Film, polarizing plate, and image display device

Abstract

The present invention addresses the problem of providing a film that is formed using a liquid crystal composition containing a leveling agent having a silicon atom, and that has excellent adhesion to an adjacent layer. A film according to the present invention is formed using a liquid crystal composition containing a liquid crystal compound and a leveling agent containing a silicon atom. The binding energy of a peak top in an inner shell photoelectron spectrum of Si2p obtained by measuring the surface of the film by X-ray photoemission spectroscopy is at least 102.0 eV, or a silicon atom to which four oxygen atoms are bonded is present in the surface of the film.

Description

Films, polarizing plates, image display devices

[0001] The present invention relates to a film, a polarizing plate, and an image display device.

[0002] Optical films such as optical compensation sheets and retardation films are used in various image display devices to eliminate image coloration or widen the viewing angle. Stretched birefringent films have been used as optical films, but in recent years, it has been proposed to use optical films having an optically anisotropic layer made of a liquid crystal compound instead of stretched birefringent films.

[0003] An optically anisotropic layer made of a liquid crystal compound is often formed by applying a liquid crystal composition containing the liquid crystal compound to form a coating film, and then performing an alignment treatment on the coating film. A leveling agent may be added to the liquid crystal composition to improve the surface properties on the air interface side when the coating film is formed. For example, Patent Document 1 discloses a liquid crystal composition to which a fluorine-based leveling agent containing a fluorine atom has been added.

[0004] International Publication No. 2019 / 160044

[0005] Recently, due to their persistence and toxicity, etc., restrictions on PFAS (perfluoroalkyl compounds and polyfluoroalkyl compounds) have been implemented, and the use of substitutes that do not use fluorine atoms, typically substitute materials containing silicon atoms, has been studied. The present inventors have studied liquid crystal compositions using leveling agents containing silicon atoms, and have found that the adhesion between a film formed using the liquid crystal composition and a layer adjacent to the film (for example, an adhesive layer) does not meet the desired level and needs to be improved.

[0006] Therefore, an object of the present invention is to provide a film formed using a liquid crystal composition containing a leveling agent having a silicon atom, which film has excellent adhesion to adjacent layers, and a polarizing plate and an image display device related to the film.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0008] [1] A film formed using a liquid crystal composition containing a liquid crystal compound and a leveling agent containing a silicon atom, wherein the peak top binding energy in a Si2p photoelectron spectrum obtained by measuring the surface of the film by X-ray photoelectron spectroscopy is 102.0 eV or more. [2] A film formed using a liquid crystal composition containing a liquid crystal compound and a leveling agent containing a silicon atom, wherein a silicon atom to which four oxygen atoms are bonded is present on the surface of the film. [3] The film according to [2], wherein the peak area assigned to the silicon atom to which four oxygen atoms are bonded in a Si2p photoelectron spectrum obtained by measuring the surface of the film by X-ray photoelectron spectroscopy is 30% or more of the peak area in the Si2p photoelectron spectrum. [4] The film according to any one of [1] to [3], wherein the surface elastic modulus of the film is 4.0 GPa or more. [5] The film according to any one of [1] to [4], wherein the surface adsorption force of the film is 12.0 nN or more. [6] A polarizing plate comprising a polarizer, an adhesive layer, and the film according to any one of [1] to [5]. [7] An image display device comprising the polarizing plate according to [6]. [8] The image display device according to [7], which is an organic electroluminescence display device. [9] The image display device according to [7], which is a liquid crystal display device.

[0009] According to the present invention, it is possible to provide a film having excellent adhesion to adjacent layers, and also to provide a polarizing plate and an image display device relating to the film.

[0010] Fig. 1 is a schematic cross-sectional view showing an example of a laminate including the film of the present invention, and Fig. 2 is a schematic cross-sectional view showing an example of a polarizing plate including the film of the present invention.

[0011] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0012] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. Furthermore, in this specification, when two or more types of a certain component are present, the "content" of that component means the total content of those two or more components. In this specification, in a numerical range described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in a numerical range described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the Examples. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0013] In this specification, the bonding direction of a divalent group (for example, -CO-O-) is not limited unless otherwise specified. For example, when Y is -CO-O- in a compound represented by the formula "X-Y-Z," the compound may be "X-O-CO-Z" or "X-CO-O-Z." In this specification, "(meth)acrylic" is a concept that includes both acrylic and methacrylic, "(meth)acryloyl" is a concept that includes both acryloyl and methacryloyl, "(meth)acrylate" is a concept that includes both acrylate and methacrylate, and "(meth)acrylonitrile" is a concept that includes both acrylonitrile and methacrylonitrile.

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

[0015] In this specification, Re(λ) and Rth(λ) represent the in-plane retardation and the thickness direction retardation, respectively, at a wavelength λ. Unless otherwise specified, the wavelength λ is 550 nm. In this specification, Re(λ) and Rth(λ) are values ​​measured at a wavelength λ using an AxoScan OPMF-1 (manufactured by Optoscience). Specifically, by inputting the average refractive index ((nx + ny + nz) / 3) and the film thickness (d (μm)) into the AxoScan OPMF-1, the following slow axis direction (°) is calculated: Re(λ) = R0(λ) Rth(λ) = ((nx + ny) / 2 - nz) × d. Although R0(λ) is displayed as a numerical value calculated by the AxoScan OPMF-1, it means Re(λ).

[0016] In this specification, the angular relationship (e.g., "perpendicular," "parallel," etc.) is intended to include the range of error acceptable in the technical field to which the present invention pertains. Specifically, this means that the angle is within a range of less than ±10° from the exact angle, and the error from the exact angle is preferably within a range of ±5° or less, and more preferably within a range of ±3° or less.

[0017] In this specification, the term "solid content" refers to components that form a film and does not include solvents. Any component that forms a film is considered to be a solid content even if it is in a liquid state.

[0018] [Film] The film of the present invention will be described in detail below. A film of a first aspect of the present invention is a film formed using a liquid crystal composition containing a liquid crystal compound and a leveling agent containing silicon atoms, and in the Si2p photoelectron spectrum obtained by measuring the surface of the film by X-ray photoelectron spectroscopy, the peak top binding energy is 102.0 eV or more. A film of a second aspect of the present invention is a film formed using a liquid crystal composition containing a liquid crystal compound and a leveling agent containing silicon atoms, and in the surface, silicon atoms to which four oxygen atoms are bonded are present. In this specification, when simply referring to "the film of the present invention," this concept includes both the film of the first aspect and the film of the second aspect.

[0019] Although the reason why a film having the above-described configuration can solve the problems of the present invention is not entirely clear, the present inventors speculate as follows. Note that the following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than the one described below, it is still within the scope of the present invention. In the film of the first aspect of the present invention, the bond energy of the peak top of the Si2p photoelectron spectrum is equal to or greater than a predetermined value on the surface. In such cases, it is believed that a high proportion of silicon atoms contained in the film have Si—O bonds, which have higher bond energy than Si—C bonds and the like. It is believed that the more Si—O bonds there are, the stronger the film surface is, and breakage is suppressed, and the surface adsorption force, polarity, etc. are improved, resulting in excellent adhesion to adjacent layers. In the film of the second aspect of the present invention, silicon atoms bonded to four oxygen atoms are present on the surface. Silicon atoms bonded to four oxygen atoms, namely, silicon dioxide (SiO ２ ) state. It is presumed that the inclusion of silicon dioxide increases the strength of the film surface, suppresses breakage, improves surface adsorption force and polarity, and as a result, provides excellent adhesion to adjacent layers. Hereinafter, the film of the present invention having better adhesion to adjacent layers will also be simply referred to as having "better effects of the present invention."

[0020] The liquid crystal composition used to form the film of the present invention, the method for producing the film, and the properties of the film will be described below in this order.

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

[0022] <Liquid Crystal Compound> 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 discotic types based on their shape. Each type is further divided into low-molecular-weight and high-molecular-weight types. High-molecular-weight compounds generally refer to those with a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, by Masao Doi, page 2, Iwanami Shoten, 1992). In the present invention, any liquid crystal compound can be used, but rod-shaped or discotic liquid crystal compounds (discotic liquid crystal compounds) are preferably used. Two or more rod-shaped liquid crystal compounds, two or more discotic liquid crystal compounds, or a mixture of a rod-shaped liquid crystal compound and a discotic liquid crystal compound may also be used.

[0023] The liquid crystal compound contained in the liquid crystal composition may be either a low molecular weight liquid crystal compound or a polymer liquid crystal compound, or a mixture thereof. From the viewpoint of alignment, the liquid crystal compound is preferably a polymerizable liquid crystal compound. A polymerizable liquid crystal compound is a liquid crystal compound having a polymerizable group, and the alignment state can be fixed by polymerization after alignment. Furthermore, the alignment state of a polymer liquid crystal compound can be fixed by removing the solvent from the liquid crystal composition and drying it after alignment.

[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 discotic liquid crystal compounds. The polymerizable group of the polymerizable liquid crystal compound is not particularly limited, but a polymerizable group capable of radical polymerization or cationic polymerization is preferred. Examples of the polymerizable group include an acryloyl group, a methacryloyl group, an epoxy group, and a vinyl group.

[0025] As the rod-shaped liquid crystal compound, those described in claim 1 of JP-A-11-513019 or paragraphs

[0026] to

[0098] of JP-A-2005-289980 are preferred, and as the discotic liquid crystal compound, those described in paragraphs

[0020] to

[0067] of JP-A-2007-108732 or paragraphs

[0013] to

[0108] of JP-A-2010-244038 are preferred.

[0026] The liquid crystal compound may be a liquid crystal compound having reverse wavelength dispersion (reverse dispersion compound). In this specification, the term "reverse wavelength dispersion" refers to a liquid crystal compound that, when the in-plane retardation (Re) value of a film produced using the compound is measured at a specific wavelength (visible light range), exhibits a constant or higher Re value as the measured wavelength increases. The liquid crystal compound of reverse wavelength dispersion is not particularly limited as long as it can form a layer of reverse wavelength dispersion, for example, the general formula (I) described in JP-A-2008-297210 compounds (particularly, the compounds described in paragraphs

[0034] to

[0039] ), the general formula (1) described in JP-A-2010-084032 compounds (particularly, the compounds described in paragraphs

[0067] to

[0073] ), the general formula (1) described in JP-A-2016-081035 compounds (particularly, the compounds described in paragraphs

[0043] to

[0055] ), and the general formula (II) described in JP-A-2016-053709 compounds (particularly, the compounds described in paragraphs

[0036] to

[0043] ). Further, paragraphs

[0027] to

[0100] of JP 2011-006360 A, paragraphs

[0028] to

[0125] of JP 2011-006361 A, paragraphs

[0034] to

[0298] of JP 2012-207765 A, paragraphs

[0016] to

[0345] of JP 2012-077055 A, Examples include the compounds described in paragraphs

[0017] to

[0072] of International Publication No. 41245, 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] The liquid crystal compound may be used alone or in combination of two or more. The content of the liquid crystal compound is preferably 50 to 99.99 mass %, more preferably 70 to 99 mass %, based on the total solid content of the liquid crystal composition.

[0028] <Leveling Agent Containing Silicon Atom> The liquid crystal composition contains a leveling agent containing a silicon atom (specific leveling agent). The structure of the specific leveling agent is not limited as long as it contains a silicon atom, but it is preferably a polymer having a repeating unit containing a silicon atom (repeating unit A).

[0029] (Repeating Unit A) The repeating unit A is a repeating unit containing a silicon atom. 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 a silicon atom in the form of a structure represented by the following formula (Ia).

[0031]

[0032] In formula (Ia), * represents the bonding position. １１ , R １２ , and R １３ each independently represents an alkyl group, alkenyl group, aryl group, or alkylenearyl group, which may have a substituent. The substituent is preferably a halogen atom, an alkyl group, an alkenyl group, an alkylcarbonyl group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, or an alkoxy group. Examples of the alkyl group include a linear alkyl group having 1 to 18 carbon atoms, and a branched or cyclic alkyl group having 3 to 18 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, and a cyclohexyl group. Examples of the alkenyl group include an alkenyl group having 2 to 12 carbon atoms. Examples of the aryl group include an aryl group having 6 to 12 carbon atoms. Examples of the alkylenearyl group include an alkylenearyl group having 7 to 30 carbon atoms. R is preferred in terms of superior leveling properties. １１ , R １２ , and R １３ are preferably all alkyl groups.

[0033] In terms of achieving better effects of the present invention, the repeating unit A preferably contains two or more structures represented by formula (Ia), more preferably contains 3 to 6 structures, and even more preferably contains 3 to 5 structures.

[0034] In terms of achieving better effects of the present invention, it is preferable that the structure represented by the formula (Ia) is bonded to a carbon atom or an oxygen atom. In other words, the repeating unit A is preferably a structure represented by -OA or -CR Ａ ２ It is preferable that the compound has a structure represented by formula (Ia)-A, where A represents a structure represented by formula (Ia). Ａ R each independently represents a hydrogen atom or a substituent. Ａ may be a structure represented by the above formula (Ia).

[0035] The repeating unit A is preferably a repeating unit represented by the following formula (a1), in that it has better leveling properties and compatibility with the liquid crystal compound.

[0036]

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

[0038] In formula (a1), R １１ , R １２ , and R １３ represents R in formula (Ia). １１ , R １２ , and R １３ It is the same as the case where there are multiple R １１ may be the same or different, and there may be multiple R １２ may be the same or different, and there may be multiple R １３ may be the same or different.

[0039] In formula (a1), R ２１ and R ２２R each independently represents a hydrogen atom or an alkyl group. Examples of the alkyl group include a linear alkyl group having 1 to 18 carbon atoms and a branched or cyclic alkyl group having 3 to 18 carbon atoms. ２１ and R ２２ is preferably a hydrogen atom.

[0040] In formula (a1), R ２３ represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an aryl group, or a substituent having a linking group and a group containing a silicon atom. Examples of the substituent having a linking group and a group containing a silicon atom include -CH ２ -CO-L １ -L ２ -(Si(R １１ ) (R １２ ) (R １３ )) ｍ Also included. １ , L ２ , R １１ , R １２ , R １３ , and m are defined as the same as the symbols in formula (a1). ２３ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms, still more 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 is —O— or —NR Ｚ - represents. Ｚ represents a hydrogen atom or a substituent. Ｚ Examples of the substituent represented by the formula: ２３ Examples of the substituent represented by the formula (I) include the groups exemplified above, and an alkyl group is preferred, a linear alkyl group having 1 to 4 carbon atoms is more preferred, and a methyl group or an ethyl group is even more preferred. １ As the group, —O— or —NH— is preferable, and —O— is more preferable.

[0042] In formula (a1), L ２represents an (m+1)-valent linking group. Suitable examples of the (m+1)-valent linking group include hydrocarbon groups having 1 to 10 carbon atoms which may have a substituent, in which some of the carbon atoms constituting the hydrocarbon group may be substituted with heteroatoms. The substituent that the hydrocarbon group may have is preferably an alkyl group, more preferably a linear alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group or an ethyl group. Examples of the heteroatom that may substitute some of the carbon atoms include a silicon atom, an oxygen atom, and a nitrogen atom. L ２ Examples of the group include a group represented by the following structural formula K-1-L, a group represented by the structural formula K-2-L, and a group represented by the structural formula K-3-L. In the sub-structural formulas, * represents L in formula (a1). １ represents the bonding position with -SiR in formula (a1), and ** represents -SiR １１ R １２ R １３ represents the bonding position with the group represented by ２ is an alkylene group -O-(SiR １４ ２ -O) ｎｌ The alkylene group may be a linear alkylene group having 1 to 4 carbon atoms. １４ The definition and preferred embodiments of R １１ , R １２ , and R １３ nl is the same as the group represented by the formula (I), and is preferably an alkyl group, more preferably a methyl group or an ethyl group. nl represents an integer of 1 or more, preferably an integer of 1 to 80, more preferably an integer of 1 to 16. ２ No-SiR １１ R １２ R １３ The atom bonded to the group represented by the formula (I) is preferably a carbon atom or an oxygen atom, and more preferably an oxygen atom. ２ As the alkyl group, a group represented by the structural formula K-1-L is preferred in that the effects of the present invention are more excellent.

[0043]

[0044] Specific examples of the repeating unit A include repeating units derived from the monomers represented by the following K-1 to K-33, where nBu represents an n-butyl group.

[0045]

[0046]

[0047] The repeating unit A may be used alone or in combination of two or more. The content of the 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, based on all repeating units (100% by mass) constituting the main chain of the specific leveling agent. The upper limit of the content of the repeating unit A may be 100% by mass, based on all repeating units (100% by mass) constituting the main chain of the specific leveling agent, but is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0048] The specific leveling agent may have a repeating unit other than the repeating unit A. From the viewpoint of controlling the alignment of the liquid crystal compound as described above, the specific leveling agent also preferably has a repeating unit containing a mesogen group (repeating unit B). From the viewpoint of better adhesion to adjacent layers, the specific leveling agent also preferably has a repeating unit containing a polymerizable group (repeating unit C). From the viewpoint of compatibility, the specific leveling agent also preferably contains a repeating unit having a poly(alkyleneoxy) group. Details of the poly(alkyleneoxy) group will be described later. The specific leveling agent preferably contains the repeating unit A and at least one repeating unit selected from the repeating unit B and the repeating unit C, and more preferably contains the repeating unit A, the repeating unit B, and the repeating unit C.

[0049] (Repeating Unit B) The repeating unit B is a repeating unit containing a mesogen group. Known mesogen groups can be used as the mesogen group. For example, see "Flussige Kristalle in Tabellen II" (VEB Deutsche Verlag fur Grundstoff Industrie, Leipzig, published in 1984), particularly pages 7 to 16, and "Liquid Crystal Handbook" edited by the Liquid Crystal Handbook Editorial Committee (Maruzen, published in 2000), particularly Chapter 3. The mesogen group is preferably a group having at least one cyclic structure selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group, and an alicyclic group. For reasons of improving the degree of alignment of the liquid crystal compound, the mesogen group is preferably a group having an aromatic hydrocarbon group or an alicyclic group, which may have a substituent; more preferably a group having two to four aromatic hydrocarbon groups, which may have a substituent; and even more preferably a group having three aromatic hydrocarbon groups, which may have a substituent. The substituent is preferably an alkyl group, an alkoxy group, an alkyl ester group, or an acetyl group, and more preferably a methyl group, a tert-butyl group, a methoxy group, or a methyl ester group.

[0050] The mesogenic group is preferably a group represented by the following formula (M1-A): １１ -L １１ ) ｎ -Cy １２ - * (M1-A)

[0051] In formula (M1-A), * represents a bonding position.

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

[0053] In formula (M1-A), Cy １１ and Cy １２ each independently represents a divalent cyclic group which may have a substituent. The divalent cyclic group may be either a monocyclic or polycyclic group, and is preferably a monocyclic group. The number of ring members in the divalent cyclic group is preferably 5 to 18, more preferably 5 to 10, and even more preferably 5 or 6.

[0054] Examples of the divalent ring group include a divalent aromatic ring group and a divalent alicyclic group. Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group obtained by removing two hydrogen atoms from an aromatic hydrocarbon ring, and a divalent aromatic heterocyclic group obtained by removing two hydrogen atoms from an aromatic heterocyclic ring. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Examples of the aromatic heterocyclic ring include a pyridine ring, a pyridazine ring, an imidazole ring, a thiophene ring, a quinoline ring, an isoquinolylene ring, a phenanthroline ring, an oxazole ring, a thiazole ring, an oxadiazole ring, a benzothiazole ring, a benzothiadiazole ring, a phthalimide ring, a thienothiazole ring, a thiazolothiazole ring, a thienothiophene ring, and a thienoxazole ring. Among these, a group obtained by removing two hydrogen atoms from a benzene ring (for example, a 1,4-phenylene group) is preferred. Examples of the divalent alicyclic group include a divalent aliphatic hydrocarbon ring group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring (e.g., a cycloalkane or a cycloalkene), and a divalent aliphatic heterocyclic group obtained by removing two hydrogen atoms from an aliphatic heterocyclic ring. Examples of the aliphatic hydrocarbon ring include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclododecane ring, and a cyclodocosane ring. Examples of the aliphatic heterocyclic group include a pyrrolidine ring, an oxolane ring, a thiolane ring, a piperidine ring, a tetrahydropyran ring, a thiane ring, a piperazine ring, and a morpholine ring. Among these, a group obtained by removing a divalent hydrogen atom from a cyclohexane ring (e.g., a 1,4-cyclohexylene group) is preferred. Examples of the divalent ring group include a divalent aromatic ring group or a divalent aliphatic hydrocarbon ring group, and a divalent aromatic ring group is more preferred.

[0055] Examples of the substituent that the divalent cyclic group may have include an alkyl ester group, an alkyl group which may have a halogen atom, an acyl group, an alkoxy group, an alkylthio group, an alkyloxycarbonyl group, a carbamoyl group, an acylamino group, a halogen atom, a cyano group, and a nitro group. An alkyl ester group, an alkyl group, or an acyl group is preferred, a methyl ester group, a linear alkyl group having 1 to 4 carbon atoms, or an acetyl group is more preferred, and a methyl ester group, a methyl group, or an ethyl group is even more preferred.

[0056] In formula (M1-A), L １１ each independently represents a single bond or a divalent linking group. Examples of the divalent linking group include -CO-, -O-, -S-, -C(=S)-, and -CR Ｌ１ R Ｌ２ -, -CR Ｌ３ =CR Ｌ４ - and -NR Ｌ５ -, and combinations of two or more thereof. Ｌ１ ~R Ｌ５ R each independently represents a hydrogen atom or a substituent. Ｌ１ ~R Ｌ５ The substituent represented by is preferably a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. １１ Examples thereof include —CO—, —O—, and —CR Ｌ１ R Ｌ２ -, -NR Ｌ５ - or a combination of the two is preferred.

[0057] n is an integer of 2 or more, and Cy １１ represents a phenylene group, in order to improve the alignment property when the liquid crystal compound is to be horizontally aligned, two or more Cy １１ Preferably, any one of the above is a meta-position linkage or an ortho-position linkage, and among these, from the viewpoint of improving alignment and repelling, a meta-position linkage is preferred. On the other hand, when a liquid crystal compound is to be vertically aligned, two or more Cy １１ Preferably, any one of the above is a para-linkage.

[0058] The repeating unit B is preferably a repeating unit represented by the following formula (b1) or a repeating unit represented by the following formula (b2), and more preferably a repeating unit represented by the following formula (b1), in terms of improving compatibility with the liquid crystal compound and providing more excellent leveling properties.

[0059]

[0060] In formulas (b1) and (b2), R ２１ , R ２２ , R ２３ , and L １ is the same as that explained in the above formula (a1). In the above formula (b2), R ２４ and R ２５ are each independently R in the above formula (a1). ２１ and R ２２ The definition and preferred embodiments are the same as those of R. ２６ is R in the above formula (a1). ２３ The definition and preferred embodiments are the same as those of the above. ２ is L in the above formula (a1). １ The definitions are the same as those of the above, and preferred embodiments are also the same.

[0061] In formulas (b1) and (b2), SP １ and SP ２ each independently represents a spacer group. The spacer group is not particularly limited as long as it is a divalent linking group that does not contain a ring structure, and examples thereof include divalent chain aliphatic hydrocarbon groups having 1 to 20 carbon atoms. As the 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. Specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a methylhexylene group, and a heptylene group. The —CH group constituting the divalent chain aliphatic hydrocarbon group is ２ One or more of the - may be independently substituted with a group selected from -O-, -S-, -CO-, and -N(Q)-. ２- may be substituted. Q represents a hydrogen atom or a substituent. The substituent represented by Q is preferably an alkyl group, more preferably a linear alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group or an ethyl group. Among others, the spacer group is preferably *-(CH ２ -CH ２ -O) ｎ１ -*, *-(CH ２ ) ｎ２ -O-*, or *-(CH ２ ) ｎ２ -O-CO-* is preferred. * represents the bonding position. n1 represents an integer of 1 to 4. n2 each independently represents an integer of 1 to 6, preferably an integer of 2 to 4.

[0062] In formula (b1) and formula (b2), M １ represents a mesogenic group. Details of the mesogenic group are as described above.

[0063] In formula (b2), T １ represents a terminal group. The terminal group represents a hydrogen atom or a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkoxycarbonyloxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms (ROC(O)-: R is an alkyl group), an acyloxy group having 1 to 10 carbon atoms, an acylamino group having 1 to 10 carbon atoms, an alkoxycarbonylamino group having 1 to 10 carbon atoms, a sulfonylamino group having 1 to 10 carbon atoms, a sulfamoyl group having 1 to 10 carbon atoms, a carbamoyl group having 1 to 10 carbon atoms, a sulfinyl group having 1 to 10 carbon atoms, a trialkylsilyloxy group having 3 to 12 carbon atoms, and a ureido group having 1 to 10 carbon atoms.

[0064] Specific examples of the repeating unit B include repeating units derived from the monomers represented by Q-1 to Q-32 below.

[0065]

[0066]

[0067] The repeating unit B may be used singly or in combination of two or more types. The content of the repeating unit B is preferably 5 to 60 mass %, more preferably 10 to 50 mass %, and even more preferably 15 to 45 mass %, based on the total repeating units (100 mass %) constituting the main chain of the specific leveling agent.

[0068] (Repeating Unit C) The repeating unit C is a repeating unit containing a reactive group. Examples of the reactive group include a radically polymerizable group or a cationically polymerizable group, with a radically polymerizable group being preferred. Examples of the reactive group include a functional group capable of forming a covalent complex with a hydroxyl group. As the radically polymerizable group, known radically polymerizable groups can be used, such as a vinyl group, an allyl group, a vinyloxy group, a maleimide group, an allyloxy group, a (meth)acryloyl group, a (meth)acryloyloxy group, and a (meth)acrylamide group. Of these, a (meth)acryloyl group or a (meth)acryloyloxy group is preferred. As the cationically polymerizable group, known cationically polymerizable groups can be used, such as an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, and a vinyloxy group. Of these, an alicyclic ether group or a vinyloxy group is preferred, with an epoxy group, an oxetanyl group, or a vinyloxy group being more preferred. The functional group capable of forming a covalent complex with a hydroxyl group is a boronic acid group (-B(OH) ２ ) and a boronic ester group (—B(OR Ｂ１ ) ２ ) group is preferred. Ｂ１R each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and a hydrogen atom or an alkyl group which may have a substituent is preferred. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. The aryl group preferably has 4 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. An example of an aryl group is a phenyl group. The heteroaryl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms. Examples of heteroatoms contained in the heteroaryl group include an oxygen atom, a nitrogen atom, and a sulfur atom. Ｂ１ R may be bonded to each other to form a ring. Ｂ１ The number of members in the ring formed by bonding together is preferably 4 to 8, and more preferably 5 to 6.

[0069] The number of reactive groups contained in the repeating unit C is 1 or more, preferably 1 to 3, and more preferably 1 or 2.

[0070] The repeating unit C is preferably a repeating unit represented by the following formula (c1) in that it has better compatibility with the liquid crystal compound.

[0071]

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

[0073] In formula (c1), L ３ represents a single bond or a divalent linking group. Examples of the divalent linking group include divalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms which may have a substituent. The aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms. The -CH constituting the divalent aliphatic hydrocarbon group ２One or more of the - may be independently substituted with a group selected from -O-, -S-, -CO-, and -N(Q)-. ２ - may be substituted. The definition and preferred embodiments of Q are as described above. ３ Among them, alkylene groups having 2 to 8 carbon atoms which may have a substituent, or *-(L ３１ -O) ｎ３ - * is preferred. * represents the bonding position. n3 represents an integer of 1 to 8. L ３１ each independently represents an alkylene group having 1 to 6 carbon atoms which may have a substituent, and preferably an alkylene group having 2 to 4 carbon atoms which may have a substituent. ３ The divalent linking group represented by the formula (I) may be a group containing a mesogen group. Examples of the group containing a mesogen group include *-SP １ -M １ - * is preferred. * indicates the bonding position. SP １ and M １ is the same as that explained in the above formula (b1). When a repeating unit contains both a reactive group and a mesogenic group, this repeating unit corresponds to repeating unit C.

[0074] Examples of the substituent that the divalent linking group may have include a hydroxy group, a halogen atom, an amino group, an alkyl group, an alkoxy group, an acyl group, an aryl group, a nitro group, a cyano group, an alkylcarbonyl group, and a sulfonyl group.

[0075] In formula (c1), P １ represents a reactive group. The definition and preferred embodiments of the reactive group are as described above.

[0076] Specific examples of repeating unit C include the repeating units shown below: In the repeating units shown below, n represents an integer of 1 or more (typically an integer of 1 to 6).

[0077]

[0078]

[0079] Examples of repeating units containing a boronic acid group or a boronic ester group as a reactive group include the repeating units described in paragraphs 0036 to 0045 of WO 2018 / 062068.

[0080] The repeating unit C may be used singly or in combination of two or more types. The content of the repeating unit C is preferably 1 to 50 mass %, more preferably 5 to 25 mass %, and even more preferably 10 to 25 mass %, based on all repeating units constituting the main chain of the specific leveling agent.

[0081] The total content of the repeating units A, B, and C is preferably 80% by mass or more, more preferably 90% by mass or more, based on all repeating units constituting the main chain of the specific leveling agent. There is no particular upper limit, and it may be 100% by mass.

[0082] (Other Repeating Units) The specific leveling agent may contain a repeating unit other than the repeating units described above. For example, the specific leveling agent may have a repeating unit containing a polar group in terms of orientation control. Examples of the polar group include a carboxy group, an amino group, an amide group, a urea group, a urethane group, a sulfonylamino group, a sulfo group, a phospho group, a hydroxy group, a mercapto group, a methylene group substituted with an electron-withdrawing group, and a methine group substituted with an electron-withdrawing group, and the like, with a carboxy group being preferred.

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

[0084]

[0085] In the above formula (K-1), R １０ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and among these, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferred, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is more preferred, and a hydrogen atom or a methyl group is even more preferred.

[0086] Examples of the monomer that forms the repeating unit represented by the formula (K-1) include acrylic acid and methacrylic acid.

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

[0088] In terms of compatibility, the specific leveling agent preferably contains a repeating unit having a poly(alkyleneoxy) group. The poly(alkyleneoxy) group is a repeating unit having a repeating unit represented by the formula *-(L ３１ -O) ｎ４ A group represented by -* is preferred. ３１ is as described above in formula (c1). n4 represents an integer of 2 or more, preferably an integer of 2 to 60, and more preferably an integer of 4 to 40. At least one of the repeating units A to C described above may contain a poly(alkyleneoxy) group, and the specific leveling agent may contain a repeating unit having a poly(alkyleneoxy) group different from the repeating units A to C. Examples of repeating units having a poly(alkyleneoxy) group include repeating units derived from a (meth)acrylic acid ester containing a poly(alkyleneoxy) group.

[0089] The content of the repeating unit having a poly(alkyleneoxy) group is preferably 0.05 to 30 mass %, more preferably 1 to 30 mass %, and even more preferably 5 to 30 mass %, based on all repeating units constituting the main chain of the specific leveling agent.

[0090] Examples of repeating units other than those mentioned above include repeating units derived from alkyl (meth)acrylate (the alkyl group moiety has 1 to 24 carbon atoms), styrene derivatives, (meth)acrylonitrile, vinyl ether derivatives, and alkyl(meth)acrylamide derivatives.

[0091] When the specific leveling agent is a copolymer containing two or more types of repeating units, the specific leveling agent may be any of a random copolymer, an alternating copolymer, and a block copolymer, or may be a mixture of random, alternating, and block copolymers.

[0092] The weight-average molecular weight of the 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. Here, the weight-average molecular weight in the present invention is a value measured by gel permeation chromatography (GPC) under the following conditions. Solvent (eluent): tetrahydrofuran Apparatus name: EcoSEC HLC-8320GPC (manufactured by Tosoh Corporation) Column: Three columns were connected: TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ200 (all manufactured by Tosoh Corporation) Column temperature: 40°C Sample concentration: 0.1% by mass Flow rate: 0.35 ml / min Calibration curve: A calibration curve using six samples of TSK standard polystyrene manufactured by Tosoh Corporation with Mw = 706,000 to 1,013 (Mw / Mn = 1.03 to 1.06) was used.

[0093] The specific leveling agent may be used alone or in combination of two or more. 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, based on the total solid content of the liquid crystal composition, in terms of more excellent effects of the present invention. Furthermore, the content of the specific leveling agent is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, based on the total solid content of the liquid crystal composition, in terms of leveling properties.

[0094] <Polymerization Initiator> The liquid crystal composition preferably contains a polymerization initiator. The polymerization initiator is not particularly limited, but a photopolymerization initiator is preferred. Known photopolymerization initiators can be used as the photopolymerization initiator. Examples include α-carbonyl compounds, acyloin ethers, α-hydrocarbon-substituted aromatic acyloin compounds, polynuclear quinone compounds, combinations of triarylimidazole dimers and p-aminophenyl ketones, acridine and phenazine compounds, oxadiazole compounds, o-acyloxime compounds, and acylphosphine oxide compounds. Commercially available photopolymerization initiators can also be used. Examples of commercially available photopolymerization initiators include Irgacure-184, Irgacure-907, Irgacure-369, Irgacure-651, Irgacure-819, Irgacure-OXE-01, and Irgacure-OXE-02, all 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, based on the total solid content of the liquid crystal composition.

[0096] <Alignment Control Agent> The liquid crystal composition may contain an alignment control agent, if necessary. The alignment control agent can form various alignment states such as homogeneous alignment, homeotropic alignment (vertical alignment), tilted alignment, hybrid alignment, and cholesteric alignment, and can also realize a specific alignment state by controlling it more uniformly and more precisely.

[0097] As the alignment control agent for promoting homogeneous alignment, for example, a low molecular weight alignment control agent and a high molecular weight alignment control agent can be used. For low molecular weight alignment control agents, for example, the descriptions in paragraphs

[0009] to

[0083] of JP 2002-020363 A, paragraphs

[0111] to

[0120] of JP 2006-106662 A, and paragraphs

[0021] to

[0029] of JP 2012-211306 A can be referred to, the contents of which are incorporated herein by reference. Regarding polymer orientation control agents, reference can be made to, for example, paragraphs

[0021] to

[0057] of JP-A No. 2004-198511 and paragraphs

[0121] to

[0167] of JP-A No. 2006-106662, the contents of which are incorporated herein by reference.

[0098] Examples of alignment control agents that form or promote homeotropic alignment include boronic acid compounds and onium salt compounds. Specifically, the compounds described in JP-A-2008-225281, paragraphs

[0023] to

[0032] , JP-A-2012-208397, paragraphs

[0052] to

[0058] , JP-A-2008-026730, paragraphs

[0024] to

[0055] , and JP-A-2016-193869, paragraphs

[0043] to

[0055] , etc., can be referred to, the contents of which are incorporated herein by reference.

[0099] Cholesteric alignment can be achieved by adding a chiral dopant to the liquid crystal composition, and the direction of rotation of the cholesteric alignment can be controlled by the chirality of the dopant. The pitch of the cholesteric alignment can be controlled by the alignment control force of the chiral dopant.

[0100] <Solvent> The liquid crystal composition preferably contains a solvent from the viewpoint of workability in forming a film, etc. Examples of the solvent include 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 cyclopentyl methyl ether), aliphatic hydrocarbons (e.g., hexane), alicyclic hydrocarbons (e.g., cyclohexane), aromatic hydrocarbons (e.g., benzene, toluene, xylene, and trimethylbenzene), halogenated carbons (e.g., dichloromethane, trichloromethane (chloroform), dichloroethane, dichlorobenzene, and chloroform), and the like. toluene), esters (e.g., methyl acetate, ethyl acetate, ethyl propionate, butyl acetate, and diethyl carbonate), alcohols (e.g., ethanol, isopropanol, butanol, and cyclohexanol), cellosolves (e.g., methyl cellosolve, ethyl cellosolve, and 1,2-dimethoxyethane), cellosolve acetates, sulfoxides (e.g., dimethyl sulfoxide), amides (e.g., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone), and heterocyclic compounds (e.g., pyridine, etc.), as well as organic solvents such as water. These solvents may be used alone or in combination of two or more.

[0101] <Other Components> The liquid crystal composition may contain other components in addition to those described above, as necessary. Examples of the other components include a chiral agent, a chain transfer agent, a tilt angle control agent, a plasticizer, and a crosslinking agent. In terms of uniformity and alignment, it is also preferable that the liquid crystal composition does not contain a filler (e.g., silicon dioxide).

[0102] [Film manufacturing method] The film of the present invention is formed using the above-mentioned liquid crystal composition. The film manufacturing method of the present invention preferably includes, in this order, a coating film forming step of applying the above-mentioned liquid crystal composition to form a coating film, an alignment step of aligning the liquid crystal compound contained in the coating film, and an alignment fixing step of fixing the alignment state. The film of the present invention is preferably an optical film.

[0103] In the coating film forming step, a liquid crystal composition is applied onto a substrate to form a coating film. The substrate is not particularly limited, but examples thereof include a support and an alignment film included in a laminate described below. The liquid crystal composition can be easily applied onto the alignment film by using a liquid crystal composition containing the solvent described above or a liquid crystal composition that has been converted into a molten liquid or the like by heating or the like. Examples of methods for applying the liquid crystal composition include known methods such as roll coating, gravure printing, spin coating, wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spraying, and inkjet printing.

[0104] The method for aligning the liquid crystal compound in the alignment step is not particularly limited, but preferably includes a heat treatment. The heating temperature is preferably 10 to 250°C, more preferably 25 to 190°C, in terms of manufacturability and the like. The heating time is preferably 1 to 300 seconds, more preferably 1 to 60 seconds. A cooling treatment may be carried out after the heat treatment. The cooling treatment is a treatment in which the coated film after heating is cooled to about room temperature (20 to 25°C). The cooling means is not particularly limited, and can be carried out by a known method.

[0105] The method of fixation in the alignment fixation step is not particularly limited, but it is preferably a step of carrying out at least one of polymerization and drying. The conditions for the polymerization are not particularly limited, but in the polymerization by light irradiation, ultraviolet light is preferably used. The irradiation dose is 10 mJ / cm. ２ ~50 J / cm ２ is preferred, and 20 mJ / cm ２ ~5 J / cm ２ More preferably, 30 mJ / cm２ ~3 J / cm ２ is more preferably 50 to 1000 mJ / cm ２ In order to accelerate the polymerization reaction, the reaction may be carried out under heating conditions.

[0106] The film manufacturing method of the present invention preferably includes a step of performing a surface modification treatment. Specific examples of the surface modification treatment include corona treatment and plasma treatment, with corona treatment being preferred. In other words, the film is preferably subjected to corona treatment or plasma treatment. The timing of the surface modification treatment is not particularly limited, but it is preferably performed after the orientation fixing step. The surface modification treatment is preferably performed on the surface of the coating film opposite the substrate. In other words, it is preferably performed on the surface on the side where the leveling agent is unevenly distributed. By performing the surface modification treatment, the bonding state of the silicon atoms contained in the specific leveling agent changes, and the bonding energy of the peak top of the Si2p photoelectron spectrum and / or the abundance of silicon atoms bonded to four oxygen atoms take more preferred forms.

[0107] The corona treatment and plasma treatment methods are not particularly limited, and known methods can be adopted, for example, known corona discharge devices and plasma treatment devices can be used. The discharge amount in the corona treatment can be adjusted appropriately depending on the composition of the film, etc., but is preferably 10 Wmin / m ２ More than 50 Wmin / m is preferable. ２ More preferably, 500 Wmin / m or more ２ The upper limit is not particularly limited, but is preferably 5000 Wmin / m ２ In most cases, it is below 2000Wmin / m ２ The following are preferred: The power and treatment time in the corona treatment can be adjusted appropriately.

[0108] The plasma treatment method is not particularly limited, and a known method can be adopted, for example, it can be performed using a known plasma treatment apparatus. Examples of the plasma treatment apparatus include various apparatuses such as those described in paragraphs

[0015] to

[0058] of JP 2018-170183 A and paragraphs

[0041] to

[0074] of JP 2013-056514 A, the contents of which are incorporated herein by reference.

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

[0110] In the plasma treatment, the gas to be converted into a plasma state (plasma raw material gas) is not particularly limited, and examples include rare gases (inert gases) such as helium gas, neon gas, argon gas, krypton gas, xenon gas, and radon gas, as well as oxygen gas, nitrogen gas, and hydrogen gas. Among these, a mixed gas containing a rare gas and one or more reactive gases selected from oxygen gas and nitrogen gas is preferred. The content of one or more reactive gases selected from oxygen gas and nitrogen gas in the mixed gas (the total content when both are included) is preferably 0.1 to 10.0 vol%, and more preferably 1.0 to 8.0 vol%, relative to the total volume of the mixed gas, in order to more easily reduce the water contact angle of the film surface after plasma treatment. Furthermore, the content of the rare gas in the mixed gas is preferably 50.0 vol% or more, more preferably 80.0 vol% or more, and even more preferably 90.0 vol% or more, relative to the total volume of the mixed gas. The upper limit of the content of the rare gas in the mixed gas is not particularly limited, and is preferably 99.9% by volume or less, and more preferably 99.0% by mass or less, relative to the total volume of the mixed gas. Rare gases are more easily converted into plasma with the application of lower energy than oxygen gas or nitrogen gas. Therefore, by setting the content of the rare gas within the above numerical range, a uniform discharge can be generated on the coating film surface, and the coating film surface can be easily modified uniformly. Among these, helium gas or argon gas is preferred as the rare gas, as it is in a metastable state and the discharge is easily sustained. Helium gas is more preferred because it has a longer lifetime in the excited state. The gas composition in the plasma raw material gas can be quantified by analyzing a sample of the plasma raw material gas using an analytical device such as gas chromatography or mass spectrometry.

[0111] It is also preferable to perform plasma treatment on the surface of the coating film while conveying the coating film using a plasma generating device that generates plasma between an electrode and a counter electrode when power is supplied. The power in the plasma treatment is preferably 100 to 8000 W. In particular, when performing plasma treatment under atmospheric pressure, the power is more preferably 600 to 8000 W, and even more preferably 2500 to 6000 W, in order to further reduce the water contact angle of the film. When performing plasma treatment under reduced pressure, the power is more preferably 100 to 1000 W, and even more preferably 100 to 500 W, in order to further reduce the water contact angle of the film. Furthermore, the lower limit of the conveying speed of the coating film to be 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, in terms of superior productivity and discharge stability (stability of in-plane uniformity of modification). The upper limit of the transport speed of the coating film to be subjected to plasma treatment is preferably 100 m / min or less, more preferably 50.0 m / min or less, still 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, in terms of being able to suppress the influence of entrained air and achieving excellent discharge stability (stability of in-plane uniformity of modification).

[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 numerical range, problems such as thermal melting of the substrate and / or deformation of the electrode are less likely to occur. Plasma treatment may be performed continuously or intermittently. When performed intermittently, it is preferable that the total treatment time be within the above range. The treatment temperature when performing plasma treatment is preferably 0 to 200°C, more preferably 15 to 150°C.

[0113] [Film Properties] The film of the present invention is formed using a liquid crystal composition. As described above, it is preferable that the orientation state of the liquid crystal compound in the film is fixed. In this specification, the "fixed" orientation state of the liquid crystal compound refers to a state in which the orientation of the liquid crystal compound is maintained. Specifically, it is more preferable that the layer has no fluidity and can stably maintain the fixed orientation state without any change in the orientation state due to an external field or external force, usually at a temperature range of 0 to 50°C, or more severely, at a temperature range of -30 to 70°C. In a film having a fixed orientation state, the liquid crystal compound may no longer exhibit liquid crystallinity. In a film, the liquid crystal compound may be a polymer of a polymerizable liquid crystal compound or a polymer liquid crystal compound that has a high molecular weight in the liquid crystal composition. That is, the film may include a polymer of a polymerizable liquid crystal compound. As described below, the film may include a polymer of a polymerizable 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 may be any of horizontal orientation, vertical orientation, tilt orientation, and twist orientation. Furthermore, a single layer may have multiple orientation states, such as the liquid crystal cured layer described in WO 2021 / 033640, which has a first region in which the orientation state of the liquid crystal compound is fixed in a twisted orientation along a helical axis extending along the thickness direction, and a second region in which the orientation state of the liquid crystal compound is fixed in a homogeneous orientation, along the thickness direction. In this specification, "horizontal orientation" refers to the principal surface of the film being parallel to the long axis direction of the liquid crystal compound. Strict parallelism is not required, and in this specification, it refers to an orientation in which the angle between the long axis direction of the liquid crystal compound and the principal surface of the film is less than 10°. In this specification, "vertical orientation" refers to the principal surface of the film being perpendicular to the long axis direction of the liquid crystal compound. Strict perpendicularity is not required, and in this specification, it refers to an orientation in which the angle between the long axis direction of the liquid crystal compound and the principal surface of the film is 170 to 110°.

[0115] The film of the present invention is preferably an optically anisotropic film. Examples of the optically anisotropic film include a positive A plate, a positive C plate, and an optically anisotropic film having, along the thickness direction, a first region in which the orientation state of liquid crystal compounds twisted along a helical axis extending along the thickness direction is fixed, and a second region in which the orientation state of liquid crystal compounds homogeneously aligned is fixed (hereinafter, this embodiment will also be referred to as "optically anisotropic film A").

[0116] A positive A plate (positive A plate) and a positive C plate (positive C plate) are defined as follows. When the refractive index in the in-plane slow axis direction of the film (the direction in which the in-plane refractive index is maximum) is nx, the refractive index in the in-plane direction perpendicular to the in-plane slow axis is ny, and the refractive index in the thickness direction is nz, a positive A plate satisfies the relationship of formula (A1), and a positive C plate satisfies the relationship of formula (C1). Note that a positive A plate has a positive Rth, and a positive C plate has a negative Rth. Formula (A1) nx>ny≒nz Formula (C1) nz>nx≒ny Note that the above "≒" encompasses not only the case where both are completely identical, but also the case where both are substantially identical. Regarding "substantially the same," for a positive A plate, "ny ≒ nz" includes, for example, a case where (ny - nz) x d (where d is the film thickness) is -10 to 10 nm, preferably -5 to 5 nm, and "nx ≒ nz" includes, for example, a case where (nx - nz) x d (where d is the film thickness) is -10 to 10 nm, preferably -5 to 5 nm. Also, for a positive C plate, "nx ≒ ny" includes, for example, a case where (nx - ny) x d (where d is the film thickness) is 0 to 10 nm, preferably 0 to 5 nm.

[0117] When the film 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, the "λ / 4 plate" is a plate having a λ / 4 function, specifically, a plate having a function of converting linearly polarized light of a certain wavelength into circularly polarized light (or circularly polarized light into linearly polarized light).

[0118] An optically anisotropic film (optically anisotropic film A) having, along the thickness direction, a first region in which the alignment state of liquid crystal compounds twisted along a helical axis extending along the thickness direction is fixed, and a second region in which the alignment state of liquid crystal compounds homogeneously aligned is fixed, will be described in detail. When the thickness of the first region of the optically anisotropic film A is d1 (nm) and the refractive index anisotropy of the first region measured at a wavelength of 550 nm is Δn1, the first region preferably satisfies the following formula (1-1) in order to enable the optically anisotropic film to be suitably applied to a circular polarizer. Formula (1-1) 100 nm≦Δn1d1≦240 nm Among these, it is more preferable to satisfy formula (1-2), and even more preferable to satisfy formula (1-3). 120 nm≦Δn1d1≦220 nm Equation (1-2) 140 nm≦Δn1d1≦200 nm Equation (1-3) The refractive index anisotropy Δn1 means 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 is preferably 60 to 120°, more preferably 70 to 110°, in order to enable the optically anisotropic film to be suitably applied to a circular polarizer. The twist angle is measured using an AxoScan from Axometrics and its instrument analysis software.

[0120] Furthermore, assuming that the thickness of the second region of the optically anisotropic film A is d2 (nm) and the refractive index anisotropy of the second region measured at a wavelength of 550 nm is Δn2, it is preferable that the second region satisfy the following formula (2-1), in order to enable the optically anisotropic film to be suitably applied to a circularly polarizing plate. Formula (2-1) 100 nm≦Δn2d2≦240 nm Among these, it is more preferable to satisfy formula (2-2), and even more preferable to satisfy formula (2-3). Formula (2-2) 120 nm≦Δn2d2≦220 nm Formula (2-3) 140 nm≦Δn2d2≦200 nm It should be noted that the refractive index anisotropy Δn2 means the refractive index anisotropy of the second region.

[0121] The film of the present invention contains silicon atoms derived from a specific leveling agent. The form of the silicon atoms is not particularly limited, and they may be contained as part of the above-mentioned specific leveling agent, or may be contained in other forms. In another form, the film may contain a component derived from the specific leveling agent (for example, silicon dioxide, which will be described later). In terms of achieving better effects of the present invention, it is also preferable that the silicon atoms are contained in the form of silicon dioxide. The presence of silicon dioxide can be determined, for example, by detecting a silicon dioxide (SiO ) when the film is subjected to time-of-flight secondary ion mass spectrometry (TOF-SIMS). ２ ) ｌ (l is an integer of 1 or more) can be determined by the presence or absence of a fragment having a molecular weight corresponding to the

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

[0123] <Requirement 1> The film of the first embodiment satisfies the following Requirement 1. Requirement 1: In the Si2p photoelectron spectrum obtained by measuring the surface of the film by X-ray photoelectron spectroscopy (XPS), the binding energy of the peak top is 102.0 eV or more. Note that it is sufficient for at least one surface of the film of the first embodiment to satisfy Requirement 1, and it is preferable that the surface of the coating film formed using the liquid crystal composition in the above-described film manufacturing method, which was on the air interface side, satisfies the above requirement.

[0124] The binding energy of the peak top of the photoelectron spectrum of Si2p is preferably 102.5 eV or more, more preferably 103.2 eV or more, in terms of more excellent effects of the present invention. The binding energy of the peak top of the photoelectron spectrum of Si2p is often 105.0 eV or less, more often 104.0 eV or less.

[0125] The photoelectron spectrum of Si2p measured by XPS is a core photoelectron spectrum corresponding to the 2p orbital of a silicon atom (Si). The specific method for measuring the photoelectron spectrum of Si2p is as follows. First, the surface of the film is measured under the following conditions to obtain the photoelectron spectrum of Si2p. A spectrum in which a peak top is observed in the range of 101.0 to 106.0 eV is assigned as the photoelectron spectrum of Si2p.

[0126] (XPS measurement conditions) Apparatus: Quantera manufactured by Ulvac-PHI X-ray source: monochromated Al-Ka ray (X-ray beam diameter 100 μmΦ, output 25 W, voltage 15 kV) Analysis area: 300 μm × 300 μm Pass energy: 55 eV Step energy: 0.05 eV Charge correction: Yes (electron gun and low-energy ion gun used together) Photoelectron take-off angle: 45 In the above measurement, the bond energy is calibrated by setting the peak top of the photoelectron spectrum of C1s derived from a C—C bond detected from the same sample to 284.8 eV.

[0127] <Requirement 2> The film of the second embodiment satisfies the following Requirement 2. Requirement 2: A silicon atom to which four oxygen atoms are bonded is present on the surface of the film. It is sufficient that at least one surface of the film of the second embodiment satisfies Requirement 2, and it is preferable that the surface of the coating film formed using the liquid crystal composition in the above-described film manufacturing method, which was on the air interface side, satisfies the above requirement.

[0128] The presence of a silicon atom to which four oxygen atoms are bonded can be confirmed by XPS, specifically, by the presence or absence of a peak attributable to a silicon atom to which four oxygen atoms are bonded in the photoelectron spectrum of Si2p measured by XPS using the same procedure as in requirement 1 above.

[0129] The method for identifying the peaks attributed to silicon atoms bonded to four oxygen atoms is explained below. The photoelectron spectrum of Si2p is fitted using the four bond energy values ​​of the first to fourth peaks shown below. The first peak is attributed to SiO_1, the second peak to SiO_2, the third peak to SiO_3, and the fourth peak to SiO_4. SiO_n (n = 1, 2, 3, 4) represents a silicon atom having n Si-O bonds and (4 - n) Si-C bonds. SiO_4 corresponds to a silicon atom bonded to four oxygen atoms. Specifically, the binding energies of the peak tops of the first to fourth peaks are fixed within the range of ±0.1 eV of the values ​​shown below, the fitting function is a Gauss-Lorentz function (Gauss ratio is 90% or more), the baseline is processed using the Shirley method, and fitting is performed so that the residual sum of squares with the actually measured spectrum is minimized. First peak (SiO_1): 101.62 eV Second peak (SiO_2): 102.15 eV Third peak (SiO_3): 102.65 eV Fourth peak (SiO_4): 103.33 eV

[0130] If the fitting results show that a fourth peak is present, it indicates that a silicon atom bonded to four oxygen atoms is present. The presence of a fourth peak means that the area of ​​the fourth peak is 4% or more of the area of ​​the photoelectron spectrum of Si2p. The area of ​​the fourth peak is preferably 30% or more, more preferably 97% or more, of the area of ​​the photoelectron spectrum of Si2p. The upper limit of the area of ​​the fourth peak is not particularly limited, and may be 100% of the area of ​​the photoelectron spectrum of Si2p.

[0131] <Silicon Atomic Weight> In order to further enhance the present invention, the content of silicon atoms on the surface of the film of the present invention is preferably 15.0 Atomic% or less, more preferably 5.0 Atomic% or less, relative to all atoms on the film surface. Furthermore, in order to further enhance leveling properties and the effects of the present invention, the content of silicon atoms on the surface of the film of the present invention is preferably 1.0 Atomic% or more, more preferably 1.5 Atomic% or more, relative to all atoms on the film surface. The silicon atom content is a value measured by the XPS described above. Specifically, XPS is performed using the same procedure as in Requirement 1 described above, the atomic concentration of all detected atoms is calculated, and the silicon atom content (Atomic%) relative to all detected atoms is calculated. It is preferable that a surface that satisfies either Requirement 1 or Requirement 2 described above satisfies the above requirement. In this case, the other surface does not necessarily have to satisfy the above requirement.

[0132] <Water Contact Angle> The water contact angle of the surface of the film of the present invention is preferably 80° or less, more preferably 70° or less, and even more preferably 50° or less. The water contact angle of the film of the present invention is often 10° or more, and preferably 20° or more. A surface that satisfies either requirement 1 or requirement 2 above preferably satisfies the above requirement. In this case, the other surface does not necessarily satisfy the above requirement. The water contact angle can be measured by a known method, for example, at 25°C using a DMo-702 manufactured by Kyowa Interface Science Co., Ltd.

[0133] <Surface Elastic Modulus> The surface elastic modulus of the film of the present invention is preferably 2.5 GPa or more, more preferably 4.0 GPa or more, and even more preferably 5.1 GPa or more. There is no particular upper limit to the surface elastic modulus of the film of the present invention, but it is often 10.0 GPa or less, and preferably 7.0 GPa or less. It is preferable that a surface that satisfies either requirement 1 or requirement 2 above satisfies the above requirement. In this case, the other surface does not need to satisfy the above requirement. Note that the surface in the above surface elastic modulus refers to the region of the film from the air interface to a depth of 20 nm or less.

[0134] The 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 a load / displacement curve obtained by performing measurements in QNM mode using an AFM device using a JKR contact mechanics model. As the AFM, for example, a DimensionIcon manufactured by Bruker can be used. Specific details of the procedure will be described in detail in the examples below.

[0135] <Surface Adsorption Force> The surface adsorption force of the film 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. There is no particular upper limit to the surface adsorption force of the film of the present invention, but it is often 50.0 nN or less, preferably 40.0 nN or less, and more preferably 30.0 nN or less. It is preferable that a surface that satisfies either the above-mentioned requirement 1 or requirement 2 satisfies the above requirement. In this case, the other surface does not need to satisfy the above requirement.

[0136] The surface adhesive force can be measured on the surface of the film using an AFM. Specifically, the surface adhesive force can be calculated by fitting a load / displacement curve obtained by performing measurements in QNM mode using an AFM device using the JKR contact mechanics model. Specific details of the procedure will be described in the Examples below.

[0137] [Laminate] The film of the present invention can be used as a laminate in combination with other layers. Examples of other layers in a laminate including the film of the present invention (hereinafter also referred to as the "laminate of the present invention") include a support and an alignment film. It is also preferable that the surface of the film satisfying at least one of the above-mentioned requirements 1 and 2 be the outermost surface of the laminate. FIG. 1 is a schematic cross-sectional view showing an example of a laminate of the present invention. Note that FIG. 1 is a schematic diagram, and the thickness and positional relationship of each layer do not necessarily correspond to the actual ones. The support and alignment film shown in FIG. 1 are both optional components. The laminate 10 shown in FIG. 1 has a support 16, an alignment film 14, and a liquid crystal layer 12, in this order. The liquid crystal layer 12 is the film of the present invention. The liquid crystal layer 12 may also be an optically anisotropic layer. Another liquid crystal layer may also be included between the liquid crystal layer 12 and the alignment film 14. For example, when the polarizing plate of the present invention described below is used as a circular polarizing plate, or when the film of the present invention is used as an optical compensation film for an IPS (In-Plane-Switching) mode or FFS (Fringe-Field-Switching) mode liquid crystal display device, the laminate preferably includes a positive A plate and a positive C plate. Various members used in the laminate of the present invention will be described in detail below.

[0138] <Support> The support is a base material for forming a film. The support is preferably transparent. Specifically, it is preferable that the light transmittance be 80% or more.

[0139] Examples of the support include glass substrates and polymer films. Examples of materials for the polymer film include cellulose-based polymers; acrylic polymers having acrylic acid ester polymers such as polymethyl methacrylate and lactone ring-containing polymers; 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 polyamide; 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; arylate-based polymers; polyoxymethylene-based polymers; epoxy-based polymers; and polymers obtained by mixing these polymers. In addition, the polarizer described below may also serve as such a support.

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

[0141] <Alignment Film> The laminate of the present invention preferably has an alignment film between the support and the film. The support may also serve as the alignment film.

[0142] Alignment films generally contain a polymer as a main component. Polymer materials for alignment films are described in numerous publications, and many commercially available products are available. The polymer material used in the present invention is preferably polyvinyl alcohol or polyimide, and derivatives thereof. Modified or unmodified polyvinyl alcohol is particularly preferred. Examples of alignment films that can be used in the present invention include those described in WO 01 / 088574, page 43, line 24 to page 49, line 8; modified polyvinyl alcohols described in paragraphs

[0071] to

[0095] of Japanese Patent No. 3907735; and liquid crystal alignment films formed using liquid crystal aligning agents described in JP 2012-155308 A.

[0143] In the present invention, it is also preferable to use a photo-alignment film as the alignment film, because it is possible to prevent deterioration of the surface condition by not contacting the alignment film surface during formation of the alignment film. The photo-alignment film is not particularly limited, but polymer materials such as polyamide compounds and polyimide compounds described in paragraphs

[0024] to

[0043] of WO 2005 / 096041; liquid crystal alignment films formed by liquid crystal aligning agents having a photo-aligning group with a cinnamic acid structure described in JP 2012-155308 A; product name LPP-JP265CP manufactured by Rolic Technologies, Inc., and the like can be used.

[0144] In the present invention, the thickness of the alignment film is not particularly limited, but from the viewpoint of reducing surface irregularities that may exist on the support and forming an optically anisotropic layer with a uniform thickness, the thickness 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 may be formed on the surface of another liquid crystal layer. The other liquid crystal layer may be a liquid crystal layer formed by fixing the above-mentioned liquid crystal composition in a predetermined alignment state, or a liquid crystal layer formed by fixing a composition containing a liquid crystal compound and, if necessary, optional components (e.g., a polymerization initiator, a dichroic material, and a leveling agent) in a predetermined alignment state.

[0146] In the laminate of the present invention, the film of the present invention may be laminated with another liquid crystal layer. When the film of the present invention is laminated with another liquid crystal layer, it is also preferable that the lamination be performed via an adhesive layer. In other words, it is also preferable that the laminate of the present invention has an adhesive layer. As described above, a liquid crystal layer formed using a liquid crystal composition containing a leveling agent containing a silicon atom (particularly a surface on which the leveling agent is unevenly distributed) may not have sufficient adhesion to adjacent layers. However, the film of the present invention satisfies at least one of the above-mentioned requirements 1 and 2, and therefore exhibits excellent adhesion even when the surface on which the leveling agent is unevenly distributed is adjacent to an adhesive layer. The other liquid crystal layer may be the film of the present invention or the other liquid crystal layer described above.

[0147] The adhesive layer is a layer formed using an adhesive. The adhesive layer is preferably a curable adhesive composition that cures upon irradiation with active energy rays or heating. Examples of curable adhesives include electron beam curable adhesives, ultraviolet curable adhesives, and visible light curable adhesives, with ultraviolet curable adhesives being preferred. Examples of curable adhesive compositions include curable adhesive compositions containing a cationically polymerizable compound (e.g., epoxy adhesives) and curable adhesive compositions containing a radically polymerizable compound (e.g., (meth)acrylate adhesives). For details of the adhesive layer, see, for example, paragraphs

[0062] to

[0080] of JP 2016-035579 A, ​​the contents of which are incorporated herein by reference.

[0148] The laminate of the present invention preferably contains an ultraviolet (UV) absorber in consideration of the effects of external light (especially ultraviolet light). The ultraviolet absorber may be contained in the film of the present invention or in a member other than the film. A suitable example of a member other than the film is a support. Any conventionally known ultraviolet absorber capable of exhibiting ultraviolet absorption properties can be used as the ultraviolet absorber. Among such ultraviolet absorbers, benzotriazole-based or hydroxyphenyltriazine-based ultraviolet absorbers are preferred from the viewpoint of achieving high ultraviolet absorption and ultraviolet absorption (ultraviolet blocking) capabilities useful in image display devices. Furthermore, in order to broaden the ultraviolet absorption bandwidth, two or more ultraviolet absorbers with different maximum absorption wavelengths can be used in combination. Specific examples of ultraviolet absorbers include the compounds described in paragraphs

[0258] to

[0259] of JP 2012-018395 A and the compounds described in paragraphs

[0055] to

[0105] of JP 2007-072163 A. Commercially available products that can be used include Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479, and Tinuvin 1577 (all manufactured by BASF).

[0149] [Polarizing Plate] The polarizing plate 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, the angle between the slow axis of the positive A plate and the absorption axis of the polarizer described below is preferably 30 to 60°, more preferably 40 to 50°, even more preferably 42 to 48°, and particularly preferably 45°, in order to enable suitable applications such as circular polarizing plates. Here, the "slow axis" refers to the direction in which the refractive index is maximized in the plane of the liquid crystal layer, and the "absorption axis" of the polarizer refers to the direction in which the absorbance is highest. When the film of the present invention is the optically anisotropic film A described above, the absolute value of the angle between the in-plane slow axis of the second region formed by fixing the alignment state of the homogeneously aligned liquid crystal compound and the absorption axis of the polarizer is preferably 5 to 25°, more preferably 10 to 20°, in order to enable suitable applications such as circular polarizing plates. The polarizing plate can also be used as an optical compensation film for IPS-type or FFS-type liquid crystal display devices. When the polarizing plate is used as an optical compensation film for an IPS-type or FFS-type liquid crystal display device, it is preferable that the above-mentioned film of the present invention be used as at least one plate of a laminate of a positive A plate and a positive C plate. In other words, the polarizing plate of the present invention has a polarizer, an adhesive layer, the film of the present invention, and a liquid crystal layer, and it is preferable that one of the film of the present invention and the liquid crystal layer is a positive A plate, and the other is a positive C plate. The liquid crystal layer may also be considered as a 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 below is perpendicular or parallel. Specifically, it is more preferable that the angle between the slow axis of the positive A plate layer and the absorption axis of the polarizer described below is 0 to 5° or 85 to 95°. When the polarizing plate of the present invention is used in the image display device described below, it is preferable that the angle between the slow axis of the liquid crystal layer and the absorption axis of the polarizer described below is parallel or parallel.

[0150] The polarizing plate 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. When the polarizer of the present invention includes a laminate of a positive A plate and a positive C plate, it is preferable that an adhesive layer be provided between the positive A plate and the positive C plate.

[0151] FIG. 2 is a schematic cross-sectional view showing an example of a polarizing plate of the present invention. The polarizing plate 20 shown in FIG. 2 includes a polarizer 22, a first adhesion layer 24, a first liquid crystal layer 26, a second adhesion layer 28, and a second liquid crystal layer 30, in this order. Note that FIG. 2 is a schematic diagram, and the thickness and positional relationship of each layer do not necessarily correspond to the actual ones. Furthermore, one of the first adhesion layer 24 and the second adhesion layer 28 is an optional component, and one of the first liquid crystal layer and the second liquid crystal layer is an optional component. In the polarizing plate of the embodiment shown in FIG. 2, at least one of the first liquid crystal layer 26 and the second liquid crystal layer 30 is a film of the present invention, and it is preferable that at least the first liquid crystal layer 26 is a film of the present invention. It is also preferable that the first liquid crystal layer 26 and the second liquid crystal layer 30 are a positive A plate and a positive C plate, respectively. In the polarizing plate of the embodiment shown in FIG. 2, it is preferable that at least one of the first adhesion layer 24 and the second adhesion layer 28 is an adhesive layer, and it is preferable that at least the second adhesion layer 28 is an adhesive layer.

[0152] [Polarizer] The polarizer is not particularly limited as long as it is a component that has the function of converting light into specific linearly polarized light, and conventionally known absorption-type polarizers, reflective-type polarizers, and coated-type polarizers can be used. Examples of absorption-type polarizers include iodine-based polarizers, dye-based polarizers using dichroic dyes, and polyene-based polarizers. Iodine-based polarizers and dye-based polarizers include coated-type polarizers and stretched-type polarizers, and either can be used. However, polarizers prepared by adsorbing iodine or a dichroic dye to polyvinyl alcohol and stretching the resulting material are preferred. Examples of coated-type polarizers include polarizers containing a cured product of a liquid crystal compound and a dichroic dye. Examples of reflective polarizers include polarizers stacked with thin films of different birefringence, wire-grid polarizers, and polarizers combining a cholesteric liquid crystal having a selective reflection region with a quarter-wave plate.

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

[0154] [Adhesive Layer] The polarizing plate of the present invention has an adhesive layer. The polarizing plate of the present invention may have an adhesive layer between the polarizer and the film of the present invention, or may have an adhesive layer between either the polarizer or the film of the present invention and another layer (e.g., a liquid crystal layer), or may have an adhesive layer between any of the layers. The adhesive layer is preferably adjacent to the film of the present invention. In particular, the adhesive layer is preferably adjacent to a surface of the film of the first embodiment that satisfies requirement 1, or a surface of the film of the second embodiment that satisfies requirement 2. Examples of adhesive layers include the adhesive layers described above.

[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, lifting or peeling does not occur between the laminated film and the polarizer, and practically acceptable adhesion strength is obtained. Furthermore, from the viewpoint of suppressing the generation of bubbles, the thickness of the adhesive layer is preferably 0.4 μm or more.

[0156] The polarizing plate of the present invention may have a pressure-sensitive adhesive layer as an adhesive layer. For example, an adhesive layer may be provided between the film of the present invention and another liquid crystal layer, or a pressure-sensitive adhesive layer may be provided between the polarizer and the polarizing plate of the present invention. Examples of pressure-sensitive adhesives contained in the pressure-sensitive adhesive layer include acrylic pressure-sensitive adhesives, epoxy pressure-sensitive adhesives, rubber pressure-sensitive adhesives, silicone pressure-sensitive adhesives, urethane pressure-sensitive adhesives, vinyl alkyl ether pressure-sensitive adhesives, polyvinyl alcohol pressure-sensitive adhesives, polyvinylpyrrolidone pressure-sensitive adhesives, polyacrylamide pressure-sensitive adhesives, and cellulose pressure-sensitive adhesives. Among these, acrylic pressure-sensitive adhesives (pressure-sensitive adhesives) are preferred because of their excellent transparency, weather resistance, heat resistance, and the like. Regarding pressure-sensitive adhesives, reference may be made to paragraphs

[0071] to

[0084] of JP 2018-060014 A, the contents of which are incorporated herein by reference.

[0157] The thickness of the pressure-sensitive 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 pressure-sensitive adhesive layer is within this range, lifting or peeling does not occur between the laminated layers, and an adhesive strength that does not cause any practical problems can be obtained.

[0158] [Image display device] The display device of the present invention is an image display device having the film of the present invention or the polarizing plate of the present invention. The display element used in the image display device is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as "EL (Electro Luminescence)") display panel, and a plasma display panel. Of these, a liquid crystal cell or an organic EL display panel is preferred. That is, the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as the display element, or an organic EL display device using an organic EL display panel as the display element.

[0159] [Organic EL Display Device] An example of an organic EL display device, which is an example of an image display device, includes, from the viewing side, a polarizer, a λ / 4 plate made of the above-mentioned film, and an organic EL display panel, in this order. The organic EL display panel is a display panel configured using an organic EL element in which an organic light-emitting layer (organic electroluminescence layer) is sandwiched between electrodes (between a cathode and an anode). The configuration of the organic EL display panel is not particularly limited, and a known configuration may be used.

[0160] [Liquid Crystal Display Device] A liquid crystal display device, which is an example of an image display device, is a liquid crystal display device having the above-described polarizing plate and a liquid crystal cell. Of the polarizing plates provided on both sides of the liquid crystal cell, it is preferable to use the above-described polarizing plate as the front-side polarizing plate, and it is more preferable to use the above-described polarizing plate as the front-side and rear-side polarizing plates.

[0161] <Liquid Crystal Cell> The liquid crystal cell used in the liquid crystal display device is 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 is not limited to these.

[0162] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0163] [Preparation of Film and Laminate] The film and laminate of the present invention were prepared as follows.

[0164] [Preparation of Support (Cellulose Acylate Dope)] The following composition was charged into a mixing tank, stirred, and further 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 dope. The solid content of the dope was 23.5% by mass, the amount of plasticizer added was the ratio relative to the cellulose acylate, and the solvent for the dope was methylene chloride / methanol / butanol = 81 / 18 / 1 (mass ratio).

[0165] ------------------------------------------------ Cellulose acylate dope -------------------------------------------------- Cellulose acylate (acetyl substitution degree 2.86, viscosity average degree of polymerization 310) 100 parts by mass Sugar ester compound 1 (formula (S4) below) 6.0 parts by mass 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 part by mass Solvent (methylene chloride / methanol / butanol) 351.9 parts by mass --------------------------------------------------

[0166]

[0167]

[0168] The dope prepared above was cast using a drum film-forming machine. The dope was cast from a die onto a metal support cooled to 0°C, and then the resulting web (film) was peeled off. The drum was made of SUS (Steel Use Stainless Steel).

[0169] The web (film) obtained by casting was peeled from the drum and then dried for 20 minutes in a tenter apparatus, in which both ends of the web were clipped and conveyed at 30 to 40°C. Subsequently, the web was post-dried by zone heating while conveying it with a roll. The obtained web was knurled and then wound up to give cellulose acylate film A1. The obtained cellulose acylate film A1 had a thickness of 40 μm, an in-plane retardation Re(550) of 1 nm at a wavelength of 550 nm, and a thickness direction retardation Rth(550) of 25 nm at a wavelength of 550 nm.

[0170] [Preparation of Laminate F1-1] <Formation of Alignment Film> A coating solution E1 for forming a photo-alignment film having the following composition was continuously coated on the above-mentioned cellulose acylate film A1 using a wire bar. The cellulose acylate film A1 on which the coating film was formed was dried with hot air at 140°C for 120 seconds, and then the coating film was irradiated with polarized ultraviolet light (10 mJ / cm ２ , using an ultra-high pressure mercury lamp) to form a photo-alignment film E1 with a thickness of 0.7 μm, thereby obtaining a TAC film with a photo-alignment film.

[0171] -------------------------------------------------- Coating liquid E1 for forming photoalignment film -------------------------------------------------- Polymer PA-2 (listed below) 100.00 parts by mass Thermal cationic polymerization initiator PAG-1 (listed below) 6.00 parts by mass Diisopropylethylamine 0.15 parts by mass Butyl acetate 622.75 parts by mass Methyl ethyl ketone 155.69 parts by mass --------------------------------------------------

[0172] Polymer PA-2 (weight average molecular weight: 45,000. The numerical value for each repeating unit represents the content (mass%) of each repeating unit relative to all repeating units.)

[0173]

[0174] Thermal cationic polymerization initiator PAG-1

[0175]

[0176] <Formation of Optical Film F1-1> A liquid crystal composition F1-1 having the following composition was applied onto the photo-alignment film E1 using a bar coater. The coating film formed on the photo-alignment film E1 was heated to 120°C with hot air and then cooled to 60°C. A high-pressure mercury lamp was used in a nitrogen atmosphere to irradiate the film with 100 mJ / cm at a wavelength of 365 nm. ２ The coating film was irradiated with ultraviolet light of 200 mJ / cm 2 while being heated to 120°C. ２ The coating film was irradiated with ultraviolet light of 1000 nm, thereby fixing the alignment of the liquid crystal compound to form an optical film F1-1, and a laminate F1-1 having a support, an alignment film, and an optical film F1-1 in this order was obtained. The optical film F1-1 had a thickness of 2.9 μm and an Re(550) of 142 nm. The optical film F1-1 also satisfied the relationship Re(450)≦Re(550)≦Re(650). Re(450) / Re(550) was 0.82. The optical film F1-1 is an optically anisotropic layer, and corresponds to a so-called λ / 4 plate.

[0177] 0.16 parts by mass of polymerizable liquid crystal compound LC-3 below; 5.00 parts by mass of polymerizable liquid crystal compound LC-4 below; 0.50 parts by mass of polymerization initiator PI-1 below; 0.06 parts by mass of leveling agent SA-1 below; Cyclopentanone 181.00 parts by mass; Methyl ethyl ketone 54.00 parts by mass ----------------------------------------------------------------------------------

[0178] Reverse dispersion compound LA-1 (tBu represents a tertiary butyl group)

[0179]

[0180] Reverse dispersion compound LA-2

[0181]

[0182] Reverse dispersion compound LA-3

[0183]

[0184] Polymerizable liquid crystal compound LC-1

[0185]

[0186] Polymerizable liquid crystal compound LC-2

[0187]

[0188] Polymerizable liquid crystal compound LC-3

[0189]

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

[0191]

[0192] Polymerization initiator PI-1

[0193]

[0194] Leveling agent SA-1 (weight average molecular weight: 20,000. The numerical value for each repeating unit in the main chain represents the content (mass ratio) of each repeating unit relative to all repeating units. The numerical value for each repeating unit in the side chain represents the number of repeating units.)

[0195]

[0196] [Preparation of Laminate F2-1] An optical film F2-1 was formed in the same manner as in the preparation of the laminate F1-1, except that a liquid crystal composition F1-2 was used in which the amount of leveling agent SA-1 added in the above-described liquid crystal composition F1-1 was changed from 0.06 parts by mass to 0.5 parts by mass, and thus a laminate F2-1 was prepared.

[0197] [Preparation of Laminates F1-2 to F1-5 and F2-2 to F2-3] The surface of optical film F1-1 of 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, and laminates F1-2 to F1-5 were prepared. The surface of optical film F2-1 of 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, and laminates F2-2 to F2-3 were prepared.

[0198] [Preparation of Laminate F1-6] The surface of the laminate F1-1 facing the optical film F1-1 was subjected to plasma treatment under atmospheric pressure to form a laminate F1-6. The plasma treatment was carried out using an apparatus configured similar to the plasma generation apparatus described in Example 1 of JP 2018-170183 A. In this case, helium gas, oxygen gas, and nitrogen gas were introduced between the electrode and the counter electrode in a volumetric flow ratio of 10 / 0.025 / 0.5, and 6000 W of power was applied to the electrode to generate plasma between the counter electrode. The transport speed of the laminate F1-1 transported between the electrode and the counter electrode was 10.0 m / min. The gas composition of the plasma raw material gas introduced into the plasma generation apparatus (analyzed by gas chromatography) was 94.1 vol% / 0.4 vol% / 5.5 vol% helium gas, oxygen gas, and nitrogen gas.

[0199] [Preparation of Positive C Plate FC-1] The coating liquid FC-1 for forming a positive C plate having the following composition was applied onto the above-mentioned cellulose acylate film A1, and the resulting coating film was heated at 60°C for 60 seconds. ２ An air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was used, and the light output was 300 mJ / cm ２ The liquid crystal compound was vertically aligned by irradiating it with ultraviolet light of 1200 W / m to fix the alignment state, and a positive C plate having a thickness of 0.5 μm and Rth(550)=−60 nm was formed. Furthermore, the surface of the obtained positive C plate was subjected to corona treatment (treatment amount 1200 W / m ). ２ ) was performed to prepare a positive C plate FC-1.

[0200] -------------------------------- Coating liquid FC-1 for forming positive C-plate ------------------------------------------------ 83 parts by mass of the above liquid crystal compound LC-1 15 parts by mass of the above liquid crystal compound LC-2 2 parts by mass of the above liquid crystal compound LC-3 Polymerizable monomer (UA-601I, manufactured by Kyoeisha Chemical Co., Ltd.) 5 parts by mass Polymerization initiator (IrgacureOXE01, manufactured by BASF) 4 parts by mass Leveling agent SC-1 described below 0.4 parts by mass Vertical alignment liquid crystal compound promoter S01 described below 1.2 parts by mass Polymer M described below 1.14 parts by mass Methyl isobutyl ketone 494.9 parts by mass Ethyl propionate 95.0 parts by mass 2-butanone 43.3 parts by mass ----------------------------------------------------------------------------------

[0201] Vertical alignment liquid crystal compound promoter S01

[0202]

[0203] Polymer M (weight average molecular weight: 60,000. The numerical value shown for each repeating unit indicates the content (mass ratio) of each repeating unit relative to all repeating units.)

[0204]

[0205] Leveling agent SC-1 (weight average molecular weight: 25,000. The numerical value shown for each repeating unit indicates the content (mass ratio) of each repeating unit relative to all repeating units.)

[0206]

[0207] [Fabrication of Polarizing Plate and Image Display Device] [Fabrication of Polarizer 1 with Protective Film] The surface of a support of cellulose triacetate film TJ25 "Z-TAC" (manufactured by Fujifilm Corporation; thickness: 25 μm) was subjected to alkaline saponification treatment. Specifically, the support was immersed in a 1.5 N sodium hydroxide aqueous solution at 55°C for 2 minutes, washed in a water wash bath at room temperature, and further neutralized with 0.1 N sulfuric acid at 30°C. After neutralization, the support was washed in a water wash bath at room temperature and further dried with hot air at 100°C to obtain a polarizer protective film. A roll-shaped polyvinyl alcohol film was stretched in the MD (machine direction) direction in an iodine aqueous solution and dried to obtain Polarizer 1 with a thickness of 14 μm. The polarizer protective film was attached to both surfaces of Polarizer 1 using a PVA adhesive, thereby producing Polarizer 1 with protective films.

[0208] [Preparation of UV adhesive 1] UV adhesive 1 was prepared having the following composition: --------------------------------------------------- UV adhesive 1 --------------------------------------------------- CEL2021P (manufactured by Daicel Corporation) 70 parts by mass 1,4-butanediol diglycidyl ether 20 parts by mass 2-ethylhexyl glycidyl ether 10 parts by mass CPI-100P 2.25 parts by mass ---------------------------------------------------

[0209] CPI-100P

[0210]

[0211] [Preparation of Polarizing Plate 1-3] The positive C plate side of the positive C plate FC-1 prepared above was attached to the surface of the optical film F1-3 of the laminate F1-3 using the UV adhesive 1, and 1000 mJ / cm 2 was applied from the positive C plate FC-1 side. ２The UV adhesive was cured by irradiating ultraviolet light of 1000 kJ / cm 2 to obtain a laminate. Subsequently, the alignment film and cellulose acylate film A1 on the laminate F1-3 side were removed to obtain a laminate FI1-3 with an optical film. The protective film-attached polarizer 1 prepared above was attached to the optical film F1-3 side of the optical film-attached laminate FI1-3 using a pressure-sensitive adhesive SK-2057 (manufactured by Soken Chemical & Engineering Co., Ltd.), and the alignment film and cellulose acylate film A1 on the positive C-plate FC-1 side were removed to complete a polarizing plate 1-3. At this time, the attachment was performed so that the angle between the absorption axis of the polarizer included in the protective film-attached polarizer 1 and the slow axis of the optical film F1-3 was 45°.

[0212] [Preparation of Polarizing Plates 1-2, 1-4 to 1-6, and 2-3] Polarizing plates 1-2, 1-4 to 1-5, and 2-3 were prepared in the same manner as polarizing plate 1-3, except that laminate F1-2, F1-4 to F1-6, or F2-3 was used instead of laminate F1-3. In all cases, polarizing plates were successfully prepared. When laminate F1-1, F2-1, or F2-2 was used instead of laminate F1-3, the UV adhesive 1 did not adhere to the optical film, and a polarizing plate could not be prepared.

[0213] [Fabrication of Image Display Device 1] A GALAXY S4 manufactured by SAMSUNG equipped with an organic EL panel (organic EL display element) was disassembled, the touch panel with a polarizing plate was peeled off from the organic EL display element, and the polarizing plate was further peeled off from the touch panel to isolate the organic EL display element, touch panel, and polarizing plate. The isolated touch panel was then reattached to the organic EL display element, and the polarizing plate 1-3 prepared above was then attached to the touch panel via an adhesive SK-2057 (manufactured by Soken Chemical & Engineering Co., Ltd.) so that the optically anisotropic layer side faced the panel side, thereby producing Organic EL Display Device 1.

[0214] [Measurement of Film Properties] [Water Contact Angle] The water contact angle was measured for the surface of each of the prepared optical films (specifically, the surface that had been subjected to corona treatment or plasma treatment in Examples 1 to 6 and Comparative Example 3) using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., DMo-702, temperature 25°C, humidity 50%, waiting time 20 seconds).

[0215] [XPS Measurement of Film Surface] The surface of each prepared optical film (specifically, the surface that had been subjected to corona treatment or plasma treatment in Examples 1 to 6 and Comparative Example 3) was subjected to XPS measurement by the method described above, and the abundance ratio of silicon atoms on the film surface and the binding energy of the peak top of the Si2p photoelectron spectrum were obtained. Furthermore, peak separation was performed on the obtained Si2p photoelectron spectrum by the method described above, and the area ratio of each peak was calculated.

[0216] [Surface Elastic Modulus and Surface Adsorption Force] For the surface of each optical film produced (specifically, for the surfaces subjected to corona treatment or plasma treatment in Examples 1 to 6 and Comparative Example 3), the surface elastic modulus and surface adsorption force were calculated by fitting the load / displacement curve obtained using the following device and conditions with the JKR contact mechanics model. Device: Bruker Dimension Icon Probe: RTESPA300 Mode: QNM Maximum load: 100 nN Indentation depth: <10 nm

[0217] [Evaluation] [Adhesion] Each polarizing plate thus prepared was cut vertically and horizontally at 1 mm intervals from the positive C-plate side to form 100 grids. Adhesive tape (polyester adhesive tape No. 31B, manufactured by Nitto Denko) was applied to the grids, and the tape was peeled off at an angle of approximately 60°. The number of peeled grids was counted, and the results were evaluated according to the following criteria. XPS confirmed that the peel interface was the interface between the cured layer of UV adhesive 1 and the optical film described above.

[0218] A: The number of peeled squares is 20 or less. B: The number of peeled squares is 21 or more and 50 or less. C: The number of peeled squares is 51 or more and 90 or less. D: The number of peeled squares is 91 or more, or the UV adhesive and the optical film surface do not adhere to each other, making it impossible to produce a polarizing plate.

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

[0220]

[0221]

[0222] From the above table, it was confirmed that the film of the present invention has excellent adhesion to adjacent layers (for example, adhesive layers).

[0223] A comparison of Examples 1 to 5 confirmed that when the surface elastic modulus was 4.0 GPa or higher, adhesion was superior, and when it was 5.1 GPa or higher, adhesion was even superior. A comparison of Examples 1 to 6 confirmed that when the surface adsorptive force was 12.0 nN or higher, adhesion was superior, and when it was 20.0 nN or higher, adhesion was even superior. A comparison of Examples 1 to 6 confirmed that when the peak top binding energy in the Si2p photoelectron spectrum obtained by measuring the film surface by X-ray photoelectron spectroscopy was 102.5 eV or higher, adhesion was superior, and when it was 103.2 eV or higher, adhesion was even superior. A comparison of Examples 1 to 6 confirmed that when the peak area assigned to a silicon atom bonded to four oxygen atoms in the Si2p photoelectron spectrum obtained by measuring the film surface by X-ray photoelectron spectroscopy was 30% or higher of the peak area in the Si2p photoelectron spectrum, adhesion was superior, and when it was 97% or higher, adhesion was even superior.

[0224] When TOF-SIMS was performed on the surface of each optical film, it was found that the optical films of Examples 1 to 6 had a thickness of 100 μm (SiO ２ ) ｌFragments with molecular weights corresponding to (l = 1 to 7) were detected. On the other hand, the above fragments were not detected in the optical films of Comparative Examples 1 to 3. That is, it was confirmed that silicon dioxide, which was not contained in the liquid crystal composition, was produced in the films of the present invention. The above results also confirmed the presence of silicon atoms to which four oxygen atoms are bonded on the surfaces of the optical films (specifically, the corona-treated surfaces in Examples 1 to 5 and the plasma-treated surface in Example 6).

[0225] [Preparation of laminate F3-1]

[0226] <Alkaline Saponification Treatment of Cellulose Acylate Film A1> The cellulose acylate film A1 was passed through a dielectric heating roll at a temperature of 60°C to raise the film surface temperature to 40°C, and then an alkaline solution having the composition shown below was applied to the band surface of the film using a bar coater in an amount of 14 ml / m. ２ The film was then conveyed for 10 seconds under a steam-type far-infrared heater manufactured by Noritake Co., Ltd. that had been heated to 110° C. Subsequently, pure water was applied to the film at a rate of 3 ml / m using the same bar coater. ２ Next, after repeating washing with water using a fountain coater and draining with an air knife three times, the film was transported to a drying zone at 70° C. for 10 seconds and dried to prepare an alkali-saponified cellulose acylate film A1.

[0227] ------------------------------------------------------------------- Alkaline solution --------------------------------------------------- Potassium hydroxide 4.7 parts by mass Water 15.8 parts by mass Isopropanol 63.7 parts by mass Surfactant: C １４ H ２９ O (CH ２ CH ２ O) ２０H 1.0 mass part Propylene glycol 14.8 mass parts

[0228] <Formation of Orientation Film Y1> An orientation film coating solution having the following composition was continuously applied to the alkaline saponified surface of the cellulose acylate film A1 using a #14 wire bar. The resulting coating film was dried with hot air at 60°C for 60 seconds and then with hot air at 100°C for 120 seconds to form the orientation film Y1.

[0229] Alignment film coating liquid -------------------------------- Polyvinyl alcohol (listed below) 10 parts by mass Water 371 parts by mass Methanol 119 parts by mass Glutaraldehyde (crosslinking agent) 0.5 parts by mass Citric acid ester (manufactured by Sankyo Chemical Co., Ltd.) 0.175 parts by mass ------------------------------------------------

[0230] (Polyvinyl alcohol)

[0231]

[0232] <Formation of Optical Film F3-1> The orientation film Y1 prepared above was continuously subjected to a rubbing treatment. At this time, the longitudinal direction of the long film was parallel to the conveying direction, and the angle between the longitudinal direction of the film (conveying direction) and the rotation axis of the rubbing roller was 76°. Assuming that the longitudinal direction of the film (conveying direction) is 90°, and the clockwise direction as observed from the film side is expressed as a positive value with the film width direction as the reference (0°), the rotation axis of the rubbing roller was at -14°. In other words, the position of the rotation axis of the rubbing roller was a position rotated 76° clockwise with the longitudinal direction of the film as the reference when observed from the film side.

[0233] A liquid crystal composition F3-1 containing a discotic liquid crystal compound having the following composition was applied to the rubbed alignment film Y1 using a Giesser coater to form a composition layer. The resulting composition layer was then heated with hot air at 80°C for 2 minutes to dry the solvent and ripen the alignment of the discotic liquid crystal compound. Subsequently, the resulting composition layer was irradiated with UV light (500 mJ / cm) at 80°C. ２ ) was performed to fix the alignment of the liquid crystal compound, thereby forming optical film F3-1. This resulted in a laminate F3-1 having, in this order, a support (cellulose acylate film A1), an alignment film Y1, and optical film F3-1. The thickness of optical film F3-1 was 1.4 μm. Furthermore, the in-plane retardation at a wavelength of 550 nm was 168 nm. The average tilt angle of the discotic surface of the discotic liquid crystal compound with respect to the film surface was 90°, confirming that the compound was aligned perpendicular to the film surface. Furthermore, the angle of the in-plane slow axis of optical film F3-1 was parallel to the rotation axis of the rubbing roller, and when the width direction of the film was 0° (the longitudinal direction was 90° counterclockwise and −90° clockwise), the in-plane slow axis was −14° when viewed from the optical film F3-1 side.

[0234] Liquid crystal composition F3-1 - 80 parts by mass of discotic liquid crystal compound DL-1 (shown below) 20 parts by mass of discotic liquid crystal compound DL-2 (shown below) Vertical alignment agent V-1 1.2 parts by mass Leveling agent SA-2 (shown below) 0.18 parts by mass Ethylene oxide modified trimethylolpropane triacrylate (V#360, manufactured by Osaka Organic Chemical Co., Ltd.) 5 parts by mass Photopolymerization initiator S-1 4.0 parts by mass Antifoaming agent B-1 2.0 parts by mass Methyl ethyl ketone 200 parts by mass -----------------------------------------------------------------

[0235] Discotic liquid crystal compound DL-1

[0236]

[0237] Discotic liquid crystal compound DL-2

[0238]

[0239] Vertical alignment agent V-1

[0240]

[0241] Leveling agent SA-2 (in the formula, a and b represent the content (% by mass) of each repeating unit relative to all repeating units, where a represents 70% by mass, b represents 24% by mass, and c represents 6% by mass. The weight-average molecular weight was 18,000.)

[0242]

[0243] Photopolymerization initiator S-1

[0244]

[0245] Defoamer B-1

[0246]

[0247] [Preparation of Laminates F3-2 to F3-4] The surface of the optical film F3-1 of the laminate F3-1 was subjected to corona treatment or plasma treatment under the conditions shown in Table 3 below to form optical films F3-2 to F3-4, thereby preparing laminates F3-2 to F3-4.

[0248] [Preparation of Laminate F4-1] A liquid crystal composition F4-1C containing a rod-shaped liquid crystal compound having the following composition was applied onto the cellulose acylate film A1 using a Giesser coater to form a composition layer. Thereafter, both ends of the film were held, and a cooling plate (9°C) was placed on the side of the film on which the composition layer was formed so as to be 5 mm away from the film, and a heater (75°C) was placed on the side opposite the side on which the composition layer was formed so as to be 5 mm away from the film, and the film was dried for 2 minutes. The film was then heated with warm air at 60°C for 1 minute, and irradiated with a 365 nm UV-LED at an irradiation dose of 100 mJ / cm while nitrogen purging was performed to maintain an atmosphere with an oxygen concentration of 100 ppm or less. ２The optical film F4-1C was then annealed with hot air at 120°C for 1 minute to form an optical film F4-1C. The obtained optical film F4-1C was irradiated with UV light (ultra-high pressure mercury lamp; UL750; manufactured by HOYA) at room temperature through a wire grid polarizer at a dose of 7.9 mJ / cm. ２ By irradiating the film with light (wavelength: 313 nm), alignment control ability was imparted to the surface. The film thickness of the formed optical film F4-1C was 0.7 μm. The in-plane retardation Re at a wavelength of 550 nm was 0 nm, and the retardation Rth in the thickness direction at a wavelength of 550 nm was −68 nm. The average tilt angle of the long axis direction of the rod-like liquid crystal compounds with respect to the film plane was 90°, and it was confirmed that the compounds were aligned perpendicular to the film plane.

[0249] 4 parts by mass of the liquid crystal compound LC-3; 4.2 parts by mass of polymerizable monomer (A-400, manufactured by Shin-Nakamura Chemical Co., Ltd.); 5.1 parts by mass of the polymerization initiator PI-1; 3.0 parts by mass of the photoacid generator D-1 described below; 2.0 parts by mass of the polymer M-1 described below; 1.9 parts by mass of the vertical alignment agent V-2 described below; 0.8 parts by mass of the photoalignment polymer P-1 described below; 0.2 parts by mass of diisopropylethylamine; 23.5 parts by mass of methyl ethyl ketone; 70.4 parts by mass of ethyl propionate; 375.0 parts by mass of methyl isobutyl ketone. ----------------------------------------------------------------------------------

[0250] Photoacid generator D-1

[0251]

[0252] Polymer M-1 (The numerical value for each repeating unit represents the content (% by mass) of all repeating units. The weight-average molecular weight was 60,000.)

[0253]

[0254] Vertical alignment agent V-2

[0255]

[0256] Photoalignment polymer P-1 (The numerical values ​​shown in the repeating units represent the content (mass%) of each repeating unit relative to all repeating units. Weight average molecular weight: 90,000. Me represents a methyl group.)

[0257]

[0258] Next, a liquid crystal composition F4-1A having the following composition was applied onto the optical film F4-1C prepared above using a Giesser coater, and heated with hot air at 80°C for 60 seconds. Subsequently, the resulting composition layer was irradiated with UV light (500 mJ / cm) at 80°C. ２ ) was performed, and the orientation of the liquid crystal compound was fixed to form optical film F4-1A, thereby obtaining laminate F4-1. The thickness of optical film F4-1A was 1.5 μm, Δnd at a wavelength of 550 nm was 164 nm, and the twist angle of the liquid crystal compound was 81°. When the width direction of the film was set to 0° (the longitudinal direction was 90°), the position of the in-plane slow axis (orientation axis angle of the liquid crystal compound) of optical film F4-1A when viewed from the optical film F4-1A side was 14° on the air side and 95° on the side in contact with optical film F4-1C. The position of the in-plane slow axis of the optical film was expressed by observing the substrate from the surface side of the optical film, with the width direction of the film set to 0° as the reference, and clockwise (right-handed) rotation being negative and counterclockwise (left-handed) rotation being positive. The twist angle of the liquid crystal compound is expressed as follows: when observing the substrate from the surface side of the optical film, the orientation axis direction of the liquid crystal compound on the surface side (front side) is taken as the reference; when the orientation axis direction of the liquid crystal compound on the substrate side (rear side) is clockwise (right-handed), it is negative; and when it is counterclockwise (left-handed), it is positive.

[0259] 58.1 parts by mass of the above liquid crystal compound LC-1 10.5 parts by mass of the above liquid crystal compound LC-2 1.4 parts by mass of the above liquid crystal compound LC-3 30.0 parts by mass of the following rod-shaped liquid crystal compound LC-4 4.0 parts by mass of ethylene oxide-modified trimethylolpropane triacrylate (V#360, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 3.0 parts by mass of photopolymerization initiator (Irgacure 819, manufactured by BASF) 0.48 parts by mass of the following chiral agent C-1 0.15 parts by mass of the above leveling agent SA-1 0.70 parts by mass of diisopropylethylamine 126.5 parts by mass of ethyl propionate 126.5 parts by mass of methyl isobutyl ketone 126.5 parts by mass ――――――――――――――――――――――――――――――――

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

[0261]

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

[0263]

[0264] By the above procedure, a laminate F4-1 was prepared in which the optical film F4-1C and the optical film F4-1A were directly laminated on a long cellulose acylate film.

[0265] [Preparation 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 preparing laminates F4-2 to F4-4.

[0266] [Preparation of Polarizing Plate 3-2] The surface of the optical film F4-2A of the laminate F4-2 was attached to the surface of the optical film F3-2 of the laminate F3-2 using the UV adhesive 1, and 1000 mJ / cm 2 was applied from the laminate F4-2 side. ２ The laminate was irradiated with ultraviolet light of 1000 W at ...

[0267] [Preparation of Polarizing Plates 3-3 to 3-4] Polarizing plate 3-3 was prepared in the same manner as polarizing plate 3-2, except that the laminate F3-3 was used instead of the laminate F3-2 and the laminate F4-3 was used instead of the laminate F4-2. Polarizing plate 3-4 was prepared in the same manner as polarizing plate 3-2, except that the laminate F3-4 was used instead of the laminate F3-2 and the laminate F4-4 was used instead of the laminate F4-2. In both cases, polarizing plates were successfully prepared. When the laminate F3-1 was used instead of the laminate F3-2 and the laminate F4-1 was used instead of the laminate F4-2, the UV adhesive 1 and the optical film did not adhere to each other, and a polarizing plate could not be prepared.

[0268] [Measurement of Film Properties] The surface properties of each optical film were measured in the same manner as in Examples 1 to 6 and Comparative Examples 1 to 3.

[0269] [Evaluation] [Adhesion] 11 cuts were made in each of the prepared polarizing plates 3-2 to 3-4 on the optical film F3-2 to F3-4 side at 1 mm intervals, vertically and horizontally, to form 100 grids. Adhesive tape (polyester adhesive tape No. 31B, manufactured by Nitto Denko) was applied to the grids, and the tape was peeled off at an angle of approximately 60°. The number of peeled grids was counted, and the results were evaluated according to the following criteria. XPS confirmed that the peel interface was either the interface between the cured layer of UV adhesive 1 and the optical films F3-2 to F3-4 described above, or the interface between the cured layer of UV adhesive 1 and the optical films F4-2A to F4-4A described above.

[0270] A: The number of peeled squares is 20 or less. B: The number of peeled squares is 21 or more and 50 or less. C: The number of peeled squares is 51 or more and 90 or less. D: The number of peeled squares is 91 or more, or the UV adhesive and the optical film surface do not adhere to each other, making it impossible to produce a polarizing plate.

[0271] [Results] The type of each optical film, as well as the corona treatment conditions and plasma treatment conditions, are shown in Table 3 below, and the surface properties and evaluation results of each film are shown in Table 4 below. For optical films F3-2 to F3-4 and optical films F4-2 to F4-4, measurements were performed on surfaces that had been subjected to corona treatment or plasma treatment. In the tables below, the SA-1 (parts by mass) column indicates the amount (parts by mass) of leveling agent SA-1 used in the liquid crystal composition used to form each optical film, and the SA-2 (parts by mass) column indicates the amount (parts by mass) of leveling agent SA-2 used in the liquid crystal composition used to form each optical film. In the tables below, the peak top (eV) column indicates the binding energy of the peak top of the Si2p photoelectron spectrum.

[0272]

[0273]

[0274] Comparison of Examples 7 to 9 and Comparative Example 4 above also confirmed that the film of the present invention has excellent adhesion to adjacent layers (for example, adhesive layers).

[0275] REFERENCE SIGNS LIST 10 Laminate 12 Liquid crystal layer 14 Alignment film 16 Support 20 Polarizing plate 22 Polarizer 24 First adhesive layer 26 First liquid crystal layer 28 Second adhesive layer 30 Second liquid crystal layer

Claims

1. A film formed using a liquid crystal composition containing a liquid crystal compound and a leveling agent containing silicon atoms, wherein the binding energy of the peak top in the Si2p photoelectron spectrum obtained by measuring the surface of the film by X-ray photoelectron spectroscopy is 102.0 eV or more.

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

3. The film described in claim 2, wherein in a photoelectron spectrum of Si2p obtained by measuring the surface of the film by X-ray photoelectron spectroscopy, the peak area assigned to a silicon atom to which four oxygen atoms are bonded is 30% or more of the peak area of ​​the photoelectron spectrum of Si2p.

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

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

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

7. An image display device comprising the polarizing plate according to claim 6.

8. The image display device according to claim 7, which is an organic electroluminescence display device.

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

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