TWI726987B - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents
Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element Download PDFInfo
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Abstract
本發明係關於含有(A)在指定溫度範圍表現液晶性的感光性側鏈型高分子、(B)反應性液晶元化合物、及(C)有機溶劑的聚合物組成物。根據本發明,提供以高效率賦予配向控制能力、烙印特性優異的液晶配向膜、賦予其之聚合物組成物及橫向電場驅動型液晶顯示元件。 The present invention relates to a polymer composition containing (A) a photosensitive side chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, (B) a reactive mesogen compound, and (C) an organic solvent. According to the present invention, there is provided a liquid crystal alignment film that imparts alignment control ability with high efficiency and is excellent in burn-in characteristics, a polymer composition imparted thereto, and a lateral electric field drive type liquid crystal display element.
Description
本發明係關於新穎的聚合物組成物與使用其之液晶配向膜、及具有該配向膜的基板之製造方法。進一步係關於用以製造傾斜角度特性優異的液晶顯示元件之新穎的方法。 The present invention relates to a novel polymer composition, a liquid crystal alignment film using the same, and a method for manufacturing a substrate having the alignment film. It further relates to a novel method for manufacturing a liquid crystal display element with excellent tilt angle characteristics.
液晶顯示元件己知為輕量、薄型且低消耗電力的顯示裝置,在近年用於大型的電視用途等有驚人的發展。液晶顯示元件由例如以具備電極的透明的一對基板挾持液晶層所構成。而,在液晶顯示元件,以液晶在基板間以所期望之配向狀態之方式,由有機材料所構成的有機膜用作為液晶配向膜。 Liquid crystal display elements are known as light-weight, thin, and low-power-consumption display devices, and they have been used for large-scale television applications in recent years. The liquid crystal display element is configured by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes, for example. However, in a liquid crystal display element, an organic film composed of an organic material is used as a liquid crystal alignment film in such a manner that the liquid crystal is in a desired alignment state between the substrates.
亦即,液晶配向膜為液晶顯示元件的構成構件,且形成於挾持液晶的基板之與液晶相接面,在該基板間具有使液晶朝一定的方向配向之角色。而,在液晶配向膜,除使液晶例如相對於基板向平行方向等、一定的方向配向之功能外,有追求控制液晶的預傾角功能之情形。如此液晶配向膜中,控制液晶的配向的能力(以下,稱配向 控制能力)藉由對構成液晶配向膜的有機膜進行配向處理而賦予。 That is, the liquid crystal alignment film is a constituent member of the liquid crystal display element, and is formed on the contact surface of the substrate holding the liquid crystal with the liquid crystal, and has the role of aligning the liquid crystal in a certain direction between the substrates. However, in the liquid crystal alignment film, in addition to the function of aligning the liquid crystal in a certain direction such as a parallel direction with respect to the substrate, there are cases where the function of controlling the pretilt angle of the liquid crystal is pursued. In such a liquid crystal alignment film, the ability to control the alignment of the liquid crystal (hereinafter referred to as the alignment The control ability) is imparted by the alignment treatment of the organic film constituting the liquid crystal alignment film.
用以賦予配向控制能力的液晶配向膜之配向處理方法方面,從以往摩擦法為己知。摩擦法係指對基板上的聚乙烯基醇或聚醯胺或聚醯亞胺等的有機膜,使其表面以綿、尼龍、聚酯等的布於一定方向擦拭(摩擦)、於擦拭方向(摩擦方向)使液晶配向的方法。該摩擦法因可簡便實現較安定的液晶的配向狀態,在以往的液晶顯示元件的製造製程中被利用。而,液晶配向膜使用的有機膜方面,主要選擇耐熱性等的信賴性或電特性優異的聚醯亞胺系的有機膜。 The alignment treatment method of the liquid crystal alignment film for imparting alignment control ability is known from the conventional rubbing method. The rubbing method refers to the organic film of polyvinyl alcohol, polyamide, or polyimide on the substrate, and the surface is wiped (rubbed) in a certain direction with a cloth of cotton, nylon, polyester, etc., in the wiping direction (Rubbing direction) A method of aligning liquid crystals. Since this rubbing method can easily realize a relatively stable alignment state of liquid crystals, it has been used in the manufacturing process of conventional liquid crystal display elements. Regarding the organic film used for the liquid crystal alignment film, polyimide-based organic films that are excellent in reliability such as heat resistance and electrical properties are mainly selected.
但,摩擦由聚醯亞胺等所構成的液晶配向膜的表面之摩擦法有產生發塵或靜電之問題。又,因近年液晶顯示元件的高精細化或對應基板上的電極或液晶驅動用之切換主動元件造成的凹凸,有無法將液晶配向膜的表面以布均勻摩擦,無法實現均勻的液晶的配向之情形。 However, the rubbing method of rubbing the surface of the liquid crystal alignment film composed of polyimide or the like has the problem of generating dust or static electricity. In addition, due to the high-definition of liquid crystal display elements in recent years or the unevenness caused by the electrodes on the substrate or the switching active element for liquid crystal driving, the surface of the liquid crystal alignment film cannot be rubbed uniformly, and uniform liquid crystal alignment cannot be achieved. situation.
因此,作為不進行摩擦的液晶配向膜之另外配向處理方法,盛行光配向法之檢討。 Therefore, as another alignment treatment method for the liquid crystal alignment film without rubbing, the review of the photo-alignment method is popular.
光配向法雖有種種方法,但藉由直線偏光或校準的光於構成液晶配向膜的有機膜內形成異方向性,依據該異方向性使液晶配向。 Although there are various methods for the photo-alignment method, linearly polarized light or collimated light is used to form anisotropy in the organic film constituting the liquid crystal alignment film, and the liquid crystal is aligned according to the anisotropy.
主要的光配向法方面,己知分解型的光配向法。例如對聚醯亞胺膜照射偏光紫外線,利用分子構造之紫外線吸收的偏光方向依存性產生異方向的分解。而,藉 由未分解而殘留的聚醯亞胺使液晶配向(例如專利文獻1作為參考)。 As for the main optical alignment method, the decomposition-type optical alignment method is known. For example, the polarized ultraviolet light is irradiated to the polyimide film, and the polarization direction dependence of the ultraviolet absorption of the molecular structure is used to cause decomposition in different directions. While, borrow The polyimide remaining undecomposed aligns the liquid crystal (for example, Patent Document 1 is referred to).
又,光交聯型之光配向法亦為習知。例如使用聚肉桂酸乙烯酯,照射偏光紫外線,在與偏光平行的2個側鏈之雙鍵部分,產生二聚化反應(交聯反應)。進而藉由在斜方向照射偏光紫外線表現預傾角(非專利文獻1作為參考)。又,使用側鏈具有香豆素的側鏈型高分子時,照射偏光紫外線,在與偏光平行的側鏈之香豆素部產生光交聯反應,使液晶配向於與偏光方向平行方向(非專利文獻2作為參考)。 Moreover, the photo-alignment method of the photo-crosslinking type is also known. For example, when polyvinyl cinnamate is used and polarized ultraviolet light is irradiated, a dimerization reaction (crosslinking reaction) occurs in the double bond portion of the two side chains parallel to the polarized light. Furthermore, the pretilt angle is expressed by irradiating polarized ultraviolet rays in an oblique direction (Non-Patent Document 1 is for reference). In addition, when a side chain type polymer having coumarin in the side chain is used, polarized ultraviolet light is irradiated to cause a photocrosslinking reaction in the coumarin portion of the side chain parallel to the polarized light, and the liquid crystal is aligned in a direction parallel to the polarization direction (non-polarized light). (Patent Document 2 is taken as a reference).
如以上的例般,在光配向法之液晶配向膜之配向處理方法,不需摩擦且無發塵或靜電產生之疑慮。而,即使對表面有凹凸的液晶顯示元件的基板亦可施以配向處理,為工業上生產製程較佳液晶配向膜之配向處理方法。此外,光配向法,因配向方向可藉由紫外線控制,故於像素中形成多個配向方向不同的區域(配向分割),可補償視野角依賴性。 As in the above example, the alignment treatment method of the liquid crystal alignment film in the photo-alignment method does not require friction and there is no doubt about dust or static electricity. However, even the substrates of liquid crystal display elements with uneven surfaces can be subjected to alignment processing, which is a better alignment processing method for liquid crystal alignment films in industrial production processes. In addition, in the optical alignment method, since the alignment direction can be controlled by ultraviolet rays, a plurality of regions with different alignment directions are formed in the pixel (alignment division), which can compensate the viewing angle dependence.
另一方面,液晶配向膜亦扮演著對液晶賦予某一定傾斜角(預傾角)之角色,賦予預傾角在液晶配向膜之開發中成為重要的課題(專利文獻3~6作為參考)。 On the other hand, the liquid crystal alignment film also plays a role of imparting a certain tilt angle (pretilt angle) to the liquid crystal, and imparting a pretilt angle has become an important issue in the development of the liquid crystal alignment film (Patent Documents 3 to 6 are for reference).
[專利文獻1]日本專利第3893659號公報 [Patent Document 1] Japanese Patent No. 3893659
[專利文獻2]日本特開平02-223916號公報 [Patent Document 2] Japanese Patent Laid-Open No. 02-223916
[專利文獻3]日本特開平04-281427號公報 [Patent Document 3] Japanese Patent Application Laid-Open No. 04-281427
[專利文獻4]日本特開平05-043687號公報 [Patent Document 4] Japanese Patent Laid-Open No. 05-043687
[專利文獻5]日本特開平10-333153號公報 [Patent Document 5] Japanese Patent Application Laid-Open No. 10-333153
[非專利文獻1]S. Kobayashi et al., Journal of Photopolymer Science and Technology, Vol.8, No.2, pp25-262(1995). [Non-Patent Document 1] S. Kobayashi et al., Journal of Photopolymer Science and Technology, Vol. 8, No. 2, pp25-262(1995).
[非專利文獻2]M. Shadt et al., Nature. Vol381, 212(1996). [Non-Patent Document 2] M. Shadt et al., Nature. Vol381, 212 (1996).
如以上般,光配向法與作為液晶顯示元件的配向處理方法的以往工業上利用的摩擦法相比,不需摩擦步驟,因此具有大優點。而,與因摩擦而配向控制能力幾乎成為一定之摩擦法相比,在光配向法,可改變偏光光之照射量而控制配向控制能力。但,在光配向法,欲實現與摩擦法之場合同程度的配向控制能力的場合,有需要大量的偏光光之照射量等、無法實現安定的液晶配向之情形。 As described above, the photo-alignment method does not require a rubbing step compared with the conventional industrially used rubbing method as an alignment processing method for liquid crystal display elements, and therefore has a great advantage. However, compared with the rubbing method where the alignment control ability is almost constant due to rubbing, in the optical alignment method, the irradiation amount of polarized light can be changed to control the alignment control ability. However, in the optical alignment method, when it is desired to realize the alignment control ability of the field contract with the rubbing method, there are situations where a large amount of polarized light irradiation is required, and stable liquid crystal alignment cannot be achieved.
例如在上述專利文獻1記載之分解型的光配向法,需要對聚醯亞胺膜照射來自輸出500W之高壓水銀 燈的紫外光60分鐘等,變得需要長時間且大量的紫外線照射。又,二聚化型或光異構化型的光配向法的場合中,亦有需要數J/cm2~數十J/cm2左右的多量的紫外線照射之情形。進而在光交聯型或光異構化型的光配向法的場合,因液晶的配向之熱安定性或光安定性差,作成液晶顯示元件的場合,有產生配向不良或影像殘留之問題。 For example, in the decomposition-type photo-alignment method described in Patent Document 1, it is necessary to irradiate the polyimide film with ultraviolet light from a high-pressure mercury lamp with an output of 500 W for 60 minutes, etc., which requires a long time and a large amount of ultraviolet radiation. In addition, in the case of a dimerization type or photoisomerization type photo-alignment method, a large amount of ultraviolet radiation of about several J/cm 2 to several tens of J/cm 2 may be required. Furthermore, in the photo-crosslinking type or photo-isomerization type photo-alignment method, the thermal stability or light stability of the alignment of the liquid crystal is poor, and when the liquid crystal display element is made, there is a problem of poor alignment or image retention.
因此,在光配向法,追求配向處理之高效率化或安定液晶配向之實現,追求可對液晶配向膜進行高效率地高配向控制能力的賦予之液晶配向膜或液晶配向劑。 Therefore, in the optical alignment method, high efficiency of alignment processing or realization of stable liquid crystal alignment is pursued, and a liquid crystal alignment film or liquid crystal alignment agent that can provide a liquid crystal alignment film with high efficiency and high alignment control ability is pursued.
本發明之目的在於提供具有以高效率賦予配向控制能力、傾斜角度特性優異的液晶顯示元件用液晶配向膜的基板及具有該基板的垂直電場驅動型液晶顯示元件(例如扭轉向列(TN:Twisted Nematic)型液晶顯示元件、垂直配向(VA:Vertical Alignment)型液晶顯示元件、STN(Super-Twisted Nematic)型液晶顯示元件、ECB(Electrically Controlled Birefringence)型液晶顯示元件及OCB(Optically Compensated Bend)型液晶顯示元件)。 The object of the present invention is to provide a substrate having a liquid crystal alignment film for a liquid crystal display element that imparts alignment control ability with high efficiency and is excellent in tilt angle characteristics, and a vertical electric field drive type liquid crystal display element (such as twisted nematic (TN: Twisted) Nematic) type liquid crystal display element, vertical alignment (VA: Vertical Alignment) type liquid crystal display element, STN (Super-Twisted Nematic) type liquid crystal display element, ECB (Electrically Controlled Birefringence) type liquid crystal display element, and OCB (Optically Compensated Bend) type Liquid crystal display element).
又,本發明之目的除上述目的外,在於提供具有更高的傾斜角度特性的垂直電場驅動型(例如扭轉向列型液晶顯示元件、VA型液晶顯示元件、STN型液晶顯示元件、ECB型液晶顯示元件及OCB型液晶顯示元件)及該元件用的液晶配向膜。又,垂直電場驅動型液晶顯示元件係指在基板面垂直方向外加電場,驅動液晶分子之方式。 In addition, the object of the present invention is to provide a vertical electric field drive type (such as twisted nematic liquid crystal display element, VA liquid crystal display element, STN liquid crystal display element, ECB liquid crystal display element, and ECB liquid crystal display element) with higher tilt angle characteristics. Display element and OCB type liquid crystal display element) and liquid crystal alignment film for the element. In addition, a vertical electric field drive type liquid crystal display element refers to a method in which an electric field is applied in a direction perpendicular to the substrate surface to drive liquid crystal molecules.
本發明者們為了達成上述課題而努力檢討結果,發現以下發明。 The inventors of the present invention worked hard to achieve the above-mentioned problems and found the following inventions.
<1>含有(A)在指定溫度範圍表現液晶性的感光性側鏈型高分子、(B)反應性液晶元化合物及有機溶劑的聚合物組成物。 <1> A polymer composition containing (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, (B) a reactive mesogen compound, and an organic solvent.
<2>上述<1>中,(B)成分的反應性液晶元化合物以下述式(I)表示的化合物者為佳。 <2> In the above <1>, the reactive mesogen compound of the component (B) is preferably a compound represented by the following formula (I).
P-Sp-X-MG-X-Sp-P (I)[式(I)中,P為聚合性基,Sp為具有碳原子1~20個的間隔基,X為選自-O-、-S-、-CO-、-COO-、-OCO-、-OCO-O-的基或單鍵,MG為液晶元基或液晶元支持基,該基較佳為依據下述式II來選擇:-(A1-Z1)m-A2-Z2-A3- (II) P-Sp-X-MG-X-Sp-P (I) [In formula (I), P is a polymerizable group, Sp is a spacer with 1-20 carbon atoms, and X is selected from -O-, -S-, -CO-, -COO-, -OCO-, -OCO-O- groups or single bonds, MG is a mesogen group or mesogen support group, the group is preferably selected according to the following formula II :-(A 1 -Z 1 ) m -A 2 -Z 2 -A 3- (II)
(式(II)中,A1、A2及A3相互獨立,為1,4-伸苯基,且該基中存在的1個或2個以上之CH基可再被N取代,或者為1,4-伸環己基,且該基中存在的1個CH2基或不相鄰的2個CH2基可再被O及(或)S取代,或者為1,4-伸環己烯基或萘-2,6-二基,且此等基全部為未取代、或者可被1個或2個以上之鹵素、氰基或硝基或者具有碳 原子1~7個的烷基、烷氧基或鏈烷醯基取代,此等基中的1個或2個以上之H原子可被F或Cl取代,Z1及Z2各自獨立,為-COO-、-OCO-、-CH2CH2-、-OCH2-、-CH2O-、-CH=CH-、-CC=、-CH=CH-COO-、-OCO-CH=CH-或單鍵,且m為0、1或2)]。 (In formula (II), A 1 , A 2 and A 3 are independent of each other and are 1,4-phenylene, and one or more CH groups existing in this group may be substituted by N again, or 1,4-cyclohexylene, and one CH 2 group or two non-adjacent CH 2 groups in the group can be substituted by O and (or) S, or 1,4-cyclohexene Group or naphthalene-2,6-diyl group, and these groups are all unsubstituted, or can be substituted by one or more halogen, cyano or nitro groups, or alkyl groups or alkyl groups with 1-7 carbon atoms. Substitution by oxy or alkanoyl. One or more of the H atoms in these groups may be substituted by F or Cl. Z 1 and Z 2 are independent of each other and are -COO-, -OCO-, -CH 2 CH 2 -, -OCH 2 -, -CH 2 O-, -CH=CH-, -CC=, -CH=CH-COO-, -OCO-CH=CH- or single bond, and m is 0, 1 Or 2)].
<3>上述<1>或<2>中,(A)成分以具有引發光交聯、光異構化、或光-弗萊斯重排的感光性側鏈者為佳。 <3> In the above-mentioned <1> or <2>, the component (A) preferably has a photosensitive side chain that initiates photocrosslinking, photoisomerization, or photo-Fries rearrangement.
<4>上述<1>或<2>中,(A)成分以具有下述式(1)~(6)所成群組中選出的任1種的感光性側鏈者為佳。 <4> In the above-mentioned <1> or <2>, the component (A) preferably has any one type of photosensitive side chain selected from the group consisting of the following formulas (1) to (6).
[式中,A、B、D各自獨立,為單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、或-O-CO-CH=CH-;S為碳數1~12的伸烷基,鍵結於彼等的氫原子可被鹵素基取代; T為單鍵或碳數1~12的伸烷基,且鍵結於彼等的氫原子可被鹵素基取代;Y1為1價苯環、萘環、聯苯環、呋喃環、吡咯環及碳數5~8的脂環式烴所選出的環、或由彼等之取代基選出的相同或相異的2~6個環透過鍵結基B鍵結而成的基,且鍵結於彼等的氫原子各自獨立,可被-COOR0(式中,R0為碳數1~5的烷基)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5的烷基、或碳數1~5的烷基氧基取代;Y2為2價苯環、萘環、聯苯環、呋喃環、吡咯環、碳數5~8的脂環式烴、及彼等之組合所成群組中選出的基,且鍵結於彼等的氫原子各自獨立,可被-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5的烷基、或碳數1~5的烷基氧基取代;R為碳數1~6的烷氧基、或與Y1同定義;X為單鍵、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-CO-O-、或-O-CO-CH=CH-,X之數為2時,X彼此可為相同或相異;Cou為香豆素-6-基或香豆素-7-基,鍵結於彼等的氫原子各自獨立,可被-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5的烷基、或碳數1~5的烷基氧基取代;q1與q2,一者為1而另一者為0;q3為0或1; P及Q各自獨立,為2價苯環、萘環、聯苯環、呋喃環、吡咯環、碳數5~8的脂環式烴、及彼等之組合所成群組中選出的基;但,X為-CH=CH-CO-O-、-O-CO-CH=CH-時,-CH=CH-鍵結側的P或Q為芳香環;l1為0或1;l2為0~2的整數;l1與l2皆為0時,T為單鍵時A亦為單鍵;l1為1時,T為單鍵時B亦為單鍵;H及I各自獨立,為2價苯環、萘環、聯苯環、呋喃環、吡咯環、及彼等之組合所選出的基」。 [In the formula, A, B, and D are independent of each other and are single bonds, -O-, -CH 2 -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO- O-, or -O-CO-CH=CH-; S is an alkylene group with 1 to 12 carbons, and the hydrogen atoms bonded to them can be substituted by halogen groups; T is a single bond or 1 to 12 carbons And the hydrogen atoms bonded to them can be substituted by halogen groups; Y 1 is a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic ring with 5 to 8 carbon atoms The ring selected by the hydrocarbon, or the same or different 2-6 rings selected by their substituents, are bonded through the bonding group B, and the hydrogen atoms bonded to them are independent, and can be By -COOR 0 (where R 0 is an alkyl group with carbon number 1 to 5), -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH-CN, halogen group, carbon number 1 Alkyl group of ~5, or alkyloxy group of carbon number 1~5; Y 2 is divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon with carbon number 5~8 , And the group selected from the group formed by their combination, and the hydrogen atoms bonded to them are independent of each other, and can be -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH- CN, halogen group, alkyl group with 1 to 5 carbons, or alkyloxy group with 1 to 5 carbons; R is alkoxy with 1 to 6 carbons, or the same definition as Y 1 ; X is a single bond , -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, X of When the number is 2, X can be the same or different from each other; Cou is coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bonded to them are independent of each other, and can be replaced by -NO 2 ,- CN, -CH=C(CN) 2 , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbons, or alkyloxy group with 1 to 5 carbons; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; P and Q are independent of each other and are a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon with 5 to 8 carbon atoms, And the group selected from the group formed by their combination; but, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, -CH=CH- P or P on the bonding side Q is an aromatic ring; l1 is 0 or 1; l2 is an integer from 0 to 2; when both l1 and l2 are 0, when T is a single bond, A is also a single bond; when l1 is 1, when T is a single bond, B is also It is a single bond; H and I are independent of each other, and are groups selected from a combination of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination thereof."
<5>上述<1>~<4>之任一中,(A)成分以進一步具有下述式(21)~(30)所成群組中選出的任1種的液晶性側鏈者為佳。 <5> In any of the above <1> to <4>, the component (A) further has any one of the liquid crystal side chains selected from the group consisting of the following formulas (21) to (30) as good.
式中,A、B、R、q1及q2具有與上述相同定義;Y3為1價苯環、萘環、聯苯環、呋喃環、含氮雜環、及碳數5~8的脂環式烴、及彼等之組合所成群組中選出的基,且鍵結於彼等的氫原子各自獨立,可被-NO2、-CN、鹵素基、碳數1~5的烷基、或碳數1~5的烷基氧基取代;R3為氫原子、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、1價苯環、萘環、聯苯環、呋喃環、含氮雜環、碳數5~8的脂環式烴、碳數1~12的烷基、或碳數1~12的烷氧基;l為1~12的整數,m為0~2的整數,但是,式(23) ~(26)中,全部的m之合計為2以上,且m1、m2及m3各自獨立,為1~3的整數;R2為氫原子、-NO2、-CN、鹵素基、1價苯環、萘環、聯苯環、呋喃環、含氮雜環、及碳數5~8的脂環式烴、及烷基、或烷基氧基;Z11、Z12為單鍵、-CO-、-CH2O-、-CH=N-、-CF2-。 In the formula, A, B, R, q1 and q2 have the same definitions as above; Y 3 is a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic ring with 5 to 8 carbon atoms The group selected from the group consisting of the formula hydrocarbon, and their combination, and the hydrogen atoms bonded to them are independent of each other, and can be -NO 2 , -CN, halogen groups, alkyl groups with 1 to 5 carbons, Or substituted by an alkyloxy group with 1 to 5 carbon atoms; R 3 is a hydrogen atom, -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH-CN, halogen group, monovalent benzene ring, Naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon with 5 to 8 carbons, alkyl with 1 to 12 carbons, or alkoxy with 1 to 12 carbons; l is 1~ An integer of 12, m is an integer of 0 to 2, but in formulas (23) to (26), the total of all m is 2 or more, and m1, m2, and m3 are independent of each other and are an integer of 1 to 3; R 2 is a hydrogen atom, -NO 2 , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon with 5 to 8 carbon atoms, and an alkyl group , Or alkyloxy; Z 11 and Z 12 are single bonds, -CO-, -CH 2 O-, -CH=N-, -CF 2 -.
<6>藉由具有[I]將上述<1>~<5>中任一記載之聚合物組成物塗佈於具有液晶驅動用電極的基板上而形成塗膜的步驟;[II]對[I]得到的塗膜從斜方向照射偏光紫外線的步驟;及[III]將[II]得到的塗膜加熱的步驟;,得到被賦予配向控制能力的垂直電場驅動型液晶顯示元件用液晶配向膜的前述具有液晶配向膜的基板之製造方法。 <6> A step of forming a coating film by applying the polymer composition described in any one of the above <1> to <5> on a substrate having an electrode for liquid crystal driving by having [I]; [II] I] the step of irradiating the obtained coating film with polarized ultraviolet rays from an oblique direction; and [III] the step of heating the coating film obtained in [II]; to obtain a liquid crystal alignment film for a vertical electric field drive type liquid crystal display element endowed with alignment control ability The aforementioned method for manufacturing a substrate with a liquid crystal alignment film.
<7>以上述<6>記載之製造方法所製造的具有垂直電場驅動型液晶顯示元件用液晶配向膜的基板。 <7> A substrate having a liquid crystal alignment film for a vertical electric field drive type liquid crystal display element manufactured by the manufacturing method described in the above <6>.
<8>具有上述<7>的基板的垂直電場驅動型液晶顯示元件。 <8> A vertical electric field drive type liquid crystal display element having the substrate of the above <7>.
<9>具有上述<7>的基板的扭轉向列型液晶顯示元件或OCB型液晶顯示元件。 <9> A twisted nematic liquid crystal display element or an OCB type liquid crystal display element having the substrate of the above-mentioned <7>.
<10>藉由具有準備上述<7>的基板(第1基板)的步驟;藉由使用上述<6>的步驟[I]~[III],而得到第2基板的步驟;及[IV]介隔著液晶以第1及第2基板的液晶配向膜相對之方式,對向配置第1及第2基板而得到液晶顯示元件的步驟;得到垂直電場驅動型液晶顯示元件的該液晶顯示元件之製造方法。 <10> A step of preparing the substrate (first substrate) of the above <7>; a step of obtaining the second substrate by using the steps [I] to [III] of the above <6>; and [IV] The step of arranging the first and second substrates facing each other with the liquid crystal alignment films of the first and second substrates facing each other through the liquid crystal to obtain a liquid crystal display element; and obtaining a vertical electric field drive type liquid crystal display element of the liquid crystal display element Production method.
<11>[IV]步驟係介隔著液晶以第1及第2基板的液晶配向膜相對之方式,使配向方向相互垂直地對向配置第1及第2基板而得到液晶顯示元件的步驟的扭轉向列型液晶顯示元件之製造方法。 <11> The step [IV] is a step of arranging the first and second substrates so that the alignment directions of the first and second substrates face each other with the liquid crystal alignment films of the first and second substrates facing each other through the liquid crystal to obtain a liquid crystal display element. Method for manufacturing twisted nematic liquid crystal display elements.
<12>由上述<10>所製造的垂直電場驅動型液晶顯示元件。 <12> The vertical electric field drive type liquid crystal display element manufactured by the above <10>.
<13>由上述<11>所製造的扭轉向列型液晶顯示元件。 <13> The twisted nematic liquid crystal display element manufactured by the above <11>.
根據本發明,可提供具有以高效率被賦予配向控制能力、傾斜角度特性優異的液晶配向膜的基板及具有該基板的垂直電場驅動型液晶顯示元件(例如扭轉向列型液晶顯示元件、VA型液晶顯示元件、STN型液晶顯示元件、ECB型液晶顯示元件及OCB型液晶顯示元件)。 According to the present invention, it is possible to provide a substrate having a liquid crystal alignment film with high-efficiency alignment control ability and excellent tilt angle characteristics and a vertical electric field drive type liquid crystal display element (such as a twisted nematic liquid crystal display element, VA type Liquid crystal display element, STN type liquid crystal display element, ECB type liquid crystal display element and OCB type liquid crystal display element).
以本發明之方法製造的垂直電場驅動型液晶顯示元件係高效率地被賦予配向控制能力,故即使長時間連續驅動亦不損及顯示特性。 The vertical electric field drive type liquid crystal display element manufactured by the method of the present invention is efficiently endowed with an alignment control ability, so even if it is continuously driven for a long time, the display characteristics will not be impaired.
本發明者進行努力研究的結果,得到以下的知識而完成本發明。 As a result of diligent research, the inventors obtained the following knowledge and completed the present invention.
本發明之製造方法中使用的聚合物組成物為具有可表現液晶性的感光性側鏈型高分子(以下,亦僅稱側鏈型高 分子),使用前述聚合物組成物所得到的塗膜為具有可表現液晶性的感光性側鏈型高分子的膜。該塗膜不進行摩擦處理而以偏光照射進行配向處理。而,偏光照射後,經將該側鏈型高分子膜加熱的步驟,成為賦予配向控制能力的塗膜(以下,亦稱液晶配向膜)。此時,因偏光照射表現的輕微異方向性成為推動力,液晶性之側鏈型高分子本身因自我組織化而更有效率地再配向。結果,作為液晶配向膜,可得到實現高效率的配向處理且被賦予高配向控制能力的液晶配向膜。 The polymer composition used in the production method of the present invention is a photosensitive side chain type polymer having liquid crystallinity (hereinafter, also referred to only as side chain type high Molecule), and the coating film obtained using the aforementioned polymer composition is a film having a photosensitive side chain type polymer that can express liquid crystallinity. The coating film is not subjected to rubbing treatment, but is oriented by polarized light irradiation. However, after polarized light irradiation, the step of heating the side chain type polymer film becomes a coating film (hereinafter, also referred to as a liquid crystal alignment film) that imparts alignment control ability. At this time, the slight anisotropy exhibited by polarized light irradiation becomes the driving force, and the liquid crystal side chain polymer itself is self-organized and realigned more efficiently. As a result, as a liquid crystal alignment film, a liquid crystal alignment film that realizes high-efficiency alignment processing and is endowed with high alignment control ability can be obtained.
以下、將本發明之實施形態詳細說明。 Hereinafter, the embodiments of the present invention will be described in detail.
(A)成分為在特定的溫度範圍表現液晶性之感光性側鏈型高分子。 (A) Component is a photosensitive side chain type polymer which expresses liquid crystallinity in a specific temperature range.
(A)側鏈型高分子以在250nm~400nm的波長範圍之光進行反應且在100℃~300℃之溫度範圍顯示液晶性者為宜。 (A) The side chain polymer reacts with light in the wavelength range of 250nm to 400nm and exhibits liquid crystallinity in the temperature range of 100°C to 300°C.
(A)側鏈型高分子以具有於250nm~400nm的波長範圍之光進行反應的感光性側鏈為佳。 (A) The side chain type polymer preferably has a photosensitive side chain that reacts with light in the wavelength range of 250 nm to 400 nm.
(A)側鏈型高分子因在100℃~300℃之溫度範圍顯示液晶性,以具有液晶原基為佳。 (A) The side chain type polymer exhibits liquid crystallinity in the temperature range of 100°C to 300°C, and preferably has a mesogenic group.
(A)側鏈型高分子於主鏈鍵結有具有感光性之側鏈,可感應光後引起交聯反應、異構化反應、或光-弗萊斯重排。具有感光性的側鏈之構造雖不特別限制,以 感應光後引起交聯反應、或光-弗萊斯重排之構造為佳、引起交聯反應者更佳。該場合,即使暴露於熱等之外部壓力,可長期間安定維持經實現的配向控制能力。可表現液晶性的感光性側鏈型高分子膜之構造為滿足如此特性者,則不特別限定,但以於側鏈構造具有剛硬的液晶原成分為佳。該場合,將該側鏈型高分子作成液晶配向膜時,可得到安定之液晶配向。 (A) The side chain type polymer has a photosensitive side chain bonded to the main chain, which can induce cross-linking reaction, isomerization reaction, or light-Fries rearrangement after sensing light. Although the structure of the photosensitive side chain is not particularly limited, it is The structure that induces cross-linking reaction or light-Fries rearrangement after sensing light is better, and the one that causes cross-linking reaction is even better. In this case, even if exposed to external pressure such as heat, the realized alignment control ability can be stably maintained for a long period of time. The structure of the photosensitive side chain type polymer film capable of expressing liquid crystallinity is not particularly limited if it satisfies such characteristics, but it is preferable to have a rigid mesogen component in the side chain structure. In this case, when the side chain polymer is used as a liquid crystal alignment film, stable liquid crystal alignment can be obtained.
該高分子的構造,例如可為具有主鏈與鍵結於其之側鏈,該側鏈為具有聯苯基、三聯苯基、苯基環己基、苯基苯甲酸酯基、偶氮苯基等之液晶原成分與鍵結於先端部的感應光後引起交聯反應或異構化反應之感光性基的構造、或具有主鏈與鍵結於其之側鏈,該側鏈亦成為液晶原成分且具有進行光-弗萊斯重排反應之苯基苯甲酸酯基之構造。 The structure of the polymer, for example, can have a main chain and a side chain bonded to it, and the side chain has a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenyl benzoate group, and an azobenzene group. The structure of the photosensitive group that causes the cross-linking reaction or isomerization reaction after the sensitive light of bonding to the tip part of the mesogen component, or the main chain and the side chain bonded to it, the side chain also becomes It has a mesogen composition and has a structure of a phenyl benzoate group that undergoes a light-Fries rearrangement reaction.
可表現液晶性的感光性側鏈型高分子之構造之更具體例子方面,以具有由烴、(甲基)丙烯酸酯、衣康酸酯、富馬酸酯、馬來酸酯、α-亞甲基-γ-丁內酯、苯乙烯、乙烯基、馬來醯亞胺、降冰片烯等的自由基聚合性基及矽氧烷所成群中選出的至少1種所構成的主鏈、與具有下述式(1)~(6)之至少1種所構成的感光性側鏈之構造為佳。 More specific examples of the structure of the photosensitive side chain type polymer that can express liquid crystallinity include hydrocarbons, (meth)acrylates, itaconates, fumarates, maleates, and α-substrates. The main chain consisting of at least one selected from the group of radically polymerizable groups such as methyl-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and silicone, It is preferable to have a structure with a photosensitive side chain composed of at least one of the following formulas (1) to (6).
式中,A、B、D各自獨立,為單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、或-O-CO-CH=CH-;S為碳數1~12的伸烷基,鍵結於彼等的氫原子可被鹵素基取代; T為單鍵或碳數1~12的伸烷基,且鍵結於彼等的氫原子可被鹵素基取代;Y1為1價苯環、萘環、聯苯環、呋喃環、吡咯環及碳數5~8的脂環式烴所選出的環、或由彼等之取代基選出的相同或相異的2~6個環透過鍵結基B鍵結而成的基,且鍵結於彼等的氫原子各自獨立,可被-COOR0(式中,R0為碳數1~5的烷基)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5的烷基、或碳數1~5的烷基氧基取代;Y2為2價苯環、萘環、聯苯環、呋喃環、吡咯環、碳數5~8的脂環式烴、及彼等之組合所成群組中選出的基,且鍵結於彼等的氫原子各自獨立,可被-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5的烷基、或碳數1~5的烷基氧基取代;R為碳數1~6的烷氧基、或與Y1同定義;X為單鍵、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-CO-O-、或-O-CO-CH=CH-,X之數為2時,X彼此可為相同或相異;Cou為香豆素-6-基或香豆素-7-基,鍵結於彼等的氫原子各自獨立,可被-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5的烷基、或碳數1~5的烷基氧基取代;q1與q2,一者為1而另一者為0;q3為0或1; P及Q各自獨立,為2價苯環、萘環、聯苯環、呋喃環、吡咯環、碳數5~8的脂環式烴、及彼等之組合所成群組中選出的基;但,X為-CH=CH-CO-O-、-O-CO-CH=CH-時,-CH=CH-鍵結側的P或Q為芳香環;l1為0或1;l2為0~2的整數;l1與l2皆為0時,T為單鍵時A亦為單鍵;l1為1時,T為單鍵時B亦為單鍵;H及I各自獨立,為2價苯環、萘環、聯苯環、呋喃環、吡咯環、及彼等之組合所選出的基。 In the formula, A, B, and D are independent of each other and are single bonds, -O-, -CH 2 -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O -, or -O-CO-CH=CH-; S is an alkylene group with 1 to 12 carbons, and the hydrogen atoms bonded to them can be substituted by halogen groups; T is a single bond or one with 1 to 12 carbons Alkylene, and the hydrogen atoms bonded to them can be substituted by halogen groups; Y 1 is a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon with 5 to 8 carbon atoms The selected ring, or the same or different 2-6 rings selected by their substituents, are bonded through the bonding group B, and the hydrogen atoms bonded to them are independent and can be -COOR 0 (where R 0 is an alkyl group with carbon number of 1 to 5), -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH-CN, halogen group, carbon number of 1~ Alkyl group 5, or alkyloxy group with 1 to 5 carbons; Y 2 is a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon with 5 to 8 carbons, And the group selected from the group formed by their combination, and the hydrogen atoms bonded to them are independent, can be -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH-CN , Halogen group, alkyl group with 1 to 5 carbons, or alkyloxy group with 1 to 5 carbons; R is an alkoxy group with 1 to 6 carbons, or the same definition as Y 1 ; X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, the number of X When it is 2, X can be the same or different from each other; Cou is coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bonded to them are independent of each other and can be replaced by -NO 2 , -CN , -CH=C(CN) 2 , -CH=CH-CN, halogen group, C1-C5 alkyl group, or C1-C5 alkyloxy group substitution; q1 and q2, one of them is 1 And the other is 0; q3 is 0 or 1; P and Q are independent of each other and are a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon with 5 to 8 carbon atoms, and The group selected from the group formed by their combination; but, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, -CH=CH- P or Q on the bonding side Is an aromatic ring; l1 is 0 or 1; l2 is an integer from 0 to 2; when both l1 and l2 are 0, when T is a single bond, A is also a single bond; when l1 is 1, when T is a single bond, B is also Single bond; H and I are each independent, and are groups selected from a combination of divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.
側鏈以下述式(7)~(10)所成群組中選出的任1種的感光性側鏈者為佳。 The side chain is preferably any one of photosensitive side chains selected from the group consisting of the following formulas (7) to (10).
式中,A、B、D、Y1、X、Y2、及R具有與上述相同定義;l為1~12的整數;m為0~2的整數,m1、m2為1~3的整數;n為0~12的整數(但n=0時B為單鍵)。 In the formula, A, B, D, Y 1 , X, Y 2 , and R have the same definitions as above; l is an integer from 1 to 12; m is an integer from 0 to 2, m1, m2 are an integer from 1 to 3 ; N is an integer from 0 to 12 (but B is a single bond when n=0).
側鏈以下述式(11)~(13)所成群組中選出的任1種的感光性側鏈者為佳。 The side chain is preferably any one of photosensitive side chains selected from the group consisting of the following formulas (11) to (13).
式中,A、X、l、m及R具有與上述相同定義。 In the formula, A, X, 1, m and R have the same definitions as above.
側鏈以下述式(14)或(15)所表示之感光性側鏈者為佳。 The side chain is preferably a photosensitive side chain represented by the following formula (14) or (15).
式中,A、Y1、X、l、m1及m2具有與上述相同定義。 In the formula, A, Y 1 , X, 1, m1 and m2 have the same definitions as above.
側鏈以下述式(16)或(17)所表示之感光性側鏈者為佳。 The side chain is preferably a photosensitive side chain represented by the following formula (16) or (17).
式中,A、X、l及m具有與上述相同定義。 In the formula, A, X, l and m have the same definitions as above.
又,側鏈以下述式(18)或(19)所表示之感光性側鏈為宜。 In addition, the side chain is preferably a photosensitive side chain represented by the following formula (18) or (19).
式中,A、B、Y1、q1、q2、m1、及m2具有與上述相同定義。 In the formula, A, B, Y 1 , q1, q2, m1, and m2 have the same definitions as above.
R1為氫原子、-NO2、-CN、-CH=C(CN)2、 -CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基。 R 1 is a hydrogen atom, -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH-CN, a halogen group, an alkyl group with 1 to 5 carbons, or an alkyl group with 1 to 5 carbons Oxy.
側鏈以下述式(20)所表示之感光性側鏈者為佳。 The side chain is preferably a photosensitive side chain represented by the following formula (20).
式中,A、Y1、X、l及m具有與上述相同定義。 In the formula, A, Y 1 , X, l and m have the same definitions as above.
又,(A)側鏈型高分子以具有下述式(21)~(30)所成群組中選出的任1種的液晶性側鏈者為佳。 In addition, the (A) side chain type polymer preferably has any one liquid crystal side chain selected from the group consisting of the following formulas (21) to (30).
式中,A、B、R、q1及q2具有與上述相同定義;Y3為1價苯環、萘環、聯苯環、呋喃環、含氮雜環、及碳數5~8的脂環式烴、及彼等之組合所成群組中選出的基,且鍵結於彼等的氫原子各自獨立,可被-NO2、-CN、鹵素基、碳數1~5的烷基、或碳數1~5的烷基氧基取代;R3為氫原子、-NO2、-CN、-CH=C(CN)2、 -CH=CH-CN、鹵素基、1價苯環、萘環、聯苯環、呋喃環、含氮雜環、碳數5~8的脂環式烴、碳數1~12的烷基、或碳數1~12的烷氧基;l為1~12的整數,m為0~2的整數,但是,式(23)~(26)中,全部的m之合計為2以上,且m1、m2及m3各自獨立,為1~3的整數;R2為氫原子、-NO2、-CN、鹵素基、1價苯環、萘環、聯苯環、呋喃環、含氮雜環、及碳數5~8的脂環式烴、及烷基、或烷基氧基;Z11、Z12為單鍵、-CO-、-CH2O-、-CH=N-、-CF2-。 In the formula, A, B, R, q1 and q2 have the same definitions as above; Y 3 is a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic ring with 5 to 8 carbon atoms The group selected from the group consisting of the formula hydrocarbon, and their combination, and the hydrogen atoms bonded to them are independent of each other, and can be -NO 2 , -CN, halogen groups, alkyl groups with 1 to 5 carbons, Or substituted by an alkyloxy group with 1 to 5 carbon atoms; R 3 is a hydrogen atom, -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH-CN, halogen group, monovalent benzene ring, Naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon with 5 to 8 carbons, alkyl with 1 to 12 carbons, or alkoxy with 1 to 12 carbons; l is 1~ An integer of 12, m is an integer of 0 to 2, but in formulas (23) to (26), the sum of all m is 2 or more, and m1, m2, and m3 are independent of each other and are an integer of 1 to 3; R 2 is a hydrogen atom, -NO 2 , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon with 5 to 8 carbon atoms, and an alkyl group , Or alkyloxy; Z 11 and Z 12 are single bonds, -CO-, -CH 2 O-, -CH=N-, -CF 2 -.
可表現上述液晶性的感光性側鏈型高分子,可藉由使上述具有感光性側鏈的光反應性側鏈單體及液晶性側鏈單體聚合而得到。 The photosensitive side chain type polymer which can express the said liquid crystallinity can be obtained by polymerizing the said photoreactive side chain monomer which has a photosensitive side chain, and a liquid crystal side chain monomer.
光反應性側鏈單體,係指形成高分子時,於高分子的側鏈部位可形成具有感光性側鏈的高分子的單體。 The photoreactive side chain monomer refers to a monomer that can form a polymer having a photosensitive side chain at the side chain portion of the polymer when forming a polymer.
側鏈所具有的光反應性基,以下述構造及其衍生物為佳。 The photoreactive group possessed by the side chain preferably has the following structure and its derivatives.
光反應性側鏈單體之更具體例子方面,以具有烴、(甲基)丙烯酸酯、衣康酸酯、富馬酸酯、馬來酸、α-亞甲基-γ-丁內酯、苯乙烯、乙烯基、馬來醯亞胺、降冰片烯等的自由基聚合性基及矽氧烷所成群中選出的至少1種所構成的聚合性基、與上述式(1)~(6)之至少1種所構成的感光性側鏈、較佳為例如上述式(7)~(10)之至少1種所構成的感光性側鏈、上述式(11)~ (13)之至少1種所構成的感光性側鏈、上述式(14)或(15)所表示之感光性側鏈、上述式(16)或(17)所表示之感光性側鏈、上述式(18)或(19)所表示之感光性側鏈、上述式(20)所表示之感光性側鏈之構造為佳。 More specific examples of photoreactive side chain monomers include hydrocarbons, (meth)acrylates, itaconates, fumarates, maleic acid, α-methylene-γ-butyrolactone, Free radical polymerizable groups such as styrene, vinyl, maleimide, norbornene, and a polymerizable group composed of at least one selected from the group of silicones, and the above formulas (1)~( 6) A photosensitive side chain composed of at least one type of, for example, a photosensitive side chain composed of at least one of the above formulas (7) to (10), and the above formula (11) to (13) at least one photosensitive side chain, the photosensitive side chain represented by the above formula (14) or (15), the photosensitive side chain represented by the above formula (16) or (17), the above The photosensitive side chain represented by the formula (18) or (19) and the photosensitive side chain represented by the above formula (20) preferably have a structure.
如此之光反應性側鏈單體方面,以照射偏光紫外線時,表現二聚化反應或異構化反應者為佳。如此之單體方面,可舉例如下述式M1-1~M1-22所選出的單體。 With regard to such photoreactive side chain monomers, it is preferable to perform dimerization reaction or isomerization reaction when irradiated with polarized ultraviolet rays. Examples of such monomers include monomers selected from the following formulas M1-1 to M1-22.
(式中,M1為氫原子或甲基,s1為伸甲基的數,為2乃至9之自然數)。 (In the formula, M1 is a hydrogen atom or a methyl group, and s1 is the number of methylidene, which is a natural number from 2 to 9).
(式中,R為碳數1~6的烷氧基,M1為氫原子或甲基,s1為伸甲基的數,為2乃至9之自然數)。 (In the formula, R is an alkoxy group having 1 to 6 carbon atoms, M1 is a hydrogen atom or a methyl group, and s1 is the number of methylidene, which is a natural number from 2 to 9).
液晶性側鏈單體係指,來自該單體的高分子表現液晶性,且該高分子可於側鏈部位形成液晶原基的單體。 The liquid crystal side chain single system refers to a monomer in which a polymer derived from the monomer exhibits liquid crystallinity, and the polymer can form a mesogenic group at a side chain site.
側鏈所具有的液晶原基,可為聯苯基或苯基苯甲酸酯 等之單獨成為液晶原構造之基或安息香酸等般側鏈彼此進行氫鍵結而成為液晶原構造之基。側鏈所具有的液晶原基以下述構造為佳。 The mesogen group in the side chain can be biphenyl or phenyl benzoate It is the base of the mesogen structure alone or the side chains of benzoic acid are hydrogen-bonded to each other to form the base of the mesogen structure. The mesogen group of the side chain preferably has the following structure.
液晶性側鏈單體之更具體例子方面,以具有烴、(甲基)丙烯酸酯、衣康酸酯、富馬酸酯、馬來酸、α-亞甲基-γ-丁內酯、苯乙烯、乙烯基、馬來醯亞胺、降冰片烯等的自由基聚合性基及矽氧烷所成群中選出的至少1種所構成的聚合性基與上述式(21)~(30)之至少1種所構成的側鏈之構造為佳。 More specific examples of liquid crystalline side chain monomers include hydrocarbon, (meth)acrylate, itaconate, fumarate, maleic acid, α-methylene-γ-butyrolactone, benzene Radical polymerizable groups such as ethylene, vinyl, maleimide, norbornene, and at least one polymerizable group selected from the group of silicones and the above formulas (21) to (30) The structure of the side chain formed by at least one of them is preferable.
如此之液晶性單體之具體例子,例如亦可使用下述式M2-1~M2-10所成群組中選出的式所表示之單體。 As a specific example of such a liquid crystal monomer, for example, a monomer represented by a formula selected from the group consisting of the following formulas M2-1 to M2-10 can also be used.
(式中,M1為氫原子或甲基,R為碳數1~6的烷氧基,M1為氫原子或甲基,s1為伸甲基的數,為2乃至9之自然數)。 (In the formula, M1 is a hydrogen atom or a methyl group, R is an alkoxy group having 1 to 6 carbon atoms, M1 is a hydrogen atom or a methyl group, and s1 is the number of methylidene groups, which is a natural number from 2 to 9).
(A)側鏈型高分子可藉由上述表現液晶性的光反應性側鏈單體的共聚合反應而得到。又,可藉由不表現液晶性的光反應性側鏈單體與液晶性側鏈單體之共聚合、或表現液晶性的光反應性側鏈單體與液晶性側鏈單體之共聚合而得到。進一步,在不損及液晶性的表現能力範圍,可與其他的單體共聚合。 (A) The side chain type polymer can be obtained by the copolymerization reaction of the above-mentioned photoreactive side chain monomer expressing liquid crystallinity. In addition, it can be achieved by the copolymerization of a photoreactive side chain monomer that does not exhibit liquid crystallinity and a liquid crystalline side chain monomer, or a copolymerization of a photoreactive side chain monomer exhibiting liquid crystallinity and a liquid crystalline side chain monomer And get. Furthermore, it can be copolymerized with other monomers within the range of performance ability that does not impair the liquid crystallinity.
其他單體方面,可舉例如可工業上取得的可進行自由基聚合反應的單體。 In terms of other monomers, for example, an industrially available monomer capable of undergoing radical polymerization can be mentioned.
其他單體之具體例子方面,可舉例如不飽和羧酸、丙烯酸酯化合物、甲基丙烯酸酯化合物、馬來醯亞胺化合物、丙烯腈、馬來酸酐、苯乙烯化合物及乙烯基化合物等。 Specific examples of other monomers include unsaturated carboxylic acids, acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.
不飽和羧酸的具體例子,可舉例如丙烯酸、甲基丙烯酸、衣康酸、馬來酸、富馬酸等。 Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.
丙烯酸酯化合物,可舉例如甲基丙烯酸酯、乙基丙烯酸酯、異丙基丙烯酸酯、苄基丙烯酸酯、萘基丙烯酸酯、蒽基丙烯酸酯、蒽基甲基丙烯酸酯、苯基丙烯酸酯、2,2,2-三氟乙基丙烯酸酯、tert-丁基丙烯酸酯、環己基丙烯酸酯、異冰片基丙烯酸酯、2-甲氧基乙基丙烯酸酯、甲氧基三乙二醇丙烯酸酯、2-乙氧基乙基丙烯酸酯、四氫糠基丙烯酸酯、3-甲氧基丁基丙烯酸酯、2-甲基-2-金 剛烷基丙烯酸酯、2-丙基-2-金剛烷基丙烯酸酯、8-甲基-8-三環癸基丙烯酸酯、及8-乙基-8-三環癸基丙烯酸酯等。 Acrylate compounds include, for example, methacrylate, ethacrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methacrylate, phenyl acrylate, 2,2,2-Trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate , 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-gold Mandyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, etc.
甲基丙烯酸酯化合物,可舉例如甲基甲基丙烯酸酯、乙基甲基丙烯酸酯、異丙基甲基丙烯酸酯、苄基甲基丙烯酸酯、萘基甲基丙烯酸酯、蒽基甲基丙烯酸酯、蒽基甲基甲基丙烯酸酯、苯基甲基丙烯酸酯、2,2,2-三氟乙基甲基丙烯酸酯、tert-丁基甲基丙烯酸酯、環己基甲基丙烯酸酯、異冰片基甲基丙烯酸酯、2-甲氧基乙基甲基丙烯酸酯、甲氧基三乙二醇甲基丙烯酸酯、2-乙氧基乙基甲基丙烯酸酯、四氫糠基甲基丙烯酸酯、3-甲氧基丁基甲基丙烯酸酯、2-甲基-2-金剛烷基甲基丙烯酸酯、2-丙基-2-金剛烷基甲基丙烯酸酯、8-甲基-8-三環癸基甲基丙烯酸酯、及8-乙基-8-三環癸基甲基丙烯酸酯等。 The methacrylate compound includes, for example, methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, and anthryl methacrylate. Esters, anthracenyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl Methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecane Methyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, etc.
乙烯基化合物,可舉例如乙烯基醚、甲基乙烯基醚、苄基乙烯基醚、2-羥基乙基乙烯基醚、苯基乙烯基醚、及丙基乙烯基醚等。 Examples of vinyl compounds include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
苯乙烯化合物,可舉例如苯乙烯、甲基苯乙烯、氯苯乙烯、溴苯乙烯等。 Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.
馬來醯亞胺化合物,可舉例如馬來醯亞胺、N-甲基馬來醯亞胺、N-苯基馬來醯亞胺、及N-環己基馬來醯亞胺等。 Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
本發明之側鏈型高分子中之光反應性側鏈含量,由液晶配向性觀點,以10莫耳%~100莫耳%為佳、 20莫耳%~95莫耳%更佳、30莫耳%~90莫耳%再更佳。 The content of photoreactive side chains in the side chain polymer of the present invention, from the viewpoint of liquid crystal orientation, is preferably 10 mol% to 100 mol%. 20 mol%~95 mol% is better, and 30 mol%~90 mol% is even better.
本發明之側鏈型高分子中之液晶性側鏈的含量,由液晶配向性觀點,以90莫耳%以下為佳、5莫耳%~80莫耳%更佳、10莫耳%~70莫耳%再更佳。 The content of liquid crystal side chains in the side chain polymer of the present invention, from the viewpoint of liquid crystal alignment, is preferably 90 mol% or less, 5 mol% to 80 mol%, and 10 mol% to 70 mol%. Mole% is even better.
本發明之側鏈型高分子可含有上述光反應性側鏈及液晶性側鏈以外的其他側鏈。其含量,在上述光反應性側鏈及液晶性側鏈的含量的合計未達100%時,為其剩餘部分。 The side chain type polymer of the present invention may contain other side chains other than the above-mentioned photoreactive side chain and liquid crystal side chain. The content is the remainder when the total content of the photoreactive side chain and the liquid crystal side chain is less than 100%.
關於本實施形態的側鏈型高分子的製造方法,不特別限定,可利用工業上使用的常用方法。具體上可藉由利用液晶性側鏈單體或光反應性側鏈單體之乙烯基的陽離子聚合或自由基聚合、陰離子聚合來製造。在此等中由反應控制之難易性等的觀點,以自由基聚合特別佳。 The manufacturing method of the side chain type polymer of this embodiment is not particularly limited, and a common method used in industry can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group of a liquid crystal side chain monomer or a photoreactive side chain monomer. Among these, from the viewpoints of ease of reaction control, etc., radical polymerization is particularly preferred.
自由基聚合的聚合起始劑方面,可使用自由基聚合起始劑或可逆性的加成-開裂型鏈轉移(RAFT)聚合試藥等的習知化合物。 Regarding the polymerization initiator for radical polymerization, conventional compounds such as a radical polymerization initiator or a reversible addition-cracking type chain transfer (RAFT) polymerization reagent can be used.
自由基熱聚合起始劑為藉由加熱至分解溫度以上,產生自由基的化合物。如此之自由基熱聚合起始劑方面,例如酮過氧化物類(甲基乙基酮過氧化物、環己酮過氧化物等)、二乙醯基過氧化物類(乙醯過氧化物、苯甲醯基過氧化物等)、過氧化氫類(過氧化氫、tert-丁基過氧化氫、異丙苯過氧化氫等)、二烷基過氧化物類(二-tert-丁基過氧化物、二異丙苯基過氧化物、二月桂醯過氧化物等)、過氧縮酮類(二丁基過氧環己烷等)、烷基 過酯類(過氧新癸烷酸-tert-丁基酯、過氧新戊酸-tert-丁基酯、過氧2-乙基環己烷酸-tert-戊基酯等)、過硫酸鹽類(過硫酸鉀、過硫酸鈉、過硫酸銨等)、偶氮系化合物(偶氮雙異丁腈、及2,2’-二(2-羥基乙基)偶氮雙異丁腈等)。如此之自由基熱聚合起始劑可1種單獨使用或2種以上組合使用。 The radical thermal polymerization initiator is a compound that generates radicals by heating to a temperature above the decomposition temperature. Such radical thermal polymerization initiators, such as ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacetyl peroxides (acetyl peroxide , Benzyl peroxide, etc.), hydrogen peroxide (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl hydroperoxide, etc.) Base peroxide, dicumyl peroxide, dilaurel peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkyl Peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy2-ethylcyclohexane acid-tert-pentyl ester, etc.), persulfuric acid Salts (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, and 2,2'-bis(2-hydroxyethyl)azobisisobutyronitrile, etc.) ). Such a radical thermal polymerization initiator can be used singly or in combination of two or more kinds.
自由基光聚合起始劑為經光照射而開始自由基聚合之化合物,則不特別限定。如此之自由基光聚合起始劑方面,可舉例如二苯甲酮、米氏酮、4,4’-雙(二乙基胺基)二苯甲酮、呫噸酮、噻噸酮、異丙基呫噸酮、2,4-二乙基噻噸酮、2-乙基蒽醌、苯乙酮、2-羥基-2-甲基丙醯苯、2-羥基-2-甲基-4’-異丙基丙醯苯、1-羥基環己基苯基酮、異丙基安息香醚、異丁基安息香醚、2,2-二乙氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、樟腦醌、苯并蒽酮、2-甲基-1-[4-(甲基硫基)苯基]-2-嗎啉代丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉代苯基)-丁酮-1、4-二甲基胺基安息香酸乙基酯、4-二甲基胺基安息香酸異戊基酯、4,4’-二(t-丁基過氧基羰基)二苯甲酮、3,4,4’-三(t-丁基過氧基羰基)二苯甲酮、2,4,6-三甲基苯甲醯基二苯基膦氧化物、2-(4’-甲氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三嗪、2-(3’,4’-二甲氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三嗪、2-(2’,4’-二甲氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三嗪、2-(2’-甲氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三嗪、2-(4’-戊基氧基苯乙烯基) -4,6-雙(三氯甲基)-s-三嗪、4-[p-N,N-二(乙氧基羰基甲基)]-2,6-二(三氯甲基)-s-三嗪、1,3-雙(三氯甲基)-5-(2’-氯苯基)-s-三嗪、1,3-雙(三氯甲基)-5-(4’-甲氧基苯基)-s-三嗪、2-(p-二甲基胺基苯乙烯基)苯並噁唑、2-(p-二甲基胺基苯乙烯基)苯並噻唑、2-巰基苯並噻唑、3,3’-羰基雙(7-二乙基胺基香豆素)、2-(o-氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-肆(4-乙氧基羰基苯基)-1,2’-聯咪唑、2,2’-雙(2,4-二氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’雙(2,4-二溴苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’-雙(2,4,6-三氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、3-(2-甲基-2-二甲基胺基丙醯基)咔唑、3,6-雙(2-甲基-2-嗎啉代丙醯基)-9-n-十二基咔唑、1-羥基環己基苯基酮、雙(5-2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1H-吡咯-1-基)-苯基)鈦、3,3’,4,4’-四(t-丁基過氧基羰基)二苯甲酮、3,3’,4,4’-四(t-己基過氧基羰基)二苯甲酮、3,3’-二(甲氧基羰基)-4,4’-二(t-丁基過氧基羰基)二苯甲酮、3,4’-二(甲氧基羰基)-4,3’-二(t-丁基過氧基羰基)二苯甲酮、4,4’-二(甲氧基羰基)-3,3’-二(t-丁基過氧基羰基)二苯甲酮、2-(3-甲基-3H-苯並噻唑-2-叉)-1-萘-2-基-乙酮、或2-(3-甲基-1,3-苯並噻唑-2(3H)-叉)-1-(2-苯甲醯基)乙酮等。此等之化合物可單獨使用或2種以上混合使用。 The radical photopolymerization initiator is a compound that starts radical polymerization upon light irradiation, and is not particularly limited. Such radical photopolymerization initiators include, for example, benzophenone, Michler’s ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, iso Propyl xanthone, 2,4-diethyl thioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropanebenzene, 2-hydroxy-2-methyl-4 '-Isopropyl propyl benzene, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy -2-Phenylacetophenone, camphorquinone, benzoanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2- Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid Isoamyl ester, 4,4'-bis(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tris(t-butylperoxycarbonyl)benzophenone, 2 ,4,6-Trimethylbenzyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-Dimethoxystyrene Yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine , 2-(4'-Pentyloxystyryl) -4,6-bis(trichloromethyl)-s-triazine, 4-[pN,N-bis(ethoxycarbonylmethyl)]-2,6-bis(trichloromethyl)-s- Triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methyl) Oxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2- Mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1 ,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole , 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'bis(2,4- Dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4 ',5,5'-tetraphenyl-1,2'-biimidazole, 3-(2-methyl-2-dimethylaminopropyl)carbazole, 3,6-bis(2-methyl 2-morpholinopropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis(5-2,4-cyclopentadien-1-yl)-bis (2,6-Difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone , 3,3',4,4'-tetra(t-hexylperoxycarbonyl)benzophenone, 3,3'-bis(methoxycarbonyl)-4,4'-bis(t-butyl Peroxycarbonyl)benzophenone, 3,4'-bis(methoxycarbonyl)-4,3'-bis(t-butylperoxycarbonyl)benzophenone, 4,4'-bis (Methoxycarbonyl)-3,3'-bis(t-butylperoxycarbonyl)benzophenone, 2-(3-methyl-3H-benzothiazole-2-ylidene)-1-naphthalene -2-yl-ethanone, or 2-(3-methyl-1,3-benzothiazole-2(3H)-ylidene)-1-(2-benzyl)ethanone, etc. These compounds can be used alone or in combination of two or more kinds.
自由基聚合法不特別限定,可使用乳化聚合 法、懸濁聚合法、分散聚合法、沈澱聚合法、塊狀聚合法、溶液聚合法等。 The radical polymerization method is not particularly limited, and emulsion polymerization can be used Method, suspension polymerization method, dispersion polymerization method, precipitation polymerization method, bulk polymerization method, solution polymerization method, etc.
可表現液晶性的感光性側鏈型高分子的聚合反應使用的有機溶劑方面,為溶解生成的高分子者,則不特別限定。其具體例可舉例如以下。 The organic solvent used in the polymerization reaction of the photosensitive side chain type polymer that can express liquid crystallinity is not particularly limited if it dissolves the produced polymer. Specific examples thereof include the following.
例如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、N-甲基己內醯胺、二甲基亞碸、四甲基尿素、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯、異丙基醇、甲氧基甲基戊醇、二戊烯、乙基戊基酮、甲基壬基酮、甲基乙基酮、甲基異戊基酮、甲基異丙基酮、甲基溶纖劑、乙基溶纖劑、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、丁基卡必醇、乙基卡必醇、乙二醇、乙二醇單乙酸酯、乙二醇單異丙基醚、乙二醇單丁基醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲基醚、丙二醇-tert-丁基醚、二丙二醇單甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲基醚、3-甲基-3-甲氧基丁醇、二異丙基醚、乙基異丁基醚、二異丁烯、戊基乙酸酯、丁基丁酯、丁基醚、二異丁基酮、甲基環己烯、丙基醚、二己基醚、二噁烷、n-己烷、n-戊烷、n-辛烷、二乙基醚、環己酮、乙烯碳酸酯、丙烯碳酸酯、乳酸甲基酯、乳酸乙基酯、乙酸甲 基酯、乙酸乙基酯、乙酸n-丁基酯、乙酸丙二醇單乙基醚、丙酮酸甲基酯、丙酮酸乙基酯、3-甲氧基丙酸甲基酯、3-乙氧基丙酸甲基乙基酯、3-甲氧基丙酸乙基酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙基酯、3-甲氧基丙酸丁基酯、二甘醇二甲醚、4-羥基-4-甲基-2-戊酮、3-甲氧基-N,N-二甲基丙烷醯胺、3-乙氧基-N,N-二甲基丙烷醯胺、3-丁氧基-N,N-二甲基丙烷醯胺等。 For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactone, Dimethyl sulfide, tetramethyl urea, pyridine, dimethyl sulfide, hexamethyl sulfide, γ-butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl pentene Methyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, Ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, Propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether Ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetic acid Ester monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isopropyl ether Butyl ether, diisobutylene, pentyl acetate, butylbutyl ester, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane , N-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate Base ester, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3-ethoxy Methyl ethyl propionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, 3-methoxy Butyl propionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropaneamide, 3-ethoxy -N,N-dimethylpropaneamide, 3-butoxy-N,N-dimethylpropaneamide, etc.
此等有機溶劑可單獨使用或混合使用。進而即使為不溶解生成之高分子的溶劑,在生成的高分子不析出的範圍,可與上述有機溶劑混合使用。 These organic solvents can be used alone or in combination. Furthermore, even if it is a solvent that does not dissolve the produced polymer, it can be used in combination with the above-mentioned organic solvent in a range where the produced polymer does not precipitate.
又,自由基聚合中,有機溶劑中的氧因成為阻礙聚合反應之原因,故有機溶劑以使用盡可能脫氣者為佳。 In addition, in radical polymerization, since oxygen in the organic solvent is a cause of hindering the polymerization reaction, the organic solvent is preferably used as degassed as possible.
自由基聚合時之聚合溫度可在30℃~150℃之任意的溫度選擇,但較佳為50℃~100℃的範圍。又,反應可在任意的濃度進行,但濃度過低則變得難以得到高分子量的聚合物,濃度過高則反應液的黏性變過高而均勻的攪拌變困難,故單體濃度較佳為1質量%~50質量%、更佳為5質量%~30質量%。反應初期在高濃度進行,之後,可追加有機溶劑。 The polymerization temperature during radical polymerization can be selected at any temperature from 30°C to 150°C, but is preferably in the range of 50°C to 100°C. In addition, the reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult, so the monomer concentration is better. It is 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass. The reaction is carried out at a high concentration in the initial stage, and then an organic solvent can be added.
上述自由基聚合反應中,自由基聚合起始劑的比率相對於單體多則得到的高分子的分子量變小、少則得到的高分子的分子量變大,故自由基起始劑的比率相對聚合單體以0.1莫耳%~10莫耳%為佳。又聚合時,可追加各種單體成分或溶劑、起始劑等。 In the above-mentioned radical polymerization reaction, the ratio of the radical polymerization initiator to that of the more monomers will decrease the molecular weight of the polymer obtained, and the smaller the ratio of the radical initiator will increase the molecular weight of the polymer obtained. The polymerized monomer is preferably 0.1 mol% to 10 mol%. During the polymerization, various monomer components, solvents, initiators, etc. may be added.
由上述反應得到的可表現液晶性的感光性側鏈型高分子的反應溶液,回收生成的高分子場合,將反應溶液投入貧溶劑後使彼等聚合物沈澱即可。沈澱使用的貧溶劑方面,可舉例如甲醇、丙酮、己烷、庚烷、丁基溶纖劑、庚烷、甲基乙基酮、甲基異丁基酮、乙醇、甲苯、苯、二乙基醚、甲基乙基醚、水等。投入貧溶劑而沈澱的聚合物進行過濾回收後,可在常壓或者減壓下進行常溫或者加熱乾燥。又,使沈澱回收的聚合物再溶解於有機溶劑,重複再沈澱回收操作2次~10次,可使聚合物中的雜質減少。此時之貧溶劑,例如醇類、酮類、烴等,使用此等之中選出的3種類以上的貧溶劑,可進一步提升精製的效率,故佳。 The reaction solution of the photosensitive side chain type polymer capable of expressing liquid crystallinity obtained by the above reaction, in the case of recovering the produced polymer, the reaction solution may be poured into a poor solvent and the polymer may be precipitated. Examples of poor solvents used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and diethyl ether. , Methyl ethyl ether, water, etc. After the polymer precipitated by inputting the poor solvent is filtered and recovered, it can be dried under normal pressure or reduced pressure at normal temperature or by heating. In addition, by re-dissolving the polymer recovered by precipitation in an organic solvent, and repeating the reprecipitation recovery operation 2 to 10 times, impurities in the polymer can be reduced. For the poor solvents at this time, such as alcohols, ketones, hydrocarbons, etc., using more than 3 types of poor solvents selected from these can further improve the efficiency of purification, so it is preferred.
本發明之(A)側鏈型高分子的分子量,考量得到的塗膜之強度、塗膜形成時的作業性、及塗膜之均勻性時,以GPC(Gel Permeation Chromatography)法測定的重量平均分子量以2000~1000000為佳、更較佳為5000~100000。 The molecular weight of the (A) side chain polymer of the present invention is a weight average measured by GPC (Gel Permeation Chromatography) when considering the strength of the resulting coating film, the workability during coating film formation, and the uniformity of the coating film The molecular weight is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000.
本發明之較佳態樣中,液晶配向劑所使用的反應性液晶元化合物為下述式I所表示的化合物:P-Sp-X-MG-X-Sp-P (I) [式(I)中,P為聚合性基,Sp為具有碳原子1~20個的間隔基,X為選自-O-、-S-、-CO-、-COO-、-OCO-、-OCO-O-的基或單鍵,MG為液晶元基或液晶元支持基,該基較佳為由下述式(II)選擇:-(A1-Z1)m-A2-Z2-A3- (II) In a preferred aspect of the present invention, the reactive mesogen compound used in the liquid crystal alignment agent is a compound represented by the following formula I: P-Sp-X-MG-X-Sp-P (I) [Formula (I) In ), P is a polymerizable group, Sp is a spacer with 1-20 carbon atoms, and X is selected from -O-, -S-, -CO-, -COO-, -OCO-, -OCO-O -Is a group or a single bond, MG is a mesogen group or a mesogen support group, and the group is preferably selected by the following formula (II): -(A 1 -Z 1 ) m -A 2 -Z 2 -A 3 -(II)
(式中,A1、A2及A3相互獨立,為1,4-伸苯基,且該基中存在的1個或2個以上之CH基可再被N取代,或者為1,4-伸環己基,且該基中存在的1個CH2基或不相鄰的2個CH2基可再被O及(或)S取代,或者為1,4-伸環己烯基或萘-2,6-二基,且此等基全部為未取代、或者可被1個或2個以上之鹵素、氰基或硝基或者具有碳原子1~7個的烷基、烷氧基或鏈烷醯基取代,此等基中的1個或2個以上之H原子可被F或Cl取代,Z1及Z2各自獨立,為-COO-、-OCO-、-CH2CH2-、-OCH2-、-CH2O-、-CH=CH-、-C C=、-CH=CH-COO-、-OCO-CH=CH-或單鍵,且m為0、1或2)]。 (In the formula, A 1 , A 2 and A 3 are independent of each other and are 1,4-phenylene groups, and one or more CH groups existing in this group may be substituted by N again, or 1,4 -Cyclohexenylene, and one CH 2 group or two non-adjacent CH 2 groups in the group can be substituted by O and (or) S, or 1,4-cyclohexenylene or naphthalene -2,6-diyl, and all of these groups are unsubstituted, or may be substituted by one or more halogen, cyano or nitro groups, or alkyl, alkoxy or carbon atoms with 1-7 Alkyl substituted, one or more of the H atoms in these groups may be substituted by F or Cl, and Z 1 and Z 2 are independent of each other and are -COO-, -OCO-, -CH 2 CH 2- , -OCH 2 -, -CH 2 O-, -CH=CH-, -CC=, -CH=CH-COO-, -OCO-CH=CH- or single bond, and m is 0, 1 or 2) ].
以含有至少2種的反應性液晶元化合物,且其至少1種為式I所表示的化合物之聚合性混合物尤佳。 A polymerizable mixture containing at least two reactive mesogen compounds, and at least one of which is a compound represented by formula I, is particularly preferred.
二環狀及三環狀液晶元化合物為佳。 Bicyclic and tricyclic mesogen compounds are preferred.
鹵素較佳為F或Cl。 Halogen is preferably F or Cl.
式I所表示的化合物中,以MG在式II中,Z1及Z2為-COO-、-OCO-、-CH2-CH2-、-CH=CH-COO-、-OCO-CH=CH-或單鍵之化合物尤佳。 In the compound represented by formula I, with MG in formula II, Z 1 and Z 2 are -COO-, -OCO-, -CH 2 -CH 2 -, -CH=CH-COO-, -OCO-CH= CH- or single bond compounds are particularly preferred.
式II所表示的較佳液晶元基的小群如下述。為了簡潔,此等之基中,Phe為1,4-伸苯基,PheL被至少1個基L取代的1,4-伸苯基,在此L為F、Cl或CN、或者具有碳原子1~4個,且可被氟化的烷基、烷氧基或鏈烷醯基,而Cyc為反式-1,4-伸環己基。 The small groups of preferred mesogen groups represented by formula II are as follows. For brevity, in these groups, Phe is 1,4-phenylene, and PheL is 1,4-phenylene substituted with at least one group L, where L is F, Cl or CN, or has a carbon atom 1 to 4, and can be fluorinated alkyl, alkoxy or alkanoyl, and Cyc is trans-1,4-cyclohexylene.
此等之較佳基中,Z1及Z2具有上述式I所示之意義。較佳為Z1及Z2為-COO-、-OCO-、-CH2CH2-或 -CH=CH-COO-。 Among these preferred groups, Z 1 and Z 2 have the meanings shown in formula I above. Preferably, Z 1 and Z 2 are -COO-, -OCO-, -CH 2 CH 2 -or -CH=CH-COO-.
L較佳為F、Cl、CN、NO2、CH3、C2H5、OCH3、OC2H5、COCH3、COC2H5、CF3、OCF3、OCHF2、OCF5、尤佳為F、Cl、CN、CH3、C2H5、OCH3、COCH3及OCF3、最佳為F、CH3、OCH3及COCH3。 L is preferably F, Cl, CN, NO 2 , CH 3 , C 2 H 5 , OCH 3 , OC 2 H 5 , COCH 3 , COC 2 H 5 , CF 3 , OCF 3 , OCHF 2 , OCF 5 , especially Preferred are F, Cl, CN, CH 3 , C 2 H 5 , OCH 3 , COCH 3 and OCF 3 , and most preferred are F, CH 3 , OCH 3 and COCH 3 .
MG以下述式所選出的化合物尤佳:
此等之式中,L具有上述意義,且r為0、1或2。 In these equations, L has the above-mentioned meaning, and r is 0, 1, or 2.
此等之較佳式中,基:
非常佳為
此等之較佳化合物中存在的R具有P-(Sp)n-所示之意義之一。 The R present in these preferred compounds has one of the meanings represented by P-(Sp) n -.
P較佳為選自CH2=CW-COO-、WCH=CH-O-、
或CH2=CH-苯基-(O)K,在此W為H、CH3或Cl,且k為0或1。 Or CH 2 =CH-phenyl-(O) K , where W is H, CH 3 or Cl, and k is 0 or 1.
P尤佳為乙烯基、丙烯酸酯基、甲基丙烯酸酯基、丙烯基或環氧基,非常佳為丙烯酸酯基。 P is particularly preferably a vinyl group, an acrylate group, a methacrylate group, an acrylic group or an epoxy group, and is very preferably an acrylate group.
作為間隔基Sp,在該目的可使用該業者習知 的全部的基。間隔基Sp較佳為透過酯或醚基、或者單鍵,鍵結於聚合性基P。間隔基Sp較佳為具有碳原子1~20個、尤其碳原子1~12個,且進一步該基中存在的1個CH2基或不相鄰的2個以上之CH2基可被-O-、-S-、-NH-、-N(CH3)-、-CO-、-O-CO-、-S-CO-、-O-COO-、-CO-S-、-CO-O-、-CH(鹵素)-、-CH(CN)-、-CH=CH-或-C≡C-取代的直鏈狀或分枝鏈狀伸烷基。 As the spacer Sp, all groups known to the industry can be used for this purpose. The spacer Sp is preferably bonded to the polymerizable group P through an ester or ether group, or a single bond. The spacer Sp preferably has 1 to 20 carbon atoms, especially 1 to 12 carbon atoms, and further, one CH 2 group or two or more non-adjacent CH 2 groups in the group may be -O -, -S-, -NH-, -N(CH 3 )-, -CO-, -O-CO-, -S-CO-, -O-COO-, -CO-S-, -CO-O -, -CH(halogen)-, -CH(CN)-, -CH=CH- or -C≡C- substituted linear or branched chain alkylene.
代表的間隔基,例如為-(CH2)0-、-(CH2CH2O)r-CH2CH2-、-CH2CH2-S-CH2CH2-或-CH2CH2-NH-CH2CH2-,且此等之基中,o為2~12的整數,而r為1~3的整數。 Representative spacers, such as -(CH 2 ) 0 -, -(CH 2 CH 2 O) r -CH 2 CH 2 -, -CH 2 CH 2 -S-CH 2 CH 2 -or -CH 2 CH 2 -NH-CH 2 CH 2 -, and in these bases, o is an integer of 2-12, and r is an integer of 1-3.
較佳間隔基,例如伸乙基、伸丙基、伸丁基、伸戊基、伸己基、伸庚基、伸辛基、伸壬基、伸癸基、伸十一基、伸十二基、伸十八基、伸乙基氧基伸乙基、伸甲基氧基伸丁基、伸乙基-硫代伸乙基、伸乙基-N-甲基亞胺基伸乙基及1-甲基伸烷基。 Preferred spacers, such as ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylylene, decylene, undecylenyl, and dodecylene , Octadecylene, ethyleneoxyethylene, ethyleneoxybutylene, ethylene-thioethylene, ethylene-N-methyliminoethylene and 1-methyl Alkylene.
式I中,2個P、Sp及X可各自相同或相異。 In formula I, the two P, Sp and X may be the same or different.
式I所表示的聚合性液晶元化合物的代表例如下述化合物列表。然而,該列表僅為例示,而不限制本發明之範圍。 Representative examples of the polymerizable mesogen compound represented by Formula I are listed below. However, this list is only an illustration, and does not limit the scope of the present invention.
此等之化合物中,x及y各自獨立,為1~12,M1為氫原子或甲基,而L1及L2各自獨立,為H、鹵素或CN、或者具有碳原子1~7個的烷基、烷氧基或鏈烷醯基。 In these compounds, x and y are independently from 1 to 12, M 1 is a hydrogen atom or a methyl group, and L 1 and L 2 are independently from each other and are H, halogen or CN, or have 1 to 7 carbon atoms的alkyl, alkoxy or alkanoyl.
此等之化合物為文獻習知、或被市售。 These compounds are known in the literature or are commercially available.
本發明使用的聚合物組成物使用的有機溶劑,為溶解樹脂成分的有機溶劑則不特別限定。其具體例列舉如下。 The organic solvent used in the polymer composition used in the present invention is not particularly limited if it is an organic solvent that dissolves the resin component. Specific examples are listed below.
可舉例如N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-甲基己內醯胺、2-吡咯啶酮、N-乙基吡咯啶酮、N-乙烯基吡咯啶酮、二甲基亞碸、四甲基尿素、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯、3-甲氧基-N,N-二甲基丙醯胺、3-乙氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺、1,3-二甲基-咪唑啉酮、乙基戊基酮、甲基壬基酮、甲基乙基酮、甲基異戊基酮、甲基異丙基酮、環己酮、乙烯碳酸酯、丙烯碳酸酯、二甘醇二甲醚、4-羥基-4-甲基-2-戊酮、丙二醇單乙酸酯、丙二醇單甲基醚、丙二醇-tert-丁基醚、二丙二醇單甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲基醚等。此等可單獨使用亦可混合使用。 For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactone, 2-pyrrolidone , N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfide, tetramethylurea, pyridine, dimethyl sulfide, hexamethyl pyrrolidone, γ-butyrolactone, 3-methyl Oxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1, 3-Dimethyl-imidazolinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, Propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl Ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether Wait. These can be used alone or in combination.
在上述基板的形成電極側塗佈聚合物組成物。 The polymer composition is applied to the electrode forming side of the above-mentioned substrate.
本發明之製造方法使用的該聚合物組成物,含有 (A)在指定溫度範圍表現液晶性的感光性側鏈型高分子、(B)反應性液晶元化合物及(C)有機溶劑。 The polymer composition used in the manufacturing method of the present invention contains (A) A photosensitive side chain polymer that exhibits liquid crystallinity in a specified temperature range, (B) a reactive mesogen compound, and (C) an organic solvent.
本發明使用的聚合物組成物,以適合液晶配向膜之形成之方式調製成塗佈液為佳。亦即,本發明使用的聚合物組成物,以調製為形成樹脂被膜用的樹脂成分溶於有機溶劑的溶液為佳。在此,該樹脂成分係指包含已說明的可表現液晶性的感光性側鏈型高分子之樹脂成分。此時,樹脂成分之含量以1質量%~20質量%為佳、更佳為3質量%~15質量%、尤佳為3質量%~10質量%。 The polymer composition used in the present invention is preferably prepared as a coating liquid in a manner suitable for the formation of the liquid crystal alignment film. That is, the polymer composition used in the present invention is preferably prepared as a solution in which the resin component for forming a resin film is dissolved in an organic solvent. Here, the resin component refers to a resin component containing the photosensitive side chain type polymer capable of expressing liquid crystallinity as described above. At this time, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.
本實施形態的聚合物組成物中,前述樹脂成分可全部為上述可表現液晶性的感光性側鏈型高分子,但在不損及液晶表現能力及感光性能範圍,可混合彼等以外之其他聚合物。此時,樹脂成分中其他聚合物的含量為0.5質量%~80質量%、較佳為1質量%~50質量%。 In the polymer composition of this embodiment, the aforementioned resin components may all be the above-mentioned photosensitive side chain type polymer capable of expressing liquid crystallinity, but other than them may be mixed without impairing the range of liquid crystal expressing ability and photosensitive performance polymer. At this time, the content of other polymers in the resin component is 0.5% by mass to 80% by mass, preferably 1% by mass to 50% by mass.
如此之其他聚合物,例如由聚(甲基)丙烯酸酯或聚醯胺酸或聚醯亞胺等所構成且非可表現液晶性的感光性側鏈型高分子的聚合物等。 Such other polymers include, for example, polymers of poly(meth)acrylate, polyamide acid, polyimide, etc., which are not photosensitive side chain type polymers that can express liquid crystallinity, and the like.
本發明使用的聚合物組成物,可含有上述(A)成分、(B)成分及(C)有機溶劑以外的成分。其例方面,可舉例如使塗佈聚合物組成物時的膜厚均勻性或表面平滑性提升之溶劑或化合物、使液晶配向膜與基板之密著性提升之化合物等,但不限於此。 The polymer composition used in the present invention may contain components other than the above-mentioned (A) component, (B) component, and (C) organic solvent. Examples thereof include solvents or compounds that improve film thickness uniformity or surface smoothness when the polymer composition is applied, and compounds that improve the adhesion between the liquid crystal alignment film and the substrate, but are not limited to these.
提升膜厚的均勻性或表面平滑性之溶劑(貧溶劑)之具體例子方面,可舉例如下。 Specific examples of solvents (lean solvents) that improve the uniformity of film thickness or surface smoothness can be given as follows.
例如異丙基醇、甲氧基甲基戊醇、甲基溶纖劑、乙基溶纖劑、丁基溶纖劑、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、丁基卡必醇、乙基卡必醇、乙基卡必醇乙酸酯、乙二醇、乙二醇單乙酸酯、乙二醇單異丙基醚、乙二醇單丁基醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲基醚、丙二醇-tert-丁基醚、二丙二醇單甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲基醚、3-甲基-3-甲氧基丁醇、二異丙基醚、乙基異丁基醚、二異丁烯、戊基乙酸酯、丁基丁酯、丁基醚、二異丁基酮、甲基環己烯、丙基醚、二己基醚、1-己醇、n-己烷、n-戊烷、n-辛烷、二乙基醚、乳酸甲基酯、乳酸乙基酯、乙酸甲基酯、乙酸乙基酯、乙酸n-丁基酯、乙酸丙二醇單乙基醚、丙酮酸甲基酯、丙酮酸乙基酯、3-甲氧基丙酸甲基酯、3-乙氧基丙酸甲基乙基酯、3-甲氧基丙酸乙基酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙基酯、3-甲氧基丙酸丁基酯、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇-1-單甲基醚-2-乙酸酯、丙二醇-1-單乙基醚-2-乙酸酯、二丙二醇、2-(2-乙氧基丙 氧基)丙醇、乳酸甲基酯、乳酸乙基酯、乳酸n-丙基酯、乳酸n-丁基酯、乳酸異戊基酯等的具有低表面張力的溶劑等。 Such as isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, Dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate mono Propyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl Ether, diisobutylene, pentyl acetate, butylbutyl, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, acetone Methyl ester, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Propionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, 1-methoxy-2-propanol, 1-ethoxy -2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2 -Acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropane (Oxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate and other solvents with low surface tension.
此等之貧溶劑可為1種類或複數種類混合使用。使用上述般溶劑的場合,以不使聚合物組成物所含之溶劑全體的溶解性顯著降低,以溶劑全體的5質量%~80質量%為佳、更佳為20質量%~60質量%。 These poor solvents can be one type or a mixture of multiple types. When the above-mentioned solvents are used, so as not to significantly reduce the solubility of the entire solvent contained in the polymer composition, 5 mass% to 80 mass% of the total solvent is preferred, and 20 mass% to 60 mass% is more preferred.
提升膜厚的均勻性或表面平滑性之化合物方面,可舉例如氟系界面活性劑、矽酮系界面活性劑及非離子系界面活性劑等。 As for the compound that improves the uniformity of the film thickness or the surface smoothness, for example, a fluorine-based surfactant, a silicone-based surfactant, and a non-ionic surfactant, etc. can be mentioned.
更具體上,可舉例如EFTOP(登錄商標)301、EF303、EF352(Thochem Products.公司製)、MEGAFAC(登錄商標)F171、F173、R-30(DIC公司製)、Fluorad FC430、FC431(住友3M公司製)、Asahiguard(登錄商標)AG710(旭硝子公司製)、Surflon(登錄商標)S-382、SC101、SC102、SC103、SC104、SC105、SC106(AGC SEIMI CHEMICAL CO.,LTD製)等。此等之界面活性劑的使用比例子,相對聚合物組成物所含有的樹脂成分之100質量份,較佳為0.01質量份~2質量份、更佳為0.01質量份~1質量份。 More specifically, for example, EFTOP (registered trademark) 301, EF303, EF352 (manufactured by Thochem Products.), MEGAFAC (registered trademark) F171, F173, R-30 (manufactured by DIC Corporation), Fluorad FC430, FC431 (Sumitomo 3M Company), Asahiguard (registered trademark) AG710 (made by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by AGC SEIMI CHEMICAL CO., LTD), etc. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass relative to 100 parts by mass of the resin component contained in the polymer composition.
提升液晶配向膜與基板之密著性的化合物的具體例子方面,可舉例如下示含官能性矽烷之化合物等。 As for specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate, the following functional silane-containing compounds can be exemplified.
例如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-三乙氧基矽烷基丙基三乙烯三胺、N-三甲氧基矽烷基丙基三乙烯三胺、10-三甲氧基矽烷基-1,4,7-三氮雜癸烷、10-三乙氧基矽烷基-1,4,7-三氮雜癸烷、9-三甲氧基矽烷基-3,6-二氮雜壬基乙酸酯、9-三乙氧基矽烷基-3,6-二氮雜壬基乙酸酯、N-苄基-3-胺基丙基三甲氧基矽烷、N-苄基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-雙(氧化乙烯)-3-胺基丙基三甲氧基矽烷、N-雙(氧化乙烯)-3-胺基丙基三乙氧基矽烷等。 For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane Alkyl, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3 -Ureaylpropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-amine Triethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4, 7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-Triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyl trimethoxysilane, N-benzyl-3-aminopropyl three Ethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(ethylene oxide)-3-amino Propyl trimethoxysilane, N-bis(oxyethylene)-3-aminopropyl triethoxysilane, etc.
進而除基板與液晶配向膜之密著性之提升,以防止構成液晶顯示元件時之背光造成的電特性之降低等目的,聚合物組成物中可含有以下般酚醛樹脂系或含環氧基化合物的添加劑。具體的酚醛樹脂系添加劑如以下所示,但不限於該構造。 Furthermore, in addition to the improvement of the adhesion between the substrate and the liquid crystal alignment film to prevent the reduction of electrical characteristics caused by the backlight when forming the liquid crystal display element, the polymer composition may contain the following phenolic resins or epoxy-containing compounds Of additives. Specific phenol resin additives are shown below, but are not limited to this structure.
具體的含環氧基化合物方面,如乙二醇二環氧丙基醚、聚乙二醇二環氧丙基醚、丙二醇二環氧丙基醚、三丙二醇二環氧丙基醚、聚丙二醇二環氧丙基醚、新戊基二醇二環氧丙基醚、1,6-己烷二醇二環氧丙基醚、甘油二環氧丙基醚、2,2-二溴新戊基二醇二環氧丙基醚、1,3,5,6-四環氧丙基-2,4-己烷二醇、N,N,N’,N’-四環氧丙基-m-二甲苯二胺、1,3-雙(N,N-二環氧丙基胺基甲基)環己烷、N,N,N’,N’-四環氧丙基-4、4’-二胺基二苯基甲烷等。 Specific epoxy-containing compounds, such as 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, glycerin diglycidyl ether, 2,2-dibromoneopentyl Diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m -Xylene diamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4, 4' -Diaminodiphenylmethane and the like.
使用提升與基板之密著性的化合物之場合,其使用量相對聚合物組成物所含有的樹脂成分之100質量份,以0.1質量份~30質量份為佳、更佳為1質量份~20質量份。使用量未達0.1質量份則無法期待密著性提升的效果,比30質量份多則有液晶的配向性變差之情形。 When using a compound that improves adhesion to the substrate, the amount used is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass relative to 100 parts by mass of the resin component contained in the polymer composition Mass parts. If the usage amount is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it is more than 30 parts by mass, the alignment of the liquid crystal may deteriorate.
作為添加劑,亦可使用光增感劑。以無色增感劑及三重態增感劑為佳。 As an additive, a photosensitizer can also be used. Colorless sensitizers and triplet sensitizers are preferred.
光增感劑方面,例如芳香族硝基化合物、香豆素(7-二乙基胺基-4-甲基香豆素、7-羥基4-甲基香豆素)、香豆素酮、羰基雙香豆素、芳香族2-羥基酮、及以 胺基取代的芳香族2-羥基酮(2-羥基二苯甲酮、單-或者二-p-(二甲基胺基)-2-羥基二苯甲酮)、苯乙酮、蒽醌、呫噸酮、噻噸酮、苯并蒽酮、噻唑啉(2-苯甲醯基亞甲基-3-甲基-β-萘並噻唑啉、2-(β-苯甲醯基亞甲基)-3-甲基苯並噻唑啉、2-(α-苯甲醯基亞甲基)-3-甲基苯並噻唑啉、2-(4-聯苯基亞甲基)-3-甲基苯並噻唑啉、2-(β-苯甲醯基亞甲基)-3-甲基-β-萘並噻唑啉、2-(4-聯苯基亞甲基)-3-甲基-β-萘並噻唑啉、2-(p-氟苯甲醯基亞甲基)-3-甲基-β-萘並噻唑啉)、噁唑啉(2-苯甲醯基亞甲基-3-甲基-β-萘並噁唑啉、2-(β-苯甲醯基亞甲基)-3-甲基苯並噁唑啉、2-(α-苯甲醯基亞甲基)-3-甲基苯並噁唑啉、2-(4-聯苯基亞甲基)-3-甲基苯並噁唑啉、2-(β-苯甲醯基亞甲基)-3-甲基-β-萘並噁唑啉、2-(4-聯苯基亞甲基)-3-甲基-β-萘並噁唑啉、2-(p-氟苯甲醯基亞甲基)-3-甲基-β-萘並噁唑啉)、苯並噻唑、硝基苯胺(m-或者p-硝基苯胺、2,4,6-三硝基苯胺)或硝基苊萘(5-硝基苊萘)、(2-[(m-羥基-p-甲氧基)苯乙烯基]苯並噻唑、安息香烷基醚、N-烷基化夫塔隆、苯乙酮縮酮(2,2-二甲氧基苯基乙酮)、萘、蒽(2-萘甲醇、2-萘羧酸、9-蒽甲醇、及9-蒽接酸)、苯并哌喃、偶氮吲哚嗪、甲基香豆素等。 In terms of photosensitizers, such as aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), coumarin ketones, Carbonyl biscoumarin, aromatic 2-hydroxy ketone, and Amino substituted aromatic 2-hydroxy ketones (2-hydroxybenzophenone, mono- or di-p-(dimethylamino)-2-hydroxybenzophenone), acetophenone, anthraquinone, Xanthone, thioxanthone, benzoanthrone, thiazoline (2-benzylmethylene-3-methyl-β-naphthazoline, 2-(β-benzylmethylene )-3-methylbenzothiazoline, 2-(α-benzylmethylene)-3-methylbenzothiazoline, 2-(4-biphenylmethylene)-3-methyl Benzothiazoline, 2-(β-benzylmethylene)-3-methyl-β-naphthazoline, 2-(4-biphenylmethylene)-3-methyl- β-naphthazoline, 2-(p-fluorobenzylmethylene)-3-methyl-β-naphthazoline), oxazoline (2-benzylmethylene-3 -Methyl-β-naphthoxazoline, 2-(β-benzylmethylene)-3-methylbenzoxazoline, 2-(α-benzylmethylene)- 3-methylbenzoxazoline, 2-(4-biphenylmethylene)-3-methylbenzoxazoline, 2-(β-benzylmethylene)-3-methyl -Β-naphthoxazoline, 2-(4-biphenylmethylene)-3-methyl-β-naphthoxazoline, 2-(p-fluorobenzamethylene) -3-methyl-β-naphthoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthylene (5 -Nitroacenaphthylene), (2-[(m-hydroxy-p-methoxy)styryl]benzothiazole, benzoin alkyl ether, N-alkylated futalone, acetophenone ketal ( 2,2-Dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalene methanol, 2-naphthalene carboxylic acid, 9-anthracene methanol, and 9-anthracene acid), benzopiperan, azoindole Doxyazine, methyl coumarin, etc.
較佳為芳香族2-羥基酮(二苯甲酮)、香豆素、香豆素酮、羰基雙香豆素、苯乙酮、蒽醌、呫噸酮、噻噸酮、及苯乙酮縮酮。 Preferably aromatic 2-hydroxy ketone (benzophenone), coumarin, coumarin ketone, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone Ketal.
具有本發明之液晶配向膜的基板之製造方法,具有:[I]將含有(A)在指定溫度範圍表現液晶性的感光性側鏈型高分子、(B)反應性液晶元化合物及有機溶劑的聚合物組成物塗佈於具有液晶驅動用電極的基板上而形成塗膜的步驟;[II]對[I]得到的塗膜照射偏光紫外線的步驟;及[III]將[II]得到的塗膜加熱的步驟。 The method for manufacturing a substrate with the liquid crystal alignment film of the present invention includes: [I] will contain (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a specified temperature range, (B) a reactive mesogen compound, and an organic solvent The step of coating the polymer composition of the polymer composition on the substrate with the electrode for liquid crystal driving to form a coating film; [II] the step of irradiating the coating film obtained by [I] with polarized ultraviolet rays; and [III] the step of applying [II] The step of heating the coating film.
藉由上述步驟,可得到被賦予配向控制能力的垂直電場驅動型液晶顯示元件(例如扭轉向列型液晶顯示元件、垂直配向型液晶顯示元件、STN型液晶顯示元件、ECB型液晶顯示元件及OCB型液晶顯示元件)用液晶配向膜,且可得到具有該液晶配向膜的基板。 Through the above steps, a vertical electric field driven liquid crystal display element (such as a twisted nematic liquid crystal display element, a vertical alignment liquid crystal display element, an STN liquid crystal display element, an ECB liquid crystal display element, and an OCB can be obtained that has been given alignment control capabilities. Type liquid crystal display element) uses a liquid crystal alignment film, and a substrate having the liquid crystal alignment film can be obtained.
又,上述得到的基板(第1基板)之外,藉由準備第2基板,可得到垂直電場驅動型液晶顯示元件(例如扭轉向列型液晶顯示元件、垂直配向型液晶顯示元件、STN型液晶顯示元件、ECB型液晶顯示元件及OCB型液晶顯示元件)。 In addition to the substrate (first substrate) obtained above, by preparing a second substrate, a vertical electric field drive type liquid crystal display element (such as a twisted nematic liquid crystal display element, a vertical alignment type liquid crystal display element, an STN liquid crystal display element) can be obtained. Display element, ECB type liquid crystal display element and OCB type liquid crystal display element).
第2基板,藉由使用上述步驟[I]~[III],可得到具有被賦予配向控制能力的液晶配向膜的第2基板。 For the second substrate, by using the above steps [I] to [III], a second substrate having a liquid crystal alignment film to which alignment control ability is imparted can be obtained.
垂直電場驅動型液晶顯示元件之製造方法具有[IV]使上述所得的第1及第2基板以介隔著液晶以第1及第2基板的液晶配向膜相對之方式,對向配置而得 到液晶顯示元件的步驟。此時,使上述所得的附第1及第2配向膜之基板,且傾斜角度為10~50度者,以摩擦方向(液晶的配向)為平行且相同方向(平行配向)之方式配置,則可得到OCB型液晶顯示元件。以相同方法,使用傾斜角度為80~90度之附配向膜之基板2枚進行,可得到垂直配向型液晶顯示元件。以摩擦方向相互垂直之方式,即約90度扭曲之方式配置,可得到扭轉向列型液晶顯示元件,以摩擦方向約260度扭曲之方式配置,可得到STN型液晶顯示元件。又,將上述所得的附第1及第2配向膜之基板以配向處理方向相互平行且相反方向(反向平行)之方式配置,則可得到ECB型液晶顯示元件。 The method for manufacturing a vertical electric field drive type liquid crystal display element has [IV] the first and second substrates obtained above are arranged so that the liquid crystal alignment films of the first and second substrates face each other through the liquid crystal, and are obtained by opposing Step to the liquid crystal display element. At this time, the substrate with the first and second alignment films obtained above and the inclination angle of 10 to 50 degrees are arranged so that the rubbing direction (alignment of the liquid crystal) is parallel and the same direction (parallel alignment), then OCB-type liquid crystal display elements can be obtained. In the same way, using two substrates with an alignment film with an inclination angle of 80 to 90 degrees, a vertical alignment type liquid crystal display element can be obtained. The rubbing directions are perpendicular to each other, that is, the twisted nematic liquid crystal display element is arranged in a manner twisted at about 90 degrees, and the STN liquid crystal display element is obtained when the rubbing direction is twisted at about 260 degrees. Furthermore, by arranging the substrates with the first and second alignment films obtained above in such a manner that the alignment processing directions are parallel to each other and opposite (anti-parallel), an ECB-type liquid crystal display element can be obtained.
以下、說明本發明之製造方法所具有的[I]~[III]、及[IV]之各步驟。 Hereinafter, each step of [I] to [III] and [IV] included in the manufacturing method of the present invention will be explained.
在步驟[I],在具有液晶驅動用電極的基板上,塗佈含有(A)在指定溫度範圍表現液晶性的感光性側鏈型高分子、(B)反應性液晶元化合物及有機溶劑的聚合物組成物而形成塗膜。 In step [I], a substrate with electrodes for driving liquid crystals is coated with (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a specified temperature range, (B) a reactive mesogen compound, and an organic solvent. The polymer composition forms a coating film.
關於基板雖不特別限定,在所製造的液晶顯示元件為透過型時,以使用透明性高的基板為佳。該場合,無特別限制,可使用玻璃基板、或丙烯酸基板或聚碳酸酯基板等 之塑膠基板等。 Although the substrate is not particularly limited, when the manufactured liquid crystal display element is a transmissive type, it is preferable to use a highly transparent substrate. In this case, there are no particular restrictions, and glass substrates, acrylic substrates, polycarbonate substrates, etc. can be used The plastic substrate and so on.
液晶驅動用的電極,以ITO(Indium Tin Oxide:氧化銦錫)、IZO(Indium Zinc Oxide:氧化銦鋅)等為佳。又,在反射型的液晶顯示元件,若僅單側的基板,亦可使用矽晶圓等之不透明物,此時的電極亦可使用鋁等之反射光的材料。 The electrode for liquid crystal driving is preferably ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), or the like. In addition, in the reflective liquid crystal display element, if only a single-sided substrate is used, an opaque material such as a silicon wafer may also be used. In this case, a light-reflecting material such as aluminum may also be used for the electrode.
在基板形成電極之方法,可使用以往習知手法。 The method of forming electrodes on the substrate can use conventionally known methods.
將上述聚合物組成物塗佈於具有液晶驅動用電極的基板上之方法不特別限定。 The method of applying the above-mentioned polymer composition on a substrate having an electrode for liquid crystal driving is not particularly limited.
塗佈方法,工業上以網版印刷、膠版印刷、柔版印刷或噴墨法等進行之方法為一般。其他的塗佈方法方面,有浸漬法、輥塗法、狹縫塗佈法、旋轉法(旋轉塗佈法)或噴霧法等,可因應目的使用此等。 The coating method is generally carried out by screen printing, offset printing, flexographic printing, or inkjet method in the industry. Other coating methods include dipping, roll coating, slit coating, spinning (spin coating), or spraying methods. These can be used according to the purpose.
在具有液晶驅動用電極的基板上塗佈聚合物組成物後,以加熱板、熱循環型烤箱或IR(紅外線)型烤箱等之加熱手段,在50~230℃、較佳為50~200℃、0.4分鐘~60分鐘、較佳為0.5分鐘~10分鐘使溶劑蒸發而可得到塗膜。此時的乾燥溫度以比側鏈型高分子的液晶相表現溫度低為佳。 After coating the polymer composition on the substrate with liquid crystal drive electrodes, use heating means such as a hot plate, thermal cycle oven or IR (infrared) oven at 50~230℃, preferably 50~200℃ , 0.4 minutes to 60 minutes, preferably 0.5 minutes to 10 minutes to evaporate the solvent to obtain a coating film. The drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the side chain type polymer.
塗膜之厚度過厚,則在液晶顯示元件的消費電力面上變得不利,過薄則有液晶顯示元件的信賴性降低之情形,故較佳為5nm~300nm、更較佳為10nm~150nm。 If the thickness of the coating film is too thick, it will become disadvantageous on the power consumption surface of the liquid crystal display element. If it is too thin, the reliability of the liquid crystal display element may decrease, so it is preferably 5nm~300nm, more preferably 10nm~150nm .
又,[I]步驟後,在接著之[II]步驟前亦可設置使形成有塗膜之基板冷卻至室溫的步驟。 Furthermore, after the step [I], a step of cooling the substrate on which the coating film is formed to room temperature may be provided before the subsequent step [II].
在步驟[II],對在步驟[I]所得到的塗膜,從斜方向照射偏光紫外線。對塗膜之膜面照射偏光紫外線場合,相對基板從一定的方向透過偏光板,照射經偏光的紫外線。使用的紫外線方面,可使用波長100nm~400nm的範圍之紫外線。較佳為因使用的塗膜之種類而透過濾波器等選擇最適當的波長。而,例如可以可選擇性地引發光交聯反應之方式,選擇波長290nm~400nm的範圍紫外線使用。紫外線方面,可使用例如從高壓水銀燈放射之光。 In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet rays from an oblique direction. When irradiating the film surface of the coating film with polarized ultraviolet rays, the polarizing plate is irradiated with polarized ultraviolet rays from a certain direction relative to the substrate. Regarding the ultraviolet rays used, ultraviolet rays with a wavelength in the range of 100nm to 400nm can be used. It is preferable to select the most appropriate wavelength according to the type of coating film used and the transmission filter or the like. However, for example, it is possible to select ultraviolet light in the range of 290nm~400nm in a way that can selectively initiate the photocrosslinking reaction. For ultraviolet light, for example, light emitted from a high-pressure mercury lamp can be used.
偏光的紫外線之照射量依使用的塗膜而異。照射量以該塗膜中實現與偏光的紫外線之偏光方向平行的方向之紫外線吸光度與垂直方向之紫外線吸光度之差ΔA之最大值(以下,亦稱ΔAmax)的偏光紫外線之量之1%~70%的範圍內為佳、1%~50%的範圍內更佳。 The amount of polarized ultraviolet radiation varies depending on the coating film used. The irradiation amount is based on the maximum value of the difference ΔA between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorbance in the vertical direction in the coating film (hereinafter, also referred to as ΔAmax), which is 1%~70 The range of% is better, and the range of 1% to 50% is more preferable.
偏光紫外線的照射方向通常相對基板為1°~89°,但較佳為10°~80°、尤佳為20°~70°。該角度過小時有預傾角變小之問題,過大時有預傾角變高之問題。 The irradiation direction of polarized ultraviolet rays is usually 1°~89° relative to the substrate, but preferably 10°~80°, and particularly preferably 20°~70°. If the angle is too small, the pretilt angle will decrease, and if it is too large, the pretilt angle will increase.
將照射方向調節為上述角度之方法方面,有使基板本身傾斜的方法、與使光源傾斜的方法,但使光源本身傾斜由產率觀點來看較佳。 Regarding the method of adjusting the irradiation direction to the above-mentioned angle, there are a method of tilting the substrate itself and a method of tilting the light source, but tilting the light source itself is preferable from the viewpoint of productivity.
在步驟[III],加熱在步驟[II]照射偏光的紫外線之塗 膜。經加熱,可賦予塗膜配向控制能力。 In step [III], heat the polarized ultraviolet coating in step [II] membrane. After heating, it can give the coating film alignment control ability.
加熱可使用加熱板、熱循環型烤箱或IR(紅外線)型烤箱等之加熱手段。加熱溫度可考量使用的塗膜之表現液晶性的溫度決定。 Heating can use heating means such as hot plate, thermal cycle oven or IR (infrared) oven. The heating temperature can be determined by considering the temperature of the coating film used to express the liquid crystallinity.
加熱溫度以側鏈型高分子表現液晶性的溫度(以下,稱液晶性表現溫度)之溫度範圍內為佳。塗膜般薄膜表面之場合,塗膜表面之液晶性表現溫度預想比將可表現液晶性的感光性側鏈型高分子以塊狀觀察場合的液晶性表現溫度低。因此,加熱溫度在塗膜表面之液晶性表現溫度的溫度範圍內更佳。亦即,偏光紫外線照射後的加熱溫度的溫度範圍以比使用的側鏈型高分子的液晶性表現溫度的溫度範圍下限低10℃的溫度為下限,比該液晶溫度範圍的上限低10℃的溫度為上限之範圍的溫度為佳。加熱溫度比為上述溫度範圍低,則有塗膜中因熱之異方向性之增幅效果變得不充分之傾向,又加熱溫度比上述溫度範圍高,則有塗膜之狀態變得接近等方性之液體狀態(等方相)的傾向,該場合,有因自我組織化而在一方向再配向變困難之情形。 The heating temperature is preferably within the temperature range at which the side chain polymer exhibits liquid crystallinity (hereinafter referred to as the liquid crystallinity expression temperature). In the case of a thin film surface like a coating film, the liquid crystal expression temperature of the coating film surface is expected to be lower than the liquid crystal expression temperature when the photosensitive side chain polymer that can express liquid crystal properties is observed in bulk. Therefore, the heating temperature is better within the temperature range of the liquid crystal display temperature of the coating film surface. That is, the temperature range of the heating temperature after the polarized ultraviolet radiation is 10°C lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain polymer used as the lower limit, and 10°C lower than the upper limit of the liquid crystal temperature range The temperature within the upper limit range is preferable. If the heating temperature is lower than the above-mentioned temperature range, the amplification effect of the coating film due to the thermal anisotropy tends to become insufficient. If the heating temperature is higher than the above-mentioned temperature range, the state of the coating film may become nearly equal. The tendency of sexual liquid state (isotropic phase). In this case, it may become difficult to re-orientate in one direction due to self-organization.
又,液晶性表現溫度在側鏈型高分子或塗膜表面產生從固體相相轉化為液晶相之玻璃轉化溫度(Tg)以上,且在產生從液晶相相轉化為均方性相(等方相)之均方性相轉化溫度(Tiso)以下的溫度。 In addition, the liquid crystallinity expression temperature is higher than the glass transition temperature (Tg) of the side chain polymer or the surface of the coating film from the solid phase to the liquid crystal phase, and when the liquid crystal phase is converted to the homogeneous phase (equal square) The temperature below the mean squareness phase transition temperature (Tiso) of phase).
加熱後形成的塗膜之厚度由步驟[I]所記載相同理由,較佳為5nm~300nm、更佳為50nm~150nm者。 The thickness of the coating film formed after heating is the same as that described in step [I], and is preferably 5 nm to 300 nm, more preferably 50 nm to 150 nm.
藉由具有以上的步驟,在本發明的製造方法,可實現高效率的對塗膜導入異方向性。而,可高效率地製造附液晶配向膜之基板。 By having the above steps, in the manufacturing method of the present invention, it is possible to efficiently introduce anisotropy to the coating film. However, the substrate with the liquid crystal alignment film can be manufactured efficiently.
[IV]步驟,為具備具有基板的形成有液晶配向膜側對向配置的2枚的[III]得到的基板、設置於基板間的液晶層、與基板與液晶層間設置的以本發明之液晶配向劑所形成的上述液晶配向膜的液晶晶胞之液晶顯示元件。如此之本發明之垂直電場驅動型液晶顯示元件,可舉例如扭曲向列型(TN:Twisted Nematic)方式、垂直配向(VA:Vertical Alignment)方式或STN(Super-Twisted Nematic)型液晶顯示元件、ECB(Electrically Controlled Birefringence)型液晶顯示元件及OCB配向(OCB:Optically Compensated Bend)等種種者。 The step [IV] includes the two substrates obtained in [III] provided with a substrate on the side where the liquid crystal alignment film is formed facing each other, a liquid crystal layer provided between the substrates, and a liquid crystal of the present invention provided between the substrate and the liquid crystal layer The liquid crystal display element of the liquid crystal cell of the liquid crystal alignment film formed by the alignment agent. Such a vertical electric field drive type liquid crystal display element of the present invention may include, for example, a twisted nematic (TN: Twisted Nematic) method, a vertical alignment (VA: Vertical Alignment) method, or an STN (Super-Twisted Nematic) type liquid crystal display element. ECB (Electrically Controlled Birefringence) type liquid crystal display elements and OCB alignment (OCB: Optically Compensated Bend), etc.
液晶晶胞或液晶顯示元件之製作例,可舉例如準備上述第1及第2基板,於其一基板的液晶配向膜上散佈間隔件,以液晶配向膜面為內側,欲得到扭轉向列型元件時,以紫外線曝光方向相互垂直之方式,欲得到其他的元件時,如上述貼合另一基板,使液晶減壓注入後密封之方法、或於散佈有間隔件的液晶配向膜面滴下液晶後,貼合基板後進行密封之方法等。此時的間隔件的徑,較佳為1μm~30μm、更較佳為2μm~10μm。該間隔件徑決定挾持液晶層之一對基板間距離、即液晶層的厚度。 An example of the production of a liquid crystal cell or a liquid crystal display element can be, for example, preparing the above-mentioned first and second substrates, spreading spacers on the liquid crystal alignment film of one of the substrates, and using the liquid crystal alignment film surface as the inner side to obtain a twisted nematic In the case of components, the ultraviolet exposure directions are perpendicular to each other. To obtain other components, the method of bonding another substrate as described above to inject the liquid crystal under reduced pressure and then sealing, or dripping liquid crystal on the surface of the liquid crystal alignment film with spacers Then, the method of sealing after bonding the substrate. The diameter of the spacer at this time is preferably 1 μm to 30 μm, more preferably 2 μm to 10 μm. The diameter of the spacer determines the distance between a pair of substrates sandwiching the liquid crystal layer, that is, the thickness of the liquid crystal layer.
得到的液晶顯示元件,進一步為了配向安定性,以進行退火處理為佳。加熱溫度為液晶的相轉化溫度、較佳為10~160℃、更較佳為50~140℃者。 The obtained liquid crystal display element is further preferably subjected to an annealing treatment for alignment stability. The heating temperature is the phase transition temperature of the liquid crystal, preferably 10 to 160°C, more preferably 50 to 140°C.
本發明的附塗膜基板的製造方法,為將聚合物組成物塗佈於基板上,形成塗膜後,照射偏光的紫外線。接著,藉由進行加熱製造實現對側鏈型高分子膜導入高效率的異方向性,且具備液晶的配向控制能力的附液晶配向膜之基板。 The method of manufacturing a substrate with a coating film of the present invention is to apply a polymer composition on a substrate to form a coating film, and then irradiate polarized ultraviolet rays. Next, a substrate with a liquid crystal alignment film is produced by heating to realize the introduction of high-efficiency anisotropy into the side chain polymer film and the ability to control the alignment of the liquid crystal.
在本發明使用的塗膜,利用側鏈的光反應與基於液晶性之自我組織化而引起的分子再配向之原理,對塗膜實現高效率的異方向性之導入。在本發明的製造方法,於側鏈型高分子具有光交聯性基作為光反應性基構造之場合,使用側鏈型高分子於基板上形成塗膜後,照射偏光的紫外線,接著,進行加熱後,製作液晶顯示元件。 The coating film used in the present invention utilizes the principle of molecular realignment caused by the photoreaction of the side chain and the self-organization based on liquid crystallinity to achieve high-efficiency introduction of anisotropy to the coating film. In the production method of the present invention, when the side chain type polymer has a photocrosslinkable group as the photoreactive group structure, the side chain type polymer is used to form a coating film on the substrate, and then polarized ultraviolet rays are irradiated. After heating, a liquid crystal display element was produced.
因此,本發明的方法使用的塗膜藉由依序進行對塗膜照射偏光的紫外線與加熱處理,高效率地導入異方向性,可作成配向控制能力優異的液晶配向膜。 Therefore, the coating film used in the method of the present invention can be made into a liquid crystal alignment film with excellent alignment control ability by sequentially irradiating the coating film with polarized ultraviolet rays and heating treatment to efficiently introduce anisotropy.
而,在本發明的方法使用的塗膜,使對塗膜照射偏光的紫外線量與加熱處理中加熱溫度最適化。藉由此,可實現高效率的對塗膜導入異方向性。 On the other hand, the coating film used in the method of the present invention optimizes the amount of ultraviolet rays that irradiate the coating film with polarized light and the heating temperature in the heat treatment. With this, it is possible to efficiently introduce anisotropy to the coating film.
對本發明使用的塗膜,高效率的異方向性之導入,最適當的偏光紫外線之照射量,對應該塗膜中最適當使感光性基進行光交聯反應或光異構化反應、或者光-弗萊斯重排反應之量的偏光紫外線之照射量。對本發明使 用的塗膜照射偏光的紫外線的結果,進行光交聯反應或光異構化反應、或者光-弗萊斯重排反應的側鏈的感光性基為少則無法有充分光反應量。此時,之後即使加熱亦不進行充分自我組織化。另一方面,在本發明使用的塗膜,對具有光交聯性基的構造照射偏光的紫外線的結果,進行交聯反應的側鏈的感光性基過量則在側鏈間過度進行交聯反應。此時,得到的膜成為剛直,有因之後的加熱妨礙自我組織化之進行之情形。又,在本發明使用的塗膜,對具有光-弗萊斯重排基的構造照射偏光的紫外線的結果,進行光-弗萊斯重排反應的側鏈的感光性基過量則塗膜之液晶性變得過於降低。此時,有得到的膜之液晶性亦降低,因之後的加熱而妨礙自我組織化進行之情形。進而對具有光-弗萊斯重排基的構造照射偏光的紫外線的場合,紫外線之照射量過多,則側鏈型高分子進行光分解,有因之後的加熱而妨礙自我組織化進行之情形。 For the coating film used in the present invention, high-efficiency introduction of anisotropy, the most appropriate amount of polarized ultraviolet radiation, should be the most appropriate for the photo-crosslinking reaction or photoisomerization reaction, or phototransaction of the photosensitive base in the coating film. -The amount of polarized ultraviolet radiation that corresponds to the amount of Fleis rearrangement reaction. To the present invention As a result of the coating film being irradiated with polarized ultraviolet rays, the photosensitive group of the side chain that undergoes a photocrosslinking reaction, a photoisomerization reaction, or a photo-Fries rearrangement reaction is small, and a sufficient amount of photoreaction cannot be obtained. At this time, the self-organization is not sufficiently self-organized even after heating. On the other hand, in the coating film used in the present invention, as a result of irradiating a structure having a photocrosslinkable group with polarized ultraviolet rays, an excessive amount of the photosensitive group of the side chain undergoing the crosslinking reaction will cause the crosslinking reaction between the side chains to proceed excessively. . At this time, the obtained film becomes rigid, and the progress of self-organization may be hindered by subsequent heating. In addition, in the coating film used in the present invention, as a result of irradiating a structure having a photo-Fries rearrangement group with polarized ultraviolet rays, an excess of the photosensitive group of the side chain undergoing the photo-Fries rearrangement reaction results in an excessive amount of the coating film The liquid crystallinity becomes too low. At this time, the liquid crystallinity of the obtained film is also reduced, and subsequent heating may hinder the progress of self-organization. Furthermore, when polarized ultraviolet rays are irradiated to a structure having a photo-Fries rearrangement group, if the amount of ultraviolet rays is too large, the side chain polymer undergoes photolysis, which may hinder self-organization due to subsequent heating.
因此,本發明使用的塗膜中,藉由偏光紫外線之照射,側鏈的感光性基進行光交聯反應或光異構化反應、或者光-弗萊斯重排反應的最適當的量以該側鏈型高分子膜具有的感光性基的0.1莫耳%~40莫耳%為佳、0.1莫耳%~20莫耳%更佳。藉由使進行光反應的側鏈的感光性基的量在如此範圍,在之後的加熱處理之自我組織化有效率地進行,可在膜中形成高效率的異方向性。 Therefore, in the coating film used in the present invention, the photosensitive group of the side chain undergoes a photocrosslinking reaction, a photoisomerization reaction, or a photo-Fries rearrangement reaction by irradiation of polarized ultraviolet rays. 0.1 mol%-40 mol% of the photosensitive group of the side chain type polymer film is preferably 0.1 mol%-20 mol%. By setting the amount of the photosensitive group of the side chain that undergoes the photoreaction in such a range, the self-organization in the subsequent heat treatment can be efficiently performed, and highly efficient anisotropy can be formed in the film.
在本發明的方法使用的塗膜,藉由偏光的紫外線之照射量的最適化,使側鏈型高分子膜之側鏈中,感 光性基的光交聯反應或光異構化反應、或光-弗萊斯重排反應的量最適化。而,與之後的加熱處理一併,實現高效率的對本發明使用的塗膜導入異方向性。此時,關於較佳偏光紫外線之量,可基於本發明使用的塗膜之紫外吸收之評估進行。 In the coating film used in the method of the present invention, by optimizing the irradiation amount of polarized ultraviolet light, the side chain of the side chain type polymer film has a feeling of The amount of the photocrosslinking reaction, photoisomerization reaction, or photo-Fries rearrangement reaction of the photoactive group is optimized. However, in conjunction with the subsequent heat treatment, it is possible to efficiently introduce anisotropy to the coating film used in the present invention. At this time, the amount of preferable polarized ultraviolet light can be evaluated based on the ultraviolet absorption of the coating film used in the present invention.
亦即,對本發明使用的塗膜,各自測定偏光紫外線照射後的、與偏光的紫外線之偏光方向平行的方向之紫外線吸收、與垂直方向之紫外線吸收。由紫外吸收的測定結果,評估該塗膜中與偏光的紫外線之偏光方向平行的方向之紫外線吸光度與垂直方向之紫外線吸光度之差ΔA。而,求出本發明使用的塗膜中,實現的ΔA之最大值(ΔAmax)與實現其之偏光紫外線之照射量。在本發明的製造方法,以實現該ΔAmax之偏光紫外線照射量為基準,可決定液晶配向膜的製造中照射之較佳量的偏光的紫外線量。 That is, for the coating film used in the present invention, the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorption in the perpendicular direction after the polarized ultraviolet rays are respectively measured. From the measurement result of the ultraviolet absorption, the difference ΔA between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the vertical direction in the coating film was evaluated. In the coating film used in the present invention, the maximum value of ΔA (ΔAmax) achieved and the irradiation amount of polarized ultraviolet rays to achieve it were determined. In the manufacturing method of the present invention, based on the amount of polarized ultraviolet irradiation that achieves the ΔAmax, the optimal amount of polarized ultraviolet irradiation in the manufacture of the liquid crystal alignment film can be determined.
在本發明的製造方法,以使本發明使用的對塗膜照射偏光的紫外線量為實現ΔAmax的偏光紫外線之量之1%~70%的範圍內為佳、1%~50%的範圍內更佳。本發明使用的塗膜中,實現ΔAmax的偏光紫外線之量之1%~50%的範圍內的偏光紫外線之照射量,相當使該側鏈型高分子膜具有的感光性基全體的0.1莫耳%~20莫耳%進形成光交聯反應之偏光紫外線之量。 In the manufacturing method of the present invention, the amount of polarized ultraviolet light used in the present invention to irradiate the coating film is preferably within the range of 1% to 70% of the amount of polarized ultraviolet light used to achieve ΔAmax, and more preferably within the range of 1% to 50%. good. In the coating film used in the present invention, the irradiation amount of polarized ultraviolet light in the range of 1% to 50% of the amount of polarized ultraviolet light that achieves ΔAmax is equivalent to 0.1 mol of the total photosensitive group that the side chain polymer film has %~20mol% enters the amount of polarized ultraviolet light that forms the photocrosslinking reaction.
由以上,在本發明的製造方法,因實現對塗膜之高效率的異方向性之導入,以該側鏈型高分子的液晶 溫度範圍為基準,決定上述般較佳加熱溫度者為宜。因此,例如本發明使用的側鏈型高分子的液晶溫度範圍在100℃~200℃之場合,以偏光紫外線照射後的加熱的溫度在90℃~190℃為佳。藉由此,本發明使用的塗膜中,被賦予更大的異方向性。 From the above, in the manufacturing method of the present invention, because the introduction of anisotropic properties to the coating film is realized with high efficiency, the liquid crystal of the side chain type polymer The temperature range is the reference, and it is appropriate to determine the above-mentioned generally preferable heating temperature. Therefore, for example, when the liquid crystal temperature range of the side chain polymer used in the present invention is 100°C to 200°C, the heating temperature after polarized ultraviolet radiation is preferably 90°C to 190°C. By this, the coating film used in the present invention is given greater anisotropy.
藉由此,由本發明提供的液晶顯示元件對光或熱等之外部壓力顯示高信賴性。 With this, the liquid crystal display element provided by the present invention exhibits high reliability against external pressure such as light or heat.
如以上,以本發明之方法製造的橫電場驅動型液晶顯示元件用基板或具有該基板的橫電場驅動型液晶顯示元件為信賴性優異者,可適合用於大畫面且高精細的液晶電視等。 As described above, the substrate for a horizontal electric field drive type liquid crystal display element manufactured by the method of the present invention or a horizontal electric field drive type liquid crystal display element having the substrate is excellent in reliability and can be suitably used for large-screen and high-definition liquid crystal televisions, etc. .
以下以實施例說明本發明,本發明不限於該實施例。 The following examples illustrate the present invention, but the present invention is not limited to this embodiment.
實施例所使用的縮寫如下。 The abbreviations used in the examples are as follows.
MA1參考Macromolecules 2007,40,6355-6360來合成。 MA1 was synthesized with reference to Macromolecules 2007, 40, 6355-6360.
PLC1購入市售品使用。 PLC1 purchased commercially available products for use.
PLC2使用可市售購入的LC242(BASF公司)。 Commercially available LC242 (BASF Corporation) was used for PLC2.
PLC4以專利文獻(日本特開平9-118717)記載之合成法合成。 PLC4 was synthesized by the synthesis method described in the patent document (Japanese Patent Application Laid-Open No. 9-118717).
PLC5為文獻等未公開的新穎化合物。PLC5雖使用PLC4及PLC5-1進行合成,但其詳細在以下「<化合物PLC5之合成>」說明。又,PLC5-1以文獻(Liquid Crystals(2005),32(8),1031-1044.)記載之合成法進行合成。 PLC5 is a novel compound that is not disclosed in the literature. Although PLC5 was synthesized using PLC4 and PLC5-1, its details are described in the following "<Synthesis of Compound PLC5>". In addition, PLC5-1 was synthesized by the synthesis method described in the literature (Liquid Crystals (2005), 32(8), 1031-1044.).
PLC6使用可市售購入的M6BC(綠化學股份公司製)。 PLC6 uses commercially available M6BC (manufactured by Green Chemical Co., Ltd.).
在500mL四口燒瓶,加入化合物PLC4(20.00g、65.3mmol)、化合物PLC5-1(14.09g、71.8mmol)、EDC(15.02g、78.4mmol)、DMAP(0.80g、6.53mmol)、THF(200g),在23℃進行反應。以HPLC進行反應追踪,確認反應完畢後,將反應溶液注入至蒸餾水(1.2L),加入乙酸乙基酯(2L),以分液操作除去水層。將有機層以蒸餾水(500mL)進行3次洗淨後,使有機層以硫酸鎂乾燥。之後,過濾、以蒸發器進行溶劑餾去,得到油狀化合物之化合物PLC5-2。接著,於得到的化合物PLC5-2中加入吡啶鎓p-甲苯磺酸(記為PPTS)(1.59g、6.3mmol)、乙醇(100g),在60℃進行加熱攪拌。以HPLC進行反應追踪,確認反應完畢後,將反應溶液在冰浴冷卻,使析出的固體過濾,以乙醇洗淨。藉由使 得到的固體減壓乾燥,得到化合物19.2g之PLC5(收率69%)。 In a 500mL four-necked flask, add compound PLC4 (20.00g, 65.3mmol), compound PLC5-1 (14.09g, 71.8mmol), EDC (15.02g, 78.4mmol), DMAP (0.80g, 6.53mmol), THF (200g ), the reaction was carried out at 23°C. Reaction tracking was performed by HPLC, and after confirming that the reaction was completed, the reaction solution was poured into distilled water (1.2 L), ethyl acetate (2 L) was added, and the water layer was removed by a liquid separation operation. After the organic layer was washed with distilled water (500 mL) three times, the organic layer was dried with magnesium sulfate. After that, it was filtered and the solvent was distilled off with an evaporator to obtain compound PLC5-2 as an oily compound. Next, pyridinium p-toluenesulfonic acid (referred to as PPTS) (1.59 g, 6.3 mmol) and ethanol (100 g) were added to the obtained compound PLC5-2, and the mixture was heated and stirred at 60°C. The reaction was followed by HPLC, and after confirming that the reaction was completed, the reaction solution was cooled in an ice bath, and the precipitated solid was filtered and washed with ethanol. By making The obtained solid was dried under reduced pressure to obtain PLC5 of 19.2 g of compound (yield 69%).
1H-NMR(400MHz,CDCl3,δppm):8.22-8.18(2H,m),8.17-8.14(2H,m),7.36-7.32(2H,m),7.00-6.96(2H,m),6.12-6.11(1H,m),5.57-5.55(1H,m),4.20-4.16(2H,m),4.06(2H,t),1.96-1.95(3H,m),1.90-1.46(8H,m). 1 H-NMR (400MHz, CDCl3, δppm): 8.22-8.18 (2H, m), 8.17-8.14 (2H, m), 7.36-7.32 (2H, m), 7.00-6.96 (2H, m), 6.12 6.11 (1H, m), 5.57-5.55 (1H, m), 4.20-4.16 (2H, m), 4.06 (2H, t), 1.96-1.95 (3H, m), 1.90-1.46 (8H, m).
又,樹脂的分子量測定條件如下。 In addition, the molecular weight measurement conditions of the resin are as follows.
裝置:泉州科學公司製常溫膠體滲透層析法(GPC)裝置(SSC-7200)、管柱:Shodex公司製管柱(KD-803、KD-805)、管柱溫度:50℃、溶離液:N,N’-二甲基甲醯胺(作為添加劑的溴化鋰-水合物(LiBr.H2O)為30mmol/L、磷酸.無水結晶(o-磷酸)為30mmol/L、四氫呋喃(THF)為10ml/L)、流速:1.0ml/分鐘、檢量線作成用標準樣本:東曹公司製TSK標準聚環氧乙烷(分子量約9000,000、150,000、100,000、 30,000)、及Polymer Laboratories Ltd.製聚乙二醇(分子量約12,000、4,000、1,000)。 Device: Room temperature colloidal permeation chromatography (GPC) device (SSC-7200) manufactured by Quanzhou Science Company, column: column (KD-803, KD-805) manufactured by Shodex Company, column temperature: 50°C, lysate: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr. H 2 O) is 30mmol/L, phosphoric acid. Anhydrous crystals (o-phosphoric acid) is 30mmol/L, tetrahydrofuran (THF) is 10ml/L), flow rate: 1.0ml/min, calibration line preparation standard sample: Tosoh Corporation TSK standard polyethylene oxide (molecular weight approximately 9000,000, 150,000, 100,000, 30,000), and Polymer Laboratories Ltd. Production of polyethylene glycol (molecular weight of about 12,000, 4,000, 1,000).
NMP:N-甲基-2-吡咯啶酮 NMP: N-methyl-2-pyrrolidone
BCS:丁基溶纖劑 BCS: Butyl cellosolve
AIBN:2,2’-偶氮二異丁腈 AIBN: 2,2’-Azobisisobutyronitrile
使MA1(28.6g、50.0mmol)溶於NMP(163.7g)中,以隔膜泵脫氣,進行氮取代後,加入AIBN(0.25g、1.5mmol),再脫氣並進行氮取代。之後在60℃進行24小時反應,得到甲基丙烯酸酯的聚合物溶液。使該聚合物溶液滴下至二乙基醚(5000ml),過濾得到的沈澱物。使該沈澱物以二乙基醚洗淨,在40℃的烤箱中進行減壓乾燥,得到甲基丙烯酸酯聚合物粉末P1。得到的甲基丙烯酸酯聚合物的數平均分子量為46,000、重量平均分子量為119,600。 MA1 (28.6 g, 50.0 mmol) was dissolved in NMP (163.7 g), degassed with a diaphragm pump, and after nitrogen substitution was performed, AIBN (0.25 g, 1.5 mmol) was added, followed by degassing and nitrogen substitution. Then, the reaction was carried out at 60°C for 24 hours to obtain a polymer solution of methacrylate. The polymer solution was dropped to diethyl ether (5000 ml), and the obtained precipitate was filtered. This deposit was washed with diethyl ether, and dried under reduced pressure in an oven at 40°C to obtain methacrylate polymer powder P1. The number average molecular weight of the obtained methacrylate polymer was 46,000, and the weight average molecular weight was 119,600.
在得到的甲基丙烯酸聚合物粉末(A)(6.0g)中加入NMP(114.0g),在室溫進行5小時攪拌使其溶解。於該溶液加入BCS(30.0g),並在室溫進行5小時攪拌而得到液晶配向劑B1。 NMP (114.0 g) was added to the obtained methacrylic polymer powder (A) (6.0 g), and the mixture was stirred and dissolved at room temperature for 5 hours. BCS (30.0g) was added to this solution, and it stirred at room temperature for 5 hours, and obtained the liquid crystal alignment agent B1.
相對合成例1所得的液晶配向劑B1 10.0g,添加合成例1所得的液晶性化合物PLC1 0.04g(相對固形分為10質量%),在室溫進行3小時攪拌使其溶解,調製液晶配向劑B2。 With respect to 10.0 g of the liquid crystal alignment agent B1 obtained in Synthesis Example 1, 0.04 g (relative solid content of 10% by mass) of the liquid crystal compound PLC1 obtained in Synthesis Example 1 was added, and stirred at room temperature for 3 hours to dissolve to prepare the liquid crystal alignment agent B2.
使得到的液晶配向劑B2在冷凍庫保存1日,解凍後,未確認有析出物。 The obtained liquid crystal alignment agent B2 was stored in the freezer for one day, and after thawing, no precipitate was confirmed.
相對合成例1所得的液晶配向劑B1 10.0g,添加合成例1所得的液晶性化合物PLC1 0.10g(相對固形分為25質量%),在室溫進行3小時攪拌使其溶解,調製液晶配向劑B3。 With respect to 10.0 g of the liquid crystal alignment agent B1 obtained in Synthesis Example 1, 0.10 g of the liquid crystal compound PLC1 obtained in Synthesis Example 1 (relative solid content 25% by mass) was added, and stirred at room temperature for 3 hours to dissolve to prepare a liquid crystal alignment agent B3.
使得到的液晶配向劑B3在冷凍庫保存1日,解凍後,未確認有析出物。 The obtained liquid crystal alignment agent B3 was stored in the freezer for 1 day, and after thawing, no precipitate was confirmed.
相對合成例1所得的液晶配向劑B1 10.0g,添加合成例1所得的液晶性化合物PLC2 0.10g(相對固形分為25質量%),在室溫進行3小時攪拌使其溶解,調製液晶配向劑B4。 With respect to 10.0 g of the liquid crystal alignment agent B1 obtained in Synthesis Example 1, 0.10 g of the liquid crystal compound PLC2 obtained in Synthesis Example 1 (relative solid content 25% by mass) was added, and stirred at room temperature for 3 hours to dissolve to prepare the liquid crystal alignment agent B4.
使得到的液晶配向劑B4在冷凍庫保存1日,解凍後,未確認有析出物。 The obtained liquid crystal alignment agent B4 was stored in the freezer for one day, and after thawing, no precipitate was confirmed.
相對合成例1所得的液晶配向劑D1 10.0g,添加合成例1所得的液晶性化合物PLC3 0.10g(相對固形分為25質量%),在室溫進行3小時攪拌使其溶解,調製液晶配向劑B5。 With respect to 10.0 g of the liquid crystal alignment agent D1 obtained in Synthesis Example 1, 0.10 g of the liquid crystal compound PLC3 obtained in Synthesis Example 1 (relative solid content 25% by mass) was added, and stirred at room temperature for 3 hours to dissolve to prepare a liquid crystal alignment agent B5.
使得到的液晶配向劑B5在冷凍庫保存1日,解凍後,未確認有析出物。 The obtained liquid crystal alignment agent B5 was stored in the freezer for one day, and after thawing, no precipitate was confirmed.
相對合成例1所得的液晶配向劑B1 10.0g,添加合成例1所得的液晶性化合物PLC4 0.10g(相對固形分為25質量%),在室溫進行3小時攪拌使其溶解,調製液晶配向劑B6。 With respect to 10.0 g of the liquid crystal alignment agent B1 obtained in Synthesis Example 1, 0.10 g of the liquid crystal compound PLC4 obtained in Synthesis Example 1 (relative solid content 25% by mass) was added, and stirred at room temperature for 3 hours to dissolve to prepare the liquid crystal alignment agent B6.
使得到的液晶配向劑B6在冷凍庫保存1日,解凍後,未確認有析出物。 The obtained liquid crystal alignment agent B6 was stored in the freezer for one day, and after thawing, no precipitate was confirmed.
相對合成例1所得的液晶配向劑B1 10.0g,添加合成例1所得的液晶性化合物PLC5 0.10g(相對固形分為25質量%),在室溫進行3小時攪拌使其溶解,調製液晶配向劑B7。 With respect to 10.0 g of the liquid crystal alignment agent B1 obtained in Synthesis Example 1, 0.10 g of the liquid crystal compound PLC5 obtained in Synthesis Example 1 (relative solid content 25% by mass) was added, and stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent. B7.
使得到的液晶配向劑B7在冷凍庫保存1日,解凍後,未確認有析出物。 The obtained liquid crystal alignment agent B7 was stored in the freezer for one day, and after thawing, no precipitate was confirmed.
相對合成例1所得的液晶配向劑B1 10.0g,添加合成例1所得的液晶性化合物PLC6 0.10g(相對固形分為25質量%),在室溫進行3小時攪拌使其溶解,調製液晶配向劑B8。 With respect to 10.0 g of the liquid crystal alignment agent B1 obtained in Synthesis Example 1, 0.10 g of the liquid crystal compound PLC6 obtained in Synthesis Example 1 (relative solid content 25% by mass) was added, and stirred at room temperature for 3 hours to dissolve to prepare the liquid crystal alignment agent B8.
使得到的液晶配向劑B8在冷凍庫保存1日,解凍後,未確認有析出物。 The obtained liquid crystal alignment agent B8 was stored in the freezer for 1 day, and after thawing, no precipitate was confirmed.
使用實施例1所得的液晶配向劑B3,以下述所示過程進行扭曲向列型液晶晶胞之製作。 Using the liquid crystal alignment agent B3 obtained in Example 1, the twisted nematic liquid crystal cell was produced by the following procedure.
將實施例1所得的液晶配向劑B3在形成有ITO電極圖型的ITO電極基板的ITO面進行旋轉塗佈,在70℃的加熱板進行90秒鐘乾燥後,對基板照射從水平方向傾斜40°的313nm的偏光紫外線50mJ/cm2,在200℃的加熱板進行10分鐘加熱,形成膜厚100nm的液晶配向膜。關於上述2枚基板,在一基板的液晶配向膜上散佈6μm的間隔珠後,由其上印刷密封劑(溶劑型熱硬化型的環氧樹脂)。接著以配向方向直行之方式與2枚基板貼合後,使密封劑硬化而製作空晶胞。在該空晶胞將液晶MLC-2003(C080)(默克公司製商品名)以減壓注入法注入,製作扭曲向列型液晶晶胞。製作的液晶晶胞,之後,置入120 ℃的熱風循環式烤箱1小時,進行液晶的再配向處理。 The liquid crystal alignment agent B3 obtained in Example 1 was spin-coated on the ITO surface of the ITO electrode substrate formed with the ITO electrode pattern, and dried on a heating plate at 70°C for 90 seconds, and then the substrate was irradiated with an inclined angle of 40 from the horizontal direction. ° 313nm polarized ultraviolet light 50mJ/cm 2 , heated on a heating plate at 200°C for 10 minutes to form a liquid crystal alignment film with a film thickness of 100nm. Regarding the above two substrates, spacer beads of 6 μm were spread on the liquid crystal alignment film of one substrate, and then a sealant (solvent-type thermosetting epoxy resin) was printed thereon. Then, after bonding the two substrates in a straight alignment direction, the sealant is hardened to produce an empty cell. Liquid crystal MLC-2003 (C080) (trade name of Merck & Co.) was injected into this empty cell by a reduced pressure injection method to produce a twisted nematic liquid crystal cell. The fabricated liquid crystal cell was then placed in a hot-air circulating oven at 120°C for 1 hour to perform the realignment treatment of the liquid crystal.
除上述偏光紫外線的角度為30°以外,與實施例4同樣地,製作扭曲向列型液晶晶胞。 A twisted nematic liquid crystal cell was produced in the same manner as in Example 4 except that the angle of the polarized ultraviolet light was 30°.
除偏光紫外線照射角度為45°以外,與實施例4同樣地,製作扭曲向列型液晶晶胞。 A twisted nematic liquid crystal cell was produced in the same manner as in Example 4 except that the polarized ultraviolet irradiation angle was 45°.
除取代液晶配向劑B3,使用液晶配向劑B4以外,與實施例4同樣地,製作扭曲向列型液晶晶胞。 Except that the liquid crystal alignment agent B4 was used instead of the liquid crystal alignment agent B3, the twisted nematic liquid crystal cell was produced in the same manner as in Example 4.
除取代液晶配向劑B3,使用液晶配向劑B4以外,與實施例5同樣地,製作扭曲向列型液晶晶胞。 A twisted nematic liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal alignment agent B4 was used in place of the liquid crystal alignment agent B3.
除取代液晶配向劑B3,使用液晶配向劑B4以外,與實施例6同樣地,製作扭曲向列型液晶晶胞。 A twisted nematic liquid crystal cell was produced in the same manner as in Example 6, except that the liquid crystal alignment agent B4 was used in place of the liquid crystal alignment agent B3.
除取代液晶配向劑B3,使用液晶配向劑B2以外,與 實施例6同樣地,製作扭曲向列型液晶晶胞。 In addition to replacing the liquid crystal aligning agent B3, using the liquid crystal aligning agent B2, and In the same manner as in Example 6, a twisted nematic liquid crystal cell was produced.
除取代實施例4的液晶配向劑B3,使用液晶配向劑B1以外,與實施例4同樣地,製作扭曲向列型液晶晶胞。 Except for replacing the liquid crystal alignment agent B3 of Example 4 and using the liquid crystal alignment agent B1, in the same manner as in Example 4, a twisted nematic liquid crystal cell was produced.
除取代液晶配向劑B3,使用液晶配向劑B1以外,與實施例6同樣地,製作扭曲向列型液晶晶胞。 Except for replacing the liquid crystal aligning agent B3 and using the liquid crystal aligning agent B1, in the same manner as in Example 6, a twisted nematic liquid crystal cell was produced.
除取代液晶配向劑B3,使用各自液晶配向劑B5~B8以外,與實施例6同樣地,製作扭曲向列型液晶晶胞。 Except for replacing the liquid crystal alignment agent B3 and using the respective liquid crystal alignment agents B5 to B8, in the same manner as in Example 6, a twisted nematic liquid crystal cell was produced.
扭曲向列型液晶晶胞的預傾角(°)係以Axo Metrix公司製的「Axo Scan」,使用穆勒矩陣法進行測定。 The pretilt angle (°) of the twisted nematic liquid crystal cell was measured using the "Axo Scan" manufactured by Axo Metrix Corporation, using the Muller matrix method.
結果如下述表1。 The results are shown in Table 1 below.
如表1所示般,在添加(B)成分之反應性液晶元化合物的實施例4~10,得到的液晶配向膜顯示適合扭曲向列型模式之預傾角。另一方面,在使用未添加(B)成分之反應性液晶元化合物的液晶配向劑之比較例5與6,預傾角成為50°乃至58°,無法成為適合於扭曲向列型模式之預傾角。又,在添加非液晶元化合物之化合物的例之比較例7乃至10,預傾角成為0°。 As shown in Table 1, in Examples 4 to 10 in which the reactive mesogen compound of component (B) was added, the obtained liquid crystal alignment film showed a pretilt angle suitable for twisted nematic mode. On the other hand, in Comparative Examples 5 and 6 using the liquid crystal alignment agent of the reactive mesogen compound without adding the component (B), the pretilt angle is 50° to 58°, which cannot be the pretilt angle suitable for the twisted nematic mode . In addition, in Comparative Examples 7 to 10, which are examples of adding compounds other than mesogen compounds, the pretilt angle is 0°.
如以上,在本發明實施例,對內包液晶化合物的配向膜,斜方向照射紫外線,可表現任意預傾角。可提供適用扭曲向列型模式之液晶配向膜。 As described above, in the embodiment of the present invention, the alignment film encapsulating the liquid crystal compound is irradiated with ultraviolet rays in an oblique direction to exhibit any pretilt angle. Can provide liquid crystal alignment film suitable for twisted nematic mode.
與實施例6相同地製作液晶晶胞後,從該液晶晶胞的外側照射透過365nm的帶通濾波器的UV5J/cm2。 After the liquid crystal cell was produced in the same manner as in Example 6, UV5 J/cm 2 passing through a 365 nm band pass filter was irradiated from the outside of the liquid crystal cell.
VHR的評估,係對得到的液晶晶胞,在60℃的溫度下外加5V電壓60μs鐘,在16.67ms後測定該液晶晶胞的保持電壓。 The evaluation of VHR is based on applying a 5V voltage to the obtained liquid crystal cell at a temperature of 60° C. for 60 μs, and measuring the holding voltage of the liquid crystal cell after 16.67 ms.
結果如下述表2。 The results are shown in Table 2 below.
如表2所示般,在本發明之實施例11,藉由照射365nm的紫外線,在液晶晶胞內液晶性化合物進行聚合,電壓保持率提升,故可提供長期信賴優異的液晶顯示元件。 As shown in Table 2, in Example 11 of the present invention, by irradiating ultraviolet rays of 365 nm, the liquid crystal compound is polymerized in the liquid crystal cell, and the voltage holding ratio is improved, so that a liquid crystal display device with excellent long-term reliability can be provided.
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