Film, polarizing plate, and image display device

Abstract

The present application provides a film formed using a liquid crystal composition containing a leveling agent having a silicon atom, which has excellent adhesion to an adjacent layer. The film of the present application is a film formed using a liquid crystal composition containing a liquid crystal compound and a leveling agent containing a silicon atom, wherein, in the inner-shell photoelectron spectrum of Si2p obtained by measuring the surface of the film by X-ray photoelectron spectroscopy, the binding energy of the peak top is 102.0 eV or more, or a silicon atom bonded to four oxygen atoms is present on the surface of the film.

Description

Technical Field

[0001] This invention relates to a film, a polarizer, and an image display device. Background Technology

[0002] Optical films such as optical compensation films and phase difference films are used in various image display devices to eliminate image tinting or expand the viewing angle. Stretched birefringent films have been used as optical films, but in recent years, it has been proposed to use optical films with optical anisotropy layers composed of liquid crystal compounds to replace stretched birefringent films.

[0003] Optical anisotropic layers composed of liquid crystal compounds are typically formed by coating a liquid crystal composition containing liquid crystal compounds to form a coated film and then aligning the coated film. In liquid crystal compositions, leveling agents are sometimes added to improve the surface properties on the air interface side during the formation of the coating film. For example, Patent Document 1 discloses a liquid crystal composition in which a fluorine-based leveling agent containing fluorine atoms is added. Previous technical documents Patent documents

[0004] Patent Document 1: International Publication No. 2019 / 160044 Summary of the Invention The technical problem to be solved by the invention

[0005] In recent years, due to their recalcitrant degradation and toxicity, efforts are being made to regulate PFAS (perfluoroalkyl and polyfluoroalkyl compounds), and research is being conducted on alternatives that do not use fluorine atoms. Typically, research is being conducted on alternative materials containing silicon atoms. The inventors have studied liquid crystal compositions using leveling agents containing silicon atoms and found that the adhesion between the film formed using the liquid crystal composition and the layer adjacent to the film (e.g., an adhesive layer) does not meet the desired level and needs to be improved.

[0006] Therefore, the objective of this invention is to provide a film that exhibits excellent adhesion to adjacent layers and is formed using a liquid crystal composition containing a leveling agent having silicon atoms. Furthermore, the present invention also aims to provide a polarizer and an image display device related to the above-mentioned film. means for solving technical problems

[0007] In order to solve the above-mentioned problems, the inventors conducted in-depth research and discovered that the following structure can solve the problems.

[0008] [1] A film formed using a liquid crystal composition comprising a liquid crystal compound and a leveling agent containing silicon atoms, wherein, The Si2p photoelectron spectrum obtained by measuring the surface of the above film using X-ray photoelectron spectroscopy shows that the binding energy at the peak is above 102.0 eV. [2] A film formed using a liquid crystal composition comprising a liquid crystal compound and a leveling agent containing silicon atoms, wherein, The surface of the above-mentioned membrane contains silicon atoms bonded to four oxygen atoms. [3] According to the membrane described in [2], wherein, In the photoelectron spectrum of Si2p obtained by measuring the surface of the above-mentioned film by X-ray photoelectron spectroscopy, the peak area attributable to silicon atoms bonded to four oxygen atoms is more than 30% relative to the peak area of ​​the above-mentioned Si2p photoelectron spectrum. [4] The membrane according to any one of [1] to [3], wherein, The surface elastic modulus of the above-mentioned membrane is above 4.0 GPa. [5] The membrane according to any one of [1] to [4], wherein, The surface adsorption force of the above-mentioned membrane is above 12.0 nN. [6] A polarizer comprising a polarizer, an adhesive layer and a film as described in any one of [1] to [5]. [7] An image display device comprising the polarizer described in [6]. [8] The image display device according to [7] is an organic electroluminescent display device. [9] The image display device according to [7] is a liquid crystal display device. Invention Effects

[0009] According to the present invention, a membrane with excellent adhesion to adjacent layers can be provided. Furthermore, it is also possible to provide a polarizer and an image display device related to the aforementioned film. Attached Figure Description

[0010] Figure 1 This is a schematic cross-sectional view showing an example of a laminate including the membrane of the present invention. Figure 2 This is a schematic cross-sectional view showing an example of a polarizer including the film of the present invention. Detailed Implementation

[0011] The present invention will now be described in detail. The following constituent elements are sometimes described in light of representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0012] In this specification, the numerical range indicated by “~” refers to the range including the values ​​recorded before and after “~” as the lower and upper limits. Furthermore, in this specification, when there are two or more components of a certain ingredient, the “content” of that component refers to the total content of these two or more components. In the numerical ranges described in this specification, the upper or lower limit value recorded in a certain numerical range can be replaced with the upper or lower limit value in other numerical ranges described in different periods. Furthermore, within the numerical ranges described in this specification, the upper or lower limit value recorded in a certain numerical range can also be replaced with the value shown in the embodiments. In this specification, a combination of two or more preferred methods is a more preferred method.

[0013] In this specification, unless otherwise specified, the bonding direction of the divalent groups (e.g., -CO-O-) is not limited. For example, when Y in a compound represented by the formula "XYZ" is -CO-O-, the compound can be "XO-CO-Z" or "X-CO-OZ". In this specification, "(meth)acrylic acid" includes both acrylic acid and methacrylic acid, "(meth)acryloyl" includes both acryloyl and methacryloyl, "(meth)acrylate" includes both acrylate and methacrylate, and "(meth)acrylonitrile" includes both acrylonitrile and methacrylonitrile.

[0014] In this specification, unless otherwise specified, the slow axis is defined as 550nm.

[0015] In this specification, Re(λ) and Rth(λ) represent the in-plane delay and the thickness-direction delay at wavelength λ, respectively. Unless otherwise specified, wavelength λ is 550 nm. Furthermore, in this specification, Re(λ) and Rth(λ) are values ​​measured at wavelength λ in an AxoScan OPMF-1 (manufactured by Opto Science, Inc.). Specifically, the following values ​​are calculated by using the average refractive index ((nx+ny+nz) / 3) and film thickness (d(μm)) input by AxoScan OPMF-1. Slow axis direction (°) Re(λ) = R0(λ) Rth(λ)=((nx+ny) / 2-nz)×d Additionally, R0(λ) shows the value calculated by AxoScan OPMF-1, but refers to Re(λ).

[0016] In this specification, angular relationships (e.g., "orthogonal", "parallel", etc.) include the range of errors permissible in the technical field to which this invention pertains. Specifically, this means within a strictly defined angle range of less than ±10°, and preferably within ±5° or less, more preferably within ±3° or less, of the strictly defined angle.

[0017] In this specification, solid components refer to film-forming components, excluding solvents. Any film-forming component, even if in liquid form, is considered a solid component.

[0018] [membrane] The membrane of the present invention will now be described in detail. The film of the first aspect of the present invention is a film formed using a liquid crystal composition comprising a liquid crystal compound and a leveling agent containing silicon atoms, wherein the binding energy of the Si2p photoelectron spectrum obtained by measuring the surface of the film by X-ray photoelectron spectroscopy is 102.0 eV or higher. The second aspect of the present invention is a film formed using a liquid crystal composition comprising a liquid crystal compound and a leveling agent containing silicon atoms, wherein silicon atoms bonded to four oxygen atoms are present on the surface of the film. In this specification, when referred to simply as "the membrane of the present invention," it means that the concept includes either the membrane of the first embodiment or the membrane of the second embodiment.

[0019] While the reason why a membrane having the above structure can solve the problem of the present invention is not clear, the inventors speculate as follows. Furthermore, the mechanism by which the effect is achieved is not limited to the following conjectures. In other words, even if the effect can be achieved through a mechanism other than those described below, it is still included within the scope of this invention. In the film of the first aspect of the present invention, the binding energy of the peak of the Si2p photoelectron spectrum at the surface is above a predetermined value. In this case, it can be considered that among the silicon atoms contained in the film, the proportion of Si-O bonds with binding energies higher than Si-C bonds is high. It is speculated that the more Si-O bonds there are, the stronger the film surface, the more suppressed the fracture, and the more the surface adsorption force and polarity are improved, resulting in excellent adhesion to adjacent layers. In the membrane of the second aspect of the present invention, silicon atoms bonded to four oxygen atoms are present on the surface. It can be assumed that the silicon atoms bonded to four oxygen atoms exist in the state of silicon dioxide (SiO2). It is speculated that by containing silicon dioxide, the strength of the membrane surface is improved, fracture is suppressed, and surface adsorption force and polarity are enhanced, resulting in excellent adhesion to adjacent layers. Hereinafter, the superior adhesion between the membrane of the present invention and adjacent layers will also be referred to as "superior effect of the present invention".

[0020] The liquid crystal composition used in the formation of the film of the present invention, the method for manufacturing the film, and the characteristics of the film will be described in turn.

[0021] [Liquid Crystal Composition] The liquid crystal composition comprises a liquid crystal compound and a leveling agent containing silicon atoms (hereinafter also referred to as "specific leveling agent").

[0022] <Liquid Crystal Compounds> The liquid crystal compound contained in the liquid crystal composition is not particularly limited. Generally, liquid crystal compounds can be classified into rod-shaped and disc-shaped types based on their shape. Furthermore, they are categorized into low-molecular-weight and high-molecular-weight types. High-molecular-weight compounds typically refer to compounds with a degree of polymerization of 100 or higher (Polymer Physics / Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992). In this invention, any liquid crystal compound can be used, but rod-shaped or disc-shaped liquid crystal compounds (disc-shaped liquid crystal compounds) are preferred. Two or more rod-shaped liquid crystal compounds, two or more disc-shaped liquid crystal compounds, or mixtures of rod-shaped and disc-shaped liquid crystal compounds can also be used.

[0023] The liquid crystal compound contained in the liquid crystal composition can be any one of low molecular weight liquid crystal compound and high molecular weight liquid crystal compound, or a mixture thereof. From the perspective of orientation, liquid crystal compounds are preferably polymerizable liquid crystal compounds. Polymerizable liquid crystal compounds are liquid crystal compounds with polymerizable groups. Their orientation state can be fixed by polymerizing them after orientation. Furthermore, polymeric liquid crystal compounds can have their orientation state fixed by removing the solvent from the liquid crystal composition after orientation and then drying it.

[0024] The polymerizable liquid crystal compound is preferably at least one polymerizable liquid crystal compound selected from the group consisting of polymerizable rod-shaped liquid crystal compounds and polymerizable disk-shaped liquid crystal compounds. The polymerizable groups in a polymerizable liquid crystal compound are not particularly limited, but preferably polymerizable groups capable of undergoing free radical polymerization or cationic polymerization. Examples of polymerizable groups include acryloyl, methacryloyl, epoxy, and vinyl groups.

[0025] As a rod-shaped liquid crystal compound, the preferred compound is the one described in claim 1 of Japanese Patent Application Publication No. 11-513019 or in paragraphs

[0026] to

[0098] of Japanese Patent Application Publication No. 2005-289980. As a disc-shaped liquid crystal compound, the preferred compound is the one described in paragraphs

[0020] to

[0067] of Japanese Patent Application Publication No. 2007-108732 or in paragraphs

[0013] to

[0108] of Japanese Patent Application Publication No. 2010-244038.

[0026] As a liquid crystal compound, a reverse wavelength dispersive liquid crystal compound (reverse dispersive compound) can be used. In this specification, a "reverse wavelength dispersive" liquid crystal compound refers to a liquid crystal compound whose in-plane retardation (Re) value becomes equal to or increases as the measurement wavelength increases when the in-plane retardation (Re) value of a film made using this liquid crystal compound is measured at a specific wavelength (visible light range). The reverse wavelength dispersive liquid crystal compound is not particularly limited as long as it can form a reverse wavelength dispersive layer. For example, the compounds represented by general formula (I) described in Japanese Patent Application Publication No. 2008-297210 (especially the compounds described in paragraphs

[0034] to

[0039] ), the compounds represented by general formula (1) described in Japanese Patent Application Publication No. 2010-084032 (especially the compounds described in paragraphs

[0067] to

[0073] ), the compounds represented by general formula (1) described in Japanese Patent Application Publication No. 2016-081035 (especially the compounds described in paragraphs

[0043] to

[0055] ), and the compounds represented by general formula (II) described in Japanese Patent Application Publication No. 2016-053709 (especially the compounds described in paragraphs

[0036] to

[0043] ). In addition, examples include paragraphs

[0027] to

[0100] of Japanese Patent Application Publication No. 2011-006360, paragraphs

[0028] to

[0125] of Japanese Patent Application Publication No. 2011-006361, paragraphs

[0034] to

[0298] of Japanese Patent Application Publication No. 2012-207765, paragraphs

[0016] to

[0345] of Japanese Patent Application Publication No. 2012-077055, and the National... The compounds described in paragraphs

[0017] to

[0072] of International Publication No. 2012 / 141245, paragraphs

[0021] to

[0088] of International Publication No. 2012 / 147904, paragraphs

[0028] to

[0115] of International Publication No. 2014 / 147904, and paragraphs

[0025] to

[0056] of International Publication No. 2021 / 060427.

[0027] Liquid crystal compounds can be used alone or in combination of two or more. The content of the liquid crystal compound is preferably 50 to 99.99% by mass, more preferably 70 to 99% by mass, relative to the total solid content of the liquid crystal composition.

[0028] Leveling agents containing silicon atoms The liquid crystal composition contains a leveling agent having silicon atoms (specific leveling agent). The structure containing the above-mentioned specific leveling agent is not limited as long as it contains silicon atoms, but preferably a polymer having repeating units (repeating unit A) containing silicon atoms.

[0029] (Repeating Unit A) Repeating unit A is a repeating unit containing silicon atoms. The number of silicon atoms contained in the repeating unit A is 1 or more, preferably 2 or more, more preferably 3 to 6, and even more preferably 3 to 5.

[0030] The repeating unit A preferably contains silicon atoms as a structure represented by the following formula (Ia).

[0031] [Chemical Formula 1]

[0032] In equation (Ia), Indicates the bonding location. R 11 R 12 and R 13 Each can be independently represented by an alkyl, alkenyl, aryl, or alkylene aryl group that may have substituents. Preferred substituents are halogen atoms, alkyl, alkenyl, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy groups. Examples of alkyl groups include straight-chain alkyl groups with 1 to 18 carbon atoms and branched or cyclic alkyl groups with 3 to 18 carbon atoms. Specifically, examples include methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, and cyclohexyl. Examples of alkenyl groups with 2 to 12 carbon atoms can be cited as examples. Examples of aryl groups with 6 to 12 carbon atoms can be cited as examples of the aforementioned aryl groups. Examples of alkylene aryl groups with 7 to 30 carbon atoms are alkylene aryl groups. From the perspective of superior leveling properties, R 11 R 12 and R 13 Preferably, all are alkyl groups.

[0033] From the viewpoint of achieving better results in this invention, the repeating unit A preferably contains two or more structures represented by formula (Ia), more preferably three to six, and even more preferably three to five.

[0034] From the viewpoint of achieving better results with the present invention, the structure represented by the above formula (Ia) is preferably bonded to carbon or oxygen atoms. In other words, repeating unit A preferably has a structure represented by -OA or -CR. A The structure represented by 2-A. A represents the structure represented by the above equation (Ia). R A Each can independently represent a hydrogen atom or a substituent, R A It can be a structure represented by the above equation (Ia).

[0035] From the viewpoint of superior leveling properties and compatibility with liquid crystal compounds, repeating unit A is preferably a repeating unit represented by the following formula (a1).

[0036] [Chemical Formula 2]

[0037] In formula (a1), m represents an integer of 1 or more. Preferably, m is an integer of 2 or more, more preferably an integer of 3 or more, even more preferably an integer of 3 to 6, and particularly preferably an integer of 3 to 5.

[0038] In equation (a1), R 11 R 12 and R 13 R in equation (Ia) 11 R 12 and R 13 The same. Additionally, there are multiple R. 11 They can be the same or different, and there can be multiple R. 12 They can be the same or different, and there can be multiple R. 13 They can be the same or different.

[0039] In equation (a1), R 21 and R 22 Each can be used to represent a hydrogen atom or an alkyl group independently. Examples of alkyl groups include straight-chain alkyl groups with 1 to 18 carbon atoms and branched or cyclic alkyl groups with 3 to 18 carbon atoms. As R 21 and R 22 Hydrogen atoms are preferred.

[0040] In equation (a1), R 23 It represents a hydrogen atom or a substituent. Examples of substituents include alkyl, alkenyl, aryl, or substituents having a linking group and a group containing a silicon atom. Substituents having a linking group and a group containing a silicon atom also include -CH2-CO-L. 1 -L2 -(Si(R) 11 (R) 12 (R) 13 )) m L 1 L 2 R 11 R 12 R 13 The symbols m and m are defined in the same way as those in equation (a1). As R 23 The preferred form is a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a straight-chain alkyl group having 1 to 4 carbon atoms, further preferably a hydrogen atom, a methyl group or an ethyl group, and particularly preferably a hydrogen atom or a methyl group.

[0041] In formula (a1), L 1 Indicates -O- or -NR Z -. R z It represents a hydrogen atom or a substituent. As a result of R Z The substituents represented, for example, can be exemplified as those derived from R 23 The substituents represented are exemplified by alkyl groups, more preferably straight-chain alkyl groups having 1 to 4 carbon atoms, and even more preferably methyl or ethyl groups. As L 1 Preferably -O- or -NH-, more preferably -O-.

[0042] In formula (a1), L 2 This indicates an m+1 valence linker. As the above-mentioned m+1 valence linking group, for example, a hydrocarbon group with an m+1 valence that can have 1 to 10 carbon atoms having substituents and a portion of the carbon atoms constituting the hydrocarbon group can be replaced by heteroatoms. As a substituent that may be present in the above-mentioned hydrocarbon group, alkyl groups are preferred, straight-chain alkyl groups with 1 to 4 carbon atoms are more preferred, and methyl or ethyl groups are even more preferred. Examples of heteroatoms that can replace a portion of the aforementioned carbon atom include silicon, oxygen, and nitrogen. As L 2 For example, examples include groups represented by the structural formula K-1-L, groups represented by the structural formula K-2-L, and groups represented by the structural formula K-3-L. Additionally, in the sub-structural formulas, L in equation (a1) 1 The bonding position, The expression represents -SiR in equation (a1) 11 R 12 R 13 The bonding position of the indicated group. L 2 It can be composed of -alkylene-O-(SiR) 14 2-O) nl - indicates the group. As the aforementioned alkylene group, a straight-chain alkylene group having 1 to 4 carbon atoms is preferred. R 14 Definition and preferred method and R 11 R 12 and R 13 The definitions and preferred methods for the groups represented are the same, with alkyl groups being preferred, and methyl or ethyl groups being more preferred. nl represents an integer of 1 or more, preferably an integer from 1 to 80, and more preferably an integer from 1 to 16. Furthermore, with L 2 The -SiR 11 R 12 R 13 The atoms bonded to the indicated groups are preferably carbon atoms or oxygen atoms, more preferably oxygen atoms. From the viewpoint that the present invention has superior effects, L 2 Preferably, the group is represented by the structural formula K-1-L.

[0043] [Chemical Formula 3]

[0044] As a specific example of repeating unit A, repeating units derived from monomers represented by K-1 to K-33 below can be cited. Additionally, nBu represents n-butyl.

[0045] [Chemical Formula 4]

[0046] [Chemical Formula 5]

[0047] Repeating unit A can be used alone or in combination with two or more types. The content of repeating unit A is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, relative to all repeating units (100% by mass) constituting the main chain of the specific leveling agent. The upper limit of the content of repeating unit A relative to all repeating units (100% by mass) constituting the main chain of the specific leveling agent can be 100% by mass, preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0048] A particular leveling agent may have repeating units other than repeating unit A. From the viewpoint of orientation control of the liquid crystal compound described above, a specific leveling agent is also preferably having repeating units (repeating unit B) containing mesocrystalline groups. From the viewpoint of better adhesion to adjacent layers, a particular leveling agent is also preferably having repeating units (repeating unit C) containing polymerizable groups. From a compatibility standpoint, certain leveling agents preferably contain repeating units having poly(alkoxide) radicals. Details regarding poly(alkoxide) radicals will be discussed later. The specific leveling agent preferably contains repeating unit A and at least one repeating unit selected from repeating unit B and repeating unit C, and more preferably contains repeating unit A, repeating unit B and repeating unit C.

[0049] (Repeating Unit B) Repeating unit B is a repeating unit containing a mesocrystalline group. As the aforementioned mesocrystalline group, a known mesocrystalline group can be used, for example, as described in "FlussigeKristalle in Tabellen II" (VEB Deutsche Verlag fur Grundstoff Industrie, Leipzig, 1984), particularly pages 7 to 16, and as described in "Liquid Crystal Handbook Editorial Committee, Liquid Crystal Handbook" (Maruzen, 2000), particularly Chapter 3. As a mesocrystalline group, it is preferably a group having at least one cyclic structure selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups and alicyclic groups. Since it can improve the orientation degree of the liquid crystal compound, the mesocrystalline group is preferably a group that can have substituents and aromatic hydrocarbon groups or a group that has alicyclic groups, more preferably a group that can have substituents and has 2 to 4 aromatic hydrocarbon groups, and even more preferably a group that can have substituents and has 3 aromatic hydrocarbon groups. As substituents, alkyl, alkoxy, alkyl ester or acetyl groups are preferred, and methyl, tert-butyl, methoxy or methyl ester groups are more preferred.

[0050] As a mesocrystalline group, it is preferred to use a group represented by the following formula (M1-A). -(Cy 11 -L 11 ) n -Cy 12 - (M1-A)

[0051] In formula (M1-A), Indicates the bonding location.

[0052] In formula (M1-A), n represents an integer greater than or equal to 1, preferably an integer from 1 to 10, more preferably an integer from 1 to 3, and even more preferably 2.

[0053] In formula (M1-A), Cy 11 and Cy 12 Each can be independently represented as a divalent cyclic group that may have substituents. The aforementioned divalent cyclic group can be either a monocyclic or polycyclic group, with a monocyclic group being preferred. The number of ring members in the above-mentioned divalent cyclic group is preferably 5 to 18, more preferably 5 to 10, and even more preferably 5 or 6.

[0054] Examples of divalent cyclic groups include divalent aromatic cyclic groups and divalent alicyclic groups. Examples of divalent aromatic ring groups include divalent aromatic hydrocarbon ring groups obtained by removing two hydrogen atoms from an aromatic hydrocarbon ring and divalent aromatic heterocyclic ring groups obtained by removing two hydrogen atoms from an aromatic heterocyclic ring. Examples of aromatic hydrocarbon rings include benzene rings, naphthyl rings, anthracene rings, and phenanthrene rings. Examples of aromatic heterocyclic rings include pyridine rings, pyridazine rings, imidazole rings, thiophene rings, quinoline rings, isoquinoline rings, phenanthrene-rholine rings, oxazole rings, thiazole rings, oxadiazole rings, benzothiazole rings, benzothiazole rings, phthalimide rings, thienothiazole rings, thiazole-thiazole rings, thienothiphene rings, and thienooxazole rings. Among these, groups obtained by removing two hydrogen atoms from a benzene ring (e.g., 1,4-phenylene) are preferred. Examples of divalent alicyclic groups include divalent aliphatic hydrocarbon cyclic groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring (e.g., cycloalkanes and cycloalkenes) and divalent aliphatic heterocyclic groups obtained by removing two hydrogen atoms from an aliphatic heterocycle. Examples of aliphatic hydrocarbon rings include cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclododecane, and cyclodocosahexane. Examples of aliphatic heterocyclic groups include pyrrolidine, oxacyclopentane, tetrahydrothiophene, piperidine, tetrahydropyran, thiocyclohexane, piperazine, and morpholine. Among these, groups obtained by removing divalent hydrogen atoms from a cyclohexane ring (e.g., 1,4-cyclohexene) are preferred. As the aforementioned divalent cyclic group, a divalent aromatic cyclic group or a divalent aliphatic hydrocarbon cyclic group is preferred, and a divalent aromatic cyclic group is more preferred.

[0055] Examples of substituents that can be present in the aforementioned divalent cycloalcohol group include alkyl ester groups, alkyl groups, acyl groups, alkoxy groups, alkoxythio groups, alkoxycarbonyl groups, carbamoyl groups, amide groups, halogen atoms, cyano groups, and nitro groups. Alkyl ester groups, alkyl groups, or acyl groups are preferred, methyl ester groups, straight-chain alkyl groups or acetyl groups having 1 to 4 carbon atoms are more preferred, and methyl ester groups, methyl groups, or ethyl groups are even more preferred.

[0056] In formula (M1-A), L 11 Each can be used independently to represent a single bond or a divalent linker. Examples of divalent linkers mentioned above include -CO-, -O-, -S-, -C(=S)-, and -CR. L1 R L2 -、-CR L3 =CR L4 -and-NR L5 - and combinations of two or more of them. R L1 ~R L5 The table represents hydrogen atoms or substituents independently. As a result of R... L1 ~R L5 The substituents indicated are preferably halogen atoms, alkyl groups having 1 to 12 carbon atoms, or alkoxy groups having 1 to 12 carbon atoms. As L 11 Preferred -CO-, -O-, -CR L1 R L2 -、-NR L5 - or a combination of two of them.

[0057] When n is an integer greater than 2, when Cy 11 When representing phenylene, from the viewpoint of improving orientation when aligning liquid crystal compounds horizontally, two or more Cy atoms are used. 11 Either of these is preferably interpositional or adjacent, with interpositional connection being preferred from the viewpoint of orientation and improving pinholes. On the other hand, when vertically aligning the liquid crystal compound, two or more Cy... 11 Either of them is preferably a positional connection.

[0058] From the viewpoint of improving compatibility with liquid crystal compounds and achieving better leveling properties, the repeating unit B is preferably a repeating unit represented by the following formula (b1) or a repeating unit represented by formula (b2), and more preferably a repeating unit represented by formula (b1).

[0059] [Chemical Formula 6]

[0060] In equations (b1) and (b2), R 21 R 22 R 23 and L 1 The same as what is described in the above formula (a1). In the above formula (b2), R 24 and R 25 The definitions are independently related to R in the above equation (a1). 21 and R 22 The definitions are the same, and the preferred methods are also the same. R 26 The definition of R in the above formula (a1) is the same as that in the above formula. 23The definitions are the same, and the preferred selection methods are also the same. L 2 The definition of L in the above formula (a1) is the same as that in the above formula. 1 The definitions are the same, and the preferred methods are also the same.

[0061] In equations (b1) and (b2), SP 1 and SP 2 Each spacer group is represented independently. The spacer group is not particularly limited as long as it is a divalent linker without a ring structure. For example, divalent chain aliphatic hydrocarbon groups with 1 to 20 carbon atoms can be cited. As the aforementioned divalent chain aliphatic hydrocarbon group having 1 to 20 carbon atoms, a chain alkylene group having 1 to 15 carbon atoms is preferred, and a chain alkylene group having 1 to 8 carbon atoms is more preferred. Specifically, examples of preferred compounds include methylene, ethylene, propylene, butylene, pentylene, hexylene, methylhexylene, and heptylene. One or more of the -CH2- groups constituting the aforementioned divalent chain aliphatic hydrocarbon group can be independently substituted by groups selected from -O-, -S-, -CO-, and -N(Q)-. Furthermore, two or more -CH2- groups can be substituted, provided that the same groups are not adjacent. Q represents a hydrogen atom or a substituent. As the substituent represented by Q, an alkyl group is preferred, a straight-chain alkyl group having 1 to 4 carbon atoms is more preferred, and methyl or ethyl groups are even more preferred. As the aforementioned spacer group, preferably, -(CH2-CH2-O) n1 - , -(CH2) n2 -O- or -(CH2) n2 -O-CO- . Indicates the bonding position. n1 represents an integer from 1 to 4. n2 represents an integer from 1 to 6 independently, preferably an integer from 2 to 4.

[0062] In equations (b1) and (b2), M 1 This indicates a mesocrystalline group. Details about mesocrystalline groups are as described above.

[0063] In equation (b2), T 1 This indicates a terminal group. A terminal group can represent a hydrogen atom or a substituent. Examples of substituents mentioned above include halogen atoms, cyano groups, nitro groups, hydroxyl groups, alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, alkylthio groups with 1 to 10 carbon atoms, alkoxycarbonyloxy groups with 1 to 10 carbon atoms, alkoxycarbonyl groups with 1 to 10 carbon atoms (ROC(O)-: R is alkyl), acyloxy groups with 1 to 10 carbon atoms, acylamino groups with 1 to 10 carbon atoms, alkoxycarbonylamino groups with 1 to 10 carbon atoms, sulfonylamino groups with 1 to 10 carbon atoms, aminosulfonyl groups with 1 to 10 carbon atoms, carbamoyl groups with 1 to 10 carbon atoms, thionyl groups with 1 to 10 carbon atoms, trialkylsiloxy groups with 3 to 12 carbon atoms, and urea groups with 1 to 10 carbon atoms.

[0064] As a specific example of repeating unit B, for example, repeating units derived from the monomers represented by Q-1 to Q-32 below can be cited.

[0065] [Chemical Formula 7]

[0066] [Chemical Formula 8]

[0067] Repeating unit B can be used alone or in combination with two or more types. The content of repeating unit B is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 45% by mass, relative to all repeating units (100% by mass) of the main chain constituting the specific leveling agent.

[0068] (Repeating Unit C) The repeating unit C is a repeating unit containing a reactive group. Examples of reactive groups include free radical polymerizable groups or cationic polymerizable groups, with free radical polymerizable groups being preferred. Examples of reactive groups include functional groups capable of forming covalent complexes with hydroxyl groups. As a free radical polymerizable group, known free radical polymerizable groups can be used, for example, vinyl, allyl, ethoxy, maleimide, allyloxy, (meth)acryloyl, (meth)acryloyloxy, and (meth)acrylamido. Among these, (meth)acryloyl or (meth)acryloyloxy is preferred. As the cationic polymerizable group, known cationic polymerizable groups can be used, such as alicyclic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, spirocyclic orthoester groups, and ethyleneoxy groups. Among these, alicyclic ether groups or ethyleneoxy groups are preferred, and epoxy groups, oxetyl groups, or ethyleneoxy groups are more preferred. As functional groups capable of forming covalent complexes with hydroxyl groups, borate groups (-B(OH)2) and borate ester groups (-B(OR)2) are preferred. B1 2) Base. R B1 Each of the following can be independently represented: a hydrogen atom, an alkyl group that may have substituents, an aryl group that may have substituents, or a heteroaryl group that may have substituents, preferably a hydrogen atom or an alkyl group that may have substituents. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5. The aryl group preferably has 4 to 20 carbon atoms, more preferably 6 to 12. For example, phenyl can be cited as an aryl group. The number of carbon atoms in the heteroaryl group is preferably 3 to 10, more preferably 3 to 5. Examples of heteroatoms contained in the heteroaryl group include oxygen, nitrogen, and sulfur atoms. R B1 They can bond together to form a ring. R B1 The number of ring members formed by mutual bonding is preferably 4 to 8, more preferably 5 to 6.

[0069] The repeating unit C has 1 or more reactive groups, preferably 1 to 3, more preferably 1 or 2.

[0070] From the viewpoint of better compatibility with liquid crystal compounds, the repeating unit C is preferably a repeating unit represented by the following formula (c1).

[0071] [Chemical Formula 9]

[0072] In equation (c1), R 21 R 22 R 23 and L 1 The same as what is described in the above formula (a1).

[0073] In equation (c1), L 3 This indicates a single bond or a divalent linker. Examples of divalent linking groups include divalent aliphatic hydrocarbon groups with 1 to 20 carbon atoms that can have substituents. The aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferably an alkylene group having 1 to 15 carbon atoms, and more preferably an alkylene group having 2 to 8 carbon atoms. One or more of the -CH2- groups constituting the above-mentioned divalent aliphatic hydrocarbon groups can be independently replaced by groups selected from -O-, -S-, -CO-, and -N(Q)-. Furthermore, two or more -CH2- groups can be replaced as long as the same groups are not adjacent. The definition and preferred embodiment of Q are as described above. As L 3Preferably, the alkylene group having 2 to 8 carbon atoms may be a substituent. -(L 31 -O) n3 - . Indicates the bonding position. n3 represents an integer from 1 to 8. L 31 Each of the following can be independently represented as an alkylene group having 1 to 6 carbon atoms and may have a substituent, preferably an alkylene group having 2 to 4 carbon atoms and may have a substituent. By L 3 The divalent linking group can be a group containing a mesocrystalline group. Preferably, the group containing a mesocrystalline group is... -SP 1 -M 1 - . Indicates the bonding location. SP 1 and M 1 The same as that described in equation (b1) above. In addition, when the repeating unit contains both reactive groups and mesocrystalline groups, the repeating unit is equivalent to repeating unit C.

[0074] Examples of substituents that can be present as the aforementioned divalent linking group include hydroxyl, halogen atom, amino, alkyl, alkoxy, acyl, aryl, nitro, cyano, alkyl carbonyl, and sulfonyl groups.

[0075] In equation (c1), P 1 This indicates a reactive group. The definition and preferred method of reactive groups are as described above.

[0076] As a specific example of the repeating unit C, the repeating unit shown below can be cited. In the repeating unit below, n represents an integer greater than 1 (typically, an integer from 1 to 6).

[0077] [Chemical Formula 10]

[0078] [Chemical Formula 11]

[0079] As a repeating unit containing a boric acid group or a borate ester group as a reactive group, for example, the repeating unit described in paragraphs 0036 to 0045 of International Publication No. 2018 / 062068 can also be cited.

[0080] The repeating unit C can be used alone or in combination with two or more types. The content of repeating unit C is preferably 1 to 50% by mass, more preferably 5 to 25% by mass, and even more preferably 10 to 25% by mass, relative to all repeating units constituting the main chain of a particular leveling agent.

[0081] The total content of repeating unit A, repeating unit B, and repeating unit C, relative to all repeating units constituting the main chain of a specific leveling agent, is preferably 80% by mass or more, more preferably 90% by mass or more. The upper limit is not particularly limited and can be 100% by mass.

[0082] (Other repeating units) Certain leveling agents may contain repeating units other than those mentioned above. For example, from the viewpoint of orientation control, a particular leveling agent may have repeating units containing polar groups. Examples of polar groups include carboxyl, amino, amide, urea, carbamate, sulfonamide, sulfonyl, phosphine, hydroxyl, mercapto, methylene substituted with an electron-withdrawing group, and methine substituted with an electron-withdrawing group, with carboxyl being preferred.

[0083] As a repeating unit containing a polar group, a repeating unit represented by the following formula (K-1) is preferred.

[0084] [Chemical Formula 12]

[0085] In the above formula (K-1), R 10 The alkyl group represents 1 to 20 hydrogen atoms or carbon atoms, wherein preferably it is an alkyl group with 1 to 10 hydrogen atoms or carbon atoms, more preferably it is an alkyl group with 1 to 4 hydrogen atoms or carbon atoms, and even more preferably it is a hydrogen atom or a methyl group.

[0086] Examples of monomers that form repeating units represented by the above formula (K-1) include acrylic acid and methacrylic acid.

[0087] The content of repeating units with polar groups is preferably 0.05 to 30% by mass, more preferably 0.1 to 15% by mass, and even more preferably 1 to 10% by mass, relative to all repeating units (100% by mass) of the main chain constituting a particular leveling agent.

[0088] From a compatibility standpoint, certain leveling agents preferably contain repeating units having a poly(alkoxide) group. As the poly(alkoxide) group, it is preferable to use a poly(alkoxide) group composed of... -(L 31 -O) n4 - The group indicated. L 31 As described in formula (c1), n4 represents an integer greater than 2, preferably an integer from 2 to 60, and more preferably an integer from 4 to 40. The poly(alkoxide) may contain at least one repeating unit from repeating units A to C mentioned above, and a specific leveling agent may contain repeating units that are different from repeating units A to C and have poly(alkoxide). Examples of repeating units having poly(alkoxide) include repeating units derived from (meth)acrylates containing poly(alkoxide).

[0089] The content of poly(alkoxy) repeating units is preferably 0.05 to 30% by mass, more preferably 1 to 30% by mass, and even more preferably 5 to 30% by mass, relative to all repeating units of the main chain constituting a particular leveling agent.

[0090] Other repeating units besides those mentioned above may include, for example, repeating units derived from alkyl methacrylates (the alkyl portion has 1 to 24 carbon atoms), styrene derivatives, (meth)acrylonitrile, vinyl ether derivatives, and alkyl (meth)acrylamide derivatives.

[0091] When a specific leveling agent is a copolymer containing two or more repeating units, the specific leveling agent can be any of a random copolymer, an alternating copolymer, or a block copolymer. Furthermore, random, alternating, and block copolymers can also be mixed together.

[0092] The weight-average molecular weight of a specific leveling agent is preferably 5,000 to 70,000, more preferably 9,000 to 40,000, and even more preferably 15,000 to 30,000. In this invention, the weight-average molecular weight is the value determined by gel permeation chromatography (GPC) under the following conditions. • Solvent (eluent): Tetrahydrofuran • Device Name: EcoSEC HLC-8320GPC (Manufactured by Tosoh Corporation) • String of tubes: Connect three tubes (TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ200, all manufactured by Tosoh Corporation) for use. • Column temperature: 40℃ • Sample concentration: 0.1% by mass • Flow rate: 0.35 ml / min • Calibration curves: Calibration curves for six samples of TSK standard polystyrene manufactured by Tosoh Corporation, with values ​​from Mw=706000 to 1013 (Mw / Mn=1.03 to 1.06).

[0093] A specific leveling agent can be used alone or in combination of two or more. From the viewpoint of achieving better results with the present invention, the content of the specific leveling agent is preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less, relative to the total solid content of the liquid crystal composition. Furthermore, from the viewpoint of leveling properties, the content of the specific leveling agent is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, relative to the total solid content of the liquid crystal composition.

[0094] <Polymerization Initiator> The liquid crystal composition preferably contains a polymerization initiator. There are no particular restrictions on the type of polymerization initiator, but photopolymerization initiators are preferred. As photopolymerization initiators, known photopolymerization initiators can be used. Examples include α-carbonyl compounds, azo dye ethers, α-hydrocarbon-substituted aromatic azo dye compounds, polynuclear quinone compounds, combinations of triarylimidazolium dimers and p-aminophenyl ketones, acridine and phenazine compounds, oxadiazole compounds, o-acyl oxime compounds, and acylphosphine oxide compounds. Commercially available products can also be used as photopolymerization initiators. Examples of commercially available products include IRGACURE-184, IRGACURE-907, IRGACURE-369, IRGACURE-651, IRGACURE-819, IRGACURE-OXE-01, and IRGACURE-OXE-02 manufactured by BASF.

[0095] The content of the polymerization initiator is preferably 0.01 to 30% by mass, more preferably 0.1 to 15% by mass, relative to the total solid content of the liquid crystal composition.

[0096] <Orientation Control Agent> Liquid crystal compositions can contain orientation control agents as needed. With the help of orientation control agents, in addition to uniform orientation, various orientation states such as vertical orientation, tilted orientation, mixed orientation, and cholesterol orientation can be formed, and specific orientation states can be controlled and achieved more uniformly and precisely.

[0097] As orientation control agents that promote uniform orientation, low-molecular-weight orientation control agents and high-molecular-weight orientation control agents can be used, for example. As a low-molecular-weight orientation control agent, for example, reference can be made to paragraphs

[0009] to

[0083] of Japanese Patent Application Publication No. 2002-020363, paragraphs

[0111] to

[0120] of Japanese Patent Application Publication No. 2006-106662, and paragraphs

[0021] to

[0029] of Japanese Patent Application Publication No. 2012-211306, the contents of which are incorporated herein by reference. As an orientation control agent for polymers, reference can be made to paragraphs

[0021] to

[0057] of Japanese Patent Application Publication No. 2004-198511 and paragraphs

[0121] to

[0167] of Japanese Patent Application Publication No. 2006-106662, the contents of which are incorporated in this application specification.

[0098] As orientation control agents for forming or promoting vertical orientation, examples include boric acid compounds and onium salt compounds. Specifically, reference can be made to compounds described in Japanese Patent Application Publication No. 2008-225281, paragraphs

[0023] to

[0032] , Japanese Patent Application Publication No. 2012-208397, paragraphs

[0052] to

[0058] , Japanese Patent Application Publication No. 2008-026730, paragraphs

[0024] to

[0055] , and Japanese Patent Application Publication No. 2016-193869, paragraphs

[0043] to

[0055] , the contents of which are incorporated herein by reference.

[0099] Cholesterol orientation can be achieved by adding a chiral agent to the liquid crystal composition, and the chiral direction of the cholesterol orientation can be controlled according to its chiral direction. Furthermore, the pitch of the cholesterol orientation can be controlled according to the orientation-restricting force of the chiral agent.

[0100] <Solvent> From the viewpoint of operability in film formation, liquid crystal compositions preferably contain a solvent. Examples of solvents include, for example, ketones (e.g., acetone, 2-butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone), ethers (e.g., dioxane, tetrahydrofuran, tetrahydropyran, dioxolane, tetrahydrofurfuryl alcohol, and cyclopentylmethyl ether), aliphatic hydrocarbons (e.g., hexane), alicyclic hydrocarbons (e.g., cyclohexane), aromatic hydrocarbons (e.g., benzene, toluene, xylene, and trimethylbenzene), carbon halogens (e.g., dichloromethane, chloroform, dichloroethane, dichlorobenzene, and chlorotoluene), and esters (e.g., Organic solvents such as methyl acetate, ethyl acetate, ethyl propionate, butyl acetate and diethyl carbonate, alcohols (e.g. ethanol, isopropanol, butanol and cyclohexanol), cellosols (e.g. methyl cellosol, ethyl cellosol and 1,2-dimethoxyethane), cellosol acetates, sulfoxides (e.g. dimethyl sulfoxide), amides (e.g. dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone and 1,3-dimethyl-2-imidazolium ketone), and heterocyclic compounds (e.g. pyridine, etc.) as well as water. These solvents can be used alone or in combination of two or more.

[0101] <Other Ingredients> The liquid crystal composition may contain other components besides those mentioned above, as needed. Other components include, for example, chiral agents, chain transfer agents, tilt angle control agents, plasticizers, and crosslinking agents. From the viewpoint of uniformity and orientation, liquid crystal compositions are also preferably free of fillers (e.g., silicon dioxide).

[0102] [Membrane manufacturing method] The film of the present invention is formed using the above-described liquid crystal composition. The method for manufacturing the film of the present invention preferably includes, in sequence: a coating forming step, coating the above-mentioned liquid crystal composition to form a coating film; an alignment step, aligning the liquid crystal compound contained in the above-mentioned coating film; and an alignment fixing step, fixing the alignment state. The membrane of the present invention is preferably an optical membrane.

[0103] In the above-described coating formation process, a liquid crystal composition is coated onto a substrate to form a coating film. The substrate is not particularly limited; for example, the support and alignment film included in the laminate described later can be cited. By using a liquid crystal composition containing the aforementioned solvent, or by using a substance that has been molten into a liquid state such as a liquid by heating, the liquid crystal composition can be easily coated onto the alignment film. Commonly known methods for coating liquid crystal compositions include roller coating, gravure printing, spin coating, wire-wound coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spray coating, and inkjet coating.

[0104] The method for aligning the liquid crystal compound in the above-described alignment process is not particularly limited, but heat treatment is preferred. From the viewpoint of manufacturing applicability, the heating temperature is preferably 10–250°C, more preferably 25–190°C. Furthermore, the heating time is preferably 1–300 seconds, more preferably 1–60 seconds. A cooling process can be performed after the above-described heat treatment. The cooling process involves cooling the heated coating film to approximately room temperature (20–25°C). There are no particular limitations on the cooling method, and it can be carried out using known methods.

[0105] The immobilization method in the above orientation fixation process is not particularly limited, but preferably involves at least one of the processes of polymerization and drying. The polymerization conditions described above are not particularly limited; however, ultraviolet light is preferred in polymerization utilizing light irradiation. The preferred irradiation dose is 10 mJ / cm². 2 ~50J / cm 2 More preferably 20 mJ / cm 2 ~5J / cm 2 Further preferred is 30 mJ / cm 2 ~3J / cm 2 The preferred value is 50–1000 mJ / cm³.2 Furthermore, irradiation can be carried out under heating conditions to promote the polymerization reaction.

[0106] The method for manufacturing the membrane of the present invention preferably includes a step of performing a surface modification treatment. Specifically, examples of the surface modification treatment include corona treatment and plasma treatment, with corona treatment being preferred. In other words, the membrane is preferably subjected to corona treatment or plasma treatment. The timing of surface modification treatment is not particularly restricted, but it is preferred to be carried out after the orientation fixing process. The surface modification treatment described above is preferably performed on the surface of the coating film opposite to the substrate. In other words, it is preferably performed on the surface on the side where the leveling agent is biased. By implementing surface modification treatment, the bonding state of silicon atoms contained in a specific leveling agent changes, and the binding energy of the peak of the Si2p photoelectron spectrum and / or the amount of silicon atoms bonded to 4 oxygen atoms are optimized.

[0107] The methods of corona treatment and plasma treatment are not particularly limited, and well-known methods can be used, such as well-known corona discharge devices and plasma treatment devices. The discharge amount in the corona treatment can be adjusted appropriately according to the composition of the membrane, etc., and is preferably 10 W / min / m. 2 The above is preferred, with 50 Wmin / m 2 The above is preferred, with 500 Wmin / m 2 That's all. The upper limit is not specifically restricted, but 5000 Wmin / m 2 The following conditions are more common, with 2000 Wmin / m being the preferred value. 2 the following. The output and processing time in corona treatment can be adjusted appropriately.

[0108] The method of plasma processing is not particularly limited, and known methods can be used, such as using known plasma processing apparatus. As plasma processing apparatus, various apparatuses such as those described in Japanese Patent Application Publication No. 2018-170183 (paragraphs

[0015] to

[0058] ) and Japanese Patent Application Publication No. 2013-056514 (paragraphs

[0041] to

[0074] ) can be referred to, and these contents are incorporated in this specification.

[0109] The plasma treatment described above can be carried out under atmospheric pressure or under reduced pressure (below 500 Pa, preferably 0 to 100 Pa).

[0110] In plasma processing, the gas used as the plasma state (plasma feed gas) is not particularly limited, and can include rare gases (inert gases) such as helium, neon, argon, krypton, xenon and radon, oxygen, nitrogen and hydrogen. The plasma feed gas is preferably a mixture of a reactive gas selected from oxygen and nitrogen and a rare gas. From the viewpoint that the water contact angle of the membrane surface after plasma treatment is more easily reduced, the content of the reactive gas selected from oxygen and nitrogen in the mixture (the total content if both are included) is preferably 0.1 to 10.0% by volume, more preferably 1.0 to 8.0% by volume, relative to the total volume of the mixture. Furthermore, relative to the total volume of the mixed gas, the content of rare gas in the mixed gas is preferably 50.0% by volume or more, more preferably 80.0% by volume or more, and even more preferably 90.0% by volume or more. Additionally, the upper limit of the rare gas content in the mixed gas is not particularly limited, but is preferably 99.9% by volume or less, more preferably 99.0% by mass or less, relative to the total volume of the mixed gas. Compared to oxygen or nitrogen, rare gases are more easily plasma-generated by applying low energy. Therefore, by setting the rare gas content within the above-mentioned numerical range, discharge can be uniformly induced on the coating surface, and the coating surface can be easily and uniformly modified. Of the aforementioned rare gases, helium or argon is preferred from the viewpoint of easily maintaining a stable discharge state, and helium is more preferred from the viewpoint of having a longer lifetime in the excited state. The gas composition of plasma feedstock gas can be quantified by analyzing the sampled plasma feedstock gas using analytical devices such as gas chromatography and mass spectrometry.

[0111] Furthermore, it is preferable to use a plasma generation device that generates plasma between the electrode and the counter electrode by supplying electricity, and to perform plasma treatment on the surface of the coating while delivering the coating. The power used in plasma treatment is preferably 100 to 8000 W. In particular, from the viewpoint of further reducing the water contact angle of the membrane, the power used for plasma treatment under atmospheric pressure is more preferably 600 to 8000 W, and even more preferably 2500 to 6000 W. From the viewpoint of further reducing the water contact angle of the membrane, the power used for plasma treatment under depressurization is more preferably 100 to 1000 W, and even more preferably 100 to 500 W. Furthermore, from the viewpoints of superior productivity and discharge stability (stability of the modified in-plane uniformity), the lower limit of the transport speed of the coating subjected to plasma treatment is preferably 1.0 m / min or more, more preferably 3.0 m / min or more, and even more preferably 5.0 m / min or more. From the viewpoints of suppressing the influence of accompanying air and excellent discharge stability (stability of the modified in-plane uniformity), the upper limit of the transport speed of the coating subjected to plasma treatment is preferably 100 m / min or less, more preferably 50.0 m / min or less, even more preferably 30.0 m / min or less, even more preferably 15.0 m / min or less, and particularly preferably less than 10.0 m / min.

[0112] When plasma treatment is performed under atmospheric pressure, the plasma treatment time is preferably 10 seconds to 10 hours, more preferably 10 seconds to 1 hour. When plasma treatment is performed under reduced pressure, the plasma treatment time is preferably 10 seconds to 10 hours, more preferably 10 seconds to 1 hour. By setting the plasma treatment time within the above-mentioned range, it is less likely to cause defects such as substrate melting due to heat and / or electrode deformation. Plasma treatment can be performed continuously or intermittently. In the case of intermittent treatment, the total treatment time is preferably within the range described above. The preferred processing temperature for plasma treatment is 0–200°C, more preferably 15–150°C.

[0113] [Properties of the membrane] The film of the present invention is formed using a liquid crystal composition. As described above, the orientation state of the liquid crystal compound is preferably immobilized in the film. Furthermore, in this specification, the state in which the orientation state of the liquid crystal compound is "immobilized" means that the orientation of the liquid crystal compound is maintained. Specifically, more preferably, it is a state in which there is no fluidity in the layer within a temperature range typically 0 to 50°C, or more severely under conditions of -30 to 70°C, and the fixed orientation shape is stably maintained without being affected by external fields or forces. In a film in which the orientation state is fixed, the liquid crystal compound may no longer exhibit liquid crystal properties. In the membrane configuration, the liquid crystal compound can be a polymer of a polymeric liquid crystal compound, or a high molecular weight liquid crystal compound that is a high molecular weight component in the liquid crystal composition. That is, the membrane can be a polymer containing a polymeric liquid crystal compound, as described later, or it can be a polymer containing a polymeric liquid crystal compound and a component derived from a specific leveling agent.

[0114] The orientation state of the liquid crystal compound in the film of the present invention can be any of the following states: horizontal orientation, vertical orientation, tilted orientation, and twisted orientation. Furthermore, as described in International Publication No. 2021 / 033640, the liquid crystal curing layer can have multiple orientation states in one layer, and the liquid crystal curing layer has, along the thickness direction, a first region formed by fixing the orientation state of a liquid crystal compound that is twisted and oriented along a spiral axis extending along the thickness direction; and a second region formed by fixing the orientation state of a uniformly oriented liquid crystal compound. Furthermore, in this specification, "horizontal alignment" means that the main surface of the film is parallel to the long axis of the liquid crystal compound. However, strict parallelism is not required; in this specification, it refers to an alignment where the angle between the long axis of the liquid crystal compound and the main surface of the film is less than 10°. Similarly, in this specification, "vertical alignment" means that the main surface of the film is orthogonal to the long axis of the liquid crystal compound. However, strict perpendicularity is not required; in this specification, it refers to an alignment where the angle between the long axis of the liquid crystal compound and the main surface of the film is 170° to 110°.

[0115] The membrane of the present invention is preferably an optically anisotropic membrane. As an optically anisotropic film, examples include a positive A plate, a positive C plate, and an optically anisotropic film (hereinafter, this method will also be referred to as "optically anisotropic film A") having, along the thickness direction, a first region in which the orientation state of a liquid crystal compound oriented in a twisted manner along a helical axis extending along the thickness direction is fixed; and a second region in which the orientation state of a uniformly oriented liquid crystal compound is fixed.

[0116] The positive A plate (positive A plate) and the positive C plate (positive C plate) are defined as follows. When the refractive index in the slow axis direction (the direction with the highest refractive index in the plane) is set as nx, the refractive index in the direction orthogonal to the slow axis in the plane is set as ny, and the refractive index in the thickness direction is set as nz, the positive A plate satisfies equation (A1), and the positive C plate satisfies equation (C1). Furthermore, Rth for the positive A plate represents a positive value, and Rth for the positive C plate represents a negative value. Equation (A1) nx>ny≈nz Equation (C1) nz>nx≈ny Furthermore, the aforementioned “≈” not only includes cases where the two are completely identical, but also cases where the two are substantially identical. Regarding the phrase "substantially identical," in the positive A-plate, for example, the case where (ny-nz)×d (where d is the film thickness) is -10 to 10 nm, preferably -5 to 5 nm, is also included in "ny≈nz," and the case where (nx-nz)×d is -10 to 10 nm, preferably -5 to 5 nm, is also included in "nx≈nz." Furthermore, in the positive C-plate, for example, even when (nx-ny)×d (where d is the film thickness) is 0 to 10 nm, preferably 0 to 5 nm, it is included in "nx≈ny."

[0117] When the membrane of the present invention is a positive A plate, from the viewpoint of functioning as a λ / 4 plate, Re (550) is preferably 100 to 180 nm, more preferably 120 to 160 nm, even more preferably 130 to 150 nm, and particularly preferably 130 to 145 nm. Here, "λ / 4 plate" refers to a plate with λ / 4 function, specifically a plate that has the function of converting linearly polarized light of a specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light).

[0118] The optical anisotropic film (optical anisotropic film A) is described in detail. The optical anisotropic film has, along the thickness direction, a first region in which the orientation state of a liquid crystal compound that is twisted and oriented along a helical axis extending along the thickness direction is fixed; and a second region in which the orientation state of a uniformly oriented liquid crystal compound is fixed. When the thickness of the first region of the optical anisotropic film A is set to d1 (nm) and the anisotropy of the refractive index of the first region measured at a wavelength of 550 nm is set to Δn1, from the viewpoint that the optical anisotropic film can be preferably applied to a circular polarizer, the first region preferably satisfies the following formula (1-1). Equation (1-1) 100nm≤Δn1d1≤240nm Among them, it is more preferable to satisfy equation (1-2), and even more preferable to satisfy equation (1-3). Equation (1-2) 120nm≤Δn1d1≤220nm Equation (1-3) 140nm≤Δn1d1≤200nm In addition, the refractive index anisotropy Δn1 represents the refractive index anisotropy of the first region.

[0119] The absolute value of the twist angle of the liquid crystal compound in the first region is not particularly limited, but from the viewpoint that the optical anisotropic film can be preferably applied to a circular polarizer, 60 to 120° is preferred, and 70 to 110° is more preferred. Regarding the method for measuring the twist angle, AxoScan from Axometrics Corporation was used, and the measurement was performed using Axometrics Corporation's device analysis software.

[0120] Furthermore, if the thickness of the second region of the optical anisotropic film A is set to d2 (nm) and the refractive index anisotropy of the second region to be measured at a wavelength of 550 nm is set to Δn2, from the viewpoint that the optical anisotropic film can be preferably applied to a circular polarizer, the second region preferably satisfies the following formula (2-1). Equation (2-1) 100nm≤Δn2d2≤240nm Among them, it is more preferable to satisfy equation (2-2), and even more preferable to satisfy equation (2-3). Equation (2-2) 120nm≤Δn2d2≤220nm Equation (2-3) 140nm≤Δn2d2≤200nm In addition, the refractive index anisotropy Δn2 represents the refractive index anisotropy of the second region.

[0121] The membrane of the present invention contains silicon atoms derived from a specific leveling agent. The form of these silicon atoms is not particularly limited; they may be part of the specific leveling agent or exist in other ways. Alternatively, the membrane may contain components derived from the specific leveling agent (e.g., silicon dioxide, described later). From the viewpoint of achieving better results with this invention, it is also preferable to contain silicon atoms in the form of silicon dioxide. The presence of silicon dioxide, for example, is equivalent to (SiO2) when time-of-flight secondary ion mass spectrometry (TOF-SIMS) is performed on the membrane. l The presence or absence of fragments with molecular weights of 1 or higher (l is an integer greater than or equal to 1) is used to determine this.

[0122] The thickness of the membrane of the present invention is not particularly limited, but is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.

[0123] <Requirement 1> The membrane of the first method satisfies the following requirement 1. Requirement 1: The binding energy of the peak in the Si2p photoelectron spectrum obtained by measuring the surface of the film using X-ray photoelectron spectroscopy (XPS) is above 102.0 eV. Furthermore, the film of the first method only needs to satisfy requirement 1 on at least one surface. In the above-described film manufacturing method, it is preferable to use the surface of the air interface side of the coating film formed by the liquid crystal composition to satisfy the above requirement.

[0124] From the viewpoint of achieving better results with the present invention, the binding energy at the peak of the photoelectron spectrum of the above-mentioned Si2p is preferably 102.5 eV or more, and more preferably 103.2 eV or more. The binding energy at the peak of the photoelectron spectrum of Si2p is often below 105.0 eV, and even more often below 104.0 eV.

[0125] The photoelectron spectrum of Si2p measured by XPS is the inner-shell photoelectron spectrum corresponding to the 2p orbital of silicon (Si). The specific method for measuring the photoelectron spectroscopy of Si2p is as follows. First, the surface of the film was measured under the following conditions to obtain the photoelectron spectrum of Si2p. The peaks observed in the range of 101.0–106.0 eV were attributed to the photoelectron spectrum of Si2p.

[0126] (XPS measurement conditions) • Device: Quantera manufactured by ULVAC-PHI, Inc. • X-ray source: Monochromatic Al-Ka rays (X-ray beam diameter 100μmΦ, output 25W, voltage 15kV) • Analytical area: 300μm × 300μm ·Pass Energy: 55eV • Step Energy: 0.05 eV • Charge compensation: present (and in conjunction with electron gun / low-velocity ion gun) • Photoelectron emission angle: 45° In the above measurements, the binding energy was calibrated by setting the peak of the photoelectron spectrum of C1s originating from the CC bond, detected from the same sample, to 284.8 eV.

[0127] <Requirement 2> The membrane of the second method satisfies the following requirement 2. Requirement 2: There are silicon atoms bonded to 4 oxygen atoms on the surface of the membrane. Furthermore, for the second type of film, at least one surface needs to satisfy requirement 2. In the above-described film manufacturing method, it is preferable to use the surface of the air interface side of the coating film formed by the liquid crystal composition to satisfy the above requirement.

[0128] The presence of silicon atoms bonded to four oxygen atoms can be confirmed by XPS. Specifically, this can be confirmed by the presence or absence of peaks attributable to silicon atoms bonded to four oxygen atoms in the Si2p photoelectron spectrum measured by XPS using the same steps as in requirement 1 above.

[0129] The method for identifying peaks belonging to silicon atoms bonded to four oxygen atoms is explained. The photoelectron spectrum of Si2p was fitted using the binding energies of the four peaks shown below (peaks 1 through 4). Peak 1 is assigned to SiO_1, peak 2 to SiO_2, peak 3 to SiO_3, and peak 4 to SiO_4. SiO_n (n=1, 2, 3, 4) represents a silicon atom with n Si-O bonds and (4-n) Si-C bonds. SiO_4 is equivalent to a silicon atom bonded to 4 oxygen atoms. Specifically, the binding energies of the peaks of the 1st to 4th peaks were fixed within ±0.1 eV of the values ​​shown below. The fitting function was set as the Gauss-Lorentz function (Gauss ratio above 90%). The baseline was processed using the Shirley method and fitted in a way that minimized the sum of squared residuals with the measured spectrum. First peak (SiO₁): 101.62 eV Second peak (SiO₂): 102.15 eV Peak 3 (SiO3): 102.65 eV Peak 4 (SiO₄): 103.33 eV

[0130] According to the obtained fitting results, when a fourth peak is present, there are silicon atoms bonded to four oxygen atoms. Furthermore, the presence of a fourth peak refers to the fact that the area of ​​the fourth peak accounts for 4% or more of the area of ​​the photoelectron spectrum of Si2p. Preferably, the area of ​​the fourth peak accounts for 30% or more of the area of ​​the photoelectron spectrum of Si2p, more preferably 97% or more. The upper limit of the area of ​​the fourth peak is not particularly limited, and the area relative to the photoelectron spectrum of Si2p can be 100%.

[0131] <Silicon atomic weight> From a viewpoint superior to the present invention, the silicon atom content on the surface of the membrane of the present invention is preferably 15.0 Atomic% or less, more preferably 5.0 Atomic% or less, relative to all atoms on the membrane surface. Furthermore, from the viewpoint of superior leveling properties and the effects of the present invention, the silicon atom content on the surface of the membrane of the present invention is preferably 1.0 Atomic% or more, more preferably 1.5 Atomic% or more, relative to all atoms on the membrane surface. The silicon atom content mentioned above is the value determined by the XPS described above. Specifically, XPS is performed using the same steps as in requirement 1 above, the atomic concentration of all detected atoms is calculated, and the silicon atom content (Atomic%) relative to all detected atoms is calculated. A surface that satisfies either requirement 1 or requirement 2 is preferably satisfied with the above requirements. In this case, other surfaces may not satisfy the above requirements.

[0132] (Water contact angle) The water contact angle of the membrane surface of the present invention is preferably 80° or less, more preferably 70° or less, and even more preferably 50° or less. Furthermore, the water contact angle of the membrane of the present invention is often 10° or more, and preferably 20° or more. A surface that satisfies either requirement 1 or requirement 2 is preferably satisfied with the above requirements. In this case, other surfaces may not satisfy the above requirements. The aforementioned water contact angle can be measured by known methods, for example, it can be measured at 25°C using a DMo-702 manufactured by Kyowa InterfaceScience Co., Ltd.

[0133] <Surface elastic modulus> The surface elastic modulus of the membrane of the present invention is preferably 2.5 GPa or higher, more preferably 4.0 GPa or higher, and even more preferably 5.1 GPa or higher. The upper limit of the surface elastic modulus of the membrane of the present invention is not particularly limited, and it is often below 10.0 GPa, preferably below 7.0 GPa. A surface that satisfies either requirement 1 or requirement 2 is preferably satisfied with the above requirements. In this case, other surfaces may not satisfy the above requirements. In addition, the surface in the above-mentioned surface elastic modulus refers to the region from the air interface of the film to below 20 nm.

[0134] The aforementioned surface elastic modulus can be measured on the surface of the film using an atomic force microscope (AFM). Specifically, the surface elastic modulus can be calculated by fitting the load / displacement curve obtained using an AFM device in QNM mode to a JKR contact mechanics model. For example, a Dimension Icon device manufactured by Bruker can be used as the AFM. Detailed steps are described in the embodiments described later.

[0135] <Surface Adsorption Force> The surface adsorption capacity of the membrane of the present invention is preferably 9.5 nN or more, more preferably 12.0 nN or more, and even more preferably 20.0 nN or more. Furthermore, the upper limit of the surface adsorption capacity of the membrane of the present invention is not particularly limited, but it is often below 50.0 nN, preferably below 40.0 nN, and more preferably below 30.0 nN. A surface that satisfies either requirement 1 or requirement 2 is preferably satisfied with the above requirements. In this case, other surfaces may not satisfy the above requirements.

[0136] The aforementioned surface adsorption forces can be measured on the surface of the membrane using AFM. Specifically, the surface adsorption force can be calculated by fitting the load / displacement curve obtained using an AFM device in QNM mode to the JKR contact mechanics model. Detailed steps are described in the embodiments described later.

[0137] [Layered Body] The membrane of the present invention can be used as a laminate in combination with other layers. Other layers in a laminate containing the film of the present invention (hereinafter also referred to as "the laminate of the present invention") may include, for example, a support and an orientation film. Furthermore, in the above-described laminate, it is preferable that the surface of the film satisfying at least one of requirements 1 and 2 is the outermost surface of the other layers. Figure 1 This is a schematic cross-sectional view illustrating an example of the laminated body of the present invention. Additionally, Figure 1 This is a schematic diagram; the thickness and positional relationship of each layer may not necessarily match the actual situation. Figure 1 The support and orientation film shown are arbitrary components. Figure 1 The laminate 10 shown has a support 16, an alignment film 14, and a liquid crystal layer 12 in sequence. The liquid crystal layer 12 is the film of the present invention. Furthermore, the liquid crystal layer 12 can be an optically anisotropic layer. Additionally, other liquid crystal layers can be included between the liquid crystal layer 12 and the alignment film 14. For example, when the polarizer of the present invention described later is used as a circular polarizer, or when the film of the present invention is used as an optical compensation film in a liquid crystal display device using IPS (In-Plane-Switching) or FFS (Fringe-Field-Switching) methods, the laminate preferably includes a positive A plate and a positive C plate. The various components used in the laminate of the present invention will be described in detail below.

[0138] <Support> The support is a substrate used to form the film. The aforementioned support is preferably transparent. Specifically, the light transmittance is preferably 80% or higher.

[0139] Examples of supports include glass substrates and polymer films. Examples of polymer film materials include cellulose-based polymers; acrylic polymers such as polymethyl methacrylate and polymers containing lactone rings; thermoplastic norbornene-based polymers; polycarbonate-based polymers; polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate; styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymers (AS resins); polyolefin-based polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers; vinyl chloride-based polymers; amide-based polymers such as nylon and aromatic polyamides; imide-based polymers; sulfone-based polymers; polyethersulfone-based polymers; polyetheretherketone-based polymers; polyphenylene sulfide-based polymers; vinylidene chloride-based polymers; vinyl alcohol-based polymers; vinyl butyral-based polymers; aromatic ester-based polymers; polyoxymethylene-based polymers; epoxy-based polymers; and polymers composed of mixtures of these polymers. Furthermore, it can also serve as a support for the deflector described later.

[0140] The thickness of the aforementioned support is not particularly limited, but is preferably 5–100 μm, more preferably 5–50 μm. The support is preferably peelable.

[0141] <Orientation film> The laminate of the present invention preferably has an alignment film between the support and the film. Alternatively, the support can also serve as the alignment film.

[0142] Alignment films are typically composed primarily of polymers. Polymer materials used in alignment films are documented in numerous publications, and several commercially available products are readily available. The polymer material used in this invention is preferably polyvinyl alcohol or polyimide and its derivatives. Modified or unmodified polyvinyl alcohol is particularly preferred. Regarding the alignment film that can be used in this invention, examples include the alignment film described on page 43, line 24 to page 49, line 8 of International Publication No. 01 / 088574; the modified polyvinyl alcohol described in paragraphs

[0071] to

[0095] of Japanese Patent No. 3907735; the liquid crystal alignment film formed by a liquid crystal alignment agent described in Japanese Patent Application Publication No. 2012-155308; and so on.

[0143] In this invention, it is preferable to use a photo-alignment film as the alignment film, based on the reason that it is possible to prevent planar deterioration by not contacting the surface of the alignment film during the formation of the alignment film. As a photoalignment film, it is not particularly limited and can use polymer materials such as polyamide compounds or polyimide compounds described in paragraphs

[0024] to

[0043] of International Publication No. 2005 / 096041; liquid crystal alignment films formed by liquid crystal alignment agents having photoalignment groups with cinnamic acid structures as described in Japanese Patent Application Publication No. 2012-155308; and products manufactured by Rolic Technologies Ltd. under the trade name LPP-JP265CP.

[0144] Furthermore, in this invention, the thickness of the orientation film is not particularly limited, but from the viewpoint of forming an optically anisotropic layer with uniform film thickness by mitigating the surface irregularities that may exist on the support, it is preferably 0.01 to 10 μm, more preferably 0.01 to 1 μm, and even more preferably 0.01 to 0.5 μm.

[0145] In the laminate of the present invention, the film of the present invention can be formed on the surface of other liquid crystal layers. Other liquid crystal layers may be liquid crystal layers formed by fixing the above-mentioned liquid crystal composition into a predetermined orientation state, or liquid crystal layers formed by fixing a composition containing a liquid crystal compound and any required components (e.g., polymerization initiator, dichroic substance and leveling agent) into a predetermined orientation state.

[0146] In the laminate of the present invention, the film of the present invention can be laminated with other liquid crystal layers. When the film of the present invention is laminated with other liquid crystal layers, it is also preferable to laminate them with an adhesive layer in between. In other words, the laminate of the present invention preferably has an adhesive layer. As described above, liquid crystal layers formed using liquid crystal compositions containing leveling agents containing silicon atoms (in particular, on the surface where the leveling agent is biased) sometimes have insufficient adhesion to adjacent layers, but the film of the present invention satisfies at least one of the above-described requirements 1 and 2, and therefore exhibits excellent adhesion even when laminated with an adhesive layer on the surface side where the leveling agent is biased. Other liquid crystal layers can be the films of this invention, or other liquid crystal layers described above.

[0147] The adhesive layer described above is a layer formed using an adhesive. Preferably, the adhesive layer is a curable adhesive composition that is cured by irradiation with active energy rays or by heating. Examples of curable adhesives include electron beam curable adhesives, ultraviolet curable adhesives, and visible light curable adhesives, with ultraviolet curable adhesives being the preferred type. Examples of curable adhesive compositions include curable adhesive compositions containing cationic polymerizable compounds (e.g., epoxy adhesives) and curable adhesive compositions containing free radical polymerizable compounds (e.g., (meth)acrylate adhesives). As an adhesive layer, for example, reference can be made to paragraphs

[0062] to

[0080] of Japanese Patent Application Publication No. 2016-035579, the contents of which are incorporated into the specification of this application.

[0148] Taking into account the influence of external light (especially ultraviolet light), the laminate of the present invention preferably contains an ultraviolet (UV) absorber. The ultraviolet absorber can be contained in the membrane of the present invention or in components other than the membrane. For example, a support is preferably included as a component other than the membrane. As a UV absorber, any conventionally known UV absorber capable of exhibiting UV absorption properties can be used. Among such UV absorbers, from the viewpoint of obtaining UV absorption capacity (UV cutoff capacity) with high UV absorption and usability in image display devices, benzotriazole-based or hydroxyphenyltriazine-based UV absorbers are preferred. Furthermore, in order to broaden the absorption width of ultraviolet light, it is possible to use two or more ultraviolet absorbers with different maximum absorption wavelengths. As ultraviolet absorbers, for example, compounds described in paragraphs

[0258] to

[0259] of Japanese Patent Application Publication No. 2012-018395 and compounds described in paragraphs

[0055] to

[0105] of Japanese Patent Application Publication No. 2007-072163 can be cited. Furthermore, as a commercially available product, it can be used with Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479 and Tinuvin 1577 (all manufactured by BASF).

[0149] [Polarizing filter] The polarizer of the present invention comprises a polarizer, an adhesive layer, and the film of the present invention. When the film of the present invention is a positive A plate, from the viewpoint that it can be preferably applied to circular polarizers, the angle between the slow axis of the positive A plate and the absorption axis of the polarizer described later is preferably 30 to 60°, more preferably 40 to 50°, even more preferably 42 to 48°, and particularly preferably 45°. Here, "slow axis" refers to the direction with the highest refractive index in the liquid crystal layer, and "absorption axis" of the polarizer refers to the direction with the highest absorbance. When the film of the present invention is the optical anisotropic film A described above, from the viewpoint that the optical anisotropic film A can be preferably applied to circular polarizers, the absolute value of the angle between the in-plane slow axis of the second region formed by fixing the orientation state of the uniformly oriented liquid crystal compound and the absorption axis of the polarizer is preferably 5 to 25°, more preferably 10 to 20°. Furthermore, polarizers can also be used as optical compensation films in IPS or FFS liquid crystal display devices. When using a polarizer as an optical compensation film in an IPS or FFS type liquid crystal display device, it is preferable to set the film of the present invention as at least one of a laminate of a positive A plate and a positive C plate. In other words, the polarizer of the present invention preferably includes a polarizer, an adhesive layer, the film of the present invention, and a liquid crystal layer, wherein one of the film and the liquid crystal layer is a positive A plate and the other is a positive C plate. Alternatively, the liquid crystal layer may also be equivalent to the film of the present invention. It is preferable that the angle between the slow axis of the positive A plate layer and the absorption axis of the polarizer (described later) is orthogonal or parallel; more preferably, the angle between the slow axis of the positive A plate layer and the absorption axis of the polarizer (described later) is 0 to 5° or 85 to 95°. When the polarizer of the present invention is used in the image display device described later, it is preferable that the angle between the slow axis of the liquid crystal layer and the absorption axis of the polarizer described later is parallel or orthogonal.

[0150] The polarizer of the present invention may have an adhesive layer between the polarizer and the film of the present invention, and the adhesive layer may be an adhesive layer. In the case where the polarizer of the present invention comprises a laminate of a positive A plate and a positive C plate, it is preferable to have an adhesive layer between the positive A plate and the positive C plate.

[0151] Figure 2 This is a schematic cross-sectional view illustrating an example of the polarizer of the present invention. Figure 2 The polarizer 20 shown sequentially includes a polarizer 22, a first sealing layer 24, a first liquid crystal layer 26, a second sealing layer 28, and a second liquid crystal layer 30. Additionally, Figure 2 This is a schematic diagram, and the thickness and positional relationship of each layer may not necessarily match the actual situation. Furthermore, one of the first sealing layer 24 and the second sealing layer 28 is an arbitrary component, and one of the first liquid crystal layer and the second liquid crystal layer is an arbitrary component. exist Figure 2 In the polarizer shown, preferably at least one of the first liquid crystal layer 26 and the second liquid crystal layer 30 is the film of the present invention, and at least the first liquid crystal layer 26 is the film of the present invention. Furthermore, preferably the first liquid crystal layer 26 and the second liquid crystal layer 30 are the positive A plate and the positive C plate, respectively. exist Figure 2 In the polarizer shown, preferably at least one of the first adhesive layer 24 and the second adhesive layer 28 is an adhesive layer, and at least the second adhesive layer 28 is an adhesive layer.

[0152] [Polarizer] A polarizer is not particularly restricted as long as it is a component that has the function of converting light into specific linearly polarized light. It can utilize existing and known absorption polarizers, reflection polarizers, and coating polarizers. As an absorption-type polarizer, iodine-based polarizers, dye-based polarizers utilizing dichroic dyes, and polyene-based polarizers can be used. Among iodine-based and dye-based polarizers, both coating-type and stretching-type polarizers are applicable, but polarizers made by adsorbing iodine or dichroic dyes onto polyvinyl alcohol and then stretching them are preferred. Examples of coating-type polarizers include polarizers containing cured liquid crystal compounds and dichroic pigments. As a reflective polarizer, polarizers can be obtained by stacking thin films with different birefringence, wire grid polarizers, and polarizers obtained by combining cholesteric liquid crystals with selective reflection regions and quarter-wave plates.

[0153] The thickness of the polarizer is not particularly limited, preferably 3-60 μm, more preferably 3-30 μm, and even more preferably 3-10 μm.

[0154] [Adhesive layer] The polarizer of the present invention has an adhesive layer. The polarizer of the present invention may have an adhesive layer between the polarizer and the film of the present invention, or an adhesive layer may be present between any one of the polarizer and the film of the present invention and other layers (e.g., a liquid crystal layer), or an adhesive layer may be present between any layers. The adhesive layer is preferably adjacent to the film of the present invention. Preferably, the adhesive layer is adjacent to the surface satisfying requirement 1 of the film of the first embodiment or to the surface satisfying requirement 2 of the film of the second embodiment. The adhesive layer mentioned above can be cited as an example.

[0155] The thickness of the adhesive layer is preferably 0.01 to 20 μm, more preferably 0.01 to 10 μm, and even more preferably 0.05 to 5 μm. If the thickness of the adhesive layer is within this range, no lifting or peeling will occur between the laminated film and the polarizer, and a practically problem-free adhesion force can be obtained. Furthermore, from the viewpoint of suppressing the generation of air bubbles, the thickness of the adhesive layer is preferably 0.4 μm or more.

[0156] The polarizer of the present invention may have an adhesive layer as a sealing layer. For example, an adhesive layer may be provided between the film of the present invention and other liquid crystal layers, and an adhesive layer may be provided between the polarizer and the polarizer of the present invention. Examples of adhesives included in the adhesive layer include acrylic adhesives, epoxy adhesives, rubber adhesives, silicone adhesives, urethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinylpyrrolidone adhesives, polyacrylamide adhesives, and cellulose adhesives. Among them, acrylic adhesives (pressure-sensitive adhesives) are preferred from the perspective of their superior transparency, weather resistance and heat resistance. As an adhesive, reference can be made to paragraphs

[0071] to

[0084] of Japanese Patent Application Publication No. 2018-060014, the contents of which are incorporated into this specification.

[0157] The thickness of the adhesive layer is preferably 0.01–20 μm, more preferably 0.01–10 μm, and even more preferably 0.05–5 μm. If the thickness of the adhesive layer is within this range, no lifting or peeling will occur between the layers, and a practically problem-free adhesion can be obtained.

[0158] [Image display device] The display device of the present invention is an image display device having the film or polarizer of the present invention. The display element used in the image display device is not particularly limited; examples include liquid crystal cells, organic electroluminescent (hereinafter referred to as "EL"). and plasma display panels. Among these, liquid crystal cells or organic EL display panels are preferred. That is, as the image display device of the present invention, a liquid crystal display device that uses liquid crystal cells as display elements and an organic EL display device that uses organic EL display panels as display elements are preferred.

[0159] [Organic EL display device] As an example of an image display device, an organic EL display device can be described as having, in order from the visual recognition side, a polarizer, a λ / 4 plate made of the aforementioned film, and an organic EL display panel. Furthermore, an organic EL display panel is a display panel constructed using organic EL elements formed by sandwiching an organic light-emitting layer (organic electroluminescent layer) between electrodes (between the cathode and the anode). There are no particular restrictions on the structure of an organic EL display panel, and known structures can be used.

[0160] [Liquid Crystal Display Device] As an example of an image display device, a liquid crystal display device is a liquid crystal display device having the aforementioned polarizer and liquid crystal unit. Furthermore, among the polarizers disposed on both sides of the liquid crystal cell, it is preferable to use the aforementioned polarizer as the front polarizer, and more preferably to use the aforementioned polarizer as both the front and rear polarizers.

[0161] <Liquid Crystal Unit> The liquid crystal cells used in the liquid crystal display device are preferably in VA (Vertical Alignment) mode, OCB (Optically Compensated Bend) mode, IPS (In-Plane-Switching) mode, FFS (Fringe-Field-Switching) mode or TN (Twisted Nematic) mode, but are not limited to these. Example

[0162] The present invention will now be described in more detail with reference to embodiments. The materials, quantities, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited to the embodiments shown below.

[0163] [Fabrication of Membranes and Laminates] The membrane and laminate of the present invention were fabricated as follows.

[0164] [Preparation of the support (cellulose acylated gel)] The following composition was added to a mixing tank and stirred, then heated at 90°C for 10 minutes. The resulting composition was then filtered through filter paper with an average pore size of 34 μm and a sintered metal filter with an average pore size of 10 μm to prepare a paste. The paste had a solids content of 23.5% by mass, and the amount of plasticizer added was relative to the cellulose acylate. The solvent for the paste was dichloromethane / methanol / butanol = 81 / 18 / 1 (by mass).

[0165] ―――――――――――――――――――――――――――――――― Cellulose acylated gel ―――――――――――――――――――――――――――――――― Cellulose acylates (Acetyl substitution degree 2.86, viscosity-uniform polymerization degree 310) 100 parts by weight • 6.0 parts by mass of sugar ester compound 1 (formula (S4) below) • Sugar ester compound 2 (formula (S5) below) 2.0 parts by mass • Silica particle dispersion (AEROSIL R972, manufactured by NIPPON AEROSIL CO.,LTD.) 0.1 parts by weight • Solvent (dichloromethane / methanol / butanol) 351.9 parts by weight ――――――――――――――――――――――――――――――――

[0166] [Chemical Formula 13]

[0167] [Chemical Formula 14]

[0168] The adhesive paste prepared above was cast using a roller film casting machine. The adhesive paste was cast from the die onto and into a metal support cooled to 0°C, and then the resulting web (film) was peeled off. The roller was made of SUS (SteelUse Stainless).

[0169] After the web (film) obtained from the casting process is peeled off from the rollers, it is dried for 20 minutes at 30–40°C using a tenter frame that clamps both ends of the web for transport. Then, it is post-dried by zone heating while being transported by rollers. The resulting web is then knurled and wound up to obtain cellulose acylated film A1. The obtained cellulose acylated membrane A1 has a thickness of 40 μm, an in-plane retardation Re(550) of 1 nm at a wavelength of 550 nm, and a thickness retardation Rth(550) of 25 nm at a wavelength of 550 nm.

[0170] [Construction of the F1-1 laminate] <Formation of Orientation Film> Using a wire rod, a photo-alignment film forming coating solution E1 with the following composition is continuously coated onto the cellulose acylate film A1 described above. The cellulose acylate film A1 with the coating is dried with warm air at 140°C for 120 seconds, and then the coating is irradiated with polarized ultraviolet light (10 mJ / cm²). 2 Using an ultra-high pressure mercury lamp, a 0.7 μm thick photo-aligned film E1 was formed, thus obtaining a TAC film with a photo-aligned film.

[0171] ―――――――――――――――――――――――――――――――― Coating solution E1 for photo-aligned film formation ―――――――――――――――――――――――――――――――― • 100.00 parts by weight of the following polymer PA-2 • 6.00 parts by weight of the following thermal cationic polymerization initiator PAG-1 0.15 parts by weight of diisopropylethylamine ·Butyl acetate 622.75 parts by weight 155.69 parts by weight of methyl ethyl ketone ――――――――――――――――――――――――――――――――

[0172] Polymer PA-2 (weight average molecular weight: 45,000. Values ​​listed in each repeating unit indicate the content (mass%) of each repeat relative to all repeating units.)

[0173] [Chemical Formula 15]

[0174] PAG-1 thermal cationic polymerization initiator

[0175] [Chemical Formula 16]

[0176] <Formation of optical film F1-1> The liquid crystal composition F1-1, as described below, was coated onto the photoalignment film E1 using a rod coater. The coating formed on the photoalignment film E1 was heated to 120°C with warm air and then cooled to 60°C. Under a nitrogen atmosphere, the coating was irradiated with a high-pressure mercury lamp at a wavelength of 365 nm at 100 mJ / cm². 2 Then, while heating to 120°C, the coating was irradiated with 200 mJ / cm² of ultraviolet light. 2 The ultraviolet light is used to fix the orientation of the liquid crystal compound to form an optical film F1-1, thereby obtaining a laminate F1-1 having a support, an alignment film and an optical film F1-1 in sequence. The optical film F1-1 has a thickness of 2.9 μm and a Re(550) of 142 nm. Furthermore, the optical film F1-1 satisfies the relationship Re(450) ≤ Re(550) ≤ Re(650). The Re(450) / Re(550) ratio is 0.82. The optical film F1-1 is an optically anisotropic layer, equivalent to a so-called λ / 4 plate.

[0177] ―――――――――――――――――――――――――――――――― Liquid crystal composition F1-1 ―――――――――――――――――――――――――――――――― • 30.00 parts by weight of the following antidispersive compound LA-1 • 30.00 parts by weight of the following antidispersive compound LA-2 • 27.00 parts by weight of the following antidispersive compound LA-3 • 6.64 parts by weight of the following polymerizable liquid crystal compound LC-1 • 1.20 parts by weight of the following polymerizable liquid crystal compound LC-2 • 0.16 parts by weight of the following polymerizable liquid crystal compound LC-3 • 5.00 parts by weight of the following polymerizable liquid crystal compound LC-4 • 0.50 parts by weight of the following polymerization initiator PI-1 • 0.06 parts by weight of the following leveling agent SA-1 · Cyclopentanone 181.00 parts by weight 54.00 parts by weight of methyl ethyl ketone ――――――――――――――――――――――――――――――――

[0178] The inversely dispersive compound LA-1 (tBu represents tert-butyl).

[0179] [Chemical Formula 17]

[0180] Inverse dispersive compound LA-2

[0181] [Chemical Formula 18]

[0182] LA-3, a compound with inverse dispersive properties

[0183] [Chemical Formula 19]

[0184] Polymerizable liquid crystal compound LC-1

[0185] [Chemical Formula 20]

[0186] Polymerizable liquid crystal compound LC-2

[0187] [Chemical Formula 21]

[0188] Polymerized liquid crystal compound LC-3

[0189] [Chemical Formula 22]

[0190] Polymerizable liquid crystal compound LC-4 (Me represents methyl).

[0191] [Chemical Formula 23]

[0192] Polymerization initiator PI-1

[0193] [Chemical Formula 24]

[0194] Leveling agent SA-1 (weight average molecular weight: 20000. The values ​​listed for each repeating unit in the main chain indicate the content (mass ratio) of each repeating unit relative to all repeating units. The values ​​listed for each repeating unit in the side chain indicate the number of repeating units.)

[0195] [Chemical Formula 25]

[0196] [Construction of layered body F2-1] A liquid crystal composition F1-2 was used in which the amount of leveling agent SA-1 added in the above-mentioned liquid crystal composition F1-1 was changed from 0.06 parts by mass to 0.5 parts by mass. Otherwise, an optical film F2-1 was formed by the same method as the laminate F1-1, thereby producing a laminate F2-1.

[0197] [Construction of laminates F1-2 to F1-5 and F2-2 to F2-3] The surface of the optical film F1-1 of the laminate F1-1 was subjected to corona treatment under the conditions shown in Table 1 below to form optical films F1-2 to F1-5, thereby fabricating the laminate F1-2 to F1-5. The optical film F2-1 of the laminate F2-1 was subjected to corona treatment under the conditions shown in Table 1 below to form optical films F2-2 to F2-3, thereby fabricating the laminate F2-2 to F2-3.

[0198] [Construction of the stacked bodies F1-6] Under atmospheric pressure, plasma treatment was performed on the surface of the optical film F1-1 side of the laminate F1-1 to form the laminate F1-6. The plasma treatment was performed using an apparatus having the structure of the plasma generation apparatus described in Example 1 of Japanese Patent Application Publication No. 2018-170183. In this plasma generation apparatus, helium, oxygen, and nitrogen were introduced between the electrode and the counter electrode at a volume flow rate ratio of 10 / 0.025 / 0.5, and a power of 6000W was applied to the counter electrode to generate plasma between the electrode and the counter electrode. Furthermore, the transport speed of the laminate F1-1 transported between the electrode and the counter electrode was set to 10.0 m / min. The gas composition (analyzed by gas chromatography) of the plasma feed gas introduced into the plasma generation device was as follows: helium, oxygen, and nitrogen were 94.1% by volume, 0.4% by volume, and 5.5% by volume, respectively.

[0199] [Construction of the FC-1 C-board] The following coating solution (FC-1) for forming positive C-plates was applied to the cellulose acylated film A1, and the resulting coating was heated at 60°C for 60 seconds. Afterwards, it was subjected to a 70 mW / cm² coating in air. 2 An air-cooled metal halide lamp (manufactured by EYEGRAPHICS Co., Ltd.) provides 300 mJ / cm² irradiation. 2 The ultraviolet light is used to fix its orientation state, thereby making the liquid crystal compound vertically oriented, forming a positive C plate with a thickness of 0.5 μm and Rth(550) = -60 nm. Furthermore, the surface of the obtained positive C-plate is subjected to corona treatment (treatment rate 1200 Wmin / m). 2 Thus, the positive C board FC-1 was created.

[0200] ―――――――――――――――――――――――――――――――― FC-1 coating liquid for forming positive C-plate ―――――――――――――――――――――――――――――――― ·83 parts by mass of the above liquid crystal compound LC-1 15 parts by weight of the above-mentioned liquid crystal compound LC-2 • 2 parts by mass of the above liquid crystal compound LC-3 • Polymerizing monomer (UA-601I, manufactured by kyoeisha Chemical Co., Ltd.) 5 parts by weight • Polymerization initiator (IrgacureOXE01, manufactured by BASF) 4 parts by weight • 0.4 parts by weight of the following leveling agent SC-1 • 1.2 parts by weight of the following vertically oriented liquid crystal compound alignment agent S01 • The following polymer M is 1.14 parts by weight 494.9 parts by weight of methyl isobutyl ketone 95.0 parts by weight of ethyl propionate · 2-Butanone 43.3 parts by weight ――――――――――――――――――――――――――――――――

[0201] Vertically oriented liquid crystal compound alignment agent S01

[0202] [Chemical Formula 26]

[0203] Polymer M (weight average molecular weight: 60,000. The values ​​recorded in each repeating unit indicate the content (mass ratio) of each repeating unit relative to all repeating units.)

[0204] [Chemical Formula 27]

[0205] Leveling agent SC-1 (weight average molecular weight: 25000. The values ​​listed in each repeating unit indicate the content (mass ratio) of each repeating unit relative to all repeating units.)

[0206] [Chemical Formula 28]

[0207] [Fabrication of Polarizers and Image Display Devices] <Fabrication of Polarizer 1 with Protective Film> The surface of the support for the cellulose triacetate membrane TJ25 "Z-TAC" (manufactured by FUJIFILM Corporation: 25 μm thick) was subjected to alkaline saponification treatment. Specifically, the support was immersed in a 1.5 equivalent sodium hydroxide aqueous solution at 55°C for 2 minutes, then cleaned in a water bath at room temperature, and further neutralized with 0.1 equivalent sulfuric acid at 30°C. After neutralization, the support was cleaned in a water bath at room temperature and further dried with warm air at 100°C, thereby obtaining the polarizer protective film. A roll of polyvinyl alcohol film was stretched in an aqueous iodine solution along the MD (Machine Direction) direction and dried to obtain a polarizer 1 with a thickness of 14 μm. The protective film of the polarizer is attached to the two surfaces of the polarizer 1 using PVA adhesive, thereby creating a polarizer 1 with a protective film.

[0208] [Preparation of UV Adhesive 1] A UV adhesive 1 with the following composition was prepared. ―――――――――――――――――――――――――――――――― UV adhesive 1 ―――――――――――――――――――――――――――――――― • CEL2021P (manufactured by Daicel Corporation) 70 parts by weight · 20 parts by weight of 1,4-Butanediol diglycidyl ether 10 parts by weight of 2-ethylhexyl glycidyl ether • CPI-100P 2.25 parts by weight ――――――――――――――――――――――――――――――――

[0209] CPI-100P

[0210] [Chemical Formula 29]

[0211] [Preparation of Polarizing Filters 1-3] Using the aforementioned UV adhesive 1, the positive C-plate side of the positive C-plate FC-1 prepared above is bonded to the surface of the optical film F1-3 of the laminate F1-3, and irradiated from the positive C-plate FC-1 side with 1000 mJ / cm². 2 Ultraviolet light is used to cure the UV adhesive, thereby obtaining a laminate. Next, the orientation film and cellulose acylate film A1 on the F1-3 side of the laminate are removed, thereby obtaining a laminate FI1-3 with an optical film. Using pressure-sensitive adhesive SK-2057 (manufactured by Soken Chemical & Engineering Co., Ltd.), the polarizer 1 with protective film prepared above is attached to the optical film F1-3 side of the above-mentioned laminate with optical film FI1-3. The alignment film and cellulose acylate film A1 on the positive C plate FC-1 side are removed, thereby completing the polarizer 1-3. At this time, the angle between the absorption axis of the polarizer included in the polarizer 1 with protective film attached and the slow axis of the optical film F1-3 is 45°.

[0212] [Fabrication of polarizers 1-2, 1-4 to 1-6 and 2-3] The aforementioned laminate F1-3 is replaced by laminates F1-2, F1-4 to F1-6, or F2-3. Otherwise, polarizers 1-2, 1-4 to F1-5, and 2-3 are manufactured using the same method as polarizer 1-3. Polarizers can be manufactured in any case. When using laminates F1-1, F2-1, or F2-2 to replace the aforementioned laminate F1-3, the UV adhesive 1 does not adhere tightly to the aforementioned optical film, making it impossible to fabricate a polarizer.

[0213] [Fabrication of image display device 1] The Samsung Galaxy S4, equipped with an organic EL panel (organic EL display element), was disassembled. The touch panel with a polarizer was peeled off from the organic EL display device, and then the polarizer was peeled off from the touch panel, thus separating the organic EL display element, touch panel, and polarizer. Next, the separated touch panel was re-attached to the organic EL display element. Furthermore, the aforementioned polarizers 1-3 were bonded to the touch panel with the optical anisotropic layer side becoming the panel side using adhesive SK-2057 (manufactured by Soken Chemical & Engineering Co., Ltd.), thereby fabricating the organic EL display device 1.

[0214] [Determination of membrane properties] [Water contact angle] For the surfaces of the optical films produced (specifically, in Examples 1-6 and Comparative Example 3, the surfaces subjected to corona treatment or plasma treatment), the water contact angle was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., DMo-702, temperature 25°C, humidity 50%, standby time 20 seconds).

[0215] [XPS measurement of membrane surface] For the surfaces of each optical film fabricated (specifically, in Examples 1-6 and Comparative Example 3, surfaces subjected to corona treatment or plasma treatment), XPS measurements were performed using the method described above to obtain the presence ratio of silicon atoms on the film surface and the peak binding energy of the Si2p photoelectron spectrum. Furthermore, for the obtained Si2p photoelectron spectrum, peak separation was performed using the method described above, and the area ratio of each peak was calculated.

[0216] [Surface elastic modulus and surface adsorption force] For the surfaces of each optical film produced (specifically, in Examples 1-6 and Comparative Example 3, the surfaces subjected to corona treatment or plasma treatment), the surface elastic modulus and surface adsorption force were calculated by fitting the load / displacement curves obtained under the following apparatus and conditions using the JKR contact mechanics model. ·Device: Bruker DimensionIcon • Probe: RTESA300 • Mode: QNM Maximum load: 100 NN • Indentation depth: <10nm

[0217] 〔evaluate〕 [Seamless] Eleven vertical and eleven horizontal cuts were made at 1mm intervals on each of the fabricated polarizers from the C-plate side to form a checkerboard pattern. Adhesive tape (polyester adhesive tape NO.31B, manufactured by Nitto Denko Corporation) was applied to the checkerboard pattern, and the tape was peeled off at an angle of approximately 60°. The number of peeled checkerboard patterns was counted, and the results were evaluated according to the following criteria. XPS confirmed that the peeling interface was the interface between the cured layer of UV adhesive 1 and the aforementioned optical film.

[0218] A: The number of chessboard squares stripped is less than 20. B: The number of chessboard squares stripped is more than 21 and less than 50. C: The number of chessboard squares stripped is more than 51 and less than 90. D: The number of peeled checkerboard patterns is more than 91, or the UV adhesive does not adhere tightly to the surface of the optical film, making it impossible to manufacture a polarizing film.

[0219] (result) The types of optical films and their corona treatment conditions are shown in Table 1 below, and the surface characteristics and evaluation results of each film are shown in Table 2 below. In the table below, the SA-1 (parts by mass) column indicates the amount (parts by mass) of leveling agent SA-1 contained in the liquid crystal composition used to form each optical film. In the table below, the peak (eV) column represents the binding energy of the peak in the photoelectron spectrum of Si2p.

[0220] [Table 1]

[0221] [Table 2]

[0222] As confirmed by the table above, the film of the present invention exhibits excellent adhesion to adjacent layers (e.g., adhesive layers).

[0223] The comparison of Examples 1 to 5 confirmed that when the surface elastic modulus is 4.0 GPa or above, the sealing performance is better, and when the surface elastic modulus is 5.1 GPa or above, the sealing performance is even better. The comparison of Examples 1 to 6 confirmed that when the surface adsorption force is 12.0 nN or more, the adhesion is better, and when the surface adsorption force is 20.0 nN or more, the adhesion is even better. The comparison of Examples 1 to 6 confirmed that when the binding energy of the peak in the Si2p photoelectron spectrum obtained by measuring the surface of the film by X-ray photoelectron spectroscopy is 102.5 eV or higher, the binding performance is better, and when it is 103.2 eV or higher, the binding performance is even better. The comparison of Examples 1 to 6 confirmed that in the photoelectron spectra of Si2p obtained by measuring the surface of the film by X-ray photoelectron spectroscopy, the adhesion is better when the peak area of ​​silicon atoms bonded to 4 oxygen atoms is 30% or more relative to the peak area of ​​the Si2p photoelectron spectrum, and the adhesion is further improved when it is 97% or more.

[0224] The results of applying TOF-SIMS to the surface of each optical film showed that (SiO2) was detected in the optical films of Examples 1 to 6. l Fragments with a molecular weight of (l=1 to 7) were detected. On the other hand, the aforementioned fragments were not detected in the optical films of Comparative Examples 1 to 3. That is, it was confirmed that silicon dioxide, which is not present in the liquid crystal composition, was generated in the film of the present invention. The results above also confirm that silicon atoms bonded to four oxygen atoms exist on the surface of the optical film (specifically, the surface subjected to corona treatment in Examples 1-5, and the surface subjected to plasma treatment in Example 6).

[0225] [Construction of Layered Body F3-1]

[0226] <Alkali saponification treatment of cellulose acylated membrane A1> After passing the cellulose acylated membrane A1 through a dielectric heating roller at 60°C to raise the membrane surface temperature to 40°C, an alkaline solution of the following composition is applied using a bar coater at a coating rate of 14 ml / m. 2 The coating was applied to the steel belt surface of the membrane, and the membrane was conveyed for 10 seconds under a steam-type far-infrared heater manufactured by NORITAKE CO., LIMITED, heated to 110°C. Then, a 3 ml / m² coating was similarly applied to the membrane using a bar coater. 2Pure water. Then, after repeating the water washing process three times using a spray coating machine and the water removal process using an air knife, the membrane was transported to a drying area at 70°C for 10 seconds to dry, thereby producing an alkali-saponified cellulose acylated membrane A1.

[0227] ―――――――――――――――――――――――――――――――― alkaline solution ―――――――――――――――――――――――――――――――― 4.7 parts by weight of potassium hydroxide 15.8 parts by weight of water 63.7 parts by weight of isopropanol Surfactant: C 14 H 29 O(CH2CH2O) 20 H 1.0 parts by weight 14.8 parts by weight of propylene glycol ――――――――――――――――――――――――――――――――

[0228] <Formation of Orientation Film Y1> On the alkali-saponified surface of the cellulose acylate film A1, an orientation film coating solution with the following composition was continuously coated using a #14 wire bar coater. The resulting coating was dried with warm air at 60°C for 60 seconds, and then dried with warm air at 100°C for 120 seconds, thereby forming the orientation film Y1.

[0229] ―――――――――――――――――――――――――――――――― Orientation film coating solution ―――――――――――――――――――――――――――――――― 10 parts by weight of the following polyvinyl alcohol 371 parts by weight of water 119 parts by weight of methanol Glutaraldehyde (crosslinking agent) 0.5 parts by weight Citrate ester (manufactured by SANKYO CHEMICAL Co., Ltd.) 0.175 parts by weight ――――――――――――――――――――――――――――――――

[0230] (Polyvinyl alcohol)

[0231] [Chemical Formula 30]

[0232] <Formation of optical film F3-1> The orientation film Y1 prepared above was continuously subjected to friction treatment. At this time, the length direction of the elongated film was parallel to the conveying direction, and the angle between the length direction of the film (conveying direction) and the rotation axis of the friction roller was set to 76°. Setting the length direction of the film (conveying direction) to 90°, if viewed from the film side, a positive value is represented by a clockwise rotation with the film width direction as the reference (0°), then the rotation axis of the friction roller is -14°. In other words, the position of the rotation axis of the friction roller is the position rotated 76° clockwise from the length direction of the film when viewed from the film side.

[0233] Using a casting coater, a liquid crystal composition F3-1 containing a disc-shaped liquid crystal compound with the following composition was coated onto the alignment film Y1 after the above-mentioned friction treatment to form a composition layer. Then, to dry the solvent and ripen the alignment of the disc-shaped liquid crystal compound, the obtained composition layer was heated with warm air at 80°C for 2 minutes. Next, the obtained composition layer was subjected to UV irradiation (500 mJ / cm²) at 80°C. 2 The orientation of the liquid crystal compound was fixed to form an optical film F3-1. Thus, a laminate F3-1 was obtained having a support (cellulose acylate film A1), an orientation film Y1, and an optical film F3-1 in sequence. The thickness of optical film F3-1 is 1.4 μm. Furthermore, the in-plane retardation at a wavelength of 550 nm is 168 nm. It was confirmed that the average tilt angle of the disk-shaped liquid crystal compound relative to the film surface is 90°, and it is perpendicularly aligned to the film surface. Moreover, the in-plane slow axis angle of optical film F3-1 is parallel to the rotation axis of the friction roller. If the width direction of the film is set to 0° (and the length direction is set to 90° counterclockwise and -90° clockwise), then when viewed from the side of optical film F3-1, the in-plane slow axis is -14°.

[0234] ―――――――――――――――――――――――――――――――― Liquid crystal composition F3-1 ―――――――――――――――――――――――――――――――― 80 parts by weight of the following disc-shaped liquid crystal compound DL-1 20 parts by weight of the following disc-shaped liquid crystal compound DL-2 Vertical orientation agent V-1 1.2 parts by weight The following leveling agent SA-2, 0.18 parts by weight Ethylene oxide modified trimethylolpropane triacrylate (V#360, manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.) 5 parts by weight Photopolymerization initiator S-1 4.0 parts by weight Defoamer B-1 2.0 parts by weight 200 parts by weight of methyl ethyl ketone ――――――――――――――――――――――――――――――――

[0235] DL-1, a disc-shaped liquid crystal compound

[0236] [Chemical Formula 31]

[0237] DL-2, a disc-shaped liquid crystal compound

[0238] [Chemical Formula 32]

[0239] Vertical Orientation Agent V-1

[0240] [Chemical Formula 33]

[0241] Leveling agent SA-2 (where a and b represent the content (mass%) of each repeating unit relative to all repeating units, a represents 70% mass, b represents 24% mass, and c represents 6% mass. Furthermore, the weight-average molecular weight is 18000.)

[0242] [Chemical Formula 34]

[0243] Photopolymerization initiator S-1

[0244] [Chemical Formula 35]

[0245] Defoamer B-1

[0246] [Chemical Formula 36]

[0247] [Construction of laminates F3-2 to F3-4] By subjecting the surface of the optical film F3-1 of the laminate F3-1 to corona treatment or plasma treatment under the conditions shown in Table 3 below, optical films F3-2 to F3-4 are formed, thereby fabricating the laminate F3-2 to F3-4.

[0248] [Construction of the F4-1 laminate] Using a casting coating machine, a liquid crystal composition F4-1C containing a rod-shaped liquid crystal compound with the following composition was coated onto the cellulose acylate film A1 to form a composition layer. Then, holding both ends of the film, a cooling plate (9°C) was placed on the side of the film where the composition layer was formed, with a distance of 5 mm between the cooling plate and the film, and a heater (75°C) was placed on the opposite side of the film where the composition layer was formed, with a distance of 5 mm between the heater and the film, and the film was dried for 2 minutes. Next, the atmosphere was heated for 1 minute under 60°C warm air, while nitrogen purging was performed to bring the oxygen concentration down to below 100 ppm, and the atmosphere was irradiated with a 365nm UV-LED at an irradiation dose of 100 mJ / cm². 2 The ultraviolet light was then used to anneal the film at 120°C for 1 minute with warm air, thus forming the optical film F4-1C. At room temperature, the obtained optical film F4-1C was irradiated with UV light (ultra-high pressure mercury lamp; UL750; manufactured by HOYA) passing through a wire grid polarizer, producing a light intensity of 7.9 mJ / cm². 2 (Wavelength: 313nm), thus giving the surface the ability to control orientation. Furthermore, the formed optical film F4-1C has a thickness of 0.7 μm. The in-plane retardation Re at 550 nm is 0 nm, and the thickness-direction retardation Rth at 550 nm is -68 nm. The average tilt angle of the long axis of the rod-shaped liquid crystal compound relative to the film surface is 90°, confirming a perpendicular orientation relative to the film surface.

[0249] ―――――――――――――――――――――――――――――――― Liquid crystal composition F4-1C ―――――――――――――――――――――――――――――――― ·83 parts by mass of the above liquid crystal compound LC-1 15 parts by weight of the above-mentioned liquid crystal compound LC-2 • 2 parts by mass of the above liquid crystal compound LC-3 • Polymerizable monomer (A-400, manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.) 4.2 parts by weight • 5.1 parts by weight of the above polymerization initiator PI-1 • 3.0 parts by weight of the following photoacid generator D-1 • 2.0 parts by weight of the following polymer M-1 • 1.9 parts by weight of the following vertical orientation agent V-2 • 0.8 parts by weight of the following photo-oriented polymer P-1 0.2 parts by weight of diisopropylethylamine 23.5 parts by weight of methyl ethyl ketone 70.4 parts by weight of ethyl propionate · 375.0 parts by weight of methyl isobutyl ketone ――――――――――――――――――――――――――――――――

[0250] Photoacid generator D-1

[0251] [Chemical Formula 37]

[0252] Polymer M-1 (the values ​​in each repeating unit represent the content (mass%) relative to all repeating units. The weight-average molecular weight is 60,000.)

[0253] [Chemical Formula 38]

[0254] Vertical Orientation Agent V-2

[0255] [Chemical Formula 39]

[0256] Photooriented polymer P-1 (The values ​​listed in the repeating units indicate the content (mass%) of each repeating unit relative to all repeating units. Weight-average molecular weight: 90,000. Me indicates methyl.)

[0257] [Chemical Formula 40]

[0258] Next, using a casting coater, a liquid crystal composition F4-1A with the following composition was coated onto the optical film F4-1C prepared above, and heated with warm air at 80°C for 60 seconds. Then, the obtained composition layer was subjected to UV irradiation (500 mJ / cm²) at 80°C. 2 The orientation of the liquid crystal compound was fixed to form an optical film F4-1A, thereby obtaining a laminate F4-1. The optical film F4-1A has a thickness of 1.5 μm, a Δnd of 164 nm at a wavelength of 550 nm, and a twist angle of 81° for the liquid crystal compound. If the width direction of the film is set to 0° (and the length direction to 90°), then when viewed from the side of the optical film F4-1A, the position of the in-plane slow axis (the orientation axis angle of the liquid crystal compound) of the optical film F4-1A is 14° on the air side and 95° on the side in contact with the optical film F4-1C. In addition, regarding the position of the in-plane slow axis of the optical film, the width direction of the film is set as the reference 0°. When observing the substrate from the surface side of the optical film, clockwise (right turn) is indicated as negative, and counterclockwise (left turn) is indicated as positive. Furthermore, regarding the twist angle of the liquid crystal compound, when observing the substrate from the surface side of the optical film, with the orientation axis direction of the liquid crystal compound on the surface side (front side) as a reference, the orientation axis direction of the liquid crystal compound on the substrate side (inner side) is negative when it is clockwise (right turn) and positive when it is counterclockwise (left turn).

[0259] ―――――――――――――――――――――――――――――――― Liquid crystal composition F4-1A ―――――――――――――――――――――――――――――――― · 58.1 parts by mass of the above-mentioned liquid crystal compound LC-1 10.5 parts by weight of the above-mentioned liquid crystal compound LC-2 • 1.4 parts by weight of the above-mentioned liquid crystal compound LC-3 • 30.0 parts by weight of the following rod-shaped liquid crystal compound LC-4 Ethylene oxide modified trimethylolpropane triacrylate (V#360, manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.) 4.0 parts by weight • Photopolymerization initiator (Irgacure 819, manufactured by BASF) 3.0 parts by weight • 0.48 parts by weight of the following chiral agent C-1 • 0.15 parts by weight of the above leveling agent SA-1 0.70 parts by weight of diisopropylethylamine 126.5 parts by weight of ethyl propionate 126.5 parts by weight of methyl isobutyl ketone ――――――――――――――――――――――――――――――――

[0260] Rod-shaped liquid crystal compound LC-4

[0261] [Chemical Formula 41]

[0262] Chiral agent C-1 (Bu represents butyl).

[0263] [Chemical Formula 42]

[0264] Through the above steps, a laminate F4-1 was prepared, in which optical films F4-1C and F4-1A are directly stacked on a strip-shaped cellulose acylate membrane.

[0265] [Construction of laminates F4-2 to F4-4] The surface of the optical film F4-1A of the laminate F4-1 was subjected to corona treatment or plasma treatment under the conditions shown in Table 3 below to form optical films F4-2A to F4-4A, thereby fabricating the laminate F4-2 to F4-4.

[0266] [Preparation of Polarizing Filter 3-2] Using the aforementioned UV adhesive 1, the surface of the optical film F4-2A of the laminate F4-2 is bonded to the surface of the optical film F3-2 of the laminate F3-2, and irradiated from the laminate F4-2 side with 1000 mJ / cm². 2 Ultraviolet light is used to cure the UV adhesive, thereby obtaining a laminate. Next, the cellulose acylate film A1 on the F4-2 side of the laminate is removed, thereby obtaining a laminate with an optical film FI3-2. Using pressure-sensitive adhesive SK-2057 (manufactured by Soken Chemical & Engineering Co., Ltd.), the polarizer 1 with protective film prepared above is attached to the optical film F4-2 side of the above-mentioned laminate with optical film FI3-2, and the orientation film and cellulose acylate film A1 on the F3-2 side of the laminate are removed, thereby completing the polarizer 3-2.

[0267] [Preparation of polarizers 3-3 to 3-4] Polarizer 3-3 is fabricated using the same method as polarizer 3-2, except that laminate F3-3 is used instead of laminate F3-2 and laminate F4-3 is used instead of laminate F4-2. Similarly, polarizer 3-4 is fabricated using the same method as polarizer 3-2, except that laminate F3-4 is used instead of laminate F3-2 and laminate F4-4 is used instead of laminate F4-2. Polarizer 3-4 can be fabricated in any case. When the above-mentioned laminate F3-1 is used instead of the above-mentioned laminate F3-2, and the above-mentioned laminate F4-1 is used instead of the above-mentioned laminate F4-2, the UV adhesive 1 is not tightly bonded to the above-mentioned optical film, and a polarizer cannot be made.

[0268] [Determination of membrane properties] The characteristics of each optical film surface were measured using the same procedures as in Examples 1-6 and Comparative Examples 1-3.

[0269] 〔evaluate〕 [Seamless] Eleven longitudinal and transverse cuts were made at 1mm intervals from the F3-2 to F3-4 sides of the optical films of each of the polarizers 3-2 to 3-4, forming 100 checkerboard patterns. Adhesive tape (polyester adhesive tape NO.31B, manufactured by NittoDenko Corporation) was applied to the checkerboard patterns, and the tape was peeled off at an angle of approximately 60°. The number of peeled checkerboard patterns was counted, and the results were evaluated according to the following criteria. XPS confirmed that the peeling interface was either the interface between the cured layer of UV adhesive 1 and the aforementioned optical films F3-2 to F3-4, or the interface between the cured layer of UV adhesive 1 and the aforementioned optical films F4-2A to F4-4A.

[0270] A: The number of chessboard squares stripped is less than 20. B: The number of chessboard squares stripped is more than 21 and less than 50. C: The number of chessboard squares stripped is more than 51 and less than 90. D: The number of peeled checkerboard patterns is more than 91, or the UV adhesive does not adhere tightly to the surface of the optical film, making it impossible to manufacture a polarizing film.

[0271] (result) The types of optical films, along with the corona treatment and plasma treatment conditions, are shown in Table 3 below. The surface characteristics and evaluation results of each film are shown in Table 4 below. In addition, for optical films F3-2 to F3-4 and optical films F4-2 to F4-4, the surfaces that underwent corona treatment or plasma treatment were measured. In the table below, column SA-1 (parts by mass) shows the amount (parts by mass) of leveling agent SA-1 contained in the liquid crystal composition used to form each optical film, and column SA-2 (parts by mass) shows the amount (parts by mass) of leveling agent SA-2 contained in the liquid crystal composition used to form each optical film. In the table below, the peak (eV) column represents the binding energy of the peak in the photoelectron spectrum of Si2p.

[0272] [Table 3]

[0273] [Table 4]

[0274] The comparison of Examples 7-9 and Comparative Example 4 above also confirms that the film of the present invention has excellent adhesion to adjacent layers (e.g., adhesive layer). Symbol Explanation

[0275] 10-Laminated body, 12-Liquid crystal layer, 14-Orientation film, 16-Support, 20-Polarizer, 22-Polarizer, 24-First sealing layer, 26-First liquid crystal layer, 28-Second sealing layer, 30-Second liquid crystal layer.

Claims

1. A film formed using a liquid crystal composition comprising a liquid crystal compound and a leveling agent containing silicon atoms, wherein, The Si2p photoelectron spectrum obtained by measuring the surface of the film using X-ray photoelectron spectroscopy shows that the binding energy at the peak is above 102.0 eV.

2. A film formed using a liquid crystal composition comprising a liquid crystal compound and a leveling agent containing silicon atoms, wherein, Silicon atoms bonded to four oxygen atoms are present on the surface of the membrane.

3. The membrane according to claim 2, wherein, In the photoelectron spectrum of Si2p obtained by measuring the surface of the film by X-ray photoelectron spectroscopy, the peak area attributable to silicon atoms bonded to four oxygen atoms is more than 30% relative to the peak area of ​​the photoelectron spectrum of Si2p.

4. The membrane according to claim 1 or 2, wherein, The surface elastic modulus of the membrane is above 4.0 GPa.

5. The membrane according to claim 1 or 2, wherein, The surface adsorption force of the membrane is above 12.0 nN.

6. A polarizer comprising a polarizer, an adhesive layer, and the film according to claim 1 or 2.

7. An image display device comprising the polarizer of claim 6.

8. The image display device according to claim 7, wherein it is an organic electroluminescent display device.

9. The image display device according to claim 7, wherein it is a liquid crystal display device.

Images