TW202244052A - Liquid-crystal composition, liquid-crystal display element production method, and liquid-crystal display element - Google Patents

Abstract

A liquid-crystal display element production method comprising a step for causing, in a state where a liquid-crystal composition containing a liquid crystal and a radically polymerizable compound represented by formula (A) is in contact with a radical-generating film, said radically polymerizable compound to undergo polymerization. (In formula (A), M represents a polymerizable group that can undergo radical polymerization, T represents an organic group represented by formula (B), and n represents an integer of 1-2.) (In formula (B), Cy represents a non-aromatic cyclic group having a 6-20 membered ring.).

Description

Liquid crystal composition, method for manufacturing liquid crystal display element, and liquid crystal display element

The present invention relates to a manufacturing method of a liquid crystal display element capable of manufacturing a weak anchor film by a method that is inexpensive and does not include complicated steps, and employs a technique of stabilizing a liquid crystal layer obtained by using a polymer, and a liquid crystal for low-voltage driving A display element, and a liquid crystal composition and a radically polymerizable compound that can be used therefor.

In recent years, liquid crystal display elements have been widely used in monitors of mobile phones, computers, and televisions. Liquid crystal display elements have the characteristics of thinness, light weight, and low power consumption. It is expected to be further applied in VR (Virtual Reality, Virtual Reality) and ultra-high-definition displays in the future. Various display modes such as TN (Twisted Nematic), IPS (In-Plane Switching), and VA (Vertical Alignment) have been proposed for the display mode of liquid crystal displays. Both use liquid crystal derivatized films (liquid crystal alignment films) in the desired alignment state.

In particular, tablet PCs, smart phones, smart TVs and other products with touch panels prefer the IPS mode, which is less prone to display confusion even when touched. In recent years, considering the improvement of contrast ratio and viewing angle characteristics, FFS has also been adopted. (Boundary Electric Field Switching, Frindge Field Switching) is a liquid crystal display element that uses non-contact technology of photo-alignment.

However, compared with IPS, FFS has a higher manufacturing cost of the substrate and has the problem of occurrence of a display defect unique to the FFS mode called Vcom shift. Also, with regard to photo-alignment, compared with the rubbing method, there are benefits of increasing the size of the device that can be manufactured and greatly improving the display characteristics, but there are still problems in the principle of photo-alignment (if it is a decomposed type, it comes from the decomposition product) If the display is poor, if it is the heterosexual type, it is due to the branding caused by insufficient alignment, etc.). In order to solve these problems, currently, various efforts have been made for manufacturers of liquid crystal display elements and manufacturers of liquid crystal alignment films.

On the other hand, in recent years, it has been proposed to use the IPS mode called weak anchoring. It is reported that by using this method, compared with the conventional IPS mode, the contrast can be improved, and the low voltage driving can be greatly reduced (refer to the patent document 1).

Specifically, a liquid crystal alignment film with strong anchoring energy is used on one side of the substrate, and a treatment to completely eliminate the alignment regulation force of the liquid crystal is applied to the substrate side with electrodes on the side where one of the transverse electric fields is generated, and they are used A method for manufacturing an IPS mode liquid crystal display element.

In recent years, there have been proposals to create a weakly anchored state and a weakly anchored IPS mode using thick polymer brushes (see Patent Document 2). According to this technology, the contrast ratio is greatly improved and the driving voltage is greatly reduced.

On the other hand, there is a problem that the response speed is significantly lowered especially when the voltage is OFF. It is caused by the reduction of driving voltage, which makes the response of the liquid crystal relatively time-consuming due to the influence of the weaker electric field compared with the usual driving method, and the extremely small anchoring force of the alignment film.

As a method for solving this problem, a method of performing weak anchoring only on the pixel electrodes has been proposed (see Patent Document 3). According to reports, this can take into account both brightness improvement and response speed. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent No. 4053530 [Patent Document 2] Japanese Unexamined Patent Publication No. 2013-231757 [Patent Document 3] Japanese Patent Laid-Open No. 2017-211566

[Problem to be solved by the invention]

By weakly anchoring only the electrode of the IPS comb electrode, it is possible to suppress the response speed delay during driving, but in order to only make the electrode weakly anchored, it is necessary to prepare for difficulties such as coating different materials in very small areas. technology, it is considered that there are major issues in actual industrialization.

Some people have studied the use of different methods to narrow the cell gap to improve the response speed. In general, a liquid crystal display element tends to have a faster response speed as the cell gap becomes narrower. However, there is a problem that the transmittance decreases. In order to solve this problem, a method of using a liquid crystal having a large birefringence difference (Δn) is exemplified. The product (retardation) of the cell gap D and Δn can be set to 300nm~400nm (measurement wavelength: 550nm), so that the decrease in transmittance can be solved. However, when Δn is large, basically, not only this parameter changes, but also parameters such as Δε (dielectric constant anisotropy) and elastic coefficient change, and it is considered that the basic physical properties of liquid crystals will change significantly. For example, in the case of weakly anchored alignment, it is considered that a case where liquid crystals are aligned in a vertical direction may also occur. Therefore, it is an important issue to obtain stable weak anchoring characteristics even if the parameters such as Δn and Δε vary.

If such a technical problem can be solved, it is considered to have a significant cost advantage for panel manufacturers, and it is also considered to be beneficial in battery power consumption reduction and image quality improvement.

The present invention aims to solve the above-mentioned problems, and aims to provide a method for manufacturing a liquid crystal display element, which can stably produce a weakly anchored transverse electric field liquid crystal display element without generating a pretilt angle when the cell gap is narrowed, and can manufacture a liquid crystal display element with Simultaneously achieving low drive voltage and high-speed response when the voltage is off, and can reduce burn-in, can achieve high backlight transmittance at low temperature and low-voltage drive transverse electric field liquid crystal display element, and provide the liquid crystal display element, and These liquid crystal compositions and radical polymerizable compounds can be used. [How to solve the problem]

As a result, the inventors of the present invention have diligently studied to solve the above-mentioned problems, found that the above-mentioned problems can be solved, and completed the present invention having the following gist.

式(A)中，M表示可自由基聚合之聚合性基，S表示單鍵、或亦可插入了鍵結基之碳數1~6之飽和烴基，T表示下式(B)表示之有機基，n為1~2之整數；n為2時，2個T可相同也可不同；惟n為2時，S表示亦可插入了鍵結基之碳數1~6之飽和烴基， [化2]

式(B)中，＊代表鍵結部位；X係選自單鍵、醚鍵、酯鍵、醯胺鍵、胺甲酸酯鍵、脲鍵、硫醚鍵、-Si(R ₁)(R ₂)-(R ₁及R ₂各自獨立地表示鍵結於Si之烷基)、-Si(R ₃)(R ₄)-O-(R ₃及R ₄各自獨立地表示鍵結於Si之烷基)、及-N(R ₅)-(R ₅表示鍵結於N之氫原子或烷基)之鍵結基，Cy表示6~20員環之非芳香族之環狀基。 [2]如[1]之液晶顯示元件之製造方法，其中，該式(B)中，Cy之該6~20員環之非芳香族之環狀基中之環為6~20員環之環狀烷。 [3]如[1]或[2]之液晶顯示元件之製造方法，其中，該式(A)中之M係選自以下之結構， [化3]

式中，＊代表鍵結部位；R ^b表示碳數2~8之直鏈烷基，E表示選自單鍵、-O-、-NR ^c-、-S-、酯鍵及醯胺鍵中之鍵結基；R ^c表示氫原子、或碳數1~4之烷基。 [4]如[1]~[3]中任一項之液晶顯示元件之製造方法，其中，該自由基發生膜係經單軸配向處理之自由基發生膜。 [5] 如[1]~[4]中任一項之液晶顯示元件之製造方法，其中，該聚合反應之步驟係於無電場條件下進行。 [6] 如[1]~[5]中任一項之液晶顯示元件之製造方法，其中，該自由基發生膜係將誘發自由基聚合之有機基固定化而成之膜。 [7] 如[1]~[5]中任一項之液晶顯示元件之製造方法，其中，該自由基發生膜係藉由將含有具有發生自由基之有機基之化合物與聚合物之組成物予以塗佈、及硬化而形成膜，以將該發生自由基之有機基固定於該膜中而獲得。 [8] 如[1]~[5]中任一項之液晶顯示元件之製造方法，其中，該自由基發生膜係由含有誘發自由基聚合之有機基之聚合物構成。 [9] 如[8]之液晶顯示元件之製造方法，其中，該含有誘發自由基聚合之有機基之聚合物，係選自使用包含含有誘發自由基聚合之有機基之二胺的二胺成分而獲得之聚醯亞胺前驅物、聚醯亞胺、聚脲及聚醯胺中之至少一種聚合物。 [10] 如[9]之液晶顯示元件之製造方法，其中，該誘發自由基聚合之有機基係下式[X-1]~[X-18]、[W]、[Y]、或[Z]表示之有機基， [化4]

式[X-1]~[X-18]中，＊代表鍵結部位，S ₁、及S ₂各自獨立地表示-O-、-NR ^a-(R ^a表示氫原子、或碳數1~10之烷基)、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-CH ₂-基之一部分也可被氧原子取代，惟S ₂R或NR ^a中，前述烷基之-CH ₂-基之一部分被氧原子取代時，該氧原子不直接鍵結於S ₂或N)； R ₁、及R ₂各自獨立地表示氫原子、鹵素原子、或碳數1~4之烷基， [化5]

式[W]、[Y]、及[Z]中，＊代表鍵結部位，Ar表示選自由也可具有有機基及/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，R ⁹及R ¹⁰各自獨立地表示碳數1~10之烷基或碳數1~10之烷氧基，R ⁹與R ¹⁰為烷基時，亦能以末端互相鍵結並形成環結構；Q表示下列中任一結構， [化6]

式中，R ¹¹表示-CH ₂-、-NR ^a-(R ^a表示氫原子或碳數1~4之烷基)、-O-、或-S-，R各自獨立地表示氫原子或碳數1~4之烷基，＊代表鍵結部位；S ³表示單鍵、-O-、-NR ^b-(R ^b表示氫原子或碳數1~14之烷基)、或-S-；R ¹²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。 [11] 如[9]或[10]之液晶顯示元件之製造方法，其中，該含有誘發自由基聚合之有機基之二胺係下式(6)、下式(7)、或下式(7’)表示之二胺， [化7]

式(6)中，R ⁶表示單鍵、-CH ₂-、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH ₂O-、-N(CH ₃)-、-CON(CH ₃)-、或-N(CH ₃)CO-， R ⁷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-CH ₂-或-CF ₂-中之一者以上也可各自獨立地被選自-CH＝CH-、二價之碳環、及二價之雜環中之基取代，再者，也能以如下列舉之任意基亦即-O-、-COO-、-OCO-、-NHCO-、-CONH-、或-NH-互不相鄰為條件，被該等基取代； R ⁸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8]

式[X-1]~[X-18]中，＊代表鍵結部位，S ₁、及S ₂各自獨立地表示-O-、-NR ^a-(R ^a表示氫原子、或碳數1~10之烷基)、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-CH ₂-基之一部分也可被氧原子取代；惟S ₂R或NR ^a中，該烷基之-CH ₂-基之一部分被氧原子取代時，該氧原子不直接鍵結於S ₂或N)；R ₁、及R ₂各自獨立地表示氫原子、鹵素原子、或碳數1~4之烷基， [化9]

[化10]

式(7)及(7’)中，T ₁及T ₂各自獨立地為單鍵、-O-、-S-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH ₂O-、-N(CH ₃)-、-CON(CH ₃)-、或-N(CH ₃)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-CH ₂-或-CF ₂-中之一者以上亦可各自獨立地被選自-CH＝CH-、二價之碳環、及二價之雜環中之基取代，再者，亦能以如下列舉之任意基亦即-O-、-COO-、-OCO-、-NHCO-、-CONH-、或-NH-互不相鄰為條件，被該等基取代， E為單鍵、-O-、-C(CH ₃) ₂-、-NH-、-CO-、-NHCO-、-COO-、-(CH ₂) _m-、-SO ₂-、-O-(CH ₂) _m-O-、-O-C(CH ₃) ₂-、-CO-(CH ₂) _m-、-NH-(CH ₂) _m-、-SO ₂-(CH ₂) _m-、-CONH-(CH ₂) _m-、-CONH-(CH ₂) _m-NHCO-、或-COO-(CH ₂) _m-OCO-，m為1~8之整數， J係選自下式[W]、[Y]及[Z]之式表示之有機基， [化11]

式[W]、[Y]、及[Z]中，＊表示和T ₂之鍵結部位，Ar表示選自由也可具有有機基及/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，R ⁹及R ¹⁰各自獨立地表示碳數1~10之烷基或碳數1~10之烷氧基，Q表示下列中任一結構， [化12]

式中，R ¹¹表示-CH ₂-、-NR ^a-(R ^a表示氫原子或碳數1~4之烷基)、-O-、或-S-，R各自獨立地表示氫原子或碳數1~4之烷基，＊代表鍵結部位； S ³表示單鍵、-O-、-NR ^b-(R ^b表示氫原子或碳數1~14之烷基)、或-S-； R ¹²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； 式(7’)中，q各自獨立地為0或1，至少1個q為1，p表示1~2之整數； T ₁、T ₂、S、J、E、及q有多數個存在時，多數個T ₁、T ₂、S、J、E、及q彼此可相同也可不同。 [12] 如[1]~[11]中任一項之液晶顯示元件之製造方法，包括下列步驟： 準備具有該自由基發生膜之第一基板、及亦可具有自由基發生膜之第二基板， 以該第一基板中之該自由基發生膜面對該第二基板之方式，將該第一基板與該第二基板予以對向配置， 於該第一基板與該第二基板之間填充該液晶組成物，及 進行前述聚合反應。 [13] 如[12]之液晶顯示元件之製造方法，其中，該第二基板係不具有自由基發生膜之第二基板。 [14] 如[12]之液晶顯示元件之製造方法，其中，該第二基板係塗佈了具有單軸配向性之液晶配向膜之基板。 [15] 如[14]之液晶顯示元件之製造方法，其中，該具有單軸配向性之液晶配向膜為水平配向用之液晶配向膜。 [16] 如[12]~[15]中任一項之液晶顯示元件之製造方法，其中，該第一基板及該第二基板中之任一者為具有梳齒電極之基板。 [17] 一種液晶組成物，其特徵為含有液晶及下式(A)表示之自由基聚合性化合物， [化13]

式(A)中，M表示可自由基聚合之聚合性基，S表示單鍵、或亦可插入了鍵結基之碳數1~6之飽和烴基，T表示下式(B)表示之有機基，n為1~2之整數；n為2時，2個T可相同也可不同；惟n為2時，S表示亦可插入了鍵結基之碳數1~6之飽和烴基， [化14]

式(B)中，＊代表鍵結部位；X係選自單鍵、醚鍵、酯鍵、醯胺鍵、胺甲酸酯鍵、脲鍵、硫醚鍵、-Si(R ₁)(R ₂)-(R ₁及R ₂各自獨立地表示鍵結於Si之烷基)、-Si(R ₃)(R ₄)-O-(R ₃及R ₄各自獨立地表示鍵結於Si之烷基)、及-N(R ₅)-(R ₅表示鍵結於N之氫原子或烷基)之鍵結基，Cy表示6~20員環之非芳香族之環狀基。 [18] 如[17]之液晶組成物，其中，該式(B)中，Cy之該6~20員環之非芳香族之環狀基中之環為6~20員環之環狀烷。 [19] 如[17]或[18]之液晶組成物，其中，該式(A)中之M係選自以下之結構， [化15]

式中，＊代表鍵結部位；R ^b表示碳數2~8之直鏈烷基，E表示選自單鍵、-O-、-NR ^c-、-S-、酯鍵及醯胺鍵之鍵結基；R ^c表示氫原子、或碳數1~4之烷基。 [20] 一種液晶顯示元件，其特徵為： 具有第一基板、對向於該第一基板而配置之第二基板、及填充於該第一基板與該第二基板之間之液晶， 係於使含有該液晶及下式(A)表示之自由基聚合性化合物之液晶組成物接觸具有自由基發生膜之該第一基板之該自由基發生膜之狀態下，使該自由基聚合性化合物聚合反應而成， [化16]

式(A)中，M表示可自由基聚合之聚合性基，S表示單鍵、或亦可插入了鍵結基之碳數1~6之飽和烴基，T表示下式(B)表示之有機基，n為1~2之整數；n為2時，2個T可相同也可不同；惟n為2時，S表示亦可插入了鍵結基之碳數1~6之飽和烴基， [化17]

式(B)中，＊代表鍵結部位；X係選自單鍵、醚鍵、酯鍵、醯胺鍵、胺甲酸酯鍵、脲鍵、硫醚鍵、-Si(R ₁)(R ₂)-(R ₁及R ₂各自獨立地表示鍵結於Si之烷基)、-Si(R ₃)(R ₄)-O-(R ₃及R ₄各自獨立地表示鍵結於Si之烷基)、及-N(R ₅)-(R ₅表示鍵結於N之氫原子或烷基)之鍵結基，Cy表示6~20員環之非芳香族之環狀基。 [21] 如[20]之液晶顯示元件，其中，該第一基板及該第二基板中之任一者係具有梳齒電極之基板。 [22] 如[20]或[21]之液晶顯示元件，係低電壓驅動橫電場液晶顯示元件。 [23] 一種自由基聚合性化合物，其特徵為以下式(A)表示， [化18]

式(A)中，M表示丙烯醯氧基或甲基丙烯醯氧基，S表示亦可插入了鍵結基之碳數1~6之飽和烴基，T表示下式(B)表示之有機基，n為1~2之整數；n為2時，2個T可相同也可不同， [化19]

式(B)中，＊代表鍵結部位；X係選自醚鍵、酯鍵、醯胺鍵、胺甲酸酯鍵、脲鍵、硫醚鍵、-Si(R ₁)(R ₂)-(R ₁及R ₂各自獨立地表示鍵結於Si之烷基)、-Si(R ₃)(R ₄)-O-(R ₃及R ₄各自獨立地表示鍵結於Si之烷基)、及-N(R ₅)-(R ₅表示鍵結於N之氫原子或烷基)之鍵結基，Cy表示12~20員環之非芳香族之環狀基。 [24] 如[23]之自由基聚合性化合物，以下式(C)表示， [化20]

式(C)中，R ₃及R ₄各自獨立地表示碳數1~6之烷基，R ₆表示碳數1~6之伸烷基，R ₇表示氫原子或甲基，p表示1~9之整數。 [發明之效果] That is, the present invention includes the following matters. [1] A method of manufacturing a liquid crystal display device, comprising: allowing a radical polymerizable compound to be reacted in a state where a liquid crystal composition containing a liquid crystal and a radical polymerizable compound represented by the following formula (A) is brought into contact with a radical generating film. The steps of the polymerization reaction, [Chem. 1]

In the formula (A), M represents a polymerizable group capable of free radical polymerization, S represents a single bond, or a saturated hydrocarbon group with 1 to 6 carbon atoms that can also be inserted into a bonding group, and T represents an organic compound represented by the following formula (B). base, n is an integer from 1 to 2; when n is 2, the two Ts can be the same or different; but when n is 2, S means that a saturated hydrocarbon group with 1 to 6 carbon atoms of the bonding group can also be inserted, [ chemical 2]

In formula (B), * represents the bonding site; X is selected from single bond, ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, -Si(R ₁ )(R ₂ )-(R ₁ and R ₂ each independently represent an alkyl group bonded to Si), -Si(R ₃ )(R ₄ )-O-(R ₃ and R ₄ each independently represent an alkyl group bonded to Si Alkyl), and -N(R ₅ )-(R ₅ represents a hydrogen atom or an alkyl group bonded to N), and Cy represents a non-aromatic cyclic group with 6 to 20 membered rings. [2] The method for producing a liquid crystal display device as described in [1], wherein, in the formula (B), the ring in the non-aromatic cyclic group of the 6-20-membered ring of Cy is a 6-20-membered ring Cycloalkane. [3] The method for producing a liquid crystal display element according to [1] or [2], wherein M in the formula (A) is a structure selected from the following, [Chem. 3]

In the formula, * represents the bonding site; R ^b represents a straight-chain alkyl group with 2 to 8 carbons, and E represents a group selected from single bonds, -O-, -NR ^c -, -S-, ester bonds and amide bonds. A bonding group; R ^c represents a hydrogen atom, or an alkyl group with 1 to 4 carbons. [4] The method for manufacturing a liquid crystal display element according to any one of [1] to [3], wherein the radical generating film is a radical generating film subjected to uniaxial alignment treatment. [5] The method for manufacturing a liquid crystal display element according to any one of [1] to [4], wherein the step of the polymerization reaction is performed under no electric field conditions. [6] The method for producing a liquid crystal display element according to any one of [1] to [5], wherein the radical generating film is a film obtained by immobilizing an organic group that induces radical polymerization. [7] The method for producing a liquid crystal display device according to any one of [1] to [5], wherein the radical generating film is a composition composed of a compound containing an organic radical generating radical and a polymer It is obtained by applying and hardening to form a film to fix the radical-generating organic radical in the film. [8] The method for producing a liquid crystal display device according to any one of [1] to [5], wherein the radical generating film is composed of a polymer containing an organic group that induces radical polymerization. [9] The method for producing a liquid crystal display device according to [8], wherein the polymer containing an organic group that induces radical polymerization is selected from diamine components containing a diamine containing an organic group that induces radical polymerization. The obtained polyimide precursor, polyimide, polyurea and at least one polymer of polyamide. [10] The method for manufacturing a liquid crystal display device as described in [9], wherein the organic group inducing radical polymerization is the following formula [X-1]~[X-18], [W], [Y], or [ Z] represents the organic group, [chemical 4]

In the formulas [X-1]~[X-18], * represents the bonding site, S ₁ and S ₂ each independently represent -O-, -NR ^a -(R ^a represents a hydrogen atom, or carbon number 1~ 10 alkyl), or -S-, R represents a hydrogen atom, or an alkyl group with 1 to 10 carbons (among the aforementioned alkyl groups with 1 to 10 carbons, -CH ₂ for an alkyl group with 2 to 10 carbons Part of the - group can also be substituted by an oxygen atom, but in S ₂ R or NR ^a , when a part of the -CH ₂ - group of the aforementioned alkyl group is replaced by 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 an alkyl group with 1 to 4 carbons, [化5]

In the formulas [W], [Y], and [Z], * represents a bonding site, and Ar represents a group selected from phenylene, naphthylene, and extension groups that may also have organic groups and/or halogen atoms as substituents. In the aromatic hydrocarbon group in the group formed by phenyl, ^R9 and R10 each independently represent an alkyl group with 1 to ¹⁰ carbons or an alkoxy group with 1 to ¹⁰ carbons, when ^R9 and R10 are alkyl groups, It can also be bonded to each other at the ends to form a ring structure; Q represents any of the following structures, [化6]

In the formula, R ¹¹ represents -CH ₂ -, -NR ^a - (R ^a represents a hydrogen atom or an alkyl group with 1 to 4 carbons), -O-, or -S-, each R independently represents a hydrogen atom or a carbon An alkyl group with a number of 1~4, * stands for a bonding site; S ³ stands for a single bond, -O-, -NR ^b - (R ^b stands for a hydrogen atom or an alkyl group with a carbon number of 1~14), 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. [11] The method for producing a liquid crystal display element according to [9] or [10], wherein the diamine containing an organic group that induces radical polymerization is represented by the following formula (6), the following formula (7), or the following formula ( 7') represents the diamine, [Chemical 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 C1-20 alkylene group, the alkene group Any one or more of -CH ₂ - or -CF ₂ - in the alkyl group may also be independently substituted by a group selected from -CH═CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and then Or, it can also be substituted by any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other; R ⁸ represents a free radical polymerization reactive group represented by a formula selected from the following formulas [X-1] to [X-18], [Chem. 8]

In the formulas [X-1]~[X-18], * represents the bonding site, S ₁ and S ₂ each independently represent -O-, -NR ^a -(R ^a represents a hydrogen atom, or carbon number 1~ 10 alkyl), or -S-, R represents a hydrogen atom, or an alkyl group with 1 to 10 carbons (among the aforementioned alkyl groups with 1 to 10 carbons, -CH ₂ for an alkyl group with 2 to 10 carbons Part of the - group can also be substituted by an oxygen atom; but in S ₂ R or NR ^a , when a part of the -CH ₂ - group of the alkyl group is replaced by 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 an alkyl group with 1 to 4 carbons, [Chemical 9]

[chemical 10]

In formulas ( ₇ ) and ( ₇ '), T1 and T2 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 fluorine atom-substituted carbon number 1 ~20 alkylene groups, any one or more of -CH ₂ - or -CF ₂ - in the alkylene group can also be independently selected from -CH═CH-, divalent carbocycles, and divalent The substituents in the valent heterocyclic ring can also be replaced by any of the following groups, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other As a condition, to be substituted by such groups, E is a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -NHCO-, -COO-, -(CH ₂ ) _m - , -SO ₂ -, -O-(CH ₂ ) _m -O-, -OC(CH ₃ ) ₂ -, -CO-(CH ₂ ) _m -, -NH-(CH ₂ ) _m -, -SO ₂ -(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -NHCO-, or -COO-(CH ₂ ) _m -OCO-, m is an integer from 1 to 8 , J is an organic group selected from the following formulas [W], [Y] and [Z], [Chem. 11]

_In the formulas [W], [Y], and [Z], * represents the bonding position with T2, and Ar represents a group selected from phenylene and naphthylene groups that may also have organic groups and/or halogen atoms as substituents. , and the aromatic hydrocarbon group in the group consisting of extended biphenyl groups, 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, and Q represents any of the following structure, [Chem. 12]

In the formula, R ¹¹ represents -CH ₂ -, -NR ^a - (R ^a represents a hydrogen atom or an alkyl group with 1 to 4 carbons), -O-, or -S-, each R independently represents a hydrogen atom or a carbon An alkyl group with a number of 1~4, * represents a bonding site; S ³ represents a single bond, -O-, -NR ^b - (R ^b represents a hydrogen atom or an alkyl group with a carbon number of 1 ~ 14), 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; in formula (7'), q are each independently 0 or 1, and at least one q is 1 , p represents an integer from 1 to 2; when there are a plurality of T ₁ , T ₂ , S, J, E, and q, the plurality of T ₁ , T ₂ , S, J, E, and q can be the same as each other or can be different. [12] The method for manufacturing a liquid crystal display element according to any one of [1] to [11], comprising the following steps: preparing a first substrate having the radical generating film, and a second substrate that may also have the free radical generating film a substrate, with the free radical generating film in the first substrate facing the second substrate, the first substrate and the second substrate are arranged facing each other, between the first substrate and the second substrate The liquid crystal composition is filled, and the aforementioned polymerization reaction is performed. [13] The method of manufacturing a liquid crystal display element according to [12], wherein the second substrate is a second substrate that does not have a radical generating film. [14] The method for manufacturing a liquid crystal display element according to [12], wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment. [15] The method for manufacturing a liquid crystal display element according to [14], wherein the liquid crystal alignment film having uniaxial alignment is a liquid crystal alignment film for horizontal alignment. [16] The method for manufacturing a liquid crystal display element according to any one of [12] to [15], wherein either one of the first substrate and the second substrate is a substrate having comb-shaped electrodes. [17] A liquid crystal composition characterized by containing a liquid crystal and a radically polymerizable compound represented by the following formula (A), [Chem. 13]

In the formula (A), M represents a polymerizable group capable of free radical polymerization, S represents a single bond, or a saturated hydrocarbon group with 1 to 6 carbon atoms that can also be inserted into a bonding group, and T represents an organic compound represented by the following formula (B). base, n is an integer from 1 to 2; when n is 2, the two Ts can be the same or different; but when n is 2, S means that a saturated hydrocarbon group with 1 to 6 carbon atoms of the bonding group can also be inserted, [ Chemical 14]

In formula (B), * represents the bonding site; X is selected from single bond, ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, -Si(R ₁ )(R ₂ )-(R ₁ and R ₂ each independently represent an alkyl group bonded to Si), -Si(R ₃ )(R ₄ )-O-(R ₃ and R ₄ each independently represent an alkyl group bonded to Si Alkyl), and -N(R ₅ )-(R ₅ represents a hydrogen atom or an alkyl group bonded to N), and Cy represents a non-aromatic cyclic group with 6 to 20 membered rings. [18] The liquid crystal composition according to [17], wherein, in the formula (B), the ring in the non-aromatic cyclic group of the 6-20-membered ring of Cy is a cyclic alkane with a 6-20-membered ring . [19] The liquid crystal composition according to [17] or [18], wherein M in the formula (A) is selected from the following structures, [Chem. 15]

In the formula, * represents the bonding site; R ^b represents a straight-chain alkyl group with 2 to 8 carbon atoms, and E represents a group selected from single bonds, -O-, -NR ^c -, -S-, ester bonds and amide bonds. Bonding group; R ^c represents a hydrogen atom or an alkyl group with 1 to 4 carbons. [20] A liquid crystal display element, characterized by: having a first substrate, a second substrate disposed opposite to the first substrate, and a liquid crystal filled between the first substrate and the second substrate; The radical polymerizable compound is polymerized in a state where the liquid crystal composition containing the liquid crystal and the radical polymerizable compound represented by the following formula (A) is in contact with the radical generating film of the first substrate having the radical generating film reacted, [Chem. 16]

In the formula (A), M represents a polymerizable group capable of free radical polymerization, S represents a single bond, or a saturated hydrocarbon group with 1 to 6 carbon atoms that can also be inserted into a bonding group, and T represents an organic compound represented by the following formula (B). base, n is an integer from 1 to 2; when n is 2, the two Ts can be the same or different; but when n is 2, S means that a saturated hydrocarbon group with 1 to 6 carbon atoms of the bonding group can also be inserted, [ Chemical 17]

In formula (B), * represents the bonding site; X is selected from single bond, ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, -Si(R ₁ )(R ₂ )-(R ₁ and R ₂ each independently represent an alkyl group bonded to Si), -Si(R ₃ )(R ₄ )-O-(R ₃ and R ₄ each independently represent an alkyl group bonded to Si Alkyl), and -N(R ₅ )-(R ₅ represents a hydrogen atom or an alkyl group bonded to N), and Cy represents a non-aromatic cyclic group with 6 to 20 membered rings. [21] The liquid crystal display element according to [20], wherein either one of the first substrate and the second substrate is a substrate having comb-shaped electrodes. [22] The liquid crystal display element as described in [20] or [21] is a liquid crystal display element driven by a low voltage transverse electric field. [23] A radically polymerizable compound characterized by being represented by the following formula (A), [Chem. 18]

In formula (A), M represents acryloxy or methacryloxy, S represents a saturated hydrocarbon group with 1 to 6 carbons that may also be inserted into a bonding group, and T represents an organic group represented by the following formula (B) , n is an integer from 1 to 2; when n is 2, the two Ts can be the same or different, [Chem. 19]

In formula (B), * represents the bonding site; X is selected from ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, -Si(R ₁ )(R ₂ )- (R ₁ and R ₂ each independently represent an alkyl group bonded to Si), -Si(R ₃ )(R ₄ )-O- (R ₃ and R ₄ each independently represent an alkyl group bonded to Si) , and -N(R ₅ )-(R ₅ represents a hydrogen atom or an alkyl group bonded to N), and Cy represents a non-aromatic cyclic group with 12 to 20 membered rings. [24] The radically polymerizable compound as described in [23], represented by the following formula (C), [Chem. 20]

In formula (C), R ₃ and R ₄ each independently represent an alkyl group with 1 to 6 carbons, R ₆ represents an alkylene group with 1 to 6 carbons, R ₇ represents a hydrogen atom or a methyl group, and p represents 1 to 6 Integer of 9. [Effect of Invention]

According to the present invention, a method for manufacturing a liquid crystal display element can be provided, which can stably produce a weakly anchored transverse electric field liquid crystal display element without generating a pretilt angle when the cell gap is narrowed, and can simultaneously achieve a low driving voltage. And when the voltage is off, the response speed is fast, and it is not easy to cause burn-in. It can achieve high backlight transmittance and low-voltage driving transverse electric field liquid crystal display element at low temperature, and can provide the liquid crystal display element and the liquid crystal that can be used in such composition, and a radically polymerizable compound.

The present invention utilizes an additive capable of suppressing the development of a pretilt angle accompanying the formation of a weak anchor film, etc., and can stably manufacture a high-reliability weak anchor transverse electric field liquid crystal display element even if the crystal cell gap is narrowed (radical polymerization of a specific structure) compound). For example, it is a method of manufacturing a weakly anchored transverse electric field liquid crystal display element, including the following steps: preparing a substrate between the first substrate or the second substrate with the free radical generating film, and the second substrate or the first substrate with the liquid crystal alignment film having a unit cell of a liquid crystal composition containing liquid crystal and a radically polymerizable compound having a specific structure; and imparting sufficient energy to the aforementioned unit cell to polymerize the aforementioned radically polymerizable compound. Preferably, it is a method for manufacturing a liquid crystal cell, comprising the following steps: preparing a first substrate or a second substrate with a free radical generating film aligned by rubbing or photo-alignment, and a liquid crystal alignment film without a free radical generating film The second substrate or the first substrate; making a unit cell in the way that each substrate faces each other; and filling the liquid crystal composition containing liquid crystal and a free radical polymerizable compound with a specific structure between the first substrate and the second substrate. For example, it is a method of manufacturing a low-voltage drive transverse electric field liquid crystal display element. One of the substrates has an alignment-treated free radical generating film, the other substrate has a uniaxial alignment-treated liquid crystal alignment film, and one of the substrates has a Comb-tooth electrodes for driving liquid crystals.

In the present invention, "weak anchoring film" means that the liquid crystal molecules have absolutely no alignment regulation force in the in-plane direction, or even if there is, it is weaker than the intermolecular force between liquid crystals. Directional uniaxially aligned film. Also, the weakly anchored membrane is not limited to a solid membrane, but also includes a liquid membrane covering a solid surface. In general, liquid crystal display devices align liquid crystals by pairing a film that regulates the alignment of liquid crystal molecules, that is, a liquid crystal alignment film. However, liquid crystals can also be aligned when this weak anchor film is used in pairs with a liquid crystal alignment film. The reason is that the alignment regulation force of the liquid crystal alignment film is also transmitted to the thickness direction of the liquid crystal layer through the intermolecular force of the liquid crystal molecules, and as a result, the liquid crystal molecules close to the weak anchor film are also aligned. Therefore, when the liquid crystal alignment film is used for horizontal alignment, the horizontal alignment state can be achieved in the entire liquid crystal cell. Horizontal alignment refers to the state in which the long axes of liquid crystal molecules are roughly aligned parallel to the surface of the liquid crystal alignment film. Slanted alignment of several degrees is also included in the category of horizontal alignment.

The applicant of this application has proposed a method for manufacturing a zero-surface anchoring film, which includes providing a method for polymerizing the above-mentioned free-radical polymerizable compound in a state where a liquid crystal composition containing liquid crystal and a free-radical polymerizable compound is in contact with a free-radical generating film. The step of sufficient energy (refer to claim 1 of International Publication No. 2019/004433). [0077] to [0086] of International Publication No. 2019/004433 exemplify radically polymerizable compounds used in this proposal.

The inventors of the present application utilize the technology proposed above to stably fabricate a weakly anchored transverse electric field liquid crystal display element without causing a pretilt angle during narrowing of the cell gap, and to simultaneously achieve low driving voltage and off voltage. The response speed is still fast, and in addition, it can still achieve high backlight transmittance and low-voltage driving transverse electric field liquid crystal display elements at low temperatures, and strive to study. As a result, it was found that by using a radically polymerizable compound with a specific structure among the radically polymerizable compounds, it is possible to stably fabricate a weakly anchored transverse electric field liquid crystal display device without causing a pretilt angle under narrowed cell gaps, and that Manufacture a horizontal electric field liquid crystal display element that can achieve low driving voltage and fast response speed when the voltage is off, and can still achieve high backlight transmittance and low voltage driving at low temperature.

Here, the radically polymerizable compound of a specific structure is represented by following formula (A).

式(A)中，M表示可自由基聚合之聚合性基，S表示單鍵、或亦可插入了鍵結基之碳數1~6之飽和烴基，T表示下式(B)表示之有機基，n為1~2之整數。n為2時，2個T可相同也可不同。惟n為2時，S表示亦可插入了鍵結基之碳數1~6之飽和烴基。 [化22]

式(B)中，＊代表鍵結部位。X為選自單鍵、醚鍵、酯鍵、醯胺鍵、胺甲酸酯鍵、脲鍵、硫醚鍵、-Si(R ₁)(R ₂)-(R ₁及R ₂各自獨立地表示鍵結於Si之烷基。)、-Si(R ₃)(R ₄)-O-(R ₃及R ₄各自獨立地表示鍵結於Si之烷基。)、及-N(R ₅)-(R ₅表示鍵結於N之氫原子或烷基。)之鍵結基，Cy表示6~20員環之非芳香族之環狀基。 [chem 21]

In the formula (A), M represents a polymerizable group capable of free radical polymerization, S represents a single bond, or a saturated hydrocarbon group with 1 to 6 carbon atoms that can also be inserted into a bonding group, and T represents an organic compound represented by the following formula (B). Base, n is an integer from 1 to 2. When n is 2, two Ts may be the same or different. However, when n is 2, S represents a saturated hydrocarbon group with 1 to 6 carbon atoms that may also be inserted into a bonding group. [chem 22]

In formula (B), * represents a bonding site. X is selected from a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, a thioether bond, -Si(R ₁ )(R ₂ )-(R ₁ and R ₂ are each independently represents an alkyl group bonded to Si.), -Si(R ₃ )(R ₄ )-O-(R ₃ and R ₄ each independently represent an alkyl group bonded to Si.), and -N(R ₅ )-(R ₅ represents a hydrogen atom or an alkyl group bonded to N.), and Cy represents a non-aromatic cyclic group with 6 to 20 membered rings.

The manufacturing method of the liquid crystal display device of the present invention includes the step of polymerizing the radical polymerizable compound in the state where the liquid crystal composition containing the liquid crystal and the radical polymerizable compound represented by the formula (A) is brought into contact with the radical generating film . The inventors of the present invention speculate that in this step, the surface of the radical generating membrane is changed by the polymerization reaction of the radical polymerizable compound utilizing the radical generated by the radical generating membrane to obtain a weakly anchored membrane. However, it is difficult to determine whether the change of the surface of the radical generating membrane caused by this step is a change of the radical generating membrane itself or a change caused by the formation of a polymerized layer of the radical polymerizable compound on the radical generating membrane. Therefore, it is not yet possible to specify the result obtained in this step.

By implementing the above steps, the present invention can stably fabricate a weakly anchored transverse electric field liquid crystal display element without pretilt angle under narrow cell gap, and can simultaneously achieve low driving voltage and response when the voltage is off The speed is accelerated, and in addition, even at low temperature, it can still achieve high backlight transmittance and low-voltage drive transverse electric field liquid crystal display element. How the radically polymerizable compound represented by the formula (A) contributes to this phenomenon is considered as follows by the present inventors. M of the radically polymerizable compound represented by formula (A) contributes to radical polymerization of the radically polymerizable compound. Therefore, a weakly anchored film can be formed, and a lower driving voltage can be achieved. In addition, the inventors speculate that the Cy (representing a non-aromatic cyclic group of a 6-20-membered ring) of the radically polymerizable compound represented by formula (A) suppresses the occurrence of pretilt angle, improves the response speed, and improves the imprinting , and high backlight transmittance at low temperature and low voltage drive burden play an important role. Also, the inventors of the present case speculate that: in formula (A), by introducing a base of a certain size between M and Cy (S in formula (A), X in formula (B)), the response can be faster Speed, improved burn-in, and further, even if the driving temperature drops, it can still make the backlight transmittance better and can be driven at low voltage. In addition, in this specification, a narrow cell gap refers to a cell gap of 3.5 μm or less.

[Free radical generating film-forming composition] The composition for forming a radical generating membrane used in the present invention contains a polymer and a radical capable of generating radicals in terms of its components. In this case, the composition may contain a polymer to which a radical-generating radical is bonded, or may be a composition having a compound having a radical-generating radical and a polymer serving as a base resin. By applying and curing such a composition to form a film, a radical generating film in which radicals capable of generating radicals are immobilized in the film can be obtained. The radical capable of generating radicals is preferably an organic radical that induces radical polymerization.

式[X-1]~[X-18]中，＊代表鍵結部位，S ₁、及S ₂各自獨立地表示-O-、-NR ^a-(R ^a表示氫原子、或碳數1~10之烷基。)、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-CH ₂-基之一部分也可被氧原子取代。惟S ₂R或NR ^a中，前述烷基之-CH ₂-基之一部分被氧原子取代時，前述氧原子不直接鍵結於S ₂或N)。R ₁、及R ₂各自獨立地表示氫原子、鹵素原子、或碳數1~4之烷基。 [化24]

式[W]、[Y]、及[Z]中，＊代表鍵結部位，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，R ⁹及R ¹⁰各自獨立地表示碳數1~10之烷基或碳數1~10之烷氧基，R ⁹與R ¹⁰為烷基時，亦能以末端互相鍵結並形成環結構。Q表示下列中任一結構。 [化25]

式中，R ¹¹表示-CH ₂-、-NR ^a-(R ^a表示氫原子或碳數1~4之烷基。)、-O-、或-S-，R各自獨立地表示氫原子或碳數1~4之烷基，＊代表鍵結部位。)。S ³表示單鍵、-O-、-NR ^b-(R ^b表示氫原子或碳數1~14之烷基。)、或-S-。R ¹²表示氫原子、鹵素原子、碳數1~10之烷基或碳數1~10之烷氧基。 Examples of such organic groups that induce radical polymerization include organic groups represented by the following formulas [X-1] to [X-18], [W], [Y], and [Z]. [chem 23]

In the formulas [X-1]~[X-18], * represents the bonding site, S ₁ and S ₂ each independently represent -O-, -NR ^a -(R ^a represents a hydrogen atom, or carbon number 1~ 10 alkyl.), or -S-, R represents a hydrogen atom, or an alkyl group with 1 to 10 carbons (among the aforementioned alkyl groups with 1 to 10 carbons, -CH for an alkyl group with 2 to 10 carbons A part of the ₂ -group can also be substituted by an oxygen atom. But in S ₂ R or NR ^a , when a part of the -CH ₂ - group of the aforementioned alkyl group is substituted by 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. [chem 24]

In the formulas [W], [Y], and [Z], * represents a bonding site, and Ar represents a phenylene group, a naphthylene group, and an extended chain group that may also have an organic group and/or a halogen atom as a substituent. In the aromatic hydrocarbon group in the group formed by phenyl, ^R9 and R10 each independently represent an alkyl group with 1 to ¹⁰ carbons or an alkoxy group with 1 to ¹⁰ carbons, when ^R9 and R10 are alkyl groups, It is also possible to bond each other at the ends to form a ring structure. Q represents any one of the following structures. [chem 25]

In the formula, R ¹¹ represents -CH ₂ -, -NR ^a - (R ^a represents a hydrogen atom or an alkyl group with 1 to 4 carbons.), -O-, or -S-, and R each independently represents a hydrogen atom or An alkyl group with 1 to 4 carbons, * represents the bonding site. ). S ³ represents a single bond, -O-, -NR ^b - (R ^b represents a hydrogen atom or an alkyl group having 1 to 14 carbons.), 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.

The polymer is preferably selected from the group consisting of polyimide precursors, polyimides, polyureas, polyamides, polyacrylates, polymethacrylates, and polyorganosiloxanes. At least one polymer is preferred.

In order to obtain the free radical generating film used in the present invention, when using a polymer having an organic group that induces the aforementioned free radical polymerization, when obtaining a polymer having a radical capable of generating free radicals, use , acrylic group, vinyl group, allyl group, coumarin group, styryl group and cinnamon group in the photoreactive side chain of at least one monomer, the side chain has the ability to decompose and generate free radicals due to ultraviolet radiation It is preferable to manufacture the monomer of the site as a monomer component. On the other hand, considering the spontaneous polymerization of the free radical-generating monomer itself, it will become an unstable compound. Therefore, in consideration of the ease of synthesis, it is preferable to use a polymerization derived from a diamine having a free radical generating site. Preferably, polyimide precursors such as polyamic acid and polyamic acid ester, polyimide, polyurea, polyamide, etc.

式(6)中，R ⁶表示單鍵、-CH ₂-、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH ₂O-、-N(CH ₃)-、-CON(CH ₃)-、或-N(CH ₃)CO-， R ⁷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-CH ₂-或-CF ₂-中之一者以上也可各自獨立地被選自-CH＝CH-、二價之碳環、及二價之雜環之基取代，再者，亦能以下列列舉之任一基亦即-O-、-COO-、-OCO-、-NHCO-、-CONH-、或-NH-互不相鄰為條件，被該等基取代； R ⁸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27]

式[X-1]~[X-18]中，＊代表鍵結部位，S ₁、及S ₂各自獨立地表示-O-、-NR ^a-(R ^a表示氫原子、或碳數1~10之烷基。)、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-CH ₂-基之一部分也可被氧原子取代。惟S ₂R或NR ^a中，前述烷基之-CH ₂-基之一部分被氧原子取代時，前述氧原子不直接鍵結於S ₂或N)。R ₁、及R ₂各自獨立地表示氫原子、鹵素原子、或碳數1~4之烷基。 The polymer containing an organic group that induces free radical polymerization is preferably a polyimide precursor, polyimide, polyurea, and At least one polymer of polyamide is preferred. Diamines containing such organic groups that induce free radical polymerization, specifically, for example: diamines that have side chains that generate free radicals and can be polymerized, can include diamines represented by the following formula (6), but are not limited thereto . [chem 26]

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 C1-20 alkylene group, the alkene group Any one or more of -CH ₂ - or -CF ₂ - in the alkyl group may also be independently substituted by a group selected from -CH═CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and , can also be substituted by any of the following groups, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH-, on the condition that they are not adjacent to each other; R ⁸ represents a radical polymerization reactive group represented by a formula selected from the following formulas [X-1] to [X-18]. [chem 27]

In the formulas [X-1]~[X-18], * represents the bonding site, S ₁ and S ₂ each independently represent -O-, -NR ^a -(R ^a represents a hydrogen atom, or carbon number 1~ 10 alkyl.), or -S-, R represents a hydrogen atom, or an alkyl group with 1 to 10 carbons (among the aforementioned alkyl groups with 1 to 10 carbons, -CH for an alkyl group with 2 to 10 carbons A part of the ₂ -group can also be substituted by an oxygen atom. But in S ₂ R or NR ^a , when a part of the -CH ₂ - group of the aforementioned alkyl group is substituted by 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.

In formula (6), the bonding positions of the two amine groups (-NH ₂ ) are not limited. Specifically, the 2,3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 position, 3,5 position. Among them, the 2,4 position, the 2,5 position, or the 3,5 position are preferable from the viewpoint of reactivity when synthesizing polyamic acid. Considering the ease of synthesizing diamines, the 2,4 positions or the 3,5 positions are more ideal.

式中，J ¹係選自單鍵、-O-、-COO-、-NHCO-、及-NH-之鍵結基，J ²表示單鍵、或非取代或經氟原子取代之碳數1~20之伸烷基。 For diamines having at least one photoreactive group selected from the group consisting of methacrylic, acrylic, vinyl, allyl, coumarin, styryl, and cinnamyl, Specifically, the following compounds are listed, but not limited thereto. [chem 28]

In the formula, J1 is ^a bonding group selected from a single bond, -O-, -COO-, -NHCO-, and -NH-, and J2 represents a single bond, or a carbon number ¹ that is unsubstituted or substituted by a fluorine atom ~20 alkylene groups.

[化30]

式(7)及(7’)中，T ₁及T ₂各自獨立地為單鍵、-O-、-S-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH ₂O-、-N(CH ₃)-、-CON(CH ₃)-、或-N(CH ₃)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-CH ₂-或-CF ₂-中之任一者以上亦可各自獨立地被選自-CH＝CH-、二價之碳環、及二價之雜環中之基取代，再者，亦能以下列列舉之任一基亦即-O-、-COO-、-OCO-、-NHCO-、-CONH-、或-NH-互不相鄰為條件，被該等基取代， E為單鍵、-O-、-C(CH ₃) ₂-、-NH-、-CO-、-NHCO-、-COO-、-(CH ₂) _m-、-SO ₂-、-O-(CH ₂) _m-O-、-O-C(CH ₃) ₂-、-CO-(CH ₂) _m-、-NH-(CH ₂) _m-、-SO ₂-(CH ₂) _m-、-CONH-(CH ₂) _m-、-CONH-(CH ₂) _m-NHCO-、或-COO-(CH ₂) _m-OCO-，m為1~8之整數， J係選自下式[W]、[Y]及[Z]中之式表示之有機基， [化31]

式[W]、[Y]、及[Z]中，＊表示和T ₂之鍵結部位，Ar表示具有選自由也可具有有機基及/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，R ⁹及R ¹⁰各自獨立地表示碳數1~10之烷基或碳數1~10之烷氧基，Q表示下列中任一結構。 [化32]

式中，R ¹¹表示-CH ₂-、-NR ^a-(R ^a表示氫原子或碳數1~4之烷基。)、-O-、或-S-，R各自獨立地表示氫原子或碳數1~4之烷基，＊代表鍵結部位。S ³表示單鍵、-O-、-NR ^b-(R ^b表示氫原子或碳數1~14之烷基。)、或-S-。R ¹²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。))式(7’)中，q各自獨立地為0或1，至少1個q為1，p表示1~2之整數。T ₁、T ₂、S、J、E、及q有多數個存在時，多數個T ₁、T ₂、S、J、E、及q彼此可相同也可不同。 Among the diamines containing organic groups that induce radical polymerization, diamines that have a side chain that is decomposed by ultraviolet radiation to generate free radicals include diamines represented by the following formula (7) or formula (7') , but not limited to this. [chem 29]

[chem 30]

In formulas ( ₇ ) and ( ₇ '), T1 and T2 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 fluorine atom-substituted carbon number 1 ~20 alkylene groups, any one or more of -CH ₂ - or -CF ₂ - in the alkylene group can also be independently selected from -CH═CH-, divalent carbocycles, and divalent The base in the valent heterocyclic ring is substituted, moreover, any of the following bases can also be used, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are mutually exclusive Ortho is a condition, it is substituted by such groups, E is a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -NHCO-, -COO-, -(CH ₂ ) _m -, -SO ₂ -, -O-(CH ₂ ) _m -O-, -OC(CH ₃ ) ₂ -, -CO-(CH ₂ ) _m -, -NH-(CH ₂ ) _m -, -SO ₂ -(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -NHCO-, or -COO-(CH ₂ ) _m -OCO-, m is between 1 and 8 An integer, J is an organic group selected from the following formulas [W], [Y] and [Z], [Chemical 31]

_In the formulas [W], [Y], and [Z], * represents the bonding position with T2, and Ar represents a phenylene group or a naphthylene group selected from an organic group and/or a halogen atom as a substituent. group, and the aromatic hydrocarbon group in the group consisting of extended biphenyl groups, ^R9 and R10 each independently represent an alkyl group with 1 to ¹⁰ carbons or an alkoxy group with 1 to 10 carbons, and Q represents any of the following a structure. [chem 32]

In the formula, R ¹¹ represents -CH ₂ -, -NR ^a - (R ^a represents a hydrogen atom or an alkyl group with 1 to 4 carbons.), -O-, or -S-, and R each independently represents a hydrogen atom or An alkyl group with 1 to 4 carbons, * represents the bonding site. S ³ represents a single bond, -O-, -NR ^b - (R ^b represents a hydrogen atom or an alkyl group having 1 to 14 carbons.), 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. )) In formula (7'), q is each independently 0 or 1, at least one q is 1, and p represents an integer of 1-2. When there are a plurality of T ₁ , T ₂ , S, J, E, and q, the plurality of T ₁ , T ₂ , S, J, E, and q may be the same as or different from each other.

In the above formula (7), the bonding positions of the two amine groups (-NH ₂ ) are not limited. Specifically, the 2,3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 position, 3,5 position. Among them, the 2,4 position, the 2,5 position, or the 3,5 position are preferable from the viewpoint of reactivity when synthesizing polyamic acid.

式中，n為2~8之整數。 In particular, considering the ease of synthesis, high versatility, and characteristics, the structure represented by the following formula is the most ideal, but not limited thereto. [chem 33]

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

In the above formula (7′), the bonding position between the amino group (—NH ₂ ) on the benzene ring and the bonding group E is not limited. Considering the availability of raw materials, the alignment grade when it is made into a liquid crystal display element, and the black brightness, the alignment is better.

式中，n為2~8之整數，E為單鍵、-O-、-C(CH ₃) ₂-、-NH-、-CO-、-NHCO-、-CONH-、-COO-、-OCO-、-(CH ₂) _m-、-SO ₂-、-O-(CH ₂) _m-O-、-O-C(CH ₃) ₂-、-C(CH ₃) ₂-O-、-CO-(CH ₂) _m-、-(CH ₂) _m-CO-、-NH-(CH ₂) _m-、-(CH ₂) _m-NH-、-SO ₂-(CH ₂) _m-、-(CH ₂) _m-SO ₂-、-CONH-(CH ₂) _m-、-(CH ₂) _m-NHCO-、-CONH-(CH ₂) _m-NHCO-或-COO-(CH ₂) _m-OCO-。m為1~8之整數。 For the diamine represented by formula (7) and formula (7'), the structure represented by the following formula is the most ideal but not limited to these, especially considering the ease of synthesis, high versatility, and characteristics. [chem 34]

In the formula, n is an integer from 2 to 8, and E is a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -NHCO-, -CONH-, -COO-, - OCO-, -(CH ₂ ) _m -, -SO ₂ -, -O-(CH ₂ ) _m -O-, -OC(CH ₃ ) ₂ -, -C(CH ₃ ) ₂ -O-, -CO -(CH ₂ ) _m -, -(CH ₂ ) _m -CO-, -NH-(CH ₂ ) _m -, -(CH ₂ ) _m -NH-, -SO ₂ -(CH ₂ ) _m -, - (CH ₂ ) _m -SO ₂ -, -CONH-(CH ₂ ) _m -, -(CH ₂ ) _m -NHCO-, -CONH-(CH ₂ ) _m -NHCO- or -COO-(CH ₂ ) _m -OCO-. m is an integer from 1 to 8.

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

The diamine having such a site where radical polymerization occurs is preferably used in an amount of 5 to 50 mol% of the total diamine component used for synthesis of the polymer contained in the radical generating film forming composition, More preferably, it is 10-40 mole %, especially preferably, it is 15-30 mole %.

In addition, when the polymer used in the radical generating membrane of the present invention is obtained from diamine, other diamines other than the above-mentioned diamine having a site for generating radicals may be used in combination as the diamine as long as the effect of the present invention is not impaired. amine component. Specifically, 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-diaminotoluene Aminophenol, 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 Benzene, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane Methane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-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'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine Aniline, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl base)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'-diaminodiphenylketone, 3,3'-diamine Diaminodiphenylketone, 3,4'-diaminodiphenylketone, 2,2'-diaminodiphenylketone, 2,3'-diaminodiphenylketone, 1,4-di Aminonaphthalene, 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-aminophenyl)benzene oxy)benzene, 4,4'-[1,4-phenylene bis(methylene)]diphenylamine, 4,4'-[1,3-phenylene bis(methylene)]diphenylamine , 3,4'-[1,4-phenylene bis(methylene)]diphenylamine, 3,4'-[1,3-phenylene bis(methylene)]diphenylamine, 3,3 '-[1,4-phenylene bis(methylene)]diphenylamine, 3,3'-[1,3-phenylene bis(methylene)]diphenylamine, 1,4-phenylene Bis[(4-aminophenyl)methanone], 1,4-phenylenebis[(3-aminophenyl)methanone], 1,3-phenylenebis[(4-aminophenyl) base)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4-phenylene bis(4-aminobenzoate), 1,4- Phenylbis(3-aminobenzoate), 1,3-phenylenebis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoic acid ester), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate , bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N,N'-(1 ,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'- (1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(3 -aminophenyl) terephthalamide, N,N'-bis(4-aminophenyl)isophthalamide, N,N'-bis(3-aminophenyl)isophthalamide Diformamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylsulfone, 2,2-bis[4-(4 -aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane Fluoropropane, 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, transformer-1,4-bis( 4-aminophenyl)cyclohexane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, bis(4-aminophenoxy)methane, 1,2-bis(4 -aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4- Aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3 -aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1 ,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane , 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis(3-aminophenoxy)decane Alkane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy) Aromatic diamines such as dodecane, 1,12-bis(3-aminophenoxy)dodecane; bis(4-aminocyclohexyl)methane, bis(4-aminophenoxy-3-methane cyclohexyl) 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, 1,11-diaminoundecane alkane, 1,12-diaminododecane and other aliphatic diamines; 1,3-bis[2-(p-aminophenyl)ethyl]urea, 1,3-bis[2-(p-amine Diamines with urea structure such as phenyl)ethyl]-1-tert-butoxycarbonylurea; N-p-aminophenyl-4-p-aminophenyl(tert-butoxycarbonyl)amine Diamines with nitrogen-containing unsaturated heterocyclic structures such as methylpiperidine; N-tert-butoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N-(4-amino Diamines such as benzyl)amine having an N-Boc group (Boc represents tert-butoxycarbonyl) and the like.

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

For the synthesis when the polymer is polyamic acid, the tetracarboxylic dianhydride reacted with the diamine component is not particularly limited. Specifically, pyromellitic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid, 1,4,5,8-naphthalene tetracarboxylic 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'-diphenyl ketone tetracarboxylic acid, bis(3,4-dicarboxyphenyl)pyridine, 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-pyridine tetracarboxylic 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, 4,4'-oxodiphthalic acid, 1,2,3,4-cyclobutane Butane tetracarboxylic acid, 1,2,3,4-cyclopentane tetracarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic acid, 1,2,3,4-tetramethyl-1, 2,3,4-cyclobutane tetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid, 1,3-dimethyl-1,2,3, 4-cyclobutane tetracarboxylic acid, 1,2,3,4-cycloheptane tetracarboxylic acid, tetrahydrofuran-2,3,4,5-tetracarboxylic acid, 2-(3,4-dicarboxycyclohexyl) Succinic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo[3.3.0]octane-2 ,4,6,8-tetracarboxylic acid, bicyclo[4.3.0]nonane-2,4,7,9-tetracarboxylic acid, bicyclo[4.4.0]decane-2,4,7,9-tetracarboxylic acid Carboxylic acid, bicyclo[4.4.0]decane-2,4,8,10-tetracarboxylic acid, tricyclo[6.3.0.0<2,6>]undecane-3,5,9,11-tetracarboxylate acid, 1,2,3,4-butanetetracarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2- Dicarboxylic acid, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3- Cyclohexane-1,2-dicarboxylic acid, tetracyclo[6.2.1.1<3,6>.0<2,7>] dodecane-4,5,9,10-tetracarboxylic acid, 3,5 ,6-tricarboxynorbornane-2:3,5:6 dicarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic acid and other tetracarboxylic dianhydrides.

Of course, tetracarboxylic dianhydrides can also be used alone or in combination according to properties such as liquid crystal alignment, polymerization sensitivity, voltage retention characteristics, and charge accumulation when forming a radical generating film.

The structure of the dialkyl tetracarboxylate reacted with the above-mentioned diamine component is not particularly limited for synthesis when the polymer is polyamide ester, and specific examples thereof are listed below.

Specific examples of aliphatic tetracarboxylic acid diesters include dialkyl 1,2,3,4-cyclobutane tetracarboxylate, 1,2-dimethyl-1,2,3,4-cyclobutane dialkyl alkane tetracarboxylate, dialkyl 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylate, 1,2,3,4-tetramethyl-1,2, Dialkyl 3,4-cyclobutane tetracarboxylate, Dialkyl 1,2,3,4-cyclopentane tetracarboxylate, Dialkyl tetrahydrofuran 2,3,4,5-tetracarboxylate, 1, Dialkyl 2,4,5-cyclohexanetetracarboxylate, dialkyl 2-(3,4-dicarboxycyclohexyl)succinate, 3,4-dicarboxy-1,2,3,4-tetra Dialkyl Hydrogen-1-Naphthalene Succinate, Dialkyl 1,2,3,4-Butane Tetracarboxylate, Dialkyl Bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylate ester, dialkyl 3,3',4,4'-dicyclohexyl tetracarboxylate, dialkyl 2,3,5-tricarboxycyclopentyl acetate, cis-3,7-dibutylcyclooctyl -1,5-diene-1,2,5,6-dialkyl tetracarboxylate, tricyclo[4.2.1.0<2,5>]nonane-3,4,7,8-tetracarboxylic acid- 3,4: 7,8-dialkyl ester, hexacyclo[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-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetra Dialkylhydronaphthalene-1,2-dicarboxylate, etc.

Dialkyl aromatic tetracarboxylates include dialkyl pyromellitate, dialkyl 3,3',4,4'-biphenyl tetracarboxylate, 2,2',3,3'-biphenyl tetracarboxylate Dialkyl carboxylate, 2,3,3',4-diphenyl tetracarboxylate, 3,3',4,4'-diphenyl ketone tetracarboxylate, 2,3,3 ',4'-diphenyl ketone tetracarboxylic acid dialkyl ester, bis(3,4-dicarboxyphenyl)ether dialkyl ester, bis(3,4-dicarboxyphenyl)pyridine dialkyl ester, 1, Dialkyl 2,5,6-naphthalene tetracarboxylate, dialkyl 2,3,6,7-naphthalene tetracarboxylate, etc.

式中R ₂、及R ₃表示碳數1~10之脂肪族烴基。 For the synthesis when the polymer is polyurea, the diisocyanate reacted with the above-mentioned diamine component is not particularly limited, and can be used depending on availability and the like. The specific structure of diisocyanate is shown below. [chem 35]

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

The aliphatic diisocyanates shown in K-1~K-5 have poor reactivity but have the advantage of improving solvent solubility. The aromatic diisocyanates shown in K-6~K-13 have high reactivity and are useful The effect of improving heat resistance, but the disadvantage of lowering solvent solubility can be cited. In terms of versatility and characteristics, K-1, K-7, K-8, K-9, and K-10 are more ideal; in terms of electrical properties, K-12 is better; in terms of liquid crystal alignment, K -13 is better. It is also possible to use two or more kinds of diisocyanates in combination, and it is preferable to use each component according to the properties to be obtained.

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

For the synthesis when the polymer is polyamide, the structure of the dicarboxylic acid to be reacted is not particularly limited, and specific examples can be listed as follows. Examples of 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.

Alicyclic dicarboxylic acids include: 1,1-cyclopropane dicarboxylic acid, 1,2-cyclopropane dicarboxylic acid, 1,1-cyclobutane dicarboxylic acid, 1,2-cyclobutane dicarboxylic acid Carboxylic acid, 1,3-cyclobutanedicarboxylic acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutanedicarboxylic acid Acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4- Cyclohexanedicarboxylic acid, 2-norbornene-1,4-dicarboxylic acid, 2-norbornene-2,3-dicarboxylic acid, bicyclo[2.2.2]octane-1,4-dicarboxylic acid Acid, bicyclo[2.2.2]octane-2,3-dicarboxylic acid, 2,5-dioxo-1,4-bicyclo[2.2.2]octanedicarboxylic acid, 1,3-adamantane Dicarboxylic acid, 4,8-dioxo-1,3-adamantanedicarboxylic acid, 2,6-spiro[3.3]heptanedicarboxylic acid, 1,3-adamantanediacetic acid, camphoric acid, etc.

Aromatic dicarboxylic acids include: phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid Formic acid, 5-hydroxyisophthalic acid, 2,5-dimethyl terephthalic acid, tetramethyl terephthalic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-anthracene dicarboxylic acid, anthraquinone-1,4-dicarboxylic acid, 2,5-biphenyl dicarboxylic acid, 4,4' -Biphenyl dicarboxylic acid, 1,5-extended biphenyl dicarboxylic acid, p-terphenyl-4,4"-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, 1,2- Bis(4-carboxyphenyl)ethane, 2,2-bis(4-carboxyphenyl)propane, 2,2-bis(4-carboxyphenyl)hexafluoropropane, diphenyl ether-4,4'- Dicarboxylic acid, bibenzyl-4,4'-dicarboxylic acid, 4,4'-stilbene dicarboxylic acid, 4,4'-ethynyl benzoic acid (4,4'-ethylenebenzoic acid), 4, 4'-Carbonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid, 4,4'-dithiodibenzoic acid, p-phenylenediacetic acid, 3,3'-p-phenylenedipropionic acid , 4-carboxycinnamic acid, p-phenylenediacrylate, 3,3'-[4,4'-(methylene di-p-phenylene)]dipropionic acid, 4,4'-[4,4' -(oxydi-p-phenylene)]dipropionic acid, 4,4'-[4,4'-(oxydi-p-phenylene)]dibutyric acid, (isopropylidene di-p-phenylene dioxy ) Dibutyric acid, bis(p-carboxyphenyl)dimethylsilane and other dicarboxylic acids.

For dicarboxylic acids containing heterocycles, 1,5-(9-oxo-oxo)dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazoledicarboxylic acid, 2-phenyl- 4,5-Thiadiazoledicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridine Dicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, etc.

The various dicarboxylic acids mentioned above may be in the structure of acyl dihalides or acid anhydrides. These dicarboxylic acids, especially if they are dicarboxylic acids that can provide polyamide with a linear structure, are ideal in terms of maintaining the alignment of liquid crystal molecules. Among them, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid acid, 1,2-bis(4-carboxyphenyl)ethane, 2,2-bis(4-carboxyphenyl)propane, 2,2-bis(4-carboxyphenyl)hexafluoropropane, p-terphenyl -4,4"-dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,5-pyridine dicarboxylic acid or their acyl dihalides are ideal. Isomers sometimes exist in these compounds , It may also be a mixture containing these isomers. Also, two or more compounds may be used in combination. Also, the dicarboxylic acids used in the present invention are not limited to the compounds exemplified above.

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

The reaction of the diamine component and the tetracarboxylic dianhydride component is relatively easy to proceed in an organic solvent, and is advantageous in terms of not generating 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 in which a polymer does not dissolve, it can be mixed with the above-mentioned solvent and used within the range in which the produced polymer does not precipitate. Moreover, the moisture in the organic solvent will hinder the polymerization reaction and further cause the hydrolysis of the generated polymer, so the organic solvent should be dehydrated and dried.

Organic solvents such as: N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methylformamide, N-methyl -2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, N - Methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfide, hexamethylphosphoramide, gamma-butyrolactone, isopropanol, methoxymethylpentanol , dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosu, ethyl cellosu, methyl cellosu B Ethyl carbitol, Ethyl carbitol, Ethyl carbitol, Ethylene glycol, Ethylene glycol monoacetate, Ethylene glycol monoiso Propyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tertiary butyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethyl ether Glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate mono Ethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl Alcohol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, di Oxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate ester, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, -Ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl- 2-pentanone, 2-ethyl-1-hexanol, etc. These organic solvents may be used alone or in combination.

When the diamine component and the tetracarboxylic dianhydride component are reacted in an organic solvent, the diamine component is dispersed or dissolved in an organic solvent and the solution is stirred and the tetracarboxylic dianhydride component is directly added, or the tetracarboxylic dianhydride component is added directly. The method of dispersing or dissolving the anhydride component in an organic solvent and then adding it, conversely the method of adding the diamine component to a solution obtained by dispersing or dissolving the tetracarboxylic dianhydride component in an organic solvent, mixing the tetracarboxylic dianhydride component and the diamine component A method of adding alternately, etc., any of these methods can be used. In addition, when the diamine component or the tetracarboxylic dianhydride component is composed of multiple compounds, they can be reacted in a pre-mixed state, or they can be individually reacted in sequence, and the low molecular weight bodies that have been individually reacted can also be mixed and reacted to form a high-molecular-weight compound. Molecular body.

The temperature when reacting the diamine component and the tetracarboxylic dianhydride component can be selected at any temperature, for example: -20~100°C, preferably in the range of -5~80°C. Moreover, reaction can be performed at arbitrary concentration, For example, the total amount of a diamine component and a tetracarboxylic dianhydride component is 1-50 mass % with respect to a reaction liquid, Preferably it is 5-30 mass %.

In the above polymerization reaction, the ratio of the total moles of the tetracarboxylic dianhydride components to the total moles of the diamine components can be selected in accordance with the molecular weight of the polyamic acid to be obtained. Like the usual polycondensation reaction, the closer the molar ratio is to 1.0, the greater the molecular weight of the polyamic acid produced. The ideal range is 0.8~1.2.

The method for synthesizing the polymer used in the present invention is not limited to the above-mentioned method. When synthesizing polyamic acid, it is the same as the general polyamic acid synthesis method, replacing the above-mentioned tetracarboxylic dianhydride with tetracarboxylic acid of the corresponding structure Or a tetracarboxylic acid derivative such as a tetracarboxylic acid dihalide can be reacted by a known method to obtain the corresponding polyamic acid. Moreover, when synthesizing polyurea, what is necessary is just to make diamine and diisocyanate react. When producing polyamide ester or polyamide, diamine is reacted with components selected from tetracarboxylic acid diester and dicarboxylic acid in the presence of known condensing agent, or derivatized into acid halide by known method , react with diamine.

Moreover, polyimide can be obtained by ring-closing (imidizing) the said polyamic acid. In addition, the imidization ratio referred to in this specification is the ratio of the imide group to the total amount of the imide group and carboxyl group derived from tetracarboxylic dianhydride. In polyimide, the imidization rate does not have to be 100%, and can be adjusted arbitrarily according to the application and purpose. Regarding the imidization rate of polyimide, considering the point of view of making the voltage retention rate high, it is better to be more than 30%. It is better below 80%.

The temperature for thermal imidization of polyamic acid in the solution is usually 100~400°C, preferably 120~250°C. It is advisable to remove the water generated by the imidization reaction to the outside of the system. better.

Catalyzed imidization of polyamic acid can be implemented by adding alkaline catalyst and acid anhydride to the solution of polyamic acid, usually at -20~250°C, preferably at 0~180°C . The amount of alkaline catalyst is usually 0.5~30 mole times of amide acid group, preferably 2~20 mole times, and the amount of acid anhydride is usually 1~50 mole times of amide acid group, preferably 3~30 mole times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferable because it has a moderate basicity to allow the reaction to proceed. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. However, using acetic anhydride is preferable since purification after the reaction becomes easy. The imidization rate of the imidization using the catalyst can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

When recovering the produced polymer from the reaction solution of the polymer, the reaction solution may be poured into a poor solvent and allowed to precipitate. Examples of poor solvents used for precipitation formation include methanol, acetone, hexane, butylcylonosulfone, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer obtained by throwing in a poor solvent and precipitating it can be collected by filtration, and dried at normal temperature or under normal pressure or reduced pressure. In addition, if the polymer that has been recovered by precipitation is redissolved in an organic solvent, and then reprecipitated and recovered, and this operation is repeated 2 to 10 times, the impurities in the polymer can be reduced. Poor solvents at this time are, for example, alcohols, ketones, hydrocarbons, etc., and it is ideal to use at least three kinds of poor solvents selected from among them because the purification efficiency will be higher.

In addition, when the aforementioned 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 contain a polymer other than a polymer containing an organic group that induces radical polymerization. other polymers. In this case, the content of other polymers is preferably 5 to 95% by mass, more preferably 30 to 70% by mass, in all the polymer components.

With respect to the molecular weight of the polymer possessed by the radical generating film forming composition, the strength of the free radical generating film obtained by coating the free radical generating film forming composition, the workability of the coating film formation, the uniformity of the coating film, etc. In this case, the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is ideally 5,000-1,000,000, more preferably 10,000-150,000.

When the free radical generating film used in the present invention is obtained by applying a compound having a radical generating free radical and a polymer composition, hardening to form a film and fixing it in the film, the polymer can be selected from The polyimide precursor produced according to the above-mentioned production method, and the polymers in the group consisting of polyimide, polyurea, polyamide, polyacrylate, polymethacrylate, etc., are used to produce The diamine at the site of radical polymerization is at least one polymer obtained from 0 mol % of the diamine component used in the synthesis of the polymer contained in the radical generating film forming composition. Compounds having radical-generating groups to be added at this time are listed below.

Compounds that generate free radicals by heat are compounds that generate free radicals by heating above the decomposition temperature. Such radical thermal polymerization initiators, for example: ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.) etc.), hydrogen peroxides (hydrogen peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tertiary butyl peroxide, dicumyl peroxide, diperoxylauryl, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkyl peroxyesters (tertiary butyl peroxyneodecanoate, trimethyl peroxide tertiary butyl acetate, third pentyl peroxide 2-ethylcyclohexanoate, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobis Isobutyronitrile, and 2,2'-bis(2-hydroxyethyl) azobisisobutyronitrile, etc.). Such a radical thermal polymerization initiator may be used individually by 1 type, or may use it 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 by irradiation with light. Examples of such radical photopolymerization initiators include diphenyl ketone, Micheler ketone, 4,4'-bis(diethylamino) diphenyl ketone, xanthrone, thioxanthone, isopropyl Oxyanthrone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-iso Propyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy -2-Phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-alphalinopropan-1-one, 2-benzyl Base-2-dimethylamino-1-(4-?-olinophenyl)-butanone-1, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl ester, 4 ,4'-bis(tertiary butylperoxycarbonyl) diphenyl ketone, 3,4,4'-tri(tertiary butyl peroxycarbonyl) diphenyl ketone, 2,4,6-trimethyl Benzoyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-trichloromethyl, 2-(3',4'- Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-tristyryl, 2-(2',4'-dimethoxystyryl)-4,6-bis( Trichloromethyl)-s-trimethoxyl, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-trimethoxyl, 2-(4'-pentyloxy Styryl)-4,6-bis(trichloromethyl)-s-trichloromethyl, 4-[p-N,N-bis(ethoxycarbonylmethyl)]-2,6-bis(tri Chloromethyl)-s-trichloromethyl, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-trichlorophenyl, 1,3-bis(trichloromethyl)- 5-(4'-Methoxyphenyl)-s-trimethoxazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzo Thiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl -1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'- Biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'bis(2, 4-Dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4 ,4',5,5'-tetraphenyl-1,2'-biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2- Methyl-2-(((5-2,4-cyclopentadien-1-yl)-9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis(5-2,4-cyclopentadien-1-yl)-bis (2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3',4,4'-tetrakis(tert-butylcarbonylperoxy)diphenylketone, 3,3',4,4 '-Tetra(tertiary hexylperoxycarbonyl) diphenyl ketone, 3,3'-bis(methoxycarbonyl)-4,4'-bis(tertiary butylperoxycarbonyl) diphenyl ketone, 3 ,4'-bis(methoxycarbonyl)-4,3'-bis(tert-butylperoxycarbonyl)diphenylketone, 4,4'-bis(methoxycarbonyl)-3,3'- Di(tertiary butylperoxycarbonyl) diphenyl ketone, 2-(3-methyl-3H-benzothiazol-2-ylidene)-1-naphthalen-2-yl-ethanone, or 2-( 3-methyl-1,3-benzothiazole-2(3H)-ylidene)-1-(2-benzoyl)ethanone and the like. These compounds may be used alone or in combination of two or more.

In addition, even when the radical generating film is composed of a polymer containing an organic group that induces radical polymerization, in order to promote radical polymerization when energy is supplied, it may contain a compound having a radical generating radical.

The composition for forming a radical generating film may contain a polymer component and, if necessary, an organic solvent for dissolving or dispersing other components such as a radical generating agent. Such an organic solvent is not particularly limited, for example: the organic solvent exemplified in the above-mentioned synthesis of polyamic acid. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N- Dimethylpropanamide and the like are ideal from the viewpoint of solubility. In particular, N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone is preferable, but 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 with an organic solvent with high solubility of the components contained in the radical generating film forming composition.

Solvents for better uniformity and smoothness of the coating film, such as: isopropanol, methoxymethylpentanol, methyl cellosulfate, ethyl cellosulfate, butyl cellosulfate (ethylene glycol mono butyl ether), methyl cellothreonate, butyl cellothreoacetate, ethyl cellothreoacetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate Esters, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tertiary butyl ether, diethylene glycol alcohol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether , 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl Cyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, methyl acetate Esters, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, 3- Ethyl methoxypropionate, 3-ethoxypropionate, 3-methoxypropionate, 3-methoxypropylpropionate, 3-methoxybutylpropionate, 1-methoxy- 2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol diacetate, propylene glycol-1-monomethyl Ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, 2-ethyl-1-hexanol, and the like. These solvents may also mix multiple types. When these solvents are used, it is preferably 5-80% by mass of the total solvent contained in the liquid crystal alignment agent, more preferably 20-60% by mass.

The composition for forming a radical generating film may contain components other than those described above. Examples thereof include compounds that improve the film thickness uniformity and surface smoothness when coating a radical-generating film-forming composition, compounds that improve the adhesion between a radical-generating film-forming composition and a substrate, A compound with better film strength of a radical-generating film-forming composition, etc.

Compounds that improve the uniformity of film thickness and surface smoothness include fluorine-based surfactants, polysiloxane-based surfactants, and nonionic surfactants. More specifically, for example: EftopEF301, EF303, EF352 (manufactured by Mitsubishi Materials Corporation), MegafacF171, F173, R-30 (manufactured by DIC Corporation), FluoradFC430, FC431 (manufactured by 3M Corporation), AsahiGuardAG710 (manufactured by AGC Corporation), Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimichemical) and the like. When using these surfactants, the proportion thereof is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the total amount of polymers contained in the radical generating film forming composition.

Specific examples of the compound for improving the adhesion between the radical generating film-forming composition and the substrate include functional silane-containing compounds, epoxy group-containing compounds, and the like. For example: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyl Trimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane Ethoxysilane, N-(3-triethoxysilylpropyl)triethylenetetramine, N-(3-trimethoxysilylpropyl)triethylenetetramine, 10-trimethoxy Silyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-di Azanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis( Oxyethylenyl)-3-aminopropyltrimethoxysilane, N-bis(oxyethylenyl)-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 Diol Glycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol , N,N,N',N'-tetraepoxypropyl-m-xylylenediamine, 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane, N,N, N',N'-tetraepoxypropyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-epoxypropyl)aminopropyltrimethoxysilane, 3-(N,N-diepoxypropyl)aminopropyltrimethoxysilane, etc.

In addition, in order to increase the film strength of the free radical generating film, 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, tetrakis(methoxymethyl)bis Phenol compounds such as phenol. When these compounds are used, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total polymer contained in the radical generating film forming composition.

Furthermore, in the composition for forming a radical generating film, within the range that does not impair the effect of the present invention, other than that, it is also possible to add a target medium for changing the electrical characteristics such as the dielectric constant and conductivity of the radical generating film. Electrons, conductive substances.

[Free radical generating film] The radical generating film of the present invention is obtained, for example, using the above-mentioned composition for forming a radical generating film. For example, the cured film obtained by coating the radical generating film-forming composition used in the present invention on a substrate, drying and firing may be directly used as a radical generating film. In addition, this cured film can be rubbed, irradiated with polarized light or light of a specific wavelength, etc., treated with ion beams, etc., to perform alignment treatment, and can also irradiate UV (ultraviolet ray) to the liquid crystal display element after filling the liquid crystal as an alignment film for PSA. ).

The substrate on which the radical generating film-forming composition is applied is not particularly limited as long as it is highly transparent, and a substrate on which transparent electrodes for driving liquid crystals are formed is preferred.

Specific examples include glass plates, polycarbonate, poly(meth)acrylate, polyethersulfone, polyarylate, polyurethane, polysulfide, polyether, polyetherketone, trimethylpentamethylene Plastic sheets such as vinyl, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triacetyl cellulose, diacetyl cellulose, cellulose acetate butyrate, etc. have formed transparent electrode substrate.

The substrate that can be used by the IPS liquid crystal display element can also use standard IPS comb electrodes, PSA herringbone electrodes and other electrode patterns, such as MVA protrusion patterns.

In addition, high-performance elements such as TFT-type elements use elements such as transistors formed between electrodes for driving liquid crystals and substrates.

When making a transmissive liquid crystal display element, the above-mentioned substrates are generally used, but when it is intended to make a reflective liquid crystal display element, if only one side of the substrate is used, an opaque substrate such as a silicon wafer can also be used. In this case, the electrodes formed on the substrate may also use materials such as aluminum that reflects light.

The coating method of the free radical generating film forming composition includes spin coating method, printing method, inkjet method, spray coating method, roll coating method, etc. In consideration of productivity, transfer printing method is widely used in industry, and the present invention can also be Ideally used.

The drying step after coating the radical generating film-forming composition is not necessary, but when the time from coating to firing is not fixed for each substrate, or when firing is not immediately after coating, it is preferable to include a drying step. The drying method is not particularly limited as long as the solvent is removed to such an 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°C, preferably 60-100°C, for 0.5-30 minutes, preferably 1-5 minutes.

The coating film formed by coating the radical-generating film-forming composition as described above can be calcined into a cured film. At this time, the calcination temperature can be generally carried out at any temperature from 100 to 350°C, but is preferably 140 to 300°C, more preferably 150 to 230°C, and even more preferably 160 to 220°C. The calcining time can usually be calcined at any time from 5 to 240. Preferably it is 10-90 points, more preferably 20-90 points. Commonly known methods can be used for heating, for example: hot plate, hot air circulation oven, IR (infrared) oven, belt furnace, etc.

The thickness of the cured film can be selected according to needs, preferably more than 5nm, more preferably more than 10nm, because the reliability of the liquid crystal display element is improved, so it is ideal. Also, when the thickness of the cured film is preferably at most 300 nm, more preferably at most 150 nm, it is preferable because the power consumption of the liquid crystal display element does not increase extremely.

The first substrate having a radical generating film can be obtained by performing the above method, but a uniaxial alignment treatment can be performed on the radical generating film. The method of performing uniaxial alignment treatment includes photo-alignment method, oblique vapor deposition method, rubbing, uniaxial alignment treatment by magnetic field, and the like.

When the alignment treatment is carried out by rubbing in one direction, for example, the substrate is moved while rotating a rubbing roller wrapped with a rubbing cloth so that the rubbing cloth and the film come into contact. When the photo-alignment method is used, an alignment treatment can be performed by irradiating the entire film with polarized UV of a specific wavelength and heating as necessary. In the case of the first substrate of the present invention that has formed comb-toothed electrodes, the direction is selected by utilizing the electrical and physical properties of liquid crystals. If a liquid crystal with positive dielectric anisotropy is used, the rubbing direction is set to the direction of the comb-toothed electrodes. The extension directions are preferably substantially the same direction.

The step of forming the weak anchor portion and the strong anchor portion includes a method of irradiating radiation in an arbitrary pattern through a photomask or the like. In this step, the radical generating film is irradiated with radiation in advance so that the radical generating site disappears, so that it is not in a weakly anchored state. The radiation used in this step includes polarized light, light of a specific wavelength, ion beam, and the like. It is particularly preferable to irradiate light of a wavelength at which the absorbance of the portion where the photoradicals are generated becomes the highest.

The second substrate of the present invention may or may not have a radical generating film. The second substrate is preferably a substrate with a conventionally known liquid crystal alignment film.

In the present invention, the first substrate may also be a substrate having comb electrodes, and the second substrate may be a counter substrate. Also, in the present invention, the second substrate may be a substrate having comb-shaped electrodes, and the first substrate may be a counter substrate.

＜Liquid crystal cell＞ The liquid crystal cell of the present invention is obtained by the following method: after forming a free radical generating film on the substrate according to the above method, the substrate with the free radical generating film (first substrate) and the substrate with a known liquid crystal alignment film (second substrate) Two substrates) are arranged in such a way that the radical generating film and the liquid crystal alignment film face each other, are fixed with a sealant between the spacers, and are obtained by injecting and sealing a liquid crystal composition containing liquid crystal and a radical polymerizable compound. In this case, the size of the spacer used is usually 1 to 30 μm, preferably 2 to 10 μm.

The method of injecting the liquid crystal composition containing the liquid crystal and the radically polymerizable compound is not particularly limited, and examples thereof include: the vacuum method of injecting a mixture containing the liquid crystal and the polymerizable compound after making the inside of the prepared liquid crystal cell a decompressed state; The liquid crystal and the polymer compound mixture are then sealed by drop method, etc.

式(A)中，M表示可自由基聚合之聚合性基，S表示單鍵、或亦可插入了鍵結基之碳數1~6之飽和烴基，T表示下式(B)表示之有機基，n為1~2之整數。n為2時，2個T可相同也可不同。惟n為2時，S表示亦可插入了鍵結基之碳數1~6之飽和烴基。 [化37]

式(B)中，＊代表鍵結部位。X為選自單鍵、醚鍵、酯鍵、醯胺鍵、胺甲酸酯鍵、脲鍵、硫醚鍵、-Si(R ₁)(R ₂)-(R ₁及R ₂各自獨立地表示鍵結於Si之烷基。)、-Si(R ₃)(R ₄)-O-(R ₃及R ₄各自獨立地表示鍵結於Si之烷基。)、及-N(R ₅)-(R ₅表示鍵結於N之氫原子或烷基。)之鍵結基，Cy表示6~20員環之非芳香族之環狀基。 <Radical polymerizable compound and liquid crystal composition> The radical polymerizable compound of the present invention is represented by the following formula (A). [chem 36]

In the formula (A), M represents a polymerizable group capable of free radical polymerization, S represents a single bond, or a saturated hydrocarbon group with 1 to 6 carbon atoms that can also be inserted into a bonding group, and T represents an organic compound represented by the following formula (B). Base, n is an integer from 1 to 2. When n is 2, two Ts may be the same or different. However, when n is 2, S represents a saturated hydrocarbon group with 1 to 6 carbon atoms that may also be inserted into a bonding group. [chem 37]

In formula (B), * represents a bonding site. X is selected from a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, a thioether bond, -Si(R ₁ )(R ₂ )-(R ₁ and R ₂ are each independently represents an alkyl group bonded to Si.), -Si(R ₃ )(R ₄ )-O-(R ₃ and R ₄ each independently represent an alkyl group bonded to Si.), and -N(R ₅ )-(R ₅ represents a hydrogen atom or an alkyl group bonded to N.), and Cy represents a non-aromatic cyclic group with 6 to 20 membered rings.

The saturated hydrocarbon group in S in formula (A) refers to the n+1 valent group formed by removing n+1 hydrogen atoms from saturated hydrocarbon (n and n in formula (A) are the same integer). When n is 1, the saturated hydrocarbon group is an alkylene group. A saturated hydrocarbon group with a carbon number of 1 to 6 inserted into a bonded group means that an n+1 valent group with a bonded group inserted between carbon-carbons in a saturated hydrocarbon group with a carbon number of 2 to 6, or an n+1 valent group with a carbon number of 1 to 6 A divalent group in which a bonding group is inserted between a saturated hydrocarbon group and an atom (for example: a carbon atom) to which it is bonded. The bonding group in S in formula (A), for example: carbon-carbon unsaturated bond, ether bond (-O-), ester bond (-COO- or -OCO-), amide bond (-CONH- or -NHCO-), etc. Carbon-carbon unsaturated bonds, such as carbon-carbon double bonds, etc., but a saturated hydrocarbon group with carbon numbers of 1 to 6 inserted into a carbon-carbon double bond should not have a carbon-carbon double bond at its end but an internal carbon-carbon double bond. When n is 1, an alkylene group having 1 to 6 carbons as a bonding group may also be inserted, for example: an alkylene group having 1 to 6 carbons, an oxyalkylene group having 1 to 6 carbons, etc. The alkylene group having 1 to 6 carbon atoms may be a straight chain alkylene group, a branched alkylene group, or a cyclic alkylene group.

R ₁ and R ₂ of -Si(R ₁ )(R ₂ )- in X of formula (B) are each independently an alkyl group bonded to Si, for example, an alkyl group having 1 to 6 carbon atoms. R ₃ and R ₄ of -Si(R ₃ )(R ₄ )-O- in X of formula (B) are each independently an alkyl group bonded to Si, for example: an alkyl group with 1 to 6 carbon atoms . R ₅ of -N(R ₅ )- in X of formula (B) is a hydrogen atom or an alkyl group bonded to N. Examples of alkyl groups: alkyl groups with 1 to 6 carbon atoms.

In formula (B), Cy is a non-aromatic cyclic group with 6-20 membered rings, preferably a non-aromatic cyclic group with 8-18 membered rings. Also, Cy may be a non-aromatic cyclic group with 12 to 20 membered rings. X in the formula (B) is bonded to atoms constituting the ring in Cy. In the cyclic group, the atomic system constituting the ring is bonded to the formula (B). Atoms constituting a ring in a non-aromatic cyclic group, such as carbon atoms, oxygen atoms, nitrogen atoms, silicon atoms, etc. The bond between atoms constituting the ring may be a single bond, a double bond, or a double bond, but a single bond is preferred. The ring in the non-aromatic cyclic group, such as: cyclic alkanes, cyclic ethers, cyclic siloxanes, etc. Cyclic ethers, e.g. crown ethers. For example: in 12-crown-4, the atoms constituting the ring are carbon atoms and oxygen atoms, and the number of members is 12. The ring may be a single ring or a plurality of rings. The number of rings in multiple rings, for example: 2~4. The ways in which the respective rings in the polycyclic ring are bonded to each other include, for example, the following three ways. ・1 atom in total: Example: spiro compound ・Two atoms in total: Like decahydronaphthalene, two rings share two atoms ・Bridged structure: Like norbornane, two rings share three or more atoms Also, in the case of polycyclic rings, the number of ring members is defined as the number of atoms constituting the ring. For example: norbornane is a 7-membered ring. The atoms constituting the ring may be bonded not to a hydrogen atom but to a halogen atom or an alkyl group having 1 to 6 carbon atoms. Halogen atom, for example: fluorine atom, chlorine atom, etc.

式中，＊代表鍵結部位。R ^b表示碳數2~8之直鏈烷基，E表示選自單鍵、-O-、-NR ^c-、-S-、酯鍵及醯胺鍵之鍵結基。R ^c表示氫原子、或碳數1~4之烷基。) In the formula, M represents a radically polymerizable polymerizable group, and the radically polymerizable polymerizable group M of the aforementioned radically polymerizable compound is preferably a polymerizable group selected from the following structures. [chem 38]

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

An example of the radically polymerizable compound represented by formula (A) satisfies, for example, the following (1) to (6). (1) M represents acryloxy or methacryloxy. (2) S represents a saturated hydrocarbon group with 1 to 6 carbon atoms in which a bonding group may also be inserted. (3) T represents the organic group represented by the formula (B). (4) n is an integer of 1~2. When n is 2, two Ts may be the same or different. (5) X is selected from an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, a thioether bond, -Si(R ₁ )(R ₂ )-(R ₁ and R ₂ are each independently represents an alkyl group bonded to Si.), -Si(R ₃ )(R ₄ )-O-(R ₃ and R ₄ each independently represent an alkyl group bonded to Si.), and -N(R ₅ )-(R ₅ represents a hydrogen atom or an alkyl group bonded to N.) A bonding group. (6) Cy represents a non-aromatic cyclic group with 12 to 20 membered rings.

式(C)中，R ₃及R ₄各自獨立地表示碳數1~6之烷基，R ₆表示碳數1~6之伸烷基，R ₇表示氫原子或甲基，p表示1~9之整數。 The radically polymerizable compound represented by the formula (A) is, for example, a radically polymerizable compound represented by the following formula (C). [chem 39]

In formula (C), R ₃ and R ₄ each independently represent an alkyl group with 1 to 6 carbons, R ₆ represents an alkylene group with 1 to 6 carbons, R ₇ represents a hydrogen atom or a methyl group, and p represents 1 to 6 Integer of 9.

The liquid crystal composition contains at least a liquid crystal and the above-mentioned radically polymerizable compound. The content of the radical polymerizable compound in the liquid crystal composition is preferably at least 0.5% by mass, more preferably at least 1% by mass, and preferably at most 10% by mass, based on the total mass of the liquid crystal and the radically polymerizable compound , more preferably 5% by mass or less.

Also, in the liquid crystal composition, a plurality of compounds having a monofunctional radical polymerizable group (hereinafter sometimes referred to as "other radical polymerizable compounds") other than the radical polymerizable compound described above may be used in combination.

Other free-radical polymerizable compounds, which have unsaturated bonds capable of free-radical polymerization in the presence of organic free radicals, such as: tert-butyl methacrylate, hexyl methacrylate, 2-ethyl methacrylate Hexyl, nonyl methacrylate, lauryl methacrylate, n-octyl methacrylate and other methacrylate monomers; tertiary butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate Acrylate monomers such as esters, lauryl acrylate, n-octyl acrylate, etc.; styrene, styrene derivatives (for example: o-, m-, p-methoxystyrene, o-, m-, p-tert-butoxystyrene , o-, m-, p-chloromethylstyrene, etc.), vinyl esters (such as: vinyl acetate, vinyl propionate, vinyl benzoate, etc.), vinyl ketones (such as: vinyl methyl ketone, ethylene Hexyl ketone, methyl isopropenyl ketone, etc.), N-vinyl compounds (for example: N-vinylpyrrolidone, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, etc.), ( Meth)acrylic acid derivatives (such as: acrylonitrile, methacrylonitrile, acrylamide, isopropylacrylamide, methacrylamide, etc.), vinyl halides (such as: vinyl chloride, vinylidene chloride, vinyl monomers such as tetrachloroethylene, hexachlorobutadiene, fluorinated ethylene, etc.), but not limited thereto. Also, they are preferably 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-、-NR ^c-、-S-、酯鍵、及醯胺鍵之鍵結基。R ^c表示氫原子、或碳數1~4之烷基。 Moreover, other radically polymerizable compounds are also preferably compounds represented by the following formula (1). [chemical 40]

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

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

又，液晶組成物中，含有自由基聚合性化合物聚合而獲得之聚合物之Tg成為100℃以下之自由基聚合性化合物較佳。 Also, for the radically polymerizable compound represented by the aforementioned formula (1), where E is an ester bond (a bond represented by -C(=O)-O- or -OC(=O)-), the ease of synthesis . It is ideal from the viewpoint of compatibility and polymerization reactivity of liquid crystals. Specifically, compounds represented by the following structures are preferred, but not particularly limited. [chem 41]

In addition, the liquid crystal composition preferably contains a radically polymerizable compound whose Tg of a polymer obtained by polymerizing the radically polymerizable compound is 100° C. or lower.

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

The polymer obtained by polymerizing a radically polymerizable compound has a Tg of preferably 100°C or lower, more preferably 0°C or lower.

In addition, liquid crystals generally refer to substances in a state that exhibits both solid and liquid properties. Representative liquid crystal phases include nematic liquid crystals and smectic liquid crystals, but the liquid crystals that can be used in the present invention are not particularly limited. For example, 4-pentyl-4'-cyanobiphenyl.

Then, energy sufficient to polymerize the radical polymerizable compound is given to the liquid crystal cell into which the mixture containing the liquid crystal and the radical polymerizable compound (liquid crystal composition) has been introduced. It can be implemented by, for example, heating or irradiating UV, and the radically polymerizable compound will exhibit desired properties through in-situ polymerization. Among them, UV irradiation is preferable from the viewpoint that alignment can be patterned and polymerization reaction can be performed in a short time.

In addition, during UV irradiation, heating may be performed. The heating temperature during UV irradiation should be within the temperature range where the introduced liquid crystal exhibits liquid crystallinity, usually above 40°C, and the heating is preferably carried out at a temperature before the liquid crystal changes to an isotropic phase.

Here, the wavelength of UV irradiation when irradiating UV irradiation should be selected to have the best wavelength of reaction quantum yield of the polymerizable compound to be reacted, and the irradiation amount of UV is usually 0.01~30J/cm ² , preferably 10J/cm ² or less, the lower the amount of UV irradiation, the more the reliability degradation caused by the destruction of the components constituting the liquid crystal display can be suppressed and the UV irradiation time can be shortened, thereby improving the takt in manufacturing, so it is more ideal.

In addition, when the polymerization is performed by heating instead of UV irradiation, it is preferable to carry out the heating at a temperature at which the polymerizable compound reacts and within a temperature range below the decomposition temperature of liquid crystals. Specifically, it is 100 to 150°C.

When sufficient energy is given for the polymerization reaction of the radically polymerizable compound, it is preferable to be in a no-electric-field state where no voltage is applied.

＜Liquid crystal display elements＞ Liquid crystal display elements can be produced using the liquid crystal cells obtained in this way. A liquid crystal display element includes, for example: a first substrate; a second substrate disposed opposite to the first substrate; and liquid crystal filled between the first substrate and the second substrate. In addition, in the liquid crystal display element, the radical polymerizable The compound is formed by polymerization reaction. Liquid crystal display elements, for example, can be made into reflective liquid crystal display elements by arranging reflective electrodes, transparent electrodes, λ/4 plates, polarizing films, color filter layers, etc. on the liquid crystal cells according to the usual methods. In addition, backlight, polarizing plate, λ/4 plate, transparent electrode, polarizing film, color filter layer, etc. can be installed in the liquid crystal cell according to the usual method to make a transmissive liquid crystal display element.

Fig. 1 is a schematic cross-sectional view showing an example of a transverse electric field liquid crystal display element of the present invention, which is an example of an IPS mode liquid crystal display element. In the transverse electric field liquid crystal display element 1 illustrated in FIG. 1 , the liquid crystal 3 is sandwiched between the comb electrode substrate 2 provided with the liquid crystal alignment film 2 c and the counter substrate 4 provided with the liquid crystal alignment film 4 a. The comb electrode substrate 2 has: a substrate 2a; a plurality of linear electrodes 2b formed on the substrate 2a and arranged in a comb-like shape; and a liquid crystal alignment formed on the substrate 2a to cover the linear electrodes 2b Membrane 2c. The opposite substrate 4 has: a base material 4b; and a liquid crystal alignment film 4a formed on the base material 4b. The liquid crystal alignment film 2 c is, for example, a weak anchor film obtained by chemically changing a free radical generating film. The liquid crystal alignment film on the comb-shaped electrode substrate side is obtained, for example, by polymerizing a radical polymerizable compound in a state where the radical generating film is in contact with a liquid crystal composition containing liquid crystal and a radical polymerizable compound. In this transverse electric field liquid crystal display element 1 , when a voltage is applied to the linear electrodes 2 b , an electric field is generated between the linear electrodes 2 b as shown by lines of force L .

Fig. 2 is a schematic cross-sectional view showing another example of a 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 transverse electric field liquid crystal display element 1 illustrated in FIG. 2 , liquid crystal 3 is sandwiched between comb electrode substrate 2 having liquid crystal alignment film 2 h and counter substrate 4 having liquid crystal alignment film 4 a. The comb 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; a plurality of wires formed on the insulating film 2f and arranged in a comb shape The linear electrode 2g; the liquid crystal alignment film 2h formed on the insulating film 2f to cover the linear electrode 2g. The opposite substrate 4 has: a base material 4b; and a liquid crystal alignment film 4a formed on the base material 4b. The liquid crystal alignment film 2h is, for example, a weak anchor film obtained by chemically changing the free radical generating film. The liquid crystal alignment film on the comb-shaped electrode substrate side is obtained, for example, by polymerizing a radical polymerizable compound in a state where the radical generating film is in contact with a liquid crystal composition containing liquid crystal and a radical polymerizable compound. In this transverse electric field liquid crystal display element 1, when a voltage is applied to the surface electrode 2e and the line electrode 2g, an electric field is generated between the surface electrode 2e and the line electrode 2g as indicated by the lines of force L. [Example]

The following examples are given to describe the present invention in detail, but the present invention is not limited to these examples. The abbreviation of the compound and the measurement method of each characteristic are as follows.

(Diamines) DA-1 to DA-5: Each is a compound represented by the following formula (DA-1) to (DA-5) [Chemical 42]

(Tetracarboxylic dianhydride) TC-1~TC-3: Each is a compound represented by the following formula (TC-1)~(TC-3) [Chem. 43]

(Additives) Add-1~Add-5: Each is a compound represented by the following formula (Add-1)~(Add-5) Add-C1~Add-C2: Each is the following formula (Add-C1)~(Add- Compound AD-1 represented by C2): a compound represented by the following formula (AD-1) [Chem. 44]

(Solvent) THF: Tetrahydrofuran CH ₂ Cl ₂ : Dichloromethane CHCl ₃ : Chloroform DMF: N,N-Dimethylformamide NMP: N-methyl-2-pyrrolidone BCS: Butylcelloxo GBL: γ -Butyrolactone (reagent) TEA: triethylamine DMAP: 4-dimethylaminopyridine (other) BHT: 2,6-di-tert-butyl-p-cresol

＜Viscosity measurement＞ The viscosity of polyamic acid solution, etc., is to use E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), with a sample volume of 1.1mL (milliliter), conical rotor TE-1 (1°34', R24), Measured at a temperature of 25°C.

<Measurement of Molecular Weight> Molecular weights of polyimide precursor and polyimide etc. were obtained by using normal temperature gel permeation chromatography (GPC) device (GPC-101) (manufactured by Showa Denko Co., Ltd.), column (GPC KD-803 , series of GPC KD-805) (manufactured by Showa Denko Co., Ltd.), and measured in the following manner. Column temperature: 50°C Eluent: N,N-dimethylformamide (additive is lithium bromide monohydrate (LiBr·H ₂ O) 30mmol/L (liter), phosphoric acid anhydrous crystal (orthophosphoric acid) 30mmol/L , Tetrahydrofuran (THF) 10mL/L) Flow rate: 1.0mL/min Standard sample for calibration line creation: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000, and 30,000) (manufactured by Tosoh Corporation) and poly Ethylene glycol (molecular weight; about 12,000, 4,000, and 1,000) (manufactured by Polymer Laboratory Corporation).

<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 % Tetramethylsilane (TMS) mixture) 1.0mL, apply ultrasound to dissolve it completely. For this solution, proton NMR at 500 MHz was measured with a Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) "AVANCE III" (manufactured by BRUKER). The chemical imidization rate is determined by taking the proton from the structure that does not change before and after imidization as the standard proton, using the peak cumulative value of this proton and the peak value from the amino acid that appears around 9.5~10.0ppm The cumulative value of the proton peak of the NH group is calculated according to the following formula. Also, in the formula, X is the cumulative value of the proton peak from the NH group of amide acid, Y is the cumulative value of the peak proton of the reference proton, and A is the relative ratio when polyamide acid (imidization rate is 0%) The ratio of the number of standard protons to one proton in the NH group of amide. Imidization rate (%)＝(1-Α・X/Y)×100

<<Synthesis of Additives (Add-1)~(Add-5) for Weak Anchoring IPS>> The products described in the following synthesis examples were identified by ¹ H-NMR analysis (analysis conditions are as follows). Device: Fourier transform type superconducting nuclear magnetic resonance device (FT-NMR) "AVANCE III" (manufactured by BRUKER) 500MHz. Solvent: DMSO-d ₆ (deuterated dimethylsulfoxide). Reference substance: tetramethylsilane (TMS) ( ¹ H is δ0.00ppm).

<Synthesis Example 1 Synthesis of 2-Acrylic acid-2-methylcyclopentadecyl (Add-1)> [Chem. 45]

Add cyclopentadecanol (20.0g: 88.3mmol), TEA (10.7g: 106.0mmol), and THF (200g) into a 300mL 4-necked flask equipped with a stirring bar, and slowly add formazan while stirring in an ice bath. Acryloyl chloride (10.2 g: 97.2 mmol), returned to room temperature after the dropwise addition, and stirred for 12 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (100 mL) was added and the precipitate was removed by filtration, washed with pure water (100 mL) and saturated brine (100 mL) in this order, and dried over anhydrous magnesium sulfate. After removing anhydrous magnesium sulfate by filtration, the solvent was removed by an evaporator to obtain a crude product. Purification was performed by column chromatography (developing solvent: ethyl acetate/hexane = 1/9 (volume ratio)), and Add-1 (21.6 g: yield 83.0%, colorless and transparent) was obtained by solvent removal. slime). ¹ H-NMR (500MHz), in DMSO-d ₆ ;

<Synthesis Example 2 Synthesis of 2-Cyclopentadecyl Acrylate (Add-2)> [Chem. 46]

Add-2 (20.5 g: 79.6% yield, colorless transparent viscous) was obtained in the same manner as in Synthesis Example 1, except that methacryl chloride was used instead of acryl chloride (9.59 g: 106.0 mmol). . ¹ H-NMR (500MHz), in DMSO-d ₆ ; )

＜Synthesis Example 3 Synthesis of 2-propenyl-2-methyl-(methoxydimethylsilyl)cyclopentadecyl ester (Add-3)＞ [Chem. 47]

Add cyclopentadecanol (20.0g: 88.3mmol), imidazole (12.0g: 176.7mmol), and chloroform (200g) into a 300mL 4-neck flask equipped with a stirring bar, and slowly add (bromine) dropwise while stirring in an ice bath. Methyl)chlorodimethylsilane (33.1g: 176.7mmol), return to room temperature after the dropwise addition, and stir for 24 hours. After confirming the completion of the reaction by HPLC, it was washed with pure water (100 mL) and saturated brine (100 mL) in this order, and dried over anhydrous magnesium sulfate. After removing anhydrous magnesium sulfate by filtration, the solvent was removed by an evaporator to obtain a crude product. Purified by distillation in an oil bath set at 180° C. for 3 hours under a high vacuum of 30 Pa to obtain Add-3-1 (18 g: yield 54.0%). Add Add-3-1 (18g: 47.7mmol), potassium methacrylate (8.9g: 71.5mmol), BHT (1.1g: 4.8mmol) and DMF (180 g) was heated and stirred at 80° C. for 4 hours. After heating and stirring, it was washed with pure water (100 ml) and saturated brine (100 ml), and dried over anhydrous magnesium sulfate. After removing anhydrous magnesium sulfate by filtration, the solvent was removed by an evaporator to obtain a crude product. Purification was carried out by column chromatography (developing solvent: ethyl acetate/hexane = 1/9 (volume ratio)). By removing the solvent, Add-3 (17.9 g: yield 98.6%, colorless transparent viscous ). ¹ H-NMR (500MHz), in DMSO-d ₆ ; , 1.32(26H), 0.20(6H)

<Synthesis Example 4 Synthesis of 2-methyl-cyclopentadecyl 2-acrylate (Add-4)> [Chem. 48]

Add-4 (21.9 g: 80.0% yield, colorless liquid) was obtained in the same manner as in Synthesis Example 1 except that cyclopentadecanol was used instead of cyclododecanol (20.0 g: 108.5 mmol). ¹ H-NMR (500MHz), in DMSO-d ₆ ; 2H), 1.36(18H)

<Synthesis Example 5 Synthesis of 2-methyl-cyclooctyl 2-acrylate (Add-5)> [Chem. 49]

Add-5 (25.9 g: 84.4% yield, colorless liquid) was obtained in the same manner as in Synthesis Example 1 except that cyclopentadecanol was used instead of cyclooctanol (20.0 g: 156.1 mmol). ¹ H-NMR (500MHz), in DMSO-d ₆ ; δ(ppm)=5.99(1H), 5.62(1H), 4.90(1H), 1.87(3H), 1.78-1.51(14H)

＜Acquisition of Add-C1 and Add-C2＞ Products from Tokyo Chemical Industry Co., Ltd. were purchased and used directly.

＜＜Synthesis of polyamic acid and polyimide＞＞ <Synthesis Example 6> Measure DA-1 (1.08g: 10.0mmol) and DA-3 (3.30g: 10.0mmol) in a 100mL four-neck flask equipped with a mechanical stirrer and a nitrogen inlet tube, add NMP (24.9g), and Stir under ambient conditions to dissolve it, then keep it below 10°C in an ice bath, add TC-2 (2.50 g: 10.0 mmol), and react at 50°C under nitrogen atmosphere for 6 hours. After returning to room temperature, TC-1 (1.84g: 9.4mmol) and NMP (10.0g) were added and allowed to react at room temperature for 18 hours to obtain a polymer with a viscosity of about 1120mPa·s and a solid content concentration of 20% by mass. Amino acid solution (PAA-1). The molecular weight of this polyamide acid is number average molecular weight: 11,200, weight average molecular weight: 31,360. The polyamic acid solution (PAA-1) (40.0 g) obtained above was measured in a 300 mL eggplant-shaped flask equipped with a stirring bar and a nitrogen gas introduction tube. Add NMP (74.3g), stir at room temperature for a period of time, add acetic anhydride (5.61g: 55.0mmol) and pyridine (2.90g, 36.7mmol), stir at room temperature for 30 minutes under nitrogen atmosphere, and then The reaction was carried out at 50°C for 3 hours. After completion of the reaction, the reaction solution was slowly poured into methanol (500 mL) cooled to below 10° C. while stirring to precipitate a solid, and stirred for 10 minutes. The precipitate was collected by filtration, and the slurry was washed with methanol (200mL) for 30 minutes, twice in total, and the solid was vacuum-dried at 80°C to obtain the desired polyimide powder (SPI-1) (7.04g , yield 88%). The imidization rate of this polyimide was 57%, the molecular weight was number average molecular weight: 10,400, and weight average molecular weight: 29,120.

<Synthesis Example 7> Measure DA-2 (3.42g: 14.0mmol) and DA-4 (4.11g: 6.0mmol) in a 100mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, add NMP (56.8g), and Stir under ambient conditions to dissolve it, keep it below 10°C in an ice bath, add TC-3 (4.26g: 19.0mmol) and NMP (10.0g), and react at room temperature for 24 hours to obtain a viscosity of Polyamic acid solution (PAA-2) with a solid content concentration of 15% by mass at about 680mPa·s. The molecular weight of this polyamide acid is number average molecular weight: 17,200, weight average molecular weight: 48,160.

<Synthesis Example 8> Measure DA-2 (3.42g: 14.0mmol) and DA-5 (1.55g: 6.0mmol) in a 100mL four-neck flask equipped with a mechanical stirrer and a nitrogen inlet tube, add NMP (42.0g), and Stir under ambient conditions to dissolve it, keep it in an ice bath below 10°C, add TC-3 (4.21g: 18.8mmol) and NMP (10.0g), and react at room temperature for 24 hours to obtain the viscosity It is a polyamic acid solution (PAA-3) at about 710mPa·s and a solid content concentration of 15% by mass. The molecular weight of this polyamide acid is number average molecular weight: 15,500, weight average molecular weight: 41,800.

＜＜Preparation of free radical generating film-forming composition and liquid crystal alignment agent＞＞ <Preparation Example 1 Preparation of Free Radical Generating Membrane Forming Composition AL-1> Measure 2.0 g of the polyimide powder (SPI-1) obtained in Synthesis Example 6 above into a 50 mL Erlenmeyer flask equipped with a stirring bar, add NMP (18.0 g), and stir at room temperature for 12 hours to dissolve it. After confirming that the solid was completely dissolved, NMP (8.0 g), BCS (12.0 g), and AD-1 (0.20 g) were added, and stirred at room temperature for 1 hour to obtain the free radical generating film-forming composition used in the present invention (AL- 1).

<Preparation Example 2 Preparation of Free Radical Generating Membrane Forming Composition AL-2> Measure 15.0 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 7 above into a 50 mL Erlenmeyer flask equipped with a stirring bar, add NMP (16.5 g) and BCS (13.5 g), and stir at room temperature for 1 hour. The radical generating film-forming composition (AL-2) used in the present invention was obtained.

＜Preparation Example 3 Preparation of liquid crystal alignment agent AL-3＞ Measure 15.0 g of the polyamic acid solution (PAA-3) obtained in Synthesis Example 8 above in a 50 mL Erlenmeyer flask equipped with a stirring bar, add NMP (16.5 g) and BCS (13.5 g), and stir at room temperature for 1 hour. The liquid crystal alignment agent (AL-3) used in the present invention was obtained.

The following shows the evaluation results of Examples and Comparative Examples among the liquid crystal display elements produced by photo-alignment. <Fabrication of liquid crystal display element> The following shows the fabrication method of a liquid crystal cell for evaluating liquid crystal alignment and electro-optic response. First prepare the substrate with electrodes. The substrate is an alkali-free glass substrate with a size of 30mm×35mm and a thickness of 0.7mm. On a substrate with a surface electrode (counter electrode: 1st layer) and a SiN film (insulating film: 2nd layer), electrodes are formed with a width of 3mm, an electrode-to-electrode interval of 6mm, and a 10° angle with respect to the long side of the substrate. The ITO (Indium-Tin-Oxide) electrode (pixel electrode: the third layer) of the comb-shaped pattern of the angle forms two pixels of the first pixel and the second pixel. The size of each pixel is 10mm in length and 5mm in width. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the function of the SiN film of the second layer. Hereinafter referred to as FFS substrate. The pixel electrode on the third layer has a comb-tooth shape in which a plurality of electrode elements with a width of 3 μm bent at an inner angle of 160° are arranged in parallel at intervals of 6 μm. One pixel connects many electrode elements. The line of the bending part is the boundary, and has the first zone and the second zone. Then, the free radical generating film-forming compositions AL-1, AL-2, liquid crystal alignment agent AL-3, and liquid crystal alignment agent SE-6414 (manufactured by Nissan Chemical Co., Ltd.) After the filter was filtered, the prepared above-mentioned FFS substrate and the glass substrate with the ITO film formed on the back of the counter substrate and the columnar spacer with a height of 3.0 μm were coated and formed by the spin coating method. Then, after drying for 2 minutes on a hot plate at 80° C., firing was performed at 230° C. for 20 minutes to obtain a coating film with a film thickness of 100 nm. For the polyimide film on the FFS substrate, the alignment treatment is carried out in the direction along the comb-tooth direction, and for the polyimide film on the glass substrate, the alignment treatment is carried out in the direction perpendicular to the comb-tooth electrodes. Also, for alignment treatment, AL-1 and SE-6414 use the friction method, with IINUMA GAUGE friction device, Yoshikawa Chemical Co. s, the roller speed is 700rpm, and the pushing pressure is 0.3mm. Both AL-2 and AL-3 use the UV exposure device made by USHIO Electric Co., Ltd. to irradiate polarized UV light, so that the linear polarized UV light with an extinction ratio of about 26:1 becomes 300mJ/cm ² based on the wavelength of 254nm. Heating at 230° C. for 20 minutes for alignment treatment. Afterwards, using the above two kinds of substrates, for the display element as the object of the embodiment, the free radical generation alignment film AL-1 or AL-2 is set on the FFS substrate side, and the liquid crystal alignment film SE-6414 or AL is set on the glass substrate side. For the combination of -3, SE-6414 or AL-3 is used for both substrates of the display element as the comparison object. The respective alignment directions were combined so that the liquid crystal injection port was left, and the surrounding was sealed (sealant; XN-1500T manufactured by Mitsui Chemicals Co., Ltd.) to obtain a ghost cell with a cell gap of about 3.0 μm. In this ghost cell, the liquid crystal mixture obtained by adding 2% by mass of (Add-1) to (Add-5) obtained in the above synthesis example, and the liquid crystal mixture without addition or the (Add-5) obtained by adding 2% by mass as the comparison object were used. -C1)~(Add-C2) liquid crystal mixtures were vacuum-injected at room temperature, and then the injection ports were sealed to obtain liquid crystal cells with antiparallel alignment. In addition, LC-A (manufactured by DIC Corporation, Δn: 0.130, Δε: 4.4) was used for the liquid crystal mixture. The obtained liquid crystal cell constitutes an IPS mode liquid crystal display element. Thereafter, the obtained liquid crystal cell was heat-treated at 120° C. for 10 minutes, and was irradiated with UV (UV lamp: FLR40SUV32/A-1) for 30 minutes using a UV-FL irradiation device manufactured by TOSHIBA LIGHTECH Co., Ltd. without applying voltage, to obtain Liquid crystal display element.

＜Evaluation of liquid crystal alignment quality＞ Using a polarizing microscope, set the polarizing plate to crossed Nicols, and fix it at the state where the brightness of the liquid crystal cell becomes the minimum. From this point, the liquid crystal cell is rotated by 1°, and the alignment state of the liquid crystal is observed. When no misalignment such as spots or microdomains was observed or very slight, it was rated as "good", and when misalignment such as spots or microdomains was clearly observed, it was rated as "poor". Also, install a photodiode on a copolarizing microscope, connect it to a potentiometer through a current-voltage conversion amplifier, and observe the voltage at which the brightness becomes the minimum condition under crossed Nicols to measure the black brightness.

＜V-T Curve Measurement and Driving Threshold Voltage, Maximum Brightness Voltage, Transmittance Evaluation＞ Install a white LED backlight and a luminance meter in such a way that the optical axes coincide, and place a liquid crystal cell (liquid crystal display element) with a polarizer installed therein so that the brightness becomes the minimum, and apply a voltage up to 8V at intervals of 1V, and measure it at each The brightness of the voltage is measured by the V-T curve. From the obtained V-T curve, the value of the voltage (Vmax) at which the luminance becomes maximum is estimated. In addition, through the liquid crystal cell with no voltage applied, the transmission luminance when parallel to the Nicols is set to 100%, and compared with the maximum transmission luminance on the V-T curve to estimate the maximum transmission (Tmax).

＜Measurement of response time (Ton, Toff)＞ Using the device used in the measurement of the V-T curve above, connect the luminance meter to an oscilloscope, and measure the response speed (Ton) when the voltage at maximum brightness is applied and the response speed (Toff) when the voltage returns to 0V.

＜Evaluation of branding caused by long-term AC drive＞ Only for the first pixel of the above-mentioned IPS driving liquid crystal cell, apply an AC voltage of ±5V at a frequency of 30Hz for 120 hours in a constant temperature environment of 60°C. After that, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited, and left at room temperature for one day in this state. After being placed, the liquid crystal cell is placed between two polarizers arranged so that the polarization axis is perpendicular to each other, and the backlight is first turned on in a state where no voltage is applied, and the arrangement of the liquid crystal cell is adjusted so that the brightness of the transmitted light becomes the minimum. angle. Then, the rotation angle for rotating the liquid crystal cell from the angle at which the first region of the second pixel becomes darkest to the angle at which the first region of the first pixel becomes darkest is calculated, expressed as an angle Δ. Similarly, the same angle Δ is calculated by comparing the second area of the second pixel with the second area of the first pixel. Then, calculate the average value of the calculated angle Δ values, and define it as the angle Δ of the liquid crystal cell. The angle Δ of the liquid crystal cell obtained above was rated as "poor" if it was 0.10° or more, and "good" if it was less than 0.10°.

＜Evaluation of driving characteristics in low temperature environment＞ Using the temperature adjustment platform made by Linkam, adjust the temperature of the liquid crystal cell between 20~-20°C, measure the V-T curve at each temperature, and compare the values of Tmax and Vmax to evaluate the low temperature driving characteristics.

＜Contents of Polymer＞ The compositions of the polymers synthesized in Synthesis Example 6 to Synthesis Example 8 are shown in Table 1.

[Table 1] polymer composition Imidization rate (%) SPI-1 TC-1(50)TC-2/DA-1(50)DA-3 57 PAA-2 TC-3/DA-2(70)DA-4 - PAA-3 TC-3/DA-2(70)DA-5 -

<Contents of Liquid Crystal Alignment Agent or Free Radical Generating Film Forming Composition> Table 2 shows the composition of the liquid crystal alignment agent or the free radical generating film-forming composition prepared in Preparation Example 1 to Preparation Example 3.

[Table 2] Liquid crystal alignment agent or free radical generating film forming composition Contains polymer Polymer solid content (mass%) Solvent (mass ratio) AL-1 SPI-1 5 NMP/BCS(65/30) AL-2 PAA-2 5 NMP/BCS(65/30) AL-3 PAA-3 5 NMP/BCS(65/30) SE-6414 - - -

＜Contents of Liquid Crystal Cell (Rubbing Alignment)＞ Table 3 shows the contents of Examples and Comparative Examples of liquid crystal cells that have undergone alignment treatment by the rubbing alignment method.

[table 3] Example FFS substrate Glass base board additive 1 AL-1 SE-6414 Add-1 2 AL-1 SE-6414 Add-2 3 AL-1 SE-6414 Add-3 4 AL-1 SE-6414 Add-4 5 AL-1 SE-6414 Add-5 Comparative example 1 SE-6414 SE-6414 no added Comparative example 2 AL-1 SE-6414 Add-C1 Comparative example 3 AL-1 SE-6414 Add-C2

＜Evaluation of Liquid Crystal Cell (Rubbing Alignment)＞ Table 4 shows the evaluation results of the characteristics of the liquid crystal cells subjected to the alignment treatment by the rubbing alignment method.

[Table 4]

The weakly anchored liquid crystal cells using the additives (Add-1)~(Add-5) of the present invention had good alignment quality and black brightness, and it was confirmed that the pretilt angle on the weakly anchored side did not occur and was below 0.1°. In addition, it can be seen that the lowering of the driving voltage significantly improves the transmittance. On the other hand, in Comparative Examples 2 to 3, using (Add-C1) or (Add-C2) as the liquid crystal display element as an additive, many rubbing streaks were confirmed, and the black brightness was not good, and compared with Comparative Example 1 The liquid crystal cell is strongly anchored, and the Vmax decreases, but the behavior of decreasing the transmittance is confirmed. It can be seen that the cause is due to the occurrence of pretilt angles accompanying the weak anchoring. In Comparative Example 2, a very large pretilt angle of about 10° and in Comparative Example 3 of 80° occurred. On the other hand, regarding the response speed, it can be seen that when the additives of Examples 1-5 are used, compared with the strongly anchored liquid crystal cell of Comparative Example 1, the response speed is slightly slower, but it is still within the allowable range, and a fast response speed can be achieved. The response speed is greatly improved compared with Comparative Examples 2~3. Furthermore, for the burn-in, when the additives of Examples 1-5 are used, it is about the same as that of Comparative Example 1, and it is greatly improved compared with Comparative Examples 2-3. When using MLC-3019 (Δn: 0.104, Δε: 9.9) manufactured by Merck as a liquid crystal, good weakly anchored IPS characteristics can be obtained even when Add-C1 used in Comparative Example 2 is used. Liquid crystals with small Δε and small Δε cannot obtain good characteristics of weakly anchored IPS. This result means, for example, that the additives used in Comparative Examples 2 to 3 cannot respond to the narrowing of the unit cell gap to manufacture a liquid crystal display device. Even if such high Δn and small Δε liquid crystals are used in the additive of the present invention, good weakly anchored IPS characteristics can be obtained, and the response speed can be improved by narrowing the unit cell gap. Furthermore, burn-in can be greatly reduced.

＜Low temperature driving evaluation (frictional alignment)＞ Table 5 shows the low-temperature evaluation results of the liquid crystal cells subjected to alignment treatment by the rubbing alignment method.

[table 5]

It can be seen that in the liquid crystal display elements using (Add-C1) or (Add-C2) as an additive in Comparative Examples 2 to 3, the driving voltage becomes higher and the transmittance decreases significantly as the temperature of the liquid crystal cell decreases. This result is due to the high pretilt angle of the liquid crystal along with the decrease of the unit cell temperature. It is revealed that the risk of pretilt angle increases in the low temperature environment. On the other hand, if the additives (Add-1)~(Add-5) of the present invention are used, relatively high transmittance and low driving voltage can be achieved even in a low temperature environment. In particular, when (Add-1) is used up to 0°C, when (Add-2) is used up to -20°C, and when (Add-3) is used up to -10°C, there is no change in Vmax and Tmax. Low temperature environment shows high drive stability. The difference due to the additives used is due to the difference in the glass transition temperature of the weakly anchored film formed by each additive. It is believed that because the unit cell temperature is lower than the glass transition temperature of the weakly anchored film, the weakly anchored film condenses and becomes It is impossible to show the original effect. From this result, it can be known that the reduction of the glass transition temperature of the weakly anchored film, the increase in the number of carbons constituting the cycloalkane core, and the installation of a linking group between the cycloalkane core and the polymerizable group are effective, and the use of acryloxy It is particularly effective as a polymerizable group.

＜Contents of liquid crystal cell (photo-alignment)＞ Table 6 shows the contents of Examples and Comparative Examples of liquid crystal cells that have undergone alignment treatment by the photo-alignment method.

[Table 6]

＜Evaluation of Liquid Crystal Cell (Photo-Alignment)＞ Table 7 shows the evaluation results of the properties of the liquid crystal cells that have been aligned by the photo-alignment method.

[Table 7]

The weakly anchored unit cells using the additives (Add-1)~(Add-5) of the present invention can still achieve alignment quality and black brightness improvement, transmittance improvement, high-speed response, and further reduce burn-in in the photo-alignment method . On the other hand, if (Add-C1) and (Add-C2) used in Comparative Examples 5 to 6 were used, micro domains would occur and the drive would not be possible. In photo-alignment, unlike the rubbing method, the anisotropy of the pre-tilt angle is not regulated. When a relatively large pre-tilt angle occurs in some methods, it will be seen in the form of micro-domains. It is speculated that the area of the micro-domain is expanded by the electric field during driving, so it cannot be driven. It can be seen that if the additive of the present invention is used, microdomains will not occur even if photo-alignment is used, and good weakly anchored IPS characteristics can be obtained, which is very useful.

＜Low temperature drive evaluation (photoalignment)＞ Table 8 shows the low-temperature evaluation results of liquid crystal cells that have undergone alignment treatment by the photo-alignment method.

[Table 8]

The weakly anchored unit cells using the additives (Add-1)~(Add-5) of the present invention can obtain relatively high transmittance and lower driving voltage even in a low-temperature environment by photo-alignment method. The values of Vmax and Tmax when using various additives in a low temperature environment have the same tendency as when using the rubbing alignment method (Table 5). It is inferred that the weak anchor film formed is uniform regardless of the alignment method. Also, in Comparative Examples 5 to 6, the failure to drive was due to the occurrence of micro-domains originating from the pretilt of the liquid crystal. [Industrial Utilization]

According to the present invention, even if liquid crystals with high Δn and low Δε are used, there will be no pretilt angle and micro domains, and a transverse electric field liquid crystal display element that can achieve high backlight transmittance and fast response speed can be provided, and a liquid crystal display with good reliability can be obtained element. Therefore, the liquid crystal display element obtained by the method of the present invention is useful as a liquid crystal display element of a transverse electric field driving method.

1: Transverse 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: Facing the substrate 4a: Liquid crystal alignment film 4b: Substrate L: power line

Fig. 1 shows a schematic cross-sectional view of an example of a transverse electric field liquid crystal display element of the present invention. Fig. 2 shows a schematic cross-sectional view of another example of the transverse electric field liquid crystal display element of the present invention.

1: Transverse electric field liquid crystal display element

2: Comb electrode substrate

2a: Substrate

2b: Wire electrode

2c: Liquid crystal alignment film

3: LCD

4: Facing the substrate

4a: Liquid crystal alignment film

4b: Substrate

L: power line

Claims (24)

A method for manufacturing a liquid crystal display device, comprising: polymerizing a radical polymerizable compound in a state where a liquid crystal composition containing a liquid crystal and a radical polymerizable compound represented by the following formula (A) is brought into contact with a radical generating film step,

In the formula (A), M represents a polymerizable group capable of free radical polymerization, S represents a single bond, or a saturated hydrocarbon group with 1 to 6 carbon atoms that can also be inserted into a bonding group, and T represents an organic compound represented by the following formula (B). base, n is an integer from 1 to 2; when n is 2, the two Ts can be the same or different; but when n is 2, S means that a saturated hydrocarbon group with 1 to 6 carbon atoms of the bonding group can also be inserted,

In formula (B), * represents the bonding site; X is selected from single bond, ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, -Si(R ₁ )(R ₂ )-(R ₁ and R ₂ each independently represent an alkyl group bonded to Si), -Si(R ₃ )(R ₄ )-O-(R ₃ and R ₄ each independently represent an alkyl group bonded to Si Alkyl), and -N(R ₅ )-(R ₅ represents a hydrogen atom or an alkyl group bonded to N), and Cy represents a non-aromatic cyclic group with 6 to 20 membered rings. The method for manufacturing a liquid crystal display element as claimed in item 1, wherein, in the formula (B), the ring in the non-aromatic cyclic group of the 6-20-membered ring of Cy is a cyclic alkane with a 6-20-membered ring . The method for manufacturing a liquid crystal display element as claimed in item 1, wherein M in the formula (A) is selected from the following structures,

In the formula, * represents the bonding site; R ^b represents a straight-chain alkyl group with 2 to 8 carbons, and E represents a group selected from single bonds, -O-, -NR ^c -, -S-, ester bonds and amide bonds. A bonding group; R ^c represents a hydrogen atom, or an alkyl group with 1 to 4 carbons. The method of manufacturing a liquid crystal display device according to claim 1, wherein the radical generating film is a radical generating film subjected to uniaxial alignment treatment. The method for manufacturing a liquid crystal display element as claimed in item 1, wherein the step of the polymerization reaction is carried out under the condition of no electric field. The method of manufacturing a liquid crystal display device according to Claim 1, wherein the radical generating film is a film formed by immobilizing organic radicals that induce radical polymerization. The method of manufacturing a liquid crystal display element according to claim 1, wherein the free radical generating film is formed by coating a composition containing a compound having a free radical-generating organic radical and a polymer, and hardening to form a film, and It is obtained by immobilizing the radical-generating organic radical in the film. The method of manufacturing a liquid crystal display device according to claim 1, wherein the radical generating film is composed of a polymer containing an organic group that induces radical polymerization. The method for manufacturing a liquid crystal display device according to Claim 8, wherein the polymer containing an organic group that induces radical polymerization is obtained by using a diamine component containing a diamine containing an organic group that induces free radical polymerization At least one polymer selected from polyimide precursor, polyimide, polyurea and polyamide. The method for manufacturing a liquid crystal display element as claimed in item 9, wherein the organic group that induces free radical polymerization is represented by the following formula [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 ^a -(R ^a represents a hydrogen atom, or carbon number 1~ 10 alkyl), or -S-, R represents a hydrogen atom, or an alkyl group with 1 to 10 carbons (among the aforementioned alkyl groups with 1 to 10 carbons, -CH ₂ for an alkyl group with 2 to 10 carbons Part of the - group can also be substituted by an oxygen atom, but in S ₂ R or NR ^a , when a part of the -CH ₂ - group of the aforementioned alkyl group is replaced by 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 an alkyl group with 1 to 4 carbons,

In the formulas [W], [Y], and [Z], * represents a bonding site, and Ar represents a group selected from phenylene, naphthylene, and extension groups that may also have organic groups and/or halogen atoms as substituents. In the aromatic hydrocarbon group in the group formed by phenyl, ^R9 and R10 each independently represent an alkyl group with 1 to ¹⁰ carbons or an alkoxy group with 1 to ¹⁰ carbons, when ^R9 and R10 are alkyl groups, It is also possible to bond each other at the ends and form a ring structure; Q represents any of the following structures,

In the formula, R ¹¹ represents -CH ₂ -, -NR ^a - (R ^a represents a hydrogen atom or an alkyl group with 1 to 4 carbons), -O-, or -S-, each R independently represents a hydrogen atom or a carbon An alkyl group with a number of 1~4, * stands for a bonding site; S ³ stands for a single bond, -O-, -NR ^b - (R ^b stands for a hydrogen atom or an alkyl group with a carbon number of 1~14), 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. The method for manufacturing a liquid crystal display element as claimed in item 9, wherein the diamine containing an organic group that induces free radical polymerization is a diamine represented by the following formula (6), the following formula (7), or the following 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 C1-20 alkylene group, the alkene group Any one or more of -CH ₂ - or -CF ₂ - in the alkyl group may also be independently substituted by a group selected from -CH═CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and then Or, it can also be substituted by any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other; R ⁸ represents a radical polymerization reactive group selected from the formulas of the following formulas [X-1] to [X-18],

In the formulas [X-1]~[X-18], * represents the bonding site, S ₁ and S ₂ each independently represent -O-, -NR ^a -(R ^a represents a hydrogen atom, or carbon number 1~ 10 alkyl), or -S-, R represents a hydrogen atom, or an alkyl group with 1 to 10 carbons (among the aforementioned alkyl groups with 1 to 10 carbons, -CH ₂ for an alkyl group with 2 to 10 carbons Part of the - group can also be substituted by an oxygen atom; but in S ₂ R or NR ^a , when a part of the -CH ₂ - group of the alkyl group is replaced by 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 an alkyl group with 1 to 4 carbons,

In formulas ( ₇ ) and ( ₇ '), T1 and T2 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 fluorine atom-substituted carbon number 1 ~20 alkylene groups, any one or more of -CH ₂ - or -CF ₂ - in the alkylene group can also be independently selected from -CH═CH-, divalent carbocycles, and divalent The substituents in the valent heterocyclic ring can also be replaced by any of the following groups, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other As a condition, to be substituted by such groups, E is a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -NHCO-, -COO-, -(CH ₂ ) _m - , -SO ₂ -, -O-(CH ₂ ) _m -O-, -OC(CH ₃ ) ₂ -, -CO-(CH ₂ ) _m -, -NH-(CH ₂ ) _m -, -SO ₂ -(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -NHCO-, or -COO-(CH ₂ ) _m -OCO-, m is an integer from 1 to 8 , J is an organic group selected from the following formulas [W], [Y] and [Z],

_In the formulas [W], [Y], and [Z], * represents the bonding position with T2, and Ar represents a group selected from phenylene and naphthylene groups that may also have organic groups and/or halogen atoms as substituents. , and the aromatic hydrocarbon group in the group consisting of extended biphenyl groups, 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, and Q represents any of the following structure,

In the formula, R ¹¹ represents -CH ₂ -, -NR ^a - (R ^a represents a hydrogen atom or an alkyl group with 1 to 4 carbons), -O-, or -S-, each R independently represents a hydrogen atom or a carbon An alkyl group with a number of 1~4, * represents a bonding site; S ³ represents a single bond, -O-, -NR ^b - (R ^b represents a hydrogen atom or an alkyl group with a carbon number of 1 ~ 14), 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; in formula (7'), q are each independently 0 or 1, and at least one q is 1 , p represents an integer from 1 to 2; when there are a plurality of T ₁ , T ₂ , S, J, E, and q, the plurality of T ₁ , T ₂ , S, J, E, and q can be the same as each other or can be different. The method for manufacturing a liquid crystal display element as claimed in claim 1, comprising the following steps: preparing the first substrate having the radical generating film, and the second substrate optionally having the free radical generating film, disposing the first substrate and the second substrate facing each other in such a way that the free radical generating film in the first substrate faces the second substrate, filling the liquid crystal composition between the first substrate and the second substrate, and The polymerization reaction is carried out. The method of manufacturing a liquid crystal display element according to claim 12, wherein the second substrate is a second substrate without a radical generating film. The method for manufacturing a liquid crystal display element according to claim 12, wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment. The method for manufacturing a liquid crystal display element according to claim 14, wherein the liquid crystal alignment film having uniaxial alignment is a liquid crystal alignment film for horizontal alignment. The method for manufacturing a liquid crystal display element according to claim 12, wherein any one of the first substrate and the second substrate is a substrate having comb electrodes. A liquid crystal composition characterized by containing liquid crystals and a radically polymerizable compound represented by the following formula (A),

In the formula (A), M represents a polymerizable group capable of free radical polymerization, S represents a single bond, or a saturated hydrocarbon group with 1 to 6 carbon atoms that can also be inserted into a bonding group, and T represents an organic compound represented by the following formula (B). base, n is an integer from 1 to 2; when n is 2, the two Ts can be the same or different; but when n is 2, S means that a saturated hydrocarbon group with 1 to 6 carbon atoms of the bonding group can also be inserted,

In formula (B), * represents the bonding site; X is selected from single bond, ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, -Si(R ₁ )(R ₂ )-(R ₁ and R ₂ each independently represent an alkyl group bonded to Si), -Si(R ₃ )(R ₄ )-O-(R ₃ and R ₄ each independently represent an alkyl group bonded to Si Alkyl), and -N(R ₅ )-(R ₅ represents a hydrogen atom or an alkyl group bonded to N), and Cy represents a non-aromatic cyclic group with 6 to 20 membered rings. The liquid crystal composition as claimed in item 17, wherein, in the formula (B), the ring in the non-aromatic cyclic group of the 6-20-membered ring of Cy is a cyclic alkane with a 6-20-membered ring. The liquid crystal composition according to claim 17, wherein M in the formula (A) is selected from the following structures,

In the formula, * represents the bonding site; R ^b represents a straight-chain alkyl group with 2 to 8 carbon atoms, and E represents a group selected from single bonds, -O-, -NR ^c -, -S-, ester bonds and amide bonds. Bonding group; R ^c represents a hydrogen atom or an alkyl group with 1 to 4 carbons. A liquid crystal display element, characterized by: having a first substrate, a second substrate disposed opposite to the first substrate, and a liquid crystal filled between the first substrate and the second substrate, so as to contain the A liquid crystal composition of a liquid crystal and a radically polymerizable compound represented by the following formula (A) is formed by polymerizing the radically polymerizable compound in a state where the radically polymerizable compound is in contact with the radically generating film of the first substrate having the radically generating film ,

In the formula (A), M represents a polymerizable group capable of free radical polymerization, S represents a single bond, or a saturated hydrocarbon group with 1 to 6 carbon atoms that can also be inserted into a bonding group, and T represents an organic compound represented by the following formula (B). base, n is an integer from 1 to 2; when n is 2, the two Ts can be the same or different; but when n is 2, S means that a saturated hydrocarbon group with 1 to 6 carbon atoms of the bonding group can also be inserted,

In formula (B), * represents the bonding site; X is selected from single bond, ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, -Si(R ₁ )(R ₂ )-(R ₁ and R ₂ each independently represent an alkyl group bonded to Si), -Si(R ₃ )(R ₄ )-O-(R ₃ and R ₄ each independently represent an alkyl group bonded to Si Alkyl), and -N(R ₅ )-(R ₅ represents a hydrogen atom or an alkyl group bonded to N), and Cy represents a non-aromatic cyclic group with 6 to 20 membered rings. The liquid crystal display element according to claim 20, wherein any one of the first substrate and the second substrate is a substrate having comb electrodes. The liquid crystal display element as claimed in item 20 is a low voltage driven transverse electric field liquid crystal display element. A radically polymerizable compound characterized by being represented by the following formula (A),

In formula (A), M represents acryloxy or methacryloxy, S represents a saturated hydrocarbon group with 1 to 6 carbons that may also be inserted into a bonding group, and T represents an organic group represented by the following formula (B) , n is an integer from 1 to 2; when n is 2, the two Ts can be the same or different,

In formula (B), * represents the bonding site; X is selected from ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, -Si(R ₁ )(R ₂ )- (R ₁ and R ₂ each independently represent an alkyl group bonded to Si), -Si(R ₃ )(R ₄ )-O- (R ₃ and R ₄ each independently represent an alkyl group bonded to Si) , and -N(R ₅ )-(R ₅ represents a hydrogen atom or an alkyl group bonded to N), and Cy represents a non-aromatic cyclic group with 12 to 20 membered rings. Such as the free radical polymerizable compound of claim 23, represented by the following formula (C),

In formula (C), R ₃ and R ₄ each independently represent an alkyl group with 1 to 6 carbons, R ₆ represents an alkylene group with 1 to 6 carbons, R ₇ represents a hydrogen atom or a methyl group, and p represents 1 to 6 Integer of 9.

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