TWI637026B - Liquid crystal alignment treatment agent and liquid crystal display element using same - Google Patents

Abstract

本發明係關於提供可形成不會降低垂直配向力，提高UV照射後之應答速度的液晶配向膜之液晶配向處理劑、及具有由該液晶配向處理劑所得之液晶配向膜，使用無添加液晶聚合性化合物之液晶，進行與PSA方式之同樣處理，提高UV照射後之應答速度的液晶顯示元件。 The present invention relates to a liquid crystal alignment treatment agent which can form a liquid crystal alignment film which does not lower the vertical alignment force and increase the response speed after UV irradiation, and a liquid crystal alignment film obtained by the liquid crystal alignment treatment agent, using no added liquid crystal polymerization. A liquid crystal display element in which the liquid crystal of the compound is treated in the same manner as in the PSA method to increase the response speed after UV irradiation.

該液晶配向處理劑為含有以下(A)成分與(B)成分。(A)成分為選自聚醯胺酸及聚醯亞胺所成群之至少一種類的聚合物；(B)成分為聚縮合含有式(1)所示烷氧基矽烷及式(3)所示烷氧基矽烷的烷氧基矽烷而得之聚矽氧烷。 The liquid crystal alignment treatment agent contains the following components (A) and (B). The component (A) is a polymer selected from the group consisting of polylysine and polyimine; the component (B) is polycondensed and contains the alkoxydecane represented by the formula (1) and the formula (3) A polyoxyalkylene of the alkoxydecane of the alkoxydecane shown.

R¹Si(OR²)₃ (1) R ¹ Si(OR ² ) ₃ (1)

(R¹表示式(2)，R²表示碳原子數1~5的烷基) (R ¹ represents the formula (2), and R ² represents an alkyl group having 1 to 5 carbon atoms)

(Y¹為單鍵等，Y²為單鍵等，Y³為單鍵等，Y⁴為苯環等2價環狀基等，Y⁵為苯環等2價環狀基等，Y⁶為碳 數1~18的烷基等，n為0~4)。 (Y ¹ is a single bond or the like, Y ² is a single bond or the like, Y ³ is a single bond or the like, Y ⁴ is a divalent cyclic group such as a benzene ring, and Y ⁵ is a divalent cyclic group such as a benzene ring, etc., Y ⁶ It is an alkyl group having 1 to 18 carbon atoms, and n is 0 to 4).

R³Si(OR⁴)₃ (3) R ³ Si(OR ⁴ ) ₃ (3)

(R³為由丙烯酸基、丙烯醯氧基、甲基丙烯酸基、甲基丙烯醯氧基或苯乙烯基所取代之碳數1~30的烷基，R⁴為碳數1~5的烷基)。 (R ³ is an alkyl group having 1 to 30 carbon atoms which is substituted by an acrylic group, an acryloxy group, a methacryl group, a methacryloxy group or a styryl group, and R ⁴ is an alkane having 1 to 5 carbon atoms; base).

Description

液晶配向處理劑及使用其之液晶顯示元件 Liquid crystal alignment treatment agent and liquid crystal display element using same 發明所屬技術領域 Technical field of the invention

本發明係關於液晶配向處理劑、具有由前述液晶配向處理劑所得之液晶配向膜、及具有該液晶配向膜之液晶顯示元件。 The present invention relates to a liquid crystal alignment treatment agent, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element having the liquid crystal alignment film.

近年來，液晶顯示元件的顯示方式中，亦以垂直(VA)方式的液晶顯示元件為廣泛利用大畫面的液晶電視或高精細行動用途(數位照相機或行動電話之顯示部)等。VA方式中，已知有將欲控制液晶的倒方向之突起形成於TFT基板或彩色濾光片基板之MVA方式(Multi Vertical Alignment)，或於基板的ITO(銦．錫氧化物)電極上形成縫隙，藉由電場控制液晶之倒方向的PVA(Patterned Vertical Alignment)方式。 In recent years, in the display mode of a liquid crystal display element, a liquid crystal display element of a vertical (VA) type is a liquid crystal television or a high-definition mobile use (a display unit of a digital camera or a mobile phone) that widely uses a large screen. In the VA method, an MVA method (Multi Vertical Alignment) in which a projection in a reverse direction for controlling a liquid crystal is formed on a TFT substrate or a color filter substrate is known, or an ITO (indium tin oxide) electrode is formed on a substrate. The gap is a PVA (Patterned Vertical Alignment) method in which the liquid crystal is reversed by an electric field.

作為其他配向方式有PSA(Polymer sustained Alignment)方式。 As another alignment method, there is a PSA (Polymer sustained Alignment) method.

VA方式之中，亦以PSA方式為近年來受到注目之技術。該方式為，於液晶中添加光聚合性化合物，於 液晶面板之製作後，輸入電場，在液晶倒下之狀態下將紫外線(UV)照射在液晶面板上。其結果因聚合性化合物進行光聚合，液晶的配向方向被固定化，產生預傾角，提高應答速度。於構成液晶面板之單側電極上製作縫隙，於對向側的電極圖型即使未設定如MVA之突起或如PVA之縫隙的結構下，亦可起作用，得到製造簡略化或優良面板透過率作為其特徵。(參照專利文獻1)。 Among the VA methods, the PSA method is also a technology that has attracted attention in recent years. In this method, a photopolymerizable compound is added to the liquid crystal, and After the liquid crystal panel is fabricated, an electric field is input, and ultraviolet rays (UV) are irradiated onto the liquid crystal panel in a state where the liquid crystal is dropped. As a result, photopolymerization is carried out by the polymerizable compound, and the alignment direction of the liquid crystal is fixed, and a pretilt angle is generated to increase the response speed. A slit is formed on the one-side electrode constituting the liquid crystal panel, and the electrode pattern on the opposite side can function even if a protrusion such as an MVA protrusion or a gap such as a PVA is not provided, and the manufacturing is simplified or the panel transmittance is excellent. As its characteristics. (Refer to Patent Document 1).

然而，對於PSA方式之液晶顯示元件中，於液晶所添加之聚合性化合物的溶解性為低，若增加該添加量時，有著於低溫時會析出之問題。又，若減少聚合性化合物之添加量時，無法得到良好配向狀態及應答速度。且，殘留於液晶中之未反應聚合性化合物成為液晶中之不純物，亦會產生降低液晶顯示元件之信賴性的問題。 However, in the PSA type liquid crystal display device, the solubility of the polymerizable compound added to the liquid crystal is low, and when the amount is increased, there is a problem that precipitation occurs at a low temperature. Further, when the amount of the polymerizable compound added is reduced, a good alignment state and a response speed cannot be obtained. Further, the unreacted polymerizable compound remaining in the liquid crystal becomes an impurity in the liquid crystal, and also causes a problem of lowering the reliability of the liquid crystal display element.

因此，將使用於聚合物分子中導入光反應性側鏈的聚合物之液晶配向處理劑塗布於基板上，經燒成所得之液晶配向膜上設置經接觸之液晶層，於該液晶層上一邊外加電壓，一邊照射紫外線，而製作液晶顯示元件下，即使於液晶中未添加聚合性化合物，亦可得到應答速度快速的液晶顯示元件的技術已被提出(參照專利文獻2)。 Therefore, a liquid crystal alignment treatment agent for a polymer having a photoreactive side chain introduced into a polymer molecule is applied onto a substrate, and a contact liquid crystal layer is provided on the liquid crystal alignment film obtained by firing, and a liquid crystal layer is provided on the liquid crystal layer. A technique of obtaining a liquid crystal display element having a fast response speed even when a polymerizable compound is not added to the liquid crystal by applying a voltage to the liquid crystal display element is disclosed (see Patent Document 2).

另一方面，與自過去使用的聚醯亞胺等有機系液晶配向膜材料之同時，無機系液晶配向膜材料亦為已知。例如作為塗布型無機系液晶配向膜材料，已被提出含有四烷氧基矽烷、三烷氧基矽烷、醇與草酸之反應生成物之液晶配向劑組成物，在液晶顯示元件之電極基板上，形 成垂直配向性、耐熱性及均勻性優良的液晶配向膜(參照專利文獻3)。 On the other hand, an inorganic liquid crystal alignment film material is known as an organic liquid crystal alignment film material such as polyimine which has been used in the past. For example, as a coating-type inorganic liquid crystal alignment film material, a liquid crystal alignment agent composition containing a reaction product of a tetraalkoxy decane, a trialkoxy decane, an alcohol, and an oxalic acid has been proposed, and is formed on an electrode substrate of a liquid crystal display device. shape A liquid crystal alignment film having excellent vertical alignment, heat resistance, and uniformity (see Patent Document 3).

又，含有與四烷氧基矽烷、特定三烷氧基矽烷及水之反應生成物、及特定甘醇醚系溶劑之液晶配向處理劑組成物已被提出，其為可防止顯示不良，即使長時間之驅動後殘像特性亦良好，將液晶進行配向之能力不會降低，且可形成對於光及熱之電壓保持率的降低亦較少的液晶配向膜(參照專利文獻4)。 Further, a liquid crystal alignment treatment composition containing a reaction product of a tetraalkoxysilane, a specific trialkoxysilane, and water, and a specific glycol ether solvent has been proposed, and it is possible to prevent display defects even if it is long. After the driving of the time, the afterimage characteristics are also good, and the ability to align the liquid crystal is not lowered, and a liquid crystal alignment film having a small decrease in the voltage holding ratio of light and heat can be formed (see Patent Document 4).

[先行技術文獻] [Advanced technical literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2004-302061號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-302061

[專利文獻2]日本特開2011-95967號公報 [Patent Document 2] Japanese Laid-Open Patent Publication No. 2011-95967

[專利文獻3]日本特開平09-281502號公報 [Patent Document 3] Japanese Patent Laid-Open No. 09-281502

[專利文獻4]日本特開2005-250244號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2005-250244

對於進行垂直配向之VA模式，雖進行垂直配向時需要強力垂直配向力，但在未使用聚合性化合物之此方式中，若提高垂直配向力時，UV照射後之應答速度變慢，若提高UV照射後之應答速度時，垂直配向力會降低。垂直配向力與UV照射後之應答速度提高有權衡關係。 For the vertical alignment VA mode, a strong vertical alignment force is required for vertical alignment. However, in the case where the polymerizable compound is not used, if the vertical alignment force is increased, the response speed after UV irradiation becomes slow, and if UV is increased When the response speed after irradiation, the vertical alignment force is lowered. The vertical alignment force has a weighted relationship with the response speed after UV irradiation.

本發明的課題為提供使用未添加聚合性化合物之液晶，進行與PSA方式之相同處理，對於提高UV照射後之應答速度的方式之液晶顯示元件，亦可無降低垂直配向力下，可形成提高UV照射後之應答速度的液晶配向膜之液晶配向處理劑、由該液晶配向處理劑所得之液晶配向膜、及具有該液晶配向膜之液晶顯示元件。 An object of the present invention is to provide a liquid crystal display device in which the liquid crystal display element having the same processing as that of the PSA method is used, and the response speed after UV irradiation is increased, and the vertical alignment force can be increased without increasing the vertical alignment force. A liquid crystal alignment treatment agent for a liquid crystal alignment film having a response speed after UV irradiation, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element having the liquid crystal alignment film.

本發明者欲達成上述目的進行詳細研究結果，發現藉由含有選自聚醯胺酸及聚醯亞胺所成群之至少一種聚合物((A)成分)與特定聚矽氧烷((B)成分)的液晶配向處理劑可達成上述目的，而完成本發明。 The present inventors have conducted detailed studies to achieve the above object, and found that at least one polymer (component (A)) and a specific polyoxane (B) are selected by a group selected from the group consisting of polylysine and polyimine. The liquid crystal alignment treatment agent of the component) can achieve the above object, and the present invention has been completed.

即，本發明為具有以下主旨者。 That is, the present invention has the following subject matter.

1.一種液晶配向處理劑，其特徵為含有下述(A)成分及(B)成分，(A)成分：選自聚醯胺酸及聚醯亞胺所成群之至少一種類聚合物。 A liquid crystal alignment treatment agent comprising the following components (A) and (B), and component (A): at least one polymer selected from the group consisting of polyamic acid and polyimine.

(B)成分：將含有式(1)所示烷氧基矽烷及式(3)所示烷氧基矽烷的烷氧基矽烷進行聚縮合所得之聚矽氧烷。 (B) component: a polyoxyalkylene obtained by polycondensing an alkoxy decane containing an alkoxy decane represented by the formula (1) and an alkoxy decane represented by the formula (3).

R¹Si(OR²)₃ (1) R ¹ Si(OR ² ) ₃ (1)

(R¹為下述式(2)之結構，R²為碳原子數1~5的烷基)。 (R ¹ is a structure of the following formula (2), and R ² is an alkyl group having 1 to 5 carbon atoms).

(Y¹為單鍵、-(CH₂)_a-(a為1~15的整數)、-O-、-CH₂O-、-COO-或-OCO-。 (Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-.

Y²為單鍵、含有雙鍵之碳數3~8的直鏈狀或者分支狀的烴基、或-(CR¹⁷R¹⁸)_b-(b為1~15的整數，R¹⁷、R¹⁸各獨立為氫原子或碳數1~3的烷基)。 Y ² is a single bond, a linear or branched hydrocarbon group having a carbon number of 3 to 8 containing a double bond, or -(CR ¹⁷ R ¹⁸ ) _b - (b is an integer of 1 to 15, and R ¹⁷ and R ^{18 are} each Independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms).

Y³為單鍵、-(CH₂)_c-(c為1~15的整數)、-O-、-CH₂O-、-COO-或-OCO-。 Y ³ is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-.

Y⁴為選自苯環、環己基環、及雜環之2價環狀基，這些環狀基上之任意氫原子可由碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟烷基、碳數1~3的含氟烷氧基、或氟原子所取代。且，Y⁴可為具有類固醇骨架之碳數12~25的2價有機基。 Y ⁴ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring, and a hetero ring, and any hydrogen atom on the ring group may be an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom is substituted. Further, Y ⁴ may be a divalent organic group having a carbon number of 12 to 25 having a steroid skeleton.

Y⁵為選自苯環、環己基環及雜環所成群之2價環狀基，這些環狀基上之任意氫原子可由碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟烷基、碳數1~3的含氟烷氧基或氟原子所取代。 Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, and any hydrogen atom on the ring group may be an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms. The oxy group, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom are substituted.

Y⁶為氫原子或碳數1~18的烷基、碳數1~18的含氟烷基、碳數1~18的烷氧基或碳數1~18的含氟烷氧基。n為0~4的整數)。 Y ⁶ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. n is an integer from 0 to 4).

R³Si(OR⁴)₃ (3) R ³ Si(OR ⁴ ) ₃ (3)

(R³為可由丙烯酸基、丙烯醯氧基、甲基丙烯酸基、 甲基丙烯醯氧基或苯乙烯基所取代之碳數1~30的烷基，R⁴為碳數1~5的烷基)。 (R ³ is an alkyl group having 1 to 30 carbon atoms which may be substituted by an acrylic group, an acryloxy group, a methacryl group, a methacryloxy group or a styryl group, and R ⁴ is an alkane having 1 to 5 carbon atoms; base).

2.如上述1所記載之液晶配向處理劑(B)成分，其為將進一步含有下述式(4)所示烷氧基矽烷的烷氧基矽烷經聚縮合所得之聚矽氧烷。 2. The component of the liquid crystal alignment treatment agent (B) according to the above-mentioned item 1, which is obtained by polycondensation of an alkoxydecane further containing an alkoxydecane represented by the following formula (4).

(R⁵)_nSi(OR⁶)_4-n (4) (R ⁵ ) _n Si(OR ⁶ ) _4-n (4)

(式(4)中，R⁵為氫原子、或可由雜原子、鹵素原子、胺基、乙二醇氧基、巰基、異氰酸酯基、脲基所取代之碳原子數1~10的烴基。R⁶為碳原子數1~5的烷基，n為0~3的整數)。 (In the formula (4), R ⁵ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a hetero atom, a halogen atom, an amine group, an ethylene glycoloxy group, a decyl group, an isocyanate group or a urea group. ⁶ is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 3).

3.如上述2所記載的液晶配向處理劑，其中前述式(4)所示烷氧基矽烷為四甲氧基矽烷或四乙氧基矽烷。 3. The liquid crystal alignment treatment agent according to the above 2, wherein the alkoxydecane represented by the above formula (4) is tetramethoxynonane or tetraethoxysilane.

4.如上述1所記載的液晶配向處理劑，其中於(B)成分之聚矽氧烷的製造上所使用之全烷氧基矽烷中，使用2~20莫耳%的式(1)所示烷氧基矽烷，且使用5~80莫耳%的式(3)所示烷氧基矽烷。 4. The liquid crystal alignment treatment agent according to the above-mentioned item 1, wherein 2 to 20 mol% of the formula (1) is used in the peralkoxy decane used for the production of the polyoxane of the component (B). Alkoxydecane is used, and 5 to 80 mol% of the alkoxydecane represented by the formula (3) is used.

5.如上述2或3所記載的液晶配向處理劑，其中於(B)成分之聚矽氧烷的製造上所使用之全烷氧基矽烷中，使用10~90莫耳%的式(4)所示烷氧基矽烷。 5. The liquid crystal alignment treatment agent according to the above 2 or 3, wherein 10 to 90 mol% of the formula (4) is used in the peralkoxy decane used for the production of the polyoxane of the component (B). ) alkoxydecane shown.

6.如上述1~5中任一所記載的液晶配向處理劑，其中對於(A)成分之100質量份而言，含有以(B)成分所具有的矽原子之SiO₂換算值為0.5~80質量份的(B) 成分。 The liquid crystal alignment treatment agent according to any one of the above-mentioned items 1 to 5, wherein the SiO ₂ conversion value of the ruthenium atom contained in the component (B) is 0.5 to 100 parts by mass of the component (A). 80 parts by mass of the component (B).

7.如上述1~6中任一項所記載的液晶配向處理劑，其中進一步含有有機溶劑，在液晶配向處理劑中含有90~99質量%之該有機溶劑。 The liquid crystal alignment treatment agent according to any one of the above-mentioned, wherein the liquid crystal alignment treatment agent further contains an organic solvent, and the liquid crystal alignment treatment agent contains 90 to 99% by mass of the organic solvent.

8.一種液晶配向膜，其特徵為將如上述1~7中任一項所記載的液晶配向處理劑塗布於基板上，並經乾燥、燒成所得者。 8. A liquid crystal alignment film which is obtained by applying the liquid crystal alignment treatment agent according to any one of the above 1 to 7 to a substrate, and drying and baking.

9.如上述8所記載的液晶配向膜，其為前述燒成在溫度100~350℃下進行而形成。 9. The liquid crystal alignment film according to the above 8, wherein the baking is performed at a temperature of 100 to 350 °C.

10.如上述8或9所記載的液晶配向膜，其為燒成後之塗膜厚度為5~300nm。 10. The liquid crystal alignment film according to the above 8 or 9, which is a coating film having a thickness of 5 to 300 nm after firing.

11.一種液晶顯示元件，其特徵為具有如上述8~10中任一項所記載的液晶配向膜。 A liquid crystal display element comprising the liquid crystal alignment film according to any one of the above 8 to 10.

根據本發明為提供不會降低垂直配向力，可形成可提高UV照射後之應答速度的液晶配向膜之液晶配向處理劑、由該液晶配向處理劑所得之液晶配向膜、及具有該液晶配向膜，使用不添加聚合性化合物之液晶，進行與PSA方式之相同處理，提高UV照射後之應答速度的方式之液晶顯示元件。 According to the present invention, in order to provide a liquid crystal alignment treatment agent for a liquid crystal alignment film which can improve a response speed after UV irradiation, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal alignment film can be provided without lowering the vertical alignment force. A liquid crystal display device of a type that performs the same treatment as the PSA method and increases the response speed after UV irradiation, using a liquid crystal to which no polymerizable compound is added.

[實施發明之形態] [Formation of the Invention] <(A)成分：聚醯胺酸及/或聚醯亞胺> <(A) component: polyglycine and/or polyimine >

本發明的液晶配向處理劑中含有選自聚醯胺酸及聚醯亞胺所成群之至少一種類聚合物。該聚醯胺酸及聚醯亞胺之具體結構並無特別限定，例如可為公知液晶配向處理劑所含有之聚醯胺酸或聚醯亞胺。 The liquid crystal alignment treatment agent of the present invention contains at least one type of polymer selected from the group consisting of polyamic acid and polyimine. The specific structure of the polyamic acid and the polyimine is not particularly limited, and for example, it may be a polyamic acid or a polyimine contained in a known liquid crystal alignment treatment agent.

聚醯胺酸可藉由四羧酸或四羧酸之衍生物與二胺之(聚縮合)反應而容易獲得。 Polylysine can be easily obtained by a (polycondensation) reaction of a derivative of a tetracarboxylic acid or a tetracarboxylic acid with a diamine.

本發明所使用的(A)成分之聚醯胺酸及聚醯亞胺的製造方法並無特別限定。一般為將選自四羧酸或其衍生物所成群之1種或複數種所成的四羧酸成分與由1種或複數種二胺化合物所成二胺成分進行反應而得到聚醯胺酸。 The method for producing the polyamic acid and the polyimine of the component (A) used in the present invention is not particularly limited. Generally, a tetracarboxylic acid component selected from one or a plurality of tetracarboxylic acids or a derivative thereof is reacted with a diamine component derived from one or a plurality of diamine compounds to obtain a polyamine. acid.

且作為得到聚醯亞胺之方法，可使用將聚醯胺酸進行亞醯胺化之方法。 Further, as a method of obtaining a polyimine, a method of imidizing polylysine can be used.

此時，所得之聚醯胺酸可藉由原料之四羧酸成分與二胺成分之適宜選擇而成為單聚合物(均聚物)或共聚物(共聚物)。 In this case, the obtained polyglycolic acid can be a single polymer (homopolymer) or a copolymer (copolymer) by appropriately selecting a tetracarboxylic acid component and a diamine component of the raw material.

其中，所謂四羧酸或其衍生物為四羧酸、四羧酸二鹵化物或四羧酸二酐。其中，亦以四羧酸二酐因與二胺化合物之反應性高而較佳。 Among them, the tetracarboxylic acid or a derivative thereof is a tetracarboxylic acid, a tetracarboxylic acid dihalide or a tetracarboxylic dianhydride. Among them, tetracarboxylic dianhydride is also preferred because it has high reactivity with a diamine compound.

具體而言可舉出均苯四甲酸、2,3,6,7-萘四羧酸、1,2,5,6-萘四羧酸、1,4,5,8-萘四羧酸、2,3,6,7-蒽四羧酸、1,2,5,6-蒽四羧酸、3,3’,4,4’-聯苯基四羧酸、2,3,3’,4’-聯苯基四羧酸、雙(3,4-二羧基苯基)醚、3,3’,4,4’-二苯甲酮四羧酸、雙(3,4-二羧基苯基)碸、雙 (3,4-二羧基苯基)甲烷、2,2-雙(3,4-二羧基苯基)丙烷、1,1,1,3,3,3-六氟-2,2-雙(3,4-二羧基苯基)丙烷、雙(3,4-二羧基苯基)二甲基矽烷、雙(3,4-二羧基苯基)二苯基矽烷、2,3,4,5-吡啶四羧酸、2,6-雙(3,4-二羧基苯基)吡啶、2,2-雙〔4-(3,4-二羧基苯氧基)苯基〕丙烷、3,3’,4,4’-二苯基碸四羧酸、3,4,9,10-苝四羧酸、1,3-二苯基-1,2,3,4-環丁烷四羧酸、氧基二鄰苯二甲酸四羧酸、1,2,3,4-環丁烷四羧酸、1,2,3,4-環戊烷四羧酸、1,2,4,5-環己烷四羧酸、1,2,3,4-四甲基-1,2,3,4-環丁烷四羧酸、1,2-二甲基-1,2,3,4-環丁烷四羧酸、1,3-二甲基-1,2,3,4-環丁烷四羧酸、1,2,3,4-環庚烷四羧酸、2,3,4,5-四氫呋喃四羧酸、3,4-二羧基-1-環己基琥珀酸、2,3,5-三羧基環戊基乙酸、3,4-二羧基-1,2,3,4-四氫-1-萘琥珀酸、聯環〔3,3,0〕辛烷-2,4,6,8-四羧酸、聯環〔4,3,0〕壬烷-2,4,7,9-四羧酸、聯環〔4,4,0〕癸烷-2,4,7,9-四羧酸、聯環〔4,4,0〕癸烷-2,4,8,10-四羧酸、三環〔6.3.0.0<2,6>〕十一烷-3,5,9,11-四羧酸、1,2,3,4-丁烷四羧酸、聯環〔2,2,2〕辛-7-烯-2,3,5,6-四羧酸、四環〔6,2,1,1,0,2,7〕十二碳-4,5,9,10-四羧酸、等四羧酸。進一步可舉出這些四羧酸之二鹵化物或四羧酸之二酐等。 Specific examples thereof include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, and 1,4,5,8-naphthalenetetracarboxylic acid. 2,3,6,7-decanetetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxybenzene Base) 碸, double (3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-dual ( 3,4-Dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyloxane, bis(3,4-dicarboxyphenyl)diphenylnonane, 2,3,4,5 -pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane, 3,3 ',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4,9,10-decanetetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid , oxydiphthalic acid tetracarboxylic acid, 1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5- Cyclohexanetetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4- Cyclobutane tetracarboxylic acid, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4 ,5-tetrahydrofuran tetracarboxylic acid, 3,4-dicarboxy-1-cyclohexyl succinic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,2,3,4- Tetrahydro-1-naphthalene succinic acid, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic acid, bicyclo[4,3,0]nonane-2,4,7 , 9-tetracarboxylic acid, bicyclo[4,4,0]nonane-2,4,7,9-tetracarboxylic acid, bicyclic [4,4,0]decane-2,4,8,10-tetracarboxylic acid, tricyclo[6.3.0.0<2,6>]undecane-3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid, tetracyclo[6,2,1, 1,0,2,7]dodecyl-4,5,9,10-tetracarboxylic acid, isotetracarboxylic acid. Further, these dicarboxylic acid dihalides or tetracarboxylic acid dianhydrides and the like can be mentioned.

其中，由塗膜之透明性的觀點來看，以脂環式四羧酸、這些二酐或這些二羧酸二鹵化物為佳。特別以1,2,3,4-環丁烷四羧酸、2,3,5-三羧基環戊基乙酸、3,4-二羧基-1,2,3,4-四氫-1-萘琥珀酸、聯環〔3,3,0〕辛烷- 2,4,6,8-四羧酸、這些四羧酸的二鹵化物、或這些四羧酸的二酐為佳。 Among them, from the viewpoint of transparency of the coating film, an alicyclic tetracarboxylic acid, these dianhydrides or these dicarboxylic acid dihalides are preferred. Especially 1,2,3,4-cyclobutanetetracarboxylic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1- Naphthalene succinic acid, bicyclo[3,3,0]octane- 2,4,6,8-tetracarboxylic acid, a dihalide of these tetracarboxylic acids, or a dianhydride of these tetracarboxylic acids is preferred.

上述四羧酸或其衍生物可配合作為液晶配向膜時的液晶配向性、電壓保持特性、累積電荷等特性，使用1種類或混合2種類以上使用。 The above-mentioned tetracarboxylic acid or a derivative thereof can be used in combination with one type or a mixture of two or more types, such as liquid crystal alignment property, voltage holding property, and accumulated electric charge when it is used as a liquid crystal alignment film.

使用於聚醯胺酸之製造的二胺並無特別限定。具體可舉出p-伸苯基二胺、2,3,5,6-四甲基-p-伸苯基二胺、2,5-二甲基-p-伸苯基二胺、m-伸苯基二胺、2,4-二甲基-m-伸苯基二胺、2,5-二胺基甲苯、2,6-二胺基甲苯、2,5-二胺基酚、2,4-二胺基酚、3,5-二胺基酚、3,5-二胺基苯甲基醇、2,4-二胺基苯甲基醇、4,6-二胺基間苯二酚、4,4’-二胺基聯苯基、3,3’-二甲基-4,4’-二胺基聯苯基、3,3’-二甲氧基-4,4’-二胺基聯苯基、3,3’-二羥基-4,4’-二胺基聯苯基、3,3’-二羧基-4,4’-二胺基聯苯基、3,3’-二氟-4,4’-聯苯基、3,3’-三氟甲基-4,4’-二胺基聯苯基、3,4’-二胺基聯苯基、3,3’-二胺基聯苯基、2,2’-二胺基聯苯基、2,3’-二胺基聯苯基、4,4’-二胺基二苯基甲烷、3,3’-二胺基二苯基甲烷、3,4’-二胺基二苯基甲烷、2,2’-二胺基二苯基甲烷、2,3’-二胺基二苯基甲烷、4,4’-二胺基二苯基醚、3,3’-二胺基二苯基醚、3,4’-二胺基二苯基醚、2,2’-二胺基二苯基醚、2,3’-二胺基二苯基醚、4,4’-磺醯基二苯胺、3,3’-磺醯基二苯胺、雙(4-胺基苯基)矽烷、雙(3-胺基苯基)矽烷、二甲基-雙(4-胺基苯基)矽烷、二甲基-雙(3-胺基苯基)矽烷、4,4’-硫代二苯胺、3,3’-硫代二苯胺、4,4’-二胺基二 苯基胺、3,3’-二胺基二苯基胺、3,4’-二胺基二苯基胺、2,2’-二胺基二苯基胺、2,3’-二胺基二苯基胺、N-甲基(4,4’-二胺基二苯基)胺、N-甲基(3,3’-二胺基二苯基)胺、N-甲基(3,4’-二胺基二苯基)胺、N-甲基(2,2’-二胺基二苯基)胺、N-甲基(2,3’-二胺基二苯基)胺、4,4’-二胺基二苯甲酮、3,3’-二胺基二苯甲酮、3,4’-二胺基二苯甲酮、1,4-二胺基萘、2,2’-二胺基二苯甲酮、2,3’-二胺基二苯甲酮、1,5-二胺基萘、1,6-二胺基萘、1,7-二胺基萘、1,8-二胺基萘、2,5-二胺基萘、2,6-二胺基萘、2,7-二胺基萘、2,8-二胺基萘、1,2-雙(4-胺基苯基)乙烷、1,2-雙(3-胺基苯基)乙烷、1,3-雙(4-胺基苯基)丙烷、1,3-雙(3-胺基苯基)丙烷、1,4-雙(4胺基苯基)丁烷、1,4-雙(3-胺基苯基)丁烷、雙(3,5-二乙基-4-胺基苯基)甲烷、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(4-胺基苯基)苯、1,3-雙(4-胺基苯基)苯、1,4-雙(4-胺基苯甲基)苯、1,3-雙(4-胺基苯氧基)苯、4,4’-〔1,4-伸苯基雙(伸甲基)〕二苯胺、4,4’-〔1,3-伸苯基雙(伸甲基)〕二苯胺、3,4’-〔1,4-伸苯基雙(伸甲基)〕二苯胺、3,4’-〔1,3-伸苯基雙(伸甲基)〕二苯胺、3,3’-〔1,4-伸苯基雙(伸甲基)〕二苯胺、3,3’-〔1,3-伸苯基雙(伸甲基)〕二苯胺、1,4-伸苯基雙〔(4-胺基苯基)甲酮〕、1,4-伸苯基雙〔(3-胺基苯基)甲酮〕、1,3-伸苯基雙〔(4-胺基苯基)甲酮〕、1,3-伸苯基雙〔(3-胺基苯基)甲酮〕、1,4-伸苯基雙(4-胺基苯甲 酸酯)、1,4-伸苯基雙(3-胺基苯甲酸酯)、1,3-伸苯基雙(4-胺基苯甲酸酯)、1,3-伸苯基雙(3-胺基苯甲酸酯)、雙(4-胺基苯基)對苯二甲酸乙二酯、雙(3-胺基苯基)對苯二甲酸乙二酯、雙(4-胺基苯基)間苯二甲酸酯、雙(3-胺基苯基)間苯二甲酸酯、N,N’-(1,4-伸苯基)雙(4-胺基苯甲醯胺)、N,N’-(1,3-伸苯基)雙(4-胺基苯甲醯胺)、N,N’-(1,4-伸苯基)雙(3-胺基苯甲醯胺)、N,N’-(1,3-伸苯基)雙(3-胺基苯甲醯胺)、N,N’-雙(4-胺基苯基)對苯二甲醯胺、N,N’-雙(3-胺基苯基)對苯二甲醯胺、N,N’-雙(4-胺基苯基)間苯二甲醯胺、N,N’-雙(3-胺基苯基)間苯二甲醯胺、9,10-雙(4-胺基苯基)蒽、4,4’-雙(4-胺基苯氧基)二苯基碸、2,2’-雙〔4-(4-胺基苯氧基)苯基〕丙烷、2,2’-雙〔4-(4-胺基苯氧基)苯基〕六氟丙烷、2,2’-雙(4-胺基苯基)六氟丙烷、2,2’-雙(3-胺基苯基)六氟丙烷、2,2’-雙(3-胺基-4-甲基苯基)六氟丙烷、2,2’-雙(4-胺基苯基)丙烷、2,2’-雙(3-胺基苯基)丙烷、2,2’-雙(3-胺基-4-甲基苯基)丙烷、3,5-二胺基苯甲酸、2,5-二胺基苯甲酸、1,3-雙(4-胺基苯氧基)丙烷、1,3-雙(3-胺基苯氧基)丙烷、1,4-雙(4-胺基苯氧基)丁烷、1,4-雙(3-胺基苯氧基)丁烷、1,5-雙(4-胺基苯氧基)戊烷、1,5-雙(3-胺基苯氧基)戊烷、1,6-雙(4-胺基苯氧基)正己烷、1,6-雙(3-胺基苯氧基)正己烷、1,7-雙(4-胺基苯氧基)庚烷、1,7-(3-胺基苯氧基)庚烷、1,8-雙(4-胺基苯氧基) 辛烷、1,8-雙(3-胺基苯氧基)辛烷、1,9-雙(4-胺基苯氧基)壬烷、1,9-雙(3-胺基苯氧基)壬烷、1,10-(4-胺基苯氧基)癸烷、1,10-(3-胺基苯氧基)癸烷、1,11-(4-胺基苯氧基)十一烷、1,11-(3-胺基苯氧基)十一烷、1,12-(4-胺基苯氧基)十二烷、1,12-(3-胺基苯氧基)十二烷、1,3-雙(4-胺基苯乙基)尿素等芳香族二胺；雙(4-胺基環己基)甲烷、雙(4-胺基-3-甲基環己基)甲烷等脂環式二胺；1,3-二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基正己烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷、1,11-二胺基十一烷、1,12-二胺基十二烷、1,3-雙(3-胺基丙基)四甲基二矽氧烷等脂肪族二胺等。 The diamine used in the production of polyamic acid is not particularly limited. Specific examples thereof include p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m- Phenyldiamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2 , 4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoisophthalic acid Diphenol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4' -diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3, 3'-Difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3 , 3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3, 3'-Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diamino group Phenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyl diphenyl Aniline, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl-bis(4-aminophenyl)decane, dimethyl-bis(3-aminobenzene) Base) decane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'-diaminodiyl Phenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diamine Diphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl (3 , 4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine , 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2 , 2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diamino Naphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2 - bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-double ( 3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl- 4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-amine Phenyl) benzene, 1,3-double (4-Aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1, 4-phenylene bis(methyl)diphenylamine, 4,4'-[1,3-phenylenebis(methyl)diphenylamine, 3,4'-[1,4-phenylene Bis(methyl)diphenylamine, 3,4'-[1,3-phenylenebis(methyl)diphenylamine, 3,3'-[1,4-phenylene bis(extension) Methyl)]diphenylamine, 3,3'-[1,3-phenylenebis(methyl)diphenylamine, 1,4-phenylphenylbis[(4-aminophenyl)methanone] , 1,4-phenylphenylbis[(3-aminophenyl)methanone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylene Bis[(3-aminophenyl)methanone], 1,4-phenylene bis(4-aminobenzoic acid) Acid ester), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3-phenylene double (3-Aminobenzoic acid ester), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-amine Phenylphenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzamide) Amine, N,N'-(1,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzene Methionine), N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)terephthalic acid Amine, N,N'-bis(3-aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl)m-xylyleneamine, N,N'-double (3-aminophenyl)m-xylyleneamine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2, 2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methyl Phenyl) hexafluoro Propane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methyl Phenyl)propane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-amine Phenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-amine Phenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)-n-hexane, 1,6-bis (3- Aminophenoxy)n-hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1,8-bis (4- Aminophenoxy) Octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,9-bis(3-aminophenoxy) ) decane, 1,10-(4-aminophenoxy)decane, 1,10-(3-aminophenoxy)decane, 1,11-(4-aminophenoxy) Monoalkane, 1,11-(3-aminophenoxy)undecane, 1,12-(4-aminophenoxy)dodecane, 1,12-(3-aminophenoxy) An aromatic diamine such as dodecane or 1,3-bis(4-aminophenethyl)urea; bis(4-aminocyclohexyl)methane or bis(4-amino-3-methylcyclohexyl) An alicyclic diamine such as methane; 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diamino-n-hexane, 1,7 -diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane, 1, An aliphatic diamine such as 12-diaminododecane or 1,3-bis(3-aminopropyl)tetramethyldioxane.

其中由電氣特性、與聚矽氧烷之相溶性等觀點來看，使用3,5-二胺基苯甲酸、2,5-二胺基苯甲酸、1,3-雙(4-胺基苯乙基)尿素、1,3-雙(3-胺基丙基)四甲基二矽氧烷為佳。 Among them, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, and 1,3-bis(4-aminobenzene) are used from the viewpoints of electrical properties and compatibility with polyoxyalkylene oxide. Ethyl) urea, 1,3-bis(3-aminopropyl)tetramethyldioxane is preferred.

又，可舉出於二胺側鏈具有烷基、含氟烷基、芳香環、脂肪族環、雜環、或彼等所成的大環狀取代體之二胺。 Further, a diamine having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring or a large cyclic substituent formed by the diamine side chain may be mentioned.

具體可例示出下述式〔A1〕~〔A20〕所示二胺。 Specific examples thereof include diamines represented by the following formulas [A1] to [A20].

(R₁為碳數1以上22以下的烷基或含氟烷基)。 (R ₁ is an alkyl group having 1 or more and 22 or less carbon atoms or a fluorine-containing alkyl group).

(R₂為-COO-、-OCO-、-CONH-、-NHCO-、-CH₂-、-O-、-CO-、或-NH-，R₃為氫原子、碳數1以上22以下之烷基或含氟烷基)。 (R ₂ is -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO-, or -NH-, and R ₃ is a hydrogen atom, and the carbon number is 1 or more and 22 or less. Alkyl or fluoroalkyl).

(R₄為-O-、-OCH₂-、-CH₂O-、-COOCH₂-、或-CH₂OCO-，R₅為碳數1以上22以下之烷基、烷氧基、含氟烷基或含氟烷氧基)。 (R ₄ is -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ -, or -CH ₂ OCO-, and R ₅ is an alkyl group having 1 or more and 22 or less carbon atoms, an alkoxy group, or a fluorine-containing group Alkyl or fluoroalkoxy).

(R₆為-COO-、-OCO-、-CONH-、-NHCO-、-COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂-、或-CH₂-。R₇為碳數1以上22以下之烷基、烷氧基、含氟烷基或含氟烷氧基)。 (R ₆ is -COO -, - OCO -, - CONH -, - NHCO -, - COOCH 2 -, - CH 2 OCO -, - CH 2 O -, - OCH 2 -, or -CH ₂ -.R ₇ It is an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group having a carbon number of 1 or more and 22 or less.

(R₈為-COO-、-OCO-、-CONH-、-NHCO-、-COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂-、-CH₂-、-O-、或-NH-，R₉為氟基、氰基、三氟甲基、硝基、偶氮基、甲醯基、乙醯基、乙醯氧基、羥基、或羧基)。 (R ₈ is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ -, -O- Or -NH-, R ₉ is a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a decyl group, an ethyl group, an ethoxy group, a hydroxyl group, or a carboxyl group).

可進一步舉出如下述式〔A21〕所示之二胺基矽氧烷等。 Further, a diamine oxirane or the like represented by the following formula [A21] can be given.

(m為1~10的整數)。 (m is an integer from 1 to 10).

如上述之二胺可配合作為液晶配向膜時的液晶配向性、電壓保持特性、累積電荷等特性，使用1種類或混合2種類以上使用。 When the diamine is used as a liquid crystal alignment film, the properties such as liquid crystal alignment property, voltage holding property, and accumulated electric charge can be used, and it can be used in one type or in a mixture of two or more types.

上述聚醯胺酸之原料中，使用具有羥基或羧基之二胺時，可提高聚醯胺酸或聚醯亞胺與後記交聯性化合物之反應效率。 When a diamine having a hydroxyl group or a carboxyl group is used as the raw material of the polyamic acid, the reaction efficiency of the polyglycolic acid or the polyimine and the post-crosslinking compound can be improved.

作為如此二胺之具體例，可舉出2,5-二胺基酚、2,4-二胺基酚、3,5-二胺基酚、3,5-二胺基苯甲基醇、2,4-二胺 基苯甲基醇、3,3’-二羥基-4,4’-二胺基聯苯基、3,3’-二羧基-4,4’-二胺基聯苯基、3,5-二胺基苯甲酸、2,5-二胺基苯甲酸、式〔A22〕~〔A25〕所示二胺等。 Specific examples of such a diamine include 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, and 3,5-diaminobenzyl alcohol. 2,4-diamine Benzobenzyl alcohol, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,5- Diaminobenzoic acid, 2,5-diaminobenzoic acid, diamines of the formula [A22] to [A25], and the like.

(R₁₀為-COO-、-OCO-、-CONH-、-NHCO-、-CH₂-、-O-、-CO-、或-NH-)。 (R ₁₀ is -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO-, or -NH-).

(R₁₁為-COO-、-OCO-、-CONH-、-NHCO-、-COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂-、-CH₂-、-O-、或-NH-。R₁₂為羥基、或羧基)。 (R ₁₁ is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ -, -O- Or -NH-. R ₁₂ is a hydroxyl group or a carboxyl group).

作為使用於製造聚醯胺酸時的溶劑，僅為可溶解所生成之聚醯胺酸者即可，並無特別限定。若要舉出該具體例，可舉出N,N-二甲基甲醯胺、N,N-二甲基乙醯 胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-甲基己內醯胺、二甲基亞碸、四甲基尿素、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯、異丙基醇、甲氧基甲基戊醇、雙戊烯、乙基戊酮、甲基壬酮、甲基乙酮、甲基異戊酮、甲基異丙酮、甲基溶纖劑、乙基溶纖劑、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、丁基卡必醇、乙基卡必醇、乙二醇、乙二醇單乙酸酯、乙二醇單異丙基醚、乙二醇單丁基醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲基醚、丙二醇-tert-丁基醚、二丙二醇單甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲基醚、3-甲基-3-甲氧基丁醇、二異丙基醚、乙基異丁基醚、二異丁烯、戊基乙酸酯、丁基丁酸酯、丁基醚、二異丁酮、甲基環己烯、丙基醚、二己基醚、二噁烷、n-己烷、n-戊烷、n-辛烷、二乙基醚、環己酮、伸乙基碳酸酯、伸丙基碳酸酯、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁基酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙基酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙基酯、3-甲氧基丙酸丁基酯、二甘醇二甲醚、4-羥基-4-甲基-2-戊酮等。 The solvent used in the production of polyamic acid is not particularly limited as long as it can dissolve the produced polyamic acid. To cite this specific example, N,N-dimethylformamide, N,N-dimethylacetamidine can be mentioned. Amine, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl Azulene, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl pentanone, methyl fluorenone, methyl ethyl ketone, methyl isoamyl ketone, methyl Acetone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene Alcohol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl Ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether , 3-methyl-3-methoxybutanol, diisopropyl Ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, dioxins Alkane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethyl ecarbonate, propyl carbonate, methyl lactate, ethyl lactate, methyl acetate, Ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, two Glyme, 4-hydroxy-4-methyl-2-pentanone, and the like.

這些可單獨使用，亦可混合後使用。且，即 使為不溶解聚醯胺酸之溶劑，若在不會析出所生成之聚醯胺酸的範圍下，亦可混合於上述溶劑中使用。又，有機溶劑中之水分會阻礙聚合反應，進一步成為使所生成之聚醯胺酸進行水解之原因，故盡量將有機溶劑經脫水乾燥後使用為佳。 These can be used alone or in combination. And that is The solvent which does not dissolve the polyamic acid may be used in the above solvent in the range in which the produced polyamic acid is not precipitated. Further, since the water in the organic solvent hinders the polymerization reaction and further causes hydrolysis of the produced polylysine, it is preferred to use the organic solvent as it is after dehydration.

作為將製造聚醯胺酸時的四羧酸或者其衍生物與二胺在有機溶劑中使其反應之方法，可舉出將二胺於有機溶劑中分散或者溶解後之溶液經攪拌後，將四羧酸或者其衍生物直接，或於有機溶劑中分散或者溶解後添加之方法、相反地將四羧酸或者其衍生物分散或溶解於有機溶劑之溶液中添加二胺之方法、四羧酸或者其衍生物與二胺以交互方式添加之方法等。這些任一方法皆可。又，四羧酸或者其衍生物、或二胺係由複數種化合物所成時，可在預先混合之狀態下進行反應，亦可各別順序進行反應，進一步可將各別反應之低分子量體進行混合反應而成為高分子量體。 As a method of reacting a tetracarboxylic acid or a derivative thereof in the production of polyamic acid with an diamine in an organic solvent, a solution obtained by dispersing or dissolving a diamine in an organic solvent may be stirred. A method in which a tetracarboxylic acid or a derivative thereof is directly or dissolved in an organic solvent or dissolved, and a method in which a tetracarboxylic acid or a derivative thereof is dispersed or dissolved in an organic solvent to add a diamine, a tetracarboxylic acid Or a method in which a derivative thereof is added to a diamine in an interactive manner. Either of these methods is acceptable. Further, when the tetracarboxylic acid or a derivative thereof or the diamine is formed from a plurality of kinds of compounds, the reaction may be carried out in a state of being mixed beforehand, or the reaction may be carried out in a separate order, and the respective low molecular weight bodies may be further reacted. The mixed reaction is carried out to obtain a high molecular weight body.

合成聚醯胺酸時的溫度可選自-20~150℃之任意溫度，但較佳為-5~100℃之範圍。 The temperature at which the polyamic acid is synthesized may be selected from any temperature of from -20 to 150 ° C, but is preferably in the range of from -5 to 100 ° C.

又，反應可在任意濃度下進行。然而，若濃度過低時，取得高分子量之聚合物成為困難，濃度若高時，反應液之黏性會變的過高，均勻地攪拌成為困難，故較佳為1~50質量%，更佳為5~30質量%。反應初期在高濃度下進行，其後亦可追加有機溶劑。 Further, the reaction can be carried out at any concentration. However, when the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight. When the concentration is high, the viscosity of the reaction liquid is too high, and it is difficult to uniformly stir. Therefore, it is preferably 1 to 50% by mass. Good is 5~30% by mass. The initial stage of the reaction is carried out at a high concentration, and thereafter an organic solvent may be added.

有關聚醯胺酸之製造，對於四羧酸或者其衍生物之莫耳數，二胺成分之莫耳數比以0.8~1.2為佳，以0.9~1.1 為較佳。與一般聚縮合反應一樣，該莫耳比越接近1.0時，所生成之聚醯胺酸的分子量越大。 Regarding the manufacture of poly-proline, for the molar number of tetracarboxylic acid or its derivative, the molar ratio of the diamine component is preferably 0.8 to 1.2, and 0.9 to 1.1. It is better. As with the general polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the produced polyamine.

作為將聚醯胺酸進行亞醯胺化之方法，藉由加熱使其熱亞醯胺化，或使用觸媒之觸媒亞醯胺化為一般方式，但在比較低溫下，進行亞醯胺化反應之觸媒亞醯胺化的方式，因所得之聚醯亞胺的分子量較難引起降低故較佳。 As a method for the imidization of polylysine, it is thermally amidoxired by heating, or a catalyst is used for amidoximation in a general manner, but at a relatively low temperature, a decylamine is carried out. The mode of the catalyst imidization of the reaction is preferred because the molecular weight of the obtained polyimine is less likely to cause a decrease.

觸媒亞醯胺化可藉由將聚醯胺酸在有機溶劑中，在鹼性觸媒與酸酐之存在下進行攪拌而進行。此時的反應溫度為-20~250℃，較佳為0~180℃。反應溫度較高時，亞醯胺化可快速進行，但若過高時，聚醯亞胺之分子量會有降低之情況。鹼性觸媒之量為醯胺酸基之0.5~30莫耳倍，較佳為2~20莫耳倍，酸酐的量為醯胺酸基之1~50莫耳倍，較佳為3~30莫耳倍。鹼性觸媒或酸酐的量若少時，反應無法充分進行，又若過多時，反應終了後要完全地除去變的困難。 The catalyst imidization can be carried out by stirring the polyamic acid in an organic solvent in the presence of a basic catalyst and an acid anhydride. The reaction temperature at this time is -20 to 250 ° C, preferably 0 to 180 ° C. When the reaction temperature is high, the amidoximation can be rapidly carried out, but if it is too high, the molecular weight of the polyimide may be lowered. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group, and the amount of the anhydride is 1 to 50 moles of the amidate group, preferably 3 to 30 moles. When the amount of the basic catalyst or acid anhydride is small, the reaction does not proceed sufficiently, and if it is too large, it is difficult to completely remove the reaction after completion of the reaction.

作為鹼性觸媒，可舉出吡啶、三乙胺、三甲胺、三丁胺、三辛胺等，其中亦以吡啶因具有使反應進行時的適度鹼性故較佳。 Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has moderate alkalinity in the progress of the reaction.

又，作為酸酐，可舉出乙酸酐、偏苯三酸酐、均苯四甲酸酐等，其中若使用乙酸酐時，因反應終了後容易純化，故較佳。 Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. When acetic anhydride is used, it is preferred because it is easily purified after completion of the reaction.

作為觸媒亞醯胺化時的有機溶劑，僅為可溶解聚醯胺酸者即可，並無特別限定。若要舉出該具體例， 可舉出N,N’-二甲基甲醯胺、N,N’-二甲基乙醯胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-甲基己內醯胺、二甲基亞碸、四甲基尿素、二甲基碸、六甲基亞碸、γ-丁內酯等。藉由觸媒亞醯胺化之亞醯胺化率，可藉由調節觸媒量與反應溫度、反應時間而控制。 The organic solvent in the case of the imidization of the catalyst is not particularly limited as long as it can dissolve the polyamic acid. To cite this specific example, N,N'-dimethylformamide, N,N'-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylhexyl Indoleamine, dimethyl hydrazine, tetramethyl urea, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, and the like. The imidization ratio by the catalyst amidoximation can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

所生成之聚醯亞胺係由將上述反應溶液投入於弱溶劑中，回收生成之沈澱物而得。此時，所使用的弱溶劑並無特別限定。例如可舉出甲醇、丙酮、己烷、丁基溶纖劑、庚烷、甲基乙酮、甲基異丁酮、乙醇、甲苯、苯、水等。投入於弱溶劑而使其沈澱之聚醯亞胺，經過濾後，在常壓或者減壓下，常溫或者經加熱乾燥後可使其成為粉末。將該聚醯亞胺粉末，進一步溶解於有機溶劑，重複進行2~10次的再沈澱操作後，可純化聚醯亞胺。若一次沈澱回收操作無法除去不純物時，進行該純化步驟為佳。 The produced polyimine is obtained by charging the above reaction solution into a weak solvent and recovering the formed precipitate. At this time, the weak solvent to be used is not particularly limited. For example, methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, etc. are mentioned. The polyimine which is poured into a weak solvent and precipitated is filtered, and then dried under normal pressure or reduced pressure at room temperature or by heating to form a powder. The polyimine powder is further dissolved in an organic solvent, and the reprecipitation operation is repeated 2 to 10 times to purify the polyimine. This purification step is preferred if a single precipitation recovery operation cannot remove impurities.

本發明所使用的聚醯亞胺之分子量並無特別限定，由容易處理、膜形成時的特性之安定性的觀點來看，重量平均分子量以2,000~200,000為佳，較佳為4,000~50,000。分子量可藉由GPC(凝膠滲透層析法)求得。 The molecular weight of the polyimine used in the present invention is not particularly limited, and the weight average molecular weight is preferably 2,000 to 200,000, more preferably 4,000 to 50,000, from the viewpoint of ease of handling and stability of properties at the time of film formation. The molecular weight can be determined by GPC (gel permeation chromatography).

<(B)成分：聚矽氧烷> <(B) component: polyoxyalkylene>

本發明的液晶配向處理劑所含有之(B)成分係為將含有式(1)所示烷氧基矽烷及式(3)所示烷氧基矽烷之 烷氧基矽烷經聚縮合所得之聚矽氧烷。 The component (B) contained in the liquid crystal alignment agent of the present invention contains an alkoxydecane represented by the formula (1) and an alkoxydecane represented by the formula (3). A polyoxyalkylene obtained by polycondensation of an alkoxydecane.

R¹Si(OR²)₃ (1) R ¹ Si(OR ² ) ₃ (1)

(R¹為下述式(2)之結構，R²為碳原子數1~5的烷基)。 (R ¹ is a structure of the following formula (2), and R ² is an alkyl group having 1 to 5 carbon atoms).

R³Si(OR⁴)₃ (3) R ³ Si(OR ⁴ ) ₃ (3)

(R³為丙烯酸基、丙烯醯氧基、甲基丙烯酸基、甲基丙烯醯氧基、或苯乙烯基所取代之碳數1~30的烷基，R⁴為碳數1~5的烷基)。 (R ³ is an alkyl group having 1 to 30 carbon atoms which is substituted by an acrylic group, an acryloxy group, a methacryl group, a methacryloxy group or a styryl group, and R ⁴ is an alkane having 1 to 5 carbon atoms; base).

式(1)所示烷氧基矽烷的R¹(以下亦稱為特定有機基)為上述之式〔2〕所示結構。 R ¹ (hereinafter also referred to as a specific organic group) of the alkoxydecane represented by the formula (1) is a structure represented by the above formula [2].

式(2)中，Y¹為單鍵、-(CH₂)_a-(a為1~15的整數)、-O-、-CH₂O-、-COO-或-OCO-。其中，選擇單鍵、-(CH₂)_a-(a為1~15的整數)、-O-、-CH₂O-或-COO-由容易側鏈結構之合成的觀點為佳。其中亦已選擇單鍵、-(CH₂)_a-(a為1~10的整數)、-O-、-CH₂O-或-COO-為較佳。 In the formula (2), Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferred from the viewpoint of easy synthesis of a side chain structure. Among them, a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or -COO- is also preferred.

Y²為單鍵、含有雙鍵之碳數3~8的直鏈狀或者分支狀的烴基、或-(CR¹⁷R¹⁸)_b-(b為1~15的整數，R¹⁷、R¹⁸各獨立為氫原子或碳數1~3的烷基)。其中，由可使液晶顯示元件之應答速度能顯著地改善的觀點來 看，以-(CH₂)_b-(b為1~10的整數)為佳。 Y ² is a single bond, a linear or branched hydrocarbon group having a carbon number of 3 to 8 containing a double bond, or -(CR ¹⁷ R ¹⁸ ) _b - (b is an integer of 1 to 15, and R ¹⁷ and R ^{18 are} each Independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). Among them, from the viewpoint that the response speed of the liquid crystal display element can be remarkably improved, -(CH ₂ ) _b - (b is an integer of 1 to 10) is preferable.

Y³為單鍵、-(CH₂)_c-(c為1~15的整數)、-O-、-CH₂O-、-COO-或-OCO-。其中，亦以選擇單鍵、-(CH₂)_c-(c為1~15的整數)、-O-、-CH₂O-、-COO-或-OCO-時，由容易側鏈結構之合成的觀點來看為佳。其中亦以選擇單鍵、-(CH₂)_c-(c為1~10的整數)、-O-、-CH₂O-、-COO-或-OCO-為較佳。 Y ³ is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Wherein, when a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- is selected, the structure is easy to be side chain The point of view of synthesis is better. Among them, a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O-, -COO- or -OCO- is preferred.

Y⁴為選自苯環、環己烷環及雜環所成群之2價環狀基，這些環狀基上的任意氫原子可由碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟烷基、碳數1~3的含氟烷氧基或氟原子所取代。且Y⁴可為選自具有類固醇骨架之碳數12~25的有機基的2價有機基。其中亦以具有苯環、環己烷環或類固醇骨架中任一者的碳數12~25的有機基為佳。 Y ⁴ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring, and any hydrogen atom on the ring group may be an alkyl group having 1 to 3 carbon atoms and a carbon number of 1 to 3 The alkoxy group, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom are substituted. And Y ⁴ may be a divalent organic group selected from an organic group having a carbon number of 12 to 25 having a steroid skeleton. Among them, an organic group having 12 to 25 carbon atoms which has any one of a benzene ring, a cyclohexane ring or a steroid skeleton is preferred.

Y⁵為選自苯環、環己烷環及雜環所成群之環狀基，這些環狀基上的任意氫原子可由碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟烷基、碳數1~3的含氟烷氧基或氟原子所取代。 Y ⁵ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on the ring group may be an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. The group is substituted with a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom.

n為0~4的整數。較佳為0~2的整數。 n is an integer from 0 to 4. Preferably, it is an integer of 0-2.

Y⁶為碳數1~18的烷基、碳數1~18的含氟烷基、碳數1~18的烷氧基或碳數1~18的含氟烷氧基。其中以碳數1~18的烷基、碳數1~10的含氟烷基、碳數1~18的烷氧基或碳數1~10的含氟烷氧基為佳。較佳為碳數1~12的烷基或碳數1~12的烷氧基。更佳為碳數1 ~9的烷基或碳數1~9的烷氧基。 Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferred. It is preferably an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. More preferably, it is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

使用導入如此側鏈與光反應性基之聚矽氧烷的液晶配向處理劑時，為何可兼具應答速度特性與良好垂直配向性之理由雖無定案，但因使用具有與液晶骨架類似的結構之側鏈時，推定可兼具一般為權衡關係之應答速度與垂直配向性。 When a liquid crystal alignment agent which introduces such a side chain and a photoreactive group of a polyoxyalkylene is used, the reason why the response speed characteristic and the good perpendicular alignment property are both provided is not fixed, but a structure similar to the liquid crystal skeleton is used. In the case of the side chain, the estimation can have both the response speed and the vertical alignment of the trade-off relationship.

作為式(2)中之Y¹、Y²、Y³、Y⁴、Y⁵、Y⁶及n的較佳組合，可舉出與國際公開公報WO2011/132751(2011.10.27公開)之第13頁~34頁的表6~表47所揭示的(2-1)~(2-629)之相同組合。且，在國際公開公報之各表中，作為本發明中之Y¹~Y⁶雖作為Y1~Y6表示，但Y1~Y6以Y¹~Y⁶表示。 Preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula (2) include the 13th of the International Publication WO2011/132751 (2011.10.27 publication) The same combination of (2-1) to (2-629) disclosed in Tables 6 to 47 of the page on page 34. Further, in each table of the international publication, Y ¹ to Y ^{6 are} represented by Y1 to Y6 in the present invention, but Y1 to Y6 are represented by Y ¹ to Y ⁶ .

式(1)所示烷氧基矽烷的R²為碳原子數1~5，較佳為1~3的烷基。更佳為R²為甲基或乙基。 R ² of the alkoxydecane represented by the formula (1) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. More preferably, R ² is a methyl group or an ethyl group.

如此式(1)所示烷氧基矽烷可藉由公知方法(日本特開昭61-28639號公報)製造。 The alkoxydecane represented by the formula (1) can be produced by a known method (JP-A-61-28639).

以下舉出該具體例，但並未限定於此。 The specific example is given below, but is not limited thereto.

(R⁵為-O-、-OCH₂-、-CH₂O-、-COOCH₂-或-CH₂OCO-，R⁶為碳數1~22的烷基、烷氧基、含氟烷基或含氟烷氧基)。 (R ⁵ is -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, and R ⁶ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, or a fluorine-containing alkyl group Or a fluorine-containing alkoxy group).

(R⁷為單鍵、-COO-、-OCO-、-COOCH₂-、-CH₂OCO-、-(CH₂)_nO-(n為1~5的整數)、-OCH₂-或-CH₂-，R⁸為碳數1~22的烷基、烷氧基、含氟烷基或含氟烷氧基)。 (R ⁷ is a single bond, -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -(CH ₂ ) _n O- (n is an integer of 1 to 5), -OCH ₂ - or - CH ₂ -, R ⁸ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group).

(R⁹為-COO-、-OCO-、-COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂-、-CH₂-或-O-，R¹⁰為氟基、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)。 (R ⁹ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ - or -O-, R ¹⁰ is a fluorine group, cyanide Base, trifluoromethyl, nitro, azo, formyl, ethyl, ethoxy or hydroxy).

(R¹¹為碳數3~12的烷基，1,4-環伸己基的順-反異 構性各為反式異構物)。 (R ¹¹ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of each of the 1,4-cyclohexyl groups is a trans isomer).

(R¹²為碳數3~12的烷基，1,4-環伸己基的順-反異構性各為反式異構物)。 (R ¹² is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of the 1,4-cyclohexyl group is a trans isomer).

(B₄為可被氟原子取代之碳數3~20的烷基，B₃為1,4-環伸己基或1,4-伸苯基。 (B ₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, and B ₃ is a 1,4-cyclohexyl group or a 1,4-phenylene group.

B₂為氧原子或-COO-*(但，附有「*」之結合鍵為與B₃結合)，B₁為氧原子或-COO-*(但，附有「*」之結合鍵為與(CH₂)a₂)結合)。 B ₂ is an oxygen atom or -COO-* (however, the bond with "*" is bonded to B ₃ ), and B ₁ is an oxygen atom or -COO-* (however, the bond with "*" is Combined with (CH ₂ )a ₂ )).

又，a₁為0或1的整數，a₂為2~10的整數，a₃為0或1的整數)。 Further, a ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1.

上述烷氧基矽烷可配合作為矽氧烷聚合物時對溶劑之溶解性、作為液晶配向膜時中的液晶配向性、預傾角角特性、電壓保持率、累積電荷等特性，使用1種類或混合2種類以上使用。又，亦可能併用含有碳數10~18之長鏈烷基的烷氧基矽烷。 The alkoxydecane may be used in combination with a solubility in a solvent as a siloxane polymer, a liquid crystal alignment property in a liquid crystal alignment film, a pretilt angle characteristic, a voltage holding ratio, and an accumulated electric charge. More than 2 types are used. Further, it is also possible to use an alkoxydecane having a long-chain alkyl group having 10 to 18 carbon atoms in combination.

具有上述特定有機基之式(1)所示烷氧基矽烷對於欲得到聚矽氧烷使用的全烷氧基矽烷中，欲得到良好液晶配向性，以1莫耳%以上為佳。較佳為1.5莫耳%以上。更佳為2莫耳%以上。又，欲得到所形成之液晶配向膜的充分硬化特性，以30莫耳%以下為佳。較佳為25莫耳%以下。更佳為20莫耳%以下。 The alkoxydecane represented by the formula (1) having the above specific organic group is preferably 1 mol% or more in order to obtain a good liquid crystal alignment property in the peralkyl alkane to be used for obtaining a polyoxyalkylene. It is preferably 1.5 mol% or more. More preferably 2 mol% or more. Further, in order to obtain sufficient curing properties of the formed liquid crystal alignment film, it is preferably 30 mol% or less. It is preferably 25 mol% or less. More preferably, it is 20 mol% or less.

式(3)所示烷氧基矽烷的R³(以下亦稱為第二特定有機基)為由丙烯酸基、丙烯醯氧基、甲基丙烯酸基、甲基丙烯醯氧基或苯乙烯基所取代之烷基。所取代之氫原子為1個以上，較佳為1個。烷基之碳原子數以1~30為佳，較佳為1~20。更佳為1~10。 R ³ (hereinafter also referred to as a second specific organic group) of the alkoxydecane represented by the formula (3) is an acrylic group, an acryloxy group, a methacryl group, a methacryloxy group or a styryl group. Substituted alkyl. The number of hydrogen atoms to be substituted is one or more, preferably one. The alkyl group preferably has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. More preferably 1~10.

式(3)所示烷氧基矽烷的R⁴為碳數1~5的烷基，較佳為碳數1~3的烷基，特佳為碳數1~2的烷基。 R ⁴ of the alkoxydecane represented by the formula (3) is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, particularly preferably an alkyl group having 1 to 2 carbon atoms.

雖舉出式(3)所示烷氧基矽烷之具體例，但並未限定於此等。例如可舉出3-甲基丙烯氧基丙基三乙氧基矽烷、甲基丙烯氧基甲基三甲氧基矽烷、甲基丙烯氧基甲基三乙氧基矽烷、3-丙烯氧基丙基三甲氧基矽烷、3-丙烯氧基丙基三乙氧基矽烷、丙烯氧基乙基三甲氧基矽烷、丙烯氧基乙基三乙氧基矽烷、苯乙烯基乙基三甲氧基矽烷、苯乙烯基乙基三乙氧基矽烷、3-(N-苯乙烯基甲基-2-胺基乙基胺基)丙基三甲氧基矽烷等。其中亦以3-甲基丙烯氧基丙基三甲氧基矽烷、乙烯基三甲氧基矽烷、或苯乙烯基乙基三甲氧基矽烷為佳。 Although a specific example of the alkoxydecane represented by the formula (3) is given, it is not limited thereto. For example, 3-methacryloxypropyl triethoxy decane, methacryloxymethyl trimethoxy decane, methacryloxymethyl triethoxy decane, 3- propyleneoxy propylene Trimethoxy decane, 3-propenyloxypropyl triethoxy decane, propylene oxyethyl trimethoxy decane, propylene oxyethyl triethoxy decane, styryl ethyl trimethoxy decane, Styrylethyltriethoxydecane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxydecane, and the like. Among them, 3-methacryloxypropyltrimethoxydecane, vinyltrimethoxydecane, or styrylethyltrimethoxydecane is preferred.

在(B)成分為聚矽氧烷的製造中，除式 (1)所示烷氧基矽烷及式(3)所示烷氧基矽烷以外，將與基板之密著性提高、與液晶分子之親和性改善等作為目的，僅不損害本發明之效果下，可使用下述式(4)所示烷氧基矽之一種或複數種。 In the manufacture of (B) component polyaerocycloxane, In addition to the alkoxydecane represented by the formula (1) and the alkoxydecane represented by the formula (3), the adhesion to the substrate is improved, the affinity with the liquid crystal molecules is improved, and the like, and the effect of the present invention is not impaired. One or a plurality of alkoxy hydrazines represented by the following formula (4) can be used.

式(4)所示烷氧基矽烷可賦予聚矽氧烷種種特性，對應必要特性，可選擇一種或複數種使用。 The alkoxydecane represented by the formula (4) can impart various properties to the polyoxane, and one or more kinds can be selected depending on the necessary characteristics.

(R⁵)_nSi(OR⁶)_4-n (4) (R ⁵ ) _n Si(OR ⁶ ) _4-n (4)

(R⁵為可由氫原子、或雜原子、鹵素原子、胺基、乙二醇氧基、巰基、異氰酸酯基、脲基所取代之碳原子數1~10的烴基。R⁶為碳原子數1~5，較佳為1~3的烷基。n為0~3，較佳為0~2的整數)。 (R ⁵ is a hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a hydrogen atom, or a hetero atom, a halogen atom, an amine group, an ethylene glycoloxy group, a decyl group, an isocyanate group or a urea group. R ⁶ is a carbon atom number 1 ~5, preferably an alkyl group of 1 to 3. n is 0 to 3, preferably an integer of 0 to 2.)

式(4)所示烷氧基矽烷的R⁵為氫原子或碳原子數為1~10的有機基(以下亦稱為第三有機基)。作為第三有機基之例子，可含有脂肪族烴；如脂肪族環、芳香族環、雜環之環結構；不飽和鍵；氧原子、氮原子、硫原子等雜原子等，亦可具有分支結構之碳原子數為1~6的有機基。且該有機基可由鹵素原子、胺基、乙二醇氧基、巰基、異氰酸酯基、脲基等所取代。 R ⁵ of the alkoxydecane represented by the formula (4) is a hydrogen atom or an organic group having 1 to 10 carbon atoms (hereinafter also referred to as a third organic group). Examples of the third organic group may include an aliphatic hydrocarbon; a ring structure such as an aliphatic ring, an aromatic ring or a heterocyclic ring; an unsaturated bond; a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom, or the like, and may have a branch The organic group having a carbon number of 1 to 6 in the structure. Further, the organic group may be substituted by a halogen atom, an amine group, an ethylene glycoloxy group, a decyl group, an isocyanate group, a urea group or the like.

雖舉出式(4)所示烷氧基矽烷之具體例，但並未限定於此等。例如可舉出3-(2-胺基乙基胺基丙基)三甲氧基矽烷、3-(2-胺基乙基胺基丙基)三乙氧基矽烷、2-胺基乙基胺基甲基三甲氧基矽烷、2-(2-胺基乙基硫乙基)三乙氧基矽烷、3-巰基丙基三乙氧基矽烷、巰基甲基三甲氧基矽烷、乙烯基三乙氧基矽烷、3-異氰酸酯丙 基三乙氧基矽烷、三氟丙基三甲氧基矽烷、氯丙基三乙氧基矽烷、溴丙基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、二甲基二乙氧基矽烷、二甲基二甲氧基矽烷、二乙基二乙氧基矽烷、二乙基二甲氧基矽烷、二苯基二甲氧基矽烷、二苯基二乙氧基矽烷、3-胺基丙基甲基二乙氧基矽烷、3-胺基丙基二甲基乙氧基矽烷、三甲基乙氧基矽烷、三甲基甲氧基矽烷、γ-脲基丙基三乙氧基矽烷、γ-脲基丙基三甲氧基矽烷、γ-脲基丙基三丙氧基矽烷等。 Although a specific example of the alkoxy decane represented by the formula (4) is given, it is not limited thereto. For example, 3-(2-aminoethylaminopropyl)trimethoxydecane, 3-(2-aminoethylaminopropyl)triethoxydecane, 2-aminoethylamine can be mentioned. Methyltrimethoxydecane, 2-(2-aminoethylthioethyl)triethoxydecane, 3-mercaptopropyltriethoxydecane, mercaptomethyltrimethoxydecane, vinyl triethyl Oxydecane, 3-isocyanate C Triethoxy decane, trifluoropropyltrimethoxydecane, chloropropyltriethoxydecane, bromopropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, dimethyldiethoxy Base decane, dimethyl dimethoxy decane, diethyl diethoxy decane, diethyl dimethoxy decane, diphenyl dimethoxy decane, diphenyl diethoxy decane, 3- Aminopropylmethyldiethoxydecane, 3-aminopropyldimethylethoxydecane, trimethylethoxydecane, trimethylmethoxydecane, γ-ureidopropyltriethyl Oxydecane, γ-ureidopropyltrimethoxydecane, γ-ureidopropyltripropoxydecane, and the like.

對於式(4)所示烷氧基矽烷，有n為0之烷氧基矽烷，係四烷氧基矽烷。四烷氧基矽烷因與式(1)及(3)所示烷氧基矽烷容易縮合，故欲得到本發明之聚矽氧烷時為佳。 For the alkoxydecane represented by the formula (4), there is an alkoxydecane wherein n is 0, which is a tetraalkoxydecane. Since the tetraalkoxydecane is easily condensed with the alkoxydecane represented by the formulae (1) and (3), it is preferred to obtain the polyoxyalkylene of the present invention.

對於如此式(4)，作為n為0之烷氧基矽烷，以四甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷或四丁氧基矽烷為較佳，特別以四甲氧基矽烷或四乙氧基矽烷為佳。 For the above formula (4), as the alkoxydecane wherein n is 0, tetramethoxynonane, tetraethoxydecane, tetrapropoxydecane or tetrabutoxydecane is preferred, particularly tetramethoxy. Preferably, decane or tetraethoxy decane is preferred.

本發明中，式(1)所示烷氧基矽烷在使用於(B)成分的聚矽氧烷之製造的全烷氧基矽烷中，較佳為使用2~20莫耳%，特佳為使用3~15莫耳%，且式(3)所示烷氧基矽烷在使用於(B)成分的聚矽氧烷之製造的全烷氧基矽烷中，較佳為使用5~80莫耳%，特佳為使用10~70莫耳%。 In the present invention, the alkoxydecane represented by the formula (1) is preferably used in a total amount of 2 to 20 mol% in the peralkoxydecane produced by using the polyoxyalkylene of the component (B). The use of 3 to 15 mol%, and the alkoxydecane represented by the formula (3), in the peralkoxy decane produced by using the polyoxyalkylene of the component (B), preferably 5 to 80 mol. %, especially good for using 10~70 mol%.

又，式(4)所示烷氧基矽烷使用於(B)成分之聚矽氧烷的製造時，所使用之全烷氧基矽烷中，較佳為10~90莫耳%，特佳為20~90莫耳%。 Further, when the alkoxydecane represented by the formula (4) is used in the production of the polyoxyalkylene of the component (B), the total alkoxysilane used is preferably 10 to 90 mol%, particularly preferably 20~90% by mole.

〔(B)成分的聚矽氧烷之製造方法〕 [Method for Producing Polyoxane of Component (B)]

欲得到使用於本發明之聚矽氧烷的方法，並無特別限定，將上述式(1)之烷氧基矽烷作為必須成分的烷氧基矽烷在有機溶劑中進行聚縮合而得。因此，以聚矽氧烷均勻地溶解於有機溶劑之溶液方式得到。 The method for obtaining the polyoxyalkylene to be used in the present invention is not particularly limited, and an alkoxydecane having an alkoxydecane of the above formula (1) as an essential component is obtained by polycondensation in an organic solvent. Therefore, it is obtained as a solution in which polyoxyalkylene is uniformly dissolved in an organic solvent.

例如可舉出將上述式(1)的烷氧基矽烷在醇或甘醇等溶劑中進行水解．縮合的方法。此時，水解．縮合反應可為部分水解及完全水解中任一種。完全水解之情況為，理論上加入烷氧基矽烷中之全烷氧化物基的0.5倍莫耳之水即可，但一般加入比0.5倍莫耳更過剩量之水為佳。 For example, the alkoxydecane of the above formula (1) can be hydrolyzed in a solvent such as an alcohol or a glycol. The method of condensation. At this point, hydrolysis. The condensation reaction may be either partial or complete hydrolysis. In the case of complete hydrolysis, it is theoretically possible to add 0.5 times mole of water of the peralkoxide group in the alkoxysilane, but it is preferred to add more excess water than 0.5 times mole.

本發明中，使用於上述反應之水量，可視所望做適宜選擇，一般為烷氧基矽烷中之全烷氧基的0.5~2.5倍莫耳之範圍下進行。較佳為0.5~2.5倍莫耳，更佳為0.5~1.5倍莫耳。 In the present invention, the amount of water used in the above reaction can be suitably selected as desired, and is generally carried out in the range of 0.5 to 2.5 times moles of the total alkoxy group in the alkoxydecane. It is preferably 0.5 to 2.5 times Mo, more preferably 0.5 to 1.5 times Mo.

又，一般以促進水解．縮合反應為目的下，使用鹽酸、硫酸、硝酸、乙酸、蟻酸、草酸、馬來酸、富馬酸等酸；氨、甲基胺、乙基胺、乙醇胺、三乙基胺等鹼；鹽酸、硫酸、硝酸等金屬鹽等觸媒。又，藉由加熱溶解烷氧基矽烷之溶液，可進一步促進水解．縮合反應亦為一般。此時，加熱溫度及加熱時間可視所望而適宜選擇。例如在50℃進行24小時加熱．攪拌，迴流下進行1小時加熱．攪拌等方法可舉出。 Also, generally to promote hydrolysis. For the purpose of the condensation reaction, an acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid or fumaric acid; an alkali such as ammonia, methylamine, ethylamine, ethanolamine or triethylamine; hydrochloric acid; A catalyst such as a metal salt such as sulfuric acid or nitric acid. Moreover, the hydrolysis can be further promoted by heating and dissolving the solution of the alkoxy decane. The condensation reaction is also general. At this time, the heating temperature and the heating time can be appropriately selected as desired. For example, heating at 50 ° C for 24 hours. Stir and heat for 1 hour under reflux. Methods such as stirring can be mentioned.

又，作為其他方法，例如可舉出將烷氧基矽 烷、溶劑及草酸之混合物進行加熱而聚縮合之方法。具體為預先於醇中加入草酸，成為草酸之醇溶液後，在加熱該溶液之狀態下，混合烷氧基矽烷之方法。此時，所使用的草酸的量，對於具有烷氧基矽烷之全烷氧基1莫耳而言，以0.2~2莫耳者為佳。該方法中之加熱可在液溫50~180℃下進行。較佳為在不會發生液體蒸發或揮散等情況下，迴流下進行數十分~十數小時加熱之方法。 Further, as another method, for example, an alkoxy group is mentioned. A method in which a mixture of an alkane, a solvent and an oxalic acid is heated to be condensed. Specifically, a method in which oxalic acid is added to an alcohol to form an alcohol solution of oxalic acid, and then the alkoxysilane is mixed while heating the solution. In this case, the amount of oxalic acid to be used is preferably 0.2 to 2 moles for the total alkoxy group 1 mole having an alkoxydecane. The heating in this method can be carried out at a liquid temperature of 50 to 180 °C. Preferably, the method of heating for several ten to ten hours under reflux is carried out without causing evaporation or volatilization of the liquid.

使用複數烷氧基矽烷得到聚矽氧烷時，可使複數烷氧基矽烷預先混合後再反應，但亦可將複數烷氧基矽烷依序混合後反應。 When a polyoxyalkylene oxide is obtained by using a plurality of alkoxy decanes, the plural alkoxy decane may be previously mixed and then reacted, but a plurality of alkoxy decane may be sequentially mixed and reacted.

聚縮合烷氧基矽烷時所使用的溶劑(以下亦稱為聚合溶劑)僅為溶解烷氧基矽烷者即可，並無特別限定。又，即使在不溶解烷氧基矽烷之情況，僅可與烷氧基矽烷之聚縮合反應的進行同時溶解者即可。一般而言，因藉由烷氧基矽烷之聚縮合反應會生成醇，故可使用與醇類、甘醇類、甘醇醚類、或醇類之相溶性良好的有機溶劑。 The solvent (hereinafter also referred to as a polymerization solvent) used in the polycondensation of the alkoxysilane is only required to dissolve the alkoxysilane, and is not particularly limited. Further, even in the case where the alkoxydecane is not dissolved, it is only necessary to simultaneously dissolve the polycondensation reaction with the alkoxydecane. In general, since an alcohol is formed by a polycondensation reaction of an alkoxysilane, an organic solvent having good compatibility with an alcohol, a glycol, a glycol ether, or an alcohol can be used.

作為上述聚合溶劑之具體例，可舉出甲醇、乙醇、丙醇、丁醇、二丙酮醇等醇類；乙二醇、二乙二醇、丙二醇、二丙二醇、伸己基甘醇、1,3-丙烷二醇、1,2-丁烷二醇、1,3-丁烷二醇、1,4-丁烷二醇、2,3-丁烷二醇、1,2-戊烷二醇、1,3-戊烷二醇、1,4-戊烷二醇、1,5-戊烷二醇、2,4-戊烷二醇、2,3-戊烷二醇、1,6-己烷二醇等甘醇類；乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基 醚、乙二醇單丁基醚、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丙基醚、乙二醇二丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丙基醚、二乙二醇單丁基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丙基醚、二乙二醇二丁基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚、丙二醇二甲基醚、丙二醇二乙基醚、丙二醇二丙基醚、丙二醇二丁基醚等甘醇醚類；N,N’-二甲基甲醯胺、N,N’-二甲基乙醯胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-甲基己內醯胺、二甲基亞碸、四甲基尿素、二甲基碸、六甲基亞碸、γ-丁內酯、m-甲酚等。本發明中，可使用將上述聚合溶劑經複數種混合者。 Specific examples of the polymerization solvent include alcohols such as methanol, ethanol, propanol, butanol, and diacetone alcohol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and hexyl glycol; - propane diol, 1,2-butane diol, 1,3-butane diol, 1,4-butane diol, 2,3-butane diol, 1,2-pentane diol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexyl Glycols such as alkanediol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl Ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether , diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, Glycol ethers such as propylene glycol dipropyl ether and propylene glycol dibutyl ether; N,N'-dimethylformamide, N,N'-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl caprolactam, dimethyl hydrazine, tetramethyl urea, dimethyl hydrazine, hexamethyl fluorene, γ-butyrolactone, m-cresol Wait. In the present invention, a mixture of the above polymerization solvents may be used.

上述方法所得之聚矽氧烷的聚合溶液(以下亦稱為聚合溶液)為，作為原料裝入的全烷氧基矽烷之矽原子換算為SiO₂之濃度(以下亦稱為SiO₂換算濃度)，以20質量%以下為佳，特別以5~15質量%為佳。藉由選自該濃度範圍中之任意濃度，可抑制凝膠之生成，而得到均質之溶液。 The polymerization solution (hereinafter also referred to as a polymerization solution) of the polyoxyalkylene obtained by the above method is a concentration of SiO _{2 in terms} of a ruthenium atom of the peralkoxy decane charged as a raw material (hereinafter also referred to as SiO ₂ conversion concentration). It is preferably 20% by mass or less, particularly preferably 5 to 15% by mass. By forming any concentration selected from the concentration range, gel formation can be suppressed, and a homogeneous solution can be obtained.

〔(B)成分的聚矽氧烷之溶液〕 [Solution of polyoxane of component (B)]

本發明中，可將由上述方法所得之聚矽氧烷的聚合溶液直接作為(B)成分之溶液，或視必要將上述方法所得之溶液經濃縮或加入溶劑使其稀釋，或取代為其他溶劑作為(B)成分之溶液。 In the present invention, the polymerization solution of the polyoxyalkylene obtained by the above method may be directly used as a solution of the component (B), or the solution obtained by the above method may be concentrated or added to a solvent to be diluted or substituted with other solvents as necessary. A solution of the component (B).

此時，所使用之溶劑(以下亦稱為添加溶劑)可與聚合溶劑相同，或可為其他溶劑。該添加溶劑僅可將聚矽氧烷均勻溶解者即可，並無特別限定，可任意選擇一種或複數種使用。 At this time, the solvent to be used (hereinafter also referred to as an additive solvent) may be the same as the polymerization solvent, or may be another solvent. The additive solvent is not particularly limited as long as it can be uniformly dissolved in the polyoxyalkylene oxide, and one type or plural types can be used arbitrarily.

作為添加溶劑之具體例，可舉出上述聚合溶劑之例子的溶劑以外，亦可舉出丙酮、甲基乙酮、甲基異丁酮等酮類、乙酸甲酯、乙酸乙酯、乳酸乙酯等酯類等。 Specific examples of the solvent to be added include, in addition to the solvent of the above-mentioned polymerization solvent, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, methyl acetate, ethyl acetate, and ethyl lactate. Esters and the like.

這些溶劑可藉由液晶配向處理劑之黏度調整、或旋塗、柔版印刷、噴墨等提高將液晶配向處理劑塗布於基板上時的塗布性。 These solvents can improve the coatability when the liquid crystal alignment agent is applied onto a substrate by viscosity adjustment of a liquid crystal alignment agent, or spin coating, flexographic printing, or inkjet.

本發明中，因與(A)成分之聚醯胺酸及/或聚醯亞胺要混合，故作為(B)成分之溶液所使用的溶劑，以N,N’-二甲基甲醯胺、N,N’-二甲基乙醯胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-甲基己內醯胺、二甲基亞碸、四甲基尿素、二甲基碸、六甲基亞碸、γ-丁內酯、乙二醇單丁基醚為佳。 In the present invention, since it is mixed with the polyamic acid and/or polyimine of the component (A), the solvent used as the solution of the component (B) is N,N'-dimethylformamide. , N,N'-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl hydrazine, tetramethyl urea Preferably, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, and ethylene glycol monobutyl ether are preferred.

且，本發明中，於與(A)成分之聚醯胺酸及/或聚醯亞胺進行混合前，在製造聚矽氧烷時所使用的醇，或產生的醇以常壓或減壓下將此餾去為佳。 Further, in the present invention, the alcohol used in the production of the polyoxyalkylene, or the alcohol produced may be at a normal pressure or a reduced pressure before being mixed with the polyamine and/or the polyimide of the component (A). This distillation is preferred.

〔液晶配向處理劑〕 [Liquid alignment treatment agent]

本發明的液晶配向處理劑中之(B)成分(聚矽氧烷)的含有量對於含有聚醯胺酸及/或聚醯亞胺之(A)成分100質量份而言，具有(B)成分之矽原子的SiO₂換算 值為0.5~80質量份，較佳為0.5~50質量份。又，MVA、PVA、PSA等垂直配向型之情況為，為了不使液晶之垂直配向性降低，(B)成分(聚矽氧烷)的含有量在相同基準下，較佳為10~80質量份，更佳為20~70質量份。 The content of the component (B) (polyoxane) in the liquid crystal alignment agent of the present invention has (B) for 100 parts by mass of the component (A) containing polyglycolic acid and/or polyimine. The SiO ₂ conversion value of the ruthenium atom of the component is 0.5 to 80 parts by mass, preferably 0.5 to 50 parts by mass. Further, in the case of the vertical alignment type such as MVA, PVA, or PSA, the content of the component (B) (polyoxane) is preferably 10 to 80 mass in the same basis in order not to lower the vertical alignment of the liquid crystal. More preferably, it is 20 to 70 parts by mass.

本發明的液晶配向處理劑雖無特別限定，一般在製作液晶配向膜時，必須於基板上形成0.01~1.0μm之均勻薄膜，故除(A)成分及(B)成分以外，含有可溶解這些成分之有機溶劑的塗布液為佳。 The liquid crystal alignment treatment agent of the present invention is not particularly limited. Generally, when a liquid crystal alignment film is produced, it is necessary to form a uniform film of 0.01 to 1.0 μm on the substrate, so that it can be dissolved in addition to the components (A) and (B). A coating liquid of an organic solvent of the component is preferred.

本發明的液晶配向處理劑為含有上述有機溶劑時，由藉由塗布可形成更均勻薄膜之觀點來看，有機溶劑的含有量在液晶配向處理劑中，以90~99質量%為佳，以92~97質量%為更佳。這些含有量可藉由作為目的之液晶配向膜的膜厚做適宜變更。 When the liquid crystal alignment agent of the present invention contains the above organic solvent, the content of the organic solvent is preferably from 90 to 99% by mass in terms of the liquid crystal alignment treatment agent from the viewpoint of forming a more uniform film by coating. 92 to 97% by mass is more preferred. These contents can be appropriately changed by the film thickness of the intended liquid crystal alignment film.

作為本發明的液晶配向處理劑所使用的有機溶劑之具體例，可舉出前述聚醯胺酸或聚醯亞胺的合成反應所使用的有機溶劑。特佳為N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、二甲基亞碸、γ-丁內酯等。這些有機溶劑可使用1種類或併用2種類以上。 Specific examples of the organic solvent used in the liquid crystal alignment agent of the present invention include an organic solvent used in the synthesis reaction of the polyamic acid or polyimine. Particularly preferred are N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl hydrazine, γ - Butyrolactone and the like. These organic solvents can be used in one type or in combination of two or more types.

又，於有機溶劑中，以提高塗膜的均勻性為目的，可含有乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚、乙二醇單戊基醚、乙二醇單己基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二 醇單丙基醚、二乙二醇單丁基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇單乙基醚乙酸酯、乙二醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇-1-單甲基醚-2-乙酸酯、丙二醇-1-單乙基醚-2-乙酸酯、二丙二醇、二丙二醇單甲基醚、二丙二醇單乙基醚、4-羥基-4-甲基-2-戊酮、2-(2-乙氧基丙氧基)丙醇、二丙酮醇、乳酸甲酯、乳酸乙酯、乳酸n-丙基酯、乳酸n-丁基酯、乳酸異戊基酯等具有低表面張力之溶劑為佳。 Further, in the organic solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether may be contained for the purpose of improving the uniformity of the coating film. , ethylene glycol monopentyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene Alcohol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol, 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, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl Ether, 4-hydroxy-4-methyl-2-pentanone, 2-(2-ethoxypropoxy)propanol, diacetone alcohol, methyl lactate, ethyl lactate, n-propyl lactate, A solvent having a low surface tension such as n-butyl lactic acid or isoamyl lactic acid is preferred.

這些溶劑一般可使用1種類或混合2種類以上使用。這些溶劑一般為溶解聚醯胺酸或聚醯亞胺之能力為低，故有機溶劑中之80質量%以下者為佳，較佳為60質量%以下。又，若期待提高塗膜之均勻性時，有機溶劑中之5質量%以上為佳，較佳為20質量%以上。 These solvents can be generally used in one type or in a mixture of two or more types. These solvents generally have a low ability to dissolve polyglycolic acid or polyimine, and therefore 80% by mass or less of the organic solvent is preferable, and preferably 60% by mass or less. In addition, when it is desired to improve the uniformity of the coating film, it is preferably 5% by mass or more, preferably 20% by mass or more, in the organic solvent.

且，本發明的液晶液晶配向處理劑可含有提高塗膜與基板之密著性的化合物、提高塗膜之平坦化性的界面活性劑等。 In addition, the liquid crystal liquid crystal alignment treatment agent of the present invention may contain a compound which improves the adhesion between the coating film and the substrate, and a surfactant which improves the flatness of the coating film.

作為提高塗膜與基板之密著性的化合物之具體例，可舉出以下所示官能性矽烷含有化合物等。例如可舉出3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-乙氧基羰基-3-胺基丙基三甲氧基矽烷、N-乙氧基羰基-3-胺基丙基 三乙氧基矽烷、N-三乙氧基矽烷基丙基三伸乙基三胺、N-三甲氧基矽烷基丙基三伸乙基三胺、10-三甲氧基矽烷基-1,4,7-三氮雜癸烷、10-三乙氧基矽烷基-1,4,7-三氮雜癸烷、9-三甲氧基矽烷基-3,6-二氮雜壬基乙酸酯、9-三乙氧基矽烷基-3,6-二氮雜壬基乙酸酯、N-苯甲基-3-胺基丙基三甲氧基矽烷、N-苯甲基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-雙(環氧乙烷)-3-胺基丙基三甲氧基矽烷、N-雙(環氧乙烷)-3-胺基丙基三乙氧基矽烷等。 Specific examples of the compound which improves the adhesion between the coating film and the substrate include the following functional decane-containing compounds and the like. Examples thereof include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyltriethoxydecane. N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-B Oxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethoxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxydecyl-1,4 , 7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazaindolyl acetate , 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-amine Propyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(ethylene oxide) 3-aminopropyltrimethoxydecane, N-bis(ethylene oxide)-3-aminopropyltriethoxydecane, and the like.

這些化合物的添加量由可得到密著性提高之效果且不會降低液晶之配向性的觀點來看，對於(A)成分100質量份而言以0.1~30質量份為佳，較佳為1~20質量份，特佳為1~10質量份。 The amount of the compound to be added is preferably from 0.1 to 30 parts by mass, preferably from 1 to 100 parts by mass of the component (A), from the viewpoint that the adhesion is improved and the alignment of the liquid crystal is not lowered. ~20 parts by mass, particularly preferably 1 to 10 parts by mass.

作為提高塗膜之平坦化性的界面活性劑，可舉出氟系界面活性劑、矽氧樹脂系界面活性劑、非離子系界面活性劑等。更具體為，例如可舉出EftopEF301、EF303、EF352(以上為Tohkem Products公司製)、MegafacF171、F173、R-30(以上為大日本油墨公司製)、FluoradFC430、FC431(以上為住友3M公司製)、AsahiguardAG710、SurflonS-382、SC101、SC102、SC103、SC104、SC105、SC106(以上為旭硝子公司製)等。 Examples of the surfactant which improves the flatness of the coating film include a fluorine-based surfactant, a silicone resin-based surfactant, and a nonionic surfactant. More specifically, Eftop EF 301, EF 303, EF 352 (above, Tohkem Products Co., Ltd.), Megafac F171, F173, R-30 (above, manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (above, Sumitomo 3M Co., Ltd.) Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (the above is manufactured by Asahi Glass Co., Ltd.).

這些界面活性劑的含有量對於(A)成分100質量份而言，較佳為0.01~2質量份，更佳為0.01~1質量份。 The content of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the component (A).

<液晶配向膜．液晶顯示元件> <Liquid alignment film. Liquid crystal display element>

本發明的液晶配向處理劑為於基板上進行塗布並燒成後，以摩擦處理或光照射等進行配向處理，或在垂直配向用途等上，即使無進行配向處理，亦可作為液晶配向膜使用。 The liquid crystal alignment treatment agent of the present invention is applied to a substrate and then fired, and then subjected to an alignment treatment by rubbing treatment or light irradiation, or in a vertical alignment application or the like, and can be used as a liquid crystal alignment film even without alignment treatment. .

此時，作為所使用的基板，僅為透明性高的基板即可，並無特別限定，可使用玻璃基板；丙烯酸基板或聚碳酸酯基板等塑質基板等。且，使用欲液晶驅動之ITO電極或IZO(銦．鋅氧化物)電極等所形成之基板時，由製程簡單化之觀點來看為佳。又，在反射型液晶顯示元件中，不僅使用單側的基板，亦可使用矽晶圓等不透明物，此時的電極亦可使用金屬鋁等反射光的材料。 In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. Further, when a substrate formed of an ITO electrode or an IZO (indium zinc oxide) electrode to be driven by a liquid crystal is used, it is preferable from the viewpoint of simplifying the process. Further, in the reflective liquid crystal display device, not only a single-sided substrate but also an opaque material such as a germanium wafer may be used, and in this case, a material that reflects light such as metal aluminum may be used.

液晶配向處理劑的塗布方法並無特別限定，以螢幕印刷、膠版印刷、柔版印刷、噴墨等進行之方法為一般。作為其他塗布方法，有浸漬、輥式塗佈機、縫隙塗佈機、轉動子等，可配合目的使用。 The coating method of the liquid crystal alignment treatment agent is not particularly limited, and a method of performing screen printing, offset printing, flexographic printing, inkjet, or the like is generally employed. As another coating method, there are an immersion, a roll coater, a slit coater, a rotor, etc., and it can be used together.

塗布液晶配向處理劑後之基板在70~100℃之熱板上放置1~3分鐘程度後使溶劑揮發並乾燥，其後進行燒成。燒成可在100~350℃之任意溫度下進行，但較佳為120~300℃，更佳為150~250℃。該燒成可藉由熱板、熱風循環爐、紅外線爐等進行。 The substrate coated with the liquid crystal alignment agent is placed on a hot plate at 70 to 100 ° C for about 1 to 3 minutes, and then the solvent is volatilized and dried, followed by firing. The firing can be carried out at any temperature of 100 to 350 ° C, but is preferably 120 to 300 ° C, more preferably 150 to 250 ° C. This baking can be performed by a hot plate, a hot air circulation furnace, an infrared furnace, or the like.

對於燒成後之塗膜厚度，若過厚時以液晶顯示元件之消費電力的層面來看為不利，過薄時會有降低液晶顯示元件之信賴性情況，故以5~300nm為佳，較佳為 10~150nm，更佳為50~100nm。使液晶呈水平配向或傾斜配向時，將燒成後之塗膜藉由摩擦或偏光紫外線照射等進行處理。 When the thickness of the coating film after firing is too thick, it is disadvantageous in terms of the power consumption of the liquid crystal display element, and when it is too thin, the reliability of the liquid crystal display element is lowered, so that it is preferably 5 to 300 nm. Good for 10 to 150 nm, more preferably 50 to 100 nm. When the liquid crystal is horizontally aligned or obliquely aligned, the coated film after firing is treated by rubbing or polarized ultraviolet irradiation or the like.

本發明的液晶顯示元件可舉出自本發明的液晶配向處理劑得到附有液晶配向膜之基板後，以公知方法製作晶胞，作為顯示元件者。若要舉出晶胞製作的一例子，可例示出準備形成液晶配向膜之1對基板，於單面的基板之液晶配向膜上形成管柱空間，或散佈珠空間，使液晶配向膜面成為內側，貼合另一單面基板，將液晶進行減壓注入使其封止之方法，或形成管柱空間或散佈珠空間之液晶配向膜面上滴入液晶後，貼合基板使其進行封止之方法等可例示。此時的空間厚度較佳為1~30μm，更佳為2~10μm。 In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is obtained, and a unit cell is produced by a known method as a display element. For example, a pair of substrates for forming a liquid crystal alignment film can be exemplified, and a column space can be formed on a liquid crystal alignment film of a single-sided substrate, or a bead space can be dispersed to make the liquid crystal alignment film surface On the inner side, the other single-sided substrate is bonded, and the liquid crystal is injected under reduced pressure to be sealed, or the liquid crystal is formed on the liquid crystal alignment film surface forming the column space or the scattered bead space, and then the substrate is bonded to be sealed. The method and the like can be exemplified. The space thickness at this time is preferably from 1 to 30 μm, more preferably from 2 to 10 μm.

[實施例] [Examples]

以下將本發明藉由實施例做進一步具體說明，但並未限定於此等解釋。 The invention is further illustrated by the following examples, but is not limited thereto.

在實施例所使用的化合物之簡稱如下所示。 The abbreviations of the compounds used in the examples are shown below.

(烷氧基矽烷單體) (alkoxydecane monomer)

TEOS：四乙氧基矽烷 TEOS: tetraethoxy decane

C18：十八烷基三乙氧基矽烷 C18: octadecyltriethoxydecane

C12：十二烷基三乙氧基矽烷 C12: dodecyltriethoxydecane

UPS：3-脲基丙基三乙氧基矽烷 UPS: 3-ureidopropyltriethoxydecane

MPMS：3-甲基丙烯氧基丙基三甲氧基矽烷 MPMS: 3-methacryloxypropyltrimethoxydecane

VTMS：乙烯基三甲氧基矽烷 VTMS: vinyl trimethoxy decane

STMS：苯乙烯基乙基三甲氧基矽烷 STMS: Styrylethyltrimethoxydecane

MTES：甲基三乙氧基矽烷 MTES: methyl triethoxy decane

(四羧酸二酐) (tetracarboxylic dianhydride)

CBDA：1,2,3,4-環丁烷四羧酸二酐 CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

BDA：1,2,3,4-環丁烷四羧酸二酐 BDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

PMDA：均苯四甲酸二酐 PMDA: pyromellitic dianhydride

BODA：聯環〔3,3,0〕辛烷-2,4,6,8-四羧酸二酐 BODA: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

(二胺化合物) (diamine compound)

m-PDA：m-伸苯基二胺 m-PDA: m-phenylene diamine

DBA：3,5-二胺基苯甲酸 DBA: 3,5-diaminobenzoic acid

DDM：4,4’-二胺基二苯基甲烷 DDM: 4,4'-diaminodiphenylmethane

4,4’DADPA：4,4’-二胺基二苯基胺 4,4'DADPA: 4,4'-diaminodiphenylamine

BAPU：1,3-雙(4-胺基苯乙基)尿素 BAPU: 1,3-bis(4-aminophenethyl)urea

Sin0：1,3-雙(3-胺基丙基)四甲基二矽氧烷 Sin0: 1,3-bis(3-aminopropyl)tetramethyldioxane

PCH7DAB：1,3-二胺基-4-〔4-(反-4-n-庚基環己基)苯氧基〕苯 PCH7DAB: 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxy]benzene

(有機溶劑) (Organic solvents)

THF：四氫呋喃 THF: tetrahydrofuran

DMF：二甲基甲醯胺 DMF: dimethylformamide

NMP：N-甲基-2-吡咯烷酮 NMP: N-methyl-2-pyrrolidone

BCS：2-丁氧基乙醇 BCS: 2-butoxyethanol

NMR之測定、分子量之測定、亞醯胺化率之測定等如以下所示進行。 The measurement of NMR, the measurement of the molecular weight, and the measurement of the imidization ratio were carried out as follows.

(¹H-NMR之測定) (Measurement of ¹ H-NMR)

¹H-NMR(500MHz、質子NMR)為使用日本電子Datam公司製的NMR測定器(JNW-ECA500)，於重氯仿(CDCl₃)中，內部標準使用四甲基矽烷(TMS)進行測定。 ¹ H-NMR (500 MHz, proton NMR) was measured using NMR measuring instrument (JNW-ECA500) manufactured by JEOL Ltd., and used in heavy chloroform (CDCl ₃ ), and the internal standard was measured using tetramethyl decane (TMS).

(聚醯胺酸及聚醯亞胺的分子量測定) (Measurement of molecular weight of polylysine and polyimine)

分子量使用昭和電工公司製 常溫凝膠浸透層析法(GPC)裝置(GPC-101)、Shodex公司製管柱(KD-803、KD-805)如以下所示測定。 The molecular weight was measured by a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Showa Denko Co., Ltd., and a column (KD-803, KD-805) manufactured by Shodex Co., Ltd. as shown below.

管柱溫度：50℃ Column temperature: 50 ° C

溶離液：N,N’-二甲基甲醯胺(作為添加劑，溴化鋰-水合物(LiBr．H₂O)為30mmol/L(公升)、磷酸．無水結晶(o-磷酸)為30mmol/L、四氫呋喃(THF)為10ml(毫升)/L) Dissolution: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr.H ₂ O) is 30 mmol/L (liter), phosphoric acid. Anhydrous crystal (o-phosphoric acid) is 30 mmol/L , tetrahydrofuran (THF) is 10ml (ml) / L)

流速：1.0ml/分 Flow rate: 1.0ml/min

檢量線作成用標準樣品：Tosoh公司製TSK標準聚氧化乙烯(分子量約900,000、150,000、100,000、及30,000)、及聚合物實驗室公司製聚乙二醇(分子量約12,000、4,000、及1,000)。 Standard sample for calibration line preparation: TSK standard polyethylene oxide (molecular weight of about 900,000, 150,000, 100,000, and 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight of about 12,000, 4,000, and 1,000) manufactured by Polymer Laboratories. .

(亞醯胺化率之測定) (Measurement of the amidation rate)

將聚醯亞胺粉末20mg放入NMR樣品管(草野科學公司製NMR標準採樣管 5)中，添加重氫化二甲基亞碸(DMSO-d6、0.05質量%TMS(四甲基矽烷)混合品)0.53mL，加入超音波使其完全溶解。將該溶液以日本電子Datam公司製之NMR測定器(JNW-ECA500)測定500MHz之質子NMR。亞醯胺化率係以來自在亞醯胺化前後無變化之結構的質子作為基準質子來鑑定，使用該質子之吸收峰積算值與來自9.5~10.0ppm附近出現的醯胺酸 的NH基之質子吸收峰積算值藉由以下式求得。 20 mg of polyimine powder was placed in an NMR sample tube (NMR standard sampling tube manufactured by Kusano Scientific Co., Ltd. In 5), 0.53 mL of dimethyl hydrazine (DMSO-d6, 0.05% by mass of TMS (tetramethyl decane) mixed) was added, and ultrasonic waves were added thereto to completely dissolve. This solution was measured for proton NMR at 500 MHz by an NMR measuring instrument (JNW-ECA500) manufactured by Nippon Denshi Datam Co., Ltd. The imidization ratio is identified by a proton derived from a structure which has not changed before and after the amidation, and the absorption peak of the proton is used to calculate the proton of the NH group from the vicinity of 9.5 to 10.0 ppm. The absorption peak product value is obtained by the following formula.

亞醯胺化率(%)=(1-α．x/y)×100 Amidoxime rate (%) = (1-α.x/y) × 100

對於上述式，x為來自醯胺酸之NH基的質子吸收峰積算值，y為基準質子之吸收峰積算值，α為聚醯胺酸(亞醯胺化率為0%)時之對醯胺酸的NH基質子1個的基準質子之個數比率。 For the above formula, x is the calculated value of the proton absorption peak derived from the NH group of proline, y is the calculated value of the absorption peak of the reference proton, and α is the opposite of the polyproline (the amidoxime rate is 0%). The ratio of the number of reference protons of one NH substrate of the amine acid.

<化合物10的合成> <Synthesis of Compound 10>

於具備磁棒攪拌器之500mL四口燒瓶中，裝入30.00g的化合物9、25.24g的碳酸鉀、及120g的DMF，在室溫下滴入溴丙烯22.10g。此後，於50℃進行11小時攪拌。將反應液以500g的乙酸乙酯稀釋，將有機層以200g的純水進行3次洗淨。將分離之有機層以硫酸鈉乾燥後並使其過濾。其後將濾液經濃縮乾燥後得到34.80g的化合物10(產率100%)。 30.00 g of the compound 9, 25.24 g of potassium carbonate, and 120 g of DMF were placed in a 500 mL four-necked flask equipped with a magnetic stirrer, and 22.10 g of bromopropene was added dropwise at room temperature. Thereafter, stirring was carried out at 50 ° C for 11 hours. The reaction solution was diluted with 500 g of ethyl acetate, and the organic layer was washed three times with 200 g of purified water. The separated organic layer was dried over sodium sulfate and filtered. Thereafter, the filtrate was concentrated to dryness to give 34.80 g of Compound 10 (yield 100%).

¹H-NMR(500MHz)in CDCl₃：0.90ppm(t,J=7.2 Hz,3H),0.99-1.09ppm(m,2H),1.18-1.46ppm(m,11H),1.84-1.89ppm(m,4H),2.37-2.44ppm(m,1H),4.51ppm(dt,J=5.4Hz,1.6Hz,2H),5.26ppm(dq,J=10.6Hz,1.6Hz,1H),5.40ppm(dq,J=17.2Hz,1.6Hz,1H),6.07ppm(ddd,J=17.2Hz,10.6Hz,5.4Hz,1H),6.83ppm(dd,J=8.8Hz,2.9Hz,2H),7.10ppm(dd,J=8.8Hz,2.9Hz,2H) ¹ H-NMR (500 MHz) in CDCl ₃ : 0.90 ppm (t, J = 7.2 Hz, 3H), 0.991.09 ppm (m, 2H), 1.18-1.46 ppm (m, 11H), 1.84-1.89 ppm (m) , 4H), 2.37-2.44ppm (m, 1H), 4.51ppm (dt, J = 5.4Hz, 1.6Hz, 2H), 5.26ppm (dq, J = 10.6Hz, 1.6Hz, 1H), 5.40ppm (dq , J = 17.2 Hz, 1.6 Hz, 1H), 6.07 ppm (ddd, J = 17.2 Hz, 10.6 Hz, 5.4 Hz, 1H), 6.83 ppm (dd, J = 8.8 Hz, 2.9 Hz, 2H), 7.10 ppm ( Dd, J = 8.8 Hz, 2.9 Hz, 2H)

<化合物11的合成> <Synthesis of Compound 11>

於具備磁棒攪拌器之300mL四口燒瓶中，放入20.00g的化合物10、及甲苯120g，於室溫下進行攪拌。其次添加karstedt觸媒(鉑(0)-1,1,3,3-四甲基二矽氧烷錯合物0.1mol/L二甲苯溶液)700μl後，滴入三甲氧基矽烷12.4mL。在室溫進行29小時攪拌後，將反應液經濃縮乾燥後得到粗物。將所得之粗物在減壓下蒸餾，在外溫245℃/壓力0.8torr之條件下使其餾出後得到12.15g之化合物11(產率43%)。 20.00 g of the compound 10 and 120 g of toluene were placed in a 300 mL four-necked flask equipped with a magnetic stirrer, and the mixture was stirred at room temperature. Next, 700 μl of a karstedt catalyst (platinum (0)-1,1,3,3-tetramethyldioxane complex 0.1 mol/L xylene solution) was added, and then 12.4 mL of trimethoxydecane was added dropwise. After stirring at room temperature for 29 hours, the reaction mixture was concentrated to dryness to give a crude material. The obtained crude product was distilled under reduced pressure, and then distilled under an external temperature of 245 ° C / pressure of 0.8 torr to give 12.15 g of Compound 11 (yield 43%).

¹H-NMR(500MHz)in CDCl₃：0.76-0.82ppm(m,2H),0.89ppm(t,J=7.2Hz,3H),0.98-1.08ppm(m,2H),1.18-1.45ppm(m,11H),1.84-1.93ppm(m,6H),2.36-2.43ppm(m,1H),3.58ppm(s,9H),3.91ppm(t,J=6.8Hz,2H),6.81ppm(d,J=8.8Hz,2H),7.08ppm(d,J=8.8Hz,2H) ¹ H-NMR (500 MHz) in CDCl ₃ : 0.76-0.82 ppm (m, 2H), 0.89 ppm (t, J = 7.2 Hz, 3H), 0.98-1.08 ppm (m, 2H), 1.18-1.45 ppm (m) , 11H), 1.84-1.93ppm (m, 6H), 2.36-2.43ppm (m, 1H), 3.58ppm (s, 9H), 3.91ppm (t, J = 6.8Hz, 2H), 6.81ppm (d, J=8.8Hz, 2H), 7.08ppm (d, J=8.8Hz, 2H)

〔(A)成分(聚醯胺酸及聚醯亞胺)的合成〕 [Synthesis of (A) component (polyglycine and polyimine) <合成例1> <Synthesis Example 1>

將四羧酸二酐成分之CBDA 97.1g(0.5mol)、與二胺成分之DBA 76.1g(0.5mol)在NMP 1270g中混合，在室溫下進行5小時反應後得到聚醯胺酸溶液。聚合反應可容易且均勻地進行。所得之聚醯胺酸的數平均分子量為16,800，重量平均分子量為48,300。且欲使該溶液成為聚醯胺酸4重量%、NMP76重量%、及BCS20重量%，而加入NMP與BCS，得到聚醯胺酸溶液(A1)。 97.1 g (0.5 mol) of a CBDA of a tetracarboxylic dianhydride component and 76.1 g (0.5 mol) of DBA of a diamine component were mixed in 1270 g of NMP, and it carried out the reaction for 5 hours at room temperature, and the poly lysine solution was obtained. The polymerization can be carried out easily and uniformly. The obtained polyamic acid had a number average molecular weight of 16,800 and a weight average molecular weight of 48,300. Further, in order to make the solution 4% by weight of polyamic acid, 76% by weight of NMP, and 20% by weight of BCS, NMP and BCS were added to obtain a polyaminic acid solution (A1).

<合成例2> <Synthesis Example 2>

將四羧酸二酐成分之BDA 79.1g(0.4mol)、與二胺成分之DBA 60.9g(0.4mol)在NMP 560g中進行混合，在室溫進行7小時反應後得到聚醯胺酸溶液。聚合反應可容易且均勻地進行。所得之聚醯胺酸的數平均分子量為9,800，重量平均分子量為31,300。且欲使該溶液成為聚醯胺酸4重量%、NMP76重量%、及BCS20重量%，而加入NMP與BCS，得到聚醯胺酸溶液(A2)。 79.3 g (0.4 mol) of BDA of the tetracarboxylic dianhydride component and 60.9 g (0.4 mol) of DBA of the diamine component were mixed in 560 g of NMP, and the reaction was carried out for 7 hours at room temperature to obtain a polyaminic acid solution. The polymerization can be carried out easily and uniformly. The obtained polyamic acid had a number average molecular weight of 9,800 and a weight average molecular weight of 31,300. Further, in order to make the solution 4% by weight of polyamic acid, 76% by weight of NMP, and 20% by weight of BCS, NMP and BCS were added to obtain a polyaminic acid solution (A2).

<合成例3> <Synthesis Example 3>

將四羧酸二酐成分之PMDA 106.1g(0.49mol)與二胺成分之DBA 76.1g(0.5mol)在NMP 1336g中進行混合，在室溫下進行5小時反應後得到聚醯胺酸溶液。聚合反應可容易且均勻地進行。所得之聚醯胺酸的數平均分子 量為15,600，重量平均分子量為44,300。且欲使該溶液成為聚醯胺酸4重量%、NMP76重量%、及BCS20重量%，而加入NMP與BCS，得到聚醯胺酸溶液(A3)。 106.1 g (0.49 mol) of PMDA of the tetracarboxylic dianhydride component and 76.1 g (0.5 mol) of DBA of the diamine component were mixed in N336 1336 g, and the reaction was carried out for 5 hours at room temperature to obtain a polyaminic acid solution. The polymerization can be carried out easily and uniformly. Number average molecule of polyphosphonic acid obtained The amount was 15,600 and the weight average molecular weight was 44,300. Further, in order to make the solution 4% by weight of polyamic acid, 76% by weight of NMP, and 20% by weight of BCS, NMP and BCS were added to obtain a polyaminic acid solution (A3).

<合成例4> <Synthesis Example 4>

將四羧酸二酐成分之PMDA 102.8g(0.47mol)與二胺成分之BAPU 149.2g(0.5mol)在NMP 1843g中進行混合，在室溫下進行5小時反應後得到聚醯胺酸溶液。聚合反應可容易且均勻地進行。所得之聚醯胺酸的數平均分子量為13,800，重量平均分子量為41,400。且欲使該溶液成為聚醯胺酸4重量%、NMP76重量%、及BCS20重量%，而加入NMP與BCS，得到聚醯胺酸溶液(A4)。 102.8 g (0.47 mol) of PMDA of the tetracarboxylic dianhydride component and 149.2 g (0.5 mol) of BAPU of the diamine component were mixed in N843 1843 g, and the reaction was carried out for 5 hours at room temperature to obtain a polyaminic acid solution. The polymerization can be carried out easily and uniformly. The obtained polyamic acid had a number average molecular weight of 13,800 and a weight average molecular weight of 41,400. Further, in order to make the solution 4% by weight of polyamic acid, 76% by weight of NMP, and 20% by weight of BCS, NMP and BCS were added to obtain a polyamic acid solution (A4).

<合成例5> <Synthesis Example 5>

將四羧酸二酐成分之CBDA 94.1g(0.48mol)與二胺成分之BAPU 149.2g(0.5mol)在NMP 1784g中進行混合，在室溫下進行5小時反應後得到聚醯胺酸溶液。聚合反應可容易且均勻地進行。所得之聚醯胺酸的數平均分子量為15,200，重量平均分子量為46,700。且欲使該溶液成為聚醯胺酸4重量%、NMP76重量%、及BCS20重量%，而加入NMP與BCS，得到聚醯胺酸溶液(A5)。 94.1 g (0.48 mol) of CBDA of the tetracarboxylic dianhydride component and 149.2 g (0.5 mol) of BAPU of the diamine component were mixed in N784 (1784 g), and the reaction was carried out for 5 hours at room temperature to obtain a polyaminic acid solution. The polymerization can be carried out easily and uniformly. The obtained polyamic acid had a number average molecular weight of 15,200 and a weight average molecular weight of 46,700. Further, in order to make the solution 4% by weight of polyaminic acid, 76% by weight of NMP, and 20% by weight of BCS, NMP and BCS were added to obtain a polyaminic acid solution (A5).

<合成例6> <Synthesis Example 6>

將四羧酸二酐成分之CBDA 78.2g(0.4mol)與二胺 成分之m-PDA 43.2g(0.4mol)在NMP 664g中進行混合，在室溫下進行5小時反應後得到聚醯胺酸溶液。聚合反應可容易且均勻地進行。所得之聚醯胺酸的數平均分子量為21,800，重量平均分子量為51,500。且欲使該溶液成為聚醯胺酸4重量%、NMP76重量%、及BCS20重量%，而加入NMP與BCS，得到聚醯胺酸溶液(A6)。 48.2 g (0.4 mol) of CBDA with a tetracarboxylic dianhydride component and a diamine The component m-PDA 43.2 g (0.4 mol) was mixed in NMP 664 g, and the reaction was carried out for 5 hours at room temperature to obtain a polyaminic acid solution. The polymerization can be carried out easily and uniformly. The obtained polyamic acid had a number average molecular weight of 21,800 and a weight average molecular weight of 51,500. Further, in order to make the solution 4% by weight of polyaminic acid, 76% by weight of NMP, and 20% by weight of BCS, NMP and BCS were added to obtain a polyaminic acid solution (A6).

<合成例7> <Synthesis Example 7>

將四羧酸二酐成分之CBDA 19.2g(0.098mol)與二胺成分之DDM 19.8g(0.1mol)在NMP 221.3g中進行混合，在室溫下進行24小時反應後得到聚醯胺酸溶液。聚合反應可容易且均勻地進行。所得之聚醯胺酸的數平均分子量為18,800，重量平均分子量為52,300。且欲使該溶液成為聚醯胺酸4重量%、NMP76重量%、及BCS20重量%，而加入NMP與BCS，得到聚醯胺酸溶液(A7)。 19.2 g (0.098 mol) of CBDA of the tetracarboxylic dianhydride component and 19.8 g (0.1 mol) of DDM of the diamine component were mixed in NMP 221.3 g, and the reaction was carried out for 24 hours at room temperature to obtain a polyamidonic acid solution. . The polymerization can be carried out easily and uniformly. The obtained polyamic acid had a number average molecular weight of 18,800 and a weight average molecular weight of 52,300. Further, in order to make the solution 4% by weight of polyamic acid, 76% by weight of NMP, and 20% by weight of BCS, NMP and BCS were added to obtain a polyaminic acid solution (A7).

<合成例8> <Synthesis Example 8>

將四羧酸二酐成分之CBDA 19.6g(0.1mol)與二胺成分之4,4’DADPA 18.7g(0.094mol)在NMP 345.1g中進行混合，在室溫下進行5小時反應後得到聚醯胺酸溶液。聚合反應可容易且均勻地進行。所得之聚醯胺酸的數平均分子量為17,500，重量平均分子量為48,100。且欲使該溶液成為聚醯胺酸4重量%、NMP76重量%、及BCS20重量%，而加入NMP與BCS，得到聚醯胺酸溶液 (A8)。 19.6 g (0.1 mol) of CBDA of the tetracarboxylic dianhydride component and 18.7 g (0.094 mol) of 4,4'DADPA of the diamine component were mixed in NMP 345.1 g, and the reaction was carried out for 5 hours at room temperature to obtain a poly Proline solution. The polymerization can be carried out easily and uniformly. The obtained polyamic acid had a number average molecular weight of 17,500 and a weight average molecular weight of 48,100. And to make the solution 4% by weight of polyaminic acid, 76% by weight of NMP, and 20% by weight of BCS, and adding NMP and BCS to obtain a polyaminic acid solution. (A8).

<合成例9> <Synthesis Example 9>

將BODA 150.1g(0.6mol)、DBA 60.9g(0.4mol)、及PCH7DAB 152.2g(0.4mol)在NMP 1290g中進行混合，在80℃進行5小時反應。其後，加入CBDA 38.8g(0.2mol)與NMP 320g，在40℃進行3小時反應後得到聚醯胺酸溶液。該聚醯胺酸溶液100.8g中加入NMP，稀釋成6質量%。其後，加入亞醯胺化觸媒之乙酸酐10.66g、及吡啶8.26g，在80℃進行3小時反應。其後將該反應溶液投入於甲醇1300ml中，過濾分離所得之沈澱物。將該沈澱物以甲醇洗淨，其次在100℃進行減壓乾燥，得到聚醯亞胺粉末(C1)。該聚醯亞胺的亞醯胺化率為55%，數平均分子量為28,500，重量平均分子量為66,100。 BODA 150.1 g (0.6 mol), DBA 60.9 g (0.4 mol), and PCH7DAB 152.2 g (0.4 mol) were mixed in NMP 1290 g, and the reaction was carried out at 80 ° C for 5 hours. Thereafter, 38.8 g (0.2 mol) of CBDA and 320 g of NMP were added, and the reaction was carried out at 40 ° C for 3 hours to obtain a polyaminic acid solution. To 100.8 g of this polyaminic acid solution, NMP was added and diluted to 6 mass%. Thereafter, 10.66 g of acetic anhydride and 8.26 g of pyridine were added to the imidization catalyst, and the reaction was carried out at 80 ° C for 3 hours. Thereafter, the reaction solution was poured into 1300 ml of methanol, and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C to obtain a polyimine powder (C1). The polyamidimide had a mercapto amination ratio of 55%, a number average molecular weight of 28,500, and a weight average molecular weight of 66,100.

於該聚醯亞胺粉末(C1)7.4g中加入41.9g的NMP，在80℃進行40小時攪拌並使其溶解。進一步欲將該溶液成為聚醯亞胺4重量%、NMP76重量%、及BCS20重量%而加入NMP與BCS，得到聚醯亞胺溶液(A9)。 41.9 g of NMP was added to 7.4 g of the polyimine powder (C1), and the mixture was stirred and dissolved at 80 ° C for 40 hours. Further, this solution was prepared by adding NMP and BCS to 4% by weight of polyimine, 76% by weight of NMP, and 20% by weight of BCS to obtain a polyimine solution (A9).

<合成例10> <Synthesis Example 10>

將BODA 7.5g(30.0mmol)、DBA 1.8(12.0mmol)、Sin0 2.0g(8.0mmol)、及PCH7DAB 7.6g(20.0mmol)在NMP 55g中混合，在80℃進行5小時反應。其後，加入CBDA 1.9g(10.0mmol)與NMP 27.0g，在40℃進行 3小時反應後得到聚醯胺酸溶液。該聚醯胺酸溶液30.0g中加入NMP，稀釋成6質量%。其後，加入亞醯胺化觸媒之乙酸酐2.99g、及吡啶2.32g，在80℃進行3小時反應。其後將該反應溶液投入於甲醇370ml中，過濾分離所得之沈澱物。將該沈澱物以甲醇洗淨，其次在100℃進行減壓乾燥，得到聚醯亞胺粉末(C2)。該聚醯亞胺的亞醯胺化率為57%，數平均分子量為26,800，重量平均分子量為63,400。 BODA 7.5 g (30.0 mmol), DBA 1.8 (12.0 mmol), Sin0 2.0 g (8.0 mmol), and PCH7DAB 7.6 g (20.0 mmol) were mixed in 55 g of NMP, and the reaction was carried out at 80 ° C for 5 hours. Thereafter, CBDA 1.9 g (10.0 mmol) and NMP 27.0 g were added and carried out at 40 ° C. A polyaminic acid solution was obtained after 3 hours of reaction. NMP was added to 30.0 g of this polyaminic acid solution, and it diluted to 6% by mass. Thereafter, 2.99 g of acetic anhydride of an imidization catalyst and 2.32 g of pyridine were added, and the reaction was carried out at 80 ° C for 3 hours. Thereafter, the reaction solution was poured into 370 ml of methanol, and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C to obtain a polyimine powder (C2). The polyamidimide had a mercapto amination rate of 57%, a number average molecular weight of 26,800, and a weight average molecular weight of 63,400.

於該聚醯亞胺粉末(C2)7.4g加入41.9g的NMP，在80℃進行40小時攪拌並使其溶解。進一步欲將該溶液成為聚醯亞胺4重量%、NMP76重量%、及BCS20重量%而加入NMP與BCS，得到聚醯亞胺溶液(A10)。 41.9 g of NMP was added to 7.4 g of the polyimine powder (C2), and the mixture was stirred and dissolved at 80 ° C for 40 hours. Further, this solution was prepared by adding NMP and BCS to 4% by weight of polyimine, 76% by weight of NMP, and 20% by weight of BCS to obtain a polyimine solution (A10).

〔(B)成分(聚矽氧烷)的合成〕 [Synthesis of (B) component (polyoxane)] <合成例11> <Synthesis Example 11>

在具備溫度計及迴流管之200mL的四口反應燒瓶中，混合BCS29.5g、TEOS38.8g、及上述所得之4.1g的化合物11，調製出烷氧基矽烷單體之溶液。將於該溶液中預先混合BCS14.7g、水10.8g及觸媒之草酸0.2g之溶液在室溫下經30分鐘滴入，進一步在室溫進行30分鐘攪拌。其後，使用油浴進行加熱並經30分鐘迴流後，加入UPS含有量為92質量%之甲醇溶液1.2g與BCS0.9g之混合液。進一步進行30分鐘迴流後放置冷卻，得到SiO₂換算濃度為12重量%之聚矽氧烷溶液。 In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 29.5 g of BCS, 38.8 g of TEOS, and 4.1 g of the compound 11 obtained above were mixed to prepare a solution of an alkoxydecane monomer. A solution of 14.7 g of BCS, 10.8 g of water, and 0.2 g of oxalic acid of a catalyst was previously added to the solution, and the solution was added dropwise at room temperature for 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated in an oil bath and refluxed over 30 minutes, and then a mixture of 1.2 g of a methanol solution having a UPS content of 92% by mass and 0.9 g of BCS was added. Further, the mixture was refluxed for 30 minutes, and then left to stand to obtain a polyoxane solution having a SiO ₂ conversion concentration of 12% by weight.

混合所得之聚矽氧烷溶液10.0g及NMP20.0g，得到SiO₂換算濃度為4重量%之聚矽氧烷溶液〔B1〕。 10.0 g of the obtained polyoxane solution and 20.0 g of NMP were mixed to obtain a polyoxyalkylene solution [B1] having a concentration of SiO ₂ of 4% by weight.

<合成例12> <Synthesis Example 12>

在具備溫度計及迴流管之200mL的四口反應燒瓶中，混合BCS29.4g、TEOS38.8g、及C18 4.2g，調製出烷氧基矽烷單體之溶液。將於該溶液中預先混合BCS14.7g、水10.8g及觸媒之草酸0.2g之溶液在室溫下經30分鐘滴入，進一步在室溫進行30分鐘攪拌。其後，使用油浴進行加熱並經30分鐘迴流後，加入UPS含有量為92質量%之甲醇溶液1.2g與BCS0.9g之混合液。進一步進行30分鐘迴流後放置冷卻，得到SiO₂換算濃度為12重量%之聚矽氧烷溶液。 A solution of alkoxy decane monomer was prepared by mixing BCS 29.4 g, TEOS 38.8 g, and C18 4.2 g in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. A solution of 14.7 g of BCS, 10.8 g of water, and 0.2 g of oxalic acid of a catalyst was previously added to the solution, and the solution was added dropwise at room temperature for 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated in an oil bath and refluxed over 30 minutes, and then a mixture of 1.2 g of a methanol solution having a UPS content of 92% by mass and 0.9 g of BCS was added. Further, the mixture was refluxed for 30 minutes, and then left to stand to obtain a polyoxane solution having a SiO ₂ conversion concentration of 12% by weight.

混合所得之聚矽氧烷溶液10.0g及NMP20.0g，得到SiO₂換算濃度為4重量%之聚矽氧烷溶液〔B2〕。 10.0 g of the obtained polyoxane solution and 20.0 g of NMP were mixed to obtain a polyoxyalkylene solution [B2] having a concentration of SiO ₂ of 4% by weight.

<合成例13> <Synthesis Example 13>

在具備溫度計及迴流管之200mL的四口反應燒瓶中，混合BCS30.2g、TEOS39.6g、及上述所得之4.1g化合物11，調製出烷氧基矽烷單體之溶液。將於該溶液中預先混合BCS14.7g、水10.8g及觸媒之草酸0.2g之溶液在室溫下經30分鐘滴入，進一步在室溫進行30分鐘攪拌。其後使用油浴進行加熱並進行60分鐘迴流後放置冷卻，得到SiO₂換算濃度為12重量%之聚矽氧烷溶液。 In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 30.2 parts of BCS, 39.6 g of TEOS, and 4.1 g of the compound 11 obtained above were mixed to prepare a solution of an alkoxydecane monomer. A solution of 14.7 g of BCS, 10.8 g of water, and 0.2 g of oxalic acid of a catalyst was previously added to the solution, and the solution was added dropwise at room temperature for 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated in an oil bath, refluxed for 60 minutes, and then left to stand to obtain a polyoxyalkylene solution having a SiO ₂ conversion concentration of 12% by weight.

混合所得之聚矽氧烷溶液10.0g及NMP20.0g，得到SiO₂換算濃度為4重量%之聚矽氧烷溶液〔B3〕。 10.0 g of the obtained polyoxane solution and 20.0 g of NMP were mixed to obtain a polyoxyalkylene solution [B3] having a concentration of SiO ₂ of 4% by weight.

<合成例14> <Synthesis Example 14>

在具備溫度計及迴流管之200mL的四口反應燒瓶中，混合BCS28.2g、TEOS37.5g、及上述所得之4.1g化合物11，調製出烷氧基矽烷單體之溶液。將於該溶液中預先混合BCS14.1g、水10.8g及觸媒之草酸0.4g之溶液在室溫下經30分鐘滴入，進一步在室溫進行30分鐘攪拌。其後，使用油浴進行加熱並經30分鐘迴流後，加入UPS含有量為92質量%之甲醇溶液2.9g與BCS2.1g之混合液。進一步進行30分鐘迴流後放置冷卻，得到SiO₂換算濃度為12重量%之聚矽氧烷溶液。 In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 28.2 g of BCS, 37.5 g of TEOS, and 4.1 g of the compound 11 obtained above were mixed to prepare a solution of an alkoxydecane monomer. To the solution, a solution of 14.1 g of BCS, 10.8 g of water, and 0.4 g of oxalic acid of a catalyst was mixed in advance at room temperature for 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated in an oil bath and refluxed over 30 minutes, and then a mixture of 2.9 g of a methanol solution having a UPS content of 92% by mass and 2.1 g of BCS was added. Further, the mixture was refluxed for 30 minutes, and then left to stand to obtain a polyoxane solution having a SiO ₂ conversion concentration of 12% by weight.

混合所得之聚矽氧烷溶液10.0g及NMP20.0g，得到SiO₂換算濃度為4重量%之聚矽氧烷溶液〔B4〕。 10.0 g of the obtained polyoxane solution and 20.0 g of NMP were mixed to obtain a polyoxyalkylene solution [B4] having a concentration of SiO ₂ of 4% by weight.

<合成例15> <Synthesis Example 15>

在具備溫度計及迴流管之200mL的四口反應燒瓶中，混合BCS25.4g、TEOS20.0g、上述所得之化合物11 8.2g、及MPMS19.9g，調製出烷氧基矽烷單體之溶液。將於該溶液中預先混合BCS12.7g、水10.8g及觸媒之草酸1.1g之溶液在室溫下經30分鐘滴入，進一步在室溫進行30分鐘攪拌。其後，使用油浴進行加熱並經30分鐘迴流後，加入UPS含有量為92質量%之甲醇溶液1.2g與 BCS0.9g之混合液。進一步進行30分鐘迴流後放置冷卻，得到SiO₂換算濃度為12重量%之聚矽氧烷溶液。 In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, BCS 25.4 g, TEOS 20.0 g, the above-obtained compound 11 8.2 g, and MPMS 19.9 g were mixed to prepare a solution of an alkoxydecane monomer. To the solution, a solution of 12.7 g of BCS, 10.8 g of water, and 1.1 g of oxalic acid of a catalyst was mixed in advance at room temperature for 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated in an oil bath and refluxed over 30 minutes, and then a mixture of 1.2 g of a methanol solution having a UPS content of 92% by mass and 0.9 g of BCS was added. Further, the mixture was refluxed for 30 minutes, and then left to stand to obtain a polyoxane solution having a SiO ₂ conversion concentration of 12% by weight.

混合所得之聚矽氧烷溶液10.0g及NMP20.0g，得到SiO₂換算濃度為4重量%之聚矽氧烷溶液〔B5〕。 10.0 g of the obtained polyoxane solution and 20.0 g of NMP were mixed to obtain a polyoxyalkylene solution [B5] having a concentration of SiO ₂ of 4% by weight.

<合成例16> <Synthesis Example 16>

在具備溫度計及迴流管之200mL的四口反應燒瓶中，混合BCS25.2g、TEOS20.0g、上述所得之化合物11 8.2g、及STMS20.2g，調製出烷氧基矽烷單體之溶液。將於該溶液中預先混合BCS12.6g、水10.8g及觸媒之草酸1.1g之溶液在室溫下經30分鐘滴入，進一步在室溫進行30分鐘攪拌。其後，使用油浴進行加熱並經30分鐘迴流後，加入UPS含有量為92質量%之甲醇溶液1.2g與BCS0.9g之混合液。進一步進行30分鐘迴流後放置冷卻，得到SiO₂換算濃度為12重量%之聚矽氧烷溶液。 In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 25.2 g of BCS, 20.0 g of TEOS, 8.2 g of the compound 11 obtained above, and 20.2 g of STMS were mixed to prepare a solution of an alkoxydecane monomer. To the solution, a solution of 12.6 g of BCS, 10.8 g of water, and 1.1 g of oxalic acid of a catalyst was mixed in advance at room temperature for 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated in an oil bath and refluxed over 30 minutes, and then a mixture of 1.2 g of a methanol solution having a UPS content of 92% by mass and 0.9 g of BCS was added. Further, the mixture was refluxed for 30 minutes, and then left to stand to obtain a polyoxane solution having a SiO ₂ conversion concentration of 12% by weight.

混合所得之聚矽氧烷溶液10.0g及NMP20.0g，得到SiO₂換算濃度為4重量%之聚矽氧烷溶液〔B6〕。 10.0 g of the obtained polyoxane solution and 20.0 g of NMP were mixed to obtain a polyoxyalkylene solution [B6] having a concentration of SiO ₂ of 4% by weight.

<合成例17> <Synthesis Example 17>

在具備溫度計及迴流管之200mL的四口反應燒瓶中，混合BCS25.8g、TEOS20.0g、C18 4.2g、C12 3.3g、及MPMS19.9g，調製出烷氧基矽烷單體之溶液。將於該溶液中預先混合BCS12.9g、水10.8g及觸媒之草酸1.1g之溶液在室溫下經30分鐘滴入，進一步在室溫進行30分 鐘攪拌。其後，使用油浴進行加熱並經30分鐘迴流後，加入UPS含有量為92質量%之甲醇溶液1.2g與BCS0.9g之混合液。進一步進行30分鐘迴流後放置冷卻，得到SiO₂換算濃度為12重量%之聚矽氧烷溶液。 In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, BCS 25.8 g, TEOS 20.0 g, C18 4.2 g, C12 3.3 g, and MPMS 19.9 g were mixed to prepare a solution of an alkoxydecane monomer. To the solution, a solution of 12.9 g of BCS, 10.8 g of water, and 1.1 g of oxalic acid of a catalyst was mixed in advance at room temperature for 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated in an oil bath and refluxed over 30 minutes, and then a mixture of 1.2 g of a methanol solution having a UPS content of 92% by mass and 0.9 g of BCS was added. Further, the mixture was refluxed for 30 minutes, and then left to stand to obtain a polyoxane solution having a SiO ₂ conversion concentration of 12% by weight.

混合所得之聚矽氧烷溶液10.0g及NMP20.0g，得到SiO₂換算濃度為4重量%之聚矽氧烷溶液〔B7〕。 10.0 g of the obtained polyoxane solution and 20.0 g of NMP were mixed to obtain a polyoxyalkylene solution [B7] having a concentration of SiO ₂ of 4% by weight.

<合成例18> <Synthesis Example 18>

在具備溫度計及迴流管之200mL的四口反應燒瓶中，混合BCS31.5g、TEOS37.1g、及MTES3.6g，調製出烷氧基矽烷單體之溶液。將於該溶液中預先混合BCS15.7g、水10.8g及觸媒之草酸0.1g之溶液在室溫下經30分鐘滴入，進一步在室溫進行30分鐘攪拌。其後使用油浴進行加熱並進行60分鐘迴流後放置冷卻，得到SiO₂換算濃度為12重量%之聚矽氧烷溶液。 A 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube was mixed with BCS 31.5 g, TEOS 37.1 g, and MTES 3.6 g to prepare a solution of an alkoxydecane monomer. To the solution, a solution of 15.7 g of BCS, 10.8 g of water, and 0.1 g of oxalic acid of a catalyst was mixed in advance at room temperature for 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated in an oil bath, refluxed for 60 minutes, and then left to stand to obtain a polyoxyalkylene solution having a SiO ₂ conversion concentration of 12% by weight.

混合所得之聚矽氧烷溶液10.0g及NMP20.0g，得到SiO₂換算濃度為4重量%之聚矽氧烷溶液〔B8〕。 10.0 g of the obtained polyoxane solution and 20.0 g of NMP were mixed to obtain a polyoxyalkylene solution [B8] having a concentration of SiO ₂ of 4% by weight.

<合成例19> <Synthesis Example 19>

在具備溫度計及迴流管之200mL的四口反應燒瓶中，混合BCS26.2g、TEOS20.8g、上述所得之化合物11 8.2g、及MPMS19.9g，調製出烷氧基矽烷單體之溶液。將於該溶液中預先混合BCS13.1g、水10.8g及觸媒之草酸1.1g之溶液在室溫下經30分鐘滴入，進一步在室溫進行 30分鐘攪拌。其後，使用油浴進行加熱並經30分鐘迴流後，加入UPS含有量為92質量%的甲醇溶液0.6g與BCS0.4g之混合液。進一步進行30分鐘迴流後放置冷卻，得到SiO₂換算濃度為12重量%之聚矽氧烷溶液。 In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 26.2 g of BCS, 20.8 g of TEOS, 8.2 g of the compound 11 obtained above, and 19.9 g of MPMS were mixed to prepare a solution of an alkoxydecane monomer. To the solution, a solution of 13.1 g of BCS, 10.8 g of water, and 1.1 g of oxalic acid of a catalyst was mixed in advance at room temperature for 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated in an oil bath and refluxed over 30 minutes, and then a mixture of 0.6 g of a methanol solution having a UPS content of 92% by mass and 0.4 g of BCS was added. Further, the mixture was refluxed for 30 minutes, and then left to stand to obtain a polyoxane solution having a SiO ₂ conversion concentration of 12% by weight.

混合所得之聚矽氧烷溶液10.0g及NMP20.0g，得到SiO₂換算濃度為4重量%之聚矽氧烷溶液〔B9〕。 10.0 g of the obtained polyoxane solution and 20.0 g of NMP were mixed to obtain a polyoxoxane solution [B9] having a concentration of SiO ₂ of 4% by weight.

晶胞之製作、及電氣特性、垂直配向性、再加工性、白化特性、應答速度等評估如以下所示進行。 The production of the unit cell, and the evaluation of electrical characteristics, vertical alignment, reworkability, whitening characteristics, and response speed were performed as follows.

〔晶胞的製作〕 [Production of unit cell]

將液晶配向處理劑以固體ITO電極所形成之ITO電極基板、或畫素尺寸為100μm×300μm(微米)下，在各形成線寬/線距為5μm的ITO電極圖型之ITO電極基板的ITO面進行旋塗。其次，在80℃之熱板上進行2分鐘乾燥後，以200℃或者220℃的熱風循環式烤箱進行30分鐘燒成，形成膜厚100nm的液晶配向膜。準備將該基板2片(皆為固體基板或固體基板與圖型基板)，於一方基板之液晶配向膜面上散佈4μm或者6μm之珠空間後，自其上塗布密封劑。另一方的基板之液晶配向膜面作為內側，貼合兩基板後，使密封劑硬化後製作出空胞。其後，於空胞藉由減壓注入法注入液晶MLC-6608(默克公司製之商品名)製做出晶胞。 ITO electrode substrate formed of a solid ITO electrode, or an ITO electrode substrate having an ITO electrode pattern having a line width/line pitch of 5 μm and having a pixel size of 100 μm × 300 μm (micrometer) The surface is spin coated. Next, it was dried on a hot plate at 80 ° C for 2 minutes, and then fired in a hot air circulating oven at 200 ° C or 220 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm. Two sheets of the substrate (all solid substrates, solid substrates, and pattern substrates) were prepared, and a bead space of 4 μm or 6 μm was spread on the liquid crystal alignment film surface of one of the substrates, and then a sealant was applied thereon. The liquid crystal alignment film surface of the other substrate is used as the inner side, and after bonding the two substrates, the sealing agent is cured to produce a hollow cell. Thereafter, a cell was produced by injecting liquid crystal MLC-6608 (trade name, manufactured by Merck & Co., Inc.) into a hollow cell by a vacuum injection method.

製作晶胞後，於晶胞一邊外加交流或直流之電壓，一邊照射熱或紫外線，而可控制液晶分子之配向。 After the unit cell is produced, an alternating current or a direct current voltage is applied to the side of the unit cell, and the alignment of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays.

〔電氣特性(電壓保持率及離子密度)的評估〕 [Evaluation of electrical characteristics (voltage holding ratio and ion density)]

將晶胞在60℃之溫度下，外加1V之電壓60μs，測定1667ms後之電壓，電壓可維持到怎樣程度，以電壓保持率(VHR)計算。 The cell was applied at a temperature of 60 ° C, and a voltage of 1 V was applied for 60 μs. The voltage after 1667 ms was measured, and the voltage was maintained to such an extent as to be calculated by the voltage holding ratio (VHR).

進一步使用上述晶胞，測定在60℃之溫度下的離子密度。即，測定於晶胞外加電壓±10V、頻率0.01Hz的三角波時之離子密度。測定裝置使用東陽Technica公司製的6245型液晶物性評估裝置。 Further, the above unit cell was used, and the ion density at a temperature of 60 ° C was measured. That is, the ion density at the time when a triangular wave having a voltage of ±10 V and a frequency of 0.01 Hz was applied to the unit cell was measured. The measuring device used a 6245 liquid crystal physical property evaluation device manufactured by Dongyang Technica Co., Ltd.

〔垂直配向性之評估〕 [Evaluation of Vertical Orientation]

將晶胞在100℃的循環式烤箱中進行30分鐘退火處理。其後將取出之晶胞，在使偏光板呈正交偏光鏡之狀態下進行顯微鏡觀察，觀察液晶之配向混亂的網域(Domain)狀態。 The unit cell was annealed in a circulating oven at 100 ° C for 30 minutes. Thereafter, the unit cell to be taken out was subjected to microscopic observation while the polarizing plate was placed in a crossed polarizing mirror, and the state of the domain in which the alignment of the liquid crystal was disordered was observed.

〔再加工性之評估〕 [Evaluation of reworkability]

將液晶配向處理劑於形成固體ITO電極之ITO電極基板上進行旋塗。其後在80℃之熱板上進行2分鐘乾燥後，在200℃或者220℃之熱風循環式烤箱中進行30分鐘燒成，形成膜厚100nm之液晶配向膜。將該基板於50℃之東京應化工業公司製的NMD-3進行10分鐘浸漬後，經水洗後，在80℃熱風循環式烤箱下進行10分鐘乾燥。其後，將浸漬前後之狀態以目視進行觀察及進行接觸角測 定，接觸角可恢復至液晶配向處理劑之塗布前狀態時評估再加工可能：○，無法恢復者評估為再加工不可：×。 The liquid crystal alignment treatment agent was spin-coated on the ITO electrode substrate on which the solid ITO electrode was formed. Thereafter, the film was dried on a hot plate at 80 ° C for 2 minutes, and then fired in a hot air circulating oven at 200 ° C or 220 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm. The substrate was immersed in NMD-3 manufactured by Tokyo Chemical Industry Co., Ltd. at 50 ° C for 10 minutes, washed with water, and dried in a hot air circulating oven at 80 ° C for 10 minutes. Thereafter, the state before and after the immersion is visually observed and the contact angle is measured. When the contact angle can be restored to the pre-coating state of the liquid crystal alignment agent, it is possible to evaluate the rework: ○, the unrecoverable person evaluates that reprocessing is not possible: ×.

〔白化特性之評估〕 [Evaluation of whitening characteristics]

將液晶配向處理劑於鉻基板(經鉻蒸鍍之玻璃基板)進行旋塗，溫度23℃，在相對濕度60%的環境下放置10分鐘，其後於塗膜面端部以目視觀察是否有聚合物之凝集物產生。 The liquid crystal alignment treatment agent was spin-coated on a chromium substrate (glass substrate evaporated by chrome plating) at a temperature of 23 ° C for 10 minutes in a relative humidity of 60%, and then visually observed at the end of the coating film surface. Polymer agglomerates are produced.

〔應答速度之評估〕 [Evaluation of response speed]

於晶胞外加±5V的AC電壓、頻率1kHz的矩形波之液晶面板的亮度時間變化由示波器讀取。將未外加電壓時的亮度作為0%，外加±5V的電壓之飽和亮度值作為100%，將亮度變化至10~90%的時間作為啟始的應答速度，對於依據上述晶胞的製作方法所得之晶胞，一邊外加交流或直流之電壓，一邊進行照射熱或紫外線後之應答速度的評估。 The brightness time change of the liquid crystal panel with an AC voltage of ±5 V and a rectangular wave of 1 kHz frequency is read by the oscilloscope. The brightness when no voltage is applied is taken as 0%, the saturation brightness value of the voltage of ±5V is taken as 100%, and the time when the brightness is changed to 10~90% is taken as the initial response speed, which is obtained according to the manufacturing method of the above unit cell. The unit cell is subjected to an evaluation of the response speed after irradiation with heat or ultraviolet light by applying an alternating current or a direct current voltage.

(參考例1) (Reference example 1)

將聚矽氧烷溶液(B1)作為液晶配向處理劑使用，進行〔垂直配向性之評估〕及〔再加工性之評估〕。結果如表1及表3所示。進一步依據〔電氣特性之評估〕，進行電壓保持率及離子密度的評估。結果如表2所示。 The polyaluminoxane solution (B1) was used as a liquid crystal alignment treatment agent, and [evaluation of vertical alignment property] and [evaluation of reworkability] were carried out. The results are shown in Tables 1 and 3. Further, based on [evaluation of electrical characteristics], evaluation of voltage holding ratio and ion density was performed. The results are shown in Table 2.

(參考例2) (Reference example 2)

混合聚矽氧烷溶液(B1)3.0g與聚醯胺酸溶液(A1)7.0g，得到液晶配向處理劑(1)。使用該液晶配向處理劑，進行〔再加工性的評估〕、〔白化特性的評估〕及〔垂直配向性的評估〕。結果如表3、表4及表5所示。進一步依據〔電氣特性的評估〕，進行電壓保持率及離子密度的評估。結果如表6所示。 3.0 g of the polyoxydecane solution (B1) and 7.0 g of the polyaminic acid solution (A1) were mixed to obtain a liquid crystal alignment treatment agent (1). Using the liquid crystal alignment agent, [evaluation of reworkability], [evaluation of whitening characteristics], and [evaluation of vertical alignment property] were carried out. The results are shown in Tables 3, 4 and 5. Further, based on [evaluation of electrical characteristics], evaluation of voltage holding ratio and ion density was performed. The results are shown in Table 6.

(參考例3) (Reference Example 3)

混合聚矽氧烷溶液(B1)3.0g與聚醯胺酸溶液(A2)7.0g，得到液晶配向處理劑(2)。使用該液晶配向處理劑，進行〔再加工性的評估〕。結果如表3所示。 3.0 g of the polyoxydecane solution (B1) and 7.0 g of the polyaminic acid solution (A2) were mixed to obtain a liquid crystal alignment treatment agent (2). The liquid crystal alignment treatment agent was used to carry out [evaluation of reworkability]. The results are shown in Table 3.

(參考例4) (Reference example 4)

混合聚矽氧烷溶液(B1)3.0g與聚醯胺酸溶液(A3)7.0g，得到液晶配向處理劑(3)。使用該液晶配向處理劑，進行〔再加工性的評估〕。結果如表3所示。 3.0 g of the polyoxydecane solution (B1) and 7.0 g of the polyaminic acid solution (A3) were mixed to obtain a liquid crystal alignment treatment agent (3). The liquid crystal alignment treatment agent was used to carry out [evaluation of reworkability]. The results are shown in Table 3.

(參考例5) (Reference example 5)

混合聚矽氧烷溶液(B1)3.0g與聚醯胺酸溶液(A4)7.0g，得到液晶配向處理劑(4)。使用該液晶配向處理劑，進行〔再加工性的評估〕。結果如表3所示。 3.0 g of the polyoxydecane solution (B1) and 7.0 g of the polyaminic acid solution (A4) were mixed to obtain a liquid crystal alignment treatment agent (4). The liquid crystal alignment treatment agent was used to carry out [evaluation of reworkability]. The results are shown in Table 3.

(參考例6) (Reference example 6)

混合聚矽氧烷溶液(B1)3.0g與聚醯胺酸溶液(A5)7.0g，得到液晶配向處理劑(5)。使用該液晶配向處理劑，進行〔再加工性的評估〕、〔白化特性的評估〕及〔垂直配向性的評估〕。結果如表3、表4及表5所示。進一步依據〔電氣特性的評估〕進行電壓保持率及離子密度的評估。結果如表6所示。 3.0 g of the polyoxydecane solution (B1) and 7.0 g of the polyaminic acid solution (A5) were mixed to obtain a liquid crystal alignment treatment agent (5). Using the liquid crystal alignment agent, [evaluation of reworkability], [evaluation of whitening characteristics], and [evaluation of vertical alignment property] were carried out. The results are shown in Tables 3, 4 and 5. Further, the voltage holding ratio and the ion density were evaluated based on [evaluation of electrical characteristics]. The results are shown in Table 6.

(參考例7) (Reference example 7)

混合聚矽氧烷溶液(B4)3.0g與聚醯胺酸溶液(A1)7.0g，得到液晶配向處理劑(6)。使用該液晶配向處理劑，進行〔白化特性的評估〕。結果如表6所示。 3.0 g of the polyoxydecane solution (B4) and 7.0 g of the polyaminic acid solution (A1) were mixed to obtain a liquid crystal alignment treatment agent (6). [Evaluation of whitening characteristics] was carried out using the liquid crystal alignment agent. The results are shown in Table 6.

(參考例8) (Reference Example 8)

混合聚矽氧烷溶液(B4)3.0g與聚醯胺酸溶液(A2)7.0g，得到液晶配向處理劑(7)。使用該液晶配向處理劑，進行〔白化特性的評估〕。結果如表6所示。 3.0 g of the polyoxydecane solution (B4) and 7.0 g of the polyaminic acid solution (A2) were mixed to obtain a liquid crystal alignment treatment agent (7). [Evaluation of whitening characteristics] was carried out using the liquid crystal alignment agent. The results are shown in Table 6.

(實施例1) (Example 1)

混合聚矽氧烷溶液(B5)3.0g與聚醯胺酸溶液(A1)7.0g，得到液晶配向處理劑(8)。使用該液晶配向處理劑，進行〔應答速度的評估〕及〔垂直配向性的評估〕。結果如表7所示。 3.0 g of the polyoxydecane solution (B5) and 7.0 g of the polyaminic acid solution (A1) were mixed to obtain a liquid crystal alignment treatment agent (8). Using the liquid crystal alignment agent, [evaluation of response speed] and [evaluation of vertical alignment property] were carried out. The results are shown in Table 7.

(實施例2) (Example 2)

混合聚矽氧烷溶液(B5)3.0g與聚醯胺酸溶液(A2)7.0g，得到液晶配向處理劑(9)。使用該液晶配向處理劑，進行〔應答速度的評估〕及〔垂直配向性的評估〕。結果如表7所示。 3.0 g of the polyoxydecane solution (B5) and 7.0 g of the polyaminic acid solution (A2) were mixed to obtain a liquid crystal alignment treatment agent (9). Using the liquid crystal alignment agent, [evaluation of response speed] and [evaluation of vertical alignment property] were carried out. The results are shown in Table 7.

(實施例3) (Example 3)

混合聚矽氧烷溶液(B5)3.0g與聚醯胺酸溶液(A3)7.0g，得到液晶配向處理劑(10)。使用該液晶配向處理劑，進行〔應答速度的評估〕及〔垂直配向性的評估〕。結果如表7所示。 3.0 g of the polyoxydecane solution (B5) and 7.0 g of the polyaminic acid solution (A3) were mixed to obtain a liquid crystal alignment treatment agent (10). Using the liquid crystal alignment agent, [evaluation of response speed] and [evaluation of vertical alignment property] were carried out. The results are shown in Table 7.

(實施例4) (Example 4)

混合聚矽氧烷溶液(B5)3.0g與聚醯胺酸溶液(A4)7.0g，得到液晶配向處理劑(11)。使用該液晶配向處理劑，進行〔應答速度的評估〕及〔垂直配向性的評估〕。結果如表7所示。 3.0 g of the polyoxydecane solution (B5) and 7.0 g of the polyaminic acid solution (A4) were mixed to obtain a liquid crystal alignment treatment agent (11). Using the liquid crystal alignment agent, [evaluation of response speed] and [evaluation of vertical alignment property] were carried out. The results are shown in Table 7.

(實施例5) (Example 5)

混合聚矽氧烷溶液(B5)3.0g與聚醯胺酸溶液(A5)7.0g，得到液晶配向處理劑(12)。使用該液晶配向處理劑，進行〔應答速度的評估〕、〔垂直配向性的評估〕、及〔再加工性的評估〕。結果如表7、表8及表10所示。進一步依據〔電氣特性的評估〕，進行電壓保持率及離子密度的評估。結果如表9所示。 3.0 g of the polyoxydecane solution (B5) and 7.0 g of the polyaminic acid solution (A5) were mixed to obtain a liquid crystal alignment treatment agent (12). Using the liquid crystal alignment agent, [evaluation of response speed], [evaluation of vertical alignment property], and [evaluation of reworkability] were carried out. The results are shown in Table 7, Table 8, and Table 10. Further, based on [evaluation of electrical characteristics], evaluation of voltage holding ratio and ion density was performed. The results are shown in Table 9.

(實施例6) (Example 6)

混合聚矽氧烷溶液(B5)3.0g與聚醯胺酸溶液(A6)7.0g，得到液晶配向處理劑(13)。使用該液晶配向處理劑，進行〔應答速度的評估〕及〔垂直配向性的評估〕。結果如表7所示。 3.0 g of the polyoxydecane solution (B5) and 7.0 g of the polyaminic acid solution (A6) were mixed to obtain a liquid crystal alignment treatment agent (13). Using the liquid crystal alignment agent, [evaluation of response speed] and [evaluation of vertical alignment property] were carried out. The results are shown in Table 7.

(實施例7) (Example 7)

混合聚矽氧烷溶液(B5)3.0g與聚醯胺酸溶液(A7)7.0g，得到液晶配向處理劑(14)。使用該液晶配向處理劑，進行〔應答速度的評估〕及〔垂直配向性的評估〕。結果如表7所示。 3.0 g of the polyoxydecane solution (B5) and 7.0 g of the polyaminic acid solution (A7) were mixed to obtain a liquid crystal alignment treatment agent (14). Using the liquid crystal alignment agent, [evaluation of response speed] and [evaluation of vertical alignment property] were carried out. The results are shown in Table 7.

(實施例8) (Example 8)

混合聚矽氧烷溶液(B5)3.0g與聚醯胺酸溶液(A8)7.0g，得到液晶配向處理劑(15)。使用該液晶配向處理劑，進行〔應答速度的評估〕及〔垂直配向性的評估〕。結果如表7所示。進一步依據〔電氣特性的評估〕，進行電壓保持率及離子密度的評估。結果如表9所示。 3.0 g of the polyoxydecane solution (B5) and 7.0 g of the polyaminic acid solution (A8) were mixed to obtain a liquid crystal alignment treatment agent (15). Using the liquid crystal alignment agent, [evaluation of response speed] and [evaluation of vertical alignment property] were carried out. The results are shown in Table 7. Further, based on [evaluation of electrical characteristics], evaluation of voltage holding ratio and ion density was performed. The results are shown in Table 9.

(實施例9) (Example 9)

混合聚矽氧烷溶液(B5)3.0g與聚醯胺酸溶液(A9)7.0g，得到液晶配向處理劑(16)。使用該液晶配 向處理劑，進行〔應答速度的評估〕、〔垂直配向性的評估〕及〔再加工性的評估〕。結果如表7及表10所示。 3.0 g of the polyoxydecane solution (B5) and 7.0 g of the polyaminic acid solution (A9) were mixed to obtain a liquid crystal alignment treatment agent (16). Use this LCD with To the treatment agent, [evaluation of response speed], [evaluation of vertical alignment], and [evaluation of reworkability] were carried out. The results are shown in Tables 7 and 10.

(實施例10) (Embodiment 10)

混合聚矽氧烷溶液(B5)3.0g與聚醯胺酸溶液(A10)7.0g，得到液晶配向處理劑(17)。使用該液晶配向處理劑，進行〔應答速度的評估〕及〔垂直配向性的評估〕。結果如表7所示。 3.0 g of the polyoxydecane solution (B5) and 7.0 g of the polyaminic acid solution (A10) were mixed to obtain a liquid crystal alignment treatment agent (17). Using the liquid crystal alignment agent, [evaluation of response speed] and [evaluation of vertical alignment property] were carried out. The results are shown in Table 7.

(實施例11) (Example 11)

混合聚矽氧烷溶液(B6)3.0g與聚醯胺酸溶液(A1)7.0g，得到液晶配向處理劑(18)。使用該液晶配向處理劑，進行〔應答速度的評估〕及〔垂直配向性的評估〕。結果如表7及表8所示。 3.0 g of the polyoxydecane solution (B6) and 7.0 g of the polyaminic acid solution (A1) were mixed to obtain a liquid crystal alignment treatment agent (18). Using the liquid crystal alignment agent, [evaluation of response speed] and [evaluation of vertical alignment property] were carried out. The results are shown in Tables 7 and 8.

(比較例1) (Comparative Example 1)

將聚矽氧烷溶液(B2)作為液晶配向處理劑使用，進行〔垂直配向性的評估〕及〔再加工性的評估〕。結果如表1及表3所示。 The polyaluminoxane solution (B2) was used as a liquid crystal alignment treatment agent, and [evaluation of vertical alignment property] and [evaluation of reworkability] were carried out. The results are shown in Tables 1 and 3.

(比較例2) (Comparative Example 2)

將聚矽氧烷溶液(B3)作為液晶配向處理劑使用，依據〔電氣特性的評估〕進行電壓保持率及離子密度的評估。結果如表2所示。進一步進行〔再加工性的評估〕。 結果如表3所示。 The polyoxane solution (B3) was used as a liquid crystal alignment treatment agent, and the voltage holding ratio and the ion density were evaluated based on [evaluation of electrical characteristics]. The results are shown in Table 2. Further [evaluation of reworkability]. The results are shown in Table 3.

(比較例3) (Comparative Example 3)

混合聚矽氧烷溶液(B2)3.0g與聚醯胺酸溶液(A1)7.0g，得到液晶配向處理劑(19)。使用該液晶配向處理劑，進行〔垂直配向性的評估〕及〔白化特性的評估〕。結果如表4及表5所示。 3.0 g of the polyoxydecane solution (B2) and 7.0 g of the polyaminic acid solution (A1) were mixed to obtain a liquid crystal alignment treatment agent (19). Using this liquid crystal alignment treatment agent, [evaluation of vertical alignment property] and [evaluation of whitening characteristics] were carried out. The results are shown in Tables 4 and 5.

(比較例4) (Comparative Example 4)

混合聚矽氧烷溶液(B2)3.0g與聚醯胺酸溶液(A5)7.0g，得到液晶配向處理劑(20)。使用該液晶配向處理劑，進行〔垂直配向性的評估〕及〔白化特性的評估〕。結果如表4及表5所示。 3.0 g of the polyoxydecane solution (B2) and 7.0 g of the polyaminic acid solution (A5) were mixed to obtain a liquid crystal alignment treatment agent (20). Using this liquid crystal alignment treatment agent, [evaluation of vertical alignment property] and [evaluation of whitening characteristics] were carried out. The results are shown in Tables 4 and 5.

(比較例5) (Comparative Example 5)

混合聚矽氧烷溶液(B3)3.0g與聚醯胺酸溶液(A1)7.0g，得到液晶配向處理劑(21)。使用該液晶配向處理劑，依據〔電氣特性的評估〕進行電壓保持率及離子密度的評估。結果如表6所示。 3.0 g of the polyoxydecane solution (B3) and 7.0 g of the polyaminic acid solution (A1) were mixed to obtain a liquid crystal alignment treatment agent (21). The liquid crystal alignment treatment agent was used to evaluate the voltage holding ratio and the ion density based on [evaluation of electrical characteristics]. The results are shown in Table 6.

(比較例6) (Comparative Example 6)

混合聚矽氧烷溶液(B3)3.0g與聚醯胺酸溶液(A5)7.0g，得到液晶配向處理劑(22)。使用該液晶配向處理劑，依據〔電氣特性的評估〕進行電壓保持率及離 子密度的評估。結果如表6所示。 3.0 g of the polyoxydecane solution (B3) and 7.0 g of the polyaminic acid solution (A5) were mixed to obtain a liquid crystal alignment treatment agent (22). Using the liquid crystal alignment agent, the voltage retention rate and the separation are performed according to [evaluation of electrical characteristics] Evaluation of subdensity. The results are shown in Table 6.

(比較例7) (Comparative Example 7)

混合聚矽氧烷溶液(B7)3.0g與聚醯胺酸溶液(A1)7.0g，得到液晶配向處理劑(23)。使用該液晶配向處理劑，進行〔應答速度的評估〕及〔垂直配向性的評估〕。結果如表7所示。 3.0 g of the polyoxydecane solution (B7) and 7.0 g of the polyaminic acid solution (A1) were mixed to obtain a liquid crystal alignment treatment agent (23). Using the liquid crystal alignment agent, [evaluation of response speed] and [evaluation of vertical alignment property] were carried out. The results are shown in Table 7.

(比較例8) (Comparative Example 8)

將聚醯亞胺/聚醯胺酸溶液(A9)作為液晶配向處理劑使用，進行〔應答速度的評估〕及〔垂直配向性的評估〕。結果如表7及表8所示。 The polyimine/polyaminic acid solution (A9) was used as a liquid crystal alignment treatment agent, and [evaluation of response speed] and [evaluation of vertical alignment property] were carried out. The results are shown in Tables 7 and 8.

(比較例9) (Comparative Example 9)

混合聚矽氧烷溶液(B8)3.0g與聚醯胺酸溶液(A5)7.0g，得到液晶配向處理劑(24)。使用該液晶配向處理劑，進行〔應答速度的評估〕及〔垂直配向性的評估〕。結果如表7所示。進一步依據〔電氣特性的評估〕進行電壓保持率及離子密度的評估。結果如表9所示。 3.0 g of the polyoxydecane solution (B8) and 7.0 g of the polyaminic acid solution (A5) were mixed to obtain a liquid crystal alignment treatment agent (24). Using the liquid crystal alignment agent, [evaluation of response speed] and [evaluation of vertical alignment property] were carried out. The results are shown in Table 7. Further, the voltage holding ratio and the ion density were evaluated based on [evaluation of electrical characteristics]. The results are shown in Table 9.

(比較例10) (Comparative Example 10)

混合聚矽氧烷溶液(B8)3.0g與聚醯胺酸溶液(A8)7.0g，得到液晶配向處理劑(25)。使用該液晶配向處理劑，進行〔應答速度的評估〕及〔垂直配向性的評 估〕。結果如表7所示。進一步依據〔電氣特性的評估〕，進行電壓保持率及離子密度的評估。結果如表9所示。 3.0 g of the polyoxydecane solution (B8) and 7.0 g of the polyaminic acid solution (A8) were mixed to obtain a liquid crystal alignment treatment agent (25). Using the liquid crystal alignment agent to perform [evaluation of response speed] and [vertical alignment evaluation estimate〕. The results are shown in Table 7. Further, based on [evaluation of electrical characteristics], evaluation of voltage holding ratio and ion density was performed. The results are shown in Table 9.

(比較例11) (Comparative Example 11)

混合聚矽氧烷溶液(B5)3.0g與聚矽氧烷溶液(B9)7.0g，得到液晶配向處理劑(26)。使用該液晶配向處理劑，進行〔應答速度的評估〕及〔再加工性的評估〕。結果如表8及表10所示。 3.0 g of a polyoxymethane solution (B5) and 7.0 g of a polyoxyalkylene solution (B9) were mixed to obtain a liquid crystal alignment treatment agent (26). Using the liquid crystal alignment agent, [evaluation of response speed] and [evaluation of reworkability] were carried out. The results are shown in Tables 8 and 10.

(比較例12) (Comparative Example 12)

混合聚矽氧烷溶液(B6)3.0g與聚矽氧烷溶液(B9)7.0g，得到液晶配向處理劑(27)。使用該液晶配向處理劑，進行〔應答速度的評估〕及〔再加工性的評估〕。結果如表8及表10所示。 3.0 g of a polyoxydecane solution (B6) and 7.0 g of a polyoxyalkylene solution (B9) were mixed to obtain a liquid crystal alignment treatment agent (27). Using the liquid crystal alignment agent, [evaluation of response speed] and [evaluation of reworkability] were carried out. The results are shown in Tables 8 and 10.

表1中，在參考例1之晶胞，於退火處理後完全無觀察到配向混亂的網域。另一方面，在比較例1之晶胞，於退火處理後觀察到多數配向混亂的網域。 In Table 1, in the unit cell of Reference Example 1, no alignment disorder was observed after the annealing treatment. On the other hand, in the unit cell of Comparative Example 1, a majority of the disordered domains were observed after the annealing treatment.

表2中，即使對於電氣特性，含有脲基之液晶配向處理劑(參考例1)與未含脲基之液晶配向處理劑(比較例2)做比較，得知其VHR(電壓保持率)較高，離子密度較低。 In Table 2, even if the urea-based liquid crystal alignment treatment agent (Reference Example 1) was compared with the urea-based liquid crystal alignment treatment agent (Comparative Example 2), the VHR (voltage retention ratio) was compared. High, low ion density.

表3中，有關再加工性，與僅含有聚矽氧烷之成分的液晶配向處理劑做比較，得知含有選自聚醯胺酸及聚醯亞胺所成群之至少一種類聚合物的液晶配向處理劑具有更高再加工性。 In Table 3, regarding the reworkability, compared with a liquid crystal alignment treatment agent containing only a component of polyoxyalkylene, it is known that at least one type of polymer selected from the group consisting of polylysine and polyimine is contained. The liquid crystal alignment treatment agent has higher reworkability.

表4中，含脲基的液晶配向處理劑與未含有脲基之液晶配向處理劑做比較，得知具有優良白化特性。 In Table 4, the urea group-containing liquid crystal alignment treatment agent was compared with a liquid crystal alignment treatment agent not containing a urea group, and it was found to have excellent whitening characteristics.

表5中，與表1同樣地，在參考例2、6的晶胞中，於退火處理後，完全無觀察到配向混亂的網域。另一方面，在比較例3、4之晶胞中，於退火處理後，觀察到多數配向混亂的網域。 In Table 5, in the same manner as in Table 1, in the unit cells of Reference Examples 2 and 6, after the annealing treatment, no domain in which the alignment disorder was observed was observed. On the other hand, in the unit cells of Comparative Examples 3 and 4, after the annealing treatment, a majority of the domains with disordered alignment were observed.

表6中，與表2同樣地有關電氣特性，含有脲基之液晶配向處理劑(參考例2、6)與未含脲基之液晶配向處理劑(比較例5、6)做比較，得知其VHR較高，離子密度較低。 In Table 6, in the same manner as in Table 2, the liquid crystal alignment treatment agent containing the urea group (Reference Examples 2 and 6) was compared with the liquid crystal alignment treatment agent without the urea group (Comparative Examples 5 and 6). Its VHR is higher and its ion density is lower.

應答速度之判定○：快(良好)×：慢(差) Determination of response speed ○: fast (good) ×: slow (poor)

退火處理後之網域觀察結果 Domain observation after annealing

×：觀察到多數網域 ×: Most domains are observed

○：良好 ○: Good

◎：非常良好 ◎: Very good

表7中，在實施例1之UV照射後的應答速度迅速，且退火處理後之網域觀察結果亦為良好結果。另一方面，對於比較例8，雖退火處理後之網域觀察結果非常良好，但UV照射後之應答速度較慢。對於比較例7，雖應答速度較快，但於退火處理後之網域多數被觀察到。 In Table 7, the response speed after the UV irradiation of Example 1 was rapid, and the network observation result after the annealing treatment was also a good result. On the other hand, in Comparative Example 8, although the observation result of the mesh after the annealing treatment was very good, the response speed after the UV irradiation was slow. For Comparative Example 7, although the response speed was faster, most of the domains after the annealing treatment were observed.

且，對於實施例2~11、比較例9及10，UV照射後的應答速度迅速，且退火處理後的網域觀察結果亦顯示非常良好結果。 Further, in Examples 2 to 11 and Comparative Examples 9 and 10, the response speed after UV irradiation was rapid, and the network observation result after the annealing treatment also showed very good results.

應答速度之判定 Decision speed

○：非常快(非常良好)<50msec ○: Very fast (very good) <50msec

△：快(良好)<50~100msec △: Fast (good) <50~100msec

×：慢(差)>200msec ×: slow (poor) > 200 msec

表8中，對於UV照射量之應答速度，與由比較例11及比較例12之聚矽氧烷單獨所成的液晶配向處理劑做比較，得知含有選自聚醯胺酸及聚醯亞胺所成群之至少一種類聚合物的液晶配向處理劑，對於UV照射具有較廣之應答速度提高範圍。 In Table 8, the response speed of the UV irradiation amount was compared with the liquid crystal alignment treatment agent formed by the polyoxane of Comparative Example 11 and Comparative Example 12, and it was found that it was selected from the group consisting of polyamic acid and polyphthalamide. A liquid crystal alignment treatment agent of at least one type of polymer in which an amine is grouped has a wide range of response speed improvement for UV irradiation.

表9中，與表2、及表6同樣地，有關電氣特性，將含有脲基之液晶配向處理劑與不含有脲基的液晶配向處理劑做比較，得知其VHR較高，且離子密度較低。 In Table 9, in the same manner as in Tables 2 and 6, the liquid crystal alignment treatment agent containing a urea group was compared with a liquid crystal alignment treatment agent containing no urea group, and the VHR was high and the ion density was obtained. Lower.

表10中，與表3同樣地，與由無機單獨所成的液晶 配向處理劑做比較，得知含有選自聚醯胺酸及聚醯亞胺所成群之至少一種類聚合物的液晶配向處理劑，其具有較高再加工性。 In Table 10, similar to Table 3, liquid crystals formed from inorganic materials alone The alignment treatment agent was compared to obtain a liquid crystal alignment treatment agent containing at least one type of polymer selected from the group consisting of polylysine and polyimine, which has high reworkability.

[產業上可利用性] [Industrial availability]

使用本發明的液晶配向處理劑所形成之液晶配向膜，其垂直配向力不會降低，UV照射後的應答速度亦優良，具有本發明之液晶配向膜的液晶顯示元件可使用於TFT液晶顯示元件、TN液晶顯示元件、VA液晶顯示元件等。 The liquid crystal alignment film formed by using the liquid crystal alignment treatment agent of the present invention does not have a vertical alignment force and is excellent in response speed after UV irradiation, and the liquid crystal display element having the liquid crystal alignment film of the present invention can be used for a TFT liquid crystal display element. , TN liquid crystal display elements, VA liquid crystal display elements, and the like.

且，於2012年8月30日申請的日本專利申請號2012-190328號之說明書、申請專利範圍、及摘要之全內容經引用於此，作為本發明之說明書的揭示內容。 The entire contents of the specification, the patent application, and the abstract of Japanese Patent Application No. 2012-190328, filed on Aug.

Claims (10)

一種液晶配向處理劑，其特徵為含有下述(A)成分及(B)成分；(A)成分：選自由聚醯胺酸及聚醯亞胺所成群之至少一種類聚合物；(B)成分：將含有式(1)所示烷氧基矽烷及式(3)所示烷氧基矽烷之烷氧基矽烷進行聚縮合所得之聚矽氧烷；R¹Si(OR²)₃ (1)(R¹為下述式(2)的結構，R²為碳原子數1~5的烷基)； (Y¹為-(CH₂)_a-(a為1~15的整數)或-CH₂O-；Y²為單鍵、含有雙鍵之碳數3~8的直鏈狀或者分支狀的烴基、或-(CR¹⁷R¹⁸)_b-(b為1~15的整數，R¹⁷、R¹⁸各獨立為氫原子或碳數1~3的烷基)；Y³為單鍵、-(CH₂)_c-(c為1~15的整數)、-O-、-CH₂O-、-COO-或-OCO-；Y⁴為選自苯環、環己基環及雜環的2價環狀基，這些環狀基上之任意氫原子可由碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟烷基、碳數1~3的含氟烷氧基或氟原子所取代；且Y⁴可為具有類固醇骨架之碳 數12~25的2價有機基；Y⁵為選自由苯環、環己基環及雜環所成群之2價環狀基，這些環狀基上的任意氫原子可由碳數1~3的烷基、碳數1~3的烷氧基、碳數1~3的含氟烷基、碳數1~3的含氟烷氧基或氟原子所取代；Y⁶為氫原子或碳數1~18的烷基、碳數1~18的含氟烷基、碳數1~18的烷氧基或碳數1~18的含氟烷氧基；n為0~4的整數)；R³Si(OR⁴)₃ (3)(R³為由丙烯酸基、丙烯醯氧基、甲基丙烯酸基、甲基丙烯醯氧基或苯乙烯基所取代之碳數1~30的烷基，R⁴為碳數1~5的烷基)。 A liquid crystal alignment treatment agent comprising the following components (A) and (B); and (A) component: at least one polymer selected from the group consisting of polyamic acid and polyamidene; Component: a polyoxyalkylene obtained by polycondensing an alkoxydecane represented by the formula (1) and an alkoxydecane represented by the formula (3); R ¹ Si(OR ² ) ₃ ( 1) (R ¹ is a structure of the following formula (2), and R ² is an alkyl group having 1 to 5 carbon atoms); (Y ¹ is -(CH ₂ ) _a - (a is an integer of 1 to 15) or -CH ₂ O-; Y ² is a single bond, and has a double bond and a linear or branched carbon number of 3 to 8 a hydrocarbon group or -(CR ¹⁷ R ¹⁸ ) _b - (b is an integer of 1 to 15, and R ¹⁷ and R ^{18 are} each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms); Y ³ is a single bond, -( CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-; Y ⁴ is a divalent value selected from the group consisting of a benzene ring, a cyclohexyl ring and a hetero ring a cyclic group, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a carbon number of 1 to 3 a fluorine-containing alkoxy group or a fluorine atom; and Y ⁴ may be a divalent organic group having a steroidal skeleton having 12 to 25 carbon atoms; and Y ⁵ is selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring; a valent cyclic group, any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a carbon number of 1 to 3 Substituted by a fluorine-containing alkoxy group or a fluorine atom; Y ⁶ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a carbon number a fluorine-containing alkoxy group of 1 to 18; n is an integer of 0 to 4; R ³ Si(OR ⁴ ) ₃ (3) (R ³ is an alkyl group having 1 to 30 carbon atoms substituted by an acrylic group, an acryloxy group, a methacryl group, a methacryloxy group or a styryl group, and R ⁴ is a carbon number of 1 ~5 alkyl). 如請求項1的液晶配向處理劑，其中(B)成分為進一步含有下述式(4)所示烷氧基矽烷，且將烷氧基矽烷經聚縮合所得之聚矽氧烷；(R⁵)_nSi(OR⁶)_4-n (4)(R⁵為氫原子或可由雜原子、鹵素原子、胺基、乙二醇氧基、巰基、異氰酸酯基、脲基所取代之碳原子數1~10的烴基；R⁶為碳原子數1~5的烷基，n為0~3的整數)。 The liquid crystal alignment treatment agent of claim 1, wherein the component (B) is a polyoxyalkylene obtained by further alkoxydecane represented by the following formula (4) and obtained by polycondensation of an alkoxydecane; (R ⁵ _n Si(OR ⁶ ) _4-n (4) (R ⁵ is a hydrogen atom or a carbon atom which may be substituted by a hetero atom, a halogen atom, an amine group, a glycol group, a decyl group, an isocyanate group or a urea group) a hydrocarbon group of ~10; R ⁶ is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 3). 如請求項2的液晶配向處理劑，其中前述式(4)所示烷氧基矽烷為四甲氧基矽烷或四乙氧基矽烷。 The liquid crystal alignment treatment agent of claim 2, wherein the alkoxydecane represented by the above formula (4) is tetramethoxynonane or tetraethoxydecane. 如請求項1的液晶配向處理劑，其中於(B)成分 的聚矽氧烷之製造所使用的全烷氧基矽烷中，使用2~20莫耳%的式(1)所示烷氧基矽烷，且使用5~80莫耳%的式(3)所示烷氧基矽烷。 The liquid crystal alignment treatment agent of claim 1, wherein the component (B) 2 to 20 mol% of the alkoxydecane represented by the formula (1) and 5 to 80 mol% of the formula (3) in the peralkoxy decane used for the production of the polyoxyalkylene. Alkoxy decane. 如請求項2或3所記載的液晶配向處理劑，其中於(B)成分的聚矽氧烷之製造所使用的全烷氧基矽烷中，使用10~90莫耳%的式(4)所示烷氧基矽烷。 The liquid crystal alignment treatment agent according to claim 2, wherein, in the peralkoxy decane used for the production of the polyoxane of the component (B), 10 to 90 mol% of the formula (4) is used. Alkoxy decane. 如請求項1~4中任一項的液晶配向處理劑，其中對於(A)成分的100質量份而言，(B)成分以(B)成分所具有的矽原子之SiO₂換算值表示時為含有0.5~80質量份。 The liquid crystal alignment treatment agent according to any one of claims 1 to 4, wherein, in the case of 100 parts by mass of the component (A), the component (B) is represented by the SiO ₂ conversion value of the ruthenium atom of the component (B). It is contained in an amount of 0.5 to 80 parts by mass. 如請求項1~4中任一項的液晶配向處理劑，其中進一步含有有機溶劑，在液晶配向處理劑中含有90~99質量%的該有機溶劑。 The liquid crystal alignment treatment agent according to any one of claims 1 to 4, which further contains an organic solvent, and contains 90 to 99% by mass of the organic solvent in the liquid crystal alignment treatment agent. 一種液晶配向膜，其特徵為由如請求項1~7中任一項的液晶配向處理劑所得之液晶配向膜。 A liquid crystal alignment film characterized by a liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of claims 1 to 7. 如請求項8的液晶配向膜，其中燒成後之塗膜厚度為5~300nm。 The liquid crystal alignment film of claim 8, wherein the film thickness after firing is 5 to 300 nm. 一種液晶顯示元件，其特徵為具有如請求項8或9中任一項之液晶配向膜。 A liquid crystal display element characterized by having a liquid crystal alignment film according to any one of claims 8 or 9.