TWI547743B - A liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element - Google Patents

Description

液晶定向處理劑、液晶定向膜及液晶顯示元件 Liquid crystal directional treatment agent, liquid crystal alignment film and liquid crystal display element

本發明係關於在製作液晶定向膜時所使用的液晶定向處理劑及使用有液晶定向處理劑之液晶定向膜及液晶顯示元件。 The present invention relates to a liquid crystal alignment treatment agent used in the production of a liquid crystal alignment film, and a liquid crystal alignment film and a liquid crystal display element using the liquid crystal alignment treatment agent.

於液晶電視、液晶顯示器等所使用的液晶顯示元件，目前係作為實現薄型、輕量的顯示裝置而被廣泛使用。使液晶定向的液晶定向膜，主要係使用：將以聚醯胺酸(亦稱為polyamic acid)等之聚醯亞胺前驅物或可溶性聚醯亞胺的溶液作為主成分之液晶定向處理劑塗佈於玻璃基板等，再經燒成而成之所謂聚醯亞胺系之液晶定向膜。 Liquid crystal display elements used in liquid crystal televisions, liquid crystal displays, and the like are currently widely used as thin and lightweight display devices. A liquid crystal alignment film for orienting a liquid crystal is mainly used by coating a liquid crystal aligning agent containing a solution of a polyamidamine precursor such as polyamic acid (also called polyamic acid) or a soluble polyimine as a main component. A so-called polyimine-based liquid crystal alignment film which is baked on a glass substrate or the like and then fired.

伴隨著液晶顯示元件之更趨大型化、高精細化，並基於所謂液晶顯示元件的對比降低之控制或殘影現象之減低的需求，於液晶定向膜中，除了優異的液晶定向性、或液晶分子對於基板面的定向傾斜角(預傾角)之穩定的展現及控制之外，高電壓保持率、藉由交流驅動而產生的殘影之控制、由施加直流電壓時少量的殘留電荷、直流電壓所導致之積蓄的殘留電荷之迅速緩和等特性亦逐漸變得重要。液晶定向處理劑的成分之聚醯胺酸等之聚醯亞胺前驅物或可溶性聚醯亞胺，一般而言係藉由四羧酸二酐等之四羧酸衍生物與二胺成分之反應而合成，四羧酸衍生物及二胺成分之結構係為了滿足上述之液晶定向膜的各特性而作 各種選擇。 In addition to the demand for reduction in control or image sticking of the so-called liquid crystal display element, the liquid crystal display element is superior in liquid crystal alignment film, in addition to excellent liquid crystal orientation, or liquid crystal. In addition to the stable display and control of the orientation tilt angle (pretilt angle) of the substrate surface, high voltage retention, control of afterimage caused by AC drive, small residual charge by application of DC voltage, DC voltage The characteristics such as the rapid relaxation of the residual charge caused by the accumulation are gradually becoming important. The polyimine precursor or the soluble polyimine of polyamine or the like which is a component of the liquid crystal aligning agent is generally reacted with a dicarboxylic acid component such as tetracarboxylic dianhydride or the like. The structure of the tetracarboxylic acid derivative and the diamine component is synthesized in order to satisfy the characteristics of the liquid crystal alignment film described above. Various choices.

例如，針對上述之液晶的預傾角特性，係提案有：使用由將具有側鏈的二胺作為原料的一部分所製造的可溶性聚醯亞胺所構成之液晶定向處理劑的方法。於此方法中，由於因應具有側鏈的二胺之使用比例而可控制預傾角，故較容易得到目的之預傾角，就增大預傾角的手段而言為有效(參照例如專利文獻1)。 For example, a method of using a liquid crystal aligning agent composed of a soluble polyimine produced by using a diamine having a side chain as a raw material is proposed for the pretilt characteristics of the liquid crystal described above. In this method, since the pretilt angle can be controlled in accordance with the use ratio of the diamine having a side chain, it is easy to obtain the intended pretilt angle, and it is effective in the means for increasing the pretilt angle (see, for example, Patent Document 1).

但，由上述之可溶性聚醯亞胺所構成的液晶定向膜係殘留電荷特性不佳。因此，為了使預傾角特性與殘留電荷特性並存，而提案有：於上述可溶性聚醯亞胺中混合有聚醯胺酸之液晶定向處理劑(參照專利文獻2)。此外，亦提案有：含有特定之2種類的聚醯亞胺的液晶定向處理劑(專利文獻3)。 However, the liquid crystal alignment film system composed of the above-mentioned soluble polyimine has poor residual charge characteristics. Therefore, in order to coexist the pre-tilt characteristics and the residual charge characteristics, a liquid crystal aligning agent in which polylysine is mixed with the above-mentioned soluble polyimine is proposed (see Patent Document 2). In addition, a liquid crystal aligning agent containing a specific two types of polyimine is proposed (Patent Document 3).

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開平5-043688號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 5-043688

[專利文獻2]日本特開平8-220541號公報 [Patent Document 2] Japanese Patent Laid-Open No. Hei 8-220541

[專利文獻3]國際公開第2008/062877號手冊 [Patent Document 3] International Publication No. 2008/062877

然而，於該等文獻之液晶定向處理劑中，塗佈液晶定向處理劑時的塗膜均勻性為低，亦即，會有於塗膜面的端 部產生聚合物之凝聚物(亦稱為白化、凝聚)的情況。 However, in the liquid crystal aligning agent of these documents, the uniformity of the coating film when the liquid crystal aligning agent is applied is low, that is, there is a side at the surface of the coating film. The part produces agglomerates of polymers (also known as whitening, agglomeration).

本發明之課題在於解決上述之先前技術的問題點，並提供一種可製造賦予液晶高預傾角，且積蓄電荷為小的液晶定向膜，並且，不會引發白化、凝聚而塗膜均勻性優異的液晶定向處理劑、液晶定向膜及液晶顯示元件。 An object of the present invention is to solve the problems of the prior art described above, and to provide a liquid crystal alignment film which imparts a high pretilt angle to a liquid crystal and which has a small accumulated charge, and which is excellent in uniformity of coating film without causing whitening or aggregation. A liquid crystal alignment treatment agent, a liquid crystal alignment film, and a liquid crystal display element.

本發明者進行銳意研究的結果發現：包含具有特定結構的側鏈且規定該側鏈之相對量的2種類之特定聚合物及特定結構之交聯性化合物的液晶定向處理劑，用來達成上述之目的極為有效，因而完成本發明。 As a result of intensive research, the present inventors have found that a liquid crystal aligning agent containing a specific polymer of a specific structure and a relative amount of the side chain and two types of specific polymers and a crosslinkable compound having a specific structure is used to achieve the above. The purpose is extremely effective, thus completing the present invention.

亦即，本發明係為具有以下之要旨者。 That is, the present invention is intended to have the following gist.

1.一種液晶定向處理劑，其特徵為含有下述之特定聚合物(A)、特定聚合物(B)及特定交聯性化合物(C)。 A liquid crystal aligning agent characterized by comprising the specific polymer (A), a specific polymer (B) and a specific crosslinkable compound (C) described below.

特定聚合物(A)：由使用具有以式[1]所表示之側鏈的二胺化合物作為原料的一部分之聚醯亞胺前驅物及聚醯亞胺所成之群中所選出之至少1種的聚合物。 Specific polymer (A): at least one selected from the group consisting of a polyimine precursor having a diamine compound having a side chain represented by the formula [1] as a raw material and a polyimine. Kind of polymer.

特定聚合物(B)：由使用具有以式[1]所表示之側鏈的二胺化合物作為原料的一部分，且原料的全部二胺成分中之具有以式[1]所表示之側鏈的二胺化合物之比例，係較特定聚合物(A)的原料之全部二胺成分中之具有以式[1]所表示之側鏈的二胺化合物之比例更少的聚醯亞胺前驅物及聚醯亞胺所成之群中所選出之至少1種的聚合物。 Specific polymer (B): a part of a raw material using a diamine compound having a side chain represented by the formula [1], and having a side chain represented by the formula [1] in all the diamine components of the raw material The ratio of the diamine compound is a polyimine precursor having a smaller ratio of the diamine compound having a side chain represented by the formula [1] to all the diamine components of the raw material of the specific polymer (A) and At least one polymer selected from the group consisting of polyimine.

特定交聯性化合物(C)：具有2個以上由環氧基、異氰酸酯基、氧雜環丁烷基及環碳酸酯基所成之群中所選出之至少1種之取代基的交聯性化合物；具有2個以上由羥基、羥烷基及碳數1~6之烷氧烷基所成之群中所選出之至少1種之取代基的交聯性化合物；或具有2個以上聚合性不飽和鍵之交聯性化合物。 Specific crosslinkable compound (C): crosslinkability of at least one substituent selected from the group consisting of an epoxy group, an isocyanate group, an oxetanyl group, and a cyclic carbonate group a compound; a crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and an alkoxyalkyl group having 1 to 6 carbon atoms; or having two or more polymerizable groups; A crosslinkable compound of an unsaturated bond.

(式[1]中，X₁係單鍵、-(CH₂)_a-(a為1~15之整數)、-O-、-CH₂O-、-COO-或-OCO-；X₂係單鍵或-(CH₂)_b-(b為1~15之整數)；X₃係單鍵、-(CH₂)_c-(c為1~15之整數)、-O-、-CH₂O-、-COO-或-OCO-；X₄係由苯環、環己烷環及雜環所成之群中所選出之2價的環狀基，或具有類固醇骨架之碳數12~25之2價的有機基；前述環狀基上之任意的氫原子係可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子所取代；X₅係由苯環、環己烷環及雜環所成之群中所選出之2價的環狀基；此等環狀基上之任意的氫原子係可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子所取代；n為0~4之整數；X₆係碳數1~18之直鏈狀或分支狀烷基、碳數1~18之直鏈狀或分支狀含氟烷基、碳數1~18之直鏈狀或分支狀烷氧基、或碳數1~18之直鏈狀或分支狀含氟烷氧基；特定聚合物(A)的原料之二胺化合物所具有之以式[1]所表 示之側鏈與特定聚合物(B)的原料之二胺化合物所具有之以式[1]所表示之側鏈係可為相同或相異)。 (In the formula [1], X ₁ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-; X ₂ A single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15); X ₃ is a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-; X ₄ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a carbon number having a steroid skeleton 12~ a 25-valent organic group; any hydrogen atom on the above cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a fluorine-containing alkyl group having 1 to 3 carbon atoms. a fluoroalkoxy group having 1 to 3 carbon atoms or a fluorine atom; X ₅ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring; Any hydrogen atom on the group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkyl group having 1 to 3 carbon atoms. Substituted by an oxy group or a fluorine atom; n is an integer of 0 to 4; X ₆ is a linear or branched alkyl group having 1 to 18 carbon atoms; and a linear or branched fluorine-containing alkyl group having 1 to 18 carbon atoms; a linear or branched alkoxy group having a carbon number of 1 to 18 or a linear or branched carbon number of 1 to 18 A fluoroalkoxy group; a diamine compound of a raw material of a specific polymer (A) having a side chain of the formula [1] and a diamine compound of a raw material of the specific polymer (B) having the formula [1] The side chains shown can be the same or different).

2.如1之液晶定向處理劑，其中當將特定聚合物(A)的原料之全部二胺成分中之具有以式[1]所表示之側鏈的二胺化合物之比例設為1時，特定聚合物(B)的原料之全部二胺成分中之具有以式[1]所表示之側鏈的二胺化合物之比例為0.3以上且未達1.0。 2. The liquid crystal aligning agent according to 1, wherein when the ratio of the diamine compound having the side chain represented by the formula [1] in all the diamine components of the raw material of the specific polymer (A) is set to 1, The proportion of the diamine compound having a side chain represented by the formula [1] among all the diamine components of the raw material of the specific polymer (B) is 0.3 or more and less than 1.0.

3.如1或2之液晶定向處理劑，其中特定聚合物(A)的原料之具有以式[1]所表示之側鏈的二胺化合物及特定聚合物(B)的原料之具有以式[1]所表示之側鏈的二胺化合物，係分別為以下述式[1a]所表示之二胺化合物。 3. The liquid crystal aligning agent according to 1 or 2, wherein the raw material of the specific polymer (A) has a diamine compound having a side chain represented by the formula [1] and a raw material of the specific polymer (B) The diamine compound of the side chain represented by [1] is a diamine compound represented by the following formula [1a], respectively.

(式[1a]中，X₁、X₂、X₃、X₄、X₅、X₆、n係與式[1]中之X₁、X₂、X₃、X₄、X₅、X₆、n相同；m為1~4之整數；特定聚合物(A)的原料之以式[1a]所表示之二胺化合物與特定聚合物(B)的原料之以式[1a]所表示之二胺化合物係可為相同或相異)。 (In the formula [1a], X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , n are X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X in the formula [1] ₆ and n are the same; m is an integer of 1 to 4; the raw material of the specific polymer (A) is represented by the formula [1a] of the diamine compound represented by the formula [1a] and the specific polymer (B) The diamine compounds may be the same or different).

4.如1~3中任一項之液晶定向處理劑，其中特定聚合物(A)及特定聚合物(B)中之至少一者，係使用以下述式[2]所表示之二胺化合物作為原料之二胺成分。 4. The liquid crystal aligning agent according to any one of 1 to 3, wherein at least one of the specific polymer (A) and the specific polymer (B) is a diamine compound represented by the following formula [2] A diamine component as a raw material.

(式[2]中，Y₁係-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCO-、-CON(CH₃)-或-N(CH₃)CO-；Y₂係單鍵、2價的碳數1~20之脂肪族烴基、非芳香族環式烴基或芳香族烴基；Y₃係單鍵、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-COO-、-OCO-、-CON(CH₃)-、-N(CH₃)CO-或-O(CH₂)_i-(i為1~5之整數)；Y₄係1價的含氮芳香族雜環；h為1~4之整數)。 (In the formula [2], Y ₁ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ ) - or -N(CH ₃ )CO-; Y ₂ single bond, divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, non-aromatic cyclic hydrocarbon group or aromatic hydrocarbon group; Y ₃ single bond, -O- , -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ )CO- or -O(CH ₂ ) _i - (i is an integer of 1 to 5); Y ₄ is a monovalent nitrogen-containing aromatic heterocyclic ring; h is an integer of 1 to 4).

5.如1~4中任一項之液晶定向處理劑，其中特定聚合物(A)及特定聚合物(B)，係使用以下述式[3]所表示之四羧酸二酐作為原料的一部分。 5. The liquid crystal aligning agent according to any one of 1 to 4, wherein the specific polymer (A) and the specific polymer (B) are using a tetracarboxylic dianhydride represented by the following formula [3] as a raw material. portion.

(式[3]中，Z₁係含有碳數4~6之非芳香族環狀烴基之碳數4~13之4價的有機基)。 (In the formula [3], Z ₁ is a tetravalent organic group having 4 to 13 carbon atoms of a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms).

6.如5之液晶定向處理劑，其中Z₁係為以下述式[3a]~式[3j]所表示之結構。 6. The liquid crystal aligning agent according to 5, wherein the Z ₁ system has a structure represented by the following formula [3a] to formula [3j].

(式[3a]中，Z₂~Z₅係氫原子、甲基、氯原子或苯環，且可各自為相同或相異，式[3g]中，Z₆及Z₇係氫原子或甲基，且可各自為相同或相異)。 (In the formula [3a], Z ₂ to Z ₅ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may each be the same or different, in the formula [3g], a Z ₆ and Z ₇ hydrogen atom or a Bases, and may each be the same or different).

7.如1~6中任一項之液晶定向處理劑，其中特定交聯性化合物(C)係具有氧雜環丁烷基之交聯性化合物、具有環碳酸酯基之交聯性化合物、或具有由羥基、羥烷基及碳數1~6之烷氧烷基所成之群中所選出之至少1種的取代基之苯或酚性化合物的交聯性化合物。 7. The liquid crystal aligning agent according to any one of 1 to 6, wherein the specific crosslinkable compound (C) is a crosslinkable compound having an oxetanyl group, a crosslinkable compound having a cyclic carbonate group, Or a crosslinkable compound having a benzene or a phenolic compound having at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and an alkoxyalkyl group having 1 to 6 carbon atoms.

8.如1~7中任一項之液晶定向處理劑，其中特定聚合物(A)及特定聚合物(B)係為聚醯胺酸。 8. The liquid crystal aligning agent according to any one of 1 to 7, wherein the specific polymer (A) and the specific polymer (B) are polyamic acid.

9.如1~7中任一項之液晶定向處理劑，其中特定聚合物(A)及特定聚合物(B)係為使聚醯胺酸脫水閉環所得之聚醯亞胺。 9. The liquid crystal aligning agent according to any one of 1 to 7, wherein the specific polymer (A) and the specific polymer (B) are polyimine obtained by dehydrating and ring-closing polylysine.

10.如1~9中任一項之液晶定向處理劑，其中相對於特定聚合物(A)及特定聚合物(B)之總量100質量份，特定交聯性化合物(C)為0.1質量份~50質量份。 10. The liquid crystal aligning agent according to any one of 1 to 9, wherein the specific crosslinkable compound (C) is 0.1 mass based on 100 parts by mass of the total of the specific polymer (A) and the specific polymer (B). ~50 parts by mass.

11.如1~10中任一項之液晶定向處理劑，其中係含有5~60質量%之不良溶劑(poor solvent)。 11. The liquid crystal aligning agent according to any one of 1 to 10, which contains 5 to 60% by mass of a poor solvent.

12.一種液晶定向膜，其特徵為使用如1~11中任一項之液晶定向處理劑所得者。 A liquid crystal alignment film which is obtained by using the liquid crystal alignment treatment agent according to any one of 1 to 11.

13.如12之液晶定向膜，其係用於液晶顯示元件，該液晶顯示元件係在具備有電極之一對的基板之間具有液晶層而成，且係經過將含有藉由活性能量線及熱之至少一者而聚合的聚合性化合物之液晶組成物配置於前述一對的基板之間，並一面將電壓施加於前述電極間一面使前述聚合性化合物聚合的步驟所製造。 13. The liquid crystal alignment film of 12, which is used for a liquid crystal display element having a liquid crystal layer between substrates having one pair of electrodes, and which is to be subjected to active energy rays and The liquid crystal composition of the polymerizable compound polymerized at least one of the heat is disposed between the pair of substrates, and is produced by a step of applying a voltage between the electrodes to polymerize the polymerizable compound.

14.一種液晶顯示元件，其特徵為具有如12或13之液晶定向膜。 A liquid crystal display element characterized by having a liquid crystal alignment film such as 12 or 13.

藉由使用本發明之液晶定向處理劑，可得到賦予液晶高預傾角，且作為液晶顯示元件時之積蓄電荷為少的液晶定向膜。再者，本發明之液晶定向處理劑係可控制白化、凝聚，且其液晶配向膜之塗膜均勻性優異。此外，藉由使用此液晶定向膜，而可提供具有高預傾角，且積蓄電荷為少的液晶顯示元件。 By using the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal alignment film which imparts a high pretilt angle to the liquid crystal and which has a small accumulated charge as a liquid crystal display element. Further, the liquid crystal aligning agent of the present invention can control whitening and agglomeration, and has excellent coating film uniformity of the liquid crystal alignment film. Further, by using this liquid crystal alignment film, it is possible to provide a liquid crystal display element having a high pretilt angle and having a small accumulated charge.

以下，針對本發明進行詳細地說明。 Hereinafter, the present invention will be described in detail.

本發明係為含有特定聚合物(A)、特定聚合物(B) 及特定交聯性化合物(C)之液晶定向處理劑。所謂液晶定向處理劑係指用以形成液晶定向膜之塗佈液，所謂液晶定向膜係指用以使液晶定向於特定的方向之膜。針對本發明之液晶定向處理劑的各成分進行以下說明。 The present invention contains a specific polymer (A), a specific polymer (B) And a liquid crystal aligning agent of the specific crosslinkable compound (C). The liquid crystal alignment treatment agent refers to a coating liquid for forming a liquid crystal alignment film, and the liquid crystal alignment film refers to a film for orienting the liquid crystal in a specific direction. The respective components of the liquid crystal alignment treatment agent of the present invention will be described below.

<特定聚合物(A)及特定聚合物(B)> <Specific polymer (A) and specific polymer (B)>

特定聚合物(A)及特定聚合物(B)係為聚醯胺酸或聚醯胺酸酯等之聚醯亞胺前驅物或聚醯亞胺。亦即，特定聚合物(A)或特定聚合物(B)係只要各自由聚醯亞胺前驅物及聚醯亞胺所成之群中所選出之至少1種即可，其組合並無特別限定。例如，可為特定聚合物(A)為聚醯亞胺且特定聚合物(B)為聚醯亞胺前驅物之組合，亦可為特定聚合物(A)及特定聚合物(B)兩者皆為聚醯亞胺前驅物之組合，此外，亦可為特定聚合物(A)及特定聚合物(B)兩者皆為聚醯亞胺之組合。聚醯亞胺前驅物係藉由使由四羧酸及其之衍生物所選擇之至少一種的四羧酸成分與二胺成分進行聚合反應而得者。而，本發明所使用之特定聚合物(A)及特定聚合物(B)，係為使用具有以上述式[1]所表示的結構作為側鏈之二胺化合物作為原料之該二胺成分所合成的聚合物。 The specific polymer (A) and the specific polymer (B) are polyimine precursors or polyimines such as polylysine or polyamidomate. That is, the specific polymer (A) or the specific polymer (B) is not particularly limited as long as it is selected from at least one selected from the group consisting of a polyimide precursor and a polyimine. limited. For example, the specific polymer (A) may be a polyimine and the specific polymer (B) may be a combination of a polyimine precursor, or may be a specific polymer (A) and a specific polymer (B). All of them are a combination of a polyimine precursor, and a combination of a specific polymer (A) and a specific polymer (B) may be a polyimine. The polyimine precursor is obtained by polymerizing a tetracarboxylic acid component of at least one selected from a tetracarboxylic acid and a derivative thereof with a diamine component. In addition, the specific polymer (A) and the specific polymer (B) used in the present invention are the diamine component using a diamine compound having a structure represented by the above formula [1] as a side chain as a raw material. Synthetic polymer.

式[1]中，如上所述，X₁係單鍵、-(CH₂)_a-(a為1~15之整數)、-O-、-CH₂O-、-COO-或-OCO-。其中，單鍵、-(CH₂)_a-(a為1~15之整數)、-O-、-CH₂O-或-COO-，係因容易進行合成而為佳。較佳為單鍵、-(CH₂)_a-(a為1~ 10之整數)、-O-、-CH₂O-或-COO-。 In the formula [1], as described above, the X ₁ -based single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- . Among them, a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferred because it is easy to synthesize. It is preferably a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

式[1]中，X₂係單鍵或-(CH₂)_b-(b為1~15之整數)。其中，以單鍵或-(CH₂)_b-(b為1~10之整數)為佳。 In the formula [1], X ₂ is a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 15). Among them, a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 10) is preferred.

式[1]中，X₃係單鍵、-(CH₂)_c-(c為1~15之整數)、-O-、-CH₂O-、-COO-或-OCO-。其中，單鍵、-(CH₂)_c-(c為1~15之整數)、-O-、-CH₂O-、-COO-或-OCO-，係因容易進行合成而為佳。較佳為單鍵、-(CH₂)_c-(c為1~10之整數)、-O-、-CH₂O-、-COO-或-OCO-。 In the formula [1], X ₃ is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- is preferred because it is easy to synthesize. It is preferably a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O-, -COO- or -OCO-.

式[1]中，X₄係由苯環、環己烷環及雜環所成之群中所選出之2價的環狀基、或具有類固醇骨架之碳數12~25之2價的有機基。而，此等環狀基上之任意的氫原子係可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子所取代。其中，以苯環、環己烷環或具有類固醇骨架之碳數12~25之2價的有機基為佳。 In the formula [1], X ₄ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring, or a divalent organic group having a steroid skeleton of 12 to 25 carbon atoms. base. Further, any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a carbon number of 1 to 3. 3 is substituted by a fluorine-containing alkoxy group or a fluorine atom. Among them, a benzene ring, a cyclohexane ring or an organic group having a valence of 12 to 25 carbon atoms having a steroid skeleton is preferred.

式[1]中，X₅係由苯環、環己烷環及雜環所成之群中所選出之2價的環狀基。而，此等環狀基上之任意的氫原子係可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子所取代。 In the formula [1], X ₅ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring. Further, any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a carbon number of 1 to 3. 3 is substituted by a fluorine-containing alkoxy group or a fluorine atom.

式[1]中，n為1~4之整數。較佳為0~2之整數。 In the formula [1], n is an integer of 1 to 4. Preferably, it is an integer of 0-2.

式[1]中，X₆係碳數1~18之直鏈狀或分支狀烷基、碳數1~18之直鏈狀或分支狀含氟烷基、碳數1~18之直鏈狀或分支狀烷氧基、或碳數1~18之直鏈狀或分支狀含氟烷氧基。其中，以碳數1~18之直鏈狀或分支狀烷基、碳數1 ~10之直鏈狀或分支狀含氟烷基、碳數1~18之直鏈狀或分支狀烷氧基、或碳數1~10之直鏈狀或分支狀含氟烷氧基為佳。較佳為碳數1~12之直鏈狀或分支狀烷基或碳數1~12之直鏈狀或分支狀烷氧基。更佳為碳數1~9之直鏈狀或分支狀烷基或碳數1~9之直鏈狀或分支狀烷氧基。 In the formula [1], X ₆ is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 18 carbon atoms, and a linear chain having 1 to 18 carbon atoms. Or a branched alkoxy group or a linear or branched fluorine-containing alkoxy group having 1 to 18 carbon atoms. Among them, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 10 carbon atoms, or a linear or branched alkoxy group having 1 to 18 carbon atoms Or a linear or branched fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferred. It is preferably a linear or branched alkyl group having 1 to 12 carbon atoms or a linear or branched alkoxy group having 1 to 12 carbon atoms. More preferably, it is a linear or branched alkyl group having 1 to 9 carbon atoms or a linear or branched alkoxy group having 1 to 9 carbon atoms.

式[1]中之X₁、X₂、X₃、X₄、X₅、X₆及n之較佳組合係如表1~表42所示。 Preferred combinations of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and n in the formula [1] are shown in Tables 1 to 42.

具有以上述式[1]所表示之側鏈的二胺化合物，係可列舉以上述式[1a]所表示之二胺化合物。式[1a]中，m為1~4之整數，較佳為1。此外，上述式[1a]中之X₁、X₂、X₃、 X₄、X₅、X₆及n之較佳的基係與上述式[1]中之X₁、X₂、X₃、X₄、X₅、X₆及n相同，較佳的組合亦與式[1]相同地如表1~表42所示。 The diamine compound having a side chain represented by the above formula [1] is a diamine compound represented by the above formula [1a]. In the formula [1a], m is an integer of 1 to 4, preferably 1. Further, the formula [1a] in the _{X 1, X 2, X 3} , X 4, X 5, X 6 and n lines of the preferred groups of [1] X in the above Formula _1, X _2, X ₃ X ₄ , X ₅ , X ₆ and n are the same, and preferred combinations are also shown in Tables 1 to 42 in the same manner as in the formula [1].

此外，於上述式[1a]中之2個胺基(-NH₂)的鍵結位置並無限制。具體而言，係可列舉：相對於側鏈之鍵結基(X₁)，苯環上之2,3之位置、2,4之位置、2,5之位置、2,6之位置、3,4之位置或3,5之位置。其中，就聚合物進行合成時的反應性之觀點而言，以2,4之位置、2,5之位置或3,5之位置為佳。若也附帶考慮二胺化合物進行合成時的容易性，則以2,4之位置或2,5之位置為更佳。 Further, the bonding position of the two amine groups (-NH ₂ ) in the above formula [1a] is not limited. Specifically, the bonding group (X ₁ ) with respect to the side chain, the position of 2, 3 on the benzene ring, the position of 2, 4, the position of 2, 5, the position of 2, 6, 3 , 4 position or 3, 5 position. Among them, from the viewpoint of reactivity in the synthesis of the polymer, it is preferably at a position of 2, 4, a position of 2, 5, or a position of 3, 5. If the ease of synthesis of the diamine compound is also taken into consideration, the position of 2, 4 or 2, 5 is more preferable.

更具體而言，式[1a]係為以例如下述式[1-1]~式[1-31]所表示之結構。 More specifically, the formula [1a] is a structure represented by, for example, the following formula [1-1] to formula [1-31].

(式[1-1]~式[1-3]中，R₁係-O-、-OCH₂-、-CH₂O-、-COOCH₂-或-CH₂OCO-；R₂係碳數1~22之直鏈狀或分支狀烷基、碳數1~22之直鏈狀或分支狀烷氧基、碳數1~22之直鏈狀或分支狀含氟烷基、或含氟烷氧基)。 (In the formula [1-1]~Form [1-3], R ₁ is -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-; R ₂ -based carbon number a linear or branched alkyl group of 1 to 22, a linear or branched alkoxy group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms, or a fluorine-containing alkane Oxy).

(式[1-4]~式[1-6]中，R₃係-COO-、-OCO-、-COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂-或-CH₂-；R₄係碳數1~22之直鏈狀或分支狀烷基、碳數1~22之直鏈狀或分支狀烷氧基、碳數1~22之直鏈狀或分支狀含氟烷基、或含氟烷氧基)。 (In the formula [1-4]~Form [1-6], R ₃ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or - CH ₂ -; R ₄ is a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxy group having 1 to 22 carbon atoms, or a linear or branched carbon number of 1 to 22 Fluorinated alkyl or fluoroalkoxy).

(式[1-7]及式[1-8]中，R₅係-COO-、-OCO-、-COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂-、-CH₂-或-O-；R₆係氟基、氰基、三氟甲烷基、硝基、偶氮基、甲醯基、乙醯基、乙醯氧基或羥基)。 (In the formula [1-7] and the formula [1-8], R ₅ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, - CH ₂ - or -O-; R ₆ is a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a decyl group, an ethyl group, an ethoxy group or a hydroxy group).

(式[1-9]及式[1-10]中，R₇係碳數3~12之直鏈狀或分支狀烷基，1,4-伸環己基之順-反異構性係各自為反式異構 物)。 (In the formula [1-9] and the formula [1-10], R ₇ is a linear or branched alkyl group having a carbon number of 3 to 12, and a cis-trans isomerism of each of the 1,4-cyclohexylene groups. Is a trans isomer).

(式[1-11]及式[1-12]中，R₈係碳數3~12之直鏈狀或分支狀烷基，1,4-伸環己基之順-反異構性係各自為反式異構物)。 (In the formula [1-11] and the formula [1-12], R ₈ is a linear or branched alkyl group having 3 to 12 carbon atoms, and each of the cis-trans isomerization systems of the 1,4-cyclohexylene group is used. Is a trans isomer).

(式[1-13]中，A₁₆係為可被氟原子所取代的碳數3~20之直鏈狀或分支狀烷基；A₁₅係為1,4-伸環己基或1,4-伸苯基；A₁₄係氧原子或-COO-＊(其中，標示有「＊」的鍵結鍵係與A₁₅鍵結)；A₁₃係氧原子或-COO-＊(其中，標示有「＊」的鍵結鍵係與(CH₂)a₂鍵結)。此外，a₁為0或1之整數；a₂為2~10之整數；a₃為0或1之整數)。 (In the formula [1-13], A ₁₆ is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom; and A ₁₅ is a 1,4-cyclohexylene group or 1,4 - a phenyl group; an A ₁₄ -type oxygen atom or -COO-* (wherein the bond bond labeled "*" is bonded to A ₁₅ ); A ₁₃ is an oxygen atom or -COO-* (wherein The bonding key of "*" is bonded to (CH ₂ )a ₂ ). Further, a ₁ is an integer of 0 or 1; a ₂ is an integer of 2 to 10; a ₃ is an integer of 0 or 1.

作為特定聚合物(A)的原料所使用之具有以上述式[1]所表示之側鏈的二胺化合物，係可與作為特定聚合物(B)的原料所使用之具有以上述式[1]所表示之側鏈的二胺化合物相同或相異。再者，亦可因應作為液晶定向膜時的液晶定向性、電壓保持率及積蓄電荷等所期望的特性，而混合使用1種或2種以上者。 The diamine compound having a side chain represented by the above formula [1] used as a raw material of the specific polymer (A), which can be used as a raw material of the specific polymer (B), has the above formula [1] The diamine compounds of the side chains indicated are the same or different. In addition, one or two or more types may be used in combination depending on the desired properties such as the liquid crystal alignability, the voltage holding ratio, and the accumulated charge when the liquid crystal alignment film is used.

作為特定聚合物(A)的原料使用之具有以上述式[1]所表示的側鏈之二胺化合物，係以長鏈烷基或環結構(飽 和或不飽和之環狀的烴基)為3個以上等之於側鏈具有疏水性更高的基之二胺化合物者為佳，具體而言，係以上述式[1-9]、式[1-10]、式[1-11]、式[1-12]、式[1-22]、式[1-23]、式[1-24]、式[1-25]、式[1-26]、式[1-27]、式[1-28]、式[1-29]、式[1-30]或式[1-31]為佳。其中，以上述式[1-9]、式[1-10]、式[1-11]或式[1-12]、式[1-22]、式[1-23]、式[1-24]、式[1-25]、式[1-28]或式[1-29]為佳。特佳為上述式[1-9]、式[1-10]、式[1-11]或式[1-12]。 A diamine compound having a side chain represented by the above formula [1], which is a raw material of a specific polymer (A), is a long-chain alkyl group or a ring structure It is preferred that the hydrocarbyl group having a cyclic or unsaturated group is a diamine compound having three or more groups having a higher hydrophobicity in the side chain, specifically, the above formula [1-9], formula [ 1-10], Formula [1-11], Formula [1-12], Formula [1-22], Formula [1-23], Formula [1-24], Formula [1-25], Formula [1] -26], the formula [1-27], the formula [1-28], the formula [1-29], the formula [1-30] or the formula [1-31] is preferred. Wherein, the above formula [1-9], formula [1-10], formula [1-11] or formula [1-12], formula [1-22], formula [1-23], formula [1- 24], the formula [1-25], the formula [1-28] or the formula [1-29] is preferred. Particularly preferred is the above formula [1-9], formula [1-10], formula [1-11] or formula [1-12].

此外，作為特定聚合物(B)的原料使用之以上述式[1]所表示之二胺化合物，係以環結構為2個以下等之具有親水性高的側鏈基之二胺化合物者為佳，具體而言，係以上述式[1-1]、式[1-2]、式[1-3]、式[1-4]、式[1-5]、式[1-6]、式[1-7]或式[1-8]為佳。 In addition, the diamine compound represented by the above formula [1] used as a raw material of the specific polymer (B) is a diamine compound having a hydrophilic group having a side chain having two or more ring structures. Preferably, specifically, the above formula [1-1], formula [1-2], formula [1-3], formula [1-4], formula [1-5], and formula [1-6] , the formula [1-7] or the formula [1-8] is preferred.

接著，於本發明中，特定聚合物(B)，其原料之全部二胺成分中之具有以上述式[1]所表示的側鏈之二胺化合物的比例，必須較特定聚合物(A)的原料之全部二胺成分中之具有以式[1]所表示之側鏈之二胺化合物的比例更少。換言之，具有以上述式[1]所表示的側鏈之二胺化合物相對於特定聚合物(B)的原料之二胺成分總量的比例，必須較具有以式[1]所表示之側鏈之二胺化合物相對於特定聚合物(A)的原料之二胺成分總量的比例更少。 Next, in the present invention, the specific polymer (B), the proportion of the diamine compound having the side chain represented by the above formula [1] among all the diamine components of the raw material must be higher than the specific polymer (A) The proportion of the diamine compound having a side chain represented by the formula [1] among the entire diamine components of the raw material is less. In other words, the ratio of the diamine compound having the side chain represented by the above formula [1] to the total amount of the diamine component of the raw material of the specific polymer (B) must have a side chain represented by the formula [1] The ratio of the diamine compound to the total amount of the diamine component of the raw material of the specific polymer (A) is less.

具有以上述式[1]所表示的側鏈之二胺化合物相對於特定聚合物(A)或特定聚合物(B)的原料之二胺成分總量的比例，除必須如上所述般特定聚合物(B)較特定聚合 物(A)更少以外並無特別限定，例如，於特定聚合物(A)中，原料之二胺成分亦可僅為以上述式[1]所表示之二胺化合物。當然，特定聚合物(A)或特定聚合物(B)的原料之二胺成分，在不損及本發明之效果的範圍內，亦可各自包含具有以上述式[1]所表示之側鏈的二胺化合物以外的其他二胺化合物，但具有以上述式[1]所表示之側鏈的二胺化合物之比例越多，越能得到可賦予液晶高預傾角的液晶定向膜。於提高此預傾角特性的目的中，特定聚合物(A)或特定聚合物(B)，係分別以原料之二胺成分總量的5~80莫耳%為具有以上述式[1]所表示的側鏈之二胺化合物者為佳。其中，就液晶定向處理劑之塗佈性或作為液晶定向膜之電特性的觀點而言，以二胺成分總量的5~60莫耳%為具有以上述式[1]所表示的側鏈之二胺化合物者為佳。但，若特定聚合物(A)的原料之全部二胺成分中之具有以式[1]所表示的側鏈之二胺化合物的量與特定聚合物(B)的原料之全部二胺成分中之具有以式[1]所表示的側鏈之二胺化合物的量之差異過大，亦即，若特定聚合物(A)中之具有以式[1]所表示的結構之側鏈的量與特定聚合物(B)中之具有以式[1]所表示的結構之側鏈的量之差異過大，則會引發特定聚合物(A)或特定聚合物(B)之凝聚，因此，以滿足上述之條件，同時極力縮小側鏈的量之差異者為佳。具體而言，當將特定聚合物(A)之全部二胺成分中之具有以式[1]所表示之側鏈的二胺化合物之比例設為1時，較佳為特定聚合物(B)的原料之全部二胺成 分中之具有以式[1]所表示之側鏈的二胺化合物之比例為0.3以上且未達1.0，更佳為0.6以上且未達1.0。另外，於本說明書中，若無特別闡述，則「比例」係以莫耳數為基準。 The ratio of the diamine compound having the side chain represented by the above formula [1] to the total amount of the diamine component of the raw material of the specific polymer (A) or the specific polymer (B), in addition to the specific polymerization as described above Object (B) is more specific polymerization The amount of the (A) is not particularly limited. For example, in the specific polymer (A), the diamine component of the raw material may be only the diamine compound represented by the above formula [1]. Of course, the diamine component of the raw material of the specific polymer (A) or the specific polymer (B) may each contain a side chain represented by the above formula [1] within a range not impairing the effects of the present invention. The other diamine compound other than the diamine compound, the more the ratio of the diamine compound having the side chain represented by the above formula [1], the more the liquid crystal alignment film which can provide a high pretilt angle to the liquid crystal. For the purpose of improving the pretilt angle characteristic, the specific polymer (A) or the specific polymer (B) is each having 5 to 80 mol% of the total amount of the diamine component of the raw material, and having the above formula [1] The diamine compound of the side chain represented is preferred. In view of the coating property of the liquid crystal aligning agent or the electrical properties of the liquid crystal alignment film, 5 to 60 mol% of the total amount of the diamine component is a side chain represented by the above formula [1]. The diamine compound is preferred. However, if the total diamine component of the raw material of the specific polymer (A) has the amount of the diamine compound having the side chain represented by the formula [1] and the entire diamine component of the raw material of the specific polymer (B) The difference in the amount of the diamine compound having the side chain represented by the formula [1] is too large, that is, the amount of the side chain having the structure represented by the formula [1] in the specific polymer (A) and If the difference in the amount of the side chain having the structure represented by the formula [1] in the specific polymer (B) is too large, aggregation of the specific polymer (A) or the specific polymer (B) is initiated, thereby satisfying The above conditions are also preferred to minimize the difference in the amount of side chains. Specifically, when the ratio of the diamine compound having the side chain represented by the formula [1] among all the diamine components of the specific polymer (A) is set to 1, the specific polymer (B) is preferred. Raw material of all diamines The ratio of the diamine compound having a side chain represented by the formula [1] in the fraction is 0.3 or more and less than 1.0, more preferably 0.6 or more and less than 1.0. In addition, in this specification, unless otherwise stated, "proportion" is based on the number of moles.

可作為特定聚合物(A)或特定聚合物(B)的原料之二胺成分所使用之具有以上述式[1]所表示的側鏈之二胺化合物以外的其他之二胺化合物，係可列舉含有雜環之二胺化合物。含有雜環之二胺化合物以使用以上述式[2]所表示之二胺化合物者為佳。另外，於上述式[2]中，-(-Y₁-Y₂-Y₃-Y₄)_h係表示取代基-Y₁-Y₂-Y₃-Y₄為h個者，且亦可各自為相同或相異。 A diamine compound other than the diamine compound having a side chain represented by the above formula [1], which is used as a diamine component of a specific polymer (A) or a specific polymer (B), may be used. The diamine compound containing a hetero ring is enumerated. The diamine compound containing a hetero ring is preferably a diamine compound represented by the above formula [2]. Further, in the above formula [2], -(-Y ₁ -Y ₂ -Y ₃ -Y ₄ ) _h represents that the substituent -Y ₁ -Y ₂ -Y ₃ -Y ₄ is h, and Each is the same or different.

式[2]中，Y₁係由-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCO-、-CON(CH₃)-或-N(CH₃)CO-所選出之2價的有機基。其中，-O-、-NH-、-CONH-、-NHCO-、-CON(CH₃)-、-CH₂O-或-OCO-係因容易將二胺化合物進行合成而為佳。特佳為-O-、-NH-、-CONH-、-NHCO-、-CON(CH₃)-或-CH₂O-。 In the formula [2], Y _{1 is} derived from -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ ) - or -N(CH ₃ )CO- selected 2-valent organic group. Among them, -O-, -NH-, -CONH-, -NHCO-, -CON(CH ₃ )-, -CH ₂ O- or -OCO- are preferred because they are easy to synthesize a diamine compound. Particularly preferred is -O -, - NH -, - CONH -, - NHCO -, - CON (CH 3) - or -CH ₂ O-.

式[2]中，Y₂係單鍵、2價的碳數1~20之脂肪族烴基、非芳香族環式烴基或芳香族烴基。 In the formula [2], Y ₂ is a single bond, a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group.

碳數1~20之脂肪族烴基係可為直鏈狀，亦可為分支狀。此外，亦可具有不飽和鍵。較佳為碳數1~10之直鏈狀或分支狀烷基或具有碳數1~10之不飽和鍵的烷基。 The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear or branched. In addition, it may have an unsaturated bond. It is preferably a linear or branched alkyl group having 1 to 10 carbon atoms or an alkyl group having an unsaturated bond having 1 to 10 carbon atoms.

非芳香族烴基之具體例係可列舉：環丙烷環、環丁烷環、環戊烷環、環己烷環、環庚烷環、環辛烷環、環壬烷 環、環癸烷環、環十一烷環、環十二烷環、環十三烷環、環十四烷環、環十五烷環、環十六烷環、環十七烷環、環十八烷環、環十九烷環、環二十烷環、三環二十烷環、三環癸烷環、雙環庚烷環、十氫萘環、降莰烯環、金剛烷環等。 Specific examples of the non-aromatic hydrocarbon group include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, and a cyclodecane. Ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, ring Octadecane ring, cyclodecadecane ring, cycloecosane ring, tricyclohexadecane ring, tricyclodecane ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring and the like.

芳香族烴基之具體例係可列舉：苯環、萘環、四氫萘環、薁環、茚環、茀環、蒽環、菲環、萉環等。 Specific examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring, an anthracene ring, an anthracene ring, an anthracene ring, a phenanthrene ring, an anthracene ring, and the like.

於式[2]中之較佳的Y₂係單鍵、碳數1~10之直鏈狀或分支狀烷基、具有碳數1~10之不飽和鍵的烷基、環丙烷環、環丁烷環、環戊烷環、環己烷環、環庚烷環、降莰烯環、金剛烷環、苯環、萘環、四氫萘環、茀環或蒽環；更佳為單鍵、碳數1~10之直鏈狀或分支狀烷基、具有碳數1~10之不飽和鍵的烷基、環己烷環、降莰烯環、金剛烷環、苯環、萘環、茀環或蒽環；再更佳為單鍵、碳數1~10之直鏈狀或分支狀烷基、環己烷環、苯環或萘環；特佳為單鍵、碳數1~5之直鏈狀或分支狀烷基或苯環。 A preferred Y ₂ -based single bond in the formula [2], a linear or branched alkyl group having 1 to 10 carbon atoms, an alkyl group having an unsaturated bond having 1 to 10 carbon atoms, a cyclopropane ring, and a ring. Butane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, anthracene ring or anthracene ring; more preferably a single bond a linear or branched alkyl group having 1 to 10 carbon atoms, an alkyl group having an unsaturated bond having 1 to 10 carbon atoms, a cyclohexane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, Anthracene or anthracene ring; more preferably a single bond, a linear or branched alkyl group having a carbon number of 1 to 10, a cyclohexane ring, a benzene ring or a naphthalene ring; particularly preferably a single bond, carbon number 1 to 5 a linear or branched alkyl or benzene ring.

式[2]中，Y₃係單鍵、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-COO-、-OCO-、-CON(CH₃)-、-N(CH₃)CO-或-O(CH₂)_i-(i為1~5之整數)；較佳為單鍵、-O-、-NH-、-CONH-、-NHCO-、-COO-、-OCO-或-O(CH₂)_i-(i為1~5之整數)；更佳為單鍵、-O-、-NH-、-CONH-、-NHCO-、-COO-、-OCO-或-O(CH₂)_i-(i為1~5之整數)；再更佳為單鍵、-O-、-CONH-、-NHCO-、-COO-、-OCO-或-O(CH₂)_i-(i為1~5之整數)。 In the formula [2], Y ₃ is a single bond, -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ ) -, -N(CH ₃ )CO- or -O(CH ₂ ) _i - (i is an integer from 1 to 5); preferably a single bond, -O-, -NH-, -CONH-, -NHCO- , -COO-, -OCO- or -O(CH ₂ ) _i - (i is an integer from 1 to 5); more preferably a single bond, -O-, -NH-, -CONH-, -NHCO-, - COO-, -OCO- or -O(CH ₂ ) _i - (i is an integer from 1 to 5); more preferably a single bond, -O-, -CONH-, -NHCO-, -COO-, -OCO -or-O(CH ₂ ) _i - (i is an integer from 1 to 5).

式[2]中，Y₄係1價之含氮芳香族雜環，且為含有由例如下述之式[2-A]、式[2-B]或式[2-C]中所選出之至少1個的結構之芳香族雜環。 In the formula [2], Y ₄ is a monovalent nitrogen-containing aromatic heterocyclic ring, and is selected to be selected from, for example, the following formula [2-A], formula [2-B] or formula [2-C]. An aromatic heterocyclic ring having at least one structure.

(式[2-C]中，A₁₇係碳數1~5之直鏈狀或分支狀烷基)。 (In the formula [2-C], A ₁₇ is a linear or branched alkyl group having 1 to 5 carbon atoms).

具體而言，係可列舉：吡咯環、咪唑環、噁唑環、噻唑環、吡唑環、吡啶環、嘧啶環、喹啉環、吡唑啉環、異喹啉環、咔唑環、嘌呤環、噻二唑環、嗒嗪環、吡唑啉環、三嗪環、吡唑啶環、***環、吡嗪環、苯并咪唑環、苯并咪唑環、喹啉(chinoline)環、啡啉環、吲哚環、喹噁啉環、苯并噻唑環、吩噻嗪環、噁二唑環、吖啶環等。 Specific examples thereof include a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, an indazole ring, and an anthracene. Ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, chinoline ring, A phenanthroline ring, an anthracene ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, an acridine ring or the like.

式[2]中，較佳之Y₄係吡咯環、咪唑環、噁唑環、噻唑環、吡唑環、吡啶環、嘧啶環、喹啉環、吡唑啉環、異喹啉環、咔唑環、嘌呤環、噻二唑環、嗒嗪環、吡唑啉環、三嗪環、吡唑啶環、***環、吡嗪環、苯并咪唑環、苯并咪唑環、喹啉(chinoline)環、啡啉環、吲哚環、喹噁啉環、苯并噻唑環、吩噻嗪環、噁二唑環或吖啶環；更佳者為吡咯環、咪唑環、吡唑環、吡啶環、嘧啶環、吡唑啉環、咔唑環、嗒嗪環、吡唑啉環、三嗪環、吡唑啶環、***環、吡嗪環、苯并咪唑環或苯并咪唑環。再更佳者為吡咯環、咪唑環、吡唑環、吡啶環、嘧啶環、嗒嗪環、三 嗪環、***環、吡嗪環、苯并咪唑環或苯并咪唑環；特佳者為吡咯環、咪唑環、吡唑環、吡啶環或嘧啶環。 In the formula [2], a Y ₂ -based pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, or a carbazole is preferred. Ring, anthracene ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoline a ring, a phenanthroline ring, an anthracene ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring or an acridine ring; more preferably a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine Ring, pyrimidine ring, pyrazoline ring, indazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring or benzimidazole ring. Further preferred are pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring or benzimidazole ring; It is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring.

此外，Y₃係以與不和Y₄中所含有的式[2-A]、式[2-B]及式[2-C]相鄰的取代基鍵結者為佳。 Further, Y ₃ is preferably a bond which is not bonded to a substituent adjacent to the formula [2-A], the formula [2-B] and the formula [2-C] contained in Y ₄ .

於式[2]中之Y₁、Y₂、Y₃及Y₄的較佳組合係如表43~表48所示。 Preferred combinations of Y ₁ , Y ₂ , Y ₃ and Y ₄ in the formula [2] are shown in Tables 43 to 48.

其中，以上述表43~表48中之[1-7]、[1-9]、[1-12]、[1-14]、[1-17]、[1-19]、[1-22]、[1-24]、[1-27]、[1-29]、[1-52]、[1-54]、[1-124]、[1-126]、[1-148]、[1-150]、[1-172]或[1-173]的組合為佳。 Among them, [1-7], [1-9], [1-12], [1-14], [1-17], [1-19], [1- in Tables 43 to 48 above 22], [1-24], [1-27], [1-29], [1-52], [1-54], [1-124], [1-126], [1-148] The combination of [1-150], [1-172] or [1-173] is preferred.

式[2]中，h為1~4之整數，就與四羧酸二酐之反應性的觀點而言，較佳為1~3之整數。 In the formula [2], h is an integer of 1 to 4, and from the viewpoint of reactivity with tetracarboxylic dianhydride, it is preferably an integer of 1 to 3.

於特定聚合物(A)及特定聚合物(B)兩者皆以含有雜環之二胺化合物作為原料時，作為特定聚合物(A)的原料所使用的含有雜環之二胺化合物，亦可與作為特定聚 合物(B)的原料所使用的含有雜環之二胺化合物為相同或相異。再者，亦可因應作為液晶定向膜時的液晶定向性、電壓保持率、積蓄電荷等之期望的特性，而混合使用1種類或2種類以上。 When the specific polymer (A) and the specific polymer (B) are both a heterocyclic diamine compound as a raw material, the heterocyclic diamine compound used as a raw material of the specific polymer (A) is also used. As a specific poly The heterocyclic-containing diamine compound used in the raw material of the compound (B) is the same or different. In addition, one type or two types or more may be used in combination depending on desired characteristics such as liquid crystal orientation, voltage holding ratio, and accumulated charge when the liquid crystal alignment film is used.

上述含有雜環之二胺化合物的比例越多，越能得到將因直流電壓所積蓄的電荷之緩和特性作了改善的液晶定向膜，亦即，積蓄電荷為小的液晶定向膜。於提高此積蓄電荷之緩和特性的目的中，上述含有雜環之二胺化合物，相對於具有以上述式[1]所表示的側鏈之二胺化合物1莫耳，係以0.01~99莫耳者為佳。更佳為0.1~50莫耳，再更佳為0.2~20莫耳，最佳為0.2~10莫耳。 The larger the ratio of the heterocyclic-containing diamine compound, the more the liquid crystal alignment film which improves the relaxation property of the electric charge accumulated by the DC voltage, that is, the liquid crystal alignment film having a small charge. For the purpose of improving the relaxation property of the charge, the diamine compound containing a hetero ring is 0.01 to 99 moles per mole of the diamine compound having the side chain represented by the above formula [1]. It is better. More preferably 0.1 to 50 moles, more preferably 0.2 to 20 moles, and most preferably 0.2 to 10 moles.

此外，具有以上述式[1]所表示之側鏈的二胺化合物以外的其他二胺化合物係可列舉：p-伸苯基二胺、2,3,5,6-四甲基-p-伸苯基二胺、2,5-二甲基-p-伸苯基二胺、m-伸苯基二胺、2,4-二甲基-m-伸苯基二胺、2,5-二胺基甲苯、2,6-二胺基甲苯、2,5-二胺基苯酚、2,4-二胺基苯酚、3,5-二胺基苯酚、3,5-二胺基苯甲醇、2,4-二胺基苯甲醇、4,6-二胺基間苯二酚、4,4’-二胺基聯苯、3,3’-二甲基-4,4’-二胺基聯苯、3,3’二甲氧基-4,4’-二胺基聯苯、3,3’-二羥基-4,4’-二胺基聯苯、3,3’-二羧基-4,4’-二胺基聯苯、3,3’-二氟-4,4’-聯苯、3,3’-三氟甲基-4,4’-二胺基聯苯、3,4’-二胺基聯苯、3,3’-二胺基聯苯、2,2’-二胺基聯苯、2,3’-二胺基聯苯、4,4’-二胺基二苯甲烷、3,3’-二胺基二苯甲烷、3,4’-二胺基二苯甲烷、2,2’-二胺基二苯甲烷、2,3’-二胺 基二苯甲烷、4,4’-二胺基二苯基醚、3,3’-二胺基二苯基醚、3,4’-二胺基二苯基醚、2,2’-二胺基二苯基醚、2,3’-二胺基二苯基醚、4,4’-磺醯基二苯胺、3,3’-磺醯基二苯胺、雙(4-胺基苯基)矽烷、雙(3-胺基苯基)矽烷、二甲基-雙(4-胺基苯基)矽烷、二甲基-雙(3-胺基苯基)矽烷、4,4’-硫化二苯胺、3,3’-硫化二苯胺、4,4’-二胺基二苯基胺、3,3’-二胺基二苯基胺、3,4’-二胺基二苯基胺、2,2’-二胺基二苯基胺、2,3’-二胺基二苯基胺、N-甲基(4,4’-二胺基二苯基)胺、N-甲基(3,3’-二胺基二苯基)胺、N-甲基(3,4’-二胺基二苯基)胺、N-甲基(2,2’-二胺基二苯基)胺、N-甲基(2,3’-二胺基二苯基)胺、4,4’-二胺基二苯基酮、3,3’-二胺基二苯基酮、3,4’-二胺基二苯基酮、1,4-二胺基萘、2,2’-二胺基二苯基酮、2,3’-二胺基二苯基酮、1,5-二胺基萘、1,6-二胺基萘、1,7-二胺基萘、1,8-二胺基萘、2,5-二胺基萘、2,6二胺基萘、2,7-二胺基萘、2,8-二胺基萘、1,2-雙(4-胺基苯基)乙烷、1,2-雙(3-胺基苯基)乙烷、1,3-雙(4-胺基苯基)丙烷、1,3-雙(3-胺基苯基)丙烷、1,4-雙(4胺基苯基)丁烷、1,4-雙(3-胺基苯基)丁烷、雙(3,5-二乙基-4-胺基苯基)甲烷、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(4-胺基苯基)苯、1,3-雙(4-胺基苯基)苯、1,4-雙(4-胺基苯甲基)苯、1,3-雙(4-胺基苯氧基)苯、4,4’-〔1,4-伸苯基雙(亞甲基)〕二苯胺、4,4’-〔1,3-伸苯基雙(亞甲基)〕二苯胺、3,4’-〔1,4-伸苯基雙(亞甲 基)〕二苯胺、3,4’-〔1,3-伸苯基雙(亞甲基)〕二苯胺、3,3’-〔1,4-伸苯基雙(亞甲基)〕二苯胺、3,3’-〔1,3-伸苯基雙(亞甲基)〕二苯胺、1,4-伸苯基雙〔(4-胺基苯基)甲酮〕、1,4-伸苯基雙〔(3-胺基苯基)甲酮〕、1,3-伸苯基雙〔(4-胺基苯基)甲酮〕、1,3-伸苯基雙〔(3-胺基苯基)甲酮〕、1,4-伸苯基雙(4-胺基苯甲酸酯)、1,4-伸苯基雙(3-胺基苯甲酸酯)、1,3-伸苯基雙(4-胺基苯甲酸酯)、1,3-伸苯基雙(3-胺基苯甲酸酯)、雙(4-胺基苯基)對苯二甲酸酯、雙(3-胺基苯基)對苯二甲酸酯、雙(4-胺基苯基)間苯二甲酸酯、雙(3-胺基苯基)間苯二甲酸酯、N,N’-(1,4-伸苯基)雙(4-胺基苯甲醯胺)、N,N’-(1,3-伸苯基)雙(4-胺基苯甲醯胺)、N,N’-(1,4-伸苯基)雙(3-胺基苯甲醯胺)、N,N’-(1,3-伸苯基)雙(3-胺基苯甲醯胺)、N,N’-雙(4-胺基苯基)對苯二甲醯胺、N,N’-雙(3-胺基苯基)對苯二甲醯胺、N,N’-雙(4-胺基苯基)間苯二甲醯胺、N,N’-雙(3-胺基苯基)間苯二甲醯胺、9,10-雙(4-胺基苯基)蒽、4,4’-雙(4-胺基苯氧基)二苯碸、2,2’-雙〔4-(4-胺基苯氧基)苯基〕丙烷、2,2’-雙〔4-(4-胺基苯氧基)苯基〕六氟丙烷、2,2’-雙(4-胺基苯基)六氟丙烷、2,2’-雙(3-胺基苯基)六氟丙烷、2,2’-雙(3-胺基-4-甲基苯基)六氟丙烷、2,2’-雙(4-胺基苯基)丙烷、2,2’-雙(3-胺基苯基)丙烷、2,2’-雙(3-胺基-4-甲基苯基)丙烷、1,3-雙(4-胺基苯氧基)丙烷、1,3-雙(3-胺基苯氧 基)丙烷、1,4-雙(4-胺基苯氧基)丁烷、1,4-雙(3-胺基苯氧基)丁烷、1,5-雙(4-胺基苯氧基)戊烷、1,5-雙(3-胺基苯氧基)戊烷、1,6-雙(4-胺基苯氧基)己烷、1,6-雙(3-胺基苯氧基)己烷、1,7-雙(4-胺基苯氧基)庚烷、1,7-(3-胺基苯氧基)庚烷、1,8-雙(4-胺基苯氧基)辛烷、1,8-雙(3-胺基苯氧基)辛烷、1,9-雙(4-胺基苯氧基)壬烷、1,9-雙(3-胺基苯氧基)壬烷、1,10-(4-胺基苯氧基)癸烷、1,10-(3-胺基苯氧基)癸烷、1,11-(4-胺基苯氧基)十一烷、1,11-(3-胺基苯氧基)十一烷、1,12-(4-胺基苯氧基)十二烷、1,12-(3-胺基苯氧基)十二烷、4-(胺基甲基)苯胺、3-(胺基甲基)苯胺、4-(2-胺基乙基)苯胺或3-(2-胺基乙基苯胺)等之芳香族二胺；雙(4-胺基環己基)甲烷或雙(4-胺基-3-甲基環己基)甲烷等之脂環式二胺、1,3-二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷、1,11-二胺基十一烷或1,12-二胺基十二烷等之脂肪族二胺。 Further, examples of the other diamine compound other than the diamine compound having the side chain represented by the above formula [1] include p-phenylenediamine and 2,3,5,6-tetramethyl-p-. Phenyldiamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5- Diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol , 2,4-Diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diamine Biphenyl, 3,3'dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxyl -4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3 , 4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diamine Diphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diamine Diphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-di Aminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl) ) decane, bis(3-aminophenyl)decane, dimethyl-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-vulcanization Diphenylamine, 3,3'-diphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine , 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl (3,3'-Diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl (2,2'-diaminodiphenyl) An amine, N-methyl (2,3'-diaminodiphenyl)amine, 4,4'-diaminodiphenyl ketone, 3,3'-diaminodiphenyl ketone, 3, 4'-Diaminodiphenyl ketone, 1,4-diaminonaphthalene, 2,2'-diaminodiphenyl ketone, 2,3'-diaminodiphenyl ketone, 1,5- Diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene 1,8-Diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-double ( 4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-amine Phenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-amine Phenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl) Benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(methylene)]diphenylamine, 4,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,4' -[1,4-phenylene bis (nara Diphenylamine, 3,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,3'-[1,4-phenylenebis(methylene)] Aniline, 3,3'-[1,3-phenylenebis(methylene)]diphenylamine, 1,4-phenylphenylbis[(4-aminophenyl)methanone], 1,4- Phenyl bis[(3-aminophenyl)methanone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3- Aminophenyl)methanone], 1,4-phenylene bis(4-aminobenzoate), 1,4-phenylphenylbis(3-aminobenzoate), 1,3 -phenylphenylbis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate), bis(4-aminophenyl)terephthalate , bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N , N'-(1,4-phenylene) bis(4-aminobenzamide), N,N'-(1,3-phenylene)bis(4-aminobenzamide) , N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenzamide) Amine, N,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(3-aminophenyl)terephthalamide, N,N'- Bis(4-amino group Phenyl) m-xylyleneamine, N,N'-bis(3-aminophenyl)m-xylyleneamine, 9,10-bis(4-aminophenyl)anthracene, 4,4' - bis(4-aminophenoxy)diphenyl hydrazine, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4- Aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2 , 2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminobenzene) Propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-amine Phenyloxy Propane, 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxyl) Pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminobenzene) Oxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1,8-bis(4-aminobenzene) Oxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,9-bis(3-amino Phenoxy)decane, 1,10-(4-aminophenoxy)decane, 1,10-(3-aminophenoxy)decane, 1,11-(4-aminophenoxyl) Ethyl undecane, 1,11-(3-aminophenoxy)undecane, 1,12-(4-aminophenoxy)dodecane, 1,12-(3-aminobenzene Oxy) dodecane, 4-(aminomethyl)aniline, 3-(aminomethyl)aniline, 4-(2-aminoethyl)aniline or 3-(2-aminoethylaniline) An aromatic diamine; an alicyclic diamine such as bis(4-aminocyclohexyl)methane or bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminopropane, 1,4-Diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diamine Nonane, 1,10-diamino decane, 1,11-diamino-1,12-undecane or dodecane diamine of aliphatic diamine.

此外，具有以上述式[1]所表示之側鏈的二胺化合物以外之其他的二胺化合物，係可使用側鏈具有烷基或含氟烷基之二胺化合物。具體而言，係可例示以下述之式[DA-1]~式[DA-12]所表示之二胺者。 Further, as the diamine compound other than the diamine compound having the side chain represented by the above formula [1], a diamine compound having an alkyl group or a fluorine-containing alkyl group in its side chain can be used. Specifically, a diamine represented by the following formula [DA-1] to formula [DA-12] can be exemplified.

(式[DA-1]~式[DA-5]中，A₁係碳數1~22之直鏈狀或分支狀烷基，或碳數1~22之直鏈狀或分支狀含氟烷基)。 (In the formula [DA-1]~form [DA-5], A ₁ is a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine-containing alkane having 1 to 22 carbon atoms; base).

(式[DA-6]~式[DA-11]中，A₂係表示-COO-、-OCO-、-CONH-、-NHCO-、CH₂-、-O-、-CO-或-NH-；A₃係表示碳數1~22之直鏈狀或分支狀烷基，或碳數1~22之直鏈狀或分支狀含氟烷基)。 (In the formula [DA-6]~form [DA-11], A ₂ represents -COO-, -OCO-, -CONH-, -NHCO-, CH ₂ -, -O-, -CO- or -NH -; A ₃ represents lines 1 to 22 carbon atoms of straight-chain or branched alkyl group, or a 1 to 22 carbon atoms of straight-chain or branched fluorine-containing alkyl).

(式[DA-12]中，p為1~10之整數)。 (In the formula [DA-12], p is an integer from 1 to 10).

此外，具有以上述式[1]所表示之側鏈的二胺化合物以外之其他的二胺化合物，係可使用以下述之式[DA-13]~式[DA-20]所表示之二胺化合物。 Further, as the diamine compound other than the diamine compound having the side chain represented by the above formula [1], a diamine represented by the following formula [DA-13] to formula [DA-20] can be used. Compound.

(式[DA-17]中，k為0~3之整數；式[DA-20]中，1為1~5之整數)。 (In the formula [DA-17], k is an integer from 0 to 3; in the formula [DA-20], 1 is an integer from 1 to 5).

再者，具有以上述式[1]所表示之側鏈的二胺化合物以外之其他的二胺化合物，係可使用以下述之式[DA-21]~式[DA-25]所表示之分子內具有羧基之二胺化合物。 In addition, as the diamine compound other than the diamine compound having the side chain represented by the above formula [1], a molecule represented by the following formula [DA-21] to formula [DA-25] can be used. A diamine compound having a carboxyl group therein.

(式[DA-21]中，m₁係1~4之整數；式[DA-22]中，A₄係單鍵、-CH₂-、-C₂H₄-、-C(CH₃)₂-、-CF₂-、-C(CF₃)-、-O-、-CO-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-CON(CH₃)-或-N(CH₃)CO-；m₂ 及m₃係各自為0~4之整數，且m₂+m₃為1~4之整數；式[DA-23]中，m₄及m₅係各自為1~5之整數；式[DA-24]中，A₅係碳數1~5之直鏈狀或分支狀烷基；m₆為1~5之整數；式[DA-25]中，A₆係單鍵、-CH₂-、-C₂H₄-、-C(CH₃)₂-、-CF₂-、-C(CF₃)-、-O-、-CO-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-CON(CH₃)-或-N(CH₃)CO-；m₇為1~4之整數)。 (In the formula [DA-21], m ₁ is an integer of 1 to 4; in the formula [DA-22], A ₄ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ )-, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-; m ₂ and m ₃ are each an integer from 0 to 4, and m ₂ + m ₃ An integer of 1 to 4; in the formula [DA-23], m ₄ and m ₅ are each an integer of 1 to 5; in the formula [DA-24], A ₅ is a linear chain having a carbon number of 1 to 5 or Branched alkyl; m ₆ is an integer from 1 to 5; in the formula [DA-25], A ₆ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, - CF ₂ -, -C(CF ₃ )-, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ - , -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-; m ₇ is an integer from 1 to 4).

再者，具有以上述式[1]所表示之側鏈的二胺化合物以外之其他的二胺化合物，係亦可使用以下述之式[DA-26]及式[DA-27]所表示之二胺化合物。 In addition, the diamine compound other than the diamine compound having the side chain represented by the above formula [1] can also be represented by the following formula [DA-26] and formula [DA-27]. Diamine compound.

上述之其他的二胺化合物，亦可因應作為液晶定向膜時的液晶定向性、電壓保持率、積蓄電荷等之特性，而混合使用1種類或2種類以上。 The other diamine compound may be used in combination of one type or two types or more depending on characteristics such as liquid crystal orientation, voltage holding ratio, and accumulated charge when used as a liquid crystal alignment film.

於本發明中，將特定聚合物(A)或特定聚合物(B)合成的方法，係將具有以上述式[1]所表示之側鏈的二胺化合物作為原料的一部分以外，其他並無特別限制。一般係使二胺成分與四羧酸成分進行反應而得。一般而言係使由四羧酸及其衍生物所成之群中所選出的至少1種之四羧酸 成分與由1種或複數種之二胺化合物所成之二胺成分進行反應，而得到聚醯胺酸。為了得到聚醯胺酸烷基酯係可採用將聚醯胺酸之羧基轉換成酯的方法等。再者，為了得到聚醯亞胺亦可為將前述之聚醯胺酸或聚醯胺酸烷基酯予以醯亞胺化而成為聚醯亞胺的方法。 In the present invention, a method of synthesizing a specific polymer (A) or a specific polymer (B) is a part of a raw material having a side chain represented by the above formula [1], and the other is not Special restrictions. Generally, it is obtained by reacting a diamine component and a tetracarboxylic acid component. Generally, at least one of the tetracarboxylic acids selected from the group consisting of tetracarboxylic acids and derivatives thereof The component is reacted with a diamine component formed from one or a plurality of diamine compounds to obtain a polyamic acid. In order to obtain a polyalkylamine alkyl ester, a method of converting a carboxyl group of polyproline into an ester or the like can be used. Further, in order to obtain a polyimine, a method in which the above-mentioned polyamic acid or polyalkyl amide is imidized to form a polyimine.

用以得到本發明之特定聚合物(A)或特定聚合物(B)的原料之四羧酸成分，以使用以上述式[3]所表示之四羧酸二酐者為佳。 The tetracarboxylic acid component of the raw material of the specific polymer (A) or the specific polymer (B) of the present invention is preferably used by using the tetracarboxylic dianhydride represented by the above formula [3].

式[3]中，就聚合反應性或合成之容易性的觀點而言，Z₁之特佳的結構係為式[3a]、式[3c]、式[3d]、式[3e]、式[3f]或式[3g]。其中，以式[3a]、式[3e]、式[3f]或式[3g]為佳。 In the formula [3], a particularly preferable structure of Z ₁ is a formula [3a], a formula [3c], a formula [3d], a formula [3e], and a formula in terms of polymerization reactivity or ease of synthesis. [3f] or formula [3g]. Among them, the formula [3a], the formula [3e], the formula [3f] or the formula [3g] is preferred.

此外，以上述式[3]所表示之四羧酸二酐相對於特定聚合物(A)或特定聚合物(B)的原料之四羧酸成分總量的比例並無特別限定，例如，原料之四羧酸成分亦可僅為以上述式[3]所表示之四羧酸二酐。當然，特定聚合物(A)或特定聚合物(B)的原料之四羧酸成分，只要不損及本發明之效果，亦可含有以上述式[3]所表示之四羧酸二酐以外的四羧酸或四羧酸衍生物。此時，以四羧酸成分總量之1莫耳%以上為以上述式[3]所表示之四羧酸二酐者為佳，較佳為5莫耳%以上，更佳為10莫耳%以上。 Further, the ratio of the tetracarboxylic dianhydride represented by the above formula [3] to the total amount of the tetracarboxylic acid component of the raw material of the specific polymer (A) or the specific polymer (B) is not particularly limited, for example, raw materials The tetracarboxylic acid component may be only the tetracarboxylic dianhydride represented by the above formula [3]. Of course, the tetracarboxylic acid component of the raw material of the specific polymer (A) or the specific polymer (B) may contain the tetracarboxylic dianhydride represented by the above formula [3] as long as the effects of the present invention are not impaired. a tetracarboxylic acid or a tetracarboxylic acid derivative. In this case, it is preferable that the total amount of the tetracarboxylic acid component is 1 mol% or more, and the tetracarboxylic acid dianhydride represented by the above formula [3] is preferably 5 mol% or more, more preferably 10 mol%. %the above.

以上述式[3]所表示之四羧酸二酐以外之其他的四羧酸二酐係可列舉：苯均四酸、2,3,6,7-萘四羧酸、1,2,5,6-萘四羧酸、1,4,5,8-萘四羧酸、2,3,6,7-蒽四羧酸、1,2,5,6-蒽 四羧酸、3,3’,4,4’-聯苯四羧酸、2,3,3’,4-聯苯四羧酸、雙(3,4-二羧基苯基)醚、3,3’,4,4’-二苯基酮四羧酸、雙(3,4-二羧基苯基)碸、雙(3,4-二羧基苯基)甲烷、2,2-雙(3,4-二羧基苯基)丙烷、1,1,1,3,3,3-六氟-2,2-雙(3,4-二羧基苯基)丙烷、雙(3,4-二羧基苯基)二甲基矽烷、雙(3,4-二羧基苯基)二苯基矽烷、2,3,4,5-吡啶四羧酸、2,6-雙(3,4-二羧基苯基)吡啶、3,3’,4,4’-二苯碸四羧酸、3,4,9,10-苝四羧酸或1,3-二苯基-1,2,3,4-環丁烷四羧酸。 Examples of the tetracarboxylic dianhydride other than the tetracarboxylic dianhydride represented by the above formula [3] include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5. ,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-nonanedicarboxylic acid, 1,2,5,6-anthracene Tetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3, 3',4,4'-diphenyl ketone tetracarboxylic acid, bis(3,4-dicarboxyphenyl)anthracene, bis(3,4-dicarboxyphenyl)methane, 2,2-bis (3, 4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxybenzene) Dimethyl decane, bis(3,4-dicarboxyphenyl)diphenyl decane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl) Pyridine, 3,3',4,4'-diphenyltetracarboxylic acid, 3,4,9,10-nonanetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-ring Butane tetracarboxylic acid.

以上述式[3]所表示之四羧酸二酐、或其他之四羧酸及四羧酸衍生物，亦可因應作為液晶定向膜時的液晶定向性、電壓保持率及積蓄電荷等所期望之特性，而混合使用1種類或2種類以上。 The tetracarboxylic dianhydride represented by the above formula [3], or other tetracarboxylic acid and tetracarboxylic acid derivative may be desired in view of liquid crystal directionality, voltage holding ratio, and accumulated charge when used as a liquid crystal alignment film. The characteristics are mixed and used in one type or two types or more.

二胺成分與四羧酸成分之反應一般係在有機溶劑中進行。此時所使用的有機溶劑係只要使所生成的聚醯亞胺前驅物溶解則無特別限制。其具體例係可列舉：N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-甲基己內醯胺、二甲基亞碸、四甲脲、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯、異丙醇、甲氧基甲基戊醇、雙戊烯、乙基戊基酮、甲基壬基酮、甲基乙基酮、甲基異戊基酮、甲基異丙基酮、甲基賽路蘇、乙基賽路蘇、甲基賽路蘇乙酸酯、乙基賽路蘇乙酸酯、丁基卡必醇、乙基卡必醇、乙二醇、乙二醇單乙酸酯、乙二醇單異丙基醚、乙二醇單丁基醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲基 醚、丙二醇-tert-丁基醚、二丙二醇單甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲基醚、3-甲基-3-甲氧基丁醇、二異丙基醚、乙基異丁基醚、倍異丁烯、乙酸戊酯、丁酸丁酯、丁基醚、二異丁基酮、甲基環己烯、丙基醚、二己基醚、二噁烷、n-己烷、n-戊烷、n-辛烷、二乙基醚、環己酮、碳酸乙烯酯、碳酸丙烯酯、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、二甘二甲醚或4-羥基-4-甲基-2-戊酮等。此等係可單獨使用，亦可混合使用。再者，在不析出所生成的聚醯亞胺前驅物的範圍內，即使是不溶解聚醯亞胺前驅物的溶劑，也可與上述溶劑混合而使用。此外，有機溶劑中之水分會阻礙聚合反應，進而成為使所生成的聚醯亞胺前驅物水解的原因，因而，有機溶劑係以使用經脫水乾燥者為佳。 The reaction of the diamine component with the tetracarboxylic acid component is generally carried out in an organic solvent. The organic solvent used at this time is not particularly limited as long as the produced polyimide precursor is dissolved. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, and Methyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl hydrazine, γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethyl amyl ketone, Methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl serotonin, ethyl sirlox, methyl sarbuta acetate, ethyl cyano Lucas acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol Monoacetate, propylene glycol monomethyl Ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether , dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, isobutylene, amyl acetate, butyl Butyl acrylate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl Ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, pyruvic acid Ethyl ester, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid , 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl , Diethylene glycol dimethyl ether, or 4-hydroxy-4-methyl-2-pentanone and the like. These may be used alone or in combination. Further, in the range in which the produced polyimide intermediate precursor is not precipitated, even a solvent which does not dissolve the polyimide precursor can be used in combination with the above solvent. Further, the water in the organic solvent hinders the polymerization reaction and further causes hydrolysis of the produced polyimide precursor. Therefore, the organic solvent is preferably dried by dehydration.

使二胺成分與四羧酸成分在有機溶劑中反應時，係可列舉：將於有機溶劑中分散或溶解有二胺成分的溶液加以攪拌，使四羧酸成分直接或分散或溶解於有機溶劑而進行添加的方法；相反地於在有機溶劑中分散或溶解有四羧酸 成分的溶液中添加二胺成分的方法；將四羧酸成分與二胺成分交互添加的方法等，使用此等中之任一種方法均可。此外，分別使用複數種二胺成分或四羧酸成分來進行反應時，係可在經事先混合的狀態下進行反應，亦可個別依序進行反應，進而可使經個別反應後的低分子量體混合反應而成為特定聚合物(A)或特定聚合物(B)。此時之聚合溫度雖可選擇-20℃~150℃之任意的溫度，但較佳為-5℃~100℃之範圍。此外，反應雖可在任意的濃度下進行，但若濃度過低則會變得難以得到高分子量之特定聚合物(A)或特定聚合物(B)，若濃度過高則反應液的黏性會過高而變得難以均勻的攪拌。因此，二胺成分及四羧酸成分的總量之濃度，在反應液中較佳為1~50質量%，更佳為5~30質量%。反應初期係可在高濃度下進行，之後再追加有機溶劑。 When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, a solution in which a diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic acid component is directly or dispersed or dissolved in an organic solvent. And the method of adding; conversely, dispersing or dissolving tetracarboxylic acid in an organic solvent A method of adding a diamine component to a solution of a component, a method of adding a tetracarboxylic acid component and a diamine component, and the like may be used. Further, when a plurality of kinds of diamine components or tetracarboxylic acid components are used for the reaction, the reaction may be carried out in a state of being mixed beforehand, or the reaction may be carried out in an individual order, and the low molecular weight body after the individual reaction may be further obtained. The reaction is carried out to form a specific polymer (A) or a specific polymer (B). The polymerization temperature at this time may be any temperature of from -20 ° C to 150 ° C, but preferably from -5 ° C to 100 ° C. Further, although the reaction can be carried out at any concentration, if the concentration is too low, it becomes difficult to obtain a specific polymer (A) or a specific polymer (B) having a high molecular weight, and if the concentration is too high, the viscosity of the reaction liquid is high. It will be too high and it will become difficult to evenly stir. Therefore, the concentration of the total amount of the diamine component and the tetracarboxylic acid component is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, based on the total amount of the reaction solution. The initial stage of the reaction can be carried out at a high concentration, and then an organic solvent is added.

於聚醯亞胺前驅物之聚合反應中，係以二胺成分之合計莫耳數與四羧酸成分之合計莫耳數的比例為0.8~1.2者為佳。與一般的聚縮合反應相同，此莫耳比越接近1.0則所生成的聚醯亞胺前驅物之分子量越大。 In the polymerization reaction of the polyimine precursor, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. As with the general polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.

經上述方式聚合而成的特定聚合物(A)或特定聚合物(B)，係為具有例如以下述式[a]所表示之重複單元的聚合物之聚醯亞胺前驅物。 The specific polymer (A) or the specific polymer (B) polymerized in the above manner is a polyimine precursor having a polymer having, for example, a repeating unit represented by the following formula [a].

(式[a]中，R₁₁為4價之有機基；R₁₂為來自原料之二胺成分的2價之有機基；A₁₁及A₁₂係為氫原子或碳數1~8之烷基，且可各自相同或相異；j係表示正整數)。 (In the formula [a], R ₁₁ is a tetravalent organic group; R ₁₂ is a divalent organic group derived from a diamine component of a raw material; and A ₁₁ and A ₁₂ are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; And may be the same or different; j is a positive integer).

於上述式[a]中，R₁₁及R₁₂可各自為1種類且具有相同的重複單元之聚合物，此外，R₁₁或R₁₂亦可為複數種且具有不同結構的重複單元之聚合物。 In the above formula [a], R ₁₁ and R ₁₂ each may be a polymer of one type and having the same repeating unit, and further, R ₁₁ or R ₁₂ may be a polymer of a plurality of repeating units having different structures. .

於上述式[a]中，R₁₁係為原料之來自以下述式[c]等所表示的四羧酸成分之基；R₁₂係為原料之來自以下述式[b]等所表示的二胺成分之基。例如，只要R₁₂為來自具有以上述式[1]所表示之側鏈的二胺之基，則為於聚醯亞胺前驅物之主鏈，亦即聚醯胺酸骨架，直接或經由適合的鍵結基而鍵結有以上述式[1]所表示的結構作為側鏈的聚合物。 In the above formula [a], R ₁₁ is a group derived from a tetracarboxylic acid component represented by the following formula [c] or the like; and R ₁₂ is a raw material derived from the following formula [b] or the like. The base of the amine component. For example, as long as R ₁₂ is a group derived from a diamine having a side chain represented by the above formula [1], it is a main chain of a polyimine precursor, that is, a poly-proline skeleton, directly or via a suitable one. The bonding group is bonded to a polymer having a structure represented by the above formula [1] as a side chain.

(式[b]及式[c]中，R₁₁及R₁₂係為與在式[a]中所定義者相同)。 (In the formula [b] and the formula [c], R ₁₁ and R ₁₂ are the same as those defined in the formula [a]).

另外，基於藉由將以上述式[b]所表示的二胺成分與以上述式[c]所表示的四羧酸二酐成分作為原料而可較簡便地獲得之理由，以由以下述式[d]所表示之重複單元的結構式所構成的聚醯胺酸或使該聚醯胺酸醯亞胺化而得的聚醯亞胺為佳。 In addition, the reason why the diamine component represented by the above formula [b] and the tetracarboxylic dianhydride component represented by the above formula [c] are used as a raw material can be easily obtained, and the following formula is used. The polyperide acid composed of the structural formula of the repeating unit represented by [d] or the polyimine obtained by imidating the polyphosphonium amide is preferred.

(式[d]中，R₁₁、R₁₂及j係為與在式[a]中所定義者相同)。 (In the formula [d], R ₁₁ , R ₁₂ and j are the same as those defined in the formula [a]).

此外，特定聚合物(A)或特定聚合物(B)亦可為使上述之聚醯亞胺前驅物脫水閉環而得之聚醯亞胺。上述之聚醯亞胺係作為用以得到液晶定向膜的聚合物為有用。 Further, the specific polymer (A) or the specific polymer (B) may be a polyimine obtained by dehydrating and ring-closing the above-mentioned polyimide precursor. The above polyimine is useful as a polymer for obtaining a liquid crystal alignment film.

使聚醯亞胺前驅物醯亞胺化的方法係可列舉：將聚醯亞胺前驅物之溶液直接加熱的熱醯亞胺化或將觸媒添加至聚醯亞胺前驅物之溶液的觸媒醯亞胺化。 The method for imidating the polyimine precursor oxime may be exemplified by hot hydrazylation of a solution in which a solution of a polyimide precursor is directly heated or a solution in which a catalyst is added to a solution of a polyimide precursor. Media imidization.

在溶液中使聚醯亞胺前驅物熱醯亞胺化時之溫度為100℃~400℃，較佳為120℃~250℃，以一面將因醯亞胺化反應所生成的水排至系外一面進行者較佳。 The temperature at which the polyimide precursor is thermally imidated in the solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, and the water formed by the imidization reaction is discharged to the system. The outer side is better.

聚醯亞胺前驅物之觸媒醯亞胺化，係可藉由將鹼性觸媒與酸酐添加至聚醯亞胺前驅物之溶液中，並在-20~250℃，較佳為0~180℃下攪拌而進行者。鹼性觸媒的量為醯 胺酸基的0.5~30莫耳倍，較佳為2~20莫耳倍；酸酐的量為醯胺酸基的1~50莫耳倍，較佳為3~30莫耳倍。鹼性觸媒係可列舉：吡啶、三乙基胺、三甲基胺、三丁基胺或三辛基胺等，其中因吡啶在反應進行中具有適度的鹼性而為佳。酸酐係可列舉：乙酸酐、偏苯三甲酸酐或苯均四酸酐等，其中若使用乙酸酐則會使反應結束後的純化變得容易而為佳。由觸媒醯亞胺化所致之醯亞胺化率係可藉由調節觸媒量與反應溫度、反應時間而加以控制。 The ruthenium imidization of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor, and is at -20 to 250 ° C, preferably 0 to Stirring at 180 ° C. The amount of alkaline catalyst is 醯 The amine group is 0.5 to 30 moles, preferably 2 to 20 moles; the amount of the anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the valerine group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferred because it has a moderate basicity in the progress of the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. When acetic anhydride is used, purification after completion of the reaction is facilitated. The imidization ratio by imidization of the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

從聚醯亞胺前驅物或聚醯亞胺之反應溶液，將所生成的聚醯亞胺前驅物或聚醯亞胺回收時，只要使反應溶液投入溶劑中而沉澱即可。沉澱所使用的溶劑係可列舉：甲醇、丙酮、己烷、丁基賽路蘇、庚烷、甲基乙基酮、甲基異丁基酮、乙醇、甲苯、苯或水等。投入溶劑而沉澱後的聚合物係可於經過濾而回收之後，在常壓或減壓下，經常溫或加熱而予以乾燥。此外，若使經沉澱回收的聚合物再溶解於有機溶劑中，反覆進行2~10次之再沉澱回收的操作，則可減少聚合物中之雜質。此時之溶劑係可列舉例如：醇類、酮類或烴等，若使用由此等當中所選出之3種以上的溶劑，則因可更進一步提昇純化之效率而為佳。 When the produced polyimine precursor or polyimine is recovered from the reaction solution of the polyimine precursor or the polyimine, the reaction solution may be precipitated by putting the reaction solution into a solvent. Examples of the solvent used for the precipitation include methanol, acetone, hexane, butyl sirolimus, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene or water. The polymer which has been precipitated by the addition of the solvent can be dried by filtration or filtration, and then dried under normal pressure or reduced pressure at room temperature or under heating. Further, if the polymer recovered by precipitation is redissolved in an organic solvent and the reprecipitation recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. The solvent in this case may, for example, be an alcohol, a ketone or a hydrocarbon. When three or more solvents selected from the above are used, the efficiency of purification can be further improved.

作為特定聚合物(A)所使用的聚醯亞胺之醯胺酸基的脫水閉環率(醯亞胺化率)並不一定要100%，可在0%至100%之範圍內視其用途或目的而任意地選擇，但就更良好的垂直定向性之觀點而言，以20%~80%為佳，40%~60%為更佳。 The dehydration ring closure ratio (the imidization ratio) of the amidino group of the polyimine used as the specific polymer (A) is not necessarily 100%, and may be used in the range of 0% to 100%. Or arbitrarily selected for the purpose, but in terms of better vertical orientation, 20% to 80% is preferable, and 40% to 60% is more preferable.

此外，作為特定聚合物(B)使用的聚醯亞胺之醯亞胺化率也同樣地並不一定要100%，可在0%至100%之範圍內視其用途或目的而任意地選擇，但就更加控制液晶定向處理劑之凝聚或吸出之觀點而言，特定聚合物(B)之醯亞胺化率，係以當特定聚合物(A)也使用聚醯亞胺時與特定聚合物(A)之醯亞胺化率相同以上者為佳，特定聚合物(A)的原料之全部二胺成分中之具有以式[1]所表示的側鏈之二胺化合物的量與特定聚合物(B)的原料之全部二胺成分中之具有以式[1]所表示的側鏈之二胺化合物的量之差異越大，亦即，特定聚合物(A)中之以式[1]所表示之側鏈的量與特定聚合物(B)中之以式[1]所表示之側鏈的量之差異越大，則特定聚合物(A)與特定聚合物(B)之醯亞胺化率之差異越大者為佳。 Further, the ruthenium imidization ratio of the polyimine used as the specific polymer (B) is not necessarily 100%, and may be arbitrarily selected depending on the use or purpose within the range of 0% to 100%. However, in terms of controlling the aggregation or aspiration of the liquid crystal aligning agent, the specific imidization ratio of the specific polymer (B) is determined by the specific polymerization when the specific polymer (A) also uses polyimine. It is preferable that the imineization rate of the substance (A) is the same or more, and the amount and specificity of the diamine compound having the side chain represented by the formula [1] among all the diamine components of the raw material of the specific polymer (A). The greater the difference in the amount of the diamine compound having the side chain represented by the formula [1] among all the diamine components of the raw material of the polymer (B), that is, the specific polymer (A) The larger the difference between the amount of the side chain represented by 1] and the amount of the side chain represented by the formula [1] in the specific polymer (B), the specific polymer (A) and the specific polymer (B) The greater the difference in the imidization rate of hydrazine is better.

本發明之液晶定向處理劑中特定聚合物(A)與特定聚合物(B)之調配比例雖無特別限制，但以例如相對於特定聚合物(A)100質量份，含有40~400質量份之特定聚合物(B)者為佳。 The ratio of the specific polymer (A) to the specific polymer (B) in the liquid crystal aligning agent of the present invention is not particularly limited, but is, for example, 40 to 400 parts by mass based on 100 parts by mass of the specific polymer (A). The specific polymer (B) is preferred.

此外，特定聚合物(A)或特定聚合物(B)之分子量，在考慮到由其所得之聚合物被膜的強度、聚合物被膜形成時的作業性、聚合物被膜的均勻性之情況中，以將依據GPC(凝膠滲透層析，Gel Permeation Chromatography)法所測定的重量平均分子量設為5,000~1,000,000者為佳，更佳為10,000~150,000。 Further, in the case where the molecular weight of the specific polymer (A) or the specific polymer (B) is considered in consideration of the strength of the polymer film obtained therefrom, the workability at the time of formation of the polymer film, and the uniformity of the polymer film, The weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

<特定交聯性化合物(C)> <Specific crosslinkable compound (C)>

本發明之液晶定向處理劑中所含有的特定交聯性化合物(C)係為具有2個以上由環氧基、異氰酸酯基、氧雜環丁烷基及環碳酸酯基所成之群中所選出之至少1種的取代基之交聯性化合物；具有2個以上由羥基、羥烷基及碳數1~6之烷氧烷基所成之群中所選出之至少1種的取代基之交聯性化合物；或具有2個以上聚合性不飽和鍵之交聯性化合物。 The specific crosslinkable compound (C) contained in the liquid crystal aligning agent of the present invention has two or more groups consisting of an epoxy group, an isocyanate group, an oxetanyl group, and a cyclic carbonate group. a crosslinkable compound of at least one substituent selected; having at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and an alkoxyalkyl group having 1 to 6 carbon atoms; a crosslinkable compound; or a crosslinkable compound having two or more polymerizable unsaturated bonds.

具有環氧基或異氰酸酯基2個以上之交聯性化合物係可列舉例如：雙酚丙酮環氧丙基醚、酚醛清漆環氧樹脂、甲酚酚醛清漆環氧樹脂、三環氧丙基異氰尿酸酯、四環氧丙基胺基聯伸苯基、四環氧丙基-m-二甲苯二胺、四環氧丙基-1,3-雙(胺基乙基)環己烷、四苯基環氧丙基醚乙烷、三苯基環氧丙基醚乙烷、雙酚六氟丙酮二環氧丙基醚、1,3-雙(1-(2,3-環氧丙氧基)-1-三氟甲基-2,2,2-三氟甲基)苯、4,4-雙(2,3-環氧丙氧基)八氟聯苯、三環氧丙基-p-胺基酚、四環氧丙基間二甲苯二胺、2-(4-(2,3-環氧丙氧基)苯基)-2-(4-(1,1-雙(4-(2,3-環氧丙氧基)苯基)乙基)苯基)丙烷或1,3-雙(4-(1-(4-(2,3-環氧丙氧基)苯基)-1-(4-(1-(4-(2,3-環氧丙氧基)苯基)-1-甲基乙基)苯基)乙基)苯氧基)-2-丙醇等。其中，以雙酚丙酮環氧丙基醚、四環氧丙基胺基聯伸苯基、或四環氧丙基-1,3-雙(胺基乙基)環己烷為佳。 Examples of the crosslinkable compound having two or more epoxy group or isocyanate groups include bisphenol acetone epoxy propyl ether, novolac epoxy resin, cresol novolac epoxy resin, and trisepoxypropyl isocyanide. Uric acid ester, tetraglycidyl propylamine-linked phenyl group, tetra-epoxypropyl-m-xylenediamine, tetra-epoxypropyl-1,3-bis(aminoethyl)cyclohexane, Tetraphenylepoxypropyl etherethane, triphenylepoxypropyl etherethane, bisphenol hexafluoroacetone diepoxypropyl ether, 1,3-bis(1-(2,3-epoxypropyl) Oxy)-1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octafluorobiphenyl, triepoxypropyl -p-Aminophenol, tetraepoxypropylm-xylylenediamine, 2-(4-(2,3-epoxypropoxy)phenyl)-2-(4-(1,1-bis( 4-(2,3-epoxypropoxy)phenyl)ethyl)phenyl)propane or 1,3-bis(4-(1-(4-(2,3-epoxypropoxy))benzene 1-(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propenyl Alcohol, etc. Among them, bisphenol acetone epoxypropyl ether, tetraglycidylamino-based phenyl group, or tetra-epoxypropyl-1,3-bis(aminoethyl)cyclohexane is preferred.

具有2個以上氧雜環丁烷基之交聯性化合物係可列 舉：至少具有2個以下述之式[4]所表示的氧雜環丁烷基之交聯性化合物。 a crosslinkable compound having two or more oxetanyl groups can be listed A crosslinkable compound having at least two oxetanyl groups represented by the following formula [4].

具體而言，係為以下述之式[4-1]~式[4-11]所表示之交聯性化合物。 Specifically, it is a crosslinkable compound represented by the following formula [4-1] to formula [4-11].

(式[4-1]中，n1為1~3之整數；式[4-7]中，n2為1~3之整數；式[4-8]中，n3為1~3之整數；式[4-9]中，n4為1~100之整數；式[4-11]中，n5為1~10之整數)。 (In the formula [4-1], n1 is an integer from 1 to 3; in the formula [4-7], n2 is an integer from 1 to 3; in the formula [4-8], n3 is an integer from 1 to 3; In [4-9], n4 is an integer from 1 to 100; in the formula [4-11], n5 is an integer from 1 to 10).

其中，以上述式[4-2]、式[4-4]、式[4-10]或式[4-11]為佳。 Among them, the above formula [4-2], formula [4-4], formula [4-10] or formula [4-11] is preferred.

具有2個以上環碳酸酯基之交聯性化合物係可列舉：至少具有2個以下述之式[5]所表示的環碳酸酯基之交聯性化合物。 The crosslinkable compound having two or more cyclic carbonate groups is a crosslinkable compound having at least two cyclic carbonate groups represented by the following formula [5].

具體而言，係可列舉以下述之式[5-1]~式[5-37]所表示之交聯性化合物。 Specifically, a crosslinkable compound represented by the following formula [5-1] to formula [5-37] can be mentioned.

(式[5-24]中，n6為1~5之整數；式[5-25]中，n7為1~5之整數；式[5-36]中，n8為1~100之整數；式[5-37]中，n9為1~10之整數)。 (in the formula [5-24], n6 is an integer from 1 to 5; in the formula [5-25], n7 is an integer from 1 to 5; in the formula [5-36], n8 is an integer from 1 to 100; In [5-37], n9 is an integer from 1 to 10).

進而，特定交聯性化合物(C)亦可列舉具有以下述之式[5-38]~式[5-40]所表示之至少1種的結構之聚矽氧烷。 Further, the specific crosslinkable compound (C) may be a polyoxyalkylene having a structure represented by at least one of the following formulas [5-38] to [5-40].

(式[5-38]~式[5-40]中，R₂₁、R₂₂、R₂₃、R₂₄及R₂₅係各自獨立為以式[5]所表示之結構、氫原子、羥基、碳數1~10之烷基、烷氧基、脂肪族環或芳香族環，且至少1者為以式[5]所表示的結構)。 (In the formula [5-38]~Form [5-40], R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ are each independently a structure represented by the formula [5], a hydrogen atom, a hydroxyl group, or a carbon. An alkyl group, an alkoxy group, an aliphatic ring or an aromatic ring of 1 to 10, and at least one of them is a structure represented by the formula [5].

更具體而言，係可列舉以下述之式[5-41]及式[5-42]所表示之化合物。 More specifically, a compound represented by the following formula [5-41] and formula [5-42] can be cited.

(式[5-41]中，R₂₆係為以上述式[5]所表示的環碳酸酯基；式[5-42]中，n10為1~10之整數)。 (In the formula [5-41], R ₂₆ is a cyclic carbonate group represented by the above formula [5]; and in the formula [5-42], n10 is an integer of 1 to 10).

其中，具有2個以上環碳酸酯基之交聯性化合物，尤以上述式[5-1]、式[5-2]、式[5-3]、式[5-5]、式[5-12]、式[5-20]、式[5-41]、或式[5-42]為佳。 Among them, a crosslinkable compound having two or more cyclic carbonate groups, particularly the above formula [5-1], formula [5-2], formula [5-3], formula [5-5], and formula [5] -12], formula [5-20], formula [5-41], or formula [5-42] is preferred.

具有由羥基、羥烷基及烷氧烷基所成之群中所選出之至少1種的取代基之交聯性化合物，係可列舉例如：羥基、具有羥基或烷氧基之胺基樹脂，例如：三聚氰胺樹脂、脲樹脂、三聚氰二胺樹脂、乙炔脲-甲醛樹脂、琥珀醯基醯胺-甲醛樹脂或伸乙脲-甲醛樹脂等。具體而言，係可使用胺基之氫原子為羥甲基或烷氧基甲基或經其兩者所取代之三聚氰胺衍生物、苯代三聚氰二胺(benzoguanamine)衍生物、或乙炔脲者。三聚氰胺衍生物或苯代三聚氰二胺衍生物亦可作為二聚物或三聚物而存在。此等係以每1個三嗪環，具有平均3個以上、6個以下之羥甲基或烷氧基甲基者為佳。 The crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and an alkoxyalkyl group may, for example, be a hydroxyl group or an amino group-containing resin having a hydroxyl group or an alkoxy group. For example: melamine resin, urea resin, melamine diamine resin, acetylene urea-formaldehyde resin, amber decyl amide-formaldehyde resin or acetaminophen-formaldehyde resin. Specifically, a melamine derivative, a benzoguanamine derivative, or an acetylene urea which is a hydrogen atom of an amine group or a hydroxymethyl group or an alkoxymethyl group or a combination thereof may be used. By. The melamine derivative or the benzoguanamine derivative may also be present as a dimer or a trimer. These are preferably those having an average of 3 or more and 6 or less hydroxymethyl groups or alkoxymethyl groups per one triazine ring.

上述之三聚氰胺衍生物或苯代三聚氰二胺衍生物之例 係可列舉：市售品之每1個三嗪環平均取代3.7個甲氧基甲基的MX-750、每1個三嗪環平均取代5.8個甲氧基甲基的MW-30(以上，SANWA CHEMICAL CO.,LTD製)、或Cymel 300、301、303、350、370、771、325、327、703、712等之甲氧基甲基化三聚氰胺、Cymel 235、236、238、212、253、254等之甲氧基甲基化丁氧基甲基化三聚氰胺、Cymel 506、508等之丁氧基甲基化三聚氰胺、Cymel 1141之類的含有羧基之甲氧基甲基化異丁氧基甲基化三聚氰胺、Cymel 1123之類的甲氧基甲基化乙氧基甲基化苯代三聚氰二胺、含有Cymel 1123-10之類的甲氧基甲基化丁氧基甲基化苯代三聚氰二胺、Cymel 1128之類的丁氧基甲基化苯代三聚氰二胺、Cymel 1125-80之類的含有羧基之甲氧基甲基化乙氧基甲基化苯代三聚氰二胺(以上，三井氰胺製)。此外，乙炔脲之例係可列舉：Cymel 1170之類的丁氧基甲基化乙炔脲、Cymel 1172之類的羥甲基化乙炔脲等、Powderlink 1174之類的甲氧基羥甲基化乙炔脲等。其中，以Cymel 303、Cymel 1141為佳。 Examples of the above melamine derivatives or benzoguanamine derivatives The MX-750 in which one triazine ring of the commercial product is substituted by 3.7 methoxymethyl groups on average, and the MW-30 which replaces 5.8 methoxymethyl groups per one triazine ring on average (above, Methoxymethylated melamine, Cymel 235, 236, 238, 212, 253, such as SANWA CHEMICAL CO., LTD., or Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. a methoxymethylated butoxymethylated melamine of 254 or the like, a butoxymethylated melamine such as Cymel 506 or 508, or a methoxymethylated isobutoxy group having a carboxyl group such as Cymel 1141 Methylated melamine, methoxymethylated ethoxymethylated phenyl melamine diamine such as Cymel 1123, methoxymethylated butoxymethylation containing Cymel 1123-10 Benzene melamine, butyloxymethylated phenyl melamine such as Cymel 1128, methoxymethylated ethoxymethylated benzene containing carboxyl group such as Cymel 1125-80 Generation of melamine (above, Mitsui Cyanamide). Further, examples of the acetylene urea include a butoxymethylated acetylene urea such as Cymel 1170, a methylolated acetylene urea such as Cymel 1172, and a methoxymethylolated acetylene such as Powderlink 1174. Urea, etc. Among them, Cymel 303 and Cymel 1141 are preferred.

此外，列舉具有羥基、羥烷基或烷氧基的苯、或具有羥基、羥烷基或烷氧基的酚性化合物，作為具有由羥基、羥烷基及烷氧烷基所成之群中所選出之至少1種的取代基之交聯性化合物之具有羥基、羥烷基或烷氧基的苯、或酚性化合物，係可列舉例如：1,3,5-參(甲氧基甲基)苯、1,2,4-參(異丙氧基甲基)苯、1,4-雙(sec-丁氧基甲基)苯或2,6-二羥基甲基-p-tert-丁基酚等。 Further, benzene having a hydroxyl group, a hydroxyalkyl group or an alkoxy group, or a phenolic compound having a hydroxyl group, a hydroxyalkyl group or an alkoxy group is exemplified as having a group consisting of a hydroxyl group, a hydroxyalkyl group and an alkoxyalkyl group. A benzene having a hydroxyl group, a hydroxyalkyl group or an alkoxy group as a crosslinkable compound of at least one selected substituent, or a phenolic compound, for example, 1,3,5-glycol (methoxyl) Benzo, 1,2,4-gin (isopropoxymethyl)benzene, 1,4-bis(sec-butoxymethyl)benzene or 2,6-dihydroxymethyl-p-tert- Butyl phenol and the like.

更具體而言，係為以下述之式[6-1]~式[6-48]所表示之交聯性化合物。 More specifically, it is a crosslinkable compound represented by the following formula [6-1] to formula [6-48].

其中，以上述式[6-14]、式[6-15]、式[6-17]、式[6-20]、式[6-21]、式[6-25]、式[6-26]為佳。 Wherein, the above formula [6-14], formula [6-15], formula [6-17], formula [6-20], formula [6-21], formula [6-25], formula [6- 26] is better.

具有聚合性不飽和鍵之交聯性化合物，係可列舉例如：分子內具有3個三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、三(甲基)丙烯醯氧基乙氧基三羥甲基丙烷或丙三醇聚環氧丙基醚聚(甲基)丙烯酸酯等之聚合性不飽和基之交聯性化合物；分子內具有2個乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙烯乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、乙烯氧化物雙酚A型二(甲基)丙烯酸酯、丙烯氧化物雙酚型二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙 烯酸酯、丙三醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、乙二醇二環氧丙基醚二(甲基)丙烯酸酯、二乙二醇二環氧丙基醚二(甲基)丙烯酸酯、鄰苯二甲酸二環氧丙基酯二(甲基)丙烯酸酯或羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯等之聚合性不飽和基之交聯性化合物；分子內具有1個2-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、2-羥基丁基(甲基)丙烯酸酯、2-苯氧基-2-羥基丙基(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基-2-羥基丙基苯二甲酸酯、3-氯-2-羥基丙基(甲基)丙烯酸酯、丙三醇單(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基磷酸酯或N-羥甲基(甲基)丙烯醯胺等之聚合性不飽和基之交聯性化合物。 Examples of the crosslinkable compound having a polymerizable unsaturated bond include, for example, three trimethylolpropane tri(meth)acrylates, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta (methyl) in the molecule. a crosslinkable compound of a polymerizable unsaturated group such as acrylate, tris(meth)acryloxyethoxyethoxytrimethylolpropane or glycerol polyepoxypropyl ether poly(meth)acrylate ; 2 molecules of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (methyl) Acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide double Phenol A type di(meth) acrylate, propylene oxide bisphenol type di(meth) acrylate, 1,6-hexane diol di(methyl) propyl Ethacrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diepoxypropyl ether di(meth)acrylate, diethylene glycol diepoxypropyl Polymeric unsaturated groups such as ether di(meth)acrylate, diepoxypropyl phthalate di(meth)acrylate or hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate a crosslinkable compound; having one 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-benzene in the molecule Oxy-2-hydroxypropyl (meth) acrylate, 2-(methyl) propylene oxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (methyl) The intersection of a polymerizable unsaturated group such as acrylate, glycerol mono(meth)acrylate, 2-(meth)acryloxyethyl phosphate or N-hydroxymethyl(meth)acrylamide A combination compound.

此外，具有聚合性不飽和鍵之交聯性化合物亦可使用以下述式[7]所表示之化合物。 Further, as the crosslinkable compound having a polymerizable unsaturated bond, a compound represented by the following formula [7] can also be used.

(式[7]中，E₁係由環己烷環、聯環己烷環、苯環、聯苯環、聯三苯環、萘環、茀環、蒽環或菲環所選出之基；E₂係由以下述之式[7a]或式[7b]所選出之基；n11為1~4之整數)。 (In the formula [7], E ₁ is a group selected from a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, an anthracene ring, an anthracene ring or a phenanthrene ring; E ₂ is a group selected by the following formula [7a] or formula [7b]; n11 is an integer of 1 to 4).

上述之特定交聯性化合物(C)，亦可因應作為液晶定向膜時的液晶定向性、電壓保持率、積蓄電荷等之特性，而混合使用1種類或2種類以上。 The above-mentioned specific crosslinkable compound (C) may be used in combination of one type or two types or more depending on the characteristics of liquid crystal alignability, voltage holding ratio, and accumulated charge when used as a liquid crystal alignment film.

可藉由含有上述之特定聚合物(A)、特定聚合物(B)及特定交聯性化合物(C)之本發明液晶定向處理劑，而得到賦予液晶高的預傾角，且作為液晶顯示元件時之積蓄電荷為小的液晶定向膜。再者，本發明之液晶定向處理劑，在塗膜面的端部並不會產生聚合物的凝聚物，也就是不會引起白化、凝聚，而塗膜均勻性優異。 The liquid crystal aligning agent of the present invention containing the specific polymer (A), the specific polymer (B), and the specific crosslinkable compound (C) described above can be used to obtain a high pretilt angle for liquid crystal, and can be used as a liquid crystal display element. The accumulated charge at that time is a small liquid crystal alignment film. Further, the liquid crystal aligning agent of the present invention does not cause aggregation of a polymer at the end portion of the coating film surface, that is, it does not cause whitening or aggregation, and the film uniformity is excellent.

本發明之構成，具體而言，係藉由成為含有特定聚合物(A)、特定聚合物(B)及特定交聯性化合物(C)之液晶定向處理劑，而得到上述之預傾角特性、積蓄電荷特性及塗膜均勻性的效果，其理由雖並未明確，但大致推測如下。 Specifically, the composition of the present invention is obtained by a liquid crystal aligning agent containing a specific polymer (A), a specific polymer (B), and a specific crosslinkable compound (C), thereby obtaining the above-described pretilt characteristics. Although the reason for the effect of accumulating charge characteristics and uniformity of the coating film is not clear, it is roughly presumed as follows.

本發明之液晶定向處理劑中所含有之特定聚合物(B)的原料之二胺成分中之具有以上述式[1]所表示的側鏈之二胺化合物的比例，係較特定聚合物(A)的原料之二胺成分中之具有以上述式[1]所表示之側鏈之二胺化合物的比例更低。因此，可推測：由本發明之液晶定向處理劑所得之液晶定向膜，由於其提高液晶定向膜的電阻之側鏈的比例(亦即側鏈的密度)較單獨使用特定聚合物(A)時更少，因此變得不易將藉由直流電壓所積蓄的電荷積存。 The ratio of the diamine compound having a side chain represented by the above formula [1] among the diamine components of the raw material of the specific polymer (B) contained in the liquid crystal aligning agent of the present invention is a specific polymer ( Among the diamine components of the raw material of A), the ratio of the diamine compound having a side chain represented by the above formula [1] is lower. Therefore, it is presumed that the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention has a higher ratio of the side chain of the resistance of the liquid crystal alignment film (i.e., the density of the side chain) than when the specific polymer (A) is used alone. Since it is small, it becomes difficult to accumulate the electric charge accumulated by the DC voltage.

在此，雖可考量單純地減少具有側鏈之二胺化合物的 量以減少積蓄電荷，但若減少具有側鏈之二胺化合物的量便會產生預傾角特性惡化的問題。於本發明中，藉由成為上述本發明之構成，原料之具有以上述式[1]所表示之側鏈的二胺化合物之比例相對較少的特定聚合物(B)位於液晶定向膜之基板側，且原料之具有以上述式[1]所表示之側鏈的二胺化合物之比例相對較多的特定聚合物(A)位於液晶定向膜表面(亦即接觸到液晶的面)，據此而可以推測，主要藉由特定聚合物(A)而使液晶展現良好的預傾角。且，可認為：由於原料之具有以上述式[1]所表示之側鏈的二胺化合物之比例相對較少的特定聚合物(B)位於液晶定向膜之基板側(亦即，不接觸到液晶之側)，因此積蓄電荷會減低。 Here, it is possible to consider simply reducing the diamine compound having a side chain. The amount is reduced to reduce the accumulated charge, but if the amount of the diamine compound having a side chain is reduced, the problem of deterioration of the pretilt characteristics is caused. In the present invention, by the constitution of the present invention, the specific polymer (B) having a relatively small proportion of the diamine compound having the side chain represented by the above formula [1] is located on the substrate of the liquid crystal alignment film. a specific polymer (A) having a relatively large proportion of a diamine compound having a side chain represented by the above formula [1] on the surface of the liquid crystal alignment film (that is, a surface contacting the liquid crystal), It can be inferred that the liquid crystal exhibits a good pretilt angle mainly by the specific polymer (A). Further, it is considered that the specific polymer (B) having a relatively small proportion of the diamine compound having a side chain represented by the above formula [1] is located on the substrate side of the liquid crystal alignment film (that is, not in contact with The side of the liquid crystal), so the accumulated charge will be reduced.

此外，可認為：本發明之液晶定向處理劑所含有的特定交聯性化合物(C)會藉由熱或紫外線而與特定聚合物(A)及特定聚合物(B)中之羧基、羧酯基(carboxyl ester group)、胺基進行反應，而將特定聚合物(A)及特定聚合物(B)之主鏈間予以交聯，且藉由特定交聯性化合物(C)之作用，以上述式[1]所表示之側鏈結構會更趨穩定化，藉此不論液晶之種類為何，液晶定向膜皆展現高且穩定的預傾角。 In addition, it is considered that the specific crosslinkable compound (C) contained in the liquid crystal aligning agent of the present invention is bonded to the carboxyl group or the carboxylic acid ester of the specific polymer (A) and the specific polymer (B) by heat or ultraviolet rays. The carboxyl ester group and the amine group are reacted to crosslink the main chain of the specific polymer (A) and the specific polymer (B), and by the action of the specific crosslinkable compound (C), The side chain structure represented by the above formula [1] is more stabilized, whereby the liquid crystal alignment film exhibits a high and stable pretilt angle regardless of the type of liquid crystal.

接著可認為：由於特定聚合物(A)之側鏈與特定聚合物(B)之側鏈兩者皆具有以式[1]所表示的結構，因此可控制因特定聚合物(A)與特定聚合物(B)之特性的差異所導致的凝聚或析出，而塗膜均勻性優異。 It can be considered that since both the side chain of the specific polymer (A) and the side chain of the specific polymer (B) have the structure represented by the formula [1], it is possible to control the specific polymer (A) and the specific The aggregation or precipitation due to the difference in the characteristics of the polymer (B) is excellent in uniformity of the coating film.

另外，上述之液晶定向膜之所謂預傾角特性、積蓄電荷特性、及塗膜均勻性全部為良好之該效果，係特定聚合物(A)及特定聚合物(B)兩者皆將具有特定結構之以上述式[1]所表示之側鏈的二胺化合物作為原料，亦即，特定聚合物(A)及特定聚合物(B)兩者皆將具有特定結構之以上述式[1]所表示之結構作為側鏈，且，為僅具有特定交聯性化合物(C)時所發揮的效果。 Further, the so-called pretilt angle characteristics, the accumulated charge characteristics, and the uniformity of the coating film of the above liquid crystal alignment film are all good, and both the specific polymer (A) and the specific polymer (B) have a specific structure. The diamine compound of the side chain represented by the above formula [1] is used as a raw material, that is, both the specific polymer (A) and the specific polymer (B) have a specific structure by the above formula [1]. The structure shown is a side chain and is an effect exerted only when the specific crosslinkable compound (C) is present.

相對於經特定聚合物(A)及特定聚合物(B)總計得100質量份，本發明之液晶定向處理劑中之特定交聯性化合物(C)的含量係以0.1~150質量份為佳，為了使交聯反應進行並展現所期望之預傾角等之特性，且不讓液晶之定向性降低，更佳為0.1~100質量份，特別是1~50質量份。 The content of the specific crosslinkable compound (C) in the liquid crystal aligning agent of the present invention is preferably 0.1 to 150 parts by mass, based on 100 parts by mass of the specific polymer (A) and the specific polymer (B). In order to carry out the crosslinking reaction and exhibit the characteristics of a desired pretilt angle or the like without lowering the orientation of the liquid crystal, it is more preferably 0.1 to 100 parts by mass, particularly 1 to 50 parts by mass.

<其他的液晶定向處理劑之成分> <Other components of liquid crystal aligning agent>

本發明之液晶定向處理劑，其聚合物成分係可僅為特定聚合物(A)及特定聚合物(B)，且可於特定聚合物(A)及特定聚合物(B)中混合有其他聚合物。此時，相對於特定聚合物(A)及特定聚合物(B)，其他的聚合物之含量係為0.5~15質量%，較佳為1.0~10質量%。其他的聚合物係可列舉：由不含具有以上述式[1]所表示之側鏈的二胺化合物之二胺成分與不含以上述式[3]所表示之四羧酸二酐的四羧酸二酐成分所得之聚醯亞胺前驅物或聚醯亞胺。再者，聚醯亞胺前驅物及聚醯亞胺以外之聚合物，具 體而言，亦可列舉：丙烯酸聚合物、甲基丙烯酸聚合物、聚苯乙烯或聚醯胺等。 The liquid crystal aligning agent of the present invention may have a polymer component of only a specific polymer (A) and a specific polymer (B), and may be mixed with a specific polymer (A) and a specific polymer (B). polymer. In this case, the content of the other polymer is 0.5 to 15% by mass, preferably 1.0 to 10% by mass based on the specific polymer (A) and the specific polymer (B). The other polymer system may be a diamine component containing no diamine compound having a side chain represented by the above formula [1] and four tetracarboxylic acid dianhydride not represented by the above formula [3]. A polyimide precursor or a polyimine obtained from a carboxylic acid dianhydride component. Furthermore, a polymer other than a polyimide precursor and a polyimine The body may also be exemplified by an acrylic polymer, a methacrylic polymer, polystyrene or polyamine.

此外，本發明之液晶定向處理劑亦可含有有機溶劑。 Further, the liquid crystal aligning agent of the present invention may contain an organic solvent.

本發明之液晶定向處理劑中之有機溶劑，就所謂藉由塗佈而形成均勻的聚合物被膜之觀點而言，有機溶劑之含量係以70~99質量%者為佳。此含量係可隨著目的之液晶定向膜的厚度而適當地變更。此時之有機溶劑係只要使上述之特定聚合物(A)及特定聚合物(B)溶解之有機溶劑則無特別限制。更具體而言，係可列舉：N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-甲基己內醯胺、2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-乙烯吡咯啶酮、二甲基亞碸、四甲脲、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯、1,3-二甲基-咪唑啶酮、乙基戊基酮、甲基壬基酮、甲基乙基酮、甲基異戊基酮、甲基異丙基酮、環己酮、碳酸乙烯酯、碳酸丙烯酯、二甘二甲醚及4-羥基-4-甲基-2-戊酮等。此等係可單獨使用，亦可加以混合而使用。 In the organic solvent in the liquid crystal aligning agent of the present invention, the content of the organic solvent is preferably from 70 to 99% by mass in terms of forming a uniform polymer film by coating. This content can be appropriately changed depending on the thickness of the intended liquid crystal alignment film. The organic solvent in this case is not particularly limited as long as the organic solvent in which the specific polymer (A) and the specific polymer (B) described above are dissolved. More specifically, it may, for example, be N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam , 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl fluorene, γ- Butyrolactone, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexyl Ketone, ethylene carbonate, propylene carbonate, diglyme and 4-hydroxy-4-methyl-2-pentanone. These may be used singly or in combination.

本發明之液晶定向處理劑中，作為促進液晶定向膜中之電荷移動，且促進使用有該液晶定向膜之液晶胞的電荷消除之化合物，以添加下述式[M1]~式[M155]所表示之含氮雜環胺化合物者為佳。該胺化合物係直接添加至使特定聚合物(A)及特定聚合物(B)溶解於上述有機溶劑等的溶液中亦無妨，但以成為適當的溶劑且濃度0.1~10質量%，且較佳為1.0~7.0質量%之溶液後再進行添加者為佳。 該含氮雜環胺化合物之溶劑，係只要使上述之特定聚合物(A)及特定聚合物(B)溶解之有機溶劑則無特別限制。 In the liquid crystal aligning agent of the present invention, as a compound which promotes charge transfer in the liquid crystal alignment film and promotes charge elimination using the liquid crystal cell having the liquid crystal alignment film, the following formula [M1]~[M155] is added. Preferably, the nitrogen-containing heterocyclic amine compound is represented. The amine compound may be added directly to a solution in which the specific polymer (A) and the specific polymer (B) are dissolved in the organic solvent or the like, but may be an appropriate solvent and have a concentration of 0.1 to 10% by mass, preferably It is preferred to add 1.0 to 7.0% by mass of the solution. The solvent of the nitrogen-containing heterocyclic amine compound is not particularly limited as long as the organic solvent in which the specific polymer (A) and the specific polymer (B) described above are dissolved.

本發明之液晶定向處理劑只要不損及本發明之效果，亦可含有使塗佈有液晶定向處理劑時的聚合物被膜之膜厚均勻性或表面平滑性提昇的有機溶劑(亦稱為不良溶劑)或化合物。再者，亦可含有使液晶定向膜與基板之密合性提昇的化合物等。 The liquid crystal aligning agent of the present invention may contain an organic solvent (also referred to as a poor film) for improving the film thickness uniformity or surface smoothness of the polymer film when the liquid crystal aligning agent is applied, as long as the effect of the present invention is not impaired. Solvent) or compound. Further, a compound or the like which improves the adhesion between the liquid crystal alignment film and the substrate may be contained.

使膜厚之均勻性或表面平滑性提昇之不良溶劑的具體例係可列舉：異丙醇、甲氧基甲基戊醇、甲基賽路蘇、乙基賽路蘇、丁基賽路蘇、甲基賽路蘇乙酸酯、乙基賽路蘇乙酸酯、丁基卡必醇、乙基卡必醇、乙基卡必醇乙酸酯、乙二醇、乙二醇單乙酸酯、乙二醇單異丙基醚、乙二醇單丁基醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲基醚、丙 二醇-tert-丁基醚、二丙二醇單甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲基醚、3-甲基-3-甲氧基丁醇、二異丙基醚、乙基異丁基醚、倍異丁烯、乙酸戊酯、丁酸丁酯、丁基醚、二異丁基酮、甲基環己烯、丙基醚、二己基醚、n-己烷、n-戊烷、n-辛烷、二乙基醚、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇-1-單甲基醚-2-乙酸酯、丙二醇-1-單乙基醚-2-乙酸酯、二丙二醇、2-(2-乙氧基丙氧基)丙醇、乳酸甲基酯、乳酸乙基酯、乳酸n-丙基酯、乳酸n-丁基酯或乳酸異戊基酯等之具有低表面張力的有機溶劑等。 Specific examples of the poor solvent for improving the uniformity of the film thickness or the surface smoothness include isopropyl alcohol, methoxymethylpentanol, methyl stilbene, ethyl stilbene, and butyl 赛苏苏. , Methyl sulphate acetate, ethyl sirolimus acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetic acid Ester, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, C Glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3- Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, isobutylene, amyl acetate, butyric acid Butyl ester, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate , ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3-ethoxy Methyl ethyl propyl propionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, 3-methoxypropane Butyl acrylate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol , 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2- Acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate or isoamyl lactate An organic solvent or the like having a low surface tension such as an ester.

此等之不良溶劑係可1種或混合複數種使用。使用如上所述之不良溶劑時，係以液晶定向處理劑中所含有之有機溶劑整體的5~80質量%者為佳，較佳為20~60質量%。 These poor solvents can be used alone or in combination of plural kinds. When the poor solvent as described above is used, it is preferably from 5 to 80% by mass, preferably from 20 to 60% by mass, based on the total of the organic solvent contained in the liquid crystal alignment treatment agent.

使膜厚之均勻性或表面平滑性提昇之化合物係可列舉：氟系界面活性劑、聚矽氧系界面活性劑、非離子系界 面活性劑等。更具體而言，係可列舉例如：E-Top EF301、EF303、EF352(TOHKEM PRODUCTS CORPORATION製)、MEGAFACE F171、F173、R-30(大日本油墨製)、Fluorad FC430、FC431(住友3M製)、AashiGuard AG710、SURFLON S-382、SC101、SC102、SC103、SC104、SC105、SC106(旭硝子製)等。相對於液晶定向處理劑中所含有的聚合物成分成分之100質量份，此等之界面活性劑之使用比例，較佳為0.01~2質量份，更佳為0.01~1質量份。 Examples of the compound which improves the uniformity of the film thickness or the surface smoothness include a fluorine-based surfactant, a polyfluorene-based surfactant, and a non-ionic boundary. Surfactant and the like. More specifically, for example, E-Top EF301, EF303, EF352 (manufactured by TOHKEM PRODUCTS CORPORATION), MEGAFACE F171, F173, R-30 (made by Dainippon Ink), Fluorad FC430, FC431 (manufactured by Sumitomo 3M), AashiGuard AG710, SURFLON S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass). The ratio of use of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the polymer component contained in the liquid crystal alignment treatment agent.

使液晶定向膜與基板之密合性提昇的化合物係可列舉含官能性矽烷化合物或含環氧基化合物，且可列舉例如：3-胺基丙基三甲基矽烷、3-胺基丙基三乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、N-乙氧基羰基-3-胺基丙基三甲氧基矽烷、N-乙氧基羰基-3-胺基丙基三乙氧基矽烷、N-三乙氧基矽丙基三伸乙基三胺、N-三甲氧基矽丙基三伸乙基三胺、10-三甲氧基矽-1,4,7-三氮雜癸烷(triazadecane)、10-三乙氧基矽-1,4,7-三氮雜癸烷、9-三甲氧基矽烷基-3,6-二氮雜壬基乙酸酯(diazanonyl acetate)、9-三乙氧基矽烷基-3,6-二氮雜壬基乙酸酯(diazanonyl acetate)、N-苄基-3-胺基丙基三甲氧基矽烷、N-苄基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙 基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-雙(氧乙烯)-3-胺基丙基三甲氧基矽烷、N-雙(氧乙烯)-3-胺基丙基三乙氧基矽烷、乙二醇二環氧丙基醚、聚乙二醇二環氧丙基醚、丙二醇二環氧丙基醚、三丙二醇二環氧丙基醚、聚丙二醇二環氧丙基醚、新戊二醇二環氧丙基醚、1,6-己二醇二環氧丙基醚、丙三醇二環氧丙基醚、2,2-二溴新戊二醇二環氧丙基醚、1,3,5,6-四環氧丙基-2,4-己二醇、N,N,N’,N’,-四環氧丙基-m-二甲苯二胺、1,3-雙(N,N-二環氧丙基胺基甲基)環己烷或N,N,N’,N’，-四環氧丙基-4,4’-二胺基二苯甲烷等。 Examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include a functional decane-containing compound or an epoxy group-containing compound, and examples thereof include 3-aminopropyltrimethylnonane and 3-aminopropyl group. Triethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane , N-(2-Aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N -ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxysulfonylpropyltriethylidene Amine, N-trimethoxysulfonylpropyltriethylamine, 10-trimethoxyindole-1,4,7-triazadecane, 10-triethoxyphosphonium-1,4 , 7-triazadecane, 9-trimethoxydecyl, 3,3-diazanonyl acetate, 9-triethoxydecyl-3,6-diaza Diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N- Propan-3-amine Trimethoxy decane, N-phenyl-3-aminopropyltriethoxy decane, N-bis(oxyethylene)-3-aminopropyltrimethoxydecane, N-bis(oxyethylene)- 3-aminopropyltriethoxydecane, ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, tripropylene glycol diepoxypropyl ether, Polypropylene glycol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, glycerol diepoxypropyl ether, 2,2-dibromo Neopentyl glycol diepoxypropyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, N,N,N',N',-tetraepoxypropyl- M-xylylenediamine, 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane or N,N,N',N',-tetraepoxypropyl-4, 4'-diaminodiphenylmethane and the like.

使用此等基板相密合的化合物時，係以相對於液晶定向處理劑中所含有的聚合物成分之100質量份為0.1~30質量份者為佳，更佳為1~20質量份。若未達0.1質量份則無法期待密合性提昇的效果，若多於30質量份則會有液晶之定向性變差的情形。 When the compound is used in an amount of 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the polymer component contained in the liquid crystal alignment treatment agent. If it is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it is more than 30 parts by mass, the orientation of the liquid crystal may be deteriorated.

於本發明之液晶定向處理劑中，係除了上述之不良溶劑及化合物之外，只要在不損及本發明之效果的範圍內，亦可添加其他以改變液晶定向膜之介電係數或導電性等之電特性為目的之介電體或導電物質。 In the liquid crystal aligning agent of the present invention, in addition to the above-mentioned poor solvent and compound, other factors may be added to change the dielectric constant or conductivity of the liquid crystal alignment film as long as the effect of the present invention is not impaired. A dielectric or conductive substance for the purpose of electrical properties.

<液晶定向膜、液晶顯示元件> <Liquid crystal alignment film, liquid crystal display element>

本發明之液晶定向處理劑係可在基板上塗佈、燒成之後，利用摩擦處理(rubbing process)或光照射等進行定向處理，而作為液晶定向膜使用。此外，用於垂直定向用 途時，即使不進行定向處理也可作為液晶定向膜使用。此時所使用的基板，係只要是透明性高的基板即不特別限制，亦可使用玻璃基板以外其他的丙烯酸系基板或聚碳酸酯基板等之塑膠基板等。就製程之簡化的觀點而言，以使用形成有液晶驅動所需之ITO電極等的基板者為佳。此外，於反射型之液晶顯示元件中，若僅為單側之基板則亦可使用矽晶圓等之不透明的基板，此時之電極亦可使用鋁等之讓光反射的材料。 The liquid crystal alignment treatment agent of the present invention can be applied to a substrate, and then subjected to orientation treatment by a rubbing process or light irradiation, and then used as a liquid crystal alignment film. In addition, for vertical orientation In the meantime, it can be used as a liquid crystal alignment film even without performing orientation treatment. The substrate to be used in this case is not particularly limited as long as it is a substrate having high transparency, and an acrylic substrate such as an acrylic substrate or a plastic substrate such as a polycarbonate substrate may be used. From the viewpoint of simplification of the process, it is preferred to use a substrate on which an ITO electrode or the like required for liquid crystal driving is formed. Further, in the reflective liquid crystal display device, an opaque substrate such as a germanium wafer may be used as the substrate on one side, and a material such as aluminum that reflects light may be used as the electrode.

液晶定向處理劑之塗佈方法雖無特別限定，但工業上普遍利用網版印刷、澆版印刷、柔版印刷或噴墨法等來進行的方法。其他的塗佈方法係有含浸法、輥式塗佈法、縫隙塗佈法、旋轉法、噴塗法等，亦可因應目的而使用此等方法。本發明之上述液晶定向處理劑，由於塗膜均勻性優異，故塗佈其所形成的塗膜係可控制白化、凝聚，且成為均勻的膜。 The coating method of the liquid crystal alignment treatment agent is not particularly limited, but a method generally performed by screen printing, pattern printing, flexographic printing, or inkjet method is widely used in the industry. Other coating methods include an impregnation method, a roll coating method, a slit coating method, a spinning method, a spray coating method, and the like, and these methods can also be used depending on the purpose. In the liquid crystal aligning agent of the present invention, since the uniformity of the coating film is excellent, the coating film formed by coating can control whitening and aggregation, and becomes a uniform film.

於基板上塗佈有液晶定向處理劑之後，係可藉由加熱板、熱循環型爐或IR(紅外線)型爐等之加熱手段使溶劑在50~300℃，較佳為80~250℃下蒸發而成為聚合物被膜(液晶定向膜)。燒成後之聚合物被膜的厚度，若過厚則對液開顯示元件之消耗電力方面變得不利，若過薄則有液晶顯示元件之可靠性降低的情況，故較佳為5~300nm、更佳為10~100nm。當使液晶水平定向或傾斜定向時，係利用摩擦或偏光紫外線照射等來處理燒成後之聚合物被膜。 After the liquid crystal aligning agent is applied onto the substrate, the solvent may be heated at 50 to 300 ° C, preferably 80 to 250 ° C by heating means such as a hot plate, a heat cycle type furnace or an IR (infrared) type furnace. Evaporated to form a polymer film (liquid crystal alignment film). When the thickness of the polymer film after firing is too large, the power consumption of the liquid-display element becomes unfavorable. If the thickness of the liquid crystal display element is too small, the reliability of the liquid crystal display element is lowered. Therefore, it is preferably 5 to 300 nm. More preferably, it is 10 to 100 nm. When the liquid crystal is oriented horizontally or obliquely, the polymer film after firing is treated by rubbing or polarized ultraviolet irradiation or the like.

本發明之液晶顯示元件，係為在藉由上述之手段而由 本發明之液晶定向處理劑得到附液晶定向膜之基板之後，利用習知的方法來製作液晶胞而作成液晶顯示元件。 The liquid crystal display element of the present invention is obtained by the above means In the liquid crystal aligning agent of the present invention, a substrate having a liquid crystal alignment film is obtained, and then a liquid crystal cell is produced by a known method to form a liquid crystal display element.

液晶胞之製作方法係可例示：準備形成有上述液晶定向膜之一對基板，且於其中一枚基板的液晶定向膜上散佈間隔物，以使液晶定向膜面成為內側的方式，來貼合另一枚基板，將液晶減壓注入並加以密封的方法，或，在將液晶滴下至散佈有間隔物的液晶定向膜面之後貼合基板而進行密封的方法等。 In the method of producing a liquid crystal cell, it is possible to form a pair of substrates on which the liquid crystal alignment film is formed, and to spread a spacer on the liquid crystal alignment film of one of the substrates so that the liquid crystal alignment film surface becomes inside. The other substrate is a method in which the liquid crystal is injected under reduced pressure and sealed, or a method in which the liquid crystal is dropped onto the liquid crystal alignment film surface on which the spacer is dispersed, and then the substrate is bonded and sealed.

液晶係使用具有正的介電異向性之正型液晶或具有負的介電異向性的負型液晶。 The liquid crystal system uses a positive liquid crystal having a positive dielectric anisotropy or a negative liquid crystal having a negative dielectric anisotropy.

進而，本發明之液晶定向處理劑，係亦適宜使用於液晶顯示元件，該液晶顯示元件在具備有電極之一對的基板之間具有液晶層而成，係經過將含有藉由活性能量線及熱之至少一者而聚合的聚合性化合物之液晶組成物配置於一對的基板之間，並一面將電壓施加於電極間一面藉由活性能量線的照射及加熱之至少一者而使聚合性化合物聚合的步驟所製造。在此，紫外線較適合作為活性能量線。 Further, the liquid crystal aligning agent of the present invention is also suitably used for a liquid crystal display device having a liquid crystal layer between substrates having one pair of electrodes, which is subjected to active energy rays and The liquid crystal composition of the polymerizable compound polymerized in at least one of the heat is disposed between the pair of substrates, and is polymerized by at least one of irradiation and heating of the active energy rays while applying a voltage between the electrodes Manufactured by the step of polymerizing the compound. Here, ultraviolet rays are more suitable as active energy rays.

上述液晶顯示元件係藉由PSA(聚合物穩定定向，Polymer Sustained Alignment)方式來將液晶分子之預傾斜(pre-tilt)作控制。於PSA方式中，係將少量的光聚合性化合物，例如光聚合性單體混入液晶材料中，在安裝有液晶胞之後，在對液晶層施加特定之電壓的狀態下對光聚合性化合物照射紫外線等，藉由所生成的聚合物來控制液晶分子的預傾斜。當聚合物生成時液晶分子之定向狀態係 即使在消除電壓之後仍有所記憶，故可藉由控制形成於液晶層的電場等，而調整液晶分子的預傾斜。此外，於PSA方式中，並不需要摩擦處理，故適於以摩擦處理難以控制預傾斜的垂直定向型之液晶層的形成。 The above liquid crystal display element controls the pre-tilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA method, a small amount of a photopolymerizable compound such as a photopolymerizable monomer is mixed into a liquid crystal material, and after the liquid crystal cell is attached, the photopolymerizable compound is irradiated with ultraviolet rays while applying a specific voltage to the liquid crystal layer. Etc., the pretilt of the liquid crystal molecules is controlled by the generated polymer. The orientation state of liquid crystal molecules when the polymer is formed Even if there is memory after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed in the liquid crystal layer. Further, in the PSA method, since the rubbing treatment is not required, it is suitable to form the liquid crystal layer of the vertical alignment type which is difficult to control the pretilt by the rubbing treatment.

亦即，本發明之液晶顯示元件，係可在藉由上述之手法而由本發明之液晶定向處理劑得到附液晶定向膜的基板之後，製作液晶胞，且藉由紫外線的照射及加熱之至少一者來使聚合性化合物進行聚合，藉此控制液晶分子之定向。 In other words, in the liquid crystal display device of the present invention, after the substrate having the liquid crystal alignment film is obtained from the liquid crystal alignment treatment agent of the present invention by the above-described method, the liquid crystal cell is produced, and at least one of irradiation and heating by ultraviolet rays is performed. The polymerizable compound is polymerized to control the orientation of the liquid crystal molecules.

若列舉製作液晶胞之一例，則可列舉：準備形成有液晶定向膜之一對基板，且於其中一枚基板的液晶定向膜上散佈間隔物，以使液晶定向膜面成為內側的方式，來貼合另一枚基板，將液晶減壓注入並加以密封的方法，或，在將液晶滴下至散佈有間隔物的液晶定向膜面之後貼合基板而進行密封的方法等。 An example of producing a liquid crystal cell is to prepare a substrate on which a liquid crystal alignment film is formed, and to spread a spacer on a liquid crystal alignment film of one of the substrates so that the liquid crystal alignment film surface becomes inside. A method of bonding another substrate, injecting and sealing the liquid crystal under reduced pressure, or a method of sealing the liquid crystal after dropping the liquid crystal onto the liquid crystal alignment film surface on which the spacer is dispersed, and then sealing the substrate.

於液晶中係混合有藉由熱或紫外線照射而聚合的聚合性化合物。聚合性化合物係可列舉：分子內具有1個以上丙烯酸酯基或甲基丙烯酸酯基等之聚合性不飽和基的化合物。此時，相對於液晶成分100質量份，聚合性化合物係以0.01~10質量份為佳，更佳為0.1~5質量份。若聚合性化合物未達0.01質量份，則聚合性化合物不進行聚合而變得無法控制液晶之定向，若高於10質量份，則未反應的聚合性化合物會變多而液晶顯示元件的燒入(burn-in)特性會降低。 A polymerizable compound which is polymerized by irradiation with heat or ultraviolet rays is mixed in the liquid crystal. The polymerizable compound is a compound having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule. In this case, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. When the amount of the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound is not polymerized and the alignment of the liquid crystal is not controlled. When the amount is more than 10 parts by mass, the unreacted polymerizable compound is increased and the liquid crystal display element is burned. (burn-in) characteristics will be reduced.

在製作有液晶胞之後，係一面將交流或直流的電壓施加於液晶胞，一面照射熱或紫外線來使聚合性化合物進行聚合。藉此，可控制液晶分子之定向。 After the liquid crystal cell is produced, a voltage of alternating current or direct current is applied to the liquid crystal cell, and the polymerizable compound is polymerized while irradiating heat or ultraviolet rays. Thereby, the orientation of the liquid crystal molecules can be controlled.

除此之外，本發明之液晶定向處理劑，係亦適宜使用於在具備有電極之一對的基板之間具有液晶層而成的液晶顯示元件，該液晶顯示元件，係經過將含有藉由活性能量線及熱之至少一者而聚合的聚合性基之液晶定向膜配置於前述一對的基板之間，並將電壓施加於電極間的步驟所製造。在此，紫外線較適合作為活性能量線。 In addition, the liquid crystal aligning agent of the present invention is also suitably used for a liquid crystal display element having a liquid crystal layer between substrates having one pair of electrodes, and the liquid crystal display element is passed through A liquid crystal alignment film in which a polymerizable group polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and a voltage is applied between the electrodes. Here, ultraviolet rays are more suitable as active energy rays.

為了得到包含由活性能量線及熱之至少一者而進行聚合的聚合性基之液晶定向膜，係可列舉：將包含該聚合性基之化合物添加於液晶定向處理劑中的方法，或使用包含聚合性基之聚合物成分的方法。液晶定向處理劑，例如若包含藉由熱或紫外線的照射而進行反應之具雙鍵部位的特定胺化合物，則可藉由紫外線的照射及加熱之至少一者而控制液晶分子的定向。 In order to obtain a liquid crystal alignment film containing a polymerizable group which is polymerized by at least one of an active energy ray and heat, a method of adding a compound containing the polymerizable group to a liquid crystal aligning agent, or a method of containing A method of polymerizing a polymer component. The liquid crystal aligning agent can control the orientation of the liquid crystal molecules by at least one of irradiation and heating of ultraviolet rays, for example, if a specific amine compound having a double bond site is reacted by irradiation with heat or ultraviolet rays.

若列舉製作液晶胞之一例，則可列舉：準備形成有液晶定向膜之一對基板，且於其中一枚基板的液晶定向膜上散佈間隔物，以使液晶定向膜面成為內側的方式，來貼合另一枚基板，將液晶減壓注入並加以密封的方法，或在將液晶滴下至散佈有間隔物的液晶定向膜面之後貼合基板而進行密封的方法等。 An example of producing a liquid crystal cell is to prepare a substrate on which a liquid crystal alignment film is formed, and to spread a spacer on a liquid crystal alignment film of one of the substrates so that the liquid crystal alignment film surface becomes inside. A method of bonding another substrate, injecting and sealing the liquid crystal under reduced pressure, or a method of sealing the liquid crystal after dropping the liquid crystal onto the liquid crystal alignment film surface on which the spacer is dispersed, and then sealing the substrate.

在製作有液晶胞之後，係一面將交流或直流的電壓施加於液晶胞，一面照射熱或紫外線，藉此而可控制液晶分 子之定向。 After the liquid crystal cell is produced, a voltage of alternating current or direct current is applied to the liquid crystal cell, and heat or ultraviolet rays are irradiated while controlling the liquid crystal. The orientation of the child.

如以上所述般，使用本發明之液晶定向處理劑所製作出的液晶顯示元件，係成為可靠性優異者，且可適合利用於大畫面且高精細的液晶電視等。 As described above, the liquid crystal display element produced by using the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be suitably used for a large-screen, high-definition liquid crystal television or the like.

[實施例] [Examples]

以下，列舉實施例進行說明。另外，本發明並不限定於此等所解說者。 Hereinafter, the examples will be described. Further, the present invention is not limited to those illustrated herein.

<特定聚合物(A)及特定聚合物(B)之合成> <Synthesis of specific polymer (A) and specific polymer (B)>

下述所使用的代號係如下所述。 The code numbers used below are as follows.

(四羧酸二酐) (tetracarboxylic dianhydride)

A-1：1,2,3,4-環丁烷四羧酸二酐 A-1:1,2,3,4-cyclobutane tetracarboxylic dianhydride

A-2：雙環[3,3,0]辛烷-2,4,6,8-四羧酸二酐 A-2: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

A-3：苯均四酸二酐 A-3: pyromellitic dianhydride

(具有以上述式[1]所表示之側鏈的二胺化合物) (a diamine compound having a side chain represented by the above formula [1])

B-1：1,3-二胺基-5-〔4-{1-(反-4-n-戊基環己基)-反-4-環己基}苯氧基甲基〕苯 B-1: 1,3-diamino-5-[4-{1-(trans-4-n-pentylcyclohexyl)-trans-4-cyclohexyl}phenoxymethyl]benzene

B-2：1,3-二胺基-4-{4-(4-n-庚基環己基)苯氧基}苯 B-2: 1,3-diamino-4-{4-(4-n-heptylcyclohexyl)phenoxy}benzene

(其他的二胺化合物) (other diamine compounds)

B-3：1,4-伸苯基二胺 B-3: 1,4-phenylenediamine

B-4：N-(3-吡啶甲基)-3,5-二胺基苯甲醯胺 B-4: N-(3-pyridylmethyl)-3,5-diaminobenzamide

B-5：3,5-二胺基苯甲酸 B-5: 3,5-diaminobenzoic acid

B-6：二胺基二苯甲烷 B-6: Diaminodiphenylmethane

(添加物) (additive)

C-1：3-胺基吡啶 C-1: 3-aminopyridine

(交聯性化合物) (crosslinkable compound)

D-1：2,2-雙(4-羥基-3,5-二羥基甲基苯基)丙烷 D-1: 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane

(有機溶劑) (Organic solvents)

NMP：N-甲基-2-吡咯啶酮 NMP: N-methyl-2-pyrrolidone

BCS：丁基賽路蘇 BCS: Butyl Cyrus

(聚醯胺酸、聚醯亞胺之分子量測量) (Measurement of molecular weight of poly-proline and polyimine)

聚醯胺酸及聚醯亞胺之分子量係使用昭和電工公司製常溫凝膠滲透層析(GPC)裝置(GPC-101)、Shodex公司製管柱(KD-803、KD-805)且依照以下的方式來測 The molecular weight of the polyaminic acid and the polyimine is a normal temperature gel permeation chromatography (GPC) device (GPC-101) manufactured by Showa Denko Co., Ltd., and a pipe column (KD-803, KD-805) manufactured by Shodex Co., Ltd. Way to measure

管柱溫度：50℃ Column temperature: 50 ° C

溶析液：N,N’-二甲基甲醯胺(作為添加劑，溴化鋰-水合物(LiBr‧H₂O)為30 mmol/L，磷酸/無水結晶(o-磷酸)為30 mmol/L，四氫呋喃(THF)為10ml/L) Eluent: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr‧H ₂ O) is 30 mmol/L, phosphoric acid/anhydrous crystal (o-phosphoric acid) is 30 mmol/L , tetrahydrofuran (THF) is 10ml / L)

流速：1.0ml/分 Flow rate: 1.0ml/min

檢量線作成用標準樣品：TOSOH CORPORATION製TSK標準聚乙烯氧化物(分子量約900,000、150,000、100,000、30,000)，及Polymer Laboratories Ltd製聚乙烯乙二醇(分子量約12,000、4,000、1,000)。 A standard sample for the calibration curve was prepared: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by TOSOH CORPORATION, and polyethylene glycol (molecular weight: about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories Ltd.

(醯亞胺化率之測量) (Measurement of yttrium imidation rate)

將20mg之聚醯亞胺粉末裝入NMR樣品管(草野科學公司製NMR取樣管標準 5)，並添加0.53ml之氘化二甲基亞碸(DMSO-d6、0.05%TMS(四甲基矽烷)混合品)，施加超音波使其完全溶解。利用JEOL DATUM LTD製NMR測定器(JNW-ECA500)測量出此溶液500MHz之質子NMR。醯亞胺化率，係將來自在醯亞胺化前後皆不改變的結構之質子作為基準質子而定，並使用此質子之峰值積分值與來自9.5至10.0ppm附近所顯現的醯胺酸之NH基的質子 峰值積分值且藉由以下的式子而求出。 20 mg of polyimine powder was charged into the NMR sample tube (the NMR sampling tube standard manufactured by Kusano Scientific Co., Ltd.) 5), and adding 0.53 ml of deuterated dimethyl hydrazine (DMSO-d6, 0.05% TMS (tetramethyl decane) mixture), applying ultrasonic waves to completely dissolve. Proton NMR of this solution at 500 MHz was measured using a NMR analyzer (JNW-ECA500) manufactured by JEOL DATUM LTD. The ruthenium imidization rate is determined by using a proton from a structure which does not change before and after the imidization as a reference proton, and the peak integral value of the proton and the NH of the proline which is present from 9.5 to 10.0 ppm are used. The proton peak integrated value of the base is obtained by the following formula.

醯亞胺化率(%)=(1-α‧x/y)×100 醯 imidization rate (%) = (1-α‧x/y) × 100

於上述式中，x係來自醯胺酸之NH基的質子峰值積分值，y係基準質子之峰值積分值，α係聚醯胺酸(醯亞胺化率為0%)時基準質子相對於1個醯胺酸之NH基質子的個數比率。 In the above formula, x is the peak value of the proton peak derived from the NH group of valine acid, the peak integral value of the y-based reference proton, and the reference proton relative to the α-poly-proline (the imidization ratio is 0%). The ratio of the number of NH protons of one proline.

<實施例1> <Example 1>

在NMP(290g)中混合A-2(48.9g，19.5 mmol)、B-1(31.0g，6.89 mmol)、B-3(17.4g，16.0 mmol)，並使其在40℃下進行反應5小時，之後，加入A-1(5.77g，2.94 mmol)與NMP(120g)，並使其在40℃下進行反應15小時，得到聚醯胺酸之溶液(濃度20.0質量%)。此聚醯胺酸之數量平均分子量為11,700，重量平均分子量為40,600。 A-2 (48.9 g, 19.5 mmol), B-1 (31.0 g, 6.89 mmol), B-3 (17.4 g, 16.0 mmol) were mixed in NMP (290 g) and allowed to react at 40 ° C. After an hour, A-1 (5.77 g, 2.94 mmol) and NMP (120 g) were added, and the reaction was carried out at 40 ° C for 15 hours to obtain a polylysine solution (concentration: 20.0% by mass). The polyamine has a number average molecular weight of 11,700 and a weight average molecular weight of 40,600.

在將NMP加入該聚醯胺酸之溶液(485g)中並稀釋成6質量%後，加入作為醯亞胺化觸媒之乙酸酐(66.2g)、吡啶(34.2g)，使其在100℃下進行反應2.5小時。將此反應溶液注入甲醇(6010g)，並將所生成的沉澱物濾出。利用甲醇來將此沉澱物予以洗淨，在100℃下進行減壓乾燥而得到聚醯亞胺之粉末(相當於特定聚合物(A))。此聚醯亞胺之醯亞胺化率係為60%，其數量平均分子量為10,900，重量平均分子量為38,900。 After adding NMP to the polyamine acid solution (485 g) and diluting it to 6 mass%, acetic anhydride (66.2 g) and pyridine (34.2 g) as a ruthenium catalyst were added thereto at 100 ° C. The reaction was carried out for 2.5 hours. This reaction solution was poured into methanol (6010 g), and the resulting precipitate was filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a powder of polyimine (corresponding to a specific polymer (A)). The polyimine has a hydrazine imidation ratio of 60%, a number average molecular weight of 10,900, and a weight average molecular weight of 38,900.

將NMP(18.8g)加入該聚醯亞胺之粉末(3.85g) 中，而在70℃下進行攪拌30小時使其溶解，之後，加入NMP、C-1之NMP溶液、BCS，並在50℃下進行攪拌20小時，調製出使聚醯亞胺成為6質量%、C-1成為0.5質量%、NMP成為48.5質量%、BCS成為45質量%之聚醯亞胺溶液(A)。 NMP (18.8 g) was added to the powder of the polyimine (3.85 g) In the middle, the mixture was stirred at 70 ° C for 30 hours to dissolve, and then NMP, C-1 NMP solution and BCS were added, and the mixture was stirred at 50 ° C for 20 hours to prepare a polyimine to be 6 mass%. A polyimine solution (A) in which C-1 is 0.5% by mass, NMP is 48.5% by mass, and BCS is 45% by mass.

<實施例2> <Example 2>

在NMP(1510g)中混合A-2(236g，94.0 mmol)、B-2(84.5g，22.2 mmol)、B-4(53.7g，22.1 mmol)、B-5(101g，66.3 mmol)，並使其在80℃下進行反應5小時，之後，加入A-1(30.4g，15.5 mmol)與NMP(506g)，並使其在40℃下進行反應5小時，得到聚醯胺酸之溶液(濃度20.0質量%)。此聚醯胺酸之數量平均分子量為12,600，重量平均分子量為61,400。 Mix A-2 (236 g, 94.0 mmol), B-2 (84.5 g, 22.2 mmol), B-4 (53.7 g, 22.1 mmol), B-5 (101 g, 66.3 mmol) in NMP (1510 g), and The reaction was carried out at 80 ° C for 5 hours, after which A-1 (30.4 g, 15.5 mmol) and NMP (506 g) were added, and the reaction was carried out at 40 ° C for 5 hours to obtain a solution of polyproline ( The concentration was 20.0% by mass). The polyamine has a number average molecular weight of 12,600 and a weight average molecular weight of 61,400.

在將NMP加入該聚醯胺酸之溶液(600g)中並稀釋成6質量%後，加入作為醯亞胺化觸媒之乙酸酐(268g)、吡啶(41.6g)，使其在100℃下進行反應4小時。將此反應溶液注入甲醇(8080g)，並將所生成的沉澱物濾出。利用甲醇來將此沉澱物予以洗淨，在100℃下進行減壓乾燥而得到聚醯亞胺之粉末(相當於特定聚合物(B))。此聚醯亞胺之醯亞胺化率係為80%，其數量平均分子量為10,900，重量平均分子量為38,900。 After NMP was added to the solution of the polyamic acid (600 g) and diluted to 6 mass%, acetic anhydride (268 g) and pyridine (41.6 g) as a ruthenium catalyst were added thereto at 100 ° C. The reaction was carried out for 4 hours. This reaction solution was poured into methanol (8080 g), and the resulting precipitate was filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a powder of polyimine (corresponding to a specific polymer (B)). The polyamidimide had an imidization ratio of 80%, a number average molecular weight of 10,900, and a weight average molecular weight of 38,900.

將NMP(18.8g)加入該聚醯亞胺之粉末(3.85g)中，而在70℃下進行攪拌30小時使其溶解，之後，加入 NMP、C-1之NMP溶液、BCS，並在50℃下進行攪拌20小時，調製出使聚醯亞胺為6質量%、C-1成為0.3質量%、NMP成為48.5質量%、BCS成為45質量%之聚醯亞胺溶液(B)。 NMP (18.8 g) was added to the powder of the polyimine (3.85 g), and stirred at 70 ° C for 30 hours to dissolve, and then, added. The NMP solution of NMP and C-1 and BCS were stirred at 50 ° C for 20 hours to prepare a polybenzamine of 6 mass%, C-1 of 0.3 mass%, NMP of 48.5% by mass, and BCS of 45. Mass% of the polyimine solution (B).

<實施例3> <Example 3>

將在實施例1所得之聚醯亞胺溶液(A)與在實施例2所得之聚醯亞胺溶液(B)在室溫下進行混合，以使聚醯亞胺溶液(A)與聚醯亞胺溶液(B)成為質量%計20：80，進而，相對於聚醯亞胺加入3質量%之D-1並加以攪拌，利用細孔徑1μm之薄膜過濾器進行加壓過濾而得到實施例3之液晶定向處理劑。 The polyimine solution (A) obtained in Example 1 and the polyimine solution (B) obtained in Example 2 were mixed at room temperature to make the polyimine solution (A) and polypeptone. The imine solution (B) was 20% by mass%, and further, 3% by mass of D-1 was added to the polyimide, and the mixture was stirred and filtered by a membrane filter having a pore size of 1 μm to obtain an example. 3 liquid crystal directional treatment agent.

<實施例4> <Example 4>

與實施例3相同地，將聚醯亞胺溶液(A)與聚醯亞胺溶液(B)在室溫下進行混合，以使聚醯亞胺溶液(A)與聚醯亞胺溶液(B)成為質量%計40：60，進而，相對於聚醯亞胺加入3質量%之D-1並加以攪拌，利用細孔徑1μm之薄膜過濾器進行加壓過濾而得到實施例4之液晶定向處理劑。 In the same manner as in Example 3, the polyimine solution (A) and the polyimine solution (B) were mixed at room temperature to obtain a polyimine solution (A) and a polyimine solution (B). The mass% was 40:60, and further, 3% by mass of D-1 was added to the polyimine, and the mixture was stirred, and subjected to pressure filtration using a membrane filter having a pore size of 1 μm to obtain a liquid crystal directional treatment of Example 4. Agent.

<實施例5> <Example 5>

與實施例3相同地，將聚醯亞胺溶液(A)與聚醯亞胺溶液(B)在室溫下進行混合，以使聚醯亞胺溶液(A)與 聚醯亞胺溶液(B)成為質量%計70：30，進而，相對於聚醯亞胺加入3質量%之D-1並加以攪拌，利用細孔徑1μm之薄膜過濾器進行加壓過濾而得到實施例5之液晶定向處理劑。 In the same manner as in Example 3, the polyimine solution (A) and the polyimine solution (B) were mixed at room temperature to make the polyimine solution (A) and The polyimine solution (B) was 70:30 by mass, and further, 3% by mass of D-1 was added to the polyimine and stirred, and pressure filtration was carried out using a membrane filter having a pore size of 1 μm. The liquid crystal aligning agent of Example 5.

<比較例1> <Comparative Example 1>

於在實施例1所得之聚醯亞胺溶液(A)中，相對於聚醯亞胺加入3質量%之D-1並加以攪拌，利用細孔徑1μm之薄膜過濾器進行加壓過濾而得到比較例1之液晶定向處理劑。 In the polyimine solution (A) obtained in Example 1, 3% by mass of D-1 was added to the polyimine and stirred, and pressure filtration was carried out using a membrane filter having a pore size of 1 μm to obtain a comparison. The liquid crystal aligning agent of Example 1.

<比較例2> <Comparative Example 2>

將在實施例1所得之聚醯亞胺溶液(A)與在實施例2所得之聚醯亞胺溶液(B)在室溫下進行混合，以使聚醯亞胺溶液(A)與聚醯亞胺溶液(B)成為質量%計20：80，利用細孔徑1μm之薄膜過濾器進行加壓過濾而得到比較例2之液晶定向處理劑。 The polyimine solution (A) obtained in Example 1 and the polyimine solution (B) obtained in Example 2 were mixed at room temperature to make the polyimine solution (A) and polypeptone. The imine solution (B) was 20:80 by mass%, and was subjected to pressure filtration using a membrane filter having a pore diameter of 1 μm to obtain a liquid crystal aligning agent of Comparative Example 2.

<比較例3> <Comparative Example 3>

參考專利文獻2的方式，在NMP(450g)中混合A-1(19.6g，10 mmol)、A-3(20.1g，9.19 mmol)、B-6(39.7g，20 mmol)，並使其在23℃下進行反應4小時得到聚醯胺酸之溶液(濃度15.0質量%)。於此溶液中加入NMP、BCS，調製出使聚醯胺酸成為6質量%、NMP成為49 質量%、BCS成為45質量%之聚醯胺酸溶液(C)。 Referring to the method of Patent Document 2, A-1 (19.6 g, 10 mmol), A-3 (20.1 g, 9.19 mmol), B-6 (39.7 g, 20 mmol) were mixed in NMP (450 g), and The reaction was carried out at 23 ° C for 4 hours to obtain a solution of polylysine (concentration: 15.0% by mass). NMP and BCS were added to the solution to prepare a polyglycine to be 6 mass% and NMP to be 49. The mass% and BCS were 45% by mass of a polyaminic acid solution (C).

將在實施例1所得之聚醯亞胺溶液(A)與聚醯胺酸溶液(C)在室溫下進行混合，以使聚醯亞胺溶液(A)與聚醯胺酸溶液(C)成為質量%計20：80。進而，相對於聚醯亞胺與聚醯胺酸之合計加入3質量%之D-1並加以攪拌，利用細孔徑1μm之薄膜過濾器進行加壓過濾而得到比較例3之液晶定向處理劑。 The polyimine solution (A) obtained in Example 1 is mixed with the polyaminic acid solution (C) at room temperature to make the polyimine solution (A) and the polyaminic acid solution (C) It becomes 20% by mass%. Furthermore, 3% by mass of D-1 was added to the total of the polyimine and the polyaminic acid, and the mixture was stirred, and subjected to pressure filtration using a membrane filter having a pore size of 1 μm to obtain a liquid crystal aligning agent of Comparative Example 3.

將在實施例及比較例中所得之液晶定向處理劑展示於表49中。 The liquid crystal aligning treatment agents obtained in the examples and the comparative examples are shown in Table 49.

<殘留DC之評估> <Evaluation of Residual DC>

將液晶定向處理劑旋轉塗佈於附ITO電極之玻璃基板，在80℃之加熱板上使其乾燥5分鐘，之後，利用230℃之熱風循環式爐進行30分鐘燒成，形成膜厚100nm之膜而得到附液晶定向膜之基板。準備2片此附液晶定向膜之基板，在其中1片的液晶定向膜面上散佈有4μm之間隔物之後，從其上印刷密封劑，在使另1片基板以朝向液晶定向膜面的方式貼合之後，使密封劑硬化而製作出空胞。藉由 減壓注入法，將液晶MLC-2041(Merck Japan公司製)注入此空胞中，並將注入口密封而得到垂直定向液晶胞。另外，使用實施例3~5及比較例1~3之液晶定向處理劑，並分別進行上述操作而得到垂直定向液晶胞。 The liquid crystal aligning agent was spin-coated on a glass substrate with an ITO electrode, and dried on a hot plate at 80 ° C for 5 minutes, and then fired in a hot air circulating furnace at 230 ° C for 30 minutes to form a film thickness of 100 nm. The film is obtained to obtain a substrate with a liquid crystal alignment film. Two sheets of the substrate with the liquid crystal alignment film were prepared, and after a spacer of 4 μm was spread on one of the liquid crystal alignment film surfaces, the sealant was printed thereon, and the other substrate was oriented toward the liquid crystal. After the bonding, the sealant is hardened to produce a hollow cell. By In a vacuum injection method, liquid crystal MLC-2041 (manufactured by Merck Japan Co., Ltd.) was injected into the hollow cell, and the injection port was sealed to obtain a vertically oriented liquid crystal cell. Further, the liquid crystal aligning agents of Examples 3 to 5 and Comparative Examples 1 to 3 were used, and the above operations were carried out to obtain vertically oriented liquid crystal cells.

將30Hz、13Vpp之交流電壓，及1V之直流電壓施加於此等之液晶胞，且使其在23℃之溫度下驅動12小時。其後評估閃爍，將其強度成為最小的施加電壓視為殘留DC。將評估結果展現於表50中。 An alternating current voltage of 30 Hz, 13 Vpp, and a direct current voltage of 1 V were applied to the liquid crystal cells, and driven at a temperature of 23 ° C for 12 hours. Thereafter, the flicker is evaluated, and the applied voltage whose intensity is minimized is regarded as residual DC. The evaluation results are shown in Table 50.

<預傾角之評估> <Evaluation of pretilt angle>

將液晶定向處理劑旋轉塗佈於附ITO電極之玻璃基板，在80℃之加熱板上使其乾燥5分鐘，之後，利用230℃之熱風循環式爐進行30分鐘燒成，形成膜厚100nm之膜而得到附液晶定向膜之基板。將本基板在輥子旋轉數1000rpm、台速度50mm/秒、輥子押入壓0.2mm下藉由棉布來摩擦。進而準備2片該基板，在其中1片的液晶定向膜面上散佈有4μm之間隔物之後，從其上印刷密封劑，在使另1片基板以朝向液晶定向膜面的方式，且使摩擦方向成為反向平行(antiparallel)的方式貼合之後，使密封劑硬化而製作出空胞。藉由減壓注入法，將液晶MLC-2041(Merck Japan公司製)注入此空胞中，並將注入口密封而得到垂直定向液晶胞。另外，使用實施例3~5及比較例1~3之液晶定向處理劑，並分別進行上述操作而得到垂直定向液晶胞。 The liquid crystal aligning agent was spin-coated on a glass substrate with an ITO electrode, and dried on a hot plate at 80 ° C for 5 minutes, and then fired in a hot air circulating furnace at 230 ° C for 30 minutes to form a film thickness of 100 nm. The film is obtained to obtain a substrate with a liquid crystal alignment film. The substrate was rubbed by a cotton cloth at a number of revolutions of the roller of 1000 rpm, a table speed of 50 mm/sec, and a roll press pressure of 0.2 mm. Further, two sheets of the substrate were prepared, and a spacer of 4 μm was spread on one of the liquid crystal alignment film surfaces, and then a sealant was printed thereon, and the other substrate was oriented toward the liquid crystal to face the film surface, and rubbing was performed. After the directions are brought into an antiparallel manner, the sealant is hardened to produce a hollow cell. Liquid crystal MLC-2041 (manufactured by Merck Japan Co., Ltd.) was injected into the hollow cell by a pressure reduction injection method, and the injection port was sealed to obtain a vertically oriented liquid crystal cell. Further, the liquid crystal aligning agents of Examples 3 to 5 and Comparative Examples 1 to 3 were used, and the above operations were carried out to obtain vertically oriented liquid crystal cells.

藉由精密量測法來測量此等之液晶胞的延遲(retardation)，並依據液晶的尋常光折射率與異常光折射率來算出液晶之預傾角。另外，本預傾角係定義為於由基板法線方向與摩擦方向所構成之面內，來自基板水平方向的角度。將評估結果展示於表50中。 The retardation of the liquid crystal cells is measured by a precision measurement method, and the pretilt angle of the liquid crystal is calculated from the ordinary light refractive index of the liquid crystal and the extraordinary light refractive index. In addition, the pretilt angle is defined as an angle from the horizontal direction of the substrate in the plane formed by the normal direction of the substrate and the rubbing direction. The results of the evaluation are shown in Table 50.

<白化、凝聚之評估> <Evaluation of whitening and cohesion>

將實施例3~5及比較例1~3之各液晶定向處理劑旋轉塗佈於鉻基板(將鉻蒸鍍後之玻璃基板)，並在溫度23℃、相對濕度60%的環境下放置10分鐘，然後，目視觀察出於塗膜面端部是否有聚合物之凝聚物產生。將評估結果展示於表51中。 Each of the liquid crystal aligning agents of Examples 3 to 5 and Comparative Examples 1 to 3 was spin-coated on a chromium substrate (a glass substrate after chromium deposition), and placed in an environment of a temperature of 23 ° C and a relative humidity of 60%. Minutes, then, visual observation was made as to whether or not polymer agglomerates were produced at the end of the coating film. The evaluation results are shown in Table 51.

其結果，於使用有含有規定之特定聚合物(A)、特定聚合物(B)及交聯性化合物(C)的實施例3~5之液晶定向處理劑的液晶胞中，其預傾角較大，且殘留DC較小。再者，於實施例3~5之液晶定向處理劑中，並不會引起白化、聚集，且其塗膜均勻性優異。 As a result, in the liquid crystal cell using the liquid crystal aligning agent of Examples 3 to 5 containing the specific polymer (A), the specific polymer (B), and the crosslinkable compound (C), the pretilt angle was higher. Large and residual DC is small. Further, in the liquid crystal aligning agents of Examples 3 to 5, whitening and aggregation were not caused, and the coating film uniformity was excellent.

另一方面，於未含有規定之特定聚合物(A)、特定聚合物(B)及交聯性化合物(C)的比較例1~3中，其並非為預傾角特性、積蓄電荷特性及液晶定向處理劑之塗膜均勻性全部皆優異者。具體而言，於使用有比較例1~3之液晶定向處理劑之液晶胞中，相較於實施例3~5，其殘留DC較高。此外，於實施例3與比較例2之比較中，於使用有未含有特定交聯性化合物(C)之比較例2的液晶定向處理劑之液晶胞中，其預傾角較小。再者，於實施例3與比較例3之比較中，於使用有未含有特定聚合物(B)之比較例3的液晶定向處理劑中，會引起白化、凝聚。 On the other hand, in Comparative Examples 1 to 3 which did not contain the predetermined specific polymer (A), specific polymer (B), and crosslinkable compound (C), they were not pretilt characteristics, accumulated charge characteristics, and liquid crystal. The coating film uniformity of the directional treatment agent is all excellent. Specifically, in the liquid crystal cells using the liquid crystal alignment treatment agents of Comparative Examples 1 to 3, the residual DC was higher than in Examples 3 to 5. Further, in the comparison of the third embodiment and the comparative example 2, the liquid crystal cell of the liquid crystal aligning agent of Comparative Example 2 which does not contain the specific crosslinkable compound (C) has a small pretilt angle. Further, in the comparison between Example 3 and Comparative Example 3, whitening and aggregation were caused in the liquid crystal aligning agent of Comparative Example 3 in which the specific polymer (B) was not contained.

Claims (14)

一種液晶定向處理劑，其特徵為含有下述之特定聚合物(A)、特定聚合物(B)及特定交聯性化合物(C)，且特定聚合物(A)及特定聚合物(B)中之至少一者，係使用以下述式[2]所表示之二胺化合物作為原料之二胺成分，特定聚合物(A)：由使用具有以式[1]所表示之側鏈的二胺化合物作為原料的一部分之聚醯亞胺前驅物及聚醯亞胺所成之群中所選出之至少1種的聚合物，特定聚合物(B)：由使用具有以式[1]所表示之側鏈的二胺化合物作為原料的一部分，且原料之全部二胺成分中之具有以式[1]所表示之側鏈的二胺化合物之比例，係較特定聚合物(A)的原料之全部二胺成分中之具有以式[1]所表示之側鏈的二胺化合物之比例更少的聚醯亞胺前驅物及聚醯亞胺所成之群中所選出之至少1種的聚合物，特定交聯性化合物(C)：具有2個以上由環氧基、異氰酸酯基、氧雜環丁烷基及環碳酸酯基所成之群中所選出之至少1種的取代基之交聯性化合物；具有2個以上由羥基、羥烷基及碳數1~6之烷氧烷基所成之群中所選出之至少1種的取代基之交聯性化合物；或具有2個以上聚合性不飽和鍵之交聯性化合物， (式[1]中，X₁係單鍵、-(CH₂)_a-(a為1~15之整數)、-O- 、-CH₂O-、-COO-或-OCO-；X₂係單鍵或-(CH₂)_b-(b為1~15之整數)；X₃係單鍵、-(CH₂)_c-(c為1~15之整數)、-O-、-CH₂O-、-COO-或-OCO-；X₄係由苯環、環己烷環及雜環所成之群中所選出之2價的環狀基、或具有類固醇骨架之碳數12~25之2價的有機基；前述環狀基上之任意的氫原子係可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子所取代；X₅係由苯環、環己烷環及雜環所成之群中所選出之2價的環狀基；此等環狀基上之任意的氫原子係可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子所取代；n為0~4之整數；X₆係碳數1~18之直鏈狀或分支狀烷基、碳數1~18之直鏈狀或分支狀含氟烷基、碳數1~18之直鏈狀或分支狀烷氧基、或碳數1~18之直鏈狀或分支狀含氟烷氧基；特定聚合物(A)的原料之二胺化合物所具有之以式[1]所表示之側鏈與特定聚合物(B)的原料之二胺化合物所具有之以式[1]所表示之側鏈係可為相同或相異) (式[2]中，Y₁係-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCO-、-CON(CH₃)-或-N(CH₃)CO-；Y₂係單鍵、2價的碳數1~20之脂肪族烴基、非芳香族環式烴基或芳香族烴基；Y₃係單鍵、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-COO-、-OCO-、-CON(CH₃)-、 -N(CH₃)CO-或-O(CH₂)_i-(i為1~5之整數)；Y₄係1價的含氮芳香族雜環；h為1~4之整數)。 A liquid crystal aligning agent characterized by comprising the specific polymer (A), a specific polymer (B) and a specific crosslinkable compound (C), and a specific polymer (A) and a specific polymer (B) At least one of them is a diamine component using a diamine compound represented by the following formula [2] as a raw material, and a specific polymer (A): using a diamine having a side chain represented by the formula [1] a polymer of at least one selected from the group consisting of a polyimine precursor and a polyimine which is a part of a raw material, and a specific polymer (B): having a formula represented by the formula [1] The diamine compound of the side chain is a part of the raw material, and the ratio of the diamine compound having the side chain represented by the formula [1] among all the diamine components of the raw material is the same as the raw material of the specific polymer (A). a polymer having at least one selected from the group consisting of a polyimine precursor having a ratio of a diamine compound represented by the formula [1] and a polyimine in the diamine component. Specific crosslinkable compound (C): having two or more of an epoxy group, an isocyanate group, an oxetanyl group, and a ring carbon a crosslinkable compound of at least one substituent selected from the group consisting of ester groups; selected from the group consisting of two or more alkoxyalkyl groups having a hydroxyl group, a hydroxyalkyl group and a carbon number of 1 to 6 a crosslinkable compound having at least one substituent; or a crosslinkable compound having two or more polymerizable unsaturated bonds, (In the formula [1], X ₁ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-; X ₂ A single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15); X ₃ is a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-; X ₄ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a carbon number having a steroid skeleton 12~ a 25-valent organic group; any hydrogen atom on the above cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a fluorine-containing alkyl group having 1 to 3 carbon atoms. a fluoroalkoxy group having 1 to 3 carbon atoms or a fluorine atom; X ₅ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring; Any hydrogen atom on the group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkyl group having 1 to 3 carbon atoms. Substituted by an oxy group or a fluorine atom; n is an integer of 0 to 4; X ₆ is a linear or branched alkyl group having 1 to 18 carbon atoms; and a linear or branched fluorine-containing alkyl group having 1 to 18 carbon atoms; a linear or branched alkoxy group having a carbon number of 1 to 18 or a linear or branched carbon number of 1 to 18 A fluoroalkoxy group; a diamine compound of a raw material of a specific polymer (A) having a side chain of the formula [1] and a diamine compound of a raw material of the specific polymer (B) having the formula [1] The side chain systems indicated can be the same or different) (In the formula [2], Y ₁ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ ) - or -N(CH ₃ )CO-; Y ₂ single bond, divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, non-aromatic cyclic hydrocarbon group or aromatic hydrocarbon group; Y ₃ single bond, -O- , -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ )CO- or -O(CH ₂ ) _i - (i is an integer of 1 to 5); Y ₄ is a monovalent nitrogen-containing aromatic heterocyclic ring; h is an integer of 1 to 4). 如申請專利範圍第1項之液晶定向處理劑，其中當將特定聚合物(A)的原料之全部二胺成分中之具有以式[1]所表示之側鏈的二胺化合物之比例設為1時，特定聚合物(B)的原料之全部二胺成分中之具有以式[1]所表示之側鏈的二胺化合物之比例為0.3以上且未達1.0。 The liquid crystal aligning agent of the first aspect of the invention, wherein the ratio of the diamine compound having the side chain represented by the formula [1] among all the diamine components of the raw material of the specific polymer (A) is set to At 1 o., the ratio of the diamine compound having a side chain represented by the formula [1] among all the diamine components of the raw material of the specific polymer (B) is 0.3 or more and less than 1.0. 如申請專利範圍第1項之液晶定向處理劑，其中特定聚合物(A)的原料之具有以式[1]所表示之側鏈的二胺化合物及特定聚合物(B)的原料之具有以式[1]所表示之側鏈的二胺化合物，係分別為以下述式[1a]所表示之二胺化合物， (式[1a]中，X₁、X₂、X₃、X₄、X₅、X₆、n係與式[1]中之X₁、X₂、X₃、X₄、X₅、X₆、n相同；m為1~4之整數；特定聚合物(A)的原料之以式[1a]所表示之二胺化合物與特定聚合物(B)的原料之以式[1a]所表示之二胺化合物係可為相同或相異)。 The liquid crystal aligning agent according to claim 1, wherein the raw material of the specific polymer (A) has a diamine compound having a side chain represented by the formula [1] and a raw material of the specific polymer (B). The diamine compound of the side chain represented by the formula [1] is a diamine compound represented by the following formula [1a], respectively. (In the formula [1a], X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , n are X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X in the formula [1] ₆ and n are the same; m is an integer of 1 to 4; the raw material of the specific polymer (A) is represented by the formula [1a] of the diamine compound represented by the formula [1a] and the specific polymer (B) The diamine compounds may be the same or different). 如申請專利範圍第1項之液晶定向處理劑，其中特定聚合物(A)及特定聚合物(B)，係使用以下述式[3]所表示之四羧酸二酐作為原料的一部分， (式[3]中，Z₁係含有碳數4~6之非芳香族環狀烴基之碳數4~13之4價的有機基)。 The liquid crystal aligning agent of the first aspect of the invention, wherein the specific polymer (A) and the specific polymer (B) are a part of a raw material using a tetracarboxylic dianhydride represented by the following formula [3]. (In the formula [3], Z ₁ is a tetravalent organic group having 4 to 13 carbon atoms of a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms). 如申請專利範圍第4項之液晶定向處理劑，其中Z₁係為以下述式[3a]~式[3j]所表示之結構， (式[3a]中，Z₂~Z₅係氫原子、甲基、氯原子或苯環，且可各自為相同或相異，式[3g]中，Z₆及Z₇係氫原子或甲基，且可各自為相同或相異)。 The liquid crystal aligning agent according to item 4 of the patent application, wherein the Z ₁ system is a structure represented by the following formula [3a] to formula [3j], (In the formula [3a], Z ₂ to Z ₅ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may each be the same or different, in the formula [3g], a Z ₆ and Z ₇ hydrogen atom or a Bases, and may each be the same or different). 如申請專利範圍第1項之液晶定向處理劑，其中特定交聯性化合物(C)係具有氧雜環丁烷基之交聯性化合物；具有環碳酸酯基之交聯性化合物；或具有由羥基、羥烷基及碳數1~6之烷氧烷基所成之群中所選出之至少1種的取代基之苯或酚性化合物的交聯性化合物。 The liquid crystal aligning agent according to claim 1, wherein the specific crosslinkable compound (C) is a crosslinkable compound having an oxetanyl group; a crosslinkable compound having a cyclic carbonate group; or A crosslinkable compound of a benzene or a phenolic compound having at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and an alkoxyalkyl group having 1 to 6 carbon atoms. 如申請專利範圍第1項之液晶定向處理劑，其中特定聚合物(A)及特定聚合物(B)係為聚醯胺酸。 The liquid crystal aligning agent according to claim 1, wherein the specific polymer (A) and the specific polymer (B) are polyamic acid. 如申請專利範圍第1項之液晶定向處理劑，其中特定聚合物(A)及特定聚合物(B)係為使聚醯胺酸脫水閉環所得之聚醯亞胺。 The liquid crystal aligning agent according to the first aspect of the invention, wherein the specific polymer (A) and the specific polymer (B) are polyimine obtained by dehydrating and ring-closing polylysine. 如申請專利範圍第1項之液晶定向處理劑，其中相對於特定聚合物(A)及特定聚合物(B)的總量100質量份，特定交聯性化合物(C)為0.1質量份~50質量份。 The liquid crystal aligning agent according to claim 1, wherein the specific crosslinkable compound (C) is 0.1 part by mass to 50 parts by mass based on 100 parts by mass of the total of the specific polymer (A) and the specific polymer (B). Parts by mass. 如申請專利範圍第1項之液晶定向處理劑，其係含有5~60質量%之不良溶劑。 The liquid crystal aligning agent of the first aspect of the patent application contains 5 to 60% by mass of a poor solvent. 一種液晶定向膜，其特徵為使用如申請專利範圍第1項~第10項中任一項之液晶定向處理劑所得者。 A liquid crystal alignment film which is obtained by using the liquid crystal alignment treatment agent according to any one of the first to tenth aspects of the patent application. 如申請專利範圍第11項之液晶定向膜，其係用於液晶顯示元件，該液晶顯示元件係在具備有電極之一對的基板之間具有液晶層而成，且係經過將含有藉由活性能量線及熱之至少一者而聚合的聚合性化合物之液晶組成物配置於前述一對的基板之間，並一面將電壓施加於前述電極間一面使前述聚合性化合物聚合的步驟所製造。 The liquid crystal alignment film according to claim 11, which is used for a liquid crystal display element having a liquid crystal layer between substrates having one pair of electrodes, and is subjected to activity by A liquid crystal composition of a polymerizable compound polymerized by at least one of an energy ray and a heat is disposed between the pair of substrates, and is produced by a step of applying a voltage between the electrodes to polymerize the polymerizable compound. 一種液晶顯示元件，其特徵為具有如申請專利範圍第11項之液晶定向膜。 A liquid crystal display element characterized by having a liquid crystal alignment film according to claim 11 of the patent application. 一種液晶顯示元件，其特徵為具有如申請專利範圍第12項之液晶定向膜。 A liquid crystal display element characterized by having a liquid crystal alignment film according to item 12 of the patent application.