TWI766889B - Diamine, polymer, liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents
Diamine, polymer, liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element Download PDFInfo
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Abstract
本發明係一種二胺,其係具有下述式[1]所表示之構造, (式[1]中,Y1 及Y2 係分別獨立為單鍵、-O-、-S-、-COO-或-OCO-,R1 及R2 係分別獨立為-H、-OH、=O或一價的有機基,R3 及R4 係分別獨立為碳原子數1~3的伸烷基,又,苯環的任意的氫原子可被一價的有機基所取代)。The present invention relates to a diamine having a structure represented by the following formula [1], (In formula [1], Y 1 and Y 2 are each independently a single bond, -O-, -S-, -COO- or -OCO-, and R 1 and R 2 are each independently -H, -OH, =O or a monovalent organic group, R 3 and R 4 are each independently an alkylene group having 1 to 3 carbon atoms, and any hydrogen atom of the benzene ring may be substituted by a monovalent organic group).
Description
本發明為關於新穎的二胺、液晶顯示元件中使用的聚合物、液晶配向劑及液晶配向膜、以及液晶顯示元件。 The present invention relates to a novel diamine, a polymer used in a liquid crystal display element, a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element.
現今,液晶顯示元件被廣泛地使用作為個人電腦或手機、電視顯影機等的顯示部。液晶顯示元件係例如具備有:挾持在元件基板與彩色濾光片基板之間的液晶層、用於對液晶層外加電場的像素電極及共通電極、用於控制液晶層的液晶分子的配向性的液晶配向膜、用於切換對像素電極供給的電信號的薄膜電晶體(TFT)等。該等之中,液晶配向膜為藉由將由聚醯亞胺前驅物的聚醯胺酸(亦稱為「聚醯胺酸」)、或該醯亞胺化物的聚醯亞胺的溶液所成之聚醯亞胺系的液晶配向劑,塗佈至基板上從而成膜來製作。 Today, liquid crystal display elements are widely used as display parts of personal computers, mobile phones, television developing machines, and the like. The liquid crystal display element includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode for applying an electric field to the liquid crystal layer, and a device for controlling the alignment of liquid crystal molecules in the liquid crystal layer. Liquid crystal alignment films, thin film transistors (TFTs) for switching electrical signals supplied to pixel electrodes, and the like. Among them, the liquid crystal alignment film is formed by adding a solution of polyimide (also referred to as "polyimide"), which is a polyimide precursor, or polyimide of the imide compound. The polyimide-based liquid crystal aligning agent is coated on a substrate to form a film.
近年,隨著液晶顯示元件的高性能化、大面積化、顯示裝置的省電力化等之進展,除此之外,為了能在各種的環境下來使用,對於液晶配向膜所要求的特性也 變得嚴格。因此,藉由聚醯胺酸或聚醯亞胺的構造的變更、加入不同特性的聚醯胺酸或聚醯亞胺的摻合物或添加劑等的各種手法,除了改善液晶配向性或電特性等以外,亦進行著預傾角的控制等。 In recent years, with the progress of high performance and large area of liquid crystal display elements, power saving of display devices, etc., in addition to these, in order to be used in various environments, the characteristics required for liquid crystal alignment films are also increasing. become strict. Therefore, by changing the structure of polyamide or polyimide, adding blends or additives of polyamide or polyimide with different characteristics, etc., in addition to improving liquid crystal alignment or electrical properties In addition to the above, the control of the pretilt angle and the like are also performed.
作為使液晶配向膜的特性提升之手法之一例,提案著適用一種聚醯胺酸的原料的具有新穎構造的二胺。例如專利文獻1中揭示著含有具有新穎構造之二胺與脂肪族四羧酸衍生物之液晶配向劑,藉由使用該液晶配向劑,可提供電壓保持率為優異、且能夠減低電荷蓄積的液晶顯示元件。 As an example of the method of improving the characteristics of a liquid crystal alignment film, a diamine having a novel structure to which a raw material of polyamic acid is applied is proposed. For example, Patent Document 1 discloses a liquid crystal aligning agent containing a diamine having a novel structure and an aliphatic tetracarboxylic acid derivative, and by using the liquid crystal aligning agent, a liquid crystal that is excellent in voltage retention and can reduce charge accumulation can be provided display element.
然而,隨著液晶顯示元件的高性能化,對液晶配向膜所要求的特性也變得嚴格,僅利用以往的技術將難以滿足全部的要求特性。 However, with the improvement of the performance of liquid crystal display elements, the properties required for the liquid crystal alignment film are also becoming stricter, and it is difficult to satisfy all the required properties only by the conventional technology.
[專利文獻1]國際公開第2010/053128號 [Patent Document 1] International Publication No. 2010/053128
本發明係有鑑於如此般的情形,其目的在於提供用於實現液晶顯示元件的特性之提升的新穎二胺、使用於液晶顯示元件之聚合物、液晶配向劑及液晶配向膜、以及液晶顯示元件。 The present invention has been made in view of such circumstances, and an object of the present invention is to provide a novel diamine for realizing the improvement of the characteristics of a liquid crystal display element, a polymer for use in a liquid crystal display element, a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element .
本發明人經深入研究之結果發現,將藉由使用特定的二胺所得之聚合物適用於液晶顯示元件時,特別是對於減低驅動初期的閃爍(flicker/明滅不定)而言極為有效,進而完成本發明。尚,後述之本發明之二胺係文獻中未記載的新穎化合物。 As a result of intensive research by the present inventors, it was found that, when a polymer obtained by using a specific diamine is applied to a liquid crystal display element, it is extremely effective in reducing flicker (flicker/blinking) at the initial stage of driving. this invention. Furthermore, the diamine of the present invention described later is a novel compound not described in the literature.
達成上述目的之本發明之二胺,其特徵係如下述式[1]所表示。 The diamine of the present invention which achieves the above object is characterized by the following formula [1].
(式[1]中,Y1及Y2係分別獨立為單鍵、-O-、-S-、-COO-或-OCO-,R1及R2係分別獨立為-H、-OH、=O或一價的有機基,R3及R4係分別獨立為碳原子數1~3的伸烷基,又,苯環的任意的氫原子可被一價的有機基所取代)。 (In formula [1], Y 1 and Y 2 are each independently a single bond, -O-, -S-, -COO- or -OCO-, and R 1 and R 2 are each independently -H, -OH, =O or a monovalent organic group, R 3 and R 4 are each independently an alkylene group having 1 to 3 carbon atoms, and any hydrogen atom of the benzene ring may be substituted by a monovalent organic group).
達成上述目的之本發明之聚合物,其特徵係由包含具有下述式[2]所表示之構造之二胺之二胺成分所得到。 The polymer of this invention which achieves the said objective is obtained from the diamine component containing the diamine which has the structure represented by following formula [2], It is characterized by the above-mentioned.
(式[2]中,Y1係單鍵、-O-、-S-、-COO-或-OCO-,R1及R2係分別獨立為-H、-OH、=O或一價的有機基,R3係碳原子數1~3的伸烷基,*係表示與其他的基鍵結之部位,又,苯環的任意的氫原子可被一價的有機基所取代)。 (In formula [2], Y 1 is a single bond, -O-, -S-, -COO- or -OCO-, and R 1 and R 2 are independently -H, -OH, =O or monovalent, respectively. In the organic group, R 3 represents an alkylene group having 1 to 3 carbon atoms, * represents a bonding site with other groups, and any hydrogen atom of the benzene ring may be substituted by a monovalent organic group).
又,上述聚合物係以由包含具有下述式[3]所表示之構造之二胺之二胺成分所得到為較佳。 Moreover, it is preferable that the said polymer is obtained from the diamine component containing the diamine which has a structure represented by following formula [3].
(式[3]中,Y1及Y2係分別獨立為單鍵、-O-、-S-、-COO-或-OCO-,R1及R2係分別獨立為-H、-OH、=O或一價的有機基,R3及R4係分別獨立為碳原子數1~3的伸烷基,*係表示與其他的基鍵結之部位,又,苯環的任意的氫原子可被一價的有機基所取代)。 (In formula [3], Y 1 and Y 2 are each independently a single bond, -O-, -S-, -COO- or -OCO-, and R 1 and R 2 are each independently -H, -OH, =O or a monovalent organic group, R 3 and R 4 are each independently an alkylene group having 1 to 3 carbon atoms, * represents a site where other groups are bonded, and an arbitrary hydrogen atom of a benzene ring may be substituted by a monovalent organic group).
又,上述聚合物係以選自包含下述式[4]所表示之構造單位之聚醯亞胺前驅物及該醯亞胺化合物的聚醯 亞胺中之至少1種為較佳。 In addition, the above-mentioned polymer is selected from a polyimide precursor including a structural unit represented by the following formula [4] and a polyimide compound of the polyimide compound. At least one of the imines is preferred.
(式[4]中,X1係源自四羧酸衍生物之四價的有機基,W1係源自具有式[2]或式[3]所表示之構造之二胺之二價的有機基,R5及R6係表示氫原子或碳原子數1~5的烷基,A1及A2係分別獨立表示氫原子、碳原子數1~5的烷基、碳原子數2~5的烯基或碳原子數2~5的炔基)。 (In formula [4], X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative, and W 1 is a divalent organic group derived from a diamine having a structure represented by formula [2] or formula [3] Organic group, R 5 and R 6 represent a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and A 1 and A 2 independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, and 2 to 2 carbon atoms. 5 alkenyl or alkynyl with 2 to 5 carbon atoms).
達成上述目的之本發明之液晶配向劑,其特徵係含有聚合物與有機溶劑。 The liquid crystal aligning agent of the present invention which achieves the above object is characterized by containing a polymer and an organic solvent.
達成上述目的之本發明之液晶配向膜,其特徵係由上述液晶配向劑所得到。 The liquid crystal alignment film of the present invention which achieves the above object is characterized by being obtained from the above-mentioned liquid crystal alignment agent.
達成上述目的之本發明之液晶顯示元件,其特徵係具備上述液晶配向膜。 The liquid crystal display element of this invention which achieves the said objective is equipped with the said liquid crystal alignment film, It is characterized by the above-mentioned.
依據本發明係可提供用於實現液晶顯示元件的特性之提升之新穎二胺、使用於液晶顯示元件之聚合物、液晶配向劑及液晶配向膜、以及液晶顯示元件。 According to the present invention, novel diamines for realizing the improvement of the characteristics of liquid crystal display elements, polymers for liquid crystal display elements, liquid crystal alignment agents and liquid crystal alignment films, and liquid crystal display elements can be provided.
以下,更詳細地來說明本發明。 Hereinafter, the present invention will be described in more detail.
本發明之二胺係下述式[1]所表示者。 The diamine of the present invention is represented by the following formula [1].
(式[1]中,Y1及Y2係分別獨立為單鍵、-O-、-S-、-COO-或-OCO-,R1及R2係分別獨立為-H、-OH、=O或一價的有機基,R3及R4係分別獨立為碳原子數1~3的伸烷基,又,苯環的任意的氫原子可被一價的有機基所取代)。 (In formula [1], Y 1 and Y 2 are each independently a single bond, -O-, -S-, -COO- or -OCO-, and R 1 and R 2 are each independently -H, -OH, =O or a monovalent organic group, R 3 and R 4 are each independently an alkylene group having 1 to 3 carbon atoms, and any hydrogen atom of the benzene ring may be substituted by a monovalent organic group).
式[1]中,作為一價的有機基,可舉出:烴基;羥基、羧基、包含羥基、硫醇基或羧基的烴基;藉由醚鍵、酯鍵、醯胺鍵等的鍵結基所連結的烴基;含有矽原子的烴基;鹵化烴基;胺基;胺基被t-丁氧基羰基等的胺甲酸酯系的保護基所保護的惰性基等。尚,烴基可以是直鏈、支鏈及環狀鏈中任一種,又可以是飽和烴,亦可以是不飽和烴。又,烴基的氫原子的一部分可被羧基、羥基、 硫醇基、矽原子、鹵素原子等所取代,亦可藉由醚鍵、酯鍵、醯胺鍵等的鍵結基來連結。 In formula [1], examples of the monovalent organic group include: a hydrocarbon group; a hydroxyl group, a carboxyl group, a hydrocarbon group including a hydroxyl group, a thiol group, or a carboxyl group; a bonding group via an ether bond, an ester bond, an amide bond, or the like A hydrocarbon group to be linked; a hydrocarbon group containing a silicon atom; a halogenated hydrocarbon group; an amine group; Furthermore, the hydrocarbon group may be any of straight chain, branched chain and cyclic chain, and may be saturated hydrocarbon or unsaturated hydrocarbon. Also, a part of the hydrogen atoms of the hydrocarbon group may be replaced by a carboxyl group, a hydroxyl group, A thiol group, a silicon atom, a halogen atom, etc. are substituted, and it is also possible to connect by a bonding group such as an ether bond, an ester bond, and an amide bond.
又,碳原子數1~3的伸烷基可以是直鏈、支鏈及環狀鏈中任一種。具體而言,可舉出亞甲基、伸乙基、n-伸丙基、異伸丙基、伸環丙基、1-甲基-伸環丙基、2-甲基-伸環丙基、1,1-二甲基-n-伸丙基、1,2-二甲基-n-伸丙基、2,2-二甲基-n-伸丙基、1-乙基-n-伸丙基、1,2-二甲基-伸環丙基、2,3-二甲基-伸環丙基、1-乙基-伸環丙基、2-乙基-伸環丙基、1,1,2-三甲基-n-伸丙基、1,2,2-三甲基-n-伸丙基、1-乙基-1-甲基-n-伸丙基、1-乙基-2-甲基-n-伸丙基、2-n-丙基-伸環丙基、1-異丙基-伸環丙基、2-異丙基-伸環丙基、1,2,2-三甲基-伸環丙基、1,2,3-三甲基-伸環丙基、2,2,3-三甲基-伸環丙基、1-乙基-2-甲基-伸環丙基、2-乙基-1-甲基-伸環丙基、2-乙基-2-甲基-伸環丙基及2-乙基-3-甲基-伸環丙基等。 In addition, the alkylene group having 1 to 3 carbon atoms may be any of straight chain, branched chain and cyclic chain. Specifically, methylene group, ethylidene group, n-propylidene group, isopropylidene group, cyclopropylene group, 1-methyl-cyclopropylene group, 2-methyl-cyclopropylene group can be mentioned. , 1,1-dimethyl-n-propylidene, 1,2-dimethyl-n-propylidene, 2,2-dimethyl-n-propylidene, 1-ethyl-n- Propylene, 1,2-Dimethyl-cyclo-extended propyl, 2,3-dimethyl-cyclo-extended propyl, 1-ethyl-cyclo-extended propyl, 2-ethyl-cyclo-extended propyl, 1,1,2-Trimethyl-n-propylidene, 1,2,2-trimethyl-n-propylidene, 1-ethyl-1-methyl-n-propylidene, 1- Ethyl-2-methyl-n-extended propyl, 2-n-propyl-cycloextended propyl, 1-isopropyl-cycloextended propyl, 2-isopropyl-cycloextended propyl, 1, 2,2-Trimethyl-cycloextended propyl, 1,2,3-trimethyl-cycloextended propyl, 2,2,3-trimethyl-cycloextended propyl, 1-ethyl-2- Methyl-cycloextended propyl, 2-ethyl-1-methyl-cycloextended propyl, 2-ethyl-2-methyl-cycloextended propyl and 2-ethyl-3-methyl-cycloextended Propyl etc.
尚,一價的有機基或碳原子數1~3的伸烷基係可因應用途來做各種選擇。 Furthermore, a monovalent organic group or an alkylene group with 1 to 3 carbon atoms can be selected in various ways according to the application.
作為式[1]所表示之二胺之具體例,可示例下述式[5-1]~式[5-13]所表示之二胺,但並不被限定於該等中。 As a specific example of the diamine represented by formula [1], the diamine represented by following formula [5-1] - formula [5-13] can be illustrated, but it is not limited to these.
尚,式[5-3]中,Boc係表示下述所示之基(tert-丁氧基羰基)。 Furthermore, in the formula [5-3], Boc represents a group (tert-butoxycarbonyl group) shown below.
接下來,對於本發明之二胺之主要合成方法來進行說 明。尚,以下所說明之方法為合成例,但並不被限定於此。 Next, the main synthesis method of the diamine of the present invention will be described Bright. Incidentally, the method described below is a synthesis example, but is not limited to this.
本發明之二胺係如下述反應式所表示般,藉由還原二硝基化合物來將硝基變換成胺基從而可得到。尚,作為下述反應式中所記載的例子,係苯環及飽和烴部的氫原子未被氟原子等的鹵素原子或胺基以外的一價的有機基所取代的二胺。 The diamine of the present invention can be obtained by converting a nitro group into an amine group by reducing a dinitro compound as represented by the following reaction formula. Furthermore, as an example described in the following reaction formula, it is a diamine in which the hydrogen atom of the benzene ring and the saturated hydrocarbon moiety is not substituted by a halogen atom such as a fluorine atom or a monovalent organic group other than an amine group.
(上述反應式中,Y1及Y2係分別獨立為單鍵、-O-、-S-、-COO-或-OCO-,R1及R2係分別獨立為-H、-OH、=O或一價的有機基,R3及R4係分別獨立為碳原子數1~3的伸烷基,又,苯環的任意的氫原子可被一價的有機基所取代)。 (In the above reaction formula, Y 1 and Y 2 are independently a single bond, -O-, -S-, -COO- or -OCO-, R 1 and R 2 are independently -H, -OH, = O or a monovalent organic group, R 3 and R 4 are each independently an alkylene group having 1 to 3 carbon atoms, and any hydrogen atom of the benzene ring may be substituted by a monovalent organic group).
還原二硝基化合物之方法並無特別限制,可示例將鈀-碳、氧化鉑、雷氏鎳、鉑黑、銠-氧化鋁、硫化鉑碳等使用作為觸媒,在乙酸乙酯、甲苯、四氫呋喃、二噁烷、醇系等的溶劑中,藉由氫氣、肼、氯化氫等來進行還原之方法。因應所需亦可使用高壓釜等在加壓下來進行。另一方面,在取代苯環或飽和烴部的氫原子的取代基的構造中包含不飽和鍵結部位時,若使用鈀碳或鉑碳等, 該不飽和鍵結部位恐將有被還原成為飽和鍵結之虞,因此以使用還原鐵或錫、氯化錫等的過渡金屬作為觸媒之還原條件為較佳。 The method for reducing the dinitro compound is not particularly limited, but palladium-carbon, platinum oxide, Raj's nickel, platinum black, rhodium-alumina, platinum sulfide carbon, etc. are used as catalysts in ethyl acetate, toluene, A method of reducing with hydrogen, hydrazine, hydrogen chloride, etc. in a solvent such as tetrahydrofuran, dioxane, or alcohol. If necessary, it can also be carried out under pressure using an autoclave or the like. On the other hand, when an unsaturated bond site is included in the structure of the substituent that replaces the hydrogen atom of the benzene ring or the saturated hydrocarbon moiety, when palladium carbon, platinum carbon or the like is used, This unsaturated bond site may be reduced to become a saturated bond, so the reduction conditions using reduced iron or transition metals such as tin and tin chloride as catalysts are preferable.
上述反應係可藉由在鹼存在下來進行。使用的鹼只要能夠合成即可並無特別限定,可舉出碳酸鉀、碳酸鈉、碳酸銫、醇鈉、醇鉀、氫氧化鈉、氫氧化鉀、氫化鈉等的無機鹼、砒啶、二甲基胺基砒啶、三甲胺、三乙胺、三丁胺等的有機鹼等。又,依據情形若併用二亞苄基丙酮鈀或二苯基膦基二茂鐵鈀之類的鈀觸媒或銅觸媒等時,將可提升收率。 The above reaction system can be carried out in the presence of a base. The base to be used is not particularly limited as long as it can be synthesized, and examples thereof include inorganic bases such as potassium carbonate, sodium carbonate, cesium carbonate, sodium alkoxide, potassium alkoxide, sodium hydroxide, potassium Organic bases such as methylaminopyridine, trimethylamine, triethylamine, tributylamine, etc. In addition, depending on the situation, when a palladium catalyst such as dibenzylideneacetone palladium or diphenylphosphinoferrocene palladium or a copper catalyst or the like is used in combination, the yield can be improved.
如此般之方式所得之本發明之二胺,可作為聚醯胺酸或聚醯胺酸酯等的聚醯亞胺前驅物、聚醯亞胺、聚脲、聚醯胺等(匯整該等稱為「聚合物」)的原料來使用。該聚合物係可例如在指定的有機溶劑中溶解並作為液晶配向劑來使用,但並不被限定於該用途中。以下,對於在該構造中包含式[1]所表示之二胺之聚合物進行說明。 The diamine of the present invention obtained in this way can be used as a polyimide precursor, polyimide, polyurea, polyamide, etc. known as "polymer") raw materials. This polymer system can be used as a liquid crystal aligning agent by dissolving it in a predetermined organic solvent, for example, but it is not limited to this use. Hereinafter, the polymer containing the diamine represented by Formula [1] in this structure is demonstrated.
本發明之聚合物係使用上述之本發明之二胺或其衍生物(如後述)所得者,且具有源自二胺成分之下述式[2]所表示之構造者。 The polymer of the present invention is obtained by using the above-mentioned diamine of the present invention or a derivative thereof (described later), and has a structure represented by the following formula [2] derived from a diamine component.
(式[2]中,Y1係單鍵、-O-、-S-、-COO-或-OCO-,R1及R2係分別獨立為-H、-OH、=O或一價的有機基,R3係碳原子數1~3的伸烷基,*係表示與其他的基鍵結之部位,又,苯環的任意的氫原子可被一價的有機基所取代)。 (In formula [2], Y 1 is a single bond, -O-, -S-, -COO- or -OCO-, and R 1 and R 2 are independently -H, -OH, =O or monovalent, respectively. In the organic group, R 3 represents an alkylene group having 1 to 3 carbon atoms, * represents a bonding site with other groups, and any hydrogen atom of the benzene ring may be substituted by a monovalent organic group).
如此般的聚合物之作為源自二胺成分之式[2]所表示之構造,係以具有下述式[3]所表示之構造者為較佳。 The structure represented by the formula [2] derived from the diamine component of such a polymer is preferably one having the structure represented by the following formula [3].
(式[3]中,Y1及Y2係分別獨立為單鍵、-O-、-S-、-COO-或-OCO-,R1及R2係分別獨立為-H、-OH、=O或一價的有機基,R3及R4係分別獨立為碳原子數1~3的伸烷基,*係表示與其他的基鍵結之部位,又,苯環的任意的氫原子可被一價的有機基所取代)。 (In formula [3], Y 1 and Y 2 are each independently a single bond, -O-, -S-, -COO- or -OCO-, and R 1 and R 2 are each independently -H, -OH, =O or a monovalent organic group, R 3 and R 4 are each independently an alkylene group having 1 to 3 carbon atoms, * represents a site where other groups are bonded, and an arbitrary hydrogen atom of a benzene ring may be substituted by a monovalent organic group).
於此,作為上述本發明之二胺之衍生物,可舉出:具有將2個以上的上述二胺連結起來的構造之二胺、或具有透過上述Y1或Y2來連結上述二胺的構造之二胺。又,源自二胺成分的構造,除了式[2]以外,亦可包含源自其他的二胺的構造(如後述)。 Here, as the derivative of the diamine of the present invention, a diamine having a structure in which two or more of the above-mentioned diamines are linked together, or a diamine having the above-mentioned diamine linked through the above-mentioned Y 1 or Y 2 can be mentioned. Structure of the diamine. Moreover, in addition to Formula [2], the structure derived from a diamine component may contain the structure derived from another diamine (it mentions later).
尚,作為式[2]及式[3]中之一價的有機基或碳原子數1~3的伸烷基,可舉出與式[1]相同者。 Further, as the monovalent organic group or the alkylene group having 1 to 3 carbon atoms in the formulas [2] and [3], the same ones as those of the formula [1] can be mentioned.
又,本發明之聚合物,就作為液晶配向劑的使用之觀點而言,以選自包含下述式[4]所表示之構造單位之聚醯亞胺前驅物及該醯亞胺化合物的聚醯亞胺中之至少1種為較佳。 In addition, the polymer of the present invention is selected from the group consisting of a polyimide precursor including a structural unit represented by the following formula [4] and a polymer of the imide compound from the viewpoint of use as a liquid crystal aligning agent. At least one kind of imide is preferred.
(式[4]中,X1係源自四羧酸衍生物之四價的有機基,W1係源自具有式[2]或式[3]所表示之構造之二胺之二價的有機基,R5及R6係表示氫原子或碳原子數1~5的烷基,A1及A2係分別獨立表示氫原子、碳原子數1~5的烷基、碳原子數2~5的烯基或碳原子數2~5的炔基)。 (In formula [4], X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative, and W 1 is a divalent organic group derived from a diamine having a structure represented by formula [2] or formula [3] Organic group, R 5 and R 6 represent a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and A 1 and A 2 independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, and 2 to 2 carbon atoms. 5 alkenyl or alkynyl with 2 to 5 carbon atoms).
式[4]中,作為碳原子數1~5的烷基,可舉出例 如甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、t-丁基、n-戊基、異戊基、s-戊基、t-戊基等;作為碳原子數2~5的烯基,可舉出例如乙烯基、烯丙基、1-丙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-戊烯基、2-戊烯基、3-戊烯基、4-戊烯基等;作為碳原子數2~5的炔基,可舉出例如乙炔基、1-丙炔基、2-丙炔(炔丙基)基、3-丁炔基、戊炔基等。該等之中,就加熱時容易進行醯亞胺化反應之觀點而言,R5及R6係以氫原子、甲基或乙基為較佳,以氫原子或甲基為又較佳,就液晶配向性之觀點而言,A1及A2係以氫原子或甲基為較佳。 In formula [4], examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, s-pentyl, t-pentyl, etc.; Examples of the alkenyl group having 2 to 5 carbon atoms include vinyl, allyl, 1-propenyl, and 1-butane. Alkenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, etc.; as an alkynyl group having 2 to 5 carbon atoms , for example, an ethynyl group, a 1-propynyl group, a 2-propynyl (propargyl) group, a 3-butynyl group, a pentynyl group, and the like are mentioned. Among them, R 5 and R 6 are preferably hydrogen atoms, methyl groups or ethyl groups, and more preferably hydrogen atoms or methyl groups, from the viewpoint that the imidization reaction is easily carried out during heating, From the viewpoint of liquid crystal alignment, A 1 and A 2 are preferably hydrogen atoms or methyl groups.
X1只要是源自四羧酸衍生物之四價的有機基即可,該構造並無特別限定。又,X1係可因應聚合物對溶劑的溶解性或液晶配向劑的塗佈性、製成液晶配向膜時之液晶的配向性、電壓保持率、蓄積電荷等所需要的特性之程度來做適當選擇,在相同聚合物中可使用1種類、亦可混合存在2種類以上。 The structure is not particularly limited as long as X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative. In addition, X 1 can be adjusted according to the degree of the solubility of the polymer in the solvent, the coatability of the liquid crystal alignment agent, the alignment of the liquid crystal when the liquid crystal alignment film is formed, the voltage retention rate, the accumulated charge, etc. Appropriately selected, one type of the same polymer may be used, or two or more types may be mixed.
不僅是四羧酸二酐,X1亦可使用該四羧酸衍生物的四羧酸、四羧酸二鹵化物化合物、四羧酸二烷基酯化合物或四羧酸二烷基酯二鹵化物化合物。作為四羧酸二酐或該衍生物,係以使用由下述式[6]所表示之四羧酸二酐或該衍生物所選出之至少1種為又較佳。 Not only tetracarboxylic dianhydride, but also tetracarboxylic acid, tetracarboxylic acid dihalide compound, tetracarboxylic acid dialkyl ester compound or tetracarboxylic acid dialkyl ester dihalogenation compound of the tetracarboxylic acid derivative can be used for X 1 compound. As the tetracarboxylic dianhydride or the derivative, at least one selected from the tetracarboxylic dianhydride represented by the following formula [6] or the derivative is preferably used.
式[6]中,V1係具有脂環式構造之四價的有機基,該構造並無特別限定。作為具體例,可舉出下述式[V1-1]~式[V1-44]。 In formula [6], V 1 is a tetravalent organic group having an alicyclic structure, and the structure is not particularly limited. Specific examples include the following formulae [V 1 -1] to [V 1 -44].
式[V1-1]~式[V1-4]中,R7~R27係分別獨立為氫原子、鹵素原子、碳原子數1~6的烷基、碳原子數2~6的烯基、碳原子數2~6的炔基、含有氟原子的碳原子數1~6之1價的有機基或苯基,可為相同或相異。就液晶配向性之觀點而言,R7~R27係以氫原子、鹵素原子、甲基或乙基為較佳,以氫原子或甲基為又較佳。 In formula [V 1 -1] to formula [V 1 -4], R 7 to R 27 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkene having 2 to 6 carbon atoms. A group, an alkynyl group having 2 to 6 carbon atoms, a fluorine atom-containing monovalent organic group having 1 to 6 carbon atoms, or a phenyl group may be the same or different. From the viewpoint of liquid crystal alignment, R 7 to R 27 are preferably a hydrogen atom, a halogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom or a methyl group.
作為式[V1-1]之具體的構造,可舉出下述式[V1-1-1]~式[V1-1-6]所表示之構造。就液晶配向性及光反應的感度之觀點而言,以下述式[V1-1-1]所表示之構造為 特佳。 As a specific structure of Formula [ V1-1 ], the structure represented by following formula [ V1-1-1 ] - Formula [ V1-1-6 ] is mentioned. The structure represented by the following formula [V 1 -1-1] is particularly preferable from the viewpoint of the liquid crystal alignment and the sensitivity of the photoreaction.
式[4]中,W1只要是源自具有式[2]或式[3]所表示之構造之二胺之二價的有機基即可,該構造並無特別限定,亦可混合存在2種類以上。又,W1係對應於本發明中所使用之二胺成分的構造,並含有具有式[1]所表示之構造之特定的二胺(例如選自由下述式[W1-1]~式[W1-13]所表示之化合物所成之群中之至少1種的二胺)。 In formula [4], W 1 is not particularly limited as long as it is a divalent organic group derived from a diamine having a structure represented by formula [2] or formula [3], and 2 may be present in combination. above types. Moreover, W 1 corresponds to the structure of the diamine component used in the present invention, and contains a specific diamine having a structure represented by the formula [1] (for example, selected from the following formulas [W 1 -1] to At least one diamine in the group of compounds represented by [W 1 -13]).
尚,式[W1-3]中,Boc係表示下述所示之基(tert-丁氧基羰基)。 Furthermore, in the formula [W 1 -3], Boc represents the group shown below (tert-butoxycarbonyl group).
但,W1的全部並不一定需要成為對應上述二胺的構造。在W1的一部分中,亦可包含對應於除了上述 二胺以外的二胺(其他的二胺)的構造。作為對應於其他的二胺的構造(以下作為「構造W2」)係可如下述式[7]所表示般成為一般式化。尚,作為下述式[7]中之A1及A2,可舉出與式[4]相同者。 However, all of W 1 need not necessarily have a structure corresponding to the above-mentioned diamine. A part of W 1 may contain a structure corresponding to a diamine (other diamine) other than the above-mentioned diamine. The structure corresponding to other diamines (hereinafter referred to as "structure W 2 ") can be generalized as represented by the following formula [7]. Furthermore, as A 1 and A 2 in the following formula [7], the same ones as those of the formula [4] can be mentioned.
又,若要示例式[7]所表示之構造W2時,以如下述式[W2-1]~式[W2-173]所表示般。 Furthermore, when the structure W 2 represented by the formula [7] is illustrated, it is as represented by the following formulae [W 2 -1] to [W 2 -173].
尚,式[W2-168]、式[W2-169]、式[W2-172]及式[W2-173]中之Boc基係表示如下述所示之tert-丁氧基羰基。 Furthermore, the Boc group in the formula [W 2 -168], the formula [W 2 -169], the formula [W 2 -172] and the formula [W 2 -173] represents a tert-butoxycarbonyl group as shown below .
包含式[4]所表示之構造單位之聚醯亞胺前驅物,若同時包含式[7]所表示之構造單位時,相對於式[4]與式[7]的合計,式[4]所表示之構造單位係以10莫耳%以上為較佳,又較佳為20莫耳%以上,特佳為30莫耳%以上。 When the polyimide precursor containing the structural unit represented by the formula [4] also contains the structural unit represented by the formula [7], with respect to the sum of the formula [4] and the formula [7], the formula [4] The indicated structural unit is preferably 10 mol % or more, more preferably 20 mol % or more, and particularly preferably 30 mol % or more.
本發明之聚合物的聚醯亞胺前驅物或聚醯亞胺的分子量,由含有該聚合物的液晶配向劑來得到液晶配向膜時,考慮該塗膜(液晶配向膜)的強度、塗膜形成時的作業性、及塗膜的均勻性,利用GPC(Gel Permeation Chromatography)法所測定的重量平均分子量係以2,000~500,000為較佳,以5,000~300,000為又較佳,以10,000~100,000為更佳。 The molecular weight of the polyimide precursor or polyimide of the polymer of the present invention, when obtaining a liquid crystal alignment film from a liquid crystal alignment agent containing the polymer, the strength of the coating film (liquid crystal alignment film), the strength of the coating film, and the For the workability during formation and the uniformity of the coating film, the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and 10,000 to 100,000. better.
接下來,對於本發明之聚合物之主要的製造方法來進行說明。尚,以下所說明之方法為製造例,並不被限定於此。 Next, the main manufacturing method of the polymer of this invention is demonstrated. In addition, the method demonstrated below is a manufacturing example, and is not limited to this.
例如,包含式[4]所表示之構造單位之聚合物若為聚醯亞胺前驅物的聚醯胺酸時,上述聚合物係可藉由四羧酸衍生物的四羧酸二酐與二胺成分之反應而得到。藉 由該反應從而得到聚醯胺酸時,可使用周知的合成方法。該合成方法係有使四羧酸二酐與二胺成分在有機溶劑中進行反應之方法。上述方法就在有機溶劑中較容易地進行、且不會產生副產物之點而言為有利。 For example, if the polymer containing the structural unit represented by the formula [4] is a polyimide precursor of polyimide, the above-mentioned polymer can be obtained by combining tetracarboxylic dianhydride and dicarboxylic acid tetracarboxylic acid derivative. obtained by the reaction of the amine component. borrow When the polyamic acid is obtained by this reaction, a known synthesis method can be used. This synthesis method is a method of reacting a tetracarboxylic dianhydride and a diamine component in an organic solvent. The above-mentioned method is advantageous in that it can be carried out relatively easily in an organic solvent and does not generate by-products.
作為使用於上述反應之有機溶劑,只要是生成的聚醯胺酸(聚合物)可溶解即可,並無特別限定,可舉出例如N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-甲基己內醯胺、二甲基亞碸、四甲脲、砒啶、二甲基碸、六甲基亞碸、γ-丁內酯、異丙醇、甲氧基甲基戊醇、二戊烯、乙基戊基酮、甲基壬基酮、甲基乙基酮、甲基異戊基酮、甲基異丙基酮、甲基溶纖劑、乙基溶纖劑、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、丁基卡必醇、乙基卡必醇、乙二醇、乙二醇單乙酸酯、乙二醇單異丙基醚、乙二醇單丁基醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲基醚、丙二醇-tert-丁基醚、二丙二醇單甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲基醚、3-甲基-3-甲氧基丁醇、二異丙基醚、乙基異丁基醚、二異丁烯、乙酸戊酯、丁酸丁酯、丁基醚、二異丁基酮、甲基環己烯、丙基醚、二己基醚、二噁烷、n-己烷、n-戊烷、n-辛烷、二乙基醚、環己酮、碳酸伸乙酯、碳酸伸丙酯、乳 酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、二甘醇二甲醚、4-羥基-4-甲基-2-戊酮、3-甲氧基-N,N-二甲基丙醯胺、3-乙氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺等。該等係可單獨使用亦可混合來使用。又,即使是不能使聚醯胺酸(聚合物)溶解的溶劑,在生成的聚醯胺酸不析出的範圍內,亦可混合在上述有機溶劑中使用。特別是,有機溶劑中的水分會成為阻礙聚合反應,進而使生成的聚醯胺酸水解之原因,因此有機溶劑係以使用儘可能脫水乾燥者為較佳。 The organic solvent used in the above-mentioned reaction is not particularly limited as long as the resulting polyamic acid (polymer) can be dissolved, and examples thereof include N,N-dimethylformamide, N,N- Dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, aridine , dimethyl sulfite, hexamethyl sulfoxide, γ-butyrolactone, isopropanol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone Ketone, Methyl Isoamyl Ketone, Methyl Isopropyl Ketone, Methyl Cellosolve, Ethyl Cellosolve, Methyl Cellosolve Acetate, Ethyl Cellosolve Acetate, Butyl Carbide Alcohol, Ethyl Carbitol, Ethylene Glycol, Ethylene Glycol Monoacetate, Ethylene Glycol Monoisopropyl Ether, Ethylene Glycol Monobutyl Ether, Propylene Glycol, Propylene Glycol Monoacetate, Propylene Glycol Monomethyl Ether , propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3- Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyric acid Butyl ester, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether , Cyclohexanone, Ethylene carbonate, Propylene carbonate, Emulsion Methyl Acetate, Ethyl Lactate, Methyl Acetate, Ethyl Acetate, N-Butyl Acetate, Propylene Glycol Monoethyl Ether, Methyl Pyruvate, Ethyl Pyruvate, Methyl 3-Methoxypropionate, 3 -Methyl ethyl ethoxypropionate, Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, 3-methylpropionate Butyl oxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropionamide, 3-ethoxy -N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, etc. These systems may be used alone or in combination. Moreover, even if it is a solvent which cannot dissolve a polyamic acid (polymer), in the range in which the produced polyamic acid does not precipitate, you may mix and use it with the said organic solvent. In particular, the moisture in the organic solvent may inhibit the polymerization reaction and further hydrolyze the produced polyamic acid. Therefore, it is preferable to use the organic solvent that is dehydrated and dried as much as possible.
使四羧酸二酐與二胺成分在有機溶劑中反應時,可舉出下述方法:攪拌使二胺成分分散或溶解於有機溶劑中而得到溶液,於前述溶液中直接添加四羧酸二酐、或是使四羧酸二酐分散或溶解於有機溶劑後再添加之方法;將四羧酸二酐分散或溶解於有機溶劑中而得到溶液,於前述溶液中添加二胺成分之方法;交替地添加四羧酸二酐與二胺成分之方法等,可使用該等之中任一種之方法。又,四羧酸二酐或二胺成分若由多種的化合物所成時,可以在預先混合的狀態下使其反應,亦可以使其個別地依序反應,進而再使個別地反應的低分子量體予以混合反應來製成高分子量體。 When the tetracarboxylic dianhydride and the diamine component are reacted in an organic solvent, the following method may be mentioned: stirring to disperse or dissolve the diamine component in the organic solvent to obtain a solution, and directly adding the tetracarboxylic acid dihydrate to the solution. Anhydride, or a method of dispersing or dissolving tetracarboxylic dianhydride in an organic solvent and then adding it; a method of dispersing or dissolving tetracarboxylic dianhydride in an organic solvent to obtain a solution, and adding a diamine component to the aforementioned solution; The method of adding a tetracarboxylic dianhydride and a diamine component alternately, etc., can use any of these methods. In addition, when the tetracarboxylic dianhydride or diamine component is composed of a plurality of compounds, it may be allowed to react in a premixed state, or may be reacted individually in sequence, and further reacted individually with low molecular weight. The body is mixed and reacted to make a high molecular weight body.
此時的縮聚合的溫度係可選擇-20℃~150℃之 任意的溫度,但較佳為-5℃~100℃的範圍。又,縮聚合反應係可以任意的濃度來進行,但若濃度過低時,則難以得到高分子量的聚合物,若濃度過高時則反應液的黏性變得過高而難均勻的攪拌,因此四羧酸二酐與二胺成分在反應溶液中之合計濃度,較佳設為1質量%~50質量%,又較佳設為5質量%~30質量%。反應初期可在高濃度下進行,之後亦可追加有機溶劑。 At this time, the temperature of the polycondensation can be selected from -20°C to 150°C Arbitrary temperature, Preferably it is the range of -5 degreeC - 100 degreeC. In addition, the polycondensation reaction system can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution will become too high, making it difficult to uniformly stir. Therefore, the total concentration of the tetracarboxylic dianhydride and the diamine component in the reaction solution is preferably set to 1% by mass to 50% by mass, and more preferably set to 5% by mass to 30% by mass. The initial stage of the reaction may be carried out at a high concentration, and an organic solvent may be added after that.
聚醯胺酸的聚合反應中,四羧酸二酐的合計莫耳數與二胺成分的合計莫耳數之比(四羧酸二酐的合計莫耳數/二胺成分的合計莫耳數)係以0.8~1.2為較佳。與通常的縮聚合反應為相同,該莫耳比越接近1.0所生成的聚醯胺酸的分子量越大。 In the polymerization reaction of polyamic acid, the ratio of the total moles of tetracarboxylic dianhydride to the total moles of diamine components (total moles of tetracarboxylic dianhydride/total moles of diamine components) ) is preferably 0.8 to 1.2. As in the general polycondensation reaction, the molecular weight of the polyamic acid produced is increased as the molar ratio is closer to 1.0.
包含式[4]所表示之構造單位的聚合物若為聚醯胺酸酯時,可藉由四羧酸二酯二醯氯與二胺成分的反應、或可藉由四羧酸二酯與二胺成分在適當的縮合劑或鹼的存在下使其反應而得到。或者,依上述之方法預先合成聚醯胺酸,再利用高分子反應使醯胺酸中的羧酸酯化亦可得到。 If the polymer containing the structural unit represented by the formula [4] is a polyamide, it can be reacted with a tetracarboxylic acid diester diacid chloride and a diamine component, or by a tetracarboxylic acid diester and a diamine component. The diamine component is obtained by reacting it in the presence of a suitable condensing agent or a base. Alternatively, it can be obtained by synthesizing polyamic acid in advance according to the above-mentioned method, and then esterifying the carboxylic acid in the polyamic acid by polymer reaction.
具體而言,可藉由例如將四羧酸二酯二醯氯與二胺,在鹼與有機溶劑之存在下以-20℃~150℃,較佳為0℃~50℃下,反應30分鐘~24小時,較佳為1小時~4小時來合成聚醯胺酸酯。 Specifically, for example, tetracarboxylic acid diester diacid chloride and diamine can be reacted for 30 minutes at -20°C to 150°C, preferably 0°C to 50°C in the presence of a base and an organic solvent. ~24 hours, preferably 1 hour to 4 hours to synthesize the polyamide.
作為鹼係可使用砒啶、三乙胺、4-二甲基胺基砒啶等,為了使反應溫和地進行故以砒啶為較佳。鹼的 添加量就容易除去的量、容易得到高分子量體之觀點而言,相對於四羧酸二酯二醯氯以2~4倍莫耳為較佳。 As the base system, arsenic, triethylamine, 4-dimethylaminopyridine, etc. can be used, and arsenic is preferable in order to allow the reaction to proceed mildly. alkaline The addition amount is preferably 2 to 4 times mol relative to the tetracarboxylic acid diester diacyl chloride from the viewpoint of an amount that can be easily removed and a high molecular weight product is easily obtained.
又,藉由在縮合劑存在下,將四羧酸二酯與二胺成分縮聚合時,作為鹼可使用三苯基亞磷酸酯、二環己基碳二醯亞胺、1-乙基-3-(3-二甲基胺基丙基)碳二醯亞胺鹽酸鹽、N,N’-羰基二咪唑、二甲氧基-1,3,5-三嗪基甲基嗎福啉鎓、O-(苯并三唑-1-基)-N,N,N’,N’-四甲基脲四氟硼酸鹽、O-(苯并三唑-1-基)-N,N,N’,N’-四甲基脲六氟磷酸鹽、(2,3-二氫-2-硫基-3-苯并噁唑基)膦酸二苯酯、4-(4,6-二甲氧基-1,3,5-三嗪-2-基)4-甲氧基嗎啉鹽酸鹽n-水合物等。 In addition, when the tetracarboxylic acid diester and the diamine component are polycondensed in the presence of a condensing agent, triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3 can be used as the base. -(3-Dimethylaminopropyl)carbodiimide hydrochloride, N,N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium , O-(benzotriazol-1-yl)-N,N,N',N'-tetramethylurea tetrafluoroborate, O-(benzotriazol-1-yl)-N,N, N',N'-tetramethylurea hexafluorophosphate, (2,3-dihydro-2-sulfanyl-3-benzoxazolyl) diphenylphosphonate, 4-(4,6-diphenyl) Methoxy-1,3,5-triazin-2-yl)4-methoxymorpholine hydrochloride n-hydrate, etc.
又,使用上述縮合劑之方法中,藉由加入路易斯酸來作為添加劑從而使反應有效率的進行。作為路易斯酸係以氯化鋰、溴化鋰等的鹵化鋰為較佳。路易斯酸的添加量,相對於反應的二胺或四羧酸二酯以0.1倍莫耳量~1.0倍莫耳量為較佳。 In addition, in the method using the above-mentioned condensing agent, the reaction proceeds efficiently by adding a Lewis acid as an additive. As the Lewis acid system, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably 0.1 to 1.0 times the molar amount relative to the reacted diamine or tetracarboxylic acid diester.
使用於上述之反應之溶劑,係可使用與在上述所表示之合成聚醯胺酸時所使用的溶劑為相同的溶劑來進行,但就單體及聚合物的溶解性而言,以N-甲基-2-吡咯啶酮、γ-丁內酯為較佳,該等係可1種或亦可混合2種以上來使用。合成時的濃度就難以引起聚合物的析出、且容易得到高分子量體之觀點而言,在四羧酸二酯二醯氯或四羧酸二酯等的四羧酸衍生物與二胺成分的反應溶液中的合計濃度係以1質量%~30質量%為較佳,以5質量%~20質量% 為又較佳。又,為了防止四羧酸二酯二醯氯的水解,使用於聚醯胺酸酯的合成之溶劑儘可能呈脫水狀態為佳,以在氮環境中防止外來氣體的混入為較佳。 The solvent used in the above-mentioned reaction can be carried out using the same solvent as the solvent used in the synthesis of the polyamic acid shown above, but in terms of the solubility of monomers and polymers, N- Methyl-2-pyrrolidone and γ-butyrolactone are preferable, and these may be used alone or in combination of two or more. The concentration at the time of synthesis is difficult to cause precipitation of the polymer, and it is easy to obtain a high-molecular-weight body. The total concentration in the reaction solution is preferably 1% by mass to 30% by mass, and 5% by mass to 20% by mass For better. In addition, in order to prevent the hydrolysis of the tetracarboxylic diester diacyl chloride, the solvent used for the synthesis of the polyamic acid ester is preferably in a dehydrated state as much as possible, and it is preferable to prevent the mixing of foreign gas in a nitrogen environment.
包含式[4]所表示之構造單位之聚合物若為聚醯亞胺時,係在主鏈具有式[2]或式[3]所表示之2價的基,藉由使上述聚醯胺酸脫水閉環而可得到。在該聚醯亞胺中,醯胺酸基的脫水閉環率(醯亞胺化率)不需要一定為100%,可因應用途或目的來任意地調整。 When the polymer containing the structural unit represented by the formula [4] is a polyimide, it has a divalent group represented by the formula [2] or the formula [3] in the main chain. Acid dehydration and ring closure can be obtained. In this polyimide, the dehydration ring closure rate (imidation rate) of the amide acid group does not necessarily have to be 100%, and can be arbitrarily adjusted according to the application and purpose.
作為使聚醯胺酸醯亞胺化之方法,可舉出直接加熱聚醯胺酸的溶液的熱醯亞胺化、或在聚醯胺酸的溶液中添加觸媒的觸媒醯亞胺化等。 As a method of imidizing a polyamic acid, thermal imidization in which a solution of polyamic acid is directly heated, or catalytic imidization in which a catalyst is added to a solution of polyamic acid can be mentioned. Wait.
在溶液中使聚醯胺酸熱醯亞胺化時的溫度為100℃~400℃,較佳為120℃~250℃,以在將藉由醯亞胺化反應生成的水排至體系外之同時來進行為較佳。 The temperature during thermal imidization of the polyamic acid in the solution is 100°C to 400°C, preferably 120°C to 250°C, so that the water generated by the imidization reaction is discharged to the outside of the system. It is better to do it at the same time.
聚醯胺酸的觸媒醯亞胺化係可藉由在聚醯胺酸的溶液中添加鹼性觸媒與酸酐,在-20℃~250℃,較佳為在0℃~180℃下進行攪拌來進行。鹼性觸媒的量係醯胺酸基的0.5莫耳倍~30莫耳倍,較佳為2莫耳倍~20莫耳倍,酸酐的量係醯胺酸基的1莫耳倍~50莫耳倍,較佳為3莫耳倍~30莫耳倍。作為鹼性觸媒,可舉出砒啶、三乙胺、三甲胺、三丁胺、三辛胺等,其中,砒啶係具有對於使反應進行而言適度的鹼性因此為較佳。作為酸酐,可舉出乙酸酐、偏苯三酸酐、焦蜜石酸二酐等,其中若使用乙酸酐時將容易進行反應結束後的純化故為較佳。藉由觸媒醯亞胺 化之醯亞胺化率係可藉由調節觸媒量與反應溫度、反應時間來控制。 The catalytic imidization of polyamide acid can be carried out by adding alkaline catalyst and acid anhydride to the solution of polyamide acid, at -20℃~250℃, preferably at 0℃~180℃. Stir to proceed. The amount of the alkaline catalyst is 0.5 mol times to 30 mol times of the amide acid group, preferably 2 mol times to 20 mol times, and the amount of the acid anhydride is 1 mol times to 50 mol times of the amide acid group. Molar times, preferably 3 mol times to 30 mol times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like, and among these, pyridine-based catalysts are preferred because they have an appropriate basicity to allow the reaction to proceed. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic dianhydride, and the like. Among them, when acetic anhydride is used, purification after completion of the reaction is easy to perform. by catalytic imide The rate of imidization of Zn can be controlled by adjusting the amount of catalyst, reaction temperature and reaction time.
又,如上述般,亦可以藉由在高溫下加熱聚醯胺酸酯來促進脫醇,使其閉環從而得到聚醯亞胺。 Moreover, as mentioned above, polyimide can also be obtained by heating a polyimide at a high temperature to promote dealcoholization and to close the ring.
尚,從聚醯胺酸、聚醯胺酸酯等的聚醯亞胺前驅物、或聚醯亞胺的反應溶液回收生成的聚醯胺酸、聚醯胺酸酯、聚醯亞胺時,將反應溶液投入至不良溶劑中而使其沉澱即可。作為沉澱使用的不良溶劑,可舉出甲醇、丙酮、己烷、丁基溶纖劑、庚烷、甲基乙基酮、甲基異丁基酮、乙醇、甲苯、苯、水等。投入至不良溶劑中而使其沉澱的聚醯亞胺前驅物或聚醯亞胺係可在過濾回收後,在常壓或者減壓下,在常溫或者加熱下來進行乾燥。又,若使沉澱回收的聚醯亞胺前驅物或聚醯亞胺再溶解至有機溶劑並重複2~10次再沉澱回收的操作時,則可減少聚合物中的雜質。作為此時的不良溶劑,可舉出例如醇類、酮類、烴等,若使用由該等之中所選出3種類以上的不良溶劑時,則純化的效率更進一步提升,故為較佳。 In addition, when recovering the resulting polyamic acid, polyamic acid ester, and polyimide from polyimide precursors such as polyamic acid and polyamic acid ester, or from the reaction solution of polyimide, The reaction solution may be poured into a poor solvent and precipitated. Examples of poor solvents used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polyimide precursor or polyimide-based which has been put into a poor solvent and precipitated can be recovered by filtration, and then dried under normal pressure or reduced pressure, at normal temperature or under heating. In addition, if the polyimide precursor or polyimide recovered by precipitation is redissolved in an organic solvent and the operation of reprecipitation and recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent in this case include alcohols, ketones, and hydrocarbons. When three or more types of poor solvents selected from these are used, the purification efficiency is further improved, which is preferable.
如此般之方式所得之本發明之聚合物,係可溶解在指定的有機溶劑中並使用作為液晶配向劑。該液晶配向劑在液晶顯示元件中係使用於控制液晶層的液晶分子的配向性之液晶配向膜。以下,對於含有本發明之聚合物之液晶配向劑來進行說明。 The polymer of the present invention obtained in this manner can be dissolved in a designated organic solvent and used as a liquid crystal aligning agent. The liquid crystal alignment agent is a liquid crystal alignment film used for controlling the alignment of liquid crystal molecules in a liquid crystal layer in a liquid crystal display element. Hereinafter, the liquid crystal aligning agent containing the polymer of this invention is demonstrated.
本發明之液晶配向劑所含有之聚合物,其係由源自上述二胺成分之包含具有式[2]所表示之構造之二胺之二胺成分所得之聚合物。又,該液晶配向劑較佳為含有源自上述二胺成分之具有式[3]所表示之構造之聚合物。又,該聚合物較佳為選自包含式[4]所表示之構造單位之聚醯亞胺前驅物及該醯亞胺化合物的聚醯亞胺中之至少1種。 The polymer contained in the liquid crystal aligning agent of the present invention is a polymer obtained from a diamine component containing a diamine having a structure represented by the formula [2] derived from the above-mentioned diamine component. Moreover, it is preferable that this liquid crystal aligning agent contains the polymer which has the structure represented by Formula [3] derived from the said diamine component. Moreover, it is preferable that this polymer is at least 1 sort(s) chosen from the polyimide precursor which contains the structural unit represented by Formula [4], and the polyimide compound of this.
但,本發明之液晶配向劑中所含有之聚合物,可以全部是本發明之聚合物,又只要是可發揮本發明所記載之效果之範圍內,本發明之聚合物中亦可含有2種以上的不同構造。或者,除了本發明之聚合物以外,亦可含有其他的聚合物,即,不具有式[2]或式[3]所表示之二價的基之聚合物。作為其他的聚合物之種類,可舉出聚醯胺酸、聚醯亞胺、聚醯胺酸酯、聚酯、聚醯胺、聚脲、聚有機矽氧烷、纖維素衍生物、聚縮醛、聚苯乙烯或該衍生物、聚(苯乙烯-苯基馬來醯亞胺)衍生物、聚(甲基)丙烯酸酯等。 However, the polymers contained in the liquid crystal aligning agent of the present invention may all be the polymers of the present invention, and the polymers of the present invention may also contain two kinds of polymers as long as the effects described in the present invention can be exhibited. different structures above. Alternatively, in addition to the polymer of the present invention, another polymer, that is, a polymer not having a divalent group represented by formula [2] or formula [3] may be contained. Examples of other types of polymers include polyamide, polyimide, polyamide, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivatives, polycondensate Aldehyde, polystyrene or derivatives thereof, poly(styrene-phenylmaleimide) derivatives, poly(meth)acrylates, and the like.
本發明之液晶配向劑若含有其他的聚合物時,相對於全部聚合物成分之本發明之聚合物的比例係以5質量%以上為較佳,作為其一例子可舉出5質量%~95質量%。本發明之聚合物的比例係可因應液晶配向劑或液晶配向膜的特性來適當選擇。 When the liquid crystal aligning agent of the present invention contains other polymers, the ratio of the polymer of the present invention relative to the total polymer components is preferably 5% by mass or more, and an example thereof includes 5% by mass to 95% by mass. quality%. The proportion of the polymer of the present invention can be appropriately selected according to the characteristics of the liquid crystal alignment agent or the liquid crystal alignment film.
本發明之液晶配向劑係被使用於製作液晶配向膜,就使形成均勻的薄膜之觀點而言,一般為採用塗佈液的形態。本發明之液晶配向劑亦以含有前述之聚合物成 分、與使該聚合物成分溶解的有機溶劑之塗佈液為較佳。此時,液晶配向劑中之聚合物的濃度係可依據想要形成的塗膜的厚度設定來做適當變更。就形成均勻且無缺點的塗膜之點而言,係以1質量%以上為較佳,就溶液的保存穩定性之點而言,係以設為10質量%以下為較佳。特佳的聚合物的濃度為2質量%~8質量%。 The liquid crystal alignment agent of the present invention is used for the production of a liquid crystal alignment film, and is generally in the form of a coating solution from the viewpoint of forming a uniform thin film. The liquid crystal alignment agent of the present invention is also composed of the aforementioned polymer. It is preferable to separate it into a coating liquid with an organic solvent in which the polymer component is dissolved. At this time, the concentration of the polymer in the liquid crystal aligning agent can be appropriately changed according to the thickness setting of the coating film to be formed. In terms of forming a uniform and defect-free coating film, 1 mass % or more is preferable, and 10 mass % or less is preferable in terms of storage stability of the solution. The concentration of a particularly preferable polymer is 2% by mass to 8% by mass.
本發明之液晶配向劑中所含有的有機溶劑,只要是使聚合物溶解的有機溶劑即可並無特別限定。作為其具體例,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-咪唑啉酮、甲基乙基酮、環己酮、環戊酮、4-羥基-4-甲基-2-戊酮等。其中,以使用N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、γ-丁內酯為較佳。尚,於此可示例的有機溶劑係可單獨使用、亦可混合來使用。進而,即使是無法溶解聚合物的溶劑,只要在生成的聚合物不析出的範圍內,亦可混合在有機溶劑中來使用。 The organic solvent contained in the liquid crystal aligning agent of the present invention is not particularly limited as long as it dissolves the polymer. Specific examples thereof 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, 4-hydroxy-4-methyl-2 -Pentanone, etc. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone are preferably used. Incidentally, the organic solvent systems exemplified here may be used alone or in combination. Furthermore, even if it is a solvent incapable of dissolving a polymer, as long as the produced polymer does not precipitate, it can be mixed with an organic solvent and used.
又,液晶配向劑中所含有的有機溶劑一般為使用混合溶劑,其係除了如上述般的溶劑以外,亦併用了在使液晶配向劑塗佈時的塗佈性或塗膜的表面平滑性提升的溶劑而成,即使是本發明之液晶配向劑中如此般的混合溶劑亦適合使用。可舉出併用的有機溶劑之具體例如下述,但並不被限定於該等的例子。 Moreover, as the organic solvent contained in the liquid crystal aligning agent, a mixed solvent is generally used, which is used in addition to the above-mentioned solvents, and is also used in combination to improve the coatability or the surface smoothness of the coating film at the time of coating the liquid crystal aligning agent. Even the mixed solvent in the liquid crystal aligning agent of the present invention is suitable for use. Specific examples of the organic solvent to be used in combination are given below, but are not limited to these examples.
可舉出例如乙醇、異丙醇、1-丁醇、2-丁醇、 異丁醇、tert-丁醇、1-戊醇、2-戊醇、3-戊醇、2-甲基-1-丁醇、異戊醇、tert-戊醇、3-甲基-2-丁醇、新戊醇、1-己醇、2-甲基-1-戊醇、2-甲基-2-戊醇、2-乙基-1-丁醇、1-庚醇、2-庚醇、3-庚醇、1-辛醇、2-辛醇、2-乙基-1-己醇、環己醇、1-甲基環己醇、2-甲基環己醇、3-甲基環己醇、1,2-乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,5-戊二醇、2-甲基-2,4-戊二醇、2-乙基-1,3-己二醇、二丙基醚、二丁基醚、二己基醚、二噁烷、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丁基醚、1,2-丁氧基乙烷、二乙二醇二甲基醚、二乙二醇二乙基醚、4-羥基-4-甲基-2-戊酮、二乙二醇甲基乙基醚、二乙二醇二丁基醚、2-戊酮、3-戊酮、2-己酮、2-庚酮、4-庚酮、3-乙氧基丁基乙酸酯、1-甲基戊基乙酸酯、2-乙基丁基乙酸酯、2-乙基己基乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、碳酸伸丙酯、碳酸伸乙酯、2-(甲氧基甲氧基)乙醇、乙二醇單丁基醚、乙二醇單異戊基醚、乙二醇單己基醚、2-(己氧基)乙醇、糠醇、二乙二醇、丙二醇、丙二醇單丁基醚、1-(丁氧基乙氧基)丙醇、丙二醇單甲基醚乙酸酯、二丙二醇、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇二甲基醚、三丙二醇單甲基醚、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單丁基醚乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯、2-(2-乙氧基乙氧基)乙基乙酸酯、二乙二醇乙酸 酯、三乙二醇、三乙二醇單甲基醚、三乙二醇單乙基醚、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸n-丙酯、乳酸n-丁酯、乳酸異戊酯等的溶劑。 For example, ethanol, isopropanol, 1-butanol, 2-butanol, Isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isoamyl alcohol, tert-pentanol, 3-methyl-2- Butanol, neopentanol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol Alcohol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methyl cyclohexanol, 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2 ,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether , dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3 -Pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-Ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylidene carbonate, ethylidene carbonate, 2-(methoxymethoxy)ethanol, ethylene glycol Monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy)ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1-(butoxy) Ethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol Alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol Alcohol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetic acid Esters, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoacetate Ethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Propionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate ester, isoamyl lactate, etc.
又,除了上述之溶劑以外,亦可使用例如下述式[S-1]~式[S-3]所表示之溶劑。 Moreover, in addition to the above-mentioned solvent, for example, the solvent represented by following formula [S-1] - formula [S-3] can also be used.
式[S-1]及式[S-2]中,R28及R29係表示碳原子數1~3的烷基。作為碳原子數1~3的烷基,可舉出例如甲基、乙基、n-丙基、異丙基等。又,式[S-3]中,R30係表示碳原子數1~4的烷基。作為碳原子數1~4的烷基,可舉出例如甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基等。 In formula [S-1] and formula [S-2], R 28 and R 29 represent an alkyl group having 1 to 3 carbon atoms. As a C1-C3 alkyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group etc. are mentioned, for example. In addition, in formula [S-3], R 30 represents an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
併用的有機溶劑之中,以使用1-己醇、環己醇、1,2-乙二醇、1,2-丙二醇、丙二醇單丁基醚、二乙二醇二乙基醚、4-羥基-4-甲基-2-戊酮、乙二醇單丁基醚或二丙二醇二甲基醚為較佳。如此般的溶劑的種類及含有量 係可因應液晶配向劑的塗佈裝置、塗佈條件、塗佈環境等來做適當選擇。 Among the organic solvents used in combination, 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, propylene glycol monobutyl ether, diethylene glycol diethyl ether, 4-hydroxyl -4-methyl-2-pentanone, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether are preferred. Types and contents of such solvents The system can be appropriately selected according to the coating device of the liquid crystal alignment agent, coating conditions, coating environment, and the like.
又,該等的溶劑係以液晶配向劑中所包含的溶劑全體的20質量%~99質量%為較佳。其中,以20質量%~90質量%為較佳。又較佳者為20質量%~70質量%。 Moreover, it is preferable that these solvent systems are 20 mass % - 99 mass % of the whole solvent contained in a liquid crystal aligning agent. Among them, 20% by mass to 90% by mass is preferable. More preferably, it is 20 mass % - 70 mass %.
本發明之液晶配向劑只要是不損及本發明之效果的範圍內,亦可追加含有除了聚合物成分及有機溶劑以外的成分。作為如此般的追加成分,可舉出用於提高液晶配向膜與基板的密著性或液晶配向膜與密封材的密著性的密著輔助劑、用於提高液晶配向膜的強度的交聯劑、用於調整液晶配向膜的介電率或電阻的介電質或導電物質等。作為該等追加成分之具體例,係如關於液晶配向劑之周知文獻中的各種揭示般,若要表示其一例子,可舉出國際公開第2015/060357號的段落[0105]~[0116]段落所揭示的成分等。 The liquid crystal aligning agent of this invention may additionally contain components other than a polymer component and an organic solvent in the range which does not impair the effect of this invention. Examples of such additional components include an adhesion adjuvant for improving the adhesion between a liquid crystal alignment film and a substrate, or between a liquid crystal alignment film and a sealing material, and a crosslinking for improving the strength of the liquid crystal alignment film. agents, dielectric or conductive substances used to adjust the dielectric constant or resistance of the liquid crystal alignment film. Specific examples of these additional components are as disclosed in various publications in the well-known literature on liquid crystal aligning agents, and to show one example, paragraphs [0105] to [0116] of International Publication No. 2015/060357 can be cited. The ingredients disclosed in the paragraph, etc.
本發明之液晶配向膜係由上述之液晶配向劑所得到。若舉出由液晶配向劑得到液晶配向膜之方法之一例子,可舉出將塗佈液形態的液晶配向劑塗佈至基板並進行乾燥,利用摩擦處理法或光配向處理法,對燒成所得之膜施予配向處理之方法。 The liquid crystal alignment film of the present invention is obtained from the above-mentioned liquid crystal alignment agent. As an example of a method for obtaining a liquid crystal alignment film from a liquid crystal alignment agent, the liquid crystal alignment agent in the form of a coating solution is applied to a substrate, dried, and then fired by a rubbing treatment method or a photo-alignment treatment method. A method of applying an alignment treatment to the resulting film.
作為塗佈本發明之液晶配向劑的基板,只要是透明性高的基板即可並無特別限定,亦可在使用玻璃基 板、氮化矽基板之同時,使用丙烯酸基板或聚碳酸酯基板等的塑膠基板等。此時,若使用形成用於驅動液晶的ITO電極等的基板時,就製程的簡單化之點而言為較佳。又,對於反射型的液晶顯示元件,若僅為單側的基板時,則可使用矽晶圓等的不透明的物質,此時的電極亦可使用鋁等的會反射光的材料。 The substrate on which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a substrate with high transparency, and a glass-based substrate may be used. In addition to boards and silicon nitride substrates, plastic substrates such as acrylic substrates or polycarbonate substrates are used. In this case, it is preferable to use a substrate for forming ITO electrodes or the like for driving the liquid crystal from the viewpoint of simplification of the process. In addition, as for the reflective liquid crystal display element, if it is only a single-sided substrate, an opaque material such as a silicon wafer can be used, and a light-reflecting material such as aluminum can also be used as the electrode in this case.
液晶配向劑之塗佈方法並無特別限定,工業上通常為網板印刷、平板印刷、柔版印刷、噴墨法等。作為其他的塗佈方法有浸漬法、輥塗佈法、縫塗佈法、旋轉器法、噴霧法等,亦可因應目的來使用該等。 The coating method of the liquid crystal alignment agent is not particularly limited, and industrially, it is usually screen printing, lithographic printing, flexographic printing, inkjet method, and the like. As another coating method, there exist a dipping method, a roll coating method, a slit coating method, a spinner method, a spray method, etc., and these can also be used according to the objective.
將液晶配向劑塗佈至基板上後的燒成,係可藉由加熱板、熱風循環爐、紅外線爐等的加熱手段以50℃~300℃,較佳以80℃~250℃下進行使溶劑蒸發,從而形成塗膜(液晶配向膜)。燒成後所形成的塗膜的厚度若過厚時,則就液晶顯示元件的消耗電力方面為不利,若過薄時,則將會有液晶顯示元件的可靠性降低之情形,因此較佳為5nm~300nm,又較佳為10nm~100nm。使液晶水平配向或傾斜配向時,利用摩擦或偏光紫外線照射等來處理燒成後的塗膜。 Firing after coating the liquid crystal aligning agent on the substrate can be carried out at 50°C to 300°C, preferably 80°C to 250°C by heating means such as a hot plate, hot air circulation furnace, and infrared furnace. Evaporated to form a coating film (liquid crystal alignment film). If the thickness of the coating film formed after firing is too thick, it will be disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may decrease, so it is preferable to use 5 nm to 300 nm, preferably 10 nm to 100 nm. When aligning a liquid crystal horizontally or diagonally, the coating film after baking is processed by rubbing, polarized ultraviolet irradiation, or the like.
將液晶配向劑塗佈至基板上後,藉由加熱板、熱循環型烘箱、IR(紅外線)型烘箱等的加熱手段,使溶劑蒸發並進行燒成。塗佈液晶配向劑後的乾燥、燒成步驟係可選擇任意的溫度與時間。通常為了充分地除去所含有的溶劑,可舉出以50℃~120℃下燒成1分~10分,之後, 以150℃~300℃下燒成5分~120分之條件。 After apply|coating a liquid crystal aligning agent to a board|substrate, it bakes by evaporating a solvent by heating means, such as a hotplate, a thermal cycle type oven, and an IR (infrared) type oven. The drying and firing steps after coating the liquid crystal aligning agent can select any temperature and time. Usually, in order to sufficiently remove the contained solvent, firing at 50°C to 120°C for 1 minute to 10 minutes, and then, Firing at 150°C to 300°C for 5 minutes to 120 minutes.
本發明之液晶配向膜係適合作為IPS方式或FFS方式等的橫電場方式之液晶顯示元件之液晶配向膜,特別是作為FFS方式之液晶顯示元件之液晶配向膜為有用。 The liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film for a liquid crystal display element of a lateral electric field method such as an IPS method or an FFS method, and is particularly useful as a liquid crystal alignment film for a liquid crystal display element of the FFS method.
本發明之液晶顯示元件係具備上述之液晶配向膜者,且得到由上述之液晶配向劑所得之附有液晶配向膜的基板後,利用已知的方法來製作液晶晶胞,並使用該液晶晶胞來製成元件。若舉出一例子,則為具備下述液晶晶胞之液晶顯示元件,該液晶晶胞具有:對向配置的2片基板、設置在基板間的液晶層、與設置在基板和液晶層之間的藉由本發明之液晶配向劑所形成的液晶配向膜。 The liquid crystal display element of the present invention is provided with the above-mentioned liquid crystal alignment film, and after obtaining the substrate with the liquid crystal alignment film obtained from the above-mentioned liquid crystal alignment agent, a liquid crystal cell is produced by a known method, and the liquid crystal crystal is used. cells to make components. As an example, it is a liquid crystal display element including a liquid crystal cell having two substrates arranged to face each other, a liquid crystal layer provided between the substrates, and a liquid crystal layer provided between the substrates and the liquid crystal layer. The liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention.
作為使用於本發明之液晶顯示元件的基板,只要是透明性高的基板即可,並無特別限定,通常是在基板上形成用於驅動液晶的透明電極的基板。作為具體例,可舉出與上述之液晶配向膜中記載的基板為相同者。 The substrate used for the liquid crystal display element of the present invention is not particularly limited as long as it is a substrate with high transparency, and is usually a substrate in which a transparent electrode for driving liquid crystal is formed on the substrate. As a specific example, the same thing as the board|substrate described in the above-mentioned liquid crystal alignment film can be mentioned.
又,液晶配向膜係藉由在該基板上塗佈本發明之液晶配向劑後進行燒成而形成的,詳細內容係如上述般。 In addition, the liquid crystal alignment film is formed by coating the liquid crystal alignment agent of the present invention on the substrate, followed by firing, and the details are as described above.
構成本發明之液晶顯示元件的液晶層的液晶材料並無特別限定,可舉出向列型液晶及層列型液晶,其中以向列型液晶為較佳,亦可使用正型液晶材料或負型液 晶材料中任一種。具體而言,可使用例如Merck公司製的MLC-2003、MLC-6608、MLC-6609、MLC-3019、MLC-2041、MLC-7026-100等。 The liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited, and examples thereof include nematic liquid crystal and smectic liquid crystal, among which nematic liquid crystal is preferred, and positive liquid crystal material or negative liquid crystal material can also be used. Type fluid any of the crystalline materials. Specifically, for example, MLC-2003, MLC-6608, MLC-6609, MLC-3019, MLC-2041, and MLC-7026-100 manufactured by Merck can be used.
具體而言,準備透明的玻璃製的基板,在一片的基板上設置共用電極,在另一片的基板上設置節段電極。該等的電極例如可製成ITO電極,被圖型化以能夠成為所期望的畫面顯示。接下來,在各基板上設置絕緣膜來被覆共用電極與節段電極。絕緣膜例如可以製成由經溶膠-凝膠法所形成的SiO2-TiO2所成的膜。接下來,依如前述般的條件在各基板上形成液晶配向膜。 Specifically, transparent glass substrates are prepared, common electrodes are provided on one substrate, and segment electrodes are provided on the other substrate. These electrodes can be made of, for example, ITO electrodes, and are patterned so that a desired screen display can be achieved. Next, an insulating film is provided on each substrate to cover the common electrode and the segment electrode. The insulating film can be made of, for example, a film of SiO 2 -TiO 2 formed by a sol-gel method. Next, a liquid crystal alignment film was formed on each substrate under the conditions as described above.
接下來,在已形成液晶配向膜的2片基板中之一片基板上的指定位置,配置例如紫外線硬化性的密封材,進而在液晶配向膜面上指定的數個位置配置液晶後,藉由以液晶配向膜呈對向之方式貼合另一片基板並壓黏,將液晶推開擴散至液晶配向膜之前面後,藉由對基板的全部照射紫外線並硬化密封材,從而得到液晶晶胞。 Next, a UV-curable sealing material, for example, is arranged at a specified position on one of the two substrates on which the liquid crystal alignment film has been formed, and then liquid crystals are arranged at specified positions on the surface of the liquid crystal alignment film. The liquid crystal alignment film is attached to another substrate in an opposite manner and pressure-bonded, and the liquid crystal is pushed away and diffused to the front and rear of the liquid crystal alignment film.
或者,作為在基板上形成液晶配向膜後之步驟,在一片基板上指定的位置設置密封材時,事先設置能夠從外部填充液晶的開口部,不配置液晶而貼合基板後,經由在密封材設置的開口部向液晶晶胞內注入液晶材料,利用接著劑密封該開口部從而得到液晶晶胞。接著,對於液晶材料的注入,可使用真空注入法、亦可使用在大氣中利用毛細管現象之方法。 Alternatively, as a step after forming a liquid crystal alignment film on a substrate, when a sealing material is provided at a predetermined position on one substrate, an opening that can be filled with liquid crystal from the outside is provided in advance, and the substrate is bonded without arranging the liquid crystal, and the sealing material is passed through the sealing material. The provided opening is injected with a liquid crystal material into the liquid crystal cell, and the opening is sealed with an adhesive to obtain a liquid crystal cell. Next, for the injection of the liquid crystal material, a vacuum injection method or a method utilizing a capillary phenomenon in the atmosphere may be used.
即使是上述之任一方法,為了確保在液晶晶 胞內液晶材料所填充的空間,以採用在一片基板上設置柱狀的突起、或在一片基板上散布間隔件、或在密封材混入間隔件、或組合該等的手段為較佳。 Even with any of the above methods, in order to ensure The space filled with the intracellular liquid crystal material is preferably by means of providing columnar protrusions on one substrate, dispersing spacers on one substrate, mixing spacers in a sealing material, or a combination of these.
接下來,進行偏光板的設置。具體而言,以在與2片基板的液晶層為相反側的表面上黏貼一對偏光板為較佳。 Next, set up the polarizer. Specifically, it is preferable to stick a pair of polarizers on the surfaces on the opposite side to the liquid crystal layers of the two substrates.
尚,本發明之液晶配向膜及液晶顯示元件,只要是使用本發明之液晶配向劑,並不被限定於上述之記載,亦可利用其他周知的手法來製作。從液晶配向劑至得到液晶顯示元件之步驟,除了例如日本特開2015-135393號公報的段落[0148]~段落[0149]等的以外,很多的文獻中亦有揭示。 Furthermore, the liquid crystal alignment film and the liquid crystal display element of the present invention are not limited to the above descriptions, as long as the liquid crystal alignment agent of the present invention is used, and other well-known methods can also be used. The steps from a liquid crystal aligning agent to obtaining a liquid crystal display element are also disclosed in many documents, in addition to, for example, paragraphs [0148] to [0149] of JP 2015-135393 A.
如以上般之方式,使用本發明之液晶配向劑所製作的液晶顯示元件係可靠性為優異,故可適合利用於大畫面且高精細的液晶電視等。 As described above, since the liquid crystal display element produced using the liquid crystal aligning agent of the present invention is excellent in reliability, it can be suitably used for large-screen and high-definition liquid crystal televisions and the like.
以下對於本發明之製造方法之詳細,以列舉檢討原料之組成或調配比率之實驗方法及其結果,以及典型的製造方法之實施例等來進行說明,但本發明並不被限定於該等的實施例中。 The details of the production method of the present invention will be described below by citing an experimental method for examining the composition or mixing ratio of raw materials and the results thereof, as well as examples of typical production methods, etc., but the present invention is not limited to these. in the examples.
尚,化合物或溶劑之縮寫、及特性評估之方法係如以下般。 Furthermore, the abbreviations of compounds or solvents, and the methods of property evaluation are as follows.
NMP:N-甲基-2-吡咯啶酮 NMP: N-methyl-2-pyrrolidone
NEP:N-乙基-2-吡咯啶酮 NEP: N-ethyl-2-pyrrolidone
GBL:γ-丁內酯 GBL: gamma-butyrolactone
BCS:丁基溶纖劑 BCS: Butyl Cellosolve
PB:丙二醇單丁基醚 PB: Propylene glycol monobutyl ether
DME:二丙二醇二甲基醚 DME: Dipropylene glycol dimethyl ether
DAA:4-羥基-4-甲基-2-戊酮 DAA: 4-Hydroxy-4-methyl-2-pentanone
DEDG:二乙二醇二乙基醚 DEDG: Diethylene glycol diethyl ether
DIBK:2,6-二甲基-4-庚酮 DIBK: 2,6-Dimethyl-4-heptanone
DIPE:二異丙基醚 DIPE: Diisopropyl ether
DIBC:2,6-二甲基-4-庚醇 DIBC: 2,6-Dimethyl-4-heptanol
Pd/C:鈀碳 Pd/C: Palladium on carbon
DMSO:二甲基亞碸 DMSO: dimethyl sulfoxide
THF:四氫呋喃 THF: Tetrahydrofuran
LS-4668:3-縮水甘油氧基丙基三乙氧基矽烷 LS-4668: 3-Glycidoxypropyltriethoxysilane
LS-3150:3-胺基丙基三乙氧基矽烷 LS-3150: 3-Aminopropyltriethoxysilane
裝置:Varian NMR system 400NB(400MHz)(Varian公司製)、及JMTC-500/54/SS(500MHz)(JEOL公司製) Apparatus: Varian NMR system 400NB (400MHz) (manufactured by Varian), and JMTC-500/54/SS (500MHz) (manufactured by JEOL)
測定溶劑:CDCl3(氘化氯仿),DMSO-d6(氘化二甲基亞碸) Assay solvent: CDCl 3 (deuterated chloroform), DMSO-d 6 (deuterated dimethyl sulfoxide)
基準物質:TMS(四甲基矽烷)(δ:0.0ppm,1H)及CDCl3(δ:77.0ppm,13C) Reference material: TMS (tetramethylsilane) (δ: 0.0ppm, 1H) and CDCl 3 (δ: 77.0ppm, 1 3 C)
使用常溫凝膠滲透色譜法(GPC)裝置(GPC-101)(昭和電工公司製)、及管柱(KD-803,KD-805)(Shodex公司製),依以下之條件來進行測定。 The measurement was performed under the following conditions using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko Corporation) and columns (KD-803, KD-805) (manufactured by Shodex Corporation).
管柱溫度:50℃ Column temperature: 50℃
溶離劑:N,N’-二甲基甲醯胺(作為添加劑,溴化鋰-水合物(LiBr‧H2O)為30mmol/L(公升)、磷酸酐結晶(o-磷酸)為30mmol/L、四氫呋喃(THF)為10ml/L) Solvent: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr·H 2 O) is 30 mmol/L (liter), phosphoric anhydride crystal (o-phosphoric acid) is 30 mmol/L, Tetrahydrofuran (THF) is 10ml/L)
流速:1.0ml/分 Flow rate: 1.0ml/min
檢量線作成用標準樣品:TSK標準聚環氧乙烷(分子量:約900,000、150,000、100,000、及30,000、Tosoh公 司製)及聚乙二醇(分子量:約12,000、4,000、及1,000、Polymer Laboratories公司製) Standard sample for calibration line preparation: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, and 30,000, Tosoh Co., Ltd. Company) and polyethylene glycol (molecular weight: about 12,000, 4,000, and 1,000, manufactured by Polymer Laboratories)
後述之合成例及比較合成例中,聚醯胺酸溶液的黏度係使用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)下來進行測定。 In the synthesis examples and comparative synthesis examples to be described later, the viscosity of the polyamide acid solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), with a sample volume of 1.1 mL and a conical rotor TE-1 (1°34). ', R24) down to measure.
在2L(公升)的四頸燒瓶中,裝入BNPU(50g,140mmol)、碳酸鉀(44.4g,320mmol)、及NMP(1000g),於翼攪拌下昇溫至50℃,以10分鐘滴入40%乙二醛水溶液(46.7g,320mmol)並攪拌12小時。藉由HPLC(高效液相層析)由於原料殘留,故進而加入碳酸鉀(44.4g,320mmol)、及40%乙二醛水溶液(46.7g,320mmol),並攪拌12小時從而得到化合物[A]。確認原料消失後,過濾鹽並滴入硫酸(15g),將溶液設成為酸性後,藉由70℃下攪拌24小時。藉由HPLC確認反應結束後,加入甲醇(1000g)、純水(1000g),以5℃下冷卻後並攪拌1小時。將析出的結晶進行減壓過濾,利用甲醇(100g)洗淨後,進行乾燥從而得到 粉末結晶(化合物[B])(收量41.7g,收率76%)。 In a 2L (liter) four-necked flask, BNPU (50g, 140mmol), potassium carbonate (44.4g, 320mmol), and NMP (1000g) were charged, the temperature was raised to 50°C under wing stirring, and 40°C was added dropwise over 10 minutes. % Aqueous glyoxal solution (46.7 g, 320 mmol) and stirred for 12 hours. Since the raw material remained by HPLC (high performance liquid chromatography), potassium carbonate (44.4 g, 320 mmol) and a 40% glyoxal aqueous solution (46.7 g, 320 mmol) were further added, and stirred for 12 hours to obtain compound [A] . After confirming the disappearance of the raw materials, the salt was filtered, and sulfuric acid (15 g) was added dropwise, and the solution was made acidic, followed by stirring at 70° C. for 24 hours. After confirming completion of the reaction by HPLC, methanol (1000 g) and pure water (1000 g) were added, and the mixture was cooled at 5°C and stirred for 1 hour. The precipitated crystals were filtered under reduced pressure, washed with methanol (100 g), and then dried to obtain Powder crystal (compound [B]) (yield 41.7 g, yield 76%).
1H-NMR(DMSO-d6):8.18-8.10(4H,m),7.56-7.50(2H,m),7.45-7.39(2H,m),3.95(2H,s),3.62-3.55(4H,m),2.97-2.91(4H,m) 1 H-NMR (DMSO-d6): 8.18-8.10(4H,m), 7.56-7.50(2H,m), 7.45-7.39(2H,m), 3.95(2H,s), 3.62-3.55(4H, m),2.97-2.91(4H,m)
將所得之化合物[B](35g、87.8mmol)、5質量%Pd/C(50%含水型)、特性白鷺活性碳(3.5g)、及二噁烷(350g)的混合物,在氫加壓條件下以60℃攪拌8小時。反應結束後,將觸媒過濾後進行濃縮,加入2-丙醇(350g),以5℃下攪拌1小時。將析出的結晶進行減壓過濾,利用2-丙醇(70g)洗淨後,進行乾燥從而得到粉末結晶DA-1(收量27g,收率92%)。 A mixture of the obtained compound [B] (35 g, 87.8 mmol), 5 mass % Pd/C (50% aqueous type), characteristic egret activated carbon (3.5 g), and dioxane (350 g) was pressurized under hydrogen The mixture was stirred at 60°C for 8 hours. After completion of the reaction, the catalyst was filtered and concentrated, 2-propanol (350 g) was added, and the mixture was stirred at 5°C for 1 hour. The precipitated crystals were filtered under reduced pressure, washed with 2-propanol (70 g), and then dried to obtain powder crystals DA-1 (27 g in yield, 92% in yield).
1H-NMR(DMSO-d6):6.87-6.84(2H,m),6.81-6.77(2H,m),6.51-6.46(4H,m),4.90(4H,s),3.79(2H,s),3.45-3.38(4H,m),2.62-2.57(4H,m) 1 H-NMR(DMSO-d6): 6.87-6.84(2H,m), 6.81-6.77(2H,m), 6.51-6.46(4H,m), 4.90(4H,s), 3.79(2H,s) ,3.45-3.38(4H,m),2.62-2.57(4H,m)
在附有攪拌裝置及氮導入管的100mL的四頸燒瓶中加入所得之DA-1(3.38g,10.0mmol)後,再加入NMP28.8g,一邊送入氮一邊攪拌使其溶解。一邊攪拌該溶液,一邊加 入CA-1(0.87g,4.0mmol)、CA-2(1.08g,5.5mmol)、及NMP 9.6g後,進而藉由以50℃條件下攪拌12小時,從而得到下述表1所表示之聚醯胺酸溶液(PAA-A1)。 The obtained DA-1 (3.38 g, 10.0 mmol) was added to a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, followed by adding 28.8 g of NMP, and stirring to dissolve it while feeding nitrogen. While stirring the solution, add After adding CA-1 (0.87 g, 4.0 mmol), CA-2 (1.08 g, 5.5 mmol), and NMP 9.6 g, it was further stirred at 50° C. for 12 hours to obtain the following Table 1. Polyamide solution (PAA-A1).
除了使用下述表1所表示之二胺成分、四羧酸成分、及NMP(N-甲基-2-吡咯啶酮)並分別設定反應溫度以外,藉由與合成例1相同地實施,從而可得到下述表1所表示之聚醯胺酸溶液(PAA-A2)及聚醯胺酸溶液(PAA-B1)~(PAA-B3)。 It was carried out in the same manner as in Synthesis Example 1, except that the diamine component, the tetracarboxylic acid component, and NMP (N-methyl-2-pyrrolidone) shown in the following Table 1 were used and the reaction temperatures were set respectively. The polyamic acid solutions (PAA-A2) and the polyamic acid solutions (PAA-B1) to (PAA-B3) shown in the following Table 1 were obtained.
以所得之液晶配向劑中之溶劑成為如下述表2及下述表3所表示之組成般,一邊攪拌將合成例1~合成例5所得之聚醯胺酸溶液,一邊加入溶劑及添加劑,進而藉由在室溫下攪拌2小時,從而分別得到液晶配向劑。 So that the solvent in the obtained liquid crystal aligning agent becomes the composition shown in the following Table 2 and the following Table 3, while stirring the polyamide solution obtained in Synthesis Example 1 to Synthesis Example 5, the solvent and additives are added, and then By stirring at room temperature for 2 hours, a liquid crystal aligning agent was obtained, respectively.
尚,表2及表3的※1~※3係如以下所表示般。 However, *1 to *3 in Table 2 and Table 3 are as follows.
※1:表示相對於全部的聚合物100重量份之各聚合物的導入量(重量份)。 *1: Indicates the introduction amount (parts by weight) of each polymer with respect to 100 parts by weight of the total polymer.
※2:表示相對於全部的聚合物100重量份之各添加劑的導入量(重量份)。 *2: Indicates the introduction amount (parts by weight) of each additive with respect to 100 parts by weight of the total polymer.
※3:表示相對於液晶配向劑100質量份之溶劑的導入量(重量份)。 *3: Indicates the introduction amount (parts by weight) of the solvent with respect to 100 parts by mass of the liquid crystal aligning agent.
準備30mm×35mm的大小、且厚度為0.7mm的附有電極的玻璃基板。在基板上作為第1層形成了構成對向電極之 具備實心狀圖型的IZO電極。在第1層的對向電極之上,作為第2層形成了藉由CVD法所成膜的SiN(氮化矽)膜。第2層的SiN膜的膜厚為500nm,其作為層間絕緣膜發揮功能。在第2層的SiN膜之上,作為第3層配置將IZO膜圖型化所形成的梳齒狀的像素電極,從而形成第1像素及第2像素這2個像素。各像素的尺寸是長10mm且寬5mm。此時,第1層的對向電極與第3層的像素電極係因第2層的SiN膜之作用而電絕緣。 A glass substrate with electrodes having a size of 30 mm×35 mm and a thickness of 0.7 mm was prepared. On the substrate, as the first layer, a structure that constitutes the counter electrode is formed. IZO electrodes with solid pattern. On the counter electrode of the first layer, a SiN (silicon nitride) film formed by a CVD method was formed as a second layer. The thickness of the SiN film of the second layer is 500 nm, and it functions as an interlayer insulating film. On the SiN film of the second layer, a comb-shaped pixel electrode formed by patterning an IZO film is arranged as a third layer, thereby forming two pixels, a first pixel and a second pixel. The size of each pixel is 10 mm in length and 5 mm in width. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer.
第3層的像素電極係如日本特開2014-77845號公報記載的圖(圖3)所表示,具有排列多個中央部分彎曲的“ㄑ”字形狀的電極要素所構成的梳齒狀的形狀。各電極要素的寬度方向的寬為3μm,電極要素間的間隔為6μm。形成各像素的像素電極係由排列多個中央部分彎曲的“ㄑ”字形狀的電極要素所構成,因此各像素的形狀不是長方形,而是具備與電極要素相同地在中央部分彎曲、且與粗體的“ㄑ”字相似的形狀。而且,各像素係以其中央的彎曲部分為界線被上下分割,具有彎曲部分的上側的第1區域與下側的第2區域。 The pixel electrode of the third layer has a comb-like shape formed by arranging a plurality of electrode elements having a “ㄑ” shape with a curved center portion, as shown in the figure ( FIG. 3 ) described in Japanese Patent Application Laid-Open No. 2014-77845 . The width of each electrode element in the width direction was 3 μm, and the interval between the electrode elements was 6 μm. The pixel electrode that forms each pixel is composed of a plurality of electrode elements having a “ㄑ” shape with a curved center portion arranged in a row. Therefore, the shape of each pixel is not a rectangle, but has the same shape as the electrode element that is curved in the center portion and has a thickness similar to that of the electrode element. The shape of the "ㄑ" character of the body is similar. Further, each pixel is divided up and down with the curved portion in the center as a boundary, and has a first area on the upper side and a second area on the lower side of the curved portion.
若比較各像素的第1區域與第2區域時,則構成此等的像素電極的電極要素的形成方向為不同。即,將後述之液晶配向膜的摩擦方向作為基準時,像素的第1區域中,像素電極的電極要素係以成為+ 10°的角度(順時針)之方式形成,像素的第2區域中,像素電極的電極要素係以成為-10°的角度(順時針)之方式形成。又,各像素的第1 區域與第2區域中,以藉由像素電極與對向電極之間的電壓外加而誘發的液晶的、在基板面內的旋轉動作(In-plane switching)的方向互為相反方向之方式來構成。 When the first region and the second region of each pixel are compared, the formation directions of the electrode elements constituting these pixel electrodes are different. That is, when the rubbing direction of the liquid crystal alignment film described later is used as a reference, in the first region of the pixel, the electrode elements of the pixel electrode are formed at an angle of +10° (clockwise), and in the second region of the pixel, The electrode elements of the pixel electrode are formed at an angle of -10° (clockwise). In addition, the first In the region and the second region, the directions of the in-plane switching (In-plane switching) of the liquid crystal induced by the application of the voltage between the pixel electrode and the counter electrode are opposite to each other. .
接下來,利用1.0μm的過濾器過濾液晶配向劑後,分別旋轉塗佈在上述附有電極的基板與作為對向基板在背面成膜有ITO膜、且具有高度為4μm的柱狀間隔件的玻璃基板上。接下來,在80℃的加熱板上乾燥5分鐘後,以230℃下燒成20分鐘,在各基板上得到膜厚60nm的聚醯亞胺膜。對該聚醯亞胺膜面,以輥徑120mm、輥旋轉數500rpm、平台移動速度30mm/sec、摩擦布壓入壓0.3mm的條件下,藉由嫘縈布施予摩擦處理後,經在純水中進行1分鐘超音波照射,再以80℃下乾燥10分鐘。 Next, after filtering the liquid crystal aligning agent with a 1.0 μm filter, spin-coating was performed on the above-mentioned substrate with electrodes and on the opposite substrate, on the back surface of which an ITO film was formed, and a columnar spacer having a height of 4 μm was formed. on the glass substrate. Next, after drying on a hot plate at 80° C. for 5 minutes, it was fired at 230° C. for 20 minutes to obtain a polyimide film having a thickness of 60 nm on each substrate. The polyimide film surface was subjected to a rubbing treatment with a rayon cloth under the conditions of a roller diameter of 120 mm, a roller rotation speed of 500 rpm, a platform moving speed of 30 mm/sec, and a rubbing cloth pressing pressure of 0.3 mm. Ultrasonic irradiation was performed in water for 1 minute, followed by drying at 80°C for 10 minutes.
使用2種類上述附有液晶配向膜的基板,以分別的摩擦方向為反向平行之方式來組合,將周圍密封但留下液晶注入口,製作晶胞間隙為3.8μm的空晶胞。向該空晶胞在常溫下真空注入液晶(Merck公司製、MLC-3019)後,將注入口密封製成反平行配向的液晶晶胞。所得之液晶晶胞係構成FFS模式液晶顯示元件。之後,以120℃下加熱液晶晶胞1小時,放置一晚後使用於評估中。 Two types of substrates with liquid crystal alignment films as described above were used, and the respective rubbing directions were anti-parallel, and the periphery was sealed but the liquid crystal injection port was left to produce an empty cell with a cell gap of 3.8 μm. After the liquid crystal (Merck Corporation make, MLC-3019) was vacuum-injected into this empty cell at normal temperature, the injection port was sealed to obtain an antiparallel alignment liquid crystal cell. The obtained liquid crystal cell system constitutes an FFS mode liquid crystal display element. Then, the liquid crystal cell was heated at 120° C. for 1 hour, and was used for evaluation after being left to stand overnight.
將製作的液晶晶胞設置於以偏光軸垂直之方式所配置的2片偏光板之間,在無外加電壓之狀態下點亮LED背光源,以透射光的亮度為最小之方式來調整液晶晶胞的配置 角度。接下來,一邊對該液晶晶胞外加周波數30Hz的交流電壓,一邊測定V-T曲線(電壓-透射率曲線),算出相對透射率為23%時的交流電壓來作為驅動電壓。 The fabricated liquid crystal cell is placed between two polarizers arranged in a way that the polarization axis is vertical, and the LED backlight is turned on under no applied voltage, and the brightness of the transmitted light is minimized to adjust the liquid crystal crystal. Cell configuration angle. Next, a V-T curve (voltage-transmittance curve) was measured while applying an AC voltage with a frequency of 30 Hz to the liquid crystal cell, and the AC voltage when the relative transmittance was 23% was calculated as a driving voltage.
對於閃爍等級的測定,將點亮的LED背光源暫時關燈並遮光放置72小時後,再次點亮LED背光源,在開始點亮背光源的同時,外加相對透射率達到23%且周波數為30Hz的交流電壓,使液晶晶胞驅動60分鐘並追蹤閃爍振幅。閃爍振幅係藉由光二極體及I-V變換放大器所連接的數據收集/數據記錄器開關單元34970A(Agilent technologies公司製)來讀取通過2片偏光板及其間的液晶晶胞之LED背光源的透射光。閃爍等級係依下述式[8]來算出。 For the measurement of flicker level, turn off the lighted LED backlight temporarily and place it in shading for 72 hours, then turn on the LED backlight again. The liquid crystal cell was driven for 60 minutes with an AC voltage of 30 Hz and the flicker amplitude was tracked. The flicker amplitude was read by a data collection/data logger switch unit 34970A (manufactured by Agilent technologies) connected to a photodiode and an I-V converter amplifier for the transmission of the LED backlight through the 2 polarizers and the liquid crystal cell in between Light. The flicker level is calculated according to the following formula [8].
閃爍等級(%)={閃爍振幅/(2×z)}×100‧‧‧[8] Flicker level (%)={flicker amplitude/(2×z)}×100‧‧‧[8]
式[8]中,z係利用數據收集/數據記錄器開關單元34970A所讀取的,通過相對透射率達到23%且周波數30Hz的交流電壓下進行驅動時的亮度的值。 In formula [8], z is a value of luminance when driven by an AC voltage with a relative transmittance of 23% and a frequency of 30 Hz, read by the data acquisition/data logger switch unit 34970A.
閃爍等級之評估係自開始點亮LED背光源及外加交流電壓之時刻起至經過60分鐘為止,閃爍等級維持在未滿3%時,定義為「○」(剛驅動開始後不易引起閃爍位移(flicker shift))。經60分鐘且閃爍等級達到3%以上時,定義為「×」(剛驅動開始後容易引起閃爍位移)來進行評估。 The evaluation of the flicker level is from the moment when the LED backlight is turned on and the AC voltage is applied to 60 minutes. When the flicker level is maintained at less than 3%, it is defined as "○" (it is not easy to cause flicker displacement just after the start of driving ( flicker shift)). When the flicker level reached 3% or more after 60 minutes, it was defined as "X" (flicker displacement is likely to occur immediately after the start of driving) and evaluated.
而且,依據上述之方法之閃爍等級之評估係以液晶晶胞的溫度在23℃的狀態之溫度條件下來進行。 Furthermore, the evaluation of the flicker level according to the above-mentioned method was performed under the temperature condition of the state that the temperature of the liquid crystal cell was 23°C.
關於使用上述實施例1、2、及比較例1、2的各液晶配向劑之液晶顯示元件,將上述所實施的殘影消去時間之評估、及剛驅動後之閃爍等級之評估的結果表示於下述表4。 Regarding the liquid crystal display elements using the liquid crystal aligning agents of the above-mentioned Examples 1 and 2 and Comparative Examples 1 and 2, the results of the evaluation of the afterimage erasing time and the evaluation of the flicker level immediately after driving are shown in Table 4 below.
如表4所示可得知般,使用實施例1及實施例2的液晶配向劑之液晶顯示元件,於剛驅動開始後不易引起閃爍位移。 As shown in Table 4, the liquid crystal display elements using the liquid crystal aligning agents of Examples 1 and 2 were less likely to cause flicker displacement immediately after the start of driving.
使用藉由本發明的二胺所得之液晶配向劑從而製作之液晶顯示元件,係可作為剛驅動開始後的閃爍位移為經減低之液晶顯示裝置,可適合被使用於藉由TN(Twisted Nematic)液晶顯示元件、STN液晶顯示元件、TFT液晶顯示元件、VA液晶顯示元件、IPS液晶顯示元件、OCB(Optically self-Compensated Birefringence)液晶顯示元件等各種的方式之顯示元件。 The liquid crystal display element produced by using the liquid crystal aligning agent obtained from the diamine of the present invention can be used as a liquid crystal display device in which the flicker displacement immediately after the start of driving is reduced, and can be suitably used for TN (Twisted Nematic) liquid crystal display devices. Display elements, STN liquid crystal display elements, TFT liquid crystal display elements, VA liquid crystal display elements, IPS liquid crystal display elements, OCB (Optically self-Compensated Birefringence) liquid crystal display elements and other types of display elements.
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