phase difference film iii at wavelength λnm, in nx iii (λ)=ny iii In the case of (λ), nx iii (λ) can be the refractive index in any direction within the film surface, d iii (This represents the thickness of the vertically oriented phase difference film iii).

[0489] If the laminate of the present invention includes the aforementioned film iii, it exhibits excellent transmittance in the frontal direction and reduces the directional anisotropy of light absorption characteristics in the oblique direction, resulting in excellent anti-viewing performance from the oblique direction. Furthermore, it easily improves the oblique reflection hue during black display when the laminate including film iii is assembled into an organic EL display device. Therefore, when the laminate of the present invention is applied to an organic EL display device, the anti-reflection effect is also excellent. Thickness phase difference Rth iii (550) More preferably, -90nm≤Rth iii (550)≤-30nm, further preferably within the range of -80nm≤Rth iii Within the range of (550)≤-40nm. Regarding the thickness phase difference Rth of film iii. iii (550) In this regard, the above-mentioned range can be adjusted appropriately by, for example, the type and / or composition ratio of the polymeric liquid crystal compound contained in film iii; the thickness of film iii; the type and / or amount of additives contained in film iii; and the manufacturing conditions of film iii. The thickness phase difference Rth of film iii iii(550) The phase difference can be measured using a phase difference measuring device, for example, by using the method described in the embodiments described later.

[0490] The vertically oriented retardation film iii preferably contains a cured polymeric liquid crystal composition comprising at least one polymeric liquid crystal compound. If film iii is a film formed from a cured polymeric liquid crystal composition comprising at least one polymeric liquid crystal compound, it has an excellent effect on improving oblique reflection hue, and when the laminate containing film iii is applied to an organic EL display device, it also has an excellent anti-reflection effect.

[0491] As the polymerizable liquid crystal compound, the same compound that can be included in the aforementioned light-absorbing anisotropic film can be used.

[0492] Regarding the content of the polymeric liquid crystal compound in the polymeric liquid crystal composition used to form the vertically aligned retardation film iii, it 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 even more preferably 90 to 95 parts by mass, relative to 100 parts by mass of the solid component of the polymeric liquid crystal composition. When the content of the polymeric liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the resulting cured liquid crystal film.

[0493] The polymeric liquid crystal composition used to form the vertically aligned retardation film iii may include, in addition to the polymeric liquid crystal compound, additives such as solvents, photopolymerization initiators, leveling agents, antioxidants, and photosensitizers. Examples of these components include those exemplified above as components that may be included in the light-absorbing anisotropic film; each component may be used individually or in combination of two or more.

[0494] Vertically oriented retardation film iii can be manufactured, for example, by a method including the following steps:

[0495] A process is described in which a polymeric liquid crystal compound and additives such as solvents used as appropriate are stirred at a specified temperature to obtain a polymeric liquid crystal composition for forming a vertically oriented phase difference film iii.

[0496] The process of coating the aforementioned polymeric liquid crystal composition onto a substrate or alignment film to obtain a coating film;

[0497] The process of drying the aforementioned coating to form a dried coating film; and,

[0498] The process of forming a vertically oriented liquid crystal curing film by irradiating a dry coating with active energy rays.

[0499] The coating of the polymeric liquid crystal composition used to form the vertically aligned retardation film iii can be formed by coating the polymeric liquid crystal composition, for example, onto a substrate or an alignment film. The substrate that can be used here is the same substrate exemplified above as a substrate that can be used to manufacture anisotropic light-absorbing films.

[0500] The alignment film can be appropriately selected from materials having a vertical alignment control force that aligns the polymeric liquid crystal compound in a direction perpendicular to the coating plane. The alignment control force can be arbitrarily adjusted by the type of alignment layer, surface condition, friction conditions, etc., and in the case of a photo-alignable polymer, it can be arbitrarily adjusted by polarized light irradiation conditions, etc. Examples of such materials include, for instance, the alignment polymers described above that can be used to manufacture anisotropic light-absorbing films. A vertically aligned film can be obtained by coating a composition containing such a material and a solvent (e.g., the solvent exemplified in anisotropic light-absorbing films) onto a substrate, removing the solvent, and then heating the coated film. From a quality perspective, a photo-alignable film is preferred as a vertically aligned film.

[0501] Next, the solvent is removed by drying, thereby forming a dried coating film. Regarding the drying method and conditions, the same drying method and conditions that can be used in the manufacturing method of the light absorption anisotropic film can be cited.

[0502] The obtained dried coating is irradiated with active energy rays (more specifically, ultraviolet light, etc.) to polymerize the polymeric liquid crystal compound while maintaining its orientation perpendicular to the coating plane, thereby forming a vertically oriented liquid crystal cured film. As a polymerization method, methods similar to those used in the manufacture of anisotropic light-absorbing films can be cited.

[0503] The thickness of the vertically oriented retardation film iii is preferably 0.2 to 3 μm, more preferably 0.2 to 2 μm. If the thickness of film iii is within the aforementioned range, the laminate of the present invention exhibits excellent effect in improving oblique reflection hue, and when applied to organic EL display devices, it also provides excellent anti-reflection performance. Furthermore, the laminate can be made thinner.

[0504] For the vertically oriented retardation film iii, its surface can be subjected to surface treatments known in the art, such as plasma treatment, corona treatment, ozone treatment, and ultraviolet irradiation treatment.

[0505] The aforementioned vertically oriented retardation film iii is preferably laminated between the aforementioned polarizer and the aforementioned horizontally oriented retardation film ii, or on the side of the aforementioned horizontally oriented retardation film ii opposite to the polarizer. When film iii is laminated on the side of the aforementioned horizontally oriented retardation film ii opposite to the polarizer, there is a tendency for a superior anti-reflection effect. In one embodiment of the invention, film iii is preferably laminated on the side of the horizontally oriented retardation film ii opposite to the polarizer.

[0506] Organic EL Display Device

[0507] The laminate of the present invention can be used in various display devices.

[0508] A display device is a device that has display elements, including light-emitting elements or devices as light sources. Examples of display devices include liquid crystal displays (LCDs), organic electroluminescent (EL) displays, inorganic electroluminescent (EL) displays, touch panel displays, electron emission displays (e.g., field emission displays (FEDs) and surface electric field emission displays (SEDs)), electronic paper (displays using electronic ink or electrophoretic elements), plasma displays, projection displays (e.g., grating light valve (GLV) displays and displays with digital micromirror devices (DMDs)), and piezoelectric ceramic displays. Liquid crystal displays also include transmissive liquid crystal displays, semi-transmissive liquid crystal displays, and reflective liquid crystal displays. This invention relates to any of the following: liquid crystal display devices, direct-view liquid crystal display devices, and projective liquid crystal display devices. These display devices can be either display devices for displaying two-dimensional images or stereoscopic display devices for displaying three-dimensional images. In particular, considering the ease with which its effects can be significantly realized, the laminate of this invention is suitable for use in organic electroluminescent (EL) display devices, and the laminate of this invention is suitable for use in liquid crystal display devices and touch panel display devices. These display devices exhibit excellent transmittance in the frontal direction and reduced directional anisotropy of light absorption characteristics in the tilt direction, thus providing excellent protection against viewing from the tilt direction.

[0509] Example

[0510] The present invention will be described in more detail below using examples. It should be noted that, unless otherwise specified, "%" and "parts" in the examples refer to mass % and mass parts, respectively.

[0511] Example 1

[0512] 1. Fabrication of anisotropic light-absorbing films

[0513] (1) Manufacturing of light-absorbing anisotropic compositions

[0514] The following components were mixed and stirred at 80°C for 1 hour to obtain an anisotropic light absorption composition. For the dichroic pigment, the azo pigment described in the examples of Japanese Patent Application Publication No. 2013-101328 was used. The following polymerizable liquid crystal compound was synthesized according to the method described in lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996).

[0515] Polymerizable liquid crystal compound 1:

[0516] [Chemical Formula 31]

[0517]

[0518] 75 copies

[0519] Polymerizable liquid crystal compound 2:

[0520] [Chemical Formula 32]

[0521]

[0522] 25 copies

[0523] Dichroic pigment 1:

[0524] [Chemical Formula 33]

[0525]

[0526] 2.8 copies

[0527] Dichroic pigment 2:

[0528] [Chemical Formula 34]

[0529]

[0530] 2.8 copies

[0531] Dichroic pigment 3:

[0532] [Chemical Formula 35]

[0533]

[0534] 2.8 copies

[0535] Polymerization initiator:

[0536] 2-Dimethylamino-2-benzyl-1-(4-morpholinophenyl)butane-1-one (Irgacure 369; manufactured by CibaSpecialty Chemicals Inc.) 6 parts

[0537] Leveling agent:

[0538] Polyacrylate compound (BYK-361N; manufactured by BYK-Chemie) 0.3 parts Solvent: 250 parts o-xylene

[0539] (2) Determination of the phase transition temperature of polymeric liquid crystal compounds

[0540] The phase transition temperatures were confirmed by textural observation using a polarizing microscope (BX-51, Olympus) while the compounds were heated on a glass substrate with an oriented film. Polymerizable liquid crystal compound 1 transitioned from a crystalline phase to a smectic A phase at 95°C, to a nematic phase at 111°C, and to an isotropic liquid phase at 113°C upon heating. Upon cooling, it was confirmed that it transitioned to a nematic phase at 112°C, to a smectic A phase at 110°C, and to a smectic B phase at 94°C. Polymerizable liquid crystal compound 2 transitioned from a crystalline phase to a smectic A phase at 81°C, to a nematic phase at 121°C, and to an isotropic liquid phase at 137°C upon heating. Upon cooling, it was confirmed that it transitioned to a nematic phase at 133°C, to a smectic A phase at 118°C, and to a smectic B phase at 78°C. The same procedure was followed to observe the texture of BASF's thermotropic nematic liquid crystal LC242. LC242 exhibited a nematic phase but not a smectic phase.

[0541] (3) Preparation of the composition for forming an orientation film

[0542] Propylene glycol monomethyl ether is added to an orientation polymer to obtain a composition for forming an orientation film. The value in parentheses for the concentration of the solid component of the orientation polymer is obtained by converting the concentration described in the delivery specification into the amount of solid component.

[0543] Oriented polymer: SUNEVER (registered trademark) SE-610 (manufactured by Nissan Chemical Industries, Ltd.)

[0544] 0.3 parts (1.0%)

[0545] Propylene glycol monomethyl ether: 27.7 parts

[0546] (4) Fabrication of light-absorbing anisotropic films

[0547] A polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., Diafoil T140E25) was subjected to corona treatment. After applying an alignment film forming composition to the corona-treated film surface using a bar coater, it was dried in a drying oven set to 120°C for 1 minute to obtain an alignment film. A light-absorbing anisotropic composition was then applied to the obtained alignment film using a bar coater. After heating at 100°C for 60 seconds, the dried film was allowed to cool naturally to room temperature. The film was then irradiated with ultraviolet light (cumulative light intensity at 365nm wavelength: 1000mJ / cm² under nitrogen atmosphere) from the surface coated with the light-absorbing anisotropic composition using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by USHIO INC.). 2 Thus, an anisotropic light absorption film 1 was obtained.

[0548] (5) Evaluation of anisotropic light absorption films

[0549] [Three-dimensional absorbance measurement]

[0550] For the light-absorbing anisotropic film 1, the absorbance was measured as described below.

[0551] Using a spectrophotometer (Shimadzu Corporation UV-3150) with a support featuring a prism polarizer, the three-dimensional absorbance at wavelengths exhibiting maximum absorption was measured in 2 nm steps within the wavelength range of 380–680 nm using the two-beam method. Here, three-dimensional absorbance refers to the absorbance (Ax, Ay, Az) in each direction for linearly polarized light, with any direction within the film surface defined as the x-axis, the direction orthogonal to the x-axis as the y-axis, and the film thickness direction as the z-axis. Specifically, for linearly polarized light used as the measurement light, the measurement was performed by rotating the sample. Furthermore, the absorbance in the z-direction is difficult to measure because light is incident from the side of the sample. Therefore, the sample's xy-plane was tilted by 60° relative to the plane of vibration of the linearly polarized light used as the measurement light, and the absorbance in the Az-direction was calculated accordingly.

[0552] Specifically, with the sample rotated 60° including the y-axis, linearly polarized light, the same as that used when measuring Ax, was incident on the sample, and Ax (z = 60°) was measured. Similarly, with the sample rotated 60° including the x-axis, linearly polarized light, the same as that used when measuring Ay, was incident on the sample, and Ay (z = 60°) was measured.

[0553] Note that in the case where there is no absorption anisotropy in the x-y plane, that is, when Ax and Ay are equal, Ax(z = 60°) = Ay(z = 60°). Therefore, Ax(z = 60°) and Ay(z = 60°) are denoted as A(z = 60°).

[0554] The light absorption anisotropic film of the present application satisfies the relationship A(z = 60°) < A(z = 90°) = Az. In addition, if A(z = 60) > (Ax + Ay) / 2, then the following formula (1) must be satisfied.

[0555] Az > (Ax + Ay) / 2 (1)

[0556] The three-dimensional absorbance of the light absorption anisotropic film 1 was measured, and as a result, maximum absorption from three kinds of pigments was obtained.

[0557] First absorption:

[0558] The three-dimensional absorbance at a wavelength of 400 nm is: Ax = 0.115, Ay = 0.115, A(z = 60°) = 0.692.

[0559] That is, the light absorption anisotropic film satisfies formulas (1), (2), and (3) as follows.

[0560] Az > A(z = 60°) > (Ax + Ay) / 2 (1)

[0561] Ax(z = 60°) / Ax = 6.0 > 5 (2)

[0562] Ay(z = 60°) / Ay = 6.0 > 5 (3)

[0563] Second absorption:

[0564] The three-dimensional absorbance at a wavelength of 526 nm is: Ax = 0.062, Ay = 0.062, A(z = 60) = 0.639.

[0565] That is, the light absorption anisotropic film satisfies formulas (1), (2), and (3) as follows.

[0566] Az > A(z = 60°) > (Ax + Ay) / 2 (1)

[0567] Ax(z = 60°) / Ax = 10.2 > 5 (2)

[0568] Ay(z = 60°) / Ay = 10.2 > 5 (3)

[0569] Third absorption:

[0570] The three-dimensional absorbance at a wavelength of 622 nm is: Ax = 0.049, Ay = 0.049, A(z = 60) = 0.468.

[0571] That is, the light-absorbing anisotropic film satisfies equations (1), (2), and (3) as follows.

[0572] Az>A(z=60°)> (Ax+Ay) / 2 (1)

[0573] Ax(z=60°) / Ax = 11.3 > 5 (2)

[0574] Ay(z=60°) / Ay = 11.3 > 5 (3)

[0575] [Film thickness measurement]

[0576] The thickness of the liquid crystal cured film in the light-absorbing anisotropic film 1 was measured using a laser microscope (LEXT, manufactured by Olympus Corporation), and the result was 2.3 μm.

[0577] 2. Polarizing film manufacturing

[0578] A polyvinyl alcohol (PVA) film with an average degree of polymerization of approximately 2,400, a saponification degree of ≥99.9 mol%, and a thickness of 75 μm was immersed in pure water at 30°C. Then, it was immersed in an aqueous solution of iodine / potassium iodide / water at a weight ratio of 0.02 / 2 / 100 at 30°C for iodine staining (iodine staining step). The iodine-stained PVA film was then immersed in an aqueous solution of potassium iodide / boric acid / water at a weight ratio of 12 / 5 / 100 at 56.5°C for boric acid treatment (boric acid treatment step). The boric acid-treated PVA film was washed with pure water at 8°C and then dried at 65°C to obtain a horizontally polarized film with iodine adsorbed and oriented on the PVA (stretched thickness of 27 μm). At this point, stretching was performed in the iodine staining and boric acid treatment steps. The total stretching ratio in this stretching was 5.3 times.

[0579] 3. Fabrication of horizontally oriented phase retardation film i

[0580] (1) Fabrication of horizontally oriented phase retardation film i

[0581] An unstretched film made of norbornene resin with a glass transition temperature (Tg) of 125°C and a thickness of 40 μm was uniaxially stretched transversely by approximately 1.5 times under an atmosphere of 128°C to obtain a roll-shaped phase reversal film with a thickness of 30 μm. The uniaxial stretching was performed using a tenter frame. This film is designated as stretched film A.

[0582] The in-plane phase difference Re(λ) of the horizontally oriented retardation film manufactured by the above method was measured using a measuring machine ("KOBRA-WPR", manufactured by Oji Measurement & Control Co., Ltd.). The phase difference Re(λ) at each wavelength was measured, and the results showed that the in-plane phase difference Re(550) of the retardation film i was 100 nm, and the in-plane phase difference Re(450) was 103 nm. Furthermore, the slow axis was oriented at 90° to the longitudinal direction of the film.

[0583] 4. Fabrication of horizontally oriented phase retardation film II

[0584] (1) Preparation of compositions for horizontally oriented film formation

[0585] Five parts of a photo-oriented material with the following structure (weight average molecular weight: 30,000) and 95 parts of cyclopentanone (solvent) were mixed as components, and the resulting mixture was stirred at 80°C for 1 hour to obtain a composition for forming a horizontally oriented film.

[0586] [Chemical Formula 36]

[0587]

[0588] (2) Preparation of polymeric liquid crystal compounds

[0589] Polymerizable liquid crystal compounds (X1) and (X2) having the following molecular structures were prepared separately. Polymerizable liquid crystal compound (X1) was manufactured according to the method described in Japanese Patent Application Publication No. 2010-31223. Polymerizable liquid crystal compound (X2) was manufactured according to the method described in Japanese Patent Application Publication No. 2009-173893. These polymerizable liquid crystal compounds were combined to form polymerizable liquid crystal compound 3.

[0590] Polymerizable liquid crystal compound (X1)

[0591] [Chemical Formula 37]

[0592]

[0593] Polymerizable liquid crystal compound (X2)

[0594] [Chemical Formula 38]

[0595]

[0596] 1 mg of polymeric liquid crystal compound (X1) was dissolved in 50 mL of tetrahydrofuran to obtain a solution. The obtained solution was placed in a measuring cuvette with an optical path length of 1 cm as the sample for measurement. The measuring cuvette was then placed in a UV-Vis spectrophotometer (Shimadzu Corporation "UV-2450") to measure the absorption spectrum. The wavelength of maximum absorbance was read from the obtained absorption spectrum. As a result, the maximum absorption wavelength λmax in the wavelength range of 300-400 nm was 350 nm.

[0597] (3) Preparation of polymeric liquid crystal composition for forming horizontally oriented phase retardation film ii

[0598] Polymerizable liquid crystal compound (X1) and polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. 0.1 parts by mass of leveling agent "BYK-361N" (manufactured by BM Chemie) and 6 parts by mass of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butane-1-one (manufactured by BASF Japan Ltd. as "Irgacure (registered trademark) 369 (Irg369)") as a photopolymerization initiator were added relative to 100 parts by mass of the obtained mixture. Further, N-methyl-2-pyrrolidone (NMP) was added at a solid content concentration of 13%. The mixture was stirred at 80°C for 1 hour, thereby obtaining a polymerizable liquid crystal composition for forming a horizontally oriented phase retardation film II.

[0599] (4) Fabrication of horizontally oriented phase retardation film II

[0600] After corona treatment on a COP film (ZF-14-50) manufactured by Zeon Co., Ltd. in Japan, a horizontally oriented film-forming composition was coated using a bar coater, dried at 80°C for 1 minute, and then irradiated with polarized UV light (SPOT CURE SP-9; manufactured by USHIO INC.). The cumulative light intensity at a wavelength of 313 nm was 100 mJ / cm². 2 Under certain conditions, polarized UV light exposure was performed to obtain a horizontally aligned film. The thickness of the obtained horizontally aligned film was measured using an ellipsometer, and the result was 200 nm.

[0601] Next, using a rod coater, the polymeric liquid crystal composition for forming the horizontally aligned phase retardation film II was coated onto the horizontally aligned film. After heating at 120°C for 60 seconds, ultraviolet light (cumulative light intensity at 365nm wavelength: 500mJ / cm² under nitrogen atmosphere) was irradiated from the surface coated with the polymeric liquid crystal composition for forming the horizontally aligned phase retardation film II using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by USHIO INC.). 2Thus, a horizontally aligned retardation film ii is formed. After confirming that there is no retardation in the COP film, a corona treatment is performed on the liquid crystal side, and the film is bonded to the glass using a 25μm pressure-sensitive adhesive manufactured by LINTEC Corporation. The COP film is then peeled off. Re(450) and Re(550) are measured using a KOBRA-WPR manufactured by Oji Measurement Equipment Co., Ltd., in the same manner as the aforementioned horizontally aligned retardation film i, and αA = Re(450) / Re(550) is calculated.

[0602] 5. Construction of layered bodies

[0603] A horizontally oriented retardation film i is cut out at a 45-degree angle relative to the polarizer. One side is corona treated, and the resulting polarizer is bonded to the polarizer using a clamping roller via an aqueous adhesive. During bonding, the slow axis of the horizontally oriented retardation film i is kept at a 45-degree angle to the absorption axis of the polarizer. The resulting laminate is dried at 80°C for 3 minutes while being subjected to tension, resulting in a laminate with the horizontally oriented retardation film i on one side. It should be noted that the aforementioned aqueous adhesive is prepared by adding 3 parts of carboxyl-modified polyvinyl alcohol (KURARAY POVALKL318 manufactured by KURARAY) and 1.5 parts of water-soluble polyamide epoxy resin (Sumirez resin 650 aqueous solution with a solid component concentration of 30%) to 100 parts of water.

[0604] The liquid crystal cured film side of the obtained anisotropic light absorption film is bonded to the side of the horizontally aligned retardation film i opposite to the polarizer of the laminate using a pressure-sensitive adhesive. Furthermore, the coated side (liquid crystal layer side) of the horizontally aligned retardation film ii is bonded to the polarizer side of the laminate using a pressure-sensitive adhesive, thus forming a laminate. During bonding, the relative angle between the slow axis of the horizontally aligned retardation film ii and the absorption axis of the polarizer is 135 degrees. A laminate comprising the anisotropic light absorption film 1, the horizontally aligned retardation film i (stretched film A), the polarizer, and the horizontally aligned retardation film ii (cured polymeric liquid crystal composition) is obtained.

[0605] Example 2

[0606] 1. Fabrication of vertically oriented retardation film III

[0607] (1) Preparation of polymeric liquid crystal composition for vertically aligned phase retardation film iii

[0608] [Chemical Formula 39]

[0609]

[0610] Compared to 100 parts by mass of polymerizable liquid crystal compound 4 (LC242), 0.25 parts by mass of leveling agent "F-556" (manufactured by DIC Corporation), 2.0 parts by mass of ionic compound A (molecular weight: 645) prepared according to Japanese Patent Application No. 2016-514802, 0.5 parts by mass of silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.), and 6 parts by mass of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butane-1-one (manufactured by BASF Japan Ltd. as "Irgacure (registered trademark) 369 (Irg369)") as a photopolymerization initiator were added. Furthermore, N-methyl-2-pyrrolidone (NMP) was added at a solid content concentration of 13%. The mixture was stirred at 80°C for 1 hour, thereby obtaining a polymerizable liquid crystal composition for vertically oriented phase retardation film iii.

[0611] Ionic compound A:

[0612] [Chemical Formula 40]

[0613]

[0614] (2) Preparation of substrate

[0615] A solution was prepared by dissolving 50 parts by weight of dipentaerythritol hexaacrylate (ARONIX M-403, a multifunctional acrylate manufactured by Toa Synthetic Co., Ltd.), 50 parts by weight of acrylate resin (EBECRYL 4858, manufactured by Daicel-UCB Co., Ltd.), and 3 parts by weight of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one (Irgacure 907; manufactured by Ciba Specialty Chemicals Inc.) in 250 parts by weight of isopropanol to obtain a composition for forming a cured resin layer containing acrylate compounds.

[0616] Next, using a rod coater, the composition for forming the cured resin layer was applied onto a TAC film (KC4UY) manufactured by KONICA MINOLTA, INC., and dried at 50°C for 1 minute. Then, the film was irradiated with ultraviolet light (cumulative light intensity at 365nm wavelength: 400mJ / cm² under a nitrogen atmosphere) using a high-pressure mercury lamp (“Unicure VB-15201BY-A”, manufactured by USHIO INC.). 2This process forms a cured resin layer. The thickness of the cured resin layer was measured using a contact thickness gauge, and the result was 2.0 μm. At this point, the phase difference Re(550) between the TAC film and the cured resin layer laminate was measured using a "KOBRA-WPR" manufactured by Oji Measuring Instruments Co., Ltd. After subtracting the phase difference Re(550) from the TAC film, the phase difference was found to be less than 3 nm, confirming that it is optically isotropic.

[0617] (3) Fabrication of vertically aligned liquid crystal curing film

[0618] On the cured resin layer of the substrate prepared as described above, a polymeric liquid crystal composition for vertically aligned phase retardation film iii is coated using a bar coater and heated at 120°C for 60 seconds. Then, while heated to 120°C, ultraviolet light (cumulative light intensity at 365nm wavelength: 500mJ / cm² under nitrogen atmosphere) is irradiated from the surface coated with the polymeric liquid crystal composition for vertically aligned phase retardation film iii using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by USHIO INC.). 2 This forms a vertically oriented phase difference film. The thickness of the obtained liquid crystal layer was measured using an ellipsometer (M-220 manufactured by Nippon Spectrophotometer Co., Ltd.), and the result was 0.6 μm.

[0619] (4) Evaluation of vertically oriented liquid crystal curing film

[0620] [Determination of thickness phase difference]

[0621] The liquid crystal side of the vertically oriented retardation film iii, prepared by the aforementioned steps, was subjected to corona treatment and then bonded to glass using a 25μm pressure-sensitive adhesive manufactured by LINTEC. The TAC and cured resin layers were then peeled off. Using a KOBRA-WPR manufactured by Oji Measurement Instrument Co., Ltd., the phase difference value on the front side and the phase difference value when tilted 40° around the fast axis were measured by changing the incident angle of the sample for measuring optical properties.

[0622] The average refractive index at each wavelength was measured using an ellipsometer M-220 manufactured by Nippon Spectrophotometer Co., Ltd. The film thickness of the polymeric liquid crystal cured layer was measured using an Optical NanoGauge C12562-01 manufactured by Hamamatsu Photonics KK. Based on the aforementioned frontal phase difference value, phase difference value tilted at 40° around the fast axis, average refractive index, and film thickness, the three-dimensional refractive index was calculated with reference to the technical data of Oji Measurement Equipment (http: / / www.oji-keisoku.co.jp / products / kobra / reference.html). Based on the obtained three-dimensional refractive index, the optical properties of the vertically oriented phase difference film were calculated according to the following formula, yielding the values ​​of Rth(450), Rth(550), and Rth(450) / Rth(550).

[0623] RthC(λ)=((nxC(λ)+nyC(λ)) / 2-nzC(λ))×dC

[0624] It should be noted that RthC(λ) represents the phase difference value in the thickness direction of the vertically oriented retardation film at wavelength λnm. Additionally, nxC(λ) represents the in-plane principal refractive index of the vertically oriented retardation film at wavelength λnm, nyC(λ) represents the refractive index in the direction orthogonal to nxC(λ) in the plane at wavelength λnm, nzC(λ) represents the refractive index in the thickness direction of the vertically oriented retardation film at wavelength λnm. When nxC(λ) = nyC(λ), nxC(λ) can be the refractive index in any in-plane direction, and dC represents the film thickness of the vertically oriented retardation film.

[0625] 2. Fabrication of layered bodies

[0626] After corona treatment of the liquid crystal curing film side of the vertically oriented retardation film iii obtained above, it is bonded to the side opposite to the polarizer of the horizontally oriented retardation film ii of the laminate prepared in the same manner as in Example 1 by means of the pressure-sensitive adhesive. A laminate comprising light absorption anisotropic film 1, horizontally oriented retardation film i (stretched film A), polarizer, horizontally oriented retardation film ii (cured polymeric liquid crystal composition) and vertically oriented retardation film iii is prepared and evaluated.

[0627] Example 3

[0628] In Example 1, instead of the stretched film A used as the horizontally aligned retardation film i, the retardation film (cured polymeric liquid crystal composition) used as the horizontally aligned retardation film ii in Example 1 was used as the horizontally aligned retardation film i in Example 3. The liquid crystal surface of this film was subjected to corona treatment, and it was bonded to the obtained polarizer using an aqueous adhesive, similar to Example 1. After bonding, the COP was peeled off. Next, the liquid crystal cured film side of the obtained light-absorbing anisotropic film was bonded to the side of the horizontally aligned retardation film i (cured polymeric liquid crystal composition) of the laminate opposite to the polarizer using a pressure-sensitive adhesive. Furthermore, on the polarizer side of the laminate, a cured polymeric liquid crystal composition was bonded as the horizontally aligned retardation film ii, similar to Example 1, using a pressure-sensitive adhesive. A laminate comprising anisotropic light absorption film 1, horizontally oriented phase retardation film i (cured polymeric liquid crystal composition), polarizer, and horizontally oriented phase retardation film ii (cured polymeric liquid crystal composition) was fabricated and evaluated.

[0629] Example 4

[0630] In Example 1, instead of the cured polymeric liquid crystal composition used as the horizontally aligned retardation film ii, the following stretched film B was used as the horizontally aligned retardation film ii. Under an atmosphere of 128°C, a roll of unstretched film made of norbornene resin with an original thickness of 50 μm was uniaxially stretched laterally by approximately 1.5 times to obtain a roll of retardation film with a thickness of 40 μm. The resulting film had an in-plane retardation Re(550) of 140 nm and a Re(450) of 145 nm. Furthermore, the relative angle between the slow axis and the absorption axis of the polarizer during lamination was set to 45 degrees.

[0631] In Example 1, on the side of the horizontally oriented retardation film i opposite to the polarizer of the laminate of the horizontally oriented retardation film i and the polarizer, the liquid crystal curing film side of the light absorption anisotropic film is bonded together with a pressure-sensitive adhesive. Furthermore, on the polarizer side of the laminate, the aforementioned stretched film B, which has undergone corona treatment on one side, is bonded together with a pressure-sensitive adhesive as the horizontally oriented retardation film ii, thus fabricating the laminate. A laminate is thus obtained, sequentially comprising the light absorption anisotropic film 1, the horizontally oriented retardation film i (stretched film A), the polarizer, and the horizontally oriented retardation film ii (stretched film B).

[0632] Example 5

[0633] In the fabrication of the light-absorbing anisotropic film, relative to 100 parts by mass of polymerizable liquid crystal compound 4 (LC242), 0.25 parts by mass of leveling agent "F-556" (manufactured by DIC Corporation), 6 parts by mass of dichroic pigment 2, 1.5 parts by mass of ionic compound A (molecular weight: 645) prepared according to Japanese Patent Application No. 2016-514802, 0.5 parts by mass of silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), and 6 parts by mass of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butane-1-one (manufactured by BASF Japan Ltd. as "Irgacure (registered trademark) 369 (Irg369)") as a photopolymerization initiator. Furthermore, N-methyl-2-pyrrolidone (NMP) is added at a solid content concentration of 13%. The mixture was stirred at 80°C for 1 hour to obtain composition 2 for making anisotropic light-absorbing films.

[0634] To this end, corona treatment was performed on a COP film (ZF-14-50) manufactured by Zeon Corporation of Japan. The composition was coated using a bar coater, heated to 120°C for 60 seconds, and then irradiated with ultraviolet light (cumulative light intensity at 365nm wavelength: 500mJ / cm² under nitrogen atmosphere) from the coated surface using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by USHIO INC.). 2 This forms an anisotropic light-absorbing film 2. The resulting film has a thickness of 1.5 μm. The three-dimensional absorbance of the anisotropic light-absorbing film 2 was measured, and the maximum absorption wavelength was found to be 600 nm. Using the anisotropic light-absorbing film 2, a laminate was fabricated in the same manner as in Example 1. A laminate was obtained comprising, in sequence, the anisotropic light-absorbing film 2, a horizontally aligned retardation film i (stretched film A), a polarizer, and a horizontally aligned retardation film ii (a cured polymeric liquid crystal composition).

[0635] Comparative Example 1

[0636] As the horizontally oriented phase retardation film i, a TAC film (KC4UY) manufactured by KONICA MINOLTA, INC., which has undergone saponification treatment, was used. Otherwise, a laminate was prepared in the same manner as in Example 4 and evaluated.

[0637] Evaluation methods and results

[0638] Visual recognition

[0639] Remove the front glass and polarizing plate from the SAMSUNG Galaxy S8 (screen size: approximately 5.8 inches, screen width: approximately 64.4 mm) to remove the organic EL display device.

[0640] Then, the substrate side of the horizontally oriented retardation film ii of the laminate prepared by the aforementioned method was bonded to the removed organic EL display device using an adhesive (25μm pressure-sensitive adhesive manufactured by LINTEC). The bonded screen displayed text and was observed visually from the front of the screen and from a 45° angle relative to the front of the screen. It should be noted that during the observation at the 45° angle, the display device was rotated while being observed from all directions.

[0641] If the displayed content can be clearly identified or the visual representation of the displayed content changes with rotation, the rating is A; if the displayed content is slightly unclear, the rating is B; and if the displayed content is unclear or cannot be visually identified, the rating is C.

[0642] Panel Reflection Hue

[0643] Similar to the visual recognition evaluation, the reflected hue of the "Galaxy S8" organic EL display device was confirmed when the power was off (in black) after the laminate was attached to the device. The following criteria were used for evaluation: Glossy black drawing paper was placed on the side of the display device at a distance of 1.5m directly below a 40W 3-wavelength lamp. The hue was visually confirmed from about 50cm away from the front (from directly above, at an angle of less than 20°). If the hue was barely perceptible, the evaluation was A. If the hue was perceptible compared to the black drawing paper and appeared slightly blue, green, or reddish, the evaluation was B. If the hue was strongly observed, the evaluation was C.

[0644] thermal shock test

[0645] For the laminates of Examples 1 and 2, they were respectively bonded to 0.7 mm thick Corning Eagle XG glass (size: 50 mm × 50 mm) using pressure-sensitive adhesive, and cyclic tests were carried out in a thermal shock test chamber. One cycle was defined as exposure to -30°C for 30 minutes followed by rapid heating to 70°C and exposure for another 30 minutes; 100 cycles were performed.

[0646] After the test, it was determined whether any obvious cracks had formed. If no cracks formed, the rating was A; if cracks formed, the rating was B.

[0647] Table 1 shows the composition and optical properties of the light absorption anisotropic film, polarizer, and phase difference film used in Examples 1 to 5 and Comparative Example 1. Table 2 shows the evaluation results of the visual recognizability of the laminate, the panel reflection hue, and the thermal shock test.

[0648] [Table 1]

[0649]

[0650] [Table 2]

[0651]

[0652] In Examples 1-5, it was confirmed that visual recognition from the tilted direction was reduced, thus achieving a privacy protection function, and further reducing the difference in visual recognition when the display device was rotated. In Examples 1-4, clear visual recognition was maintained from the frontal direction. On the other hand, in Example 5, it was confirmed that while transmittance decreased slightly when viewed from the frontal direction, clear visual recognition was maintained. Furthermore, when viewed from an angle, a privacy protection function was achieved, and further reducing the difference in visual recognition when the display device was rotated. In addition, in Examples 1-3 and 5, reflected colors were suppressed, resulting in good black levels. Furthermore, in Example 2, compared to Example 1, in addition to the above results, with the display device powered off (in black display), the display device was placed 1.5m directly below a 40W 3-wavelength lamp, at an elevation angle of approximately 60° and about 50cm away. While rotating the display device 360° and visually checking the hue, the reflected hue from the tilted direction was suppressed, and visual recognition was further improved.

[0653] Example 6

[0654] In the preparation of the light-absorbing anisotropic film, relative to a total of 100 parts by mass of polymerizable liquid crystal compounds 1 and 2, 0.25 parts by mass of leveling agent "F-556" (manufactured by DIC Corporation), 2.8 parts by mass of dichroic pigment 2, and 6 parts by mass of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butane-1-one (manufactured by BASF Japan Ltd. as "Irgacure (registered trademark) 369 (Irg369)") as a photopolymerization initiator were added. Furthermore, o-xylene was added at a solid content concentration of 30%. The mixture was stirred at 80°C for 1 hour, thereby obtaining composition 3 for preparing the light-absorbing anisotropic film.

[0655] To this end, corona treatment was performed on a TAC film (KC4UY) manufactured by KONICA MINOLTA, INC. The composition was coated using a bar coater, heated to 100°C for 60 seconds, and then irradiated with ultraviolet light (cumulative light intensity at 365nm wavelength: 500mJ / cm² under nitrogen atmosphere) from the coated surface using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by USHIO INC.). 2Thus, an anisotropic light-absorbing film 3 was formed. The thickness of the obtained film was 1.8 μm. The three-dimensional absorbance of the anisotropic light-absorbing film 3 was measured, and the maximum absorption wavelength was found to be 622 nm. In addition, the in-plane phase difference Rei(λ) of the horizontally oriented phase difference film i was 99 nm, and (λMAX / 4) / (Rei(λ)) was 1.58.

[0656] Using the light-absorbing anisotropic film 3, a laminate was fabricated in the same manner as in Example 1. A laminate comprising the light-absorbing anisotropic film 3, a horizontally aligned retardation film i (stretched film A), a polarizer, and a horizontally aligned retardation film ii (a cured polymeric liquid crystal composition) was fabricated. Visual discernibility and panel reflectance hue were evaluated for the obtained laminate in the same manner as in Example 1. Furthermore, visual discernibility when viewed through polarized sunglasses was evaluated according to the following method. The structure of the laminate and the characteristics of each component are described in Table 3, and the evaluation results of the laminate are described in Table 4.

[0657] Regarding visual recognition when viewed through polarized sunglasses, for a panel containing the obtained laminate, the observer visually confirms the tonal changes while rotating the panel through polarized sunglasses. Cases where no tonal change is noticed are rated A, cases where a slight tonal change is noticed are rated B, and cases where the tonal change is large or darkens are rated C.

[0658] Example 7

[0659] In addition to dichroic pigment 2, 2.8 parts by weight of dichroic pigment 4 were added. Otherwise, the same procedure was performed as for composition 3 for making anisotropic light-absorbing film to obtain composition 4 for making anisotropic light-absorbing film.

[0660] In this regard, the same procedure as in Example 6 was followed to form an anisotropic light-absorbing film 4 on the TAC film (KC4UY). The thickness of the resulting film was 2.0 μm. The three-dimensional absorbance of the anisotropic light-absorbing film 4 was measured, and the maximum absorption wavelength was found to be 573 nm. The in-plane phase difference Rei(λ) was 100 nm, and (λMAX / 4) / (Rei(λ)) was 1.44.

[0661] Using the light-absorbing anisotropic film 4, a laminate was fabricated in the same manner as in Example 2. A laminate comprising the light-absorbing anisotropic film 4, a horizontally oriented retardation film i (stretched film A), a polarizer, a horizontally oriented retardation film ii (cured polymeric liquid crystal composition), and a vertically oriented retardation film iii was fabricated and evaluated in the same manner as in Example 6. The structure of the laminate and the characteristics of each component are described in Table 3, and the evaluation results of the laminate are described in Table 4.

[0662] Dichroic pigment 4:

[0663] [Chemical Formula 41]

[0664]

[0665] Example 8

[0666] Instead of dichroic pigment 2, 2.8 parts of dichroic pigment 5 were added. Otherwise, the same procedure was followed as with composition 3 for making anisotropic light-absorbing films to obtain composition 5 for making anisotropic light-absorbing films.

[0667] In this regard, the same procedure as in Example 6 was followed to form an anisotropic light-absorbing film 5 on the TAC film (KC4UY). The thickness of the resulting film was 2.0 μm. The three-dimensional absorbance of the anisotropic light-absorbing film 5 was measured, and the maximum absorption wavelength was found to be 476 nm. The in-plane phase difference Rei(λ) was 102 nm, and (λMAX / 4) / (Rei(λ)) was 1.16.

[0668] Using the light-absorbing anisotropic film 5, a laminate was fabricated in the same manner as in Example 2. A laminate comprising the light-absorbing anisotropic film 5, a horizontally oriented retardation film i (stretched film A), a polarizer, a horizontally oriented retardation film ii (cured polymeric liquid crystal composition), and a vertically oriented retardation film iii was fabricated and evaluated in the same manner as in Example 6. The structure of the laminate and the characteristics of each component are described in Table 3, and the evaluation results of the laminate are described in Table 4.

[0669] Dichroic pigment 5:

[0670] [Chemical Formula 42]

[0671]

[0672] Example 9

[0673] In the fabrication of the horizontally oriented retardation film i, a roll of unstretched film made of norbornene resin with a glass transition temperature (Tg) of 125°C and a thickness of 50 μm was uniaxially stretched by approximately 1.8 times under an atmosphere of 128°C to obtain a roll-shaped retardation film (stretched film C) with a thickness of approximately 35 μm. The in-plane phase difference Re(550) of the obtained film is 120 nm, and Re(450) is 123 nm. In addition, the direction of the slow axis is at 90° with the longitudinal direction of the film. The in-plane phase difference Rei(λ) is 122 nm, and (λMAX / 4) / (Rei(λ)) is 0.97.

[0674] The horizontally oriented retardation film i was changed from stretch film A to stretch film C, and the laminate was fabricated in the same manner as in Example 8. A laminate comprising, in sequence, a light absorption anisotropic film 5, a horizontally oriented retardation film i (stretch film C), a polarizer, a horizontally oriented retardation film ii (a cured polymeric liquid crystal composition), and a vertically oriented retardation film iii was fabricated and evaluated in the same manner as in Example 6. The structure of the laminate and the characteristics of each component are described in Table 3, and the evaluation results of the laminate are described in Table 4.

[0675] Example 10

[0676] Instead of the stretched film A used as horizontally aligned retardation film i in Example 8, a retardation film (cured polymeric liquid crystal composition) used as horizontally aligned retardation film ii in Example 1 was used. Otherwise, the laminate was fabricated in the same manner as in Example 8. The in-plane retardation Rei(λ) was 126 nm, and (λMAX / 4) / (Rei(λ)) was 0.94. A laminate comprising, in sequence, a light absorption anisotropic film 5, horizontally aligned retardation film i (cured polymeric liquid crystal composition), a polarizer, horizontally aligned retardation film ii (cured polymeric liquid crystal composition), and vertically aligned retardation film iii was fabricated and evaluated in the same manner as in Example 6. The structure of the laminate and the characteristics of each component are described in Table 3, and the evaluation results of the laminate are described in Table 4.

[0677] For Comparative Example 1, the visual recognition performance when viewed through polarized sunglasses was evaluated in the same manner as in Example 6. The results are shown in Table 4.

[0678] [Table 3]

[0679]

[0680] [Table 4]

[0681]

[0682] In Examples 6-10, it was confirmed that the visual recognizability of the color portion corresponding to the complementary color of each maximum absorption wavelength was reduced from the tilt direction, thus achieving anti-peeping function, and further reducing the difference in visual recognizability when the display device is rotated. In addition, in Examples 6-10, clear visual recognizability was maintained from the front direction. Furthermore, in Examples 6-10, reflected colors were also suppressed, resulting in good black. In Examples 7-10, compared with Examples 1 and 6, in addition to the above results, when the display device was powered off (in black display), the display device was placed 1.5m directly below a 40W 3-wavelength lamp, at an elevation angle of approximately 60° and about 50cm away, and the hue was visually checked while rotating the display device 360°. As a result, the hue reflected from the tilt direction was also suppressed, and visual recognizability was further improved.

[0683] When comparing Examples 6 and 7, it was confirmed that the difference in visual recognizability when the display device is rotated in Example 7 was further reduced. In addition, when comparing Examples 8, 9, and 10, it was confirmed that the difference in visual recognizability when the display device is rotated in Examples 8 and 9 was further reduced compared to Example 10. Furthermore, a further reduction was confirmed in Example 9.

[0684] When the display device is powered on and the display content is checked through polarized sunglasses while the display device is rotated, in Comparative Example 1, when the absorption axis of the polarized sunglasses is at a 90° angle to the absorption axis of the polarizer in the laminate, the display dims, resulting in insufficient visual recognition from all directions. On the other hand, for the laminates of Examples 6 to 10, the display content can be visually recognized when the display device is rotated. In particular, for Examples 6 to 9, compared with Example 10, the color tone change is smaller when the display device is rotated.

Claims

1. A laminate comprising, in sequence, an anisotropic light-absorbing film, a horizontally oriented retardation film i, a polarizer, and a horizontally oriented retardation film ii. The light-absorbing anisotropic film is a light-absorbing anisotropic film formed by curing a liquid crystal composition containing a dichroic pigment and a liquid crystal compound. When any position direction in the film surface is set as the x-axis, the direction orthogonal to the x-axis in the film surface is set as the y-axis, and the film thickness direction orthogonal to both the x-axis and y-axis is set as the z-axis, the light-absorbing anisotropic film satisfies the following equations (1) to (3): Az>(Ax+Ay) / 2 (1) Ax(z=60°) / Ax>5 (2) Ay(z=60°) / Ay>5 (3) In equations (1) to (3), Ax, Ay, Az, Ax(z=60°), and Ay(z=60°) are all the absorbance at the wavelength of maximum absorption of the dichroic pigment in the anisotropic light-absorbing film. Ax represents the absorbance of linearly polarized light vibrating along the x-axis. Ay represents the absorbance of linearly polarized light vibrating along the y-axis. Az represents the absorbance of linearly polarized light vibrating along the z-axis. Ax (z = 60°) represents the absorbance of linearly polarized light vibrating along the x-axis when the membrane is rotated 60° about the y-axis. Ay(z=60°) represents the absorbance of linearly polarized light vibrating along the y-axis when the membrane is rotated 60° about the x-axis. The horizontally oriented phase difference film i satisfies the following equation (4): 70nm≤Re i (550)≤170nm (4) In equation (4), Re i (λ) represents the in-plane phase difference value of the horizontally oriented phase difference film i at a wavelength of λnm; The horizontally oriented phase difference film ii satisfies the following equation (5): 120nm≤Re ii (550)≤160nm (5) In equation (5), Re ii (λ) represents the in-plane phase difference value of the horizontally oriented phase difference film ii at a wavelength of λnm.

2. The laminated body as claimed in claim 1, wherein, The horizontally oriented phase difference film ii satisfies the following equation (6): Re ii (450) / Re ii (550)<1.00 (6) In equation (6), Re ii (λ) has the same meaning as in equation (5) above; The angle θ between the slow axis of the horizontally oriented phase retardation film ii and the absorption axis of the polarizer. ii The range is defined by the following formula (7): 15°≤|θ ii |≤75° (7).

3. The laminate as described in claim 1 or 2, wherein, The horizontally oriented phase difference film i satisfies the following equation (8): Re i (450) / Re i (550)≥1.00 (8) In equation (8), Re i (λ) has the same meaning as in equation (4) above; The angle θ between the slow axis of the horizontally oriented phase retardation film i and the absorption axis of the polarizer. i The range is defined by the following formula (9): 15°≤|θ i |≤75° (9).

4. The laminate as described in claim 1 or 2, wherein, The horizontally oriented phase difference film i and the polarizer are laminated together by an adhesive.

5. The laminate as described in claim 1 or 2, wherein, The horizontally oriented phase difference film i is formed from a film that has been stretched in at least one direction.

6. The laminate as described in claim 1 or 2, wherein, The horizontally oriented phase retardation film ii is formed from a cured polymeric liquid crystal composition containing at least one polymeric liquid crystal compound.

7. The laminate as described in claim 1 or 2, wherein, The liquid crystal compound contained in the light-absorbing anisotropic film exhibits a smectic liquid crystal phase.

8. The laminate as described in claim 1 or 2, wherein, A transparent protective film is also included on the surface of the light-absorbing anisotropic film opposite to the horizontally oriented phase difference film i.

9. The laminate as claimed in claim 1 or 2, further comprising a vertically oriented retardation film iii satisfying the following formula (10), -100nm≤Rth iii (550)≤-20nm (10) In equation (10), Rth iii (λ) represents the thickness phase difference value of the vertically oriented phase difference film iii at wavelength λnm; The vertically oriented phase retardation film iii is stacked between the polarizer and the horizontally oriented phase retardation film ii, or on the side of the horizontally oriented phase retardation film ii opposite to the polarizer.

10. The laminate as claimed in claim 9, wherein, The vertically oriented phase difference film iii satisfies the following equation (11): Rth iii (450) / Rth iii (550)>1.00 (11) In equation (11), Rth iii (λ) represents the thickness phase difference value of the vertically oriented phase difference film iii at wavelength λnm.

11. The laminate as claimed in claim 9, wherein, The vertically oriented phase retardation film iii is formed from a cured polymeric liquid crystal composition containing at least one polymeric liquid crystal compound.

12. An organic EL display device comprising the laminate as described in claim 1 or 2.

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