TWI628232B - Liquid crystal alignment treatment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Liquid crystal alignment treatment agent, liquid crystal alignment film and liquid crystal display element Download PDF

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TWI628232B
TWI628232B TW103130405A TW103130405A TWI628232B TW I628232 B TWI628232 B TW I628232B TW 103130405 A TW103130405 A TW 103130405A TW 103130405 A TW103130405 A TW 103130405A TW I628232 B TWI628232 B TW I628232B
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crystal alignment
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三木徳俊
片山雅章
巴幸司
国見奈穂
保坂和義
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日產化學工業股份有限公司
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Abstract

本發明係提供形成既使曝露於長時間高溫及光照射後,仍可發現安定的預傾角、抑制電壓保持率降低,且加速緩和所蓄積殘留電荷之液晶配向膜的液晶配向處理劑、液晶配向膜及液晶顯示元件。 The invention provides a liquid crystal alignment treatment agent and a liquid crystal alignment agent for forming a liquid crystal alignment film that can find a stable pretilt angle, suppress a decrease in voltage retention rate, and accelerate and alleviate the accumulated residual charge even after being exposed to high temperature and light irradiation for a long time. Film and liquid crystal display element.

該液晶配向處理劑為,含有下述(A)成分及(B)成分。 This liquid crystal alignment treatment agent contains the following (A) component and (B) component.

(A)成分:含有由含有具有式[1]之支鏈結構的二胺化合物之二胺成分,與四羧酸成分反應所得的聚醯亞胺先驅物及聚醯亞胺中至少一方的聚合物。 (A) Component: Polymerization of at least one of polyimide precursor and polyimide containing a diamine component containing a diamine compound having a branched structure of formula [1] and reacting with a tetracarboxylic acid component Thing.

(B)成分:含有由未含有具有式[1]所表示之支鏈結構的二胺化合物之二胺成分,與四羧酸成分反應所得的聚醯亞胺先驅物及聚醯亞胺中至少一方的聚合物。 (B) Component: at least one of polyimide precursors and polyimide containing a diamine component that does not contain a diamine compound having a branched structure represented by formula [1], and a reaction with a tetracarboxylic acid component Polymer on one side.

(Y1、Y2、Y3為單鍵結、伸烷基等;Y4、Y5為苯環等之二價的環狀基;n為0~4之整數;Y6為碳數1~18之烷基等)。 (Y 1 , Y 2 , Y 3 are single bonds, alkylene groups, etc .; Y 4 , Y 5 are bivalent cyclic groups such as benzene rings; n is an integer from 0 to 4; Y 6 is a carbon number of 1 ~ 18 alkyl, etc.).

Description

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

本發明係有關液晶顯示元件所使用的液晶配向處理劑、液晶配向膜及液晶顯示元件。 The present invention relates to a liquid crystal alignment treatment agent, a liquid crystal alignment film, and a liquid crystal display element used in a liquid crystal display element.

液晶顯示元件目前係廣泛使用於實現薄型、輕量之顯示器。一般液晶顯示元件中為了決定液晶之配向狀態係使用液晶配向膜。 Liquid crystal display elements are currently widely used to realize thin and lightweight displays. In order to determine the alignment state of liquid crystal in a general liquid crystal display element, a liquid crystal alignment film is used.

液晶配向膜所要求的特性之一為,可使相對於基板面的液晶分子之配向傾斜角保持任意之值,及控制所謂液晶的預傾角。已知預傾角的大小可藉由選擇構成液晶配向膜用的聚醯亞胺之結構而變更。既使為藉由聚醯亞胺之結構以控制預傾角的技術,以具有支鏈之二胺作為聚醯亞胺原料之一部分用的方法也可因應二胺之使用比例而控制預傾角,故較容易得到目的之預傾角,適用為增加預傾角之方法(例如參考專利文獻1)。又,有關增加液晶之預傾角用的二胺成分,曾檢討為了改善預傾角之安定性及步驟依存性用的結構,而提案以含有苯基、環己基等之環結構之物作為其支鏈結構用(例如參考專利文獻2)。 One of the characteristics required for a liquid crystal alignment film is that the alignment tilt angle of the liquid crystal molecules with respect to the substrate surface can be maintained at an arbitrary value, and the so-called pretilt angle of the liquid crystal can be controlled. It is known that the magnitude of the pretilt angle can be changed by selecting the structure of the polyimide used for the liquid crystal alignment film. Even if it is a technique for controlling the pretilt angle through the structure of polyimide, the method of using a branched diamine as a part of the raw material of the polyimide can also control the pretilt angle according to the proportion of the diamine used, so It is easier to obtain the intended pretilt angle, and it is suitable to increase the pretilt angle (for example, refer to Patent Document 1). In addition, regarding the diamine component for increasing the pretilt angle of liquid crystals, a structure for improving the stability and step dependence of the pretilt angle has been reviewed, and it has been proposed to use a cyclic structure such as phenyl and cyclohexyl as its branch chain. For structure (for example, refer to Patent Document 2).

又,伴隨著液晶顯示元件高精細化,就抑制液晶顯示元件降低對比及減少殘像顯像之觀點,次要重要為,既使所使用的液晶配向膜也具有較高電壓保持率,減少施加直流電壓時之蓄積電荷或加速緩和因直流電壓所蓄積之電荷的特性逐漸變得重要。 In addition, with the high definition of liquid crystal display elements, it is of secondary importance to suppress the liquid crystal display elements from reducing the contrast and reducing the afterimage development. Even the liquid crystal alignment film used has a high voltage retention rate and reduces the application. The characteristics of accumulating electric charges at a DC voltage or accelerating and alleviating the electric charges accumulated by a DC voltage are becoming important.

有關聚醯亞胺系之液晶配向膜,已知的縮短因直流電壓而發生之殘像至消失所需時間之物如,使用除了聚醯胺酸或含有醯亞胺基之聚醯胺酸,另含有特定結構之三級胺的液晶配向處理劑之物(例如參考專利文獻3),及使用含有原料係使用具有吡啶骨架等之特定二胺的可溶性聚醯亞胺的液晶配向處理劑之物(例如參考專利文獻4)等。又,已知的提高電壓保持率,且縮短因直流電壓而發生之殘像至消失所需時間之物如,使用除了聚醯胺酸及其醯亞胺化聚合物等,另含有極少量的由分子內含有1個羧酸基之化合物、分子內含有1個羧酸酐基之化合物及分子內含有1個三級胺基之化合物中所選出的化合物的液晶配向處理劑之物(例如參考專利文獻5)。 Regarding polyimide-based liquid crystal alignment films, it is known to shorten the time required for the afterimage to disappear by a DC voltage. For example, in addition to polyimide or polyimide containing polyimide, In addition, a liquid crystal alignment treatment agent containing a tertiary amine with a specific structure (for example, refer to Patent Document 3), and a liquid crystal alignment treatment agent containing a soluble polyfluorene imide containing a specific diamine having a pyridine skeleton as a raw material. (For example, refer to Patent Document 4). In addition, it is known to increase the voltage holding ratio and shorten the time required for the afterimage to disappear after the DC voltage is applied. For example, in addition to polyamic acid and its imidized polymer, it contains a very small amount of A liquid crystal alignment treatment agent selected from a compound containing one carboxylic acid group in the molecule, a compound containing one carboxylic acid anhydride group in the molecule, and a compound containing one tertiary amine group in the molecule (for example, refer to a patent Reference 5).

先前技術文獻 Prior art literature 專利文獻 Patent literature

專利文獻1:特開平2-282726號公報 Patent Document 1: Japanese Unexamined Patent Publication No. 2-282726

專利文獻2:特開平9-278724號公報 Patent Document 2: Japanese Unexamined Patent Publication No. 9-278724

專利文獻3:特開平9-316200號公報 Patent Document 3: Japanese Unexamined Patent Publication No. 9-316200

專利文獻4:特開平10-104633號公報 Patent Document 4: Japanese Unexamined Patent Publication No. 10-104633

專利文獻5:特開平8-76128號公報 Patent Document 5: Japanese Unexamined Patent Publication No. 8-76128

液晶配向膜也作為控制相對於基板之液晶的角度,即液晶之預傾角用。特別是VA(Vertical Alignment)模式或PSA(Polymer Sustained Alignment)模式等,需使液晶垂直配向,因此要求液晶配向膜具有使液晶垂直配向之能力(也可稱為垂直配向性或高預傾角)。另外液晶配向膜除了較高垂直配向性外,相對於其安定性也係重要。特別是使用為了得到高亮度而增加發熱量,且光照射量較多之背光的液晶顯示元件,例如汽車導航系統或大型電視,係使用或放置於曝露於長時間高溫及光照射之環境下。該嚴酷條件下會降低垂直配向性,而有無法得到初期之顯示特性,或顯示時發生斑點等之問題。 The liquid crystal alignment film is also used to control the angle of the liquid crystal relative to the substrate, that is, the pretilt angle of the liquid crystal. Especially VA (Vertical Alignment) mode or PSA (Polymer Sustained Alignment) mode, etc., need to align the liquid crystal vertically, so the liquid crystal alignment film is required to have the ability to align the liquid crystal vertically (also called vertical alignment or high pretilt angle). In addition to the high vertical alignment, the liquid crystal alignment film is also important relative to its stability. In particular, a liquid crystal display element, such as a car navigation system or a large television, which uses a backlight that increases the amount of heat to obtain high brightness and has a large amount of light exposure, is used or placed in an environment exposed to long periods of high temperature and light exposure. Under such severe conditions, vertical alignment is reduced, and there are problems such that initial display characteristics cannot be obtained, and speckles occur during display.

又,有關液晶顯示元件的電氣特性之一的電壓保持率,上述嚴酷條件下也要求高安定性。即,電壓保持率會因來自背光的光照射而降低,故易發生液晶顯示元件的顯示不良之一的燒結不良(也稱為線燒結),而無法得到高信賴性之液晶顯示元件。因此液晶配向膜除了需具有良好初期特性,另外要求既使曝露於長時間光照射後,也不易降低電壓保持率。另外相對於另一燒結不良的面燒結,也要求加速緩和因來自背光的光照射,而因直流電壓所蓄積的殘留電荷之液晶配向膜。 Further, regarding the voltage holding ratio, which is one of the electrical characteristics of the liquid crystal display element, high stability is also required under the severe conditions described above. That is, the voltage holding ratio is lowered by the light irradiation from the backlight, so that sintering failure (also referred to as wire sintering), which is one of the display failures of liquid crystal display elements, easily occurs, and a highly reliable liquid crystal display element cannot be obtained. Therefore, in addition to the good initial characteristics of the liquid crystal alignment film, it is also required that it is not easy to reduce the voltage holding ratio even after being exposed to long-term light irradiation. In addition, it is also required to accelerate and alleviate the residual charge accumulated by the DC voltage due to the light irradiation from the backlight with respect to the sintering of another poorly sintered surface.

故本發明之目的為,提供形成既使曝露於長時間高溫及光照射後,仍可發現安定之預傾角,另外既使曝露於長時間光照射後,也可抑制電壓保持率降低,且加速緩和因直流電壓所蓄積的殘留電荷之液晶配向膜的液晶配向處理劑。 Therefore, the object of the present invention is to provide a stable pretilt angle that can be found even after being exposed to long-term high temperature and light irradiation. In addition, even after being exposed to long-term light irradiation, the voltage retention rate can be suppressed from decreasing and accelerated. Liquid crystal alignment treatment agent for liquid crystal alignment film that alleviates residual charge accumulated by DC voltage.

又,本發明之目的為,提供具有上述特性之液晶配向膜,及備有該液晶配向膜之液晶顯示元件。 Another object of the present invention is to provide a liquid crystal alignment film having the above-mentioned characteristics, and a liquid crystal display element provided with the liquid crystal alignment film.

經本發明者專心研究後發現,具有具有特定結構之2個聚合物的液晶配向處理劑,對達成上述目的極有效而完成本發明。 After intensive research by the inventors, it was 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,本發明具有下述要旨。 That is, this invention has the following summary.

1.一種液晶配向處理劑,其特徵為含有下述(A)成分及(B)成分,(A)成分:由含有具有下述式[1]所表示的結構之二胺的二胺成分,與四羧酸成分反應所得的聚醯亞胺先驅物及聚醯亞胺所成群中所選出的至少一種之聚合物,(B)成分:由未含有具有下述式[1]所表示的結構之二胺的二胺成分,與四羧酸成分反應所得的聚醯亞胺先驅物及聚醯亞胺所成群中所選出的至少一種之聚合物, A liquid crystal alignment treatment agent comprising the following components (A) and (B), (A): a diamine component containing a diamine having a structure represented by the following formula [1], Polyimide precursors obtained by reacting with a tetracarboxylic acid component and at least one polymer selected from the group consisting of polyimide, component (B): which does not contain a compound represented by the following formula [1] A diamine component of a diamine having a structure, a polyimide precursor obtained by reacting with a tetracarboxylic acid component, and at least one polymer selected from the group consisting of polyimide,

(Y1表示單鍵結、-(CH2)a-(a為1~15之整數)、-O-、-CH2O-、-COO-或OCO-;Y2表示單鍵結或(CH2)b-(b為1~15之整數);Y3表示單鍵結、-(CH2)c-(c為1~15之整數)、-O-、-CH2O-、-COO-或OCO-;Y4表示由苯環、環己烷環及雜環中所選出的二價之環狀基,或具有類固醇骨架的碳數17~51之二價的有機基,前述環狀基上之任意的氫原子可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟的烷基、碳數1~3之含氟的烷氧基或氟原子取代;Y5表示苯環、環己烷環及雜環中所選出的二價之環狀基,該等環狀基上之任意的氫原子可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟的烷基、碳數1~3之含氟的烷氧基或氟原子取代;n表示0~4之整數;Y6表示碳數1~18之烷基、碳數1~18之含氟的烷基、碳數1~18之烷氧基或碳數1~18之含氟的烷氧基)。 (Y 1 represents a single bond,-(CH 2 ) a- (a is an integer from 1 to 15), -O-, -CH 2 O-, -COO- or OCO-; Y 2 represents a single bond or ( CH 2 ) b- (b is an integer from 1 to 15); Y 3 represents a single bond,-(CH 2 ) c- (c is an integer from 1 to 15), -O-, -CH 2 O-,- COO- or OCO-; Y 4 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton. Any hydrogen atom on the base can be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkyl group having 1 to 3 carbon atoms. Alkoxy or fluorine atom substitution; Y 5 represents a bivalent cyclic group selected from benzene ring, cyclohexane ring and heterocyclic ring, and any hydrogen atom on these cyclic groups may be 1 to 3 carbon atoms Substituted by alkyl group, alkoxy group having 1 to 3 carbon atoms, fluorine-containing alkyl group having 1 to 3 carbon atoms, fluorine-containing alkoxy group having 1 to 3 carbon atoms or fluorine atom substitution; n represents an integer of 0 to 4 ; Y 6 represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms).

2.如上述1所記載的液晶配向處理劑,其中具有前述式[1]所表示的結構之二胺為,下述式[1a]所表示,式(1a)中Y1、Y2、Y3、Y4、Y5、n、Y6及m與前述定義相同。 2. The liquid crystal alignment treatment agent according to the above 1, wherein the diamine having the structure represented by the formula [1] is represented by the following formula [1a], and Y 1 , Y 2 , and Y in the formula (1a) 3, Y 4, Y 5, n, Y 6 and m are the same as previously defined.

3.如上述1或2所記載的液晶配向處理劑,其中前述 (B)成分為,由含有具有由羧基(COOH基)及羥基(OH基)中所選出的至少一種之取代基的二胺之二胺成分,與四羧酸成分反應所得的聚醯亞胺先驅物及聚醯亞胺所成群中所選出的至少一種之聚合物。 3. The liquid crystal alignment treatment agent according to 1 or 2 above, wherein The component (B) is a polyimide obtained by reacting a diamine component containing a diamine having a substituent selected from at least one of a carboxyl group (COOH group) and a hydroxyl group (OH group) with a tetracarboxylic acid component. A polymer of at least one selected from the group consisting of a precursor and a polyimide.

4.如上述1、2或3所記載的液晶配向處理劑,其中前述(A)成分為,二胺成分另使用含有具有由羧基(COOH基)及羥基(OH)中所選出的至少一種之取代基的二胺的聚合物。 4. The liquid crystal alignment treatment agent according to the above 1, 2 or 3, wherein the component (A) is a diamine component and further contains one having at least one selected from a carboxyl group (COOH group) and a hydroxyl group (OH). Polymers of substituted diamines.

5.如上述3或4所記載的液晶配向處理劑,其中具有由前述羧基及羥基中所選出的至少一種之取代基的二胺為,下述式[2a]所表示, 5. The liquid crystal alignment treatment agent according to the above 3 or 4, wherein the diamine having a substituent selected from at least one of the carboxyl group and the hydroxyl group is represented by the following formula [2a],

(A1表示由下述式[2a-1]及式[2a-2]中所選出的至少1個取代基,m1表示1~4之整數)。 (A 1 represents at least one substituent selected from the following formulas [2a-1] and [2a-2], and m1 represents an integer of 1 to 4).

[化4]-(CH2)d-COOH [2a-1] -(CH2)e-OH [2a-2] [Chem. 4]-(CH 2 ) d -COOH [2a-1]-(CH 2 ) e -OH [2a-2]

(d表示0~4之整數,e表示0~4之整數)。 (d represents an integer from 0 to 4, and e represents an integer from 0 to 4.)

6.如上述1~5中任一項所記載的液晶配向處理劑,其中前述(A)成分及(B)成分之聚合物為,二胺成分使用下述式[3a]所表示的二胺之聚合物, (B1表示-O-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-CH2O-、-OCO-、-CON(CH3)-或N(CH3)CO-;B2表示單鍵結、碳數1~20之伸烷基、非芳香族環或芳香族環;B3表示單鍵結、-O-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-COO-、-OCO-、-CON(CH3)-、N(CH3)CO-、或-O(CH2)m2-(m2為1~5之整數);B4表示含氮之雜環;n1表示1~4之整數,n1為2以上時,-B1-B2-B3-B4可相同或相異)。 6. The liquid crystal alignment treatment agent according to any one of the above 1 to 5, wherein the polymer of the component (A) and the component (B) is a diamine component using a diamine represented by the following formula [3a] Polymer (B 1 represents -O-, -NH-, -N (CH 3 )-, -CONH-, -NHCO-, -CH 2 O-, -OCO-, -CON (CH 3 )-or N (CH 3 ) CO-; B 2 represents a single bond, an alkylene group having 1 to 20 carbon atoms, a non-aromatic ring or an aromatic ring; B 3 represents a single bond, -O-, -NH-, -N (CH 3 )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH 3 )-, N (CH 3 ) CO-, or -O (CH 2 ) m2- (m2 is 1 ~ 5 An integer); B 4 represents a nitrogen-containing heterocyclic ring; n1 represents an integer of 1 to 4; when n1 is 2 or more, -B 1 -B 2 -B 3 -B 4 may be the same or different).

7.如上述6所記載的液晶配向處理劑,其中前述式[3a]中之B1為-O-、-NH-、-CONH-、-NHCO-、-CH2O-、-OCO-或CON(CH3)-。 7. The liquid crystal alignment treatment agent according to the above 6, wherein B 1 in the formula [3a] is -O-, -NH-, -CONH-, -NHCO-, -CH 2 O-, -OCO- or CON (CH 3 )-.

8.如上述6或7所記載的液晶配向處理劑,其中前述式[3a]中之B2為單鍵結、碳數1~5之伸烷基、環己烷環或苯環。 8. The liquid crystal alignment treatment agent according to 6 or 7, wherein B 2 in the formula [3a] is a single bond, an alkylene group having 1 to 5 carbon atoms, a cyclohexane ring, or a benzene ring.

9.如上述6~8中任一項所記載的液晶配向處理劑,其中前述式[3a]中之B3為單鍵結、-O-、-OCO-或O(CH2)2-(m2為1~5之整數)。 9. The liquid crystal alignment treatment agent according to any one of 6 to 8, wherein B 3 in the formula [3a] is a single bond, -O-, -OCO-, or O (CH 2 ) 2- ( m2 is an integer from 1 to 5).

10.如上述6~9中任一項所記載的液晶配向處理劑,其中前述式[3a]中之B4為吡咯環、咪唑環、吡唑環、吡啶環或嘧啶環。 10. The liquid crystal alignment treatment agent according to any one of 6 to 9, wherein B 4 in the formula [3a] is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring.

11.如上述6所記載的液晶配向處理劑,其中前述式[3a]中之B1表示-CONH-、B2表示碳數1~5之伸烷基,B3 表示單鍵結,B4表示咪唑環或吡啶環,n1為1。 11. The liquid crystal alignment treatment agent according to the above 6, wherein B 1 in the formula [3a] represents -CONH-, B 2 represents an alkylene group having 1 to 5 carbon atoms, B 3 represents a single bond, and B 4 Represents an imidazole ring or a pyridine ring, and n1 is 1.

12.如上述1~11中任一項所記載的液晶配向處理劑,其中前述(A)成分及(B)成分之至少一方的四羧酸成分為,含有下述式[4]所表示的四羧酸二酐, 12. The liquid crystal alignment treatment agent according to any one of 1 to 11 above, wherein the tetracarboxylic acid component of at least one of the (A) component and (B) component is a component represented by the following formula [4] Tetracarboxylic dianhydride,

(Z1為由下述式[4a]~式[4k]中所選出的基)。 (Z 1 is a base selected from the following formulas [4a] to [4k]).

(Z2~Z5表示各自獨立的氫原子、甲基、氯原子或苯環,Z6、Z7表示各自獨立的氫原子或甲基)。 (Z 2 to Z 5 each independently represent a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring, and Z 6 and Z 7 each independently represent a hydrogen atom or a methyl group).

13.如上述1~12中任一項所記載的液晶配向處理劑,其中含有N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮及γ-丁內酯中至少一種之溶劑。 13. The liquid crystal alignment treatment agent according to any one of 1 to 12 above, which contains a solvent of at least one of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone.

14.如上述1~13中任一項所記載的液晶配向處理劑,其中含有由下述式[D-1]~式[D-3]中所選出的至少一種之溶 劑, 14. The liquid crystal alignment treatment agent according to any one of 1 to 13 above, which contains at least one solvent selected from the following formulas [D-1] to [D-3],

(D1表示碳數1~3之烷基,D2表示碳數1~3之烷基,D3表示碳數1~4之烷基)。 (D 1 represents an alkyl group having 1 to 3 carbon atoms, D 2 represents an alkyl group having 1 to 3 carbon atoms, and D 3 represents an alkyl group having 1 to 4 carbon atoms).

15.如上述1~14中任一項所記載的液晶配向處理劑,其中含有由1-己醇、環己醇、1,2-乙二醇、1,2-丙二醇、丙二醇單丁基醚、乙二醇單丁基醚及二丙二醇二甲基醚中所選出的至少一種之溶劑。 15. The liquid crystal alignment treatment agent according to any one of 1 to 14 above, which contains 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, and propylene glycol monobutyl ether. A solvent of at least one selected from the group consisting of ethylene glycol monobutyl ether and dipropylene glycol dimethyl ether.

16.如上述1~15中任一項所記載的液晶配向處理劑,其中液晶配向處理劑中含有,由具有環氧基、異氰酸酯基、環氧丙烷基或環碳酸酯基之交聯性化合物、具有由羥基、羥基烷基及低級烷氧基烷基所成群中所選出的至少一種之取代基的交聯性化合物,及具有聚合性不飽和鍵結的交聯性化合物中所選出的至少一種之交聯性化合物。 16. The liquid crystal alignment treatment agent according to any one of the above 1 to 15, wherein the liquid crystal alignment treatment agent contains a crosslinkable compound having an epoxy group, an isocyanate group, a propylene oxide group, or a cyclic carbonate group. A cross-linkable compound having at least one selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group; and a cross-linkable compound having a polymerizable unsaturated bond At least one crosslinkable compound.

17.一種液晶配向膜,其為由如上述1~16中任一項所記載的液晶配向處理劑所得。 17. A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of 1 to 16 above.

18.一種液晶配向膜,其為藉由噴墨印刷法印刷如上述1~16中任一項所記載的液晶配向處理劑所得。 18. A liquid crystal alignment film obtained by printing the liquid crystal alignment treatment agent according to any one of 1 to 16 by an inkjet printing method.

19.一種液晶顯示元件,其為具有如上述17或18所記載的液晶配向膜。 19. A liquid crystal display element having the liquid crystal alignment film according to 17 or 18 above.

20.如上述17或18所記載的液晶配向膜,其係使用 於經由一對備有電極之基板間具有液晶層,將含有藉由活性能量線及熱中至少一方而聚合的聚合性化合物之液晶組成物配置於前述一對基板之間,將電壓施加於前述電極間的同時聚合前述聚合性化合物之步驟所製造的液晶顯示元件。 20. The liquid crystal alignment film according to 17 or 18 above, which is used A liquid crystal layer is provided between a pair of substrates provided with electrodes, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and a voltage is applied to the electrodes. A liquid crystal display device produced by the step of simultaneously polymerizing the polymerizable compound.

21.如上述17或18所記載的液晶配向膜,其為使用於一對備有電極之基板間具有液晶層所構成,經由將含有藉由活性能量線及熱中至少一方而聚合之聚合性基的液晶配向膜配置於前述一對基板之間,將電壓施加於前述電極間的同時聚合前述聚合性基之步驟製造的液晶顯示元件。 21. The liquid crystal alignment film according to the above 17 or 18, which is composed of a liquid crystal layer used between a pair of substrates provided with electrodes, and contains a polymerizable group which is polymerized by at least one of active energy rays and heat. The liquid crystal alignment film is a liquid crystal display device produced by a step of polymerizing the polymerizable group while applying a voltage between the pair of substrates while applying a voltage between the electrodes.

22.一種液晶顯示元件,其為具有如上述20或21所記載的液晶配向膜。 22. A liquid crystal display element comprising the liquid crystal alignment film according to 20 or 21 above.

本發明的具有由含有特定結構之聚醯亞胺先驅物及聚醯亞胺中所選出的至少一種之聚合物與由未含特定結構之聚醯亞胺先驅物及聚醯亞胺中所選出的至少一種之聚合物的2個聚合物之液晶配向處理劑為,可得既使曝露於長時間高溫及光照射後,仍可發現安定的預傾角之液晶配向膜。又,可得既使曝露於長時間光照射後,仍可抑制電壓保持率降低,且加速緩和因直流電壓所蓄積的殘留電荷之液晶配向膜。因此具有由本發明之液晶配向處理劑所得的液晶配向膜之液晶顯示元件為,具有優良之信賴 性,適用於大畫面且高精細之液晶電視等。 The polymer having at least one selected from among polyfluorene imide precursors containing a specific structure and polyamimine according to the present invention, and from among polyfluorene imide precursors and polyfluorene containing no specific structure The liquid crystal alignment treatment agent for the two polymers of at least one polymer is a liquid crystal alignment film with a stable pretilt angle that can be found even after being exposed to high temperature and light irradiation for a long time. In addition, a liquid crystal alignment film capable of suppressing a decrease in the voltage holding rate even after being exposed to long-term light irradiation and accelerating and alleviating the residual charge accumulated by the DC voltage can be obtained. Therefore, a liquid crystal display device having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability. It is suitable for large-screen and high-definition LCD TVs.

實施發明之形態 Embodiment of the invention

本發明的液晶配向處理劑為,含有下述(A)成分及(B)成分。 The liquid-crystal aligning agent of this invention contains the following (A) component and (B) component.

(A)成分:含有由含有具有上述式[1]所表示的支鏈結構(也稱為特定支鏈結構)之二胺化合物的二胺成分,與四羧酸成分反應所得的聚醯亞胺先驅物及聚醯亞胺中所選出的至少任何一方的聚合物(也稱為特定聚合物(A))。 (A) Component: Polyfluorene imide obtained by reacting a diamine component containing a diamine compound having a branched structure (also referred to as a specific branched structure) represented by the above formula [1] with a tetracarboxylic acid component A polymer (also referred to as a specific polymer (A)) selected from at least one of a precursor and a polyimide.

(B)成分:含有由未含有具有上述式[1]所表示的支鏈結構之二胺化合物的二胺成分,與四羧酸成分反應所得的聚醯亞胺先驅物及聚醯亞胺中所選出的至少任何一方的聚合物(也稱為特定聚合物(B))。 (B) Component: a polyimide precursor and a polyimide obtained by reacting a diamine component that does not contain a diamine compound having a branched structure represented by the above formula [1] and reacting with a tetracarboxylic acid component A polymer selected from at least one of them (also referred to as a specific polymer (B)).

本發明之液晶配向處理劑中又以含有下述(A)成分及(B)成分,且僅(A)成分係使用具有特定支鏈結構之二胺化合物為佳。 The liquid crystal alignment treatment agent of the present invention further contains the following (A) component and (B) component, and it is preferable that only the (A) component is a diamine compound having a specific branched structure.

(A)成分:含有由二胺成分與四羧酸成分反應所得的聚醯亞胺先驅物及聚醯亞胺中所選出的至少任何一方的聚合物。 (A) Component: A polymer containing at least one selected from a polyimide precursor and a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.

(B)成分:含有由二胺成分與四羧酸成分反應所得的聚醯亞胺先驅物及聚醯亞胺中所選出的至少任何一方的聚合物。 (B) Component: A polymer containing at least one selected from the group consisting of a polyimide precursor and a polyimide obtained by a reaction between a diamine component and a tetracarboxylic acid component.

本發明的特定聚合物(A)所含之式[1]所表 示的特定支鏈結構為,支鏈部位具有由苯環、環己基環及雜環中所選出的至少一種之基,或具有類固醇骨架的碳數17~51之二價的有機基。該等環及有機基之支鏈結構,比較先前使液晶垂直配向之技術的長鏈烷基之支鏈結構時,可得更剛直之結構。因此由具有特定支鏈結構之液晶配向處理劑所得的液晶配向膜,比較先前長鏈烷基之支鏈構造物時,可得更安定的液晶垂直配向性。 The specific polymer (A) of the present invention is represented by the formula [1] The specific branched chain structure shown is a branched site having at least one selected from a benzene ring, a cyclohexyl ring, and a heterocyclic ring, or a bivalent organic group having 17 to 51 carbon atoms having a steroid skeleton. The branched structures of these rings and organic groups are more rigid when compared to the branched structures of the long-chain alkyl groups of the prior art in which liquid crystals are vertically aligned. Therefore, a liquid crystal alignment film obtained from a liquid crystal alignment treatment agent having a specific branched structure can obtain a more stable vertical alignment of the liquid crystal when compared with a branched structure of a long chain alkyl group.

又,特定支鏈結構比較先前的長鏈烷基之支鏈結構時,相對於紫外線等光線較為安定。因此特定支鏈結構既使曝露於長時間光照射,也可抑制電壓保持率降低,且可抑制因直流電壓而蓄積殘留電荷的支鏈成分之分解。 Moreover, when a specific branched structure is compared with the branched structure of the previous long-chain alkyl group, it is more stable with respect to light, such as an ultraviolet-ray. Therefore, even if the specific branched chain structure is exposed to long-term light irradiation, it is possible to suppress a decrease in the voltage holding ratio, and to suppress the decomposition of branched chain components that accumulate residual charges due to a DC voltage.

另外本發明的液晶配向處理劑為,具有特定聚合物(A)及特定聚合物(B)之液晶配向處理劑,特定聚合物(B)為不含特定支鏈結構。因此由本發明之液晶配向處理劑所得的液晶配向膜為,可減少會提高液晶配向膜之體積電阻的支鏈成分之含量,而抑制因直流電流所蓄積的殘留電荷。 The liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment treatment agent having a specific polymer (A) and a specific polymer (B), and the specific polymer (B) does not contain a specific branched structure. Therefore, the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention can reduce the content of the branched chain components that can increase the volume resistance of the liquid crystal alignment film, and suppress the residual charge accumulated by the direct current.

故本發明的液晶配向處理劑可得,既使曝露於長時間高溫及光照射後,仍可發現安定之預傾角的液晶配向膜。又,可得既使曝露於長時間光照射後,仍可抑制電壓保持率降低,且加速緩和因直流電壓所蓄積的殘留電荷。 Therefore, the liquid crystal alignment treatment agent of the present invention can be obtained, and even after being exposed to high temperature and light irradiation for a long time, a stable liquid crystal alignment film with a pretilt angle can be found. In addition, even after being exposed to long-term light irradiation, it is possible to suppress the decrease in the voltage holding ratio and accelerate and reduce the residual charge accumulated by the DC voltage.

<特定支鏈結構> <Specific branch chain structure>

本發明的特定聚合物(A)為,含有由含有具 有下述式[1]所表示的特定支鏈結構之二胺化合物的二胺成分,與四羧酸成分反應所得的聚醯亞胺先驅物及聚醯亞胺中所選出的至少任何一方的聚合物。 The specific polymer (A) of the present invention is At least one selected from the group consisting of a diamine component of a diamine compound having a specific branched chain structure represented by the following formula [1], and a polyimide precursor obtained by reacting with a tetracarboxylic acid component, and polyimide polymer.

(式[1]中,Y1、Y2、Y3、Y4、Y5、Y6及n之定義與上述相同)。 (In the formula [1], the definitions of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 and n are the same as above).

式[1]中,Y1就原料之取得性及合成容易性的觀點,較佳為單鍵結、-(CH2)a-(a為1~15之整數)、-O-、-CH2O-或COO-。更佳為單鍵結、-(CH2)a-(a為1~10之整數)、-O-、-CH2O-或COO-。Y2又以單鍵結或(CH2)b-(b為1~10之整數)為佳。Y3就合成容易性的觀點,較佳為單鍵結、-(CH2)c-(c為1~15之整數)、-O-、-CH2O-、或COO-。更佳為單鍵結、-(CH2)c-(c為1~10之整數)、-O-、-CH2O-或COO-。Y4就合成容易性的觀點,較佳為苯環、環己烷環或具有類固醇骨架的碳數17~51之有機基。Y5又以苯環或環己烷環為佳。n就原料之取得性及合成容易性的觀點,較佳為0~3。更佳為0~2。Y6又以碳數1~18之烷基、碳數1~10之含氟的烷基、碳數1~18之烷氧基或碳數1~10之含氟的烷氧基為佳。更佳為碳數1~12之烷基或碳數1~12之烷氧基。特佳為碳數1~9之烷基或碳數1~9之烷氧基。 In the formula [1], Y 1 is preferably a single bond,-(CH 2 ) a- (a is an integer of 1 to 15), -O-, -CH from the viewpoint of availability of raw materials and ease of synthesis. 2 O- or COO-. More preferably, it is a single bond,-(CH 2 ) a- (a is an integer of 1 to 10), -O-, -CH 2 O-, or COO-. Y 2 is preferably a single bond or (CH 2 ) b- (b is an integer from 1 to 10). From the viewpoint of ease of synthesis, Y 3 is preferably a single bond,-(CH 2 ) c- (c is an integer of 1 to 15), -O-, -CH 2 O-, or COO-. More preferably, it is a single bond,-(CH 2 ) c- (c is an integer of 1 to 10), -O-, -CH 2 O-, or COO-. From the viewpoint of ease of synthesis, Y 4 is preferably a benzene ring, a cyclohexane ring, or an organic group having 17 to 51 carbon atoms having a steroid skeleton. Y 5 is preferably a benzene ring or a cyclohexane ring. From the viewpoint of availability of raw materials and ease of synthesis, n is preferably 0 to 3. More preferably, it is 0 to 2. Y 6 is preferably an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

式[1]中,Y1、Y2、Y3、Y4、Y5、Y6及n之較 佳組合如,與國際公開公報WO 2011/132751(2011.10.27公開)之13頁~34頁的表6~表47所揭示的(2-1)~(2-629)相同之組合。又,國際公開公報之各表中,本發明的Y1~Y6係以Y1~Y6表示,Y1~Y6可解讀為Y1~Y6之物。又,國際公開公報之各表所揭示的(2-605)~(2-629)中,本發明的具有類固醇骨架的碳數17~51之有機基係表示為具有類固醇骨架的碳數12~25之有機基,又具有類固醇骨架的碳數12~25之有機基可解讀為具有類固醇骨架的碳數17~51之有機基之物。 In the formula [1], a preferred combination of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 and n is, for example, as shown in pages 13 to 34 of International Publication WO 2011/132751 (published on 2011.10.27). The same combinations as (2-1) to (2-629) disclosed in Tables 6 to 47 on the page. In the tables of the International Publication, Y 1 to Y 6 of the present invention are represented by Y 1 to Y 6 , and Y 1 to Y 6 can be interpreted as Y 1 to Y 6 . Further, in (2-605) to (2-629) disclosed in the tables of the International Publication, the organic group having 17 to 51 carbon atoms having a steroid skeleton of the present invention is represented as having 12 to 6 carbon atoms having a steroid skeleton. The organic group of 25, and the organic group of 12 to 25 carbons having a steroid skeleton can be interpreted as the organic group of 17 to 51 carbons having a steroid skeleton.

其中較佳為(2-25)~(2-96)、(2-145)~(2-168)、(2-217)~(2-240)、(2-268)~(2-315)、(2-364)~(2-387)、(2-436)~(2-483)、或(2-603)~(2-615)之組合。特佳之組合為(2-49)~(2-96)、(2-145)~(2-168)、(2-217)~(2-240)、(2-603)~(2-606)、(2-607)~(2-609)、(2-611)、(2-612)或(2-624)。 Among them, (2-25) ~ (2-96), (2-145) ~ (2-168), (2-217) ~ (2-240), (2-268) ~ (2-315) ), (2-364) ~ (2-387), (2-436) ~ (2-483), or (2-603) ~ (2-615). The best combination is (2-49) ~ (2-96), (2-145) ~ (2-168), (2-217) ~ (2-240), (2-603) ~ (2-606) ), (2-607) to (2-609), (2-611), (2-612), or (2-624).

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

特定聚合物(A)及特定聚合物(B)為,含有由二胺成分與四羧酸成分反應所得的聚醯亞胺先驅物及聚醯亞胺(也總稱為聚醯亞胺系聚合物)中所選出的至少任何一方的聚合物。 The specific polymer (A) and the specific polymer (B) include a polyimide precursor and a polyimide (also collectively referred to as a polyimide polymer) obtained by reacting a diamine component and a tetracarboxylic acid component. A polymer selected from at least one of the above).

聚醯亞胺先驅物係指下述式[A]所表示的結構。 The polyfluorene imide precursor refers to a structure represented by the following formula [A].

(R1為四價之有機基,R2為二價之有機基,A1及A2表示氫原子或碳數1~8之烷基,可各自相同或相異,A3及A4表示氫原子、碳數1~5之烷基或乙醯基,可各自相同或相異,n2表示正整數)。 (R 1 is a tetravalent organic group, R 2 is a divalent organic group, A 1 and A 2 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, which may be the same or different from each other, and A 3 and A 4 represent A hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an ethynyl group may be the same as or different from each other, and n2 represents a positive integer).

前述二胺成分為,分子內具有2個一級或二級胺基的二胺化合物,四羧酸成分如,四羧酸化合物、四羧酸二酐、四羧酸二鹵化合物、四羧酸二烷基酯化合物或四羧酸二烷基酯二鹵化合物。 The diamine component is a diamine compound having two primary or secondary amine groups in the molecule, and a tetracarboxylic acid component such as a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a tetracarboxylic dihalide compound, and a tetracarboxylic acid di An alkyl ester compound or a dialkyl tetracarboxylic acid dihalide compound.

本發明的聚醯亞胺系聚合物係以下述式[B]所表示的四羧酸二酐與下述式[C]所表示的二胺化合物為原料,就較簡便製造之理由,較佳為由下述式[D]所表示的重覆單位之結構式所形成的聚醯胺酸或該聚醯胺酸被醯亞胺化而得的聚醯亞胺。其中特定聚合物(A)及特定聚合物(B)就液晶配向膜的物理性及化學性之安定性的觀點,又以使用聚醯亞胺為佳。 The polyfluorene imide polymer of the present invention is preferably made from a tetracarboxylic dianhydride represented by the following formula [B] and a diamine compound represented by the following formula [C] as raw materials, and is preferable for reasons of simpler production. The polyamidic acid formed by the structural formula of the repeating unit represented by the following formula [D], or the polyamidoimide obtained by polyimidating this polyamidic acid. Among them, the specific polymer (A) and the specific polymer (B) are preferably polyimide from the viewpoint of the physical and chemical stability of the liquid crystal alignment film.

(R1及R2與式[A]之定義相同)。 (R 1 and R 2 are the same as defined in formula [A]).

(R1、R2及n2與式[A]之定義相同)。 (R 1 , R 2 and n2 are the same as defined in formula [A]).

又,一般合成方法中,可將式[A]所表示的A1及A2的碳數1~8之烷基,及式[A]所表示的A3及A4的碳數1~5之烷基或乙醯基導入上述所得的式[D]之聚合物中。 Further, in a general synthesis method, an alkyl group having 1 to 8 carbon atoms of A 1 and A 2 represented by the formula [A], and 1 to 5 carbon atoms of A 3 and A 4 represented by the formula [A] can be used. The alkyl group or acetamidine group is introduced into the polymer of the formula [D] obtained above.

特定聚合物(A)為,使用含有具有特定支鏈結構之二胺化合物的二胺成分所得的聚醯亞胺系聚合物。此時具有特定支鏈結構之二胺化合物較佳為,使用下述式[1a]所表示的二胺化合物(也稱為特定支鏈型二胺化合物)。 The specific polymer (A) is a polyfluorene-imide-based polymer obtained by using a diamine component containing a diamine compound having a specific branched structure. In this case, the diamine compound having a specific branched structure is preferably a diamine compound (also referred to as a specific branched diamine compound) represented by the following formula [1a].

式[1a]中,Y1、Y2、Y3、Y4、Y5、Y6及n各自與上述式[1]之定義相同,各自之較佳定義也相同。 In the formula [1a], Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6, and n are each the same as the definition of the above formula [1], and their preferred definitions are also the same.

又,Y1、Y2、Y3、Y4、Y5、Y6及n之較佳組合也與上 述式[1]所記載之物相同。又,m為1~4之整數。較佳為1之整數。 The preferred combinations of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6, and n are also the same as those described in the above formula [1]. In addition, m is an integer of 1 to 4. It is preferably an integer of 1.

具體例如,下述式[1a~1]~式[1a-31]所表示的結構。 Specific examples are the structures represented by the following formulas [1a to 1] to [1a-31].

(R1表示-O-、-OCH2-、-CH2O-、-COOCH2-或CH2OCO-、R2為碳數1~22之直鏈狀或支鏈狀烷基、碳數1~22之直鏈狀或支鏈狀烷氧基、碳數1~22之直鏈狀或支鏈狀含氟的烷基或含氟的烷氧基)。 (R 1 represents -O-, -OCH 2- , -CH 2 O-, -COOCH 2 -or CH 2 OCO-, and R 2 is a linear or branched alkyl group having 1 to 22 carbon atoms and carbon number. 1 to 22 linear or branched alkoxy groups, 1 to 22 carbon straight or branched chain fluorine-containing alkyl groups or fluorine-containing alkoxy groups).

(R3表示-COO-、-OCO-、-CONH-、-NHCO-、-COOCH2-、-CH2OCO-、-CH2O-、-OCH2-或CH2-,R4為碳數1~22之直鏈狀或支鏈狀烷基、碳數1~22之直鏈狀或支鏈狀烷氧基、碳數1~22之直鏈狀或支鏈狀含氟的烷基或含氟的烷氧基)。 (R 3 represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH 2- , -CH 2 OCO-, -CH 2 O-, -OCH 2 -or CH 2- , and R 4 is carbon Linear or branched alkyl group having 1 to 22 carbon atoms, linear or branched alkoxy group having 1 to 22 carbon atoms, linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms Or fluorine-containing alkoxy).

(R5表示-COO-、-OCO-、-CONH-、-NHCO-、-COOCH2-、-CH2OCO-、-CH2O-、-OCH2-、-CH2-、-O-或NH-,R6為氟基、氰基、三氟甲烷基、硝基、偶氮基、甲醯基、乙醯基、乙醯氧基或羥基)。 (R 5 represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH 2- , -CH 2 OCO-, -CH 2 O-, -OCH 2- , -CH 2- , -O- Or NH-, and R 6 is fluoro, cyano, trifluoromethyl, nitro, azo, formamyl, ethenyl, ethenyloxy, or hydroxy).

(R7為碳數3~12之直鏈狀或支鏈狀烷基,1,4-環伸己基之順-反異構各自為反異構體)。 (R 7 is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomers of 1,4-cyclohexyl are each an isomer).

(R8為碳數3~12之直鏈狀或支鏈狀烷基,1,4-環伸己基之順-反異構各自為反異構體)。 (R 8 is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomers of 1,4-cyclohexyl are each an isomer).

(A4為可被氟原子取代的碳數3~20之直鏈狀或支鏈狀烷基,A3為1,4-環伸己基或1,4-伸苯基,A2為氧原子或COO- *(又,附「*」之鍵結鍵係與A3鍵結),A1為氧原子或COO- *(又,附「*」之鍵結鍵係與(CH2)a2鍵結)。又,a1為0或1之整數,a2為2~10之整數,a3為0或1之整數)。 (A 4 is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, A 3 is 1,4-cyclohexyl or 1,4-phenylene, and A 2 is an oxygen atom Or COO- * (again, the bond system with "*" is bonded to A 3 ), A 1 is an oxygen atom or COO- * (again, the bond system with "*" is connected to (CH 2 ) a 2 bond). Also, a 1 is an integer of 0 or 1, a 2 is an integer of 2 to 10, and a 3 is an integer of 0 or 1.).

上述式[1a-1]~[1a-31]中,特佳結構之二胺化合物為式[1a-1]~式[1a-6]、式[1a-9]~式[1a-13]或式[1a-22]~式[1a-31]。 In the above formulas [1a-1] to [1a-31], the diamine compound having a particularly preferable structure is formula [1a-1] to formula [1a-6], formula [1a-9] to formula [1a-13] Or formula [1a-22] ~ formula [1a-31].

特定聚合物(A)之特定支鏈型二胺化合物較佳為,二胺成分全體的10莫耳%以上80莫耳%以下。特佳為10莫耳%以上70莫耳%以下。 The specific branched diamine compound of the specific polymer (A) is preferably 10 mol% or more and 80 mol% or less of the entire diamine component. Particularly preferred is 10 mol% to 70 mol%.

特定支鏈型二胺化合物可因應特定聚合物(A)相對於溶劑之溶解性、液晶配向處理劑之塗佈性、作為液晶配向膜用時之液晶的配向性、電壓保持率、蓄積電荷等之特性,使用一種或二種以上混合使用。 The specific branched diamine compound can respond to the solubility of the specific polymer (A) with respect to the solvent, the coating property of the liquid crystal alignment treatment agent, the alignment property of the liquid crystal when used as a liquid crystal alignment film, the voltage holding ratio, and the accumulated charge, etc. Characteristics, use one or two or more mixed.

製作特定聚合物(A)及特定聚合物(B)時之二胺成分較佳為,同時使用特定支鏈型二胺化合物與其他的二胺化合物(也稱為特定第二之二胺化合物)。 When the specific polymer (A) and the specific polymer (B) are produced, the diamine component is preferably used together with a specific branched diamine compound and another diamine compound (also referred to as a specific second diamine compound). .

其中又以使用具有由羧基(COOH基)及羥 基(OH基)中所選出的至少一種之取代基的二胺化合物。 Among them, the carboxyl group (COOH group) and hydroxyl group are used. A diamine compound of at least one selected from the group (OH group).

具體上較佳為使用下述式[2a]所表示的二胺化合物。 Specifically, it is preferable to use a diamine compound represented by the following formula [2a].

式[2a]中,A1表示由下述式[2a-1]及式[2a-2]中所選出的至少1個結構之取代基。其中較佳為式[2a-1]所表示的結構之取代基。 In formula [2a], A 1 represents a substituent of at least one structure selected from the following formula [2a-1] and formula [2a-2]. Among these, a substituent of the structure represented by Formula [2a-1] is preferable.

式[2a]中,m1表示1~4之整數。其中較佳為1。 In the formula [2a], m1 represents an integer of 1 to 4. Among them, 1 is preferred.

[化26]-(CH2)d-COOH [2a-1] -(CH2)e-OH [2a-2] [Chem. 26]-(CH 2 ) d -COOH [2a-1]-(CH 2 ) e -OH [2a-2]

式[2a-1]中,d表示0~4之整數。其中較佳為0或1。 In the formula [2a-1], d represents an integer of 0 to 4. Among them, 0 or 1 is preferred.

式[2a-2]中,e表示0~4之整數。其中較佳為0或1。 In the formula [2a-2], e represents an integer of 0 to 4. Among them, 0 or 1 is preferred.

更具體如,2,4-二胺基苯酚、3,5-二胺基苯酚、3,5-二胺基苄醇、2,4-二胺基苄醇、4,6-二胺基間苯二酚、2,4-二胺基苯甲酸、2,5-二胺基苯甲酸或3,5-二胺基苯甲酸。其中較佳為2,4-二胺基苯甲酸、2,5-二胺基苯甲 酸或3,5-二胺基苯甲酸。 More specifically, for example, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diamino group Resorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, or 3,5-diaminobenzoic acid. Among them, 2,4-diaminobenzoic acid and 2,5-diaminobenzoic acid are preferred. Acid or 3,5-diaminobenzoic acid.

又,特定第二之二胺化合物可為,使用下述式[2b-1]~式[2b-4]所表示的二胺化合物。 The specific second diamine compound may be a diamine compound represented by the following formulas [2b-1] to [2b-4].

(A1表示單鍵結、-CH2-、-C2H4-、-C(CH3)2-、-CF2-、-C(CF3)2-、-O-、-CO-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-CH2O-、-OCH2-、-COO-、-OCO-、-CON(CH3)-或N(CH3)CO-、m1及m2各自表示0~4之整數,且m1+m2表示1~4之整數,式[2b-2]中,m3及m4各自表示1~5之整數,式[2b-3]中,A2表示碳數1~5之直鏈或支鏈烷基,m5表示1~5之整數,式[2b-4]中,A3表示單鍵結、-CH2-、-C2H4-、-C(CH3)2-、-CF2-、-C(CF3)2-、-O-、-CO-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-CH2O-、-OCH2-、-COO-、-OCO-、-CON(CH3)-或N(CH3)CO-、m6表示1~4之整數)。 (A 1 represents a single bond, -CH 2- , -C 2 H 4- , -C (CH 3 ) 2- , -CF 2- , -C (CF 3 ) 2- , -O-, -CO- , -NH-, -N (CH 3 )-, -CONH-, -NHCO-, -CH 2 O-, -OCH 2- , -COO-, -OCO-, -CON (CH 3 )-or N ( CH 3 ) CO-, m 1 and m 2 each represent an integer of 0 to 4, and m 1 + m 2 represents an integer of 1 to 4; in formula [2b-2], m 3 and m 4 each represent 1 to 5 Integer, in the formula [2b-3], A 2 represents a linear or branched alkyl group having 1 to 5 carbon atoms, m 5 represents an integer of 1 to 5, and in the formula [2b-4], A 3 represents a single bond Junction, -CH 2- , -C 2 H 4- , -C (CH 3 ) 2- , -CF 2- , -C (CF 3 ) 2- , -O-, -CO-, -NH-,- N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - CON (CH 3) - or N (CH 3) CO-, m 6 represents an integer of 1 to 4).

特定第二之二胺化合物可使用於特定聚合物(A)或 特定聚合物(B)中任一種聚醯亞胺系聚合物的二胺成分,或可使用於特定聚合物(A)及特定聚合物(B)雙方之特定聚合物的二胺成分。其中較佳為,僅使用於特定聚合物(A)之二胺成分,或僅使用於特定聚合物(B)之二胺成分。 Specific second diamine compounds can be used for specific polymers (A) or The diamine component of any of the polyfluorene-imide-based polymers of the specific polymer (B) may be a diamine component of a specific polymer that can be used for both the specific polymer (A) and the specific polymer (B). Among these, it is preferable to use only the diamine component of a specific polymer (A), or to use only the diamine component of a specific polymer (B).

特定第二之二胺化合物較佳為,二胺成分全體的10莫耳%以上。其中又以20莫耳%以上為佳,特佳為30莫耳%以上。 The specific second diamine compound is preferably 10 mol% or more of the entire diamine component. Among them, more than 20 mol% is preferred, and particularly preferred is more than 30 mol%.

特定第二之二胺化合物可因應特定聚合物(A)及特定聚合物(B)相對於溶劑之溶解性、液晶配向處理劑之塗佈性、作為液晶配向膜用時之液晶的配向性、電壓保持率、蓄積電荷等,可使用一種或二種以上混合使用。 The specific second diamine compound can respond to the solubility of the specific polymer (A) and the specific polymer (B) with respect to the solvent, the coating property of the liquid crystal alignment treatment agent, the alignment property of the liquid crystal when used as a liquid crystal alignment film, The voltage holding ratio and the stored charge can be used singly or in combination of two or more kinds.

本發明的特定聚合物(A)及特定聚合物(B)之二胺成分較佳為,同時使用特定支鏈型二胺化合物與特定第二之二胺化合物,以及下述式[3a]所表示的二胺化合物(也稱為特定第三之二胺化合物)。 The diamine component of the specific polymer (A) and the specific polymer (B) of the present invention is preferably a combination of a specific branched diamine compound and a specific second diamine compound, and the following formula [3a] Represents a diamine compound (also referred to as a specific third diamine compound).

式[3a]中,B1表示-O-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-CH2O-、-OCO-、-CON(CH3)-或N(CH3)CO-。其中就易合成二胺化合物較佳為-O-、-NH- 、-CONH-、-NHCO-、-CH2O-、-OCO-、-CON(CH3)-或N(CH3)CO-。特佳為-O-、-NH-、-CONH-、-NHCO-、-CH2O-、-OCO-或CON(CH3)-。更佳為-O-、-CONH-或CH2O-。 In Formula [3a], B 1 represents -O-, -NH-, -N (CH 3 )-, -CONH-, -NHCO-, -CH 2 O-, -OCO-, -CON (CH 3 )- Or N (CH 3 ) CO-. Among these, it is preferable to easily synthesize a diamine compound -O-, -NH-, -CONH-, -NHCO-, -CH 2 O-, -OCO-, -CON (CH 3 )-or N (CH 3 ) CO -. Particularly preferred is -O -, - NH -, - CONH -, - NHCO -, - CH 2 O -, - OCO- or CON (CH 3) -. More preferably -O -, - CONH-, or CH 2 O-.

式[3a]中,B2表示單鍵結、碳數1~20之伸烷基、非芳香族環或芳香族環。 In the formula [3a], B 2 represents a single bond, an alkylene group having 1 to 20 carbon atoms, a non-aromatic ring or an aromatic ring.

碳數1~20之伸烷基可為直鏈狀或支鏈狀。又,可具有不飽和鍵結。特佳為碳數1~10之伸烷基。 The alkylene group having 1 to 20 carbon atoms may be linear or branched. Moreover, it may have an unsaturated bond. Particularly preferred is an alkylene group having 1 to 10 carbon atoms.

非芳香族環之具體例如,環丙烷環、環丁烷環、環戊烷環、環己烷環、環庚烷環、環辛烷環、環壬烷環、環癸烷環、環十一烷環、環十二烷環、環十三烷環、環十四烷環、環十五烷環、環十六烷環、環十七烷環、環十八烷環、環十九烷環、環二十烷環、三環二十烷環、三環、二環庚烷環、十氫萘環、降冰片烯環或金剛烷環等。其中較佳為環丙烷環、環丁烷環、環戊烷環、環己烷環、環庚烷環、降冰片烯環或金剛烷環。 Specific examples of the non-aromatic ring include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, and a ring eleven Alkanes, cyclododecanes, cyclotridecanes, cyclotetradecanes, cyclopentadecans, cyclohexadecanes, cycloheptadecans, cyclooctadecanes, cyclononadecanes , Cycloeicosane ring, tricyclic eicosane ring, tricyclic, dicycloheptane ring, decalin ring, norbornene ring or adamantane ring, etc. Among them, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring or an adamantane ring are preferred.

芳香族環之具體例如,苯環、萘環、四氫萘環、薁環、茚環、芴環、蒽環、菲環或萉環等。其中較佳為苯環、萘環、四氫萘環、芴環或蒽環。 Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among them, a benzene ring, a naphthalene ring, a tetralin ring, a fluorene ring, or an anthracene ring is preferred.

式[3a]中B2較佳為單鍵結、碳數1~10之伸烷基、環丙烷環、環丁烷環、環戊烷環、環己烷環、環庚烷環、降冰片烯環、金剛烷環、苯環、萘環、四氫萘環、芴環或蒽環。其中又以單鍵結、碳數1~5之伸烷基、環己烷環或苯環為佳。 B 2 in formula [3a] is preferably a single bond, an alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, or norbornyl. Ethene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring or anthracene ring. Among them, a single bond, an alkylene group having 1 to 5 carbon atoms, a cyclohexane ring or a benzene ring is preferred.

式[3a]中,B3表示單鍵結、-O-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-COO-、-OCO-、-CON(CH3)-或N(CH3)CO-、-O(CH2)m2-(m2為1~5之整數)。其中較佳為單鍵結、-O-、-COO-、-OCO-或O(CH2)m2-(m2為1~5之整數),特佳為單鍵結、-O-、-OCO-或O(CH2)m2-(m2為1~5之整數)。 In formula [3a], B 3 represents a single bond, -O-, -NH-, -N (CH 3 )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH 3 )-Or N (CH 3 ) CO-, -O (CH 2 ) m2- (m2 is an integer from 1 to 5). Among them, a single bond, -O-, -COO-, -OCO- or O (CH 2 ) m2- (m2 is an integer of 1 to 5) is preferred, and a single bond, -O-, -OCO is particularly preferred -Or O (CH 2 ) m2- (m2 is an integer from 1 to 5).

式[3a]中,B4為含氮的雜環,含有由下述式[a]、式[b]及式[c]中所選出的至少1個結構的雜環。 In the formula [3a], B 4 is a nitrogen-containing heterocyclic ring and contains a heterocyclic ring having at least one structure selected from the following formulas [a], [b], and [c].

(式[c]中,Z表示碳數1~5之烷基)。 (In the formula [c], Z represents an alkyl group having 1 to 5 carbon atoms).

更具體如,吡咯環、咪唑環、噁唑環、噻唑環、吡唑環、吡啶環、嘧啶環、喹啉環、吡唑啉環、異喹啉環、咔唑環、嘌呤環、噻二唑環、噠嗪環、吡唑啉環、三嗪環、吡唑啶環、三唑環、吡嗪環、苯并咪唑環(benzimidazole環;benzoimidazole環)、噌啉環、菲繞啉環、吲哚環、喹喔啉環、苯并噻唑環、吩噻嗪環、噁二唑環或吖啶環等。其中較佳為吡咯環、咪唑環、吡唑環、吡啶環、嘧啶環、噠嗪環、三嗪環、三唑環、吡嗪環、苯并咪唑環(benzimidazole環;benzoimidazole環),特佳為吡咯環、咪唑環、吡唑環、吡啶環或嘧啶環。 More specifically, for example, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiazole Azole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazidine ring, triazole ring, pyrazine ring, benzimidazole ring (benzoimidazole ring), perylene ring, phenanthroline ring, Indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring or acridine ring and the like. Among them, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, and a benzimidazole ring (benzoimidazole ring) are preferred, and particularly preferred It is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring.

又,式[3a]中B3較佳為,與未與B4所含有式[a]、式[b]及式[c]接鄰之取代基鍵結。 In addition, in formula [3a], B 3 is preferably bonded to a substituent which is not adjacent to formula [a], formula [b], and formula [c] contained in B 4 .

式[3a]中較佳的B1、B2、B3及B4之組合如下述表1~表31所示。又,表1~表31中X1、X2、X3及X4可各自解讀為B1、B2、B3及B4之物。 The preferred combinations of B 1 , B 2 , B 3 and B 4 in formula [3a] are shown in Tables 1 to 31 below. In addition, in Tables 1 to 31, X 1 , X 2 , X 3 and X 4 can be interpreted as B 1 , B 2 , B 3 and B 4 respectively .

式[3a]中,n1為1~4之整數,就與四羧酸成分之反應性的觀點,較佳為1或2。 In the formula [3a], n1 is an integer of 1 to 4, and from the viewpoint of reactivity with a tetracarboxylic acid component, 1 or 2 is preferable.

式[3a]中特佳的B1、B2、B3、B4及n1之組合為,B1表示-CONH-,B2表示碳數1~5之烷基,B3表示單鍵結,B4表示咪唑環或吡啶環,n1表示1之二胺化合物。 The particularly preferred combination of B 1 , B 2 , B 3 , B 4 and n1 in formula [3a] is: B 1 represents -CONH-, B 2 represents an alkyl group having 1 to 5 carbon atoms, and B 3 represents a single bond , B 4 represents an imidazole ring or a pyridine ring, and n1 represents a diamine compound of 1.

式[3a]中2個胺基(-NH2)之鍵結位置無限定。具體如,相對於支鏈之鍵結基(B1)的苯環上2,3之位置、2,4之位置、2,5之位置、2,6之位置、3,4之位置或3,5之位置。其中就合成聚醯胺酸時之反應性的觀點,較佳為2,4之位置、2,5之位置或3,5之位置。另加上合成二胺化合物時之容易性,更佳為2,4之位置或2,5之位置。 The bonding position of the two amine groups (-NH 2 ) in the formula [3a] is not limited. Specifically, for example, the position of 2,3 on the benzene ring with respect to the branched bonding group (B 1 ), the position of 2,4, the position of 2,5, the position of 2,6, the position of 3,4 or 3 , The position of 5. Among them, from the viewpoint of reactivity when synthesizing polyamic acid, the positions of 2, 4 and 2, 5 or 3 and 5 are preferred. In addition, the ease of synthesizing the diamine compound is more preferably a position of 2,4 or a position of 2,5.

特定第三之二胺化合物可使用於特定聚合物(A)或特定聚合物(B)中任一方之聚醯亞胺系聚合物的二胺成分中,也可使用於特定聚合物(A)及特定聚合 物(B)雙方之特定聚合物的二胺成分中。其中特定聚合物(A)之二胺成分係使用特定第二之二胺化合物時,特定第三之二胺化合物較佳為使用於特定聚合物(B)之二胺成分中。又,特定聚合物(B)之二胺成分係使用特定第二之二胺化合物時,特定第三之二胺化合物較佳為使用於特定聚合物(A)之二胺成分。即,相對於各特定聚合物較佳為,特定第二之二胺化合物與特定第三之二胺化合物各自使用於二胺成分。 The specific third diamine compound can be used in the diamine component of the polyimide-based polymer of either the specific polymer (A) or the specific polymer (B), and can also be used in the specific polymer (A). And specific aggregations (B) in the diamine component of the specific polymer on both sides. When the diamine component of the specific polymer (A) is a specific second diamine compound, the specific third diamine compound is preferably used for the diamine component of the specific polymer (B). When the diamine component of the specific polymer (B) is a specific second diamine compound, the specific third diamine compound is preferably a diamine component used in the specific polymer (A). That is, it is preferable that the specific second diamine compound and the specific third diamine compound are each used for a diamine component with respect to each specific polymer.

特定第三之二胺化合物較佳為,二胺成分全體的5莫耳%以上。其中又以10莫耳%以上為佳,特佳為15莫耳%以上。 The specific third diamine compound is preferably 5 mol% or more of the entire diamine component. Among them, more than 10 mol% is preferred, and particularly preferred is more than 15 mol%.

特定第三之二胺化合物可因應特定聚合物(A)及特定聚合物(B)相對於溶劑之溶解性、液晶配向處理劑之塗佈性、作為液晶配向膜用時之液晶的配向性、電壓保持率、蓄積電荷等之特性,可使用一種或二種以上混合使用。 The specific third diamine compound can respond to the solubility of the specific polymer (A) and the specific polymer (B) with respect to the solvent, the coating property of the liquid crystal alignment treatment agent, the alignment property of the liquid crystal when used as a liquid crystal alignment film, The characteristics of the voltage holding rate and the stored charge can be used singly or in combination of two or more kinds.

特定聚合物(A)及特定聚合物(B)的二胺成分於無損本發明之效果的範圍內,可同時使用特定支鏈型二胺化合物、特定第二之二胺化合物及特定第三之二胺化合物,與其他的二胺化合物(也稱為其他二胺化合物)。 As long as the diamine component of the specific polymer (A) and the specific polymer (B) does not impair the effect of the present invention, a specific branched diamine compound, a specific second diamine compound, and a specific third Diamine compounds, and other diamine compounds (also known as other diamine compounds).

其他二胺化合物具體如,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、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’-二胺基二苯基醚、3,3’-二胺基二苯基醚、3,4’-二胺基二苯基醚、2,2’-二胺基二苯基醚、2,3’-二胺基二苯基醚、4,4’-磺醯二苯胺、3,3’-磺醯二苯胺、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’-硫二苯胺、3,3’-硫二苯胺、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-胺基苯醯胺)、N,N’-(1,3-伸苯基)雙(4-胺基苯醯胺)、N,N’-(1,4-伸苯基)雙(3-胺基苯醯胺)、N,N’-(1,3-伸苯基)雙(3-胺基苯醯胺)、N,N’-雙(4-胺基苯基)對苯二甲醯胺、N,N’-雙(3-胺基苯基)對苯二甲醯胺、N,N’-雙(4-胺基苯基)間苯二甲醯胺、N,N’-雙(3-胺基苯基)間苯二甲醯胺、9,10-雙(4-胺基苯基)蒽、4,4’-雙(4-胺基苯氧基)二苯基碸、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-雙(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-雙(4-胺基苯氧基)癸烷、1,10-雙(3-胺基苯氧基)癸烷、1,11-雙(4-胺基苯氧基)十一烷、1,11-雙(3-胺基苯氧基)十一烷、1,12-雙(4-胺基苯氧基)十二烷、1,12-雙(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1,12-二胺基十二烷等。 Specific examples of other diamine compounds include 2,4-dimethyl-m-phenylene diamine, 2,6-diamino toluene, m-phenylene diamine, p-phenylene diamine, 4, 4'-diaminobiphenyl, 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, 2,3'-diaminobiphenyl, 4,4'-diaminobiphenyl Methane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diamine Diphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-di Amino diphenyl ether, 2,3'-diamino diphenyl ether, 4,4'-sulfohydrazine diphenylamine, 3,3'-sulfohydrazine diphenylamine, 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 2,2'-diaminodiphenylamine, 2,3'-diaminodiamine Amino, 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'-Diaminobenzophenone, 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-Diaminonaphthalene, 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-amine Phenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, Bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene , 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3- Bis (4-aminophenoxy) benzene, 4,4 '-[1,4-phenylenebis (methylene)] diphenylamine, 4,4'-[1,3-phenylenebis ( Methylene)] diphenylamine, 3,4 '-[1,4-phenylene bis (methylene)] diphenylamine, 3,4'-[1,3-phenylene bis (methylene) ] Diphenylamine, 3,3 '-[1,4-phenylenebis (methylene)] diphenylamine, 3,3'-[1,3-phenylenebis (methylene)] diphenylamine, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylphenylbis [(3-aminophenyl) methanone], 1,4-phenylphenylbis (4-aminobenzoic acid) Esters), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis ( 3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) Group) isophthalate, bis (3-aminophenyl) m-xylylene Acid ester, N, N '-(1,4-phenylene) bis (4-aminophenylhydrazine), N, N'-(1,3-phenylene) bis (4-aminophenylhydrazone) Amine), N, N '-(1,4-phenylene) bis (3-aminophenylhydrazone), N, N'-(1,3-phenylene) bis (3-aminophenylhydrazone) Amine), N, N'-bis (4-aminophenyl) p-xylylenediamine, N, N'-bis (3-aminophenyl) p-xylylenediamine, N, N'- Bis (4-aminophenyl) m-xylylenediamine, N, N'-bis (3-aminophenyl) m-xylylenediamine, 9,10-bis (4-aminophenyl) Anthracene, 4,4'-bis (4-aminophenoxy) diphenylphosphonium, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'- Bis [4- (4-aminophenoxy) phenyl] hexafluoro Propane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-amino- 4-methylphenyl) hexafluoropropane, 2,2'-bis (4-aminophenyl) propane, 2,2'-bis (3-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-bis (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-bis (4-aminophenoxy) decane, 1,10-bis (3-aminophenoxy) decane, 1,11-bis (4-aminophenoxy) undec Alkane, 1,11-bis (3-aminophenoxy) undecane, 1,12-bis (4-aminophenoxy) dodecane, 1,12-bis (3-aminophenoxy) ) Dodecane, bis (4-aminocyclohexyl) methyl , 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 the like.

又,其他二胺化合物可使用下述式[D1]~式[DA25]所表示的二胺化合物。 As the other diamine compounds, diamine compounds represented by the following formulas [D1] to [DA25] can be used.

(A1表示碳數1~22之烷基或含氟的烷基)。 (A 1 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).

(A1表示-COO-、-OCO-、-CONH-、-NHCO-、-CH2-、-O-、-CO-或NH-,A2表示碳數1~22之直鏈狀或支鏈狀烷基或碳數1~22之直鏈狀或支鏈狀含氟的烷基)。 (A 1 represents -COO-, -OCO-, -CONH-, -NHCO-, -CH 2- , -O-, -CO- or NH-, and A 2 represents a linear or branched carbon having 1 to 22 carbon atoms. Chain alkyl or linear or branched fluorine-containing alkyl having 1 to 22 carbon atoms).

(p表示1~10之整數)。 (p represents an integer from 1 to 10).

(m表示0~3之整數,n表示1~5之整數)。 (m represents an integer from 0 to 3, and n represents an integer from 1 to 5.)

其他二胺化合物可使用於特定聚合物(A)或特定聚合物(B)中任一方的聚醯亞胺系聚合物之二胺成分中,又可使用於特定聚合物(A)及特定聚合物(B)雙方的特定聚合物之二胺成分中。 Other diamine compounds can be used in the diamine component of the polyfluorene-imide polymer of either the specific polymer (A) or the specific polymer (B), and can also be used in the specific polymer (A) and the specific polymerization. (B) in the diamine component of the specific polymer on both sides.

又,其他二胺化合物可因應特定聚合物(A)及特定聚合物(B)相對於溶劑之溶解性、液晶配向處理劑之塗佈性、作為液晶配向膜用時之液晶的配向性、電壓 保持率、蓄積電荷等之特性,使用一種或二種以上混合使用。 In addition, other diamine compounds may respond to the solubility of the specific polymer (A) and the specific polymer (B) in a solvent, the coating property of a liquid crystal alignment treatment agent, the alignment property of a liquid crystal when used as a liquid crystal alignment film, and a voltage. Retention rate, accumulated charge, and other characteristics are used in combination of one kind or two or more kinds.

製作特定聚合物(A)及特定聚合物(B),即該等聚醯亞胺系聚合物用的四羧酸成分較佳為,使用下述式[4]所表示的四羧酸二酐(特定四羧酸二酐)。此時除了式[4]所表示的特定四羧酸二酐,也可使用該四羧酸衍生物的四羧酸、四羧酸二鹵化合物、四羧酸二烷基酯化合物或四羧酸二烷基酯二鹵化合物。 It is preferable to use the tetracarboxylic dianhydride represented by the following formula [4] to prepare the specific polymer (A) and the specific polymer (B), that is, the tetracarboxylic acid component for the polyfluorene-based polymer. (Specific tetracarboxylic dianhydride). In this case, in addition to the specific tetracarboxylic dianhydride represented by the formula [4], a tetracarboxylic acid, a tetracarboxylic dihalide compound, a tetracarboxylic dialkyl ester compound, or a tetracarboxylic acid of the tetracarboxylic acid derivative may be used. Dialkyl ester dihalide.

(Z1為由下述式[4a]~式[4k]中所選出的結構之基)。 (Z 1 is a base selected from the following formulas [4a] to [4k]).

式[4a]中,Z2~Z5表示氫原子、甲基、氯原子 或苯環,可各自相同或相異。 In the formula [4a], Z 2 to Z 5 represent a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring, and may be the same or different.

式[4g]中,Z6及Z7表示氫原子或甲基,可各自相同或相異。 In formula [4g], Z 6 and Z 7 represent a hydrogen atom or a methyl group, and may be the same or different.

式[4]中之Z1就合成容易性及製造聚合物時之聚合反應性的容易性之觀點,較佳為式[4a]、式[4c]、式[4d]、式[4e]、式[4f]、式[4g]或式[4k]所表示的結構之四羧酸二酐及其四羧酸衍生物。更佳為式[4a]、式[4e]、式[4f]、式[4g]或式[4k]所表示的結構物,特佳為式[4e]、式[4f]、式[4g]或式[4k]之物。 Z 1 in the formula [4] is preferably a formula [4a], a formula [4c], a formula [4d], a formula [4e], from the viewpoints of ease of synthesis and ease of polymerization reactivity when manufacturing a polymer. A tetracarboxylic dianhydride having a structure represented by Formula [4f], Formula [4g], or Formula [4k] and a tetracarboxylic acid derivative thereof. More preferably, it is a structure represented by Formula [4a], [4e], [4f], [4g], or [4k], and particularly preferably [4e], [4f], or [4g]. Or something of formula [4k].

本發明的聚醯亞胺系聚合物於無損本發明之效果的範圍內,也可使用特定四羧酸二酐以外之其他四羧酸成分。 The polyfluorene-imide polymer of the present invention may use other tetracarboxylic acid components other than the specific tetracarboxylic dianhydride, as long as the effect of the present invention is not impaired.

其他四羧酸成分如下述四羧酸化合物、四羧酸二酐、四羧酸二鹵化合物、四羧酸二烷基酯化合物或四羧酸二烷基酯二鹵化合物。 Other tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic dihalide compounds, tetracarboxylic acid dialkyl ester compounds, or tetracarboxylic acid dialkyl ester dihalogen compounds.

即,其他四羧酸成分如,均苯四酸、2,3,6,7-萘四羧酸、1,2,5,6-萘四羧酸、1,4,5,8-萘四羧酸、2,3,6,7-蒽四羧酸、1,2,5,6-蒽四羧酸、3,3’,4,4’-聯苯四羧酸、2,3,3’,4’-聯苯四羧酸、雙(3,4-二羧基苯基)醚、3,3’,4,4’-二苯甲酮四羧酸、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。 That is, other tetracarboxylic acid components such as pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid Carboxylic acid, 2,3,6,7-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3 ', 4'-Biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3', 4,4'-benzophenone tetracarboxylic acid, bis (3,4-dicarboxyl Phenyl) 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-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2 , 3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxybenzene ) Pyridine, 3,3 ', 4,4'-diphenylfluorenetetracarboxylic acid, 3,4,9,10-fluorenetetracarboxylic acid or 1,3-diphenyl-1,2,3,4 -Cyclobutane tetracarboxylic acid.

特定聚合物(A)及特定聚合物(B)之四羧酸成分較佳為,各特定聚合物之特定四羧酸二酐為四羧酸成分的10莫耳%以上。其中又以20莫耳%以上為佳,特佳為30莫耳%以上。四羧酸成分可全為特定四羧酸二酐。 The tetracarboxylic acid component of the specific polymer (A) and the specific polymer (B) is preferably such that the specific tetracarboxylic dianhydride of each specific polymer is 10 mol% or more of the tetracarboxylic acid component. Among them, more than 20 mol% is preferred, and particularly preferred is more than 30 mol%. The tetracarboxylic acid components may all be specific tetracarboxylic dianhydrides.

特定四羧酸二酐及其他四羧酸成分可因應特定聚合物(A)及特定聚合物(B)相對於溶劑之溶解性、液晶配向處理劑之塗佈性、作為液晶配向膜用時之液晶的配向性、電壓保持率、蓄積電荷等之特性,使用一種或二種以上混合使用。 The specific tetracarboxylic dianhydride and other tetracarboxylic acid components can be used in accordance with the solubility of the specific polymer (A) and the specific polymer (B) in a solvent, the coating property of a liquid crystal alignment treatment agent, and the liquid crystal alignment film. Liquid crystals have characteristics such as alignment, voltage retention, and accumulated charge, and are used by mixing one or two or more kinds.

<特定聚合物(A)及特定聚合物(B)之製造方法> <Production method of specific polymer (A) and specific polymer (B)>

本發明的特定聚合物(A)為,由含有具有前述式[1]所表示的特定支鏈結構之二胺化合物的二胺成分,與四羧酸成分反應所得的聚醯亞胺先驅物及聚醯亞胺所成群中所選出的至少一種之聚合物。此時具有特定支鏈結構的二胺化合物較佳為,使用前述式[1a]所表示的特定支鏈型二胺化合物。 The specific polymer (A) of the present invention is a polyimide precursor obtained by reacting a diamine component containing a diamine compound having a specific branched structure represented by the aforementioned formula [1] with a tetracarboxylic acid component, and A polymer of at least one selected from the group consisting of polyimide. In this case, the diamine compound having a specific branched structure is preferably a specific branched diamine compound represented by the formula [1a].

又,特定聚合物(A)中,特定支鏈型二胺化合物可併用具有由羧基及羥基中所選出的至少一種之取代基的二胺化合物,及/或前述式[3a]所表示的特定第三之二胺化合物。此時具有由羧基及羥基中所選出的至少一種之取代基 的二胺化合物較佳為,使用前述式[2a]所表示的特定第二之二胺化合物。 In the specific polymer (A), a specific branched diamine compound may be used in combination with a diamine compound having at least one selected from a carboxyl group and a hydroxyl group, and / or a specific compound represented by the formula [3a]. Third diamine compound. In this case, it has at least one selected from a carboxyl group and a hydroxyl group. The diamine compound is preferably a specific second diamine compound represented by the aforementioned formula [2a].

併用特定第二之二胺化合物時的使用比例較佳為,相對於二胺成分全體100莫耳%之特定支鏈型二胺化合物為10~80莫耳%,特定第二之二胺化合物為10~90莫耳%。更佳為,特定支鏈型二胺化合物為10~80莫耳%,特定第二之二胺化合物為20~70莫耳%。 When the specific second diamine compound is used in combination, the specific branched diamine compound is preferably 100-80 mol% with respect to 100 mol% of the total diamine component, and the specific second diamine compound is 10 ~ 90 mol%. More preferably, the specific branched diamine compound is 10 to 80 mol%, and the specific second diamine compound is 20 to 70 mol%.

併用特定第三之二胺化合物時的使用比例較佳為,相對於二胺成分全體100莫耳%的特定支鏈型二胺化合物為10~80莫耳%,特定第三之二胺化合物為10~90莫耳%。更佳為,特定支鏈型二胺化合物為10~80莫耳%,特定第三之二胺化合物為20~70莫耳%。 When using a specific tertiary diamine compound in combination, the specific branched diamine compound is preferably 10 to 80 mol% relative to 100 mol% of the total diamine component, and the specific tertiary diamine compound is 10 ~ 90 mol%. More preferably, the specific branched diamine compound is 10 to 80 mol%, and the specific third diamine compound is 20 to 70 mol%.

併用特定第二之二胺化合物及特定第三之二胺化合物時的使用比例較佳為,相對於二胺成分全體100莫耳%的特定支鏈型二胺化合物為10~80莫耳%,特定第二之二胺化合物為10~80莫耳%,特定第三之二胺化合物為10~80莫耳%。更佳為,特定支鏈型二胺化合物為10~80莫耳%,特定第二之二胺化合物為20~70莫耳%,特定第三之二胺化合物為20~70莫耳%。本發明中特定聚合物(A)較佳為併用特定第三之二胺化合物。 When the specific second diamine compound and the specific third diamine compound are used in combination, the specific branched chain diamine compound is preferably 10 to 80 mol% relative to 100 mol% of the total diamine component. The specific second diamine compound is 10 to 80 mole%, and the specific third diamine compound is 10 to 80 mole%. More preferably, the specific branched diamine compound is 10 to 80 mol%, the specific second diamine compound is 20 to 70 mol%, and the specific third diamine compound is 20 to 70 mol%. In the present invention, the specific polymer (A) is preferably a combination of a specific third diamine compound.

本發明的特定聚合物(B)為,由二胺成分未含具有特定支鏈結構之二胺化合物的二胺成分,與四羧酸成分反應所得的聚醯亞胺先驅物及聚醯亞胺所成群中所選出的至少一種之聚合物。此時特定聚合物(B)較佳為, 使用具有由羧基及羥基中所選出的至少一種之取代基的二胺化合物。更佳為前述式[2a]所表示的特定第二之二胺化合物。 The specific polymer (B) of the present invention is a polyimide precursor and polyimide obtained by reacting a diamine component that does not contain a diamine compound having a specific branched structure with a diamine component and reacting with a tetracarboxylic acid component. A polymer of at least one selected from the group. In this case, the specific polymer (B) is preferably, A diamine compound having at least one selected from a carboxyl group and a hydroxyl group is used. More preferably, it is a specific second diamine compound represented by the said Formula [2a].

特定第二之二胺化合物的使用比例如上述,相對於二胺成分全體100莫耳%較佳為10莫耳%以上。更佳為20莫耳%以上,特佳為30莫耳%以上。 The use ratio of the specific second diamine compound is, for example, as described above, preferably 100 mol% or more with respect to 100 mol% of the entire diamine component. More preferably, it is 20 mol% or more, and particularly preferable is 30 mol% or more.

又,特定聚合物(B)可併用特定第二之二胺化合物與特定第三之二胺化合物。此時之使用比例較佳為,相對於二胺成分全體100莫耳%的特定第二之二胺化合物為10~80莫耳%,特定第三之二胺化合物為10~80莫耳%。更佳為,特定第二之二胺化合物為20~70莫耳%,特定第三之二胺化合物為20~70莫耳%。 The specific polymer (B) may be used in combination with a specific second diamine compound and a specific third diamine compound. In this case, it is preferable that the specific second diamine compound is 10 to 80 mol%, and the specific third diamine compound is 10 to 80 mol% relative to 100 mol% of the entire diamine component. More preferably, the specific second diamine compound is 20 to 70 mole%, and the specific third diamine compound is 20 to 70 mole%.

本發明中製作特定聚合物(A)及特定聚合物(B),即該等聚醯亞胺系聚合物的方法無特別限定。一般係由二胺成分與四羧酸成分反應所得。一般如,使由四羧酸二酐及該四羧酸之衍生物所成群中所選出的至少一種之四羧酸成分,與由一種或複數種二胺化合物所形成的二胺成分反應,得聚醯胺酸之方法。具體上可使用,使四羧酸二酐與一級或二級之二胺化合物聚縮合而得聚醯胺酸之方法、使四羧酸與一級或二級之二胺化合物脫水聚縮合反應而得聚醯胺酸的方法或四羧酸二鹵化物與一級或二級之二胺化合物反應而得聚醯胺酸的方法。 The method for producing the specific polymer (A) and the specific polymer (B) in the present invention, that is, the polyfluorene-based polymer is not particularly limited. Generally, it is obtained by reacting a diamine component and a tetracarboxylic acid component. Generally, for example, reacting at least one tetracarboxylic acid component selected from the group consisting of a tetracarboxylic dianhydride and a derivative of the tetracarboxylic acid with a diamine component formed from one or more kinds of diamine compounds, Method for obtaining polyamic acid. Specifically, the method can be obtained by polycondensing a tetracarboxylic dianhydride with a primary or secondary diamine compound to obtain polyamidonic acid, or by dehydrating polycondensation reaction between a tetracarboxylic acid and a primary or secondary diamine compound. A method of polyamidic acid or a method of obtaining a polyamidic acid by reacting a tetracarboxylic dihalide with a primary or secondary diamine compound.

製作聚醯胺酸烷基酯時可使用,使羧酸基被二烷基酯化所得的四羧酸與一級或二級之二胺化合物聚縮 合的方法、使羧酸基被二烷基酯化所得的四羧酸二鹵化物與一級或二級之二胺化合物反應的方法或聚醯胺酸之羧基被轉換為酯的方法。 It can be used in the production of polyalkylamino alkyl esters. Polytetracarboxylic acid obtained by esterifying a carboxylic acid group with a dialkyl group is polycondensed with a primary or secondary diamine compound. A method of reacting, a method of reacting a tetracarboxylic dihalide obtained by esterifying a carboxylic acid group with a dialkyl group and a primary or secondary diamine compound, or a method of converting a carboxyl group of a polyamic acid into an ester.

製作聚醯亞胺時可使用,使前述聚醯胺酸或聚醯胺酸烷基酯閉環而得聚醯亞胺的方法。 In the production of polyimide, a method of obtaining a polyimide by ring-closing the polyamic acid or a polyalkylamic acid alkyl ester can be used.

二胺成分與四羧酸成分的反應一般為,於有機溶劑中進行二胺成分與四羧酸成分的反應。此時所使用的有機溶劑可為,能溶解所生成的聚醯亞胺先驅物之物無特別限定。下面將舉反應用之有機溶劑的具體例,但非限定於該為例示。 The reaction of the diamine component and the tetracarboxylic acid component is generally performed by reacting the diamine component and the tetracarboxylic acid component in an organic solvent. The organic solvent used in this case is not particularly limited as long as it can dissolve the produced polyimide precursor. Specific examples of the organic solvent used for the reaction will be given below, but the invention is not limited to these examples.

例如,N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、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-咪唑啉酮。 For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylformamide Alkylidene or 1,3-dimethyl-imidazolinone.

又,聚醯亞胺先驅物之溶劑溶解性較高時,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]所表示的溶劑。 When the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [ D-1] to a solvent represented by the formula [D-3].

(D1表示碳數1~3之烷基,D2表示碳數1~3之烷基,D3表示碳數1~4之烷基)。 (D 1 represents an alkyl group having 1 to 3 carbon atoms, D 2 represents an alkyl group having 1 to 3 carbon atoms, and D 3 represents an alkyl group having 1 to 4 carbon atoms).

該等可單獨使用或混合使用。又,既使無法溶解聚醯亞胺先驅物之溶劑,於不析出所生成的聚醯亞胺 先驅物之範圍內,可與上述溶劑混合使用。又,有機溶劑中之水分會阻礙聚合反應,且成為所生成的聚醯亞胺先驅物被水解之原因,因此有機溶劑較佳為使用脫水乾燥後之物。 These can be used alone or in combination. In addition, even if the solvent of the polyimide precursor cannot be dissolved, the generated polyimide is not precipitated. Within the scope of the precursor, it can be used in combination with the above solvents. In addition, the water in the organic solvent hinders the polymerization reaction and causes the produced polyimide precursor to be hydrolyzed. Therefore, it is preferable to use a dehydrated organic solvent as the organic solvent.

有機溶劑中使二胺成分與四羧酸成分反應之方法如,攪拌二胺成分分散或溶解於有機溶劑所得的溶液下,直接將四羧酸成分或分散或溶解於有機溶劑後加入的方法,或相反地將二胺成分加入四羧酸成分分散或溶解於有機溶劑所得的溶液之方法,或交互添加二胺成分與四羧酸成分的方法等,可使用該等中任何方法。又,各自使用複數種二胺成分與四羧酸成分進行反應時,可以預先混合之狀態進行反應、可各自依序進行反應,或使各自反應所得的低分子量物進行混合反應而得聚合物。此時之聚合溫度可選擇-20℃~150℃之任意溫度,但較佳為-5℃~100℃之範圍。又,可以任意濃度進行反應,但濃度太低時難得到高分子量之聚合物,濃度太高時會過度增加反應液之黏性而難均勻攪拌。因此較佳為1~50質量%,更佳為5~30質量%。反應初期可以高濃度進行,其後追加有機溶劑。 A method for reacting a diamine component with a tetracarboxylic acid component in an organic solvent is, for example, a method in which the diamine component is dispersed or dissolved in an organic solvent while stirring, and the tetracarboxylic acid component is directly dispersed or dissolved in an organic solvent and added, Alternatively, a method in which a diamine component is added to a solution obtained by dispersing or dissolving a tetracarboxylic acid component in an organic solvent or a method in which a diamine component and a tetracarboxylic acid component are alternately added may be used. In addition, when a plurality of diamine components and a tetracarboxylic acid component are each reacted, the reaction may be performed in a state of being mixed in advance, the reactions may be sequentially performed in each case, or the low molecular weight substances obtained by the respective reactions may be mixed to obtain a polymer. The polymerization temperature at this time can be selected from any temperature of -20 ° C to 150 ° C, but is preferably in the range of -5 ° C to 100 ° C. In addition, the reaction can be performed at any concentration, but when the concentration is too low, it is difficult to obtain a polymer with a high molecular weight, and when the concentration is too high, the viscosity of the reaction solution is excessively increased, and it is difficult to uniformly stir. Therefore, it is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction can be performed at a high concentration in the initial stage, and an organic solvent is added thereafter.

聚醯亞胺先驅物之聚合反應中,二胺成分之合計莫耳數與四羧酸成分的合計莫耳數之比較佳為0.8~1.2。與一般的聚縮合反應相同,該莫耳比近似1.0時可增加所生成的聚醯亞胺先驅物之分子量。 In the polymerization reaction of the polyimide precursor, the total molar number of the diamine component and the total molar number of the tetracarboxylic acid component is preferably 0.8 to 1.2. Like the general polycondensation reaction, when the molar ratio is approximately 1.0, the molecular weight of the resulting polyfluorene imine precursor can be increased.

本發明的聚醯亞胺為前述聚醯亞胺先驅物閉環所得的聚醯亞胺,該聚醯亞胺中醯胺酸基之閉環率(也 稱為醯亞胺化率)非需為100%,可因應用途或目的而任意調整。其中本發明就抑制曝露長時間光照射後之電壓保持率降低的觀點較佳為,特定聚合物(A)為30~100%,特定聚合物(B)為30~100%。更佳為,特定聚合物(A)為40~90%,特定聚合物(B)為40~90%。特佳為,特定聚合物(A)為50~85%,特定聚合物(B)為50~85%。 The polyimide of the present invention is a polyimide obtained by ring closure of the aforementioned polyimide precursor, and the ring closure ratio of the amino acid group in the polyimide (also It is called imidization ratio, but it is not required to be 100%, and it can be adjusted arbitrarily according to use or purpose. Among them, in the present invention, from the viewpoint of suppressing a decrease in the voltage retention rate after exposure to long-term light irradiation, the specific polymer (A) is preferably 30 to 100%, and the specific polymer (B) is 30 to 100%. More preferably, the specific polymer (A) is 40 to 90%, and the specific polymer (B) is 40 to 90%. Particularly preferred is that the specific polymer (A) is 50 to 85%, and the specific polymer (B) is 50 to 85%.

使聚醯亞胺先驅物被醯亞胺化的方法如,直接加熱聚醯亞胺先驅物之溶液的熱醯亞胺化,或將觸媒加入聚醯亞胺先驅物之溶液的觸媒醯亞胺化。 The method for making the polyfluorene imide precursor be fluorinated, for example, directly heating the solution of the polyfluorene imide precursor by thermal hydration, or adding a catalyst to the catalyst of the polyfluorene imide precursor solution Imidization.

溶液中使聚醯亞胺先驅物被熱醯亞胺化時之溫度為100℃~400℃,較佳為120℃~250℃,又以將醯亞胺化反應所生成的水排除至系外為佳。 The temperature at which the polyimide precursor is thermally imidized in the solution is 100 ° C to 400 ° C, preferably 120 ° C to 250 ° C, and the water generated by the imidization reaction is excluded from the system. good.

聚醯亞胺先驅物的觸媒醯亞胺化可藉由,將鹼性觸媒與酸酐加入聚醯亞胺先驅物之溶液中,-20~250℃,較佳為0~180℃下攪拌進行。鹼性觸媒之量為醯胺酸基的0.5~30莫耳倍,較佳為2~20莫耳倍,酸酐之量為醯胺酸基的1~50莫耳倍,較佳為3~30莫耳倍。鹼性觸媒如,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持有適度鹼性而為佳。酸酐如,乙酸酐、偏苯三酸酐或均苯四酸酐等,其中又以使用乙酸酐時結束反應後易精製而為佳。藉由觸媒醯亞胺化之醯亞胺化率可藉由調節觸媒量、反應溫度與反應時間而控制。 The catalyst of polyimide precursor can be imidized by adding basic catalyst and acid anhydride to the solution of polyimide precursor, and stirring at -20 ~ 250 ℃, preferably 0 ~ 180 ℃ get on. The amount of the alkaline catalyst is 0.5 to 30 mol times of the amino acid group, preferably 2 to 20 mol times, and the amount of the acid anhydride is 1 to 50 mol times of the amino acid group, preferably 3 to 30 mol times. 30 mol times. Basic catalysts, such as pyridine, triethylamine, trimethylamine, tributylamine, or trioctylamine, etc., among which pyridine is preferred to have moderate alkalinity during the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, acetic anhydride is preferably used for purification after the reaction is completed. The rate of ammonium imidization through catalyst imidization can be controlled by adjusting the amount of catalyst, reaction temperature and reaction time.

由聚醯亞胺先驅物或聚醯亞胺之反應溶液回收所生成的聚醯亞胺先驅物或聚醯亞胺時,可將反應溶液投入溶劑進行沈澱。沈澱用的溶劑如,甲醇、乙醇、異丙醇、丙酮、己烷、丁基溶纖劑、庚烷、甲基乙基酮、甲基異丁基酮、甲苯、苯、水等。將投入溶劑而沈澱的聚合物過濾回收後,常壓或減壓下,可以常溫或加熱進行乾燥。又,重覆2~10次將沈澱回收的聚合物再溶解於有機溶劑後,再沈澱回收之操作,可減少聚合物中之不純物。此時之溶劑如,醇類、酮類或烴等,使用由該等中所選出的三種以上之溶劑時,可進一步提升精製效率而為佳。 When the polyfluorene imide precursor or polyfluorene imine is recovered from the polyfluorene imide precursor or the polyfluorene imide reaction solution, the reaction solution can be put into a solvent to precipitate. The solvent used for the precipitation is, for example, methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, and the like. After the polymer precipitated by adding the solvent is filtered and recovered, the polymer can be dried at normal temperature or under reduced pressure. In addition, repeating the operation of re-dissolving the polymer recovered by precipitation 2 to 10 times in an organic solvent and re-precipitating and recovering can reduce impurities in the polymer. At this time, solvents such as alcohols, ketones, or hydrocarbons are used. When three or more solvents selected from these are used, the purification efficiency can be further improved.

本發明的聚醯亞胺系聚合物之分子量就考量所得液晶配向膜的強度、液晶配向膜形成時的作業性及塗膜性時,以GPC(Gel Permeation Chromatography)法測定的重量平均分子量較佳為5,000~1,000,000,更佳為10,000~150,000。 In consideration of the molecular weight of the polyfluorene imide polymer of the present invention, the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is preferred when considering the strength of the obtained liquid crystal alignment film, the workability during the formation of the liquid crystal alignment film, and the coating properties. It is 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

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

本發明的液晶配向處理劑為,形成液晶配向膜(也稱為樹脂被膜)用的塗佈溶液,含有特定聚合物(A)、特定聚合物(B)及溶劑之形成液晶配向膜用的塗佈溶液。 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 a coating for forming a liquid crystal alignment film containing a specific polymer (A), a specific polymer (B), and a solvent. Cloth solution.

液晶配向處理劑中特定聚合物(A)及特定聚合物(B)的比例較佳為,相對於特定聚合物(A)100質量份的特定聚合物(B)為10~900質量份。更佳為,特定聚合物(B)為20~800質量份、特佳為,特定聚合物(B)為 30~700質量份。 The ratio of the specific polymer (A) and the specific polymer (B) in the liquid crystal alignment treatment agent is preferably 10 to 900 parts by mass with respect to 100 parts by mass of the particular polymer (B). More preferably, the specific polymer (B) is 20 to 800 parts by mass, particularly preferably, the specific polymer (B) is 30 ~ 700 parts by mass.

本發明的液晶配向處理劑中全部之聚合物成分可為,全部為本發明的特定聚合物(A)及特定聚合物(B),又可混合其他的聚合物。此時該其他的聚合物之含量,相對於特定聚合物(A)及特定聚合物(B)合計100質量份為0.5質量份~15質量份,較佳為1質量份~10質量份。該其他的聚合物如,纖維素系聚合物、丙烯酸聚合物、甲基丙烯酸聚合物、聚碸、聚醯胺或聚矽氧烷等。 All the polymer components in the liquid crystal alignment treatment agent of the present invention may be all the specific polymer (A) and the specific polymer (B) of the present invention, and other polymers may be mixed. At this time, the content of the other polymer is 0.5 to 15 parts by mass, and preferably 1 to 10 parts by mass based on 100 parts by mass of the specific polymer (A) and the specific polymer (B) in total. The other polymers include, for example, a cellulose polymer, an acrylic polymer, a methacrylic polymer, polyfluorene, polyamine, or silicone.

本發明的液晶配向處理劑中之溶劑就藉由塗佈可形成均勻液晶配向膜的觀點,液晶配向處理劑中溶劑之含量較佳為70~99.9質量%。該含量可因應目的之液晶配向膜的膜厚而適當改變。 The solvent in the liquid crystal alignment treatment agent of the present invention is from the viewpoint of forming a uniform liquid crystal alignment film by coating, and the content of the solvent in the liquid crystal alignment treatment agent is preferably 70 to 99.9% by mass. The content can be appropriately changed according to the film thickness of the liquid crystal alignment film according to the purpose.

本發明的液晶配向處理劑所使用的溶劑可為,能溶解特定聚合物(A)及特定聚合物(B)之溶劑(也稱為良溶劑)無特別限定。下面將舉良溶劑之具體例,但非限定於該等例示。 The solvent used for the liquid crystal alignment treatment agent of the present invention may be a solvent (also referred to as a good solvent) capable of dissolving the specific polymer (A) and the specific polymer (B), and is not particularly limited. Specific examples of good solvents are given below, but 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-吡咯烷酮、N-乙基-2-吡咯烷酮、二甲基亞碸、γ-丁內酯、1,3-二甲基-咪唑啉酮、甲基乙基酮、環己酮、環庚酮或4-羥基-4-甲基-2-庚酮等。 For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylmethylene, γ- Butyrolactone, 1,3-dimethyl-imidazolinone, methyl ethyl ketone, cyclohexanone, cycloheptanone, 4-hydroxy-4-methyl-2-heptanone, and the like.

其中較佳為使用N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、γ-丁內酯。 Among these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone are preferably used.

又,特定聚合物(A)及特定聚合物(B)相對於溶劑之溶解性較高時,較佳為使用前述式[D-1]~式 [D-3]所表示的溶劑。 When the solubility of the specific polymer (A) and the specific polymer (B) with respect to a solvent is high, it is preferable to use the above formulas [D-1] to [D-3] The solvent shown.

本發明的液晶配向處理劑中良溶劑較佳為,液晶配向處理劑所含的溶劑全體之10~100質量%。其中又以20~90質量%為佳,更佳為30~80質量%。 The good solvent in the liquid crystal alignment treatment agent of the present invention is preferably 10 to 100% by mass of the entire solvent contained in the liquid crystal alignment treatment agent. Among them, 20 to 90% by mass is preferable, and 30 to 80% by mass is more preferable.

本發明的液晶配向處理劑於無損本發明之效果的範圍內,可使用提升塗佈液晶配向處理劑時之液晶配向膜的塗膜性及表面平滑性用之溶劑(也稱為弱溶劑)。下面將舉弱溶劑之具體例,但非限定於該等例示。 As long as the liquid crystal alignment treatment agent of the present invention does not impair the effect of the present invention, a solvent (also referred to as a weak solvent) for improving the coating property and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used. Specific examples of weak solvents are given below, but 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-戊二醇、2-甲基-2,4-戊二醇、2-乙基-1,3-己二醇、二丙基醚、二丁基醚、二己基醚、二噁烷、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丁基醚、1,2-丁氧基乙烷、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇甲基乙基醚、二乙二醇二丁基醚、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、伸丙基碳酸酯、伸乙基碳酸酯、2-(甲氧基甲氧 基)乙醇、乙二醇單丁基醚、乙二醇單異戊基醚、乙二醇單己基醚、2-(己氧基)乙醇、糠醇、二乙二醇、丙二醇、丙二醇單丁基醚、1-(丁氧基乙氧基)丙醇、丙二醇單甲基醚乙酸酯、二丙二醇、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇二甲基醚、三丙二醇單甲基醚、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單丁基醚乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯、2-(2-乙氧基乙氧基)乙基乙酸酯、二乙二醇乙酸酯、三乙二醇、三乙二醇單甲基醚、三乙二醇單乙基醚、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、乳酸甲基酯、乳酸乙基酯、乳酸n-丙基酯、乳酸n-丁基酯、乳酸異戊基酯或前述式[D-1]~式[D-3]所表示的溶劑等。 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, 1,2-ethylene glycol, 1,2-propylene glycol, 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, dihexyl 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 ethyl ether, diethylene glycol dibutyl ether, 2- Pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl Acetate, 2-ethylhexylethyl Acid ester, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, butyl carbonate, 2- (methoxymethoxy) Based) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisopentyl 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, tripropylene glycol Monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol di Acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol Acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid Propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3- Ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid , Butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate or the aforementioned formulas [D-1] ~ [D-3] The solvent and the like.

其中較佳為使用1-己醇、環己醇、1,2-乙二醇、1,2-丙二醇、丙二醇單丁基醚、乙二醇單丁基醚、二乙二醇二甲基醚或前述式[D-1]~式[D-3]所表示的溶劑。 Among these, 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, and diethylene glycol dimethyl ether are preferably used. Or the solvent represented by said formula [D-1]-formula [D-3].

該等弱溶劑較佳為,液晶配向處理劑所含的溶劑全體之1~70質量%。其中又以1~60質量%為佳,更佳為5~60質量%。 These weak solvents are preferably 1 to 70% by mass of the entire solvent contained in the liquid crystal alignment treatment agent. Among them, 1 to 60% by mass is more preferable, and 5 to 60% by mass is more preferable.

本發明的液晶配向處理劑較佳為,導入具有 環氧基、異氰酸酯基、環氧丙烷基或環碳酸酯基之交聯性化合物、具有由羥基、羥基烷基及低級烷氧基烷基所成群中所選出的至少一種之取代基的交聯性化合物,或具有聚合性不飽和鍵結之交聯性化合物。該等取代基或聚合性不飽和鍵結需為,交聯性化合物中具有2個以上。 The liquid crystal alignment treatment agent of the present invention is preferably one having Cross-linking compound of epoxy group, isocyanate group, propylene oxide group or cyclic carbonate group, cross-linking having at least one selected from the group consisting of hydroxyl group, hydroxyalkyl group and lower alkoxyalkyl group Crosslinkable compounds, or crosslinkable compounds with polymerizable unsaturated bonds. These substituents or polymerizable unsaturated bonds need to be 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如,雙酚丙酮縮水甘油醚、苯酚酚醛清漆環氧樹脂、甲酚酚醛清漆環氧樹脂、三縮水甘油基三聚異氰酸酯、四縮水甘油基胺基二伸苯酯、四縮水甘油基-m-二甲苯二胺、四縮水甘油基-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)八氟聯苯、三縮水甘油基-p-胺基苯酚、四縮水甘油基間二甲苯二胺、2-(4-(2,3-環氧丙氧基)苯基)-2-(4-(1,1-雙(4-(2,3-環氧丙氧基)苯基)乙基)苯基)丙烷或1,3-雙(4-(1-(4-(2,3-環氧丙氧基)苯基)-1-(4-(1-(4-(2,3-環氧丙氧基)苯基)-1-甲基乙基)苯基)乙基)苯氧基)-2-丙醇等。 Crosslinkable compounds having epoxy or isocyanate groups such as bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl trimeric isocyanate, tetraglycidylamine group Diphenylene ester, tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenylglycidyl ether ethane, triphenylglycidyl Glyceryl ether ethane, bisphenol hexafluoroacetamidine diglycidyl ether, 1,3-bis (1- (2,3-glycidoxy) -1-trifluoromethyl-2,2,2-tris Fluoromethyl) benzene, 4,4-bis (2,3-glycidoxy) octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl-m-xylylenediamine, 2- (4- (2,3-glycidoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-glycidoxy) phenyl) ethyl) benzene Yl) propane or 1,3-bis (4- (1- (4- (2,3-glycidoxy) phenyl) -1- (4- (1- (4- (2,3-cyclo Oxypropoxy) 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為,具有至少2個下述式[4A]所表示的環氧丙烷基之交聯性化合物。 The crosslinkable compound having a propylene oxide group is a crosslinkable compound having at least two propylene oxide groups represented by the following formula [4A].

具體如,國際公開公報WO2011/132751(2011.10.27公開)之58項~59項所揭示的式[4a]~式[4k]所表示的交聯性化合物。 Specifically, for example, the crosslinkable compounds represented by formulas [4a] to [4k] disclosed in items 58 to 59 of International Publication WO2011 / 132751 (published on 2011.10.27).

具有環碳酸酯基之交聯性化合物為,具有至少2個下述式[5A]所表示的環碳酸酯基之交聯性化合物。 The crosslinkable compound having a cyclic carbonate group is a crosslinkable compound having at least two cyclic carbonate groups represented by the following formula [5A].

具體如,國際公開公報WO2012/014898(2012.2.2公開)之76項~82項所揭示的式[5-1]~式[5-42]所表示的交聯性化合物。 Specifically, for example, the cross-linkable compounds represented by the formulas [5-1] to [5-42] disclosed in items 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中所選出的至少一種之取代基的交聯性化合物如,具有由羥基及烷氧基中所選出的至少一種之取代基的胺基樹脂,例如三聚氰胺樹脂、尿素樹脂、鳥糞胺樹脂、甘脲-甲醛樹脂、琥珀醯酵醯胺-甲醛樹脂或伸乙基尿素-甲醛樹脂等。具體上可使用胺基之氫原子被羥甲基或烷氧基甲基或雙方取代的三聚氰胺衍生物、苯并鳥糞胺衍生物,或甘脲。該三聚氰胺衍生物或苯并鳥糞胺衍生物可以二聚物或三聚物存在。該等較佳為相對於每1個三嗪環,平均具有3個以上6個以下 之羥甲基或烷氧基甲基之物。 A crosslinkable compound having at least one selected from the group consisting of a hydroxyl group and an alkoxy group, such as an amine-based resin having at least one selected from the group consisting of a hydroxyl group and an alkoxy group, such as a melamine resin. , Urea resin, guanoamine resin, glycoluril-formaldehyde resin, succinylpyramine-formaldehyde resin, or ethyl urea-formaldehyde resin, etc. Specifically, a melamine derivative, a benzoguanamine derivative, or a glycoluril may be used in which the hydrogen atom of the amine group is substituted with methylol or alkoxymethyl or both. The melamine derivative or benzoguanamine derivative may exist as a dimer or a trimer. These are preferably 3 to 6 on average per triazine ring Of methylol or alkoxymethyl.

該等三聚氰胺衍生物或苯并鳥糞胺衍生物如,市售物的每1個三嗪環被平均3.7個甲氧基甲基取代的MX-750、每1個三嗪環被平均5.8個甲氧基甲基取代的MW-30(以上為三和化學公司製)、或賽美爾300、301、303、350、370、771、325、327、703、712等之甲氧基甲基化三聚氰胺、賽美爾235、236、238、212、253、254等之甲氧基甲基化丁氧基甲基化三聚氟胺、賽美爾506、508等之丁氧基甲基化三聚氰胺、賽美爾1141般含有羧基之甲氧基甲基化異丁氧基甲基化三聚氰胺、賽美爾1123般甲氧基甲基化乙氧基甲基化苯并鳥糞胺、賽美爾1123-10般甲氧基甲基化丁氧基甲基化苯并鳥糞胺、賽美爾1128般丁氧基甲基化苯并鳥糞胺、賽美爾1125-80般含有羧基之甲氧基甲基化乙氧基甲基化苯并鳥糞胺(以上為三井賽艾那公司製)。又,甘脲如,賽美爾1170般丁氧基甲基化甘脲、賽美爾1172般羥甲基化甘脲等,帕鳥達1174般甲氧基羥甲基化甘脲等。 Such melamine derivatives or benzoguanamine derivatives, for example, MX-750 substituted with an average of 3.7 methoxymethyl groups per triazine ring on the market, and an average of 5.8 per triazine ring Methoxymethyl substituted MW-30 (above manufactured by Sanwa Chemical Co., Ltd.), or methoxymethyl 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. Methoxymethylated butylated methylated melamine, semyl 235, 236, 238, 212, 253, 254, etc. melamine, butoxymethylated melamine 506, 508, etc. Melamine, methionized isobutoxy methylated melamine containing carboxyl like 1141, melamine, methoxymethylated ethoxymethylated benzoguanamine like melamine, 1123 like semyl, semyl 1123-10 methoxymethylated butoxymethylated benzoguanamine, semyl 1128 butoxymethylated benzoguanamine, semyl 1125-80 containing carboxyl groups Methoxymethylated ethoxymethylated benzoguanamine (the above is made by Mitsui Saina). Examples of glycoluril include butoxymethylated glycoluril, such as 1170, and methylolated glycoluril, such as 1170, and methoxymethylolated glycoluril, like 1174.

具有羥基或烷氧基之苯或苯酚性化合物如,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-丁基苯酚等。 Benzene or phenolic compounds having a hydroxyl or alkoxy group such as 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 and the like.

更具體如,國際公開公報WO2011/132751(2011.10.27公開)之62頁~66頁所揭示的式[6-1]~式[6-48]所表示的交聯性化合物。 More specifically, for example, the crosslinkable compounds represented by the formulas [6-1] to [6-48] disclosed on pages 62 to 66 of International Publication WO2011 / 132751 (published on 2011.10.27).

具有聚合性不飽和鍵結之交聯性化合物如,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甘油聚縮水甘油醚聚(甲基)丙烯酸酯等之分子內具有3個聚合性不飽和基之交聯性化合物,又如,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、環氧乙烷雙酚A型二(甲基)丙烯酸酯、環氧丙烷雙酚型二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、甘油二(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)丙烯酸酯等之分子內具有2個聚合性不飽和基之交聯性化合物,或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、甘油單(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基磷酸酯或N-羥甲基(甲基)丙烯醯胺等之分子內具有1個聚合性不飽和基之交聯性化合物。 Crosslinkable compounds having polymerizable unsaturated bonds such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (methyl) ) Cross-linking compounds having 3 polymerizable unsaturated groups in the molecule such as propylene ethoxyethoxytrimethylolpropane or glycerol polyglycidyl ether poly (meth) acrylate, for example, ethylene glycol Di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 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) acrylic acid Ester, propylene oxide bisphenol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol di (meth) acrylate, ethyl Diethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl bis ( Cross-linking compound having two polymerizable unsaturated groups in the molecule such as acrylate) or hydroxytrimethylacetic acid neopentyl glycol di (meth) acrylate, or 2-hydroxyethyl (meth) acrylic acid Ester, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (methyl) Acrylic acid 2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 2- (meth) acrylic acid A crosslinkable compound having one polymerizable unsaturated group in the molecule such as phosphoric acid phosphate ester or N-hydroxymethyl (meth) acrylamide.

又,可使用下述式[7A]所表示的化合物。 In addition, a compound represented by the following formula [7A] can be used.

(式[7A]中,E1表示由環己烷環、二環己烷環、苯環、聯苯環、叔苯環、萘環、芴環、蒽環及菲環所成群中所選出的基,E2表示由下述式[7a]及式[7b]中所選出的基,n表示1~4之整數)。 (In formula [7A], E 1 represents a group selected from the group consisting of cyclohexane ring, bicyclohexane ring, benzene ring, biphenyl ring, tertiary benzene ring, naphthalene ring, fluorene ring, anthracene ring, and phenanthrene ring. E 2 represents a base selected from the following formulas [7a] and [7b], and n represents an integer of 1 to 4).

上述化合物為交聯性化合物一例,但非限定於該等。又,本發明之液晶配向處理劑所使用的交聯性化合物可為一種,或二種以上組合。 The said compound is an example of a crosslinkable compound, It is not limited to these. 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.

本發明的液晶配向處理劑中,交聯性化合物之含量相對於全部聚合物成分100質量份,較佳為0.1~150質量份。為了進行交聯反應以發現目的效果,相對於全部聚合物成分100質量份更佳為0.1~100質量份,最佳為1~50質量份。 In the liquid crystal alignment treatment agent of the present invention, the content of the crosslinkable compound is preferably 0.1 to 150 parts by mass relative to 100 parts by mass of the entire polymer component. In order to perform the crosslinking reaction to find the desired effect, it is more preferably 0.1 to 100 parts by mass, and most preferably 1 to 50 parts by mass, relative to 100 parts by mass of the entire polymer component.

本發明的液晶配向處理劑於無損本發明之效果的範圍內,可使用提升塗佈液晶配向處理劑時之液晶配向膜的膜厚均勻性及表面平滑性用之化合物。 As long as the liquid crystal alignment treatment agent of the present invention does not impair the effect of the present invention, a compound for improving the uniformity of the film thickness and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used.

提升液晶配向膜之膜厚的均勻性及表面平滑性用的化合物如,氟系表面活性劑、聚矽氧系表面活性 劑、非離子系表面活性劑等。 Compounds for improving the uniformity and surface smoothness of the liquid crystal alignment film, such as fluorine-based surfactants and polysiloxane-based surfactants Agents, non-ionic surfactants, etc.

更具體如,耶佛特EF301、EF303、EF352(以上為特肯姆公司製)、美佳凡F171、F173、R-30(以上為大日本油墨公司製)、佛洛拉FC430、FC431(以上為住友3M公司製)、艾薩西AG710、薩佛隆S-382、SC101、SC102、SC103、SC104、SC105、SC106(以上為旭硝子公司製)等。該等表面活性劑之使用比例,相對於液晶配向處理劑所含的全部聚合物成分100質量份較佳為0.01~2質量份,更佳為0.01~1質量份。 More specifically, Jeffrey EF301, EF303, EF352 (the above are manufactured by Teckem), Megan F171, F173, R-30 (the above are manufactured by Dainippon Ink), Flora FC430, FC431 (the above are (Made by Sumitomo 3M), Assassi AG710, Saffron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (the above are made by Asahi Glass Co., Ltd.), etc. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of all polymer components contained in the liquid crystal alignment treatment agent.

另外本發明的液晶配向處理劑可添加促進液晶配向膜中電荷移動而促進元件電荷脫離用之化合物,例如國際公開公報WO2011/132751(2011.10.27公開)之69頁~73頁所揭示的式[M1]~式[M156]所表示的含氮之雜環胺化合物。該胺化合物可直接加入液晶配向處理劑中,但較佳為以適當溶劑形成濃度0.1質量%~10質量%,較佳為1質量%~7質量%之溶液再添加。該溶劑可為能溶解上述特定聚合物(A)及特定聚合物(B)之有機溶劑無特別限定。 In addition, the liquid crystal alignment treatment agent of the present invention may add a compound for promoting charge movement in the liquid crystal alignment film and accelerating charge release of the device, for example, the formulas disclosed in pages 69 to 73 of International Publication WO2011 / 132751 (published on 2011.10.27) [ M1] to a nitrogen-containing heterocyclic amine compound represented by the formula [M156]. The amine compound can be directly added to the liquid crystal alignment treatment agent, but it is preferably added in a solution having a concentration of 0.1% to 10% by mass, preferably 1% to 7% by mass, with an appropriate solvent. The solvent may be any organic solvent that can dissolve the specific polymer (A) and the specific polymer (B).

本發明的液晶配向處理劑除了上述弱溶劑、交聯性化合物、提升樹脂被膜或液晶配向膜之膜厚的均勻性及表面平滑性用的化合物,及促進電荷脫離用的化合物,於無損本發明之效果的範圍內,可另添加改變液晶配向膜之介電率或導電性等之電氣特性用的介電體或導電物質。 The liquid crystal alignment treatment agent of the present invention, in addition to the above-mentioned weak solvent, crosslinkable compound, a compound for improving the uniformity and surface smoothness of the film thickness of the resin film or the liquid crystal alignment film, and a compound for promoting charge release, does not damage the present invention. Within the scope of the effect, a dielectric body or a conductive substance for changing the electrical characteristics such as the dielectric constant and conductivity of the liquid crystal alignment film may be added.

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

將本發明的液晶配向處理劑塗佈於基板上,焙燒後進行摩擦處理或光照射等之配向處理,可作為液晶配向膜用。又,使用於垂直配向用途等時既使無配向處理也可作為液晶配向膜用。此時所使用的基板可為透明性較高之基板無特別限定,除了玻璃基板,可另使用丙烯酸基板或聚碳酸酯基板等之塑料基板等。就步驟簡單化之觀點較佳為,使用形成液晶驅動用之ITO電極等的基板。又,反射型之液晶顯示元件中,可僅單側基板使用矽晶圓等之不透明基板,此時的電極可使用鋁等能反射光之材料。 The liquid crystal alignment treatment agent of the present invention is coated on a substrate and subjected to an alignment treatment such as rubbing treatment or light irradiation after firing, and can be used as a liquid crystal alignment film. When used for vertical alignment applications, it can be used as a liquid crystal alignment film even without alignment treatment. The substrate used at this time is not particularly limited, and in addition to a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used. From the viewpoint of simplifying the steps, it is preferable to use a substrate for forming an ITO electrode or the like for liquid crystal driving. In the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used for only one side substrate, and an electrode capable of reflecting light such as aluminum can be used for the electrode at this time.

液晶配向處理劑之塗佈方法無特別限定,一般為工業上以網版印刷、膠版印刷、柔性印刷或噴墨印刷法等進行之方法。其他塗佈方法如,浸漬法、輥塗佈法、縫隙塗佈法、旋轉塗佈法或噴霧法等,可因應目的使用。 The application method of the liquid crystal alignment treatment agent is not particularly limited, and is generally industrially performed by screen printing, offset printing, flexible printing, or inkjet printing. Other coating methods such as a dipping method, a roll coating method, a gap coating method, a spin coating method, or a spray method can be used depending on the purpose.

將液晶配向處理劑塗佈於基板後,藉由熱板、熱循環型烤箱或IR(紅外線)型烤箱等之加熱方法,因應液晶配向處理劑所使用的溶劑,以30~300℃,較佳以30~250℃之溫度使溶劑蒸發,得液晶配向膜。焙燒後液晶配向膜之厚度為,因太厚時不利於液晶顯示元件之消耗電力方面,太薄時會降低液晶顯示元件之信賴性,故較佳為5~300nm,更佳為10~100nm。為了使液晶水平配向或傾斜配向,而對焙燒後之液晶配向膜實施摩擦或照 射偏光紫外線等處理。 After applying the liquid crystal alignment treatment agent to the substrate, the heating method such as a hot plate, a thermal cycle type oven, or an IR (infrared) type oven is preferably 30 to 300 ° C. according to the solvent used for the liquid crystal alignment treatment agent. The solvent was evaporated at a temperature of 30 to 250 ° C to obtain a liquid crystal alignment film. The thickness of the liquid crystal alignment film after firing is 5 to 300 nm, and more preferably 10 to 100 nm, because it is not good for the power consumption of the liquid crystal display element when it is too thick, and the reliability of the liquid crystal display element is reduced when it is too thin. In order to make the liquid crystal horizontal alignment or oblique alignment, the calcined liquid crystal alignment film is rubbed or illuminated. Processing such as polarized ultraviolet radiation.

本發明的液晶顯示元件為,藉由上述方法由本發明的液晶配向處理劑得附液晶配向膜之基板後,以已知方法製作液晶單元作為液晶顯示元件用之物。 The liquid crystal display element of the present invention is obtained by using the liquid crystal alignment treatment agent of the present invention to obtain a substrate with a liquid crystal alignment film by the above method, and then fabricating a liquid crystal cell as a liquid crystal display element by a known method.

液晶單元之製作方法如,準備一對形成液晶配向膜之基板,將調距物散佈於單方基板之液晶配向膜上,以液晶配向膜面為內側之方式貼合另一方基板後,減壓注入液晶再密封的方法,或將液晶滴在散佈調距物之液晶配向膜面後貼合基板再密封的方法等。 The manufacturing method of the liquid crystal cell is, for example, preparing a pair of substrates forming a liquid crystal alignment film, dispersing a distance adjusting object on the liquid crystal alignment film of a single substrate, bonding the other substrate with the liquid crystal alignment film surface inside, and then injecting under reduced pressure. A method of reseal the liquid crystal, or a method of bonding the substrate and reseal the liquid crystal by dripping the liquid crystal on the liquid crystal alignment film surface of the distance-adjusting object.

又,本發明的液晶配向處理劑適用於,一對備有電極之基板間具有液晶層所構成,經由將含有藉由活性能量線及熱中至少一方而聚合的聚合性化合物之液晶組成物配置於一對基板之間後,將電壓施加於電極間,同時藉由照射活性能量線及加熱中至少一方聚合聚合性化合物之步驟所製造的液晶顯示元件。該活性能量線較佳為紫外線。紫外線之波長為300~400nm,較佳為310~360nm。藉由加熱而聚合時,加熱溫度為40~120℃,較佳為60~80℃。又,可同時進行紫外線與加熱。 In addition, the liquid crystal alignment treatment agent of the present invention is preferably configured by having a liquid crystal layer between a pair of substrates provided with electrodes, and disposing a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat. A liquid crystal display element produced by applying a voltage between electrodes between a pair of substrates and polymerizing a polymerizable compound by at least one of irradiating active energy rays and heating. The active energy ray is preferably ultraviolet. The wavelength of the ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. When polymerization is performed by heating, the heating temperature is 40 to 120 ° C, and preferably 60 to 80 ° C. Moreover, ultraviolet rays and heating can be performed simultaneously.

上述液晶顯示元件為,藉由PSA(Polymer Sustained Alignment)方式控制液晶分子之預傾之物。PSA方式中係將少量光聚合性化合物,例如光聚合性單體混入液晶材料中,組裝液晶單元後,於液晶層施加一定電壓之狀態下將紫外線等照射於光聚合性化合物,藉由所生成的聚合物以控制液晶分子之預傾。其因去除電壓後 仍可記憶生成聚合物時之液晶分子的配向狀態,故藉由控制形成於液晶層之電場等,可調整液晶分子之預傾。又,PSA方式無需摩擦處理,因此適用於形成藉由摩擦處理而難控制預傾之垂直配向型的液晶層。 The liquid crystal display element is a substance that controls the pretilt of liquid crystal molecules by a PSA (Poly Sustained Alignment) method. In the PSA method, a small amount of a photopolymerizable compound, such as a photopolymerizable monomer, is mixed into a liquid crystal material. After assembling a liquid crystal cell, ultraviolet light or the like is irradiated to the photopolymerizable compound while a certain voltage is applied to the liquid crystal layer. Polymer to control the pretilt of liquid crystal molecules. After removing the voltage The alignment state of the liquid crystal molecules when the polymer is formed can still be memorized, so the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field and the like formed in the liquid crystal layer. In addition, the PSA method does not require rubbing treatment, and is therefore suitable for forming a liquid crystal layer of a vertical alignment type in which pretilt is difficult to control by rubbing treatment.

即,本發明的液晶顯示元件可為,藉由上述方法由液晶配向處理劑得附液晶配向膜之基板後,製作液晶單元,再藉由照射紫外線及加熱中至少一者使聚合性化合物聚合以控制液晶分子之配向之物。 That is, the liquid crystal display element of the present invention may be obtained by obtaining a substrate with a liquid crystal alignment film from a liquid crystal alignment treatment agent by the method described above, preparing a liquid crystal cell, and polymerizing a polymerizable compound by irradiating at least one of ultraviolet rays and heating. An object that controls the alignment of liquid crystal molecules.

舉製作PSA方式之液晶單元一例,即,準備一對形成液晶配向膜之基板,將調距物散佈於單方基板之液晶配向膜上,以液晶配向膜面為內側方式貼合另一方基板後,減壓注入液晶再密封的方法,或將液晶滴在散佈調距物之液晶配向膜面後貼合基板再密封的方法等。 As an example of making a PSA-type liquid crystal cell, that is, prepare a pair of substrates forming a liquid crystal alignment film, disperse the spacers on the liquid crystal alignment film of a single-sided substrate, and attach the other substrate with the liquid crystal alignment film surface as the inner side. A method of injecting liquid crystal under reduced pressure and resealing, or a method of attaching a substrate to a liquid crystal by dripping liquid crystals on the surface of the liquid crystal alignment film on which the distance-adjusting objects are dispersed, and then sealing.

液晶內混合藉由熱或照射紫外線而聚合的聚合性化合物。聚合性化合物如,分子內具有1個以上之丙烯酸酯基或甲基丙烯酸酯基等之聚合性不飽和基的化合物。此時聚合性化合物相對於液晶成分100質量份較佳為0.01~10質量份,更佳為0.1~5質量份。聚合性化合物未達0.01質量份時,無法聚合聚合性化合物而無法控制液晶配向,多於10質量份時,會因未反應之聚合性化合物而降低液晶顯示元件之燒結特性。 A polymerizable compound polymerized by heat or ultraviolet radiation is mixed in the liquid crystal. The polymerizable compound is, for example, a compound having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule. In this case, the polymerizable compound is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass based on 100 parts by mass of the liquid crystal component. When the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound cannot be polymerized and the liquid crystal alignment cannot be controlled. When the polymerizable compound is more than 10 parts by mass, the sintering characteristics of the liquid crystal display element are reduced due to the unreacted polymerizable compound.

製作液晶單元後將交流或直流之電壓施加於液晶單元,同時照射熱或紫外線而聚合聚合性化合物。藉此可控制液晶分子之配向。 After the liquid crystal cell is manufactured, an AC or DC voltage is applied to the liquid crystal cell, and at the same time, a polymerizable compound is polymerized by irradiating heat or ultraviolet rays. This can control the alignment of the liquid crystal molecules.

又,本發明的液晶配向處理劑適用於,一對備有電極之基板之間具有液晶層所構成,經由將含有藉由活性能量線及熱中至少一方而聚合之聚合性基的液晶配向膜配置於前述一對基板之間,再將電壓施加於電極間之步驟所製造的液晶顯示元件,即SC-PVA模式。該活性能量線較佳為紫外線。紫外線之波長為300~400nm,較佳為310~360nm。藉由加熱而聚合時,加熱溫度為40~120℃,較佳為60~80℃。又,可同時進行紫外線與加熱。 In addition, the liquid crystal alignment treatment agent of the present invention is suitable for a liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal alignment film containing a polymerizable group polymerized by at least one of active energy rays and heat. The SC-PVA mode is a liquid crystal display device manufactured by applying a voltage between electrodes between the aforementioned pair of substrates. The active energy ray is preferably ultraviolet. The wavelength of the ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. When polymerization is performed by heating, the heating temperature is 40 to 120 ° C, and preferably 60 to 80 ° C. Moreover, ultraviolet rays and heating can be performed simultaneously.

製作含有藉由活性能量線及熱中至少一方而聚合之聚合性基的液晶配向膜之方法如,將含有該聚合性基之化合物加入液晶配向處理劑中之方法,或使用含有聚合性基之聚合物成分的方法。 A method for producing a liquid crystal alignment film containing a polymerizable group polymerized by at least one of active energy ray and heat, such as a method of adding a compound containing the polymerizable group to a liquid crystal alignment treatment agent, or using a polymer containing a polymerizable group Material composition method.

舉製作SC-PVA模式之液晶單元一例,即,準備一對形成本發明的液晶配向膜之基板,將調距物散佈於單方基板之液晶配向膜上,以液晶配向膜為內側方式貼合另一方基板後,減壓注入液晶再密封的方法,或將液晶滴在散佈調距物之液晶配向膜面後貼合基板再密封的方法等。 Take an example of making a liquid crystal cell in the SC-PVA mode, that is, prepare a pair of substrates forming the liquid crystal alignment film of the present invention, and disperse the spacers on the liquid crystal alignment film of the unilateral substrate, and attach the liquid crystal alignment film as the inner After one substrate is placed, the liquid crystal is injected under reduced pressure and resealed, or the liquid crystal is dropped on the surface of the liquid crystal alignment film on which the distance-adjuster is dispersed, and then the substrate is sealed again.

製作液晶單元後,將交流或直流之電壓施加於液晶單元,同時照射熱或紫外線,可控制液晶分子之配向。 After the liquid crystal cell is manufactured, the AC or DC voltage is applied to the liquid crystal cell and at the same time it is irradiated with heat or ultraviolet rays to control the alignment of the liquid crystal molecules.

如上述使用本發明的液晶配向處理劑可提供,即使曝露於長時間高溫及光照射後,仍可發現安定之預傾角的液晶配向膜。又可得,既使曝露於長時間高溫及光照射後,也可抑制電壓保持率降低,且快速緩和因直流電壓而蓄積之殘留電荷的液晶配向膜。特別是本發明的液 晶配向處理劑適用於使用PSA模式及SC-PVA模式之液晶顯示元件的液晶配向膜。因此使用本發明的液晶配向處理劑所製作的液晶顯示元件為,具有優良信賴性之物,適用於大型液晶電視、中小型汽車導航器、智慧型手機等。 As described above, the liquid crystal alignment treatment agent of the present invention can be used to provide a liquid crystal alignment film with a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. It is also possible to obtain a liquid crystal alignment film capable of suppressing a decrease in the voltage holding ratio even after being exposed to a long-term high temperature and light irradiation, and quickly mitigating the residual charge accumulated by a DC voltage. Especially the liquid of the present invention The crystal alignment treatment agent is suitable for a liquid crystal alignment film using liquid crystal display elements of PSA mode and SC-PVA mode. Therefore, the liquid crystal display element produced by using the liquid crystal alignment treatment agent of the present invention is a substance having excellent reliability, and is suitable for large-scale liquid crystal televisions, small and medium-sized car navigation systems, and smart phones.

實施例 Examples

下面將舉實施例更詳細說明本發明,但非限定於該等。又,下面所使用的代號如下所述。 The present invention will be described in more detail with reference to the following examples, but is not limited thereto. The symbols used below are as follows.

(特定支鏈型二胺化合物) (Specific branched diamine compound)

A1:1,3-二胺基-4-[4-(反-4-n-庚基環己基)苯氧基]苯 A1: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene

A2:1,3-二胺基-5-[4-(反-4-n-庚基環己基)苯氧基甲基]苯 A2: 1,3-diamino-5- [4- (trans-4-n-heptylcyclohexyl) phenoxymethyl] benzene

A3:1,3-二胺基-4-{4-[反-4-(反-4-n-庚基環己基)環己基]苯氧基}苯 A3: 1,3-diamino-4- {4- [trans-4- (trans-4-n-heptylcyclohexyl) cyclohexyl] phenoxy} benzene

A4:下述式[A4]所表示的二胺化合物 A4: a diamine compound represented by the following formula [A4]

(特定第二之二胺化合物) (Specific second diamine compound)

B1:3,5-二胺基苯甲酸(具有羧基(COOH基)的特定第二之二胺化合物) B1: 3,5-diaminobenzoic acid (specific second diamine compound having a carboxyl group (COOH group))

(特定第三之二胺化合物) (Specific tertiary diamine compound)

C1:下述式[C1]所表示的二胺化合物 C1: a diamine compound represented by the following formula [C1]

C2:下述式[C2]所表示的二胺化合物 C2: a diamine compound represented by the following formula [C2]

(其他二胺化合物) (Other diamine compounds)

D1:p-伸苯基二胺 D1: p-phenylene diamine

D2:m-伸苯基二胺 D2: m-phenylene diamine

D3:1,3-二胺基-4-十八烷氧基苯 D3: 1,3-diamino-4-octadecyloxybenzene

(特定四羧酸二酐) (Specific tetracarboxylic dianhydride)

E1:1,2,3,4-環丁烷四羧酸二酐 E1: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

E2:二環[3,3,0]辛烷-2,4,6,8-四羧酸二酐 E2: Bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride

E3:下述式[E3]所表示的四羧酸二酐 E3: tetracarboxylic dianhydride represented by the following formula [E3]

E4:下述式[E4]所表示的四羧酸二酐 E4: tetracarboxylic dianhydride represented by the following formula [E4]

E5:下述式[E5]所表示的四羧酸二酐 E5: tetracarboxylic dianhydride represented by the following formula [E5]

<導入液晶配向處理劑中之交聯性化合物> <Crosslinkable compound introduced into liquid crystal alignment treatment agent>

M1:下述式[M1]所表示的交聯性化合物 M1: a crosslinkable compound represented by the following formula [M1]

<本發明所使用的溶劑> <Solvents used in the present invention>

NMP:N-甲基-2-吡咯烷酮 NMP: N-methyl-2-pyrrolidone

NEP:N-乙基-2-吡咯烷酮 NEP: N-ethyl-2-pyrrolidone

γ-BL:γ-丁內酯 γ-BL: γ-butyrolactone

BCS:乙二醇單丁基醚 BCS: ethylene glycol monobutyl ether

PB:丙二醇單丁基醚 PB: propylene glycol monobutyl ether

EC:二乙二醇單乙基醚 EC: Diethylene glycol monoethyl ether

DME:二丙二醇二甲基醚 DME: Dipropylene glycol dimethyl ether

[測定聚醯亞胺系聚合物之分子量] [Determination of molecular weight of polyfluorene-based polymer]

合成例中聚醯亞胺先驅物及聚醯亞胺之分子量係使用常溫凝膠浸透色譜(GPC)裝置(GPC-101)(昭和電工公司製)、管柱(KD-803,KD-805)(Shodex公司製),以下述方法測定。 In the synthesis examples, the molecular weights of the polyimide precursors and polyimide were measured using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko Corporation) and column (KD-803, KD-805). (Manufactured by Shodex), and measured by the following method.

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-水合物(LiBr-H2O)30mmol/L(升)、磷酸酐結晶(o-磷酸)30mmol/L,及四氫呋喃(THF)10ml/L) Eluent: N, N'-dimethylformamide (additives: lithium bromide-hydrate (LiBr-H 2 O) 30mmol / L (liter), phosphoric anhydride crystal (o-phosphoric acid) 30mmol / L, and tetrahydrofuran (THF) 10ml / L)

流速:1.0ml/分 Flow rate: 1.0ml / min

檢量線製作用標準樣品:TSK標準聚環氧乙烷(分子量:約900,000、150,000、100,000及30,000)(東索公司製)及聚乙二醇(分子量:約12,000、4,000及1,000)(波里曼公司製)。 Standard samples for calibration line production: TSK standard polyethylene oxide (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) (wave Freeman Corporation).

「測定聚醯亞胺之醯亞胺化率」 "Determination of Polyimide Imidation Rate"

以下述方法測定合成例中聚醯亞胺之醯亞胺化率。將聚醯亞胺粉末20mg放入NMR(核磁共振)樣品管(NMR取樣管標準, 5(草野科學公司製)內,加入氘化二甲基亞碸(DMSO-d6,0.05質量%TMS(四甲基矽烷)混合品)(0.53ml)後,施加超音波使其完全溶解。使用NMR測定機(JNW-ECA500)(日本電子丹達姆公司製)測定該溶液的500MHz之質子NMR。醯亞胺化率係以來自醯亞胺化前後未改變之結構的質子作為基準質子而決定,使用該質子之峰積算值與出現於9.5ppm~10.0ppm附近的來自醯胺酸之NH基的質子峰積算值,以下述式求取。 The fluorene imidation rate of polyfluorene imine in the synthesis example was measured by the following method. Put 20 mg of polyfluorene imine powder into an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, In 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 then an ultrasonic wave 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 Nippon Dendam Co., Ltd.). The hydrazone imidization rate is determined by using protons from structures that have not changed before and after hydrazone as the reference protons. The peak value of the protons and the NH groups from the NH group derived from sulfamic acid appear in the vicinity of 9.5 ppm to 10.0 ppm. The proton peak 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為來自醯胺酸之NH基的質子峰積算值,y為基準質子的峰積算值,α為聚醯胺酸(醯亞胺化率為0%)時相對於醯胺酸之NH基質子1個的基準質子之個數比例。 In the above formula, x is an integrated value of a proton peak derived from an NH group of amidine, y is an integrated peak value of a reference proton, and α is a polyamic acid (amidation ratio of 0%) relative to amidine Proportion of the number of reference protons per NH matrix proton.

「合成聚醯亞胺系聚合物」 `` Synthetic polyfluorene-based polymer '' <合成例1> <Synthesis example 1>

於NEP(37.1g)中混合E1(5.21g,26.6mmol)、A1(5.12g,13.5mmol)及B1(2.05g,13.5mmol)後,40℃下反應8小時,得樹脂固體成分濃度25質量%之聚醯胺酸溶液(1)。該聚醯胺酸之Mn(數平均分子量)為25,800,Mw(重量平均分子量)為86,900。 E1 (5.21g, 26.6mmol), A1 (5.12g, 13.5mmol) and B1 (2.05g, 13.5mmol) were mixed with NEP (37.1g), and then reacted at 40 ° C for 8 hours to obtain a resin solid content concentration of 25 mass % Polyamic acid solution (1). The polyamic acid had a Mn (number average molecular weight) of 25,800 and a Mw (weight average molecular weight) of 86,900.

<合成例2> <Synthesis example 2>

於NEP(24.8g)中混合E2(3.22g,12.9mmol)、A2(4.62g,11.7mmol)、B1(1.78g,11.7mmol)及D1(0.28g,2.60mmol)後,80℃下反應5小時,再加入E1(2.52g,12.9mmol)與NEP(12.4g),40℃下反應6小時,得樹脂固體成分濃度為25質量%之聚醯胺酸溶液(2)。該聚醯胺酸之Mn為23,100,Mw為76,400。 E2 (3.22g, 12.9mmol), A2 (4.62g, 11.7mmol), B1 (1.78g, 11.7mmol) and D1 (0.28g, 2.60mmol) were mixed in NEP (24.8g), and then reacted at 80 ° C for 5 After 1 hour, E1 (2.52 g, 12.9 mmol) and NEP (12.4 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution (2) having a resin solid content concentration of 25% by mass. The polyamic acid had Mn of 23,100 and Mw of 76,400.

<合成例3> <Synthesis example 3>

將NEP加入合成例2所得的聚醯胺酸溶液(2)(30.0g)中稀釋為6質量%後,加入作為醯亞胺化觸媒用的乙酸酐(3.95g)及吡啶(2.40g),70℃下反應3.5小時。將該反應溶液投入甲醇(460ml)中,濾取所得的沈澱物。以甲醇洗淨該沈澱物後,100℃下減壓乾燥得聚醯亞胺粉末(3)。該聚醯亞胺之醯亞胺化率為75%,Mn為21,100,Mw為57,500。 NEP was added to the polyamidic acid solution (2) (30.0 g) obtained in Synthesis Example 2 and diluted to 6 mass%, and then acetic anhydride (3.95 g) and pyridine (2.40 g) were used as the phosphonium imidization catalyst. The reaction was carried out at 70 ° C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol and then dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (3). The polyimide has a hydrazone imidization ratio of 75%, Mn of 21,100, and Mw of 57,500.

<合成例4> <Synthesis example 4>

於NMP(24.5g)中混合E2(1.31g,5.23mmol)、A3(3.44g,7.94mmol)、C1(2.57g,10.6mmol)及D2(0.86g,7.94mmol)後,80℃下反應5小時,再加入E1(4.10g,20.9mmol)與NMP(12.3g),40℃下反應6小時,得樹脂固體成分濃度為25質量%之聚醯胺酸溶液。 E2 (1.31g, 5.23mmol), A3 (3.44g, 7.94mmol), C1 (2.57g, 10.6mmol), and D2 (0.86g, 7.94mmol) were mixed in NMP (24.5g), and then reacted at 80 ° C for 5 After 1 hour, E1 (4.10 g, 20.9 mmol) and NMP (12.3 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

將NMP加入所得的聚醯胺酸溶液(30.0g)中稀釋為6質量%後,加入作為醯亞胺化觸媒用的乙酸酐(4.50g)及吡啶(3.30g),80℃下反應3.5小時。將該反應溶液投入甲醇(460ml)中,濾取所得的沈澱物。以甲醇洗淨該沈澱物後,100℃下減壓乾燥得聚醯亞胺粉末(4)。該聚醯亞胺之醯亞胺化率為80%,Mn為15,900,Mw為43,800。 NMP was added to the obtained polyfluorenic acid solution (30.0g) and diluted to 6% by mass, and then acetic anhydride (4.50g) and pyridine (3.30g) were added as the phosphonium imidization catalyst, and the reaction was carried out at 80 ° C for 3.5. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C. to obtain a polyimide powder (4). The polyimide has a fluorene imidation ratio of 80%, Mn of 15,900, and Mw of 43,800.

<合成例5> <Synthesis example 5>

於NMP(24.2g)中混合E2(1.23g,4.91mmol)、A2(3.92g,9.94mmol)、C2(2.58g,9.94mmol)及D2(0.54g,4.97mmol)後,80℃下反應5小時,再加入E1(3.85g,19.6mmol)與NMP(12.1g),40℃下反應6小時,得樹脂固體成分濃度為25質量%之聚醯胺酸溶液。 E2 (1.23g, 4.91mmol), A2 (3.92g, 9.94mmol), C2 (2.58g, 9.94mmol), and D2 (0.54g, 4.97mmol) were mixed in NMP (24.2g), and then reacted at 80 ° C for 5 After 1 hour, E1 (3.85 g, 19.6 mmol) and NMP (12.1 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

將NMP加入所得的聚醯胺酸溶液(30.0g)中稀釋為6質量%後,加入作為醯亞胺化觸媒用的乙酸酐(3.85g)及吡啶(2.50g),60℃下反應2小時。將該反應溶液投入甲醇(460ml)中,濾取所得的沈澱物。以甲醇洗淨該 沈澱物後,100℃下減壓乾燥得聚醯亞胺粉末(5)。該聚醯亞胺之醯亞胺化率為55%,Mn為16,900,Mw為46,900。 After adding NMP to the obtained polyamidic acid solution (30.0g) and diluting it to 6 mass%, acetic anhydride (3.85g) and pyridine (2.50g) were added as the phosphonium imidization catalyst, and reacted at 60 ° C. 2 hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. Wash this with methanol After the precipitate was dried under reduced pressure at 100 ° C., a polyimide powder (5) was obtained. The polyimide has an imidization ratio of 55%, Mn of 16,900, and Mw of 46,900.

<合成例6> <Synthesis example 6>

於NEP(24.8g)中混合E2(2.55g,10.2mmol)、A4(2.55g,5.17mmol)、B1(0.39g,2.58mmol)、C2(3.35g,12.9mmol)及D2(0.56g,5.17mmol)後,80℃下反應5小時,再加入E1(3.00g,15.3mmol)與NEP(12.4g),40℃下反應6小時,得樹脂固體成分濃度為25質量%之聚醯胺酸溶液。 Mix E2 (2.55g, 10.2mmol), A4 (2.55g, 5.17mmol), B1 (0.39g, 2.58mmol), C2 (3.35g, 12.9mmol) and D2 (0.56g, 5.17) in NEP (24.8g) After reacting at 80 ° C for 5 hours, E1 (3.00g, 15.3mmol) and NEP (12.4g) were added, and the reaction was performed at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass. .

將NEP加入所得的聚醯胺酸溶液(30.5g)中稀釋為6質量%後,加入作為醯亞胺化觸媒用的乙酸酐(3.95g)及吡啶(2.55g),60℃下反應3小時。將該反應溶液投入甲醇(460ml)中,濾取所得的沈澱物。以甲醇洗淨該沈澱物後,100℃下減壓乾燥得聚醯亞胺粉末(6)。該聚醯亞胺之醯亞胺化率為61%,Mn為16,000,Mw為44,800。 After adding NEP to the obtained polyamidic acid solution (30.5g) and diluting it to 6% by mass, acetic anhydride (3.95g) and pyridine (2.55g) were added as the phosphonium imidization catalyst, and reacted at 60 ° C for 3 hours. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C. to obtain a polyimide powder (6). The polyimide has a fluorene imidization rate of 61%, Mn of 16,000, and Mw of 44,800.

<合成例7> <Synthesis example 7>

於NEP(24.7g)中混合E2(3.40g,13.6mmol)、B1(4.19g,27.6mmol)及D1(0.74g,6.89mmol)後,80℃下反應5小時,再加入E1(4.00g,20.4mmol)與NEP(12.3g),40℃下反應6小時,得樹脂固體成分濃度為 25質量%之聚醯胺酸溶液(7)。該聚醯胺酸之Mn為27,500,Mw為90,100。 After mixing E2 (3.40 g, 13.6 mmol), B1 (4.19 g, 27.6 mmol) and D1 (0.74 g, 6.89 mmol) in NEP (24.7 g), the reaction was performed at 80 ° C for 5 hours, and then E1 (4.00 g, 20.4mmol) and NEP (12.3g), reacted at 40 ° C for 6 hours, the resin solid content concentration was 25% by mass polyamic acid solution (7). The polyamic acid had Mn of 27,500 and Mw of 90,100.

<合成例8> <Synthesis example 8>

將NEP加入合成例7所得的聚醯胺酸溶液(7)(30.0g)中稀釋為6質量%後,加入作為醯亞胺化觸媒用的乙酸酐(4.40g)及吡啶(3.30g),80℃下反應3.5小時。將該反應溶液投入甲醇(460ml)中,濾取所得的沈澱物。以甲醇洗淨該沈澱物後,100℃下減壓乾燥得聚醯亞胺粉末(8)。該聚醯亞胺之醯亞胺化率為80%,Mn為23,400,Mw為64,500。 NEP was added to the polyamidic acid solution (7) (30.0 g) obtained in Synthesis Example 7 and diluted to 6 mass%, and then acetic anhydride (4.40 g) and pyridine (3.30 g) were used as the phosphonium imidization catalyst. The reaction was carried out at 80 ° C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C. to obtain a polyimide powder (8). The polyimide has an imidization ratio of 80%, Mn of 23,400, and Mw of 64,500.

<合成例9> <Synthesis example 9>

於NEP(24.2g)中混合E2(3.96g,15.8mmol)、B1(4.14g,27.2mmol)、C1(0.39g,1.60mmol)及D2(0.35g,3.20mmol)後,80℃下反應5小時,再加入E1(3.10g,15.8mmol)與NEP(12.1g),40℃下反應6小時,得樹脂固體成分濃度為25質量%之聚醯胺酸溶液。 E2 (3.96g, 15.8mmol), B1 (4.14g, 27.2mmol), C1 (0.39g, 1.60mmol), and D2 (0.35g, 3.20mmol) were mixed in NEP (24.2g), and then reacted at 80 ° C for 5 After 1 hour, E1 (3.10 g, 15.8 mmol) and NEP (12.1 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

將NEP加入所得的聚醯胺酸溶液(30.0g)中稀釋為6質量%後,加入作為醯亞胺化觸媒用的乙酸酐(4.00g)及吡啶(2.50g),60℃下反應2小時。將該反應溶液投入甲醇(460ml)中,濾取所得的沈澱物。以甲醇洗淨該沈澱物後,100℃下減壓乾燥得聚醯亞胺粉末(9)。該聚醯亞胺之醯亞胺化率為53%,Mn為19,900,Mw為 55,100。 After adding NEP to the obtained polyamidic acid solution (30.0g) and diluting it to 6% by mass, acetic anhydride (4.00g) and pyridine (2.50g) as the phosphonium imidization catalyst were added and reacted at 60 ° C. 2 hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C. to obtain a polyimide powder (9). The polyimide has a fluorinated imidization rate of 53%, Mn of 19,900, and Mw of 55,100.

<合成例10> <Synthesis example 10>

於NMP(35.9g)中混合E3(5.90g,26.3mmol)、A2(4.21g,10.7mmol)、B1(0.41g,2.67mmol)及D2(1.44g,13.3mmol)後,40℃下反應8小時,得樹脂固體成分濃度為25質量%之聚醯胺酸溶液。 E3 (5.90 g, 26.3 mmol), A2 (4.21 g, 10.7 mmol), B1 (0.41 g, 2.67 mmol), and D2 (1.44 g, 13.3 mmol) were mixed in NMP (35.9 g), and then reacted at 40 ° C. 8 A polyamic acid solution having a resin solid content concentration of 25% by mass was obtained for hours.

將NMP加入所得的聚醯胺酸溶液(30.0g)中稀釋為6質量%後,加入作為醯亞胺化觸媒用的乙酸酐(4.50g)及吡啶(3.35g),80℃下反應3.5小時。將該反應溶液投入甲醇(460ml)中,濾取所得的沈澱物。以甲醇洗淨該沈澱物後,100℃下減壓乾燥得聚醯亞胺粉末(10)。該聚醯亞胺之醯亞胺化率為81%,Mn為18,200,Mw為51,600。 After adding NMP to the obtained polyamidic acid solution (30.0g) and diluting to 6% by mass, acetic anhydride (4.50g) and pyridine (3.35g) were added as the phosphonium imidization catalyst, and the reaction was carried out at 80 ° C for 3.5. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C. to obtain a polyimide powder (10). The polyimide has a fluorene imidization ratio of 81%, Mn of 18,200, and Mw of 51,600.

<合成例11> <Synthesis example 11>

於NMP(36.7g)中混合E3(5.50g,24.5mmol)、A4(2.45g,4.97mmol)、B1(0.19g,1.24mmol)及C2(3.54g,13.7mmol)及D2(0.54g,4.97mmol)後,40℃下反應8小時,得樹脂固體成分濃度為25質量%之聚醯胺酸溶液。 E3 (5.50g, 24.5mmol), A4 (2.45g, 4.97mmol), B1 (0.19g, 1.24mmol) and C2 (3.54g, 13.7mmol) and D2 (0.54g, 4.97) were mixed in NMP (36.7g) mmol), and then reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

將NMP加入所得的聚醯胺酸溶液(30.5g)中稀釋為6質量%後,加入作為醯亞胺化觸媒用的乙酸酐(3.90g)及吡啶(2.60g),60℃下反應3.5小時。將該反應溶液投 入甲醇(460ml)中,濾取所得的沈澱物。以甲醇洗淨該沈澱物後,100℃下減壓乾燥得聚醯亞胺粉末(11)。該聚醯亞胺之醯亞胺化率為65%,Mn為18,500,Mw為50,200。 After adding NMP to the obtained polyamidic acid solution (30.5g) and diluting it to 6 mass%, acetic anhydride (3.90g) and pyridine (2.60g) were added as the phosphonium imidization catalyst, and the reaction was carried out at 60 ° C for 3.5. hour. Throw the reaction solution It was poured into methanol (460 ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C. to obtain a polyimide powder (11). The polyimide has a fluorene imidization rate of 65%, Mn of 18,500, and Mw of 50,200.

<合成例12> <Synthesis example 12>

於NMP(37.3g)中混合E3(7.50g,33.5mmol)、B1(3.61g,23.7mmol)、C1(0.41g,1.69mmol)及D1(0.92g,8.47mmol)後,40℃下反應8小時,得樹脂固體成分濃度為25質量%之聚醯胺酸溶液。 E3 (7.50g, 33.5mmol), B1 (3.61g, 23.7mmol), C1 (0.41g, 1.69mmol), and D1 (0.92g, 8.47mmol) were mixed in NMP (37.3g), and then reacted at 40 ° C for 8 A polyamic acid solution having a resin solid content concentration of 25% by mass was obtained for hours.

將NMP加入所得的聚醯胺酸溶液(30.0g)中稀釋為6質量%後,加入作為醯亞胺化觸媒用的乙酸酐(4.20g)及吡啶(3.10g),80℃下反應2.5小時。將該反應溶液投入甲醇(460ml)中,濾取所得的沈澱物。以甲醇洗淨該沈澱物後,100℃下減壓乾燥得聚醯亞胺粉末(12)。該聚醯亞胺之醯亞胺化率為75%,Mn為19,800,Mw為53,900。 After adding NMP to the obtained polyamidic acid solution (30.0g) and diluting it to 6 mass%, acetic anhydride (4.20g) and pyridine (3.10g) were added as the phosphonium imidization catalyst, and the reaction was carried out at 80 ° C for 2.5 hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C. to obtain a polyimide powder (12). The polyimide has a hydrazone imidization rate of 75%, Mn of 19,800, and Mw of 53,900.

<合成例13> <Synthesis Example 13>

於NEP(23.8g)中混合E4(5.21g,17.3mmol)、A1(4.60g,12.1mmol)、B1(0.67g,4.39mmol)及D1(0.59g,5.49mmol)後,80℃下反應6小時,再加入E1(0.85g,4.33mmol)與NEP(11.9g),40℃下反應6小時,得樹脂固體成分濃度為25質量%之聚醯胺酸溶液。 E4 (5.21g, 17.3mmol), A1 (4.60g, 12.1mmol), B1 (0.67g, 4.39mmol), and D1 (0.59g, 5.49mmol) were mixed in NEP (23.8g), and then reacted at 80 ° C. 6 After 1 hour, E1 (0.85 g, 4.33 mmol) and NEP (11.9 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

將NEP加入所得的聚醯胺酸溶液(30.0g)中稀釋為6質量%後,加入作為醯亞胺化觸媒用的乙酸酐(3.80g)及吡啶(2.50g),60℃下反應2小時。將該反應溶液投入甲醇(460ml)中,濾取所得的沈澱物。以甲醇洗淨該沈澱物後,100℃下減壓乾燥得聚醯亞胺粉末(13)。該聚醯亞胺之醯亞胺化率為55%,Mn為16,800,Mw為45,300。 After adding NEP to the obtained polyamidic acid solution (30.0g) and diluting to 6% by mass, acetic anhydride (3.80g) and pyridine (2.50g) were added as the phosphonium imidization catalyst, and reacted at 60 ° C. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C. to obtain a polyimide powder (13). The polyimide has a fluorene imidation rate of 55%, Mn of 16,800, and Mw of 45,300.

<合成例14> <Synthesis Example 14>

於NMP(23.9g)中混合E4(3.29g,11.0mmol)、A2(3.51g,8.88mmol)、C1(1.61g,6.66mmol)、C2(1.15g,4.44mmol)及D2(0.24g,2.22mmol)後,80℃下反應6小時,再加入E1(2.15g,11.0mmol)與NMP(12.0g),40℃下反應6小時,得樹脂固體成分濃度為25質量%之聚醯胺酸溶液。 E4 (3.29g, 11.0mmol), A2 (3.51g, 8.88mmol), C1 (1.61g, 6.66mmol), C2 (1.15g, 4.44mmol) and D2 (0.24g, 2.22) were mixed in NMP (23.9g) After reacting at 80 ° C for 6 hours, E1 (2.15g, 11.0mmol) and NMP (12.0g) were added, and the reaction was conducted at 40 ° C for 6 hours to obtain a polyamine solution having a resin solid content concentration of 25% by mass. .

將NMP加入所得的聚醯胺酸溶液(30.1g)中稀釋為6質量%後,加入作為醯亞胺化觸媒用的乙酸酐(4.20g)及吡啶(3.15g),80℃下反應2.5小時。將該反應溶液投入甲醇(460ml)中,濾取所得的沈澱物。以甲醇洗淨該沈澱物後,100℃下減壓乾燥得聚醯亞胺粉末(14)。該聚醯亞胺之醯亞胺化率為73%,Mn為15,900,Mw為43,800。 NMP was added to the obtained polyamidic acid solution (30.1 g) and diluted to 6% by mass, and then acetic anhydride (4.20 g) and pyridine (3.15 g) were added as the phosphonium imidization catalyst, and the reaction was performed at 80 ° C for 2.5. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol and then dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (14). The polyimide has a fluorene imidation rate of 73%, Mn of 15,900, and Mw of 43,800.

<合成例15> <Synthesis Example 15>

於NMP(23.5g)中混合E5(4.30g,20.3mmol)、A3(3.89g,8.98mmol)、C2(1.33g,5.13mmol)及D2(1.25g,11.6mmol)後,80℃下反應6小時,再加入E1(0.99g,5.07mmol)與NMP(11.8g),40℃下反應6小時,得樹脂固體成分濃度為25質量%之聚醯胺酸溶液。 E5 (4.30 g, 20.3 mmol), A3 (3.89 g, 8.98 mmol), C2 (1.33 g, 5.13 mmol), and D2 (1.25 g, 11.6 mmol) were mixed in NMP (23.5 g), and reacted at 80 ° C. 6 After 1 hour, E1 (0.99 g, 5.07 mmol) and NMP (11.8 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

將NMP加入所得的聚醯胺酸溶液(30.0g)中稀釋為6質量%後,加入作為醯亞胺化觸媒用的乙酸酐(3.85g)及吡啶(2.40g),60℃下反應2小時。將該反應溶液投入甲醇(460ml)中,濾取所得的沈澱物。以甲醇洗淨該沈澱物後,100℃下減壓乾燥得聚醯亞胺粉末(15)。該聚醯亞胺之醯亞胺化率為51%,Mn為15,700,Mw為44,500。 NMP was added to the obtained polyamidic acid solution (30.0g) and diluted to 6% by mass, and then acetic anhydride (3.85g) and pyridine (2.40g) were added as the phosphonium imidization catalyst, and reacted at 60 ° C. 2 hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (15). The polyimide has a fluorinated imidization rate of 51%, Mn of 15,700, and Mw of 44,500.

<合成例16> <Synthesis example 16>

於NEP(23.9g)中混合E5(2.95g,13.9mmol)、A2(3.71g,9.39mmol)、B1(0.36g,2.35mmol)、C1(1.14g,4.70mmol)、C2(1.22g,4.70mmol)及D1(0.25g,2.35mmol)後,80℃下反應6小時,再加入E2(2.32g,9.27mmol)與NEP(11.9g),80℃下反應6小時,得樹脂固體成分濃度為25質量%之聚醯胺酸溶液。 E5 (2.95g, 13.9mmol), A2 (3.71g, 9.39mmol), B1 (0.36g, 2.35mmol), C1 (1.14g, 4.70mmol), C2 (1.22g, 4.70) were mixed in NEP (23.9g) mmol) and D1 (0.25g, 2.35mmol), reacted at 80 ° C for 6 hours, then added E2 (2.32g, 9.27mmol) and NEP (11.9g), and reacted at 80 ° C for 6 hours. 25% by mass polyamic acid solution.

將NMP加入所得的聚醯胺酸溶液(30.0g)中稀釋為6質量%後,加入作為醯亞胺化觸媒用的乙酸酐(4.20g)及吡啶(3.20g),80℃下反應2小時。將該反應溶液投入甲醇(460ml)中,濾取所得的沈澱物。以甲醇洗淨該 沈澱物後,100℃下減壓乾燥得聚醯亞胺粉末(16)。該聚醯亞胺之醯亞胺化率為68%,Mn為15,500,Mw為45,100。 NMP was added to the obtained polyfluorenic acid solution (30.0g) and diluted to 6% by mass, and then acetic anhydride (4.20g) and pyridine (3.20g) were used as the phosphonium imidization catalyst, and reacted at 80 ° C. 2 hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. Wash this with methanol The precipitate was dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (16). The polyimide has a fluorene imidation ratio of 68%, Mn of 15,500, and Mw of 45,100.

<合成例17> <Synthesis example 17>

於NMP(24.3g)中混合E5(4.10g,19.3mmol)、B1(4.47g,29.4mmol)及D2(0.35g,3.26mmol)後,80℃下反應6小時,再加入E2(3.22g,12.9mmol)與NMP(12.1g),80℃下反應6小時,得樹脂固體成分濃度為25質量%之聚醯胺酸溶液。 After mixing E5 (4.10 g, 19.3 mmol), B1 (4.47 g, 29.4 mmol) and D2 (0.35 g, 3.26 mmol) in NMP (24.3 g), the reaction was performed at 80 ° C for 6 hours, and then E2 (3.22 g, 12.9 mmol) and NMP (12.1 g) were reacted at 80 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

將NMP加入所得的聚醯胺酸溶液(30.0g)中稀釋為6質量%後,加入作為醯亞胺化觸媒用的乙酸酐(4.20g)及吡啶(3.20g),80℃下反應2.5小時。將該反應溶液投入甲醇(460ml)中,濾取所得的沈澱物。以甲醇洗淨該沈澱物後,100℃下減壓乾燥得聚醯亞胺粉末(17)。該聚醯亞胺之醯亞胺化率為73%,Mn為16,200,Mw為48,100。 After adding NMP to the obtained polyamidic acid solution (30.0g) and diluting to 6% by mass, acetic anhydride (4.20g) and pyridine (3.20g) were added as the phosphonium imidization catalyst, and the reaction was carried out at 80 ° C for 2.5 hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C. to obtain a polyimide powder (17). This polyfluorene imine has a sulfonium imidization ratio of 73%, Mn of 16,200, and Mw of 48,100.

<合成例18> <Synthesis example 18>

於NEP(23.8g)中混合E2(2.85g,11.4mmol)、A1(2.20g,5.77mmol)及B1(3.51g,23.1mmol)後,80℃下反應5小時,再加入E1(3.35g,17.1mmol)與NEP(11.9g),40℃下反應6小時,得樹脂固體成分濃度為25質量%之聚醯胺酸溶液(18)。該聚醯胺酸之Mn為 24,800,Mw為80,200。 E2 (2.85g, 11.4mmol), A1 (2.20g, 5.77mmol) and B1 (3.51g, 23.1mmol) were mixed in NEP (23.8g), and then reacted at 80 ° C for 5 hours, and then E1 (3.35g, 17.1 mmol) and NEP (11.9 g) were reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution (18) having a resin solid content concentration of 25% by mass. The Mn of the polyamic acid is 24,800, Mw is 80,200.

<合成例19> <Synthesis example 19>

於NEP加入合成例18所得的聚醯胺酸溶液(18)(30.0g)中稀釋為6質量%後,加入作為醯亞胺化觸媒用的乙酸酐(4.40g)及吡啶(3.35g),80℃下反應3.5小時。將該反應溶液投入甲醇(460ml)中,濾取所得的沈澱物。以甲醇洗淨該沈澱物後,100℃下減壓乾燥得聚醯亞胺粉末(19)。該聚醯亞胺之醯亞胺化率為79%,Mn為18,400,Mw為47,200。 The polyamine solution (18) (30.0 g) obtained by adding Synthesis Example 18 to NEP was diluted to 6% by mass, and then acetic anhydride (4.40 g) and pyridine (3.35 g) were used as the phosphonium imidization catalyst. The reaction was carried out at 80 ° C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C to obtain a polyimide powder (19). The polyimide has a fluorene imidation ratio of 79%, Mn of 18,400, and Mw of 47,200.

<合成例20> <Synthesis example 20>

於NMP(24.7g)中混合E2(3.25g,13.0mmol)、B1(1.80g,11.9mmol)、D1(0.28g,2.60mmol)及D3(4.46g,11.9mmol)後,80℃下反應5小時,再加入E1(2.55g,13.0mmol)與NMP(12.4g),40℃下反應6小時,得樹脂固體成分濃度為25質量%之聚醯胺酸溶液。 E2 (3.25g, 13.0mmol), B1 (1.80g, 11.9mmol), D1 (0.28g, 2.60mmol), and D3 (4.46g, 11.9mmol) were mixed in NMP (24.7g) and reacted at 80 ° C for 5 After 1 hour, E1 (2.55 g, 13.0 mmol) and NMP (12.4 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

將NMP加入所得的聚醯胺酸溶液(30.0g)中稀釋為6質量%後,加入作為醯亞胺化觸媒用的乙酸酐(4.20g)及吡啶(3.20g),80℃下反應3小時。將該反應溶液投入甲醇(460ml)中,濾取所得的沈澱物。以甲醇洗淨該沈澱物後,100℃下減壓乾燥得聚醯亞胺粉末(20)。該聚醯亞胺之醯亞胺化率為75%,Mn為14,600,Mw為41,200。 NMP was added to the obtained polyfluorenic acid solution (30.0g) and diluted to 6% by mass, and then acetic anhydride (4.20g) and pyridine (3.20g) were used as the phosphonium imidization catalyst, and reacted at 80 ° C for 3 hours. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol and then dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (20). The polyfluorene imine has a hydrazone imidation ratio of 75%, Mn of 14,600, and Mw of 41,200.

聚醯亞胺系聚合物如表32~表34所示。 The polyfluorene-based polymers are shown in Tables 32 to 34.

[製造液晶配向處理劑] [Manufacturing liquid crystal alignment treatment agent]

下述實施例1~20及比較例1~7中所記載為,液晶配向處理劑的製造例。又,該液晶配向處理劑也作為評估用。 The following Examples 1 to 20 and Comparative Examples 1 to 7 are examples of manufacturing liquid crystal alignment treatment agents. The liquid crystal alignment treatment agent is also used for evaluation.

所得的液晶配向處理劑如表35~表37所示。又,表35~表37中下述* 1~* 5各自表示下述定義。 The obtained liquid crystal aligning agent is shown in Table 35-Table 37. The following * 1 to * 5 in Tables 35 to 37 each indicate the following definitions.

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

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

* 3:相對於全部溶劑100質量份的各溶劑之導入量(質量份)。 * 3: The amount of each solvent introduced (100 parts by mass) relative to 100 parts by mass of the entire solvent.

* 4:液晶配向處理劑中全部聚合物所佔之比例。 * 4: The proportion of all polymers in the liquid crystal alignment treatment agent.

* 5:液晶配向處理劑中全部聚合物所佔之比例。 * 5: The proportion of all polymers in the liquid crystal alignment treatment agent.

使用實施例及比較例所得的液晶配向處理劑,進行下述「評估液晶配向處理劑之噴墨印刷塗佈 性」、「製作液晶單元及評估預傾角(一般單元)」、「評估電壓保持率(一般單元)」、「評估殘留電荷之緩和(一般單元)」及「製作液晶單元及評估液晶配向性(PSA單元)」。 Using the liquid crystal alignment treatment agents obtained in the examples and comparative examples, the following "Evaluation of inkjet printing coating of liquid crystal alignment treatment agents" was performed Properties "," Making a liquid crystal cell and evaluating a pretilt angle (general cell) "," Evaluating a voltage retention rate (general cell) "," Evaluating the mitigation of residual charge (general cell) ", and" Making a liquid crystal cell and evaluating liquid crystal alignment ( PSA unit) ".

「評估液晶配向處理劑之噴墨印刷塗佈性」 "Evaluating the inkjet printing coatability of liquid crystal alignment treatment agents"

使用細孔徑1μm之膜濾器加壓過濾實施例4所得的液晶配向處理劑(4)、實施例7所得的液晶配向處理劑(7)、實施例10所得的液晶配向處理劑(10)、實施例13所得的液晶配向處理劑(13)及實施例18所得的液晶配向處理劑(18)後,評估噴墨印刷塗佈性。所使用的噴墨印刷塗佈機為HIS-200(日立設備技術公司製)。塗佈時係於以純水及IPA洗淨後之ITO(氧化銦錫)蒸鍍基板上,以塗佈面積為70×70mm、噴嘴間距為0.423mm、掃描間距為0.5mm、塗佈速度為40mm/秒,由塗佈至煅乾燥之時間為60秒、煅乾燥係為熱板上70℃下5分鐘之條件進行。 The liquid crystal alignment treatment agent (4) obtained in Example 4; the liquid crystal alignment treatment agent (7) obtained in Example 7; the liquid crystal alignment treatment agent (10) obtained in Example 10; After the liquid crystal alignment treatment agent (13) obtained in Example 13 and the liquid crystal alignment treatment agent (18) obtained in Example 18, the inkjet printing coatability was evaluated. The inkjet printing coater used was HIS-200 (manufactured by Hitachi Equipment Technology Co., Ltd.). The coating was performed on an ITO (indium tin oxide) evaporation substrate washed with pure water and IPA. The coating area was 70 × 70mm, the nozzle pitch was 0.423mm, the scanning pitch was 0.5mm, and the coating speed was 40 mm / sec. The time from coating to calcination drying was 60 seconds, and calcination drying was performed at 70 ° C for 5 minutes on a hot plate.

確認所得的附液晶配向膜之基板的塗膜性。具體上係於鈉燈下進行目視觀察,確認有無針孔。結果任何實施例所得的液晶配向膜之塗膜上均無針孔,可得塗膜性優良的液晶配向膜。 The coating property of the obtained substrate with a liquid crystal alignment film was confirmed. Specifically, visual observation was performed under a sodium lamp to confirm the presence or absence of pinholes. As a result, there were no pinholes in the coating film of the liquid crystal alignment film obtained in any of the examples, and a liquid crystal alignment film having excellent coating film properties was obtained.

「製作液晶單元及評估預傾角(一般單元)」 "Making LCD Cells and Evaluating Pretilt Angle (General Units)"

使用細孔徑1μm之膜濾器加壓過濾實施例及比較例所得的液晶配向處理劑後,製作液晶單元(一般單元)。將該溶液旋轉塗佈於以純水及IPA洗淨後的100×100mm附ITO電極之基板(長100mm×寬100mm,厚0.7mm)的ITO面後,依序以熱板上100℃下5分鐘、熱循環型無菌烤箱中230℃下30分鐘之加熱處理,得膜厚100nm之附聚醯亞胺液晶配向膜的ITO基板。又,以與上述「評估液晶配向處理劑之噴墨印刷塗佈性」相同之條件,使用實施例4所得的液晶配向處理劑(4)、實施例7所得的液晶配向處理劑(7)、實施例10所得的液晶配向處理劑(10)、實施例13所得的液晶配向處理劑(13)及實施例18所得的液晶配向處理劑(18)製作附液晶配向膜之基板後,於熱循環型無菌烤箱中230℃下加熱處理30分鐘,得膜厚100nm之附聚醯亞胺液晶配向膜的ITO基板。 The liquid crystal alignment treatment agents obtained in the examples and comparative examples were pressure-filtered using a membrane filter having a pore size of 1 μm, and then a liquid crystal cell (general cell) was produced. This solution was spin-coated on the ITO surface of a 100 × 100mm substrate (100mm × 100mm in width and 0.7mm in thickness) with an ITO electrode washed with pure water and IPA. A heat treatment was performed at 230 ° C for 30 minutes in a thermal cycle type aseptic oven for 30 minutes to obtain an ITO substrate with an agglomerated polyimide liquid crystal alignment film having a film thickness of 100 nm. In addition, the liquid crystal alignment treatment agent (4) obtained in Example 4 and the liquid crystal alignment treatment agent (7) obtained in Example 7 were used under the same conditions as the above "evaluating the inkjet printing coatability of the liquid crystal alignment treatment agent". The liquid crystal alignment treatment agent (10) obtained in Example 10, the liquid crystal alignment treatment agent (13) obtained in Example 13, and the liquid crystal alignment treatment agent (18) obtained in Example 18 were used to prepare a substrate with a liquid crystal alignment film, and then subjected to thermal cycling. In an aseptic oven at 230 ° C. for 30 minutes, an ITO substrate with agglomerated fluorene imine liquid crystal alignment film with a film thickness of 100 nm was obtained.

使用輥徑為120mm之摩擦裝置以人造絲布、輥回轉數為1000rpm、輥行進速度為50mm/sec、押入量為0.1mm之條件對該ITO基板之塗膜面進行摩擦處理。 A friction device with a roll diameter of 120 mm was used to rub the coated film surface of the ITO substrate under conditions of rayon cloth, roll revolutions of 1000 rpm, roll travel speed of 50 mm / sec, and push-in amount of 0.1 mm.

準備2枚所得的附液晶配向膜之ITO基板,以液晶配向膜面為內側之方式挾持6μm的調距物,組合後以密封劑接合四周製作空單元。藉由減壓注入法將MLC-6608(美爾庫製)注入該空單元內,密封注入口後得液晶單元(一般單元)。 Two obtained ITO substrates with a liquid crystal alignment film were prepared, and a 6 μm distance adjuster was held so that the liquid crystal alignment film surface was inside. After the combination, a sealant was used to join the surroundings to make an empty cell. MLC-6608 (Merco) was injected into the empty cell by a reduced pressure injection method, and a liquid crystal cell (general cell) was obtained after the injection port was sealed.

其次測定該液晶單元(一般單元)之預傾角。預 傾角係於進行液晶之同位處理(95℃下加熱處理5分鐘)後,測定該加熱處理(120℃下加熱處理5小時)後之液晶單元所得。 Next, the pretilt angle of the liquid crystal cell (general cell) was measured. Advance The inclination angle was obtained after the liquid crystal cell was subjected to the isotopic treatment of the liquid crystal (heat treatment at 95 ° C for 5 minutes), and the liquid crystal cell after the heat treatment (heat treatment at 120 ° C for 5 hours) was measured.

另外同樣測定對以上述相同之條件製作的液晶單元進行同位處理後,照射365nm換算下10J/cm2之紫外線後的液晶單元。又,預傾角係使用PAS-301(ELSICON製)以室溫測定。照射紫外線係使用桌上型UV硬化裝置(HCT3B28HEX-1)(先來特製)進行。 In addition, a liquid crystal cell prepared under the same conditions as described above was subjected to an in-situ treatment, and then the liquid crystal cell was irradiated with ultraviolet rays of 10 J / cm 2 at 365 nm conversion. The pretilt angle was measured at room temperature using PAS-301 (manufactured by ELSICON). Ultraviolet irradiation is performed using a desktop UV curing device (HCT3B28HEX-1) (specially made first).

評估方法為,將相對於液晶之同位處理後(也稱為Iso處理後)的預傾角,加熱處理後(也稱為高溫處理後)及照射紫外線後(也稱為紫外線照射後)的預傾角變化比較小者視為良好(表38~表40係表示Iso處理後、高溫處理後及紫外線照射後之預傾角的值)。 The evaluation method is based on the pretilt angle of the liquid crystal after the parity treatment (also called the Iso treatment), the heat treatment (also called the high temperature treatment), and the pretilt angle after the ultraviolet irradiation (also called the ultraviolet irradiation). Those with relatively small changes are considered good (Tables 38 to 40 show values of the pretilt angle after Iso treatment, after high temperature treatment, and after ultraviolet irradiation).

表38~表40為標記實施例及比較例所得之結果。 Tables 38 to 40 show the results obtained in the marked examples and comparative examples.

「評估電壓保持率(一般單元)」 `` Evaluation of voltage holding ratio (general unit) ''

使用以與上述「製作液晶單元及評估預傾角(一般單元)」相同之條件製作的液晶單元(一般單元),評估電壓保持率。具體上係於80℃之溫度下,將60μs之1V的電壓施加於上述方法所得的液晶單元(一般單元)上,測定50ms後之電壓,再計算可保有多少電壓作為電壓保持率(稱為VHR)用。又,測定時係使用電壓保持率測定裝置(VHR-1,東陽技術公司製),以設定為Voltage:±1V,Pulse Width:60μs,Flame Period:50ms之方式進 行。 The voltage holding ratio was evaluated using a liquid crystal cell (general cell) manufactured under the same conditions as the above-mentioned "producing a liquid crystal cell and evaluating a pretilt angle (general cell)". Specifically, at a temperature of 80 ° C, a voltage of 1V at 60 μs is applied to the liquid crystal cell (general cell) obtained by the above method, the voltage after 50ms is measured, and then how much voltage can be maintained as the voltage retention rate (referred to as VHR) )use. The measurement was performed using a voltage holding ratio measuring device (VHR-1, manufactured by Toyo Technology Co., Ltd.), and the voltage was set to Voltage: ± 1V, Pulse Width: 60μs, and Flame Period: 50ms. Row.

另外使用桌上型UV硬化裝置(HCT3B28HEX-1,先來特公司製),將365nm換算下50J/cm2之紫外線照射於結束上述製作液晶單元後立即測定電壓保持率後的液晶單元上,再以與上述相同之條件測定電壓保持率。 In addition, using a desktop UV curing device (HCT3B28HEX-1, first manufactured by special company), 50 J / cm 2 of ultraviolet light converted at 365 nm was irradiated onto the liquid crystal cell immediately after measuring the voltage holding ratio after the production of the liquid crystal cell, and then The voltage holding ratio was measured under the same conditions as above.

評估方法為,將液晶單元製作後立即測得的電壓保持率之值較高,且相對於液晶單元製作後立即測定的電壓保持率之值,紫外線照射後之值下降程度較小者視為良好(表41~表43係表示液晶單元製作後立即及紫外線照射後的VHR之值)。表41~表43係表示實施例及比較例所得的結果。 The evaluation method is that the value of the voltage holding ratio measured immediately after the liquid crystal cell is made is high, and the value of the voltage holding ratio measured immediately after the liquid crystal cell is made, the smaller the value after the ultraviolet irradiation is, the better. (Tables 41 to 43 show the VHR values immediately after the production of the liquid crystal cell and after the ultraviolet irradiation). Tables 41 to 43 show the results obtained in the examples and comparative examples.

「評估殘留電荷之緩和(一般單元)」 "Assessment of Reduction of Residual Charges (General Unit)"

使用以與上述「製作液晶單元及評估預傾角(一般單元)」相同之條件所製作的液晶單元(一般單元),評估殘留電荷之緩和。具體上係將直流電壓10V施加於液晶單元上30分鐘後使其短路1秒,再測定1800秒的液晶單元內所發生的電位。其中使用50秒後之殘留電荷值,評估殘留電荷之緩和。又,測定時係使用6254型液晶物性評估裝置(東陽技術公司製)。 The liquid crystal cell (general cell) produced under the same conditions as the above-mentioned "producing a liquid crystal cell and evaluating the pretilt angle (general cell)" was used to evaluate the relaxation of the residual charge. Specifically, a DC voltage of 10 V was applied to the liquid crystal cell for 30 minutes and then short-circuited for 1 second, and then the potential generated in the liquid crystal cell was measured for 1800 seconds. The residual charge value after 50 seconds was used to evaluate the relaxation of the residual charge. In the measurement, a 6254 type liquid crystal physical property evaluation device (manufactured by Toyo Technology Co., Ltd.) was used.

另外使用桌上型UV硬化裝置(HCT3B28HEX-1)(先來特公司製),將365nm換算下30J/cm2之紫外線照射於結束上述製作液晶單元後立即測定殘留電荷後的液晶單元上,以與上述相同之條件測定殘留電荷。 In addition, using a desk-type UV curing device (HCT3B28HEX-1) (manufactured by Toray Co., Ltd.), 30 J / cm 2 of ultraviolet light converted at 365 nm was irradiated onto the liquid crystal cell immediately after the above-mentioned production of the liquid crystal cell was measured for residual charge. The residual charge was measured under the same conditions as above.

評估方法為,將液晶單元製作後立即及照射紫外線後測定的殘留電荷值較小者視為良好(表41~表43係表示液晶單元製作後立即及照射紫外線後之VHR值)。表41~表43係表示實施例及比較例所得的結果。 The evaluation method is that the smaller the residual charge value measured immediately after the liquid crystal cell is manufactured and after the irradiation with ultraviolet rays is regarded as good (Tables 41 to 43 show the VHR values immediately after the liquid crystal cell is manufactured and after ultraviolet rays are irradiated). Tables 41 to 43 show the results obtained in the examples and comparative examples.

「製作液晶單元及評估液晶配向性(PSA單元)」 "Making a liquid crystal cell and evaluating liquid crystal alignment (PSA cell)"

以細孔徑1μm之膜濾器加壓過濾實施例2所得的液晶配向處理劑(2)、實施例3所得的液晶配向處理劑(3)、實施例9所得的液晶配向處理劑(9)、實施例11所得的液晶配向處理劑(11)及實施例14所得的液晶配向處理劑(14)後,製作液晶單元及評估液晶配向性(PSA單元)。將該溶液旋轉塗佈於以純水及IPA洗淨後中心附10×10mm之圖型間隔20μm的ITO電極之基板(長40mm×寬30mm,厚0.7mm)與中心附10×40mm之ITO電極的基板(長40mm×寬30mm,厚0.7mm)之ITO面後,依序進行熱板上100℃下5分鐘,熱循環型無菌烤箱中230℃下30分鐘的加熱處理,得膜厚100nm之聚醯亞胺塗膜。 The liquid crystal alignment treatment agent (2) obtained in Example 2, the liquid crystal alignment treatment agent (3) obtained in Example 3, the liquid crystal alignment treatment agent (9) obtained in Example 9, and the pressure were filtered through a membrane filter with a pore size of 1 μm. After the liquid crystal alignment treatment agent (11) obtained in Example 11 and the liquid crystal alignment treatment agent (14) obtained in Example 14, a liquid crystal cell was prepared and the liquid crystal alignment property (PSA cell) was evaluated. This solution was spin-coated on a substrate (length 40mm × width 30mm, thickness 0.7mm) with a 10 × 10mm pattern interval ITO electrode at the center and a 10 × 40mm ITO electrode at the center after washing with pure water and IPA. After the ITO surface of the substrate (length 40mm × width 30mm, thickness 0.7mm), heat treatment was performed on the hot plate at 100 ° C. for 5 minutes and 230 ° C. for 30 minutes in a thermal cycle type aseptic oven to obtain a film thickness of 100 nm. Polyimide coating film.

以液晶配向膜面為內側之方式,使該附液晶配向膜之基板挾持6μm之調距物組合後,以密封劑黏合四周製作空單元,藉由減壓注入法於向列型液晶(MLC-6608)(美爾庫日本公司製)中,將下述式所示聚合性化合物(1)以相對於向列型液晶(MLC-6608)100質量%為0.3質量%之聚合性化合物(1)混合所得之液晶注入該空單 元內,密封注入口後得液晶單元。 With the liquid crystal alignment film surface as the inner side, the substrate with the liquid crystal alignment film was held by a 6 μm distance adjusting combination, and then the surrounding cells were made with a sealant to make empty cells, and the nematic liquid crystal (MLC- 6608) (Mercury Japan Co., Ltd.), a polymerizable compound (1) having a polymerizable compound (1) represented by the following formula in an amount of 0.3% by mass relative to 100% by mass of nematic liquid crystal (MLC-6608) The resulting liquid crystal is injected into the empty sheet In the cell, a liquid crystal cell is obtained after the injection port is sealed.

將交流5V之電壓施加於所得液晶單元的同時,使用照明度60mW之金屬鹵素燈,於切斷350nm以下之波長下照射365nm換算下20J/cm2之紫外線,得液晶之配向方向被控制的液晶單元(PSA單元)。液晶單元照射紫外線時照射裝置內的溫度為50℃。 While applying an AC voltage of 5V to the obtained liquid crystal cell, a metal halide lamp with an illuminance of 60mW was used to cut off a wavelength of less than 350nm and irradiate 20J / cm 2 of ultraviolet light at 365nm conversion to obtain a liquid crystal with controlled orientation direction of the liquid crystal. Unit (PSA unit). When the liquid crystal cell was irradiated with ultraviolet rays, the temperature inside the irradiation device was 50 ° C.

測定該液晶單元之照射紫外線前及照射紫外線後的液晶應答速度。應答速度係測定透過率90%至透過率10%的T90→T10。 The response speed of the liquid crystal cell before and after ultraviolet irradiation was measured. The response speed is measured from T90 to T10 from 90% transmittance to 10% transmittance.

任一實施例所得的PSA單元為,比較照射紫外線前之液晶單元,照射紫外線後的液晶單元之應答速度較快,故確認液晶之配向方向被控制。又,藉由偏光顯微鏡(ECLIPSE E600WPOL)(尼康公司製)觀察任一液晶單元,確認液晶呈均勻地配向。 The PSA cell obtained in any of the embodiments is a comparison of the liquid crystal cell before ultraviolet radiation, and the response speed of the liquid crystal cell after ultraviolet radiation is faster, so it is confirmed that the alignment direction of the liquid crystal is controlled. In addition, each of the liquid crystal cells was observed with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation), and it was confirmed that the liquid crystals were uniformly aligned.

<實施例1> <Example 1>

將NEP(13.3g)、BCS(9.80g)、EC(3.30g)及M1(0.21g)加入合成例1所得的樹脂固體成分濃度25質量%之聚醯胺酸溶液(1)(5.00g)及合成例7所得的樹 脂固體成分濃度25質量%之聚醯胺酸溶液(7)(3.30g)中,25℃下攪拌6小時,得液晶配向處理劑(1)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NEP (13.3 g), BCS (9.80 g), EC (3.30 g), and M1 (0.21 g) were added to a polyamic acid solution (1) (5.00 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 1. And tree obtained in Synthesis Example 7 In a polyamic acid solution (7) (3.30 g) having a fat solid content concentration of 25% by mass, it was stirred at 25 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (1). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<實施例2> <Example 2>

將NEP(14.9g)及BCS(14.5g)加入合成例2所得的樹脂固體成分濃度25質量%之聚醯胺酸溶液(2)(6.50g)及合成例7所得的樹脂固體成分濃度25質量%之聚醯胺酸溶液(7)(2.80g)中,25℃下攪拌4小時,得液晶配向處理劑(2)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NEP (14.9 g) and BCS (14.5 g) were added to the polyamic acid solution (2) (6.50 g) of the resin solid content concentration of 25% by mass obtained in Synthesis Example 2 and the resin solid content concentration of 25 masses by the synthesis example 7 In a polyamic acid solution (7) (2.80 g) in%, it was stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (2). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<實施例3> <Example 3>

將NEP(17.2g)加入合成例3所得的聚醯亞胺粉末(3)(1.00g)及合成例8所得的聚醯亞胺粉末(8)(1.00g)中,70℃下攪拌24小時使其溶解。將PB(14.1g)加入該溶液中,40℃下攪拌4小時,得液晶配向處理劑(3)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NEP (17.2 g) was added to the polyimide powder (3) (1.00 g) obtained in Synthesis Example 3 and the polyimide powder (8) (1.00 g) obtained in Synthesis Example 8, and stirred at 70 ° C. for 24 hours. Let it dissolve. PB (14.1 g) was added to the solution, and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (3). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<實施例4> <Example 4>

將NEP(19.2g)加入合成例3所得的聚醯亞胺粉末(3)(0.65g)及合成例8所得的聚醯亞胺粉末(8) (0.65g)中,70℃下攪拌24小時使其溶解。將BCS(7.20g)及PB(10.8g)加入該溶液中,40℃下攪拌4小時,得液晶配向處理劑(4)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NEP (19.2 g) was added to the polyimide powder (3) (0.65 g) obtained in Synthesis Example 3 and the polyimide powder (8) obtained in Synthesis Example 8. (0.65 g), the solution was stirred at 70 ° C for 24 hours to be dissolved. BCS (7.20 g) and PB (10.8 g) were added to the solution and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (4). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<實施例5> <Example 5>

將NMP(18.5g)加入合成例4所得的聚醯亞胺粉末(4)(1.65g)及合成例8所得的聚醯亞胺粉末(8)(0.71g)中,70℃下攪拌24小時使其溶解。將BCS(18.5g)及M1(0.12g)加入該溶液中,40℃下攪拌6小時,得液晶配向處理劑(5)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NMP (18.5 g) was added to the polyimide powder (4) (1.65 g) obtained in Synthesis Example 4 and the polyimide powder (8) (0.71 g) obtained in Synthesis Example 8, and stirred at 70 ° C. for 24 hours. Let it dissolve. BCS (18.5 g) and M1 (0.12 g) were added to the solution, and stirred at 40 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (5). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<實施例6> <Example 6>

將NMP(2.96g)及NEP(4.48g)加入合成例5所得的聚醯亞胺粉末(5)(0.95g)中,70℃下攪拌24小時使其溶解。將PB(7.44g)加入該溶液中,40℃下攪拌4小時得溶液。 NMP (2.96 g) and NEP (4.48 g) were added to the polyfluorene imine powder (5) (0.95 g) obtained in Synthesis Example 5, and stirred at 70 ° C for 24 hours to dissolve. PB (7.44 g) was added to the solution, and the solution was stirred at 40 ° C for 4 hours.

又,將NMP(4.44g)及NEP(6.72g)加入合成例9所得的聚醯亞胺粉末(9)(1.43g)中,70℃下攪拌24小時使其溶解。將PB(11.2g)加入該溶液中,40℃下攪拌4小時得溶液。 Further, NMP (4.44 g) and NEP (6.72 g) were added to the polyfluorene imine powder (9) (1.43 g) obtained in Synthesis Example 9, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. PB (11.2 g) was added to the solution, and the solution was stirred at 40 ° C for 4 hours.

混合上述所得的2種溶液,25℃下攪拌4小時,得液晶配向處理劑(6)。該液晶配向處理劑未出現混濁及析 出等異常,確認為均勻溶液。 The two solutions obtained above were mixed and stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (6). The liquid crystal alignment treatment agent did not appear turbid and separated. An abnormality was detected and it was confirmed to be a homogeneous solution.

<實施例7> <Example 7>

將NMP(4.10g)及NEP(20.7g)加入合成例5所得的聚醯亞胺粉末(5)(0.45g)及合成例9所得的聚醯亞胺粉末(9)(1.05g)中,70℃下攪拌24小時使其溶解。將PB(16.5g)加入該溶液中,40℃下攪拌4小時,得液晶配向處理劑(7)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NMP (4.10 g) and NEP (20.7 g) were added to the polyimide powder (5) (0.45 g) obtained in Synthesis Example 5 and the polyimide powder (9) (1.05 g) obtained in Synthesis Example 9, It was stirred at 70 ° C for 24 hours to dissolve it. PB (16.5 g) was added to the solution, and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (7). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<實施例8> <Example 8>

將NMP(21.5g)加入合成例5所得的聚醯亞胺粉末(5)(0.75g)及合成例17所得的聚醯亞胺粉末(17)(1.75g)中,70℃下攪拌24小時使其溶解。將BCS(13.7g)、DME(3.90g)及M1(0.25g)加入該溶液中,40℃下攪拌6小時,得液晶配向處理劑(8)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NMP (21.5 g) was added to the polyimide powder (5) (0.75 g) obtained in Synthesis Example 5 and the polyimide powder (17) (1.75 g) obtained in Synthesis Example 17, and stirred at 70 ° C. for 24 hours. Let it dissolve. BCS (13.7 g), DME (3.90 g), and M1 (0.25 g) were added to the solution, and stirred at 40 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (8). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<實施例9> <Example 9>

將NEP(11.8g)加入合成例6所得的聚醯亞胺粉末(6)(1.25g)中,70℃下攪拌24小時使其溶解。將BCS(1.98g)及PB(5.89g)加入該溶液中,40℃下攪拌4小時得溶液。 NEP (11.8 g) was added to the polyfluorene imine powder (6) (1.25 g) obtained in Synthesis Example 6, and stirred at 70 ° C. for 24 hours to dissolve it. BCS (1.98 g) and PB (5.89 g) were added to the solution, and the solution was stirred at 40 ° C for 4 hours.

又,將NEP(9.60g)加入合成例12所得的聚醯亞胺粉末(12)(1.02g)中,70℃下攪拌24小時使其溶解。將BCS(1.62g)及PB(4.81g)加入該溶液中,40℃下攪拌4小時得溶液。 Further, NEP (9.60 g) was added to the polyfluorene imine powder (12) (1.02 g) obtained in Synthesis Example 12, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (1.62 g) and PB (4.81 g) were added to the solution, and the solution was stirred at 40 ° C for 4 hours to obtain a solution.

混合上述所得的2種溶液後加入M1(0.07g),40℃下攪拌4小時,得液晶配向處理劑(9)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 After mixing the two solutions obtained above, M1 (0.07 g) was added and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (9). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<實施例10> <Example 10>

將NMP(19.0g)及γ-BL(3.80g)加入合成例6所得的聚醯亞胺粉末(6)(0.55g)及合成例12所得的聚醯亞胺粉末(12)(0.83g)中,70℃下攪拌24小時使其溶解。將PB(15.2g)加入該溶液中,40℃下攪拌4小時,得液晶配向處理劑(10)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NMP (19.0 g) and γ-BL (3.80 g) were added to the polyimide powder (6) (0.55 g) obtained in Synthesis Example 6 and the polyimide powder (12) (0.83 g) obtained in Synthesis Example 12. The solution was stirred at 70 ° C for 24 hours to be dissolved. PB (15.2 g) was added to the solution and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (10). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<實施例11> <Example 11>

將NMP(3.40g)及NEP(17.0g)加入合成例10所得的聚醯亞胺粉末(10)(0.65g)及合成例8所得的聚醯亞胺粉末(8)(1.52g)中,70℃下攪拌24小時使其溶解。將BCS(3.40g)及PB(10.2g)加入該溶液中,40℃下攪拌4小時,得液晶配向處理劑(11)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NMP (3.40 g) and NEP (17.0 g) were added to the polyimide powder (10) (0.65 g) obtained in Synthesis Example 10 and the polyimide powder (8) (1.52 g) obtained in Synthesis Example 8, It was stirred at 70 ° C for 24 hours to dissolve it. BCS (3.40 g) and PB (10.2 g) were added to the solution, and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (11). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<實施例12> <Example 12>

將NEP(16.6g)及γ-BL(3.70g)加入合成例11所得的聚醯亞胺粉末(11)(1.65g)及合成例12所得的聚醯亞胺粉末(12)(0.71g)中,70℃下攪拌24小時使其溶解。將PB(16.6g)及M1(0.24g)加入該溶液中,40℃下攪拌6小時,得液晶配向處理劑(12)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NEP (16.6 g) and γ-BL (3.70 g) were added to the polyimide powder (11) (1.65 g) obtained in Synthesis Example 11 and the polyimide powder (12) (0.71 g) obtained in Synthesis Example 12. The solution was stirred at 70 ° C for 24 hours to be dissolved. PB (16.6 g) and M1 (0.24 g) were added to the solution, and stirred at 40 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (12). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<實施例13> <Example 13>

將NMP(3.90g)及NEP(15.6g)加入合成例11所得的聚醯亞胺粉末(11)(0.85g)及合成例12所得的聚醯亞胺粉末(12)(0.57g)中,70℃下攪拌24小時使其溶解。將PB(19.5g)加入該溶液中,40℃下攪拌4小時,得液晶配向處理劑(13)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NMP (3.90 g) and NEP (15.6 g) were added to the polyimide powder (11) (0.85 g) obtained in Synthesis Example 11 and the polyimide powder (12) (0.57 g) obtained in Synthesis Example 12, It was stirred at 70 ° C for 24 hours to dissolve it. PB (19.5 g) was added to the solution, and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (13). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<實施例14> <Example 14>

將NMP(7.50g)及NEP(3.75g)加入合成例13所得的聚醯亞胺粉末(13)(1.20g)中,70℃下攪拌24小時使其溶解。將BCS(3.75g)及DME(3.75g)加入該溶液中,40℃下攪拌4小時得溶液。 NMP (7.50 g) and NEP (3.75 g) were added to the polyfluorene imine powder (13) (1.20 g) obtained in Synthesis Example 13, and stirred at 70 ° C for 24 hours to dissolve. BCS (3.75 g) and DME (3.75 g) were added to the solution, and the solution was stirred at 40 ° C for 4 hours.

又,將NMP(7.50g)及NEP(3.75g)加入合成例9所得的聚醯亞胺粉末(9)(1.20g)中,70℃下攪拌24小時使其溶解。將BCS(3.75g)及DME(3.75g)加入該 溶液中,40℃下攪拌4小時得溶液。 Further, NMP (7.50 g) and NEP (3.75 g) were added to the polyfluorene imine powder (9) (1.20 g) obtained in Synthesis Example 9, and stirred at 70 ° C for 24 hours to dissolve. Add BCS (3.75g) and DME (3.75g) to the The solution was stirred at 40 ° C for 4 hours to obtain a solution.

混合上述所得的2種溶液,25℃下攪拌4小時,得液晶配向處理劑(14)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 The two solutions obtained above were mixed and stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (14). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<實施例15> <Example 15>

將NMP(5.70g)及NEP(15.1g)加入合成例14所得的聚醯亞胺粉末(14)(1.45g)及合成例8所得的聚醯亞胺粉末(8)(0.97g)中,70℃下攪拌24小時使其溶解。將PB(17.0g)及M1(0.07g)加入該溶液中,40℃下攪拌6小時,得液晶配向處理劑(15)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NMP (5.70 g) and NEP (15.1 g) were added to the polyimide powder (14) (1.45 g) obtained in Synthesis Example 14 and the polyimide powder (8) (0.97 g) obtained in Synthesis Example 8, It was stirred at 70 ° C for 24 hours to dissolve it. PB (17.0 g) and M1 (0.07 g) were added to the solution and stirred at 40 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (15). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<實施例16> <Example 16>

將NMP(6.90g)及NEP(13.7g)加入合成例15所得的聚醯亞胺粉末(15)(1.75g)及合成例9所得的聚醯亞胺粉末(9)(0.44g)中,70℃下攪拌24小時使其溶解。將PB(13.7g)加入該溶液中,40℃下攪拌4小時,得液晶配向處理劑(16)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NMP (6.90g) and NEP (13.7g) were added to the polyfluorene imine powder (15) (1.75g) obtained in Synthesis Example 15 and the polyfluorene imine powder (9) (0.44g) obtained in Synthesis Example 9, It was stirred at 70 ° C for 24 hours to dissolve it. PB (13.7 g) was added to the solution and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (16). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<實施例17> <Example 17>

將NMP(11.9g)及NEP(6.80g)加入合成例16所得的聚醯亞胺粉末(16)(0.65g)及合成例17所得的聚 醯亞胺粉末(17)(1.52g)中,70℃下攪拌24小時使其溶解。將BCS(15.3g)加入該溶液中,40℃下攪拌4小時,得液晶配向處理劑(17)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NMP (11.9 g) and NEP (6.80 g) were added to the polyimide powder (16) (0.65 g) obtained in Synthesis Example 16 and the polymer obtained in Synthesis Example 17 The amidine imine powder (17) (1.52 g) was dissolved by stirring at 70 ° C for 24 hours. BCS (15.3 g) was added to the solution and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (17). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<實施例18> <Example 18>

將NEP(11.6g)及γ-BL(5.80g)加入合成例16所得的聚醯亞胺粉末(16)(0.35g)及合成例17所得的聚醯亞胺粉末(17)(1.05g)中,70℃下攪拌24小時使其溶解。將PB(21.2g)加入該溶液中,40℃下攪拌4小時,得液晶配向處理劑(18)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NEP (11.6 g) and γ-BL (5.80 g) were added to the polyimide powder (16) (0.35 g) obtained in Synthesis Example 16 and the polyimide powder (17) (1.05 g) obtained in Synthesis Example 17. The solution was stirred at 70 ° C for 24 hours to be dissolved. PB (21.2 g) was added to the solution, and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (18). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<實施例19> <Example 19>

將NMP(7.80g)及NEP(13.7g)加入合成例16所得的聚醯亞胺粉末(16)(0.75g)及合成例8所得的聚醯亞胺粉末(8)(1.75g)中,70℃下攪拌24小時使其溶解。將PB(13.7g)、EC(3.90g)及M1(0.13g)加入該溶液中,40℃下攪拌6小時,得液晶配向處理劑(19)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NMP (7.80 g) and NEP (13.7 g) were added to the polyimide powder (16) (0.75 g) obtained in Synthesis Example 16 and the polyimide powder (8) (1.75 g) obtained in Synthesis Example 8, It was stirred at 70 ° C for 24 hours to dissolve it. PB (13.7g), EC (3.90g) and M1 (0.13g) were added to the solution, and stirred at 40 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (19). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<實施例20> <Example 20>

將NEP(15.7g)加入合成例2所得的樹脂固體成分 濃度25質量%之聚醯胺酸溶液(2)(1.88g)及合成例17所得的聚醯亞胺粉末(17)(0.50g)中,70℃下攪拌24小時使其溶解。將BCS(7.40g)及PB(7.40g)加入該溶液中,40℃下攪拌4小時,得液晶配向處理劑(20)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NEP (15.7 g) was added to the resin solid content obtained in Synthesis Example 2 The 25% by mass polyamine solution (2) (1.88 g) and the polyimide powder (17) (0.50 g) obtained in Synthesis Example 17 were stirred at 70 ° C for 24 hours to be dissolved. BCS (7.40 g) and PB (7.40 g) were added to the solution, and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (20). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<比較例1> <Comparative example 1>

將NEP(15.2g)及BCS(14.9g)加入合成例2所得的樹脂固體成分濃度25質量%之聚醯胺酸溶液(2)(9.50g)中,25℃下攪拌4小時,得液晶配向處理劑(21)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NEP (15.2g) and BCS (14.9g) were added to the 25% by mass polyamic acid solution (2) (9.50g) of the resin solid content concentration obtained in Synthesis Example 2, and stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment. Treatment agent (21). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<比較例2> <Comparative example 2>

將NEP(14.4g)及BCS(14.1g)加入合成例7所得的樹脂固體成分濃度25質量%之聚醯胺酸溶液(7)(9.00g)中,25℃下攪拌4小時,得液晶配向處理劑(22)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NEP (14.4 g) and BCS (14.1 g) were added to a polyamic acid solution (7) (9.00 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 7, and stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment. Treatment agent (22). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<比較例3> <Comparative example 3>

將NEP(19.4g)加入合成例3所得的聚醯亞胺粉末(3)(2.25g)中,70℃下攪拌24小時使其溶解。將PB (15.9g)加入該溶液中,40℃下攪拌4小時,得液晶配向處理劑(23)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NEP (19.4 g) was added to the polyfluorene imine powder (3) (2.25 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Will PB (15.9 g) was added to the solution, and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (23). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<比較例4> <Comparative Example 4>

將NEP(19.0g)加入合成例8所得的聚醯亞胺粉末(8)(2.20g)中,70℃下攪拌24小時使其溶解。將PB(15.5g)加入該溶液中,40℃下攪拌4小時,得液晶配向處理劑(24)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NEP (19.0 g) was added to the polyfluorene imine powder (8) (2.20 g) obtained in Synthesis Example 8, and stirred at 70 ° C for 24 hours to dissolve. PB (15.5 g) was added to the solution and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (24). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<比較例5> <Comparative example 5>

將NEP(16.0g)及BCS(15.7g)加入合成例2所得的樹脂固體成分濃度25質量%之聚醯胺酸溶液(2)(7.00g)及合成例18所得的樹脂固體成分濃度25質量%之聚醯胺酸溶液(18)(3.00g)中,25℃下攪拌4小時,得液晶配向處理劑(25)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NEP (16.0 g) and BCS (15.7 g) were added to a polyamic acid solution (2) (7.00 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 2 and a resin solid content concentration of 25 masses obtained in Synthesis Example 18. The polyamic acid solution (18) (3.00 g) was stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (25). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<比較例6> <Comparative Example 6>

將NEP(18.1g)加入合成例3所得的聚醯亞胺粉末(3)(1.05g)及合成例19所得的聚醯亞胺粉末(19)(1.05g)中,70℃下攪拌24小時使其溶解。將PB(14.8g)加入該溶液中,40℃下攪拌4小時,得液晶配 向處理劑(26)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NEP (18.1 g) was added to the polyimide powder (3) (1.05 g) obtained in Synthesis Example 3 and the polyimide powder (19) (1.05 g) obtained in Synthesis Example 19, and stirred at 70 ° C for 24 hours. Let it dissolve. PB (14.8g) was added to the solution, and stirred at 40 ° C for 4 hours to obtain a liquid crystal compound. 向 处理 剂 (26). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<比較例7> <Comparative Example 7>

將NEP(17.2g)加入合成例20所得的聚醯亞胺粉末(20)(1.00g)及合成例8所得的聚醯亞胺粉末(8)(1.00g)中,70℃下攪拌24小時使其溶解。將PB(14.1g)加入該溶液中,40℃下攪拌4小時,得液晶配向處理劑(27)。該液晶配向處理劑未出現混濁及析出等異常,確認為均勻溶液。 NEP (17.2 g) was added to the polyimide powder (20) (1.00 g) obtained in Synthesis Example 20 and the polyimide powder (8) (1.00 g) obtained in Synthesis Example 8, and stirred at 70 ° C. for 24 hours. Let it dissolve. PB (14.1 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (27). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<評估液晶配向處理劑> <Evaluation of liquid crystal alignment treatment agent>

使用上述實施例1~20及比較例1~7各自所得的液晶配向處理劑,進行「製作液晶單元及評估預傾角(一般單元)」、「評估電壓保持率(一般單元)」及「評估殘留電荷之緩和(一般單元)」。又,針對實施例4、7、10、13、18各自所得的液晶配向處理劑,評估其噴墨印刷塗佈性。 Using the liquid crystal alignment treatment agents obtained in the above Examples 1 to 20 and Comparative Examples 1 to 7, respectively, "producing a liquid crystal cell and evaluating a pretilt angle (general cell)", "evaluating a voltage holding ratio (general cell)", and "evaluating residual Ease of Charge (General Unit) ". The liquid crystal alignment treatment agents obtained in Examples 4, 7, 10, 13, and 18 were evaluated for inkjet printing coatability.

該等評估結果合示於下述表39~表43。 The evaluation results are shown in Table 39 to Table 43 below.

由上述結果得知,實施例之液晶配向處理劑比較比較例時,液晶單元既使進行高溫處理及照射紫外 線,也可得安定的預傾角。又,既使照射紫外線,仍可抑制電壓保持率降低,且加速緩和因直流電壓所蓄積的殘留電荷。即,本發明的液晶配向處理劑既使曝露於長時間高溫及光照射後,仍可形成發現安定預傾角的液晶配向膜,又可形成,既使曝露於長時間光照射後,仍能抑制電壓保持率降低,且加速緩和因直流電壓所蓄積的殘留電荷之液晶配向膜。 From the above results, it is known that in the comparative example of the liquid crystal alignment treatment agent of the example, the liquid crystal cell is subjected to high-temperature treatment and ultraviolet irradiation. Line, you can also get a stable pre-tilt angle. In addition, even when the ultraviolet rays are irradiated, the decrease in the voltage holding ratio can be suppressed, and the residual charge accumulated by the DC voltage can be accelerated and relaxed. That is, the liquid crystal alignment treatment agent of the present invention can form a liquid crystal alignment film in which a stable pretilt angle is found even after being exposed to long-term high temperature and light irradiation, and can be formed even after being exposed to long-term light irradiation. The liquid crystal alignment film having a reduced voltage holding ratio and accelerating and alleviating the residual charge accumulated by the DC voltage.

具體為,比較使用特定聚合物(A)及特定聚合物(B)之液晶配向處理劑的實施例,與未使用該等中任一方之液晶配向處理劑的實施例,即,比較實施例2與比較例1或比較例2,比較實施例3與比較例3或比較例4。該等僅使用特定聚合物(A)的比較例1及比較例3,比較對應之實施例時,進行高溫處理及照射紫外線後會大幅改變預傾角,且相對於該等處理會大幅降低電壓保持率,及增加殘留電荷之值。其中特別是大幅降低電壓保持率。又,比較例2及比較例4中,液晶未垂直配向。 Specifically, the embodiment using the liquid crystal alignment treatment agent of the specific polymer (A) and the specific polymer (B) is compared with the embodiment where the liquid crystal alignment treatment agent of any of these is not used, that is, Comparative Example 2 Compared with Comparative Example 1 or Comparative Example 2, Example 3 and Comparative Example 3 or Comparative Example 4 were compared. These comparative examples 1 and 3 using only the specific polymer (A), when comparing the corresponding examples, the pretilt angle is greatly changed after high temperature treatment and ultraviolet irradiation, and the voltage retention is greatly reduced compared to these treatments. Rate, and increase the value of residual charge. Among them, the voltage holding ratio is significantly reduced. In Comparative Examples 2 and 4, the liquid crystals were not vertically aligned.

又,比較使用實施例特定聚合物(A)及特定聚合物(B)之液晶配向處理劑的實施例,與使用特定聚合物(A)及使用具有前述式[1]所表示的特定支鏈結構之特定支鏈型二胺化合物的聚合物之液晶配向處理劑的比較例,即,比較實施例2與比較例5,比較實施例3與比較例6。該等比較例比較對應的實施例時,進行高溫處理及照射紫外線後會大幅改變預傾角,且相對於該等處理會大幅降低電壓保持率,及增加殘留電荷之值。特別是會降低 電壓保持率及增加殘留電荷之值。 In addition, an example using the liquid crystal alignment treatment agent of the specific polymer (A) and the specific polymer (B) of the example is compared with the use of the specific polymer (A) and the specific branched chain having the formula [1]. A comparative example of a liquid crystal alignment treatment agent for a polymer of a specific branched-chain diamine compound having a structure, that is, Comparative Example 2 and Comparative Example 5, and Comparative Example 3 and Comparative Example 6. When these comparative examples are compared with the corresponding examples, the pretilt angle is greatly changed after high-temperature treatment and ultraviolet irradiation, and the voltage retention rate is greatly reduced and the value of the residual charge is increased relative to these treatments. Especially lower The voltage holding rate and the value of increasing the residual charge.

又,比較使用特定聚合物(A)與特定聚合物(B)之液晶配向處理劑的實施例,與使用具有先前型支鏈結構之聚合物與特定聚合物(B)之液晶配向處理劑的比較例,即,比較實施例3與比較例7。該比較例7比較實施例3時,進行高溫處理及照射紫外線後會大幅改變預傾角,且相對於該等處理會降低電壓保持率,及增加殘留電荷之值。特別是會大幅降低照射紫外線後之預傾角。 In addition, an example in which the liquid crystal alignment treatment agent using the specific polymer (A) and the specific polymer (B) was compared with the liquid crystal alignment treatment agent using the polymer having the conventional branched structure and the specific polymer (B) was compared. Comparative example, that is, Example 3 and Comparative Example 7 are compared. When Comparative Example 7 is compared with Example 3, the pretilt angle is significantly changed after high-temperature treatment and ultraviolet irradiation, and the voltage retention ratio is reduced and the value of the residual charge is increased relative to these treatments. In particular, the pretilt angle after UV irradiation is greatly reduced.

產業上利用可能性 Industrial use possibility

本發明的液晶配向處理劑可提供,既使曝露於長時間高溫及光照射後,仍可發現安定預傾角之液晶配向膜。又可提供,既使曝露於長時間光照射後,仍能抑制電壓保持率降低,且加速緩和因直流電壓所蓄積的殘留電荷之液晶配向膜。另外可提供,可提供具有上述液晶配向膜之液晶顯示元件,上述液晶配向膜的液晶配向處理劑。 The liquid crystal alignment treatment agent of the present invention can provide a liquid crystal alignment film with a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. Furthermore, it is possible to provide a liquid crystal alignment film capable of suppressing a decrease in the voltage holding rate even after being exposed to long-term light irradiation, and accelerating and alleviating the residual charge accumulated by the DC voltage. In addition, a liquid crystal display device having the liquid crystal alignment film, and a liquid crystal alignment treatment agent for the liquid crystal alignment film can be provided.

因此具有由本發明的液晶配向處理劑所得的液晶配向膜之液晶顯示元件為,具有優良信賴性之物,適用於大畫面且高精細之液晶電視等,適用為TN元件、STN元件、TFT液晶元件,特別是垂直配向型之液晶顯示元件。 Therefore, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is a substance having excellent reliability, and is suitable for large-screen and high-definition liquid crystal televisions. It is suitable for TN elements, STN elements, and TFT liquid crystal elements. , Especially vertical alignment type liquid crystal display elements.

又,由本發明的液晶配向處理劑所得的液晶配向膜相對於製作液晶顯示元件時,需照射紫外線的液晶顯示元件也具有適用性。即,相對於一對備有電極之基板 間具有液晶層所構成,經由將含有藉由活性能量線及熱中至少一方而聚合之聚合性化合物的液晶組成物配置於前述一對基板之間,將電壓施加於前述電極的同時聚合前述聚合性化合物之步驟所製造的液晶顯示元件,及一對備有電極之基板間具有液晶層所構成,經由將含有藉由活性能量線及熱中至少一方而聚合之聚合性基的液晶配向膜配置於前述一對基板之間,將電壓施加於前述電極間的同時聚合前述聚合性基之步驟所製造的液晶顯示元件也具有適用性。 The liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is also applicable to a liquid crystal display element that needs to be irradiated with ultraviolet rays when a liquid crystal display element is produced. That is, for a pair of substrates with electrodes It has a liquid crystal layer in between, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and the polymerizability is polymerized while a voltage is applied to the electrodes. The liquid crystal display element produced by the compound step and a pair of electrodes provided with a liquid crystal layer between the substrates are arranged through a liquid crystal alignment film containing a polymerizable group polymerized by at least one of active energy rays and heat. The liquid crystal display element manufactured by the step of polymerizing the polymerizable group while applying a voltage between the electrodes between a pair of substrates is also applicable.

又,引用2013年9月3日所申請的日本專利申請2013-182352號之說明書、專利申請範圍及摘要的全部內容,且納入於本發明之說明內容。 The entire contents of the specification, patent application scope, and abstract of Japanese Patent Application No. 2013-182352, filed on September 3, 2013, are incorporated in the description of the present invention.

Claims (22)

一種液晶配向處理劑,其特徵為含有下述成分(A)及成分(B),(A)成分:由含有具有下述式[1]所表示的結構之二胺的二胺成分,與四羧酸成分反應所得的聚醯亞胺先驅物及聚醯亞胺所成群中所選出的至少一種之聚合物,(B)成分:由未含有具有下述式[1]所表示的結構之二胺的二胺成分,與四羧酸成分反應所得的聚醯亞胺先驅物及聚醯亞胺所成群中所選出的至少一種之聚合物,但,(A)成分及(B)成分皆不具有,包含選自甲基丙烯醯基、丙烯醯基、乙烯基、烯丙基、香豆素基、苯乙烯基及桂皮醯基之至少一種之光反應性側鏈;Y1表示單鍵結、-(CH2)a-(a為1~15之整數)、-O-、-CH2O-、-COO-或OCO-;Y2表示單鍵結或(CH2)b-(b為1~15之整數);Y3表示單鍵結、-(CH2)c-(c為1~15之整數)、-O-、-CH2O-、-COO-或OCO-;Y4表示由苯環、環己烷環及雜環中所選出的二價之環狀基,或具有類固醇骨架的碳數17~51之二價的有機基,前述環狀基上之任意的氫原子可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟的烷基、碳數1~3之含氟的烷氧基或氟原子取代;Y5表示由苯環、環己烷環及雜環中所選出的二價之環狀基,該等環狀基上之任意的氫原子可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟的烷基、碳數1~3之含氟的烷氧基或氟原子取代;n表示0~4之整數;Y6表示碳數1~18之烷基、碳數1~18之含氟的烷基、碳數1~18之烷氧基或碳數1~18之含氟的烷氧基。A liquid crystal alignment treatment agent, which is characterized by containing the following component (A) and component (B), (A) component: a diamine component containing a diamine having a structure represented by the following formula [1], and Polyimide precursors obtained by the reaction of carboxylic acid components and at least one polymer selected from the group consisting of polyimide, component (B): a component that does not contain a structure represented by the following formula [1] A diamine component of a diamine, a polyimide precursor obtained by reacting with a tetracarboxylic acid component, and at least one polymer selected from the group consisting of polyimide, but (A) component and (B) component None of which has a photoreactive side chain including at least one selected from the group consisting of methacrylfluorenyl, acrylfluorenyl, vinyl, allyl, coumarin, styryl, and cinnamyl; Y 1 represents a single bond,-(CH 2 ) a- (a is an integer from 1 to 15), -O-, -CH 2 O-, -COO- or OCO-; Y 2 represents a single bond or (CH 2 ) b- (b is an integer from 1 to 15); Y 3 represents a single bond,-(CH 2 ) c- (c is an integer from 1 to 15), -O-, -CH 2 O-, -COO -Or OCO-; Y 4 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton, and the aforementioned ring Any hydrogen atom on the base can be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkyl group having 1 to 3 carbon atoms. Oxygen or fluorine atom substitution; Y 5 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups may be 1 to 3 carbon atoms Substituted by alkyl group, alkoxy group having 1 to 3 carbon atoms, fluorine-containing alkyl group having 1 to 3 carbon atoms, fluorine-containing alkoxy group having 1 to 3 carbon atoms or fluorine atom substitution; n represents an integer of 0 to 4 ; Y 6 represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. 如請求項1之液晶配向處理劑,其中具有前述式[1]所表示的結構之二胺為,下述式[1a]所表示,Y1、Y2、Y3、Y4、Y5、n、Y6及m表示與前述相同之定義。The liquid crystal alignment treatment agent according to claim 1, wherein the diamine having the structure represented by the aforementioned formula [1] is represented by the following formula [1a], Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , n, Y 6 and m represent the same definitions as described above. 如請求項1之液晶配向處理劑,其中前述(B)成分為,由含有具有由羧基(COOH基)及羥基(OH基)中所選出的至少一種之取代基的二胺之二胺成分,與四羧酸成分反應所得的聚醯亞胺先驅物及聚醯亞胺所成群中所選出的至少一種之聚合物。The liquid crystal alignment treatment agent according to claim 1, wherein the component (B) is a diamine component composed of a diamine having at least one selected from a carboxyl group (COOH group) and a hydroxyl group (OH group), A polyimide precursor obtained by reacting with a tetracarboxylic acid component and a polymer of at least one selected from the group consisting of polyimide. 如請求項1之液晶配向處理劑,其中前述(A)成分為,二胺成分另使用含有具有由羧基(COOH基)及羥基(OH基)中所選出的至少一種之取代基的二胺的聚合物。In the liquid crystal alignment treatment agent according to claim 1, wherein the component (A) is a diamine component, a diamine containing a diamine having at least one selected from a carboxyl group (COOH group) and a hydroxyl group (OH group) is used. polymer. 如請求項3或4之液晶配向處理劑,其中具有由前述羧基及羥基中所選出的至少一種之取代基的二胺為,下述式[2a]所表示,A1表示由下述式[2a-1]及式[2a-2]中所選出的至少1個取代基;m1表示1~4之整數,[化4]-(CH2)d-COOH [2a-1] -(CH2)e-OH [2a-2]d表示0~4之整數;e表示0~4之整數。In the liquid crystal alignment treatment agent according to claim 3 or 4, wherein the diamine having a substituent selected from at least one of the carboxyl group and the hydroxyl group is represented by the following formula [2a], A 1 represents at least one substituent selected from the following formulas [2a-1] and [2a-2]; m1 represents an integer of 1 to 4, and [Chem 4]-(CH 2 ) d -COOH [ 2a-1]-(CH 2 ) e -OH [2a-2] d represents an integer from 0 to 4; e represents an integer from 0 to 4. 如請求項1之液晶配向處理劑,其中前述(A)成分及(B)成分之聚合物為,二胺成分使用下述式[3a]所表示的二胺的聚合物,B1表示-O-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-CH2O-、-OCO-、-CON(CH3)-或N(CH3)CO-;B2表示單鍵結、碳數1~20之伸烷基、非芳香族環或芳香族環;B3表示單鍵結、-O-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-COO-、-OCO-、-CON(CH3)-、N(CH3)CO-、或-O(CH2)m2-(m2為1~5之整數);B4表示含氮的雜環;n1表示1~4之整數,n1為2以上時,-B1-B2-B3-B4可相同或相異。The liquid crystal alignment treatment agent according to claim 1, wherein the polymer of the components (A) and (B) is a polymer of a diamine component using a diamine represented by the following formula [3a], B 1 represents -O-, -NH-, -N (CH 3 )-, -CONH-, -NHCO-, -CH 2 O-, -OCO-, -CON (CH 3 )-, or N (CH 3 ) CO-; B 2 represents a single bond, an alkylene group having 1 to 20 carbon atoms, a non-aromatic ring or an aromatic ring; B 3 represents a single bond, -O-, -NH-, -N (CH 3 ) -, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH 3 )-, N (CH 3 ) CO-, or -O (CH 2 ) m2- (m2 is 1 to 5 (Integer); B 4 represents a nitrogen-containing heterocyclic ring; n1 represents an integer of 1 to 4; when n1 is 2 or more, -B 1 -B 2 -B 3 -B 4 may be the same or different. 如請求項6之液晶配向處理劑,其中前述式[3a]中之B1為,-O-、-NH-、-CONH-、-NHCO-、-CH2O-、-OCO-或CON(CH3)-。The liquid crystal alignment treatment agent according to claim 6, wherein B 1 in the foregoing formula [3a] is -O-, -NH-, -CONH-, -NHCO-, -CH 2 O-, -OCO-, or CON ( CH 3 )-. 如請求項6之液晶配向處理劑,其中前述式[3a]中之B2為,單鍵結、碳數1~5之伸烷基、環己烷環或苯環。The liquid crystal alignment treatment agent according to claim 6, wherein B 2 in the foregoing formula [3a] is a single bond, an alkylene group having 1 to 5 carbon atoms, a cyclohexane ring, or a benzene ring. 如請求項6之液晶配向處理劑,其中前述式[3a]中之B3為,單鍵結、-O-、-OCO-或O(CH2)m2-(m2為1~5之整數)。For example, the liquid crystal alignment treatment agent of claim 6, wherein B 3 in the foregoing formula [3a] is a single bond, -O-, -OCO-, or O (CH 2 ) m2- (m2 is an integer from 1 to 5) . 如請求項6之液晶配向處理劑,其中前述式[3a]中之B4為,吡咯環、咪唑環、吡唑環、吡啶環或嘧啶環。The liquid crystal alignment treatment agent according to claim 6, wherein B 4 in the foregoing formula [3a] is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring. 如請求項6之液晶配向處理劑,其中前述式[3a]中之B1表示-CONH-、B2表示碳數1~5之伸烷基,B3表示單鍵結,B4表示咪唑環或吡啶環,n1為1。For example, the liquid crystal alignment treatment agent of claim 6, wherein B 1 in the foregoing formula [3a] represents -CONH-, B 2 represents an alkylene group having 1 to 5 carbon atoms, B 3 represents a single bond, and B 4 represents an imidazole ring Or pyridine ring, n1 is 1. 如請求項1之液晶配向處理劑,其中前述(A)成分及(B)成分中至少一方之四羧酸成分為,含有下述式[4]所表示的四羧酸二酐,Z1為由下述式[4a]~式[4k]中所選出之基,Z2~Z5表示各自獨立的氫原子、甲基、氯原子或苯環;Z6、Z7表示各自獨立的氫原子或甲基。The liquid crystal alignment treatment agent according to claim 1, wherein the tetracarboxylic acid component of at least one of the components (A) and (B) is a tetracarboxylic dianhydride represented by the following formula [4], Z 1 is a base selected from the following formulas [4a] to [4k], Z 2 to Z 5 each independently represent a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring; Z 6 and Z 7 each independently represent a hydrogen atom or a methyl group. 如請求項1之液晶配向處理劑,其中含有N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮及γ-丁內酯中至少一種之溶劑。The liquid crystal alignment treatment agent according to claim 1, which contains a solvent of at least one of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone. 如請求項1之液晶配向處理劑,其中含有由下述式[D-1]~式[D-3]中所選出的至少一種之溶劑,D1表示碳數1~3之烷基,D2表示碳數1~3之烷基,D3表示碳數1~4之烷基。For example, the liquid crystal alignment treatment agent of claim 1, which contains at least one solvent selected from the following formulas [D-1] to [D-3], D 1 represents an alkyl group having 1 to 3 carbon atoms, D 2 represents an alkyl group having 1 to 3 carbon atoms, and D 3 represents an alkyl group having 1 to 4 carbon atoms. 如請求項1之液晶配向處理劑,其中含有由1-己醇、環己醇、1,2-乙二醇、1,2-丙二醇、丙二醇單丁基醚、乙二醇單丁基醚及二丙二醇二甲基醚中所選出的至少一種之溶劑。For example, the liquid crystal alignment treatment agent of claim 1, which contains 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, and A solvent of at least one selected from 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,由具有環氧基、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、羥基烷基及低級烷氧基烷基所成群中所選出的至少一種之取代基的交聯性化合物,及具有聚合性不飽和鍵結的交聯性化合物中所選出的至少一種之交聯性化合物。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, A crosslinkable compound of at least one selected from the group consisting of lower alkoxyalkyl groups, and a crosslinkable compound of at least one selected from the crosslinkable compounds having a polymerizable unsaturated bond. 一種液晶配向膜,其為由如請求項1~16中任一項之液晶配向處理劑所得。A liquid crystal alignment film is obtained from the liquid crystal alignment treatment agent according to any one of claims 1 to 16. 一種液晶配向膜,其為藉由噴墨印刷法印刷如請求項1~16中任一項之液晶配向處理劑所得。A liquid crystal alignment film is obtained by printing the liquid crystal alignment treatment agent according to any one of claims 1 to 16 by an inkjet printing method. 一種液晶顯示元件,其為具有如請求項17或18之液晶配向膜。A liquid crystal display element having a liquid crystal alignment film as claimed in claim 17 or 18. 如請求項17或18之液晶配向膜,其係使用於經由一對備有電極之基板間具有液晶層,將含有藉由活性能量線及熱中至少一方而聚合之聚合性化合物的液晶組成物配置於前述一對基板之間,將電壓施加於前述電極間的同時聚合前述聚合性化合物之步驟所製造的液晶顯示元件。For example, the liquid crystal alignment film of claim 17 or 18 is used for disposing a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat through a liquid crystal layer between a pair of substrates provided with electrodes. A liquid crystal display device produced by the step of polymerizing the polymerizable compound while applying a voltage between the pair of substrates between the electrodes. 如請求項17或18之液晶配向膜,其係使用於一對備有電極之基板間具有液晶層所構成,經由將含有藉由活性能量線及熱中至少一方而聚合之聚合性基的液晶配向膜配置於前述一對基板之間,將電壓施加於前述電極間的同時聚合前述聚合性基之步驟所製造的液晶顯示元件。For example, the liquid crystal alignment film of claim 17 or 18 is composed of a liquid crystal layer having a liquid crystal layer between a pair of substrates provided with electrodes. The liquid crystal alignment film contains a polymerizable group polymerized by at least one of active energy rays and heat. A film is disposed between the pair of substrates, and a liquid crystal display device manufactured by the step of polymerizing the polymerizable group while applying a voltage between the electrodes. 一種液晶顯示元件,其中具有如請求項20或21之液晶配向膜。A liquid crystal display element having a liquid crystal alignment film as claimed in claim 20 or 21.
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