Polymerizable liquid crystal composition, optically anisotropic film, laminate, polarizing plate, and image display device

Abstract

The invention relates to a polymerizable liquid crystal composition, an optically anisotropic film, a laminate, a polarizing plate, and an image display device. The present invention addresses the problem of providing an optically anisotropic film capable of suppressing a change in phase difference due to heat, a laminate, a polarizing plate including the optically anisotropic film, and an image display device including the optically anisotropic film and the laminate. [Solution] The optically anisotropic film satisfies formula (1). In formula (1), O < S > represents the oxygen atomic ratio at a position 10 nm from the film surface of the optically anisotropic film, and O < C > represents the oxygen atomic ratio at the central portion of the optically anisotropic film. O / O C > = 1.1 (1).

Description

Technical Field

[0001] The present invention relates to a polymerizable liquid crystal composition, an optically anisotropic film, a laminate including an optically anisotropic layer, a polarizing plate including the optically anisotropic film, and an image display device. Background Art

[0002] Generally, in the case of an in-plane switching (IPS) liquid crystal display device, it is known that when visually recognized from an oblique direction at an angle of 45 degrees relative to the absorption axis of the polarizer, the black display has a large light leakage, which is prone to a decrease in contrast and color shift. This phenomenon is caused by the fact that the angle formed by the absorption axes of the polarizers arranged on the front and back sides of the liquid crystal unit does not apparently reach 90 degrees.

[0003] In order to reduce light leakage when visually recognized from the aforementioned oblique direction, a method of configuring a phase difference film between a liquid crystal unit and a polarizer has been proposed. For example, Patent Document 1 describes a method of reducing light leakage in an IPS-type liquid crystal display device by configuring a stretched phase difference film having a refractive index anisotropy of nx>ny>nz and a stretched phase difference film having a refractive index anisotropy of nz>nx>ny.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2009-139747 Summary of the invention

[0007] Problems to be solved by the invention

[0008] The polarizing plate stacked with a polarizer and a phase difference film described in Patent Document 1 can be suitably used to reduce light leakage in an IPS-type liquid crystal display device. However, in a liquid crystal display device having this structure, as the use environment of the image display device becomes more severe, the phase difference layer used is also required to further suppress the phase difference change.

[0009] In view of the above problems, the object of the present invention is to provide a new solution, that is, to provide a new optical anisotropic film formed by a new polymerizable liquid crystal composition. In addition, the object of the present invention is to provide an optical anisotropic film capable of suppressing the phase difference change caused by heat, a laminate, and a polarizing plate comprising the above optical anisotropic film, and an image display device having the same.

[0010] Means for solving problems

[0011] The inventors of the present application have conducted intensive studies to solve the above-mentioned problems and have completed the present invention. That is, the present invention includes the following aspects.

[0012] [1] An optically anisotropic film satisfying the following formula (1).

[0013] Ο S / Ο C ≥1.1 (1)

[0014] [In formula (1), S is the oxygen atomic ratio of the optically anisotropic film at a position 10 nm away from the film surface, O C Indicates the oxygen atomic ratio in the central portion of the optically anisotropic film.]

[0015] [2] An optically anisotropic film satisfying the following formula (2).

[0016] 0.95≤A1 / A2≤1.06 (2)

[0017] [In formula (2), A1 represents the absorbance in the range of 300 nm to 400 nm when measured at a certain angle relative to the in-plane direction, and A2 represents the absorbance in the range of 300 nm to 400 nm when measured at an angle rotated 90 degrees from the angle when A1 is measured toward the in-plane direction.]

[0018] [3] The optically anisotropic film according to [1] or [2] above, which satisfies the following formula (3).

[0019] nx≈ny <nz (3)

[0020] [In formula (3), nx represents the principal refractive index in the direction parallel to the film plane in the refractive index ellipsoid formed by the phase difference layer. ny represents the refractive index in the direction parallel to the film plane and orthogonal to the direction of nx in the refractive index ellipsoid formed by the phase difference layer. nz represents the refractive index in the direction perpendicular to the film plane in the refractive index ellipsoid formed by the phase difference layer. )]

[0021] [4] The optically anisotropic film according to [1] or [2], wherein the thickness is 0.1 μm or more and 3 μm or less.

[0022] [5] The optically anisotropic film according to [1] or [2] above, which satisfies the following formula (4).

[0023] -180nm≤RthC(550)≤-30nm (4)

[0024] [In formula (4), RthC(550) represents the phase difference value in the thickness direction at a wavelength of 550 nm.]

[0025] [6] The optically anisotropic film according to [1] or [2] above, which satisfies the following formula (5).

[0026] RthC(450) / RthC(550)≤1.04 (5)

[0027] [In formula (5), RthC(450) represents the phase difference value in the thickness direction at a wavelength of 450 nm, and RthC(550) represents the phase difference value in the thickness direction at a wavelength of 550 nm.]

[0028] [7] A laminate comprising: the optically anisotropic film according to [1] or [2] above; and an optically anisotropic layer.

[0029] [8] A polarizing plate comprising: a polarizing film; and the optically anisotropic film described in [1] or [2].

[0030] [9] An image display device comprising the polarizing plate described in [8] above.

[0031]

[10] A polymerizable liquid crystal composition having:

[0032] At least one polymerizable liquid crystal compound; and

[0033] The reactive group-containing non-liquid crystal compound contains 3 to 18 parts by mass of the reactive group-containing non-liquid crystal compound based on 100 parts by mass of the total polymerizable liquid crystal compound, wherein the reactive group-containing non-liquid crystal compound has at least one reactive group selected from the group consisting of an acryloyloxy group and a methacryloyloxy group.

[0034]

[11] The polymerizable liquid crystal composition according to

[10] above, wherein the weight average molecular weight of the non-liquid crystal compound containing a reactive group is 1200 or less.

[0035]

[12] The polymerizable liquid crystal composition according to

[10] , further comprising a solvent.

[0036]

[13] The polymerizable liquid crystal composition according to

[10] above, further comprising a polymerization initiator.

[0037]

[14] The polymerizable liquid crystal composition according to

[10] , further comprising a leveling agent.

[0038] Effects of the Invention

[0039] According to the present invention, it is possible to provide an optically anisotropic film and a laminated body in which a phase difference change due to heat is small, a polarizing plate including the laminated body, and an image display device including the same. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 This is a schematic cross-sectional view showing an example of the layer structure of the optically anisotropic film of the present invention.

[0041] Figure 2This is a schematic cross-sectional view showing an example of the layer structure of the laminated body of the present invention.

[0042] Figure 3 This is a schematic cross-sectional view showing an example of the layer structure of the polarizing plate of the present invention.

[0043] Description of Reference Numerals

[0044] 1: Optically anisotropic film

[0045] 2: Optically anisotropic layer

[0046] 3: Polarizing film

[0047] 10: Laminated body

[0048] 20: Polarizing plate DETAILED DESCRIPTION

[0049] 〔Optically anisotropic film〕

[0050] The following is based on Figure 1 Although the optically anisotropic film of the present invention is described, the present invention is not limited to these embodiments.

[0051] The optically anisotropic film of the present invention satisfies the following formula (1).

[0052] Ο S / Ο C ≥1.1 (1)

[0053] [In formula (1), S is the oxygen atomic ratio of the optically anisotropic film at a position 10 nm away from the film surface, O C Indicates the oxygen atomic ratio in the central portion of the optically anisotropic film.]

[0054] When the optically anisotropic film satisfies the formula (1), the optically anisotropic film shows a property that a compound having the O element segregates on the film surface.

[0055] Such an optically anisotropic film is excellent in heat resistance and phase difference change after a heat resistance test. S / Ο C The value of is preferably 1.15 or more, more preferably 1.2 or more, and is usually 2.5 or less, preferably 2.0 or less, more preferably 1.8 or less. S / Ο C When the value of is within the above range, a laminated body can be obtained in which a change in phase difference is suppressed when a heat resistance test is performed on the optically anisotropic film.

[0056] Furthermore, the optically anisotropic film of the present invention satisfies the following formula (2).

[0057] 0.95≤A1 / A2≤1.06 (2)

[0058] [In formula (2), A1 represents the absorbance in the range of 300 nm to 400 nm when measured at a certain angle relative to the in-plane direction, and A2 represents the absorbance in the range of 300 nm to 400 nm when measured at an angle rotated 90 degrees from the angle when A1 is measured toward the in-plane direction.]

[0059] When the optically anisotropic film satisfies the formula (2), the optically anisotropic film shows isotropy in which the absorbance does not change in the in-plane direction.

[0060] Such an optically anisotropic film has excellent heat resistance and phase difference change after a heat resistance test. In addition, in formula (2), the value of A1 / A2 is preferably 0.97 or more, more preferably 0.98 or more, and preferably 1.03 or less, more preferably 1.02 or less. When the value of A1 / A2 is within the above range, a laminated body in which the phase difference change is suppressed when the optically anisotropic film is subjected to a heat resistance test can be obtained.

[0061] Furthermore, the optically anisotropic film preferably satisfies the following formula (3).

[0062] nx≈ny <nz (3)

[0063] [In formula (3), nx represents the principal refractive index in the direction parallel to the film plane in the refractive index ellipsoid formed by the phase difference layer. ny represents the refractive index in the direction parallel to the film plane and orthogonal to the direction of nx in the refractive index ellipsoid formed by the phase difference layer. nz represents the refractive index in the direction perpendicular to the film plane in the refractive index ellipsoid formed by the phase difference layer. )]

[0064] The thickness of the optically anisotropic film is usually 0.1 μm to 3 μm, preferably 0.3 μm to 2 μm, and more preferably 0.5 μm to 1.5 μm. When the thickness of the optically anisotropic layer film satisfies the above range, both lightweight and optical properties of the image display device can be achieved.

[0065] The in-plane retardation value Re(550) of the optically anisotropic film is usually in the range of 0 to 10 nm, preferably in the range of 0 to 5 nm.

[0066] In addition, the phase difference value in the thickness direction preferably satisfies the following formula (4).

[0067] -180nm≤RthC(550)≤-30nm (4)

[0068] [In formula (4), RthC(550) represents the phase difference value in the thickness direction at a wavelength of 550 nm.]

[0069] Examples of the optically anisotropic film of the present invention include a cured product of a polymerizable liquid crystal composition obtained by curing a polymerizable liquid crystal compound in a state of being aligned in a vertical direction with respect to a film plane (hereinafter also referred to as a “vertically aligned liquid crystal cured film”).

[0070] As a cured product of a polymerizable liquid crystal composition in which a polymerizable liquid crystal compound is cured in a state oriented in a vertical direction relative to the film plane, a nematic liquid crystal or a discotic liquid crystal can be used to form it. The in-plane phase difference value of the cured product layer of the polymerizable liquid crystal composition can be adjusted by controlling the type of the polymerizable liquid crystal compound, the orientation state of the cured product of the polymerizable liquid crystal compound, and the thickness of the cured product layer.

[0071] In the present invention, the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film refers to a liquid crystal compound having a polymerizable group, and is particularly preferably a polymerizable liquid crystal compound having at least one radical polymerizable group.

[0072] The polymerizable group refers to a group that can participate in a polymerization reaction using active free radicals, acids, etc. generated by a polymerization initiator. Examples of the polymerizable group include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloyloxy, methacryloyloxy, oxacyclopropyl, and oxetanyl. Among them, a free radical polymerizable group is preferred, and acryloyloxy, methacryloyloxy, vinyl, and vinyloxy are more preferred, and acryloyloxy and methacryloyloxy are further preferred.

[0073] The liquid crystal property exhibited by the polymerizable liquid crystal compound may be a thermotropic liquid crystal or a lyotropic liquid crystal. From the viewpoint of enabling precise film thickness control, a thermotropic liquid crystal is preferred.

[0074] As the polymerizable liquid crystal compound, there can be mentioned a polymerizable liquid crystal compound that generally exhibits positive wavelength dispersion and a polymerizable liquid crystal compound that exhibits reverse wavelength dispersion. Only one polymerizable liquid crystal compound can be used, or two polymerizable liquid crystal compounds can be mixed and used. From the perspective of preventing light leakage and color shift when visually recognized from an oblique direction during black display, it is preferred to adjust the composition in such a way that the optically anisotropic film satisfies the following formula (5).

[0075] RthC(450) / RthC(550)≤1.04 (5)

[0076] [In formula (5), RthC(450) represents the phase difference value in the thickness direction at a wavelength of 450 nm, and RthC(550) represents the phase difference value in the thickness direction at a wavelength of 550 nm.]

[0077] As the polymerizable liquid crystal compound showing reverse wavelength dispersion, a compound having the following characteristics (A) to (D) is preferred.

[0078] (A) is a compound that can form a nematic phase or a smectic phase.

[0079] (B) The polymerizable liquid crystal compound has π electrons in the long-axis direction (a).

[0080] (C) It has π electrons in a direction intersecting the long axis direction (a) (intersecting direction (b)).

[0081] (D) The π electron density in the long axis direction (a) of the polymerizable liquid crystal compound defined by the following formula (i), where the total number of π electrons present in the long axis direction (a) is N(πa) and the total molecular weight present in the long axis direction is N(Aa):

[0082] D(πa)=N(πa) / N(Aa)(i), and,

[0083] The total number of π electrons present in the cross direction (b) is denoted as N(πb), and the total number of molecular weights present in the cross direction (b) is denoted as N(Ab), and the π electron density in the cross direction (b) of the polymerizable liquid crystal compound is defined by the following formula (ii):

[0084] D(πb)=N(πb) / N(Ab) (ii)

[0085] The relationship of existence (iii) is:

[0086] 0≤〔D(πa) / D(πb)〕<1 (iii)

[0087] [That is, the π electron density in the cross direction (b) is greater than the π electron density in the long axis direction (a)].

[0088] In addition, as described above, the polymerizable liquid crystal compound having π electrons in the long axis and in the direction intersecting therewith forms, for example, a T-shaped structure.

[0089] In the above-mentioned features (A) to (D), the major axis direction (a) and the number of π electrons N are defined as follows.

[0090] The major axis direction (a) refers to the major axis direction of the rod, for example, in the case of a compound having a rod-like structure.

[0091] The number of π electrons N(πa) present in the major axis direction (a) does not include π electrons that disappear due to the polymerization reaction.

[0092] The number of π electrons N(πa) present in the long axis direction (a) is the total number of π electrons on the long axis and π electrons conjugated thereto, for example, including the number of π electrons present in the ring that exists in the long axis direction (a) and satisfies the Huckel rule.

[0093] The number of π electrons N(πb) present in the crossing direction (b) does not include π electrons that disappear due to the polymerization reaction.

[0094] The polymerizable liquid crystal compound satisfying the above conditions has a mesostructure in the long-axis direction, and exhibits a liquid crystal phase (nematic phase, smectic phase) due to the mesostructure.

[0095] By applying a polymerizable liquid crystal compound satisfying the above (A) to (D) on a film (layer) forming a liquid crystal cured film and heating it to a temperature above the phase transition temperature, a liquid crystal phase such as a nematic phase or a smectic phase can be formed. The liquid crystal phase formed by the orientation of the polymerizable liquid crystal compound is usually oriented in a manner that the long axis directions of the polymerizable liquid crystal compound are parallel to each other, and the long axis direction becomes the orientation direction of the liquid crystal phase. If such a polymerizable liquid crystal compound is made into a film and polymerized in a liquid crystal phase, a polymer film formed by polymerizing in a state of orientation along the long axis direction (a) can be formed. The polymer film absorbs ultraviolet rays by π electrons in the long axis direction (a) and π electrons in the cross direction (b). Here, the absorption maximum wavelength of ultraviolet rays absorbed by the π electrons in the cross direction (b) is recorded as λbmax. λbmax is usually 300nm to 400nm. The density of π electrons satisfies the above formula (iii), and the density of π electrons in the cross direction (b) is greater than that in the long axis direction (a), so that the absorption of linearly polarized ultraviolet light (wavelength λbmax) having a vibration plane in the cross direction (b) is greater than that of linearly polarized ultraviolet light (wavelength λbmax) having a vibration plane in the long axis direction (a). The ratio (absorbance in the cross direction (b) of linearly polarized ultraviolet light / absorbance in the long axis direction (a)) is, for example, greater than 1.0, preferably greater than 1.2, and usually 30 or less, for example, 10 or less.

[0096] The polymerizable liquid crystal compound having the above-mentioned characteristics usually shows reverse wavelength dispersion. Specifically, for example, there can be mentioned a compound represented by the following formula (X) (hereinafter also referred to as a “polymerizable liquid crystal compound (X)”).

[0097] [Chemical formula 1]

[0098]

[0099] In formula (X), Ar represents a divalent group containing an aromatic group which may have a substituent. The aromatic group referred to herein refers to a group having a π electron number of [4n+2] in the ring structure according to the Huckel rule, for example, an Ar group such as (Ar-1) to (Ar-23) described later may have two or more Ar groups exemplified by divalent linking groups. Here, n represents an integer. In the case where a ring structure is formed by containing heteroatoms such as -N= and -S-, the case where the non-covalent bond electron pairs on these heteroatoms satisfy the Huckel rule and thus have aromaticity is also included. It is preferred that at least one of a nitrogen atom, an oxygen atom, and a sulfur atom is contained in the aromatic group. The aromatic group contained in the divalent group Ar may be one or more. In the case where the aromatic group is one, the divalent group Ar may be a divalent aromatic group which may have a substituent. When the divalent group Ar contains two or more aromatic groups, the two or more aromatic groups may be bonded to each other via a single bond, a divalent bonding group such as -CO-O-, or -O-.

[0100] G 1 and G 2 Each independently represents a divalent aromatic group or a divalent alicyclic hydrocarbon group. Here, the hydrogen atoms contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted by a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and the carbon atoms constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted by an oxygen atom, a sulfur atom or a nitrogen atom.

[0101] L 1 , L 2 , B 1 and B 2 Each is independently a single bond or a divalent linking group.

[0102] k and l each independently represent an integer from 0 to 3, and satisfy the relationship 1≤k+1. Here, when 2≤k+1, B 1 and B 2 , G 1 and G 2 They can be the same as or different from each other.

[0103] E 1 and E 2 Each independently represents an alkanediyl group having 1 to 17 carbon atoms, and more preferably an alkanediyl group having 4 to 12 carbon atoms. In addition, the hydrogen atoms contained in the alkanediyl group may be substituted with halogen atoms, and the -CH 2 - can be -O-, -S-, -SiH 2-, -C(=O)- replacement.

[0104] P 1 and P 2 Each independently represents a polymerizable group or a hydrogen atom, and at least one of them is a polymerizable group.

[0105] G 1 and G 2 Each independently preferably is a 1,4-phenylenediyl group which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, or a 1,4-cyclohexanediyl group which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms. More preferably, it is a 1,4-phenylenediyl group substituted with a methyl group, an unsubstituted 1,4-phenylenediyl group, or an unsubstituted 1,4-trans-cyclohexanediyl group. Especially preferably, it is an unsubstituted 1,4-phenylenediyl group or an unsubstituted 1,4-trans-cyclohexanediyl group.

[0106] In addition, it is preferred that there are multiple G 1 and G 2 At least one of them is a divalent alicyclic hydrocarbon group, and more preferably 1 or L 2 Bonded G 1 and G 2 At least one of them is a divalent alicyclic hydrocarbon group.

[0107] L 1 and L 2 Each of them is independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R a1 OR a2 -、-R a3 COOR a4 -、-R a5 OCOR a6 -、R a7 OC=OOR a8 -、-N=N-、-CR c =CR d -, or -C≡C-. Here, R a1 ~R a8 Each independently represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R c and R d represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. 1 and L 2 Each independently is more preferably a single bond, -OR a2-1 -、-CH 2 -、-CH 2 CH 2-、-COOR a4-1 -, or -OCOR a6-1 -. Here, R a2-1 , R a4-1 , R a6-1 Each independently represents a single bond, -CH 2 -、-CH 2 CH 2 -Any one of L 1 and L 2 Each of them is independently more preferably a single bond, -O-, -CH 2 CH 2 -、-COO-、-COOCH 2 CH 2 -, or -OCO-.

[0108] B 1 and B 2 Each of them is independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R a9 OR a10 -、-R a11 COOR a12 -、-R a13 OCOR a14 -, or R a15 OC=OOR a16 -. Here, R a9 ~R a16 Each independently represents a single bond or an alkylene group having 1 to 4 carbon atoms. 1 and B 2 Each independently is more preferably a single bond, -OR a10-1 -、-CH 2 -、-CH 2 CH 2 -、-COOR a12 -1 -, or -OCOR a14-1 -. Here, R a10-1 , R a12-1 , R a14-1 Each independently represents a single bond, -CH 2 -、-CH 2 CH 2 -Any one of B. 1 and B 2 Each of them is independently more preferably a single bond, -O-, -CH 2 CH 2 -、-COO-、-COOCH 2 CH 2 -, -OCO-, or -OCOCH 2 CH 2-.

[0109] From the viewpoint of exhibiting reverse wavelength dispersion, k and l are preferably in the range of 2≤k+l≤6, preferably k+l=4, and more preferably k=2 and l=2. k=2 and l=2 are preferred because a symmetrical structure is obtained.

[0110] As P 1 or P 2 The polymerizable group represented by , includes epoxy, vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloyloxy, methacryloyloxy, oxirane, and oxetanyl, etc. Among them, acryloyloxy, methacryloyloxy, vinyl, and vinyloxy are preferred, and acryloyloxy and methacryloyloxy are more preferred.

[0111] Ar preferably has at least one selected from an aromatic hydrocarbon ring that may have a substituent, an aromatic heterocycle that may have a substituent, and an electron-withdrawing group. As the aromatic hydrocarbon ring, for example, benzene ring, naphthalene ring, anthracene ring, etc. can be cited, preferably benzene ring, naphthalene ring. As the aromatic heterocycle, furan ring, benzofuran ring, pyrrole ring, indole ring, thiophene ring, benzothiophene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazole ring, triazine ring, pyrroline ring, imidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, thienothiazole ring, oxazole ring, benzoxazole ring, and phenanthroline ring, etc. can be cited. Among them, preferably have thiazole ring, benzothiazole ring or benzofuran ring, further preferably have benzothiazolyl. In addition, when Ar contains a nitrogen atom, the nitrogen atom preferably has π electrons.

[0112] In formula (X), the total number Nπ of π electrons contained in the divalent aromatic group represented by Ar is preferably 8 or more, more preferably 10 or more, further preferably 14 or more, and particularly preferably 16 or more. It is preferably 30 or less, more preferably 26 or less, and further preferably 24 or less.

[0113] Examples of the aromatic group represented by Ar include the following groups.

[0114] [Chemical formula 2]

[0115]

[0116] In the formulas (Ar-1) to (Ar-23), the symbol * represents a connecting portion, and Z 0 , Z 1 and Z 2Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 12 carbon atoms, an alkylsulfonyl group having 1 to 12 carbon atoms, a carboxyl group, a fluoroalkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, an N-alkylamino group having 1 to 12 carbon atoms, an N,N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 12 carbon atoms, or an N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms. 0 , Z 1 and Z 2 A polymerizable group may be contained.

[0117] Q 1 and Q 2 Each independently represents -CR 2’ R 3’ -、-S-、-NH-、-NR 2’ -, -CO- or -O-, R 2’ and R 3’ Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0118] J 1 , and J 2 Each independently represents a carbon atom or a nitrogen atom.

[0119] Y 1 , Y 2 and Y 3 Each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may be substituted.

[0120] W 1 and W 2 Each independently represents a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0-6.

[0121] As Y 1 , Y 2 and Y 3 The aromatic hydrocarbon group in the group includes aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as phenyl, naphthyl, anthracenyl, phenanthrenyl, and biphenyl, preferably phenyl and naphthyl, and more preferably phenyl. The aromatic heterocyclic group includes aromatic heterocyclic groups having 4 to 20 carbon atoms, such as furanyl, pyrrolyl, thienyl, pyridyl, thiazolyl, and benzothiazolyl, which contain at least one hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom, preferably furanyl, thienyl, pyridyl, thiazolyl, and benzothiazolyl.

[0122] Y 1 , Y 2 and Y 3Each independently may be a substituted polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group. The polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring collection. The polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from an aromatic ring collection.

[0123] Z 0 , Z 1 and Z 2 Each of them is independently preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, or an alkoxy group having 1 to 12 carbon atoms, and Z0 is more preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cyano group. 1 and Z 2 More preferably, Z is a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a cyano group. 0 , Z 1 and Z 2 A polymerizable group may be contained.

[0124] Q 1 and Q 2 Preferred are -NH-, -S-, -NR 2’ -、-O-,R 2’ A hydrogen atom is preferred, and -S-, -O-, and -NH- are particularly preferred.

[0125] Among the formulae (Ar-1) to (Ar-23), the formulae (Ar-6) and (Ar-7) are preferred from the viewpoint of molecular stability.

[0126] In the formulas (Ar-16) to (Ar-23), Y 1 The nitrogen atom and Z that can be bonded to it 0 Together, they form an aromatic heterocyclic group. Examples of the aromatic heterocyclic group include the aromatic heterocyclic rings that Ar may have and are described above, for example, a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, an indole ring, a quinoline ring, an isoquinoline ring, a purine ring, a pyrrolidine ring, etc. The aromatic heterocyclic group may have a substituent. In addition, Y 1 The nitrogen atom and Z that can be bonded to it 0 Together, they form the above-mentioned optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group, for example, a benzofuran ring, a benzothiazole ring, a benzoxazole ring, etc.

[0127] In addition, in the present invention, as a polymerizable liquid crystal compound for forming a vertically aligned liquid crystal cured film, for example, a compound containing a group represented by the following formula (Y) (hereinafter also referred to as "polymerizable liquid crystal compound (Y)") can be used. Polymerizable liquid crystal compounds generally tend to show positive wavelength dispersion. The polymerizable liquid crystal compound can be used alone or in combination of two or more, and the polymerizable liquid crystal compound (X) can be used in combination with the polymerizable liquid crystal compound (Y).

[0128] P11-B11-E11-B12-A11-B13-(Y)

[0129] [In formula (Y), P11 represents a polymerizable group.

[0130] 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 substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro group, and the hydrogen atoms contained in the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be substituted with a fluorine atom.

[0131] B11 represents -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR 16 -、-NR 16 -CO-, -CO-, -CS- or a single bond. 16 It represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0132] B12 and B13 each independently represent -C≡C-, -CH=CH-, -CH 2 -CH 2 -, -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -OC(=O)-O-, -CH=N-, -N=CH-, -N=N-, -C(=O)-NR 16 -、-NR 16 -C(=O)-, -OCH 2 -、-OCF 2 -、-CH 2 O-、-CF 2 O-, -CH=CH-C(=O)-O-, -OC(=O)-CH=CH- or a single bond.

[0133] E11 represents an alkanediyl group having 1 to 12 carbon atoms, wherein the hydrogen atoms contained in the alkanediyl group may be substituted by an alkoxy group having 1 to 5 carbon atoms, and the hydrogen atoms contained in the alkoxy group may be substituted by a halogen atom. 2- may be replaced by -O- or -CO-.]

[0134] The number of carbon atoms of 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. A11 is preferably cyclohexane-1,4-diyl or 1,4-phenylene.

[0135] E11 is preferably a linear alkanediyl group having 1 to 12 carbon atoms. 2 - can be replaced by -O-.

[0136] Specifically, there can be mentioned a straight-chain alkanediyl group having 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; -CH 2 -CH 2 -O-CH 2 -CH 2 -、-CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH 2 - and - CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH 2 -wait.

[0137] B11 is preferably -O-, -S-, -CO-O-, or -O-CO-, and among them, -CO-O- is more preferred.

[0138] B12 and B13 are each independently preferably -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, or -OC(=O)-O-, and among them, -O- or -OC(=O)-O- is more preferable.

[0139] As the polymerizable group represented by P11, from the perspective of high polymerization reactivity, especially photopolymerization reactivity, it is preferably a free radical polymerizable group or a cationic polymerizable group. From the perspective of easy operation and easy manufacture of the liquid crystal compound itself, the polymerizable group is preferably a group represented by the following formula (P-11) to (P-15).

[0140] [Chemical formula 3]

[0141]

[0142] [In formulas (P-11) to (P-15), R 17 ~R 21 Each independently represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.]

[0143] Specific examples of the groups represented by formula (P-11) to formula (P-15) include groups represented by the following formula (P-16) to formula (P-20).

[0144] [Chemical formula 4]

[0145]

[0146] P11 is preferably a group represented by formula (P-14) to formula (P-20), and more preferably a vinyl group, a p-stilbene group, an epoxy group, or an oxetanyl group.

[0147] The group represented by P11-B11- is more preferably an acryloyloxy group or a methacryloyloxy group.

[0148] Examples of the polymerizable liquid crystal compound (Y) include compounds represented by formula (I), formula (II), formula (III), formula (IV), formula (V) or formula (VI).

[0149] P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-B16-E12-B17-P12(I)

[0150] P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-F11(II)

[0151] P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-E12-B17-P12

[0152] (III)

[0153] P11-B11-E11-B12-A11-B13-A12-B14-A13-F11(IV)

[0154] P11-B11-E11-B12-A11-B13-A12-B14-E12-B17-P12(V)

[0155] P11-B11-E11-B12-A11-B13-A12-F11(VI)

[0156] (Where,

[0157] A12 to A14 each independently have the same meaning as A11, B14 to B16 each independently have the same meaning as B12, B17 has the same meaning as B11, and E12 has the same meaning as E11.

[0158] F11 represents a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 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 sulfone group (-SO 3 H), a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or a halogen atom, the -CH 2 - can be replaced by -O-. )

[0159] Specific examples of polymerizable liquid crystal compounds (Y) include compounds having polymerizable groups recorded in "3.8.6 Network (Completely Cross-linked Type)" and "6.5.1 Liquid Crystal Materials b. Polymerizable Nematic Liquid Crystal Materials" of Liquid Crystal Handbook (edited by Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2000), and polymerizable liquid crystals recorded in Japanese Patent Gazette No. 2010-31223, Japanese Patent Gazette No. 2010-270108, Japanese Patent Gazette No. 2011-6360 and Japanese Patent Gazette No. 2011-207765.

[0160] Specific examples of polymerizable liquid crystal compounds (Y) include compounds represented by the following formulae (I-1) to (I-10). It should be noted that in the following formulae, k1 and k2 each independently represent an integer of 2 to 12. These polymerizable liquid crystal compounds (Y) are preferred from the perspective of ease of synthesis or ease of availability.

[0161] [Chemical formula 5]

[0162]

[0163] In the present invention, the vertically aligned liquid crystal cured film preferably has at least one maximum absorption between wavelengths of 300 and 400 nm, and the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film preferably contains at least one polymerizable liquid crystal compound having a maximum absorption wavelength between wavelengths of 300 and 400 nm. When a photopolymerization initiator is included in the polymerizable liquid crystal composition, the polymerization reaction and gelation of the polymerizable liquid crystal compound may proceed during long-term storage. However, if the maximum absorption wavelength of the polymerizable liquid crystal compound is 300 to 400 nm, even if it is exposed to ultraviolet light during storage, the generation of reactive species from the photopolymerization initiator and the polymerization reaction and gelation of the polymerizable liquid crystal compound caused by the reactive species can be effectively suppressed. Therefore, it is advantageous in terms of the long-term stability of the polymerizable liquid crystal composition, and the orientation and uniformity of the film thickness of the obtained liquid crystal cured film can be improved. It should be noted that the maximum absorption wavelength of the polymerizable liquid crystal compound can be measured in a solvent using an ultraviolet-visible spectrophotometer. The solvent is a solvent that can dissolve the polymerizable liquid crystal compound, and chloroform and the like can be cited as examples.

[0164] Regarding the content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition that forms the vertically oriented liquid crystal cured film, relative to 100 parts by mass of the solid content of the polymerizable liquid crystal composition, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and further preferably 90 to 95 parts by mass. When the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the perspective of the orientation of the obtained liquid crystal cured film. It should be noted that in the present invention, the solid content of the polymerizable liquid crystal composition refers to all components after removing volatile components such as organic solvents from the polymerizable liquid crystal composition.

[0165] In the present invention, the polymerizable liquid crystal composition preferably comprises: at least one polymerizable liquid crystal compound; and 3 to 18 parts by mass of a non-liquid crystal compound relative to 100 parts by mass of all polymerizable liquid crystal compounds, wherein the non-liquid crystal compound has at least one reactive group selected from acryloxy and methacryloxy. By including a non-liquid crystal compound containing a reactive group having at least one reactive group selected from acryloxy and methacryloxy, in addition to promoting vertical alignment, it is also possible to suppress the change in the phase difference value of the obtained liquid crystal cured film after a heat resistance test.

[0166] As non-liquid crystal compounds containing reactive groups, for example, monofunctional (meth) acrylates and multifunctional (meth) acrylates can be cited. Monofunctional refers to having one reactive group, and multifunctional refers to having multiple reactive groups. In the present invention, the non-liquid crystal compound containing reactive groups constituting the optically anisotropic film is preferably selected from at least one of monofunctional (meth) acrylates and multifunctional (meth) acrylates, more preferably selected from at least one of monofunctional acrylates and multifunctional acrylates, and from the perspective of the polymerization reaction of the polymerizable liquid crystal compound and the non-liquid crystal compound containing reactive groups being easily and continuously carried out, it is further preferably a multifunctional acrylate. As a non-liquid crystal compound containing reactive groups, one can be used alone, or two or more can be used in combination. It should be noted that in this specification, (meth) acrylate refers to acrylate or methacrylate, and the same is true for (meth) acryloyloxy, etc. In addition, since the monofunctional (meth) acrylate and the multifunctional (meth) acrylate are non-liquid crystal, it is preferred that they do not have a mesogenic structure. Furthermore, the coating film of the optically anisotropic film-forming composition may contain a urethane structure, an amino structure, an epoxy structure, an ethylene glycol structure, and a polyester structure in the molecule within a range that does not disturb the liquid crystal phase of the polymerizable liquid crystal compound contained therein.

[0167] A monofunctional (meth)acrylate refers to a methacrylate having one (meth)acryloyloxy group in the molecule. 2 =CHCOO-) or methacryloyloxy (CH 2 =C(CH 3 )COO-)〕compound.

[0168] Examples of the monofunctional (meth)acrylate having one (meth)acryloyloxy group include alkyl (meth)acrylates having 4 to 16 carbon atoms, β-carboxyalkyl (meth)acrylates having 2 to 14 carbon atoms, alkylated phenyl (meth)acrylates having 2 to 14 carbon atoms, methoxypolyethylene glycol (meth)acrylates, phenoxypolyethylene glycol (meth)acrylates, and isobornyl (meth)acrylate.

[0169] The polyfunctional (meth)acrylate refers to a compound having two or more (meth)acryloyloxy groups in the molecule. In the present invention, the polyfunctional (meth)acrylate used as the non-liquid crystal compound containing a reactive group preferably has 2 to 8 (meth)acryloyloxy groups in the molecule.

[0170] Examples of bifunctional (meth)acrylates having two (meth)acryloyloxy groups include 1,3-butanediol di(meth)acrylate; 1,3-butanediol (meth)acrylate; 1,6-hexanediol di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; neopentyl glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol diacrylate; bis(acryloyloxyethyl) ether of bisphenol A; ethoxylated bisphenol A di(meth)acrylate; propoxylated neopentyl glycol di(meth)acrylate; ethoxylated neopentyl glycol di(meth)acrylate and 3-methylpentanediol di(meth)acrylate.

[0171] Examples of the polyfunctional (meth)acrylate having 3 to 6 (meth)acryloyloxy groups include:

[0172] Trimethylolpropane tri(meth)acrylate; Pentaerythritol tri(meth)acrylate; Tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate; Ethoxylated trimethylolpropane tri(meth)acrylate; Propoxylated trimethylolpropane tri(meth)acrylate; Pentaerythritol tetra(meth)acrylate; Dipentaerythritol penta(meth)acrylate; Dipentaerythritol hexa(meth)acrylate; Tripentaerythritol tetra(meth)acrylate; Tripentaerythritol penta(meth)acrylate; Tripentaerythritol hexa(meth)acrylate; Tripentaerythritol hepta(meth)acrylate; Tripentaerythritol octa(meth)acrylate;

[0173] The reaction product of pentaerythritol tri(meth)acrylate and acid anhydride; the reaction product of dipentaerythritol penta(meth)acrylate and acid anhydride; the reaction product of tripentaerythritol hepta(meth)acrylate and acid anhydride;

[0174] Caprolactone modified trimethylolpropane tri(meth)acrylate; Caprolactone modified pentaerythritol tri(meth)acrylate; Caprolactone modified tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate; Caprolactone modified pentaerythritol tetra(meth)acrylate; Caprolactone modified dipentaerythritol penta(meth)acrylate; Caprolactone modified dipentaerythritol hexa(meth)acrylate; Caprolactone modified tripentaerythritol tetra(meth)acrylate; Caprolactone modified tripentaerythritol Pentaerythritol penta(meth)acrylate; caprolactone-modified tripentaerythritol hexa(meth)acrylate; caprolactone-modified tripentaerythritol hepta(meth)acrylate; caprolactone-modified tripentaerythritol octa(meth)acrylate; a reaction product of caprolactone-modified pentaerythritol tri(meth)acrylate and anhydride; a reaction product of caprolactone-modified dipentaerythritol penta(meth)acrylate and anhydride, and a reaction product of caprolactone-modified tripentaerythritol hepta(meth)acrylate and anhydride, etc. It should be noted that the so-called caprolactone modification refers to the introduction of a ring-opened body or a ring-opened polymer of caprolactone between the alcohol-derived portion of the (meth)acrylate compound and the (meth)acryloyloxy group.

[0175] Examples of the polyfunctional (meth)acrylate having 7 or more (meth)acryloyloxy groups include: tripentaerythritol hepta(meth)acrylate; tripentaerythritol octa(meth)acrylate; a reaction product of tripentaerythritol hepta(meth)acrylate and an acid anhydride; caprolactone-modified tripentaerythritol hepta(meth)acrylate; caprolactone-modified tripentaerythritol octa(meth)acrylate; a reaction product of caprolactone-modified tripentaerythritol hepta(meth)acrylate and an acid anhydride, and the like.

[0176] As the non-liquid crystal compound containing a reactive group, commercially available multifunctional (meth)acrylates may also be used. Examples of such commercially available products include A-DOD-N, A-HD-N, A-NOD-N, APG-100, APG-200, APG-400, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, HD-N, NOD-N, NPG, and TMPT (all manufactured by Shin-Nakamura Chemical Co., Ltd.), ARONIX M-220, ARONIX M-325, ARONIX M-240, ARONIX M-270, ARONIX M-309, ARONIX M-310, ARONIX M-321, ARONIX M-350, ARONIX M-360, ARONIX M-305, ARONIX M-306, ARONIX M-450, ARONIX M-451, ARONIX M-408, ARONIX M-400, ARONIX M-402, ARONIX M-403, ARONIX M-404, ARONIX M-405, ARONIX M-406 (all manufactured by Toagosei Co., Ltd.), EBECRYL 11, EBECRYL 145, EBECRYL 150, EBECRYL 40, EBECRYL 140, EBECRYL 180, DPGDA, HDDA, TPGDA, HPNDA, PETIA, PETRA, TMPTA, TMPEOTA, DPHA, EBECRYL series (all manufactured by Daicel Cytec Co., Ltd.), etc.

[0177] Preferred polyfunctional (meth)acrylates include compounds represented by the following formulae (B-1) to (B-14), respectively.

[0178] [Chemical formula 6]

[0179]

[0180] The non-liquid crystal compound containing a reactive group preferably has more than 2 reactive groups less than 12 in the molecule, more preferably has more than 2 polymerizable groups less than 12 in the molecule, and more preferably has more than 2 polymerizable groups less than 12 in the molecule. Multifunctional (meth) acrylates having polymerizable groups of less than 12 in the molecule. From the viewpoint of more easily improving film strength, the reactive group (number of polymerizable groups) possessed by the non-liquid crystal compound containing a reactive group is preferably more than 3 in one molecule, more preferably more than 4, and more preferably more than 5. The number of polymerizable groups possessed by the non-liquid crystal compound containing a reactive group is preferably less than 10 in one molecule, more preferably less than 9, and more preferably less than 8.

[0181] In the present invention, the reactive group (polymerizable group) possessed by the non-liquid crystal compound containing a reactive group is preferably the same as the polymerizable group possessed by the polymerizable liquid crystal compound. It should be noted that, in the case where at least one compound selected from the polymerizable liquid crystal compound and the non-liquid crystal compound containing a reactive group has a plurality of reactive groups, it is preferred that at least one polymerizable group possessed by the polymerizable liquid crystal compound is the same as at least one reactive group possessed by the non-liquid crystal compound containing a reactive group. For example, in the case where the non-liquid crystal compound containing a reactive group is a monofunctional (meth) acrylate, it is preferred that the polymerizable liquid crystal compound also has a (meth) acryloyloxy group. In the case where the non-liquid crystal compound containing a reactive group is a multifunctional (meth) acrylate, it is preferred that the polymerizable liquid crystal compound also has a (meth) acryloyloxy group.

[0182] Relative to 100 parts by mass of all polymerizable liquid crystal compounds in the composition, the content of the non-liquid crystal compound containing a reactive group in the polymerizable liquid crystal composition is 3 parts by mass or more and 18 parts by mass or less. The non-liquid crystal compound containing a reactive group is not easy to disturb the orientation of the polymerizable liquid crystal compound, and it is easy to suppress the change in the phase difference value after the heat resistance test while having high vertical orientation. From the perspective of the balance between the ability to suppress the change of the appropriate phase difference and the orderly orientation of the polymerizable liquid crystal compound, the content of the non-liquid crystal compound containing a reactive group is more preferably 5 parts by mass or more, and more preferably 15 parts by mass or less, relative to 100 parts by mass of all polymerizable liquid crystal compounds.

[0183] The weight average molecular weight of the non-liquid crystal compound containing a reactive group is preferably 1200 or less, more preferably 100 or less, and preferably 100 or more, more preferably 200 or more. When the weight average molecular weight of the non-liquid crystal compound containing a reactive group is within the above range, it is easy to suppress the change in the phase difference value after the heat resistance test while having high vertical alignment. The weight average molecular weight of the non-liquid crystal compound containing a reactive group can be measured, for example, by gel permeation chromatography (GPC).

[0184] Regarding the content of the non-liquid crystal compound containing a reactive group in the optically anisotropic film, it is preferably 3 parts by mass or more and 18 parts by mass or less relative to 100 parts by mass of the polymerizable liquid crystal compound constituting the optically anisotropic film. When the content of the non-liquid crystal compound containing a reactive group is within the aforementioned range, the non-liquid crystal compound containing a reactive group is not easy to disturb the orientation of the polymerizable liquid crystal compound, and it is easy to suppress the change in the phase difference value after the heat resistance test while having high vertical orientation. From the perspective of the balance between the ability to suppress the change of the appropriate phase difference and the orderly orientation of the polymerizable liquid crystal compound, the content of the non-liquid crystal compound containing a reactive group is more preferably 5 parts by mass or more, and more preferably 15 parts by mass or less relative to 100 parts by mass of the polymerizable liquid crystal compound constituting the optically anisotropic film.

[0185] The polymerizable liquid crystal composition used in the formation of the vertically aligned liquid crystal cured film may contain additives such as solvents, polymerization initiators, leveling agents, antioxidants, and photosensitizers in addition to other polymerizable liquid crystal compounds and vertical alignment promoters. Each of these components may be used alone or in combination of two or more.

[0186] The polymerizable liquid crystal composition used in the formation of the vertically aligned liquid crystal cured film is usually applied to a substrate, a vertically aligned film, etc. in a state dissolved in a solvent, and therefore preferably contains a solvent. As the solvent, it is preferably a solvent that can dissolve the polymerizable liquid crystal compound, and it is also preferably a solvent that is inactive for the polymerization reaction of the polymerizable liquid crystal compound. Examples of the solvent include alcohol solvents such as water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; 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; alicyclic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorinated solvents such as chloroform and chlorobenzene; amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone; and the like. These solvents may be used alone or in combination of two or more. Among them, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents, and aromatic hydrocarbon solvents are preferred.

[0187] Relative to 100 parts by mass of polymerizable liquid crystal composition, the content of the solvent in the polymerizable liquid crystal composition is preferably 50 to 98 parts by mass, more preferably 70 to 95 parts by weight. Therefore, the solid component preferably accounts for 2 to 50 parts by mass in 100 parts by mass of the polymerizable liquid crystal composition. When the solid component is less than 50 parts by mass, the viscosity of the polymerizable liquid crystal composition decreases, so the thickness of the film becomes roughly uniform, and there is a tendency to be less prone to unevenness. The above-mentioned solid component can be appropriately determined considering the thickness of the liquid crystal cured film to be manufactured.

[0188] The polymerization initiator is a compound that generates reactive species by the contribution of heat or light and can initiate a polymerization reaction of a polymerizable liquid crystal compound or the like. As reactive species, there can be mentioned active species such as free radicals, cations or anions. Among them, from the viewpoint of easy control of the reaction, a photopolymerization initiator that generates free radicals by light irradiation is preferred.

[0189] Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, benzyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, oxime compounds, triazine compounds, iodonium salts, and sulfonium salts. Specific examples include Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, and Irgacure 379EG (all manufactured by BASF Japan Co., Ltd.), SEIKUOL BZ, SEIKUOL Z, and SEIKUOL BEE (all manufactured by Seiko Chemical Industries, Ltd.), kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), kayacure UVI-6992 (manufactured by DOW), and ADEKA OPTOMER. SP-152, ADEKA OPTOMER SP-170, ADEKA OPTOMER N-1717, ADEKA OPTOMER N-1919, ADEKA ARKLS NCI-831, ADEKA ARKLS NCI-930 (the above are made by ADEKA Co., Ltd.), TAZ-A, TAZ-PP (the above are made by NihonSiberHegner KK) and TAZ-104 (Sanwa Chemical Co., Ltd.).

[0190] The photopolymerization initiator preferably has a maximum absorption wavelength of 300 nm to 400 nm, more preferably 300 nm to 380 nm, in order to fully utilize the energy emitted from the light source and achieve excellent productivity. Among them, α-acetophenone-based polymerization initiators and oxime-based photopolymerization initiators are preferred.

[0191] Examples of the α-acetophenone compound include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)-1-propanone, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzyl-1-butanone, and 2-dimethylamino-1-(4-morpholinophenyl)-2-(4-methylphenylmethyl)-1-butanone. More preferred examples include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)-1-propanone and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzyl-1-butanone. Examples of commercially available products of the α-acetophenone compound include Irgacure 369, 379EG, and 907 (all manufactured by BASF Japan Co., Ltd.) and Seikuol BEE (manufactured by Seiko Chemical Industries, Ltd.).

[0192] Oxime-based photopolymerization initiators generate free radicals such as phenyl radicals and methyl radicals by irradiating light. The polymerization of the polymerizable liquid crystal compound is appropriately carried out by the free radical, wherein the oxime-based photopolymerization initiator that can generate methyl radicals is preferred from the perspective of high initiation efficiency of the polymerization reaction. In addition, from the perspective of making the polymerization reaction more efficient, it is preferred to use a photopolymerization initiator that can efficiently utilize ultraviolet rays of more than 350nm. As a photopolymerization initiator that can efficiently utilize ultraviolet rays of more than 350nm, it is preferably a triazine compound or a carbazole compound containing an oxime structure, and from the perspective of sensitivity, it is more preferably a carbazole compound containing an oxime ester structure. As a carbazole compound containing an oxime structure, 1-[4-(phenylthio)1,2-octanedione 2-(O-benzoyl oxime)], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethanone-1-(O-acetyl oxime) and the like can be cited. Examples of commercially available products of oxime ester photopolymerization initiators include Irgacure OXE-01, Irgacure OXE-02, and Irgacure OXE-03 (all manufactured by BASF Japan Co., Ltd.), ADEKA OPTOMER N-1919, and ADEKA ARKLS NCI-831 (all manufactured by ADEKA Corporation).

[0193] The content of the photopolymerization initiator is generally 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 15 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. Within the above range, the reaction of the polymerizable group proceeds sufficiently and the alignment of the polymerizable liquid crystal compound is not easily disturbed.

[0194] The leveling agent refers to an additive having the function of adjusting the fluidity of the polymerizable liquid crystal composition and making the coating film obtained by applying the composition flatter, and examples thereof include silicone-based, polyacrylate-based, and perfluoroalkyl-based leveling agents.As the leveling agent, commercially available products can be used, and specific examples thereof include DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, and FZ2123 (all manufactured by Dow Corning Toray Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, and KF6001 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (all manufactured by Momentive Performance Materials Japan LLC), fluorinert (registered trademark) FC-72, fluorinert FC-40, fluorinert FC-43, fluorinert FC-3283 (all manufactured by Sumitomo 3M Co., Ltd.), MEGAFACE (registered trademark) R-08, MEGAFACE R-30, MEGAFACE R-90, MEGAFACE F-410, MEGAFACE F-411, MEGAFACE F-443, MEGAFACE F-445, MEGAFACE F-470, MEGAFACE F-477, MEGAFACE F-479, MEGAFACE F-482, MEGAFACE F-483, MEGAFACE F-556 (all manufactured by DIC Corporation), EFTOP (trade name) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC=105, KH=40, SA=100 (all manufactured by AGC Seimi Chemical Co., Ltd.), trade name E1830, trade name E5844 (manufactured by Daikin Fine Chemical Kenkyusho, KK), BM-1000, BM-1100, BYK-352, BYK-353 and BYK-361N (all trade names: manufactured by BM Chemie), etc.The leveling agent can be used alone or in combination of two or more.

[0195] The content of the leveling agent is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. When the content of the leveling agent is within the above range, it is easy to align the polymerizable liquid crystal compound and the resulting liquid crystal cured film tends to be smoother, so it is preferred.

[0196] By combining an antioxidant, the polymerization reaction of the polymerizable liquid crystal compound can be controlled. As an antioxidant, it can be a primary antioxidant selected from phenolic antioxidants, amine antioxidants, quinone antioxidants, and nitroso antioxidants, or it can be a secondary antioxidant selected from phosphorus antioxidants and sulfur antioxidants. In order to polymerize the polymerizable liquid crystal compound without disturbing the orientation of the polymerizable liquid crystal compound, the content of the antioxidant is generally 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. Antioxidants can be used alone or in combination of two or more.

[0197] In addition, by using a photosensitizer, the photopolymerization initiator can be highly sensitive. As a photosensitizer, for example, there can be mentioned: xanthone such as xanthone and thioxanthone; anthracenes with substituents such as anthracene and alkyl ether; phenothiazine; rubrene. The photosensitizer can be used alone or in combination of two or more. The content of the photosensitizer is generally 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound.

[0198] The polymerizable liquid crystal composition used for forming the vertically aligned liquid crystal cured film can be obtained by stirring a polymerizable liquid crystal compound, a solvent, a photopolymerization initiator, and components other than the polymerizable liquid crystal compound at a predetermined temperature.

[0199] [Optically anisotropic layer]

[0200] The optically anisotropic film of the present application is preferably used in combination with an optically anisotropic layer other than the optically anisotropic film. The optically anisotropic layer may be, for example, a stretched film or a cured layer of a polymerizable liquid crystal composition in which the polymerizable liquid crystal compound is cured in a state of being oriented in a horizontal direction relative to the film plane.

[0201] As stretched films, for example, uniaxially stretched polycarbonate (PC) films, uniaxially stretched triacetyl cellulose (TAC) films, and uniaxially stretched cycloolefin polymer (COP) films can be cited. The in-plane phase difference value of these stretched films can be adjusted by controlling the composition of the resin constituting the stretched film, the stretching method, and the thickness of the stretched film.

[0202] The thickness of the optically anisotropic layer is preferably 0.5 μm to 5 μm, more preferably 0.6 μm to 4.5 μm, and further preferably 0.7 μm to 4 μm. The thinner the thickness, the more preferred. Therefore, as described below, the optically anisotropic layer is preferably a cured product of a polymerizable liquid crystal composition in which a polymerizable liquid crystal compound is cured in a state oriented in a horizontal direction relative to the film plane (hereinafter also referred to as a "horizontally oriented liquid crystal cured film"), and further preferably a liquid crystal cured film in which a polymerizable liquid crystal compound having at least one free radical polymerizable group is cured in a state horizontally oriented relative to the in-plane direction of the cured film. By providing a horizontally oriented liquid crystal cured film whose thickness of the optically anisotropic layer satisfies the above range, it is possible to achieve lightweight image display devices.

[0203] The polymerizable liquid crystal compound constituting the horizontally aligned liquid crystal curing film is not particularly limited, and for example, a polymerizable liquid crystal compound previously known in the field of phase difference film can be used. Specifically, it is possible to use a polymerizable liquid crystal compound (X) or a polymerizable liquid crystal compound (Y) exemplified as a polymerizable liquid crystal compound that can be used in the formation of a horizontally aligned liquid crystal curing film, wherein it is preferred to include at least one polymerizable liquid crystal compound that exhibits so-called reverse wavelength dispersion, for example, a polymerizable liquid crystal compound (X) can be preferably used. In the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal curing film, the polymerizable liquid crystal compound can be used alone or in combination of two or more, and a polymerizable liquid crystal compound (X) and a polymerizable liquid crystal compound (Y) can also be used in combination.

[0204] The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition used in the formation of the horizontally aligned liquid crystal cured film is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and further preferably 90 to 95 parts by mass, relative to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. When the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the obtained liquid crystal cured film.

[0205] The polymerizable liquid crystal composition used in the formation of the horizontal alignment liquid crystal cured film may contain additives such as a solvent, a polymerization initiator, a leveling agent, an antioxidant, and a photosensitizer in addition to the polymerizable liquid crystal compound. As these components, the same components as those exemplified above as components that can be used in the vertical alignment liquid crystal cured film can be cited, and only one of each can be used, or two or more can be used in combination.

[0206] The polymerizable liquid crystal composition used for forming the horizontally aligned liquid crystal cured film can be obtained by stirring a polymerizable liquid crystal compound, a solvent, a photopolymerization initiator and other components other than the polymerizable liquid crystal compound at a predetermined temperature.

[0207] [Laminate and method for producing laminate]

[0208] The laminate of the present invention comprises an optically anisotropic film and an optically anisotropic layer. In one embodiment of the present invention, when the optically anisotropic film of the present invention and the optically anisotropic layer are laminated, as Figure 2 As shown, a laminate including an optically anisotropic film 1 and an optically anisotropic layer 2 in this order is a laminate 10. As the optically anisotropic film, for example, a cured product of a polymerizable liquid crystal composition in which a polymerizable liquid crystal compound is cured in a state oriented in a direction perpendicular to the film plane (vertically oriented liquid crystal cured film) can be used. In addition, as the optically anisotropic layer, as described above, for example, a stretched film or a cured product layer of a polymerizable liquid crystal composition in which a polymerizable liquid crystal compound is cured in a state oriented in a horizontal direction relative to the film plane (horizontally oriented liquid crystal cured film) can be used.

[0209] For example, the laminate of the present invention can be manufactured by the following process: forming a coating film of a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film containing a polymerizable liquid crystal compound on a stretched film, and forming a vertically aligned liquid crystal cured film from the coating film (hereinafter also referred to as "vertically aligned liquid crystal cured film forming process").

[0210] With regard to the laminate of the present invention, for example, a laminate having an optically anisotropic film directly on an optically anisotropic layer can be manufactured by the following method, which sequentially comprises: forming a coating film of a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film containing a polymerizable liquid crystal compound, a step of forming a horizontally aligned liquid crystal cured film from the coating film (hereinafter also referred to as a "horizontally aligned liquid crystal cured film forming step"); and a vertically aligned liquid crystal cured film forming step.

[0211] In the laminate of the present invention, when the optically anisotropic layer is formed of a horizontally aligned liquid crystal cured film, it is preferred that a step of forming a coating film of a horizontally aligned film-forming composition and forming a horizontally aligned film from the coating film is included before forming the horizontally aligned liquid crystal cured film (hereinafter also referred to as a "horizontal alignment film forming step"), and the horizontal alignment film forming step and the horizontal alignment liquid crystal cured film forming step are preferably performed sequentially and continuously. By a manufacturing method including a horizontal alignment film forming step, an optically anisotropic layer composed of a horizontally aligned liquid crystal cured film formed on a horizontal alignment film is obtained.

[0212] In the horizontal alignment liquid crystal cured film forming step, the horizontal alignment liquid crystal cured film can be produced, for example, by the following method, which includes:

[0213] A step of applying a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film onto a substrate or an alignment film to obtain a coating film;

[0214] A step of drying the coating to form a dried coating; and

[0215] A step of irradiating the dried coating film with active energy rays to form a horizontally aligned liquid crystal cured film.

[0216] The coating film of the polymerizable liquid crystal composition can be formed by, for example, applying the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film on a substrate, an alignment film described later, or the like.

[0217] As the substrate, for example, a glass substrate, a film substrate, etc. can be cited, but from the viewpoint of processability, a resin film substrate is preferred. As the resin constituting the film substrate, for example, 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; plastics such as polyphenylene sulfide and polyphenylene ether. Such resins can be made into substrates by known means such as solvent casting and melt extrusion. The surface of the substrate can have a protective layer formed by acrylic resin, methacrylic resin, epoxy resin, oxetane resin, polyurethane resin, melamine resin, etc., and surface treatments such as mold release treatment, corona treatment, and plasma treatment such as silicone treatment can also be implemented.

[0218] As the substrate, commercially available products can be used. Examples of commercially available cellulose ester substrates include cellulose ester substrates manufactured by Fuji Photo Film Co., Ltd. such as Fujitack Film; cellulose ester substrates manufactured by Konica Minolta Opto Co., Ltd. such as "KC8UX2M", "KC8UY", and "KC4UY", etc. Examples of commercially available cyclic olefin resins include 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 Co., Ltd. such as "ZEONOR (Registered Trademark)" and "ZEONEX (Registered Trademark)"; and cyclic olefin resins manufactured by Mitsui Chemicals, Inc. such as "Apel (Registered Trademark). Commercially available cyclic olefin resin substrates may also be used. Examples of commercially available cyclic olefin resin substrates include cyclic olefin resin substrates such as "Escena (registered trademark)" and "SCA40 (registered trademark)" manufactured by Sekisui Chemical Co., Ltd.; cyclic olefin resin substrates such as "ZEONORFILM (registered trademark)" manufactured by OPTES Co., Ltd.; and cyclic olefin resin substrates such as "ARTONFILM (registered trademark)" manufactured by JSR Co., Ltd.

[0219] From the viewpoints of thinning the laminate, ease of peeling of the substrate, and operability of the substrate, the thickness of the substrate is usually 5 to 300 μm, preferably 10 to 150 μm. In addition, when the substrate is arranged in the laminate of the present invention, from the viewpoint of optical compensation described later, the substrate is preferably optically isotropic. In the present invention, optical isotropy means that the in-plane phase difference value of the substrate is 3 nm or less.

[0220] Examples of a method for applying the polymerizable liquid crystal composition to a substrate include known methods such as spin coating, extrusion, gravure coating, die coating, bar coating, and applicator coating, and printing methods such as flexographic printing.

[0221] Then, the solvent is removed by drying, etc. to form a dry coating. As a drying method, natural drying, ventilation drying, heating drying and reduced pressure drying methods, etc. can be cited. At this time, by heating the coating obtained by the polymerizable liquid crystal composition, the polymerizable liquid crystal compound can be oriented in the horizontal direction relative to the coating plane while the solvent is dried and removed from the coating. The heating temperature of the coating can be appropriately determined by considering the materials of the polymerizable liquid crystal compound used and the substrate to be formed, but in order to make the polymerizable liquid crystal compound phase change to a liquid crystal phase state, it is usually necessary to be a temperature above the liquid crystal phase transition temperature. In order to remove the solvent contained in the polymerizable liquid crystal composition and make the polymerizable liquid crystal compound become a horizontal orientation state, for example, it can be heated to a temperature above the liquid crystal phase transition temperature (smectic phase transition temperature or nematic phase transition temperature) of the polymerizable liquid crystal compound contained in the above-mentioned polymerizable liquid crystal composition.

[0222] It should be noted that the liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), etc., which are equipped with a temperature regulating station. In addition, when two or more kinds are used in combination as polymerizable liquid crystal compounds, the above-mentioned phase transition temperature refers to: a mixture of polymerizable liquid crystal compounds obtained by mixing all polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition in the same ratio as the composition in the polymerizable liquid crystal composition, and the temperature measured by operating in the same manner as when using one polymerizable liquid crystal compound. It should be noted that it is known that the following situation usually exists: the liquid crystal phase transition temperature of the polymerizable liquid crystal compound in the aforementioned polymerizable liquid crystal composition is lower than the liquid crystal phase transition temperature of the polymerizable liquid crystal compound monomer.

[0223] The heating time can be appropriately determined depending on the heating temperature, the type of polymerizable liquid crystal compound used, the type of solvent, its boiling point and its amount, etc., and is usually 15 seconds to 10 minutes, preferably 0.5 to 5 minutes.

[0224] The removal of the solvent from the coating can be carried out simultaneously with the heating reaching the liquid crystal phase transition temperature of the polymerizable liquid crystal compound, or it can be carried out independently, but from the viewpoint of improving productivity, it is preferably carried out simultaneously. Before the heating reaching the liquid crystal phase transition temperature of the polymerizable liquid crystal compound, a pre-drying process for appropriately removing the solvent in the coating under the condition that the polymerizable liquid crystal compound contained in the coating obtained by the polymerizable liquid crystal composition is not polymerized can be provided. As the drying method in the pre-drying process, natural drying method, ventilation drying method, heating drying and reduced pressure drying method, etc. can be cited, and the drying temperature (heating temperature) in the drying process can be appropriately determined according to the type of polymerizable liquid crystal compound used, the type of solvent, its boiling point and its amount, etc.

[0225] Then, in the obtained dry coating, while maintaining the horizontal orientation state of the polymerizable liquid crystal compound, the polymerizable liquid crystal compound is polymerized to form a horizontally oriented liquid crystal cured film. As a polymerization method, thermal polymerization and photopolymerization can be cited. From the viewpoint of easy control of polymerization reaction, photopolymerization is preferred. In photopolymerization, as the light irradiated to the dry coating, it can be appropriately selected according to the type of polymerization initiator contained in the dry coating, the type of polymerizable liquid crystal compound (especially the type of polymerizable group possessed by the polymerizable liquid crystal compound) and its amount. As a specific example, more than one light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α rays, β rays and γ rays, and active electron beams can be cited. Among them, from the aspect of easy control of the progress of the polymerization reaction, it can be used as a photopolymerization device and the device widely used in the art is considered, preferably ultraviolet light, preferably in a way that can be photopolymerized using ultraviolet light. The type of polymerizable liquid crystal compound and polymerization initiator contained in the polymerizable liquid crystal composition is pre-selected. In addition, during polymerization, it is also possible to utilize appropriate cooling means to cool the dried coating film while performing light irradiation, thereby controlling the polymerization temperature. If the polymerization of the polymerizable liquid crystal compound is implemented at a lower temperature by adopting such cooling means, even if a substrate with lower heat resistance is used, a horizontally oriented liquid crystal cured film can be appropriately formed. In addition, within the range of the unfavorable conditions (deformation of the substrate due to heat, etc.) caused by the heat during light irradiation, it is also possible to promote the polymerization reaction by increasing the polymerization temperature. During photopolymerization, by shielding, developing, etc., a patterned cured film can also be obtained.

[0226] As the light source of the aforementioned active energy rays, for example, there can be mentioned a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excimer laser, an LED light source emitting light in the wavelength range of 380 to 440 nm, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, a metal halide lamp, and the like.

[0227] UV radiation intensity is usually 10 to 3,000 mW / cm 2 The ultraviolet irradiation intensity is preferably an intensity in the wavelength region effective for activating the photopolymerization initiator. The irradiation time is usually 0.1 second to 10 minutes, preferably 0.1 second to 5 minutes, more preferably 0.1 second to 3 minutes, and further preferably 0.1 second to 1 minute. When irradiating once or more times with such ultraviolet irradiation intensity, the cumulative light amount is 10 to 3,000 mJ / cm 2 , preferably 50 to 2,000 mJ / cm 2 , more preferably 100 to 1,000 mJ / cm 2 .

[0228] Since the alignment order of the horizontally aligned liquid crystal cured film can be improved, it is preferred in the present invention that the coating film of the polymerizable liquid crystal composition for forming the horizontally aligned liquid crystal cured film is formed on the horizontally aligned film having an alignment control force in the horizontal direction relative to the plane of the obtained liquid crystal cured film. Therefore, in the laminate of the present invention, it is preferred that the optically anisotropic layer is formed on the horizontally aligned film, and the horizontally aligned liquid crystal cured film is sequentially included.

[0229] The alignment control force of the alignment film can be arbitrarily adjusted by the type of the alignment film, the surface state, the rubbing conditions, etc., and when the alignment film is formed of a photo-aligning polymer, it can be arbitrarily adjusted by the polarized light irradiation conditions, etc.

[0230] As the horizontal alignment film, it is preferred that the horizontal alignment film has solvent resistance that does not dissolve due to the coating of the polymerizable liquid crystal composition, and has heat resistance in the heat treatment for the removal of the solvent and the orientation of the polymerizable liquid crystal compound described later. As the alignment film, there can be cited alignment films containing an aligning polymer, photoalignment films, groove alignment films having a concave-convex pattern and a plurality of grooves on the surface, and stretched films stretched along the alignment direction. From the perspective of the accuracy and quality of the alignment angle, the photoalignment film is preferred.

[0231] As the oriented polymer, for example, polyamides having amide bonds in the molecule, gelatins, polyimides having imide bonds in the molecule and polyamic acid as their hydrolyzates, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinyl pyrrolidone, polyacrylic acid and polyacrylates can be cited. Among them, polyvinyl alcohol is preferred. The oriented polymer can be used alone or in combination of two or more.

[0232] The oriented film containing the oriented polymer can be obtained by applying a composition obtained by dissolving the oriented polymer in a solvent (hereinafter, sometimes referred to as "oriented polymer composition") to a substrate and removing the solvent, or applying the oriented polymer composition to a substrate and removing the solvent, and rubbing (rubbing method). As the solvent, the same solvent as the solvent exemplified in the above text as a solvent that can be used for the polymerizable liquid crystal composition can be cited.

[0233] The concentration of the oriented polymer in the oriented polymer composition may be within a range in which the oriented polymer material can be completely dissolved in the solvent, and is preferably about 0.1 to 20%, more preferably about 0.1 to 10%, based on the solid content of the solution.

[0234] As the oriented polymer composition, a commercially available oriented film material may be used as it is. Examples of commercially available oriented film materials include SUNEVER (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and OPTMER (registered trademark, manufactured by JSR Corporation).

[0235] As a method for applying the oriented polymer composition to the substrate, the same method as the method exemplified above as the method for applying the polymerizable liquid crystal composition to the substrate can be mentioned.

[0236] Examples of a method for removing the solvent contained in the oriented polymer composition include a natural drying method, a ventilation drying method, a heat drying method, and a reduced pressure drying method.

[0237] In order to impart an orientation control force to the oriented film, a rubbing treatment (rubbing method) may be performed as required. As a method for imparting an orientation control force using the rubbing method, the following method may be cited: a film of an oriented polymer formed on the surface of a substrate by coating an oriented polymer composition on a substrate and annealing the oriented polymer composition is brought into contact with a rubbing roller wound with a rubbing cloth and rotating. If shielding is performed during the rubbing treatment, multiple regions (patterns) with different orientation directions can also be formed on the oriented film.

[0238] In one suitable embodiment of the present invention, the horizontal alignment film is a photoalignment film formed of a polymer having a (meth)acryloyl group. When the horizontal alignment film has a polymerizable group similar to or the same as the polymerizable liquid crystal compound constituting the horizontal alignment liquid crystal cured film, there is a tendency that the adhesion between the horizontal alignment film and the horizontal alignment liquid crystal cured film is further improved, so it is preferred that the horizontal alignment film is formed of a polymer having a (meth)acryloyl group, and the horizontal alignment liquid crystal cured film is formed of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having a (meth)acryloyl group.

[0239] The photo-alignment film can be generally obtained by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter also referred to as a "photo-alignment film-forming composition") to a substrate, removing the solvent, and then irradiating with polarized light (preferably polarized UV light). The photo-alignment film is advantageous in that the direction of the orientation control force can be arbitrarily controlled by selecting the polarization direction of the irradiated polarized light.

[0240] The so-called photoreactive group refers to a group that generates liquid crystal orientation ability by irradiation with light. Specifically, groups that participate in the photoreactions that are the origin of the liquid crystal orientation ability, such as the orientation induction or isomerization reaction, dimerization reaction, photocrosslinking reaction or photodecomposition reaction of molecules generated by irradiation with light, can be cited. Among them, from the perspective of excellent orientation, it is preferably a group that participates in dimerization reaction or photocrosslinking reaction. As a photoreactive group, it is preferably a group having an unsaturated bond, especially a double bond, and it is particularly preferably a group having at least one selected from the group consisting of a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), a nitrogen-nitrogen double bond (N=N bond) and a carbon-oxygen double bond (C=O bond).

[0241] As photoreactive groups having C=C bonds, vinyl, polyene, stilbene, stilbazole, stilbenazolium, chalcone, and cinnamoyl groups can be cited. As photoreactive groups having C=N bonds, groups having structures such as aromatic Schiff bases and aromatic hydrazones can be cited. As photoreactive groups having N=N bonds, azophenyl, azonaphthyl, aromatic heterocyclic azo, disazo, formazan, and groups having an oxidized azobenzene structure can be cited. As photoreactive groups having C=O bonds, benzophenone, coumarin, anthraquinone, and maleimide groups can be cited. These groups can have substituents such as alkyl, alkoxy, aryl, allyloxy, cyano, alkoxycarbonyl, hydroxyl, sulfonic acid, and halogenated alkyl.

[0242] Among them, photoreactive groups that participate in the photodimerization reaction are preferred, and azo, cinnamoyl and chalcone groups are preferred from the viewpoint that the amount of polarized light irradiation required for photo-alignment is small and a photo-alignment film with excellent thermal stability and temporal stability can be easily obtained. As the polymer having a photoreactive group, a polymer having an azo or cinnamoyl group is preferred, and from the viewpoint of improving the adhesion between the horizontal alignment film and the horizontal alignment liquid crystal cured film, a polymer having a cinnamoyl group such as a cinnamic acid structure at the terminal of the polymer side chain is particularly preferred.

[0243] By applying the photo-alignment film-forming composition on a substrate, a photo-alignment inducing layer can be formed on the substrate. The solvent contained in the composition may be the same solvent as the solvent previously exemplified as a solvent that can be used in the polymerizable liquid crystal composition, and may be appropriately selected according to the solubility of the polymer or monomer having a photoreactive group.

[0244] The content of the polymer or monomer having a photoreactive group in the composition for forming a photo-alignment film can be appropriately adjusted according to the type of the polymer or monomer and the thickness of the target photo-alignment film, and is preferably set to 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 a photo-alignment film. The composition for forming a photo-alignment film may also contain a polymer material such as polyvinyl alcohol and polyimide, and a photosensitizer within a range that does not significantly impair the properties of the photo-alignment film.

[0245] As a method for applying the photo-alignment film-forming composition to a substrate, the same method as the method for applying the oriented polymer composition to a substrate can be cited. As a method for removing the solvent from the applied photo-alignment film-forming composition, for example, natural drying, ventilation drying, heating drying, and reduced pressure drying can be cited.

[0246] When irradiating polarized light, it can be a method of directly irradiating polarized UV light to the product obtained after removing the solvent from the composition for forming a photo-alignment film applied on the substrate, or it can be a method of irradiating polarized light from the substrate side and transmitting the polarized light. In addition, it is particularly preferred that the polarized light is substantially parallel light. The wavelength of the irradiated polarized light is preferably a wavelength in the wavelength region where the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) in the range of 250 to 400 nm is particularly preferred. As the light source used in the polarized light irradiation, xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, ultraviolet lasers such as KrF and ArF can be cited, and high-pressure mercury lamps, ultra-high-pressure mercury lamps and metal halide lamps are more preferred. Among them, high-pressure mercury lamps, ultra-high-pressure mercury lamps and metal halide lamps are preferred because of the large luminous intensity of ultraviolet rays with a wavelength of 313 nm. Polarized UV light can be irradiated by passing light from the aforementioned light source through an appropriate polarizer. As the polarizer, a polarizing filter, a polarizing prism such as Glan-Thompson or Glan-Taylor, or a wire grid type polarizer can be used.

[0247] It should be noted that, by shielding during rubbing or polarized light irradiation, a plurality of regions (patterns) in which the directions of liquid crystal alignment are different can be formed.

[0248] The groove oriented film is a film having a concavo-convex pattern or multiple grooves (grooves) on the film surface. When a polymerizable liquid crystal compound is applied to a film having multiple linear grooves arranged at equal intervals, the liquid crystal molecules will be oriented in the direction along the grooves.

[0249] As methods for obtaining a grooved oriented film, there are: a method of exposing the surface of a photosensitive polyimide film through an exposure mask having a slit in a pattern shape, and then developing and rinsing to form a concave-convex pattern; a method of forming a layer of a UV-curable resin before curing on a plate-like original plate having grooves on its surface, transferring the formed resin layer to a substrate, and then curing it; and a method of pressing a roll-shaped original plate having a plurality of grooves against a film of a UV-curable resin before curing formed on a substrate to form convex-concave and concave, and then curing it; and the like.

[0250] The thickness of the alignment film (alignment film or photoalignment film containing an aligning polymer) is usually 100 to 5000 nm, preferably 100 to 1000 nm, more preferably 100 to 500 nm, further preferably 100 to 300 nm, and particularly preferably 100 to 250 nm. When the thickness of the alignment film is within the above range, the alignment film has sufficient horizontal alignment control power, and cohesive failure is not likely to occur at the alignment film in the laminate.

[0251] When the optically anisotropic film in the laminate of the present invention is formed of a vertically aligned liquid crystal cured film,

[0252] The vertically aligned liquid crystal cured film can be produced by, for example, a method including the following steps in the vertically aligned liquid crystal cured film forming step, wherein the laminate having the optically anisotropic film directly on the optically anisotropic layer is:

[0253] A step of applying a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film onto a stretched film (optically anisotropic layer) to obtain a coating film;

[0254] A step of drying the coating to form a dried coating; and

[0255] A step of irradiating the dried coating film with active energy rays to form a vertically aligned liquid crystal cured film.

[0256] The formation of the coating film of the polymerizable liquid crystal composition can be carried out, for example, by coating the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film on a stretched film. As a coating method of the polymerizable liquid crystal composition, the same method as that used in the method for producing a horizontally aligned liquid crystal cured film can be cited.

[0257] The vertically aligned liquid crystal cured film can be produced by, for example, a method in which the vertically aligned liquid crystal cured film forming process includes the following steps:

[0258] A step of applying a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film onto the horizontally aligned liquid crystal cured film to obtain a coating film;

[0259] A step of drying the coating to form a dried coating; and

[0260] A step of irradiating the dried coating film with active energy rays to form a vertically aligned liquid crystal cured film.

[0261] The formation of the coating film of the polymerizable liquid crystal composition can be carried out, for example, by coating the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film on the horizontally aligned liquid crystal cured film. As a coating method of the polymerizable liquid crystal composition, the same method as that used in the method for manufacturing the horizontally aligned liquid crystal cured film can be cited.

[0262] In addition, the formation of the coating of the polymerizable liquid crystal composition can be carried out, for example, by applying a polymerizable liquid crystal composition for forming a vertically oriented liquid crystal cured film on the aforementioned substrate. As a substrate, a substrate exemplified in the method for manufacturing a horizontally oriented liquid crystal cured film can be used. In addition, in the case where the substrate is configured in the laminate of the present invention, from the perspective of optical compensation described later, the substrate is preferably optically isotropic. In the present invention, optical isotropy refers to an in-plane phase difference value of the substrate of less than 3nm.

[0263] As far as the laminated body of the present invention is concerned, the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film can be laminated via other layers as long as the effect of the present invention is not affected. As such other layers, for example, an adhesive bonding layer can be cited. When the laminated body of the present invention includes an adhesive bonding layer, the thickness of the adhesive bonding layer is preferably 0.1 to 30 μm, more preferably 0.5 to 20 μm.

[0264] Examples of the adhesive layer include pressure-sensitive adhesives and energy-ray-curable adhesives, of which acrylic adhesives, epoxy adhesives, and urethane adhesives are preferred because of their high transparency and excellent heat resistance.

[0265] In addition, the laminate of the present invention may include a cured resin layer, a hard coating layer, etc. for the purpose of improving or enhancing the mechanical strength of the liquid crystal curing film as the above-mentioned other layer. When the laminate of the present invention includes such other layers between the horizontally oriented liquid crystal curing film and the vertically oriented liquid crystal curing film, the thickness of the above-mentioned other layer is preferably 0.1 to 4 μm, and more preferably 0.5 to 3 μm. When the laminate of the present invention includes such other layers between the horizontally oriented liquid crystal curing film and the vertically oriented liquid crystal curing film, the other layers can be formed after the horizontally oriented liquid crystal curing film is formed, and then a coating film of a polymerizable liquid crystal composition for forming a vertically oriented liquid crystal curing film is formed on the aforementioned other layers.

[0266] The aforementioned cured resin layer can be formed of, for example, acrylic resin, methacrylic resin, epoxy resin, oxetane resin, polyurethane resin, melamine resin, etc. By providing the cured resin layer, even if the liquid crystal cured film formed adjacent to the cured resin layer is a thin film, the cured resin layer can serve as a protective layer or a reinforcing layer to fully supplement the strength of the liquid crystal cured film.

[0267] After forming the coating of polymerizable liquid crystal composition, the solvent is removed by drying, etc., thereby forming a dry coating. As a drying method, natural drying method, ventilation drying method, heating drying and reduced pressure drying method, etc. can be cited. From the aspect of productivity, it is preferably heated and dried, and for the heating temperature in this case, the solvent can be preferably removed, and it is above the phase transition temperature of the polymerizable liquid crystal compound. About the steps and conditions in the process, the steps and conditions that can be adopted in the manufacture method of the horizontally oriented liquid crystal cured film can be cited.

[0268] The obtained dried coating film is irradiated with active energy rays (more specifically, ultraviolet rays, etc.), and the polymerizable liquid crystal compound is polymerized while maintaining the state of being oriented in a vertical direction relative to the coating film plane, thereby forming a vertically oriented liquid crystal cured film. As a polymerization method, the same method as that used in the method for producing a horizontally oriented liquid crystal cured film can be cited.

[0269] The laminated body of the present invention may be a laminated body in which an optically anisotropic layer is arranged on an optically anisotropic film.

[0270] A laminate having an optically anisotropic layer disposed on an optically anisotropic film can be produced by the following method, which sequentially comprises:

[0271] A step of applying a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film to a substrate to obtain a coating film;

[0272] A step of drying the coating to form a dried coating;

[0273] The step of irradiating the dried coating film with active energy rays to form a vertically aligned liquid crystal cured film;

[0274] A step of applying a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film on the vertically aligned liquid crystal cured film to obtain a coating film;

[0275] A step of drying the coating to form a dried coating; and

[0276] A step of irradiating the dried coating film with active energy rays to form a horizontally aligned liquid crystal cured film.

[0277] In the laminate of the present invention, when an optically anisotropic layer is formed on an optically anisotropic film, it is preferred that a step of forming a horizontal alignment film by a horizontal alignment film forming step is included before forming a horizontal alignment liquid crystal cured film. Here, the horizontal alignment film forming step can be the same step as the method exemplified in the aforementioned horizontal alignment liquid crystal cured film forming step.

[0278] [Polarizing plate]

[0279] The present invention includes a polarizing plate comprising the optically anisotropic film of the present invention and a polarizing film.

[0280] The polarizing film is a film having a polarizing function, and examples thereof include a stretched film adsorbed with a dye having absorption anisotropy, a film coated with a dye having absorption anisotropy as a polarizer, etc. As the dye having absorption anisotropy, for example, a dichroic dye can be mentioned.

[0281] For a film that includes a stretched film adsorbed with a dye having absorption anisotropy as a polarizer, it is usually produced by clamping a transparent protective film on at least one side of the following polarizer via an adhesive, and the polarizer is manufactured through the following steps: a step of uniaxially stretching a polyvinyl alcohol resin film; a step of dyeing the polyvinyl alcohol resin film with a dichroic dye so that it adsorbs the dichroic dye; a step of treating the polyvinyl alcohol resin film adsorbed with the dichroic dye with an aqueous boric acid solution; and a step of washing with water after the treatment with the aqueous boric acid solution.

[0282] The polyvinyl alcohol resin is obtained by saponifying a polyvinyl acetate resin. As the polyvinyl acetate resin, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, copolymers of vinyl acetate and other monomers copolymerizable therewith can be used. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

[0283] The saponification degree of the polyvinyl alcohol resin is usually about 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin may be modified, for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used. The degree of polymerization of the polyvinyl alcohol resin is usually about 1,000 to 10,000, preferably in the range of 1,500 to 5,000.

[0284] The film made of such a polyvinyl alcohol resin can be used as a raw film of a polarizing film. The method of making a polyvinyl alcohol resin into a film is not particularly limited, and the film can be made by a known method. The film thickness of the polyvinyl alcohol raw film can be, for example, about 10 to 150 μm.

[0285] The uniaxial stretching of the polyvinyl alcohol resin film can be performed before, at the same time as, or after dyeing based on a dichroic pigment. In the case of uniaxial stretching after dyeing, the uniaxial stretching can be performed before or during the boric acid treatment. In addition, the uniaxial stretching can be performed in multiple stages thereof. When the uniaxial stretching is performed, the uniaxial stretching can be performed between rollers having different peripheral speeds, or the uniaxial stretching can be performed using a hot roller. In addition, the uniaxial stretching can be dry stretching performed in the atmosphere, or wet stretching performed in a state where the polyvinyl alcohol resin film is swollen with a solvent. The stretching ratio is usually about 3 to 8 times.

[0286] The polyvinyl alcohol-based resin film can be dyed with a dichroic dye by, for example, a method of immersing the polyvinyl alcohol-based resin film in an aqueous solution containing a dichroic dye.

[0287] As the dichroic pigment, specifically, iodine and dichroic organic dyes can be used. As the dichroic organic dyes, dichroic direct dyes formed by disazo compounds such as CI Direct Red (DIRECT RED) 39, and dichroic direct dyes formed by compounds such as triazo and tetrakis azo can be cited. For the polyvinyl alcohol-based resin film, it is preferably immersed in water before dyeing.

[0288] When iodine is used as a dichroic pigment, a method of dyeing a polyvinyl alcohol-based resin film by immersing it in an aqueous solution containing iodine and potassium iodide can generally be adopted. The content of iodine in the aqueous solution is generally about 0.01 to 1 part by mass relative to 100 parts by mass of water. In addition, the content of potassium iodide is generally about 0.5 to 20 parts by mass relative to 100 parts by mass of water. The temperature of the aqueous solution used for dyeing is generally about 20 to 40°C. In addition, the immersion time (dyeing time) in the aqueous solution is generally about 20 to 1,800 seconds.

[0289] On the other hand, when a dichroic organic dye is used as the dichroic pigment, a method of dyeing the polyvinyl alcohol-based resin film by immersing the film in an aqueous solution containing a water-soluble dichroic dye can be generally adopted. The content of the dichroic organic dye in the aqueous solution is generally 1×10 -4 ~10 parts by mass, preferably 1×10 -3 ~1 mass part, more preferably 1×10 -3 ~1×10 -2The aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing auxiliary. The temperature of the dichroic dye aqueous solution used for dyeing is usually about 20 to 80° C. In addition, the immersion time (dyeing time) in the aqueous solution is usually about 10 to 1,800 seconds.

[0290] Boric acid treatment after dyeing based on dichroic pigments can usually be carried out by immersing the dyed polyvinyl alcohol-based resin film in an aqueous solution of boric acid. The content of boric acid in the aqueous solution of boric acid is usually about 2 to 15 parts by mass, preferably 5 to 12 parts by mass, relative to 100 parts by mass of water. When iodine is used as a dichroic pigment, the aqueous solution of boric acid preferably contains potassium iodide, and the content of potassium iodide at this time is usually about 0.1 to 15 parts by mass, preferably 5 to 12 parts by mass, relative to 100 parts by mass of water. The immersion time in the aqueous solution of boric acid is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds. The temperature of the boric acid treatment is usually above 50°C, preferably 50 to 85°C, and more preferably 60 to 80°C.

[0291] Generally, the polyvinyl alcohol-based resin film treated with boric acid can be subjected to a water washing treatment. The water washing treatment can be performed, for example, by immersing the polyvinyl alcohol-based resin film treated with boric acid in water. The temperature of water in the water washing treatment is generally about 5 to 40° C. In addition, the immersion time is generally about 1 to 120 seconds.

[0292] A drying treatment can be performed after washing to obtain a polarizer. The drying treatment can be performed, for example, using a hot air dryer or a far-infrared heater. The temperature of the drying treatment is usually about 30 to 100°C, preferably 50 to 80°C. The time of the drying treatment is usually about 60 to 600 seconds, preferably 120 to 600 seconds. By drying, the moisture content of the polarizer can be reduced to a practical level. The moisture content is usually about 5 to 20% by mass, preferably 8 to 15% by mass. When the moisture content is less than 5% by mass, the flexibility of the polarizer is lost, and the polarizer is sometimes damaged or broken after it is dried. In addition, when the moisture content is higher than 20% by mass, there is a possibility that the thermal stability of the polarizer will deteriorate.

[0293] The thickness of the polarizer obtained by uniaxially stretching the polyvinyl alcohol-based resin film, dyeing it with a dichroic dye, treating it with boric acid, washing it with water, and drying it as described above is preferably 5 to 40 μm.

[0294] As a film formed by coating a pigment having absorption anisotropy, a film obtained by coating a composition containing a dichroic pigment having liquid crystal properties or a composition containing a dichroic pigment and polymerizable liquid crystal, etc. can be cited. The film preferably has a protective film on one or both sides. As the protective film, a film identical to the resin film exemplified in the above text as a base material that can be used in the manufacture of a horizontally oriented liquid crystal cured film can be cited.

[0295] The film formed by coating the dye having absorption anisotropy is preferably as thin as possible, but if it is too thin, the strength decreases and the processability tends to be poor. The thickness of the film is usually 20 μm or less, preferably 5 μm or less, and more preferably 0.5 to 3 μm.

[0296] Specific examples of the film formed by coating a dye having absorption anisotropy include films described in JP-A-2012-33249 and the like.

[0297] A transparent protective film may be laminated on at least one side of the polarizer obtained as described above via, for example, an adhesive layer. As the transparent protective film, the same transparent film as the resin film exemplified above as a base material that can be used in the production of a liquid crystal cured film can be used.

[0298] The polarizing plate of the present invention comprises the optically anisotropic film of the present invention and a polarizing film, and can be obtained by laminating the optically anisotropic film of the present invention and the polarizing film with an adhesive layer interposed therebetween, for example.

[0299] In one embodiment of the present invention, when the laminate of the present invention is laminated with a polarizing film, Figure 3 The example includes a polarizing film 3 and an optically anisotropic film ( Figure 3 The laminate of the layer 1 in the laminate becomes the polarizing plate 20. At this time, the polarizing plate of the present invention can be obtained by laminating the optically anisotropic film to the polarizing film 3 via an adhesive layer. In the present invention, when an optically anisotropic layer is laminated in addition to the polarizing film and the optically anisotropic film, it is preferred that the laminate is laminated in such a way that the angle between the slow axis (optical axis) of the optically anisotropic layer constituting the laminate and the absorption axis of the polarizing film becomes 90±5°.

[0300] As the adhesive layer for bonding the polarizing film and the optically anisotropic film or the optically anisotropic layer, the same layer as exemplified as the other layer for bonding the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film can be used.

[0301] The polarizing plate of the present invention may have a structure as that of a conventional polarizing plate, or a polarizing film and a phase difference film. Such a structure may include, for example, an adhesive layer (sheet) for attaching the polarizing plate to a display element such as a liquid crystal display device, a protective film used to protect the surface of the polarizing film and the liquid crystal curing film from damage or contamination, and the like.

[0302] The laminate and polarizing plate of the present invention can be used in various display devices.

[0303] The so-called display device is a device having a display element, including a light-emitting element or a light-emitting device as a light source. As the display device, there can be cited a liquid crystal display device, an organic electroluminescent (EL) display device, an inorganic electroluminescent (EL) display device, a touch panel display device, an electron emission display device (such as a field emission display device (FED), a surface field emission display device (SED)), an electronic paper (a display device using electronic ink, an electrophoretic element, a plasma display device, a projection type display device (such as a grating light valve (GLV) display device, a display device with a digital micromirror device (DMD)) and a piezoelectric ceramic display, etc. The liquid crystal display device includes any one of a transmissive liquid crystal display device, a semi-transmissive liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device and a projection type liquid crystal display device. In particular, with respect to the laminate and the polarizing plate of the present invention, from the aspect of being easy to significantly exert their effects, they can be suitably used in liquid crystal display devices, and are particularly preferably used as IPS (in-plane By using the laminate or polarizing plate of the present invention, it is easy to realize a thinner display device, and a display device that can exhibit the following characteristics can be obtained, which is a characteristic of preventing light leakage and color shift when the liquid crystal display device is visually recognized from an oblique direction when black is displayed.

[0304] Example

[0305] 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. In addition, the apparatus and measurement methods used in the following examples are as follows.

[0306] The corona treatment was performed once using AGF-B10 manufactured by Kasuga Electric Co., Ltd. under the conditions of an output of 0.3 kW and a treatment speed of 3 m / min.

[0307] As the high-pressure mercury lamp, Unicure VB-15201BY-A manufactured by Ushio Electric Co., Ltd. was used.

[0308] The retardation value Rth(λ) in the thickness direction and the film thickness were measured using an ellipsometer M-220 manufactured by JASCO Corporation.

[0309] [Preparation of Composition for Forming Optically Anisotropic Film (Compositions 1 to 3)]

[0310] To 100 parts of a mixture of the polymerizable liquid crystal compound A and the polymerizable liquid crystal compound B described below, 0.2 parts of a leveling agent (BYK361N; manufactured by BASF Japan Co., Ltd.), 6 parts of a polymerization initiator 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)-1-butanone (Irgacure 369 (Irg369); manufactured by BASF Japan Co., Ltd.), and 8 parts of dipentaerythritol hexaacrylate (DPHA; manufactured by Tokyo Chemical Industry Co., Ltd.) were added.

[0311] Furthermore, cyclopentanone was added as a solvent so that the solid content concentration became 12%, and the mixture was stirred at 50° C. for 1 hour to obtain an optically anisotropic film-forming composition. It should be noted that the mixture ratio of the polymerizable liquid crystal compound A and the polymerizable liquid crystal compound B was added according to the target RthC (450) / RthC (550) as described in Table 1, so that the names of the respective compositions were as described in Table 1.

[0312] The ratio of polymerizable liquid crystal compound A and B in Table 1 is the number of parts relative to 100 parts of the total amount of polymerizable liquid crystal compounds.

[0313] [Table 1]

[0314]

[0315] The polymerizable liquid crystal compound A was produced by the method described in Japanese Patent Application Laid-Open No. 2010-31223. The polymerizable liquid crystal compound B was produced by the method described in Japanese Patent Application Laid-Open No. 2009-173893. The molecular structures of each are shown below.

[0316] Polymerizable liquid crystal compound A:

[0317] [Chemical formula 7]

[0318]

[0319] Polymerizable liquid crystal compound B:

[0320] [Chemical formula 8]

[0321]

[0322] (Example 1)

[0323] The surface of a 40 μm thick cycloolefin polymer (COP) film ZF-14 (substrate) manufactured by Zeon Corporation of Japan was subjected to corona treatment, and then coated with the optically anisotropic film-forming composition 1. After drying at 90° C. for 1 minute, the coated surface was irradiated with ultraviolet light (in nitrogen atmosphere, cumulative light intensity at a wavelength of 365 nm: 500 mJ / cm 2 ), thereby forming an optically anisotropic film 1, and obtaining a laminate 1. The film thickness of the obtained optically anisotropic film was measured by an ellipsometer and found to be 1.4 μm.

[0324] The laminate 1 was placed on an ultraviolet visible spectrophotometer ("UV-2450" manufactured by Shimadzu Corporation), and within the range of 300nm to 400nm, the absorbance (A1) when measured at a certain angle relative to the in-plane direction and the absorbance (A2) when measured at a 90-degree rotation from the angle when A1 was measured were measured every 1nm. The results showed that the maximum value of the absorbance ratio: A1 / A2 was 1.00 and the minimum value was 0.97.

[0325] <Evaluation of Orientation>

[0326] The obtained laminate 1 was observed using a polarizing microscope ("BX-51" manufactured by Olympus Corporation) at a magnification of 200. A case where the vertical alignment was confirmed was marked as ○, and a case where the vertical alignment was not confirmed was marked as ×.

[0327] <Analysis of constituent elements>

[0328] In the laminated body including the optically anisotropic film and the substrate produced by the aforementioned method, etching was performed from the interface on the opposite side of the optically anisotropic film to the substrate under the etching conditions described in Table 2 below using an Ar gas cluster ion beam, and element information was confirmed using XPS (K-Alpha+ manufactured by Thermo Fisher Scientific). After confirming the etching time from the interface on the opposite side of the substrate to the interface on the substrate side, element analysis information at a position 10 nm away from the interface on the opposite side of the substrate was extracted, thereby confirming the constituent elements in the liquid crystal cured film at a position 10 nm in the thickness direction from the interface on the opposite side of the optically anisotropic film to the liquid crystal cured film side. In addition, similarly, the element ratio of the central portion of the liquid crystal cured film layer was also confirmed, and the oxygen atomic ratio (O) at a position 10 nm away from the interface on the opposite side of the substrate was calculated. S ) and the oxygen atomic ratio (O C ) ratio (ΟS / Ο C ) are shown in Table 5.

[0329] [Table 2]

[0330]

[0331] <Production of double-sided glass laminate>

[0332] The laminate 1 obtained as described above was cut into a size of 10 cm×10 cm, the substrate side was subjected to a corona treatment, and the laminate was bonded to glass via a 25 μm pressure-sensitive adhesive manufactured by LINTEC.

[0333] Next, the liquid crystal cured film side was also subjected to corona treatment, and was bonded to a saponified triacetate cellulose film (KC4UYTAC, manufactured by Konica Minolta Co., Ltd., thickness 40 μm) via a 25 μm pressure-sensitive adhesive manufactured by LINTEC, and then the triacetate cellulose film surface was bonded to glass via a 25 μm pressure-sensitive adhesive manufactured by LINTEC, thereby obtaining a double-sided glass laminate comprising glass·adhesive·substrate (ZeonorFilm)·optically anisotropic film·adhesive·triacetate cellulose film·adhesive·glass.

[0334] <Initial phase difference measurement>

[0335] The retardation value in the thickness direction of the double-sided glass laminate was measured as follows.

[0336] Using KOBRA-WPR manufactured by Oji Instruments Co., Ltd., the incident angle of light to the sample for measuring optical properties (double-sided glass laminate) was changed to measure the front phase difference value and the phase difference value when tilted 40 degrees around the fast axis. The average refractive index at each wavelength was measured using an ellipsometer M-220 manufactured by JASCO Corporation. In addition, the film thickness was measured using an Optical NanoGauge film thickness meter C12562-01 manufactured by Hamamatsu Photonics KK. Based on the aforementioned front phase difference value, the phase difference value when tilted 50 degrees around the fast axis, the average refractive index, and the film thickness value, the three-dimensional refractive index was calculated with reference to the Oji Instruments technical data (http: / / www.oji-keisoku.co.jp / products / kobra / reference.html). Based on the obtained three-dimensional refractive index, the optical properties of each optically anisotropic film were calculated according to the following formula. The results are shown in Table 5.

[0337] RthC(λ)=((nxC(λ)+nyC(λ)) / 2-nzC(λ))×dC

[0338] It should be noted that RthC(λ) represents the phase difference value in the film thickness direction of the optical anisotropic film at a wavelength of λnm. In addition, nxC(λ) represents the in-plane principal refractive index of the optical anisotropic film at a wavelength of λnm, nyC(λ) represents the refractive index in the direction orthogonal to nxC(λ) in the plane at a wavelength of λnm, nzC(λ) represents the refractive index in the thickness direction of the optical anisotropic film at a wavelength of λnm, and when nxC(λ)=nyC(λ), nxC(λ) can be set to the refractive index in any direction in the film plane, and dC represents the film thickness of the optical anisotropic film.

[0339] (Wherein, Rth(450) represents the out-of-plane phase difference value relative to light with a wavelength of 450 nm, Rth(550) represents the out-of-plane phase difference value relative to light with a wavelength of 550 nm, and Rth(630) represents the out-of-plane phase difference value relative to light with a wavelength of 630 nm.)

[0340] <Measurement of phase difference value after durability test>

[0341] After the above-mentioned double-sided glass laminate was placed in a thermostatic chamber set at 105°C for 250 hours, the double-sided glass laminate was taken out of the thermostatic chamber and placed in a room temperature (25°C 55%) environment for 1 hour, and the phase difference value was measured using the method described above. The case where the phase difference value changed by 20nm or less from the initial stage was set as ○, and the case where the phase difference value changed by more than 20nm from the initial stage was set as ×. The results are shown in Table 5.

[0342] [Manufacturing of polarizing film]

[0343] A polyvinyl alcohol film having an average degree of polymerization of about 2,400, a saponification degree of 99.9 mol % or more and a thickness of 75 μm was immersed in pure water at 30°C, and then immersed in an aqueous solution having a weight ratio of iodine / potassium iodide / water of 0.02 / 2 / 100 at 30°C for iodine dyeing (iodine dyeing process). The polyvinyl alcohol film that had undergone the iodine dyeing process was immersed in an aqueous solution having a weight ratio of potassium iodide / boric acid / water of 12 / 5 / 100 at 56.5°C for boric acid treatment (boric acid treatment process). The polyvinyl alcohol film that had undergone the boric acid treatment process was washed with pure water at 8°C, and then dried at 65°C to obtain a polarizer with iodine adsorbed and oriented on the polyvinyl alcohol (thickness 27 μm after stretching). At this time, stretching was performed in the iodine dyeing process and the boric acid treatment process. The total stretching ratio of the stretching is 5.3 times. The polarizer obtained is bonded to a saponified triacetate cellulose film (KC4UYTAC 40μm manufactured by Konica Minolta) by means of a water-based adhesive using a clamping roller. While maintaining the tension of the obtained bond at 430N / m, it is dried at 60°C for 2 minutes to obtain a polarizing film having a triacetate cellulose film as a protective film on one side. It should be noted that the aforementioned water-based adhesive is prepared by adding 3 parts of carboxyl-modified polyvinyl alcohol (Kuraray Poval KL318 manufactured by Kuraray) and 1.5 parts of a water-soluble polyamide epoxy resin (Sumirez Resin 650 manufactured by Sumika Chemtex Company, a 30% solid content concentration aqueous solution) to 100 parts of water.

[0344] The optical properties of the obtained polarizing film were measured. The polarizer surface of the polarizing film obtained above was used as the incident surface, and the measurement was carried out using a spectrophotometer (V7100, manufactured by JASCO Corporation). The obtained visibility-corrected single transmittance was 42.1%, the visibility-corrected polarization degree was 99.996%, the single hue a was -1.1, and the single hue b was 3.7.

[0345] After the optically anisotropic film surface of the laminate 1 obtained above is subjected to corona treatment, it is attached to the polarizer side of the polarizing film manufactured by the aforementioned method via an adhesive (5 μm of pressure-sensitive adhesive manufactured by LINTEC). Next, a cycloolefin polymer film (substrate) (ZeonorFilm, manufactured by Zeon Co., Ltd., Japan) having a thickness of 40 μm and a front phase difference of 120 nm and a surface corona treated is attached to the ZF-14 side of the laminate via an adhesive (5 μm of pressure-sensitive adhesive manufactured by LINTEC), forming a polarizing plate 1 comprising a protective film / aqueous adhesive / polarizer / adhesive / optically anisotropic film / substrate (ZF-14) / adhesive / cycloolefin polymer film (front phase difference of 120 nm).

[0346] <Confirmation of oblique hue>

[0347] The obtained polarizing plate 1 was attached to a backlight via an adhesive, and then visually observed from a distance of 50 cm from an elevation angle of 60° and an azimuth angle of 0 to 360° to confirm the oblique hue. Clear black was marked as ○, black with a little light leakage was marked as △, and light leakage was marked as ×.

[0348] (Examples 2 and 3)

[0349] The same method as in Example 1 was used except that the optically anisotropic film-forming composition 1 was changed to 2 or 3 to form optically anisotropic films 2 and 3, thereby obtaining laminates 2 and 3. The same method as in Example 1 was used except that the obtained laminates 2 and 3 were further used to obtain polarizing plates 2 and 3. The same method as in Example 1 was used to perform evaluation. The results are shown in Table 5.

[0350] (Examples 4 to 7)

[0351] Optically anisotropic film-forming compositions 4 to 7 were obtained in the same manner as in Example 2 except that the amount of dipentaerythritol hexaacrylate (DPHA; manufactured by Tokyo Chemical Industry Co., Ltd.) added was changed as shown in Table 3.

[0352] Optically anisotropic films 4 to 7 were formed in the same manner as in Example 2 except that optically anisotropic film-forming compositions 4 to 7 were used to obtain laminates 4 to 7. Polarizing plates 4 to 7 were obtained using the obtained laminates. Evaluations were performed in the same manner as in Example 2. The results are shown in Table 5.

[0353] [Table 3]

[0354]

[0355] (Example 8)

[0356] The same operation as in Example 1 was performed except that the substrate was changed to a cycloolefin polymer film (substrate) having a thickness of 40 μm and a front phase difference value of 120 nm (Zeonor Film, manufactured by Zeon Co., Ltd., Japan), to form an optically anisotropic film 1 and obtain a laminate 8. The optically anisotropic film surface of the obtained laminate 8 was further subjected to a corona treatment, and then bonded to a polarizing film manufactured by the above method via an adhesive (pressure-sensitive adhesive 5 μm manufactured by LINTEC Co., Ltd.) to form a polarizing plate 8. In addition, the same operation as in Example 1 was performed to perform evaluation. The results are shown in Table 5.

[0357] (Example 9)

[0358] The same operation as in Example 2 was performed except that the substrate was changed to a cycloolefin polymer film (substrate) having a thickness of 40 μm and a front phase difference value of 120 nm (Zeonor Film, manufactured by Zeon Co., Ltd., Japan), to form an optically anisotropic film 2, thereby obtaining a laminate 9. The same operation as in Example 8 was performed except that the obtained laminate 9 was further used to form a polarizing plate 9. In addition, the same operation as in Example 1 was performed to perform evaluation. The results are shown in Table 5.

[0359] (Example 10)

[0360] The same operation as in Example 3 was performed except that the substrate was changed to a cycloolefin polymer film (substrate) having a thickness of 40 μm and a front phase difference value of 120 nm (Zeonor Film, manufactured by Zeon Co., Ltd., Japan) to form an optically anisotropic film 3 and obtain a laminate 10. The same operation as in Example 8 was performed except that the obtained laminate 10 was further used to form a polarizing plate 10. In addition, the same operation as in Example 1 was performed to perform evaluation. The results are shown in Table 5.

[0361] (Comparative Example 1)

[0362] [Preparation of an Alignment Film Composition for Forming an Optically Anisotropic Film]

[0363] A silane coupling agent KBM-9103 manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in a mixed solvent of ethanol and water at a ratio of 9:1 (weight ratio) to obtain an alignment film-forming composition having a solid content of 1%.

[0364] [Preparation of Composition for Forming Optically Anisotropic Film (Composition 8)]

[0365] An optically anisotropic film-forming composition 8 was obtained in the same manner as in Example 2 except that dipentaerythritol hexaacrylate (DPHA; manufactured by Tokyo Chemical Industry Co., Ltd.) was not added.

[0366] The surface of a 40 μm thick cycloolefin polymer (COP) film ZF-14 (substrate) manufactured by Zeon Co., Ltd. was subjected to corona treatment, and then coated with an oriented film composition for forming an optically anisotropic film using a bar coater, and dried at 120° C. for 1 minute to obtain an oriented film for forming an optically anisotropic film. The film thickness of the obtained oriented film for forming an optically anisotropic film was measured using an ellipsometer and found to be 100 nm.

[0367] Next, the optically anisotropic film-forming composition 8 was applied to the optically anisotropic film-forming oriented film using a bar coater, dried at 90° C. for 1 minute, and then irradiated with ultraviolet light (in nitrogen atmosphere, cumulative light intensity at a wavelength of 365 nm: 500 mJ / cm2 ), thereby forming an optically anisotropic film 8, and obtaining a laminate 11. Except for further using the obtained laminate 11, the same operation as in Example 1 was carried out to obtain a polarizing plate 11. In addition, the same operation as in Example 1 was carried out to perform evaluation. The results are shown in Table 5.

[0368] (Comparative Example 2)

[0369] [Preparation of Composition for Forming Optically Anisotropic Film (Composition 9)]

[0370] An optically anisotropic film-forming composition 9 was obtained in the same manner as in Example 2, except that 2 parts of the following ionic compound 1 described in JP-A-2019-139168 were added instead of dipentaerythritol hexaacrylate (DPHA; manufactured by Tokyo Chemical Industry Co., Ltd.).

[0371] Ionic compound 1:

[0372] [Chemical formula 9]

[0373]

[0374] The same method as in Example 2 was used except that the optically anisotropic film-forming composition 9 was used to form an optically anisotropic film 9 and obtain a laminate 12. The same method as in Example 1 was used to obtain a polarizing plate 12 except that the obtained laminate 12 was used. The same method as in Example 1 was used to perform evaluation. The results are shown in Table 5.

[0375] (Comparative Examples 3 and 4)

[0376] Optically anisotropic film-forming compositions 10 and 11 were obtained in the same manner as in Example 2 except that the amount of dipentaerythritol hexaacrylate (DPHA; manufactured by Tokyo Chemical Industry Co., Ltd.) added was changed as shown in Table 4.

[0377] Optically anisotropic films 10 and 11 were formed in the same manner as in Example 2, except that the optically anisotropic film-forming compositions 10 and 11 were used, thereby obtaining laminates 13 and 14. Furthermore, polarizing plates 13 and 14 were obtained in the same manner as in Example 1, except that the obtained laminates 13 and 14 were used. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 5.

[0378] [Table 4]

[0379] Composition name DPHA addition amount (parts) Composition 10 2 Composition 11 20

[0380] [Table 5]

[0381]

[0382] According to the present invention, it is possible to provide an optically anisotropic film and a laminated body in which a phase difference change due to heat is small, a polarizing plate including the laminated body, and an image display device including the same.

Claims

1. An optically anisotropic film satisfying the following formula (1): THE S / THE C ≥1.1 (1) In formula (1), S is the oxygen atomic ratio of the optically anisotropic film at a position 10 nm away from the film surface, O C It represents the oxygen atomic ratio in the central portion of the optically anisotropic film.

2. An optically anisotropic film satisfying the following formula (2): 0.95≤A1 / A2≤1.06 (2) In formula (2), A1 represents the absorbance in the range of 300 nm to 400 nm when measured at a certain angle relative to the in-plane direction, and A2 represents the absorbance in the range of 300 nm to 400 nm when measured at an angle rotated 90 degrees from the angle when A1 is measured.

3. The optically anisotropic film according to claim 1 or 2, which satisfies the following formula (3): nx≈ny <nz (3) In formula (3), nx represents the principal refractive index in the direction parallel to the film plane in the refractive index ellipsoid formed by the phase difference layer; ny represents the refractive index in the direction parallel to the film plane and orthogonal to the direction of nx in the refractive index ellipsoid formed by the phase difference layer; nz represents the refractive index in the direction perpendicular to the film plane in the refractive index ellipsoid formed by the phase difference layer. 4 . The optically anisotropic film according to claim 1 , which has a thickness of 0.1 μm to 3 μm.

5. The optically anisotropic film according to claim 1 or 2, which satisfies the following formula (4): -180nm≤RthC(550)≤-30nm (4) In the formula (4), RthC(550) represents the phase difference value in the thickness direction at a wavelength of 550 nm.

6. The optically anisotropic film according to claim 1 or 2, which satisfies the following formula (5): RthC(450) / RthC(550)≤1.04 (5) In the formula (5), RthC(450) represents the phase difference value in the thickness direction at a wavelength of 450 nm, and RthC(550) represents the phase difference value in the thickness direction at a wavelength of 550 nm. 7 . A laminate comprising: the optically anisotropic film according to claim 1 ; and an optically anisotropic layer. 8 . A polarizing plate comprising: a polarizing film; and the optically anisotropic film according to claim 1 . 9 . An image display device comprising the polarizing plate according to claim 8 .

10. A polymerizable liquid crystal composition having: At least one polymerizable liquid crystal compound; and The reactive group-containing non-liquid crystal compound is 3 to 18 parts by mass based on 100 parts by mass of the total polymerizable liquid crystal compound, wherein the reactive group-containing non-liquid crystal compound has at least one reactive group selected from an acryloyloxy group and a methacryloyloxy group.

11. The polymerizable liquid crystal composition according to claim 10, wherein: The weight average molecular weight of the non-liquid crystal compound containing a reactive group is 1,200 or less. The polymerizable liquid crystal composition according to claim 10 , further comprising a solvent. The polymerizable liquid crystal composition according to claim 10 , further comprising a polymerization initiator. The polymerizable liquid crystal composition according to claim 10 , further comprising a leveling agent.

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