TW202130703A - Method for manufacturing patterned liquid crystal display element - Google Patents

Abstract

Provided is a method for manufacturing, in a simple, low-cost manner, a liquid crystal display element that includes two or three different orientation regions (an in-plane (uniaxial) orientation region, an out-of-plane orientation region, and an inclined orientation region) in the same element. The present invention provides a method for manufacturing a liquid crystal display element in which at least two regions of an in-plane orientation region, an out-of-plane orientation region, and an inclined orientation region are used as patterns therein. The method includes: a step (A) for forming, on a substrate, a radical generation film that could generate radicals as a result of being irradiated with light; and a step (B) for bringing a liquid crystal composition, which contains liquid crystals and a radical-polymerizable compound, into contact with the radical generation film and for irradiating, while maintaining said state, the liquid crystal composition with light having a peak at 240-400 nm, which is sufficient to cause a polymerization reaction of the radical-polymerizable compound. The radical-polymerizable compound has a function of vertically orienting the liquid crystals as a result of being polymerized. Furthermore, the method includes at least one of requirements (Z1) and (Z2). Requirement (Z1): a step (c) for deactivating the radical generation ability of the radical generation film by irradiating the radical generation film obtained in the step (A) with the light having a peak at 240-400 nm is additionally included between the step (A) and the step (B). Requirement (Z2): the step for irradiating the liquid crystal composition with the light having a peak at 240-400 nm in the step (B) is performed via a photomask.

Description

Manufacturing method of patterned liquid crystal display element

The present invention relates to a method for manufacturing a liquid crystal display element in which at least two of the in-plane alignment area, the out-of-plane alignment area, and the oblique alignment area are patterned by using an inexpensive method that does not include complicated steps.

In recent years, liquid crystal display elements have been widely used in mobile phones, computers, and TV monitors. Liquid crystal display elements have the characteristics of thinness, light weight, and low power consumption. In the future, they are expected to be used in VR (Virtual Reality), ultra-high-definition displays, and more. As far as the display mode of liquid crystal displays is concerned, various display modes such as TN (Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), etc. have been proposed. All modes A film (liquid crystal alignment film) that induces the liquid crystal into a desired alignment state is used.

In particular, products with touch panels such as tablet PCs, smartphones, and smart TVs prefer to use the IPS mode that is not easily disturbed even when touched. In recent years, considering the viewpoint of improving contrast and improving viewing angle characteristics, FFS has gradually been adopted. (Frindge Field Switching) Liquid crystal display elements use optical alignment technology that uses non-contact technology.

However, FFS has the following problem: Compared with IPS, the manufacturing cost of the substrate is high, and display defects unique to the FFS mode called Vcom shift occur. In addition, with regard to optical alignment, compared to the rubbing method, the size of the device that can be manufactured can be increased, and the display characteristics can be greatly improved. However, the principle of optical alignment can be cited (if it is a decomposition type, It is due to poor display from the decomposition product, if it is an isomerized type, it is due to the imprinting caused by insufficient alignment power, etc.). In order to solve these problems, current liquid crystal display element manufacturers and liquid crystal alignment film manufacturers are making various efforts.

On the other hand, in recent years, some people have proposed an IPS mode that uses zero-plane anchoring (also known as weak anchoring). It is reported that by using this method, compared with the previous IPS mode, the contrast can be improved and it can be driven at a significantly low voltage. (Refer to Patent Document 1).

Specifically, a liquid crystal alignment film with strong anchoring energy is used on a single-sided substrate, and a treatment is applied to the side of the substrate with electrodes that generate a transverse electric field to lose all the alignment constraints of the liquid crystal, and use this Etc. to produce the method of IPS mode liquid crystal display element.

In recent years, some people have used thick polymer brushes to create a zero-plane state, and a technology of zero-plane anchoring IPS mode has been proposed (for example, refer to Patent Document 2). With this technology, the contrast ratio is greatly improved and the driving voltage is greatly reduced. On the other hand, there is a problem that the response speed, especially the response speed when the voltage is OFF, is significantly reduced. This is because the driving voltage becomes lower, compared with the usual driving method, the response is caused by a weaker electric field, and because the anchoring force of the alignment film is extremely small, the recovery of the liquid crystal takes time. As a solution to this problem, a method of zero anchoring only on the pixel electrode has been proposed (for example, refer to Patent Document 3). It is reported that this can take into account both the improvement of brightness and the speed of response. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 4053530 [Patent Document 2] JP 2013-231757 A [Patent Document 3] JP 2017-211566 A

[The problem to be solved by the invention]

If you use an alignment film that is appropriately designed for the application, you can control the alignment state of various liquid crystals. Especially when used for an alignment film with an anchoring force in a uniaxial direction in a plane, an in-plane uniaxial alignment can be obtained, and when an alignment film with an anchoring force in an out-of-plane direction is used, an out-of-plane alignment can be obtained. On the other hand, it is very difficult to manufacture a liquid crystal element having both an in-plane uniaxial alignment region and an out-of-plane alignment region in the same element. This is because it is necessary to make areas with greatly different anchoring forces in the same element. In order to achieve this, the anchoring force of any area must be changed after the liquid crystal element is made, or the substrate of the constituent element must be coated with different anchors in advance. The alignment film of Dingli. As for the former, there are still no reported cases, and the latter has become a major issue in industrialization because it needs to be applied separately in very small areas and prepared to apply the alignment treatment technology. If such a technical problem is solved, a liquid crystal element with an arbitrary alignment state can be formed in any area, and it can be expected to be applied to optical films, optical property modulation elements, and the like. In order to solve the above-mentioned problems, the present invention aims to provide a method for manufacturing a liquid crystal display device, which induces a chemical reaction due to the contact interface between the alignment film and the liquid crystal, and induces a chemical reaction in any area in the direction of the alignment film. , And the surface energy and anchoring energy of the interface reaction area are controlled to any state, and it is manufactured in a simple and low-cost method. It has 2 or 3 different alignment areas (in-plane (uniaxial) alignment area, out-of-plane) in the same device Alignment area, and oblique alignment area) of the liquid crystal display element. [Means to solve the problem]

As a result of diligent researches conducted by the inventors of the present application to solve the above-mentioned problems, they found that the above-mentioned problems can be solved, and completed the present invention having the following gist.

式(1)中，A表示誘發自由基聚合之有機基。 [6] 如[4]或[5]之液晶顯示元件之製造方法，其中，前述聚合物係選自使用包含含有誘發自由基聚合之有機基之二胺的二胺成分而獲得之聚醯亞胺前驅體、聚醯亞胺、聚脲、及聚醯胺中之至少一種。 [7] 如[5]之液晶顯示元件之製造方法，其中，前述誘發自由基聚合之有機基係下式(3)表示之基。 [化2]

式(3)中，虛線表示與苯環之鍵結，R⁶ 表示單鍵、-CH₂ -、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH₂ O-、-N(CH₃ )-、-CON(CH₃ )-、或-N(CH₃ )CO-； R⁷ 表示單鍵、或非取代或經氟原子取代之碳數1～20之伸烷基，該伸烷基之任意之-CH₂ -或-CF₂ -中之一者以上也可各自獨立地置換為選自-CH＝CH-、二價碳環、及二價雜環之基，另外，亦能以下列所列舉之任意基，亦即-O-、-COO-、-OCO-、-NHCO-、-CONH-、或-NH-彼此不相鄰為條件而置換為該等基； R⁸ 表示選自式[X-1]～[X-18]、[W]、[Y]及[Z]之式表示之誘發自由基聚合之有機基； [化3]

式[X-1]～[X-18]中，＊表示與R⁷ 之鍵結部位，S₁ 及S₂ 各自獨立地表示-O-、-NR-、或-S-，R表示氫原子、鹵素原子、碳數1～10之烷基、或碳數1～10之烷氧基，R₁ 及R₂ 各自獨立地表示氫原子、鹵素原子、或碳數1～4之烷基； [化4]

式[W]、[Y]、[Z]中，＊表示與R⁷ 之鍵結部位，S³ 表示單鍵、-O-、-S-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH₂ O-、-N(CH₃ )-、-CON(CH₃ )-、或-N(CH₃ )CO-，Ar表示選自由亦可具有有機基及/或鹵素原子作為取代基之伸苯基、伸萘基、及伸聯苯基構成之群組中之芳香族烴基，R⁹ 及R¹⁰ 各自獨立地為碳數1～10之烷基、烷氧基、苄基、或苯乙基，為烷基、烷氧基時，R⁹ 及R¹⁰ 亦可形成環； Q表示下列任一結構； [化5]

式中，R¹¹ 表示-CH₂ -、-NR-、-O-、或-S-，R表示氫原子或碳數1～4之烷基，＊表示原子鍵； R¹² 表示氫原子、鹵素原子、碳數1～10之烷基或碳數1～10之烷氧基。 [8] 如[6]之液晶顯示元件之製造方法，其中，前述含有誘發自由基聚合之有機基的二胺，係具有下式(2)表示之結構的二胺。 [化6]

式(2)中，A¹ 及A² 各自獨立地表示氫原子或下式(3)表示之基，惟，A¹ 及A² 中之至少1者表示下式(3)表示之基， E表示單鍵、-O-、-C(CH₃ )₂ -、-NH-、-CO-、-NHCO-、-COO-、-(CH₂ )_m -、-SO₂ -、或由該等之任意組合構成之2價有機基，m表示1～8之整數。 p表示0～2之整數。p為2時，多個A² 及E各自獨立地具有前述定義。又，p為0時，A¹ 由下式(3)表示之基構成。 [化7]

式(3)中，虛線表示與苯環之鍵結，R⁶ 表示單鍵、-CH₂ -、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH₂ O-、-N(CH₃ )-、-CON(CH₃ )-、或-N(CH₃ )CO-， R⁷ 表示單鍵、或非取代或經氟原子取代之碳數1～20之伸烷基，該伸烷基之任意之-CH₂ -或-CF₂ -中之一者以上也可各自獨立地置換為選自-CH＝CH-、二價碳環、及二價雜環之基，另外，亦能以下列所列舉之任意基，亦即-O-、-COO-、-OCO-、-NHCO-、-CONH-、或-NH-彼此不相鄰為條件而置換為該等基； R⁸ 表示選自式[X-1]～[X-18]、[W]、[Y]及[Z]之式表示之誘發自由基聚合之有機基； [化8]

式[X-1]～[X-18]中，＊表示與R⁷ 之鍵結部位，S₁ 、S₂ 各自獨立地表示-O-、-NR-、-S-，R表示氫原子、鹵素原子、碳數1～10之烷基、碳數1～10之烷氧基，R₁ 、R₂ 各自獨立地表示氫原子、鹵素原子、碳數1～4之烷基； [化9]

式[W]、[Y]、[Z]中，＊表示與R⁷ 之鍵結部位，S³ 表示單鍵、-O-、-S-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH₂ O-、-N(CH₃ )-、-CON(CH₃ )-、或-N(CH₃ )CO-，Ar表示選自由亦可具有有機基及/或鹵素原子作為取代基之伸苯基、伸萘基、及伸聯苯基構成之群組中之芳香族烴基，R⁹ 及R¹⁰ 各自獨立地為碳數1～10之烷基、烷氧基、苄基、或苯乙基，為烷基、烷氧基時，R⁹ 及R¹⁰ 亦可形成環； Q表示下列任一結構； [化10]

式中，R¹¹ 表示-CH₂ -、-NR-、-O-、或-S-，R表示氫原子或碳數1～4之烷基，＊表示原子鍵； R¹² 表示氫原子、鹵素原子、碳數1～10之烷基或碳數1～10之烷氧基。 [9] 如[1]～[8]中任一項之液晶顯示元件之製造方法，其中，前述自由基聚合性化合物中之至少一種係與液晶具有相容性的於一分子中具有一個聚合性不飽和鍵之化合物。 [10] 如[9]之液晶顯示元件之製造方法，其中，前述自由基聚合性化合物所具有之聚合反應性基選自下列結構。 [化11]

式中，＊表示與化合物分子之聚合性不飽和鍵以外之部分的鍵結部位。R^b 表示碳數3～20之烷基，E表示選自單鍵、-O-、-NR^c -、-S-、酯鍵及醯胺鍵之鍵結基。R^c 表示氫原子、碳數1～4之烷基，R^b 之烷基表示直鏈、分支、或環狀之烷基。 [11] 如[1]～[10]中任一項之液晶顯示元件之製造方法，其中，前述含有液晶及自由基聚合性化合物之液晶組成物中，含有將前述自由基聚合性化合物聚合而獲得之聚合物之Tg為100℃以下的自由基聚合性化合物。 [12] 如[1]～[11]中任一項之液晶顯示元件之製造方法，更具有下列步驟： 準備具有自由基產生膜之第一基板、與第二基板， 以前述第一基板上之自由基產生膜面對前述第二基板的方式進行配置， 於前述第一基板與前述第二基板之間，填充含有液晶及自由基聚合性化合物之液晶組成物，藉此製作液晶胞。 [13] 如[12]之液晶顯示元件之製造方法，其中，前述第二基板具有自由基產生膜。 [14] 如[12]之液晶顯示元件之製造方法，其中，前述第二基板係塗覆有具有單軸配向性之液晶配向膜的基板。 [15] 如[14]之液晶顯示元件之製造方法，其中，前述具有單軸配向性之液晶配向膜係水平配向用之液晶配向膜。 [16] 如[12]～[15]中任一項之液晶顯示元件之製造方法，其中，前述具有自由基產生膜之第一基板係具有梳齒電極之基板。 [發明之效果]The present invention includes the following aspects. [1] A method for manufacturing a liquid crystal display element, characterized by: comprising: Step (A): forming a radical generating film capable of generating free radicals by light irradiation on a substrate; and Step (B): containing The liquid crystal composition of the liquid crystal and the radical polymerizable compound is in contact with the radical generating film, while maintaining the state, the liquid crystal composition is irradiated enough to cause the radical polymerizable compound to polymerize. The peak has a peak at 240-400 nm Light; The aforementioned radical polymerizable compound has the function of aligning the aforementioned liquid crystal vertically by polymerization; It also contains at least one of the following requirements (Z1) and (Z2), and manufactures in-plane alignment regions and out-of-plane alignment regions A liquid crystal display element in which at least two of the alignment area and the oblique alignment area are patterned; Requirement (Z1): there is a step (C) between the aforementioned step (A) and the aforementioned step (B), which corresponds to the aforementioned The radical generating film obtained in step (A) is irradiated with light having a peak at 240-400 nm to deactivate the radical generating ability of the radical generating film. Requirement (Z2): The step of irradiating the liquid crystal composition with light having a peak at 240 to 400 nm in the step (B) is performed through a photomask. [2] The method for manufacturing a liquid crystal display element according to [1], wherein the radical generating film is a film that has been uniaxially aligned. [3] The method of manufacturing a liquid crystal display element as in [1] or [2], wherein the step (B) of irradiating the liquid crystal composition with light having a peak at 240 to 400 nm is performed under no electric field . [4] 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 induces radical polymerization. [5] The method for manufacturing a liquid crystal display element according to [4], wherein the aforementioned polymer containing an organic group that induces radical polymerization has a structural unit represented by the following formula (1) in the main chain. [化1]

In formula (1), A represents an organic group that induces radical polymerization. [6] The method for producing a liquid crystal display element according to [4] or [5], wherein the polymer is selected from polyamides obtained by using a diamine component containing a diamine containing an organic group that induces radical polymerization At least one of an amine precursor, polyimine, polyurea, and polyamide. [7] The method for manufacturing a liquid crystal display element according to [5], wherein the organic group that induces radical polymerization is a group represented by the following formula (3). [化2]

In formula (3), the dotted line represents the bond with the benzene ring, and R ⁶ represents a single bond, -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-; R ⁷ represents a single bond, or the number of carbons substituted by fluorine atoms 1 ～20 alkylene, any _{one or more of -CH 2} -or -CF ₂ -of the alkylene can also be independently replaced by one selected from -CH=CH-, divalent carbocyclic ring, and two The group of a valent heterocyclic ring, in addition, can also be conditioned on any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other And substituted with these groups; R ⁸ represents an organic group that induces free radical polymerization represented by the formulas selected from the formulas [X-1]～[X-18], [W], [Y] and [Z]; [化] 3]

In formulas [X-1] ~ [X-18], * represents the bonding site ^{with R 7} _{, S 1} and S ₂ each independently represent -O-, -NR-, or -S-, and R represents a hydrogen atom , A halogen atom, an alkyl group with 1 to 10 carbons, or an alkoxy group with 1 to 10 carbons, R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, or an alkyl group with 1 to 4 carbons; [化4]

In the formulas [W], [Y], [Z], * represents the bonding site ^{with R 7 and S 3} represents a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, _{-CON(CH 3} )-, or -N(CH ₃ )CO-, Ar represents selected from or may have an organic group and / Or an aromatic hydrocarbon group in the group consisting of phenylene, naphthylene, and biphenyl with halogen atoms as substituents, R ⁹ and R ¹⁰ are each independently an alkyl group or alkane with 1 to 10 carbon atoms When the oxy, benzyl, or phenethyl group is an alkyl group or an alkoxy group, R ⁹ and R ¹⁰ may also form a ring; Q represents any of the following structures; [化5]

In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O-, or -S-, R represents a hydrogen atom or an alkyl group with 1 to 4 carbons, * represents an atomic bond; R ¹² represents a hydrogen atom, halogen Atom, C 1-10 alkyl group or C 1-10 alkoxy group. [8] The method for manufacturing a liquid crystal display element according to [6], wherein the aforementioned diamine containing an organic group that induces radical polymerization is a diamine having a structure represented by the following formula (2). [化6]

In formula (2), A ¹ and A ² each independently represent a hydrogen atom or a group represented by the following formula (3), but ^{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(CH ₃ ) ₂ -, -NH-, -CO-, -NHCO-, -COO-, -(CH ₂ ) _m -, -SO ₂ -, or these Any combination of the divalent organic group, m represents an integer of 1-8. p represents an integer of 0-2. When p is 2, a plurality of A ² and E each independently have the aforementioned definition. In addition, when p is 0, A ^{1 is} composed of a group represented by the following formula (3). [化7]

In formula (3), the dotted line represents the bond with the benzene ring, and R ⁶ represents a single bond, -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-, R ⁷ represents a single bond, or unsubstituted or substituted by a fluorine atom, carbon number 1 ～20 alkylene, any _{one or more of -CH 2} -or -CF ₂ -of the alkylene can also be independently replaced by one selected from -CH=CH-, divalent carbocyclic ring, and two The group of a valent heterocyclic ring, in addition, can also be provided that any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other as a condition And substituted with these groups; R ⁸ represents an organic group that induces free radical polymerization represented by the formulas selected from the formulas [X-1]～[X-18], [W], [Y] and [Z]; [化8]

In the formulas [X-1] to [X-18], * represents the bonding site ^{with R 7} _{, S 1} and S ₂ each independently represent -O-, -NR-, -S-, and R represents a hydrogen atom, A halogen atom, an alkyl group with 1 to 10 carbons, and an alkoxy group with 1 to 10 carbons, R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, and an alkyl group with 1 to 4 carbons; [化9]

In the formulas [W], [Y], [Z], * represents the bonding site ^{with R 7 and S 3} represents a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, _{-CON(CH 3} )-, or -N(CH ₃ )CO-, Ar represents selected from or may have an organic group and / Or an aromatic hydrocarbon group in the group consisting of phenylene, naphthylene, and biphenyl with halogen atoms as substituents, R ⁹ and R ¹⁰ are each independently an alkyl group or alkane with 1 to 10 carbon atoms When the oxy, benzyl, or phenethyl group is an alkyl group or an alkoxy group, R ⁹ and R ¹⁰ may also form a ring; Q represents any of the following structures; [化10]

In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O-, or -S-, R represents a hydrogen atom or an alkyl group with 1 to 4 carbons, * represents an atomic bond; R ¹² represents a hydrogen atom, halogen Atom, an alkyl group with 1 to 10 carbons or an alkoxy group with 1 to 10 carbons. [9] The method for manufacturing a liquid crystal display element according to any one of [1] to [8], wherein at least one of the aforementioned radically polymerizable compounds is compatible with liquid crystal and has one polymer in one molecule. Compounds with sexually unsaturated bonds. [10] The method for manufacturing a liquid crystal display element according to [9], wherein the polymerization reactive group possessed by the radically polymerizable compound is selected from the following structures. [化11]

In the formula, * represents the bonding site with the part other than the polymerizable unsaturated bond of the compound molecule. R ^b represents an 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, an alkyl group having 1 to 4 carbon atoms, and the alkyl group of R ^b represents a linear, branched, or cyclic alkyl group. [11] The method for producing a liquid crystal display element according to any one of [1] to [10], wherein the liquid crystal composition containing a liquid crystal and a radical polymerizable compound contains The Tg of the obtained polymer is a radically polymerizable compound of 100°C or less. [12] The method for manufacturing a liquid crystal display element as described in any one of [1] to [11] further has the following steps: Prepare a first substrate with a radical generating film, and a second substrate, on the first substrate The radical generating film is arranged to face the second substrate, and a liquid crystal composition containing liquid crystal and a radical polymerizable compound is filled between the first substrate and the second substrate to produce a liquid crystal cell. [13] The method for manufacturing a liquid crystal display element according to [12], wherein the second substrate has a radical generating film. [14] The method for manufacturing a liquid crystal display element according to [12], wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment. [15] The method for manufacturing a liquid crystal display element according to [14], wherein the aforementioned liquid crystal alignment film with uniaxial alignment is a liquid crystal alignment film for horizontal alignment. [16] The method for manufacturing a liquid crystal display element according to any one of [12] to [15], wherein the first substrate with the radical generating film is a substrate with comb-shaped electrodes. [Effects of Invention]

According to the present invention, it is possible to provide a simple and inexpensive method for manufacturing a liquid crystal display element having two or three different alignment regions (in-plane (uniaxial) alignment regions, out-of-plane alignment regions, and inclined alignment regions) in the same device The manufacturing method of the liquid crystal display element.

Hereinafter, the manufacturing method of the liquid crystal display element of the present invention will be described in detail, but the description of the constituent elements described below is an example of an embodiment of the present invention, and is not specific to these contents.

(Method of manufacturing liquid crystal display element) The manufacturing method of the liquid crystal display element of the present invention includes the following steps (A) and the following steps (B). Step (A): A step of forming a radical generating film capable of generating radicals by light irradiation on a substrate. Step (B): The liquid crystal composition containing the liquid crystal and the radical polymerizable compound is brought into contact with the radical generating film, and while maintaining this state, the liquid crystal composition is irradiated at 240 to 400 nm sufficient to polymerize the radical polymerizable compound. Step with peak light. The radically polymerizable compound in the above step (B) is a compound having a function of vertically aligning liquid crystals by polymerization. In addition, the manufacturing method of the liquid crystal display element of the present invention includes at least one of the following requirements (Z1) and (Z2). Requirement (Z1): There is step (C) between step (A) and step (B). The radical generating film obtained in step (A) is irradiated with light with a peak at 240-400 nm to make The free radical generating ability of the free radical generating membrane is inactivated. Requirement (Z2): The step (B) of irradiating the liquid crystal composition with light having a peak at 240 to 400 nm is performed through a photomask. The present invention, which includes the above steps (A) and (B), and satisfies at least one of the requirements (Z1) and (Z2), can produce at least one of the in-plane alignment area, the out-of-plane alignment area, and the inclined alignment area 2 patterned liquid crystal display elements.

＜Free radical generating film＞ In the present invention, a radical generating film is formed on the substrate. Here, the free radical generating film refers to a film that generates free radicals. The radical generating film is formed of, for example, a radical generating film forming composition.

<Free radical generating film forming composition> The components of the radical generating film forming composition include a polymer and a radical generating radical. At this time, the radical generating film forming composition may be a composition containing a polymer bonded with a radical generating radical, a compound having a radical generating radical, and a polymer that becomes a base resin. The composition of the thing. By coating such a radical generating film forming composition on a substrate and hardening the coating film, a radical generating film in which radicals generating radicals are immobilized in the film can be obtained. The base that generates free radicals is preferably an organic base that induces free radical polymerization.

式(1)中，A表示誘發自由基聚合之有機基。When the radical generating film is composed of a polymer containing an organic group that induces radical polymerization, the polymer containing an organic group that induces radical polymerization may be exemplified in the polymerization of the main chain having a structural unit represented by the following formula (1) Things. [化12]

In formula (1), A represents an organic group that induces radical polymerization.

When using a polymer containing an organic group that induces free radical polymerization, in order to obtain a polymer with a group that can generate free radicals, it is suitable to use a polymer containing a group selected from methacrylic group, acrylic group, vinyl, allyl, and coumadin. A monomer with a photoreactive side chain of at least one of a base, a styryl group, and a cassia cinnamon group, and a monomer having a site that decomposes and generate free radicals in the side chain due to light irradiation are used as monomer components. good. On the other hand, monomers that generate free radicals have problems such as spontaneous polymerization of themselves, and may become unstable compounds. Therefore, considering the ease of synthesis, a polymer derived from a diamine having free radical generation sites is preferable, and a polyimide precursor such as polyamide acid and polyamide ester, and polyamide are more preferable. Imine, polyurea, polyamide, etc.

式(3)中，虛線表示與苯環之鍵結，R⁶ 表示單鍵、-CH₂ -、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH₂ O-、-N(CH₃ )-、-CON(CH₃ )-、或-N(CH₃ )CO-， R⁷ 表示單鍵、或非取代或經氟原子取代之碳數1～20之伸烷基，該伸烷基之任意之-CH₂ -或-CF₂ -中之一者以上也可各自獨立地置換為選自-CH＝CH-、二價碳環、及二價雜環之基，另外，亦能以下列所列舉之任意基，亦即-O-、-COO-、-OCO-、-NHCO-、-CONH-、或-NH-彼此不相鄰為條件而置換為該等基； R⁸ 表示選自式[X-1]～[X-18]、[W]、[Y]及[Z]之式表示之誘發自由基聚合之有機基， [化14]

式[X-1]～[X-18]中，＊表示與R⁷ 之鍵結部位，S₁ 及S₂ 各自獨立地表示-O-、-NR-、或-S-，R表示氫原子、鹵素原子、碳數1～10之烷基、或碳數1～10之烷氧基，R₁ 及R₂ 各自獨立地表示氫原子、鹵素原子、或碳數1～4之烷基。Examples of the organic group that induces radical polymerization include the group represented by the following formula (3). [化13]

In formula (3), the dotted line represents the bond with the benzene ring, and R ⁶ represents a single bond, -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-, R ⁷ represents a single bond, or unsubstituted or substituted by a fluorine atom, carbon number 1 ～20 alkylene, any _{one or more of -CH 2} -or -CF ₂ -of the alkylene can also be independently replaced by one selected from -CH=CH-, divalent carbocyclic ring, and two The group of a valent heterocyclic ring, in addition, can also be conditioned on any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other And substituted with these groups; R ⁸ represents an organic group selected from the formulas [X-1]～[X-18], [W], [Y] and [Z] to induce free radical polymerization, [化14]

In formulas [X-1] ~ [X-18], * represents the bonding site ^{with R 7} _{, S 1} and S ₂ each independently represent -O-, -NR-, or -S-, and R represents a hydrogen atom , A halogen atom, an alkyl group having 1 to 10 carbons, or an alkoxy group having 1 to 10 carbons, R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbons.

式[W]、[Y]、[Z]中，＊表示與R⁷ 之鍵結部位，S³ 表示單鍵、-O-、-S-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH₂ O-、-N(CH₃ )-、-CON(CH₃ )-、或-N(CH₃ )CO-，Ar表示選自由亦可具有有機基及/或鹵素原子作為取代基之伸苯基、伸萘基、及伸聯苯基構成之群組中之芳香族烴基，R⁹ 及R¹⁰ 各自獨立地為碳數1～10之烷基、烷氧基、苄基、或苯乙基，為烷基、烷氧基時，R⁹ 及R¹⁰ 亦可形成環， Q表示下列任一結構， [化16]

式中，R¹¹ 表示-CH₂ -、-NR-、-O-、或-S-，R表示氫原子或碳數1～4之烷基，＊表示原子鍵， R¹² 表示氫原子、鹵素原子、碳數1～10之烷基或碳數1～10之烷氧基。[化15]

In the formulas [W], [Y], [Z], * represents the bonding site ^{with R 7 and S 3} represents a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, _{-CON(CH 3} )-, or -N(CH ₃ )CO-, Ar represents selected from or may have an organic group and / Or an aromatic hydrocarbon group in the group consisting of phenylene, naphthylene, and biphenyl with halogen atoms as substituents, R ⁹ and R ¹⁰ are each independently an alkyl group or alkane with 1 to 10 carbon atoms When the oxy, benzyl, or phenethyl group is an alkyl group or an alkoxy group, R ⁹ and R ¹⁰ may also form a ring, and Q represents any of the following structures, [formation 16]

In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O-, or -S-, R represents a hydrogen atom or an alkyl group with 1 to 4 carbons, * represents an atomic bond, and R ¹² represents a hydrogen atom, halogen Atom, C 1-10 alkyl group or C 1-10 alkoxy group.

The organic group represented by the formula selected from the above-mentioned [W], [Y], and [Z], specifically, is preferably the following. In particular, considering the reliability of the obtained liquid crystal display element, (b) and (c) are better. [化17]

An ideal embodiment of a polymer containing an organic group that induces free radical polymerization includes diamines having an organic group that induces free radical polymerization. The diamine containing such a radical generating site specifically includes a diamine having a side chain capable of generating radicals and polymerizing, for example, a diamine represented by the following formula (2) is exemplified. In addition, it is not limited to these.

式(2)中，A¹ 及A² 各自獨立地表示氫原子或上述式(3)表示之基，惟，A¹ 及A² 中之至少1者表示上述式(3)表示之基， E表示單鍵、-O-、-C(CH₃ )₂ -、-NH-、-CO-、-NHCO-、-COO-、-(CH₂ )_m -、-SO₂ -、或由該等之任意組合構成的2價有機基，m表示1～8之整數。 「該等之任意組合」，可列舉-O-(CH₂ )_m -O-、-O-C(CH₃ )₂ -、-CO-(CH₂ )_m -、-NH-(CH₂ )_m -、-SO₂ -(CH₂ )_m -、-CONH-(CH₂ )_m -、-CONH-(CH₂ )_m -NHCO-、-COO-(CH₂ )_m -OCO-等，但不限於該等。 p表示0～2之整數。p為2時，多個A² 及E各自獨立地具有前述定義。又，p為0時，A¹ 由下式(3)表示之基構成。[化18]

In formula (2), A ¹ and A ² each independently represent a hydrogen atom or a group represented by the above formula (3), but ^{at least one of A 1} and A ² represents a group represented by the above formula (3), E Represents a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -NHCO-, -COO-, -(CH ₂ ) _m -, -SO ₂ -, or these Any combination of the divalent organic group, m represents an integer of 1-8. "Any combination of these" includes -O-(CH ₂ ) _m -O-, -OC(CH ₃ ) ₂ -, -CO-(CH ₂ ) _m -, -NH-(CH ₂ ) _m- , -SO ₂ -(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -NHCO-, -COO-(CH ₂ ) _m -OCO- etc., but not limited to Such. p represents an integer of 0-2. When p is 2, a plurality of A ² and E each independently have the aforementioned definition. In addition, when p is 0, A ^{1 is} composed of a group represented by the following formula (3).

In the above formula (2), the bonding position _{of the two amino groups (-NH 2) when p=0 is not limited.} Specifically, the bonding group relative to the side chain can be listed as 2, 3 positions, 2, 4 positions, 2, 5 positions, 2, 6 positions, 3, 4 positions, 3 on the benzene ring. ,5's position. Among them, considering the reactivity when synthesizing polyamide acid, the preferred position is 2,4 position, 2,5 position, or 3,5 position. Considering the ease of synthesis of the diamine, the position 2,4, or the position 3,5 is more preferable.

A diamine containing at least one photoreactive group selected from the group consisting of a methacrylic group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamyl group, specifically In particular, the following compounds can be cited, but are not limited to these. [化19]

式中，J¹ 表示單鍵、-O-、-COO-、-NHCO-、或-NH-鍵結基，J² 表示單鍵、或非取代或經氟原子取代之碳數1～20之伸烷基。[化20]

In the formula, J ¹ represents a single bond, -O-, -COO-, -NHCO-, or -NH-bonding group, J ² represents a single bond, or unsubstituted or substituted by a fluorine atom, with a carbon number of 1-20 Alkylene.

式中，n為2～8之整數，E表示單鍵、-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-或-COO-(CH₂ )_m -OCO-，m為1～8之整數。 [化22]

式中，n為2～8之整數。A diamine having an organic group represented by the formula selected from the above-mentioned [W], [Y] and [Z], in view of ease of synthesis, versatility, characteristics, etc., the structure represented by the following formula is the best , But not limited to these. [化21]

In the formula, n is an integer of 2-8, E represents a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -NHCO-, -COO-, -(CH ₂ ) _m -, -SO ₂ -, -O-(CH ₂ ) _m -O-, -OC(CH ₃ ) ₂ -, -CO-(CH ₂ ) _m -, -NH-(CH ₂ ) _m -,- SO ₂ -(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -NHCO- or -COO-(CH ₂ ) _m -OCO-, m is 1～8 Integer. [化22]

In the formula, n is an integer of 2-8.

The above-mentioned diamines may be used singly or in combination of two or more according to characteristics such as liquid crystal alignment when forming a radical generating film, sensitivity during polymerization, voltage retention characteristics, and charge accumulation.

The diamine having such a site where radical polymerization occurs is preferably used in an amount of 5-50 mol% of the entire diamine component used in the synthesis of the polymer contained in the radical generating film forming composition. It is more preferably 10-40 mol%, particularly preferably 15-30 mol%.

In addition, when the polymer used in the radical generating film of the present invention is obtained from a diamine, a diamine other than the above-mentioned diamine having a site for generating free radicals can be used 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 Biphenyl, 2,3'-diaminodiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenyl Methane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane Phenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyl diphenylamine, 3,3'-sulfonyl diphenylamine, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl -Bis(3-aminophenyl)silane, 4,4'-sulfodiphenylamine, 3,3'-sulfodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diamino Diphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenylamine Phenyl)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'-di Aminobenzophenone, 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-amino) Phenoxy)benzene, 4,4'-[1,4-phenylenebis(methylene)]diphenylamine, 4,4'-[1,3-phenylenebis(methylene)]di Aniline, 3,4'-[1,4-phenylenebis(methylene)]diphenylamine, 3,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3, 3'-[1,4-phenylenebis(methylene)]diphenylamine, 3,3'-[1,3-phenylenebis(methylene)]diphenylamine, 1,4-phenylene Bis[(4-aminophenyl) ketone], 1,4-phenylene bis[(3-aminophenyl) ketone], 1,3-phenylene bis[(4-amino Phenyl) ketone], 1,3-phenylene bis[(3-aminophenyl) ketone], 1,4-phenylene bis(4-aminobenzoate), 1,4 -Phenylene bis(3-amino benzoate), 1,3-phenylene bis(4-amino benzoate), 1,3-phenylene bis(3-amino benzoate) Acid ester), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalic acid Ester, bis(3-aminophenyl) isophthalate, N,N'-(1,4-phenylene) bis(4-aminobenzoamide), N,N'-( 1,3-phenylene) bis(4-aminobenzoamide), N,N'-(1,4-phenylene)bis(3-aminobenzoamide), N,N' -(1,3-phenylene) bis(3-aminobenzoamide), N,N'-bis(4-aminophenyl)p-xylylenedimethamide, N,N'-bis( 3-aminophenyl)p-xylylenedimethamide, N,N'-bis(4-aminophenyl)m-xylylenedimethamide, N,N'-bis(3-aminophenyl)m Xylylenedimethamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenyl sulfide, 2,2'-bis[4-( 4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminobenzene) Yl)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 , 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane Alkyl, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminobenzene Oxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-amino) Phenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-amine Phenyloxy)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 and other aromatic diamines; bis(4-aminocyclohexyl)methane, bis(4 -Amino-3-methylcyclohexyl) methane and other alicyclic diamines; 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, Aliphatic diamines such as 11-diaminoundecane and 1,12-diaminododecane; 1,3-bis[2-(p-aminophenyl)ethyl]urea, 1,3-bis [2-(p-aminophenyl) ethyl]-1-tertiary butoxycarbonyl urea and other diamines with urea structure; N-p-aminophenyl-4-p-aminophenyl (third-butyl (Oxycarbonyl)aminomethylpiperidine and other diamines with nitrogen-containing unsaturated heterocyclic structure; N-tertiary butoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N -(4-Aminobenzyl)amine, etc., a diamine having an N-Boc group (Boc represents a tertiary butoxycarbonyl group), and the like.

The above-mentioned other diamines can also be used singly or in a mixture of two or more according to the characteristics of liquid crystal alignment when forming a radical generating film, sensitivity during polymerization, voltage retention characteristics, and charge accumulation.

In the synthesis when the polymer is polyamide acid, the tetracarboxylic dianhydride that reacts with the above-mentioned diamine component is not particularly limited. Specifically, examples 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-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, 2,3,3', 4'-Biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl) ether, 3,3',4,4'-benzophenone tetracarboxylic acid, bis(3,4-dicarboxyphenyl) ), 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'-diphenyl tetracarboxylic acid, 3,4,9, 10-perylene tetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid, oxydiphthalate tetracarboxylic 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-cyclobutane tetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic 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-cyclohexylsuccinic acid Acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic 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 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-Butanetetracarboxylic acid, 4-(2,5-Dioxytetrahydrofuran-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-di-side oxytetrahydrofuranyl)-3-methyl-3-cyclohexane -1,2-Dicarboxylic acid, tetracyclic [6.2.1.1<3,6>.0<2,7>] twelve-4,5,9,10-tetracarboxylic acid, 3,5,6-tri The dianhydrides of tetracarboxylic acids such as carboxynorbornane-2:3,5:6 dicarboxylic acid and 1,2,4,5-cyclohexanetetracarboxylic acid.

Of course, tetracarboxylic dianhydride can also be used in one type or two or more types in accordance with the characteristics of liquid crystal alignment, sensitivity during polymerization, voltage retention, and charge accumulation when forming a radical generating film.

In the synthesis when the polymer is a polyamide, the structure of the dialkyl tetracarboxylic acid that reacts with the above-mentioned diamine component is not particularly limited, and specific examples thereof are listed below. Specific examples of aliphatic tetracarboxylic acid diesters include: 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutane Alkyl tetracarboxylic acid dialkyl ester, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1, 2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofurantetracarboxylic acid dioxane Dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1-cyclohexyl dialkyl succinate, 3,4-dicarboxy-1,2 ,3,4-Tetrahydro-1-naphthalene succinate dialkyl ester, 1,2,3,4-butane tetracarboxylic acid dialkyl ester, bicyclo[3.3.0]octane-2,4,6 ,8-tetracarboxylic acid dialkyl ester, 3,3',4,4'-dicyclohexyl tetracarboxylic acid dialkyl ester, 2,3,5-tricarboxycyclopentyl acetate dialkyl ester, cis Formula-3,7-Dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclic [4.2.1.0<2,5>]nonane- 3,4,7,8-tetracarboxylic acid-3,4: 7,8-dialkyl ester, six ring [6.6.0.1<2,7>.0<3,6>.1<9,14> .0<10,13>]hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dialkyl ester, 4-(2,5-di-side oxytetrahydrofuran- 3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dialkyl ester and the like.

Aromatic tetracarboxylic acid dialkyl esters include: pyromellitic acid dialkyl ester, 3,3',4,4'-biphenyl tetracarboxylic acid dialkyl ester, 2,2',3,3' -Diphenyl tetracarboxylic acid dialkyl ester, 2,3,3',4-biphenyl tetracarboxylic acid dialkyl ester, 3,3',4,4'-benzophenone tetracarboxylic acid dialkyl ester Ester, 2,3,3',4'-benzophenone tetracarboxylic acid dialkyl ester, bis(3,4-dicarboxyphenyl) ether dialkyl ester, bis(3,4-dicarboxybenzene) Group) dialkyl esters of chrysene, 1,2,5,6-naphthalenetetracarboxylic acid dialkyl esters, 2,3,6,7-naphthalenetetracarboxylic acid dialkyl esters, etc.

式中R₂ 、R₃ 表示碳數1～10之脂肪族烴基。In the synthesis when the polymer is a polyurea, the diisocyanate that reacts with the above-mentioned diamine component is not particularly limited, and it can be used in accordance with availability and the like. The specific structure of the diisocyanate is shown below. [化23]

In the formula, R ₂ and R ₃ represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms.

Although the aliphatic diisocyanates shown in K-1～K-5 have poor reactivity, they have the advantage of improving solvent solubility. For example, the aromatic diisocyanates shown in K-6～K-7 are highly reactive and make It has the effect of improving heat resistance, but it has the disadvantage of reducing solvent solubility. Considering versatility and characteristics, it should be K-1, K-7, K-8, K-9, K-10. Considering the viewpoint of electrical characteristics, it should be K-12. Considering the viewpoint of liquid crystal orientation, it is suitable. For K-13. More than one type of diisocyanate can also be used, and it is appropriate to use various diisocyanates according to the characteristics to be obtained. In addition, a part of the diisocyanate can also be replaced with the tetracarboxylic dianhydride described above, and can be used in the form of a copolymer of polyamide acid and polyurea, and can also be chemically imidized to form a polyamide Used in the form of copolymer of imine and polyurea.

In the synthesis when the polymer is polyamide, the structure of the dicarboxylic acid to be reacted is not particularly limited, and specific examples are listed below. Specific examples of aliphatic dicarboxylic acids include: malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, and 2-methyl adipic acid , Trimethyladipic acid, Pimelic acid, 2,2-Dimethylglutaric acid, 3,3-Diethylsuccinic acid, Azelaic acid, Sebacic acid, Suberic acid and other dicarboxylic acids.

Examples of alicyclic dicarboxylic acids include: 1,1-cyclopropane dicarboxylic acid, 1,2-cyclopropane dicarboxylic acid, 1,1-cyclobutane dicarboxylic acid, 1,2-cyclobutane dicarboxylic acid Acid, 1,3-cyclobutane dicarboxylic acid, 3,4-diphenyl-1,2-cyclobutane dicarboxylic acid, 2,4-diphenyl-1,3-cyclobutane dicarboxylic acid , 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid, 1,1-cyclopentane dicarboxylic acid, 1,2-cyclopentane dicarboxylic acid , 1,3-cyclopentane dicarboxylic acid, 1,1-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclo Hexane dicarboxylic acid, 1,4-(2-norbornene) dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid, bicyclo[2.2.2]octane-1,4-dicarboxylic acid Acid, bicyclo[2.2.2]octane-2,3-dicarboxylic acid, 2,5-di-side oxy-1,4-bicyclo[2.2.2]octanedicarboxylic acid, 1,3-adamantane Dicarboxylic acid, 4,8-diposide oxy-1,3-adamantane dicarboxylic acid, 2,6-spiro[3.3]heptane dicarboxylic acid, 1,3-adamantane diacetic acid, camphoric acid, etc.

Aromatic dicarboxylic acids include: phthalic acid, isophthalic acid, terephthalic acid, 5-methyl isophthalic acid, 5-tertiary butyl isophthalic acid, 5-amino isophthalic acid Formic 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-anthracene dicarboxylic acid, 1,4-anthraquinone dicarboxylic acid, 2,5-biphenyl dicarboxylic acid, 4,4'- Biphenyl dicarboxylic acid, 1,5-biphenyl dicarboxylic acid, 4,4''-terphenyl dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenyl Ethane dicarboxylic acid, 4,4'-diphenylpropane dicarboxylic acid, 4,4'-diphenylhexafluoropropane dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4 '-Bibenzyl dicarboxylic acid, 4,4'-stilbene dicarboxylic acid, 4,4'-ethynyl dibenzoic acid, 4,4'-carbonyl dibenzoic acid, 4,4'-sulfonamide Dibenzoic acid, 4,4'-dithiodibenzoic acid, p-phenylene diacetic acid, 3,3'-p-phenylene dipropionic acid, 4-carboxycinnamic acid, p-phenylene diacrylic acid, 3 ,3'-[4,4'-(methylenebis-paraphenylene)]dipropionic acid, 4,4'-[4,4'-(oxydi-paraphenylene)]dipropylene Acid, 4,4'-[4,4'-(oxydi-p-phenylene)] dibutyric acid, (isopropylidene bis-p-phenylene dioxy) dibutyric acid, bis(p-phenylene) Carboxyphenyl) dimethyl silane and other dicarboxylic acids.

Examples of dicarboxylic acids containing heterocycles include: 1,5-(9-side oxyfluoride) dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazole dicarboxylic acid, 2-phenyl-4 ,5-thiazole dicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridine dicarboxylic acid Carboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, etc.

The above-mentioned various dicarboxylic acids may be dihalide or anhydride structures. These dicarboxylic acids, especially those that can provide a linear structure of polyamide, are preferable in terms of maintaining the alignment of liquid crystal molecules. Among them, can be used ideally: terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenyl Methane dicarboxylic acid, 4,4'-diphenylethane dicarboxylic acid, 4,4'-diphenylpropane dicarboxylic acid, 4,4'-diphenylhexafluoropropane dicarboxylic acid, 2,2 -Bis(phenyl)propane dicarboxylic acid, 4,4"-terphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,5-pyridine dicarboxylic acid or their dihalides, etc. There are isomers of the compounds, and they may be mixtures containing them. In addition, two or more compounds may be used. In addition, the dicarboxylic acids used in the present invention are not limited to the above-exemplified compounds.

Using diamine (also referred to as "diamine component") as a raw material and selected from tetracarboxylic dianhydride (also referred to as "tetracarboxylic dianhydride component"), tetracarboxylic diester, diisocyanate and When the components of the dicarboxylic acid are reacted to obtain polyamide acid, polyamide ester, polyurea, and polyamide, a known synthesis method can be used. Generally, there is a method of reacting a diamine component and one or more components selected from a tetracarboxylic dianhydride component, a tetracarboxylic acid diester, a diisocyanate, and a dicarboxylic acid in an organic solvent.

The reaction of the diamine component and the tetracarboxylic dianhydride component is advantageous from the viewpoint that it proceeds easily in an organic solvent and does not produce by-products.

The organic solvent used in the above reaction is not particularly limited as long as it can dissolve the produced polymer. In addition, even if it is an organic solvent that does not dissolve the polymer, it can be used in combination with the above-mentioned solvent within a range where the polymer produced does not precipitate. In addition, the moisture in the organic solvent will hinder the polymerization reaction and cause the resulting polymer to be hydrolyzed. Therefore, the organic solvent should preferably be dehydrated and dried.

As for the organic solvent, for example, 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-dimethyl Propanamide, N-methylcaprolactone, dimethyl sulfide, tetramethylurea, pyridine, dimethyl sulfide, hexamethylphosphotriamide, gamma-butyrolactone, isopropanol, formaldehyde Oxymethylpentanol, dipentene, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl serosol, ethyl serosol , Methyl Cyloxe Acetate, Butyl Cyloxe Acetate, Ethyl Cyloxe Acetate, Butyl Carbitol, Ethyl Carbitol, Ethylene Glycol, Ethylene Glycol Monoacetic Acid Ester, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tertiary butyl ether, dipropylene glycol monomethyl ether, propylene glycol mono Methyl 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 ring Hexene, propyl ether, dihexyl ether, diethane, 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, methyl 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 mixture.

When the diamine component and the tetracarboxylic dianhydride component are reacted in an organic solvent, the following method can be cited: a solution obtained by dispersing or dissolving the diamine component in an organic solvent is stirred, and the tetracarboxylic dianhydride component is directly added, Or a method of dispersing or dissolving it in an organic solvent and then adding it; conversely, a method of adding a diamine component to a solution obtained by dispersing or dissolving the tetracarboxylic dianhydride component in an organic solvent; The method of alternately adding amine components, etc., can use any of these methods. In addition, when the diamine component or the tetracarboxylic dianhydride component is composed of multiple compounds, it can be reacted in a pre-mixed state, or it can be reacted individually and sequentially, or the oligomers that have been reacted individually can be mixed and reacted. , And made into high molecular polymer.

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

The ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component in the above polymerization reaction can be selected according to the molecular weight of the polyamide acid to be obtained. As in the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polyamide acid produced. The ideal range is 0.8 to 1.2.

The method of synthesizing the polymer used in the present invention is not limited to the above method. When synthesizing polyamide acid, it can be the same as the general synthesis method of polyamide acid, and the above-mentioned tetracarboxylic dianhydride can be replaced with tetracarboxylic dianhydride of the corresponding structure. Tetracarboxylic acid derivatives such as carboxylic acid or tetracarboxylic dihalide are reacted by a known method to obtain the corresponding polyamide acid. Moreover, when synthesizing polyurea, what is necessary is just to make diamine and diisocyanate react. When producing polyamide esters or polyamides, diamine and a component selected from tetracarboxylic acid diesters and dicarboxylic acids can be derivatized into halides in the presence of a known condensing agent or by a known method. Just make it react with diamine.

The method of making the above-mentioned polyamide acid into polyimide can be enumerated as follows: directly heating the polyamide acid solution to heat the imidization method; adding contact to the polyamide acid solution The catalyst of the medium is imidized. In addition, the conversion rate of polyimide from polyamide acid to polyimide is preferably 30% or more, and more preferably 30-99%, considering that the voltage holding rate can be improved. On the other hand, considering the whitening suppression properties, that is, the viewpoint of suppressing the precipitation of the polymer in the varnish, it is preferably 70% or less. Considering the two characteristics, 40 to 80% is better.

The temperature for the thermal imidization of polyamide acid in a solution is usually 100-400°C, preferably 120-250°C, and it is better to implement it while removing the water generated by the imidization reaction to the outside of the system.

The catalyst imidization of polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a solution of polyamic acid, usually at -20 to 250°C, preferably at 0 to 180°C and stirring. The amount of alkaline catalyst is usually 0.5 to 30 molar times of the amide acid group, preferably 2 to 20 molar times, and the amount of acid anhydride is usually 1 to 50 molar times of the amide acid group, preferably 3 to 30 mol times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is suitably alkaline for the reaction to proceed, and is therefore preferred. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, acetic anhydride is preferably used because purification after completion of the reaction becomes easy. The rate of imidization of the catalyst can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

When recovering the polymer produced from the reaction solution of the polymer, the reaction solution may be poured into a poor solvent and precipitated. Examples of poor solvents used in the formation of precipitation include methanol, acetone, hexane, butyl celosine, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer put into the poor solvent and precipitated can be dried under normal pressure or reduced pressure at normal temperature or under heating after filtration and recovery. In addition, if the polymer obtained by precipitation recovery is re-dissolved in an organic solvent and the re-precipitation recovery operation is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, and hydrocarbons. If three or more poor solvents selected from these are used, the purification efficiency is further improved, which is preferable.

In addition, when the above-mentioned radical generating film is composed of a polymer containing an organic group that induces radical polymerization, the radical generating film forming composition used in the present invention may also include a polymer other than a polymer containing an organic group that induces radical polymerization. Other polymers. At this time, the content of other polymers in all the components of the polymer is preferably 5 to 95% by mass, more preferably 30 to 70% by mass.

When considering the molecular weight of the polymer of the radical generating film forming composition, the strength of the free radical generating film obtained by coating the radical generating film forming composition, the workability during coating film formation, and the uniformity of the coating film are considered. The weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is preferably 5,000-1,000,000, more preferably 10,000-150,000.

The polymer for obtaining the radical-generating film used in the present invention by applying a composition of a compound having a radical-generating group and a polymer and curing it to form a film and immobilizing it in the film can be used It is a polymer selected from the group consisting of polyimide precursors, polyimine, polyurea, polyamide, polyacrylate, polymethacrylate, etc., prepared according to the above-mentioned manufacturing method, and The diamine having a site where radical polymerization occurs uses at least one type of polymer obtained by synthesizing the polymer contained in the radical generating film forming composition with 0 mol% of the total diamine component used in the synthesis of the diamine component. The compound having a radical generating group to be added at this time includes the following.

The compound that generates radicals by light is not particularly limited as long as it is a compound that initiates radical polymerization due to light irradiation. Such radical photopolymerization initiators include: benzophenone, Michler’s ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropyl Xanthone, 2,4-Diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'- Cumyl Propiophenone, 1-Hydroxycyclohexyl Phenone, Cumene Ether, Isobutyl Benzene Ether, 2,2-Diethoxyacetophenone, 2,2-Dimethoxy 2-phenylacetophenone, camphorquinone, benzoanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-𠰌line propane-1-one, 2- Benzyl-2-dimethylamino-1-(4-𠰌olinylphenyl)-butan-1-one, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzene Isoamyl formate, 4,4'-bis(tertiary butylperoxycarbonyl)benzophenone, 3,4,4'-tris(tertiary butylperoxycarbonyl)benzophenone, 2,4 ,6-Trimethylbenzyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-tris, 2-( 3',4'-Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-tris, 2-(2',4'-Dimethoxystyryl)- 4,6-bis(trichloromethyl)-s-tris, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-tris, 2- (4'-Pentyloxystyryl)-4,6-bis(trichloromethyl)-s-tris, 4-[p-N,N-bis(ethoxycarbonylmethyl)]-2 ,6-Bis(trichloromethyl)-s-tris, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-tris, 1,3-bis( Trichloromethyl)-5-(4'-methoxyphenyl)-s-tris, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylamine Styryl) benzothiazole, 2-mercaptobenzothiazole (mercaptobenzothiazole), 3,3'-carbonyl bis (7-diethylamino coumarin), 2-(o-chlorophenyl)-4, 4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-four (4-ethoxy Carbonyl phenyl)-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-dimethylaminopropyl) ) Carbazole, 3,6-bis(2-methyl-2-𠰌linylpropionyl)-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'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)benzophenone, 3 ,3'-bis(methoxycarbonyl)-4,4'-bis(tertiary butylperoxycarbonyl)benzophenone, 3,4'-bis(methoxycarbonyl)-4,3'- Di(tertiary butylperoxycarbonyl)benzophenone, 4,4'-bis(methoxycarbonyl)-3,3'-bis(tertiary butylperoxycarbonyl)benzophenone, 2- (3-Methyl-3H-benzothiazol-2-ylidene)-1-naphthalene-2-yl-ethanone, or 2-(3-methyl-1,3-benzothiazole-2(3H) -Subunit)-1-(2-benzyl)ethanone and the like. These compounds may be used alone, or two or more of them may be mixed and used.

In addition, even when the radical generating film is composed of a polymer containing an organic group that induces radical polymerization, it may contain a compound having the radical generating group for the purpose of promoting radical polymerization during light irradiation.

The radical generating film forming composition may contain an organic solvent that dissolves or disperses the polymer component, and optionally contains components other than the radical generator. Such an organic solvent is not particularly limited, and examples thereof include the organic solvents exemplified in the synthesis of the above-mentioned polyamide acid. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N- Dimethylpropaneamide and the like are preferable from the viewpoint of solubility. Particularly, N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone is preferable, and a mixed solvent of two or more kinds can also be used.

In addition, it is preferable to mix and use a solvent that improves the uniformity and smoothness of the coating film and an organic solvent that is highly soluble in the components contained in the radical generating film forming composition.

As a solvent to improve the uniformity and smoothness of the coating film, for example, isopropanol, methoxymethylpentanol, methyl serosol, ethyl serosol, butyl serosol, methyl serosol Loxoacetate, butyl siloxe acetate, ethyl siloxe acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethyl 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-tertiary butyl ether, dipropylene glycol mono Methyl 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 mono Methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetic acid Ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl Ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate Ester, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate Ester, 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 two Acetate, 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. A plurality of these solvents may be mixed. When these solvents are used, it is preferably 5 to 80% by mass of the total solvent contained in the liquid crystal alignment agent, and more preferably 20 to 60% by mass.

The radical generating film forming composition may contain components other than the above. Examples include: compounds that improve the film thickness uniformity and surface smoothness when coating the radical generating film forming composition; compounds that improve the adhesion between the radical generating film forming composition and the substrate; further improving the free radical generating film formation The compound of the film strength of the composition, etc.

Examples of compounds that improve the uniformity of film thickness and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, EFTOP EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), 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), etc. When these surfactants are used, the use ratio is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass relative to 100 parts by mass of the total amount of polymers contained in the radical generating film forming composition.

Specific examples of the compound for improving the adhesion between the radical generating film forming composition and the substrate include a compound containing a functional silane, a compound containing an epoxy group, and the like. Examples include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-urea Propyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyl Triethoxysilane, N-triethoxysilylpropyl triethylenetriamine, N-trimethoxysilylpropyl triethylenetriamine, 10-trimethoxysilyl-1,4, 7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-Triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyl trimethoxysilane, N-benzyl-3-aminopropyl three Ethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3- Aminopropyltrimethoxysilane, N-bis(oxyethylene)-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, glycerin dicyclic Propylene oxide, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, N,N,N', N'-tetraepoxypropyl-m-xylenediamine, 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane, N,N,N',N'-tetra Glycidyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-glycidyl)aminopropyl trimethoxysilane, 3-(N,N- Diepoxypropyl) aminopropyl trimethoxysilane and the like.

In addition, in order to further improve the film strength of the free radical generating film, 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, tetra(methoxymethyl)bisphenol can also be added And other phenolic compounds. When these compounds are used, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass relative to 100 parts by mass of the total amount of polymers contained in the radical generating film forming composition.

In addition, in addition to the above, in the radical generating film forming composition, if the effect of the present invention is not impaired, a dielectric for changing the electrical properties such as the dielectric rate and conductivity of the radical generating film may be added. Electric body, conductive material.

＜Method of making free radical generating film＞ The radical generating film of the present invention is obtained by using the above-mentioned radical generating film forming composition. For example, after the radical generating film forming composition used in the present invention is applied to a substrate, it is dried and fired to obtain a cured film, and the cured film can be used as a radical generating film as it is. In addition, the cured film may be rubbed, or irradiated with polarized light or light of a specific wavelength, or processed with ion beams. For the alignment film for PSA, the liquid crystal display element filled with liquid crystal may also be irradiated with UV.

When producing the radical generating film, the irradiated light used is not particularly limited, and can be appropriately selected according to the purpose. For example, light having a peak at 240 to 400 nm can be cited. Light having a peak at 250-365nm is more preferred, and light having a peak at 250-360nm is particularly preferred. More specifically, for example, light having a peak in the vicinity of 254 nm and 313 nm is used. In addition, a well-known cut-off filter may be used to cut off light with a specific wavelength, or above or below a specific wavelength, as needed.

The substrate on which the radical generating film forming composition is applied is not particularly limited as long as it is a highly transparent substrate, and it is not limited to electrodes. For example, an ideal aspect may be a substrate on which a transparent electrode for driving liquid crystal is formed on the substrate. Specific examples include glass plates, polycarbonates, poly(meth)acrylates, polyethers, polyarylates, polyurethanes, polyethers, polyethers, polyether ketones, trimethyl Plastics such as pentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triacetyl cellulose, 2,3-butanedione cellulose, cellulose acetate butyrate, etc. A substrate on which a transparent electrode is formed, such as a plate.

The substrates that can be used for IPS mode liquid crystal display elements can also use standard IPS comb-tooth electrodes, PSA herringbone electrodes and other electrode patterns, and MVA and other protrusion patterns. In addition, in high-function devices such as TFT-type devices, a device such as a transistor is formed between an electrode for driving liquid crystal and a substrate. When manufacturing a transmissive liquid crystal display element, the above-mentioned substrate is generally used, but when manufacturing a reflective liquid crystal display element, if it is a single-sided substrate, an opaque substrate such as a silicon wafer can also be used. At this time, the electrode formed on the substrate can also use a material that reflects light, such as aluminum.

The coating method of the radical generating film forming composition includes spin coating, printing, inkjet, spraying, roll coating, etc. However, in terms of productivity, the transfer printing method is widely used in the industry. The invention can also be used ideally.

The drying step after coating the radical generating film forming composition is not necessary, but it is preferable to include the drying step when the time from coating to firing of each substrate is not fixed or when not firing immediately after coating. The drying method is not particularly limited as long as the solvent is removed to the extent that the shape of the coating film is not deformed due to substrate transportation or the like. For example, drying on a hot plate at a temperature of 40 to 150°C, preferably 60 to 100°C, for 0.5 to 30 minutes, preferably 1 to 5 minutes.

The coating formed by applying the radical generating film forming composition by the above-mentioned method, the so-called radical generating film, can be calcined to form a cured film. At this time, the calcination temperature can usually be performed at any temperature from 100 to 350°C, preferably 140 to 300°C, more preferably 150 to 230°C, and still more preferably 160 to 220°C. The calcination time can usually be calcination at any time from 5 to 240 minutes. It is preferably 10 to 90 minutes, more preferably 20 to 90 minutes. A generally known method can be used for heating, and for example, a hot plate, a hot air circulation type oven, an IR (infrared) type oven, a belt furnace, etc. can be used.

The thickness of the radical generating film after curing can be selected according to needs, preferably 5 nm or more, and more preferably 10 nm or more, since the reliability of the liquid crystal display element can be easily obtained, so it is more desirable. In addition, when the thickness of the cured film is preferably 300 nm or less, and more preferably 150 nm or less, the power consumption of the liquid crystal display element does not become extremely large, which is preferable.

In the above manner, the first substrate having the radical generating film can be obtained, but the radical generating film can be subjected to uniaxial alignment treatment. The method of performing uniaxial alignment treatment includes photo-alignment method, oblique vapor deposition method, friction, uniaxial alignment treatment using a magnetic field, and the like.

When the alignment treatment is performed by performing the rubbing treatment in one direction, for example, while the rubbing roller wound with the rubbing cloth is rotated, the substrate is moved so that the rubbing cloth is brought into contact with the film. In the case of the first substrate of the present invention formed with comb-teeth electrodes, the direction is selected by using the electrical properties of liquid crystals, but when using liquid crystals with positive dielectric anisotropy, the rubbing direction should be the same as the extension direction of the comb-teeth electrodes Roughly the same direction.

<Liquid crystal composition containing liquid crystal and radical polymerizable compound> The liquid crystal display element of the present invention is produced using a liquid crystal composition containing a liquid crystal and a radical polymerizable compound. The polymerizable compound used with the liquid crystal is not particularly limited as long as it is a radical polymerizable compound. For example, it may be a compound having one or two or more polymerizable unsaturated bonds in one molecule. It is preferably a compound having one polymerizable unsaturated bond in one molecule (hereinafter, sometimes referred to as "a compound having a monofunctional polymerization-reactive group", "a compound having a monofunctional polymerization-reactive group", etc.). The polymerizable unsaturated bond is preferably a radical polymerizable unsaturated bond, such as a vinyl bond.

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

式中，＊表示與化合物分子之聚合性不飽和鍵以外之部分的鍵結部位。R^b 表示碳數3～20之烷基，E表示選自單鍵、-O-、-NR^c -、-S-、酯鍵及醯胺鍵之鍵結基。R^c 表示氫原子、碳數1～4之烷基，R^b 之烷基表示直鏈、分支、或環狀之烷基。In addition, the polymerization reactive group of the radically polymerizable compound is preferably a polymerizable group selected from the following structures. [化24]

In the formula, * represents the bonding site with the part other than the polymerizable unsaturated bond of the compound molecule. R ^b represents an 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 and an alkyl group having 1 to 4 carbon atoms, and the alkyl group of R ^b represents a linear, branched, or cyclic alkyl group.

In addition, the liquid crystal composition containing a liquid crystal and a radical polymerizable compound preferably contains a radical polymerizable compound having a Tg of 100° C. or lower for the polymer obtained by polymerizing the radical polymerizable compound.

A compound having a monofunctional radical polymerization reactive group is a compound having an unsaturated bond that can undergo radical polymerization in the presence of organic radicals. Examples include: tert-butyl methacrylate and hexyl methacrylate , 2-ethylhexyl methacrylate, nonyl methacrylate, lauryl methacrylate, n-octyl methacrylate and other methacrylate-based monomers; t-butyl acrylate, hexyl acrylate, acrylic acid 2 -Ethylhexyl, nonyl acrylate, benzyl acrylate, lauryl acrylate, n-octyl acrylate and other acrylate monomers; styrene, styrene derivatives (for example, ortho, meta, p-methoxystyrene, Ortho, meta, p-tertiary butoxy styrene, ortho, meta, p-chloromethyl styrene, etc.), vinyl esters (for example, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl acetate Etc.), vinyl ketones (for example, vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, etc.), N-vinyl compounds (for example, N-vinylpyrrolidone, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, etc.), (meth)acrylic acid derivatives (for example, acrylonitrile, methacrylonitrile, acrylamide, isopropylacrylamide, methacrylamide Etc.), vinyl monomers such as vinyl halides (for example, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropylene, vinyl fluoride, etc.), but are not limited to these. These various radical polymerizable monomers may be used alone, or two or more of them may be used. In addition, these should be compatible with liquid crystals.

式(A)中，R^a 及R^b 各自獨立地表示碳數3～20之烷基，E表示選自單鍵、-O-、-NR^c -、-S-、酯鍵、醯胺鍵之鍵結基，R^c 表示氫原子、碳數1～4之烷基，R^a 或R^b 之烷基表示直鏈、分支、或環狀之烷基。In addition, the radically polymerizable compound is preferably a compound represented by the following formula (A). [化25]

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

式(A-1)及(A-2)中，R^a 及R^b 各自獨立地表示碳數3～20之烷基，R^a 及R^b 之烷基各自獨立地表示直鏈、分支、或環狀之烷基。In addition, for the radically polymerizable compound represented by formula (A), where E is an ester bond (-C(=O)-O- or -OC(=O)-), it is easy to synthesize The viewpoints of compatibility, compatibility with liquid crystals, and polymerization reactivity are preferable. Specifically, a compound having the following structure is preferable, but it is not particularly limited. [化26]

Of formula (A-1) and (A-2), R ^a is and R ^b each independently represent 3 to 20 carbon atoms of the alkyl group, R ^a and R ^b each independently represent an alkyl group of a straight-chain, branched, or Cyclic alkyl.

式[S1]中，X¹ 及X² 獨立地表示單鍵、-(CH₂ )_a -(a為1～15之整數)、-CONH-、-NHCO-、-CON(CH₃ )-、-NH-、-O-、-COO-、-OCO-、或-((CH₂ )_a1 -A₁ )_m1 -(多個A1各自獨立地表示1～15之整數，多個A₁ 各自獨立地表示氧原子或-COO-，m₁ 為1或2。)。其中，考量原料的取得性、合成容易性的觀點，宜為單鍵、-(CH₂ )_a -(a為1～15之整數)、-O-、-CH₂ O-或-COO-。更佳為單鍵、-(CH₂ )_a -(a為1～10之整數)、-O-、-CH₂ O-或-COO-。 G¹ 及G² 獨立地為選自碳數6～12之2價芳香族基或碳數3～8之2價脂環族基的2價環狀基，上述環狀基上之任意氫原子亦可經碳數1～3之烷基、碳數1～3之烷氧基、碳數1～3之含氟烷基、碳數1～3之含氟烷氧基或氟原子取代，m及n獨立地為0～3之整數，且它們的合計為0～4，R¹ 為碳數1～20之烷基、碳數1～20之烷氧基、或碳數2～20之烷氧基烷基，該等基中之任意氫亦可經氟置換，惟，m及n之合計為0時，R¹ 亦可為具有類固醇骨架之基。 碳數6～12之2價芳香族基，例如可列舉伸苯基、伸聯苯基、伸萘基等。又，碳數3～8之2價脂環族基，例如可列舉伸環丙基、伸環己基等。The radically polymerizable compound of the present invention may also have a vertical alignment group. Examples of the vertical alignment group possessed by the radically polymerizable compound used in the present invention include a group represented by the following formula [S1]. [化27]

In the formula [S1], X ¹ and X ² independently represent a single bond, -(CH ₂ ) _a- (a is an integer of 1-15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -COO-, -OCO-, or -((CH ₂ ) _a1 -A ₁ ) _m1- (a plurality of A1s each independently represents an integer of 1-15, and a plurality of A _1s are each independently Ground represents an oxygen atom or -COO-, and m ₁ is 1 or 2.). Among them, from the viewpoint of availability of raw materials and ease of synthesis, a single bond, -(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferable. More preferably, it is a single bond, -(CH ₂ ) _a- (a is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-. G ¹ and G ^{2 are} independently a divalent cyclic group selected from a divalent aromatic group with 6 to 12 carbons or a divalent alicyclic group with 3 to 8 carbons, and any hydrogen atom on the cyclic group It can also be substituted by a C1-C3 alkyl group, a C1-C3 alkoxy group, a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxy group or a fluorine atom, m And n are independently an integer of 0 to 3, and their total is 0 to 4, R ¹ is an alkyl group with 1 to 20 carbons, an alkoxy group with 1 to 20 carbons, or an alkane with 2 to 20 carbons In the oxyalkyl group, any hydrogen in these groups may be replaced with fluorine, but when the total of m and n is 0, R ¹ may also be a group having a steroid skeleton. Examples of the divalent aromatic group having 6 to 12 carbon atoms include phenylene, biphenylene, and naphthylene. In addition, the divalent alicyclic group having 3 to 8 carbon atoms includes, for example, cyclopropylene and cyclohexylene.

式[S1-x1]～[S1-x7]中，R¹ 為碳數1～20之烷基，X^p 表示-(CH₂ )_a -(a為1～15之整數)，A₁ 為氧原子或-COO-＊(惟，標註有「＊」之原子鍵係與(CH₂ )_a2 鍵結)、A₂ 為氧原子或＊-COO-(惟，標註有「＊」之原子鍵係與(CH₂ )_a2 鍵結)，a₁ 、a₃ 各自獨立地為0或1之整數，a₂ 為2～10之整數，Cy為1,4-伸環己基或1,4-伸苯基。Ideal specific examples of the formula [S1] include the structures of the following formulas [S1-x1] to [S1-x7]. [化28]

In the formulas [S1-x1]～[S1-x7], R ¹ is an alkyl group with 1 to 20 carbons, X ^p represents -(CH ₂ ) _a- (a is an integer of 1 to 15), and A ₁ is oxygen Atom or -COO-* (except, the atomic bond system marked with "*" is bonded to (CH ₂ ) _a2 ), A ₂ is an oxygen atom or *-COO- (except, the atomic bond system marked "*" _Bonded with (CH ₂ ) a2), a ₁ and a ₃ are each independently an integer of 0 or 1, a ₂ is an integer of 2-10, and Cy is 1,4-cyclohexylene or 1,4-phenylene base.

式[S3-x]中，Col表示上述式[Col1]～[Col4]中之任一者，G表示上述式[G1]～[G2]中之任一者。＊表示鍵結位置。 本發明之自由基聚合性化合物之理想態樣，例如可列舉於上述垂直配向性基[S1]鍵結有上述自由基聚合性基中之任一者的具有垂直配向性基之自由基聚合性化合物。A desirable specific example of the above-mentioned group having a steroid skeleton includes the following formula [S3-x]. [化29]

In the formula [S3-x], Col represents any of the aforementioned formulas [Col1] to [Col4], and G represents any of the aforementioned formulas [G1] to [G2]. ＊Indicating the bonding position. The ideal aspect of the radically polymerizable compound of the present invention can be exemplified by the above-mentioned vertical-alignment group [S1] bonded to any one of the above-mentioned radically polymerizable groups. Compound.

These various radical polymerizable monomers may be used alone, or two or more of them may be used. In addition, these should be compatible with liquid crystals.

The content of the radical polymerizable compound in the liquid crystal composition, relative to the total mass of the liquid crystal and the radical polymerizable compound, is preferably 3% by mass or more, more preferably 5% by mass or more, preferably 50% by mass or less, more preferably It is 20% by mass or less.

In addition, liquid crystal generally refers to a substance in a state that exhibits the properties of both solid and liquid. Representative liquid crystal phases include nematic liquid crystal and smectic liquid crystal. The liquid crystal that can be used in the present invention is not particularly limited. To give one example, it is 4-pentyl-4'-cyanobiphenyl.

＜Liquid crystal cell＞ The liquid crystal display element of the present invention can be made into the cell structure described below, for example. After the radical generating film is formed on the substrate by the above method, the first substrate and the second substrate with the radical generating film are arranged such that the radical generating film on the first substrate faces the second substrate, and the A liquid crystal composition containing a liquid crystal and a radical polymerizable compound is filled between the first substrate and the second substrate to produce a liquid crystal cell. The liquid crystal display element manufactured in the present invention can use the liquid crystal cell obtained in this way.

To describe in more detail the production method of the above-mentioned liquid crystal cell, after disposing the radical generating film on the first substrate facing the second substrate, the two substrates are fixed by the sealant with the spacers between the first and second substrates. A liquid crystal composition containing a liquid crystal and a radical polymerizable compound is injected between the substrates and sealed, thereby obtaining a liquid crystal cell. The size of the spacer used at this time is usually 1-30 μm, preferably 2-10 μm. The method of injecting a liquid crystal composition containing a liquid crystal and a radical polymerizable compound is not particularly limited. Examples include a vacuum method in which a mixture containing liquid crystal and a polymerizable compound is injected after depressurizing the inside of the obtained liquid crystal cell ; The dropping method of sealing after dropping the mixture containing liquid crystal and polymerizable compound.

The above-mentioned second substrate is preferably formed with an alignment film for aligning liquid crystals. The alignment film may be a well-known liquid crystal alignment film, or may be any one of the radical generating films of the present invention, and may be appropriately selected according to the purpose. Uniaxial alignment processing can be applied to the alignment film formed on the second substrate. As described later, for example, when an out-of-plane alignment region is formed in a liquid crystal display element, it is preferable to form a radical generating film on the second substrate. In addition, for example, when the liquid crystal display element forms an in-plane alignment area or an oblique alignment area, it is suitable to form a liquid crystal alignment film for horizontal alignment that has undergone a uniaxial alignment treatment on the second substrate.

<Formation of in-plane alignment, out-of-plane alignment, and inclined alignment regions> For a liquid crystal cell formed 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, irradiation is sufficient to cause the radical polymerizable compound to undergo polymerization reaction Light. As above, the present invention forms a free radical generating film with anchoring force on the substrate, and makes the liquid crystal containing a specific polymerizable compound contact the free radical generating film, and the free radical generating film is applied to the area where the anchoring force is to be maintained. Irradiate light. When the polymerizable compound is polymerized, the liquid crystal is aligned vertically, and as a result, an out-of-plane alignment (vertical alignment) region is formed in the region irradiated with light.

Here, the irradiated light can be exemplified by light having a peak at 240 to 400 nm. In addition, it is preferable to irradiate light of a wavelength at which the absorbance of the part where the light radicals are generated is high. The light is more preferably light having a peak at 250-365nm, especially light having a peak at 250-360nm. good. More specifically, it can be used for light having a peak near 313 nm, for example. In addition, if necessary, a known cut filter can be used to cut off light with a specific wavelength, or above or below the specific wavelength. The amount of light irradiation is usually 0.01-30J, preferably 10J or less. The less the amount of light is irradiated, the lower the reliability caused by the destruction of the components constituting the liquid crystal display element can be suppressed, and it is more desirable to reduce the light irradiating time to improve the takt in manufacturing.

In addition, heating can also be performed when irradiating light. The heating temperature when irradiated with light is preferably the temperature range where the introduced liquid crystal exhibits liquid crystallinity, usually above 40°C, and it is better to heat before the temperature at which the liquid crystal changes into an isotropic phase.

In addition, when the radical polymerizable compound is subjected to light irradiation during the polymerization reaction, it is preferable to proceed in a state without an electric field without applying a voltage.

On the other hand, when the liquid crystal cell is irradiated with light, a photomask is placed on the outside of the liquid crystal cell and the light is irradiated through the photomask, the unexposed area (= the region where no radicals are generated) will form an in-plane alignment (horizontal alignment) ) Area, the exposed portion will form an out-of-plane alignment (vertical alignment) area as described above. The pattern shape and pattern size of the mask used are not particularly limited, and can be appropriately selected according to the purpose. As for the pattern shape, for example, a line pattern shape, a line/space (L/S) pattern shape, a dot shape, etc. can be cited. As far as the pattern size is concerned, it can be made into a micron-sized pattern. For example, if a photomask with a L/S pattern shape with a pitch of 5 μm is used, an alignment pattern with a pitch of 5 μm can be formed.

In addition, by irradiating the radical generating film with light before assembling the unit cell of the liquid crystal cell, and deactivating the radical generating ability of the radical generating film, an in-plane alignment (horizontal alignment) region can also be formed. By irradiating the free radical generating film with light in advance, the free radical generating ability disappears, and the anchor strength in the in-plane direction can be maintained at all times. That is, by using a free radical generating film that has inactivated the free radical generating ability to produce a liquid crystal cell, and irradiating the liquid crystal cell with light, it is also possible to form an in-plane alignment (horizontal alignment) region in the region where the free radical generating ability is inactivated . In addition, the light used to deactivate the radical generating ability of the radical generating film includes light having a peak at 240 to 400 nm. In addition, the light is more preferably light having a peak at 250-365 nm, and particularly preferably light having a peak at 250-360 nm. More specifically, it can be used for light having a peak near 313 nm, for example. In addition, if necessary, a known cut filter can be used to cut off light with a specific wavelength, or above or below the specific wavelength. The amount of light irradiation is usually 0.01-30J, preferably 10J or less.

In the unexposed area and the region where the free radical generating ability is inactivated, it is preferable to apply uniaxial alignment treatment to the free radical generating film in order to align the liquid crystal well in the ground. In addition, in the unexposed area and the region where the free radical generating ability is inactivated, in order to align the liquid crystal well in the ground, the free radical generating film in the free radical generating film forming composition should preferably not contain Those with the function of vertical alignment.

As mentioned above, when a radical generating film is used to form the out-of-plane alignment region, the first and second substrates on which the radical generating film is formed can be used to make a unit cell, and after injecting a liquid crystal composition containing a predetermined radical polymerizable compound, Light is irradiated from the outside of the unit cell to polymerize the polymerizable compound, and the liquid crystal is vertically aligned. On the other hand, when a radical generating film is used to form the in-plane alignment region, the first and second substrates on which the radical generating film is formed can be pre-irradiated with light before the unit cell is assembled to deactivate the free radical generating ability. Assemble the unit cell, so that even if the liquid crystal cell is irradiated with light, the interface reaction can be suppressed. Or, for the liquid crystal cell prepared without inactivating the free radical generating ability, a photomask can be arranged on the outside of the liquid crystal cell, and light is irradiated through the photomask, so that free radicals are not generated in the unexposed area, and no free radicals are generated. Induce interface reaction.

In the liquid crystal display device, by fabricating the liquid crystal cell in such a way that the in-plane alignment area and the out-of-plane alignment area face each other, a tilt orientation area can be formed. For example, when a radical generating film is used for both the first substrate and the second substrate, by appropriately combining the method of forming the out-of-plane alignment region and the method of forming the in-plane alignment region, the inclined alignment region can be produced. More specifically, for example, one of the first substrate and the second substrate uses a radical generating film to form an out-of-plane alignment region, and the other substrate uses a radical generating film that deactivates the radical generating ability. An in-plane alignment area is formed, and a tilt orientation area can be formed.

In addition, 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 that does not have the ability to generate radicals is used on another substrate, the liquid crystal alignment film can be an in-plane alignment film or an out-of-plane alignment film. By combining with the above-mentioned method of producing in-plane alignment regions and out-of-plane alignment regions using radical generating films, various patterns composed of various combinations of in-plane alignment regions, inclined alignment regions, and out-of-plane alignment regions can be formed. The liquid crystal alignment film should be uniaxially aligned.

In addition, in the method for manufacturing a liquid crystal display element of the present invention, the liquid crystal composition can be adjusted in a liquid crystal composition by adjusting the content of the radical polymerizable compound and the amount of light irradiated to the liquid crystal cell, so that the liquid crystal can be oriented rather than perpendicularly. Alignment, and form an inclined alignment area. As described above, according to the method of manufacturing a liquid crystal display element of the present invention, in a liquid crystal display element with a radical generating film, at least two of the in-plane alignment area, the out-of-plane alignment area, and the oblique alignment area are patterned Chemical liquid crystal display element.

＜Liquid crystal display element＞ According to the manufacturing method of the present invention, a liquid crystal display element in which at least two of the in-plane alignment area, the out-of-plane alignment area, and the oblique alignment area are patterned can be manufactured with good productivity in the industry. Therefore, the liquid crystal display element manufactured by the manufacturing method of the present invention can be widely used in practice. For example, a reflective electrode, a transparent electrode, a λ/4 plate, a polarizing film, a color filter layer, etc. can be arranged in the liquid crystal cell according to the conventional method as needed, and it can be used as a reflective liquid crystal display element. In addition, it can be used as a transmissive liquid crystal display element by installing a backlight, a polarizing plate, a λ/4 plate, a transparent electrode, a polarizing film, a color filter layer, etc., in the liquid crystal cell according to the usual method. 10 is a schematic cross-sectional view showing an example of the liquid crystal display element of the present invention, which is an example of an IPS mode liquid crystal display element. In the liquid crystal display element 101 illustrated in FIG. 10, a liquid crystal composition 103 is sandwiched between a comb-shaped electrode substrate 102 provided with a radical generating film 102c and a counter substrate 104 provided with a liquid crystal alignment film 104a. The comb-tooth 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-tooth shape, and a radical generator formed on the base material 102a so as to cover the linear electrodes 102b膜102c. The counter substrate 104 has a base material 104b, and a liquid crystal alignment film 104a formed on the base material 104b. 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 indicated by the lines of force L. 11 is a schematic cross-sectional view showing another example of the liquid crystal display element of the present invention, which is an example of an FFS mode liquid crystal display element. In the liquid crystal display element 101 illustrated in FIG. 11, a liquid crystal composition 103 is sandwiched between a comb-shaped electrode substrate 102 provided with a radical generating film 102h and a counter substrate 104 provided with a liquid crystal alignment film 104a. The comb-tooth electrode substrate 102 has: a substrate 102d, a surface electrode 102e formed on the substrate 102d, an insulating film 102f formed on the surface electrode 102e, and a plurality of lines formed on the insulating film 102f and arranged in a comb-like shape The electrode 102g and the radical generating film 102h formed on the insulating film 102f so as to cover the linear electrode 102g. The counter substrate 104 has a base material 104b, and a liquid crystal alignment film 104a formed on the base material 104b. In this liquid crystal display element 101, when a voltage is applied to the surface electrode 102e and the linear electrode 102g, an electric field is generated between the surface electrode 102e and the linear electrode 102g as indicated by the electric force line L. [Example]

The following examples further describe the present invention, but the scope of the present invention is not limited to these examples.

In the examples, the abbreviations of the compounds used in the preparation of the polymer polymerization and the radical generating film forming composition and the methods for evaluating the characteristics are as follows.

[化31]

[化30]

[化31]

NMP: N-methyl-2-pyrrolidone, BCS: Butyl Serosu

＜Viscosity measurement＞ For the polyamic acid solution, an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) was used to measure the viscosity at 25°C with a sample volume of 1.1 mL and a cone rotor TE-1 (1°34', R24).

<Measurement of molecular weight> The molecular weight is measured with 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. GPC device: GPC-101 (manufactured by Showa Denko), column: GPC KD-803, GPC KD-805 (manufactured by Showa Denko) in series, column temperature: 50°C, eluent: N,N-two Methylformamide (for additives, lithium bromide monohydrate (LiBr･H2O) is 30mmol/L, phosphoric acid-anhydrous crystal (o-phosphoric acid) is 30mmol/L, tetrahydrofuran (THF) is 10mL/L), flow rate ：1.0mL/min Standard samples for making calibration lines: 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) (Polymer Laboratories Corporation).

<Measurement of the imidization rate> Put 20 mg of polyimide powder into the NMR sample tube (NMR standard sampling tube φ5 manufactured by Kusano Scientific Co., Ltd.), and add deuterated dimethyl sulfide (DMSO-d ₆ , 0.05 mass %TMS (tetramethylsilane) mixture) 0.53mL, apply ultrasonic wave to make it completely dissolved. The 500 MHz proton NMR of the solution was measured with a measuring device (manufactured by JEOL, JNW-ECA500). The rate of imidization is determined by using the protons from the unchanged structure before and after imidization as the reference protons, using the peak cumulative value of the protons and the ratio of the NH derived from the amido group that appears near 9.5 to 10.0 ppm. The cumulative value of the proton peak is calculated according to the following formula. The imidization rate (%)=(1-α･x/y)×100 where x is the peak cumulative value of NH from the amide group, y is the peak cumulative value of the reference proton, and α is The ratio of the number of reference protons to 1 NH proton of the amide group in the case of polyamide acid (the imidization rate is 0%).

＜第1步驟＞ 對於4,4’-二硝基-[1,1’-聯苯]-2,2’-二羧酸(20.0g、60.2mmol)，加入四氫呋喃(120g)、2-羥基-4’-(2-羥基乙氧基)-2-甲基苯丙酮(28.4g、126mmol)、1-乙基-3-(3-二甲基胺基丙基)碳二亞胺(28.0g、181mmol)、及N,N-二甲基胺基吡啶(0.735g、6.02mmol)，於室溫徹夜攪拌。反應結束後，利用水/氯仿分液萃取2次，將獲得之有機相進行濃縮，得到水飴狀茶色油。將其以乙酸乙酯/己烷＝3/1(體積比)混合溶劑利用管柱層析法進行精製。將獲得之精製物(fraction)濃縮，結果成為黃色透明油，繼續靜置，結果從油析出白色結晶。將析出的結晶以乙酸乙酯/己烷＝3/1(體積比)混合溶劑進行漿液洗淨，過濾並使結晶乾燥，得到化合物(DA-4-1)(產量：29.8g、40.0mmol、產率67%)。¹ H-NMR(500MHz)，於DMSO-d₆ ：8.57(d, J＝2.5Hz, 2H), 8.37(dd, J＝8.5Hz, 2.5Hz, 2H), 8.18(d, J＝9.0Hz, 4H), 7.55(d, J＝8.5Hz, 2H), 6.85(d, J＝9.0Hz, 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).(Synthesis of Compound DA-4) Compound DA-4 was obtained by the following method. [化32]

<Step 1> For 4,4'-dinitro-[1,1'-biphenyl]-2,2'-dicarboxylic acid (20.0g, 60.2mmol), add tetrahydrofuran (120g) and 2-hydroxyl -4'-(2-hydroxyethoxy)-2-methylpropiophenone (28.4g, 126mmol), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (28.0 g, 181 mmol), and N,N-dimethylaminopyridine (0.735 g, 6.02 mmol), stirred at room temperature overnight. After the completion of the reaction, it was separated and extracted twice with water/chloroform, and the obtained organic phase was concentrated to obtain a watery brown oil. This was purified by column chromatography using a mixed solvent of ethyl acetate/hexane=3/1 (volume ratio). The obtained fraction was concentrated, and it turned into a yellow transparent oil, and it continued to stand still. As a result, white crystals were precipitated from the oil. The precipitated crystals were washed with 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, The yield is 67%). ¹ H-NMR (500MHz), in DMSO-d ₆ : 8.57(d, J=2.5Hz, 2H), 8.37(dd, J=8.5Hz, 2.5Hz, 2H), 8.18(d, J=9.0Hz, 4H), 7.55(d, J=8.5Hz, 2H), 6.85(d, J=9.0Hz, 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).

<The second step> To the compound (DA-4-1) (29.8 g, 40.0 mmol) obtained in the first step, tetrahydrofuran (240 g) was added, and after nitrogen replacement, 3% platinum carbon (water-containing product) (2.38) was added g) and perform nitrogen replacement, install a tedlar bag and stir at room temperature for about 17 hours. After the reaction, the platinum carbon was removed by a membrane filter, then concentrated and dried to obtain compound (DA-4) (yield: 27.4 g, 40.0 mmol, quant). ¹ H-NMR(500MHz), in DMSO-d ₆ : 8.20(dd, J=7.1Hz, 1.9Hz, 4H), 6.99(d, J=2.5Hz, 2H), 6.92(dd, J=7.3Hz, 1.9Hz, 4H), 6.80(d, J=8.2Hz, 2H), 6.67(dd, J=8.2Hz, 2.5Hz, 2H), 5.64(s, 2H), 5.24(s, 4H), 4.22(t , J=4.5Hz, 4H), 4.00(br, 4H), 1.39(s, 12H).

(Polymer polymerization and preparation of free radical generating film forming composition) <Synthesis example 1> Synthesis of TC-1(50)TC-2(50)/DA-1(70)DA-2(30) polyimide In a 100 mL 4-neck flask equipped with a nitrogen inlet tube, an air cooling tube, and a mechanical stirrer, measure 3.78 g (35.0 mmol) of DA-1 and 4.96 g (15.0 mmol) of DA-2, and add 35.0 g of DA-1 The NMP was stirred under nitrogen to completely dissolve it. After confirming the 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. After that, 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 TC-1 was further added to make the polymerization viscosity 1000 mPa･s, and a polymerization solution with a polyamide acid concentration of 20% by mass was obtained. In a 200 mL Erlenmeyer flask equipped with a magnetic stirrer, weigh 50.0 g of the polyamide acid solution obtained above, and add 92.9 g of NMP to prepare a solution with a solid content of 7% by mass, and add acetic anhydride while stirring 10.6 g (103 mmol) and 3.28 g (41.4 mmol) of pyridine were stirred at room temperature for 30 minutes, and then heated and stirred at 60°C for 3 hours. After that, the solution was returned to room temperature and poured into 500 mL of methanol while stirring to precipitate a solid. After repeating this operation twice, it was air-dried and dried in a vacuum oven set at 60°C to obtain a polyimide powder (PI-1) with Mn of 11,453, Mw of 27,655, and 67.0% ).

<Synthesis example 2> Synthesis of TC-1(50)TC-2(50)/DA-1(50)DA-2(50) polyimide Except changing the amount of monomers used as shown in Table 1, the same method as in Synthesis Example 1 was used to obtain polyimide powder (PI-2). The Mn of the polyimide powder was 21,959, the Mw was 67,088, and the imidization rate was 62.2%.

<Synthesis Example 3> Synthesis of TC-1(50)TC-2(50)/DA-2(100) Polyimide Except changing the amount of monomers used as shown in Table 1, the same method as in Synthesis Example 1 was used to obtain polyimide powder (PI-3). The Mn of the polyimide powder was 21,959, the Mw was 67,088, and the imidization rate was 72.0%.

<Synthesis example 4> Polymerization of TC-3(100)/DA-3(50)DA-4(50) polyamide acid In a 100mL 4-necked flask equipped with a nitrogen inlet tube, an air cooling tube, and a mechanical stirrer, weigh 2.44g (10.00mmol) of DA-3 and 6.85g (10.00mmol) of DA-4, and add 52.6g of The NMP was stirred under nitrogen to completely dissolve it. After confirming the dissolution, 4.21 g (18.80 mmol) of TC-3 and 23.9 g of NMP were added, and heated and stirred at 40° C. for 12 hours under a nitrogen atmosphere. The polymerization viscosity was confirmed, and TC-3 was further added to make the polymerization viscosity 400 mPa･s, and a polymerization solution (PAA-1) with a polyamide acid concentration of 15% by mass was obtained. The Mn of the polyamide acid is 16,331, and the Mw is 42,999.

<Synthesis example 5> Synthesis of AC-1(40)AC-2(60) polymethacrylate In a 100mL 4-necked flask equipped with a nitrogen inlet tube, an air cooling tube, and a mechanical stirrer, weigh out 5.00g (15.0mmol) of AC-1, 6.91g (22.6mmol) of AC-2, and 0.185g (1.13) mmol) AIBN, add 67.5 g of NMP and stir under a nitrogen atmosphere to completely dissolve it. After the solution was vacuum degassed, it was heated and stirred at 60° C. for 12 hours in a nitrogen atmosphere. After that, the solution was returned to room temperature and poured into 300 mL of methanol while stirring to precipitate a solid. After repeating this operation twice, it was air-dried and dried in a vacuum oven set at 60°C, thereby obtaining polymethacrylate powder (PMA-1) with Mn of 37,197 and Mw of 116,919.

<Free radical generating film forming composition: Preparation of AL-1> In a 15 mL vial equipped with a magnetic stirrer, weigh 0.90 g of the polyimide powder (PI-1) obtained in Synthesis Example 1, and add 5.10 g of NMP, and heat and stir at 50°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, thereby obtaining the radical generating film forming composition of the present invention: AL-1 (solid content: 6.0% by mass, NMP: 74% by mass, BCS: 20% by mass).

<Free radical generating film forming composition: Preparation of AL-2> Using the polyimide powder (PI-2) obtained in Synthesis Example 2, the radical generating film forming composition of 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).

<Free radical generating film forming composition: Preparation of AL-3> Using the polyimide powder (PI-3) obtained in Synthesis Example 3, the radical generating film forming composition of 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).

<Free radical generating film forming composition: Preparation of AL-4> In a 15 mL vial equipped with a magnetic stirrer, weigh 6.00 g of the polyamide acid (PAA-1) obtained in Synthesis Example 4, add 6.00 g of NMP and 3.00 g of BCS, and stir for 3 For hours, the radical generating film forming composition of the present invention: AL-4 (solid content: 6.0% by mass, NMP: 74% by mass, and BCS: 20% by mass) was obtained by this.

<Free radical generating film forming composition: Preparation of AL-5> In a 15 mL vial equipped with a magnetic stirrer, measure 0.27 g of the polymethacrylate powder (PMA-1) obtained in Synthesis Example 5 and 0.63 g of the polymethacrylate powder obtained in Synthesis Example 3 Amine powder (PI-3) was added with 5.10g of NMP, and heated and stirred at 60°C to obtain a polymer solution with a solid content 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 of the present invention: AL-5 (solid content: 6.0% by mass, NMP: 74% by mass, BCS: 20% by mass).

<Free radical generating film forming composition: Preparation of AL-6> In a 15 mL vial equipped with a magnetic stirrer, weigh 0.45 g of the polymethacrylate powder (PMA-1) obtained in Synthesis Example 5 and 0.45 g of the polymethacrylate powder obtained in Synthesis Example 3 Amine powder (PI-3) was added with 5.10g of NMP, and heated and stirred at 60°C to obtain a polymer solution with a solid content 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 of the present invention: AL-6 (solid content: 6.0% by mass, NMP: 74% by mass, BCS: 20% by mass).

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

The composition of polyamide acid and polyimide is shown in Table 1 below. [Table 1] Tetracarboxylic dianhydride (mol%) Diamine (mol%) TC-1 TC-2 TC-3 DA-1 DA-2 DA-3 DA-4 PI-1 50 50 - 70 30 - - PI-2 50 50 - 50 50 - - PI-3 50 50 - - 100 - - PAA-1 - - 100 - - 50 50

The composition of polymethacrylate is shown in Table 2 below. [Table 2] Methacrylic acid (mol%) AC-1 AC-2 PMA-1 40 60

The composition of the radical generating film forming composition and the non-radical generating film forming composition are shown in Table 3 below. [table 3] Polyimide solid content (%) Polyamide acid solid content (%) Polymethacrylate solid content (%) NMP mass% BCS quality% AL-1 PI-1(6.0) - - 74 20 AL-2 PI-2(6.0) - - 74 20 AL-3 PI-3(6.0) - - 74 20 AL-4 - PAA-1(6.0) - 74 20 AL-5 PI-3(1.8) - PMA-1(4.2) 74 20 AL-6 PI-3(3.0) - PMA-1(3.0) 74 20 AL-7 - - PMA-1(6.0) 74 20

The composition of the liquid crystal species is shown in Table 4 below. [Table 4] Use LCD Polymeric compound (additive) name Addition amount (mass%) LC-1 MLC-7026 - - LC-2 MLC-3019 - - LC-3 MLC-7026 DMA 1 LC-4 MLC-7026 DMA 3 LC-5 MLC-7026 DMA 5 LC-6 MLC-3019 DMA 5 LC-7 MLC-7026 DMA 10 LC-8 MLC-7026 IC-12 5 LC-9 MLC-7026 AAA-C6C6 5 LC-10 MLC-3019 AAA-C6C6 5 LC-11 MLC-7026 MACH-C5 5

於安裝有Dean-Stark管之4口燒瓶中，量取伊康酸30.0g(231mmol)、及1-十二醇81.6g(438mmol)，以環己烷(700mL)使其完全溶解。確認溶解後，加入濃硫酸1.13g(11.5mmol)、及二丁基羥基甲苯(BHT)0.51g(2.31mmol)，於氮氣環境下在120℃加熱攪拌24小時。利用核磁共振光譜(¹ H-NMR光譜)確認反應結束後，在反應溶液中加入正己烷100mL，以10%碳酸鈉水溶液100g洗淨3次，並以純水100mL洗淨3次，利用無水硫酸鎂使其乾燥。過濾、濃縮後，進行真空乾燥，藉此得到白色固體78.0g(167mmol：產率76.3%)。就結構而言利用¹ H-NMR光譜確認係目的物。測定數據如下所示。¹ H-NMR(400MHz,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)(Polymerizable compound) The polymerizable compound (additive) described in Table 4 was obtained in the following manner. <Synthesis Example 1 of Polymeric Compounds> Synthesis of Didodecyl Iconate (IC-12) [Chemical 33]

In a 4-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 the mixture was completely dissolved in cyclohexane (700 mL). After confirming the 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 in a nitrogen atmosphere. After confirming the completion of the reaction by nuclear magnetic resonance spectroscopy ( ¹ H-NMR spectrum), add 100 mL of n-hexane to the reaction solution, wash with 100 g of 10% sodium carbonate aqueous solution 3 times, and wash with 100 mL of pure water 3 times, using anhydrous sulfuric acid Magnesium dries it. After filtration and concentration, vacuum drying was performed to obtain 78.0 g (167 mmol: yield 76.3%) of a white solid. In terms of structure, the ^{target product was confirmed by 1} H-NMR spectrum. The measurement data is shown below. ¹ H-NMR (400MHz, CDCl ₃ ) 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)

於4口燒瓶中，量取二己胺33.3g(180mmol)、及三乙胺27.3g(270mmol)，並加入500mL之THF，於室溫使其完全溶解。確認溶解後，將反應容器進行冰冷，並保持系內為0℃，緩慢滴加丙烯醯氯17.9g(198mmol)。利用核磁共振光譜(¹ H-NMR光譜)確認反應結束後，在反應溶液中加入乙酸乙酯100mL，以10%碳酸鈉水溶液100g洗淨3次，並以純水100mL洗淨3次，利用無水硫酸鎂使其乾燥。過濾、濃縮後，進行真空乾燥，藉此得到透明油狀液體33.6g(140mmol：產率78.1%)。就結構而言利用¹ H-NMR光譜確認係目的物。測定數據如下所示。¹ H-NMR(400MHz,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)<Synthesis example 2 of polymerizable compound> Synthesis of dihexylacrylamide (AAA-C6C6) [Chemical 34]

In a 4-necked flask, 33.3 g (180 mmol) of dihexylamine and 27.3 g (270 mmol) of triethylamine were measured, 500 mL of THF was added, and it was completely dissolved at room temperature. After confirming the dissolution, the reaction vessel was ice-cooled, and while maintaining the system at 0°C, 17.9 g (198 mmol) of acrylic chloride was slowly added dropwise. After confirming the completion of the reaction by nuclear magnetic resonance spectroscopy ( ¹ H-NMR spectrum), add 100 mL of ethyl acetate to the reaction solution, wash with 100 g of 10% sodium carbonate aqueous solution 3 times, and wash with 100 mL of pure water 3 times, using anhydrous Magnesium sulfate makes it dry. After filtration and concentration, vacuum drying was performed to obtain 33.6 g (140 mmol: 78.1% yield) of a transparent oily liquid. In terms of structure, the ^{target product was confirmed by 1} H-NMR spectrum. The measurement data is shown below. ¹ H-NMR (400MHz, DMSO-d ₆ ) 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)

於4口燒瓶中，量取4-戊基環己醇25.0g(147mmol)、及三乙胺22.3g(220mmol)，加入400mL之THF，於室溫使其完全溶解。確認溶解後，在冰浴中保持系內為0℃，緩慢滴加甲基丙烯醯氯18.4g(176mmol)。利用核磁共振光譜(¹ H-NMR光譜)確認反應結束後，在反應溶液中加入己烷100mL，以10%碳酸鈉水溶液100g洗淨3次，並以純水100mL洗淨3次，利用無水硫酸鎂使其乾燥。過濾、濃縮後，進行真空乾燥，藉此得到透明油狀液體20.3g(86.2mmol：產率58.0%)。就結構而言利用¹ H-NMR光譜確認係目的物。測定數據如下所示。¹ H-NMR(400 MHz,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)<Polymerizable compound synthesis example 3> Synthesis of 4-pentylcyclohexyl methacrylate (MACH-C5) [Chemical 35]

In a 4-necked flask, measure 25.0 g (147 mmol) of 4-pentylcyclohexanol and 22.3 g (220 mmol) of triethylamine, add 400 mL of THF, and dissolve it completely at room temperature. After confirming the dissolution, the system was kept at 0°C in an ice bath, and 18.4 g (176 mmol) of methacrylic acid chloride was slowly added dropwise. After confirming the completion of the reaction by nuclear magnetic resonance spectroscopy ( ¹ H-NMR spectrum), add 100 mL of hexane to the reaction solution, wash with 100 g of 10% sodium carbonate aqueous solution 3 times, and wash with 100 mL of pure water 3 times, using anhydrous sulfuric acid Magnesium dries it. After filtration and concentration, vacuum drying was performed to obtain 20.3 g (86.2 mmol: yield 58.0%) of a transparent oily liquid. In terms of structure, the ^{target product was confirmed by 1} H-NMR spectrum. The measurement data is shown below. ¹ H-NMR (400 MHz, DMSO-d ₆ )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)

＜Purchase of polymerizable compounds＞ The polymerizable compound DMA is directly purchased from Tokyo Chemical Industry Co., Ltd. (TCI).

(Production of liquid crystal display element) Using the AL-1 to AL-7 obtained above, and SE-6414, NRB-U438 (manufactured by Nissan Chemical Co., Ltd.), which are liquid crystal alignment agents for horizontal alignment, were used to fabricate liquid crystal cells, and the structures shown in Table 5 below were fabricated Liquid crystal display element.

The composition of the liquid crystal cell is shown in Table 5 below. [table 5] Cell number of liquid crystal cell First substrate Second substrate Alignment processing of the first and second substrates Liquid crystal species Secondary exposure (J/cm ² ) 1 AL-2 without Friction treatment LC-5 10 2 AL-2 SE-6414 Friction treatment LC-5 10 3 AL-2 AL-2 Friction treatment LC-1 10 4 AL-2 AL-2 Friction treatment LC-2 10 5 AL-2 AL-2 Friction treatment LC-3 10 6 AL-2 AL-2 Friction treatment LC-4 10 7 AL-2 AL-2 Friction treatment LC-5 10 8 AL-2 AL-2 Friction treatment LC-6 30 9 AL-2 AL-2 Friction treatment LC-7 10 10 AL-1 AL-1 Friction treatment LC-5 10 11 AL-3 AL-3 Friction treatment LC-5 10 12 AL-2 AL-2 Friction treatment LC-5 0 13 AL-2 AL-2 Friction treatment LC-5 1 14 AL-2 AL-2 Friction treatment LC-5 3 15 AL-2 AL-2 Friction treatment LC-5 5 16 AL-2 AL-2 Friction treatment LC-5 10 17 AL-2 AL-2 Friction treatment LC-8 5 18 AL-2 AL-2 Friction treatment LC-9 5 19 AL-2 AL-2 Friction treatment LC-10 30 20 AL-2 AL-2 Friction treatment LC-11 5 twenty one AL-4 AL-4 Optical alignment LC-5 10 twenty two AL-5 AL-5 Optical alignment LC-5 10 twenty three AL-6 AL-6 Optical alignment LC-5 10 twenty four AL-5 AL-7 Optical alignment LC-5 10 25 AL-6 AL-7 Optical alignment LC-5 10 26 AL-7 AL-7 Optical alignment LC-5 10 27 SE-6414 SE-6414 Friction treatment LC-5 10 28 NRB-U438 NRB-U438 Optical alignment LC-5 10

＜First and second substrates＞ The first and second substrates are alkali-free glass substrates with a size of 30mm×40mm and a thickness of 1.1mm. 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.

＜Surface treatment steps of AL-1, AL-2, AL-3, SE-6414＞ After filtering AL-1, AL-2, AL-3, and SE-6414 with a filter with a pore size of 1.0μm, apply spin coating to the electrode forming surfaces of the first and second substrates, and heat at 80°C Dry the board for 2 minutes. Then, it was calcined 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. The first and second substrates with the coating film obtained above were subjected to rubbing treatment. After bonding, the rubbing direction of the first substrate system is the rubbing process from the long side direction, and the rubbing direction of the second substrate system is the rubbing process from the short side direction so that the rubbing direction becomes antiparallel. As far as the type of friction cloth is concerned, Yoshikawa Chemical's rayon cloth: YA-20R, roll diameter 120mm is used. The friction treatment of AL-1, AL-2, and AL-3 is performed under the conditions of rotation speed of 500rpm, moving speed of 30mm/sec, and pushing amount of 0.3mm. In addition, the friction treatment of SE-6414 is performed under the conditions of a rotation speed of 1000 rpm, a moving speed of 20 mm/sec, and a pressing amount of 0.4 mm. After the rubbing treatment, ultrasonic washing was performed in pure water for 1 minute, and dried at 80°C for 15 minutes.

<Surface treatment steps of AL-4, AL-5, AL-6, AL-7, NRB-U438> After filtering AL-5, AL-6, AL-7 with a filter with a pore size of 1.0 μm, use a spinner The coating method is applied to the electrode forming surfaces of the first and second substrates, and dried on a hot plate at 70°C for 90 seconds. After that, using a high-pressure mercury lamp (313 nm band pass filter manufactured by CERMA PRECISION), the linearly polarized light with a wavelength of 313 nm was exposed to 0.005 J/cm ² and calcined on a hot plate at 150° C. for 30 minutes. After filtering AL-4 and NRB-U438 with a filter with a pore size of 1.0 μm, they were applied to the electrode formation surfaces of the first and second substrates by spin coating, dried on a hot plate at 80°C for 2 minutes, and then contained Calcined in a thermal cycle heating furnace at 230°C for 30 minutes. After that, using a low-pressure mercury lamp (short-wavelength cut-off filter below 240nm made by Ushio Electric Co., Ltd.), the linearly polarized light with a wavelength of 254nm was exposed to 0.3J/cm ² , and it was calcined in a thermal cycle heating furnace at an internal temperature of 230°C for 30 minute.

<One exposure> After finishing the surface treatment step, the two substrates (first and second substrates) with the liquid crystal alignment film attached, use a high-pressure mercury lamp (short-wavelength cut-off filter below 300nm made by CERMA PRECISION) to reduce the wavelength of 313nm The light is exposed to 10J/cm ² . To selectively irradiate light, a photomask (100, 50, 30, 5 μm L/S with chromium wiring made by Mitani Micronics) is placed on the substrate, and pattern exposure is performed. This operation is described as one exposure afterwards. In addition, one exposure is for the purpose of deliberately deactivating radicals contained in the alignment film, and is only suitable for Examples 23, 24, 27, 28, 29, 30, and 32.

＜Production of liquid crystal cell＞ Use the two substrates (first and second substrates) with the liquid crystal alignment film after the completion of the surface treatment step and the further one exposure step for Examples 23, 24, 27, 28, 29, 30, and 32, The liquid crystal injection port is kept and the surroundings are sealed to produce an empty cell with a cell gap of about 4 μm. In addition, the surface treatment step includes a rubbing treatment, and the empty cell is made in such a way that the rubbing direction of the first substrate and the second substrate becomes anti-parallel. In this empty cell, liquid crystals are injected under vacuum at room temperature (as shown in Table 4, positive liquid crystal MLC-3019 for IPS manufactured by Merck Corporation or negative liquid crystal MLC-7026 for IPS manufactured by Merck Corporation, with the addition of relative liquid crystal After the specified amount of each additive), 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 was heat-treated at 120°C for 10 minutes.

＜Double exposure＞ For the prepared liquid crystal cell, a high-pressure mercury lamp (a short-wavelength cut-off filter below 300 nm manufactured by CERMA PRECISION) was used to irradiate light with a wavelength of 313 nm. The exposure is shown in Table 5. When it is desired to selectively irradiate 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 described as a double exposure. In addition, the secondary exposure is for the purpose of allowing the radical-generating radical contained in the alignment film to react with the polymerizable compound (additive) in the liquid crystal.

(Result of visual evaluation of liquid crystal orientation after second exposure) Use a polarizing plate configured as crossed nicols to confirm the alignment state of the liquid crystal cell after the second exposure. In addition, the angle between the uniaxial alignment direction of the liquid crystal and the polarization direction is set to 45 degrees. At this time, light is transmitted through uniaxial alignment of the liquid crystal, and light is not transmitted through out-of-plane alignment. As far as the embodiment is concerned, the unit cell 7 (Embodiment 5) can perform out-of-plane alignment control, so the exposed part becomes a dark field (FIG. 1A and FIG. 1B). Fig. 1A shows a photograph of a liquid crystal display element, and a schematic diagram of a photograph of the liquid crystal display element of Fig. 1A is shown in Fig. 1B (the same applies to Figs. 2 to 5, and Fig. 9 below, and a photograph of the liquid crystal display element is shown in Fig. A schematic diagram of this photo is shown in Figure B). In FIG. 1 (also collectively referred to as FIG. 1A and FIG. 1B), the exposed part of symbol 1 indicates a dark field (black), and the non-exposed part of symbol 2 indicates a bright field (white). The unit cell 27 (Comparative Example 4) cannot perform out-of-plane alignment control, so the exposed part becomes a bright field (FIG. 2A and FIG. 2B). In Fig. 2 (also collectively referred to as Fig. 2 as Fig. 2A and Fig. 2B), the exposed part and the non-exposed part both indicate the bright field (white). The unit cell 1 (Example 1) has a tilt alignment (part of it is out-of-plane alignment), so the coloration of the exposed part is reduced (part of it is a dark field), showing a gray intermediate color (FIG. 3A and FIG. 3B). In Fig. 3 (also collectively referred to as Fig. 3A and Fig. 3B), the exposure part of symbol 1 has a dark field (black) part b and a light and dark intermediate color (gray) part a mixed together. The non-exposed part of the symbol 2 indicates the bright field (white).

The liquid crystal display elements in the respective Examples and Comparative Examples shown in Tables 6 to 8 below were evaluated by the same method as those shown in FIGS. 1 to 3. In Tables 6 to 8, the secondary exposure position represents dark field (black) and can perform out-of-plane alignment, the controller is marked as ○, which means bright field (white) and cannot perform out-of-plane alignment, and the controller is marked as ×, which represents intermediate color (gray). ) And uniaxial alignment and uneven alignment with a tilt angle are marked as △.

The results of the visual evaluation of the liquid crystal orientation after the second exposure are shown in Table 6 below. [Table 6] Cell number of liquid crystal cell Orientation state Example 1 1 △(Picture 3) Example 2 2 △ Example 3 5 △ Example 4 6 〇 Example 5 7 〇 (Picture 1) Example 6 9 〇 Example 7 10 〇 Example 8 11 〇 Example 9 13 △ Example 10 14 〇 Example 11 15 〇 Example 12 16 〇 Comparative example 1 3 X Comparative example 2 4 X Comparative example 3 12 X Comparative example 4 27 ×(Picture 2) In order to induce out-of-plane alignment from the in-plane uniaxial alignment state, it is necessary to (i) include a radical generating radical in the alignment film, (ii) include a polymerizable compound (additive) in the liquid crystal, and (iii) perform light irradiation. In addition, in order to form a good out-of-plane alignment at this time, it is effective to consider the content of radicals that generate radicals, the content of polymerizable compounds, and the amount of light irradiation.

The results of the visual evaluation of the liquid crystal orientation after the second exposure are shown in Table 7 below. [Table 7] Cell number of liquid crystal cell Orientation state Example 5 7 〇 Example 13 17 〇 Example 14 18 〇 Example 15 20 〇 Example 16 8 △ Example 17 19 〇 The polymerizable compound (additive) required for out-of-plane alignment control is not limited to DMA. As long as it is an additive with an appropriate structure, it can be controlled out-of-plane alignment. In addition, the type of liquid crystal is not limited to MLC-7026, which is a liquid crystal with a negative permittivity. Even MLC-3019 with a liquid crystal with a positive permittivity can perform out-of-plane alignment control.

The results of the visual evaluation of the liquid crystal orientation after the second exposure are shown in Table 8 below. [Table 8] Cell number of liquid crystal cell Orientation state Example 18 twenty one 〇 Example 19 twenty two 〇 Example 20 twenty three 〇 Example 21 twenty four 〇 Example 22 25 〇 Comparative example 5 26 X Comparative example 6 28 X When using a photo-alignment film that has undergone photo-alignment treatment, out-of-plane alignment control can also be performed, regardless of the type of polymer constituting the alignment film and the exposure wavelength required for photo-alignment. In addition, as shown in the liquid crystal cells 22, 23, etc. used in Examples 19, 20, etc., when an alignment film material that does not have a radical generating radical is used, a polymer material with a radical generating radical is used. Mixing can be controlled out-of-plane alignment. At this time, the out-of-plane alignment control can be performed as long as an appropriate amount of radical-generating radicals is introduced. In addition, as in Examples 21 and 22, only when the first substrate is coated with a photo-alignment film with radical generating ability, out-of-plane alignment control may also be performed. It depends on the type of photo-alignment film used. For example, when the alignment binding force of the liquid crystal is small, it will be observed when the alignment binding force of the liquid crystal decreases due to light irradiation.

(The result of visual evaluation of the orientation of the liquid crystal adapted to one exposure) Use a polarizing plate configured as a crossed Nicol to confirm the alignment of the liquid crystal cell after the second exposure. In addition, the angle formed by the uniaxial alignment direction of the liquid crystal cell and the polarization direction is set to 45 degrees. The results are shown in Table 9 below.

[Table 9] Cell number of liquid crystal cell One exposure condition Second exposure conditions Orientation state Example 23 7 Full-surface exposure (only the first substrate) Full exposure Tilt alignment (Figure 4) Example 24 7 Full-surface exposure (first and second substrates) Full exposure In-plane uniaxial alignment (Figure 5) For one exposure, if only the entire surface of the first substrate is exposed, a tilt alignment is formed (FIG. 4A and FIG. 4B). In Fig. 4 (also collectively referred to as Fig. 4A and Fig. 4B), the part indicated by symbol 3 is an area where only the first substrate is exposed by one exposure and the entire surface is exposed by second exposure. The part indicated by the symbol 3 represents an intermediate color of gray and forms a tilt alignment. The part denoted by the symbol 4 is a non-exposed area where only the first substrate is exposed by one exposure and is not exposed by the second exposure. The part denoted by symbol 4 represents a bright field (white) and forms an in-plane alignment. If the entire surface of the first substrate and the second substrate are exposed in one exposure, an in-plane alignment is formed (FIG. 5A and FIG. 5B). In Fig. 5 (also collectively referred to as Fig. 5A and Fig. 5B), the part indicated by symbol 5 is the area where the first and second substrates are exposed by one exposure, and the entire surface is exposed by the second exposure. The part denoted by symbol 6 is a non-exposed area where the first and second substrates are exposed by one exposure and not exposed by the second exposure. The parts of symbols 5 and 6 both indicate a bright field (white) and form an in-plane alignment. It can be confirmed that by irradiating light on the substrate before the unit cell is fabricated, the radicals that generate free radicals contained in the alignment film are inactivated, and the reaction with the polymerizable compound (additive) is not induced during the second exposure. Will form out-of-plane alignment.

(Evaluation of Alignment Patterning) Using a polarizing plate configured as a crossed Nicol, confirm the alignment state of the liquid crystal display element after pattern exposure. In addition, the angle formed by the uniaxial alignment direction of the liquid crystal cell and the polarization direction is set to 45 degrees. The evaluation of the alignment pattern is based on visual observation and judgment from the viewpoints of whether the alignment can be controlled by light irradiation, the uniformity of the alignment, and the sharpness of the alignment control surface (the interface between the in-plane uniaxial alignment and the out-of-plane alignment). The results are shown in Table 10 below.

[Table 10] Cell number of liquid crystal cell Patterned state Example 25 7 Uniform and clear (picture 6 left) Example 26 twenty one Uniform and clear (picture 6 right) The alignment change from in-plane (uniaxial) alignment to out-of-plane alignment caused by light irradiation can be uniformly controlled, and the interface between different alignments is distinct (Figure 6). As shown in FIG. 6, it can be confirmed that the in-plane alignment area in the bright field (white) and the out-of-plane alignment area in the dark field (black) can be clearly patterned. In addition, this does not depend on the type of polymer constituting the alignment film and the alignment treatment method. The alignment patterns can be made with significantly different types of materials. Therefore, it can be inferred that the examples in Tables 6 to 8 that can perform out-of-plane alignment control can all be aligned and patterned.

(Evaluation of fine alignment patterning) Using a polarizing plate configured as a crossed Nicol, confirm the alignment state of the liquid crystal display element after pattern exposure. In addition, the angle formed by the uniaxial alignment direction of the liquid crystal cell and the polarization direction is set to 45 degrees. The evaluation of alignment patterning is to visually observe and judge whether the alignment can be controlled by light irradiation, the uniformity of the alignment, and the sharpness of the alignment control surface (the interface between the in-plane uniaxial alignment and the out-of-plane alignment) . The results are shown in Table 11 below.

[Table 11] Cell number of liquid crystal cell Mask L/S width (μm) One exposure condition Second exposure conditions Patterned state Example 27 7 100 Pattern exposure (only the first substrate) Full exposure Uniform and clear (Figure 7) Example 28 7 50 Pattern exposure (only the first substrate) Full exposure Uniform and clear Example 29 7 30 Pattern exposure (only the first substrate) Full exposure Uniform and clear Example 30 7 5 Pattern exposure (only the first substrate) Full exposure Uniform and clear (Figure 8) Example 31 7 100 without Pattern exposure Clear Example 32 7 100 Pattern exposure (first and second substrates) pattern direction is vertical Full exposure Uniform and clear (Figure 9) Regarding one exposure, the liquid crystal display element produced by using the pattern-exposed substrate can produce uniform and clear fine alignment patterns regardless of the L/S width of the mask. For example, a photograph of the liquid crystal display element obtained in Example 27 is shown in FIG. 7. At this time, only pattern exposure is performed on the first substrate for one exposure, so the intermediate color (gray) portion indicated by symbol 7 in FIG. 7 is in a tilted alignment state. The dark field (black) portion indicated by symbol 8 in FIG. 7 is in an out-of-plane alignment state. FIG. 8 shows the result of Example 30 obtained by changing the L/S width of the mask of Example 27. In FIG. 8, the difference between the intermediate color (gray) part and the dark field (black) part is illustrated in FIG. 7. In addition, when the intermediate color (gray) portion is to be in-plane uniaxially aligned, the second substrate is also exposed with the same pattern as the first substrate, and the exposed parts are bonded to each other to form a liquid crystal cell, and then the second exposure is performed. Can. As shown in Example 31, the liquid crystal display element that does not perform a single exposure, but performs pattern exposure for the second exposure, can confirm that the alignment patterning can be performed under the condition that the L/S width of the photomask is 100 μm. In the liquid crystal display device of Example 31, the bright field (white) in-plane alignment area and the dark field (black) out-of-plane alignment area can also be clearly patterned. In addition, as shown in Example 32, it can be confirmed that by pattern exposure on both the first and second substrates, the pattern direction is vertically bonded to produce the liquid crystal cell, and then the second exposure can be performed on a liquid crystal display. Three alignment states of in-plane uniaxial alignment, out-of-plane alignment, and inclined alignment are produced in the component. The results of the liquid crystal display element obtained in Example 32 are shown (FIG. 9A and FIG. 9B). FIG. 9A shows a photograph of the liquid crystal display element, and a schematic diagram of the photograph of the liquid crystal display element of FIG. 9A is shown in FIG. 9B. As shown in FIG. 9 (also referred to as FIG. 9A and FIG. 9B collectively as FIG. 9), the dark field (black) portion indicated by symbol 9 is in an out-of-plane alignment state. The bright field (white) portion indicated by symbol 10 forms an in-plane alignment. The part of the intermediate color (gray) indicated by the symbol 11 (the part indicated by the diagonal line pattern in FIG. 9B) forms a tilted alignment state. [Industrial Utilization]

According to the present invention, a liquid crystal display element with patterned at least two of the in-plane alignment area, the out-of-plane alignment area, and the oblique alignment area can be manufactured with good productivity in the industry.

1: Dark field (black) a: The mid-color part of dark field (black) 1 b: The black part of dark field (black) 1 2: Bright field (white) 3: Intermediate color (gray) 4: Bright field (white) 5: Bright field (white) 6: Bright field (white) 7: Intermediate color (gray) 8: Dark field (black) 9: Dark field (black) 10: Bright field (white) 11: Intermediate color (gray) 101: liquid crystal display element 102: Comb electrode substrate 102a: Substrate 102b: Wire electrode 102c: free radical generating membrane 102d: substrate 102e: Surface electrode 102f: insulating film 102g: wire electrode 102h: free radical generating membrane 103: Liquid crystal composition 104: Opposite substrate 104a: Liquid crystal alignment film 104b: Substrate

[Fig. 1A] Fig. 1A is a photograph of the liquid crystal display element obtained in Example 5. [Fig. [Fig. 1B] Fig. 1B is a schematic diagram showing a photograph of the liquid crystal display element of Fig. 1A. [Fig. 2A] Fig. 2A is a photograph of the liquid crystal display element obtained in Comparative Example 4. [Fig. [Fig. 2B] Fig. 2B is a schematic diagram showing a photograph of the liquid crystal display element of Fig. 2A. [Fig. 3A] Fig. 3A is a photograph of the liquid crystal display element obtained in Example 1. [Fig. [Fig. 3B] Fig. 3B is a schematic diagram showing a photograph of the liquid crystal display element of Fig. 3A. [Fig. 4A] Fig. 4A is a photograph of the liquid crystal display element obtained in Example 23. [Fig. [Fig. 4B] Fig. 4B is a schematic diagram showing a photograph of the liquid crystal display element of Fig. 4A. [Fig. 5A] Fig. 5A is a photograph of the liquid crystal display element obtained in Example 24. [Fig. [Fig. 5B] Fig. 5B is a schematic diagram showing a photograph of the liquid crystal display element of Fig. 5A. [Fig. 6] Fig. 6 is a photograph of the liquid crystal display element obtained in Example 25 and Example 26. [Fig. 7] Fig. 7 is a photograph of the liquid crystal display element obtained in Example 27. [Fig. 8] Fig. 8 is a photograph of the liquid crystal display element obtained in Example 30. [Fig. 9A] Fig. 9A is a photograph of the liquid crystal display element obtained in Example 32. [Fig. [Fig. 9B] Fig. 9B is a schematic diagram showing a photograph of the liquid crystal display element of Fig. 9A. Fig. 10 is a schematic cross-sectional view showing an example of the liquid crystal display element of the present invention. Fig. 11 is a schematic cross-sectional view showing another example of the liquid crystal display element of the present invention.

Claims (16)

A method for manufacturing a liquid crystal display element, which is characterized by: Include: Step (A): a step of forming a free radical generating film that can generate free radicals by light irradiation on a substrate; and Step (B): Bring a liquid crystal composition containing a liquid crystal and a radical polymerizable compound into contact with the radical generating film, while maintaining the state, the liquid crystal composition is irradiated sufficiently to polymerize the radical polymerizable compound. 240~400nm has a peak light step; The radically polymerizable compound has a function of vertically aligning the liquid crystal through polymerization; It further 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 area, the out-of-plane alignment area, and the oblique alignment area are patterned; Requirement (Z1): There is a step (C) between the step (A) and the step (B). The radical generating film obtained in the step (A) is irradiated with a peak at 240-400 nm Light to inactivate the free radical generating ability of the free radical generating film; Requirement (Z2): The step of irradiating the liquid crystal composition with light having a peak at 240 to 400 nm in the step (B) is performed through a photomask. The method for manufacturing a liquid crystal display element according to claim 1, wherein the radical generating film is a film that has been uniaxially aligned. The method for manufacturing a liquid crystal display element according to claim 1, wherein the step (B) of irradiating the liquid crystal composition with light having a peak at 240 to 400 nm is performed under no electric field. The method for manufacturing a liquid crystal display element according to claim 1, wherein the radical generating film has a polymer containing an organic group that induces radical polymerization. The method for manufacturing a liquid crystal display element of claim 4, wherein the polymer containing an organic group that induces 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 induces radical polymerization. The method for manufacturing a liquid crystal display element according to claim 4, wherein the polymer is selected from a polyimide precursor and a polyimide obtained by using a diamine component containing a diamine containing an organic group that induces radical polymerization. At least one of amine, polyurea, and polyamide. The method for manufacturing a liquid crystal display element of claim 5, wherein the organic group that induces radical polymerization is a group represented by the following formula (3);

In formula (3), the dotted line represents the bond with the benzene ring, and R ⁶ represents a single bond, -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-; R ⁷ represents a single bond, or the number of carbons substituted by fluorine atoms 1 ～20 alkylene, any _{one or more of -CH 2} -or -CF ₂ -of the alkylene can also be independently replaced by one selected from -CH=CH-, divalent carbocyclic ring, and two The group of a valent heterocyclic ring, in addition, can also be conditioned on any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other Replace with these groups; R ⁸ represents an organic group that induces free radical polymerization represented by the formulas [X-1]～[X-18], [W], [Y] and [Z];

In formulas [X-1] ~ [X-18], * represents the bonding site ^{with R 7} _{, S 1} and S ₂ each independently represent -O-, -NR-, or -S-, and R represents a hydrogen atom , A halogen atom, an alkyl group with 1 to 10 carbons, or an alkoxy group with 1 to 10 carbons, R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, or an alkyl group with 1 to 4 carbons;

In the formulas [W], [Y], [Z], * represents the bonding site ^{with R 7 and S 3} represents a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, _{-CON(CH 3} )-, or -N(CH ₃ )CO-, Ar represents selected from or may have an organic group and / Or an aromatic hydrocarbon group in the group consisting of phenylene, naphthylene, and biphenyl with halogen atoms as substituents, R ⁹ and R ¹⁰ are each independently an alkyl group or alkane with 1 to 10 carbon atoms When the oxy, benzyl, or phenethyl group is an alkyl group or an alkoxy group, R ⁹ and R ¹⁰ may also form a ring; Q represents any of the following structures;

In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O-, or -S-, R represents a hydrogen atom or an alkyl group with 1 to 4 carbons, * represents an atomic bond; R ¹² represents a hydrogen atom, halogen Atom, C 1-10 alkyl group or C 1-10 alkoxy group. The method for manufacturing a liquid crystal display element according to claim 6, wherein the diamine containing an organic group that induces radical polymerization is a diamine represented by the following formula (2);

In formula (2), A ¹ and A ² each independently represent a hydrogen atom or a group represented by the following formula (3), but ^{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(CH ₃ ) ₂ -, -NH-, -CO-, -NHCO-, -COO-, -(CH ₂ ) _m -, -SO ₂ -, or these Any combination of divalent organic groups, m represents an integer from 1 to 8; p represents an integer from 0 to 2; when p is 2, a plurality of A ² and E each independently have the aforementioned definition; and when p is 0 , A ^{1 is} composed of the base represented by the following formula (3);

In formula (3), the dotted line represents the bond with the benzene ring, and R ⁶ represents a single bond, -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-, R ⁷ represents a single bond, or unsubstituted or substituted by a fluorine atom, carbon number 1 ～20 alkylene, any _{one or more of -CH 2} -or -CF ₂ -of the alkylene can also be independently replaced by one selected from -CH=CH-, divalent carbocyclic ring, and two The group of a valent heterocyclic ring, in addition, can also be conditioned on any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other Replace with these groups; R ⁸ represents an organic group that induces free radical polymerization represented by the formulas [X-1]～[X-18], [W], [Y] and [Z];

In formulas [X-1] ~ [X-18], * represents the bonding site ^{with R 7} _{, S 1} and S ₂ each independently represent -O-, -NR-, or -S-, and R represents a hydrogen atom , A halogen atom, an alkyl group with 1 to 10 carbons, or an alkoxy group with 1 to 10 carbons, R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, or an alkyl group with 1 to 4 carbons;

In the formulas [W], [Y], [Z], * represents the bonding site ^{with R 7 and S 3} represents a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, _{-CON(CH 3} )-, or -N(CH ₃ )CO-, Ar represents selected from or may have an organic group and / Or an aromatic hydrocarbon group in the group consisting of phenylene, naphthylene, and biphenyl with halogen atoms as substituents, R ⁹ and R ¹⁰ are each independently an alkyl group or alkane with 1 to 10 carbon atoms When the oxy, benzyl, or phenethyl group is an alkyl group or an alkoxy group, R ⁹ and R ¹⁰ may also form a ring; Q represents any of the following structures;

In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O-, or -S-, R represents a hydrogen atom or an alkyl group with 1 to 4 carbons, * represents an atomic bond; R ¹² represents a hydrogen atom, halogen Atom, C 1-10 alkyl group or C 1-10 alkoxy group. The method for manufacturing a liquid crystal display element according to claim 1, wherein at least one of the radically polymerizable compounds is a compound having a polymerizable unsaturated bond in one molecule that is compatible with the liquid crystal. The method for manufacturing a liquid crystal display element according to claim 9, wherein the polymerization reactive group possessed by the radically polymerizable compound is selected from the following structures;

In the formula, * represents the bonding site with the part other than the polymerizable unsaturated bond of the compound molecule; R ^b represents an alkyl group with 3 to 20 carbon atoms, and E represents a single bond, -O-, -NR ^c -, -S-, an ester bond and a bonding group of an amide bond; R ^c represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and the alkyl group of R ^b represents a linear, branched, or cyclic alkyl group. The method for manufacturing a liquid crystal display element of claim 1, wherein the liquid crystal composition containing a liquid crystal and a radical polymerizable compound contains a polymer obtained by polymerizing the radical polymerizable compound with a Tg of 100°C or lower Radical polymerizable compound. For example, the method for manufacturing a liquid crystal display element of any one of claims 1 to 11 further has the following steps: Prepare a first substrate and a second substrate with a radical generating film, The radical generating film on the first substrate faces the second substrate, A liquid crystal composition containing a liquid crystal and a radical polymerizable compound is filled between the first substrate and the second substrate, thereby producing a liquid crystal cell. The method for manufacturing a liquid crystal display element of claim 12, wherein the second substrate has a radical generating film. According to claim 12, the method for manufacturing a liquid crystal display element, wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment. The method for manufacturing a liquid crystal display element according to claim 14, wherein the liquid crystal alignment film with uniaxial alignment is a liquid crystal alignment film for horizontal alignment. The method for manufacturing a liquid crystal display element according to claim 12, wherein the first substrate with a radical generating film is a substrate with comb-shaped electrodes.

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