TW202146632A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents
Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element Download PDFInfo
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Abstract
Description
本發明為關於液晶配向劑、液晶配向膜及液晶顯示元件。The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film and a liquid crystal display element.
以往以來，液晶顯示裝置被廣泛地作為個人電腦、智慧型手機、行動電話、電視接收器等的顯示部使用。液晶顯示裝置具備有例如：被挾持在元件基板與彩色濾光片基板之間的液晶層、對於液晶層外加電場的像素電極及共通電極、控制液晶層之液晶分子之配向性的配向膜、切換供給於像素電極之電訊號的薄膜電晶體(TFT)等。作為液晶分子之驅動方式，已知有TN方式、VA方式等的縱向電場方式或IPS方式、FFS(邊緣電場切換)方式等的橫向電場方式。Conventionally, liquid crystal display devices have been widely used as display units of personal computers, smart phones, mobile phones, television receivers, and the like. The liquid crystal display device includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode to which an electric field is applied to the liquid crystal layer, an alignment film that controls the alignment of liquid crystal molecules in the liquid crystal layer, and a switching device. Thin film transistors (TFTs), etc., which supply electrical signals to the pixel electrodes. As a driving method of liquid crystal molecules, a vertical electric field method such as a TN method and a VA method, and a lateral electric field method such as an IPS method and an FFS (Fringe Field Switching) method are known.
現今，工業上最普及的液晶配向膜，係藉由將形成在電極基板上的含有聚醯胺酸及/或將該聚醯胺酸醯亞胺化而得的聚醯亞胺所組成之膜的表面，以綿、尼龍、聚酯等的布朝一個方向擦拭(亦即，進行摩擦處理)來製作。摩擦處理係簡便且生產性優異的工業上有用之方法。然而，隨著液晶顯示元件的高性能化、高精細化、大型化，由於以摩擦處理所產生的配向膜表面的傷痕、發塵、機械性力量或靜電而造成影響，進而，配向處理面內的不均勻性等的各種問題已非常明確。作為取代摩擦處理的配向處理方法，已知有藉由照射經偏光的放射線，來賦予液晶配向能之光配向法。光配向法係已提案有利用光異構化反應者、利用光交聯反應者、利用光分解反應者等(參考非專利文獻1、專利文獻1)。At present, the most popular liquid crystal alignment film in the industry is a film composed of a polyimide formed on an electrode substrate and/or a polyimide obtained by imidizing the polyamic acid. The surface is made by wiping (that is, rubbing) with a cloth such as cotton, nylon, polyester, etc. in one direction. The rubbing treatment is an industrially useful method that is simple and excellent in productivity. However, with the increase in performance, definition, and size of liquid crystal display elements, scratches, dust generation, mechanical force, or static electricity on the surface of the alignment film caused by the rubbing treatment are affected. Various problems such as the inhomogeneity of the As an alignment treatment method in place of the rubbing treatment, a photo-alignment method for imparting alignment energy to a liquid crystal by irradiating polarized radiation is known. As the photo-alignment method, those utilizing a photoisomerization reaction, a photocrosslinking reaction, a photolysis reaction, and the like have been proposed (refer to Non-Patent Document 1 and Patent Document 1).
液晶顯示元件之構成構件的液晶配向膜，其係用來使液晶均勻地配列之膜，液晶配向性是重要特性之一。然而，利用上述光配向法所得到的液晶配向膜，相較於利用以往的摩擦處理所得到的液晶配向膜，具有液晶配向性變低之傾向，而具備該液晶配向膜的液晶顯示裝置之適用範圍係受到限制。 [先前技術文獻] [專利文獻]A liquid crystal alignment film, which is a constituent member of a liquid crystal display element, is a film for uniformly arranging liquid crystals, and liquid crystal alignment is one of the important characteristics. However, the liquid crystal alignment film obtained by the above-mentioned photo-alignment method has a tendency that the liquid crystal alignment is lower than that of the liquid crystal alignment film obtained by the conventional rubbing treatment. The range is limited. [Prior Art Literature] [Patent Literature]
[專利文獻1]日本特開平9-297313號公報 [專利文獻2]國際公開第2015/050135號說明書 [非專利文獻][Patent Document 1] Japanese Patent Application Laid-Open No. 9-297313 [Patent Document 2] International Publication No. 2015/050135 [Non-patent literature]
[非專利文獻1]「液晶光配向膜」木戸脇、市村 機能材料 1997年11月號 Vol.17、No.11第13~22頁[Non-Patent Document 1] "Liquid crystal photo-alignment film" Kitowaki, Ichimura Functional Materials Nov. 1997 Vol.17, No.11 pp. 13-22
[發明所欲解決之課題][The problem to be solved by the invention]
又，實際的液晶顯示元件，會因為製造上的不均等而造成於液晶顯示元件面內的扭轉角度(twist angle)的些微不均。如此一來，起因於如此般的面內不均，會造成液晶顯示元件的黑色顯示時的亮度於面內為不均之情況。 本發明為有鑑於上述情事而完成之發明，目的之一為提供一種適合於光配向法用的液晶配向劑，可得到具有高的液晶配向性、黑色顯示時於面內的亮度不均為受到抑制且對比度為經提升的液晶顯示元件。 [解決課題之手段]In addition, in actual liquid crystal display elements, slight variations in twist angles within the plane of the liquid crystal display element are caused by nonuniformity in manufacturing. In this way, due to such in-plane unevenness, the luminance at the time of black display of the liquid crystal display element may be uneven in the plane. The present invention has been made in view of the above-mentioned circumstances, and one of the objects is to provide a liquid crystal aligning agent suitable for a photo-alignment method, which can obtain a liquid crystal aligning agent with high liquid crystal alignability, and in-plane brightness unevenness during black display is not affected. Suppression and contrast are enhanced liquid crystal display elements. [Means of Solving Problems]
本發明人經進行深入研究之結果發現，藉由使用含有特定成分的液晶配向劑將能夠解決上述課題，因而完成本發明。具體而言係將下述作為要旨之發明。 尚，本說明書整體當中，作為鹵素原子，可舉出氟原子、氯原子、溴原子、碘原子等，＊表示鍵結鍵。As a result of intensive research, the present inventors found that the above-mentioned problems can be solved by using a liquid crystal aligning agent containing a specific component, and thus completed the present invention. Specifically, it is an invention having the following as the gist. In addition, throughout this specification, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, and * represents a bond.
一種液晶配向劑，其係含有下述式(0)所表示的重複單元(a0)及下述式(1)所表示的重複單元(a1)的聚醯亞胺前驅物的醯亞胺化聚合物，其特徵在於，含有上述醯亞胺化聚合物的醯亞胺化率為80~95%的聚合物(A)。
藉由本發明，可提供液晶配向性為高、及黑色顯示時於面內的亮度不均為受到抑制且對比度為優異的液晶顯示元件，以及提供可得到該液晶顯示元件的適合於光配向法用的液晶配向劑。According to the present invention, it is possible to provide a liquid crystal display element with high liquid crystal alignment, suppressed in-plane luminance unevenness during black display, and excellent contrast, and a liquid crystal display element suitable for photoalignment that can be obtained. liquid crystal alignment agent.
[實施發明之最佳形態][The best form of implementing the invention]
＜聚合物(A)＞
本發明的液晶配向劑，其係含有上述式(0)所表示的重複單元(a0)及上述式(1)所表示的重複單元(a1)的聚醯亞胺前驅物的醯亞胺化聚合物，且含有上述醯亞胺化聚合物的醯亞胺化率為80~95%的聚合物(A)。
在此，上述條件(3)的所謂的「來自於胺基的二個碳-氮鍵結軸相互為平行」，係意味著利用球・棒狀的分子結構模型(例如丸善出版公司製HGS分子結構模型)來表示芳香族二胺時，可將來自於胺基的二個碳-氮鍵結軸以成為相互平行之方式配置之情形。又，上述條件(2)的所謂的「來自於胺基的二個碳-氮鍵結軸相互不為平行」，係意味著利用球・棒狀的分子結構模型來表示芳香族二胺時，無法將來自於胺基的二個碳-氮鍵結軸以成為相互平行之方式配置之情形。Here, the so-called "two carbon-nitrogen bond axes derived from the amine group are parallel to each other" in the above condition (3) means that a ball-and-rod molecular structure model (for example, HGS molecule manufactured by Maruzen Publishing Co., Ltd.) is used. When an aromatic diamine is represented by a structural model), the two carbon-nitrogen bonding axes derived from the amine group can be arranged so as to be parallel to each other. In addition, the so-called "two carbon-nitrogen bond axes derived from the amine group are not parallel to each other" in the above condition (2) means that when the aromatic diamine is represented by a spherical/rod-shaped molecular structure model, It is impossible to arrange the two carbon-nitrogen bonding axes derived from the amine group so as to be parallel to each other.
作為上述以外的方法，例如，使用分子模擬(Chem3D Ultra Version 16.0.1.4)，藉由預設MM2力場設定來進行，並使最小(均方根)RMS梯度收斂於0.010來進行分子結構的最佳化及能量最低化時，將來自於胺基的二個碳-氮鍵結軸以成為相互平行之方式配置之情形，定義為上述條件(3)的「來自於胺基的二個碳-氮鍵結軸相互為平行」；將來自於胺基的二個碳-氮鍵結軸無法成為相互平行之方式配置之情形，定義為上述條件(2)的「來自於胺基的二個碳-氮鍵結軸相互不為平行」。As a method other than the above, for example, using molecular simulation (Chem3D Ultra Version 16.0.1.4), the optimization of the molecular structure is performed with the preset MM2 force field setting and the minimum (root mean square) RMS gradient is converged to 0.010. In the case of optimization and energy minimization, the case where the two carbon-nitrogen bonding axes derived from the amine group are arranged so as to be parallel to each other is defined as "the two carbon-nitrogen bonds derived from the amine group" in the above condition (3). The nitrogen bond axes are parallel to each other"; the case where the two carbon-nitrogen bond axes derived from the amine group cannot be arranged so as to be parallel to each other is defined as "the two carbon-nitrogen bond axes derived from the amine group" in the above condition (2) - The nitrogen bond axes are not parallel to each other".
作為上述式(g)的R1 ~R4 中的碳數1~6的烷基之具體例，可舉出甲基、乙基、丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、n-戊基等。作為上述R1 ~R4 中的碳數2~6的烯基之具體例，可舉例如乙烯基、丙烯基、丁烯基等，該等可為直鏈狀或分支狀。作為上述R1 ~R4 中的碳數2~6的炔基之具體例，可舉例如乙炔基、1-丙炔基、2-丙炔基等。作為上述R1 ~R4 中的鹵素原子，可舉出氟原子、氯原子、溴原子、碘原子等。作為含有氟原子的碳數1~6的1價的有機基，可舉出氟甲基、三氟甲基等。又，上述烷基、烯基、炔基及含有氟原子的碳數1~6的1價的有機基中所包含的-CH2 -的一部分可被-O-所取代。 尚，就有效率地得到本發明之效果之觀點而言，R1 至R4 中的至少一個係表示上述定義中的氫原子以外之基。藉由設為上述構成，聚醯亞胺膜的光反應性會變高、所得到的液晶配向膜的面內異向性會變高，故可抑制因為製造時所產生的於液晶顯示元件面內的扭轉角度不均所造成的對比度之降低。 Specific examples of the alkyl group having 1 to 6 carbon atoms in R 1 to R 4 of the above formula (g) include methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl. , sec-butyl, tert-butyl, n-pentyl, etc. Specific examples of the alkenyl groups having 2 to 6 carbon atoms in the above R 1 to R 4 include vinyl groups, propenyl groups, butenyl groups, and the like, and these may be linear or branched. Specific examples of the alkynyl group having 2 to 6 carbon atoms in the above R 1 to R 4 include , for example, an ethynyl group, a 1-propynyl group, a 2-propynyl group, and the like. Examples of the R 1 ~ R 4 is a halogen atom, include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. As a C1-C6 monovalent organic group containing a fluorine atom, a fluoromethyl group, a trifluoromethyl group, etc. are mentioned. Further, the above-described alkyl group, alkenyl group, alkynyl group, and the carbon number of fluorine atom-containing monovalent organic group having 1 to 6 included in -CH 2 - is replaced by -O- portion. Furthermore, from the viewpoint of efficiently obtaining the effects of the present invention , at least one of R 1 to R 4 represents a group other than a hydrogen atom in the above definition. By setting it as the above-mentioned structure, the photoreactivity of the polyimide film becomes high, and the in-plane anisotropy of the obtained liquid crystal alignment film becomes high, so that it is possible to suppress the occurrence of generation on the surface of the liquid crystal display element during production. Contrast reduction caused by uneven torsion angles within.
上述式(g)所表示的4價的有機基，就光反應性為高之觀點而言，其中較佳為下述式(g-1)~(g-5)之任一者所表示的4價的有機基，更佳為下述式(g-1)所表示的4價的有機基。＊表示鍵結鍵。
上述式(O)中的Ar的環上的任意的氫原子可被鹵素原子、碳數1~6的烷基、碳數2~6的烯基、碳數2~6的炔基、含有氟原子的碳數1~6的1價的有機基等的1價的有機基所取代。作為該等的1價的有機基之具體例，可舉出在上述R1 ~R4 所示例的結構。Arbitrary hydrogen atom on the ring of Ar in the above formula (O) may be replaced by a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a fluorine-containing group. It is substituted with a monovalent organic group such as a monovalent organic group having 1 to 6 carbon atoms in the atom. As a specific example of these monovalent organic groups, the structures exemplified in the above-mentioned R 1 to R 4 are exemplified.
(芳香族二胺(d0))
上述芳香族二胺(d0)，就有效率地得到本發明之效果之觀點而言，其中較佳為碳數4~40的芳香族二胺。作為具體例，可舉出：分子內含有一個芳香環的芳香族二胺；分子內含有二個芳香環的芳香族二胺，且該二個的芳香環係以-CH2
-、-C(CH3
)2
-、-O-、-C(=O)-、-O-C(=O)-、-NR-C(=O)-、-NR-(R表示氫原子、碳數1~5的烷基、苯基、tert-丁氧基羰基)、碳數2~20的伸烷基或該伸烷基的-CH2
-的一部分被-O-、-Si(CH3
)2
-、-C(=O)-、-O-C(=O)-、-NR-C(=O)-、-NR-所取代的2價的有機基所連結，且連結基所具有的主鏈方向的碳原子、氧原子、矽原子及氮原子之合計數為奇數個；分子內具有一個芳香環與茚烷(indane)結構的芳香族二胺；分子內具有三個以上的芳香環的芳香族二胺；具有雜環結構的芳香族二胺。作為上述芳香環，可舉例如苯環、萘環、蒽環，較佳為苯環及萘環，又較佳為苯環。又，上述芳香環上的氫原子的一部分可被羥基、碳數1~5的烷基、碳數1~5的烷氧基、羧基、鹵素原子、含有氟原子的碳數1~5的1價的有機基、上述碳數1~5的烷基上的氫原子的一部分被羥基所取代之基或-NH(Boc)(Boc表示tert-丁氧基羰基)所取代。
更具體而言，可舉出下述式(d0-1)~(d0-15)所表示的芳香族二胺、1,3-雙(4-胺基苯氧基)苯、雙[4-(4-胺基苯氧基)苯基]醚。
上述式(1)中的Y，就提高液晶配向性之觀點而言，較佳為來自於1,3-二胺基苯、2,4-二胺基甲苯、2,6-二胺基甲苯、3,3’-二胺基二苯基甲烷、4,4’-二胺基二苯基甲烷、雙(4-胺基苯氧基)甲烷、1,5-雙(4-胺基苯氧基)戊烷、1,3-雙(4-胺基苯乙基)脲、4,4’-二胺基二苯基醚、2,2-雙(3-胺基苯基)丙烷、2,2-雙(4-胺基苯基)丙烷、4,4’-二胺基二苯甲酮或1,3-雙(4-胺基苯氧基)苯的2價的有機基。Y in the above formula (1) is preferably derived from 1,3-diaminobenzene, 2,4-diaminotoluene, and 2,6-diaminotoluene from the viewpoint of improving liquid crystal alignment. , 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis(4-aminophenoxy)methane, 1,5-bis(4-aminobenzene) oxy)pentane, 1,3-bis(4-aminophenethyl)urea, 4,4'-diaminodiphenyl ether, 2,2-bis(3-aminophenyl)propane, A divalent organic group of 2,2-bis(4-aminophenyl)propane, 4,4'-diaminobenzophenone, or 1,3-bis(4-aminophenoxy)benzene.
(芳香族二胺(d1)) 上述芳香族二胺(d1)，就有效率地得到本發明之效果之觀點而言，其中較佳為碳數4~40的芳香族二胺。又，上述(d1)中的Q2 所具有的主鏈方向的碳原子及氧原子之合計數較佳為偶數個。作為主鏈方向的碳原子及氧原子的較佳的合計數為2n(n表示1~9的整數，較佳為1~8，又較佳為1~6)。作為芳香族二胺之具體例，可舉出於上述式(O)所表示的部分結構上鍵結二個胺基而成的芳香族二胺。(Aromatic diamine (d1)) The above-mentioned aromatic diamine (d1) is preferably an aromatic diamine having 4 to 40 carbon atoms from the viewpoint of efficiently obtaining the effects of the present invention. In addition, the total number of carbon atoms and oxygen atoms in the main chain direction that Q 2 in the above (d1) has is preferably an even number. A preferable total number of carbon atoms and oxygen atoms in the main chain direction is 2n (n represents an integer of 1 to 9, preferably 1 to 8, and more preferably 1 to 6). As a specific example of an aromatic diamine, the aromatic diamine which couple|bonded two amine groups to the partial structure represented by the said formula (O) is mentioned.
上述式(1)中的Y1,
就提高液晶配向性之觀點而言，較佳為來自於下述式(d1-1)~(d1-14)所表示的二胺的2價的有機基。
上述聚合物(A)亦可為進而具有與上述重複單元(a0)或(a1)不同的下述式(2)所表示的重複單元(a2)的聚醯亞胺前驅物的醯亞胺化聚合物。
上述式(2)中，X2
表示4價的有機基，Y2
表示來自於不具有碳數6以上的側鏈基的芳香族二胺的2價的有機基，R、Z係與上述式(0)的R、Z為同義。但若X2
與上述式(g)所表示的4價的有機基為同義時，Y2
表示上述式(0)中的Y所定義的2價的有機基或上述式(1)中的Y1
所定義的2價的有機基以外之結構。作為X2
之具體例，除了上述式(g)所表示的4價的有機基以外，可舉出下述式(X-1)~(X-25)之任一者所表示的4價的有機基、來自於芳香族四羧酸二酐的4價的有機基等。
在此，所謂的芳香族四羧酸二酐，係指鍵結於苯環、萘環等的芳香環的羧基經分子內脫水而得到的酸二酐。舉出具體例時，可舉出下述式(Xa-1)~(Xa-2)之任一者所表示的4價的有機基、下述式(Xr-1)~(Xr-7)所表示的4價的有機基。Here, the term "aromatic tetracarboxylic dianhydride" refers to an acid dianhydride obtained by intramolecular dehydration of a carboxyl group bonded to an aromatic ring such as a benzene ring and a naphthalene ring. Specific examples include a tetravalent organic group represented by any one of the following formulae (Xa-1) to (Xa-2), and the following formulae (Xr-1) to (Xr-7) The represented tetravalent organic group.
上述式(Xa-1)或(Xa-2)所表示的4價的有機基，亦可為下述式(Xa-3)~(Xa-19)之任一者所表示之結構。The tetravalent organic group represented by the above formula (Xa-1) or (Xa-2) may have a structure represented by any one of the following formulae (Xa-3) to (Xa-19).
作為Y2 的2價的有機基之具體例，除了上述式(0)中的Y所定義的2價的有機基或上述式(1)中的Y1 所定義的2價的有機基以外，可舉出：由p-苯二胺、4,4’-二胺基-2,2’-二甲基聯苯、3,3’-二甲氧基-4,4’-二胺基聯苯、3,3’-二羥基-4,4’-二胺基聯苯、3,3’-二氟-4,4’-二胺基聯苯、3,3’-雙(三氟甲基)-4,4’-二胺基聯苯、1,4-二胺基萘、1,5-二胺基萘、1,4-雙(4-胺基苯氧基)苯、4,4’-雙(4-胺基苯氧基)聯苯、4,4’-二胺基苯甲醯苯胺等的二胺中除去二個胺基而成之基；下述式(h-1)所表示的2價的有機基；下述式(h-2)~(h-4)等的具有光配向性基的2價的有機基；(h-5)所表示的2價的有機基；由4-(2-(甲基胺基)乙基)苯胺、4-(2-胺基乙基)苯胺、2,5-二胺基苯甲酸、4,4’-二胺基聯苯-3,3’-二羧酸、下述式(Dp-5)~(Dp-6)等的具有二苯基胺骨架的二胺、下述式(5-5)~(5-9)等的分子內具有「-N(D)-(D表示胺甲酸酯(carbamate)系保護基，又較佳為表示tert-丁氧基羰基)」的二胺、(z-18)~(z-23)所表示的二胺等的二胺中除去二個胺基而成之基。Specific examples of the divalent organic group of Y 2 include a divalent organic group defined by Y in the above formula (0) or a divalent organic group defined by Y 1 in the above formula (1), Examples include: p-phenylenediamine, 4,4'-diamino-2,2'-dimethylbiphenyl, 3,3'-dimethoxy-4,4'-diamino-linked Benzene, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl) base)-4,4'-diaminobiphenyl, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,4-bis(4-aminophenoxy)benzene, 4, 4'-bis(4-aminophenoxy)biphenyl, 4,4'-diaminobenzylaniline and other diamines by removing two amine groups; the following formula (h-1 ) represented by a divalent organic group; a divalent organic group having a photoalignment group represented by the following formulae (h-2) to (h-4); a divalent organic group represented by (h-5) base; from 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 2,5-diaminobenzoic acid, 4,4'-diaminobenzidine Benzene-3,3'-dicarboxylic acid, diamines having a diphenylamine skeleton such as the following formulas (Dp-5) to (Dp-6), and the following formulas (5-5) to (5-9) ) and other diamines, (z-18)~ A group obtained by removing two amine groups from diamines such as diamine represented by (z-23).
上述聚合物(A)亦可為進而具有與上述重複單元(a0)、(a1)、(a2)不同的下述式(3)所表示的重複單元(a3)的聚醯亞胺前驅物的醯亞胺化聚合物。
式中，X3 表示4價的有機基，Y3 表示上述式(2)中的Y2 所定義的2價的有機基以外的2價的有機基，R、Z係與上述式(0)的R、Z為同義。但若X3 與上述式(g)所表示的4價的有機基為同義時，Y3 表示上述式(0)中的Y所定義的2價的有機基或上述式(1)中的Y1 所定義的2價的有機基以外之結構。作為X3 之具體例，可舉出上述式(2)中的X2 所示例之結構，就可適合得到本發明之效果之觀點而言，較佳為上述式(g)所表示的4價的有機基。In the formula, X 3 represents a tetravalent organic group, Y 3 represents a divalent organic group other than the divalent organic group defined by Y 2 in the above formula (2), and R and Z are related to the above formula (0) R and Z are synonymous. However, when X 3 is synonymous with the tetravalent organic group represented by the above formula (g), Y 3 represents a divalent organic group defined by Y in the above formula (0) or Y in the above formula (1) structure other than a divalent organic group having 1 defined above. Specific examples of X 3 include the structures exemplified by X 2 in the above formula (2), and from the viewpoint that the effects of the present invention can be suitably obtained, a tetravalent valence represented by the above formula (g) is preferred. organic base.
作為Y3 的2價的有機基之具體例，可舉出：由N-苯基-3,6-二胺基咔唑、甲基丙烯酸2-(2,4-二胺基苯氧基)乙酯、2,4-二胺基-N,N-二烯丙基苯胺等的末端具有光聚合性基的二胺、膽甾烷基氧基-3,5-二胺基苯、膽甾烯基氧基-3,5-二胺基苯、膽甾烷基氧基-2,4-二胺基苯、3,5-二胺基苯甲酸膽甾烷基酯、3,5-二胺基苯甲酸膽甾烯基酯、3,5-二胺基苯甲酸羊毛甾烷基酯、3,6-雙(4-胺基苯甲醯基氧基)膽甾烷等的具有類固醇骨架的二胺、下述式(V-1)~(V-6)所表示的二胺、下述式(z-24)~(z-25)所表示的二胺、下述式(5-10)~(5-13)所表示的二胺、雙(4-胺基環己基)甲烷、雙(4-胺基-3-甲基環己基)甲烷等的脂環式二胺、1,3-二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷、1,11-二胺基十一烷、1,12-二胺基十二烷等的脂肪族二胺等的二胺中除去二個胺基而成之基、國際公開公報2018/117239號中記載的式(Y-1)~(Y-167)之任一者所表示之基。就可適合得到本發明之效果之觀點而言，Y3 較佳為由式(5-10)~(5-13)所表示的二胺中除去二個胺基而成之基。Specific examples of the divalent organic group of Y 3 include N-phenyl-3,6-diaminocarbazole, methacrylic acid 2-(2,4-diaminophenoxy) Diamines having a photopolymerizable group at the terminal such as ethyl ester, 2,4-diamino-N,N-diallylaniline, cholestyloxy-3,5-diaminobenzene, cholesteryl Alkenyloxy-3,5-diaminobenzene, cholestyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestyl, 3,5-diaminobenzene Steroid skeletons such as cholestyl aminobenzoate, lanostanyl 3,5-diaminobenzoate, 3,6-bis(4-aminobenzyloxy)cholestane, etc. diamines, diamines represented by the following formulas (V-1) to (V-6), diamines represented by the following formulas (z-24) to (z-25), Alicyclic diamines such as diamines represented by 10) to (5-13), bis(4-aminocyclohexyl)methane, and bis(4-amino-3-methylcyclohexyl)methane, 1, 3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8 -Diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, etc. A group obtained by removing two amine groups from diamines such as aliphatic diamines, and a group represented by any one of formulae (Y-1) to (Y-167) described in International Publication No. 2018/117239. From the viewpoint that the effects of the present invention can be suitably obtained, Y 3 is preferably a group obtained by removing two amine groups from the diamines represented by the formulae (5-10) to (5-13).
(上述式(V-1)~(V-6)中，Xv1 ~Xv4 、Xp1 ~Xp2 分別獨立表示-(CH2 )a -(a為1~15的整數)、-CONH-、-NHCO-、-CON(CH3 )-、-NH-、-O-、-CH2 O-、-CH2 OCO-、-COO-或 -OCO-，Xv5 表示-O-、-CH2 O-、-CH2 OCO-、-COO-或-OCO-，Xa表示單鍵、-O-、-NH-、-O-(CH2 )m -O-(m表示1~6的整數)，Rv1 ~Rv4 、R1a ~R1b 分別獨立表示碳數1~20的烷基、碳數1~20的烷氧基或碳數2~20的烷氧基烷基)。(In the above formulas (V-1) to (V-6), X v1 to X v4 and X p1 to X p2 independently represent -(CH 2 ) a - (a is an integer of 1 to 15), -CONH- , -NHCO-, -CON(CH 3 )-, -NH-, -O-, -CH 2 O-, -CH 2 OCO-, -COO- or -OCO-, X v5 represents -O-, -CH 2 O-, -CH 2 OCO-, -COO- or -OCO-, Xa represents a single bond, -O-, -NH-, -O-(CH 2 ) m -O-(m represents an integer from 1 to 6 ), R v1 ~R v4 and R 1a ~R 1b independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms).
就得到本發明之效果之觀點而言，聚合物(A)中重複單元(a0)、重複單元(a1)及該等的經醯亞胺化的重複單元之合計，相對於全重複單元，較佳為5莫耳%以上，又較佳為10莫耳%以上。From the viewpoint of obtaining the effects of the present invention, the sum of the repeating unit (a0), the repeating unit (a1), and the imidized repeating units in the polymer (A) is higher than the total repeating unit. Preferably it is 5 mol% or more, and more preferably 10 mol% or more.
就得到本發明之效果之觀點而言，聚合物(A)係以含有相對於全重複單元為1~40莫耳%的重複單元(a1)及該經醯亞胺化的重複單元為較佳，又較佳為含有1~35莫耳%，更佳為含有1~30莫耳%。From the viewpoint of obtaining the effects of the present invention, the polymer (A) preferably contains 1 to 40 mol% of the repeating unit (a1) and the imidized repeating unit based on the total repeating unit. , and preferably contains 1-35 mol%, more preferably contains 1-30 mol%.
就得到本發明之效果之觀點而言，聚合物(A)係以含有相對於全重複單元為1~95莫耳%的重複單元(a2)及該經醯亞胺化的重複單元為較佳，又較佳為含有1~90莫耳%，更佳為含有5~90莫耳%。From the viewpoint of obtaining the effects of the present invention, the polymer (A) preferably contains 1 to 95 mol% of the repeating unit (a2) and the imidized repeating unit based on the total repeating unit. , and preferably contains 1-90 mol%, more preferably contains 5-90 mol%.
就得到本發明之效果之觀點而言，聚合物(A)係以含有相對於全重複單元為1~40莫耳%的重複單元(a3)及該經醯亞胺化的重複單元為較佳，又較佳為含有1~30莫耳%，更佳為含有1~25莫耳%。From the viewpoint of obtaining the effect of the present invention, the polymer (A) preferably contains 1 to 40 mol% of the repeating unit (a3) and the imidized repeating unit based on the total repeating unit. , and preferably contains 1-30 mol %, more preferably contains 1-25 mol %.
尚，聚合物(A)所具有的經醯亞胺化的重複單元為95莫耳%以下。 若聚合物(A)含有重複單元(a0)、重複單元(a1)及該等的經醯亞胺化的重複單元以外的重複單元時，重複單元(a0)、重複單元(a1)及該等的經醯亞胺化的重複單元之合計較佳為95莫耳%以下，更佳為90莫耳%以下。Furthermore, the imidized repeating unit possessed by the polymer (A) is 95 mol % or less. When the polymer (A) contains repeating units (a0), repeating units (a1) and repeating units other than those imidized repeating units, repeating units (a0), repeating units (a1) and these repeating units The total of the imidized repeating units is preferably 95 mol % or less, more preferably 90 mol % or less.
＜聚合物(B)＞
本發明的液晶配向劑，除了上述聚合物(A)以外，亦可含有選自由聚醯亞胺前驅物及醯亞胺化率為未滿80%的聚醯亞胺所組成之群之至少1種的聚合物(B)。就有效率地得到本發明之效果之觀點而言，作為聚合物(B)，可舉出具有下述式(4)所表示的重複單元的聚合物。
作為上述式(4)的X4 中的4價的有機基，可舉出來自於脂肪族四羧酸二酐的4價的有機基、來自於脂環式四羧酸二酐的4價的有機基或來自於芳香族四羧酸二酐的4價的有機基，作為具體例，可舉出在上述X2 所示例的4價的有機基。就有效率地得到本發明之效果之觀點而言，X4 較佳為上述式(g)所表示的4價的有機基、上述式(X-1)~(X-25)之任一者所表示的4價的有機基、上述式(Xa-1)~(Xa-2)所表示的4價的有機基或上述式(Xr-1)~(Xr-7)所表示的4價的有機基(亦將該等總稱為「特定的4價的有機基」)。 Examples of the tetravalent organic group in X 4 of the above formula (4) include a tetravalent organic group derived from aliphatic tetracarboxylic dianhydride and a tetravalent organic group derived from alicyclic tetracarboxylic dianhydride. The organic group or the tetravalent organic group derived from the aromatic tetracarboxylic dianhydride is exemplified by the tetravalent organic group exemplified by X 2 above. From the viewpoint of efficiently obtaining the effects of the present invention, X 4 is preferably a tetravalent organic group represented by the above formula (g) or any one of the above formulas (X-1) to (X-25). The tetravalent organic group represented by the above formulas (Xa-1) to (Xa-2), or the tetravalent organic group represented by the above formulas (Xr-1) to (Xr-7) Organic groups (these are also collectively referred to as "specific tetravalent organic groups").
關於聚合物(B)，就有效率地得到本發明之效果之觀點而言，相對於聚合物(B)中所包含的全重複單元，較佳含有5莫耳%以上的X4 為上述特定的4價的有機基的重複單元，又較佳含有10莫耳%以上。 Regarding the polymer (B), from the viewpoint of efficiently obtaining the effects of the present invention, X 4 is preferably contained in 5 mol% or more with respect to the total repeating units contained in the polymer (B). The repeating unit of the tetravalent organic group preferably contains 10 mol% or more.
作為上述式(4)的Y4 中的2價的有機基，可舉出在上述式(0)中的Y或上述式(1)~(3)中的Y1 ~Y3 所示例的2價的有機基。就來自於殘留DC的殘影為少之觀點而言，聚合物(B)係以包含Y4 為下述重複單元的聚合物為較佳，Y4 為選自由下述的2價的有機基所組成之群之2價的有機基(亦將該等總稱為「特定的2價的有機基」)：由具有選自由含氮雜環、第二級胺基及第三級胺基所成之群之至少1種的含氮結構(以下，亦稱為含氮結構)的二胺、2,4-二胺基苯酚、3,5-二胺基苯酚、3,5-二胺基苯甲醇、2,4-二胺基苯甲醇、4,6-二胺基間苯二酚、具有羧基的二胺中除去二個胺基而成的2價的有機基、及由1,3-雙(4-胺基苯乙基)脲等的具有脲鍵的二胺中除去二個胺基而成的2價的有機基。Examples of the divalent organic group in Y 4 in the above formula (4) include Y in the above formula (0) or 2 exemplified by Y 1 to Y 3 in the above formulas (1) to (3). valent organic base. The polymer (B) is preferably a polymer containing Y 4 as the following repeating unit, and Y 4 is a divalent organic group selected from the following: The bivalent organic group of the group (also collectively referred to as "specific bivalent organic group"): composed of a group selected from nitrogen-containing heterocycles, secondary amine groups and tertiary amine groups Diamine, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzene having at least one type of nitrogen-containing structure (hereinafter, also referred to as nitrogen-containing structure) of the group Methanol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, a divalent organic group obtained by removing two amine groups from a diamine having a carboxyl group, and a 1,3- A divalent organic group obtained by removing two amine groups from a diamine having a urea bond such as bis(4-aminophenethyl)urea.
作為上述含氮雜環，可舉例如吡咯、咪唑、吡唑、***、吡啶、嘧啶、嗒嗪、吡嗪、吲哚、苯并咪唑、嘌呤、喹啉、異喹啉、萘啶、喹喔啉、酞嗪、三嗪、咔唑、吖啶、哌啶、哌嗪、吡咯啶、六亞甲基亞胺等。其中，較佳為吡啶、嘧啶、吡嗪、哌啶、哌嗪、喹啉、咔唑或吖啶。Examples of the nitrogen-containing heterocycle include pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyrazine, pyrazine, indole, benzimidazole, purine, quinoline, isoquinoline, naphthyridine, quinoline Oxaline, phthalazine, triazine, carbazole, acridine, piperidine, piperazine, pyrrolidine, hexamethyleneimine, etc. Among them, pyridine, pyrimidine, pyrazine, piperidine, piperazine, quinoline, carbazole or acridine is preferable.
具有含氮結構的二胺可具有的第二級胺基及第三級胺基係例如下述式(n)所表示。
上述式(n)中，R表示氫原子或碳數1~10的1價的烴基，「＊」表示鍵結於烴基的鍵結鍵。 作為上述式(n)中的R的1價的烴基，可舉例如甲基、乙基、丙基等的烷基；環己基等的環烷基；苯基、甲基苯基等的芳基等。R較佳為氫原子或甲基。In the above formula (n), R represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and "*" represents a bond to the hydrocarbon group. Examples of the monovalent hydrocarbon group of R in the above formula (n) include alkyl groups such as methyl, ethyl, and propyl; cycloalkyl groups such as cyclohexyl; and aryl groups such as phenyl and methylphenyl. Wait. R is preferably a hydrogen atom or a methyl group.
作為具有含氮結構的二胺之具體例，可舉例如2,6-二胺基吡啶、3,4-二胺基吡啶、2,4-二胺基嘧啶、3,6-二胺基咔唑、N-甲基-3,6-二胺基咔唑、1,4-雙-(4-胺基苯基)-哌嗪、3,6-二胺基吖啶、N-乙基-3,6-二胺基咔唑、N-苯基-3,6-二胺基咔唑、N,N’-雙(4-胺基苯基)-聯苯胺、N,N’-雙(4-胺基苯基)-N,N’-二甲基聯苯胺、4,4’-二胺基二苯基胺、N,N-雙(4-胺基苯基)-甲基胺、上述式(Dp-1)~式(Dp-6)所表示的二胺或上述式(z-1)~式(z-25)所表示的二胺。Specific examples of the diamine having a nitrogen-containing structure include 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, and 3,6-diaminocarbazone. azole, N-methyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, 3,6-diaminoacridine, N-ethyl- 3,6-Diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis( 4-aminophenyl)-N,N'-dimethylbenzidine, 4,4'-diaminodiphenylamine, N,N-bis(4-aminophenyl)-methylamine, The diamine represented by the said formula (Dp-1) - a formula (Dp-6), or the diamine represented by the said formula (z-1) - a formula (z-25).
作為上述具有羧基的二胺之具體例，可舉出2,4-二胺基苯甲酸、2,5-二胺基苯甲酸、3,5-二胺基苯甲酸或4,4’-二胺基聯苯-3,3’-二羧酸。Specific examples of the above-mentioned diamine having a carboxyl group include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, or 4,4'-diaminobenzoic acid. Aminobiphenyl-3,3'-dicarboxylic acid.
就來自於殘留DC的殘影為少之觀點而言，聚合物(B)可含有相對於聚合物(B)中所包含的全重複單元為1莫耳%以上的「Y4 為上述特定的2價的有機基的重複單元」，亦可含有5莫耳%以上的「Y4 為上述特定的2價的有機基的重複單元」。 The polymer (B) may contain 1 mol % or more of "Y 4 is the above-mentioned specific one with respect to the total repeating units contained in the polymer (B), from the viewpoint of less image sticking due to residual DC. The repeating unit of a divalent organic group" may contain 5 mol% or more of "Y 4 is a repeating unit of the above-mentioned specific divalent organic group".
就來自於殘留DC的殘影為少之觀點而言，聚合物(A)與聚合物(B)之含有比例，以[聚合物(A)]/[聚合物(B)]之質量比計可為10/90~90/10，亦可為20/80~90/10，亦可為20/80~80/20。The content ratio of the polymer (A) and the polymer (B) is based on the mass ratio of [polymer (A)]/[polymer (B)] from the viewpoint of less image sticking due to residual DC It can be 10/90~90/10, it can also be 20/80~90/10, it can also be 20/80~80/20.
＜聚醯胺酸、聚醯胺酸酯及聚醯亞胺之製造方法＞ 本發明中所使用的聚醯亞胺前驅物的聚醯胺酸酯、聚醯胺酸及其醯亞胺化聚合物的聚醯亞胺，可利用例如國際公開公報WO2013/157586中所記載般的周知方法來進行合成。<The manufacturing method of polyamide acid, polyamide ester and polyimide> The polyimide of the polyimide precursor used in the present invention, the polyimide acid, and the polyimide of the imidized polymer thereof can be used, for example, as described in International Publication WO2013/157586. well-known methods for synthesis.
藉由將上述的聚醯亞胺前驅物進行醯亞胺化，而得到本發明的聚合物(A)。聚合物(A)中聚醯亞胺前驅物所具有的重複單元為閉環，但相對於聚醯亞胺前驅物所具有的全重複單元，閉環的重複單元之比例(亦稱為閉環率或醯亞胺化率)為80~95%，較佳為82~95%，又較佳為85~95%。 藉由設為上述構成，所得到的液晶配向膜將具有高的液晶配向性，故能得到上述本發明之效果。The polymer (A) of the present invention is obtained by imidizing the above-mentioned polyimide precursor. The repeating unit of the polyimide precursor in the polymer (A) is a closed ring, but relative to the total repeating unit of the polyimide precursor, the ratio of the closed repeating unit (also known as the ring closure ratio or The imidization rate) is 80~95%, preferably 82~95%, and preferably 85~95%. By setting it as the said structure, since the liquid crystal alignment film obtained will have high liquid crystal alignment, the effect of this invention mentioned above can be acquired.
＜聚合物的溶液黏度・分子量＞ 本發明中所使用的聚醯胺酸、聚醯胺酸酯及聚醯亞胺，將其製成濃度10~15質量%的溶液時，就作業性之觀點而言，以具有例如10~1000mPa・s的溶液黏度為較佳，但並未特別限定。尚，上述聚合物的溶液黏度(mPa・s)係如下述般測量所得到之值：使用良溶劑(例如γ-丁內酯、N-甲基-2-吡咯啶酮等)將該聚合物調製成濃度10~15質量%的聚合物溶液，對於該聚合物溶液使用E型回轉黏度計在25℃進行測量。 上述聚醯胺酸、聚醯胺酸酯及聚醯亞胺藉由凝膠滲透層析(GPC)測量所得到之聚苯乙烯換算的重量平均分子量(Mw)，較佳為1,000~500,000，又較佳為2,000~300,000。又，以Mw、與藉由GPC測量所得到之聚苯乙烯換算的數平均分子量(Mn)之比所表示的分子量分布(Mw/Mn)，較佳為15以下，又較佳為10以下。藉由設為如此般的分子量範圍，可確保液晶顯示元件之良好的配向性及穩定性。<Solution viscosity and molecular weight of polymer> When the polyamic acid, polyamic acid ester, and polyimide used in the present invention are prepared as a solution having a concentration of 10 to 15 mass %, they should have, for example, 10 to 1000 mPa from the viewpoint of workability. The solution viscosity of s is preferable, but not particularly limited. Furthermore, the solution viscosity (mPa·s) of the above polymer is a value obtained by measuring the polymer using a good solvent (such as γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) A polymer solution having a concentration of 10 to 15% by mass was prepared, and the polymer solution was measured at 25°C using an E-type rotational viscometer. The weight-average molecular weight (Mw) in terms of polystyrene, which is measured by gel permeation chromatography (GPC), is preferably 1,000 to 500,000, and Preferably it is 2,000-300,000. Moreover, the molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene conversion number average molecular weight (Mn) obtained by GPC measurement is preferably 15 or less, and more preferably 10 or less. By setting it as such a molecular weight range, favorable orientation and stability of a liquid crystal display element can be ensured.
＜液晶配向劑＞ 本發明的液晶配向劑含有聚合物(A)及因應所需的聚合物(B)。除了聚合物(A)、聚合物(B)以外，本發明的液晶配向劑亦可含有其他的聚合物。作為其他的聚合物之種類，可舉出聚酯、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。<Liquid crystal alignment agent> The liquid crystal aligning agent of the present invention contains a polymer (A) and a polymer (B) as required. In addition to the polymer (A) and the polymer (B), the liquid crystal aligning agent of the present invention may contain other polymers. Examples of other types of polymers include polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivatives, polyacetal, polystyrene or derivatives thereof, poly(styrene-benzene) maleimide) derivatives, poly(meth)acrylates, etc.
液晶配向劑係用以製作液晶配向膜而使用之物，就所謂的形成均勻薄膜之觀點而言，採用塗佈液的形態。本發明的液晶配向劑亦以含有上述的聚合物成分、與有機溶劑之塗佈液為較佳。此時，液晶配向劑中的聚合物的濃度，可依據所欲形成的塗膜厚度之設定來予以適當變更。就形成均勻且無缺陷之塗膜之觀點而言，較佳為質量%以上，就溶液之保存穩定性之觀點而言，較佳為10質量%以下。特佳的聚合物的濃度為2~8質量%。The liquid crystal aligning agent is used for producing a liquid crystal aligning film, and takes the form of a coating liquid from the viewpoint of so-called formation of a uniform thin film. The liquid crystal aligning agent of the present invention is also preferably a coating liquid containing the above-mentioned polymer component and an organic solvent. At this time, the concentration of the polymer in the liquid crystal aligning 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 10% by mass, and from the viewpoint of the storage stability of the solution, it is preferably at most 10% by mass. The concentration of a particularly preferable polymer is 2 to 8 mass %.
液晶配向劑中所含有的有機溶劑，只要是能將聚合物成分均勻溶解的溶劑即可，並未特別限定。作為該具體例，可舉出N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、二甲基亞碸、γ-丁內酯、1,3-二甲基-咪唑啶酮(imidazolidinone)、甲基乙基酮、環己酮、環戊酮、3-甲氧基-N,N-二甲基丙烷醯胺、3-丁氧基-N,N-二甲基丙烷醯胺(亦總稱該等為「良溶劑」)等。其中，較佳為N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、3-甲氧基-N,N-二甲基丙烷醯胺、3-丁氧基-N,N-二甲基丙烷醯胺或γ-丁內酯。良溶劑的含量，較佳為液晶配向劑中所包含的溶劑整體的20~99質量%，又較佳為20~90質量%，特佳為30~80質量%。The organic solvent contained in the liquid crystal aligning agent is not particularly limited as long as it can dissolve the polymer component uniformly. Specific examples of this include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidine Ketone, dimethyl sulfoxide, gamma-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N , N-dimethylpropaneamide, 3-butoxy-N,N-dimethylpropaneamide (also collectively referred to as "good solvent") and the like. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropaneamide, 3-butoxy- N,N-dimethylpropaneamide or γ-butyrolactone. The content of the good solvent is preferably 20 to 99% by mass of the entire solvent contained in the liquid crystal alignment agent, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass.
又，液晶配向劑中所含有的有機溶劑，較佳為使用混合溶劑，其係除了上述溶劑以外，亦併用了使塗佈液晶配向劑時之塗佈性或塗膜的表面平滑性提升之溶劑(亦稱為不良溶劑)。將併用的不良溶劑之具體例表示如下，但並不限定於該等。 例如，可舉出二異丙基醚、二異丁基醚、二異丁基甲醇(carbinol)(2,6-二甲基-4-庚醇)、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、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、碳酸丙烯酯、碳酸乙烯酯、乙二醇單丁基醚、乙二醇單異戊基醚、乙二醇單己基醚、丙二醇單丁基醚、1-(2-丁氧基乙氧基)-2-丙醇、2-(2-丁氧基乙氧基)-1-丙醇、丙二醇單甲基醚乙酸酯、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇二甲基醚、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、丙二醇二乙酸酯、乙酸n-丁酯、乙酸丙二醇單乙基醚、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-甲氧基丙酸乙酯、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、乳酸n-丁酯、乳酸異戊酯、二乙二醇單乙基醚、二異丁基酮(2,6-二甲基-4-庚酮)等。Moreover, as the organic solvent contained in the liquid crystal aligning agent, it is preferable to use a mixed solvent, which, in addition to the above-mentioned solvent, is also used in combination with a solvent which improves the coatability when the liquid crystal aligning agent is applied or the surface smoothness of the coating film (also known as poor solvent). Although the specific example of the poor solvent used together is shown below, it is not limited to these. For example, diisopropyl ether, diisobutyl ether, diisobutyl methanol (carbinol) (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol Alcohol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl ether -2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethyl Butyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol Monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol, 2-(2-butoxyethoxy)- 1-Propanol, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol mono Acetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl Acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate , Ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether , Diisobutyl ketone (2,6-dimethyl-4-heptanone), etc.
其中，較佳為二異丁基甲醇(carbinol)、丙二醇單丁基醚、丙二醇二乙酸酯、二乙二醇二乙基醚、二丙二醇單甲基醚、二丙二醇二甲基醚、4-羥基-4-甲基-2-戊酮、乙二醇單丁基醚、乙二醇單丁基醚乙酸酯或二異丁基酮。Among them, diisobutyl methanol (carbinol), propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4 -Hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate or diisobutyl ketone.
不良溶劑的含量，較佳為液晶配向劑中所包含的溶劑整體的1~80質量%，又較佳為20~80質量%，特佳為20~70質量%。不良溶劑的種類及含量，可因應液晶配向劑的塗佈裝置、塗佈條件、塗佈環境等而予以適當選擇。The content of the poor solvent is preferably 1 to 80% by mass of the entire solvent contained in the liquid crystal alignment agent, more preferably 20 to 80% by mass, and particularly preferably 20 to 70% by mass. The type and content of the poor solvent can be appropriately selected according to the coating apparatus of the liquid crystal aligning agent, coating conditions, coating environment, and the like.
作為良溶劑與不良溶劑之較佳的溶劑的組合，可舉出N-甲基-2-吡咯啶酮與乙二醇單丁基醚、N-甲基-2-吡咯啶酮與γ-丁內酯與乙二醇單丁基醚、N-甲基-2-吡咯啶酮與γ-丁內酯與丙二醇單丁基醚、N-乙基-2-吡咯啶酮與丙二醇單丁基醚、N-甲基-2-吡咯啶酮與γ-丁內酯與4-羥基-4-甲基-2-戊酮與二乙二醇二乙基醚、N-甲基-2-吡咯啶酮與γ-丁內酯與丙二醇單丁基醚與二異丁基酮、N-甲基-2-吡咯啶酮與γ-丁內酯與丙二醇單丁基醚與二異丙基醚、N-甲基-2-吡咯啶酮與γ-丁內酯與丙二醇單丁基醚與二異丁基甲醇、N-甲基-2-吡咯啶酮與γ-丁內酯與二丙二醇二甲基醚、N-甲基-2-吡咯啶酮與丙二醇單丁基醚與二丙二醇二甲基醚等。As a preferable combination of a good solvent and a poor solvent, N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butane are exemplified Lactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether , N-methyl-2-pyrrolidone and γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N-methyl-2-pyrrolidine Ketone and γ-butyrolactone and propylene glycol monobutyl ether and diisobutyl ketone, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisopropyl ether, N -Methyl-2-pyrrolidone with γ-butyrolactone and propylene glycol monobutyl ether with diisobutylmethanol, N-methyl-2-pyrrolidone with γ-butyrolactone and dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol dimethyl ether, etc.
本發明的液晶配向劑可追加性含有聚合物成分及有機溶劑以外的成分(以下，亦稱為添加劑成分)。作為如此般的添加劑成分，可舉出用以提高液晶配向膜與基板的密著性或液晶配向膜與密封劑的密著性之密著助劑、用以促進醯亞胺化之化合物、用以提高液晶配向膜的強度之化合物(以下，亦稱為交聯性化合物)、用以調整液晶配向膜的介電率或電阻之介電質或導電物質等。The liquid crystal aligning agent of the present invention may additionally contain components other than the polymer component and the organic solvent (hereinafter, also referred to as additive components). Examples of such additive components include 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 sealant, compounds for promoting imidization, and Compounds (hereinafter, also referred to as cross-linking compounds) to improve the strength of the liquid crystal alignment film, dielectric or conductive substances for adjusting the permittivity or resistance of the liquid crystal alignment film, and the like.
作為上述交聯性化合物，就對於AC殘影展現出良好的耐性、膜強度之改善較高之觀點而言，亦可為下述之化合物(以下，亦總稱該等為化合物(C))：具有選自由環氧乙烷基(oxiranyl)、氧雜環丁烷基、保護異氰酸酯基、保護異硫氰酸酯基、包含噁唑啉環結構之基、包含米氏酸(Meldrum’s acid)結構之基、環碳酸酯基、及下述式(d)所表示之基所組成之群之至少1種之基之化合物，以及，選自由下述式(e)所表示之化合物所組成之群之至少1種之化合物。
作為具有環氧乙烷基之化合物之具體例，可舉出日本特開平10-338880號公報之段落[0037]中記載之化合物、或國際公開公報WO2017/170483號中記載之具有三嗪環骨架之化合物等的具有2個以上的環氧乙烷基之化合物。該等之中，亦可為N,N,N’,N’-四縮水甘油基-m-二甲苯二胺、1,3-雙(N,N-二縮水甘油胺基甲基)環己烷、N,N,N’,N’-四縮水甘油基-4,4’-二胺基二苯基甲烷、N,N,N’,N’-四縮水甘油基-p-苯二胺、下述式(r-1)~(r-3)所表示之化合物等的含有氮原子之化合物。
作為具有氧雜環丁烷基之化合物之具體例，可舉出國際公開公報2011/132751號之段落[0170]~[0175]中記載之具有2個以上的氧雜環丁烷基之化合物等。Specific examples of the compound having an oxetanyl group include compounds having two or more oxetanyl groups described in paragraphs [0170] to [0175] of International Publication No. 2011/132751. .
作為具有保護異氰酸酯基之化合物之具體例，可舉出日本特開2014-224978號公報之段落[0046]~ [0047]中記載之具有2個以上的保護異氰酸酯基之化合物、國際公開公報2015/141598號之段落[0119]~[0120]中記載之具有3個以上的保護異氰酸酯基之化合物等，亦可為下述式(bi-1)~(bi-3)所表示之化合物。
作為具有保護異硫氰酸酯基之化合物之具體例，可舉出日本特開2016-200798號公報中記載之具有2個以上的保護異硫氰酸酯基之化合物。 作為具有包含噁唑啉環結構之基之化合物之具體例，可舉出日本特開2007-286597號公報之段落[0115]中記載之包含2個以上的噁唑啉環結構之化合物。As a specific example of the compound which has a protected isothiocyanate group, the compound which has two or more protected isothiocyanate groups described in Unexamined-Japanese-Patent No. 2016-200798 is mentioned. As a specific example of the compound which has a group containing an oxazoline ring structure, the compound containing two or more oxazoline ring structures described in the paragraph [0115] of Unexamined-Japanese-Patent No. 2007-286597 is mentioned.
作為具有包含米氏酸結構之基之化合物之具體例，可舉出國際公開公報WO2012/091088號中記載之具有2個以上的米氏酸結構之化合物。 作為具有環碳酸酯基之化合物之具體例，可舉出國際公開公報WO2011/155577號中記載之化合物。 作為式(d)所表示之基之R2 、R3 之碳數1~3的烷基，可舉出甲基、乙基、丙基、異丙基。As a specific example of the compound which has a group containing a Michaelis acid structure, the compound which has two or more Michaelis acid structures described in International Publication No. WO2012/091088 is mentioned. As a specific example of the compound which has a cyclocarbonate group, the compound described in International Publication No. WO2011/155577 can be mentioned. A methyl group, an ethyl group, a propyl group, and an isopropyl group are mentioned as a C1-C3 alkyl group of R 2 and R 3 of the group represented by the formula (d).
作為具有式(d)所表示之基之化合物之具體例，可舉出國際公開公報WO2015/072554號、或日本特開2016-118753號公報之段落[0058]中記載之具有2個以上的式(d)所表示之基之化合物、日本特開2016-200798號公報中記載之化合物等，亦可為下述式(hd-1)~(hd-8)所表示之化合物。
作為式(e)的A中的具有芳香環的(m+n)價的有機基，可舉出碳數6~30的(m+n)價的芳香族烴基、碳數6~30的芳香族烴基為直接鍵結或透過連結基鍵結而成的(m+n)價的有機基、具有芳香族雜環的(m+n)價之基。作為芳香族烴基，可舉例如苯、萘等。作為芳香族雜環，可舉例如吡咯環、咪唑環、吡唑環、吡啶環、嘧啶環、喹啉環、異喹啉環、咔唑環、嗒嗪環、吡嗪環、苯并咪唑環、吲哚環、喹喔啉環、吖啶環等。作為連結基，可舉出：-NR-(R為氫原子或甲基)、由碳數1~10的伸烷基或伸烷基中除去一個氫原子而成之基、2價或3價的環己烷環等。尚，伸烷基的任意的氫原子可被氟原子或三氟甲基等的有機基所取代。作為式(e)的R中的碳數1~5的烷基，可舉出在上述式(g)中的R1
~R4
所示例之烷基之具體例。
若舉出具體例時，可舉出國際公開公報WO2010/074269號中記載之化合物、下述式(e-1)~(e-10)所表示之化合物。
上述化合物為交聯性化合物之一例，並非被限定於該等。例如，可舉出國際公開公報2015/060357號第53頁[0105]~第55頁[0116]中所揭示的上述以外的成分等。又，交聯性化合物亦可組合2種類以上來使用。 本發明的液晶配向劑中交聯性化合物的含量，相對於液晶配向劑中所包含的聚合物成分100質量份，較佳為0.5~20質量份，就使交聯反應進行，且對於AC殘影展現出良好的耐性之觀點而言，又較佳為1~15質量份。The above-mentioned compound is an example of a crosslinkable compound, and is not limited to these. For example, components other than the above-mentioned components disclosed in International Publication No. 2015/060357, pages 53 [0105] to 55 [0116], etc. can be mentioned. Moreover, you may use a crosslinkable compound in combination of 2 or more types. The content of the crosslinking compound in the liquid crystal aligning agent of the present invention is preferably 0.5 to 20 parts by mass relative to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent, so that the crosslinking reaction proceeds, and for AC residual From the viewpoint that the film exhibits good resistance, it is also preferably 1 to 15 parts by mass.
作為上述密著助劑，可舉例如3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-胺基丙基二乙氧基甲基矽烷、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-三乙氧基矽烷基丙基三乙烯三胺、N-三甲氧基矽烷基丙基三乙烯三胺、10-三甲氧基矽烷基-1,4,7-三氮雜癸烷、10-三乙氧基矽烷基-1,4,7-三氮雜癸烷、9-三甲氧基矽烷基-3,6-二氮雜壬基乙酸酯、9-三乙氧基矽烷基-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、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、p-苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、參-(三甲氧基矽烷基丙基)異氰脲酸酯、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷等的矽烷偶合劑。若使用矽烷偶合劑時，就對於AC殘影展現出良好的耐性之觀點而言，相對於液晶配向劑中所包含的聚合物成分100質量份，較佳為0.1~30質量份，又較佳為0.1~20質量份。Examples of the above-mentioned adhesion aid include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-amine propyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl) yl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-amine Ethylpropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyl Triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethyl Oxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropane Trimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyl Triethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, vinyltrimethoxysilane Silane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxy propylpropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3- Methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3 - Methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, para-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropyl Silane coupling agents such as methyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc. When a silane coupling agent is used, it is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent from the viewpoint of exhibiting good resistance to AC image sticking, and more preferably It is 0.1-20 mass parts.
作為上述用以促進醯亞胺化之化合物，以具有鹼性部位(例如：1級胺基、脂肪族雜環(例如：吡咯啶骨架)、芳香族雜環(例如：咪唑環、吲哚環)、或胍基等)之化合物(但上述交聯性化合物及密著助劑除外)、或可於燒成時產生上述鹼性部位之化合物為佳。較佳為可於燒成時產生上述鹼性部位之化合物，若舉出具體例時，可舉出下述式(B-1)~(B-17)所表示之化合物。用以促進醯亞胺化之化合物的含量，相對於聚合物(A)所具有的醯胺酸或醯胺酸酯部位1莫耳，較佳為2莫耳以下，又較佳為1莫耳以下，更佳以0.5莫耳以下為良好。
＜液晶配向膜之製造方法＞ 使用本發明的液晶配向劑之液晶配向膜之製造方法，其特徵為依序進行下述之步驟：將上述液晶配向劑塗佈在基板上之步驟(步驟(1))、加熱經塗佈的液晶配向劑而得到膜之步驟(步驟(2))、對於以步驟(2)所得到的膜照射經偏光的紫外線之步驟(步驟(3))，並因應所需地進一步將以步驟(3)所得到的膜利用100℃以上且高於步驟(2)的溫度來進行燒成之步驟(步驟(4))。<Manufacturing method of liquid crystal alignment film> The method for producing a liquid crystal alignment film using the liquid crystal alignment agent of the present invention is characterized by sequentially performing the following steps: coating the liquid crystal alignment agent on a substrate (step (1)), heating the coated The step of obtaining a film from a liquid crystal aligning agent (step (2)), the step of irradiating the film obtained in step (2) with polarized ultraviolet rays (step (3)), and as required, further step (3) ) The obtained film is subjected to a step (step (4)) of firing at a temperature of 100° C. or higher and higher than that of the step (2).
＜步驟(1)＞ 作為塗佈本發明中所使用的液晶配向劑的基板，只要是透明性高之基板即可，並未特別限定，亦可使用玻璃基板、氮化矽基板、丙烯酸基板或聚碳酸酯基板等的塑膠基板等。此時，使用已形成用以驅動液晶之ITO電極等的基板時，就製程之簡單化之點而言為較佳。又，於反射型之液晶顯示元件時，若僅為單側之基板的話，則矽晶圓等的不透明物亦可使用，此時，作為電極亦可使用鋁等的會反射光的材料。 液晶配向劑之塗佈方法並未特別限定，但工業上，一般而言為以絲網印刷、膠印印刷、柔版印刷或噴墨法等來進行之方法。作為其他的塗佈方法，例如有浸漬法、輥塗法、狹縫塗佈法、旋轉器法或噴灑法等，可因應目的使用該等。<Step (1)> The substrate on which the liquid crystal aligning agent used in the present invention is applied is not particularly limited as long as it is a substrate with high transparency, and a glass substrate, a silicon nitride substrate, an acrylic substrate, or a polycarbonate substrate may also be used. Plastic substrates, etc. In this case, it is preferable to use a substrate on which ITO electrodes and the like for driving the liquid crystal are formed, from the viewpoint of simplification of the process. In addition, in the case of a reflective liquid crystal display element, if only a single-sided substrate is used, an opaque material such as a silicon wafer can also be used. In this case, a light-reflecting material such as aluminum can also be used as the electrode. The coating method of the liquid crystal alignment agent is not particularly limited, but industrially, generally, it is a method performed by screen printing, offset printing, flexographic printing, or inkjet method. As another coating method, there exist a dip method, a roll coating method, a slit coating method, a spinner method, a spray method, etc., for example, and these can be used according to the objective.
＜步驟(2)＞ 步驟(2)為加熱經塗佈至基板上的液晶配向劑，而形成膜之步驟。具體而言，將以步驟(1)所塗佈至基板上的液晶配向劑藉由熱板、熱循環型烘箱或IR(紅外線)型烘箱等的加熱手段，來使溶劑蒸發，或可進行聚合物中的醯胺酸或醯胺酸酯的熱醯亞胺化。以步驟(1)所塗佈至基板上的液晶配向劑之加熱步驟，可選擇任意之溫度與時間，亦可進行複數次。作為加熱溫度，可以例如40~180℃來進行，就縮短製程之觀點而言，較佳為以40~150℃來進行，又較佳為以40~120℃來進行。作為加熱時間並未特別限定，可舉出1~10分鐘或1~5分鐘。若進行聚合物中的醯胺酸或醯胺酸酯之熱醯亞胺化之情形時，於上述步驟後，能以例如190~250℃、或200~240℃之溫度範圍來進行加熱步驟。作為加熱時間並未特別限定，可舉出5~40分鐘或5~30分鐘的加熱時間。<Step (2)> Step (2) is a step of heating the liquid crystal aligning agent coated on the substrate to form a film. Specifically, the liquid crystal aligning agent coated on the substrate in step (1) is used to evaporate the solvent by heating means such as a hot plate, a thermal cycle oven, or an IR (infrared) oven, or it can be polymerized Thermal imidization of aramidic acids or aramidic acid esters. The heating step of the liquid crystal aligning agent coated on the substrate in step (1) can be selected at any temperature and time, and can also be performed several times. As a heating temperature, 40-180 degreeC can be performed, for example, From a viewpoint of shortening a process, it is preferable to perform at 40-150 degreeC, and it is more preferable to perform at 40-120 degreeC. Although it does not specifically limit as a heating time, 1-10 minutes or 1-5 minutes are mentioned. In the case of thermal imidization of the amide acid or amide ester in the polymer, after the above step, the heating step can be performed at a temperature range of, for example, 190 to 250°C or 200 to 240°C. The heating time is not particularly limited, and a heating time of 5 to 40 minutes or 5 to 30 minutes is mentioned.
＜步驟(3)＞ 步驟(3)係對於以步驟(2)所得到的膜照射經偏光的紫外線之步驟。作為紫外線之波長，較佳為200~400nm，其中，更佳為200~300nm。為了改善液晶配向性，可一邊將已塗膜有液晶配向膜之基板以50~250℃加熱，一邊照射紫外線。又，上述放射線的照射量較佳為1~10,000mJ/cm2 ，又較佳為100~5,000mJ/cm2 。如此進行所製作之液晶配向膜，可使液晶分子穩定地往一定的方向配向。 由於經偏光的紫外線之消光比越高時，可賦予更高的各向異性，故為較佳。具體而言，經偏光為直線的紫外線之消光比較佳為10：1以上，又較佳為20：1以上。<Step (3)> Step (3) is a step of irradiating the film obtained by the step (2) with polarized ultraviolet rays. As the wavelength of the ultraviolet rays, 200 to 400 nm is preferable, and among them, 200 to 300 nm is more preferable. In order to improve the liquid crystal alignment, the substrate on which the liquid crystal alignment film has been coated can be heated at 50-250° C. while irradiating ultraviolet rays. Moreover, the irradiation dose of the said radiation becomes like this. Preferably it is 1-10,000mJ/cm<2> , More preferably, it is 100-5,000mJ/cm<2> . The liquid crystal alignment film produced in this way can stably align the liquid crystal molecules in a certain direction. Since the higher the extinction ratio of polarized ultraviolet rays, the higher the anisotropy can be imparted, which is preferable. Specifically, the extinction ratio of the polarized ultraviolet rays is preferably 10:1 or more, and more preferably 20:1 or more.
＜步驟(4)＞ 步驟(4)係將以步驟(3)所得到的膜利用100℃以上且高於步驟(2)的溫度來進行燒成之步驟。燒成溫度只要是100℃以上且高於在步驟(2)的燒成溫度即可，並未特別限定，較佳為150~300℃，又較佳為150~250℃，更佳為200~250℃。燒成時間較佳為5~120分鐘，又較佳為5~60分鐘，更佳為5~30分鐘。 燒成後的液晶配向膜的厚度過薄時，由於液晶顯示元件的可靠性會有降低之情形，故較佳為5~300nm，又較佳為10~200nm。<Step (4)> The step (4) is a step of firing the film obtained in the step (3) at a temperature of 100° C. or higher and higher than the step (2). The firing temperature is not particularly limited as long as it is 100°C or higher and higher than the firing temperature in step (2), but is preferably 150 to 300°C, more preferably 150 to 250°C, and more preferably 200 to 200°C. 250°C. The firing time is preferably 5 to 120 minutes, more preferably 5 to 60 minutes, and more preferably 5 to 30 minutes. When the thickness of the liquid crystal alignment film after firing is too thin, since the reliability of the liquid crystal display element may decrease, it is preferably 5 to 300 nm, and more preferably 10 to 200 nm.
進而，進行上述步驟(3)或(4)之任一步驟後，亦可將所得到的液晶配向膜使用水或溶劑，進行接觸處理。 作為上述接觸處理中所使用之溶劑，只要是能溶解因紫外線之照射而從液晶配向膜中所生成之分解物之溶劑即可，並未特別限定。作為具體例，可舉出水、甲醇、乙醇、2-丙醇、丙酮、甲基乙基酮、1-甲氧基-2-丙醇、1-甲氧基-2-丙醇乙酸酯、丁基溶纖劑、乳酸乙酯、乳酸甲酯、二丙酮醇、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙酸丙酯、乙酸丁酯或乙酸環己酯等。其中，就通用性或溶劑之安全性之觀點而言，較佳為水、2-丙醇、1-甲氧基-2-丙醇或乳酸乙酯。更佳為水、1-甲氧基-2-丙醇或乳酸乙酯。溶劑可為1種類，亦可組合2種類以上。Furthermore, after performing any one of the above-mentioned steps (3) or (4), the obtained liquid crystal alignment film may be subjected to a contact treatment using water or a solvent. The solvent used in the above-mentioned contact treatment is not particularly limited as long as it can dissolve the decomposed products generated from the liquid crystal alignment film by irradiation with ultraviolet rays. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, and 1-methoxy-2-propanol acetate , butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate or cyclohexyl acetate, etc. . Among them, water, 2-propanol, 1-methoxy-2-propanol, or ethyl lactate are preferable from the viewpoint of generality and safety of the solvent. More preferred is water, 1-methoxy-2-propanol or ethyl lactate. One type of solvent may be used, or two or more types may be combined.
作為上述的接觸處理(亦即，對於照射經偏光的紫外線的液晶配向膜進行水或溶劑之處理之方法)，可舉出浸漬處理或噴霧處理(亦稱為噴灑處理)。該等的處理的處理時間，就有效率地溶解因紫外線而從液晶配向膜中所生成之分解物之觀點而言，較佳為10秒~1小時。其中，較佳為進行1~30分鐘浸漬處理。又，上述接觸處理時的溶劑，雖然常溫或進行加溫皆可，但較佳為10~80℃，又較佳為20~50℃。此外，就分解物之溶解性之觀點而言，因應所需亦可進行超音波處理等。Examples of the above-mentioned contact treatment (that is, a method of treating a liquid crystal alignment film irradiated with polarized ultraviolet rays with water or a solvent) include immersion treatment or spray treatment (also referred to as spray treatment). The treatment time of these treatments is preferably 10 seconds to 1 hour from the viewpoint of efficiently dissolving the decomposed products generated from the liquid crystal alignment film by ultraviolet rays. Among them, it is preferable to perform the immersion treatment for 1 to 30 minutes. In addition, the solvent in the above-mentioned contact treatment may be at room temperature or heated, but is preferably 10 to 80°C, and more preferably 20 to 50°C. In addition, from the viewpoint of the solubility of the decomposition product, ultrasonic treatment and the like may be performed as necessary.
較佳為於上述接觸處理之後，進行藉由水、甲醇、乙醇、2-丙醇、丙酮或甲基乙基酮等的低沸點溶劑的清洗(亦稱為淋洗)或液晶配向膜的燒成。此時，可進行淋洗與燒成之任一種，或亦可進行兩者。燒成的溫度較佳為150~300℃。其中，又較佳為180~250℃。更佳為200~ 230℃。又，燒成的時間較佳為10秒~30分鐘。其中，又較佳為1~10分鐘。Preferably, after the above-mentioned contact treatment, washing with a low-boiling solvent such as water, methanol, ethanol, 2-propanol, acetone or methyl ethyl ketone (also called rinsing) or calcination of the liquid crystal alignment film is performed. become. At this time, either of rinsing and firing may be performed, or both may be performed. The firing temperature is preferably 150 to 300°C. Among them, 180-250 degreeC is also preferable. More preferably, it is 200-230 degreeC. Moreover, the time of baking is preferably 10 seconds to 30 minutes. Among them, 1 to 10 minutes are further preferred.
＜液晶配向膜＞ 本發明的液晶配向膜係由上述液晶配向劑所得到。 本發明的液晶配向膜適合作為IPS方式或FFS方式等的橫向電場方式的液晶顯示元件之液晶配向膜，尤其是作為FFS方式的液晶顯示元件之液晶配向膜為有用的。<Liquid crystal alignment film> The liquid crystal alignment film of the present invention is obtained from the above-mentioned liquid crystal alignment agent. The liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film for a lateral electric field type liquid crystal display element such as an IPS method or an FFS method, and is particularly useful as a liquid crystal alignment film for an FFS method liquid crystal display element.
＜液晶顯示元件＞ 本發明的液晶顯示元件，其係具備上述液晶配向膜。 液晶顯示元件係如下述般來製作：製得附有由本發明的液晶配向劑所得到的液晶配向膜之基板後，利用已知之方法製作液晶晶胞，使用該液晶晶胞來得到液晶顯示元件。 作為液晶晶胞的製作方法之一例，將被動矩陣結構之液晶顯示元件作為例子來進行說明。尚，亦可為於構成畫像顯示之各像素部分設置TFT(Thin Film Transistor)等的切換元件而成的主動矩陣結構之液晶顯示元件。<Liquid crystal display element> The liquid crystal display element of this invention is equipped with the said liquid crystal alignment film. The liquid crystal display element is produced as follows: after the substrate with the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention is produced, a liquid crystal cell is produced by a known method, and a liquid crystal display element is obtained by using the liquid crystal cell. As an example of the production method of a liquid crystal cell, the liquid crystal display element of a passive matrix structure is demonstrated as an example. Furthermore, it can also be a liquid crystal display element of an active matrix structure in which switching elements such as TFT (Thin Film Transistor) are arranged in each pixel portion constituting the image display.
具體而言，準備透明的玻璃製的基板，於一側的基板之上設置共用電極，並於另一側的基板之上設置節段電極。該等的電極，可設為例如ITO電極，並且被圖型化成可以顯示所期望的畫像。接下來，於各基板之上以被覆共用電極與節段電極之方式，來設置絕緣膜。絕緣膜可設為例如藉由溶膠-凝膠法所形成的SiO2 -TiO2 之膜。 接下來，於各基板之上形成液晶配向膜，將另一側的基板以彼此之液晶配向膜面成為對向的方式重疊在一側的基板，並將周邊以密封劑進行接著。為了控制基板間隙，密封劑中通常係以先混入間隔物，又，即使於未設置密封劑的面內部分，亦先散布基板間隙控制用之間隔物為較佳。對於密封劑的一部分，先設置可從外部填充液晶之開口部。接下來，通過設置於密封劑之開口部，對於以2片之基板與密封劑所包圍之空間內注入液晶材料，然後，將此開口部以接著劑密封。注入可使用真空注入法，亦可使用於大氣中利用毛細管現象之方法。液晶材料可使用正型液晶材料或負型液晶材料之任一種。接下來，進行偏光板之設置。具體而言，於和2片基板之液晶層為相反側之面貼附一對偏光板。Specifically, a transparent glass substrate is prepared, common electrodes are provided on one substrate, and segment electrodes are provided on the other substrate. These electrodes can be, for example, ITO electrodes, and are patterned to display a desired image. Next, an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode. The insulating film can be, for example, a film of SiO 2 -TiO 2 formed by a sol-gel method. Next, a liquid crystal alignment film is formed on each substrate, the other substrate is superimposed on the one substrate so that the liquid crystal alignment film surfaces face each other, and the periphery is bonded with a sealant. In order to control the gap between the substrates, a spacer is usually mixed into the sealant first, and even in the in-plane portion where the sealant is not provided, it is preferable to first spread the spacer for controlling the gap between the substrates. A part of the sealant is provided with an opening that can be filled with liquid crystal from the outside. Next, the liquid crystal material was injected into the space surrounded by the two substrates and the sealant through the opening provided in the sealant, and then the opening was sealed with the adhesive. For the injection, a vacuum injection method or a method utilizing capillary phenomenon in the atmosphere may be used. As the liquid crystal material, either a positive type liquid crystal material or a negative type liquid crystal material can be used. Next, set the polarizer. Specifically, a pair of polarizing plates is attached to the surface opposite to the liquid crystal layer of the two substrates.
藉由使用本發明之製造方法，可抑制在IPS驅動方式或FFS驅動方式的液晶顯示元件中所產生的因為長期交流驅動而造成的殘影。又，藉由在步驟(2)，以40~ 150℃的溫度範圍來去除有機溶劑後，實施步驟(3)，相較於以往之技術，能夠以更少之步驟數而得到液晶配向膜。本發明的液晶配向劑特佳可使用於包含下述步驟之液晶配向膜之製造方法：在步驟(2)，以40~150℃的溫度範圍來去除有機溶劑後，實施步驟(3)。 [實施例]By using the manufacturing method of the present invention, it is possible to suppress image sticking caused by long-term AC driving in a liquid crystal display element of an IPS driving method or an FFS driving method. Furthermore, by performing step (3) after removing the organic solvent at a temperature range of 40 to 150° C. in step (2), a liquid crystal alignment film can be obtained with fewer steps than the prior art. The liquid crystal alignment agent of the present invention is particularly preferably used in a method for producing a liquid crystal alignment film comprising the following steps: in step (2), after removing the organic solvent at a temperature range of 40-150°C, step (3) is performed. [Example]
以下為列舉實施例，更具體地說明本發明，但本發明並不被限定於該等。在以下之化合物的簡稱及各特性的測量方法係如以下。 (溶劑) NMP：N-甲基-2-吡咯啶酮(N-methyl-2-pyrrolidone) BCS：丁基溶纖劑(butyl cellosolve) (二胺) DA-1~DA-13：分別為下述式(DA-1)~式(DA-13)所表示之化合物 (四羧酸二酐) CA-1~CA-3：分別為下述式(CA-1)~式(CA-3)所表示之化合物(添加劑) C-1：下述式(C-1)所表示之化合物 S-1：下述式(S-1)所表示之化合物 F-1：下述式(F-1)所表示之化合物Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. The abbreviations of the compounds below and the measurement methods of each characteristic are as follows. (solvent) NMP: N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone) BCS: butyl cellosolve (diamine) DA-1 to DA-13: compounds represented by the following formulas (DA-1) to (DA-13), respectively (tetracarboxylic dianhydride) CA-1 to CA-3: compounds (additives) represented by the following formulae (CA-1) to (CA-3), respectively C-1: a compound represented by the following formula (C-1) S-1: a compound represented by the following formula (S-1) F-1: a compound represented by the following formula (F-1)
＜醯亞胺化率的測量＞ 將聚醯亞胺粉末20mg放入在NMR樣品管(NMR sampling tube stand，ϕ5(草野科學公司製))中，添加重氫化二甲基亞碸(DMSO-d6，0.05%TMS(四甲基矽烷)混合品) (0.53mL)，並施以超音波使其完全溶解。藉由NMR測量機(JNW-ECA500)(JEOL DATUM公司製)來測量該溶液的500MHz的質子NMR。醯亞胺化率係將來自於醯亞胺化前後未變化的結構的質子作為基準質子，使用該質子的波峰累積值與在9.5ppm~10.0ppm附近所出現的來自於醯胺酸的NH基的質子波峰累積值，並藉由以下之式而可求得。 醯亞胺化率(%)=(1-α・x/y)×100 上述式中，x係來自於醯胺酸的NH基的質子波峰累積值；y係基準質子的波峰累積值；α係聚醯胺酸(醯亞胺化率為0%)時，基準質子對醯胺酸的1個NH基質子的個數比例。<Measurement of imidization rate> 20 mg of polyimide powder was put into an NMR sampling tube stand (NMR sampling tube stand, ϕ5 (manufactured by Kusano Scientific Co., Ltd.)), and deuterated dimethylsulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) was added. ) mixture) (0.53 mL), and sonicated to dissolve it completely. The 500 MHz proton NMR of the solution was measured by an NMR measuring machine (JNW-ECA500) (manufactured by JEOL DATUM). The imidization rate is based on the proton derived from the unchanged structure before and after imidization as the reference proton, and the peak accumulation value of the proton and the NH group derived from the imidic acid appearing in the vicinity of 9.5 ppm to 10.0 ppm are used. The cumulative value of the proton peaks of , and can be obtained by the following formula. Imidization rate (%)=(1-α・x/y)×100 In the above formula, x is the cumulative peak value of protons derived from the NH group of aramidic acid; y represents the peak cumulative value of reference protons; when α-based polyamide acid (imidation rate is 0%), the reference proton pair The number ratio of 1 NH proton of amide acid.
[聚合物的合成例] ＜合成例1＞ 在附有攪拌裝置及氮導入管的100mL的茄型燒瓶中，量取5.62g(19.2mmol)的DA-2、4.18g(10.5mmol)的DA-10及2.92g(5.24mmol)的DA-7，並加入50.9g的NMP，邊送氮邊攪拌來使其溶解。將該二胺溶液在水冷下邊攪拌邊添加4.50g(22.7mmol)的CA-3，進一步加入18.0g的NMP，在氮環境下以50℃攪拌1小時。進一步，添加2.63g(11.7mmol)的CA-1，並以濃度成為20質量%之方式來添加NMP，以40℃攪拌24小時而得到聚醯胺酸的溶液。 分離25.0g的該聚醯胺酸的溶液於放入有攪拌子的100mL三角燒瓶中，對此添加8.33g的NMP、2.96g(按對聚醯胺酸莫耳之比值為3等量)的乙酸酐、0.766g(按對聚醯胺酸莫耳之比值為等量)的吡啶，以室溫攪拌30分鐘後，以55℃使其反應3小時。將該反應溶液投入至170g的甲醇中，過濾取出所得到的沉殿物。將該沉殿物利用甲醇洗淨後，以溫度80℃進行減壓乾燥，而得到聚醯亞胺樹脂粉末(醯亞胺化率：86%)。進一步，分離4.00g的該聚醯亞胺樹脂粉末於放入有攪拌子的500mL三角燒瓶中，對此添加29.3g的NMP，以70℃攪拌24小時來使其溶解，而得到聚醯亞胺溶液(PI-1)。 ＜合成例2＞ 在附有攪拌裝置及氮導入管的200mL的四頸燒瓶中，量取2.44g(10.0mmol)的DA-1、2.37g(10.0mmol)的DA-3、2.30g(10.0mmol)的DA-4、2.98g(10.0mmol)的DA-6及3.44g(10.0mmol)的DA-9，並以濃度成為12質量%之方式來添加NMP，邊送氮邊攪拌來使其溶解。將該二胺溶液邊攪拌邊添加10.6g(47.2mmol)的CA-1，並以濃度成為12質量%之方式來添加NMP，以40℃攪拌24小時而得到聚醯胺酸的溶液。 分離35g(8.7mmol)的所得到的聚醯胺酸溶液於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，對此添加11.7g的NMP並攪拌30分鐘。對於所得到的聚醯胺酸溶液加入2.67g(按對聚醯胺酸莫耳之比值為3等量)的乙酸酐、0.69g(按對聚醯胺酸莫耳之比值為等量)的吡啶，以55℃使其反應3小時，來進行化学醯亞胺化。將所得到的反應液邊投入至150ml的甲醇中邊攪拌，過濾取出已析出的沉澱物，藉由實施2次相同的操作並將樹脂粉末洗淨後，以60℃減壓乾燥12小時，而得到聚醯亞胺樹脂粉末。該聚醯亞胺樹脂粉末的醯亞胺化率為86%。分離3.60g的所得到的聚醯亞胺樹脂粉末於100ml三角燒瓶中，並以固形分濃度成為12質量%之方式來添加NMP，以70℃攪拌24小時來使其溶解，而得到聚醯亞胺溶液(PI-2)。[Synthesis example of polymer] <Synthesis example 1> In a 100 mL eggplant-shaped flask equipped with a stirring device and a nitrogen introduction tube, 5.62 g (19.2 mmol) of DA-2, 4.18 g (10.5 mmol) of DA-10, and 2.92 g (5.24 mmol) of DA- 7, and 50.9 g of NMP was added, and the mixture was dissolved while stirring while supplying nitrogen. To this diamine solution, 4.50 g (22.7 mmol) of CA-3 was added with stirring under water cooling, 18.0 g of NMP was further added, and the mixture was stirred at 50° C. for 1 hour under nitrogen atmosphere. Furthermore, 2.63 g (11.7 mmol) of CA-1 was added, and NMP was added so that the concentration might be 20 mass %, and the solution was stirred at 40° C. for 24 hours to obtain a polyamic acid solution. The solution of 25.0g of this polyamic acid was separated into a 100mL conical flask with a stirring bar, and 8.33g of NMP, 2.96g (according to the ratio of mol to polyamic acid was 3 equivalents) were added to this. Acetic anhydride and 0.766 g (equivalent in molar ratio to polyamide) of pyridine were stirred at room temperature for 30 minutes, and then reacted at 55°C for 3 hours. The reaction solution was poured into 170 g of methanol, and the resulting precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at a temperature of 80° C. to obtain a polyimide resin powder (imide rate: 86%). Further, 4.00 g of this polyimide resin powder was separated into a 500 mL conical flask with a stirrer, 29.3 g of NMP was added thereto, and it was dissolved by stirring at 70° C. for 24 hours to obtain polyimide. solution (PI-1). <Synthesis example 2> In a 200 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 2.44 g (10.0 mmol) of DA-1, 2.37 g (10.0 mmol) of DA-3, and 2.30 g (10.0 mmol) of DA- 4. 2.98 g (10.0 mmol) of DA-6 and 3.44 g (10.0 mmol) of DA-9 were added with NMP so that the concentration would be 12% by mass, and the mixture was dissolved while stirring while feeding nitrogen. 10.6 g (47.2 mmol) of CA-1 was added to this diamine solution while stirring, and NMP was added so that the concentration might be 12 mass %, and the solution was stirred at 40° C. for 24 hours to obtain a polyamic acid solution. 35 g (8.7 mmol) of the obtained polyamic acid solution was separated into a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 11.7 g of NMP was added thereto, and the mixture was stirred for 30 minutes. To the obtained polyamic acid solution, add 2.67 g (equivalent according to the ratio of the molar to the polyamic acid) of acetic anhydride, 0.69 g (equivalent according to the ratio of the molar to the polyamic acid) of acetic anhydride Pyridine was reacted at 55°C for 3 hours to carry out chemical imidization. The obtained reaction solution was poured into 150 ml of methanol while stirring, and the precipitated precipitate was collected by filtration, and the resin powder was washed by performing the same operation twice, and then dried under reduced pressure at 60° C. for 12 hours. A polyimide resin powder was obtained. The imidization rate of the polyimide resin powder was 86%. 3.60 g of the obtained polyimide resin powder was separated into a 100-ml Erlenmeyer flask, NMP was added so that the solid content concentration would be 12 mass %, and it was dissolved by stirring at 70° C. for 24 hours to obtain a polyimide. Amine solution (PI-2).
＜合成例3~5＞ 除了將所使用的單體的種類及數量變更成如下述之表1中之記載以外，其餘係與合成例2以相同的手法而得到聚醯亞胺溶液(PI-3)~(PI-5)。<Synthesis Examples 3 to 5> Polyimide solutions (PI-3) to (PI-5 were obtained in the same manner as in Synthesis Example 2, except that the types and quantities of the monomers used were changed as described in Table 1 below. ).
＜合成例6＞ 在附有攪拌裝置及氮導入管的200mL四頸燒瓶中，量取2.69g(9.0mmol)的DA-6及7.17g(36.0mmol)的DA-11，並以濃度成為12質量%之方式來添加NMP，邊送氮邊攪拌來使其溶解。將該二胺溶液邊攪拌邊添加12.2g(41.4mmol)的CA-2，並以濃度成為12質量%之方式來添加NMP，以70℃攪拌24小時而得到聚醯胺酸的溶液(PAA-1)。 尚，表1中之括弧內的數值為：關於四羧酸成分，係表示相對於合成時所使用的四羧酸衍生物的合計量100莫耳份的各化合物的調配比例(莫耳份)；關於二胺成分，係表示相對於合成時所使用的二胺的合計量100莫耳份的各化合物的調配比例(莫耳份)。關於有機溶劑，係表示相對於聚醯亞胺溶液之調製時所使用的有機溶劑的合計量100質量份的各有機溶劑的調配比例(質量份)。<Synthesis example 6> 2.69 g (9.0 mmol) of DA-6 and 7.17 g (36.0 mmol) of DA-11 were weighed in a 200 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and the concentration was 12% by mass. NMP was added, and it was made to melt|dissolve while stirring nitrogen supply. 12.2 g (41.4 mmol) of CA-2 was added to this diamine solution while stirring, and NMP was added so that the concentration would be 12% by mass, and the solution was stirred at 70° C. for 24 hours to obtain a polyamic acid solution (PAA- 1). Further, the numerical values in parentheses in Table 1 are: about the tetracarboxylic acid component, it represents the compounding ratio (mol part) of each compound relative to 100 mol parts of the total amount of the tetracarboxylic acid derivatives used in the synthesis ; About the diamine component, it shows the compounding ratio (mol part) of each compound with respect to 100 mol parts of the total amount of diamines used for synthesis. About an organic solvent, it shows the compounding ratio (mass part) of each organic solvent with respect to the total amount of 100 mass parts of organic solvents used for the preparation of a polyimide solution.
[液晶配向劑的調製] ＜比較例1＞ 在放入攪拌子的樣品管中加入以合成例1所得到的聚醯亞胺溶液(PI-1)，對此加入NMP及BCS來稀釋，以分別相對於聚合物固形分100質量份為成為1質量份、10質量份及15質量份之方式來添加S-1、C-1及F-1，攪拌30分鐘。如此般地操作，得到聚醯亞胺(PI-1)之固形分濃度為6質量%、溶劑組成以質量比計為NMP：BCS=80：20的液晶配向劑(R1)。[Preparation of liquid crystal alignment agent] <Comparative Example 1> The polyimide solution (PI-1) obtained in Synthesis Example 1 was put into the sample tube put in the stirrer, and NMP and BCS were added to this to dilute so as to be 100 parts by mass based on the solid content of the polymer, respectively. S-1, C-1, and F-1 were added as 1 part by mass, 10 parts by mass, and 15 parts by mass, and stirred for 30 minutes. In this way, the solid content concentration of polyimide (PI-1) was 6 mass %, and the liquid crystal aligning agent (R1) whose solvent composition was NMP:BCS=80:20 in mass ratio was obtained.
＜實施例1~8＞ 除了將所使用的聚合物成分變更成如下述之表2中之記載以外，其餘係與上述比較例1以相同的手法而分別得到液晶配向劑(1)~(8)。表2中之括弧內的數值為：關於聚合物及添加劑，係分別表示相對於液晶配向劑的調製時所使用的聚合物成分的合計100質量份的各聚合物成分或添加劑的調配比例(質量份)。關於有機溶劑，係表示相對於液晶配向劑的調製時所使用的有機溶劑的合計量100質量份的各有機溶劑的調配比例(質量份)。<Examples 1 to 8> Liquid crystal aligning agents (1) to (8) were obtained in the same manner as in Comparative Example 1 above, except that the polymer components used were changed as described in Table 2 below. The numerical values in parentheses in Table 2 are: Regarding polymers and additives, they represent the blending ratio (mass) of each polymer component or additive with respect to the total of 100 parts by mass of the polymer component used in the preparation of the liquid crystal aligning agent. share). About an organic solvent, it shows the compounding ratio (mass part) of each organic solvent with respect to the total amount of 100 mass parts of organic solvents used at the time of preparation of a liquid crystal aligning agent.
使用如上述般之操作而得到的液晶配向劑，依據以下所示之程序來製作FFS驅動液晶晶胞，並進行特性評估。Using the liquid crystal aligning agent obtained as described above, FFS-driven liquid crystal cells were produced according to the procedure shown below, and characteristics were evaluated.
[FFS驅動液晶晶胞之構成] 邊緣電場切換(Fringe Field Switching：FFS)模式用的液晶晶胞，係將於表面形成有由面形狀的共通電極-絕緣層-梳齒形狀的像素電極所組成之FOP(Finger on Plate)電極層之第1玻璃基板、與於表面具有高3.5μm之柱狀間隔物且於背面形成有用以防止帶電之ITO膜之第2玻璃基板設為一組。上述像素電極具有使中央部分以內角160°彎折之寬3μm之電極要素空出6μm之間隔平行地排列的複數個梳齒形狀，1個像素以將複數個電極要素之彎折部連結之線為邊界而具有第1區域及第2區域。 尚，形成於第1玻璃基板上之液晶配向膜，係以將像素彎折部之內角等分之方向與液晶之配向方向呈現正交之方式來進行配向處理；形成於第2玻璃基板上之液晶配向膜，係以將製作液晶晶胞時的第1基板上之液晶配向方向與第2基板上之液晶配向方向呈一致之方式來進行配向處理。[The composition of the FFS-driven liquid crystal cell] A liquid crystal cell for fringe field switching (FFS) mode is formed on the surface with an FOP (Finger on Plate) electrode layer consisting of a planar common electrode, an insulating layer, and a comb-shaped pixel electrode. The 1st glass substrate, and the 2nd glass substrate which has the columnar spacer of 3.5 micrometers high on the surface and the ITO film formed in the back surface to prevent electric charge are set as one set. The above-mentioned pixel electrode has a plurality of comb-teeth shapes arranged in parallel with electrode elements having a width of 3 μm bent at an inner angle of 160° in a central portion with an interval of 6 μm arranged in parallel, and one pixel has a line connecting the bent portions of the plurality of electrode elements. It has a 1st area and a 2nd area as a boundary. Furthermore, the liquid crystal alignment film formed on the first glass substrate is subjected to alignment treatment in such a way that the bisected direction of the inner angle of the pixel bending portion is orthogonal to the alignment direction of the liquid crystal; it is formed on the second glass substrate In the liquid crystal alignment film, the alignment treatment is performed in a manner that the alignment direction of the liquid crystal on the first substrate and the alignment direction of the liquid crystal on the second substrate during the production of the liquid crystal cell are consistent.
[液晶晶胞之製作] 於上述一組的玻璃基板的分別的表面上，將經1.0μm之過濾器過濾之液晶配向劑進行旋轉塗佈，於80℃之熱板上乾燥2分鐘。之後，隔著偏光板對於塗膜面照射消光比26：1之經直線偏光之波長254nm之紫外線150~350mJ/cm2 ，其次以230℃之熱風循環式烘箱進行30分鐘燒成，而得到附液晶配向膜(膜厚100nm)之基板2片。 其次，在上述一組的附液晶配向膜之基板之一側上印刷密封劑，將另一側基板以液晶配向膜面對向之方式進行貼合，使密封劑硬化來製作空晶胞。藉由減壓注入法，以常溫下於該空晶胞中真空注入液晶(MERCK公司製，MLC-3019)，密封注入口，而得到FFS驅動液晶晶胞。之後，將所得到的液晶晶胞於120℃加熱1小時(以下亦稱為「ISO處理」)，放置一晚後，使用於各評估。[Production of Liquid Crystal Cell] The liquid crystal aligning agent filtered through a 1.0 μm filter was spin-coated on the respective surfaces of the glass substrates of the above-mentioned group, and dried on a hot plate at 80° C. for 2 minutes. After that, irradiate 150~350mJ/cm 2 of linearly polarized ultraviolet rays with a wavelength of 254nm and a wavelength of 254nm to the coating film surface through a polarizing plate, followed by firing in a hot air circulating oven at 230°C for 30 minutes to obtain the coating film. 2 substrates of liquid crystal alignment film (film thickness 100nm). Next, a sealant is printed on one side of the substrate with the liquid crystal alignment film of the above group, and the other side of the substrate is attached with the liquid crystal alignment film facing, and the sealant is hardened to make an empty cell. Liquid crystal (MLC-3019, manufactured by MERCK Corporation) was vacuum-injected into the empty cell at room temperature by a reduced pressure injection method, the injection port was sealed, and an FFS-driven liquid crystal cell was obtained. Then, the obtained liquid crystal cell was heated at 120 degreeC for 1 hour (henceforth "ISO process"), and was used for each evaluation after leaving to stand overnight.
＜液晶配向性評估＞ 使用ISO處理前的液晶晶胞，將具有初期流動配向者定義為「不良」，及將無初期流動配向者定義為「良好」，來進行評估。 ＜對比度的面內均勻性評估＞ 使用SHINTEC公司製OPTIPRO-micro來進行液晶顯示元件的扭轉角度之評估。將已製作的液晶晶胞設置於測量台，在無外加電壓之狀態下測量第1像素面內的20點，並算出標準偏差。評估係將扭轉角度標準偏差為0.5以上之情形定義為「不良」，將未滿0.5之情形定義為「良好」，來進行評估。<Evaluation of liquid crystal alignment> Using the liquid crystal cell before ISO treatment, those with initial flow alignment were defined as "poor", and those without initial flow alignment were defined as "good" for evaluation. <In-plane uniformity evaluation of contrast ratio> The evaluation of the twist angle of the liquid crystal display element was performed using OPTIPRO-micro manufactured by SHINTEC Corporation. The produced liquid crystal cell was placed on a measuring stage, and 20 points in the first pixel plane were measured in a state where no voltage was applied, and the standard deviation was calculated. The evaluation was performed by defining a case where the torsion angle standard deviation was 0.5 or more as "poor", and a case where it was less than 0.5 as "good".
＜評估結果＞ 使用以上述實施例1~8及比較例1所得到液晶配向劑(1)~(8)及(R1)來得到液晶顯示元件，關於該等液晶顯示元件的評估結果係表示於表3中。＜Evaluation results＞ Liquid crystal display elements were obtained using the liquid crystal aligning agents (1) to (8) and (R1) obtained in the above-mentioned Examples 1 to 8 and Comparative Example 1, and Table 3 shows the evaluation results of these liquid crystal display elements.
本發明的液晶配向劑被廣泛使用於TN方式、VA方式等的縱向電場方式、特別是IPS方式、FFS方式等的橫向電場方式的液晶顯示元件中。 尚，將2020年3月6日提出申請的日本特願2020-039387號及2020年7月17日提出申請的日本特願2020-123014號的說明書、申請專利範圍及摘要的全部內容引用於此，而予以援用作為本發明的說明書之揭示內容。The liquid crystal aligning agent of this invention is widely used in the liquid crystal display element of the vertical electric field system, such as TN system and VA system, especially the transverse electric field system, such as IPS system and FFS system. Shang, the entire contents of the specification, patent application scope and abstract of Japanese Patent Application No. 2020-039387 filed on March 6, 2020 and Japanese Patent Application No. 2020-123014 filed on July 17, 2020 are incorporated herein by reference. , and be incorporated as the disclosure content of the specification of the present invention.
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| KR (1) | KR20220151604A (en) |
| CN (1) | CN115210637A (en) |
| TW (1) | TW202146632A (en) |
| WO (1) | WO2021177080A1 (en) |
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| TW202146524A (en) * | 2020-06-10 | 2021-12-16 | 奇美實業股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| CN114058384A (en) * | 2021-11-26 | 2022-02-18 | 深圳市道尔顿电子材料有限公司 | Polyimide photo-alignment agent solution and preparation method thereof, photo-alignment film and liquid crystal box |
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| JP3893659B2 (en) | 1996-03-05 | 2007-03-14 | 日産化学工業株式会社 | Liquid crystal alignment treatment method |
| CN101548228B (en) * | 2006-11-24 | 2011-11-16 | 日产化学工业株式会社 | Liquid crystal orientation treatment agent and liquid crystal display element produced by using the same |
| KR102266365B1 (en) | 2013-10-01 | 2021-06-16 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal aligning agent for in-plate switching, liquid crystal alignment film and liquid crystal display element using same |
| TWI527844B (en) * | 2014-06-06 | 2016-04-01 | 奇美實業股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device |
| TWI560240B (en) * | 2014-11-05 | 2016-12-01 | Chi Mei Corp | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| WO2018030489A1 (en) * | 2016-08-10 | 2018-02-15 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN112602013A (en) * | 2018-08-20 | 2021-04-02 | 日产化学株式会社 | Liquid crystal aligning agent, method for producing same, liquid crystal alignment film, and liquid crystal display element |
-
2021
- 2021-02-22 JP JP2022505130A patent/JPWO2021177080A1/ja active Pending
- 2021-02-22 WO PCT/JP2021/006672 patent/WO2021177080A1/en active Application Filing
- 2021-02-22 CN CN202180018328.4A patent/CN115210637A/en active Pending
- 2021-02-22 KR KR1020227025881A patent/KR20220151604A/en active Search and Examination
- 2021-03-02 TW TW110107222A patent/TW202146632A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN115210637A (en) | 2022-10-18 |
| KR20220151604A (en) | 2022-11-15 |
| JPWO2021177080A1 (en) | 2021-09-10 |
| WO2021177080A1 (en) | 2021-09-10 |
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