TW202132412A - Radical generation film-forming composition, radical generation film, and method for manufacturing horizontal-electric-field liquid crystal cell - Google Patents

Abstract

In order to obtain a horizontal-electric-field liquid crystal display element by which favorable black displaying is possible, and high backlight transmittance and fast response speed can be achieved, a radical generation film-forming composition used for the horizontal-electric-field liquid crystal display element is provided. This radical generation film-forming composition contains: a component (A) which is a polymer having, in a main chain, a structural unit represented by formula (1); and a component (B) which is a polymer used as an alignment component of a liquid crystal aligning agent for driving a horizontal electric field. (In the formula, A represents an organic group that induces radical polymerization.).

Description

Free radical generating film forming composition, free radical generating film, and manufacturing method of transverse electric field liquid crystal cell

The present invention relates to a radical generating film forming composition and a radical generating film that can be ideally used for weakly anchored liquid crystal display elements and the like. In addition, the present invention relates to a method for producing a transverse electric field liquid crystal cell using the radical generating film forming composition and the radical generating film.

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

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

In recent years, with the goal of higher definition and higher contrast in 4K, 8K, etc., the high brightness of the backlight has also progressed. Along with this, liquid crystal display elements are also aimed at improving transmittance and lowering driving voltage. In particular, the FFS mode is not only used for TV applications, but also used in tablets, smart phones, etc., so the transmittance improvement and the reduction of driving voltage become Very big subject.

Regarding the improvement of the transmittance of the liquid crystal display element, the method of using negative liquid crystal has been proposed for the FFS mode, and it has actually been put into practical use. On the other hand, when using negative type liquid crystal, although the effect of improving the transmittance is great, the response time is also deteriorated and the driving voltage is increased, so the power consumption reduction effect is low, and the negative type liquid crystal itself can be mentioned. Easily dissolve contaminants and easily cause problems such as unevenness and burn-in.

Recently, in terms of technologies that can improve the transmittance of liquid crystal display elements and reduce the driving voltage, technologies such as weakly anchored IPS using a film with a very low anchoring energy as a liquid crystal alignment film have attracted much attention. The weakly anchored IPS technology, even if an IPS substrate with a certain width of the comb-tooth electrode is used as the substrate, the transmittance can be greatly improved, and the driving voltage can also be reduced. Therefore, if it can be put into practical use, the cost advantage of the substrate will be significant, and it can be suppressed. This is the advantage of the occurrence of flicker, which is a problem specific to the FFS mode (refer to Patent Document 1).

In recent years, some people have used thick polymer brushes to create a zero-face anchored state, and a technique of zero-face anchored IPS mode (also called weak anchored IPS mode) has been proposed (refer to Patent Document 2). With this technology, the contrast ratio is greatly improved and the driving voltage is greatly reduced. [Prior Technical Literature] [Patent Literature]

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

[The problem to be solved by the invention]

On the other hand, this technology has a problem in principle. The first point is that in order to stably produce a polymer brush on a substrate, it needs to be performed under very fine conditions, which is not realistic when considering mass production. The second point is that although the alignment film has important functions such as suppression of burn-in, it is difficult to control the necessary electrical properties when using a polymer brush or the like. The third point can be cited as far as the driving principle is concerned, the response speed when the voltage is Off will be very slow. By making the alignment binding force zero, the resistance to the driving of the liquid crystal is eliminated, and the threshold voltage is greatly reduced, and the brightness improvement due to the reduction of the poor alignment area during driving can be expected. However, the recovery of the liquid crystal is due to the recovery of the liquid crystal. The power depends on the elastic force of the liquid crystal, and it is thought that the speed will drop significantly compared to when there is an alignment film.

If such a technical problem can be solved, it is believed that for panel manufacturers, there are significant advantages in cost, as well as advantages in suppressing battery consumption and improving image quality.

The present invention is to solve the above-mentioned problems, and aims to provide a polymer stabilization technology that can produce weak anchor films, and can simultaneously achieve non-contact alignment and low driving voltage and acceleration at room temperature in a simple and low-cost method. A horizontal electric field liquid crystal display element with response speed when the voltage is Off. In particular, it aims to provide a horizontal electric field liquid crystal display element that can perform good black display, and can achieve high backlight transmittance and fast response speed. In addition, in order to obtain such an excellent horizontal electric field liquid crystal display element, the present invention aims to provide a radical generating film forming composition used in the horizontal electric field liquid crystal display element. [Means to solve the problem]

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

式(1)中，A表示誘發自由基聚合之有機基。 [2]如[1]之自由基產生膜形成組成物，其中，前述係(A)成分之聚合物，係選自於使用包含含有誘發自由基聚合之有機基之二胺的二胺成分而獲得之聚醯亞胺前驅體、聚醯亞胺、聚脲及聚醯胺中之至少一種聚合物。That is, the present invention includes the following contents. [1] A radical generating film-forming composition comprising: a polymer having a structural unit represented by the following formula (1) in the main chain of the component (A); and a liquid crystal for driving a transverse electric field as the component (B) The polymer used for the alignment component of the alignment agent. [化1]

In formula (1), A represents an organic group that induces radical polymerization. [2] The radical generating film forming composition according to [1], wherein the polymer of the component (A) is selected from the use of a diamine component containing a diamine containing an organic group that induces radical polymerization. The obtained polyimide precursor, polyimine, polyurea and at least one polymer of polyimide.

式(2)中，A¹ 及A² 各自表示氫原子或誘發自由基聚合之有機基，惟，A¹ 及A² 中之至少1者表示誘發自由基聚合之有機基； E表示單鍵、-O-、-C(CH₃ )₂ -、-NH-、-CO-、-NHCO-、-COO-、-(CH₂ )_m -、-SO₂ -、或由該等之任意組合構成的2價有機基，m表示1～8之整數。[3] The radical generating film forming composition according to [2], wherein the aforementioned diamine containing an organic group that induces radical polymerization is a diamine represented by the following formula (2). [化2]

In formula (2), A ¹ and A ² each represent a hydrogen atom or an organic group that induces free radical polymerization, but ^{at least one of A 1} and A ² represents an organic group that induces free radical polymerization; E represents a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -NHCO-, -COO-, -(CH ₂ ) _m -, -SO ₂ -, or any combination of these In the divalent organic group, m represents an integer of 1-8.

式(3)中，虛線表示與苯環之鍵結，R⁶ 表示單鍵、-CH₂ -、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH₂ O-、-N(CH₃ )-、-CON(CH₃ )-、或-N(CH₃ )CO-； R⁷ 表示單鍵、或非取代或經氟原子取代之碳數1～20之伸烷基，該伸烷基之任意之-CH₂ -或-CF₂ -中之一者以上也可各自獨立地置換為選自-CH=CH-、二價碳環、及二價雜環之基，另外，亦能以下列所列舉之任意基，亦即-O-、-COO-、-OCO-、-NHCO-、-CONH-、或-NH-彼此不相鄰為條件而置換為該等基。p represents an integer of 0-2. When p is 2, each of a plurality of A ² independently has the aforementioned definition. In addition, when p is 0, A ^{1 is} composed of an organic group that induces radical polymerization. [4] The radical generating film forming composition according to any one of [1] to [3], wherein the aforementioned organic group that induces radical polymerization is a group represented by the following formula (3). [化3]

In formula (3), the dotted line represents the bond with the benzene ring, and R ⁶ represents a single bond, -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-; R ⁷ represents a single bond, or the number of carbons substituted by fluorine atoms 1 ～20 alkylenes, any _{one or more of -CH 2} -or -CF ₂ -of the alkylenes can also be independently substituted with selected from -CH=CH-, divalent carbocyclic ring, and two The group of a valent heterocyclic ring, in addition, can also be conditioned on any of the groups listed below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- are not adjacent to each other And replace with these bases.

式[X-1]～[X-18]中，＊表示與R⁷ 之鍵結部位，S₁ 及S₂ 各自獨立地表示-O-、-NR-、或-S-，R表示氫原子、鹵素原子、碳數1～10之烷基、或碳數1～10之烷氧基，R₁ 及R₂ 各自獨立地表示氫原子、鹵素原子、或碳數1～4之烷基；R ⁸ represents an organic group which is selected from the formulas [X-1]～[X-18], [W], [Y] and [Z] to induce radical polymerization; [化4]

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

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

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

式中，R¹¹ 表示-CH₂ -、-NR-、-O-、或-S-，R表示氫原子或碳數1～4之烷基，＊表示原子鍵； R¹² 表示氫原子、鹵素原子、碳數1～10之烷基或碳數1～10之烷氧基。Q represents any of the following structures; [化6]

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

[5] A radical generating film obtained by using the radical generating film forming composition of any one of [1] to [4]. [6] A method for manufacturing a transverse electric field liquid crystal cell, including the following steps: Prepare a first substrate with a liquid crystal alignment film and a second substrate with a radical generating film as in [5]; Fabricating the unit cell in such a way that the radical generating film on the second substrate faces the first substrate; and Between the first substrate and the second substrate, a liquid crystal composition containing liquid crystal and a radical polymerizable compound is filled; Either one of the first substrate and the second substrate is a comb-tooth electrode substrate, and the other is a counter substrate. [7] The method for manufacturing a transverse electric field liquid crystal cell according to [6], wherein the first substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment. [8] The method for manufacturing a transverse electric field liquid crystal cell according to [7], wherein the aforementioned liquid crystal alignment film with uniaxial alignment is a liquid crystal alignment film for horizontal alignment. [9] The method for manufacturing a transverse electric field liquid crystal cell according to any one of [6] to [8], wherein the comb-shaped electrode substrate is an IPS substrate or an FFS substrate. [Effects of Invention]

According to the present invention, in order to obtain a horizontal electric field liquid crystal display element that can perform good black display, high backlight transmittance and fast response speed, and can be effectively used for the free radical generating film of the horizontal electric field liquid crystal display element Form a composition.

(Free radical generating film forming composition) The radical generating film forming composition of the present invention contains (A) component and (B) component.

＜(A) Ingredient＞ The present invention contains a polymer having the structural unit represented by the above formula (1) in the main chain as the (A) component. As a result, the radical generating film forming composition of the present invention contains an organic group that induces radical polymerization. By coating and curing such a composition to form a film, a liquid crystal alignment film with various functions can be obtained by fixing radicals that generate radicals in the film.

The organic group that induces radical polymerization in this way can be exemplified by the group represented by the above formula (3).

As the organic group represented by the formula selected from the above-mentioned [W], [Y], and [Z], specifically, the following groups are preferable. In particular, considering the reliability of the obtained liquid crystal display element, (b) and (c) are preferable. [化7]

When using a polymer having an organic group that induces radical polymerization, which is the component (A) used in the present invention, in order to obtain a polymer having a group that generates radicals, it is preferable to use a polymer having a group selected from methacrylic acid, The monomer of photoreactive side chain of at least one of acrylic group, vinyl group, allyl group, coumarin group, styryl group, and cinnamon group, and the side chain has a site that decomposes and generates free radicals due to ultraviolet radiation. The monomer is preferably manufactured as a monomer component. On the other hand, it is considered that the monomer that generates free radicals itself polymerizes spontaneously and becomes an unstable compound. Therefore, considering the ease of synthesis, it is preferable to be derived from a diamine having free radical generating sites. The polymer is preferably polyimide precursors such as polyamide acid and polyamide ester, and more preferably polyimide, polyurea, polyamide, etc.

Such a diamine containing a radical generating site is specifically, for example, a diamine having a side chain capable of generating free radicals and polymerizing. The diamine represented by the above formula (2) may be mentioned, but it is not limited thereto. In the above formula (2), E represents a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -NHCO-, -COO-, -(CH ₂ ) _m -,- SO ₂ -, or a divalent organic group composed of any combination of these. Here, "any combination of these" includes -O-(CH ₂ ) _m -O-, -OC(CH ₃ ) ₂ -, -CO-(CH ₂ ) _m -, -NH-(CH ₂ ) _m -, -SO ₂ -(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -NHCO-, -COO-(CH ₂ ) _m -OCO-, etc., but not limited to these.

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

A diamine containing at least one photoreactive group selected from the group consisting of a methacrylic group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamyl group, specifically In particular, the following compounds can be cited, but are not limited to these. [化8]

式中，J¹ 表示單鍵、-O-、-COO-、-NHCO-、或-NH-，J² 表示單鍵、或非取代或經氟原子取代之碳數1～20之伸烷基。[化9]

In the formula, J ¹ represents a single bond, -O-, -COO-, -NHCO-, or -NH-, J ² represents a single bond, or unsubstituted or substituted by a fluorine atom, a C 1-20 alkylene group .

式中，n為2～8之整數，E表示單鍵、-O-、-C(CH₃ )₂ -、-NH-、-CO-、-NHCO-、-COO-、-(CH₂ )_m -、-SO₂ -、-O-(CH₂ )_m -O-、-O-C(CH₃ )₂ -、-CO-(CH₂ )_m -、-NH-(CH₂ )_m -、-SO₂ -(CH₂ )_m -、-CONH-(CH₂ )_m -、-CONH-(CH₂ )_m -NHCO-或-COO-(CH₂ )_m -OCO-，m為1～8之整數。A diamine having an organic group represented by the formula selected from the above-mentioned [W], [Y] and [Z], in view of ease of synthesis, versatility, characteristics, etc., the structure represented by the following formula is the best , But not limited to these. [化10]

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

式中，n為2～8之整數。[化11]

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

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

The diamine having such a site where radical polymerization occurs is preferably 5-100 mol% of the total diamine component used in the synthesis of the polymer of the component (A) contained in the radical generating film forming composition The amount of is preferably used, more preferably 10 to 80 mol%, particularly preferably 30 to 50 mol%.

In addition, when the polymer of component (A) used in the radical generating film forming composition of the present invention is obtained from diamine, other diamines other than the above-mentioned diamine having free radical generating sites can be used as the diamine. Element. Specifically, examples include: p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4 -Dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5- Diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3, 3'-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4 '-Diaminobiphenyl, 3,3'-Dicarboxy-4,4'-Diaminobiphenyl, 3,3'-Difluoro-4,4'-Diaminobiphenyl, 3,3' -Bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl Biphenyl, 2,3'-diaminodiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenyl Methane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane Phenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyl diphenylamine, 3,3'-sulfonyl diphenylamine, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl -Bis(3-aminophenyl)silane, 4,4'-sulfodiphenylamine, 3,3'-sulfodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diamino Diphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenylamine Phenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl(2, 2'-diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-di Aminobenzophenone, 3,4'-diaminobenzophenone, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,4- Diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-Diaminonaphthalene, 2,7-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4- Bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3 -Bis(4-aminophenoxy)benzene, 1,4-bis (4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-amino) Phenoxy)benzene, 4,4'-[1,4-phenylenebis(methylene)]diphenylamine, 4,4'-[1,3-phenylenebis(methylene)]di Aniline, 3,4'-[1,4-phenylenebis(methylene)]diphenylamine, 3,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3, 3'-[1,4-phenylenebis(methylene)]diphenylamine, 3,3'-[1,3-phenylenebis(methylene)]diphenylamine, 1,4-phenylene Bis[(4-aminophenyl) ketone], 1,4-phenylene bis[(3-aminophenyl) ketone], 1,3-phenylene bis[(4-amino Phenyl) ketone], 1,3-phenylene bis[(3-aminophenyl) ketone], 1,4-phenylene bis(4-aminobenzoate), 1,4 -Phenylene bis(3-amino benzoate), 1,3-phenylene bis(4-amino benzoate), 1,3-phenylene bis(3-amino benzoate) Acid ester), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalic acid Ester, bis(3-aminophenyl) isophthalate, N,N'-(1,4-phenylene) bis(4-aminobenzoamide), N,N'-( 1,3-phenylene) bis(4-aminobenzoamide), N,N'-(1,4-phenylene)bis(3-aminobenzoamide), N,N' -(1,3-phenylene) bis(3-aminobenzoamide), N,N'-bis(4-aminophenyl)p-xylylenedimethamide, N,N'-bis( 3-aminophenyl)p-xylylenedimethamide, N,N'-bis(4-aminophenyl)m-xylylenedimethamide, N,N'-bis(3-aminophenyl)m Xylylenedimethamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenyl sulfide, 2,2'-bis[4-( 4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminobenzene) Yl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2 '-Bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, Trans-1,4-bis(4-aminophenyl)cyclohexane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, bis(4-aminophenoxy) Methane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane , 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane Alkyl, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminobenzene Oxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-amino) Phenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-amine Phenyloxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis(3- Aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-bis (4-aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)dodecane and other aromatic diamines; bis(4-aminocyclohexyl)methane, bis(4 -Amino-3-methylcyclohexyl) methane and other alicyclic diamines; 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1, 6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1, Aliphatic diamines such as 11-diaminoundecane and 1,12-diaminododecane; 1,3-bis[2-(p-aminophenyl)ethyl]urea, 1,3-bis [2-(p-aminophenyl) ethyl]-1-tertiary butoxycarbonyl urea and other diamines with urea structure; N-p-aminophenyl-4-p-aminophenyl (third-butyl (Oxycarbonyl)aminomethylpiperidine and other diamines with nitrogen-containing unsaturated heterocyclic structure; N-tertiary butoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N -(4-Aminobenzyl)amine, etc., a diamine having an N-Boc group (Boc represents a tertiary butoxycarbonyl group), and the like.

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

In the synthesis when the polymer is polyamide acid, the tetracarboxylic dianhydride that reacts with the above-mentioned diamine component is not particularly limited. Specifically, examples include: pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid , 2,3,6,7-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, 2,3,3', 4'-Biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl) ether, 3,3',4,4'-benzophenone tetracarboxylic acid, bis(3,4-dicarboxyphenyl) ), bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2, 2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethylsilane, bis(3,4-dicarboxyphenyl)diphenylsilane, 2,3 ,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenyl tetracarboxylic acid, 3,4,9, 10-perylene tetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid, oxydiphthalate tetracarboxylic acid, 1,2,3,4- Cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-tetramethyl-1 ,2,3,4-cyclobutane tetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid, 1,3-dimethyl-1,2,3 ,4-Cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid, 3,4-dicarboxy-1-cyclohexylsuccinic acid Acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, bicyclo[3.3.0]octane-2, 4,6,8-tetracarboxylic acid, bicyclo[4.3.0]nonane-2,4,7,9-tetracarboxylic acid, bicyclo[4.4.0]decane-2,4,7,9-tetracarboxylic acid Acid, bicyclo[4.4.0]decane-2,4,8,10-tetracarboxylic acid, tricyclo[6.3.0.0<2,6>]undecane-3,5,9,11-tetracarboxylic acid , 1,2,3,4-butanetetracarboxylic acid, 4-(2,5-di-side oxytetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-di Carboxylic acid, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 5-(2,5-di-side oxytetrahydrofuranyl)-3-methyl-3-ring Hexane-1,2-dicarboxylic acid, tetracyclic [6.2.1.1<3,6>.0<2,7>] twelve-4,5,9,10-tetracarboxylic acid, 3,5,6 -Tricarboxynorbornane-2:3,5:6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid and other tetracarboxylic dianhydrides.

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

In the synthesis when the polymer is a polyamide, the structure of the dialkyl tetracarboxylic acid that reacts with the above-mentioned diamine component is not particularly limited, and specific examples thereof are listed below.

Specific examples of aliphatic tetracarboxylic acid diesters include: 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutane Alkyl tetracarboxylic acid dialkyl ester, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1, 2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofurantetracarboxylic acid dioxane Dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1-cyclohexyl dialkyl succinate, 3,4-dicarboxy-1,2 ,3,4-Tetrahydro-1-naphthalene succinate dialkyl ester, 1,2,3,4-butane tetracarboxylic acid dialkyl ester, bicyclo[3.3.0]octane-2,4,6 ,8-tetracarboxylic acid dialkyl ester, 3,3',4,4'-dicyclohexyl tetracarboxylic acid dialkyl ester, 2,3,5-tricarboxycyclopentyl acetate dialkyl ester, cis Formula-3,7-Dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclic [4.2.1.0<2,5>]nonane- 3,4,7,8-tetracarboxylic acid-3,4: 7,8-dialkyl ester, six ring [6.6.0.1<2,7>.0<3,6>.1<9,14> .0<10,13>]hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dialkyl ester, 4-(2,5-di-side oxytetrahydrofuran- 3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dialkyl ester and the like.

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

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

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

Although the aliphatic diisocyanates shown in K-1～K-5 have poor reactivity, they have the advantage of improving solvent solubility. For example, the aromatic diisocyanates shown in K-6～K-7 are highly reactive and make It has the effect of improving heat resistance, but it has the disadvantage of reducing solvent solubility. Considering versatility and characteristics, it should be K-1, K-7, K-8, K-9, K-10. Considering the viewpoint of electrical characteristics, it should be K-12. Considering the viewpoint of liquid crystal orientation, it is suitable. For K-13. More than one type of diisocyanate can also be used, and it is appropriate to use various diisocyanates according to the characteristics to be obtained.

In addition, a part of the diisocyanate can also be replaced with the tetracarboxylic dianhydride described above, and can be used in the form of a copolymer of polyamide acid and polyurea, and can also be chemically imidized to form a polyamide Used in the form of copolymer of imine and polyurea.

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

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

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

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

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

The polyimide having a divalent group represented by the formula (1) in the main chain includes a polyimide obtained by ring-closing the aforementioned polyimine precursor. In the polyimide, the ring-closure rate of the amide acid group (also referred to as the imidization rate) does not have to be 100%, and can be adjusted arbitrarily according to the application and purpose. The method for the imidization of the polyimide precursor can include thermal imidization in which the solution of the polyimide precursor is directly heated, or the catalyst is added to the solution of the polyimide precursor. Mediator imidization.

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

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

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

As for the organic solvent, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methylformamide , N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethyl Propanamide, N-methylcaprolactone, dimethyl sulfide, tetramethylurea, pyridine, dimethyl sulfide, hexamethylphosphotriamide, gamma-butyrolactone, isopropanol, formaldehyde Oxymethylpentanol, dipentene, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl serosol, ethyl serosol , Methyl Cyloxe Acetate, Butyl Cyloxe Acetate, Ethyl Cyloxe Acetate, Butyl Carbitol, Ethyl Carbitol, Ethylene Glycol, Ethylene Glycol Monoacetic Acid Ester, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tertiary butyl ether, dipropylene glycol monomethyl ether, propylene glycol mono Methyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether , Dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl Ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl ring Hexene, propyl ether, dihexyl ether, diethane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, Methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diethylene glycol Dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, etc. These organic solvents can be used alone or in mixture.

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

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

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

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

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

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

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

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

上述式(6)中，X₁ 為來自四羧酸衍生物之4價有機基，Y₁ 為來自式(2)之二胺之2價有機基，R₄ 為氫原子或碳數1～5之烷基。就R₄ 而言，考量利用加熱所為之醯亞胺化的容易性的觀點，宜為氫原子、甲基或乙基。The polymer of the component (A) of the present invention, considering its use as a liquid crystal alignment agent, is selected from polyimide precursors containing structural units represented by the following formula (6), and those based on their imide compounds At least one of polyimine is more preferable. [化13]

In the above formula (6), X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ₁ is a divalent organic group derived from a diamine of formula (2), and R ₄ is a hydrogen atom or a carbon number of 1 to 5之alkyl. Regarding R ₄ , considering the ease of imidization by heating, it is preferably a hydrogen atom, a methyl group, or an ethyl group.

<Tetracarboxylic dianhydride> X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, and its structure is not particularly limited. In addition, X ₁ in the polyimide precursor can be adapted to the solubility of the polymer in the solvent, the coating property of the liquid crystal alignment agent, the alignment of the liquid crystal when the liquid crystal alignment film is formed, the voltage retention rate, the accumulated charge, etc. The degree of the characteristics is appropriately selected, and one type may exist in the same polymer, or two or more types may be mixed together. A specific example of the ₁ X, then, include the International Publication No. 2015/119168 discloses 13 ~ 14 of the formula (X-1) ~ (X -46) of the structure.

₁ over the structure of X shown below, but the present invention is not limited to such. [化14]

上述結構中，(A-1)、(A-2)就光配向性的觀點係特佳，(A-4)就進一步改善蓄積電荷之緩和速度的觀點係特佳，(A-15)～(A-17)等就進一步改善液晶配向性與蓄積電荷之緩和速度的觀點係特佳。[化15]

Among the above structures, (A-1) and (A-2) are particularly preferred from the viewpoint of photo-alignment, (A-4) are particularly preferred from the viewpoint of further improving the relaxation speed of the accumulated charge, (A-15)~ (A-17) It is particularly preferable to further improve the liquid crystal orientation and the relaxation speed of the accumulated charge.

式(7)中，X₂ 為來自四羧酸衍生物的4價有機基，Y₂ 為來自不含式(1)之結構之二胺的2價有機基，R₅ 係與上述式(6)之R₄ 之定義相同，表示氫原子或碳數1～5之烷基，R₆ 表示氫原子或碳數1～4之烷基。又，2個R₆ 中之至少一者表示氫原子較佳。<Polymer (other structural unit)> The polyimide precursor containing the structural unit represented by the formula (6) may also contain a polyimide precursor selected from the group represented by the following formula (7) within the range that does not impair the effect of the present invention At least one of the structural unit and the polyimide which is the imide compound thereof. [化16]

In formula (7), X ₂ is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ₂ is a divalent organic group derived from a diamine without the structure of formula (1), and R ₅ is the same as the above formula (6 _{R 4} in) has the same definition and represents a hydrogen atom or an alkyl group with 1 to 5 carbons, and R ₆ represents a hydrogen atom or an alkyl group with 1 to 4 carbons. In addition, it is preferable that at least one of the _{two R 6 represents a hydrogen atom.}

Specific examples of X ₂ including ideal examples include the same structures as those exemplified for _{X 1 of formula (6). In addition, Y 2} in the polyimide precursor is a divalent organic group derived from a diamine that does not contain the structure of formula (1), and its structure is not particularly limited. In addition, Y ₂ can be appropriately selected according to the degree of the necessary characteristics such as the solubility of the polymer in the solvent, the coating property of the liquid crystal alignment agent, the alignment of the liquid crystal when the liquid crystal alignment film is formed, the voltage retention rate, and the accumulated charge. There may be one type in the same polymer, or two or more types may be mixed together.

Specific examples of Y ₂ include the structure of formula (2) disclosed in item 4 of the International Publication Bulletin 2015/119168, and formulae (Y-1) to (Y-97) disclosed in items 8 to 12, ( The structure of Y-101)～(Y-118); the bivalent organic group formed by removing two amine groups from formula (2) disclosed in item 6 of International Publication 2013/008906; 8 of International Publication 2015/122413 The article discloses the removal of two amine groups from the formula (1) to form a divalent organic group; the structure of the formula (3) disclosed in the 8th item of International Publication 2015/060360; the 8th item of the Japanese Laid-open Patent Publication 2012-173514 A divalent organic group is formed by removing two amine groups from formula (1); Item 9 of International Publication 2010-050523 discloses a divalent organic group formed by removing two amine groups from formulas (A)～(F) Wait.

_{The ideal structure of Y 2} is shown below, but the present invention is not limited to these. [化17]

[化18]

[化19]

[化20]

Among the above structures, (B-28), (B-29), etc. are particularly preferred from the viewpoint of further improving the film hardness, and (B-1) to (B-3) are particularly preferred from the viewpoint of further improving the orientation of the liquid crystal. , (B-14)～(B-18) and (B-27) are particularly good in terms of further improving the rate of relaxation of the accumulated charge, and (B-26) are more favorable in terms of further improving the voltage retention rate. good.

When the polyimide precursor containing the structural unit represented by formula (6) also contains the structural unit represented by formula (7), the structural unit represented by formula (6) is relative to the sum of formula (6) and formula (7) , Preferably 5 mol% to 80 mol%, more preferably 10 mol% to 50 mol%.

The polyimide having a divalent group represented by the formula (1) in the main chain includes a polyimide obtained by ring-closing the aforementioned polyimine precursor. In the polyimide, the ring-closure rate of the amide acid group (also referred to as the imidization rate) does not have to be 100%, and can be adjusted arbitrarily according to the application and purpose. The method for the imidization of the polyimide precursor can include thermal imidization in which the solution of the polyimide precursor is directly heated, or the catalyst is added to the solution of the polyimide precursor. Mediator imidization.

＜(B) Ingredient＞ The polymer of component (B) contained in the radical generating film forming composition agent of the present invention is preferably a polymer obtained by using diamine. Specifically, polyamide acid, polyamide acid ester, polyimide, polyurea, polyamide, etc. can be cited. Considering the point of use as a radical generating film forming composition, it is selected from the above formula (6 ) Represented by the structural unit, and the structural unit represented by the above formula (7), the polyimide precursor containing only the structural unit represented by the above formula (7), and the polyimide which is its imide compound At least one of them is better. The ideal tetracarboxylic dianhydride and diamine are as exemplified by the above-mentioned formula (7).

Furthermore, in the radical generating film forming composition as a liquid crystal alignment agent of the present invention, it is preferable that neither the polymer of component (A) nor the polymer of component (B) contains a vertical alignment group for vertically aligning liquid crystals. Better.

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

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

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

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

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

The radical generating film forming composition of the present invention may additionally contain components other than polymer components and organic solvents. Such additional components include an adhesion assistant for improving the adhesion between the radical generating film and the substrate, the adhesion between the radical generating film and the sealant, and the compound for increasing the strength of the radical generating film (hereinafter, also It is called a cross-linking compound.), a dielectric, conductive material, etc. used to adjust the permittivity and resistance of the radical generating film.

式中，R₇₁ 及R₇₂ 各自獨立地表示氫原子、碳數1～3之烷基或基「＊-CH₂ -OH」。＊表示係原子鍵。A表示具有芳香環之(m+n)價有機基。m表示1～6之整數，n表示0～4之整數。R₇₃ 表示碳數1～5之烷基。Regarding the above-mentioned cross-linking compound, considering the fact that AC residual images are less and the film strength improvement effect is high, it is preferably selected from having two or more selected from the group consisting of ethylene oxide and oxetanyl groups. , Protected isocyanate group, protected isothiocyanate group, oxazoline ring structure group, group containing Meldrum's acid structure, cyclocarbonate group, the group represented by the following formula (d) A compound of at least one group in the constituent group, or a compound of a compound represented by the following formula (e) (hereinafter, these are also collectively referred to as compound (C)) are preferred. [化21]

In the formula, R ₇₁ and R ₇₂ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a group "*-CH ₂ -OH". * Represents the atomic bond. A represents an (m+n) valent organic group having an aromatic ring. m represents an integer of 1 to 6, and n represents an integer of 0 to 4. R ₇₃ represents an alkyl group having 1 to 5 carbon atoms.

Specific examples of the compound having an oxirane group include, for example, the compound described in paragraph [0037] of Japanese Patent Application Laid-Open No. 10-338880, the compound described in International Publication No. WO2017/170483 having a three-ring skeleton, etc. Compounds with more than 2 oxirane groups. Among them, N,N,N',N'-tetraglycidyl-m-xylene diamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane Alkyl, N,N,N',N'-tetraepoxypropyl-4, 4'-diaminodiphenylmethane, N,N,N',N'-tetraepoxypropyl-terephthalene Nitrogen-containing compounds such as amines and compounds represented by the following formulas (r-1) to (r-3) are particularly preferred. [化22]

Specific examples of compounds having oxetanyl groups include, for example, compounds having two or more oxetanyl groups described in paragraphs [0170] to [0175] of International Publication No. 2011/132751.

Specific examples of the compound having a protected isocyanate group include, for example, the compound having two or more protected isocyanate groups described in paragraphs [0046] to [0047] of JP 2014-224978 A, International Publication Gazette 2015/141598 No. 2015/141598 paragraph [0119] ~ [0120] described in the compound having more than 3 protected isocyanate groups, etc. Among these, compounds represented by the following formulas (bi-1) to (bi-3) are preferred. [化23]

Specific examples of the compound having a protected isothiocyanate group include, for example, a compound having two or more protected isothiocyanate groups described in Japanese Patent Application Laid-Open No. 2016-200798.

Specific examples of the compound having a group containing an azoline ring structure include, for example, a compound containing two or more azoline structures described in paragraph [0115] of JP 2007-286597 A.

Specific examples of the compound having a group containing a Mildrum's acid structure include, for example, a compound having two or more Mildrum's acid structures described in International Publication No. WO2012/091088.

Specific examples of the compound having a cyclic carbonate group include, for example, the compound described in International Publication No. WO2011/155577.

_{The alkyl groups having 1 to 3 carbon atoms of R 71} and R ₇₂ of the group represented by the above formula (d) include methyl, ethyl, propyl and the like.

Specific examples of the compound having the group represented by the above formula (d) include, for example, the above-mentioned formula (d ) Represents the compound of the group, the compound described in JP 2016-200798 A, etc. Among these, compounds represented by the following formulas (hd-1) to (hd-8) are preferable. [化24]

The (m+n)-valent organic group having an aromatic ring in A of the above formula (e) includes (m+n)-valent aromatic hydrocarbon groups with 5 to 30 carbons, and aromatic hydrocarbon groups with 5 to 30 carbons. Or an (m+n) valent organic group bonded via a linking group, or an (m+n) valent group with an aromatic heterocyclic ring. As said aromatic hydrocarbon, benzene, naphthalene, etc. are mentioned, for example. Examples of aromatic heterocyclic rings include pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, isoquinoline ring, carbazole ring, pyridine ring, pyridine ring, and benzimidazole ring. , Benzimidazole ring, indole ring, quinoline ring, acridine ring, etc. Examples of the linking group include an alkylene group having 1 to 10 carbon atoms, a group obtained by removing one hydrogen atom from the alkylene group, a divalent or trivalent cyclohexane ring, and the like. In addition, any hydrogen atom of the above-mentioned alkylene group may be substituted with an organic group such as an alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a trifluoromethyl group. _{The alkyl group of R 73} in the above formula (e) includes methyl, ethyl, propyl and the like. Specific examples include the compounds described in International Publication No. WO2010/074269.

Preferred specific examples include the following formulas (e-1) to (e-9). [化25]

The above-mentioned compound is an example of a crosslinkable compound, and it is not limited to these. For example, the ingredients other than the above disclosed in International Publication No. 2015/060357, page 53 [0105] to page 55 [0116], etc. can be cited. In addition, the crosslinkable compound contained in the radical generating film forming composition of the present invention may be one type or a combination of two or more types. The content of the crosslinkable compound in the radical generating film forming composition of the present invention is preferably 0.5 to 20 parts by mass relative to 100 parts by mass of the polymer component contained in the radical generating film forming composition, considering the crosslinking From the viewpoint that the effect of the purpose is reflected and displayed, and the occurrence of AC residual images is less, it is more preferably 1 to 15 parts by mass.

The above-mentioned adhesion aids include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2 -Aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-amine Ethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3 -Aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyl triethylenetriamine, N-trimethoxy Silylpropyl triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane , 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3 -Aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3- Aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltriethoxy Methyl silane, vinyl trimethoxy silane, vinyl triethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxy propyl methyl dimethyl dimethyl Oxyoxy silane, 3-glycidoxy propyl trimethoxy silane, 3-glycidoxy propyl methyl diethoxy silane, 3-glycidoxy propyl triethoxy silane, P-styryl trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyl Diethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, ginseng-(trimethoxysilylpropyl) isocyanuric acid Ester, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane and other silane coupling agents. When these silane coupling agents are used, considering that AC residual images are less likely to occur, it is preferably 0.1-30 parts by mass, more preferably 0.1-20 parts by mass relative to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent .

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

In addition, the free radical generating film forming composition of the present invention is a liquid crystal alignment agent with free radical generating ability. In addition, the liquid crystal alignment film obtained from the radical generating film forming composition is specifically referred to as a radical generating film in this specification.

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

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

The substrate on which the radical generating film forming composition is applied is not particularly limited as long as it is a highly transparent substrate. Specific examples include: glass plates, polycarbonates, poly(meth)acrylates, polyethers, polyarylates, polyurethanes, polyethers, polyethers, polyether ketones, trimethyl Plastics such as pentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triacetyl cellulose, 2,3-butanedione cellulose, cellulose acetate butyrate, etc. Board and so on.

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

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

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

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

When the alignment treatment is performed by performing the rubbing treatment in one direction, for example, while the rubbing roller wound with the rubbing cloth is rotated, the substrate is moved so that the rubbing cloth is brought into contact with the film.

When the photo-alignment process is used to impart the liquid crystal alignment ability of the coating film, the radiation irradiated to the coating film may be, for example, ultraviolet rays and visible rays including light with a wavelength of 150 to 800 nm. When the radiation is polarized light, it may be linearly polarized light or partially polarized light. In addition, when the radiation used is linearly polarized light or partially polarized light, the irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction, or a combination of these may be performed. When irradiating non-polarized radiation, the irradiating direction is oblique.

As for the light source used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. can be used. Ultraviolet rays in the ideal wavelength range can be obtained by using a light source, such as optical filters, diffraction grids, and other effective means. The radiation dose is preferably 10 to 2,000 mJ/cm ² , more preferably 30 to 1,000 mJ/cm ² .

In addition, the light irradiation of the coating film can be performed while heating the coating film in order to increase the reactivity. The temperature during heating is usually 30 to 250°C, preferably 40 to 200°C, more preferably 50 to 150°C.

In addition, when using ultraviolet rays containing light with a wavelength of 150 to 800 nm, the light irradiation film obtained in the above steps can be directly used as a liquid crystal alignment film, or the light irradiation film can be calcined, washed with water, and organic solvents. , Or a combination of them. The calcination temperature at this time is preferably 80 to 300°C, more preferably 80 to 250°C. The calcination time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. In addition, the number of calcinations can be performed once or more than twice. The photo-alignment process here is equivalent to the process of irradiating light in a state where it is not in contact with the liquid crystal layer.

The organic solvent used in the above cleaning is not particularly limited, and specific examples include: methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2- Propanol acetate, butyl cerosine, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate Ester or cyclohexyl acetate, etc.

For the liquid crystal cell of the present invention, for the liquid crystal alignment film arranged on one substrate side, the radical generating film of the present invention can be used, and for the liquid crystal alignment film arranged on the other substrate side, it can be used as the liquid crystal alignment film. Liquid crystal alignment film used in the film. Regarding the liquid crystal alignment film of this embodiment arranged on the other substrate side, a commonly used liquid crystal alignment agent is used instead of the above-mentioned radical generating film forming composition. Otherwise, the same method as the radical generating film can be used get.

In addition, the substrate coated with the radical generating film forming composition and the substrate coated with the liquid crystal alignment agent are preferably a substrate on which a transparent electrode for driving liquid crystal is formed on any of the above-mentioned substrates. The substrates that can be used for IPS mode liquid crystal display elements can also use standard IPS comb-tooth electrodes, PSA herringbone electrodes and other electrode patterns, and MVA and other protrusion patterns. In addition, in high-function devices such as TFT-type devices, a device such as a transistor is formed between an electrode for driving liquid crystal and a substrate.

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

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

(Liquid crystal cell) The liquid crystal cell of the present invention is achieved by combining a substrate with a liquid crystal alignment film (first substrate) and a substrate with a radical generating film formed on the substrate (second substrate) using the above-mentioned method, with the radical generating film facing the liquid crystal It is obtained by arranging the alignment film, sandwiching the spacer and fixing it with a sealant, and injecting and sealing a liquid crystal composition containing a liquid crystal and a radical polymerizable compound. The size of the spacer used at this time is usually 1-30 μm, preferably 2-10 μm. In addition, by setting the alignment direction of the first substrate and the alignment direction of the second substrate to be parallel, it can be used in IPS mode and FFS mode. If the rubbing direction is arranged orthogonally, it can be used in twisted nematic mode. . Either one of the first substrate and the second substrate is preferably a comb-shaped electrode substrate. The alignment film formed on the above-mentioned first substrate may be a known liquid crystal alignment film or any one of the radical generating films of the present invention, and may be appropriately selected according to the purpose. The alignment film formed on the above-mentioned first substrate may be subjected to uniaxial alignment processing. Furthermore, it is preferable to form a liquid crystal alignment film for horizontal alignment that has undergone uniaxial alignment treatment on the first substrate.

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

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

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

式中，＊表示與化合物分子之聚合性反應基以外之部分的鍵結部位。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、碳數1～4之烷基。In addition, the polymerizable group of the radical polymerizable compound is preferably a polymerizable group selected from the following structures. [化26]

In the formula, * represents the bonding site with the part other than the polymerizable reactive group of the compound molecule. R ^b represents a linear alkyl group having 2 to 8 carbon atoms, and E represents a _{bonding group selected from a single bond, -O-, -NR c} -, -S-, an ester bond, and an amide bond. R _c represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms.

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

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

式(A)中，R^a 及R^b 各自獨立地表示碳數2～8之直鏈烷基，E表示選自單鍵、-O-、-NR_c -、-S-、酯鍵、醯胺鍵之鍵結基。文中R_c 表示氫原子、碳數1～4之烷基。Moreover, it is also preferable that the said radically polymerizable compound is a compound represented by the following formula (A). [化27]

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

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

式(A-1)及(A-2)中，R^a 及R^b 各自獨立地表示碳數2～8之直鏈烷基。In addition, for the radically polymerizable compound represented by the above formula (A), the formula where E is an ester bond (-C(=O)-O- or -OC(=O)-) is synthesized The viewpoints of ease, compatibility with liquid crystals, and polymerization reactivity are preferable. Specifically, a compound having the following structure is preferable, but it is not particularly limited. [化28]

In the formulas (A-1) and (A-2), R ^a and R ^b each independently represent a linear alkyl group having 2 to 8 carbon atoms.

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

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

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

Then, the liquid crystal cell into which the mixture (liquid crystal composition) containing the liquid crystal and the radical polymerizable compound is introduced is provided with energy sufficient to cause the radical polymerizable compound to undergo a polymerization reaction. It can be implemented by heating or UV irradiation, for example, by polymerizing the radically polymerizable compound in situ to exhibit desired characteristics. Among them, the use of UV can make the alignment patterning. In addition, considering the viewpoint of the polymerization reaction in a short time, UV irradiation is preferable. In addition, when used in the twisted nematic mode, in addition to the above-mentioned liquid crystal composition, a chiral dopant can be introduced into the liquid crystal cell as necessary.

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

Here, the UV irradiation wavelength during UV irradiation should be the wavelength with the best reaction quantum yield of the polymerizable compound to be reacted. The amount of UV irradiation is usually 0.5-30J/cm ² , preferably 1-10J/cm ^{2. The lower the} UV exposure, the more reliable the decrease in reliability caused by the destruction of the components constituting the liquid crystal display can be suppressed, and the takt in manufacturing can be improved by reducing the UV exposure time, which is ideal.

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

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

(Liquid crystal display element) The liquid crystal cell obtained in this way can be used to produce a liquid crystal display element. For example, a reflective electrode, a transparent electrode, a λ/4 plate, a polarizing film, a color filter layer, etc. are arranged in the liquid crystal cell according to the usual method as needed, thereby making a reflective liquid crystal display element. In addition, the liquid crystal cell is equipped with a backlight, a polarizing plate, a λ/4 plate, a transparent electrode, a polarizing film, a color filter layer, etc., according to a conventional method as required, so that a transmissive liquid crystal display element can be made. FIG. 1 is a schematic cross-sectional view showing an example of the liquid crystal display element of the present invention, which is an example of an IPS mode liquid crystal display element. In the liquid crystal display element 1 illustrated in FIG. 1, a liquid crystal composition 3 is sandwiched between a comb-shaped electrode substrate 2 provided with a radical generating film 2c and a counter substrate 4 provided with a liquid crystal alignment film 4a. The comb-tooth electrode substrate 2 has: a base material 2a, a plurality of linear electrodes 2b formed on the base material 2a and arranged in a comb-like shape, and a radical generator formed on the base material 2a so as to cover the linear electrodes 2b膜2c. The counter substrate 4 has a base material 4b, and a liquid crystal alignment film 4a formed on the base material 4b. In this liquid crystal display element 1, when a voltage is applied to the linear electrodes 2b, an electric field is generated between the linear electrodes 2b as indicated by the lines of force L. 2 is a schematic cross-sectional view showing another example of the liquid crystal display element of the present invention, which is an example of an FFS mode liquid crystal display element. In the liquid crystal display element 1 illustrated in FIG. 2, the liquid crystal composition 3 is sandwiched between the comb-shaped electrode substrate 2 provided with the radical generating film 2h and the counter substrate 4 provided with the liquid crystal alignment film 4a. The comb-tooth electrode substrate 2 has: a substrate 2d, a surface electrode 2e formed on the substrate 2d, an insulating film 2f formed on the surface electrode 2e, and a plurality of linear shapes formed on the insulating film 2f and arranged in a comb-like shape The electrode 2g and the radical generating film 2h formed on the insulating film 2f so as to cover the linear electrode 2g. The counter substrate 4 has a base material 4b, and a liquid crystal alignment film 4a formed on the base material 4b. In this liquid crystal display element 1, when a voltage is applied to the surface electrode 2e and the linear electrode 2g, an electric field is generated between the surface electrode 2e and the linear electrode 2g as indicated by the electric force line L. [Example]

The present invention is specifically explained by the examples, but the present invention is not limited to these examples. The abbreviations of the compounds used in the polymerization of the polymer and the preparation of the film-forming composition, and the methods for evaluating the characteristics are as follows. [化29]

NMP：N-甲基-2-吡咯烷酮、 BCS：丁基賽珞蘇[化30]

NMP: N-Methyl-2-pyrrolidone, BCS: Butyl Cyrosu

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

<Molecular weight measurement> The molecular weight is measured with a GPC (gel permeation chromatography) device at room temperature, and the number average molecular weight (Mn) and weight average molecular weight (Mw) are calculated in terms of polyethylene glycol and polyethylene oxide conversion values. . GPC device: GPC-101 (manufactured by Showa Denko), column: GPC KD-803, GPC KD-805 (manufactured by Showa Denko) in series, column temperature: 50°C, eluent: N,N-two Methylformamide (for additives, lithium bromide monohydrate (LiBr･H ₂ O) is 30mmol/L, phosphoric acid-anhydrous crystal (o-phosphoric acid) is 30mmol/L, and tetrahydrofuran (THF) is 10mL/L) , Flow rate: 1.0mL/min. Standard sample for calibration line production: TSK standard polyethylene oxide (molecular weight; approximately 900,000, 150,000, 100,000, and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; approximately 12,000 , 4,000 and 1,000) (manufactured by Polymer Laboratories).

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

<Synthesis of compound DA-5> [Chemical 31]

(Step 1) For 4,4'-dinitro-[1,1'-biphenyl]-2,2'-dicarboxylic acid (20.0g, 60.2mmol), add tetrahydrofuran (120g) and 2-hydroxyl -4'-(2-hydroxyethoxy)-2-methylpropiophenone (28.4g, 126mmol), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (28.0 g, 181 mmol), and N,N-dimethylaminopyridine (0.735 g, 6.02 mmol), stirred at room temperature overnight. After the completion of the reaction, it was separated and extracted twice with water/chloroform, and the obtained organic phase was concentrated to obtain a watery brown oil. This was purified by column chromatography using a mixed solvent of ethyl acetate/hexane=3/1 (volume ratio). The obtained fraction was concentrated, and it turned into a yellow transparent oil, and it continued to stand still. As a result, white crystals were precipitated from the oil. The precipitated crystals were washed with a mixed solvent of ethyl acetate/hexane=3/1 (volume ratio), filtered and the crystals were dried to obtain compound [1] (yield: 29.8 g, 40.0 mmol, 67% yield) ). ¹ H-NMR(500MHz) in DMSO-d ₆ ：8.57(d,J=2.5Hz,2H), 8.37(dd,J=8.5Hz,2.5Hz,2H), 8.18(d,J=9.0Hz,4H ),7.55(d,J=8.5Hz,2H),6.85(d,J=9.0Hz,4H),5.631(s,2H),4.39-4.35(m,4H),4.02-3.99(m,2H) ,3.96-3.94(m,2H),1.40(s,12H).

(Step 2) To the compound [1] (29.8g, 40.0mmol) obtained in the first step, add tetrahydrofuran (240g), replace with nitrogen, add 3% platinum carbon (aqueous product) (2.38g) and proceed Replace with nitrogen, install a tedlar bag and stir at room temperature for about 17 hours. After the reaction, the platinum carbon was removed by a membrane filter, then concentrated and dried to obtain DA-5 (yield: 27.4 g, 40.0 mmol, quant). ¹ H-NMR(500MHz) in DMSO-d ₆ ：8.20(dd,J=7.1Hz,1.9Hz,4H),6.99(d,J=2.5Hz,2H),6.92(dd,J=7.3Hz,1.9 Hz, 4H), 6.80 (d, J = 8.2 Hz, 2H), 6.67 (dd, J = 8.2 Hz, 2.5 Hz, 2H), 5.64 (s, 2H), 5.24 (s, 4H), 4.22 (t, J=4.5Hz,4H), 4.00(br,4H), 1.39(s,12H).

＜Synthesis of polyamide acid and polyimide＞ <Synthesis Example 1> TC-1/DA-1, DA-2(50) Polyamide acid (PAA-1) polymerization Measure DA-1 (1.62g:15.0mmol), DA-2 (3.66g:15.0mmol) and NMP (55.4g) in a 100mL 4-necked flask equipped with a mechanical stirrer and nitrogen introduction tube, and stir for a while After time to dissolve, add TC-1 (6.25g: 27.9mmol) and NMP (10.0g), and react at 40°C for 6 hours under a nitrogen atmosphere to obtain a polyamide acid with a solid content concentration of 15% by mass Solution (PAA-1). The viscosity is 390mPa･s, and the weight average molecular weight is about 32,100.

<Synthesis example 2> TC-3/DA-3(100) Polyamide acid (PAA-2) polymerization In a 100mL 4-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, weigh DA-3 (5.73g: 20.0mmol) and NMP (61.8g), stir for a while to dissolve, then add TC-3 ( 4.06 g: 18.6 mmol) and NMP (10.0 g) were reacted at 23° C. for 6 hours under a nitrogen atmosphere to obtain a polyamide acid solution (PAA-2) with a solid content concentration of 12% by mass. The viscosity is 240mPa･s, and the weight average molecular weight is about 25,900.

<Synthesis example 3> Polymerization of TC-2, TC-4(50)/DA-1, DA-4(50) polyamide acid (PAA-3) Measure DA-1 (1.08g: 10.0mmol), DA-4 (3.30g: 10.0mmol) and NMP (32.9g) in a 50mL 4-necked flask equipped with a mechanical stirrer and nitrogen introduction tube. After stirring for a period of time to dissolve under the environment, TC-4 (2.50g:10.0mmol) was added, and after reacting for 6 hours at 40°C under a nitrogen environment, TC-2 (1.88g: 9.6mmol) and NMP (2.1g) were added. ), reacted at 40°C for 12 hours in a nitrogen atmosphere, thereby obtaining a polyamide acid solution (PAA-3) with a solid content concentration of 20% by mass. The viscosity is 980mPa･s, and the weight average molecular weight is about 35,900.

<Synthesis Example 4> Synthesis of soluble polyimide (SPI-1) TC-2, TC-4(50)/DA-1, DA-4(50) In a 100 mL eggplant-shaped flask equipped with a nitrogen introduction tube, an air cooling tube, and a stir bar, measure the polyamide acid solution (PAA-3) (30.0g) obtained in the synthesis example 3 above, and add NMP (70.0g), Acetic anhydride (3.14 g: 30.9 mmol) and pyridine (1.62 g: 20.6 mmol) were stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then stirred at 50°C for 3 hours. After the completion of the reaction, the reaction solution was returned to room temperature, and was slowly poured into methanol (300 mL) that had been cooled to 10°C to precipitate solids and stirred for 10 minutes. The obtained solid was recovered by filtration, and the obtained solid was further stirred and washed for 10 minutes with methanol (100 mL) for a total of 2 times, and dried in a vacuum drying oven at 80°C for 6 hours to obtain the desired polyimide powder (SPI-1). The imidization rate is 62%.

<Synthesis example 5> Polymerization of TC-2, TC-4(50)/DA-4(100) polyamide acid (PAA-4) Measure DA-4 (6.61g: 20.0mmol) and NMP (34.1g) in a 50mL 4-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, stir for a while under a nitrogen environment to dissolve, then add TC-4 (2.50g: 10.0mmol), after reacting for 6 hours at 40°C under nitrogen atmosphere, add TC-2 (1.92g: 9.8mmol) and NMP (10.0g), and react under nitrogen atmosphere at 40°C For 12 hours, a polyamide acid solution (PAA-4) with a solid content concentration of 20% by mass was obtained. The viscosity is 1,120mPa･s, and the weight average molecular weight is about 38,400.

<Synthesis Example 6> Synthesis of TC-2, TC-4(50)/DA-4(100) soluble polyimide (SPI-2) In a 100 mL eggplant-shaped flask equipped with a nitrogen introduction tube, an air cooling tube, and a stir bar, measure the polyamide acid solution (PAA-4) (30.0 g) obtained in the synthesis example 5 above, and add NMP (70.0 g), Acetic anhydride (3.33 g: 32.7 mmol) and pyridine (1.72 g: 21.8 mmol) were stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then stirred at 50°C for 3 hours. After the completion of the reaction, the reaction solution was returned to room temperature, and was slowly poured into methanol (300 mL) that had been cooled to 10°C to precipitate solids and stirred for 10 minutes. The obtained solid was recovered by filtration, and the obtained solid was further stirred and washed for 10 minutes with methanol (100 mL) for a total of 2 times, and dried in a vacuum drying oven at 80°C for 6 hours to obtain the desired polyimide powder (SPI-2). The imidization rate is 59%.

<Synthesis example 7> Polymerization of TC-1/DA-2, DA-4(50) polyamide acid (PAA-5) Measure DA-2 (1.57g: 7.00mmol), DA-4 (4.79g: 7.00mmol) and NMP (42.60g) in a 50mL 4-necked flask equipped with a mechanical stirrer and nitrogen introduction tube, and stir for a while After time to dissolve, TC-1 (2.92g: 13.02mmol) and NMP (10.0g) were added and reacted at 40°C for 6 hours under a nitrogen atmosphere, thereby obtaining a polyamide acid solution (PAA-5). The viscosity is 440mPa･s, and the weight average molecular weight is about 32,600.

<Synthesis example 8> TC-1/DA-2, DA-4 (50) soluble polyimide (SPI-3) synthesis In a 100 mL eggplant-shaped flask equipped with a nitrogen introduction tube, an air cooling tube, and a stir bar, measure the polyamide acid solution (PAA-5) (30.0g) obtained in Synthesis Example 7 above, and add NMP (45.0g), Acetic anhydride (1.85 g: 18.0 mmol) and pyridine (0.95 g: 12.0 mmol) were stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then stirred at 50°C for 3 hours. After the completion of the reaction, the reaction solution was returned to room temperature, and was slowly poured into methanol (300 mL) that had been cooled to 10°C to precipitate solids and stirred for 10 minutes. The obtained solid was recovered by filtration, and the obtained solid was further stirred and washed for 10 minutes with methanol (100 mL) for a total of 2 times, and dried in a vacuum drying oven at 80°C for 6 hours to obtain the desired polyimide powder (SPI-3). The imidization rate is 72%.

<Synthesis Example 9> Polymerization of TC-1/DA-2, DA-5(50) polyamide acid (PAA-6) Measure DA-2 (2.44g:10.00mmol), DA-5 (6.85g:10.00mmol) and NMP (66.0g) in a 50mL 4-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, and stir for a while After time to dissolve, TC-1 (4.12g: 18.38mmol) and NMP (10.0g) were added and reacted at 40°C for 6 hours under a nitrogen atmosphere to obtain a polyamide acid with a solid content concentration of 15% by mass Solution (PAA-6). The viscosity is 380mPa･s, and the weight average molecular weight is about 29,600.

<Synthesis Example 10> Synthesis of TC-1/DA-2, DA-5(50) soluble polyimide (SPI-4) In a 100 mL eggplant-shaped flask equipped with a nitrogen introduction tube, an air cooling tube, and a stir bar, measure the polyamide acid solution (PAA-6) (30.0g) obtained in the synthesis example 9 above, and add NMP (45.0g), Acetic anhydride (2.42 g: 23.7 mmol) and pyridine (1.25 g: 15.8 mmol) were stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then stirred at 50°C for 3 hours. After the completion of the reaction, the reaction solution was returned to room temperature, and was slowly poured into methanol (300 mL) that had been cooled to 10°C to precipitate solids and stirred for 10 minutes. The obtained solid was recovered by filtration, and the obtained solid was further stirred and washed for 10 minutes with methanol (100 mL) for a total of 2 times, and dried in a vacuum drying oven at 80°C for 6 hours to obtain the desired polyimide powder (SPI-4). The imidization rate is 68%.

(Example 1) Preparation of Highly Anchored Liquid Crystal Alignment Agent (also known as Strongly Anchored Liquid Crystal Alignment Agent) AL-1 In a 50mL Erlenmeyer flask equipped with a stir bar, measure the polyamide acid solution (PAA-1) (20.0g) obtained in Synthesis Example 1 above, and add NMP (15.0g), BCS (15.0g) and Add -1 (0.15g), stirred at room temperature for 30 minutes, thereby preparing liquid crystal alignment agent AL-1.

(Example 2) Preparation of Highly Anchored Liquid Crystal Alignment Agent AL-2 In a 50mL Erlenmeyer flask equipped with a stir bar, measure the polyamide acid solution (PAA-2) (20.0g) obtained in Synthesis Example 2 above, and add NMP (8.0g), BCS (12.0g) and Add -2 (0.12g), stirred at room temperature for 30 minutes, thereby preparing liquid crystal alignment agent AL-2.

(Examples 3 to 6) Preparation of free radical generating film forming composition AL-3 to AL-6 In a 2-necked eggplant-shaped flask equipped with a nitrogen introduction tube and a stir bar, weigh the polyimide powder (SPI-1) (2.0g) obtained in Synthesis Example 4 above, add NMP (18.0g), and Stir at 40°C for 6 hours to dissolve. After confirming complete dissolution, NMP (3.3 g), BCS (10.0 g), and Add-2 (0.10 g) were added, and stirred at room temperature for 30 minutes, thereby preparing a radical generating film forming composition AL-3. In addition, SPI-2 to SPI-4 are used instead of SPI-1, and Add-2 is used for SPI-2, and Add-1 is used for SPI-3 and SPI-4. The free radical generating film forming compositions AL-4 to AL-6 were obtained.

(Example 7) Preparation of free radical generating film forming composition AL-7 Into a 40 mL sample bottle equipped with a stir bar, add the strong anchoring liquid crystal alignment agent AL-1 (5.0 g) prepared in Example 1 and AL-3 (5.0 g) prepared in Example 3, Stir at room temperature for 30 minutes, thereby preparing the radical generating film forming composition AL-7 of the present invention.

(Example 8) Preparation of free radical generating film forming composition AL-8 Into a 40 mL sample bottle equipped with a stir bar, add the strong anchoring liquid crystal alignment agent AL-1 (5.0 g) prepared in Example 1 and AL-4 (5.0 g) prepared in Example 4, Stir at room temperature for 30 minutes, thereby preparing the radical generating film forming composition AL-8 of the present invention.

(Example 9) Preparation of free radical generating film forming composition AL-9 Into a 40 mL sample bottle equipped with a stir bar, add the strong anchoring liquid crystal alignment agent AL-1 (5.0 g) prepared in Example 1 and AL-5 (5.0 g) prepared in Example 5, Stir at room temperature for 30 minutes, thereby preparing the radical generating film forming composition AL-9 of the present invention.

(Example 10) Preparation of free radical generating film forming composition AL-10 Into a 40 mL sample bottle equipped with a stir bar, add the strong anchoring liquid crystal alignment agent AL-1 (5.0 g) prepared in Example 1 and AL-6 (5.0 g) prepared in Example 6, Stir at room temperature for 30 minutes, thereby preparing the radical generating film forming composition AL-10 of the present invention.

(Example 11) Preparation of free radical generating film forming composition AL-11 Into a 40 mL sample bottle equipped with a stir bar, add the strong anchoring liquid crystal alignment agent AL-2 (5.0 g) prepared in Example 2 and AL-3 (5.0 g) prepared in Example 3, Stir at room temperature for 30 minutes, thereby preparing the radical generating film forming composition AL-11 of the present invention.

(Example 12) Preparation of free radical generating film forming composition AL-12 Into a 40 mL sample bottle equipped with a stir bar, add the strong anchoring liquid crystal alignment agent AL-2 (5.0 g) prepared in Example 2 and AL-4 (5.0 g) prepared in Example 4, Stir at room temperature for 30 minutes, thereby preparing the radical generating film forming composition AL-12 of the present invention.

＜Production of liquid crystal cell＞ Hereinafter, a method of manufacturing a liquid crystal cell for evaluating the alignment of liquid crystal is shown.

First, prepare the substrate with electrodes. The substrate is a glass substrate with a size of 30mm×35mm and a thickness of 0.7mm. An IZO electrode with an entire surface pattern as a counter electrode of the first layer is formed on the substrate. A SiN (silicon nitride) film formed by a CVD (chemical vapor deposition) method is formed as a second layer on the counter electrode of the first layer. The SiN film of the second layer has a thickness of 500 nm and functions as an interlayer insulating film. On the second layer of SiN film, a comb-shaped pixel electrode formed by patterning the IZO film as the third layer is arranged to form two pixels of a first pixel and a second pixel. The size of each pixel is 10 mm in the vertical direction and approximately 5 mm in the horizontal direction. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer. The pixel electrode of the third layer has a comb-tooth shape in which multiple electrode elements with a width of 3μm are bent at an internal angle of 160° at an interval of 6μm. One pixel is connected in parallel. The line of the bent portion of each electrode element has a first area and a second area as a boundary. When the first area and the second area of each pixel are compared, the formation directions of the electrode elements constituting the pixel electrodes are different. That is, when the alignment direction of the liquid crystal alignment film described later is used as a reference, the first area of the pixel is formed so that the electrode element of the pixel electrode becomes an angle of +80° (clockwise), and the second area of the pixel is It is formed in such a way that the electrode element of the pixel electrode becomes an angle of -80° (counterclockwise). That is, the first area and the second area of each pixel are in the direction of the rotation (in-plane switching) of the liquid crystal in the substrate surface induced by the voltage application between the pixel electrode and the counter electrode. It is constructed in the opposite direction. Hereinafter, it is referred to as an FFS substrate (first substrate).

Then, the free radical generating film forming composition AL-3 to AL12 obtained by the above method, the liquid crystal alignment agent AL-1, and the liquid crystal alignment agent SE-6414 (manufactured by Nissan Chemical Co., Ltd.) for horizontal alignment were used to use the aperture After filtering with a 1.0μm filter, it was coated on the prepared first substrate by spin coating, and a glass substrate ( (Hereinafter referred to as the second substrate) and film formation is performed. Then, after drying on a hot plate at 80°C for 80 minutes, it was fired at 230°C for 20 minutes to obtain a coating film with a film thickness of 100 nm. The polyimide film on the first substrate side is aligned in the direction along the direction of the comb teeth, and the polyimide film on the second substrate side is aligned in the direction orthogonal to the comb teeth. . In addition, in terms of alignment processing, SE-6414, AL-3, AL-4, AL-11, AL-12 are processed by friction processing, AL-1, AL-5, AL-6, AL-7, The AL-8, AL-9, and AL-10 systems use optical alignment. Regarding the rubbing treatment, the rubbing cloth is made by Yoshikawa Chemical's rayon cloth YA-20R under the conditions of 12mm roller system, 700rpm rotation speed, 30mm/s pedestal conveying speed, and 0.4mm pushing pressure. Regarding the free radical generating film, It is carried out under the conditions of rotation speed of 300 rpm, pedestal conveying speed of 50 mm/s, and pushing pressure of 0.2 mm. In addition, the optical alignment uses a UV exposure device manufactured by Ushio Electric Co., Ltd., with an extinction ratio of approximately 26:1 for linearly polarized UV, with a wavelength of 254nm as a reference, and an irradiation amount between ^{50 and 500mJ/cm 2} Irradiated with polarized light UV, heated at 230°C for 30 minutes, and compared the conditions with the best alignment quality of each.

After that, the above-mentioned two kinds of substrates were used. Regarding the display element that is the object of the embodiment, AL-1 or SE-6414 is used on the first substrate side, and the free radical generating films AL-7 and AL- are used on the second substrate side. 8. A combination of AL-9, AL-10, AL-11, and AL-12. In the display element to be compared, the two substrates use AL-1 or SE-6414, and the first substrate Radical generating films AL-3, AL-4, AL-5, AL-6 are used on the side, and AL-1 is used on the second substrate side. Combine them in such a way that their respective alignment directions become parallel, leaving the liquid crystal injection port and sealing the surroundings to produce an empty cell with a cell gap of about 4 μm. In this empty cell, liquid crystal (with 3% by mass of additive IC6 added to MLC-3019 manufactured by Merck) was vacuum-injected into this empty cell, and then the injection port was sealed to produce an anti-parallel-aligned liquid crystal cell. The obtained liquid crystal cell constitutes an FFS mode liquid crystal display element. After that, the obtained liquid crystal cell was heat-treated at 120°C for 10 minutes and irradiated with UV (UV lamp: FLR40SUV32/A-1) for 30 minutes using a UV-FL irradiation device manufactured by TOSHIBA LIGHTING & TECHNOLOGY without applying voltage. Liquid crystal display element.

＜Evaluation of liquid crystal orientation＞ Using a polarizing microscope, the polarizing plate was set to crossed nicols, and the liquid crystal cell was fixed in a state where the brightness of the liquid crystal cell was minimized. From this state, the liquid crystal cell was rotated by 1° to observe the alignment state of the liquid crystal. When unevenness, rough surface, etc. were not observed or very slight, it was evaluated as "good", and when it was clearly observed, it was evaluated as "bad". In addition, a photodiode is installed in the homopolarizing microscope, and the current-voltage conversion amplifier is connected to the electrometer, and the voltage under the condition where the brightness becomes the minimum is detected under a crossed Nicol, thereby measuring the black brightness.

＜Measurement of V-T curve and evaluation of drive threshold voltage and maximum brightness voltage＞ Set the white LED backlight and the brightness meter so that the optical axis is aligned. Between them, set the polarizer-mounted liquid crystal cell (liquid crystal display element) so that the brightness becomes the smallest. Apply the voltage at 1V intervals to 8V, and measure the voltage. The brightness below is used to measure the VT curve. From the obtained V-T curve, the drive threshold voltage and the voltage value at which the brightness becomes the maximum are estimated. In addition, assuming that the transmission brightness of parallel polarized light (Parallel Nicol) is 100% through the liquid crystal cell with no voltage applied, the maximum transmission brightness of the V-T curve is compared, and the maximum transmission brightness is estimated.

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

＜Content of polymer＞ [Table 1]

<Contents of liquid crystal alignment agent or radical generating film forming composition> [Table 2]

<Contents of the liquid crystal cell of the embodiment> The structure of the liquid crystal cell is shown in Table 3 below. [table 3]

＜Results＞ [Table 4]

Comparative example 1 is an example of a combination of optically-aligned strong anchor alignment films, and comparative example 2 and comparative example 3 are examples when the constituent components of the radical generating film are individual components. Examples 13 to 16 are examples when the radical generating membrane is mixed with a strong anchoring component and a radical generating component. It can be seen that the black brightness of Examples 13-16 can achieve almost the same level of characteristics as the combination of the strong anchor alignment films of Comparative Example 1. Compared with Comparative Example 2 and Comparative Example 3, the black brightness is also good, and the transmittance is also large. Improve, the delay of response time is suppressed. It can be seen that especially in the case of using the non-aligned radical generating film component (Example 13, Example 14), good alignment, black brightness, and good weak anchoring characteristics can also be obtained. On the other hand, it can be seen that the black brightness and transmittance of Comparative Example 3 are better, but compared with the individual components, by mixing the strong anchoring component (Example 16), the black brightness can be improved and the response time can be improved.

Comparative Example 4 is an example of a combination of strong anchor alignment films for friction, and Comparative Example 5 and Comparative Example 6 are examples when a radical generating film of a single component that is not optically aligned is used. In contrast, Example 17 and Example 18 are examples when a strong anchoring component for friction and a radical generating component are mixed. It can be seen that the orientation and black brightness of Example 17 and Example 18 are at the same level as SE-6414, the transmittance is also improved, and the response time delay is also suppressed.

Therefore, from these tests, it can be seen that by using the radical generating film forming composition of the present invention mixed with a strong anchoring component and a free radical generating component, good alignment can be maintained, and the transmittance can be improved and Liquid crystal display element with suppressed response time. [Industrial Utilization]

By using the radical generating film forming composition of the present invention, it is possible to provide a transverse electric field liquid crystal display element that can perform a good black display, and can realize a high backlight transmittance and a fast response speed. In addition, the liquid crystal display element obtained by the method of the present invention is useful as a liquid crystal display element of a horizontal electric field driving method.

1: liquid crystal display element 2: Comb electrode substrate 2a: Substrate 2b: Wire electrode 2c: free radical generating membrane 2d: substrate 2e: Surface electrode 2f: insulating film 2g: wire electrode 2h: free radical generating membrane 3: Liquid crystal composition 4: Opposite substrate 4a: Liquid crystal alignment film 4b: Substrate

Fig. 1 is a schematic cross-sectional view showing an example of the liquid crystal display element of the present invention. Fig. 2 is a schematic cross-sectional view showing another example of the liquid crystal display element of the present invention.

Claims (9)

A free radical generating film-forming composition comprising: a polymer having a component (A) having a structural unit represented by the following formula (1) in the main chain; and a component (B) as a liquid crystal alignment agent for lateral electric field driving The polymer used in the alignment component;

In formula (1), A represents an organic group that induces radical polymerization. The radical generating film forming composition of claim 1, wherein the polymer of the component (A) is selected from a polyamine component obtained by using a diamine containing an organic group that induces radical polymerization At least one polymer selected from the group consisting of an imine precursor, polyimine, polyurea, and polyamide. According to the free radical generating film forming composition of claim 2, wherein the diamine containing an organic group that induces free radical polymerization is a diamine represented by the following formula (2);

In formula (2), A ¹ and A ² each represent a hydrogen atom or an organic group that induces free radical polymerization, but ^{at least one of A 1} and A ² represents an organic group that induces free radical polymerization; E represents a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -NHCO-, -COO-, -(CH ₂ ) _m -, -SO ₂ -, or any combination of these M represents an integer from 1 to 8; p represents an integer from 0 to 2; when p is 2, a plurality of A ² each independently has the aforementioned definition; and when p is 0, A ¹ is induced to be free The base polymerized organic base composition. According to the free radical generating film forming composition of claim 1, wherein the organic group that induces free radical polymerization is a group represented by the following formula (3);

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

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

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

In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O-, or -S-, R represents a hydrogen atom or an alkyl group with 1 to 4 carbons, * represents an atomic bond; R ¹² represents a hydrogen atom, halogen Atom, C 1-10 alkyl group or C 1-10 alkoxy group. A radical generating film obtained by using the radical generating film forming composition according to any one of claims 1 to 4. A method for manufacturing a transverse electric field liquid crystal cell includes the following steps: Prepare a first substrate with a liquid crystal alignment film and a second substrate with a radical generating film as in claim 5; Fabricating a unit cell in such a way that the radical generating film on the second substrate faces the first substrate; and Between the first substrate and the second substrate, a liquid crystal composition containing liquid crystal and a radical polymerizable compound is filled; Either one of the first substrate and the second substrate is a comb-tooth electrode substrate, and the other is an opposite substrate. According to claim 6, the method for manufacturing a transverse electric field liquid crystal cell, wherein the first substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment. The method for manufacturing a transverse electric field liquid crystal cell of claim 7, wherein the liquid crystal alignment film with uniaxial alignment is a liquid crystal alignment film for horizontal alignment. According to claim 6, the method for manufacturing a transverse electric field liquid crystal cell, wherein the comb-shaped electrode substrate is an IPS substrate or an FFS substrate.

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