TWI820010B - Manufacturing method of liquid crystal alignment film, liquid crystal alignment film and liquid crystal display element - Google Patents
Manufacturing method of liquid crystal alignment film, liquid crystal alignment film and liquid crystal display element Download PDFInfo
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- TWI820010B TWI820010B TW106145151A TW106145151A TWI820010B TW I820010 B TWI820010 B TW I820010B TW 106145151 A TW106145151 A TW 106145151A TW 106145151 A TW106145151 A TW 106145151A TW I820010 B TWI820010 B TW I820010B
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- Prior art keywords
- liquid crystal
- crystal alignment
- alignment film
- manufacturing
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 241
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 60
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- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 19
- 238000010304 firing Methods 0.000 claims abstract description 14
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- 239000002243 precursor Substances 0.000 claims abstract description 9
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- 150000003949 imides Chemical class 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 125000000962 organic group Chemical group 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000000304 alkynyl group Chemical group 0.000 claims description 7
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- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
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- 238000005259 measurement Methods 0.000 description 2
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
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- YJUUZFWMKJBVFJ-UHFFFAOYSA-N 1,3-dimethylimidazolidin-4-one Chemical compound CN1CN(C)C(=O)C1 YJUUZFWMKJBVFJ-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
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- CRORGGSWAKIXSA-UHFFFAOYSA-N 3-methylbutyl 2-hydroxypropanoate Chemical compound CC(C)CCOC(=O)C(C)O CRORGGSWAKIXSA-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
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- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 1
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- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 1
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- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1025—Preparatory processes from tetracarboxylic acids or derivatives and diamines polymerised by radiations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本發明係一種液晶配向膜之製造方法，其特徵係具有下述(A)、(B)、(C)、及(D)之步驟，且連續進行步驟(B)與步驟(C)。 步驟(A)：塗佈含有由下述四羧酸衍生物成分與二胺成分所得之聚醯亞胺前驅物之醯亞胺化物的聚醯亞胺的液晶配向劑的步驟。 其中四羧酸衍生物成分為含有選自下述式(1)表示之四羧酸二酐、及其衍生物之至少1種類及選自下述式(2)表示之四羧酸二酐、及其衍生物之至少1種類的四羧酸衍生物成分， 步驟(B)：將塗佈後之液晶配向劑以實質上未進行熱醯亞胺化的條件下加熱，得到膜的步驟。 步驟(C)：對步驟(B)所得的膜照射偏光之紫外線的步驟。 步驟(D)：將在步驟(C)照射紫外線的膜以100℃以上、且比在步驟(B)加熱的溫度更高的溫度進行燒成的步驟。 The present invention is a method for manufacturing a liquid crystal alignment film, which is characterized by having the following steps (A), (B), (C), and (D), and performing step (B) and step (C) continuously. Step (A): The step of applying a liquid crystal alignment agent containing a polyimide containing an imide of a polyimide precursor obtained from the following tetracarboxylic acid derivative component and a diamine component. The tetracarboxylic acid derivative component contains at least one type of tetracarboxylic dianhydride represented by the following formula (1) and its derivatives, and a tetracarboxylic dianhydride represented by the following formula (2), At least one kind of tetracarboxylic acid derivative component of its derivatives, step (B): heating the coated liquid crystal alignment agent under conditions that do not substantially perform thermal imidization to obtain a film. Step (C): A step of irradiating the film obtained in step (B) with polarized ultraviolet light. Step (D): A step of firing the film irradiated with ultraviolet rays in step (C) at a temperature of 100° C. or higher and higher than the temperature heated in step (B).
Description
本發明為關於液晶配向膜之製造方法、藉由此製造方法所得之液晶配向膜、及具備所得之液晶配向膜的液晶顯示元件。The present invention relates to a manufacturing method of a liquid crystal alignment film, a liquid crystal alignment film obtained by the manufacturing method, and a liquid crystal display element provided with the obtained liquid crystal alignment film.
被使用於液晶電視、液晶顯示器等的液晶顯示元件，通常在元件內設置有控制液晶之排列狀態用的液晶配向膜。現在，工業上最普及的液晶配向膜係將形成於電極基板上之由聚醯胺酸及/或將此聚醯胺酸進行醯亞胺化之聚醯亞胺所成之膜的表面，藉由以綿、尼龍、聚酯等的布，於一方向摩擦，進行所謂的摩擦處理來製作。Liquid crystal display elements used in liquid crystal televisions, liquid crystal displays, etc. usually have a liquid crystal alignment film inside the element for controlling the alignment state of liquid crystals. Nowadays, the most popular liquid crystal alignment film in the industry is formed on the surface of a film made of polyamide acid and/or polyimide that has undergone imidization of the polyamide acid on an electrode substrate. It is made by rubbing a cloth made of cotton, nylon, polyester, etc. in one direction and performing a so-called rubbing treatment.
摩擦處理係簡便且生產性優異可用於工業的方法。但是伴隨液晶顯示元件之高性能化、高精細化、大型化，因摩擦處理所產生之配向膜表面受傷、產生灰塵、因機械力或靜電所造成的影響、及配向處理面內之不均勻性等各種問題明顯。取代摩擦處理之液晶配向處理方法，已知藉由照射經偏光之放射線，賦予液晶配向能的光配向法。藉由光配向法之液晶配向處理，提案利用光異構化反應者，利用光交聯反應者及利用光分解反應者等(參照非專利文獻1)。The friction treatment is a simple and highly productive method that can be used industrially. However, as liquid crystal display elements become more high-performance, high-definition, and large-scale, the surface of the alignment film caused by rubbing treatment is damaged, dust is generated, the influence caused by mechanical force or static electricity, and the unevenness within the alignment treatment surface Various problems are apparent. As a liquid crystal alignment treatment method that replaces the rubbing treatment, a photo-alignment method is known that imparts alignment energy to the liquid crystal by irradiating polarized radiation. Liquid crystal alignment treatment by the photoalignment method has been proposed using photoisomerization reactions, photocrosslinking reactions, and photodecomposition reactions (see Non-Patent Document 1).
又，專利文獻1提案將主鏈上具有環丁烷環等之脂環構造的聚醯亞胺膜用於光配向法。如上述之光配向法，作為可省略摩擦處理之非摩擦之配向處理方法，在工業上以簡便的製造程序可賦予液晶配向能。不僅如此，在IPS驅動方式或邊緣電場切換(以下為Fringe Field Switching: FFS)驅動方式之液晶顯示元件中，藉由光配向法賦予液晶配向能的液晶配向膜，相較於藉由摩擦處理賦予液晶配向能的液晶配向膜，可期待提昇液晶顯示元件之對比或視角特性。因此，如上述的光配向法，可作為有希望的液晶配向處理方法而受矚目。IPS驅動方式或FFS驅動方式的液晶顯示元件所使用的液晶配向膜，除了優異之液晶配向性或電特性等之基本特性，還有必須抑制因長期交流驅動所造成的殘影。Furthermore, Patent Document 1 proposes using a polyimide film having an alicyclic structure such as a cyclobutane ring in the main chain for a photo-alignment method. The above-mentioned photo-alignment method is a non-rubbing alignment treatment method that can omit rubbing treatment, and can impart alignment energy to liquid crystals in an industrially simple manufacturing process. Not only that, in liquid crystal display elements using the IPS driving method or the fringe field switching (hereinafter referred to as Fringe Field Switching: FFS) driving method, the liquid crystal alignment film that imparts alignment energy to the liquid crystal through the photo-alignment method is more efficient than the liquid crystal alignment film that is imparted through the rubbing process. Liquid crystal alignment films with liquid crystal alignment capabilities can be expected to improve the contrast or viewing angle characteristics of liquid crystal display elements. Therefore, the above-mentioned photo-alignment method is attracting attention as a promising liquid crystal alignment treatment method. The liquid crystal alignment film used in IPS-driven or FFS-driven liquid crystal display elements, in addition to its basic properties such as excellent liquid crystal alignment and electrical properties, must also suppress image retention caused by long-term AC driving.
但是藉由光配向法被賦予液晶配向能的液晶配向膜，相較於以摩擦被賦予液晶配向能者，有對高分子膜之配向方向的異向性小的問題。異向性小時，無法得到充分的液晶配向性，作為液晶顯示元件時，會產生殘影等的問題。相對於此，藉由光配向法被賦予液晶配向能的液晶配向膜之提高異向性的方法，有提案除去於光照射後，因該光照射，聚醯亞胺之主鏈被切斷而生成的低分子量成分(專利文獻2)。 [先前技術文獻] [專利文獻]However, a liquid crystal alignment film that is endowed with liquid crystal alignment energy through a photoalignment method has a problem of smaller anisotropy to the alignment direction of the polymer film than one that is endowed with liquid crystal alignment energy through rubbing. If the anisotropy is small, sufficient liquid crystal alignment cannot be obtained, and problems such as image sticking may occur when used as a liquid crystal display element. In contrast, there is a proposal to improve the anisotropy of a liquid crystal alignment film that has been given liquid crystal alignment energy by a photoalignment method. It is proposed to remove the film after light irradiation. The main chain of the polyimide is cut due to the light irradiation. The resulting low molecular weight component (Patent Document 2). [Prior art documents] [Patent documents]
[專利文獻1]日本特開平9-297313號公報 [專利文獻2]日本特開2011-107266號公報 [非專利文獻][Patent Document 1] Japanese Patent Application Laid-Open No. 9-297313 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-107266 [Non-patent Document]
[非專利文獻1]「液晶光配向膜」木戶脇、市村 機能材料1997年11月號 Vol.17、No.11 13~22頁[Non-patent document 1] "Liquid crystal photo-alignment film" Kidowaki, Ichimura, Functional Materials, November 1997, Vol. 17, No. 11, pages 13~22
[發明所欲解決之課題][Problem to be solved by the invention]
本發明人等檢討的結果，得知前述聚醯亞胺之主鏈被切斷而生成之低分子量成分除去不充分時，殘存的低分子化合物使液晶顯示器的性能惡化。具體而言，得知殘存的低分子化合物會阻礙液晶之配向，產生配向不均，因殘存的低分子化合物而產生亮點等之不良的情況。但是為了除去上述低分子量成分時，必須實施加熱處理或以有機溶劑之接觸處理，故增加製造液晶配向膜的步驟，而液晶顯示元件之製造中良率惡化，有無法得到更高品質之液晶顯示元件的問題。As a result of examination by the present inventors, it was found that if the low molecular weight components generated by cutting the main chain of the polyimide are not sufficiently removed, the remaining low molecular weight compounds will deteriorate the performance of the liquid crystal display. Specifically, it was found that the remaining low molecular weight compounds will hinder the alignment of the liquid crystal, causing uneven alignment, and causing defects such as bright spots due to the remaining low molecular weight compounds. However, in order to remove the above-mentioned low molecular weight components, it is necessary to perform heat treatment or contact treatment with an organic solvent, so the steps of manufacturing the liquid crystal alignment film are increased, and the yield of the liquid crystal display element is deteriorated, and a higher quality liquid crystal display may not be obtained. Component issues.
本發明之目的係提供可抑制因IPS驅動方式或FFS驅動方式之液晶顯示元件中發生之長期交流驅動所造成之殘影，可比以往更少的步驟數製造沒有因低分子量化合物殘存所發生之不良情況的液晶配向膜之液晶配向膜的製造方法、藉由該製造方法所得之上述液晶配向膜、及具有該液晶配向膜之液晶顯示元件。 [用以解決課題之手段]The object of the present invention is to provide a liquid crystal display element with an IPS drive system or an FFS drive system that can suppress image sticking caused by long-term AC driving and can be manufactured in a smaller number of steps than in the past without any defects caused by residual low molecular weight compounds. In this case, there is a method for manufacturing a liquid crystal alignment film, the above-mentioned liquid crystal alignment film obtained by the manufacturing method, and a liquid crystal display element having the liquid crystal alignment film. [Means used to solve problems]
本發明人等為了達成上述之目的，精心檢討的結果，發現藉由下述要旨的發明，可達成上述之目的。In order to achieve the above-mentioned object, the present inventors conducted careful examination and found that the above-mentioned object can be achieved by the invention having the following gist.
1.一種液晶配向膜之製造方法，其特徵係具有下述(A)、(B)、(C)、及(D)之步驟，且連續進行步驟(B)與步驟(C)， 步驟(A)：塗佈含有由下述四羧酸衍生物成分與二胺成分所得之聚醯亞胺前驅物之醯亞胺化物的聚醯亞胺的液晶配向劑的步驟。 其中四羧酸衍生物成分為含有選自下述式(1)表示之四羧酸二酐、及其衍生物之至少1種類及選自下述式(2)表示之四羧酸二酐、及其衍生物之至少1種類的四羧酸衍生物成分， 步驟(B)：將塗佈後之液晶配向劑以實質上未進行熱醯亞胺化的條件下加熱，得到膜的步驟。 步驟(C)：對步驟(B)所得的膜照射偏光之紫外線的步驟。 步驟(D)：將在步驟(C)照射紫外線的膜以100℃以上、且比在步驟(B)加熱的溫度更高的溫度進行燒成的步驟。1. A method for manufacturing a liquid crystal alignment film, which is characterized by having the following steps (A), (B), (C), and (D), and step (B) and step (C) are performed continuously, and step ( A): The step of applying a liquid crystal alignment agent containing a polyimide containing an imide product of a polyimide precursor obtained from the following tetracarboxylic acid derivative component and a diamine component. The tetracarboxylic acid derivative component contains at least one type of tetracarboxylic dianhydride represented by the following formula (1) and its derivatives, and a tetracarboxylic dianhydride represented by the following formula (2), At least one kind of tetracarboxylic acid derivative component of its derivatives, Step (B): The step of heating the coated liquid crystal alignment agent under conditions that do not substantially undergo thermal imidization to obtain a film. Step (C): The step of irradiating the film obtained in step (B) with polarized ultraviolet light. Step (D): A step in which the film irradiated with ultraviolet rays in step (C) is fired at a temperature of 100°C or higher and higher than the temperature heated in step (B).
X1 為下述式(X1-1)~(X1-4)表示之構造，X2 為下述式(X2-1)~(X2-2)表示之構造， X 1 has a structure represented by the following formulas (X1-1) ~ (X1-4), X 2 has a structure represented by the following formulas (X2-1) ~ (X2-2),
R3 至R6 各自獨立為氫原子、鹵素原子、碳數1~6之烷基、碳數2~6之烯基、碳數2~6之炔基、含有氟原子之碳數1~6之1價之有機基、或苯基，可相同或相異，但是至少1個為氫原子以外，R7 至R23 各自獨立為氫原子、鹵素原子、碳數1~6之烷基、碳數2~6之烯基、碳數2~6之炔基、含有氟原子之碳數1~6之1價之有機基、或苯基，可相同或不同， R 3 to R 6 are each independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an alkynyl group with 2 to 6 carbon atoms, or a fluorine atom containing 1 to 6 carbon atoms. The monovalent organic groups or phenyl groups may be the same or different, but at least one of them is other than a hydrogen atom. R 7 to R 23 are each independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, or An alkenyl group with 2 to 6 carbon atoms, an alkynyl group with 2 to 6 carbon atoms, a monovalent organic group with 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, may be the same or different,
。 .
2.如1.之液晶配向膜之製造方法，其中前述步驟(A)中之前述聚醯亞胺的醯亞胺化率為10%~100%。2. The method for manufacturing a liquid crystal alignment film as in 1., wherein the imidization rate of the polyimide in step (A) is 10% to 100%.
3.如1.或2.之液晶配向膜之製造方法，其中前述式(2)表示之四羧酸二酐或其衍生物，相對於全四羧酸衍生物成分1莫耳，含有1~30莫耳%。3. The method for manufacturing a liquid crystal alignment film as in 1. or 2., wherein the tetracarboxylic dianhydride or its derivative represented by the aforementioned formula (2) contains 1~ 30 mol%.
4.如1.~3.中任一項之液晶配向膜之製造方法，其中前述式(1)中之X1 之構造為選自下述式(X1-12)~(X1-16)表示之構造中之至少1種，4. The method for manufacturing a liquid crystal alignment film according to any one of 1. to 3., wherein the structure of X 1 in the aforementioned formula (1) is selected from the following formulas (X1-12) to (X1-16). At least one of the structures,
。 .
5.如1.~4.中任一項之液晶配向膜之製造方法，其中前述式(1)中之X1 之構造為前述式(X1-12)表示之構造。5. The method for manufacturing a liquid crystal alignment film according to any one of 1. to 4., wherein the structure of X 1 in the aforementioned formula (1) is the structure represented by the aforementioned formula (X1-12).
6.如1.~5.中任一項之液晶配向膜之製造方法，其中前述式(2)中之X2 之構造為前述式(X2-1)表示之構造。6. The method for manufacturing a liquid crystal alignment film according to any one of 1. to 5., wherein the structure of X 2 in the aforementioned formula (2) is the structure represented by the aforementioned formula (X2-1).
7.如1.~6.中任一項之液晶配向膜之製造方法，其中前述二胺成分為選自下述式(3)~下述式(4)表示之構造中之至少1種，7. The method for manufacturing a liquid crystal alignment film according to any one of 1. to 6., wherein the diamine component is at least one selected from the structures represented by the following formula (3) to the following formula (4),
A1 為單鍵、酯鍵、醯胺鍵、硫酯鍵、或碳數2~20之2價之有機基，A2 為氫原子、鹵素原子、羥基、胺基、巰基、硝基、磷酸基、或碳數1~20之1價之有機基，a為1~4之整數，a為2以上的情形，A1 之構造可相同或不同，b及c各自獨立為1~2之整數。 A 1 is a single bond, ester bond, amide bond, thioester bond, or a divalent organic group with 2 to 20 carbon atoms. A 2 is a hydrogen atom, a halogen atom, a hydroxyl group, an amine group, a mercapto group, a nitro group, or a phosphoric acid group. radical, or a monovalent organic radical with a carbon number of 1 to 20, a is an integer from 1 to 4, and when a is 2 or more, the structure of A 1 can be the same or different, b and c are each independently an integer from 1 to 2 .
8.如1.~7.中任一項之液晶配向膜之製造方法，其中前述二胺成分為選自下述式(DA-1)~(DA-20)中之至少1種，8. The method for manufacturing a liquid crystal alignment film according to any one of 1. to 7., wherein the aforementioned diamine component is at least one selected from the following formulas (DA-1) to (DA-20),
。 .
9.如1.~8.中任一項之液晶配向膜之製造方法，其中在前述步驟(B)中，以50~150℃進行燒成。9. The method for manufacturing a liquid crystal alignment film according to any one of 1. to 8., wherein in the aforementioned step (B), the firing is performed at 50 to 150°C.
10.如1.~9.中任一項之液晶配向膜之製造方法，其中在前述步驟(D)中，將膜以150~300℃進行燒成。10. The method for manufacturing a liquid crystal alignment film according to any one of 1. to 9., wherein in the aforementioned step (D), the film is fired at 150 to 300°C.
11.一種液晶配向膜，其特徵係藉由如1.~10.中任一項之液晶配向膜之製造方法而製得者。11. A liquid crystal alignment film, characterized by being produced by the method for manufacturing a liquid crystal alignment film according to any one of 1. to 10.
12.一種液晶顯示元件，其特徵係具備如11.之液晶配向膜。12. A liquid crystal display element, characterized by having a liquid crystal alignment film as in 11.
13.如12.液晶顯示元件，其中前述液晶顯示元件為以橫電場驅動液晶者。 [發明效果]13. The liquid crystal display element as in 12. wherein the liquid crystal display element drives the liquid crystal with a transverse electric field. [Effects of the invention]
依據本發明之製造液晶配向膜的製造方法時，可比以往更少的步驟數可製造可抑制因IPS驅動方式或FFS驅動方式之液晶顯示元件中發生之長期交流驅動所造成之殘影，沒有因低分子量化合物殘存而發生之不良情況的液晶配向膜。又，藉由本發明之製造方法所得之液晶配向膜，可以較少步驟數製造，故可提高液晶顯示元件的良率，可更有效率製造液晶顯示元件。又，藉由使用以本發明之製造方法所得之液晶配向膜，可抑制因IPS驅動方式或FFS驅動方式之液晶顯示元件中發生之長期交流驅動所造成之殘影。According to the method of manufacturing a liquid crystal alignment film of the present invention, the number of steps can be reduced than before, and the image sticking caused by the long-term AC driving that occurs in the liquid crystal display element of the IPS driving method or the FFS driving method can be suppressed without causing any problems. Liquid crystal alignment film that causes problems caused by residual low molecular weight compounds. In addition, the liquid crystal alignment film obtained by the manufacturing method of the present invention can be manufactured with a smaller number of steps, so the yield of the liquid crystal display element can be improved and the liquid crystal display element can be manufactured more efficiently. In addition, by using the liquid crystal alignment film obtained by the manufacturing method of the present invention, it is possible to suppress image sticking caused by long-term AC driving that occurs in an IPS-driven or FFS-driven liquid crystal display element.
此外，藉由本發明之製造方法所製得之液晶配向膜係因聚醯亞胺之主鏈被切斷而生成之低分子量成分之發生量較少，故可抑制配向不良或亮點之發生等、因低分子量化合物殘存所發生之不良情況，可製造更優異的液晶顯示元件。因此，具備藉由本發明之製造方法所製得之液晶配向膜的液晶顯示元件成為殘影特性或信賴性優異者，可適用於大畫面，且高精細之液晶電視或中小型之汽車導航系統或智慧型手機等。 [實施發明之形態]In addition, the liquid crystal alignment film produced by the manufacturing method of the present invention has a small amount of low molecular weight components generated by cutting the main chain of the polyimide, so it can suppress the occurrence of poor alignment or bright spots, etc. It is possible to manufacture better liquid crystal display elements due to defects caused by residual low molecular weight compounds. Therefore, the liquid crystal display element equipped with the liquid crystal alignment film produced by the manufacturing method of the present invention has excellent image sticking characteristics or reliability, and can be applied to large-screen, high-definition LCD televisions or small and medium-sized car navigation systems or Smartphones, etc. [Form of carrying out the invention]
本發明之製造液晶配向膜的製造方法係使用含有：由含有具有特定構造之四羧酸衍生物的四羧酸衍生物成分與二胺成分所得之聚醯亞胺前驅物之醯亞胺化物的聚醯亞胺(以下也稱為特定聚合物)的液晶配向劑。The method for manufacturing a liquid crystal alignment film of the present invention uses an imide compound of a polyimide precursor obtained from a tetracarboxylic acid derivative component containing a tetracarboxylic acid derivative having a specific structure and a diamine component. Liquid crystal alignment agent of polyimide (hereinafter also referred to as specific polymer).
＜特定聚合物＞ 本發明之製造方法所使用的特定聚合物為具有特定構造之聚醯亞胺前驅物之醯亞胺化物的聚醯亞胺。聚醯亞胺前驅物只要是藉由聚醯胺酸、聚醯胺酸酯等之加熱或觸媒所得之化學醯亞胺化，形成醯亞胺環的聚醯亞胺前驅物時，即無特別限定。從加熱或化學醯亞胺化容易進行的觀點，聚醯亞胺前驅物更佳為聚醯胺酸、或聚醯胺酸酯。聚醯亞胺之醯亞胺化率，無特別限定，較佳為10~100%，更佳為50~100%，又更佳為50~80%。以下詳述構成上述特定聚合物之原料的各成分。<Specific polymer> The specific polymer used in the production method of the present invention is a polyimide that is an imide product of a polyimide precursor having a specific structure. As long as the polyimide precursor is chemically imidized by heating polyamide acid, polyamide ester, etc. or using a catalyst to form an imine ring, there is no need for polyimide precursors. Specially limited. From the viewpoint that heating or chemical imidization is easy, the polyimide precursor is more preferably polyamide acid or polyamide ester. The imidization rate of polyimide is not particularly limited, but is preferably 10 to 100%, more preferably 50 to 100%, and still more preferably 50 to 80%. Each component constituting the raw material of the above-mentioned specific polymer will be described in detail below.
＜四羧酸衍生物成分＞ 本發明之製造方法使用之用於特定聚合物之聚合的四羧酸衍生物成分，不僅使用四羧酸二酐，也可使用其四羧酸衍生物的四羧酸、四羧酸二鹵化物化合物、四羧酸二烷酯化合物或四羧酸二烷酯二鹵化物化合物。<Tetracarboxylic acid derivative component> The tetracarboxylic acid derivative component used in the polymerization of a specific polymer used in the manufacturing method of the present invention is not only tetracarboxylic dianhydride, but also tetracarboxylic acid derivatives thereof. Acid, tetracarboxylic acid dihalide compound, tetracarboxylic acid dialkyl ester compound or tetracarboxylic acid dialkyl ester dihalide compound.
用於特定聚合物之聚合的四羧酸二酐或其衍生物係含有選自下述式(1)表示之四羧酸二酐及其衍生物之至少1種類與、選自下述式(2)表示之四羧酸二酐及其衍生物之至少1種類。The tetracarboxylic dianhydride or derivatives thereof used for polymerization of a specific polymer contains at least one type selected from the group consisting of tetracarboxylic dianhydride represented by the following formula (1) and its derivatives and selected from the group consisting of the following formula (1) 2) At least one type of the represented tetracarboxylic dianhydride and its derivatives.
X1 為下述式(X1-1)~(X1-4)表示之構造。 X 1 has a structure represented by the following formulas (X1-1) to (X1-4).
R3 至R6 各自獨立為氫原子、鹵素原子、碳數1~6之烷基、碳數2~6之烯基、碳數2~6之炔基、含有氟原子之碳數1~6之1價之有機基、或苯基，可相同或相異，但是至少1個為氫原子以外。R7 至R23 各自獨立為氫原子、鹵素原子、碳數1~6之烷基、碳數2~6之烯基、碳數2~6之炔基、含有氟原子之碳數1~6之1價之有機基、或苯基，可相同或不同。 R 3 to R 6 are each independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an alkynyl group with 2 to 6 carbon atoms, or a fluorine atom containing 1 to 6 carbon atoms. The monovalent organic groups or phenyl groups may be the same or different, but at least one of them is other than a hydrogen atom. R 7 to R 23 are each independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an alkynyl group with 2 to 6 carbon atoms, or a fluorine atom containing 1 to 6 carbon atoms. The monovalent organic groups or phenyl groups may be the same or different.
從抑制因長期交流驅動所造成之殘影等的觀點，X1 之構造係以選自下述式(X1-12)~(X1-16)表示之構造之至少1種為佳，特佳為下述式(X1-12)。From the viewpoint of suppressing image sticking caused by long-term AC driving, the structure of The following formula (X1-12).
上述式(1)表示之四羧酸二酐或其衍生物之比率係相對於全四羧酸二酐或其衍生物1莫耳，較佳為50莫耳%以上，更佳為70莫耳%以上，又更佳為80莫耳%以上。The ratio of the tetracarboxylic dianhydride or its derivative represented by the above formula (1) is preferably 50 mol% or more, more preferably 70 mole per 1 mole of the total tetracarboxylic dianhydride or its derivative. % or more, and more preferably 80 mol% or more.
上述式(2)中，X2 為下述式(X2-1)~(X2-2)表示之構造。In the above formula (2), X 2 has a structure represented by the following formulas (X2-1) to (X2-2).
從抑制因長期交流驅動所造成之殘影等的觀點，X2 之構造為上述式(X2-1)表示之構造為佳。上述式(2)表示之四羧酸二酐或其衍生物之比率係相對於全四羧酸二酐或其衍生物(全四羧酸衍生物成分)1莫耳，較佳為1~30莫耳%，更佳為10~30%，又更佳為10~20%。From the viewpoint of suppressing image sticking caused by long-term AC driving, the structure of X 2 is preferably a structure represented by the above formula (X2-1). The ratio of the tetracarboxylic dianhydride or its derivative represented by the above formula (2) is 1 mole relative to the total tetracarboxylic dianhydride or its derivative (the total tetracarboxylic acid derivative component), preferably 1 to 30 Mol%, preferably 10~30%, further preferably 10~20%.
用於特定聚合物之聚合的四羧酸二酐及其衍生物，除上述式(1)及(2)以外，也可使用下述式(6)表示之四羧酸二酐及其衍生物。Tetracarboxylic dianhydride and its derivatives used for polymerization of specific polymers, in addition to the above formulas (1) and (2), tetracarboxylic dianhydride and its derivatives represented by the following formula (6) can also be used .
X3 為4價之有機基，其構造無特別限定。具體例，可列舉下述式(X-9)~(X-47)之構造。就化合物之取得之容易性的觀點，X3 之構造，可列舉X-17、X-25、X-26、X-27、X-28、X-32、X-35、X-37、X-39、X-43、X-44、X-45、X-46、及X-47。又，可得到因直流電壓而蓄積之殘留電荷快速緩和之液晶配向膜的觀點，使用具有芳香族環構造之四羧酸二酐為佳，X3 之構造，更佳為X-26、X-27、X-28、X-32、X-35、及X-37。 X 3 is a tetravalent organic group, and its structure is not particularly limited. Specific examples include structures of the following formulas (X-9) to (X-47). From the perspective of the ease of obtaining the compound, the structure of X 3 can include X-17, X-25, X-26, X-27, X-28, -39, X-43, X-44, X-45, X-46, and X-47. In addition, from the viewpoint of obtaining a liquid crystal alignment film in which residual charges accumulated due to DC voltage can be quickly relaxed, it is preferable to use tetracarboxylic dianhydride having an aromatic ring structure. The structure of X3 is more preferably X-26, X- 27, X-28, X-32, X-35, and X-37.
＜二胺＞ 本發明之製造方法使用之用於特定聚合物之聚合的二胺成分為公知之二胺時，即無特別限定。就抑制因長期交流驅動所造成之殘影的觀點，選自下述式(3)及下述式(4)之至少1種類為佳。<Diamine> If the diamine component used in the polymerization of a specific polymer used in the production method of the present invention is a known diamine, it is not particularly limited. From the viewpoint of suppressing image sticking caused by long-term AC driving, at least one type selected from the following formula (3) and the following formula (4) is preferred.
A1 為單鍵、酯鍵、醯胺鍵、硫酯鍵、或碳數2~20之2價之有機基，A2 為氫原子、鹵素原子、羥基、胺基、巰基、硝基、磷酸基、或碳數1~20之1價之有機基，a為1~4之整數，a為2以上的情形，A1 之構造可相同或不同。b及c各自獨立為1~2之整數。 A 1 is a single bond, ester bond, amide bond, thioester bond, or a divalent organic group with 2 to 20 carbon atoms. A 2 is a hydrogen atom, a halogen atom, a hydroxyl group, an amine group, a mercapto group, a nitro group, or a phosphoric acid group. radical, or a monovalent organic radical with a carbon number of 1 to 20, a is an integer from 1 to 4, and when a is 2 or more, the structures of A 1 may be the same or different. b and c are each independently an integer between 1 and 2.
就抑制因長期交流驅動所造成之殘影等的觀點，上述式(3)及上述式(4)之具體的構造，較佳為下述式(DA-1)~(DA-20)之構造。其中，更佳為DA-1、DA-2、DA-4、DA-5、DA-7。From the viewpoint of suppressing image sticking caused by long-term AC driving, the specific structures of the above formula (3) and the above formula (4) are preferably structures of the following formulas (DA-1) to (DA-20) . Among them, DA-1, DA-2, DA-4, DA-5, and DA-7 are more preferred.
上述式(3)及上述式(4)表示之二胺之含量係相對於全二胺成分1莫耳，較佳為50~100莫耳%，更佳為70~100莫耳%。用於特定聚合物之聚合的二胺，除上述式(3)及(4)以外，也可使用下述式(7)表示之二胺。The content of the diamine represented by the above formula (3) and the above formula (4) is preferably 50 to 100 mol%, more preferably 70 to 100 mol% based on 1 mole of the total diamine component. As the diamine used for polymerization of a specific polymer, in addition to the above formulas (3) and (4), a diamine represented by the following formula (7) can also be used.
A3 各自獨立為氫原子或、碳數1~5之烷基、碳數2~5之烯基、碳數2~5之炔基，可相同或不同。就液晶配向性的觀點，A3 為氫原子、或甲基為佳。Y1 為2價有機基，可列舉下述式(Y-1)~(Y-49)及(Y-57)~(Y-167)。 A 3 is each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, and may be the same or different. From the viewpoint of liquid crystal alignment, A 3 is preferably a hydrogen atom or a methyl group. Y 1 is a divalent organic group, and examples thereof include the following formulas (Y-1) to (Y-49) and (Y-57) to (Y-167).
就提高聚合物之溶解性的觀點，Y1 之構造中包含下述式(8)表示之構造為佳。From the viewpoint of improving the solubility of the polymer, the structure of Y 1 preferably includes a structure represented by the following formula (8).
D為t-丁氧基羰基。 D is t-butoxycarbonyl.
包含上述式(8)表示之構造之Y1 的具體例，可列舉Y-158、Y-159、Y-160、Y-161、Y-162、Y-163。Specific examples of Y 1 including the structure represented by the above formula (8) include Y-158, Y-159, Y-160, Y-161, Y-162, and Y-163.
＜聚醯胺酸酯、聚醯胺酸及聚醯亞胺之製造方法＞ 本發明所使用之聚醯亞胺前驅物之聚醯胺酸酯、聚醯胺酸及聚醯亞胺，例如可使用國際公開公報WO2013/157586所記載之習知的方法來合成。<Method for producing polyamide ester, polyamide acid and polyimide> The polyamide ester, polyamide acid and polyimide precursor used in the present invention can be, for example, It was synthesized using a conventional method described in International Publication No. WO2013/157586.
＜液晶配向劑＞ 本發明所使用之液晶配向劑係具有聚合物成分溶解於有機溶劑中之溶液形態。聚合物之分子量係以重量平均分子量，較佳為2,000~500,000，更佳為5,000~300,000，又更佳為10,000~100,000。又，數平均分子量，較佳為1,000 ~250,000，更佳為2,500~150,000，又更佳為5,000~50,000。<Liquid crystal alignment agent> The liquid crystal alignment agent used in the present invention has a solution form in which a polymer component is dissolved in an organic solvent. The molecular weight of the polymer is based on the weight average molecular weight, and is preferably 2,000~500,000, more preferably 5,000~300,000, and still more preferably 10,000~100,000. Moreover, the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.
本發明所使用之液晶配向劑之聚合物的濃度，可藉由欲形成之塗膜厚度之設定，進行適當變更，但是就使形成均勻且無缺陷之塗膜的觀點而言，以1重量%以上為佳，就溶液之保存安定性的觀點，以10重量%以下為佳。特佳之聚合物的濃度為2~8質量%。The concentration of the polymer of the liquid crystal alignment agent used in the present invention can be appropriately changed by setting the thickness of the coating film to be formed. However, from the perspective of forming a uniform and defect-free coating film, 1% by weight is used. The above is preferred, and from the viewpoint of storage stability of the solution, 10% by weight or less is preferred. A particularly preferred polymer concentration is 2 to 8% by mass.
本發明所使用之液晶配向劑所含有之有機溶劑，只要是可使聚合物成分均勻地溶解者時，即無特別限定。其具體例，可列舉N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-甲基己內醯胺、2-吡咯烷酮、N-乙烯基-2-吡咯烷酮、二甲基亞碸、二甲基碸、γ-丁內酯、1,3-二甲基-咪唑啉酮、3-甲氧基-N,N-二甲基丙醯胺等。此等可使用1種或混合2種以上使用。又，即使為單獨無法使聚合物成分均勻地溶解的溶劑，只要在聚合物不會析出的範圍內，可混合於上述有機溶劑中。The organic solvent contained in the liquid crystal alignment agent used in the present invention is not particularly limited as long as it can dissolve the polymer component uniformly. Specific examples thereof include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N- Ethyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyltrisoxide, dimethyltrisone, γ-butyrolactone, 1,3- Dimethyl-imidazolinone, 3-methoxy-N,N-dimethylpropylamine, etc. These can be used 1 type or in mixture of 2 or more types. In addition, even if it is a solvent that alone cannot dissolve the polymer component uniformly, it can be mixed with the above-mentioned organic solvent as long as the polymer does not precipitate.
本發明所使用之液晶配向劑，除了使聚合物成分溶解用之有機溶劑外，也可含有將液晶配向劑塗佈於基板時，提高塗膜均勻性用的溶劑。此溶劑一般使用表面張力比上述有機溶劑低的溶劑。其具體例，可列舉乙基溶纖劑、丁基溶纖劑、乙基卡必醇、丁基卡必醇、乙基卡必醇乙酸酯、乙二醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇-1-單甲醚-2-乙酸酯、丙二醇-1-單乙醚-2-乙酸酯、丁基溶纖劑乙酸酯、二丙二醇、2-(2-乙氧基丙氧基)丙醇、乳酸甲酯、乳酸乙酯、乳酸n-丙酯、乳酸n-丁酯、乳酸異戊酯等。此等之溶劑也可併用2種以上。The liquid crystal alignment agent used in the present invention, in addition to the organic solvent used to dissolve the polymer component, may also contain a solvent used to improve the uniformity of the coating film when the liquid crystal alignment agent is applied to the substrate. This solvent generally uses a solvent with a lower surface tension than the above-mentioned organic solvent. Specific examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, and 1-methoxy-2-propanol. Alcohol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1 -Monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, butyl cellosolve acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, lactic acid Methyl ester, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, etc. Two or more types of these solvents may be used in combination.
本發明之液晶配向劑中，除了上述外，在不損及本發明效果的範圍內時，也可添加特定聚合物以外之聚合物、改變液晶配向膜之介電常數或導電性等之電特性之目的之介電體或導電物質、提高液晶配向膜與基板之密著性之目的之矽烷偶合劑、提高作為液晶配向膜時之膜的硬度或緻密度之目的之交聯性化合物、及塗膜燒成時，為了有效進行聚醯胺酸之醯亞胺化之目的之醯亞胺化促進劑等。In the liquid crystal alignment agent of the present invention, in addition to the above, within the scope that does not impair the effect of the present invention, polymers other than specific polymers can also be added to change the electrical properties such as the dielectric constant or conductivity of the liquid crystal alignment film. Dielectrics or conductive substances for the purpose, silane coupling agents for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate, cross-linking compounds for the purpose of improving the hardness or density of the film when used as a liquid crystal alignment film, and coatings When the film is fired, an imidization accelerator, etc. is used for the purpose of effectively carrying out imidization of polyamide acid.
＜液晶配向膜之製造方法＞ 本發明之製造液晶配向膜的製造方法係將含有上述特定聚合物之液晶配向劑塗佈於基板上而得的塗膜，以實質上未進行特定聚合物之熱醯亞胺化的條件下加熱，然後，在以往的液晶配向膜製造步驟進行之特定聚合物之熱醯亞胺化，且未經使殘存溶劑幾乎完全蒸發的步驟(以後也稱為燒成步驟)，而進行偏光紫外線照射後，進行燒成步驟。<Method for manufacturing a liquid crystal alignment film> The method for manufacturing a liquid crystal alignment film of the present invention is to apply a liquid crystal alignment agent containing the above-mentioned specific polymer to a coating film on a substrate, without substantially heating the specific polymer. Heating under conditions of imidization, and then thermally imidizing a specific polymer in the conventional liquid crystal alignment film manufacturing process without a step of almost completely evaporating the remaining solvent (hereinafter also referred to as a baking step) ), and after polarized ultraviolet irradiation, a firing step is performed.
藉此可減少製造步驟數，同時具備製得之液晶配向膜而得的液晶顯示元件，令人驚訝可抑制因長期交流驅動所造成之殘影，而不會發生因低分子量化合物殘存而產生之亮點等之不良情況。This can reduce the number of manufacturing steps, and at the same time, the liquid crystal display element equipped with the prepared liquid crystal alignment film can surprisingly suppress image retention caused by long-term AC driving without causing problems caused by residual low molecular weight compounds. Highlights and other adverse conditions.
具體而言，其特徵係具有下述(A)、(B)、(C)、及(D)之步驟，且連續進行步驟(B)與步驟(C)， 步驟(A)：塗佈含有特定聚合物之液晶配向劑的步驟(步驟(A))，將塗佈後之液晶配向劑以實質上未進行熱醯亞胺化的條件下加熱，得到膜的步驟(步驟(B))，對步驟(B)所得的膜照射偏光之紫外線的步驟(步驟(C))，將在步驟(C)照射紫外線的膜以100℃以上、且比在步驟(B)加熱的溫度更高的溫度進行燒成的步驟(步驟(D)，且步驟(B)與步驟(C)連續進行。Specifically, it is characterized by having the following steps (A), (B), (C), and (D), and performing step (B) and step (C) continuously. Step (A): Coating containing The step of specifying a liquid crystal alignment agent of a polymer (step (A)), and the step of heating the coated liquid crystal alignment agent under conditions that do not substantially undergo thermal imidization to obtain a film (step (B)), In the step of irradiating the film obtained in step (B) with polarized ultraviolet rays (step (C)), the film irradiated with ultraviolet rays in step (C) is heated to a temperature of 100° C. or higher and higher than the temperature heated in step (B). The step of firing (step (D)) is performed, and step (B) and step (C) are performed continuously.
＜步驟(A)＞ 塗佈本發明之製造方法所使用之液晶配向劑的基板，只要是透明性高的基板即可無特別限定，可使用玻璃基板、氮化矽基板，同時亦可使用丙烯酸基板或聚碳酸酯基板等之塑膠基板等。此時，使用形成有驅動液晶用之ITO電極等的基板時，就製程之簡化的觀點為佳。又，反射型的液晶顯示元件，若僅為單側之基板時，也可使用矽晶圓等之不透明的物質，此時的電極也可使用鋁等反射光的材料。<Step (A)> The substrate on which the liquid crystal alignment agent used in the manufacturing method of the present invention is coated is not particularly limited as long as it is a highly transparent substrate. Glass substrates, silicon nitride substrates, and acrylic substrates can also be used. Plastic substrates such as substrates or polycarbonate substrates. In this case, it is preferable from the viewpoint of simplifying the manufacturing process to use a substrate on which ITO electrodes for driving liquid crystal are formed. In addition, if the reflective liquid crystal display element has only one side of the substrate, an opaque material such as a silicon wafer can also be used. In this case, the electrode can also use a light-reflecting material such as aluminum.
液晶配向劑之塗佈方法無特別限定，但工業上一般以網版印刷、平版印刷、凸版印刷或噴墨法等進行塗佈的方法。其他的塗佈方法，有浸漬法、輥塗佈法、狹縫塗佈法、旋轉器法或噴霧法等，也可依目的來使用此等。The coating method of the liquid crystal alignment agent is not particularly limited, but in industry, the coating method is generally screen printing, offset printing, letterpress printing or inkjet method. Other coating methods include dipping method, roll coating method, slit coating method, spinner method, spray method, etc., and these can also be used depending on the purpose.
＜步驟(B)＞ 步驟(B)係將塗佈於基板上之液晶配向劑以實質上未進行熱醯亞胺化的條件下加熱，形成膜的步驟。將液晶配向劑塗佈於基板上後，藉由加熱板、熱循環型烤箱或IR(紅外線)型烤箱等的加熱手段，使溶劑蒸發，可作為液晶配向膜。此步驟可選擇任意之溫度與時間。只要為可除去液晶配向劑之有機溶劑的溫度時，無特別限定，通常為了充分地除去所含有的溶劑時，以50~150℃加熱1~10分鐘為佳，以50~120℃加熱1~5分鐘更佳。<Step (B)> Step (B) is a step of forming a film by heating the liquid crystal alignment agent applied on the substrate without substantially performing thermal imidization. After the liquid crystal alignment agent is coated on the substrate, the solvent is evaporated by heating means such as a hot plate, thermal cycle oven or IR (infrared) oven, and can be used as a liquid crystal alignment film. You can choose any temperature and time for this step. There is no particular limit as long as the temperature of the organic solvent of the liquid crystal alignment agent can be removed. Generally, in order to fully remove the contained solvent, it is better to heat at 50~150°C for 1~10 minutes, and to heat at 50~120°C for 1~10 minutes. 5 minutes is better.
＜步驟(C)＞ 步驟(C)係對步驟(B)所得的膜照射偏光之紫外線的步驟。又，步驟(B)與步驟(C)連續進行。紫外線係使用具有200~400nm之波長的紫外線為佳，其中以具有200~300nm之波長的紫外線更佳。為了改善液晶配向性，也可將形成有液晶配向膜塗膜的基板，邊以50~250℃加熱，邊照紫外線。又，前述放射線的照射量，以1~10,000mJ/cm2 為佳。其中，以100~5,000mJ/cm2 為更佳。如此製作的液晶配向膜，可使液晶分子於一定方向穩定配向。經偏光之紫外線的消光比越高，由於可賦予更高的異向性，故較佳。具體而言，經直線偏光之紫外線的消光比，以10：1以上為佳，20：1以上為更佳。<Step (C)> Step (C) is a step of irradiating the film obtained in step (B) with polarized ultraviolet light. Moreover, step (B) and step (C) are performed continuously. It is preferable to use ultraviolet rays with a wavelength of 200 to 400 nm, and among them, ultraviolet rays with a wavelength of 200 to 300 nm are more preferred. In order to improve the liquid crystal alignment, the substrate on which the liquid crystal alignment film is formed can also be heated at 50 to 250°C and irradiated with ultraviolet rays. In addition, the irradiation dose of the aforementioned radiation is preferably 1 to 10,000 mJ/cm 2 . Among them, 100~5,000mJ/ cm2 is better. The liquid crystal alignment film produced in this way can stably align liquid crystal molecules in a certain direction. A higher extinction ratio of polarized ultraviolet rays is preferable because it can provide higher anisotropy. Specifically, the extinction ratio of linearly polarized ultraviolet rays is preferably 10:1 or more, and more preferably 20:1 or more.
＜步驟(D)＞ 步驟(D)係將在步驟(C)照射紫外線的膜進行燒成的步驟。具體而言，以100℃以上、且比在步驟(B)加熱的溫度更高的溫度進行燒成的步驟。燒成溫度係在100℃以上、且比在步驟(B)加熱的溫度更高的溫度時，無特別限定，較佳為150~300℃，更佳為150~250℃，又更佳為200~ 250℃。燒成時間係以5~120分鐘為佳，更佳為5~60分鐘，又更佳為5~30分鐘。燒成後之液晶配向膜之厚度，過薄時，液晶顯示元件之信賴性有降低的情形，故較佳為5~300nm，更佳為10~200nm。此外，前述步驟(D)之後，可將製得之液晶配向膜使用水或溶劑，進行接觸處理。<Step (D)> Step (D) is a step of firing the film irradiated with ultraviolet rays in step (C). Specifically, the step of calcining is performed at a temperature of 100° C. or higher and higher than the temperature of heating in step (B). When the firing temperature is 100°C or higher and higher than the heating temperature in step (B), it is not particularly limited, but is preferably 150~300°C, more preferably 150~250°C, and more preferably 200°C. ~250℃. The firing time is preferably 5 to 120 minutes, more preferably 5 to 60 minutes, and still more preferably 5 to 30 minutes. If the thickness of the liquid crystal alignment film after firing is too thin, the reliability of the liquid crystal display element may be reduced, so it is preferably 5 to 300 nm, and more preferably 10 to 200 nm. In addition, after the aforementioned step (D), the prepared liquid crystal alignment film can be contacted with water or a solvent.
上述接觸處理所使用的溶劑，只要是溶解藉由紫外線之照射，由液晶配向膜生成之分解物的溶劑即可，無特別限定。具體例，可列舉水、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，就泛用性或溶劑之安全性而言，以水、2-丙醇、1-甲氧基-2-丙醇或乳酸乙酯為佳。更佳為水、1-甲氧基-2-丙醇或乳酸乙酯。溶劑可為1種類、也可組合2種類以上。The solvent used in the above-mentioned contact treatment is not particularly limited as long as it is a solvent that dissolves decomposition 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, 1-methoxy-2-propanol acetate, and butyl sol. fiber agent, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate or cyclohexyl acetate, etc. Among them, in terms of versatility or safety of the solvent, water, 2-propanol, 1-methoxy-2-propanol or ethyl lactate are preferred. More preferably, it is water, 1-methoxy-2-propanol or ethyl lactate. The solvent may be one type, or two or more types may be combined.
上述接觸處理，亦即對照射了經偏光之紫外線的液晶配向膜接觸水或溶劑的處理，可列舉浸漬處理或噴霧處理(也稱為spray處理)。此等處理中之處理時間，就有效地溶解藉由紫外線，由液晶配向膜生成之分解物的點而言，以10秒鐘~1小時為佳。其中，以浸漬處理1分鐘~30分鐘為佳。又，前述接觸處理時之溶劑，可在常溫或加溫，但是較佳為10~80℃。其中，以20~50℃為佳。此外，就分解物之溶解性的點而言，必要時，也可進行超音波處理等。The above-mentioned contact treatment, that is, the treatment in which the liquid crystal alignment film irradiated with polarized ultraviolet rays is contacted with water or a solvent, may include immersion treatment or spray treatment (also called spray treatment). The processing time in these treatments is preferably 10 seconds to 1 hour in order to effectively dissolve the decomposed products generated from the liquid crystal alignment film by ultraviolet rays. Among them, the immersion treatment is preferably 1 minute to 30 minutes. In addition, the solvent used in the aforementioned contact treatment can be at normal temperature or heated, but is preferably 10 to 80°C. Among them, 20~50℃ is preferred. In addition, in view of the solubility of the decomposed products, ultrasonic treatment, etc. may also be performed when necessary.
上述接觸處理之後，以藉由水、甲醇、乙醇、2-丙醇、丙酮或甲基乙基酮等之低沸點溶劑之洗滌(也稱清洗)或液晶配向膜進行燒成為佳。此時，可進行清洗與燒成之任一者、或亦可進行兩者。燒成之溫度，以150~300℃為佳。其中，以180~250℃為更佳。又更佳者為200~230℃。又，燒成的時間以10秒鐘~30分鐘為佳。其中，以1~10分鐘為更佳。After the above contact treatment, it is better to wash (also called cleaning) with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone or methyl ethyl ketone or to bake the liquid crystal alignment film. At this time, either cleaning or baking may be performed, or both may be performed. The best firing temperature is 150~300℃. Among them, 180~250℃ is more preferable. More preferably, it is 200~230℃. In addition, the firing time is preferably 10 seconds to 30 minutes. Among them, 1 to 10 minutes is better.
本發明之液晶配向膜，適合作為IPS方式或FFS方式等之橫電場方式之液晶顯示元件的液晶配向膜，特別是可作為FFS方式之液晶顯示元件的液晶配向膜使用。液晶顯示元件係得到由本發明之液晶配向劑所得之附液晶配向膜的基板後，依已知的方法製作液晶胞，使用該液晶胞而得。液晶胞之製作方法之一例，以被動矩陣構造之液晶顯示元件為例來說明。又，也可為在構成圖像顯示之各畫素部分，設置有TFT(Thin Film Transistor)等之切換元件之主動式矩陣構造的液晶顯示元件。The liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film for a transverse electric field liquid crystal display element such as an IPS method or an FFS method, and particularly can be used as a liquid crystal alignment film for an FFS method liquid crystal display element. The liquid crystal display element is obtained by obtaining a substrate with a liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention, making a liquid crystal cell according to a known method, and using the liquid crystal cell. An example of a method for manufacturing a liquid crystal cell is explained by taking a liquid crystal display element with a passive matrix structure as an example. Alternatively, a liquid crystal display element with an active matrix structure in which a switching element such as a TFT (Thin Film Transistor) is provided in each pixel portion constituting an image display may be used.
具體而言，準備透明的玻璃製基板，在其中之一的基板上設置共用(Common)電極，在另一基板上設置片段(Segment)電極。此等電極，例如可作為ITO電極，為了能顯示所期望的圖像而被圖型化。接著，在各基板上以被覆共用電極與片段電極來設置絕緣膜。絕緣膜可作為例如藉由溶膠-凝膠法所形成之SiO2 -TiO2 的膜。Specifically, transparent glass substrates are prepared, a common electrode is provided on one of the substrates, and a segment electrode is provided on the other substrate. These electrodes, for example, can be used as ITO electrodes and are patterned in order to display a desired image. Next, an insulating film is provided on each substrate to cover the common electrode and the segment electrode. The insulating film may be, for example, a SiO 2 -TiO 2 film formed by a sol-gel method.
接著，在各基板上形成液晶配向膜，在其中之一的基板與另一基板，使彼此之液晶配向膜面呈對向方式重疊，並以密封劑黏接周邊。為了控制基板間隙，通常在密封劑中混入間隔物，又，在未設置密封劑的面內部分，也可以散佈基板間隙控制用的間隔物為佳。密封劑之一部分，設置可從外部填充液晶的開口部。接著，通過設置於密封劑上的開口部，在被2片基板與密封劑所包圍的空間內注入液晶材料，然後，使接著劑密封此開口部。注入可使用真空注入法、也可使用在大氣中利用毛細管現象的方法。液晶材料可使用正型液晶材料或負型液晶材料中任一者。其次，設置偏光板。具體而言，在與2片基板之液晶層相反側之面上黏貼一對偏光板。Then, a liquid crystal alignment film is formed on each substrate, and the liquid crystal alignment film surfaces of one of the substrates and the other substrate are overlapped in an opposite manner, and the periphery is bonded with a sealant. In order to control the substrate gap, spacers are usually mixed into the sealant. It is also preferable to spread spacers for substrate gap control in the in-plane portion where the sealant is not provided. A part of the sealant that provides an opening that can be filled with liquid crystal from the outside. Next, a liquid crystal material is injected into the space surrounded by the two substrates and the sealant through the opening provided in the sealant, and then the opening is sealed with the adhesive. For injection, a vacuum injection method or a method utilizing capillary phenomena in the atmosphere may be used. As the liquid crystal material, either a positive liquid crystal material or a negative liquid crystal material can be used. Next, set up the polarizer. Specifically, a pair of polarizing plates are bonded to the surface opposite to the liquid crystal layer of the two substrates.
如上述，藉由使用本發明之製造方法，可得到可抑制因IPS驅動方式或FFS驅動方式之液晶顯示元件中發生之長期交流驅動所造成之殘影，沒有因低分子量化合物殘存發生之不良情況，且可比以往更少的步驟數可製造的液晶配向膜。As described above, by using the manufacturing method of the present invention, it is possible to suppress the image sticking caused by the long-term AC driving that occurs in the liquid crystal display element of the IPS drive system or the FFS drive system, and there is no problem caused by the residual low molecular weight compound. , and can produce a liquid crystal alignment film in fewer steps than ever before.
[實施例][Example]
以下舉實施例，更具體地說明本發明，但本發明不限定於此等者。以下中之化合物的簡略符號及各特性之測定方法如下述。 NMP：N-甲基-2-吡咯烷酮 GBL：γ-丁內酯 BCS：丁基溶纖劑 DA-1：參照下述式(DA-1) DA-2：參照下述式(DA-2) DA-3：參照下述式(DA-3) DA-4：參照下述式(DA-4) DA-5：參照下述式(DA-5) DA-6：參照下述式(DA-6) DA-7：參照下述式(DA-7) DA-8：參照下述式(DA-8) DA-9：參照下述式(DA-9) CA-1：參照下述式(CA-1) CA-2：參照下述式(CA-2) CA-3：參照下述式(CA-3) CA-4：參照下述式(CA-4) CA-5：參照下述式(CA-5) CA-6：參照下述式(CA-6)The following examples will be given to illustrate the present invention more specifically, but the present invention is not limited thereto. The abbreviated symbols of the following compounds and the measurement methods of each characteristic are as follows. NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone BCS: Butyl cellosolve DA-1: Refer to the following formula (DA-1) DA-2: Refer to the following formula (DA-2) DA- 3: Refer to the following formula (DA-3) DA-4: Refer to the following formula (DA-4) DA-5: Refer to the following formula (DA-5) DA-6: Refer to the following formula (DA-6) DA-7: Refer to the following formula (DA-7) DA-8: Refer to the following formula (DA-8) DA-9: Refer to the following formula (DA-9) CA-1: Refer to the following formula (CA- 1) CA-2: Refer to the following formula (CA-2) CA-3: Refer to the following formula (CA-3) CA-4: Refer to the following formula (CA-4) CA-5: Refer to the following formula ( CA-5) CA-6: Refer to the following formula (CA-6)
[黏度] 溶液之黏度為使用E型黏度計TVE-22H(東機產業公司製)，以樣品量1.1ml、錐形轉子TE-1(1°34’、R24)，在溫度25℃下測量。[Viscosity] The viscosity of the solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Industrial Co., Ltd.) with a sample volume of 1.1ml and a conical rotor TE-1 (1°34', R24) at a temperature of 25°C. .
[分子量] 分子量係藉由GPC(常溫凝膠滲透色譜法)裝置測定，以聚乙二醇、聚環氧乙烷換算值算出數平均分子量(Mn)與重量平均分子量(Mw)。 GPC裝置：Shodex公司製(GPC-101)、管柱：Shodex公司製(KD803、KD805之串聯)、管柱溫度：50℃、溶離液：N,N-二甲基甲醯胺(添加劑為溴化鋰-水合物(LiBr･H2 O)為30mmol/L、磷酸･無水結晶(o-磷酸)為30mmol/L、四氫呋喃(THF)為10ml/L)、流速：1.0ml/分鐘[Molecular Weight] The molecular weight is measured with a GPC (normal temperature gel permeation chromatography) device, and the number average molecular weight (Mn) and weight average molecular weight (Mw) are calculated using polyethylene glycol and polyethylene oxide conversion values. GPC device: Shodex Co., Ltd. (GPC-101), Column: Shodex Co., Ltd. (KD803, KD805 in series), Column temperature: 50°C, Eluent: N,N-dimethylformamide (the additive is lithium bromide -Hydrate (LiBr･H 2 O) is 30mmol/L, phosphoric acid･anhydrous crystal (o-phosphoric acid) is 30mmol/L, tetrahydrofuran (THF) is 10ml/L), flow rate: 1.0ml/min
檢量線製作用標準樣品：Tosoh公司製TSK標準聚環氧乙烷(重量平均分子量(Mw)約900,000、150,000、100,000、30,000)及Polymer Laboratories製聚乙二醇(峰頂分子量(Mp)約12,000、4,000、1,000)。測量為了避免波峰重疊，而分別測量混合有900,000、100,000、12,000、1,000之4種類的樣品、及混合有150,000、30,000、4,000之3種類之2樣品。Standard samples for calibration line preparation: TSK standard polyethylene oxide manufactured by Tosoh Corporation (weight average molecular weight (Mw) approximately 900,000, 150,000, 100,000, 30,000) and polyethylene glycol manufactured by Polymer Laboratories (peak molecular weight (Mp) approximately 12,000, 4,000, 1,000). In order to avoid overlapping of peaks, the measurement was performed on 4 samples mixed with 900,000, 100,000, 12,000, and 1,000, and 2 samples mixed with 3 types 150,000, 30,000, and 4,000.
[醯亞胺化率之測量] 將聚醯亞胺粉末20mg置入NMR樣品管(NMR sampling tube stand，φ5(草野科學公司製))中，添加氘化二甲基亞碸(DMSO-d6，0.05%TMS(四甲基矽烷)混合品)(0.53ml)，施加超音波使完全溶解。此溶液藉由NMR測定機(JNW-ECA500)(日本電子datum製)測定500MHz之質子NMR。醯亞胺化率係以來自醯亞胺化前後未變化之構造的質子作為基準質子，使用此質子之波峰積算值與在9.5ppm~10.0ppm附近出現之來自醯胺酸之NH基的質子波峰積算值，藉由以下式求得。 醯亞胺化率(%)=(1-α･x/y)×100[Measurement of imidization rate] Place 20 mg of polyimide powder into an NMR sampling tube stand (φ5 (manufactured by Kusano Scientific Co., Ltd.)), and add deuterated dimethylsulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture) (0.53ml), apply ultrasonic waves to completely dissolve. This solution was measured for proton NMR at 500 MHz with an NMR measuring machine (JNW-ECA500) (manufactured by JEOL Datum). The acyl imidization rate is based on the proton from the unchanged structure before and after acyl imidization as the standard proton, and uses the peak integrated value of this proton and the proton peak derived from the NH group of amide acid that appears around 9.5 ppm ~ 10.0 ppm. The accumulated value is obtained by the following formula. acyl imidization rate (%) = (1-α･x/y)×100
上述式中，x係來自醯胺酸之NH基的質子波峰積算值，y係基準質子的波峰積算值，α係聚醯胺酸(醯亞胺化率為0%)時之基準質子相對於醯胺酸之1個NH基質子的個數比例。In the above formula, x is the peak integrated value of the protons derived from the NH group of amide, y is the integrated peak value of the reference proton, and α is the reference proton relative to the reference proton in polyamide acid (imidation rate of 0%). The ratio of the number of NH protons in one amino acid.
[液晶配向性評價用液晶胞之製作及評價] 藉由旋轉塗佈法將液晶配向劑塗佈於30mm×40mm之ITO基板上，在80℃之加熱板上使乾燥2分鐘，對塗膜面照射消光比10：1以上之直線偏光之波長254nm的紫外線後，以150~230℃之熱風循環式烤箱進行30分鐘燒成，得到膜厚100nm之附液晶配向膜(聚醯亞胺膜)的基板。將上述2片基板為一組，使膜面為內側，夾著6μm的間隔物，在基板上印刷密封劑，以使液晶配向膜面相向的配向方向成為0°的方式來貼合另1片基板後，使密封劑硬化而製作空晶胞。藉由減壓注入法，將液晶MLC-3019(Merck公司製)注入於此空晶胞，並密封注入口，得到液晶胞。以偏光顯微鏡(ECLIPSE E600WPOL)(Nikon公司製)觀察上述製作之液晶胞的配向狀態，無配向缺陷者評價為「良好」，有配向缺陷者評價為「不良」。[Preparation and Evaluation of Liquid Crystal Cells for Evaluation of Liquid Crystal Alignment] Coat the liquid crystal alignment agent on a 30 mm × 40 mm ITO substrate by spin coating, dry it on a hot plate at 80°C for 2 minutes, and inspect the coating surface. After irradiating linearly polarized ultraviolet light with a wavelength of 254nm with an extinction ratio of 10:1 or more, bake it in a hot air circulation oven at 150~230℃ for 30 minutes to obtain a liquid crystal alignment film (polyimide film) with a film thickness of 100nm. substrate. Put the above two substrates into a set, with the film surface on the inside, sandwich a 6 μm spacer, print a sealant on the substrate, and laminate the other piece so that the alignment direction of the liquid crystal alignment film surface facing each other becomes 0°. After the substrate is formed, the sealant is hardened to create an empty unit cell. Liquid crystal MLC-3019 (manufactured by Merck) was injected into this empty unit cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell. The alignment state of the liquid crystal cell produced above was observed with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation). Those without alignment defects were evaluated as "good", and those with alignment defects were evaluated as "poor".
[FFS模式用液晶胞之製作] 製作具備有邊緣電場切換(Fringe Field Switching：FFS)模式液晶顯示元件之構成的液晶胞。首先，準備附電極的基板。基板為30mm×50mm的大小、厚度為0.7mm的玻璃基板。於基板上，形成有作為第1層之構成對向電極之具備固體狀之圖型的ITO電極。在第1層之對向電極上，形成有作為第2層之藉由CVD法成膜的SiN(氮化矽)膜。第2層之SiN膜的膜厚為500nm，作為層間絕緣膜產生功能。第2層之SiN膜上配置將作為第3層之ITO膜經圖型化所形成之梳齒狀畫素電極，形成第1畫素及第2畫素的2種畫素。各畫素之尺寸為長10mm、寬約5mm。此時，第1層之對向電極與第3層之畫素電極，係藉由第2層之SiN膜的作用而被電絕緣。[Preparation of liquid crystal cell for FFS mode] A liquid crystal cell having a structure of a fringe field switching (Fringe Field Switching: FFS) mode liquid crystal display element is produced. First, prepare a substrate with electrodes attached. The substrate is a glass substrate with a size of 30mm×50mm and a thickness of 0.7mm. On the substrate, an ITO electrode having a solid pattern and constituting the counter electrode is formed as the first layer. On the counter electrode of the first layer, a SiN (silicon nitride) film formed by a CVD method as a second layer is formed. The SiN film of the second layer has a film thickness of 500 nm and functions as an interlayer insulating film. The comb-shaped pixel electrode formed by patterning the ITO film as the third layer is disposed on the SiN film of the second layer to form two types of pixels, the first pixel and the second pixel. The size of each pixel is 10mm long and about 5mm wide. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the SiN film of the second layer.
第3層之畫素電極具有中央部分彎曲之“く”字形狀之電極元件多數排列而構成之梳齒狀的形狀。各電極元件之短邊方向的寬為3μm，電極元件間的間隔為6μm。形成各畫素的畫素電極為中央部分彎曲之「く字」形狀的電極元件多數排列所構成，因此各畫素的形狀非長方形狀，而是具備與電極元件相同，中央部分彎曲之類似粗體之「く字」的形狀。然後，各畫素以其中央之彎曲部分為界被上下分割，具有彎曲部分之上側的第1區域與下側的第2區域。The pixel electrode of the third layer has a comb-tooth shape composed of a plurality of electrode elements arranged in a "く" shape with a central portion curved. The width of each electrode element in the short side direction is 3 μm, and the interval between electrode elements is 6 μm. The pixel electrode forming each pixel is composed of a plurality of electrode elements arranged in a "く" shape with a central portion curved. Therefore, the shape of each pixel is not a rectangular shape, but has the same thickness as the electrode elements, with a central portion curved. The shape of the body's "く" character. Then, each pixel is divided up and down with a central curved portion as a boundary, and has a first region above the curved portion and a second region below the curved portion.
比較各畫素之第1區域與第2區域時，構成彼等之畫素電極之電極元件的形成方向為不同。亦即，以後述之液晶配向膜的摩擦方向作為基準時，畫素之第1區域中，以構成+10°的角度(順時針方向)來形成畫素電極的電極元件，畫素之第2區域中，以構成-10°的角度(順時針方向)來形成畫素電極的電極元件。亦即，各畫素之第1區域與第2區域中，藉由畫素電極與對向電極之間之電壓外加所誘發之液晶在基板面內的旋轉動作(平面轉換)的方向為彼此相反方向所構成。When comparing the first region and the second region of each pixel, the formation directions of the electrode elements constituting the pixel electrodes are different. That is, when the rubbing direction of the liquid crystal alignment film described below is used as a reference, in the first area of the pixel, the electrode element of the pixel electrode is formed at an angle of +10° (clockwise direction), and in the second area of the pixel, the electrode element is formed at an angle of +10° (clockwise). In the area, the electrode elements of the pixel electrodes are formed at an angle of -10° (clockwise direction). That is, in the first area and the second area of each pixel, the directions of the rotational movement (in-plane switching) of the liquid crystal in the substrate surface induced by the application of voltage between the pixel electrode and the counter electrode are opposite to each other. composed of directions.
接著，使用1.0μm之過濾器過濾液晶配向劑後，藉由旋轉塗佈法塗佈於已準備之上述附電極之基板與內面形成有ITO膜之具有高度4μm之柱狀間隔物的玻璃基板上。在80℃的加熱板上使乾燥2分鐘後，對塗膜面經由偏光板照射消光比10：1以上之直線偏光之波長254nm的紫外線後，以230℃之熱風循環式烤箱進行30分鐘燒成，形成膜厚100nm之塗膜。將上述2片基板為一組，在基板上印刷密封劑，以使液晶配向膜面相向的配向方向成為0°的方式來貼合另1片基板後，使密封劑硬化而製作空晶胞。藉由減壓注入法，將液晶MLC-3019(Merck公司製)注入於此空晶胞，並密封注入口，得到FFS驅動液晶胞。然後，將製得之液晶胞於110℃下加熱1小時，放置一晩後，使用於各評價。Next, after filtering the liquid crystal alignment agent with a 1.0 μm filter, the liquid crystal alignment agent is coated by spin coating on the prepared substrate with electrodes and a glass substrate with columnar spacers with a height of 4 μm and an ITO film formed on the inner surface. superior. After drying on a hot plate at 80°C for 2 minutes, the coating surface was irradiated with linearly polarized ultraviolet light with a wavelength of 254nm with an extinction ratio of 10:1 or more through a polarizing plate, and then baked in a hot air circulation oven at 230°C for 30 minutes. , forming a coating with a film thickness of 100nm. The above two substrates are combined into a set, a sealant is printed on the substrate, and the other substrate is bonded so that the alignment direction of the liquid crystal alignment film surfaces facing each other becomes 0°, and then the sealant is cured to create an empty unit cell. Liquid crystal MLC-3019 (manufactured by Merck) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS driven liquid crystal cell. Then, the prepared liquid crystal cell was heated at 110° C. for 1 hour and left overnight before being used for each evaluation.
[長期交流驅動所造成之殘影評價] 準備與使用於上述殘影評價之液晶胞同樣構造的液晶胞。使用此液晶胞，在60℃之恆溫環境下，以頻率60Hz、±5V的交流電壓施加120小時。然後，使液晶胞之畫素電極與對向電極之間形成短路的狀態，該狀態下室溫放置一日。放置後，將液晶胞設置於偏光軸以正交配置之2片偏光板間，以電壓無外加的狀態點亮背光，調整液晶胞之配置角度，使透過光的亮度成為最小。然後，由第1畫素之第2區域成為最暗的角度至第1區域成為最暗的角度為止，旋轉液晶胞時之旋轉角度作為角度Δ來算出。第2畫素也同樣，比較第2區域與第1區域，算出同樣的角度Δ。[Evaluation of image retention caused by long-term AC driving] Prepare a liquid crystal cell with the same structure as the liquid crystal cell used for the above image retention evaluation. This liquid crystal cell was used and an AC voltage of ±5V with a frequency of 60Hz was applied for 120 hours in a constant temperature environment of 60°C. Then, a short-circuit state was formed between the pixel electrode and the counter electrode of the liquid crystal cell, and the liquid crystal cell was left at room temperature for one day. After placement, the liquid crystal cell is placed between two polarizing plates whose polarization axes are arranged orthogonally. The backlight is lit with no external voltage, and the arrangement angle of the liquid crystal cell is adjusted to minimize the brightness of the transmitted light. Then, the rotation angle when the liquid crystal cell is rotated from the angle at which the second area of the first pixel becomes the darkest to the angle at which the first area becomes the darkest is calculated as the angle Δ. The same applies to the second pixel. The second area and the first area are compared, and the same angle Δ is calculated.
[液晶胞之亮點評價(對比)] 上述製作的液晶胞進行亮點評價。液晶胞之亮點評價係以偏光顯微鏡(ECLIPSE E600WPOL)(Nikon公司製)觀察液晶胞。具體而言，將液晶胞以直交偏光設置，並以倍率為5倍之偏光顯微鏡觀察液晶胞，計算經確認之亮點數，亮點數未達10個評價為「良好」，亮點數為10個以上評價為「不良」。[Evaluation of bright spots of liquid crystal cells (comparison)] The liquid crystal cells produced above were evaluated for bright spots. The highlight of the liquid crystal cell was evaluated by observing the liquid crystal cell using a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation). Specifically, set the liquid crystal cell with cross-polarized light, observe the liquid crystal cell with a polarizing microscope with a magnification of 5 times, and calculate the number of confirmed bright spots. If the number of bright spots does not reach 10, it will be evaluated as "good", and if the number of bright spots exceeds 10, it will be evaluated as "good". The rating is "Bad".
＜合成例1＞ 在附攪拌裝置及附氮導入管之100ml四口燒瓶中，秤取DA-1(4.76g，19.5mmol)、DA-3(4.44g，13.0mmol)、DA-4(1.41g，13.0mmol)、DA-5(6.25g，19.5mmol)，添加NMP 122g，邊送入氮邊攪拌使溶解。邊攪拌此二胺溶液，邊添加CA-1(11.4g，50.6mmol)、CA-2(2.44g，9.75 mmol)，再添加NMP 52.1g，使固體成分濃度成為15質量%，於40℃下攪拌24小時，得到聚醯胺酸溶液(A)(黏度：549mPa･s)。聚醯胺酸之分子量為Mn=11500、Mw=27600。<Synthesis Example 1> In a 100 ml four-necked flask with a stirring device and a nitrogen introduction tube, weigh DA-1 (4.76g, 19.5mmol), DA-3 (4.44g, 13.0mmol), and DA-4 (1.41 g, 13.0 mmol), DA-5 (6.25 g, 19.5 mmol), add 122 g of NMP, and stir to dissolve while adding nitrogen. While stirring this diamine solution, add CA-1 (11.4g, 50.6mmol), CA-2 (2.44g, 9.75mmol), and then add 52.1g of NMP so that the solid content concentration becomes 15% by mass, at 40°C. Stir for 24 hours to obtain a polyamide solution (A) (viscosity: 549 mPa･s). The molecular weight of polyamide is Mn=11500, Mw=27600.
＜合成例2~20＞ 使用下述表1-1所示之二胺成分、四羧酸成分，分別以表1-2所示之NMP量、反應溫度、固體成分濃度，藉由與合成例1同樣實施，得到聚醯胺酸溶液(B)~(T)。又，所得之聚醯胺酸之黏度、及分子量，如下述表1-2所示。<Synthetic Examples 2 to 20> Using the diamine component and tetracarboxylic acid component shown in the following Table 1-1, the NMP amount, reaction temperature, and solid content concentration shown in Table 1-2 were used. 1 is carried out in the same manner to obtain polyamide solutions (B) ~ (T). Moreover, the viscosity and molecular weight of the obtained polyamic acid are shown in Table 1-2 below.
＜合成例21＞ 在附攪拌裝置及附氮導入管之100ml四口燒瓶中，秤取製得之聚醯胺酸溶液(A)67.0g，添加NMP 33.5g，攪拌30分鐘。於所得之聚醯胺酸溶液中，添加乙酸酐5.80g、吡啶1.50g，於55℃下加熱3小時，進行化學醯亞胺化。將所得之反應液，邊攪拌邊投入於427ml的甲醇中，析出的沉澱物經過濾取得，接著，以427ml的甲醇洗淨3次。所得之樹脂粉末於60℃下乾燥12小時，得到聚醯亞胺樹脂粉末(A)。此聚醯亞胺樹脂粉末的醯亞胺化率為62%，Mn=12200、Mw=30600。<Synthesis Example 21> In a 100 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, weigh 67.0g of the prepared polyamide solution (A), add 33.5g of NMP, and stir for 30 minutes. To the obtained polyamic acid solution, 5.80 g of acetic anhydride and 1.50 g of pyridine were added, and the mixture was heated at 55° C. for 3 hours to perform chemical imidization. The obtained reaction liquid was added to 427 ml of methanol while stirring, and the precipitated precipitate was collected by filtration, and then washed three times with 427 ml of methanol. The obtained resin powder was dried at 60°C for 12 hours to obtain polyimide resin powder (A). The imidization rate of this polyimide resin powder is 62%, Mn=12200, Mw=30600.
＜合成例22~39＞ 除了使用下述表2所示之聚醯胺酸溶液、NMP、乙酸酐、吡啶、及甲醇外，與合成例21同樣實施，得到下述表2所示之聚醯亞胺樹脂粉末(B)~(S)。<Synthesis Examples 22 to 39> Except using the polyamide solution, NMP, acetic anhydride, pyridine, and methanol shown in Table 2 below, the same procedure as Synthesis Example 21 was carried out to obtain the polyamide shown in Table 2 below. Imine resin powder (B)~(S).
＜實施例1＞ 在100ml三角燒瓶中，秤取合成例21所得之聚醯亞胺樹脂粉末(A)1.80g，添加NMP 13.2g使固體成分濃度成為15%，於70℃下攪拌24小時使溶解，得到聚醯亞胺溶液(A)。此聚醯亞胺溶液中，添加NMP 2.90g、GBL 9.00g、BCS 6.00g，室溫下攪拌3小時，得到液晶配向劑(1)。此液晶配向劑未發現混濁或析出等之異常，確認為均勻的溶液。<Example 1> In a 100 ml Erlenmeyer flask, 1.80 g of the polyimide resin powder (A) obtained in Synthesis Example 21 was weighed, 13.2 g of NMP was added so that the solid content concentration became 15%, and the mixture was stirred at 70°C for 24 hours. Dissolve to obtain polyimide solution (A). To this polyimide solution, add 2.90g of NMP, 9.00g of GBL, and 6.00g of BCS, and stir at room temperature for 3 hours to obtain a liquid crystal alignment agent (1). No abnormalities such as turbidity or precipitation were found in this liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
＜實施例2~13、比較例1~2＞ 除了使用聚醯亞胺樹脂粉末(B)~(O)取代聚醯亞胺樹脂粉末(A)外，與實施例1同樣實施，而得到聚醯亞胺溶液(B)~(O)，使用此聚醯亞胺溶液(B)~(O)，得到液晶配向劑(2)~(15)。<Examples 2 to 13, Comparative Examples 1 to 2> Except using polyimide resin powder (B) to (O) instead of polyimide resin powder (A), the same procedure as in Example 1 was carried out to obtain a polyimide resin powder. Polyamide imine solutions (B) ~ (O) are used to obtain liquid crystal alignment agents (2) ~ (15).
＜實施例14＞ 在100ml三角燒瓶中，秤取與實施例1同樣得到之聚醯亞胺溶液(A)4.80g、及合成例20所得之聚醯胺酸溶液(T) 7.20g，添加NMP 3.00g、GBL 9.00g、BCS 6.00g，室溫下攪拌3小時，得到液晶配向劑(16)。此液晶配向劑未發現混濁或析出等之異常，確認為均勻的溶液。<Example 14> In a 100 ml Erlenmeyer flask, 4.80 g of the polyimide solution (A) obtained in the same manner as Example 1 and 7.20 g of the polyamide acid solution (T) obtained in Synthesis Example 20 were weighed, and NMP was added. 3.00g, GBL 9.00g, BCS 6.00g, and stirred at room temperature for 3 hours to obtain liquid crystal alignment agent (16). No abnormalities such as turbidity or precipitation were found in this liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
＜比較例3＞ 在100ml三角燒瓶中，秤取合成例34所得之聚醯亞胺樹脂粉末(N)1.80g，添加NMP 13.2g使固體成分濃度成為15%，於70℃下攪拌24小時使溶解，得到聚醯亞胺溶液(N)。在100ml三角燒瓶中，秤取此聚醯亞胺溶液4.80g及合成例20所得之聚醯胺酸溶液(T)7.20g，添加NMP 3.00 g、GBL 9.00g、BCS 6.00g，室溫下攪拌3小時，得到液晶配向劑(17)。此液晶配向劑未發現混濁或析出等之異常，確認為均勻的溶液。<Comparative Example 3> In a 100 ml Erlenmeyer flask, 1.80 g of the polyimide resin powder (N) obtained in Synthesis Example 34 was weighed, 13.2 g of NMP was added so that the solid content concentration became 15%, and the mixture was stirred at 70°C for 24 hours. Dissolve to obtain polyimide solution (N). In a 100 ml Erlenmeyer flask, weigh 4.80 g of the polyimide solution and 7.20 g of the polyamide acid solution (T) obtained in Synthesis Example 20, add 3.00 g of NMP, 9.00 g of GBL, and 6.00 g of BCS, and stir at room temperature. After 3 hours, the liquid crystal alignment agent (17) was obtained. No abnormalities such as turbidity or precipitation were found in this liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
＜比較例4＞ 除了使用聚醯亞胺樹脂粉末(O)取代聚醯亞胺樹脂粉末(N)外，與實施例14同樣操作，得到聚醯亞胺溶液(O)，使用此聚醯亞胺溶液(O)得到液晶配向劑(18)。此液晶配向劑未發現混濁或析出等之異常，確認為均勻的溶液。<Comparative Example 4> Except that polyimide resin powder (O) was used instead of polyimide resin powder (N), the same operation was carried out as in Example 14 to obtain a polyimide solution (O). This polyimide solution (O) was obtained. Amine solution (O) obtains liquid crystal alignment agent (18). No abnormalities such as turbidity or precipitation were found in this liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
＜實施例15＞ 除了使用聚醯亞胺樹脂粉末(P)取代聚醯亞胺樹脂粉末(N)外，與實施例14同樣操作，得到聚醯亞胺溶液(P)，使用此聚醯亞胺溶液(P)得到液晶配向劑(19)。此液晶配向劑未發現混濁或析出等之異常，確認為均勻的溶液。<Example 15> Except that polyimide resin powder (P) was used instead of polyimide resin powder (N), the same operation was performed as in Example 14 to obtain a polyimide solution (P). This polyimide solution (P) was obtained. The amine solution (P) is used to obtain the liquid crystal alignment agent (19). No abnormalities such as turbidity or precipitation were found in this liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
＜實施例16＞ 除了使用聚醯亞胺樹脂粉末(Q)取代聚醯亞胺樹脂粉末(N)外，與實施例14同樣操作，得到聚醯亞胺溶液(Q)，使用此聚醯亞胺溶液(Q)得到液晶配向劑(20)。此液晶配向劑未發現混濁或析出等之異常，確認為均勻的溶液。<Example 16> Except that polyimide resin powder (Q) was used instead of polyimide resin powder (N), the same operation was carried out as in Example 14 to obtain a polyimide solution (Q). This polyimide solution (Q) was obtained. Amine solution (Q) obtains liquid crystal alignment agent (20). No abnormalities such as turbidity or precipitation were found in this liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
＜實施例17＞ 將實施例1所得之液晶配向劑(1)以1.0μm的過濾器過濾後，藉由旋轉塗佈法將液晶配向劑塗佈於30mm×40mm之ITO基板上，在80℃之加熱板上使乾燥2分鐘後，對塗膜面經由偏光板照射消光比26：1之直線偏光之波長254nm的紫外線0.35J/cm2 後，以230℃之熱風循環式烤箱進行30分鐘燒成，得到附液晶配向膜之基板。將所得之上述2片基板為一組，在基板上印刷密封劑，以使液晶配向膜面相向的配向方向成為0°的方式來貼合另1片基板後，使密封劑硬化而製作空晶胞。藉由減壓注入法，將液晶MLC-3019(Merck公司製)注入於此空晶胞，並密封注入口，得到液晶配向性液晶胞。確認液晶之配向狀態的結果，無配向缺陷，且良好。<Example 17> After filtering the liquid crystal alignment agent (1) obtained in Example 1 with a 1.0 μm filter, the liquid crystal alignment agent was coated on a 30mm×40mm ITO substrate by a spin coating method, and the liquid crystal alignment agent was heated at 80°C. After drying on a hot plate for 2 minutes, irradiate the coating surface with 0.35J/cm 2 of linearly polarized ultraviolet light with an extinction ratio of 26:1 and a wavelength of 254nm through a polarizing plate, then bake it in a hot air circulation oven at 230°C for 30 minutes. to obtain a substrate with a liquid crystal alignment film. The above-mentioned two substrates were combined into a set, a sealant was printed on the substrate, and the other substrate was bonded so that the alignment direction of the liquid crystal alignment film surfaces facing each other became 0°, and then the sealant was cured to produce a hollow crystal. cell. Liquid crystal MLC-3019 (manufactured by Merck Corporation) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal alignment liquid crystal cell. The result of confirming the alignment state of the liquid crystal showed that there were no alignment defects and it was in good condition.
＜實施例18~32、比較例5~8＞ 除了分別使用表3所示之液晶配向劑取代液晶配向劑(1)，及紫外線之照射量、及燒成溫度設為如表4所示者外，使用與實施例17同樣的方法製作液晶配向性評價用液晶胞。各自之液晶配向性之評價結果如表4所示。<Examples 18 to 32, Comparative Examples 5 to 8> In addition to using the liquid crystal alignment agent shown in Table 3 instead of the liquid crystal alignment agent (1), the irradiation amount of ultraviolet rays and the firing temperature were set to those shown in Table 4 Except for this, the same method as in Example 17 was used to prepare a liquid crystal cell for liquid crystal alignment evaluation. The evaluation results of respective liquid crystal alignment properties are shown in Table 4.
＜實施例33＞ 將上述液晶配向劑(1)以1.0μm的過濾器過濾後，藉由旋轉塗佈法塗佈於已準備之上述附電極基板與內面形成ITO膜之具有高度4μm之柱狀間隔物的玻璃基板上。在80℃之加熱板上使乾燥2分鐘後，對塗膜面經由偏光板照射消光比26：1之直線偏光之波長254nm的紫外線0.35 J/cm2 後，以230℃之熱風循環式烤箱進行30分鐘燒成，得到膜厚100nm之附液晶配向膜的基板。將所得之上述2片基板為一組，在基板上印刷密封劑，以使液晶配向膜面相向的配向方向成為0°的方式來貼合另1片基板後，使密封劑硬化而製作空晶胞。藉由減壓注入法，將液晶MLC-3019(Merck公司製)注入於此空晶胞，並密封注入口，得到FFS驅動液晶胞。然後，將所得之液晶胞以110℃加熱1小時，並放置一晩後，實施長期交流驅動所產生之殘影評價。長期交流驅動後之此液晶胞之角度Δ的值為0.05。又，觀察晶胞中之亮點的結果，亮點數未達10個，評價為良好。<Example 33> After filtering the above-mentioned liquid crystal alignment agent (1) with a 1.0 μm filter, the above-mentioned electrode-attached substrate and the pillars with a height of 4 μm with an ITO film formed on the inner surface were coated by spin coating. spacers on the glass substrate. After drying on a hot plate at 80°C for 2 minutes, the coating surface was irradiated with linearly polarized ultraviolet rays of 0.35 J/cm 2 with an extinction ratio of 26:1 and a wavelength of 254nm through a polarizing plate, and then dried in a hot air circulation oven at 230°C. After firing for 30 minutes, a substrate with a liquid crystal alignment film with a film thickness of 100 nm was obtained. The above-mentioned two substrates were combined into a set, a sealant was printed on the substrate, and the other substrate was bonded so that the alignment direction of the liquid crystal alignment film surfaces facing each other became 0°, and then the sealant was cured to produce a hollow crystal. cell. Liquid crystal MLC-3019 (manufactured by Merck) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS driven liquid crystal cell. Then, the obtained liquid crystal cell was heated at 110° C. for 1 hour and left overnight, and then the image sticking caused by long-term AC driving was evaluated. The value of the angle Δ of this liquid crystal cell after long-term AC driving is 0.05. Furthermore, when the bright spots in the unit cell were observed, the number of bright spots did not reach 10, so the evaluation was good.
＜實施例34~42、比較例9~12＞ 除了分別使用表5所示之液晶配向劑取代液晶配向劑(1)，及紫外線之照射量設為如表5所示者外，使用與實施例33同樣的方法製作FFS驅動液晶胞，實施評價長期交流驅動所造成之殘影。各自之長期交流驅動後之此液晶胞之角度Δ之值、及亮點評價結果如表5所示。<Examples 34 to 42, Comparative Examples 9 to 12> In addition to using the liquid crystal alignment agent shown in Table 5 instead of the liquid crystal alignment agent (1), and setting the amount of ultraviolet irradiation to that shown in Table 5, the use and implementation Example 33: Use the same method to prepare an FFS driven liquid crystal cell, and evaluate the image retention caused by long-term AC driving. The value of the angle Δ of the liquid crystal cell after long-term AC driving and the evaluation results of the bright spots are shown in Table 5.
[產業上之可利用性] [Industrial availability]
藉由本發明之製造方法所得之液晶配向膜，可以少的步驟數製造，故可提高液晶顯示元件的良率，可更有效率製造液晶顯示元件。又，藉由使用以本發明之製造方法所製得之液晶配向膜，可抑制因IPS驅動方式或FFS驅動方式之液晶顯示元件中發生之長期交流驅動所造成之殘影。此外，本發明之製造方法所得之液晶配向膜，因聚醯亞胺之主鏈被切斷而生成之低分子量成分之發生量較少，故可抑制配向不良或亮點之發生，可製造更優品質的液晶顯示元件。因此，具備藉由本發明之製造方法所製得之液晶配向膜的液晶顯示元件成為殘影特性或信賴性優異者，可適用於大畫面，且高精細之液晶電視或中小型之汽車導航系統或智慧型手機等。The liquid crystal alignment film obtained by the manufacturing method of the present invention can be manufactured in a small number of steps, so the yield of the liquid crystal display element can be improved and the liquid crystal display element can be manufactured more efficiently. In addition, by using the liquid crystal alignment film produced by the manufacturing method of the present invention, it is possible to suppress image sticking caused by long-term AC driving that occurs in IPS driving or FFS driving liquid crystal display elements. In addition, the liquid crystal alignment film obtained by the manufacturing method of the present invention has a smaller amount of low molecular weight components generated by cutting the main chain of the polyimide, so the occurrence of poor alignment or bright spots can be suppressed, and better quality can be produced. Quality LCD components. Therefore, the liquid crystal display element equipped with the liquid crystal alignment film produced by the manufacturing method of the present invention has excellent image sticking characteristics or reliability, and can be applied to large-screen, high-definition LCD televisions or small and medium-sized car navigation systems or Smartphones, etc.
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