JP2012180482A - Composition containing maleimide-based polymer, and method for producing copolymer of maleimide-based polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel composition that contains bismaleimide and can also be used for forming a liquid crystal orientation membrane having excellent properties, as well as a novel copolymer of bismaleimide and acidic addition agent, and to provide a method for producing a novel copolymer.SOLUTION: The composition containing a maleimide-based polymer, an additive agent and a solvent is a novel composition, and has excellent properties, therefore is expected to be applied to various uses. Moreover, the copolymer obtained by performing copolymerization of an acidic additive agent with bismaleimide is a novel copolymer and has excellent properties, and is expected to be applied as a novel material.

Description

  The present invention relates to a composition containing a maleimide polymer obtained by polymerization using bismaleimide and diamine, an additive, and a solvent, a method for producing a maleimide polymer copolymer, and a novel maleimide polymer The present invention relates to a molecular copolymer.

One application field of the present invention is a liquid crystal display element.
Liquid crystal display elements are used in various liquid crystal display devices such as monitors for notebook computers and desktop computers, video camera viewfinders, and projection displays. Recently, they have also been used as televisions. . Furthermore, liquid crystal display elements are also used as optoelectronic-related elements such as optical printer heads, optical Fourier transform elements, and light valves.

  The liquid crystal display element usually has 1) a pair of substrates arranged opposite to each other, 2) electrodes formed on one or both of the opposed surfaces of each of the pair of substrates, and 3) each of the pair of substrates. And 4) a liquid crystal layer formed between the pair of substrates.

As the liquid crystal display element, a display element using a nematic liquid crystal is mainly used. As the liquid crystal display element, for example, 1) a TN (twisted nematic) type liquid crystal display element twisted by 90 degrees, and 2) an STN twisted by 180 degrees or more are usually used. Super Twisted Nematic) type liquid crystal display element, 3) So-called TFT (Thin) using a thin film transistor
A film transistor type liquid crystal display element is known. Moreover, as a liquid crystal display element in which the viewing angle in these liquid crystal display elements is further improved, for example, 4) a TN-TFT type liquid crystal display element using an optical compensation film, and 5) a vertical alignment and an optical compensation film. VA (Vertical Alignment) type liquid crystal display element used, 6) MVA (Multi Domain Vertical) using both vertical alignment and protrusion structure technology
Alignment type liquid crystal display element, 7) In-plane switching type IPS (In-Plane Switching) type liquid crystal display element, 8) ECB (Electrically Controlled Birefringence) type liquid crystal display element, and 9) Optically Compensated Bend Optically
A self-compensated birefringence (OCB) type liquid crystal display element is known.

  The development of the technology of the liquid crystal display element is achieved not only by simply improving these driving methods and element structures, but also by improving the components used in the liquid crystal display element. Among the components used in the liquid crystal display element, the liquid crystal alignment film is one of the important elements related to the display quality of the liquid crystal display element. Roles are becoming important year after year.

  The liquid crystal alignment film is formed from a liquid crystal aligning agent. As a typical liquid crystal aligning agent conventionally used, a polyamic acid or a soluble polyimide obtained by reacting a tetracarboxylic anhydride or a derivative thereof with a diamine or a derivative thereof is dissolved in an organic solvent. Solutions are known.

On the other hand, in addition to polyimide, that is, polyamic acid or soluble polyimide, maleimide polymer obtained by reacting bismaleimide and diamine is also used as a liquid crystal aligning agent to form a liquid crystal aligning film having good electro-optical properties. It is known that it can be performed (for example, refer to Patent Document 1).

The polyimide can form various types of molded products such as films, substrates, fibers, and particles by firing, and further add functionality as necessary to form adhesives and separation membranes. In addition, a functional film such as an electrolyte film can be formed. The maleimide polymer is also expected to be applied to such various uses.
In particular, the maleimide polymer is different from the above polyimide, and when forming a molded product, firing at a high temperature for imidization, strict control of firing conditions for obtaining a desired imidization rate, or soluble polyimide A complicated process such as an imidization reaction in a solution for obtaining the above is unnecessary. For this reason, for example, by using a maleimide polymer instead of polyimide, shortening of the process, shortening of working time, improvement of ease of working, or improvement of quality stabilization, etc. are expected, and further improvements are expected. As a result, effects such as reduction in energy required for production or cost reduction are also expected.

  On the other hand, in addition to polyimide, it is known that a composition containing a polymer obtained by reacting bismaleimide and diamine (hereinafter, also referred to as maleimide polymer) can be used as a liquid crystal aligning agent (for example, (See Patent Document 2 and Patent Document 3). When the polymers described in these documents are used, the liquid crystal alignment and electro-optical properties are good. However, the polymerization reaction of bismaleimide and diamine described in these documents must be carried out in a phenolic solvent such as cresol, which is problematic in terms of toxicity and odor. It was not practical to use it as an agent. That is, a phenolic solvent is present in the polymer solution after the polymerization, and in order to remove the phenolic solvent from this solution, the polymer obtained once in a poor solvent such as methanol is precipitated, Complicated operations such as redissolving in a solvent such as N-methyl-2-pyrrolidone and other compositions to prepare a liquid crystal aligning agent are necessary.

  Further, it is known that a composition containing a polymer obtained by reacting bismaleimide and diamine (hereinafter, also referred to as a maleimide polymer), another substance, and a solvent can be used as an adhesive. (For example, refer to Patent Document 4). The polymerization reaction of bismaleimide and diamine described in these documents must also be performed in a phenolic solvent such as cresol, which is problematic in terms of toxicity and odor, and the obtained polymer solution is used as a composition as it is. It was not practical to use. That is, a phenolic solvent is present in the polymer solution after the polymerization, and in order to remove the phenolic solvent from this solution, the polymer obtained once in a poor solvent such as methanol is precipitated, A complicated operation such as redissolving in another solvent to prepare an adhesive composition was necessary. In addition, in this prior art, there is no description or suggestion of an effect relating to excellent electro-optical characteristics, etc., which the liquid crystal aligning agent using the composition of the present invention has.

Japanese Patent Laid-Open No. 07-110483 JP 7-043725 A Japanese Patent Application Laid-Open No. 7-110483 JP 11-246840 A

The present invention provides a novel composition containing a maleimide polymer that can also be used to form a liquid crystal alignment film having good characteristics. Moreover, the manufacturing method of a maleimide-type polymer copolymer and a novel maleimide-type polymer copolymer are provided.

  The present inventors have intensively studied to solve the above problems. As a result, when a composition containing a maleimide polymer, an additive, and a solvent is used as a liquid crystal aligning agent, the electrical properties of the liquid crystal aligning agent are improved and the ion density of the liquid crystal display element is decreased. The headline and the present invention were completed. When the additive is a specific compound, a copolymer obtained by copolymerizing the compound and a maleimide polymer was a novel copolymer. The present invention is as follows.

［８］前記溶剤はアルコール性水酸基を有する溶剤又はプロトン性アミド系溶剤を含有し、溶剤全量に対して前記アルコール性水酸基を有する溶剤又はプロトン性アミド系溶剤を２０重量％以上含有する、［１］〜［７］のいずれかに記載の組成物。
［９］前記マレイミド系高分子は、重合後に溶剤置換する工程を含まない方法で製造された、［１］〜［８］のいずれかに記載の組成物。
［１０］前記添加剤が酸性基の構造、重合性基の構造、及び環状エステルの構造からなる群から選択されるいずれか１種以上の構造を含む、［１］〜［９］のいずれかに記載の組成物。
［１１］前記添加剤が酸性基を含み、該酸性基がカルボキシル基、スルホン酸基、及びフェノール性水性基からなる群から選択されるいずれか１種以上を含む、［１０］に記載の組成物。
［１２］前記添加剤が酸性基を含み、該酸性基を含む添加剤が、ポリアミック酸、ポリエステル酸、及びポリマレアミック酸からなる群から選択されるいずれか１種以上を含む、［１１］に記載の組成物。
［１３］前記添加剤が酸性基を含み、該酸性基を含む添加剤が、前記マレイミド系高分子鎖中に組み込まれている、［１０］〜［１２］のいずれかに記載の組成物。
［１４］前記添加剤が酸性基を含み、該酸性基を含む添加剤が、ノボラック樹脂、ポリビニルフェノール、フラボノイド系フェノール、及びベンゾオキサジン化合物からなる群から選択されるいずれか１種以上を含む、［１］〜［１３］のいずれかに記載の組成物。
［１５］前記添加剤が、環状エステル系化合物、エポキシ化合物、エポキシ化合物用硬化剤、マレイミド、ナジイミド、アクリル化合物、メタクリル化合物、ビニルスルホン化合物、チオール化合物、オキサゾリン化合物、チイラン化合物、金属化合物、界面活性剤、及び顔料からなる群から選択されるいずれか１種以上を含む、［１］〜［１４］のいずれかに記載の組成物。
［１６］前記添加剤が、エポキシ化合物、及び／又はオキサゾリンである［１５］に記載の組成物。
［１７］前記添加剤が、ノボラックエポキシ化合物である、［１５］又は［１６］に記載の組成物。
［１８］前記添加剤が、ラクトンである、［１５］〜［１７］のいずれかに記載の組成物。
［１９］ビスマレイミドとジアミンとを重合させて得られるマレイミド系高分子、並びにリンゴ酸ジメチル、リンゴ酸ジエチル、リンゴ酸ジプロピル、リンゴ酸ジブチル、二酢酸グリセロール、及び下記式（２）、（４）、（５）〜（１０）、（１２）〜（１４）、及び（１７）〜（１９）からなる群から選択されたいずれか１種以上の溶剤を含有する組成物。

［２０］前記ジアミンが脂肪族ジアミン又は脂環式ジアミンである、［１９］に記載の組成物。
［２１］前記ビスマレイミドが下記式（Ｍ１）、（Ｍ２）、（Ｍ７）、及び（Ｍ８）で示される化合物からなる群から選択される一以上であり、前記ジアミンが下記式（ＩＩ−１−５）、（ＩＩ−１−６）、（ＩＩ−１−２２）、（ＩＩ−１−２４）、（ＩＩ−１−３０）、（ＩＶ−１−１）、及び（ＩＶ−１−２）で示される化合物からなる群から選択されるいずれか１種以上を含む、［１９］又は［２０］に記載の組成物。

［２２］前記溶剤が、該溶剤全量に対してリンゴ酸ジメチル、リンゴ酸ジエチル、リンゴ酸ジプロピル、リンゴ酸ジブチル、二酢酸グリセロール、及び式（２）、（４）、（５）〜（１０）、（１２）〜（１４）、（１７）〜（１９）からなる群から選択されたいずれか１種以上の溶剤を合計で２０重量％以上含有する、［１９］〜［２１］のいずれか一項に記載の組成物。
［２３］ビスマレイミドとジアミンとを含有する原料を、リンゴ酸ジメチル、リンゴ酸ジエチル、リンゴ酸ジプロピル、リンゴ酸ジブチル、二酢酸グリセロール、及び下記式（２）、（４）、（５）〜（１０）、（１２）〜（１４）、（１７）〜（１９）からなる群から選択されたいずれか１種以上の溶剤を含有する溶剤中で重合させて高分子を得る工程を含む、前記高分子と下記式（２）、（４）、（５）〜（１０）、（１２）〜（１４）、（１７）〜（１９）からなる群から選択されたいずれか１種以上の溶剤を含有する組成物の製造方法。

［２４］前記ジアミンが脂肪族ジアミン又は脂環式ジアミンである、［２３］に記載の方法。
［２５］前記ビスマレイミドが下記式（Ｍ１）、（Ｍ２）、（Ｍ７）、及び（Ｍ８）で示される化合物からなる群から選択されるいずれか１種以上を含み、前記ジアミンが下記式（ＩＩ−１−５）、（ＩＩ−１−６）、（ＩＩ−１−２２）、（ＩＩ−１−２４）、（ＩＩ−１−３０）、（ＩＶ−１−１）、及び（ＩＶ−１−２）で示される化合物からなる群から選択されるいずれか１種以上を含む、［２３］または［２４］に記載の方法。

［２６］前記溶剤が、該溶剤全量に対してリンゴ酸ジメチル、リンゴ酸ジエチル、リンゴ酸ジプロピル、リンゴ酸ジブチル、二酢酸グリセロール、及び式（２）、（４）、（５）〜（１０）、（１２）〜（１４）、（１７）〜（１９）からなる群から選択されたいずれか１種以上の溶剤を合計で２０重量％以上含有する、［２３］〜［２５］のいずれかに記載の方法。
［２７］３−アミノピロリジン−２，５−ジオン構成単位、並びにアミック酸構成単位を含むマレイミド系高分子共重合体の製造方法であって、（イ）：ビスマレイミドと過剰のジアミンを反応させることでアミノ基末端のオリゴマーを作製し、それに（ロ）：テトラカルボン酸無水物、トリカルボン酸塩化物無水物、又はジカルボン酸塩化物を添加することで共重合させる、マレイミド系高分子共重合体の製造方法。
［２８］３−アミノピロリジン−２，５−ジオン構成単位、並びにアミック酸構成単位を含むマレイミド系高分子共重合体の製造方法であって、（イ）：ビスマレイミドと過剰のジアミンを反応させることでアミノ基末端のオリゴマーを作製し、それに（ハ）：過剰のテトラカルボン酸無水物、トリカルボン酸塩化物無水物、又はジカルボン酸塩化物、及びジアミン又はジオールとを用いて合成した酸無水物末端のオリゴマーを混合することで共重合させる、マレイミド系高分子共重合体の製造方法。
［２９］３−アミノピロリジン−２，５−ジオン構成単位、並びにマレアミック酸構成単位を含むマレイミド系高分子共重合体の製造方法であって、（ニ）：過剰の無水マレイン
酸とジアミンを反応させることでマレアミック酸基末端のオリゴマーを作製し、それに（ホ）：ジアミン及びビスマレイミドを混合することで共重合させる、マレイミド系高分子共重合体の製造方法。
［３０］３−アミノピロリジン−２，５−ジオン構成単位、並びにマレアミック酸構成単位を含むマレイミド系高分子共重合体の製造方法であって、（ニ）：過剰の無水マレイン酸とジアミンを反応させることでマレアミック酸基末端のオリゴマーを作製し、それに（ヘ）：過剰のジアミン及びビスマレイミドとを用いて合成したアミノ基末端のオリゴマーを混合して共重合させる、マレイミド系高分子共重合体の製造方法。
［３１］３−アミノピロリジン−２，５−ジオン構成単位、並びにマレアミック酸構成単位を含むマレイミド系高分子共重合体の製造方法であって、（イ）：ビスマレイミドと過剰のジアミンを反応させることでアミノ基末端のオリゴマーを作製し、それに（ト）：無水マレイン酸、次いでジアミンを混合して共重合させる、マレイミド系高分子共重合体の製造方法。
［３２］主鎖中に、ジアミンとテトラカルボン酸誘導体から誘導されたアミック酸構成単位と、ジアミンとビスマレイミドから誘導された３−アミノピロリジン−２，５−ジオン構成単位とを有する共重合体。
［３３］前記アミック酸構成単位の構築において、２級アミンを用いる、［３２］に記載の共重合体。
［３４］主鎖中に、ジオールとテトラカルボン酸誘導体から誘導されたエステル酸構成単位と、ジアミンとビスマレイミドから誘導された３−アミノピロリジン−２，５−ジオン構成単位とを有する共重合体。
［３５］主鎖中に、無水マレイン酸とジアミンから誘導されたスクシンアミック酸構成単位と、ジアミンとビスマレイミドから誘導された３−アミノピロリジン−２，５−ジオン構成単位とを有する共重合体。
［３６］前記スクシンアミック酸構成単位の構築において、２級アミンを用いる、［３５］に記載の共重合体。
［３７］［１］〜［２２］のいずれかに記載の組成物、［２３］〜［２６］のいずれかに記載の方法により製造された組成物、［２７］〜［３１］のいずれかに記載の製造方法により製造された共重合体、及び［３２］〜［３６］のいずれかに記載の共重合体、から選択されるいずれかを含有する被覆材料。
［３８］［１］〜［２２］のいずれかに記載の組成物、［２３］〜［２６］のいずれかに記載の方法により製造された組成物、［２７］〜［３１］のいずれかに記載の製造方法により製造された共重合体、及び［３２］〜［３６］のいずれかに記載の共重合体、から選択されるいずれかを含有する絶縁材料。
［３９］［１］〜［２２］のいずれかに記載の組成物、［２３］〜［２６］のいずれかに記載の方法により製造された組成物、［２７］〜［３１］のいずれかに記載の製造方法により製造された共重合体、及び［３２］〜［３６］のいずれかに記載の共重合体、から選択されるいずれかを含有するプリント配線基板用材料。
［４０］［１］〜［２２］のいずれかに記載の組成物、［２３］〜［２６］のいずれかに記載の方法により製造された組成物、［２７］〜［３１］のいずれかに記載の製造方法により製造された共重合体、及び［３２］〜［３６］のいずれかに記載の共重合体、から選択されるいずれかを含有する液晶配向剤。
［４１］［４０］に記載の液晶配向剤の塗膜が加熱処理されて形成される液晶配向膜。
［４２］一対の基板と、液晶分子を含有し、前記一対の基板の間に形成される液晶層と、液晶層に電圧を印加する電極と、前記液晶分子を所定の方向に配向させる液晶配向膜とを有する液晶表示素子において、
前記液晶配向膜が［４１］に記載の液晶配向膜である液晶表示素子。
［４３］［１］〜［２２］のいずれかに記載の組成物、［２３］〜［２６］のいずれかに記載の方法により製造された組成物、［２７］〜［３１］のいずれかに記載の製造方法により製造された共重合体、及び［３２］〜［３６］のいずれかに記載の共重合体、から選
択されるいずれかを含有する接着剤。
［４４］［１］〜［２２］のいずれかに記載の組成物、［２３］〜［２６のいずれかに記載の方法により製造された組成物、［２７］〜［３１］のいずれかに記載の製造方法により製造された共重合体、及び［３２］〜［３６］のいずれかに記載の共重合体、から選択されるいずれかを含有する封止材。
［４５］［１］〜［２２］のいずれかに記載の組成物、［２３］〜［２６］のいずれかに記載の方法により製造された組成物、［２７］〜［３１］のいずれかに記載の製造方法により製造された共重合体、及び［３２］〜［３６］のいずれかに記載の共重合体、から選択されるいずれかを含有する成形材料。
［４６］［１］〜［２２］のいずれかに記載の組成物、［２３］〜［２６］のいずれかに記載の方法により製造された組成物、［２７］〜［３１］のいずれかに記載の製造方法により製造された共重合体、及び［３２］〜［３６］のいずれかに記載の共重合体、から選択されるいずれかを含有するガス分離膜材料。
［４７］［１］〜［２２］のいずれかに記載の組成物、［２３］〜［２６］のいずれかに記載の方法により製造された組成物、［２７］〜［３１］のいずれかに記載の製造方法により製造された共重合体、及び［３２］〜［３６］のいずれかに記載の共重合体、から選択されるいずれかから形成した線材用材料。 [1] A composition containing any one or more solvents selected from the group consisting of maleimide polymers, additives, solvents having alcoholic hydroxyl groups, and protic amide solvents.
[2] The composition according to [1], wherein the maleimide polymer has a weight average molecular weight of 3,000 to 500,000.
[3] The composition according to [1] or [2], wherein the maleimide polymer is a polymer obtained by Michael addition reaction using bismaleimide and diamine.
[4] The composition according to [3], wherein the diamine is an aliphatic diamine or an alicyclic diamine.
[5] The maleimide polymer is polymerized in a solvent containing at least one selected from the group consisting of a solvent having an alcoholic hydroxyl group and a protic amide solvent. [4] The composition according to any one of [4].
[6] The solvent having an alcoholic hydroxyl group is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, 1-hexanol, 2-ethylhexanol. Benzyl alcohol, (o-, m-, or p-) methylbenzyl alcohol, (o-, m-, or p-) methoxybenzyl alcohol, 1-phenylethyl alcohol, 2-phenylethyl alcohol, ethylene glycol, glycerol 3-methyl-3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monoethyl ether, triethylene glycol monoalkyl ether From highly polar alcohols having any one or more groups selected from the group consisting of ter, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and 1) alcoholic hydroxyl group, and 2) amide, ester, and cyclic ether The composition according to [5], which is a solvent containing any one or more selected from the group consisting of:
[7] The highly polar alcohol is methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, 2-hydroxy Any one selected from the group consisting of methyl-3-butenoate, dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, and compounds represented by the following formulas (1) to (21) The composition according to [6], including one or more, wherein the protic amide solvent includes any one or more selected from the group consisting of compounds represented by the following formulas (22) to (26).

[8] The solvent contains a solvent having an alcoholic hydroxyl group or a protic amide solvent, and contains 20% by weight or more of the solvent having a alcoholic hydroxyl group or a protic amide solvent based on the total amount of the solvent. ] The composition in any one of [7].
[9] The composition according to any one of [1] to [8], wherein the maleimide polymer is produced by a method that does not include a step of solvent substitution after polymerization.
[10] Any one of [1] to [9], wherein the additive includes at least one structure selected from the group consisting of an acidic group structure, a polymerizable group structure, and a cyclic ester structure. A composition according to 1.
[11] The composition according to [10], wherein the additive contains an acidic group, and the acidic group contains any one or more selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phenolic aqueous group. object.
[12] The additive includes an acidic group, and the additive including the acidic group includes any one or more selected from the group consisting of polyamic acid, polyester acid, and polymaleamic acid. [11] A composition according to 1.
[13] The composition according to any one of [10] to [12], wherein the additive contains an acidic group, and the additive containing the acidic group is incorporated in the maleimide polymer chain.
[14] The additive includes an acidic group, and the additive including the acidic group includes any one or more selected from the group consisting of a novolak resin, polyvinylphenol, flavonoid phenol, and a benzoxazine compound. [1] The composition according to any one of [13].
[15] The additive is a cyclic ester compound, epoxy compound, epoxy compound curing agent, maleimide, nadiimide, acrylic compound, methacrylic compound, vinyl sulfone compound, thiol compound, oxazoline compound, thiirane compound, metal compound, surface activity. The composition in any one of [1]-[14] containing any 1 or more types selected from the group which consists of an agent and a pigment.
[16] The composition according to [15], wherein the additive is an epoxy compound and / or an oxazoline.
[17] The composition according to [15] or [16], wherein the additive is a novolac epoxy compound.
[18] The composition according to any one of [15] to [17], wherein the additive is a lactone.
[19] Maleimide polymer obtained by polymerizing bismaleimide and diamine, dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, and the following formulas (2) and (4) A composition containing any one or more solvents selected from the group consisting of: (5) to (10), (12) to (14), and (17) to (19).

[20] The composition according to [19], wherein the diamine is an aliphatic diamine or an alicyclic diamine.
[21] The bismaleimide is one or more selected from the group consisting of compounds represented by the following formulas (M1), (M2), (M7), and (M8), and the diamine is represented by the following formula (II-1) -5), (II-1-6), (II-1-22), (II-1-24), (II-1-30), (IV-1-1), and (IV-1- The composition according to [19] or [20], comprising any one or more selected from the group consisting of compounds represented by 2).

[22] The solvent is dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, and formulas (2), (4), (5) to (10) with respect to the total amount of the solvent. Any one of one or more solvents selected from the group consisting of (12) to (14) and (17) to (19), containing a total of 20% by weight or more, [19] to [21] The composition according to one item.
[23] Raw materials containing bismaleimide and diamine are dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, and the following formulas (2), (4), (5) to ( 10), including a step of polymerizing in a solvent containing at least one solvent selected from the group consisting of (12) to (14) and (17) to (19) to obtain a polymer. Any one or more solvents selected from the group consisting of polymers and the following formulas (2), (4), (5) to (10), (12) to (14), and (17) to (19) The manufacturing method of the composition containing this.

[24] The method according to [23], wherein the diamine is an aliphatic diamine or an alicyclic diamine.
[25] The bismaleimide contains one or more selected from the group consisting of compounds represented by the following formulas (M1), (M2), (M7), and (M8), and the diamine has the following formula ( II-1-5), (II-1-6), (II-1-22), (II-1-24), (II-1-30), (IV-1-1), and (IV The method according to [23] or [24], comprising any one or more selected from the group consisting of compounds represented by -1-2).

[26] The solvent is dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, and formulas (2), (4), (5) to (10) with respect to the total amount of the solvent. Any one of one or more solvents selected from the group consisting of (12) to (14) and (17) to (19), in a total amount of 20% by weight or more, [23] to [25] The method described in 1.
[27] A method for producing a maleimide polymer copolymer containing a 3-aminopyrrolidine-2,5-dione structural unit and an amic acid structural unit, wherein (b): bismaleimide is reacted with excess diamine The maleimide polymer is prepared by preparing an oligomer having an amino group terminal and copolymerizing it by adding (b): tetracarboxylic acid anhydride, tricarboxylic acid chloride anhydride, or dicarboxylic acid chloride. Manufacturing method.
[28] A method for producing a maleimide polymer copolymer containing a 3-aminopyrrolidine-2,5-dione structural unit and an amic acid structural unit, wherein (b): bismaleimide is reacted with excess diamine. An amino acid-terminated oligomer was prepared by using (c) an excess of tetracarboxylic acid anhydride, tricarboxylic acid chloride anhydride, or dicarboxylic acid chloride, and diamine or diol. A method for producing a maleimide polymer copolymer, which comprises copolymerization by mixing terminal oligomers.
[29] A process for producing a maleimide polymer comprising a 3-aminopyrrolidine-2,5-dione structural unit and a maleamic acid structural unit, wherein (d): an excess of maleic anhydride is reacted with a diamine A maleimide polymer copolymer is prepared by preparing a oligomer at the terminal of the maleamic acid group and copolymerizing it by mixing (e): diamine and bismaleimide.
[30] A method for producing a maleimide-based polymer copolymer containing a 3-aminopyrrolidine-2,5-dione structural unit and a maleamic acid structural unit, wherein (d): an excess of maleic anhydride is reacted with a diamine To produce a maleic acid group-terminated oligomer, and (f): an amino group-terminated oligomer synthesized using an excess of diamine and bismaleimide, and then copolymerized. Manufacturing method.
[31] A process for producing a maleimide polymer copolymer comprising a 3-aminopyrrolidine-2,5-dione structural unit and a maleamic acid structural unit, wherein (b): bismaleimide is reacted with an excess of diamine Thus, an oligomer having an amino group terminal is prepared, and (g): maleic anhydride and then diamine are mixed and copolymerized.
[32] A copolymer having an amic acid structural unit derived from a diamine and a tetracarboxylic acid derivative and a 3-aminopyrrolidine-2,5-dione structural unit derived from a diamine and bismaleimide in the main chain .
[33] The copolymer according to [32], wherein a secondary amine is used in the construction of the amic acid structural unit.
[34] A copolymer having an ester acid structural unit derived from a diol and a tetracarboxylic acid derivative and a 3-aminopyrrolidine-2,5-dione structural unit derived from a diamine and bismaleimide in the main chain .
[35] Copolymer having a succinic acid structural unit derived from maleic anhydride and diamine and a 3-aminopyrrolidine-2,5-dione structural unit derived from diamine and bismaleimide in the main chain Coalescence.
[36] The copolymer according to [35], wherein a secondary amine is used in the construction of the succinic acid structural unit.
[37] The composition according to any one of [1] to [22], the composition produced by the method according to any of [23] to [26], and any one of [27] to [31] A coating material containing any one selected from the copolymer produced by the production method described in 1. and the copolymer described in any of [32] to [36].
[38] The composition according to any one of [1] to [22], the composition produced by the method according to any of [23] to [26], and any one of [27] to [31] An insulating material containing any one selected from the copolymer produced by the production method described in 1. and the copolymer described in any one of [32] to [36].
[39] The composition according to any one of [1] to [22], the composition produced by the method according to any of [23] to [26], and any of [27] to [31] A printed wiring board material containing any one selected from the copolymer produced by the production method described in 1. and the copolymer described in any of [32] to [36].
[40] The composition according to any one of [1] to [22], the composition produced by the method according to any of [23] to [26], and any one of [27] to [31] A liquid crystal aligning agent comprising any one selected from the copolymer produced by the production method described in 1. and the copolymer described in any one of [32] to [36].
[41] A liquid crystal alignment film formed by heat-treating a coating film of the liquid crystal aligning agent according to [40].
[42] A pair of substrates, a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment for aligning the liquid crystal molecules in a predetermined direction In a liquid crystal display element having a film,
The liquid crystal display element whose said liquid crystal aligning film is a liquid crystal aligning film as described in [41].
[43] The composition according to any one of [1] to [22], the composition produced by the method according to any of [23] to [26], and any one of [27] to [31] An adhesive containing any one selected from the copolymer produced by the production method described in 1. and the copolymer described in any one of [32] to [36].
[44] The composition according to any one of [1] to [22], the composition produced by the method according to any one of [23] to [26], and any one of [27] to [31] The sealing material containing either selected from the copolymer manufactured by the manufacturing method of description, and the copolymer in any one of [32]-[36].
[45] The composition according to any one of [1] to [22], the composition produced by the method according to any of [23] to [26], and any one of [27] to [31] A molding material containing any one selected from the copolymer produced by the production method described in 1. and the copolymer described in any of [32] to [36].
[46] The composition according to any one of [1] to [22], the composition produced by the method according to any of [23] to [26], and any of [27] to [31] A gas separation membrane material containing any one selected from the copolymer produced by the production method described in 1. and the copolymer described in any one of [32] to [36].
[47] The composition according to any one of [1] to [22], the composition produced by the method according to any of [23] to [26], and any one of [27] to [31] A wire material formed from any one selected from the copolymer produced by the production method described in 1. and the copolymer described in any one of [32] to [36].

  According to the present invention, when a composition containing a maleimide polymer is used as a liquid crystal aligning agent, the electrical characteristics are improved by adding the additive. That is, the composition of the present invention can provide a composition having good electrical characteristics. Moreover, according to this invention, a novel copolymer can be provided.

In the present invention, -CH ₂ in the alkylene - is -O -, - NH -, - CO -, - CHY 2 -, - C (Y 2) 2 -, - NY 2 -, - S -, - SO- , —SO ₂ —, or —Si (Y ²² ) ₂ —, in which —CH ₂ CH ₂ — in alkylene is —CH═CH—, —C≡C—, —Si (CH ₃ ). _When defined as _2- O-Si (CH ₃ ) _2- , or -N = N-, the following embodiments are included.
For example, when alkylene is — (CH ₂ ) ₄ —, one or more of —CH ₂ — is replaced with —O— to replace —O— (CH ₂ ) ₃ — or —O—CH ₂ —O—CH. ₂ may be substituted, and one or more of —CH ₂ CH ₂ — may be replaced by —CH═CH—, and —CH═CH— (CH ₂ ) ₂ — or —CH═CH—CH═CH— Or —CH ₂ — and —CH ₂ CH ₂ — may be simultaneously replaced with —O— and —CH═CH— to give —O—CH ₂ —CH═CH—.
The same applies to the case where alkylene is alkyl in the above example. For example, when alkyl is — (CH ₂ ) ₃ CH ₃ , one or more —CH ₂ — is replaced by —O— and —O— (CH ₂ ) ₂ CH ₃ — or —O—CH ₂ —O—CH ₃ , wherein one or more —CH ₂ CH ₂ — is replaced by —CH═CH—, and —CH═CH —CH ₂ —CH ₃ — or —CH═CH—CH═CH ₂ , or —CH ₂ — and —CH ₂ CH ₂ — may be replaced with —O— and —CH═CH— at the same time. It may be —O—CH ₂ —CH═CH ₂ .
In the case where —CH ₂ — or —CH ₂ CH ₂ — in the above alkylene may be substituted, or —CH ₂ — or —CH ₂ CH ₂ — in alkyl may be substituted, each group The same applies to the case where the number or type of group options that may be replaced by is different.
In the present invention, a group in which —CH ₂ — or —CH ₂ CH ₂ — in alkylene is replaced may be referred to as “substituted alkylene” in the present invention, and —CH ₂ — in the above alkyl or A group in which —CH ₂ CH ₂ — is replaced may be referred to as “substituted alkyl” in the present invention.
In the present invention, it is not preferable that two consecutive —CH ₂ — are replaced by —O— to form —O—O—.

  The composition of the present invention contains a maleimide polymer, an additive, and a solvent. More specifically, it is a composition containing any one or more solvents selected from the group consisting of maleimide polymers, additives, solvents having alcoholic hydroxyl groups, and protic amide solvents.

  The content of the maleimide polymer in the composition of the present invention can be determined from the range of 0.05 to 80% by weight depending on the solubility of the maleimide polymer in the solvent and the use of the composition. For example, when the composition is a liquid crystal aligning agent, the content of the maleimide polymer is preferably 0.1 to 40% by weight. The total content of the maleimide polymer and the additive in the composition of the present invention can be determined from the range of 0.05 to 90% by weight depending on the use of the composition. For example, when the composition is a liquid crystal aligning agent, the total content of the maleimide polymer and the additive is preferably 0.1 to 60% by weight.

  The viscosity of the composition can be appropriately determined depending on various conditions such as its use and working means employed, the concentration of the maleimide polymer, the type of the maleimide polymer, the type and ratio of the solvent, and the like. For example, when the use of the composition is a liquid crystal aligning agent and a coating film is formed by a printing machine, from the viewpoint of obtaining a sufficient film thickness of the coating film and suppressing the occurrence of printing unevenness, the viscosity of the composition is It is preferably 5 to 100 mPa · s, and more preferably 10 to 80 mPa · s. Moreover, when forming a coating film by spin coating, it is preferable that the viscosity of a composition is 5-200 mPa * s, and it is more preferable that it is 10-100 mPa * s.

The viscosity of the composition can be measured by a rotational viscosity measurement method. For example, it can be measured at a measurement temperature of 25 ° C. using a rotational viscometer (TVE-20L type manufactured by Toki Sangyo).
In the present invention, a group in which left and right are asymmetric is defined as that the left and right may be oriented in either direction (for example, -COCH = CH- represents "-COCH = CH-" or "-CH = CHCO- "). When —CH ₂ — in alkyl or alkylene is replaced by —O—, —O— is not consecutive. Alkyl or alkylene shall be either linear or branched.
In the present invention, when the same symbols are used in the same general formula or different general formulas, the respective symbols have meanings independent from each other within the definition.

  The maleimide polymer is a structure of a reaction product of bismaleimide and a diamine, and is a polymer structure (3-aminopyrrolidine-2, 2) formed by the addition reaction of the amino group of the diamine to the unsaturated bond of bismaleimide. What has many 5-dione structural units) is preferable. The maleimide polymer used in the present invention is a Michael polymer of bismaleimide and diamine, rather than a polymer having many units with remarkable branching, crosslinking, or coloring of the polymer chain due to the reaction between double bonds. A polymer having a large number of linear and less colored units by addition reaction is preferable.

  When synthesizing the maleimide polymer by an addition reaction between bismaleimide and diamine, side reaction during the reaction (polymerization) (reaction caused by branching or cross-linking of polymer chains due to reaction between double bonds) From the viewpoint of suppressing solidification or gelation of the liquid, or coloring), it is preferable to use a solvent having an alcoholic hydroxyl group or a solvent containing a protic amide solvent as a solvent to be used during polymerization.

Examples of the solvent having an alcoholic hydroxyl group used as a solvent for polymerization include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, 1-hexanol, Aliphatic monoalcohols such as 2-ethylhexanol, benzyl alcohol, (o-, m-, or p-) methylbenzyl alcohol, (o-, m-, or p-) methoxybenzyl alcohol, 1-phenylethyl alcohol, Aromatic alcohols such as 2-phenylethyl alcohol, alkoxy monoalcohols such as 3-methyl-3-methoxybutanol; aliphatic polyhydric alcohols such as ethylene glycol and glycerol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol monoalkyl ether such as tylene glycol mono-n-butyl ether; diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether; propylene glycol monoalkyl ether such as triethylene glycol monoalkyl ether and propylene glycol monobutyl ether; dipropylene glycol monomethyl ether A dipolar glycol monoalkyl ether such as 1) an alcoholic hydroxyl group, and 2) a highly polar alcohol having at least one group selected from the group consisting of amides, esters, and cyclic ethers, a protic amide solvent, or A solvent containing these mixtures can be used.
Specific examples of the highly polar alcohol include methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, 2- Hydroxyl-containing esters such as methyl hydroxy-3-butenoate, dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate and glycerol diacetate, and compounds represented by the following formulas (1) to (21) It is done.

プロトン性アミド系溶剤として、具体的には、下記式（２２）〜（２６）で示される化合物などが挙げられる。

Specific examples of the protic amide solvent include compounds represented by the following formulas (22) to (26).

When using the solvent having an alcoholic hydroxyl group or a protic amide solvent as the solvent used in the polymerization, the amount used is 10 to 100% by weight based on the total amount of the solvents used in the polymerization. From the viewpoint of suppressing branching due to side reactions (reactions between double bonds) during reaction (polymerization), crosslinking (solidification or gelation of reaction solution), or coloring. The reaction solution after the polymerization reaction is diluted with a solvent other than the solvent having an alcoholic hydroxyl group or a protic amide solvent, and as a result, the solvent having a alcoholic hydroxyl group or the protic amide solvent in the solution is Even if it falls below 10% by weight with respect to the total amount of the solvent, there is no problem.
Among these solvents, the use of a solvent containing a solvent having a highly polar alcoholic hydroxyl group as a polymerization solvent means that these solvents can dissolve bismaleimide, diamine, and a polymer obtained by polymerization, and the addition reaction. This is preferable from the viewpoint of suppressing the solidification or gelation of the reaction solution.
Use of dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, and compounds represented by general formulas (2) to (7) and (17) to (19) as the highly polar alcohol From the above viewpoint, it is more preferable.
When the solvent having an alcoholic hydroxyl group or a protic amide solvent is used as a solvent used during polymerization, it can be used as a resin composition while containing the solvent used during polymerization because of low odor. Since it can manufacture by the method which does not include the process to substitute, it is preferable. When these solvents are used, it is also preferable from the viewpoint of suppressing side reactions (maleimide group ring opening) during the reaction (polymerization).
When these solvents are used, a maleimide polymer having a high degree of polymerization can be obtained without using a catalyst such as a proton donor, a tertiary amine, or a combination thereof in the reaction system during the reaction (polymerization). Is preferable. Further, since it is not necessary to add a catalyst to the reaction system at the time of reaction (at the time of polymerization), a polymer with less impurities can be obtained, which is preferable in terms of quality. Furthermore, a step of purifying the polymer after the polymerization is unnecessary, and the reaction solution after the polymerization can be used for a desired application as it is, which is preferable in terms of man-hours. Or when forming a film using a polymer solution, generation | occurrence | production of the vapor | steam with an odor, toxicity, or corrosiveness is suppressed, and it is preferable.
Examples of the proton donor include inorganic acids (for example, hydrogen chloride, sulfuric acid, phosphoric acid, or perchloric acid), carboxylic acids (for example, formic acid, acetic acid, propionic acid, benzoic acid, or trifluoroacetic acid), phenols ( For example, phenol, cresols, chlorophenols, xylenols, hydroquinone, etc.) or salts (eg, ammonium chloride, ammonium sulfide, tributylammonium chloride, boron trifluoride monoethylamine, aluminum chloride, etc.), etc. Examples of the primary amines include triethylamine, pyridine, dimethylaminopyridine, diazabicycloundecene, and the like.
When the high polar alcohol solvent or the protic amide solvent is used as the solvent used in the polymerization, it is preferable because the storage stability of the resin composition is good because the polymer has high solubility.
When a solvent having an aromatic alcohol such as benzyl alcohol is used as a solvent for polymerization, the polymer having a high ratio of rigid structure has a high dissolving power for the polymer, and the operability during polymerization and the storage stability of the resin composition. This is preferable when such a composition is used.
In addition, it is not preferable to use a solvent having a phenolic hydroxyl group as a solvent to be used for polymerization, because there may be a problem of toxicity and odor accompanying the volatilization of the solvent when the composition is used.

  When the solvent used at the time of polymerization is a solvent having an alcoholic hydroxyl group or a protic amide solvent, the amount used is the above raw material relative to the total of the bismaleimide and diamine which are raw materials in the addition reaction and the solvent. From the viewpoint of suppressing the solidification or gelation of the reaction solution in the addition reaction process, the concentration of is preferably from 0.5 to 70% by weight, and more preferably from 1 to 50% by weight. preferable.

The reaction (polymerization) temperature for obtaining the maleimide polymer may be appropriately changed according to the reactivity of the monomer. Preferably, it is −50 ° C. to the boiling point of the solvent. More preferably, -20
C to boiling point of the solvent.
The reaction time may be appropriately changed according to the reactivity of the monomer. Preferably it is 1 to 200 hours. More preferably, it is 2 to 100 hours. Moreover, it is preferable that it is a normal pressure as a pressure at the time of superposition | polymerization.

  The maleimide polymer of the present invention is obtained by subjecting a raw material in which the bismaleimide and the diamine are present in a molar ratio of 0.8: 1.2 to 1.2: 0.8 to the reaction. It is more preferable that the molar ratio of the raw materials is 0.9: 1.1 to 1.1: 0.9. When the additive combined with the maleimide polymer is a polymer or a compound having a polymerizable group, the bismaleimide and the diamine have a molar ratio of 0.5: 1.0 to 1.0: A ratio of 0.5 is preferred.

  The weight average molecular weight of the maleimide polymer is preferably from 3,000 to 500,000, more preferably from 5,000 to 250,000, from the viewpoint of handleability during use. More preferably, it is 200,000, and it is especially preferable that it is 20,000-150,000. In addition, when the additive combined with the maleimide polymer is a polymer or a compound having a polymerizable group, it is preferable that the maleimide polymer has a weight average molecular weight of 3,000 or less.

  The weight average molecular weight was measured using Alliance 2695, manufactured by WATERS, 1% phosphoric acid-containing N, N-dimethylformamide as a developing solvent, (polystyrene) as a standard sample, and HSPgel (registered trademark) RTMB as a column. It can be measured by performing liquid chromatography analysis using -M, manufactured by WATERS.

  The bismaleimide constituting the maleimide polymer of the present invention can be produced from diamine or a derivative thereof. Specifically, for example, a known method (Japanese Patent Laid-Open No. 05-140096), such as a method in which a diamine and maleic anhydride in a molar ratio of 2 or more with respect to the diamine are subjected to an addition reaction, and then dehydration imidation in the presence of an acid. Etc.).

  The bismaleimide constituting the maleimide polymer of the present invention is not particularly limited, and any structure can be used. Examples thereof include bismaleimide having a structure represented by the following formula (M) and bismaleimide described in JP-A No. 2002-265541.

  In said formula (M), R represents C1-C5 alkyl each independently. Specific examples of R include methyl, ethyl, propyl, butylpentyl, isopropyl, isobutyl, tertiary butyl, isopentyl, secondary isopentyl, neopentyl and tertiary pentyl.

The diamine constituting the maleimide polymer of the present invention is not particularly limited, and any structure such as aromatic diamine, aliphatic diamine, alicyclic diamine, and siloxane skeleton diamine can be used. For example, the compound represented with the following general formula (I) is mentioned.
^{Y 20 -HN-X 1 -X 1} -X 1 -X 1 -X 1 -X 1 -X 1 -NH-Y 20 (I)

In the general formula (I), Y ²⁰ independently represents the following general formula (XXI),
^{~A 1 -A 1 -A 1 -A 1} -A 1 -A 1 -A 2 (XXI)

In general formula (XXI):
A ¹ independently represents a single bond, alkylene having 1 to 12 carbons, or a ring having a sum of 3 to 30 of carbon, nitrogen, oxygen, sulfur and silicon constituting the skeleton,
If A ¹ is alkylene, -CH ₂ in the alkylene - is independently ^{-NH -, - CHY 2 -,} - C (Y 2) 2 -, or -NY ² - may be replaced by, Y ² Independently represents —H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons, and —CH ₂ CH ₂ — in the alkylene of A ¹ is independently —CH═CH—, or — C≡C— may be substituted, and —CH ₂ — not adjacent to —NH— in alkylene may be independently replaced with —O— or —CO—, and not adjacent to —NH— in alkylene. —CH ₂ CH ₂ — may be independently replaced by —N═N—, and —H on the alkylene of A ¹ or substituted alkylene is independently —F, —Cl, —Br, —C≡. _{N, -OH, -COOH, -SO 3} H, or -PO ₃ H _2, or the following general formula Often replaced by XXII),
When A ¹ is a ring, —H on the ring is independently —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , —N. (Y ² ) ₂ or the following general formula (XXII) may be substituted,
^{~A 3 -A 3 -A 3 -A 2} (XXII)

In general formula (XXII),
A ³ independently represents a single bond, a linear or branched alkylene having 1 to 30 carbon atoms, or a ring having a sum of 3 to 30 carbon, nitrogen, oxygen, sulfur and silicon constituting the skeleton;
When A ³ is alkylene, —CH ₂ — in the alkylene may be independently replaced with —O—, —NH—, —CO—, or —NY ² —, and Y ² is independently —H Represents an alkyl having 1 to 20 carbons or an alkenyl having 2 to 20 carbons, and —CH ₂ CH ₂ — in the alkylene of A ³ is independently —CH═CH—, —C≡C—, or — N = N— may be substituted, and —H on the alkylene of A ³ or the substituted alkylene is independently —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO _3. H, —PO ₃ H ₂ , alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons may be substituted;
When A ³ is a ring, —H on the ring is independently —F, —Cl, —Br, —C≡N, —CH ₃ , —OCH ₃ , —OCH ₂ F, —OCHF ₂ , —OCF. ₃ , —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or —N (Y ² ) ₂ , wherein Y ² is independently —H, alkyl having 1 to 20 carbons, Or alkenyl having 2 to 20 carbon atoms,

In general formula (I):
X ¹ independently represents a single bond, an alkylene having 1 to 30 carbon atoms, or a divalent group having a ring in which the sum of carbon, nitrogen, oxygen, sulfur and silicon constituting the skeleton is 3 to 30 ,
When X ¹ is alkylene, —CH ₂ — in the alkylene may be independently replaced with —NH—, —CHY ¹ —, —C (Y ¹ ) ₂ —, or —NY ¹ —;
—CH ₂ CH ₂ — in the alkylene of X ¹ may be independently replaced with —CH═CH— or —C≡C—, and —CH ₂ — which is not adjacent to —NH— in the alkylene is independently , - - -O Te CO -, - S -, - SO -, - SO 2 -, or -Si (Y ²²⁾ ₂ - in replaced often, -CH ₂ CH not adjacent in the alkylene -NH- ₂ -may be independently replaced by -N = N-, and -H on X ¹ alkylene or substituted alkylene is independently -F
, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, or —PO ₃ H ₂ ,
When X ¹ is a ring, —H on the ring having 3 to 30 carbon atoms, nitrogen, oxygen, sulfur, and silicon constituting the skeleton independently represents —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or —Y ¹ may be substituted, —CHY ¹ —, —C (Y ¹ ) ₂ —, and —Y ^1. Y ¹ in each independently represents —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or the following general formula (XXI). represents, -NY ¹ - in Y ¹ represents the following general formula (XXI),
^{~A 1 -A 1 -A 1 -A 1} -A 1 -A 1 -A 2 (XXI)

In general formula (XXI):
A ¹ independently represents a single bond, alkylene having 1 to 12 carbons, or a carbon having a skeleton, nitrogen, and a ring having a sum of 3 to 30 oxygen, sulfur, and silicon;
When A ¹ is alkylene, —CH ₂ — in the alkylene may be independently replaced with —O—, —NH—, —CO—, or —NY ² —, and Y ² is independently —H Represents an alkyl having 1 to 20 carbons or an alkenyl having 2 to 20 carbons, and —CH ₂ CH ₂ — in the alkylene of A ¹ is independently —CH═CH—, —C≡C—, or — N = N— may be substituted, and —H on the alkylene of A ¹ or the substituted alkylene is independently —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO _3. H, or —PO ₃ H ₂ , or the following general formula (XXII) may be substituted,
When A ¹ is a ring, —H on the ring is independently —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , —N. (Y ² ) ₂ or the following general formula (XXII) may be substituted,
^{~A 3 -A 3 -A 3 -A 2} (XXII)

In general formula (XXII),
A ³ independently represents a single bond, a linear or branched alkylene having 1 to 30 carbon atoms, or a ring having a sum of 3 to 30 carbon, nitrogen, oxygen, sulfur and silicon constituting the skeleton;
When A ³ is alkylene, —CH ₂ — in the alkylene may be independently replaced with —O—, —NH—, —CO—, or —NY ² —, and Y ² is independently —H Represents an alkyl having 1 to 20 carbons or an alkenyl having 2 to 20 carbons, and —CH ₂ CH ₂ — in the alkylene of A ³ is independently —CH═CH—, —C≡C—, or — N = N— may be substituted, and —H on the alkylene of A ³ or the substituted alkylene is independently —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO _3. H, —PO ₃ H ₂ , alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons may be substituted;
When A ³ is a ring, —H on the ring is independently —F, —Cl, —Br, —C≡N, —CH ₃ , —OCH ₃ , —OCH ₂ F, —OCHF ₂ , —OCF. ₃ , —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or —N (Y ² ) ₂ , wherein Y ² is independently —H, alkyl having 1 to 20 carbons, Or alkenyl having 2 to 20 carbon atoms,

In general formula (XXI) or general formula (XXII),
A ² independently represents —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or alkyl having 1 to 40 carbon atoms. ,
When A ² is alkyl, —CH ₂ — in alkyl may be independently replaced with —O—, —NH—, or —CO—, and —CH ₂ CH ₂ — in alkyl is independently -CH = CH-, -C≡C-, or -N = N- may be substituted, and -H on the alkyl or substituted alkyl is independently -F, -Cl, -Br, -C≡ _{N, -OH, -COOH, -SO 3} H, or may be replaced with -PO ₃ H _2,

In each group constituting the general formula (I), Y ²² independently represents —H, alkyl having 1 to 20 carbons, alkenyl having 1 to 20 carbons, or phenyl, and —H on the phenyl independently. Te -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, may be replaced by alkyl of -PO ₃ H _2, or 1 to 30 carbon atoms,

In the general formula (I), Y ²⁰ is a Y ²⁰ of the other amino group, or independently coupled to the X ¹ may form a ring, when Y ¹ there are a plurality of bonded together May form a ring, provided that at least one of X ¹ is alkylene having 1 to 30 carbon atoms, or the sum of carbon, nitrogen, oxygen, sulfur and silicon constituting the skeleton is 3 to 30 Represents a ring.

  The diamine that can be used in the present invention is specifically represented by the following general formula (II), (III), (IV), (V), (VI), (VII), (VIII), or (IX). Indicated.

In general formulas (III), (IV), (V), (VI), (VII), (VIII), and (IX),
One —H on —NH ₂ may be independently replaced by alkyl of 1 to 12 carbons;
—CH ₂ — in alkyl may be independently replaced by —NH—, —CHY ² —, —C (Y ² ) ₂ —, or —NY ² —, where Y ² is independently —H, carbon Represents alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms, and —CH ₂ CH ₂ — in alkyl may be independently replaced by —CH═CH— or —C≡C— —CH ₂ — that is not adjacent to —NH _{2 in the group} may be independently replaced with —O— or —CO—, and —CH ₂ CH ₂ — that is not adjacent to —NH _{2 in} the alkyl is independently — N = N— may be substituted, and —H on alkyl or substituted alkyl is independently —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, or often replaced by -PO ₃ H _2,
In general formula (II),
Y ²¹ independently represents —H, alkyl having 1 to 20 carbons, or alkylene having 1 to 20 carbons, and —CH ₂ — in the alkyl or alkylene is independently —NH—, —CHY ² —. , —C (Y ² ) ₂ —, or —NY ² —, Y ² independently represents —H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons; Or —CH ₂ CH ₂ — in alkylene may be independently replaced with —CH═CH—, or —C≡C—, and —CH ₂ — not adjacent to —NH— in alkyl or alkylene is independently -O-, or -CO- may be substituted, and -CH ₂ CH _2- not adjacent to -NH- in alkyl or alkylene may be independently replaced by -N = N- Alkylene or substituted al Is -H on Le or replaced alkylene independently -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or -PO ₃ H _2, in replaced well, if Y ²¹ is the alkylene having 1 to 20 carbon atoms, Y ²¹ is a Y ²¹ of the other amino group, or independently bonded to Y ¹ to form a ring,
In the general formulas (III), (IV), (V), (VI), (VII) and (VIII),
And -NH _2, cyclohexane ring, benzene ring, or cyclopropane these rings are replaced, cyclobutane, cyclopentane, methylcyclopentane, cycloheptane, methylcyclohexane, cyclooctane, dimethylcyclohexane, oxirane, azetidine, oxetane, thietane , Pyrrolidine, tetrahydrofuran, tetrahydropyran, oxazoline, oxazolidine, dioxooxazolidine, thiazoline, thiazolidine, dioxothiazolidine, morpholine, thiomorpholine, piperazine, pyrrolidine, piperidine, morpholine, thiomorpholine, 1,3-dioxane, 1,4- Dioxane, hexahydro-furo [3.2-b] furan, naphthalene, anthracene, acenaphthylene, fluorene, phenalene, phenanthate , Triphenylene, pyrene, naphthacene, chrysene, perylene, picene, pentacene, furan, thiophene, pyran, chromene, isochromene, oxazole, isoxazole, thiazole, isothiazole, pyrrole, imidazole, pyrazole, oxadiazole, thiadiazole, triazole, Tetrazole, pyrazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, indole, isoindole, 1H-indazole, benzimidazole, benzoxazole, benzothiazole, 1H-benzotriazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, phthalazine, naphthyridine , Purine, pteridine, carbazole, acridine, phenoxazine, phenothiazine, phenazine , Indolizine, furazane, benzofuran, isobenzofuran, 9H-xanthene, benzo [b] thiophene, phenoxathiin, thianthrene, cyclopenta [a] phenanthrene (steroid), bicyclo [2.2.1] heptane, or bicyclo [2 . 2.2] The single bond between octane may be replaced by alkylene having 1 to 12 carbons, and —CH ₂ — in alkylene is independently —NH—, —CHY ² —, —C ( Y ² ) ₂ — or —NY ² — may be substituted, and Y ² independently represents —H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons, and —CH in alkylene ₂ CH ₂ - is -CH = CH- independently or -C≡C- may be replaced by, -CH ₂ nonadjacent and NH ₂ in the alkylene - is independently -O-, or -C - it may be replaced by, -CH ₂ CH ₂ which is not adjacent to the NH ₂ in the alkylene - may be replaced independently by -N = N-, is -H on alkylene or replaced alkylene independently -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, may be replaced by -PO ₃ H _2, or alkyl of 1 to 10 carbon atoms,

In general formula (II):
X ² independently represents an alkylene having 1 to 12 carbon atoms,
—CH ₂ — in alkylene may be independently replaced with —NH—, —CHY ² —, —C (Y ² ) ₂ —, or —NY ² —, and Y ² is independently —H, carbon Represents an alkyl having 1 to 20 or alkenyl having 2 to 20 carbon atoms, and —CH ₂ CH ₂ — in the alkylene may be independently replaced by —CH═CH— or —C≡C—. —CH ₂ — that is not adjacent to —NH— may be independently replaced with —O— or —CO—, and —CH ₂ CH ₂ — that is not adjacent to —NH— in alkylene is independently — N = N— may be substituted, and —H on the alkylene or substituted alkylene is independently —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, — PO ₃ H ₂ or C 1-10 alkyl may be substituted,

In general formulas (IV), (VI), (VII) and (VIII)
X ³ is independently a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —CONH—, —COO—, —NH—, —N (CH ₃ ). _{- (CH 2) m -N (} CH 3) -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) m -, - O- (CH 2) m -O _{-, - S- (CH 2)} m -S- (m represents an integer of 1~6), - COCH = CH - , - N = N-, or -C≡C- a group including,

In general formula (IX),
X ⁴ independently represents alkylene having 1 to 6 carbons or phenylene, and —H on phenylene may be independently substituted with alkyl having 1 to 30 carbons;
Y ²² independently represents —H, alkyl having 1 to 20 carbons, alkenyl having 1 to 20 carbons, or phenyl, and —H on phenyl independently represents —F, —Cl, —Br, —C ≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or alkyl having 1 to 30 carbon atoms may be substituted,
l represents an integer of 1 to 10,

In the general formulas (II) to (VIII),
Y ¹ independently represents —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or the following general formula (XXI);
^{~A 1 -A 1 -A 1 -A 1} -A 1 -A 1 -A 2 (XXI)

In general formula (XXI):
A ¹ independently represents a single bond, alkylene having 1 to 12 carbons, or a ring having a sum of 3 to 30 of carbon, nitrogen, oxygen, sulfur and silicon constituting the skeleton,
When A ¹ is alkylene, —CH ₂ — in the alkylene may be independently replaced with —O—, —NH—, —CO—, or —NY ² —, and Y ² is independently —H Represents an alkyl having 1 to 20 carbons or an alkenyl having 2 to 20 carbons, and —CH ₂ CH ₂ — in the alkylene of A ¹ is independently —CH═CH—, —C≡C—, or — N = N— may be substituted, and —H on the alkylene of A ¹ or the substituted alkylene is independently —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO _3. H, —PO ₃ H ₂ , or the following general formula (XXII) may be substituted,
When A ¹ is a ring, —H on the ring is independently —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , —N. (Y ² ) ₂ or the following general formula (XXII) may be substituted,
^{~A 3 -A 3 -A 3 -A 2} (XXII)

In general formula (XXII),
A ³ independently represents a single bond, a linear or branched alkylene having 1 to 30 carbon atoms, or a ring having a sum of 3 to 30 carbon, nitrogen, oxygen, sulfur and silicon constituting the skeleton;
When A ³ is alkylene, —CH ₂ — in the alkylene is independently —O—, —NH—,
—CO— or —NY ² — may be substituted, and Y ² independently represents —H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons, and — in the alkylene of A ³ CH ₂ CH ₂ — may be independently replaced with —CH═CH—, —C≡C—, or —N═N—, and —H on A ³ alkylene or substituted alkylene is independently -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, -PO 3 H 2, is replaced by alkenyl alkyl, or C2-20 C20 You can
When A ³ is a ring, —H on the ring is independently —F, —Cl, —Br, —C≡N, —CH ₃ , —OCH ₃ , —OCH ₂ F, —OCHF ₂ , —OCF. ₃ , —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or —N (Y ² ) ₂ , wherein Y ² is independently —H, alkyl having 1 to 20 carbons, Or alkenyl having 2 to 20 carbon atoms,

In general formula (XXI) or general formula (XXII),
A ² independently represents —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or alkyl having 1 to 40 carbon atoms. ,
When A ² is alkyl, —CH ₂ — in alkyl may be independently replaced with —O—, —NH—, or —CO—, and —CH ₂ CH ₂ — in alkyl is independently -CH = CH-, -C≡C-, or -N = N- may be substituted, and -H on the alkyl or substituted alkyl is independently -F, -Cl, -Br, -C≡ _{N, -OH, -COOH, -SO 3} H, or may be replaced with -PO ₃ H _2,

In general formulas (II), (III), (IV), (V), (VI), (VII), and (VIII), a represents an integer of 0 to 4 depending on the structure of the bond destination,
In general formulas (III), (IV), (V), (VI), (VII), and (VIII), the cyclohexane ring or benzene ring is independently cyclopropane, cyclobutane, cyclopentane, methylcyclopentane, cyclo Heptane, methylcyclohexane, cyclooctane, dimethylcyclohexane, oxirane, azetidine, oxetane, thietane, pyrrolidine, tetrahydrofuran, tetrahydropyran, oxazoline, oxazolidine, dioxooxazolidine, thiazoline, thiazolidine, dioxothiazolidine, morpholine, thiomorpholine, piperazine, pyrrolidine , Piperidine, morpholine, thiomorpholine, 1,3-dioxane, 1,4-dioxane, hexahydro-furo [3.2-b] furan, naphthalene, anthracene, aceto Butylene, fluorene, phenalene, phenanthrene, triphenylene, pyrene, naphthacene, chrysene, perylene, picene, pentacene, furan, thiophene, pyran, chromene, isochromene, oxazole, isoxazole, thiazole, isothiazole, pyrrole, imidazole, pyrazole, oxadi Azole, thiadiazole, triazole, tetrazole, pyrazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, indole, isoindole, 1H-pyridine, 1H-1-pyridine, 1H-2-pyridine, benzimidazole, benzoxazole, benzothiazole, 1H-benzotriazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, phthalazine, naphthyridine , Purine, pteridine, carbazole, acridine, phenoxazine, phenothiazine, phenazine, indolizine, furazane, benzofuran, isobenzofuran, 9H-xanthene, benzo [b] thiophene, phenoxathiin, thianthrene, cyclopenta [a] phenanthrene (steroid) , Bicyclo [2.2.1] heptane, or bicyclo [2.2.2] octane.

The diamine that can be used in the present invention can be appropriately used depending on the required properties.
For example, it is preferable to use a diamine having an oriented side chain structure for a VA or TN liquid crystal display element or the like. A diamine having an oriented side chain structure, for example, has a substituent (side chain) branched from the main chain when the substituent connecting two amino groups is the main chain, and is perpendicular to the liquid crystal Or a diamine having a property of developing a pretilt angle. The side chain may be appropriately selected according to the required orientation.
On the other hand, it is preferable to use a diamine having no oriented side chain structure for an IPS liquid crystal display element or the like.
In these diamines, when two amino groups are bonded to the same six-membered carbon, they are preferably bonded to each other meta or para.

  Specific examples of the diamine that can be used in the present invention include general formulas (II-1), (II-2), (III-1), (IV-1), (V-1), and (V-2). ), (V-3), (V-11), (VI-1), (VI-2), (VI-3), (VI-11), (VI-12), (VI-21), (VI-22), (VII-1), (VII-2), (VII-3), (VII-11), (VII-12), (VII-13), (VIII-1), (VIII -2), (VIII-3), (VIII-4), (VIII-11), or a compound represented by (IX-1).

Formulas (II-2), (III-1), (IV-1), (V-1), (V-2), (V-3), (V-11), (VI-1), (VI-2), (VI-3), (VI-11), (VI-12), (VI-21), (VI-22), (VII-1), (VII-2), (VII -3), (VII-11), (VII-12), (VII-13), (VIII-1), (VIII-2), (VIII-3), (VIII-4), (VIII-11) ) And (IX-1)
One —H on —NH ₂ may be independently replaced by alkyl of 1 to 12 carbons;
—CH ₂ — in alkyl may be independently replaced by —NH—, —CHY ² —, —C (Y ² ) ₂ —, or —NY ² —, where Y ² is independently —H, carbon Represents alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms, and —CH ₂ CH ₂ — in alkyl may be independently replaced by —CH═CH— or —C≡C— —CH ₂ — that is not adjacent to NH _{2 in} it may be independently replaced by —O— or —CO—, and is not adjacent to NH ₂ in alkyl—
CH ₂ CH ₂ — may be independently replaced with —N═N—, and —H on the alkyl or substituted alkyl is independently —F, —Cl, —Br, —C≡N, —OH. , -COOH, -SO ₃ H, or may be replaced with -PO ₃ H _2,
In general formula (II-1),
Y ²¹ independently represents —H, alkyl having 1 to 20 carbons, or alkylene having 1 to 20 carbons, and —CH ₂ — in the alkyl or alkylene is independently —NH—, —CHY ² —. , —C (Y ² ) ₂ —, or —NY ² —, Y ² independently represents —H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons; Or —CH ₂ CH ₂ — in alkylene may be independently replaced with —CH═CH—, or —C≡C—, and —CH ₂ — not adjacent to —NH in alkyl or alkylene is independently -O-, or -CO- may be replaced by, -CH ₂ CH ₂ which is not adjacent to the -NH alkyl or alkylene - may be replaced by at -N = N-independently, the alkyl or alkylene, Or substituted alkyl Properly is -H on replaced alkylene independently -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or -PO ₃ H _2, in replaced well, if Y ²¹ is the alkylene having 1 to 20 carbon atoms, Y ²¹ is a Y ²¹ of the other amino group, or independently bonded to Y ³ to form a ring,
Formulas (III-1), (IV-1), (V-1), (V-2), (V-11), (VI-1), (VI-2), (VI-3), (VI-11), (VI-12), (VI-21), (VI-22), (VII-1), (VII-2), (VII-3), (VII-11), (VII -12), (VII-13), (VIII-1), (VIII-2), (VIII-3), (VIII-4), and (VIII-11),
-NH ₂ and a cyclohexane ring, a benzene ring, or a piperazine ring, piperidine ring, morpholine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, triazole ring in which these are replaced, Pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, pyrrolidine ring, pyridine ring, indolizine ring, indole ring, isoindole ring, indazole ring, steroid ring, bicyclo [2.2.1] heptane ring, bicyclo [2.2.2] Octane ring, hexahydro-furo [3.2-b] furan ring, quinoline ring, isoquinoline ring, benzofuran ring, chromene ring, isochromene ring, 9H-xanthene ring, naphthalene ring, anthracene ring, phenanthrene Between ring or fluorene ring Single bond can be substituted by an alkylene having 1 to 12 carbon atoms,
—CH ₂ — in alkylene may be independently replaced with —NH—, —CHY ² —, —C (Y ² ) ₂ —, or —NY ² —, and Y ² is independently —H, carbon Represents alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms,
-CH ₂ CH ₂ in the alkylene - may be replaced by -CH = CH-, or -C≡C-, independently,
—CH ₂ — that is not adjacent to —NH _{2 in} alkylene may be independently replaced with —O— or —CO—, and —CH ₂ CH ₂ — that is not adjacent to —NH ₂ in alkylene is independently -N = N- may be substituted,
-H on alkylene or replaced alkylene is independently -F, -Cl, -Br, -C≡N, -OH, -COOH, may be replaced by -SO ₃ H, or -PO ₃ H ₂ ,

In General Formula (II-1), X ¹¹ represents an alkylene having 1 to 12 carbon atoms having 0 to 4 —Y ³ as a substituent,
In (V-3) and (VII-13), X ¹¹ independently represents alkylene having 1 to 12 carbons,
(II-2) in, X ¹¹ represents an alkylene having 1 to 12 carbon atoms having as the substituent a -X ¹² -Y ^11,
In X ¹¹ of the general formulas (II-1), (II-2), (V-3), and (VII-13),
—CH ₂ — in alkylene may be independently replaced with —NH—, —CHY ² —, —C (Y ² ) ₂ —, or —NY ² —, and Y ² is independently —H, carbon Represents alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms,
-CH ₂ CH ₂ in the alkylene - may be replaced by -CH = CH-, or -C≡C-, independently,
—CH ₂ — that is not adjacent to NH _{2 in} alkylene may be independently replaced with —O— or —CO—, and —CH ₂ CH ₂ — that is not adjacent to NH ₂ in alkylene is independently —N ═N—, and —H on alkylene or substituted alkylene may be independently substituted with alkyl having 1 to 10 carbons;
In the general formula (II-2), X ¹² represents a single bond or a divalent organic group.
In the general formulas (VI-11), (VII-11), and (VIII-11), X ⁵ independently represents —COCH═CH—, —N═N—, or —C≡C—.

Formulas (IV-1), (VI-1), (VI-2), (VI-3), (VI-11), (VI-12), (VII-1), (VII-3), In (VII-11), (VII-12), (VIII-1), (VIII-2), (VIII-3), (VIII-4), and (VIII-11),
X ⁶ is independently a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —CONH—, —COO—, —NH—, —N (CH ₃ ). _{- (CH 2) m -N (} CH 3) -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) m -, - O- (CH 2) m -O —, —S— (CH ₂ ) _m —S— (m represents an integer of 1 to 6), —COCH═CH—, —N═N—, or —C≡C—.

In general formula (IX-1),
X ⁷ independently represents alkylene having 1 to 6 carbon atoms or phenylene, and when X ⁷ is phenylene, —H on phenylene may be independently substituted with alkyl having 1 to 30 carbon atoms.
In general formula (VIII-2),
X ⁸ independently represents a single bond or alkylene having 1 to 3 carbon atoms,
X ⁹ independently represents a single bond, 1,4-phenylene or 1,4-cyclohexylene.

In general formulas (V-2) and (VI-3),
X ¹⁰ is independently a single bond, —O—, —COO—, —CO—, —CONH—, — (CH ₂ ) _m — (m represents an integer of 1 to 6), —CHY ² —, — C (Y ² ) ₂ — or —NY ² — is represented, and Y ² independently represents —H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons.
In the general formula (V-3), X ¹³ independently represents a single bond or alkylene having 1 to 30 carbon atoms,
When X ¹³ is alkylene, —CH ₂ — in the alkylene is independently —O—, —NH—, —CO—, —CHY ² —, —C (Y ² ) ₂ —, —NY ² —, —S—, —SO—, —SO ₂ —, or —Si (Y ²² ) ₂ — may be substituted, and Y ² is independently —H, alkyl having 1 to 20 carbons, or 2 to 2 carbons. alkenyl of 20, -CH ₂ CH ₂ in the alkylene of X ¹³ - is independently -CH = CH -, - C≡C-, or -N = may be replaced by N-, alkylene of X ¹³ Or —H on the substituted alkylene is independently —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , C 1-20; alkyl, or may be replaced by alkenyl of 2 to 20 carbon atoms, Y ²² is independently -H, alkyl having 1 to 20 carbon atoms, Alkenyl prime 1-20, or phenyl, -H on the phenyl are independently -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, -PO 3 H ₂ or may be substituted with alkyl having 1 to 30 carbon atoms.

  Formulas (II-1), (III-1), (IV-1), (V-1), (V-11), (VI-1), (VI-2), (VI-3), (VI-11), (VI-12), (VII-1), (VII-2), (VII-3), (VII-11), (VII-12), (VII-13), (VIII -1), (VIII-2), (VIII-3), (VIII-4), and (VIII-11), a represents an integer of 0 to 4 depending on the structure of the bond destination.

In General Formulas (V-3), (VII-3), (VII-13), and (VIII-4), Y ² is independently -H, alkyl having 1 to 20 carbons, or 2 to 2 carbons. Represents 20 alkenyl.
Formulas (II-1), (III-1), (IV-1), (VI-1), (VI-2), (VI-3), (VI-11), (VI-12), In (VII-1), (VII-11), (VII-12), (VIII-1), (VIII-2), (VIII-3), (VIII-4), and (VIII-11),
Y ³ independently represents —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or alkyl having 1 to 2 carbon atoms. Represent,
When Y ³ is alkyl, —CH ₂ — in alkyl may be independently replaced with —O—, —NH—, or —CO—, and —CH ₂ CH ₂ — in alkyl is independently -CH = CH-, -C≡C-, or -N = N- may be substituted, and -H on the alkyl or substituted alkyl is independently -F, -Cl, -Br, -C≡ _{N, -OH, -COOH, -SO 3} H, or may be replaced with -PO ₃ H _2,
When a plurality of Y ³ are present, they may be bonded to each other to form a ring.

In general formula (V-1),
Y ⁴ independently represents benzyl, —H, —F, —Cl, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , —NHY ⁵ , or —N (Y ⁵ ) ₂ ; ⁵ independently represents alkyl having 1 to 30 carbons or alkenyl having 2 to 30 carbons.
In General Formula (IX-1), Y ⁶ independently represents alkyl having 1 to 3 carbons or phenyl, and l represents an integer of 1 to 10.
In General Formula (VI-2), Y ⁷ independently represents alkyl having 1 to 30 carbons, cyclohexyl, or bicyclohexyl,
When Y ⁷ is cyclohexyl or bicyclohexyl, —H on cyclohexyl or bicyclohexyl may be independently substituted with alkyl having 1 to 30 carbons.

In general formula (VIII-2),
Y ⁸ represents —H or alkyl having 1 to 30 carbons,
When Y ⁸ is alkyl, —CH ₂ — in alkyl may be independently replaced with —O—, —NH—, or —CO—, and —CH ₂ CH ₂ — in alkyl is independently -CH = CH-, -C≡C-, or -N = N- may be substituted, and -H on the alkyl or substituted alkyl is independently -F, -Cl, -Br, -C≡ It may be replaced with N, —OH, —COOH, —SO ₃ H, or —PO ₃ H ₂ .

In general formula (VIII-3),
Y ⁹ represents an alkyl having 6 to 30 carbon atoms,
Y ¹⁰ represents alkyl having 1 to 30 carbon atoms.

In general formula (VII-2),
Y ¹⁷ represents —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or alkyl having 1 to 20 carbon atoms. —CH ₂ — may be independently replaced by —O—, —NH—, or —CO—, and —CH ₂ CH ₂ — in alkyl is independently —CH═CH—, —C≡C -, Or -N = N- may be substituted, and -H on the alkyl or substituted alkyl is independently -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO ₃ H, or replaced with -PO ₃ H _2.

In General Formulas (II-2), (V-2), and (VI-3), Y ¹¹ has a group represented by the following General Formula (XXIII),

In general formula (XXIII),
Ring S is independently a cyclopentane ring, cyclohexane ring, 1,3-dioxane ring, piperidine ring, piperazine ring, pyrrolidine ring, phenylene ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, pyrrole ring, Furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, triazole ring, naphthalene ring, anthracene ring, indole ring, steroid ring, hexahydro-furo [3.2-b] furan ring, succinimide ring, glutarimide ring, Represents a group having a phthalimide ring or a spiro [4.5] decane ring;
-H on the ring S is independently -F, -Cl, -OH, -COOH, -SO 3 H, -PO 3 H 2, may be replaced alkyl having 1 to 30 carbon atoms, or phenyl,
When —H on ring S is replaced by alkyl, —CH ₂ — in alkyl may be independently further replaced by —O—, —NH—, or —CO—, and —CH _{2 in} alkyl CH ₂ — may independently be further replaced by —CH═CH—, —C≡C—, —Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ —, or —N═N—, —H on alkyl or substituted alkyl is independently further substituted with —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, or —PO ₃ H _2. Often,
If -H on the ring S is replaced by phenyl, -H on the phenyl are independently, -F, -Cl, -Br, -C≡N , -CH 3, -OCH 3, -OCH 2 F _{, -OCHF 2, -OCF 3, -OH} , -COOH, -SO 3 H, or may be further replaced by -PO ₃ H _2,
A ⁴ independently represents a single bond or alkylene having 1 to 12 carbons,
When A ⁴ is alkylene, —CH ₂ — in alkylene may be independently replaced by —O—, —NH—, or —CO—, and —CH ₂ CH ₂ — in alkylene is independently —CH═CH—, —C≡C—, or —N═N— may be substituted, and —H on the alkylene or substituted alkylene is independently —F, —Cl, —Br, —C≡. _{N, -OH, -COOH, -SO 3} H, or may be replaced with -PO ₃ H _2,
Y ¹² independently represents a group having —F, —CH ₃ , or a succinimide ring;
b independently represents an integer of 0 to 1, c, d, and e independently represent an integer of 0 to 3, f independently represents an integer of 0 to 4, c + d + e ≧ 1, and 6 ≧ b + c + d + e,
Y ¹³ represents —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or alkyl having 1 to 30 carbon atoms;
When Y ¹³ is alkyl, —CH ₂ — in alkyl may be independently replaced with —O—, —NH—, or —CO—, and —CH ₂ CH ₂ — in alkyl is independently —CH═CH—, —C≡C—, —Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ —, or —N═N— may be substituted on the alkyl or substituted alkyl. -H is independently -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or replaced with -PO ₃ H _2.

In the general formulas (V-11), (VI-12), (VI-21), (VI-22), and (VII-12), Y ¹⁴ independently represents the following general formula (XXI).
^{~A 1 -A 1 -A 1 -A 1} -A 1 -A 1 -A 2 (XXI)

In general formula (XXI):
A ¹ independently represents a single bond, a linear or branched alkylene having 1 to 30 carbon atoms, or a ring having a sum of carbon, nitrogen, and oxygen, sulfur, and silicon constituting 3 to 30 carbon atoms constituting the skeleton. ,
When A ¹ is alkylene, —CH ₂ — in the alkylene may be independently replaced with —O—, —NH—, —CO—, or —NY ² —, and Y ² is independently —H Represents an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, and —CH ₂ CH ₂ — in alkylene is independently —CH═CH—, —C≡C—, or —N═N. - may be replaced by, is -H on alkylene or replaced alkylene independently -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, -PO 3 H ₂ or the following general formula (XXII)
When A ¹ is a ring, —H on the ring is independently —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or It may be replaced by general formula (XXII).
^{~A 3 -A 3 -A 3 -A 2} (XXII)

In general formula (XXII),
A ³ independently represents a single bond, a linear or branched alkylene having 1 to 30 carbon atoms, or a ring having a sum of 3 to 30 carbon, nitrogen, oxygen, sulfur and silicon constituting the skeleton;
When A ³ is alkylene, —CH ₂ — in the alkylene may be independently replaced with —O—, —NH—, —CO—, or —NY ² —, and Y ² is independently —H Represents an alkyl having 1 to 20 carbons or an alkenyl having 2 to 20 carbons, and —CH ₂ CH ₂ — in the alkylene of A ³ is independently —CH═CH—, —C≡C—, or — N = N— may be substituted, and —H on the alkylene of A ³ or the substituted alkylene is independently —F, —Br, —Cl, —C≡N, —OH, —COOH, —SO _3. H, —PO ₃ H ₂ , alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons may be substituted;
When A ³ is a ring, —H on the ring is independently —F, —Cl, —Br, —C≡N, —CH ₃ , —OCH ₃ , —OCH ₂ F, —OCHF ₂ , —OCF. ₃ , —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or —N (Y ² ) ₂ ,
A ² is independently —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or a linear or branched carbon number of 1 to Represents 40 alkyls,
When A ² is alkyl, —CH ₂ — in alkyl may be independently replaced with —O—, —NH—, or —CO—, and —CH ₂ CH ₂ — in alkyl is independently -CH = CH-, -C≡C-, or -N = N- may be substituted, and -H on the alkyl or substituted alkyl is independently -F, -Cl, -Br, -C≡ _{N, -OH, -COOH, -SO 3} H, or may be replaced with -PO ₃ H _2,
However, at least one of Y ¹⁴ is a group containing —COCH═CH—, —N═N—, or —C≡C—.

Formulas (III-1), (IV-1), (V-1), (V-2), (V-11), (VI-1), (VI-2), (VI-3), (VI-11), (VI-12), (VI-21), (VI-22), (VII-1), (VII-2), (VII-3), (VII-11), (VII -12), (VIII-1), (VIII-2), (VIII-3), (VIII-4), and (VIII-11),
Cyclohexane ring or benzene ring is independently piperazine ring, piperidine ring, morpholine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, triazole ring, pyridine ring, pyrazine ring, pyridazine Ring, pyrimidine ring, triazine ring, pyrrolidine ring, 1H-1-pyridine ring, 1H-2-pyridine ring, indolizine ring, indole ring, isoindole ring, indazole ring, steroid ring, bicyclo [2.2.1] Heptane ring, bicyclo [2.2.2] octane ring, hexahydro-furo [3.2-b] furan ring, quinoline ring, isoquinoline ring, benzofuran ring, chromene ring, isochromene ring, 9H-xanthene ring, naphthalene ring, Anthracene ring, phenanthrene ring, or fluorene It may be replaced by.

More specifically, compounds represented by the following general formula are exemplified.
Examples of the diamine represented by the general formula (II-1) include the following general formulas (II-1-1) to (II-1-14) and (II-1-21) to (II-1-30). The diamine represented by this is mentioned.

  Examples of the diamine represented by the general formula (II-2) include diamines represented by the following general formulas (II-2-1) to (II-2-4).

  Examples of the diamine represented by the general formula (III-1) include diamines represented by the following general formulas (III-1-1) and (III-1-5).

  Examples of the diamine represented by the general formula (IV-1) include diamines represented by the following general formulas (IV-1-1) to (IV-1-4).

  Examples of the diamine represented by the general formula (V-1) include diamines represented by the following general formulas (V-1-1) to (V-1-26).

  Examples of the diamine represented by the general formula (V-2) include diamines represented by the following general formulas (V-2-1) to (V-2-54).

In the general formulas (V-2-1) to (V-2-54),
Y ² independently represents -H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
Y ⁵ independently represents alkyl having 1 to 30 carbons or alkenyl having 2 to 30 carbons;
Y ¹⁶ independently represents -H, alkyl having 1 to 30 carbons, alkoxy having 1 to 29 carbons, or alkenyl having 2 to 30 carbons;
Y ¹⁸ independently represents -F, -CF ₃ , or -OCF ₃ .

  As a diamine represented by general formula (V-3), the diamine represented by the following general formula (V-3-1) is mentioned, for example.

  Examples of the diamine represented by the general formula (V-11) include the following general formulas (V-11-1) to (V-11-19) and (V-11-21) to (V-11-23). And diamines represented by (V-11-31) to (V-11-55).

  Examples of the diamine represented by the general formula (VI-1) include diamines represented by the following general formulas (VI-1-1) to (VI-1-40).

Examples of the diamine represented by the general formula (VI-2) include diamines represented by the following general formulas (VI-2-1) to (VI-2-8).

In general formulas (VI-2-1) to (VI-2-8),
Y ¹⁵ independently represents alkyl having 3 to 30 carbons, alkoxy having 3 to 29 carbons, or alkenyl having 3 to 30 carbons.
Y ¹⁶ independently represents -H, alkyl having 1 to 30 carbons, alkoxy having 1 to 29 carbons, or alkenyl having 2 to 30 carbons.

Examples of the diamine represented by the general formula (VI-3) include diamines represented by the following general formulas (VI-3-1) to (VI-3-2).

In general formulas (VI-3-1) to (VI-3-2),
Y ¹⁵ independently represents alkyl having 3 to 30 carbons, alkoxy having 3 to 29 carbons, or alkenyl having 3 to 30 carbons.
Y ¹⁶ independently represents -H, alkyl having 1 to 30 carbons, alkoxy having 1 to 29 carbons, or alkenyl having 2 to 30 carbons.

  Examples of the diamine represented by the general formula (VI-11) include diamines represented by the following general formulas (VI-11-1) to (VI-11-16).

  As a diamine represented by general formula (VI-12), the diamine represented by the following general formula (VI-12-1) is mentioned, for example.

  Examples of the diamine represented by the general formula (VI-21) include diamines represented by the following general formulas (VI-21-1) to (VI-21-6).

Examples of the diamine represented by the general formula (VI-22) include diamines represented by the following general formulas (VI-22-1) to (VI-22-2).

  Examples of the diamine represented by the general formula (VII-1) include diamines represented by the following general formulas (VII-1-1) to (VII-1-6).

Examples of the diamine represented by the general formula (VII-2) include the following general formula (VII-2-
Examples thereof include compounds represented by 1) to (VII-2-15).

  Examples of the diamine represented by the general formula (VII-3) include compounds represented by the following general formulas (VII-3-1) to (VII-3-4).

  Examples of the diamine represented by the general formula (VII-11) include diamines represented by the following general formulas (VII-11-1) to (VII-11-6).

  As a diamine represented by general formula (VII-12), the diamine represented by the following general formula (VII-12-1) is mentioned, for example.

As the diamine represented by the general formula (VII-13), for example, the following general formula (VII-1)
The diamine represented by 3-1)-(VII-13-4) is mentioned.

  Examples of the diamine represented by the general formula (VIII-1) include diamines represented by the following general formulas (VIII-1-1) to (VIII-1-16).

  Examples of the diamine represented by the general formula (VIII-2) include diamines represented by the following general formulas (VIII-2-1) to (VIII-2-8).

In general formulas (VIII-2-1) to (VIII-2-8),
Y ¹⁶ independently represents -H, alkyl having 1 to 30 carbons, alkoxy having 1 to 29 carbons, or alkenyl having 2 to 30 carbons.

  Examples of the diamine represented by the general formula (VIII-3) include diamines represented by the following general formulas (VIII-3-1) to (VIII-3-3).

In general formulas (VIII-3-1) to (VIII-3-3),
Y ¹⁶ independently represents -H, alkyl having 1 to 30 carbons, alkoxy having 1 to 29 carbons, or alkenyl having 2 to 30 carbons;
Y ⁹ represents alkyl having 6 to 30 carbon atoms.

  Examples of the diamine represented by the general formula (VIII-4) include compounds represented by the following general formulas (VIII-4-1) to (VIII-4-8).

  As a diamine represented by general formula (VIII-11), the diamine represented by the following general formula (VIII-11-1) is mentioned, for example.

  Examples of the diamine represented by the general formula (IX-1) include compounds represented by the following general formula (IX-1-1).

  Examples of diamines other than those represented by the general formula include naphthalene-based diamines having a naphthalene structure and fluorene-based diamines having a fluorene structure.

The diamine constituting the maleimide polymer of the present invention is the above general formulas (II-1), (III-1), (IV-1), and (IX-1) from the viewpoint of reactivity. , (V-1-20) to (V-1-22), or (VI-1-40), aliphatic diamines or alicyclic diamines are preferably used.
In particular, when an aliphatic diamine or an alicyclic diamine is used as the diamine as a monomer constituting the maleimide polymer, a catalyst such as a proton donor, a tertiary amine, or a combination of them is used during the reaction (polymerization). Even if it is not used in the reaction system, a maleimide polymer having a high degree of polymerization can be obtained, which is preferable. Further, since it is not necessary to add a catalyst to the reaction system at the time of reaction (at the time of polymerization), a polymer with less impurities can be obtained, which is preferable in terms of quality. Furthermore, a step of purifying the polymer after the polymerization is unnecessary, and the reaction solution after the polymerization can be used for a desired application as it is, which is preferable in terms of man-hours. Or when forming a film using a polymer solution, generation | occurrence | production of the vapor | steam with an odor, toxicity, or corrosiveness is suppressed, and it is preferable.
Examples of the proton donor include inorganic acids (for example, hydrogen chloride, sulfuric acid, phosphoric acid, or perchloric acid), carboxylic acids (for example, formic acid, acetic acid, propionic acid, benzoic acid, or trifluoroacetic acid), phenols ( For example, phenol, cresols, chlorophenols, xylenols, hydroquinone, etc.) or salts (eg, ammonium chloride, ammonium sulfide, tributylammonium chloride, boron trifluoride monoethylamine, aluminum chloride, etc.), etc. Examples of the primary amines include triethylamine, pyridine, dimethylaminopyridine, diazabicycloundecene, and the like.

The composition of the present invention contains an additive and a solvent in addition to the maleimide polymer.
The additive is not particularly limited as long as it can be added to the composition, and low molecular compounds such as various monomers, high molecular compounds such as polyimide, and the like can be used. Furthermore, the said additive is divided roughly into an acidic additive and another additive.
In the case of using a volatile additive, the above-mentioned additive, in order to avoid problems such as corrosion due to the volatilized additive, or toxicity or odor of the additive, use of those having no or few of these problems, Alternatively, it is preferable to use an additive having a polymerizable group in the molecule. The use of non-volatile additives is preferred because these problems associated with volatilization do not occur.

  The acidic additive is an additive containing an acidic group, and examples of the acidic group include a carboxyl group, a sulfonic acid group, and a phenolic hydroxyl group. Examples of acidic additives include carboxylic acid additives such as polyamic acid, polyester acid, and polymaleamic acid, novolak resins, polyvinylphenol resins, flavonoid phenols, or benzoxazine compounds that generate phenolic hydroxyl groups during the reaction. Phenolic additives, and the like. The acidic additive is preferably non-volatile in order to avoid problems such as corrosion due to the additive or toxicity or odor of the additive.

  The polyamic acid is obtained by reacting a tetracarboxylic acid anhydride and a diamine, the polyester acid is obtained by reacting a tetracarboxylic acid anhydride and a diol, and the polymaleic acid is maleic anhydride. It can be obtained by reacting with diamine. The reaction may be performed by a known method. For example, in the case of polyamic acid, diamine is charged into a reaction vessel equipped with a raw material inlet, a nitrogen inlet, a thermometer, a stirrer, and a condenser. Next, a solvent (for example, N-methyl-2-pyrrolidone or dimethylformamide which is an amide polar solvent) and tetracarboxylic acid are added. It can be obtained by reacting at a temperature of 0 to 70 ° C. for 1 to 48 hours under stirring.

The weight average molecular weight of the polyamic acid as an additive is preferably 500 to 500,000, and more preferably 1,000 to 250,000. Moreover, it is preferable that the weight average molecular weights of the said polyester acid as an additive are 500-500,000, and it is more preferable that it is 1,000-250,000. Moreover, the weight average molecular weight of the polymaleamic acid as an additive is preferably 500 to 500,000, and more preferably 1,000 to 250,000.
The carboxylic acid-based additive is preferably added in an amount of 0.01 to 10,000 parts by weight, more preferably 0.05 to 1,000 parts by weight with respect to 100 parts by weight of the maleimide polymer.

  As the diamine used for preparing the polyamic acid or the polymaleamic acid, known diamines can be used, and examples thereof include the diamines described in the formula (I).

In addition, when these diamines are used as raw materials for carboxylic acid additives such as polyamic acid, polyester acid, and polymaleamic acid, a diamine in which one —H on —NH ₂ is replaced by alkyl or the like is used. Thus, it is possible to design a molecule having a structure in which imidization does not occur during heat treatment. Therefore, mixing these additives that do not cause imidization and maleimide polymer at an arbitrarily calculated ratio can reduce variations in imidization rate due to fluctuations in conditions during heat treatment of the coating film. This makes it possible to suppress changes in the adhesion of the coating film to the substrate, electrical characteristics, or pretilt angle when the coating film is used for a liquid crystal alignment film. Quality products can be obtained.

  Examples of the tetracarboxylic acid anhydride used for the preparation of the polyamic acid and polyester acid include aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and alicyclic tetracarboxylic dianhydride. .

  Examples of the tetracarboxylic dianhydride used in the present invention include tetracarboxylic dianhydrides represented by formulas (K-1) to (K-12).

In the formula (K-1), G ¹¹ represents a single bond, an alkylene having 1 to 12 carbon atoms, a 1,4-phenylene ring, or a 1,4-cyclohexylene ring, and Q ¹ each independently represents a single bond or It represents CH _2, for example, tetracarboxylic acid dianhydride represented by the following structural formula (K-1-1) ~ (K -1-12) can be mentioned.

In the formula (K-2), R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ independently represent hydrogen, methyl, ethyl, or phenyl. For example, the following structural formulas (K-2-1) to (K— And tetracarboxylic dianhydride represented by 2-7).

In the formula (K-3), ring A ⁵ represents a cyclohexane ring or a benzene ring. For example, a tetracarboxylic dianhydride represented by the following structural formula (K-3-1) or (K-3-2) is Can be mentioned.

In Formula (K-4), G ¹² represents a single _{bond, -CH 2 -, - CH 2} CH 2 -, - O -, - S -, - C (CH 3) 2 -, - SO-, or -C (CF ₃ ) ₂ —, and each ring A ⁵ independently represents a cyclohexane ring or a benzene ring. For example, tetracarboxylic acids represented by the following structural formulas (K-4-1) to (K-4-22) An acid dianhydride is mentioned.

In the formula (K-5), R ¹⁷ represents hydrogen or methyl, and examples thereof include a tetracarboxylic dianhydride represented by the following structural formula (K-5-1) or (K-5-2). .

In the formula (K-6), Q ¹ each independently represents a single bond or —CH ₂ —, v represents 1 or 2, for example, the following structural formula (K-6-1) or (K-6-6) And tetracarboxylic dianhydride represented by 11).

In the formula (K-7), Q ¹ represents a single bond or —CH ₂ —, for example, a tetracarboxylic dianhydride represented by the following structural formula (K-7-1) or (K-7-2) Is mentioned.

In the formula (K-8), R ¹⁸ represents hydrogen, methyl, ethyl, or phenyl, and the ring A ⁶ represents a cyclohexane ring or a cyclohexene ring. For example, the following structural formulas (K-8-1) to (K-8) And tetracarboxylic dianhydride represented by -20).

In formula (K-9), w1 and w2 represent 0 or 1. Examples thereof include tetracarboxylic dianhydrides represented by the following structural formulas (K-9-1) to (K-9-3).

Formula (K-10) is the following tetracarboxylic dianhydride.

In formula (K-11), ring A ⁵ represents a cyclohexane ring or a benzene ring. Examples thereof include tetracarboxylic dianhydrides represented by the following structural formulas (K-11-1) to (K-11-3).

In the formula (K-12), Q ² represents an alkyl having 2 to 6 carbon atoms, and examples thereof include a tetracarboxylic dianhydride represented by the following structural formula (K-12-1).

Preferred tetracarboxylic dianhydrides include the following structures.

As the diol used for the preparation of the polyester acid, known diols can be used. 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1, 5-pentanediol, 2,4-pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6-hexanetriol 1,2-heptanediol, 1,7-heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2,8 -Octanetriol, 1,2-nonanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanedio Le, 1,10-decanediol, 1,2,10- decanted triol, 1,2-dodecanediol or 1,12-dodecanediol, and the like.

  Examples of novolak resins include phenol novolac resins and bisphenol novolac resins. These are known resins, and commercially available products can be used. When the novolak resin is used as an additive, it is preferably added in an amount of 0.01 to 100 parts by weight, more preferably 0.05 to 50 parts by weight, based on 100 parts by weight of the maleimide polymer.

  Examples of polyvinylphenol resins are poly-o-vinylphenol, poly-m-vinylphenol, poly-p-vinylphenol, poly-o-isopropenylphenol, poly-m-isopropenylphenol, or poly-p-iso And propenylphenol. Further, these polymers may be copolymers containing other structural units. These are also known resins and can be polymerized by a known method or a commercially available product can be used. When using the said polyvinyl phenol resin as an additive, it is preferable to add 0.01-100 weight part with respect to 100 weight part of maleimide type polymers, and it is more preferable to add 0.05-50 weight part.

Examples of flavonoid phenols are 5-hydroxyflavone, 6-hydroxyflavone, 7-hydroxyflavone, 6-hydroxyflavan-4-one, 7-hydroxyflavan-4-one, 2′-hydroxyflavan-4-one, 3'-hydroxyflavan-4-one, 4'-hydroxyflavan-4-one, 5,7-dihydroxyflavone, 5,7-dihydroxy-4 ', 6-dimethoxyflavone, 5,7-dihydroxy-4'- Methoxyflavone, 3,5,7-trihydroxyflavone, 4 ′, 5,7-trihydroxyflavone, 5,6,7-trihydroxyflavone, 4 ′, 5,7-trihydroxyflavan-4-one, 3 , 3 ′, 4 ′, 7-tetrahydroxyflavone, 3,4 ′, 5,7-tetrahydroxyflavone, 3 ′, 4 ′, 5,7-tetra Droxyflavone, 4 ', 5,6,7-tetrahydroxyflavone, 3,3', 4 ', 5-tetrahydroxy-7-methoxyflavone, 2', 3,4 ', 5,7-pentahydroxyflavone 3,3 ′, 4 ′, 5,7-pentahydroxyflavone, 3,3 ′, 4 ′, 5,5 ′, 7-hexahydroxyflavone, 3,3 ′, 4 ′, 5,6,7- Hexahydroxyflavone, (2S) -4 ′, 5-dihydroxy-7-methoxyflavan-4-one, (2S) -3 ′, 4 ′, 5,7-tetrahydroxyflavan-4-one, (2R, 3S ) -Flavan-3,4 ′, 5,7-tetraol, (2R, 3S) -flavan-3,3 ′, 4 ′, 5,7-pentaol, (2R, 3S) -flavan-3,3 ', 4', 5,5 ', 7-hexaol, 3,5,7-trihydroxy-2- (3 4,5-trihydroxyphenyl) -4H-1-benzopyran-4-one, 3,5,7-trihydroxy-2- (4-hydroxyphenyl) -4H-1-benzopyran-4-one, 3,5 , 7-trihydroxy-2-phenyl-4H-1-benzopyran-4-one, (2R-trans) -2- (3,4-dihydroxyphenyl) -3,4-dihydro-2H-1-benzopyran-3 , 5,7-triol, (2R-trans) -3,4-dihydro-2- (3,4,5-trihydroxyphenyl) -2H-1-benzopyran-3,5,7-triol, (2R- trans) -3,4-dihydro-2- (4-hydroxyphenyl) -2H-1-benzopyran-3,5,7-triol, (S) -2- (3,4-dihydroxyphenyl) -2, 3-dihydro-5,7-dihydroxy-4H-1-benzopyran-4-one, (S) -2,3-dihydro-5-hydroxy-2- (4-hydroxyphenyl) -7-methoxy-4H-1 -Benzopyran-4-one, 2- (2,4-dihydroxyphenyl) -3,5,7-trihydroxy-4H-1-benzopyran-4-one, 2- (3,4-dihydroxyphenyl) -3, 5,6,7-tetrahydroxy-4H-1-benzopyran-4-one, 2- (3,4-dihydroxyphenyl) -3,5,7-trihydroxy-4H-1-benzopyran-4-one, 2 -(3,4-dihydroxyphenyl) -3,5-dihydroxy-7-methoxy-4H-1-benzopyran-4-one or 2- (3,4-dihydroxyphenyl) -3,7-dihydroxy -4H-1-benzopyran-4-one, and the like silybin. These are known substances, and commercially available products can be used as compounds, mixtures, or extracts containing them. Or it can obtain by well-known methods, such as an alcohol extraction method, as a compound, a mixture, or an extract containing these from a natural product. When using the said flavonoid type phenol as an additive, it is preferable to add 0.01-10 weight part with respect to 100 weight part of maleimide-type polymers, and it is more preferable to add 0.05-5 weight part.

  The structure of the oxazine of the benzoxazine compound is not particularly limited, and examples thereof include an oxazine structure having an aromatic group including a condensed polycyclic aromatic group such as benzoxazine and naphthoxazine.

  Examples of the benzoxazine compound include compounds represented by the following general formulas (a) to (f). In the following general formula, the bond displayed toward the center of the ring indicates that it is bonded to any carbon that forms the ring and can be bonded to a substituent.

In general formulas (a) to (c), R ¹ and R ² independently represent an organic group having 1 to 30 carbon atoms. In general formulas (a) to (f), R ^{3 to} R ⁶ independently represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. In the general formulas (c), (d), and (f), X is independently a single bond, —O—, —S—, —SS—, —SO ₂ —, —CO—, — CONH -, - NHCO -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) m -, - O- (CH 2) m -O -, - S- (CH ₂ ) Represents _m -S-. Here, m is an integer of 1-6. In general formulas (e) and (f), Y is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —. Or it represents C1-C3 alkylene. The benzene ring of the Y, hydrogen bonded to the naphthalene ring, -F _{independently, -CH 3, -OH, -COOH,} -SO 3 H, may be replaced with -PO ₃ H _2.

  The benzoxazine compound includes an oligomer or polymer having an oxazine structure in the side chain, and an oligomer or polymer having a benzoxazine structure in the main chain.

  The benzoxazine compound can be produced by a method similar to the method described in International Publication No. 2004/009708, JP-A-11-12258, and JP-A-2004-352670.

  When using the said benzoxazine compound as an additive, it is preferable to add 0.01-100 weight part with respect to 100 weight part of maleimide type polymers, and it is more preferable to add 0.05-50 weight part.

  Additives other than acidic additives include cyclic ester compounds, epoxy compounds, epoxy compound curing agents, maleimides, nadiimides, acrylic compounds, methacrylic compounds, vinylsulfone compounds, thiol compounds, oxazoline compounds, thiirane compounds, metal compounds , Surfactants, and pigments.

  Examples of cyclic ester compounds include γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, the compound represented by formula (18), or the compound represented by formula (19), Known lactone compounds can be used. When using the said lactone type compound as an additive, it is preferable to add 1-100,000 weight part with respect to 100 weight part of maleimide type polymers, and it is more preferable to add 10-100,000 weight part. Further, when the compound represented by the formula (18) or the compound represented by the formula (19) is used as a solvent at the time of polymerization, those contained in the obtained polymer solution are regarded as additives as they are. May be.

The epoxy compound is preferably a compound having two or more epoxy groups. The epoxy compound may be one type or two or more types.
Examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic aliphatic epoxy compound.

  Examples of the glycidyl ether include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, bisphenol type epoxy compound, hydrogenated bisphenol-A type epoxy compound, hydrogenated bisphenol-F type epoxy compound, hydrogenated bisphenol. -S type epoxy compound, hydrogenated bisphenol type epoxy compound, brominated bisphenol-A type epoxy compound, brominated bisphenol-F type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, brominated phenol novolak type epoxy compound Brominated cresol novolac type epoxy compound, bisphenol A novolac type epoxy compound, naphthalene skeleton-containing epoxy compound, aromatic polymer Glycidyl ether compounds, dicyclopentadiene phenol type epoxy compound, alicyclic diglycidyl ether compounds, aliphatic polyglycidyl ether compound, a polysulfide-type diglycidyl ether compound, and biphenol type epoxy compound.

Examples of the glycidyl ester include a diglycidyl ester compound and a glycidyl ester epoxy compound.
Examples of glycidylamine include polyglycidylamine compounds and glycidylamine type epoxy compounds.

Examples of the epoxy group-containing acrylic compound include homopolymers and copolymers of monomers having oxiranyl.
Examples of glycidyl amide include glycidyl amide type epoxy compounds.
Examples of the chain aliphatic epoxy compound include compounds containing an epoxy group obtained by oxidizing a carbon-carbon double bond of an alkene compound.
Examples of the cycloaliphatic epoxy compound include a compound containing an epoxy group obtained by oxidizing a carbon-carbon double bond of a cycloalkene compound.

  When using the said epoxy compound as an additive, it is preferable to add 0.01-100 weight part with respect to 100 weight part of maleimide type polymers, and it is more preferable to add 0.05-50 weight part.

When using an epoxy compound, an epoxy resin curing agent can be used in combination. Examples of epoxy resin curing agents include acid anhydrides and amines.
Examples of acid anhydrides used as curing agents for epoxy resins include the above-mentioned tetracarboxylic dianhydrides, and other examples include trimellitic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and the like. 4-methylhexahydrophthalic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, Ricacid HNA100 (trade name; manufactured by Shin Nippon Rika Co., Ltd.), maleic anhydride, citraconic anhydride, etc. Can be mentioned.

  Examples of amines used as curing agents for epoxy resins include the above-mentioned diamines, and other examples include diethylenetriamine, triethylenetetramine; polyamide, ketamine; benzyldimethylamine, 2,4,6-trisdimethylaminophenol. Etc.

  When using the said epoxy resin hardening | curing agent as an additive, it is preferable to add 0.1-20 weight part with respect to 100 weight part of epoxy resin, and it is more preferable to add 0.1-10 weight part.

Examples of maleimide include monomaleimide and polymaleimide.
Monomaleimide is a compound represented by the following general formula and is called N-substituted maleimide. Specific examples of the N-substituted maleimide used in the present invention include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, and N-butylmaleimide. is there. Particularly preferred are N-phenylmaleimide and N-cyclohexylmaleimide. N-cyclohexylmaleimide and N-phenylmaleimide are mentioned.

（上記一般式中、Ｒは１価の有機基である。）
ポリマレイミドは分子中に１個を超える数のマレイミド基を有する化合物であり、前記のビスマレイミド等が挙げられる。

(In the above general formula, R is a monovalent organic group.)
Polymaleimide is a compound having more than one maleimide group in the molecule, and examples thereof include the bismaleimide described above.

  When using the said maleimide as an additive, it is preferable to add 0.01-100 weight part with respect to 100 weight part of maleimide type polymers, and it is more preferable to add 0.05-50 weight part.

Examples of nadiimide include compounds represented by the following general formula (Ina).

In the general formula (Ina), L ¹ and L ² each independently represent hydrogen, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl or benzyl. , N represents 1 or 2.
When n = 1, W is alkyl of 1 to 12 carbon atoms, alkenyl having 2 to 6 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, having 6 to 12 carbon atoms aryl, benzyl, -Z ¹ - (O) _{^{q - (Z 2 O) r}} -Z 3 -H (Z 1, Z 2 and Z ³ represents an alkylene of 2 to 6 carbon atoms independently, q represents 0 or 1, and r is 1 to 30 -(Z ⁴ ) _s -BZ ⁵ -H (wherein Z ⁴ and Z ⁵ are independently alkylene having 1 to 4 carbon atoms or cyclo having 5 to 8 carbon atoms). Represents a alkylene, B represents phenylene, and s represents 0 or 1.) —B—T—B—H (B represents phenylene, and T represents —CH ₂ —, — _{C (CH 3) 2 -,} - O -, - CO -, - S- or SO ₂ -. representing a group represented by), or one to three hydrogen of these groups with a hydroxyl group and Representing a conversion has been based on.
At this time, preferable W is alkyl having 1 to 8 carbons, alkenyl having 3 to 4 carbons, cyclohexyl, phenyl, benzyl, poly (ethyleneoxy) ethyl having 4 to 10 carbons, phenyloxyphenyl, phenylmethylphenyl, Phenyl isopropylidene phenyl and groups in which one or two hydrogens of these groups are replaced by hydroxyl groups.

Formula when n = 2 in (Ina), W is an alkylene of 2 to 20 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, arylene having 6 to 12 carbon ^{atoms, -Z 1 -O- (Z 2 O} ) _r— Z ³ — (Z ¹ , Z ² and Z ³ independently represent alkylene having 2 to 6 carbon atoms, q represents 0 or 1, and r represents an integer of 1 to 30). -Z ⁴ -BZ ^5- (Z ⁴ and Z ⁵ independently represent alkylene having 1 to 4 carbon atoms or cycloalkylene having 5 to 8 carbon atoms, and B represents phenylene). a group represented _{by, -B- (O-B) s} -T- (B-O) s -B- (B represents a phenylene, T is alkylene of 1 to 3 carbon atoms, -O- or -SO ₂ -And s represents 0 or 1.), or a group in which 1 to 3 hydrogens of these groups are replaced by a hydroxyl group.
In this case, preferable W is alkylene having 2 to 12 carbon atoms, cyclohexylene, phenylene, tolylene, xylylene, —C ₃ H ₆ —O— (Z ² —O) _r —O—C ₃ H ₆ — (Z ² is It represents an alkylene having 2 to 6 carbon atoms, r groups represented by represented by 1 or 2), -B-T-B- (B represents a phenylene, and T is -CH ₂ -., - O— or —SO ₂ —)), a group represented by —B—O—B—C ₃ H ₆ —B—O—B— (B represents phenylene), and These are groups in which one or two hydrogens of these groups are replaced by hydroxyl groups.

Such a nadiimide compound is synthesized by, for example, maintaining a nadic acid anhydride derivative and a diamine at a temperature of 80 to 220 ° C. for 0.5 to 20 hours as described in Japanese Patent No. 2729565. The obtained compound or a commercially available compound can be used. When using the said nadiimide as an additive, it is preferable to add 0.01-100 weight part with respect to 100 weight part of maleimide type polymers, and it is more preferable to add 0.05-50 weight part.

  As acrylic compounds and methacrylic compounds, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl ( Meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, etc. Can be mentioned.

  When the acrylic compound or methacrylic compound is used as an additive, it is preferably added in an amount of 0.01 to 100 parts by weight, more preferably 0.05 to 50 parts by weight, based on 100 parts by weight of the maleimide polymer.

  Examples of the vinyl sulfone compound include phenyl vinyl sulfone.

When using the said vinyl sulfone compound as an additive, it is preferable to add 0.01-100 weight part with respect to 100 weight part of maleimide type polymers, and it is more preferable to add 0.05-50 weight part.
Examples of the thiol compound include polythiol QE-340M (manufactured by Toray Fine Chemical Co., Ltd.).

  When using the said thiol compound as an additive, it is preferable to add 0.001-10 weight part with respect to 100 weight part of maleimide type polymers, and it is more preferable to add 0.005-5 weight part.

The acrylic compound, methacrylic compound, vinyl sulfone compound, or thiol compound can be incorporated into the maleimide polymer as a monomer to be incorporated into the polymer, not as an additive defined in the present invention. That is, when a maleimide polymer is produced, a part of bismaleimide is replaced with a bisacrylic compound, a bismethacrylic compound, or a bisvinylsulfone compound, or a part of a diamine is replaced with a bisthiol compound to carry out copolymerization. It can be incorporated into a polymer.
For example, in the case of an acrylic compound, a methacrylic compound, or a vinyl sulfone compound, bismaleimide, and a mixture of one or a plurality of compounds selected from a bisacrylic compound, a bismethacrylic compound, and a bisvinylsulfone compound, a diamine, Can be reacted to obtain a copolymer with a maleimide polymer.
Similarly, in the case of a thiol compound, for example, (b): an oligomer at the maleimide group terminal is prepared by reacting an excess of bismaleimide and a diamine, and (b): a bisthiol compound is added thereto for copolymerization. As a result, a copolymer with a maleimide polymer can be obtained. When the above (b) is added, a diamine can be further added as necessary.
The copolymer thus obtained is different from the “new maleimide polymer copolymer of the present invention”, and the copolymer thus obtained is used in the composition of the present invention. In this case, the composition of the present invention is combined with an additive and a solvent defined in the present invention.

Examples of the bisacrylic compound or bismethacrylic compound include 4,4′-isopropylidene diphenol dimethacrylate, 1,3-butanediol dimethacrylate, 1,
6-bis (acryloyloxy) -2,2,3,3,4,4,5,5-octafluorohexane, 1,4-bis (acryloyloxy) butane, 1,6-bis (acryloyloxy) hexane, Triethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, N, N′-diacryloylethylenediamine, N, N ′-(1,2-dihydroxyethylene) bisacrylamide, or 1,4-bis ( And acryloyl) piperazine.
Examples of the bisvinylsulfone compound include compounds represented by the following formulas (VS-1) and (VS-2).

  The addition amount of the bisacrylic compound, bismethacrylic compound, or bisvinylsulfone compound is selected from the viewpoint of obtaining a polymer having an appropriate molecular weight, from bismaleimide / (sum of bisacrylic compound, bismethacrylic compound, and bisvinylsulfone compound). The molar ratio is preferably 100/0 to 10/90.

  Examples of the bisthiol compound include compounds represented by the following formulas (HS-1) and (HS-2).

  From the viewpoint of obtaining a polymer having an appropriate molecular weight, the bisthiol compound is preferably added at a molar ratio of diamine / bisthiol compound of 100/0 to 50/50.

  An oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be a kind of compound or two or more kinds of compounds. Examples of the oxazoline compound include 2,2′-bis (2-oxazoline), 1,2,4-tris- (2-oxazolinyl-2) -benzene, 4-furan-2-ylmethylene-2-phenyl-4H—. Oxazol-5-one, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, 1,3-bis (4,5-dihydro-2-oxazolyl) benzene, 2,3-bis (4- Isopropenyl-2-oxazolin-2-yl) butane, 2,2′-bis-4-benzyl-2-oxazoline, 2,6-bis (isopropyl-2-oxazolin-2-yl) pyridine, 2,2 ′ -Isopropylidenebis (4-tert-butyl-2-oxazoline), 2,2'-isopropylidenebis (4-phenyl-2-oxazoline), 2,2'-methylenebis (4 tert- butyl-2-oxazoline), and 2,2'-methylenebis (4-phenyl-2-oxazoline) and the like. In addition to these, polymers and oligomers having oxazolyl such as Epocross (trade name, manufactured by Nippon Shokubai Co., Ltd.) are also included.

When using the said oxazoline compound as an additive, it is preferable to add 0.01-100 weight part with respect to 100 weight part of maleimide type polymers, and it is more preferable to add 0.05-50 weight part.

Examples of thiirane compounds include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl propylene oxide, styrene oxide, hexafluoropropylene oxide, cyclohexene oxide, N-glycidyl phthalimide, (nonafluoro-N-butyl) epoxide, Perfluoroethyl glycidyl ether, epichlorohydrin, epibromohydrin, N, N-diglycidyl aniline, and 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxypropane, ethylene glycol diglycidyl ether , Polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether Ter, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, and 3- (N, N-diglycidyl) aminopropyltrimethoxy Silane, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidyl Aminomethyl) cyclohexane, N, N, N ′, N ′,-tetraglycidyl-4,4′-diaminodiphenylmethane, and oxygen of the glycidyl group in 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane. For example, J. et al. Org. Chem. , 28, 229 (1963), a compound in which sulfur is substituted and the glycidyl group is substituted with an ethylene sulfide group.

  When using the said thiirane compound as an additive, it is preferable to add 0.01-100 weight part with respect to 100 weight part of maleimide type polymers, and it is more preferable to add 0.05-50 weight part.

Examples of the metal compound include the following compounds.
Examples of the silane compound include heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane. Silane, hexadecyltriethoxysilane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, undecyltriethoxysilane, undecyl Trimethoxysilane, 21-docosenyltriethoxysilane, allyloxyundecyltriethoxysilane, tridecafluorooctyltrimethyl Xylsilane, tridecafluorooctyltriethoxysilane, isooctyltriethoxysilane, phenethyltriethoxysilane, pentafluorophenylpropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N- (triethoxysilylpropyl) dansylamide, styrylethyltri Ethoxysilane, (R) -N-1-phenylethyl-N′-triethoxysilylpropylurea, (1-naphthyl) triethoxysilane, (1-naphthyl) trimethoxysilane, m-styrylethyltrimethoxysilane, p -Styrylethyltrimethoxysilane, N- [3- (triethoxysilyl) propyl] phthalamic acid, 1-trimethoxysilyl-2- (p-aminomethyl) phenylethane, 1-trimethoxysilyl- -(M-aminomethyl) phenylethane, benzoyloxypropyltrimethoxysilane, 3- (4-methoxyphenoxy) propyltrimethoxysilane, N-triethoxysilylpropylquinine urethane, 3- (N-cyclohexylamino) propyltrimethoxy Silane, 1-[(2-triethoxysilyl) ethyl] cyclohexane-3,4-epoxide, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, N- (1
, 3-Dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, N- (6-aminohexyl) aminopropyltri Methoxysilane, aminoethylaminomethylphenethyltrimethoxysilane, 11-bromoundecyltrimethoxysilane, 2- (diphenylphosphino) ethyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyl Triethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-amino-propyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, methyltripropoxy Lan, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, 3- (2-aminoethylaminopropyl) trimethoxysilane, 3- (2-aminoethylaminopropyl) triethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 2- (2-aminoethylthioethyl) triethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptomethyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, allyltriethoxysilane, 3-methyl Acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, 3,3,3-trifluoro Propyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-bromopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane , Metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diphenyldiet Sisilane, diphenyldimethoxysilane, methyldiethoxysilane, methyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-ureidopropylmethyldiethoxy Silane, 3-ureidopropylmethyldimethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, dimethylphenylethoxysilane, dimethylphenylmethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-ureidopropyldimethylethoxy Silane, 3-aminopropyldimethylmethoxysilane, trimethoxysilane, triethoxysilane, tripropoxysila And tributoxysilane.

Other metal compounds include tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetra n-propoxy titanium, tetra n-butoxy titanium, tetraisobutoxy titanium, tetra t-butoxy titanium, tetrapentoxy titanium, and tetra Isopropyl bis (dioctyl phosphite) titanate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate, dibutyltin diacetylacetonate, tri-i-propoxyaluminum, di-i-propoxyethylacetoacetate aluminum Di-i-propoxy acetylacetonate aluminum, i-propoxy bis (ethylacetoacetate) aluminum, i-propoxy bis (a Tylacetonato) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonate bis (ethylacetoacetate) aluminum, tetra-n-butoxyzirconium, tri-n-butoxyethylaceto Acetate zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, n-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (n-propyl acetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, and tetrakis ( Ethyl acetoacetate) zirconium and the like.

  When using the said metal compound as an additive, it is preferable to add 0.01-100 weight part with respect to 100 weight part of maleimide type polymers, and it is more preferable to add 0.05-50 weight part.

Examples of the surfactant include silicon surfactants, acrylic surfactants, and fluorine surfactants.
Specifically, as the silicon-based surfactant, Byk-300, Byk-306, Byk-335, Byk-310, Byk-341, Byk-344, and Byk-370 (respectively trade names: Big Chemie Japan ( Examples of acrylic surfactants include Byk-354, Byk-358, and Byk-361 (each trade name; manufactured by BYK Chemie Japan Co., Ltd.) and the like, and fluorine-based interfaces. As the activator, DFX-18, Aftergent 250, or Aftergent 251 (each trade name; manufactured by Neos Co., Ltd.), F470, F475, F479, F553, F554, F477, MCF350 (each trade name; DIC Corporation) ))).
When using the said surfactant as an additive, it is preferable to add 0.01-5 weight part with respect to 100 weight part of compositions of this invention, and it is more preferable to add 0.01-1 weight part.

Examples of the pigment include various organic pigments or inorganic pigments. Specific examples of such pigments include C.I. I. Pigment black 1, C.I. I. Pigment black 6, C.I. I. Pigment black 7, C.I. I. Pigment black 8, C.I. I. Pigment black 9, C.I. I. Pigment black 11, C.I. I. Pigment white 6, titanium black, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 202, C.I. I. Pigment red 209, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment violet 23, C.I. I. Pigment violet 37, C.I. I. Pigment orange 43, C.I. I. Pigment orange 71 and the like.
In the present invention, the pigment (B) may be a single type or a mixture of two or more types.

  When using the said pigment as an additive, it is preferable to add 0.1-30 weight part with respect to 100 weight part of compositions of this invention, and it is more preferable to add 0.3-20 weight part.

  These additives are added to the solvent together with the maleimide polymer, but when the additive is an acidic additive and has a structure such as polyamic acid, polyester acid, or maleamic acid. Incorporation into a maleimide polymer, that is, it may be copolymerized with a maleimide polymer.

Specifically, when polyamic acid and polyester acid are used as additives, for example, (i): An amino group-terminated oligomer is prepared by reacting bismaleimide with excess diamine, and (b): It can be copolymerized by adding tetracarboxylic acid anhydride, tricarboxylic acid chloride anhydride, or dicarboxylic acid chloride. When adding the above (b), a diamine or diol can be further added as necessary.
Alternatively, (i): an amino-terminated oligomer is produced by reacting bismaleimide with an excess of diamine, and (c): excess tetracarboxylic anhydride, tricarboxylic acid anhydride, or dicarboxylate. And an acid anhydride-terminated oligomer synthesized using a diamine or a diol can be copolymerized.

When using maleamic acid as an additive, for example, (d): reacting excess maleic anhydride with a diamine to produce a maleamic acid group-terminated oligomer, (e) adding a diamine, and If necessary, it can be copolymerized by mixing bismaleimide.
Or (d): A maleic acid group-terminated oligomer is prepared by reacting excess maleic anhydride and diamine, and (f): Amino-terminated oligomer synthesized using excess diamine and bismaleimide. Can be copolymerized by mixing.
Alternatively, (i): a bismaleimide and an excess of diamine are reacted to prepare an amino group-terminated oligomer, and (g): maleic anhydride and then diamine are mixed together for copolymerization.

In (i), (b), (c), and (d), by using a secondary amine when constructing the amic acid structural unit, and when constructing the amic acid, ester acid, and maleamic acid structural units, By using a secondary diamine in which one —H on NH ₂ is replaced with alkyl or the like, it is possible to design a molecule having such a structure that imidization does not occur when the coating film is heated. Therefore, by eliminating the imidization additive and maleimide polymer at the calculated ratio, the variation of imidation rate due to fluctuations in conditions during heat treatment of coating film is eliminated. It is possible to suppress the respective changes such as the adhesion of the coating film to the substrate, the electrical characteristics, or the pretilt angle when the coating film is used for the liquid crystal alignment film. You can get a quality product.

  The copolymer obtained by copolymerizing maleimide polymer and polyamic acid is composed of an amic acid structure using diamine and tetracarboxylic acid in the main chain, and 3-aminopyrrolidine using diamine and bismaleimide. A copolymer having a -2,5-dione structure.

  A copolymer obtained by copolymerizing a maleimide polymer and polyester acid has an ester acid structure using diol and tetracarboxylic acid in the main chain, and 3-aminopyrrolidine using diamine and bismaleimide. A copolymer having a -2,5-dione structure.

  The copolymer obtained by copolymerizing maleimide polymer and maleamic acid is composed of a maleamic acid structure using maleic anhydride and diamine in the main chain, and 3-aminopyrrolidine using diamine and bismaleimide. A copolymer having a -2,5-dione structure. These copolymers are all novel compounds, and the formation of the copolymer is a phenomenon in which the viscosity of the reaction solution increases during polymerization, or the liquid chromatography analysis described above increases the molecular weight after the polymerization compared to the intermediate oligomer. This can be confirmed by the phenomenon that occurs.

  In the case of the copolymer, the copolymerization ratio of the maleimide polymer and the acidic additive is preferably 10,000: 1 to 1: 100, and preferably 10,000: 5 to 1:10. Is more preferable.

The solvent used in the composition of the present invention is appropriately selected from various viewpoints. For example, the solvent is used from the viewpoint of adjusting the physical properties of the composition (viscosity, solubility, surface tension, etc.), ease of handling (evaporation rate is appropriate, or there is no corrosiveness, odor, or toxicity). Can be used. One type of solvent may be used, or two or more types may be mixed and used. Examples of the solvent include the above-mentioned solvent having an alcoholic hydroxyl group and a protic amide solvent, which are used for preparing the polymer used in the composition of the present invention, but the following solvents are also used. For example, a polar organic solvent having a high ability to dissolve the maleimide polymer and a coating property improving solvent having a high ability to improve the coating property of the composition by changing the surface tension can be mentioned, and the solvent is a mixed solvent containing them. It is also preferable that there is. When using the composition of this invention as a composition for application | coating, the aspect which contains the said application | coating improvement solvent in the composition of this invention can illustrate preferably.

  Examples of the polar organic solvent include N-methyl-2-pyrrolidone, N, N′-dimethylimidazolidinone, N-methylcaprolactam, N, N-dimethylpropionamide, N, N-dimethylacetamide, N, N— Diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N, N, N ′, N′-tetramethylurea, dimethylsulfoxide, γ-butyrolactone, γ-valerolactone, δ-valerolactone, and ε -Caprolactone. The polar organic solvent is N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N′-dimethylimidazolidinone, γ-butyrolactone, γ-valerolactone, δ-valero. It is preferable to include any one or more selected from the group consisting of lactone and ε-caprolactone.

  Examples of the coating property improving solvent include 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl ether such as ethylene glycol monobutyl ether, diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether, ethylene glycol monoalkyl or phenyl. Acetate, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether such as propylene glycol monobutyl ether, dialkyl malonate such as diethyl malonate, dipropylene glycol monoalkyl ether such as dipropylene glycol monomethyl ether, and these acetates An ester compound is mentioned. The coating property improving solvent preferably contains one or more selected from the group consisting of the highly polar alcohol, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether.

In addition to the examples given in the above definitions, the following examples can be given for each structure.
Ether systems such as diethyl ether, methyl-t-butyl ether, diisopropyl ether, 1,4-dioxane and tetrahydrofuran; chain ester systems such as ethyl acetate and butyl acetate; ketone systems such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone; Aromatics such as toluene and xylene. These can be used alone or in combination of two or more.

  The composition of the present invention can form a liquid crystal alignment film. The liquid crystal alignment film is a method similar to the preparation of the liquid crystal alignment film from the polyimide-based liquid crystal aligning agent, that is, a step of forming a coating film, a step of heat-treating the formed coating film, and a step of performing an alignment treatment if necessary. It can produce by the method containing.

  The step of forming the coating film can be performed, for example, by applying the liquid crystal aligning agent of the present invention to a substrate for a liquid crystal display element or a measurement substrate such as calcium fluoride or silicon. Moreover, the said heat processing process can be performed by heating the obtained coating film at 50-400 degreeC, for example, Preferably it is 120-280 degreeC for 1 minute-3 hours, Preferably it is 1 minute-1 hour. Here, the film thickness of the liquid crystal alignment film is preferably 10 to 300 nm, and more preferably 30 to 150 nm.

In addition, the production of the liquid crystal alignment film may include further steps depending on the application. As such a further process, for example, in the case of producing a liquid crystal alignment film for IPS type or a liquid crystal alignment film for TN type, one main chain of the polymer in the liquid crystal alignment film obtained by the heat treatment is used. A rubbing process for aligning in the direction may be mentioned.
Further, the production of the liquid crystal alignment film may include a further process depending on the material. As such a further step, for example, when the main chain or side chain structure of maleimide contains a group having a photo-alignment property such as an azo group, a carbon-carbon double bond, or a carbon-carbon triple bond, such maleimide is used. Examples include a step of irradiating a coating film of a liquid crystal aligning agent containing a polymer used as a monomer with radiation such as ultraviolet rays to align the polymer in the coating film in one direction. As the liquid crystal aligning agent to which such a photo-alignment step can be applied, a liquid crystal alignment agent containing a polymer in which the structural unit including the group having the photo-alignment property is 5% or more with respect to all the structural units of the polymer. Agents. Such a photo-alignment process can be performed as described in, for example, Japanese Patent Application Laid-Open Nos. 2007-248637 and 2007-296991.

  The film thickness of the liquid crystal aligning film of this invention can be adjusted with the viscosity of a liquid crystal aligning agent, and the coating method of a liquid crystal aligning agent. The film thickness of the liquid crystal alignment film can be measured by a known film thickness measuring device such as a step meter or an ellipsometer. Furthermore, the components in the liquid crystal alignment film can be analyzed using a normal analysis means such as IR or MS after performing a treatment such as hydrolysis as necessary.

  The liquid crystal display element of the present invention has the liquid crystal alignment film of the present invention described above. The configuration of the liquid crystal display element of the present invention is not particularly limited except that the liquid crystal alignment film is the liquid crystal alignment film of the present invention described above.

  For example, in the liquid crystal display element, a pair of substrates arranged opposite to each other, electrodes formed on one or both of the opposed surfaces of the pair of substrates, and the pair of substrates are opposed to each other. A liquid crystal alignment film of the present invention formed on the surface and a liquid crystal layer formed between the pair of substrates.

  The pair of substrates with electrodes arranged opposite to each other is preferably a transparent substrate (for example, a glass substrate).

  An electrode is provided on the surface of at least one or both of the pair of substrates according to the form of the liquid crystal display element. The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Examples of such electrodes include ITO and metal vapor deposition films. The electrode may be formed on the entire surface of the substrate, or may be formed in a predetermined shape that is patterned, for example. Further, the electrode may be provided on only one of the pair of substrates, or may be provided on both.

  The liquid crystal alignment film of the present invention is formed on the surface of the electrode or the surface of the substrate. The formation of the liquid crystal alignment film of the present invention is as described above.

  The liquid crystal layer sandwiched between the pair of substrates includes a liquid crystal composition. Here, the liquid crystal composition is not particularly limited, and either a liquid crystal composition having a positive dielectric anisotropy or a liquid crystal composition having a negative dielectric anisotropy may be used depending on the driving mode. it can. One or more optically active compounds may be added to the liquid crystal composition having a positive or negative dielectric anisotropy.

  Of course, the liquid crystal display element of the present invention may have other members.

The liquid crystal display element of the present invention can be manufactured by any method. For example, the above-described methods can be summarized as follows: 1) a step of applying a liquid crystal aligning agent on the two transparent substrates (coating film forming step), 2) A step of drying the applied liquid crystal aligning agent by heat treatment, 3) a step of aligning the obtained liquid crystal alignment film as necessary, and 4) a liquid crystal composition between the two substrates after being bonded together Or a step of dropping a liquid crystal composition onto one substrate and then bonding to the other substrate.

  As a coating method in the step of applying the liquid crystal aligning agent, a spinner method, a printing method, a dipping method, a dropping method, an ink jet method and the like are generally known. These methods are also applicable in the present invention.

  Moreover, as a method for performing the heat treatment step, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. These methods are also applicable in the present invention. The heat treatment may be carried out in one time, divided into multiple times, or gradually raised in temperature, but may be performed at a low temperature to prevent foaming and to sufficiently remove the solvent. A method of combining drying at high temperature is preferred. That is, it is preferable to perform the drying process of the first heat treatment at a relatively low temperature (50 to 140 ° C.) within a range in which the solvent can be gradually evaporated. The second heat treatment step is performed at a relatively high temperature (140 to 400 ° C.) for the purpose of removing the remaining solvent as much as possible or for the purpose of accelerating the reaction when a heat-reactive additive is used. Preferably it is done. Also preferred is a method in which the heat treatment is started at a relatively low temperature (50 to 140 ° C.), and then the temperature is gradually increased and the heat treatment is terminated at a relatively high temperature (140 to 400 ° C.).

  Next, an adhesive is applied onto one substrate, and the liquid crystal composition is injected in a vacuum. In the case of the dropping injection method, the liquid crystal composition is dropped on a substrate before bonding, and then bonded on the other substrate. The liquid crystal display element of the present invention is produced by curing the adhesive used for bonding with heat or ultraviolet rays.

  A polarizing plate (polarizing film), a wave plate, a light scattering film, a driving circuit, and the like may be mounted on the liquid crystal display element of the present invention.

  The composition of the present invention can be used for an adhesive, a filter and the like in addition to the liquid crystal aligning agent, depending on the type of the additive, and can be prepared using a known method.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. The compounds used in the examples are as follows.
<Bismaleimide>

<Diamine>

<Tetracarboxylic acid anhydride>
Pyromellitic dianhydride: T1,
1,2,3,4-cyclobutanetetracarboxylic dianhydride: T2,
3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride: T3

<Diol>
-4,4'-bicyclohexanol: L1,
Tetradecane-1,2-diol: L2,
・ Trimethylolethane: L3

<Maleic anhydride>

<Novolac resin>
Bisphenol A novolak resin: H1 (trade name: VH4170, manufactured by DIC Corporation) <Polyvinylphenol resin>
-Polyparavinylphenol: H2 (trade name: Marca Linker M, manufactured by Maruzen Petrochemical Co., Ltd.)
<Benzoxazine>
Bisphenol S-type benzoxazine: H3 (trade name: BS-BXZ, manufactured by Konishi Chemical Industries, Ltd.)
<Epoxy compound>
Bisphenol A novolac type epoxy compound: N1 (trade name: 157S70, manufactured by Mitsubishi Chemical Corporation)
N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane: N2 (manufactured by Aldrich)
3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate: N3 (trade name: Celoxide 2021P, manufactured by Daicel Chemical Industries, Ltd.) Bisphenol A type epoxy compound: N4 (trade name: 828, (Mitsubishi Chemical Corporation)

<Nadiimide>
Bis (4-nadiimidophenyl) methane: N5 (trade name: BANI-M, manufactured by Maruzen Petrochemical Co., Ltd.)
<Acrylic compound>
Amine-modified bisphenol A type epoxy acrylate: N6 (trade name: EBECRYL 3703, manufactured by Daicel Cytec)
N, N '-(2,3-dihydroxybutane-1,4-diyl) bis (acrylamide): N7 (manufactured by Aldrich)
Phosphoric acid-modified epoxy acrylate: N8 (trade name: 168, manufactured by Daicel Cytec Co., Ltd.) <Vinyl sulfone compound>
Bis (vinylsulfonyl) methane: VS-1
<Thiol compound>
Bismuthiol: HS-1
・ 4,4′-thiobisbenzenethiol: HS-2
<Oxazoline compound>
1,3-bis (4,5-dihydro-2-oxazolyl) benzene: N9 (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Thiirane compound>
-2,3-manufactured according to a known method from glycidyl methacrylate and thiourea (method described in Phosphorus, Sulfur and Silicon and the Related Elements, 2005, vol. 180, # 8 p. 1809-1814, etc.) A copolymer solution having a molar ratio of 2/8, in which epithiopropyl methacrylate and N-phenylmaleimide are polymerized according to a known method (method described in JP-A-7-5684, etc.): N10
<Silane compound>
・ Glycidyloxydimethoxysilane: N11 (manufactured by Chisso Corporation)
・ 3-Aminopropyltrimethoxysilane: N12 (manufactured by Chisso Corporation)
<Allyl compound>
A known method from allyl bromide and 4,4′-diaminodiphenylmethane (Journal of the
N, N, N ′, N′-tetraallyl-4,4′-diaminodiphenylmethane produced according to the method described in American Chemical Society, 2007, vol.129, # 35 p.10707-10713 etc .: N13

<Solvent>
Tetrahydrofurfuryl alcohol: S1
N-methylpyrrolidone: S2
・ Γ-butyrolactone: S3
・ Butyl cellosolve (ethylene glycol monobutyl ether): S4
・ Xylene: S5
・ Benzyl alcohol: S6
M-cresol: S16

・その他
ｐ−トルエンスルホン酸：Ｚ１

Other p-toluenesulfonic acid: Z1

[Reference Example 1] Production of bismaleimide M3 80 mL of S2 and 13.242 g (31.328 mmol) of A10 were placed in a 300 mL four-necked flask equipped with a thermometer, stirrer, raw material inlet and nitrogen gas inlet, and dried. It stirred and melt | dissolved under nitrogen stream. Next, 6.758 g (68.921 mmol) of D1 was added to the obtained solution under ice cooling, and the mixture was reacted at room temperature for 3 hours. After 3 hours, 2.0 g of Z1 and 240 mL of S5 were added and gradually heated to raise the temperature. When refluxing started, the reaction was continued for 7 hours while removing the produced water out of the system. After completion of the reaction, the reaction solution was cooled to room temperature and concentrated under reduced pressure. The residue was poured into water and the solid was collected by filtration. Further purification by column chromatography (SiO ₂ , toluene / ethyl acetate = 5/1 (volume ratio)) gave 13.10 g (23.183 mmol, yield 74%) of M3.

Reference Example 2 Production of Bismaleimide M5 80 mL of S2 and 10.722 g (24.895 mmol) of A11 were placed in a 300 mL four-necked flask equipped with a thermometer, stirrer, raw material inlet and nitrogen gas inlet, and dried. The mixture was stirred and suspended in a nitrogen stream. Next, 5.31 g (54.769 mmol) of D1 was added to the obtained suspension under ice cooling, and the mixture was reacted at room temperature for 3 hours. When the reaction temperature rose during the reaction, the reaction temperature was kept at about 80 ° C. or lower for the reaction. After 3 hours, 2.0 g of Z1 and 240 mL of S5 were added and gradually heated to raise the temperature. When refluxing started, the reaction was continued for 7 hours while removing the produced water out of the system. After completion of the reaction, the reaction solution was cooled to room temperature and concentrated under reduced pressure. The residue was poured into water and the solid was collected by filtration. Furthermore, the residue was dissolved in toluene and reprecipitated in ethanol to obtain 10.090 g (17.022 mmol, yield 74%) of M5.

[Reference Example 3] Production of bismaleimide M6 In a 500 mL four-necked flask equipped with a thermometer, stirrer, raw material inlet and nitrogen gas inlet, 100 mL of S2 and 18.362 g (86.495 mmol) of A12 were placed and dried. It stirred and melt | dissolved under nitrogen stream. Next, 18.659 g (190.29 mmol) of D1 was added to the obtained solution under ice cooling, and the mixture was reacted at room temperature for 3 hours. After 3 hours, a solution in which 3.0 g of Z1 was dissolved in 300 mL of S5 was added to the reaction solution, which was gradually heated to raise the temperature. When refluxing started, the reaction was continued for 7 hours while removing the produced water out of the system. After completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration. The solid was washed with water and recrystallized using S2, to obtain 19.325 g (51.897 mmol, yield 60%) of M6.

<1. Synthesis of maleimide polymer>
[Production Example A1]
In a 100 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet, 0.978 g (11.35 mmol) of A1 and 23.5 g of S1 were placed and dissolved under stirring in a dry nitrogen stream. Next, 5.022 g (11.35 mmol) of M1 and 23.5 g of S1 were added to the obtained solution, and the mixture was reacted for 24 hours in a room temperature environment. After 24 hours, 47.0 g of S2 was added to the reaction solution and stirred until uniform to obtain a maleimide polymer solution having a concentration of 6% by weight. This polymer solution is designated as PM1. Table 1 shows the composition ratio and physical properties of PM1.

[Production Examples A2 to A4]
As shown in Table 1, polymer solutions PM2 to 4 were prepared in accordance with Production Example 1 except that bismaleimide, diamine, or the solvent at the time of dilution was changed.

[Production Examples A5 to A14]
As shown in Table 1, polymer solutions PM5 to 14 were prepared according to Production Example 1 except that the solvent during polymerization and the solvent during dilution were changed.

[Production Example A15]
3.758 g (14.11 mmol) of A13 and 23.5 g of S16 were placed in a 100 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet, and dissolved under stirring in a dry nitrogen stream. Next, 6.242 g (14.11 mmol) of M1 and 23.5 g of S1 were added to the obtained solution, and the mixture was reacted for 24 hours in a room temperature environment. After 24 hours, 47.0 g of S2 was added to the reaction solution and stirred until uniform to obtain a maleimide polymer solution having a concentration of 10% by weight. This polymer solution is designated as PM15. The composition ratio and physical properties of PM15 are shown in Table 1.

<2. Synthesis of Amic Acid-Maleimide Copolymer>
[Production Example B1]
In a 100 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet, 1.023 g (11.88 mmol) of A1 and 23.5 g of S1 were placed and dissolved under stirring in a dry nitrogen stream. Next, 4.731 g (10.69 mmol) of M1 and 23.5 g of S1 were added to the obtained solution, and the reaction was performed for 5 hours in a room temperature environment. After 5 hours, 0.130 g (0.594 mmol) of T1 and 0.116 g (0.594 mmol) of T2 were added under ice cooling. Further, 47.0 g of S2 was added and reacted for 15 hours in a room temperature environment to obtain a solution of an amic acid-maleimide copolymer having a concentration of 6% by weight. This polymer solution is designated as PMA1, and the composition ratio and physical properties of PMA1 are shown in Table 2.

[Production Example B2]
In a 100 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet, 0.947 g (10.99 mmol) of A1 and 23.5 g of S1 were placed and dissolved under stirring in a dry nitrogen stream. Next, 3.927 g (8.874 mmol) of M1 and 23.5 g of S1 were added to the obtained solution, and the mixture was reacted for 5 hours in a room temperature environment. After 5 hours, 0.194 g (2.252 mmol) of A1 was added to the reaction solution under ice cooling, and then 0.491 g (2.252 mmol) of T1 and 0.442 g (2.252 mmol) of T2 were added. Further, 47.0 g of S2 was added and reacted at room temperature for 15 hours to give an amic acid having a concentration of 6% by weight.
A solution of maleimide copolymer was obtained. This polymer solution is designated as PMA2, and the composition ratio and physical properties of PMA2 are shown in Table 2.

[Production Examples B3 to B15]
Except having changed each raw material ratio as shown in Table 2, polymer solution PMA3-PMA15 was obtained based on manufacture example B2. Table 2 shows the composition ratio and physical properties of PMA3 to PMA15.

<3. Synthesis of Maleamic Acid-Maleimide Polymer>
[Production Example B16]
In a 100 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, 0.22 g (1.145 mmol) of A2 and 23.5 g of S2 were placed and dissolved under stirring in a dry nitrogen stream. Next, 0.225 g (2.291 mmol) of D1 and 23.5 g of S2 were added to the obtained solution under ice cooling, and the mixture was reacted for 24 hours in a room temperature environment. After 5 hours, 47.0 g of S1 was added to the reaction solution, 0.987 g (11.454 mmol) of A1 and 4.562 g (10.309 mmol) of A1 were added, and the mixture was reacted at 70 ° C. for 15 hours to obtain a concentration of 6 A solution of a weight percent maleamic acid-maleimide copolymer was obtained. This polymer solution is designated as PMA16, and the composition ratio and physical properties of PMA16 are shown in Table 3.

<4. Synthesis of polyester acid>
[Production Example C1]
In a 100 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, 3.64 g (12.489 mmol) of T3, 2.326 g (12.489 mmol) of L1, and g of S2 were placed. The mixture was stirred for 3 hours at 120 ° C. in a dry nitrogen stream to obtain a polyester acid solution (PE1) having a solid content of 6% by weight. Table 4 shows the composition ratio and physical properties of PE1.

[Production Example C2]
As shown in Table 3, except that the tetracarboxylic anhydride was changed to T1 (2.918 g, 13.378 mmol) and the diol was changed to L2 (3.082 g, 13.378 mmol), A molecular solution (PE2) was prepared. Table 4 shows the composition ratio and physical properties of PE2.

<5. Synthesis of polyester amic acid>
[Production Example D1]
In a 100 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet, 1.705 g (7.818 mmol) of T1, 1.533 g (7.818 mmol) of T2, and 0.282 g of L3 (2.345 mmol) and 54.0 g of S2 were added, and the mixture was stirred at 120 ° C. for 1 hour under a dry nitrogen stream. After cooling to 25 ° C., 2.480 g (12.508 mmol) of A2 was added to the reaction solution. After reacting for 30 hours while maintaining the temperature of the reaction system at 25 ° C., 25.0 g of S4 and 15.0 g of S3 were added, the temperature was raised to 50 ° C. and stirring was continued, and the polyester-polyamic acid solution (PEA1) Got. Table 5 shows the composition ratio and physical properties of PEA1.

<6. Synthesis of polyamic acid>
[Production Example E1]
In a 100 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, 2.934 g (14.801 mmol) of A1 and 54.0 g of S2 were placed and ice-cooled. Next, 1.14 g (7.401 mmol) of T1 and 1.451 g (7.401 mmol) of T2 were added to the resulting solution while stirring under ice cooling, and the reaction was performed for 30 hours while maintaining the temperature of the reaction system at 25 ° C. After that, 25.0 g of S4 and 15.0 g of S3 were added to the reaction solution, and the temperature was raised to 50 ° C. and stirring was continued to obtain a polyamic acid solution (PA1) having a concentration of 6 wt%. PA
Table 6 shows the composition ratio and physical properties of No. 1.

[Production Examples E2 to E5]
Polyamic acid solutions PA2 to PA5 were prepared according to Synthesis Example 1 except that tetracarboxylic dianhydride and diamine were changed as shown in Table 6. Table 6 shows the composition ratio and physical properties of PA2 to PA5.

<7. Synthesis of vinylsulfone compound-maleimide copolymer>
[Production Example F1]
In a 100 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet, 1.078 g (12.52 mmol) of A1 and 23.5 g of S1 were placed and dissolved under stirring in a dry nitrogen stream. Next, 4.431 g (10.01 mmol) of M1, 0.491 g (2.503 mmol) of VS1, and 23.5 g of S1 were added to the obtained mixture, and the mixture was reacted for 24 hours in a room temperature environment. After 24 hours, 47.0 g of S2 was added to the reaction solution and stirred until uniform to obtain a vinylsulfone compound-maleimide polymer solution having a concentration of 6% by weight. This polymer solution is designated as PMS1. Table 7 shows the composition ratio and physical properties of PM1.

[Production Example F2]
Except that bismaleimide and diamine were changed as shown in Table 7, polymer solution PMS2 was prepared according to Production Example F1. Table 7 shows the composition ratio and physical properties of PMS2.
[Production Example F3]
Except having changed the solvent as shown in Table 7, polymer solution PMS3 was prepared based on manufacture example F1. Table 7 shows the composition ratio and physical properties of PMS3.

<8. Synthesis of Thiol Compound-Maleimide Copolymer>
[Production Example G1]
In a 100 ml four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet and a nitrogen gas inlet, 1.534 g (7.290 mmol) of A8 and 23.5 g of S1 were placed and dissolved under stirring in a dry nitrogen stream. . Then, 3.919 g (10.93 mmol) of M2 and 10.0 g of S1 were added to the obtained mixture, and the mixture was reacted for 8 hours in a room temperature environment. After 8 hours, 0.548 g (3.645 mmol) of HS1 and 13.5 g of S1 were added to the mixture and allowed to react for 16 hours in a room temperature environment. After 16 hours, 47.0 g of S2 was added to the reaction solution and stirred until uniform, thereby obtaining a thiol compound-maleimide polymer solution having a concentration of 6% by weight. This polymer solution is designated as PMT1. Table 8 shows the composition ratio and physical properties of PMT1.

[Production Example G2]
A polymer solution PMT2 was prepared according to Production Example G1 except that the thiol was changed as shown in Table 8. Table 8 shows the composition ratio and physical properties of PMT2.
[Production Example G3]
Except having changed the solvent as shown in Table 8, polymer solution PMT3 was prepared based on manufacture example G1. Table 8 shows the composition ratio and physical properties of PMT3.

<9. Production of liquid crystal display element>
[Example 1]
6% by weight maleimide polymer solution (PM1) obtained in Production Example A1 and 6% by weight polyamic acid solution (PA1) obtained in Production Example E1 were mixed at 8/2 (weight ratio), Further, a mixed solvent of S1 / S2 = 1/1 (weight ratio) was added and the whole was diluted so that the concentration of the polymer was 4% by weight to obtain a liquid crystal aligning agent.

[Examples 2 to 43, 48 to 56, Comparative Examples 1, 2, and 3]
After mixing with the compositions shown in Tables 9, 10, and 11, as in Example 1, a mixed solvent of S1 / S2 = 1/1 (weight ratio) was added, and the whole had a polymer concentration of 4% by weight. The liquid crystal aligning agent was obtained by diluting to obtain

<Method for Manufacturing Liquid Crystal Display Element (Examples 1-36, 48-56, Comparative Examples 1 and 3)>
Using the obtained liquid crystal aligning agent, a liquid crystal display element was produced as follows.
The liquid crystal aligning agent was applied to two glass substrates with an ITO electrode with a spinner to form a film with a thickness of 70 nm. After coating, the film was heated and dried at 80 ° C. for about 5 minutes, and then heat-treated at 210 ° C. for 20 minutes to form a liquid crystal alignment film. Next, the surface of the substrate on which the liquid crystal alignment film was formed was rubbed with a rubbing apparatus to perform the alignment treatment. First, the obtained liquid crystal alignment film A was rubbed with a rubbing treatment device manufactured by Iinuma Gauge Co., Ltd., and the amount of push of the rubbing cloth (hair length 1.8 mm: rayon) was 0.40 mm, and the stage moving speed was 60 mm. / Sec, and a rubbing treatment was performed at a roller rotation speed of 1,000 rpm. Thereafter, the liquid crystal alignment film was ultrasonically cleaned in ultrapure water for 5 minutes and then dried in an oven at 120 ° C. for 30 minutes.

  One glass substrate was sprayed with a 7 μm gap material, and the surface on which the liquid crystal alignment film was formed was placed inside so as to face each other so that the rubbing direction was anti-parallel, and then sealed with an epoxy curing agent, and the gap was 7 μm. A parallel cell was produced. The liquid crystal composition shown below was injected into the cell, and the injection port was sealed with a photocuring agent. Next, a heat treatment was performed at 110 ° C. for 30 minutes to manufacture a liquid crystal display element.

<Method for Manufacturing Liquid Crystal Display Element (Examples 37 to 43, Comparative Example 2)>
Using the obtained liquid crystal aligning agent, a liquid crystal display element was produced as follows.
The liquid crystal aligning agent was applied to two glass substrates with an ITO electrode with a spinner to form a film with a thickness of 70 nm. After coating, the film was heated and dried at 80 ° C. for about 5 minutes, and then heat-treated at 210 ° C. for 20 minutes to form a liquid crystal alignment film. Thereafter, the liquid crystal alignment film was ultrasonically cleaned in ultrapure water for 5 minutes and then dried in an oven at 120 ° C. for 30 minutes.

  A 7 μm gap material was sprayed on one glass substrate, and the surface on which the liquid crystal alignment film was formed was placed inside, and then sealed with an epoxy curing agent to produce a cell with a gap of 7 μm. The liquid crystal composition shown below was injected into the cell, and the injection port was sealed with a photocuring agent. Subsequently, the heat processing were performed at 110 degreeC for 30 minute (s), and the liquid crystal display element concerning Examples 37-43 and the comparative example 2 was produced.

<10. Evaluation of orientation characteristics>
In the liquid crystal display elements produced in Examples 1 to 43, 48 to 56, and Comparative Examples 1 and 2, the liquid crystal composition was injected and the element before heat treatment was sandwiched between two polarizing plates, a backlight was applied, and a liquid crystal The orientation state was observed and evaluated by the presence or absence of fluid orientation. Those having no fluid orientation can be said to have good orientation. The results are shown in Tables 9, 10 and 11.

<11. Evaluation of electrical characteristics>
With respect to the liquid crystal display elements produced in Examples 1 to 43, 48 to 56 and Comparative Examples 1 and 2, ion density measurement and long-term reliability measurement were performed as follows.

1) Measurement of ion density (Examples 1 to 35, 37 to 43, 48 to 56, Comparative Examples 1 and 2)
The ion density of the liquid crystal display element was measured using a liquid crystal property evaluation apparatus 6254 type manufactured by Toyo Technica. The measurement conditions were waveform: triangular wave, frequency: 0.01 Hz, voltage: ± 10 V, and measurement temperature was 60 ° C. It can be said that the smaller this value, the better the electrical characteristics. The results are shown in Tables 9 and 11.

2) Measurement of ion density retention characteristics (Example 36, Comparative Example 1)
About the produced liquid crystal display element, ion density [pC] was calculated | required with time and the holding | maintenance characteristic was evaluated. As a test method for the holding characteristics, a method was adopted in which the liquid crystal display element was left in an atmosphere at a temperature of 100 ° C., and the ion density [pC] was taken out after a predetermined time. It can be said that the smaller the numerical value of the ion density after 500 hours, the better the ion density retention property and the better the long-term reliability of the electrical properties. The data after 500 hours are shown in Table 10.

As can be seen from Tables 9, 10 and 11, it can be seen that the molded article made of the composition containing the maleimide polymer of the present invention is very excellent in electrical characteristics. Therefore, it is particularly suitable for use in a liquid crystal alignment film.
In Comparative Example 3, since the odor of the solvent was strong, the solution could not be applied to obtain a film.

<11. Formation of coating>
[Example 44]
The polymer solution (PMS1) obtained in Production Example F1 was diluted with a mixed solvent of S1 / S2 = 1/1 (weight ratio) so that the concentration of the polymer was 4% by weight, A coating solution was obtained. The obtained solution was applied to a glass substrate with a spinner to form a film having a thickness of 70 nm. After coating, the film was heated and dried at 80 ° C. for about 5 minutes to form a film.

[Examples 45 to 47, Comparative Examples 4 and 5]
As in Example 44, the polymer solution shown in Table 12 was mixed with a mixed solvent of S1 / S2 = 1/1 (weight ratio) to dilute the whole so that the concentration of the polymer was 4% by weight. A coating solution was obtained. The obtained solution was applied to a glass substrate with a spinner to form a film having a thickness of 70 nm. After coating, the film was heated and dried at 80 ° C. for about 5 minutes to form a film.

In Examples 44 to 47, a uniform film could be obtained.
In Comparative Examples 4 and 5, since the odor of the solvent was strong, it was not possible to obtain a film by applying the solution as it was.

Since the maleimide polymer is formed by an addition reaction between bismaleimide and diamine, a tetracarboxylic dianhydride containing an acid dianhydride group and a secondary or tertiary amino group adjacent thereto is used as a raw material. A configuration difficult to form with a polyamic acid-derived polyimide polymer can be realized. Therefore, in the functional material derived from polyimide, further improvement of the function of the functional material and expression of a new function are expected, and further diversification of the functional material conventionally derived from polyimide is expected.
Specific examples of such applications include coating materials, insulating materials, printed wiring board materials, adhesives, sealing materials, molding materials, gas separation membrane materials, and wire materials.

Claims (47)

  A composition containing at least one solvent selected from the group consisting of a maleimide polymer, an additive, a solvent having an alcoholic hydroxyl group, and a protic amide solvent.   The composition according to claim 1, wherein the maleimide polymer has a weight average molecular weight of 3,000 to 500,000.   The composition according to claim 1 or 2, wherein the maleimide polymer is a polymer obtained by Michael addition reaction using bismaleimide and diamine.   The composition according to claim 3, wherein the diamine is an aliphatic diamine or an alicyclic diamine.   5. The polymer according to claim 1, wherein the maleimide polymer is polymerized in a solvent containing at least one selected from the group consisting of a solvent having an alcoholic hydroxyl group and a protic amide solvent. The composition according to claim 1.   The solvent having an alcoholic hydroxyl group is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, 1-hexanol, 2-ethylhexanol, benzyl alcohol. , (O-, m-, or p-) methylbenzyl alcohol, (o-, m-, or p-) methoxybenzyl alcohol, 1-phenylethyl alcohol, 2-phenylethyl alcohol, ethylene glycol, glycerol, 3- Methyl-3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monoethyl ether, triethylene glycol monoalkyl ether Propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and 1) an alcoholic hydroxyl group, and 2) a highly polar alcohol having at least one group selected from the group consisting of amides, esters, and cyclic ethers. The composition according to claim 5, which is a solvent containing any one or more selected from the group. The highly polar alcohol is methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, 2-hydroxy-3- Any one or more selected from the group consisting of methyl butenoate, dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, and compounds represented by the following formulas (1) to (21) The composition according to claim 6, wherein the protic amide solvent contains at least one selected from the group consisting of compounds represented by the following formulas (22) to (26).

  The solvent contains a solvent having an alcoholic hydroxyl group or a protic amide solvent, and contains 20% by weight or more of the solvent having an alcoholic hydroxyl group or a protic amide solvent based on the total amount of the solvent. The composition of any one of these.   The said maleimide type polymer is a composition of any one of Claims 1-8 manufactured by the method which does not include the process of solvent substitution after superposition | polymerization.   10. The additive according to any one of claims 1 to 9, wherein the additive includes at least one structure selected from the group consisting of an acidic group structure, a polymerizable group structure, and a cyclic ester structure. Composition.   The composition according to claim 10, wherein the additive includes an acidic group, and the acidic group includes any one or more selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phenolic aqueous group.   The said additive contains an acidic group, The additive containing this acidic group contains any 1 or more types selected from the group which consists of a polyamic acid, a polyester acid, and a polymaleamic acid of Claim 11. Composition.   The composition according to any one of claims 10 to 12, wherein the additive contains an acidic group, and the additive containing the acidic group is incorporated in the maleimide polymer chain.   The said additive contains an acidic group, The additive containing this acidic group contains any 1 or more types selected from the group which consists of a novolak resin, polyvinylphenol, a flavonoid type phenol, and a benzoxazine compound. The composition of any one of -13.   The additive is a cyclic ester compound, an epoxy compound, an epoxy compound curing agent, maleimide, nadiimide, acrylic compound, methacrylic compound, vinylsulfone compound, thiol compound, oxazoline compound, thiirane compound, metal compound, surfactant, and The composition according to any one of claims 1 to 14, comprising any one or more selected from the group consisting of pigments.   The composition according to claim 15, wherein the additive includes one or more selected from the group consisting of an epoxy compound and oxazoline.   The composition according to claim 15 or 16, wherein the additive is a novolac epoxy compound.   The composition according to any one of claims 15 to 17, wherein the additive is a lactone. Maleimide polymer obtained by polymerizing bismaleimide and diamine, dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, and the following formulas (2), (4), (5 ) To (10), (12) to (14), and a composition containing any one or more solvents selected from the group consisting of (17) to (19).

  The composition according to claim 19, wherein the diamine is an aliphatic diamine or an alicyclic diamine. The bismaleimide is one or more selected from the group consisting of compounds represented by the following formulas (M1), (M2), (M7), and (M8), and the diamine is represented by the following formula (II-1-5) , (II-1-6), (II-1-22), (II-1-24), (II-1-30), (IV-1-1), and (IV-1-2) 21. A composition according to claim 19 or 20, comprising any one or more selected from the group consisting of the indicated compounds.

  The solvent is dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, and formulas (2), (4), (5) to (10), (12) with respect to the total amount of the solvent. ) To (14), (17) to (19), wherein one or more solvents selected from the group consisting of 20% by weight or more in total are contained. Composition. Raw materials containing bismaleimide and diamine are dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, and the following formulas (2), (4), (5) to (10), (12) to (14) and (17) to (19), the polymer including a step of polymerizing in a solvent containing any one or more solvents selected from the group consisting of Contains at least one solvent selected from the group consisting of the following formulas (2), (4), (5) to (10), (12) to (14), and (17) to (19) A method for producing the composition.

  24. The method of claim 23, wherein the diamine is an aliphatic diamine or an alicyclic diamine. The bismaleimide contains at least one selected from the group consisting of compounds represented by the following formulas (M1), (M2), (M7), and (M8), and the diamine has the following formula (II-1) -5), (II-1-6), (II-1-22), (II-1-24), (II-1-30), (IV-1-1), and (IV-1- The method according to claim 23 or 24, comprising any one or more selected from the group consisting of compounds represented by 2).

  The solvent is dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, and formulas (2), (4), (5) to (10), (12) with respect to the total amount of the solvent. 26) The composition according to any one of claims 23 to 25, which contains a total of 20% by weight or more of any one or more solvents selected from the group consisting of (14) and (17) to (19). Method.   A method for producing a maleimide polymer copolymer comprising a 3-aminopyrrolidine-2,5-dione structural unit and an amic acid structural unit, wherein (a): amino is obtained by reacting bismaleimide with excess diamine. A process for producing a maleimide polymer, wherein an oligomer at the base end is prepared and copolymerized by adding (b): tetracarboxylic acid anhydride, tricarboxylic acid chloride anhydride, or dicarboxylic acid chloride to it . A method for producing a maleimide polymer copolymer comprising a 3-aminopyrrolidine-2,5-dione structural unit and an amic acid structural unit, wherein (a): amino is obtained by reacting bismaleimide with excess diamine. An oligomer at the terminal of the acid end synthesized by using (iii) an excess of tetracarboxylic acid anhydride, tricarboxylic acid chloride anhydride, or dicarboxylic acid chloride, and a diamine or diol. A method for producing a maleimide polymer copolymer, wherein the copolymer is copolymerized by mixing.   A method for producing a maleimide polymer comprising a 3-aminopyrrolidine-2,5-dione structural unit and a maleamic acid structural unit, wherein (d): an excess of maleic anhydride and diamine are reacted. A method for producing a maleimide polymer copolymer, wherein a maleamic acid group-terminated oligomer is prepared and copolymerized by mixing (e): diamine and bismaleimide.   A method for producing a maleimide polymer comprising a 3-aminopyrrolidine-2,5-dione structural unit and a maleamic acid structural unit, wherein (d): an excess of maleic anhydride and diamine are reacted. A method for producing a maleimide polymer copolymer, in which a maleamic acid group-terminated oligomer is prepared, and (f): an amino-terminated oligomer synthesized using excess diamine and bismaleimide is mixed and copolymerized. .   A method for producing a maleimide polymer comprising a 3-aminopyrrolidine-2,5-dione structural unit and a maleamic acid structural unit, wherein (a): amino is obtained by reacting bismaleimide with excess diamine. A process for producing a maleimide polymer copolymer, in which an oligomer at the base end is prepared, and (g): maleic anhydride and then diamine are mixed and copolymerized.   A copolymer having an amic acid structural unit derived from a diamine and a tetracarboxylic acid derivative and a 3-aminopyrrolidine-2,5-dione structural unit derived from a diamine and bismaleimide in the main chain.   The copolymer according to claim 32, wherein a secondary amine is used in the construction of the amic acid structural unit.   A copolymer having an ester acid structural unit derived from a diol and a tetracarboxylic acid derivative and a 3-aminopyrrolidine-2,5-dione structural unit derived from a diamine and bismaleimide in the main chain.   A copolymer having a succinic acid structural unit derived from maleic anhydride and diamine and a 3-aminopyrrolidine-2,5-dione structural unit derived from diamine and bismaleimide in the main chain.   36. The copolymer of claim 35, wherein a secondary amine is used in the construction of the succinic acid building block.   The composition according to any one of claims 1 to 22, the composition produced by the method according to any one of claims 23 to 26, and the composition according to any one of claims 27 to 31. A coating material comprising any one selected from a copolymer produced by a production method and the copolymer according to any one of claims 32-36.   The composition according to any one of claims 1 to 22, the composition produced by the method according to any one of claims 23 to 26, and the composition according to any one of claims 27 to 31. An insulating material comprising any one selected from a copolymer produced by a production method and the copolymer according to any one of claims 32-36. The composition according to any one of claims 1 to 22, the composition produced by the method according to any one of claims 23 to 26, and the composition according to any one of claims 27 to 31. A printed wiring board material comprising any one selected from a copolymer produced by a production method and the copolymer according to any one of claims 32-36.   The composition according to any one of claims 1 to 22, the composition produced by the method according to any one of claims 23 to 26, and the composition according to any one of claims 27 to 31. A liquid crystal aligning agent comprising any one selected from a copolymer produced by a production method and the copolymer according to any one of claims 32 to 36.   The liquid crystal aligning film formed by heat-processing the coating film of the liquid crystal aligning agent of Claim 40. A pair of substrates, a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment film for aligning the liquid crystal molecules in a predetermined direction In a liquid crystal display element having
The liquid crystal display element whose said liquid crystal aligning film is a liquid crystal aligning film of Claim 41.   The composition according to any one of claims 1 to 22, the composition produced by the method according to any one of claims 23 to 26, and the composition according to any one of claims 27 to 31. An adhesive comprising any one selected from a copolymer produced by a production method and the copolymer according to any one of claims 32-36.   The composition according to any one of claims 1 to 22, the composition produced by the method according to any one of claims 23 to 26, and the composition according to any one of claims 27 to 31. The sealing material containing either selected from the copolymer manufactured by the manufacturing method, and the copolymer of any one of Claims 32-36.   The composition according to any one of claims 1 to 22, the composition produced by the method according to any one of claims 23 to 26, and the composition according to any one of claims 27 to 31. 37. A molding material comprising any one selected from a copolymer produced by a production method and the copolymer according to any one of claims 32-36.   The composition according to any one of claims 1 to 22, the composition produced by the method according to any one of claims 23 to 26, and the composition according to any one of claims 27 to 31. A gas separation membrane material containing any one selected from a copolymer produced by a production method and the copolymer according to any one of claims 32-36.   The composition according to any one of claims 1 to 22, the composition produced by the method according to any one of claims 23 to 26, and the composition according to any one of claims 27 to 31. A wire material formed from any one selected from a copolymer produced by a production method and the copolymer according to any one of claims 32-36.