TW202118812A - Lateral-electric-field liquid crystal display element, and method for manufacturing lateral-electric-field liquid crystal cell - Google Patents

Abstract

A lateral-electric-field liquid crystal display element in which an interdigital electrode substrate provided with a liquid crystal alignment film and a counter substrate provided with a liquid crystal alignment film are provided so that the two liquid crystal alignment films face each other, and a liquid crystal composition is filled between the liquid crystal alignment film and the liquid crystal alignment film, wherein the uncoupling energy of the liquid crystal alignment film on the counter substrate side is less than the uncoupling energy of the liquid crystal alignment film on the interdigital electrode substrate side.

Description

Horizontal electric field liquid crystal display element and method for manufacturing horizontal electric field liquid crystal cell

The present invention relates to a horizontal electric field liquid crystal display element that has both high-speed response and high backlight light transmittance and high voltage retention, and a method for manufacturing a horizontal electric field liquid crystal cell that can be used in the manufacture of the horizontal electric field liquid crystal display element.

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

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

In recent years, an IPS mode using weak anchoring has been proposed. It is reported that by using this method, compared with the conventional IPS mode, the transmittance can be greatly improved and can be driven at a low voltage (see Patent Document 1). Specifically, a liquid crystal alignment film with strong anchoring energy is used on a single-sided substrate, and a treatment is applied to the other substrate with electrodes that generate a transverse electric field to lose the alignment constraint of the liquid crystal, and use these To make the method of IPS mode liquid crystal display element.

In addition, in recent years, some people have used thick polymer brushes to create a weakly anchored state, and techniques for weakly anchored IPS mode have been proposed (Patent Document 2 and Patent Document 3). 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] JP 2013-231757 A [Patent Document 3] International Patent Application Publication No. 2019-004433 Pamphlet

[The problem to be solved by the invention]

The above-mentioned technology using weak anchoring can improve the transmittance by using the IPS mode. Therefore, it is believed that the Vcom shift, which is a problem of the FFS mode, can be eliminated and the expensive substrate cost. However, the IPS mode can be used in the miniaturization of comb-shaped electrodes. Issues can also include problems such as difficulty in patterning quality management and poor productivity. Therefore, it is considered that there is a need for a technology that can be applied even with FFS.

On the other hand, this technology has a problem in principle. In the FFS driving method, if the anchor energy on the electrode substrate side is reduced, depending on the liquid crystal state of the weak anchor film interface, the transmittance of the light from the backlight will be deteriorated. Propensity. It is known that FFS is different from IPS in that the application of the electric field is not uniform. It is believed that even if a slight anchoring energy is generated in the polar angle direction, especially in the weak anchoring state, the liquid crystal will not be subjected to the alignment constraint force in the weak anchoring state. It moves with a weak force. Therefore, the liquid crystal in the area near the vertical electric field on the side of the electrode substrate, which does not normally move, moves, resulting in disclination, which will reduce the transmittance. In addition, the weak anchoring obtained by adding a polymerizable compound to the liquid crystal is thought to cause a decrease in voltage holding ratio, image retention, etc. due to additives. If such a technical problem can be solved, panel manufacturers will also have advantages in suppressing battery consumption and improving image quality.

The present invention is made to solve the above-mentioned problems, and aims to provide a horizontal electric field liquid crystal display element that has both high-speed response and high backlight light transmittance, high voltage retention, and low image retention, and can be used in the electric field Horizontal electric field liquid crystal cell for the manufacture of liquid crystal display elements. [Means to solve the problem]

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

式[X-1]~[X-18]中，＊表示鍵結部位，S₁ 、及S₂ 各自獨立地表示-O-、-NR-、或-S-，R表示氫原子、或碳數1~10之烷基(前述碳數1~10之烷基之中，碳數2~10之烷基之一部分的-CH₂ -基也可置換為氧原子。惟，S₂ R或NR中，前述烷基之一部分的-CH₂ -基置換為氧原子時，前述氧原子不直接鍵結於S₂ 或N。)。R¹ 、及R² 各自獨立地表示氫原子、鹵素原子、或碳數1~4之烷基。 [化2]

式[W]、[Y]、及[Z]中，＊表示鍵結部位，Ar表示選自由亦可具有有機基及/或鹵素原子作為取代基之伸苯基、伸萘基、及伸聯苯基構成之群組中之芳香族烴基，R⁹ 及R¹⁰ 各自獨立地表示碳數1~10之烷基或碳數1~10之烷氧基，R⁹ 與R¹⁰ 為烷基時，亦可末端彼此鍵結而形成環結構。Q表示下列任一結構。 [化3]

式中，R¹¹ 表示-CH₂ -、-NR-、-O-、或-S-，R各自獨立地表示氫原子或碳數1~4之烷基，＊表示鍵結部位。S³ 表示單鍵、-O-、-NR-(R表示氫原子或碳數1~4之烷基。)、或-S-。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]之橫電場液晶顯示元件，其中，前述含有誘發自由基聚合之有機基的二胺，係具有下列通式(6)或下列通式(7)表示之結構的二胺。 [化4]

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置換為選自-CH＝CH-、二價碳環、及二價雜環之基，另外，亦能以下列所列舉之任意基，亦即-O-、-COO-、-OCO-、-NHCO-、-CONH-、或-NH-彼此不相鄰為條件而置換為該等基； R⁸ 表示選自下式[X-1]~[X-18]之式表示之自由基聚合反應性基。 [化5]

式[X-1]~[X-18]中，＊表示鍵結部位，S₁ 、及S₂ 各自獨立地表示-O-、-NR-、或-S-，R表示氫原子、或碳數1~10之烷基(前述碳數1~10之烷基之中，碳數2~10之烷基之一部分的-CH₂ -基也可置換為氧原子。惟，S₂ R或NR中，前述烷基之一部分的-CH₂ -基置換為氧原子時，前述氧原子不直接鍵結於S₂ 或N。)。R¹ 、及R² 各自獨立地表示氫原子、鹵素原子、或碳數1~4之烷基。 [化6]

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置換為選自-CH＝CH-、二價碳環、及二價雜環之基，另外，亦能以下列所列舉之任意基，亦即-O-、-COO-、-OCO-、-NHCO-、-CONH-、或-NH彼此不相鄰為條件而置換為該等基； J係選自下式[W]、[Y]及[Z]之式表示之有機基。 [化7]

式[W]、[Y]、及[Z]中，＊表示與T₂ 之鍵結部位，Ar表示選自由亦可具有有機基及/或鹵素原子作為取代基之伸苯基、伸萘基、及伸聯苯基構成之群組中之芳香族烴基，R⁹ 及R¹⁰ 各自獨立地表示碳數1~10之烷基或碳數1~10之烷氧基； Q表示下列任一結構。 [化8]

式中，R¹¹ 表示-CH₂ -、-NR-、-O-、或-S-，R各自獨立地表示氫原子或碳數1~4之烷基，＊表示鍵結部位。 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。 S³ 表示單鍵、-O-、-NR-(R表示氫原子或碳數1~4之烷基。)、或-S-。 [10]如[4]~[9]中任一項之橫電場液晶顯示元件，其中，前述自由基聚合性化合物中之至少一種係與液晶具有相容性的於一分子中具有一個聚合性反應基之化合物。 [11]如[10]之橫電場液晶顯示元件，其中，前述自由基聚合性化合物之聚合性反應基選自下列結構。 [化9]

式中，＊表示鍵結部位。R^b 表示碳數2~8之直鏈烷基，E表示選自單鍵、-O-、-NRc-、-S-、酯鍵及醯胺鍵之鍵結基。Rc表示氫原子、或碳數1~4之烷基。 [12]如[4]~[11]中任一項之橫電場液晶顯示元件，其中，前述自由基聚合性化合物係將前述自由基聚合性化合物進行聚合而獲得之聚合物之Tg為100℃以下的自由基聚合性化合物。 [13]一種橫電場液晶胞之製造方法，包含下列步驟： 準備係具有液晶配向膜之第一基板的梳齒電極基板、及係具有自由基產生膜之第二基板的對向基板； 以前述第二基板上之前述自由基產生膜面對前述第一基板的方式製作晶胞；及 在前述第一基板與前述第二基板之間填充含有液晶及自由基聚合性化合物之液晶組成物。 [14]如[13]之橫電場液晶胞之製造方法，其中，前述第二基板係塗覆有具有單軸配向性之液晶配向膜的基板。 [15]如[14]之橫電場液晶胞之製造方法，其中，前述具有單軸配向性之液晶配向膜係水平配向用之液晶配向膜。 [16]如[13]~[15]中任一項之橫電場液晶胞之製造方法，其中，前述梳齒電極基板係IPS基板或FFS基板。 [發明之效果]That is, the present invention includes the following contents. [1] A transverse electric field liquid crystal display element having a comb-shaped electrode substrate provided with a liquid crystal alignment film and a counter substrate provided with a liquid crystal alignment film. The two liquid crystal alignment films face each other, and the liquid crystal alignment film and the liquid crystal alignment film face each other. The liquid crystal alignment film is filled with liquid crystal; the feature is that the anchoring energy of the liquid crystal alignment film on the side of the counter substrate is smaller than the anchoring energy of the liquid crystal alignment film on the side of the comb-tooth electrode substrate. [2] The horizontal electric field liquid crystal display element of [1], wherein the liquid crystal alignment film on the side of the comb-teeth electrode substrate and the liquid crystal alignment film on the side of the counter substrate are both liquid crystal alignment films subjected to uniaxial alignment treatment, And only the liquid crystal alignment film on the opposite substrate side undergoes weak anchoring treatment. [3] The horizontal electric field liquid crystal display device of [1] or [2], wherein the comb-shaped electrode substrate is an IPS substrate or an FFS substrate. [4] The transverse electric field liquid crystal display element according to any one of [1] to [3], wherein the liquid crystal alignment film on the counter substrate side is composed of a liquid crystal containing the liquid crystal and a radical polymerizable compound It is obtained by subjecting the aforementioned radical polymerizable compound to a polymerization reaction in a state in which the substance contacts the radical generating film. [5] The horizontal electric field liquid crystal display element of [4], wherein the radical generating film is a film obtained by immobilizing an organic group that induces radical polymerization. [6] The lateral electric field liquid crystal display element of [4] or [5], wherein the radical generating film is composed of a polymer containing an organic group that induces radical polymerization. [7] The horizontal electric field liquid crystal display element of [6], wherein the polymer containing an organic group that induces radical polymerization is selected from the use of a diamine component containing a diamine containing an organic group that induces radical polymerization. The obtained polyimide precursor, polyimine, polyurea and at least one polymer of polyimide. [8] The horizontal electric field liquid crystal display element of [6] or [7], wherein the aforementioned organic group that induces free radical polymerization has the following structure [X-1]~[X-18], [W], [Y] , Or [Z] represents the organic group. [化1]

In the formulas [X-1]~[X-18], * represents the bonding site, S ₁ and S ₂ each independently represent -O-, -NR-, or -S-, and R represents a hydrogen atom or carbon An alkyl group of 1 to 10 (in the aforementioned alkyl group of 1 to 10 carbons, the -CH ₂ -group of a part of the alkyl group of 2 to 10 carbons can also be replaced with an oxygen atom. However, S ₂ R or NR _{When the -CH 2} -group of a part of the aforementioned alkyl group is replaced with an oxygen atom, the aforementioned oxygen atom is not directly bonded to S ₂ or N.). R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. [化2]

In formulas [W], [Y], and [Z], * represents the bonding site, and Ar represents selected from phenylene, naphthylene, and phenylene which may also have organic groups and/or halogen atoms as substituents In the aromatic hydrocarbon group in the group consisting of phenyl, R ⁹ and R ¹⁰ each independently represent an alkyl group with 1 to 10 carbons or an alkoxy group with 1 to 10 carbons. 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. [化3]

In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O-, or -S-, R each independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, and * represents a bonding site. S ³ represents a single bond, -O-, -NR- (R represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms.), or -S-. R ¹² represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbons, or an alkoxy group with 1 to 10 carbons. [9] The horizontal electric field liquid crystal display element of [7], wherein the aforementioned diamine containing an organic group that induces radical polymerization is a diamine having a structure represented by the following general formula (6) or the following general formula (7) . [化4]

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 substituted fluorine atom substituted alkylene group with 1 to 20 carbons, the extension 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-, divalent carbocyclic ring, and divalent heterocyclic ring. In addition, also It can be replaced with any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other as a condition; R ⁸ It represents a radical polymerization reactive group represented by a formula selected from the following formulas [X-1] to [X-18]. [化5]

In the formulas [X-1]~[X-18], * represents the bonding site, S ₁ and S ₂ each independently represent -O-, -NR-, or -S-, and R represents a hydrogen atom or carbon An alkyl group of 1 to 10 (in the aforementioned alkyl group of 1 to 10 carbons, the -CH ₂ -group of a part of the alkyl group of 2 to 10 carbons can also be replaced with an oxygen atom. However, S ₂ R or NR _{When the -CH 2} -group of a part of the aforementioned alkyl group is replaced with an oxygen atom, the aforementioned oxygen atom is not directly bonded to S ₂ or N.). R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. [化6]

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 unsubstituted or substituted by fluorine atoms, carbon number 1-20 alkylene Group, any _{one or more of -CH 2} -or -CF ₂ -of the alkylene group may be independently substituted with a group selected from -CH=CH-, divalent carbocyclic ring, and divalent heterocyclic ring In addition, it is also possible to substitute any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH are not adjacent to each other as a condition to replace them with these groups ; J is an organic group selected from the following formulas [W], [Y] and [Z]. [化7]

Formula [W], [Y], and [Z], * represents a bonding site with the T _2, Ar represents an organic group selected from the group consisting of may, and / or a halogen atom as a substituent of the phenylene group, a naphthyl group extension , And the aromatic hydrocarbon group in the group consisting of biphenyl, R ⁹ and R ¹⁰ each independently represent an alkyl group with 1 to 10 carbons or an alkoxy group with 1 to 10 carbons; Q represents any of the following structures . [化8]

In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O-, or -S-, R each independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, and * represents a bonding site. R ¹² represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbons, or an alkoxy group with 1 to 10 carbons. S ³ represents a single bond, -O-, -NR- (R represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms.), or -S-. [10] The transverse electric field liquid crystal display element of any one of [4] to [9], wherein at least one of the aforementioned radically polymerizable compounds is compatible with liquid crystal and has one polymerizable property in one molecule. Reactive compound. [11] The horizontal electric field liquid crystal display device of [10], wherein the polymerizable reactive group of the radical polymerizable compound is selected from the following structures. [化9]

In the formula, * represents the bonding site. R ^b represents a linear alkyl group having 2 to 8 carbon atoms, and E represents a bonding group selected from a single bond, -O-, -NRc-, -S-, an ester bond, and an amide bond. Rc represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. [12] The transverse electric field liquid crystal display element of any one of [4] to [11], wherein the radical polymerizable compound is a polymer obtained by polymerizing the radical polymerizable compound and the Tg of a polymer is 100°C The following radically polymerizable compounds. [13] A method for manufacturing a transverse electric field liquid crystal cell, comprising the following steps: preparing a comb-shaped electrode substrate having a first substrate with a liquid crystal alignment film and a counter substrate having a second substrate with a radical generating film; The unit cell is fabricated in such a way that the radical generating film on the second substrate faces the first substrate; and a liquid crystal composition containing liquid crystal and a radical polymerizable compound is filled between the first substrate and the second substrate. [14] The method for manufacturing a transverse electric field liquid crystal cell according to [13], wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment. [15] The method for manufacturing a transverse electric field liquid crystal cell according to [14], wherein the aforementioned liquid crystal alignment film with uniaxial alignment is a liquid crystal alignment film for horizontal alignment. [16] The method for manufacturing a transverse electric field liquid crystal cell according to any one of [13] to [15], wherein the comb-tooth electrode substrate is an IPS substrate or an FFS substrate. [Effects of Invention]

According to the transverse electric field liquid crystal display element of the present invention, image retention is not easy, and high backlight light transmittance, fast response speed and high voltage retention can be achieved.

The liquid crystal display element for transverse electric field of the present invention has a comb-tooth electrode substrate with a liquid crystal alignment film and a counter substrate with a liquid crystal alignment film. The two liquid crystal alignment films face each other and are between the two liquid crystal alignment films. It is filled with a liquid crystal composition; it is characterized in that the anchoring energy of the liquid crystal alignment film on the side of the opposite substrate is smaller than the anchoring energy of the liquid crystal alignment film on the side of the comb-tooth electrode substrate. More preferably, the liquid crystal alignment film on the counter substrate side is a lateral electric field liquid crystal display element in which a weak anchor film is used. In addition, in this specification, the anchoring energy refers to the anchoring energy in the in-plane direction of the liquid crystal alignment film, that is, the azimuthal anchoring energy. The azimuth anchor energy can be estimated by, for example, the method of using the driving threshold voltage in the electro-optical response of the liquid crystal cell (Fréedericksz transition method), and the method of using the threshold voltage in the change of electrostatic capacitance (strong electric field method, electrostatic capacitance method). ), the method of applying a strong magnetic field to the liquid crystal cell and evaluating the optical response of the liquid crystal (detailed in the Journal of the Liquid Crystal Society of Japan, Heisei 2017, Vol. 9. No. 4 Liquid Crystal Chemistry Experiment Lecture: Measurement of Interface Anchor Energy Coefficient method). However, there are various prerequisites for the aforementioned methods, and only membranes with strong anchoring energy are discussed. The correct method for obtaining very weak anchoring energy is currently being studied.

FIG. 1 is a schematic cross-sectional view showing an example of a lateral electric field liquid crystal display element of the present invention, which is an example of an IPS mode liquid crystal display element. In the horizontal electric field liquid crystal display element 1 illustrated in FIG. 1, a liquid crystal 3 is sandwiched between a comb-shaped electrode substrate 2 provided with a liquid crystal alignment film 2c and a counter substrate 4 provided with a liquid crystal alignment film 4a. The comb-tooth electrode substrate 2 has a substrate 2a, a plurality of linear electrodes 2b formed on the substrate 2a and arranged in a comb-tooth shape, and a liquid crystal alignment film 2c formed on the substrate 2a to cover the linear electrodes 2b . The counter substrate 4 has a base material 4b and a liquid crystal alignment film 4a formed on the base material 4b. In the horizontal electric field liquid crystal display element 1, the anchoring energy of the liquid crystal alignment film 4a on the side of the counter substrate 4 is smaller than the anchoring energy of the liquid crystal alignment film 2c on the side of the comb-shaped electrode substrate 2. The liquid crystal alignment film 4a is, for example, a weak anchor film obtained by chemically changing a radical generating film. The liquid crystal alignment film on the counter substrate side is obtained by, for example, allowing a liquid crystal composition containing a liquid crystal and a radical polymerizable compound to contact the radical generating film and subjecting the radical polymerizable compound to a polymerization reaction. In this horizontal electric field liquid crystal display element 1, when a voltage is applied to the linear electrodes 2b, an electric field is generated between the linear electrodes 2b as indicated by the lines of force L.

2 is a schematic cross-sectional view showing another example of the transverse electric field liquid crystal display element of the present invention, which is an example of an FFS mode liquid crystal display element. In the horizontal electric field liquid crystal display element 1 illustrated in FIG. 2, a liquid crystal 3 is sandwiched between a comb-shaped electrode substrate 2 provided with a liquid crystal alignment film 2h and a counter substrate 4 provided with a liquid crystal alignment film 4a. The comb-tooth electrode substrate 2 has a substrate 2d, a surface electrode 2e formed on the substrate 2d, an insulating film 2f formed on the surface electrode 2e, and a plurality of linear electrodes formed on the insulating film 2f and arranged in a comb-like shape. 2g, and a liquid crystal alignment film 2h formed on the insulating film 2f so as to cover the linear electrode 2g. The counter substrate 4 has a base material 4b and a liquid crystal alignment film 4a formed on the base material 4b. In the transverse electric field liquid crystal display element 1, the anchoring energy of the liquid crystal alignment film 4a on the side of the counter substrate 4 is smaller than the anchoring energy of the liquid crystal alignment film 2h on the side of the comb-shaped electrode substrate 2. The liquid crystal alignment film 4a is, for example, a weak anchor film obtained by chemically changing a radical generating film. The liquid crystal alignment film on the counter substrate side is obtained by, for example, allowing a liquid crystal composition containing a liquid crystal and a radical polymerizable compound to contact the radical generating film and subjecting the radical polymerizable compound to a polymerization reaction. In this horizontal electric field liquid crystal display element 1, when a voltage is applied to the surface electrode 2e and the linear electrode 2g, an electric field is generated between the surface electrode 2e and the linear electrode 2g as indicated by the electric force line L.

"Weak anchor film" means that there is no alignment binding force of the liquid crystal molecules in the in-plane direction, or even if there is, it is weaker than the intermolecular force of the liquid crystals. The film alone cannot make the liquid crystal molecules uniaxially align in any direction的膜。 The film. In addition, the weakly anchored film is not limited to a solid film, but also includes a liquid film covering a solid surface. Usually in liquid crystal display elements, a film that constrains the alignment of liquid crystal molecules is used in pairs, that is, a liquid crystal alignment film to align the liquid crystal, but when the weak anchor film and the liquid crystal alignment film are used in pairs, the liquid crystal can also be aligned . This is because the alignment constraint force of the liquid crystal alignment film can also be transmitted to the thickness direction of the liquid crystal layer by the intermolecular force between the liquid crystal molecules, and as a result, the liquid crystal molecules near the weak anchor film will also be aligned. Thereby, when a liquid crystal alignment film for horizontal alignment is used for the liquid crystal alignment film, a horizontal alignment state can be generated in the entire liquid crystal cell. Horizontal alignment refers to the state in which the long axes of the liquid crystal molecules are aligned almost parallel to the surface of the liquid crystal alignment film, and the single-digit tilt alignment is also included in the category of horizontal alignment.

As for the weak anchor film, for example, it can be obtained by polymerizing the polymerizable compound by UV or heat in a state where the liquid crystal containing the specific polymerizable compound is brought into contact with the radical generating film. More specifically, it is a manufacturing method of a weak anchor film including the following steps: preparing a liquid crystal and a radical polymerizable compound between a first substrate with a liquid crystal alignment film and a second substrate with a radical generating film The unit cell of the liquid crystal composition; and the radical polymerizable compound is polymerized in the unit cell. It is preferably a method of manufacturing a liquid crystal cell including the following steps: preparing a first substrate with a liquid crystal alignment film and a second substrate with a free radical generating film; making the cell such that the free radical generating film and the first substrate are opposed to each other ; And filling a liquid crystal composition containing liquid crystal and a radical polymerizable compound between the first substrate and the second substrate. For example, a method for manufacturing a low-voltage driving horizontal electric field liquid crystal display element in which the first substrate does not have a radical generating film, but has a liquid crystal alignment film subjected to uniaxial alignment treatment, and the first substrate is a substrate with comb-shaped electrodes.

On the other hand, the weakly anchored state refers to a state with a slight alignment binding force. Although it does not have the binding force to align the liquid crystal, it has an optically anisotropic state, which is equivalent to the magnitude of the anchoring energy. The range of 10 ^-3 ~10 ^-6 (J/m ² ). Regarding the weak anchoring state, for example, it can be obtained by a manufacturing method using a weak anchoring film due to the state in which the aforementioned second substrate with a radical generating film is subjected to an alignment treatment. The alignment treatment can be implemented using a rubbing method, or can be implemented using optical alignment.

[Free radical generating film forming composition] The radical generating film forming composition used in the present invention for forming a radical generating film contains, for example, a polymer in terms of ingredients and a radical capable of generating radicals. In this case, the composition may be a polymer having a radical-generating group bonded thereto, or a compound having a radical-generating group and a polymer that becomes a base resin. By coating and curing such a composition to form a film, a radical generating film in which radicals generating radicals are immobilized in the film can be obtained. The group capable of generating free radicals is preferably an organic group that induces free radical polymerization.

As the organic group that induces radical polymerization in this way, an organic group represented by a formula selected from the above-mentioned formulas [X-1] to [X-18], [W], [Y], and [Z] can be cited. Here, Ar in the formulas [W], [Y], and [Z] represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylene. In addition, the aromatic hydrocarbon group may have an organic group and/or a halogen atom as a substituent. In the R of the formula [X-1]~[X-18], the -CH ₂ -group of a part of the alkyl group can also be replaced with an oxygen atom of a carbon number 2-10 alkyl group, for example, carbon number 1-9的alkoxy。 However, _{R in S 2} R or NR is not an alkoxy group.

As for the polymer, for example, it is preferably at least one selected from the group consisting of polyimide precursors, and polyimine, polyurea, polyamide, polyacrylate, polymethacrylate, etc. polymer.

In order to obtain the free radical generating film used in the present invention, when a polymer having an organic group that induces radical polymerization is used, in order to obtain a polymer having a radical generating group, it is preferable to use a polymer containing a group selected from the group consisting of methacrylic acid. , Acrylic, vinyl, allyl, coumarin, styryl, and cinnamyl at least one of the photoreactive side chain monomers, the side chain has a side chain that will decompose due to ultraviolet radiation and produce free The monomer at the base site is preferably produced as a monomer component. On the other hand, considering that the monomer that generates free radicals itself polymerizes spontaneously and becomes an unstable compound, considering the ease of synthesis, it is preferable to be derived from a diamine with free radical generating sites. The polymer is more preferably polyimide precursors such as polyamide acid and polyamide ester, polyimide, polyurea, polyamide, etc.

Such a diamine containing a radical generating site, specifically, for example, the diamine represented by the above formula (6) having a side chain that generates free radicals and can polymerize, but is not limited to this.

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

式中，J¹ 為選自單鍵、-O-、-COO-、-NHCO-、及-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。A diamine containing at least one photoreactive group selected from the group consisting of a methacrylic group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamyl group, specifically In particular, the following compounds can be cited, but are not limited to these. [化10]

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

Examples of diamines having a side chain that decomposes and generate radicals due to ultraviolet irradiation include diamines represented by the above formula (7), but are not limited thereto.

The bonding position of the two amino groups (-NH ₂ ) in the above formula (7) is not limited. Specifically, the bonding group relative to the side chain can be listed as 2, 3 positions, 2, 4 positions, 2, 5 positions, 2, 6 positions, 3, 4 positions, 3 on the benzene ring. ,5's position. Among them, considering the reactivity when synthesizing polyamide acid, the preferred position is 2,4 position, 2,5 position, or 3,5 position.

式中，n為2~8之整數。Especially in view of the ease of synthesis, the level of versatility, characteristics, etc., the structure represented by the following formula is the best, but it is not limited to these. [化11]

In the formula, n is an integer from 2 to 8.

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

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

In addition, when the polymer used in the radical generating film of the present invention is obtained from a diamine, as long as the effect of the present invention is not impaired, other diamines other than the above-mentioned diamine having a site for generating radicals can be used as the diamine. Amine component. Specifically, examples include: p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4 -Dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5- Diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3, 3'-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4 '-Diaminobiphenyl, 3,3'-Dicarboxy-4,4'-Diaminobiphenyl, 3,3'-Difluoro-4,4'-Diaminobiphenyl, 3,3' -Bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl Biphenyl, 2,3'-diaminodiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenyl Methane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane Phenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyl diphenylamine, 3,3'-sulfonyl diphenylamine, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl -Bis(3-aminophenyl)silane, 4,4'-sulfodiphenylamine, 3,3'-sulfodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diamino Diphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenylamine Phenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl(2, 2'-diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-di Aminobenzophenone, 3,4'-diaminobenzophenone, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,4- Diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-Diaminonaphthalene, 2,7-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4- Bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3 -Bis(4-aminophenoxy)benzene, 1,4-bis (4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-amino) Phenoxy)benzene, 4,4'-[1,4-phenylenebis(methylene)]diphenylamine, 4,4'-[1,3-phenylenebis(methylene)]di Aniline, 3,4'-[1,4-phenylenebis(methylene)]diphenylamine, 3,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3, 3'-[1,4-phenylenebis(methylene)]diphenylamine, 3,3'-[1,3-phenylenebis(methylene)]diphenylamine, 1,4-phenylene Bis[(4-aminophenyl) ketone], 1,4-phenylene bis[(3-aminophenyl) ketone], 1,3-phenylene bis[(4-amino Phenyl) ketone], 1,3-phenylene bis[(3-aminophenyl) ketone], 1,4-phenylene bis(4-aminobenzoate), 1,4 -Phenylene bis(3-amino benzoate), 1,3-phenylene bis(4-amino benzoate), 1,3-phenylene bis(3-amino benzoate) Acid ester), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalic acid Ester, bis(3-aminophenyl) isophthalate, N,N'-(1,4-phenylene) bis(4-aminobenzoamide), N,N'-( 1,3-phenylene) bis(4-aminobenzoamide), N,N'-(1,4-phenylene)bis(3-aminobenzoamide), N,N' -(1,3-phenylene) bis(3-aminobenzoamide), N,N'-bis(4-aminophenyl)p-xylylenedimethamide, N,N'-bis( 3-aminophenyl)p-xylylenedimethamide, N,N'-bis(4-aminophenyl)m-xylylenedimethamide, N,N'-bis(3-aminophenyl)m Xylylenedimethamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenyl sulfide, 2,2'-bis[4-( 4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminobenzene Yl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2 '-Bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, Trans-1,4-bis(4-aminophenyl)cyclohexane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, bis(4-aminophenoxy) Methane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane , 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane Alkyl, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminobenzene Oxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-amino) Phenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-amine Phenyloxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis(3- Aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-bis (4-aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)dodecane and other aromatic diamines; bis(4-aminocyclohexyl)methane, bis(4 -Amino-3-methylcyclohexyl) methane and other alicyclic diamines; 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1, 6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1, Aliphatic diamines such as 11-diaminoundecane and 1,12-diaminododecane; 1,3-bis[2-(p-aminophenyl)ethyl]urea, 1,3-bis [2-(p-aminophenyl) ethyl]-1-tertiary butoxycarbonyl urea and other diamines with urea structure; N-p-aminophenyl-4-p-aminophenyl (third-butyl Oxycarbonyl) aminomethylpiperidine and other diamines with nitrogen-containing unsaturated heterocyclic structure; N-tertiary butoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N -(4-Aminobenzyl)amine, etc., a diamine having an N-Boc group (Boc represents a tertiary butoxycarbonyl group), and the like.

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

In the synthesis when the polymer is polyamide acid, the tetracarboxylic dianhydride that reacts with the above-mentioned diamine component is not particularly limited. Specifically, examples include: pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid , 2,3,6,7-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, 2,3,3', 4'-Biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl) ether, 3,3',4,4'-benzophenone tetracarboxylic acid, bis(3,4-dicarboxyphenyl) ), bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2, 2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethylsilane, bis(3,4-dicarboxyphenyl)diphenylsilane, 2,3 ,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenyl tetracarboxylic acid, 3,4,9, 10-perylene tetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid, oxydiphthalate tetracarboxylic acid, 1,2,3,4- Cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-tetramethyl-1 ,2,3,4-cyclobutane tetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid, 1,3-dimethyl-1,2,3 ,4-Cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid, 3,4-dicarboxy-1-cyclohexylsuccinic acid Acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, bicyclo[3,3,0]octane- 2,4,6,8-tetracarboxylic acid, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]decane-2,4, 7,9-tetracarboxylic acid, 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-diside oxytetrahydrofuran-3-yl)-1,2,3,4-tetra Hydronaphthalene-1,2-dicarboxylic acid, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 5-(2,5-di-side oxytetrahydrofuranyl )-3-methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo[6,2,1,1,0<2,7>] twelve-4,5,9,10- Tetracarboxylic acid, 3,5,6-tricarboxynorbornane-2:3,5:6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid and other tetracarboxylic dianhydrides.

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

In the synthesis when the polymer is a polyamide, the structure of the dialkyl tetracarboxylic acid that reacts with the above-mentioned diamine component is not particularly limited, and specific examples thereof are listed below. Specific examples of aliphatic tetracarboxylic acid diesters include: 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutane Alkyl tetracarboxylic acid dialkyl ester, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1, 2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofurantetracarboxylic acid dioxane Dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1-cyclohexyl dialkyl succinate, 3,4-dicarboxy-1,2 ,3,4-Tetrahydro-1-naphthalenesuccinate 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-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclic [4.2.1.0<2,5>] nonane Alkyl-3,4,7,8-tetracarboxylic 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-di pendant oxy Tetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dialkyl ester and the like.

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

式中R₂₂ 、及R₂₃ 表示碳數1~10之脂肪族烴基。In the synthesis when the polymer is a polyurea, the diisocyanate that reacts with the above-mentioned diamine component is not particularly limited, and it can be used in accordance with availability and the like. The specific structure of the diisocyanate is shown below. [化12]

In the formula, R ₂₂ and R ₂₃ represent an aliphatic hydrocarbon group with 1 to 10 carbon atoms.

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

In the synthesis when the polymer is polyamide, the structure of the dicarboxylic acid to be reacted is not particularly limited, and specific examples are listed below. Aliphatic dicarboxylic acids include: malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyl Dicarboxylic acids such as adipic 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, 1,2-cyclobutane dicarboxylic acid Acid, 1,3-cyclobutane dicarboxylic acid, 3,4-diphenyl-1,2-cyclobutane dicarboxylic acid, 2,4-diphenyl-1,3-cyclobutane dicarboxylic acid , 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid, 1,1-cyclopentane dicarboxylic acid, 1,2-cyclopentane dicarboxylic acid , 1,3-cyclopentane dicarboxylic acid, 1,1-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclo Hexane dicarboxylic acid, 1,4-(2-norbornene) dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo[2.2.2]octane-1,4-dicarboxylic acid, Bicyclo[2.2.2]octane-2,3-dicarboxylic acid, 2,5-di-side oxy-1,4-bicyclo[2.2.2]octane dicarboxylic acid, 1,3-adamantane dicarboxylic acid Acid, 4,8-di-side oxy-1,3-adamantane dicarboxylic acid, 2,6-spiro[3.3]heptane dicarboxylic acid, 1,3-adamantane diacetic acid, camphor acid, etc.

Aromatic dicarboxylic acids include: phthalic acid, isophthalic acid, terephthalic acid, 5-methyl isophthalic acid, 5-tertiary butyl isophthalic acid, 5-amino isophthalic acid Formic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid, tetramethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2, 6-Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracene dicarboxylic acid, 1,4-anthraquinone dicarboxylic acid, 2,5-biphenyl dicarboxylic acid, 4,4'- Biphenyl dicarboxylic acid, 1,5-biphenyl dicarboxylic acid, 4,4''-terphenyl dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenyl Ethane dicarboxylic acid, 4,4'-diphenylpropane dicarboxylic acid, 4,4'-diphenylhexafluoropropane dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4 '-Bibenzyl dicarboxylic acid, 4,4'-stilbene dicarboxylic acid, 4,4'-ethynyl dibenzoic acid, 4,4'-carbonyl dibenzoic acid, 4,4'-sulfonamide Dibenzoic acid, 4,4'-dithiodibenzoic acid, p-phenylene diacetic acid, 3,3'-p-phenylene dipropionic acid, 4-carboxycinnamic acid, p-phenylene diacrylic acid, 3 ,3'-[4,4'-(methylenebis-paraphenylene)]dipropionic acid, 4,4'-[4,4'-(oxydi-paraphenylene)]dipropylene Acid, 4,4'-[4,4'-(oxydi-p-phenylene)] dibutyric acid, (isopropylidene bis-p-phenylene dioxy) dibutyric acid, bis(p-phenylene) Carboxyphenyl) dimethyl silane and other dicarboxylic acids.

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

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

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

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

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

As for the organic solvent, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methylformamide , N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethyl Propane amide, N-methyl caprolactone, dimethyl sulfide, tetramethyl urea, pyridine, dimethyl sulfide, hexamethyl sulfide, γ-butyrolactone, isopropanol, methoxy Methyl amyl alcohol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl serosol, ethyl serosol, methyl Kiseloxu Acetate, Butyl Cerosu Acetate, Ethyl Cerosu Acetate, Butyl Carbitol, Ethyl Carbitol, Ethylene Glycol, Ethylene Glycol Monoacetate, Ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tertiary butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, two Propylene 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, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, acetic acid Methyl ester, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3 -Ethyl methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diethylene glycol two Methyl ether, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, etc. These organic solvents can be used alone or in mixture.

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

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

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

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

The method of making the above-mentioned polyamide acid into polyimide can be enumerated as follows: directly heating the polyamide acid solution to heat the imidization method; adding contact to the polyamide acid solution The catalyst of the medium is imidized. In addition, the conversion rate of polyimide from polyamide acid to polyimide should be 30% or more in consideration of improving the voltage retention rate. On the other hand, considering the whitening property, that is, the inhibition of the polymer The viewpoint of precipitation in the varnish is preferably 80% or less.

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

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

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

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

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

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

A compound that generates free radicals by heat is a compound that generates free radicals by heating above the decomposition temperature. Such radical thermal polymerization initiators include, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzyl peroxide, etc.) ), hydrogen peroxide (hydrogen peroxide, tertiary butyl hydroperoxide, cumene hydrogen peroxide, etc.), dialkyl peroxides (di tertiary butyl peroxide, diisopropyl peroxide, etc.) Benzene, dilaurel peroxide, etc.), peroxide ketals (dibutylperoxycyclohexane, etc.), alkyl peroxides (neodecanoic acid-tert-butyl peroxide, trimethyl peroxide Acetic acid-tert-butyl ester, 2-ethylcyclohexanoic acid-tert-pentyl peroxide, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azo Bisisobutyronitrile, and 2,2'-bis(2-hydroxyethyl)azobisisobutyronitrile, etc.). Such a radical thermal polymerization initiator can be used individually by 1 type or in combination of 2 or more types.

The compound that generates radicals by light is not particularly limited as long as it is a compound that initiates radical polymerization due to light irradiation. Such radical photopolymerization initiators include: benzophenone, Michler’s ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropyl Xanthone, 2,4-Diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'- Cumyl Propiophenone, 1-Hydroxycyclohexyl Phenone, Cumene Ether, Isobutyl Benzene Ether, 2,2-Diethoxyacetophenone, 2,2-Dimethoxy 2-phenylacetophenone, camphorquinone, benzoanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-𠰌line propane-1-one, 2- Benzyl-2-dimethylamino-1-(4-𠰌olinylphenyl)-butanone-1,4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopropyl Amyl ester, 4,4'-bis(tertiary butylperoxycarbonyl)benzophenone, 3,4,4'-tris(tertiary butylperoxycarbonyl)benzophenone, 2,4,6 -Trimethylbenzyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-tris, 2-(3' ,4'-Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-tris, 2-(2',4'-Dimethoxystyryl)-4, 6-bis(trichloromethyl)-s-tris, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-tris, 2-(4 '-Pentyloxystyryl)-4,6-bis(trichloromethyl)-s-tris, 4-[p-N,N-bis(ethoxycarbonylmethyl)]-2,6 -Bis(trichloromethyl)-s-trichloromethyl, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-trichloromethyl, 1,3-bis(trichloromethyl) Methyl)-5-(4'-methoxyphenyl)-s-tris, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminobenzene Vinyl) benzothiazole, 2-mercaptobenzothiazole (mercaptobenzothiazole), 3,3'-carbonyl bis(7-diethylamino coumarin), 2-(o-chlorophenyl)-4,4' ,5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(4-ethoxycarbonyl) Phenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole , 2,2'bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4, 6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 3-(2-methyl-2-dimethylaminopropyl)carbazone Oxazole, 3,6-bis(2-methyl-2-pyrolinylpropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis(5-2,4- Cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3, 3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetrakis(third hexylperoxycarbonyl)benzophenone, 3,3 '-Bis(methoxycarbonyl)-4,4'-bis(tert-butylperoxycarbonyl)benzophenone, 3,4'-bis(methoxycarbonyl)-4,3'-bis( Tertiary butylperoxycarbonyl)benzophenone, 4,4'-bis(methoxycarbonyl)-3,3'-bis(tertiary butylperoxycarbonyl)benzophenone, 2-(3 -Methyl-3H-benzothiazol-2-ylidene)-1-naphthalene-2-yl-ethanone, or 2-(3-methyl-1,3-benzothiazole-2(3H)-ylidene Group)-1-(2-benzyl)ethanone and the like. These compounds may be used alone, or two or more of them may be mixed and used.

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

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

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

As a solvent to improve the uniformity and smoothness of the coating film, for example, isopropanol, methoxymethylpentanol, methyl serosol, ethyl serosol, butyl serosol, methyl serosol Loxoacetate, butyl siloxe acetate, ethyl siloxe acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethyl acetate, butyl carbitol, ethyl carbitol, ethyl carbitol, ethyl carbitol, ethyl carbitol, ethyl carbitol, ethyl carbitol, ethyl carbitol, ethyl carbitol, ethyl carbitol Glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tertiary butyl ether, dipropylene glycol mono Methyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol mono Methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetic acid Ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl Ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, Propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethyl Oxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxy butyl propionate, 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-ethyl Ester, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy) propanol, n-propyl lactate, n-butyl lactate, isoamyl lactate, 2 -Ethyl-1-hexanol, etc. A plurality of these solvents may be mixed. When using these solvents, it is preferably 5 to 80% by mass of the total solvent contained in the liquid crystal alignment agent, and more preferably 20 to 60% by mass.

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

Examples of compounds that improve the uniformity of film thickness and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, EFTOP EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Megafac F171, F173, R-30 (manufactured by DIC Corporation), Fluorad FC430, FC431 (manufactured by 3M), AsahiGuard AG710 , Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC), etc. When these surfactants are used, the use ratio is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass relative to 100 parts by mass of the total amount of the polymer contained in the radical generating film forming composition.

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

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

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

[Free radical generating film and liquid crystal alignment film] The radical generating film of this embodiment can be obtained, for example, using the above-mentioned radical generating film forming composition. For example, after the radical generating film forming composition used in the present invention is applied to a substrate, it is dried and fired to obtain a cured film, and the cured film can be used as a radical generating film as it is. In addition, the cured film can be aligned by rubbing, polarizing or irradiating light of a specific wavelength, or ion beam processing. For the alignment film for PSA, the liquid crystal display element filled with liquid crystal can also be irradiated with UV.

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

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

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

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

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

When the alignment treatment is performed by performing the rubbing treatment in one direction, for example, while the rubbing roller wound with the rubbing cloth is rotated, the substrate is moved so that the rubbing cloth is brought into contact with the film. When using the photo-alignment method, the entire surface of the film can be irradiated with polarized UV of a specific wavelength and heated as needed to perform the alignment process.

The liquid crystal alignment film of this embodiment described above is obtained by the same method as the radical generation film except that a liquid crystal alignment agent is used instead of the radical generating film forming composition.

The substrate on which the radical generating film forming composition is applied is not particularly limited as long as it is a highly transparent substrate. Specific examples include: glass plates, polycarbonates, poly(meth)acrylates, polyethers, polyarylates, polyurethanes, polyethers, polyethers, polyether ketones, trimethyl Plastic boards such as pentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triacetyl cellulose, diacetyl cellulose, cellulose acetate butyrate, etc.

As the substrate on which the liquid crystal alignment film is applied, it is preferable to form a transparent electrode for driving liquid crystal on the above-mentioned substrate. The substrates that can be used for IPS-type liquid crystal display elements can also use standard IPS comb-shaped electrodes, PSA herringbone electrodes and other electrode patterns, and MVA and other protrusion patterns. In addition, in high-function devices such as TFT-type devices, a device such as a transistor is formed between an electrode for driving liquid crystal and a substrate.

When manufacturing a transmissive liquid crystal display element, the above-mentioned substrate is generally used, but when manufacturing a reflective liquid crystal display element, if it is a single-sided substrate, an opaque substrate such as a silicon wafer can also be used. At this time, the electrode formed on the substrate can also use a material such as aluminum that reflects light.

In addition, when rubbing the liquid crystal alignment film on the substrate on which the comb-teeth electrodes are formed, the electrical properties of the liquid crystal are used to select the rubbing direction, but when using liquid crystals with positive dielectric anisotropy, the rubbing direction should be the same as that of the comb teeth. The extending direction of the electrodes is approximately the same direction.

＜Liquid crystal cell＞ The liquid crystal cell of the present invention, for example, by using the above-mentioned method to form a free radical generating film on the substrate (second substrate) and a substrate with a liquid crystal alignment film attached electrode (first substrate) to generate free radicals The film and the liquid crystal alignment film are arranged so as to face each other, the spacer is sandwiched and fixed with a sealant, and a liquid crystal composition containing a liquid crystal and a radical polymerizable compound is injected and sealed. At this time, the size of the spacer used is usually 1~30μm, preferably 2~10μm. In addition, by setting the rubbing direction of the first substrate and the rubbing direction of the second substrate to be parallel, it can be used in IPS mode and FFS mode. If the rubbing direction is arranged orthogonally, it can be used in twisted nematic mode. . In addition, the IPS substrate, which is a comb-teeth electrode substrate used in the IPS (In-Plane Switching) mode, has a substrate, a plurality of linear electrodes formed on the substrate and arranged in a comb-like shape, and to cover the linear electrodes The way is to form a liquid crystal alignment film on the substrate. In addition, the FFS substrate used in the FFS (Frindge Field Switching) mode is a comb-tooth electrode substrate, which has a substrate, a surface electrode formed on the substrate, an insulating film formed on the surface electrode, and an insulating film formed on the insulating film. A plurality of linear electrodes in a comb-tooth shape, and a liquid crystal alignment film formed on the insulating film to cover the linear electrodes.

The method of injecting a liquid crystal composition containing a liquid crystal and a radical polymerizable compound is not particularly limited. Examples include: a vacuum method of injecting a mixture of the liquid crystal and the polymerizable compound after depressurizing the inside of the obtained liquid crystal cell; dripping The dropping method of sealing after containing the mixture of liquid crystal and polymerizable compound, etc.

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

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

式中，＊表示鍵結部位。R^b 表示碳數2~8之直鏈烷基，E表示選自單鍵、-O-、-NRc-、-S-、酯鍵及醯胺鍵之鍵結基。Rc表示氫原子、或碳數1~4之烷基。In addition, the polymerizable group of the radical polymerizable compound is preferably a polymerizable group selected from the following structures. [化13]

In the formula, * represents the bonding site. R ^b represents a linear alkyl group having 2 to 8 carbon atoms, and E represents a bonding group selected from a single bond, -O-, -NRc-, -S-, an ester bond, and an amide bond. Rc represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

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

The compound having a monofunctional radical polymerizable group is a compound having a reactive group capable of radical polymerization in the presence of an organic radical. Examples include: tert-butyl methacrylate, hexyl methacrylate, methyl Methacrylate monomers such as 2-ethylhexyl acrylate, nonyl methacrylate, lauryl methacrylate, n-octyl methacrylate, etc.; t-butyl acrylate, hexyl acrylate, 2-ethyl acrylate Acrylic monomers such as hexyl ester, nonyl acrylate, benzyl acrylate, lauryl acrylate, n-octyl acrylate; styrene, styrene derivatives (for example, ortho, meta, p-methoxystyrene, ortho, meta , P-tertiary butoxystyrene, ortho, meta, p-chloromethyl styrene, etc.), vinyl esters (for example, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl acetate, etc.), ethylene Base ketones (for example, vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, etc.), N-vinyl compounds (for example, N-vinylpyrrolidone, N-vinylpyrrole, N-vinyl Carbazole, N-vinyl indole, etc.), (meth)acrylic acid derivatives (for example, acrylonitrile, methacrylonitrile, acrylamide, isopropylacrylamide, methacrylamide, etc.), halogenated Vinyl monomers such as ethylene (for example, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachlorobutadiene, vinyl fluoride, etc.), but are not limited to these. These various radical polymerizable monomers may be used alone, or two or more of them may be used. In addition, these should be compatible with liquid crystals.

式(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-、-NRc-、-S-、酯鍵、及醯胺鍵之鍵結基。文中Rc表示氫原子或碳數1~4之烷基。In addition, the radically polymerizable compound is preferably a compound represented by the following formula (1). [化14]

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 selected from a single bond, -O-, -NRc-, -S-, ester bond, and 醯The bonding group of the amine bond. In the text, Rc represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms.

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 radically polymerizable compound represented by formula (1), where E is an ester bond (-C(=O)-O- or -OC(=O)-), it is easy to synthesize The viewpoints of compatibility, compatibility with liquid crystals, and polymerization reactivity are preferable. Specifically, a compound having the following structure is preferable, but it is not particularly limited. [化15]

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

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

The polymer obtained by polymerizing a radically polymerizable compound preferably has a Tg of 100°C or less.

In addition, liquid crystal generally refers to a substance in a state that shows the properties of both solid and liquid. Representative liquid crystal phases include nematic liquid crystal and smectic liquid crystal. The liquid crystals that can be used in the present invention are not particularly limited. To give one 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 radical polymerizable compound is introduced is provided with energy sufficient to cause the radical polymerizable compound to undergo a polymerization reaction. It can be implemented by heating or UV irradiation, for example, by polymerizing the radically polymerizable compound in situ to exhibit desired characteristics. Among them, the use of UV can make the alignment patterning. In addition, considering the viewpoint of the polymerization reaction in a short time, UV irradiation is preferable. In addition, when used in the twisted nematic mode, in addition to the above-mentioned liquid crystal composition, a chiral dopant can be introduced into the liquid crystal cell as necessary.

In addition, heating can also be performed during UV irradiation. The heating temperature during UV irradiation is preferably the temperature range where the introduced liquid crystal will exhibit liquid crystallinity, usually above 40°C, and it is better to heat before the temperature at which the liquid crystal changes into an isotropic phase.

Here, the UV irradiation wavelength during UV irradiation should be the wavelength with the best reaction quantum yield of the polymerizable compound to be reacted. The amount of UV irradiation is usually 0.01~30J/cm ² , preferably 10J/cm ² or less , The less the UV irradiation amount, the more the reduction in reliability caused by the destruction of the components constituting the liquid crystal display can be suppressed, and the tact in manufacturing can be improved by reducing the UV irradiation time, which is ideal.

In addition, it is preferable to perform heating during polymerization by heating only without UV irradiation, which is preferably a temperature range at which the polymerizable compound reacts and does not reach the decomposition temperature of the liquid crystal. Specifically, it is 100 to 150°C.

When the energy sufficient to cause the radical polymerizable compound to undergo a polymerization reaction is provided, it is preferably in an electric field-free state where no voltage is applied.

＜Liquid crystal display element＞ The liquid crystal cell obtained in this way can be used to produce a liquid crystal display element. For example, a reflective electrode, a transparent electrode, a λ/4 plate, a polarizing film, a color filter layer, etc. are arranged in the liquid crystal cell according to the usual method as needed, thereby making a reflective liquid crystal display element. In addition, a backlight, a polarizing plate, a λ/4 plate, a transparent electrode, a polarizing film, a color filter layer, etc. are arranged in the liquid crystal cell according to the usual method as needed, thereby making a transmissive liquid crystal display element. [Example]

NMP：N-甲基-2-吡咯烷酮、 GBL：γ-丁內酯、 BCS：丁基賽珞蘇Hereinafter, the present invention will be specifically explained using examples, but the present invention is not limited to these examples. The abbreviations and characteristics evaluation methods of the compounds used in the polymerization of the polymer and the preparation of the film forming composition are as follows. [化16]

NMP: N-Methyl-2-pyrrolidone, GBL: γ-butyrolactone, BCS: Butyl-Serosol

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

<Molecular weight measurement> The molecular weight system uses a normal temperature gel permeation chromatography (GPC) device (GPC-101) (manufactured by Showa Denko) and columns (KD-803, KD-805) (manufactured by Showa Denko) as follows Perform the measurement. Column temperature: 50℃ Eluent: N,N-dimethylformamide (for additives, lithium bromide monohydrate (LiBr･H ₂ O) 30mmol/L (liter)), phosphoric acid-anhydrous crystals (o-phosphoric acid) 30mmol/L, tetrahydrofuran (THF) 10mL/L) Flow rate: 1.0mL/min. Standard sample for calibration line production: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (Manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; approximately 12,000, 4,000, and 1,000) (manufactured by Polymer Laboratories).

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

<Polymer polymerization and preparation of free radical generating film forming composition> Synthesis example 1 Polymerization of TC-1, TC-2(50)/DA-1(50), DA-2(50) polyimide In a 100mL 4-necked flask equipped with a nitrogen inlet tube, an air cooling tube, and a mechanical stirrer, weigh out 1.62g (15.0mmol) of DA-1 and 4.96g (15.0mmol) of DA-2, and add 51.9g The NMP is stirred in a nitrogen atmosphere to completely dissolve it. After confirming the dissolution, 3.75 g (15.0 mmol) of TC-2 was added and reacted at 60°C for 3 hours under a nitrogen atmosphere. Return to room temperature again, add 2.64 g (13.5 mmol) of TC-1, and react at 40° C. for 12 hours under a nitrogen atmosphere. The polymerization viscosity was confirmed, and TC-1 was further added so that the polymerization viscosity became about 1000 mPa･s, and a polymerization solution with a polyamide acid concentration of 20% by mass was obtained. In a 200 mL Erlenmeyer flask equipped with a magnetic stirrer, weigh 60 g of the polyamide acid solution obtained above, and add 111.4 g of NMP to prepare a solution with a concentration of 7% by mass. While stirring, add 8.38 g of acetic anhydride ( 81.4 mmol), and 3.62 g (45.8 mmol) of pyridine, stirred at room temperature for 30 minutes, and then stirred at 55°C for 3 hours to react. After the completion of the reaction, the solution was returned to room temperature, and the reaction solution was poured into 500 mL of methanol while stirring to precipitate a solid. The solid was recovered by filtration, and the solid was further poured into 300 mL of methanol, stirred and washed for 30 minutes for a total of 2 times. After the solid was recovered by filtration and air-dried, it was dried in a vacuum oven at 60°C to obtain the number average molecular weight ( Polyimide powder (PI-1) with Mn) of 16,200, weight average molecular weight (Mw) of 35,200, and 59% of imidization rate.

Synthesis Example 2 Polymerization of TC-1, TC-2(50)/DA-2(100) polyimide Measure 9.91g (30.0mmol) of DA-2 in a 100mL 4-necked flask equipped with nitrogen introduction tube, air cooling tube, and mechanical stirrer, add 65.95g of NMP, and stir under nitrogen to make it complete Dissolve. After confirming the dissolution, 3.75 g (15.0 mmol) of TC-2 was added and reacted at 60°C for 3 hours under a nitrogen atmosphere. After returning to room temperature again, 2.82 g (14.4 mmol) of TC-1 was added and reacted at 40° C. for 12 hours under a nitrogen atmosphere. The polymerization viscosity was confirmed, and TC-1 was further added so that the polymerization viscosity became about 1000 mPa･s, and a polymerization solution with a polyamide acid concentration of 20% by mass was obtained. In a 200 mL Erlenmeyer flask equipped with a magnetic stirrer, weigh 70 g of the polyamide acid solution obtained above, and add 130.0 g of NMP to prepare a solution with a concentration of 7% by mass, and add 6.90 g of acetic anhydride while stirring. 67.5 mmol), and 2.96 g (37.4 mmol) of pyridine, stirred at room temperature for 30 minutes, and then stirred at 55°C for 3 hours to react. After the completion of the reaction, the solution was returned to room temperature, and the reaction solution was poured into 500 mL of methanol while stirring to precipitate a solid. The solid was recovered by filtration, and the solid was further poured into 300 mL of methanol, stirred and washed for 30 minutes for a total of 2 times. After the solid was recovered by filtration and air-dried, it was dried in a vacuum oven at 60°C to obtain an Mn of 18,300. Polyimide powder (PI-2) with an Mw of 38,900 and an imidization rate of 62%.

Preparation of free radical generating film forming composition AL-1 In a 50 mL Erlenmeyer flask equipped with a magnetic stirrer, weigh 2.0 g of the polyimide powder (PI-1) obtained in Synthesis Example 1, and add 18.0 g of NMP, and stir at 50°C to completely dissolve it. 6.7 g of NMP and 6.7 g of BCS were further added and stirred for 3 hours to obtain the radical generating film forming composition of the present invention: AL-1 (solid content: 6.0% by mass, NMP: 74% by mass, BCS : 20% by mass).

Preparation of free radical generating film forming composition AL-2 In a 50 mL Erlenmeyer flask equipped with a magnetic stirrer, measure 2.0 g of the polyimide powder (PI-2) obtained in Synthesis Example 2, and add 18.0 g of NMP, and stir at 50°C to completely dissolve it. 6.7 g of NMP and 6.7 g of BCS were further added and stirred for 3 hours to obtain the radical generating film forming composition of the present invention: AL-2 (solid content: 6.0% by mass, NMP: 74% by mass, BCS : 20% by mass).

Hereinafter, a method of manufacturing a liquid crystal cell for evaluating the alignment of liquid crystal is shown. First, prepare the substrate with electrodes. The substrate is a glass substrate with a size of 30mm×35mm and a thickness of 0.7mm. On the substrate, an IZO electrode with an entire surface pattern, which constitutes the counter electrode of the first layer, is formed. A SiN (silicon nitride) film formed by a CVD (chemical vapor deposition) method is formed as a second layer on the counter electrode of the first layer. The SiN film of the second layer has a thickness of 500 nm and functions as an interlayer insulating film. On the second layer of SiN film, a comb-shaped pixel electrode formed by patterning the IZO film as the third layer is arranged to form two pixels of a first pixel and a second pixel. The size of each pixel is 10 mm in the vertical direction and approximately 5 mm in the horizontal direction. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer. The pixel electrode of the third layer is the same as Figure 3 described in JP 2014-77845 (Japanese Laid Open Patent Gazette). It has an electrode element with a width of 3μm that is bent at an internal angle of 160° at the center and is separated by 6μm. A comb-tooth shape arranged in parallel at intervals, and one pixel has a first area and a second area with the line connecting the bent portions of the plurality of electrode elements as the boundary. When the first area and the second area of each pixel are compared, the formation directions of the electrode elements constituting the pixel electrodes are different. That is, when the rubbing direction of the liquid crystal alignment film described later is used as a reference, the first area of the pixel is formed so that the electrode element of the pixel electrode becomes an angle of +10° (clockwise), and the second area of the pixel is It is formed in such a way that the electrode elements of the pixel electrode have an angle of -10° (counterclockwise). That is, the first area and the second area of each pixel are in the direction of the rotation (in-plane switching) of the liquid crystal in the substrate surface induced by the voltage application between the pixel electrode and the counter electrode. It is constructed in the opposite direction. Hereinafter, it is referred to as an FFS substrate (first substrate). In addition, a glass substrate (hereinafter referred to as a second substrate) with an ITO film formed on the back surface and a columnar spacer having a height of 3.3 μm was prepared as a counter substrate. Then, the free radical generating film forming composition obtained by the aforementioned method or the liquid crystal alignment material SUNEVER SE-6414 manufactured by Nissan Chemical Co., Ltd. is filtered with a filter with a pore size of 1.0 μm, and then coated on the prepared by spin coating method. The first substrate and the second substrate are combined to form a film. Then, after drying on a hot plate at 80°C for 80 minutes, it was calcined at 220°C for 20 minutes to obtain a coating film with a film thickness of 100 nm. The polyimide film on the first substrate side is rubbed in the direction along the direction of the comb teeth, and the polyimide film on the second substrate side faces the second substrate and the first substrate. The rubbing treatment is performed in the direction orthogonal to the direction of the comb teeth of the comb teeth electrode of the first substrate at the time of placement. In addition, the cloth used in the rubbing treatment was rubbed with rayon cloth made by Yoshikawa Chemical Industry: YA-20R (roll diameter 120mm). Regardless of the substrate, the substrate coated with SE-6414 is rubbed at a rotation speed of 700 rpm, a moving speed of 30 mm/sec, and a pressing amount of 0.4 mm. The substrate coated with a radical generating film forming composition is moved at a rotation speed of 500 rpm. The friction treatment is performed under the conditions of a speed of 30mm/sec and a pressing amount of 0.2mm. After the rubbing treatment, ultrasonic irradiation was performed in pure water for 1 minute, and dried at 80°C for 10 minutes. After that, using the above-mentioned two types of substrates, the display element that is the object of the example was a combination of SE-6414 on the side of the first substrate and a radical generating film on the side of the second substrate. On the other hand, in the display element to be compared, a combination of both substrates using SE-6414, or a combination of using a radical generating film on the first substrate side and SE-6414 on the second substrate side . In addition, in each combination, the first substrate and the second substrate were combined in such a way that the rubbing directions of the second substrate were anti-parallel, leaving the liquid crystal injection port and sealing the surroundings to produce an empty cell with a cell gap of about 3.3 μm. After injecting a liquid crystal (with 2% by mass of the additive IDHex in MLC-3019 manufactured by Merck) into the empty cell under vacuum at room temperature, the injection port was sealed to produce an antiparallel-aligned liquid crystal cell. The obtained liquid crystal cell constitutes an FFS mode liquid crystal display element. After that, the obtained liquid crystal cell was heated at 120°C for 10 minutes, and UV-FL irradiation equipment manufactured by TOSHIBA LIGHTING & TECHNOLOGY was used to irradiate UV for 30 minutes without applying voltage (UV lamp: FLR40SUV32/A-1) , To obtain a liquid crystal display element.

＜Measurement of V-T curve and evaluation of drive threshold voltage and maximum brightness voltage＞ Set the white LED backlight and the brightness meter so that the optical axis is aligned. Between them, set the liquid crystal cell (liquid crystal display element) with the polarizing plate installed in such a way that the brightness is minimized. Apply the voltage at intervals of 1V until 8V, and measure The brightness under voltage is used to measure the VT curve. From the obtained V-T curve, the drive threshold voltage and the voltage value at which the brightness becomes the maximum are estimated. In addition, suppose that the transmission brightness of parallel polarized light (Parallel Nicol) is 100% through the liquid crystal cell without voltage applied, and the maximum transmission brightness of the V-T curve is compared and estimated as the maximum transmission rate.

<Measurement of response time (Ton, Toff)> In addition to the aforementioned measurement, an oscilloscope was used to measure the time change of the brightness when the voltage at the maximum brightness was applied and the time change of the brightness when the voltage returned to 0V, thereby measuring the response time Ton and Toff.

＜Evaluation of voltage holding ratio (VHR)＞ Apply an AC pulse voltage with offset voltage of 0V, amplitude of 2Vp-p, frequency of 0.6Hz, and voltage application time of 60μs to the liquid crystal cell in a hot air circulation oven at 60℃, and measure the voltage immediately after the voltage application is stopped and the voltage after 1667ms (positive and negative) Both), and calculate the ratio of the voltage before and after the application to determine the voltage holding ratio (VHR). In addition, the measuring device used VHR-1 manufactured by TOYO Corporation. The higher the VHR, the better.

<Image retention evaluation> A rectangular wave voltage (60 Hz) of maximum brightness was applied to the first area of each pixel of each liquid crystal cell, and no voltage was applied to the second area of the other pixel. The liquid crystal cell was driven at 60°C for 168 hours and matured. The brightness of the first area of the pixel after the maturation and the second area of the pixel are compared to evaluate the image retention. When the brightness ratio is below 1.10, it is defined as "good", and when it is greater than 1.10, it is defined as "bad".

[Table 1] 1st board side (FFS board side) 2nd substrate side (back ITO substrate side) Example 1 SE-6414 AL-1 Example 2 SE-6414 AL-2 Comparative example 1 SE-6414 SE-6414 Comparative example 2 AL-1 SE-6414 Comparative example 3 AL-2 SE-6414

<Drive threshold voltage, maximum brightness voltage, maximum transmittance, response time>

[Table 2] Drive threshold voltage V _Th [V] Maximum brightness voltage V _max [V] Maximum transmittance [%] Response time Ton [ms] Response time Toff [ms] Example 1 1.4 4.1 82 13.7 13.4 Example 2 1.3 4 80 13.8 13.2 Comparative example 1 1.4 4.1 72 13.1 13.3 Comparative example 2 1.2 3.6 75 17.6 15.9 Comparative example 3 1 3.3 78 18.3 18.7

＜VHR, image retention evaluation＞

[table 3] Voltage holding rate VHR [%] Image retention (brightness ratio) Example 1 82.3 Good (1.06) Example 2 84.7 Good (1.04) Comparative example 1 79.9 Good (1.07) Comparative example 2 67.9 Bad (1.14) Comparative example 3 73 Bad (1.12)

Comparative example 1 is the characteristics of the conventional FFS display element using a strong anchoring alignment film, Comparative Examples 2 and 3 are the characteristics of the FFS display element using a weak anchoring film on the first substrate side, and Examples 1 and 2 are The present invention has characteristics of an FFS display element using a weak anchor film on the second substrate side. That is, in Examples 1 and 2, the anchoring energy of the liquid crystal alignment film (weak anchor film) on the side of the counter substrate (second substrate) is higher than that of the liquid crystal alignment film on the side of the comb-shaped electrode substrate (first substrate). Set energy is small. In Comparative Examples 2 and 3 of the structure reported so far (the case where a weak anchor film is used on the first substrate side), the threshold voltage and the maximum brightness voltage are shifted to a low voltage, and the transmittance is also improved along with this. On the other hand, a tendency to deteriorate the response time was observed. It is considered that this is a result of the decrease in the anchoring energy on the first substrate side. It can be seen that the anchoring energy of Comparative Example 3 is lower than that of Comparative Example 2. As a result, the transmittance is improved, but The response time tends to deteriorate. On the other hand, it can be seen that in the case of the present invention using a weak anchor film on the second substrate side, the threshold voltage and maximum brightness voltage are unchanged, but the transmittance is increased, and the response time is almost the same as that of the conventional FFS of Comparative Example 1. The same characteristics of the display components. It is known that the response time of the transverse electric field method is _{inversely proportional to (driving voltage V-driving threshold voltage V Th} ). Regarding Examples 1 and 2, the driving threshold voltage V _Th and the maximum brightness voltage V _max are unchanged from the previous configuration, so It is presumed that the structure of the present invention will not have a large impact on the response time. In addition, it can be seen that in the configuration of the conventional weakly anchored FFS display device of Comparative Examples 2 and 3, the VHR is deteriorated and the image retention characteristic is worse than that of the conventional strong anchored FFS display device, but it becomes the weak anchor of the present invention. With the fixed structure, VHR has been improved, and along with this, image retention has also become better. [Industrial Utilization]

According to the present invention, it is possible to provide a transverse electric field liquid crystal display element capable of achieving high image retention characteristics (VHR, image retention characteristics), high backlight light transmittance, and fast response speed. In addition, the liquid crystal display element obtained by the method of the present invention is useful as a liquid crystal display element of a lateral electric field driving method.

1: Horizontal electric field liquid crystal display element 2: Comb electrode substrate 2a: Substrate 2b: Wire electrode 2c: Liquid crystal alignment film 2d: substrate 2e: Surface electrode 2f: insulating film 2g: wire electrode 2h: Liquid crystal alignment film 3: LCD 4: Opposite substrate 4a: Liquid crystal alignment film 4b: Substrate L: Power line

[Fig. 1] A schematic cross-sectional view showing an example of the horizontal electric field liquid crystal display element of the present invention. Fig. 2 is a schematic cross-sectional view showing another example of the horizontal electric field liquid crystal display element of the present invention.

Claims (16)

A transverse electric field liquid crystal display element, which has a comb-shaped electrode substrate provided with a liquid crystal alignment film and a counter substrate provided with a liquid crystal alignment film. The two liquid crystal alignment films face each other, and between the liquid crystal alignment film and the liquid crystal alignment film Filled with liquid crystal between; Its characteristics are: The anchoring energy of the liquid crystal alignment film on the side of the counter substrate is smaller than the anchoring energy of the liquid crystal alignment film on the side of the comb-tooth electrode substrate. The transverse electric field liquid crystal display element of claim 1, wherein the liquid crystal alignment film on the side of the comb-shaped electrode substrate and the liquid crystal alignment film on the side of the counter substrate are both liquid crystal alignment films subjected to uniaxial alignment treatment, and only the liquid crystal alignment film The liquid crystal alignment film on the opposite substrate side is weakly anchored. The horizontal electric field liquid crystal display element of claim 1 or 2, wherein the comb-shaped electrode substrate is an IPS substrate or an FFS substrate. The transverse electric field liquid crystal display element of claim 1 or 2, wherein the liquid crystal alignment film on the counter substrate side is in a state where the liquid crystal composition containing the liquid crystal and the radical polymerizable compound is in contact with the radical generating film, It is obtained by subjecting this radically polymerizable compound to a polymerization reaction. The horizontal electric field liquid crystal display element of claim 4, wherein the radical generating film is a film obtained by immobilizing an organic group that induces radical polymerization. The transverse electric field liquid crystal display element of claim 4, wherein the radical generating film is composed of a polymer containing an organic group that induces radical polymerization. The horizontal electric field liquid crystal display element of claim 6, wherein the polymer containing an organic group that induces radical polymerization is selected from a polyamine component obtained by using a diamine containing a diamine containing an organic group that induces radical polymerization. At least one polymer selected from the group consisting of an imine precursor, polyimine, polyurea, and polyamide. Such as the transverse electric field liquid crystal display element of claim 6, wherein the organic radicals that induce radical polymerization are represented by the following structures [X-1]~[X-18], [W], [Y], or [Z] Organic base

In the formulas [X-1]~[X-18], * represents the bonding site, S ₁ and S ₂ each independently represent -O-, -NR-, or -S-, and R represents a hydrogen atom or carbon An alkyl group with 1 to 10 carbon numbers. Among the alkyl groups with carbon number 1 to 10, the -CH ₂ -group of a part of the alkyl group with carbon numbers 2 to 10 can also be replaced with an oxygen atom. However, S ₂ R or NR _{When the -CH 2} -group of a part of the alkyl group is replaced with an oxygen atom, the oxygen atom is not directly bonded to S ₂ or N; R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a carbon Alkyl group of 1~4;

In formulas [W], [Y], and [Z], * represents the bonding site, and Ar represents selected from phenylene, naphthylene, and phenylene which may also have organic groups and/or halogen atoms as substituents In the aromatic hydrocarbon group in the group consisting of phenyl, R ⁹ and R ¹⁰ each independently represent an alkyl group with 1 to 10 carbons or an alkoxy group with 1 to 10 carbons. When R ⁹ and R ¹⁰ are alkyl groups, The ends may also be bonded to each other to form a ring structure; Q represents any of the following structures;

In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O-, or -S-, R each independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, * represents a bonding site; S ³ represents Single bond, -O-, -NR- or -S-, R represents a hydrogen atom or an alkyl group with 1 to 4 carbons; R ¹² represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbons or a carbon number 1. ~10 Alkoxy. The horizontal electric field liquid crystal display element of claim 7, wherein the diamine containing an organic group that induces radical polymerization is a diamine having a structure represented by the following general formula (6) or the following general formula (7);

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 with 1 to 20 carbon atoms, the extension 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-, divalent carbocyclic ring, and divalent heterocyclic ring. In addition, also It can be replaced with any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other as a condition; R ⁸ Represents a radical polymerization reactive group represented by a formula selected from the following formulas [X-1]~[X-18];

In the formulas [X-1]~[X-18], * represents the bonding site, S ₁ and S ₂ each independently represent -O-, -NR-, or -S-, and R represents a hydrogen atom or carbon An alkyl group with 1 to 10 carbon numbers. Among the alkyl groups with carbon number 1 to 10, the -CH ₂ -group of a part of the alkyl group with carbon numbers 2 to 10 can also be replaced with an oxygen atom. However, S ₂ R or NR _{When the -CH 2} -group of a part of the alkyl group is replaced with an oxygen atom, the oxygen atom is not directly bonded to S ₂ or N; R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a carbon Alkyl group of 1~4;

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 unsubstituted or substituted by fluorine atoms, carbon number 1-20 alkylene Group, any _{one or more of -CH 2} -or -CF ₂ -of the alkylene group may be independently substituted with a group selected from -CH=CH-, divalent carbocyclic ring, and divalent heterocyclic ring In addition, it is also possible to substitute any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH are not adjacent to each other as a condition to replace them with these groups ; J is an organic group selected from the following formulas [W], [Y] and [Z];

Formula [W], [Y], and [Z], * represents a bonding site with the T _2, Ar represents an organic group selected from the group consisting of may, and / or a halogen atom as a substituent of the phenylene group, a naphthyl group extension , And the aromatic hydrocarbon group in the group consisting of biphenyl, R ⁹ and R ¹⁰ each independently represent an alkyl group with 1 to 10 carbons or an alkoxy group with 1 to 10 carbons; Q represents any of the following structures ；

In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O-, or -S-, R each independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, * represents a bonding site; R ¹² represents Hydrogen atom, halogen atom, C1-C10 alkyl group or C1-C10 alkoxy group; S ³ represents a single bond, -O-, -NR-, or -S-, R represents a hydrogen atom or carbon Number of alkyl groups from 1 to 4. The transverse electric field liquid crystal display element of claim 4, wherein at least one of the radically polymerizable compounds is a compound having a polymerizable reactive group in one molecule that is compatible with liquid crystal. The transverse electric field liquid crystal display element of claim 10, wherein the polymerizable reactive group of the radical polymerizable compound is selected from the following structures;

In the formula, * represents the bonding site; R ^b represents a linear alkyl group with 2 to 8 carbons, and E represents a bond selected from single bond, -O-, -NRc-, -S-, ester bond and amide bond Bonding group; Rc represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. The lateral electric field liquid crystal display element of claim 4, wherein the radically polymerizable compound is a radically polymerizable compound whose Tg of a polymer obtained by polymerizing the radically polymerizable compound is 100° C. or lower. A method for manufacturing a transverse electric field liquid crystal cell includes the following steps: Prepare a comb-shaped electrode substrate with a first substrate with a liquid crystal alignment film, and a counter substrate with a second substrate with a radical generating film; Fabricating a unit cell in such a way that the radical generating film on the second substrate faces the first substrate; and A liquid crystal composition containing a liquid crystal and a radical polymerizable compound is filled between the first substrate and the second substrate. According to claim 13, the method for manufacturing a transverse electric field liquid crystal cell, wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment. The method for manufacturing a transverse electric field liquid crystal cell of claim 14, wherein the liquid crystal alignment film with uniaxial alignment is a liquid crystal alignment film for horizontal alignment. The method for manufacturing a transverse electric field liquid crystal cell according to any one of claims 13 to 15, wherein the comb-shaped electrode substrate is an IPS substrate or an FFS substrate.

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