TWI791614B - Diamine, polymer, liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Diamine, polymer, liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element Download PDF

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TWI791614B
TWI791614B TW107132267A TW107132267A TWI791614B TW I791614 B TWI791614 B TW I791614B TW 107132267 A TW107132267 A TW 107132267A TW 107132267 A TW107132267 A TW 107132267A TW I791614 B TWI791614 B TW I791614B
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藤枝司
杉山暁子
結城達也
豊田美希
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日商日產化學股份有限公司
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    • C07D263/10Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
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Abstract

本發明提供一種於摩擦(rubbing)時不易產生膜之剝離或傷痕,且電壓保持率高,高溫高濕條件下之抗老化性良好,並且與密封劑之密著性優異之液晶配向膜、可取得該液晶配向膜之液晶配向劑、可取得該液晶配向劑之聚合物、成為該聚合物之原料之新穎二胺化合物。 The present invention provides a liquid crystal alignment film that is less prone to film peeling or scratches during rubbing, has a high voltage retention rate, has good aging resistance under high temperature and high humidity conditions, and has excellent adhesion to a sealant. The liquid crystal alignment agent for obtaining the liquid crystal alignment film, the polymer from which the liquid crystal alignment agent can be obtained, and the novel diamine compound used as a raw material for the polymer.

其特徵為液晶配向劑含有具有式(1)所示之噁唑啉骨架之聚合物。 It is characterized in that the liquid crystal alignment agent contains a polymer having an oxazoline skeleton represented by formula (1).

Figure 107132267-A0305-02-0001-1
Figure 107132267-A0305-02-0001-1

(R1表示氫或一價有機基,*表示與其他基之鍵結部位。) (R 1 represents hydrogen or a monovalent organic group, and * represents a bonding site with other groups.)

Description

二胺、聚合物、液晶配向劑、液晶配向膜及液晶顯示元件 Diamine, polymer, liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element

本發明係關於液晶配向劑、由該液晶配向劑而得知液晶配向膜、及具有該液晶配向膜之液晶顯示元件,以及適用於該等之新穎二胺及聚合物。 The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film obtained from the liquid crystal alignment agent, a liquid crystal display element with the liquid crystal alignment film, and novel diamines and polymers suitable for them.

液晶顯示元件係廣泛使用於個人電腦、行動電話、智慧型電話、電視等。近年來在車輛上搭載之汽車導航或計量器、設置於屋外之產業機器或計測機器之顯示部位等,在高溫‧高濕下使用液晶顯示元件之機會也逐漸變多。 Liquid crystal display devices are widely used in personal computers, mobile phones, smart phones, televisions, etc. In recent years, there are more and more opportunities to use liquid crystal display elements in high temperature and high humidity conditions such as car navigation or gauges mounted on vehicles, industrial equipment installed outdoors, or display parts of measuring equipment.

此種液晶顯示元件一般係具備挾持在元件基板與濾色器基板之間之液晶層、對液晶層施加電場之畫素電極及共通電極、控制液晶層之液晶分子配向性之液晶配向膜、切換供給至畫素電極之電信號之薄膜電晶體(TFT)等。 This type of liquid crystal display element generally has a liquid crystal layer sandwiched between the element substrate and the color filter substrate, pixel electrodes and common electrodes that apply an electric field to the liquid crystal layer, a liquid crystal alignment film that controls the alignment of liquid crystal molecules in the liquid crystal layer, and switching Thin film transistor (TFT) etc. for electrical signals supplied to pixel electrodes.

液晶顯示元件中,以畫素電極及共通電極挾持液晶層而成者係作用當作液晶單元。液晶單元在其之電壓保持率(VHR:Voltage Holding Ratio)為低時,變得即使施加電壓仍難以對液晶分子施加充分電壓。因此,由於高 溫‧高濕下之使用或長期使用等,電壓保持率若降低時,顯示對比降低,或顯示產生閃爍(flicker)等,而顯示變得不易觀看。 In the liquid crystal display element, the pixel electrode and the common electrode sandwich the liquid crystal layer and act as a liquid crystal unit. When the voltage holding ratio (VHR: Voltage Holding Ratio) of the liquid crystal cell is low, it becomes difficult to apply a sufficient voltage to the liquid crystal molecules even if a voltage is applied. Therefore, due to the high If the voltage retention rate is lowered under high temperature and high humidity or long-term use, the display contrast will decrease, or the display will flicker, etc., making the display difficult to see.

尤其,在電視或車上顯示器中,該等液晶顯示元件為了取得高亮度,而使用發熱量大之背光,又,車載用途上使用之例如汽車導航系統或計量器面板會有在長時間高溫環境下使用或放置之情況。在此種過苛條件下,預傾角在經過徐徐變化之情況,會有引起變得無法取得初期之顯示特性,顯示上產生不均等之問題。並且,在驅動液晶之際之電壓保持特性或電荷蓄積特性也受到液晶配向膜之影響,在電壓保持率為低時,會產生顯示畫面之對比降低,在對直流電壓之電荷蓄積為大時,顯示畫面會產生稱為烙印之現象。 In particular, in TVs or car displays, these liquid crystal display elements use backlights that generate a lot of heat in order to achieve high brightness. Also, car navigation systems or meter panels used in car applications may be exposed to high temperatures for a long time. The following conditions of use or storage. Under such harsh conditions, the gradual change of the pretilt angle may cause the problem that the initial display characteristics cannot be obtained, resulting in unevenness in the display. In addition, the voltage retention characteristics and charge accumulation characteristics when driving liquid crystals are also affected by the liquid crystal alignment film. When the voltage retention rate is low, the contrast of the display screen will be reduced. When the charge accumulation for DC voltage is large, A phenomenon called burn-in occurs on the display screen.

此種液晶顯示元件之驅動方式之一如有使對於基板呈垂直配向之液晶分子藉由電場而應答之方式(亦稱為垂直配向(VA)方式)。垂直配向方式之液晶顯示元件係已知有預先在液晶組成物中添加光聚合性化合物且使用聚醯亞胺系等之垂直配向膜,藉由對液晶單元施加電壓並同時照射紫外線,而加快液晶應答速度之技術(聚合物穩定配向,PSA(Polymer Sustained Alignment)方式元件,例如,參照如專利文獻1及非專利文獻1)。 One of the driving methods of such a liquid crystal display element is a method in which liquid crystal molecules that are vertically aligned with respect to the substrate respond to an electric field (also called a vertical alignment (VA) method). The liquid crystal display element of the vertical alignment method is known to add a photopolymerizable compound to the liquid crystal composition in advance and use a vertical alignment film such as a polyimide system to accelerate the liquid crystal by applying a voltage to the liquid crystal cell and irradiating ultraviolet rays at the same time. Response speed technology (polymer stabilized alignment, PSA (Polymer Sustained Alignment) type device, for example, refer to Patent Document 1 and Non-Patent Document 1).

又液晶顯示元件之驅動方式之一如有使對於基板呈水平配向之液晶分子藉由電場而應答之方式(亦稱為水平配向(IPS:In-Plane Swiching)方式)。水平配向方式之液晶顯示元件一般已知有藉由使用聚醯亞胺系等之水平配向膜,且以布等摩擦液晶配向膜(所謂之摩擦處理),而控制液晶之配向方向之方法,且現在工業上亦受到廣泛使用。 該摩擦處理已知有、因液晶配向膜受到磨損而產生之粉塵或傷痕導致顯示元件之顯示品位降低的問題。因此,對液晶配向膜要求伴隨摩擦處理所產生之粉塵或對液晶配向膜之損傷為少之高摩擦耐性。Also, one of the driving methods of the liquid crystal display element is the method of making the liquid crystal molecules aligned horizontally to the substrate respond to the electric field (also known as the horizontal alignment (IPS: In-Plane Swiching) method). In the liquid crystal display element of the horizontal alignment mode, a method of controlling the alignment direction of the liquid crystal is generally known by using a horizontal alignment film such as polyimide, and rubbing the liquid crystal alignment film with a cloth (so-called rubbing treatment), and It is also widely used in industry now. This rubbing treatment is known to have a problem that the display quality of the display element is lowered due to dust or scratches generated by the abrasion of the liquid crystal alignment film. Therefore, the liquid crystal alignment film is required to have high rubbing resistance with little dust generated during rubbing or damage to the liquid crystal alignment film.

專利文獻2、3揭示一種以提供不易引起因摩擦處理造成之塗膜之磨損或損傷之液晶配向膜為目的之液晶配向劑。又專利文獻4揭示一種以提供加上液晶配向膜之摩擦耐性,即使在高溫下液晶顯示元件之電壓保持率仍高,且離子密度為低之高信賴性液晶配向膜為目的之液晶配向劑。 [先前技術文獻] [專利文獻]Patent Documents 2 and 3 disclose a liquid crystal alignment agent for the purpose of providing a liquid crystal alignment film that is unlikely to cause abrasion or damage to the coating film due to rubbing treatment. Furthermore, Patent Document 4 discloses a liquid crystal alignment agent aimed at providing a highly reliable liquid crystal alignment film with low ion density and high voltage retention even at high temperatures, in addition to the rubbing resistance of the liquid crystal alignment film. [Prior Art Literature] [Patent Document]

[專利文獻1]日本特開2003-307720號公報 [專利文獻2]日本特開2008-203332號公報 [專利文獻3]國際公開公報2010/053128 [專利文獻4]國際公開公報2010/050523 [非專利文獻][Patent Document 1] Japanese Unexamined Patent Publication No. 2003-307720 [Patent Document 2] Japanese Patent Laid-Open No. 2008-203332 [Patent Document 3] International Publication 2010/053128 [Patent Document 4] International Publication 2010/050523 [Non-patent literature]

[非專利文獻1]K.Hanaoka, SID 04 DIGEST, P1200-1202[Non-Patent Document 1] K. Hanaoka, SID 04 DIGEST, P1200-1202

[發明所欲解決之課題][Problem to be Solved by the Invention]

除了上述之外,近年來伴隨液晶顯示元件之高性能化,對液晶配向膜期待之特性亦逐漸變得嚴苛。因此,過往之技術變得更加難以對應因近年來高性能化而對液晶配向膜或液晶顯示元件之特性之期待。 此外,最近之液晶顯示元件為了擴大化有效畫素面積,而在基板周邊外框部上縮小不形成畫素之邊框領域,即要求所謂之細邊框化。伴隨該面板之細邊框化,而變得需要在聚醯亞胺系液晶配向膜上塗佈使2枚基板接著在製造液晶顯示元件之際所使用之密封劑,但由於聚醯亞胺上沒有極性基或極性基少,故在密封劑與液晶配向膜表面不會形成共價鍵,而有基板彼此接著變得不充分的問題點。因此,使聚醯亞胺系液晶配向膜與密封劑或基板之接著性(密著性)提升就成為課題。 又,液晶配向膜與密封劑或基板之密著性之改善必須係在不使液晶配向膜所具有之液晶配向性或電特性降低之狀態下達成。In addition to the above, with the high performance of liquid crystal display elements in recent years, the expected characteristics of liquid crystal alignment films have gradually become more stringent. Therefore, it becomes more difficult for the conventional technology to respond to the expectation of the properties of the liquid crystal alignment film or the liquid crystal display element due to the high performance in recent years. In addition, in recent liquid crystal display devices, in order to enlarge the effective pixel area, the frame area where pixels are not formed is reduced on the peripheral frame portion of the substrate, which requires so-called thinner frame. With the thinner frame of the panel, it becomes necessary to coat the polyimide-based liquid crystal alignment film with a sealant used to make two substrates and then manufacture the liquid crystal display element, but since there is no Since there are few polar groups or polar groups, a covalent bond is not formed on the surface of the sealing agent and the liquid crystal alignment film, and there is a problem that the bonding between the substrates becomes insufficient. Therefore, it becomes a subject to improve the adhesion (adhesion) between the polyimide-based liquid crystal alignment film and the sealant or the substrate. In addition, the improvement of the adhesion between the liquid crystal alignment film and the sealant or the substrate must be achieved without reducing the liquid crystal alignment or electrical properties of the liquid crystal alignment film.

本發明所欲解決之課題在於提供一種在摩擦時不易產生膜之剝離或損傷,且電壓保持率高,在高溫高濕條件下之抗老化性良好,並且與密封劑之密著性優異之液晶配向膜,提供一種可取得該液晶配向膜之液晶配向劑,提供一種可取得該液晶配向劑之聚合物,及提供一種成為該聚合物原料之新穎二胺化合物。 [用以解決課題之手段]The problem to be solved by the present invention is to provide a liquid crystal that is less prone to film peeling or damage during rubbing, has a high voltage retention rate, has good aging resistance under high temperature and high humidity conditions, and has excellent adhesion to the sealant Alignment film, providing a liquid crystal alignment agent from which the liquid crystal alignment film can be obtained, providing a polymer from which the liquid crystal alignment agent can be obtained, and providing a novel diamine compound as a raw material of the polymer. [Means to solve the problem]

本發明者等為了解決上述課題進行精心研討之結果,進而達成本發明者,本發明具有下述之態樣。 (1)一種液晶配向劑,其特徵為含有:具有下述式(1)所示之噁唑啉骨架之聚合物。

Figure 02_image003
(R1 表示氫或一價有機基,*表示與其他基之鍵結部位。) (2)如上述(1)之液晶配向劑,其中前述式(1)所示之噁唑啉骨架為源自二胺。 (3)如上述(1)之液晶配向劑,其中具有前述式(1)所示之噁唑啉骨架之聚合物為源自選自後述之式(2-1)、(2-2)及(2-4)之二胺之聚合物。 (4)如上述(1)之液晶配向劑,其中具有前述噁唑啉骨架之聚合物為源自由包含下述式(6)所示之構造單位之聚醯亞胺前驅物,及其醯亞胺化物之聚醯亞胺所成群之至少1種。
Figure 02_image005
(式(6)中,X1 表示源自四羧酸衍生物之4價有機基。Y1 表示源自包含式(1)之構造之二胺之2價有機基。R4 表示氫原子或碳數1~5之烷基。) (5)如請求項4之液晶配向劑,其中前述式(6)中,X1 之構造為選自後述之式(A-1)~(A-21)之構造之至少1種。 (6)如上述(4)或(5)之液晶配向劑,其中相對於前述聚合物之全部構造單位,前述式(6)所示之構造單位為10莫耳%以上。 (7)一種液晶配向膜,其係由如上述(1)~(6)中任一項之液晶配向劑所得。 (8)一種液晶顯示元件,其係具備如上述(7)之液晶配向膜。 (9)一種二胺,其係具有如下述式(2-1)、(2-2)或(2-3)所示之噁唑啉骨架。
Figure 02_image007
(各記號之定義係如後述所示。) (10)一種聚合物,其係具有源自如上述(9)之二胺之噁唑啉骨架。 (11)如上述(10)之聚合物,其中前述具有噁唑啉骨架之聚合物為包含下述式(6)所示之構造單位之聚醯亞胺前驅物,及其醯亞胺化物之聚醯亞胺。
Figure 02_image009
(式(6)中之各記號之定義係與上述(4)中之記載相同。) (12)如上述(11)之聚合物,其中前述式(6)中,X1 之構造為選自後述之式(A-1)~(A-21)之構造之至少1種。 (13)如上述(11)或(12)之聚合物,其中相對於前述聚合物之全部構造單位,前述式(6)所示之構造單位為10莫耳%以上。 [發明之效果]As a result of intensive studies by the present inventors in order to solve the above-mentioned problems, the present invention has the following aspects. (1) A liquid crystal alignment agent characterized by containing: a polymer having an oxazoline skeleton represented by the following formula (1).
Figure 02_image003
(R 1 represents hydrogen or a monovalent organic group, and * represents a bonding site with other groups.) (2) The liquid crystal alignment agent as described in (1) above, wherein the oxazoline skeleton represented by the above formula (1) is the source from diamines. (3) The liquid crystal alignment agent as in the above (1), wherein the polymer having the oxazoline skeleton represented by the aforementioned formula (1) is derived from the following formula (2-1), (2-2) and (2-4) Polymer of diamine. (4) The liquid crystal alignment agent as in the above (1), wherein the polymer having the aforementioned oxazoline skeleton is derived from a polyimide precursor comprising a structural unit represented by the following formula (6), and its imide At least one type of polyimide group of aminated compounds.
Figure 02_image005
(In formula (6), X 1 represents a 4-valent organic group derived from a tetracarboxylic acid derivative. Y 1 represents a divalent organic group derived from a diamine comprising a structure of formula (1). R 4 represents a hydrogen atom or An alkyl group with 1 to 5 carbon atoms.) (5) The liquid crystal alignment agent according to claim 4, wherein in the aforementioned formula (6), the structure of X1 is selected from the following formulas (A-1) to (A-21 ) of at least one structure. (6) The liquid crystal alignment agent according to (4) or (5) above, wherein the structural unit represented by the aforementioned formula (6) is 10 mol% or more relative to all structural units of the aforementioned polymer. (7) A liquid crystal alignment film obtained from the liquid crystal alignment agent according to any one of the above (1) to (6). (8) A liquid crystal display element comprising the liquid crystal alignment film as described in (7) above. (9) A diamine having an oxazoline skeleton represented by the following formula (2-1), (2-2) or (2-3).
Figure 02_image007
(Definitions of each symbol are as follows.) (10) A polymer having an oxazoline skeleton derived from the diamine as described in (9) above. (11) The polymer as in the above (10), wherein the aforementioned polymer having an oxazoline skeleton is a polyimide precursor comprising a structural unit represented by the following formula (6), and an imide compound thereof Polyimide.
Figure 02_image009
(The definition of each symbol in the formula (6) is the same as that described in the above (4).) (12) The polymer as in the above (11), wherein in the above formula (6), the structure of X1 is selected from At least one structure of formulas (A-1) to (A-21) described below. (13) The polymer according to (11) or (12) above, wherein the structural unit represented by the aforementioned formula (6) is 10 mol% or more relative to all structural units of the aforementioned polymer. [Effect of Invention]

根據本發明,可取得一種使摩擦耐性與電壓保持特性提升,高溫高濕條件下之抗老化性良好,並且與密封劑之密著性優異之液晶配向膜。換言之,作為液晶配向劑之成分,藉由使用具有噁唑啉骨架之聚合物,而可取得在摩擦時不易產生膜之剝離或損傷,並且電壓保持率及高溫高濕抗老化性皆高,與密封劑之密著性優異之液晶配向膜。 具備由本發明之液晶配向劑所得之液晶配向膜之液晶顯示元件則成為因液晶配向膜之削損或傷痕造成之顯示缺陷為少,且信賴性高,與密封劑之密著性優異之液晶顯示元件。According to the present invention, it is possible to obtain a liquid crystal alignment film with improved rubbing resistance and voltage retention characteristics, good aging resistance under high temperature and high humidity conditions, and excellent adhesion with a sealant. In other words, by using a polymer with an oxazoline skeleton as a component of the liquid crystal alignment agent, it is difficult to cause peeling or damage of the film during friction, and the voltage retention rate and high temperature and high humidity aging resistance are high. Liquid crystal alignment film with excellent adhesiveness of sealant. The liquid crystal display element equipped with the liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention has few display defects due to damage or scratches of the liquid crystal alignment film, has high reliability, and has excellent adhesion to the sealant. element.

本發明之液晶配向劑為含有:具有下述式(1)所示構造之聚合物(以下亦稱為特定聚合物)之液晶配向劑。 <特定構造>

Figure 02_image011
上述式(1)中,R1 表示氫、或一價有機基,*表示與其他基之鍵結部位。本發明中之特定聚合物係以由具有上述式(1)之構造之二胺所得之聚合物為佳。The liquid crystal alignment agent of the present invention is a liquid crystal alignment agent containing: a polymer having a structure represented by the following formula (1) (hereinafter also referred to as a specific polymer). <specific structure>
Figure 02_image011
In the above formula (1), R 1 represents hydrogen or a monovalent organic group, and * represents a bonding site with other groups. The specific polymer in the present invention is preferably a polymer obtained from a diamine having the structure of the above formula (1).

<特定二胺> 具有上述式(1)所示之噁唑啉骨架之二胺(以下亦稱為特定二胺)可舉出如選自下述式(2-1)~式(2-3)所示之群之二胺。<Specific diamines> Examples of diamines having an oxazoline skeleton represented by the above formula (1) (hereinafter also referred to as specific diamines) include those selected from the group represented by the following formulas (2-1) to (2-3). of diamines.

Figure 02_image013
Figure 02_image013

上述式(2-1)~式(2-3)中,R1 之定義係與上述式(1)中記載者相同。R2 表示選自單鍵、-O-、-COO-、 -OCO-、-(CH2 )l -、-O(CH2 )l O-、-CONR11 -、-NR11 CO-及 -NR11 -之鍵結,或由該等之組合所構成之2價有機基,W1 表示選自下述群(3-1)之構造、W2 表示選自下述群(3-2)之構造、W3 表示選自下述群(3-3)之構造、W4 表示選自下述群(3-4)之構造。在此,R11 表示氫,或一價有機基,l表示1~12之整數,a表示0或1之整數。In the above formula (2-1) to formula (2-3), the definition of R 1 is the same as that described in the above formula (1). R 2 is selected from single bond, -O-, -COO-, -OCO-, -(CH 2 ) l -, -O(CH 2 ) l O-, -CONR 11 -, -NR 11 CO- and - A bond of NR 11 -, or a divalent organic group composed of these combinations, W 1 represents a structure selected from the following group (3-1), W 2 represents a structure selected from the following group (3-2) W 3 represents a structure selected from the following group (3-3), and W 4 represents a structure selected from the following group (3-4). Here, R 11 represents hydrogen or a monovalent organic group, l represents an integer of 1-12, and a represents an integer of 0 or 1.

Figure 02_image015
Figure 02_image015

上述群(3-1)中,*1 表示與式(2-1)至(2-3)中之胺基鍵結之部位,*2 表示與噁唑啉環鍵結之部位。群(3-2)中,*1 表示與式(2-1)至(2-3)中之胺基鍵結之部位,*3 表示與R2 鍵結之部位。群(3-3)中,*3 表示與R2 鍵結之部位。群(3-4)中,*2 表示與噁唑啉環鍵結之部位。X表示取代基,氫原子;鹵素原子;甲基、乙基、丙基等之碳數1~6之烷基;三氟甲基等之碳數1~6之鹵化烷基;二甲基胺基等之取代胺基;甲氧基、乙氧基等之碳數1~6之烷氧基;NHCOCH3 或NHCOCH2 CH3 、NHCOOtBu等之醯胺基。tBu表示第3級丁基。In the above-mentioned group (3-1), * 1 represents the site bonded to the amino group in formulas (2-1) to (2-3), and * 2 represents the site bonded to the oxazoline ring. In the group (3-2), * 1 represents the site bonded to the amine group in formulas (2-1) to (2-3), and * 3 represents the site bonded to R 2 . In the group (3-3), * 3 represents a bonding site to R 2 . In the group (3-4), * 2 represents a bonding site to the oxazoline ring. X represents a substituent, a hydrogen atom; a halogen atom; an alkyl group with 1 to 6 carbons such as methyl, ethyl, and propyl; a halogenated alkyl group with 1 to 6 carbons such as trifluoromethyl; dimethylamine Substituted amino groups such as methoxy and ethoxy groups; alkoxy groups with 1 to 6 carbon atoms such as methoxy and ethoxy groups; amido groups such as NHCOCH 3 or NHCOCH 2 CH 3 , NHCOOtBu, etc. tBu represents the tertiary butyl group.

上述式(2-1)~(2-3)之二胺之具體例係如以下所例示者。

Figure 02_image017
Specific examples of the diamines of the above formulas (2-1) to (2-3) are illustrated below.
Figure 02_image017

上述式中,R1 之定義係與上述式(1)中記載者相同,尤其係以氫原子、甲基(Me)或乙基(Et)為佳。R11 之定義係與上述式(1)中記載者相同,尤其係以氫原子、Me基或Et基為佳。n表示1~6之整數,m表示1~12之整數。In the above formula, the definition of R 1 is the same as that described in the above formula (1), especially a hydrogen atom, a methyl group (Me) or an ethyl group (Et). The definition of R 11 is the same as that described in the above formula (1), especially hydrogen atom, Me group or Et group is preferred. n represents an integer of 1-6, and m represents an integer of 1-12.

<特定二胺之合成方法> 合成本發明之特定二胺之方法,可舉出例如合成出下述式(4-1)~(4-3)所示之二硝基化合物,再將硝基予以還原而轉換成胺基之方法。

Figure 02_image019
上述式(4-1)~(4-3)中,R1 、R2 、W1 、W2 、W3 、W4 及a之定義係與上述式(2-1)~(2-3)中記載者相同。<Synthesis method of specific diamine> The method for synthesizing the specific diamine of the present invention includes, for example, synthesizing dinitro compounds represented by the following formulas (4-1) to (4-3), and then adding nitro A method of converting it into an amine group by reduction.
Figure 02_image019
In the above formulas (4-1) to (4-3), the definitions of R 1 , R 2 , W 1 , W 2 , W 3 , W 4 and a are the same as those in the above formulas (2-1) to (2-3) ) are the same.

上述硝基之還原反應所使用之觸媒係以能得作為市售品之活性碳載持金屬為佳,可舉出例如、鈀-活性碳、鉑-活性碳、銠-活性碳等。又,氫氧化鈀、氧化鉑、雷尼鎳等也可不必為活性碳載持型之金屬觸媒。其中係以鈀-活性碳為佳。The catalyst used for the reduction reaction of the nitro group is preferably a commercially available metal supported on activated carbon, for example, palladium-activated carbon, platinum-activated carbon, rhodium-activated carbon and the like. Also, palladium hydroxide, platinum oxide, Raney nickel, etc. do not need to be activated carbon-supported metal catalysts. Among them, palladium-activated carbon is preferred.

為了使上述還原反應更加有效進行,也會有在活性碳之共存下實施反應的情況。此時,使用之活性碳之量在相對於二硝基化合物而言,以1~30質量%為佳,以10~20質量%為較佳。根據相同理由,也有加壓下實施反應的情況。於此情況,為了避免苯核還原,以20氣壓以下為佳,較佳為至10氣壓為止之範圍下實施反應。In order to make the reduction reaction described above proceed more efficiently, the reaction may be carried out in the coexistence of activated carbon. At this time, the amount of activated carbon to be used is preferably 1 to 30% by mass, more preferably 10 to 20% by mass relative to the dinitro compound. For the same reason, the reaction may be carried out under pressure. In this case, in order to avoid the reduction of benzene nuclei, it is preferable to carry out the reaction under 20 atmospheres, more preferably up to 10 atmospheres.

上述還原反應中之溶劑只要係不會與各原料反應之溶劑,即可無限制地使用。例如,可使用非質子性極性有機溶劑(DMF、DMSO、DMAc、NMP等);醚類(Et2 O、i-Pr2 O、TBME、CPME、THF、二噁烷等);脂肪族烴類(戊烷、己烷、庚烷、石油醚等);芳香族烴類(苯、甲苯、二甲苯、均三甲苯、氯苯、二氯苯、硝基苯、四氫萘等);鹵系烴類(氯仿、二氯甲烷、四氯化碳、二氯乙烷等);低級脂肪酸酯類(乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酸甲酯等);腈類(乙腈、丙腈、丁腈等)等。該等溶劑係可在考慮到引起反應之容易度後適宜選擇,亦可混合2種以上使用。因應必要,亦可使用適當脫水劑或乾燥劑來乾燥溶劑而使用當作非水溶劑。溶劑之使用量(反應濃度)相對於二硝基化合物為0.1~100質量倍,以0.5~30質量倍為佳,更佳為1~10質量倍。 反應溫度係在從-100℃至使用之溶劑之沸點為止範圍,以-50~150℃為佳。反應時間通常為0.05~350小時,以0.5~100小時為佳。The solvent in the above reduction reaction can be used without limitation as long as it does not react with each raw material. For example, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.); ethers (Et 2 O, i-Pr 2 O, TBME, CPME, THF, dioxane, etc.); aliphatic hydrocarbons can be used (pentane, hexane, heptane, petroleum ether, etc.); aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.); halogen series Hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.); lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.); nitriles (acetonitrile, propionitrile, butyronitrile, etc.), etc. These solvents may be appropriately selected in consideration of the easiness of inducing a reaction, and may be used in combination of two or more. If necessary, a suitable dehydrating agent or desiccant can also be used to dry the solvent and use it as a non-aqueous solvent. The usage amount (reaction concentration) of the solvent is 0.1 to 100 times by mass, preferably 0.5 to 30 times by mass, more preferably 1 to 10 times by mass relative to the dinitro compound. The reaction temperature ranges from -100°C to the boiling point of the solvent used, preferably -50 to 150°C. The reaction time is usually 0.05 to 350 hours, preferably 0.5 to 100 hours.

[式(4-1)、式(4-3)之二硝基化合物之製法] 合成式(4-1)及(4-3)之化合物之方法係例如下述反應式所示般,藉由使式(5-1)或(5-2)所示之化合物與鹵硝基苯在鹼之存在下反應而可取得(4-1-1)或(4-3-1)。

Figure 02_image021
[Methods for preparing dinitro compounds of formula (4-1), formula (4-3)] The method of synthesizing the compounds of formula (4-1) and (4-3) is as shown in the following reaction formula, by (4-1-1) or (4-3-1) can be obtained by reacting the compound represented by formula (5-1) or (5-2) with halonitrobenzene in the presence of a base.
Figure 02_image021

上述反應係以在鹼之存在下進行為佳。作為鹼,可將例如氫氧化鈉、氫氧化鉀等之鹼金屬氫氧化物、碳酸鈉、碳酸鉀等之鹼金屬碳酸鹽、碳酸氫鈉、碳酸氫鉀等之鹼金屬重碳酸鹽、磷酸鉀、1,8-二吖雙環[5,4,0]-7-十一烯或三乙基胺等之有機鹼等,較佳以相對於(5-1)或(5-2)而言使用1~4當量。The above reaction is preferably carried out in the presence of a base. As the base, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate, potassium phosphate , 1,8-diacribicyclo[5,4,0]-7-undecene or organic bases such as triethylamine, etc., preferably relative to (5-1) or (5-2) 1 to 4 equivalents are used.

作為反應溶劑,以非質子性極性有機溶劑(DMF、DMSO、DMAc、NMP等)為佳。溶劑之使用量(反應濃度)在相對於(5-1)或(5-2)而言,以0.1~100質量倍為佳,較佳為0.5~30質量倍。 反應溫度係以從-10℃至所使用之溶劑之沸點為止之範圍為佳,較佳為0~150℃。反應時間通常為0.05~350小時,以0.5~100小時為佳。As the reaction solvent, an aprotic polar organic solvent (DMF, DMSO, DMAc, NMP, etc.) is preferable. The usage amount (reaction concentration) of the solvent is preferably 0.1 to 100 times by mass, more preferably 0.5 to 30 times by mass relative to (5-1) or (5-2). The reaction temperature is preferably in the range from -10°C to the boiling point of the solvent used, preferably 0 to 150°C. The reaction time is usually 0.05 to 350 hours, preferably 0.5 to 100 hours.

作為製造上述二硝基化合物之其他手法,對(5-1-1)或(5-2-1)所示之醇化合物導入脫離基(LG)而取得(5-1-1a)或(5-2-1a)後,藉由在鹼之存在下使其與酚化合物或胺化合物反應而可取得式(4-1-2)或(4-3-2)。

Figure 02_image023
As another method for producing the above-mentioned dinitro compounds, (5-1-1a) or (5 - After 2-1a), the formula (4-1-2) or (4-3-2) can be obtained by reacting it with a phenol compound or an amine compound in the presence of a base.
Figure 02_image023

上述脫離基(LG)係可在三乙基胺或吡啶等之鹼之存在下,與甲烷磺醯基氯化物、乙烷磺醯基氯化物、或p-甲苯磺醯基氯化物等反應來導入。The above-mentioned leaving group (LG) can be reacted with methanesulfonyl chloride, ethanesulfonyl chloride, or p-toluenesulfonyl chloride in the presence of a base such as triethylamine or pyridine. import.

(5-1-1a)或(5-2-1a)與酚化合物或胺化合物之反應係以在鹼之存在下進行為佳。作為鹼,可將例如氫氧化鈉、氫氧化鉀等之鹼金屬氫氧化物、碳酸鈉、碳酸鉀等之鹼金屬碳酸鹽,以相對於(5-1-1a)或(5-2-1a)而言使用1~4當量。The reaction of (5-1-1a) or (5-2-1a) with a phenolic compound or an amine compound is preferably carried out in the presence of a base. As the base, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate can be used relative to (5-1-1a) or (5-2-1a ) using 1 to 4 equivalents.

藉由使(5-1)或(5-2)所示之化合物與酸氯化物在三乙基胺或吡啶等之鹼之存在下反應,而可取得(4-1-2)或(4-3-3)。

Figure 02_image025
(4-1-2) or (4 -3-3).
Figure 02_image025

[式(4-2)之製法] 合成式(4-2)之化合物之方法並無特別限制。例如下述反應式所示般,藉由使式(5-1)所示之化合物與酸氯化物在三乙基胺或吡啶等之鹼之存在下反應而可取得(4-2-1)或(4-2-2)。

Figure 02_image027
[Method for producing formula (4-2)] The method for synthesizing the compound of formula (4-2) is not particularly limited. For example, as shown in the following reaction formula, (4-2-1) can be obtained by reacting a compound represented by formula (5-1) with an acid chloride in the presence of a base such as triethylamine or pyridine. or (4-2-2).
Figure 02_image027

[式(5-1)及(5-2)之製法] 合成式(5-1)及式(5-2)之方法並無特別限制。例如參考文獻(J. Org. Chem. 2014, 79, 8668-8677)如下述反應式所示般,藉由使氰基化合物與胺基乙醇化合物在鹼之存在下反應而可取得(5-1-1)或(5-2-1)。

Figure 02_image029
[Methods for preparing formulas (5-1) and (5-2)] The methods for synthesizing formulas (5-1) and (5-2) are not particularly limited. For example, the reference (J. Org. Chem. 2014, 79, 8668-8677) can be obtained by reacting a cyano compound with an aminoethanol compound in the presence of a base as shown in the following reaction formula (5-1 -1) or (5-2-1).
Figure 02_image029

上述反應係以在鹼之存在下進行為佳。作為鹼,可將例如氫氧化鈉、氫氧化鉀等之鹼金屬氫氧化物、碳酸鈉、碳酸鉀等之鹼金屬碳酸鹽、磷酸鈉、磷酸鉀等之無機化合物、1,8-二吖雙環[5,4,0]-7-十一烯等之有機鹼等,以相對於氰基化合物而言使用1~4當量。其中係以碳酸鈉、碳酸鉀等之鹼金屬碳酸鹽為佳。The above reaction is preferably carried out in the presence of a base. As the base, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, inorganic compounds such as sodium phosphate and potassium phosphate, 1,8-diazene bicyclo Organic bases such as [5,4,0]-7-undecene and the like are used in an amount of 1 to 4 equivalents to the cyano compound. Among them, alkali metal carbonates such as sodium carbonate and potassium carbonate are preferred.

作為反應溶劑,可使用如非質子性極性有機溶劑(DMF、DMSO、DMAc、NMP等);醚類(Et2 O、i-Pr2 O、TBME、CPME、THF、二噁烷等);脂肪族烴類(戊烷、己烷、庚烷、石油醚等);芳香族烴類(苯、甲苯、二甲苯、均三甲苯、氯苯、二氯苯、硝基苯、四氫萘等);鹵系烴類(氯仿、二氯甲烷、四氯化碳、二氯乙烷等);低級脂肪酸酯類(乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酸甲酯等);腈類(乙腈、丙腈、丁腈等);醇類(甲醇、乙醇、2-丙醇等)等。該等溶劑係可在考慮到引起反應之容易度後適宜選擇,可單獨使用1種或可將2種以上混合使用。因應必要,亦可使用適當脫水劑或乾燥劑來乾燥溶劑而使用當作非水溶劑。尤其係以醇類(甲醇、乙醇、2-丙醇等)為佳。As the reaction solvent, for example, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.); ethers (Et 2 O, i-Pr 2 O, TBME, CPME, THF, dioxane, etc.); aliphatic Aromatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.); Aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.) ; Halogenated hydrocarbons (chloroform, methylene chloride, carbon tetrachloride, ethylene dichloride, etc.); lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.); nitriles (acetonitrile, propionitrile, butyronitrile, etc.); alcohols (methanol, ethanol, 2-propanol, etc.), etc. These solvents can be appropriately selected in consideration of the easiness of causing the reaction, and may be used alone or in combination of two or more. If necessary, a suitable dehydrating agent or desiccant can also be used to dry the solvent and use it as a non-aqueous solvent. In particular, alcohols (methanol, ethanol, 2-propanol, etc.) are preferred.

使下述(5-1-1a)或(5-2-1a)與酞醯亞胺鉀(Phthalimide potassium)反應而取得(5-1-1b)或(5-2-1b)後,藉由使用胼一水合物進行脫保護而可取得(5-1-2)或(5-2-2)。又,藉由使過剩量之2級胺化合物與(5-1-1a)或(5-2-1a)反應而可取得(5-1-3)或(5-2-3)。

Figure 02_image031
After making the following (5-1-1a) or (5-2-1a) react with phthalimide potassium (Phthalimide potassium) to obtain (5-1-1b) or (5-2-1b), by Deprotection using hydrazine monohydrate affords (5-1-2) or (5-2-2). Also, (5-1-3) or (5-2-3) can be obtained by reacting an excess amount of the secondary amine compound with (5-1-1a) or (5-2-1a).
Figure 02_image031

尚且,至今為止之製造流程之式中,R1 、W1 、W2 、W3 、W4 之定義係與上述式(2-1)~(2-3)中之情況相同,但R1 係以氫原子或Me基、Et基為佳。Y表示OH、NH2 或NHR11 ,Y1 表示O、NH或NR11 ,R11 之定義係與上述式(1)中之情況相同,但以氫原子、Me基及Et基為佳。Z表示F、Cl、Br、I,n表示1~6之整數,m表示1~12之整數。Also, in the formulas of the manufacturing process so far, the definitions of R 1 , W 1 , W 2 , W 3 , and W 4 are the same as those in the above formulas (2-1) to (2-3), but R 1 It is preferably a hydrogen atom or a Me group or an Et group. Y represents OH, NH 2 or NHR 11 , Y 1 represents O, NH or NR 11 , the definition of R 11 is the same as that in the above formula (1), but hydrogen atom, Me group and Et group are preferred. Z represents F, Cl, Br, I, n represents an integer of 1-6, and m represents an integer of 1-12.

<聚合物> 本發明之具有噁唑啉骨架之聚合物為具有上述式(1)所示之構造。作為具體例,可舉出如聚醯胺酸、聚醯胺酸酯、聚醯亞胺、聚脲、聚醯胺等。從做為液晶配向劑之觀點,以選自包含下述式(6)所示之構造單位之聚醯亞胺前驅物、及該醯亞胺化物之聚醯亞胺之至少1種為較佳。

Figure 02_image033
上述式(6)中,X1 為源自四羧酸衍生物之4價有機基,Y1 為源自包含式(1)之構造之二胺之2價有機基,R4 為氫原子或碳數1~5之烷基。R4 在從由加熱所成之醯亞胺化之容易度之觀點,以氫原子、甲基或乙基為佳。<Polymer> The polymer having an oxazoline skeleton of the present invention has a structure represented by the above formula (1). Specific examples include polyamic acid, polyamic acid ester, polyimide, polyurea, and polyamide. From the viewpoint of being used as a liquid crystal alignment agent, at least one selected from a polyimide precursor containing a structural unit represented by the following formula (6) and a polyimide of the imide compound is preferred. .
Figure 02_image033
In the above formula (6), X 1 is a quaternary organic group derived from a tetracarboxylic acid derivative, Y 1 is a divalent organic group derived from a diamine comprising the structure of formula (1), R 4 is a hydrogen atom or An alkyl group with 1 to 5 carbon atoms. R 4 is preferably a hydrogen atom, a methyl group or an ethyl group from the viewpoint of easiness of imidization by heating.

<四羧酸二酐> 上述式(6)之聚醯亞胺前驅物中之X1 係可因應聚合物對溶劑之溶解性或液晶配向劑之塗佈性、作成液晶配向膜時之液晶之配向性、電壓保持率、蓄積電荷等所必須之特性程度而適宜選擇,可相同聚合物中可為1種類,亦可混合存在2種類以上。 若例示X1 之具體例,可舉出如在國際公開公報2015/119168之第13項~第14項揭示之式(X-1)~(X-46)之構造等。<Tetracarboxylic dianhydride> X1 in the polyimide precursor of the above formula (6) can be used in accordance with the solubility of the polymer to the solvent or the coating property of the liquid crystal alignment agent, and the liquid crystal when it is made into a liquid crystal alignment film. Alignment, voltage retention, charge storage, and other necessary characteristics are appropriately selected, and one type may be used in the same polymer, or two or more types may be mixed. Specific examples of X1 include the structures of formulas (X-1) to (X-46) disclosed in Items 13 to 14 of International Publication No. 2015/119168.

以下展示較佳之X1 之構造。

Figure 02_image035
The structure of the preferred X1 is shown below.
Figure 02_image035

上述當中,從更加提升摩擦耐性之觀點,特佳為(A-1)、(A-2),從更加提升蓄積電荷之緩和速度之觀點,特佳為(A-4),從更加提升液晶配向性與蓄積電荷之緩和速度之觀點,特佳為(A-15)~(A-17)等。 又,上述當中,從更加提升電壓保持率之觀點,以(A-1)、(A-4)、(A-5)、(A-7)為佳。Among the above, (A-1) and (A-2) are particularly preferable from the viewpoint of further improving the friction resistance, and (A-4) is particularly preferable from the viewpoint of further improving the relaxation speed of accumulated electric charges. From the viewpoint of alignment and relaxation speed of accumulated charge, (A-15) to (A-17) and the like are particularly preferable. Also, among the above, (A-1), (A-4), (A-5), and (A-7) are preferable from the viewpoint of further improving the voltage retention ratio.

<二胺> 上述式(6)中,作為Y1 之具體例,可舉出如從前述式(2-1)、(2-2)或(2-3)之二胺去除2個胺基後之構造。<Diamine> In the above formula (6), specific examples of Y 1 include removing two amino groups from the diamine of the above formula (2-1), (2-2) or (2-3). subsequent structure.

<聚合物(其他構造單位)> 包含式(6)所示之構造單位之聚醯亞胺前驅物在不損及本發明之效果範圍內,亦可包含下述式(7)所示之構造單位。

Figure 02_image037
式(7)中,X2 為源自四羧酸衍生物之4價有機基,Y2 為源自不包含式(1)之構造之二胺之2價有機基,R4 係與前述式(6)之定義相同,R5 表示氫原子或碳數1~4之烷基。又,2個R4 之至少一者係以氫原子為佳。<Polymer (other structural unit)> The polyimide precursor containing the structural unit represented by the formula (6) may also contain the structure represented by the following formula (7) within the scope not to impair the effect of the present invention unit.
Figure 02_image037
In formula (7), X 2 is a quaternary organic group derived from tetracarboxylic acid derivatives, Y 2 is a divalent organic group derived from a diamine that does not contain the structure of formula (1), R 4 is the same as the aforementioned formula The definition of (6) is the same, and R 5 represents a hydrogen atom or an alkyl group having 1 to 4 carbons. Also, at least one of the two R 4 is preferably a hydrogen atom.

作為X2 之具體例,其中也包括較佳例,可舉出如與式(6)之X1 所例示者相同之構造。又,聚醯亞胺前驅物中之Y2 為源自不包含式(1)之構造之二胺之二價有機基,且其之構造並無特別限定。又,Y2 係可因應聚合物對溶劑之溶解性或液晶配向劑之塗佈性、作成液晶配向膜時之液晶之配向性、電壓保持率、蓄積電荷等所必須之特性程度而適宜選擇,在相同聚合物中亦可混合存在2種類以上。Specific examples of X2 , including preferred examples, include the same structures as those exemplified for X1 in formula (6). In addition, Y 2 in the polyimide precursor is a divalent organic group derived from a diamine that does not contain the structure of formula (1), and its structure is not particularly limited. In addition, Y2 can be appropriately selected according to the solubility of the polymer to the solvent or the coating property of the liquid crystal alignment agent, the alignment of the liquid crystal when the liquid crystal alignment film is made, the voltage retention rate, and the accumulated charge. Two or more types may be mixed in the same polymer.

若例示Y2 之具體例,可舉出如國際公開公報2015/119168之第4項揭示之式(2)之構造,及,第8項~第12項揭示之式(Y-1)~(Y-97)、(Y-101)~(Y-118)之構造;從國際公開公報2013/008906之第6項揭示之從式(2)去除2個胺基後之二價有機基;從國際公開公報2015/122413之第8項揭示之式(1)去除2個胺基後之二價有機基;國際公開公報2015/060360之第8項揭示之式(3)之構造;從日本特開公報2012-173514之第8項記載之式(1)去除2個胺基後之二價有機基;從國際公開公報2010-050523之第9項揭示之式(A)~(F)去除2個胺基後之二價有機基等。If a specific example of Y2 is illustrated, the structure of formula (2) disclosed in item 4 of International Publication No. 2015/119168, and the formulas (Y-1)~( The structure of Y-97), (Y-101)~(Y-118); the divalent organic group after removing two amine groups from formula (2) disclosed in item 6 of International Publication 2013/008906; from The structure of formula (3) disclosed in item 8 of International Publication 2015/122413 after removing two amine groups from formula (1) disclosed in International Publication 2015/122413; the structure of formula (3) disclosed in International Publication 2015/060360; The divalent organic group obtained by removing two amine groups from the formula (1) described in Item 8 of the Publication No. 2012-173514; the formula (A)-(F) disclosed in Item 9 of the International Publication No. 2010-050523 removes 2 A divalent organic group after an amine group, etc.

<其他二胺> 除了上述二胺成分,亦可使用下述所示之二胺成分作為其他二胺。 <其他二胺:具有式(0)之構造之二胺> 其他二胺具有下述式(0)之構造。

Figure 02_image039
<Other diamines> In addition to the above-mentioned diamine components, the diamine components shown below can also be used as other diamines. <Other diamine: the diamine which has the structure of formula (0)> Other diamine has the structure of following formula (0).
Figure 02_image039

上述式(0)中,A1 及A5 係各自獨立表示單鍵或碳數1~5之伸烷基。在從與貼合上下基板之密封材中之官能基之反應性的觀點,以單鍵或亞甲基為佳。In the above formula (0), A 1 and A 5 each independently represent a single bond or an alkylene group having 1 to 5 carbon atoms. From the viewpoint of reactivity with the functional group in the sealing material for laminating the upper and lower substrates, a single bond or a methylene group is preferable.

又,上述式(0)中,A2 及A4 係各自獨立表示碳數1~5之伸烷基,以亞甲基或伸乙基為佳。A3 表示碳數1~6之伸烷基或環伸烷基,從與密封材中之官能基之反應性之觀點,以亞甲基或伸乙基為佳。Also, in the above formula (0), A 2 and A 4 each independently represent an alkylene group having 1 to 5 carbon atoms, preferably a methylene group or an ethylene group. A 3 represents an alkylene or cycloalkylene group having 1 to 6 carbon atoms, preferably a methylene group or an ethylene group from the viewpoint of reactivity with functional groups in the sealing material.

又,上述式(0)中,B1 及B2 係各自獨立表示單鍵、-O-、-NH-、-N(CH3 )-、-CO-、-COO-、-OCO-、 -CONH-、-NHCO-、-CON(CH3 )-或-N(CH3 )CO。從取得之液晶配向膜之配向性的觀點,以單鍵或-O-為佳。In addition, in the above formula (0), B 1 and B 2 each independently represent a single bond, -O-, -NH-, -N(CH 3 )-, -CO-, -COO-, -OCO-, - CONH-, -NHCO-, -CON( CH3 )- or -N( CH3 )CO. From the viewpoint of the alignment of the obtained liquid crystal alignment film, a single bond or -O- is preferable.

又,上述式(0)中,D1 表示因熱而取代成氫原子之保護基。D1 係功用作為胺基之保護基者,且係因熱而取代成氫原子之官能基。從液晶配向劑保存安定性之觀點,D1 係以在室溫下不會脫離為佳,以因80℃以上之熱而脫離之保護基為佳,以因100℃以上,特別係因120℃以上之熱而脫離之保護基為更加。脫離之溫度係以250℃以下為佳,以230℃以下為較佳。過高之脫離溫度會有導致聚合物分解之可能性。作為此種D1 之例,可舉出如tert-丁氧基羰基(t-Boc)基、9-茀基甲氧基羰基等。其中從因溫度造成之脫離性之觀點,以t-Boc基為佳。Also, in the above formula (0), D 1 represents a protecting group substituted with a hydrogen atom due to heat. D1 is a functional group that functions as a protecting group for an amine group, and is a functional group that is substituted with a hydrogen atom due to heat. From the perspective of storage stability of the liquid crystal alignment agent, D1 is preferably a protecting group that will not detach at room temperature, and is preferably a protecting group that detaches due to heat above 80°C, especially when it is above 120°C. The protective group detached from the above heat is even more. The detachment temperature is preferably below 250°C, more preferably below 230°C. Excessively high release temperature may lead to the possibility of polymer decomposition. Examples of such D1 include tert-butoxycarbonyl (t-Boc) group, 9-tertilylmethoxycarbonyl group and the like. Among them, the t-Boc group is preferable from the viewpoint of detachability due to temperature.

又,上述式(0)中,a為0或1。A2 及A3 (a為1時),A3 及A4 (a為1時)、或A2 及A4 (a為0時)不會互相結合。亦即,a為1時,不會藉由A2 及A3 、A3 及A4 來形成環,鍵結於D1 之N原子不會構成該環之一部分。同樣地,a為0時,不會藉由A2 及A4 來形成環,鍵結於D1 之N原子不會構成該環之一部分。In addition, in the above formula (0), a is 0 or 1. A 2 and A 3 (when a is 1), A 3 and A 4 (when a is 1), or A 2 and A 4 (when a is 0) do not combine with each other. That is, when a is 1, a ring will not be formed by A 2 and A 3 , A 3 and A 4 , and the N atom bonded to D 1 will not constitute a part of the ring. Similarly, when a is 0, a ring will not be formed by A2 and A4 , and the N atom bonded to D1 will not constitute a part of the ring.

又,上述式(0)中,*表示與其他基之鍵結部位。從*處來看,相對於苯環之A1 及/或A5 之鍵結位置可為鄰位、間位、對位之任一者,但從液晶配向膜之液晶配向性之觀點,以對位為佳。即,上述式(0)係以下述式(0’)或下述式(0”)為佳。

Figure 02_image041
上述式(0’)及上述式(0”)中,A1 ~A5 、B1 、B2 、D1 、a以及*係與上述式(0)之情況相同。Moreover, in said formula (0), * represents the bonding site with another group. From the perspective of *, the bonding position of A1 and/or A5 relative to the benzene ring can be any of the ortho, meta, and para positions, but from the perspective of the liquid crystal alignment of the liquid crystal alignment film, Counterpoint is good. That is, the above-mentioned formula (0) is preferably the following formula (0') or the following formula (0").
Figure 02_image041
In the above formula (0') and the above formula (0"), A 1 to A 5 , B 1 , B 2 , D 1 , a, and * are the same as those in the above formula (0).

作為此種特定二胺之具體例,可舉出例如下述式(0-1)~(0-21)所示之二胺。

Figure 02_image043
As a specific example of such specific diamine, the diamine shown by following formula (0-1)-(0-21), for example is mentioned.
Figure 02_image043

<其他二胺:具有展現垂直配向性之特定側鏈構造之二胺> 在使用作為VA方式之液晶顯示元件中之液晶配向劑時,以使用具有展現垂直配向能力之特定側鏈構造之二胺來調製特定聚合物為佳。此具有特定側鏈構造之二胺係具有選自下述式[S1]~[S3]所示之群之至少1種側鏈構造。以下,依序說明關於該具有特定側鏈構造之二胺之例,即式[S1]~[S3]所示之二胺。<Other diamines: Diamines having a specific side chain structure exhibiting vertical alignment> When using a liquid crystal alignment agent in a VA-type liquid crystal display element, it is preferable to prepare a specific polymer using a diamine having a specific side chain structure exhibiting vertical alignment capability. This diamine having a specific side chain structure has at least one side chain structure selected from the group represented by the following formulas [S1] to [S3]. Hereinafter, the example about the diamine which has this specific side chain structure, ie, the diamine represented by formula [S1]-[S3] is demonstrated sequentially.

[A]:具有下述式[S1]所示之特定側鏈構造之二胺

Figure 02_image045
上述式[S1]中,X1 及X2 係各自獨立表示單鍵、-(CH2 )a -(a為1~15之整數)、-CONH-、-NHCO-、-CON(CH3 )-、 -NH-、-O-、-COO-、-OCO-或-((CH2 )a1 -A1 )m1 -。其中,複數之a1係各自獨立為1~15之整數,複數之A1 係各自獨立表示氧原子或-COO-,m1為1~2。[A]: Diamine having a specific side chain structure represented by the following formula [S1]
Figure 02_image045
In the above formula [S1], X 1 and X 2 each independently represent a single bond, -(CH 2 ) a - (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH 3 ) -, -NH-, -O-, -COO-, -OCO-, or -((CH 2 ) a1 -A 1 ) m1 -. Among them, a1 in plural is independently an integer of 1-15, A1 in plural is independently an oxygen atom or -COO-, and m1 is 1-2.

其中,從原料取得性或合成容易度之觀點,X1 及X2 係以各自獨立為單鍵、-(CH2 )a -(a為1~15之整數)、-O-、-CH2 O-或-COO-為佳,以單鍵、-(CH2 )a -(a為1~10之整數)、-O-、-CH2 O-或-COO-為較佳。Among them, from the viewpoint of availability of raw materials or ease of synthesis, X 1 and X 2 are each independently a single bond, -(CH 2 ) a - (a is an integer of 1 to 15), -O-, -CH 2 O- or -COO- is preferred, and a single bond, -(CH 2 ) a - (a is an integer of 1 to 10), -O-, -CH 2 O- or -COO- is preferred.

又,上述式[S1]中,G1 及G2 係各自獨立表示選自碳數6~12之2價芳香族基或碳數3~8之2價脂環式基之2價環狀基。該環狀基上之任意氫原子可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子所取代。m及n係各自獨立為0~3之整數,且m及n之合計為1~4。Also, in the above formula [S1], G1 and G2 each independently represent a divalent cyclic group selected from a divalent aromatic group having 6 to 12 carbons or a divalent alicyclic group having 3 to 8 carbons. . Any hydrogen atom on the cyclic group can be replaced by an alkyl group with 1 to 3 carbons, an alkoxy group with 1 to 3 carbons, a fluorine-containing alkyl group with 1 to 3 carbons, or a fluoroalkane with 1 to 3 carbons. Oxygen or fluorine atoms are substituted. m and n are each independently an integer of 0-3, and the total of m and n is 1-4.

又,上述式[S1]中,R1 表示碳數1~20之烷基、碳數1~20之烷氧基或碳數2~20之烷氧基烷基。形成R1 之任意之氫亦可經氟取代。其中,作為碳數6~12之2價芳香族基之例,可舉出如伸苯基、伸聯苯基、萘等。又,作為碳數3~8之2價脂環式基之例,可舉出如伸環丙基、伸環己基等。In addition, in the above formula [S1], R 1 represents an alkyl group having 1 to 20 carbons, an alkoxy group having 1 to 20 carbons, or an alkoxyalkyl group having 2 to 20 carbons. Any hydrogen forming R1 may also be replaced by fluorine. Among these, examples of divalent aromatic groups having 6 to 12 carbon atoms include phenylene, biphenylene, and naphthalene. Moreover, examples of the divalent alicyclic group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclohexylene group, and the like.

因此,作為上述式[S1]之較佳具體例,可舉出如下述式[S1-x1]~[S1-x7]。

Figure 02_image047
Therefore, as a preferable specific example of said formula [S1], following formula [S1-x1]-[S1-x7] can be mentioned.
Figure 02_image047

上述式[S1-x1]~[S1-x7]中,R1 係與上述式[S1]之情況相同。Xp 表示-(CH2 )a -(a為1~15之整數)、 -CONH-、-NHCO-、-CON(CH3 )-、-NH-、-O-、-CH2 O-、 -COO-或-OCO-。A1 表示氧原子或-COO-*(附加「*」之鍵結處係與(CH2 )a2 鍵結)。A2 表示氧原子或*-COO-(附加「*」之鍵結處係與(CH2 )a2 鍵結)。a1 為0或1之整數,a2 為2~10之整數。Cy表示1,4-伸環已基或1,4-伸苯基。In the above formulas [S1-x1] to [S1-x7], R 1 is the same as in the case of the above formula [S1]. X p represents -(CH 2 ) a - (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH 3 )-, -NH-, -O-, -CH 2 O-, -COO- or -OCO-. A 1 represents an oxygen atom or -COO-* (the bond with "*" is bonded to (CH 2 ) a2 ). A 2 represents an oxygen atom or *-COO- (the bond with "*" is bonded with (CH 2 ) a2 ). a 1 is an integer of 0 or 1, and a 2 is an integer of 2-10. Cy represents 1,4-cyclohexylene or 1,4-phenylene.

[B]:具有下述式[S2]所示之特定側鏈構造之二胺

Figure 02_image049
上述式[S2]中,X3 表示單鍵、-CONH-、-NHCO-、 -CON(CH3 )-、-NH-、-O-、-CH2 O-、-COO-或-OCO-。其中,從液晶配向劑之液晶配向性之觀點,X3 係以-CONH-、 -NHCO-、-O-、-CH2 O-、-COO-或-OCO-為佳。[B]: Diamine having a specific side chain structure represented by the following formula [S2]
Figure 02_image049
In the above formula [S2], X 3 represents a single bond, -CONH-, -NHCO-, -CON(CH 3 )-, -NH-, -O-, -CH 2 O-, -COO- or -OCO- . Among them, from the viewpoint of the liquid crystal alignment of the liquid crystal alignment agent, X 3 is preferably -CONH-, -NHCO-, -O-, -CH 2 O-, -COO- or -OCO-.

又,上述式[S2]中,R2 表示碳數1~20之烷基或碳數2~20之烷氧基烷基。形成R2 之任意之氫係亦可經氟取代。其中,從液晶配向劑之液晶配向性之觀點,R2 係以碳數3~20之烷基或碳數2~20之烷氧基烷基為佳。Also, in the above formula [S2], R 2 represents an alkyl group having 1 to 20 carbons or an alkoxyalkyl group having 2 to 20 carbons. Any hydrogens forming R2 may also be substituted with fluorine. Among them, from the viewpoint of liquid crystal alignment of the liquid crystal alignment agent, R 2 is preferably an alkyl group with 3 to 20 carbons or an alkoxyalkyl group with 2 to 20 carbons.

[C]:具有下述式[S3]所示之特定側鏈構造之二胺

Figure 02_image051
上述式[S3]中,X4 表示-CONH-、-NHCO-、-O-、 -COO-或-OCO-。R3 表示具有類固醇骨架之構造。在此之類固醇骨架係具有3個六員環及1個五員環結合而成之下述式(st)所示之骨架。
Figure 02_image053
[C]: Diamine having a specific side chain structure represented by the following formula [S3]
Figure 02_image051
In the above formula [S3], X 4 represents -CONH-, -NHCO-, -O-, -COO- or -OCO-. R 3 represents a structure having a steroid skeleton. The steroid skeleton here has a skeleton represented by the following formula (st) in which three six-membered rings and one five-membered ring are combined.
Figure 02_image053

作為上述式[S3]之例,可舉出如下述式[S3-x]。

Figure 02_image055
As an example of said formula [S3], following formula [S3-x] is mentioned.
Figure 02_image055

上述式[S3-x]中,X表示上述式[X1]或[X2]。又,Col表示選自由上述式[Col1]~[Col4]所成群之至少1種,G表示上述式[G1]或[G2]。*表示與其他基之鍵結部位。In said formula [S3-x], X represents said formula [X1] or [X2]. Moreover, Col represents at least 1 sort(s) selected from the group which consists of said formula [Col1]-[Col4], and G represents said formula [G1] or [G2]. *Indicates the bonding site with other groups.

作為上述式[S3-x]中之X、Col及G之較佳組合之例,可舉出例如下述之組合。即,[X1]與[Col1]與[G1]、[X1]與[Col1]與[G2]、[X1]與[Col2]與[G1]、[X1]與[Col2]與[G2]、[X1]與[Col3]與[G2]、[X1]與[Col4]與[G2]、[X1]與[Col3]與[G1]、[X1]與[Col4]與[G1]、[X2]與[Col1]與[G2]、[X2]與[Col2]與[G2]、[X2]與[Col2]與[G1]、[X2]與[Col3]與[G2]、[X2]與[Col4]與[G2]、[X2]與[Col1]與[G1]、[X2]與[Col4]與[G1]。As an example of the preferable combination of X, Col, and G in said formula [S3-x], the following combination is mentioned, for example. That is, [X1] and [Col1] and [G1], [X1] and [Col1] and [G2], [X1] and [Col2] and [G1], [X1] and [Col2] and [G2], [X1] and [Col3] and [G2], [X1] and [Col4] and [G2], [X1] and [Col3] and [G1], [X1] and [Col4] and [G1], [X2] ] and [Col1] and [G2], [X2] and [Col2] and [G2], [X2] and [Col2] and [G1], [X2] and [Col3] and [G2], [X2] and [Col4] and [G2], [X2] and [Col1] and [G1], [X2] and [Col4] and [G1].

又,作為上述式[S3]之具體例,可舉出如從日本特開平4-281427號公報之段落[0024]記載之類固醇化合物去除羥基(羥基)後之構造,從同公報之段落[0030]記載之類固醇化合物去除酸氯基後之構造,從同公報之段落[0038]記載之類固醇化合物去除胺基後之構造,從同公報之段落[0042]記載之類固醇化合物去除鹵基後之構造,及日本特開平8-146421之段落[0018]~[0022]記載之構造等。Also, as a specific example of the above-mentioned formula [S3], a structure in which a hydroxyl group (hydroxyl group) has been removed from a steroid compound as described in paragraph [0024] of JP-A-4-281427, from paragraph [0030] of the same publication The structure of the steroid compound described in ] after removing the acid chlorine group, the structure after removing the amino group from the steroid compound described in paragraph [0038] of the same publication, and the structure after removing the halogen group from the steroid compound described in paragraph [0042] of the same publication , and the structures described in paragraphs [0018] to [0022] of Japanese Patent Application Laid-Open No. 8-146421, etc.

尚且,作為類固醇骨架之代表例,可舉出如膽固醇(上述式[S3-x]中之[Col1]及[G2]之組合),但也可利用不包含該膽固醇之類固醇骨架。即,作為具有類固醇骨架之二胺,可舉出例如3,5-二胺基安息香酸膽固烷基酯等,但也可作成不包含具有該膽固醇骨架之二胺之二胺成分。又,作為具有特定側鏈構造之二胺,也可利用二胺與側鏈之連結位置不包含醯胺者。即使利用此種二胺,在本實施形態中,即使利用不包含具有膽固醇骨架之二胺的二胺成分,仍能提供可取得經過長時間仍能確保高電壓保持率之液晶配向膜或液晶顯示元件的液晶配向劑。Furthermore, as a representative example of the steroid skeleton, cholesterol (combination of [Col1] and [G2] in the above formula [S3-x]) is mentioned, but a steroid skeleton not including this cholesterol can also be used. That is, examples of the diamine having a steroid skeleton include cholesteryl 3,5-diaminobenzoate and the like, but diamine components that do not contain the diamine having the cholesterol skeleton can also be used. Moreover, as a diamine which has a specific side chain structure, the thing which does not contain an amide can also be utilized in the linking position of a diamine and a side chain. Even if such a diamine is used, in this embodiment, even if a diamine component that does not contain a diamine having a cholesterol skeleton is used, it is possible to provide a liquid crystal alignment film or a liquid crystal display that can secure a high voltage retention rate over a long period of time. Liquid crystal alignment agent for components.

尚且,具有上述式[S1]~[S3]所示之側鏈構造之二胺係分別為如下述式[1-S1]-[1-S3]之構造所示者。

Figure 02_image057
上述式[1-S1]中,X1 、X2 、G1 、G2 、R1 、m及n係與上述式[S1]中之情況相同。上述式[1-S2]中,X3 及R2 係與上述式[S2]中之情況相同。上述式[1-S3]中,X4 及R3 係與上述式[S3]中之情況相同。Furthermore, diamines having a side chain structure represented by the above formulas [S1] to [S3] are represented by structures of the following formulas [1-S1] to [1-S3], respectively.
Figure 02_image057
In the above formula [1-S1], X 1 , X 2 , G 1 , G 2 , R 1 , m and n are the same as those in the above formula [S1]. In the above formula [1-S2], X 3 and R 2 are the same as those in the above formula [S2]. In the above formula [1-S3], X 4 and R 3 are the same as those in the above formula [S3].

<其他二胺:具有展現垂直配向性之二側鏈型之特性側鏈構造的二胺> 在使用作為VA方式之液晶顯示元件中之液晶配向劑時,亦可使用具有2個垂直配向性之特定側鏈構造之二側鏈型之二胺來調製特定聚合物。 可作為該二胺成分而包含之二側鏈二胺係例如下述式[1]所示者。

Figure 02_image059
<Other diamines: diamines having a characteristic side chain structure of a double side chain type exhibiting vertical alignment> When using as a liquid crystal alignment agent in a VA liquid crystal display element, one having two vertical alignment properties can also be used Two side chain type diamines with specific side chain structure can be used to prepare specific polymers. The two side chain diamine which can be contained as this diamine component is represented by following formula [1], for example.
Figure 02_image059

上述式[1]中,X表示單鍵、-O-、-C(CH3 )2 -、-NH-、-CO-、-NHCO-、-COO-、-(CH2 )m -、-SO2 -或由該等之任意組合所構成之2價有機基。其中,X係以單鍵、 -O-、-NH-、-O-(CH2 )m -O-為佳。作為「該等之任意組合」之例,可舉出如-O-(CH2 )m -O-、-O-C(CH3 )2 -、-CO-(CH2 )m -、-NH-(CH2 )m -、-SO2 -(CH2 )m -、-CONH-(CH2 )m -、-CONH-(CH2 )m -NHCO-、-COO-(CH2 )m -OCO-等。m為1~8之整數。 又,上述式[1]中,2個Y係各自獨立表示下述式[1-1]之構造。

Figure 02_image061
In the above formula [1], X represents a single bond, -O-, -C(CH 3 ) 2 -, -NH-, -CO-, -NHCO-, -COO-, -(CH 2 ) m -, - SO 2 -or a divalent organic group formed by any combination of these. Among them, X is preferably a single bond, -O-, -NH-, -O-(CH 2 ) m -O-. Examples of "any combination of these" include -O-(CH 2 ) m -O-, -OC(CH 3 ) 2 -, -CO-(CH 2 ) m -, -NH-( CH 2 ) m -, -SO 2 -(CH 2 ) m -, -CONH-(CH 2 ) m -, -CONH-(CH 2 ) m -NHCO-, -COO-(CH 2 ) m -OCO- wait. m is an integer of 1-8. Moreover, in the said formula [1], two Ys represent the structure of following formula [1-1] each independently.
Figure 02_image061

上述式[1-1]中,Y1 及Y3 係各自獨立表示單鍵、-(CH2 )a -(a為1~15之整數)、-O-、-CH2 O-、-COO-或 -OCO-。Y2 表示單鍵或-(CH2 )b -(b為1~15之整數)。但,Y1 或Y3 為單鍵或-(CH2 )a -時,Y2 為單鍵。又,Y1 為-O-、 -CH2 O-、-COO-或-OCO-,及/或Y3 為-O-、-CH2 O-、-COO-或-OCO-時,Y2 為單鍵或-(CH2 )b -。 又,式[1-1]中,Y4 表示選自由苯環、環己烷環及雜環所成群之至少1種之2價環狀基或具有類固醇骨架之碳數17~51之2價有機基。形成該環狀基之任意之氫原子亦可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子所取代。In the above formula [1-1], Y 1 and Y 3 each independently represent 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 of 1 to 15). However, when Y 1 or Y 3 is a single bond or -(CH 2 ) a -, Y 2 is a single bond. Also, when Y 1 is -O-, -CH 2 O-, -COO- or -OCO-, and/or Y 3 is -O-, -CH 2 O-, -COO- or -OCO-, Y 2 is a single bond or -(CH 2 ) b -. In addition, in the formula [1-1], Y 4 represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocycle, or 2 of 17 to 51 carbons having a steroid skeleton. Valence organic base. Any hydrogen atom forming the cyclic group can also be replaced by an alkyl group with 1 to 3 carbons, an alkoxy group with 1 to 3 carbons, a fluorine-containing alkyl group with 1 to 3 carbons, or a fluorine-containing alkyl group with 1 to 3 carbons. substituted by fluoroalkoxy or fluorine atoms.

又,上述式[1-1]中,Y5 表示選自由苯環、環己烷環及雜環所成群之至少1種環狀基。形成該環狀基之任意之氫原子亦可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子所取代。 又,上述式[1-1]中,Y6 表示選自由碳數1~18之烷基、碳數2~18之烯基、碳數1~18之含氟烷基、碳數1~18之烷氧基及碳數1~18之含氟烷氧基所成群之至少1種。n為0~4之整數。In addition, in the above formula [1-1], Y 5 represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocycle. Any hydrogen atom forming the cyclic group can also be replaced by an alkyl group with 1 to 3 carbons, an alkoxy group with 1 to 3 carbons, a fluorine-containing alkyl group with 1 to 3 carbons, or a fluorine-containing alkyl group with 1 to 3 carbons. substituted by fluoroalkoxy or fluorine atoms. In addition, in the above formula [1-1], Y 6 represents an alkyl group selected from an alkyl group having 1 to 18 carbons, an alkenyl group having 2 to 18 carbons, a fluorine-containing alkyl group having 1 to 18 carbons, an alkyl group having 1 to 18 carbons at least one of the group consisting of an alkoxy group having 1 to 18 carbon atoms and a fluorine-containing alkoxy group. n is an integer of 0-4.

又,上述式[1]中,Y在從X之位置來看可為間位亦可為鄰位,較佳係以鄰位為宜。即,上述式[1]係以下述式[1’]為佳。

Figure 02_image063
Also, in the above formula [1], Y can be in the meta position or in the ortho position when viewed from the position of X, preferably in the ortho position. That is, the above-mentioned formula [1] is preferably the following formula [1'].
Figure 02_image063

又,上述式[1]中,2個胺基(-NH2 )之位置可為在苯環上之任意位置,以下述式[1]-a1~[1]-a3所示之位置為佳,以下述式[1]-a1為較佳。下述式中,X係與上述式[1]中之情況相同。尚且,下述式[1]-a1~[1]-a3為說明2個胺基之位置者,故省略上述式[1]中所示之Y之記號。

Figure 02_image065
Also, in the above formula [1], the positions of the two amino groups (-NH 2 ) can be any position on the benzene ring, and the positions shown in the following formulas [1]-a1 to [1]-a3 are preferred , the following formula [1]-a1 is preferred. In the following formula, X is the same as in the above formula [1]. Furthermore, the following formulas [1]-a1 to [1]-a3 are for explaining the positions of two amino groups, so the symbol of Y shown in the above-mentioned formula [1] is omitted.
Figure 02_image065

因此,若基於上述式[1’]及[1]-a1~[1]-a3,上述式[1]係以選自下述式[1]-a1-1~[1]-a3-2之任一之構造為佳,以下述式[1]-a1-1所示之構造為較佳。下述式中,X及Y係分別與式[1]中之情況相同。

Figure 02_image067
Therefore, if based on the above-mentioned formula [1'] and [1]-a1~[1]-a3, the above-mentioned formula [1] is selected from the following formulas [1]-a1-1~[1]-a3-2 Any one of the structures is preferable, and the structure represented by the following formula [1]-a1-1 is more preferable. In the following formula, X and Y are respectively the same as those in the formula [1].
Figure 02_image067

又,作為上述式[1-1]之例,可舉出如下述式[1-1]-1~[1-1]-22。其中,作為上述式[1-1]之例,以下述式[1-1]-1~[1-1]-4、[1-1]-8或[1-1]-10為佳。尚且,下述式中,*表示與上述式[1]、[1’]及[1]-a1~[1]-a3中之苯基之鍵結位置。

Figure 02_image069
Moreover, as an example of said formula [1-1], following formula [1-1]-1-[1-1]-22 is mentioned. Among them, the following formulas [1-1]-1 to [1-1]-4, [1-1]-8, or [1-1]-10 are preferable as examples of the formula [1-1]. In addition, in the following formula, * represents the bonding position with the phenyl group in said formula [1], [1'] and [1]-a1-[1]-a3.
Figure 02_image069

Figure 02_image071
Figure 02_image071

二胺成分藉由含有具有規定構造之二側鏈二胺,而成為即使在受到過度加熱之情況,使液晶垂直配向之能力仍變得不易降低之液晶配向膜。又,二胺成分藉由含有該二側鏈二胺,也會成為即使在膜與任何之異物接觸且受到損傷之際,使液晶垂直配向能力仍變得不易降低之液晶配向膜。即,二胺成分藉由含有該二側鏈二胺,而變得能提供可取得各種上述特性優異之液晶配向膜之液晶配向劑。The diamine component contains diamines having two side chains having a predetermined structure, thereby forming a liquid crystal alignment film in which the ability to vertically align liquid crystals does not easily decrease even when overheated. Moreover, when a diamine component contains this diamine of two side chains, even if a film contacts with any foreign matter and is damaged, it becomes a liquid crystal alignment film which does not reduce the vertical alignment ability of a liquid crystal so easily. That is, a diamine component can provide the liquid crystal aligning agent which can acquire the liquid crystal aligning film excellent in various said characteristics by containing this diamine of two side chains.

<其他二胺:具有光反應性側鏈之二胺> 使用作為PSA方式之液晶顯示元件中之液晶配向劑時,以提高聚合性化合物之反應性為目的,亦可使用具有光反應性側鏈之二胺來調製特定聚合物。 該二胺成分亦可含有具有光反應性側鏈之二胺作為其他二胺。二胺成分藉由含有具有光反應性側鏈之二胺,變得能對特定聚合物或其以外之聚合物導入光反應性側鏈。<Other diamines: diamines with photoreactive side chains> When using it as a liquid crystal alignment agent in a PSA type liquid crystal display element, for the purpose of improving the reactivity of a polymerizable compound, a specific polymer may be prepared using a diamine having a photoreactive side chain. This diamine component may contain the diamine which has a photoreactive side chain as another diamine. The diamine component can introduce a photoreactive side chain into a specific polymer or other polymers by containing the diamine which has a photoreactive side chain.

作為具有光反應性側鏈之二胺,可舉出例如下述式[VIII]或[IX]所示者。

Figure 02_image073
As a diamine which has a photoreactive side chain, what is represented by following formula [VIII] or [IX] is mentioned, for example.
Figure 02_image073

上述式[VIII]及[IX]中,2個胺基(-NH2 )之位置可為苯環上之任一位置,可舉出例如相對於側鏈之鍵結基而言,苯環上之2,3之位置、2,4之位置、2,5之位置、2,6之位置、3,4之位置或3,5之位置。從合成聚醯胺酸之際之反應性的觀點,以2,4之位置、2,5之位置或3,5之位置為佳。若加上合成二胺之際之容易性之觀點時,以2,4之位置或3,5之位置為較佳。In the above formulas [VIII] and [IX], the positions of the two amino groups (-NH 2 ) can be any position on the benzene ring, for example, with respect to the bonding group of the side chain, on the benzene ring The 2,3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 position or 3,5 position. The 2,4 position, the 2,5 position, or the 3,5 position are preferable from the viewpoint of the reactivity at the time of polyamide acid synthesis. From the viewpoint of the ease of synthesizing diamine, the 2,4 position or the 3,5 position is preferable.

又,上述式[VIII]中,R8 表示單鍵、-CH2 -、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH2 O-、-N(CH3 )-、-CON(CH3 )-或-N(CH3 )CO-。尤其,R8 係以單鍵、-O-、-COO-、-NHCO-或-CONH-為佳。In addition, in the above formula [VIII], R 8 represents a single bond, -CH 2 -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH 2 O-, -N(CH 3 )-, -CON(CH 3 )- or -N(CH 3 )CO-. In particular, R 8 is preferably a single bond, -O-, -COO-, -NHCO- or -CONH-.

又,上述式[VIII]中,R9 表示單鍵或可經氟原子取代之碳數1~20之伸烷基。在此之伸烷基之-CH2 -係可任意地被-CF2 -或-CH=CH-所取代,在不與以下之任意之基互為相鄰時,亦可被該等之基所取代;-O-、-COO-、 -OCO-、-NHCO-、-CONH-、-NH-、二價之碳環或雜環。尚且,該二價之碳環或雜環係具體地可例示如下述式(1a)者。

Figure 02_image075
Also, in the above formula [VIII], R 9 represents a single bond or an alkylene group having 1 to 20 carbon atoms which may be substituted by a fluorine atom. The -CH 2 - of the alkylene group here can be optionally substituted by -CF 2 - or -CH=CH-, and when it is not adjacent to any of the following groups, it can also be replaced by these groups Substituted; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, divalent carbocycle or heterocycle. Furthermore, the divalent carbocyclic or heterocyclic ring system can specifically be exemplified by the following formula (1a).
Figure 02_image075

又,上述式[VIII]中,R9 係能以通常之有機合成手法使其形成,在從合成容易性之觀點,以單鍵或碳數1~12之伸烷基為佳。Also, in the above formula [VIII], R 9 can be formed by common organic synthesis techniques, and from the viewpoint of ease of synthesis, a single bond or an alkylene group having 1 to 12 carbons is preferable.

又,上述式[VIII]中,R10 表示選自由下述式(1b)所成群之光反應性基。其中,R10 從光反應性之觀點,以甲基丙烯醯基、丙烯醯基或乙烯基為佳。

Figure 02_image077
In addition, in the above-mentioned formula [VIII], R 10 represents a photoreactive group selected from the group consisting of the following formula (1b). Among them, R 10 is preferably methacryl, acryl or vinyl from the viewpoint of photoreactivity.
Figure 02_image077

又,上述式[IX]中,Y1 表示-CH2 -、-O-、 -CONH-、-NHCO-、-COO-、-OCO-、-NH-或-CO-。Y2 表示碳數1~30之伸烷基、二價之碳環或雜環。在此之伸烷基、二價之碳環或雜環中之1個或複數之氫原子係可被氟原子或有機基所取代。Y2 在以下之基不互為相鄰時, -CH2 -亦可被該等之基所取代;-O-、-NHCO-、-CONH-、 -COO-、-OCO-、-NH-、-NHCONH-、-CO-。In addition, in the above formula [IX], Y 1 represents -CH 2 -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH- or -CO-. Y 2 represents an alkylene group having 1 to 30 carbon atoms, a divalent carbocyclic ring or a heterocyclic ring. One or more hydrogen atoms in the alkylene group, divalent carbocyclic ring or heterocyclic ring may be substituted by fluorine atoms or organic groups. When Y 2 is not adjacent to each other, -CH 2 - can also be substituted by these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH- , -NHCONH-, -CO-.

又,上述式[IX]中,Y3 表示-CH2 -、-O-、 -CONH-、-NHCO-、-COO-、-OCO-、-NH-、-CO-或單鍵。Y4 表示桂皮醯基。Y5 表示單鍵、碳數1~30之伸烷基、二價之碳環或雜環。在此之伸烷基、二價之碳環或雜環中之1個或複數之氫原子亦可被氟原子或有機基所取代。Y5 在以下之基不互為相鄰時,-CH2 -亦可被該等之基所取代;-O-、-NHCO-、-CONH-、-COO-、-OCO-、-NH-、 -NHCONH-、-CO-。Y6 表示丙烯醯基或甲基丙烯醯基等之光聚合性基。In addition, in the above formula [IX], Y 3 represents -CH 2 -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO- or a single bond. Y 4 represents a cinnamyl group. Y 5 represents a single bond, an alkylene group having 1 to 30 carbon atoms, or a divalent carbocyclic or heterocyclic ring. One or more hydrogen atoms in the alkylene group, divalent carbocyclic ring or heterocyclic ring may be substituted by a fluorine atom or an organic group. When Y 5 is not adjacent to each other, -CH 2 - can also be substituted by these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH- , -NHCONH-, -CO-. Y6 represents a photopolymerizable group such as an acryl group or a methacryl group.

作為該種具有上述式[VIII]或[IX]所示之光反應性側鏈之二胺之具體例,可舉出如下述式(1c)。

Figure 02_image079
上述式(1c)中,X9 及X10 係各自獨立表示單鍵、-O-、 -COO-、-NHCO-或-NH-之鍵結基。Y表示可經氟原子取代之碳數1~20之伸烷基。As a specific example of the diamine which has the photoreactive side chain represented by the said formula [VIII] or [IX], the following formula (1c) is mentioned.
Figure 02_image079
In the above formula (1c), X 9 and X 10 each independently represent a single bond, -O-, -COO-, -NHCO- or -NH-bonding group. Y represents an alkylene group having 1 to 20 carbons which may be substituted by a fluorine atom.

作為具有光反應性側鏈之二胺,也可舉出如下述式[VII]之二胺。式[VII]之二胺係在側鏈具有自由基產生構造之部位。自由基產生構造係藉由紫外線照射進行分解而產生自由基。

Figure 02_image081
上述式[VII]中,Ar表示選自由伸苯基、伸萘基及伸聯苯基所成群之至少1種芳香族烴基,該等環之氫原子亦可被鹵素原子所取代。羰基所鍵結之Ar由於參與紫外線之吸收波長,故在長波長化之情況,以伸萘基或伸聯苯基般之共軛長度為長之構造為佳。另一方面,Ar在成為伸萘基或伸聯苯基般之構造時,有溶解性變差之情況,於此情況下,合成難易度變高。紫外線之波長若在250nm~380nm之範圍,即便為苯基仍能取得充分特性,故Ar係以苯基為最佳。As diamine which has a photoreactive side chain, the diamine of following formula [VII] is also mentioned. The diamine of the formula [VII] has a radical generating structure in the side chain. The free radical generating structure is decomposed by ultraviolet irradiation to generate free radicals.
Figure 02_image081
In the above formula [VII], Ar represents at least one aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene, and the hydrogen atoms of these rings may be replaced by halogen atoms. Since the Ar bonded by the carbonyl group participates in the absorption wavelength of ultraviolet rays, in the case of a longer wavelength, a structure with a long conjugation length such as naphthyl or biphenyl is preferable. On the other hand, when Ar has a structure such as naphthyl or biphenyl, the solubility may deteriorate, and in this case, the difficulty of synthesis becomes high. If the wavelength of ultraviolet light is in the range of 250nm to 380nm, sufficient characteristics can be obtained even if it is phenyl, so phenyl is the best Ar system.

上述Ar中,芳香族烴基上亦可設有取代基。作為在此之取代基之例,以烷基、羥基、烷氧基、胺基等、電子供給性之有機基為佳。In the above-mentioned Ar, a substituent may be provided on the aromatic hydrocarbon group. Examples of the substituent here are preferably electron-donating organic groups such as alkyl groups, hydroxyl groups, alkoxy groups, and amino groups.

又,上述式[VII]中,R1 及R2 係各自獨立表示碳原子數1~10之烷基、烷氧基、苄基或苯乙基。在烷基或烷氧基之情況,亦可藉由R1 及R2 來形成環。In addition, in the above formula [VII], R 1 and R 2 each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group or a phenethyl group. In the case of an alkyl or alkoxy group, a ring may also be formed by R 1 and R 2 .

又,上述式[VII]中,T1 及T2 係各自獨立表示單鍵、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、 -CH2 O-、-N(CH3 )-、-CON(CH3 )-或-N(CH3 )CO-之鍵結基。In addition, in the above formula [VII], T1 and T2 each independently represent a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH 2 O- , -N(CH 3 )-, -CON(CH 3 )- or -N(CH 3 )CO- bonding group.

又,式[VII]中,S表示單鍵、非取代或被氟原子取代之碳原子數1~20之伸烷基。在此之伸烷基之 -CH2 -或-CF2 -亦可任意被-CH=CH-取代,以下列舉之任意之基在互不相鄰時,亦可被該等之基所取代;-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、二價之碳環、二價之雜環。Also, in formula [VII], S represents a single bond, unsubstituted or fluorine atom-substituted C1-C20 alkylene group. The -CH 2 - or -CF 2 - of the alkylene group here can also be optionally substituted by -CH=CH-, any of the groups listed below can also be substituted by these groups when they are not adjacent to each other; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, divalent carbocycle, and divalent heterocycle.

又,式[VII]中,Q表示選自下述式(1d)之構造。

Figure 02_image083
上述式(1d)中,R表示氫原子或碳原子數1~4之烷基。R3 表示-CH2 -、-NR-、-O-、或-S-。In addition, in formula [VII], Q represents a structure selected from the following formula (1d).
Figure 02_image083
In the above formula (1d), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 3 represents -CH 2 -, -NR-, -O-, or -S-.

又,上述式[VII]中,Q係以電子供給性之有機基為佳,以上述Ar之例所舉出之烷基、羥基、烷氧基、胺基等為佳。Q為胺基衍生物時,在聚醯亞胺前驅物即聚醯胺酸之聚合之際,由於有所產生之羧酸基與胺基形成鹽等之不良情況產生之可能性,故以羥基或烷氧基為較佳。In addition, in the above formula [VII], Q is preferably an electron-donating organic group, preferably an alkyl group, a hydroxyl group, an alkoxy group, an amino group, etc. as mentioned above as examples of Ar. When Q is an amino derivative, when the polyimide precursor, that is, polyamic acid, is polymerized, due to the possibility of undesirable situations such as the formation of a salt between the carboxylic acid group and the amine group, the hydroxyl group Or alkoxy is preferred.

又,上述式[VII]中,2個胺基(-NH2 )之位置可為o-伸苯基二胺、m-伸苯基二胺或p-伸苯基二胺之任一者,從與酸二酐之反應性之觀點,以m-伸苯基二胺或p-伸苯基二胺為佳。Also, in the above formula [VII], the positions of the two amine groups (-NH 2 ) may be any of o-phenylenediamine, m-phenylenediamine, or p-phenylenediamine, From the viewpoint of reactivity with acid dianhydride, m-phenylenediamine or p-phenylenediamine is preferable.

因此,作為上述式[VII]之較佳具體例,從合成容易度、泛用性之高度、特性等之觀點,可舉出如下述式。尚且,下述式中,n為2~8之整數。

Figure 02_image085
Therefore, as a preferable specific example of the said formula [VII], the following formula can be mentioned from viewpoints, such as synthesis|combination easiness, the height of versatility, and a characteristic. In addition, in the following formulae, n is an integer of 2-8.
Figure 02_image085

具有該等上述式[VII]、[VIII]或[IX]所示之光反應性側鏈之二胺係可單獨使用1種或可混合2種以上使用。因應作成液晶配向膜時之液晶配向性、預傾角、電壓保持特性、蓄積電荷等之特性、作成液晶顯示元件時之液晶之應答速度等來單獨使用1種或混合2種以上使用,並且在混合2種以上使用,其之比例等適宜調整即可。The diamines which have the photoreactive side chain represented by the said formula [VII], [VIII] or [IX] can be used individually by 1 type or in mixture of 2 or more types. According to the characteristics of liquid crystal alignment, pre-tilt angle, voltage retention characteristics, accumulated charge, etc. when making liquid crystal alignment films, and the response speed of liquid crystals when making liquid crystal display elements, etc., use alone or in combination of two or more types, and when mixed Two or more kinds are used, and the ratio thereof may be adjusted as appropriate.

<其他二胺:上述以外之二胺> 取得特定聚合物用之二胺成分可包含之上述以外之二胺並不受限於具有上述特定構造之二胺等。作為該等之上述以外之二胺之例,可舉出如下述式[2]所示者。

Figure 02_image087
<Other diamines: diamines other than those mentioned above> Diamines other than those mentioned above that may be included in the diamine component for obtaining a specific polymer are not limited to diamines having the above-mentioned specific structure. What is shown by following formula [2] is mentioned as an example of these diamines other than the above.
Figure 02_image087

上述式[2]中,A1 及A2 係各自獨立表示氫原子、碳數1~5之烷基、碳數2~5之烯基或碳數2~5之炔基。其中,從單體之反應性之觀點,A1 及A2 係以氫原子或甲基為佳。又,若例示Y11 之構造,可舉出如下述式(Y-1)~(Y-178)。In the above formula [2], A 1 and A 2 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbons, an alkenyl group having 2 to 5 carbons, or an alkynyl group having 2 to 5 carbons. Among them, from the viewpoint of monomer reactivity, A1 and A2 are preferably hydrogen atoms or methyl groups. Also, if the structure of Y11 is exemplified, the following formulas (Y-1) to (Y-178) can be mentioned.

Figure 02_image089
Figure 02_image089

Figure 02_image091
Figure 02_image091

Figure 02_image093
Figure 02_image093

Figure 02_image095
Figure 02_image095

Figure 02_image097
Figure 02_image097

Figure 02_image099
Figure 02_image099

Figure 02_image101
Figure 02_image101

Figure 02_image103
Figure 02_image103

Figure 02_image105
Figure 02_image105

Figure 02_image107
Figure 02_image107

Figure 02_image109
Figure 02_image109

Figure 02_image111
Figure 02_image111

Figure 02_image113
Figure 02_image113

Figure 02_image115
Figure 02_image115

Figure 02_image117
Figure 02_image117

Figure 02_image119
Figure 02_image119

Figure 02_image121
Figure 02_image121

Figure 02_image123
上述式中,對於n之範圍無特別記載者,則n為1~6之整數。又,上述式中,Me表示甲基。
Figure 02_image123
In the above formula, n is an integer of 1-6, unless there is a particular description about the range of n. In addition, in the above formula, Me represents a methyl group.

Figure 02_image125
Figure 02_image125

Figure 02_image127
上述式中,Boc表示tert-丁氧基羰基。
Figure 02_image127
In the above formula, Boc represents tert-butoxycarbonyl.

以上已說明之上述以外之二胺係可組合2種以上使用。二胺成分在含有上述以外之二胺時,特定聚合物中之相對於其他二胺之特定二胺係以特定二胺成為5~70mol%,較佳成為10~50mol%,更佳成為10~40mol%之量為宜。The diamines other than those described above can be used in combination of two or more. When the diamine component contains diamines other than the above, the specific diamine in the specific polymer relative to other diamines is 5 to 70 mol% of the specific diamine, preferably 10 to 50 mol%, more preferably 10 to 50 mol%. The amount of 40mol% is advisable.

本發明使用之聚醯亞胺前驅物係由二胺成分與四羧酸衍生物之反應而得者,可舉出如聚醯胺酸或聚醯胺酸酯等。 包含式(6)所示之構造單位之聚醯亞胺前驅物在同時包含式(7)所示之構造單位的情況,相對於式(6)與式(7)之合計而言,式(6)所示之構造單位係以10莫耳%以上為佳,較佳為20莫耳%以上,特佳為30莫耳%以上。 本發明使用之聚醯亞胺前驅物之分子量,其重量平均分子量係以2,000~500,000為佳,較佳為5,000~300,000,更佳為10,000~100,000。The polyimide precursor used in the present invention is obtained from the reaction of diamine components and tetracarboxylic acid derivatives, such as polyamic acid or polyamic acid ester. When the polyimide precursor comprising the structural unit shown in formula (6) contains the structural unit shown in formula (7) at the same time, with respect to the total of formula (6) and formula (7), the formula ( 6) The structural unit shown is preferably at least 10 mol%, more preferably at least 20 mol%, and most preferably at least 30 mol%. The molecular weight of the polyimide precursor used in the present invention is preferably 2,000-500,000, more preferably 5,000-300,000, more preferably 10,000-100,000.

作為在主鏈具有式(1)所示之2價基之聚醯亞胺,可舉出如使前述聚醯亞胺前驅物閉環而得之聚醯亞胺。此聚醯亞胺中,醯胺酸基之閉環率(亦稱為醯亞胺化率)並不必須為100%,可因應用途或目的而任意調整。 作為使聚醯亞胺前驅物醯亞胺化之方法,可舉出如直接加熱聚醯亞胺前驅物溶液之熱醯亞胺化,或對聚醯亞胺前驅物溶液添加觸媒之觸媒醯亞胺化。Examples of polyimides having a divalent group represented by the formula (1) in the main chain include polyimides obtained by ring-closing the aforementioned polyimide precursor. In this polyimide, the ring-closing rate of the amide acid group (also referred to as the imidization rate) does not have to be 100%, and can be adjusted arbitrarily according to the application or purpose. As a method for imidizing the polyimide precursor, thermal imidization by directly heating the polyimide precursor solution, or adding a catalyst to the polyimide precursor solution can be mentioned. imidization.

<液晶配向劑> 本發明之液晶配向劑含有上述之特定聚合物,但亦可含有2種以上相異構造之特定聚合物。又,除了含有特定聚合物,亦可含有其他聚合物,即亦可含有不具有式(1)所示之2價基之聚合物。作為聚合物之形式,可舉出如聚醯胺酸、聚醯亞胺、聚醯胺酸酯、聚酯、聚醯胺、聚脲、聚有機矽氧烷、纖維素衍生物、聚縮醛、聚苯乙烯或其衍生物、聚(苯乙烯-苯基馬來醯亞胺)衍生物、聚(甲基)丙烯酸酯等。本發明之液晶配向劑在含有其他聚合物時,相對於全聚合物成分之特定聚合物之比例係以5質量%以上為佳,可舉出例如5~95質量%。<Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention contains the above-mentioned specific polymers, but may also contain two or more specific polymers with different structures. Moreover, other polymers may be contained other than a specific polymer, ie, the polymer which does not have the divalent group represented by formula (1) may be contained. Examples of polymer forms include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivatives, polyacetal , polystyrene or its derivatives, poly(styrene-phenylmaleimide) derivatives, poly(meth)acrylate, etc. When the liquid crystal alignment agent of the present invention contains other polymers, the ratio of the specific polymer to the total polymer component is preferably 5% by mass or more, for example, 5 to 95% by mass.

液晶配向劑在從使均勻薄膜形成之觀點,一般係採用塗佈液之形態。本發明之液晶配向劑也係以含有上述聚合物成分與使該聚合物成分溶解之有機溶劑之塗佈液為佳。此時,液晶配向劑中之聚合物之濃度係可根據所欲形成之塗膜厚度之設定而適宜變更。從形成均勻且無缺陷之塗膜之觀點,以1質量%以上為佳,從溶液保存安定性之觀點,以10質量%以下為佳。特佳之聚合物之濃度為2~8質量%。From the viewpoint of forming a uniform thin film, the liquid crystal alignment agent is generally in the form of a coating solution. The liquid crystal alignment agent of the present invention is also preferably a coating liquid containing the above-mentioned polymer component and an organic solvent for dissolving the polymer component. At this time, the concentration of the polymer in the liquid crystal alignment agent can be appropriately changed according to the setting of the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, it is preferably at least 1% by mass, and from the viewpoint of solution storage stability, it is preferably at most 10% by mass. The concentration of the particularly preferred polymer is 2 to 8% by mass.

液晶配向劑所含有之有機溶劑只要係使聚合物成分均勻溶解者,即無特別限定。若舉出具體例,如N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、二甲亞碸、γ-丁內酯、1,3-二甲基-咪唑啉酮、甲基乙基酮、環己酮、環戊酮等。其中亦以使用N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、或γ-丁內酯為佳。The organic solvent contained in the liquid crystal alignment agent is not particularly limited as long as it dissolves the polymer component uniformly. If specific examples are given, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone , Dimethylsulfone, γ-butyrolactone, 1,3-dimethyl-imidazolinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, etc. Among them, it is also preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone.

又,本發明之液晶配向劑所含有之有機溶劑係除了可使用上述溶劑,也可使用、塗佈液晶配向劑時之塗佈性或使塗膜之表面平滑性提升之溶劑。該有機溶劑之具體例係列舉出如下述。In addition, the organic solvent contained in the liquid crystal alignment agent of the present invention can be used in addition to the above-mentioned solvents, and can also be used to improve the applicability of the liquid crystal alignment agent or the surface smoothness of the coating film. Specific examples of the organic solvent are listed below.

可舉出例如,乙醇、異丙基醇、1-丁醇、2-丁醇、異丁基醇、tert-丁基醇、1-戊醇、2-戊醇、3-戊醇、2-甲基-1-丁醇、異戊基醇、tert-戊基醇、3-甲基-2-丁醇、新戊基醇、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、2,6-二甲基-4-庚醇、1,2-乙烷二醇、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-已二醇、二異丙基醚、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、4-羥基-4-甲基-2-戊酮、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、2,6-二甲基-4-庚酮、4,6-二甲基-2-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、碳酸伸丙酯、碳酸伸乙酯、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、糠基醇、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、二乙二醇單乙基醚、二乙二醇單甲基醚、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-丁基酯、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-乙氧基丙酸乙酯、3-乙氧基丙酸甲基乙基、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙基、3-甲氧基丙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸n-丙基酯、乳酸n-丁基酯、乳酸異戊基酯、上述式[D-1]~[D-3]所示之溶劑等。Examples include ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2- Methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 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, 2,6-dimethyl-4-heptanol, 1,2-ethyl Alkanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1, 5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, diisopropyl ether, 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, di Ethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone , 2-hexanone, 2-heptanone, 4-heptanone, 2,6-dimethyl-4-heptanone, 4,6-dimethyl-2-heptanone, 3-ethoxybutyl ethyl ester, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, biscarbonate Propyl ester, ethyl carbonate, 2-(methoxymethoxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy ) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1-(butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, diethylene glycol mono Ethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetic acid Esters, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate ester, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol mono Methyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, pyruvate ethyl ester, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methylethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Propionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate Lactate, isoamyl lactate, solvents represented by the above formulas [D-1] to [D-3], etc.

其中,有機溶劑係以使用1-己醇、環己醇、1,2-乙烷二醇、1,2-丙二醇、丙二醇單丁基醚、二乙二醇二乙基醚、4-羥基-4-甲基-2-戊酮、乙二醇單丁基醚或二丙二醇二甲基醚為佳。此種溶劑之種類及含量係因應液晶配向劑之塗佈裝置、塗佈條件、塗佈環境等而適宜選擇。Among them, the organic solvent is based on the use of 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propylene glycol, propylene glycol monobutyl ether, diethylene glycol diethyl ether, 4-hydroxy- 4-Methyl-2-pentanone, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether are preferred. The type and content of the solvent are appropriately selected according to the coating device, coating conditions, and coating environment of the liquid crystal alignment agent.

本發明之液晶配向劑亦可追加含有聚合物成分及有機溶劑以外之成分。作為此種追加成分,可舉出如提高液晶配向膜與基板之密著性或液晶配向膜與密封材之密著性用之密著助劑、提高液晶配向膜強度用之交聯劑、調整液晶配向膜之介電率或電阻用之介電體或導電物質等。作此等追加成分之具體例,可舉出如國際公開第2015/060357號第53頁段落[0104]~60頁段落[0116]揭示之貧溶劑或交聯性化合物。The liquid crystal alignment agent of the present invention may additionally contain components other than the polymer component and the organic solvent. Such additional components include, for example, adhesion aids for improving the adhesion between the liquid crystal alignment film and the substrate or the adhesion between the liquid crystal alignment film and the sealing material, crosslinking agents for improving the strength of the liquid crystal alignment film, adjusting Dielectric or conductive substances for dielectric rate or resistance of liquid crystal alignment film. Specific examples of these additional components include poor solvents or cross-linking compounds as disclosed in paragraph [0104] on page 53 to paragraph [0116] on page 60 of International Publication No. 2015/060357.

作為提升液晶配向膜與基板之密著性之化合物,可舉出如含官能性矽烷之化合物或含環氧基之化合物,可舉出例如,3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、N-乙氧基羰基-3-胺基丙基三甲氧基矽烷、N-乙氧基羰基-3-胺基丙基三乙氧基矽烷、N-三乙氧基矽基丙基三伸基乙三胺、N-三甲氧基矽基丙基三伸乙基三胺、10-三甲氧基矽基-1,4,7-三氮雜癸烷、10-三乙氧基矽基-1,4,7-三氮雜癸烷、9-三甲氧基矽基-3,6-二氮雜壬基乙酸酯、9-三乙氧基矽基-3,6-二氮雜壬基乙酸酯、N-苄基-3-胺基丙基三甲氧基矽烷、N-苄基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-雙(氧乙烯)-3-胺基丙基三甲氧基矽烷、N-雙(氧乙烯)-3-胺基丙基三乙氧基矽烷、乙二醇二環氧丙基醚、聚乙二醇二環氧丙基醚、丙二醇二環氧丙基醚、三丙二醇二環氧丙基醚、聚丙二醇二環氧丙基醚、新戊二醇二環氧丙基醚、1,6-已二醇二環氧丙基醚、丙三醇二環氧丙基醚、2,2-二溴新戊二醇二環氧丙基醚、1,3,5,6-四環氧丙基-2,4-已二醇、N,N,N’,N’,-四環氧丙基-m-二甲苯二胺、1,3-雙(N,N-二環氧丙基胺基甲基)環己烷或N,N,N’,N’,-四環氧丙基-4、4’-二胺基二苯基甲烷等。As the compound that enhances the adhesion between the liquid crystal alignment film and the substrate, compounds containing functional silanes or compounds containing epoxy groups can be mentioned, for example, 3-aminopropyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-Glycidoxypropyltriethoxysilane, 3-Glycidoxypropyltrimethoxysilane, 3-Glycidoxypropylmethyl Diethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane , N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N -Ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltrienylethyl Triamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1, 4,7-Triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl ethyl Ester, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxy Silane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-amino Propyltriethoxysilane, Ethylene Glycol Diglycidyl Ether, Polyethylene Glycol Diglycidyl Ether, Propylene Glycol Diglycidyl Ether, Tripropylene Glycol Diglycidyl Ether, Polypropylene Glycol Diglycidyl Ether Oxypropyl Ether, Neopentyl Glycol Diglycidyl Ether, 1,6-Hexanediol Diglycidyl Ether, Glycerol Diglycidyl Ether, 2,2-Dibromoneopentyl Glycol Diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylene Diamine, 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane or N,N,N',N',-tetraepoxypropyl-4,4'-di Aminodiphenylmethane, etc.

又,本發明之液晶配向劑為了提升液晶配向膜之機械強度,亦可含有如以下之添加物。

Figure 02_image129
Moreover, in order to improve the mechanical strength of the liquid crystal alignment film, the liquid crystal alignment agent of the present invention may also contain the following additives.
Figure 02_image129

相對於液晶配向劑所含有之聚合物成分之100質量份,上述之添加劑係以0.1~30質量份為佳。由於未滿0.1質量份時則無法期待效果,超過30質量份時則液晶之配向性降低,故較佳為0.5~20質量份。The amount of the above-mentioned additives is preferably 0.1-30 parts by mass relative to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent. Since the effect cannot be expected when it is less than 0.1 mass parts, and since the alignment property of a liquid crystal will fall when it exceeds 30 mass parts, it is preferable that it is 0.5-20 mass parts.

本發明之液晶配向劑除了上述之外,亦可含有本發明記載之特定聚合物以外之聚合物、以使液晶配向膜之介電率或導電性等之電特性變化為目的之介電體、以提升液晶配向膜與基板之密著性為目的之矽烷耦合劑、以提高作成液晶配向膜時之膜硬度或緻密度為目的之交聯性化合物,以及在煆燒塗膜時以使聚醯亞胺前驅物之因加熱所成之醯亞胺化有效進行為目的之醯亞胺化促進劑等。In addition to the above, the liquid crystal alignment agent of the present invention may also contain polymers other than the specific polymers described in the present invention, dielectrics for the purpose of changing the electrical characteristics such as the dielectric constant or conductivity of the liquid crystal alignment film, A silane coupling agent for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate, a cross-linking compound for the purpose of increasing the film hardness or density when making a liquid crystal alignment film, and a polyamide compound used for kneading the coating film Accelerators for imidization of imine precursors for the purpose of efficient imidization by heating.

<液晶配向膜> 本發明之液晶配向膜係由前述液晶配向劑所得者。若例舉由液晶配向劑取得液晶配向膜之方法之一例,可舉出如對於將塗佈液形態之液晶配向劑塗佈於基板並進行乾燥、煆燒而得之膜,以摩擦處理法或光配向處理法施加配向處理之方法。尚且,VA方式中,亦可不施加配向處理而直接使用。<Liquid crystal alignment film> The liquid crystal alignment film of the present invention is obtained from the aforementioned liquid crystal alignment agent. If one example of the method of obtaining a liquid crystal alignment film from a liquid crystal alignment agent is given, for example, for a film obtained by applying a liquid crystal alignment agent in the form of a coating liquid to a substrate, drying, and sintering, rubbing treatment or Photo-alignment treatment method A method of applying alignment treatment. In addition, in the VA system, it can also be used as it is without applying an alignment treatment.

作為塗佈液晶配向劑之基板,只要係高透明性之基板即無特別限定,可使用玻璃基板、氮化矽基板,以及丙烯酸基板、聚碳酸酯基板等之塑料基板等。於此之際,若使用已形成使液晶驅動用之ITO電極等之基板時,從製程簡易化之觀點為佳。又,反射型之液晶顯示元件中,若僅為單側之基板,即使係矽晶圓等之不透明之物也可使用,此時之電極也可使用鋁等之反射光之材料。The substrate on which the liquid crystal alignment agent is applied is not particularly limited as long as it is a highly transparent substrate, and plastic substrates such as glass substrates, silicon nitride substrates, acrylic substrates, and polycarbonate substrates can be used. On this occasion, it is preferable from the viewpoint of process simplification to use a substrate on which ITO electrodes and the like for driving liquid crystals have been formed. In addition, in reflective liquid crystal display elements, if only one side of the substrate is used, even opaque objects such as silicon wafers can be used. At this time, light-reflecting materials such as aluminum can also be used for the electrodes.

液晶配向劑之塗佈方法在工業上一般為網版印刷、平板印刷、柔版印刷、噴墨法等。作為其他塗佈方法,如有浸漬法、輥塗佈法、狹縫塗佈法、旋塗法、噴霧法等,因應目的亦可使用該等。The coating method of liquid crystal alignment agent is generally screen printing, offset printing, flexo printing, inkjet method, etc. in the industry. As other coating methods, there are a dipping method, a roll coater method, a slit coater method, a spin coater method, a spray method, etc., and these can also be used according to the objective.

將液晶配向劑塗佈基板上後,藉由加熱板、熱循環型烤箱、IR(紅外線)型烤箱等之加熱手段使溶劑蒸發並進行煆燒。塗佈液晶配向劑後之乾燥、煆燒步驟係能選擇任意之溫度與時間。並不一定需要乾燥之步驟,但從塗佈後到煆燒為止之時間在整個基板並未固定之情況,或塗佈後並未隨及煆燒之情況,則以實施乾燥步驟為佳。此乾燥係將溶劑去除至基板藉由搬送等而不會導致塗膜形狀變形之程度即可,關於該乾燥手段,可舉出例如,在溫度40℃~150℃,較佳60℃~100℃之加熱板上,乾燥0.5分~30分,較佳乾燥1分~5分之方法。After the liquid crystal alignment agent is coated on the substrate, the solvent is evaporated and burned by heating means such as a heating plate, a thermal circulation oven, and an IR (infrared) oven. The drying and sintering steps after coating the liquid crystal alignment agent can choose any temperature and time. The drying step is not necessarily required, but if the entire substrate is not fixed in the time from coating to firing, or if the coating is not followed by firing, it is preferable to perform the drying step. This drying is to remove the solvent to the extent that the shape of the coating film will not be deformed by conveying the substrate. As for the drying means, for example, at a temperature of 40°C to 150°C, preferably at a temperature of 60°C to 100°C On the heating plate, dry for 0.5 minutes to 30 minutes, preferably for 1 minute to 5 minutes.

藉由塗佈液晶配向劑而形成之塗膜之煆燒溫度為例如100~350℃,較佳為120~300℃,更佳為150℃~250℃。煆燒時間為5分~240分,較佳為10分~90分,更佳為20分~90分。加熱係能以通常公知之方法,例如以加熱板、熱風循環爐、紅外線爐等進行。 由於煆燒後之液晶配向膜之厚度若過薄時則有液晶顯示元件之信賴性降低之情況,以5~300nm為佳,以10~200nm為較佳。The firing temperature of the coating film formed by coating the liquid crystal alignment agent is, for example, 100-350°C, preferably 120-300°C, more preferably 150-250°C. The burning time is 5 minutes to 240 minutes, preferably 10 minutes to 90 minutes, more preferably 20 minutes to 90 minutes. Heating can be performed by a generally known method, such as a hot plate, a hot air circulation furnace, an infrared furnace, and the like. If the thickness of the liquid crystal alignment film after firing is too thin, the reliability of the liquid crystal display element may decrease, so it is preferably 5-300nm, more preferably 10-200nm.

在製造TN型、STN型、IPS型或FFS型之液晶顯示元件時,對以上述步驟來形成之塗膜實施賦予液晶配向能力之處理。作為配向能力賦予處理,可舉出如對塗膜以捲附有例如由尼龍、嫘縈、棉等之纖維所構成之布的輥朝向固定方向摩擦之摩擦處理,對塗膜照射偏光或非偏光放射線之光配向處理等。另一方面,在製造VA型液晶顯示元件時,可直接將以上述步驟形成之塗膜使用作為液晶配向膜,亦可對該塗膜施以配向能力賦予處理。When manufacturing TN-type, STN-type, IPS-type or FFS-type liquid crystal display elements, the coating film formed by the above-mentioned steps is subjected to the treatment of imparting liquid crystal alignment ability. Examples of alignment-imparting treatment include rubbing the coating film in a fixed direction with a roller wrapped with a cloth made of fibers such as nylon, rayon, and cotton, and irradiating the coating film with polarized or non-polarized light. Radiation light alignment processing, etc. On the other hand, when manufacturing VA-type liquid crystal display elements, the coating film formed by the above steps can be directly used as a liquid crystal alignment film, and the coating film can also be subjected to alignment ability imparting treatment.

光配向處理中,作為對塗膜照射之放射線,可使用例如包含150~800nm之波長光線之紫外線及可見光線。放射線為偏光時,可為直線偏光亦可為部分偏光。又,所使用之放射線為直線偏光或部分偏光時,照射係可對基板面從垂直之方向來進行,可從斜面方向來進行,或亦可組合該等來進行。在照射非偏光之放射線時,照射之方向係設為斜面方向。 作為使用之光源,可使用例如低壓水銀燈、高壓水銀燈、氘燈、金屬鹵素燈、氬共振燈、氙氣燈、準分子雷射、LED燈等。較佳波長區域之紫外線係可藉由將光源與例如過濾器、繞射柵等併用之手段等而得。放射線之照射量係以100~50,000J/m2 為佳,較佳為300~20,000J/m2In the photo-alignment treatment, as the radiation irradiated to the coating film, for example, ultraviolet rays and visible rays including wavelength rays of 150 to 800 nm can be used. When the radiation is polarized, it may be linearly polarized or partially polarized. Also, when the radiation used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination thereof. When irradiating non-polarized radiation, the direction of irradiation is set as the oblique direction. As the light source used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, an LED lamp, or the like can be used. Ultraviolet rays in a preferable wavelength region can be obtained by means such as combining a light source with a filter, a diffraction grating, and the like. The radiation dose is preferably 100-50,000 J/m 2 , more preferably 300-20,000 J/m 2 .

又,對塗膜之光照射為了提高反應性,可加溫塗膜並同時進行。加溫時之溫度通常為30~250℃,以40~200℃為佳,較佳為50~150℃。 光配向處理係亦可在光照射時實施加熱處理,亦可在光配向處理後實施加熱處理。此時之加熱溫度係以80~300℃為佳,較佳為120~250℃。加熱時間係以5~200分為佳,較佳為10~100分。又,取代前述加熱處理,亦可進行使用有機溶劑或水之洗淨處理,亦可組合洗淨處理與加熱處理。In addition, the light irradiation to the coating film may be carried out simultaneously with heating the coating film in order to increase the reactivity. The temperature during heating is usually 30-250°C, preferably 40-200°C, more preferably 50-150°C. In the photo-alignment treatment system, heat treatment may be performed during light irradiation, or heat treatment may be performed after photo-alignment treatment. The heating temperature at this time is preferably 80-300°C, more preferably 120-250°C. The heating time is preferably 5-200 minutes, more preferably 10-100 minutes. Moreover, instead of the aforementioned heat treatment, washing treatment using an organic solvent or water may be performed, and washing treatment and heat treatment may be combined.

亦可對於摩擦處理後之液晶配向膜,更藉由對液晶配向膜之一部分照射紫外線,而使液晶配向膜之一部分之領域之預傾角變化之處理,或實施在液晶配向膜表面之一部分上形成抗蝕膜後,又在與先前之摩擦處理相異之方向上進行摩擦處理後去除抗蝕膜之處理,而使液晶配向膜根據領域而具有不同之液晶配向能力。於此情況,則能改善取得之液晶顯示元件之視野特性。It is also possible to treat the liquid crystal alignment film after the rubbing treatment by irradiating ultraviolet rays to a part of the liquid crystal alignment film to change the pretilt angle of a part of the liquid crystal alignment film, or implement a part of the surface of the liquid crystal alignment film to form After the resist film is removed, the process of removing the resist film after rubbing treatment is carried out in a direction different from the previous rubbing treatment, so that the liquid crystal alignment film has different liquid crystal alignment capabilities according to the field. In this case, the viewing characteristics of the obtained liquid crystal display element can be improved.

適宜VA型之液晶顯示元件之液晶配向膜也係能適宜使用於PSA(Polymer Sustained Alignment)型之液晶顯示元件。The liquid crystal alignment film suitable for VA-type liquid crystal display elements can also be suitably used for PSA (Polymer Sustained Alignment) type liquid crystal display elements.

本發明之液晶配向膜也適宜作為IPS方式或邊緣電場切換(FFS,Fringe Field Switching)方式等之橫向電場方式之液晶顯示元件之液晶配向膜,作為VA方式,特別係PSA模式之液晶顯示元件之液晶配向膜也極為有用。The liquid crystal alignment film of the present invention is also suitable as the liquid crystal alignment film of the liquid crystal display element of the transverse electric field method such as the IPS method or the fringe field switching (FFS, Fringe Field Switching) method, as the liquid crystal alignment film of the VA method, especially the liquid crystal display element of the PSA mode. Liquid crystal alignment films are also extremely useful.

<液晶顯示元件> 本發明之液晶顯示元件係在取得附有由上述液晶配向劑而得之液晶配向膜之基板後,以既知方法製作液晶單元,並利用該液晶單元而作成元件者。作為能製作液晶顯示元件之具體例,如具備液晶單元之液晶顯示元件,該液晶單元具有:呈對向配置之2枚基板,與設置於基板間之液晶層,及設置基板與液晶層之間之藉由本發明之液晶配向劑所形成之上述液晶配向膜。更具體而言,如藉由將本發明之液晶配向劑塗佈於2枚基板上並進行煆燒而形成液晶配向膜,以使此液晶配向膜成為對向之方式配置2枚基板,於此2枚基板之間挾持以液晶所構成之液晶層,即,使其與液晶配向膜接觸而設置液晶層之液晶顯示元件,在PSA模式下,更具備藉由對液晶配向膜及液晶層施加電壓並同時照射紫外線而製作之液晶單元之液晶顯示元件。<Liquid crystal display elements> The liquid crystal display element of the present invention is obtained by obtaining a substrate with a liquid crystal alignment film obtained from the above-mentioned liquid crystal alignment agent, producing a liquid crystal cell by a known method, and using the liquid crystal cell to make a device. As a specific example of a liquid crystal display element that can be manufactured, such as a liquid crystal display element with a liquid crystal unit, the liquid crystal unit has: two substrates arranged in opposite directions, a liquid crystal layer disposed between the substrates, and a liquid crystal layer disposed between the substrates and the liquid crystal layer The liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention. More specifically, if a liquid crystal alignment film is formed by coating the liquid crystal alignment agent of the present invention on two substrates and firing, the two substrates are arranged so that the liquid crystal alignment films are facing each other. A liquid crystal layer made of liquid crystal is sandwiched between two substrates, that is, a liquid crystal display element in which a liquid crystal layer is provided in contact with a liquid crystal alignment film. The liquid crystal display element of the liquid crystal unit produced by irradiating ultraviolet rays at the same time.

作為液晶單元之製作方法之一例,採用被動陣列構造之液晶顯示元件為例進行說明。具體而言,準備透明基板,其次在如前述之條件下,在各基板上形成液晶配向膜。基板係如上述般,通常為在基板上已形成使液晶驅動用之透明電極之基板。作為具體例,可舉出如與上述液晶配向膜所記載之基板為相同者。As an example of a method of manufacturing a liquid crystal cell, a liquid crystal display element using a passive matrix structure will be described as an example. Specifically, transparent substrates were prepared, and then a liquid crystal alignment film was formed on each substrate under the aforementioned conditions. As mentioned above, the substrate is usually a substrate on which transparent electrodes for driving liquid crystals have been formed. As a specific example, the same thing as the substrate described in the said liquid crystal alignment film can be mentioned.

一側之基板之上設置共用電極,在另一側之基板之上設置節段電極。該等電極係可作成例如ITO電極,且能圖型化成所欲之畫像顯示。其次,在各基板之上,被覆共用電極與節段電極之方式設置絕緣膜。絕緣膜係可作成例如藉由溶膠-凝膠法所形成之由SiO2 -TiO2 所構成之膜。A common electrode is arranged on one side of the substrate, and a segment electrode is arranged on the other side of the substrate. These electrodes can be made as ITO electrodes, and can be patterned into desired image display. Next, an insulating film is provided on each substrate so as to cover the common electrodes and the segment electrodes. The insulating film can be, for example, a film composed of SiO 2 -TiO 2 formed by a sol-gel method.

PSA模式之液晶顯示元件中,即使係在單側基板上形成例如1~10μm之線路/狹縫電極圖型,且在對向基板上未形成狹縫圖型或突起圖型之構造仍能運作,藉由此構造之液晶顯示元件,能簡略化製造時之製程,且取得高穿透率。In the liquid crystal display element of PSA mode, even if a line/slit electrode pattern of 1-10 μm is formed on one side substrate, and no slit pattern or protrusion pattern is formed on the opposite substrate, it can still operate. , the liquid crystal display element with this structure can simplify the manufacturing process and obtain high transmittance.

在製造IPS型或FFS型之液晶顯示元件之情況,在設置有由已圖型化成梳齒型之透明導電膜或金屬膜所構成之電極之基板的電極形成面,與未設置電極之對向基板之一面上分別塗佈液晶配向劑,其次藉由加熱各塗佈面而形成塗膜。作為金屬膜,可使用例如由鉻等之金屬所構成之膜。In the case of manufacturing IPS-type or FFS-type liquid crystal display elements, on the electrode formation surface of the substrate that is provided with electrodes composed of patterned comb-shaped transparent conductive films or metal films, the opposite side of the electrode is not provided. A liquid crystal alignment agent is coated on one surface of the substrate respectively, and then a coating film is formed by heating each coated surface. As the metal film, for example, a film made of metal such as chromium can be used.

又,在如TFT型元件之高機能元件中,使用在用來驅動液晶之電極與基板之間已形成如電晶體之元件者。Also, among high-performance devices such as TFT devices, devices such as transistors are used between electrodes for driving liquid crystals and a substrate.

在穿透型之液晶顯示元件之情況,一般係使用如上述之基板,但在反射型液晶顯示元件中,若僅為單側之基板,也能使用矽晶圓等之不透明基板。於此之際,形成於基板上之電極,也可使用反射光之如鋁之材料。In the case of a transmissive liquid crystal display device, the above-mentioned substrate is generally used, but in a reflective liquid crystal display device, if only one side of the substrate is used, an opaque substrate such as a silicon wafer can also be used. On this occasion, the electrodes formed on the substrate may also use materials such as aluminum that reflect light.

構成垂直配向方式之液晶顯示元件之液晶層的液晶材料並無特別限定,可使用過往之垂直配向方式所使用之液晶材料,例如、默克公司製之MLC-6608或MLC-6609、MLC-3022等之負型液晶。又,PSA模式中也可使用含有聚合性化合物之液晶即MLC-3023。其他也可使用例如含有下述式所示般之聚合性化合物之液晶。

Figure 02_image131
The liquid crystal material constituting the liquid crystal layer of the vertical alignment liquid crystal display element is not particularly limited, and the liquid crystal material used in the past vertical alignment method can be used, for example, MLC-6608 or MLC-6609, MLC-3022 manufactured by Merck & Co. Etc. Negative type liquid crystal. In addition, MLC-3023, which is a liquid crystal containing a polymerizable compound, can also be used in the PSA mode. Other liquid crystals containing, for example, a polymerizable compound represented by the following formula can also be used.
Figure 02_image131

另一方面,構成IPS或FFS等之水平配向方式之液晶顯示元件之液晶層的液晶材料,也可使用過往水平配向方式所使用之液晶材料,例如,默克公司製之MLC-2003或MLC-2041等之負正型之液晶或MLC-6608等之負型液晶。On the other hand, the liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the horizontal alignment method such as IPS or FFS can also use the liquid crystal material used in the past horizontal alignment method, for example, MLC-2003 or MLC- Negative and positive liquid crystals such as 2041 or negative liquid crystals such as MLC-6608.

作為將液晶層挾持於2枚基板之間之方法,可舉出如公知之方法。可舉出例如,準備已形成液晶配向膜之1對基板,在一側基板之液晶配向膜上散布珠粒等之間隔器,以使已形成液晶配向膜側之面成為內側之方式貼合另一側之基板,減壓注入液晶並密封之方法。又,準備已形成液晶配向膜之1對基板,在一側基板之液晶配向膜上散布珠粒等之間隔器後滴入液晶,其後以使已形成液晶配向膜側之面成為內側之方式貼合另一側之基板並進行密封之方法也可能製作液晶單元。上述間隔器之厚度係以1~30μm為佳,較佳為2~10μm。As a method of pinching a liquid crystal layer between two board|substrates, a well-known method is mentioned. For example, prepare a pair of substrates on which a liquid crystal alignment film has been formed, and spread spacers such as beads on the liquid crystal alignment film of one substrate, so that the surface on which the liquid crystal alignment film has been formed is on the inside and bonded to the other. A method of injecting liquid crystal into one side of the substrate under reduced pressure and sealing it. Also, prepare a pair of substrates on which the liquid crystal alignment film has been formed, spread spacers such as beads on the liquid crystal alignment film of one substrate, drop liquid crystals, and then make the surface on which the liquid crystal alignment film has been formed become the inner side It is also possible to make a liquid crystal cell by attaching and sealing the substrate on the other side. The thickness of the spacer is preferably 1-30 μm, more preferably 2-10 μm.

PSA模式方式係在挾持液晶後,藉由對液晶配向膜及液晶層施加電壓並同時照射紫外線來製作液晶單元。作為該步驟,可舉出例如藉由對設置於基板上之電極間施加電壓,而對液晶配向膜及液晶層施加電場,在保持此電場之狀態下照射紫外線之方法。在此,作為施加於電極間之電壓,例如5~30Vp-p或DC2.5~15V,較佳為10~30Vp-p或DC5~15V。又,作為照射之光,以包含300~400nm之波長光之紫外線為佳。作為照射光之光源,則係如同先前所述。紫外線之照射量係例如1~60J,較佳為40J以下,紫外線照射量較少為適宜,其係由於能抑制因構成液晶顯示元件之構件損壞所產生之信賴性降低,且藉由減少紫外線照射時間,而使製造效率提升。The PSA mode method is to produce a liquid crystal cell by applying voltage to the liquid crystal alignment film and the liquid crystal layer and irradiating ultraviolet rays at the same time after holding the liquid crystal. As this step, for example, by applying a voltage between electrodes provided on the substrate, an electric field is applied to the liquid crystal alignment film and the liquid crystal layer, and a method of irradiating ultraviolet rays while maintaining the electric field is exemplified. Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p or DC2.5 to 15V, preferably 10 to 30Vp-p or DC5 to 15V. In addition, as the light to be irradiated, ultraviolet rays including light having a wavelength of 300 to 400 nm are preferable. As a light source for irradiating light, it is as described above. The amount of irradiation of ultraviolet rays is, for example, 1 to 60J, preferably less than 40J. The lesser amount of ultraviolet irradiation is suitable because it can suppress the decrease in reliability caused by damage to the components constituting the liquid crystal display element, and by reducing the amount of ultraviolet irradiation time, thereby improving manufacturing efficiency.

如上述般,對液晶配向膜及液晶層施加電壓並同時照射紫外線時,聚合性化合物進行反應而形成聚合物,且藉由該聚合物,液晶分子傾斜之方向受到記憶,故能加快取得之液晶顯示元件之應答速度。又,對液晶配向膜及液晶層施加電壓並同時照射紫外線時,由於選自具有使液晶垂直配向之側鏈與光反應性側鏈之聚醯亞胺前驅物,及,使此聚醯亞胺前驅物醯亞胺化而得之聚醯亞胺之至少一種聚合物所具有之光反應性之側鏈彼此,或聚合物所具有之光反應性之側鏈與聚合性化合物進行反應,故可加快取得之液晶顯示元件之應答速度。 以上之步驟結束後,實施在液晶單元上設置偏光板,具體而言,以在2枚之基板之與液晶層為反對側之面上貼附一對偏光板為佳。As mentioned above, when a voltage is applied to the liquid crystal alignment film and the liquid crystal layer and ultraviolet rays are irradiated simultaneously, the polymerizable compound reacts to form a polymer, and the direction in which the liquid crystal molecules are inclined is memorized by the polymer, so that the obtained liquid crystal can be accelerated Displays the response speed of the device. In addition, when a voltage is applied to the liquid crystal alignment film and the liquid crystal layer while ultraviolet rays are irradiated, the polyimide is selected from a polyimide precursor having a side chain and a photoreactive side chain that make the liquid crystal vertically aligned, and the polyimide The photoreactive side chains of at least one polymer of the polyimide obtained by imidizing the precursor react with each other, or the photoreactive side chains of the polymer react with the polymerizable compound, so that Accelerate the response speed of obtained liquid crystal display elements. After the above steps are completed, install polarizing plates on the liquid crystal cell. Specifically, it is better to stick a pair of polarizing plates on the opposite side of the two substrates from the liquid crystal layer.

尚且,本發明之液晶配向膜及液晶顯示元件只要係使用本發明之液晶配向劑,則並非係受到限定者,亦可為使用其他之公知手法來製作者。由液晶配向劑取得液晶顯示元件為止之步驟係揭示於例如日本特開公報2015-135393之第17頁[0074]~第19頁[0081]。Furthermore, the liquid crystal alignment film and liquid crystal display element of the present invention are not limited as long as they use the liquid crystal alignment agent of the present invention, and may be produced using other known methods. The steps up to obtaining a liquid crystal display element from a liquid crystal alignment agent are disclosed in, for example, page 17 [0074] to page 19 [0081] of Japanese Patent Laid-Open Publication No. 2015-135393.

本發明之液晶顯示元件係能有效適用於各種裝置,可使用在例如時鐘、攜帶型遊戲機、文字處理器、筆記型個人電腦、汽車導航系統、攝像機、PDA、數位相機、行動電話、智慧型電話、各種螢幕、液晶電視、資訊顯示器等之各種顯示裝置。 [實施例]The liquid crystal display element of the present invention can be effectively applied to various devices, such as clocks, portable game machines, word processors, notebook personal computers, car navigation systems, video cameras, PDAs, digital cameras, mobile phones, smart phones, etc. Various display devices such as telephones, various screens, LCD TVs, and information displays. [Example]

以下例舉實施例更加詳細說明本發明,但本發明並非係受到該等所限定者。實施例中所使用之化合物之略稱之意義係如以下所示。 (酸二酐) BODA:雙環[3,3,0]辛烷-2,4,6,8-四羧酸二酐。 CBDA:1,2,3,4-環丁烷四羧酸二酐。 PMDA:苯-1,2,4,5-四羧酸酐。 TCA:2,3,5-三羧基環戊基乙酸-1,4,2,3-二酐 (二胺) p-PDA:1,4-伸苯基二胺、DDM:4,4‘-亞甲基二苯胺 DBA:3,5-二胺基安息香酸The following examples are given to describe the present invention in more detail, but the present invention is not limited thereto. The meanings of the abbreviations of the compounds used in the examples are as follows. (acid dianhydride) BODA: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride. CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride. PMDA: benzene-1,2,4,5-tetracarboxylic anhydride. TCA: 2,3,5-tricarboxycyclopentylacetic acid-1,4,2,3-dianhydride (diamine) p-PDA: 1,4-phenylene diamine, DDM: 4,4'-methylene diphenylamine DBA: 3,5-diaminobenzoic acid

Figure 02_image133
Figure 02_image133

Figure 02_image135
Figure 02_image135

Figure 02_image137
Figure 02_image137

<溶劑> NMP:N-甲基-2-吡咯啶酮、BCS:丁基溶纖劑。<Solvent> NMP: N-methyl-2-pyrrolidone, BCS: butyl cellosolve.

<聚醯亞胺之分子量測量> 測量裝置:泉州科學公司製 常溫凝膠滲透層析(GPC)(SSC-7200)、 管柱:Shodex公司製管柱(KD-803、KD-805)、管柱溫度:50℃、溶析液:N,N’-二甲基甲醯胺(作為添加劑,溴化鋰-水合物(LiBr・H2 O)30mmol/L、磷酸・無水結晶(o-磷酸)30mmol/L、四氫呋喃(THF)10ml/L)、 流速:1.0ml/分、 檢量線作成用標準試樣:東曹公司製TSK 標準聚環氧乙烷(分子量約9000,000、150,000、100,000、30,000)、及、聚合物研究室公司製聚乙二醇(分子量 約12,000、4,000、1,000)。<Molecular weight measurement of polyimide> Measuring device: Gel Permeation Chromatography (GPC) (SSC-7200) made by Quanzhou Science Co., Ltd., Column: Shodex Co., Ltd. Column temperature: 50°C, eluent: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr・H2O ) 30mmol/L, phosphoric acid・anhydrous crystal (o-phosphoric acid) 30mmol /L, tetrahydrofuran (THF) 10ml/L), flow rate: 1.0ml/min, standard sample for calibration curve creation: TSK standard polyethylene oxide (molecular weight: about 9000,000, 150,000, 100,000, 30,000), and polyethylene glycol (molecular weight about 12,000, 4,000, 1,000) manufactured by Polymer Laboratory Co., Ltd.

<醯亞胺化率之測量> 將聚醯亞胺粉末20mg放入NMR試樣管(草野科學公司製NMR取樣管標準φ5),添加氘化二甲亞碸(DMSO-d6 、0.05%TMS混合品)1.0ml,施加超音波使其完全溶解。將該溶液在日本電子資料公司製NMR測量器(JNW-ECA500)中測量500MHz之質子NMR。 (化學)醯亞胺化率係將源自在醯亞胺化前後不會變化之構造之質子決定當作基準質子,並使用該質子之波峰累算值,與出現在9.5~10.0ppm附近之源自醯胺酸之NH基之質子波峰累算值,根據以下之式而求出者。尚且,式中,x為源自醯胺酸之NH基之質子波峰累算值,y為基準質子之波峰累算值,α係基準質子對在聚醯胺酸(醯亞胺化率為0%)情況之醯胺酸之NH基之1個質子的個數比例。 醯亞胺化率(%)=(1-α・x/y)×100<Measurement of imidization rate> Put 20 mg of polyimide powder into an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Science Co., Ltd.), add deuterated dimethyl oxide (DMSO-d 6 , 0.05% TMS Mixture) 1.0ml, apply ultrasonic waves to dissolve completely. This solution was measured for proton NMR at 500 MHz with an NMR measuring device (JNW-ECA500) manufactured by JEOL Ltd. (Chemical) imidization ratio is determined by determining the proton derived from the structure that does not change before and after imidization as a reference proton, and using the peak cumulative value of the proton, and the value that appears near 9.5 to 10.0ppm The calculated value of the proton peak derived from the NH group of amide acid is calculated according to the following formula. Moreover, in the formula, x is the accumulated value of the proton peak derived from the NH group of amide acid, y is the accumulated value of the peak of the reference proton, and α is the reference proton pair in polyamide acid (imidization rate is 0 %) The ratio of the number of 1 proton of the NH group of the amino acid in the case. Imidization rate (%)=(1-α・x/y)×100

化合物DA-O1~DA-O4為新穎化合物,藉由以下操作而經合成者。 由下述單體之合成例1~4而得之生成物係藉由1 H-NMR分析進行辨識。分析條件係如以下所述。 裝置:Varian NMR System 400 NB (400 MHz) 測量溶劑:DMSO-d6 、 基準物質:四甲基矽烷(TMS)(δ0.0 ppm for1 H)Compounds DA-O1 to DA-O4 are novel compounds synthesized by the following operations. Products obtained from Synthesis Examples 1 to 4 of the following monomers were identified by 1 H-NMR analysis. Analysis conditions are as follows. Device: Varian NMR System 400 NB (400 MHz) Measurement solvent: DMSO-d 6 , Reference material: Tetramethylsilane (TMS) (δ0.0 ppm for 1 H)

<<合成例1:DA-O1之合成>>

Figure 02_image139
<<Synthesis Example 1: Synthesis of DA-O1>>
Figure 02_image139

<化合物[1]之合成> 將甲醇(320g)、p-硝基苄腈(40.0g,270mmol)、2-胺基-2-甲基-1,3-丙二醇(142.3g)、及碳酸鈉(28.6g)放入燒瓶中,在氮環境迴流條件下使其反應22小時。反應結束後,將反應溶液注入純水(960g)而使結晶析出,並實施過濾、甲醇洗淨。其次,將取得之粗物以乙酸乙酯(260g)與己烷(40g)混合溶劑進行漿液洗淨,藉由過濾、乾燥而取得化合物[1]作為白色結晶(收量:46.8g、收率:73%)。1 H-NMR(400MHz) in DMSO-d6 :8.29-8.33ppm(m,2H), 8.07-8.11ppm(m,2H), 4.97ppm(t,J =6.0Hz,1H), 4.46ppm (d,J =8.4Hz,1H), 4.07ppm(d,J =8.4Hz,1H), 3.36-3.47ppm (m,2H), 1.25ppm(s,3H)<Synthesis of Compound [1]> Methanol (320g), p-nitrobenzonitrile (40.0g, 270mmol), 2-amino-2-methyl-1,3-propanediol (142.3g), and sodium carbonate were mixed (28.6g) was put into a flask, and it was made to react for 22 hours under the reflux condition of nitrogen environment. After completion of the reaction, the reaction solution was poured into pure water (960 g) to precipitate crystals, followed by filtration and washing with methanol. Next, the obtained crude product was slurry washed with a mixed solvent of ethyl acetate (260g) and hexane (40g), and compound [1] was obtained as white crystals by filtration and drying (yield: 46.8g, yield : 73%). 1 H-NMR(400MHz) in DMSO-d 6 : 8.29-8.33ppm(m,2H), 8.07-8.11ppm(m,2H), 4.97ppm(t, J =6.0Hz,1H), 4.46ppm (d , J =8.4Hz,1H), 4.07ppm(d, J =8.4Hz,1H), 3.36-3.47ppm (m,2H), 1.25ppm(s,3H)

<化合物[2]之合成> 將N-甲基-2-吡咯啶酮(380g)、化合物[1](44.7g,189mmol)、4-氟硝基苯(45.9g)、及氫氧化鈉(12.6g)放入燒瓶中,在室溫條件下使其反應約5天。反應結束後,將反應液注入純水(1124g)而使結晶析出,藉由過濾來回收粗結晶。其次,以甲醇(179g)進行室溫漿液洗淨,其後以乙酸乙酯(560g)進行漿液洗淨。漿液洗淨後,藉由過濾、乾燥而取得化合物[2]作為淡黃色結晶(收量:51.4g、收率:76%)。1 H-NMR(400MHz) in DMSO-d6 :8.30-8.32ppm(m,2H), 8.15-8.19ppm(m,2H), 8.09-8.12ppm(m,2H), 7.13-7.18ppm (m,2H), 4.56ppm(d,J =8.8Hz,1H), 4.27ppm(d,J =8.4Hz,1H), 4.26ppm(d,J =9.6Hz,1H), 4.21ppm(d,J =10.0Hz,1H), 1.25ppm (s,3H)<Synthesis of compound [2]> N-methyl-2-pyrrolidone (380 g), compound [1] (44.7 g, 189 mmol), 4-fluoronitrobenzene (45.9 g), and sodium hydroxide ( 12.6 g) was put into a flask, and it was reacted for about 5 days at room temperature. After completion of the reaction, the reaction solution was poured into pure water (1124 g) to precipitate crystals, and the crude crystals were recovered by filtration. Next, room-temperature slurry washing was performed with methanol (179 g), and then slurry washing was performed with ethyl acetate (560 g). After the slurry was washed, compound [2] was obtained by filtration and drying as pale yellow crystals (amount: 51.4 g, yield: 76%). 1 H-NMR(400MHz) in DMSO-d 6 : 8.30-8.32ppm(m,2H), 8.15-8.19ppm(m,2H), 8.09-8.12ppm(m,2H), 7.13-7.18ppm (m, 2H), 4.56ppm(d, J =8.8Hz,1H), 4.27ppm(d, J =8.4Hz,1H), 4.26ppm(d, J =9.6Hz,1H), 4.21ppm(d, J =10.0 Hz,1H), 1.25ppm (s,3H)

<DA-O1之合成> 將四氫呋喃(397g)及甲醇(99g)、化合物[2](49.7g,139mmol)、5%鈀-碳(約50%水濕潤品)(3.46g)放入燒瓶中,在氫環境室溫條件下使其反應24小時。反應結束後,藉由過濾而去除5%鈀-碳,藉由減壓濃縮而將內部總重量作成73.4g。其次,添加2-丙醇(250g)加熱至50℃使其溶解,在冰冷條件下使結晶析出,藉由過濾、乾燥而取得DA-O1作為白色結晶(收量:30.2g、收率:73%)。1 H-NMR(400MHz) in DMSO-d6 :7.50-7.54ppm(m,2H), 6.62-6.66ppm(m,2H), 6.53-6.56ppm(m,2H), 6.45-6.49ppm (m,2H), 5.7ppm(s,2H), 4.61ppm(s, 2H), 4.31ppm(d,J = 8.4Hz,1H), 4.00ppm(d,J =8.40Hz,1H), 3.74-3.79ppm(m,2H), 1.30ppm(s,3H)<Synthesis of DA-O1> Put tetrahydrofuran (397g), methanol (99g), compound [2] (49.7g, 139mmol), 5% palladium-carbon (approximately 50% water wet product) (3.46g) into a flask , and allowed to react for 24 hours under hydrogen ambient room temperature conditions. After completion of the reaction, 5% palladium-carbon was removed by filtration, and the total internal weight was adjusted to 73.4 g by concentration under reduced pressure. Next, add 2-propanol (250g) and heat to 50°C to dissolve it, precipitate crystals under ice-cooling conditions, and obtain DA-O1 as white crystals by filtration and drying (yield: 30.2g, yield: 73 %). 1 H-NMR(400MHz) in DMSO-d 6 : 7.50-7.54ppm(m,2H), 6.62-6.66ppm(m,2H), 6.53-6.56ppm(m,2H), 6.45-6.49ppm (m, 2H), 5.7ppm(s,2H), 4.61ppm(s, 2H), 4.31ppm(d, J = 8.4Hz,1H), 4.00ppm(d, J =8.40Hz,1H), 3.74-3.79ppm( m,2H), 1.30ppm(s,3H)

<<合成例2:DA-O2之合成之合成>>

Figure 02_image141
<<Synthesis Example 2: Synthesis of DA-O2 Synthesis>>
Figure 02_image141

<化合物[3]之合成> 將甲醇(240g)、p-硝基苄腈(30.0g,203mmol)、2-胺基-1,3-丙二醇(55.6g)、及碳酸鈉(21.6g)放入燒瓶中,在氮環境迴流條件下使其反應23小時。反應結束後,將反應溶液注入純水(720g)而使結晶析出,並實施過濾、甲醇洗淨。其次,將取得之粗物以乙酸乙酯(150g)與己烷(30g)混合溶劑進行漿液洗淨,藉由過濾、乾燥而取得化合物[3]作為淡黃色結晶(收量:30.9g、收率:69%)。1 H-NMR(400MHz)in DMSO-d6 :8.11-8.33ppm(m,2H), 8.09-8.12ppm(m,2H), 4.90ppm(t,J =5.6Hz,1H), 4.48-4.90 ppm(m,1H), 4.33-4.41ppm(m,2H), 3.36-3.64ppm(m,2H)<Synthesis of compound [3]> Methanol (240g), p-nitrobenzonitrile (30.0g, 203mmol), 2-amino-1,3-propanediol (55.6g), and sodium carbonate (21.6g) were put into into a flask, and reacted for 23 hours under reflux under a nitrogen environment. After completion of the reaction, the reaction solution was poured into pure water (720 g) to precipitate crystals, followed by filtration and washing with methanol. Next, the obtained crude product was slurry washed with a mixed solvent of ethyl acetate (150 g) and hexane (30 g), and compound [3] was obtained as light yellow crystals by filtration and drying (yield: 30.9 g, yield rate: 69%). 1 H-NMR(400MHz)in DMSO-d 6 : 8.11-8.33ppm(m,2H), 8.09-8.12ppm(m,2H), 4.90ppm(t, J =5.6Hz,1H), 4.48-4.90ppm (m,1H), 4.33-4.41ppm(m,2H), 3.36-3.64ppm(m,2H)

<化合物[4]之合成> 將N-甲基-2-吡咯啶酮(138g)、化合物[3](27.8g,126mmol)、4-氟硝基苯(28.8g)、及氫氧化鈉(7.6g)放入燒瓶中,在室溫條件下使其反應約4天。反應結束後,對反應液添加乙酸乙酯(504g)及純水(224g)之結果,結晶析出。藉由過濾來回收結晶,將經回收之結晶以甲醇(140g)與純水(140g)混合溶劑進行室溫漿液洗淨。漿液洗淨後,藉由過濾、甲醇洗淨、乾燥而取得化合部物[4]作為淡黃色結晶(收量:31.3g、收率:72%)。1 H-NMR(400MHz)in DMSO-d6 :8.31-8.33ppm(m,2H), 8.17-8.21ppm(m,2H), 8.11-8.14ppm(m,2H), 7.15-7.19ppm (m,2H), 4.76-4.83ppm(m,1H), 4.66-4.70ppm(m,1H), 4.42-4.46ppm(m,1H), 4.32-4.38ppm(m,1H)<Synthesis of compound [4]> N-methyl-2-pyrrolidone (138 g), compound [3] (27.8 g, 126 mmol), 4-fluoronitrobenzene (28.8 g), and sodium hydroxide ( 7.6 g) was put into a flask, and it was reacted for about 4 days at room temperature. After completion of the reaction, ethyl acetate (504 g) and pure water (224 g) were added to the reaction liquid, and crystals were deposited. The crystals were recovered by filtration, and the recovered crystals were subjected to room temperature slurry washing with a mixed solvent of methanol (140 g) and pure water (140 g). After the slurry was washed, the compound product [4] was obtained by filtration, washing with methanol, and drying as light yellow crystals (amount: 31.3 g, yield: 72%). 1 H-NMR(400MHz)in DMSO-d 6 : 8.31-8.33ppm(m,2H), 8.17-8.21ppm(m,2H), 8.11-8.14ppm(m,2H), 7.15-7.19ppm (m, 2H), 4.76-4.83ppm(m,1H), 4.66-4.70ppm(m,1H), 4.42-4.46ppm(m,1H), 4.32-4.38ppm(m,1H)

<DA-O2之合成> 將四氫呋喃(217g)及甲醇(62.6g)、化合物[4](31.3g,91.2mmol)、及5%鈀-碳(約50%水濕潤品)(2.34g)放入燒瓶中,在氫環境40℃條件下使其反應4天。反應結束後,藉由過濾而去除5%鈀-碳,藉由減壓濃縮去除溶劑而取得粗物。其次,以甲醇(243g)進行室溫漿液洗淨,藉由過濾、乾燥而取得DA-O2作為淡粉紅色結晶(收量:17.5g、收率:68%)。1 H-NMR(400MHz)in DMSO-d6 :7.53-7.56ppm(m,2H), 6.64-6.68ppm(m,2H), 6.54-6.57ppm(m,2H), 6.47-6.51ppm (m,2H), 5.73ppm(s,2H), 4.62ppm(s,2H), 4.41-4.47ppm (m,2H), 4.15-4.18ppm(m,1H), 3.96-3.99ppm(m,1H), 3.79-3.83ppm(m,1H)<Synthesis of DA-O2> Tetrahydrofuran (217g), methanol (62.6g), compound [4] (31.3g, 91.2mmol), and 5% palladium-carbon (approximately 50% water wet product) (2.34g) were put into a flask, and reacted for 4 days under a hydrogen environment at 40°C. After the reaction was completed, 5% palladium-carbon was removed by filtration, and the solvent was removed by concentration under reduced pressure to obtain a crude product. Next, room temperature slurry was washed with methanol (243 g), and DA-O2 was obtained as pale pink crystals by filtration and drying (yield: 17.5 g, yield: 68%). 1 H-NMR(400MHz)in DMSO-d 6 : 7.53-7.56ppm(m,2H), 6.64-6.68ppm(m,2H), 6.54-6.57ppm(m,2H), 6.47-6.51ppm (m, 2H), 5.73ppm(s,2H), 4.62ppm(s,2H), 4.41-4.47ppm (m,2H), 4.15-4.18ppm(m,1H), 3.96-3.99ppm(m,1H), 3.79 -3.83ppm(m,1H)

<<合成例3:DA-O3之合成>>

Figure 02_image143
<<Synthesis Example 3: Synthesis of DA-O3>>
Figure 02_image143

<化合物[5]之合成> 將甲醇(400g)、對苯二腈(50.2g,392ammol)、2-胺基-2-甲基-1,3-丙二醇(165g)、及碳酸鈉(83.9g)放入燒瓶中,在氮環境迴流條件下使其反應20小時。反應結束後,在純水(1200g)中注入反應液而使結晶析出,藉由過濾來回收粗物。藉由將取得之粗物以純水(300g×6次)洗淨,其後以甲醇(200g×2次)洗淨,而取得化合物[5]作為白色結晶(粗收量:109.6g、粗收率:100%)。1 H-NMR(400MHz)in DMSO-d6 :7.92ppm(s,4H), 4.94 ppm(t,J =5.2Hz,2H), 4.41ppm(d,J =8.0Hz,2H), 4.01ppm (d,J =8.0Hz,2H), 3.36-3.44ppm(m,4H), 1.23ppm(s,6H)<Synthesis of Compound [5]> Methanol (400 g), terephthalonitrile (50.2 g, 392 mmol), 2-amino-2-methyl-1,3-propanediol (165 g), and sodium carbonate (83.9 g ) was put into a flask, and it was reacted for 20 hours under nitrogen ambient reflux conditions. After completion of the reaction, the reaction solution was poured into pure water (1200 g) to precipitate crystals, and the crude product was recovered by filtration. By washing the obtained crude product with pure water (300 g x 6 times) and then with methanol (200 g x 2 times), compound [5] was obtained as white crystals (crude yield: 109.6 g, crude Yield: 100%). 1 H-NMR(400MHz)in DMSO-d 6 : 7.92ppm(s,4H), 4.94ppm(t, J =5.2Hz,2H), 4.41ppm(d, J =8.0Hz,2H), 4.01ppm ( d, J =8.0Hz,2H), 3.36-3.44ppm(m,4H), 1.23ppm(s,6H)

<化合物[6]之合成> 將N-甲基-2-吡咯啶酮(327g)、化合物[5](40.8g,146mmol)、及氫氧化鉀(21.2g)放入燒瓶中,在氮環境水冷條件下滴入溶解於N-甲基-2-吡咯啶酮(19.9g)之4-氟硝基苯(45.7g)。滴入結束後,以N-甲基-2-吡咯啶酮(21.4g)洗淨滴入漏斗,在室溫條件下使其反應2小時。反應結束後,在純水(1200g)中注入反應液而使結晶析出,並實施過濾、純水、甲醇洗淨。其次,將取得之粗結晶以甲醇(300g)進行室溫漿液洗淨。其後,使粗結晶加熱溶解於氯仿(10009g),添加甲醇(466g)而使結晶析出,藉由過濾、乾燥,而取得化合物[6]作為淡黃色結晶(收量:63.2g、收率:79%)。1 H-NMR(400MHz)in DMSO-d6 :8.16-8.19ppm(m,4H), 7.95ppm(s,4H), 7.13-7.16ppm(m,4H), 4.52ppm (d,J =8.4Hz, 2H), 4.19-4.22ppm(m,6H), 1.42ppm(s,6H)<Synthesis of compound [6]> Put N-methyl-2-pyrrolidone (327g), compound [5] (40.8g, 146mmol), and potassium hydroxide (21.2g) into a flask, 4-Fluoronitrobenzene (45.7 g) dissolved in N-methyl-2-pyrrolidone (19.9 g) was added dropwise under water cooling. After completion of the dropping, the dropping funnel was washed with N-methyl-2-pyrrolidone (21.4 g), and reacted at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into pure water (1200 g) to precipitate crystals, and then filtered, purified water, and methanol were washed. Next, the obtained crude crystals were slurry-washed with methanol (300 g) at room temperature. Thereafter, the crude crystals were heated and dissolved in chloroform (10009 g), methanol (466 g) was added to precipitate crystals, and compound [6] was obtained as pale yellow crystals by filtration and drying (yield: 63.2 g, yield: 79%). 1 H-NMR(400MHz)in DMSO-d 6 : 8.16-8.19ppm(m,4H), 7.95ppm(s,4H), 7.13-7.16ppm(m,4H), 4.52ppm (d, J =8.4Hz , 2H), 4.19-4.22ppm(m,6H), 1.42ppm(s,6H)

<DA-O3之合成> 將四氫呋喃(509g)、甲醇(62.3g)、化合物[6](62.7g,115mmol)、及5%鈀-碳(約50%水濕潤品)(3.66g)放入燒瓶中,在氫環境40℃條件下使其反應4天。反應結束後,藉由過濾而去除5%鈀-碳。其次,以過剩量之N,N-二甲基甲醯胺洗淨過濾物。減壓濃縮取得之濾液,添加甲醇(660g)而使結晶析出,藉由過濾而取得DA-O3作為淡粉紅色結晶(收量:20.9g、收率:38%)。1 H-NMR(400MHz)in DMSO-d6 :7.96ppm(s,4H), 6.62-6.65ppm(m,4H), 6.46-6.49ppm(m,4H), 4.61ppm(s,4H), 4.47 ppm(d,J =8.4Hz,2H), 4.16ppm(d,J =8.4Hz,2H), 3.87ppm (d,J =9.2Hz,2H), 3.60ppm(d,J =9.2Hz,2H), 1.36ppm(s,6H)<Synthesis of DA-O3> Put tetrahydrofuran (509g), methanol (62.3g), compound [6] (62.7g, 115mmol), and 5% palladium-carbon (about 50% water wet product) (3.66g) into In the flask, it was reacted for 4 days under a hydrogen atmosphere at 40°C. After the reaction was complete, 5% palladium-carbon was removed by filtration. Next, the filtrate was washed with excess N,N-dimethylformamide. The obtained filtrate was concentrated under reduced pressure, methanol (660 g) was added to precipitate crystals, and DA-O3 was obtained by filtration as pale pink crystals (yield: 20.9 g, yield: 38%). 1 H-NMR(400MHz)in DMSO-d 6 : 7.96ppm(s,4H), 6.62-6.65ppm(m,4H), 6.46-6.49ppm(m,4H), 4.61ppm(s,4H), 4.47 ppm(d, J =8.4Hz,2H), 4.16ppm(d, J =8.4Hz,2H), 3.87ppm (d, J =9.2Hz,2H), 3.60ppm(d, J =9.2Hz,2H) , 1.36ppm(s,6H)

<<合成例4:DA-O4之合成>>

Figure 02_image145
<<Synthesis Example 4: Synthesis of DA-O4>>
Figure 02_image145

<化合物[7]之合成> 將N-甲基-2-吡咯啶酮(400g)、化合物[5](40.0g,143mmol)、及三乙基胺(38.0g)放入燒瓶中,在氮環境水冷條件下以4等分投入4-硝基苄醯基氯化物(60.7g)。投入後,由於發生攪拌不良,故添加N-甲基-2-吡咯啶酮(160g)來確保攪拌性,在室溫條件下使其反應約15小時。反應結束後,將反應液注入於純水(1500g)中而使結晶析出,並實施過濾、純水及甲醇洗淨。其次,使取得之粗物以50℃加熱溶解於四氫呋喃(560g),添加甲醇(400g)而使結晶析出。並且,對取得之結晶以四氫呋喃(160g)進行漿液洗淨,藉由過濾、乾燥而取得化合物[7]作為白色結晶(收量:47.4g、收率:55%)。1 H-NMR(400MHz)in DMSO-d6 :8.24-8.30ppm(m,4H), 8.06-8.11ppm(m,4H), 7.93ppm(s,4H), 4.58-4.60ppm(m,2H), 4.35-4.43ppm(m,4H), 4.19-4.22ppm(m,2H), 1.43ppm(s,6H)<Synthesis of compound [7]> N-methyl-2-pyrrolidone (400 g), compound [5] (40.0 g, 143 mmol), and triethylamine (38.0 g) were placed in a flask, and 4-Nitrobenzyl chloride (60.7 g) was charged in 4 aliquots under ambient water cooling. After charging, since stirring failure occurred, N-methyl-2-pyrrolidone (160g) was added and stirring property was ensured, and it was made to react at room temperature for about 15 hours. After completion of the reaction, the reaction liquid was poured into pure water (1500 g) to precipitate crystals, followed by filtration and washing with pure water and methanol. Next, the obtained crude product was heated and dissolved in tetrahydrofuran (560 g) at 50°C, and methanol (400 g) was added to precipitate crystals. Then, the obtained crystals were slurry-washed with tetrahydrofuran (160 g), and compound [7] was obtained as white crystals by filtration and drying (amount: 47.4 g, yield: 55%). 1 H-NMR(400MHz)in DMSO-d 6 : 8.24-8.30ppm(m,4H), 8.06-8.11ppm(m,4H), 7.93ppm(s,4H), 4.58-4.60ppm(m,2H) , 4.35-4.43ppm(m,4H), 4.19-4.22ppm(m,2H), 1.43ppm(s,6H)

<DA-O4之合成> 將四氫呋喃(453g)、甲醇(95.6g)、N,N-二甲基甲醯胺(400g)、化合物[7](47.4g,78.6mmol)、及5%鈀-碳(約50%水濕潤品)(2.90g)放入燒瓶中,在氫環境室溫條件下使其反應約3天。藉由過濾而去除5%鈀-碳,藉由減壓濃縮而將內部重量作成130g。對取得之均勻溶液添加甲醇(390g)而使結晶析出,藉由過濾、乾燥而取得DA-O4作為白色結晶(收量:17.3g、收率:41%)。1 H-NMR(400MHz)in DMSO-d6 :7.96ppm(s,4H), 7.52-7.55ppm(m,4H), 6.46-6.50ppm(m,4H), 5.96ppm(s,4H), 4.48 ppm(d,J =8.8Hz,2H), 4.16-4.22ppm(m,6H), 1.39ppm(s,6H)<Synthesis of DA-O4> Tetrahydrofuran (453g), methanol (95.6g), N,N-dimethylformamide (400g), compound [7] (47.4g, 78.6mmol), and 5% palladium- Carbon (approximately 50% water wet product) (2.90g) was put into a flask, and it was reacted for about 3 days under hydrogen ambient room temperature conditions. 5% palladium-carbon was removed by filtration, and the internal weight was adjusted to 130 g by concentration under reduced pressure. Methanol (390 g) was added to the obtained homogeneous solution to precipitate crystals, and DA-O4 was obtained as white crystals by filtration and drying (yield: 17.3 g, yield: 41%). 1 H-NMR(400MHz)in DMSO-d 6 : 7.96ppm(s,4H), 7.52-7.55ppm(m,4H), 6.46-6.50ppm(m,4H), 5.96ppm(s,4H), 4.48 ppm(d, J =8.8Hz,2H), 4.16-4.22ppm(m,6H), 1.39ppm(s,6H)

<製造例1> 使BODA(1.25g、5.00mmol)、DA-O1(2.08g、7.00 mmol)及DA-S1(1.14g、3.00mmol)溶解於NMP(17.9g)中,以60℃使其反應3小時後,添加CBDA(0.92g、4.70mmol)與NMP(3.70g),在40℃下使其反應4小時而取得聚醯胺酸溶液。此聚醯胺酸之Mn為10200,Mw為25800。藉由對此聚醯胺酸溶液(5.4g)添加NMP(5.40g)與BCS(7.20g)並在室溫下攪拌2小時而取得液晶配向劑PAA-1。<Manufacturing example 1> BODA (1.25g, 5.00mmol), DA-O1 (2.08g, 7.00mmol) and DA-S1 (1.14g, 3.00mmol) were dissolved in NMP (17.9g), and reacted at 60°C for 3 hours. CBDA (0.92g, 4.70mmol) and NMP (3.70g) were added, it was made to react at 40 degreeC for 4 hours, and the polyamic-acid solution was obtained. The Mn of this polyamic acid is 10200, and the Mw is 25800. The liquid crystal alignment agent PAA-1 was obtained by adding NMP (5.40 g) and BCS (7.20 g) to the polyamic acid solution (5.4 g) and stirring at room temperature for 2 hours.

<製造例2> 使BODA(1.25g、5.00mmol)、DA-O2(1.98g、7.00 mmol)及DA-S1(1.14g、3.00mmol)溶解於NMP(17.5g)中,在60℃下使其反應3小時後,添加CBDA(0.89g、4.55mmol)與NMP(3.60g),在40℃下使其反應4小時而取得聚醯胺酸溶液。此聚醯胺酸之Mn為9800,Mw為47700。藉由此聚醯胺酸溶液(5.4g)添加NMP(5.40g)與BCS(7.20g)並在室溫下攪拌2小時而取得液晶配向劑PAA-2。<Manufacturing example 2> BODA (1.25g, 5.00mmol), DA-O2 (1.98g, 7.00mmol) and DA-S1 (1.14g, 3.00mmol) were dissolved in NMP (17.5g), and reacted at 60°C for 3 hours , CBDA (0.89g, 4.55mmol) and NMP (3.60g) were added, it was made to react at 40 degreeC for 4 hours, and the polyamic-acid solution was obtained. The Mn of this polyamic acid is 9800, and the Mw is 47700. The liquid crystal alignment agent PAA-2 was obtained by adding NMP (5.40 g) and BCS (7.20 g) to the polyamic acid solution (5.4 g) and stirring at room temperature for 2 hours.

<製造例3> 使BODA(3.13g、12.5mmol)、p-PDA(1.89g、17.5 mmol)及DA-S1(2.85g、7.50mmol)溶解於NMP(31.5g)中,在60℃下使其反應3小時後,添加CBDA(2.40g、12.3mmol)與NMP(9.60g),在40℃下使其反應4小時而取得聚醯胺酸溶液。此聚醯胺酸之Mn為10800,Mw為28000。藉由對聚醯胺酸溶液(5.4g)添加NMP(5.40g)與BCS(7.20g)並在室溫下攪拌2小時而取得液晶配向劑PAA-3。<Manufacturing example 3> BODA (3.13g, 12.5mmol), p-PDA (1.89g, 17.5mmol) and DA-S1 (2.85g, 7.50mmol) were dissolved in NMP (31.5g), and reacted at 60°C for 3 hours , CBDA (2.40g, 12.3mmol) and NMP (9.60g) were added, it was made to react at 40 degreeC for 4 hours, and the polyamic-acid solution was acquired. The Mn of this polyamic acid is 10800, and the Mw is 28000. The liquid crystal alignment agent PAA-3 was obtained by adding NMP (5.40 g) and BCS (7.20 g) to the polyamic acid solution (5.4 g) and stirring at room temperature for 2 hours.

<製造例4> 使BODA(1.25g、5.00mmol)、DA-O1(2.08g、7.00 mmol)及DA-S1(1.14g、3.00mmol)溶解於NMP(17.9g)中,在60℃下使其反應3小時後,添加CBDA(0.92g、4.70mmol)與NMP(3.70g),在40℃下使其反應4小時而取得聚醯胺酸溶液。對此聚醯胺酸溶液(15g)添加NMP稀釋成6.5質量%後,添加作為醯亞胺化觸媒之無水乙酸(2.81g)及吡啶(0.87g),在50℃下使其反應3小時。將此反應溶液投入甲醇(170g),並過濾分離取得之沉澱物。以甲醇洗淨此沉澱物,在60℃下減壓乾燥而取得聚醯亞胺粉末。此聚醯亞胺之醯亞胺化率為51%,Mn為10100,Mw為25000。 對取得之聚醯亞胺粉末(2.0g)添加NMP(18.0g),在70℃下攪拌12小時使其溶解。藉由對此溶液添加BCS(13.3g)並在室溫下攪拌2小時而取得液晶配向劑SPI-1。<Manufacturing example 4> BODA (1.25g, 5.00mmol), DA-O1 (2.08g, 7.00mmol) and DA-S1 (1.14g, 3.00mmol) were dissolved in NMP (17.9g), and reacted at 60°C for 3 hours , CBDA (0.92g, 4.70mmol) and NMP (3.70g) were added, it was made to react at 40 degreeC for 4 hours, and the polyamic-acid solution was acquired. After adding NMP to this polyamic acid solution (15g) and diluting it to 6.5% by mass, anhydrous acetic acid (2.81g) and pyridine (0.87g) were added as imidization catalysts, and reacted at 50°C for 3 hours . The reaction solution was poured into methanol (170 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 60° C. to obtain a polyimide powder. The imidization rate of this polyimide was 51%, Mn was 10100, and Mw was 25000. NMP (18.0 g) was added to the obtained polyimide powder (2.0 g), and it stirred and melt|dissolved at 70 degreeC for 12 hours. Liquid crystal alignment agent SPI-1 was obtained by adding BCS (13.3 g) to this solution and stirring at room temperature for 2 hours.

<製造例5> 使BODA(3.13g、12.5mmol)、p-PDA(1.89g、17.5mmol)及DA-S1(2.85g、7.50mmol)溶解於NMP(31.5g)中,在60℃下使其反應3小時後,添加CBDA(2.40g、12.3mmol)與NMP(9.60g),在40℃下使其反應4小時而取得聚醯胺酸溶液。 對此聚醯胺酸溶液(20g)添加NMP稀釋成6.5質量%後,添加作為醯亞胺化觸媒之無水乙酸(4.94g)及吡啶(1.53g),在50℃下使其反應3小時。將此反應溶液投入甲醇(240g),並過濾分離取得之沉澱物。以甲醇洗淨此沉澱物,在60℃下減壓乾燥而取得聚醯亞胺粉末。此聚醯亞胺之醯亞胺化率為49%,Mn為10600,Mw為27500。 對取得之聚醯亞胺粉末(2.0g)添加NMP(18.0g),在70℃下攪拌12小時使其溶解。藉由對溶液添加BCS(13.3g)並在室溫下攪拌2小時而取得液晶配向劑SPI-2。<Manufacturing example 5> BODA (3.13g, 12.5mmol), p-PDA (1.89g, 17.5mmol) and DA-S1 (2.85g, 7.50mmol) were dissolved in NMP (31.5g), and reacted at 60°C for 3 hours , CBDA (2.40g, 12.3mmol) and NMP (9.60g) were added, it was made to react at 40 degreeC for 4 hours, and the polyamic-acid solution was acquired. After adding NMP to this polyamic acid solution (20g) and diluting it to 6.5% by mass, anhydrous acetic acid (4.94g) and pyridine (1.53g) were added as imidization catalysts, and reacted at 50°C for 3 hours . The reaction solution was poured into methanol (240 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 60° C. to obtain a polyimide powder. The imidization rate of this polyimide was 49%, Mn was 10600, and Mw was 27500. NMP (18.0 g) was added to the obtained polyimide powder (2.0 g), and it stirred and melt|dissolved at 70 degreeC for 12 hours. Liquid crystal alignment agent SPI-2 was obtained by adding BCS (13.3 g) to the solution and stirring at room temperature for 2 hours.

<製造例6> 使DA-O1(1.49g、5.01mmol)溶解於NMP(13.7g)中,添加CBDA(0.93g、4.73mmol)與NMP(4.01g),在40℃下使其反應4小時而取得聚醯胺酸溶液。此聚醯胺酸之Mn為6500,Mw為13800。 藉由對此聚醯胺酸溶液(12.1g)添加NMP(4.45g)與BCS(7.67g)並在室溫下攪拌2小時而取得液晶配向劑PAA-4。<Manufacturing example 6> Dissolve DA-O1 (1.49g, 5.01mmol) in NMP (13.7g), add CBDA (0.93g, 4.73mmol) and NMP (4.01g), and react at 40°C for 4 hours to obtain polyamide acid solution. The Mn of this polyamic acid is 6500, and the Mw is 13800. The liquid crystal alignment agent PAA-4 was obtained by adding NMP (4.45 g) and BCS (7.67 g) to the polyamic acid solution (12.1 g) and stirring at room temperature for 2 hours.

<製造例7> 使DA-O1(0.40g、1.34mmol)、p-PDA(0.14g及1.33 mmol)溶解於NMP(5.90g)中,添加CBDA(0.50g、2.55 mmol)與NMP(1.71g),在室溫下使其反應18小時而取得聚醯胺酸溶液。此聚醯胺酸之Mn為6000,Mw為13200。藉由對此聚醯胺酸溶液(8.65g)添加NMP(5.20g)與BCS(3.46g)並在室溫下攪拌2小時而取得液晶配向劑PAA-5。<Manufacturing example 7> DA-O1 (0.40g, 1.34mmol), p-PDA (0.14g and 1.33mmol) were dissolved in NMP (5.90g), and CBDA (0.50g, 2.55mmol) and NMP (1.71g) were added, at room temperature The reaction was carried out for 18 hours to obtain a polyamic acid solution. The Mn of this polyamic acid is 6000, and the Mw is 13200. The liquid crystal alignment agent PAA-5 was obtained by adding NMP (5.20 g) and BCS (3.46 g) to the polyamic acid solution (8.65 g) and stirring at room temperature for 2 hours.

<製造例8> 使p-PDA(2.17g、20.1mmol)溶解於NMP(41.8g)中,添加CBDA(3.61g、18.4mmol)與NMP(9.46g),在40℃下使其反應4小時而取得聚醯胺酸溶液。此聚醯胺酸之Mn為4800,Mw為11200。 對此聚醯胺酸溶液(49.1g)添加NMP(15.2g)與BCS(16.1g)並在室溫下攪拌2小時而取得液晶配向劑PAA-6。<Manufacturing example 8> Dissolve p-PDA (2.17g, 20.1mmol) in NMP (41.8g), add CBDA (3.61g, 18.4mmol) and NMP (9.46g), and react at 40°C for 4 hours to obtain polyamide acid solution. The Mn of this polyamic acid is 4800, and the Mw is 11200. NMP (15.2 g) and BCS (16.1 g) were added to the polyamic acid solution (49.1 g), and stirred at room temperature for 2 hours to obtain liquid crystal alignment agent PAA-6.

<製造例9> 使DA-O1(2.97g、10.0mmol)溶解於NMP(33.1g)中,添加PMDA(2.05g、9.4mmol)與NMP(3.7g),在室溫下使其反應15小時而取得聚醯胺酸溶液。藉由從該聚醯胺酸溶液之中取出部分(15.0g),添加NMP(15.0g)與BCS(10.0g)並在室溫下攪拌2小時而取得液晶配向劑PAA-7。<Manufacturing example 9> DA-O1 (2.97g, 10.0mmol) was dissolved in NMP (33.1g), PMDA (2.05g, 9.4mmol) and NMP (3.7g) were added, and reacted at room temperature for 15 hours to obtain polyamide acid solution. Liquid crystal alignment agent PAA-7 was obtained by taking out part (15.0 g) from the polyamic acid solution, adding NMP (15.0 g) and BCS (10.0 g) and stirring at room temperature for 2 hours.

<製造例10> 使DA-O2(2.83g、10.0mmol)溶解於NMP(32.2g)中,添加PMDA(2.05g、9.4mmol)與NMP(3.60g),在室溫下使其反應15小時而取得聚醯胺酸溶液。藉由從該聚醯胺酸溶液之中取出部分(15.0g),添加NMP(15.0g)與BCS(10.0g)並在室溫下攪拌2小時而取得液晶配向劑PAA-8。<Manufacturing example 10> DA-O2 (2.83g, 10.0mmol) was dissolved in NMP (32.2g), PMDA (2.05g, 9.4mmol) and NMP (3.60g) were added, and reacted at room temperature for 15 hours to obtain polyamide acid solution. Liquid crystal alignment agent PAA-8 was obtained by taking out part (15.0 g) from the polyamic acid solution, adding NMP (15.0 g) and BCS (10.0 g) and stirring at room temperature for 2 hours.

<製造例11> 使DA-P1(15.7g、60.0mmol)溶解於NMP(159.0g)中,添加PMDA(11.39g、58.8mmol)與NMP(39.8g),在室溫下使其反應15小時而取得聚醯胺酸溶液。藉由從該聚醯胺酸溶液之中取出部分(15.0g),添加NMP(15.0g)與BCS(10.0g)並在室溫下攪拌2小時而取得液晶配向劑PAA-9。<Manufacturing example 11> DA-P1 (15.7g, 60.0mmol) was dissolved in NMP (159.0g), PMDA (11.39g, 58.8mmol) and NMP (39.8g) were added, and reacted at room temperature for 15 hours to obtain polyamide acid solution. Liquid crystal alignment agent PAA-9 was obtained by taking out part (15.0 g) from the polyamic acid solution, adding NMP (15.0 g) and BCS (10.0 g) and stirring at room temperature for 2 hours.

<製造例12> 使DA-O3(0.730g、1.50mmol)、p-PDA(0.164g、1.52mmol)溶解於NMP(10.7g)中,添加CBDA(0.559g、2.85mmol)並在室溫下使其反應14小時而取得聚醯胺酸溶液。此聚醯胺酸之Mn為7700,Mw為20000。藉由對此聚醯胺酸溶液添加NMP(7.23g)與BCS(4.84g)並在室溫下攪拌2小時而取得液晶配向劑PAA-10。<Manufacturing example 12> DA-O3 (0.730g, 1.50mmol), p-PDA (0.164g, 1.52mmol) were dissolved in NMP (10.7g), CBDA (0.559g, 2.85mmol) was added and reacted at room temperature for 14 hours And obtain polyamide acid solution. The Mn of this polyamic acid is 7700, and the Mw is 20000. The liquid crystal alignment agent PAA-10 was obtained by adding NMP (7.23 g) and BCS (4.84 g) to the polyamic acid solution and stirring at room temperature for 2 hours.

<製造例13> 使DA-O4(0.325g、0.599mmol)、p-PDA(0.261g、2.41 mmol)溶解於NMP(8.45g)中,添加CBDA(0.559g、2.85 mmol),在室溫下使其反應14小時而取得聚醯胺酸溶液。此聚醯胺酸之Mn為8700,Mw為22000。藉由對此聚醯胺酸溶液添加NMP(5.67g)與BCS(3.81g)並在室溫下攪拌2小時而取得液晶配向劑PAA-11。<Manufacturing example 13> DA-O4 (0.325g, 0.599mmol), p-PDA (0.261g, 2.41mmol) were dissolved in NMP (8.45g), CBDA (0.559g, 2.85mmol) was added, and it was made to react at room temperature for 14 hours And obtain polyamide acid solution. The Mn of this polyamic acid is 8700, and the Mw is 22000. The liquid crystal alignment agent PAA-11 was obtained by adding NMP (5.67 g) and BCS (3.81 g) to the polyamic acid solution and stirring at room temperature for 2 hours.

<製造例14> 使TCA(5.55g、25.5mmol)、DA-O1(5.31g、17.90 mmol)及DA-S1(2.91g、7.65mmol)溶解於NMP(55.1g)中,在60℃下使其反應6小時而取得聚醯胺酸溶液。 對此聚醯胺酸溶液(23g)添加NMP稀釋成6.5質量%後,添加作為醯亞胺化觸媒之無水乙酸(8.59g)及吡啶(1.33g),在80℃下使其反應3小時。將此反應溶液投入甲醇(320g),並過濾分離取得之沉澱物。以甲醇洗淨此沉澱物,在60℃下減壓乾燥而取得聚醯亞胺粉末。此聚醯亞胺之醯亞胺化率為59%,Mn為15900,Mw為81000。 對取得之聚醯亞胺粉末(4.2g)添加NMP(37.8g),在70℃下攪拌12小時使其溶解。藉由對此溶液添加BCS(28.0g)並在室溫下攪拌2小時而取得液晶配向劑SPI-3。<Manufacturing example 14> TCA (5.55 g, 25.5 mmol), DA-O1 (5.31 g, 17.90 mmol) and DA-S1 (2.91 g, 7.65 mmol) were dissolved in NMP (55.1 g), and reacted at 60° C. for 6 hours to obtain Obtain a polyamide solution. After adding NMP to this polyamic acid solution (23g) and diluting it to 6.5% by mass, anhydrous acetic acid (8.59g) and pyridine (1.33g) were added as imidization catalysts, and reacted at 80°C for 3 hours . The reaction solution was poured into methanol (320 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 60° C. to obtain a polyimide powder. The imidization rate of this polyimide was 59%, Mn was 15900, and Mw was 81000. NMP (37.8g) was added to the obtained polyimide powder (4.2g), and it stirred and melt|dissolved at 70 degreeC for 12 hours. Liquid crystal alignment agent SPI-3 was obtained by adding BCS (28.0 g) to this solution and stirring at room temperature for 2 hours.

<製造例15> 對製造例14取得之聚醯胺酸溶液(23g)添加NMP而稀釋成6.5質量%後,添加作為醯亞胺化觸媒之無水乙酸(8.59g)及吡啶(1.33g),在80℃下使其反應5小時。將此反應溶液投入甲醇(320g),並過濾分離取得之沉澱物。以甲醇洗淨此沉澱物,在60℃下減壓乾燥而取得聚醯亞胺粉末。此聚醯亞胺之醯亞胺化率為70%,Mn為14100,Mw為69200。 對取得之聚醯亞胺粉末(4.2g)添加NMP(37.8g)並在70℃下攪拌12小時使其溶解。藉由對此溶液添加BCS(28.0g)並在室溫下攪拌2小時而取得液晶配向劑SPI-4。<Manufacturing example 15> After adding NMP to the polyamic acid solution (23g) obtained in Production Example 14 and diluting it to 6.5% by mass, anhydrous acetic acid (8.59g) and pyridine (1.33g) were added as imidization catalysts, and at 80°C It was allowed to react for 5 hours. The reaction solution was poured into methanol (320 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 60° C. to obtain a polyimide powder. The imidization rate of this polyimide was 70%, Mn was 14100, and Mw was 69200. NMP (37.8g) was added to the obtained polyimide powder (4.2g), and it stirred and melt|dissolved at 70 degreeC for 12 hours. Liquid crystal alignment agent SPI-4 was obtained by adding BCS (28.0 g) to this solution and stirring at room temperature for 2 hours.

<製造例16> 使TCA(3.35g、15.0mmol)、p-PDA(1.14g、10.5mmol)及DA-S1(1.71g、4.50mmol)溶解於NMP(24.8g)中,在60℃下使其反應6小時而取得聚醯胺酸溶液。 對此聚醯胺酸溶液(20g)添加NMP稀釋成6.5質量%後,添加作為醯亞胺化觸媒之無水乙酸(4.93g)及吡啶(1.53g)並在110℃下使其反應4小時。將此反應溶液投入甲醇(238g),並過濾分離取得之沉澱物。以甲醇洗淨此沉澱物,在60℃下減壓乾燥而取得聚醯亞胺粉末。此聚醯亞胺之醯亞胺化率為80%,Mn為6660,Mw為16300。 對取得之聚醯亞胺粉末(3.6g)添加NMP(32.4g)並在70℃下攪拌12小時使其溶解。藉由對此溶液添加BCS(24.0g)並在室溫下攪拌2小時而取得液晶配向劑SPI-5。<Manufacturing example 16> TCA (3.35g, 15.0mmol), p-PDA (1.14g, 10.5mmol) and DA-S1 (1.71g, 4.50mmol) were dissolved in NMP (24.8g), and reacted at 60°C for 6 hours to obtain Obtain a polyamide solution. After adding NMP to this polyamic acid solution (20g) and diluting it to 6.5% by mass, anhydrous acetic acid (4.93g) and pyridine (1.53g) were added as imidization catalysts and reacted at 110°C for 4 hours . The reaction solution was poured into methanol (238 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 60° C. to obtain a polyimide powder. The imidization rate of this polyimide was 80%, Mn was 6660, and Mw was 16300. NMP (32.4g) was added to the obtained polyimide powder (3.6g), and it stirred and melt|dissolved at 70 degreeC for 12 hours. The liquid crystal alignment agent SPI-5 was obtained by adding BCS (24.0 g) to this solution and stirring at room temperature for 2 hours.

<製造例17> 使TCA(2.91g、13.0mmol)、DA-O1(5.41g、18.2mmol)及DA-S1(2.97g、7.80mmol)溶解於NMP(54.9g)中,在60℃下使其反應3小時後,添加CBDA(2.42g、12.3mmol)與NMP(9.69g),在40℃下使其反應4小時而取得聚醯胺酸溶液。 對此聚醯胺酸溶液(23g)添加NMP稀釋成6.5質量%後,添加作為醯亞胺化觸媒之無水乙酸(4.41g)及吡啶(1.37g),在75℃下使其反應2.75小時。將此反應溶液投入甲醇(306g),並過濾分離取得之沉澱物。以甲醇洗淨此沉澱物,在60℃下減壓乾燥而取得聚醯亞胺粉末。此聚醯亞胺之醯亞胺化率為70%,Mn為13800,Mw為39000。 對取得之聚醯亞胺粉末(4.2g)添加NMP(37.8g),在70℃下攪拌12小時使其溶解。藉由對此溶液添加BCS(28.0g)並在室溫下攪拌2小時而取得液晶配向劑SPI-6。<Manufacturing example 17> TCA (2.91g, 13.0mmol), DA-O1 (5.41g, 18.2mmol) and DA-S1 (2.97g, 7.80mmol) were dissolved in NMP (54.9g), and reacted at 60°C for 3 hours , CBDA (2.42g, 12.3mmol) and NMP (9.69g) were added, it was made to react at 40 degreeC for 4 hours, and the polyamic-acid solution was acquired. After adding NMP to this polyamic acid solution (23g) and diluting it to 6.5% by mass, anhydrous acetic acid (4.41g) and pyridine (1.37g) were added as imidization catalysts, and reacted at 75°C for 2.75 hours . The reaction solution was poured into methanol (306 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 60° C. to obtain a polyimide powder. The imidization rate of this polyimide was 70%, Mn was 13800, and Mw was 39000. NMP (37.8g) was added to the obtained polyimide powder (4.2g), and it stirred and melt|dissolved at 70 degreeC for 12 hours. Liquid crystal alignment agent SPI-6 was obtained by adding BCS (28.0 g) to this solution and stirring at room temperature for 2 hours.

<製造例18> 使TCA(3.92g、17.5mmol)、p-PDA(2.65g、24.5mmol)及DA-S1(4.00g、10.5mmol)溶解於NMP(42.3g)中,在60℃下使其反應3小時後,添加CBDA(3.26g、16.6mmol)與NMP(13.0g),在40℃下使其反應4小時而取得聚醯胺酸溶液。 對此聚醯胺酸溶液(23g)添加NMP稀釋成6.5質量%後,添加作為醯亞胺化觸媒之無水乙酸(5.87g)及吡啶(1.82g),在50℃下使其反應3小時。將此反應溶液投入甲醇(320g),並過濾分離取得之沉澱物。以甲醇洗淨此沉澱物,在60℃下減壓乾燥而取得聚醯亞胺粉末。此聚醯亞胺之醯亞胺化率為85%,Mn為12800,Mw為19900。 對取得之聚醯亞胺粉末(4.2g)添加NMP(37.8g),在70℃下攪拌12小時使其溶解。藉由對此溶液添加BCS(28.0g)並在室溫下攪拌2小時而取得液晶配向劑SPI-7。<Manufacturing example 18> TCA (3.92g, 17.5mmol), p-PDA (2.65g, 24.5mmol) and DA-S1 (4.00g, 10.5mmol) were dissolved in NMP (42.3g), and reacted at 60°C for 3 hours , CBDA (3.26g, 16.6mmol) and NMP (13.0g) were added, it was made to react at 40 degreeC for 4 hours, and the polyamic-acid solution was acquired. After adding NMP to this polyamic acid solution (23g) and diluting it to 6.5% by mass, anhydrous acetic acid (5.87g) and pyridine (1.82g) were added as imidization catalysts, and reacted at 50°C for 3 hours . The reaction solution was poured into methanol (320 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 60° C. to obtain a polyimide powder. The imidization rate of this polyimide was 85%, Mn was 12800, and Mw was 19900. NMP (37.8g) was added to the obtained polyimide powder (4.2g), and it stirred and melt|dissolved at 70 degreeC for 12 hours. The liquid crystal alignment agent SPI-7 was obtained by adding BCS (28.0 g) to this solution and stirring at room temperature for 2 hours.

<製造例19> 使BODA(2.63g、10.5mmol)、DA-P2(1.67g、8.40 mmol)、DA-O1(2.50g、8.40mmol)及DA-S2(1.65g、4.20 mmol)溶解於NMP(33.8g)中,在60℃下使其反應3小時後,添加CBDA(1.96g、9.98mmol)與NMP(7.82g),在40℃下使其反應4小時而取得聚醯胺酸溶液。此聚醯胺酸之Mn為8500,Mw為20100。藉由對此聚醯胺酸溶液(15g)添加NMP(15g)與BCS(20g)並在室溫下攪拌2小時而取得液晶配向劑PAA-12。<Manufacturing example 19> BODA (2.63g, 10.5mmol), DA-P2 (1.67g, 8.40mmol), DA-O1 (2.50g, 8.40mmol) and DA-S2 (1.65g, 4.20mmol) were dissolved in NMP (33.8g) , After making it react at 60 degreeC for 3 hours, CBDA (1.96g, 9.98mmol) and NMP (7.82g) were added, it was made to react at 40 degreeC for 4 hours, and the polyamic-acid solution was obtained. The Mn of this polyamic acid is 8500, and the Mw is 20100. The liquid crystal alignment agent PAA-12 was obtained by adding NMP (15 g) and BCS (20 g) to the polyamic acid solution (15 g) and stirring at room temperature for 2 hours.

<製造例20> 使BODA(2.69g、10.8mmol)、DA-P2(1.71g、8.60 mmol)、DA-O1(1.28g、4.30mmol)、DA-P3(1.04g、4.30 mmol)及DA-S2(1.69g、4.30mmol)溶解於NMP(33.7g)中,在60℃下使其反應3小時後,添加CBDA(2.00g、10.2mmol)與NMP(8.01g),在40℃下使其反應4小時而取得聚醯胺酸溶液。此聚醯胺酸之Mn為9300,Mw為24000。藉由對此聚醯胺酸溶液(15g)添加NMP(15g)與BCS(20g)並在室溫下攪拌2小時而取得液晶配向劑PAA-13。<Manufacturing example 20> BODA (2.69g, 10.8mmol), DA-P2 (1.71g, 8.60mmol), DA-O1 (1.28g, 4.30mmol), DA-P3 (1.04g, 4.30mmol) and DA-S2 (1.69g, 4.30mmol) was dissolved in NMP (33.7g) and reacted at 60°C for 3 hours, then CBDA (2.00g, 10.2mmol) and NMP (8.01g) were added and reacted at 40°C for 4 hours to obtain polyamide solution. The Mn of this polyamic acid is 9300, and the Mw is 24000. The liquid crystal alignment agent PAA-13 was obtained by adding NMP (15 g) and BCS (20 g) to the polyamic acid solution (15 g) and stirring at room temperature for 2 hours.

<製造例21> 使BODA(2.75g、11.0mmol)、DA-P2(1.75g、8.80 mmol)、DA-P3(2.13g、8.80mmol)及DA-S2(1.67g、4.40 mmol)溶解於NMP(33.3g)中,在60℃下使其反應3小時後,添加CBDA(2.07g、10.6mmol)與NMP(8.28g),在40℃下使其反應4小時而取得聚醯胺酸溶液。此聚醯胺酸之Mn為10600,Mw為33000。藉由對此聚醯胺酸溶液(15g)添加NMP(15g)與BCS(20g)並在室溫下攪拌2小時而取得液晶配向劑PAA-14。<Manufacturing example 21> BODA (2.75g, 11.0mmol), DA-P2 (1.75g, 8.80mmol), DA-P3 (2.13g, 8.80mmol) and DA-S2 (1.67g, 4.40mmol) were dissolved in NMP (33.3g) , After making it react at 60 degreeC for 3 hours, CBDA (2.07g, 10.6mmol) and NMP (8.28g) were added, it was made to react at 40 degreeC for 4 hours, and the polyamic-acid solution was acquired. The Mn of this polyamic acid is 10600, and the Mw is 33000. The liquid crystal alignment agent PAA-14 was obtained by adding NMP (15 g) and BCS (20 g) to the polyamic acid solution (15 g) and stirring at room temperature for 2 hours.

<製造例22> 使BODA(1.15g、4.6mmol)、DBA(0.70g、4.60 mmol)、DA-O1(1.37g、4.60mmol)、DA-P3(1.67g、6.90 mmol)及DA-S1(2.63g、6.90mmol)溶解於NMP(30.1g)中,在60℃下使其反應3小時後,添加CBDA(2.59、34.2mmol)與NMP(10.4g),在室溫下使其反應1小時後,添加PMDA(1.00g、4.60mmol)與NMP(4.01g),在室溫下使其反應3小時而取得聚醯胺酸溶液。 對此聚醯胺酸溶液(28g)添加NMP稀釋成6.5質量%後,添加作為醯亞胺化觸媒之無水乙酸(5.86g)及吡啶(1.81g),在80℃下使其反應3小時。將此反應溶液投入甲醇(370g),並過濾分離取得之沉澱物。以甲醇洗淨此沉澱物,在60℃下減壓乾燥而取得聚醯亞胺粉末。此聚醯亞胺之醯亞胺化率為87%,Mn為12600,Mw為33300。 對取得之聚醯亞胺粉末(4.2g)添加NMP(37.8g),在70℃下攪拌12小時使其溶解。藉由對此溶液添加BCS(28.0g)並在室溫下攪拌2小時而取得液晶配向劑SPI-8。<Manufacturing example 22> BODA (1.15g, 4.6mmol), DBA (0.70g, 4.60mmol), DA-O1 (1.37g, 4.60mmol), DA-P3 (1.67g, 6.90mmol) and DA-S1 (2.63g, 6.90mmol ) was dissolved in NMP (30.1 g), and after reacting at 60°C for 3 hours, CBDA (2.59, 34.2 mmol) and NMP (10.4 g) were added, and after reacting at room temperature for 1 hour, PMDA ( 1.00 g, 4.60 mmol) and NMP (4.01 g) were reacted at room temperature for 3 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (28g) and diluting it to 6.5% by mass, anhydrous acetic acid (5.86g) and pyridine (1.81g) were added as imidization catalysts, and reacted at 80°C for 3 hours . The reaction solution was poured into methanol (370 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 60° C. to obtain a polyimide powder. The imidization rate of this polyimide was 87%, Mn was 12600, and Mw was 33300. NMP (37.8g) was added to the obtained polyimide powder (4.2g), and it stirred and melt|dissolved at 70 degreeC for 12 hours. The liquid crystal alignment agent SPI-8 was obtained by adding BCS (28.0 g) to this solution and stirring at room temperature for 2 hours.

<製造例23> 使BODA(4.88g、19.5mmol)、DDM(1.93g、9.75 mmol)、DA-P4(1.29g、3.90mmol)、DA-P5(2.78g、11.7 mmol)及DA-S2(5.39g、13.7mmol)溶解於NMP(65.3g)中,在60℃下使其反應3小時後,添加CBDA(3.63、18.5mmol)與NMP(14.5g),在40℃下使其反應4小時而取得聚醯胺酸溶液。 對此聚醯胺酸溶液(55g)添加NMP稀釋成6.5質量%後,添加作為醯亞胺化觸媒之無水乙酸(10.9g)及吡啶(3.38g),在80℃下使其反應3小時。將此反應溶液投入甲醇(730g),並過濾分離取得之沉澱物。以甲醇洗淨此沉澱物,在60℃下減壓乾燥而取得聚醯亞胺粉末。此聚醯亞胺之醯亞胺化率為74%,Mn為13900,Mw為40700。 對取得之聚醯亞胺粉末(4.2g)添加NMP(37.8g),在70℃下攪拌12小時使其溶解。對此溶液添加BCS(28.0g)並在室溫下攪拌2小時而取得液晶配向劑SPI-9。<Manufacturing example 23> BODA (4.88g, 19.5mmol), DDM (1.93g, 9.75mmol), DA-P4 (1.29g, 3.90mmol), DA-P5 (2.78g, 11.7mmol) and DA-S2 (5.39g, 13.7mmol ) was dissolved in NMP (65.3g) and reacted at 60°C for 3 hours, then CBDA (3.63, 18.5mmol) and NMP (14.5g) were added and reacted at 40°C for 4 hours to obtain polyamide acid solution. After adding NMP to this polyamic acid solution (55g) and diluting it to 6.5% by mass, anhydrous acetic acid (10.9g) and pyridine (3.38g) were added as imidization catalysts, and reacted at 80°C for 3 hours . The reaction solution was poured into methanol (730 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 60° C. to obtain a polyimide powder. The imidization ratio of this polyimide was 74%, Mn was 13900, and Mw was 40700. NMP (37.8g) was added to the obtained polyimide powder (4.2g), and it stirred and melt|dissolved at 70 degreeC for 12 hours. BCS (28.0g) was added to this solution, and it stirred at room temperature for 2 hours, and obtained liquid crystal aligning agent SPI-9.

<製造例24> 使BODA(1.00g、4.00mmol)、DBA(1.22g、8.00 mmol)、DA-P3(1.45g、6.00mmol)及DA-S1(2.28g、6.00 mmol)溶解於NMP(23.8g)中,在60℃下使其反應3小時後,添加CBDA(2.27、11.6mmol)與NMP(9.01g),在室溫下使其反應1小時後,添加PMDA(0.87g、4.00mmol)與NMP(3.49g),在室溫下使其反應3小時而取得聚醯胺酸溶液。 對此聚醯胺酸溶液(g)添加NMP稀釋成6.5質量%後,添加作為醯亞胺化觸媒之無水乙酸(g)及吡啶(g),在80℃下使其反應3小時。將此反應溶液投入甲醇(370g),並過濾分離取得之沉澱物。以甲醇洗淨此沉澱物,在60℃下減壓乾燥而取得聚醯亞胺粉末。此聚醯亞胺之醯亞胺化率為74%,Mn為11000,Mw為27400。 對取得之聚醯亞胺粉末(4.2g)添加NMP(37.8g),在70℃下攪拌12小時使其溶解。藉由對此溶液添加BCS(28g)並在室溫下攪拌2小時而取得液晶配向劑SPI-10。<Manufacturing example 24> BODA (1.00g, 4.00mmol), DBA (1.22g, 8.00mmol), DA-P3 (1.45g, 6.00mmol) and DA-S1 (2.28g, 6.00mmol) were dissolved in NMP (23.8g), in After reacting at 60° C. for 3 hours, CBDA (2.27, 11.6 mmol) and NMP (9.01 g) were added, and after reacting at room temperature for 1 hour, PMDA (0.87 g, 4.00 mmol) and NMP (3.49 g ), it was reacted at room temperature for 3 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (g) and diluting to 6.5% by mass, anhydrous acetic acid (g) and pyridine (g) were added as an imidization catalyst, and it was made to react at 80 degreeC for 3 hours. The reaction solution was poured into methanol (370 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 60° C. to obtain a polyimide powder. The imidization rate of this polyimide was 74%, Mn was 11000, and Mw was 27400. NMP (37.8g) was added to the obtained polyimide powder (4.2g), and it stirred and melt|dissolved at 70 degreeC for 12 hours. Liquid crystal alignment agent SPI-10 was obtained by adding BCS (28 g) to this solution and stirring at room temperature for 2 hours.

<製造例25> 藉由將製造例22取得之液晶配向劑SPI-8(7.00g)及製造例23取得之液晶配向劑SPI-9(3.00g)在室溫下攪拌3小時而取得液晶配向劑SPI-11。<Manufacturing example 25> The liquid crystal alignment agent SPI-11 was obtained by stirring the liquid crystal alignment agent SPI-8 (7.00 g) obtained in Production Example 22 and the liquid crystal alignment agent SPI-9 (3.00 g) obtained in Production Example 23 at room temperature for 3 hours.

<製造例26> 藉由將製造例22取得之液晶配向劑SPI-8(7.00g)、製造例23取得之液晶配向劑SPI-9(3.00g)及AD-1(0.06g)在室溫下攪拌3小時而取得液晶配向劑SPI-12。<Manufacturing example 26> By stirring the liquid crystal alignment agent SPI-8 (7.00g) obtained in Production Example 22, the liquid crystal alignment agent SPI-9 (3.00g) and AD-1 (0.06g) obtained in Production Example 23 at room temperature for 3 hours. Obtain liquid crystal alignment agent SPI-12.

<製造例27> 藉由將製造例22取得之液晶配向劑SPI-8(7.00g)、製造例23取得之液晶配向劑SPI-9(3.00g)及AD-2(0.06g)在室溫下攪拌3小時而取得液晶配向劑SPI-13。<Manufacturing example 27> By stirring the liquid crystal alignment agent SPI-8 (7.00g) obtained in Production Example 22, the liquid crystal alignment agent SPI-9 (3.00g) and AD-2 (0.06g) obtained in Production Example 23 at room temperature for 3 hours Obtain liquid crystal alignment agent SPI-13.

<製造例28> 使BODA(1.25g、5.00mmol)、DA-O3(3.41g、7.00 mmol)、及DA-S1(1.14g、3.00mmol)溶解於NMP(23.2g)中,在60℃下使其反應3小時後,添加CBDA(0.88g、4.50mmol)與NMP(3.50g),在40℃下使其反應4小時而取得聚醯胺酸溶液。此聚醯胺酸之數平均分子量為10500,重量平均分子量為30700。 藉由對此聚醯胺酸溶液(5.4g)添加NMP(5.40g)與BCS(7.20g)並在室溫下攪拌2小時而取得液晶配向劑PAA-15。<Manufacturing example 28> BODA (1.25g, 5.00mmol), DA-O3 (3.41g, 7.00mmol), and DA-S1 (1.14g, 3.00mmol) were dissolved in NMP (23.2g), and reacted at 60°C for 3 hours Then, CBDA (0.88g, 4.50mmol) and NMP (3.50g) were added, it was made to react at 40 degreeC for 4 hours, and the polyamic-acid solution was obtained. The number average molecular weight of this polyamide acid is 10500, and the weight average molecular weight is 30700. The liquid crystal alignment agent PAA-15 was obtained by adding NMP (5.40 g) and BCS (7.20 g) to the polyamic acid solution (5.4 g) and stirring at room temperature for 2 hours.

<製造例29> 使BODA(1.88g、7.50mmol)、DA-P4(2.48g、7.50 mmol)、DA-O1(1.12g、3.75mmol)、及DA-S3(2.84g、3.75 mmol)溶解於NMP(33.2g)中,在60℃下使其反應3小時後,添加CBDA(1.43g、7.31mmol)與NMP(5.50g),在40℃下使其反應4小時而取得聚醯胺酸溶液。 對此聚醯胺酸溶液(25g)添加NMP稀釋成6.5質量%後,添加作為醯亞胺化觸媒之無水乙酸(3.92g)及吡啶(1.21g),在80℃下使其反應3小時。將此反應溶液投入甲醇(287g),並過濾分離取得之沉澱物。以甲醇洗淨此沉澱物,在60℃下減壓乾燥而取得聚醯亞胺粉末。此聚醯亞胺之醯亞胺化率為76%,、Mn為15000,Mw為55800。 對取得之聚醯亞胺粉末(2.0g)添加NMP(18.0g),在70℃下攪拌12小時使其溶解。藉由對此溶液添加BCS(13.3g)並在室溫下攪拌2小時而取得液晶配向劑SPI-14。<Manufacturing example 29> BODA (1.88g, 7.50mmol), DA-P4 (2.48g, 7.50mmol), DA-O1 (1.12g, 3.75mmol), and DA-S3 (2.84g, 3.75mmol) were dissolved in NMP (33.2g) In, after making it react at 60 degreeC for 3 hours, CBDA (1.43g, 7.31mmol) and NMP (5.50g) were added, it was made to react at 40 degreeC for 4 hours, and the polyamic-acid solution was obtained. After adding NMP to this polyamic acid solution (25g) and diluting it to 6.5% by mass, anhydrous acetic acid (3.92g) and pyridine (1.21g) were added as imidization catalysts, and reacted at 80°C for 3 hours . The reaction solution was poured into methanol (287 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 60° C. to obtain a polyimide powder. The imidization rate of this polyimide was 76%, Mn was 15000, and Mw was 55800. NMP (18.0 g) was added to the obtained polyimide powder (2.0 g), and it stirred and melt|dissolved at 70 degreeC for 12 hours. Liquid crystal alignment agent SPI-14 was obtained by adding BCS (13.3 g) to this solution and stirring at room temperature for 2 hours.

<製造例30> 使BODA(2.13g、8.50mmol)、DA-P4(2.81g、8.50 mmol)、p-PDA(0.46g、4.25mmol)、及DA-S3(3.22g、4.25 mmol)溶解於NMP(34.4g)中,在60℃下使其反應3小時後,添加CBDA(1.59g、8.11mmol)與NMP(6.40g),在40℃下使其反應4小時而取得聚醯胺酸溶液。 對此聚醯胺酸溶液(45.1g)添加NMP稀釋成6.5質量%後,添加作為醯亞胺化觸媒之無水乙酸(7.62g)及吡啶(2.36g),在75℃下使其反應2.5小時。將此反應溶液投入甲醇(456g),並過濾分離取得之沉澱物。以甲醇洗淨此沉澱物,在60℃下減壓乾燥而取得聚醯亞胺粉末。此聚醯亞胺之醯亞胺化率為75%,Mn為16500,Mw為46600。 對取得之聚醯亞胺粉末(2.0g)添加NMP(18.0g),在70℃下攪拌12小時使其溶解。藉由對此溶液添加BCS(13.3g)並在室溫下攪拌2小時而取得液晶配向劑SPI-15。<Manufacturing example 30> BODA (2.13g, 8.50mmol), DA-P4 (2.81g, 8.50mmol), p-PDA (0.46g, 4.25mmol), and DA-S3 (3.22g, 4.25mmol) were dissolved in NMP (34.4g) In, after making it react at 60 degreeC for 3 hours, CBDA (1.59g, 8.11mmol) and NMP (6.40g) were added, it was made to react at 40 degreeC for 4 hours, and the polyamic-acid solution was obtained. After adding NMP to this polyamic acid solution (45.1g) and diluting it to 6.5% by mass, anhydrous acetic acid (7.62g) and pyridine (2.36g) were added as imidization catalysts and reacted at 75°C for 2.5 Hour. The reaction solution was poured into methanol (456 g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 60° C. to obtain a polyimide powder. The imidization rate of this polyimide was 75%, Mn was 16500, and Mw was 46600. NMP (18.0 g) was added to the obtained polyimide powder (2.0 g), and it stirred and melt|dissolved at 70 degreeC for 12 hours. The liquid crystal alignment agent SPI-15 was obtained by adding BCS (13.3 g) to this solution and stirring at room temperature for 2 hours.

上述製造例1~30取得之各液晶配向劑之規格係如下述之表1-1~表1-3所示。The specifications of the liquid crystal alignment agents obtained in the above manufacturing examples 1 to 30 are shown in the following Tables 1-1 to 1-3.

Figure 02_image147
Figure 02_image147

Figure 02_image149
Figure 02_image149

Figure 02_image151
Figure 02_image151

<實施例1> 使用製造例1取得之液晶配向劑PAA-1,以下述所示之操作順序進行液晶單元之製作。將液晶配向劑PAA-1旋轉塗佈於附ITO電極之玻璃基板上,在80℃加熱板上乾燥90秒鐘後,使用230℃之熱風循環式烤箱進行30分鐘煆燒,而形成膜厚100nm之液晶配向膜。準備2枚此附液晶配向膜之基板,在其1枚之液晶配向膜上印刷熱硬化性密封劑(協立化學公司製XN-1500T)。其次,將以另一方之基板之已形成液晶配向膜側之面朝向內側之方式貼合至先前之基板後,使密封劑硬化而製作成空單元。藉由減壓注入法對此空單元注入含PSA用聚合性化合物之液晶MLC-3023(默克公司製商品名),而製作成液晶單元。測量此液晶單元之電壓保持率(VHR)。<Example 1> Using the liquid crystal alignment agent PAA-1 obtained in Production Example 1, a liquid crystal cell was prepared in the following operation procedure. Spin-coat liquid crystal alignment agent PAA-1 on a glass substrate with ITO electrodes, dry it on a hot plate at 80°C for 90 seconds, and then bake it in a hot air circulation oven at 230°C for 30 minutes to form a film with a thickness of 100nm The liquid crystal alignment film. Two of these substrates with liquid crystal alignment films were prepared, and a thermosetting sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on one of the liquid crystal alignment films. Next, after affixing the other substrate to the previous substrate so that the surface on which the liquid crystal alignment film has been formed faces inward, the sealant is cured to form an empty cell. Liquid crystal MLC-3023 (trade name manufactured by Merck) containing a polymerizable compound for PSA was injected into this empty cell by a reduced-pressure injection method to produce a liquid crystal cell. The voltage holding ratio (VHR) of this liquid crystal cell was measured.

其次,PSA處理該液晶單元,並測量PSA處理後之電壓保持率。並且,在高溫高濕條件下使該單元老化,並測量老化後之電壓保持率。 [電壓保持率之評價] 在60℃之熱風循環烤箱中,施加1V電壓60μs,其後測量1667msec後之電壓,並計算電壓能保持多久時間作為電壓保持率。電壓保持率之測量係使用東陽科技公司製之VHR-1。Next, the liquid crystal cell was treated with PSA, and the voltage retention rate after PSA treatment was measured. And, the unit was aged under high-temperature and high-humidity conditions, and the voltage retention rate after aging was measured. [Evaluation of voltage retention rate] In a hot air circulation oven at 60°C, apply a voltage of 1V for 60μs, then measure the voltage after 1667msec, and calculate how long the voltage can be maintained as the voltage retention rate. The measurement of the voltage retention ratio uses VHR-1 manufactured by Dongyang Technology Co., Ltd.

[PSA處理] 在施加15V之DC電壓之狀態,從液晶單元之外側照射通過325nm以下切斷濾光器之10J/cm2 之UV 。尚且,UV之照度係使用ORC公司製UV-MO3A進行測量。其後以使殘留於液晶單元中之未反應聚合性化合物失活為目的,在未施加電壓之狀態下使用東芝照明科技公司製UV-FL照射裝置照射UV(UV燈:FLR40SUV32/A-1)30分鐘。 [老化] 將PSA處理後之液晶單元放置於設定成85℃、濕度85%之恆溫恆濕槽中10天。[PSA treatment] In the state where a DC voltage of 15V was applied, 10J/cm 2 of UV which passed through a cutoff filter of 325nm or less was irradiated from the outside of the liquid crystal cell. In addition, the UV illuminance was measured using UV-MO3A manufactured by ORC Corporation. Thereafter, for the purpose of deactivating the unreacted polymerizable compound remaining in the liquid crystal cell, UV was irradiated with a UV-FL irradiation device manufactured by Toshiba Lighting Technology Co., Ltd. (UV lamp: FLR40SUV32/A-1) in a state where no voltage was applied. 30 minutes. [Aging] The PSA-treated liquid crystal cell was placed in a constant temperature and humidity chamber set at 85°C and a humidity of 85% for 10 days.

<實施例2、3、10、11、12、13、14,比較例1、2、5、6、7> 除了取代液晶配向劑PAA-1而分別改用液晶配向劑PAA-2、PAA-3、PAA-15、SPI-1、SPI-2、SPI-3、SPI-4、SPI-5、SPI-6、SPI-7、SPI-14、SPI-15以外,其他係與實施例1同樣地操作而製作出個別之液晶單元。 對於取得之各液晶單元,與實施例1地同樣地操作,並測量初期、PSA處理後、老化後之電壓保持率、因老化導致之電壓保持率之下降值(Δ(PSA處理後-老化後))。將個別之結果展示於下述表2。<Examples 2, 3, 10, 11, 12, 13, 14, Comparative Examples 1, 2, 5, 6, 7> In addition to replacing the liquid crystal alignment agent PAA-1, the liquid crystal alignment agent PAA-2, PAA-3, PAA-15, SPI-1, SPI-2, SPI-3, SPI-4, SPI-5, SPI-6 were used instead , SPI-7, SPI-14, and SPI-15, the others were operated in the same manner as in Example 1 to produce individual liquid crystal cells. For each liquid crystal cell obtained, operate in the same manner as in Example 1, and measure the voltage retention rate at the initial stage, after PSA treatment, after aging, and the drop value (Δ(after PSA treatment-after aging) of the voltage retention rate due to aging )). Individual results are shown in Table 2 below.

Figure 02_image153
Figure 02_image153

如表2所示,在與使用不包含具有噁唑啉骨架之聚合物之液晶配向劑PAA-3、SPI-2、SPI-5、SPI-7、SPI-15之比較例1、2、5、6、7相比,在使用包含具有噁唑啉骨架之聚合物之液晶配向劑PAA-1、PAA-2、PAA-15、SPI-1、SPI-3、SPI-4、SPI-6、SPI-14之實施例1、2、10、3、11、12、13、14中發現到因老化導致之電壓保持率之下降為小。 因此,得知包含具有噁唑啉骨架之聚合物之液晶配向劑可取得不易引起因老化導致之電壓保持率下降之液晶配向膜。As shown in Table 2, in Comparative Examples 1, 2, and 5 using liquid crystal alignment agents PAA-3, SPI-2, SPI-5, SPI-7, and SPI-15 that do not contain polymers with an oxazoline skeleton , 6, and 7, when using liquid crystal alignment agents PAA-1, PAA-2, PAA-15, SPI-1, SPI-3, SPI-4, SPI-6, In Examples 1, 2, 10, 3, 11, 12, 13, and 14 of SPI-14, it was found that the decrease in the voltage retention rate due to aging was small. Therefore, it is known that a liquid crystal alignment agent comprising a polymer having an oxazoline skeleton can obtain a liquid crystal alignment film that is less prone to decrease in voltage retention due to aging.

[摩擦耐性] 將液晶配向劑旋轉塗佈於全表面附有ITO電極之玻璃基板之ITO面上,在70℃之加熱板上使其暫時乾燥90秒鐘。其後,在230℃之IR式烤箱中進行30分鐘煆燒,使膜厚100nm之塗膜形成,而取得附液晶配向膜之基板。對此液晶配向膜以嫘縈布進行摩擦(軋輥直徑:120mm、軋輥旋轉數:1000rpm、移動速度:20mm/sec、壓入長度:0.6mm)。使用顯微鏡進行觀察本基板,將膜面上未發現因摩擦造成之條痕者評為「良好」,將發現條痕者評為「不良」。[Friction Resistance] The liquid crystal alignment agent was spin-coated on the ITO surface of the glass substrate with ITO electrodes attached to the entire surface, and temporarily dried on a heating plate at 70°C for 90 seconds. Thereafter, it was baked in an IR oven at 230° C. for 30 minutes to form a coating film with a thickness of 100 nm to obtain a substrate with a liquid crystal alignment film. The liquid crystal alignment film was rubbed with rayon cloth (roll diameter: 120 mm, roll rotation speed: 1000 rpm, moving speed: 20 mm/sec, press-in length: 0.6 mm). The substrate was observed with a microscope, and those on which no streaks due to friction were found on the film surface were rated as "good", and those where streaks were found were rated as "poor".

<實施例4~9、比較例3、4> 對於液晶配向劑PAA-4、PAA-5、PAA-6、PAA-7、PAA-8、PAA-9、PAA-10、及PAA-11,進行上述摩擦耐性之評價。將個別之結果展示於下述表3。<Examples 4 to 9, Comparative Examples 3 and 4> For the liquid crystal alignment agents PAA-4, PAA-5, PAA-6, PAA-7, PAA-8, PAA-9, PAA-10, and PAA-11, the above rubbing resistance was evaluated. Individual results are shown in Table 3 below.

Figure 02_image155
Figure 02_image155

如表3所示,關於在包含具有噁唑啉骨架之聚合物之液晶配向劑PAA-4、PAA-5、PAA-7、PAA-8、PAA-10、PAA-11之實施例4、5、6、7、8、9中,未發現因摩擦處理造成條痕,故為良好者。另一方面,在關於不包含具有噁唑啉骨架之聚合物之液晶配向劑PAA-6、PAA-9之比較例3、4中,發現諸多因摩擦造成之條痕,故為不良者。 因此,得知包含具有噁唑啉骨架之聚合物之液晶配向劑可取得不易產生因摩擦處理造成之膜剝離或傷痕之液晶配向膜。As shown in Table 3, examples 4 and 5 of liquid crystal alignment agents PAA-4, PAA-5, PAA-7, PAA-8, PAA-10, and PAA-11 containing polymers with an oxazoline skeleton , 6, 7, 8, and 9, no streaks due to rubbing treatment were found, so it was good. On the other hand, in Comparative Examples 3 and 4 of liquid crystal alignment agents PAA-6 and PAA-9 not containing a polymer having an oxazoline skeleton, many streaks due to rubbing were found, so they were unfavorable. Therefore, it is known that a liquid crystal alignment agent containing a polymer having an oxazoline skeleton can obtain a liquid crystal alignment film that is less prone to film peeling or scratches caused by rubbing treatment.

<實施例15> 使用製造例19取得之液晶配向劑PAA-12,以下述所示之操作順序進行密著性評價試樣之製作。將液晶配向劑PAA-12旋轉塗佈於附ITO電極之玻璃基板上,在80℃之加熱板上乾燥90秒鐘後,在230℃之熱風循環式烤箱中進行30分鐘煆燒,而形成膜厚100nm之液晶配向膜。<Example 15> Using the liquid crystal alignment agent PAA-12 obtained in manufacture example 19, the preparation of the adhesion evaluation sample was performed by the operation procedure shown below. Spin-coat liquid crystal alignment agent PAA-12 on a glass substrate with ITO electrodes, dry it on a heating plate at 80°C for 90 seconds, and then bake it in a hot air circulation oven at 230°C for 30 minutes to form a film Liquid crystal alignment film with a thickness of 100nm.

準備藉此而得之2枚基板,在一側基板之液晶配向膜面上塗佈4μm間隔珠後,滴入密封劑(協立化學公司製XN-1500T)。其次,以使另一側基板之液晶配向膜面朝向內側,且基板之重疊寬度成為1cm之方式進行貼合。於此之際,以貼合後之密封劑之直徑成為3mm之方式來調整密封劑滴入量。使用夾具固定已貼合之2枚基板後,以150℃使其熱硬化1小時,而製作出密著性評價用之試樣。 [密著性之測量] 將上述試樣基板在桌上形精密萬能試驗機(島津製作所公司製AGS-X 500N)中,固定上下基板之邊端部分後,從基板中央部之上部進行押入,並測量剝離時之力度(N)。Two substrates thus obtained were prepared, and after coating 4 μm spacer beads on the liquid crystal alignment film surface of one substrate, a sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was dropped. Next, it bonded so that the liquid crystal alignment film surface of the other board|substrate faced inward, and the overlapping width of a board|substrate became 1 cm. On this occasion, the sealing agent dropping amount was adjusted so that the diameter of the bonding sealing agent may become 3 mm. After fixing the bonded two boards with a jig, they were thermally cured at 150°C for 1 hour to prepare a sample for adhesion evaluation. [Measurement of Adhesion] The above-mentioned sample substrates were placed in a desktop precision universal testing machine (AGS-X 500N manufactured by Shimadzu Corporation), and after fixing the edge portions of the upper and lower substrates, they were pushed in from the upper part of the central part of the substrates, and the force at the time of peeling was measured ( N).

<實施例16、17、18、19、20、比較例10、11> 除了取代液晶配向劑PAA-12而分別改用液晶配向劑PAA-13、PAA-14、SPI-8、SPI-10、SPI-11、SPI-12、SPI-13以外,其他係與實施例15同樣地操作並測量個別之密著性。將個別之結果展示於下述表4。<Examples 16, 17, 18, 19, 20, Comparative Examples 10, 11> Except that the liquid crystal alignment agent PAA-12 is replaced by the liquid crystal alignment agent PAA-13, PAA-14, SPI-8, SPI-10, SPI-11, SPI-12, and SPI-13, the other systems are the same as in Example 15. Do the same and measure the individual adhesion. Individual results are shown in Table 4 below.

Figure 02_image157
Figure 02_image157

如表4所示,在與使用不包含具有噁唑啉骨架之聚合物之液晶配向劑PAA-14、SPI-10之比較例10、11相比,在使用包含具有噁唑啉骨架之聚合物之液晶配向劑PAA-12、PAA-13、SPI-8、SPI-11、SPI-12、SPI-13之實施例15、16、17、18、19、20中確認到密封密著性較強。As shown in Table 4, compared with Comparative Examples 10 and 11 using liquid crystal alignment agents PAA-14 and SPI-10 that do not contain a polymer with an oxazoline skeleton, when using a polymer with an oxazoline skeleton The liquid crystal alignment agents PAA-12, PAA-13, SPI-8, SPI-11, SPI-12, and SPI-13 in Examples 15, 16, 17, 18, 19, and 20 confirmed that the seal adhesion is strong .

尚且,將2017年9月13日提出申請之日本專利申請案第2017-175632號之說明書、申請專利範圍、圖式、及摘要之全部內容引用至此,作為本發明說明書之開示內容並予以導入者。Moreover, the entire content of the Japanese patent application No. 2017-175632 filed on September 13, 2017, including the specification, scope of claims, drawings, and abstract, is hereby cited as the disclosure content of the specification of the present invention and introduced .

Claims (11)

一種液晶配向劑,其特徵為含有具有噁唑啉骨架之聚合物,且該聚合物為源自選自下述式(2-1)、(2-2)及(2-3)之二胺之聚合物;
Figure 107132267-A0305-02-0102-4
Figure 107132267-A0305-02-0102-5
Figure 107132267-A0305-02-0102-6
R1表示氫或一價有機基;R2表示由選自由單鍵、-O-、-COO-、-OCO-、-(CH2)l-、-O(CH2)lO-、-CONR11-、-NR11CO-及-NR11-所成群之至少一種所構成之2價有機基;W1表示選自下述群(3-1)之構造;W2表示選自下述群(3-2)之構造;W3表示選自下述群(3-3)之構造;W4表示選自下述群(3-4)之構造;在此,R11表示氫,或1價有機基,l表示1~12之整數,a表示0或1之整數;
Figure 107132267-A0305-02-0103-7
Figure 107132267-A0305-02-0103-8
Figure 107132267-A0305-02-0103-12
Figure 107132267-A0305-02-0103-23
群(3-1)中,*1表示與式(2-1)~(2-3)中之胺基鍵結之部位,*2表示與噁唑啉環鍵結之部位;群(3-2)中,*1表示與式(2-1)~(2-3)中之胺基鍵結之部位,*3表示與R2鍵結之部位;群(3-3)中,*3表示與R2鍵結之部位;群(3-4)中,*2表示與噁唑啉環鍵結之部位;X表示氫原子、鹵素原子、碳數1~6之烷基、碳數1~6之鹵化烷基、取代胺基、碳數1~6之烷氧基,或醯胺基。
A liquid crystal alignment agent, characterized by containing a polymer with an oxazoline skeleton, and the polymer is derived from a diamine selected from the following formulas (2-1), (2-2) and (2-3) the polymer;
Figure 107132267-A0305-02-0102-4
Figure 107132267-A0305-02-0102-5
Figure 107132267-A0305-02-0102-6
R 1 represents hydrogen or a monovalent organic group; R 2 represents a group consisting of a single bond, -O-, -COO-, -OCO-, -(CH 2 ) l -, -O(CH 2 ) l O-, - A divalent organic group composed of at least one of CONR 11 -, -NR 11 CO- and -NR 11 -; W 1 represents a structure selected from the following group (3-1); W 2 represents a structure selected from the following The structure of said group (3-2); W 3 represents the structure selected from the following group (3-3); W 4 represents the structure selected from the following group (3-4); Here, R 11 represents hydrogen, Or a monovalent organic group, l represents an integer from 1 to 12, and a represents an integer from 0 or 1;
Figure 107132267-A0305-02-0103-7
Figure 107132267-A0305-02-0103-8
Figure 107132267-A0305-02-0103-12
Figure 107132267-A0305-02-0103-23
In the group (3-1), * 1 represents the position bonded to the amino group in the formula (2-1) ~ (2-3), and * 2 represents the position bonded to the oxazoline ring; the group (3- 2), * 1 represents the position bonded to the amino group in formula (2-1) ~ (2-3), * 3 represents the position bonded to R 2 ; in group (3-3), * 3 Represents the site bonded to R2 ; in group (3-4), * 2 represents the site bonded to the oxazoline ring; X represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbons, and a carbon number 1 ~6 halogenated alkyl groups, substituted amino groups, alkoxy groups with 1~6 carbon atoms, or amido groups.
如請求項1之液晶配向劑,其中前述具有噁唑啉骨架之聚合物為選自由包含下述式(6)所示之構造單位之聚醯 亞胺前驅物,及其醯亞胺化物之聚醯亞胺所成群之至少1種;
Figure 107132267-A0305-02-0104-14
X1表示源自四羧酸衍生物之4價有機基;Y1表示源自二胺之2價有機基,且該二胺包含從前述式(2-1)、(2-2)或(2-3)之二胺去除2個胺基的構造;R4表示氫原子或碳數1~5之烷基。
The liquid crystal alignment agent as claimed in item 1, wherein the aforementioned polymer having an oxazoline skeleton is a polyimide precursor selected from a structural unit represented by the following formula (6), and a polyimide compound thereof. At least one type of group of imides;
Figure 107132267-A0305-02-0104-14
X 1 represents a 4-valent organic group derived from a tetracarboxylic acid derivative; Y 1 represents a 2-valent organic group derived from a diamine, and the diamine comprises the following formula (2-1), (2-2) or ( 2-3) The structure in which two amino groups are removed from the diamine; R 4 represents a hydrogen atom or an alkyl group with 1 to 5 carbons.
如請求項2之液晶配向劑,其中前述式(6)中,X1之構造為選自下述構造中之至少1種;
Figure 107132267-A0305-02-0104-16
Figure 107132267-A0305-02-0105-17
The liquid crystal alignment agent according to claim 2, wherein in the aforementioned formula (6), the structure of X1 is at least one selected from the following structures;
Figure 107132267-A0305-02-0104-16
Figure 107132267-A0305-02-0105-17
如請求項2或3之液晶配向劑,其中相對於前述聚合物之全部構造單位,前述式(6)所示之構造單位為10莫耳%以上。 The liquid crystal alignment agent according to claim 2 or 3, wherein the structural unit represented by the aforementioned formula (6) is more than 10 mol % relative to all structural units of the aforementioned polymer. 一種液晶配向膜,其係由如請求項1~4中任一項之液晶配向劑所得。 A liquid crystal alignment film obtained from the liquid crystal alignment agent according to any one of claims 1-4. 一種液晶顯示元件,其係具備如請求項5之液晶配向膜。 A liquid crystal display element, which is provided with the liquid crystal alignment film according to claim 5. 一種二胺,其係具有如下述式(2-1)、(2-2)或(2-3)所示之噁唑啉骨架
Figure 107132267-A0305-02-0106-18
Figure 107132267-A0305-02-0106-19
Figure 107132267-A0305-02-0106-20
各記號之定義係與請求項1中之記載相同。
A kind of diamine, it has the oxazoline skeleton shown in following formula (2-1), (2-2) or (2-3)
Figure 107132267-A0305-02-0106-18
Figure 107132267-A0305-02-0106-19
Figure 107132267-A0305-02-0106-20
The definition of each symbol is the same as that described in Claim 1.
一種聚合物,其係具有源自如請求項7之二胺之噁唑啉骨架。 A polymer having an oxazoline skeleton derived from the diamine as claimed in claim 7. 如請求項8之聚合物,其中前述具有噁唑啉骨架之聚合物為包含下述式(6)所示之構造單位之聚醯亞胺前驅物,及其醯亞胺化物之聚醯亞胺
Figure 107132267-A0305-02-0106-21
各記號之定義係與請求項2中之記載相同。
The polymer as claimed in item 8, wherein the aforementioned polymer having an oxazoline skeleton is a polyimide precursor comprising a structural unit shown in the following formula (6), and a polyimide of an imidate thereof
Figure 107132267-A0305-02-0106-21
The definition of each symbol is the same as that described in claim 2.
如請求項9之聚合物,其中前述式(6)中,X1之構造為選自下述構造中之至少1種
Figure 107132267-A0305-02-0107-22
The polymer as claimed in item 9, wherein in the aforementioned formula (6), the structure of X1 is at least one selected from the following structures
Figure 107132267-A0305-02-0107-22
如請求項9或10之聚合物,其中相對於前述聚合物之全部構造單位,前述式(6)所示之構造單位為10莫耳%以上。 The polymer according to claim 9 or 10, wherein the structural unit represented by the aforementioned formula (6) is 10 mol% or more relative to all structural units of the aforementioned polymer.
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