JP4847432B2 - Branched oligoimide or branched oligoamic acid containing a functional group capable of thermosetting or photocuring at the terminal and method for producing the same - Google Patents

Description

  The present invention relates to a branched oligoimide or branched oligoamidic acid containing a functional group capable of thermosetting or photocuring at the terminal.

  With the development of the display industry, the demand for liquid crystal displays is greatly increasing because they provide low drive voltage, high resolution, reduced monitor volume, and flat monitors. One of the core technologies in such a liquid crystal display technology is a technology for successfully aligning liquid crystals in a desired direction.

Conventionally, as a normal method for aligning liquid crystals, a contact rubbing method in which a polymer film such as polyimide is applied to a substrate such as glass and the surface is rubbed in a certain direction with fibers such as nylon or polyester is used. used. However, the contact rubbing method may generate fine dust and electrostatic discharge (ESD) when the fiber and the polymer film rub against each other, and may cause a serious problem when manufacturing a liquid crystal panel due to difficulty in the process.
In order to solve the problems of the contact rubbing method as described above, research on the production of a non-contact type liquid crystal alignment film has recently been actively conducted as a new method.

  As a manufacturing method of the non-contact type liquid crystal alignment film, there are a photo alignment method, an energy beam alignment method, a vapor deposition alignment method, an etching method using lithography, and the like. Among these methods, the most realistic method has emerged: the photosensitive polymer thin film is irradiated with linearly polarized light to cause an anisotropic chemical reaction, resulting in liquid crystal alignment. Is a photo-alignment method for inducing.

  The photo-alignment method can be divided into a photoisomerization method, a photopolymerization method, a photolysis method, or the like depending on the reaction mechanism. Among these, a photodecomposition method using a polyimide thin film that has already been widely commercialized as a liquid crystal alignment film has attracted much attention. Polyimide used for the photolysis method is a straight polymer. The photolysis method is a method of inducing liquid crystal alignment by selectively photolyzing a polymer main chain that matches linear polarized light, and when a polyimide is decomposed by light, a small unit of decomposition by-product is inevitable. Is generated. Such decomposition by-products can cause very serious problems in alignment stability, long-term reliability, especially in the afterimage plane, when a liquid crystal display is actually manufactured. Such problems of alignment stability, long-term reliability, and afterimage surface have emerged as the biggest problems that hinder commercialization of the photoalignment method.

  Accordingly, there is a need for a liquid crystal alignment film that removes a decomposition byproduct of polyimide generated by a photodecomposition method to improve alignment stability, improve long-term reliability and afterimage, and a new liquid crystal substance that can be used therefor.

  Therefore, while the present inventors are studying liquid crystal alignment films with improved alignment stability, long-term reliability, and afterimages, functionalities capable of thermosetting or photocuring at the ends of the branched oligoimide or branched oligoamic acid main chain. It was confirmed that a compound into which a group was introduced could be used as an excellent liquid crystal substance, and the present invention was completed.

  The present invention provides a branched oligoimide or branched oligoamic acid containing a functional group capable of heat curing or photocuring at the terminal represented by the following general formula (1).

前記一般式（１）において、
ＡはＣ３対称またはＣ４対称のアミンであり、
Ｂはオリゴイミドまたはオリゴアミド酸であり、
Ｃは熱硬化または光硬化が可能な官能基であり、
ｎは単位反復体の個数であって、３以上、好ましくは６以下であり、
前記一般式（１）で示される化合物の重量平均分子量は５００〜３０，０００である。

In the general formula (1),
A is a C3 symmetric or C4 symmetric amine;
B is an oligoimide or oligoamic acid,
C is a functional group capable of thermal curing or photocuring,
n is the number of unit repeats and is 3 or more, preferably 6 or less,
The compound represented by the general formula (1) has a weight average molecular weight of 500 to 30,000.

The present invention also provides:
a) a step of producing an oligoimide or oligoamic acid by condensation reaction of diamine and dianhydride;
b) adding a C3 symmetric or C4 symmetric amine to the oligoimide or oligoamic acid; and c) capping a curable functional group at the end of the oligoimide or oligoamic acid bound to the C3 symmetric or C4 symmetric amine. Provided is a method for producing a branched oligoimide or branched oligoamic acid.

  The branched oligoimide or branched oligoamic acid containing a functional group capable of thermosetting or photocuring at the terminal according to the present invention has a functional group capable of thermosetting or photocuring at the terminal of the branched oligoimide or branched oligoamic acid instead of polyimide. By introducing it, it is possible to minimize the generation of decomposition byproducts generated when using polyimide, and it is excellent in coating properties, orientation, thermal stability, and afterimage improvement effects.

Hereinafter, the present invention will be described in detail.
In the compound of the general formula (1) of the present invention, A is an amine having C3 symmetry or C4 symmetry. Here, the C3 symmetry is a group meaning 120 ° symmetry, meaning that there are three reactive groups in one molecule, and the C4 symmetry is a group meaning 90 ° symmetry, This means that there are four reactive groups in one molecule. Preferred examples of C3 symmetric or C4 symmetric amines include, but are not limited to, trisaminophenoxybenzene, trisaminophenylbenzene, trisaminophenylamine, or trisaminoethylamine.

B is an oligoimide or oligoamic acid, which can be produced by a condensation reaction of diamine and dianhydride.
The diamine is preferably an aromatic diamine, and specific examples include phenylenediamine, diaminobiphenyl, methylenedianiline, oxydianiline, thiodianiline, diaminobenzophenone, diaminonaphthalene or diaminoanthracene, but are not limited thereto. It is not something. Examples of the dianhydrides include pyromellitic dianhydride, biphthalic dianhydride, oxydiphthalic dianhydride, benzophenone tetracarboxylic dianhydride, hexafluoroisopropylidenediphthalic dianhydride, cycloalkyl dianhydride, and bicyclo Examples include, but are not limited to, alkyl dianhydrides.

  C is a functional group capable of thermal curing or photocuring, preferably maleimide, 4-ethynylaniline, nadimide, propargyl ether, acetylene, benzocyclobutane or cyanate, more preferably maleimide, 4-ethynylaniline.

  n means the number of oligoimide or oligoamic acid bonded according to the number of reactive groups of A. For example, in a branched oligoimide or branched oligoamic acid in which maleimide is introduced as a functional group capable of thermal curing or photocuring, when A is C3 symmetrical, that is, n = 3, it can be represented by the general formula (2). When A is C4 symmetrical, that is, n = 4, it can be represented by the general formula (3).

前記一般式（２）または一般式（３）において、ＸおよびＹは互いに独立して水素、炭素数１〜６個のアルキル、アリール、ハロゲンまたはニトリルである。

In the general formula (2) or the general formula (3), X and Y are each independently hydrogen, alkyl having 1 to 6 carbon atoms, aryl, halogen, or nitrile.

  The branched oligomer or branched oligoamic acid containing a functional group capable of heat curing or photocuring at the terminal of the present invention is a polymer produced by polymerizing at a low degree of unit, and the weight average molecular weight is 500-30, It is preferable that it exists in the range of 000, More preferably, it is 2,000-10,000.

The present invention also provides:
a) a step of producing an oligoimide or oligoamic acid by condensation reaction of diamine and dianhydride;
b) adding a C3 symmetric or C4 symmetric amine to the oligoimide or oligoamic acid; and c) capping a curable functional group at the end of the oligoimide or oligoamic acid bound to the C3 symmetric or C4 symmetric amine. Provided is a method for producing a branched oligoimide or branched oligoamic acid.

  The a) is a step of producing an oligoimide or oligoamic acid by subjecting a diamine and dianhydride to a condensation reaction. The diamine is preferably an aromatic diamine, and specific examples include phenylenediamine, diaminobiphenyl, methylenedianiline, oxydianiline, thiodianiline, diaminobenzophenone, diaminonaphthalene, or diaminoanthracene. It is not something. As dianhydrides, pyromellitic dianhydride, biphthalic dianhydride, oxydiphthalic dianhydride, benzophenone tetracarboxylic dianhydride, hexafluoroisopropylidenediphthalic dianhydride, cycloalkyl dianhydride or bicycloalkyl Although there are dianhydrides, it is not limited to them.

  The b) is a step of adding a C3 symmetric or C4 symmetric amine to form a branched structure in the prepared oligoimide or oligoamic acid. Examples of the C3 symmetric or C4 symmetric amine added to form the branched structure include trisaminophenoxybenzene, trisaminophenylbenzene, trisaminophenylamine, and trisaminoethylamine, but are not limited thereto. Absent.

  The c) is a step of capping a curable functional group at the end of the oligoimide or oligoamic acid bonded to the C3 symmetric or C4 symmetric amine. Examples of the curable functional group capped at the terminal of the C3 symmetric or C4 symmetric amine include, but are not limited to, maleimide, 4-ethynylaniline, nadimide, propargyl ether, acetylene, benzocyclobutane or cyanate. is not.

  In general, when polyimide is decomposed by light, a small unit of decomposition by-product is generated. However, the branched oligoimide or branched oligoamic acid decomposition by-product generated by photolysis is polymerized again through the subsequent curing step of the curable functional group and no longer exists as a decomposition by-product. Therefore, there is an excellent improvement effect not only in the alignment stability but also in the afterimage plane when the alignment film is manufactured.

  The form of the branched oligomer or branched oligoamidic acid can further improve the density of the curable functional group compared to the polymer, and has the advantage of maximizing the effect of curing, which is a subsequent process, as well as the weight average compared to the existing oligomer. It has the advantages of having a large molecular weight, excellent coating properties, and a compact and more rigid network structure.

  In addition, the polymer produced by introducing a curable functional group at the end of a branched oligomer or branched oligoamic acid form is a network, and provides a much stronger and more stable alignment film than a linear polymer polyimide. Can do. In addition, polyimide is soluble only in NMP (N-methyl pyrrolidone) solvent, while branched oligoimide or branched oligoamidic acid is soluble in most organic solvents, so the choice of solvent is much more diverse. Polyimide can only be roll-printed, while branched oligoimides can be applied not only to roll-printing but also an ink-jet method, and can be applied in consideration of subsequent process selection for thin film generation.

  Hereinafter, preferred embodiments will be presented to help understanding of the present invention. However, the following examples are provided only for easier understanding of the present invention and are not intended to limit the scope of the present invention.

Production Example 1 Production of C3 Symmetric Amine Functional Group 20.2 g of phloroglucinol was dissolved in 800 ml of DMAc and 40 ml of distilled water, and then 80 g of K ₂ CO ₃ was added thereto and stirred at 130 ° C. for 4 hours. . The reaction solution was cooled at 70 ° C., 75.6 g of 4-chloronitrobenzene was added thereto, and the mixture was stirred under reflux for 12 hours. Thereafter, the excess solvent was removed by distillation under reduced pressure, and the residue was added to a 5 wt% aqueous NaOH solution to obtain a precipitate. The resulting brown precipitate was recrystallized using pyridine and distilled water to obtain 61 g of 1,3,5-tris (4-nitrophenyloxy) benzene. 160 ml of THF was added thereto, followed by stirring under reflux. Subsequently, a solution obtained by mixing 300 g of SnCl ₂ and 300 ml of HCl was slowly added during 1 hour, and the mixture was stirred at reflux again for about 8 hours. The solution was cooled at room temperature, added to 1 L of concentrated HCl, and the precipitate formed was filtered, dissolved again in 100 ml distilled water, and then added to 1 L of 5 wt% NaOH to obtain a precipitate. . The gray precipitate was washed with distilled water many times and dried, and then purified by column chromatography using hexane / ethyl acetate / triethylamine (50/50/1) solvent to obtain 1,3,5-tris ( There were obtained 22.5 g of 4-aminophenyloxy) benzene.
¹ H NMR (DMSO-d6): 4.98 (6H), 5.92 (3H), 6.55 (6H), 6.72 (6H)

Example 1 : Production of branched oligomer 1 solution 3.92 g of cyclobutanetetracarboxylic dianhydride and 3.33 g of 4,4'-oxydianiline were dissolved in 48 ml of NMP, and then stirred at room temperature for 8 hours. Thereafter, a solution prepared by dissolving 0.377 g of 1,3,5-tris (4-aminophenyloxy) benzene synthesized in Preparation Example 1 in 48 ml of NMP was slowly added during 3 hours, and then 4-amino After adding 0.722 g of phenylmaleimide, the mixture was further stirred at room temperature for 8 hours to produce an 8 wt% branched oligomer 1 solution.
¹ H NMR (DMSO-d6): 4.05, 6.30, 6.42, 6.44, 6.67, 6.94, 7.39
Molecular weight 3680

Example 2 Production of Branched Oligomer 2 Solution 3.92 g of cyclobutanetetracarboxylic dianhydride and 3.33 g of 4,4′-oxydianiline were dissolved in 48 ml of NMP, and then stirred at room temperature for 8 hours. Thereafter, a solution prepared by dissolving 0.377 g of 1,3,5-tris (4-aminophenyloxy) benzene synthesized in Preparation Example 1 in 48 ml of NMP was slowly added over 3 hours, and then 4-ethynyl. After adding 0.449 g of aniline, the mixture was further stirred at room temperature for 8 hours to prepare an 8 wt% branched oligomer 2 solution.
¹ H NMR (DMSO-d6): 4.06, 6.33, 6.40, 6.54, 6.78, 6.94, 7.65
Molecular weight 3570

Example 3 Production of Branched Oligomer 3 Solution After dissolving 3.92 g of 4,4′-biphthalic dianhydride and 3.33 g of 4,4′-oxydianiline in 48 ml of NMP, the mixture was stirred at room temperature for 8 hours. Thereafter, a solution prepared by dissolving 0.377 g of 1,3,5-tris (4-aminophenyloxy) benzene synthesized in Preparation Example 1 in 48 ml of NMP was slowly added during 3 hours, and then 4-amino After adding 0.722 g of phenylmaleimide, the mixture was further stirred at room temperature for 8 hours to prepare an 8 wt% branched oligomer 3 solution.
¹ H NMR (DMSO-d6): 6.30, 6.42, 6.44, 6.67, 6.94, 7.39, 8.03, 8.40, 8.56
Molecular weight 4520

Example 4 Production of Branched Oligomer 4 Solution 3.92 g of 4,4′-biphthalic dianhydride and 3.33 g of 4,4′-oxydianiline were dissolved in 48 ml of NMP, and then stirred at room temperature for 8 hours. Thereafter, a solution prepared by dissolving 0.377 g of 1,3,5-tris (4-aminophenyloxy) benzene synthesized in Preparation Example 1 in 48 ml of NMP was slowly added over 3 hours, and then 4-ethynyl. After adding 0.449 g of aniline, the mixture was further stirred at room temperature for 8 hours to produce an 8 wt% branched oligomer 4 solution.
¹ H NMR (DMSO-d6): 6.32, 6.41, 6.45, 6.71, 7.01, 7.32, 8.07, 8.43, 8.59
Molecular weight 4410

Example 5 : Production of branched oligomer 5 solution After dissolving 4.92 g of 4,4'-biphthalic dianhydride and 3.33 g of 4,4'-diaminobiphenyl in 48 ml of NMP, the mixture was stirred at room temperature for 8 hours. Thereafter, a solution prepared by dissolving 0.377 g of 1,3,5-tris (4-aminophenyloxy) benzene synthesized in Preparation Example 1 in 48 ml of NMP was slowly added during 3 hours, and then 4-amino After adding 0.722 g of phenylmaleimide, the mixture was further stirred at room temperature for 8 hours to prepare an 8 wt% branched oligomer 3 solution.
¹ H NMR (DMSO-d6): 6.30, 6.44, 6.52, 6.94, 7.23, 7.39, 8.03, 8.40, 8.56
Molecular weight 5860

Example 6 : Production of branched oligomer 6 solution After dissolving 3.92 g of 4,4'-biphthalic dianhydride and 3.33 g of 4,4'-diaminobiphenyl in 48 ml of NMP, the mixture was stirred at room temperature for 8 hours. Thereafter, a solution prepared by dissolving 0.377 g of 1,3,5-tris (4-aminophenyloxy) benzene synthesized in Preparation Example 1 in 48 ml of NMP was slowly added over 3 hours, and then 4-ethynyl. After adding 0.449 g of aniline, the mixture was further stirred at room temperature for 8 hours to produce an 8 wt% branched oligomer 4 solution.
¹ H NMR (DMSO-d6): 6.31, 6.46, 6.53, 6.97, 7.29, 7.49, 8.13, 8.44, 8.58
Molecular weight 5790

Claims (7)

Branched oligoimide or branched oligoamic acid containing a functional group capable of thermal curing or photocuring at the terminal represented by the general formula (1):

In the general formula (1),
A is a C3-symmetric amine and is trisaminophenoxybenzene, trisaminophenylbenzene, trisaminophenylamine or trisaminoethylamine;
B is an oligoimide or oligoamic acid,
C is a functional group capable of thermal curing or photocuring and is maleimide or 4-ethynylaniline;
n is the number of unit repeats and is 3,
The compound represented by the general formula (1) has a weight average molecular weight of 500 to 30,000,
The bond of AB and CB is each independently an imide bond or an amide bond. The branched oligoimide or branched oligoamic acid according to claim 1, wherein the branched oligoimide or branched oligoamic acid has a weight average molecular weight of 2,000 to 10,000. The branched oligoimide or branched oligoamic acid according to claim 1, wherein the maleimide among the functional groups capable of thermosetting or photocuring is 4-aminophenylmaleimide. a) a step of producing an oligoimide or oligoamic acid by a condensation reaction of diamine and dianhydride;
b) adding to said oligoimide or oligoamic acid a C3 symmetric amine which is trisaminophenoxybenzene, trisaminophenylbenzene, trisaminophenylamine or trisaminoethylamine; and c) at the end of said C3 symmetric amine; maleimide or 4 Echiniruaniri branched oligo-imide represented a thermosetting or photocurable functional group is down by the general formula (1) comprising the step of capping or method of manufacturing a branch oligoamic acid.

In the general formula (1),
A is a C3-symmetric amine and is trisaminophenoxybenzene, trisaminophenylbenzene, trisaminophenylamine or trisaminoethylamine;
B is an oligoimide or oligoamic acid,
C is a functional group capable of thermal curing or photocuring and is maleimide or 4-ethynylaniline;
n is the number of unit repeats and is 3,
The compound represented by the general formula (1) has a weight average molecular weight of 500 to 30,000,
The bond of AB and CB is each independently an imide bond or an amide bond. 5. The branched oligoimide or branched oligoamic acid of claim 4, wherein the diamine is selected from the group consisting of phenylenediamine, diaminobiphenyl, methylenedianiline, oxydianiline, thiodianiline, diaminobenzophenone, diaminonaphthalene, and diaminoanthracene. Production method. The dianhydrides include pyromellitic dianhydride, biphthalic dianhydride, oxydiphthalic dianhydride, benzophenone tetracarboxylic dianhydride, hexafluoroisopropylidenediphthalic dianhydride, cycloalkyl dianhydride, and The method for producing a branched oligoimide or branched oligoamic acid according to claim 4, which is selected from the group consisting of bicycloalkyl dianhydrides. The method for producing a branched oligoimide or branched oligoamic acid according to claim 4, wherein the maleimide of the functional groups capable of thermosetting or photocuring is 4-aminophenylmaleimide.