TW201500462A - Polymer, liquid crystal orientation treating agent, liquid crystal orientation film and liquid crystal display element - Google Patents
Polymer, liquid crystal orientation treating agent, liquid crystal orientation film and liquid crystal display element Download PDFInfo
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Abstract
Description
本發明係關於聚合物、在液晶顯示元件之製造中所使用的液晶配向處理劑、由該液晶配向處理劑所得之液晶配向膜及使用該液晶配向膜的液晶顯示元件者。 The present invention relates to a polymer, a liquid crystal alignment treatment agent used in the production of a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element using the liquid crystal alignment film.
作為與過去TN(Twisted Nematic)模式之液晶顯示元件相比具有優良的視野角特性之液晶顯示元件,已知有由寬視角所得之MVA(Multi-domain Vertical Alignment)模式。在MVA模式中使用具有負的介電常數各向異性之液晶、將液晶呈垂直配向之液晶配向膜、進一步控制液晶配向方向之配向控制用的結構物。而輸入電壓時,液晶會沿著配向控制用結構物,往垂直方向傾斜。然而,在MVA模式中配向控制用之結構物突起因形成於畫素內,故與TN模式等相比開口率變低,使得自背光的光透過率降低。 As a liquid crystal display element having excellent viewing angle characteristics as compared with a conventional TN (Twisted Nematic) mode liquid crystal display element, a MVA (Multi-domain Vertical Alignment) mode obtained from a wide viewing angle is known. In the MVA mode, a liquid crystal having a negative dielectric anisotropy, a liquid crystal alignment film in which the liquid crystal is vertically aligned, and a structure for controlling the alignment of the liquid crystal alignment direction are used. When the voltage is input, the liquid crystal is tilted in the vertical direction along the alignment control structure. However, in the MVA mode, since the structure protrusion for alignment control is formed in the pixel, the aperture ratio is lower than that in the TN mode or the like, and the light transmittance from the backlight is lowered.
對於此問題,在高光透過率下欲進一步加速液晶應答速度時,使用聚合物控制驅動時的液晶配向方向之方法已被提案(例如參照專利文獻1)。在該方法中, 於液晶使用混合藉由熱或紫外線照射進行聚合的聚合性化合物(亦稱為單體)之液晶材料。在該方法中,於基板間輸入電壓使液晶分子呈現傾斜狀態下,藉由熱或紫外線照射聚合單體形成聚合物(以上方法亦稱為PSA化處理)。藉此,即使無輸入電壓,亦可得到具有所定傾斜角(Pretilt angle)之液晶層,且高光透過率下液晶之應答速度可進一步加速的液晶顯示元件。 In order to further accelerate the liquid crystal response speed under high light transmittance, a method of controlling the liquid crystal alignment direction during driving using a polymer has been proposed (for example, see Patent Document 1). In the method, A liquid crystal material of a polymerizable compound (also referred to as a monomer) polymerized by heat or ultraviolet irradiation is used in the liquid crystal. In this method, when a voltage is applied between the substrates to cause the liquid crystal molecules to be tilted, the polymer is polymerized by heat or ultraviolet irradiation to form a polymer (the above method is also referred to as PSA treatment). Thereby, even if there is no input voltage, a liquid crystal layer having a predetermined tilt angle can be obtained, and the response speed of the liquid crystal at a high light transmittance can be further accelerated.
〔專利文獻1〕特開2003-149647號公報 [Patent Document 1] JP-A-2003-149647
在液晶顯示元件之製作中,於形成液晶配向膜的2片基板之間(晶胞間隙),填充液晶之步驟為必要。至今於液晶之填充係利用大氣壓與真空之壓力差,於2片基板間填充液晶之真空注入方式為一般方法。然而,現今以提高生產效率為目的,使用液晶滴落方式(ODF(One Drop Fill)方式)作為液晶之填充方法。 In the production of a liquid crystal display element, a step of filling a liquid crystal between two substrates (formation cell gap) in which a liquid crystal alignment film is formed is necessary. Up to now, in the filling of liquid crystals, a vacuum injection method in which liquid crystal is filled between two substrates is a general method using a pressure difference between atmospheric pressure and vacuum. However, in order to improve production efficiency, a liquid crystal dropping method (ODF (One Drop Fill) method) is used as a filling method of liquid crystal.
在ODF方式中,欲將液晶直接滴落於液晶配向膜上,必須於液晶滴落時對液晶配向膜施予物理性壓力,或於面板全區域填充液晶,故必須增加液晶滴落點。因此,於與液晶滴落部或液晶之液滴鄰接的液滴接觸部 分,會產生所謂滴落痕跡或格子不均勻之配向不均勻,將此作為液晶顯示元件時,會產生因配向不均勻所引起的顯示不均勻之問題。 In the ODF method, in order to directly drop the liquid crystal on the liquid crystal alignment film, it is necessary to apply physical pressure to the liquid crystal alignment film when the liquid crystal is dropped, or to fill the liquid crystal in the entire area of the panel, so it is necessary to increase the liquid crystal dropping point. Therefore, at the droplet contact portion adjacent to the droplet of the liquid crystal drop or the liquid crystal When the liquid crystal display element is used as a liquid crystal display element, display unevenness due to misalignment of the alignment occurs.
又,藉由構成液晶顯示元件之背光的照射加熱液晶顯示元件時,亦會有預傾角產生變化而產生顯示不良之問題。因此,對熱的高穩定性被要求。 Further, when the liquid crystal display element is heated by the irradiation of the backlight constituting the liquid crystal display element, there is a problem that the pretilt angle changes and display failure occurs. Therefore, high stability to heat is required.
於此本發明係以提供可改善液晶配向膜之配向不均勻,且預傾角耐熱性優良的聚合物、液晶配向處理劑、液晶配向膜及液晶顯示元件為目的。 The present invention has an object of providing a polymer, a liquid crystal alignment treatment agent, a liquid crystal alignment film, and a liquid crystal display element which are capable of improving the alignment unevenness of the liquid crystal alignment film and having excellent pretilt heat resistance.
本發明者進行詳細研究結果,發現含有選自將持有具有特定結構之四羧酸二酐的四羧酸成分與持有具有特定結構之二胺化合物的二胺成分進行反應所得之聚醯亞胺前驅物及該聚醯亞胺前驅物進行醯亞胺化所得之聚醯亞胺的至少1種聚合物之液晶配向處理劑可達成上述目的時極有效而完成本發明。 As a result of detailed investigation, the present inventors have found that a polyphthalocyanine obtained by reacting a tetracarboxylic acid component having a tetracarboxylic dianhydride having a specific structure with a diamine component having a diamine compound having a specific structure is obtained. The liquid crystal alignment treatment agent of at least one polymer of the polyimide precursor obtained by the ruthenium imidization of the amine precursor and the polyimide precursor is extremely effective in achieving the above object, and the present invention has been completed.
即,本發明為具有以下要旨者。 That is, the present invention has the following gist.
(1)一種液晶配向處理劑,其特徵為含有選自下述聚醯亞胺的至少1種聚合物者,該聚醯亞胺為將含有下述式〔1〕所示四羧酸二酐之四羧酸成分與含有具有下述式〔2〕所示側鏈的二胺化合物之二胺成分進行反應所得之聚醯亞胺前驅物及該聚醯亞胺前驅物經醯亞胺化所得者;
(2)前述四羧酸成分為含有下述式〔3〕所 示四羧酸酐者為特徵之上述(1)所記載的液晶配向處理劑。 (2) The tetracarboxylic acid component contains the following formula [3] The liquid crystal alignment treatment agent according to the above (1), which is characterized by the tetracarboxylic anhydride.
(3)作為液晶配向處理劑中之溶劑,含有N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮或γ-丁內酯者為特 徵之上述(1)或上述(2)所記載的液晶配向處理劑。 (3) As a solvent in the liquid crystal alignment treatment agent, it is characterized by containing N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone. The liquid crystal alignment treatment agent according to the above (1) or (2) above.
(4)作為液晶配向處理劑中之溶劑,含有選自下述式〔D-1〕~式〔D-3〕所示溶劑的溶劑之上述(1)~上述(3)中任一所記載的液晶配向處理劑。 (4) The solvent in the liquid crystal alignment agent containing any solvent (1) to (3) selected from the solvents of the formula [D-1] to the formula [D-3] Liquid crystal alignment treatment agent.
(5)使用上述(1)~上述(4)所記載的液晶配向處理劑而得為特徵之液晶配向膜。 (5) A liquid crystal alignment film which is characterized by using the liquid crystal alignment treatment agent according to the above (1) to (4).
(6)使用上述(1)~上述(4)所記載的液晶配向處理劑,以噴墨法而得為特徵之液晶配向膜。 (6) A liquid crystal alignment film characterized by an inkjet method using the liquid crystal alignment treatment agent according to the above (1) to (4).
(7)具有上述(5)或上述(6)所記載的液晶配向膜者為特徵之液晶顯示元件。 (7) A liquid crystal display element characterized by having the liquid crystal alignment film according to (5) or (6) above.
(8)如上述(5)或上述(6)所記載的液晶配向膜,其為使用於液晶顯示元件者,該液晶顯示元件為,於具備電極的一對基板之間具有液晶層所成,經由於前述一對基板之間配置含有藉由活性能量線及熱之至少一方進行聚合的聚合性化合物之液晶組成物,於前述電極間輸入電壓之同時,聚合前述聚合性化合物之步驟所製造。 (8) The liquid crystal alignment film according to the above (5) or (6), which is used for a liquid crystal display element, which is formed by a liquid crystal layer between a pair of substrates including electrodes. A liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and a step of polymerizing the polymerizable compound is performed while a voltage is input between the electrodes.
(9)一種液晶顯示元件,其特徵為具有上述(8)所記載的液晶配向膜。 (9) A liquid crystal display element comprising the liquid crystal alignment film according to (8) above.
(10)如上述(5)或上述(6)所記載的液晶配向膜,其為使用於液晶顯示元件,該液晶顯示元件為,於具備電極的一對基板之間具有液晶層所成,經由於前述一對基板之間配置含有藉由活性能量線及熱之至少一方進行聚合的聚合性基之液晶配向膜,於前述電極間輸入電壓之同時,聚合前述聚合性基之步驟所製造。 (10) The liquid crystal alignment film according to the above (5) or (6), which is used in a liquid crystal display device which has a liquid crystal layer formed between a pair of substrates having electrodes. A liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and a step of polymerizing the polymerizable group is performed while a voltage is input between the electrodes.
(11)一種液晶顯示元件,其特徵為具有上述(10)所記載的液晶配向膜。 (11) A liquid crystal display element comprising the liquid crystal alignment film according to (10) above.
(12)一種聚合物,其特徵為選自以下聚醯亞胺的至少1種所成者,該聚醯亞胺為將含有下述式〔1〕所示四羧酸二酐之四羧酸成分與含有具有下述式〔2〕所示側鏈之二胺化合物的二胺成分進行反應所得之聚醯亞胺前驅物及該聚醯亞胺前驅物經醯亞胺化所得者;
依據本發明,藉由使用選自含有將含有具有特定結構之四羧酸二酐之四羧酸成分與含有具有特定結構之側鏈的二胺化合物之二胺成分進行反應所得之聚醯亞胺前驅物及該聚醯亞胺前驅物經醯亞胺化所得之聚醯亞胺的至少1種聚合物之液晶配向處理劑時,可改善以ODF方式所製作之液晶顯示元件所產生的配向不均勻。特別採用PSA模式時,可使含於液晶顯示元件之聚合性化合物的分 散性均勻,可進一步改善配向不均勻。又,藉由使用本發明的液晶配向處理劑,可使其成為預傾角之耐熱性優良者。因此,具有本發明的液晶配向膜之液晶顯示元件不會有因配向不均勻所引起的配向缺陷,又因耐熱性優良,故可成為信賴性高之液晶顯示元件。 According to the present invention, a polyfluorene imine obtained by reacting a diamine component containing a tetracarboxylic acid component containing a tetracarboxylic dianhydride having a specific structure with a diamine compound having a side chain having a specific structure is used. When the precursor and the polyimine precursor are subjected to a liquid crystal alignment treatment agent of at least one polymer of the polyimine obtained by imidization, the alignment of the liquid crystal display element produced by the ODF method can be improved. Evenly. When the PSA mode is used in particular, the fraction of the polymerizable compound contained in the liquid crystal display element can be made. Uniform dispersion can further improve the uneven alignment. Moreover, by using the liquid crystal alignment treatment agent of the present invention, it is possible to make it excellent in heat resistance at a pretilt angle. Therefore, the liquid crystal display element having the liquid crystal alignment film of the present invention does not have an alignment defect due to uneven alignment, and is excellent in heat resistance, so that it can be a highly reliable liquid crystal display element.
本發明的液晶配向處理劑為含有選自以下經醯亞胺化所得之聚醯亞胺的至少一種聚合物(亦稱為特定聚合物),該聚醯亞胺係將由將含有下述式〔1〕所示四羧酸二酐(亦稱為特定四羧酸二酐)之四羧酸成分、與含有具有下述式〔2〕所示側鏈之二胺化合物(亦稱為特定側鏈型二胺化合物)之二胺成分進行反應所得之聚醯亞胺前驅物及該聚醯亞胺前驅物進行醯亞胺化而得。 The liquid crystal alignment treatment agent of the present invention is at least one polymer (also referred to as a specific polymer) containing a polyimine obtained by the following mercapto imidization, which will contain the following formula [ 1) a tetracarboxylic acid component of a tetracarboxylic dianhydride (also referred to as a specific tetracarboxylic dianhydride) and a diamine compound (also referred to as a specific side chain) having a side chain represented by the following formula [2]; The polyimine precursor obtained by reacting the diamine component of the type diamine compound and the polyimine precursor are obtained by imidization.
其中,所謂聚醯亞胺前驅物為聚醯胺酸(Polyamide acid)或聚醯胺酸烷基酯。聚醯亞胺前驅物係由四羧酸成分(例如四羧酸化合物、四羧酸二酐、二羧酸二鹵化物化合物、二羧酸二烷基酯化合物、二烷基酯二鹵化物化合物)與分子內具有2個1級或2級胺基之二胺化合物的二胺成分進行反應而得,聚醯亞胺可使該聚醯胺酸進行脫水閉環(醯亞胺化)、或者藉由將聚醯胺酸烷基酯進行加熱閉環(醯亞胺化)而得。此等聚醯胺酸、聚醯胺酸烷基酯及聚醯亞胺皆作為含於本發明的液晶配向劑之特定聚合物使用。 Among them, the polyimine precursor is polyamide acid or polyalkyl amide. The polyimine precursor is composed of a tetracarboxylic acid component (for example, a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a dicarboxylic acid dihalide compound, a dicarboxylic acid dialkyl ester compound, a dialkyl ester dihalide compound). a reaction with a diamine component of a diamine compound having two primary or secondary amine groups in the molecule, which can be subjected to dehydration ring closure (deuteration) or by borrowing It is obtained by heating and blocking a polyalkyl amide alkyl ester. These polyamines, polyalkyl amides and polyimines are all used as specific polymers contained in the liquid crystal alignment agent of the present invention.
含有本發明的液晶配向處理劑所含有之聚合物的原料之四羧酸成分的特定四羧酸二酐為下述式〔1〕所示四羧酸二酐。 The specific tetracarboxylic dianhydride of the tetracarboxylic acid component of the raw material of the polymer contained in the liquid crystal alignment agent of the present invention is a tetracarboxylic dianhydride represented by the following formula [1].
式〔1〕所示四羧酸二酐為全四羧酸成分中之20莫耳%~100莫耳%時為佳。其中亦以30莫耳%~70莫耳%為更佳。特佳為30莫耳%~50莫耳%。 The tetracarboxylic dianhydride represented by the formula [1] is preferably 20 mol% to 100 mol% of the tetracarboxylic acid component. It is also preferably 30% to 70% by mole. Particularly good is 30% by mole to 50% by mole.
本發明中,以不損害本發明之效果的範圍下,可將特定四羧酸二酐以外之其他四羧酸化合物(亦稱為其他四羧酸化合物)作為四羧酸成分併用。 In the present invention, other tetracarboxylic acid compounds (also referred to as other tetracarboxylic acid compounds) other than the specific tetracarboxylic dianhydride may be used in combination as a tetracarboxylic acid component insofar as the effects of the present invention are not impaired.
其中亦以使用下述式〔3〕所示四羧酸二酐或該四羧酸衍生物之四羧酸化合物及二羧酸二鹵化物化合物(皆總稱為其他四羧酸化合物)為佳。 Further, it is preferred to use a tetracarboxylic dianhydride represented by the following formula [3] or a tetracarboxylic acid compound and a dicarboxylic acid dihalide compound (all collectively referred to as other tetracarboxylic acid compounds) of the tetracarboxylic acid derivative.
式〔3a〕中,Z2~Z5表示氫原子、甲基、氯原子或苯環,各可相同或相異。 In the formula [3a], Z 2 to Z 5 represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different.
式〔3g〕中,Z6及Z7表示氫原子或甲基,各可相同或相異。 In the formula [3g], Z 6 and Z 7 represent a hydrogen atom or a methyl group, and each may be the same or different.
式〔3〕所示結構中,Z1由合成的容易度或製造聚合物時的聚合反應容易度來看,以式〔3a〕、式〔3c〕、式〔3d〕、式〔3e〕、式〔3f〕或式〔3g〕所示結構為佳。較佳為式〔3a〕、式〔3e〕、式〔3f〕或式〔 3g〕所示結構,特佳為式〔3e〕、式〔3f〕或式〔3g〕。 In the structure represented by the formula [3], Z 1 is represented by the formula [3a], the formula [3c], the formula [3d], the formula [3e], and the easiness of the synthesis or the ease of polymerization in the production of the polymer. The structure represented by the formula [3f] or the formula [3g] is preferred. The structure represented by the formula [3a], the formula [3e], the formula [3f] or the formula [3g] is preferably a formula [3e], a formula [3f] or a formula [3g].
本發明的液晶配向處理劑所含有之特定聚合物中之四羧酸成分,已不損害本發明的效果之範圍下,可使用特定四羧酸二酐及其他四羧酸化合物以外的四羧酸化合物。 The tetracarboxylic acid component other than the tetracarboxylic acid component in the specific polymer contained in the liquid crystal alignment agent of the present invention can be used without using the specific tetracarboxylic dianhydride and other tetracarboxylic acid compounds. Compound.
作為該具體例,可舉出以下所示四羧酸二酐、四羧酸化合物或二羧酸二鹵化物化合物。 Specific examples of the tetracarboxylic dianhydride, the tetracarboxylic acid compound or the dicarboxylic acid dihalide compound shown below are mentioned below.
即可舉出均苯四甲酸、2,3,6,7-萘四羧酸、1,2,5,6-萘四羧酸、1,4,5,8-萘四羧酸、2,3,6,7-蒽四羧酸、1,2,5,6-蒽四羧酸、3,3’,4,4’-聯苯基四羧酸、2,3,3’,4’-聯苯基四羧酸、雙(3,4-二羧基苯基)醚、3,3’,4,4’-二苯甲酮四羧酸、雙(3,4-二羧基苯基)碸、雙(3,4-二羧基苯基)甲烷、2,2-雙(3,4-二羧基苯基)丙烷、1,1,1,3,3,3-六氟-2,2-雙(3,4-二羧基苯基)丙烷、雙(3,4-二羧基苯基)二甲基矽烷、雙(3,4-二羧基苯基)二苯基矽烷、2,3,4,5-吡啶四羧酸、2,6-雙(3,4-二羧基苯基)吡啶、3,3’,4,4’-二苯基碸四羧酸、3,4,9,10-苝四羧酸或1,3-二苯基-1,2,3,4-環丁烷四羧酸。 Examples thereof include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2, 3,6,7-decanetetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4' -biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl) Bismuth, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2 - bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyl decane, bis(3,4-dicarboxyphenyl)diphenyl decane, 2,3, 4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4,9, 10-decanetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.
其他四羧酸化合物及上述四羧酸化合物為配合本發明的特定聚合物對溶劑之溶解性或液晶配向處理劑的塗布性、作為液晶配向膜時的液晶的配向性、電壓保持率、累積電荷等特性,可使用1種類或混合2種類以上使用。 The other tetracarboxylic acid compound and the tetracarboxylic acid compound are the solubility of a specific polymer of the present invention with respect to a solvent or a coating property of a liquid crystal alignment treatment agent, the alignment property of a liquid crystal when a liquid crystal alignment film is used, a voltage retention ratio, and an accumulated charge. Other characteristics can be used in one type or in a mixture of two or more types.
本發明的液晶配向處理劑所含有之聚合物的原料之二胺成分所含之特定側鏈二胺化合物為具有下述式〔2〕所示側鏈之二胺化合物。且,本說明書中,所謂二胺化合物之側鏈表示自結合2個胺基之結構分支出的結構。 The specific side chain diamine compound contained in the diamine component of the raw material of the polymer contained in the liquid crystal alignment agent of the present invention is a diamine compound having a side chain represented by the following formula [2]. Further, in the present specification, the side chain of the diamine compound means a structure branched from a structure in which two amine groups are bonded.
具有式〔2〕所示側鏈之二胺化合物為全二胺成分中之20莫耳%~70莫耳%者為佳。其中亦以20莫耳%~50莫耳%者為佳。特佳為20莫耳%~40莫耳%。 The diamine compound having a side chain represented by the formula [2] is preferably 20 mol% to 70 mol% of the total diamine component. Among them, 20% to 50% of the total is also preferred. Very good is 20% to 40% by mole.
式〔2〕中,Y1表示單鍵、-(CH2)a-(a為1~15的整數)、-O-、-CH2O-、-COO-或-OCO-。其中亦以原料的取得容易度或合成容易度來看,以單鍵、-(CH2)a-(a為1~15的整數)、-O-、-CH2O-或-COO-為佳。較佳為單鍵、-(CH2)a-(a為1~10的整數)、-O-、-CH2O-或-COO-。 In the formula [2], Y 1 represents a single bond, -(CH 2 ) a - (a is an integer of 1 to 15), -O-, -CH 2 O-, -COO- or -OCO-. Among them, in terms of ease of obtaining raw materials or ease of synthesis, a single bond, -(CH 2 ) a - (a is an integer of 1 to 15), -O-, -CH 2 O- or -COO- is good. It is preferably a single bond, -(CH 2 ) a - (a is an integer of 1 to 10), -O-, -CH 2 O- or -COO-.
式〔2〕中,Y2表示單鍵或-(CH2)b-(b為1~15的整數)。其中亦以單鍵或-(CH2)b-(b為1~10的整數)為佳。 In the formula [2], Y 2 represents a single bond or -(CH 2 ) b - (b is an integer of 1 to 15). Among them, a single bond or -(CH 2 ) b - (b is an integer of 1 to 10) is preferred.
式〔2〕中,Y3表示單鍵、-(CH2)c-(c為1~15的整數)、-O-、-CH2O-、-COO-或-OCO-。其中亦以合成的容易度來看,以單鍵、-(CH2)c-(c為1~15 的整數)、-O-、-CH2O-或-COO-為佳。較佳為單鍵、-(CH2)c-(c為1~10的整數)、-O-、-CH2O-或-COO-。 In the formula [2], Y 3 represents a single bond, -(CH 2 ) c - (c is an integer of 1 to 15), -O-, -CH 2 O-, -COO- or -OCO-. Among them, in terms of ease of synthesis, a single bond, -(CH 2 ) c - (c is an integer of 1 to 15), -O-, -CH 2 O- or -COO- is preferred. It is preferably a single bond, -(CH 2 ) c - (c is an integer of 1 to 10), -O-, -CH 2 O- or -COO-.
式〔2〕中,Y4表示選自苯環、環己烷環或雜環的2價環狀基,此等環狀基上的任意氫原子可由碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟之烷基、碳數1~3的含氟之烷氧基或氟原子所取代。且,Y4可為選自具有類固醇骨架之碳數17~51的有機基之2價有機基。其中亦以合成的容易度來看,以苯環、環己烷環或具有類固醇骨架之碳數17~51的有機基為佳。 In the formula [2], Y 4 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms and a carbon number. The alkoxy group of 1 to 3, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom is substituted. Further, Y 4 may be a divalent organic group selected from an organic group having a carbon number of 17 to 51 having a steroid skeleton. Among them, in view of ease of synthesis, an organic group having a benzene ring, a cyclohexane ring or a carbon number of 17 to 51 having a steroid skeleton is preferred.
式〔2〕中,Y5表示選自苯環、環己烷環或雜環的2價環狀基,此等環狀基上的任意氫原子可由碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟之烷基、碳數1~3的含氟之烷氧基或氟原子所取代。其中亦以苯環或環己烷環為佳。 In the formula [2], Y 5 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms and a carbon number. The alkoxy group of 1 to 3, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom is substituted. Among them, a benzene ring or a cyclohexane ring is preferred.
式〔2〕中,n表示0~4的整數。其中亦以原料的取得容易度或合成容易度來看,以0~3為佳。較佳為0~2。 In the formula [2], n represents an integer of 0 to 4. Among them, in view of ease of obtaining raw materials or ease of synthesis, it is preferable to use 0 to 3. It is preferably 0 to 2.
式〔2〕中,Y6表示碳數1~18的烷基、碳數1~18的含氟之烷基、碳數1~18的烷氧基或碳數1~18的含氟之烷氧基。其中亦以碳數1~18的烷基、碳數1~10的含氟之烷基、碳數1~18的烷氧基或碳數1~10的含氟之烷氧基為佳。較佳為碳數1~12的烷基或碳數1~12的烷氧基。特佳為碳數1~9的烷基或碳數1~9的烷 氧基。 In the formula [2], Y 6 represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkane having 1 to 18 carbon atoms. Oxygen. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferred. It is preferably an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.
作為式〔2〕中之Y1、Y2、Y3、Y4、Y5、Y6及n的較佳組合,可舉出與國際公開公報WO2011/132751的第13頁~34頁之表6~表47所揭示的(2-1)~(2-629)之相同組合。且在國際公開公報之各表中,本發明中之Y1~Y6以Y1~Y6表示,故Y1~Y6以Y1~Y6讀取。又,具有類固醇骨架之碳數12~25的有機基以具有類固醇骨架之碳數17~51的有機基讀取。 A preferred combination of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 and n in the formula [2] is shown in Tables 13 to 34 of International Publication WO2011/132751. 6~ The same combination of (2-1)~(2-629) disclosed in Table 47. Further, in the tables of the International Publications, Y 1 to Y 6 in the present invention are represented by Y1 to Y6, and thus Y1 to Y6 are read as Y 1 to Y 6 . Further, the organic group having a carbon number of 12 to 25 having a steroid skeleton is read with an organic group having a steroid number of 17 to 51 carbon atoms.
作為具有式〔2〕所示側鏈之二胺化合物的具體例,可舉出下述式〔2b-1〕~式〔2b-31〕所示二胺化合物。 Specific examples of the diamine compound having a side chain represented by the formula [2] include a diamine compound represented by the following formula [2b-1] to the formula [2b-31].
使用具有式〔2〕所示側鏈之二胺化合物的液 晶配向處理劑做成液晶配向膜時,可提高液晶之預傾角。此時,將提高此等效果為目的,上述二胺化合物中亦以使用式〔2b-1〕~式〔2b-13〕或式〔2b-22〕~〔2b-31〕所示二胺化合物為佳。較佳為式〔2b-1〕~式〔2b-12〕或式〔2b-22〕~式〔2b-29〕所示二胺化合物。又,欲進一步提高這些效果,這些二胺化合物以二胺成分全體之5莫耳%以上80莫耳%以下者為佳。較佳為由液晶配向處理劑之塗布性或作為液晶配向膜之電氣特性來看,這些二胺化合物為二胺成分全體之5莫耳%以上60莫耳%以下。 A liquid using a diamine compound having a side chain represented by the formula [2] When the crystal is formed into a liquid crystal alignment film to the treatment agent, the pretilt angle of the liquid crystal can be increased. In this case, for the purpose of improving the effects, the diamine compound represented by the formula [2b-1] to the formula [2b-13] or the formula [2b-22] to [2b-31] is also used in the above diamine compound. It is better. The diamine compound represented by the formula [2b-1] to the formula [2b-12] or the formula [2b-22] to the formula [2b-29] is preferred. Moreover, in order to further improve these effects, it is preferable that these diamine compounds are 5 mol% or more and 80 mol% or less of the whole diamine component. The diamine compound is preferably 5 mol% or more and 60 mol% or less of the entire diamine component, in view of the coatability of the liquid crystal alignment agent or the electrical properties of the liquid crystal alignment film.
具有前述式〔2〕所示側鏈之二胺化合物為配合特定聚合物對溶劑之溶解性或液晶配向處理劑之塗布性、作為液晶配向膜時的液晶配向性、電壓保持率、累積電荷等特性,可使用1種類或混合2種類以上使用。 The diamine compound having the side chain represented by the above formula [2] is suitable for the solubility of a specific polymer in a solvent or the coating property of a liquid crystal alignment treatment agent, liquid crystal alignment property, a voltage retention ratio, a cumulative charge, etc. when used as a liquid crystal alignment film. The characteristics can be used in one type or in a mixture of two or more types.
作為製作本發明的液晶配向處理劑所含有之特定聚合物的二胺成分,除可使用具有式〔2〕所示側鏈之二胺化合物以外,亦可使用公知二胺化合物。 As the diamine component of the specific polymer contained in the liquid crystal alignment agent of the present invention, a known diamine compound may be used in addition to the diamine compound having a side chain represented by the formula [2].
其中亦以使用具有下述式〔4a〕所示結構之二胺化合物為佳。 Among them, a diamine compound having a structure represented by the following formula [4a] is also preferred.
[化27]-(CH[化27]-(CH 22 )) aa -COOH [4a]-COOH [4a]
式〔4a〕中,a表示0~4的整數。其中亦以原料的取得容易度或合成容易度來看,0或1的整數為 佳。 In the formula [4a], a represents an integer of 0 to 4. In view of the ease of obtaining raw materials or the ease of synthesis, the integer of 0 or 1 is good.
作為具有式〔4a〕所示結構之二胺化合物,具體可舉出下述式〔4a-1〕所示二胺化合物。 Specific examples of the diamine compound having a structure represented by the formula [4a] include a diamine compound represented by the following formula [4a-1].
式〔4a-1〕中,a表示0~4的整數。其中亦以原料的取得容易度或合成容易度來看,0或1為佳。 In the formula [4a-1], a represents an integer of 0-4. Among them, 0 or 1 is preferable in terms of ease of obtaining raw materials or ease of synthesis.
式〔4a-1〕中,n表示1~4的整數。其中亦以合成的容易度來看以1為佳。 In the formula [4a-1], n represents an integer of 1 to 4. Among them, it is preferable to use 1 in terms of ease of synthesis.
製造前述式〔4a〕所示二胺化合物之方法並無特別限定,作為較佳方法可舉出下述所示者。作為一例,式〔4a-1〕所示二胺化合物係由合成下述式〔4a-A〕所示二硝基體化合物,再將該硝基還原後變換為胺基而得。 The method for producing the diamine compound represented by the above formula [4a] is not particularly limited, and preferred examples thereof include the following. As an example, the diamine compound represented by the formula [4a-1] is obtained by synthesizing a dinitro compound represented by the following formula [4a-A], and then converting the nitro group to an amine group.
將式〔4a-A〕所示二硝基體化合物之二硝基進行還原之方法並無特別限定,一般為乙酸乙酯、甲苯、四氫呋喃、二噁烷或醇系溶劑等溶劑中,將鈀-碳、氧化鉑、雷尼鎳、鉑黑、銠-氧化鋁或硫化鉑碳等作為觸媒使用,在氫氣、聯胺或氯化氫下進行反應之方法。 The method for reducing the dinitro group of the dinitro compound represented by the formula [4a-A] is not particularly limited, and is usually a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol solvent. A method in which carbon, platinum oxide, Raney nickel, platinum black, ruthenium-alumina or sulphide platinum carbon is used as a catalyst, and the reaction is carried out under hydrogen, hydrazine or hydrogen chloride.
作為前述式〔4a〕所示二胺化合物,可進一步舉出下述式〔4a-2〕~式〔4a-5〕所示二胺化合物。 Further, as the diamine compound represented by the above formula [4a], a diamine compound represented by the following formula [4a-2] to formula [4a-5] can be further mentioned.
式〔4a-2〕中,A1表示單鍵、-CH2-、-C2H4-、-C(CH3)2-、-CF2-、-C(CF3)2-、-O-、-CO-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-CH2O-、-OCH2-、-COO-、-OCO-、-CON(CH3)-或-N(CH3)CO-。其中亦以合成的容易度來看,以單鍵、-CH2-、-C(CH3)2-、-O-、-CO-、-NH-、-N(CH3)-、-CONH-、-NHCO-、 -COO-或-OCO-為佳。較佳為單鍵、-CH2-、-C(CH3)2-、-O-、-CO-、-NH-或-N(CH3)-。 In the formula [4a-2], A 1 represents a single bond, -CH 2 -, -C 2 H 4 -, -C(CH 3 ) 2 -, -CF 2 -, -C(CF 3 ) 2 -, - O-, -CO-, -NH-, -N(CH 3 )-, -CONH-, -NHCO-, -CH 2 O-, -OCH 2 -, -COO-, -OCO-, -CON(CH 3 )- or -N(CH 3 )CO-. Among them, in terms of ease of synthesis, a single bond, -CH 2 -, -C(CH 3 ) 2 -, -O-, -CO-, -NH-, -N(CH 3 )-, -CONH -, -NHCO-, -COO- or -OCO- is preferred. Preferred is a single bond, -CH 2 -, -C(CH 3 ) 2 -, -O-, -CO-, -NH- or -N(CH 3 )-.
式〔4a-2〕中,m1及m2各表示0~4的整數,且m1+m2表示1~4的整數。其中亦以m1+m2為1或2為佳。 In the formula [4a-2], m 1 and m 2 each represent an integer of 0 to 4, and m 1 + m 2 represents an integer of 1 to 4. It is also preferable that m 1 + m 2 is 1 or 2.
式〔4a-3〕中,m3及m4各表示1~5的整數。其中亦以合成的容易度來看,1或2為佳。 In the formula [4a-3], m 3 and m 4 each represent an integer of 1 to 5. Among them, 1 or 2 is preferable in terms of ease of synthesis.
式〔4a-4〕中,A2表示碳數1~5的直鏈或分支烷基。其中亦以碳數1~3的直鏈烷基為佳。 In the formula [4a-4], A 2 represents a linear or branched alkyl group having 1 to 5 carbon atoms. Among them, a linear alkyl group having 1 to 3 carbon atoms is preferred.
式〔4a-4〕中,m5表示1~5的整數。其中亦以1或2為佳。 In the formula [4a-4], m 5 represents an integer of 1 to 5. It is also preferably 1 or 2.
式〔4a-5〕中,A3表示單鍵、-CH2-、-C2H4-、-C(CH3)2-、-CF2-、-C(CF3)2-、-O-、-CO-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-CH2O-、-OCH2-、-COO-、-OCO-、-CON(CH3)-或-N(CH3)CO-。其中亦以單鍵、-CH2-、-C(CH3)2-、-O-、-CO-、-NH-、-CONH-、-NHCO-、-CH2O-、-OCH2-、-COO-或-OCO-為佳。較佳為-O-、-CO-、-NH-、-CONH-、-NHCO-、-CH2O-、-OCH2-、-COO-或-OCO-。 In the formula [4a-5], A 3 represents a single bond, -CH 2 -, -C 2 H 4 -, -C(CH 3 ) 2 -, -CF 2 -, -C(CF 3 ) 2 -, - O-, -CO-, -NH-, -N(CH 3 )-, -CONH-, -NHCO-, -CH 2 O-, -OCH 2 -, -COO-, -OCO-, -CON(CH 3 )- or -N(CH 3 )CO-. Among them, a single bond, -CH 2 -, -C(CH 3 ) 2 -, -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH 2 O-, -OCH 2 - , -COO- or -OCO- is preferred. Preferred are -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH 2 O-, -OCH 2 -, -COO- or -OCO-.
式〔4a-5〕中,m6表示1~4的整數。其中亦以合成的容易度來看,1為佳。 In the formula [4a-5], m 6 represents an integer of 1 to 4. Among them, in terms of ease of synthesis, 1 is preferred.
前述式〔4a-1〕~式〔4a-5〕所示二胺化合物以全二胺成分中之30莫耳%~80莫耳%者為佳,較佳為50莫耳%~80莫耳%者。 The diamine compound represented by the above formula [4a-1] to formula [4a-5] is preferably 30 mol% to 80 mol% of the total diamine component, preferably 50 mol% to 80 mol%. %By.
前述式〔4a-1〕~式〔4a-5〕所示二胺化合物為配合特定聚合物對溶劑之溶解性或液晶配向處理劑的塗布性、作為液晶配向膜時的液晶的配向性、電壓保持率、累積電荷等特性,可使用1種類或混合2種類以上使用。 The diamine compound represented by the above formula [4a-1] to formula [4a-5] is suitable for the solubility of a specific polymer in a solvent or the coating property of a liquid crystal alignment treatment agent, and the alignment property and voltage of a liquid crystal when used as a liquid crystal alignment film. The characteristics such as the retention ratio and the accumulated electric charge can be used in one type or in a mixture of two or more types.
作為製作本發明的液晶配向處理劑所含有之特定聚合物的二胺成分,使用下述式〔4b〕所示二胺化合物者為佳。 The diamine component of the specific polymer contained in the liquid crystal alignment agent of the present invention is preferably a diamine compound represented by the following formula [4b].
式〔4b〕中,Y表示選自下述式〔4b-1〕、式〔4b-2〕、式〔4b-3〕、或式〔4b-4〕的至少1種1價基,m表示0~4的整數,-(Y)m表示取代基Y有m個。 In the formula [4b], Y represents at least one monovalent group selected from the following formula [4b-1], formula [4b-2], formula [4b-3], or formula [4b-4], and m represents An integer of 0 to 4, -(Y) m indicates that there are m substituents Y.
式〔4b-1〕中,a表示0~4的整數。其中亦以原料的取得容易度或合成容易度來看,0或1的整數為 佳。 In the formula [4b-1], a represents an integer of 0-4. In view of the ease of obtaining raw materials or the ease of synthesis, the integer of 0 or 1 is good.
式〔4b-2〕中,Y7表示碳數8~22的烷基。 In the formula [4b-2], Y 7 represents an alkyl group having 8 to 22 carbon atoms.
式〔4b-3〕中,Y8及Y9各獨立表示碳數1~12的烴基。 In the formula [4b-3], Y 8 and Y 9 each independently represent a hydrocarbon group having 1 to 12 carbon atoms.
式〔4b-4〕中,Y10表示碳數1~8的烷基。 In the formula [4b-4], Y 10 represents an alkyl group having 1 to 8 carbon atoms.
製造前述式〔4b〕所示二胺化合物之方法並無特別限定,作為較佳方法,可舉出下述所示者。 The method for producing the diamine compound represented by the above formula [4b] is not particularly limited, and preferred examples thereof include the following.
作為一例,式〔4b〕所示二胺化合物係由合成下述式〔4b-A〕所示二硝基體化合物,再將該硝基進行還原後變換為胺基而得。 As an example, the diamine compound represented by the formula [4b] is obtained by synthesizing a dinitro compound represented by the following formula [4b-A], and then converting the nitro group to an amine group.
將式〔4b-A〕所示二硝基體化合物的二硝基進行還原之方法並無特別限制,一般為乙酸乙酯、甲苯、四氫呋喃、二噁烷或醇系溶劑等溶劑中,將鈀-碳、氧化鉑、雷尼鎳、鉑黑、銠-氧化鋁或硫化鉑碳等作為觸媒使用,在氫氣、聯胺或氯化氫下進行反應之方法。 The method for reducing the dinitro group of the dinitro compound represented by the formula [4b-A] is not particularly limited, and is usually a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol solvent. A method in which carbon, platinum oxide, Raney nickel, platinum black, ruthenium-alumina or sulphide platinum carbon is used as a catalyst, and the reaction is carried out under hydrogen, hydrazine or hydrogen chloride.
下述舉出前述式〔4b〕所示二胺化合物之具 體結構,但並未限定於此等例。 The following is a formula for the diamine compound represented by the above formula [4b]. The body structure is not limited to these examples.
即,作為式〔4b〕所示二胺化合物,可舉出m-伸苯基二胺、2,4-二甲基-m-伸苯基二胺、2,6-二胺基甲苯、2,4-二胺基酚、3,5-二胺基酚、3,5-二胺基苯甲基醇、2,4-二胺基苯甲基醇、4,6-二胺基間苯二酚以外,亦可舉出下述式〔4b-6〕~〔4b-15〕所示結構之二胺化合物。 That is, examples of the diamine compound represented by the formula [4b] include m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, and 2 , 4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoisophthalic acid In addition to the diphenol, a diamine compound having the structure represented by the following formula [4b-6] to [4b-15] can also be mentioned.
作為製作本發明的液晶配向處理劑所含有之特定聚合物的二胺成分,可將式〔4a-1〕~式〔4a-5〕所示二胺化合物及式〔4b〕所示二胺化合物以外之二胺化合物(亦稱為其他二胺化合物)作為二胺成分使用。下述舉出該具體例,但並未限定於此等例。 The diamine component of the specific polymer contained in the liquid crystal alignment agent of the present invention may be a diamine compound represented by the formula [4a-1] to the formula [4a-5] and a diamine compound represented by the formula [4b]. A diamine compound other than the other (also referred to as another diamine compound) is used as the diamine component. The specific examples are given below, but are not limited to these examples.
例如可舉出4,4’-二胺基聯苯基、3,3’-二甲基-4,4’-二胺基聯苯基、3,3’-二甲氧基-4,4’-二胺基聯苯基、3,3’-二羥基-4,4’-二胺基聯苯基、3,3’-二羧基-4,4’-二胺基聯苯基、3,3’-二氟-4,4’-二胺基聯苯基、3,3’-三氟甲基-4,4’-二胺基聯苯基、3,4’-二胺基聯苯基、3,3’-二胺基聯苯基、2,2’-二胺基聯苯基、2,3’-二胺基聯苯基、4,4’-二胺基二苯基甲烷、3,3’-二胺基二苯基甲烷、3,4’-二胺基二苯基甲烷、2,2’-二胺基二苯基甲烷、2,3’-二胺基二苯基甲烷、4,4’-二胺基二苯基醚、3,3’-二胺基二苯基醚、3,4’-二胺基二苯基醚、2,2’-二胺基二苯基醚、2,3’-二胺基二苯基醚、4,4’-磺醯基二苯胺、3,3’-磺醯基二苯胺、雙(4-胺基苯基)矽烷、雙(3-胺基苯基)矽烷、二甲基-雙(4-胺基苯基)矽烷、二甲基-雙(3-胺基苯基)矽烷、4,4’-硫代二苯胺、3,3’-硫代二苯胺、4,4’-二胺基二苯基胺、3,3’-二胺 基二苯基胺、3,4’-二胺基二苯基胺、2,2’-二胺基二苯基胺、2,3’-二胺基二苯基胺、N-甲基(4,4’-二胺基二苯基)胺、N-甲基(3,3’-二胺基二苯基)胺、N-甲基(3,4’-二胺基二苯基)胺、N-甲基(2,2’-二胺基二苯基)胺、N-甲基(2,3’-二胺基二苯基)胺、4,4’-二胺基二苯甲酮、3,3’-二胺基二苯甲酮、3,4’-二胺基二苯甲酮、1,4-二胺基萘、2,2’-二胺基二苯甲酮、2,3’-二胺基二苯甲酮、1,5-二胺基萘、1,6-二胺基萘、1,7-二胺基萘、1,8-二胺基萘、2,5-二胺基萘、2,6-二胺基萘、2,7-二胺基萘、2,8-二胺基萘、1,2-雙(4-胺基苯基)乙烷、1,2-雙(3-胺基苯基)乙烷、1,3-雙(4-胺基苯基)丙烷、1,3-雙(3-胺基苯基)丙烷、1,4-雙(4-胺基苯基)丁烷、1,4-雙(3-胺基苯基)丁烷、雙(3,5-二乙基-4-胺基苯基)甲烷、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(4-胺基苯基)苯、1,3-雙(4-胺基苯基)苯、1,4-雙(4-胺基苯甲基)苯、1,3-雙(4-胺基苯氧基)苯、4,4’-〔1,4-伸苯基雙(伸甲基)〕二苯胺、4,4’-〔1,3-伸苯基雙(伸甲基)〕二苯胺、3,4’-〔1,4-伸苯基雙(伸甲基)〕二苯胺、3,4’-〔1,3-伸苯基雙(伸甲基)〕二苯胺、3,3’-〔1,4-伸苯基雙(伸甲基)〕二苯胺、3,3’-〔1,3-伸苯基雙(伸甲基)〕二苯胺、1,4-伸苯基雙〔(4-胺基苯基)甲酮〕、1,4-伸苯基雙〔(3-胺基苯基)甲酮〕、1,3-伸苯基雙〔(4-胺基苯基)甲酮〕、1,3-伸苯基雙〔(3-胺基苯基)甲酮〕、1,4-伸苯基雙(4-胺基苯甲酸酯)、1,4- 伸苯基雙(3-胺基苯甲酸酯)、1,3-伸苯基雙(4-胺基苯甲酸酯)、1,3-伸苯基雙(3-胺基苯甲酸酯)、雙(4-胺基苯基)對苯二甲酸乙二酯、雙(3-胺基苯基)對苯二甲酸乙二酯、雙(4-胺基苯基)間苯二甲酸、雙(3-胺基苯基)間苯二甲酸、N,N’-(1,4-伸苯基)雙(4-胺基苯甲醯胺)、N,N’-(1,3-伸苯基)雙(4-胺基苯甲醯胺)、N,N’-(1,4-伸苯基)雙(3-胺基苯甲醯胺)、N,N’-(1,3-伸苯基)雙(3-胺基苯甲醯胺)、N,N’-雙(4-胺基苯基)對苯二甲醯胺、N,N’-雙(3-胺基苯基)對苯二甲醯胺、N,N’-雙(4-胺基苯基)間苯二甲醯胺、N,N’-雙(3-胺基苯基)間苯二甲醯胺、9,10-雙(4-胺基苯基)蒽、4,4’-雙(4-胺基苯氧基)二苯基碸、2,2’-雙〔4-(4-胺基苯氧基)苯基〕丙烷、2,2’-雙〔4-(4-胺基苯氧基)苯基〕六氟丙烷、2,2’-雙(4-胺基苯基)六氟丙烷、2,2’-雙(3-胺基苯基)六氟丙烷、2,2’-雙(3-胺基-4-甲基苯基)六氟丙烷、2,2’-雙(4-胺基苯基)丙烷、2,2’-雙(3-胺基苯基)丙烷、2,2’-雙(3-胺基-4-甲基苯基)丙烷、1,3-雙(4-胺基苯氧基)丙烷、1,3-雙(3-胺基苯氧基)丙烷、1,4-雙(4-胺基苯氧基)丁烷、1,4-雙(3-胺基苯氧基)丁烷、1,5-雙(4-胺基苯氧基)戊烷、1,5-雙(3-胺基苯氧基)戊烷、1,6-雙(4-胺基苯氧基)己烷、1,6-雙(3-胺基苯氧基)己烷、1,7-雙(4-胺基苯氧基)庚烷、1,7-(3-胺基苯氧基)庚烷、1,8-雙(4-胺基苯氧基)辛烷、1,8-雙(3-胺基苯氧基)辛烷、1,9-雙(4-胺基苯氧基)壬烷、1,9-雙 (3-胺基苯氧基)壬烷、1,10-雙(4-胺基苯氧基)癸烷、1,10-雙(3-胺基苯氧基)癸烷、1,11-雙(4-胺基苯氧基)十一烷、1,11-雙(3-胺基苯氧基)十一烷、1,12-雙(4-胺基苯氧基)十二烷、1,12-雙(3-胺基苯氧基)十二烷、雙(4-胺基環己基)甲烷、雙(4-胺基-3-甲基環己基)甲烷、1,3-二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷、1,11-二胺基十一烷或1,12-二胺基十二烷等。 For example, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4, 4 '-Diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3 , 3'-difluoro-4,4'-diaminobiphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diamine linkage Phenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenyl Methane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodi Phenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diamine Diphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl) Decane, bis(3-aminophenyl)decane, dimethyl-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-thio Diphenylamine, 3,3'-thiodiphenylamine, 4,4'- Amino diphenylamine, 3,3'-diamine Diphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl ( 4,4'-Diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl) Amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4'-diaminodiphenyl Methyl ketone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone , 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-Diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)B Alkane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1, 4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1 , 4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3- Bis(4-aminophenyl)benzene, 1, 4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylene bis(methyl) Diphenylamine, 4,4'-[1,3-phenylenebis(methyl)diphenylamine, 3,4'-[1,4-phenylenebis(methyl)diphenylamine, 3 , 4'-[1,3-phenylenebis(methyl)diphenylamine, 3,3'-[1,4-phenylenebis(methyl)diphenylamine, 3,3'- [1,3-phenylene bis(methyl))diphenylamine, 1,4-phenylene bis[(4-aminophenyl)methanone], 1,4-phenylene bis[(3) -aminophenyl)methanone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone 〕, 1,4-phenylene bis(4-aminobenzoate), 1,4- Phenyl bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3-phenylene bis(3-aminobenzoic acid) Ester), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalic acid , bis(3-aminophenyl)isophthalic acid, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N,N'-(1,3 -phenyl)bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1 , 3-phenylene) bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(3-amine Phenyl phenyl phthalamide, N, N'-bis(4-aminophenyl) m-xylyleneamine, N,N'-bis(3-aminophenyl) meta-xylene Indoleamine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'-bis[4-(4- Aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl) Hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'- double( 4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 1,3- Bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-double (3-Aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6- Bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7 -(3-Aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9 - bis(4-aminophenoxy)decane, 1,9-double (3-Aminophenoxy)decane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis(3-aminophenoxy)decane, 1,11- Bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)dodecane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 1,3-two Aminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diamine Alkyl octane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane.
又作為其他二胺化合物,可使用於二胺側鏈具有烷基、含氟之烷基、芳香環、脂肪族環或雜環者,進一步可使用具有此等所成的大環狀取代體者,以不損害本發明的效果之限定下使用。具體可例示出下述式〔DA1〕~〔DA13〕所示二胺化合物。 Further, as the other diamine compound, an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocyclic ring may be used for the side chain of the diamine, and a large cyclic substituent having such a group may be further used. It is used without limitation to the effects of the present invention. Specific examples thereof include diamine compounds represented by the following formulas [DA1] to [DA13].
且不損害本發明的效果之限定下,亦可使用下述式〔DA14〕所示二胺化合物。 The diamine compound represented by the following formula [DA14] can also be used without departing from the effects of the present invention.
另外作為其他二胺化合物,可使用下述式〔DA15〕及式〔DA16〕所示二胺化合物。 Further, as the other diamine compound, a diamine compound represented by the following formula [DA15] and formula [DA16] can be used.
作為其他二胺化合物,可使用下述式〔DA17〕所示二胺化合物。 As the other diamine compound, a diamine compound represented by the following formula [DA17] can be used.
於下述舉出式〔DA17〕所示二胺化合物之具體結構,但並未限定於此等例。 The specific structure of the diamine compound represented by the formula [DA17] is shown below, but is not limited to these examples.
即,作為式〔DA17〕所示二胺化合物,可舉出下述式〔DA17-1〕~〔DA17-6〕所示結構之二胺化合物。 In other words, the diamine compound represented by the formula [DA17] may, for example, be a diamine compound having the structure represented by the following formula [DA17-1] to [DA17-6].
上述其他二胺化合物為配合本發明的特定聚合物對溶劑之溶解性或液晶配向處理劑的塗布性、作為液晶配向膜時的液晶之配向性、電壓保持率、累積電荷等特性,可使用1種類或混合2種類以上使用。 The other diamine compound may be used in combination with the solubility of a specific polymer of the present invention, the solubility of a liquid crystal alignment agent, the alignment property of a liquid crystal when a liquid crystal alignment film, a voltage retention ratio, and an accumulated charge. It can be used in two types or more.
本發明的液晶配向劑所含有之特定聚合物係為,選自將反應含有前述式〔1〕所示四羧酸二酐之前述四羧酸成分,與含有具有前述式〔2〕所示側鏈之二胺化合物的上述二胺成分後所得之聚醯亞胺前驅物及該聚醯亞胺前驅物經醯亞胺化後而得之聚醯亞胺的至少1種聚合物。 The specific polymer contained in the liquid crystal alignment agent of the present invention is selected from the group consisting of the tetracarboxylic acid component containing the tetracarboxylic dianhydride represented by the above formula [1] and containing the side represented by the above formula [2]. The polyimine precursor obtained by the above diamine component of the chain diamine compound and at least one polymer of the polyimine obtained by imidization of the polyimine precursor.
反應含有前述式〔1〕所示四羧酸二酐之前述四羧酸成分,與含有具有前述式〔2〕所示側鏈的二胺化合物之前述二胺成分所得之聚醯亞胺前驅物,例如為下述式〔A〕所示結構者。 The polyimine precursor obtained by reacting the tetracarboxylic acid component of the tetracarboxylic dianhydride represented by the above formula [1] with the aforementioned diamine component of the diamine compound having the side chain represented by the above formula [2] For example, it is a structure represented by the following formula [A].
本發明的液晶配向處理劑所含有之特定聚合物為將下述式〔B〕所示四羧酸成分與下述式〔C〕所示 二胺化合物作為原料,故可比較簡便地獲得,由此理由得知將由下述式〔D〕所示重複單位之結構式所成的聚醯胺酸或該聚醯胺酸進行醯亞胺化之聚醯亞胺為佳。 The specific polymer contained in the liquid crystal alignment agent of the present invention is a tetracarboxylic acid component represented by the following formula [B] and represented by the following formula [C]. Since the diamine compound is used as a raw material, it can be obtained relatively easily. From this reason, it is known that the polyaminic acid or the polyamic acid formed by the structural formula of the repeating unit represented by the following formula [D] is ruthenium imidized. Polyimine is preferred.
又,在一般合成手法中,於上述所得之式〔D〕的聚合物中,可導入式〔A〕所示A1及A2之碳數1~8的烷基、及式〔A〕所示A3及A4之碳數1~5的烷基或乙醯基。 Further, in the general synthetic method, an alkyl group having 1 to 8 carbon atoms of A 1 and A 2 represented by the formula [A] and a formula [A] can be introduced into the polymer of the formula [D] obtained above. An alkyl group or an ethylidene group having 1 to 5 carbon atoms of A 3 and A 4 is shown.
本發明中,特定聚合物為使上述二胺成分與上述四羧 酸成分進行反應而得。具體可使用將四羧酸二酐與二胺成分進行聚縮合而得聚醯胺酸之方法、將四羧酸與二胺成分進行脫水聚縮合反應而得聚醯胺酸之方法或將二羧酸二鹵化物與二胺成分進行聚縮合而得聚醯胺酸之方法。 In the present invention, the specific polymer is such that the above diamine component and the above tetracarboxylic acid The acid component is obtained by a reaction. Specifically, a method of polycondensing a tetracarboxylic dianhydride with a diamine component to obtain a poly-proline, a method of dehydrating polycondensation of a tetracarboxylic acid and a diamine component to obtain a poly-proline, or a dicarboxylic acid can be used. A method in which an acid dihalide and a diamine component are polycondensed to obtain a polyamic acid.
欲得到聚醯胺酸烷基酯,可使用聚縮合將羧酸基進行二烷基酯化之四羧酸與二胺成分的方法、聚縮合將羧酸基進行二烷基酯化之二羧酸二鹵化物與二胺成分之方法或使聚醯胺酸之羧基變換為酯之方法。 In order to obtain a polyalkyl phthalate, a method of polycondensing a tetracarboxylic acid of a carboxylic acid group and a diamine component, and a polycondensation of a dialkyl ester of a carboxylic acid group by a polycondensation may be used. A method of converting an acid dihalide with a diamine component or a method of converting a carboxyl group of a polylysine to an ester.
欲得到聚醯亞胺,可使用使前述聚醯胺酸或聚醯胺酸烷基酯進行閉環得到聚醯亞胺之方法。 To obtain a polyimine, a method of subjecting the aforementioned polyamic acid or polyalkyl amide to ring closure to obtain a polyimine can be used.
二胺成分與四羧酸成分之反應,一般將二胺成分與四羧酸成分在有機溶劑中進行。作為此時所使用的有機溶劑,僅可溶解所生成之聚醯亞胺前驅物者即可並無特別限定。下述舉出使用於反應之有機溶劑的具體例,但並未限定於此等。 The reaction of the diamine component and the tetracarboxylic acid component is generally carried out by using a diamine component and a tetracarboxylic acid component in an organic solvent. The organic solvent used at this time is not particularly limited as long as it can dissolve only the produced polyimide precursor. Specific examples of the organic solvent used in the reaction are listed below, but are not limited thereto.
例如可舉出N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮或γ-丁內酯、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、二甲基亞碸、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-戊酮或下述式〔D-1〕~式〔D-3〕所示溶劑等。 For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, Dimethyl sulfonium, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula [ D-1]~ a solvent represented by the formula [D-3].
這些可單獨使用,亦可混合使用。且即使為不溶解聚醯亞胺前驅物之溶劑,僅不析出所生成之聚醯亞胺前驅物的範圍下,可混合於上述溶劑中使用。又,有機溶劑中之水分會阻礙聚合反應,進一步成為水解所生成之聚醯亞胺前驅物的原因,故使用有機溶劑經脫水乾燥者為佳。 These can be used alone or in combination. Further, even if it is a solvent which does not dissolve the polyimide precursor, it can be used in the above solvent in the range in which only the produced polyimide intermediate precursor is not precipitated. Further, since the water in the organic solvent hinders the polymerization reaction and further causes the polyimine precursor formed by the hydrolysis, it is preferred to use an organic solvent to be dried by dehydration.
將二胺成分與四羧酸成分在有機溶劑中進行反應時,可舉出攪拌分散或溶解二胺成分於有機溶劑之溶液,直接添加四羧酸成分,或分散或溶解於有機溶劑之狀態下添加之方法、相反地於將四羧酸成分分散或溶解於有機溶劑之溶液中添加二胺成分之方法、將二胺成分與四羧酸成分以交互方式添加的方法等,可使用此等任一方法。又,使用各複數種二胺成分或四羧酸成分進行反應時,可預先以混合狀態下進行反應,亦可各別順序進行反應,進一步亦將各別反應的低分子量體進行混合反應後作為聚合物。此時的聚合溫度為選自-20℃~150℃之任意溫度,較佳為-5℃~100℃之範圍。又,反應可在任意濃度下進 行,若濃度過低時,得到高分子量之聚合物變難,若濃度過高時,反應液之黏性會過高而難以進行均勻攪拌。因此,較佳為1~50質量%,更佳為5~30質量%。反應初期在高濃度下進行,其後可追加有機溶劑。 When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, a solution in which a diamine component is dissolved or dissolved in an organic solvent is added, and a tetracarboxylic acid component is directly added or dispersed or dissolved in an organic solvent. A method of adding, a method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent, or a method of adding a diamine component and a tetracarboxylic acid component in an interactive manner, etc., can be used. A method. Further, when a plurality of kinds of diamine components or tetracarboxylic acid components are used for the reaction, the reaction may be carried out in a mixed state in advance, or the reaction may be carried out in a separate order, and the low-molecular weight bodies of the respective reactions may be further mixed and reacted. polymer. The polymerization temperature at this time is any temperature selected from the range of -20 ° C to 150 ° C, preferably in the range of -5 ° C to 100 ° C. Also, the reaction can be carried out at any concentration. If the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid is too high and it is difficult to uniformly stir. Therefore, it is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and thereafter an organic solvent can be added.
對於聚醯亞胺前驅物之聚合反應,二胺成分之合計莫耳數與四羧酸成分之合計莫耳數的比以0.8~1.2者為佳。與一般聚縮合反應同樣地,該莫耳比越接近1.0時,所生成之聚醯亞胺前驅物的分子量越大。 In the polymerization reaction of the polyimine precursor, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similarly to the general polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.
本發明的聚醯亞胺為將前述聚醯亞胺前驅物進行閉環後所得之聚醯亞胺,對於該聚醯亞胺,醯胺酸基之閉環率(亦稱為醯亞胺化率)無須為100%,可配合用途或目的做任意調整。 The polyimine of the present invention is a polyimine obtained by subjecting the polyimine precursor to ring closure, and a ring closure ratio (also referred to as a ruthenium imidation ratio) of the amidino group for the polyimide. It does not need to be 100%, and can be adjusted to suit the purpose or purpose.
作為將聚醯亞胺前驅物進行醯亞胺化之方法,可舉出於直接加熱的聚醯亞胺前驅物之溶液的熱醯亞胺化或聚醯亞胺前驅物之溶液中添加觸媒之觸媒醯亞胺化。 As a method for carrying out the ruthenium imidization of the polyimide precursor, the hot hydrazide of the solution of the directly heated polyimide precursor or the catalyst added to the solution of the polyimide precursor may be added. The catalyst is imidized.
將聚醯亞胺前驅物在溶液中使其熱醯亞胺化時的溫度為100℃~400℃,較佳為120℃~250℃,一邊將藉由醯亞胺化反應所生成之水排除於系統外下進行為佳。 The temperature at which the polyimide precursor is thermally imidated in a solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, and the water formed by the ruthenium imidization reaction is excluded. It is better to perform it outside the system.
聚醯亞胺前驅物之觸媒醯亞胺化為於聚醯亞胺前驅物之溶液中,添加鹼性觸媒與酸酐,可在-20~250℃,較佳為在0~180℃下進行攪拌。鹼性觸媒之量為醯胺酸基之0.5~30莫耳倍,較佳為2~20莫耳倍,酸酐之 量為醯胺酸基的1~50莫耳倍,較佳為3~30莫耳倍。作為鹼性觸媒,可舉出吡啶、三乙基胺、三甲基胺、三丁基胺或三辛基胺等,其中亦以吡啶因具有進行反應時的適度鹼性而較佳。作為酸酐,可舉出乙酸酐、偏苯三酸酐或均苯四甲酸酐等,其中使用乙酸酐時,可使反應終了後之純化較容易進行故較佳。藉由觸媒醯亞胺化之醯亞胺化率可藉由調節觸媒量與反應溫度、反應時間而控制。 The ruthenium imide of the polyimide precursor is imidized into a solution of the polyimide precursor, and the basic catalyst and the acid anhydride are added at -20 to 250 ° C, preferably at 0 to 180 ° C. Stir. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group. The amount is 1 to 50 moles, preferably 3 to 30 moles, of the prolyl group. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is also preferred because it has moderate alkalinity in the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. When acetic anhydride is used, purification after completion of the reaction can be easily carried out, which is preferable. The imidization ratio of the imidization by the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.
由聚醯亞胺前驅物或聚醯亞胺之反應溶液中,回收所生成之聚醯亞胺前驅物或聚醯亞胺時,僅將反應溶液投入於溶劑中使其沈澱即可。作為使用於沈澱之溶劑,可舉出甲醇、乙醇、異丙基醇、丙酮、己烷、丁基溶纖劑、庚烷、甲基乙基酮、甲基異丁基酮、甲苯、苯、水等。投與於溶劑後沈澱之聚合物經過濾並回收後,在常壓或者減壓下,可在常溫或者加熱下進行乾燥。又,將沈澱回收後之聚合物,於有機溶劑中再溶解,再沈澱回收之操作重複2~10次時,可減少聚合物中之不純物(雜質)。作為此時的溶劑,例如可舉出醇類、酮類或烴等,使用選自彼等內之3種類以上溶劑時,可進一步提高純化效率故較佳。 When the produced polyimine precursor or polyimine is recovered from the reaction solution of the polyimine precursor or the polyimine, only the reaction solution may be placed in a solvent to precipitate. Examples of the solvent used for the precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, and the like. . After the polymer precipitated by the solvent is filtered and recovered, it can be dried at normal temperature or under reduced pressure under normal pressure or reduced pressure. Further, the polymer recovered by precipitation is redissolved in an organic solvent, and the operation of reprecipitation and recovery is repeated 2 to 10 times to reduce impurities (impurities) in the polymer. Examples of the solvent in this case include alcohols, ketones, and hydrocarbons. When three or more types of solvents selected from the group are used, the purification efficiency can be further improved, which is preferable.
本發明的液晶配向處理劑所含有之特定聚合物之分子量,若考慮到所得之液晶配向膜的強度、液晶配向膜形成時之作業性及塗膜性時,以GPC(Gel Permeation Chromatography)法所測定之重量平均分子量為5,000~1,000,000者為佳,較佳為10,000~150,000。 The molecular weight of the specific polymer contained in the liquid crystal alignment agent of the present invention is determined by GPC (Gel Permeation Chromatography) in consideration of the strength of the obtained liquid crystal alignment film, workability at the time of formation of the liquid crystal alignment film, and coating property. The weight average molecular weight measured is preferably 5,000 to 1,000,000, preferably 10,000 to 150,000.
本發明的液晶配向處理劑為使用於形成液晶配向膜之塗布溶液,含有聚合物成分及溶劑,使用於形成聚合物被膜之塗布溶液。 The liquid crystal alignment treatment agent of the present invention is a coating solution for forming a liquid crystal alignment film, and contains a polymer component and a solvent, and is used for forming a coating solution of a polymer film.
而如上述,本發明的液晶配向處理劑中,作為聚合物成分,上述特定聚合物,即含有以下聚合物者,該聚合物為選自將反應含有上述式〔1〕所示四羧酸二酐之四羧酸成分與具有含有上述式〔2〕所示側鏈之二胺化合物的二胺成分所得之聚醯亞胺前驅物及該聚醯亞胺前驅物進行醯亞胺化所得之聚醯亞胺中的至少1種,具有液晶滴落時對於液晶配向膜之物理性壓力可減輕的結構,因具有較高疏水性之結構,故如後述實施例所示,可具備使用本發明的液晶配向處理劑所得之液晶配向膜的液晶顯示元件之配向不均勻經改善,且具有優良預傾角之耐熱性者。 As described above, in the liquid crystal alignment treatment agent of the present invention, as the polymer component, the specific polymer, that is, the polymer having the following polymer, is selected from the group consisting of the tetracarboxylic acid represented by the above formula [1]. Polyimide component obtained from a tetracarboxylic acid component of an anhydride and a diamine component having a diamine component containing a side chain compound represented by the above formula [2], and a polyimidine precursor obtained by the ruthenium imidization At least one of the quinone imines has a structure in which the physical pressure of the liquid crystal alignment film can be reduced when the liquid crystal is dropped, and has a structure having a high hydrophobicity. Therefore, as described in the following examples, the present invention can be provided. The alignment unevenness of the liquid crystal display element of the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent is improved, and the heat resistance of the excellent pretilt angle is improved.
詳細說明為液晶顯示元件之配向不均勻為於藉由ODF方式之液晶滴落時,於液晶配向膜施予物理性壓力,故可能產生液晶之垂直配向性降低。又,附著於液晶配向膜表面之吸附水或不純物,可於ODF步驟中藉由滴下的液晶而掃除,此可能為在液晶滴落部或液晶之液滴彼此接觸部分因吸附水或不純物的量變的相異而產生。於此,所謂ODF方式為將液晶直接滴落於形成於基板上之液晶配向膜而言。 In detail, the alignment unevenness of the liquid crystal display element is such that when the liquid crystal by the ODF method is dropped, physical pressure is applied to the liquid crystal alignment film, so that the vertical alignment of the liquid crystal may be lowered. Further, the adsorbed water or the impurities adhering to the surface of the liquid crystal alignment film may be removed by dropping the liquid crystal in the ODF step, which may be caused by the amount of adsorbed water or impurities in the liquid crystal dropping portion or the liquid crystal droplets contacting each other. The difference is produced. Here, the ODF method is a liquid crystal alignment film formed by directly dropping liquid crystal on a substrate.
本發明的液晶配向處理劑所含有之上述特定 聚合物因於主鏈上具有來自式〔1〕所示四羧酸二酐之伸甲基,故為可撓性(柔軟),將液晶配向處理劑塗布於基板時,特定聚合物容易移至塗膜(最終為液晶配向膜)之表層(即與基板為反對側)。而該特定聚合物因具有式〔2〕所示側鏈之二胺化合物上具有來自式〔2〕所示側鏈,故對於塗膜或液晶配向膜表層之式〔2〕所示側鏈的密度變高。如此藉由特定聚合物往表層移行,且表層之式〔2〕所示側鏈的密度變高,可減輕液晶滴落時之對液晶配向膜的物理性壓力。 The above specific content contained in the liquid crystal alignment treatment agent of the present invention Since the polymer has a methyl group derived from the tetracarboxylic dianhydride represented by the formula [1] in the main chain, it is flexible (soft), and when a liquid crystal alignment treatment agent is applied to a substrate, the specific polymer is easily moved to The surface layer of the coating film (finally the liquid crystal alignment film) (ie, the opposite side to the substrate). Further, since the specific polymer has a side chain represented by the formula [2] on the diamine compound having a side chain represented by the formula [2], the side chain represented by the formula [2] on the surface layer of the coating film or the liquid crystal alignment film is used. The density becomes higher. By shifting the specific polymer to the surface layer as described above, and the density of the side chain represented by the formula [2] in the surface layer is increased, the physical pressure on the liquid crystal alignment film at the time of liquid crystal dropping can be reduced.
而藉由特定聚合物往表層移行,且表層的式〔2〕所示側鏈之密度變高,液晶配向膜之疏水性變高。且藉由使用式〔1〕所示四羧酸二酐,將液晶配向處理劑塗布於基板後進行燒成時所產生的熱醯亞胺化變的容易進行,液晶配向膜之疏水性亦變高。如此因其為疏水性較高者,可使液晶滴落部等之吸附水或不純物的量均勻。 On the other hand, when the specific polymer migrates to the surface layer and the density of the side chain represented by the formula [2] in the surface layer becomes high, the hydrophobicity of the liquid crystal alignment film becomes high. Further, by using the tetracarboxylic dianhydride represented by the formula [1], the liquid crystal alignment treatment agent is applied to the substrate, and the heat-induced imidization of the liquid crystal alignment treatment is easily performed, and the hydrophobicity of the liquid crystal alignment film is also changed. high. Thus, since it is a highly hydrophobic one, the amount of adsorbed water or impurities which are liquid crystal dropping parts etc. can be made uniform.
該結果被推測為可實現在ODF方式所產生的配向不均勻之改善。 This result is presumed to be an improvement in alignment unevenness which is caused by the ODF method.
特別對於PSA模式,將藉由ODF方式將含有單體(聚合性化合物)之液晶滴落於液晶配向膜上時,當液晶濕潤擴散時,引起單體之分離現象(亦稱為層析顯像),在該狀態下進行PSA化處理時,產生液晶之預傾角相異的區域,容易產生配向不均勻。其中,所謂PSA,將對於基板呈垂直配向之液晶分子藉由電場,使其應答之方式(垂直配向方式)的液晶顯示元件中,預先於液晶組 成物中添加聚合性化合物者。又,所謂聚合性化合物為,藉由活性能量線及熱的至少一方進行聚合的化合物。 Especially for the PSA mode, when the liquid crystal containing a monomer (polymerizable compound) is dropped on the liquid crystal alignment film by the ODF method, when the liquid crystal is wet-diffused, the separation phenomenon of the monomer (also referred to as chromatographic imaging) is caused. When the PSA treatment is performed in this state, a region in which the pretilt angles of the liquid crystals are different is generated, and alignment unevenness is likely to occur. Among them, the PSA is a liquid crystal display element in which a liquid crystal molecule whose substrate is vertically aligned is subjected to an electric field and is responsive (vertical alignment mode), in advance of the liquid crystal group. A polymerizable compound is added to the product. Further, the polymerizable compound is a compound which is polymerized by at least one of an active energy ray and heat.
對於如此PSA模式之情況,所謂本發明的液晶配向處理劑,因其為疏水性較高者,可使單體之分散性均勻,可抑制預傾角之偏差,而改善配向不均勻。 In the case of the PSA mode, the liquid crystal alignment treatment agent of the present invention has a higher hydrophobicity and can make the dispersion of the monomer uniform, thereby suppressing variations in the pretilt angle and improving alignment unevenness.
又,可推測藉由特定聚合物於表層上移行,且表層的式〔2〕所示側鏈之密度變高時,可使式〔2〕所示側鏈安定,使預傾角之耐熱性變的良好。 Further, it is presumed that when the specific polymer migrates on the surface layer and the density of the side chain represented by the formula [2] in the surface layer becomes high, the side chain represented by the formula [2] can be stabilized, and the heat resistance of the pretilt angle can be changed. Good.
而本發明的液晶配向處理劑係為具有優良印刷性者,可得到無眼洞或膜厚不均勻之均勻塗膜。 On the other hand, the liquid crystal alignment treatment agent of the present invention has excellent printability, and a uniform coating film having no eye hole or uneven film thickness can be obtained.
具有使用如此本發明的液晶配向處理劑所製作之液晶配向膜的液晶顯示元件並無配向不均勻所引起的配向缺陷,且因預傾角之熱安定性優良,故成為顯示品位優良的信賴性高之液晶顯示元件。 The liquid crystal display element having the liquid crystal alignment film produced by using the liquid crystal alignment treatment agent of the present invention has no alignment defect due to misalignment, and has excellent thermal stability due to the pretilt angle, so that it has excellent reliability in display quality. Liquid crystal display element.
本發明的液晶配向處理劑中之所有聚合物成分,可皆為特定聚合物,亦可混合此以外的其他聚合物。此時,此以外的其他聚合物的含有量為,特定聚合物之0.5質量%~15質量%,較佳為1質量%~10質量%。作為此以外的其他聚合物,可舉出不使用前述式〔1〕所示四羧酸二酐之聚醯亞胺前驅物或聚醯亞胺。且,可舉出丙烯酸聚合物、甲基丙烯酸聚合物、聚苯乙烯、聚醯胺或聚矽氧烷等。 All of the polymer components in the liquid crystal alignment agent of the present invention may be specific polymers or may be mixed with other polymers. In this case, the content of the other polymer other than the above is 0.5% by mass to 15% by mass of the specific polymer, preferably 1% by mass to 10% by mass. The polymer other than this may, for example, be a polyimine imine or a polyimine which does not use the tetracarboxylic dianhydride represented by the above formula [1]. Further, examples thereof include an acrylic polymer, a methacrylic polymer, polystyrene, polyamine or polyoxyalkylene.
本發明的液晶配向處理劑中之固體成分濃度可藉由所形成之液晶配向膜厚度的設定做適宜變更,以 0.5~10質量%為佳,以1~8質量%為較佳。固體成分濃度未達0.5質量%時,形成均勻且無缺點之塗膜變的困難,若比10質量%多時,溶液之保存安定性會有變差的情況。此所謂固體成分為,自液晶配向處理劑除去溶劑之成分,表示上述特定聚合物或此以外的其他聚合物、後述各種添加劑。 The solid content concentration in the liquid crystal alignment treatment agent of the present invention can be appropriately changed by setting the thickness of the liquid crystal alignment film formed, It is preferably 0.5 to 10% by mass, preferably 1 to 8% by mass. When the solid content concentration is less than 0.5% by mass, it is difficult to form a coating film which is uniform and free from defects, and if it is more than 10% by mass, the storage stability of the solution may be deteriorated. The solid component is a component which removes a solvent from a liquid crystal alignment treatment agent, and shows the above-mentioned specific polymer or other polymer other than this, and various additives mentioned later.
本發明的液晶配向處理劑中的有機溶劑由藉由塗布形成均勻液晶配向膜之觀點來看,以有機溶劑的含有量為70~99.9質量%者為佳。該含有量可藉由作為目的之液晶配向膜膜厚而適宜地變更。 The organic solvent in the liquid crystal alignment treatment agent of the present invention is preferably from 70 to 99.9% by mass in terms of the content of the organic solvent from the viewpoint of forming a uniform liquid crystal alignment film by coating. The content can be appropriately changed by the thickness of the intended liquid crystal alignment film.
使用於本發明的液晶配向處理劑之有機溶劑僅可溶解特定聚合物之有機溶劑(亦稱為良溶劑)即可,並無特別限定。下述可舉出良溶劑之具體例,但並未限定於此等例子。 The organic solvent used in the liquid crystal alignment agent of the present invention is not particularly limited as long as it can dissolve only the organic solvent (also referred to as a good solvent) of the specific polymer. Specific examples of the good solvent are exemplified below, but are not limited thereto.
例如可舉出N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、二甲基亞碸、γ-丁內酯、1,3-二甲基-咪唑啉酮、甲基乙基酮、環己酮、環戊酮或4-羥基-4-甲基-2-戊酮等。其中亦可舉出N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、γ-丁內酯或上述前述式〔D-1〕~式〔D-3〕所示溶劑等。這些可單獨使用,亦可混合使用。 For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl fluorene, Γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone. Further, examples thereof include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, and a solvent represented by the above formula [D-1] to formula [D-3]. These can be used alone or in combination.
其中亦以使用N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、γ-丁內酯為佳。且特定聚合物對溶劑之溶解性高時,使用前述式〔D-1〕~式〔D-3〕所示溶劑為佳。 Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone are preferably used. When the solubility of a specific polymer in a solvent is high, it is preferred to use a solvent represented by the above formula [D-1] to formula [D-3].
本發明的液晶配向處理劑中之良溶劑以含於液晶配向處理劑之溶劑全體的10~100質量%者為佳。其中亦以20~90質量%為佳。較佳為30~80質量%。 The good solvent in the liquid crystal alignment agent of the present invention is preferably 10 to 100% by mass based on the total amount of the solvent contained in the liquid crystal alignment treatment agent. Among them, 20 to 90% by mass is preferred. It is preferably 30 to 80% by mass.
本發明的液晶配向處理劑以不損害本發明的效果下,可使用提高塗布液晶配向處理劑時的液晶配向膜之塗膜性或表面平滑性的有機溶劑(亦稱為弱溶劑)。下述可舉出弱溶劑之具體例,但並非限定於這些例子。 In the liquid crystal alignment treatment agent of the present invention, an organic solvent (also referred to as a weak solvent) for improving the coating property or surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used without impairing the effects of the present invention. Specific examples of the weak solvent are exemplified below, but are not limited to these examples.
例如可舉出乙醇、異丙基醇、1-丁醇、2-丁醇、異丁基醇、tert-丁基醇、1-戊醇、2-戊醇、3-戊醇、2-甲基-1-丁醇、異戊基醇、tert-戊基醇、3-甲基-2-丁醇、新戊基醇、1-己醇、2-甲基-1-戊醇、2-甲基-2-戊醇、2-乙基-1-丁醇、1-庚醇、2-庚醇、3-庚醇、1-辛醇、2-辛醇、2-乙基-1-己醇、環己醇、1-甲基環己醇、2-甲基環己醇、3-甲基環己醇、1,2-乙烷二醇、1,2-丙烷二醇、1,3-丙烷二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,5-戊烷二醇、2-甲基-2,4-戊烷二醇、2-乙基-1,3-己烷二醇、二丙基醚、二丁基醚、二己基醚、二噁烷、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丁基醚、1,2-丁氧基乙烷、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇甲基乙基醚、二乙二醇二丁基醚、2-戊酮、3-戊酮、2-己酮、2-庚酮、4-庚酮、3-乙氧基丁基乙酸酯、1-甲基戊基乙酸酯、2-乙基丁基乙酸酯、2-乙基己基乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、伸丙基碳酸酯、伸乙基碳酸酯、2-(甲氧基甲氧基)乙醇、乙二醇單丁基醚、乙二醇 單異戊基醚、乙二醇單己基醚、2-(己氧基)乙醇、糠基醇、二乙二醇、丙二醇、丙二醇單丁基醚、1-(丁氧基乙氧基)丙醇、丙二醇單甲基醚乙酸酯、二丙二醇、二丙二醇單甲基醚、二丙二醇單乙基醚、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、丙酮酸乙基、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙基、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙基、3-甲氧基丙酸丁酯、乳酸甲基酯、乳酸乙基酯、乳酸n-丙基酯、乳酸n-丁基酯、乳酸異戊酯或上述前述式〔D-1〕~式〔D-3〕所示溶劑等。 For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl 1-butanol, isoamyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2- Methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1- Hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1, 3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl Base-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether , ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Ethyl 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, propyl carbonate, ethyl carbonate, 2-(A Oxymethoxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol Monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy)ethanol, mercapto alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1-(butoxyethoxy)propyl Alcohol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol single Ethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol Monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethyl Glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxy Methyl propyl propionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropane Acid propyl, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, milk n- propyl, n- butyl lactate, isopentyl lactate or the above formula [D-1] to Formula [D-3] FIG solvent.
其中亦以使用1-己醇、環己醇、1,2-乙烷二醇、1,2-丙烷二醇、丙二醇單丁基醚或乙二醇單丁基醚、或上述前述式〔D-1〕~式〔D-3〕所示溶劑為佳。 Wherein 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether or ethylene glycol monobutyl ether, or the above formula [D] The solvent represented by the formula [1-3] is preferably a solvent represented by the formula [D-3].
這些弱溶劑以含於液晶配向處理劑之有機溶劑全體的1~70質量%者為佳。其中亦以1~60質量%為佳。更佳為5~60質量%。 These weak solvents are preferably from 1 to 70% by mass based on the total of the organic solvent contained in the liquid crystal alignment agent. Among them, 1 to 60% by mass is preferred. More preferably, it is 5 to 60% by mass.
本發明的液晶配向處理劑中,以不損害本發明的效果下,可含有具有環氧基、異氰酸酯基、氧雜環丁 烷基或環碳酸酯基之交聯性化合物、具有選自由羥基、羥基烷基及低級烷氧基烷基所成群的至少1種取代基的交聯性化合物、或具有聚合性不飽和鍵之交聯性化合物。這些取代基或聚合性不飽和鍵必須於交聯性化合物中具有2個以上。 The liquid crystal alignment treatment agent of the present invention may contain an epoxy group, an isocyanate group or an oxetane in order not to impair the effects of the present invention. a crosslinkable compound of an alkyl group or a cyclic carbonate group, a crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group, or a polymerizable unsaturated bond a crosslinkable compound. These substituents or polymerizable unsaturated bonds must have two or more of the crosslinkable compounds.
作為具有環氧基或異氰酸酯基之交聯性化合物,例如可舉出雙酚丙酮縮水甘油醚、酚清漆環氧樹脂、甲酚清漆環氧樹脂、三縮水甘油異氰脲酸酯、四縮水甘油胺基二伸苯基、四縮水甘油-m-二甲苯二胺、四縮水甘油-1,3-雙(胺基乙基)環己烷、四苯基縮水甘油醚乙烷、三苯基縮水甘油醚乙烷、雙酚六氟乙醯二縮水甘油醚、1,3-雙(1-(2,3-環氧丙氧基)-1-三氟甲基-2,2,2-三氟甲基)苯、4,4-雙(2,3-環氧丙氧基)八氟聯苯基、三縮水甘油-p-胺基酚、四縮水甘油對二甲苯二胺、2-(4-(2,3-環氧丙氧基)苯基)-2-(4-(1,1-雙(4-(2,3-環氧丙氧基)苯基)乙基)苯基)丙烷或1,3-雙(4-(1-(4-(2,3-環氧丙氧基)苯基)-1-(4-(1-(4-(2,3-環氧丙氧基)苯基)-1-甲基乙基)苯基)乙基)苯氧基)-2-丙醇等。 Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol varnish epoxy resin, cresol epoxide epoxy resin, triglycidyl isocyanurate, and tetraglycidyl alcohol. Aminodiphenyl, tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyl ether, triphenyl shrinkage Glycerol ether, bisphenol hexafluoroacetic acid diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-three Fluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl p-xylenediamine, 2-( 4-(2,3-epoxypropoxy)phenyl)-2-(4-(1,1-bis(4-(2,3-epoxypropoxy)phenyl)ethyl)phenyl Propane or 1,3-bis(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-(4-(1-(4-(2,3-epoxy)) Propoxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol and the like.
具有氧雜環丁烷基之交聯性化合物為具有至少2個的下述式〔4〕所示氧雜環丁烷基之交聯性化合物。 The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetanyl groups represented by the following formula [4].
具體可舉出國際公開公報WO2011/132751之第58~59頁所揭示的式〔4a〕~式〔4k〕所示交聯性化合物。 Specifically, a crosslinkable compound represented by the formula [4a] to the formula [4k] disclosed on pages 58 to 59 of International Publication WO2011/132751 can be mentioned.
具有環碳酸酯基之交聯性化合物為具有至少2個的下述式〔5〕所示環碳酸酯基之交聯性化合物。 The crosslinkable compound having a cyclic carbonate group is a crosslinkable compound having at least two cyclic carbonate groups represented by the following formula [5].
具體可舉出國際公開公報WO2011/132751的第76~82頁所揭示的式〔5-1〕~式〔5-42〕所示交聯性化合物。 Specifically, a crosslinkable compound represented by the formula [5-1] to the formula [5-42] disclosed on pages 76 to 82 of International Publication WO2011/132751 can be mentioned.
作為具有選自羥基及烷氧基所成群之至少1種取代基的交聯性化合物,例如可舉出具有羥基或烷氧基之胺基樹脂,例如可舉出三聚氰胺樹脂、尿素樹脂、胍胺樹脂、甘脲-甲醛樹脂、琥珀醯基醯胺-甲醛樹脂或乙烯脲-甲醛樹脂等。具體可使用胺基之氫原子由羥甲基或烷氧基甲基或該雙方所取代之三聚氰胺衍生物、苯並胍胺衍生物、或甘脲。該三聚氰胺衍生物或苯並胍胺衍生物可存在2量體或3量體。此等為每1個三嗪環,平均具有3個以上6個以下的羥甲基或烷氧基甲基者為佳。 The crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group may, for example, be an amine-based resin having a hydroxyl group or an alkoxy group, and examples thereof include a melamine resin, a urea resin, and a hydrazine. Amine resin, glycoluril-formaldehyde resin, amber mercaptophthalamide-formaldehyde resin or ethylene urea-formaldehyde resin. Specifically, a hydrogen atom of an amine group may be used, which is a methylol or alkoxymethyl group or a melamine derivative, a benzoguanamine derivative, or a glycoluril. The melamine derivative or the benzoguanamine derivative may be present in two or three doses. These are preferably one or more than 6 or less methylol groups or alkoxymethyl groups per one triazine ring.
作為如此三聚氰胺衍生物或苯並胍胺衍生物 之例子,可舉出販賣品之每1個三嗪環,由平均3.7個甲氧基甲基所取代之MX-750、每1個三嗪環,由平均5.8個甲氧基甲基所取代之MW-30(以上為三和化學公司製)或Cymel300、301、303、350、370、771、325、327、703、712等甲氧基甲基化三聚氰胺、Cymel235、236、238、212、253、254等甲氧基甲基化丁氧基甲基化三聚氰胺、Cymel506、508等丁氧基甲基化三聚氰胺、如Cymel1141之含有羧基之甲氧基甲基化異丁氧基甲基化三聚氰胺、如Cymel1123之甲氧基甲基化乙氧基甲基化苯並胍胺、如Cymel1123-10之甲氧基甲基化丁氧基甲基化苯並胍胺、如Cymel1128之丁氧基甲基化苯並胍胺、如Cymel1125-80之含有羧基的甲氧基甲基化乙氧基甲基化苯並胍胺(以上為三井氰胺公司製)。又,作為甘脲之例子,可舉出如Cymel1170之丁氧基甲基化甘脲、如Cymel1172之羥甲基化甘脲等、如Powder link1174之甲氧基羥甲基化甘脲等。 As such a melamine derivative or a benzoguanamine derivative As an example, each of the triazine rings of the sold product, MX-750 substituted by an average of 3.7 methoxymethyl groups, and each triazine ring is substituted by an average of 5.8 methoxymethyl groups. MW-30 (above is manufactured by Sanwa Chemical Co., Ltd.) or Cymel300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. methoxymethylated melamine, Cymel 235, 236, 238, 212, 253, 254 and other methoxymethylated butoxymethylated melamine, Cymel 506, 508 and other butoxymethylated melamine, such as Cymel1141 containing carboxyl group methoxymethylated isobutoxymethylated melamine a methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1123, a methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, a butoxy group such as Cymel 1128 Benzobenzamide, a carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 (manufactured by Mitsui Cyanamide Co., Ltd.). Further, examples of the glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and methoxymethylolated glycoluril such as Powder Link 1174.
作為具有羥基或烷氧基之苯或酚性化合物,例如可舉出1,3,5-參(甲氧基甲基)苯、1,2,4-參(異丙氧基甲基)苯、1,4-雙(sec-丁氧基甲基)苯或2,6-二羥基甲基-p-tert-丁基酚等。 Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxy group include 1,3,5-glycol(methoxymethyl)benzene and 1,2,4-cis (isopropoxymethyl)benzene. 1,4-bis(sec-butoxymethyl)benzene or 2,6-dihydroxymethyl-p-tert-butylphenol.
更具體可舉出國際公開公報WO2011/132751的第62~66頁所揭示的式〔6-1〕~式〔6-48〕所示交聯性化合物。 More specifically, a crosslinkable compound represented by the formula [6-1] to the formula [6-48] disclosed on pages 62 to 66 of International Publication WO2011/132751 can be mentioned.
作為具有聚合性不飽和鍵之交聯性化合物,例如可舉出三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、三(甲基)丙烯醯氧基乙氧基三羥甲基丙烷或甘油聚縮水甘油醚聚(甲基)丙烯酸酯等分子內具有3個聚合性不飽和基之交聯性化合物,進一步可舉出乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、環氧乙烷雙酚A型二(甲基)丙烯酸酯、環氧丙烷雙酚型二(甲基)丙烯酸酯、1,6-己烷二醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、乙二醇二縮水甘油醚二(甲基)丙烯酸酯、二乙二醇二縮水甘油醚二(甲基)丙烯酸酯、鄰苯二甲酸二縮水甘油酯二(甲基)丙烯酸酯或羥基特戊酸新戊二醇二(甲基)丙烯酸酯等分子內具有2個聚合性不飽和基之交聯性化合物,另外可舉出2-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、2-羥基丁基(甲基)丙烯酸酯、2-苯氧基-2-羥基丙基(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基-2-羥基丙基鄰苯二甲酸酯、3-氯-2-羥基丙基(甲基)丙烯酸酯、甘油單(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基磷酸酯或N-羥甲基(甲基)丙烯酸醯胺等分子內具有1個聚合性不飽和基之交聯性化合物。 Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and three. a crosslinkable compound having three polymerizable unsaturated groups in a molecule such as (meth)acryloxyethoxy trimethylolpropane or glycerol polyglycidyl ether poly(meth)acrylate, and further examples thereof Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol II Methyl) acrylate, polypropylene glycol di(meth) acrylate, butane diol di(meth) acrylate, neopentyl glycol di(meth) acrylate, ethylene oxide bisphenol A type II (A) Acrylate, propylene oxide bisphenol type di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, glycerol di(meth) acrylate, pentaerythritol di(methyl) Acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, o-benzene a crosslinkable compound having two polymerizable unsaturated groups in a molecule such as diglycidyl dicarboxylate di(meth)acrylate or hydroxypivalic acid neopentyl glycol di(meth)acrylate, and may also be mentioned 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (methyl) Acrylate, 2-(methyl)propenyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono(meth)acrylic acid A crosslinkable compound having one polymerizable unsaturated group in the molecule such as an ester, 2-(meth)acryloyloxyethyl phosphate or N-methylol (meth)acrylic acid decylamine.
另外亦可使用下述式〔7〕所示化合物。 Further, a compound represented by the following formula [7] can also be used.
上述化合物為交聯性化合物之一例子,但未限定於此等。又,使用於本發明的液晶配向處理劑之交聯性化合物可為1種類,亦可為組合2種類以上者。 The above compound is an example of a crosslinkable compound, but is not limited thereto. In addition, the crosslinkable compound to be used in the liquid crystal alignment agent of the present invention may be one type or two or more types.
本發明的液晶配向處理劑中之交聯性化合物的含有量,對於所有聚合物成分100質量份而言,以0.1~150質量份者為佳。進行交聯反應,表現目的效果時,對於所有聚合物成分100質量份而言,以0.1~100質量份為較佳,特別以1~50質量份為最佳。 The content of the crosslinkable compound in the liquid crystal alignment agent of the present invention is preferably 0.1 to 150 parts by mass based on 100 parts by mass of all the polymer components. When the crosslinking reaction is carried out and the intended effect is exhibited, it is preferably 0.1 to 100 parts by mass, and particularly preferably 1 to 50 parts by mass, based on 100 parts by mass of all the polymer components.
使用本發明的液晶配向處理劑作為液晶配向膜時,促進液晶配向膜中之電荷移動,作為促進使用該液晶配向膜之液晶胞的放電之化合物,以添加於國際公開公 報WO2011/132751的第69~73頁所揭示的式〔M1〕~式〔M156〕所示氮含有雜環胺化合物者為佳。該胺化合物可直接添加於組成物,亦可以適當溶劑溶解為濃度0.1質量%~10質量%,較佳為1質量%~7質量%之溶液後再添加為佳。作為該溶劑,僅可溶解上述特定聚合物之有機溶劑即可,並無特別限定。 When the liquid crystal alignment treatment agent of the present invention is used as a liquid crystal alignment film, the charge movement in the liquid crystal alignment film is promoted, and the compound which promotes discharge of the liquid crystal cell using the liquid crystal alignment film is added to the international public. It is preferred that the nitrogen represented by the formula [M1] to the formula [M156] disclosed on pages 69 to 73 of WO2011/132751 contains a heterocyclic amine compound. The amine compound may be directly added to the composition, or may be dissolved in a suitable solvent to a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass, and then preferably added. The solvent is not particularly limited as long as it can dissolve only the organic solvent of the specific polymer.
本發明的液晶配向處理劑以不損害本發明效果下,可使用提高塗布液晶配向處理劑時的液晶配向膜之膜厚均勻性或表面平滑性的化合物。進一步可使用提高液晶配向膜與基板之密著性的化合物等。 In the liquid crystal alignment treatment agent of the present invention, a compound which improves the film thickness uniformity or surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used without impairing the effects of the present invention. Further, a compound or the like which improves the adhesion between the liquid crystal alignment film and the substrate can be used.
作為提高液晶配向膜之膜厚均勻性或表面平滑性的化合物,可舉出氟系界面活性劑、矽氧系界面活性劑、分離子系界面活性劑等。 Examples of the compound which improves the film thickness uniformity or the surface smoothness of the liquid crystal alignment film include a fluorine-based surfactant, a rhodium-based surfactant, and a separator-based surfactant.
更具體,例如可舉出EftopEF301、EF303、EF352(以上為Tohkem Products公司製)、MEGAFACF171、F173、R-30(以上為大日本墨水公司製)、FloradFC430、FC431(以上為住友3M公司製)、Asahi GuardAG710、SurflonS-382、SC101、SC102、SC103、SC104、SC105、SC106(以上為旭硝子公司製)等。這些界面活性劑之使用比率,對於含於液晶配向處理劑之所有聚合物成分100質量份而言,較佳為0.01~2質量份,更佳為0.01~1質量份。 More specifically, for example, Eftop EF 301, EF 303, EF 352 (above, Tohkem Products Co., Ltd.), MEGAFACF 171, F173, R-30 (above, manufactured by Dainippon Ink Co., Ltd.), Florad FC430, FC431 (above, Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.). The use ratio of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of all the polymer components contained in the liquid crystal alignment treatment agent.
作為提高液晶配向膜與基板之密著性的化合物之具體例,可舉出以下所示含有官能性矽烷之化合物或 含有環氧基之化合物。 Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include the following compounds containing a functional decane or An epoxy group-containing compound.
例如可舉出3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、N-乙氧基羰基-3-胺基丙基三甲氧基矽烷、N-乙氧基羰基-3-胺基丙基三乙氧基矽烷、N-三乙氧基甲矽烷基丙基三伸乙基三胺、N-三甲氧基甲矽烷基丙基三伸乙基三胺、10-三甲氧基甲矽烷基-1,4,7-三氮雜癸烷、10-三乙氧基甲矽烷基-1,4,7-三氮雜癸烷、9-三甲氧基甲矽烷基-3,6-二氮雜壬基乙酸酯、9-三乙氧基甲矽烷基-3,6-二氮雜壬基乙酸酯、N-苯甲基-3-胺基丙基三甲氧基矽烷、N-苯甲基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-雙(氧乙烯)-3-胺基丙基三甲氧基矽烷、N-雙(氧乙烯)-3-胺基丙基三乙氧基矽烷、乙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚、1,6-己烷二醇二縮水甘油醚、甘油二縮水甘油醚、2,2-二溴新戊二醇二縮水甘油醚、1,3,5,6-四縮水甘油-2,4-己烷二醇、N,N,N’,N’-四縮水甘油-m-二甲苯二胺、1,3-雙(N,N-二縮水甘油胺基甲基)環己烷或N,N,N’,N’-四縮水甘油-4,4’-二胺基二苯基甲烷等。 Examples thereof include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyltriethoxydecane. N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-urea Propyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethoxy decane, N-triethoxymethane alkyl propyl triethylamine, N-trimethoxymethyl propyl propyl triethylamine, 10-trimethoxy carboxyalkyl -1,4,7-triazadecane, 10-triethoxycarbamido-1,4,7-triazadecane, 9-trimethoxycarbamido-3,6-diaza Heteroalkyl acetate, 9-triethoxycarbamido-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzene Methyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N- Bis(oxyethylene)-3-aminopropyltrimethoxyfluorene , N-bis(oxyethylene)-3-aminopropyltriethoxydecane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-double (N , N-diglycidylaminomethyl)cyclohexane or N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like.
使用這些與基板密著的化合物時,對於含於液晶配向處理劑之所有聚合物成分100質量份而言,以0.1~30質量份者為佳,較佳為1~20質量份。未達0.1質量份時,無法期待密著性提高效果,若比30質量份多時,會有液晶配向處理劑之保存安定性惡化之情況。 When the compound is adhered to the substrate, it is preferably 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment agent. When the amount is less than 0.1 part by mass, the adhesion improving effect cannot be expected. When the amount is more than 30 parts by mass, the storage stability of the liquid crystal alignment agent may be deteriorated.
於本發明的液晶配向處理劑中,可添加上述弱溶劑、交聯性化合物、提高液晶配向膜之膜厚均勻性或表面平滑性的化合物及使與基板密著之化合物以外,僅不損害本發明的效果之範圍下,可添加以變化液晶配向膜之介電常數或導電性等電氣特性為目的的介電體或導電物質。 In the liquid crystal alignment treatment agent of the present invention, the weak solvent, the crosslinkable compound, the compound which improves the film thickness uniformity or the surface smoothness of the liquid crystal alignment film, and the compound which adheres to the substrate can be added without damaging the present invention. Within the scope of the effects of the invention, a dielectric or a conductive material for the purpose of changing electrical characteristics such as dielectric constant or conductivity of the liquid crystal alignment film may be added.
本發明的液晶配向處理劑於基板上進行塗布、燒成後,以摩擦處理或光照射等進行配向處理,可作為液晶配向膜使用。又,在垂直配向用途等時,可不經配向處理而作為液晶配向膜使用。作為此時所使用的基板,僅為透明性高之基板即可,並無特別限定,可使用玻璃基板以外的丙烯酸基板或聚碳酸酯基板等塑質基板等。由步驟的簡單化的觀點來看,使用形成欲進行液晶驅動的ITO電極等基板為佳。又,在反射型液晶顯示元件中,若僅為單側基板,亦可使用矽晶圓等不透明基板,作為此時的電極,亦可使用鋁等反射光之材料。 The liquid crystal alignment treatment agent of the present invention is applied to a substrate and fired, and then subjected to alignment treatment by rubbing treatment or light irradiation, and can be used as a liquid crystal alignment film. Moreover, when it is a vertical alignment use etc., it can use as a liquid-crystal alignment film without the alignment process. The substrate to be used in this case is not particularly limited as long as it has a high transparency, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate other than the glass substrate can be used. From the viewpoint of simplification of the steps, it is preferred to use a substrate such as an ITO electrode to be driven by liquid crystal. Further, in the reflective liquid crystal display device, an opaque substrate such as a germanium wafer can be used as the single-sided substrate, and a material that reflects light such as aluminum can be used as the electrode at this time.
液晶配向處理劑之塗布方法並無特別限定, 在工業上一般進行絲網印刷、膠版印刷、柔版印刷或噴墨法等方法。作為其他塗布方法,可舉出浸漬法、輥塗法、狹縫塗佈機法、旋轉法或噴霧法等,可配合目的使用。 The coating method of the liquid crystal alignment treatment agent is not particularly limited. Screen printing, offset printing, flexographic printing or ink jet methods are generally carried out in the industry. Examples of the other coating method include a dipping method, a roll coating method, a slit coater method, a spinning method, and a spray method, and the like can be used for the purpose.
將液晶配向處理劑塗布於基板上後,藉由加熱板、熱循環型烤箱或IR(紅外線)型烤箱等加熱手段,配合使用於液晶配向處理劑之溶劑,以30~300℃,較佳為30~250℃之溫度下使溶劑蒸發並作成液晶配向膜。燒成後之液晶配向膜的厚度若過厚時,在液晶顯示元件之消費電力層面變的不利,若過薄時,會有降低液晶顯示元件之信賴性的情況,故較佳為5~300nm,更佳為10~100nm。將液晶呈現水平配向或傾斜配向時,將燒成後液晶配向膜以摩擦或偏光紫外線照射等進行處理。 After the liquid crystal alignment agent is applied onto the substrate, it is preferably used in a solvent of a liquid crystal alignment treatment agent by a heating means such as a hot plate, a heat cycle type oven or an IR (infrared) type oven, at 30 to 300 ° C, preferably The solvent was evaporated at a temperature of 30 to 250 ° C to form a liquid crystal alignment film. When the thickness of the liquid crystal alignment film after firing is too thick, it is disadvantageous in the power consumption level of the liquid crystal display element. If it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 to 300 nm. More preferably, it is 10~100nm. When the liquid crystal is horizontally aligned or obliquely aligned, the liquid crystal alignment film after firing is treated by rubbing or polarized ultraviolet irradiation or the like.
本發明的液晶顯示元件為藉由上述手法,自本發明的液晶配向處理劑得到附有液晶配向膜之基板後,以公知方法製作液晶胞作為液晶顯示元件者。若要舉出一例子,其為具備配置呈面對面的2片基板、設置於基板間之液晶層、與具有設置於基板與液晶層之間的藉由本發明液晶配向處理劑所形成之上述液晶配向膜的液晶胞之液晶顯示元件。作為如此本發明的液晶顯示元件,可舉出垂直配向(VA:Vertical Alignment)方式,或水平配向(IPS:In-Plane Switching)方式、扭曲向列(TN:Twisted Nematic)方式、OCB配向(OCB:Optically Compensated Bend)方式等種種,又亦可為PSA(Polymer Sustained Alignment)方式等方式。且液晶配 向膜可設置於2片基板中至少一方即可。 In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film is obtained from the liquid crystal alignment treatment agent of the present invention by the above-described method, and a liquid crystal cell is produced as a liquid crystal display element by a known method. To be exemplified, the liquid crystal layer disposed between the substrates and the liquid crystal layer disposed between the substrates and the liquid crystal alignment layer formed by the liquid crystal alignment treatment agent of the present invention disposed between the substrate and the liquid crystal layer A liquid crystal display element of a liquid crystal cell of a film. Examples of the liquid crystal display device of the present invention include a vertical alignment (VA) method, an IPS (In-Plane Switching) method, a twisted nematic (TN: Twisted Nematic) method, and an OCB alignment (OCB). :Optically Compensated Bend), etc., or PSA (Polymer Sustained Alignment). And LCD with The film may be provided on at least one of the two substrates.
作為液晶胞之製作方法,可例示出準備液晶配向膜所形成之一對基板,於單方基板的液晶配向膜上散佈間隔物,貼合另一方基板使液晶配向膜面成為內側,將液晶減壓下注入使其密封的方法,或於散佈間隔物之液晶配向膜面上,滴上液晶後貼合基板使其密封的法等。在如此ODF方式中,容易產生配向不均勻,但藉由使用本發明的液晶配向處理劑,即使使用ODF方式,亦可抑制配向不均勻之產生。 As a method of producing a liquid crystal cell, a pair of substrates formed by preparing a liquid crystal alignment film can be exemplified, and a spacer is spread on a liquid crystal alignment film of a single substrate, and the other substrate is bonded so that the liquid crystal alignment film surface becomes inside, and the liquid crystal is decompressed. A method of injecting and sealing the film, or a method of laminating a liquid crystal on a liquid crystal alignment film surface of a spacer, and bonding the substrate to seal it. In the ODF method, the alignment unevenness is likely to occur. However, by using the liquid crystal alignment treatment agent of the present invention, even if the ODF method is used, the occurrence of alignment unevenness can be suppressed.
製造PSA方式之液晶顯示元件時,具有一邊對液晶胞之液晶配向膜或液晶層施予電壓下,一邊照射紫外線之步驟。且,PSA方式之液晶顯示元件為,使用於液晶混合藉由活性能量線及熱之至少一方進行聚合之聚合性化合物的液晶材料(液晶組成物),其為一邊對液晶胞施予電壓下,一邊照射紫外線所得者。 When a PSA type liquid crystal display element is produced, it has a step of irradiating ultraviolet rays while applying a voltage to a liquid crystal alignment film or a liquid crystal layer of a liquid crystal cell. Further, the liquid crystal display device of the PSA type is a liquid crystal material (liquid crystal composition) for polymerizing a polymerizable compound which is polymerized by at least one of an active energy ray and heat, and is applied to a liquid crystal cell. Those who are exposed to ultraviolet rays.
作為聚合性化合物,例如可舉出如下述式(III)所示於2個末端各具有進行光聚合之基的聚合性化合物、持有具有如下述式(IV)所示進行光聚合的基之末端與具有進行光交聯之基的末端之聚合性化合物,或如下述式(V)所示2個末端各具有進行光交聯之基的聚合性化合物。且,對於下述式(III)~(V),R12為H或碳數1~4的烷基,Z1表示可由碳數1~12的烷基或碳數1~12的烷氧基所取代之二價芳香環或者雜環,Z2表示一價芳香環或雜環,該一價芳香環或雜環可由選自碳數1~ 12的烷基及碳數1~12的烷氧基之1種以上的取代基所取代,Q1為二價有機基。Q1表示具有伸苯基(-C6H4-)、聯伸苯基(-C6H4-C6H4-)或環伸己基(-C6H10-)等環結構者為佳。此為與液晶之相互作用容易變大之故。 The polymerizable compound is a polymerizable compound having a photopolymerizable group at each of two terminals, and a group having a photopolymerization group represented by the following formula (IV), as shown by the following formula (III). A polymerizable compound having a terminal having a terminal to be photocrosslinked or a polymerizable compound having a photocrosslinking group at each of two terminals represented by the following formula (V). Further, in the following formulae (III) to (V), R 12 is H or an alkyl group having 1 to 4 carbon atoms, and Z 1 represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. a divalent aromatic ring or a heterocyclic ring substituted, Z 2 represents a monovalent aromatic ring or a heterocyclic ring, and the monovalent aromatic ring or heterocyclic ring may be selected from an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms. Substituted by one or more substituents of the group, Q 1 is a divalent organic group. Q 1 represents a ring structure having a stretching phenyl group (-C 6 H 4 -), a stretching phenyl group (-C 6 H 4 -C 6 H 4 -) or a cyclohexyl group (-C 6 H 10 -). good. This is because the interaction with the liquid crystal is likely to become large.
作為式(III)所示聚合性化合物的具體例,可舉出下述聚合性化合物。式中,V為單鍵或-R19O-所示,R19為直鏈或者分支的碳數1~10之伸烷基,較佳為 -R19O-所示,R19為直鏈或者分支的碳數2~6之伸烷基。又,W為單鍵或-OR20-所示,R20為直鏈或者分支的碳數1~10之伸烷基,較佳為-OR20-所示,R20為直鏈或者分支的碳數2~6之伸烷基。且,V及W可相同結構,亦可為相異,若為相同時容易進行合成。 Specific examples of the polymerizable compound represented by the formula (III) include the following polymerizable compounds. Wherein V is a single bond or -R 19 O-, and R 19 is a linear or branched alkyl group having 1 to 10 carbon atoms, preferably -R 19 O-, and R 19 is a linear chain. Or a branched alkyl group having 2 to 6 carbon atoms. Further, W is a single bond or -OR 20 -, and R 20 is a linear or branched alkyl group having 1 to 10 carbon atoms, preferably -OR 20 -, and R 20 is linear or branched. Alkyl groups having a carbon number of 2 to 6. Further, V and W may have the same structure or may be different, and if they are the same, they are easily synthesized.
又,作為式(III)所示聚合性化合物之其他具體例,可舉出下述式之聚合性化合物。 Moreover, as another specific example of the polymerizable compound represented by the formula (III), a polymerizable compound of the following formula may be mentioned.
如此聚合性化合物之製造方法並無特別限定,例如下述式(1)所示聚合性化合物可藉由組合有機合成化學中之方法進行合成。例如可藉由下述反應式所示 Talaga等在P.Talaga,M.Schaeffer,C.Benezra and J.L.Stampf,Synthesis,530(1990)之提案的方法,可使用SnCl2,將2-(溴甲基)丙烯酸(2-(bromomethyl)propenoic acid)與醛或酮進行反應後合成者。且Amberlyst 15為羅門哈斯公司製之強酸性離子交換樹脂。 The method for producing the polymerizable compound is not particularly limited. For example, the polymerizable compound represented by the following formula (1) can be synthesized by a combination of methods in organic synthetic chemistry. For example, 2-(bromomethyl) can be used using SnCl 2 by the method proposed by Talaga et al., P. Talaga, M. Schaeffer, C. Benezra and JLStampf, Synthesis, 530 (1990), as shown in the following reaction formula. Acrylic (2-(bromomethyl)propenoic acid) is synthesized after reaction with an aldehyde or a ketone. Amberlyst 15 is a strong acid ion exchange resin manufactured by Rohm and Haas Company.
又,2-(溴甲基)丙烯酸可由下述反應式所示Ramarajan等在K.Ramarajan,K.Kamalingam,D.J.O' Donnell and K.D.Berlin,Organic Synthesis,vol.61,56-59(1983)所提案之方法進行合成。 Further, 2-(bromomethyl)acrylic acid can be represented by the following reaction formula by Ramarajan et al., K. Ramarajan, K. Kamalingam, DJO' Donnell and KDBerlin, Organic Synthesis, vol. 61, 56-59 (1983). The method is synthesized.
作為具體合成例,合成V為-R1O-,W為-OR2-,R1與R2為相同之上述式(1)所示聚合性化合物時,可舉出下述反應式所示2種方法。 As a specific synthesis example, when a polymerizable compound represented by the above formula (1) wherein R is -R 1 O- and W is -OR 2 - and R 1 and R 2 are the same, the following reaction formula is shown. 2 methods.
又,合成R19與R20為相異之上述式(1)所 示聚合性化合物時,可舉出下述反應式所示方法。 Further, when the polymerizable compound represented by the above formula (1) is synthesized in which R 19 and R 20 are different, a method represented by the following reaction formula can be mentioned.
而合成V及W為單鍵之上述式(1)所示聚合性化合物時,可舉出下述反應式所示方法。 When the polymerizable compound represented by the above formula (1) in which V and W are a single bond is synthesized, the method represented by the following reaction formula can be mentioned.
一邊於液晶配向膜或液晶層施予電壓,一邊照射紫外線製造液晶胞的步驟(PSA化處理),例如可舉出藉由於設置在基板上之電極間施予電壓後於液晶配向膜及液晶層賦予電場,保持該電場下,照射紫外線之方法。其中作為對電極間所施予的電壓,例如為5~30Vp-p,較佳為5~20Vp-p。紫外線的照射量,例如為1~60J,較佳為40J以下,紫外線照射量較少時,可抑制因構成液晶顯 示元件之構件的破壞所產生的信賴性降低,且藉由減少紫外線照射時間,可提高製造效率,故較佳。又,所照射之紫外線的波長,例如為200nm~400nm。 In the step of applying a voltage to the liquid crystal alignment film or the liquid crystal layer to produce a liquid crystal cell by irradiation with ultraviolet rays, for example, a liquid crystal alignment film and a liquid crystal layer are applied by applying a voltage between electrodes provided on the substrate. A method of applying an electric field and maintaining the electric field to irradiate ultraviolet rays. The voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The amount of ultraviolet light to be irradiated is, for example, 1 to 60 J, preferably 40 J or less, and when the amount of ultraviolet irradiation is small, the liquid crystal display can be suppressed. It is preferable that the reliability of the destruction of the member of the display element is lowered, and the manufacturing efficiency is improved by reducing the ultraviolet irradiation time. Further, the wavelength of the ultraviolet ray to be irradiated is, for example, 200 nm to 400 nm.
如此一邊對液晶配向膜或液晶層施予電壓下,一邊照射紫外線時,可使聚合性化合物進行反應而形成聚合物,藉由該聚合物可記憶液晶分子的傾斜方向,而可加速所得到的液晶顯示元件之應答速度。 When the ultraviolet ray is irradiated to the liquid crystal alignment film or the liquid crystal layer, the polymerizable compound can be reacted to form a polymer, and the polymer can memorize the tilt direction of the liquid crystal molecules, thereby accelerating the obtained polymer. The response speed of the liquid crystal display element.
在PSA方式中,藉由ODF方式將含有單體 (聚合性化合物)之液晶於液晶配向膜上滴落時,在液晶濕潤擴充時,引起單體之分離現象,在該狀態下進行PSA化處理時,會產生與液晶之預傾角相異的區域,容易產生配向不均勻,但在本發明的液晶顯示元件中,因使用上述本發明的液晶配向處理劑,可成為可抑制配向不均勻者。 In the PSA mode, the monomer is contained by the ODF method. When the liquid crystal of the (polymerizable compound) is dropped on the liquid crystal alignment film, the separation phenomenon of the monomer is caused when the liquid crystal is wet-expanded, and when the PSA treatment is performed in this state, a region different from the pretilt angle of the liquid crystal is generated. In the liquid crystal display device of the present invention, the liquid crystal alignment treatment agent of the present invention can be used to suppress uneven alignment.
在上述已對使於形成液晶配向膜之液晶含有聚合性化合物後所製造的PSA方式的液晶顯示元件做說明,本發明的液晶顯示元件亦可為,使含有於液晶配向處理劑藉由活性能量線及熱的至少一方進行聚合的聚合性基的成分,含於其中而製作者(SC-PVA方式)。含有藉由活性能量線及熱的至少一方進行聚合的聚合性基之成分為,含有與上述PSA方式為相同的聚合性化合物,或含有藉由活性能量線及熱的至少一方進行聚合之聚合性基的聚合物。如此SC-PVA方式之情況為,與上述PSA方式同樣地,具有一邊對液晶胞的液晶配向膜或液晶層施予電壓下,一邊照射紫外線的步驟。如此一邊對液晶配向膜或液 晶層施予電壓下,一邊照射紫外線時,聚合性化合物或含有聚合性基之聚合物會起反應而形成聚合物,故藉此可記憶液晶分子的傾斜方向,故可加速所得之液晶顯示元件的應答速度。 In the above-described PSA liquid crystal display device which is produced by containing a polymerizable compound in a liquid crystal forming a liquid crystal alignment film, the liquid crystal display device of the present invention may be such that the liquid crystal alignment agent is contained in the liquid crystal alignment agent. The component of the polymerizable group in which at least one of the wire and the heat is polymerized is contained in the producer (SC-PVA method). The component containing a polymerizable group polymerized by at least one of an active energy ray and heat includes a polymerizable compound which is the same as the PSA method described above, or a polymerizable property which is polymerized by at least one of an active energy ray and heat. Base polymer. In the case of the SC-PVA method, in the same manner as the above-described PSA method, there is a step of irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film or the liquid crystal layer of the liquid crystal cell. So on the liquid crystal alignment film or liquid When the ultraviolet layer is irradiated with ultraviolet light, the polymerizable compound or the polymer containing the polymerizable group reacts to form a polymer, whereby the tilt direction of the liquid crystal molecules can be memorized, so that the obtained liquid crystal display element can be accelerated. The speed of response.
具有使用如此本發明的液晶配向處理劑所製作之液晶配向膜的液晶顯示元件,無配向不均勻所引起的配向缺陷,且具有優良的預傾角熱安定性,故成為顯示品質優良的信賴性高之液晶顯示元件。特別可利用於大畫面且高精細的液晶電視等。 A liquid crystal display element having a liquid crystal alignment film produced by using the liquid crystal alignment agent of the present invention has excellent misalignment thermal stability without uneven alignment unevenness, and thus has high reliability in display quality. Liquid crystal display element. It is especially useful for large-screen and high-definition LCD TVs.
以下舉出實施例,更詳細說明本發明,但未限定於此等。 Hereinafter, the present invention will be described in more detail by way of examples, but not limited thereto.
在合成例、實施例1~15及比較例1~5所使用的簡稱如以下所示。 The abbreviations used in the synthesis examples, Examples 1 to 15 and Comparative Examples 1 to 5 are as follows.
A1:下述式〔A1〕所示四羧酸二酐 A1: tetracarboxylic dianhydride represented by the following formula [A1]
A2:1,2,3,4-環丁烷四羧酸二酐(下述式〔A2〕所示四羧酸二酐) A2: 1,2,3,4-cyclobutanetetracarboxylic dianhydride (tetracarboxylic dianhydride represented by the following formula [A2])
A3:聯環〔3.3.0〕辛烷-2,4,6,8-四羧酸二酐(下述式〔A3〕所示四羧酸二酐) A3: bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride (tetracarboxylic dianhydride represented by the following formula [A3])
A4:下述式〔A4〕所示四羧酸二酐 A4: tetracarboxylic dianhydride represented by the following formula [A4]
A5:下述式〔A5〕所示四羧酸二酐 A5: tetracarboxylic dianhydride represented by the following formula [A5]
B1:1,3-二胺基-4-〔4-(反-4-n-庚基環己基)苯氧 基〕苯(下述式〔B1〕所示二胺化合物) B1: 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxy Benzobenzene (diamine compound represented by the following formula [B1])
B2:1,3-二胺基-5-〔4-(反-4-n-庚基環己基)苯氧基甲基〕苯(下述式〔B2〕所示二胺化合物) B2: 1,3-diamino-5-[4-(trans-4-n-heptylcyclohexyl)phenoxymethyl]benzene (diamine compound represented by the following formula [B2])
B3:1,3-二胺基-4-{4-〔反-4-(反-4-n-戊基環己基)環己基〕苯氧基}苯(下述式〔B3〕所示二胺化合物) B3: 1,3-diamino-4-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxy}benzene (shown in the following formula [B3]) Amine compound)
B4:1,3-二胺基-5-{4-〔4-(反-4-n-戊基環己基)環己基〕苯氧基甲基}苯(下述式〔B4〕所示二胺化合物) B4: 1,3-diamino-5-{4-[4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxymethyl}benzene (shown by the following formula [B4] Amine compound)
B5:下述式〔B5〕所示特定側鏈型二胺化合物 B5: specific side chain type diamine compound represented by the following formula [B5]
C1:m-伸苯基二胺(下述式〔C1〕所示二胺化合物) C1: m-phenylenediamine (diamine compound represented by the following formula [C1])
C2:p-伸苯基二胺(下述式〔C2〕所示二胺化合物) C2: p-phenylenediamine (diamine compound represented by the following formula [C2])
C3:3,5-二胺基安息香酸(下述式〔C3〕所示二胺化合物) C3: 3,5-diamino benzoic acid (diamine compound represented by the following formula [C3])
C4:下述式〔C4〕所示二胺化合物 C4: a diamine compound represented by the following formula [C4]
C5:下述式〔C5〕所示二胺化合物 C5: a diamine compound represented by the following formula [C5]
C6:1,3-二胺基-4-十八氧基苯(下述式〔C6〕所示二胺化合物) C6: 1,3-diamino-4-octadecylbenzene (diamine compound represented by the following formula [C6])
D1:YH-434L(東都化成製)(環氧系交聯性化合物) D1: YH-434L (made by Toki Chemical Co., Ltd.) (epoxy-based cross-linking compound)
D2:OXT-221(東亞合成製)(氧雜環丁烷系交聯性化合物) D2: OXT-221 (made by East Asia Synthetic) (oxetane-based cross-linking compound)
D3:下述式所示交聯性化合物(羥基化酚系交聯性化合物) D3: a crosslinkable compound represented by the following formula (hydroxylated phenol-based crosslinkable compound)
NMP:N-甲基-2-吡咯烷酮 NMP: N-methyl-2-pyrrolidone
NEP:N-乙基-2-吡咯烷酮 NEP: N-ethyl-2-pyrrolidone
G-BL:γ-丁內酯 G-BL: γ-butyrolactone
BCS:2-丁氧基乙醇 BCS: 2-butoxyethanol
PB:丙二醇單丁基醚 PB: propylene glycol monobutyl ether
合成例中之聚醯亞胺前驅物及聚醯亞胺的分子量為使用常溫凝膠浸透層析法(GPC)裝置(GPC-101)(昭和電工公司製)、管柱(KD-803,KD-805)(Shodex公司製),如下述進行測定。 The molecular weight of the polyimine precursor and the polyimine in the synthesis example is a room temperature gel permeation chromatography (GPC) device (GPC-101) (manufactured by Showa Denko Co., Ltd.), and a column (KD-803, KD). -805) (manufactured by Shodex Co., Ltd.), and the measurement was carried out as follows.
管柱溫度:50℃ Column temperature: 50 ° C
溶離液:N,N’-二甲基甲醯胺(作為添加劑,溴化鋰一水合物(LiBr‧H2O)30mmol/L(公升)、磷酸‧無水結晶(鄰磷酸)30mmol/L、四氫呋喃(THF)10ml/L) Dissolution: N,N'-dimethylformamide (as an additive, lithium bromide monohydrate (LiBr‧H 2 O) 30 mmol / L (liter), phosphoric acid ‧ anhydrous crystals (o-phosphoric acid) 30 mmol / L, tetrahydrofuran ( THF) 10ml/L)
流速:1.0ml/分鐘 Flow rate: 1.0ml/min
校準曲線作成用標準樣品: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)(聚合物實驗室公司製)。 The calibration curve was prepared using standard samples: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000, and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; about 12,000, 4,000, and 1,000) (polymerization) Laboratory company).
合成例中之聚醯亞胺的醯亞胺化率如以下進行測定。將聚醯亞胺粉末20mg放入NMR(核磁共振)樣品管 (NMR取樣標準管, 5(草野科學公司製)),添加重氫化二甲基亞碸(DMSO-d6,0.05質量%TMS(四甲基矽烷)混合品)(0.53ml),施予超音波使其完全溶解。將該溶液以NMR測定機(JNW-ECA500)(日本電子數據公司製)測定500MHz的質子NMR。醯亞胺化率係將來自在醯亞胺化前後無變化的結構之質子作為基準質子而決定,使用該質子之波峰積算值與來自出現於9.5ppm~10.0ppm附近的醯胺酸的NH基之質子波峰積算值,藉由以下式子求得。 The oxime imidization ratio of the polyimine in the synthesis example was measured as follows. 20 mg of polyimine powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling standard tube, 5 (manufactured by Kusano Scientific Co., Ltd.), a solution of dimethyl hydrazine (DMSO-d6, 0.05% by mass of TMS (tetramethyl decane)) (0.53 ml) was added thereto, and ultrasonic waves were applied to completely dissolve them. This solution was measured for 500 MHz proton NMR by an NMR measuring machine (JNW-ECA500) (manufactured by JEOL Ltd.). The ruthenium imidization rate is determined by using a proton from a structure which does not change before and after imidization as a reference proton, and the peak value of the proton is used and the NH group derived from proline which is present in the vicinity of 9.5 ppm to 10.0 ppm. The proton peak product value is obtained by the following formula.
醯亞胺化率(%)=(1-α‧x/y)×100 醯 imidization rate (%) = (1-α‧x/y) × 100
上述式中,x為來自醯胺酸之NH基的質子波峰積算值,y為基準質子之波峰積算值,α為聚醯胺酸(醯亞胺化率為0%)之情況中對於1個醯胺酸之NH基質子的基準質子之個數比率。 In the above formula, x is the proton peak product value derived from the NH group of proline, y is the peak integrated value of the reference proton, and α is one for the case of polyproline (the imidization ratio is 0%). The ratio of the number of reference protons of the NH proton of proline.
合成例1~15的聚醯胺酸及聚醯亞胺如表1表示。 The polylysine and the polyimide of Synthesis Examples 1 to 15 are shown in Table 1.
將A1(3.44g,16.2mmol)、B1(3.70g,9.73mmol)、C1(2.45g,22.7mmol)於NMP(28.1g)中混合,在40℃進行5小時反應後,加入A2(3.18g,16.2mmol)與NMP(23.0g),在40℃進行6小時反應,得到固體成分濃度為20.0質量%之聚醯胺酸溶液(A)。該聚醯胺酸之數平均分子量為11,500,重量平均分子量為38,600。 A1 (3.44 g, 16.2 mmol), B1 (3.70 g, 9.73 mmol), C1 (2.45 g, 22.7 mmol) were mixed in NMP (28.1 g), and after reacting at 40 ° C for 5 hours, A2 (3.18 g) was added. 16.2 mmol) and NMP (23.0 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (A) having a solid concentration of 20.0% by mass. The polyamine has a number average molecular weight of 11,500 and a weight average molecular weight of 38,600.
於在合成例1所得之固體成分濃度為20.0質量%之聚醯胺酸溶液(A)(15.0g)中加入NMP,稀釋至6質量%後,作為醯亞胺化觸媒加入乙酸酐(2.33g)、吡啶(1.21g),在40℃進行3小時反應。將該反應溶液投入於甲醇(350ml)中,過濾分離所得之沈澱物。將該沈澱物以甲醇洗淨,在60℃減壓乾燥後得到聚醯亞胺粉末(B)。該聚醯亞胺之醯亞胺化率為52%,數平均分子量為10,980,重量平均分子量為33,200。 NMP was added to the polyamic acid solution (A) (15.0 g) having a solid content concentration of 20.0% by mass obtained in Synthesis Example 1, and after diluting to 6 mass%, acetic anhydride (2.33) was added as a ruthenium catalyst. g), pyridine (1.21 g), and reacted at 40 ° C for 3 hours. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (B). The polyimine had a ruthenium iodide ratio of 52%, a number average molecular weight of 10,980, and a weight average molecular weight of 33,200.
將A1(3.31g,15.6mmol)、B1(3.56g,9.36mmol)、C4(2.67g,21.8mmol)在NMP(27.7g)中混合,在40℃進行5小時反應後,加入A2(3.06g,15.6mmol)與NMP(22.7g),在40℃進行6小時反應,得到固體成分濃度為20.0質量%之聚醯胺酸溶液。 A1 (3.31 g, 15.6 mmol), B1 (3.56 g, 9.36 mmol), C4 (2.67 g, 21.8 mmol) were mixed in NMP (27.7 g), and after reacting at 40 ° C for 5 hours, A2 (3.06 g) was added. 15.6 mmol) and NMP (22.7 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a solid concentration of 20.0% by mass.
於所得之聚醯胺酸溶液(20.5g)中加入NMP,稀釋至6質量%後,作為醯亞胺化觸媒加入乙酸酐(2.32g)、吡啶(1.21g),在40℃進行3小時反應。將該反應溶液投入於甲醇(350ml)中,過濾分離所得之沈澱物。將該沈澱物以甲醇洗淨,在60℃減壓乾燥後得到聚醯亞胺粉末(C)。該聚醯亞胺之醯亞胺化率為72%,數平均分子量為11,800,重量平均分子量為32,400。 NMP was added to the obtained polyamic acid solution (20.5 g), and after diluting to 6% by mass, acetic anhydride (2.32 g) and pyridine (1.21 g) were added as a ruthenium catalyzed catalyst, and the mixture was carried out at 40 ° C for 3 hours. reaction. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (C). The polyimine had a hydrazine imidation ratio of 72%, a number average molecular weight of 11,800, and a weight average molecular weight of 32,400.
將A1(2.59g,12.2mmol)、B3(3.70g,8.56mmol)、C2(1.72g,15.9mmol)在NMP(24.4g)中混合,在40℃進行5小時反應後,加入A3(3.06g,12.2mmol)與NMP(19.9g),在50℃進行5小時反應,得到固體成分濃度為20.0質量%之聚醯胺酸溶液。 A1 (2.59 g, 12.2 mmol), B3 (3.70 g, 8.56 mmol), C2 (1.72 g, 15.9 mmol) were mixed in NMP (24.4 g), and after reacting at 40 ° C for 5 hours, A3 (3.06 g) was added. 12.2 mmol) and NMP (19.9 g) were reacted at 50 ° C for 5 hours to obtain a polyamic acid solution having a solid concentration of 20.0% by mass.
於所得之聚醯胺酸溶液(15.0g)中,加入NMP並稀釋至6質量%後,作為醯亞胺化觸媒加入乙酸酐(2.03g)、吡啶(1.04g),在40℃進行3.5小時反應。將該反應溶液投入於甲醇(350ml)中,過濾分離所得之沈澱物。將該沈澱物以甲醇洗淨,在60℃減壓乾燥後得到聚醯亞胺粉末(D)。該聚醯亞胺之醯亞胺化率為51%,數平均分子量為12,100,重量平均分子量為35,200。 After adding NMP and diluting to 6 mass%, the obtained poly-proline solution (15.0 g) was added to acetic anhydride (2.03 g) and pyridine (1.04 g) as a ruthenium hydride catalyst, and it was carried out at 40 ° C. Hour response. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to give a polyimine powder (D). The polyimine had a hydrazine imidation ratio of 51%, a number average molecular weight of 12,100, and a weight average molecular weight of 35,200.
將A1(1.98g,9.35mmol)、B2(4.61g,9.35mmol)、C3(2.13g,14.0mmol)在NMP(25.2g)中混合,在40℃進行5小時反應後,加入A2(2.75g,14.0mmol)與NMP(20.7g),在40℃進行6小時反應,得到固體成分濃度為20.0質量%之聚醯胺酸溶液。 A1 (1.98 g, 9.35 mmol), B2 (4.61 g, 9.35 mmol), C3 (2.13 g, 14.0 mmol) were mixed in NMP (25.2 g), and after reacting at 40 ° C for 5 hours, A2 (2.75 g) was added. 14.0 mmol) and NMP (20.7 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a solid concentration of 20.0% by mass.
於所得之聚醯胺酸溶液(15.1g)中,加入NMP並稀釋至6質量%後,作為醯亞胺化觸媒加入乙酸酐 (2.04g)、吡啶(1.05g),在40℃進行3小時反應。將該反應溶液投入於甲醇(350ml)中,過濾分離所得之沈澱物。將該沈澱物以甲醇洗淨,在60℃減壓乾燥後得到聚醯亞胺粉末(E)。該聚醯亞胺之醯亞胺化率為70%,數平均分子量為13,000,重量平均分子量為34,200。 After adding NMP and diluting to 6 mass% in the obtained polyamic acid solution (15.1 g), acetic anhydride was added as a ruthenium amide catalyst. (2.04 g) and pyridine (1.05 g) were reacted at 40 ° C for 3 hours. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to give a polyimine powder (E). The polyimine had a hydrazine imidation ratio of 70%, a number average molecular weight of 13,000, and a weight average molecular weight of 34,200.
將A1(1.34g,6.29mmol)、B4(2.81g,6.29mmol)、C4(1.79g,14.7mmol)在NMP(19.4g)中混合,在40℃進行5小時反應後,加入A2(2.88g,14.7mmol)與NMP(15.9g),在40℃進行6小時反應,固體成分濃度為20.0質量%之聚醯胺酸溶液。 A1 (1.34 g, 6.29 mmol), B4 (2.81 g, 6.29 mmol), C4 (1.79 g, 14.7 mmol) were mixed in NMP (19.4 g), and after reacting at 40 ° C for 5 hours, A2 (2.88 g) was added. 14.7 mmol) was reacted with NMP (15.9 g) at 40 ° C for 6 hours to obtain a polyamic acid solution having a solid concentration of 20.0% by mass.
於所得之聚醯胺酸溶液(15.0g)中,加入NMP並稀釋至6質量%後,作為醯亞胺化觸媒加入乙酸酐(1.01g)、吡啶(0.79g),在40℃進行1.5小時反應。將該反應溶液投入於甲醇(350ml)中,過濾分離所得之沈澱物。將該沈澱物以甲醇洗淨,在60℃減壓乾燥後得到聚醯亞胺粉末(F)。該聚醯亞胺之醯亞胺化率為52%,數平均分子量為14,200,重量平均分子量為35,100。 After adding NMP and diluting to 6 mass%, the obtained poly-proline solution (15.0 g) was added to acetic anhydride (1.01 g) and pyridine (0.79 g) as a ruthenium catalyst, and 1.5 at 40 ° C. Hour response. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (F). The polyimine had a ruthenium iodide ratio of 52%, a number average molecular weight of 14,200, and a weight average molecular weight of 35,100.
將A1(1.40g,6.60mmol)、B5(3.79g,7.70mmol)、C3(1.84g,12.1mmol)在NMP(22.1g)中混合,在40℃ 進行5小時反應後,加入A2(3.02g,15.4mmol)與NMP(18.1g),在40℃進行6小時反應,得到固體成分濃度為20.0質量%之聚醯胺酸溶液。 A1 (1.40 g, 6.60 mmol), B5 (3.79 g, 7.70 mmol), C3 (1.84 g, 12.1 mmol) were mixed in NMP (22.1 g) at 40 ° C After reacting for 5 hours, A2 (3.02 g, 15.4 mmol) and NMP (18.1 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyamic acid solution having a solid concentration of 20.0% by mass.
於所得之聚醯胺酸溶液(15.0g)中,加入NMP並稀釋至6質量%後,作為醯亞胺化觸媒加入乙酸酐(2.01g)、吡啶(1.04g),在40℃進行2.5小時反應。將該反應溶液投入於甲醇(350ml)中,過濾分離所得之沈澱物。將該沈澱物以甲醇洗淨,在60℃減壓乾燥後得到聚醯亞胺粉末(G)。該聚醯亞胺之醯亞胺化率為53%,數平均分子量為10,800,重量平均分子量為31,100。 After adding NMP and diluting to 6 mass%, the obtained polyamic acid solution (15.0 g) was added to acetic anhydride (2.01 g) and pyridine (1.04 g) as a ruthenium catalyzed catalyst, and it was carried out at 40 ° C at 2.5 ° C. Hour response. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (G). The polyimine had a hydrazine imidation ratio of 53%, a number average molecular weight of 10,800, and a weight average molecular weight of 31,100.
將A1(2.54g,12.0mmol)、B1(4.56g,12.0mmol)、C2(1.94g,18.0mmol)在NMP(28.7g)中混合,在40℃進行5小時反應後,加入A4(4.03g,18.0mmol)與NMP(28.7g),在40℃進行8小時反應,得到固體成分濃度為20.0質量%之聚醯胺酸溶液(H)。該聚醯胺酸之數平均分子量為12,900,重量平均分子量為36,300。 A1 (2.54 g, 12.0 mmol), B1 (4.56 g, 12.0 mmol), C2 (1.94 g, 18.0 mmol) were mixed in NMP (28.7 g), and after reacting at 40 ° C for 5 hours, A4 (4.03 g) was added. 18.0 mmol) and NMP (28.7 g) were reacted at 40 ° C for 8 hours to obtain a polyamic acid solution (H) having a solid concentration of 20.0% by mass. The polyamine has a number average molecular weight of 12,900 and a weight average molecular weight of 36,300.
將A1(3.22g,15.2mmol)、B5(4.99g,10.1mmol)、C5(5.51g,40.5mmol)在NMP(40.0g)中混合,在40℃進行5小時反應後,加入A4(7.94g,35.4mmol)與NMP (32.7g),在40℃進行小時反應,得到固體成分濃度為20.0質量%之聚醯胺酸溶液。 A1 (3.22 g, 15.2 mmol), B5 (4.99 g, 10.1 mmol), C5 (5.51 g, 40.5 mmol) were mixed in NMP (40.0 g), and reacted at 40 ° C for 5 hours, then A4 (7.94 g) was added. , 35.4mmol) with NMP (32.7 g), the reaction was carried out at 40 ° C for an hour to obtain a polyamic acid solution having a solid concentration of 20.0% by mass.
於所得之聚醯胺酸溶液(15.0g)中,加入NMP並稀釋至6質量%後,作為醯亞胺化觸媒加入乙酸酐(2.15g)、吡啶(1.11g),在40℃進行1.5小時反應。將該反應溶液投入於甲醇(350ml)中,過濾分離所得之沈澱物。將該沈澱物以甲醇洗淨,在60℃減壓乾燥後得到聚醯亞胺粉末(I)。該聚醯亞胺之醯亞胺化率為50%,數平均分子量為12,200,重量平均分子量為33,700。 After adding NMP and diluting to 6 mass%, the obtained poly-proline acid solution (15.0 g) was added to acetic anhydride (2.15 g) and pyridine (1.11 g) as a ruthenium amide catalyst, and 1.5 at 40 ° C. Hour response. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (I). The polyimine had a hydrazine imidation ratio of 50%, a number average molecular weight of 12,200, and a weight average molecular weight of 33,700.
將A1(2.98g,14.1mmol)、B3(6.08g,14.1mmol)、C4(4.00g,32.8mmol)在NMP(50.4g)中混合,在40℃進行5小時反應後,加入A5(9.84g,32.8mmol)與NMP(41.2g),在40℃進行8小時反應,得到固體成分濃度為20.0質量%之聚醯胺酸溶液。 A1 (2.98 g, 14.1 mmol), B3 (6.08 g, 14.1 mmol), C4 (4.00 g, 32.8 mmol) were mixed in NMP (50.4 g), and reacted at 40 ° C for 5 hours, then A5 (9.84 g) was added. 32.8 mmol) and NMP (41.2 g) were reacted at 40 ° C for 8 hours to obtain a polyamic acid solution having a solid concentration of 20.0% by mass.
於所得之聚醯胺酸溶液(15.0g)中,加入NMP並稀釋至6質量%後,作為醯亞胺化觸媒加入乙酸酐(1.88g)、吡啶(1.00g),在40℃進行2小時反應。將該反應溶液投入於甲醇(350ml)中,過濾分離所得之沈澱物。將該沈澱物以甲醇洗淨,在60℃減壓乾燥後得到聚醯亞胺粉末(J)。該聚醯亞胺之醯亞胺化率為74%,數平均分子量為11,500,重量平均分子量為35,600。 After adding NMP and diluting to 6 mass%, the obtained poly-proline acid solution (15.0 g) was added to acetic anhydride (1.88 g) and pyridine (1.00 g) as a ruthenium amide catalyst, and it was carried out at 40 ° C. Hour response. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (J). The polyimine had a ruthenium iodide ratio of 74%, a number average molecular weight of 11,500, and a weight average molecular weight of 35,600.
將A1(3.40g,16.0mmol)、C6(3.62g,9.61mmol)、C1(2.42g,22.4mmol)在NMP(19.8g)中混合,在40℃進行5小時反應後,加入A2(3.14g,16.0mmol)與NMP(16.2g),在40℃進行6小時反應,得到固體成分濃度為20.0質量%之聚醯胺酸溶液(K)。該聚醯胺酸之數平均分子量為12,100,重量平均分子量為32,000。 A1 (3.40 g, 16.0 mmol), C6 (3.62 g, 9.61 mmol), C1 (2.42 g, 22.4 mmol) were mixed in NMP (19.8 g), and reacted at 40 ° C for 5 hours, then A2 (3.14 g) was added. 16.0 mmol) and NMP (16.2 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (K) having a solid concentration of 20.0% by mass. The polyamic acid had a number average molecular weight of 12,100 and a weight average molecular weight of 32,000.
將A1(3.30g,15.6mmol)、C6(3.51g,9.33mmol)、C4(2.66g,21.8mmol)在NMP(19.8g)中混合,在40℃進行5小時反應後,加入A2(3.05g,15.6mmol)與NMP(16.2g),在40℃進行6小時反應,得到固體成分濃度為20.0質量%之聚醯胺酸溶液。 A1 (3.30 g, 15.6 mmol), C6 (3.51 g, 9.33 mmol), C4 (2.66 g, 21.8 mmol) were mixed in NMP (19.8 g), and after reacting at 40 ° C for 5 hours, A2 (3.05 g) was added. 15.6 mmol) and NMP (16.2 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a solid concentration of 20.0% by mass.
於所得之聚醯胺酸溶液(15.0g)中,加入NMP並稀釋至6質量%後,作為醯亞胺化觸媒加入乙酸酐(2.28g)、吡啶(1.17g),在40℃進行3小時反應。將該反應溶液投入於甲醇(350ml)中,過濾分離所得之沈澱物。將該沈澱物以甲醇洗淨,在60℃減壓乾燥後得到聚醯亞胺粉末(L)。該聚醯亞胺之醯亞胺化率為73%,數平均分子量為12,000,重量平均分子量為29,100。 After adding NMP and diluting to 6 mass%, the obtained poly-proline solution (15.0 g) was added to acetic anhydride (2.28 g) and pyridine (1.17 g) as a ruthenium hydride catalyst, and it was carried out at 40 ° C. Hour response. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (L). The polyimine had a ruthenium iodide ratio of 73%, a number average molecular weight of 12,000, and a weight average molecular weight of 29,100.
將A2(3.53g,18.0mmol)、B1(2.05g,5.40mmol)、C1(1.36g,12.6mmol)在NMP(30.1g)中混合,在40℃進行8小時反應,得到固體成分濃度為20.0質量%之聚醯胺酸溶液。 A2 (3.53 g, 18.0 mmol), B1 (2.05 g, 5.40 mmol), C1 (1.36 g, 12.6 mmol) were mixed in NMP (30.1 g), and the reaction was carried out at 40 ° C for 8 hours to obtain a solid concentration of 20.0. Mass% polyamine solution.
於所得之聚醯胺酸溶液(15.0g)中,加入NMP並稀釋至6質量%後,作為醯亞胺化觸媒加入乙酸酐(1.59g)、吡啶(0.74g),在40℃進行2.5小時反應。將該反應溶液投入於甲醇(350ml)中,過濾分離所得之沈澱物。將該沈澱物以甲醇洗淨,在60℃減壓乾燥後得到聚醯亞胺粉末(M)。該聚醯亞胺之醯亞胺化率為50%,數平均分子量為14,700,重量平均分子量為40,100。 After adding NMP and diluting to 6 mass%, the obtained polyamic acid solution (15.0 g) was added to acetic anhydride (1.59 g) and pyridine (0.74 g) as a ruthenium catalyzed catalyst, and it was carried out at 40 ° C at 2.5 ° C. Hour response. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to give a polyimine powder (M). The polyimine had a hydrazine imidation ratio of 50%, a number average molecular weight of 14,700, and a weight average molecular weight of 40,100.
將A3(1.51g,6.05mmol)、B4(2.70g,6.05mmol)、C4(1.73g,14.1mmol)在NMP(19.2g)中混合,在80℃進行5小時反應後,加入A2(2.77g,14.1mmol)與NMP(19.2g),在40℃進行6小時反應,得到固體成分濃度為20.0質量%之聚醯胺酸溶液。 A3 (1.51 g, 6.05 mmol), B4 (2.70 g, 6.05 mmol), C4 (1.73 g, 14.1 mmol) were mixed in NMP (19.2 g), and after reacting at 80 ° C for 5 hours, A2 (2.77 g) was added. 14.1 mmol) and NMP (19.2 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a solid concentration of 20.0% by mass.
於所得之聚醯胺酸溶液(15.0g)中,加入NMP並稀釋至6質量%後,作為醯亞胺化觸媒加入乙酸酐(2.15g)、吡啶(1.11g),在40℃進行2.5小時反應。將該反應溶液投入於甲醇(350ml)中,過濾分離所得之沈澱物。將該沈澱物以甲醇洗淨,在60℃減壓乾燥後得 到聚醯亞胺粉末(N)。該聚醯亞胺之醯亞胺化率為53%,數平均分子量為13,800,重量平均分子量為37,700。 After adding NMP and diluting to 6 mass%, the obtained poly-proline solution (15.0 g) was added to acetic anhydride (2.15 g) and pyridine (1.11 g) as a ruthenium catalyzed catalyst, and it was carried out at 40 ° C at 2.5 ° C. Hour response. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 60 ° C. To polyimine powder (N). The polyimine had a hydrazine imidization ratio of 53%, a number average molecular weight of 13,800, and a weight average molecular weight of 37,700.
將A3(3.43g,13.7mmol)、B3(4.15g,9.60mmol)、C2(1.93g,17.8mmol)在NMP(26.8g)中混合,在80℃進行5小時反應後,加入A2(2.69g,13.7mmol)與NMP(22.0g),在40℃進行6小時反應,得到固體成分濃度為20.0質量%之聚醯胺酸溶液。 A3 (3.43 g, 13.7 mmol), B3 (4.15 g, 9.60 mmol), C2 (1.93 g, 17.8 mmol) were mixed in NMP (26.8 g), and reacted at 80 ° C for 5 hours, then A2 (2.69 g) was added. 13.7 mmol) and NMP (22.0 g) were reacted at 40 ° C for 6 hours to obtain a polyglycine solution having a solid concentration of 20.0% by mass.
於所得之聚醯胺酸溶液(15.0g)中,加入NMP並稀釋至6質量%後,作為醯亞胺化觸媒加入乙酸酐(3.57g)、吡啶(1.66g),在50℃進行3小時反應。將該反應溶液投入於甲醇(350ml)中,過濾分離所得之沈澱物。將該沈澱物以甲醇洗淨,在60℃減壓乾燥後得到聚醯亞胺粉末(O)。該聚醯亞胺之醯亞胺化率為52%,數平均分子量為15,600,重量平均分子量為32,700。 After adding NMP and diluting to 6 mass%, the obtained poly-proline solution (15.0 g) was added to acetic anhydride (3.57 g) and pyridine (1.66 g) as a ruthenium catalyzed catalyst, and it was carried out at 50 ° C. Hour response. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (O). The polyimine had a ruthenium iodide ratio of 52%, a number average molecular weight of 15,600, and a weight average molecular weight of 32,700.
將在合成例1所得之固體成分濃度20.0質量%之聚醯胺酸溶液(A)(9.03g)、NMP(8.91g)及BCS(12.0g)在25℃進行6小時混合,得到液晶配向處理劑(1)。於該液晶配向處理劑中未見到混濁或析出物等異常現像,確認為均勻之溶液。 Polylysine solution (A) (9.03 g), NMP (8.91 g), and BCS (12.0 g) having a solid content concentration of 20.0% by mass obtained in Synthesis Example 1 were mixed at 25 ° C for 6 hours to obtain a liquid crystal alignment treatment. Agent (1). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
將合成例2所得之聚醯亞胺粉末(B)(1.80g)、NMP(2.72g)、NEP(9.03g)及BCS(16.5g)在25℃下進行8小時混合,得到液晶配向處理劑(2)。於該液晶配向處理劑中未見到混濁或析出物等異常現像,確認為均勻之溶液。 The polyimine powder (B) (1.80 g) obtained in Synthesis Example 2, NMP (2.72 g), NEP (9.03 g), and BCS (16.5 g) were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent. (2). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
將合成例3所得之聚醯亞胺粉末(C)(1.80g)、NEP(13.2g)、BCS(7.50g)及PB(7.53g)在25℃下進行8小時混合,得到液晶配向處理劑(3)。於該液晶配向處理劑中未見到混濁或析出物等異常現像,確認為均勻之溶液。 The polyimine powder (C) (1.80 g), NEP (13.2 g), BCS (7.50 g) and PB (7.53 g) obtained in Synthesis Example 3 were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent. (3). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
將合成例4所得之聚醯亞胺粉末(D)(1.81g)、NMP(7.41g)、NEP(9.10g)、BCS(6.00g)及PB(6.04g)在25℃下進行8小時混合,得到液晶配向處理劑(4)。於該液晶配向處理劑中未見到混濁或析出物等異常現像,確認為均勻之溶液。 The polyimine powder (D) (1.81 g) obtained in Synthesis Example 4, NMP (7.41 g), NEP (9.10 g), BCS (6.00 g), and PB (6.04 g) were mixed at 25 ° C for 8 hours. A liquid crystal alignment treatment agent (4) was obtained. No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
將合成例5所得之聚醯亞胺粉末(E)(1.79g)、 NMP(4.20g)、NEP(11.9g)及PB(11.9g)在25℃下進行8小時混合,得到液晶配向處理劑(5)。於該液晶配向處理劑中未見到混濁或析出物等異常現像,確認為均勻之溶液。 The polyimine powder (E) (1.79 g) obtained in Synthesis Example 5, NMP (4.20 g), NEP (11.9 g), and PB (11.9 g) were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent (5). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
將合成例6所得之聚醯亞胺粉末(F)(1.80g)、NEP(7.20g)、G-BL(9.06g)及BCS(12.0g)在25℃下進行8小時混合,得到液晶配向處理劑(6)。於該液晶配向處理劑中未見到混濁或析出物等異常現像,確認為均勻之溶液。 The polyimine powder (F) (1.80 g), NEP (7.20 g), G-BL (9.06 g) and BCS (12.0 g) obtained in Synthesis Example 6 were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment. Treatment agent (6). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
將合成例7所得之聚醯亞胺粉末(G)(1.80g)、NEP(13.2g)、G-BL(6.02g)、BCS(6.01g)及PB(3.00g)在25℃下進行8小時混合,得到液晶配向處理劑(7)。於該液晶配向處理劑中未見到混濁或析出物等異常現像,確認為均勻之溶液。 The polyimine powder (G) (1.80 g), NEP (13.2 g), G-BL (6.02 g), BCS (6.01 g), and PB (3.00 g) obtained in Synthesis Example 7 were subjected to 8 at 25 ° C. The mixture was mixed in an hour to obtain a liquid crystal alignment treatment agent (7). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
將合成例8所得之固體成分濃度20.0質量%之聚醯胺酸溶液(H)(9.00g)、G-BL(9.00g)、BCS(6.04g)及PB(6.00g)在25℃進行6小時混合,得到液晶配向處理劑(8)。於該液晶配向處理劑中未見到混濁或析出物 等異常現像,確認為均勻之溶液。 Polylysine solution (H) (9.00 g), G-BL (9.00 g), BCS (6.04 g), and PB (6.00 g) having a solid content concentration of 20.0% by mass obtained in Synthesis Example 8 were carried out at 25 ° C. The mixture was mixed in an hour to obtain a liquid crystal alignment treatment agent (8). No turbidity or precipitates were observed in the liquid crystal alignment agent The abnormal image is confirmed to be a homogeneous solution.
將合成例9所得之聚醯亞胺粉末(I)(1.80g)、NMP(14.7g)及BCS(13.5g)在25℃下進行8小時混合,得到液晶配向處理劑(9)。於該液晶配向處理劑中未見到混濁或析出物等異常現像,確認為均勻之溶液。 The polyimine powder (I) (1.80 g), NMP (14.7 g) and BCS (13.5 g) obtained in Synthesis Example 9 were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent (9). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
將合成例10所得之聚醯亞胺粉末(J)(1.80g)、NMP(1.22g)、NEP(12.0g)、BCS(9.01g)及PB(6.00g)在25℃下進行8小時混合,得到液晶配向處理劑(10)。於該液晶配向處理劑中未見到混濁或析出物等異常現像,確認為均勻之溶液。 The polyimine powder (J) (1.80 g) obtained in Synthesis Example 10, NMP (1.22 g), NEP (12.0 g), BCS (9.01 g), and PB (6.00 g) were mixed at 25 ° C for 8 hours. A liquid crystal alignment treatment agent (10) was obtained. No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
將合成例2所得之聚醯亞胺粉末(B)(1.80g)、NMP(1.23g)、NEP(12.0g)、BCS(9.02g)、PB(6.03g)及D1(0.05g)在25℃下進行8小時混合,得到液晶配向處理劑(11)。於該液晶配向處理劑中未見到混濁或析出物等異常現像,確認為均勻之溶液。 The polyimine powder (B) (1.80 g), NMP (1.23 g), NEP (12.0 g), BCS (9.02 g), PB (6.03 g) and D1 (0.05 g) obtained in Synthesis Example 2 were in 25 The mixture was mixed for 8 hours at ° C to obtain a liquid crystal alignment treatment agent (11). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
將合成例3所得之聚醯亞胺粉末(C)(1.80g)、G- BL(19.2g)、BCS(9.01g)及D2(0.05g)在25℃下進行8小時混合,得到液晶配向處理劑(12)。於該液晶配向處理劑中未見到混濁或析出物等異常現像,確認為均勻之溶液。 The polyimine powder (C) (1.80 g) obtained in Synthesis Example 3, G- BL (19.2 g), BCS (9.01 g), and D2 (0.05 g) were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent (12). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
將合成例3所得之聚醯亞胺粉末(C)(1.80g)、NMP(8.70g)、G-BL(9.00g)、BCS(9.01g)、PB(9.00g)及D3(0.05g)在25℃下進行8小時混合,得到液晶配向處理劑(13)。於該液晶配向處理劑中未見到混濁或析出物等異常現像,確認為均勻之溶液。 Polyimine powder (C) (1.80 g) obtained in Synthesis Example 3, NMP (8.70 g), G-BL (9.00 g), BCS (9.01 g), PB (9.00 g), and D3 (0.05 g) The mixture was mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent (13). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
將合成例2所得之聚醯亞胺粉末(B)(1.05g)、NMP(2.00g)、G-BL(9.02g)、BCS(9.02g)及PB(9.02g)在25℃下進行8小時混合,得到液晶配向處理劑(14)。於該液晶配向處理劑中未見到混濁或析出物等異常現像,確認為均勻之溶液。 The polyimine powder (B) (1.05 g), NMP (2.00 g), G-BL (9.02 g), BCS (9.02 g), and PB (9.02 g) obtained in Synthesis Example 2 were subjected to 8 at 25 ° C. The mixture was mixed in an hour to obtain a liquid crystal alignment treatment agent (14). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
將合成例3所得之聚醯亞胺粉末(C)(1.06g)、NMP(5.01g)、NEP(9.10g)、BCS(7.60g)及PB(7.60g)在25℃下進行8小時混合,得到液晶配向處理劑(15)。於該液晶配向處理劑中未見到混濁或析出物等 異常現像,確認為均勻之溶液。 The polyimine powder (C) (1.06 g) obtained in Synthesis Example 3, NMP (5.01 g), NEP (9.10 g), BCS (7.60 g), and PB (7.60 g) were mixed at 25 ° C for 8 hours. A liquid crystal alignment treatment agent (15) was obtained. No turbidity, precipitates, etc. were observed in the liquid crystal alignment agent An abnormal image was confirmed as a homogeneous solution.
將合成例11所得之固體成分濃度19.9質量%之聚醯胺酸溶液(K)(9.03g)、NMP(9.30g)及BCS(12.2g)在25℃進行6小時混合,得到液晶配向處理劑(16)。於該液晶配向處理劑中未見到混濁或析出物等異常現像,確認為均勻之溶液。 Polylysine solution (K) (9.03 g), NMP (9.30 g), and BCS (12.2 g) having a solid content concentration of 19.9% by mass obtained in Synthesis Example 11 were mixed at 25 ° C for 6 hours to obtain a liquid crystal alignment treatment agent. (16). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
將合成例12所得之聚醯亞胺粉末(L)(1.80g)、NEP(13.2g)、BCS(7.52g)及PB(7.50g)在25℃下進行8小時混合,得到液晶配向處理劑(17)。於該液晶配向處理劑中未見到混濁或析出物等異常現像,確認為均勻之溶液。 The polyimine powder (L) (1.80 g) obtained in Synthesis Example 12, NEP (13.2 g), BCS (7.52 g), and PB (7.50 g) were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent. (17). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
將合成例13所得之聚醯亞胺粉末(M)(1.80g)、NMP(2.71g)NEP(9.00g)及BCS(16.5g)在25℃下進行8小時混合,得到液晶配向處理劑(18)。於該液晶配向處理劑中未見到混濁或析出物等異常現像,確認為均勻之溶液。 The polyimine powder (M) (1.80 g) obtained in Synthesis Example 13 and NMP (2.71 g) NEP (9.00 g) and BCS (16.5 g) were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent ( 18). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
將合成例14所得之聚醯亞胺粉末(N)(1.80g)、NEP(7.25g)、G-BL(9.06g)及BCS(12.0g)在25℃下進行8小時混合,得到液晶配向處理劑(19)。於該液晶配向處理劑中未見到混濁或析出物等異常現像,確認為均勻之溶液。 The polyimine powder (N) (1.80 g) obtained in Synthesis Example 14, NEP (7.25 g), G-BL (9.06 g), and BCS (12.0 g) were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment. Treatment agent (19). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
將合成例15所得之聚醯亞胺粉末(O)(1.80g)、NMP(7.19g)、NEP(9.00g)、BCS(6.00g)及PB(5.99g)在25℃下進行8小時混合,得到液晶配向處理劑(20)。於該液晶配向處理劑中未見到混濁或析出物等異常現像,確認為均勻之溶液。 The polyimine powder (O) (1.80 g) obtained in Synthesis Example 15, NMP (7.19 g), NEP (9.00 g), BCS (6.00 g), and PB (5.99 g) were mixed at 25 ° C for 8 hours. A liquid crystal alignment treatment agent (20) was obtained. No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.
使用實施例1~15及比較例1~5所得之液晶配向處理劑,進行「液晶胞之製作(一般液晶胞)」、「預傾角之熱耐性的評估(一般液晶胞)」、「電氣特性(電壓保持率)之評估(一般液晶胞)」、「液晶胞之製作及單體之分散性評估(PSA胞)」。該條件如下述。 Using the liquid crystal alignment treatment agents obtained in Examples 1 to 15 and Comparative Examples 1 to 5, "production of liquid crystal cells (general liquid crystal cell)", "evaluation of heat resistance of pretilt angle (general liquid crystal cell)", and "electrical characteristics" were performed. (Evaluation of voltage holding ratio) (general liquid crystal cell), "production of liquid crystal cell, and evaluation of dispersibility of monomer (PSA cell)". This condition is as follows.
將實施例1~15及比較例1~5所得之液晶配向處理劑旋轉塗布於附有30×40mmITO電極之基板的ITO面,於加熱板上進行80℃之5分鐘加熱處理,在熱循環型無塵烤箱中進行230℃之30分鐘加熱處理,得到膜厚 100nm的附有液晶配向膜(聚醯亞胺膜)之基板。 The liquid crystal alignment treatment agents obtained in Examples 1 to 15 and Comparative Examples 1 to 5 were spin-coated on an ITO surface of a substrate having a 30×40 mm ITO electrode, and heat-treated at 80° C. for 5 minutes on a hot plate to form a heat cycle type. Heat treatment at 230 ° C for 30 minutes in a dust-free oven to obtain a film thickness A substrate of 100 nm with a liquid crystal alignment film (polyimine film).
將所得之聚醯亞胺膜面,使用輥徑120mm之摩擦裝置,以輥轉動數300rpm、輥進行速度20mm/sec、押入量0.2mm之條件下,以人造纖維布進行摩擦處理,得到附有液晶配向膜之基板。 The obtained polyimide film surface was rubbed with a man-made fiber cloth using a friction device having a roll diameter of 120 mm at a roller rotation speed of 300 rpm, a roll speed of 20 mm/sec, and a pushing amount of 0.2 mm. The substrate of the liquid crystal alignment film.
準備2片附有摩擦處理後之液晶配向膜的基板,將液晶配向膜面作為內側,夾著40μm之間隔物,組合成摩擦方向為相反方向,以密封劑黏著周圍製作出空胞。於該空胞藉由減壓注入法,注入液晶MLC-2003(默克日本公司製),密封注入口後得到反平行配向之向列液晶胞。 Two sheets of the liquid crystal alignment film with the rubbed treatment were prepared, and the liquid crystal alignment film surface was placed inside, and a spacer of 40 μm was interposed, and the rubbing direction was combined in the opposite direction, and the cells were formed by adhering the sealant around the inside. In the empty cell, a liquid crystal MLC-2003 (manufactured by Merck Japan Co., Ltd.) was injected by a vacuum injection method, and an antiparallel alignment nematic liquid crystal cell was obtained by sealing the injection port.
測定上述所製作之液晶胞的預傾角。又將該液晶胞在熱循環型烤箱中以120℃進行24小時加熱後,測定預傾角。且,使用傾斜測定裝置(ELSICON公司製模型PAS-301)進行。結果如表2所示。 The pretilt angle of the liquid crystal cell produced above was measured. Further, the liquid crystal cell was heated in a heat cycle type oven at 120 ° C for 24 hours, and then the pretilt angle was measured. Further, it was carried out using a tilt measuring device (model PAS-301 manufactured by ELSICON Co., Ltd.). The results are shown in Table 2.
將實施例1~5、比較例3及5所得之液晶配向處理劑,旋轉塗布於附有30×40mm ITO電極之基板的ITO面,於加熱板上以80℃進行5分鐘,在熱循環型無塵烤箱中以230℃進行30分鐘加熱處理後,得到附有膜厚100nm之聚醯亞胺液晶配向膜的基板。 The liquid crystal alignment treatment agents obtained in Examples 1 to 5 and Comparative Examples 3 and 5 were spin-coated on the ITO surface of a substrate having a 30×40 mm ITO electrode, and baked on a hot plate at 80° C. for 5 minutes in a heat cycle type. After heat-treating at 230 ° C for 30 minutes in a dust-free oven, a substrate having a polyimine liquid crystal alignment film having a thickness of 100 nm was obtained.
準備所得之附有液晶配向膜之基板2片,將液晶配向膜面作為內側,組合為夾著6μm之間隔物,以 密封劑黏著周圍後製作出空胞。於該空胞中藉由減壓注入法,注入MLC-6608(默克日本製),密封注入口後得到向列液晶胞。 Prepare two pieces of the obtained substrate with the liquid crystal alignment film, and set the liquid crystal alignment film surface as the inner side, and combine them to sandwich the spacer of 6 μm. The sealant adheres to the surrounding area to create a hollow cell. MLC-6608 (manufactured by Merck Japan) was injected into the cell by a reduced pressure injection method, and a nematic liquid crystal cell was obtained by sealing the injection port.
於上述所製作之液晶胞中,在80℃之溫度下施予1V的電壓60μm,測定經16.67ms後、及50ms後之電壓,將保持到怎樣程度的電壓作為電壓保持率(VHR)而計算。且,測定為使用VHR-1電壓保持率測定裝置(東陽Technica製),以Voltage:±1V、Pulse Width:60μs、Flame Period:16.67ms或50ms之設定下進行。於電壓保持率的測定結束後的液晶胞上,以365nm換算之50J/cm2的紫外線進行照射後,在與上述同樣條件下,進行電壓保持率之測定。且,紫外線照射為使用桌上型UV硬化裝置(HCT3B28HEX-1)(Sen Light製(SEN LIGHT CORPORATION))進行。結果如表3所示。 In the liquid crystal cell produced as described above, a voltage of 1 V was applied at a temperature of 80 ° C for 60 μm, and a voltage after 16.67 ms and after 50 ms was measured, and how much voltage was maintained as a voltage holding ratio (VHR). . Further, the measurement was carried out using a VHR-1 voltage retention ratio measuring device (manufactured by Toyo Technica) at a setting of Voltage: ±1 V, Pulse Width: 60 μs, Flame Period: 16.67 ms, or 50 ms. After the irradiation of the ultraviolet ray of 50 J/cm 2 in terms of 365 nm on the liquid crystal cell after the measurement of the voltage holding ratio was completed, the voltage holding ratio was measured under the same conditions as above. Further, ultraviolet irradiation was carried out using a desktop type UV curing device (HCT3B28HEX-1) (manufactured by Sen Light (SEN LIGHT CORPORATION)). The results are shown in Table 3.
將實施例1~8、實施例12~15及比較例1~5所得之液晶配向處理劑以細孔徑1μm之膜過濾器進行加壓過濾,使用在-15℃進行48小時保管的溶液,進行單體分散性之評估(PSA胞)。將該溶液旋轉塗布於以純水及異丙基醇(IPA)洗淨之中心上附有10×10mm之圖型間隔20μm的ITO電極之基板(縱40mm×橫30mm、厚度0.7mm)與中心上附有10×40mm的ITO電極之基板(縱40mm×橫30mm、厚度0.7mm)之ITO面,在加熱板上以 100℃進行5分鐘加熱處理後得到膜厚為100nm之聚醯亞胺塗膜。將塗膜面以純水洗淨後,在熱循環型無塵烤箱中以100℃進行15分鐘加熱處理,得到附有液晶配向膜之基板。 The liquid crystal alignment treatment agents obtained in the examples 1 to 8 and the examples 12 to 15 and the comparative examples 1 to 5 were subjected to pressure filtration using a membrane filter having a pore diameter of 1 μm, and the solution was stored at -15 ° C for 48 hours. Evaluation of monomer dispersion (PSA cells). This solution was spin-coated on a substrate (length 40 mm × width 30 mm, thickness 0.7 mm) and a center of an ITO electrode having a pattern of 20 × 10 mm in a pattern of 10 × 10 mm in a center washed with pure water and isopropyl alcohol (IPA). An ITO surface with a 10×40 mm ITO electrode substrate (40 mm in length × 30 mm in width, 0.7 mm in thickness) is attached to the hot plate. After heat treatment at 100 ° C for 5 minutes, a polyimide film having a film thickness of 100 nm was obtained. The surface of the coating film was washed with pure water, and then heat-treated at 100 ° C for 15 minutes in a heat cycle type dust-free oven to obtain a substrate with a liquid crystal alignment film.
於該附有液晶配向膜之基板的液晶配向膜面上,固著4μm之間隔物,於向列液晶(MLC-6608)(默克日本公司製),將下述式所示聚合性化合物(亦稱為單體)(1)與對向列液晶(MLC-6608)混合之液晶滴入1點,其中對於對向列液晶(MLC-6608)之100質量%而言,聚合性化合物(1)為0.7質量%,貼合面板,以密封劑黏著周圍後得到單體分散性評估用之液晶胞。 On the liquid crystal alignment film surface of the substrate with the liquid crystal alignment film, a spacer of 4 μm was fixed, and a polymerizable compound represented by the following formula was added to a nematic liquid crystal (MLC-6608) (manufactured by Merck Japan Co., Ltd.). (1) A liquid crystal mixed with a nematic liquid crystal (MLC-6608) is dropped at 1 point, wherein a polymerizable compound (1) is 100% by mass of the nematic liquid crystal (MLC-6608). ) was 0.7% by mass, and the panel was bonded to the liquid crystal cell for evaluation of monomer dispersion after adhering to the surrounding with a sealant.
存在於液晶胞中之單體所存在之地方因電阻 降低,故於所得之液晶胞施予交流5V之電壓時,液晶胞內之單體的分散區域會顯示黑色。藉由測定在施予電壓時所產生的黑色顯示之圓大小,可評估單體之分散性。將在施予電壓時所產生的黑色顯示之圓直徑所測定之結果如表2所示。 Where the monomer present in the liquid crystal cell exists due to resistance When it is lowered, when the obtained liquid crystal cell is supplied with a voltage of 5 V, the dispersed region of the monomer in the liquid crystal cell shows black. The dispersibility of the monomer can be evaluated by measuring the size of the circle of the black display produced when the voltage is applied. The results of measuring the diameter of the circle of the black display generated when the voltage was applied are shown in Table 2.
又,對於實施例9~11所得之液晶配向處理劑,取代聚合性化合物(1)使用聚合性化合物(2)以外,其他與上述相同下進行單體之分散性評估。 In addition, the liquid crystal alignment treatment agent obtained in each of Examples 9 to 11 was evaluated for the dispersibility of the monomer in the same manner as described above except that the polymerizable compound (2) was used instead of the polymerizable compound (1).
將本發明的實施例14所得之液晶配向處理劑(14)及實施例15所得之液晶配向處理劑(15)以細孔徑1μm的膜過濾器進行加壓過濾,進行噴墨塗布性之評估。噴墨塗布機為使用HIS-200(日立Plant Technologies公司製)。塗布為於以純水及IPA洗淨之ITO(氧化銦錫)蒸鍍基板上,以塗布面積為70×70mm,噴嘴間距為0.423mm,掃描間距為0.5mm,塗布速度為40mm/秒,自塗布至假乾燥的時間為60秒,假乾燥在加熱板上以70℃進行5分鐘之條件下進行。由該結果得知,所有實施例為在所得之液晶配向膜上未見到眼洞或針孔,得到均勻塗布之液晶配向膜。 The liquid crystal alignment treatment agent (14) obtained in Example 14 of the present invention and the liquid crystal alignment treatment agent (15) obtained in Example 15 were subjected to pressure filtration using a membrane filter having a pore diameter of 1 μm to evaluate inkjet coating properties. The inkjet coater was HIS-200 (manufactured by Hitachi Plant Technologies Co., Ltd.). The coating was applied to an ITO (Indium Tin Oxide) vapor-deposited substrate washed with pure water and IPA to have a coating area of 70×70 mm, a nozzle pitch of 0.423 mm, a scanning pitch of 0.5 mm, and a coating speed of 40 mm/sec. The time of application to the dummy drying was 60 seconds, and the dummy drying was carried out on a hot plate at 70 ° C for 5 minutes. From the results, it was found that all the examples showed that no eye holes or pinholes were observed on the obtained liquid crystal alignment film, and a uniformly coated liquid crystal alignment film was obtained.
如上述結果得知,由實施例1~實施例15之液晶配向處理劑所得之液晶配向膜,與由比較例1~比較例5之液晶配向處理劑所得之液晶配向膜做比較,單體之 分散較為廣。因此,可確定實施例1~15之疏水性高且配向不均勻較少。且,實施例3與取代B1使用C6以外,其他皆與實施例3相同的比較例2做比較時,確定實施例3為單體分散性非常廣。又,對於液晶配向性之評估,自實施例1~實施例15之液晶配向處理劑所得之液晶配向膜與自比較例1~比較例5之液晶配向處理劑所得之液晶配向膜做比較,預傾角之加熱前後的變化較小,且預傾角之耐熱性優良。 As a result of the above, it was found that the liquid crystal alignment films obtained from the liquid crystal alignment treatment agents of Examples 1 to 15 were compared with the liquid crystal alignment films obtained by the liquid crystal alignment treatment agents of Comparative Examples 1 to 5, respectively. It is widely dispersed. Therefore, it was confirmed that the hydrophobicity of Examples 1 to 15 was high and the alignment unevenness was small. Further, in the case of Comparative Example 2 in which Example 3 and Substituting B1 were both C6 and Comparative Example 2 which was the same as Example 3, it was confirmed that Example 3 has a very large monomer dispersibility. Further, in the evaluation of the liquid crystal alignment property, the liquid crystal alignment films obtained from the liquid crystal alignment treatment agents of Examples 1 to 15 were compared with the liquid crystal alignment films obtained from the liquid crystal alignment treatment agents of Comparative Examples 1 to 5, and The change before and after the heating of the inclination angle is small, and the heat resistance of the pretilt angle is excellent.
而未含特定四羧酸二酐之比較例3~比較例5或未含特定側鏈型二胺化合物之比較例1、比較例2為單體擴充較為狹隘,預傾角之耐熱性亦較差。 In Comparative Example 3 to Comparative Example 5 which did not contain a specific tetracarboxylic dianhydride or Comparative Example 1 and Comparative Example 2 which did not contain a specific side chain type diamine compound, the monomer expansion was narrow, and the heat resistance of the pretilt angle was also inferior.
又,由表3得知,自實施例之液晶配向處理劑所得之液晶胞即使曝曬於紫外線下,其電壓保持率之降低較小。具體例子為實施例1與不使用A1以外其他與實施例1為同樣構成的比較例3做比較時、或實施例4與取代A1使用A3以外與實施例4為相同之比較例5做比較時。如此藉由使用本發明的液晶配向處理劑,可得到電壓保持率對光耐性為優良的液晶顯示元件。此推測為本發明的液晶配向處理劑含有將〔1〕所示四羧酸二酐作為原料之聚合物(聚醯亞胺或聚醯亞胺前驅物),故形成液晶配向膜時的燒成中,因來自〔1〕所示四羧酸二酐之結構與聚合物交聯等原因,使在聚合物分子間亦產生醯亞胺化,而可得到電壓保持率對於光耐性優良者。 Further, as is clear from Table 3, the liquid crystal cell obtained from the liquid crystal alignment treatment agent of the example had a small decrease in voltage holding ratio even when exposed to ultraviolet light. Specific examples are the comparison between Example 1 and Comparative Example 3 which is the same as Example 1 except that A1 is not used, or Comparative Example 5 in which Example 4 and Example A are the same as Example 4 except that A1 is used instead of A1. . By using the liquid crystal alignment treatment agent of the present invention, a liquid crystal display element having excellent voltage retention and light resistance can be obtained. It is presumed that the liquid crystal alignment agent of the present invention contains a polymer (polyimine or polyimine precursor) containing the tetracarboxylic dianhydride represented by [1] as a raw material, so that firing is performed when a liquid crystal alignment film is formed. In the case where the structure of the tetracarboxylic dianhydride shown in [1] is crosslinked with a polymer or the like, ruthenium imidation is also caused between the polymer molecules, and the voltage holding ratio is excellent in light resistance.
本發明的液晶配向處理劑可得到配向不均勻經改善,且預傾角之耐熱性優良的液晶配向膜。因此,具有由本發明的液晶配向處理劑所得之液晶配向膜的液晶顯示元件可成為信賴性優良者,適合使用於在大畫面下亦具有高精細之液晶電視等,可使用於TN元件、STN元件、TFT液晶元件,特別對於垂直配向型之液晶顯示元件上。 The liquid crystal alignment treatment agent of the present invention can provide a liquid crystal alignment film which is improved in alignment unevenness and excellent in heat resistance at a pretilt angle. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention can be excellent in reliability, and can be suitably used for a liquid crystal television or the like having a high definition in a large screen, and can be used for a TN element or an STN element. , TFT liquid crystal elements, especially for vertical alignment type liquid crystal display elements.
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US8741397B2 (en) * | 2009-11-09 | 2014-06-03 | Jnc Corporation | Liquid crystal display element, liquid crystal composition, aligning agent, method for producing liquid crystal display element, and use of liquid crystal composition |
WO2012014898A1 (en) * | 2010-07-26 | 2012-02-02 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
JP5630451B2 (en) * | 2011-02-23 | 2014-11-26 | 信越化学工業株式会社 | Adhesive composition and adhesive dry film |
WO2012133829A1 (en) * | 2011-03-31 | 2012-10-04 | 日産化学工業株式会社 | Liquid crystal aligning agent, and liquid crystal alignment film produced using same |
-
2014
- 2014-02-26 KR KR1020157026351A patent/KR102184058B1/en active IP Right Grant
- 2014-02-26 CN CN201480024175.4A patent/CN105164579B/en active Active
- 2014-02-26 JP JP2015502996A patent/JP6368955B2/en active Active
- 2014-02-26 WO PCT/JP2014/054766 patent/WO2014133042A1/en active Application Filing
- 2014-02-27 TW TW103106757A patent/TWI620791B/en active
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2018
- 2018-01-19 JP JP2018007700A patent/JP6504377B2/en active Active
Also Published As
Publication number | Publication date |
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JP2018087343A (en) | 2018-06-07 |
CN105164579B (en) | 2018-03-09 |
JP6368955B2 (en) | 2018-08-08 |
TWI620791B (en) | 2018-04-11 |
JPWO2014133042A1 (en) | 2017-02-02 |
KR102184058B1 (en) | 2020-11-27 |
KR20150122210A (en) | 2015-10-30 |
JP6504377B2 (en) | 2019-04-24 |
CN105164579A (en) | 2015-12-16 |
WO2014133042A1 (en) | 2014-09-04 |
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