KR20190117735A - Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element - Google Patents

Abstract

[화학식 2]

식 (1) 중, X 는 -(CH₂)n- 를 나타내고, n 은 8 또는 9 의 자연수이다.
식 (2) 중, Y₁ 은 아미노기 등을 갖는 2 가의 유기기이며, B₁, B₂ 는 각각 독립적으로 수소 원자 등이다. At least 1 type of polymer (A) chosen from the polyamic acid obtained by using the tetracarboxylic dianhydride component and the diamine component containing the diamine represented by following formula (1), and the imidation polymer of this polyamic acid. And at least one kind of polymer (B) selected from the polyamic acid obtained using the tetracarboxylic dianhydride component and the diamine component containing the diamine represented by following formula (2), and the imidation polymer of this polyamic acid. It relates to a liquid crystal aligning agent to be mentioned. ADVANTAGE OF THE INVENTION According to this invention, the liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element which are excellent in voltage retention, quick relaxation of an accumulation charge, and the favorable liquid crystal alignment stability are obtained can be provided.
[Formula 1]

[Formula 2]

Formula (1), X is - (CH ₂₎ represents an n-, n is a natural number of eight or nine.
In formula (2), Y <_1> is a divalent organic group which has an amino group, etc., B <_1> , B <_2> is a hydrogen atom etc. each independently.

Description

Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element

This invention relates to a novel liquid crystal aligning agent, a liquid crystal aligning film, and the liquid crystal display element using the same.

Liquid crystal display elements are widely used as display units such as personal computers, mobile phones, smart phones, and televisions. The liquid crystal display device includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode for applying an electric field to the liquid crystal layer, a common electrode, an alignment film for controlling the alignment of liquid crystal molecules of the liquid crystal layer, and a pixel electrode. And a thin film transistor (TFT) for switching the supplied electrical signal. As a drive system of liquid crystal molecules, longitudinal electric field systems, such as a TN system and VA system, and a transverse electric field system, such as an IPS system and an FFS system, are known. In the transverse electric field system in which an electrode is formed only on one side of the substrate and an electric field is applied in a direction parallel to the substrate, it has a wide viewing angle characteristic as compared with the conventional electric field system in which a voltage is applied to electrodes formed on the upper and lower substrates to drive the liquid crystal. Moreover, it is known as a liquid crystal display element which can display high quality.

The transverse electric field type liquid crystal cell has excellent viewing angle characteristics, but since there are few electrode portions formed in the substrate, when the voltage holding ratio is low, sufficient voltage is not applied to the liquid crystal and display contrast is lowered. Moreover, when the stability of liquid crystal orientation is small, when a liquid crystal is driven for a long time, a liquid crystal will not return to an initial state, and it will cause a contrast fall and an afterimage, and therefore stability of liquid crystal orientation is important. In addition, static electricity tends to accumulate in the liquid crystal cell, and charges accumulate in the liquid crystal cell even by application of a positive asymmetric voltage generated by driving, and these accumulated charges affect display as the liquid crystal alignment is disturbed or afterimage. The display quality of a liquid crystal element is remarkably reduced. In addition, even when the backlight light is irradiated to the liquid crystal cell immediately after the driving, electric charges accumulate, and afterimage driving occurs even after a short driving time, causing problems such as the change of the flicker (blinking) size during the driving.

As a liquid crystal aligning agent which was excellent in voltage retention and reduced charge accumulation, when used for a liquid crystal display element of such a transverse electric field system, Patent Literature 1 includes liquid crystal alignment containing a specific diamine and an aliphatic tetracarboxylic acid derivative. I am disclosed. Moreover, as a method of shortening the time until an afterimage disappears, the orientation film with low volume resistivity like patent document 2, or the alignment film with volume resistivity like patent document 3 hard to change even with the backlight of a liquid crystal display element is used. It is proposed how to. However, with the high performance of a liquid crystal display element, the characteristic requested | required of a liquid crystal aligning film is also becoming severe, and it is difficult to fully satisfy all the required characteristic with these conventional techniques.

International publication WO2004 / 021076 pamphlet International publication WO2004 / 053583 pamphlet International publication WO2013 / 008822 pamphlet

An object of this invention is to provide the liquid crystal aligning agent, the liquid crystal aligning film, and the liquid crystal display element which are excellent in voltage retention, quick relaxation of an accumulation charge, and can obtain the liquid crystal aligning film with favorable stability of liquid crystal aligning.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, it discovered that various characteristics improve simultaneously by introducing a specific structure in the polymer contained in a liquid crystal aligning agent, and completed this invention. This invention is based on this knowledge and makes the following a summary.

At least one kind of polymer (A) selected from the polyamic acid obtained by using the diamine component containing a <1> tetracarboxylic dianhydride component and the diamine represented by following formula (1), and this polyamic acid; ,

At least one kind of polymer (B) chosen from the polyamic acid obtained by using the tetracarboxylic dianhydride component and the diamine component containing the diamine represented by following formula (2), and the imidation polymer of this polyamic acid.

It contains, a liquid crystal aligning agent.

[Formula 1]

[Formula 2]

Formula (1), X is - (CH ₂₎ represents an n-, n is - (CH ₂₎ - is a natural number representing the number of 8 or 9, any - (CH ₂₎ - are, each independently, Groups selected from -O-, -S-, -COO-, -OCO-, -CONH- and -NHCO-, these groups may be substituted on condition that they are not adjacent to each other, and R ₁ and R ₂ are each independently It is a monovalent organic group, and p1 and p2 are the integers of 0-4 each independently.

In formula (2), Y <_1> is a divalent organic group which has at least 1 sort (s) of structure chosen from the group which consists of an amino group, an imino group, and a nitrogen-containing heterocyclic ring, B <_1> , B <_2> are respectively independently a hydrogen atom, Or a C1-C10 alkyl group, alkenyl group, and alkynyl group which may have a substituent.

<2> equation (2) in Y is _1, the formula (YD-1) ~ at least one of, the liquid crystal of the <1> is selected from the structure (YD-5).

[Formula 3]

(In formula (YD-1), A <_1> is a C3-C15 nitrogen atom containing heterocyclic ring, and Z <_1> is a C1-C20 hydrocarbon group which may have a hydrogen atom or a substituent. In -2), W ₁ is a hydrocarbon group of 1 to 10 carbon atoms, and A ₂ is a divalent group substituted with a C 3 to C 15 monovalent organic group having a nitrogen atom-containing heterocyclic ring or an aliphatic group having 1 to 6 carbon atoms. In Formula (YD-3), W ₂ is a divalent organic group having 6 to 15 carbon atoms and having 1 to 2 benzene rings, and W ₃ is alkylene or biphenyl having 2 to 5 carbon atoms. is alkylene or a carbon number of 12 to 18 divalent organic group that includes a heterocyclic ring containing a nitrogen atom, Z ₂ is an alkyl group, or a benzene ring of the hydrogen atoms, having a carbon number of 1 ~ 5, a is an integer from 0 to 1. expression ( In YD-4), A ₃ is a nitrogen atom-containing hetero ring having 3 to 15 carbon atoms. In A ₄ , A ₄ is a nitrogen atom-containing hetero ring having 3 to 15 carbon atoms, and W ₅ is alkylene having 2 to 5 carbon atoms.)

<3> A ₁ , A ₂ , A ₃ , and A ₄ described in formulas (YD-1), (YD-2), (YD-4), and (YD-5) are pyrrolidine, pyrrole, Said <at least one kind selected from the group consisting of imidazole, pyrazole, oxazole, thiazole, piperidine, piperazine, pyridine, pyrazine, indole, benzoimidazole, quinoline, isoquinoline, and carbazole 1> or <2> liquid crystal aligning agent.

<4> formula (2) Y ₁ is the following formula (YD-6) ~ at least one of the <1> is selected from the group consisting of divalent groups organic group having a structure of (YD-22) ~ in The liquid crystal aligning agent in any one of <3>.

[Formula 4]

(H is an integer of 1-3 in a formula (YD-17), and j is an integer of 0-3 in a formula (YD-14) and (YD-21) and (YD-22).)

<5> Expression is Y ₁ in (2), the formula (YD-14), (YD -18), (YD-21) and (YD-22) structure from the group consisting of divalent groups organic group having a It is at least 1 sort (s) chosen, The liquid crystal aligning agent in any one of said <1>-<4>.

<6> The liquid crystal aligning film obtained by apply | coating and baking the liquid crystal aligning agent in any one of said <1>-<5>.

The liquid crystal display element provided with the liquid crystal aligning film of <7> said <6>.

By using the liquid crystal aligning agent of this invention, the liquid crystal aligning film which is excellent in voltage retention, quickens | restorates of an accumulation charge, and is excellent in stability of liquid crystal orientation, and the liquid crystal display element excellent in display characteristic is provided.

It is not clear what can solve the said subject by this invention, but thinks as follows.

The structure of said (2) which the polymer contained in the liquid crystal aligning agent of this invention has a conjugated structure. Thereby, for example, in a liquid crystal aligning film, a movement of electric charge can be accelerated | stimulated and relaxation of an accumulation charge can be accelerated | stimulated.

The liquid crystal aligning agent of this invention is a composition used for forming a liquid crystal aligning film, The specific polymer obtained from the specific polymer (A) obtained from the diamine represented by the said Formula (1), and the diamine which has a structure of the said Formula (2) It is characterized by containing a liquid crystal aligning agent containing a polymer (B).

That is, this invention relates to the liquid-crystal aligning polymer composition containing the said characteristic polymer (A) and the said specific polymer (B).

Content of specific polymer (A) and specific polymer (B) is 5-90 weight% of specific polymer (A) with respect to the total amount of a specific polymer (A) and a specific polymer (B), More preferably, it is 10- 50 wt%. That is, with respect to the total amount of a specific polymer (A) and a specific polymer (B), a specific polymer (B) is 95 to 10 weight%, More preferably, it is 90 to 50 weight%. When there are too few specific polymers (A), the stability of liquid crystal aligning will deteriorate, and when there are too few specific polymers (B), the relaxation characteristic of accumulated charge will deteriorate. The specific polymer (A) and the specific polymer (B) contained in the liquid crystal aligning agent of this invention may be one type, respectively, or two or more types may be sufficient as them.

<Polymer of (A) Component>

The polymer of this invention is a polymer obtained from the diamine component containing the diamine represented by the said Formula (1), and the acid dianhydride component containing tetracarboxylic dianhydride. Although a polyamic acid, polyamic acid ester, polyimide, polyurea, polyamide etc. are mentioned as a specific example, From the viewpoint of use as a liquid crystal aligning agent, the polyimide precursor containing the structural unit represented by following formula (3) And at least one selected from polyimides which are imides thereof. In the heating process after polarized light irradiation, a polyimide precursor is more preferable at the point which is redirected by higher order because there are many free rotation sites in a polymer.

[Formula 5]

In the formula (3), X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ₁₁ is a divalent organic group derived from the diamine of formula (1), and R ₁₁ is a hydrogen atom or carbon number It is an alkyl group of 1-5. R ₁₁ is preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom in terms of ease of imidization by heating.

<Diamine having a Specific Structure>

The liquid crystal aligning agent of this invention is at least 1 sort (s) chosen from the polyamic acid obtained using the tetraamine dianhydride component and the diamine component containing the diamine represented by following formula (1), and the imidation polymer of this polyamic acid. At least one kind of polymer selected from the polyamic acid obtained using the diamine component containing a polymer (A), the tetracarboxylic dianhydride component, and the diamine represented by following formula (2) ( It is a liquid crystal aligning agent containing B) and an organic solvent.

[Formula 6]

(Formula (1), X is - (CH ₂₎ represents an n-, n is - (CH ₂₎ - is a natural number representing the number of 8 or 9, any - (CH ₂₎ - are each independently , -O-, -S-, -COO-, -OCO-, -CONH- and -NHCO- are groups selected from, and these groups may be substituted under the condition that they are not adjacent to each other, and R ₁ and R ₂ are each independently Is a monovalent organic group, and p1 and p2 are each independently an integer of 0 to 4).

Examples of the monovalent organic group herein include an alkyl group, an alkenyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkenyl group, or a fluoroalkoxy group having 1 to 10, preferably 1 to 3 carbon atoms. . Especially, as monovalent organic group, a methyl group is preferable.

Moreover, when the sum total of the atomic number of the carbon atom, oxygen atom, sulfur atom, and nitrogen atom which participate in the length of a principal chain in the number of atoms of X is even, the linearity of the polymer obtained becomes high after rubbing or a polarized ultraviolet ray. In the heating process after irradiation, since it is possible to obtain the liquid crystal aligning film to which the high orientation control ability was provided by reorienting in higher order, it is preferable. In addition, the sum of the number of atoms of a carbon atom, an oxygen atom, a sulfur atom, and a nitrogen atom which concerns on the length of a main chain means 1 number per methylene of a main chain, 1 number per ether bond, and a sulfide bond It is the sum total when the number per piece is 1, the number per ester bond is 2, and the number per amide bond is 2.

Any-(CH ₂ )-in X has a weaker hydrogen bonding force and is replaced by any one of -O-, -S-, -COO-, or -OCO- in that it is redirected in a higher order. Preferred, and -O- is particularly preferred.

As p1 and p2, since phenyl group is easy to overlap because there is little steric hindrance, 0 is preferable at the point which rearranges to higher order.

Diamines of the formula (1) in the (CH ₂₎ n-, n is 8 or more, the polymer (B) blended with a case where the liquid crystal aligning agent and a degree on the substrate, alignment control force with the high polymer (A) The transferability to the virtual layer, that is, the interface other than the substrate side is high, thus contributing to the improvement of the orientation. Moreover, when n is ten or more, the orientation regulation force of a polymer (A) itself falls large. Therefore, if n is not 8 or 9, the effect of this invention is not acquired. Although the following can be illustrated as a specific example of these diamine, It is not limited to these.

[Formula 7]

[Formula 8]

Here, when r is 6 or t is 2 or 4 in the said formula, as a result, the linearity of the polymer obtained becomes high and, as a result, the liquid crystal to which high orientation control ability was provided by reorienting to higher order in the heating process after polarized light irradiation. An alignment film can be obtained.

<Tetracarboxylic dianhydride>

X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, and the structure is not particularly limited. Moreover, X <_1> in a polyimide precursor is the grade of required characteristics, such as the solubility to the solvent of a polymer, the applicability | paintability of a liquid crystal aligning agent, and the liquid crystal aligning film in the case of using a liquid crystal aligning film, voltage retention, and an accumulated charge. It selects accordingly, one type may be sufficient as the same polymer, and two or more types may be mixed.

If the specific example of X <_1> is shown daringly, the structure of Formula (X-1)-(X-46) etc. which were published by 13-14 clause of international publication 2015/119168 will be mentioned.

Although the structure of preferable X <_1> is shown below, this invention is not limited to these.

[Formula 9]

Among them, from the viewpoint of photoreactivity, liquid crystal orientation and voltage retention, (A-1) (A-2) is preferable.

<Polymer (Other Structural Unit)>

The polyimide precursor containing the structural unit represented by Formula (3) is at least chosen from the polyimide which is a structural unit represented by following formula (4), and its imide in the range which does not impair the effect of this invention. One kind may be included.

[Formula 10]

In Formula (4), X <_2> is the tetravalent organic group derived from tetracarboxylic-acid derivative, Y <_12> is the divalent organic group derived from diamine, R <_12> is represented by R <_11> of said Formula (3) It is the same as a definition, R <_22> represents a hydrogen atom or a C1-C4 alkyl group. Moreover, it is preferable that at least one of two R <_22> is a hydrogen atom.

Examples of X ₂ include the structures of formulas (X-1) to (X-46) disclosed in 13 to 14 of the International Publication 2015/119168, and the above (A-1) to The structure of (A-21) is mentioned.

Y ₁₂ is a divalent organic group derived from diamine, and the structure is not specifically limited. Further, Y ₁₂ is appropriately selected according to the degree of the characteristics as orientation, voltage holding ratio, accumulated charges, etc., required of the liquid crystal in a case where the solubility and the coating of the liquid crystal aligning agent property, the liquid crystal alignment film of the polymer solvent, One type may be sufficient as the same polymer, and two or more types may be mixed.

If the specific example of Y <_12> is shown, the structure of Formula (2) published in the 4th term of international publication 2015/119168, and Formula (Y-1)-(Y-) which were published in the term 8-12 97) and (Y-101) to (Y-118); Divalent organic groups obtained by removing two amino groups from Formula (2), as described in 6 of International Publication 2013/008906; Divalent organic groups obtained by removing two amino groups from Formula (1) disclosed in 8 of International Publication 2015/122413; The structure of formula (3) in paragraph 8 of International Publication No. 2015/060360; Divalent organic groups obtained by removing two amino groups from Formula (1) according to item 8 of JP-A-2012-173514; The divalent organic group etc. which removed two amino groups from Formula (A)-(F) published by 9 of international publication 2010-050523 are mentioned.

As a preferable structure of Y <_12>, the structure of following formula (5) is mentioned.

[Formula 11]

In formula (5), R <^32> is a single bond or a divalent organic group, and a single bond is preferable.

R ³³ is a structure represented by-(CH ₂ ) _n- . n is an integer of 2-10, and 3-7 are preferable. Optional -CH ₂ -may be substituted with ether, ester, amide, urea, carbamate bond on the condition that they are not adjacent to each other.

R ³⁴ is a single bond or a divalent organic group.

Any hydrogen atom on a benzene ring may be substituted by monovalent organic group, and a fluorine atom or a methyl group is preferable.

Although the following structures are mentioned specifically as a structure represented by Formula (5), It is not limited to these.

[Formula 12]

[Formula 13]

[Formula 14]

When the polyimide precursor containing the structural unit represented by Formula (3) contains the structural unit represented by Formula (4) simultaneously, the structural unit represented by Formula (3) is a thing of Formula (3) and Formula (4) It is preferable that they are 30 mol%-100 mol% with respect to a sum total, More preferably, they are 50 mol%-100 mol%, Especially preferably, they are 70 mol%-100 mol%.

<Polymer of (B) Component>

The (B) component used for the liquid crystal aligning agent of this invention is a polyamic acid obtained using the diamine component containing the tetracarboxylic dianhydride component and the diamine represented by said Formula (2), and the imidation polymer of this polyamic acid. At least one polymer selected.

<Tetracarboxylic dianhydride component>

As tetracarboxylic dianhydride used for manufacture of (B) component of this invention, tetracarboxylic dianhydride represented by following formula (6) is mentioned.

[Formula 15]

In formula, as X <_3> , the structure chosen from said (A-1)-(A-21) described by (A) component is mentioned. Moreover, in manufacture of (B) component, the tetracarboxylic dianhydride component to be used may be one type, and may be two or more types.

<Diamine component>

The diamine component used for manufacture of the liquid crystal aligning agent of this invention contains the diamine of said Formula (2). In the formula (2), Y ₁ is an amino group, an imino group, and also is a divalent organic group having at least one kind of structure selected from the group consisting of a nitrogen heterocyclic ring, B ₁ ~ B ₂ are each independently a hydrogen atom Or a C1-C10 alkyl group, alkenyl group, or alkynyl group which may have a substituent.

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, t-butyl group, hexyl group, octyl group, decyl group, cyclopentyl group and cyclohexyl group. As an alkenyl group, what substituted one or more CH-CH structures which exist in the said alkyl group by C = C structure is mentioned, More specifically, a vinyl group, an allyl group, 1-propenyl group, isopropenyl group , 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group, cyclopropenyl group, cyclopentenyl group, cyclohexenyl group and the like. Alkynyl group is, there may be mentioned that one or more CH ₂ -CH ₂ structures present in the alkyl group was substituted with C≡C structure, more specifically, ethynyl group, 1-propynyl group, 2-propynyl group Can be mentioned.

The said alkyl group, alkenyl group, and alkynyl group may have a substituent as a whole if it is C1-C10, Furthermore, you may form a ring structure by a substituent. In addition, forming a ring structure by a substituent means that a substituent or a part of a substituent and a parent skeleton couple | bonds and becomes a ring structure.

Examples of this substituent include halogen group, hydroxyl group, thiol group, nitro group, aryl group, organooxy group, organothio group, organosilyl group, acyl group, ester group, thioester group, phosphate ester group, amide group, alkyl group And alkenyl groups and alkynyl groups.

As a halogen group which is a substituent, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

A phenyl group is mentioned as an aryl group which is a substituent. The other substituent mentioned above may further substitute by this aryl group.

As an organooxy group which is a substituent, the structure represented by O-R can be shown. This R may be same or different and can illustrate an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc. which were mentioned above. The substituent mentioned above may further substitute by such R. As a specific example of an alkyloxy group, a methoxy group, an ethoxy group, a propyloxy group, butoxy group, a pentyloxy group, hexyloxy group, heptyloxy group, an octyloxy group, etc. are mentioned.

As an organothio group which is a substituent, the structure represented by -S-R can be shown. As said R, the alkyl group, alkenyl group, alkynyl group, aryl group, etc. which were mentioned above can be illustrated. The substituent mentioned above may further substitute by such R. Specific examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group and the like.

As an organosilyl group which is a substituent, the structure represented by -Si- (R) ₃ can be shown. This R may be same or different and can illustrate an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc. which were mentioned above. The substituent mentioned above may further substitute by such R. Specific examples of the alkylsilyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, tripentylsilyl group, trihexylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, and the like. Can be.

As an acyl group which is a substituent, the structure represented by -C (O) -R can be shown. As this R, the alkyl group, alkenyl group, aryl group, etc. which were mentioned above can be illustrated. The substituent mentioned above may further substitute by such R. Specific examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, benzoyl group and the like.

As ester group which is a substituent, the structure represented by -C (O) O-R or -OC (O) -R can be shown. As said R, the alkyl group, alkenyl group, alkynyl group, aryl group, etc. which were mentioned above can be illustrated. The substituent mentioned above may further substitute by such R.

As a thioester group which is a substituent, the structure represented by -C (S) O-R or -OC (S) -R can be shown. As said R, the alkyl group, alkenyl group, alkynyl group, aryl group, etc. which were mentioned above can be illustrated. The substituent mentioned above may further substitute by such R.

As a phosphate ester group which is a substituent, the structure represented by -OP (O)-(OR) ₂ can be shown. This R may be same or different and can illustrate an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc. which were mentioned above. The substituent mentioned above may further substitute by such R.

Substituent of the amide group is represented by the structure -C (O) NH _2,, or, -C (O) NHR, -NHC (O) R, -C (O) N (R) 2, -NRC (O) R Can be represented. This R may be same or different and can illustrate an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc. which were mentioned above. The substituent mentioned above may further substitute by such R.

As an aryl group which is a substituent, the thing similar to the aryl group mentioned above is mentioned. The other substituent mentioned above may further substitute by this aryl group.

As an alkyl group which is a substituent, the thing similar to the alkyl group mentioned above is mentioned. The other substituent mentioned above may further substitute by this alkyl group.

As an alkenyl group which is a substituent, the same thing as the alkenyl group mentioned above is mentioned. The other substituent mentioned above may further substitute by this alkenyl group.

As an alkynyl group which is a substituent, the thing similar to the alkynyl group mentioned above is mentioned. The other substituent mentioned above may further substitute by this alkynyl group.

In general, when a bulky structure is introduced, the reactivity and liquid crystal alignment of the amino group may be lowered. As B ₁ and B ₂ , an alkyl group having 1 to 5 carbon atoms which may have a hydrogen atom or a substituent is more preferable. And a hydrogen atom, a methyl group or an ethyl group is particularly preferable.

As a structure of Y <_1> in Formula (2), if it has at least 1 sort (s) of structure chosen from the group which consists of an amino group, an imino group, and a nitrogen-containing heterocyclic ring, the structure is not specifically limited. If the specific example is given, the divalent organic which has at least 1 sort (s) of structure chosen from the group which consists of an amino group, an imino group, and a nitrogen-containing heterocyclic ring represented by following formula (YD-1) (YD-5)- The group can be mentioned.

[Formula 16]

In formula (YD-1), A <_1> is a C3-C15 nitrogen atom containing heterocyclic ring, Z <_1> is a C1-C20 hydrocarbon group which may have a hydrogen atom or a substituent.

In formula (YD-2), W <_1> is a C1-C10 hydrocarbon group, A <_2> is a C3-C15 monovalent organic group which has a nitrogen atom containing heterocyclic ring, or a C1-C6 aliphatic group Substituted di-substituted amino groups.

In the formula (YD-3), W ₂ has a carbon number of 6 to 15, and also is a divalent organic group having 1 to 2 benzene rings, W ₃ is alkylene or biphenylene or a nitrogen atom having a carbon number of 2 to 5 It is a C12-18 divalent organic group containing a containing hetero ring, Z <_2> is a hydrogen atom, a C1-C5 alkyl group, or a benzene ring, and a is an integer of 0-1.

In formula (YD-4), A <_3> is a C3-C15 nitrogen atom containing heterocyclic ring.

In the formula (YD-5), A ₄ is a heterocyclic ring containing the nitrogen atom of a carbon number of 3 ~ 15, W ₅ is an alkylene group having a carbon number of 2-5.

As a C3-C15 nitrogen atom containing heterocyclic ring of Formula (YD-1), (YD-2), (YD-4), and (YD-5) A <_1> , A <_2> , A <_3> , and A <_4> If it is a well-known structure, it will not specifically limit. Among them, pyrrolidine, pyrrole, imidazole, pyrazole, oxazole, thiazole, piperidine, piperazine, pyridine, pyrazine, indole, benzimidazole, quinoline, isoquinoline and carbazole, Piperazine, piperidine, indole, benzimidazole, imidazole, carbazole, pyrrole, and pyridine are more preferred.

Moreover, as a specific example of Y <_2> in Formula (2), the divalent organic group which has the nitrogen atom shown by following formula (YD-6)-(YD-43) is mentioned, and charge accumulation by alternating current drive is carried out. In addition, the formula (YD-14), (YD-18), (YD-19), (YD-20), (YD-21), and (YD) -23) to (YD-30) and (YD-40) to (YD-43) are more preferable, and (YD-14), (YD-18), (YD-23), (YD-25) and (YD-40)-(YD-43) are especially preferable.

[Formula 17]

H is an integer of 1-3 in a formula (YD-17), j is an integer of 0-3 in a formula (YD-14) and (YD-21) and (YD-22).

[Formula 18]

J is an integer of 0-3 in a formula (YD-25), (YD-26), (YD-29), and (YD-30).

[Formula 19]

J is an integer of 0-3 in a formula (YD-41), (YD-42), and (YD-43).

It is preferable that the ratio of the diamine represented by Formula (2) in the polyamic acid and imidation polymer of polyamic acid of this invention is 10-100 mol% with respect to 1 mol of all diamine, More preferably, it is 30-100 Mol%, More preferably, it is 50-100 mol%.

Although the diamine represented by Formula (2) in the imidation polymer of the polyamic acid and polyamic acid which are (B) component of this invention may be used independently and may use multiple together, in that case also by Formula (2) It is preferable to use the said preferable quantity as a total in the diamine shown.

You may use the diamine represented by following formula (7) other than the diamine represented by the said Formula (2) for the imidation polymer of the polyamic acid and polyamic acid which are (B) component contained in the liquid crystal aligning agent of this invention. Y <_2> in following formula (7) is a divalent organic group, The structure is not specifically limited, Two or more types may be mixed. If the specific example is shown, following (Y-1)-(Y-75) will be mentioned.

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

In the imidation polymer of the polyamic acid and polyamic acid which are (B) component contained in the liquid crystal aligning agent of this invention, when the ratio of the diamine represented by Formula (7) increases, there exists a possibility that it may inhibit the effect of this invention. , Not preferred. Therefore, as for the ratio of the diamine represented by Formula (7), 0-90 mol% is preferable with respect to 1 mol of all diamine, More preferably, it is 0-50 mol%, More preferably, it is 0-20 mol%.

<Method for producing polyamic acid ester>

The polyamic acid ester which is a polyimide precursor used for this invention can be synthesize | combined by the method of (1), (2) or (3) shown below.

(1) When synthesized from polyamic acid

Polyamic acid ester can be synthesize | combined by esterifying the polyamic acid obtained from tetracarboxylic dianhydride and diamine.

Specifically, the polyamic acid and the esterifying agent are synthesized by reacting in the presence of an organic solvent at -20 ° C to 150 ° C, preferably at 0 ° C to 50 ° C for 30 minutes to 24 hours, preferably 1 to 4 hours. Can be.

As an esterification agent, what can be easily removed by refinement | purification is preferable, N, N- dimethylformamide dimethyl acetal, N, N- dimethylformamide diethyl acetal, N, N- dimethylformamide dipropyl acetal, N, N-dimethylformamide dineopentylbutyl acetal, N, N-dimethylformamide di-t-butylacetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene , 1-propyl-3-p-tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride, and the like. As for the addition amount of an esterifying agent, 2-6 molar equivalent is preferable with respect to 1 mol of repeating units of a polyamic acid.

The solvent used for the reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the solubility of the polymer, and these may be used alone or in combination of two or more thereof. You may use it. 1-30 mass% is preferable, and, as for the density | concentration at the time of a synthesis | combination from a viewpoint that a precipitation of a polymer does not occur easily and a high molecular weight body is easy to obtain, 5-20 mass% is more preferable.

(2) When synthesized by reaction of tetracarboxylic acid diester dichloride and diamine

Polyamic acid ester can be synthesize | combined from tetracarboxylic-acid diester dichloride and diamine.

Specifically, tetracarboxylic acid diester dichloride and diamine are present in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably 1 to It can synthesize | combine by making it react for 4 hours.

As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds mildly. It is preferable that the addition amount of a base is the quantity which is easy to remove, and is 2-4 times mole with respect to tetracarboxylic-acid diester dichloride from a viewpoint that a high molecular weight body is easy to obtain.

As for the solvent used for the said reaction, N-methyl- 2-pyrrolidone or (gamma) -butyrolactone is preferable from the solubility of a monomer and a polymer, These may be used 1 type or in mixture of 2 or more types. 1-30 mass% is preferable, and, as for the polymer concentration at the time of synthesis | combination from a viewpoint that a precipitation of a polymer does not occur easily and a high molecular weight body is easy to obtain, 5-20 mass% is more preferable. Moreover, in order to prevent hydrolysis of tetracarboxylic-acid diester dichloride, it is preferable that the solvent used for the synthesis | combination of a polyamic acid ester is dehydrated as much as possible, and it is preferable to prevent mixing of external air in nitrogen atmosphere.

(3) When synthesized polyamic acid ester from tetracarboxylic acid diester and diamine

Polyamic acid ester can be synthesize | combined by polycondensing tetracarboxylic-acid diester and diamine.

Specifically, tetracarboxylic acid diester and diamine in the presence of a condensing agent, a base, and an organic solvent at 0 ° C to 150 ° C, preferably 0 ° C to 100 ° C, 30 minutes to 24 hours, preferably 3 It can synthesize | combine by making it react for 15 hours.

As said condensing agent, a triphenyl phosphite, dicyclohexyl carbodiimide, 1-

Ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium, O- (benzotriazole- 1-yl) -N, N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N, N', N'-tetramethyluronium Hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzooxazolyl) phosphonic acid diphenyl, etc. can be used. As for the addition amount of a condensing agent, 2-3 times mole is preferable with respect to tetracarboxylic-acid diester.

As the base, tertiary amines such as pyridine and triethylamine can be used. The addition amount of base is the quantity which is easy to remove, and 2-4 times mole is preferable with respect to a diamine component from a viewpoint that a high molecular weight body is easy to obtain.

In the above reaction, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. As for the addition amount of a Lewis acid, 0-1.0 times mole is preferable with respect to a diamine component.

Since high molecular weight polyamic acid ester is obtained among the synthesis | combining method of said three polyamic acid ester, the synthesis method of said (1) or said (2) is especially preferable.

The solution of the polyamic acid ester obtained as mentioned above can deposit a polymer by inject | pouring into a poor solvent, stirring well. Precipitation is carried out several times, followed by washing with a poor solvent, followed by normal temperature or heat drying to obtain a purified polyamic acid ester powder. Although the poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, etc. are mentioned.

<Synthesis of polyamic acid>

When obtaining a specific polymer (A) or a specific polymer (B) by reaction of tetracarboxylic dianhydride and diamine, the method of mixing and reacting tetracarboxylic dianhydride and diamine in an organic solvent is simple.

The organic solvent used in the reaction is not particularly limited as long as the produced polyamic acid is dissolved. However, if the specific examples are given, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl 2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma -butyrolactone, etc. are mentioned. You may use these individually or in mixture. Moreover, even if it is a solvent which does not melt a polyamic acid, you may mix and use it with the said solvent in the range in which the produced polyamic acid does not precipitate. In addition, since water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyamic acid, it is preferable to use an organic solvent that is dehydrated and dried as much as possible.

As a method of mixing a tetracarboxylic dianhydride component and a diamine component in an organic solvent, the solution which disperse | distributed or dissolved the diamine component in the organic solvent is stirred, and the tetracarboxylic dianhydride component is disperse | distributed as it is or in an organic solvent. Or the method of dissolving and adding, the method of adding a diamine component to the solution which disperse | distributed or dissolved the tetracarboxylic dianhydride component in the organic solvent, the method of alternately adding the tetracarboxylic dianhydride component and a diamine component, etc. These may be mentioned and any method of these may be sufficient in this invention. Moreover, when a tetracarboxylic dianhydride component or a diamine component consists of multiple types of compounds, you may make it react in the state which mixed these multiple types of components previously, and may make them react individually one by one.

The temperature at the time of making a tetracarboxylic dianhydride component and a diamine component react in an organic solvent is 0-150 degreeC normally, Preferably it is 5-100 degreeC, More preferably, it is 10-80 degreeC. The higher the temperature, the faster the polymerization reaction is completed, but when the temperature is too high, a high molecular weight polymer may not be obtained. In addition, the reaction can be carried out at any concentration. However, if the concentration is too low, it is difficult to obtain a high molecular weight polymer. If the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. 1 to 50% by weight, more preferably 5 to 30% by weight. The reaction initial stage may be performed in high concentration | density, and may add an organic solvent after that.

It is preferable that the ratio of the tetracarboxylic dianhydride component and diamine component used for the polymerization reaction of a polyamic acid is 1: 0.8-1.2 in molar ratio. Moreover, since the coloring of a solution may become large for the polyamic acid obtained by making the diamine component excess, what is necessary is just to set it as 1: 0.8-1 when the coloring of a solution is anxious. As in the normal polycondensation reaction, the closer the molar ratio is to 1: 1, the larger the molecular weight of the polyamic acid obtained. When the molecular weight of a polyamic acid is too small, the intensity | strength of the coating film obtained from it may become inadequate, On the contrary, when the molecular weight of a polyamic acid is too large, the viscosity of the liquid-crystal aligning agent manufactured from it will become high too much, and workability at the time of coating film formation The uniformity of a coating film may worsen. Therefore, 0.1-2.0 are preferable at a reduced viscosity (concentration 0.5dl / g, 30 degreeC in NMP), and, as for the polyamic acid used for the liquid crystal aligning agent of this invention, More preferably, it is 0.2-1.5.

When not using the solvent used for superposition | polymerization of a polyamic acid in the liquid crystal aligning agent of this invention, or when an unreacted monomer component or an impurity exists in a reaction solution, this precipitation collection and purification are performed. It is preferable to introduce | transduce a polyamic-acid solution into the stirring poor solvent, and to collect and collect the method. Although it does not specifically limit as a poor solvent used for precipitation collection of a polyamic acid, methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, etc. can be illustrated. . The polyamic acid precipitated by adding to the poor solvent can be collected by filtration and washing, recovered, and then subjected to normal temperature or heat drying under normal pressure or reduced pressure to obtain a powder. When this powder is melt | dissolved in a good solvent further and the operation of reprecipitation is repeated 2-10 times, a polyamic acid can also be refine | purified. When all impurities are not removed by one precipitation recovery operation, it is preferable to perform this purification step. It is preferable to use three or more kinds of poor solvents such as alcohols, ketones, and hydrocarbons as the poor solvent at this time, because the efficiency of purification is further increased.

<Method for producing polyimide>

The polyimide used for this invention can be manufactured by imidating the said polyamic acid ester or polyamic acid. When manufacturing a polyimide from polyamic acid ester, chemical imidation which adds a basic catalyst to the polyamic acid solution obtained by melt | dissolving the said polyamic acid ester solution or polyamic acid ester resin powder in an organic solvent is easy. Chemical imidation is preferable because the imidation reaction advances at a comparatively low temperature, and molecular weight fall of a polymer hardly occurs in the course of imidation.

When producing a polyimide from a polyamic acid, chemical imidation which adds a catalyst to the solution of the said polyamic acid obtained by reaction of a diamine component and tetracarboxylic dianhydride is easy. Chemical imidation is preferable because the imidation reaction advances at a comparatively low temperature, and molecular weight fall of a polymer hardly occurs in the course of imidation.

Chemical imidation can be performed by stirring the polymer to make it imidate in presence of a basic catalyst and an acid anhydride in an organic solvent. As an organic solvent, the solvent used at the time of the polymerization reaction mentioned above can be used. Pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. are mentioned as a basic catalyst. Especially, pyridine is preferable because it has a basicity suitable for advancing reaction. Moreover, acetic anhydride, trimellitic anhydride, a pyromellitic dianhydride, etc. are mentioned as acid anhydride, Especially, when acetic anhydride is used, since refinement | purification after completion | finish of reaction becomes easy, it is preferable.

The temperature at the time of performing an imidation reaction is -20 degreeC-140 degreeC, Preferably it is 0 degreeC-100 degreeC, and reaction time can be implemented in 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times, of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times of the amic acid group. The imidation ratio of the polymer obtained can be controlled by adjusting catalyst amount, temperature, and reaction time.

Since the added catalyst etc. remain in the solution after the imidation reaction of polyamic acid ester or polyamic acid, the imidated polymer obtained is collect | recovered by the means described below, redissolved in an organic solvent, and the liquid crystal of this invention It is preferable to set it as an aligning agent.

The polymer of the polyimide obtained as mentioned above can be precipitated by inject | pouring into a poor solvent, stirring well. Precipitation is carried out several times, followed by washing with a poor solvent, followed by normal temperature or heat drying to obtain a purified polyamic acid ester powder.

Although the said poor solvent is not specifically limited, Methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, etc. are mentioned.

As for the molecular weight of the polyimide precursor which is (A) component and (B) component used for this invention, 2,000-500,000 are preferable at a weight average molecular weight, More preferably, it is 5,000-300,000, More preferably, it is 10,000-100,000 to be.

As a polyimide which is (A) component and (B) component used for this invention, the polyimide obtained by ring-closing the said polyimide precursor is mentioned. In this polyimide, the closed ring ratio (also called imidation ratio) of the amic acid group does not necessarily need to be 100%, and can be arbitrarily adjusted according to a use or a purpose.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention is a composition used for forming a liquid crystal aligning film, The specific polymer (A) which has a structure represented by said Formula (1), and the specific polymer containing the structure of said Formula (2) ( It contains B) and 1 type may be sufficient as specific polymer (A) and specific polymer (B) contained in the liquid crystal aligning agent of this invention, respectively and may be two or more types. Moreover, in addition to a specific polymer, you may contain the other polymer, ie, the polymer which does not have the bivalent airway represented by Formula (1), and the bivalent airway represented by Formula (2). Examples of the other polymers include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or derivatives thereof, and poly (styrene-phenylmaleimide ) Derivatives, poly (meth) acrylates, and the like. When the liquid crystal aligning agent of this invention contains another polymer, it is preferable that the ratio of the specific polymer in all the polymer components is 5 mass% or more, and 5-95 mass% is mentioned as an example.

A liquid crystal aligning agent is used in order to produce a liquid crystal aligning film, and generally takes the form of a coating liquid from a viewpoint of forming a uniform thin film. Also in the liquid crystal aligning agent of this invention, it is preferable that it is a coating liquid containing said polymer component and the organic solvent which melt | dissolves this polymer component. In that case, the density | concentration of the polymer in a liquid crystal aligning agent can be suitably changed with the setting of the thickness of the coating film to form. It is preferable that it is 1 mass% or more from the point which forms a uniform and defect-free coating film, and it is preferable to set it as 10 mass% or less from the point of the storage stability of a solution. The density | concentration of especially preferable polymer is 2-8 mass%.

The organic solvent contained in a liquid crystal aligning agent will not be specifically limited if a polymer component melt | dissolves uniformly. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide and γ-buty. Rolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone and the like. Especially, it is preferable to use N-methyl- 2-pyrrolidone, N-ethyl- 2-pyrrolidone, or (gamma) -butyrolactone.

Moreover, as for the organic solvent contained in a liquid crystal aligning agent, it is common to use the mixed solvent which used together the solvent which improves the coating property at the time of apply | coating a liquid crystal aligning agent, and the surface smoothness of a coating film in addition to the above-mentioned solvent, Also in the liquid crystal aligning agent of this invention, such a mixed solvent is used preferably. Although the specific example of the organic solvent used together is given below, it is not limited to these examples.

For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methyl Cyclohexanol, 3-methylcyclohexanol, 2,6-dimethyl-4-heptanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1 , 3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, diisopropyl ether , Dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-part Ethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methylethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3 -Pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 2,6-dimethyl-4-heptanone, 4,6-dimethyl-2-heptanone, 3-ethoxybutyl acetate, 1- Methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol Monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monobutyl ether , 1- (butock Ethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) Ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol Noethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid , 3-methoxy propyl propionate, 3-methoxy butyl propionate, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, the following formula [D-1] to [ D-3], etc. are mentioned.

[Formula 25]

Of the formula ^[D-1], D 1 represents an alkyl group having a carbon number of 1 to 3, wherein ^[D-2], D 2 represents an alkyl group having a carbon number of 1 to 3, formula ^[D-3], D 3 Represents an alkyl group having 1 to 4 carbon atoms.

Especially, as a preferable solvent combination, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, ethylene glycol monobutyl ether, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, and propylene glycol mono Butyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and di Ethylene glycol diethyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone, propylene glycol monobutyl ether, 2,6-dimethyl-4-heptanone, N-methyl-2-pyrrolidone and γ Butyrolactone, propylene glycol monobutyl ether, diisopropyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, 2,6-dimethyl-4-heptanol, N -Methyl-2-pyrrolidone, gamma -butyrolactone, dipropylene glycol dimethyl ether, etc. are mentioned. The kind and content of such a solvent are suitably selected according to the coating device of a liquid crystal aligning agent, application | coating conditions, application environment, etc.

In addition, in order to improve the adhesiveness of the coating film to a board | substrate, you may add additives, such as a silane coupling agent, and may add another resin component to the liquid crystal aligning agent of this invention.

As a compound which improves the adhesiveness of a liquid crystal aligning film and a board | substrate, a functional silane containing compound and an epoxy group containing compound are mentioned, For example, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3 -Glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureido Propyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxy Silyl-1,4,7-triadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxy Silyl-3,6-diazanyl 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-aminopropyltriethoxysilane, ethylene glycol di Glycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-te Raglycidyl-2,4-hexanediol, N, N, N ', N',-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl ) Cyclohexane or N, N, N ', N',-tetraglycidyl-4,4'- diamino diphenylmethane, etc. are mentioned.

Moreover, you may add the following additives to the liquid crystal aligning agent of this invention in order to raise the mechanical strength of a film | membrane.

[Formula 26]

[Formula 27]

It is preferable that these additives are 0.1-30 mass parts with respect to 100 mass parts of the polymer component contained in a liquid crystal aligning agent. If it is less than 0.1 mass part, an effect cannot be expected, and when it exceeds 30 mass parts, since the orientation of a liquid crystal is reduced, More preferably, it is 0.5-20 mass parts.

<Liquid crystal aligning film>

The liquid crystal aligning film of this invention is obtained from the said liquid crystal aligning agent. If an example of the method of obtaining a liquid crystal aligning film from a liquid crystal aligning agent is given, the method of performing an orientation process by the rubbing process or the photo-alignment process method with respect to the film | membrane obtained by apply | coating the liquid crystal aligning agent of a coating liquid form to a board | substrate, drying, and baking. Can be mentioned.

As a board | substrate which apply | coats a liquid crystal aligning agent, if it is a board | substrate with high transparency, it will not specifically limit, Plastic board | substrates, such as an acryl substrate and a polycarbonate board | substrate, etc. can also be used with a glass substrate and a silicon nitride substrate. In that case, it is preferable at the point of a process simplification to use the board | substrate with which the ITO electrode etc. for driving a liquid crystal were formed. Moreover, in a reflective liquid crystal display element, as long as it is only one side board | substrate, even an opaque thing, such as a silicon wafer, can be used, and the material which reflects light, such as aluminum, can also be used for the electrode in this case.

Although the coating method of a liquid crystal aligning agent is not specifically limited, Industrially, screen printing, offset printing, flexographic printing, the inkjet method, etc. are common. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method, a spray method, and the like, and may be used depending on the purpose.

After apply | coating a liquid crystal aligning agent on a board | substrate, a solvent is evaporated and baked by heating means, such as a hotplate, a thermocyclic oven, and an IR (infrared rays) oven. The drying after apply | coating a liquid crystal aligning agent, and the baking process can select arbitrary temperature and time. Usually, in order to remove the solvent contained enough, baking is carried out at 50-120 degreeC for 1 to 10 minutes, Then, the conditions baked at 150-300 degreeC for 5 to 120 minutes are mentioned.

Although the thickness of the liquid crystal aligning film after baking is not specifically limited, Since the reliability of a liquid crystal display element may fall when too thin, it is preferable that it is 5-300 nm, and 10-200 nm is more preferable.

The liquid crystal aligning film of this invention is preferable as a liquid crystal aligning film of the liquid crystal display element of transverse electric field systems, such as an IPS system and a FFS system, and is especially useful as a liquid crystal aligning film of the liquid crystal display element of a FFS system.

<Liquid crystal display element>

After obtaining the board | substrate with which the liquid crystal aligning film obtained from the said liquid crystal aligning agent was formed, the liquid crystal display element of this invention produces a liquid crystal cell by a known method, and sets it as an element using the liquid crystal cell.

As an example of the manufacturing method of a liquid crystal cell, the liquid crystal display element of a passive matrix structure is given and demonstrated. Moreover, the liquid crystal display element of an active matrix structure in which switching elements, such as TFT (Thin Film Transistor), was formed in each pixel part which comprises an image display may be sufficient.

Specifically, the transparent glass substrate is prepared, a common electrode is formed on one board | substrate, and a segment electrode is formed on the other board | substrate. These electrodes can be made into an ITO electrode, for example, and are patterned so that desired image display can be performed. Next, an insulating film is formed on each board | substrate so that a common electrode and a segment electrode may be coat | covered. The insulating film can be, for example, a film made of SiO ₂ -TiO ₂ formed by the sol-gel method. Next, a liquid crystal aligning film is formed on each board | substrate on the conditions similar to the above.

Next, after arrange | positioning an ultraviolet curable sealing material, for example in the predetermined place on one board | substrate among two board | substrates which formed the liquid crystal aligning film, and arrange | positioning a liquid crystal to the predetermined resin point on the liquid crystal aligning film surface, a liquid crystal aligning film opposes. After spreading and spreading a liquid crystal on the front surface of a liquid crystal aligning film by bonding the other board | substrate together and crimping | bonding so that a liquid crystal cell may be obtained by irradiating an ultraviolet-ray to the whole surface of a board | substrate and hardening a sealing material.

Or as a process after forming a liquid crystal aligning film on a board | substrate, when arrange | positioning a sealing material in the predetermined place on one board | substrate, after forming the opening part which can fill a liquid crystal from the outside, after bonding a board | substrate without arranging a liquid crystal, The liquid crystal material is inject | poured into a liquid crystal cell through the opening part formed in the sealing material, and then this opening part is sealed with an adhesive agent and a liquid crystal cell is obtained. As injection of a liquid crystal material, the vacuum injection method may be sufficient and the method using the capillary phenomenon in air | atmosphere may be sufficient.

In any of the above methods, in order to secure a space in which the liquid crystal material is filled in the liquid crystal cell, columnar protrusions are formed on one substrate, the spacers are dispersed on one substrate, or the spacer is mixed in the sealing material, Or a combination thereof.

As said liquid crystal material, a nematic liquid crystal and a smectic liquid crystal are mentioned, Especially, a nematic liquid crystal is preferable and you may use either a positive liquid crystal material or a negative liquid crystal material. Next, the polarizing plate is installed. Specifically, it is preferable to affix a pair of polarizing plate on the surface on the opposite side to the liquid crystal layer of two board | substrates.

In addition, the liquid crystal aligning film and liquid crystal display element of this invention are not limited to the said base material, as long as the liquid crystal aligning agent of this invention is used, What was produced by other well-known methods may be sufficient. The process until obtaining a liquid crystal display element from a liquid crystal aligning agent is disclosed, for example in Paragraph 0074 of page 17 of Unexamined-Japanese-Patent No. 2015-135393-paragraph 19 of page 19 etc., for example.

<Method for Manufacturing Substrate Having Liquid Crystal Alignment Film> and <Method for Manufacturing Liquid Crystal Display Element>

As an example of the manufacturing method of the board | substrate which has the liquid crystal aligning film of this invention, the manufacturing method of the liquid crystal aligning film for transverse electric field drive-type liquid crystal display elements is shown below.

[I] at least one polymer (A) selected from a polyamic acid obtained by using a tetracarboxylic dianhydride component and a diamine component containing the diamine represented by the formula (1) and an imidized polymer of the polyamic acid; At least 1 sort (s) of polymer (B) chosen from the polyamic acid obtained using the tetracarboxylic dianhydride component and the diamine component containing the diamine represented by said formula (2), and the imidation polymer of this polyamic acid After apply | coating a liquid crystal aligning agent on the board | substrate which has a conductive film for transverse electric field drive, drying, and forming a coating film;

[II] A step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; And

[III] a step of heating the coating film obtained in [II];

Has

By the said process, the liquid crystal aligning film for transverse electric field drive-type liquid crystal display elements to which orientation control ability was provided can be obtained, and the board | substrate which has this liquid crystal aligning film can be obtained.

Moreover, a transverse electric field drive-type liquid crystal display element can be obtained by preparing a 2nd board | substrate other than the said obtained board | substrate (1st board | substrate).

As the second substrate, instead of using a substrate having a conductive film for transverse electric field drive, a substrate having no conductive film for transverse electric field drive is used, and the above-mentioned steps [I] to [III] (the conductive film for transverse electric field drive Since the board | substrate which does not have is used, for convenience, the 2nd board | substrate which has a liquid crystal aligning film to which alignment control ability was provided can be obtained by using (in this application, it may abbreviate as process [I ']-[III']). .

The manufacturing method of the transverse electric field drive-type liquid crystal display element,

[IV] a step of arranging the first and second substrates obtained above so as to face each other so that the liquid crystal alignment films of the first and second substrates face each other via liquid crystal;

Has Thereby, a transverse electric field drive-type liquid crystal display element can be obtained.

Hereinafter, each process of [I]-[III] and [IV] which the manufacturing method of this invention has is demonstrated.

<Process [I]>

In process [I], the polymer composition containing a photosensitive main chain type polymer and an organic solvent is apply | coated on the board | substrate which has a conductive film for lateral electric field drive, and it dries and forms a coating film. The photosensitive main chain polymer in the present invention is a specific polymer (A).

<Substrate>

Although it does not specifically limit about a board | substrate, When the liquid crystal display element manufactured is a transmissive type, it is preferable that the board | substrate with high transparency is used. In that case, it does not specifically limit, Plastic substrates, such as a glass substrate or an acrylic substrate, a polycarbonate substrate, etc. can be used.

Moreover, in consideration of application to a reflective liquid crystal display element, an opaque substrate, such as a silicon wafer, can also be used.

<Conductive Film for Transverse Electric Field Driving>

The substrate has a conductive film for transverse electric field drive.

Examples of the conductive film include, but are not limited to, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and the like when the liquid crystal display element is a transmission type.

Moreover, in the case of a reflective liquid crystal display element, although the material which reflects light, such as aluminum, etc. are mentioned as a conductive film, it is not limited to these.

As a method of forming a conductive film on a substrate, a conventionally well-known method can be used.

The method of apply | coating the polymer composition mentioned above on the board | substrate which has a conductive film for transverse electric field drive is not specifically limited.

Industrially, the coating method is generally carried out by screen printing, offset printing, flexographic printing, inkjet printing, or the like. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method (rotary coating method), a spray method, and the like, and may be used according to the purpose.

After apply | coating a polymer composition on the board | substrate which has a conductive film for transverse electric field drive, it is 30-150 degreeC by heating means, such as a hotplate, a thermocyclic oven, or an IR (infrared) type oven, Preferably it is 70-110 The coating film can be obtained by evaporating a solvent at ° C. If the drying temperature is too low, there is a tendency that the drying of the solvent is insufficient, and if the heating temperature is too high, thermal imidization proceeds, and as a result, the photolysis reaction proceeds excessively by polarized light exposure, in which case self-organization Reorientation in one direction may be difficult and the orientation stability may be impaired. Therefore, it is preferable that the drying temperature at this time is a temperature from which thermal imidation of a specific polymer does not progress substantially from a viewpoint of liquid-crystal orientation stability.

When the thickness of a coating film is too thick, it becomes disadvantageous in terms of the power consumption of a liquid crystal display element, and when too thin, the reliability of a liquid crystal display element may fall, Preferably it is 5 nm-300 nm, More preferably, it is 10 nm To 150 nm.

Moreover, it is also possible to provide the process of cooling the board | substrate with a coating film to room temperature after the [I] process and before the following [II] process.

<Step [II]>

In process [II], the ultraviolet-ray which polarized to the coating film obtained by process [I] is irradiated. When irradiating the polarized ultraviolet-ray to the film surface of a coating film, the ultraviolet-ray which polarized through the polarizing plate from a fixed direction with respect to a board | substrate is irradiated. As an ultraviolet-ray to be used, the ultraviolet-ray of the range of 100 nm-400 nm can be used. Preferably, an optimal wavelength is selected through a filter etc. according to the kind of coating film used. For example, ultraviolet rays having a wavelength of 240 nm to 400 nm can be selected and used so as to selectively cause a photolysis reaction. As the ultraviolet ray, for example, light emitted from a high pressure mercury lamp or a metal halide lamp can be used.

The irradiation amount of the polarized ultraviolet rays depends on the coating film to be used. The amount of irradiation is the amount of polarized ultraviolet light that realizes the maximum value of ΔA (hereinafter also referred to as ΔAmax) in the coating film, which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorbance in the vertical direction. It is preferable to carry out in 1%-70% of range, and it is more preferable to carry out in 1%-50% of range.

<Step [III]>

In process [III], the coating film irradiated with the ultraviolet-ray polarized by process [II] is heated. By heating, orientation controllability can be provided to a coating film.

Heating can use heating means, such as a hotplate, a thermocyclic oven, or an IR (infrared) oven. Heating temperature can be determined in consideration of the temperature which expresses favorable liquid-crystal orientation stability and electrical property in the coating film to be used.

It is preferable that heating temperature exists in the temperature range in which a principal chain polymer expresses favorable liquid-crystal orientation stability. When heating temperature is too low, there exists a tendency for the amplification effect and thermal imidation by heat to become inadequate, and when heating temperature is too high than temperature range, there exists a tendency for the anisotropy provided by polarized light exposure to lose | disappear. In some cases, it is difficult to redirect in one direction due to self-organization.

The thickness of the coating film formed after the heating is preferably 5 nm to 300 nm, more preferably 50 nm to 150 nm, for the same reason described in step [I].

By having the above process, in the manufacturing method of this invention, introduction of the anisotropy to a coating film of high efficiency can be implement | achieved. And the board | substrate with a liquid crystal aligning film can be manufactured with high efficiency.

<Process [IV]>

The process [IV] comprises the electrically conductive film obtained by said [I ']-[III'] similarly to the board | substrate (1st board | substrate) which has a liquid crystal aligning film on the electrically conductive film for transverse electric field drive obtained in [III]. The board | substrate (2nd board | substrate) with which the liquid crystal aligning film which does not have was formed is mutually arrange | positioned so that both liquid crystal aligning films may face through a liquid crystal, a liquid crystal cell is produced by a well-known method, and a transverse electric field drive-type liquid crystal display element is produced It is a process. In the step [I], the steps [I '] to [III'] are used instead of the substrate having the conductive film for transverse electric field drive. It can carry out similarly to I]-[III]. The difference between the steps [I] to [III] and the steps [I '] to [III'] is only the presence or absence of the above-described conductive film, and thus the description of the steps [I '] to [III'] is omitted.

If an example of preparation of a liquid crystal cell or a liquid crystal display element is given, the above-mentioned 1st and 2nd board | substrate are prepared, a spacer is spread | dispersed on the liquid crystal aligning film of a single side board | substrate, so that a liquid crystal aligning film surface may become inside, and another The method of bonding a board | substrate of one side, injecting a liquid crystal under reduced pressure, and sealing it, or dropping a liquid crystal on the liquid crystal aligning film surface which spread | dispersed a spacer, and then bonding a board | substrate together and sealing etc. can be illustrated. At this time, it is preferable to use the board | substrate which has an electrode of the same structure as the comb teeth for transverse electric field drive for the board | substrate of one side. The diameter of the spacer at this time is preferably 1 µm to 30 µm, more preferably 2 µm to 10 µm. This spacer diameter determines the distance between a pair of substrates sandwiching the liquid crystal layer, that is, the thickness of the liquid crystal layer.

In the manufacturing method of the board | substrate with which the coating film of this invention was formed, after apply | coating a polymer composition on a board | substrate and forming a coating film, it irradiates the ultraviolet-ray which polarized. Subsequently, high efficiency anisotropy introduction into a main chain polymer film is implemented by heating, and the board | substrate with a liquid crystal aligning film provided with the orientation control ability of a liquid crystal is manufactured.

In the coating film used for this invention, the high efficiency anisotropic introduction to a coating film is implement | achieved using the principle of molecular reorientation caused by the self-organization based on the photoreaction of a principal chain. In the manufacturing method of this invention, in the case of the structure which has a photodegradable group as a photoreactive group in a main chain type polymer, after forming a coating film on a board | substrate using a main chain type polymer, it irradiates the ultraviolet-ray which polarized, and then heats After carrying out, the liquid crystal display element is produced.

Therefore, the coating film used for the method of this invention can introduce | transduce anisotropy with high efficiency, and can be made into the liquid crystal aligning film excellent in orientation control ability by performing irradiation and heat processing of the polarized ultraviolet-ray to a coating film sequentially.

And in the coating film used for the method of this invention, the irradiation amount of the polarized ultraviolet-ray to a coating film and the heating temperature in heat processing are optimized. As a result, anisotropic introduction into the coating film with high efficiency can be realized.

The irradiation amount of polarized ultraviolet light which is optimal for the high efficiency anisotropic introduction to the coating film used for this invention corresponds to the irradiation amount of the polarized ultraviolet light which optimizes the quantity which the photosensitive group photodecomposes in the coating film. As a result of irradiating the ultraviolet-ray which polarized with respect to the coating film used for this invention, when there are few photosensitive groups which photodecomposes, sufficient amount of photoreaction will not become. In that case, sufficient self-organization does not advance even if it heats after that.

Therefore, in the coating film used for this invention, it is preferable that the optimal amount which a photosensitive group photodecomposes by irradiation of a polarized ultraviolet-ray is 0.1 mol%-90 mol% of the polymer film, and 0.1 mol%-80 mol% It is more preferable to set it as. By setting the amount of the photosensitive group to be photoreactive in such a range, self-organization in the subsequent heat treatment proceeds efficiently and high efficiency anisotropic formation in the film becomes possible.

In the coating film used for the method of this invention, the quantity of the photodegradation reaction of the photosensitive group in the principal chain of a polymer film is optimized by optimization of the irradiation amount of the polarized ultraviolet-ray. In addition to the subsequent heat treatment, anisotropic introduction into the coating film used in the present invention with high efficiency is realized. In that case, about the preferable quantity of polarized ultraviolet-ray, it is possible to implement based on evaluation of the ultraviolet absorption of the coating film used for this invention.

That is, about the coating film used for this invention, the ultraviolet absorption of the direction parallel to the polarization direction of the polarized ultraviolet ray after polarized ultraviolet irradiation, and the ultraviolet absorption of a perpendicular direction are measured, respectively. From the measurement result of ultraviolet absorption, (DELTA) A which is the difference of the ultraviolet absorbance of the direction parallel to the polarization direction of the polarized ultraviolet-ray in the coating film, and the ultraviolet absorbance of the perpendicular | vertical direction is evaluated. And the maximum value (DELTA) Amax of (DELTA) A realized in the coating film used for this invention, and the irradiation amount of the polarization ultraviolet-ray which implements it are calculated | required. In the manufacturing method of this invention, the amount of the polarized ultraviolet-ray of a preferable quantity irradiated in manufacture of a liquid crystal aligning film can be determined based on the amount of polarized ultraviolet-ray irradiation which realizes this (DELTA) Amax.

As mentioned above, in the manufacturing method of this invention, in order to implement | achieve highly efficient anisotropic introduction into a coating film, based on the temperature range which the main chain type polymer | macromolecule liquid-crystal orientation stability, the preferable heating temperature as mentioned above is It is good to decide. Therefore, for example, the temperature range in which the main chain polymer used in the present invention impart liquid crystal alignment stability can be determined in consideration of the temperature at which good liquid crystal alignment stability and electrical properties are expressed in the coating film to be used. It can set in the temperature range based on the liquid crystal aligning film which consists of polyimide. That is, it is preferable to set it as 150 degreeC-300 degreeC, and, as for the temperature of the heating after polarized ultraviolet irradiation, it is more preferable to set it as 180 degreeC-250 degreeC. By doing in this way, in the coating film used for this invention, larger anisotropy is provided.

By doing so, the liquid crystal display device provided by the present invention exhibits high reliability against external stress such as light or heat.

As mentioned above, the transverse electric field drive-type liquid crystal display element board | substrate or the transverse electric field drive-type liquid crystal display element which has this board | substrate manufactured using the polymer of this invention are excellent in reliability, and are large screen and high definition liquid crystal television Etc. can be preferably used. Moreover, since the liquid crystal aligning film manufactured by the method of this invention has the outstanding liquid-crystal orientation stability and reliability, it can be used also for the variable phase group which used liquid crystal, and this variable phase group can vary resonant frequency, for example. It can be used preferably for an antenna.

EXAMPLE

EMBODIMENT OF THE INVENTION Although an Example etc. are given to this invention concretely below, this invention is not limited to these Examples.

In addition, the symbol of a compound and a solvent is as follows.

NMP: N-methyl-2-pyrrolidone

BCS: Butyl Cellosolve

DA-1: compound represented by the following structural formula (DA-1)

DA-2: compound represented by the following structural formula (DA-2)

DA-3: compound represented by the following structural formula (DA-3)

DA-4: compound represented by the following structural formula (DA-4)

DA-5: compound represented by the following structural formula (DA-5)

DA-6: compound represented by the following structural formula (DA-6)

DA-7: compound represented by the following structural formula (DA-7)

DA-8: compound represented by the following structural formula (DA-8)

CA-1: a compound represented by the following structural formula (CA-1)

CA-2: Compound represented by the following structural formula (CA-2)

CA-3: Compound represented by the following structural formula (CA-3)

[Formula 28]

[Formula 29]

<Measurement of viscosity>

In the synthesis example, the viscosity of the polymer solution was measured at a sample amount of 1.1 mL, cone rotor TE-1 (1 ° 34 ', R24) and a temperature of 25 ° C. using an E-type viscometer TVE-22H (manufactured by Torquay Industries, Ltd.). It was.

<Synthesis example 1>

3.91 g (13.0 mmol) of DA-1 were weighed, 25.7 g of NMP was added to a 100 mL four-necked flask equipped with a stirring apparatus and a nitrogen inlet tube, and the mixture was stirred and dissolved while sending nitrogen. 1.76 g (8.97 mmol) addition of CA-1, stirring this diamine solution under water cooling, stirring at 23 degreeC under nitrogen atmosphere for 3 hours, 0.81 g (3.25 mmol) addition of CA-2, and further NMP Was added, and it stirred at 50 degreeC for 20 hours in nitrogen atmosphere, and obtained the solution of polyamic acid. The viscosity in the temperature of 25 degreeC of this solution of polyamic acid was 571 mPa * s.

12.1 g of this polyamic acid was collected into a 100 mL Erlenmeyer flask containing a stirrer, 16.1 g of NMP and 12.1 g of BCS were added, followed by stirring with a magnetic stirrer for 2 hours to form a liquid crystal aligning agent (PAA-1). Got it.

<Synthesis example 2>

To a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 2.79 g (14.0 mmol) of DA-2 and 1.47 g (6.00 mmol) of DA-3 were weighed, 50.5 g of NMP was added, and nitrogen was added. It stirred by sending and dissolved. 5.59 g (19.0 mmol) was added for CA-3, stirring this diamine solution under water cooling, 21.7 g of NMP were further added, and it stirred at 50 degreeC for 20 hours in nitrogen atmosphere, and obtained the solution of polyamic acid. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 480 mPa * s.

The solution of this polyamic acid was aliquoted into 14.5 g of a 100 mL Erlenmeyer flask containing a stirrer, 12.6 g of NMP and 11.6 g of BCS were added, followed by stirring with a magnetic stirrer for 2 hours to form a liquid crystal aligning agent (PAA-2). Got it.

<Synthesis example 3>

To a 100 mL four-necked flask equipped with a stirring apparatus and a nitrogen introduction tube, 1.59 g (8.00 mmol) of DA-2 and 0.40 g (2.00 mmol) of DA-4 were weighed, 24.0 g of NMP was added, and nitrogen was added. It stirred by sending and dissolved. CA-1 was added 1.81g (9.25 mmol), stirring this diamine solution under water cooling, Furthermore, 10.3g of NMP were added, and it stirred at 23 degreeC for 4 hours in nitrogen atmosphere, and obtained the solution of polyamic acid. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 134 mPa * s.

The solution of this polyamic acid was collected 17.7g into a 100 mL Erlenmeyer flask containing a stirrer, 9.83 g of NMP and 11.8 g of BCS were added, followed by stirring with a magnetic stirrer for 2 hours to form a liquid crystal aligning agent (PAA-3). Got it.

<Synthesis example 4>

To a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 1.49 g (7.00 mmol) of DA-5, 0.73 g (3.00 mmol) of DA-3 were weighed, 25.8 g of NMP was added, and nitrogen was added. It stirred by sending and dissolved. While stirring this diamine solution under water cooling, 2.80g (9.50 mmol) was added for CA-3, 11.0g of NMP were further added, and it stirred at 50 degreeC for 20 hours in nitrogen atmosphere, and obtained the solution of polyamic acid. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 432 mPa * s.

The solution of this polyamic acid was collected by 14.7 g into a 100 mL Erlenmeyer flask containing a stirrer, 12.7 g of NMP, and 11.8 g of BCS were added, followed by stirring with a magnetic stirrer for 2 hours to form a liquid crystal aligning agent (PAA-4). Got it.

<Synthesis example 5>

In a 100 mL four-necked flask with a stirrer and nitrogen introduction tube, 0.80 g (4.0 mmol) for DA-2, 0.73 g (3.00 mmol) for DA-3, and 1.18 g (3.00 mmol) for DA-6 Then, 28.3 g of NMP was added, followed by stirring while sending nitrogen to dissolve it. While stirring this diamine solution under water cooling, 2.80g (9.50mmol) was added for CA-3, 12.1g of NMP were further added, and it stirred at 50 degreeC for 20 hours in nitrogen atmosphere, and obtained the solution of polyamic acid. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 512 mPa * s.

The solution of this polyamic acid was collected by 14.5 g in a 100 mL Erlenmeyer flask containing a stirrer, 12.6 g of NMP, and 11.6 g of BCS were added, followed by stirring with a magnetic stirrer for 2 hours to form a liquid crystal aligning agent (PAA-5). Got it.

<Comparative Synthesis Example 1>

In a 100 mL four-necked flask equipped with a stirring apparatus and a nitrogen introduction tube, 3.54 g (13.0 mmol) of DA-7 was weighed, 24.2 g of NMP was added, and dissolved by stirring while sending nitrogen. 1.76 g (8.97 mmol) addition of CA-1, stirring this diamine solution under water cooling, stirring at 23 degreeC under nitrogen atmosphere for 3 hours, 0.81 g (3.25 mmol) addition of CA-2, and further NMP 10.4g was added, and it stirred at 50 degreeC for 20 hours in nitrogen atmosphere, and obtained the solution of polyamic acid. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 627 mPa * s.

11.9 g of this polyamic acid solution was fractionated into a 100 mL Erlenmeyer flask containing a stirrer, 15.9 g of NMP and 11.9 g of BCS were added, followed by stirring with a magnetic stirrer for 2 hours to form a liquid crystal aligning agent (PAA-a). Got it.

<Comparative Synthesis Example 2>

4.27 g (13.0 mmol) of DA-8 were weighed, 27.1 g of NMP was added to a 100 mL four-necked flask equipped with a stirring apparatus and a nitrogen introduction tube, and dissolved by sending nitrogen. 1.76 g (8.97 mmol) addition of CA-1, stirring this diamine solution under water cooling, stirring at 23 degreeC under nitrogen atmosphere for 3 hours, 0.81 g (3.25 mmol) addition of CA-2, and further NMP 11.6g was added, and it stirred at 50 degreeC for 20 hours in nitrogen atmosphere, and obtained the solution of polyamic acid. The viscosity in the temperature of 25 degreeC of the solution of this polyamic acid was 483 mPa * s.

12.2 g of this polyamic acid solution was aliquoted into a 100 mL Erlenmeyer flask containing a stirrer, 16.3 g of NMP and 12.2 g of BCS were added, followed by stirring with a magnetic stirrer for 2 hours, thereby providing a liquid crystal aligning agent (PAA-b). Got it.

<Example 1>

In a 50 mL Erlenmeyer flask containing a stirrer, 4.03 g of the polyimide solution (PAA-1) obtained in Synthesis Example 1 and 6.05 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2 were weighed, and a magnetic stirrer was used. It stirred for 2 hours and obtained the liquid crystal aligning agent (A-1).

<Example 2>

In a 50 mL Erlenmeyer flask containing a stirrer, 4.01 g of the polyimide solution (PAA-1) obtained in Synthesis Example 1 and 6.02 g of the polyamic acid solution (PAA-3) obtained in Synthesis Example 3 were weighed, and a magnetic stirrer was used. It stirred for 2 hours and obtained the liquid crystal aligning agent (A-2).

<Example 3>

In a 50 mL Erlenmeyer flask containing a stirrer, 4.04 g of the polyimide solution (PAA-1) obtained in Synthesis Example 1 and 6.07 g of the polyamic acid solution (PAA-4) obtained in Synthesis Example 4 were weighed, and a magnetic stirrer was used. It stirred for 2 hours and obtained the liquid crystal aligning agent (A-3).

<Example 4>

In a 50 mL Erlenmeyer flask containing a stirrer, 4.03 g of the solution of polyimide obtained in Synthesis Example 1 (PAA-1) and 6.04 g of the polyamic acid solution (PAA-5) obtained in Synthesis Example 5 were weighed, and a magnetic stirrer was used. It stirred for 2 hours and obtained the liquid crystal aligning agent (A-4).

<Comparative Example 1>

The solution (PAA-1) of the polyimide obtained by the synthesis example 1 was used as the liquid crystal aligning agent (B-1).

<Comparative Example 2>

In a 50 mL Erlenmeyer flask containing a stirrer, 4.03 g of the solution of polyimide (PAA-a) obtained in Comparative Synthesis Example 1 and 6.05 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2 were weighed, and a magnetic stirrer was used. It stirred for 2 hours, and obtained the liquid crystal aligning agent (B-2).

<Comparative Example 3>

In a 50 mL Erlenmeyer flask containing a stirrer, 4.00 g of a solution of polyimide (PAA-b) obtained in Comparative Synthesis Example 2 and 6.00 g of a polyamic acid solution (PAA-2) obtained in Synthesis Example 2 were weighed, and a magnetic stirrer was used. It stirred for 2 hours, and obtained the liquid crystal aligning agent (B-3).

<Production of Liquid Crystal Cell for Liquid Crystal Orientation and Relaxation Characteristics Evaluation of Accumulated Charge>

Below, the manufacturing method of the liquid crystal cell for evaluating liquid crystal alignability and the relaxation characteristic of accumulation charge is shown.

The liquid crystal cell provided with the structure of the liquid crystal display element of an FFS system was produced. Initially, the board | substrate with an electrode was prepared. The substrate is a glass substrate having a size of 30 mm × 35 mm and a thickness of 0.7 mm. On the board | substrate, the IZO electrode which comprises a counter electrode as a 1st layer was formed in the whole surface. On the counter electrode of 1st layer, the SiN (silicon nitride) film | membrane formed into a film by CVD method was formed as 2nd layer. The film thickness of the SiN film of 2nd layer is 500 nm, and functions as an interlayer insulation film. On the SiN film of a 2nd layer, the comb-tooth shaped pixel electrode formed by patterning an IZO film was arrange | positioned as a 3rd layer, and two pixels of a 1st pixel and a 2nd pixel were formed. Each pixel has a size of 10 mm in length and 5 mm in width. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer.

The pixel electrode of the 3rd layer has the comb-tooth shaped shape comprised by putting in multiple arrangement | array | sequence the "<"-shaped electrode element in which the center part was bent similarly to the figure described in Unexamined-Japanese-Patent No. 2014-77845 (Japanese Unexamined Patent Publication). The width | variety of the width direction of each electrode element is 3 micrometers, and the space | interval between electrode elements is 6 micrometers. Since the pixel electrode which forms each pixel was comprised by arranging a plurality of "<"-shaped electrode elements in which the center part was bent, the shape of each pixel is not rectangular but is boldly curved in the center part like an electrode element. It is equipped with a shape similar to 자. Each pixel is divided up and down on the center of the bent portion, and has a first region that is the upper side of the bent portion and a second region that is the lower side.

When the 1st area | region and 2nd area | region of each pixel are compared, the formation direction of the electrode element of the pixel electrode which comprises them differs. That is, in the case where the polarization plane of the polarized ultraviolet light, which will be described later, is based on the direction of the line segment projected on the substrate, in the first region of the pixel, the electrode element of the pixel electrode is formed to form an angle of + 10 ° (clockwise), In the second region of, the electrode elements of the pixel electrode were formed to form an angle of -10 ° (clockwise). That is, in the 1st area | region and 2nd area | region of each pixel, it is comprised so that the direction of rotation operation (in-plane switching) in liquid crystal surface caused by voltage application between a pixel electrode and a counter electrode may be reversed mutually. It was.

Next, after filtering the liquid crystal aligning agent obtained in Examples 1-4 and Comparative Examples 1-3 with a 1.0 micrometer filter, it applied to the prepared said board | substrate with an electrode by spin coating. Then, it dried for 90 second on the hotplate set to 70 degreeC. Subsequently, Ushio Electric Co., Ltd. exposure apparatus: APL-L050121S1S-APW01 was used, and the linearly polarized light of the ultraviolet-ray was irradiated from the perpendicular direction with respect to the board | substrate through a wavelength selective filter and a polarizing plate. At this time, the polarization plane direction was set so that the direction of the line segment which projected the polarization plane of polarized ultraviolet-ray to the board | substrate became the direction which inclined 10 degrees with respect to the 3rd layer IZO comb electrode. Subsequently, baking was performed for 30 minutes with the IR (infrared) type oven set to 230 degreeC, and the board | substrate with a polyimide liquid crystal aligning film of 100 nm of film thickness in which the orientation process was performed was obtained. Moreover, the board | substrate with a polyimide liquid crystal aligning film in which the orientation process was performed similarly to the above was obtained also to the glass substrate which has a columnar spacer of 4 micrometers in height in which the ITO electrode is formed in the back surface as an opposing board | substrate. The board | substrate with these two liquid crystal aligning films was made into one set, the sealing compound was printed in the form which left the liquid crystal injection hole on the one side board | substrate, the other one board | substrate faces the liquid crystal aligning film surface, and the polarizing surface of polarized ultraviolet light is board | substrate. The line segments projected onto the substrate were bonded to each other so that the directions of the line segments were parallel to each other, and they were pressed. Thereafter, the sealing agent was cured to prepare an empty cell having a cell gap of 4 µm. Liquid crystal MLC-7026-100 (Negative liquid crystal by Merck Corporation) was injected into this empty cell, the injection port was sealed, and the liquid crystal cell of the FFS system was obtained. Then, the obtained liquid crystal cell was heated at 120 degreeC for 30 minutes, and left to stand at 23 degreeC overnight, and was used for evaluation of the liquid crystal alignability and the relaxation characteristic of accumulated charge.

<Evaluation of Liquid Crystal Orientation>

Using the said liquid crystal cell, the alternating voltage of 16 VPP was applied for 96 hours at the frequency of 30 Hz in 70 degreeC constant temperature environment. Then, it was made to short-circuit between the pixel electrode and the counter electrode of a liquid crystal cell, and it was left to stand at 23 degreeC overnight.

After standing, the liquid crystal cell was provided between two polarizing plates arranged so that the polarization axes were orthogonal, the backlight was turned on in the absence of voltage, and the arrangement angle of the liquid crystal cell was adjusted so that the luminance of transmitted light was the smallest. The rotation angle when the liquid crystal cell was rotated from the darkest angle of the second region of the first pixel to the darkest angle of the first region was calculated as the angle Δ. Similarly, the second pixel was compared with the second region to calculate the same angle Δ. And the average value of the angle (DELTA) value of a 1st pixel and a 2nd pixel was computed as angle (DELTA) of a liquid crystal cell. When the value of angle (DELTA) of this liquid crystal cell was less than 1.0 degree, it defined as "good" and when the value of angle (DELTA) was 1.0 degrees or more, it defined and evaluated as "poor."

<Evaluation of relaxation characteristics of accumulated charge>

The liquid crystal cell is provided between two polarizing plates arranged so that the polarization axes are orthogonal, and the LED backlight is irradiated from below the two polarizing plates while the pixel electrode and the counter electrode are shorted to the same potential. The angle of the liquid crystal cell was adjusted so that the brightness of the LED backlight transmitted light to be measured may be minimum.

Next, while applying the square wave of frequency 30Hz to this liquid crystal cell, the V-T characteristic (voltage-transmittance characteristic) under the temperature of 23 degreeC was measured, and the alternating voltage whose relative transmittance becomes 23% was computed. Since this AC voltage corresponds to a region where the change in luminance with respect to the voltage is large, it is good for evaluating the accumulated charge through the luminance.

Next, after applying the square wave of frequency 30Hz for 5 minutes at the alternating voltage whose relative transmittance becomes 23% under the temperature of 23 degreeC, it was driven for 30 minutes, superimposing the DC voltage of + 1.0V. Thereafter, the DC voltage was cut off, and only a square wave having a frequency of 30 Hz was further applied for 30 minutes at an AC voltage at which the relative transmittance became 23%.

The faster the relaxation of the accumulated charge is, the faster the charge is accumulated in the liquid crystal cell when the DC voltages are superimposed, so that the relaxation characteristics of the accumulated charges are from a state in which the relative transmittance immediately after the DC voltages are 30% or more. It evaluated by what extent the relative transmittance | permeability after 30 minutes fell. That is, when the relative transmittance | permeability after 30 minutes of DC voltage superimposition fell to less than 28%, it evaluated as "good | favorableness" and when the relative transmittance | permeability was 28% or more.

<Production of Liquid Crystal Cell for Voltage Retention Rate Evaluation>

Of the liquid crystal cell for evaluation of the liquid crystal alignment and relaxation characteristics of the accumulated charge, except that 4 μm of beads spacers were scattered on the liquid crystal alignment film surface on the one-side substrate before printing of the sealing agent by using the glass substrate on which the ITO electrode was formed. In the same procedure as the preparation, a liquid crystal cell for measuring the voltage retention was produced.

<Evaluation of Voltage Retention Rate>

The voltage retention was evaluated using the said liquid crystal cell. Specifically, an AC voltage of 2 VPP is applied to the liquid crystal cell obtained by the above method at a temperature of 70 ° C. for 60 μsec, the voltage after 167 milliseconds is measured, and how much the voltage is maintained is determined by the voltage retention rate ( Also referred to as VHR). In addition, the measurement used the voltage retention measuring apparatus (VHR-1, the Toyo Technica Co., Ltd.), Voltage: ± 1V, Pulse Width: 60 microseconds, Flame Period: 167 It carried out by setting of ms. When the value of the voltage retention of this liquid crystal cell was 95% or more, it defined as "good" and when the value of the voltage retention was less than 95%, it defined and evaluated as "poor."

<Example 5>

Two types of liquid crystal cells were produced as above-mentioned using the liquid crystal aligning agent (A-1) obtained in Example 1. Irradiation of polarized ultraviolet-ray was performed using the high pressure mercury lamp through the wavelength selective filter: 240 LCF, and the 254 nm type polarizing plate. The irradiation amount of a polarized ultraviolet-ray measures the amount of light using the Ushio Electric Co., Ltd. illuminometer UVD-S254SB, and changes it in the range of 600-1800 mJ / cm <2> in wavelength 254 nm, respectively, and implements three different from each other. The above liquid crystal cell was produced.

As a result of evaluating liquid crystal orientation about these liquid crystal cells, the polarized ultraviolet irradiation amount whose angle (DELTA) was the best was 1500 mJ / cm <2>, and angle (DELTA) was 0.56 degrees and was favorable.

Moreover, the relative transmittance | permeability after 30 minutes of direct current voltage superimposition was favorable for the relaxation characteristic of the accumulated electric charge of the same polarized ultraviolet irradiation amount evaluated previously before liquid crystal aligning property.

Moreover, as a result of evaluating voltage retention about the liquid crystal cell produced by the same amount of polarized ultraviolet irradiation, the voltage retention was 96.8% and was favorable.

<Examples 6 to 8>

Except having used the liquid crystal aligning agent obtained in Examples 2-4, the liquid crystal aligning property, the relaxation characteristic of accumulated charge, and voltage retention were evaluated by the method similar to Example 5.

<Comparative Examples 4-6>

Except having used the liquid crystal aligning agent obtained by Comparative Examples 1-3, the liquid crystal aligning property, the relaxation characteristic of accumulated charge, and voltage retention were evaluated by the method similar to Example 5.

In Table 1, as a result of evaluation of the polarized-ultraviolet-ray irradiation amount which the angle (DELTA) was the best when using the liquid crystal aligning agent obtained by Examples 1-4 and Comparative Examples 1-3, the evaluation of liquid crystal alignability, The results and the results of the evaluation of the voltage retention are shown.

As shown in Table 1, in Examples 5-8, the angle (DELTA) which is a difference of the orientation azimuth angle before and behind AC drive is favorable to less than 1.0 degree, and the relative transmittance | permeability 30 minutes after the DC voltage superposition which shows the relaxation characteristic of accumulated charge is good. Silver is good at less than 28.0%, the voltage retention is also good at 95% or more, and is excellent in the display quality of the liquid crystal display device in that all are good afterimage characteristics. On the other hand, in Comparative Examples 4-6, neither the angle (DELTA), the relative transmittance | permeability 30 minutes after DC voltage superimposition, and voltage retention were all the favorable results.

Thus, it was confirmed that the liquid crystal display element manufactured by the method of this invention shows the outstanding afterimage characteristic.

Industrial availability

The transverse electric field drive type liquid crystal display element substrate manufactured using the composition of this invention or the transverse electric field drive type liquid crystal display element which has this board | substrate becomes excellent in reliability, and can be used suitably for a large screen high definition liquid crystal television etc. have. Moreover, since the liquid crystal aligning film manufactured by the method of this invention has the outstanding liquid-crystal orientation stability and reliability, it can be used also for the variable phase group which used liquid crystal, and this variable phase group can vary resonant frequency, for example. It can be used preferably for an antenna.

Claims (7)

At least one kind of polymer (A) selected from the polyamic acid obtained by using the tetracarboxylic dianhydride component and the diamine component containing the diamine represented by following formula (1), and the imidation polymer of this polyamic acid, and
At least one kind of polymer (B) chosen from the polyamic acid obtained by using the tetracarboxylic dianhydride component and the diamine component containing the diamine represented by following formula (2), and the imidation polymer of this polyamic acid.
It contains, a liquid crystal aligning agent.

Formula (1), X is - (CH ₂₎ represents an n-, n is - (CH ₂₎ - is a natural number representing the number of 8 or 9, any - (CH ₂₎ - are, each independently, Groups selected from -O-, -S-, -COO-, -OCO-, -CONH- and -NHCO-, these groups may be substituted on condition that they are not adjacent to each other, and R ₁ and R ₂ are each independently It is a monovalent organic group, and p1 and p2 are the integers of 0-4 each independently.
In formula (2), Y <_1> is a divalent organic group which has at least 1 sort (s) of structure chosen from the group which consists of an amino group, an imino group, and a nitrogen-containing heterocyclic ring, B <_1> , B <_2> are respectively independently a hydrogen atom, Or a C1-C10 alkyl group, alkenyl group, and alkynyl group which may have a substituent. The method of claim 1,
Y ₁ in Formula (2) is at least 1 sort (s) chosen from the structure of following formula (YD-1)-(YD-5), The liquid crystal aligning agent.

(In formula (YD-1), A <_1> is a C3-C15 nitrogen atom containing heterocyclic ring, and Z <_1> is a C1-C20 hydrocarbon group which may have a hydrogen atom or a substituent. In -2), W ₁ is a hydrocarbon group of 1 to 10 carbon atoms, and A ₂ is a divalent group substituted with a C 3 to C 15 monovalent organic group having a nitrogen atom-containing heterocyclic ring or an aliphatic group having 1 to 6 carbon atoms. In Formula (YD-3), W ₂ is a divalent organic group having 6 to 15 carbon atoms and having 1 to 2 benzene rings, and W ₃ is alkylene or biphenyl having 2 to 5 carbon atoms. is alkylene or a carbon number of 12 to 18 divalent organic group that includes a heterocyclic ring containing a nitrogen atom, Z ₂ is an alkyl group, or a benzene ring of the hydrogen atoms, having a carbon number of 1 ~ 5, a is an integer from 0 to 1. expression ( In YD-4), A ₃ is a nitrogen atom-containing hetero ring having 3 to 15 carbon atoms. In A <_4> , A <_4> is a C3-C15 nitrogen atom containing heterocyclic ring, W <_5> is C2-C5 alkylene). The method according to claim 1 or 2,
A ₁ , A ₂ , A ₃ , and A ₄ described in formulas (YD-1), (YD-2), (YD-4), and (YD-5) are pyrrolidine, pyrrole, imidazole, A liquid crystal aligning agent, which is at least one kind selected from the group consisting of pyrazole, oxazole, thiazole, piperidine, piperazine, pyridine, pyrazine, indole, benzoimidazole, quinoline, isoquinoline, and carbazole. The method according to any one of claims 1 to 3,
Y ₁ in Formula (2) is at least 1 sort (s) chosen from the group which consists of a divalent organic group which has a structure of following formula (YD-6)-(YD-22).

(H is an integer of 1-3 in a formula (YD-17), and j is an integer of 0-3 in a formula (YD-14) and (YD-21) and (YD-22)). The method according to any one of claims 1 to 4,
Y ₁ in formula (2) is at least selected from the group consisting of divalent organic groups having the structures of the formulas (YD-14), (YD-18), (YD-21) and (YD-22). It is one kind, Liquid crystal aligning agent. The liquid crystal aligning film obtained using the liquid crystal aligning agent in any one of Claims 1-5. The liquid crystal display element which comprises the liquid crystal aligning film of Claim 6.