TWI275630B - Composition of containing polyamic acid blends and liquid crystal alignment layer and cell using them - Google Patents
Composition of containing polyamic acid blends and liquid crystal alignment layer and cell using them Download PDFInfo
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- TWI275630B TWI275630B TW093136791A TW93136791A TWI275630B TW I275630 B TWI275630 B TW I275630B TW 093136791 A TW093136791 A TW 093136791A TW 93136791 A TW93136791 A TW 93136791A TW I275630 B TWI275630 B TW I275630B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract
Description
1275630 玖、發明說明: 本發明係有關於一種含有低極性聚醯胺酸樹脂之垂 直配向型組成物’及使用該垂直配向型組成物之液晶配向 膜和液晶晶胞,更詳言之,本發明係有關於一種新聚醯胺 酸混合組成物,和使用該聚醢胺酸混合組成物之具有非常 優良的低表面粗糙度、印刷性、耐熱性及透明性之液晶配 向膜,以及使用該聚醯胺酸混合組成物之具有8 9度以上 預傾角(pretilt angle)及 99%以上電壓保持率之液晶晶 胞。該新聚醯胺酸混合組成物,具有優良耐熱性、表面硬 度、透明性及液晶之配向性,係以適當的比率混合低極性 的聚醯胺酸樹脂和聚醯胺酸衍生物而成,該低極性的聚酿 胺酸樹脂係由二酸酐(含有脂環族系二酸酐)與芳香族二亞 胺類(含有醯亞胺環側鏈基之芳香族二胺)係藉由溶液聚合 成。 【先前技術】 通常,聚醯亞胺樹脂係指芳香族四羧酸或是其衍生物 與芳香族二胺或是芳香族二異氰酯進行縮聚合後,醯亞胺 化而製成之高耐熱性樹脂。 聚醯亞胺樹脂依照所使用單體之種類,可以得到各種 的分子結構。通常,芳香族四羧酸成分可以使用焦蜜石酸 二酐(PMDA)或是雙苯二曱酸二酐(BPDA)等,芳香族二胺 成分可以使用對苯二胺(p-PDA)、間苯二胺(m-PDA)、4,4-氧基二苯胺(ODA)、4,4-亞甲基二苯胺(MDA)、2,2-二胺基 苯基六氟丙烷(HFDA)、間雙胺基苯氧基二苯颯 (m-BAPS)、對雙胺基苯氧基二苯颯(;?-;6八?3)、1,4-雙胺基 苯氧基苯(TPE-Q)、l,3-雙胺基苯氧基苯(丁?£-11)、2,2-雙胺 基苯氧基苯基丙烷(BAPP)、2,2-雙胺基苯氧基苯基六氟丙 烷(HFBAPP)等,進行縮聚合而製得。 大部分的聚醯亞胺樹脂係不溶及不熔之超高耐熱樹 脂’具有(1)優良的耐熱抗氧化性、(2)可以使用溫度高、 1275630 (3)顯示具有約260°C之長期可以使用溫度及約480°C之短 期町以使用溫度之優良的耐熱等性、(4)耐放射線性、(5) 優良的低溫特性、以及(6)優良的耐藥品性等特性。 但是,僅管聚醯亞胺樹脂具有如此之特性,起因於電 荷移動錯合物(charge transfer complex)之形成,在可見光 線領域之透光性較低而有難以應用於要求透明性之領域 的問題點存在。因此,有各式各樣種類之主鏈型脂肪族聚 醯亞胺樹脂被製造,應用於如液晶配向膜等要求具有優良 光穿透性領域。 目前為止,所開發出來之在主鏈導入脂環基之液晶配 向膜用聚醯亞胺樹脂,係為了顯現預傾角而在側鏈導入長 的烧鏈基來使用,具代表性的有可以溶解在溶劑中的可溶 性聚醯亞胺樹脂及聚醯胺酸系樹脂。但是,可溶性聚醯亞 胺樹脂時,因為對通常之有機溶劑之溶解度差而有印刷性 不良之問題,聚醯胺酸系配向膜時,因為高表面極性而有 電壓保持率(VHR,v〇ltage h〇lding川⑷降低之缺點。而 ^,為了應用作為可以適應各式各樣的驅動方式之配向 膜,要求控制預傾角。 【發明 因 脂所製 落等問 鏈之聚 物,在 是對有 性、透 因 明性、 又 物,提 及透明 内容】 以往使用聚醯亞胺系樹 溶解性及電壓保持性低 。發現將具有低極性侧 脂環族系聚醯胺酸衍生 合而成的組成物,不只 ’而且具有優良的耐熱 性,而完成了本發明。 種具有優良耐熱性、透 直配向型組成物。 用前述垂直配向型組成 優良的印刷性、财熱性 具有優良的預傾角角及 此,本發明者等,為了解決 得液晶配向膜之光穿透性、 題點而專心深入地進行研究 醯胺酸樹脂,與芳香族或是 溶液狀態下以一定的比率混 機洛劑具有優良的溶解性 明性、表面硬度及垂直配向 此,本發明之目的是提供一 表面硬度及垂直配向性之垂 ’本發明之另外目的,係使 供一種具有低表面粗輪度' 性之液晶配向膜,以及一種 4 1275630 電壓保持率之液晶晶胞。 依照本發明實施例,本發明係提供混合下式(1)所表示 含有低極性側鏈之聚醯胺酸樹脂與含有下式(2)所表示之 聚醯胺酸衍生物而成之垂直配向型組成物。 [化學式1]1275630 发明, invention description: The present invention relates to a vertical alignment type composition containing a low polarity polyphthalic acid resin and a liquid crystal alignment film and a liquid crystal cell using the vertical alignment type composition, more specifically, The present invention relates to a novel polyphthalic acid mixed composition, and a liquid crystal alignment film having a very excellent low surface roughness, printability, heat resistance and transparency using the polyamic acid mixed composition, and using the same A liquid crystal unit cell having a pretilt angle of 89 degrees or more and a voltage holding ratio of 99% or more of the polyaminic acid mixed composition. The novel polylysine mixed composition has excellent heat resistance, surface hardness, transparency, and alignment of liquid crystals, and is obtained by mixing a low-polarity polyamic acid resin and a poly-proline derivative at an appropriate ratio. The low-polarity polyacrylic acid resin is obtained by solution polymerization from a dianhydride (containing an alicyclic dianhydride) and an aromatic diimide (an aromatic diamine having a sulfhydryl ring side chain group). . [Prior Art] In general, a polyimine resin refers to an aromatic tetracarboxylic acid or a derivative thereof which is polycondensed by an amidation reaction with an aromatic diamine or an aromatic diisocyanate. Heat resistant resin. The polyimine resin can have various molecular structures depending on the kind of the monomer to be used. Usually, the aromatic tetracarboxylic acid component may be pyromellitic dianhydride (PMDA) or bisphthalic acid dianhydride (BPDA), and the aromatic diamine component may be p-phenylene diamine (p-PDA). M-phenylenediamine (m-PDA), 4,4-oxydiphenylamine (ODA), 4,4-methylenediphenylamine (MDA), 2,2-diaminophenylhexafluoropropane (HFDA) , bis-aminophenoxydiphenyl hydrazine (m-BAPS), p-diaminophenoxydiphenyl hydrazine (;?-; 6 VIII? 3), 1,4-diaminophenoxybenzene ( TPE-Q), l,3-diaminophenoxybenzene (butyl?-11), 2,2-diaminophenoxyphenylpropane (BAPP), 2,2-diaminophenoxy Phenyl hexafluoropropane (HFBAPP) or the like is obtained by condensation polymerization. Most of the polyimide resin is insoluble and infusible. The high heat resistant resin has (1) excellent heat and oxidation resistance, (2) high temperature, 1275630 (3) and long period of about 260 °C. The temperature and the short-term temperature of about 480 ° C can be used, and the temperature is excellent in heat resistance, (4) radiation resistance, (5) excellent low-temperature characteristics, and (6) excellent chemical resistance. However, only the polyimine resin has such a characteristic, which is caused by the formation of a charge transfer complex, has low light transmittance in the visible light field, and is difficult to be applied to a field requiring transparency. The problem exists. Therefore, various types of main chain type aliphatic polyimine resins have been produced and used in fields requiring excellent light penetration such as liquid crystal alignment films. The polyimine resin for liquid crystal alignment film which has been introduced into the alicyclic group in the main chain has been developed so that a long burnt chain group is introduced into the side chain in order to exhibit a pretilt angle, and a representative one can be dissolved. A soluble polyimine resin and a polyaminic acid resin in a solvent. However, in the case of a soluble polyimine resin, there is a problem of poor printability due to poor solubility in a usual organic solvent, and a polymethylamine-based alignment film has a voltage holding ratio (VHR, v〇) due to high surface polarity. Ltage h〇ldingchuan (4) reduces the disadvantages. However, in order to apply it as an alignment film that can adapt to various driving methods, it is required to control the pretilt angle. For the purpose of sexuality, transparency, and transparency, the use of polyimine-based trees has low solubility and low voltage retention. It has been found that a low-polarity alicyclic polyglycine is derived. The composition is not only 'and has excellent heat resistance, and the present invention has been completed. The composition has excellent heat resistance and a direct alignment type composition. The above-mentioned vertical alignment type composition has excellent printability and richness, and has excellent pretilt angle. In order to solve the problem of the light transmittance and the problem of the liquid crystal alignment film, the present inventors have intensively studied the proline resin, with an aromatic or a solution. Under the certain ratio, the mixed agent has excellent solubility, surface hardness and vertical alignment. The purpose of the present invention is to provide a surface hardness and vertical alignment. The other object of the present invention is to provide a A liquid crystal alignment film having a low surface coarseness and a liquid crystal cell having a voltage retention of 4 1275630. According to an embodiment of the present invention, the present invention provides a mixture of low polarity side chains represented by the following formula (1) A vertical alignment type composition comprising a proline resin and a polyglycine derivative represented by the following formula (2).
[化學式2][Chemical Formula 2]
[式中 係選自由In the formula
)OC )〇Λ〇( )σ°τ〇( )0¾ ⑹)OC )〇Λ〇( )σ°τ〇( )03⁄4 (6)
)Dr°^°^〇C ch3 中1種或2種以上的4價基,必須含有選自由結構式 1275630 (a)、(b)、(c)、(d)、以及(e)中1種或2種以上的脂環族系 4價基;以及 及 係各自含有選自由 CF3 ’ > , , ~<0>-8(f)One or two or more kinds of tetravalent groups of Dr ° ° ° ° ° C ch3 must contain one selected from the structural formula 1275630 (a), (b), (c), (d), and (e) Species or two or more alicyclic tetravalent groups; and each of the steroids selected from CF3 ' > , , ~<0>-8(f)
0-ss^N^g.Q (CH 2)nCH 3 (此時n為1〜30範圍之自然數)中i種或2種以上的2 價基,前述必須含有前述結構式(f)之院基琥 拍酿亞胺側鏈之芳香族2價基;係“Μ卜_ 範圍之自然數] 又,依照本發明之另外 . 布前述聚醯胺酸混合物組成 月係提供一種塗 晶晶胞。 战物而製成之液晶配向膜及液 依照本發明,係提供 種聚醯胺酸混合組成物,該聚 6 1275630 酿胺酸混合組成物所会右^ 極性側鏈,不僅具有非::二酿胺酸,具有新穎結構之低 用作為要求嚴格的特性以及高預傾角,此等使 日赦*瞪芬久絲丨 特性之TFT_TN及STN LCD用液 明配向膜及各種尖端耐熱結構材料,乃是有用的。 【實施方式】 以下詳細說明本發明。 本發二月係有關於一種垂直配向型組成物,係以 tm· (1)所表示之含有低極性侧鏈之聚醯胺酸樹 月曰,、刖式(2)所表不之聚醯胺酸衍生物而成。而且,係有 於一種具有優良耐熱性、透明性、表面硬度、高電壓保持 率及預傾角性等特性之液晶配向膜或是液晶晶胞,藉由塗 布前記垂直配向型組成物而成。 、則式(1)所表示之含有低極性側鏈之聚醯胺酸樹脂,與 前式(2)所表示之聚醯胺酸衍生物,係在1〜99重量% :〜99 重量%之混合比範圍内使用。 本發明有關之前式(1)所表示之含有低極性側鏈之聚 醯胺酸樹脂和前式(2)所表示之聚醯胺酸衍生物,係將芳香 族四羧酸或是其衍生物與芳香族二胺或是芳香族二異氰 酸酯,進行縮聚合製得,依照所使用之單體的種類可以具 有各種的分子結構。通常,芳香族四羧酸單體可以選自由 焦蜜石酸二酐(PMDA)、二苯基酮四羧酸二酐、羥基聯笨 二甲酸二酐、聯苯二曱酸二酐(BPDA)、以及六氟異亞丙基 聯苯二甲酸二酐等來使用。又,芳香族二胺單體通常可二 選自由對苯二胺(P-PDA)、間苯二胺(m-PDA)、4,4-氧基二 苯胺(ODA)、4,4-亞甲基二苯胺(MDA)、2,2-二胺基笨基六 氟丙烷(HFDA)、間雙胺基苯氧基二苯颯(m-BAPS)、詞·雙、 胺基苯氧基二苯MQ9-BAPS)、1,4-雙胺基苯氧基苯 (TPE-Q)、1,3-雙胺基苯氧基苯(TPE-R)、2,2-雙胺基笨氣基 苯基丙烷(BAPP)、2,2-雙胺基苯氧基苯基六氟丙烷 a (HFBAPP)等來使用。 1275630 ,發明有關之含有前式⑴所表示低極性侧 胺酸樹月旨和前式(2)所表示之聚醯胺酸衍生物,除了前= 常的芳香族單體以夕卜,亦含有前述結構式 以: 肪族四羧酸二酐單體和前述結構式 === 亞f =之芳香族二胺作為必要成分之二胺單體:Ϊ 行聚合製造。 术進 亦即,前述(1)所表示之含有低極性側鏈之聚醯 脂係二酸酐單"了通常之芳香族四㈣單體以:酸: 含有脂肪族四羧酸二酐,選自由U2,3,扣環丁烷四羧酸二 酐[CBDA,(a)]、1,2,3,4-環丙烷四羧酸二酐[CPDa 5-(2,5-二氧四氫呋喃基)-3·甲基環己烷-U2-二羧酸二 [DOCDA, (c)]、4-(2,5-二側氧基四氫呋喃基基)·四氫芏 -1,2·二羧酸二酐[DOTDA; (d)]、以及辛烯-2,3_5,6•四羧酸 二酐[BOD A ; (e)]中1種或2種以上之脂肪族四羧酸二酐 作為必要成分。^時,前述結構式(a)〜(6)所表示脂肪族四 羧酸二酐之使用量,係在相對於全二酸酐單體為!〜99莫 耳%之範圍使用。 ' 前式(1)所表示之含有低極性側鏈之聚醯胺酸樹脂 時’其構造具有脂肪族基之側鍵基之同時,亦同時結合燒 基琥珀醯亞胺基之特徵,藉此,二胺單體除了通常的芳香 族二胺單體以外,亦含有前述結構式(f)所表示之烷基琥珀 酿亞胺基取代之方香無二胺為必要成分,來進’行聚合製 造。此時,前述結構式(f)所表示之芳香族二胺之使用量, 相對於全二胺單體為1〜99莫耳%之範圍。 藉此,將前述(f)所表示之芳香族二胺使用作為必要單 體所製成之新穎混合物,係藉由與聚醯胺酸樹脂(導入含有 低極性烷基取代之琥泊酸亞胺側鏈基)混合,可以改善透明 性、印刷性、機械特性,並且,使用前述組成物所製成之 液晶晶胞的電光學特性,特別地得到改善。 含有如前述之前式(1)所表示低極性側鏈之聚醯胺酸 樹脂,其重量平均分子量(Mw)為5,000〜15〇,〇〇〇g/莫耳範 圍,固有粘度為0·1〜1.5dL/g範圍,玻璃轉移溫度為 1275630 15 0〜300 C fe圍。又’前式(1)所表示之可溶性聚醯亞胺樹 脂,對以二曱基乙醯胺(DMAc)、二曱基甲醯胺(DMF)、N_ 曱基-2-毗洛σ定酮(NMP)、丙酮、乙酸乙酯等非質子性極性 溶劑為首之如間曱苯酚的有機溶劑,在常溫具有容易溶解 的特性。 又,前式(2)所表示之聚醯胺酸衍生物,因為二酸酐單 體係使用則述結構式(a)〜(e)所表示之脂肪族四羧酸酐作 為必要單體,所以能夠製造可以提升機械特性、在使耐埶 性降低最小之同時,亦可以改善印刷性之聚醯胺酸衍= 物。以前述單體之組成藉由溶液聚合製成之前式(2)所表示 之聚酿胺酸衍生物,具有重量平均分子量(Mw)為 10,000〜200,000g/莫耳範圍,固有黏度為〇3〜2〇dL/g範 圍’玻璃轉移溫度為200〜40(TC範圍,醯亞胺化 200〜300°C範圍之特性。 則式(2)所表示之聚醯胺酸衍生物 又 ‘ π 1河如二甲基乙 醯胺(DMA)、二曱基曱酿胺(DMF)、Ν_曱基_2"比咯啶酮 (ΝΜΡ)、丙酮、乙酸乙酯等非質子性極性 甲苯酚等有機溶劑在常溫具有易溶解之特性。^ I二 四氫呋喃(THF)、氯仿等低沸點溶劑及r〜 狀=疋對如 性溶劑在常溫顯示有10重量%以上之高溶解度知?= 等之混合溶劑亦顯示高溶解度。 、 又,使用通常該領域所使用的方法,塗布人火, 所表示低極性側鏈之聚醯胺酸樹脂及前 ^有前^式(1) 胺酸衍生物所製成之液晶配向膜或是液斤表示聚酿 光學特性結果,預傾角(pretile angle)為87曰日乂評。價★其電 電壓保持率(voltage holding ratio)為 98.0 〜99 q。範圍 壓(residual-D.C)為1〇〇〜400mV範圍。如前述%,殘留電 為在保持聚醯胺酸原有之優良特性之同時,二^特性,因 配向特性亦優良,所以可以使用作為以各種=w性及液晶 太空、航空等尖端產業為核心之耐熱材料。器、電子、 (實施例) 以下,藉由下述之實施例來詳細說明本發明,作是本 9 1275630 發明並不限定於該等,在本發明之技術思想範圍内可以有 種種的變形及修正。 [製造例 1] 1-(3,5-二胺苯基)-3-(1-己烯)-琥珀醢亞 胺 (DN-IM-6)之製造 邊使氮氣慢慢地通過配置有攪拌機、氮氣注入裝置之 250mL反應器,邊在作為反應溶劑之50mL乙酸中溶解9.2g (0.05莫耳)之3,5-二硝苯胺後,邊通過氮氣邊加入9.1g (0.05莫耳)之2 -己烯-1-基-琥珀酸酐,回流24小時。在常 溫冷卻反應溶液後,得到析出之固體。0-ss^N^gQ (CH 2)nCH 3 (where n is a natural number in the range of 1 to 30), or two or more kinds of divalent groups, and the above-mentioned formula (f) The aromatic divalent group of the side chain of the succinimide; the "natural number of the range", in addition, according to the invention. The composition of the polyamic acid mixture described above provides a smear cell. According to the present invention, a liquid crystal alignment film and a liquid are provided, and a mixed composition of polyglycine is provided, and the poly 6 1275630 urethane mixed composition has a right side polar side chain, which not only has a non-:: Amino acid, which has a novel structure and low use as a demanding property and a high pretilt angle, is a liquid alignment film for TFT_TN and STN LCD and various tip heat-resistant structural materials which are used for the characteristics of the 赦 瞪 瞪 久 久 久 久[Embodiment] The present invention will be described in detail below. The second aspect of the present invention relates to a vertical alignment type composition, which is a polyglycine tree containing a low-polarity side chain represented by tm·(1). , a lysine derivative of the formula (2), which is represented by the formula (2). A liquid crystal alignment film or a liquid crystal cell having excellent heat resistance, transparency, surface hardness, high voltage holding ratio, and pretilt angle, is formed by coating a vertical alignment type composition, and then a formula (1) The polyamic acid resin containing a low-polarity side chain is used, and the poly-proline derivative represented by the above formula (2) is used in a mixing ratio of 1 to 99% by weight: to 99% by weight. The present invention relates to a polyamic acid resin containing a low-polarity side chain represented by the above formula (1) and a poly-proline derivative represented by the above formula (2), which is an aromatic tetracarboxylic acid or a derivative thereof. The aromatic diamine or the aromatic diisocyanate is obtained by polycondensation, and may have various molecular structures depending on the kind of the monomer to be used. Usually, the aromatic tetracarboxylic acid monomer may be selected from pyromic acid dianhydride. (PMDA), diphenyl ketone tetracarboxylic dianhydride, hydroxybiphenyldicarboxylic dianhydride, biphenyl dicarboxylic acid dianhydride (BPDA), and hexafluoroisopropylidene dianhydride dianhydride are used. Further, the aromatic diamine monomer can usually be selected from p-phenylene diamine (P-PD). A), m-phenylenediamine (m-PDA), 4,4-oxydiphenylamine (ODA), 4,4-methylenediphenylamine (MDA), 2,2-diaminophenyl hexafluoropropane (HFDA), m-diaminophenoxydiphenyl hydrazine (m-BAPS), the word bis, aminophenoxydiphenyl MQ9-BAPS), 1,4-diaminophenoxybenzene (TPE- Q), 1,3-diaminophenoxybenzene (TPE-R), 2,2-diamino-p-phenylene phenylpropane (BAPP), 2,2-diaminophenoxyphenyl hexa Fluoropropane a (HFBAPP) or the like is used. 1275630, the present invention relates to a poly-proline derivative represented by the low-polarity side acid tree represented by the above formula (1) and the above formula (2), except for the former = The aromatic monomer also contains the above structural formula: an aliphatic tetracarboxylic dianhydride monomer and a diamine monomer having the above structural formula === subf = aromatic diamine as an essential component: Ϊ Polymerization manufacturing. The above-mentioned (1) is a poly-aromatic dianhydride containing a low-polarity side chain. The usual aromatic tetra-(tetra) monomer is: acid: contains an aliphatic tetracarboxylic dianhydride, and is selected. Free U2,3, deducted butane tetracarboxylic dianhydride [CBDA, (a)], 1,2,3,4-cyclopropane tetracarboxylic dianhydride [CPDa 5-(2,5-dioxotetrahydrofuranyl) -3·Methylcyclohexane-U2-dicarboxylic acid II [DOCDA, (c)], 4-(2,5-di-oxytetrahydrofuranyl)·tetrahydroindole-1,2·dicarboxylate Acid dianhydride [DOTDA; (d)], and one or more aliphatic tetracarboxylic dianhydrides of octene-2,3_5,6•tetracarboxylic dianhydride [BOD A ; (e)] Essential ingredients. In the case of ^, the amount of the aliphatic tetracarboxylic dianhydride represented by the above structural formulae (a) to (6) is based on the total diacid anhydride monomer! ~99% of the range is used. When the polyamic acid resin containing a low-polarity side chain represented by the former formula (1) has a side bond group having an aliphatic group, it also combines the characteristics of a burnt amber quinone imide group. The diamine monomer, in addition to the usual aromatic diamine monomer, also contains the alkyl amber-bromide-substituted pericyrene-free diamine represented by the above structural formula (f) as an essential component for the polymerization. Manufacturing. In this case, the amount of the aromatic diamine represented by the above structural formula (f) is in the range of 1 to 99 mol% based on the total diamine monomer. Thereby, the novel mixture prepared by using the aromatic diamine represented by the above (f) as an essential monomer is obtained by mixing with a polyaminic acid resin (introduction of a succinate substituted with a low polarity alkyl group) The side chain group is mixed to improve transparency, printability, and mechanical properties, and the electrooptical characteristics of the liquid crystal cell made using the above composition are particularly improved. The polyamic acid resin containing a low-polarity side chain represented by the above formula (1) has a weight average molecular weight (Mw) of 5,000 to 15 Å, a 〇〇〇g/mole range, and an intrinsic viscosity of 0·1~ In the range of 1.5dL/g, the glass transition temperature is 1275630 15 0~300 C fe. Also a soluble polyimine resin represented by the former formula (1), p-dimethylacetamide (DMAc), dimercaptocarboxamide (DMF), N-mercapto-2-pyrrolidone An organic solvent such as (NMP), an aprotic polar solvent such as acetone or ethyl acetate, such as m-phenol, has a property of being easily dissolved at normal temperature. Further, since the polyphthalic acid derivative represented by the above formula (2) is used as a dianhydride single-system, the aliphatic tetracarboxylic anhydride represented by the structural formulae (a) to (e) is an essential monomer, and therefore It is possible to produce a poly-proline derivative which can improve the mechanical properties and minimize the deterioration of the scratch resistance while also improving the printability. The polyamic acid derivative represented by the above formula (2) is prepared by solution polymerization from the composition of the aforementioned monomers, and has a weight average molecular weight (Mw) of 10,000 to 200,000 g/mole, and an intrinsic viscosity of 〇3~ 2 〇dL / g range 'glass transition temperature is 200 ~ 40 (TC range, yttrium imidation 200 ~ 300 ° C range characteristics. Then the formula (2) represented by the poly-proline derivative again ' π 1 river Such as dimethyl acetamide (DMA), dimercaptoamine (DMF), Ν 曱 _2 _2 " pyrrolidone (ΝΜΡ), acetone, ethyl acetate and other aprotic polar cresols and other organic The solvent has a property of being easily soluble at room temperature. I. Low-boiling solvent such as dihydrofuran (THF) or chloroform, and r~-like = 疋. For a solvent, it has a high solubility of 10% by weight or more at room temperature. It also shows high solubility. Moreover, it is made by using a method generally used in the field, coating a human fire, a poly-proline resin represented by a low-polarity side chain, and a precursor acid derivative (1). The liquid crystal alignment film or liquid jin indicates the result of the optical characteristics of the brewing, and the pretil angle is 87. The price of the voltage is 98.0 ~ 99 q. The range voltage (residual-DC) is in the range of 1 〇〇 ~ 400 mV. As the above %, the residual electricity is in the maintenance of poly-proline In addition to the excellent characteristics of the original, the characteristics of the two characteristics are excellent, so it can be used as a heat-resistant material with various types of =w and liquid crystal space, aviation and other cutting-edge industries. Instruments, Electronics, (Example) The present invention will be described in detail by the following examples, which are not limited thereto, and may be variously modified and modified within the scope of the technical idea of the present invention. [Manufacturing Example 1] 1- Preparation of (3,5-diaminophenyl)-3-(1-hexene)-succinimide (DN-IM-6) while slowly passing nitrogen through a 250 mL reaction equipped with a stirrer and a nitrogen injection device After dissolving 9.2 g (0.05 mol) of 3,5-dinitroaniline in 50 mL of acetic acid as a reaction solvent, 9.1 g (0.05 mol) of 2-hexen-1-yl group was added by nitrogen gas. - Succinic anhydride, refluxed for 24 hours. After cooling the reaction solution at normal temperature, a precipitated solid was obtained.
使前述所得到之固體在甲.醇中再結晶,製得12.7g之 1-(3,5-二胺苯基)-3-(1-己烯)-琥珀醯亞胺 (DN-IM-6)(產 率 73%)。 [製造例 2] 1-(3,5-二胺苯基)-3-(1-辛烯)-琥珀醯亞 胺(DN-IM-8)之製造 除了使用l〇.5g (0.05莫耳)之2-辛烯-1-基-琥珀酸酐 代替2 -己烯-1 -基-琥珀酸酐以外,進行與前述製造例1同 樣的反應,得到1-(3,5-二胺苯基)-3-(1-辛烯)-琥珀醯亞胺 (DN-IM-8)。 使前述所得到之固體在曱醇中再結晶,製得1 3 · 1 g之 1-(3,5-二胺苯基)-3-(1-辛烯)-琥珀醯亞胺 (DN-IM-8)(產 率 70%)。The solid obtained above was recrystallized from methyl alcohol to obtain 12.7 g of 1-(3,5-diaminophenyl)-3-(1-hexene)-succinimide (DN-IM- 6) (yield 73%). [Production Example 2] Production of 1-(3,5-diaminophenyl)-3-(1-octene)-succinimide (DN-IM-8) except for the use of 〇.5 g (0.05 mol) The same reaction as in the above Production Example 1 was carried out except that 2-octene-1-yl-succinic anhydride was used instead of 2-hexene-1-yl-succinic anhydride to obtain 1-(3,5-diaminephenyl). -3-(1-octene)-amber imine (DN-IM-8). The solid obtained above was recrystallized from decyl alcohol to obtain 1 3 · 1 g of 1-(3,5-diaminophenyl)-3-(1-octene)-succinimide (DN- IM-8) (yield 70%).
[製造例 3] 1-(3,5-二胺苯基)-3-( 1-癸烯)·琥拍醯亞 胺 (DN-IM-10)之製造 除了使用11.9g (0.05莫耳)之2-癸烯-1-基-琥珀酸酐 代替2 -己烯-1 -基-琥珀酸酐以外,進行與前述製造例1同 樣的反應,得到1-(3,5-二胺苯基)-3-(1-癸烯)-琥珀醯亞胺 (DN-IM-10)。 使前述所得到之固體在曱醇中再結晶,製得14· 5g之 1-(3,5-二胺苯基)-3-(1-癸烯)-琥珀醯亞胺(〇>1-1]\1-10)(產 率 70%)。 [製造例 4] 1-(3,5-二胺苯基)-3-(1-十二烯)-琥珀醯 亞胺 (DN-IM-12)之製造 10 1275630 除了使用13.3g (0.05莫耳)之2-十二烯-1-基-琥珀酸 酐代替 2 -己烯-1 -基-琥珀酸酐以外,進行與前述製造例1 同樣的反應,得到1-(3,5-二胺苯基)-3-(1-十二烯)-琥珀醯 亞胺(DN-IM-12)。 使前述所得到之固體在曱醇中再結晶,製得1 4.0g之 1-(3,5-二胺苯基)-3-(1-十二烯)-琥珀醯亞胺 (DN-IM-12) (產率65%)。 [製造例 5] 1-(3,5-二胺苯基)-3-(1-十四烯)-琥珀醯 亞胺 (DN-IM-14)之製造 除了使用14.7g (0.05莫耳)之2-十四烯-1-基-琥珀酸 酐代替2 -己烯-1 -基-琥珀酸酐以外,進行與前述製造例1 同樣的反應,得到1-(3,5-二胺苯基)-3-(1-十四烯)-琥珀醯 亞胺(DN-IM-14)。 使前述所得到之固體在甲醇中再結晶,製得14.9g之 1-(3,5-二胺苯基)-3-(1-十四烯)-琥珀醯亞胺 (DN-IM-14) (產率65%)。 [製造例 6] 1-(3,5-二胺苯基)-3-(1-十六烯)-琥珀醯 亞胺 (DN-IM-16)之製造 除了使用16.1 g (0.05莫耳)之2-十六烯-1-基-琥珀酸 酐代替2-己烯-1 -基-琥珀酸酐以外,進行與前述製造例 1 同樣的反應,得到1-(3,5-二胺苯基)-3-(1-十六烯)-琥珀醯 亞胺(DN-IM-16)。 使前述所得到之固體在曱醇中再結晶,製得1 5.4g之 1-(3,5-二胺苯基)-3-(1-十六烯)-琥珀醯亞胺 (DN-IM-16) (產率63%)。 [製造例 7] 1-(3,5-二胺苯基)-3-(1-十八烯)-琥珀醯 亞胺(DN-IM-18)之製造 除了使用17.5g (0.05莫耳)之2-十八烯-1-基-琥珀酸 酐代替2-己烯-1 -基-琥珀酸酐以外,進行與前述製造例 1 同樣的反應,得到1-(3,5-二胺苯基)-3-(1-十八烯)-琥珀醯 亞胺(DN-IM-18)。 使前述所得到之固體在曱醇中再結晶,製得16.2g之 11 1275630 卜(3,5_ 一胺笨基十八烯)-琥珀醯亞胺(DN-IM-18) (產率63%)。 [製造例8] U(3,5-二胺苯基)-3_己基-琥珀醯亞胺 (DA-IM-6)之製造 ^ Dn*IM-6 6,9g (0.02 莫耳)溶解於 i〇〇mL 之 NMP 和乙醇(1/3體積比)後,與〇 &之pd/c(5%)觸媒(在碳粒子 ,面塗布5%量之I巴金屬而成之觸媒)同時投入氫反應器 後’在60 C進行2小時還原反應。將反應物過濾後,對反 應溶劑進行減壓蒸餾。[Manufacturing Example 3] Production of 1-(3,5-diaminophenyl)-3-(1-decene)·sodium bromide (DN-IM-10) except for the use of 11.9 g (0.05 m) The same reaction as in the above Production Example 1 was carried out except that 2-decene-1-yl-succinic anhydride was used instead of 2-hexene-1-yl-succinic anhydride to obtain 1-(3,5-diaminephenyl)- 3-(1-decene)-succinimide (DN-IM-10). The solid obtained above was recrystallized from decyl alcohol to obtain 14.5 g of 1-(3,5-diaminophenyl)-3-(1-decene)-succinimide (〇>1 -1]\1-10) (yield 70%). [Manufacturing Example 4] Production of 1-(3,5-diaminophenyl)-3-(1-dodecene)-succinimide (DN-IM-12) 10 1275630 In addition to the use of 13.3 g (0.05 Mo The same reaction as in the above Production Example 1 was carried out except that 2-dodecen-1-yl-succinic anhydride of the ear was used instead of 2-hexene-1-yl-succinic anhydride to obtain 1-(3,5-diaminobenzene). Benzyl-3-(1-dodecene)-succinimide (DN-IM-12). The solid obtained above was recrystallized from decyl alcohol to obtain 14.0 g of 1-(3,5-diaminophenyl)-3-(1-dodecene)-succinimide (DN-IM). -12) (yield 65%). [Production Example 5] Production of 1-(3,5-diaminophenyl)-3-(1-tetradecene)-succinimide (DN-IM-14) except for the use of 14.7 g (0.05 m) The same reaction as in the above Production Example 1 was carried out except that 2-tetradecen-1-yl-succinic anhydride was used instead of 2-hexene-1-yl-succinic anhydride to obtain 1-(3,5-diaminephenyl). -3-(1-tetradecene)-succinimide (DN-IM-14). The solid obtained above was recrystallized from methanol to obtain 14.9 g of 1-(3,5-diaminophenyl)-3-(1-tetradecene)-succinimide (DN-IM-14). ) (yield 65%). [Manufacturing Example 6] Production of 1-(3,5-diaminophenyl)-3-(1-hexadecenyl)-succinimide (DN-IM-16) except for the use of 16.1 g (0.05 m) The same reaction as in the above Production Example 1 was carried out except that 2-hexadecen-1-yl-succinic anhydride was used instead of 2-hexene-1-yl-succinic anhydride to obtain 1-(3,5-diaminephenyl). -3-(1-hexadecenyl)-succinimide (DN-IM-16). The solid obtained above was recrystallized from decyl alcohol to obtain 1 5.4 g of 1-(3,5-diaminophenyl)-3-(1-hexadecenyl)-succinimide (DN-IM). -16) (yield 63%). [Production Example 7] Production of 1-(3,5-diaminophenyl)-3-(1-octadecene)-succinimide (DN-IM-18) except 17.5 g (0.05 m) was used. The same reaction as in the above Production Example 1 was carried out except that 2-octadecen-1-yl-succinic anhydride was used instead of 2-hexene-1-yl-succinic anhydride to obtain 1-(3,5-diaminephenyl). -3-(1-octadecene)-amber imine (DN-IM-18). The solid obtained above was recrystallized from decyl alcohol to obtain 16.2 g of 11 1275630 (3,5-amine-aldolyl octadecene)-succinimide (DN-IM-18) (yield 63%) ). [Production Example 8] Production of U(3,5-diaminophenyl)-3-hexyl-succinimide (DA-IM-6) ^ Dn*IM-6 6,9 g (0.02 mol) dissolved in i〇〇mL of NMP and ethanol (1/3 volume ratio), and 〇 & pd / c (5%) catalyst (in the carbon particles, coated with 5% of the amount of I bar metal catalyst After the hydrogen reactor was simultaneously charged, the reduction reaction was carried out at 60 C for 2 hours. After the reaction product was filtered, the reaction solvent was distilled under reduced pressure.
在己燒/乙酸乙醋之共溶劑中使前述所得到之固體再 結晶’製得3.1 8g之1-(3,5-二胺苯基)-3 -己基-琥珀醯亞胺 (DA-IM-6)(產率 55%) 〇 [製造例9] K (3,5-二胺苯基)-3-辛基-琥ίό醯亞胺 (DA-IM-8)之製造 除 了使用 7.5g (〇·02 莫耳)之 dn-IM-8 代替 DN-IM-6 以外’進行與前述製造例8同樣的反應,得到二胺 本基)-3 -辛基-琥珀酿亞胺(da_im-8)。 使前述所得到之固體在甲醇中再結晶,製得3 · 6 8 g之 1-(3,5-二胺苯基)-3-辛基-琥珀醯亞胺(Da-IM-8)(產率 5 8%) ° [製造例10] 1-(3,5-二胺苯基)-3-癸基-琥珀醯亞胺The above-obtained solid was recrystallized in a co-solvent of hexane/ethyl acetate to prepare 3.18 g of 1-(3,5-diaminophenyl)-3-hexyl-succinimide (DA-IM). -6) (yield 55%) 〇 [Production Example 9] K (3,5-diaminophenyl)-3-octyl-succinimide (DA-IM-8) was produced in addition to 7.5 g. (〇·02 Moer) dn-IM-8 The same reaction as in the above Production Example 8 was carried out except for DN-IM-6 to obtain a diamine-based group -3 -octyl-succinimide (da_im- 8). The solid obtained above was recrystallized from methanol to obtain 3 · 6 8 g of 1-(3,5-diaminophenyl)-3-octyl-succinimide (Da-IM-8) ( Yield 5 8%) ° [Production Example 10] 1-(3,5-diaminophenyl)-3-indolyl-succinimide
(DA-IM-10)之製造 除 了使用 8.1g(〇.〇2 莫耳)之 DN-IM-10 代替 DN-IM-6 以外’進行與前述製造例8同樣的反應,得到二胺 苯基)-3-癸基-號珀醯亞胺(DA-IM-10)。 使前述所得到之固體在曱醇中再結晶,製得4 _ 1 5 g之 1-(3,5-二胺苯基)_3-癸基-琥珀醯亞胺(DA-IM-10)(產率 60%) ° [製造例11] 1-(3,5-二胺苯基)_3_十二烷基-琥珀醯亞 胺(DA-IM-12)之製造 除 了使用 8.6g(〇.〇2 莫耳)之 DN-IM-12 代替 DN-IM-6 以外,進行與前述製造例8同樣的反應,得到1-(3,5_二胺 12 1275630 苯基)-3-十二烷基-琥珀醯亞胺(dA-IM-12)。 使前述所得到之固體在己烷/乙酸乙酯中再結晶,製得 4.48g之1-(3,5-二胺苯基)-3 -十二燒基-破珀醯亞胺 (DA-IM-12)(產率 60%)。 [製造例12] M3,5-二胺苯基)-3-十四烷基·琥珀醯 亞胺(DA-IM-14)之製造 除 了使用 9.2g (0.02 莫耳)之 DN-IM-14 代替 DN-IM-6 以外,進行與前述製造例8同樣的反應,得到^^弘二胺 苯基)-3-十四烷基-琥珀醯亞胺(DA-IM-14)。 使前述所得到之固體在曱醇中再結晶,製得5.6g之 1-(3,5 -二胺苯基)-3 -十四烷基-琥珀醢亞胺(DA-IM-14) (產率70%)。 [製造例13] M3,5-二胺苯基)-3-十六烷基-琥珀醯 亞胺(DA-IM-16)之製造 除 了使用 9.8g(0.〇2 莫耳)之 DN-IM-16 代替 DN-IM-6 以外,進行與前述製造例8同樣的反應,得到1-(3,5·二胺 苯基)-3-十六烷基-琥珀醯亞胺(DA-IM-16)。 使前述所得到之固體在己烷/乙酸乙酯中再結晶,製得 6.01g之 1-(3,5 -二胺苯基)·3 -十六烷基-琥珀醯亞胺 (DA-IM-16)(產率 70%)。 [製造例14] 1-(3,5-二胺苯基)-3-十八烷基-琥珀醯 亞胺(DA-IM-18)之製造 除 了使用 10.3g (〇.〇2 莫耳)之 DN-IM-18 代替 DN-IM-6 以外,進行與前述製造例8同樣的反應,得到1-(3,5-二胺 苯基)-3-十八烷基-琥珀醯亞胺(DA-IM-18)。 使前述所得到之固體在己烷/乙酸乙酯中再結晶,製得 6.87g之 1-(3,5 -二胺苯基)-3-十八烷基-琥珀醯亞胺 (DA-IM-18)(產率 75%)。 前述製造例8〜1 4所製得之具有低極性烷基取代之琥 珀醯亞胺側鏈基之二胺單體DA-IM-6〜18,可以確認再結 晶後之產率為5 0%以上’並顯示在空氣中具有非常優良的 儲存安定性。 13 Ϊ275630 [製造例1 5]含有低極性側鏈之聚醯胺酸樹酯(PAA-1 ) 之製造 邊使氮氣慢慢地通過配置有攪拌機、溫度調節裝置、 氮氣注入裝置及冷卻器之250mL反應器,邊在作為反應溶 劑之 N-甲基-2-毗咯啶酮中溶解 9.15g (〇·〇2莫耳)之 u(3,5-二胺苯基)-3 -十八烷基-琥珀醯亞胺 (DA-IM-18) 後,邊通過氮氣邊慢慢地加入5.28g (0.02莫耳)之固體狀 的5-(2,5-二氧基四氫呋喃)-3 -甲基環己烷-1,2-二羧酸二 酐。此時,固體成分濃度(solid content)固定在20重量%, 邊保持反應溫度在〇°C以下邊攪拌24小時,得到聚醯胺酸 溶液(PAA-1)。 [製造例1 6]含有低極性側鏈之聚醢胺酸樹酯(pAA-2) 之製造 邊使氮氣慢慢地通過配置有攪拌機、溫度調節裝置、 氮氣注入裝置及冷卻器之25 OmL反應器,邊在作為反應溶 劑之 N-曱基-2 -毗咯啶酮中溶解 9.15g (〇.〇2莫耳)之 1-(3,5 -二胺苯基)-3 -十八烷基-琥珀醯亞胺 (DA-IM-18) 後,邊通過氮氣邊慢慢地加入固體狀的3.92g (0.02莫耳) 之1,2,3,4-環丁烷四羧酸二酐。此時,固體成分濃度(s〇Hd content)固定在20重量%,邊保持反應溫度在〇°c以下邊 攪拌24小時,得到聚醯胺酸溶液(paA-2)。 [製造例17]聚醯胺酸(PAA-3)之製造 邊使氮氣慢慢地通過配置有攪拌機、氮氣注入裝置之 5 00mL反應器,邊在作為反應溶劑之N-曱基吡咯啶酮 中溶解19.8g(0.1莫耳)之亞甲二苯胺後,邊通過氮氣邊慢 慢地加入固體狀的19.6g (〇1莫耳)之12,3,4·環丁烷四羧 酸二酐。此時,固體成分濃度(s〇lid content)固定在15重 量% ’邊保持反應溫度在〇它以下邊攪拌36小時,得到聚 醢胺酸溶液(PAA-3)。 [製造例18]可溶性聚醯胺酸樹酯(SPI)之製造 邊使氮氣慢慢地通過配置有攪拌機、溫度調節褒置、 氮氣注入裝置及冷卻器之25〇mL反應器,邊在作為反應溶 14 1275630 劑之 N-曱基-2 -毗咯啶酮中溶解 9.15g (0.02 莫耳)之 1-(3,5 -二胺苯基)-3 -十八烷基-琥珀醯亞胺 (DA-IM-1 8) 後,邊通過氮氣邊慢慢地加入固體狀的5 · 2 8 g (0 · 02莫耳) 之5-(2,5-二氧四氫呋喃)-3 -曱基環己烷-1,2-二羧酸二酐。 此時,固體成分濃度(solid content)固定在20重量%,邊 保持反應溫度在0 °C以下邊攪拌24小時,得到聚醯胺酸溶 液。(DA-IM-10) Production The same reaction as in the above Production Example 8 was carried out except that 8.1 g of DN-IM-10 was used instead of DN-IM-6 to obtain a diamine phenyl group. )-3-mercapto-pyrazine (DA-IM-10). The solid obtained above was recrystallized from decyl alcohol to obtain 4 to 15 g of 1-(3,5-diaminophenyl)-3-indolyl-succinimide (DA-IM-10) ( Yield 60%) ° [Production Example 11] Production of 1-(3,5-diaminophenyl)_3-dodecyl-succinimide (DA-IM-12) except 8.6 g (〇. The same reaction as in the above Production Example 8 was carried out except that DN-IM-12 was used instead of DN-IM-6 to obtain 1-(3,5-diamine 12 1275630 phenyl)-3-dodecane. Alkyl-succinimide (dA-IM-12). The solid obtained above was recrystallized from hexane/ethyl acetate to give 4.48 g of 1-(3,5-diaminophenyl)-3 -doderyl-dipperimide (DA- IM-12) (yield 60%). [Production Example 12] M3,5-diaminephenyl)-3-tetradecylsuccinimide (DA-IM-14) was produced except that 9.2 g (0.02 mol) of DN-IM-14 was used. The same reaction as in the above-mentioned Production Example 8 was carried out, except for DN-IM-6, to obtain the crude diamine phenyl)-3-tetradecyl-succinimide (DA-IM-14). The solid obtained above was recrystallized from decyl alcohol to obtain 5.6 g of 1-(3,5-diaminophenyl)-3-tetradecyl-succinimide (DA-IM-14) ( Yield 70%). [Production Example 13] M3,5-diaminephenyl)-3-hexadecyl-succinimide (DA-IM-16) was produced except that 9.8 g (0. 〇 2 mol) of DN was used. The same reaction as in the above Production Example 8 was carried out except that DN-IM-6 was used to obtain 1-(3,5·diaminophenyl)-3-hexadecyl-succinimide (DA-IM). -16). The solid obtained above was recrystallized from hexane/ethyl acetate to obtain 6.01 g of 1-(3,5-diaminophenyl)·3 -hexadecyl-succinimide (DA-IM). -16) (yield 70%). [Production Example 14] Production of 1-(3,5-diaminophenyl)-3-octadecyl-succinimide (DA-IM-18) except for the use of 10.3 g (〇.〇2 Mo) The same reaction as in the above Production Example 8 was carried out except that DN-IM-18 was used instead of DN-IM-6 to obtain 1-(3,5-diaminophenyl)-3-octadecyl-succinimide ( DA-IM-18). The solid obtained above was recrystallized from hexane/ethyl acetate to give 6.87 g of 1-(3,5-diaminophenyl)-3-octadecyl-succinimide (DA-IM). -18) (yield 75%). The diamine monomers DA-IM-6 to 18 having the low-polarity alkyl-substituted amber imine side chain group obtained in the above Production Examples 8 to 14 can be confirmed to have a yield of 50% after recrystallization. The above 'and shows that it has very good storage stability in the air. 13 Ϊ 275630 [Production Example 15] Production of polyamic acid anhydride (PAA-1) containing a low-polarity side chain, while slowly passing nitrogen gas through a 250 mL equipped with a stirrer, a temperature adjusting device, a nitrogen gas injection device, and a cooler In the reactor, 9.15 g of (u,5-diaminophenyl)-3-octadecane was dissolved in N-methyl-2-pyrrolidone as a reaction solvent. After the base-succinimide (DA-IM-18), 5.28 g (0.02 mol) of 5-(2,5-dioxytetrahydrofuran)-3-A was slowly added by nitrogen. Cyclohexane-1,2-dicarboxylic dianhydride. At this time, the solid content was fixed at 20% by weight, and while stirring at a reaction temperature of 〇 ° C or lower for 24 hours, a polyaminic acid solution (PAA-1) was obtained. [Production Example 16] Production of polyamic acid anhydride (pAA-2) containing a low-polarity side chain, while slowly passing nitrogen gas through a 25 mL reaction equipped with a stirrer, a temperature adjusting device, a nitrogen gas injection device, and a cooler 1. Dissolve 9.15 g of 1-(3,5-diaminophenyl)-3-octadecane in N-mercapto-2-pyrrolidone as a reaction solvent. After the base-succinimide (DA-IM-18), a solid 3.92 g (0.02 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was slowly added while passing nitrogen. . At this time, the solid content concentration (s〇Hd content) was fixed at 20% by weight, and while stirring at a reaction temperature of 〇°c or lower for 24 hours, a polyaminic acid solution (paA-2) was obtained. [Production Example 17] Production of polyacrylic acid (PAA-3) While slowly passing nitrogen gas through a 500 mL reactor equipped with a stirrer and a nitrogen gas injection device, N-mercaptopyrrolidone as a reaction solvent was used. After dissolving 19.8 g (0.1 mol) of methylenediphenylamine, a solid 19.6 g (〇1 mol) of 12,3,4·cyclobutane tetracarboxylic dianhydride was slowly added while passing nitrogen. At this time, the solid content concentration (s〇lid content) was fixed at 15 wt%, and the reaction temperature was kept under the crucible for 36 hours to obtain a polyaminic acid solution (PAA-3). [Production Example 18] Production of soluble polyamido resin (SPI) while passing nitrogen gas slowly through a 25 〇 mL reactor equipped with a stirrer, a temperature adjustment device, a nitrogen gas injection device, and a cooler, as a reaction Dissolving 9.15 g (0.02 mol) of 1-(3,5-diaminophenyl)-3-octadecyl-succinimide in N-mercapto-2-pyrrolidone dissolved in 14 1275630 After (DA-IM-1 8), a solid 5·28 g (0·02 mol) of 5-(2,5-dioxotetrahydrofuran)-3-fluorenyl group was slowly added while passing nitrogen gas. Cyclohexane-1,2-dicarboxylic dianhydride. At this time, the solid content was fixed at 20% by weight, and the mixture was stirred for 24 hours while maintaining the reaction temperature at 0 ° C or lower to obtain a polyamic acid solution.
在前述之聚醯胺酸溶液中加入乙酸酐6.12g (0.06莫 耳)和说啶0.1 g (0.1莫耳),在常溫攪拌24小時後,在120 °C攪拌3小時後,用甲醇洗淨數次,得到可溶性聚醯胺酸 樹酯(SPI)。 [實施例1 ]含有低極性側鏈的聚醯胺酸樹脂與聚醯胺 酸之混合物(BPAA-2)之製造 邊使氮氣慢慢地通過配置有攪拌機、氮氣注入裝置之 1000mL反應器,邊在作為稀釋溶劑之80g N-曱基-2-毗咯 啶酮、120g 7 -丁内酯、60g 2 -正丁氧基乙醇中溶解 1.973g前述製造例1 5之含有低極性側鏈之聚醯胺酸樹脂 溶液和50g前述製造例17之聚醯胺酸溶液,攪拌24小時, 製得黏度為25cps之溶液。 [實施例2 ]含有低極性側鏈的聚醯胺酸樹脂與聚醯胺 酸之混合物(BPAA-3)之製造To the above polyamic acid solution, 6.12 g (0.06 mol) of acetic anhydride and 0.1 g (0.1 mol) of pyridine were added, and after stirring at room temperature for 24 hours, stirring at 120 ° C for 3 hours, and then washing with methanol. Several times, a soluble polyamine resin (SPI) was obtained. [Example 1] Production of a mixture of a polyamic acid resin and a polyaminic acid (BPAA-2) containing a low-polarity side chain while slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen gas injection device 1.97 g of the low-polar side chain-containing polypolymer of the above-mentioned Production Example 15 was dissolved in 80 g of N-mercapto-2-pyrrolidone, 120 g of 7-butyrolactone, and 60 g of 2-n-butoxyethanol as a diluent solvent. The proline resin solution and 50 g of the polyamic acid solution of the above-mentioned Production Example 17 were stirred for 24 hours to obtain a solution having a viscosity of 25 cps. [Example 2] Production of a mixture of a polyamic acid resin and a polyaminic acid (BPAA-3) containing a low-polarity side chain
邊使氮氣慢慢地通過配置有攪拌機、氮氣注入裝置之 10 00mL反應器,邊在作為稀釋溶劑之80g N-甲基-2-毗咯 啶酮、120g r-丁内酯、60g 2 -正丁氧基乙醇中溶解 4 · 1 6 6 g前述製造例1 5之含有低極性側鏈之聚醯胺酸樹脂 溶液和5 0g前述製造例1 7之聚醯胺酸溶液,攪拌24小時, 製得黏度為25cps之溶液。 [實施例3 ]含有低極性側鏈的聚醯胺酸樹脂與聚醯胺 酸之混合物(BPAA-4)之製造 邊使氮氣慢慢地通過配置有攪拌機、氮氣注入裝置之 1000mL反應器,邊在作為稀釋溶劑之75 g N-甲基-2-毗咯 啶酮、120g r-丁内酯、60g 2 -正丁氧基乙醇中溶解 15 1275630 16.073g前述製造例15之含有低極性側鏈之聚醢胺酸樹脂 溶液和5 0g前述製造例1 7之聚醯胺酸溶液,攪拌24小時, 製得黏度為2 5 c p s之溶液。 [實施例4 ]含有低極性侧鏈的聚醯胺酸樹脂與聚醯胺 酸之混合物(BPAA-5)之製造 邊使氮氣慢慢地通過配置有攪拌機、氮氣注入裝置之 10 00mL反應器,邊在作為稀釋溶劑之75 g N-甲基-2-毗咯 啶酮、120g r_ 丁内酯、60g 2 -正丁氧基乙醇中溶解 3 7 · 5 0 3 g前述製造例1 5之含有低極性側鏈之聚醯胺酸樹脂 溶液和5 0g前述製造例1 7之聚醯胺酸溶液,攪拌24小時, 製得黏度為2 5 c ps之溶液。 [實施例5 ]含有低極性側鏈的聚醯胺酸樹脂與聚醯胺 酸之混合物(BPAA-6)之製造 邊使氮氣慢慢地通過配置有攪拌機、氮氣注入裝置之 lOOOmL反應器,邊在作為稀釋溶劑之75g N-曱基-2-毗咯 啶酮、120g 7 - 丁内酯、60g 2 -正丁氧基乙醇中溶解87.5g 前述製造例 1 5之含有低極性側鏈之聚酿胺酸樹脂溶液和 5 0g前述製造例1 7之聚醯胺酸溶液,攪拌24小時,製得 黏度為2 5 c p s之溶液。 [實施例6 ]含有低極性側鏈的聚醯胺酸樹脂與聚醯胺 酸之混合物(BPAA-7)之製造 邊使氮氣慢慢地通過配置有攪拌機、氮氣注入裝置之 lOOOmL反應器,邊在作為稀釋溶劑之75 g N-甲基-2-毗咯 啶酮、120g r_ 丁内酯、60g2-正丁氧基乙醇中溶解337.3g 前述製造例 15之低極性側鏈之含有聚醯胺酸樹脂溶液和 50g前述製造例1 7之聚醯胺酸溶液,攪拌24小時,製得 黏度為2 5 c p s之溶液。 [實施例7 ]含有低極性側鏈的聚醯胺酸樹脂與聚醯胺 酸之混合物(BPAA-8)之製造 邊使氮氣慢慢地通過配置有攪拌機、氮氣注入裝置之 lOOOmL反應器,邊在作為稀釋溶劑之80g N-曱基-2-毗咯 啶酮、120g 丁内酯、60g2-正丁氧基乙醇中溶解0.765g 16 1275630 前述製造例1 6之含有低極性側鏈之聚醯胺酸樹脂溶液和 5 〇g前述製造例1 7之聚醯胺酸溶液,攪拌24小時’製得 黏度為2 5 c p s之溶液。 [實施例8 ]含有低極性側鏈的聚醯胺酸樹脂與聚醯胺 酸之混合物(BPAA-9)之製造While slowly passing nitrogen through a 100 mL reactor equipped with a stirrer and a nitrogen injection device, 80 g of N-methyl-2-pyrrolidone, 120 g of r-butyrolactone, and 60 g of 2 - 4·16 6 g of the polyamic acid resin solution containing the low-polarity side chain of the above-mentioned Production Example 15 and 50 g of the polyamic acid solution of the above-mentioned Production Example 7 were dissolved in butoxyethanol, and stirred for 24 hours. A solution with a viscosity of 25 cps was obtained. [Example 3] Production of a mixture of a polyamic acid resin and a polyaminic acid (BPAA-4) containing a low-polarity side chain while slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen gas injection device Dissolved in a solution of 75 g of N-methyl-2-pyrrolidone, 120 g of r-butyrolactone, and 60 g of 2-n-butoxyethanol as a diluent solvent. 15 1275630 16.073 g of the low-polarity side chain of the above-mentioned production example 15 The polyamic acid resin solution and 50 g of the polyamic acid solution of the above-mentioned Production Example 7 were stirred for 24 hours to obtain a solution having a viscosity of 25 cps. [Example 4] Production of a mixture of a polyamic acid resin and a polyaminic acid (BPAA-5) containing a low-polarity side chain, while allowing nitrogen gas to slowly pass through a 100 mL reactor equipped with a stirrer and a nitrogen gas injection device. Dissolving 3 7 · 5 0 3 g of the above-mentioned production example 15 in 75 g of N-methyl-2-pyrrolidone, 120 g of r-butyrolactone, and 60 g of 2-n-butoxyethanol as a diluent solvent The polyamic acid chain resin solution of the low polarity side chain and 50 g of the polyamic acid solution of the above-mentioned Production Example 7 were stirred for 24 hours to obtain a solution having a viscosity of 25 c ps. [Example 5] Production of a mixture of a polyamic acid resin and a polyaminic acid (BPAA-6) containing a low-polarity side chain while slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen gas injection device 87.5 g of the above-mentioned production example 15 having a low-polarity side chain was dissolved in 75 g of N-mercapto-2-pyrrolidone, 120 g of 7-butyrolactone, and 60 g of 2-n-butoxyethanol as a diluent solvent. A solution of the amino acid resin and 50 g of the polyamic acid solution of the above-mentioned Production Example 7 were stirred for 24 hours to obtain a solution having a viscosity of 25 cps. [Example 6] Production of a mixture of a polyamic acid resin and a polyaminic acid (BPAA-7) containing a low-polarity side chain while slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen gas injection device 337.3 g of the low-polarity side chain-containing polyamine contained in the above-mentioned Production Example 15 was dissolved in 75 g of N-methyl-2-pyrrolidone, 120 g of r-butyrolactone, and 60 g of 2-n-butoxyethanol as a diluent solvent. The acid resin solution and 50 g of the polyamic acid solution of the above-mentioned Production Example 7 were stirred for 24 hours to obtain a solution having a viscosity of 25 cps. [Example 7] Production of a mixture of a polyamic acid resin and a polyaminic acid (BPAA-8) containing a low-polarity side chain while slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen gas injection device Dissolve 0.765 g of 16 1275630 in 80 g of N-mercapto-2-pyrrolidone as a diluent solvent, 120 g of butyrolactone, and 60 g of 2-n-butoxyethanol. The polyfluorene-containing polyfluorene of the above-mentioned Production Example 16. The amino acid resin solution and 5 μg of the polyamic acid solution of the above-mentioned Production Example 7 were stirred for 24 hours to obtain a solution having a viscosity of 25 cps. [Example 8] Production of a mixture of a polyamic acid resin and a polyaminic acid (BPAA-9) containing a low-polarity side chain
邊使氮氣慢慢地通過配置有攪拌機、氮氣注入裝置之 lOOOmL反應器,邊在作為稀釋溶劑之80g N-甲基-2-吡咯 啶酮、120g 7 -丁内酯、60g2-正丁氧基己醇中溶解LMeg 前述製造例1 6之含有低極性側鏈之聚醯胺酸树月日溶液和 5 〇g前述製造例17之聚醯胺酸溶液,攪拌24小時,製得 黏度為25cps之溶液。 [實施例9 ]含有低極性側鏈的聚醯胺酸樹脂與聚醯胺 酸之混合物(BPAA-10)之製造 邊使氮氣慢慢地通過配置有攪拌機、敗氣注入裝置之 1000mL反應器,邊在作為稀釋溶劑之80gN -甲基-2-吡咯 咬酮、l2〇g 7-丁内酯、60g2 -正丁氧基乙醇中溶解々.bGg 前述製造例1 6之含有低極性側鏈之聚醯胺酸樹脂溶液和 5 〇g前述製造例1 7之聚醯胺酸溶液,攪拌24小時,製得 黏度為2 5 c p s之溶液。 [實施例1 0]含有低極性側鏈的聚感胺酸樹脂與聚醯 胺酸之混合物(BPAA-11)之製造While slowly passing nitrogen through a 100 mL reactor equipped with a stirrer and a nitrogen injection device, 80 g of N-methyl-2-pyrrolidone, 120 g of 7-butyrolactone, and 60 g of 2-n-butoxy group as a diluent solvent were used. LMeg was dissolved in hexan. The poly-proline lysate solution containing the low-polarity side chain of the above-mentioned Production Example 16 and 5 〇g of the polyamic acid solution of the above-mentioned Production Example 17 were stirred for 24 hours to obtain a viscosity of 25 cps. Solution. [Example 9] Production of a mixture of a polyamic acid resin and a polyaminic acid (BPAA-10) containing a low-polarity side chain, while allowing nitrogen gas to slowly pass through a 1000 mL reactor equipped with a stirrer and a gas injection device. Dissolving 々.bGg in 80 g of N-methyl-2-pyrrole ketone, l2 〇g 7-butyrolactone, and 60 g of 2-n-butoxyethanol as a diluent solvent, and the low-polarity side chain of the above-mentioned production example 16 The polyamic acid resin solution and 5 μg of the polyamic acid solution of the above-mentioned Production Example 7 were stirred for 24 hours to obtain a solution having a viscosity of 25 cps. [Example 1 0] Manufacture of a mixture of a poly (amino acid) resin and a polyaminic acid (BPAA-11) containing a low-polarity side chain
邊使氮氣慢慢地通過配置有攪拌機、氮氣注入裝置之 l〇〇〇mL反應器,邊在作為稀釋溶劑之75g N-甲基-2-吡咯 啶酮、120g 7-丁内g旨、6〇g2 -正丁氧基乙醇中溶解l6.〇5g 前述製造例1 6之含有低極性側鏈之聚醯胺酸樹脂溶液和 5〇g前述製造例17之聚醯胺酸溶液,攪拌24小時,製得 黏度為25cps之溶液。 [實施例11 ]含有低極性側鏈的聚醯胺酸樹脂與聚醯 胺酸之混合物(BPAA-12)之製造 邊使氮氣慢慢地通過配置有攪拌機、氛氣注入裝置之 10OOmL反應器,邊在作為稀釋溶劑之75g N -甲基-2·吡咯 啶酮、120g 7· 丁内酯、60g 2 -正丁氧基乙醇中溶解 17 1275630 37.5〇3g前述製造例16之含有低極性側鏈之聚醯胺酸樹脂 溶液和50g前述製造例1 7之聚醯胺酸溶液,攪拌24小時’ 製得黏度為2 5 c p s之溶液。 [實施例1 2 ]含有低極性側鏈的聚醯胺酸樹脂與聚酿 胺酸之混合物斤?八人-13)之製造While slowly passing nitrogen through a l〇〇〇mL reactor equipped with a stirrer and a nitrogen injection device, 75 g of N-methyl-2-pyrrolidone as a diluent solvent, 120 g of 7-butane, and 6 〇g2 - n-butoxyethanol dissolved l6. 〇 5g The polyamic acid resin solution containing the low polarity side chain of the above-mentioned production example 16 and 5 〇g of the polyamic acid solution of the above-mentioned production example 17 were stirred for 24 hours. A solution having a viscosity of 25 cps was prepared. [Example 11] Production of a mixture of a polyamic acid resin and a polyaminic acid (BPAA-12) containing a low-polarity side chain, while allowing nitrogen gas to slowly pass through a 10,000 mL reactor equipped with a stirrer and an atmosphere injection device. Dissolving 17 1275630 37.5 〇 3 g of the low-polarity side chain of the above-mentioned Production Example 16 in 75 g of N-methyl-2-pyrrolidone, 120 g of 7-butyrolactone, and 60 g of 2-n-butoxyethanol as a diluent solvent The polyamic acid resin solution and 50 g of the polyamic acid solution of the above-mentioned Production Example 7 were stirred for 24 hours to obtain a solution having a viscosity of 25 cps. [Example 1 2 ] A mixture of a polyamic acid resin having a low-polarity side chain and a poly-aracine acid? Manufacture of eight people-13)
邊使氮氣慢慢地通過配置有攪拌機、氮氣注入裝置之 lOOOmL反應器,邊在作為稀釋溶劑之75g N-甲基比洛 啶酮、120g r-丁内酯、60g2 -正丁氧基乙醇中溶解87.5g 前述製造例1 6之含有低極性側鏈之聚醯胺酸樹脂溶液和 5〇g前述製造例17之聚醯胺酸溶液,攪拌24小時’製得 黏度為2 5 c p卩之溶液。 [實施例1 3 ]含有低極性側鏈的聚醯胺酸樹脂與聚酿 胺酸之混合物(BPAA-14)之製造 邊使氮氣慢慢地通過配置有授拌機、氮氣注入裝置之 1000mL反應器,邊在作為稀釋溶劑之75g N-甲基比哈 啶酮、120g r-丁内酯、60g2 -正丁氧基乙醇中溶解337*3g 前述製造例1 6之含有低極性側鏈之聚醯胺酸樹脂溶液和 50g前述製造例1 7之聚醯胺酸溶液,攪拌24小時’製得 黏度為25cps之溶液。Nitrogen gas was slowly passed through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device while being used as a diluent solvent for 75 g of N-methylpirolone, 120 g of r-butyrolactone, and 60 g of 2-n-butoxyethanol. 87.5 g of the polyamic acid resin solution containing the low-polarity side chain of the above-mentioned Production Example 16 and 5 μg of the polyamic acid solution of the above-mentioned Production Example 17 were dissolved, and stirred for 24 hours to obtain a solution having a viscosity of 25 cp. . [Example 1 3] Production of a mixture of a polyamic acid resin containing a low-polarity side chain and a poly-aracine acid (BPAA-14) while passing nitrogen gas through a reaction of 1000 mL equipped with a mixer and a nitrogen injection device 337*3g of the low-polar side chain of the above-mentioned production example 16 was dissolved in 75 g of N-methylbihadone, 120 g of r-butyrolactone, and 60 g of 2-n-butoxyethanol as a diluent solvent. The proline resin solution and 50 g of the polyamic acid solution of the above-mentioned Production Example 7 were stirred for 24 hours to prepare a solution having a viscosity of 25 cps.
[比較例1 ]含有低極性側鏈的聚醯胺酸樹脂(PAA_1) 之製造 邊使氮氣慢慢地通過配置有攪拌機、氮氣注入裝置及 冷卻器之25 OmL反應器,邊在作為反應溶劑之N-甲基-2-毗哈β定酮中溶解9.15g (〇.〇2莫耳)之1-(3,5 -二胺苯基)-3-十八烧基-破珀醯亞胺(DA-IM-18)後,邊通過I氣邊慢慢 地加入固體狀的5.28g (〇·〇2莫耳)之5-(2,5_二氧四虱吹 喃)-3-甲基環己烷-1,2 -二羧酸二酐。此時,固體成分濃度 (solid content)固定在20重量%,邊保持反應溫度在〇°C以 下邊攪拌24小時,得到聚醯胺酸溶液(PAA-1)。 [比較例2]含有低極性側鏈的聚醯胺酸樹脂(PAA-2) 之製造 邊使氮氣慢慢地通過配置有攪拌機、氮氣注入裝置及 18 1275630 冷卻器之25OmL反應器,邊在作為反應溶劑之Ν·甲基-2-毗咯啶酮中溶解9.15g (0.02莫耳)之1-(3,5-二胺苯基)-3-十八烧基-號站醢亞胺(DA-IM-18)後,邊通過氛氣邊慢慢 地加入固體狀的3.92g (0.02莫耳)之1,2,3,4-環丁烷四羧 酸二野。此時,固體成分濃度(solid content)固定在20重 量% ’邊保持反應溫度在0 °C以下邊攪拌24小時,得到聚 醯胺酸溶液(PAA-2)。 [比較例3]聚醯胺酸(PAA-3)之製造 邊使氮氣慢慢地通過配置有攪拌機、氮氣注入裝置及 冷卻器之500mL反應器,邊在作為反應溶劑之N-甲基-2-毗咯啶綱中溶解19· 8g (0.1莫耳)之亞曱二苯胺後,邊通過 氮氣邊慢慢地加入固體狀的19.6g (0·1莫耳)之1,2,3,4-環 丁炫四幾酸二野。此時,固體成分漢度(solid content)固定 在1 5重量%,邊保持反應溫度在〇 以下邊攪拌3 6小時, 得到聚醯胺酸溶液(PAA-3)。 [比較例4]含有可溶性聚醯亞胺之聚醯胺酸(PAA-4) 的製造 邊使氮氣慢慢地通過配置有攪拌機、氮氣注入裝置及 冷卻器之500mL反應器,邊在作為稀釋溶劑之s〇g N-甲 基- 2-p比咯啶酮、i20g 7 -丁内酯、60g2-正丁氧基乙醇中 溶解5 0 g前述製造例1 7之聚醯胺酸樹脂和〇. 3 9 5 g前述製 造例1 8之可溶性聚醯亞胺溶液,攪拌24小時,製得黏度 為25cps之溶液。 [實驗例1 ] 將依照前述實施例1〜1 3及比較例1〜4所製得之溶 液,以0.05〜0.2微米厚度塗布於ITO玻璃板後,在230 °C 之溫度熱硬化3 0分鐘所得到之聚醯亞胺衍生物薄膜的物 性,如下述表1所示。 19 1275630 [表l] 區 分 成分(重量%) f寺性 組成物 PA A- 1 PAA-2 PAA-3 固有黏度*) 表面張力 鉛筆 (dL/g) (dyne/cm) 硬度 1 BPAA-2 5 95 1.10 37.6 5H 2 BPAA-3 10 90 0.86 37.2 4H 3 BPAA-4 30 70 0.74 36.8 3H 4 BPAA-5 50 50 0.56 36.5 3H 5 BPAA-6 30 70 0.43 36.4 3H 實 6 BPAA-7 90 10 0.34 36.4 1H 施 7 BPAA-8 2 98 1.38 37.6 5H 例 8 BPAA-9 5 95 1.16 37.1 5H 9 BPAA-1 0 10 90 0.94 36.2 4H 10 BPAA-1 1 30 70 0.86 36.3 4H 11 BPAA-12 50 50 0.76 36.3 3H 12 BPAA-13 30 70 0.58 36.3 3H 13 BPAA-1 4 90 10 0.49 36.3 2H 比 1 PAA-1 100 0.15 36.4 1H 較 2 PAA-2 100 0.2 36.3 2H 例 3 PAA-3 100 1.50 47.5 5H 4 SPAA SPI(5) :PAA3 (95) 1.26 36.6 1H *)使用NMP作為溶劑,在0.5g/dL濃度、30°C測定。 如前述表1所示,可以確認本發明有關之含有低極性 側鏈之聚醯胺酸樹脂全部係具有明亮南瓜色之透明樹 脂,具有固有黏度0.49〜1.38dL/g範圍,藉由溶劑澆鑄成 型前述樹脂具有非常優良的薄膜成形性及機械特性。 又,本發明有關之聚醯亞胺薄膜之鉛筆硬度為1H〜5 Η 範圍,平均在3 Η且均勻,比較例1、2及4則明顯地低落。 薄膜之表面張力,係隨著導入有琥珀醯亞胺側鏈基(導入有 含有亞胺環之環系側鏈基)之二胺的含量增加而顯示有減 少的傾向,顯示在36.2〜37.2dyne/cm之均勻值。 [實驗例2 ] 20 1275630 將前述實施例 1〜1 3 4 7 » 垃+ a 、田 J J及比較例1〜4所得到之溶液,徂 :在::,溶液黏度為20〜〜後,藉由薄膜 :[Comparative Example 1] Production of a polyamic acid resin (PAA_1) containing a low-polarity side chain, while slowly passing nitrogen gas through a 25 OmL reactor equipped with a stirrer, a nitrogen gas injection device, and a cooler, as a reaction solvent Dissolving 9.15 g of 1-(3,5-diaminophenyl)-3-octadecyl-spholeimide in N-methyl-2-pyha-β- ketone After (DA-IM-18), slowly add 5.28 g of solid (5,5-dioxanthene) to the solid. Cyclohexane-1,2-dicarboxylic dianhydride. At this time, the solid content was fixed at 20% by weight, and the reaction temperature was kept at 〇 ° C for 24 hours while maintaining the reaction temperature to obtain a polyaminic acid solution (PAA-1). [Comparative Example 2] Production of a polyamic acid resin (PAA-2) containing a low-polarity side chain while slowly passing nitrogen gas through a 25 OmL reactor equipped with a stirrer, a nitrogen gas injection device, and an 18 1275630 cooler 9.15 g (0.02 mol) of 1-(3,5-diaminophenyl)-3-octadecyl-sodium imine (dissolved in the reaction solvent) in methyl 2-pyrrolidone ( After DA-IM-18), a solid 3.92 g (0.02 mol) of 1,2,3,4-cyclobutanetetracarboxylic acid was added slowly through the atmosphere. At this time, the solid content was fixed at 20% by weight, and the reaction temperature was kept at 0 ° C or lower for 24 hours to obtain a polyaminic acid solution (PAA-2). [Comparative Example 3] Production of polyacrylic acid (PAA-3) while passing nitrogen gas slowly through a 500 mL reactor equipped with a stirrer, a nitrogen gas injection device, and a cooler, while using N-methyl-2 as a reaction solvent After dissolving 19·8 g (0.1 mol) of the hydrazine diphenylamine in the pyrrole group, 19.6 g (0.1 mol) of 1, 2, 3, 4 was slowly added to the solid by nitrogen gas. - Huan Ding Hyun four acid and two wild. At this time, the solid content of the solid content was fixed at 15% by weight, and the reaction temperature was maintained at 〇 for 3 hours while stirring to obtain a polyaminic acid solution (PAA-3). [Comparative Example 4] Production of polyaminic acid (PAA-4) containing soluble polyimine, while passing nitrogen gas slowly through a 500 mL reactor equipped with a stirrer, a nitrogen gas injection device, and a cooler, as a diluent solvent 〇 〇 N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N 3 9 5 g of the above-mentioned soluble polyimide solution of Production Example 18 was stirred for 24 hours to obtain a solution having a viscosity of 25 cps. [Experimental Example 1] The solutions prepared in accordance with the above Examples 1 to 13 and Comparative Examples 1 to 4 were applied to an ITO glass plate at a thickness of 0.05 to 0.2 μm, and then thermally cured at a temperature of 230 ° C for 30 minutes. The physical properties of the obtained polyimide film of the polyimide derivative are shown in Table 1 below. 19 1275630 [Table l] Component (% by weight) f Temple composition PA A-1 PAA-2 PAA-3 Intrinsic viscosity*) Surface tension pencil (dL/g) (dyne/cm) Hardness 1 BPAA-2 5 95 1.10 37.6 5H 2 BPAA-3 10 90 0.86 37.2 4H 3 BPAA-4 30 70 0.74 36.8 3H 4 BPAA-5 50 50 0.56 36.5 3H 5 BPAA-6 30 70 0.43 36.4 3H Real 6 BPAA-7 90 10 0.34 36.4 1H Shi 7 BPAA-8 2 98 1.38 37.6 5H Example 8 BPAA-9 5 95 1.16 37.1 5H 9 BPAA-1 0 10 90 0.94 36.2 4H 10 BPAA-1 1 30 70 0.86 36.3 4H 11 BPAA-12 50 50 0.76 36.3 3H 12 BPAA-13 30 70 0.58 36.3 3H 13 BPAA-1 4 90 10 0.49 36.3 2H Ratio 1 PAA-1 100 0.15 36.4 1H Compared to 2 PAA-2 100 0.2 36.3 2H Example 3 PAA-3 100 1.50 47.5 5H 4 SPAA SPI (5 : PAA3 (95) 1.26 36.6 1H *) Using NMP as a solvent, it was measured at a concentration of 0.5 g/dL at 30 °C. As shown in the above Table 1, it can be confirmed that all of the polyamic acid resins containing the low-polarity side chain of the present invention have a transparent pumpkin-colored transparent resin, and have an intrinsic viscosity of 0.49 to 1.38 dL/g, which is formed by solvent casting. The aforementioned resin has very excellent film formability and mechanical properties. Further, the pencil hardness of the polyimide film of the present invention was in the range of 1H to 5 ,, and the average was 3 Η and uniform, and the comparative examples 1, 2 and 4 were markedly lowered. The surface tension of the film tends to decrease as the content of the diamine introduced into the side chain of the amber quinone imine (the side chain group containing the ring of the imine ring introduced) is decreased, and it is shown in 36.2 to 37.2 dyne. A uniform value of /cm. [Experimental Example 2] 20 1275630 The solution obtained in the above Examples 1 to 1 3 4 7 » R + a, YJ J and Comparative Examples 1 to 4, 徂: at::, the solution viscosity was 20~~, borrowed By film:
Pm、25秒)來製得薄膜。隨後,藉由 .,)製成液晶晶胞後,測定前述所製得之液晶晶胞之^ 性’ νΌ果如以下表2所示。 、 使用目視藉由偏光顯微鏡觀察液晶之配向狀態,使用 結晶旋轉法(crystal rotation method^〗定各液晶晶胞之預 (pretilt angles) ’將邊改變Dc偏壓邊對液晶板測定電 容量所得到C-V hysteresis曲線之電容變化率為2〇%之處 當作為基準,求得在同一電容之電壓差來測定殘留電壓 (residual D.C) ° [表2] 區分 配向膜 預傾角 (度) VHR(%) R· D · C(mV) 摩擦前 摩擦後 (常溫) 實施例 1 BPAA-2 89.6 90.0 99.7 154 ^^ 實施例 2 BPAA-3 8 9.6 89.4 99.5 258 ' 實施例 3 BPAA-4 89.6 89.5 99.3 272 — ^' 實施例 4 BPAA-5 89.6 89.5 99.1 330 ' 實施例 5 BPAA-6 89.6 89.5 99.1 325 ' 實施例 6 BPAA-7 89.7 89.6 99.6 398 ' 實施例 7 BPAA-8 89.6 79.6 99.1 136 ^ 實施例 8 BPAA-9 89.3 88.8 99.6 89 實施例 9 BPAA- 1 0 89.8 90.0 99.5 134 ~ 實施例 10 BPAA- 1 1 89.4 89.5 9 9.4 170 ' 實施例 11 BPAA- 1 2 89.6 89.3 9 9.4 213 〜 實施例 12 BPAA-1 3 89.5 89.4 99.2 3 67 ^' 實施例 13 BPAA-14 89.3 89.5 99.9 3 95 ^〜 比較例 1 PAA-1 89.7 89.6 98.5 547 ' 比較例 2 PAA-2 89.2 89.4 98.8 5 16 ^' 比較例 3 PAA-3 7.3 4.9 97.1 65 8 ' 比較例 4 SPAA 90.0 70.3 97.5 260 ^' 如前表2所示,得知使用實施例1〜13所製得含有聚 醯胺酸(具有本發明有關之低極性側鏈)之聚醯胺酸混合級 21 1275630 成物所製得之液晶晶胞,顯示具有非常高的預傾角、電選 保持率,顯示具有優良的殘留電壓特性。 預傾角為90度程度,由於和比較例2(未含有結構中 含有低極性側鏈之聚醯胺酸)比較時大為增加,在摩擦後亦 保持平均8 9度以上之高預傾角,和含有可溶性聚醯亞胺 樹脂之比較例4比較時,可以得知可以改良特性。在常溫 之電壓保持率為9 9 · 1〜9 9 · 9 %範圍,都在9 9 %以上,和比較 例1〜4比較時,可以確認較為優良,特別是,和使用含有 可溶性聚醯亞胺之聚醯胺酸混合物組成物所製造之比較 例4比較時,結果顯示電壓保持率增加。又,含有聚醯胺 酸(具有低極性側鏈)之混合組成物,結果顯示其液晶晶胞 之殘留電壓顯示降低至89〜3 95mV。這和比較例1〜3比較 時,顯示明顯地降低,由此可以確認本發明之殘留電壓更 為優良。 因此,綜合前述實驗例1及實驗例2之結果而言,可 以確認本發明有關實施例1〜1 3之由式(1)所表示含有低極 性側鏈之聚醮胺酸樹脂與含有下式(2)所表示之聚醢胺酸 衍生物所混合而成的聚醯胺酸混合組成物,顯示所具有之 特性非常適合使用於垂直配向型TFT-TN及STN LCD用液 晶配向膜、以及液晶晶胞。 【圖式簡車說明】 第1圖係本發明之1-(3,5_二胺苯基)-3-十八烷基-琥拍醢亞 胺(DN-IM-18)之1H-NMR 譜。 第2圖係依照本發明製造例15所製得PAA-1之1H-NMR 譜。 第3圖係依照本發明製造例17所製得PAA_3之1H-NMR 譜。 第4圖係依照本發明實施例1和實施例7〜10所製得 BPAA-2和BPAA-8〜11之UV光譜,以及依照比較例2〜4 所製得PAA-2〜3和SPPA之UV光譜。 22Pm, 25 seconds) to make a film. Subsequently, after the liquid crystal cell was formed by . . . , the liquid crystal cell obtained by the above was measured as shown in Table 2 below. Observing the alignment state of the liquid crystal by a polarizing microscope using a polarizing microscope, and determining the capacitance of the liquid crystal panel by changing the Dc bias side by using a crystal rotation method (pretilt angles of each liquid crystal cell) When the capacitance change rate of the CV hysteresis curve is 2〇%, the voltage difference between the same capacitance is used as a reference to determine the residual voltage (residual DC) ° [Table 2] Area distribution to the film pretilt angle (degrees) VHR (%) R·D · C(mV) After pre-friction friction (normal temperature) Example 1 BPAA-2 89.6 90.0 99.7 154 ^^ Example 2 BPAA-3 8 9.6 89.4 99.5 258 'Example 3 BPAA-4 89.6 89.5 99.3 272 — ^' Example 4 BPAA-5 89.6 89.5 99.1 330 'Example 5 BPAA-6 89.6 89.5 99.1 325 'Example 6 BPAA-7 89.7 89.6 99.6 398 'Example 7 BPAA-8 89.6 79.6 99.1 136 ^ Example 8 BPAA-9 89.3 88.8 99.6 89 Example 9 BPAA- 1 0 89.8 90.0 99.5 134 ~ Example 10 BPAA- 1 1 89.4 89.5 9 9.4 170 'Example 11 BPAA- 1 2 89.6 89.3 9 9.4 213 ~ Example 12 BPAA- 1 3 89.5 89.4 99.2 3 67 ^' Example 13 BPAA-14 89.3 89.5 99.9 3 95 ^~ Comparative Example 1 PAA-1 89.7 89.6 98.5 547 'Comparative Example 2 PAA-2 89.2 89.4 98.8 5 16 ^' Comparative Example 3 PAA-3 7.3 4.9 97.1 65 8 ' Comparative Example 4 SPAA 90.0 70.3 97.5 260 ^' As shown in Table 2 above, it was found that the polyglycine mixed grade 21 1275630 containing the poly-proline (having the low-polarity side chain of the present invention) prepared in Examples 1 to 13 was obtained. The liquid crystal cell prepared by the object exhibits a very high pretilt angle and electroselective retention, and exhibits excellent residual voltage characteristics. The pretilt angle is about 90 degrees, and compared with Comparative Example 2 (not containing a structure having low polarity) The side chain poly-proline acid) is greatly increased in comparison, and maintains a high pretilt angle of an average of 89 degrees or more after rubbing, and can be improved when compared with Comparative Example 4 containing a soluble polyimine resin. . The voltage holding ratio at room temperature is in the range of 9 9 · 1 to 9 9 · 9 %, and all of them are above 9 %. When compared with Comparative Examples 1 to 4, it can be confirmed that it is excellent, in particular, and contains soluble poly When Comparative Example 4 produced by the amine polyamine amide mixture composition was compared, the results showed that the voltage holding ratio was increased. Further, a mixed composition containing polylysine (having a low-polarity side chain) showed that the residual voltage of the liquid crystal cell showed a decrease to 89 to 3 95 mV. When this was compared with Comparative Examples 1 to 3, the display was remarkably lowered, and it was confirmed that the residual voltage of the present invention was more excellent. Therefore, by combining the results of the above Experimental Example 1 and Experimental Example 2, it can be confirmed that the polyamic acid resin containing a low-polar side chain represented by the formula (1) of the present invention in relation to Examples 1 to 13 of the present invention contains the following formula (2) The polyglycine mixed composition obtained by mixing the poly-proline derivatives represented by the present invention is excellent in the properties of the liquid crystal alignment film for vertical alignment type TFT-TN and STN LCD, and liquid crystal. Unit cell. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a 1H-NMR of 1-(3,5-diaminophenyl)-3-octadecyl-succinimide (DN-IM-18) of the present invention. Spectrum. Fig. 2 is a 1H-NMR spectrum of PAA-1 obtained in Production Example 15 of the present invention. Fig. 3 is a 1H-NMR spectrum of PAA_3 prepared in accordance with Production Example 17 of the present invention. Fig. 4 is a UV spectrum of BPAA-2 and BPAA-8 to 11 prepared in accordance with Inventive Example 1 and Examples 7 to 10, and PAA-2 to 3 and SPPA prepared in accordance with Comparative Examples 2 to 4. UV spectrum. twenty two
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KR1020040087422A KR100559264B1 (en) | 2004-10-29 | 2004-10-29 | Composition of containing polyamic acid blends and liquid crystal alignment layer and cell using them |
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JP5077558B2 (en) * | 2007-02-15 | 2012-11-21 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
JP5071659B2 (en) * | 2007-02-22 | 2012-11-14 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
JP5293927B2 (en) * | 2007-02-26 | 2013-09-18 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
JP5105071B2 (en) * | 2007-02-27 | 2012-12-19 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
JP5013105B2 (en) * | 2007-03-06 | 2012-08-29 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
JP5088563B2 (en) * | 2007-03-07 | 2012-12-05 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
JP5013106B2 (en) * | 2007-03-16 | 2012-08-29 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
JP4905701B2 (en) * | 2007-05-18 | 2012-03-28 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
JP5156894B2 (en) * | 2007-09-13 | 2013-03-06 | 独立行政法人物質・材料研究機構 | Liquid crystal aligning agent, liquid crystal aligning film, manufacturing method thereof, and liquid crystal display element |
KR100927704B1 (en) | 2007-12-07 | 2009-11-18 | 제일모직주식회사 | Liquid crystal aligning agent, Liquid crystal aligning film containing this, Liquid crystal display containing this |
US8730437B2 (en) * | 2010-04-14 | 2014-05-20 | Chi Mei Corporation | Method for making a treated polymer for a liquid crystal alignment agent, the treated polymer made thereby, and liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element containing the treated polymer |
JP6841069B2 (en) * | 2016-04-28 | 2021-03-10 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film and its manufacturing method, and liquid crystal element |
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TW556029B (en) * | 2000-10-16 | 2003-10-01 | Nissan Chemical Ind Ltd | Aligning agent for liquid crystal for in-plane switching, liquid-crystal alignment film, and liquid-crystal display element |
KR100491944B1 (en) * | 2002-12-09 | 2005-05-30 | 한국화학연구원 | Polyimide derivatives with pendant imide group and method for preparing them |
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JP4260733B2 (en) | 2009-04-30 |
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