TWI654222B - Liquid crystal alignment treatment agent and liquid crystal display element using the same - Google Patents

Liquid crystal alignment treatment agent and liquid crystal display element using the same

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TWI654222B
TWI654222B TW103133591A TW103133591A TWI654222B TW I654222 B TWI654222 B TW I654222B TW 103133591 A TW103133591 A TW 103133591A TW 103133591 A TW103133591 A TW 103133591A TW I654222 B TWI654222 B TW I654222B
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crystal alignment
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TW201522422A (en
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鉄谷尚士
桜井宏之
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日商日產化學工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

一種液晶配向處理劑，其特徵為，含有下述(A)成份及(B)成份。 A liquid crystal alignment treatment agent, which comprises the following components (A) and (B).

(A)成份：含有由具有具氮原子的結構之聚醯亞胺前驅體及聚醯亞胺所選出之至少任一種的聚合物。 (A) Ingredient: A polymer containing at least one selected from a polyimide precursor having a structure having a nitrogen atom and a polyimide.

(B)成份：含有由具有脲結構或硫脲結構的聚醯亞胺前驅體及聚醯亞胺所選出之至少任一種的聚合物。 (B) Ingredient: A polymer containing at least one selected from a polyimide precursor having a urea structure or a thiourea structure and a polyimide.

Description

液晶配向處理劑及使用其之液晶顯示元件 Liquid crystal alignment treatment agent and liquid crystal display element using the same

本發明為有關液晶顯示元件的製造中所使用的液晶配向處理劑、由此液晶配向處理劑所得之液晶配向膜及使用此液晶配向膜所得之液晶顯示元件之發明。 The present invention relates to a liquid crystal alignment treatment agent used in the manufacture of a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element obtained by using the liquid crystal alignment film.

近年來，液晶顯示元件伴隨大畫面的液晶電視或高精密度之可攜帶用途(數位相機或携帶電話的顯示部份)而廣泛地實用化，故與以往相比較時，所使用的基板會形成大型化、基板段差的凹凸也會增大。於此種狀況下，顯示特性之部份，對於大型基板或段差，則尋求一種可形成均勻塗膜之液晶配向膜。該液晶配向膜的製作步驟中，將作為聚醯亞胺前驅體的聚醯胺酸或溶劑可溶性聚醯亞胺(亦稱為可溶性聚醯亞胺)的液晶配向處理劑(亦稱為塗佈溶液)塗佈於基板之情形，於工業上一般多進行凸版印刷法或噴霧塗佈法等。此時，塗佈溶液之溶劑中，除對樹脂具有優良溶解性的溶劑(亦稱為良溶劑)之N-甲基-2-吡咯啶酮或γ-丁內酯等以外，為提高液晶配向膜的塗膜均勻性之目的，亦有混合樹脂之溶解性較低之溶劑 (亦稱為貧溶劑)的丁基溶纖劑(cellosolve)等(例如專利文獻1)。 In recent years, liquid crystal display elements have been widely put into practical use with large-screen liquid crystal televisions or high-precision portable applications (display portions of digital cameras or mobile phones). Therefore, compared with the past, the substrates used are formed. Enlargement and unevenness of substrate steps also increase. Under such conditions, a part of the display characteristics, for a large substrate or a step, seeks a liquid crystal alignment film that can form a uniform coating film. In the manufacturing step of the liquid crystal alignment film, a liquid crystal alignment treatment agent (also referred to as a coating) of a polyamic acid or a solvent-soluble polyimide (also called a soluble polyimide) as a polyimide precursor is used. When a solution is applied to a substrate, a letterpress printing method or a spray coating method is generally used in the industry. At this time, among the solvents of the coating solution, in addition to N-methyl-2-pyrrolidone or γ-butyrolactone, which is a solvent (also referred to as a good solvent) having excellent solubility in the resin, in order to improve the alignment of the liquid crystal For the purpose of film uniformity of the film, there are also solvents with low solubility for mixed resins (Also referred to as lean solvent) butyl cellosolve and the like (for example, Patent Document 1).

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

[專利文獻1]特開平2-37324號公報 [Patent Document 1] Japanese Patent Application Laid-Open No. 2-37324

液晶配向膜中，於控制液晶配向狀態(亦稱為液晶配向性)的同時，對於液晶顯示元件中之信賴性或殘影特性等電氣特性而言，亦尋求其機能之提升。對於此點，使用具有液晶配向性之特性的聚醯胺酸或可溶性聚醯亞胺的聚合物，與具有電氣特性的聚合物混合所得之液晶配向處理劑之方式，為被使用作為提高前述特性之方法。 In the liquid crystal alignment film, while controlling the liquid crystal alignment state (also referred to as liquid crystal alignment), it is also seeking to improve its functions for electrical properties such as reliability or afterimage characteristics in liquid crystal display elements. In this regard, a method of using a liquid crystal alignment treatment agent obtained by mixing a polymer of polyamic acid or soluble polyimide having characteristics of liquid crystal alignment with a polymer having electrical characteristics is used to improve the aforementioned characteristics. Method.

但是，該些聚合物中，因聚合物之溶劑溶解性不同、聚合物之極性不同等情形極多。伴隨此點，含有該些聚合物之液晶配向處理劑中，於保管液晶配向處理劑之期間，聚合物成份常容易析出。如此，若聚合物成份發生析出現象時，於液晶配向處理劑塗佈於基板時，液晶配向膜的塗膜均勻性會有降低之傾向。即，受到析出聚合物成份之影響，會產生凹陷或沙孔等，而於作為液晶顯示元件之際，該部份將形成顯示上之缺陷。又，即使具有提高液晶配向處理劑的保存安定性之優點，但於液晶配向處理 劑塗佈於基板上之際，基板上也會產生聚合物成份凝聚(亦稱為白化‧凝聚)之情形。引起該白化‧凝聚之情形時，與前述說明相同般，會降低液晶配向膜之塗膜均勻性，而未能得到均勻的塗膜性，於液晶顯示元件中也為顯示上之缺陷。 However, there are many cases where these polymers have different solvent solubility and different polarities of the polymers. With this, in the liquid crystal alignment treatment agent containing these polymers, polymer components often precipitate easily during storage of the liquid crystal alignment treatment agent. In this way, if a polymer component is precipitated, when the liquid crystal alignment treatment agent is applied to a substrate, the uniformity of the coating film of the liquid crystal alignment film tends to decrease. That is, under the influence of the precipitated polymer component, depressions, sand holes, etc. may be generated, and when used as a liquid crystal display element, this part will cause display defects. In addition, even if it has the advantage of improving the storage stability of the liquid crystal alignment treatment agent, When the agent is coated on the substrate, the polymer component may also agglomerate (also known as whitening and agglomeration) on the substrate. In the case of causing such whitening and agglomeration, the uniformity of the coating film of the liquid crystal alignment film will be reduced as in the foregoing description, and uniform coating film properties will not be obtained. This is also a display defect in the liquid crystal display element.

近年來，使用光線照射量極多之背光源的液晶顯示元件，例如，汽車導航系統或大型電視，多為長時間暴露於高溫及光線照射環境下使用，或放置之情形。故即使在該些嚴苛條件下，關於液晶顯示元件的電氣特性之一的電壓保持率，也被要求具有高度之安定性。即，電壓保持率若受到背光源產生之光照射而降低時，將容易發生液晶顯示元件的顯示缺陷之一的殘影缺陷(亦稱為線性殘影)，而無法製得具有高信賴性的液晶顯示元件。因此，液晶配向膜，被尋求一種除初期特性需為良好以外，例如，長時間暴露於光線照射之後，電壓保持率也不容易降低之特性。 In recent years, a liquid crystal display element using a backlight source with a large amount of light exposure, such as a car navigation system or a large television, is mostly used or placed under a long-term exposure to high temperature and light exposure. Therefore, even under these severe conditions, a high voltage stability is required for one of the electrical characteristics of the liquid crystal display element. That is, if the voltage holding ratio is reduced by the light generated by the backlight, an afterimage defect (also referred to as a linear afterimage), which is one of display defects of a liquid crystal display element, is likely to occur, and a highly reliable Liquid crystal display element. Therefore, in addition to the initial characteristics, the liquid crystal alignment film is required to have good characteristics. For example, after being exposed to light for a long time, the voltage holding ratio is not easily reduced.

因此，本發明為，提供兼備上述特性的液晶配向處理劑為目的。即，本發明之目的為，提供一種含有相異的2種類以上之聚合物的液晶配向處理劑，其為具有優良保存安定性之液晶配向處理劑，且，於液晶配向處理劑塗佈於基板上之際，可抑制聚合物成份的白化‧凝聚現象，而可提供具有優良塗膜均勻性的液晶配向膜為目的。此外，並提供一種除具有良好初期特性以外，即使長時間暴露於光線照射之後，也可以抑制電壓保持率之下降的液 晶配向膜為目的。 Therefore, this invention aims at providing the liquid-crystal aligning agent which has the said characteristic. That is, an object of the present invention is to provide a liquid crystal alignment treatment agent containing two or more different polymers, which is a liquid crystal alignment treatment agent having excellent storage stability, and wherein the liquid crystal alignment treatment agent is coated on a substrate. In this case, the purpose is to provide a liquid crystal alignment film with excellent coating film uniformity while suppressing whitening and aggregation of polymer components. In addition, in addition to having good initial characteristics, it is possible to suppress a drop in voltage holding ratio even after prolonged exposure to light. Crystal alignment film for the purpose.

又，本發明為以提供一種具有前述液晶配向膜的液晶顯示元件為目的。 Moreover, this invention aims at providing the liquid crystal display element which has the said liquid crystal alignment film.

此外，本發明以提供一種可提供前述液晶配向膜的液晶配向處理劑為目的。 Moreover, this invention aims at providing the liquid-crystal aligning agent which can provide the said liquid-crystal alignment film.

本發明者們，進行深入研究結果，發現具有具特定結構的2個聚合物之液晶配向處理劑，就達成上述目的之觀點極為有效，進而完成本發明。 As a result of intensive research, the present inventors have found that a liquid crystal alignment treatment agent having two polymers having a specific structure is extremely effective in achieving the above-mentioned object, and completed the present invention.

即，本發明為具有以下主要特徵者。 That is, the present invention has the following main features.

(1)含有下述(A)成份及(B)成份之液晶配向處理劑。 (1) A liquid crystal alignment treatment agent containing the following components (A) and (B).

(A)成份：含有由具有具氮原子的結構之聚醯亞胺前驅體及聚醯亞胺所選出之至少任一種的聚合物。 (A) Ingredient: A polymer containing at least one selected from a polyimide precursor having a structure having a nitrogen atom and a polyimide.

(B)成份：含有由具有下述式〔2〕所示結構的聚醯亞胺前驅體及聚醯亞胺所選出之至少任一種的聚合物。 (B) Ingredient: A polymer containing at least one selected from a polyfluorene imide precursor having a structure represented by the following formula [2] and a polyfluorene.

(式〔2〕中，Y1及Y7各自獨立表示由單鍵、碳數1~10之伸烷基、-O-、-N(R1)-(R1表示氫原子或碳數1~3之伸烷基)、-CON(R2)-(R2表示氫原子或碳數1 ~3之伸烷基)、-N(R3)CO-(R3表示氫原子或碳數1~3之伸烷基)、-CH2O-、-COO-及-OCO-所選出之至少1種的有機基，Y2及Y6各自獨立表示碳數1~10之伸烷基，Y3及Y5各自獨立表示氫原子或碳數1~10之伸烷基，Y4表示氧原子或硫原子)。 (In formula [2], Y 1 and Y 7 each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R 1 )-(R 1 represents a hydrogen atom or carbon number 1 ~ 3 alkylene), -CON (R 2 )-(R 2 represents a hydrogen atom or carbon number of 1 to 3), -N (R 3 ) CO- (R 3 represents a hydrogen atom or carbon number At least one selected from the group consisting of 1 to 3 alkyl groups), -CH 2 O-, -COO-, and -OCO-, and Y 2 and Y 6 each independently represent an alkylene group having 1 to 10 carbon atoms, Y 3 and Y 5 each independently represent a hydrogen atom or an alkylene group having 1 to 10 carbon atoms, and Y 4 represents an oxygen atom or a sulfur atom).

(2)上述(1)所記載之液晶配向處理劑，前述(A)成份中之具有氮原子的結構，為由下述式〔1a〕~式〔1c〕所示結構所選出之至少1種的結構。 (2) The liquid crystal alignment treatment agent described in (1) above, the structure having a nitrogen atom in the component (A) is at least one selected from the structures shown by the following formulas [1a] to [1c] Structure.

(式〔1a〕中，X1表示苯環或含氮芳香族雜環，X2表示氫原子或被碳數1~12的脂肪族基所取代之二取代胺基，式〔1b〕中，X3及X7各自獨立表示具有6~15個碳原子，且具有1~2個苯環之芳香族基，X4及X6各自獨立表示氫原子或碳數1~5之伸烷基，X5表示碳數2~5之伸烷基或聯苯基，m表示0或1之整數，式〔1c〕中，X8及X10各自獨立表示由下述式〔1c-a〕及式〔1c-b〕所示結構所選出之至少1種的結構，X9表示碳數1~5之伸烷基或苯環)。 (In the formula [1a], X 1 represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring, X 2 represents a hydrogen atom or a disubstituted amine group substituted with an aliphatic group having 1 to 12 carbon atoms. In the formula [1b], X 3 and X 7 each independently represent an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings, X 4 and X 6 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms, X 5 represents an alkylene group or a biphenyl group having 2 to 5 carbon atoms, m represents an integer of 0 or 1, and in the formula [1c], X 8 and X 10 each independently represent the following formula [1c-a] and formula the configuration shown in [1c-b] at least one of the selected structure, X 9 represents a benzene ring carbon atoms or alkylene of 1 to 5).

(3)上述(1)或上述(2)所記載之液晶配向處理劑，前述(A)成份之聚合物為，使用下述式〔1-1〕所示二胺化合物作為原料的一部份而製得之聚合物。 (3) The liquid crystal alignment treatment agent according to the above (1) or (2), the polymer of the component (A) is a part of a raw material using a diamine compound represented by the following formula [1-1] And the polymer made.

(式〔1-1〕中，XA表示具有由前述式〔1a〕~式〔1c〕所示結構所選出之至少1種的結構的碳數5~50的有機基，A1及A2各自獨立表示氫原子或碳數1~5之伸烷基)。 (In the formula [1-1], X A represents an organic group having 5 to 50 carbon atoms having at least one structure selected from the structures represented by the aforementioned formulas [1a] to [1c], A 1 and A 2 Each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms).

(4)上述(3)所記載之液晶配向處理劑，前述二胺化合物，為使用下述式〔1a-1〕~式〔1c-1〕所示二胺化合物作為原料的一部份而製得之聚合物。 (4) The liquid crystal alignment treatment agent described in (3) above, the diamine compound is prepared by using a diamine compound represented by the following formulae [1a-1] to [1c-1] as a part of a raw material. Got the polymer.

(式〔1a-1〕中，X1表示苯環或含氮芳香族雜環，X2 表示氫原子或被碳數1~12的脂肪族基所取代之二取代胺基，式〔1b-1〕中，X3及X7各自獨立表示具有6~15個碳原子，且具有1~2個苯環之芳香族基，X4及X6各自獨立表示氫原子或碳數1~5之伸烷基，X5表示碳數2~5之伸烷基或聯苯基，m表示0或1之整數，式〔1c-1〕中，X8及X10各自獨立表示由前述式〔1c-a〕及式〔1c-b〕所示結構所選出之至少1種的結構，X9表示碳數1~5之伸烷基或苯環，式〔1a-1〕~式〔1c-1〕中，A1~A6各自獨立表示氫原子或碳數1~5之伸烷基)。 (In the formula [1a-1], X 1 represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring, X 2 represents a hydrogen atom or a disubstituted amine group substituted with an aliphatic group having 1 to 12 carbon atoms, and the formula [1b- 1], X 3 and X 7 each independently represent an aromatic group having 6 to 15 carbon atoms and having 1 to 2 benzene rings, and X 4 and X 6 each independently represent a hydrogen atom or a carbon number of 1 to 5 Alkyl, X 5 represents an alkyl or biphenyl group having 2 to 5 carbon atoms, and m represents an integer of 0 or 1. In the formula [1c-1], X 8 and X 10 each independently represent the formula [1c -a] and at least one selected from the structures shown in formula [1c-b], X 9 represents an alkylene or benzene ring having 1 to 5 carbon atoms, and formulas [1a-1] to [1c-1 In [], A 1 to A 6 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

(5)上述(4)所記載之液晶配向處理劑，前述二胺化合物為由下述式〔1-1a〕~式〔1-4a〕所示二胺化合物所選出之至少1種的二胺化合物。 (5) The liquid crystal alignment treatment agent according to (4), wherein the diamine compound is at least one type of diamine selected from the diamine compounds represented by the following formulas [1-1a] to [1-4a]. Compound.

(式〔1-3a〕中，R1表示氫原子或碳數1~5之伸烷基，式〔1-4a〕中，n表示1~10之整數，式〔1-1a〕~式〔1-4a〕中，A1~A8各自獨立表示氫原子或碳數1~5 之伸烷基)。 (In formula [1-3a], R 1 represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms; in formula [1-4a], n represents an integer of 1 to 10; formula [1-1a] to formula [ 1-4a], A 1 to A 8 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms).

(6)上述(1)~上述(5)之任一者所記載的液晶配向處理劑，前述(B)成份之聚合物為使用下述式〔2-1〕所示二胺化合物作為原料的一部份而製得之聚合物。 (6) The liquid crystal alignment treatment agent according to any one of the above (1) to (5), wherein the polymer of the component (B) uses a diamine compound represented by the following formula [2-1] as a raw material Partly made polymer.

(式〔2-1〕中，YA表示具有前述式〔2〕所示結構的有機基，A1及A2各自獨立表示氫原子或碳數1~5之伸烷基)。 (In the formula [2-1], Y A represents an organic group having a structure represented by the aforementioned formula [2], and A 1 and A 2 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms).

(7)上述(6)所記載之液晶配向處理劑，前述二胺化合物為使用下述式〔2a〕所示二胺化合物作為原料的一部份而製得之聚合物。 (7) The liquid crystal alignment treatment agent according to the above (6), wherein the diamine compound is a polymer prepared by using a diamine compound represented by the following formula [2a] as a part of a raw material.

(式〔2a〕中，Y1及Y7各自獨立表示由單鍵、碳數1~10之伸烷基、-O-、-N(R1)-(R1表示氫原子或碳數1~3之伸烷基)、-CON(R2)-(R2表示氫原子或碳數1~3之伸烷基)、-N(R3)CO-(R3表示氫原子或碳數1~3之伸烷基)、-CH2O-、-COO-及-OCO-所選出之至少1 種的有機基，Y2及Y6各自獨立表示碳數1~10之伸烷基，Y3及Y5各自獨立表示氫原子或碳數1~10之伸烷基，Y4表示氧原子或硫原子，A1及A2各自獨立表示氫原子或碳數1~5之伸烷基)。 (In formula [2a], Y 1 and Y 7 each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R 1 )-(R 1 represents a hydrogen atom or carbon number 1 ~ 3 alkylene), -CON (R 2 )-(R 2 represents a hydrogen atom or a carbon number of 1 to 3), -N (R 3 ) CO- (R 3 represents a hydrogen atom or a carbon number At least one selected from the group consisting of 1 to 3 alkyl groups), -CH 2 O-, -COO-, and -OCO-, and Y 2 and Y 6 each independently represent an alkylene group having 1 to 10 carbon atoms, Y 3 and Y 5 each independently represent a hydrogen atom or an alkylene group having 1 to 10 carbon atoms, Y 4 represents an oxygen atom or a sulfur atom, and A 1 and A 2 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms ).

(8)上述(7)所記載之液晶配向處理劑，前述二胺化合物為由下述式〔2-1a〕~式〔2-3a〕所示二胺化合物所選出之至少1種的二胺化合物。 (8) The liquid crystal alignment treatment agent according to (7), wherein the diamine compound is at least one type of diamine selected from the diamine compounds represented by the following formulae [2-1a] to [2-3a]. Compound.

(式〔2-1a〕~式〔2-3a〕中，A1~A6各自獨立表示氫原子或碳數1~5之伸烷基)。 (In the formulae [2-1a] to [2-3a], A 1 to A 6 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.)

(9)上述(1)~上述(8)之任一者所記載的液晶配向處理劑，前述(A)成份之聚合物及(B)成份之聚合物為，由使用下述式〔3〕所示四羧酸成份而製得之聚醯亞胺前驅體及聚醯亞胺所選出之至少1種的聚合物。 (9) The liquid crystal alignment treatment agent according to any one of (1) to (8) above, wherein the polymer of the component (A) and the polymer of the component (B) are obtained by using the following formula [3] A polyimide precursor prepared from the tetracarboxylic acid component shown and at least one polymer selected from polyimide.

(式〔3〕中，Z表示由下述式〔3a〕~式〔3k〕所示結構所選出之至少1種的結構)。 (In the formula [3], Z represents at least one structure selected from the structures represented by the following formulas [3a] to [3k]).

(式〔3a〕中，Z1~Z4表示氫原子、甲基、乙基、丙基、氯原子或苯環，其可分別為相同亦可、相異亦可，式〔3g〕中，Z5及Z6表示氫原子或甲基，其可分別為相同亦可、相異亦可)。 (In the formula [3a], Z 1 to Z 4 represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom, or a benzene ring, which may be the same as or different from each other. In the formula [3g], Z 5 and Z 6 represent a hydrogen atom or a methyl group, and they may be the same as or different from each other).

(10)上述(9)所記載之液晶配向處理劑，前述四羧酸成份為，前述式〔3〕中之Z為由前述式〔3a〕及式〔3e〕~式〔3g〕所示結構所選出之至少1種的結構的四羧酸成份。 (10) The liquid crystal alignment treatment agent according to the above (9), wherein the tetracarboxylic acid component is: Z in the formula [3] is a structure represented by the formulas [3a] and [3e] to [3g] A tetracarboxylic acid component of at least one selected structure.

(11)上述(4)~上述(10)之任一者所 記載的液晶配向處理劑，前述(A)成份之聚合物中，前述式〔1a-1〕~式〔1c-1〕所示二胺化合物，於全部的二胺成份100莫耳%中，為5莫耳%~95莫耳%。 (11) Any of the above (4) to (10) In the liquid crystal alignment treatment agent described above, in the polymer of the component (A), the diamine compound represented by the formulas [1a-1] to [1c-1] is 100 mol% of the total diamine component, which is 5 mole% to 95 mole%.

(12)上述(7)~上述(11)之任一者所記載的液晶配向處理劑，前述(B)成份之聚合物中，前述式〔2a〕所示二胺化合物，於全部的二胺成份100莫耳%中，為5莫耳%~95莫耳%。 (12) The liquid crystal alignment treatment agent according to any one of (7) to (11) above, in the polymer of the component (B), the diamine compound represented by the formula [2a] is present in all the diamines Among the 100 mol% of ingredients, it ranges from 5 mol% to 95 mol%.

(13)上述(1)~上述(12)之任一者所記載的液晶配向處理劑，前述(B)成份之聚合物，相對於前述(A)成份之聚合物100質量份，為0.5質量份~950質量份。 (13) The liquid crystal alignment treatment agent according to any one of the above (1) to (12), wherein the polymer of the component (B) is 0.5 mass based on 100 parts by mass of the polymer of the component (A). Parts ~ 950 parts by mass.

(14)上述(1)~上述(13)之任一者所記載的液晶配向處理劑，液晶配向處理劑的溶劑為，含有由N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮及γ-丁內酯所選出之至少1種的溶劑。 (14) The liquid crystal alignment treatment agent according to any one of the above (1) to (13), wherein the solvent of the liquid crystal alignment treatment agent is N-methyl-2-pyrrolidone, N-ethyl- At least one selected from 2-pyrrolidone and γ-butyrolactone.

(15)上述(1)~上述(14)之任一者所記載的液晶配向處理劑，液晶配向處理劑的溶劑為，含有由1-己醇、環己醇、1,2-乙二醇、1,2-丙二醇、丙二醇單丁醚、乙二醇單丁醚及二丙二醇二甲醚所選出之至少1種的溶劑。 (15) The liquid crystal alignment treatment agent according to any one of the above (1) to (14), wherein the solvent of the liquid crystal alignment treatment agent is 1-hexanol, cyclohexanol, and 1,2-ethylene glycol 1,2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, and dipropylene glycol dimethyl ether.

(16)上述(1)~上述(15)之任一者所記載的液晶配向處理劑，液晶配向處理劑中含有，具有環氧基、異氰酸酯基、環氧丙烷基或環碳酸酯基的交聯性化合物、具有由羥基、羥烷基或低級烷氧基烷基所成群所選 出之至少1種的取代基的交聯性化合物，及由具有聚合性不飽和鍵結的交聯性化合物所選出之至少1種的交聯性化合物。 (16) The liquid crystal alignment treatment agent according to any one of the above (1) to (15), which is contained in the liquid crystal alignment treatment agent and has an epoxy group, an isocyanate group, a propylene oxide group, or a cyclic carbonate group. Associated compounds, selected from groups consisting of hydroxy, hydroxyalkyl, or lower alkoxyalkyl At least one type of crosslinkable compound selected from the substituents, and at least one type of crosslinkable compound selected from the group of crosslinkable compounds having a polymerizable unsaturated bond.

(17)一種液晶配向膜，上述(1)~上述(16)之任一者所記載的液晶配向處理劑所製得。 (17) A liquid crystal alignment film produced by the liquid crystal alignment treatment agent according to any one of (1) to (16) above.

(18)一種液晶配向膜，其為使用上述(1)~上述(16)之任一者所記載的液晶配向處理劑，以噴墨法而得。 (18) A liquid crystal alignment film obtained by using an inkjet method using the liquid crystal alignment treatment agent according to any one of (1) to (16) above.

(19)一種液晶顯示元件，其具有上述(17)或上述(18)所記載之液晶配向膜。 (19) A liquid crystal display element comprising the liquid crystal alignment film according to the above (17) or (18).

本發明之含有2種類的由具有特定結構之聚醯亞胺前驅體或聚醯亞胺所選出之至少1種的聚合物之液晶配向處理劑，其為具有優良保存安定性之液晶配向處理劑，且，於液晶配向處理劑塗佈於基板上之際，可抑制聚合物成份的白化‧凝聚現象，而可得到具有優良塗膜均勻性之液晶配向膜。此外，為一種除具有良好初期特性以外，即使長時間暴露於光線照射之後，也可以抑制電壓保持率降低的液晶配向膜。因此，具有由本發明之液晶配向處理劑所得之液晶配向膜的液晶顯示元件，為具有優良信賴性者，而適合被使用於大畫面且高精密的液晶電視，或中小型汽車導航系統或智慧型手機等。 The liquid crystal alignment treatment agent of the present invention containing two types of polyimide precursors having a specific structure or at least one polymer selected from polyimide, which is a liquid crystal alignment treatment agent with excellent storage stability In addition, when the liquid crystal alignment treatment agent is coated on the substrate, the whitening and agglomeration of the polymer component can be suppressed, and a liquid crystal alignment film having excellent uniformity of the coating film can be obtained. In addition, it is a liquid crystal alignment film capable of suppressing a decrease in voltage retention even after being exposed to light for a long time, in addition to having good initial characteristics. Therefore, a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is a person with excellent reliability, and is suitable for being used in a large-screen and high-precision liquid crystal television, or a small and medium-sized car navigation system or a smart type. Mobile phone, etc.

〔實施發明之形態〕 [Form of Implementing Invention]

以下，將對本發明作詳細之說明。 Hereinafter, the present invention will be described in detail.

本發明為，一種含有下述(A)成份及(B)成份之液晶配向處理劑、使用該該液晶配向處理劑所得之液晶配向膜、及，具有該液晶配向膜之液晶顯示元件。 The present invention is a liquid crystal alignment treatment agent containing the following components (A) and (B), a liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent, and a liquid crystal display element having the liquid crystal alignment film.

(A)成份：含有由具有具氮原子的結構之聚醯亞胺前驅體及聚醯亞胺所選出之至少任一種的聚合物(亦稱為特定聚合物(A))。 (A) Ingredient: A polymer (also referred to as a specific polymer (A)) containing at least one selected from a polyimide precursor having a structure having a nitrogen atom and a polyimide.

(B)成份：含有由具有下述式〔2〕所示結構(亦稱為特定結構(2))的聚醯亞胺前驅體及聚醯亞胺所選出之至少任一種的聚合物(亦稱為特定聚合物(B))。 (B) Ingredient: A polymer containing at least one selected from a polyimide precursor having a structure represented by the following formula [2] (also referred to as a specific structure (2)) and a polyimide (also (Referred to as a specific polymer (B)).

(式〔2〕中，Y1及Y7各自獨立表示由單鍵、碳數1~10之伸烷基、-O-、-N(R1)-(R1表示氫原子或碳數1~3之伸烷基)、-CON(R2)-(R2表示氫原子或碳數1~3之伸烷基)、-N(R3)CO-(R3表示氫原子或碳數1~3之伸烷基)、-CH2O-、-COO-及-OCO-所選出之至少1種的有機基，Y2及Y6各自獨立表示碳數1~10之伸烷基，Y3及Y5各自獨立表示氫原子或碳數1~10之伸烷基，Y4表示氧原子或硫原子)。 (In formula [2], Y 1 and Y 7 each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R 1 )-(R 1 represents a hydrogen atom or carbon number 1 ~ 3 alkylene), -CON (R 2 )-(R 2 represents a hydrogen atom or a carbon number of 1 to 3), -N (R 3 ) CO- (R 3 represents a hydrogen atom or a carbon number At least one selected from the group consisting of 1 to 3 alkyl groups), -CH 2 O-, -COO-, and -OCO-, and Y 2 and Y 6 each independently represent an alkylene group having 1 to 10 carbon atoms, Y 3 and Y 5 each independently represent a hydrogen atom or an alkylene group having 1 to 10 carbon atoms, and Y 4 represents an oxygen atom or a sulfur atom).

本發明之液晶配向處理劑所製得液晶配向 膜，其可解決本發明問題之理由，仍未完全明瞭，但應為下述說明內容。 Liquid crystal alignment prepared by liquid crystal alignment treatment agent of the present invention The reason why the film can solve the problems of the present invention is not fully understood, but it should be the following description.

即，特定聚合物(A)中所含之具有氮原子的結構中的氮原子與特定聚合物(B)中的羧基(COOH基)相互作用，與特定聚合物(B)中前述式〔2〕中的氮原子與特定聚合物(A)中的羧基相互作用結果，使特定聚合物(A)與特定聚合物(B)相溶，而可抑制於保存液晶配向處理劑期間，該些聚合物成份之析出及塗佈於基板上之際產生之白化‧凝聚現象。 That is, a nitrogen atom in a structure having a nitrogen atom contained in the specific polymer (A) interacts with a carboxyl group (COOH group) in the specific polymer (B), and interacts with the aforementioned formula [2] in the specific polymer (B). As a result of the interaction between the nitrogen atom in [] and the carboxyl group in the specific polymer (A), the specific polymer (A) and the specific polymer (B) are compatible, and the polymerization can be suppressed during the storage of the liquid crystal alignment treatment agent. The phenomenon of whitening and agglomeration that occurs when the components are deposited and coated on the substrate.

又，特定聚合物(A)中，具有氮原子的結構，推測可捕集造成電壓保持率降低要因之離子性雜質成份。即，液晶顯示元件，可捕集因長時間暴露於光線照射所發生的離子性雜質，因此同時也可以抑制電壓保持率之下降。 In addition, the specific polymer (A) has a structure having a nitrogen atom, and it is estimated that an ionic impurity component that causes a decrease in the voltage holding ratio can be trapped. That is, the liquid crystal display device can trap ionic impurities generated by long-term exposure to light irradiation, and can also suppress a decrease in voltage holding ratio at the same time.

由以上各點得知，本發明之含有2種類的由具有特定結構之聚醯亞胺前驅體或聚醯亞胺所選出之至少1種的聚合物之液晶配向處理劑，其為具有優良保存安定性之液晶配向處理劑，且，於液晶配向處理劑塗佈於基板上之際，可抑制聚合物成份的白化‧凝聚現象，而可得到具有優良塗膜均勻性之液晶配向膜。此外，亦為一種除具有良好初期特性以外，即使長時間暴露於光線照射之後，也可以抑制電壓保持率之下降的液晶配向膜。 From the above points, it is known that the liquid crystal alignment treatment agent of the present invention containing two types of polymers selected from at least one type of polyimide precursor or polyimide having a specific structure is excellent in preservation. A stable liquid crystal alignment treatment agent. When the liquid crystal alignment treatment agent is coated on a substrate, the whitening and agglomeration of polymer components can be suppressed, and a liquid crystal alignment film having excellent uniformity of the coating film can be obtained. In addition, it is a liquid crystal alignment film that can suppress a decrease in voltage holding ratio even after being exposed to light for a long time, in addition to having good initial characteristics.

<具有氮原子的結構> <Structure with nitrogen atom>

本發明之特定聚合物(A)為，含有由具有具氮原子的結構之聚醯亞胺前驅體及聚醯亞胺所選出之至少任一種的聚合物。 The specific polymer (A) of the present invention is a polymer containing at least one selected from a polyimide precursor having a structure having a nitrogen atom and a polyimide.

具有氮原子的結構之具體性結構，可列舉如，下述式〔1a〕~式〔1c〕所示結構等。 Specific examples of the structure having a nitrogen atom include a structure represented by the following formulas [1a] to [1c].

式〔1a〕中，X1表示苯環或含氮芳香族雜環。 In the formula [1a], X 1 represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring.

式〔1a〕中，X2表示氫原子或被碳數1~12之脂肪族基所取代的二取代胺基。 In the formula [1a], X 2 represents a hydrogen atom or a di-substituted amine group substituted with an aliphatic group having 1 to 12 carbon atoms.

又，式〔1a〕中，X2為氫原子之情形，X1表示含氮芳香族雜環，X2為被碳數1~12之脂肪族基所取代的二取代胺基之情形，X1表示苯環。 In the formula [1a], when X 2 is a hydrogen atom, X 1 represents a nitrogen-containing aromatic heterocyclic ring, X 2 is a disubstituted amino group substituted with an aliphatic group having 1 to 12 carbon atoms, X 1 represents a benzene ring.

式〔1b〕中，X3及X7各自獨立表示具有6~15個碳原子，且具有1~2個苯環的芳香族基。 In the formula [1b], X 3 and X 7 each independently represent an aromatic group having 6 to 15 carbon atoms and having 1 to 2 benzene rings.

式〔1b〕中，X4及X6各自獨立表示氫原子或碳數1~5之伸烷基。 In the formula [1b], X 4 and X 6 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

式〔1b〕中，X5表示碳數2~5之伸烷基或聯苯基。 In the formula [1b], X 5 represents an alkylene group or a biphenyl group having 2 to 5 carbon atoms.

式〔1b〕中，m表示0或1之整數。 In Formula [1b], m represents an integer of 0 or 1.

式〔1c〕中，X8及X10各自獨立表示由下述式〔1c-a〕及式〔1c-b〕所示結構所選出之至少1種的結構。 In the formula [1c], X 8 and X 10 each independently represent at least one structure selected from the structures represented by the following formulas [1c-a] and [1c-b].

式〔1c〕中，X9表示碳數1~5之伸烷基或苯環。 In the formula [1c], X 9 represents an alkylene group or a benzene ring having 1 to 5 carbon atoms.

<特定結構(2)> <Specific Structure (2)>

本發明之特定聚合物(B)為，含有由具有下述式〔2〕所示特定結構(2)的聚醯亞胺前驅體及聚醯亞胺所選出之至少任一種之聚合物。 The specific polymer (B) of the present invention is a polymer containing at least one selected from a polyfluorene imide precursor having a specific structure (2) represented by the following formula [2] and a polyfluorene imine.

式〔2〕中，Y1及Y7各自獨立表示由單鍵、碳數1~10之伸烷基、-O-、-S-、-N(R1)-(R1表示氫原子或碳數1~3之伸烷基)、-CON(R2)-(R2表示氫原子或碳數1~3之伸烷基)、-N(R3)CO-(R3表示氫原子或碳數1~3之伸烷基)、-CH2O-、-COO-及-OCO-所選出之至少1種的有機基。其中，又以單鍵、-O-、-S-、 -OCO-或-COO-為佳。更佳者，就液晶配向性與液晶配向膜之膜硬度等觀點，可例如，單鍵、-O-或-S-。 In Formula [2], Y 1 and Y 7 each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -S-, -N (R 1 )-(R 1 represents a hydrogen atom or C1-C3 alkylene), -CON (R 2 )-(R 2 represents a hydrogen atom or C1-C3 alkylene), -N (R 3 ) CO- (R 3 represents a hydrogen atom Or an alkylene group having 1 to 3 carbon atoms), -CH 2 O-, -COO-, and -OCO- selected from at least one organic group. Among them, a single bond, -O-, -S-, -OCO-, or -COO- is more preferable. More preferably, from the viewpoints of liquid crystal alignment and film hardness of the liquid crystal alignment film, for example, a single bond, -O-, or -S- can be used.

式〔2〕中，Y2及Y6各自獨立表示碳數1~10之伸烷基。其中，又以碳數1~3之伸烷基為佳，其結構可為直鏈或支鏈之任一者皆可。具體而言，就液晶配向性與液晶配向膜之膜硬度等觀點，以具有自由迴轉部位，且立體障礙較小的結構之伸甲基(-CH2-)、伸乙基(-CH2CH2-)、伸丙基(-(CH2)3-)或異丙基(-C(CH2)2-)為佳。 In the formula [2], Y 2 and Y 6 each independently represent an alkylene group having 1 to 10 carbon atoms. Among them, an alkylene group having 1 to 3 carbon atoms is preferable, and the structure may be either straight chain or branched chain. Specifically, from the viewpoints of liquid crystal alignment and film hardness of the liquid crystal alignment film, from the viewpoints of liquid crystal alignment film and free-rotation part, and a structure with relatively small steric hindrance, the methyl group (-CH 2- ) and the ethyl group (-CH 2 CH 2- ), propyl (-(CH 2 ) 3- ) or isopropyl (-C (CH 2 ) 2- ) are preferred.

式〔2〕中，Y3及Y5各自獨立表示氫原子或碳數1~10之烷基。其中，又以氫原子或碳數1~3之烷基為佳。特佳為氫原子。 In the formula [2], Y 3 and Y 5 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. Particularly preferred is a hydrogen atom.

式〔2〕中，Y4表示氧原子或硫原子。其中，就液晶配向膜之膜硬度之觀點，又以氧原子為佳。 In the formula [2], Y 4 represents an oxygen atom or a sulfur atom. Among them, from the viewpoint of the film hardness of the liquid crystal alignment film, an oxygen atom is preferred.

<特定聚合物(A)‧特定聚合物(B)> <Specific polymer (A) ‧Specific polymer (B)>

本發明之特定聚合物(A)及特定聚合物(B)，為由聚醯亞胺前驅體及聚醯亞胺(亦統稱為聚醯亞胺系聚合物)所選出之至少1種的聚合物。其中，本發明之聚醯亞胺系聚合物，又以由二胺成份與四羧酸成份反應所得之聚醯亞胺前驅體或聚醯亞胺為佳。 The specific polymer (A) and the specific polymer (B) of the present invention are polymerizations of at least one selected from a polyimide precursor and a polyimide (also collectively referred to as a polyimide-based polymer). Thing. Among them, the polyfluorene imide polymer of the present invention is preferably a polyfluorene imide precursor or a polyfluorene imide obtained by reacting a diamine component with a tetracarboxylic acid component.

聚醯亞胺前驅體為，如下述式〔A〕所示結構。 The polyfluorene imide precursor has a structure represented by the following formula [A].

(式〔A〕中，R1為4價之有機基，R2為2價之有機基，A1及A2各自獨立表示氫原子或碳數1~5之伸烷基，A3及A4各自獨立表示氫原子、碳數1~5之伸烷基或乙醯基，n表示正整數)。 (In the formula [A], R 1 is a tetravalent organic group, R 2 is a divalent organic group, A 1 and A 2 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms, A 3 and A 4 each independently represents a hydrogen atom, an alkylene group having 1 to 5 carbon atoms, or an ethenyl group, and n represents a positive integer).

前述二胺成份，例如，分子內具有2個一級或二級之胺基的二胺化合物等。 The diamine component is, for example, a diamine compound having two primary or secondary amine groups in a molecule.

又，前述四羧酸成份，可列舉如，四羧酸化合物、四羧酸二酐、四羧酸二鹵化物化合物、四羧酸二烷酯化合物或四羧酸二烷酯二鹵化物化合物等。 Examples of the tetracarboxylic acid component include a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, and a tetracarboxylic acid dialkyl ester dihalide compound. .

為製得式〔A〕中之A1及A2為氫原子的聚醯胺酸時，前述分子內具有2個一級或二級之胺基的二胺化合物，與四羧酸化合物或四羧酸酐進行反應而可製得。 In order to obtain a polyamidic acid in which A 1 and A 2 in formula [A] are hydrogen atoms, the aforementioned diamine compound having two primary or secondary amine groups in the molecule, and a tetracarboxylic acid compound or tetracarboxylic acid It can be prepared by reacting acid anhydride.

為製得式〔A〕中之A1及A2為碳數1~5之伸烷基的聚醯胺酸烷酯時，可使前述二胺化合物，與四羧酸二鹵化物化合物、四羧酸二烷酯化合物或四羧酸二烷酯二鹵化物化合物進行反應而可製得。又，亦可於前述方法所製得之聚醯胺酸中，導入式〔A〕所示A1及A2之碳數1~5的伸烷基。 In order to obtain a polyalkylamino alkyl alkanoate in which A 1 and A 2 in the formula [A] are alkylene groups having 1 to 5 carbon atoms, the aforementioned diamine compound, a tetracarboxylic dihalide compound, and A dialkyl carboxylic acid compound or a dicarboxylic acid dialkyl dihalide compound can be prepared by reacting. Further, an alkylene group having 1 to 5 carbon atoms of A 1 and A 2 represented by the formula [A] may be introduced into the polyamic acid prepared by the method described above.

本發明之特定聚合物(A)為，具有具氮原子的結構之聚合物。其中，又以前述式〔1a〕~式〔1c〕所 示結構為佳。 The specific polymer (A) of the present invention is a polymer having a structure having a nitrogen atom. Among them, according to the aforementioned formulas [1a] to [1c] The structure is better.

將本發明之具有氮原子的結構導入特定聚合物(A)中之方法，並未有特別之限定，又以將具有前述式〔1a〕~式〔1c〕所示結構的二胺化合物作為原料的一部份予以使用者為佳。 The method for introducing the structure having a nitrogen atom of the present invention into a specific polymer (A) is not particularly limited, and a diamine compound having a structure represented by the aforementioned formulas [1a] to [1c] is used as a raw material. Part of it is better for users.

具體而言，以使用下述式〔1-1〕所示二胺化合物(亦稱為特定二胺化合物(1))為佳。 Specifically, it is preferable to use a diamine compound (also referred to as a specific diamine compound (1)) represented by the following formula [1-1].

式〔1-1〕中，XA表示具有由前述式〔1a〕~式〔1c〕所示結構所選出之至少1種的結構的有機基。 In the formula [1-1], X A represents an organic group having at least one structure selected from the structures represented by the aforementioned formulas [1a] to [1c].

式〔1-1〕中，A1及A2各自獨立表示氫原子或碳數1~5之伸烷基。 In Formula [1-1], A 1 and A 2 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

更具體而言，以使用下述式〔1a-1〕~式〔1c-1〕所示二胺化合物為佳。 More specifically, it is preferable to use a diamine compound represented by the following formula [1a-1] to [1c-1].

式〔1a-1〕中，X1表示苯環或含氮芳香族雜環。 In the formula [1a-1], X 1 represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring.

式〔1a-1〕中，X2表示氫原子或被碳數1~12 之脂肪族基所取代的二取代胺基。 In the formula [1a-1], X 2 represents a hydrogen atom or a disubstituted amine group substituted with an aliphatic group having 1 to 12 carbon atoms.

又，式〔1a-1〕中，X2為氫原子之情形，X1表示含氮芳香族雜環，X2為被碳數1~12之脂肪族基所取代的二取代胺基之情形，X1表示苯環。 In the formula [1a-1], when X 2 is a hydrogen atom, X 1 represents a nitrogen-containing aromatic heterocyclic ring, and X 2 is a disubstituted amino group substituted with an aliphatic group having 1 to 12 carbon atoms. X 1 represents a benzene ring.

式〔1b-1〕中，X3及X7各自獨立表示具有6~15個碳原子，且具有1~2個苯環的芳香族基。 In the formula [1b-1], X 3 and X 7 each independently represent an aromatic group having 6 to 15 carbon atoms and having 1 to 2 benzene rings.

式〔1b-1〕中，X4及X6各自獨立表示氫原子或碳數1~5之伸烷基。 In the formula [1b-1], X 4 and X 6 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

式〔1b-1〕中，X5表示碳數2~5之伸烷基或聯苯基。 In the formula [1b-1], X 5 represents an alkylene group or a biphenyl group having 2 to 5 carbon atoms.

式〔1b-1〕中，m表示0或1之整數。 In the formula [1b-1], m represents an integer of 0 or 1.

式〔1c-1〕中，X8及X10各自獨立表示由下述式〔1c-a〕及式〔1c-b〕所示結構所選出之至少1種的結構。 In the formula [1c-1], X 8 and X 10 each independently represent at least one structure selected from the structures shown by the following formula [1c-a] and formula [1c-b].

式〔1c-1〕中，X9表示碳數1~5之伸烷基或苯環。 In the formula [1c-1], X 9 represents an alkylene group or a benzene ring having 1 to 5 carbon atoms.

本發明之特定二胺化合物(1)之具體的二胺化合物，可列舉如，下述式〔1-1a〕~式〔1-4a〕所示二胺化合物等。 Specific examples of the diamine compound of the specific diamine compound (1) of the present invention include diamine compounds represented by the following formulas [1-1a] to [1-4a].

式〔1-3a〕中，R1表示氫原子或碳數1~5之伸烷基。 In the formula [1-3a], R 1 represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

式〔1-4a〕中，n表示1~10之整數。 In Formula [1-4a], n represents an integer of 1-10.

式〔1-1a〕~式〔1-4a〕中，A1~A8各自獨立表示氫原子或碳數1~5之伸烷基。 In the formulae [1-1a] to [1-4a], A 1 to A 8 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

其中，又以使用前述式〔1-3a〕或式〔1-4a〕所示二胺化合物為佳。 Among them, it is more preferable to use the diamine compound represented by the formula [1-3a] or the formula [1-4a].

本發明之特定聚合物(A)中之特定二胺化合物(1)，於全部的二胺成份100莫耳%中，以1莫耳%~95莫耳%為佳。其中，又以5莫耳%~95莫耳%為佳。更佳者為20莫耳%~80莫耳%。 The specific diamine compound (1) in the specific polymer (A) of the present invention is preferably 1 mol% to 95 mol% out of 100 mol% of the total diamine component. Among them, 5 mole% to 95 mole% is preferred. More preferred is 20 mol% to 80 mol%.

本發明之特定二胺化合物(1)，可依本發明之特定聚合物(A)對於溶劑之溶解性或液晶配向處理劑之塗佈性、作為液晶配向膜之情形中的液晶配向性、電壓保持率、蓄積電荷等之特性，將1種類或2種類以上混合 使用。 The specific diamine compound (1) of the present invention may be based on the solubility of the specific polymer (A) of the present invention in a solvent or the coatability of a liquid crystal alignment treatment agent, the liquid crystal alignment property and the voltage in the case of a liquid crystal alignment film Characteristics of retention rate, accumulated charge, etc., mix 1 type or more use.

本發明之特定聚合物(B)，為具有特定結構(2)之聚合物。 The specific polymer (B) of the present invention is a polymer having a specific structure (2).

將本發明之特定結構(2)導入特定聚合物(B)中之方法，並未有特別之限定，又以使用將具有特定結構(2)的二胺化合物作為二胺成份使用者為佳。特佳為使用具有前述式〔2〕所示結構的二胺化合物。 The method for introducing the specific structure (2) of the present invention into the specific polymer (B) is not particularly limited, and it is preferable to use a diamine compound having the specific structure (2) as a diamine component user. It is particularly preferable to use a diamine compound having a structure represented by the aforementioned formula [2].

具體而言，又以使用下述式〔2-1〕所示二胺化合物(亦稱為特定二胺化合物(2))為佳。 Specifically, it is also preferable to use a diamine compound (also referred to as a specific diamine compound (2)) represented by the following formula [2-1].

式〔2-1〕中，YA表示具有前述式〔2〕所示結構之有機基。 In the formula [2-1], Y A represents an organic group having a structure represented by the aforementioned formula [2].

式〔2-1〕中，A1及A2各自獨立表示氫原子或碳數1~5之伸烷基。 In Formula [2-1], A 1 and A 2 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

更具體而言，以使用下述式〔2a〕所示二胺化合物為佳。 More specifically, it is preferable to use a diamine compound represented by the following formula [2a].

式〔2a〕中，Y1及Y7各自獨立表示由單鍵、 碳數1~10之伸烷基、-O-、-S-、-N(R1)-(R1表示氫原子或碳數1~3之伸烷基)、-CON(R2)-(R2表示氫原子或碳數1~3之伸烷基)、-N(R3)CO-(R3表示氫原子或碳數1~3之伸烷基)、-CH2O-、-COO-及-OCO-所選出之至少1種的有機基。其中，又以單鍵、-O-、-S-、-OCO-或-COO-為佳。更佳為，就液晶配向性與膜硬度之觀點，例如具有更為柔軟，且具有立體障礙較小的結構之單鍵、-O-或-S-。 In formula [2a], Y 1 and Y 7 each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -S-, -N (R 1 )-(R 1 represents a hydrogen atom or C1-C3 alkylene), -CON (R 2 )-(R 2 represents a hydrogen atom or C1-C3 alkylene), -N (R 3 ) CO- (R 3 represents a hydrogen atom Or an alkylene group having 1 to 3 carbon atoms), -CH 2 O-, -COO-, and -OCO- selected from at least one organic group. Among them, a single bond, -O-, -S-, -OCO-, or -COO- is more preferable. More preferably, from the viewpoint of liquid crystal alignment and film hardness, for example, a single bond, -O- or -S-, which has a softer structure and a smaller steric hindrance.

式〔2a〕中，Y2及Y6各自獨立表示碳數1~10之伸烷基。其中，又以碳數1~3之伸烷基為佳，其結構可為直鏈或支鏈之任一者皆可。具體而言，就液晶配向性與液晶配向膜之膜硬度等觀點，以具有自由迴轉部位，且立體障礙較小的結構之伸甲基(-CH2-)、伸乙基(-CH2CH2-)、伸丙基(-(CH2)3-)或異丙基(-C(CH2)2-)為佳。 In the formula [2a], Y 2 and Y 6 each independently represent an alkylene group having 1 to 10 carbon atoms. Among them, an alkylene group having 1 to 3 carbon atoms is preferable, and the structure may be either straight chain or branched chain. Specifically, from the viewpoints of liquid crystal alignment and film hardness of the liquid crystal alignment film, from the viewpoints of liquid crystal alignment film and free-rotation part, and a structure with relatively small steric hindrance, the methyl group (-CH 2- ) and the ethyl group (-CH 2 CH 2- ), propyl (-(CH 2 ) 3- ) or isopropyl (-C (CH 2 ) 2- ) are preferred.

式〔2a〕中，Y3及Y5各自獨立表示氫原子或碳數1~10之烷基。其中，又以氫原子或碳數1~3之烷基為佳。特佳為氫原子。 In the formula [2a], Y 3 and Y 5 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. Particularly preferred is a hydrogen atom.

式〔2a〕中，Y4表示氧原子或硫原子。其中，就液晶配向膜之膜硬度之觀點，又以氧原子為佳。 In the formula [2a], Y 4 represents an oxygen atom or a sulfur atom. Among them, from the viewpoint of the film hardness of the liquid crystal alignment film, an oxygen atom is preferred.

式〔2a〕中，較佳之Y1、Y2、Y3、Y4、Y5、Y6及Y7的組合，例如，下述表1所示之內容。 In formula [2a], preferred combinations of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6, and Y 7 are, for example, those shown in Table 1 below.

其中，又以式〔2-1a〕、式〔2-2a〕、式[2-4a]、式〔2-5a〕、式[2-7a]及式〔2-8a〕所示組合為佳。 Among them, the combination shown by formula [2-1a], formula [2-2a], formula [2-4a], formula [2-5a], formula [2-7a], and formula [2-8a] is preferable. .

式〔2a〕中，A1及A2各自獨立表示氫原子或碳數1~5之伸烷基。 In the formula [2a], A 1 and A 2 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

本發明之特定二胺化合物(2)之具體的二胺化合物，可列舉如，下述式〔2-1a〕~式〔2-3a〕所示二胺化合物等。 Specific examples of the diamine compound of the specific diamine compound (2) of the present invention include diamine compounds represented by the following formulas [2-1a] to [2-3a].

(式〔2-1a〕~式〔2-3a〕中，A1~A6各自獨立表示氫原子或碳數1~5之伸烷基)。 (In the formulae [2-1a] to [2-3a], A 1 to A 6 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.)

本發明之特定聚合物(B)中之特定二胺化合物(2)，於全部二胺成份100莫耳%中，以1莫耳%~95莫耳%為佳。其中，又以5莫耳%~95莫耳%為佳。更佳者為20莫耳%~80莫耳%。 The specific diamine compound (2) in the specific polymer (B) of the present invention is preferably 1 mol% to 95 mol% out of 100 mol% of the total diamine component. Among them, 5 mole% to 95 mole% is preferred. More preferred is 20 mol% to 80 mol%.

本發明之特定二胺化合物(2)，可依本發明之特定聚合物(B)對於溶劑之溶解性或液晶配向處理劑之塗佈性、作為液晶配向膜之情形中的液晶配向性、電壓保持率、蓄積電荷等之特性，將1種類或2種類以上混合使用。 The specific diamine compound (2) of the present invention may be based on the solubility of the specific polymer (B) of the present invention in a solvent or the coating property of a liquid crystal alignment treatment agent, and the liquid crystal alignment property and voltage when used as a liquid crystal alignment film. Retention rate, accumulated charge, and other characteristics are used by mixing one or more types.

本發明之特定聚合物(A)及特定聚合物(B)的二胺成份，於未損害本發明之效果的範圍內，亦可使用特定二胺化合物(1)及特定二胺化合物(2)以外的其他二胺化合物(亦稱為其他二胺化合物)。 As for the diamine component of the specific polymer (A) and the specific polymer (B) of the present invention, the specific diamine compound (1) and the specific diamine compound (2) may be used within a range that does not impair the effects of the present invention. Other diamine compounds (also known as other diamine compounds).

具體而言，2,4-二甲基-m-伸苯基二胺、2,6-二胺基甲苯、m-伸苯基二胺、p-伸苯基二胺、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’-聯苯基、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’-二胺基二苯基甲烷、3,3’-二胺基二苯基甲烷、3,4’-二胺基二苯基甲烷、2,2’-二胺基二苯基甲烷、2,3’-二胺基二苯基甲烷、4,4’-二胺基二苯醚、3,3’-二胺基二苯醚、3,4’-二胺基二苯醚、2,2’-二胺基二苯醚、2,3’-二胺基二苯醚、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’-硫代二苯胺、3,3’-硫代二苯胺、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’-二胺基二苯甲酮、3,3’-二胺基二苯甲酮、3,4’-二胺基二苯甲酮、1,4-二胺基萘、2,2’-二胺基二苯甲酮、2,3’-二胺基二苯甲酮、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-胺基苄基)苯、1,3-雙(4-胺基苯氧基)苯、4,4’-〔1,4-伸苯基雙(伸甲基)〕二苯胺、4,4’-〔1,3-伸苯基雙(伸甲基)〕二苯胺、3,4’-〔1,4-伸苯基雙(伸甲基)〕二苯胺、3,4’-〔1,3-伸苯基雙(伸甲基)〕二苯胺、3,3’-〔1,4-伸苯基雙(伸甲基)〕二苯胺、3,3’-〔1,3-伸苯基雙(伸甲基)〕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)對酞醯胺、N,N’-雙(3-胺基苯基)對酞醯胺、N,N’-雙(4-胺基苯基)間酞醯胺、N,N’-雙(3-胺基苯基)間酞醯胺、9,10-雙(4-胺基苯基)蒽、4,4’-雙(4-胺基苯氧基)二苯基碸、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、雙(4-胺基環己基)甲烷、雙(4-胺基-3-甲基環己基)甲烷、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，此外，又例如該些胺基為二級胺基之二胺化合物等。 Specifically, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, m-phenylenediamine, p-phenylenediamine, 4,4'- Diamine Benzene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy -4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3, 3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl Benzene, 2,3'-diaminodiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenyl Methane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl Ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfobiphenylaniline, 3 , 3'-sulfofluorenyldiphenylamine, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl -Bis (3-aminophenyl) silane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 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) amine, N- Methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diamine Benzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-Diaminonaphthalene, 1,7-Diaminonaphthalene, 1,8-Diaminonaphthalene, 2,5-Diaminonaphthalene, 2,6-Diaminonaphthalene, 2,7-Di Aminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-amino Phenyl) butane, 1,4-bis (3-aminophenyl) butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-amine Phenylphenoxy) 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-phenylphenylbis ( (Methyl)] diphenylamine, 4,4 '-[1,3-phenylenebis (methyl)] diphenylamine, 3,4'-[1,4-phenylenebis (methyl)] Diphenylamine, 3,4 '-[1,3-phenylenebis (methylidene)] diphenylamine, 3,3'-[1,4-phenylenebis (methylidene)] diphenylamine, 3 , 3 '-[1,3-phenylenebis (methylene)] diphenylamine, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylene Bis [(3-aminophenyl) methanone], 1,3-phenylphenylbis [(4-aminophenyl) methanone], 1,3-phenylphenylbis [(3-aminophenylbenzene) Methyl) ketone], 1,4-phenylene bis (4-aminobenzoate), 1,4-phenylene bis (3-aminobenzoate), 1,3-phenylene Bis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis ( 3-aminophenyl) Diformate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N '-(1,4-phenylene ) Bis (4-aminobenzidine), N, N '-(1,3-phenylene) bis (4-aminobenzidine), N, N'-(1,4-phenylene) Phenyl) bis (3-aminobenzamide), N, N '-(1,3-phenylene) bis (3-aminobenzamide), N, N'-bis (4- Aminophenyl) p-phthalamide, N, N'-bis (3-aminophenyl) p-phthalamide, N, N'-bis (4-aminophenyl) m-phthalamide, N, N'-bis (3-aminophenyl) m-phthalimide, 9,10-bis (4-aminophenyl) anthracene, 4,4'-bis (4-aminophenoxy) diphenyl Hydrazone, 2,2'-bis [4- (4-amino (Phenoxy) phenyl] propane, 2,2'-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoro Propane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2'-bis ( 4-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (3-amino-4-methylphenyl) propane, 1,3- Bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3-Aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6- Bis (4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7 -(3-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9 -Bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10 -(3-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12 -(4-aminophenoxy) dodecane, 1,12- (3 -Aminophenoxy) dodecane, bis (4-aminocyclohexyl) methane, 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 -Diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, or 1,12-diaminododecane, and for example, these amine groups are secondary Amine-based diamine compounds and the like.

又，亦可使用二胺化合物的側鏈具有高疏水性的長鏈烷基之二胺化合物。 In addition, a diamine compound having a long chain alkyl group having a high hydrophobicity in the side chain of the diamine compound may be used.

本發明之其他二胺化合物，可配合本發明之特定聚合物(A)及特定聚合物(B)對溶劑之溶解性或液晶配向處理劑之塗佈性、作為液晶配向膜之情形中的液晶配向性、電壓保持率、蓄積電荷等特性，將1種類或2種類以上混合使用。 The other diamine compounds of the present invention can be used in combination with the specific polymer (A) and the specific polymer (B) of the present invention in the solubility of a solvent or the coating property of a liquid crystal alignment treatment agent, and in the case of a liquid crystal alignment film. Characteristics such as alignment, voltage retention, and accumulated charge are used by mixing one or more types.

本發明之特定聚合物(A)及特定聚合物(B)，即，欲製作該些聚醯亞胺系聚合物時所使用的四羧酸成份，以使用下述式〔3〕所示四羧酸二酐為佳。此時，不僅式〔3〕所示四羧酸二酐，亦可使用其四羧酸衍生物的四羧酸、四羧酸二鹵化物化合物、四羧酸二烷酯化合物或四羧酸二烷酯二鹵化物化合物(式〔3〕所示四羧酸二酐及及其衍生物亦統稱為特定四羧酸成份)。 The specific polymer (A) and the specific polymer (B) of the present invention, that is, the tetracarboxylic acid component used when the polyfluorene-imide-based polymers are to be produced, are represented by the following formula [3]: Carboxylic dianhydride is preferred. In this case, not only the tetracarboxylic dianhydride represented by the formula [3], but also a tetracarboxylic acid, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or a tetracarboxylic acid dicarboxylic acid whose tetracarboxylic acid derivative is used Alkyl ester dihalide compounds (the tetracarboxylic dianhydrides and their derivatives represented by formula [3] are also collectively referred to as specific tetracarboxylic acid components).

(式〔3〕中，Z表示由下述式〔3a〕~式〔3k〕所示結構所選出之至少1種的結構)。 (In the formula [3], Z represents at least one structure selected from the structures represented by the following formulas [3a] to [3k]).

式〔3a〕中，Z1~Z4表示氫原子、甲基、乙基、丙基、氯原子或苯環，其可分別為相同亦可、相異亦可。 In the formula [3a], Z 1 to Z 4 represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom, or a benzene ring, and they may be the same as or different from each other.

式〔3g〕中，Z5及Z6各自獨立表示氫原子或甲基，其可分別為相同亦可、相異亦可。 In the formula [3g], Z 5 and Z 6 each independently represent a hydrogen atom or a methyl group, and they may be the same as or different from each other.

式〔3〕中之Z中，就合成之容易度或製造聚合物時之聚合反應性之容易度的觀點，以式〔3a〕、式〔3c〕~式〔3g〕或式〔3k〕所示結構之四羧酸二酐及其四羧酸衍生物為佳。更佳者為式〔3a〕或式〔3e〕~式〔3g〕所示結構者。特佳為式〔3a〕、式〔3e〕或式〔3f〕所示結構之四羧酸二酐及其四羧酸衍生物。 In Z in the formula [3], from the viewpoint of ease of synthesis or ease of polymerization reactivity at the time of manufacturing a polymer, the formula [3a], [3c] to [3g], or [3k] Tetracarboxylic dianhydride having a structure and a tetracarboxylic acid derivative thereof are preferable. More preferred are the structures shown by formula [3a] or formula [3e] to formula [3g]. Particularly preferred is a tetracarboxylic dianhydride having a structure represented by the formula [3a], [3e] or [3f] and a tetracarboxylic acid derivative thereof.

本發明之特定聚合物(A)及特定聚合物(B)中之特定四羧酸成份，於全部的四羧酸成份100莫耳%中，以1莫耳%~100莫耳%為佳。其中，又以5莫耳%~95莫耳%為佳。更佳者為20莫耳%~80莫耳%。 The specific tetracarboxylic acid component in the specific polymer (A) and the specific polymer (B) of the present invention is preferably 100 mol% to 100 mol% of the total tetracarboxylic acid components. Among them, 5 mole% to 95 mole% is preferred. More preferred is 20 mol% to 80 mol%.

本發明之特定四羧酸成份，可配合本發明之 特定聚合物(A)及特定聚合物(B)對溶劑之溶解性，或液晶配向處理劑之塗佈性、作為液晶配向膜之情形中的液晶之配向性、電壓保持率、蓄積電荷等特性，而可使用1種類或將2種類以上混合使用。 The specific tetracarboxylic acid component of the present invention can be matched with the present invention. Specific polymer (A) and specific polymer (B) solubility in a solvent, coating property of a liquid crystal alignment treatment agent, liquid crystal alignment property in the case of a liquid crystal alignment film, voltage holding ratio, accumulated charge and other characteristics You can use 1 type or a mixture of 2 or more types.

本發明之特定聚合物(A)及特定聚合物(B)的聚醯亞胺系聚合物中，於未損害本發明之效果的範圍內，亦可使用特定四羧酸成份以外的其他四羧酸成份。 In the polyimide-based polymer of the specific polymer (A) and the specific polymer (B) of the present invention, other tetracarboxylic acids other than the specific tetracarboxylic acid component may be used within a range not impairing the effects of the present invention. Acid ingredients.

其他四羧酸成份，可列舉如，以下所示之四羧酸化合物、四羧酸二酐、四羧酸二鹵化物化合物、四羧酸二烷酯化合物或四羧酸二烷酯二鹵化物化合物等。 Examples of other tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic dihalide compounds, tetracarboxylic dialkyl ester compounds, or tetracarboxylic dialkyl dihalides. Compounds etc.

即，其他之四羧酸成份，可列舉如，1,2,5,6-萘四羧酸、1,4,5,8-萘四羧酸、1,2,5,6-蒽四羧酸、3,3’,4,4’-聯苯基四羧酸、2,3,3’,4-聯苯基四羧酸、雙(3,4-二羧基苯基)醚、3,3’,4,4’-二苯甲酮四羧酸、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’-二苯基碸四羧酸、3,4,9,10-苝四羧酸或1,3-二苯基-1,2,3,4-環丁烷四羧酸等。 That is, other tetracarboxylic acid components include 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, and 1,2,5,6-anthracenetetracarboxylic acid. Acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3, 3 ', 4,4'-benzophenone tetracarboxylic acid, bis (3,4-dicarboxyphenyl) fluorene, 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) Yl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) ) Pyridine, 3,3 ', 4,4'-diphenylfluorenetetracarboxylic acid, 3,4,9,10-fluorenetetracarboxylic acid or 1,3-diphenyl-1,2,3,4- Cyclobutane tetracarboxylic acid and the like.

本發明之其他四羧酸成份，可配合本發明之特定聚合物(A)及特定聚合物(B)對溶劑之溶解性或 液晶配向處理劑之塗佈性、作為液晶配向膜之情形中的液晶配向性、電壓保持率、蓄積電荷等特性，將1種類或2種類以上混合使用。 The other tetracarboxylic acid components of the present invention may be compatible with the solubility of the specific polymer (A) and the specific polymer (B) of the present invention in a solvent or The liquid crystal alignment treatment agent is applied in a mixture of 1 type or 2 or more characteristics such as the liquid crystal alignment property, the voltage retention ratio, and the stored charge in the case of a liquid crystal alignment film.

<特定聚合物(A)‧特定聚合物(B)之製作方法> <Production method of specific polymer (A) and specific polymer (B)>

本發明中，特定聚合物(A)及特定聚合物(B)，即，製作該些聚醯亞胺系聚合物所使用之方法並未有特別之限定。通常可由二胺成份與四羧酸成份反應而得。一般而言，可列舉如，使由四羧酸二酐及其四羧酸之衍生物所成群中所選出之至少1種的四羧酸成份，與由1種或複數種的二胺化合物所成之二胺成份進行反應，而製得聚醯胺酸之方法等。具體而言，可使用例如，使四羧酸二酐與一級或二級的二胺化合物進行聚縮合反應而製得聚醯胺酸之方法、使四羧酸與一級或二級的二胺化合物進行脫水聚縮合反應而製得聚醯胺酸之或四羧酸二鹵化物與一級或二級的二胺化合物進行聚縮合反應，而製得聚醯胺酸之方法。 In the present invention, the specific polymer (A) and the specific polymer (B), that is, the method used to prepare the polyfluorene-imide-based polymers are not particularly limited. It is usually obtained by reacting a diamine component with a tetracarboxylic acid component. Generally, for example, a tetracarboxylic dianhydride and a derivative of a tetracarboxylic dianhydride are selected from the group consisting of at least one type of tetracarboxylic acid component and one or more types of diamine compounds. The resulting diamine component is reacted to prepare a polyamine acid and the like. Specifically, for example, a method in which polycarboxylic acid is produced by subjecting a tetracarboxylic dianhydride to a primary or secondary diamine compound to a polycondensation reaction, and a tetracarboxylic acid and a primary or secondary diamine compound can be used. Method for preparing polyamidic acid or tetracarboxylic dihalide by performing dehydration polycondensation reaction and first or second stage diamine compound by polycondensation reaction to prepare polyamidic acid.

製得聚醯胺酸烷酯之方法，例如可使用使羧酸基經二烷酯化而得之四羧酸與一級或二級的二胺化合物進行聚縮合之方法、羧酸基經二烷酯化而得之四羧酸二鹵化物與一級或二級的二胺化合物進行聚縮合之方法或使聚醯胺酸的羧基變換為酯之方法。 The method for producing a polyalkylammonium ester may be, for example, a method of polycondensing a tetracarboxylic acid obtained by dialkylating a carboxylic acid group with a primary or secondary diamine compound, A method of polycondensing a tetracarboxylic dihalide obtained by esterification with a primary or secondary diamine compound or a method of converting a carboxyl group of a polyamic acid into an ester.

製得聚醯亞胺之方法，例如可使用使前述聚醯胺酸或聚醯胺酸烷酯進行閉環反應以形成聚醯亞胺之方法。 As a method for producing polyimide, for example, a method of subjecting the aforementioned polyamidate or polyalkylamidate to a ring-closing reaction to form polyimide can be used.

二胺成份與四羧酸成份之反應，通常，為使二胺成份與四羧酸成份於溶劑中進行。此時所使用的溶劑，只要可使所生成的聚醯亞胺前驅體溶解之溶劑時，並未有特別之限定。下述內容中，將列舉反應所使用之溶劑的具體例，但並不僅限定於該些例示。 The reaction between the diamine component and the tetracarboxylic acid component is generally performed in a solvent. The solvent used in this case is not particularly limited as long as it is a solvent that can dissolve the produced polyfluorene imine precursor. In the following, specific examples of the solvent used in the reaction will be listed, but the invention is not limited to these examples.

例如，N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮或γ-丁內酯、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、二甲基亞碸或1,3-二甲基-四氫咪唑酮等。又，聚醯亞胺前驅體之溶劑溶解性為較高之情形，可使用甲基乙基酮、環己酮、環戊酮、4-羥基-4-甲基-2-戊酮或下述式〔D-1〕~式〔D-3〕所示溶劑。 For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N, N-dimethylformamidine, N, N-dimethylacetamidine Amines, dimethylsulfinium or 1,3-dimethyl-tetrahydroimidazolone. When the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following can be used. Solvents represented by formulas [D-1] to [D-3].

(式〔D-1〕中，D1表示碳數1~3之伸烷基，式〔D-2〕中，D2表示碳數1~3之伸烷基，式〔D-3〕中，D3表示碳數1~4之伸烷基)。 (In formula [D-1], D 1 represents an alkylene group having 1 to 3 carbon atoms, in formula [D-2], D 2 represents an alkylene group having 1 to 3 carbon atoms, and in formula [D-3] , D 3 represents an alkylene group having 1 to 4 carbon atoms).

該些溶劑可單獨使用亦可、混合使用亦可。此外，即使為不溶解聚醯亞胺前驅體之溶劑，只要為不會析出生成之聚醯亞胺前驅體之範圍，亦可與前述溶劑混合使用。又，溶劑中之水分為阻礙聚合反應，甚至會造成生成之聚醯亞胺前驅體水解之原因，故溶劑以使用脫水乾燥 者為佳。 These solvents may be used alone or in combination. Moreover, even if it is a solvent which does not dissolve a polyfluorene imide precursor, as long as it is the range which does not precipitate the generated polyfluorene imide precursor, you may mix and use it with the said solvent. In addition, the water in the solvent is the reason for hindering the polymerization reaction and even causing the hydrolysis of the resulting polyimide precursor. Therefore, the solvent is dehydrated and dried. Those are better.

二胺成份與四羧酸成份於溶劑中進行反應之際，例如可使用，使二胺成份分散或溶解於溶劑的溶液於攪拌中，將四羧酸成份無處理下，或使其分散或溶解於溶劑下進行添加之方法，或相反地，於四羧酸成份分散於溶劑，或溶解所得之溶液中，添加二胺成份之方法、將二胺成份與四羧酸成份交互添加之方法等，上述任一種方法皆可使用。又，二胺成份或四羧酸成份分別使用複數種進行反應之情形，可以預先混合之狀態下進行反應亦可、各別依序進行反應亦可、將各別反應所得之低分子量體進行混合反應以製得之聚合物亦可。此時之聚合溫度可選擇於-20℃~150℃之任意溫度，較佳為-5℃~100℃之範圍。又，反應可於任意濃度下進行亦可，但濃度過低時將不易得到高分子量的聚合物，濃度過高時，因反應液的黏性過高而不易進行均勻的攪拌。因此，較佳為1~50質量%、更佳為5~30質量%。也可以在反應初期以高濃度進行，其後再追加溶劑亦可。 When the diamine component and the tetracarboxylic acid component are reacted in a solvent, for example, a solution in which the diamine component is dispersed or dissolved in the solvent can be used while stirring, and the tetracarboxylic acid component is left untreated or dispersed or dissolved. A method of adding under a solvent, or conversely, a method of adding a diamine component to a solution obtained by dispersing a tetracarboxylic acid component in a solvent or dissolving, a method of adding a diamine component and a tetracarboxylic acid component alternately, etc. Either method can be used. In the case where the diamine component or the tetracarboxylic acid component is reacted by using a plurality of types, the reaction may be carried out in a state of being mixed in advance, the reactions may be performed in order, and the low-molecular weight bodies obtained by the respective reactions may be mixed. The polymer obtained by the reaction may also be used. The polymerization temperature at this time may be selected at any temperature of -20 ° C to 150 ° C, and preferably in the range of -5 ° C to 100 ° C. In addition, the reaction may be carried out at any concentration, but if the concentration is too low, a polymer with a high molecular weight may not be easily obtained, and if the concentration is too high, it is difficult to perform uniform stirring due to too high viscosity of the reaction solution. Therefore, it is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction may be performed at a high concentration in the initial stage of the reaction, and a solvent may be added thereafter.

聚醯亞胺前驅體的聚合反應中，二胺成份的合計莫耳數與四羧酸成份的合計莫耳數之比，以0.8~1.2為佳。其與通常之聚縮合反應相同般，該莫耳比越趨近1.0時，所生成之聚醯亞胺前驅體的分子量越大。 In the polymerization reaction of the polyfluorene imide precursor, the ratio of the total molar number of the diamine component to the total molar number of the tetracarboxylic acid component is preferably 0.8 to 1.2. It is the same as the usual polycondensation reaction. As the molar ratio approaches 1.0, the molecular weight of the resulting polyfluorene imine precursor increases.

本發明之聚醯亞胺為使前述聚醯亞胺前驅體經閉環而得之聚醯亞胺，此聚醯亞胺中，醯胺酸基之閉環率(亦稱為醯亞胺化率)，並非必須為100%，而可配合 用途或目的作任意的調整。 The polyimide of the present invention is a polyimide obtained by subjecting the aforementioned polyimide precursor to ring closure. In this polyimide, the ring closure ratio of the amido acid group (also referred to as the amidation ratio) , Does not have to be 100%, but can cooperate Use or purpose to make arbitrary adjustments.

使聚醯亞胺前驅體醯亞胺化之方法，可列舉如，使聚醯亞胺前驅體的溶液於無處理下進行加熱使其熱醯亞胺化，或於聚醯亞胺前驅體的溶液中添加觸媒而進行觸媒醯亞胺化之方法等。 Examples of the method for polyimide precursor polyimide include heating the solution of polyimide precursor without heat treatment to thermally imidize the polyimide precursor, or the method of polyimide precursor. A method of adding a catalyst to the solution to perform the catalyst sulfidation.

使聚醯亞胺前驅體於溶液中進行熱醯亞胺化之情形的溫度為100℃~400℃，較佳為120℃~250℃，又以將醯亞胺化反應所生成的水排除於反應系外之方式進行為佳。 The temperature of the case where the polyfluorene imine precursor is thermally fluorinated in a solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and water generated by the fluorene imidization reaction is excluded. The reaction is preferably performed in a manner outside the system.

聚醯亞胺前驅體之觸媒醯亞胺化之方法為，將鹼性觸媒與酸酐添加於聚醯亞胺前驅體之溶液中，於-20℃~250℃，較佳為於0℃~180℃中以攪拌方式進行。鹼性觸媒的量為醯胺酸基之0.5莫耳倍~30莫耳倍，較佳為2莫耳倍~20莫耳倍，酸酐的量為醯胺酸基之1莫耳倍~50莫耳倍，較佳為3莫耳倍~30莫耳倍。鹼性觸媒，可列舉如，吡啶、三乙基胺、三甲基胺、三丁基胺或三辛基胺等，其中，又以吡啶於進行反應時可維持適當之鹼性而為較佳。酸酐，可列舉如，乙酸酐、偏苯三酸酐或苯均四酸二酐等，其中，又以使用乙酸酐時，於反應結束後容易進行精製而為較佳。觸媒醯亞胺化之醯亞胺化率，可以依調節觸媒量與反應溫度、反應時間等方式予以控制。 The catalyst for polyimide precursors is to be imidized by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursors, at -20 ° C to 250 ° C, preferably at 0 ° C. ~ 180 ° C with stirring. The amount of alkaline catalyst is 0.5 mol times to 30 mol times, preferably 2 mol times to 20 mol times, and the amount of acid anhydride is 1 mol times to 50 mol times. Molar times, preferably 3 to 30 mole times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine can maintain an appropriate basicity during the reaction. good. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic dianhydride. Among them, when acetic anhydride is used, it is more preferable to perform purification after completion of the reaction. The rate of catalyst imidization can be controlled by adjusting the amount of catalyst, the reaction temperature, and the reaction time.

由聚醯亞胺前驅體或聚醯亞胺的反應溶液中，回收所生成之聚醯亞胺前驅體或聚醯亞胺之方式，只 要將反應溶液投入溶劑中使其沈澱即可。沈澱所使用的溶劑，可列舉如，甲醇、乙醇、異丙醇、丙酮、己烷、丁基溶纖劑、庚烷、甲基乙基酮、甲基異丁酮、甲苯、苯、水等。將投入溶劑使其沈澱之聚合物經濾過回收後，可於常壓或減壓下，以常溫或加熱予以乾燥。又，重複2次~10次將沈澱回收之聚合物再溶解於溶劑、再沈澱回收之操作後，可降低聚合物中之雜質。此時之溶劑，例如，醇類、酮類或烴等，由該些之中選擇3種類以上的溶劑使用時，以其可進一步提高精製之效率而為較佳。 The method of recovering the produced polyimide precursor or polyimide from the polyimide precursor or polyimide reaction solution, only The reaction solution can be put into a solvent to precipitate it. Examples of the solvent used for the precipitation include methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. After the polymer which has been put into the solvent to precipitate is filtered and recovered, it can be dried at normal temperature or heating under normal pressure or reduced pressure. In addition, repeating the operation of re-dissolving the polymer recovered by precipitation 2 to 10 times in a solvent and re-precipitation recovery can reduce impurities in the polymer. In this case, the solvent, for example, alcohols, ketones, or hydrocarbons, when three or more types of solvents are selected for use, it is preferable to further improve the efficiency of purification.

<液晶配向處理劑> <Liquid crystal alignment treatment agent>

本發明之液晶配向處理劑為，形成液晶配向膜(亦稱為樹脂被膜)所使用的塗佈溶液，其為形成含有特定聚合物(A)、特定聚合物(B)及溶劑的液晶配向膜所使用之塗佈溶液。 The liquid crystal alignment treatment agent of the present invention is a coating solution for forming a liquid crystal alignment film (also referred to as a resin film), and is a liquid crystal alignment film containing a specific polymer (A), a specific polymer (B), and a solvent. The coating solution used.

本發明之特定聚合物(A)，可使用聚醯胺酸、聚醯胺酸烷酯及聚醯亞胺中之任一種聚醯亞胺系聚合物皆可。其中，又以聚醯胺酸烷酯或聚醯亞胺為佳。更佳為聚醯亞胺。具體而言，以醯亞胺化率為50%以上的聚醯亞胺為佳，以醯亞胺化率為70%以上的聚醯亞胺為更佳。 As the specific polymer (A) of the present invention, any one of polyimide-based polymers such as polyamidic acid, polyalkylamic acid polyamidate, and polyimide may be used. Among them, polyalkylamidate or polyimide is more preferred. More preferred is polyimide. Specifically, polyfluorene imine having a fluorene imidization rate of 50% or more is preferable, and polyfluorene imine having a fluorene imidization rate of 70% or more is more preferable.

本發明之特定聚合物(B)，可使用聚醯胺酸、聚醯胺酸烷酯及聚醯亞胺中之任一種聚醯亞胺系聚合物皆可。其中，又以聚醯胺酸或聚醯胺酸烷酯為佳。更佳為聚醯胺酸。 As the specific polymer (B) of the present invention, any one of polyamidoimide-based polymers, polyamidoimide, polyalkylamidoate, and polyimide may be used. Among them, polyamidic acid or polyalkylaminoalkyl esters are more preferred. More preferred is polyamic acid.

本發明之液晶配向處理劑中，特定聚合物(A)與特定聚合物(B)之比例為，相對於特定聚合物(A)100質量份，特定聚合物(B)以0.5質量份~950質量份為佳。其中，又以10質量份~900質量份為佳，更佳者為10質量份~400質量份。 In the liquid crystal alignment treatment agent of the present invention, the ratio of the specific polymer (A) to the specific polymer (B) is 0.5 to 950 parts by mass with respect to 100 parts by mass of the specific polymer (A). Mass parts are preferred. Among them, 10 parts by mass to 900 parts by mass are more preferable, and 10 parts by mass to 400 parts by mass are more preferable.

本發明之液晶配向處理劑中，所有的聚合物成份，可全部為本發明之特定聚合物(A)及特定聚合物(B)亦可，或與該些以外的其他聚合物混合者亦可。該些以外的聚合物，可列舉如，不具有本發明之氮原子的結構的聚醯亞胺系聚合物，及不具有特定結構(2)的聚醯亞胺系聚合物等。此外，又例如，纖維素系聚合物、丙烯酸聚合物、甲基丙烯酸聚合物、聚苯乙烯、聚醯胺或聚矽氧烷等。此時，該些以外的其他聚合物之含量為，相對於本發明之特定聚合物(A)及特定聚合物(B)全部的特定聚合物100質量份，為0.5質量份~30質量份。其中，又以1質量份~20質量份為佳。 In the liquid crystal alignment treatment agent of the present invention, all of the polymer components may be the specific polymer (A) and the specific polymer (B) of the present invention, or may be mixed with other polymers other than these. . Examples of the polymers other than these include polyimide-based polymers which do not have the structure of the nitrogen atom of the present invention, and polyimide-based polymers which do not have a specific structure (2). In addition, for example, a cellulose polymer, an acrylic polymer, a methacrylic polymer, polystyrene, polyamine, or polysiloxane. At this time, the content of other polymers other than these is 0.5 to 30 parts by mass based on 100 parts by mass of the specific polymers of the specific polymer (A) and the specific polymer (B) in the present invention. Among them, 1 to 20 parts by mass is preferred.

又，本發明之液晶配向處理劑中之溶劑之含量，以70質量%~99.9質量%為佳。此含量可配合液晶配向處理劑的塗佈方法或作為目的之液晶配向膜的膜厚度，作適當之變更。 The content of the solvent in the liquid crystal alignment treatment agent of the present invention is preferably 70% by mass to 99.9% by mass. This content can be appropriately changed according to the coating method of the liquid crystal alignment treatment agent or the film thickness of the liquid crystal alignment film to be used.

本發明之液晶配向處理劑所使用之溶劑，只要為可溶解特定聚合物(A)及特定聚合物(B)的溶劑(亦稱良溶劑)時，並未有特別之限定。以下將列舉良溶劑的具體例示，但並不僅限定於該些例示。 The solvent used for the liquid crystal alignment treatment agent of the present invention is not particularly limited as long as it is a solvent (also referred to as a good solvent) that can dissolve the specific polymer (A) and the specific polymer (B). Specific examples of good solvents are listed below, but they are not limited to these examples.

例如，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-乙基-2-吡咯啶酮、二甲基亞碸、γ-丁內酯、1,3-二甲基-四氫咪唑酮、甲基乙基酮、環己酮、環戊酮或4-羥基-4-甲基-2-戊酮等。 For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylimine Rhenium, γ-butyrolactone, 1,3-dimethyl-tetrahydroimidazolidone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like.

其中，又以使用N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、γ-丁內酯為佳。 Among these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone are more preferably used.

此外，特定聚合物(A)及特定聚合物(B)對溶劑具有高度溶解性之情形，以使用前述式〔D-1〕~式〔D-3〕所示溶劑為佳。 When the specific polymer (A) and the specific polymer (B) have high solubility in a solvent, it is preferable to use a solvent represented by the aforementioned formulas [D-1] to [D-3].

本發明之液晶配向處理劑中之良溶劑，以佔液晶配向處理劑所含溶劑全體的20質量%~99質量%為佳。其中，又以20質量%~90質量%為佳。更佳者為30質量%~80質量%。 The good solvent in the liquid crystal alignment treatment agent of the present invention is preferably 20% to 99% by mass of the entire solvent contained in the liquid crystal alignment treatment agent. Among them, it is preferably 20% by mass to 90% by mass. More preferably, it is 30% to 80% by mass.

本發明之液晶配向處理劑，於無損本發明之效果之範圍，於塗佈液晶配向處理劑之際，可使用提升液晶配向膜的塗膜性或表面平滑性之溶劑(亦稱為貧溶劑)。以下將列舉貧溶劑之具體例示，但並不僅限定於該些例示。 The liquid crystal alignment treatment agent of the present invention is in a range that does not impair the effect of the present invention. When the liquid crystal alignment treatment agent is applied, a solvent (also referred to as a lean solvent) that improves the coating property or surface smoothness of the liquid crystal alignment film can be used . Specific examples of the lean solvent will be listed below, but they are not limited to these examples.

例如，乙醇、異丙醇、1-丁醇、2-丁醇、異丁醇、tert-丁醇、1-戊醇、2-戊醇、3-戊醇、2-甲基-1-丁醇、異戊醇、tert-戊醇、3-甲基-2-丁醇、新戊醇、1-己醇、2-甲基-1-戊醇、2-甲基-2-戊醇、2-乙基-1-丁醇、1-庚醇、2-庚醇、3-庚醇、1-辛醇、2-辛醇、2-乙基-1-己醇、環己醇、1-甲基環己醇、2-甲基環己醇、3-甲基環己 醇、1,2-乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,5-戊烷二醇、2-甲基-2,4-戊烷二醇、2-乙基-1,3-已二醇、二丙醚、二丁醚、二己醚、二噁烷、乙二醇二甲醚、乙二醇二***、乙二醇二丁醚、1,2-丁氧基乙烷、二乙二醇二甲醚、二乙二醇二***、二乙二醇甲基***、二乙二醇二丁醚、2-戊酮、3-戊酮、2-己酮、2-庚酮、4-庚酮、3-乙氧基丁基乙酸酯、1-甲基戊基乙酸酯、2-乙基丁基乙酸酯、2-乙基己基乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、丙烯碳酸酯、乙烯碳酸酯、2-(甲氧基甲氧基)乙醇、乙二醇單丁醚、乙二醇單異戊醚、乙二醇單己醚、2-(己基氧基)乙醇、糠醇、二乙二醇、丙二醇、丙二醇單丁醚、1-(丁氧基乙氧基)丙醇、丙二醇單甲醚乙酸酯、二丙二醇、二丙二醇單甲醚、二丙二醇單***、二丙二醇二甲醚、三丙二醇單甲醚、乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、乙二醇單丁醚乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、二乙二醇單***乙酸酯、二乙二醇單丁醚乙酸酯、2-(2-乙氧基乙氧基)乙基乙酸酯、二乙二醇乙酸酯、三乙二醇、三乙二醇單甲醚、三乙二醇單***、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***、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、乳酸甲酯、乳酸乙酯、乳酸n-丙酯、乳酸n-丁酯、 乳酸異戊酯或前述式〔D-1〕~式〔D-3〕所示溶劑等。 For example, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol Alcohol, isoamyl alcohol, tert-pentanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1 -Methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol Alcohol, 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3- Butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexane Ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Diethylene glycol methyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl ethyl Acid ester, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate Ester, ethylene carbonate, 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol , Diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1- (butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Dimethyl ether, three Glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate , Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethyl Glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, Ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxy Propionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, Isoamyl lactate, a solvent represented by the above formula [D-1] to [D-3], and the like.

其中，又以使用1-己醇、環己醇、1,2-乙二醇、1,2-丙二醇、丙二醇單丁醚、乙二醇單丁醚或二丙二醇二甲醚為佳。 Among these, 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, or dipropylene glycol dimethyl ether are more preferably used.

該些貧溶劑，以佔液晶配向處理劑中所含溶劑全體的1質量%~80質量%為佳。其中，又以10質量%~80質量%為佳。更佳為20質量%~70質量%。 These poor solvents are preferably 1% to 80% by mass of the entire solvent contained in the liquid crystal alignment treatment agent. Among them, 10% to 80% by mass is preferred. More preferably, it is 20% to 70% by mass.

本發明之液晶配向處理劑中，以導入具有環氧基、異氰酸酯基、環氧丙烷基或環碳酸酯基的交聯性化合物、具有由羥基、羥烷基及低級烷氧基烷基所成群所選出之至少1種的取代基之交聯性化合物，或具有聚合性不飽和鍵結的交聯性化合物者為佳。該些取代基或聚合性不飽和鍵結，於交聯性化合物中必須具有2個以上。 In the liquid crystal alignment treatment agent of the present invention, a crosslinkable compound having an epoxy group, an isocyanate group, a propylene oxide group, or a cyclic carbonate group is introduced, and the compound is composed of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group. A crosslinkable compound having at least one kind of substituent selected from the group, or a crosslinkable compound having a polymerizable unsaturated bond is preferred. These substituents or polymerizable unsaturated bonds must have two or more in the crosslinkable compound.

具有環氧基或異氰酸酯基之交聯性化合物，例如，雙酚丙酮縮水甘油醚、酚-酚醛清漆環氧樹脂、甲酚-酚醛清漆環氧樹脂、三縮水甘油異三聚氰酸酯、四縮水甘油胺基二亞苯、四縮水甘油-m-二甲苯二胺、四縮水甘油-1,3-雙(胺基乙基)環己烷、四苯基縮水甘油醚乙烷、三苯基縮水甘油醚乙烷、雙酚六氟乙醯二縮水甘油醚、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)九氟聯苯基、三縮水甘油-p-胺基酚、四縮水甘油甲基二甲苯二胺、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。 Crosslinkable compounds having an epoxy group or an isocyanate group, for example, bisphenol acetone glycidyl ether, phenol-phenol novolac epoxy resin, cresol-novolac epoxy resin, triglycidyl isotricyanate, Glycidylamino diphenylene, tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenylglycidyl ether ethane, triphenyl Glycidyl ether ethane, bisphenol hexafluoroacetamidine diglycidyl ether, 1,3-bis (1- (2,3-glycidoxy) -1-trifluoromethyl-2,2,2- Trifluoromethyl) benzene, 4,4-bis (2,3-glycidoxy) nonafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidylmethylxylene diamine, 2 -(4- (2,3-glycidoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-glycidoxy) phenyl) ethyl) Phenyl) propane or 1,3-bis (4- (1- (4- (2,3-glycidoxy) phenyl) -1- (4- (1- (4- (2,3-glycidoxy) phenyl) -1-methylethyl) phenyl ) Ethyl) phenoxy) -2-propanol and the like.

具有環氧丙烷基之交聯性化合物，例如，至少具有2個下述式〔4A〕所示環氧丙烷基的交聯性化合物。 The crosslinkable compound having a propylene oxide group is, for example, a crosslinkable compound having at least two propylene oxide groups represented by the following formula [4A].

具體而言，例如，國際公開公報WO2011/132751(2011.10.27公開)之58頁~59頁所揭示之式〔4a〕~式〔4k〕所示交聯性化合物等。 Specifically, for example, the cross-linking compounds represented by the formulas [4a] to [4k] disclosed in pages 58 to 59 of International Publication WO2011 / 132751 (published on 2011.10.27) are described.

具有環碳酸酯基之交聯性化合物，例如，至少具有2個下述式〔5A〕所示環碳酸酯基之交聯性化合物。 The crosslinkable compound having a cyclic carbonate group is, for example, a crosslinkable compound having at least two cyclic carbonate groups represented by the following formula [5A].

具體而言，例如，國際公開公報WO2012/014898(2012.2.2公開)之76頁~82頁所揭示之式〔5-1〕~式〔5-42〕所示交聯性化合物。 Specifically, for example, the cross-linking compounds represented by the formulas [5-1] to [5-42] disclosed on pages 76 to 82 of International Publication WO2012 / 014898 (published on 2012.2.2).

具有由羥基及烷氧基所成群所選出之至少1種的取代基之交聯性化合物，例如，具有羥基或烷氧基的胺基樹脂，例如，三聚氰胺樹脂、尿素樹脂、呱樹脂、乙炔脲-甲醛樹脂、琥珀醯基醯胺-甲醛樹脂或乙烯尿素-甲醛樹脂等。具體而言，例如，可使用胺基的氫原子被羥甲基或烷氧基甲基或其二者所取代之三聚氰胺衍生物、苯併呱衍生物，或乙炔脲。該三聚氰胺衍生物或苯併呱衍生物，亦可以2聚物或3聚物方式存在。該些以每一個三環，平均具有3個以上，6個以下之羥甲基或烷氧基甲基者為佳。 A crosslinkable compound having at least one selected from the group consisting of a hydroxyl group and an alkoxy group, for example, an amine resin having a hydroxyl group or an alkoxy group, for example, a melamine resin, a urea resin, or fluorene Resin, acetylene urea-formaldehyde resin, succinimidylamine-formaldehyde resin or ethylene urea-formaldehyde resin. Specifically, for example, a melamine derivative, a benzofluorene, in which a hydrogen atom of an amine group is replaced by a methylol group or an alkoxymethyl group, or both can be used. Derivatives, or acetylene urea. The melamine derivative or benzofluorene Derivatives may exist as dimers or trimers. Should take every three The ring has three or more hydroxymethyl or alkoxymethyl groups on average.

該些三聚氰胺衍生物或苯併呱衍生物之例示，例如，市售品之每一個三環平均有3.7個取代之甲氧基甲基的MX-750、每一個三環平均有5.8個取代之甲氧基甲基的MW-30(以上，三和化學公司製)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等含羧基之甲氧基甲基化異丁氧基甲基化三聚氰胺、CYMEL-1123等甲氧基甲基化乙氧基甲基化苯併呱、CYMEL-1123-10等甲氧基甲基化丁氧基甲基化苯併呱、CYMEL-1128等丁氧基甲基化苯併呱、CYMEL-1125-80等含羧基之甲氧基甲基化乙氧基甲基化苯併呱(以上，三井氰酸公司製)等。又，乙炔脲之例 如，CYMEL-1170等丁氧基甲基化乙炔脲、CYMEL-1172等羥甲基化乙炔脲等，POWER-LINK1174等甲氧基羥甲基化乙炔脲等。 These melamine derivatives or benzofluorene Examples of derivatives, for example, every three The ring has an average of 3.7 substituted methoxymethyl groups MW-30 (above, manufactured by Sanwa Chemical Co., Ltd.) or CYMEL-300,301,303,350,370,771,325,327,703,712, etc. Methoxymethylated melamine, CYMEL-235, 236, 238, 212, 253, 254, etc. methoxymethylated butoxymethylated melamine, CYMEL-506, 508, etc. butoxymethylated melamine , CYMEL-1141 and other carboxyl-containing methoxymethylated isobutoxymethylated melamine, CYMEL-1123 and other methoxymethylated ethoxymethylated benzofluorene Methoxymethylated butoxymethylated benzopyrene, CYMEL-1123-10, etc. , CYMEL-1128, etc. , CYMEL-1125-80 and other carboxyl-containing methoxymethylated ethoxymethylated benzopyrene (Above, manufactured by Mitsui Cyanide Co., Ltd.) and the like. Examples of the acetylene urea include butoxymethylated acetylene urea such as CYMEL-1170, hydroxymethylated acetylene urea such as CYMEL-1172, and the like, and methoxymethylolated acetylene urea such as POWER-LINK1174.

具有羥基或烷氧基的苯或酚性化合物，例如，1,3,5-三(甲氧基甲基)苯、1,2,4-三(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。 Benzene or phenolic compound having a hydroxy or alkoxy group, for example, 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1, 4-bis (sec-butoxymethyl) benzene or 2,6-dihydroxymethyl-p-tert-butylphenol.

更具體而言，例如，國際公開公報WO2011/132751(2011.10.27公開)之62頁~66頁所揭示之、式〔6-1〕~式〔6-48〕所示交聯性化合物等。 More specifically, for example, the cross-linking compounds represented by Formulas [6-1] to [6-48] disclosed in pages 62 to 66 of International Publication WO2011 / 132751 (published on 2011.10.27) are disclosed.

具有聚合性不飽和鍵結的交聯性化合物，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縮水甘油醚聚(甲基)丙烯酸酯等之聚合性不飽和基的交聯性化合物，此外，又如分子內具有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、氧化乙烯雙酚A型二(甲基)丙烯酸酯、氧化丙烯雙酚型二(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、乙二醇二縮水甘油醚二(甲基)丙烯 酸酯、二乙二醇二縮水甘油醚二(甲基)丙烯酸酯、酞酸二縮水甘油酯二(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的交聯性化合物，此外，又如分子內具有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-羥基丙基酞酸酯、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)丙烯醯胺等聚合性不飽和基的交聯性化合物等。 A crosslinkable compound having a polymerizable unsaturated bond, for example, having 3 trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylic acid in the molecule Polymerizable unsaturated cross-linking compounds such as esters, tris (meth) acryloxyethoxytrimethylolpropane or glycerol polyglycidyl ether poly (meth) acrylate, and For example, it has 2 ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) Acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A Type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol di (Meth) acrylate, ethylene glycol diglycidyl ether di (meth) propylene Acid ester, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl di (meth) acrylate, or hydroxytrimethyl acetate neopentyl glycol di (meth) acrylate, etc. It is a polymerizable unsaturated group crosslinkable compound, and also has 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl in the molecule. (Meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloxy-2-hydroxypropyl phthalate, 3-chloro-2 -Hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 2- (meth) acryloxyethyl phosphate, N-hydroxymethyl (meth) acrylamide, etc. Polymerizable unsaturated group-crosslinkable compounds and the like.

此外，亦可使用下述式〔7A〕所示化合物。 Alternatively, a compound represented by the following formula [7A] may be used.

(式〔7A〕中，E1為為表示由環己烷環、雙環己烷環、苯環、聯苯基環、聯三苯環、萘環、茀環、蒽環或菲環所成群所選出之基，E2表示由下述式〔7a〕或式〔7b〕所選出之基，n表示1~4之整數)。 (In formula [7A], E 1 is a group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a bitriphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, or a phenanthrene ring For the selected base, E 2 represents a base selected by the following formula [7a] or [7b], and n represents an integer of 1 to 4).

上述化合物為交聯性化合物之一例示，但並 不僅限定於該些內容。又，本發明之液晶配向處理劑所使用之交聯性化合物，可為1種類亦可、2種類以上之組合亦可。 The above compound is an example of a crosslinkable compound, but It is not limited to these contents. The crosslinkable compound used in the liquid crystal alignment treatment agent of the present invention may be one type or a combination of two or more types.

本發明之液晶配向處理劑中，交聯性化合物之含量，相對於全部聚合物成份100質量份，以0.1質量份~150質量份為佳。其中，又以進行交聯反應可達目的之效果等觀點，相對於全部聚合物成份100質量份，以0.1質量份~100質量份為佳。更佳者為1質量份~50質量份。 The content of the crosslinkable compound in the liquid crystal alignment treatment agent of the present invention is preferably 0.1 to 150 parts by mass relative to 100 parts by mass of the entire polymer component. Among them, from the viewpoint of the effect that the crosslinking reaction can achieve the purpose, etc., it is preferably 0.1 to 100 parts by mass relative to 100 parts by mass of the entire polymer component. More preferred is 1 to 50 parts by mass.

本發明之液晶配向處理劑，於無損本發明之效果之範圍，於塗佈液晶配向處理劑之際，可使用提高液晶配向膜的膜厚均勻性或表面平滑性等化合物。 The liquid crystal alignment treatment agent of the present invention can use a compound that improves the uniformity of the film thickness of the liquid crystal alignment film or the surface smoothness when the liquid crystal alignment treatment agent is applied, so long as the effect of the present invention is not impaired.

提高液晶配向膜的膜厚均勻性或表面平滑性之化合物，例如，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。 Compounds that improve the uniformity or surface smoothness of the liquid crystal alignment film, for example, fluorine-based surfactants, polysiloxane-based surfactants, and non-ionic surfactants.

更具體而言，例如，F-Top EF301、EF303、EF352(以上，道康寧化學製程公司製)、MEGAFACE F171、F173、R-30(以上，大日本塗料公司製)、FLUORAD FC430、FC431(以上，住友3M公司製)、AsahiGuard AG710、SurflonS-382、SC101、SC102、SC103、SC104、SC105、SC106(以上，旭硝子公司製)等。 More specifically, for example, F-Top EF301, EF303, EF352 (above, manufactured by Dow Corning Chemical Process Company), MEGAFACE F171, F173, R-30 (above, manufactured by Dainippon Paint Co., Ltd.), FLUORAD FC430, FC431 (above, (Made by Sumitomo 3M), AsahiGuard AG710, SurflonS-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.), etc.

該些界面活性劑之使用比例，相對於液晶配向處理劑所含有的全部聚合物成份100質量份，較佳為 0.01質量份~2質量份、更佳為0.01質量份~1質量份。 The use ratio of these surfactants is preferably 100 parts by mass with respect to all polymer components contained in the liquid crystal alignment treatment agent. 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass.

此外，本發明之液晶配向處理劑中，作為促進液晶配向膜中之電荷移動所使用的促進元件解除電荷之化合物，可添加國際公開公報WO2011/132751(2011.10.27公開)之69頁~73頁所揭示之式〔M1〕~式〔M156〕所示含氮雜環之胺化合物。此胺化合物，可直接添加於液晶配向處理劑中亦可，可以適當之溶劑調整為濃度0.1質量%~10質量%，較佳為1質量%~7質量%之溶液方式添加為佳。此溶劑只要可溶解上述特定聚合物(A)及特定聚合物(B)之溶劑時，並未有特別之限定。 In addition, in the liquid crystal alignment treatment agent of the present invention, as a compound that promotes charge removal in the liquid crystal alignment film to promote charge removal of the element, pages 69 to 73 of International Publication WO2011 / 132751 (published on 2011.10.27) can be added. The disclosed formulas [M1] to [M156] are nitrogen-containing heterocyclic amine compounds. This amine compound may be directly added to the liquid crystal alignment treatment agent. It may be adjusted by a suitable solvent to a concentration of 0.1 mass% to 10 mass%, preferably 1 mass% to 7 mass% in a solution manner. This solvent is not particularly limited as long as it can dissolve the solvent of the specific polymer (A) and the specific polymer (B).

本發明之液晶配向處理劑中，除上述貧溶劑、交聯性化合物、提高樹脂被膜或液晶配向膜的膜厚均勻性或表面平滑性的化合物及促進解除電荷之化合物以外，只要為不損害本發明效果之範圍，可添加以改變液晶配向膜的介電係數或導電性等電氣特性為目的的介電體或導電物質。 In the liquid crystal alignment treatment agent of the present invention, in addition to the above-mentioned poor solvents, crosslinkable compounds, compounds that improve the film thickness uniformity or surface smoothness of the resin film or liquid crystal alignment film, and compounds that promote de-charge, as long as they do not harm the present invention The range of the effect of the invention may include a dielectric body or a conductive substance for the purpose of changing electrical characteristics such as the dielectric constant and conductivity of the liquid crystal alignment film.

<液晶配向膜‧液晶顯示元件> <Liquid crystal alignment film and liquid crystal display element>

本發明之液晶配向處理劑為，於塗佈、燒結於基板上之後，可經施以摩擦處理或光照射等配向處理，而作為液晶配向膜使用者。又，於垂直配向等用途之情形中，亦可不施以配向處理而作為液晶配向膜使用。此時所使用之基板，只要為具有高度透明性之基板時，並未有特別之限 定，除玻璃基板以外，其他亦可使用丙烯酸基板或聚碳酸酯基板等塑膠基板等。就製程簡單化之觀點，就進行液晶驅動之觀點，以使用形成有ITO電極等之基板為佳。又，為反射型之液晶顯示元件中，若僅為單側之基板時，亦可使用矽晶圓等不透明之基板，該情形之電極，亦可使用鋁等反射光線之材料。 After the liquid crystal alignment treatment agent of the present invention is applied and sintered on a substrate, it can be subjected to an alignment treatment such as rubbing treatment or light irradiation to serve as a liquid crystal alignment film user. In addition, in the case of applications such as vertical alignment, it may be used as a liquid crystal alignment film without applying alignment treatment. The substrate used at this time is not particularly limited as long as it is a substrate having high transparency. In addition to glass substrates, plastic substrates such as acrylic substrates and polycarbonate substrates can also be used. From the viewpoint of simplification of the process and from the viewpoint of driving the liquid crystal, it is preferable to use a substrate formed with an ITO electrode or the like. In the case of a reflective liquid crystal display element, if it is only a single-sided substrate, an opaque substrate such as a silicon wafer may be used. In this case, an electrode such as aluminum may be used as a material that reflects light.

液晶配向處理劑之塗佈方法，並未有特別之限定，工業上，一般可使用網版印刷、平版印刷、凸版印刷或噴墨法等方式進行。其他之塗佈方法，例如，浸漬法、輥塗佈法、縫狀塗佈法、旋轉法或噴霧法等，其可配合目的而使用該些方法使用即可。 The application method of the liquid crystal alignment treatment agent is not particularly limited, and industrially, it can generally be performed by screen printing, lithography, letterpress printing, or inkjet. Other coating methods, such as a dipping method, a roll coating method, a slit coating method, a spin method, or a spray method, may be used in accordance with the purpose.

液晶配向處理劑塗佈於基板上之後，可使用加熱板、熱循環型烘箱或IR(紅外線)型烘箱等加熱手段，配合液晶配向處理劑所使用的溶劑，於30~300℃，較佳為30~250℃之溫度，使溶劑蒸發而形成液晶配向膜。燒結後的液晶配向膜之厚度，若過厚時就液晶顯示元件的消費電力之觀點而言為不利，過薄時將會造成液晶顯示元件信賴性降低等情形，故較佳為5~300nm，更佳為10~100nm。欲使液晶成為水平配向或傾斜配向之情形，可對燒結後的液晶配向膜進行摩擦或偏光紫外線照射等方式進行處理。 After the liquid crystal alignment treatment agent is coated on the substrate, heating means such as a hot plate, a thermal cycle type oven, or an IR (infrared) type oven can be used, and the solvent used for the liquid crystal alignment treatment agent is 30 to 300 ° C, preferably At a temperature of 30 to 250 ° C, the solvent is evaporated to form a liquid crystal alignment film. If the thickness of the sintered liquid crystal alignment film is too thick, it is disadvantageous from the viewpoint of the power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element will be reduced. Therefore, it is preferably 5 to 300 nm. More preferably, it is 10 to 100 nm. If the liquid crystal is to be aligned horizontally or obliquely, the sintered liquid crystal alignment film may be processed by rubbing or polarizing ultraviolet rays.

本發明之液晶顯示元件，可依上述之手法，本發明之液晶配向處理劑製得附有液晶配向膜之基板之後，再依公知方法製作液晶晶胞而作為液晶顯示元件。 According to the liquid crystal display element of the present invention, a substrate with a liquid crystal alignment film is prepared by the liquid crystal alignment treatment agent of the present invention according to the method described above, and then a liquid crystal cell is produced according to a known method as a liquid crystal display element.

液晶晶胞之製作方法，可例如，準備形成有液晶配向膜的一對之基板，於一側的基板之液晶配向膜上散佈間隔器，使液晶配向膜面為內側之方式，將另一側的基板貼合，並減壓注入液晶後予以密封之方法，或，將液晶滴入散佈有間隔器之液晶配向膜面之後，再貼合基板進行密封之方法等例示。 The method for manufacturing a liquid crystal cell may be, for example, preparing a pair of substrates on which a liquid crystal alignment film is formed, and spreading a spacer on the liquid crystal alignment film of the substrate on one side so that the liquid crystal alignment film surface is inside, and the other side A method of laminating substrates and injecting liquid crystals under reduced pressure and sealing them, or a method of sealing the substrates by dripping liquid crystals onto the liquid crystal alignment film surface on which the spacers are dispersed, and then sealing the substrates.

如以上所述般，本發明之液晶配向處理劑，為具有優良保存安定性之液晶配向處理劑，且，於液晶配向處理劑塗佈於基板上之際，可抑制聚合物成份的白化‧凝聚現象，而可得到具有優良塗膜均勻性之液晶配向膜。此外，除具有良好初期特性以外，即使長時間暴露於光線照射之後，也可以抑制電壓保持率之下降的液晶配向膜。因此，具有由本發明之液晶配向處理劑所得之液晶配向膜的液晶顯示元件，為具有優良信賴性者，而適合被使用於大畫面且高精密的液晶電視，或中小型汽車導航系統或智慧型手機等。 As described above, the liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment treatment agent with excellent storage stability, and when the liquid crystal alignment treatment agent is coated on a substrate, whitening and aggregation of polymer components can be suppressed. Phenomenon, and a liquid crystal alignment film having excellent coating film uniformity can be obtained. In addition, in addition to having good initial characteristics, a liquid crystal alignment film that can suppress a decrease in voltage retention even after long-term exposure to light irradiation. Therefore, a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is a person with excellent reliability, and is suitable for being used in a large-screen and high-precision liquid crystal television, or a small and medium-sized car navigation system or a smart type. Mobile phone, etc.

〔實施例〕 [Example]

以下將列舉實施例對本發明作更詳細之說明，但並不僅限定於該些內容。 The following examples are used to describe the present invention in more detail, but are not limited to these contents.

「本發明之合成例、實施例及比較例所使用之簡稱」 "Abbreviations used in the synthesis examples, examples, and comparative examples of the present invention"

合成例、實施例及比較例所使用之簡稱，係如以下所 示。 Abbreviations used in Synthesis Examples, Examples and Comparative Examples are as follows Show.

<製作本發明之聚醯亞胺系聚合物所使用的單體> <Monomer used for production of polyfluorene-based polymer of the present invention> (本發明之特定二胺化合物(1)) (Specific diamine compound (1) of the present invention)

A1：下述式〔A1〕所示二胺化合物 A1: a diamine compound represented by the following formula [A1]

A2：下述式〔A2〕所示二胺化合物 A2: a diamine compound represented by the following formula [A2]

(本發明之特定二胺化合物(2)) (Specific diamine compound (2) of the present invention)

B1：下述式〔B1〕所示二胺化合物 B1: a diamine compound represented by the following formula [B1]

(其他二胺化合物) (Other diamine compounds)

C1：p-伸苯基二胺 C1: p-phenylene diamine

C2：下述式〔C2〕所示二胺化合物 C2: a diamine compound represented by the following formula [C2]

C3：下述式〔C3〕所示二胺化合物 C3: a diamine compound represented by the following formula [C3]

(本發明之特定四羧酸成份) (Specific tetracarboxylic acid component of the present invention)

D1：1,2,3,4-環丁烷四羧酸二酐 D1: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

D2：雙環〔3,3,0〕辛烷-2,4,6,8-四羧酸二酐 D2: Bicyclic [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride

D3：下述式〔D3〕所示四羧酸二酐 D3: tetracarboxylic dianhydride represented by the following formula [D3]

(其他四羧酸成份) (Other tetracarboxylic acid ingredients)

E1：苯均四酸二酐 E1: pyromellitic dianhydride

「本發明所使用之交聯性化合物」 "Crosslinkable compound used in the present invention"

K1：下述式〔K1〕所示交聯性化合物 K1: a crosslinkable compound represented by the following formula [K1]

「本發明所使用之溶劑」 "Solvents used in the present invention"

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

γ-BL：γ-丁內酯 γ-BL: γ-butyrolactone

BCS：乙二醇單丁醚 BCS: ethylene glycol monobutyl ether

DPM：二丙二醇單甲醚 DPM: Dipropylene glycol monomethyl ether

「本發明之聚醯亞胺系聚合物分子量之測定」 "Determination of molecular weight of polyimide-based polymer of the present invention"

合成例中之聚醯亞胺前驅體及聚醯亞胺之分子量，為使用常溫凝膠滲透色層分析儀(GPC)裝置(GPC-101)(昭和電工公司製)、管柱(KD-803，KD-805)(Shodex公司製)，依以下方式測定者。 The molecular weights of the polyimide precursor and polyimide in the synthesis examples are a normal temperature gel permeation chromatography (GPC) device (GPC-101) (manufactured by Showa Denko Corporation) and a column (KD-803 , KD-805) (manufactured by Shodex), and measured in the following manner.

管柱溫度：50℃ Column temperature: 50 ℃

溶離液：N,N’-二甲基甲醯胺(添加劑為，溴化鋰-水和物(LiBr‧H2O)為30mmol/L(公升)、磷酸‧無水結晶(o-磷酸)為30mmol/L、四氫呋喃(THF)為10ml/L) Eluent: N, N'-dimethylformamide (additive: lithium bromide-water compound (LiBr‧H 2 O): 30mmol / L (liter); phosphoric acid‧anhydrous crystal (o-phosphoric acid): 30mmol / L L, tetrahydrofuran (THF) is 10ml / L)

流速：1.0ml/分 Flow rate: 1.0ml / min

檢量線製作用之標準樣品：TSK標準聚氧乙烯(分子量；約900,000、150,000、100,000及30,000)(東曹公司製)及聚乙二醇(分子量；約12,000、4,000及1,000)(Polymer Laboratories公司製)。 Standard samples for calibration line production: TSK standard polyoxyethylene (molecular weight; approximately 900,000, 150,000, 100,000, and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; approximately 12,000, 4,000, and 1,000) (Polymer Laboratories Company).

「本發明之聚醯亞胺的醯亞胺化率之測定」 "Determination of the hydrazone imidization rate of the polyfluorene imide of the present invention"

合成例中之聚醯亞胺的醯亞胺化率係依下式測定者。即，將聚醯亞胺粉末20mg置入NMR(核磁共振)採樣管(NMR標準採樣管， 5(草野科學公司製))，添加氘代二甲基亞碸(DMSO-d6，0.05質量%TMS(四甲基矽烷)混合品)(0.53ml)，施以超音波使其完全溶解。使用NMR測定機(JNW-ECA500)(日本電子DATUM公司製)測定此溶液的500MHz之質子NMR。醯亞胺化率為，以醯亞胺化前後未變化的結構所產生之質子作為基準質子予以決定，使用此質子的波峰積算值，與9.5ppm~10.0ppm附近出現的醯胺酸的NH基所產生的質子波峰積算值，並依下式求得者。 The polyimide imidization ratio in the synthesis example was measured according to the following formula. That is, 20 mg of polyfluorene imine powder was placed in an NMR (nuclear magnetic resonance) sampling tube (NMR standard sampling tube, 5 (manufactured by Kusano Science Co., Ltd.)), deuterated dimethylsulfinium (DMSO-d6, 0.05% by mass TMS (tetramethylsilane) mixed product) (0.53 ml) was added, and ultrasound was applied to completely dissolve it. A 500 MHz proton NMR of this solution was measured using an NMR measuring machine (JNW-ECA500) (manufactured by Japan Electronics DATUM). The hydrazone imidization rate is determined by using protons generated by the structure that has not changed before and after hydrazone imidization as the reference protons. The peak value of this proton is used to calculate the NH group of sulfamic acid that appears near 9.5 ppm to 10.0 ppm. The resulting proton wave integrated value is obtained by the following formula.

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

上述式中，x為由醯胺酸的NH基產生的質子波峰積算值、y為基準質子的波峰積算值、α為聚醯胺酸(醯亞胺化率為0%)之情形中，相對於醯胺酸的1個NH基質子之基準質子的個數比例。 In the above formula, in the case where x is the integrated value of the proton peak generated by the NH group of the amino acid, y is the integrated value of the peak of the reference proton, and α is the poly (aminoimidization rate of 0%), Proportion of the number of reference protons per NH matrix proton in ammonium acid.

「本發明之聚醯亞胺系聚合物之合成」 "Synthesis of Polyimide Polymers of the Present Invention" <合成例1> <Synthesis example 1>

將D3(13.5g，45.0mmol)、B1(2.69g，9.02mmol)、C1(3.40g，31.4mmol)及C3(1.56g，4.48mmol)於NMP(84.7g)中混合，於40℃下反應20小時，製得樹脂固形分濃度為20質量%的聚醯胺酸溶液。此聚醯胺酸於溫度25℃下的黏度為900mPa‧s。 D3 (13.5g, 45.0mmol), B1 (2.69g, 9.02mmol), C1 (3.40g, 31.4mmol) and C3 (1.56g, 4.48mmol) were mixed in NMP (84.7g) and reacted at 40 ° C In 20 hours, a polyamic acid solution having a resin solid content concentration of 20% by mass was prepared. The viscosity of this polyamidic acid at a temperature of 25 ° C was 900 mPa‧s.

將NMP(200.0g)加入所得聚醯胺酸溶液(80.0g)稀釋後，加入作為醯亞胺化觸媒之乙酸酐(36.5g)及吡啶(17.0g)，於40℃下反應3小時。將此反應溶液投入甲醇(1170ml)中，濾出所得沈澱物。此沈澱物以甲醇洗淨，於100℃下減壓乾燥，而製得聚醯亞胺粉末(1)。此聚醯亞胺的醯亞胺化率為85%，數平均分子量為11,900、重量平均分子量為28,500。 After NMP (200.0 g) was added to the obtained polyamic acid solution (80.0 g) and diluted, acetic anhydride (36.5 g) and pyridine (17.0 g) were added as the imidization catalyst, and the reaction was carried out at 40 ° C for 3 hours. This reaction solution was poured into methanol (1170 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (1). The polyimide has a hydrazone imidation rate of 85%, a number average molecular weight of 11,900, and a weight average molecular weight of 28,500.

<合成例2> <Synthesis example 2>

將D2(2.25g，8.99mmol)、D3(10.8g，36.0mmol)、B1(2.68g，8.98mmol)、C1(3.40g，31.4mmol)及C3(1.57g，4.50mmol)於NMP(82.9g)中混合，於40℃下反應24小時，製得樹脂固形分濃度為20質量%的聚醯胺酸溶液。此聚醯胺酸於溫度25℃下的黏度為980mPa‧s。 D2 (2.25g, 8.99mmol), D3 (10.8g, 36.0mmol), B1 (2.68g, 8.98mmol), C1 (3.40g, 31.4mmol) and C3 (1.57g, 4.50mmol) in NMP (82.9g ), And reacted at 40 ° C. for 24 hours to prepare a polyamidic acid solution having a resin solid content concentration of 20% by mass. The viscosity of this polyamidic acid at a temperature of 25 ° C was 980 mPa · s.

將NMP(200.0g)加入所得聚醯胺酸溶液(80.0g)稀釋後，加入作為醯亞胺化觸媒之乙酸酐 (37.2g)及吡啶(17.3g)，於40℃下反應3小時。將此反應溶液投入甲醇(1170ml)中，濾出所得沈澱物。此沈澱物以甲醇洗淨，於100℃下減壓乾燥，而製得聚醯亞胺粉末(2)。此聚醯亞胺的醯亞胺化率為65%，數平均分子量為10,200、重量平均分子量為21,500。 NMP (200.0g) was added to the obtained polyamidic acid solution (80.0g) and diluted, and then acetic anhydride was added as a phosphonium imidization catalyst. (37.2 g) and pyridine (17.3 g), and reacted at 40 ° C for 3 hours. This reaction solution was poured into methanol (1170 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (2). The polyimide has a fluorene imidation ratio of 65%, a number average molecular weight of 10,200, and a weight average molecular weight of 21,500.

<合成例3> <Synthesis example 3>

將D1(3.92g，20.0mmol)、E1(3.66g，16.8mmol)、A2(2.55g，12.0mmol)及C2(5.55g，28.0mmol)於NMP(44.2g)及γ-BL(44.2g)中混合，於25℃下反應2小時，製得樹脂固形分濃度15質量%之聚醯胺酸溶液(3)。此聚醯胺酸於溫度25℃下的黏度為340mPa‧s。又，此聚醯胺酸的數平均分子量為14,200、重量平均分子量為29,900。 D1 (3.92g, 20.0mmol), E1 (3.66g, 16.8mmol), A2 (2.55g, 12.0mmol) and C2 (5.55g, 28.0mmol) in NMP (44.2g) and γ-BL (44.2g) The mixture was mixed at room temperature and reacted at 25 ° C for 2 hours to obtain a polyamic acid solution (3) having a resin solid content concentration of 15% by mass. The viscosity of this polyamic acid at a temperature of 25 ° C was 340 mPa · s. The number average molecular weight of this polyamic acid was 14,200, and the weight average molecular weight was 29,900.

<合成例4> <Synthesis example 4>

將D1(3.92g，20.0mmol)、E1(3.66g，16.8mmol)、A1(2.39g，12.0mmol)及C2(5.55g，28.0mmol)於NMP(44.2g)及γ-BL(44.2g)中混合，於25℃下反應2小時，製得樹脂固形分濃度15質量%之聚醯胺酸溶液(4)。此聚醯胺酸於溫度25℃下的黏度為330mPa‧s。又，此聚醯胺酸的數平均分子量為13,300、重量平均分子量為27,900。 D1 (3.92g, 20.0mmol), E1 (3.66g, 16.8mmol), A1 (2.39g, 12.0mmol) and C2 (5.55g, 28.0mmol) in NMP (44.2g) and γ-BL (44.2g) The mixture was mixed with the mixture and reacted at 25 ° C for 2 hours to obtain a polyamic acid solution (4) having a resin solid content concentration of 15% by mass. The viscosity of this polyamic acid at a temperature of 25 ° C was 330 mPa · s. The number average molecular weight of this polyamic acid was 13,300, and the weight average molecular weight was 27,900.

<合成例5> <Synthesis example 5>

將D1(5.65g，28.8mmol)、D3(2.40g，7.99mmol)、A1(6.38g，32.0mmol)及C2(1.58g，7.97mmol)於NMP(44.2g)及γ-BL(44.2g)中混合，於25℃下反應2小時，製得樹脂固形分濃度10質量%之聚醯胺酸溶液(5)。此聚醯胺酸於溫度25℃下的黏度為170mPa‧s。又，此聚醯胺酸的數平均分子量為16,700、重量平均分子量為35,700。 D1 (5.65g, 28.8mmol), D3 (2.40g, 7.99mmol), A1 (6.38g, 32.0mmol) and C2 (1.58g, 7.97mmol) in NMP (44.2g) and γ-BL (44.2g) The mixture was mixed with the mixture and reacted at 25 ° C for 2 hours to prepare a polyamic acid solution (5) having a resin solid content concentration of 10% by mass. The viscosity of this polyamic acid at a temperature of 25 ° C was 170 mPa · s. The number average molecular weight of this polyamidic acid was 16,700, and the weight average molecular weight was 35,700.

<合成例6> <Synthesis example 6>

將D3(14.4g，48.0mmol)、C1(4.67g，43.2mmol)及C3(1.67g，4.79mmol)於NMP(83.0g)中混合，於40℃下反應20小時，製得樹脂固形分濃度為20質量%的聚醯胺酸溶液。此聚醯胺酸於溫度25℃下的黏度為890mPa‧s。 D3 (14.4g, 48.0mmol), C1 (4.67g, 43.2mmol) and C3 (1.67g, 4.79mmol) were mixed in NMP (83.0g), and reacted at 40 ° C for 20 hours to obtain the solid content concentration of the resin It is a 20% by mass polyamic acid solution. The viscosity of this polyamic acid at a temperature of 25 ° C was 890 mPa · s.

將NMP(200.0g)加入所得聚醯胺酸溶液(80.0g)稀釋後，加入作為醯亞胺化觸媒之乙酸酐(41.7g)及吡啶(19.1g)，於40℃下反應3小時。將此反應溶液投入甲醇(1190ml)中，濾出所得沈澱物。此沈澱物以甲醇洗淨，於100℃下減壓乾燥，而製得聚醯亞胺粉末(6)。此聚醯亞胺的醯亞胺化率為85%，數平均分子量為10,300、重量平均分子量為22,800。 After NMP (200.0 g) was added to the obtained polyamidic acid solution (80.0 g) and diluted, acetic anhydride (41.7 g) and pyridine (19.1 g) were added as the imidization catalyst, and the reaction was carried out at 40 ° C for 3 hours. This reaction solution was poured into methanol (1190 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (6). The polyimide has a fluorene imidization rate of 85%, a number average molecular weight of 10,300, and a weight average molecular weight of 22,800.

<合成例7> <Synthesis example 7>

將D1(3.92g，20.0mmol)、E1(3.66g，16.8mmol)及C2(7.93g，40.0mmol)於NMP(44.2g)及γ-BL(44.2g)中混合，於25℃下反應2小時，製得樹脂固形分濃度15質量%之聚醯胺酸溶液(7)。此聚醯胺酸於溫度25℃下的黏度為330mPa‧s。又，此聚醯胺酸的數平均分子量為13,600、重量平均分子量為34,200。 D1 (3.92g, 20.0mmol), E1 (3.66g, 16.8mmol) and C2 (7.93g, 40.0mmol) were mixed in NMP (44.2g) and γ-BL (44.2g), and reacted at 25 ° C. 2 After 1 hour, a polyamic acid solution (7) having a resin solid content concentration of 15% by mass was prepared. The viscosity of this polyamic acid at a temperature of 25 ° C was 330 mPa · s. The number average molecular weight of this polyamic acid was 13,600, and the weight average molecular weight was 34,200.

本發明之聚醯亞胺系聚合物係如表2所示。 The polyimide-based polymer of the present invention is shown in Table 2.

＊ 1：聚醯胺酸。* 1: Polyamic acid.

「本發明之液晶配向處理劑之製造」 "Manufacture of liquid crystal alignment treatment agent of the present invention"

下述實施例1~實施例6及比較例1~比較例3中，為記載液晶配向處理劑之製造例。又，該液晶配向處理劑，亦被使用於評估內容中。 The following Examples 1 to 6 and Comparative Examples 1 to 3 describe production examples of the liquid crystal alignment treatment agent. The liquid crystal alignment treatment agent was also used for evaluation.

本發明之液晶配向處理劑係如表3及表4所示。 The liquid crystal alignment treatment agent of the present invention is shown in Tables 3 and 4.

使用本發明之實施例及比較例所得之液晶配向處理劑，進行「液晶配向處理劑的保存安定性之評估」、「液晶配向處理劑之白化‧凝聚之評估」及「電壓保持率之評估」。 Using the liquid crystal alignment treatment agents obtained in the examples and comparative examples of the present invention, "evaluation of storage stability of the liquid crystal alignment treatment agent", "evaluation of whitening and agglomeration of the liquid crystal alignment treatment agent", and "evaluation of the voltage holding ratio" .

「液晶配向處理劑的保存安定性之評估」 "Assessment of Storage Stability of Liquid Crystal Alignment Treatment Agent"

將本發明之實施例及比較例所得之液晶配向處理劑，使用細孔徑1μm的膜式過濾器進行加壓過濾，於-15℃下保管48小時。隨後，以目視觀察方式，確認液晶配向處理劑中是否產生混濁或析出物。 The liquid crystal alignment treatment agents obtained in the examples and comparative examples of the present invention were subjected to pressure filtration using a membrane filter having a pore size of 1 μm, and stored at -15 ° C. for 48 hours. Subsequently, it was confirmed by visual observation whether turbidity or precipitates were generated in the liquid crystal alignment treatment agent.

表5及表6中，為標記實施例及比較例所得之結果。又，表中，未發現混濁、析出物而呈均勻溶液者標記為○，發現混濁或析出物者標記為×。 Tables 5 and 6 show the results obtained in the marked examples and comparative examples. In addition, in the table, those who did not find turbidity or precipitates and found a homogeneous solution were marked as ○, and those who found turbidity or precipitates were marked as ×.

又，將上述於-15℃下保管48小時之液晶配向處理劑，旋轉塗佈於經進行純水及IPA洗淨之附有30×40mmITO電極的基板(縱40mm×橫30mm、厚度0.7mm)之ITO面上，於加熱板上進行100℃、5分鐘加熱處理，而製得附有液晶配向膜之ITO基板。隨後，評估所製得之附有液晶配向膜的基板上之沙孔。 In addition, the liquid crystal alignment treatment agent stored at -15 ° C for 48 hours was spin-coated on a substrate with a 30 × 40 mm ITO electrode (40 mm in height × 30 mm in width and 0.7 mm in thickness) washed with pure water and IPA. The ITO surface was heated at 100 ° C. for 5 minutes on a hot plate to prepare an ITO substrate with a liquid crystal alignment film. Subsequently, the sand holes on the substrate with the liquid crystal alignment film produced were evaluated.

評估，為於鈉燈下以目視方式觀察此基板。具體而言，計算於附有液晶配向膜之基板上所觀察之沙孔數目，沙孔之數目越少時，表示液晶配向處理劑中之析出物越少，於本評估中評定為優(表5及表6中為標記沙孔之數目)。 Evaluation is to visually observe this substrate under a sodium lamp. Specifically, the number of sand holes observed on the substrate with the liquid crystal alignment film is calculated. When the number of sand holes is smaller, it means that there are fewer precipitates in the liquid crystal alignment treatment agent, which is evaluated as excellent in this evaluation (Table 5 and Table 6 are the number of marked sand holes).

表5及表6中，為標記實施例及比較例所得之結果。 Tables 5 and 6 show the results obtained in the marked examples and comparative examples.

「液晶配向處理劑之白化‧凝聚之評估」 "Whitening and coagulation evaluation of liquid crystal alignment treatment agent"

將本發明之實施例及比較例所得之液晶配向處理劑，使用細孔徑1μm的膜式過濾器進行加壓過濾，滴入1ml於100×100mm之Cr基板上。隨後，將其放置於溫度27℃、濕度65%之環境下，測定滴下之液晶配向處理劑至產生混濁(白化‧凝聚)為止之時間。 The liquid crystal alignment treatment agents obtained in the examples and comparative examples of the present invention were subjected to pressure filtration using a membrane filter having a pore diameter of 1 μm, and 1 ml was dropped on a 100 × 100 mm Cr substrate. Then, it was left to stand in an environment with a temperature of 27 ° C and a humidity of 65%, and the time from the dropping of the liquid crystal alignment treatment agent to turbidity (whitening and agglomeration) was measured.

評估結果為，產生混濁為止之時間越長時，表示液晶配向處理劑之白化‧凝聚特性為良好之意(表5及表6為標示時間)。 As a result of the evaluation, the longer the time until turbidity occurred, the better the whitening and agglomeration characteristics of the liquid crystal alignment treatment agent (Tables 5 and 6 indicate the time).

表5及表6中，為標記實施例及比較例所得之結果。 Tables 5 and 6 show the results obtained in the marked examples and comparative examples.

「電壓保持率之評估」 `` Evaluation of voltage holding ratio ''

將本發明之實施例及比較例所得之液晶配向處理劑，使用細孔徑1μm的膜式過濾器進行加壓過濾後，旋轉塗佈於經進行純水及IPA洗淨之40×30mm附有ITO電極之基板(縱40mm×橫30mm、厚度0.7mm)之ITO面，於加熱板上以80℃進行90秒、IR(紅外線)型無塵烘箱中以230℃進行15分鐘加熱處理，製得膜厚為100nm的附有聚醯亞胺液晶配向膜之ITO基板。 The liquid crystal alignment treatment agents obtained in the examples and comparative examples of the present invention were subjected to pressure filtration using a membrane filter with a pore size of 1 μm, and then spin-coated on 40 × 30 mm with ITO washed with pure water and IPA. The ITO surface of the electrode substrate (40mm in height × 30mm in width and 0.7mm in thickness) was heated on a hot plate at 80 ° C for 90 seconds and IR (infrared) type dust-free oven was heated at 230 ° C for 15 minutes to obtain a film. 100 nm thick ITO substrate with polyfluorene imide liquid crystal alignment film.

將此ITO基板的塗膜面置於滾筒徑為120mm 之摩擦裝置，使用棉布，以滾筒迴轉數為1000rpm、滾筒進行速度為35mm/sec、加壓量為0.7mm之條件下進行摩擦處理。 Place the coating film side of this ITO substrate on a roller diameter of 120mm The friction device uses cotton cloth to perform a rubbing treatment under the conditions that the number of revolutions of the drum is 1000 rpm, the speed of the drum is 35 mm / sec, and the amount of pressure is 0.7 mm.

準備2片此附有液晶配向膜的ITO基板，將液晶配向膜面設為內側之方式，製作組合有挾夾4μm的間隔器，使用密封劑黏著周圍所得之空晶胞。將MLC-3018U(默克‧日本公司製)使用減壓注入法注入此空晶胞內，密封注入口而製得液晶晶胞。 Two pieces of the ITO substrate with a liquid crystal alignment film were prepared, and the liquid crystal alignment film surface was set to the inside. A spacer having a 4 μm clip was assembled, and a surrounding empty cell was adhered with a sealant. MLC-3018U (manufactured by Merck, Japan) was injected into the empty cell using a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell.

使用所得之液晶晶胞，進行電壓保持率之評估。具體而言，於90℃之溫度下施加60μs之4V的電壓，測定166.7ms後之電壓，計算電壓能保持之程度作為電壓保持率(亦稱為VHR)。又，測定為使用電壓保持率測定裝置(VHR-1)(東陽科技公司製)，於Voltage：±1V、Pulse Width：60μs、Flame Period：166.7ms之設定下進行。 The obtained liquid crystal cell was used to evaluate the voltage holding ratio. Specifically, a voltage of 4 V of 60 μs was applied at a temperature of 90 ° C., and the voltage after 166.7 ms was measured, and the degree to which the voltage can be maintained was calculated as a voltage holding rate (also referred to as VHR). The measurement was performed using a voltage holding ratio measuring device (VHR-1) (manufactured by Toyo Technology Co., Ltd.) and was performed under the settings of Voltage: ± 1 V, Pulse Width: 60 μs, and Flame Period: 166.7 ms.

此外，使用桌上型UV硬化裝置(HCT3B28HEX-1)(SEN LIGHT公司製)，以365nm換算為5J/cm2之紫外線照射經測定上述液晶晶胞製作後之即時電壓保持率後的液晶晶胞，並依與上述相同條件下進行電壓保持率之測定。 In addition, using a desktop UV curing device (HCT3B28HEX-1) (manufactured by SEN Light), the liquid crystal cell was measured by measuring the instantaneous voltage holding ratio of the liquid crystal cell after the ultraviolet ray was converted at a wavelength of 365 nm into 5 J / cm 2 . , And under the same conditions as above to measure the voltage retention rate.

評估結果為，液晶晶胞製作後立即之電壓保持率之值為較高，且，對於液晶晶胞製作後立即測得之電壓保持率之值而言，紫外線照射後之數值降低度越小時，表示為良好(表5及表6中，為表示液晶晶胞製作後立即 及紫外線照射後之VHR之數值)。 As a result of the evaluation, the value of the voltage retention rate immediately after the liquid crystal cell was manufactured was higher, and the smaller the value of the value of the voltage retention rate measured immediately after the liquid crystal cell was manufactured after the ultraviolet irradiation was decreased, Indicated as good (in Tables 5 and 6, it means that the liquid crystal cell immediately after fabrication And the value of VHR after UV irradiation).

表5及表6中，為標記實施例及比較例所得之結果。 Tables 5 and 6 show the results obtained in the marked examples and comparative examples.

<實施例1> <Example 1>

於合成例1之合成手法所得之聚醯亞胺粉末(1)(3.00g)中，加入NMP(11.0g)及γ-BL(11.0g)，以50℃攪拌20小時，使其溶解。於此溶液中，加入NMP(4.00g)、γ-BL(6.00g)、BCS(10.0g)及DPM(5.00g)，於50℃下攪拌20小時，製得聚合物溶液。 NMP (11.0 g) and γ-BL (11.0 g) were added to the polyfluorene imine powder (1) (3.00 g) obtained by the synthesis method of Synthesis Example 1, and the mixture was stirred at 50 ° C for 20 hours to be dissolved. To this solution, NMP (4.00 g), γ-BL (6.00 g), BCS (10.0 g), and DPM (5.00 g) were added and stirred at 50 ° C for 20 hours to obtain a polymer solution.

另外，添加NMP，使依合成例3之合成手法所得之聚醯胺酸溶液(3)中的樹脂固形分濃度達6質量%，而製得聚合物溶液。 In addition, NMP was added so that the concentration of the resin solid content in the polyamic acid solution (3) obtained according to the synthesis method of Synthesis Example 3 was 6% by mass, thereby preparing a polymer solution.

隨後，將前述2個聚合物溶液混合，於該溶液中加入K1(0.15g)，以25℃攪拌20小時，得液晶配向處理劑(1)。此液晶配向處理劑中，未發現混濁或析出等異常現象，而確認為均勻之溶液。 Subsequently, the two polymer solutions were mixed, K1 (0.15 g) was added to the solution, and the mixture was stirred at 25 ° C. for 20 hours to obtain a liquid crystal alignment treatment agent (1). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, but it was confirmed to be a uniform solution.

使用所得之液晶配向處理劑(1)，進行「液晶配向處理劑的保存安定性之評估」、「液晶配向處理劑之白化‧凝聚之評估」及「電壓保持率之評估」。 Using the obtained liquid crystal alignment treatment agent (1), "evaluation of storage stability of the liquid crystal alignment treatment agent", "evaluation of whitening and agglomeration of the liquid crystal alignment treatment agent", and "evaluation of the voltage holding ratio" were performed.

<實施例2> <Example 2>

於依合成例1之合成手法所得之聚醯亞胺粉末(1)(3.00g)中，加入NMP(11.0g)及γ-BL(11.0g)，於 50℃下攪拌20小時，使其溶解。於此溶液中，加入NMP(4.00g)、γ-BL(6.00g)、BCS(10.0g)及DPM(5.00g)，於50℃下攪拌20小時，製得聚合物溶液。 NMP (11.0 g) and γ-BL (11.0 g) were added to the polyimide powder (1) (3.00 g) obtained according to the synthesis method of Synthesis Example 1. It stirred at 50 degreeC for 20 hours, and was made to melt | dissolve. To this solution, NMP (4.00 g), γ-BL (6.00 g), BCS (10.0 g), and DPM (5.00 g) were added and stirred at 50 ° C for 20 hours to obtain a polymer solution.

另外，添加NMP，使合成例4之合成手法所得之聚醯胺酸溶液(4)中之樹脂固形分濃度達6質量%，而製得聚合物溶液。 In addition, NMP was added so that the resin solid content concentration in the polyamic acid solution (4) obtained by the synthesis method of Synthesis Example 4 was 6% by mass, and a polymer solution was prepared.

隨後，將前述2個聚合物溶液混合，於該溶液中，加入K1(0.15g)，於25℃下攪拌20小時，而製得液晶配向處理劑(2)。此液晶配向處理劑中，未發現混濁或析出等異常現象，而確認為均勻之溶液。 Subsequently, the two polymer solutions were mixed, K1 (0.15 g) was added to the solution, and the mixture was stirred at 25 ° C. for 20 hours to prepare a liquid crystal alignment treatment agent (2). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, but it was confirmed to be a uniform solution.

使用所得之液晶配向處理劑(2)，進行「液晶配向處理劑的保存安定性之評估」、「液晶配向處理劑之白化‧凝聚之評估」及「電壓保持率之評估」。 Using the obtained liquid crystal alignment treatment agent (2), "evaluation of storage stability of the liquid crystal alignment treatment agent", "evaluation of whitening and agglomeration of the liquid crystal alignment treatment agent", and "evaluation of the voltage holding ratio" were performed.

<實施例3> <Example 3>

於依合成例1之合成手法所得之聚醯亞胺粉末(1)(3.00g)中，加入NMP(11.0g)及γ-BL(11.0g)，於50℃下攪拌20小時，使其溶解。於此溶液中，加入NMP(4.00g)、γ-BL(6.00g)、BCS(10.0g)及DPM(5.00g)，於50℃下攪拌20小時，製得聚合物溶液。 NMP (11.0 g) and γ-BL (11.0 g) were added to the polyimide powder (1) (3.00 g) obtained according to the synthesis method of Synthesis Example 1, and stirred at 50 ° C for 20 hours to dissolve it. . To this solution, NMP (4.00 g), γ-BL (6.00 g), BCS (10.0 g), and DPM (5.00 g) were added and stirred at 50 ° C for 20 hours to obtain a polymer solution.

另外，添加NMP，使依合成例5之合成手法所得之聚醯胺酸溶液(5)中之樹脂固形分濃度達6質量%，而製得聚合物溶液。 In addition, NMP was added so that the concentration of the resin solid content in the polyamic acid solution (5) obtained according to the synthesis method of Synthesis Example 5 was 6% by mass, thereby preparing a polymer solution.

隨後，將前述2個聚合物溶液混合，於該溶 液中，加入K1(0.15g)，於25℃下攪拌20小時，而製得液晶配向處理劑(3)。此液晶配向處理劑中，未發現混濁或析出等異常現象，而確認為均勻之溶液。 Subsequently, the two polymer solutions are mixed, To the solution, K1 (0.15 g) was added, and the mixture was stirred at 25 ° C for 20 hours to prepare a liquid crystal alignment treatment agent (3). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, but it was confirmed to be a uniform solution.

使用所得之液晶配向處理劑(3)，進行「液晶配向處理劑的保存安定性之評估」、「液晶配向處理劑之白化‧凝聚之評估」及「電壓保持率之評估」。 Using the obtained liquid crystal alignment treatment agent (3), "evaluation of storage stability of the liquid crystal alignment treatment agent", "evaluation of whitening and agglomeration of the liquid crystal alignment treatment agent", and "evaluation of voltage holding ratio" were performed.

<實施例4> <Example 4>

於依合成例2之合成手法所得之聚醯亞胺粉末(2)(3.00g)中，加入NMP(11.0g)及γ-BL(11.0g)，於50℃下攪拌20小時，使其溶解。於此溶液中，加入NMP(4.00g)、γ-BL(6.00g)、BCS(10.0g)及DPM(5.00g)，於50℃下攪拌20小時，製得聚合物溶液。 NMP (11.0 g) and γ-BL (11.0 g) were added to the polyimide powder (2) (3.00 g) obtained according to the synthesis method of Synthesis Example 2, and stirred at 50 ° C for 20 hours to dissolve it. . To this solution, NMP (4.00 g), γ-BL (6.00 g), BCS (10.0 g), and DPM (5.00 g) were added and stirred at 50 ° C for 20 hours to obtain a polymer solution.

另外，添加NMP，使依合成例3之合成手法所得之聚醯胺酸溶液(3)中之樹脂固形分濃度達6質量%，而製得聚合物溶液。 In addition, NMP was added so that the concentration of the resin solid content in the polyamic acid solution (3) obtained according to the synthesis method of Synthesis Example 3 was 6% by mass, thereby preparing a polymer solution.

隨後，將前述2個聚合物溶液混合，於該溶液中，加入K1(0.15g)，於25℃下攪拌20小時，而製得液晶配向處理劑(4)。此液晶配向處理劑中，未發現混濁或析出等異常現象，而確認為均勻之溶液。 Subsequently, the two polymer solutions were mixed, K1 (0.15 g) was added to the solution, and the mixture was stirred at 25 ° C. for 20 hours to obtain a liquid crystal alignment treatment agent (4). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, but it was confirmed to be a uniform solution.

使用所得之液晶配向處理劑(4)，進行「液晶配向處理劑的保存安定性之評估」、「液晶配向處理劑之白化‧凝聚之評估」及「電壓保持率之評估」。 Using the obtained liquid crystal alignment treatment agent (4), "evaluation of the storage stability of the liquid crystal alignment treatment agent", "evaluation of the whitening and agglomeration of the liquid crystal alignment treatment agent", and "evaluation of the voltage holding ratio" were performed.

<實施例5> <Example 5>

於依合成例2之合成手法所得之聚醯亞胺粉末(2)(3.00g)中，加入NMP(11.0g)及γ-BL(11.0g)，於50℃下攪拌20小時，使其溶解。於此溶液中，加入NMP(4.00g)、γ-BL(6.00g)、BCS(10.0g)及DPM(5.00g)，於50℃下攪拌20小時，製得聚合物溶液。 NMP (11.0 g) and γ-BL (11.0 g) were added to the polyimide powder (2) (3.00 g) obtained according to the synthesis method of Synthesis Example 2, and stirred at 50 ° C for 20 hours to dissolve it. . To this solution, NMP (4.00 g), γ-BL (6.00 g), BCS (10.0 g), and DPM (5.00 g) were added and stirred at 50 ° C for 20 hours to obtain a polymer solution.

另外，添加NMP，使依合成例4之合成手法所得之聚醯胺酸溶液(4)中之樹脂固形分濃度達6質量%，而製得聚合物溶液。 In addition, NMP was added so that the concentration of the resin solid content in the polyamic acid solution (4) obtained according to the synthesis method of Synthesis Example 4 was 6% by mass, thereby preparing a polymer solution.

隨後，將前述2個聚合物溶液混合，於該溶液中，加入K1(0.15g)，於25℃下攪拌20小時，而製得液晶配向處理劑(5)。此液晶配向處理劑中，未發現混濁或析出等異常現象，而確認為均勻之溶液。 Subsequently, the two polymer solutions were mixed, K1 (0.15 g) was added to the solution, and the mixture was stirred at 25 ° C. for 20 hours to prepare a liquid crystal alignment treatment agent (5). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, but it was confirmed to be a uniform solution.

使用所得之液晶配向處理劑(5)，進行「液晶配向處理劑的保存安定性之評估」、「液晶配向處理劑之白化‧凝聚之評估」及「電壓保持率之評估」。 Using the obtained liquid crystal alignment treatment agent (5), "evaluation of the storage stability of the liquid crystal alignment treatment agent", "evaluation of the whitening and agglomeration of the liquid crystal alignment treatment agent", and "evaluation of the voltage holding ratio" were performed.

<實施例6> <Example 6>

於依合成例2之合成手法所得之聚醯亞胺粉末(2)(3.00g)中，加入NMP(11.0g)及γ-BL(11.0g)，於50℃下攪拌20小時，使其溶解。於此溶液中，加入NMP(4.00g)、γ-BL(6.00g)、BCS(10.0g)及DPM(5.00g)，於50℃下攪拌20小時，製得聚合物溶液。 NMP (11.0 g) and γ-BL (11.0 g) were added to the polyimide powder (2) (3.00 g) obtained according to the synthesis method of Synthesis Example 2, and stirred at 50 ° C for 20 hours to dissolve it. . To this solution, NMP (4.00 g), γ-BL (6.00 g), BCS (10.0 g), and DPM (5.00 g) were added and stirred at 50 ° C for 20 hours to obtain a polymer solution.

另外，添加NMP，使依合成例5之合成手法 所得之聚醯胺酸溶液(5)中之樹脂固形分濃度達6質量%，而製得聚合物溶液。 In addition, NMP was added to make the synthesis method according to Synthesis Example 5 The resin solid content concentration in the obtained polyamic acid solution (5) was 6 mass%, and a polymer solution was prepared.

隨後，將前述2個聚合物溶液混合，於該溶液中，加入K1(0.15g)，於25℃下攪拌20小時，而製得液晶配向處理劑(6)。此液晶配向處理劑中，未發現混濁或析出等異常現象，而確認為均勻之溶液。 Subsequently, the two polymer solutions were mixed, K1 (0.15 g) was added to the solution, and the mixture was stirred at 25 ° C. for 20 hours to prepare a liquid crystal alignment treatment agent (6). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, but it was confirmed to be a uniform solution.

使用所得之液晶配向處理劑(6)，進行「液晶配向處理劑的保存安定性之評估」、「液晶配向處理劑之白化‧凝聚之評估」及「電壓保持率之評估」。 Using the obtained liquid crystal alignment treatment agent (6), "evaluation of storage stability of liquid crystal alignment treatment agent", "evaluation of whitening and agglomeration of liquid crystal alignment treatment agent", and "evaluation of voltage holding ratio" were performed.

<比較例1> <Comparative example 1>

於依合成例6之合成手法所得之聚醯亞胺粉末(6)(3.00g)中，加入NMP(11.0g)及γ-BL(11.0g)，於50℃下攪拌20小時，使其溶解。於此溶液中，加入NMP(4.00g)、γ-BL(6.00g)、BCS(10.0g)及DPM(5.00g)，於50℃下攪拌20小時，製得聚合物溶液。 NMP (11.0 g) and γ-BL (11.0 g) were added to the polyimide powder (6) (3.00 g) obtained by the synthesis method of Synthesis Example 6, and stirred at 50 ° C for 20 hours to dissolve it. . To this solution, NMP (4.00 g), γ-BL (6.00 g), BCS (10.0 g), and DPM (5.00 g) were added and stirred at 50 ° C for 20 hours to obtain a polymer solution.

另外，添加NMP，使依合成例7之合成手法所得之聚醯胺酸溶液(7)中之樹脂固形分濃度達6質量%，而製得聚合物溶液。 In addition, NMP was added so that the concentration of the resin solid content in the polyamic acid solution (7) obtained according to the synthesis method of Synthesis Example 7 was 6% by mass, thereby preparing a polymer solution.

隨後，將前述2個聚合物溶液混合，於該溶液中，加入K1(0.15g)，於25℃下攪拌20小時，而製得液晶配向處理劑(7)。此液晶配向處理劑中，未發現混濁或析出等異常現象，而確認為均勻之溶液。 Subsequently, the two polymer solutions were mixed, K1 (0.15 g) was added to the solution, and the mixture was stirred at 25 ° C. for 20 hours to prepare a liquid crystal alignment treatment agent (7). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, but it was confirmed to be a uniform solution.

使用所得之液晶配向處理劑(7)，進行「液 晶配向處理劑的保存安定性之評估」、「液晶配向處理劑之白化‧凝聚之評估」及「電壓保持率之評估」。 Using the obtained liquid crystal alignment treatment agent (7), "Evaluation of storage stability of crystal alignment treatment agent", "Evaluation of whitening and agglomeration of liquid crystal alignment treatment agent", and "Evaluation of voltage retention rate".

<比較例2> <Comparative example 2>

於合成例1之合成手法所得之聚醯亞胺粉末(1)(3.00g)中，加入NMP(11.0g)及γ-BL(11.0g)，於50℃下攪拌20小時，使其溶解。於此溶液中，加入NMP(4.00g)、γ-BL(6.00g)、BCS(10.0g)及DPM(5.00g)，於50℃下攪拌20小時，製得聚合物溶液。 NMP (11.0 g) and γ-BL (11.0 g) were added to the polyfluorene imine powder (1) (3.00 g) obtained by the synthetic method of Synthesis Example 1, and the mixture was stirred at 50 ° C for 20 hours to be dissolved. To this solution, NMP (4.00 g), γ-BL (6.00 g), BCS (10.0 g), and DPM (5.00 g) were added and stirred at 50 ° C for 20 hours to obtain a polymer solution.

另外，添加NMP，使依合成例7之合成手法所得之聚醯胺酸溶液(7)中之樹脂固形分濃度達6質量%，而製得聚合物溶液。 In addition, NMP was added so that the concentration of the resin solid content in the polyamic acid solution (7) obtained according to the synthesis method of Synthesis Example 7 was 6% by mass, thereby preparing a polymer solution.

隨後，將前述2個聚合物溶液混合，於該溶液中，加入K1(0.15g)，於25℃下攪拌20小時，而製得液晶配向處理劑(8)。此液晶配向處理劑中，未發現混濁或析出等異常現象，而確認為均勻之溶液。 Subsequently, the two polymer solutions were mixed, K1 (0.15 g) was added to the solution, and the mixture was stirred at 25 ° C. for 20 hours to prepare a liquid crystal alignment treatment agent (8). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, but it was confirmed to be a uniform solution.

使用所得之液晶配向處理劑(8)，進行「液晶配向處理劑的保存安定性之評估」、「液晶配向處理劑之白化‧凝聚之評估」及「電壓保持率之評估」。 Using the obtained liquid crystal alignment treatment agent (8), "evaluation of the storage stability of the liquid crystal alignment treatment agent", "evaluation of the whitening and agglomeration of the liquid crystal alignment treatment agent", and "evaluation of the voltage holding ratio" were performed.

<比較例3> <Comparative example 3>

於依合成例6之合成手法所得之聚醯亞胺粉末(6)(3.00g)中，加入NMP(11.0g)及γ-BL(11.0g)，於50℃下攪拌20小時，使其溶解。於此溶液中，加入NMP (4.00g)、γ-BL(6.00g)、BCS(10.0g)及DPM(5.00g)，於50℃下攪拌20小時，製得聚合物溶液。 NMP (11.0 g) and γ-BL (11.0 g) were added to the polyimide powder (6) (3.00 g) obtained by the synthesis method of Synthesis Example 6, and stirred at 50 ° C for 20 hours to dissolve it. . In this solution, add NMP (4.00g), γ-BL (6.00g), BCS (10.0g) and DPM (5.00g), and stirred at 50 ° C for 20 hours to obtain a polymer solution.

另外，添加NMP，使依合成例3之合成手法所得之聚醯胺酸溶液(3)中之樹脂固形分濃度達6質量%，而製得聚合物溶液。 In addition, NMP was added so that the concentration of the resin solid content in the polyamic acid solution (3) obtained according to the synthesis method of Synthesis Example 3 was 6% by mass, thereby preparing a polymer solution.

隨後，將前述2個聚合物溶液混合，於該溶液中，加入K1(0.15g)，於25℃下攪拌20小時，而製得液晶配向處理劑(9)。此液晶配向處理劑中，未發現混濁或析出等異常現象，而確認為均勻之溶液。 Subsequently, the two polymer solutions were mixed, K1 (0.15 g) was added to the solution, and the mixture was stirred at 25 ° C. for 20 hours to prepare a liquid crystal alignment treatment agent (9). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, but it was confirmed to be a uniform solution.

使用所得之液晶配向處理劑(9)，進行「液晶配向處理劑的保存安定性之評估」、「液晶配向處理劑之白化‧凝聚之評估」及「電壓保持率之評估」。 Using the obtained liquid crystal alignment treatment agent (9), "evaluation of the storage stability of the liquid crystal alignment treatment agent", "evaluation of the whitening and agglomeration of the liquid crystal alignment treatment agent", and "evaluation of the voltage holding ratio" were performed.

＊ 1：表示相對於全部聚合物100質量份，特定聚合物(A)之導入量(質量份)。 * 1: The amount (parts by mass) of the specific polymer (A) introduced relative to 100 parts by mass of the entire polymer.

＊ 2：表示相對於全部聚合物100質量份，特定聚合 物(B)之導入量(質量份)。 ＊ 2: Represents specific polymerization with respect to 100 parts by mass of all polymers. The amount (parts by mass) of the substance (B).

＊ 3：表示相對於全部溶劑100質量份，其他聚合物之導入量(質量份)。 ＊ 3: It means the introduction amount (parts by mass) of other polymers relative to 100 parts by mass of the entire solvent.

＊ 1：表示相對於全部聚合物100質量份，特定聚合物(A)之導入量(質量份)。 * 1: The amount (parts by mass) of the specific polymer (A) introduced relative to 100 parts by mass of the entire polymer.

＊ 2：表示相對於全部聚合物100質量份，特定聚合物(B)之導入量(質量份)。 * 2: Represents the introduction amount (parts by mass) of the specific polymer (B) relative to 100 parts by mass of the entire polymer.

＊ 3：表示相對於全部溶劑100質量份，其他聚合物之導入量(質量份)。 ＊ 3: It means the introduction amount (parts by mass) of other polymers relative to 100 parts by mass of the entire solvent.

由上述之結果得知，本發明之實施例的液晶配向處理劑，與比較例的液晶配向處理劑相比較得知，其為具有優良保存安定性之液晶配向處理劑，且，於液晶配向處理劑塗佈於基板上之際，可抑制聚合物成份之白化‧凝聚現象。此外，除具有良好初期特性以外，即使長時間暴露於光線照射之後，也可以抑制電壓保持率之降低。 From the above results, it is known that the liquid crystal alignment treatment agent according to the embodiment of the present invention is compared with the liquid crystal alignment treatment agent of the comparative example, and it is known that it is a liquid crystal alignment treatment agent with excellent storage stability, and is subjected to liquid crystal alignment treatment. When the agent is applied on the substrate, the whitening and aggregation of the polymer component can be suppressed. In addition, in addition to having good initial characteristics, it is possible to suppress a decrease in voltage holding ratio even after long-term exposure to light irradiation.

具體而言，使用本發明之特定聚合物(A)與特定聚合物(B)之液晶配向處理劑的實施例，與使用不含特定二胺化合物(1)之聚合物與不含特定二胺化合物(2)之聚合物所得之液晶配向處理劑的比較，即，為實施例1與比較例1之比較。此比較例，與對應之實施例相比較時，得知液晶配向處理劑於保管中，容易產生混濁或析出物，且，於液晶配向處理劑塗佈於基板上之際，聚合物成份容易產生白化‧凝聚現象等。此外，關於電壓保持率，得知液晶晶胞製作後立即測定之數值以外，暴露於長時間光照射之後，亦大幅降低。 Specifically, the examples using the liquid crystal alignment treatment agent of the specific polymer (A) and the specific polymer (B) of the present invention, and the use of the polymer containing no specific diamine compound (1) and the absence of specific diamine The comparison of the liquid crystal alignment treatment agent obtained from the polymer of the compound (2) is a comparison between Example 1 and Comparative Example 1. When this comparative example is compared with the corresponding example, it is known that the liquid crystal alignment treatment agent is liable to generate turbidity or precipitates during storage, and that the polymer component is liable to be generated when the liquid crystal alignment treatment agent is coated on the substrate. Albinism and agglomeration. In addition, as for the voltage holding ratio, it was found that, in addition to the value measured immediately after the liquid crystal cell was manufactured, it was also significantly reduced after being exposed to long-term light irradiation.

此外，使用本發明之特定聚合物(A)與特定聚合物(B)之液晶配向處理劑的實施例，與未使用其中任一者所得之液晶配向處理劑的實施例之比較，即，實施 例1與比較例2或比較例3之比較。該些比較例中，與前述內容相同般，其與對應之實施例相比較時，得知液晶配向處理劑於保管中，容易產生混濁或析出物，且，於液晶配向處理劑塗佈於基板上之際，聚合物成份容易產生白化‧凝聚現象等。此外，關於電壓保持率，得知液晶晶胞製作後立即測定之數值以外，暴露於長時間光照射之後，亦大幅降低。 In addition, the embodiment using the liquid crystal alignment treatment agent of the specific polymer (A) and the specific polymer (B) of the present invention is compared with the embodiment obtained without using any of the liquid crystal alignment treatment agents, that is, the implementation Comparison of Example 1 with Comparative Example 2 or Comparative Example 3. These comparative examples are the same as those described above. When compared with the corresponding examples, it is found that the liquid crystal alignment treatment agent is easily stored during storage, and turbidity or precipitates are easily generated. The liquid crystal alignment treatment agent is coated on the substrate. At this time, the polymer component is prone to whitening and agglomeration. In addition, as for the voltage holding ratio, it was found that, in addition to the value measured immediately after the liquid crystal cell was manufactured, it was also significantly reduced after being exposed to long-term light irradiation.

〔產業上之可利用性〕 [Industrial availability]

本發明之液晶配向處理劑，其為具有優良保存安定性之液晶配向處理劑，且，於液晶配向處理劑塗佈於基板上之際，可抑制聚合物成份的白化‧凝聚現象，可提供具有優良塗膜均勻性之液晶配向膜。此外，除具有良好初期特性以外，即使長時間暴露於光線照射之後，也可以抑制電壓保持率之下降的液晶配向膜。 The liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment treatment agent having excellent storage stability, and when the liquid crystal alignment treatment agent is coated on a substrate, it can suppress the whitening and agglomeration of polymer components, and can provide Liquid crystal alignment film with excellent coating film uniformity. In addition, in addition to having good initial characteristics, a liquid crystal alignment film that can suppress a decrease in voltage retention even after long-term exposure to light irradiation.

因此，具有由本發明之液晶配向處理劑所得之液晶配向膜的液晶顯示元件，為具有優良信賴性者，而適合被使用於大畫面且高精密的液晶電視，或中小型汽車導航系統或智慧型手機等。 Therefore, a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is a person with excellent reliability, and is suitable for being used in a large-screen and high-precision liquid crystal television, or a small and medium-sized car navigation system or a smart type. Mobile phone, etc.

Claims (19)

一種液晶配向處理劑，其特徵為，含有下述(A)成份及(B)成份，(A)成份：含有由具有選自下述式〔1a〕~式〔1c〕所示結構之至少1種結構之聚醯亞胺前驅體及聚醯亞胺所選出之至少任一種的聚合物；(B)成份：含有由具有下述式〔2〕所示結構的聚醯亞胺前驅體及聚醯亞胺所選出之至少任一種的聚合物；(式〔2〕中，Y1及Y7各自獨立表示單鍵、碳數1~10之伸烷基、-O-、-N(R1)-(R1表示氫原子或碳數1~3之伸烷基)、-CON(R2)-(R2表示氫原子或碳數1~3之伸烷基)、-N(R3)CO-(R3表示氫原子或碳數1~3之伸烷基)、-CH2O-、-COO-及-OCO-所選出之至少1種的有機基，Y2及Y6各自獨立表示碳數1~10之伸烷基，Y3及Y5各自獨立表示氫原子或碳數1~10之伸烷基，Y4表示氧原子或硫原子)；(式〔1a〕中，X1表示苯環或含氮芳香族雜環，X2表示氫原子或被碳數1~12的脂肪族基所取代之二取代胺基，式〔1b〕中，X3及X7各自獨立表示具有6~15個碳原子，且具有1~2個苯環之芳香族基，X4及X6各自獨立表示氫原子或碳數1~5之伸烷基，X5表示碳數2~5之伸烷基或聯苯基，m表示0或1之整數，式〔1c〕中，X8及X10各自獨立表示由下述式〔1c-a〕及式〔1c-b〕所示結構所選出之至少1種的結構，X9表示碳數1~5之伸烷基或苯環) A liquid crystal alignment treatment agent, characterized in that it contains the following components (A) and (B), and (A) component: at least 1 having a structure selected from the following formulae [1a] to [1c] Polyimide precursor of this structure and at least one polymer selected from polyimide; (B) component: containing a polyimide precursor having a structure represented by the following formula [2] and a polymer A polymer selected from at least any one of iminium; (In the formula [2], Y 1 and Y 7 each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R 1 )-(R 1 represents a hydrogen atom or 1 to 10 carbon atoms) 3 alkylene), -CON (R 2 )-(R 2 represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), -N (R 3 ) CO- (R 3 represents a hydrogen atom or carbon number 1 ~ 3 alkylene group), -CH 2 O-, -COO- and -OCO- selected at least one kind of organic group, Y 2 and Y 6 each independently represent an alkylene group having 1 to 10 carbon atoms, Y 3 and Y 5 each independently represent a hydrogen atom or an alkylene group having 1 to 10 carbon atoms, and Y 4 represents an oxygen atom or a sulfur atom); (In the formula [1a], X 1 represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring, X 2 represents a hydrogen atom or a disubstituted amine group substituted with an aliphatic group having 1 to 12 carbon atoms. In the formula [1b], X 3 and X 7 each independently represent an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings, X 4 and X 6 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms, X 5 represents an alkylene group or a biphenyl group having 2 to 5 carbon atoms, m represents an integer of 0 or 1, and in the formula [1c], X 8 and X 10 each independently represent the following formula [1c-a] and formula [1c-b] At least one selected from the structures shown in the structure, X 9 represents an alkylene or benzene ring having 1 to 5 carbon atoms) 如請求項1之液晶配向處理劑，其中，前述(A)成份之聚合物為，使用下述式〔1-1〕所示二胺化合物作為原料的一部份而製得之聚合物，(式〔1-1〕中，XA表示具有由前述式〔1a〕~式〔1c〕所示結構所選出之至少1種的結構的碳數5~50的有機基，A1及A2各自獨立表示氫原子或碳數1~5之伸烷基)。For example, the liquid crystal alignment treatment agent of claim 1, wherein the polymer of the component (A) is a polymer prepared by using a diamine compound represented by the following formula [1-1] as a part of a raw material, (In the formula [1-1], X A represents an organic group having 5 to 50 carbon atoms having at least one structure selected from the structures represented by the aforementioned formulas [1a] to [1c], A 1 and A 2 Each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms). 如請求項2之液晶配向處理劑，其中，前述二胺化合物，為使用下述式〔1a-1〕~式〔1c-1〕所示二胺化合物作為原料的一部份而製得之聚合物，(式〔1a-1〕中，X1表示苯環或含氮芳香族雜環，X2表示氫原子或被碳數1~12的脂肪族基所取代之二取代胺基，式〔1b-1〕中，X3及X7各自獨立表示具有6~15個碳原子，且具有1~2個苯環之芳香族基，X4及X6各自獨立表示氫原子或碳數1~5之伸烷基，X5表示碳數2~5之伸烷基或聯苯基，m表示0或1之整數，式〔1c-1〕中，X8及X10各自獨立表示由前述式〔1c-a〕及式〔1c-b〕所示結構所選出之至少1種的結構，X9表示碳數1~5之伸烷基或苯環，式〔1a-1〕~式〔1c-1〕中，A1~A6各自獨立表示氫原子或碳數1~5之伸烷基)。The liquid crystal alignment treatment agent according to claim 2, wherein the diamine compound is a polymer prepared by using a diamine compound represented by the following formulae [1a-1] to [1c-1] as a part of a raw material. Things (In the formula [1a-1], X 1 represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring, X 2 represents a hydrogen atom or a disubstituted amine group substituted with an aliphatic group having 1 to 12 carbon atoms, and the formula [1b- 1], X 3 and X 7 each independently represent an aromatic group having 6 to 15 carbon atoms and having 1 to 2 benzene rings, and X 4 and X 6 each independently represent a hydrogen atom or a carbon number of 1 to 5 Alkyl, X 5 represents an alkyl or biphenyl group having 2 to 5 carbon atoms, and m represents an integer of 0 or 1. In the formula [1c-1], X 8 and X 10 each independently represent the formula [1c -a] and at least one selected from the structures shown in formula [1c-b], X 9 represents an alkylene or benzene ring having 1 to 5 carbon atoms, and formulas [1a-1] to [1c-1 In [], A 1 to A 6 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms. 如請求項3之液晶配向處理劑，其中，前述二胺化合物為由下述式〔1-1a〕~式〔1-4a〕所示二胺化合物所選出之至少1種的二胺化合物，(式〔1-3a〕中，R1表示氫原子或碳數1~5之伸烷基，式〔1-4a〕中，n表示1~10之整數，式〔1-1a〕~式〔1-4a〕中，A1~A8各自獨立表示氫原子或碳數1~5之伸烷基)。The liquid crystal alignment treatment agent according to claim 3, wherein the diamine compound is at least one type of diamine compound selected from the diamine compounds represented by the following formulae [1-1a] to [1-4a], (In formula [1-3a], R 1 represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms; in formula [1-4a], n represents an integer of 1 to 10; formula [1-1a] to formula [ 1-4a], A 1 to A 8 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms). 如請求項1之液晶配向處理劑，其中，前述(B)成份之聚合物為使用下述式〔2-1〕所示二胺化合物作為原料的一部份而製得之聚合物，(式〔2-1〕中，YA表示具有前述式〔2〕所示結構的有機基，A1及A2各自獨立表示氫原子或碳數1~5之伸烷基)。For example, the liquid crystal alignment treatment agent of claim 1, wherein the polymer of the component (B) is a polymer prepared by using a diamine compound represented by the following formula [2-1] as a part of a raw material, (In the formula [2-1], Y A represents an organic group having a structure represented by the aforementioned formula [2], and A 1 and A 2 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms). 如請求項5之液晶配向處理劑，其中，前述二胺化合物為使用下述式〔2a〕所示二胺化合物作為原料的一部份而製得之聚合物，(式〔2a〕中，Y1及Y7各自獨立表示單鍵、碳數1~10之伸烷基、-O-、-N(R1)-(R1表示氫原子或碳數1~3之伸烷基)、-CON(R2)-(R2表示氫原子或碳數1~3之伸烷基)、-N(R3)CO-(R3表示氫原子或碳數1~3之伸烷基)、-CH2O-、-COO-及-OCO-所選出之至少1種的有機基，Y2及Y6各自獨立表示碳數1~10之伸烷基，Y3及Y5各自獨立表示氫原子或碳數1~10之伸烷基，Y4表示氧原子或硫原子’A1及A2各自獨立表示氫原子或碳數1~5之伸烷基)。The liquid crystal alignment treatment agent according to claim 5, wherein the diamine compound is a polymer prepared by using a diamine compound represented by the following formula [2a] as a part of a raw material, (In the formula [2a], Y 1 and Y 7 each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R 1 )-(R 1 represents a hydrogen atom or 1 to 10 carbon atoms) 3 alkylene), -CON (R 2 )-(R 2 represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), -N (R 3 ) CO- (R 3 represents a hydrogen atom or carbon number 1 ~ 3 alkylene group), -CH 2 O-, -COO- and -OCO- selected at least one kind of organic group, Y 2 and Y 6 each independently represent an alkylene group having 1 to 10 carbon atoms, Y 3 and Y 5 each independently represent a hydrogen atom or an alkylene group having 1 to 10 carbon atoms, and Y 4 represents an oxygen atom or a sulfur atom ; A 1 and A 2 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms) . 如請求項6之液晶配向處理劑，其中，前述二胺化合物為由下述式〔2-1a〕~式〔2-3a〕所示二胺化合物所選出之至少1種的二胺化合物，(式〔2-1a〕~式〔2-3a〕中，A1~A6各自獨立表示氫原子或碳數1~5之伸烷基)。The liquid crystal alignment treatment agent according to claim 6, wherein the diamine compound is at least one diamine compound selected from the diamine compounds represented by the following formulas [2-1a] to [2-3a], (In the formulae [2-1a] to [2-3a], A 1 to A 6 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.) 如請求項1之液晶配向處理劑，其中，前述(A)成份之聚合物及(B)成份之聚合物為，由使用下述式〔3〕所示四羧酸成份而製得之聚醯亞胺前驅體及聚醯亞胺所選出之至少1種的聚合物，(式〔3〕中，Z表示由下述式〔3a〕~式〔3k〕所示結構所選出之至少1種的結構)(式〔3a〕中，Z1~Z4表示氫原子、甲基、乙基、丙基、氯原子或苯環，其可分別為相同亦可、相異亦可，式〔3g〕中，Z5及Z6表示氫原子或甲基，其可分別為相同亦可、相異亦可)。For example, the liquid crystal alignment treatment agent of claim 1, wherein the polymer of the component (A) and the polymer of the component (B) are polyfluorene prepared by using a tetracarboxylic acid component represented by the following formula [3] Polymer of at least one selected from imine precursor and polyimide, (In formula [3], Z represents at least one structure selected from the structures shown in the following formulas [3a] to [3k]) (In the formula [3a], Z 1 to Z 4 represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom, or a benzene ring, which may be the same as or different from each other. In the formula [3g], Z 5 and Z 6 represent a hydrogen atom or a methyl group, and they may be the same as or different from each other). 如請求項8之液晶配向處理劑，其中，前述四羧酸成份為前述式〔3〕中之Z為由〔3a〕及式〔3e〕~式〔3g〕所示結構所選出之至少1種的結構的四羧酸成份。In the liquid crystal alignment treatment agent according to claim 8, wherein the tetracarboxylic acid component is Z in the formula [3], at least one selected from the structures shown in the formulas [3a] and [3e] to [3g]. Structure of the tetracarboxylic acid component. 如請求項3之液晶配向處理劑，其中，前述(A)成份之聚合物中，前述式〔1a-1〕~式〔1c-1〕所示二胺化合物，於全部的二胺成份100莫耳%中，為5莫耳%~95莫耳%。The liquid crystal alignment treatment agent according to claim 3, wherein, among the polymer of the component (A), the diamine compound represented by the formula [1a-1] to [1c-1] is 100 moles in all the diamine components. Among the ear%, it ranges from 5 mole% to 95 mole%. 如請求項6之液晶配向處理劑，其中，前述(B)成份之聚合物中，前述式〔2a〕所示二胺化合物，於全部的二胺成份100莫耳%中，為5莫耳%~95莫耳%。The liquid crystal alignment treatment agent according to claim 6, wherein in the polymer of the component (B), the diamine compound represented by the formula [2a] is 5 mol% out of 100 mol% of all the diamine components. ~ 95 Mol%. 如請求項1之液晶配向處理劑，其中，前述(B)成份之聚合物，相對於前述(A)成份之聚合物100質量份，為0.5質量份~950質量份。The liquid crystal alignment treatment agent according to claim 1, wherein the polymer of the component (B) is 0.5 to 950 parts by mass relative to 100 parts by mass of the polymer of the component (A). 如請求項1之液晶配向處理劑，其中，液晶配向處理劑的溶劑為，含有由N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮及γ-丁內酯所選出之至少1種的溶劑。The liquid crystal alignment treatment agent according to claim 1, wherein the solvent of the liquid crystal alignment treatment agent contains N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone. At least one selected solvent. 如請求項1之液晶配向處理劑，其中，液晶配向處理劑的溶劑為，含有由1-己醇、環己醇、1,2-乙二醇、1,2-丙二醇、丙二醇單丁醚、乙二醇單丁醚及二丙二醇二甲醚所選出之至少1種的溶劑。For example, the liquid crystal alignment treatment agent of claim 1, wherein the solvent of the liquid crystal alignment treatment agent contains 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, propylene glycol monobutyl ether, At least one selected from the group consisting of ethylene glycol monobutyl ether and dipropylene glycol dimethyl ether. 如請求項1之液晶配向處理劑，其中，液晶配向處理劑中含有，具有環氧基、異氰酸酯基、環氧丙烷基或環碳酸酯基的交聯性化合物、具有由羥基、羥烷基或低級烷氧基烷基所成群所選出之至少1種的取代基的交聯性化合物，及由具有聚合性不飽和鍵結的交聯性化合物所選出之至少1種的交聯性化合物。The liquid crystal alignment treatment agent according to claim 1, wherein the liquid crystal alignment treatment agent contains a crosslinkable compound having an epoxy group, an isocyanate group, an propylene oxide group, or a cyclic carbonate group, and has a hydroxyl group, a hydroxyalkyl group, or a A crosslinkable compound of at least one kind of substituent selected from the group consisting of a lower alkoxyalkyl group, and a crosslinkable compound of at least one kind selected from a crosslinkable compound having a polymerizable unsaturated bond. 一種液晶配向膜，其特徵為，由請求項1~請求項15之任一項之液晶配向處理劑所製得。A liquid crystal alignment film, which is prepared by a liquid crystal alignment treatment agent according to any one of claim 1 to claim 15. 一種液晶配向膜，其特徵為，使用請求項1~請求項15之任一項之液晶配向處理劑，以噴墨法而製得者。A liquid crystal alignment film, which is prepared by an inkjet method using the liquid crystal alignment treatment agent according to any one of claim 1 to claim 15. 一種液晶顯示元件，其特徵為，具有請求項16之液晶配向膜。A liquid crystal display element comprising the liquid crystal alignment film of claim 16. 一種液晶顯示元件，其特徵為，具有請求項17之液晶配向膜。A liquid crystal display element having the liquid crystal alignment film of claim 17.
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