JP5761183B2 - LIQUID CRYSTAL ALIGNING AGENT CONTAINING THERMALLEELABLE GROUP-CONTAINING COMPOUND, AND LIQUID CRYSTAL Alignment Film - Google Patents

Description

  The present invention has high mechanical strength, excellent resistance to rubbing treatment, liquid crystal orientation, particularly excellent electrical characteristics such as voltage holding ratio and ion density at high temperature, and a reliability that provides a high pretilt angle. The present invention relates to a liquid crystal aligning agent that can form a liquid crystal aligning film having high properties, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display element.

  A liquid crystal display element used in a liquid crystal television, a liquid crystal display, or the like is usually provided with a liquid crystal alignment film for controlling the alignment state of liquid crystals. Conventionally, as the liquid crystal alignment film, a polyimide-based liquid crystal alignment film obtained by applying a liquid crystal alignment agent mainly composed of a polyimide precursor such as polyamic acid (polyamic acid) or a solution of soluble polyimide to a glass substrate or the like and baking it is mainly used. It is used.

  As liquid crystal display elements have become higher in definition, liquid crystal alignment films have high liquid crystal alignment characteristics and stable pretilt angles in addition to the demands for suppressing the decrease in contrast and reducing the afterimage phenomenon. Characteristics such as a voltage holding ratio, suppression of an afterimage generated by AC driving, a small residual charge when a DC voltage is applied, and / or an early relaxation of a residual charge accumulated by a DC voltage are becoming increasingly important.

  Various proposals have been made for polyimide-based liquid crystal aligning agents in order to meet the above requirements. For example, in addition to polyamic acid and imide group-containing polyamic acid, a liquid crystal aligning agent containing a tertiary amine having a specific structure (see Patent Document 1), a soluble polyimide using a specific diamine compound having a pyridine skeleton as a raw material A liquid crystal aligning agent (see Patent Document 2) has been proposed.

  Further, in addition to polyamic acid and its imidized polymer, etc., a compound containing one carboxylic acid group in the molecule, a compound containing one carboxylic anhydride group in the molecule, and 1 in the molecule A liquid crystal aligning agent containing a very small amount of a compound selected from compounds containing three tertiary amino groups (see Patent Document 3), a tetracarboxylic dianhydride having a specific structure and a tetracarboxylic dianhydride having cyclobutane A liquid crystal aligning agent containing a polyamic acid obtained from the diamine compound or an imidized polymer thereof (see Patent Document 4) is known.

  Further, at least selected from a liquid crystal aligning agent (see Patent Document 5) containing an imide group-containing monomer having a specific structure or an amic acid site-containing monomer, together with polyamic acid or polyimide, polyamic acid and an imidized polymer of polyamic acid. A liquid crystal aligning agent (see Patent Document 6) containing one kind of polymer and at least one compound selected from an amic acid compound and an imide compound has been proposed.

JP 9-316200 A JP-A-10-104633 JP-A-8-76128 JP 9-138414 A JP-A-6-110061 JP-A-9-269491

  However, in recent years, LCD TVs with larger screens and high-definition have become the main, and the demand for liquid crystal display elements has become more stringent, and even for liquid crystal alignment films that are closely related to the characteristics of liquid crystal display elements. Excellent high-reliability characteristics are required, and even higher characteristics are required. Not only the initial characteristics are good, but also high reliability that maintains good characteristics even after long-term exposure to high temperatures. Sex is required.

  The present invention provides a liquid crystal alignment film having a large mechanical strength, excellent resistance to rubbing treatment, and excellent liquid crystal alignment properties, particularly electrical characteristics such as voltage holding ratio and ion density at high temperatures, An object of the present invention is to provide a liquid crystal aligning agent capable of forming a highly reliable liquid crystal aligning film that gives a high pretilt angle.

  The present inventor has intensively studied to achieve the above object, and as a result, a polyimide precursor obtained by reacting a diamine compound and a tetracarboxylic acid derivative, which are components of a conventional liquid crystal aligning agent, and / or Or a compound having an amino group protected by a heat-releasable group that replaces hydrogen by heating and having an amic acid or an amic acid ester structure (hereinafter referred to as “thermal desorption”). It was also found that the above-mentioned object can be achieved by a liquid crystal aligning agent containing a release group-containing compound.

  A compound having an amino group protected by a heat-releasable group that replaces hydrogen by heating added to the liquid crystal aligning agent and having an amic acid or amic acid ester structure (hereinafter referred to as a heat-releasable group-containing compound) Is a novel compound not yet published in the literature before the filing of the present application, but when such a heat-releasable group-containing compound is added to the liquid crystal aligning agent, the film has high mechanical strength and resistance to rubbing treatment. It was found that a liquid crystal alignment film having excellent reliability and excellent electrical properties such as liquid crystal alignment properties, in particular, voltage holding ratio and ion density at high temperatures, and giving a high pretilt angle can be formed. .

（式中、Ｘは４価の有機基であり、Ｒ _１ は水素原子、又は炭素数１〜５のアルキル基であり、Ｚは下記式（２）で表される構造である。）

（式中、Ｚ _１ は単結合、又は炭素数１〜３０の２価の有機基である。Ｒ _２ 及びＲ _３ は、それぞれ独立して水素原子、又は置換基を有してもよい炭素数１〜３０のアルキル基、アルケニル基、アルキニル基、アリール基若しくはそれらの組み合わせであり、環構造を形成してもよい。Ｒ _４ は水素原子又は置換基を有してもよい炭素数１〜３０のアルキル基である。Ｄ _１ は熱脱離性基である。）
２．前記ポリイミド前駆体が、下記の式（７）で表わされる繰り返し単位を有する上記１に記載の液晶配向剤。 Thus, the present invention has the following gist.
1. Protected by a polyimide precursor obtained by reacting a diamine compound and a tetracarboxylic acid derivative, and / or a polyimide imidized with the polyimide precursor, and a thermally desorbable group that replaces hydrogen by heating at 80 to 300 ° C. liquid crystal aligning agent characterized by containing a compound you express the following formula (1) having an amic acid or amic acid ester structure having an amino group.

(In the formula, X is a tetravalent organic group, R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Z is a structure represented by the following formula (2).)

(In the formula, Z ₁ is a single bond or a divalent organic group having 1 to 30 carbon atoms. R ₂ and R ₃ are each independently a hydrogen atom or a carbon number that may have a substituent. 1 to 30 alkyl groups, alkenyl groups, alkynyl groups, aryl groups, or combinations thereof, which may form a ring structure, and R ₄ may have a hydrogen atom or a substituent and may have 1 to 30 carbon atoms. D ₁ is a thermally leaving group.)
2. 2. The liquid crystal aligning agent according to 1 above, wherein the polyimide precursor has a repeating unit represented by the following formula (7).

（式中Ｘ_１は４価の有機基であり、Ｙ_１は２価の有機基であり、Ｒ_６は、水素原子又は炭素数１〜５のアルキル基である。Ａ_１及びＡ_２はそれぞれ独立して水素原子、又は置換基を有してもよい炭素数１〜１０のアルキル基、アルケニル基若しくはアルキニル基である。）
３．前記ポリイミド前駆体及び前記ポリイミドが、それらの合計量で液晶配向剤中０．５〜１５質量％含有され、加熱により水素に置き換わる熱脱離性基により保護されたアミノ基を有するアミック酸若しくはアミック酸エステル構造を有する式（１）で表される化合物が、上記式（７）で表される繰り返し単位を有するポリイミド前駆体及び該ポリイミド前駆体のイミド化重合体の繰り返し単位１ユニットに対して、０．５〜５０モル％含有される上記２に記載の液晶配向剤。

(Wherein X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, and R ₆ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A ₁ and A ₂ are respectively Independently a hydrogen atom or an optionally substituted alkyl group, alkenyl group or alkynyl group having 1 to 10 carbon atoms.
3. The polyimide precursor and the polyimide are contained in a total amount of 0.5 to 15% by mass in the liquid crystal aligning agent, and an amic acid or an amic acid having an amino group protected by a thermally desorbable group that replaces hydrogen by heating. The compound represented by the formula (1) having an acid ester structure is a polyimide precursor having a repeating unit represented by the above formula (7) and 1 unit of a repeating unit of an imidized polymer of the polyimide precursor. the liquid crystal aligning agent according to above SL 2 contained 0.5 to 50 mol%.

4 . 4. The liquid crystal aligning agent according to any one of 1 to 3 above, wherein the thermally leaving group is a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group.
5 . The liquid crystal aligning agent in any one of said 1-4 whose said X is either selected from the group which consists of a structure represented by a following formula.

６．上記１〜５のいずれかに記載の液晶配向剤を塗布、焼成して得られる膜を配向処理した液晶配向膜。
７．前記配向処理が、ラビング処理、又は偏光された放射線の照射処理である上記６に記載の液晶配向膜。
８．上記６又は７に記載の液晶配向膜を具備する液晶表示素子。
９．下記式（１）で表されるアミック酸若しくはアミック酸エステル構造を有する化合物。

6 . 6. A liquid crystal alignment film obtained by aligning a film obtained by applying and baking the liquid crystal aligning agent according to any one of 1 to 5 above.
7 . 7. The liquid crystal alignment film according to 6 above, wherein the alignment treatment is rubbing treatment or irradiation treatment with polarized radiation.
8 . 8. A liquid crystal display device comprising the liquid crystal alignment film as described in 6 or 7 above.
9 . The compound which has an amic acid or an amic acid ester structure represented by following formula (1).

（式中、Ｘは４価の有機基、Ｒ_１は水素原子、又は炭素数１〜５のアルキル基であり、Ｚは下記式（２）で表される構造である。）

(In the formula, X is a tetravalent organic group, R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Z is a structure represented by the following formula (2).)

（式中、Ｚ_１は単結合、又は炭素数１〜３０の２価の有機基である。Ｒ_２及びＲ_３は、それぞれ独立して水素原子、又は置換基を有してもよい炭素数１〜３０のアルキル基、アルケニル基、アルキニル基、アリール基若しくはそれらの組み合わせであり、環構造を形成してもよい。Ｒ_４は水素原子又は置換基を有してもよい炭素数１〜３０のアルキル基である。Ｄ_１は熱脱離性基である。）
１０．下記式（３）で表されるビスクロロカルボニル化合物と下記式（４）で表されるモノアミン化合物とを塩基の存在下に、（ビスクロロカルボニル化合物／モノアミン化合物）のモル比が１／２〜１／３で反応させて得られる上記９に記載の化合物。

(In the formula, Z ₁ is a single bond or a divalent organic group having 1 to 30 carbon atoms. R ₂ and R ₃ are each independently a hydrogen atom or a carbon number that may have a substituent. 1 to 30 alkyl groups, alkenyl groups, alkynyl groups, aryl groups, or combinations thereof, which may form a ring structure, and R ₄ may have a hydrogen atom or a substituent and may have 1 to 30 carbon atoms. D ₁ is a thermally leaving group.)
10 . In the presence of a base , a bischlorocarbonyl compound represented by the following formula (3) and a monoamine compound represented by the following formula (4) have a molar ratio of ( bischlorocarbonyl compound / monoamine compound ) of 1/2 to 10. The compound according to 9 above, obtained by reacting at 1/3.

（式中、Ｘ、Ｚ_１、Ｒ_２、Ｒ_３、Ｒ_４、及びＤ_１は前記式（１）及び（２）における定義と同じであり、Ｒ_５は炭素数１〜５のアルキル基である。）
１１．下記式（５）で表されるテトラカルボン酸誘導体と上記式（４）で表されるモノアミン化合物とを縮合剤の存在下に、（テトラカルボン酸誘導体／モノアミン化合物）のモル比が１／２〜１／３で反応させて得られる上記９に記載の化合物。

_{(Wherein, X, Z 1, R 2} , R 3, R 4, and _{D 1} are as defined in previous following formula (1) and (2), _{R 5} represents an alkyl group having 1 to 5 carbon atoms .)
11 . A tetracarboxylic acid derivative represented by the following formula (5) and a monoamine compound represented by the above formula (4) in the presence of a condensing agent have a molar ratio of (tetracarboxylic acid derivative / monoamine compound ) of 1/2. 10. The compound according to 9 above, obtained by reacting at １ ／.

（式中、Ｘ及びＲ_５は上記式（１）及び（３）における定義と同じである。）
１２．下記式（６）で表されるテトラカルボン酸二無水物と上記式（４）で表されるモノアミン化合物を（テトラカルボン酸二無水物／モノアミン化合物）のモル比が１／２〜１／３で反応させて得られる上記９に記載の化合物。

(Wherein, X and _{R 5} are the same as defined in the formula (1) or (3).)
12 . The molar ratio of the tetracarboxylic dianhydride represented by the following formula (6) and the monoamine compound represented by the above formula (4) to (tetracarboxylic dianhydride / monoamine compound ) is 1/2 to 1/3. 10. The compound according to 9 above, obtained by reacting with

（式中、Ｘは上記式（１）における定義と同じである。）
１３．上記式（６）で表されるテトラカルボン酸二水物と上記式（４）で表されるモノアミン化合物とを（テトラカルボン酸二無水物／モノアミン化合物）のモル比が１／２〜１／３で反応させて、さらにエステル化剤でカルボキシル基をエステル化することで得られる上記９に記載の化合物。
１４．上記Ｘが、下記式で表される構造からなる群から選ばれるいずれかである上記９〜１３のいずれかに記載の化合物。

(In the formula, X has the same definition as in the above formula (1).)
13 . The tetracarboxylic acid dihydrate represented by the above formula (6) and the monoamine compound represented by the above formula (4) have a molar ratio of (tetracarboxylic dianhydride / monoamine compound ) of 1/2 to 1 / The compound of said 9 obtained by making it react by 3 and also esterifying a carboxyl group with an esterifying agent further.
14 . 14. The compound according to any one of 9 to 13 , wherein X is any selected from the group consisting of structures represented by the following formulae.

１５．上記Ｒ_１が炭素数１〜５のアルキル基である上記９〜１４のいずれかに記載の化合物。

15 . 15. The compound according to any one of 9 to 14 above, wherein R ₁ is an alkyl group having 1 to 5 carbon atoms.

  According to the present invention, the obtained liquid crystal alignment film has high mechanical strength, excellent resistance to rubbing treatment, and excellent liquid crystal alignment properties, in particular, electrical characteristics such as voltage holding ratio and ion density at high temperatures, In addition, a liquid crystal alignment agent capable of forming a highly reliable liquid crystal alignment film giving a high pretilt angle is provided.

  The liquid crystal aligning agent of the present invention can form a liquid crystal aligning film having the above-mentioned excellent characteristics, and is excellent in long-term storage stability when stored before using the liquid crystal aligning agent.

  Further, a compound having an amino group protected by a thermally desorbable group contained in the liquid crystal aligning agent of the present invention and having an amic acid or an amic acid ester structure is a novel compound, and such a novel compound is also provided. Is done.

  The mechanism of why the liquid crystal aligning agent of the present invention has excellent characteristics as described above is not necessarily clear, but is estimated as follows.

  The thermally desorbable group-containing compound contained in the liquid crystal aligning agent of the present invention has a heat desorbing property at a temperature during the firing process when the liquid crystal aligning agent is applied to the substrate surface and baked to form a liquid crystal alignment film. The group is decomposed and a highly reactive primary or secondary amine is generated. The generated primary or secondary amine accelerates the imidization reaction of the polyimide precursor and / or the polymer of the polyimide, which is the main component contained in the liquid crystal aligning agent, and brings about a high imidization ratio. This causes a cross-linking reaction and gives a large mechanical strength to the liquid crystal alignment film obtained from the liquid crystal alignment agent. The increase in mechanical strength results in improved rubbing resistance and stability of liquid crystal characteristics at high temperatures.

In addition, the thermally detachable group-containing compound has the same amic acid or amic acid ester structure as the polyimide precursor and / or polyimide polymer, which is the main component contained in the liquid crystal aligning agent, When this is added to the liquid crystal aligning agent, the liquid crystal alignment is improved rather than inhibiting the liquid crystal alignment, and as a result, the liquid crystal characteristics such as voltage holding ratio, ion density, and pretilt angle are improved.
Furthermore, since the thermally detachable group-containing compound does not decompose until a high temperature is applied, it has no adverse effect on the storage stability of the liquid crystal aligning agent containing the compound. Never give.

  According to the present invention, the obtained liquid crystal alignment film has high mechanical strength, excellent resistance to rubbing treatment, and excellent liquid crystal alignment properties, in particular, electrical characteristics such as voltage holding ratio and ion density at high temperatures, In addition, a liquid crystal alignment agent capable of forming a highly reliable liquid crystal alignment film giving a high pretilt angle is provided.

<Heat-leaving group-containing compound>
The thermally detachable group-containing compound added to the liquid crystal aligning agent in the present invention is a compound having an amino group protected by a thermally detachable group and having an amic acid or an amic acid ester structure, In the case of a temperature of 80 to 300 ° C., preferably 100 to 250 ° C., particularly preferably 150 to 230 ° C., the thermally desorbable group is decomposed and replaced with a hydrogen atom. For this reason, a liquid crystal aligning agent is apply | coated to the board | substrate of a liquid crystal display element, and a thermally detachable group will detach | leave at 150-300 degreeC which is normal temperature at the time of baking, and will be substituted by hydrogen.

  The heat-leaving group-containing compound used in the present invention is preferably represented by the following general formula (1).

式中、Ｘは4価の有機基であり、Ｒ_１は水素原子、又は炭素数１〜５のアルキル基であり、Ｚは下記式（２）で表される構造である。

In the formula, X is a tetravalent organic group, R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Z is a structure represented by the following formula (2).

式中、Ｚ_１は単結合、又は炭素数１〜３０の２価の有機基であり、Ｒ_２及びＲ_３は、それぞれ独立して水素原子、又は置換基を有してもよい炭素数１〜３０のアルキル基、アルケニル基、アルキニル基、アリール基、又はそれらの組み合わせであり、環構造を形成してもよく、Ｒ_４は水素原子又は置換基を有してもよい炭素数１〜３０のアルキル基であり、Ｄ_１は加熱により、水素原子に置き換わるアミノ基の保護基である。
上記式（１）において、Ｒ₁は、水素原子、又は炭素数１〜５アルキル基である。Ｒ_１が嵩高い構造である場合、液晶配向膜として用いた場合に、液晶の配向を阻害する可能性があるため、Ｒ₁としては、水素原子、メチル基、又はエチル基がより好ましく、水素原子又はメチル基が特に好ましい。

In the formula, Z ₁ is a single bond or a divalent organic group having 1 to 30 carbon atoms, and R ₂ and R ₃ are each independently a hydrogen atom or a carbon number of 1 that may have a substituent. -30 alkyl group, alkenyl group, alkynyl group, aryl group, or a combination thereof, may form a ring structure, and R ₄ may have a hydrogen atom or a substituent having 1 to 30 carbon atoms. And D ₁ is an amino-protecting group that replaces a hydrogen atom by heating.
In the above formula (1), R ₁ is a hydrogen atom, or a number from 1 to 5 alkyl group carbon atoms. When R ₁ has a bulky structure, when used as a liquid crystal alignment film, there is a possibility that the alignment of the liquid crystal may be inhibited. Therefore, R ₁ is more preferably a hydrogen atom, a methyl group, or an ethyl group, An atom or a methyl group is particularly preferred.

  In the above formula (1), X is a tetravalent organic group, and its structure is not particularly limited. If the specific example of X is shown, X-1 to X-46 shown below will be mentioned. Among them, X-1, X-2, X-3, X-4, X-5, X-6, X-8, X-16, X-19, X-21, X-25, X-26 X-27, X-28 or X-32 is preferred.

上記式（２）において、Ｒ_２及びＲ_３は、それぞれ独立して水素原子、又は置換基を有してもよい炭素数１〜３０のアルキル基、アルケニル基、アルキニル基、アリール基、又はそれらの組み合わせであり、環構造を形成してもよい。

In the above formula (2), R ₂ and R ₃ are each independently a hydrogen atom, or an optionally substituted alkyl group having 1 to 30 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, or these And may form a ring structure.

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, cyclohexyl group, and bicyclohexyl group. Examples of the alkenyl group include those obtained by replacing one or more CH—CH structures present in the above alkyl group with C═C structures, and more specifically, vinyl groups, allyl groups, 1-propenyl groups. , 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 groups include those in which one or more CH ₂ —CH ₂ structures present in the alkyl group are replaced with C≡C structures, and more specifically, ethynyl groups, 1-propynyl groups, 2 -A propynyl group etc. are mentioned. As the aryl group, for example, phenyl group, α-naphthyl group, β-naphthyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1 -Phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.

  The above alkyl group, alkenyl group, alkynyl group, and aryl group may have a substituent as long as it has 1 to 20 carbon atoms as a whole, and may further form a ring structure by the substituent. Note that forming a ring structure with a substituent means that the substituents or a substituent and a part of the mother skeleton are bonded to form a ring structure.

Examples of this substituent include halogen groups, hydroxyl groups, thiol groups, nitro groups, organooxy groups, organothio groups, organosilyl groups, acyl groups, ester groups, thioester groups, phosphate ester groups, amide groups, aryl groups, alkyls. A group, an alkenyl group and an alkynyl group.
Examples of the halogen group as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The organooxy group as a substituent can have a structure represented by —O—R such as an alkoxy group, an alkenyloxy group, an aryloxy group. Examples of R include the above-described alkyl group, alkenyl group, and aryl group. These Rs may be further substituted with the substituent described above. Specific examples of the alkyloxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, and a lauryloxy group. .

  The organothio group as a substituent can have a structure represented by —S—R such as an alkylthio group, an alkenylthio group, and an arylthio group. Examples of R include the above-described alkyl group, alkenyl group, and aryl group. These Rs may be further substituted with the substituent described above. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, an octylthio group, a nonylthio group, a decylthio group, and a laurylthio group.

As the organosilyl group which is a substituent, a structure represented by -Si- (R) ₃ can be shown. The R may be the same or different, and examples thereof include the alkyl groups and aryl groups described above. These Rs may be further substituted with the substituent described above. Specific examples of the alkylsilyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, tripentylsilyl group, trihexylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, octyldimethylsilyl group, Examples include decyldimethylsilyl group.

As an acyl group which is a substituent, the structure represented by -C (O) -R can be shown. Examples of R include the above-described alkyl group, alkenyl group, and aryl group. These Rs may be further substituted with the substituent described above. 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 an ester group which is a substituent, the structure represented by -C (O) O-R or -OC (O) -R can be shown. Examples of R include the above-described alkyl group, alkenyl group, and aryl group. These Rs may be further substituted with the substituent described above.
As a thioester group which is a substituent, the structure represented by -C (S) O-R or -OC (S) -R can be shown. Examples of R include the above-described alkyl group, alkenyl group, and aryl group. These Rs may be further substituted with the substituent described above.
As a phosphate group which is a substituent, the structure represented by -OP (O)-(OR) ₂ can be shown. The R may be the same or different, and examples thereof include the alkyl groups and aryl groups described above. These Rs may be further substituted with the substituent described above.
As the amide group as a substituent, —C (O) NH ₂ , or —C (O) NHR, —NHC (O) R, —C (O) N (R) ₂ , —NRC (O) R The structure represented by can be shown. The R may be the same or different, and examples thereof include the alkyl groups and aryl groups described above. These Rs may be further substituted with the substituent described above.

Examples of the aryl group as a substituent include the same aryl groups as described above. This aryl group may be further substituted with the other substituent described above.
Examples of the alkyl group as a substituent include the same alkyl groups as described above. This alkyl group may be further substituted with the other substituent described above.
Examples of the alkenyl group as a substituent include the same alkenyl groups as described above. This alkenyl group may be further substituted with the other substituent described above.
Examples of the alkynyl group that is a substituent include the same alkynyl groups as described above. This alkynyl group may be further substituted with the other substituent described above.

In the above formula (2), R ₄ is a hydrogen atom or an alkyl group substituent 1 to 30 carbon atoms which may have a. Specific examples of the alkyl group and the substituent include the same alkyl groups and substituents as described above.
In the above formula (2), Z ₁ is a single bond or a divalent organic group having 1 to 30 carbon atoms. When Z ₁ is a divalent organic group having 1 to 30 carbon atoms, preferably a divalent organic group represented by the following formula (8).

（式（８）中、Ｂ_１及びＢ_２はそれぞれ独立して単結合、又は２価の連結基である。ただし、Ｂ_１及びＢ_２の少なくともどちらか一方は2価の連結基である。Ｒ_８及びＲ_９はそれぞれ独立して単結合又は置換基を有してもよい炭素数１〜２０のアルキレン基、アルケニレン基、アルキニレン基、アリーレン基、又はそれらの組み合わせである。）
上記Ｂ_１及びＢ_２の具体的な例を以下に示すが、これに限定されない。

(In Formula (8), B ₁ and B ₂ are each independently a single bond or a divalent linking group, provided that at least _one of B ₁ and B ₂ is a divalent linking group. R ₈ and R ₉ are each independently a single bond or an optionally substituted alkylene group having 1 to 20 carbon atoms, an alkenylene group, an alkynylene group, an arylene group, or a combination thereof.
Specific examples of the B ₁ and B ₂ are shown below, but is not limited thereto.

上記Ｂ−５〜Ｂ−８、Ｂ−１０、Ｂ−１１において、Ｒ^１０及びＲ^１１は水素原子又は置換基を有してもよいアルキル基、アルケニル基、アルキニル基、アリール基、又はそれらの組み合わせであり、環構造を形成してもよい。アルキル基、アルケニル基、アルキニル基、アリール基、及び置換基の具体例としては、前述したものと同じものを挙げることができる。

In the above B-5 to B-8, B-10, and B-11, R ¹⁰ and R ¹¹ are a hydrogen atom or an alkyl group, alkenyl group, alkynyl group, aryl group which may have a substituent, or those It is a combination and may form a ring structure. Specific examples of the alkyl group, alkenyl group, alkynyl group, aryl group, and substituent include the same ones as described above.

When R ¹⁰ and R ¹¹ have a bulky structure such as an aromatic ring or an alicyclic structure, when used as a liquid crystal alignment film, the liquid crystal alignment may be lowered. Therefore, methyl group, ethyl group, propyl group , An alkyl group such as a butyl group, or a hydrogen atom is preferable, and a hydrogen atom is more preferable.
In the formula (8), when R ₈ and R ₉ are an alkylene group having 1 to 20 carbon atoms, an alkenylene group, an alkynylene group, an arylene group, or a combination thereof, specific examples thereof are listed below. It is not limited to.

  As said alkylene group, the structure remove | excluding one hydrogen atom from the alkyl group is mentioned. More specifically, a methylene group, 1,1-ethylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group, 1,2-butylene group 1,2-pentylene group, 1,2-hexylene group, 1,2-nonylene group, 1,2-dodecylene group, 2,3-butylene group, 2,4-pentylene group, 1,2-cyclopropylene Group, 1,2-cyclobutylene group, 1,3-cyclobutylene group, 1,2-cyclopentylene group, 1,2-cyclohexylene group, 1,2-cyclononylene group, 1,2-cyclododecylene, etc. Can be mentioned. The alkenylene group includes a structure in which one hydrogen atom is removed from an alkenyl group. More specifically, 1,1-ethenylene group, 1,2-ethenylene group, 1,2-ethenylenemethylene group, 1-methyl-1,2-ethenylene group, 1,2-ethenylene-1,1- Ethylene group, 1,2-ethenylene-1,2-ethylene group, 1,2-ethenylene-1,2-propylene group, 1,2-ethenylene-1,3-propylene group, 1,2-ethenylene-1, Examples include 4-butylene group, 1,2-ethenylene-1,2-butylene group, 1,2-ethenylene-1,2-heptylene group, 1,2-ethenylene-1,2-decylene group and the like. The alkynylene group includes a structure in which one hydrogen atom is removed from the alkynyl group. More specifically, an ethynylene group, an ethynylene methylene group, an ethynylene-1,1-ethylene group, an ethynylene-1,2-ethylene group, an ethynylene-1,2-propylene group, an ethynylene-1,3-propylene group, Examples include ethynylene-1,4-butylene group, ethynylene-1,2-butylene group, ethynylene-1,2-heptylene group, ethynylene-1,2-decylene group and the like. The arylene group includes a structure in which one hydrogen atom is removed from an aryl group. More specifically, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,2-naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2, Examples include 3-naphthylene group, 2,6-naphthylene group, 3-phenyl-1,2-phenylene group, 2,2′-diphenylene group.

The above alkylene group, alkenylene group, alkynylene group, arylene group, and a combination thereof may have a substituent as long as the number of carbon atoms is 1 to 20 as a whole, and further a ring structure depending on the substituent. May be formed. Note that forming a ring structure with a substituent means that the substituents or a substituent and a part of the mother skeleton are bonded to form a ring structure.
Examples of this substituent include the same ones as described above.

When R ₈ and R ₉ have a small number of carbon atoms, the liquid crystal orientation is improved when used as a liquid crystal alignment film. Therefore, an alkylene group having 1 to 5 carbon atoms, an alkenylene group having 1 to 5 carbon atoms, and a carbon number 1-5 alkynylene groups are preferred. Moreover, it is preferable that both or one of R ₈ and R ₉ is a single bond.

In formula (2), D ₁ is an amino-protecting group, and its structure is not particularly limited as long as it is a functional group that can be replaced by a hydrogen atom by heating. From the viewpoint of the storage stability of the liquid crystal aligning agent of the present invention, this protecting group D ₁ is preferably not desorbed at room temperature, preferably a protecting group that is deprotected by heat of 80 ° C. or more, more preferably 100 It is a protecting group that is deprotected by heat at a temperature of at least ° C. Moreover, from the viewpoint of the efficiency of promoting thermal imidation of polyamic acid ester and the crosslinking reaction with the polyimide precursor or polyimide, it is preferably a protective group that is deprotected with heat of 300 ° C. or less, more preferably 250 ° C. The protecting group is deprotected with the following heat, and more preferably the protecting group is deprotected with a heat of 200 ° C. or less. As the structure of D ₁ as described above, an ester group represented by the following formula is preferable.

（式中、Ｒ_１１は炭素数１〜２２の炭化水素である。）

(In the formula, R ₁₁ is a hydrocarbon having 1 to 22 carbon atoms.)

  Specific examples of the ester group represented by the above formula (9) include methoxycarbonyl group, trifluoromethoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, tert- Examples include butoxycarbonyl group, sec-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, 9-fluorenylmethoxycarbonyl group and the like. Among these, a structure in which the elimination reaction efficiently proceeds at a baking temperature of 150 ° C. to 300 ° C., which is a firing temperature when obtaining a liquid crystal alignment film, is more preferable, and a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group is more preferable. A tert-butoxycarbonyl group is particularly preferred.

  Hereinafter, preferred specific examples of the structure represented by the formula (2) include the structures of D-1 to D-24, but are not limited thereto.

また、本発明の化合物としては、以下の構造を挙げることができるが、これに限定されない。

The compounds of the present invention can include the following structures, but are not limited thereto.

[Method for Synthesizing Compound of the Present Invention]
The compound of the present invention is a bischlorocarbonyl compound represented by the following formula (3), a tetracarboxylic acid derivative represented by the following formula (5), or a tetracarboxylic dianhydride represented by the following formula (6). And a monoamine compound represented by the following formula (4) as a raw material, and can be synthesized by various methods. Specific examples include the methods (i) to (iii), but are not limited thereto.

（式中、Ｒ_５は炭素数１〜５のアルキル基、Ｘ、Ｚ_１、Ｒ_２、Ｒ_３、Ｒ_４及びＤ_１はそれぞれ式（１）及び（２）で定義したものと同様である。）
上記式（３）のビスクロロカルボニル化合物は、例えば上記式（６）のテトラカルボン酸二無水物とＲ_５ＯＨで表されるアルコールとを反応させて、テトラカルボン酸ジアルキルエステルとした後、塩素化剤にてカルボキシル基をクロロカルボニル基に変換することで得ることができる。

(Wherein R ₅ is an alkyl group having 1 to ₅ carbon atoms, and X, Z ₁ , R ₂ , R ₃ , R ₄ and D ₁ are the same as those defined in formulas (1) and (2), respectively. .)
The bischlorocarbonyl compound of the above formula (3) is obtained by reacting, for example, a tetracarboxylic dianhydride of the above formula (6) with an alcohol represented by R ₅ OH to form a tetracarboxylic acid dialkyl ester, It can be obtained by converting a carboxyl group into a chlorocarbonyl group with an agent.

The tetracarboxylic acid derivative of the above formula (5) can be obtained, for example, by reacting the tetracarboxylic dianhydride of the above formula (6) with an alcohol represented by R ₅ OH.
The monoamine compound of the above formula (4) is a method of reacting a compound having a primary or secondary amino group represented by the following formula and di-tert-butyl dicarbonate in the presence of a base, or a primary or secondary compound. Although it is obtained by a method in which chloroformic acid-9-fluorenylmethyl is allowed to act on a compound having an amino group in the presence of a base, it is not particularly limited as long as it is a known method.

上記方法で得られた置換基を有する化合物をニトロ化合物、モノアミン化合物、ジアミン化合物又はその誘導体に付加し、さらに必要に応じて、ニトロ基の還元やアミノ基の導入を行うことで、熱脱離性の保護基を有するモノアミン化合物が得られる。

Addition of a compound having a substituent obtained by the above method to a nitro compound, a monoamine compound, a diamine compound or a derivative thereof, and further reducing the nitro group or introducing an amino group, if necessary, thermal desorption A monoamine compound having a protective group is obtained.

  Examples of the method for synthesizing the compound of the present invention include, but are not limited to, the following methods (i) to (iii).

(I) Method of synthesizing from bischlorocarbonyl compound and monoamine compound The compound of the present invention is obtained by reacting the biscarbonyl compound represented by the above formula (3) with the monoamine compound represented by the above formula (4). Can be synthesized.
Specifically, a bischlorocarbonyl compound and a monoamine compound are -20 ° C to 80 ° C, preferably 0 ° C to 50 ° C, in the presence of a base and an organic solvent, preferably 30 minutes to 24 hours, preferably 1 to 4 hours. It can be synthesized by reacting.
As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds gently. The addition amount of the base is preferably 2 to 4 times the mol of the bischlorocarbonyl compound from the viewpoint of easy removal.

(Ii) Method of synthesizing from tetracarboxylic acid derivative and monoamine compound The compound of the present invention is obtained by dehydrating condensation of a tetracarboxylic acid derivative represented by the above formula (5) and a monoamine compound represented by the above formula (4). Can be synthesized.
Specifically, a tetracarboxylic acid derivative and a monoamine compound are present in the presence of a condensing agent, a base, and an organic solvent at 0 ° C. to 80 ° C., preferably at 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 3 to 15 It can synthesize | combine by making it react for time.

Examples of the condensing agent include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazi Nylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ′, N′-tetramethyluronium hexafluorophosphate, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate, and the like. It is preferable that the addition amount of a condensing agent is 2-3 times mole with respect to the tetracarboxylic acid derivative.
As the base, tertiary amines such as pyridine and triethylamine can be used. The addition amount of the base is preferably 2 to 4 moles relative to the diamine component from the viewpoint of easy removal. 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. The addition amount of the Lewis acid is preferably 0 to 1.0 times the mole of the monoamine compound.

(Iii) Method of synthesizing from tetracarboxylic dianhydride and monoamine compound The compound of the present invention comprises a tetracarboxylic dianhydride represented by the above formula (6) and a monoamine compound represented by the above formula (4). It can be synthesized by reacting.
Specifically, the tetracarboxylic dianhydride and the monoamine compound are -20 ° C to 80 ° C, preferably 0 ° C to 50 ° C in the presence of an organic solvent, for 30 minutes to 24 hours, preferably 1 to 12 hours. It can be synthesized by reacting. The solvent used in the above reaction is N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide because of the solubility of tetracarboxylic dianhydride, monoamine compound, and product. , Tetrahydrofuran, chloroform and the like, and N-methyl-2-pyrrolidone, N, N-dimethylformamide, or tetrahydrofuran is preferable, and these may be used alone or in combination. The concentration during synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass.
Furthermore, in the compound of the present invention in which R ₁ in the above formula (1) is an alkyl group having 1 to 5 carbon atoms, various esterifying agents are added to a reaction solution of a tetracarboxylic dianhydride and a monoamine compound. And can be synthesized by esterification of the carboxyl group.

  Specifically, tetracarboxylic dianhydride, monoamine compound, and esterifying agent are present in the presence of an organic solvent at −20 ° C. to 80 ° C., preferably 0 ° C. to 50 ° C. for 30 minutes to 24 hours, preferably It can be synthesized by reacting for 1 to 4 hours.

  As the esterifying agent, those that can be easily removed by purification are preferred, and N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide Dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 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. The addition amount of the esterifying agent is preferably 2 to 6 molar equivalents relative to 1 mol of tetracarboxylic dianhydride.

  The solvents used in the reactions (i) to (iii) are N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N- Examples thereof include dimethylacetamide, tetrahydrofuran, chloroform and the like, and N-methyl-2-pyrrolidone, N, N-dimethylformamide, or tetrahydrofuran is preferable, and these may be used alone or in combination. The concentration during synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass. Moreover, when using a bischlorocarbonyl compound, in order to prevent a hydrolysis of a bischlorocarbonyl compound, it is preferable to dehydrate the solvent used at the time of synthesis | combination as much as possible, and it is preferable to prevent mixing of external air in nitrogen atmosphere.

The reaction solution obtained by the reactions (i) to (iii) can be used as it is as the composition of the present invention. In particular, when the compound of the present invention in which R ₁ in formula (1) is a hydrogen atom is obtained by the above method (iii), it is a reaction between an acid anhydride and an amine, and therefore reaction by-products and removal are necessary. No base or condensing agent. Therefore, the compound of the present invention as described above is particularly preferably used as it is as the composition of the present invention.

  Moreover, the compound of this invention can be precipitated by inject | pouring into the poor solvent, stirring well the reaction solution obtained by reaction of said (i)-(iii). Precipitation is performed several times, washed with a poor solvent, and then purified at room temperature or by heating and drying to obtain a powder of the compound of the present invention. Although a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, etc. are mentioned. When the purity of the obtained compound is low, when a film obtained from the composition is used as an electronic material, the electrical characteristics may be deteriorated. Therefore, purification by various methods is preferable. Examples of the purification method include silica gel column chromatography, recrystallization, and washing with an organic solvent. Recrystallization is more preferable from the viewpoint of simplicity of operation and high purification efficiency. As long as the organic solvent used for recrystallization is an organic solvent which can recrystallize the compound of this invention, it may select the kind and may recrystallize with 2 or more types of mixed solvents.

<Polyimide precursor and polyimide>
The polyimide precursor contained in the liquid crystal aligning agent of this invention is a polymer which has the site | part which can perform the imidation reaction shown below by heating.

本発明に使用されるポリイミド前駆体は、下記式（７）で表わされる構造を有する。

The polyimide precursor used in the present invention has a structure represented by the following formula (7).

In the above formula, R ₆ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably 1 to 2 carbon atoms. A ₁ and A ₂ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms 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, cyclohexyl group, and bicyclohexyl group. The above alkyl group may have a substituent, and may further form a ring structure with the substituent. Note that forming a ring structure with a substituent means that the substituents or a substituent and a part of the mother skeleton are bonded to form a ring structure.
Examples of such substituents are halogen groups, hydroxyl groups, thiol groups, nitro groups, aryl groups, organooxy groups, organothio groups, organosilyl groups, acyl groups, ester groups, thioester groups, phosphate ester groups, amide groups, alkyls. A group, an alkenyl group and an alkynyl group.

In general, when a bulky structure is introduced in the polyimide precursor, the reactivity of the amino group and the liquid crystal orientation may be lowered. Therefore, A ₁ and A ₂ have a hydrogen atom or a substituent. More preferred is an alkyl group having 1 to 5 carbon atoms, particularly preferably a hydrogen atom, a methyl group or an ethyl group.

In the formula (7), X ₁ is a tetravalent organic group, and Y ₁ is a divalent organic group. Two or more kinds of X ₁ may be mixed in the polyimide precursor. If the specific example is shown, in the structure represented by the formula (2) which is a preferable compound of the above-described heat-leaving group-containing compound, X-1 to X-46, which are the same as those described as examples of X, are Can be mentioned.
In formula (7), Y ₁ is a divalent organic group and is not particularly limited. In the polyimide precursor, two or more types of Y ₁ may be mixed. Specific examples of Y1 include the following Y- ₁ to Y-97.

Among them, in order to obtain a good liquid crystal alignment property, a high diamine polyimide precursor linearity, or preferably be introduced into the polyimide, as Y ₁ is, Y-7, Y-10 , Y-11, Y-12, Y-13, Y-21, Y-22, Y-23, Y-25, Y-26, Y-27, Y-41, Y-42, Y-43, Y-44, Y- More preferred are diamines of 45, Y-46, Y-48, Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y-74, Y-75, Y-98. . In order to increase the pretilt angle, a diamine having a long chain alkyl group, an aromatic ring, an aliphatic ring, a steroid skeleton, or a combination of these in the side chain may be introduced into the polyimide precursor or polyimide. Preferably, Y ₁ is Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y-86. , Y-87, Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96, or Y-97 is more preferred. . By adding 1 to 50 mol% of these diamines, any pretilt angle can be expressed.

<Method for producing polyimide precursor>
In the present invention, examples of the polyimide precursor include polyamic acid esters and polyamic acids. Among them, the polyamic acid ester can be obtained by reaction of any of the tetracarboxylic acid derivatives represented by the following formulas (10) to (12) with the diamine compound represented by the formula (13).

（式中、Ｘ_１、Ｙ_１、Ｒ_６、Ａ_１及びＡ_２はそれぞれ上記式（７）中の定義と同じである。）
上記式（１）で表されるポリアミック酸エステルは、上記モノマーを用いて、以下に示す（１）〜（３）の方法で合成することができる。

(Wherein X ₁ , Y ₁ , R ₆ , A ₁ and A ₂ are the same as defined in the above formula (7).)
The polyamic acid ester represented by the above formula (1) can be synthesized by the following methods (1) to (3) using the monomer.

(1) When synthesizing from polyamic acid The polyamic acid ester can be synthesized by esterifying a polyamic acid obtained from tetracarboxylic dianhydride and diamine.

具体的には、ポリアミック酸とエステル化剤を有機溶剤の存在下で−２０℃〜１５０℃、好ましくは０℃〜５０℃において、３０分〜２４時間、好ましくは１〜４時間反応させることによって合成することができる。

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

  As the esterifying agent, those that can be easily removed by purification are preferred, and N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide Dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 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. The addition amount of the esterifying agent is preferably 2 to 6 molar equivalents per 1 mol of the polyamic acid repeating unit.

  The solvent used in the above 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. Good. The concentration at the time of synthesis is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight body is easily obtained.

  (2) When synthesized by reaction of tetracarboxylic acid diester dichloride and diamine Polyamic acid ester can be synthesized from tetracarboxylic acid diester dichloride and diamine.

具体的には、テトラカルボン酸ジエステルジクロリドとジアミンとを塩基と有機溶剤の存在下で−２０℃〜１５０℃、好ましくは０℃〜５０℃において、３０分〜２４時間、好ましくは１〜４時間反応させることによって合成することができる。

Specifically, tetracarboxylic acid diester dichloride and diamine in the presence of a base and an organic solvent are −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., 30 minutes to 24 hours, preferably 1 to 4 hours. It can be synthesized by reacting.

  As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds gently. The addition amount of the base is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.

  The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone in view of the solubility of the monomer and polymer, and these may be used alone or in combination. The polymer concentration at the time of synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation hardly occurs and a high molecular weight body is easily obtained. In order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent mixing of outside air in a nitrogen atmosphere.

(3) When synthesizing from tetracarboxylic acid diester and diamine Polyamic acid ester can be synthesized by polycondensation of tetracarboxylic acid diester and diamine.

具体的には、テトラカルボン酸ジエステルとジアミンを縮合剤、塩基、有機溶剤の存在下で０℃〜１５０℃、好ましくは０℃〜１００℃において、３０分〜２４時間、好ましくは３〜１５時間反応させることによって合成することができる。

Specifically, tetracarboxylic acid diester and diamine in the presence of a condensing agent, a base and an organic solvent are 0 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., 30 minutes to 24 hours, preferably 3 to 15 hours. It can be synthesized by reacting.

  Examples of the condensing agent include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazi Nylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ′, N′-tetramethyluronium hexafluorophosphate, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate, and the like. It is preferable that the addition amount of a condensing agent is 2-3 times mole with respect to tetracarboxylic-acid diester.

As the base, tertiary amines such as pyridine and triethylamine can be used. The addition amount of the base is preferably 2 to 4 moles relative to the diamine component from the viewpoint that it can be easily removed and a high molecular weight product can be easily obtained.
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. The addition amount of the Lewis acid is preferably 0 to 1.0 times the mole of the diamine component.
Among the methods for synthesizing the three polyamic acid esters, since a high molecular weight polyamic acid ester is obtained, the synthesis method (1) or (2) is particularly preferable.

  The polyamic acid ester solution obtained as described above can be polymerized by pouring into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying. Although a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.

  The weight average molecular weight of the polyamic acid ester is preferably 5,000 to 300,000, and more preferably 10,000 to 200,000. The number average molecular weight is preferably 2,500 to 150,000, more preferably 5,000 to 100,000.

  On the other hand, when the polyimide precursor is a polyamic acid, the polyamic acid can be obtained by a reaction between a tetracarboxylic dianhydride represented by the following formula (12) and a diamine compound represented by the formula (13).

（式中、Ｘ_１、Ｙ_１、Ａ_１及びＡ_２はそれぞれ上記式（７）中の定義と同じである。）
具体的には、テトラカルボン酸二無水物とジアミンとを有機溶媒の存在下で−２０℃〜１５０℃、好ましくは０℃〜５０℃において、３０分〜２４時間、好ましくは１〜１２時間反応させることによって合成できる。

(In the formula, X ₁ , Y ₁ , A ₁ and A ₂ are the same as defined in the above formula (7).)
Specifically, tetracarboxylic dianhydride and diamine are reacted in the presence of an organic solvent at −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 12 hours. Can be synthesized.

The organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the solubility of the monomer and the polymer, and these may be used alone or in combination of two or more. It may be used. The concentration of the polymer is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that the polymer is hardly precipitated and a high molecular weight body is easily obtained.
The polyamic acid obtained as described above can be recovered by precipitating the polymer by pouring into the poor solvent while thoroughly stirring the reaction solution. Moreover, the powder of polyamic acid refine | purified by performing precipitation several times, washing | cleaning with a poor solvent, and normal temperature or heat-drying can be obtained. Although a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.

  The weight average molecular weight of the polyamic acid is preferably 10,000 to 300,000, and more preferably 20,000 to 200,000. Further, the number average molecular weight is preferably 2,500 to 15,000, and more preferably 5,000 to 100,000.

<Polyimide>
The imidization reaction for dehydrating and cyclizing the polyimide precursor is generally thermal imidization or chemical imidation, but chemical imidation in which the imidization reaction proceeds at a relatively low temperature may reduce the molecular weight of the resulting polyimide. Less likely to occur.

Chemical imidation can be performed by stirring the polyimide precursor in an organic solvent in the presence of a basic catalyst and an acid anhydride. The reaction temperature at this time is -20 to 250 ° C, preferably 0 to 180 ° C, and the reaction time can be 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 polyimide precursor, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the polyimide precursor. Is double. If the amount of the basic catalyst or acid anhydride is small, the reaction does not proceed sufficiently. If the amount is too large, it becomes difficult to completely remove the reaction after completion of the reaction.
Examples of the basic catalyst used for imidization include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Of these, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.

  Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. As an organic solvent, the solvent used at the time of the polyamic acid polymerization reaction mentioned above can be used. The imidation rate by chemical imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

  In the polyimide solution thus obtained, the added catalyst remains in the solution. Therefore, in order to use it for the liquid crystal aligning agent of the present invention, this polyimide solution is put into a poor solvent which is being stirred. It is preferable to use the polyimide after precipitation. Although it does not specifically limit as a poor solvent used for precipitation collection | recovery of a polyimide, Methanol, acetone, hexane, a butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene etc. can be illustrated. The polyimide precipitated by adding it to a poor solvent can be recovered by filtration, washing and drying at room temperature or under reduced pressure at normal temperature or by heating. If the operation of dissolving this powder in a good solvent and reprecipitating is repeated 2 to 10 times, the polyimide can be purified. When impurities cannot be completely removed by a single precipitation recovery operation, it is preferable to repeat this purification step. Mixing or sequentially using, for example, three or more kinds of poor solvents such as alcohols, ketones, and hydrocarbons as the poor solvent in the repeated purification step is preferable because the purification efficiency is further increased.

  The imidation ratio of the polyimide contained in the liquid crystal aligning agent of this invention is not specifically limited. What is necessary is just to set to arbitrary values in consideration of the solubility of a polyimide. The molecular weight of the polyimide contained in the liquid crystal aligning agent of the present invention is not particularly limited, but if the molecular weight of the polyimide is too small, the strength of the resulting coating film may be insufficient, and conversely, the molecular weight of the polyimide is too large. And the viscosity of the liquid crystal aligning agent manufactured may become high too much, and the workability | operativity at the time of coating-film formation and the uniformity of a coating film may worsen. Therefore, the weight average molecular weight of the polyimide used for the liquid crystal aligning agent of the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of this invention is a form of the solution which said polyimide precursor and / or polyimide melt | dissolved in the organic solvent. As long as it has such a form, for example, when a polyimide precursor such as polyamic acid ester and / or polyamic acid is synthesized in an organic solvent, the resulting reaction solution itself may be used. It may be diluted with a solvent. Moreover, when a polyimide precursor and / or a polyimide is obtained as a powder, it may be dissolved in an organic solvent to form a solution.

  The content (concentration) of the polyimide precursor and / or polyimide (hereinafter also referred to as polymer) in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the setting of the thickness of the polyimide film to be formed. From the viewpoint of forming a uniform and defect-free coating film, the polymer content is preferably 0.5% by mass or more with respect to the organic solvent, and preferably 15% by mass or less from the viewpoint of storage stability of the solution. More preferably, it is 1-10 mass%.

In addition to the polymer, the above-described heat-leaving group-containing compound is added to the liquid crystal aligning agent of the present invention. The heat-leaving group-containing compound is preferably added in an amount of 0.5 to 50 mol% with respect to 1 unit of the repeating unit of the polyimide precursor and the imidized polymer of the polyimide precursor.
The content of the heat-leaving group-containing compound is more preferably 1 to 30 mol%, particularly preferably 5 to 20 mol%. When the content is excessively small, the imidization reaction or crosslinking reaction of the polyimide precursor becomes insufficient, and when it is excessively large, the liquid crystal orientation may be adversely affected. It is not preferable.

  The said organic solvent contained in the liquid crystal aligning agent of this invention will not be specifically limited if a polymer melt | dissolves uniformly. Specific examples thereof include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, Examples include 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide and the like. You may use these 1 type or in mixture of 2 or more types. Moreover, even if it is a solvent which cannot melt | dissolve a polymer uniformly independently, as long as a polymer does not precipitate, you may mix with said organic solvent.

  The liquid crystal aligning agent of this invention may contain the solvent for improving the coating-film uniformity at the time of apply | coating a liquid crystal aligning agent to a board | substrate other than the organic solvent for dissolving a polymer. As such a solvent, a solvent having a surface tension lower than that of the organic solvent is generally used. Specific examples thereof include ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1- Butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, di Propylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactic acid Isoamyl ester, and the like. Two types of these solvents may be used in combination.

  The liquid crystal aligning agent of this invention may contain various additives, such as a silane coupling agent and a crosslinking agent. The silane coupling agent is added for the purpose of improving the adhesion between the substrate on which the liquid crystal alignment agent is applied and the liquid crystal alignment film formed thereon. Although the specific example of a silane coupling agent is given to the following, it is not limited to this.

  3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-phenylaminopropyltri Amine-based silane coupling agents such as methoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-aminopropyldiethoxymethylsilane; vinyltrimethoxysilane, vinyltriethoxysilane, Vinyl-based silane couplings such as vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, vinyltriacetoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, p-styryltrimethoxysilane Agents: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4- Epoxy cyclohexyl) Epoxy silane coupling agent such as ethyltrimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri Methacrylic silane coupling agents such as ethoxysilane; Acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; Ureido silane cups such as 3-ureidopropyltriethoxysilane Sulfide-based silane coupling agents such as bis (3- (triethoxysilyl) propyl) disulfide and bis (3- (triethoxysilyl) propyl) tetrasulfide; 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyl Mercapto silane coupling agents such as trimethoxysilane and 3-octanoylthio-1-propyltriethoxysilane; Isocyanate silane coupling agents such as 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxysilane; Aldehyde-based silane coupling agents such as butyraldehyde; carbamates such as triethoxysilylpropylmethylcarbamate and (3-triethoxysilylpropyl) -t-butylcarbamate Mate silane coupling agent.

If the amount of the silane coupling agent added is too large, unreacted ones may adversely affect the liquid crystal orientation, and if too small, the effect on adhesion will not appear, so the amount of the silane coupling agent is 0 with respect to the solid content of the polymer. 0.01 to 5.0% by weight is preferable, and 0.1 to 1.0% by weight is more preferable.
When adding the said silane coupling agent, in order to prevent precipitation of a polymer, it is preferable to add before adding the solvent for improving the above-mentioned coating-film uniformity.
An imidization accelerator may be added to efficiently advance imidization of the polyamic acid ester when the coating film is baked.

  In addition to the above, the liquid crystal aligning agent of the present invention has the purpose of changing the electrical properties such as the polymer other than the polymer and the dielectric constant and conductivity of the liquid crystal aligning film as long as the effects of the present invention are not impaired. A dielectric or conductive material, and further a crosslinkable compound for the purpose of increasing the hardness and density of the liquid crystal alignment film may be added.

  The liquid crystal aligning agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate and then subjected to alignment treatment by rubbing treatment, light irradiation or the like, or without alignment treatment in vertical alignment applications. In this case, the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, or the like can be used, and an ITO electrode for driving a liquid crystal is formed. It is preferable to use a prepared substrate from the viewpoint of simplification of the process. In the reflection type liquid crystal display element, an opaque substance such as a silicon wafer can be used as long as only one substrate is used. In this case, a material that reflects light such as aluminum can be used.

  The application method of the liquid crystal aligning agent is not particularly limited, but industrially, a method of screen printing, offset printing, flexographic printing, ink jet, or the like is common. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.

  The substrate coated with the liquid crystal aligning agent can be baked at an arbitrary temperature of 100 to 350 ° C., preferably 150 to 300 ° C., more preferably 180 to 250 ° C. The polyimide precursor contained in the liquid crystal aligning agent changes in conversion ratio to polyimide depending on the baking temperature, but the liquid crystal aligning agent does not necessarily need to be 100% imidized. For this reason, the firing time can be set to an arbitrary time, but if the firing time is too short, display failure may occur due to the influence of the residual solvent. Therefore, the firing time is preferably 5 to 60 minutes, more preferably 10 to 40 minutes.

In this firing process, the thermally detachable group-containing compound contained in the liquid crystal aligning agent of the present invention, as described above, decomposes the thermally detachable group, resulting in a highly reactive primary or secondary amine. Occur. The generated primary or secondary amine accelerates the imidization reaction of the polyimide precursor and / or the polymer of the polyimide, which is the main component contained in the liquid crystal aligning agent, and brings about a high imidization ratio. This causes a cross-linking reaction and gives a large mechanical strength to the liquid crystal alignment film obtained from the liquid crystal aligning agent. An increase in mechanical strength results in improved rubbing resistance and stability of liquid crystal properties at high temperatures.
If the thickness of the coating film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered, so it is preferably 5 to 300 nm, more preferably 10-100 nm. When the liquid crystal is horizontally or tilted, the fired coating film is treated by rubbing or irradiation with polarized ultraviolet rays.

  The liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.

  To give an example of liquid crystal cell production, prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside. Examples include a method of bonding the other substrate and injecting the liquid crystal under reduced pressure, or a method of sealing the liquid crystal after dropping the liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed, and the like. . The thickness of the spacer at this time is preferably 1 to 30 μm, more preferably 2 to 10 μm.

The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. The abbreviations of the compounds used in the examples and comparative examples, and the measuring methods of the respective properties are as follows.
1,3DMCBDE-Cl: Dimethyl 1,3-bis (chlorocarbonyl) -1,3-dimethylcyclobutane-2,4-dicarboxylate CBDE-Cl: Dimethyl 2,4-bis (chlorocarbonyl) cyclobutane-1,3 -Dicarboxylate CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride PMDA: pyromellitic dianhydride NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone BCS: butyl cellosolve PAE: polyamic acid Ester PAA: Polyamic acid

[ ¹ HNMR]
Apparatus: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (manufactured by Varian) 400 MHz
Solvent: deuterated dimethyl sulfoxide (DMSO-d ₆ ), deuterated chloroform (CDCl ₃ )
Standard substance: Tetramethylsilane (TMS)
[viscosity]
In the synthesis example, the viscosity of the polyamic acid ester and the polyamic acid solution is an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), sample amount 1.1 mL, cone rotor TE-1 (1 ° 34 ′, R24). ), Measured at a temperature of 25 ° C.

[Molecular weight]
The molecular weight of the polyamic acid ester is measured by a GPC (normal temperature gel permeation chromatography) apparatus, and is a number average molecular weight (hereinafter also referred to as Mn) and a weight average molecular weight (hereinafter also referred to as Mw) as polyethylene glycol and polyethylene oxide equivalent values. ) Was calculated.
GPC device: manufactured by Shodex (GPC-101)
Column: manufactured by Shodex (series of KD803 and KD805)
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L, tetrahydrofuran) (THF) is 10 ml / L)
Flow rate: 1.0 ml / min Standard sample for preparing calibration curve: TSK standard polyethylene oxide (weight average molecular weight (Mw) of about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polymer laboratory Polyethylene glycol manufactured by the company (peak top molecular weight (Mp) of about 12,000, 4,000, 1,000). In order to avoid the overlapping of peaks, the measurement was performed by mixing four types of 900,000, 100,000, 12,000, and 1,000, and three types of 150,000, 30,000, and 4,000. Two samples of the mixed sample were measured separately.
[FT-IR measurement]
Apparatus: NICOLET5700 (manufactured by Thermo ELECTRON)
Smart Orbit accessory measurement method: ATR method

[Rubbing resistance of liquid crystal alignment film]
A liquid crystal aligning agent was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at a temperature of 80 ° C. for 5 minutes, and baked at a temperature of 230 ° C. for 20 minutes to form an imidized film having a thickness of 100 nm. After this coating film was rubbed, the surface state of the film was observed to evaluate the presence or absence of rubbing scratches, the presence or absence of scraped film, and the presence or absence of film peeling.

[Liquid crystal orientation]
A liquid crystal aligning agent is spin-coated on a glass substrate with a transparent electrode, dried for 5 minutes on a hot plate at a temperature of 80 ° C, and baked for 20 minutes in a hot air circulation oven at 230 ° C to form a coating film having a thickness of 100 nm. I let you. The coating surface was rubbed or photo-aligned to obtain a substrate with a liquid crystal alignment film. Two substrates with such a liquid crystal alignment film are prepared, and a 6 μm spacer is sprayed on the liquid crystal alignment film surface of one of the substrates, and then the two substrates are combined so that the alignment is antiparallel. The periphery was sealed and the empty cell having a cell gap of 6 μm was produced. Liquid crystal (MLC-2041, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature, and the inlet was sealed to obtain a liquid crystal cell. Using this liquid crystal cell, the liquid crystal alignment was observed with a polarizing microscope, and the liquid crystal alignment was evaluated according to the following criteria.
<Evaluation criteria>
○: No flow alignment is observed, and no light leakage occurs under crossed Nicols.
Δ: Some flow alignment is observed, and light leakage is observed under crossed Nicols.
X: Flow orientation is observed throughout the cell.

[Voltage holding ratio]
The voltage holding ratio of the liquid crystal cell was measured as follows.
By applying a voltage of 4 V for 60 μs and measuring the voltage after 16.67 ms, the fluctuation from the initial value was calculated as the voltage holding ratio. During the measurement, the temperature of the liquid crystal cell was set to 23 ° C., 60 ° C., and 90 ° C., and the measurement was performed at each temperature.
[Ion density]
The measurement of the ion density of the liquid crystal cell was performed as follows.
Measurement was performed using a 6254 type liquid crystal property evaluation apparatus manufactured by Toyo Technica. A triangular wave of 10 V and 0.01 Hz was applied, and an area corresponding to the ion density of the obtained waveform was calculated by a triangle approximation method to obtain an ion density. At the time of measurement, the temperature of the liquid crystal cell was 23 ° C. and 60 ° C., and the measurement was performed at each temperature.
[Pretilt angle measurement]
The pretilt angle of the liquid crystal cell was measured using an AxoScan manufactured by Axometrics.

５００ｍＬ のナスフラスコにプロパルギルアミン (8.81 g, 160 mmol) 、N,N-ジメチルホルムアミド (112 mL) 、炭酸カリウム (18.5 g, 134 mmol) の順に入れ、0 ℃ にし、ブロモ酢酸t-ブチル (21.9 g, 112 mmol) をN,N-ジメチルホルムアミド (80 mL) に溶かした溶液を約1時間で、撹拌しながら滴下した。滴下終了後、反応溶液を室温にし、20時間撹拌した。その後、固形物をろ過により除去し、ろ液に酢酸エチルを 1 L 加え、300 mL の水で 4 回、300 mL の飽和食塩水で 1 回洗浄した。その後、有機層を硫酸マグネシウムで乾燥し、溶媒を減圧留去した。最後に、残留した油状物を 0.6 Torr, 70 ℃で減圧蒸留することにより、無色液体のN-プロパルギルアミノ酢酸t-ブチル（化合物（Ａ５））を得た。収量は 12.0 g、収率は63% であった。(Synthesis Example 1)
A diamine compound (DA-1) was synthesized by the following four-step route.
First step: Synthesis of compound (A5)

Into a 500 mL eggplant flask, put propargylamine (8.81 g, 160 mmol), N, N-dimethylformamide (112 mL), potassium carbonate (18.5 g, 134 mmol) in this order, bring it to 0 ° C., and add t-butyl bromoacetate (21.9 g, 112 mmol) in N, N-dimethylformamide (80 mL) was added dropwise with stirring over about 1 hour. After completion of the dropwise addition, the reaction solution was brought to room temperature and stirred for 20 hours. Thereafter, the solid matter was removed by filtration, 1 L of ethyl acetate was added to the filtrate, and the mixture was washed 4 times with 300 mL of water and once with 300 mL of saturated saline. Thereafter, the organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. Finally, the remaining oil was distilled under reduced pressure at 0.6 Torr and 70 ° C. to obtain t-butyl N-propargylaminoacetate (compound (A5)) as a colorless liquid. The yield was 12.0 g, and the yield was 63%.

1 L のナスフラスコに上記N-プロパルギルアミノ酢酸t-ブチル (12.0 g, 70.9 mmol)、ジクロロメタン (600 mL) を入れて溶液とし、攪拌氷冷しながら、二炭酸ジt-ブチル (15.5 g, 70.9 mmol) をジクロロメタン (100 mL) に溶かした溶液を１時間で滴下した。滴下終了後、反応溶液を室温にし、20時間攪拌した。反応終了後、反応溶液を300 mL の飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した。その後、溶媒を減圧留去することで、薄黄色液体のN-プロパルギル-N-t-ブトキシカルボニルアミノ酢酸t-ブチル（化合物（Ａ６））を得た。収量は 18.0 g、収率は 94% であった。Second step: Synthesis of compound (A6)

In a 1 L eggplant flask, the above N-propargylaminoacetic acid t-butyl (12.0 g, 70.9 mmol) and dichloromethane (600 mL) were added to form a solution. While stirring and cooling with ice, di-t-butyl dicarbonate (15.5 g, A solution of 70.9 mmol) in dichloromethane (100 mL) was added dropwise over 1 hour. After completion of the dropwise addition, the reaction solution was brought to room temperature and stirred for 20 hours. After completion of the reaction, the reaction solution was washed with 300 mL of saturated brine and dried over magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to obtain N-propargyl-Nt-butoxycarbonylaminoacetic acid t-butyl (compound (A6)) as a light yellow liquid. The yield was 18.0 g, and the yield was 94%.

300 mL の四つ口フラスコに2-ヨード-4-ニトロアニリン (22.5 g, 85.4 mmol)、ビス(トリフェニルホスフィン)パラジウムジクロリド (1.20 g, 1.71 mmol)、ヨウ化銅 (0.651 g, 3.42 mmol)を入れ、窒素置換した後、ジエチルアミン (43.7 g, 598 mmol)、N,N-ジメチルホルムアミド (128 mL) を加え、氷冷攪拌しながら、前記N-プロパルギルアミノ-N-t-ブトキシカルボニル酢酸t-ブチル (27.6 g, 102 mmol) を加え、室温で20時間攪拌した。反応終了後、1 L の酢酸エチルを加え、1 mol/L の塩化アンモニウム水溶液 150 mL で3回、150 mL の飽和食塩水で1回洗浄し、硫酸マグネシウムで乾燥した。その後、溶媒を減圧留去することで析出した固体を200 mL の酢酸エチルに溶かし、1 L のヘキサンを加えることで再結晶を行った。この固体をろ取し、減圧乾燥することで、黄色固体の2-{3-(N-t-ブトキシカルボニル-N-t-ブトキシカルボニルメチルアミノ)-1-プロピニル)}-4-ニトロアニリン（化合物（Ａ７））を得た。収量は23.0 g, 収率は66%であった。Third step: Synthesis of compound (A7)

2-Iodo-4-nitroaniline (22.5 g, 85.4 mmol), bis (triphenylphosphine) palladium dichloride (1.20 g, 1.71 mmol), copper iodide (0.651 g, 3.42 mmol) in a 300 mL four-necked flask After adding nitrogen and replacing with nitrogen, diethylamine (43.7 g, 598 mmol) and N, N-dimethylformamide (128 mL) were added, and while stirring on ice, the N-propargylamino-Nt-butoxycarbonyl acetate t-butyl was added. (27.6 g, 102 mmol) was added and stirred at room temperature for 20 hours. After completion of the reaction, 1 L of ethyl acetate was added, washed with 150 mL of a 1 mol / L aqueous ammonium chloride solution three times and once with 150 mL of saturated brine, and dried over magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure, and the precipitated solid was dissolved in 200 mL of ethyl acetate and recrystallized by adding 1 L of hexane. This solid was collected by filtration and dried under reduced pressure to give 2- {3- (Nt-butoxycarbonyl-Nt-butoxycarbonylmethylamino) -1-propynyl)}-4-nitroaniline (compound (A7)) as a yellow solid. ) The yield was 23.0 g, and the yield was 66%.

¹H NMR (DMSO-d₆): δ 6.54-6.42 (m, 3H, Ar), 3.49, 3.47 (each s, 2H, NCH₂CO₂t-Bu), 3.38-3.30 (m, 2H, CH₂CH₂N), 2.51-2.44 (m, 2H, ArCH₂), 1.84-1.76 (m, 2H, CH₂CH₂CH₂), 1.48-1.44 (m, 18H, NCO₂t-Bu and CH₂CO₂t-Bu).Fourth step: Reduction of compound (A7)
In a 500 mL four-necked flask, add 2- {3- (Nt-butoxycarbonyl-Nt-butoxycarbonylmethylamino) -1-propynyl)}-4-nitroaniline (22.0 g, 54.2 mmol) and ethanol ( 200 g) was added, and the inside of the system was replaced with nitrogen. Then, palladium carbon (2.20 g) was added, the inside of the system was replaced with hydrogen, and the mixture was stirred at 50 ° C. for 48 hours. After completion of the reaction, palladium carbon was removed by Celite filtration, activated carbon was added to the filtrate, and the mixture was stirred at 50 ° C. for 30 minutes. Thereafter, the activated carbon was filtered, the organic solvent was distilled off under reduced pressure, and the residual oil was dried under reduced pressure to obtain a diamine compound (DA-1). The yield was 19.8 g, and the yield was 96%.
The diamine compound (DA-1) was confirmed by ¹ H NMR.

¹ H NMR (DMSO-d ₆ ): δ 6.54-6.42 (m, 3H, Ar), 3.49, 3.47 (each s, 2H, NCH ₂ CO ₂ t-Bu), 3.38-3.30 (m, 2H, CH ₂ CH ₂ N), 2.51-2.44 (m, 2H, ArCH ₂ ), 1.84-1.76 (m, 2H, CH ₂ CH ₂ CH ₂ ), 1.48-1.44 (m, 18H, NCO ₂ t-Bu and CH ₂ CO ₂ t-Bu).

(Synthesis Example 2)
Synthesis of dimethyl 1,3-bis (chlorocarbonyl) -1,3-dimethylcyclobutane-2,4-dicarboxylate (1,3DMCBDE-Cl) a-1: Synthesis of dialkyl ester of tetracarboxylic acid

Under a nitrogen stream, a 3-L four-necked flask was charged with 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride (compound of formula (5-1), hereinafter referred to as 1,3-DM. -CBDA) 220 g (0.981 mol) and methanol 2200 g (6.87 mol, 10 wt times relative to 1,3-DM-CBDA) were charged and refluxed at 65 ° C. for 30 minutes. A homogeneous solution was obtained. The reaction solution was stirred for 4 hours and 30 minutes under heating and reflux. This reaction solution was measured by high performance liquid chromatography (hereinafter abbreviated as HPLC). The analysis of the measurement result will be described later.
After evaporating the solvent from the reaction solution with an evaporator, 1301 g of ethyl acetate was added, heated to 80 ° C., and refluxed for 30 minutes. Then, it cooled until the internal temperature became 25 degreeC at the speed | rate of 2-3 degreeC in 10 minutes, and stirred for 30 minutes as it was at 25 degreeC. The precipitated white crystals were taken out by filtration, washed twice with 141 g of ethyl acetate, and then dried under reduced pressure to obtain 103.97 g of white crystals.
This crystal was confirmed to be compound (1-1) from the results of 1H NMR analysis and X-ray crystal structure analysis (HPLC relative area 97.5%) (yield 36.8%).
1H NMR (DMSO-d6, δppm); 12.82 (s, 2H), 3.60 (s, 6H), 3.39 (s, 2H), 1.40 (s, 6H).

窒素気流下中、３Ｌの四つ口フラスコに、化合物（１−１）２３４．１５ｇ（０．８１ｍｏｌ）、ｎ−ヘプタン１１７０．７７ｇ（１１．６８ｍｏｌ．５ｗｔ倍）を仕込んだ後、ピリジン０．６４ｇ（０．０１ｍｏｌ）を加え、マグネチックスターラー攪拌下にて７５℃まで加熱撹拌した。続いて、塩化チオニル２８９．９３ｇ（１１．６８ｍｏｌ）を１時間かけて滴下した。滴下直後から発泡が開始し、滴下終了３０分後に反応溶液は均一となり、発泡は停止した。続いてそのまま７５℃にて１時間３０分撹拌した後、エバポレーターにて水浴４０℃で内容量が９２４．４２ｇになるまで溶媒を留去した。これを６０℃に加熱し、溶媒留去時に析出した結晶を溶解させ、６０℃にて熱時ろ過を行うことで不溶物をろ過した後、ろ液を２５℃まで１０分間に１℃の速度で冷却した。そのまま２５℃で３０分撹拌させた後、析出した白色結晶をろ過により取り出し、この結晶をｎ−ヘプタン２６４．２１ｇにて洗浄した。これを減圧乾燥することで、白色結晶を２２６．０９ｇ得た。Synthesis of a-2.1,3-DM-CBDE-C1

In a nitrogen stream, after charging 234.15 g (0.81 mol) of compound (1-1) and 117.77 g (11.68 mol.5 wt times) of n-heptane in a 3 L four-necked flask, the pyridine was mixed with 0.1. 64 g (0.01 mol) was added, and the mixture was heated and stirred to 75 ° C. while stirring with a magnetic stirrer. Subsequently, 289.93 g (11.68 mol) of thionyl chloride was added dropwise over 1 hour. Foaming started immediately after the dropping, and the reaction solution became uniform 30 minutes after the completion of the dropping, and the foaming stopped. Subsequently, the mixture was stirred as it was at 75 ° C. for 1 hour and 30 minutes, and then the solvent was distilled off with an evaporator until the internal volume reached 924.42 g in a water bath at 40 ° C. This was heated to 60 ° C., the crystals precipitated when the solvent was distilled off were dissolved, the insoluble matter was filtered by performing hot filtration at 60 ° C., and then the filtrate was heated to 25 ° C. at a rate of 1 ° C. for 10 minutes. It was cooled with. After stirring as it was at 25 ° C. for 30 minutes, the precipitated white crystal was taken out by filtration, and this crystal was washed with 264.21 g of n-heptane. This was dried under reduced pressure to obtain 226.09 g of white crystals.

Subsequently, 226.09 g of the white crystals obtained above and 454.18 g of n-heptane were charged into a 3 L four-necked flask in a nitrogen stream, and heated and stirred at 60 ° C. to dissolve the crystals. Thereafter, the mixture was cooled and stirred at a rate of 1 ° C. for 10 minutes to 25 ° C. to precipitate crystals. After stirring as it was at 25 ° C. for 1 hour, the precipitated white crystals were taken out by filtration, washed with 113.04 g of n-hexane, and then dried under reduced pressure to obtain 203.91 g of white crystals. According to the result of 1H NMR analysis, this crystal was found to be compound (3-1), that is, dimethyl-1,3-bis (chlorocarbonyl) -1,3-dimethylcyclobutane-2,4-dicarboxylate (hereinafter referred to as 1,3). -DM-CBDE-C1.) (HPLC relative area 99.5%) (yield 77.2%).
1H NMR (CDCl3, δppm): 3.78 (s, 6H), 3.72 (s, 2H), 1.69 (s, 6H).

(Synthesis Example 3)
A 3L four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere. 10.9293 g (0.101 mol) of p-phenylenediamine and 10.8177 g (0.0285 mol) of diamine (DA-1) were added, 472 g of NMP, base As a result, 23.12 g (0.292 mol) of pyridine was added and dissolved by stirring. Next, 39.6013 g (0.122 mol) of 1,3DM-CBDE-Cl was added while stirring the diamine solution, and the mixture was reacted for 4 hours under water cooling. To the obtained polyamic acid ester solution, 2101 g of NMP was added and stirred for 30 minutes to obtain an obtained polyamic acid ester solution having a solid content concentration of 5 wt%. The polyamic acid ester solution is poured into 5247 g of water while stirring, and the precipitated white precipitate is collected by filtration, and then washed once with 5247 g of water, once with 5247 g of ethanol, and three times with 1312 g of ethanol. Then, 45.90 g of a white polyamic acid ester resin powder was obtained by drying. The yield was 87.7%. Moreover, the molecular weight of this polyamic acid ester was Mn = 16,556 and Mw = 35,901.
35.99 g of the obtained polyamic acid ester resin powder was placed in a 300 ml Erlenmeyer flask, 230.85 g of GBL was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-1).

(Synthesis Example 4)
A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 10.532 g (53.12 mmol) of 4,4′-diaminodiphenylmethane was added, 197.63 g of NMP, and 9.00 g (113.8 mmol) of pyridine as a base. Added and stirred to dissolve. Next, while stirring the diamine solution, 15.4194 g (47.42 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. The obtained polyamic acid ester solution was poured into 2196 g of water while stirring, and the precipitated white precipitate was collected by filtration, followed by 2196 g of water once, 2196 g of ethanol once, and 549 g of ethanol. By washing 3 times and drying, 20.37 g of white polyamic acid ester resin powder was obtained. The yield was 92.8%. Moreover, the molecular weight of this polyamic acid ester was Mn = 11,659 and Mw = 25,571.
3.9648 g of the obtained polyamic acid ester resin powder was placed in a 100 ml Erlenmeyer flask, 35.7135 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-2).

(Synthesis Example 5)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 5.8936 g (30.05 mmol) of CBDA was added, and then 56.11 g of NMP was added, and the mixture was stirred while feeding nitrogen to form a slurry. While stirring this slurry solution, 3.0196 g (27.92 mmol) of p-PDA was added, NMP was further added so that the solid content concentration was 10% by mass, and the mixture was stirred at room temperature for 24 hours to polyamic acid (PAA). A solution of -1) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 136.5 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 13,391 and Mw = 32,745.

以下に、４ステップの経路で化合物（１−ａ）を合成した。Example 1 Synthesis of Compound (1-a)

Hereinafter, compound (1-a) was synthesized by a four-step route.

３００ｍｌ四つ口フラスコに、２−（４−ニトロフェニル）エチルアミン塩酸塩を１８．７８ｇ（９２．６８ｍｍｏｌ）入れ、次いで、トルエンを１５２ｍｌ、トリエチルアミンを９．８４７ｇ（９７．３１ｍｍｏｌ）加えて、０℃（氷浴）にて撹拌した。滴下ロートに二炭酸ジ−ｔｅｒｔ−ブチルを２１．２４ｇ（９７．３１ｍｍｏｌ）を、四つ口フラスコ中の溶液に３０分かけて滴下した。滴下終了後、室温（２０℃）にて８時間撹拌した。反応終了後、反応溶液に純水５００ｍｌを加え、抽出した。得られた有機層を純水で２回洗浄し、無水硫酸マグネシウムで乾燥した。乾燥剤を除去後、溶媒留去し、白色固体を得た。この白色固体にヘキサンを１００ｍｌ、酢酸エチルを２０ｍｌ加えて、再結晶を行った。析出した固体を吸引ろ取し、減圧乾燥した。^１ＨＮＭＲより得られた白色固体が前駆体（１−ａ１）であることを確認した。収量は２０．９２ｇ、収率は８５％であった。
¹H NMR (400MHz, CDCl₃, δppm)：1.43(s, 9H), 2.92(t, J=6.8Hz, 2H), 3.41(q, J=6.8Hz, 2H), 4.56(bs, 1H), 7.35(d, J=8.8Hz, 2H), 8.16(d, J=8.8Hz, 2H).First step: synthesis of precursor (1-a1)

In a 300 ml four-necked flask, 18.78 g (92.68 mmol) of 2- (4-nitrophenyl) ethylamine hydrochloride was added, and then 152 ml of toluene and 9.847 g (97.31 mmol) of triethylamine were added. (Ice bath). To the dropping funnel, 21.24 g (97.31 mmol) of di-tert-butyl dicarbonate was added dropwise to the solution in the four-necked flask over 30 minutes. After completion of dropping, the mixture was stirred at room temperature (20 ° C.) for 8 hours. After completion of the reaction, 500 ml of pure water was added to the reaction solution and extracted. The obtained organic layer was washed twice with pure water and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off to obtain a white solid. The white solid was recrystallized by adding 100 ml of hexane and 20 ml of ethyl acetate. The precipitated solid was collected by suction filtration and dried under reduced pressure. ^The white solid obtained from ¹ HNMR was confirmed to be the precursor (1-a1). The yield was 20.92 g and the yield was 85%.
¹ H NMR (400MHz, CDCl ₃ , δppm): 1.43 (s, 9H), 2.92 (t, J = 6.8Hz, 2H), 3.41 (q, J = 6.8Hz, 2H), 4.56 (bs, 1H), 7.35 (d, J = 8.8Hz, 2H), 8.16 (d, J = 8.8Hz, 2H).

５００ｍｌナス型フラスコに前駆体（１−ａ１）を２０．９０ｇ（７８．４９ｍｍｏｌ）入れ、テトラヒドロフラン２００ｍｌを加えた。反応容器を窒素置換した後、パラジウムカーボンを２．０９ｇ加え、窒素置換した。反応容器を水素置換し、２０℃にて、１９時間撹拌した。反応終了後、セライトろ過により、パラジウムカーボンを除去し、ろ液から溶媒を除去し、白色固体を得た。得られた固体を酢酸エステル２０ｍｌに溶解し、ヘキサンを１４０ｍｌ加えて、再結晶を行った。析出した固体を吸引ろ取し、減圧乾燥した。^１ＨＮＭＲより得られた白色固体が前駆体（１−ａ２）であることを確認した。収量は１６．５４ｇ、収率は８９％であった。
¹H NMR (400MHz, CDCl₃, δppm)：1.43(s, 9H), 2.67(t, J=6.8Hz, 2H), 3.31(q, J=6.8Hz, 2H), 3.59(bs, 2H), 4.52(bs, 1H), 6.64(d, J=8.0Hz, 2H), 6.97(d, J=8.0Hz, 2H).Second step: synthesis of precursor (1-a2)

In a 500 ml eggplant-shaped flask, 20.90 g (78.49 mmol) of the precursor (1-a1) was placed, and 200 ml of tetrahydrofuran was added. After the reaction vessel was purged with nitrogen, 2.09 g of palladium carbon was added and purged with nitrogen. The reaction vessel was purged with hydrogen and stirred at 20 ° C. for 19 hours. After completion of the reaction, palladium carbon was removed by Celite filtration, and the solvent was removed from the filtrate to obtain a white solid. The obtained solid was dissolved in 20 ml of acetic ester, and 140 ml of hexane was added for recrystallization. The precipitated solid was collected by suction filtration and dried under reduced pressure. ^The white solid obtained from ¹ HNMR was confirmed to be the precursor (1-a2). The yield was 16.54 g, and the yield was 89%.
¹ H NMR (400MHz, CDCl ₃ , δppm): 1.43 (s, 9H), 2.67 (t, J = 6.8Hz, 2H), 3.31 (q, J = 6.8Hz, 2H), 3.59 (bs, 2H), 4.52 (bs, 1H), 6.64 (d, J = 8.0Hz, 2H), 6.97 (d, J = 8.0Hz, 2H).

Third Step: Synthesis of Compound (1-a) A 100 ml four-necked flask was put in a nitrogen atmosphere, and 5.00 g (15.38 mmol) of 1,3DM-CBDE-Cl was added thereto, and then 25 ml of tetrahydrofuran (dehydrated) was added. 2.68 g (33.83 mmol) of pyridine was added and stirred to obtain an acid chloride solution. Next, 7.45 g (31.53 mmol) of the precursor (1-a2) was placed in a 100 ml Erlenmeyer flask, and then 15 ml of tetrahydrofuran (dehydrated) was added to obtain a monoamine solution. This monoamine solution was transferred to a dropping funnel, and the monoamine solution was dropped into a four-necked flask over 15 minutes. After dropping, the mixture was stirred for 20 hours. After 20 hours, the reaction solution was poured into 200 ml of water, and extracted with 100 ml of chloroform. The obtained organic layer was washed twice with pure water and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off to obtain a white solid. The obtained solid was dissolved in 30 ml of tetrahydrofuran, and recrystallized by adding 100 ml of diisopropyl ether. The precipitated solid was collected by suction filtration and dried under reduced pressure. It was confirmed that the white solid obtained from ¹ HNMR was the compound (1-a). The yield was 8.38 g, and the yield was 75%.
¹ H NMR (400MHz, CDCl ₃ , δppm): 1.43 (s, 18H), 1.58 (s, 6H), 2.78 (t, J = 6.8Hz, 4H), 3.53 (m, 4H), 3.84 (s, 6H ), 4.10 (s, 2H), 4.55 (bs, 2H), 7.18 (d, J = 8.0Hz, 4H), 7.45 (d, J = 8.0Hz, 4H), 8.62 (s, 2H).

以下に、３ステップの経路で化合物（１−ｂ）を合成した。Example 2 Synthesis of Compound (1-b)

Hereinafter, compound (1-b) was synthesized by a three-step route.

窒素置換した１００ｍｌ四つ口フラスコに４−ブロモニトロベンゼンを８．９５ｇ（４４．３０ｍｍｏｌ）、ビス（トリフェニルホスフィン）パラジウム（ＩＩ）ジクロリドを０．３１１ｇ（０．４４ｍｍｏｌ）、ヨウ化銅を０．１６９ｇ（０．８９ｍｍｏｌ）、トリエチルアミンを５．３８ｇ（５３．１６ｍｍｏｌ）を入れ、テトラヒドロフランを３０ｍｌ加えて、室温（２０℃）で１０分間攪拌した。次に、１００ｍｌ三角フラスコにＮ−（ｔｅｒｔ−ブトキシカルボニル）プロパルギルアミンを８．２５ｇ（５３．１６ｍｍｏｌ）を入れ、テトラヒドロフランを１５ｍｌ加えて、溶解した。この溶液を滴下ロートに移し、四つ口フラスコ中の溶液へ５分間かけて滴下した。滴下後、６０℃にて３時間加熱撹拌した。３時間後、反応溶液を２５０ｍｌの純水に投入し、固体を析出させた。析出した固体を吸引ろ取した後、得られた固体をトルエン４０ｍｌに溶解し、ヘキサン２５ｍｌを加えて、再結晶した。析出した固体を吸引ろ取し、減圧乾燥した。^１ＨＮＭＲより得られた茶色固体が前駆体（１−ｂ１）であることを確認した。収量は７．６６ｇ、収率は６２．５％であった。
¹H NMR (400MHz, CDCl₃, δppm)：1.43(s, 9H), 4.20(s, 2H), 4.82(bs, 1H), 7.56(d, J=8.0Hz, 2H), 8.18(d, J=8.0Hz, 2H).First step: synthesis of precursor (1-b1)

In a 100 ml four-necked flask purged with nitrogen, 8.95 g (44.30 mmol) of 4-bromonitrobenzene, 0.311 g (0.44 mmol) of bis (triphenylphosphine) palladium (II) dichloride, and 0.1% of copper iodide were added. 169 g (0.89 mmol) and 5.38 g (53.16 mmol) of triethylamine were added, 30 ml of tetrahydrofuran was added, and the mixture was stirred at room temperature (20 ° C.) for 10 minutes. Next, 8.25 g (53.16 mmol) of N- (tert-butoxycarbonyl) propargylamine was placed in a 100 ml Erlenmeyer flask, and 15 ml of tetrahydrofuran was added and dissolved. This solution was transferred to a dropping funnel and added dropwise to the solution in the four-necked flask over 5 minutes. After dropping, the mixture was stirred with heating at 60 ° C. for 3 hours. After 3 hours, the reaction solution was poured into 250 ml of pure water to precipitate a solid. After the precipitated solid was collected by suction filtration, the obtained solid was dissolved in 40 ml of toluene and recrystallized by adding 25 ml of hexane. The precipitated solid was collected by suction filtration and dried under reduced pressure. It was confirmed that the brown solid obtained from ¹ HNMR was the precursor (1-b1). The yield was 7.66 g, and the yield was 62.5%.
¹ H NMR (400MHz, CDCl ₃ , δppm): 1.43 (s, 9H), 4.20 (s, 2H), 4.82 (bs, 1H), 7.56 (d, J = 8.0Hz, 2H), 8.18 (d, J = 8.0Hz, 2H).

５００ｍｌナス型フラスコに前駆体（１−ｂ１）を１２．８７ｇ（４６．５８ｍｍｏｌ）入れ、メタノール１３０ｍｌを加えた。反応容器を窒素置換した後、パラジウムカーボンを１．２８ｇ加え、窒素置換した。反応容器を水素置換し、５０℃にて、２４時間加熱撹拌した。反応終了後、セライトろ過により、パラジウムカーボンを除去し、ろ液から溶媒を除去し、茶色のアメ状化合物を得た。得られたアメ状化合物をシリカゲルカラムクロマトグラフィー（酢酸エチル：ヘキサン＝５０：５０）にて精製し、茶色のアメ状化合物を得た。^１ＨＮＭＲより得られた茶色のアメ状化合物が前駆体（１−ｂ２）であることを確認した。収量は４．４２ｇ、収率は３７．９％であった。
¹H NMR (400MHz, CDCl₃, δppm)：1.43(s, 9H), 1.75(quin, J=6.8Hz, 2H), 2.55(t, J=6.8Hz, 2H), 3.16(q, J=6.8Hz, 2H), 3.59(bs, 2H), 4.56(bs, 1H), 6.67(d, J=8.0Hz, 2H), 6.96(d, J=8.0Hz, 2H).Second step: synthesis of precursor (1-b2)

12.87 g (46.58 mmol) of the precursor (1-b1) was placed in a 500 ml eggplant type flask, and 130 ml of methanol was added. After the reaction vessel was purged with nitrogen, 1.28 g of palladium carbon was added and purged with nitrogen. The reaction vessel was purged with hydrogen and stirred at 50 ° C. for 24 hours. After completion of the reaction, palladium carbon was removed by Celite filtration, and the solvent was removed from the filtrate to obtain a brown candy-like compound. The obtained candy-like compound was purified by silica gel column chromatography (ethyl acetate: hexane = 50: 50) to obtain a brown candy-like compound. It was confirmed that the brown candy-like compound obtained from ¹ HNMR was the precursor (1-b2). The yield was 4.42 g, and the yield was 37.9%.
¹ H NMR (400MHz, CDCl ₃ , δppm): 1.43 (s, 9H), 1.75 (quin, J = 6.8Hz, 2H), 2.55 (t, J = 6.8Hz, 2H), 3.16 (q, J = 6.8 Hz, 2H), 3.59 (bs, 2H), 4.56 (bs, 1H), 6.67 (d, J = 8.0Hz, 2H), 6.96 (d, J = 8.0Hz, 2H).

Third Step: Synthesis of Compound (1-b) A 100 ml four-necked flask was placed in a nitrogen atmosphere, and 2.40 g (15.38 mmol) of 1,3DM-CBDE-Cl was added thereto, followed by 10 ml of tetrahydrofuran (dehydrated). , 1.29 g (16.24 mmol) of pyridine was added and stirred to obtain an acid chloride solution. Next, 4.07 g (16.24 mmol) of the precursor (1-b2) was placed in a 50 ml Erlenmeyer flask, and then 10 ml of tetrahydrofuran (dehydrated) was added to obtain a monoamine solution. This monoamine solution was transferred to a dropping funnel, and the monoamine solution was dropped into a four-necked flask over 5 minutes. After dropping, the mixture was stirred for 3 hours. After 20 hours, the reaction solution was poured into 60 ml of water and extracted by adding 40 ml of chloroform. The obtained organic layer was washed twice with pure water and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off to obtain a white solid. The obtained solid was purified by silica gel column chromatography (ethyl acetate: hexane = 1: 1) to obtain a white solid. It was confirmed that the white solid obtained from ¹ HNMR was the compound (1-b). The yield was 3.72 g, and the yield was 66.9%.
¹ H NMR (400MHz, DMSO-d6, δppm): 1.43 (s, 18H), 1.58 (s, 6H), 1.67 (quin, J = 6.8Hz, 4H), 2.55 (m, 4H), 2.97 (q, J = 6.8Hz, 4H), 3,59 (s, 6H), 3.62 (s, 2H), 6.86 (t, J = 6.8Hz, 2H), 7.16 (d, J = 8.0Hz, 4H), 7.45 ( d, J = 8.0Hz, 4H), 9.43 (s, 2H).

以下に、３ステップの経路で化合物（１−ｃ）を合成した。Example 3 Synthesis of Compound (1-c)

Hereinafter, compound (1-c) was synthesized by a three-step route.

２Ｌ四つ口フラスコに３−ブロモプロピルアミン臭化水素酸塩を５０．４２ｇ（０．２３０ｍｏｌ）入れ、ジクロロメタンを６７２ｇ、二炭酸ジ−ｔｅｒｔ−ブチルを５６．２８ｇ（０．２５８ｍｏｌ）加え、０℃（氷浴）にて撹拌した。滴下ロートにＮ，Ｎ−ジジイソプロピルエチルアミンを６０．８６ｇ（０．４７１ｍｏｌ）入れ、四つ口フラスコ中のスラリー溶液へ３０分かけて滴下した。滴下開始後、反応溶液が激しく発泡し、白色固体が析出した。滴下終了後、３時間撹拌した。反応終了後、反応溶液に純水５００ｍｌを加え、抽出した。得られた有機層を純水で２回洗浄し、無水硫酸マグネシウムで乾燥した。乾燥剤を除去後、溶媒留去し、無色透明のオイルを得た。このオイル状物質にヘキサン５００ｍｌを加え、−７８℃で晶析し、白色固体を得た。固体を吸引ろ取し、減圧乾燥した。^１ＨＮＭＲより得られた白色固体がｔｅｒｔ−ブチル−３−ブロモプロピルカルバメート、すなわち前駆体（１−ｃ１）であることを確認した。収量は４２．９９ｇ、収率は７８．５％であった。
¹H NMR (400MHz, CDCl₃, δppm)：1.44(s, 9H), 2.05(quin, J=6.4Hz, 2H), 3.27(q, J=6.4Hz, 2H), 3.45(t, J=6.4Hz,2H), 4.69(bs, 1H).First step: synthesis of precursor (1-c1)

In a 2 L four-necked flask, 50.42 g (0.230 mol) of 3-bromopropylamine hydrobromide was added, 672 g of dichloromethane and 56.28 g (0.258 mol) of di-tert-butyl dicarbonate were added. Stir at ° C (ice bath). 60.86 g (0.471 mol) of N, N-didiisopropylethylamine was placed in the dropping funnel and added dropwise to the slurry solution in the four-necked flask over 30 minutes. After the start of dropping, the reaction solution foamed vigorously and a white solid was precipitated. It stirred for 3 hours after completion | finish of dripping. After completion of the reaction, 500 ml of pure water was added to the reaction solution and extracted. The obtained organic layer was washed twice with pure water and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off to obtain a colorless and transparent oil. To this oily substance, 500 ml of hexane was added and crystallized at -78 ° C. to obtain a white solid. The solid was filtered off with suction and dried under reduced pressure. It was confirmed that the white solid obtained from ¹ HNMR was tert-butyl-3-bromopropylcarbamate, that is, the precursor (1-c1). The yield was 42.99 g, and the yield was 78.5%.
¹ H NMR (400MHz, CDCl ₃ , δppm): 1.44 (s, 9H), 2.05 (quin, J = 6.4Hz, 2H), 3.27 (q, J = 6.4Hz, 2H), 3.45 (t, J = 6.4 Hz, 2H), 4.69 (bs, 1H).

１Ｌ四つ口フラスコに前駆体（１−ｃ１）を４０．００ｇ（０．１６８ｍｏｌ）、炭酸カリウムを３２．８６ｇ（０．２３８ｍｏｌ）入れ、ＤＭＦを４８１ｇ加えて、６０℃にて７時間加熱撹拌した。７時間後、得られた反応溶液を３Ｌの純水に撹拌しながら投入し、酢酸エステルを１Ｌ加え、抽出した。得られた有機層を純水で２回、１Ｍ水酸化ナトリウム水溶液５００ｍｌで洗浄し、無水硫酸マグネシウムで乾燥した。乾燥剤を除去後、溶媒留去し、黄色固体を得た。得られた固体を酢酸エステル２００ｍｌに溶解し、撹拌しながらヘキサンを１Ｌ加えて、固体を析出された。得られた固体を吸引ろ取し、減圧乾燥した。^１ＨＮＭＲより得られた黄色固体が前駆体（１−ｃ２）であることを確認した。収量は３５．４９ｇ、収率は７１．３％であった。
¹H NMR (400MHz, CDCl₃, δppm)：1.44(s, 9H), 2.03(quin, J=6.4Hz, 2H), 3.34(q, J=6.4Hz, 2H), 4.12(t, J=6.4Hz, 2H), 4.72(bs, 1H), 6.95(d, 8.0Hz, 2H), 8.20(d, 8.0Hz, 2H).Second step: Synthesis of precursor (1-c2)

Add 40.00 g (0.168 mol) of precursor (1-c1) and 32.86 g (0.238 mol) of potassium carbonate to a 1 L four-necked flask, add 481 g of DMF, and heat and stir at 60 ° C. for 7 hours. did. After 7 hours, the obtained reaction solution was poured into 3 L of pure water with stirring, and 1 L of acetate was added for extraction. The obtained organic layer was washed twice with pure water with 500 ml of 1M aqueous sodium hydroxide solution and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off to obtain a yellow solid. The obtained solid was dissolved in 200 ml of acetic ester, and 1 L of hexane was added with stirring to precipitate a solid. The obtained solid was collected by suction filtration and dried under reduced pressure. It was confirmed that the yellow solid obtained from ¹ HNMR was the precursor (1-c2). The yield was 35.49 g, and the yield was 71.3%.
¹ H NMR (400MHz, CDCl ₃ , δppm): 1.44 (s, 9H), 2.03 (quin, J = 6.4Hz, 2H), 3.34 (q, J = 6.4Hz, 2H), 4.12 (t, J = 6.4 Hz, 2H), 4.72 (bs, 1H), 6.95 (d, 8.0Hz, 2H), 8.20 (d, 8.0Hz, 2H).

５００ｍｌナス型フラスコに前駆体（１−ｃ２）を３０．０４ｇ（０．１０２ｍｏｌ）を入れ、エタノール１７０ｇを加えた。反応容器を窒素置換した後、パラジウムカーボンを３．１１ｇ加え、窒素置換した。反応容器を水素置換し、２０℃にて、４８時間撹拌した。反応終了後、セライトろ過により、パラジウムカーボンを除去し、ろ液から溶媒を除去し、固体を得た。得られた固体を酢酸エステル１００ｍｌに溶解し、撹拌しながらヘキサンを４００ｍｌ加え、さらに−５０℃に冷却することにより、白色固体が析出した。析出した固体を吸引ろ取し、減圧乾燥した。^１ＨＮＭＲより得られた黄色固体が前駆体（１−ｃ３）であることを確認した。収量は２６．６４ｇ、収率は９７．７％であった。
¹H NMR (400MHz, CDCl₃, δppm)：1.44(s, 9H), 1.93(quin, J=6.4Hz, 2H), 3.32(q, J=6.4Hz, 2H), 3.44(bs, 2H), 3.94(t, J=6.4Hz,2H), 4.85(bs, 1H), 6.63(d, 8.0Hz, 2H), 6.73(d, 8.0Hz, 2H).Third step: Synthesis of precursor (1-c3)

30.04 g (0.102 mol) of the precursor (1-c2) was placed in a 500 ml eggplant-shaped flask, and 170 g of ethanol was added. After the reaction vessel was purged with nitrogen, 3.11 g of palladium carbon was added and purged with nitrogen. The reaction vessel was purged with hydrogen and stirred at 20 ° C. for 48 hours. After completion of the reaction, palladium carbon was removed by Celite filtration, and the solvent was removed from the filtrate to obtain a solid. The obtained solid was dissolved in 100 ml of acetic ester, 400 ml of hexane was added with stirring, and the mixture was further cooled to −50 ° C. to precipitate a white solid. The precipitated solid was collected by suction filtration and dried under reduced pressure. It was confirmed that the yellow solid obtained from ¹ HNMR was the precursor (1-c3). The yield was 26.64 g and the yield was 97.7%.
¹ H NMR (400MHz, CDCl ₃ , δppm): 1.44 (s, 9H), 1.93 (quin, J = 6.4Hz, 2H), 3.32 (q, J = 6.4Hz, 2H), 3.44 (bs, 2H), 3.94 (t, J = 6.4Hz, 2H), 4.85 (bs, 1H), 6.63 (d, 8.0Hz, 2H), 6.73 (d, 8.0Hz, 2H).

Fourth Step: Synthesis of Compound (1-c) A 300 ml four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 12.26 g (46.0 mmol) of the precursor (1-c3) was added, 241 g of NMP was used as the base 5.31 g (67.1 mmol) of pyridine was added and dissolved by stirring. Next, while stirring the monoamine solution, 7.43 g (22.9 mol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. The obtained reaction solution was poured into 1800 g of water with stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 1800 g of water, once with 1800 g of ethanol, and three times with 540 g of ethanol. A white solid was obtained. The obtained white solid was dissolved in ethyl acetate, and hexane was added for recrystallization. The precipitated solid was collected by suction filtration and dried under reduced pressure. It was confirmed that the yellow solid obtained from ¹ HNMR was the precursor (1-c). The yield was 15.23 g, and the yield was 84.4%.
¹ H NMR (400MHz, CDCl ₃ δppm): 1.44 (s, 18H), 1.58 (s, 6H), 1.97 (quin, J = 6.4Hz, 4H), 3.31 (q, J = 6.4Hz, 4H), 3.85 (s, 6H), 3.99 (t, J = 6.4Hz, 4H), 4.80 (bs, 2H), 6.85 (d, 8.0Hz, 4H), 7.42 (d, 8.0Hz, 4H), 8.50 (s, 2H ).

撹拌装置付きの３００ｍｌ四つ口フラスコを窒素雰囲気とし、２，５−ビス（メトキシカルボニル）テレフタル酸を１．８７ｇ（６．６３ｍｍｏｌ）、ピリジンを１．１０ｇ（１３．９ｍｍｏｌ）を入れ、脱水テトラヒドロフランを４０ｍｌ加え、加熱還流した。この溶液に塩化チオニルを１．５４ｇ（１２．９ｍｍｏｌ）加え、１時間加熱還流した。１時間後、反応溶液に前駆体（１−ａ２）を３．１３g (１９．５６ｍｍｏｌ)入れ、さらに２時間加熱還流した。得られた反応溶液を、５００ｇ の水に撹拌しながら投入し、析出した白色沈殿をろ取し、続いて、５００ｇ の水で１回、５００g のメタノールで１回、２４０g のメタノールで３回洗浄し、白色固体を得た。得られた白色固体を２００ｍｌナス型フラスコに入れ、酢酸エチル１００ｍｌを加えて、加熱撹拌した。残った固体を吸引ろ取し、減圧乾燥した。^１ＨＮＭＲより得られた白色固体が化合物（１−ｄ）であることを確認した。収量は１．９７ｇ、収率は４１．４％であった。
¹H NMR (400MHz, DMSO-d6 δppm)：1.38(s, 18H), 2.67(t, J=8.0Hz, 4H) , 3.13(q J=8.0Hz, 4H), 3.81(s, 6H), 6.89(t, J=5.6Hz,2H), 7.18(d, 8.8Hz, 4H), 7.42(d, 8.8Hz, 4H), 8.03(s,2H), 10.56(s, 2H).Example 4 Synthesis of Compound (1-d)

A 300 ml four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 1.87 g (6.63 mmol) of 2,5-bis (methoxycarbonyl) terephthalic acid and 1.10 g (13.9 mmol) of pyridine were added thereto. Was added and heated to reflux. To this solution, 1.54 g (12.9 mmol) of thionyl chloride was added and heated under reflux for 1 hour. After 1 hour, 3.13 g (19.56 mmol) of the precursor (1-a2) was added to the reaction solution, and the mixture was further heated to reflux for 2 hours. The obtained reaction solution was poured into 500 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 500 g of water, once with 500 g of methanol, and three times with 240 g of methanol. A white solid was obtained. The obtained white solid was put into a 200 ml eggplant type flask, 100 ml of ethyl acetate was added, and the mixture was heated and stirred. The remaining solid was collected by suction filtration and dried under reduced pressure. It was confirmed that the white solid obtained from ¹ HNMR was the compound (1-d). The yield was 1.97 g, and the yield was 41.4%.
¹ H NMR (400MHz, DMSO-d6 δppm): 1.38 (s, 18H), 2.67 (t, J = 8.0Hz, 4H), 3.13 (q J = 8.0Hz, 4H), 3.81 (s, 6H), 6.89 (t, J = 5.6Hz, 2H), 7.18 (d, 8.8Hz, 4H), 7.42 (d, 8.8Hz, 4H), 8.03 (s, 2H), 10.56 (s, 2H).

撹拌装置付きの３０ｍｌ四つ口フラスコを窒素雰囲気とし、前駆体（１−ａ２）を１．０４g (４．４２ｍｍｏｌ)入れ、NMPを２０g、塩基としてピリジンを０．５８g （７．４３ｍｍｏｌ) 加え撹拌して溶解させた。次にこのモノアミン溶液を撹拌しながらＣＢＤＥ−Ｃｌを０．６５８g （２．２２ｍｏｌ）添加し、水冷下２時間反応させた。得られた反応溶液を、２００g の水に撹拌しながら投入し、析出した白色沈殿をろ取し、続いて、２００ｇ の水で１回、２００g のエタノールで１回、１００g のエタノールで３回洗浄し、白色固体を得た。得られた白色固体を５０ｍｌナス型フラスコに入れ、酢酸エチルを３０ｍｌ加え、８０℃にて３０分間加熱撹拌した。３０分後、残った固体を吸引ろ取し、減圧乾燥した。^１ＨＮＭＲより得られた白色固体が前駆体（１−ｊ）であることを確認した。収量は０．４２ｇ、収率は２７．３％であった。
¹H NMR (400MHz, DMSO-d6 δppm)：1.33(s, 18H), 1.58(s, 6H), 2.59(t, J=7.2Hz, 4H) , 3.06(q, J=7.2Hz, 4H), 3.47(s, 6H),3.56〜3.63(m,2H), 3.86〜3.91(m,2H),6.83(t, J=5.6Hz, 4H), 7.08(d, 8.4Hz, 4H), 7.43(d, 8.4Hz, 4H), 10.10(s,2H).Example 5 Synthesis of Compound (1-j)

A 30 ml four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 1.04 g (4.42 mmol) of the precursor (1-a2) was added, 20 g of NMP, and 0.58 g (7.43 mmol) of pyridine as a base were added and stirred. And dissolved. Next, while stirring this monoamine solution, 0.658 g (2.22 mol) of CBDE-Cl was added and reacted for 2 hours under water cooling. The obtained reaction solution was poured into 200 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 200 g of water, once with 200 g of ethanol, and three times with 100 g of ethanol. A white solid was obtained. The obtained white solid was put into a 50 ml eggplant type flask, 30 ml of ethyl acetate was added, and the mixture was heated and stirred at 80 ° C. for 30 minutes. After 30 minutes, the remaining solid was filtered off with suction and dried under reduced pressure. It was confirmed that the white solid obtained from ¹ HNMR was the precursor (1-j). The yield was 0.42 g, and the yield was 27.3%.
¹ H NMR (400MHz, DMSO-d6 δppm): 1.33 (s, 18H), 1.58 (s, 6H), 2.59 (t, J = 7.2Hz, 4H), 3.06 (q, J = 7.2Hz, 4H), 3.47 (s, 6H), 3.56 to 3.63 (m, 2H), 3.86 to 3.91 (m, 2H), 6.83 (t, J = 5.6Hz, 4H), 7.08 (d, 8.4Hz, 4H), 7.43 (d , 8.4Hz, 4H), 10.10 (s, 2H).

撹拌装置付きの３０ｍｌ四つ口フラスコを窒素雰囲気とし、前駆体（１−ｃ３）を１．０６g (３．９９ｍｍｏｌ)入れ、NMPを２０g、塩基としてピリジンを０．５８g （７．４３ｍｍｏｌ) 加え撹拌して溶解させた。次にこのモノアミン溶液を撹拌しながらＣＢＤＥ−Ｃｌを０．６５８g （１．９９ｍｏｌ）添加し、水冷下２時間反応させた。得られた反応溶液を、２００g の水に撹拌しながら投入し、析出した白色沈殿をろ取し、続いて、２００ｇ の水で１回、２００g のエタノールで１回、１００g のエタノールで３回洗浄し、白色固体を得た。得られた白色固体を５０ｍｌナス型フラスコに入れ、酢酸エチルを３０ｍｌ加え、８０℃にて３０分間加熱撹拌した。３０分後、残った固体を吸引ろ取し、減圧乾燥した。^１ＨＮＭＲより得られた白色固体が前駆体（１−ｋ）であることを確認した。収量は０．５８ｇ、収率は３８．４％であった。
¹H NMR (400MHz, DMSO-d6 δppm)：1.44(s, 18H), 1.79(quin, J=6.4Hz, 4H) , 3.06(q, J=6.4Hz, 4H), 3.60(s, 6H), 3.59〜3.66(m, 2H), 3.86〜3.96(m, 6H), 6.86(d, 8.0Hz, 4H), 6.90(t, J=6.4Hz, 2H), 7.46(d, 8.0Hz, 4H), 10.06(s,2H).Example 6 Synthesis of Compound (1-k)

A 30 ml four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 1.06 g (3.99 mmol) of the precursor (1-c3) was added, 20 g of NMP, and 0.58 g (7.43 mmol) of pyridine as a base were added and stirred. And dissolved. Next, while stirring this monoamine solution, 0.658 g (1.99 mol) of CBDE-Cl was added and reacted for 2 hours under water cooling. The obtained reaction solution was poured into 200 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 200 g of water, once with 200 g of ethanol, and three times with 100 g of ethanol. A white solid was obtained. The obtained white solid was put into a 50 ml eggplant type flask, 30 ml of ethyl acetate was added, and the mixture was heated and stirred at 80 ° C. for 30 minutes. After 30 minutes, the remaining solid was filtered off with suction and dried under reduced pressure. ^The white solid obtained from ¹ HNMR was confirmed to be the precursor (1-k). The yield was 0.58 g, and the yield was 38.4%.
¹ H NMR (400MHz, DMSO-d6 δppm): 1.44 (s, 18H), 1.79 (quin, J = 6.4Hz, 4H), 3.06 (q, J = 6.4Hz, 4H), 3.60 (s, 6H), 3.59 ~ 3.66 (m, 2H), 3.86 ~ 3.96 (m, 6H), 6.86 (d, 8.0Hz, 4H), 6.90 (t, J = 6.4Hz, 2H), 7.46 (d, 8.0Hz, 4H), 10.06 (s, 2H).

撹拌装置付きの５０ｍｌ二口フラスコを窒素雰囲気とし、２，５−ビス（メトキシカルボニル）テレフタル酸を０．６２ｇ（２．２０ｍｍｏｌ）、ピリジンを０．３８ｇ（４．８０ｍｍｏｌ）を入れ、脱水テトラヒドロフランを２０ｍｌ加え、加熱還流した。この溶液に塩化チオニルを０．５５ｇ（４．６２ｍｍｏｌ）加え、１時間加熱還流した。１時間後、反応溶液に前駆体（１−ｃ３）を１．２３g (４．６２ｍｍｏｌ)入れ、さらに２時間加熱還流した。得られた反応溶液を、２００ｇ の水に撹拌しながら投入し、析出した白色沈殿をろ取し、続いて、１００ｇ の水で１回、１００g のエタノールで１回、５０g のエタノールで３回洗浄し、淡黄色固体を得た。得られた淡黄色固体を５０ｍｌナス型フラスコに入れ、酢酸エチルを２０ｍｌ加えて、加熱撹拌した。残った固体を吸引ろ取し、減圧乾燥した。^１ＨＮＭＲより得られた白色固体が化合物（１−ｉ）であることを確認した。収量は０．５７ｇ、収率は３３．１％であった。
¹H NMR (400MHz, DMSO-d6 δppm)：1.38(s, 18H), 1.83(quin, J=6.4Hz, 4H), 3.08(q J=6.4Hz, 4H), 3.81(s, 6H), 3.96(t, J=6.4Hz, 4H), 6.86〜7.00(m, 6H), 7.58(d, 7.2Hz, 4H), 8.02(s,2H), 10.47(s, 2H).Example 7 Synthesis of Compound (1-i)

A 50 ml two-necked flask equipped with a stirrer is placed in a nitrogen atmosphere, 0.62 g (2.20 mmol) of 2,5-bis (methoxycarbonyl) terephthalic acid and 0.38 g (4.80 mmol) of pyridine are added, and dehydrated tetrahydrofuran is added. 20 ml was added and heated to reflux. To this solution, 0.55 g (4.62 mmol) of thionyl chloride was added and heated to reflux for 1 hour. After 1 hour, 1.23 g (4.62 mmol) of the precursor (1-c3) was added to the reaction solution, and the mixture was further heated to reflux for 2 hours. The obtained reaction solution was poured into 200 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 100 g of water, once with 100 g of ethanol, and three times with 50 g of ethanol. To obtain a pale yellow solid. The obtained pale yellow solid was put into a 50 ml eggplant type flask, 20 ml of ethyl acetate was added, and the mixture was heated and stirred. The remaining solid was collected by suction filtration and dried under reduced pressure. It was confirmed that the white solid obtained from ¹ HNMR was compound (1-i). The yield was 0.57 g, and the yield was 33.1%.
¹ H NMR (400MHz, DMSO-d6 δppm): 1.38 (s, 18H), 1.83 (quin, J = 6.4Hz, 4H), 3.08 (q J = 6.4Hz, 4H), 3.81 (s, 6H), 3.96 (t, J = 6.4Hz, 4H), 6.86 ~ 7.00 (m, 6H), 7.58 (d, 7.2Hz, 4H), 8.02 (s, 2H), 10.47 (s, 2H).

撹拌装置付き及び窒素導入管付きの５０ｍＬ四つ口フラスコに、前駆体（１−ａ２）を２．３７ｇ（１０．０３ｍｍｏｌ）入れ、次いで、ＮＭＰを９．４０ｇ加えて、窒素を送りながら撹拌し、モノアミン溶液とした。このモノアミン溶液を撹拌しながら、ＣＢＤＡを０．９８ｇ（５．００ｍｍｏｌ）添加し、更に固形分濃度が２０質量％になるようにＮＭＰを加え、室温で２４時間撹拌して化合物（１−ｅ）含有溶液を得た。
得られた溶液の一部に対し、１−メチル−３−ｐ−トリルトリアゼンを加えて、カルボン酸のメチルエステル化を行ったところ、^１ＨＮＭＲより実施例５で得られた（１−ｊ）と同一の化合物が得られたことを確認した。このことから、上記溶液には、（１−ｅ）が含まれることが確認された。(Example 8) Preparation of a solution containing compound (1-e)

2.37 g (10.03 mmol) of the precursor (1-a2) was placed in a 50 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, and then 9.40 g of NMP was added and stirred while feeding nitrogen. A monoamine solution was obtained. While stirring the monoamine solution, 0.98 g (5.00 mmol) of CBDA was added, NMP was further added so that the solid content concentration was 20% by mass, and the mixture was stirred at room temperature for 24 hours to obtain the compound (1-e). A containing solution was obtained.
When 1-methyl-3-p-tolyltriazene was added to a part of the obtained solution to carry out methyl esterification of carboxylic acid, it was obtained in Example 5 from ¹ HNMR (1-j It was confirmed that the same compound was obtained. From this, it was confirmed that the solution contains (1-e).

撹拌装置付き及び窒素導入管付きの５０ｍＬ四つ口フラスコに、前駆体（１−ａ２）を２．３７ｇ（１０．０３ｍｍｏｌ）入れ、次いで、ＮＭＰを９．６２ｇ加えて、窒素を送りながら撹拌し、モノアミン溶液とした。このモノアミン溶液を撹拌しながら、ＰＭＤＡを１．０９ｇ（５．００ｍｍｏｌ）添加し、更に固形分濃度が２０質量％になるようにＮＭＰを加え、室温で２４時間撹拌して化合物（１−ｆ）含有溶液を得た。
得られた溶液の一部に対し、１−メチル−３−ｐ−トリルトリアゼンを加えて、カルボン酸のメチルエステル化を行ったところ、^１ＨＮＭＲより実施例４で得られた（１−ｄ）と同一の化合物が得られたことを確認した。このことから、上記溶液には、（１−ｆ）が含まれることが確認された。Example 9 Preparation of Compound (1-f) -Containing Solution

2.37 g (10.03 mmol) of the precursor (1-a2) was placed in a 50 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, and then 9.62 g of NMP was added and stirred while feeding nitrogen. A monoamine solution was obtained. While stirring this monoamine solution, 1.09 g (5.00 mmol) of PMDA was added, NMP was further added so that the solid concentration was 20% by mass, and the mixture was stirred at room temperature for 24 hours to give compound (1-f). A containing solution was obtained.
When 1-methyl-3-p-tolyltriazene was added to a part of the obtained solution to carry out methyl esterification of carboxylic acid, it was obtained in Example 4 from ¹ HNMR (1-d It was confirmed that the same compound was obtained. From this, it was confirmed that the above solution contains (1-f).

撹拌装置付き及び窒素導入管付きの５０ｍＬ四つ口フラスコに、前駆体（１−ｃ３）を２．６６ｇ（９．９９ｍｍｏｌ）入れ、次いで、ＮＭＰを１０．１９ｇ加えて、窒素を送りながら撹拌し、モノアミン溶液とした。このモノアミン溶液を撹拌しながら、ＣＢＤＡを１．０９ｇ（５．００ｍｍｏｌ）添加し、更に固形分濃度が２０質量％になるようにＮＭＰを加え、室温で２４時間撹拌して化合物（１−ｇ）含有溶液を得た。
得られた溶液の一部に対し、１−メチル−３−ｐ−トリルトリアゼンを加えて、カルボン酸のメチルエステル化を行ったところ、^１ＨＮＭＲより実施例６で得られた（１−ｋ）と同一の化合物が得られたことを確認した。このことから、上記溶液には、（１−ｇ）が含まれることが確認された。Example 10 Preparation of Compound (1-g) -Containing Solution

2.66 g (9.99 mmol) of the precursor (1-c3) is placed in a 50 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, and then 10.19 g of NMP is added and stirred while feeding nitrogen. A monoamine solution was obtained. While stirring the monoamine solution, 1.09 g (5.00 mmol) of CBDA was added, NMP was further added so that the solid content concentration was 20% by mass, and the mixture was stirred at room temperature for 24 hours to give compound (1-g). A containing solution was obtained.
When 1-methyl-3-p-tolyltriazene was added to a part of the obtained solution to carry out methyl esterification of carboxylic acid, it was obtained in Example 6 from ¹ HNMR (1-k It was confirmed that the same compound was obtained. From this, it was confirmed that the above solution contains (1-g).

撹拌装置付き及び窒素導入管付きの５０ｍＬ四つ口フラスコに、前駆体（１−ｃ３）を３．９９ｇ（１５．０ｍｍｏｌ）入れ、次いで、ＮＭＰを１６．９１ｇ加えて、窒素を送りながら撹拌し、モノアミン溶液とした。このモノアミン溶液を撹拌しながら、ＰＭＤＡを１．６４ｇ（７．５２ｍｍｏｌ）添加し、更に固形分濃度が２０質量％になるようにＮＭＰを加え、室温で２４時間撹拌して化合物（１−ｈ）含有溶液を得た。
得られた溶液の一部に対し、１−メチル−３−ｐ−トリルトリアゼンを加えて、カルボン酸のメチルエステル化を行ったところ、^１ＨＮＭＲより実施例７で得られた（１−ｉ）と同一の化合物が得られたことを確認した。このことから、上記溶液には、（１−ｈ）が含まれることが確認された。(Example 11) Preparation of a solution containing compound (1-h)

In a 50 mL four-necked flask with a stirrer and a nitrogen inlet tube, 3.99 g (15.0 mmol) of the precursor (1-c3) was added, and then 16.91 g of NMP was added and stirred while feeding nitrogen. A monoamine solution was obtained. While stirring this monoamine solution, 1.64 g (7.52 mmol) of PMDA was added, NMP was further added so that the solid content concentration was 20% by mass, and the mixture was stirred at room temperature for 24 hours to give compound (1-h). A containing solution was obtained.
When 1-methyl-3-p-tolyltriazene was added to a part of the obtained solution to carry out methyl esterification of carboxylic acid, it was obtained in Example 7 from ¹ HNMR (1-i It was confirmed that the same compound was obtained. From this, it was confirmed that the above solution contains (1-h).

(Example 12)
In a 100 ml Erlenmeyer flask, 44.3382 g of the polyamic acid ester solution (PAE-1) obtained in Synthesis Example 3 was added, and then 19.6930 g of GBL and 16.0839 g of BCS were added, and a diluted polyamic acid ester solution was added. Obtained.
5.02 g of the above solution was placed in a 20 ml sample tube containing a stir bar, and then 0.0645 g of the compound (1-a) obtained in Example 1 (0.005 g per 1 mol of the polyamic acid ester repeating unit). 1 mol equivalent) was added, and the mixture was stirred at room temperature for 30 minutes to completely dissolve the compound (1-a) to obtain a liquid crystal aligning agent (A1-1).

(Example 13)
Instead of compound (1-a), compound (1-c) obtained in Example 3 was used in the same manner as in Example 12 except that 0.1 molar equivalent was used per 1 mol of the polyamic acid ester repeating unit. Thus, a liquid crystal aligning agent (A1-2) was obtained.

(Example 14)
Instead of the compound (1-a), the compound (1-e) -containing solution obtained in Example 8 was added in an amount of 0.1 molar equivalent based on 1 mole of the compound (1-e) repeating unit of the polyamic acid ester. The liquid crystal aligning agent (A1-3) was obtained like Example 12 except having added so that it might become.

(Example 15)
Instead of the compound (1-a), the compound (1-f) -containing solution obtained in Example 9 was added in an amount of 0.1 molar equivalent based on 1 mole of the compound (1-f) repeating unit of the polyamic acid ester. The liquid crystal aligning agent (A1-4) was obtained like Example 12 except having added so that it might become.

(Example 16)
Instead of the compound (1-a), the compound (1-g) -containing solution obtained in Example 10 was added in an amount of 0.1 molar equivalent based on 1 mole of the compound (1-g) repeating unit of the polyamic acid ester. The liquid crystal aligning agent (A1-5) was obtained like Example 12 except having added so that it might become.

(Example 17)
Instead of the compound (1-a), the compound (1-h) -containing solution obtained in Example 11 was added in an amount of 0.1 mol equivalent to 1 mol of the polyamic acid ester repeating unit of the compound (1-h). The liquid crystal aligning agent (A1-6) was obtained like Example 12 except having added so that it might become.

(Example 18)
Into a 20-ml sample tube containing a stir bar, 4.4560 g of the polyamic acid ester solution (PAE-2) obtained in Synthesis Example 4 was added, and then 1.8437 g of NMP and 1.5021 g of BCS were added, and further implementation was performed. Add 0.1023 g of compound (1-a) obtained in Example 1 (0.2 mol equivalent to 1 mol of polyamic acid ester repeating unit) and stir at room temperature for 30 minutes to give compound (1-a). It was made to melt | dissolve completely and the liquid crystal aligning agent (A2-1) was obtained.

(Example 19)
Instead of compound (1-a), compound (1-d) obtained in Example 4 was used in the same manner as in Example 18 except that 0.2 molar equivalent was used per 1 mol of the polyamic acid ester repeating unit. Thus, a liquid crystal aligning agent (A2-2) was obtained.

(Example 20)
Instead of the compound (1-a), the compound (1-e) -containing solution obtained in Example 8 was added in an amount of 0.2 molar equivalent based on 1 mol of the polyamic acid ester repeating unit of the compound (1-e). The liquid crystal aligning agent (A2-3) was obtained like Example 18 except having added so that it might become.

(Example 21)
Instead of the compound (1-a), the compound (1-f) -containing solution obtained in Example 9 was added in an amount of 0.2 molar equivalent relative to 1 mol of the polyamic acid ester repeating unit of the compound (1-f). The liquid crystal aligning agent (A2-4) was obtained like Example 18 except having added so that it might become.

(Example 22)
Into a 20-ml sample tube containing a stir bar, 4.4156 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 5 was added, and then 1.3409 g of NMP and 1.4426 g of BCS were added. 0.2113 g of compound (1-a) obtained in 1 (0.2 molar equivalent to 1 mol of polyamic acid repeating unit) was added, and the mixture was stirred at room temperature for 30 minutes to completely dissolve compound (1-a). It was made to melt | dissolve and the liquid crystal aligning agent (A3-1) was obtained.

(Example 23)
Instead of compound (1-a), compound (1-d) obtained in Example 4 was used in the same manner as in Example 22 except that 0.2 molar equivalent was used per 1 mol of the polyamic acid repeating unit. Thus, a liquid crystal aligning agent (A3-2) was obtained.

(Example 24)
Instead of the compound (1-a), the compound (1-e) -containing solution obtained in Example 8 was mixed with 0.2 mole equivalent of the compound (1-e) based on 1 mole of the polyamic acid repeating unit. The liquid crystal aligning agent (A3-3) was obtained like Example 22 except having added so that it might become.

(Example 25)
Instead of the compound (1-a), the compound (1-f) -containing solution obtained in Example 9 was mixed with 0.2 mole equivalent of the compound (1-f) based on 1 mole of the polyamic acid repeating unit. The liquid crystal aligning agent (A3-4) was obtained like Example 22 except having added so that it might become.

(Comparative Example 1)
Into a 20 ml sample tube containing a stir bar, 2.7692 g of the polyamic acid ester solution (PAE-1) obtained in Synthesis Example 3 was added, and then 1.2308 g of GBL and 1.012 g of BCS were added. The mixture was stirred for 30 minutes to obtain a liquid crystal aligning agent (B1-1).

(Comparative Example 2)
Into a 20 ml sample tube containing a stir bar, 4.3431 g of the polyamic acid ester solution (PAE-2) obtained in Synthesis Example 4 was added, and then 1.4722 g of NMP and 1.4589 g of BCS were added at room temperature. The mixture was stirred for 30 minutes to obtain a liquid crystal aligning agent (B2-1).

(Comparative Example 3)
Into a 20 ml sample tube containing a stir bar, 4.7100 g of the polyamic acid ester solution (PAE-2) obtained in Synthesis Example 4 was added, and then 1.5935 g of NMP and 1.5892 g of BCS were added. 0.0985 g of the precursor (1-a2) obtained in Example 1 (0.4 molar equivalent with respect to 1 mol of the polyamic acid ester repeating unit) was added and stirred at room temperature for 30 minutes to obtain a liquid crystal aligning agent. (B2-2) was obtained.

(Comparative Example 4)
To a 20 ml sample tube containing a stir bar, 3.9775 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 5 was added, and then 1.2069 g of NMP and 1.2953 g of BCS were added, and 30 ml at room temperature was added. The mixture was stirred for a minute to obtain a liquid crystal aligning agent (B3-1).

(Comparative Example 5)
Into a 20-ml sample tube containing a stir bar, 4.3645 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 5 was added, and then 1.3462 g of NMP and 1.4297 g of BCS were added. The precursor (1-a2) obtained in Example 1 was added in an amount of 0.1357 g (0.4 molar equivalent with respect to 1 mol of the polyamic acid repeating unit) and stirred at room temperature for 30 minutes to obtain a liquid crystal aligning agent (B3 -2) was obtained.

(Example 26)
The liquid crystal aligning agent (A1-1) obtained in Example 12 was filtered through a 1.0 μm membrane filter, spin-coated on a glass substrate, dried on a hot plate at a temperature of 80 ° C. for 5 minutes, and then 230. The film was baked at 10 ° C. for 10 minutes to obtain an imidized film having a thickness of 100 nm. This coating film was scraped off, an FT-IR spectrum was measured by the ATR method, and the imidization rate was calculated. The results are shown in Table 1.

(Examples 27 to 31)
Using the liquid crystal aligning agents (A1-2) to (A1-6) obtained in Examples 13 to 17, an imidized film was prepared in the same manner as in Example 26, and an FT-IR spectrum was measured. The imidization rate was calculated. The results are shown in Table 1.

(Comparative Example 6)
Using the liquid crystal aligning agent (B1-1) obtained in Comparative Example 1, an imidized film was produced in the same manner as in Example 26, the FT-IR spectrum was measured, and the imidization ratio was calculated. The results are shown in Table 1.

実施例２６〜３１と比較例６の結果より、本発明の化合物は、ポリアミック酸エステルのイミド化反応を促進することが確認された。

From the results of Examples 26 to 31 and Comparative Example 6, it was confirmed that the compound of the present invention promotes the imidization reaction of the polyamic acid ester.

(Example 32)
The liquid crystal aligning agent (A2-1) obtained in Example 18 was filtered through a 1.0 μm membrane filter, spin-coated on a glass substrate, dried on a hot plate at a temperature of 80 ° C. for 5 minutes, then 20 The film was baked at 10 ° C. for 10 minutes to obtain an imidized film having a thickness of 100 nm. This coating film was scraped off, an FT-IR spectrum was measured by the ATR method, and the imidization rate was calculated. The results are shown in Table 2.

(Examples 33 to 35)
Using the liquid crystal aligning agents (A2-2) to (A2-4) of the present invention obtained in Examples 19 to 21, an imidized film was prepared in the same manner as in Example 32, and the FT-IR spectrum was measured. And the imidization ratio was calculated. The results are shown in Table 2.

(Comparative Examples 7-8)
Using the liquid crystal aligning agents (B2-1) and (B2-2) obtained in Comparative Examples 2 and 3, imidized films were prepared in the same manner as in Example 32, and FT-IR spectra were measured. And the imidization ratio was calculated. The results are shown in Table 2.

実施例３２〜３５と比較例７の結果より、本発明の化合物は、ポリアミック酸エステルのイミド化反応を促進することが確認された。また、実施例３４、３５と比較例８の結果より、テトラカルボン酸二無水物と前駆体（１−ａ２）の反応生成物が、ポリアミック酸エステルのイミド化反応を促進することが確認された。

From the results of Examples 32-35 and Comparative Example 7, it was confirmed that the compound of the present invention promotes the imidization reaction of the polyamic acid ester. Moreover, from the results of Examples 34 and 35 and Comparative Example 8, it was confirmed that the reaction product of tetracarboxylic dianhydride and the precursor (1-a2) promotes the imidization reaction of the polyamic acid ester. .

(Example 36)
The liquid crystal aligning agent (A3-1) obtained in Example 22 was filtered through a 1.0 μm membrane filter, spin-coated on a glass substrate with a transparent electrode, and placed on a hot plate at a temperature of 80 ° C. for 5 minutes. After drying, baking was performed at 230 ° C. for 20 minutes to obtain an imidized film having a film thickness of 100 nm. This polyimide film was rubbed with a rayon cloth (roll diameter: 120 mm, rotation speed: 1000 rpm, moving speed: 20 mm / sec, indentation amount: 0.4 mm), and then the surface condition of the polyimide film was observed. No debris or peeling of the polyimide film was observed.

(Example 37)
A polyimide film was produced in the same manner as in Example 36 except that the liquid crystal aligning agent (A3-2) obtained in Example 23 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing, scraping of the polyimide film, and peeling of the polyimide film were not observed.

(Example 38)
A polyimide film was prepared and rubbed in the same manner as in Example 36 except that the liquid crystal aligning agent (A3-3) obtained in Example 24 was used. When the surface state of the polyimide film was observed, scratches due to rubbing, scraping of the polyimide film, and peeling of the polyimide film were not observed.

(Example 39)
A polyimide film was produced in the same manner as in Example 36 except that the liquid crystal aligning agent (A3-4) obtained in Example 25 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing, scraping of the polyimide film, and peeling of the polyimide film were not observed.

(Comparative Example 9)
A polyimide film was produced in the same manner as in Example 36 except that the liquid crystal aligning agent (B3-1) obtained in Comparative Example 4 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing and scraped scraps of the polyimide film were observed.

(Comparative Example 10)
A polyimide film was prepared and rubbed in the same manner as in Example 36 except that the liquid crystal aligning agent (B3-2) obtained in Comparative Example 5 was used. When the surface state of the polyimide film was observed, scratches due to rubbing and scraped scraps of the polyimide film were observed.
From the results of Examples 36 to 39 and Comparative Example 9, by applying and baking a polyamic acid solution to which the compound of the present invention is added, an imidized film excellent in mechanical strength that is hardly damaged by rubbing can be obtained. confirmed. In addition, the results of Examples 38 and 39 and Comparative Example 10 confirm that the reaction product of tetracarboxylic dianhydride and precursor (1-a2) improves the mechanical strength of the resulting imidized film. It was done.

(Example 40)
The liquid crystal aligning agent (A2-1) obtained in Example 18 was filtered through a 1.0 μm membrane filter, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C. for 5 minutes. After the baking for 20 minutes at a temperature of 230 ° C., an imidized film having a film thickness of 100 nm was formed. This coating film is rubbed with a rayon cloth (roll diameter: 120 mm, rotation speed: 300 rpm, moving speed: 20 mm / sec, indentation amount: 0.4 mm), cleaned by irradiating with ultrasonic waves in pure water for 1 minute, and air blown After removing the water droplets at, the substrate was dried at 80 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film.
Two substrates with such a liquid crystal alignment film are prepared, and a 6 μm spacer is sprayed on the liquid crystal alignment film surface of one of the substrates, and then combined so that the rubbing directions of the two substrates are antiparallel, The periphery was sealed and the empty cell having a cell gap of 6 μm was produced. Liquid crystal (MLC-2041, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature, and the liquid crystal cell with the injection port sealed was observed for liquid crystal orientation, pretilt angle measurement, voltage holding ratio measurement, and ion density measurement. Went. The results are shown in Tables 3 and 4 below.

(Example 41)
A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal aligning agent (A2-2) obtained in Example 19 was used. The liquid crystal cell was observed for liquid crystal orientation, pretilt angle measurement, voltage holding ratio measurement, and ion density measurement. The results are shown in Tables 3 and 4 below.

(Example 42)
A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal aligning agent (A3-1) obtained in Example 22 was used. The liquid crystal cell was observed for liquid crystal orientation, pretilt angle measurement, voltage holding ratio measurement, and ion density measurement. The results are shown in Tables 3 and 4.

(Example 43)
A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal aligning agent (A3-2) obtained in Example 23 was used. The liquid crystal cell was observed for liquid crystal orientation, pretilt angle measurement, voltage holding ratio measurement, and ion density measurement. The results are shown in Tables 3 and 4.

(Comparative Example 11)
A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal aligning agent (B2-1) obtained in Comparative Example 2 was used and the firing time was set to 1 hour. The liquid crystal cell was observed for liquid crystal orientation, pretilt angle measurement, voltage holding ratio measurement, and ion density measurement. The results are shown in Tables 3 and 4.

(Comparative Example 12)
A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal aligning agent (B3-1) obtained in Comparative Example 4 was used. The liquid crystal cell was observed for liquid crystal orientation, pretilt angle measurement, voltage holding ratio measurement, and ion density measurement. The results are shown in Tables 3 and 4.

実施例４０〜４３と比較例１１、１２の結果より、本発明の液晶配向膜を用いることで、液晶配向性が良好な液晶表示素子が得られることが確認された。また、本発明の液晶配向膜を用いることにより、プレチルト角が高くなることが確認された。

From the results of Examples 40 to 43 and Comparative Examples 11 and 12, it was confirmed that by using the liquid crystal alignment film of the present invention, a liquid crystal display element having good liquid crystal alignment was obtained. It was also confirmed that the pretilt angle was increased by using the liquid crystal alignment film of the present invention.

実施例４０〜４３と比較例１１、１２の結果より、本発明の液晶配向膜を用いることにより、高温時でも電圧保持率が高く、イオン密度が低い液晶表示素子が得られることが確認された。

From the results of Examples 40 to 43 and Comparative Examples 11 and 12, it was confirmed that by using the liquid crystal alignment film of the present invention, a liquid crystal display element having a high voltage holding ratio and a low ion density was obtained even at high temperatures. .

(Example 44)
The liquid crystal aligning agent (A3-1) obtained in Example 22 was filtered through a 1.0 μm membrane filter, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C. for 5 minutes. After the baking for 20 minutes at a temperature of 230 ° C., an imidized film having a film thickness of 100 nm was formed. The coating surface was irradiated with 1 J / cm ^{2 of} 254 nm ultraviolet light through a polarizing plate to obtain a substrate with a liquid crystal alignment film.
Two substrates with this liquid crystal alignment film are prepared, and a 6 μm spacer is spread on the liquid crystal alignment film surface of one of the substrates, and then the two substrates are combined so that the alignment of the two substrates is antiparallel, leaving a liquid crystal injection port. The periphery was sealed, and an empty cell having a cell gap of 6 μm was produced. Liquid crystal (MLC-2041, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature, and the liquid crystal cell in which the injection port was sealed was observed for liquid crystal orientation, voltage holding ratio measurement, and ion density measurement. The results are shown in Table 5 below.

(Example 45)
A liquid crystal cell was produced in the same manner as in Example 44 except that the liquid crystal aligning agent (A3-2) obtained in Example 23 was used. The liquid crystal cell was observed for liquid crystal orientation, pretilt angle measurement, voltage holding ratio measurement, and ion density measurement. The results are shown in Table 5.

(Comparative Example 13)
A liquid crystal cell was produced in the same manner as in Example 44 except that the liquid crystal aligning agent (B3-1) obtained in Comparative Example 4 was used. The liquid crystal cell was observed for liquid crystal orientation, pretilt angle measurement, voltage holding ratio measurement, and ion density measurement. The results are shown in Table 5.

実施例４４、４５と比較例１３の結果より、本発明の液晶配向膜を用いることにより、光配向においても、良好な液晶配向性を示し、高温でも電圧保持率が高く、イオン密度が低い信頼性に優れた液晶表示素子が得られることが確認された。

From the results of Examples 44 and 45 and Comparative Example 13, by using the liquid crystal alignment film of the present invention, the liquid crystal alignment property is good even in the photo alignment, the voltage holding ratio is high even at high temperature, and the ion density is low. It was confirmed that a liquid crystal display element having excellent properties can be obtained.

According to the liquid crystal aligning agent of the present invention, the mechanical strength is large, the resistance to rubbing treatment is excellent, and the liquid crystal alignment property, in particular, the electrical characteristics such as voltage holding ratio and ion density at high temperature, A highly reliable liquid crystal alignment film giving a high pretilt angle can be formed. As a result, the present invention is widely useful for TN elements, STN elements, TFT liquid crystal elements, and vertical alignment type liquid crystal display elements.
It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2010-123471 filed on May 28, 2010 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (16)

Protected by a polyimide precursor obtained by reacting a diamine compound and a tetracarboxylic acid derivative, and / or a polyimide imidized with the polyimide precursor, and a thermally desorbable group that replaces hydrogen by heating at 80 to 300 ° C. liquid crystal aligning agent characterized by containing a compound which you express by the following formula (1) having an amic acid or amic acid ester structure having an amino group.

(In the formula, X is a tetravalent organic group, R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Z is a structure represented by the following formula (2).)

(In the formula, Z ₁ is a single bond or a divalent organic group having 1 to 30 carbon atoms. R ₂ and R ₃ are each independently a hydrogen atom or a carbon number that may have a substituent. 1 to 30 alkyl groups, alkenyl groups, alkynyl groups, aryl groups, or combinations thereof, which may form a ring structure, and R ₄ may have a hydrogen atom or a substituent and may have 1 to 30 carbon atoms. D ₁ is a thermally leaving group.) The liquid crystal aligning agent of Claim 1 in which the said polyimide precursor has a repeating unit represented by following formula (7).

(Wherein X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, and R ₆ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A ₁ and A ₂ are respectively Independently a hydrogen atom or an optionally substituted alkyl group, alkenyl group or alkynyl group having 1 to 10 carbon atoms. The polyimide precursor and the polyimide are contained in a total amount of 0.5 to 15% by mass in the liquid crystal aligning agent, and an amic acid having an amino group protected by a thermally desorbable group that replaces hydrogen by heating. or amic acid compound is Ru represented by ester formula having the structure (1) is a polyimide precursor and the polyimide precursor recurring unit 1 of the imidized polymer having a repeating unit represented by the before following formula (7) The liquid crystal aligning agent of Claim 2 contained 0.5-50 mol% with respect to a unit. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein said heat-leaving group is tert- butoxycarbonyl group, or a 9-fluorenylmethoxycarbonyl group. The liquid crystal aligning agent in any one of 1-4 whose said X is either selected from the group which consists of a structure represented by a following formula.

Claim 1 is applied to the liquid crystal alignment agent according to any one of 5, the liquid crystal alignment film a film obtained by baking the alignment process. The liquid crystal alignment film according to claim 6 , wherein the alignment treatment is rubbing treatment or irradiation treatment with polarized radiation. The liquid crystal display device having a liquid crystal alignment film according to claim 6 or 7. The compound which has an amic acid or an amic acid ester structure represented by following formula (1).

(In the formula, X is a tetravalent organic group, R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Z is a structure represented by the following formula (2).)

(In the formula, Z ₁ is a single bond or a divalent organic group having 1 to 30 carbon atoms. R ₂ and R ₃ are each independently a hydrogen atom or a carbon number that may have a substituent. 1 to 30 alkyl groups, alkenyl groups, alkynyl groups, aryl groups, or combinations thereof, which may form a ring structure, and R ₄ may have a hydrogen atom or a substituent and may have 1 to 30 carbon atoms. D ₁ is a thermally leaving group.) In the presence of a base , a bischlorocarbonyl compound represented by the following formula (3) and a monoamine compound represented by the following formula (4) have a molar ratio of ( bischlorocarbonyl compound / monoamine compound ) of 1/2 to The compound of Claim 9 obtained by making it react with 1/3.

_{(Wherein, X, Z 1, R 2} , R 3, R 4, and _{D 1} are as defined in previous following formula (1) and (2), _{R 5} represents an alkyl group having 1 to 5 carbon atoms .) The following equation (5) tetracarboxylic acid derivative represented by the monoamine compound represented by the formula of claim 10 (4) in the presence of a condensing agent, the molar ratio of (tetracarboxylic acid derivative / monoamine compound) There a compound according to claim 9 obtainable by reacting at 1 / 2-1 / 3.

(Wherein, X and _{R 5} are as defined before following formula (1) and (3).) A tetracarboxylic dianhydride represented by the following formula (6) and a monoamine compound represented by the formula (4) according to claim 10 have a molar ratio of (tetracarboxylic dianhydride / monoamine compound ): The compound of Claim 9 obtained by making it react by 1 / 2-1 / 3.

(Wherein, X is the same as defined before following formula (1).) A tetracarboxylic acid dihydrate represented by the formula (6) according to claim 12 and a monoamine compound represented by the formula (4) according to claim 10 are converted into (tetracarboxylic dianhydride / monoamine compound). ) molar ratio are reacted in 1 / 2-1 / 3 of the further compound according to claim 9 obtained by esterifying the carboxyl group with an esterifying agent. Before Symbol X is A compound according to any one of claims 9 to 13 is any one selected from the group consisting of structures represented by the following formula.

Before the title compound as claimed in any one of claims 9 to 14 _{R 1} is an alkyl group having 1 to 5 carbon atoms. The compound in any one of following formula (1-a)-(1-o).