TWI814796B - Liquid crystal alignment agent, polymer for obtaining the liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using the liquid crystal alignment film - Google Patents
Liquid crystal alignment agent, polymer for obtaining the liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using the liquid crystal alignment film Download PDFInfo
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- TWI814796B TWI814796B TW108109950A TW108109950A TWI814796B TW I814796 B TWI814796 B TW I814796B TW 108109950 A TW108109950 A TW 108109950A TW 108109950 A TW108109950 A TW 108109950A TW I814796 B TWI814796 B TW I814796B
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- Prior art keywords
- liquid crystal
- crystal alignment
- formula
- carbon atoms
- group
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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Abstract
本發明提供一種液晶配向劑，使用了由下式(1)表示之二胺衍生物、二異氰酸酯衍生物、有特定側鏈之選自二胺或二異氰酸酯之單體獲得之聚合物。 式中，A表示選自脂肪族烴基或芳香族烴基之二價有機基，B及C各自獨立，表示單鍵、或碳數1~5之脂肪族烴基。R1 表示碳數1~4之烷基且也可以分支。R2 表示氫原子、碳數1~4之脂肪族烴基、或式(1-1)表示之有機基。Ra及Rb各自獨立，表示氫原子、或碳數1~2之脂肪族烴基。The present invention provides a liquid crystal alignment agent using a polymer obtained from a diamine derivative represented by the following formula (1), a diisocyanate derivative, and a monomer having a specific side chain selected from diamine or diisocyanate. In the formula, A represents a divalent organic group selected from an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and B and C each independently represent a single bond or an aliphatic hydrocarbon group with 1 to 5 carbon atoms. R 1 represents an alkyl group having 1 to 4 carbon atoms and may be branched. R 2 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or an organic group represented by formula (1-1). Ra and Rb each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 2 carbon atoms.
Description
本發明係關於液晶配向劑、為了獲得此液晶配向劑之聚合物、液晶配向膜、及使用了此液晶配向膜之液晶顯示元件。 The present invention relates to a liquid crystal alignment agent, a polymer for obtaining the liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element using the liquid crystal alignment film.
液晶顯示元件中，液晶配向膜的作用係使液晶沿一定的方向配向。現在，工業上利用的主要的液晶配向膜，係藉由將由聚醯胺酸(也稱為聚醯亞胺前驅物、聚醯胺酸)、聚醯亞胺溶液構成的聚醯亞胺系之液晶配向劑塗佈在基板並進行煅燒以成膜。 In liquid crystal display elements, the function of the liquid crystal alignment film is to align the liquid crystal in a certain direction. At present, the main liquid crystal alignment film used industrially is a polyimide system composed of polyamide acid (also known as polyamide precursor, polyamide acid) and polyimide solution. The liquid crystal alignment agent is coated on the substrate and calcined to form a film.
為了改善液晶顯示元件之顯示特性，已有許多技術被提案。例如：專利文獻1(日本特開平2-287324號公報)，提案為了獲得高電壓保持率(VHR)，使用有特定之重複結構之聚醯亞胺樹脂。又，專利文獻2(日本特開平10-104633號公報)，提案為了縮短直到殘像消除的時間，使用醯亞胺基以外更有氮原子之可溶性聚醯亞胺。 In order to improve the display characteristics of liquid crystal display elements, many technologies have been proposed. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2-287324) proposes the use of a polyimide resin with a specific repeating structure in order to obtain a high voltage retention rate (VHR). Furthermore, Patent Document 2 (Japanese Patent Application Laid-Open No. 10-104633) proposes the use of a soluble polyimide containing nitrogen atoms in addition to the imide group in order to shorten the time until the afterimage is eliminated.
[專利文獻1]日本特開平2-287324號公報 [Patent Document 1] Japanese Patent Application Laid-Open No. 2-287324
[專利文獻2]日本特開平10-104633號公報 [Patent Document 2] Japanese Patent Application Publication No. 10-104633
近年來，伴隨液晶顯示器(LCD面板)之多機能化、多樣化，從開發使用玻璃基板之顯示器，也逐漸積極開發使用樹脂基板(塑膠基板亦即薄膜基板)之可撓性顯示器。因而，需要能夠以於低溫煅燒獲得之液晶配向膜，此外，亦要求對於液晶配向膜所要求之可靠性(高電壓保持率等)。 In recent years, with the multifunctionality and diversification of liquid crystal displays (LCD panels), displays using glass substrates have been developed, and flexible displays using resin substrates (plastic substrates, also known as film substrates) have been actively developed. Therefore, there is a need for a liquid crystal alignment film that can be obtained by sintering at a low temperature. In addition, the reliability (high voltage retention, etc.) required for the liquid crystal alignment film is also required.
液晶配向膜中使用的材料可列舉聚醯胺酸、聚醯胺酸酯等聚醯亞胺前驅物、藉由將其利用煅燒或化學反應而脫水以獲得之聚醯亞胺等。其中，聚醯胺酸合成容易且對溶劑之溶解性優異，所以能獲得對基板之塗佈性、成膜性優異之液晶配向劑。但是聚醯胺酸因為結構方面，容易因水解等分解，所以使用其獲得之液晶配向膜，難長期確保可靠性。 Examples of materials used in the liquid crystal alignment film include polyimide precursors such as polyamide acid and polyamide ester, and polyimides obtained by dehydrating them by calcination or chemical reactions. Among them, polyamide is easy to synthesize and has excellent solubility in solvents, so it is possible to obtain a liquid crystal alignment agent that is excellent in coating properties on substrates and film-forming properties. However, due to its structure, polyamide is easily decomposed due to hydrolysis, etc., so it is difficult to ensure long-term reliability of the liquid crystal alignment film obtained by using it.
另一方面，可溶性聚醯亞胺(因聚醯胺酸之脫水反應獲得之可溶於溶劑之聚醯亞胺)，因已預醯亞胺化，無需加熱使其醯亞胺化之熱硬化步驟，故可於相對 比較低溫進行煅燒。又，化學的安定性、耐熱性優異，故使用可溶性聚醯亞胺獲得之液晶配向膜，易長期確保可靠性。但是能夠使可溶性聚醯亞胺溶解的溶劑的選項少，故能使用之溶劑有限，其結果，當使用可溶性聚醯亞胺時，容易於塗佈中、成膜中出現析出等，塗膜易出現缺陷。伴隨近年LCD面板的大型化、高精細化、使用環境之多樣化，為了解決各自的問題，需要探索能夠使各種特性更好的方法。 On the other hand, soluble polyimide (solvent-soluble polyimide obtained from the dehydration reaction of polyamide acid) has been pre-imidized and does not require heat-hardening to imidize it. steps, so it can be compared to the relative Calcination is performed at a relatively low temperature. In addition, it has excellent chemical stability and heat resistance, so the liquid crystal alignment film obtained by using soluble polyimide can easily ensure long-term reliability. However, there are few options for solvents that can dissolve soluble polyimide, so the solvents that can be used are limited. As a result, when soluble polyimide is used, precipitation, etc. tend to occur during coating and film formation, and the coating film is easy to Defects occur. In recent years, as LCD panels have become larger, more sophisticated, and used in more diversified environments, it is necessary to explore ways to improve various characteristics in order to solve the respective problems.
本發明有鑑於上述情事，課題在於提供能於低溫煅燒且印刷性(獲得之聚合物對有機溶劑之溶解性)良好的液晶配向劑。又，提供可獲得上述液晶配向劑之聚合物。又，提供液晶配向性良好(亦即可達成高預傾角)且電壓保持率高之液晶配向膜。並提供有上述液晶配向膜之液晶顯示元件。 In view of the above situation, the object of the present invention is to provide a liquid crystal alignment agent that can be calcined at low temperature and has good printability (solubility of the obtained polymer in organic solvents). Furthermore, a polymer capable of obtaining the above-mentioned liquid crystal alignment agent is provided. In addition, a liquid crystal alignment film with good liquid crystal alignment (that is, high pretilt angle can be achieved) and high voltage retention is provided. And provide liquid crystal display elements with the above-mentioned liquid crystal alignment film.
本案發明人努力研究，結果發現有特定之結構之聚合物、及使用此聚合物之液晶配向劑對於達成上述目的有效，乃完成本發明。又，上述聚合物係新穎的，為了獲得上述聚合物之單體也包括新穎化合物。 The inventor of this case worked hard and found that a polymer with a specific structure and a liquid crystal alignment agent using this polymer are effective in achieving the above purpose, and thus completed the present invention. In addition, the above-mentioned polymer is novel, and the monomer for obtaining the above-mentioned polymer also includes novel compounds.
亦即，本發明以以下1.~10.為要旨。 That is, the present invention is based on the following 1. to 10.
1.一種液晶配向劑，使用了由下式(1)表示之二胺衍生物、二異氰酸酯衍生物、及有特定側鏈之選自二胺或二異氰酸酯之單體獲得之聚合物；【化1】
式中，A表示選自脂肪族烴基或芳香族烴基中之二價有機基，B及C各自獨立而表示單鍵、或碳數1~5之脂肪族烴基；R1表示碳數1~4之烷基，也可分支；R2表示氫原子、碳數1~4之脂肪族烴基、或式(1-1)表示之有機基；Ra及Rb各自獨立而表示氫原子、或碳數1~2之脂肪族烴基。 In the formula, A represents a divalent organic group selected from an aliphatic hydrocarbon group or an aromatic hydrocarbon group; B and C each independently represent a single bond or an aliphatic hydrocarbon group with 1 to 5 carbon atoms; R 1 represents a carbon number of 1 to 4 The alkyl group may also be branched; R 2 represents a hydrogen atom, an aliphatic hydrocarbon group with 1 to 4 carbon atoms, or an organic group represented by formula (1-1); Ra and Rb each independently represent a hydrogen atom, or a carbon number of 1 ~2 aliphatic hydrocarbon group.
2.如1.之液晶配向劑，其中，該含有特定側鏈之單體以下式(2)表示；
式中，N表示胺基或異氰酸酯基，R3表示單鍵、或二價有機基，X1、X2、及X3各自獨立地表示苯環或環己烷環，p、q、r各自獨立，表示0或1之整數，R4表示氫原子、碳數1~22之烷基、或有類固醇骨架之碳數12~25之二價有機基。 In the formula, N represents an amine group or an isocyanate group, R 3 represents a single bond or a divalent organic group, X 1 , X 2 , and X 3 each independently represent a benzene ring or a cyclohexane ring, and p, q, and r each independently Independent, represents an integer of 0 or 1, R 4 represents a hydrogen atom, an alkyl group with 1 to 22 carbon atoms, or a divalent organic group with 12 to 25 carbon atoms with a steroid skeleton.
3.如2.之液晶配向劑，其中，該二胺衍生物為下式(3)表示之二胺基化合物；
式中，Ar表示伸芳基，D表示單鍵、或碳數1~5之脂肪族烴基；R1、R2、Ra及Rb和上述R1、R2、Ra及Rb相同含意。 In the formula, Ar represents an aryl group, D represents a single bond or an aliphatic hydrocarbon group with 1 to 5 carbon atoms; R 1 , R 2 , Ra and Rb have the same meaning as the above-mentioned R 1 , R 2 , Ra and Rb.
4.如3.之液晶配向劑，其中，該二胺衍生物為下式(3-a)表示之二胺基化合物；
式中，D及R1和上述D及R1相同含意。 In the formula, D and R 1 have the same meaning as D and R 1 mentioned above.
5.一種聚合物，係由下式(3-1)表示之二胺基化合物、二異氰酸酯衍生物、有特定側鏈之選自二胺或二異氰酸酯之單體獲得；
式中，R1表示碳數1~4之烷基，且也可以有分支；B表示單鍵、或碳數1~5之脂肪族烴基；Ra及Rb各自獨立，表示氫原子、或碳數1~2之脂肪族烴基。 In the formula, R 1 represents an alkyl group with 1 to 4 carbon atoms, and may also be branched; B represents a single bond, or an aliphatic hydrocarbon group with 1 to 5 carbon atoms; Ra and Rb each independently represent a hydrogen atom, or a carbon number. 1~2 aliphatic hydrocarbon group.
6.如5.之聚合物，其中，該含有特定側鏈之單體以下式(2)表示；
式中，N表示胺基或異氰酸酯基，R3表示單鍵、或二價有機基，X1、X2、及X3各自獨立，表示苯環或環己烷環，p、q、r各自獨立，表示0或1之整數，R4表示氫原子、碳數1~22之烷基、或有類固醇骨架之碳數12~25之二價有機基。 In the formula, N represents an amino group or an isocyanate group, R 3 represents a single bond or a divalent organic group, X 1 , X 2 , and X 3 are each independently a benzene ring or a cyclohexane ring, and p, q, and r each represent Independent, represents an integer of 0 or 1, R 4 represents a hydrogen atom, an alkyl group with 1 to 22 carbon atoms, or a divalent organic group with 12 to 25 carbon atoms with a steroid skeleton.
7.如6.之聚合物，其中，該二異氰酸酯衍生物係下式(4-1)~式(4-13)表示之結構中之至少一者；
式中，R5及R6各自獨立，表示碳數1~10之脂肪族烴基。 In the formula, R 5 and R 6 are each independent and represent an aliphatic hydrocarbon group with 1 to 10 carbon atoms.
8.一種液晶配向劑，使用了如5.~7.中任一項之聚合物。 8. A liquid crystal alignment agent using the polymer according to any one of 5. to 7..
9.一種液晶配向膜，係由如1.~4.及8.中任一項之液晶配向劑獲得。 9. A liquid crystal alignment film obtained from the liquid crystal alignment agent according to any one of 1. to 4. and 8..
10.一種液晶顯示元件，使用了如9.之液晶配向膜。 10. A liquid crystal display element using the liquid crystal alignment film of 9.
依照本發明，能提供可於低溫煅燒且獲得高品質之液晶配向膜且印刷性優異之液晶配向劑。又，依照本發明，能提供用以獲得上述液晶配向劑之新穎聚合物。又，依照本發明，能提供可達成高預傾角，且電壓保持率高之液晶配向膜。又，依照本發明，可提供使用了上述液晶配向膜之液晶顯示元件。 According to the present invention, a liquid crystal alignment agent that can be calcined at low temperature to obtain a high-quality liquid crystal alignment film and has excellent printability can be provided. Furthermore, according to the present invention, a novel polymer for obtaining the above-mentioned liquid crystal alignment agent can be provided. Furthermore, according to the present invention, a liquid crystal alignment film that can achieve a high pretilt angle and has a high voltage retention rate can be provided. Furthermore, according to the present invention, a liquid crystal display element using the above-mentioned liquid crystal alignment film can be provided.
本發明之一態樣之液晶配向劑含有本發明之一態樣之聚合物，該聚合物係由式(1)表示之二胺衍生物(以下有時稱為「二胺」)、二異氰酸酯衍生物(以下有時稱為「二異氰酸酯」)、及有特定側鏈之選自二胺或二異氰酸酯之單體(以下有時稱為「含側鏈之單體」)獲得。 The liquid crystal alignment agent according to one aspect of the present invention contains the polymer according to one aspect of the present invention. The polymer is a diamine derivative represented by formula (1) (hereinafter sometimes referred to as "diamine"), diisocyanate Derivatives (hereinafter sometimes referred to as "diisocyanates"), and monomers having specific side chains selected from diamines or diisocyanates (hereinafter sometimes referred to as "side chain-containing monomers") are obtained.
<本發明使用之二胺> <Diamine used in the present invention>
本發明使用之二胺以式(1)表示。 The diamine used in the present invention is represented by formula (1).
【化8】
式中，A表示脂肪族烴基或芳香族烴基之二價有機基，B及C各自獨立，表示單鍵、或碳數1~5之脂肪族烴基。R1表示碳數1~4之烷基且也可分支。R2表示氫原子、碳數1~4之脂肪族烴基、或式(1-1)表示之有機基。Ra及Rb各自獨立，表示氫原子、或碳數1~2之脂肪族烴基。 In the formula, A represents a divalent organic group of an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and B and C each independently represent a single bond or an aliphatic hydrocarbon group with 1 to 5 carbon atoms. R 1 represents an alkyl group having 1 to 4 carbon atoms and may be branched. R 2 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or an organic group represented by formula (1-1). Ra and Rb each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 2 carbon atoms.
考量可獲得單體之聚合反應性、耐熱性、液晶配向性優異之液晶配向膜等觀點，式(1)中，A為芳香族烴基、B為碳數1~3之脂肪族烴基、C為單鍵較佳。式(1)具體而言可列舉下列結構。 Considering the viewpoints of obtaining a liquid crystal alignment film with excellent monomer polymerization reactivity, heat resistance, and liquid crystal alignment, in formula (1), A is an aromatic hydrocarbon group, B is an aliphatic hydrocarbon group with 1 to 3 carbon atoms, and C is Single key is better. Specific examples of formula (1) include the following structures.
式中，Ar表示伸芳基，D表示單鍵、或碳數1~5之脂肪族烴基。R1、R2、Ra及Rb和上述R1、R2、Ra及Rb相同含意。 In the formula, Ar represents an aryl group, and D represents a single bond or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. R 1 , R 2 , Ra and Rb have the same meaning as the above-mentioned R 1 , R 2 , Ra and Rb.
考量容易取得合成二胺之試藥、和二異氰酸酯之反應性良好、獲得之上述聚合物之物性良好等觀點時，式(3)中，Ar宜為伸芳基較理想，R2宜為氫原子較佳。因此式(3)較佳為以下式(3-a)’表示之結構。其中，式(3)中，Ra及Rb各為氫原子較佳。因此式(3)尤佳以式(3-a)表示。 When considering the easy availability of reagents for synthesizing diamines, good reactivity with diisocyanates, and good physical properties of the above-mentioned polymer obtained, in formula (3), Ar is preferably an aryl group, and R 2 is preferably hydrogen. Atoms are better. Therefore, formula (3) is preferably a structure represented by the following formula (3-a)'. Among them, in the formula (3), it is preferred that Ra and Rb each be a hydrogen atom. Therefore, formula (3) is preferably represented by formula (3-a).
式中，D及R1和上述D及R1相同含意。 In the formula, D and R 1 have the same meaning as D and R 1 mentioned above.
考量能理想地獲得目的單體之上述特性皆容易變得良好等觀點，上式(3-a)’較佳以下式(3-1)表示。 From the viewpoint that the above-mentioned characteristics of the target monomer can be ideally obtained and are easily improved, the above formula (3-a)' is preferably represented by the following formula (3-1).
式中，B、R1、Ra及Rb和上述B、R1、Ra及Rb相同含意。式(3-1)中，B為碳數1及2，Ra及Rb各為氫原子的話，式(3-1)以式(3-1a)及式(3-1b)表示。 In the formula, B, R 1 , Ra and Rb have the same meanings as the above-mentioned B, R 1 , Ra and Rb. In formula (3-1), if B represents carbon number 1 and 2, and Ra and Rb each represent a hydrogen atom, formula (3-1) is represented by formula (3-1a) and formula (3-1b).
式中，R1和上述R1相同含意。 In the formula, R 1 has the same meaning as R 1 mentioned above.
惟式(1)表示之二胺之具體例不限於式(3)表示之二胺。若為無損本發明之效果(例如：可達成高預傾角)之範圍，則合成上述聚合物時也可以將式(1)或式(3)表示之二胺之一部分置換成後述式(5)表示之二胺。 However, specific examples of the diamine represented by formula (1) are not limited to the diamine represented by formula (3). As long as the effect of the present invention is not impaired (for example, a high pretilt angle can be achieved), part of the diamine represented by formula (1) or formula (3) can be replaced with the following formula (5) when synthesizing the above polymer. Represents diamine.
<本發明使用之二異氰酸酯> <Diisocyanate used in the present invention>
本發明使用之二異氰酸酯以下式(4)表示。 The diisocyanate used in the present invention is represented by the following formula (4).
【化13】OCN-X-NCO (4) 【Chemical 13】OCN-X-NCO (4)
式中，X表示二價有機基。式(4)較佳為以式(4-1)~式(4-13)表示。 In the formula, X represents a divalent organic group. Formula (4) is preferably represented by formula (4-1) to formula (4-13).
式中，R5及R6各自獨立，表示碳數1~10之脂肪族烴基。 In the formula, R 5 and R 6 are each independent and represent an aliphatic hydrocarbon group with 1 to 10 carbon atoms.
使用式(4-1)~式(4-5)表示之脂肪族二異氰酸酯時，相較於使用式(4-6)~式(4-13)表示之芳香族二異氰酸酯時，獲得之聚合物會良好地溶解於溶劑。另一方面，上述芳香族二異氰酸酯相較於上述脂肪族二異氰酸酯，會和二胺較良好地反應。例如：如式(4-6)、式(4-7)所示之芳香族二異氰酸酯，會和二胺良好地反應，使獲得之液晶配向膜之耐熱性更好。 When using aliphatic diisocyanate represented by formula (4-1) ~ formula (4-5), compared with using aromatic diisocyanate represented by formula (4-6) ~ formula (4-13), the polymerization obtained The substance will dissolve well in the solvent. On the other hand, the above-mentioned aromatic diisocyanate reacts with diamine more favorably than the above-mentioned aliphatic diisocyanate. For example, aromatic diisocyanates such as formulas (4-6) and (4-7) will react well with diamines, making the liquid crystal alignment film obtained better in heat resistance.
考量為了獲得上述聚合物之泛用性高的化合物、獲得之上述聚合物之特性良好等觀點，式(4)宜為式(4-1)、式(4-7)、式(4-8)、式(4-9)、或式(4-10)較佳。又，考量獲得之液晶配向膜之電特性良好之觀點，式(4)宜為式(4-12)較理想，又，考量獲得之液晶配向膜之液晶配向性良好之觀點，式(4-13)較佳。 From the viewpoint of obtaining a compound with high versatility of the above-mentioned polymer and obtaining the above-mentioned polymer with good characteristics, the formula (4) is preferably formula (4-1), formula (4-7), or formula (4-8). ), formula (4-9), or formula (4-10) are preferred. Furthermore, considering the fact that the obtained liquid crystal alignment film has good electrical properties, formula (4) is preferably formula (4-12). Also, considering the point that the obtained liquid crystal alignment film has good liquid crystal alignment properties, formula (4- 13) Better.
惟若為本發明之主旨之範圍內則式(4)不限於上述。能因應獲得之聚合物、液晶配向劑、及液晶配向膜等之目標特性，理想地使用取得容易的二異氰酸酯。二異氰酸酯也可併用2種以上。 However, the formula (4) is not limited to the above as long as it is within the scope of the gist of the present invention. Diisocyanate, which is easy to obtain, can be ideally used according to the target properties of the obtained polymer, liquid crystal alignment agent, and liquid crystal alignment film. Two or more types of diisocyanates may be used in combination.
<本發明使用之含側鏈之單體> <Monomer containing side chains used in the present invention>
本發明使用之含側鏈之單體以式(2)表示。 The side chain-containing monomer used in the present invention is represented by formula (2).
式中，N表示胺基或異氰酸酯基，R3表示單鍵、或二價有機基，X1、X2、及X3各自獨立，表示苯環或環己烷環，p、q、r各自獨立，表示0或1之整數，R4表示氫原子、或碳數1~22之烷基或選自有類固醇骨架之碳數12~25之二價有機基。 In the formula, N represents an amino group or an isocyanate group, R 3 represents a single bond or a divalent organic group, X 1 , X 2 , and X 3 are each independently a benzene ring or a cyclohexane ring, and p, q, and r each represent Independently, it represents an integer of 0 or 1, and R 4 represents a hydrogen atom, or an alkyl group with 1 to 22 carbon atoms, or a divalent organic group with 12 to 25 carbon atoms selected from a steroid skeleton.
式(2)表示之含側鏈之單體，貢獻於增大液晶之預傾角。含側鏈之單體為二胺時，該二胺宜有長鏈烷基、全氟烷基、芳香族環狀基、脂肪族環狀基、及它們組合成的取代基、類固醇骨架基等較佳。預傾角的理想大小取決於液晶顯示器之顯示模式而有各種不同，可藉由選擇上述含側鏈之單體之結構、導入量而獲得目的之預傾角。 The side chain-containing monomer represented by formula (2) contributes to increasing the pretilt angle of the liquid crystal. When the side-chain-containing monomer is a diamine, the diamine should have long-chain alkyl groups, perfluoroalkyl groups, aromatic cyclic groups, aliphatic cyclic groups, substituents composed of them, steroid skeleton groups, etc. Better. The ideal size of the pretilt angle varies depending on the display mode of the liquid crystal display. The desired pretilt angle can be obtained by selecting the structure and introduction amount of the above-mentioned side chain-containing monomers.
於要求比起後述VA模式更低之3°~5°之預傾角之TN模式、要求8°~20°之預傾之OCB模式等，宜使用增大預傾角之作用(傾斜展現能力)較小的含側鏈之單體較佳。傾斜展現能力比較小的含側鏈之單體，例如：式(2)中，R3為-O-、或-NHCO-(或-CONH-)較理想，p為0~1、q為0~1、r為0較理想，p及/或q為1時，R4為碳數1~12之直鏈烷基較理想，p=q=r=0時，R4為碳數10~22之直鏈烷基、或有類固醇骨架之碳數12~25之有機基即二價有機基較佳。傾斜展現能力小的含側鏈之單體之具體結構示於表1，但式(2)不限於表1之結構。又，表1之[2-16]~[2-30]中，R3之「-NHCO-」也可書寫替換為「-CONH-」。 In the TN mode, which requires a lower pretilt angle of 3° to 5° than the VA mode described later, and the OCB mode, which requires a pretilt angle of 8° to 20°, it is better to use the effect of increasing the pretilt angle (tilt display capability). Small monomers containing side chains are preferred. Monomers containing side chains with relatively small tilt display ability, for example: in formula (2), R 3 is -O-, or -NHCO- (or -CONH-) ideally, p is 0~1, q is 0 ~1. It is ideal for r to be 0. When p and/or q is 1, it is ideal for R 4 to be a straight chain alkyl group with 1 to 12 carbon atoms. When p=q=r=0, R 4 is for carbon number 10~ A straight-chain alkyl group of 22, or an organic group with a carbon number of 12 to 25 having a steroid skeleton, that is, a divalent organic group, is preferred. The specific structure of the side chain-containing monomer with small tilt display ability is shown in Table 1, but the formula (2) is not limited to the structure in Table 1. In addition, in [2-16]~[2-30] of Table 1, "-NHCO-" in R 3 can also be written and replaced with "-CONH-".
【表1】
考量獲得之液晶配向膜之電特性良好的觀點，宜為如表1之[2-1]~[2-3]之有長鏈烷基側鏈之含側鏈之單體較佳。又，考量使獲得之液晶配向膜之液晶配向性及預傾安定性更好的觀點，表1之[2-25]~[2-27]表示之含側鏈之單體較佳。 Considering that the obtained liquid crystal alignment film has good electrical properties, side chain-containing monomers having long-chain alkyl side chains such as [2-1] to [2-3] in Table 1 are preferred. In addition, from the viewpoint of improving the liquid crystal alignment and pretilt stability of the obtained liquid crystal alignment film, side chain-containing monomers shown in [2-25] to [2-27] in Table 1 are preferred.
另一方面，藉由使用傾斜展現能力大之含側鏈之單體，液晶容易垂直地配向。因此VA模式之式(2)之結構，例如：R3為-O-、-COO-、或-CH2O-較理想，p為0~1、q為0~1、r為0~1較理想，R4為碳數2~22較佳。p=q=r=0時，R4為碳數18~22之直鏈烷基、或有類固醇骨架之碳數12~25之有機基即二價有機基較佳。傾斜展現能力大之含側鏈之單體之具體結構示於表2-1及表2-2，但式(2)不限於表 2-1及表2-2之結構。 On the other hand, by using side chain-containing monomers with large tilt display capabilities, liquid crystals can be easily aligned vertically. Therefore, the structure of the VA mode formula (2), for example: R 3 is -O-, -COO-, or -CH 2 O- is ideal, p is 0~1, q is 0~1, r is 0~1 Preferably, R 4 has a carbon number of 2 to 22. When p=q=r=0, R4 is preferably a linear alkyl group with 18 to 22 carbon atoms, or an organic group with 12 to 25 carbon atoms with a steroid skeleton, that is, a divalent organic group. The specific structures of side chain-containing monomers with large tilt display capabilities are shown in Table 2-1 and Table 2-2, but formula (2) is not limited to the structures in Table 2-1 and Table 2-2.
【表2-2】
表2-1及表2-2之含側鏈之單體，傾斜展現能力大，故適合使用VA模式的情形。尤其[2-43]、[2-92]等，傾斜展現能力大，即使是比較少的側鏈量也容易使液晶垂直地配向。尤其[2-52]、[2-101]，傾斜展現能力極大，即使是非常少側鏈量，也能使液晶垂直地配向。因此該等含側鏈之單體就使液晶配向劑之印刷性更好的觀點較理想。 The side chain-containing monomers in Table 2-1 and Table 2-2 have great tilt display capabilities, so they are suitable for use in VA mode. In particular, [2-43], [2-92], etc. have a large tilt display ability and can easily align liquid crystals vertically even with a relatively small amount of side chains. In particular, [2-52] and [2-101] have great tilt display capabilities, and can align liquid crystals vertically even with a very small amount of side chains. Therefore, it is ideal to think that these side chain-containing monomers can make the liquid crystal alignment agent have better printability.
另一方面，式(2)表示之含側鏈之單體，係選自二胺或二異氰酸酯。惟二異氰酸酯係使高毒性的光氣等作用於二胺而衍生得到。故考量含側鏈之單體之取得容易的觀點，使用二胺作為含側鏈之單體較簡便。因而式(2)之N宜為胺基較佳。 On the other hand, the side chain-containing monomer represented by formula (2) is selected from diamine or diisocyanate. But diisocyanate is derived by reacting highly toxic phosgene with diamine. Therefore, considering the ease of obtaining the side chain-containing monomer, it is simpler to use diamine as the side chain-containing monomer. Therefore, N in formula (2) is preferably an amine group.
在表1、表2-1及表2-2中重複的單體，有時在TN模式、OCB模式等中使用的情形，及在VA模式等使用之情形都可使用。獲得上述聚合物時，含側鏈之單體之含量在本發明之主旨之範圍內係為任意。例如：相對於式(1)表示之二胺及含側鏈之單體之合計莫耳數，含側鏈之單體之莫耳數可設為0.05~0.5。 Monomers repeated in Table 1, Table 2-1, and Table 2-2 can be used when used in TN mode, OCB mode, etc., or when used in VA mode, etc. When obtaining the above-mentioned polymer, the content of the side chain-containing monomer is arbitrary within the scope of the gist of the present invention. For example: relative to the total molar number of the diamine and the side chain-containing monomer represented by formula (1), the molar number of the side chain-containing monomer can be set to 0.05~0.5.
<二胺> <Diamine>
當獲得上述聚合物時，也可將式(1)表示之二胺的一部分置換成其他二胺(其他二胺，亦即，不該當式(1)表示之二胺且也不該當含側鏈之單體之二胺)。一般而言，二胺的種類豐富，且帶有具各種功能之有機基的化合物也多，所以藉由併用其他二胺，有時能對於上述聚合物賦予更進一步的效果、或使上述二胺之上述效果更為改善。其他二胺之莫耳數相對於式(1)表示之二胺之莫耳數之比，在無損本發明效果(例如能達到高預傾角)之範圍內係為任意。當然，也可不併用其他二胺。如此的其他二胺，例如：下式(5)表示之二胺。 When the above polymer is obtained, a part of the diamine represented by formula (1) may also be replaced with other diamines (other diamines, that is, the diamine represented by formula (1) should not be used and should not contain side chains. monomer diamine). Generally speaking, there are many kinds of diamines, and there are many compounds with organic groups having various functions. Therefore, by using other diamines in combination, it is sometimes possible to provide further effects to the above-mentioned polymers, or to make the above-mentioned diamines The above effect is even better. The ratio of the molar number of other diamines to the molar number of the diamine represented by formula (1) is arbitrary as long as the effect of the present invention is not impaired (for example, a high pretilt angle can be achieved). Of course, other diamines may not be used together. Such other diamines include, for example, the diamine represented by the following formula (5).
式中，Y代表二價有機基。Y之具體的結構，例如可列舉下式(Y-1)~式(Y-147)但不限定於此等。式(Y-1)~式(Y-147)中，黑點代表向氮原子之鍵結部位。R7各自獨立，代表氫原子、甲基、或乙基。在四羧酸二酐與二胺之反應中得到聚醯胺酸，在二異氰酸酯與二胺之反應中得到聚脲。 In the formula, Y represents a divalent organic radical. Specific structures of Y include, for example, the following formulas (Y-1) to formula (Y-147), but are not limited thereto. In Formula (Y-1)~Formula (Y-147), the black dots represent the bonding sites to nitrogen atoms. R 7 each independently represents a hydrogen atom, methyl group, or ethyl group. Polyamic acid is obtained by the reaction of tetracarboxylic dianhydride and diamine, and polyurea is obtained by the reaction of diisocyanate and diamine.
【化18】
【化19】
式(Y-108)~式(Y-112)中，A1表示碳數2~24之烷基或含氟烷基。 In formula (Y-108) to formula (Y-112), A 1 represents an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group.
【化21】
式(Y-113)~式(Y-114)中，A2表示-O-、-OCH2-、-CH2O-、-COOCH2-、或-CH2OCO-，A3表示碳數1~22之烷基、烷氧基、含氟烷基或含氟烷氧基。 In formula (Y-113) ~ formula (Y-114), A 2 represents -O-, -OCH 2 -, -CH 2 O-, -COOCH 2 -, or -CH 2 OCO-, and A 3 represents the carbon number 1 to 22 alkyl groups, alkoxy groups, fluorine-containing alkyl groups or fluorine-containing alkoxy groups.
式(Y-115)~式(Y-117)中，A4表示-COO-、-OCO-、-CONH-、-NHCO-、-COOCH2-、-CH2OCO-、-CH2O-、-OCH2-、或-CH2-，A5表示碳數1~22之烷基、烷氧基、含氟烷基或含氟烷氧基。 In formula (Y-115) ~ formula (Y-117), A 4 represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH 2 -, -CH 2 OCO-, -CH 2 O- , -OCH 2 -, or -CH 2 -, A 5 represents an alkyl group, alkoxy group, fluorine-containing alkyl group or fluorine-containing alkoxy group having 1 to 22 carbon atoms.
式(Y-118)~式(Y-119)中，A6表示-COO-、-OCO-、-CONH-、-NHCO-、-COOCH2-、-CH2OCO-、-CH2O-、-OCH2-、-CH2-、-O-、或-NH-，A7表示氟基、氰基、三氟甲烷基、硝基、偶氮基、甲醯基、乙醯基、乙醯氧基、或羥基。 In formula (Y-118) ~ formula (Y-119), A 6 represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH 2 -, -CH 2 OCO-, -CH 2 O- , -OCH 2 -, -CH 2 -, -O-, or -NH-, A 7 represents fluorine group, cyano group, trifluoromethanyl group, nitro group, azo group, formyl group, acetyl group, ethyl group Cyloxy group, or hydroxyl group.
【化24】
式(Y-120)~式(Y-121)中，A8表示碳數3~12之烷基，1,4-伸環己基之順式-反式異構，各為反式異構物。 In formula (Y-120) ~ formula (Y-121), A 8 represents an alkyl group with 3 to 12 carbon atoms, and the cis-trans isomer of 1,4-cyclohexylene group, each is a trans isomer. .
式(Y-122)~式(Y-123)中，A9表示碳數3~12之烷基，1,4-伸環己基之順式-反式異構，各為反式異構物。 In formula (Y-122) ~ formula (Y-123), A 9 represents an alkyl group with 3 to 12 carbon atoms, and the cis-trans isomer of 1,4-cyclohexylene group, each is a trans isomer. .
【化26】
式(Y-132)~式(Y-137)中，A12表示-COO-、-OCO-、-CONH-、-NHCO-、-CH2-、-O-、-CO-、或-NH-，A13表示碳數1~22之烷基或含氟烷基。 In formula (Y-132) ~ formula (Y-137), A 12 represents -COO-, -OCO-, -CONH-, -NHCO-, -CH 2 -, -O-, -CO-, or -NH -, A 13 represents an alkyl group with 1 to 22 carbon atoms or a fluorine-containing alkyl group.
【化27】
式(Y-140)、式(Y-144)及式(Y-145)中，n表示1~10之整數。 In formula (Y-140), formula (Y-144) and formula (Y-145), n represents an integer from 1 to 10.
<聚合物> <Polymer>
上述聚合物(聚脲及聚脲共聚物)，以式(6)表示。 The above-mentioned polymer (polyurea and polyurea copolymer) is represented by formula (6).
式中，X表示來自二異氰酸酯之二價有機基，Y表示來自二胺之二價有機基。R1表示碳數1~4之烷基且也可分支。R2表示氫原子、碳數1~4之脂肪族烴基、 或下式(1-1)表示之有機基。Ra及Rb各自獨立，表示氫原子、或碳數1~2之脂肪族烴基。 In the formula, X represents a divalent organic group derived from diisocyanate, and Y represents a divalent organic group derived from diamine. R 1 represents an alkyl group having 1 to 4 carbon atoms and may be branched. R 2 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or an organic group represented by the following formula (1-1). Ra and Rb each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 2 carbon atoms.
式中，黑點代表向氮原子之鍵結部位，R1、Ra及Rb，和上述R1、Ra及Rb同義。 In the formula, the black dots represent the bonding sites to nitrogen atoms, and R 1 , Ra and Rb are synonymous with the above-mentioned R 1 , Ra and Rb.
聚脲，係利用脲鍵部位的極性而鍵結牢固的氫鍵，故獲得之膜的機械強度優異。另一方面，此強氫鍵力成為聚合物凝聚的要因，有時會使聚合物溶液之安定性等不佳(聚合物溶液之黏度增加、聚合物之一部分析出、聚合物溶液凝膠化等)。所以，取決於聚脲之結構，能使用的溶劑受限，例如需使用高極性且高沸點之溶劑。 Polyurea uses the polarity of the urea bond site to form strong hydrogen bonds, so the resulting film has excellent mechanical strength. On the other hand, this strong hydrogen bonding force is a factor in polymer aggregation, which may lead to poor stability of the polymer solution (increased viscosity of the polymer solution, precipitation of part of the polymer, gelation of the polymer solution, etc.) ). Therefore, depending on the structure of the polyurea, the solvents that can be used are limited. For example, solvents with high polarity and high boiling point need to be used.
上述聚合物，具式(6)表示之結構，亦即具在聚脲之N原子上經式(1-1)表示之有機基取代之結構。式(1-1)表示之有機基會妨礙氫鍵之形成，因而能抑制聚合物彼此凝聚。所以，聚合物溶液之安定性會大幅改善。因而當獲得聚脲之聚合物溶液時，能夠加廣能使用之溶劑之選擇廣度，甚至也能使在低溫之煅燒、印刷性大為改善。又，脲鍵的部位，取決於成膜時之煅燒溫度，有時會形成乙內醯脲環、分子間交聯。 The above-mentioned polymer has a structure represented by formula (6), that is, a structure in which the N atom of the polyurea is substituted by an organic group represented by formula (1-1). The organic group represented by formula (1-1) can hinder the formation of hydrogen bonds and thus inhibit the aggregation of polymers with each other. Therefore, the stability of the polymer solution will be greatly improved. Therefore, when a polyurea polymer solution is obtained, the selection of solvents that can be used can be broadened, and even low-temperature calcination and printability can be greatly improved. In addition, depending on the calcination temperature during film formation, the position of the urea bond may form a hydantoin ring or intermolecular cross-linking.
<反應溶液> <Reaction solution>
就反應溶液(為了獲得上述聚合物之反應使用之有機溶劑)而言，只要是上述聚合物會溶解之溶液即無特殊限制。其具體例可以列舉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、四甲基脲、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯、異丙醇、甲氧基甲基戊醇、二戊烯、乙基戊基酮、甲基壬基酮、甲乙酮、甲基異戊基酮、甲基異丙基酮、甲基賽珞蘇、乙基賽珞蘇、甲基賽珞蘇乙酸酯、乙基賽珞蘇乙酸酯、丁基卡比醇、乙基卡比醇、乙二醇、乙二醇單乙酸酯、乙二醇單異丙醚、乙二醇單丁醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲醚、丙二醇-第三丁醚、二丙二醇單甲醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲醚、二丙二醇單乙酸酯單甲醚、二丙二醇單甲醚、二丙二醇單***、二丙二醇單乙酸酯單***、二丙二醇單丙醚、二丙二醇單乙酸酯單丙醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲醚、3-甲基-3-甲氧基丁醇、二異丙醚、乙基異丁醚、二異丁烯、乙酸戊酯、丁酸丁酯、丁醚、二異丁基醚、甲基環己烯、丙醚、二己醚、二
又，反應溶液中之水分會妨礙聚合反應，進而成為使生成之聚合物水解之原因，故宜使用經脫水乾燥之反應溶液較佳。二異氰酸酯與二胺在反應溶液中反應時，可列舉將已分散或溶解二胺之反應溶液攪拌，並直接添加二異氰酸酯或使其分散或溶解於反應溶液後並添加之方法、反之於已分散或溶解二異氰酸酯之反應溶液中添加二胺之方法、將二異氰酸酯與二胺交替地添加到反應溶液之方法等，該等任一方法皆可使用。 In addition, the moisture in the reaction solution will hinder the polymerization reaction and cause hydrolysis of the generated polymer. Therefore, it is better to use a dehydrated and dried reaction solution. When diisocyanate and diamine react in a reaction solution, the reaction solution in which the diamine has been dispersed or dissolved can be stirred and the diisocyanate is directly added, or the diisocyanate is dispersed or dissolved in the reaction solution and then added, and vice versa. Either a method of adding diamine to a reaction solution in which diisocyanate is dissolved, a method of alternately adding diisocyanate and diamine to the reaction solution, etc., any of these methods can be used.
又，二異氰酸酯或二胺由多數種化合物構成時，能以已預先混合之狀態反應，也可個別地依序使其反應，也可使個別反應之低分子量體混合反應，製成高分子量體。此時之聚合溫度可以從-20℃至150℃之任意溫度選擇，較佳為-5℃至100℃之範圍。又，反應可於任意濃度進行，濃度若過低則難獲得高分子量之聚合物，濃度若過高則反應溶液之黏性變得過高，難以均勻的攪拌。因此二異氰酸酯(式(4)表示之二異氰酸酯)與二胺(式(1)及(5)表示之二異氰酸酯)在反應溶液中之合計濃度，較佳為1質量%至50質量%，更佳為5質量%至30質量%。反應初期於高濃度進行，之後追加反應溶液亦可。 In addition, when diisocyanate or diamine is composed of a plurality of compounds, they can be reacted in a state of being mixed in advance, or they can be reacted individually and sequentially, or low molecular weight compounds that have been individually reacted can be mixed and reacted to form a high molecular weight compound. . The polymerization temperature at this time can be selected from any temperature between -20°C and 150°C, preferably within the range of -5°C to 100°C. In addition, the reaction can be carried out at any concentration. If the concentration is too low, it will be difficult to obtain a high molecular weight polymer. If the concentration is too high, the viscosity of the reaction solution will become too high, making it difficult to stir uniformly. Therefore, the total concentration of diisocyanate (diisocyanate represented by formula (4)) and diamine (diisocyanate represented by formula (1) and (5)) in the reaction solution is preferably 1 to 50 mass%, more preferably Preferably, it is 5% by mass to 30% by mass. The reaction may be carried out at a high concentration in the initial stage, and the reaction solution may be added later.
聚脲之聚合反應中，二異氰酸酯(式(4)表示之二異氰酸酯)之合計莫耳數與二胺(式(1)及式(5)表示之二胺)之合計莫耳數之比宜為0.8至1.2較佳。和通常的縮聚反應同樣，此莫耳比越接近1.0則生成之聚合物之分子量越大。 In the polymerization reaction of polyurea, the ratio of the total molar number of diisocyanate (diisocyanate represented by formula (4)) to the total molar number of diamine (diamine represented by formula (1) and formula (5)) is suitable It is better to be 0.8 to 1.2. As with normal polycondensation reactions, the closer the molar ratio is to 1.0, the greater the molecular weight of the polymer produced.
[聚合物之回收] [Polymer recycling]
為了從反應溶液回收生成之上述聚合物，將反應溶液投入到不良溶劑並使上述聚合物沉澱即可。不良溶劑可列舉甲醇、丙酮、己烷、丁基賽珞蘇、庚烷、甲乙酮、甲基異丁基酮、乙醇、甲苯、苯、水等。投入到不良溶劑並沉澱之上述聚合物，進行過濾並回收後，可於常壓或減壓下於常溫或加熱使其乾燥。又，若使回收之上述聚合物再溶於有機溶劑，進行再沉澱及再回收之操作，重複2次至10次，則能夠減少上述聚合物中之雜質。此時之不良溶劑例如：醇類、酮類、烴等，若使用從該等之中選擇的3種以上之不良溶劑，則精製之效率可更提高，故較理想。 In order to recover the above-mentioned polymer produced from the reaction solution, the reaction solution is put into a poor solvent and the above-mentioned polymer is precipitated. Examples of poor solvents include methanol, acetone, hexane, butylcellulose, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The above-mentioned polymer precipitated by being put into a poor solvent is filtered and recovered, and then dried under normal pressure or reduced pressure at normal temperature or by heating. Furthermore, if the recovered polymer is redissolved in an organic solvent, and the operations of reprecipitation and recovery are repeated from 2 to 10 times, the impurities in the polymer can be reduced. Examples of poor solvents at this time include alcohols, ketones, hydrocarbons, etc. If three or more types of poor solvents selected from these are used, the efficiency of purification can be further improved, which is preferable.
上述聚合物之分子量，當考量從上述聚合物獲得之塗膜之強度、及形成塗膜時之作業容易性、塗膜膜厚之均勻性等時，按GPC(Gel Permeation Chromatography)法測定之重量平均分子量，宜為5,000至1,000,000較理想，更佳為10,000至150,000。 The molecular weight of the above-mentioned polymer is measured according to the GPC (Gel Permeation Chromatography) method when considering the strength of the coating film obtained from the above-mentioned polymer, the ease of operation when forming the coating film, the uniformity of the coating film thickness, etc. The average molecular weight is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.
<液晶配向劑> <Liquid crystal alignment agent>
本發明之一態樣之液晶配向劑，係為了形成液晶配向膜之塗佈液，為了形成塗膜(樹脂被膜)之樹脂成分溶於有機溶劑。樹脂成分含有至少一種之上述聚合物。液晶配向劑中之樹脂成分之含量為2質量%至20質量%較理想，更佳為3質量%至15質量%，尤佳為3質量%至10質量%。本發明中，樹脂成分中含有的聚合物可皆為上述聚合物(聚脲及聚脲共聚物)，若為本發明之大意之範圍內，也可以含有除此以外之聚合物(其他聚合物)。樹脂成分中，其他聚合物之含量為0.5質量% 至15質量%，較佳為1質量%至10質量%。該其他聚合物例如：丙烯酸系聚合物、甲基丙烯酸系聚合物、酚醛清漆樹脂、聚羥基苯乙烯、聚醯亞胺前驅物、聚醯亞胺、聚醯胺、聚酯、纖維素、聚矽氧烷等。 The liquid crystal alignment agent according to one aspect of the present invention is a coating liquid for forming a liquid crystal alignment film, and a resin component for forming a coating film (resin film) is dissolved in an organic solvent. The resin component contains at least one of the above-mentioned polymers. The content of the resin component in the liquid crystal alignment agent is preferably 2 mass% to 20 mass%, more preferably 3 mass% to 15 mass%, and particularly preferably 3 mass% to 10 mass%. In the present invention, the polymers contained in the resin component may all be the above-mentioned polymers (polyurea and polyurea copolymer). If it is within the scope of the present invention, other polymers (other polymers) may also be included. ). In the resin component, the content of other polymers is 0.5 mass% to 15 mass%, preferably 1 to 10 mass%. Examples of the other polymers include: acrylic polymers, methacrylic polymers, novolac resins, polyhydroxystyrene, polyimide precursors, polyimide, polyamide, polyester, cellulose, polyamide Siloxane etc.
上述液晶配向劑使用之有機溶劑，若為使樹脂成分溶解之有機溶劑則無特殊限制。其具體例可列舉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-甲基己內醯胺、2-吡咯烷酮、N-乙基吡咯烷酮、N-乙烯基吡咯烷酮、二甲基亞碸、四甲基脲、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、1,3-二甲基-咪唑啶酮、乙基戊基酮、甲基壬基酮、甲乙酮、甲基異戊基酮、甲基異丙基酮、環己酮、碳酸伸乙酯、碳酸伸丙酯、二甘二甲醚、4-羥基-4-甲基-2-戊酮等。它們可單獨使用也可混用2種以上。 The organic solvent used in the above-mentioned liquid crystal alignment agent is not particularly limited as long as it is an organic solvent that dissolves the resin component. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N -Ethylpyrrolidone, N-vinylpyrrolidone, dimethylsairn, tetramethylurea, pyridine, dimethylsulfuric acid, hexamethylstyrene, γ-butyrolactone, 3-methoxy-N,N -Dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl- Imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isopentyl ketone, methyl isopropyl ketone, cyclohexanone, ethyl carbonate, propyl carbonate, diglycandimethyl Ether, 4-hydroxy-4-methyl-2-pentanone, etc. These can be used individually or in mixture of 2 or more types.
上述液晶配向劑也可以含有上述以外之成分。其例為使塗佈液晶配向劑而形成之塗膜之膜厚之均勻性、表面之平滑性更好的溶劑、化合物、或使液晶配向膜與基板之密合性更好的化合物等。 The above-mentioned liquid crystal alignment agent may also contain components other than those mentioned above. Examples include solvents and compounds that improve the uniformity of film thickness and smoothness of the surface of the coating film formed by applying the liquid crystal alignment agent, or compounds that improve the adhesion between the liquid crystal alignment film and the substrate.
作為使膜厚之均勻性、表面之平滑性更好的溶劑(不良溶劑)為有低表面張力之溶劑，例如：異丙醇、甲氧基甲基戊醇、甲基賽珞蘇、乙基賽珞蘇、丁基賽珞蘇、甲基賽珞蘇乙酸酯、乙基賽珞蘇乙酸酯、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、乙二醇單異丙醚、乙二醇單丁醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲醚、丙二醇-第三丁醚、二丙二醇單甲醚、 二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲醚、二丙二醇單乙酸酯單甲醚、二丙二醇單甲醚、二丙二醇單***、二丙二醇單乙酸酯單***、二丙二醇單丙醚、二丙二醇單乙酸酯單丙醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲醚、3-甲基-3-甲氧基丁醇、二異丙醚、乙基異丁醚、二異丁烯、戊基乙酸酯、丁酸丁酯、丁醚、二異丁基酮、甲基環己烯、丙醚、二己醚、1-己醇、正己烷、正戊烷、正辛烷、二***、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸丙二醇單***、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇-1-單甲醚-2-乙酸酯、丙二醇-1-單***-2-乙酸酯、二丙二醇、2-(2-乙氧基丙氧基)丙醇、乳酸甲酯、乳酸乙酯、乳酸正丙酯、乳酸正丁酯、乳酸異戊基酯等。該等不良溶劑可使用1種也可混用多數種。使用上述不良溶劑時，宜為液晶配向劑中含有的有機溶劑全體之5質量%至80質量%較佳，更佳為20質量%至60質量%。 Solvents (poor solvents) that can improve the uniformity of film thickness and surface smoothness are solvents with low surface tension, such as: isopropyl alcohol, methoxymethylpentanol, methylcellulose, ethyl Cellosulfate, butyl cellosulfate, methylcellulose acetate, ethyl cellulose acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethyl carbitol acetate Glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tertiary butyl ether, dipropylene glycol monomethyl ether 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 mono Diethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl ether Alcohol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, 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 acetate, methyl pyruvate, acetone Ethyl acid ester, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropane Acid, 3-methoxypropylpropionate, 3-methoxybutylpropionate, 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-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isopentyl lactate, etc. These poor solvents may be used alone or in combination of multiple types. When using the above poor solvent, it is preferably 5% to 80% by mass of the total organic solvent contained in the liquid crystal alignment agent, more preferably 20% to 60% by mass.
作為使膜厚之均勻性、塗膜表面之平滑性更好的化合物可列舉氟系界面活性劑、聚矽氧系界面活性劑、非離子系界面活性劑等。更具體而言，例如：EFTOP EF301、EF303、EF352(Tohkem Products公司製)、MegafacF171、F173、R-30(大日本油墨公司製)、Fluorad FC430、FC431(住友3M公司製)、AsahiGuard AG710、surflon S-382、SC101、SC102、SC103、SC104、SC105、SC106(旭硝子公司製)等。該等界面活性劑之使用比例，相對於液晶配向劑中含有的樹脂成分100質量份，較佳為0.01質量份至2質量份，更佳為0.01質量份至1質量份。 Examples of compounds that improve the uniformity of the film thickness and the smoothness of the coating surface include fluorine-based surfactants, polysiloxane-based surfactants, and nonionic surfactants. More specifically, for example: EFTOP EF301, EF303, EF352 (manufactured by Tohkem Products Co., Ltd.), Megafac F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), AsahiGuard AG710, surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), etc. The usage 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 liquid crystal alignment agent.
作為使液晶配向膜與基板之密合性更好的化合物的具體例，可列舉如下所示之含官能性矽烷之化合物、含環氧基之化合物等。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-脲丙基三甲氧基矽烷、3-脲丙基三乙氧基矽烷、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-三乙氧基矽基丙基三乙烯三胺、N-三甲氧基矽基丙基三乙烯三胺、10-三甲氧基矽基-1,4,7-三氮雜癸烷、10-三乙氧基矽基-1,4,7-三氮雜癸烷、9-三甲氧基矽基-3,6-二氮雜壬基乙酸酯、9-三乙氧基矽基-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(氧伸乙基)-3-胺基丙基三甲氧基矽烷、N-雙(氧伸乙基)-3-胺基丙基三乙氧基矽烷、乙二醇二環氧丙醚、聚乙二醇二環氧丙醚、丙二醇二環氧丙醚、三丙二醇二環氧丙醚、聚丙二醇二環氧丙醚、新戊二醇二環氧丙醚、1,6-己烷二醇二環氧丙醚、甘油二環氧丙醚、2,2-二溴新戊二醇二環氧丙醚、1,3,5,6-四環氧丙基-2,4-己烷二醇、N,N,N’,N”-四環氧丙基間二甲苯二胺、1,3-雙(N,N-二環氧丙胺基甲基)環己烷、N,N,N’,N”-四環氧丙基-4、4’-二胺基二苯基甲烷等。 Specific examples of compounds that improve the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds, epoxy group-containing compounds, and the like. For example: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-Aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyl Trimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxy Silane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane alkane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonylacetate, 9-triethoxy Silyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N -Phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethyl)-3-aminopropyltrimethoxy Silane, N-bis(oxyethyl)-3-aminopropyltriethoxysilane, ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether , tripropylene glycol diepoxypropyl ether, polypropylene glycol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, glycerin diepoxypropyl ether, 2, 2-Dibromoneopentyl glycol diepoxypropyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, N,N,N',N”-tetraepoxy Propyl m-xylenediamine, 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane, N,N,N',N”-tetraepoxypropyl-4, 4' -Diaminodiphenylmethane, etc.
又，除了基板與膜之密合性改善以外，為了防止由於背光導致之光之照射成為原因的電特性下降等，也可添加如下之之酚醛塑料(phenoplast)系之添加劑。具體的酚醛塑料系添加劑如下所示，但不限於此結構。 In addition to improving the adhesion between the substrate and the film, the following phenoplast-based additives may also be added in order to prevent deterioration in electrical characteristics caused by light irradiation due to backlight. Specific phenolic plastic additives are shown below, but are not limited to this structure.
使用使基板與膜之密合性改善的化合物時，此化合物之使用量相對於液晶配向劑中含有的樹脂成分100質量份為0.1質量份至30質量份較佳，更佳為1質量份至20質量份。使用量若未達上述值，有時密合性不易改善，若超過上述值，則有時液晶配向性會變差。 When using a compound that improves the adhesion between the substrate and the film, the usage amount of the compound is preferably 0.1 to 30 parts by mass, and more preferably 1 to 30 parts by mass relative to 100 parts by mass of the resin component contained in the liquid crystal alignment agent. 20 parts by mass. If the usage amount is less than the above value, the adhesion may not be easily improved, and if the usage amount exceeds the above value, the liquid crystal alignment may be deteriorated.
上述液晶配向劑中，除了如上述溶劑、化合物以外，若為無損本發明效果之範圍，為了使液晶配向膜之介電常數、導電性等電特性改變、為了使介電體、導電物質、進而製成液晶配向膜時之膜之硬度、緻密度提高，也可以添加預定之交聯性化合物。 In the above-mentioned liquid crystal alignment agent, in addition to the above-mentioned solvents and compounds, as long as the effect of the present invention is not impaired, in order to change the electrical properties such as dielectric constant and conductivity of the liquid crystal alignment film, in order to make dielectrics, conductive substances, and further When making a liquid crystal alignment film, the hardness and density of the film can be improved, and a predetermined cross-linking compound can also be added.
<液晶配向膜、液晶顯示元件> <Liquid crystal alignment film, liquid crystal display element>
上述液晶配向劑塗佈在基板上並煅燒後，若有需要時進行配向處理，在垂直配向之用途等即使無配向處理，也能獲得本發明之一態樣之液晶配向膜。基板可以使用透明性高之玻璃基板、或塑膠基板(例如：丙烯酸基板、聚碳酸酯基板)等。又，使用已形成使液晶驅動用之ITO電極等的基板的話，從使製造液晶顯示元件之處理簡化的觀點係較理想。又，反射型之液晶顯示元件中，可於單側基板使用矽晶圓等不透明物，此時之電極亦可使用鋁等反射光的材料。塗佈液晶配向劑之方法不特別限定，工業上，一般採用旋塗印刷、網版印刷、平版印刷、柔版印刷、噴墨印刷等。其他塗佈方法有浸塗、輥塗、狹縫塗佈、旋塗等，可因應目的來使用該等方法。 After the above-mentioned liquid crystal alignment agent is coated on the substrate and calcined, alignment treatment is performed if necessary. Even without alignment treatment for vertical alignment applications, a liquid crystal alignment film of one aspect of the present invention can be obtained. The substrate can be a glass substrate with high transparency or a plastic substrate (for example, an acrylic substrate, a polycarbonate substrate), or the like. In addition, using a substrate on which ITO electrodes and the like for driving liquid crystals are formed is preferable from the viewpoint of simplifying the process of manufacturing a liquid crystal display element. In addition, in reflective liquid crystal display elements, opaque materials such as silicon wafers can be used on one side of the substrate. In this case, the electrodes can also use light-reflecting materials such as aluminum. The method of applying the liquid crystal alignment agent is not particularly limited. Industrially, spin coating printing, screen printing, offset printing, flexographic printing, inkjet printing, etc. are generally used. Other coating methods include dip coating, roller coating, slit coating, spin coating, etc. These methods can be used according to the purpose.
煅燒可利用熱板等加熱手段，在50℃至300℃，較佳為80℃至250℃進行。藉由使液晶配向劑中之有機溶劑蒸發，能夠形成塗膜。塗膜之厚度若過厚則易增加液晶顯示元件之耗電，若過薄則有時液晶顯示元件之可靠性會下降，故較佳為5nm至300nm，更佳為10nm至150nm。 Calcining can be performed using heating means such as a hot plate at 50°C to 300°C, preferably 80°C to 250°C. By evaporating the organic solvent in the liquid crystal alignment agent, a coating film can be formed. If the thickness of the coating film is too thick, it is easy to increase the power consumption of the liquid crystal display element. If it is too thin, the reliability of the liquid crystal display element may decrease. Therefore, the thickness is preferably 5 nm to 300 nm, and more preferably 10 nm to 150 nm.
依上述方法，由上述液晶配向劑獲得附液晶配向膜之基板後，藉由以公知之方法來製作液晶晶胞，可獲得本發明之一態樣之液晶顯示元件。作為製作液晶晶胞之方法之一例，可列舉準備已形成液晶配向膜之一對基板，在其中一片基板的液晶配向膜上散布間隔件，使液晶配向膜面成為內側，並貼合另一片基板，將液晶減壓注入並密封之方法。或在已散布間隔件之液晶配向膜面滴加液晶後，貼合基板並密封之方法。此時之間隔件之厚度，較佳為1μm至30μm，更 佳為2μm至10μm。使用上述液晶配向劑製作之上述液晶顯示元件，可靠性優異，故適合利用在大畫面且高精細之液晶電視等。 According to the above method, after obtaining the substrate with the liquid crystal alignment film from the above liquid crystal alignment agent, the liquid crystal display element of one aspect of the present invention can be obtained by manufacturing a liquid crystal cell by a known method. An example of a method for manufacturing a liquid crystal cell is to prepare a pair of substrates on which a liquid crystal alignment film has been formed, spread spacers on the liquid crystal alignment film of one of the substrates, so that the liquid crystal alignment film surface is inside, and laminate the other substrate , a method of injecting liquid crystal under reduced pressure and sealing it. Or the method is to drop liquid crystal on the surface of the liquid crystal alignment film where the spacer has been spread, and then attach the substrate to the substrate and seal it. At this time, the thickness of the spacer is preferably 1 μm to 30 μm, more Preferably, it is 2 μm to 10 μm. The above-mentioned liquid crystal display element produced using the above-mentioned liquid crystal alignment agent has excellent reliability and is therefore suitable for use in large-screen and high-definition LCD televisions.
<二胺之合成> <Synthesis of diamine>
實施例1 Example 1
(4-胺基苄基)甘胺酸乙酯(ethyl(4-aminobenzyl)glycinate)[NG4ABA]之合成 Synthesis of ethyl (4-aminobenzyl)glycinate [NG4ABA]
第1步驟 Step 1
於配備氮氣導入管與回流管之1L之4口燒瓶中加入甘胺酸乙基鹽酸鹽105.6g(0.694mol)、THF300g、三乙胺93.6g(0.925mol)，使用機械攪拌器於室溫攪拌1小時後，於THF會回流之溫度(設定70℃)加熱，使4-硝基苄基溴50.0g(0.231mol)溶於THF500.0g，緩慢滴加，滴加結束後，再反應24小時。於4-硝基苄基溴消失的時點作為反應結束，將析出的固體以過濾除去，並將THF以旋轉蒸發器除去，使獲得之粗製物再溶於乙酸乙酯300.0g。將此溶液以純水100g洗淨3次，加入10%鹽酸水溶液300g，攪拌1小時，回收水層側，並將此水層以乙酸乙酯100g洗淨3次。於水層中再加入乙酸乙酯300g，緩慢添加碳酸鉀，調整pH 為約10，攪拌1小時，回收有機相側，以純水100g洗淨3次。在此有機相中加入無水硫酸鎂，使其乾燥並過濾，加入活性碳，攪拌一段時間後，利用過濾去除活性碳，以旋轉蒸發器去除溶劑，獲得目的物(硝基體)淡黃色之黏體46.0g(0.193mol)。以1H-NMR確認已獲得了目的物。 Add 105.6g of glycine ethyl hydrochloride (0.694mol), 300g of THF, and 93.6g of triethylamine (0.925mol) to a 1L 4-neck flask equipped with a nitrogen inlet tube and a reflux tube, and use a mechanical stirrer to stir at room temperature. After stirring for 1 hour, heat at a temperature where THF will reflux (set at 70°C) to dissolve 50.0g (0.231mol) of 4-nitrobenzyl bromide in 500.0g of THF. Add slowly and dropwise. After the dropwise addition is completed, react for 24 seconds. hours. The reaction was deemed to have ended when 4-nitrobenzyl bromide disappeared. The precipitated solid was removed by filtration, THF was removed with a rotary evaporator, and the obtained crude product was redissolved in 300.0 g of ethyl acetate. Wash this solution three times with 100g of pure water, add 300g of 10% hydrochloric acid aqueous solution, stir for 1 hour, collect the water layer side, and wash this water layer three times with 100g of ethyl acetate. Add 300g of ethyl acetate to the water layer, slowly add potassium carbonate, adjust the pH to about 10, stir for 1 hour, recover the organic phase side, and wash 3 times with 100g of pure water. Add anhydrous magnesium sulfate to the organic phase, dry it and filter it, add activated carbon, stir for a period of time, remove the activated carbon by filtration, and remove the solvent with a rotary evaporator to obtain the target substance (nitrobody) as a light yellow viscous substance. 46.0g(0.193mol). It was confirmed by 1 H-NMR that the target product was obtained.
1H NMR(500MHz、CDCl3)：δ 8.2(2H)、7.53(2H)、4.22(2H)、3.93(2H)、3.42(2H)、1.89(1H)、1.27(3H) 1 H NMR (500MHz, CDCl 3 ): δ 8.2(2H), 7.53(2H), 4.22(2H), 3.93(2H), 3.42(2H), 1.89(1H), 1.27(3H)
第2步驟 Step 2
於配備氮氣導入管與攪拌子之500ml之4口燒瓶中加入上述獲得之硝基體45.0g(0.19mol)、THF300.0g、摻雜鐵型鉑碳4.5g，小心地將容器內取代成氫氣環境，於室溫反應24小時。於原料消失之時點作為反應結束，將鉑碳以濾膜除去，於濾液中加入活性碳(白鷺製)，於40℃攪拌30分鐘。之後再過濾，以旋轉蒸發器去除溶劑後，以高真空泵浦使其乾燥，獲得為目的物之淡黃色之黏體35.4g(0.17mol：產率89%)。以1H-NMR確認已獲得目的物(NG4ABA)。 Into a 500ml 4-neck flask equipped with a nitrogen inlet tube and a stirrer, add 45.0g (0.19mol) of the nitrobody obtained above, 300.0g of THF, and 4.5g of iron-doped platinum carbon, and carefully replace the container with a hydrogen atmosphere. , react at room temperature for 24 hours. The reaction was deemed to have ended when the raw materials disappeared, and the platinum carbon was removed with a filter. Activated carbon (manufactured by Egret) was added to the filtrate, and the mixture was stirred at 40° C. for 30 minutes. After that, it was filtered, and the solvent was removed with a rotary evaporator, and then dried with a high vacuum pump to obtain 35.4 g of a light yellow viscous substance of the target substance (0.17 mol: yield 89%). It was confirmed by 1 H-NMR that the target compound (NG4ABA) was obtained.
1H NMR(500MHz、CDCl3)：δ 6.99(2H)、6.63(2H)、4.15(2H)、3.70(2H)、3.38(2H)、3.00(2H)、1.24(3H) 1 H NMR (500MHz, CDCl 3 ): δ 6.99(2H), 6.63(2H), 4.15(2H), 3.70(2H), 3.38(2H), 3.00(2H), 1.24(3H)
實施例2 Example 2
(4-胺基苯乙基)甘胺酸乙酯(ethyl(4-aminophenethyl)glycinate)[NG4APhA]之合成 Synthesis of ethyl(4-aminophenethyl)glycinate[NG4APhA]
【化32】
第1步驟 Step 1
於配備氮氣導入管與回流管之1L之4口燒瓶中加入4-硝基苯乙基胺鹽酸鹽50g(0.246mol)、THF500g、三乙胺62.1g(0.604mol)，使用機械攪拌器於室溫攪拌1小時，於THF會回流之溫度(設定70℃)加熱，使2-氯乙酸乙酯25.1g(0.205mol)溶於THF300g，將其緩慢滴加，滴加結束後，再反應24小時。於2-氯乙酸乙酯消失(以HPLC確認)之時點作為反應結束，將析出之固體以過濾除去，將THF以旋轉蒸發器除去，使獲得之粗製物再溶於乙酸乙酯500g。將此溶液以純水100g洗淨3次，加入10%鹽酸水溶液500g，攪拌1小時，將水層側回收，並將此水層以乙酸乙酯100g洗淨3次。於水層中更加入乙酸乙酯500g，緩慢添加碳酸鉀，調整pH為約10，攪拌1小時，回收有機相側，以純水100g洗淨3次。於此有機相中加入無水硫酸鎂，使其乾燥，過濾，加入活性碳，攪拌一段時間後，利用過濾去除活性碳，以旋轉蒸發器去除溶劑，獲得為目的物之淡黃色之黏體34.2g(0.136mol：產率66%)。以1H-NMR確認已獲得目的物(硝基體)。 Add 50g (0.246mol) of 4-nitrophenylethylamine hydrochloride, 500g of THF, and 62.1g of triethylamine (0.604mol) to a 1L 4-neck flask equipped with a nitrogen inlet tube and a reflux tube, and use a mechanical stirrer to Stir at room temperature for 1 hour, heat at a temperature where THF will reflux (set at 70°C), dissolve 25.1g (0.205mol) of 2-chloroethyl acetate in 300g of THF, and slowly add it dropwise. After the dropwise addition is completed, react for 24 seconds. hours. The reaction ended when ethyl 2-chloroacetate disappeared (confirmed by HPLC). The precipitated solid was removed by filtration, THF was removed with a rotary evaporator, and the obtained crude product was redissolved in 500 g of ethyl acetate. Wash this solution three times with 100g of pure water, add 500g of 10% hydrochloric acid aqueous solution, stir for 1 hour, recover the water layer side, and wash this water layer three times with 100g of ethyl acetate. Add 500g of ethyl acetate to the water layer, slowly add potassium carbonate, adjust the pH to about 10, stir for 1 hour, recover the organic phase side, and wash 3 times with 100g of pure water. Anhydrous magnesium sulfate was added to the organic phase, dried, filtered, activated carbon was added, and after stirring for a period of time, the activated carbon was removed by filtration, and the solvent was removed with a rotary evaporator to obtain 34.2g of the target light yellow sticky substance. (0.136 mol: yield 66%). It was confirmed by 1 H-NMR that the target product (nitroform) was obtained.
1H NMR(500MHz、CDCl3)：δ 8.14(2H)、7.37(2H)、4.16(2H)、3.43(2H)、2.95(4H)、2.19(1H)、1.25(3H) 1 H NMR (500MHz, CDCl 3 ): δ 8.14(2H), 7.37(2H), 4.16(2H), 3.43(2H), 2.95(4H), 2.19(1H), 1.25(3H)
第2步驟 Step 2
於配備氮氣導入管與攪拌子之500ml之4口燒瓶中加入上述獲得之硝基體30.0g、THF300g、摻鐵型鉑碳3.0g，小心地將容器內取代成氫氣環境，於室溫反 應24小時。於原料消失之時點作為反應結束，將鉑碳以濾膜除去，於濾液中加入活性碳(白鷺製)，於40℃攪拌30分鐘。之後再過濾，以旋轉蒸發器去除溶劑後，以高真空泵浦使其乾燥，獲得為目的物(NG4APhA)之淡黃色之黏體25.1g(0.113mol：產率95%)。以1H-NMR確認已獲得目的物。 Into a 500ml 4-neck flask equipped with a nitrogen inlet tube and a stirrer, add 30.0g of the nitrobody obtained above, 300g of THF, and 3.0g of iron-doped platinum carbon, carefully replace the container with a hydrogen environment, and react at room temperature for 24 hours. . The reaction was deemed to have ended when the raw materials disappeared, and the platinum carbon was removed with a filter. Activated carbon (manufactured by Egret) was added to the filtrate, and the mixture was stirred at 40° C. for 30 minutes. Afterwards, it was filtered, and the solvent was removed with a rotary evaporator, and then dried with a high vacuum pump to obtain 25.1 g (0.113 mol: yield 95%) of a light yellow sticky substance of the target compound (NG4APhA). It was confirmed by 1 H-NMR that the target product was obtained.
1H NMR(500MHz、CDCl3)：δ 6.99(2H)、6.60(2H)、4.18(2H)、3.42(2H)、2.89(2H)、2.86(2H)、2.75(2H)、1.24(3H) 1 H NMR (500MHz, CDCl 3 ): δ 6.99(2H), 6.60(2H), 4.18(2H), 3.42(2H), 2.89(2H), 2.86(2H), 2.75(2H), 1.24(3H)
<簡稱等> <Abbreviation, etc.>
液晶配向劑之製備使用之簡稱如下。 The abbreviations for the preparation and use of liquid crystal alignment agents are as follows.
(二異氰酸酯) (diisocyanate)
IDI：異佛爾酮二異氰酸酯 IDI: Isophorone diisocyanate
DI-2MG：1,2-雙(4-異氰氧基苯氧基)乙烷 DI-2MG: 1,2-bis(4-isocyanooxyphenoxy)ethane
(二胺) (diamine)
p-PDA：對苯二胺 p-PDA: p-phenylenediamine
NG4ABA：(4-胺基苄基)甘胺酸乙酯 NG4ABA: (4-Aminobenzyl)glycinate ethyl ester
NG4APhA：(4-胺基苯乙基)甘胺酸乙酯 NG4APhA: (4-Aminophenylethyl)glycinate ethyl ester
Me4APhA：N-甲基-4-胺基苯乙基胺 Me4APhA: N-methyl-4-aminophenylethylamine
DA-3MG：1,3-二(4-胺基苯氧基)丙烷 DA-3MG: 1,3-bis(4-aminophenoxy)propane
APC16：2-十六烷氧基-1,3-二胺基苯 APC16: 2-Hexadecyloxy-1,3-diaminobenzene
PCH7：4-(4-(4-庚基環己基)苯氧基)苯-1,3-二胺 PCH7: 4-(4-(4-heptylcyclohexyl)phenoxy)benzene-1,3-diamine
(四羧酸二酐) (tetracarboxylic dianhydride)
CBDA：環丁烷四羧酸二酐 CBDA: cyclobutanetetracarboxylic dianhydride
(溶劑) (solvent)
NMP：N-甲基-2-吡咯烷酮 NMP: N-methyl-2-pyrrolidone
BCS：丁基賽珞蘇 BCS: Dinkycellosu
GBL：γ丁內酯 GBL: gamma butyrolactone
又，聚醯亞胺之分子量測定條件如下。 In addition, the molecular weight measurement conditions of polyimide are as follows.
裝置：SENSHU科學公司製常溫凝膠滲透層析(GPC)裝置(SSC-7200) Device: Normal temperature gel permeation chromatography (GPC) device (SSC-7200) manufactured by SENSHU Scientific Co., Ltd.
管柱：Shodex公司製管柱(KD-803、KD-805) Pipe column: Pipe column manufactured by Shodex Company (KD-803, KD-805)
管柱溫度：50℃ Column temperature: 50℃
溶離液：N,N’-二甲基甲醯胺(作為添加劑之溴化鋰-水合物(LiBr‧H2O)為30mmol/L、磷酸‧無水結晶(正磷酸)為30mmol/L、THF為10ml/L) Eluate: N,N'-dimethylformamide (lithium bromide-hydrate (LiBr‧H 2 O) as an additive is 30mmol/L, phosphoric acid‧anhydrous crystal (orthophosphoric acid) is 30mmol/L, THF is 10ml /L)
流速：1.0ml/分 Flow rate: 1.0ml/min
檢量線製作用標準樣本：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 Laboratory公司製聚乙二醇(分子量約12,000、4,000、1,000) Standard samples for calibration line production: TSK standard polyethylene oxide manufactured by Tosoh Corporation (molecular weight approximately 9000,000, 150,000, 100,000, 30,000), and polyethylene glycol manufactured by Polymer Laboratory Corporation (molecular weight approximately 12,000, 4,000, 1,000 )
<聚合物之合成> <Synthesis of Polymers>
實施例3 Example 3
DI-2MG/NG4ABA、APC16 DI-2MG/NG4ABA, APC16
於配備氮氣導入管與攪拌子之50ml之2口燒瓶中量取DI-2MG2.00g(6.75mmol)，加入NMP19.61g使其溶解，加入APC16 0.24g(0.68mmol)後，於室溫使其反應1小時。再加入NG4ABA1.22g(5.88mmol)，於氮氣環境下於40℃反應24小時。藉此，獲得濃度15質量%、黏度220mPas之聚合物(聚合物溶液：P-1)。獲得之聚合物之重量平均分子量為Mw：37200。 Measure 2.00g (6.75mmol) of DI-2MG into a 50ml 2-neck flask equipped with a nitrogen inlet tube and a stirrer, add 19.61g of NMP to dissolve it, add 0.24g (0.68mmol) of APC16, and let it stand at room temperature. Reaction takes 1 hour. Then add 1.22g (5.88mmol) of NG4ABA and react at 40°C for 24 hours in a nitrogen atmosphere. Thereby, a polymer (polymer solution: P-1) with a concentration of 15% by mass and a viscosity of 220 mPas was obtained. The weight average molecular weight of the obtained polymer was Mw: 37200.
實施例4 Example 4
DI-2MG/NG4APhA、APC16 DI-2MG/NG4APhA, APC16
於配備氮氣導入管與攪拌子之50ml之2口燒瓶中量取DI-2MG2.00g(6.75mmol)，加入NMP20.12g，使其溶解，加入APC16 0.24g(0.68mmol)後，於室溫反應1小時。再加入NG4APhA1.31g(5.88mmol)，於氮氣環境下於40℃反應24小時。藉此，獲得濃度15質量%、黏度280mPas之聚合物(聚合物溶液：P-2)。獲得之聚合物之重量平均分子量為Mw：39100。 Measure 2.00g (6.75mmol) of DI-2MG into a 50ml 2-neck flask equipped with a nitrogen inlet tube and a stirrer. Add 20.12g of NMP to dissolve it. Add 0.24g (0.68mmol) of APC16 and react at room temperature. 1 hour. Then add 1.31g (5.88mmol) of NG4APhA and react at 40°C for 24 hours in a nitrogen atmosphere. Thereby, a polymer (polymer solution: P-2) with a concentration of 15% by mass and a viscosity of 280 mPas was obtained. The weight average molecular weight of the obtained polymer was Mw: 39100.
實施例5 Example 5
DI-2MG/NG4ABA、PCH7 DI-2MG/NG4ABA, PCH7
於配備氮氣導入管與攪拌子之50ml之2口燒瓶中量取DI-2MG2.00g(6.75mmol)，加入NMP20.57g，使其溶解，添加PCH7 0.52g(1.36mmol)後，於室溫反應1小時。再加入NG4ABA1.11g(5.34mmol)，於氮氣環境下於40℃反應24小時。藉此，獲得濃度15質量%、黏度230mPas之聚合物(聚合物溶液：P-3)。獲得之聚合物之重量平均分子量為Mw：40200。 Measure 2.00g (6.75mmol) of DI-2MG into a 50ml 2-neck flask equipped with a nitrogen inlet tube and a stirrer, add 20.57g of NMP to dissolve it, add 0.52g (1.36mmol) of PCH7, and react at room temperature. 1 hour. Then add 1.11g (5.34mmol) of NG4ABA and react at 40°C for 24 hours in a nitrogen atmosphere. Thereby, a polymer (polymer solution: P-3) with a concentration of 15% by mass and a viscosity of 230 mPas was obtained. The weight average molecular weight of the obtained polymer was Mw: 40200.
實施例6 Example 6
IDI、DI-2MG/NG4ABA、PCH7 IDI, DI-2MG/NG4ABA, PCH7
於配備氮氣導入管與攪拌子之50ml之2口燒瓶中，加入DI-2MG1.00g(3.38mmol)、NMP14.05g，使其溶解，添加PCH7 0.37g(0.97mmol)後，於室溫反應1小時。再加入IDI0.32g(1.45mmol)、NG4ABA0.79g(3.81mmol)，於氮氣環境下於40℃反應24小時。藉此，獲得濃度15質量%、黏度300mPas之聚合物(聚合物溶液：P-4)。獲得之聚合物之重量平均分子量為Mw：44200。 In a 50ml 2-neck flask equipped with a nitrogen inlet tube and a stirrer, add 1.00g (3.38mmol) of DI-2MG and 14.05g of NMP to dissolve them. Add 0.37g (0.97mmol) of PCH7 and react at room temperature 1 hours. Then add 0.32g (1.45mmol) of IDI and 0.79g (3.81mmol) of NG4ABA, and react at 40°C for 24 hours in a nitrogen atmosphere. Thereby, a polymer (polymer solution: P-4) with a concentration of 15% by mass and a viscosity of 300 mPas was obtained. The weight average molecular weight of the obtained polymer was Mw: 44200.
比較例1 Comparative example 1
DI-2MG/Me4APhA、APC16 DI-2MG/Me4APhA, APC16
於配備氮氣導入管與攪拌子之50ml之2口燒瓶中量取DI-2MG2.00g(6.75mmol)，加入NMP17.73g，使其溶解，添加APC16 0.24g(0.68mmol)後，於室溫反應1小時。再加入Me4APhA0.89g(5.94mmol)，於氮氣環境下於40℃反應24小時。藉此，獲得濃度15質量%、黏度320mPas之聚合物(聚合物溶液：PRef-1)。獲得之聚合物之重量平均分子量為Mw：39900。 Measure 2.00g (6.75mmol) of DI-2MG into a 50ml 2-neck flask equipped with a nitrogen inlet tube and a stirrer, add 17.73g of NMP to dissolve it, add 0.24g (0.68mmol) of APC16, and react at room temperature. 1 hour. Then add 0.89g (5.94mmol) of Me4APhA, and react at 40°C for 24 hours in a nitrogen atmosphere. Thereby, a polymer (polymer solution: PRef-1) with a concentration of 15% by mass and a viscosity of 320 mPas was obtained. The weight average molecular weight of the obtained polymer was Mw: 39900.
比較例2 Comparative example 2
DI-2MG/Me4APhA、PCH7 DI-2MG/Me4APhA, PCH7
於配備氮氣導入管與攪拌子之50ml之2口燒瓶中，量取DI-2MG2.00g(6.75mmol)，加入NMP18.7g，使其溶解，添加PCH7 0.51g(1.35mmol)後，於室溫反應1小時。再添加Me4APhA0.79g(5.27mmol)，於氮氣環境下於40℃反應24小時。藉此，獲得濃度15質量%、黏度280mPas之聚合物(聚合物溶液：PRef-2)。獲得之聚合物之重量平均分子量為Mw：37200。 In a 50ml 2-neck flask equipped with a nitrogen inlet tube and a stirrer, measure 2.00g (6.75mmol) of DI-2MG, add 18.7g of NMP, dissolve it, add 0.51g (1.35mmol) of PCH7, and stir at room temperature. Reaction takes 1 hour. Then 0.79g (5.27mmol) of Me4APhA was added, and the reaction was carried out at 40°C for 24 hours in a nitrogen atmosphere. Thereby, a polymer (polymer solution: PRef-2) with a concentration of 15% by mass and a viscosity of 280 mPas was obtained. The weight average molecular weight of the obtained polymer was Mw: 37200.
比較例3 Comparative example 3
CBDA/p-PDA、PCH7 CBDA/p-PDA, PCH7
於配備氮氣導入管與攪拌子之50ml之2口燒瓶中量取p-PDA1.00g(9.24mmol)、PCH7 0.88g(2.31mmol)，加入NMP23.12g，使其溶解。之後添加CBDA2.20g(11.20mmol)，於氮氣環境下於室溫反應24小時。藉此，獲 得濃度15質量%、黏度380mPas之聚合物(聚合物溶液：PRef-3)。獲得之聚合物之重量平均分子量為Mw：44200。 Measure 1.00g (9.24mmol) of p-PDA and 0.88g (2.31mmol) of PCH7 into a 50ml 2-neck flask equipped with a nitrogen inlet tube and a stirrer, add NMP23.12g and dissolve them. Afterwards, 2.20g (11.20mmol) of CBDA was added, and the reaction was carried out at room temperature under nitrogen atmosphere for 24 hours. By this, get A polymer (polymer solution: PRef-3) with a concentration of 15% by mass and a viscosity of 380 mPas was obtained. The weight average molecular weight of the obtained polymer was Mw: 44200.
<液晶配向劑之製備> <Preparation of liquid crystal alignment agent>
實施例7 Example 7
於配備攪拌子之50ml之三角燒瓶中量取實施例3獲得之聚合物(P-1)10.0g，添加NMP2.5g、GBL5.0g、BCS7.5g後，於室溫攪拌30分鐘。藉此，獲得固體成分6.0質量%、NMP44質量%、GBL20質量%、BCS30質量%之液晶配向劑(AL-1)。 Measure 10.0 g of the polymer (P-1) obtained in Example 3 into a 50 ml Erlenmeyer flask equipped with a stirrer, add 2.5 g of NMP, 5.0 g of GBL, and 7.5 g of BCS, and stir at room temperature for 30 minutes. In this way, a liquid crystal alignment agent (AL-1) with a solid content of 6.0 mass%, NMP 44 mass%, GBL 20 mass%, and BCS 30 mass% was obtained.
實施例8 Example 8
於配備攪拌子之50ml之三角燒瓶中量取實施例4獲得之聚合物(P-2)10.0g，添加NMP2.5g、GBL5.0g、BCS7.5g後，於室溫攪拌30分鐘。藉此，獲得固體成分6.0質量%、NMP44質量%、GBL20質量%、BCS30質量%之液晶配向劑(AL-2)。 Measure 10.0 g of the polymer (P-2) obtained in Example 4 into a 50 ml Erlenmeyer flask equipped with a stirrer, add 2.5 g of NMP, 5.0 g of GBL, and 7.5 g of BCS, and stir at room temperature for 30 minutes. In this way, a liquid crystal alignment agent (AL-2) with a solid content of 6.0 mass%, NMP44 mass%, GBL20 mass%, and BCS30 mass% was obtained.
實施例9 Example 9
於配備攪拌子之50ml之三角燒瓶中量取實施例5獲得之聚合物(P-3)10.0g，添加NMP2.5g、GBL5.0g、BCS7.5g後，於室溫攪拌30分鐘。藉此，獲得固體成分6.0質量%、NMP44質量%、GBL20質量%、BCS30質量%之液晶配向劑(AL-3)。 Measure 10.0 g of the polymer (P-3) obtained in Example 5 into a 50 ml Erlenmeyer flask equipped with a stirrer, add 2.5 g of NMP, 5.0 g of GBL, and 7.5 g of BCS, and stir at room temperature for 30 minutes. In this way, a liquid crystal alignment agent (AL-3) with a solid content of 6.0 mass%, NMP 44 mass%, GBL 20 mass%, and BCS 30 mass% was obtained.
實施例10 Example 10
於配備攪拌子之50ml之三角燒瓶中量取實施例6獲得之聚合物(P-4)10.0g，添加NMP2.5g、GBL5.0g、BCS7.5g後，於室溫攪拌30分鐘。藉此，獲得固體成分 6.0質量%、NMP44質量%、GBL20質量%、BCS30質量%之液晶配向劑(AL-4)。 Measure 10.0 g of the polymer (P-4) obtained in Example 6 into a 50 ml Erlenmeyer flask equipped with a stirrer, add 2.5 g of NMP, 5.0 g of GBL, and 7.5 g of BCS, and stir at room temperature for 30 minutes. Thus, the solid content is obtained 6.0 mass%, NMP44 mass%, GBL20 mass%, BCS30 mass% liquid crystal alignment agent (AL-4).
比較例4 Comparative example 4
於配備攪拌子之50ml之三角燒瓶中量取比較例1獲得之聚合物(PRef-1)10.0g，添加NMP2.5g、GBL5.0g、BCS7.5g後，於室溫攪拌30分鐘。藉此，獲得固體成分6.0質量%、NMP44質量%、GBL20質量%、BCS30質量%之液晶配向劑(AL-5)。 10.0 g of the polymer (PRef-1) obtained in Comparative Example 1 was measured into a 50 ml Erlenmeyer flask equipped with a stirrer, 2.5 g of NMP, 5.0 g of GBL, and 7.5 g of BCS were added, and the mixture was stirred at room temperature for 30 minutes. In this way, a liquid crystal alignment agent (AL-5) with a solid content of 6.0 mass%, NMP 44 mass%, GBL 20 mass%, and BCS 30 mass% was obtained.
比較例5 Comparative example 5
於配備攪拌子之50ml之三角燒瓶中量取比較例2獲得之聚合物(PRef-2)10.0g，添加NMP2.5g、GBL5.0g、BCS7.5g後，於室溫攪拌30分鐘。藉此，獲得固體成分6.0質量%、NMP44質量%、GBL20質量%、BCS30質量%之液晶配向劑(AL-6)。 10.0 g of the polymer (PRef-2) obtained in Comparative Example 2 was measured into a 50 ml Erlenmeyer flask equipped with a stirrer, and 2.5 g of NMP, 5.0 g of GBL, and 7.5 g of BCS were added, and the mixture was stirred at room temperature for 30 minutes. In this way, a liquid crystal alignment agent (AL-6) with a solid content of 6.0 mass%, NMP 44 mass%, GBL 20 mass%, and BCS 30 mass% was obtained.
比較例6 Comparative example 6
於配備攪拌子之50ml之三角燒瓶中量取比較例3獲得之聚合物(PRef-3)10.0g，添加NMP2.5g、GBL5.0g、BCS7.5g後，於室溫攪拌30分鐘。藉此，獲得固體成分6.0質量%、NMP44質量%、GBL20質量%、BCS30質量%之液晶配向劑(AL-7)。 10.0 g of the polymer (PRef-3) obtained in Comparative Example 3 was measured into a 50 ml Erlenmeyer flask equipped with a stirrer, and 2.5 g of NMP, 5.0 g of GBL, and 7.5 g of BCS were added, and the mixture was stirred at room temperature for 30 minutes. In this way, a liquid crystal alignment agent (AL-7) with a solid content of 6.0 mass%, NMP 44 mass%, GBL 20 mass%, and BCS 30 mass% was obtained.
使用實施例7~10之液晶配向劑(AL-1~AL-4)及比較例4~6之液晶配向劑(AL-5~AL-7)，依照下列方法來評價液晶配向膜。 The liquid crystal alignment agents (AL-1 to AL-4) of Examples 7 to 10 and the liquid crystal alignment agents (AL-5 to AL-7) of Comparative Examples 4 to 6 were used to evaluate the liquid crystal alignment film according to the following method.
<白化耐性及塗佈性(印刷性)之評價> <Evaluation of whitening resistance and coating properties (printability)>
將獲得之液晶配向劑分別滴1滴在充分洗淨的Cr基板，於室溫25℃、濕度60%放置，測定直到變白(白化)的時間。依據測得的時間來評價白化耐性。 Put one drop of the obtained liquid crystal alignment agent on a fully cleaned Cr substrate, place it at room temperature of 25°C and a humidity of 60%, and measure the time until it turns white (whitening). The bleaching resistance was evaluated based on the measured time.
將液晶配向劑以1.0μm的濾器過濾後，在洗淨的Cr板上使用配向膜印刷機(日本寫真印刷公司製「ANGSTROMER」)進行柔版印刷以實施塗佈性試驗。 After filtering the liquid crystal alignment agent with a 1.0 μm filter, flexographic printing was performed on a cleaned Cr plate using an alignment film printer ("ANGSTROMER" manufactured by Nippon Photo Printing Co., Ltd.) to conduct a coatability test.
於網紋輥滴加約1.0ml的液晶配向劑，實施10次空運轉後，停止印刷機10分鐘，使印刷版乾燥。之後於1片Cr基板進行印刷，將印刷後之基板在70℃之熱板上放置5分鐘，進行塗膜的臨時乾燥，觀察膜狀態。以目視、及光學顯微鏡(尼康公司製「ECLIPSE ME600」)的倍率50倍，主要觀察膜厚不均、邊緣部的膜厚不均。 Add approximately 1.0 ml of liquid crystal alignment agent to the anilox roller, and after performing 10 dry runs, stop the printing press for 10 minutes to dry the printing plate. Then, print on a Cr substrate, place the printed substrate on a hot plate at 70°C for 5 minutes, temporarily dry the coating film, and observe the film state. The film thickness unevenness and the film thickness unevenness at the edge were mainly observed with visual inspection and an optical microscope ("ECLIPSE ME600" manufactured by Nikon Corporation) at a magnification of 50 times.
<液晶配向性、電壓保持率、及預傾角之評價> <Evaluation of liquid crystal alignment, voltage retention, and pretilt angle>
[液晶配向性之觀察、及液晶晶胞之製作] [Observation of liquid crystal alignment and production of liquid crystal cells]
將液晶配向劑以1.0μm的濾器過濾後，利用旋塗印刷塗佈在附電極之基板(橫30mm×縱40mm的大小，厚度為1.1mm之玻璃基板。電極係寬度10mm×長度40mm之矩形且厚度35nm的ITO電極)。於50℃之熱板上進行5分鐘乾燥後，於180℃之IR式烘箱進行20分鐘煅燒，形成膜厚100nm之塗膜。將此膜以縲縈布(吉川化工製YA-20R)磨擦(輥輪直徑：120mm、輥輪轉速：1000rpm、移動速度：20mm/sec、推入長：0.4mm)後，於純水中照射超音波1分鐘並洗淨，以空吹去除水滴後，於 80℃乾燥15分鐘，獲得附液晶配向膜之基板。 After filtering the liquid crystal alignment agent with a 1.0 μm filter, the liquid crystal alignment agent is applied to a substrate with an electrode (a glass substrate with a size of 30 mm in width x 40 mm in length and a thickness of 1.1 mm) by spin coating. The electrode is a rectangle with a width of 10 mm x 40 mm in length. ITO electrode with thickness 35nm). After drying on a hot plate at 50°C for 5 minutes, it was calcined in an IR oven at 180°C for 20 minutes to form a coating film with a thickness of 100 nm. This film was rubbed with a lining cloth (YA-20R manufactured by Yoshikawa Chemical Industry) (roller diameter: 120mm, roller rotation speed: 1000rpm, moving speed: 20mm/sec, push length: 0.4mm), and then irradiated in pure water Ultrasonic for 1 minute and wash, remove water droplets with air blowing, and then Dry at 80°C for 15 minutes to obtain a substrate with a liquid crystal alignment film.
準備2片上述附液晶配向膜之基板，在其中1片液晶配向膜面上散佈4μm之間隔件後，從其上印刷密封劑，並將另1片基板以磨擦方向為反方向且膜面面對的方式貼合後，使密封劑硬化，製作空晶胞。對此空晶胞以減壓注入法注入MLC-2041(Merck(股)公司製)，將注入口密封，獲得液晶晶胞。之後，觀察液晶配向性後，將液晶晶胞於110℃加熱1小時，於23℃放置一晚，得到電壓保持率測定用之液晶晶胞。 Prepare two substrates with liquid crystal alignment films as mentioned above. Spread 4 μm spacers on one of the liquid crystal alignment film surfaces, print the sealant from it, and place the other substrate with the rubbing direction in the opposite direction and the film surface After attaching them in the right way, the sealant is hardened to create an empty unit cell. MLC-2041 (manufactured by Merck Co., Ltd.) was injected into the empty cell using a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell. After that, after observing the alignment of the liquid crystal, the liquid crystal cell was heated at 110°C for 1 hour and left at 23°C overnight to obtain a liquid crystal cell for voltage retention measurement.
使用上述程序獲得之電壓保持率測定用之液晶晶胞，於60℃之溫度下以60μs的間距施加1V的電壓，測定166.7ms後之電壓，計算電壓能以何程度保持，作為電壓保持率。又，電壓保持率之測定係使用東陽科技公司製之VHR-1電壓保持率測定裝置。 Using the liquid crystal cell for measuring the voltage retention rate obtained through the above procedure, apply a voltage of 1V at an interval of 60μs at a temperature of 60°C, measure the voltage after 166.7ms, and calculate to what extent the voltage can be maintained as the voltage retention rate. In addition, the voltage holding rate was measured using the VHR-1 voltage holding rate measuring device manufactured by Dongyang Technology Co., Ltd.
[預傾角之評價] [Evaluation of pretilt angle]
預傾角之測定使用Optometric公司製Axo Scan Mueller Matrix Polarimeter。 The pretilt angle was measured using an Axo Scan Mueller Matrix Polarimeter manufactured by Optometric Corporation.
上述各種評價結果示於表3。 The various evaluation results mentioned above are shown in Table 3.
【表3】
實施例7~10之液晶配向劑，相較於比較例，白化耐性較優異、印刷性也較良好。比較例6是聚醯胺酸系之材料，故是白化耐性、印刷性良好的材料系。實施例7~10，針對白化耐性、印刷性，可期待獲得和比較例5同等以上之特性。 Compared with the comparative examples, the liquid crystal alignment agents of Examples 7 to 10 have better whitening resistance and better printability. Comparative Example 6 is a polyamide-based material, so it has good whitening resistance and printability. Examples 7 to 10 are expected to have properties equal to or greater than those of Comparative Example 5 in terms of whitening resistance and printability.
又，使用實施例7~10之液晶配向劑獲得之液晶晶胞，為高預傾角且可獲得高電壓保持率。例如：本實施例使用之含側鏈之單體，貢獻於增大液晶之預傾角，故藉由對於含側鏈之單體單體之結構、導入量進行各種選擇，期待可獲得目的之預傾角。本發明之一態樣液晶配向膜據認為作為能於低溫煅燒之液晶配向膜是非常有前景。又，使用實施例7~10中任一液晶配向劑，皆能理想地獲得液晶配向膜及液晶顯示元件。 In addition, the liquid crystal cells obtained using the liquid crystal alignment agents of Examples 7 to 10 have a high pretilt angle and can obtain a high voltage retention rate. For example, the side chain-containing monomer used in this embodiment contributes to increasing the pretilt angle of the liquid crystal. Therefore, by making various selections on the structure and introduction amount of the side chain-containing monomer, it is expected that the intended purpose can be achieved. inclination angle. The liquid crystal alignment film according to one aspect of the present invention is considered to be very promising as a liquid crystal alignment film that can be calcined at low temperature. In addition, using any of the liquid crystal alignment agents in Examples 7 to 10, a liquid crystal alignment film and a liquid crystal display element can be obtained ideally.
使用本發明之液晶配向劑製作之液晶顯示元件，可成為可靠性高的液晶顯示器件，適合使用在TN液晶顯示元件、STN液晶顯示元件、TFT液晶顯示元件、VA液晶顯示元件、OCB液晶顯示元件等利用各種方式的顯示元件。 Liquid crystal display elements produced by using the liquid crystal alignment agent of the present invention can become highly reliable liquid crystal display devices, and are suitable for use in TN liquid crystal display elements, STN liquid crystal display elements, TFT liquid crystal display elements, VA liquid crystal display elements, and OCB liquid crystal display elements. etc. using various forms of display components.
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