Method for manufacturing a patterned liquid crystal display element

Abstract

The present invention provides a method for manufacturing a liquid crystal display element having two or three different alignment regions (in-plane (uniaxial) alignment region, out-of-plane alignment region, and tilted alignment region) within the same element, which is a simple and inexpensive method. The method for manufacturing a liquid crystal display element includes: step (A): a step of forming a radical generating film capable of generating radicals by light irradiation on a substrate; and step (B): bringing a liquid crystal composition containing a liquid crystal and a radical polymerizable compound into contact with the radical generating film, and while maintaining this state, irradiating the liquid crystal composition with light having a peak in the range of 240 to 400 nm sufficient to cause a polymerization reaction of the radical polymerizable compound. The radical polymerizable compound, by polymerization, has a function of vertically aligning the liquid crystal. Further, it includes at least one of the following requirements (Z1) and (Z2), and manufactures a liquid crystal display element in which at least two of the in-plane alignment region, out-of-plane alignment region, and tilted alignment region are patterned. Requirement (Z1): There is also a step (C) of irradiating the radical generating film obtained in step (A) with light having a peak in the range of 240 to 400 nm between step (A) and step (B) to inactivate the radical generating ability of the radical generating film. Requirement (Z2): The step of irradiating the liquid crystal composition with light having a peak in the range of 240 to 400 nm in step (B) is performed through a photomask.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a liquid crystal display element in which at least two regions of an in-plane alignment region, an out-of-plane alignment region, and an inclined alignment region are patterned by using a method that is inexpensive and does not include complicated processes. Background Art

[0002] In recent years, liquid crystal display elements have been widely used in displays of mobile phones, computers, televisions, and the like. Liquid crystal display elements have characteristics such as being thin, lightweight, and having low power consumption, and are expected to be further applied to VR (Virtual Reality) or ultra-high-definition displays in the future. Various display mode proposals such as TN (Twisted Nematic), IPS (In-Plane Switching), and VA (Vertical Alignment) have been proposed for liquid crystal displays, but all modes use a film (liquid crystal alignment film) that induces liquid crystal into a desired alignment state.

[0003] In particular, in products having a touch panel such as a tablet PC, a smartphone, or a smart TV, the IPS mode in which the display is not easily disturbed even when touched is preferred. In recent years, in terms of improving the contrast ratio or the viewing angle characteristics, a liquid crystal display element using FFS (Fringe Field Switching) and a technique using photo-alignment, which is a non-contact technique, have been gradually adopted.

[0004] However, FFS has the following problems: compared with IPS, the manufacturing cost of the substrate is high, and display defects peculiar to the FFS mode called Vcom shift occur. In addition, regarding photo-alignment, compared with the rubbing method, it has the advantages of being able to increase the size of the element that can be manufactured or being able to significantly improve the display characteristics, but problems in the principle of photo-alignment can be cited (in the case of the decomposition type, display defects from decomposition products, and in the case of the isomerization type, afterimages due to insufficient alignment force, etc.). In order to solve these problems, various studies are currently being conducted by liquid crystal display element manufacturers or liquid crystal alignment film manufacturers.

[0005] On the other hand, in recent years, a proposal for an IPS mode using zero surface anchoring (also called weak anchoring) has been made, and it has been reported that by using this method, it is possible to improve the contrast ratio or achieve significant low-voltage driving compared with the conventional IPS mode (see Patent Document 1).

[0006] Specifically, a method for manufacturing an IPS mode liquid crystal display element is provided, in which a liquid crystal alignment film having a strong anchoring energy is used on one side substrate, and a treatment for removing all the alignment constraints of the liquid crystal is applied to the other substrate side provided with an electrode for generating a lateral electric field, and these are used.

[0007] In recent years, a zero surface state has been produced using a thick polymer brush or the like, and a technical solution of a zero surface anchoring IPS mode (also referred to as a weak anchoring IPS mode) has been proposed (see Reference 2). By this technique, a significant improvement in contrast ratio or a significant reduction in driving voltage is achieved.

[0008] On the other hand, there is a problem that the response speed, particularly the response speed when the voltage is OFF, is significantly reduced. This is because the driving voltage becomes lower, and thus the liquid crystal is made to respond with a weaker electric field as compared with the normal driving method, and since the anchoring force of the alignment film is extremely small, it takes time for the liquid crystal to recover.

[0009] As a method for solving this problem, a method of performing zero anchoring only on the pixel electrode has been proposed (for example, see Patent Document 3). Thereby, it has been reported that an improvement in brightness and a response speed can be achieved simultaneously.

[0010] Prior Art Documents

[0011] Patent Documents

[0012] Patent Document 1: Japanese Patent No. 4053530 Gazette

[0013] Patent Document 2: Japanese Unexamined Patent Application Publication No. 2013 - 231757

[0014] Patent Document 3: Japanese Unexamined Patent Application Publication No. 2017 - 211566 Summary of the Invention

[0015] Problems to be Solved by the Invention

[0016] When using an alignment film appropriately designed according to the use, it is possible to control various liquid crystal alignment states. In particular, when using an alignment film having an anchoring force in the in-plane uniaxial direction, in-plane uniaxial alignment is obtained, and when using an alignment film having an anchoring force in the out-of-plane direction, out-of-plane alignment is obtained.

[0017] On the other hand, it is very difficult to fabricate a liquid crystal element that simultaneously has an in-plane uniaxial alignment region and an out-of-plane alignment region within the same element. This is because regions with significantly different anchoring forces need to be fabricated within the same element. To achieve this, it is necessary to change the anchoring force of an arbitrary region after fabricating the liquid crystal element, or to separately coat alignment films with different anchoring forces on the substrates constituting the element in advance. There is still no reported example for the former, and the latter also poses a major challenge in industrialization because it requires precise separate coating in very fine regions and the preparation of techniques for performing alignment processing.

[0018] If such technical problems can be solved, a liquid crystal element with an arbitrary alignment state in an arbitrary region can be formed, and applications such as optical films or optical property modulation elements can be expected.

[0019] The present invention is made to solve the above problems, and an object thereof is to provide a method for manufacturing a liquid crystal display element, which controls the surface energy or anchoring energy of an interfacial reaction region to an arbitrary state by inducing a chemical reaction at the interface between an alignment film and a liquid crystal and inducing a chemical reaction in an arbitrary region in the in-plane direction of the alignment film, and manufactures a liquid crystal display element having two or three different alignment regions (in-plane (uniaxial) alignment region, out-of-plane alignment region, and tilted alignment region) within the same element in a simple and inexpensive manner.

[0020] Technical solutions for solving the problems

[0021] As a result of intensive research by the present inventors to solve the above problems, it has been found that the above problems can be solved, and the present invention with the following gist has been completed.

[0022] The present invention includes the following. [1]

[0024] A method for manufacturing a liquid crystal display element, characterized by comprising:

[0025] Step (A): a step of forming a radical generating film capable of generating radicals by irradiation with light on a substrate; and

[0026] Step (B): bringing a liquid crystal composition containing a liquid crystal and a radical polymerizable compound into contact with the radical generating film, and while maintaining this state, irradiating the liquid crystal composition with light having a peak in the range of 240 to 400 nm sufficient to cause the radical polymerizable compound to undergo a polymerization reaction,

[0027] The radical polymerizable compound has a function of vertically aligning the liquid crystal through polymerization,

[0028] Furthermore, a liquid crystal display element that includes at least one of the following requirements (Z1) and (Z2), and in which at least two of a in-plane alignment region, an out-of-plane alignment region, and an inclined alignment region are patterned.

[0029] Requirement (Z1): There is also a step (C) between step (A) and step (B) of irradiating the radical generating film obtained in step (A) with light having a peak in the range of 240 to 400 nm to deactivate the radical generating ability of the radical generating film.

[0030] Requirement (Z2): The step of irradiating the liquid crystal composition in step (B) with light having a peak in the range of 240 to 400 nm is performed through a photomask. [2]

[0032] The method for manufacturing a liquid crystal display element according to [1], wherein the radical generating film is a uniaxially oriented coating film. [3]

[0034] The method for manufacturing a liquid crystal display element according to [1] or [2], wherein the step of irradiating the liquid crystal composition in step (B) with light having a peak in the range of 240 to 400 nm is performed in the absence of an electric field. [4]

[0036] The method for manufacturing a liquid crystal display element according to any one of [1] to [3], wherein the radical generating film has a polymer containing an organic group that initiates radical polymerization. [5]

[0038] The method for manufacturing a liquid crystal display element according to [4], wherein the polymer containing an organic group that initiates radical polymerization has a structural unit represented by the following formula (1) in the main chain,

[0039] [Chemical formula 1]

[0040]

[0041] (In formula (1), A represents an organic group that initiates radical polymerization). [6]

[0043] The method for manufacturing a liquid crystal display element according to [4] or [5], wherein the polymer is selected from at least one of a polyimide precursor, polyimide, polyurea, and polyamide obtained using a diamine component containing a diamine having an organic group that initiates radical polymerization. [7]

[0045] The manufacturing method of the liquid crystal display element according to [5], wherein the organic group that initiates radical polymerization is a group represented by the following formula (3).

[0046] [Chemical formula 2]

[0047]

[0048] (In formula (3), the dashed line represents the bond with the benzene ring, and R 6 represents a single bond, -CH2-, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH2O-, -N(CH3)-, -CON(CH3)- or -N(CH3)CO-.

[0049] R 7 represents a single bond, or an unsubstituted or fluorine atom-substituted alkylene group having 1 to 20 carbon atoms. One or more of any -CH2- or -CF2- in the alkylene group are each independently optionally replaced by a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and further optionally replaced by any of the following groups, namely -O-, -COO-, -OCO-, -NHCO-, -CONH- or -NH-, provided that these groups are not adjacent to each other.

[0050] R 8 represents an organic group that initiates radical polymerization and is represented by a formula selected from formulae [X-1] to [X-18], [W], [Y], [Z].

[0051] [Chemical formula 3]

[0052]

[0053] In formulae [X-1] to [X-18], * represents the bonding site with R 7 , S1 and S2 each independently represent -O-, -NR-, or -S-, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R1 and R2 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.

[0054] [Chemical formula 4]

[0055]

[0056] In formulae [W], [Y], [Z], * represents the bonding site with R 7 , and S 3represents a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH2O-, -N(CH3)-, -CON(CH3)-, or -N(CH3)CO-; Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylene which may optionally have an organic group and / or a halogen atom as a substituent; R 9 and R 10 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group, or a phenethyl group. When it is an alkyl group or an alkoxy group, R 9 and R 10 may optionally form a ring.

[0057] Q represents any one of the following structures:

[0058] [Chemical Formula 5]

[0059]

[0060] In the formula, R 11 represents -CH2-, -NR-, -O-, or -S-; R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; * represents a bonding position.

[0061] R 12 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms). [8]

[0063] According to the method for manufacturing a liquid crystal display element described in [6], wherein the diamine containing an organic group that initiates radical polymerization is a diamine represented by the following formula (2):

[0064] [Chemical Formula 6]

[0065]

[0066] (In formula (2), A 1 and A 2 each represent a hydrogen atom or a group represented by the following formula (3). Among them, at least one of A 1 and A 2 represents a group represented by the following formula (3).

[0067] E represents a single bond, -O-, -C(CH3)2-, -NH-, -CO-, -NHCO-, -COO-, -(CH2) m -, -SO2-, or a divalent organic group composed of any combination of these; m represents an integer from 1 to 8.

[0068] p represents an integer from 0 to 2. When p is 2, multiple A2 and E each independently have the above definitions. Additionally, when p is 0, A 1 is composed of a group represented by the following formula (3).

[0069] [Chemical formula 7]

[0070]

[0071] (In formula (3), the dashed line represents the bonding to the benzene ring, and R 6 represents a single bond, -CH2-, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH2O-, -N(CH3)-, -CON(CH3)-, or -N(CH3)CO-

[0072] R 7 represents a single bond, or an unsubstituted or fluorine atom-substituted alkylene group having 1 to 20 carbon atoms. One or more of any -CH2- or -CF2- in the alkylene group are each independently optionally replaced by a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring. Further, under the condition that any of the following groups, namely -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other, they are optionally replaced by these groups.

[0073] R 8 represents an organic group that initiates radical polymerization and is represented by a formula selected from formulae [X-1] to [X-18], [W], [Y], and [Z].[[]END]]

[0074] [Chemical formula 8]

[0075]

[0076] In formulae [X-1] to [X-18], * represents the bonding site to R 7 , S1 and S2 each independently represent -O-, -NR-, or -S-, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R1 and R2 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.

[0077] [Chemical formula 9]

[0078]

[0079] In formulae [W], [Y], and [Z], * represents the bonding site to R 7 , and S 3represents a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH2O-, -N(CH3)-, -CON(CH3)-, or -N(CH3)CO-; Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylene which may optionally have an organic group and / or a halogen atom as a substituent; R 9 and R 10 each independently represents an alkyl group, an alkoxy group, a benzyl group, or a phenethyl group having 1 to 10 carbon atoms. When it is an alkyl group or an alkoxy group, R 9 and R 10 optionally form a ring.

[0080] Q represents any of the following structures:

[0081] [Chemical Formula 10]

[0082]

[0083] In the formula, R 11 represents -CH2-, -NR-, -O-, or -S-; R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; * represents a bonding position.

[0084] R 12 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms). [9]

[0086] The method for manufacturing a liquid crystal display element according to any one of [1] to [8], wherein at least one of the radical polymerizable compounds is a compound having one polymerizable unsaturated bond in one molecule and being compatible with liquid crystal.

[10]

[0088] The method for manufacturing a liquid crystal display element according to [9], wherein the polymerization reactive group possessed by the radical polymerizable compound is selected from the following structures:

[0089] [Chemical Formula 11]

[0090]

[0091] (In the formula, * represents a site bonded to a part other than the polymerizable unsaturated bond of the compound molecule; R b represents an alkyl group having 3 to 20 carbon atoms; E represents a bonding group selected from a single bond, -O-, -NRc-, -S-, an ester bond, and an amide bond. R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; the alkyl group of R b represents a straight-chain, branched, or cyclic alkyl group).

[11]

[0093] The method for manufacturing a liquid crystal display element according to any one of [1] to

[10] , wherein, in the liquid crystal composition containing a liquid crystal and a radical polymerizable compound, a radical polymerizable compound having a Tg of 100 °C or lower of a polymer obtained by polymerizing the radical polymerizable compound is contained.

[12]

[0095] The method for manufacturing a liquid crystal display element according to any one of [1] to

[11] , further comprising a step of manufacturing a liquid crystal cell by the following steps:

[0096] Preparing a first substrate having a radical generating film and a second substrate;

[0097] Disposing the radical generating film on the first substrate to face the second substrate; and

[0098] Filling a liquid crystal composition containing a liquid crystal and a radical polymerizable compound between the first substrate and the second substrate.

[13]

[0100] The method for manufacturing a liquid crystal display element according to

[12] , wherein the second substrate has a radical generating film.

[14]

[0102] The method for manufacturing a liquid crystal display element according to

[12] , wherein the second substrate is a substrate covered with a liquid crystal alignment film having uniaxial orientation.

[15]

[0104] The method for manufacturing a liquid crystal display element according to

[14] , wherein the liquid crystal alignment film having uniaxial orientation is a liquid crystal alignment film for horizontal alignment.

[16]

[0106] The method for manufacturing a liquid crystal display element according to any one of

[12] to

[15] , wherein the first substrate having a radical generating film is a substrate having a comb-shaped electrode.

[0107] Advantages of the Invention

[0108] According to the present invention, it is possible to provide a method for manufacturing a liquid crystal display element that can manufacture a liquid crystal display element having two or three different alignment regions (in-plane (uniaxial) alignment region, out-of-plane alignment region, and tilted alignment region) in the same element in a simple and inexpensive manner. BRIEF DESCRIPTION OF THE DRAWINGS

[0109] Figure 1AIt is a photograph of the liquid crystal display element obtained in Example 5.

[0110] Figure 1B It schematically shows Figure 1A a figure of the photograph of the liquid crystal display element.

[0111] Figure 2A It is a photograph of the liquid crystal display element obtained in Comparative Example 4.

[0112] Figure 2B It schematically shows Figure 2A a figure of the photograph of the liquid crystal display element.

[0113] Figure 3A It is a photograph of the liquid crystal display element obtained in Example 1.

[0114] Figure 3B It schematically shows Figure 3A a figure of the photograph of the liquid crystal display element.

[0115] Figure 4A It is a photograph of the liquid crystal display element obtained in Example 23.

[0116] Figure 4B It schematically shows Figure 4A a figure of the photograph of the liquid crystal display element.

[0117] Figure 5A It is a photograph of the liquid crystal display element obtained in Example 24.

[0118] Figure 5B It schematically shows Figure 5A a figure of the photograph of the liquid crystal display element.

[0119] Figure 6 It is a photograph of the liquid crystal display element obtained in Example 25 and Example 26.

[0120] Figure 7 It is a photograph of the liquid crystal display element obtained in Example 27.

[0121] Figure 8 It is a photograph of the liquid crystal display element obtained in Example 30.

[0122] Figure 9A It is a photograph of the liquid crystal display element obtained in Example 32.

[0123] Figure 9B It schematically shows Figure 9A a figure of the photograph of the liquid crystal display element.

[0124] Figure 10 It is a schematic cross-sectional view showing an example of the liquid crystal display element according to the present invention.

[0125] Figure 11 This is a schematic cross-sectional view showing other examples of the liquid crystal display element according to the present invention. Detailed Description of the Invention

[0126] Hereinafter, the manufacturing method of the liquid crystal display element of the present invention has been described in detail. However, the description of the structural elements described below is an example of one embodiment of the present invention and is not limited to these contents.

[0127] (Manufacturing Method of Liquid Crystal Display Element)

[0128] The manufacturing method of the liquid crystal display element of the present invention includes the following step (A) and the following step (B).

[0129] Step (A): A step of forming a radical generating film capable of generating radicals by irradiation with light on a substrate;

[0130] Step (B): A liquid crystal composition containing a liquid crystal and a radical polymerizable compound is brought into contact with the radical generating film, and while maintaining this state, light having a peak in the range of 240 to 400 nm sufficient to cause the radical polymerizable compound to undergo a polymerization reaction is irradiated onto the liquid crystal composition.

[0131] The radical polymerizable compound in the above step (B) is a compound that, through polymerization, has the function of vertically aligning the liquid crystal;

[0132] Furthermore, the manufacturing method of the liquid crystal display element of the present invention includes at least one of the following requirements (Z1) and (Z2).

[0133] Requirement (Z1): There is also a step (C) of irradiating the radical generating film obtained in step (A) with light having a peak in the range of 240 to 400 nm to inactivate the radical generating ability of the radical generating film between step (A) and step (B).

[0134] Requirement (Z2): The step of irradiating the liquid crystal composition with light having a peak in the range of 240 to 400 nm in step (B) is performed through a photomask.

[0135] The present invention including the above step (A) and step (B) and further satisfying at least one of the requirements (Z1) and (Z2) can manufacture a liquid crystal display element in which at least two regions among the in-plane alignment region, the out-of-plane alignment region, and the tilted alignment region are patterned.

[0136] <Radical Generating Film>

[0137] In the present invention, a radical generating film is formed on a substrate.

[0138] Here, the free radical generating film refers to a coated film that generates free radicals.

[0139] The free radical generating film is formed, for example, from a free radical generating film forming composition.

[0140] <Free radical generating film forming composition>

[0141] As components of the free radical generating film forming composition, a polymer and a group capable of generating free radicals are included. At this time, the free radical generating film forming composition may be a composition containing a polymer bonded with a group capable of generating free radicals, or may be a composition of a compound having a group capable of generating free radicals and a polymer serving as a base resin.

[0142] By coating such a free radical generating film forming composition on a substrate and curing the coated film, a free radical generating film in which a group capable of generating free radicals is immobilized in the film can be obtained. The group capable of generating free radicals is preferably an organic group that initiates free radical polymerization.

[0143] When the free radical generating film is composed of a polymer containing an organic group that initiates free radical polymerization, examples of the polymer containing the organic group that induces the free radical polymerization include polymers having a structural unit represented by the following formula (1) in the main chain.

[0144] [Chemical formula 12]

[0145]

[0146] In formula (1), A represents an organic group that initiates free radical polymerization.

[0147] When using a polymer containing an organic group that initiates free radical polymerization, in order to obtain a polymer having a group capable of generating free radicals, it is preferably manufactured using, as monomer components, at least one monomer having a photoreactive side chain selected from methacryloyl, acryloyl, vinyl, allyl, coumarin, styryl, and cinnamoyl, or a monomer that decomposes upon light irradiation to have a free radical generating site on the side chain. On the other hand, considering problems such as the fact that the free radical generating monomer itself may spontaneously polymerize, there is a risk of finally forming an unstable compound.

[0148] Therefore, in terms of ease of synthesis, a polymer derived from a diamine having a free radical generating site is preferred, and polyamic acid, polyamic acid ester and other polyimide precursors, polyimide, polyurea, polyamide, etc. are more preferred.

[0149] Examples of the organic group that initiates free radical polymerization include the group represented by the following formula (3).

[0150] [Chemical Formula 13]

[0151]

[0152] (In Formula (3), the dashed line represents bonding to the benzene ring, and R 6 represents a single bond, -CH2-, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH2O-, -N(CH3)-, -CON(CH3)-, or -N(CH3)CO-;

[0153] R 7 represents a single bond, or an unsubstituted or fluorine atom-substituted alkylene group having 1 to 20 carbon atoms, and one or more of any -CH2- or -CF2- in the alkylene group are each independently optionally replaced by a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and further optionally replaced by any of the following groups, namely -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH-, provided that these groups are not adjacent to each other;

[0154] R 8 represents an organic group that initiates radical polymerization represented by a formula selected from Formulas [X-1] to [X-18], [W], [Y], and [Z];

[0155] [Chemical Formula 14]

[0156]

[0157] In Formulas [X-1] to [X-18], * represents the bonding site to R 7 , S1 and S2 each independently represent -O-, -NR-, or -S-, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R1 and R2 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms;

[0158] [Chemical Formula 15]

[0159]

[0160] In Formulas [W], [Y], and [Z], * represents the bonding site to R 7 , S 3 represents a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH2O-, -N(CH3)-, -CON(CH3)-, or -N(CH3)CO-, Ar represents an aromatic hydrocarbon group selected from the group consisting of a phenylene group, a naphthylene group, and a biphenylene group that may optionally have an organic group and / or a halogen atom as a substituent, and R9 and R 10 each independently represents an alkyl group, an alkoxy group, a benzyl group, or a phenethyl group having 1 to 10 carbon atoms. In the case of being an alkyl group or an alkoxy group, formed by R 9 and R 10 optionally form a ring,

[0161] Q represents any of the following structures,

[0162] [Chemical formula 16]

[0163]

[0164] In the formula, R 11 represents -CH2-, -NR-, -O-, or -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bonding position,

[0165] R 12 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

[0166] As the organic group represented by the formula selected from the above [W], [Y], and [Z], the following organic groups are specifically preferred. In particular, from the viewpoint of the reliability of the obtained liquid crystal display element, (b) and (c) are more preferred.

[0167] [Chemical formula 17]

[0168]

[0169] As a preferred embodiment of the polymer containing an organic group that initiates radical polymerization, a diamine having an organic group that initiates radical polymerization can be mentioned.

[0170] Such a diamine containing a radical generating site is specifically a diamine having a side chain capable of generating radicals and polymerizing, for example, a diamine represented by the following formula (2) can be mentioned. However, it is not limited thereto.

[0171] [Chemical formula 18]

[0172]

[0173] In formula (2), A 1 and A 2 each represent a hydrogen atom or a group represented by the above formula (3), wherein at least one of A 1 and A 2 represents a group represented by the above formula (3),

[0174] E represents a single bond, -O-, -C(CH3)2-, -NH-, -CO-, -NHCO-, -COO-, -(CH2)m -, -SO2-, or a divalent organic group composed of any combination of these, where m represents an integer from 1 to 8.

[0175] As "any combination of these", examples include: -O-(CH2) m -O-, -OC(CH3)2-, -CO-(CH2) m -, -NH-(CH2) m -, -SO2-(CH2) m -, -CONH-(CH2) m -, -CONH-(CH2) m -NHCO-, -COO-(CH2) m -OCO-, etc., but not limited thereto.

[0176] p represents an integer from 0 to 2. When p is 2, multiple A 2 and E each independently have the above definition. Additionally, when p is 0, A 1 is composed of the group represented by the following formula (3).

[0177] In the above formula (2), when p = 0, the bonding positions of the two amino groups (-NH2) are not limited. Specifically, examples include the bonding groups to the side chain, and the 2,3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 position, and 3,5 position on the benzene ring. Among them, from the perspective of the reactivity during the synthesis of polyamic acid, the 2,4 position, 2,5 position, or 3,5 position is preferred. If the ease of synthesizing diamine is also considered, the 2,4 position or 3,5 position is more preferred.

[0178] As a diamine having a photoreactive group containing at least one selected from the group consisting of methacryloyl, acryloyl, vinyl, allyl, coumarin, styryl, and cinnamoyl, specifically, the following compounds can be cited, but are not limited thereto.

[0179] [Chemical formula 19]

[0180]

[0181] [Chemical formula 20]

[0182]

[0183] (In the formula, J 1 represents a single bond, -O-, -COO-, -NHCO-, or -NH-, and J 2 represents a single bond, or an unsubstituted or fluorine atom-substituted alkylene group having 1 to 20 carbon atoms).

[0184] As the diamine of the organic group represented by the formula selected from the above [W], [Y] and [Z], in view of ease of synthesis, level of versatility, properties, etc., the structure represented by the following formula is most preferred, but not limited thereto.

[0185] [Chemical formula 21]

[0186]

[0187] (In the formula, n is an integer of 2 to 8, and E is a single bond, -O-, -C(CH3)2-, -NH-, -CO-, -NHCO-, -COO-, -(CH2) m -, -SO2-, -O-(CH2) m -O-, -O-C(CH3)2-, -CO-(CH2) m -, -NH-(CH2) m -, -SO2-(CH2) m -, -CONH-(CH2) m -, -CONH-(CH2) m -NHCO- or -COO-(CH2) m -OCO-, and m is an integer of 1 to 8).

[0188] [Chemical formula 22]

[0189]

[0190] (In the formula, n is an integer of 2 to 8).

[0191] The above diamine can also be used alone or in combination of two or more according to characteristics such as the liquid crystal alignment property when forming a radical generating film, the sensitivity in the polymerization reaction, the voltage holding property, and the accumulated charge.

[0192] For the diamine having a site generated by radical polymerization, it is preferably used in an amount of 5 to 50 mol%, more preferably 10 to 40 mol%, and particularly preferably 15 to 30 mol% of the total diamine component used for the synthesis of the polymer contained in the radical generating film forming composition.

[0193] In addition, in the case of obtaining the polymer used in the radical generating film of the present invention from a diamine, other diamines other than the above-mentioned diamine having a radical generating site can be used in combination as the diamine component. Specifically, examples include: p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-Bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(methylene)]dianiline, 4,4'-[1,3-phenylenebis(methylene)]dianiline, 3,4'-[1,4-phenylenebis(methylene)]dianiline, 3,4'-[1,3-phenylenebis(methylene)]dianiline, 3,3'-[1,4-phenylenebis(methylene)]dianiline, 3,3'-[1,3-phenylenebis(methylene)]dianiline, 1,4-phenylenebis[(4-aminophenyl)methanone], 1,4-phenylenebis[(3-aminophenyl)methanone], 1,3-phenylenebis[(4-aminophenyl)methanone], 1,3-phenylenebis[(3-aminophenyl)methanone], 1,4-phenylenebis(4-aminobenzoate), 1,4-phenylenebis(3-aminobenzoate), 1,3-phenylenebis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N,N'-(1,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(3-aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl)isophthalamide, N,N'-bis(3-aminophenyl)isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenyl sulfone, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, trans-1,4-bis(4-aminophenyl)cyclohexane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, bis(4-aminophenoxy)methane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,Aromatic diamines such as 4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis(3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)dodecane; Alicyclic diamines such as bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane; Aliphatic diamines such as 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane; Diamines with urea structure such as 1,3-bis[2-(p-aminophenyl)ethyl]urea, 1,3-bis[2-(p-aminophenyl)ethyl]-1-tert-butoxycarbonylurea; Diamines with nitrogen-containing unsaturated heterocyclic structure such as N-p-aminophenyl-4-p-aminophenyl(tert-butoxycarbonyl)aminomethylpiperidine; Diamines with N-Boc group (Boc represents tert-butoxycarbonyl) such as N-tert-butoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N-(4-aminobenzyl)amine, etc.,

[0194] These other diamines can also be used alone or in combination of two or more according to characteristics such as the liquid crystal alignment property when forming a radical generation film, the sensitivity in the polymerization reaction, the voltage holding property, and the accumulated charge, etc.,

[0195] In the synthesis when the polymer is polyamic acid, the tetracarboxylic dianhydride reacting with the diamine component described above is not particularly limited. Specifically, examples thereof include: pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3',4,4-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl) ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl) sulfone, bis(3,4-dicarboxyphenyl) methane, 2,2-bis(3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl) propane, bis(3,4-dicarboxyphenyl) dimethylsilane, bis(3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl) pyridine, 3,3',4,4'-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, oxydiphthalic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid, 3,4-dicarboxy-1-cyclohexyl succinic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid, bicyclo[4.3.0]nonane-2,4,7,9-tetracarboxylic acid, bicyclo[4.4.0]decane-2,4,7,9-tetracarboxylic acid, bicyclo[4.4.0]decane-2,4,8,10-tetracarboxylic acid, tricyclo[6.3.0.0<2,6>]undecane-3,5,9,11-tetracarboxylic acid, 1,2,3,4-butane tetracarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo[6.2.1.1<3,6>.0<2,7>]dodecane-4,5,9,10-tetracarboxylic acid, 3,5,6-tricarboxynorbornane-2:3,5:6-dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, etc., dianhydrides of tetracarboxylic acids.

[0196] Of course, the tetracarboxylic dianhydride can also be used singly or in combination of two or more kinds according to the liquid crystal orientation when forming the free radical generating film, the sensitivity in the polymerization reaction, the voltage holding characteristics, the accumulated charge, and other characteristics.

[0197] In the synthesis when the polymer is polyamic acid ester, the structure of the tetraalkyl ester of tetracarboxylic acid reacting with the above diamine component is not particularly limited, and specific examples thereof are given below.

[0198] Specific examples of the aliphatic tetracarboxylic diester include: dialkyl 1,2,3,4-cyclobutanetetracarboxylate, dialkyl 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylate, dialkyl 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylate, dialkyl 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylate, dialkyl 1,2,3,4-cyclopentanetetracarboxylate, dialkyl 2,3,4,5-tetrahydrofurantetracarboxylate, dialkyl 1,2,4,5-cyclohexanetetracarboxylate, dialkyl 3,4-dicarboxy-1-cyclohexyl succinate, dialkyl 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinate, dialkyl 1,2,3,4-butanetetracarboxylate, dialkyl bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylate, dialkyl 3,3',4,4'-bicyclohexanetetracarboxylate, dialkyl 2,3,5-tricarboxycyclopentyl acetate, dialkyl cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylate, 3,4:7,8-dialkyl tricyclo[4.2.1.0<2,5>]nonane-3,4,7,8-tetracarboxylate, 4,5:11,12-dialkyl hexacyclo[6.6.0.1<2,7>.0<3,6>.1<9,14>.0<10,13>]hexadecane-4,5,11,12-tetracarboxylate, dialkyl 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylate, and the like.

[0199] Specific examples of the aromatic tetracarboxylic dialkyl ester include: dialkyl pyromellitate, dialkyl 3,3',4,4'-biphenyltetracarboxylate, dialkyl 2,2',3,3'-biphenyltetracarboxylate, dialkyl 2,3,3',4-biphenyltetracarboxylate, dialkyl 3,3',4,4'-benzophenonetetracarboxylate, dialkyl 2,3,3',4'-benzophenonetetracarboxylate, dialkyl bis(3,4-dicarboxyphenyl) ether, dialkyl bis(3,4-dicarboxyphenyl) sulfone, dialkyl 1,2,5,6-naphthalenetetracarboxylate, dialkyl 2,3,6,7-naphthalenetetracarboxylate, and the like.

[0200] In the synthesis when the polymer is a polyurea, the diisocyanate that reacts with the above diamine component is not particularly limited and can be used according to availability and the like. Specific structures of the diisocyanate are shown below.

[0201] [Chemical formula 23]

[0202]

[0203] In the formula, R2 and R3 represent aliphatic hydrocarbons having 1 to 10 carbon atoms.

[0204] The aliphatic diisocyanates represented by K-1 to K-5 have poor reactivity but have the advantage of improving solvent solubility. The aromatic diisocyanates represented by K-6 to K-7 have the effects of being rich in reactivity and improving heat resistance, but have the disadvantage of reducing solvent solubility. In terms of versatility or characteristics, K-1, K-7, K-8, K-9, and K-10 are particularly preferred. From the viewpoint of electrical properties, K-12 is preferred, and from the viewpoint of liquid crystal orientation, K-13 is preferred. One or more diisocyanates can also be used in combination, and various applications are preferably carried out according to the desired characteristics.

[0205] In addition, part of the diisocyanate can be replaced with the tetracarboxylic dianhydride described above, and it can also be used in the form of a copolymer of polyamic acid and polyurea, or can be used in the form of a copolymer of polyimide and polyurea by chemical imidization.

[0206] In the synthesis when the polymer is a polyamide, the structure of the dicarboxylic acid to be reacted is not particularly limited. If specific examples are given below, they are as follows. Specific examples of aliphatic dicarboxylic acids include dicarboxylic acids such as malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, hexadiene diacid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, and suberic acid.

[0207] As alicyclic dicarboxylic acids, examples thereof include: 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutanedicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-(2-norbornene)dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid, bicyclo[2.2.2]octane-1,4-dicarboxylic acid, bicyclo[2.2.2]octane-2,3-dicarboxylic acid, 2,5-dioxo-1,4-bicyclo[2.2.2]octanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 4,8-dioxo-1,3-adamantanedicarboxylic acid, 2,6-spiro[3.3]heptanedicarboxylic acid, 1,3-adamantanediacetic acid, camphoric acid, and the like.

[0208] As aromatic dicarboxylic acids, examples thereof include: phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid, tetramethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,4-anthraquinonedicarboxylic acid, 2,5-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,5-biphenyldicarboxylic acid, 4,4''-terphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-bibenzyldicarboxylic acid, 4,4'-diphenylethylenedicarboxylic acid, 4,4'-diphenylacetylenecarboxylic acid, 4,4'-carbonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid, 4,4'-dithiobibenzoic acid, p-phenylenediacetic acid, 3,3'-p-phenylenedipropionic acid, 4-carboxycinnamic acid, p-phenylenediacrylic acid, 3,3'-[4,4'-(methylenedip-phenylene)]dipropionic acid, 4,4'-[4,4'-(oxydip-phenylene)]dipropionic acid, 4,4'-[4,4'-(oxydip-phenylene)]dibutyric acid, (isopropylidenedip-phenylenedioxy)dibutyric acid, bis(p-carboxyphenyl)dimethylsilane and other dicarboxylic acids.

[0209] Examples of the dicarboxylic acid containing a heterocyclic ring include 1,5-(9-oxofluorenyl)dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazoledicarboxylic acid, 2-phenyl-4,5-thiazoledicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, etc.

[0210] The above various dicarboxylic acids may have the structure of acid dihalide or acid anhydride. From the aspect of maintaining the orientation of liquid crystal molecules, these dicarboxylic acids are particularly preferably those that can give a polyamide with a linear structure. Among them, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis(phenyl)propanedicarboxylic acid, 4,4”-terphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,5-pyridinedicarboxylic acid or acid dihalides thereof are preferably used. These compounds may have isomers and may also be mixtures containing these. In addition, two or more compounds may be used in combination. In addition, the dicarboxylic acids used in the present invention are not limited to the above-exemplified compounds.

[0211] When obtaining polyamic acid, polyamic acid ester, polyurea, or polyamide by reacting a diamine (also referred to as "diamine component") as a raw material with a component selected from tetracarboxylic dianhydride (also referred to as "tetracarboxylic dianhydride component"), tetracarboxylic diester, diisocyanate, and dicarboxylic acid, known synthesis means can be used. Generally, it is a method of reacting the diamine component with one or more components selected from the tetracarboxylic dianhydride component, tetracarboxylic diester, diisocyanate, and dicarboxylic acid in an organic solvent.

[0212] The reaction between the diamine component and the tetracarboxylic dianhydride component is advantageous in that it is relatively easy to carry out in an organic solvent and no by-products are generated.

[0213] As the organic solvent used in the above reaction, there is no particular limitation as long as it is an organic solvent that dissolves the generated polymer. Furthermore, even an organic solvent that does not dissolve the polymer can be used in combination with the above solvent within the range where the generated polymer does not precipitate. In addition, since moisture in the organic solvent becomes a cause for hindering the polymerization reaction and further hydrolyzing the generated polymer, it is preferable to use an organic solvent that has been dehydrated and dried.

[0214] Examples of organic solvents include: N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethylphosphoric triamide, γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isopentyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, etc. These organic solvents can be used alone or in combination.

[0215] When reacting a diamine component with a tetracarboxylic dianhydride component in an organic solvent, the following methods can be cited: a method of stirring a solution obtained by dispersing or dissolving the diamine component in an organic solvent and directly adding, or dispersing or dissolving and adding, the tetracarboxylic dianhydride component; conversely, a method of adding the diamine component to a solution obtained by dispersing or dissolving the tetracarboxylic dianhydride component in an organic solvent; a method of alternately adding the tetracarboxylic dianhydride component and the diamine component, etc. Any of these methods can be used. In addition, when the diamine component or the tetracarboxylic dianhydride component is composed of multiple compounds, they can be reacted in a pre-mixed state, or they can be reacted separately in sequence, or the low molecular weight bodies obtained by separate reactions can be further mixed and reacted to form a high molecular weight body.

[0216] The temperature when reacting the diamine component with the tetracarboxylic dianhydride component can be selected arbitrarily, for example, it is in the range of -20 to 100 °C, preferably -5 to 80 °C. In addition, the reaction can be carried out at any concentration. For example, relative to the reaction solution, the total amount of the diamine component and the tetracarboxylic dianhydride component is 1 to 50% by mass, preferably 5 to 30% by mass.

[0217] The ratio of the total molar number of the tetracarboxylic dianhydride component to the total molar number of the diamine component in the above polymerization reaction can be selected arbitrarily according to the molecular weight of the polyamic acid to be obtained. Similar to the usual polycondensation reaction, the closer this molar ratio is to 1.0, the larger the molecular weight of the generated polyamic acid. As a preferred range, it is 0.8 to 1.2.

[0218] The method for synthesizing the polymer used in the present invention is not limited to the above method. In the case of synthesizing polyamic acid, similar to the usual method for synthesizing polyamic acid, instead of the above tetracarboxylic dianhydride, tetracarboxylic acid derivatives such as corresponding-structured tetracarboxylic acid or tetracarboxylic diacyl halide are used, and the reaction is carried out by a known method to obtain the corresponding polyamic acid. In addition, in the case of synthesizing polyurea, it is only necessary to react a diamine with a diisocyanate. In the manufacture of polyamic acid ester or polyamide, it is only necessary to react a diamine with a component selected from tetracarboxylic diester and dicarboxylic acid in the presence of a known condensing agent, or after derivatizing it into acid acyl halide by a known method, and then reacting it with the diamine.

[0219] As a method for imidizing the above polyamic acid to form polyimide, thermal imidization of directly heating the solution of polyamic acid and catalyst imidization of adding a catalyst to the solution of polyamic acid can be cited. In addition, from the viewpoint of being able to improve the voltage holding ratio, the imidization rate from polyamic acid to polyimide is preferably 30% or more, more preferably 30 to 99%. On the other hand, from the viewpoint of suppressing the whitening property, that is, the precipitation of the polymer in the varnish, it is preferably 70% or less. Considering both properties, it is more preferably 40 to 80%.

[0220] When the polyamic acid is thermally imidized in solution, the temperature is generally 100 to 400 °C, preferably 120 to 250 °C, and it is preferably carried out while removing the water generated by the imidization reaction out of the system.

[0221] The catalyst imidization of polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to the solution of polyamic acid and stirring usually at -20 to 250 °C, preferably 0 to 180 °C. The amount of the basic catalyst is usually 0.5 to 30 molar times, preferably 2 to 20 molar times, and the amount of the acid anhydride is usually 1 to 50 molar times, preferably 3 to 30 molar times, based on the amic acid group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. Among them, pyridine has an appropriate basicity to promote the reaction, so it is preferred. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic dianhydride, etc. Among them, if acetic anhydride is used, the purification after the reaction is easy, so it is preferred. The imidization rate based on catalyst imidization can be controlled by adjusting the amount of the catalyst, the reaction temperature, the reaction time, etc.

[0222] When recovering the produced polymer from the reaction solution of the polymer, it is sufficient to pour the reaction solution into a poor solvent to precipitate it. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, etc. The polymer precipitated by pouring it into a poor solvent can be dried at normal pressure or reduced pressure, at room temperature or by heating after being recovered by filtration. In addition, if the operation of redissolving the polymer obtained by precipitation recovery in an organic solvent and reprecipitating and recovering it is repeated 2 to 10 times, the impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons, etc. If three or more kinds of poor solvents selected therefrom are used, the purification efficiency is further improved, so it is preferred.

[0223] In addition, when the radical generating film is composed of a polymer containing an organic group that initiates radical polymerization, the radical generating film-forming composition used in the present invention may contain other polymers in addition to the polymer containing an organic group that initiates radical polymerization. At this time, the content of the other polymer in all components of the polymer is preferably 5 to 95% by mass, more preferably 30 to 70% by mass.

[0224] In consideration of the strength of the radical-generating film obtained by coating the radical-generating film-forming composition, the workability during film formation, the uniformity of the coating film, etc., the molecular weight of the polymer contained in the radical-generating film-forming composition is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000, in terms of the weight-average molecular weight measured by the GPC (Gel Permeation Chromatography) method.

[0225] When obtaining the radical-generating film used in the present invention by immobilizing it in a film by coating a composition of a compound having a radical-generating group and a polymer and curing to form a film, the polymer can be selected from the group consisting of polyimide precursors obtained by the above manufacturing method, polyimide, polyurea, polyamide, polyacrylate, polymethacrylate, etc., which are obtained by using 0 mol% of the diamine component as the diamine component used in the synthesis of the polymer contained in the radical-generating film-forming composition as the diamine component having a site for radical polymerization. As the compound having a radical-generating group added at this time, the following compounds can be mentioned.

[0226] The compounds that generate free radicals using light are not particularly limited as long as they are compounds that initiate free radical polymerization upon light irradiation. Examples of such free radical photoinitiators include: benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, 4,4'-bis(tert-butylperoxycarbonyl)benzophenone, 3,4,4'-tris(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 4-[p-N,N-bis(ethoxycarbonylmethyl)]-2,6-bis(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetrakis(tert-hexylperoxycarbonyl)benzophenone, 3,3'-bis(methoxycarbonyl)-4,4'-bis(tert-butylperoxycarbonyl)benzophenone, 3,4'-bis(methoxycarbonyl)-4,3'-bis(tert-butylperoxycarbonyl)benzophenone, 4,4'-bis(methoxycarbonyl)-3,3'-bis(tert-butylperoxycarbonyl)benzophenone, 2-(3-methyl-3H-benzothiazol-2-ylidene)-1-naphthalen-2-yl-ethanone, or 2-(3-methyl-1,3-benzothiazol-2(3H)-ylidene)-1-(2-benzoyl)ethanone, etc. These compounds can be used alone or in combination of two or more.

[0227] In addition, even when the above radical-generating film is composed of a polymer containing an organic group that initiates radical polymerization, for the purpose of promoting radical polymerization during light irradiation, a compound having the above radical-generating group can also be contained.

[0228] The radical-generating film-forming composition can contain an organic solvent that dissolves or disperses polymer components and other contained components other than the radical generator used as needed. Such an organic solvent is not particularly limited, and examples include the organic solvents exemplified in the synthesis of the above polyamic acid. Among them, from the viewpoint of solubility, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, etc. are preferred. Particularly preferred is N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone, and a mixed solvent of two or more can also be used.

[0229] In addition, it is preferable to mix a solvent that improves the uniformity or smoothness of the coating film with an organic solvent having high solubility for the contained components of the radical-generating film-forming composition.

[0230] As solvents for improving the uniformity or smoothness of the coating film, for example, isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, 2-ethyl-1-hexanol, etc. These solvents can be mixed in multiple kinds. When using these solvents, it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, of the total solvents contained in the liquid crystal aligning agent.

[0231] The radical generating film-forming composition may contain components other than those described above. As examples thereof, compounds for improving the film thickness uniformity or surface smoothness when coating the radical generating film-forming composition, compounds for improving the adhesion between the radical generating film-forming composition and the substrate, compounds for further improving the film strength of the radical generating film-forming composition, etc. can be cited.

[0232] Examples of compounds for improving the uniformity of film thickness or surface smoothness include fluorosurfactants, silicone surfactants, nonionic surfactants, etc. More specifically, for example, Eftop EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), MEGAFAC F171, F173, R-30 (manufactured by DIC Corporation), FLUORAD FC430, FC431 (manufactured by 3M), AsahiGuard AG710, SURFLON S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC, Inc.), etc. When using these surfactants, the usage ratio is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the total amount of the polymer contained in the radical generating film-forming composition.

[0233] As specific examples of the compound for improving the adhesion between the radical-generating film-forming composition and the substrate, compounds containing functional silanes or compounds containing epoxy groups can be cited. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diaza-nonyl acetate, 9-triethoxysilyl-3,6-diaza-nonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(ethylene oxide)-3-aminopropyltrimethoxysilane, N-bis(ethylene oxide)-3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-phenylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxysilane, 3-(N,N-diglycidyl)aminopropyltrimethoxysilane, etc.

[0234] In addition, in order to further improve the film strength of the radical-generating film, phenolic compounds such as 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane and tetrakis(methoxymethyl)bisphenol can be added. When using the above compounds, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the polymer contained in the radical-generating film-forming composition.

[0235] Furthermore, in the radical generating film-forming composition, in addition to the above, within the range that does not impair the effects of the present invention, a dielectric or a conductive substance for the purpose of changing electrical properties such as the dielectric constant or conductivity of the radical generating film may also be added.

[0236] <Method for Producing Radical Generating Film>

[0237] The radical generating film according to the present invention is obtained by using the above-described radical generating film-forming composition. For example, the cured film may be directly used as the radical generating film. The cured film is obtained by coating the radical generating film-forming composition used in the present invention on a substrate and then drying / sintering. In addition, the cured film may be rubbed, or irradiated with polarized light or light of a specific wavelength, or treated with an ion beam, etc., or the liquid crystal display element filled with liquid crystal may be irradiated with UV as an alignment film for PSA.

[0238] When producing the radical generating film, the irradiation light used is not particularly limited and can be appropriately selected according to the purpose. For example, light having a peak in the range of 240 to 400 nm can be cited. Light having a peak in the range of 250 to 365 nm is preferred, and light having a peak in the range of 250 to 360 nm is more preferred. More specifically, for example, light having a peak near 254 nm or 313 nm can be cited.

[0239] In addition, if necessary, a known cut-off filter may be used to cut off light of a specific wavelength or above or below a specific wavelength.

[0240] The substrate for coating the radical generating film-forming composition is not particularly limited as long as it is a substrate with high transparency, and is not limited to electrodes.

[0241] For example, as a preferred mode, a substrate having a transparent electrode for driving liquid crystal formed thereon can be cited.

[0242] If specific examples are cited, substrates having a transparent electrode formed on plastic plates such as glass plates, polycarbonate, poly(meth)acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyether ketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triacetyl cellulose, diacetyl cellulose, cellulose acetate butyrate, etc. can be cited.

[0243] On the substrate that can be used for a liquid crystal display element of the IPS mode, electrode patterns such as standard IPS comb electrodes or PSA fishbone electrodes or protrusion patterns such as MVA can also be used.

[0244] In addition, in a high-functional element such as a TFT-type element, an element in which a transistor is formed between the electrode for driving liquid crystal and the substrate is used.

[0245] In the case of a transmissive liquid crystal display element, the substrates described above are generally used. However, in the case of a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used as long as it is only a single-sided substrate. At this time, materials such as aluminum that can reflect light can also be used for the electrodes formed on the substrate.

[0246] As a coating method of the radical generating film forming composition, spin coating method, printing method, inkjet method, spraying method, roll coating method, etc. can be cited. However, from the viewpoint of productivity, the transfer printing method is widely used industrially, and the transfer printing method is also preferably used in the present invention.

[0247] The step of drying after coating the radical generating film forming composition is not necessarily required. However, when the time from coating to sintering is not uniform for each substrate, or when sintering is not performed immediately after coating, a drying step is preferably included. This drying only needs to remove the solvent to such an extent that the shape of the coating film does not deform due to transportation of the substrate or the like, and there is no particular limitation on the drying means. For example, the following methods can be cited: drying on a hot plate at a temperature of 40°C to 150°C, preferably 60°C to 100°C, for 0.5 to 30 minutes, preferably 1 to 5 minutes.

[0248] The coating film formed by coating the radical generating film forming composition by the above method, that is, the radical generating film, can be sintered to form a cured film. At this time, the sintering temperature can generally be carried out at any temperature from 100°C to 350°C, preferably 140°C to 300°C, more preferably 150°C to 230°C, and further preferably 160°C to 220°C. The sintering time can generally be carried out for any time from 5 minutes to 240 minutes. It is preferably 10 to 90 minutes, more preferably 20 to 90 minutes. Heating can generally be carried out using a known method, such as a hot plate, a hot air circulation oven, an IR (infrared) oven, a belt furnace, etc.

[0249] The thickness of the cured radical generating film can be selected as needed. However, when it is preferably 5 nm or more, more preferably 10 nm or more, the reliability of the liquid crystal display element can be easily obtained, so it is preferred. In addition, when the thickness of the cured film is preferably 300 nm or less, more preferably 150 nm or less, the power consumption of the liquid crystal display element will not become extremely large, so it is preferred.

[0250] The first substrate having a radical generating film can be obtained in the above manner, but a uniaxial orientation treatment can also be performed on the radical generating film. As a method for performing the uniaxial orientation treatment, a photoorientation method, an inclined evaporation method, rubbing, a uniaxial orientation treatment based on a magnetic field, etc. can be cited.

[0251] In the case of performing an alignment treatment by performing a rubbing treatment unidirectionally, for example, while rotating a rubbing roller around which a rubbing cloth is wound, a substrate is moved in such a manner that the rubbing cloth comes into contact with the film. In the case of the first substrate of the present invention on which comb electrodes are formed, a direction is selected according to the electrophysical properties of the liquid crystal. However, in the case of using a liquid crystal having a positive dielectric anisotropy, it is preferable that the rubbing direction is substantially the same as the direction in which the comb electrodes extend.

[0252] <Liquid crystal composition containing a liquid crystal and a radically polymerizable compound>

[0253] The liquid crystal display element of the present invention is produced using a liquid crystal composition containing a liquid crystal and a radically polymerizable compound.

[0254] The polymerizable compound used together with the liquid crystal is not particularly limited as long as it is a radically polymerizable compound. For example, it is a compound having one or more polymerizable unsaturated bonds in one molecule. A compound having one polymerizable unsaturated bond in one molecule (hereinafter, sometimes referred to as "a compound having a monofunctional polymerizable group", "a compound having a monovalent polymerizable group", etc.) is preferable. The polymerizable unsaturated bond is preferably a radically polymerizable unsaturated bond, such as a vinyl bond.

[0255] At least one of the radically polymerizable compounds is preferably a compound having a polymerizable unsaturated bond in one molecule and being compatible with the liquid crystal, that is, a compound having a monofunctional radically polymerizable group.

[0256] Moreover, as the polymerizable group of the radically polymerizable compound, a polymerizable group selected from the following structures is preferable.

[0257] [Chemical formula 24]

[0258]

[0259] (In the formula, * represents a site bonded to a part other than the polymerizable unsaturated bond of the compound molecule; R b represents a linear alkyl group having 3 to 20 carbon atoms, and E represents a bonding group selected from a single bond, -O-, -NR c -, -S-, an ester bond, and an amide bond. R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group of R b represents a linear, branched, or cyclic alkyl group).

[0260] In addition, in the liquid crystal composition containing a liquid crystal and a radically polymerizable compound, it is preferable to contain the following radically polymerizable compound: the Tg of the polymer obtained by polymerizing the above radically polymerizable compound reaches 100 °C or lower.

[0261] A compound having a monofunctional polymerizable reactive group is a compound capable of radical polymerization in the presence of an organic radical. Examples thereof include: methacrylate monomers such as tert-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, lauryl methacrylate, and n-octyl methacrylate; acrylate monomers such as tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, benzyl acrylate, lauryl acrylate, and n-octyl acrylate; styrene, styrene derivatives (e.g., o-, m-, p-methoxystyrene, o-, m-, p-tert-butoxystyrene, o-, m-, p-chloromethylstyrene, etc.), vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl benzoate, vinyl acetate, etc.), vinyl ketones (e.g., vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, etc.), N-vinyl compounds (e.g., N-vinylpyrrolidone, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, etc.), (meth)acrylic acid derivatives (e.g., acrylonitrile, methacrylonitrile, acrylamide, isopropylacrylamide, methacrylamide, etc.), vinyl halides (e.g., vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachlorobutadiene, vinyl fluoride, etc.), and other vinyl monomers, but are not limited thereto. These various radical polymerizable monomers can be used alone or in combination of two or more. In addition, these are preferably compatible with liquid crystals.

[0262] In addition, as the above radical polymerizable compound, a compound represented by the following formula (A) is also preferred.

[0263] [Chemical formula 25]

[0264]

[0265] (In formula (A), R a and R b each independently represent an alkyl group having 3 to 20 carbon atoms, E represents a bonding group selected from a single bond, -O-, -NR c -, -S-, an ester bond, and an amide bond, R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group of R a or R b represents a straight-chain, branched, or cyclic alkyl group).

[0266] Moreover, as the radical polymerizable compound represented by formula (A), from the viewpoints of ease of synthesis, compatibility with liquid crystals, and polymerization reactivity, a compound in which E in the formula is an ester bond (-C(=O)-O- or -O-C(=O)-) is preferred, and specifically preferred are compounds having the following structures, without particular limitation.

[0267] [Chemical formula 26]

[0268]

[0269] (In formulas (A-1) and (A-2), R a and R b each independently represent a linear alkyl group having 3 to 20 carbon atoms, and the alkyl groups of R a and R b each independently represent a linear, branched, or cyclic alkyl group).

[0270] The radically polymerizable compound according to the present invention may also have a vertical alignment group.

[0271] As the vertical alignment group possessed by the radically polymerizable compound used in the present invention, for example, a group represented by the following formula [S1] can be cited.

[0272] [Chemical formula 27]

[0273]

[0274] In formula [S1], X 1 and X 2 independently represent a single bond, -(CH2) a -(where a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -COO-, -OCO-, or -((CH2) a1 -A1) m1- (a plurality of a1 each independently represent an integer from 1 to 15, a plurality of A1 each independently represent an oxygen atom or -COO-, and m1 is 1 or 2). Among them, from the viewpoints of availability of raw materials and ease of synthesis, a single bond, -(CH2) a -(where a is an integer from 1 to 15), -O-, -CH2O-, or -COO- is preferred. More preferably, a single bond, -(CH2) a -(where a is an integer from 1 to 10), -O-, -CH2O-, or -COO-.

[0275] G 1 and G 2 independently are divalent cyclic groups selected from divalent aromatic groups having 6 to 12 carbon atoms or divalent alicyclic groups having 3 to 8 carbon atoms, and any hydrogen atom on the above-mentioned cyclic group may also be replaced by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms, or a fluorine atom. m and n independently are integers from 0 to 3, and the sum of these is from 0 to 4, R 1is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms, and any hydrogen in these groups may also be replaced by fluorine. When the sum of m and n is 0, R 1 may also be a group having a steroid skeleton.

[0276] Examples of the divalent aromatic group having 6 to 12 carbon atoms include phenylene, biphenylene, naphthylene, etc. In addition, examples of the divalent alicyclic group having 3 to 8 carbon atoms include cyclopropylene, cyclohexylene, etc.

[0277] As preferred specific examples of the formula [S1], the structures of the following formulas [S1-x1] to [S1-x7] can be cited.

[0278] [Chemical formula 28]

[0279]

[0280] In the formulas [S1-x1] to [S1-x7], R 1 is an alkyl group having 1 to 20 carbon atoms, X p represents -(CH2) a -(a is an integer from 1 to 15), A1 is an oxygen atom or -COO-*(where the bonding position marked with "*" is bonded to (CH2) a2 bonded), A2 is an oxygen atom or *-COO-(where the bonding position marked with "*" is bonded to (CH2) a2 bonded), a1 and a3 are each independently an integer of 0 or 1, a2 is an integer from 2 to 10, and Cy is 1,4-cyclohexylene or 1,4-phenylene.

[0281] As preferred specific examples of the above group having a steroid skeleton, the following formula [S3-x] can be cited.

[0282] [Chemical formula 29]

[0283]

[0284] In the formula [S3-x], Col represents any one of the above formulas [Col1] to [Col4], and G represents any one of the above formulas [G1] to [G2]. * represents the bonding position.

[0285] As a preferred embodiment of the radical polymerizable compound according to the present invention, for example, a radical polymerizable compound having a vertically orienting group in which any one of the above radical polymerizable groups is bonded to the above vertically orienting group [S1] can be cited.

[0286] These various radically polymerizable monomers can be used alone or in combination of two or more. In addition, these are preferably compatible with liquid crystals.

[0287] The content of the radically polymerizable compound in the liquid crystal composition is preferably 3% by mass or more, more preferably 5% by mass or more, preferably 50% by mass or less, and more preferably 20% by mass or less, based on the total mass of the liquid crystal and the radically polymerizable compound.

[0288] In addition, a liquid crystal generally refers to a substance in a state showing the properties of both a solid and a liquid. As representative liquid crystal phases, there are nematic liquid crystals and smectic liquid crystals, and the liquid crystals that can be used in the present invention are not particularly limited. For example, 4-pentyl-4'-cyanobiphenyl.

[0289] <Liquid crystal cell>

[0290] The liquid crystal display element according to the present invention can be formed into, for example, the cell structure described below.

[0291] After forming a radical generating film on a substrate by the above method, the first substrate having the radical generating film and the second substrate are arranged such that the radical generating film on the first substrate faces the second substrate, and a liquid crystal composition containing a liquid crystal and a radically polymerizable compound is filled between the first substrate and the second substrate, thereby producing a liquid crystal cell.

[0292] The liquid crystal display element manufactured in the present invention can use the liquid crystal cell obtained in this way.

[0293] If the manufacturing method of the above liquid crystal cell is described in more detail, after arranging the radical generating film on the first substrate to face the second substrate, a spacer is clamped, and the two substrates are fixed with a sealant. A liquid crystal composition containing a liquid crystal and a radically polymerizable compound is injected between the first and second substrates and sealed, thereby obtaining a liquid crystal cell.

[0294] The size of the spacer used at this time is usually 1 to 30 μm, preferably 2 to 10 μm.

[0295] The method of injecting a liquid crystal composition containing a liquid crystal and a radically polymerizable compound is not particularly limited, and examples include a vacuum method in which the inside of the produced liquid crystal cell is depressurized and then a mixture containing a liquid crystal and a polymerizable compound is injected, and a dropping method in which a mixture containing a liquid crystal and a polymerizable compound is dropped and then sealed.

[0296] An alignment film for aligning the liquid crystal is preferably formed on the second substrate.

[0297] As the alignment film, it can be a well-known liquid crystal alignment film or any one of the radical generating films involved in the present invention, and can be appropriately selected according to the purpose.

[0298] A uniaxial alignment treatment can be performed on the alignment film formed on the above-mentioned first substrate.

[0299] As described later, for example, when forming an out-of-plane alignment region on a liquid crystal display element, it is preferable to form a radical generating film on the second substrate.

[0300] In addition, for example, when forming an in-plane alignment region or an inclined alignment region on a liquid crystal display element, it is preferable to form a liquid crystal alignment film for horizontal alignment that has been subjected to uniaxial alignment treatment on the second substrate.

[0301] <Formation of In-Plane Alignment, Out-of-Plane Alignment, and Inclined Alignment Regions>

[0302] For a liquid crystal cell obtained by using a substrate on which a radical generating film is formed and disposing a mixture (liquid crystal composition) containing a liquid crystal and a radical polymerizable compound between the substrates, light sufficient to cause a polymerization reaction of the radical polymerizable compound is irradiated.

[0303] In this way, in the present invention, a radical generating film having an anchoring force is formed on a substrate, and in a state where a liquid crystal containing a specific polymerizable compound is in contact with the radical generating film, light is irradiated to the radical generating film in a region where the anchoring force is desired to be maintained. Through the polymerization of the polymerizable compound, the liquid crystal is vertically aligned, and as a result, an out-of-plane alignment (vertical alignment) region is formed in the region where the light is irradiated.

[0304] Here, the irradiated light may include light having a peak in the range of 240 to 400 nm. In addition, it is preferable to irradiate light having a wavelength at which the absorbance of the portion corresponding to the photo-radical generation site becomes higher. This light is more preferably light having a peak in the range of 250 to 365 nm, and further preferably light having a peak in the range of 250 to 360 nm.

[0305] More specifically, for example, light having a peak around 313 nm can be used. In addition, if necessary, light having a specific wavelength or wavelengths above or below a specific wavelength can be cut off using a well-known cut-off filter.

[0306] The irradiation amount of light is usually 0.01 to 30 J, and can preferably be 10 J or less. The smaller the irradiation amount of light, the more the reduction in reliability caused by the damage of the components constituting the liquid crystal display element can be suppressed, and the manufacturing tact can be improved by reducing the light irradiation time, so it is preferable.

[0307] In addition, heating can also be performed when irradiating light. The heating temperature when irradiating light is preferably in the temperature range at which the introduced liquid crystal exhibits liquid crystallinity, usually 40°C or higher, and preferably heating is performed at a temperature below the temperature at which the liquid crystal changes to the isotropic phase.

[0308] In addition, preferably, during light irradiation when the radical polymerizable compound is subjected to a polymerization reaction, it is performed in a state without an applied voltage, i.e., in a non-electric field state.

[0309] On the other hand, when irradiating light to the liquid crystal cell, a photomask is disposed outside the liquid crystal cell. When the spacer photomask irradiates light, an in-plane alignment (horizontal alignment) region is formed in the unexposed portion (i.e., the region where no radicals are generated), and an out-of-plane alignment (vertical alignment) region is formed in the exposed portion as described above.

[0310] There are no particular limitations on the pattern shape or pattern size of the photomask used, and it can be appropriately selected according to the purpose. As the pattern shape, for example, a line pattern shape, a line / space (L / S) pattern shape, a dot shape, etc. can be cited. As the pattern size, a pattern in the micron size can be formed. For example, if a photomask having an L / S pattern shape with a pitch of 5 μm is used, an alignment pattern with a pitch of 5 μm can be formed.

[0311] In addition, by irradiating light to the radical generating film before assembling the liquid crystal cell and inactivating the radical generating ability of the radical generating film, an in-plane alignment (horizontal alignment) region can also be formed. By previously irradiating light to the radical generating film to eliminate the radical generating ability, a state in which the anchoring strength in the in-plane direction is always maintained can be achieved. That is, a liquid crystal cell is fabricated using the radical generating film in which the radical generating ability is inactivated, and the liquid crystal cell is irradiated with light, and an in-plane alignment (horizontal alignment) region can also be formed in the region where the radical generating ability is inactivated.

[0312] In addition, as the light used to inactivate the radical generating ability of the radical generating film, light having a peak in the range of 240 to 400 nm can be cited. In addition, this light is preferably light having a peak in the range of 250 to 365 nm, and more preferably light having a peak in the range of 250 to 360 nm. More specifically, for example, light having a peak near 313 nm can be used. In addition, according to needs, light having a specific wavelength or wavelengths above or below a specific wavelength cut off by a known cut-off filter can also be used.

[0313] The irradiation amount of light is usually 0.01 to 30 J, and can also be preferably 10 J or less.

[0314] In the above unexposed portion or the region where the radical generating ability is inactivated, in order to make the liquid crystal align well in the plane, it is preferable to perform a uniaxial alignment treatment on the radical generating film.

[0315] In addition, in the above-described unexposed portion or the region where the radical generating ability is inactivated, in order to achieve good in-plane alignment of the liquid crystal, the polymer contained in the radical generating film-forming composition in the radical generating film is preferably a polymer that does not contain a portion having a function of vertical alignment.

[0316] As described above, when using a radical generating film to form an out-of-plane alignment region, it is only necessary to use the first and second substrate manufacturing units formed with a radical generating film, inject a liquid crystal composition containing a predetermined radical polymerizable compound, and then irradiate light from the outside of the unit to polymerize the polymerizable compound, thereby achieving vertical alignment of the liquid crystal.

[0317] On the other hand, when using a radical generating film to form an in-plane alignment region, it is only necessary to pre-irradiate light to inactivate the radical generating ability of the first and second substrates formed with a radical generating film before unit assembly, and then perform unit assembly. Thus, even if light is irradiated on the fabricated liquid crystal cell, the interfacial reaction can be suppressed.

[0318] Alternatively, it is also possible to dispose a photomask outside the liquid crystal cell for a liquid crystal cell prepared without inactivating the radical generating ability, and irradiate light at intervals of the photomask. Thus, no radicals are generated in the unexposed portion, and the interfacial reaction is not induced.

[0319] In a liquid crystal display element, a tilt orientation region can be formed by fabricating a liquid crystal cell with the in-plane alignment region and the out-of-plane alignment region facing each other.

[0320] For example, when using a radical generating film on both the first substrate and the second substrate, a tilt orientation region can be fabricated by appropriately combining the above method for forming an out-of-plane alignment region and the method for forming an in-plane alignment region.

[0321] More specifically, for example, by using a radical generating film on one of the first substrate and the second substrate to form an out-of-plane alignment region, and using a radical generating film with inactivated radical generating ability on the other substrate to form an in-plane alignment region, a tilt orientation region can be formed.

[0322] Alternatively, a radical generating film may be used on one of the first substrate and the second substrate, and a liquid crystal alignment film having no radical generating ability may be used on the other substrate. When a liquid crystal alignment film having no radical generating ability is used on the other substrate, as the liquid crystal alignment film, an in-plane alignment film or an out-of-plane alignment film may be used. By combining with the method of forming in-plane alignment regions and out-of-plane alignment regions using a radical generating film as described above, various patterns composed of various combinations of in-plane alignment regions, tilted alignment regions, and out-of-plane alignment regions can be formed.

[0323] The liquid crystal alignment film is preferably uniaxially aligned.

[0324] In addition, in the method for manufacturing a liquid crystal display element of the present invention, the content of the radical polymerizable compound contained in the liquid crystal composition or the irradiation amount when irradiating light to the liquid crystal cell can also be adjusted so that the liquid crystal is tilted rather than vertically aligned, and a tilted alignment region is formed.

[0325] As described above, according to the method for manufacturing a liquid crystal display element of the present invention, a liquid crystal display element in which at least two regions of an in-plane alignment region, an out-of-plane alignment region, and a tilted alignment region are patterned can be manufactured in a liquid crystal display element having a radical generating film.

[0326] <Liquid Crystal Display Element>

[0327] According to the manufacturing method of the present invention, a liquid crystal display element in which at least two regions of an in-plane alignment region, an out-of-plane alignment region, and a tilted alignment region are patterned can be produced industrially with good productivity. Therefore, the liquid crystal display element produced by using the manufacturing method of the present invention can be widely used in practice.

[0328] For example, a reflective liquid crystal display element can be used by providing a reflective electrode, a transparent electrode, a λ / 4 plate, a polarizing film, a color filter layer, etc. in the liquid crystal cell as needed according to a conventional method.

[0329] In addition, a backlight, a polarizing plate, a λ / 4 plate, a transparent electrode, a polarizing film, a color filter layer, etc. can be provided in the liquid crystal cell as needed according to a conventional method to use it as a transmissive liquid crystal display element.

[0330] Figure 10 is a schematic cross-sectional view showing an example of the liquid crystal display element of the present invention, and is an example of an IPS mode liquid crystal display element.

[0331] In Figure 10In the illustrated liquid crystal display element 101, a liquid crystal composition 103 is sandwiched between a comb-shaped electrode substrate 102 having a radical generating film 102c and a counter substrate 104 having a liquid crystal alignment film 104a. The comb-shaped electrode substrate 102 has: a base material 102a, a plurality of linear electrodes 102b formed on the base material 102a and arranged in a comb shape, and a radical generating film 102c formed on the base material 102a so as to cover the linear electrodes 102b. The counter substrate 104 has: a base material 104b and a liquid crystal alignment film 104a formed on the base material 104b.

[0332] In this liquid crystal display element 101, when a voltage is applied to the linear electrodes 102b, an electric field is generated between the linear electrodes 102b as shown by the power lines L.

[0333] Figure 11 It is a schematic cross-sectional view showing another example of the liquid crystal display element of the present invention, and is an example of an FFS mode liquid crystal display element.

[0334] In Figure 11 In the illustrated liquid crystal display element 101, a liquid crystal composition 103 is sandwiched between a comb-shaped electrode substrate 102 having a radical generating film 102h and a counter substrate 104 having a liquid crystal alignment film 104a. The comb-shaped electrode substrate 102 has: a base material 102d, a surface electrode 102e formed on the base material 102d, an insulating film 102f formed on the surface electrode 102e, a plurality of linear electrodes 102g formed on the insulating film 102f and arranged in a comb shape, and a radical generating film 102h formed on the insulating film 102f so as to cover the linear electrodes 102g. The counter substrate 104 has: a base material 104b and a liquid crystal alignment film 104a formed on the base material 104b.

[0335] In this liquid crystal display element 101, when a voltage is applied to the surface electrode 102e and the linear electrodes 102g, an electric field is generated between the surface electrode 102e and the linear electrodes 102g as shown by the power lines L.

[0336] [Examples]

[0337] Examples are given below to further detail the present invention, but the scope of the present invention is not limited to these examples.

[0338] In the examples, the abbreviations of the compounds used in the polymerization of the polymer and the preparation of the radical generating film forming composition and the methods for property evaluation are as follows.

[0339] [Chemical formula 30]

[0340]

[0341] [Chemical formula 31]

[0342]

[0343] NMP: N-methyl-2-pyrrolidone,

[0344] BCS: butyl cellosolve

[0345] <Viscosity measurement>

[0346] For the polyamic acid solution, use an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) to measure the viscosity at 25 °C with a sample volume of 1.1 mL and a conical rotor (Cone Rotor) TE-1 (1°34', R24).

[0347] <Measurement of molecular weight>

[0348] The molecular weight is measured by a normal temperature GPC (gel permeation chromatography) device, and the number average molecular weight (Mn) and weight average molecular weight (Mw) are calculated as polyethylene glycol and polyethylene oxide conversion values.

[0349] GPC device: GPC-101 (manufactured by Showa Denko KK), column: tandem of GPC KD-803 and GPC KD-805 (manufactured by Showa Denko KK), column temperature: 50 °C, eluent: N,N-dimethylformamide (as an additive, lithium bromide monohydrate (LiBr·H2O) is 30 mmol / L, phosphoric acid·anhydrous crystal (o-phosphoric acid) is 30 mmol / L, tetrahydrofuran (THF) is 10 mL / L), flow rate: 1.0 mL / min

[0350] Standard samples for making the standard curve: TSK standard polyethylene oxide (molecular weight; approximately 900,000, 150,000, 100,000, and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; approximately 12,000, 4,000, and 1,000) (manufactured by Polymer Laboratories).

[0351] <Measurement of imidization rate>

[0352] Put 20 mg of polyimide powder into an NMR sample tube (NMR sampling tube standard manufactured by Kusano Kagaku Co., Ltd.) ) and add 0.53 mL of deuterated dimethyl sulfoxide (DMSO-d6, a mixture of 0.05 mass% TMS (tetramethylsilane)), and apply ultrasound to completely dissolve it. Measure the proton NMR at 500 MHz of this solution using a measuring device (manufactured by JEOL DATUM, JNW-ECA500).

[0353] The imidization rate is determined using the protons from the structure that remains unchanged before and after imidization as the reference protons. Using the integrated peak value of these protons and the integrated peak value of the protons from the NH of the amide group that appears around 9.5 - 10.0 ppm, it is calculated by the following mathematical formula.

[0354] Imidization rate (%) = (1 - α·x / y) × 100

[0355] In the formula, x is the integrated peak value of the protons from the NH of the amide group, y is the integrated peak value of the reference protons, and α is the ratio of the number of reference protons to the NH protons of one amide group in the case of polyamic acid (imidization rate is 0%).

[0356] <Synthesis of Compound DA - 4>

[0357] [Chemical Formula 32]

[0358]

[0359] (First Step)

[0360] To 4,4'-dinitro-[1,1'-biphenyl]-2,2'-dicarboxylic acid (20.0 g, 60.2 mmol), tetrahydrofuran (120 g), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone (28.4 g, 126 mmol), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (28.0 g, 181 mmol), and N,N-dimethylaminopyridine (0.735 g, 6.02 mmol) were added, and the mixture was stirred overnight at room temperature. After the reaction was completed, liquid-liquid extraction was performed twice with water / chloroform, and the obtained organic phase was concentrated to obtain a sugary light brown oil. This was purified by column chromatography in a mixed solvent of ethyl acetate / hexane = 3 / 1 (volume ratio). After concentrating the obtained fractions, a yellow transparent oil was obtained. Continuing to let it stand, white crystals precipitated from the oil. The precipitated crystals were washed with a slurry of a mixed solvent of ethyl acetate / hexane = 3 / 1 (volume ratio), filtered, and the crystals were dried to obtain Compound DA - 4 - 1 (yield: 29.8 g, 40.0 mmol, yield 67%).

[0361] 1H-NMR (500 MHz) in DMSO-d6: δ 8.57 (d, J = 2.5 Hz, 2H), 8.37 (dd, J = 8.5 Hz, 2.5 Hz, 2H), 8.18 (d, J = 9.0 Hz, 4H), 7.55 (d, J = 8.5 Hz, 2H), 6.85 (d, J = 9.0 Hz, 4H), 5.631 (s, 2H), 4.39 - 4.35 (m, 4H), 4.02 - 3.99 (m, 2H), 3.96 - 3.94 (m, 2H), 1.40 (s, 12H).

[0362] (Second process)

[0363] To the compound DA-4-1 (29.8 g, 40.0 mmol) obtained in the first process, tetrahydrofuran (240 g) was added. After purging with nitrogen, 3% platinum on carbon (hydrous product) (2.38 g) was added and further purged with nitrogen. A hydrogen Tedlar bag was installed, and the mixture was stirred at room temperature for about 17 hours. After completion of the reaction, the platinum on carbon was removed through a membrane filter, and then concentrated / dried to obtain the compound (DA-4) (yield: 27.4 g, 40.0 mmol, quantitative yield).

[0364] 1 H-NMR (500 MHz) in DMSO-d6: δ 8.20 (dd, J = 7.1 Hz, 1.9 Hz, 4H), 6.99 (d, J = 2.5 Hz, 2H), 6.92 (dd, J = 7.3 Hz, 1.9 Hz, 4H), 6.80 (d, J = 8.2 Hz, 2H), 6.67 (dd, J = 8.2 Hz, 2.5 Hz, 2H), 5.64 (s, 2H), 5.24 (s, 4H), 4.22 (t, J = 4.5 Hz, 4H), 4.00 (br, 4H), 1.39 (s, 12H).

[0365] (Polymerization of polymer and preparation of radical generating film-forming composition)

[0366] <Synthesis Example 1> Polymerization of TC-1(50) TC-2(50) / DA-1(70) DA-2(30) polyamic acid

[0367] In a 100 mL four-necked flask equipped with a nitrogen inlet tube, an air-cooling tube, and a mechanical stirrer, 3.78 g (35.0 mmol) of DA-1 and 4.96 g (15.0 mmol) of DA-2 were measured, 35.0 g of NMP was added, and the mixture was stirred under a nitrogen atmosphere until completely dissolved. After confirming dissolution, 6.26 g (25.0 mmol) of TC-2 and 25.0 g of NMP were added, and the mixture was heated and stirred at 60 °C for 3 hours under a nitrogen atmosphere. Then, 4.12 g (21.0 mmol) of TC-1 and 16.5 g of NMP were added, and the mixture was stirred at room temperature for 12 hours. The polymerization viscosity was confirmed, and further TC-1 was added to make the polymerization viscosity 1000 mPa·s, obtaining a polymerization solution with a polyamic acid concentration of 20% by mass.

[0368] In a 200 mL conical flask equipped with a magnetic stirrer, 50.0 g of the polyamic acid solution obtained above was measured, 92.9 g of NMP was added to prepare a solution with a solid component concentration of 7% by mass. While stirring, 10.6 g (103 mmol) of acetic anhydride and 3.28 g (41.4 mmol) of pyridine were added. After stirring at room temperature for 30 minutes, the mixture was heated and stirred at 60 °C for 3 hours. Then, the solution was allowed to return to room temperature and poured into 500 mL of methanol while stirring to precipitate the solid. After repeating this operation twice, the precipitate was air-dried and dried in a vacuum oven set at 60 °C, thereby obtaining a polyimide powder (PI-1) with Mn of 11,453, Mw of 27,655, and an imidization rate of 67.0%.

[0369] <Synthesis Example 2>

[0370] Synthesis of Polyimide with TC-1(50) TC-2(50) / DA-1(50) DA-2(50)

[0371] As shown in Table 1, the amounts of the monomers used were changed, and except for this, the same method as in Synthesis Example 1 was used to obtain a polyimide powder (PI-2). The Mn of this polyimide powder was 21,959, Mw was 67,088, and the imidization rate was 62.2%.

[0372] <Synthesis Example 3>

[0373] Synthesis of Polyimide with TC-1(50) TC-2(50) / DA-2(100)

[0374] As shown in Table 1, the amounts of the monomers used were changed, and except for this, the same method as in Synthesis Example 1 was used to obtain a polyimide powder (PI-3). The Mn of this polyimide powder was 21,959, Mw was 67,088, and the imidization rate was 72.0%.

[0375] <Synthesis Example 4> Polymerization of TC-3(100) / DA-3(50)DA-4(50) Polyamic Acid

[0376] In a 100 mL four-necked flask equipped with a nitrogen inlet tube, an air-cooling tube, and a mechanical stirrer, 2.44 g (10.00 mmol) of DA-3 and 6.85 g (10.00 mmol) of DA-4 were measured, 52.6 g of NMP was added, and the mixture was stirred under a nitrogen atmosphere until completely dissolved. After confirming dissolution, 4.21 g (18.80 mmol) of TC-3 and 23.9 g of NMP were added, and the mixture was heated and stirred at 40 °C for 12 hours under a nitrogen atmosphere. The polymerization viscosity was confirmed, and further TC-3 was added to make the polymerization viscosity 400 mPa·s, obtaining a polymerization solution (PAA-1) with a polyamic acid concentration of 15% by mass. The Mn of this polyamic acid was 16,331, and the Mw was 42,999.

[0377] <Synthesis Example 5> Synthesis of AC-1(40)AC-2(60) Polymethacrylate

[0378] In a 100 mL four-necked flask equipped with a nitrogen inlet tube, an air-cooling tube, and a mechanical stirrer, 5.00 g (15.0 mmol) of AC-1, 6.91 g (22.6 mmol) of AC-2, and 0.185 g (1.13 mmol) of AIBN were measured, 67.5 g of NMP was added, and the mixture was stirred under a nitrogen atmosphere until completely dissolved. After vacuum degassing this solution, it was heated and stirred at 60 °C for 12 hours under a nitrogen atmosphere. Then, the solution was allowed to return to room temperature, and while stirring, it was poured into 300 mL of methanol to precipitate the solid. After repeating this operation twice, it was air-dried and dried in a vacuum oven set at 60 °C, thereby obtaining a polymethacrylate powder (PMA-1) with Mn of 37,197 and Mw of 116,919.

[0379] <Preparation of Free Radical Generation Film-Forming Composition: AL-1>

[0380] In a 15 mL vial equipped with a magnetic stirrer, 0.90 g of the polyimide powder (PI-1) obtained in Synthesis Example 1 was measured, 5.10 g of NMP was added, and the mixture was heated and stirred at 50 °C to obtain a polymer solution with a solid component concentration of 15% by mass. 6.00 g of NMP and 3.00 g of BCS were added thereto, and further stirred for 3 hours, thereby obtaining the free radical generation film-forming composition according to the present invention: AL-1 (solid component: 6.0% by mass, NMP: 74% by mass, BCS: 20% by mass).

[0381] <Preparation of Free Radical Generation Film-Forming Composition: AL-2>

[0382] Using the polyimide powder (PI-2) obtained in Synthesis Example 2, a radical-generating film-forming composition according to the present invention was obtained by the same method as the preparation of AL-1: AL-2 (solid content: 6.0% by mass, NMP: 74% by mass, BCS: 20% by mass).

[0383] <Preparation of Radical-Generating Film-Forming Composition: AL-3>

[0384] Using the polyimide powder (PI-3) obtained in Synthesis Example 3, a radical-generating film-forming composition according to the present invention was obtained by the same method as the preparation of AL-1: AL-3 (solid content: 6.0% by mass, NMP: 74% by mass, BCS: 20% by mass).

[0385] <Preparation of Radical-Generating Film-Forming Composition: AL-4>

[0386] In a 15 mL vial equipped with a magnetic stirrer, 6.00 g of the polyamic acid (PAA-1) obtained in Synthesis Example 4 was measured, and 6.00 g of NMP and 3.00 g of BCS were added, followed by stirring for 3 hours, thereby obtaining a radical-generating film-forming composition according to the present invention: AL-4 (solid content: 6.0% by mass, NMP: 74% by mass, BCS: 20% by mass).

[0387] <Preparation of Radical-Generating Film-Forming Composition: AL-5>

[0388] In a 15 mL vial equipped with a magnetic stirrer, 0.27 g of the polymethacrylate powder (PMA-1) obtained in Synthesis Example 5 and 0.63 g of the polyimide powder (PI-3) obtained in Synthesis Example 3 were measured, and 5.10 g of NMP was added, followed by heating and stirring at 60 °C to obtain a polymer solution with a solid content concentration of 15% by mass. 6.00 g of NMP and 3.00 g of BCS were added thereto, and further stirring was carried out for 3 hours, thereby obtaining a radical-generating film-forming composition according to the present invention: AL-5 (solid content: 6.0% by mass, NMP: 74% by mass, BCS: 20% by mass).

[0389] <Preparation of Radical-Generating Film-Forming Composition: AL-6>

[0390] In a 15 mL vial equipped with a magnetic stirrer, 0.45 g of the polymethacrylate powder (PMA-1) obtained in Synthesis Example 5 and 0.45 g of the polyimide powder (PI-3) obtained in Synthesis Example 3 were measured, and 5.10 g of NMP was added. The mixture was heated and stirred at 60 °C to obtain a polymer solution with a solid content concentration of 15% by mass. 6.00 g of NMP and 3.00 g of BCS were added thereto, and further stirred for 3 hours to obtain the radical-generating film-forming composition according to the present invention: AL-6 (solid content: 6.0% by mass, NMP: 74% by mass, BCS: 20% by mass).

[0391] <Preparation of non-radical generating film-forming composition: AL-7>

[0392] Using the polymethacrylate powder (PMA-1) obtained in Synthesis Example 5, the non-radical generating film-forming composition according to the comparative object of the present invention: AL-7 (solid content: 6.0% by mass, NMP: 74% by mass, BCS: 20% by mass) was obtained by the same method as the preparation of AL-1.

[0393] The compositions of the polyamic acid and the polyimide are shown in Table 1 below.

[0394] [Table 1]

[0395]

[0396] The composition of the polymethacrylate is shown in Table 2 below.

[0397] [Table 2]

[0398]

[0399]

[0400] The compositions of the radical-generating film-forming composition and the non-radical generating film-forming composition are shown in Table 3 below.

[0401] [Table 3]

[0402]

[0403] The composition of the liquid crystal species is shown in Table 4 below.

[0404] [Table 4]

[0405]

[0406] (Polymerizable compound)

[0407] The polymerizable compound (additive) described in Table 4 was obtained in the following manner.

[0408] <Synthesis Example 1 of Polymerizable Compound>

[0409] Synthesis of Dodecyl Itaconate (IC-12)

[0410] [Chemical Formula 33]

[0411]

[0412] In a four-necked flask equipped with a Dean-Stark tube, 30.0 g (231 mmol) of itaconic acid and 81.6 g (438 mmol) of 1-dodecanol were measured, and they were completely dissolved with cyclohexane (700 mL). After confirming dissolution, 1.13 g (11.5 mmol) of concentrated sulfuric acid and 0.51 g (2.31 mmol) of dibutylhydroxytoluene (BHT) were added, and the mixture was heated and stirred at 120 °C for 24 hours under a nitrogen atmosphere. After confirming the completion of the reaction by nuclear magnetic resonance spectroscopy ( 1 1H-NMR spectrum), 100 mL of n-hexane was added to the reaction solution, and it was washed three times with 100 g of 10% aqueous sodium carbonate solution and three times with 100 mL of pure water, and then dried with anhydrous magnesium sulfate. After filtration and concentration, vacuum drying was carried out to obtain 78.0 g of a white solid (167 mmol: yield 76.3%). The structure was confirmed to be the target product by 1 1H-NMR spectrum. The measurement data are shown below.

[0413] 1 1H-NMR (400 MHz, CDCl3) δ: 6.30 (1H), 5.65 (1H), 4.20 - 4.00 (4H), 3.32 (2H), 1.64 - 1.58 (4H), 1.40 - 1.25 (36H), 0.96 - 0.83 (6H)

[0414] <Synthesis Example 2 of Polymerizable Compound>

[0415] Synthesis of Dihexylacrylamide (AAA-C6C6)

[0416] [Chemical Formula 34]

[0417]

[0418] In a four-necked flask, 33.3 g (180 mmol) of dihexylamine and 27.3 g (270 mmol) of triethylamine were measured, and 500 mL of THF was added, and they were completely dissolved at room temperature. After confirming dissolution, the reaction vessel was cooled with ice and maintained at 0 °C in the system, and 17.9 g (198 mmol) of acryloyl chloride was slowly added dropwise. By nuclear magnetic resonance spectroscopy (1 After confirming the completion of the reaction by \(^{1}H-NMR\) spectrum, 100 mL of ethyl acetate was added to the reaction solution, and it was washed 3 times with 100 g of 10% aqueous sodium carbonate solution and 3 times with 100 mL of pure water, and dried over anhydrous magnesium sulfate. After filtration and concentration, vacuum drying was carried out to obtain 33.6 g of a transparent oily liquid (140 mmol: yield 78.1%). The structure was confirmed to be the target product by 1 \(^{1}H-NMR\) spectrum. The measurement data are shown below.

[0419] 1 \(^{1}H-NMR\) (400 MHz, DMSO-d6) δ: 6.62 (1H), 6.04 (1H), 5.58 (1H), 3.20 - 4.00 (4H), 3.35 - 3.25 (4H), 1.64 - 1.58 (4H), 1.30 - 1.25 (12H), 0.96 - 0.83 (6H)

[0420] <Polymerizable Compound Synthesis Example 3>

[0421] Synthesis of 4-Pentylcyclohexyl Methacrylate (MACH-C5)

[0422] [Chemical Formula 35]

[0423]

[0424] In a four-necked flask, 25.0 g (147 mmol) of 4-pentylcyclohexanol and 22.3 g (220 mmol) of triethylamine were measured, 400 mL of THF was added, and it was completely dissolved at room temperature. After confirming the dissolution, the system was maintained at 0 °C in an ice bath, and 18.4 g (176 mmol) of methacryloyl chloride was slowly added dropwise. By nuclear magnetic resonance spectroscopy ( 1 \(^{1}H-NMR\) spectrum) After confirming the completion of the reaction, 100 mL of hexane was added to the reaction solution, and it was washed 3 times with 100 g of 10% aqueous sodium carbonate solution and 3 times with 100 mL of pure water, and dried over anhydrous magnesium sulfate. After filtration and concentration, vacuum drying was carried out to obtain 20.3 g of a transparent oily liquid (86.2 mmol: yield 58.0%). The structure was confirmed to be the target product by 1 \(^{1}H-NMR\) spectrum. The measurement data are shown below.

[0425] 1H-NMR(400MHz, DMSO-d6) δ: 6.15 - 5.95(1H), 5.65 - 5.60(1H), 4.95 - 4.90(0.60H), 4.65 - 4.57(0.40H), 1.89 - 1.86(3H), 1.79 - 1.74(2H), 1.56 - 1.50(2H), 1.36 - 1.15(11H), 0.87 - 0.84(3H)

[0426] <Purchase of Polymerizable Compound>

[0427] The polymerizable compound DMA was directly used as purchased from Tokyo Chemical Industry Co., Ltd. (TCI).

[0428] (Fabrication of Liquid Crystal Display Element)

[0429] Using the obtained AL-1 to AL-7 and SE-6414 and NRB-U438 (manufactured by Nissan Chemical Industries, Ltd.) which are liquid crystal alignment agents for horizontal alignment, a liquid crystal cell was fabricated, and a liquid crystal display element having the structure shown in Table 5 below was fabricated.

[0430] The structure of the liquid crystal cell is as shown in Table 5 below.

[0431] [Table 5]

[0432]

[0433] <First / Second Substrate>

[0434] The first / second substrate is an alkali-free glass substrate with a size of 30 mm × 40 mm and a thickness of 1.1 mm. An ITO (Indium-Tin-Oxide) electrode with a thickness of 10 μm is formed on the substrate. The first substrate and the second substrate are the same substrate, and the names are separated for convenience.

[0435] <Surface Treatment Process of AL-1, AL-2, AL-3, SE-6414>

[0436] After filtering AL-1, AL-2, AL-3, and SE-6414 using a filter with a pore size of 1.0 μm, they were coated on the electrode formation surface of the above-mentioned first / second substrate by spin coating and dried on a hot plate at 80°C for two minutes. Then, they were sintered in a thermal cycle heating furnace with an internal temperature of 230°C for 30 minutes to obtain a coating film with a film thickness of 100 nm.

[0437] The first / second substrates with the attached coating films obtained above are subjected to rubbing treatment. After lamination, in such a manner that the rubbing directions are anti-parallel, for the first substrate, the rubbing direction is rubbing treatment along the long side direction, and for the second substrate, the rubbing direction is rubbing treatment along the short side direction. The type of rubbing cloth used is rayon cloth (YA-20R) manufactured by Yoshikawa Chemical Industry Co., Ltd., and the roller diameter is 120 mm.

[0438] The rubbing treatment of AL-1, AL-2, and AL-3 is carried out under the conditions of a rotation speed of 500 rpm, a moving speed of 30 mm / sec, and a pushing amount of 0.3 mm.

[0439] In addition, the rubbing treatment of SE-6414 is carried out under the conditions of a rotation speed of 1000 rpm, a moving speed of 20 mm / sec, and a pushing amount of 0.4 mm.

[0440] After the rubbing treatment, ultrasonic washing is performed in pure water for 1 minute, and drying is carried out at 80 °C for 15 minutes.

[0441] <Surface treatment process for AL-4, AL-5, AL-6, AL-7, and NRB-U438>

[0442] After filtering AL-5, AL-6, and AL-7 using a filter with a pore size of 1.0 μm, they are coated on the electrode formation surfaces of the above-mentioned first / second substrates by spin coating, and dried on a heating plate at 70 °C for 90 seconds.

[0443] After that, using a high-pressure mercury lamp (313 nm band-pass filter manufactured by CERMA PRECISION), linearly polarized light with a wavelength of 313 nm is irradiated at 0.005 J / cm 2 for exposure, and sintered on a heating plate at 150 °C for 30 minutes.

[0444] After filtering AL-4 and NRB-U438 using a filter with a pore size of 1.0 μm, they are coated on the electrode formation surfaces of the above-mentioned first and second substrates by spin coating, dried on a heating plate at 80 °C for two minutes, and sintered in a thermal cycling heating furnace with an internal temperature of 230 °C for 30 minutes. After that, using a low-pressure mercury lamp (240 nm short-wavelength cut-off filter manufactured by Ushio Electric Co., Ltd.), linearly polarized light with a wavelength of 254 nm is irradiated at 0.3 J / cm 2 for exposure, and sintered in a thermal cycling heating furnace with an internal temperature of 230 °C for 30 minutes.

[0445] <First exposure>

[0446] After the surface treatment process is completed, two substrates (first / second substrates) with a liquid crystal alignment film are irradiated with light of wavelength 313 nm at 10 J / cm using a high-pressure mercury lamp (a 300 nm or less short-wavelength cut-off filter manufactured by CERMA PRECISION). 2 Exposure. When selectively irradiating light, a photomask (100, 50, 30, 5 μm L / S with chromium wiring manufactured by Mitani Micronics) is placed on the substrate, and pattern exposure is performed. After that, this operation is recorded as one exposure.

[0447] In addition, one exposure is for the purpose of deliberately inactivating the radical-generating groups contained in the alignment film, and is only applicable to Examples 23, 24, 27, 28, 29, 30, and 32.

[0448] <Fabrication of liquid crystal cell>

[0449] Using the completed surface treatment method, for the two substrates (first / second substrates) with a liquid crystal alignment film after the one-exposure method further performed for Examples 23, 24, 27, 28, 29, 30, and 32, the periphery is sealed while leaving the liquid crystal injection port, and an empty cell with a cell gap of about 4 μm is fabricated. In addition, the process including the rubbing process in the surface treatment process fabricates the empty cell in such a way that the rubbing directions of the first substrate and the second substrate are anti-parallel.

[0450] In this empty cell, at room temperature and under vacuum, liquid crystal (as shown in Table 4, liquid crystal with specified amounts of various additives added to the positive IPS liquid crystal MLC-3019 manufactured by Merck or the negative IPS liquid crystal MLC-7026 manufactured by Merck) is injected, and then the injection port is sealed to form a liquid crystal cell. The obtained liquid crystal cell constitutes an IPS-mode liquid crystal display element. After that, the obtained liquid crystal cell is heat-treated at 120 °C for 10 minutes.

[0451] <Second exposure>

[0452] The fabricated liquid crystal cell is irradiated with light of wavelength 313 nm using a high-pressure mercury lamp (a 300 nm or less short-wavelength cut-off filter manufactured by CERMA PRECISION). The irradiation amount is as shown in Table 5. In addition, when selectively irradiating light, a photomask (100, 50, 30, 5 μm L / S with chromium wiring manufactured by Mitani Micronics) is placed on the liquid crystal cell, and pattern exposure is performed. After that, this operation is recorded as the second exposure. In addition, the second exposure is for the purpose of causing the reaction between the radical-generating groups contained in the alignment film and the polymerizable compound (additive) in the liquid crystal.

[0453] (Results of Visual Evaluation of Liquid Crystal Orientation after Double Exposure)

[0454] The orientation state of the liquid crystal unit after the double exposure was confirmed using a polarizing plate configured to be crossed nicols. In addition, the angle between the uniaxial orientation direction of the liquid crystal and the polarization direction was set to 45 degrees. At this time, light is transmitted when the liquid crystal is uniaxially oriented, and light is not transmitted when it is out-of-plane oriented.

[0455] As an example, unit 7 (Example 5) can perform out-of-plane orientation control, so the exposed area becomes a dark field ( Figure 1A as well as Figure 1B ).

[0456] Figure 1A A photograph showing a liquid crystal display element, in Figure 1B It is schematically shown in Figure 1A A photograph of a liquid crystal display element (hereinafter, in FIGS. 2 to 5 and 9 , a photograph of a liquid crystal display element is shown in FIG A , and a schematic diagram of the photograph is shown in FIG B ).

[0457] Figure 1 (also Figure 1A as well as Figure 1B In FIG. 1 , the exposed portion denoted by 1 is a dark field (black), and the non-exposed portion denoted by 2 is a bright field (white).

[0458] Unit 27 (Comparative Example 4) could not perform out-of-plane alignment control, so the exposed portion became a bright field ( Figure 2A as well as Figure 2B ).

[0459] In Figure 2 (also Figure 2A as well as Figure 2B In FIG. 2 , both the exposed area and the non-exposed area are shown as a bright field (white).

[0460] Unit 1 (Example 1) is tilted (tilt) oriented (partially out-of-plane oriented), so the coloring of the exposed part is reduced (partially dark field), and is represented by a gray intermediate color ( Figure 3A as well as Figure 3B ).

[0461] In Figure 3 (also Figure 3A as well as Figure 3B In FIG. 3 , the exposed area denoted by 1 is a mixture of the dark field (black) b and the intermediate color (gray) a. The non-exposed area denoted by 2 is a bright field (white).

[0462] The liquid crystal display elements in the respective Examples and Comparative Examples shown in the following Tables 6 to 8 were evaluated by the same method as that shown in FIGS. 1 to 3 .

[0463] In Tables 6 to 8, the areas of the second exposure are shown as dark field (black), and the areas where out-of-plane orientation control can be performed are marked with ○, the areas shown as bright field (white) and where out-of-plane orientation control cannot be performed are marked with ×, and the areas shown as intermediate color (gray) and having a uniaxial orientation or non-uniform orientation with an inclination angle are marked with △.

[0464] The results of visual evaluation of the liquid crystal orientation after the second exposure are shown in Table 6 below.

[0465] [Table 6]

[0466]

[0467]

[0468] In order to induce out-of-plane orientation from the in-plane uniaxial orientation state, it is necessary to (i) make the alignment film contain a group capable of generating free radicals, (ii) make the liquid crystal contain a polymerizable compound (additive), and (iii) perform light irradiation. In addition, at this time, it is effective to consider the content of the group capable of generating free radicals, the content of the polymerizable compound, the irradiation amount of light, etc. in order to form a good out-of-plane orientation state.

[0469] The results of visual evaluation of the liquid crystal orientation after the second exposure are shown in Table 7 below.

[0470] [Table 7]

[0471] Cell number of the liquid crystal cell Alignment state Example 12 17 〇 Example 13 17 〇 Example 14 18 〇 Example 15 20 〇 Example 16 8 △ Example 17 19 〇

[0472] The polymerizable compound (additive) required for out-of-plane orientation control is not limited to DMA. As long as it is an additive with an appropriate structure, out-of-plane orientation control can be performed. In addition, the liquid crystal species is not limited to MLC-7026 which is a liquid crystal with a negative dielectric constant. Even for MLC-3019 which is a liquid crystal with a positive dielectric constant, out-of-plane orientation control can be performed.

[0473] The results of visual evaluation of the liquid crystal orientation after the second exposure are shown in Table 8 below.

[0474] [Table 8]

[0475] Cell number of the liquid crystal cell Alignment state Example 18 21 〇 Example 19 22 〇 Example 20 23 〇 Example 21 24 〇 Example 22 25 〇 Comparative Example 5 26 × Comparative Example 6 28 ×

[0476] When using a photo-aligned film that has undergone photo-alignment treatment, out-of-plane alignment control can also be performed, regardless of the type of polymer that constitutes the alignment film and the exposure wavelength required for photo-alignment. In addition, as shown in the liquid crystal cells 22 or 23 used in Examples 19, 20, etc., when using an alignment film material that does not have a radical-generating group, out-of-plane alignment control can be achieved by mixing it with a polymer material that has a group capable of generating radicals. At this time, as long as an appropriate amount of the group capable of generating radicals is introduced, out-of-plane alignment control can be performed. In addition, as in Examples 21 and 22, when only a photo-aligned film with radical-generating ability is coated on the first substrate, out-of-plane alignment control can sometimes be achieved. This depends on the type of photo-aligned film used. For example, when the alignment constraint force of the liquid crystal is small, it can be observed when the alignment constraint force of the liquid crystal decreases due to light irradiation.

[0477] (Results of visual evaluation of liquid crystal alignment properties during single exposure)

[0478] Using a polarizing plate configured as crossed Nicol, the alignment state of the liquid crystal cell after double exposure was confirmed. In addition, the angle formed between the uniaxial alignment direction of the liquid crystal cell and the polarization direction was set to 45 degrees. The results are shown in Table 9 below.

[0479] [Table 9]

[0480]

[0481] As a single exposure, if the entire first substrate is exposed, an inclined (tilt) alignment ( Figure 4A and Figure 4B ) is formed.

[0482] In Figure 4 (which also collectively refers to Figure 4A and Figure 4B as Figure 4), the part indicated by the symbol 3 is the area where only the first substrate is exposed by single exposure and the entire surface is exposed by double exposure. The part indicated by the symbol 3 shows a gray intermediate color and forms an inclined (tilt) alignment. The part indicated by the symbol 4 is the non-exposed area where only the first substrate is exposed by single exposure and not exposed by double exposure. The part indicated by the symbol 4 shows a bright field (white) and forms an in-plane alignment.

[0483] When the entire first substrate and the second substrate are exposed by single exposure, an in-plane alignment ( Figure 5A and Figure 5B ) is formed.

[0484] In Figure 5 (which also collectively refers to Figure 5A and Figure 5BIn the part denoted by symbol 5 in the overall (Figure 5), the area where the first / second substrates are exposed by single exposure and the entire surface is exposed by double exposure. The part denoted by symbol 6 is the non-exposed area where the first and second substrates are exposed by single exposure but not by double exposure. The parts of symbols 5 and 6 are both shown as bright field (white), forming in-plane alignment. Thus, it can be confirmed that by irradiating the substrate before cell fabrication, the groups capable of generating free radicals contained in the alignment film are inactivated, and no reaction with the polymerizable compound (additive) is induced during double exposure, and out-of-plane alignment is not formed.

[0485] (Evaluation of alignment patterning)

[0486] Using a polarizer configured as crossed Nicol, the alignment state of the pattern-exposed liquid crystal display element was confirmed. In addition, the angle formed by the uniaxial alignment direction of the liquid crystal cell and the polarization direction was set to 45 degrees. The evaluation of the alignment pattern was visually observed and judged from the viewpoints of whether alignment control could be performed based on light irradiation, the uniformity of alignment, and the sharpness of the alignment control surface (the interface between in-plane uniaxial alignment and out-of-plane alignment). The results are shown in Table 10 below.

[0487] [Table 10]

[0488] Cell number of the liquid crystal cell Patterning state Example 25 7 Uniform and distinct ( Figure 6 left) Example 26 21 Uniform and distinct ( Figure 6 right)

[0489] The alignment change from in-plane (uniaxial) alignment to out-of-plane alignment based on light irradiation can be uniformly controlled, and the interface between different alignments is sharp ( Figure 6 ). As Figure 6 shown, it can be confirmed that the in-plane alignment area in bright field (white) and the out-of-plane alignment area in dark field (black) are clearly patterned.

[0490] In addition, this does not depend on the type of polymer constituting the alignment film or the alignment treatment method. Alignment patterns can be fabricated using materials that are significantly different in type, so it can be inferred that the examples capable of out-of-plane alignment control in Tables 6 to 8 can all be alignment-patterned.

[0491] (Evaluation of fine alignment patterning)

[0492] Using a polarizer configured as crossed Nicol, the alignment state of the pattern-exposed liquid crystal display element was confirmed. In addition, the angle formed by the uniaxial alignment direction of the liquid crystal cell and the polarization direction was set to 45 degrees. The evaluation of the alignment pattern was visually observed and judged from the viewpoints of whether alignment control could be performed based on light irradiation, the uniformity of alignment, and the sharpness of the alignment control surface (the interface between in-plane uniaxial alignment and out-of-plane alignment). The results are shown in Table 11 below.

[0493] [Table 11]

[0494]

[0495] As a single exposure, a liquid crystal display element produced using a substrate exposed with a pattern can form a uniform and clear fine alignment pattern regardless of the L / S width of the photomask.

[0496] For example, a photograph of the liquid crystal display element obtained in Example 27 is shown in Figure 7 . At this time, since only the first substrate is pattern-exposed as a single exposure, Figure 7 the intermediate color (gray) portion indicated by the symbol 7 forms a tilt alignment state. Figure 7 The dark field (black) portion indicated by the symbol 8 forms an out-of-plane alignment state.

[0497] Figure 8 The results of Example 30 obtained by changing the L / S width of the photomask of Example 27 are shown. In Figure 8 , the difference between the intermediate color (gray) portion and the dark field (black) portion is as Figure 7 explained.

[0498] In addition, when it is desired to make the intermediate color (gray) portion an in-plane uniaxial alignment, the second substrate is also pattern-exposed in the same manner as the first substrate, and after the exposed portions are bonded to each other to form a liquid crystal cell, a second exposure is performed.

[0499] As a liquid crystal display element that performs pattern exposure by second exposure without performing single exposure, as shown in Example 31, it can be recognized that alignment patterning can be performed under the condition that the L / S width of the photomask is 100 μm. In the liquid crystal display element of Example 31, the in-plane alignment region of the bright field (white) and the out-of-plane alignment region of the dark field (black) can also be clearly patterned.

[0500] In addition, as shown in Example 32, it can be confirmed that by pattern-exposing both the first / second substrates, bonding the pattern directions perpendicularly to form a liquid crystal cell, and then performing a second exposure, three alignment states of in-plane uniaxial alignment, out-of-plane alignment, and tilt alignment can be formed in one liquid crystal display element.

[0501] The results of the liquid crystal display element obtained in Example 32 are shown ([[]]END]] Figure 9A and Figure 9B ). Figure 9A A photograph of the liquid crystal display element is shown, Figure 9A and a schematic diagram of the photograph of the liquid crystal display element is shown in Figure 9B .

[0502] As shown in FIG. 9 (also Figure 9A andFigure 9B As shown in the overall view (Figure 9), the dark field (black) portion indicated by symbol 9 forms an out-of-plane orientation state. The bright field (white) portion indicated by symbol 10 forms an in-plane orientation. The intermediate color (gray) portion indicated by symbol 11 ( Figure 9B in which is the portion represented by the slanted pattern) forms a tilt orientation state.

[0503] Industrial Applicability

[0504] According to the present invention, it is possible to industrially produce, with good productivity, a liquid crystal display element in which at least two regions of an in-plane orientation region, an out-of-plane orientation region, and a tilt orientation region are patterned.

[0505] Explanation of Symbols

[0506] 101 Liquid crystal display element

[0507] 102 Comb electrode substrate

[0508] 102a Substrate

[0509] 102b Linear electrode

[0510] 102c Free radical generating film

[0511] 102d Substrate

[0512] 102e Planar electrode

[0513] 102f Insulating film

[0514] 102g Linear electrode

[0515] 102h Free radical generating film

[0516] 103 Liquid crystal composition

[0517] 104 Opposite substrate

[0518] 104a Liquid crystal alignment film

[0519] 104b Substrate

Claims

1. A method for manufacturing a liquid crystal display element, characterized in that, Comprising: Step (A): forming a radical generating film capable of generating radicals upon light irradiation on one substrate, and forming a radical generating film capable of generating radicals upon light irradiation on another substrate; And Step (B): bringing a liquid crystal composition containing a liquid crystal and a radical polymerizable compound into contact with the radical generating film, and while maintaining this state, irradiating the liquid crystal composition with light having a peak in the range of 240 to 400 nm sufficient to cause the radical polymerizable compound to undergo a polymerization reaction; Said one substrate and said another substrate form a pair of substrates; Said radical polymerizable compound has the function of vertically aligning the liquid crystal through polymerization; The radical generating film formed on said one substrate and the radical generating film formed on said another substrate are uniaxially oriented coated films and have the function of forming in-plane orientation; Furthermore, said manufacturing method includes, for at least one of said pair of substrates, a step of requirement (Z1), In the step of requirement (Z1), when irradiating the radical generating film with light, in the case of pattern exposure, it includes the following step (a), and in the case of full-surface exposure, it includes the following step (b); And manufacturing a liquid crystal display element in which at least two different types of regions including any one of the combinations of (i) a tilted alignment region and an in-plane alignment region, (ii) a tilted alignment region and an out-of-plane alignment region, and (iii) a tilted alignment region, an in-plane alignment region, and an out-of-plane alignment region are patterned; Wherein, said tilted alignment region is: a region formed by arranging said one substrate with in-plane alignment and said another substrate with out-of-plane alignment in the pair of substrates facing each other, or arranging said one substrate with out-of-plane alignment and said another substrate with in-plane alignment in the pair of substrates facing each other; Said in-plane alignment region is: a region formed by arranging said one substrate with in-plane alignment and said another substrate with in-plane alignment in the pair of substrates facing each other; Said out-of-plane alignment region is: a region formed by arranging said one substrate with out-of-plane alignment and said another substrate with out-of-plane alignment in the pair of substrates facing each other; Requirement (Z1): There is a step (C) between said step (A) and said step (B), wherein the radical generating film obtained in said step (A) is irradiated with light having a peak in the range of 240 to 400 nm to inactivate the radical generating ability of the radical generating film; Step (a): Through said pattern exposure, forming a part that inactivates the radical generating ability of the radical generating film and a part that does not inactivate the radical generating ability of the radical generating film; Step (b): Through said full-surface exposure, in the case of inactivating the radical generating ability of the radical generating film, it further includes the following requirement (Z2); Requirement (Z2): The step of irradiating the liquid crystal composition with light having a peak in the range of 240 to 400 nm in said step (B) is carried out through a photomask.

2. The manufacturing method of the liquid crystal display element according to claim 1, wherein, The step of irradiating the liquid crystal composition with light having a peak in the range of 240 to 400 nm in the step (B) is carried out without an electric field.

3. The manufacturing method of the liquid crystal display element according to claim 1 or 2, wherein, Among the radical generating films formed on the one substrate and the radical generating films formed on the other substrate, at least one of the radical generating films has a polymer containing an organic group that initiates radical polymerization.

4. The manufacturing method of the liquid crystal display element according to claim 3, wherein, The polymer containing an organic group that initiates radical polymerization has a structural unit represented by the following formula (1) in the main chain. ； In formula (1), A represents an organic group that initiates radical polymerization.

5. The manufacturing method of the liquid crystal display element according to claim 3, wherein, The polymer is at least one selected from polyimide precursors, polyimides, polyureas, and polyamides obtained using a diamine component, and the diamine component includes a diamine containing an organic group that initiates radical polymerization.

6. The manufacturing method of the liquid crystal display element according to claim 4, wherein, The organic group that initiates radical polymerization is a group represented by the following formula (3). ； In formula (3), the dashed line represents a bond connected to the benzene ring, and R 6 represents a single bond, -CH2-, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH2O-, -N(CH3)-, -CON(CH3)-, or -N(CH3)CO- R 7 represents a single bond, or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted with fluorine atoms, and one or more of any -CH2- or -CF2- in the alkylene group are each independently replaced or not replaced by a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and further, under the condition that any one of the following groups, namely -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other, it is replaced or not replaced by these groups R 8 represents an organic group that initiates radical polymerization and is represented by a formula selected from the formulas [X-1] to [X-18], [W], [Y], and [Z] ； In formulas [X-1] to [X-18], represents the bonding site with R 7 , S1 and S2 each independently represent -O-, -NR-, or -S-, where R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R1 and R2 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. ； In formulas [W], [Y], and [Z], represents the bonding site with R 7 ; S 3 represents a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH2O-, -N(CH3)-, -CON(CH3)-, or -N(CH3)CO-; Ar represents an aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene which may or may not have an organic group and / or a halogen atom as a substituent; R 9 and R 10 each independently represents an alkyl group, an alkoxy group, a benzyl group, or a phenethyl group having 1 to 10 carbon atoms. When it is an alkyl group or an alkoxy group, R 9 and R 10 may or may not form a ring; Q represents any of the following structures. ； In the formula, R 11 represents -CH2-, -NR-, -O-, or -S-, where R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, represents a bond position, R 12 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

7. The manufacturing method of the liquid crystal display element according to claim 5, wherein, The diamine containing an organic group that initiates radical polymerization is a diamine represented by the following formula (2). ； In formula (2), A 1 and A 2 each represent a hydrogen atom or a group represented by the following formula (3), where at least one of A 1 and A 2 represents a group represented by the following formula (3). E represents a single bond, -O-, -C(CH3)2-, -NH-, -CO-, -NHCO-, -COO-, -(CH2) m -, -SO2-, or a divalent organic group formed by any combination thereof, m represents an integer from 1 to 8, p represents an integer from 0 to 2; when p is 2, multiple A 2 and E each independently have the aforementioned definitions; in addition, when p is 0, A 1 contains a group represented by the following formula (3), ； In formula (3), the dashed line represents a bond connected to the benzene ring, and R 6 represents a single bond, -CH2-, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH2O-, -N(CH3)-, -CON(CH3)-, or -N(CH3)CO- R 7 represents a single bond, or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by fluorine atoms, and one or more of any -CH2- or -CF2- in the alkylene group are each independently replaced or not replaced by a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and further, under the condition that any one of the following groups, namely -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other, it is replaced or not replaced by these groups R 8 represents an organic group that initiates radical polymerization and is represented by a formula selected from formulas [X-1] to [X-18], [W], [Y], and [Z] ； In Formulas [X-1] to [X-18], represents the bonding site with R 7 , S1 and S2 each independently represent -O-, -NR-, or -S-, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R1 and R2 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. ； In formulas [W], [Y], and [Z], represents the bonding site with R 7 ; S 3 represents a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH2O-, -N(CH3)-, -CON(CH3)-, or -N(CH3)CO-; Ar represents an aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene which may or may not have an organic group and / or a halogen atom as a substituent; R 9 and R 10 each independently represent an alkyl group, an alkoxy group, a benzyl group, or a phenethyl group having 1 to 10 carbon atoms. When it is an alkyl group or an alkoxy group, R 9 and R 10 may form a ring or may not form a ring; Q represents any of the following structures. ； In the formula, R 11 represents -CH2-, -NR-, -O-, or -S-, and R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, represents a bond position, R 12 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

8. The manufacturing method of the liquid crystal display element according to claim 1 or 2, wherein, At least one of the radical polymerizable compounds is a compound that is compatible with liquid crystal and has one polymerizable unsaturated bond in one molecule.

9. The manufacturing method of the liquid crystal display element according to claim 8, wherein, The polymerization reactive groups possessed by the radical polymerizable compounds are selected from the following structures. ； In the formula, represents a site bonded to a portion other than the polymerizable unsaturated bond of the compound molecule; R b represents an alkyl group having 3 to 20 carbon atoms; E represents a linking group selected from a single bond, -O-, -NR c -, -S-, an ester bond, and an amide bond, wherein R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; the alkyl group of R b represents a straight-chain, branched, or cyclic alkyl group.

10. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein, The radical polymerizable compounds contained in the liquid crystal composition containing liquid crystal and radical polymerizable compounds satisfy the following condition: the Tg of the polymer obtained by polymerizing the radical polymerizable compounds is 100 °C or lower.

11. The manufacturing method of the liquid crystal display element according to claim 1, wherein, The one substrate is a substrate having comb-shaped electrodes.

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