TW202004296A - Method of producing zero plane anchoring film, and liquid crystal display element - Google Patents

Abstract

An object of the invention is to provide an industrial method for producing a zero plane anchoring film, a favorable liquid crystal display element that uses this film, and a method for producing the liquid crystal display element. The method for producing the zero plane anchoring film of the invention includes a step of applying sufficient energy to a liquid crystal composition containing a liquid crystal and a radical polymerizable compound having a structure represented by formula (1) shown below to induce a polymerization reaction of the radical polymerizable compound, while the liquid crystal composition is in contact with a radical generating film. Furthermore, a method for creating a functional film includes a step of preparing a cell which has a liquid crystal composition containing a liquid crystal and a radical polymerizable compound having a structure represented by formula (1) shown below sandwiched between a first substrate that has a radical generating film and a second substrate that does not have a radical generating film, and a step of applying sufficient energy to the cell to induce a polymerization reaction of the radical polymerizable compound.

In formula (1), each of R^a and R^b independently represents a linear alkyl group of 2 to 8 carbon atoms, E represents a linking group selected from among a single bond, -O-, -NR^c -, -S-, an ester linkage, and an amide linkage. R^c in the text represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms.

Description

Manufacturing method of zero-plane anchoring film and liquid crystal display element

The present invention relates to a manufacturing method using a polymer stabilization technology that can manufacture a zero-plane anchoring film by a method that does not include complicated steps, and a liquid crystal display device using the manufacturing method to achieve lower voltage driving and the like Manufacturing method.

In recent years, liquid crystal display elements have been widely used in mobile phones, computers, and television monitors. Liquid crystal display elements have characteristics such as thinness, lightness, and low power consumption, and they are expected to be used for further applications such as VR and ultra-high-definition displays. LCD display methods have been proposed by TN (Twisted Nematic, Twisted Nematic), IPS (In-Plane Switching, In-Plane Switching), VA (Vertical Alignment, Vertical Alignment) and other various display modes, all Both modes use a film (liquid crystal alignment film) that induces liquid crystal to a desired alignment state.

In particular, products with touch panels, such as tablet PCs, smart phones, and smart TVs, prefer to use the IPS mode that is not easily disturbed even when touched. In recent years, FFS has gradually adopted the concept of improving contrast and improving the viewing angle characteristics. (Boundary electric field switching, Frindge Field Switching) LCD technology uses non-contact technology for optical alignment.

However, compared with IPS, FFS has a problem that the manufacturing cost of the substrate is relatively large, and a display defect unique to the FFS mode called Vcom shift occurs. In addition, regarding the optical alignment, compared with the friction method, the size of the device that can be manufactured is increased, and the display characteristics are greatly improved, but there will be a problem in the principle of optical alignment (if it is a decomposition type, there is a decomposition product). The display is poor, if it is a heterosexual type, there will be imprint caused by insufficient alignment, etc.). In order to solve these problems, various efforts have been made by manufacturers of liquid crystal display elements and manufacturers of liquid crystal alignment films.

On the other hand, in recent years, it has been proposed to use the IPS mode of zero-plane anchoring. By using this method, it is reported that compared with the conventional IPS mode, the contrast can be improved and the voltage can be driven by a greatly reduced voltage (refer to Patent Document 1) .

Specifically, a liquid crystal alignment film with strong anchoring energy is used on one side of the substrate, and the substrate side with the electrode that generates one side of the horizontal electric field is subjected to a process that completely eliminates the alignment constraint of the liquid crystal to produce IPS Mode of liquid crystal display device method.

In recent years, some people have used thick polymer brushes to create a zero plane state, and have proposed a technical proposal for zero plane anchor IPS mode (Reference 2). With this technology, the contrast ratio is greatly improved, and the driving voltage is greatly reduced. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 4053530 [Patent Document 2] Japanese Patent Application Publication No. 2013-231757

(Problem to be solved by invention)

On the other hand, this technique has a problem that will occur in principle. The first point is that, for example, to stably generate polymer brushes on the substrate, it needs to be performed under very slim conditions, and it is not practical to consider mass production. The second point is that, for example, the alignment film is responsible for suppressing important functions such as branding. However, when a polymer brush is used, it is not easy to control the necessary electrical properties. The third point, for example, in terms of driving principle, the response speed when the voltage is Off will become very slow. The alignment constraint force is zero, and the resistance to the liquid crystal during driving is eliminated. It is expected that the threshold voltage will be greatly reduced, and the poor alignment area during driving will be reduced to increase the brightness. However, for the recovery of the liquid crystal, due to the liquid crystal recovery The power depends on the elasticity of the liquid crystal, and it is thought that the speed will drop significantly compared to when there is an alignment film. If such technical problems can be solved, there is a significant cost advantage for panel manufacturers, and it is also considered to be advantageous in terms of battery consumption suppression and image quality improvement. The present invention is to solve the above-mentioned problems, and its object is to provide a manufacturing method using a polymer stabilization technology capable of manufacturing a zero-plane anchoring film, and to achieve non-contact alignment and low driving at room temperature in a simple and inexpensive way Transverse electric field liquid crystal display device that is voltageized and accelerates response speed when off and its manufacturing method. (How to solve the problem)

In order to solve the above-mentioned problems, the inventors of the present invention have worked hard to find out that they can solve the above-mentioned problems and have completed the present invention with the following gist.

式(1)中，R^a 及R^b 各自獨立地表示碳數2～8之直鏈烷基，E表示選自單鍵、-O-、-NR^c -、-S-、酯鍵、醯胺鍵中之鍵結基，R^c 表示氫原子、碳數1～4之烷基。 [2] 如[1]之零面錨定膜之製造方法，其中，該第一基板具有之自由基發生膜係經單軸配向處理之自由基發生膜。 [3] 如[1]或[2]之零面錨定膜之製造方法，其中，該給予能量之步驟係於無電場進行。 [4] 如[1]至[3]中任一項之零面錨定膜之製造方法，其中，該自由基發生膜係將誘發自由基聚合之有機基固定化而形成之膜。 [5] 如[1]至[3]中任一項之零面錨定膜之製造方法，其中，該自由基發生膜係藉由將具有產生自由基之基之化合物與聚合物之組成物進行塗佈、硬化而形成膜以固定於膜中而獲得。 [6] 如[1]至[3]中任一項之零面錨定膜之製造方法，其中，該自由基發生膜係由含有誘發自由基聚合之有機基之聚合物構成。 [7] 如[6]之零面錨定膜之製造方法，其中，該含有誘發自由基聚合之有機基之聚合物，係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選自聚醯亞胺前驅物、聚醯亞胺、聚脲及聚醯胺中之至少一種聚合物。 [8] 如[4]、[6]及[7]中任一項之零面錨定膜之製造方法，其中，該誘發自由基聚合之有機基係下列結構[X-1]～[X-18]、[W]、[Y]、及[Z]中任一者表示之有機基； [化2]

式[X-1]～[X-18]中，＊代表與化合物分子之聚合性不飽和鍵以外之部分之鍵結部位，S₁ 、S₂ 各自獨立地表示-O-、-NR-、-S-，R表示氫原子或碳原子數1～4之烷基，R₁ ，R₂ 各自獨立地表示氫原子、鹵素原子、碳數1～4之烷基； [化3]

式[W]、[Y]、[Z]中，＊代表與化合物分子之聚合性不飽和鍵以外之部分之鍵結部位，Ar表示也可以具有有機基及/或鹵素原子作為取代基之選自由伸苯基、伸萘基、及伸聯苯基構成之群組中之芳香族烴基，R⁹ 及R¹⁰ 各自獨立地表示碳數1～10之烷基或碳數1～10之烷氧基，R⁹ 與R¹⁰ 為烷基時，末端也可互相鍵結並形成環結構；Q代表下列之任一結構； [化4]

式中，R¹¹ 表示-CH₂ -、-NR-、-O-、或-S-，R表示氫原子或碳原子數1～4之烷基，＊代表和化合物分子之Q以外之部分之鍵結部位； 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[7]之零面錨定膜之製造方法，其中，該含有誘發自由基聚合之有機基之二胺係具下列通式(6)或下列通式(7)表示之結構之二胺； [化5]

式(6)中，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替換成選自-CH=CH-、二價之碳環、及二價之雜環中之基，再者，也可以下列列舉中之任一基亦即，-O-、-COO-、-OCO-、-NHCO-、-CONH-、或-NH-互相不相鄰為條件而替換成該等基； R⁸ 表示選自下式中之自由基聚合反應性基； [化6]

式[X-1]～[X-18]中，＊表示和化合物分子之自由基聚合反應性基以外之部分之鍵結部位，S₁ 、S₂ 各自獨立地表示-O-、-NR-、-S-，R表示氫原子或碳原子數1～4之烷基，R₁ ，R₂ 各自獨立地表示氫原子、鹵素原子、碳數1～4之烷基； [化7]

式(7)中，T₁ 及T₂ 各自獨立地為單鍵、-O-、-S-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH₂ O-、-N(CH₃ )-、-CON(CH₃ )-、或-N(CH₃ )CO-， S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替換為選自-CH=CH-、二價之碳環、及二價之雜環中之基，再者，也可以下列列舉中之任一基，亦即-O-、-COO-、-OCO-、-NHCO-、-CONH-、或-NH-互相不相鄰為條件而替換為該等基， J係下式任一者表示之有機基， [化8]

式[W]、[Y]、[Z]中，＊表示和T₂ 之鍵結部位，Ar表示也可以具有有機基及/或鹵素原子作為取代基之選自由伸苯基、伸萘基、及伸聯苯基構成之群組中之芳香族烴基，R⁹ 及R¹⁰ 各自獨立地表示碳數1～10之烷基或碳數1～10之烷氧基，Q代表下列之任一結構； [化9]

式中，R¹¹ 表示-CH₂ -、-NR-、-O-、或-S-，R表示氫原子或碳原子數1～4之烷基，＊代表和化合物分子之Q以外之部分之鍵結部位； 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。 [10] 如[1]～[9]中任一項之零面錨定膜之製造方法，其中，該通式(1)中之E為酯鍵。 [11] 一種液晶晶胞之製造方法，使用如[1]～[10]中任一項之零面錨定膜之製造方法， 包括下列步驟： 準備具有自由基發生膜之第一基板及也可以有自由基發生膜之第二基板； 以第一基板上之自由基發生膜面對第二基板的方式製作晶胞；及 在第一基板與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。 [12] 如[11]之液晶晶胞之製造方法，其中，該第二基板係不具自由基發生膜之第二基板。 [13] 如[12]之液晶晶胞之製造方法，其中，該第二基板被覆了具有單軸配向性之液晶配向膜。 [14] 如[13]之液晶晶胞之製造方法，其中，該具單軸配向性之液晶配向膜係水平配向用之液晶配向膜。 [15] 如[11]～[14]中任一項之液晶晶胞之製造方法，其中，該具有自由基發生膜之第一基板為有梳齒電極之基板。 [16] 一種液晶組成物，含有液晶及具下式(1)表示之結構之自由基聚合性化合物， [化10]

式(1)中，R^a 及R^b 各自獨立地表示碳數2～8之直鏈烷基，E表示選自單鍵、-O-、-NR^c -、-S-、酯鍵、醯胺鍵中之鍵結基，R^c 表示氫原子、碳數1～4之烷基。 [17] 如[16]之液晶組成物，其中，該通式(1)中之E為酯鍵。 [18] 一種液晶顯示元件之製造方法，使用了作出使用如[1]～[15]中任一項之方法獲得之零面錨定狀態之膜。 [19] 一種液晶顯示元件，係使用如[18]之液晶顯示元件之製造方法獲得。 [20] 如[19]之液晶顯示元件，其中，第一基板或第二基板具有電極。 [21] 如[19]或[20]之液晶顯示元件，係低電壓驅動橫電場液晶顯示元件。 (發明之效果)That is, the present invention includes the following. [1] A method for manufacturing a zero-plane anchoring film, including the following steps: In a state where a liquid crystal composition containing a liquid crystal and a radically polymerizable compound having a structure represented by the following formula (1) is in contact with a free radical generating film, Give sufficient energy to polymerize the radically polymerizable compound;

In formula (1), R ^a and R ^b each independently represent a straight-chain alkyl group having 2 to 8 carbon atoms, and E represents a single bond, -O-, -NR ^c -, -S-, ester bond, or amide The bonding group in the amine bond, R ^c represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms. [2] The method for manufacturing a zero-plane anchoring film according to [1], wherein the radical generating film possessed by the first substrate is a radical generating film subjected to uniaxial alignment treatment. [3] The method for manufacturing a zero-plane anchoring film according to [1] or [2], wherein the step of applying energy is performed without an electric field. [4] The method for manufacturing a zero-plane anchoring film according to any one of [1] to [3], wherein the radical generating film is a film formed by fixing an organic group that induces radical polymerization. [5] The method for manufacturing a zero-plane anchoring film according to any one of [1] to [3], wherein the radical generating film is formed by combining a compound having a radical generating group and a polymer It is obtained by coating and curing to form a film to be fixed in the film. [6] The method for manufacturing a zero-plane anchor film according to any one of [1] to [3], wherein the radical generating film is composed of a polymer containing an organic group that induces radical polymerization. [7] The method for manufacturing a zero-plane anchoring film according to [6], wherein the polymer containing a radical polymerization-inducing organic group is a diamine component containing a diamine containing a radical polymerization-inducing organic group At least one polymer selected from the group consisting of polyimide precursor, polyimide, polyurea, and polyamide is obtained. [8] The method for manufacturing a zero-plane anchoring film according to any one of [4], [6] and [7], wherein the organic group that induces radical polymerization is the following structure [X-1] to [X -18] An organic group represented by any of [W], [Y], and [Z]; [Chem 2]

In formulas [X-1] to [X-18], * represents a bonding site other than the polymerizable unsaturated bond with the compound molecule, and S ₁ and S ₂ each independently represent -O-, -NR-, -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms;

In the formulas [W], [Y], [Z], * represents the bonding site of the part other than the polymerizable unsaturated bond with the compound molecule, Ar means that it may have an organic group and/or a halogen atom as a substituent Aromatic hydrocarbon groups in the group consisting of free phenylene, naphthyl and biphenylene, R ⁹ and R ¹⁰ each independently represent a C 1-10 alkyl group or a C 1-10 alkoxy group When R ⁹ and R ¹⁰ are alkyl groups, the ends can also be bonded to each other to form a ring structure; Q represents any of the following structures; [Chem 4]

In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O-, or -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a portion other than Q of the compound molecule Bonding position; R ₁₂ represents a hydrogen atom, a halogen atom, a C 1-10 alkyl group or a C 1-10 alkoxy group. [9] The method for manufacturing the zero-plane anchoring film according to [7], wherein the diamine containing an organic group that induces free radical polymerization has a structure represented by the following general formula (6) or the following general formula (7) Diamine;

In formula (6), 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 an unsubstituted or fluorine atom-substituted alkylene group having 1 to 20 carbon atoms, which extends One or more of any -CH ₂ -or -CF ₂ -of the alkyl group may be independently replaced with a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, In addition, any of the following groups, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- may not be adjacent to each other and replaced with these Group; R ⁸ represents a radical polymerization reactive group selected from the following formula; [Chem 6]

In formulas [X-1] to [X-18], * represents a bonding site with a portion other than the radical polymerization reactive group of the compound molecule, and S ₁ and S ₂ each independently represent -O- and -NR- , -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms;

In formula (7), T ₁ and T ₂ are each independently a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O -, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-, S represents a single bond, or an unsubstituted or fluorine atom-substituted C 1-20 alkylene One or more of any -CH ₂ -or -CF ₂ -of the alkylene group may be independently substituted with -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring The base in, or any of the following enumerations, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other can be Replaced by these radicals, J is an organic radical represented by any of the following formulas, [化8]

In the formulas [W], [Y], [Z], * represents a bonding site with T ₂ , Ar represents an organic group and/or a halogen atom may be substituted as a substituent selected from phenylene, naphthyl, And aromatic hydrocarbon groups in the group consisting of biphenylene, R ⁹ and R ¹⁰ each independently represent a C 1-10 alkyl group or a C 1-10 alkoxy group, and Q represents any of the following structures ; [化9]

In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O-, or -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a portion other than Q of the compound molecule Bonding position; R ¹² represents a hydrogen atom, a halogen atom, a C 1-10 alkyl group or a C 1-10 alkoxy group. [10] The method for producing a zero-plane anchor film according to any one of [1] to [9], wherein E in the general formula (1) is an ester bond. [11] A method for manufacturing a liquid crystal cell, using the method for manufacturing a zero-plane anchor film as described in any one of [1] to [10], including the following steps: preparing a first substrate with a free radical generating film and also A second substrate that may have a free radical generating film; a unit cell is made such that the free radical generating film on the first substrate faces the second substrate; and a liquid crystal and free radical polymerization are filled between the first substrate and the second substrate Liquid crystal composition of a sexual compound. [12] The method for manufacturing a liquid crystal cell according to [11], wherein the second substrate is a second substrate without a radical generating film. [13] The method for manufacturing a liquid crystal cell according to [12], wherein the second substrate is covered with a liquid crystal alignment film having uniaxial alignment. [14] The method for manufacturing a liquid crystal cell according to [13], wherein the liquid crystal alignment film with uniaxial alignment is a liquid crystal alignment film for horizontal alignment. [15] The method for manufacturing a liquid crystal cell according to any one of [11] to [14], wherein the first substrate having a radical generating film is a substrate with comb-shaped electrodes. [16] A liquid crystal composition containing a liquid crystal and a radically polymerizable compound having a structure represented by the following formula (1), [Chem. 10]

In formula (1), R ^a and R ^b each independently represent a straight-chain alkyl group having 2 to 8 carbon atoms, and E represents a single bond, -O-, -NR ^c -, -S-, ester bond, or amide The bonding group in the amine bond, R ^c represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms. [17] The liquid crystal composition of [16], wherein E in the general formula (1) is an ester bond. [18] A method for manufacturing a liquid crystal display element, using a film in which the zero plane anchoring state obtained by the method as described in any one of [1] to [15] is used. [19] A liquid crystal display element obtained by using the method of manufacturing a liquid crystal display element as in [18]. [20] The liquid crystal display element of [19], wherein the first substrate or the second substrate has electrodes. [21] The liquid crystal display device according to [19] or [20] is a low voltage driven transverse electric field liquid crystal display device. (Effect of invention)

According to the present invention, the zero-plane anchoring film can be produced industrially with good yield. Using the method of the present invention, a liquid crystal display element similar to the zero-plane anchored IPS mode liquid crystal display element described in Patent Documents 1 and 2 can be easily manufactured with inexpensive raw materials and existing manufacturing methods. In addition, the liquid crystal display device obtained by the manufacturing method of the present invention can provide a faster response speed of the liquid crystal when it is off compared to the conventional technology, and has a low driving voltage, no bright spots, and can suppress Vcom deviation when it is in the IPS mode. When shifting to the FFS mode, the liquid crystal display device with these excellent characteristics can be more highly refined.

The present invention is a method for manufacturing a zero-plane anchoring film, which is characterized in that the radical generating film is in contact with liquid crystal containing a specific polymerizable compound, and the polymerizable compound is polymerized using UV or heat. More specifically, it is a method for manufacturing a zero-plane anchoring film, which includes the following steps: preparing a liquid crystal-containing liquid crystal and a free radical between a first substrate with a free radical generating film and a second substrate that may also have a free radical generating film A unit cell of a liquid crystal composition of a polymerizable compound; and sufficient energy is given to the unit cell for the polymerization reaction of the radical polymerizable compound. It is preferably a method for manufacturing a liquid crystal cell, having the following steps: preparing a first substrate with a free radical generating film and a second substrate without a free radical generating film; making crystals in such a way that the free radical generating film faces the second substrate Cells; and, a liquid crystal composition containing liquid crystal and a radical polymerizable compound is filled between the first substrate and the second substrate. For example, a method for manufacturing a low-voltage driven IPS liquid crystal display device, the second substrate does not have a radical generating film, and is a substrate with a liquid crystal alignment film subjected to uniaxial alignment treatment, and the first substrate is a substrate with comb-shaped electrodes.

In the present invention, "zero plane anchoring film" means that the liquid crystal molecules in the in-plane direction have no alignment binding force at all, or even if there is, the intermolecular force of the liquid crystals is weaker than each other. Uniaxially oriented film in either direction. In addition, the zero-plane anchoring film is not limited to a solid film, but also includes a liquid film covering a solid surface. Generally, in a liquid crystal display element, a liquid crystal alignment film that restricts the alignment of liquid crystal molecules, that is, a liquid crystal alignment film is used in pairs to align the liquid crystal, but the zero plane anchor film and the liquid crystal alignment film can also be used to pair the liquid crystal alignment film. . The reason is that the alignment restraint force of the liquid crystal alignment film is also transmitted to the thickness direction of the liquid crystal layer through the intermolecular force of the liquid crystal molecules, and as a result, the liquid crystal molecules close to the zero plane anchor film are also aligned. Therefore, when a liquid crystal alignment film for horizontal alignment is used for the liquid crystal alignment film, the entire liquid crystal cell can make a horizontal alignment state. Horizontal alignment refers to a state in which the long axes of liquid crystal molecules are approximately parallel to the surface of the liquid crystal alignment film. Even if there is an inclined alignment of about several degrees, it is included in the category of horizontal alignment.

[Free radical generating film forming composition] In order to form the radical generating film-forming composition of the radical generating film used in the present invention, the components include a polymer and a radical generating radical. In this case, the composition may include a polymer to which a radical-generating group is bonded, or a composition of a compound having a radical-generating group and a polymer that becomes a base resin. By applying such a composition and hardening to form a film, a radical generating film based on immobilization in the film that can generate free radicals can be obtained. The radical generating radical is preferably an organic radical that induces radical polymerization.

式[X-1]～[X-18]中，＊代表與化合物分子之聚合性不飽和鍵以外之部分之鍵結部位，S₁ 、S₂ 各自獨立地表示-O-、-NR-、-S-，R表示氫原子或碳原子數1～4之烷基，R₁ ，R₂ 各自獨立地表示氫原子、鹵素原子、碳數1～4之烷基； [化12]

式[W]、[Y]、[Z]中，＊代表與化合物分子之聚合性不飽和鍵以外之部分之鍵結部位，Ar表示也可以具有有機基及/或鹵素原子作為取代基之選自由伸苯基、伸萘基、及伸聯苯基構成之群組中之芳香族烴基，R⁹ 及R¹⁰ 各自獨立地表示碳數1～10之烷基或碳數1～10之烷氧基，R⁹ 與R¹⁰ 為烷基時，末端也可互相鍵結並形成環結構。Q代表下列之任一結構。 [化13]

式中，R¹¹ 表示-CH₂ -、-NR-、-O-、或-S-，R表示氫原子或碳原子數1～4之烷基，＊代表和化合物分子之Q以外之部分之鍵結部位。 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。Examples of such organic groups that induce radical polymerization include organic groups represented by any of [X-1] to [X-18], [W], [Y], and [Z] represented by the following structures. [Chem 11]

In formulas [X-1] to [X-18], * represents a bonding site other than the polymerizable unsaturated bond with the compound molecule, and S ₁ and S ₂ each independently represent -O-, -NR-, -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms;

In the formulas [W], [Y], [Z], * represents the bonding site of the part other than the polymerizable unsaturated bond with the compound molecule, Ar means that it may have an organic group and/or a halogen atom as a substituent Aromatic hydrocarbon groups in the group consisting of free phenylene, naphthyl and biphenylene, R ⁹ and R ¹⁰ each independently represent a C 1-10 alkyl group or a C 1-10 alkoxy group When R ⁹ and R ¹⁰ are alkyl groups, the ends may be bonded to each other to form a ring structure. Q represents any of the following structures. [Chem 13]

In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O-, or -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a portion other than Q of the compound molecule Bonding site. R ₁₂ represents a hydrogen atom, a halogen atom, a C 1-10 alkyl group or a C 1-10 alkoxy group.

Polymers such as polyimide precursors, and at least one polymer selected from the group consisting of polyimide, polyurea, polyamide, polyacrylate, polymethacrylate, etc. are preferred .

In order to obtain the radical generating film used in the present invention, when using the aforementioned polymer having an organic group that induces radical polymerization, in order to obtain a polymer having a radical generating group, it is preferable to use A monomer having a photoreactive side chain selected from at least one of methacrylic group, acrylic group, vinyl group, allyl group, coumarin group, styryl group, and cinnamyl group, the side chain has decomposition by ultraviolet irradiation And it is better to manufacture the monomer at the site where free radicals are generated. On the other hand, considering the problem that the monomers that generate free radicals will spontaneously polymerize, etc., they will become unstable compounds. Therefore, considering the ease of synthesis, the polymer derived from the diamine having a free radical generating site is preferred. Ideally, polyimide precursors such as polyamic acid and polyamic acid ester, polyimide, polyurea, polyamide, etc. are more preferred.

式(6)中，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取代為選自-CH=CH-、二價之碳環、及二價之雜環中之基，再者，亦能以下列舉出之任一基亦即，-O-、-COO-、-OCO-、-NHCO-、-CONH-、或-NH-互不相鄰為條件，以該等基來取代； R⁸ ，表示從下式選出之自由基聚合反應性基： [化15]

式[X-1]～[X-18]中，＊表示和化合物分子之自由基聚合反應性基以外之部分之鍵結部位，S₁ 、S₂ 各自獨立地表示-O-、-NR-、-S-，R表示氫原子或碳原子數1～4之烷基，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，R₁ ，R₂ 各自獨立地表示氫原子、鹵素原子、碳數1～4之烷基；Such a diamine containing a radical generating site, specifically, for example, a diamine having a side chain capable of generating free radicals and polymerizing, such as the diamine represented by the following general formula (6) but not limited thereto. [化14]

In formula (6), 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 an unsubstituted or fluorine atom-substituted alkylene group having 1 to 20 carbon atoms, which extends Any one or more of -CH ₂ -or -CF ₂ -of the alkyl group may be independently substituted with a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, Furthermore, any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- may not be adjacent to each other, provided that these groups To substitute; R ⁸ represents a radical polymerization reactive group selected from the following formula: [化15]

In formulas [X-1] to [X-18], * represents a bonding site with a portion other than the radical polymerization reactive group of the compound molecule, and S ₁ and S ₂ each independently represent -O- and -NR- , -S-, R represents a hydrogen atom or a C 1-4 alkyl group, R ₁₂ represents a hydrogen atom, a halogen atom, a C 1-10 alkyl group or a C 1-10 alkoxy group, R ₁ , R ₂ each independently represents a hydrogen atom, a halogen atom, and a C 1-4 alkyl group;

In the formula (6), the bonding position of the two amine groups (-NH ₂ ) is not limited. Specifically, the bonding group with respect to the side chain is 2,3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 position, 3 on the benzene ring ,5 position. Among them, from the viewpoint of the reactivity when synthesizing polyamide, the position of 2,4, the position of 2,5, or the position of 3,5 is preferable. If the ease of synthesizing the diamine is also considered, the position of 2,4 or the position of 3,5 is more ideal.

式中，J¹ 表示選自單鍵、-O-、-COO-、-NHCO-、或-NH-之鍵結基，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。As the diamine having at least one photoreactive group selected from the group consisting of methacrylic group, acrylic group, vinyl group, allyl group, coumarin group, styryl group and cinnamyl group, Specifically, the following compounds may be mentioned, but not limited thereto. [Chem 16]

In the formula, J ¹ represents a bonding group selected from a single bond, -O-, -COO-, -NHCO-, or -NH-, and J ² represents a single bond, or a carbon number 1 that is unsubstituted or substituted with a fluorine atom ~20 alkylene.

式(7)中，T₁ 及T₂ 各自獨立地為單鍵、-O-、-S-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH₂ O-、-N(CH₃ )-、-CON(CH₃ )-、或-N(CH₃ )CO-， S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 -之一者以上也可各自獨立地取代為選自-CH=CH-、二價之碳環、及二價之雜環中之基，再者也可以下列舉出的任一基亦即-O-、-COO-、-OCO-、-NHCO-、-CONH-、或-NH-互不相鄰的條件，經該等基取代， J為下式表示之有機基， [化18]

式[W]、[Y]、[Z]中，＊表示和T₂ 之鍵結部位，Ar表示也可以具有有機基及/或鹵素原子作為取代基之選自由伸苯基、伸萘基、及伸聯苯基構成之群組中之芳香族烴基，R⁹ 及R¹⁰ 各自獨立地表示碳數1～10之烷基或碳數1～10之烷氧基，Q代表下列之任一結構。 [化19]

式中，R¹¹ 表示-CH₂ -、-NR-、-O-、或-S-，R表示氫原子或碳原子數1～4之烷基，＊代表和化合物分子之Q以外之部分之鍵結部位。 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。As for the diamine having a site decomposed by ultraviolet irradiation and generating free radicals as a side chain, the diamine represented by the following general formula (7) can be cited but is not limited thereto. [化17]

In formula (7), T ₁ and T ₂ are each independently a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O -, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-, S represents a single bond, or an unsubstituted or fluorine atom-substituted C 1-20 alkylene One or more of -CH ₂ -or -CF ₂ -of the alkylene group may be independently substituted with -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring In addition, any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- may not be adjacent to each other. Group substitution, J is an organic group represented by the following formula, [Chem 18]

In the formulas [W], [Y], [Z], * represents a bonding site with T ₂ , Ar represents an organic group and/or a halogen atom may be substituted as a substituent selected from phenylene, naphthyl, And aromatic hydrocarbon groups in the group consisting of biphenylene, R ⁹ and R ¹⁰ each independently represent a C 1-10 alkyl group or a C 1-10 alkoxy group, and Q represents any of the following structures . [Chem 19]

In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O-, or -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a portion other than Q of the compound molecule Bonding site. R ₁₂ represents a hydrogen atom, a halogen atom, a C 1-10 alkyl group or a C 1-10 alkoxy group.

The bonding position of the two amine groups (-NH ₂ ) in the above formula (7) is not limited. Specifically, the bonding group with respect to the side chain is 2,3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 position, 3 on the benzene ring ,5 position. Among them, from the viewpoint of the reactivity when synthesizing polyamide, the position of 2,4, the position of 2,5, or the position of 3,5 is preferable. If the ease of synthesizing the diamine is also considered, the 2,4 position or the 3,5 position is more desirable.

式中，n為2～8之整數。In particular, considering the ease of synthesis, height of versatility, and characteristics, the structure represented by any one of the following formulas is the most ideal, but is not limited thereto. [化20]

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

The above-mentioned diamines may be used alone or in combination of two or more in accordance with the characteristics of liquid crystal alignment, sensitivity during polymerization, voltage retention characteristics, accumulated charge, etc. when forming a radical generating film.

Such a diamine having a site where free radical polymerization occurs is preferably used in an amount of 5 to 50 mol% of the total amount of the diamine component used for the synthesis of the polymer contained in the free radical generating film-forming composition. It is preferably 10 to 40 mol%, and particularly preferably 15 to 30 mol%.

In addition, when the polymer used in the radical generating film of the present invention is obtained from a diamine, other diamines other than the diamine having a radical generating site can be used as the diamine without limiting the effect of the present invention. Use ingredients together. Specifically, for example: 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-diamine Phenol, 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'-biphenyl, 3,3'-trifluoromethyl -4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'- Diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'- Diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'- Diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyl Diphenylamine, bis(4-aminophenyl) silane, bis(3-aminophenyl) silane, dimethyl-bis(4-aminophenyl) silane, dimethyl-bis(3-amino group (Phenyl) silane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'- Diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl)amine, N-methyl (3,3'-diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl) Group) amine, N-methyl (2,3'-diaminodiphenyl)amine, 4,4'-diaminodiphenyl ketone, 3,3'-diaminodiphenyl ketone, 3 ,4'-diaminodiphenyl ketone, 1,4-diaminonaphthalene, 2,2'-diaminodiphenyl ketone, 2,3'-diaminodiphenyl ketone, 1,5 -Diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene , 2,7-diaminonaphthalene, 2,8-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-amine Phenoxy)benzene, 4,4'-[1,4-phenylene bis(methylene)] diphenylamine, 4,4'-[1,3-phenylene bis(methylene)] Diphenylamine, 3,4'-[1,4-phenylene bis(methylene)] diphenylamine, 3,4'-[1,3-phenylene bis(methylene)] diphenylamine, 3 ,3'-[1,4-Phenylbis(methylene)]diphenylamine, 3,3'-[1,3-Phenylbis(methylene)]diphenylamine, 1,4-Extrude Phenylbis[(4-aminophenyl)methanone], 1,4-phenylenebis[(3-aminophenyl)methanone], 1,3-phenylenebis[(4-amine Phenyl) ketone], 1,3-phenylene bis[(3-aminophenyl) ketone], 1,4-phenylene bis(4-aminobenzoate), 1, 4-Phenylbis(3-aminobenzoate), 1,3-Phenylbis(4-aminobenzoate), 1,3-Phenylbis(3-aminobenzene) Formate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) meta-xylylene Ester, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzylamide), N,N'- (1,3-Phenylphenyl)bis(4-aminobenzylamide), N,N'-(1,4-Phenylphenyl)bis(3-aminobenzylamide), N,N '-(1,3-Phenylphenyl)bis(3-aminobenzylamide), N,N'-bis(4-aminophenyl)p-xylylenediamine, N,N'-bis (3-Aminophenyl) p-xylylenediamine, N,N'-bis(4-aminophenyl) m-xylylenediamine, N,N'-bis(3-aminophenyl) M-xylylenediamine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylsulfone, 2,2'-bis[4 -(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-amine Phenyl)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, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-amine Phenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3- Aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4 -Aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis( 3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12 -Aromatic diamines such as bis(4-aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)dodecane; 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, Aliphatic diamines such as 1,11-diaminoundecane, 1,12-diaminododecane; 1,3-bis[2-(p-aminophenyl)ethyl]urea, 1,3 -Bis[2-(p-aminophenyl)ethyl]-1-third butoxycarbonyl urea and other diamines with urea structure; N-p-aminophenyl-4-p-aminophenyl (section Tributoxycarbonyl) aminomethylpiperidine and other diamines with nitrogen-containing unsaturated heterocyclic structure; N-third butoxycarbonyl-N-(2-(4-aminophenyl)ethyl) -N-(4-aminobenzyl)amine and the like include N-Boc group diamine and the like.

The other diamines mentioned above can be used alone or in combination of two or more depending on the characteristics of liquid crystal alignment, sensitivity during polymerization, voltage retention characteristics, charge accumulation, etc. when forming a radical generating film.

In the synthesis when the polymer is polyamic acid, the tetracarboxylic dianhydride reacted with the above diamine component is not particularly limited. Specifically, 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'-biphenyltetracarboxylic acid, 2,3,3',4 '-Biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl) ether, 3,3',4,4'-diphenylketone tetracarboxylic acid, bis(3,4-dicarboxyphenyl) Ash, 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'-diphenylbenzene tetracarboxylic acid, 3,4,9, 10-Perylene tetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid, oxydiphthalyl tetracarboxylic acid, 1,2,3,4-cyclobutane Tetracarboxylic acid, 1,2,3,4-cyclopentane tetracarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic 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- Cyclobutane tetracarboxylic acid, 1,2,3,4-cycloheptane tetracarboxylic acid, 2,3,4,5-tetrahydrofuran tetracarboxylic acid, 3,4-dicarboxy-1-cyclohexyl succinic acid, 2 ,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo[3,3,0]octane-2,4 ,6,8-tetracarboxylic acid, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]decane-2,4,7,9 -Tetracarboxylic acid, bicyclo[4,4,0]decane-2,4,8,10-tetracarboxylic acid, tricyclo[6.3.0.0>2,6>]undecane-3,5,9, 11-tetracarboxylic acid, 1,2,3,4-butane tetracarboxylic acid, 4-(2,5-bi- pendant tetrahydrofuran-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-bi- pendant tetrahydrofuranyl)-3 -Methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo[6,2,1,1,0>2,7>]dodecane-4,5,9,10-tetracarboxylic acid Acid, 3,5,6-tricarboxynorbornane-2:3,5:6 dicarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic acid and other dianhydrides of tetracarboxylic acid.

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

In the synthesis when the polymer is a polyamic acid ester, the structure of the dialkyl tetracarboxylic acid reacted with the above diamine component is not particularly limited, and specific examples are as follows. Specific examples of aliphatic tetracarboxylic acid diesters, such as 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclo Butane 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-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-cyclopentane tetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dialkyl ester, 1 , 2,4,5-Cyclohexane dicarboxylic acid dialkyl ester, 3,4-dicarboxy-1-cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetra Hydrogen-1-naphthalene succinic acid 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-3,7-dibutyl Cyclooctane-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo[4.2.1.0>2,5>]nonane-3,4,7,8-tetracarboxylic acid Acid-3,4: 7,8-dialkyl ester, hexacyclic [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-bi- pendant tetrahydrofuran-3-yl)-1,2,3,4 -Dihydronaphthalene-1,2-dicarboxylic acid dialkyl ester and the like.

Examples of the aromatic dicarboxylic acid dialkyl esters include pyromellitic acid dialkyl esters, 3,3',4,4'-biphenyltetracarboxylic acid dialkyl esters, 2,2',3,3'-biphenyltetracarboxylic acid Dialkyl carboxylate, 2,3,3',4-biphenyl tetracarboxylic acid dialkyl ester, 3,3',4,4'-diphenyl ketone tetracarboxylic acid dialkyl ester, 2,3,3 ',4'-diphenyl ketone tetracarboxylic acid dialkyl ester, bis(3,4-dicarboxyphenyl) ether dialkyl ester, bis(3,4-dicarboxyphenyl) lanthanide dialkyl ester, 1, 2,5,6-Naphthalene tetracarboxylic acid dialkyl ester, 2,3,6,7-naphthalene tetracarboxylic acid dialkyl ester, etc.

式中R₂ 、R₃ 表示碳數1～10之脂肪族烴。In the synthesis when the polymer is polyurea, the diisocyanate that reacts with the above diamine component is not particularly limited, and can be used according to availability and the like. The specific structure of the diisocyanate is shown below. [化21]

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

The aliphatic diisocyanates shown in K-1～K-5 have poor reactivity but have the advantage of better solvent solubility, and the aromatic diisocyanates shown in K-6～K-7 are rich in reactivity and have heat resistance The effect of improving the performance, but has the disadvantage of low solvent solubility. Considering the versatility and characteristics, K-1, K-7, K-8, K-9, and K-10 are particularly preferred. Considering the electrical characteristics, K-12 is ideal. From the viewpoint of liquid crystal alignment, K -13 is preferred. One or more diisocyanates can be used in combination, and it is preferable to adopt them according to the characteristics to be obtained. In addition, a part of the diisocyanate can be replaced with the tetracarboxylic dianhydride described above, and can be used in the form of a copolymer of polyamic acid and polyurea, or it can be chemically imidized into polyimide and Polyurea copolymers are used in this form.

In the synthesis when the polymer is polyamidoamine, the structure of the dicarboxylic acid to be reacted is not particularly limited, and specific examples include the following. Specific examples of the aliphatic dicarboxylic acid include malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, Dicarboxylic acids such as trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid.

Examples of alicyclic dicarboxylic acids include 1,1-cyclopropane dicarboxylic acid, 1,2-cyclopropane dicarboxylic acid, 1,1-cyclobutane dicarboxylic acid, and 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 Hexanedicarboxylic acid, 1,4-(2-norcamene) dicarboxylic acid, norcamene-2,3-dicarboxylic acid, bicyclo[2.2.2]octane-1,4-dicarboxylic acid, Bicyclo[2.2.2]octane-2,3-dicarboxylic acid, 2,5-bi- pendant-1,4-bicyclo[2.2.2]octane dicarboxylic acid, 1,3-adamantanedicarboxylic acid Acid, 4,8-bi- pendant-1,3-adamantane dicarboxylic acid, 2,6-spiro[3.3]heptane dicarboxylic acid, 1,3-adamantane diacetic acid, camphoric acid, etc.

Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tributylbutyl isophthalic acid, and 5-aminoisophthalic acid , 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid, tetramethylterephthalic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6 -Naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-anthracene dicarboxylic acid, 1,4-anthraquinone dicarboxylic acid, 2,5-biphenyl dicarboxylic acid, 4,4'-bi Phthalic acid, 1,5-biphenylene dicarboxylic acid, 4,4”-terphenylenedicarboxylic acid, 4,4′-diphenylmethane dicarboxylic acid, 4,4′-diphenyl Ethane dicarboxylic acid, 4,4'-diphenylpropane dicarboxylic acid, 4,4'-diphenyl hexafluoropropane dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4' -Bibenzyl dicarboxylic acid, 4,4'-stilbene dicarboxylic acid, 4,4'-ethynylbisbenzoic acid, 4,4'-carbonyldibenzoic acid, 4,4'- Sulfodibenzoic 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'-(methylene di-p-phenylene)] dipropionic acid, 4,4'-[4,4'-(oxydi-p-phenylene)] dipropylene Acid, 4,4'-[4,4'-(oxydip-phenylene)] dibutyric acid, (isopropylidene dip-phenylene dioxy) dibutyric acid, bis (p-carboxyphenyl ) Dicarboxylic acid such as dimethyl silane.

Examples of the dicarboxylic acids containing heterocycles include 1,5-(9-oxo stilbene) dicarboxylic acid, 3,4-furan dicarboxylic acid, 4,5-thiazole dicarboxylic acid, and 2-phenyl-4, 5-thiazoledicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-diazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid 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 also have an amide dihalide or anhydride structure. If these dicarboxylic acids are dicarboxylic acids that can give a linear structure of polyamide, it is preferable in terms of maintaining the alignment of liquid crystal molecules. Among these, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis(phenyl ) Propane dicarboxylic acid, 4,4-biphenyldicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,5-pyridine dicarboxylic acid, or the like's dihalide. These compounds may also have isomers, and may also be a mixture including them. In addition, two or more kinds of compounds may be used in combination. In addition, the dicarboxylic acids used in the present invention are not limited to the above-exemplified compounds.

The diamine used as a raw material (also described as "diamine component"), and the one selected as a raw material are selected from tetracarboxylic dianhydride (also described as "tetracarboxylic dianhydride component"), tetracarboxylic acid diester, and diisocyanate When reacting with the components in the dicarboxylic acid to obtain polyamic acid, polyamic acid ester, polyurea, and polyamidoamine, a known synthesis method can be used. In general, there is a method of reacting a diamine component with at least one component 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 relatively easy to proceed in an organic solvent and does not produce by-products, which is advantageous from this viewpoint.

The organic solvent used in the above reaction is not particularly limited as long as it can dissolve the polymer produced. Furthermore, even organic solvents that do not dissolve the polymer can be used in combination with the above-mentioned solvents within the range where the resulting polymer does not precipitate. In addition, the moisture in the organic solvent will hinder the polymerization reaction and further cause the resulting polymer to hydrolyze. Therefore, it is preferable to use an organic solvent that is dehydrated and dried.

Organic solvents, 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-dimethylpropane amide, N -Methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfoxide, hexamethyl sulfoxide, γ-butyrolactone, isopropanol, methoxymethylpentanol, Dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl sialon, ethyl sialon, methyl sialon Ester, butylcellulose acetate, ethylcellulose acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoiso Propyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-third butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, di Ethylene 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, diethylene glycol Propylene 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 butyl ester, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether , Dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethyl carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate Ester, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxypropion Ethyl acetate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, diglyme, 4-hydroxy- 4-methyl-2-pentanone, 2-ethyl-1-hexanol, etc. These organic solvents can be used alone or in combination.

When reacting the diamine component and the tetracarboxylic dianhydride component in an organic solvent, the following methods may be mentioned: the solution obtained by dispersing or dissolving the diamine component in an organic solvent is stirred, and the tetracarboxylic dianhydride component is directly added, Or the method of adding it after dispersing or dissolving it in an organic solvent, the method of adding a diamine component to a solution obtained by dispersing or dissolving the tetracarboxylic dianhydride component in the organic solvent, and the tetracarboxylic dianhydride component and As a method of adding diamine components alternately, any of these methods can be used. In addition, when the diamine component or the tetracarboxylic dianhydride component is composed of many kinds of compounds, it can be reacted in a pre-mixed state, or it can be reacted individually sequentially, or the low-molecular-weight body reacted separately can be mixed Reaction, and made into high molecular weight body.

The temperature at which the diamine component reacts with the tetracarboxylic dianhydride component can be selected at any temperature, for example: -20 to 100°C, preferably -5 to 80°C. The reaction can be carried out at any concentration. For example, the total amount of the diamine component and the tetracarboxylic dianhydride component is 1 to 50% by mass, preferably 5 to 30% by mass relative to the reaction solution.

In the above polymerization reaction, the ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component can be arbitrarily selected according to the molecular weight of the polyamic acid to be obtained. Like the normal polycondensation reaction, the closer the molar ratio is to 1.0, the greater the molecular weight of the polyamic acid produced. The ideal range is 0.8 to 1.2.

The method for synthesizing the polymer used in the present invention is not limited to the above method. When synthesizing polyamic acid, it is possible to replace the above tetracarboxylic dianhydride with the corresponding structure four in the same way as the general synthetic method of polyamic acid Tetracarboxylic acid derivatives such as carboxylic acid or tetracarboxylic amide dihalide are reacted by a known method to obtain the corresponding polyamic acid. In addition, when synthesizing polyurea, the diamine and diisocyanate may be reacted. When manufacturing polyamide or polyamine, the diamine and the component selected from tetracarboxylic acid diester and dicarboxylic acid can be used in the presence of a well-known condensing agent, or derivatized into a amide halide by a well-known method To react with diamine.

The method of preparing the polyimide by subjecting the polyamic acid to imidization can be exemplified by the following methods: hot imidization of the solution of polyamic acid directly heated, adding a solution to the solution of polyamic acid The catalyst is imidized. In addition, considering the viewpoint of making the voltage retention rate high from the conversion of the polyamic acid to the polyimide, the ratio of the imidization is preferably 30% or more, and more preferably 30 to 99%. On the other hand, considering the whitening characteristics, that is, the viewpoint of suppressing polymer precipitation varnish, 70% or less is preferable. If considering the characteristics of both parties, 40 to 80% is more ideal.

The temperature of polyamido acid in a solution for thermal imidization is usually 100-400°C, preferably 120-250°C. It is advisable to drain the water generated by the amide imidization reaction to the outside of the system for comparison good.

The catalyst of polyamic acid can be imidized by adding an alkaline catalyst and an acid anhydride due to the solution of polyamic acid, usually at -20 to 250°C, preferably 0 to 180°C, with stirring. The amount of the alkaline catalyst is usually 0.5 to 30 mole times for the amide acid group, preferably 2 to 20 mole times, and the amount of the acid anhydride is usually 1 to 50 mole times for the amide acid group, preferably It is 3 to 30 mole times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has a moderate alkalinity for the reaction to proceed. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, if acetic anhydride is used, the purification after the reaction is easy, which is preferable. The rate of acylation obtained by acylation of the catalyst can be controlled by adjusting the amount of catalyst, reaction temperature, reaction time, etc.

When recovering the produced polymer from the reaction solution of the polymer, the reaction solution can be thrown into a poor solvent and precipitated. Poor solvents used for precipitation formation include methanol, acetone, hexane, butylcellulose, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer which is put into the poor solvent and precipitated can be dried at room temperature or under normal pressure or reduced pressure after filtration and recovery. In addition, if the polymer recovered by precipitation is further dissolved in an organic solvent, and reprecipitation is recovered, and this operation is repeated 2 to 10 times, impurities in the polymer can be reduced. The poor solvents at this time are, for example, alcohols, ketones, hydrocarbons, etc. If three or more of the poor solvents selected among them are used, the purification efficiency will be better, which is preferable.

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

The molecular weight of the polymer contained in the radical generating film forming composition, when considering the strength of the radical generating film obtained by coating the radical generating film, the workability at the time of forming the coating film, the uniformity of the coating film, etc., The weight average molecular weight determined by GPC (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

When a radical generating film used in the present invention is obtained by coating and curing a composition having a radical generating compound and a polymer to form a film, the polymer is a polymer produced according to the above production method Precursor of imide, and a polymer selected from the group consisting of polyimide, polyurea, polyamide, polyacrylate, polymethacrylate, etc., which can generate radical polymerization sites The diamine is at least one polymer obtained from a diamine component of 0 mol% of the total diamine component used in the synthesis of the polymer contained in the radical generating film forming composition. The compound having a radical generating group added at this time can be listed as follows.

Compounds that generate free radicals with heat are compounds that generate free radicals by heating above the decomposition temperature. Such free-radical thermal polymerization initiators, for example: ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzophenone peroxide) Etc.), hydrogen peroxides (hydrogen peroxide, third butyl hydrogen peroxide, cumene hydrogen peroxide, etc.), dialkyl peroxides (di-third butyl peroxide, dicumyl Base peroxide, lauryl diperoxide, etc.), ketal peroxides (dibutyl cyclohexane peroxide, etc.), alkyl peresters (neodecanoic acid-third butyl peroxide, peroxide Trimethyl acetic acid-tertiary butyl ester, tertiary amyl peroxide 2-ethylcyclohexane acid, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (Azobisisobutyronitrile, and 2,2'-bis(2-hydroxyethyl)azobisisobutyronitrile, etc.). Such a radical thermal polymerization initiator can be used alone or in combination of two or more.

啉代丙-1-酮、2-苄基-2-二甲胺基-1-(4-

啉代苯基)-丁酮-1,4-二甲胺基苯甲酸乙酯、4-二甲胺基苯甲酸異戊酯、4,4’-二(第三丁基過氧羰基)二苯酮、3,4,4’-三(第三丁基過氧羰基)二苯酮、2,4,6-三甲基苯甲醯基二苯基氧化膦、2-(4’-甲氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三

、2-(3’,4’-二甲氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三

、2-(2’,4’-二甲氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三

、2-(2’-甲氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三

、2-(4’-戊氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三

、4-[對N,N-二(乙氧基羰基甲基)]-2,6-二(三氯甲基)-s-三

、1,3-雙(三氯甲基)-5-(2’-氯苯基)-s-三

、1,3-雙(三氯甲基)-5-(4’-甲氧基苯基)-s-三

、2-(對二甲胺基苯乙烯基)苯并㗁唑、2-(對二甲胺基苯乙烯基)苯并噻唑、2-巰基苯并噻唑、3,3’-羰基雙(7-二乙胺基香豆素)、2-(鄰氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-肆(4-乙氧基羰基苯基)-1,2’-聯咪唑、2,2’-雙(2,4-二氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’雙(2,4-二溴苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’-雙(2,4,6-三氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、3-(2-甲基-2-二甲胺基丙醯基)咔唑、3,6-雙(2-甲基-2-

啉代丙醯基)-9-正十二基咔唑、1-羥基環己基苯酮、雙(5-2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1H-吡咯-1-基)-苯基)鈦、3,3’,4,4’-四(第三丁基過氧羰基)二苯酮、3,3’,4,4’-四(第三己基過氧羰基)二苯酮、3,3’-二(甲氧基羰基)-4,4’-二(第三丁基過氧羰基)二苯酮、3,4’-二(甲氧基羰基)-4,3’-二(第三丁基過氧羰基)二苯酮、4,4’-二(甲氧基羰基)-3,3’-二(第三丁基過氧羰基)二苯酮、2-(3-甲基-3H-苯并噻唑-2-亞基)-1-萘-2-基-乙酮、或2-(3-甲基-1,3-苯并噻唑-2(3H)-亞基)-1-(2-苯甲醯基)乙酮等。該等化合物可單獨使用，也可混用2種以上。The compound that generates free radicals by light is not particularly limited as long as it starts radical polymerization due to light. Examples of such free radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-Diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylbenzeneacetone, 2-hydroxy-2-methyl-4'-isopropylbenzeneacetone , 1-hydroxycyclohexyl benzophenone, cumene benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl Acetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-

Prolinone-1-one, 2-benzyl-2-dimethylamino-1-(4-

Phenylphenyl)-butanone-1,4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4,4'-di (third butylperoxycarbonyl) di Benzophenone, 3,4,4'-tri(third butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzyl diphenylphosphine oxide, 2-(4'-methyl Oxystyryl)-4,6-bis(trichloromethyl)-s-tri

, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-tri

, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-tri

, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-tri

, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl)-s-tri

, 4-[p-N,N-bis(ethoxycarbonylmethyl)]-2,6-bis(trichloromethyl)-s-tri

, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-tri

, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-tri

, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7 -Diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2- (Chlorophenyl)-4,4',5,5'-(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl )-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'bis(2,4-dibromophenyl)-4,4',5,5'- Tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'- Biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-

(Porphyrinopropyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexyl benzophenone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro -3-(1H-pyrrol-1-yl)-phenyl) titanium, 3,3',4,4'-tetrakis (third butylperoxycarbonyl) benzophenone, 3,3',4,4 '-Tetra (trihexylperoxycarbonyl) benzophenone, 3,3'-bis(methoxycarbonyl)-4,4'-di(third butylperoxycarbonyl) benzophenone, 3,4 '-Bis(methoxycarbonyl)-4,3'-bis(third butylperoxycarbonyl) benzophenone, 4,4'-bis(methoxycarbonyl)-3,3'-di(section Tributylperoxycarbonyl) 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-benzoyl)ethanone, etc. These compounds may be used alone or in combination of two or more.

Furthermore, even if the radical generating film is composed of a polymer having an organic group that induces radical polymerization, in order to promote radical polymerization when energy is applied, a compound having the radical generating group may be contained.

The radical generating film forming composition may contain an organic solvent that dissolves or disperses the polymer component and components other than the radical generating agent as needed. Such an organic solvent is not particularly limited, for example, the organic solvent exemplified in the synthesis of the above-mentioned polyamide. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N- Dimethylpropane amide, etc., is ideal for considering solubility. In particular, N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone is preferred, but a mixture of two or more solvents 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 in an organic solvent having a high solubility of the components contained in the radical generating film forming composition.

Solvents that improve the uniformity and smoothness of the coating film, such as: isopropyl alcohol, methoxymethylpentanol, methylcellulose, ethylcellulose, butylcellulose, methylcellulose Threoacetate, butylcellulose acetate, ethylcellulose acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol Alcohol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-third butyl ether, dipropylene glycol monomethyl ether Ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether Ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate , Tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, Methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate Monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Propionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2- Propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate , Propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, Isoamyl lactate, 2-ethyl-1-hexanol, etc. These solvents can also be mixed. When such 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 uniformity of the film thickness and surface smoothness when the radical generating film forming composition is applied, and compounds that improve the adhesion between the radical generating film forming composition and the substrate. Compounds with better film strength of the radical generating film forming composition.

Examples of the compound that improves the uniformity of the film thickness and the surface smoothness include fluorine-based surfactants, polysiloxane-based surfactants, and nonionic surfactants. More specifically, for example: EFTOP EF301, EF303, EF352 (manufactured by Tohkem Products)), Megafac F171, F173, R-30 (manufactured by Great Ink and Ink Corporation), Fluorad FC430, FC431 (manufactured by Sumitomo 3M), AsahiGuard AG710 , SurflonS-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), etc. When these surfactants are used, the use ratio thereof is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the total amount of polymers contained in the radical generating film forming composition.

As a specific example of a compound that improves the adhesion between the radical generating film forming composition and the substrate, a compound containing a functional silane, a compound containing an epoxy group, etc. may be mentioned. For example: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyl Trimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrisilane Ethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 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-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxy Silane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethyl)-3-amino Propyltrimethoxysilane, N-bis(oxyethylidene)-3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol di Glycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether Ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidoxy-2,4-hexanediol, N,N,N',N' -Tetraglycidyl m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl- 4,4'-Diaminodiphenylmethane, 3-(N-allyl-N-epoxypropyl)aminopropyltrimethoxysilane, 3-(N,N-diepoxypropyl) ) Aminopropyltrimethoxysilane etc.

In addition, in order to further improve the film strength of the radical generating film, 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane and tetra(methoxymethyl)bis Phenol and other phenol 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 the radical generating film forming composition, in addition to the above, as long as the effect of the present invention is not impaired, a dielectric for changing the electrical characteristics such as the dielectric constant and conductivity of the radical generating film may be added Body, conductive material.

[Free radical generating film] The radical generating film of the present invention can be obtained using the above radical generating film forming composition. For example, the radical generating film-forming composition used in the present invention can be applied to a substrate, dried, and calcined to obtain a cured film, which can be used directly as a radical generating film. Alternatively, the cured film may be rubbed, polarized, irradiated with light of a specific wavelength, or treated with an ion beam, or the liquid crystal display element filled with liquid crystal as a PSA alignment film may be irradiated with UV.

The substrate to which the radical generating film forming composition is applied is not particularly limited as long as it is a substrate with high transparency, and it is preferably a substrate in which a transparent electrode for driving liquid crystal is formed on the substrate. Specific examples include glass plates, polycarbonates, poly(meth)acrylates, polyether socks, polyarylate, polyurethanes, poly socks, polyethers, polyether ketones, and trimethyl Plastic electrodes such as pentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triethyl acetyl cellulose, diethyl acetyl cellulose, cellulose acetate butyrate, etc. form transparent electrodes Of the substrate.

For the substrate that can be used in the IPS liquid crystal display element, standard electrode patterns such as IPS comb-tooth electrodes, PSA fishbone electrodes, and protrusion patterns such as MVA can also be used. In addition, in a high-performance device such as a TFT type device, an element 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 a reflective liquid crystal display element is to be manufactured, if it is a single-sided substrate, an opaque substrate such as a silicon wafer may also be used. At this time, materials such as aluminum that reflects light may also be used for the electrodes formed on the substrate.

As the coating method of the radical generating film forming composition, spin coating method, printing method, inkjet method, spray coating method, roll coating method, etc. may be mentioned, but from the aspect of productivity, the transfer printing method is widely used in industry. The present invention can also be used ideally.

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

The coating film formed by coating the radical generating film-forming composition by the above-mentioned method can be calcined and made into a cured film. In this case, the calcination temperature can be generally any temperature between 100°C and 350°C, preferably 140°C to 300°C, more preferably 150°C to 230°C, and still more preferably 160°C to 220°C. The calcination time can usually be calcined at any time from 5 minutes to 240 minutes. It is preferably 10 to 90 minutes, and more preferably 20 to 90 minutes. For heating, generally known methods can be used, for example, hot plate, hot air circulation oven, IR oven, belt furnace, and the like.

The thickness of the cured film can be selected according to needs, preferably 5 nm or more, and more preferably 10 nm or more, because it is easy to obtain the reliability of the liquid crystal display element, which is ideal. 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 desirable.

The first substrate having a radical generating film can be obtained in the above manner, but the radical generating film can be subjected to uniaxial alignment treatment. Examples of the method for performing uniaxial alignment treatment include optical alignment method, oblique vapor deposition method, friction, and uniaxial alignment treatment using a magnetic field.

When the alignment process is performed by performing the rubbing process in one direction, for example, the substrate is moved so that the friction cloth and the film are in contact while rotating the friction roller around which the friction cloth is wound. In the case of the first substrate of the present invention in which comb-teeth electrodes have been formed, the electrical properties of the liquid crystal are used to select the direction, but when using liquid crystals with positive dielectric anisotropy, the rubbing direction is preferably set to that of the comb-teeth electrode. It is preferable that the extending direction is substantially the same direction.

The second substrate of the present invention is the same as the above-mentioned first substrate except that it does not have a radical generating film. Preferably, it is a substrate having a conventionally known liquid crystal alignment film.

>LCD cell> In the liquid crystal cell of the present invention, after the radical generating film is formed on the substrate by the above method, the substrate with the radical generating film (first substrate) and the substrate with the known liquid crystal alignment film (second substrate) are free The base generating film and the liquid crystal alignment film are arranged so as to face each other, fixed with a sealant sandwiching the spacer, and injecting and sealing a liquid crystal composition containing liquid crystal and a radically polymerizable compound to obtain. The size of the spacer used at this time is usually 1 to 30 μm, preferably 2 to 10 μm. In addition, the rubbing direction of the first substrate and the rubbing direction of the second substrate are parallel, and can be used in the IPS mode or the FFS mode. If the rubbing directions are arranged to intersect perpendicularly, the twisted nematic mode can be used. The method of injecting the liquid crystal composition containing the liquid crystal and the radically polymerizable compound is not particularly limited, and the vacuum method of injecting the mixture containing the liquid crystal and the polymerizable compound into the liquid crystal cell after the reduced pressure in the prepared liquid crystal cell and the dropwise addition After the mixture of the liquid crystal and the polymerizable compound is sealed, a drop method is added.

式(1)中，R^a 及R^b 各自獨立地表示碳數2～8之直鏈烷基，E表示單鍵、選自-O-、-NR^c -、-S-、酯鍵、醯胺鍵中之鍵結基，R^c 表示氫原子、碳數1～4之烷基。>Liquid crystal composition containing a liquid crystal and a radically polymerizable compound> The polymerizable compound used with the liquid crystal when the liquid crystal display element of the present invention is produced is a compound represented by the following formula (1). [化22]

In formula (1), R ^a and R ^b each independently represent a straight-chain alkyl group having 2 to 8 carbon atoms, and E represents a single bond, selected from -O-, -NR ^c -, -S-, ester bond, and amide The bonding group in the amine bond, R ^c represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms.

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

式(1-1)及(1-2)中，Ra及Rb各自獨立地表示碳數2～8之直鏈烷基。In addition, for the radical polymerizable compound represented by the aforementioned formula (1), where E is an ester bond (a bond represented by -C(=O)-O- or -OC(=O)-), The viewpoints of ease of synthesis, 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23]

In formulas (1-1) and (1-2), Ra and Rb each independently represent a linear alkyl group having 2 to 8 carbon atoms.

Furthermore, the liquid crystal composition containing the liquid crystal and the radically polymerizable compound preferably contains a radically polymerizable compound having a Tg of 100° C. or lower in a polymer obtained by polymerizing the radically polymerizable compound.

These various radical polymerizable monomers may be used alone or in combination of two or more. Also, they are preferably compatible with liquid crystals.

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

The polymer obtained by polymerizing the radical polymerizable compound preferably has a Tg of 100°C or lower.

In addition, the liquid crystal generally refers to a substance in a state showing the properties of both solid and liquid, and the representative liquid crystal phase includes nematic liquid crystal and smectic liquid crystal, and the liquid crystal usable in the present invention is not particularly limited. As an example, it is 4-pentyl-4'-cyanobiphenyl.

Then, the liquid crystal cell into which the mixture (liquid crystal composition) containing the liquid crystal and the radically polymerizable compound is introduced is given sufficient energy to cause the radically polymerizable compound to undergo a polymerization reaction. It can be implemented by, for example, heating, or irradiating UV, and by polymerizing the radically polymerizable compound in situ, it exhibits desired characteristics. Among them, the use of UV can make the alignment patternable, and the polymerization reaction can be carried out in a short time. From this point of view, UV irradiation is preferred. In addition, when used in the twisted nematic mode, chiral dopants may be introduced into the liquid crystal cell except for the above-mentioned liquid crystal composition.

In addition, it can be heated during UV irradiation. The heating temperature at the time of UV irradiation is preferably a temperature range in which the introduced liquid crystal exhibits liquid crystallinity, usually 40° C. or higher, preferably at a temperature at which the liquid crystal does not change to an isotropic phase.

Here, for the UV irradiation wavelength when performing UV irradiation, it is preferable to select the optimal wavelength for the reaction quantum yield of the polymerizable compound to be reacted, and the UV irradiation amount is usually 0.01 to 30 J/cm ² , preferably 10 J/cm ² or less, the smaller the amount of UV irradiation, the better the reduction in reliability caused by the destruction of the components constituting the liquid crystal display, and the improvement of the tact in manufacturing by reducing the UV irradiation time, which is ideal.

In addition, when the polymerization is performed only by heating without UV irradiation, it is preferable to carry out the temperature range in which the polymerizable compound reacts and does not reach the decomposition temperature of the liquid crystal. Specifically, for example: 100°C or higher and 150°C or lower.

When sufficient energy is given to allow the radically polymerizable compound to undergo a polymerization reaction, it is preferably in a state of no electric field where no voltage is applied.

>LCD display element> The liquid crystal cell obtained in this way can be used to manufacture a liquid crystal display element. For example, the liquid crystal cell is provided with a reflective electrode, a transparent electrode, a λ/4 plate, a polarizing film, a color filter layer, etc. according to the usual method, and a reflective liquid crystal display element can be made. In addition, the liquid crystal cell is provided with a backlight, a polarizing plate, a λ/4 plate, a transparent electrode, a polarizing film, a color filter layer, etc. according to the usual method, and a transmissive liquid crystal display element can be made. [Example]

The present invention is described more specifically with examples, but the present invention is not limited to these examples. The abbreviation of the compound used in the polymerization of the polymer and the preparation of the film-forming composition, and the method of property evaluation are as follows.

[化24]

NMP: N-methyl-2-pyrrolidone, GBL: γ-butyl lactone, BCS: Butylcello.

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

>Determination of Amidation Rate> Put 20 mg of polyimide powder in an NMR sample tube (NMR standard sample tube φ5 made by Kusano Scientific Corporation), and add deuterated dimethyl sulfoxide (DMSO-d6, 0.05% by mass TMS (tetramethylsilane) mixture) 0.53ml, applying ultrasound to completely dissolve. Proton NMR at 500 MHz of this solution was measured with a measuring device (manufactured by Nippon Electronics Data Corporation, JNW-ECA500). The rate of amide imidization is determined based on protons from a structure that does not change before and after amide imidization. The peak value of this proton is used to accumulate the protons and NH protons from amide groups appearing near 9.5 to 10.0 ppm. The cumulative value of the peak is calculated according to the following formula. Amidification rate (%) = (1-α‧x/y)×100 In the formula, x is the accumulation value of the proton peak of the NH from the amide group, y is the accumulation value of the peak of the reference proton, and α is the amide group when the polyamic acid (acid imidization rate is 0%) The ratio of the number of reference protons targeted by 1 NH proton.

>Polymerization of polymers and preparation of free radical generating film-forming compositions> Synthesis Example 1 TC-1, TC-2(50)/DA-1(50), DA-2(50) polymerization of polyimide In a 100ml 4-neck flask equipped with a nitrogen introduction tube, an air cooling tube, and a mechanical stirrer, measure 1.62g of DA-1 (15.00mmol), 3.96g of DA-2 (15.00mmol), and add NMP 48.2g, Stir under a nitrogen atmosphere to dissolve completely. After confirming the dissolution, 3.75 g of TC-2 (15.00 mmol) was added and reacted at 60°C for 3 hours under a nitrogen atmosphere. After returning to room temperature, 2.71 g of TC-1 (13.80 mmol) was added and reacted at 40°C for 12 hours under a nitrogen atmosphere. After confirming the polymerization viscosity, TC-1 was added in such a way that the polymerization viscosity became 1000 mPa‧s to obtain a polymerization solution with a polyamic acid concentration of 20% by mass. In a 200ml Erlenmeyer flask equipped with a magnetic stirrer, measure 60g of the polyamic acid solution obtained above, add 111.4g of NMP to prepare a 7 mass% solution, and add 9.10g (88.52mmol) of acetic anhydride while stirring. 3.76 g (47.53 mmol) of pyridine was stirred at room temperature for 30 minutes and then stirred at 55°C for 3 hours to react. After the reaction was completed, the solution was returned to room temperature, and the reaction solution was injected while stirring in 500 ml of methanol to precipitate a solid. Recover the solid by filtration, then put the solid in 300ml of methanol and stir for 30 minutes to wash, a total of 2 times, recover the solid by filtration, and dry it in a vacuum oven at 60 ℃ after air drying to obtain a number average molecular weight of 11,300, Polyimide (PI-1) with a weight average molecular weight of 32900 and an imidization ratio of 53%.

Free radical generating film forming composition: preparation of AL1 In a 50 ml Erlenmeyer flask equipped with a magnetic stirrer, 2.0 g of the polyimide powder (PI-1) obtained in Synthesis Example 1 was weighed, 18.0 g of NMP was added, and stirred at 50°C to completely dissolve it. Furthermore, NMP6.7g and BCS6.7g were added, and it stirred for further 3 hours, and obtained the radical generating film formation composition of this invention: AL1 (solid content: 6.0 mass %, NMP: 66 mass %, BCS: 30 mass %).

第1步驟：2-羥基甲基丙烯酸乙酯之合成 於安裝了氮氣導入管之500ml之四口燒瓶中，量取4-甲氧基苯酚10mg、DABCO(1,4-二氮雜雙環[2.2.2]辛烷)21.88g(195.1mmol)，加入純水50ml，於氮氣環境下邊於10℃以下攪拌邊加入三聚甲醛11.52g(390.1mmol)，攪拌1小時。確認已從漿液狀態變化為溶液狀態，加入乙腈300ml，邊滴加丙烯酸乙酯19.53g(195.1mmol)，並於50℃反應5小時。反應結束後將反應溶液移到分液漏斗，並加入正己烷50ml。確認已分為3層，回收下面2層，重複此操作3次。再加鹽酸直到pH成為4～5，使用乙酸乙酯萃取。於已萃取之溶液中加入無水硫酸鎂，攪拌並使其乾燥後，進行過濾、濃縮，獲得無色透明的油狀液體22.9g (175.6mmol、產率90%)。結構以核磁共振光譜(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：6.81(1H)、5.80(1H)、4.31(2H)、4.17(1H)、1.98(1H)、0.93(3H)Polymeric Compound Synthesis Example 1 Synthesis of ethyl 2-(heptanoyloxymethyl)acrylate [Chem. 25]

Step 1: Synthesis of 2-hydroxyethyl methacrylate In a 500ml four-necked flask equipped with a nitrogen introduction tube, measure 10 mg of 4-methoxyphenol, DABCO (1,4-diazabicyclo[2.2 .2] Octane) 21.88g (195.1mmol), add 50ml of pure water, add 11.52g (390.1mmol) of paraformaldehyde under a nitrogen atmosphere while stirring at 10°C or less, and stir for 1 hour. It was confirmed that the slurry state had changed to the solution state, 300 ml of acetonitrile was added, 19.53 g (195.1 mmol) of ethyl acrylate was added dropwise, and the reaction was carried out at 50°C for 5 hours. After the reaction, the reaction solution was transferred to a separatory funnel, and 50 ml of n-hexane was added. Confirm that it has been divided into 3 layers, recover the next 2 layers, and repeat this operation 3 times. Hydrochloric acid was added until the pH became 4 to 5, and extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the extracted solution, stirred and dried, and then filtered and concentrated to obtain 22.9 g (175.6 mmol, 90% yield) of a colorless and transparent oily liquid. The structure was confirmed by nuclear magnetic resonance spectroscopy ( ¹ H-NMR spectroscopy). The measured data is shown below. ¹ H NMR (400 MHz, CDCl ₃ ) δ: 6.81 (1H), 5.80 (1H), 4.31 (2H), 4.17 (1H), 1.98 (1H), 0.93 (3H)

Step 2: Synthesis of ethyl 2-(heptanoyloxymethyl)acrylate In a 500ml 4-neck flask equipped with a nitrogen introduction tube, measure 19.9g (152.9mmol) of 2-hydroxymethacrylic acid obtained by the above method ), 300 ml of THF and 23.2 g (229.3 mmol) of triethylamine were added, kept under 10° C. under a nitrogen atmosphere, 25.0 g (168.2 mmol) of heptanyl chloride was added dropwise, and reacted for 6 hours. After the reaction, the precipitated triethylamine hydrochloride was removed by filtration, and the reaction solution was concentrated, redissolved with 300 ml of ethyl acetate, washed three times with 100 ml of 10% potassium carbonate aqueous solution, and washed with 50 ml of pure water. After drying with anhydrous magnesium sulfate, it was filtered and concentrated to obtain a pale yellow viscous body. Then, it was purified by flash column chromatography (developing solvent: ethyl acetate: n-hexane=20:80), the solvent was removed, and vacuum drying was performed to obtain 32.2 g (133.0 mmol: 87% yield) of a colorless and transparent oily liquid. The structure system confirmed the target object by nuclear magnetic resonance spectroscopy ( ¹ H-NMR spectrum). The measured data is shown below. ¹ H NMR (400 MHz, CDCl ₃ ) δ: 6.37 (1H), 5.80 (1H), 3.80 (2H), 4.23-4.21 (2H), 2.39-2.37 (2H), 1.64-1.58 (2H), 1.30-1.27 (9H), 0.86 (3H)

第1步驟：2-羥基甲基丙烯酸丁酯之合成 變更丙烯酸乙酯為丙烯酸丁酯，和前述第1步驟同樣的操作進行合成，獲得無色透明的油24.3g(26.2g：產率85%)。結構以核磁共振光譜(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：6.81(1H)、5.80(1H)、4.31(2H)、4.17(1H)、1.98(1H)、1.67-1.64(2H)、1.42-1.38(2H)、0.93(3H)Polymeric Compound Synthesis Example 2 Synthesis of 2-(heptanoyloxymethyl) butyl acrylate [Chem. 26]

Step 1: Synthesis of 2-hydroxymethacrylate. Change ethyl acrylate to butyl acrylate and synthesize in the same way as in step 1 above to obtain 24.3 g of colorless and transparent oil (26.2 g: yield 85%) . The structure was confirmed by nuclear magnetic resonance spectroscopy ( ¹ H-NMR spectroscopy). The measured data is shown below. ¹ H NMR (400MHz, CDCl ₃ ) δ: 6.81 (1H), 5.80 (1H), 4.31 (2H), 4.17 (1H), 1.98 (1H), 1.67-1.64 (2H), 1.42-1.38 (2H), 0.93(3H)

Step 2: Synthesis of 2-(heptanoyloxymethyl) acrylate Replace the 2-hydroxymethacrylic acid in the second step above with 2-((heptanoyloxy)methyl) acrylate obtained by the above method , The synthesis was carried out in the same operation, and 34.2 g of a colorless and transparent oily liquid was obtained (126.7: yield 82.8%). The structure was confirmed by nuclear magnetic resonance spectroscopy ( ¹ H-NMR spectroscopy). The measured data is shown below. ¹ H NMR (400 MHz, CDCl ₃ ) δ: 6.36 (1H), 5.81 (1H), 4.80 (2H), 4.19-4.16 (2H), 2.35-2.31 (2H), 1.64-1.58 (4H), 1.40-1.25 (8H), 0.96-0.83(6H)

於安裝了迪安斯塔克管之4口燒瓶中量取衣康酸23.8g(182.9mmol)、1-己醇35.5g(347.5mmol)，加入環己烷500ml、濃硫酸0.9g(9.1mmol)、二丁基羥基甲苯(BHT)0.04g(1.82mmol)，設為氮氣環境，於110℃進行24小時脫水縮合反應。反應結束後於反應溶液中加入正己烷100ml，以10%碳酸鈉水溶液100g洗淨3次，以純水100ml洗淨3次，以無水硫酸鎂乾燥。藉由過濾、濃縮後真空乾燥，獲得無色透明的油狀液體48.6g(162.8mmol：產率89%)。結構以核磁共振光譜(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(12H)、0.96-0.83(6H)Polymeric Compound Synthesis Example 3 Synthesis of Dihexyl Itaconic Acid [Chem. 27]

Measure 23.8g (182.9mmol) of itaconic acid and 35.5g (347.5mmol) of 1-hexanol in a 4-neck flask equipped with Dean Stark tube, add 500ml of cyclohexane and 0.9g (9.1mmol) of concentrated sulfuric acid ), dibutylhydroxytoluene (BHT) 0.04g (1.82mmol), set in a nitrogen atmosphere, at 110 ° C for 24 hours dehydration condensation reaction. After the reaction, 100 ml of n-hexane was added to the reaction solution, washed 3 times with 100 g of 10% aqueous sodium carbonate solution, washed 3 times with 100 ml of pure water, and dried over anhydrous magnesium sulfate. After filtration, concentration and vacuum drying, 48.6 g (162.8 mmol: 89% yield) of a colorless and transparent oily liquid was obtained. The structure was confirmed by nuclear magnetic resonance spectroscopy ( ¹ H-NMR spectroscopy). The measured data is shown below. ¹ H NMR (400 MHz, 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 (12H), 0.96-0.83 (6H)

(First substrate) The first substrate (hereinafter also referred to as IPS substrate) is an alkali-free glass substrate having a size of 30 mm×35 mm and a thickness of 0.7 mm. An ITO (Indium-Tin-Oxide) electrode with a comb-shaped pattern with an electrode width of 10 μm and an electrode-electrode spacing of 10 μm is formed on the substrate, and pixels are formed. The size of each pixel is 10mm long and 5mm wide. AL1 and SE-6414 were filtered with a 1.0 μm filter, then applied on the electrode forming surface of the IPS substrate by spin coating, and dried on a hot plate at 80° C. for 1 minute. Then, it was calcined at 220°C for 20 minutes to form a coating film having a thickness of 100 nm each. When the friction treatment is "Yes", the friction is performed so that the rubbing direction becomes parallel to the comb electrode. The friction system is made of Yoshikawa Chemical Co., Ltd.: YA-20R, under the conditions of roller diameter 120mm, rotation speed 300rpm, moving speed 50mm/sec, and pushing amount 0.4mm. Only the film coated with SE-6414 is set to 1000 rpm. After the rubbing treatment, ultrasonic irradiation was carried out in pure water for 1 minute, and dried at 80°C for 10 minutes.

(Second substrate) The second substrate (also called the back ITO substrate) is an alkali-free glass substrate with a size of 30 mm×35 mm and a thickness of 0.7 mm, and an ITO film is formed on the back surface (the surface facing the outside of the cell). In addition, a columnar spacer with a height of 4 μm is formed on the surface (the surface facing the inside of the cell). After filtering with a filter of 1.0 μm, SE-6414 was applied by spin coating and dried on a hot plate at 80°C for 1 minute. Then, calcination was carried out for 20 minutes to obtain a coating film having a thickness of 100 nm each, and then subjected to rubbing treatment. The friction treatment system uses a rayon cloth made by Yoshikawa Chemical Co., Ltd.: YA-20R, and rubs under the conditions of a roll diameter of 120 mm, a rotation speed of 1000 rpm, a moving speed of 50 mm/sec, and a pressing amount of 0.4 mm. After the rubbing treatment, it was irradiated with ultrasound for 1 minute in pure water, and dried at 80°C for 10 minutes.

(Production of liquid crystal cell) Using the two types of substrates (first substrate and second substrate) with liquid crystal alignment film described above, leaving a liquid crystal injection port to seal the surroundings, an empty cell with a cell gap of about 4 μm was produced. At this time, if the first substrate is not rubbed, the comb electrode of the first substrate and the rubbing direction of the second substrate are combined in parallel. When the first substrate is rubbed, the first substrate is used. It is combined in such a way that the rubbing direction with the second substrate becomes antiparallel. From this empty cell, the liquid crystal compositions LC-1 to LC-4 (those in which MLC-3019 manufactured by Merck Corporation were added with the above-mentioned polymerizable compounds in their respective optimal amounts) were prepared at room temperature with a vacuum of about 300 Pa A vacuum injector, and a vacuum injector after degassing at a vacuum of about 1 Pa for 1 hour, the injection port was sealed to prepare 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 heated at 120°C for 10 minutes. When UV treatment is used, a high-pressure mercury lamp is used to irradiate ultraviolet rays to the liquid crystal cell through a band-pass filter with a wavelength of 313 nm to make the exposure amount 3000 mJ.

>Evaluation of LCD alignment> A polarizing plate mounted on cross nicol was used to confirm the alignment of the liquid crystal cell. Those with no defects and alignment were rated as ○, those with slight alignment defects were rated as △, and those without alignment were rated as ×.

>Measurement of V-T curve and evaluation of driving threshold voltage and maximum brightness voltage> Install the white LED backlight and brightness meter in a way that matches the optical axis. Between them, place the liquid crystal cell (liquid crystal display element) with the polarizing plate installed at the minimum brightness. Apply a voltage at 1V intervals up to 8V. The brightness of the voltage is measured by the VT curve. From the obtained V-T curve, it is estimated that the driving threshold value voltage and brightness become the maximum voltage value.

In addition, the liquid crystal compositions LC-1 to LC-4 are obtained by adding the polymerizable compounds described in the following table to the MLC-3019 at the following introduction amounts. [Table 1]

※自由基發生膜係使用未磨擦者。>Alignment results> [Table 2]

※The free radical generating film is used without friction.

The liquid crystals (LC-1, LC-2) with IDBu and IDHex and the liquid crystals with C2C6 and C4C6 are introduced. Even when tested at a relatively high vacuum, they still show very good alignment.

※使用液晶注入時的真空度係於300Pa實施的晶胞>Results of electro-optical characteristics> Then, the driving threshold value voltage, maximum brightness, and response speed of those who have not rubbed the free radical generating film in the aforementioned liquid crystal with zero anchor alignment are summarized as follows. [table 3]

※Using the liquid crystal when the vacuum degree is 300Pa

It was confirmed that when using the polymerizable compound of the present invention, the driving voltage decreased regardless of whether or not there was friction treatment, and by the friction treatment, it was observed that the response speed tended to be better. Therefore, it can be seen that the polymerizable compound of the present invention can simultaneously achieve zero anchoring under high vacuum and a better response speed due to friction. [Industry availability]

According to the present invention, the zero-plane anchoring film can be industrially produced from inexpensive raw materials with good efficiency. In addition, the liquid crystal display device obtained by the method of the present invention is useful as a liquid crystal display device of a vertical alignment method such as a PSA type liquid crystal display or an SC-PVA type liquid crystal display.

Claims (21)

A method for manufacturing a zero-plane anchoring film includes the following steps: In a state where a liquid crystal composition containing a liquid crystal and a radically polymerizable compound having a structure represented by the following formula (1) is in contact with a free radical generating film, The sufficient energy for the polymerization reaction of the radical polymerizable compound;

In formula (1), R ^a and R ^b each independently represent a straight-chain alkyl group having 2 to 8 carbon atoms, and E represents a single bond, -O-, -NR ^c -, -S-, ester bond, or amide The bonding group in the amine bond, R ^c represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms. For example, the method for manufacturing a zero-plane anchoring film according to item 1 of the patent application, wherein the radical generating film possessed by the first substrate is a radical generating film subjected to uniaxial alignment treatment. For example, the method for manufacturing a zero-plane anchoring film according to item 1 or 2 of the patent application, wherein the step of applying energy is performed without an electric field. The method for manufacturing a zero-plane anchoring film according to any one of claims 1 to 3, wherein the radical generating film is a film formed by fixing an organic group that induces radical polymerization. The method for manufacturing a zero-plane anchoring film according to any one of the patent application items 1 to 3, wherein the radical generating film is formed by coating a composition of a compound having a radical generating group and a polymer The cloth is hardened to form a film to be fixed in the film. The method for manufacturing a zero-plane anchoring film according to any one of claims 1 to 3, wherein the radical generating film is composed of a polymer containing an organic group that induces radical polymerization. For example, the method for manufacturing a zero-plane anchoring film according to item 6 of the patent application, wherein the polymer containing an organic group that induces free radical polymerization is a diamine component containing a diamine containing an organic group that induces free radical polymerization At least one polymer selected from the group consisting of polyimide precursor, polyimide, polyurea, and polyamide is obtained. For example, the method for manufacturing the zero-plane anchoring film according to any one of the items 4, 6 and 7 of the patent application scope, wherein the organic group that induces radical polymerization is the following structure [X-1]～[X-18], Organic groups represented by any of [W], [Y], and [Z];

In formulas [X-1] to [X-18], * represents a bonding site other than the polymerizable unsaturated bond with the compound molecule, and S ₁ and S ₂ each independently represent -O-, -NR-, -S, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, and an alkyl group having 1 to 4 carbon atoms;

In the formulas [W], [Y], [Z], * represents the bonding site of the part other than the polymerizable unsaturated bond with the compound molecule, Ar means that it may have an organic group and/or a halogen atom as a substituent Aromatic hydrocarbon groups in the group consisting of free phenylene, naphthyl and biphenylene, R ⁹ and R ¹⁰ each independently represent a C 1-10 alkyl group or a C 1-10 alkoxy group When R ⁹ and R ¹⁰ are alkyl groups, the ends can also be bonded to each other and form a ring structure; 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 having 1 to 4 carbon atoms, and * represents a portion other than Q of the compound molecule Bonding position; R ₁₂ represents a hydrogen atom, a halogen atom, a C 1-10 alkyl group or a C 1-10 alkoxy group. For example, the method for manufacturing the zero-plane anchoring film according to item 7 of the patent application, wherein the diamine containing an organic group that induces radical polymerization has a structure represented by the following general formula (6) or the following general formula (7) Diamine

In formula (6), 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 an unsubstituted or fluorine atom-substituted alkylene group having 1 to 20 carbon atoms, which extends One or more of any -CH ₂ -or -CF ₂ -of the alkyl group may be independently replaced with a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, In addition, any of the following groups, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- may not be adjacent to each other and replaced with these Group; R ⁸ represents a radical polymerization reactive group selected from the following formula;

In formulas [X-1] to [X-18], * represents a bonding site with a portion other than the radical polymerization reactive group of the compound molecule, and S ₁ and S ₂ each independently represent -O- and -NR- , -S, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, and an alkyl group having 1 to 4 carbon atoms;

In formula (7), T ₁ and T ₂ are each independently a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O -, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-, S represents a single bond, or an unsubstituted or fluorine atom-substituted C 1-20 alkylene One or more of any -CH ₂ -or -CF ₂ -of the alkylene group may be independently substituted with -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring The base in, or any of the following enumerations, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other can be Replaced by these radicals, J is an organic radical represented by any of the following formulas,

In the formulas [W], [Y], [Z], * represents a bonding site with T ₂ , Ar represents an organic group and/or a halogen atom may be substituted as a substituent selected from phenylene, naphthyl, And aromatic hydrocarbon groups in the group consisting of biphenylene, R ⁹ and R ¹⁰ each independently represent a C 1-10 alkyl group or a C 1-10 alkoxy group, and 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 having 1 to 4 carbon atoms, and * represents a portion other than Q of the compound molecule Bonding position; R ¹² represents a hydrogen atom, a halogen atom, a C 1-10 alkyl group or a C 1-10 alkoxy group. For example, the method for manufacturing a zero-plane anchoring film according to any one of items 1 to 9 of the patent application, wherein E in the general formula (1) is an ester bond. A method for manufacturing a liquid crystal cell, using the method for manufacturing a zero-plane anchoring film as described in any one of patent application items 1 to 10, It includes the following steps: Prepare a first substrate with a free radical generating film and a second substrate that can also have a free radical generating film; Making a unit cell in such a way that the free radical generating film on the first substrate faces 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. For example, in the method for manufacturing a liquid crystal cell according to claim 11, the second substrate is a second substrate without a free radical generating film. For example, in the method for manufacturing a liquid crystal cell of claim 12, the second substrate is covered with a liquid crystal alignment film having uniaxial alignment. For example, in the method of manufacturing a liquid crystal cell according to claim 13, the liquid crystal alignment film with uniaxial alignment is a liquid crystal alignment film for horizontal alignment. The method for manufacturing a liquid crystal cell according to any one of claims 11 to 14, wherein the first substrate with a radical generating film is a substrate with comb-shaped electrodes. A liquid crystal composition containing liquid crystal and a radical polymerizable compound having a structure represented by the following formula (1),

In formula (1), R ^a and R ^b each independently represent a straight-chain alkyl group having 2 to 8 carbon atoms, and E represents a single bond, -O-, -NR ^c -, -S-, ester bond, or amide The bonding group in the amine bond, R ^c represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms. For example, in the liquid crystal composition of claim 16, the E in the general formula (1) is an ester bond. A method for manufacturing a liquid crystal display element using a film having a zero-plane anchoring state obtained by using the method as described in any one of patent application items 1 to 15. A liquid crystal display element is obtained by using the manufacturing method of the liquid crystal display element as claimed in item 18 of the patent scope. As in the liquid crystal display element of claim 19, the first substrate or the second substrate has electrodes. For example, the liquid crystal display element of the 19th or 20th patent application is a low voltage driven horizontal electric field liquid crystal display element.