TWI653494B - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents
Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element Download PDFInfo
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- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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Abstract
本發明提供一種可形成耐紫外線衰退性佳與無色相不均 的液晶顯示元件的液晶配向劑、液晶配向膜以及具有上述液晶配向膜的液晶顯示元件。液晶配向劑包括聚合物(A)、聚矽氧烷(B)、光聚合性化合物(C)以及溶劑(D)。聚合物(A)是由混合物反應而獲得,混合物包括四羧酸二酐組份(a1)及二胺組份(a2)。二胺組份(a2)包括由式(II)表示的二胺化合物(a2-1)中的至少一者。 The present invention provides a method capable of forming excellent UV-resistant decay and colorless unevenness. A liquid crystal alignment agent for a liquid crystal display element, a liquid crystal alignment film, and a liquid crystal display element having the liquid crystal alignment film. The liquid crystal alignment agent includes a polymer (A), a polysiloxane (B), a photopolymerizable compound (C), and a solvent (D). The polymer (A) is obtained by reacting a mixture including a tetracarboxylic dianhydride component (a1) and a diamine component (a2). The diamine component (a2) includes at least one of the diamine compounds (a2-1) represented by the formula (II).
Description
本發明是關於一種液晶配向劑、液晶配向膜及液晶顯示元件,特別是關於一種可形成耐紫外線衰退性佳與無色相不均的液晶顯示元件的液晶配向劑、由上述液晶配向劑形成的液晶配向膜以及具有上述液晶配向膜的液晶顯示元件。 The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film and a liquid crystal display element, and more particularly to a liquid crystal alignment agent capable of forming a liquid crystal display element with excellent ultraviolet decay resistance and colorless phase unevenness, and a liquid crystal formed by the liquid crystal alignment agent. An alignment film and a liquid crystal display element having the liquid crystal alignment film.
隨著液晶顯示器朝向大尺寸的顯示規格發展,為了克服大尺寸顯示下的視角問題,液晶顯示面板的廣視角技術也必須不停地進步與突破。多域垂直配向型(Multi-domain Vertical Alignment,MVA)液晶顯示面板即為常見的一種廣視角技術。多域垂直配向型的液晶顯示面板是在液晶面板中形成突起物,此突起物可限定液晶分子傾倒的方向,藉此可達到廣視角的顯示效果。然而,多域垂直配向型的液晶顯示面板卻無法避免源自於突起物的透光率及對比度不足以及液晶分子應答速度緩慢的問題。 With the development of liquid crystal displays toward large-sized display specifications, in order to overcome the problem of viewing angles in large-sized displays, the wide-viewing angle technology of liquid crystal display panels must also continue to improve and breakthrough. Multi-domain vertical alignment (MVA) liquid crystal display panel is a common wide viewing angle technology. The multi-domain vertical alignment type liquid crystal display panel is formed with protrusions in the liquid crystal panel, and the protrusions can limit the direction in which the liquid crystal molecules are tilted, thereby achieving a wide viewing angle display effect. However, the multi-domain vertical alignment type liquid crystal display panel cannot avoid problems caused by insufficient transmittance and contrast of the protrusions and slow response speed of the liquid crystal molecules.
近年來,為了解決上述問題,目前發展出一種聚合物穩 定配向型(Polymer Sustained Alignment,PSA)的技術。此技術乃是在由具有圖案狀導電膜的基板與不具有圖案狀導電膜的基板所組成的一對基板的間隙中、或者由兩枚具有圖案狀導電膜的基板所組成的一對基板的間隙中,挾持含有聚合性化合物的液晶組成物,於導電膜間施加電壓的狀態下,對液晶組成物照射紫外光而使聚合性化合物進行聚合,藉此展現出預傾角特性,並控制液晶配向方向。此技術可使導電膜形成特定的構成,而達到擴大視角及使液晶分子應答高速化的效果,從而解決了多域垂直配向型的液晶顯示面板無法避免的透光率及對比度不足的問題。 In recent years, in order to solve the above problems, a polymer stabilizer has been developed. Technology of Polymer Sustained Alignment (PSA). This technology uses a gap between a pair of substrates composed of a substrate with a patterned conductive film and a substrate without a patterned conductive film, or a pair of substrates composed of two substrates with a patterned conductive film. In the gap, a liquid crystal composition containing a polymerizable compound is held, and the liquid crystal composition is irradiated with ultraviolet light to polymerize the polymerizable compound while a voltage is applied between the conductive films, thereby exhibiting a pretilt angle characteristic and controlling the liquid crystal alignment direction. This technology enables the conductive film to form a specific structure, thereby achieving the effects of widening the viewing angle and speeding up the response of liquid crystal molecules, thereby solving the problems of unavoidable light transmittance and contrast of the multi-domain vertical alignment type liquid crystal display panel.
然而,為了使聚合性化合物產生聚合而必須照射如100,000J/m2的大量紫外線,因此除了液晶分子有分解之虞,照射紫外線而未聚合的未反應化合物也同時殘存於液晶層中,形成雜質汙染(contamination),而使液晶顯示元件產生色相不均(mura)的問題,特別是對電氣特性有不良的影響。此外,液晶層所使用的液晶分子的種類也必須因應所添加的聚合性化合物,而有所限制。 However, in order to polymerize a polymerizable compound, a large amount of ultraviolet rays such as 100,000 J / m 2 must be irradiated. Therefore, in addition to the possibility that liquid crystal molecules may be decomposed, unreacted compounds that are not polymerized by irradiating ultraviolet rays also remain in the liquid crystal layer and form impurities. Contamination causes a problem of mura in the liquid crystal display element, and particularly adversely affects electrical characteristics. In addition, the type of liquid crystal molecules used in the liquid crystal layer must also be limited depending on the polymerizable compound added.
因此,如何解決上述液晶層存在雜質污染的問題,並且提供一種耐紫外線衰退性佳與無色相不均的液晶顯示元件,實為目前本領域技術人員積極研究的課題。 Therefore, how to solve the problem of impurity contamination in the liquid crystal layer and provide a liquid crystal display element with excellent UV resistance and no color unevenness is a subject actively studied by those skilled in the art.
有鑑於此,本發明研發了表面控制垂直配向(Surface Control Vertical Alignment,SCVA)技術,並且提供一種可形成耐紫外線衰退性佳與無色相不均的液晶顯示元件的液晶配向劑、由上述液晶配向劑形成的液晶配向膜以及具有上述液晶配向膜的液晶顯示元件。 In view of this, the present invention has developed a surface controlled vertical alignment (Surface (Control Vertical Alignment, SCVA) technology, and provides a liquid crystal alignment agent capable of forming a liquid crystal display element with excellent ultraviolet decay resistance and no color unevenness, a liquid crystal alignment film formed from the liquid crystal alignment agent, and a liquid crystal having the liquid crystal alignment film. Display element.
本發明提供一種液晶配向劑,其包括聚合物(A)、聚矽氧烷(B)、光聚合性化合物(C)以及溶劑(D)。聚合物(A)是由混合物反應而獲得,混合物包括四羧酸二酐組份(a1)及二胺組份(a2)。二胺組份(a2)包括由式(II)表示的二胺化合物(a2-1)中的至少一者。 The invention provides a liquid crystal alignment agent, which includes a polymer (A), a polysiloxane (B), a photopolymerizable compound (C), and a solvent (D). The polymer (A) is obtained by reacting a mixture including a tetracarboxylic dianhydride component (a1) and a diamine component (a2). The diamine component (a2) includes at least one of the diamine compounds (a2-1) represented by the formula (II).
具體而言,由式(II)表示的二胺化合物(a2-1)如下所示。 Specifically, the diamine compound (a2-1) represented by Formula (II) is shown below.
式(II)中,R14表示-O-、、、、或。R15表示由式(II-1)表示的有機基。 In formula (II), R 14 represents -O-, , , , or . R 15 represents an organic group represented by the formula (II-1).
由式(II-1)表示的有機基如下所示。 The organic group represented by formula (II-1) is shown below.
式(II-1)中,R16表示氫原子、氟原子或甲基。R17、R18或R19各自獨立表示單鍵、-O-、、、、、或碳數為1至3的伸烷基。R20表示或,其中,R22及R23各自獨立表示氫原子、氟原子或甲基。R21表示氫原子、氟原子、碳數為1至12的烷基、碳數為1至12的氟烷基、碳數為1至12的烷氧基、-OCH2F、-OCHF2或-OCF3。k表示1或2。l、m及n各自獨立表示0至4的整數。o、p及q各自獨立表示0至3的整數,且o+p+q≧3。r及s各自獨立表示1或2。當存在多個R16、R17、R18、R19、R20、R22或R23的情況下,多個R16、R17、R18、R19、R20、R22或R23各自為相同或不同。 In the formula (II-1), R 16 represents a hydrogen atom, a fluorine atom, or a methyl group. R 17 , R 18 or R 19 each independently represents a single bond, -O-, , , , , Or an alkylene group having 1 to 3 carbon atoms. R 20 means or Wherein R 22 and R 23 each independently represent a hydrogen atom, a fluorine atom or a methyl group. R 21 represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, -OCH 2 F, -OCHF 2 or -OCF 3 . k represents 1 or 2. l, m, and n each independently represent an integer of 0 to 4. o, p, and q each independently represent an integer from 0 to 3, and o + p + q ≧ 3. r and s each independently represent 1 or 2. When multiple R 16 , R 17 , R 18 , R 19 , R 20 , R 22 or R 23 are present, multiple R 16 , R 17 , R 18 , R 19 , R 20 , R 22 or R 23 Each is the same or different.
並且,聚矽氧烷(B)含有乙烯性不飽和基,以及選自由、、-O-及所組成的族群中的至少一種官能基。 In addition, the polysiloxane (B) contains an ethylenically unsaturated group, and is selected from the group consisting of , , -O- and At least one functional group in the formed group.
在本發明的一實施例中,上述的乙烯性不飽和基包括由、、表示的基中的至少一者。 In an embodiment of the present invention, the ethylenically unsaturated group includes , , At least one of the bases represented.
在本發明的一實施例中,上述的光聚合性化合物(C)為由式(3)表示的化合物。 In one embodiment of the present invention, the photopolymerizable compound (C) is a compound represented by the formula (3).
式(3)中,R1各自獨立表示由式(3-1)至式(3-5)表示的聚合性官能基、氫原子、鹵素原子、-CN、-CF3、-CF2H、-CFH2、-OCF3、-OCF2H、-N=C=O、-N=C=S或碳數為1至20之烷基,其中烷基中任意的-CH2-可經-O-、-S-、-SO2-、-CO-、-COO-、-OCO-、-CH=CH-、-CF=CF-或-C≡C-取代,且含氫原子的官能基中,任意的氫原子可經鹵素原子或-CN取代;R1的至少1者為由式(3-1)至式(3-5)表示的聚合性官能基;Y獨立表示碳數為3至20的飽和或不飽和的獨立環、縮合環或螺環的2價基,其中環中任意的-CH2-可經-O-取代,任意的-CH=可經-N=取代,任意的-H可經鹵素原子、-CN、-NO2、-NC、-N=C=O、-N=C=S、經1至3個具有碳數為1至4的烷基或苯基取代的矽基、碳數為1至10的直鏈烷基、碳數為1至10的支鏈烷基或碳數為1至10的鹵烷基取代,且烷基中,任意的-CH2-可經-O-、-CO-、-COO-、-OCO-、-OCOO-、 -CH=CH-或-C≡C-取代;Z各自獨立表示單鍵或碳數為1至20的伸烷基,其中,伸烷基中任意的-CH2-可經-O-、-S-、-SO2-、-CO-、-COO-、-OCO-、-OCOO-、-CH=CH-、-CF=CF-、-CH=N-、-N=CH-、-N=N-、-N(O)=N-或-C≡C-取代,且任意的-H可經鹵素原子、碳數為1至10的烷基或碳數為1至10的鹵烷基取代;f表示1至6之整數,且當f為2至6之整數時,多個-Y-Z-為相同或不同。 In formula (3), R 1 each independently represents a polymerizable functional group represented by formula (3-1) to formula (3-5), a hydrogen atom, a halogen atom, -CN, -CF 3 , -CF 2 H, -CFH 2 , -OCF 3 , -OCF 2 H, -N = C = O, -N = C = S, or an alkyl group having 1 to 20 carbon atoms, wherein any -CH 2 in the alkyl group may be passed through- Functional group substituted with O-, -S-, -SO 2- , -CO-, -COO-, -OCO-, -CH = CH-, -CF = CF-, or -C≡C-, and containing a hydrogen atom In the formula, any hydrogen atom may be substituted by a halogen atom or -CN; at least one of R 1 is a polymerizable functional group represented by formula (3-1) to formula (3-5); Y independently represents a carbon number of 3 Divalent group of saturated or unsaturated independent ring, condensed ring or spiro ring to 20, wherein any -CH 2 -in the ring may be substituted by -O-, any -CH = may be substituted by -N =, any -H can pass through a halogen atom, -CN, -NO 2 , -NC, -N = C = O, -N = C = S, through 1 to 3 alkyl or phenyl groups having 1 to 4 carbon atoms. Substituted silyl, linear alkyl having 1 to 10 carbons, branched alkyl having 1 to 10 carbons, or haloalkyl having 1 to 10 carbons, and in the alkyl group, any -CH 2 -may be substituted by -O-, -CO-, -COO-, -OCO-, -OCOO-, -CH = CH- or -C≡C-; Z each independently represents a single bond or an alkylene group having a carbon number of 1 to 20, wherein any -CH 2 -in the alkylene group may pass through -O-, -S-, -SO 2- , -CO-,- COO-, -OCO-, -OCOO-, -CH = CH-, -CF = CF-, -CH = N-, -N = CH-, -N = N-, -N (O) = N- or -C≡C- substituted, and any -H may be substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms; f represents an integer of 1 to 6, and when f When it is an integer of 2 to 6, a plurality of -YZ- are the same or different.
由式(3-1)至式(3-5)表示的聚合性官能基如下所示。 The polymerizable functional groups represented by the formulas (3-1) to (3-5) are shown below.
式(3-1)至式(3-5)中,R2表示氫原子、鹵素原子、-CF3或碳數為1至5的烷基。 In the formulae (3-1) to (3-5), R 2 represents a hydrogen atom, a halogen atom, -CF 3 or an alkyl group having 1 to 5 carbon atoms.
在本發明的一實施例中,上述的光聚合性化合物(C)的R1的至少一者為由式(3-1)至(3-3)表示的聚合性官能基。 In one embodiment of the present invention, at least one of R 1 of the photopolymerizable compound (C) is a polymerizable functional group represented by the formulae (3-1) to (3-3).
在本發明的一實施例中,上述的光聚合性化合物(C)的Y各自獨立表示1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、萘-2,6-二基、四氫化萘-2,6-二基、芴-2,7-二基、雙環[2.2.2]辛烷-1,4-二基、雙環[3.1.0]己烷-3,6-二基或三蝶烯-1,4-二基的二價基團;在環中的任意的-CH2-可經-O-取代,任意的-CH=可經-N=取代,任意的-H可經鹵素原子、-CN、-NO2、-NC、-N=C=O、-N=C=S、經1至3個具有碳數為1至4的烷基或苯基取代的矽基(亦即,矽基的1個至3個氫原子經具有碳數為1至4的烷基或苯基取代所形成的基團)、碳數為1至10的直鏈烷基或支鏈烷基,或者碳數為1至10的鹵烷基取代;且於烷基中,任意的-CH2-可經-O-、-CO-、-COO-、-OCO-、-OCOO-、-CH=CH-或-C≡C-取代。 In an embodiment of the present invention, each of Y of the photopolymerizable compound (C) independently represents 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, or naphthalene -2,6-diyl, tetralin-2,6-diyl, fluorene-2,7-diyl, bicyclic [2.2.2] octane-1,4-diyl, bicyclic [3.1.0] Divalent group of hexane-3,6-diyl or triptycene-1,4-diyl; any -CH 2 -in the ring may be substituted by -O-, any -CH = may be -N = substitution, any -H may pass through a halogen atom, -CN, -NO 2 , -NC, -N = C = O, -N = C = S, have 1 to 4 carbon atoms through 1 to 3 Alkyl or phenyl substituted silyl (that is, a group formed by substitution of 1 to 3 hydrogen atoms of a silyl group with an alkyl or phenyl group having 1 to 4 carbon atoms), a carbon number of 1 A linear or branched alkyl group of 10 to 10, or a haloalkyl group having 1 to 10 carbon atoms; and in the alkyl group, any -CH 2 -may be -O-, -CO-, -COO -, -OCO-, -OCOO-, -CH = CH- or -C≡C- substitution.
在本發明的一實施例中,上述的Y各自獨立表示選自由式(3-6)至式(3-30)表示的官能基所組成的族群中的至少一者。 In one embodiment of the present invention, each of the aforementioned Ys independently represents at least one selected from the group consisting of functional groups represented by formula (3-6) to formula (3-30).
式(3-6)至式(3-30)中,R3表示鹵素原子、碳數為1至3的烷基、碳數為1至3的烷氧基或碳數為1至3的鹵烷基。 In the formulae (3-6) to (3-30), R 3 represents a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen group having 1 to 3 carbon atoms. alkyl.
在本發明的一實施例中,上述的光聚合性化合物(C)選自由式(3-31)至式(3-42)表示的化合物所組成的族群中的至少一者。 In one embodiment of the present invention, the photopolymerizable compound (C) is at least one selected from the group consisting of compounds represented by formula (3-31) to formula (3-42).
式(3-31)至式(3-42)中,R4各自獨立表示氫原子或甲基;R5各自獨立表示氫原子、鹵素原子、甲基、-CF3、-OCH3、苯基或同一碳原子上的2個R5形成碳數為6至15的飽和或不飽和的烴環;g及h各自獨立表示1至20的整數。 In the formulae (3-31) to (3-42), each of R 4 independently represents a hydrogen atom or a methyl group; each of R 5 independently represents a hydrogen atom, a halogen atom, a methyl group, -CF 3 , -OCH 3 , or phenyl group. Or two R 5 on the same carbon atom form a saturated or unsaturated hydrocarbon ring having 6 to 15 carbon atoms; g and h each independently represent an integer of 1 to 20.
在本發明的一實施例中,上述的聚合物(A)的醯亞胺化率為30%至90%。 In one embodiment of the present invention, the fluorene imidization rate of the polymer (A) is 30% to 90%.
在本發明的一實施例中,基於所述聚合物(A)為100重量份,所述聚矽氧烷(B)的使用量為3至25重量份;所述光聚合性化合物(C)的使用量為1至35重量份;所述溶劑(D)的使 用量為800至4000重量份。 In an embodiment of the present invention, based on 100 parts by weight of the polymer (A), the used amount of the polysiloxane (B) is 3 to 25 parts by weight; the photopolymerizable compound (C) Is used in an amount of 1 to 35 parts by weight; the use of the solvent (D) The amount is 800 to 4000 parts by weight.
本發明還提供一種液晶配向膜,其是由上述的液晶配向劑而形成。 The present invention also provides a liquid crystal alignment film, which is formed by the above-mentioned liquid crystal alignment agent.
本發明另提供一種液晶顯示元件,其包括如上述的液晶配向膜。 The present invention further provides a liquid crystal display device including the liquid crystal alignment film as described above.
基於上述,本發明的表面控制垂直配向型液晶配向劑中,除了含有聚合物以及溶劑之外,更將光聚合性化合物添加於液晶配向劑中,因此不會有液晶層受到雜質污染的問題。進一步而言,本發明的表面控制垂直配向型液晶配向劑同時含有特定結構的聚矽氧烷及光聚合性化合物,而使液晶顯示元件的耐紫外線衰退性佳,並且無色相不均的問題,因此適用於製造液晶配向膜及液晶顯示元件。 Based on the above, in the surface-controlled vertical alignment type liquid crystal alignment agent of the present invention, in addition to the polymer and the solvent, a photopolymerizable compound is added to the liquid crystal alignment agent. Therefore, the liquid crystal layer is not contaminated by impurities. Further, the surface-controlled vertical alignment type liquid crystal alignment agent of the present invention contains both a polysiloxane and a photopolymerizable compound having a specific structure, so that the liquid crystal display element has excellent resistance to ultraviolet decay and has no problem of color unevenness. Therefore, it is suitable for manufacturing liquid crystal alignment films and liquid crystal display elements.
為讓本發明的上述特徵和優點能更明顯易懂,下文特舉實施例詳細說明如下。 In order to make the above features and advantages of the present invention more comprehensible, the following specific embodiments are described in detail below.
本發明提供一種液晶配向劑,其包括聚合物(A)、聚矽氧烷(B)、光聚合性化合物(C)以及溶劑(D)。此外,若需要, 液晶配向劑可更包括添加劑(E)。 The invention provides a liquid crystal alignment agent, which includes a polymer (A), a polysiloxane (B), a photopolymerizable compound (C), and a solvent (D). In addition, if needed, The liquid crystal alignment agent may further include an additive (E).
在下文中,將詳細說明用於本發明的液晶配向劑的各個成分。 Hereinafter, each component of the liquid crystal alignment agent used in the present invention will be described in detail.
在此說明的是,以下是以(甲基)丙烯酸表示丙烯酸及/或甲基丙烯酸,並以(甲基)丙烯酸酯表示丙烯酸酯及/或甲基丙烯酸酯;同樣地,以(甲基)丙烯醯基表示丙烯醯基及/或甲基丙烯醯基。 Here, it is explained that acrylic acid and / or methacrylic acid are represented by (meth) acrylic acid, and acrylate and / or methacrylic acid ester are represented by (meth) acrylic acid ester; similarly, (meth) Acrylofluorenyl refers to acrylfluorenyl and / or methacrylfluorenyl.
聚合物(A)是由混合物反應而獲得,混合物包括四羧酸二酐組份(a1)及二胺組份(a2)。 The polymer (A) is obtained by reacting a mixture including a tetracarboxylic dianhydride component (a1) and a diamine component (a2).
詳細而言,聚合物(A)包括聚醯胺酸、聚醯亞胺、聚醯胺酸-聚醯亞胺嵌段共聚合物或這些聚合物的組合。其中,聚醯亞胺系嵌段共聚合物包括聚醯胺酸嵌段共聚合物、聚醯亞胺嵌段共聚合物、聚醯胺酸-聚醯亞胺嵌段共聚合物或上述聚合物的組合。聚醯胺酸聚合物、聚醯亞胺聚合物及聚醯胺酸-聚醯亞胺嵌段共聚合物皆可由四羧酸二酐組份(a1)及二胺組份(a2)的混合物反應所製得。 In detail, the polymer (A) includes polyamidic acid, polyamidoimide, polyamidopolyimide block copolymer, or a combination of these polymers. Among them, the polyfluorene-based block copolymer includes a polyfluoride-based block copolymer, a polyfluoride-based imide block copolymer, a polyfluoride-based polyimide-block copolymer, or the above-mentioned polymerization. Combination of things. Polyamic acid polymers, polyimide polymers, and polyamic acid-polyimide block copolymers may be composed of a mixture of a tetracarboxylic dianhydride component (a1) and a diamine component (a2). Prepared by the reaction.
四羧酸二酐組份(a1)包括脂肪族四羧酸二酐化合物、脂環族四羧酸二酐化合物、芳香族四羧酸二酐化合物、由式(I-1) 至式(I-6)表示的四羧酸二酐化合物中的至少一種,或上述化合物的組合。 The tetracarboxylic dianhydride component (a1) includes an aliphatic tetracarboxylic dianhydride compound, an alicyclic tetracarboxylic dianhydride compound, an aromatic tetracarboxylic dianhydride compound, and a compound of formula (I-1) To at least one of the tetracarboxylic dianhydride compounds represented by formula (I-6), or a combination of the aforementioned compounds.
以下列舉脂肪族四羧酸二酐化合物、脂環族四羧酸二酐化合物、芳香族四羧酸二酐化合物的具體例,但本發明並不限於這些具體例。 Specific examples of the aliphatic tetracarboxylic dianhydride compound, the alicyclic tetracarboxylic dianhydride compound, and the aromatic tetracarboxylic dianhydride compound are listed below, but the present invention is not limited to these specific examples.
脂肪族四羧酸二酐化合物的具體例可包括但不限於乙烷四羧酸二酐(ethane tetracarboxylic dianhydride)、丁烷四羧酸二酐(butane tetracarboxylic dianhydride)或上述化合物的組合。 Specific examples of the aliphatic tetracarboxylic dianhydride compound may include, but are not limited to, ethane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, or a combination thereof.
脂環族四羧酸二酐化合物的具體例可包括但不限於1,2,3,4-環丁烷四羧酸二酐、1,2-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,3-二氯-1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-四甲基-1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐、1,2,4,5-環己烷四羧酸二酐、3,3’,4,4’-二環己基四羧酸二酐、順式-3,7-二丁基環庚基-1,5-二烯-1,2,5,6-四羧酸二酐、2,3,5-三羧基環戊基醋酸二酐、雙環[2.2.2]-辛-7-烯-2,3,5,6-四羧酸二酐或上述化合物的組合。 Specific examples of the alicyclic tetracarboxylic dianhydride compound may include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclo Butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutyl Cycloheptyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, bicyclo [2.2.2] -oct-7 -Ene-2,3,5,6-tetracarboxylic dianhydride or a combination thereof.
芳香族四羧酸二酐化合物的具體例可包括但不限於3,4-二羧基-1,2,3,4-四氫萘-1-琥珀酸二酐、苯均四羧酸二酐、3,3’,4,4’-二苯甲酮四羧酸二酐、3,3’,4,4’-聯苯碸四羧酸二酐、1,4,5,8-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐、3,3’-4,4’-二苯基乙烷四羧酸二酐、3,3’,4,4’-二甲基二苯基矽烷四羧酸二酐、3,3’,4,4’-四苯基矽烷四羧酸二酐、1,2,3,4-呋喃四羧酸二酐、4,4’-雙(3,4-二羧基苯氧基) 二苯硫醚二酐、4,4’-雙(3,4-二羧基苯氧基)二苯碸二酐、4,4’-雙(3,4-二羧基苯氧基)二苯丙烷二酐(4,4’-bis(3,4-dicarboxy phenoxy)diphenylpropane dianhydride)、3,3’,4,4’-全氟異亞丙基二苯二酸二酐、3,3’,4,4’-二苯基四羧酸二酐、雙(苯二酸)苯膦氧化物二酐、對-伸苯基-雙(三苯基苯二酸)二酐、間-伸苯基-雙(三苯基苯二酸)二酐、雙(三苯基苯二酸)-4,4’-二苯基醚二酐、雙(三苯基苯二酸)-4,4’-二苯基甲烷二酐、乙二醇-雙(脫水偏苯三酸酯)、丙二醇-雙(脫水偏苯三酸酯)、1,4-丁二醇-雙(脫水偏苯三酸酯)、1,6-己二醇-雙(脫水偏苯三酸酯)、1,8-辛二醇-雙(脫水偏苯三酸酯)、2,2-雙(4-羥苯基)丙烷-雙(脫水偏苯三酸酯)、2,3,4,5-四氫呋喃四羧酸二酐、1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二側氧基-3-呋喃基)-萘并[1,2-c]-呋喃-1,3-二酮{(1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione)}、1,3,3a,4,5,9b-六氫-5-甲基-5-(四氫-2,5-二側氧基-3-呋喃基)-萘并[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-5-乙基-5-(四氫-2,5-二側氧基-3-呋喃基)-萘并[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-7-甲基-5-(四氫-2,5-二側氧基-3-呋喃基)-萘并[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-7-乙基-5-(四氫-2,5-二側氧基-3-呋喃基)-萘并[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-8-甲基-5-(四氫-2,5-二側氧基-3-呋喃基)-萘并[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-8-乙基-5-(四氫-2,5-二側氧基-3-呋喃基)-萘并[1,2-c]-呋喃-1,3-二酮、 1,3,3a,4,5,9b-六氫-5,8-二甲基-5-(四氫-2,5-二側氧基-3-呋喃基)-萘并[1,2-c]-呋喃-1,3-二酮、5-(2,5-二側氧基四氫呋喃基)-3-甲基-3-環己烯-1,2-二羧酸二酐等芳香族四羧酸二酐化合物或上述化合物的組合。 Specific examples of the aromatic tetracarboxylic dianhydride compound may include, but are not limited to, 3,4-dicarboxyl-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylpyrenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3'-4,4'-diphenylethanetetracarboxylic dianhydride, 3,3 ', 4,4'- Dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4, 4'-bis (3,4-dicarboxyphenoxy) Diphenyl sulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylhydrazone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane Dianhydride (4,4'-bis (3,4-dicarboxy phenoxy) diphenylpropane dianhydride), 3,3 ', 4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3', 4 , 4'-Diphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene- Bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-di Phenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydromellitate), 1,4-butanediol-bis (anhydromellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane- Bis (anhydrotrimellitic acid ester), 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5- Dioxo-3-furyl) -naphtho [1,2-c] -furan-1,3-dione {(1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro- 2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-di one)}, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5- (tetrahydro-2,5-dioxo-3 -Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro- 2,5-dioxo-3-furyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7 -Ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3 -Dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- (tetrahydro-2,5-dioxo-3-furyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furyl) -naphtho [1,2 -c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride A group tetracarboxylic dianhydride compound or a combination of the aforementioned compounds.
由式(I-1)至式(I-6)表示的四羧酸二酐化合物如下所示。 The tetracarboxylic dianhydride compounds represented by formula (I-1) to formula (I-6) are shown below.
式(I-5)中,A1表示含有芳香環的二價基團;r表示1至2的整數;A2及A3可為相同或不同,且可各自獨立表示氫原子或烷基。由式(I-5)表示的四羧酸二酐化合物的具體例包括由式(I-5-1)至式(I-5-3)表示的化合物中的至少一種。 In Formula (I-5), A 1 represents a divalent group containing an aromatic ring; r represents an integer of 1 to 2; A 2 and A 3 may be the same or different, and each may independently represent a hydrogen atom or an alkyl group. Specific examples of the tetracarboxylic dianhydride compound represented by the formula (I-5) include at least one of compounds represented by the formula (I-5-1) to the formula (I-5-3).
式(I-6)中,A4表示含有芳香環的二價基團;A5及A6可為相同或不同,且各自獨立表示氫原子或烷基。由式(I-6)表示的四羧酸二酐化合物較佳為由式(I-6-1)表示的化合物。 In Formula (I-6), A 4 represents a divalent group containing an aromatic ring; A 5 and A 6 may be the same or different, and each independently represents a hydrogen atom or an alkyl group. The tetracarboxylic dianhydride compound represented by the formula (I-6) is preferably a compound represented by the formula (I-6-1).
四羧酸二酐組份(a1)可以單獨使用或者組合多種來使用。 The tetracarboxylic dianhydride component (a1) can be used alone or in combination.
四羧酸二酐組份(a1)的具體例較佳為包括1,2,3,4-環丁烷四羧酸二酐(1,2,3,4-cyclobutane tetracarboxylic acid dianhydride)、1,2,3,4-環戊烷四羧酸二酐、2,3,5-三羧基環戊基醋酸二酐(2,3,5-tricarboxycyclopentylacetic acid dianhydride)、1,2,4,5-環己烷四羧酸二酐、3,4-二羧基-1,2,3,4-四氫萘-1-琥珀酸二酐、苯均四羧酸二酐(pyromellitic dianhydride)、3,3’,4,4’-二苯甲酮四羧酸二酐以及3,3’,4,4’-聯苯碸四羧酸二酐,或上述化合物的組合。 Specific examples of the tetracarboxylic dianhydride component (a1) preferably include 1,2,3,4-cyclobutane tetracarboxylic dianhydride (1,2,3,4-cyclobutane tetracarboxylic acid dianhydride), 1, 2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,4,5-cyclo Hexanetetracarboxylic dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3 ' , 4,4'-benzophenonetetracarboxylic dianhydride and 3,3 ', 4,4'-biphenylfluorenetetracarboxylic dianhydride, or a combination of the above compounds.
基於二胺組份(a2)的總莫耳數為100莫耳,四羧酸二酐組份(a1)的使用量範圍較佳為20莫耳至200莫耳;四羧酸二酐組份(a1)的使用量範圍更佳為30莫耳至120莫耳。 Based on the total mole number of the diamine component (a2) is 100 moles, the amount of the tetracarboxylic dianhydride component (a1) is preferably in the range of 20 moles to 200 moles; the tetracarboxylic dianhydride component The amount of (a1) is more preferably in the range of 30 to 120 mol.
二胺組份(a2)包括式(II)表示的二胺化合物(a2-1)。具體而言,由式(II)表示的二胺化合物(a2-1)如下所示。 The diamine component (a2) includes a diamine compound (a2-1) represented by the formula (II). Specifically, the diamine compound (a2-1) represented by Formula (II) is shown below.
式(II)中,R14表示-O-、、、、或;R15表示由式(II-1)表示的有機基。 In formula (II), R 14 represents -O-, , , , or R 15 represents an organic group represented by formula (II-1).
式(II-1)中,R16表示氫原子、氟原子或甲基;R17、R18或R19各自獨立表示單鍵、-O-、、、、、或碳數為1至3的伸烷基;R20表示或,其中,R22及R23各自獨立表示氫原子、氟原子或甲基;R21表示氫原子、氟原子、碳數為1至12的烷基、碳數為1至12的氟烷基、碳數為1至12的烷氧基、-OCH2F、-OCHF2或-OCF3;k表示1或2;l、m及n各自獨立表示0至4的整數;o、p及q各自獨立表示0至3的整數,且o+p+q≧3;r及s各自獨立表示1或2;當存在多個R16、R17、R18、R19、R20、R22或R23的情況下,多個R16、R17、R18、R19、R20、R22或R23各自為相同或不同。 In formula (II-1), R 16 represents a hydrogen atom, a fluorine atom, or a methyl group; R 17 , R 18, or R 19 each independently represents a single bond, -O-, , , , , Or an alkylene group having 1 to 3 carbon atoms; R 20 represents or Wherein R 22 and R 23 each independently represent a hydrogen atom, a fluorine atom or a methyl group; R 21 represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, Alkoxy, -OCH 2 F, -OCHF 2 or -OCF 3 having a carbon number of 1 to 12; k represents 1 or 2; l, m, and n each independently represent an integer of 0 to 4; o, p, and q each Independently represents an integer from 0 to 3, and o + p + q ≧ 3; r and s each independently represent 1 or 2; when there are multiple R 16 , R 17 , R 18 , R 19 , R 20 , R 22 or R In the case of 23 , a plurality of R 16 , R 17 , R 18 , R 19 , R 20 , R 22, or R 23 are each the same or different.
二胺化合物(a2-1)的具體例包括由式(II-2)至式(II-9)表示的二胺化合物中的至少一種,或上述化合物的組合。 Specific examples of the diamine compound (a2-1) include at least one of the diamine compounds represented by the formula (II-2) to the formula (II-9), or a combination thereof.
式(II-2)至式(II-9)中,B11為氫原子、碳數為1至10的烷基或碳數為1至10的烷氧基。 In the formulae (II-2) to (II-9), B 11 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
由式(II-2)至式(II-9)表示的二胺化合物較佳為由式(II-10)至式(II-14)表示的二胺化合物中的至少一種,或上述化合物的組合。 The diamine compound represented by the formula (II-2) to the formula (II-9) is preferably at least one of the diamine compounds represented by the formula (II-10) to the formula (II-14), or combination.
上述的二胺化合物(a2-1)可單獨使用或組合多種來使用。 The above-mentioned diamine compound (a2-1) can be used alone or in combination.
基於二胺組份(a2)的總使用量為100莫耳,二胺化合物(a2-1)的使用量可為5莫耳至50莫耳,較佳為10莫耳至40莫耳,更佳為15莫耳至30莫耳。 Based on the total amount of the diamine component (a2) being 100 mol, the amount of the diamine compound (a2-1) may be 5 mol to 50 mol, preferably 10 mol to 40 mol, more It is preferably 15 mol to 30 mol.
若液晶配向劑的二胺組份(a2)未使用二胺化合物(a2-1),則液晶顯示元件的耐紫外線衰退性不佳。 If the diamine component (a2) of the liquid crystal alignment agent does not use the diamine compound (a2-1), the liquid crystal display element has poor UV resistance.
二胺化合物(a2-2)包括脂肪族二胺化合物、脂環族二胺化合物、芳香族二胺化合物、具有式(III-1)至式(III-25)的二胺化合物、或其組合。 The diamine compound (a2-2) includes an aliphatic diamine compound, an alicyclic diamine compound, an aromatic diamine compound, a diamine compound having a formula (III-1) to a formula (III-25), or a combination thereof .
脂肪族二胺化合物的具體例包括但不限於1,2-二胺基乙烷、1,3-二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷、4,4’-二胺基庚烷、1,3-二胺基-2,2-二甲基丙烷、1,6-二胺基-2,5-二甲基己烷、1,7-二胺基-2,5-二甲基庚烷、1,7-二胺基-4,4-二甲基庚烷、1,7-二胺基-3-甲基庚烷、1,9-二胺基-5-甲基壬烷、2,11-二胺基十二烷、1,12-二胺基十八烷、1,2-雙(3-胺基丙氧基)乙烷,或上述化合物的組合。 Specific examples of the aliphatic diamine compound include, but are not limited to, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane , 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane , 4,4'-diaminoheptane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7 -Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1, 9-diamino-5-methylnonane, 2,11-diaminododecane, 1,12-diaminooctadecane, 1,2-bis (3-aminopropoxy) ethyl Alkane, or a combination of the above.
脂環族二胺化合物的具體例包括但不限於4,4’-二胺基二環己基甲烷、4,4’-二胺基-3,3’-二甲基二環己基胺、1,3-二胺基環己烷、1,4-二胺基環己烷、異佛爾酮二胺、四氫二環戊二烯二胺、三環[6.2.1.02,7]-十一碳烯二甲基二胺、4,4’-亞甲基雙(環己基胺),或上述化合物的組合。 Specific examples of the alicyclic diamine compound include, but are not limited to, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, 1, 3-diaminocyclohexane, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene diamine, tricyclo [6.2.1.0 2,7 ] -unda Carbenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine), or a combination thereof.
芳香族二胺化合物的具體例包括但不限於4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基乙烷、4,4’-二胺基二苯基碸、4,4’-二胺基苯甲醯苯胺、4,4’-二胺基二苯基醚、3,4’-二胺基二苯基醚、1,5-二胺基萘、5-胺基-1-(4’-胺基苯基)-1,3,3-三甲基氫茚、6-胺基-1-(4’-胺基苯基)-1,3,3-三甲基氫茚、六氫-4,7-甲橋伸氫茚 基二亞甲基二胺、3,3’-二胺基二苯甲酮、3,4’-二胺基二苯甲酮、4,4’-二胺基二苯甲酮、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[4-(4-胺基苯氧基)苯基]碸、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、9,9-雙(4-胺基苯基)-10-氫蒽、9,10-雙(4-胺基苯基)蒽[9,10-bis(4-aminophenyl)anthracene]、2,7-二胺基茀、9,9-雙(4-胺基苯基)茀、4,4’-亞甲基-雙(2-氯苯胺)、4,4’-(對-伸苯基異亞丙基)雙苯胺、4,4’-(間-伸苯基異亞丙基)雙苯胺、2,2’-雙[4-(4-胺基-2-三氟甲基苯氧基)苯基]六氟丙烷、4,4’-雙[(4-胺基-2-三氟甲基)苯氧基]-八氟聯苯、5-[4-(4-正戊烷基環己基)環己基]苯基-亞甲基-1,3-二胺基苯{5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene}、1,1-雙[4-(4-胺基苯氧基)苯基]-4-(4-乙基苯基)環己烷{1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane},或上述化合物的組合。 Specific examples of the aromatic diamine compound include, but are not limited to, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl Hydrazone, 4,4'-diaminobenzylanilide, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylhydroindene, 6-amino-1- (4'-aminophenyl) -1,3, 3-trimethylindane, hexahydro-4,7-methyl bridgedindene Dimethylenediamine, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 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 [4- (4-aminophenoxy) phenyl] fluorene, 1,4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 9 , 10-bis (4-aminophenyl) anthracene [9,10-bis (4-aminophenyl) anthracene], 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene , 4,4'-methylene-bis (2-chloroaniline), 4,4 '-(p-phenylene isopropylidene) bisaniline, 4,4'-(m-phenylene isopropylidene) Propyl) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-bis [(4-amino -2-trifluoromethyl) phenoxy] -octafluorobiphenyl, 5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenyl-methylene-1,3-diamine Benzene {5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenylmethylene-1,3-diaminobenzene}, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4 -Ethylbenzene ) {1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl) cyclohexane}, cyclohexane or a combination of the above compounds.
具有式(III-1)至式(III-25)的二胺化合物如下所示。 The diamine compounds having the formula (III-1) to the formula (III-25) are shown below.
式(III-1)中,B12表示-O-、、、、 ,或;B13表示具有甾(膽固醇(steroid))骨架的基、三氟甲基、氟基、碳數為2至30的烷基、或衍生自吡啶、嘧啶、三嗪、哌啶或哌嗪等含氮原子環狀結構的一價基團。 In formula (III-1), B 12 represents -O-, , , , ,or ; B 13 represents a group having a steroid (cholesterol) skeleton, a trifluoromethyl group, a fluoro group, an alkyl group having 2 to 30 carbon atoms, or derived from pyridine, pyrimidine, triazine, piperidine, or piperazine, etc. A monovalent group containing a nitrogen atom ring structure.
由式(III-1)表示的化合物的具體例包括但不限於2,4-二胺基苯基甲酸乙酯(2,4-diaminophenyl ethyl formate)、3,5-二胺基苯基甲酸乙酯(3,5-diaminophenyl ethyl formate)、2,4-二胺基苯基甲酸丙酯(2,4-diaminophenyl propyl formate)、3,5-二胺基苯基甲酸丙酯(3,5-diaminophenyl propyl formate)、1-十二烷氧基-2,4-二胺基苯(1-dodecoxy-2,4-diaminobenzene)、1-十六烷氧基-2,4-二胺基苯(1-hexadecoxy-2,4-diaminobenzene)、1-十八烷氧基-2,4-二胺基苯(1-octadecoxy-2,4-diaminobenzene)、由式(III-1-1)至式(III-1-6)表示的化合物中的至少其中一種,或上述化合物的組合。 Specific examples of the compound represented by formula (III-1) include, but are not limited to, 2,4-diaminophenyl ethyl formate, 3,5-diaminophenyl ethyl formate Ester (3,5-diaminophenyl ethyl formate), 2,4-diaminophenyl propyl formate, 3,5-diaminophenyl propyl formate (3,5- diaminophenyl propyl formate), 1-dodecoxy-2,4-diaminobenzene, 1-dodecoxy-2,4-diaminobenzene, 1-dodecoxy-2,4-diaminobenzene ( 1-hexadecoxy-2,4-diaminobenzene), 1-octadecoxy-2,4-diaminobenzene, from formula (III-1-1) to formula At least one of the compounds represented by (III-1-6), or a combination thereof.
由式(III-1-1)至式(III-1-6)表示的化合物如下所示。 The compounds represented by the formula (III-1-1) to the formula (III-1-6) are shown below.
式(III-2)中,B12與式(III-1)中的B12相同,B14及B15各自獨立表示二價脂肪族環、二價芳香族環或二價雜環基團;B16表示碳數為3至18的烷基、碳數為3至18的烷氧基、碳數為1至5的氟烷基、碳數為1至5的氟烷氧基、氰基或鹵素原子。 (III-2), the same formula (III-1) of the formula B 12 and B 12, B 14 and B 15 each independently represents a divalent aliphatic ring, a divalent aromatic ring or a divalent heterocyclic group; B 16 represents an alkyl group having 3 to 18 carbons, an alkoxy group having 3 to 18 carbons, a fluoroalkyl group having 1 to 5 carbons, a fluoroalkoxy group having 1 to 5 carbons, cyano or Halogen atom.
由式(III-2)表示的化合物的具體例包括由式(III-2-1)至式(III-2-13)表示的化合物中的至少其中一種。具體而言,由式(III-2-1)至式(III-2-13)表示的化合物如下所示。 Specific examples of the compound represented by the formula (III-2) include at least one of compounds represented by the formula (III-2-1) to the formula (III-2-13). Specifically, the compounds represented by formula (III-2-1) to formula (III-2-13) are shown below.
式(III-2-10)至式(III-2-13)中,s表示3至12的整數。 In the formulae (III-2-10) to (III-2-13), s represents an integer of 3 to 12.
式(III-3)中,B17各自獨立表示氫原子、碳數為1至5的醯基、碳數為1至5的烷基、碳數為1至5的烷氧基或鹵素原子,且每個重複單元中的B17可為相同或不同;u表示1至3的整數。 In formula (III-3), B 17 each independently represents a hydrogen atom, a fluorenyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an alkoxy group or a halogen atom having 1 to 5 carbon atoms, And B 17 in each repeating unit may be the same or different; u represents an integer of 1 to 3.
由式(III-3)表示的化合物的具體例包括當u為1時:對-二胺苯、間-二胺苯、鄰-二胺苯或2,5-二胺基甲苯等;當u為2時:4,4’-二胺基聯苯、2,2’-二甲基-4,4’-二胺基聯苯、3,3’-二甲基-4,4’-二胺基聯苯、3,3’-二甲氧基-4,4’-二胺基聯苯、2,2’-二氯-4,4’-二胺基聯苯、3,3’-二氯-4,4’-二胺基聯苯、2,2’,5,5’-四氯-4,4’-二胺 基聯苯、2,2’-二氯-4,4’-二胺基-5,5’-二甲氧基聯苯或4,4’-二胺基-2,2’-雙(三氟甲基)聯苯等;或當u為3時:1,4-雙(4’-胺基苯基)苯等。 Specific examples of the compound represented by the formula (III-3) include when u is 1: p-diaminebenzene, m-diaminebenzene, o-diaminebenzene, 2,5-diaminotoluene, and the like; when u When 2: 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-di Aminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'- Dichloro-4,4'-diaminobiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diamine Biphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl or 4,4'-diamino-2,2'-bis (tri Fluoromethyl) biphenyl and the like; or when u is 3: 1,4-bis (4'-aminophenyl) benzene and the like.
由式(III-3)表示的化合物的具體例較佳為包括對-二胺苯、2,5-二胺基甲苯、4,4’-二胺基聯苯、3,3’-二甲氧基-4,4’-二胺基聯苯、1,4-雙(4’-胺基苯基)苯或上述化合物的組合。 Specific examples of the compound represented by the formula (III-3) preferably include p-diaminobenzene, 2,5-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-dimethyl Oxy-4,4'-diaminobiphenyl, 1,4-bis (4'-aminophenyl) benzene or a combination of the foregoing.
式(III-4)中,v表示2至12的整數。 In formula (III-4), v represents an integer of 2 to 12.
式(III-5)中,w表示1至5的整數。由式(III-5)表示的化合物較佳為4,4’-二胺基-二苯基硫醚。 In Formula (III-5), w represents an integer of 1 to 5. The compound represented by the formula (III-5) is preferably 4,4'-diamino-diphenylsulfide.
式(III-6)中,B18及B20各自獨立表示二價有機基團,且B18及B20可為相同或不同;B19表示衍生自吡啶、嘧啶、三嗪、哌啶或哌嗪等含氮原子的環狀結構的二價基團。 In formula (III-6), B 18 and B 20 each independently represent a divalent organic group, and B 18 and B 20 may be the same or different; B 19 represents a derivative derived from pyridine, pyrimidine, triazine, piperidine, or piperidine Divalent group of a cyclic structure containing a nitrogen atom such as a azine.
式(III-7)中,B21、B22、B23及B24各自獨立表示碳數為1至12的烴基,且B21、B22、B23及B24可為相同或不同;X1各自獨立表示1至3的整數;X2表示1至20的整數。 In formula (III-7), B 21 , B 22 , B 23 and B 24 each independently represent a hydrocarbon group having a carbon number of 1 to 12, and B 21 , B 22 , B 23 and B 24 may be the same or different; X1 Each independently represents an integer of 1 to 3; X2 represents an integer of 1 to 20.
式(III-8)中,B25表示氧原子或伸環己烷基;B26表示亞甲 基(methylene,-CH2-);B27表示伸苯基或伸環己烷基;B28表示氫原子或庚基。 In formula (III-8), B 25 represents an oxygen atom or a cyclohexyl group; B 26 represents a methylene group (methylene, -CH 2- ); B 27 represents a phenylene group or a cyclohexane group; B 28 Represents a hydrogen atom or a heptyl group.
由式(III-8)表示的化合物的具體例包括由式(III-8-1)表示的化合物、由式(III-8-2)表示的化合物或上述化合物的組合。 Specific examples of the compound represented by the formula (III-8) include a compound represented by the formula (III-8-1), a compound represented by the formula (III-8-2), or a combination thereof.
由式(III-9)至式(III-30)表示的化合物如下所示。 The compounds represented by the formula (III-9) to the formula (III-30) are shown below.
式(III-17)至式(III-25)中,B29較佳為表示碳數為1至10的烷基或碳數為1至10的烷氧基;B30較佳為表示氫原子、碳數為1至10的烷基或碳數為1至10的烷氧基。 In formulae (III-17) to (III-25), B 29 is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; B 30 is preferably a hydrogen atom An alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
上述的二胺化合物(a2)可單獨使用或組合多種來使用。 The aforementioned diamine compound (a2) may be used alone or in combination.
二胺化合物(a2)的具體例較佳為包括但不限於1,2-二胺基乙烷、4,4’-二胺基二環己基甲烷、4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基醚、5-[4-(4-正戊烷基環己基)環己基]苯基亞甲基-1,3-二胺基苯、1,1-雙[4-(4-胺基苯氧基)苯基]-4-(4-乙基苯基)環己烷、2,4-二胺基苯基甲酸乙酯、由式(III-1-1)表示的化合物、由式(III-1-2)表示的化合物、由式(III-1-5)表示的化合物、由式(III-2-1)表示的化合物、由式(III-2-11)表示的化合物、對-二胺苯、間-二胺苯、鄰-二胺苯、由式(III-8-1)表示的化合物,或上述化合物的組合。 Specific examples of the diamine compound (a2) preferably include, but are not limited to, 1,2-diaminoethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenyl ether, 5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenylmethylene-1,3-diaminobenzene, 1, 1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl) cyclohexane, ethyl 2,4-diaminophenylformate, -1-1), a compound represented by formula (III-1-2), a compound represented by formula (III-1-5), a compound represented by formula (III-2-1), The compound represented by (III-2-11), p-diaminebenzene, m-diaminebenzene, o-diaminebenzene, a compound represented by formula (III-8-1), or a combination of the above-mentioned compounds.
基於所述二胺組份(a2)的總使用量為100莫耳,二胺化合物(a2-2)的使用量可為50莫耳至95莫耳,較佳為60莫耳至90莫耳,更佳為70莫耳至85莫耳。 Based on the total amount of the diamine component (a2) being 100 mol, the amount of the diamine compound (a2-2) may be 50 mol to 95 mol, preferably 60 mol to 90 mol , More preferably 70 mol to 85 mol.
當液晶配向劑中聚合物(A)含有式(III-1)、式(III-2)表示的二胺化合物中的至少一種時,可進一步改善液晶顯示元件 的色相不均的問題。 When the polymer (A) in the liquid crystal alignment agent contains at least one of the diamine compounds represented by the formula (III-1) and the formula (III-2), the liquid crystal display element can be further improved. The problem of uneven hue.
聚合物(A)可包括聚醯胺酸及聚醯亞胺中的至少一者。另外,聚合物(A)可更包括聚醯亞胺系嵌段共聚合物。以下進一步說明上述各種聚合物的製備方法。 The polymer (A) may include at least one of polyamic acid and polyimide. The polymer (A) may further include a polyfluorene-based block copolymer. The methods for preparing the various polymers described above are further described below.
聚合物(A)可包括聚醯胺酸及聚醯亞胺中的至少一者。另外,聚合物(A)可更包括聚醯亞胺系嵌段共聚合物。以下進一步說明上述各種聚合物的製備方法。 The polymer (A) may include at least one of polyamic acid and polyimide. The polymer (A) may further include a polyfluorene-based block copolymer. The methods for preparing the various polymers described above are further described below.
製備聚醯胺酸的方法為先將混合物溶解於溶劑中,其中混合物包括四羧酸二酐組份(a1)與二胺組份(a2),並於0℃至100℃的溫度下進行聚縮合反應。反應1小時至24小時後,以蒸發器對反應溶液進行減壓蒸餾,即可得到聚醯胺酸。或者,將反應溶液倒入大量的貧溶劑中,以得到析出物。接著,以減壓乾燥的方式乾燥析出物,即可得到聚醯胺酸。 The method for preparing polyamic acid is to first dissolve the mixture in a solvent, where the mixture includes a tetracarboxylic dianhydride component (a1) and a diamine component (a2), and polymerize at a temperature of 0 ° C to 100 ° C. Condensation reaction. After reacting for 1 hour to 24 hours, the reaction solution is distilled under reduced pressure using an evaporator to obtain polyamic acid. Alternatively, the reaction solution is poured into a large amount of a lean solvent to obtain a precipitate. Then, the precipitate is dried under reduced pressure to obtain polyamic acid.
用於聚縮合反應中的溶劑可與下述液晶配向劑中的溶劑相同或不同,且用於聚縮合反應中的溶劑並無特別的限制,只要是可溶解反應物與生成物即可。溶劑較佳為包括但不限於(1)非質子系極性溶劑,例如:N-甲基-2-吡咯烷酮(N-methyl-2-pyrrolidinone;NMP)、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、 二甲基亞碸、γ-丁內酯、四甲基尿素或六甲基磷酸三胺等的非質子系極性溶劑;或(2)酚系溶劑,例如:間-甲酚、二甲苯酚、酚或鹵化酚類等的酚系溶劑。基於混合物的總使用量為100重量份,用於聚縮合反應中的溶劑的使用量較佳為200重量份至2000重量份,且更佳為300重量份至1800重量份。 The solvent used in the polycondensation reaction may be the same as or different from the solvent in the liquid crystal alignment agent described below, and the solvent used in the polycondensation reaction is not particularly limited as long as it can dissolve the reactant and the product. The solvent preferably includes, but is not limited to (1) an aprotic polar solvent, such as: N-methyl-2-pyrrolidinone (NMP), N, N-dimethylacetamide, N, N-dimethylformamide, Aprotic polar solvents such as dimethyl sulfene, γ-butyrolactone, tetramethyl urea or hexamethyl phosphate triamine; or (2) phenolic solvents such as m-cresol, xylenol, Phenol-based solvents such as phenols and halogenated phenols. The use amount of the solvent used in the polycondensation reaction is preferably 200 parts by weight to 2000 parts by weight, and more preferably 300 parts by weight to 1800 parts by weight based on the total use amount of the mixture.
值得注意的是,於聚縮合反應中,溶劑可併用適量的貧溶劑,其中貧溶劑不會造成聚醯胺酸析出。貧溶劑可以使用單獨一種或者組合多種來使用,且其包括但不限於(1)醇類,例如:甲醇、乙醇、異丙醇、環己醇、乙二醇、丙二醇、1,4-丁二醇或三乙二醇等的醇類;(2)酮類,例如:丙酮、甲基乙基酮、甲基異丁基酮、環己酮等的酮類;(3)酯類,例如:醋酸甲酯、醋酸乙酯、醋酸丁酯、草酸二乙酯、丙二酸二乙酯或乙二醇乙基醚醋酸酯等的酯類;(4)醚類,例如:二乙基醚、乙二醇甲基醚、乙二醇乙基醚、乙二醇正丙基醚、乙二醇異丙基醚、乙二醇正丁基醚、乙二醇二甲基醚或二乙二醇二甲基醚等的醚類;(5)鹵化烴類,例如:二氯甲烷、1,2-二氯乙烷、1,4-二氯丁烷、三氯乙烷、氯苯或鄰-二氯苯等的鹵化烴類;或(6)烴類,例如:四氫呋喃、己烷、庚烷、辛烷、苯、甲苯或二甲苯等的烴類或上述溶劑的任意組合。基於二胺組份(a2)的使用量為100重量份,貧溶劑的用量較佳為0重量份至60重量份,且更佳為0重量份至50重量份。 It is worth noting that in the polycondensation reaction, an appropriate amount of a lean solvent can be used in combination with the solvent, wherein the lean solvent does not cause the polyamic acid to precipitate. The lean solvent can be used singly or in combination, and it includes but is not limited to (1) alcohols, such as: methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butane Alcohols or alcohols such as triethylene glycol; (2) ketones, such as: ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; (3) esters, such as: Esters such as methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, or ethylene glycol ethyl ether acetate; (4) ethers, such as diethyl ether, Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, or diethylene glycol dimethyl ether Ethers such as alkyl ethers; (5) halogenated hydrocarbons, such as: dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, or o-dichloro Halogenated hydrocarbons such as benzene; or (6) hydrocarbons, for example: hydrocarbons such as tetrahydrofuran, hexane, heptane, octane, benzene, toluene or xylene, or any combination of the above solvents. Based on the use amount of the diamine component (a2) being 100 parts by weight, the use amount of the lean solvent is preferably 0 to 60 parts by weight, and more preferably 0 to 50 parts by weight.
製備聚醯亞胺的方法為將上述製備聚醯胺酸的方法所製的聚醯胺酸在脫水劑及觸媒的存在下進行加熱而得。在加熱過程中,聚醯胺酸中的醯胺酸官能基可經由脫水閉環反應轉變成醯亞胺官能基(即醯亞胺化)。 The method for preparing polyimide is obtained by heating the polyamidic acid prepared by the method for preparing polyamidic acid in the presence of a dehydrating agent and a catalyst. During the heating process, the arsenic acid functional group in the polyarsenic acid can be converted into the arsonimine functional group (ie, arsonimation) via a dehydration ring-closure reaction.
用於脫水閉環反應中的溶劑可與液晶配向劑中的溶劑(D)相同,故在此不另贅述。基於聚醯胺酸的使用量為100重量份,用於脫水閉環反應中的溶劑的使用量較佳為200重量份至2000重量份,且更佳為300重量份至1800重量份。 The solvent used in the dehydration ring-closing reaction can be the same as the solvent (D) in the liquid crystal alignment agent, so it will not be repeated here. The amount of the solvent used in the dehydration ring-closing reaction is preferably 200 to 2000 parts by weight, and more preferably 300 to 1800 parts by weight, based on 100 parts by weight of the polyamic acid used.
為獲得較佳的聚醯胺酸的醯亞胺化程度,脫水閉環反應的操作溫度較佳為40℃至200℃,更佳為40℃至150℃。若脫水閉環反應的操作溫度低於40℃時,醯亞胺化的反應不完全,而降低聚醯胺酸的醯亞胺化程度。然而,若脫水閉環反應的操作溫度高於200℃時,所得的聚醯亞胺的重量平均分子量偏低。 In order to obtain a better degree of polyimidation of the polyimide, the operating temperature of the dehydration ring-closing reaction is preferably 40 ° C to 200 ° C, and more preferably 40 ° C to 150 ° C. If the operating temperature of the dehydration ring-closing reaction is lower than 40 ° C, the imidization reaction is not complete, and the degree of imidization of the polyacid is reduced. However, if the operating temperature of the dehydration ring-closing reaction is higher than 200 ° C, the weight average molecular weight of the obtained polyfluorene imine is low.
用於脫水閉環反應中的脫水劑可選自於酸酐類化合物’其具體例如:醋酸酐、丙酸酐或三氟醋酸酐等的酸酐類化合物。基於聚醯胺酸為1莫耳,脫水劑的使用量為0.01莫耳至20莫耳。用於脫水閉環反應中的觸媒可選自於(1)吡啶類化合物,例如:吡啶、三甲基吡啶或二甲基吡啶等的吡啶類化合物;(2)三級胺類化合物,例如:三乙基胺等的三級胺類化合物。基於脫水劑的使用量為1莫耳,觸媒的使用量可為0.5莫耳至10莫耳。 The dehydrating agent used in the dehydration ring-closing reaction may be selected from acid anhydride compounds', and specific examples thereof include acid anhydride compounds such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. Based on 1 mole of polyamic acid, the amount of dehydrating agent used is 0.01 to 20 moles. The catalyst used in the dehydration ring-closing reaction may be selected from (1) pyridine compounds, such as pyridine, trimethylpyridine, or dimethylpyridine; and (2) tertiary amine compounds, such as: Tertiary amines such as triethylamine. Based on the amount of dehydrating agent used is 1 mole, the amount of catalyst used can be 0.5 to 10 moles.
聚合物(A)的醯亞胺化率可為30%至90%,較佳為35% 至88%,且更佳為30%至85%。當液晶配向劑中聚合物(A)的醯亞胺化率在上述範圍內時,可進一步提升液晶顯示元件的耐紫外線衰退性。 The amidation ratio of the polymer (A) may be 30% to 90%, preferably 35% To 88%, and more preferably 30% to 85%. When the fluorinated imidization ratio of the polymer (A) in the liquid crystal alignment agent is within the above range, the ultraviolet decay resistance of the liquid crystal display element can be further improved.
聚醯亞胺系嵌段共聚合物為選自聚醯胺酸嵌段共聚合物、聚醯亞胺嵌段共聚合物、聚醯胺酸-聚醯亞胺嵌段共聚合物或上述聚合物的任意組合。 The polyimide-based block copolymer is selected from the group consisting of a polyimide block copolymer, a polyimide block copolymer, a polyimide-polyimide block copolymer, or the above-mentioned polymerization. Any combination of things.
製備聚醯亞胺系嵌段共聚合物的方法較佳為先將起始物溶解於溶劑中,並進行聚縮合反應,其中起始物包括至少一種聚醯胺酸及/或至少一種聚醯亞胺,且可進一步包括羧酸酐組份與二胺組份。 The method for preparing a polyfluorene-based block copolymer is preferably firstly dissolving a starting material in a solvent and performing a polycondensation reaction, wherein the starting material includes at least one polyamidic acid and / or at least one polyfluorene Imine, and may further include a carboxylic anhydride component and a diamine component.
起始物中的羧酸酐組份與二胺組份可與製備聚醯胺酸的方法中所使用的四羧酸二酐組份(a1)與二胺組份(a2)相同,且用於聚縮合反應中的溶劑可與下述液晶配向劑中的溶劑相同,在此不另贅述。 The carboxylic acid anhydride component and the diamine component in the starting material may be the same as the tetracarboxylic dianhydride component (a1) and the diamine component (a2) used in the method for preparing a polyamic acid, and are used for The solvent in the polycondensation reaction may be the same as the solvent in the liquid crystal alignment agent described below, and details are not described herein again.
基於起始物的使用量為100重量份,用於聚縮合反應中的溶劑的使用量較佳為200重量份至2000重量份,且更佳為300重量份至1800重量份。聚縮合反應的操作溫度較佳為0℃至200℃,且更佳為0℃至100℃。 The used amount of the solvent used in the polycondensation reaction is preferably 200 to 2000 parts by weight, and more preferably 300 to 1800 parts by weight based on the used amount of the starting material. The operating temperature of the polycondensation reaction is preferably 0 ° C to 200 ° C, and more preferably 0 ° C to 100 ° C.
起始物較佳為包括但不限於(1)二種末端基相異且結構相異的聚醯胺酸;(2)二種末端基相異且結構相異的聚醯亞胺;(3) 末端基相異且結構相異的聚醯胺酸及聚醯亞胺;(4)聚醯胺酸、羧酸酐組份與二胺組份,其中,羧酸酐組份與二胺組份之中的至少一種與形成聚醯胺酸所使用的羧酸酐組份與二胺組份的結構相異;(5)聚醯亞胺、羧酸酐組份與二胺組份,其中,羧酸酐組份與二胺組份中的至少一種與形成聚醯亞胺所使用的羧酸酐組份與二胺組份的結構相異;(6)聚醯胺酸、聚醯亞胺、羧酸酐組份與二胺組份,其中,羧酸酐組份與二胺組份中的至少一種與形成聚醯胺酸或聚醯亞胺所使用的羧酸酐組份與二胺組份的結構相異;(7)二種結構相異的聚醯胺酸、羧酸酐組份與二胺組份;(8)二種結構相異的聚醯亞胺、羧酸酐組份與二胺組份;(9)二種末端基為酸酐基且結構相異的聚醯胺酸以及二胺組份;(10)二種末端基為胺基且結構相異的聚醯胺酸以及羧酸酐組份;(11)二種末端基為酸酐基且結構相異的聚醯亞胺以及二胺組份;或者(12)二種末端基為胺基且結構相異的聚醯亞胺以及羧酸酐組份。 The starting material preferably includes, but is not limited to, (1) two polyamido acids with different terminal groups and different structures; (2) two polyimines with different terminal groups and different structures; (3 ) Polyamines and polyimines having different terminal groups and different structures; (4) Polyamines, carboxylic anhydride components, and diamine components, among which the carboxylic anhydride component and the diamine component At least one of them is different from the structure of the carboxylic acid anhydride component and the diamine component used to form the polyamidic acid; (5) the polyfluorene imine, the carboxylic acid anhydride component, and the diamine component, wherein the carboxylic acid anhydride component And at least one of the diamine component is different from the structure of the carboxylic acid anhydride component and the diamine component used to form the polyfluorene imine; (6) the polyfluorine acid, the polyfluorene imine, the carboxylic acid anhydride component and A diamine component, wherein at least one of the carboxylic acid anhydride component and the diamine component is different from the structure of the carboxylic acid anhydride component and the diamine component used to form the polyamidic acid or the polyimide; (7 ) Two kinds of polyfluorinated acid, carboxylic anhydride and diamine components with different structures; (8) two kinds of polyfluorinated imine, carboxylic anhydride and diamine components with different structures; (9) two Polyamino acids and diamine components with different terminal groups being acid anhydride groups and different structures; (10) polyamino acids and carboxylic acid anhydride components with different terminal groups having amine groups and structural differences; (11) two Anhydride And structurally distinct polyimide and a diamine component; or (12) two terminal amino groups of the polyimide and structurally distinct parts and a carboxylic anhydride group.
在不影響本發明的功效的範圍內,聚醯胺酸、聚醯亞胺以及聚醯亞胺系嵌段共聚合物較佳為先進行分子量調節後的末端修飾型聚合物。藉由使用末端修飾型的聚合物,可改善液晶配向劑的塗佈性能。製備末端修飾型聚合物的方式可藉由在聚醯胺酸進行聚縮合反應的同時,加入單官能性化合物來製得。 As long as the efficacy of the present invention is not affected, the polyamidic acid, polyamidoimide, and polyamidoimide block copolymer are preferably terminally modified polymers after molecular weight adjustment. By using a terminal-modified polymer, the coating performance of the liquid crystal alignment agent can be improved. The method for preparing the terminal-modified polymer can be prepared by adding a polyfunctional compound while the polyamic acid is undergoing a polycondensation reaction.
單官能性化合物的具體例包括但不限於(1)一元酸酐,例如:馬來酸酐、鄰苯二甲酸酐、衣康酸酐、正癸基琥珀酸酐、正十二烷基琥珀酸酐、正十四烷基琥珀酸酐或正十六烷基琥珀酸 酐等一元酸酐;(2)單胺化合物,例如:苯胺、環己胺、正丁胺、正戊胺、正己胺、正庚胺、正辛胺、正壬胺、正癸胺、正十一烷胺、正十二烷胺、正十三烷胺、正十四烷胺、正十五烷胺、正十六烷胺、正十七烷胺、正十八烷胺或正二十烷胺等單胺化合物;或(3)單異氰酸酯化合物,例如:異氰酸苯酯或異氰酸萘基酯等單異氰酸酯化合物。 Specific examples of monofunctional compounds include, but are not limited to (1) monobasic anhydrides, such as: maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecyl Alkyl succinic anhydride or n-hexadecyl succinic acid Monobasic acid anhydrides such as anhydrides; (2) Monoamine compounds, such as: aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecyl Alkylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecanylamine, n-octadecylamine, or n-eicosylamine And other monoamine compounds; or (3) monoisocyanate compounds, such as monoisocyanate compounds such as phenyl isocyanate or naphthyl isocyanate.
本發明的聚合物(A),根據凝膠滲透色層分析法(Gel Permeation Chromatography,GPC)所測得經聚苯乙烯換算的重量平均分子量為2,000至200,000,較佳為3,000至100,000,更佳為4,000至50,000。 The polymer (A) of the present invention has a polystyrene-equivalent weight average molecular weight as measured by Gel Permeation Chromatography (GPC) of 2,000 to 200,000, preferably 3,000 to 100,000, and more preferably It is 4,000 to 50,000.
聚矽氧烷(B)含有乙烯性不飽和基,以及選自由、、-O-及所組成的族群中的至少一種官能基。 The polysiloxane (B) contains an ethylenically unsaturated group, and is selected from the group consisting of , , -O- and At least one functional group in the formed group.
製備聚矽氧烷(B)的步驟包括:步驟(i)由含環氧基的矽烷化合物(b1)自行聚縮合成聚矽氧烷化合物;或者由含環氧基的矽烷化合物(b1)與其它矽烷化合物(b2)共聚縮合(copolycondensation)成聚矽氧烷化合物;以及步驟(ii)使上述聚矽氧烷化合物與乙烯性不飽和化合物(b3)反應,以獲得聚矽氧烷(B)。 The step of preparing the polysiloxane (B) includes: step (i) self-condensing the polysiloxane compound containing the epoxy group-containing silane compound (b1); or the epoxy group-containing silane compound (b1) and Copolycondensation of other silane compounds (b2) to polysiloxane compounds; and step (ii) reacting the above polysiloxane compounds with ethylenically unsaturated compounds (b3) to obtain polysiloxanes (B) .
含環氧基的矽烷化合物(b1)所含有的含環氧基的基團包括由式(1-1)表示的基、由式(1-2)表示的基以及由式(1-3)表示的基中的至少一者。 The epoxy group-containing silane compound (b1) contains an epoxy group-containing group including a group represented by formula (1-1), a group represented by formula (1-2), and a group represented by formula (1-3) At least one of the bases represented.
具體而言,由式(1-1)表示的基、由式(1-2)表示的基以及由式(1-3)表示的基如下所示。 Specifically, the group represented by Formula (1-1), the group represented by Formula (1-2), and the group represented by Formula (1-3) are shown below.
式(1-1)中,B表示氧原子或單鍵;c表示1至3的整數;d表示0至6的整數,其中當d表示0時,B為單鍵。 In the formula (1-1), B represents an oxygen atom or a single bond; c represents an integer of 1 to 3; d represents an integer of 0 to 6, wherein when d represents 0, B is a single bond.
另外,由式(1-2)表示的基如下所示。 The base represented by the formula (1-2) is shown below.
式(1-2)中,e表示0至6的整數。 In Formula (1-2), e represents an integer of 0 to 6.
由式(1-3)表示的基如下所示。 The base represented by the formula (1-3) is shown below.
式(1-3)中,D表示碳數為2至6的伸烷基;E表示氫原子或碳數為1至6的烷基。 In the formula (1-3), D represents an alkylene group having 2 to 6 carbon atoms; E represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
在下文中,將詳細說明含環氧基的矽烷化合物(b1)、其他矽烷化合物(b2)、乙烯性不飽和化合物(b3)以及聚矽氧烷(B)的製備方法。 Hereinafter, a method for producing the epoxy group-containing silane compound (b1), other silane compound (b2), ethylenically unsaturated compound (b3), and polysiloxane (B) will be described in detail.
含環氧基的矽烷化合物(b1)所含有的含環氧基的基團例如是縮水甘油基(glycidyl group)、縮水甘油醚基(glycidyloxy group)、環氧環己基(epoxycyclohexyl group)或環氧丙烷基(oxetanyl group)。 The epoxy group-containing silane compound (b1) contains an epoxy group-containing group such as a glycidyl group, a glycidyloxy group, an epoxycyclohexyl group, or an epoxy group. Oxetanyl group.
具體而言,含環氧基的基團可包括由上述式(1-1)表示的基、由上述式(1-2)表示的基以及由上述式(1-3)表示的基中的至少一者。 Specifically, the epoxy group-containing group may include a group represented by the above formula (1-1), a group represented by the above formula (1-2), and a group represented by the above formula (1-3) At least one.
含環氧基的基團較佳為包括由式(1-1-1)表示的基、由式(1-2-1)表示的基以及由式(1-3-1)表示的基中的至少一者。 The epoxy group-containing group preferably includes a group represented by the formula (1-1-1), a group represented by the formula (1-2-1), and a group represented by the formula (1-3-1) At least one of them.
含環氧基的矽烷化合物(b1)的具體例包括3-(N,N-二縮水甘油基)胺基丙基三甲氧基矽烷、3-(N-烯丙基-N-縮水甘油基)胺基丙基三甲氧基矽烷、3-縮水甘油醚基丙基三甲氧基矽烷、3-縮水甘油醚基丙基三乙氧基矽烷、3-縮水甘油醚基丙基甲基二甲氧基矽烷、3-縮水甘油醚基丙基甲基二乙氧基矽烷、3-縮水甘油醚基丙基二甲基甲氧基矽烷、3-縮水甘油醚基丙基二甲基乙氧基矽烷、2-縮水甘油醚基乙基三甲氧基矽烷、2-縮水甘油醚基乙基三乙氧基矽烷、2-縮水甘油醚基乙基甲基二甲氧基矽烷、2-縮水甘油醚基乙基甲基二乙氧基矽烷、2-縮水甘油醚基乙基二甲基甲氧基矽烷、2-縮水甘油醚基乙基二甲基乙氧基矽烷、4-縮水甘油醚基丁基三甲氧基矽烷、4-縮水甘油醚基丁基三乙氧基矽烷、4-縮水甘油醚基丁基甲基二甲氧基矽烷、4-縮水甘油醚基丁基甲基二乙氧基矽烷、4-縮水甘油醚基丁基二甲基甲氧基矽烷、4-縮水甘油醚基丁基二甲基乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三乙氧基矽烷、3-(3,4-環氧環己基)丙 基三甲氧基矽烷、3-(3,4-環氧環己基)丙基三乙氧基矽烷、((3-乙基-3-環氧丙烷基)甲氧基)丙基三甲氧基矽烷、((3-乙基-3-環氧丙烷基)甲氧基)丙基三乙氧基矽烷、((3-乙基-3-環氧丙烷基)甲氧基)丙基甲基二甲氧基矽烷或((3-乙基-3-環氧丙烷基)甲氧基)丙烷二甲基甲氧基矽烷,或上述化合物的組合。 Specific examples of the epoxy-containing silane compound (b1) include 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, 3- (N-allyl-N-glycidyl) Aminopropyltrimethoxysilane, 3-glycidyletherpropyltrimethoxysilane, 3-glycidyletherpropyltriethoxysilane, 3-glycidyletherpropylmethyldimethoxy Silane, 3-glycidyl ether propyl methyl diethoxy silane, 3-glycidyl ether propyl dimethyl methoxy silane, 3-glycidyl ether propyl dimethyl ethoxy silane, 2-glycidyl ether ethyltrimethoxysilane, 2-glycidyl ether ethyltriethoxysilane, 2-glycidyl ether ethylmethyldimethoxysilane, 2-glycidyl ether ethyl Methyl methyl diethoxysilane, 2-glycidyl ether ethyl dimethyl methoxysilane, 2-glycidyl ether ethyl dimethyl ethoxysilane, 4-glycidyl ether butyl trimethyl Oxysilane, 4-glycidyl ether butyl triethoxy silane, 4-glycidyl ether butyl methyl dimethoxy silane, 4-glycidyl ether butyl methyl diethoxy silane, 4-glycidyl Oleyl butyl dimethyl methoxysilane, 4-glycidyl butyl dimethyl ethoxy silane, 2- (3,4-epoxycyclohexyl) ethyl trimethoxy silane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propane Trimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, ((3-ethyl-3-epoxypropylalkyl) methoxy) propyltrimethoxysilane ((3-ethyl-3-glycidyl) methoxy) propyltriethoxysilane, ((3-ethyl-3-glycidyl) methoxy) propylmethyldi Methoxysilane or ((3-ethyl-3-glycidyl) methoxy) propanedimethylmethoxysilane, or a combination thereof.
含環氧基的矽烷化合物(b1)的具體例較佳為包括3-縮水甘油醚基丙基三甲氧基矽烷、2-縮水甘油醚基乙基三甲氧基矽烷、4-縮水甘油醚基丁基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三乙氧基矽烷、((3-乙基-3-環氧丙烷基)甲氧基)丙基三甲氧基矽烷、((3-乙基-3-環氧丙烷基)甲氧基)丙基三乙氧基矽烷或上述化合物的組合。 Specific examples of the epoxy group-containing silane compound (b1) include 3-glycidyletherpropyltrimethoxysilane, 2-glycidyletherethyltrimethoxysilane, and 4-glycidyletherbutyl. Trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, ((3-ethyl Propyl-3-glycidyl) methoxy) propyltrimethoxysilane, ((3-ethyl-3-glycidyl) methoxy) propyltriethoxysilane or a combination of the above compounds .
基於含環氧基的矽烷化合物(b1)及其他矽烷化合物(b2)的合計使用量為1.00莫耳,含環氧基的矽烷化合物(b1)的使用量為0.30至1.00莫耳,較佳為0.35至0.95莫耳,更佳為0.40至0.90莫耳。 The total amount of the epoxy group-containing silane compound (b1) and other silane compounds (b2) is 1.00 mol, and the amount of the epoxy group-containing silane compound (b1) is 0.30 to 1.00 mol, preferably 0.35 to 0.95 moles, more preferably 0.40 to 0.90 moles.
其他矽烷化合物(b2)例如是具有1個矽原子的化合物。具有1個矽原子的化合物包括具有4個水解性基團的矽烷化合物、具有3個水解性基團的矽烷化合物、具有2個水解性基團的矽烷化合物、具有1個水解性基團的矽烷化合物,或其組合。 The other silane compound (b2) is, for example, a compound having one silicon atom. The compound having one silicon atom includes a silane compound having four hydrolyzable groups, a silane compound having three hydrolyzable groups, a silane compound having two hydrolyzable groups, and a silane having one hydrolyzable group. Compound, or a combination thereof.
具有4個水解性基團的矽烷化合物的具體例包括四氯矽 烷、四甲氧基矽烷、四乙氧基矽烷、四正丙氧基矽烷、四異丙氧基矽烷、四正丁氧基矽烷、四第二丁氧基矽烷,或上述化合物的組合。 Specific examples of the silane compound having four hydrolyzable groups include tetrachlorosilane Alkane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-second butoxysilane, or a combination thereof.
具有3個水解性基團的矽烷化合物的具體例包括三氯矽烷、三甲氧基矽烷、三乙氧基矽烷、氟三氯矽烷、氟三甲氧基矽烷、氟三乙氧基矽烷、甲基三氯矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、2-(三氟甲基)乙基三氯矽烷、2-(三氟甲基)乙基三甲氧基矽烷、2-(三氟甲基)乙基三乙氧基矽烷、羥甲基三氯矽烷、羥甲基三甲氧基矽烷、羥乙基三甲氧基矽烷、巰甲基三氯矽烷、3-巰丙基三氯矽烷、巰甲基三甲氧基矽烷、巰甲基三乙氧基矽烷、3-巰丙基三甲氧基矽烷、3-巰丙基三乙氧基矽烷、苯基三氯矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷,或上述化合物的組合。 Specific examples of the silane compound having three hydrolyzable groups include trichlorosilane, trimethoxysilane, triethoxysilane, fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, and methyltrisiloxane. Chlorosilane, methyltrimethoxysilane, methyltriethoxysilane, 2- (trifluoromethyl) ethyltrichlorosilane, 2- (trifluoromethyl) ethyltrimethoxysilane, 2- ( (Trifluoromethyl) ethyltriethoxysilane, hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane, mercaptomethyltrichlorosilane, 3-mercaptopropyltrichlorosilane Silane, thiomethyltrimethoxysilane, thiomethyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane Silane, phenyltriethoxysilane, or a combination thereof.
具有2個水解性基團的矽烷化合物的具體例包括甲基二氯矽烷、甲基二甲氧基矽烷、甲基二乙氧基矽烷、二甲基二氯矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、甲基[2-(全氟正辛基)乙基]二氯矽烷、甲基[2-(全氟正辛基)乙基]二甲氧基矽烷、3-巰丙基甲基二氯矽烷、3-巰丙基甲基二甲氧基矽烷、、二苯基二氯矽烷、二苯基二甲氧基矽烷,或上述化合物的組合。 Specific examples of the silane compound having two hydrolyzable groups include methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, dimethyldichlorosilane, and dimethyldimethoxy Silane, dimethyldiethoxysilane, methyl [2- (perfluoron-octyl) ethyl] dichlorosilane, methyl [2- (perfluoron-octyl) ethyl] dimethoxysilane , 3-mercaptopropylmethyldichlorosilane, 3-mercaptopropylmethyldimethoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, or a combination thereof.
具有1個水解性基團的矽烷化合物的具體例包括氯二甲基矽烷、甲氧基二甲基矽烷、氯三甲基矽烷、溴三甲基矽烷、碘三甲基矽烷、甲氧基三甲基矽烷、、氯甲基二苯基矽烷、甲氧基 甲基二苯基矽烷,或上述化合物的組合。 Specific examples of the silane compound having one hydrolyzable group include chlorodimethylsilane, methoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, and methoxytrimethylsilane. Methylsilane, chloromethyldiphenylsilane, methoxy Methyldiphenylsilane, or a combination of the above.
其他矽烷化合物(b2)的市售商品的具體例可列舉KC-89、KC-89S、X-21-3153、X-21-5841、X-21-5842、X-21-5843、X-21-5844、X-21-5845、X-21-5846、X-21-5847、X-21-5848、X-22-160AS、X-22-170B、X-22-170BX、X-22-170D、X-22-170DX、X-22-176B、X-22-176D、X-22-176DX、X-22-176F、X-40-2308、X-40-2651、X-40-2655A、X-40-2671、X-40-2672、X-40-9220、X-40-9225、X-40-9227、X-40-9246、X-40-9247、X-40-9250、X-40-9323、X-41-1053、X-41-1056、X-41-1805、X-41-1810、KF6001、KF6002、KF6003、KR212、KR-213、KR-217、KR220 L、KR242A、KR271、KR282、KR300、KR311、KR401N、KR500、KR510、KR5206、KR5230、KR5235、KR9218、KR9706(信越化學製);玻璃樹脂(GLASS RESIN,昭和電工製);SH804、SH805、SH806A、SH840、SR2400、SR2402、SR2405、SR2406、SR2410、SR2411、SR2416、SR2420(東麗道康寧製);FZ3711、FZ3722(NUC製);DMS-S12、DMS-S15、DMS-S21、DMS-S27、DMS-S31、DMS-S32、DMS-S33、DMS-S35、DMS-S38、DMS-S42、DMS-S45、DMS-S51、DMS-227、PSD-0332、PDS-1615、PDS-9931、XMS-5025(JNC製);MS51、MS56(三菱化學製);以及GR100、GR650、GR908、GR950(昭和電工製)等的部分縮合物。 Specific examples of commercially available products of other silane compounds (b2) include KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, and X-21. -5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D , X-22-170DX, X-22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X -40-2671, X-40-2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40 -9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220 L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (made by Shin-Etsu Chemical); glass resin (GLASS RESIN, manufactured by Showa Denko); SH804, SH805, SH806A, SH840, SR2400, SR2402 SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (made by Toray Dow Corning); FZ3711, FZ3722 (made by NUC); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, D MS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (manufactured by JNC); MS51, MS56 (manufactured by Mitsubishi Chemical); and partial condensation of GR100, GR650, GR908, GR950 (manufactured by Showa Denko), etc. Thing.
其他矽烷化合物(b2)較佳為四甲氧基矽烷、四乙氧基矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、苯基三甲氧基矽 烷、苯基三乙氧基矽烷、3-巰丙基三甲氧基矽烷、3-巰丙基三乙氧基矽烷、巰甲基三甲氧基矽烷、巰甲基三乙氧基矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷,或上述化合物的組合。 Other silane compounds (b2) are preferably tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane Alkane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, thiomethyltrimethoxysilane, thiomethyltriethoxysilane, dimethyl Dimethoxysilane, dimethyldiethoxysilane, or a combination thereof.
基於含環氧基的矽烷化合物(b1)及其他矽烷化合物(b2)的合計使用量為1.00莫耳,其他矽烷化合物(b2)的使用量為0.00至0.70莫耳,較佳為0.05至0.65莫耳,更佳為0.10至0.60莫耳。 The total amount of the epoxy-based silane compound (b1) and other silane compounds (b2) is 1.00 mol, and the amount of other silane compounds (b2) is 0.00 to 0.70 mol, preferably 0.05 to 0.65 mol. Ear, more preferably 0.10 to 0.60 mole.
乙烯性不飽和化合物(b3)包括具有羧酸基的乙烯性不飽和化合物、具有胺基的乙烯性不飽和化合物、具有羥基的乙烯性不飽和化合物,或其組合。 The ethylenically unsaturated compound (b3) includes an ethylenically unsaturated compound having a carboxylic acid group, an ethylenically unsaturated compound having an amine group, an ethylenically unsaturated compound having a hydroxyl group, or a combination thereof.
具有羧酸基的乙烯性不飽和化合物的具體例包括(甲基)丙烯酸、2-羧乙基(甲基)丙烯酸酯、鄰苯二甲酸-2-(甲基)丙烯醯氧乙酯、六氫鄰苯二甲酸-2-(甲基)丙烯醯氧乙酯、馬來酸、馬來酸單甲酯、馬來酸單乙酯、富馬酸、富馬酸單甲酯、富馬酸單乙酯、衣康酸、桂皮酸、巴豆酸、紫蘇酸、4-乙烯醯氧基苯乙烯、對-乙烯基苯甲酸、2-丙烯醯氧基乙基-2-羥基乙基-鄰苯二甲酸、4-(2-甲基-丙烯醯氧基)苯甲酸、(甲基)丙烯醯氧基乙基琥珀酸、鄰苯二甲酸單羥基乙基丙烯酸酯或上述化合物的組合。作為所述化合物的商品,可以列舉出例如Light-ester HO-MS、Light-ester HO-HH、HOA-MPL、HOA-MS、HOA-HH(共榮社製)、M-5400(東亞合成製)等。 Specific examples of the ethylenically unsaturated compound having a carboxylic acid group include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2- (meth) acrylic acid ethyl phthalate, and 2- (meth) acrylic acid ethyl phthalate, maleic acid, monomethyl maleate, monoethyl maleate, fumaric acid, monomethyl fumarate, fumaric acid Monoethyl ester, itaconic acid, cinnamic acid, crotonic acid, perillic acid, 4-vinylacetoxystyrene, p-vinylbenzoic acid, 2-propenyloxyethyl-2-hydroxyethyl-o-benzene Dicarboxylic acid, 4- (2-methyl-acrylic acid) benzoic acid, (meth) acrylic acid ethyl succinic acid, phthalic acid monohydroxyethyl acrylate, or a combination of the foregoing compounds. Examples of products of the compound include Light-ester HO-MS, Light-ester HO-HH, HOA-MPL, HOA-MS, HOA-HH (manufactured by Kyoeisha), and M-5400 (manufactured by Toa Synthetic Corporation). )Wait.
具有胺基的乙烯性不飽和化合物的具體例包括乙烯基芐胺(vinylbenzylamine)、(甲基)丙烯酸胺基乙酯(aminoethyl(meth)acrylate),或上述化合物的組合。 Specific examples of the ethylenically unsaturated compound having an amine group include vinylbenzylamine, aminoethyl (meth) acrylate, or a combination thereof.
具有羥基的乙烯性不飽和化合物的具體例包括由式(b3-1)至(b3-10)表示的化合物。 Specific examples of the ethylenically unsaturated compound having a hydroxyl group include compounds represented by the formulae (b3-1) to (b3-10).
式(b3-1)至(b3-10)中,R6表示氫原子或甲基,t1、t2以及t3表示1以上的整數。 In the formulae (b3-1) to (b3-10), R 6 represents a hydrogen atom or a methyl group, and t1, t2, and t3 represent an integer of 1 or more.
乙烯性不飽和化合物(b3)的具體例較佳為包括(甲基)丙烯酸、2-羧乙基(甲基)丙烯酸酯、鄰苯二甲酸-2-(甲基)丙烯醯氧乙酯、六氫鄰苯二甲酸-2-(甲基)丙烯醯氧乙酯、對-乙烯基苯甲酸、對-乙烯基芐胺、甲基丙烯酸胺基乙酯、2-甲基丙烯酸羥乙酯、2-甲基丙烯酸羥丙酯、對-乙烯基苯酚、鄰-(2-甲基烯丙氧基)苯酚,或上述化合物的組合。 Specific examples of the ethylenically unsaturated compound (b3) include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2- (meth) acrylic acid ethyl phthalate, Hexahydrophthalate 2- (meth) acrylic acid ethyl ester, p-vinylbenzoic acid, p-vinylbenzylamine, aminoethyl methacrylate, hydroxyethyl 2-methacrylate, Hydroxypropyl 2-methacrylate, p-vinylphenol, o- (2-methylallyloxy) phenol, or a combination thereof.
乙烯性不飽和化合物(b3)與含環氧基的矽烷化合物(b1)的莫耳當量比例(b3)/(b1)為0.20~0.80,較佳0.25~0.70,更佳0.30~0.60。 The molar equivalent ratio (b3) / (b1) of the ethylenically unsaturated compound (b3) to the epoxy-containing silane compound (b1) is 0.20 to 0.80, preferably 0.25 to 0.70, and more preferably 0.30 to 0.60.
當液晶配向劑中的聚矽氧烷(B)使用乙烯性不飽和化合物(b3)時,可改善液晶顯示元件的色相不均的問題。特別是當 乙烯性不飽和化合物(b3)含有包括由、、表示的基中的至少一者時,可進一步改善液晶顯示元件的色相不均的問題。 When the polysiloxane (B) in the liquid crystal alignment agent uses an ethylenically unsaturated compound (b3), the problem of uneven hue of the liquid crystal display element can be improved. Especially when the ethylenically unsaturated compound (b3) contains , , With at least one of the groups shown, the problem of uneven hue of the liquid crystal display element can be further improved.
本發明的聚矽氧烷(B),根據凝膠滲透色層分析法所測得經聚苯乙烯換算的重量平均分子量為500至100,000,較佳為800至50,000,更佳為1,000至20,000。 The polysiloxane (B) of the present invention has a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography method of 500 to 100,000, preferably 800 to 50,000, and more preferably 1,000 to 20,000.
聚矽氧烷化合物的聚縮合反應可使用一般的方法,例如,在上述矽烷化合物或其混合物中添加有機溶劑、水或選擇性地進一步添加觸媒,接著利用油浴等進行50℃至150℃的加熱,較佳加熱時間為0.5小時至120小時。加熱中,可將混合液進行攪拌,也可以置於回流條件下。 The polycondensation reaction of the polysiloxane compound can be carried out by a general method. For example, an organic solvent, water, or a further selective catalyst is added to the silane compound or a mixture thereof, followed by an oil bath or the like at 50 ° C to 150 ° C. The heating time is preferably 0.5 to 120 hours. During heating, the mixed solution may be stirred or placed under reflux conditions.
上述有機溶劑並沒有特別限制,可與本發明液晶配向劑中所含的溶劑(D)為相同或不同。 The organic solvent is not particularly limited, and may be the same as or different from the solvent (D) contained in the liquid crystal alignment agent of the present invention.
該有機溶劑的具體例包括甲苯、二甲苯等的烴類化合物;甲基乙基酮、甲基異丁基酮、甲基正戊基酮、二乙基酮、環己酮等的酮類化合物;醋酸乙酯、醋酸正丁酯、醋酸異戊酯、丙二醇單甲基醚醋酸酯、醋酸-3-甲氧基丁酯、乳酸乙基等的酯類化合物;乙二醇二甲基醚、乙二醇二乙基醚、四氫呋喃、二噁烷(dioxane)等的醚類化合物;1-己醇、4-甲基2-戊醇、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單正丙基醚、乙二醇單正丁基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單正丙基醚等的醇類化合物,或上述有機溶劑的組合。 Specific examples of the organic solvent include hydrocarbon compounds such as toluene and xylene; ketone compounds such as methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, diethyl ketone, and cyclohexanone. ; Ester compounds such as ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, etc .; ethylene glycol dimethyl ether, Ether compounds such as ethylene glycol diethyl ether, tetrahydrofuran, and dioxane; 1-hexanol, 4-methyl 2-pentanol, ethylene glycol monomethyl ether, and ethylene glycol monoethyl Alcohol compounds such as ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, or a combination of the above organic solvents .
上述有機溶劑可單獨使用或組合多種來使用。 These organic solvents may be used alone or in combination.
基於所有矽烷化合物為100重量份,有機溶劑的使用量較佳為10重量份至1200重量份,更佳為30重量份至1,000重量份。 The use amount of the organic solvent is preferably 10 to 1200 parts by weight, and more preferably 30 to 1,000 parts by weight, based on 100 parts by weight of all the silane compounds.
基於所有矽烷化合物的水解性基團為1莫耳,水的使用量較佳為0.5莫耳至100莫耳,更佳為1莫耳至30莫耳。 Based on the hydrolyzable group of all silane compounds being 1 mol, the amount of water used is preferably 0.5 mol to 100 mol, more preferably 1 mol to 30 mol.
該觸媒沒有特別的限制,較佳地,該觸媒是選自於酸、鹼金屬化合物、有機鹼、鈦化合物、鋯化合物,或其組合。 The catalyst is not particularly limited. Preferably, the catalyst is selected from the group consisting of an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound, or a combination thereof.
酸的具體例包括鹽酸、硝酸、硫酸、氟酸、草酸、磷酸、醋酸、三氟醋酸、蟻酸、多元羧酸、多元酸酐,或其組合。 Specific examples of the acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid, polybasic acid anhydride, or a combination thereof.
鹼金屬化合物的具體例包括氫氧化鈉、氫氧化鉀、甲醇鈉、甲醇鉀、乙醇鈉、乙醇鉀,或其組合。 Specific examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, or a combination thereof.
有機鹼的具體例包括乙胺、二乙胺、哌嗪(piperazine)、哌啶(piperidine)、吡咯啶(pyrrolidine)、吡咯(pyrrole)等的一級或二級的有機胺;三乙胺、三正丙胺、三正丁胺、吡啶(pyridine)、4-二甲胺基吡啶、二氮雜二環十一烯(diazabicycloundecene)等的三級有機胺;四甲基氫氧化銨等的四級有機胺等,或上述化合物的組合。 Specific examples of the organic base include primary or secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; triethylamine, triethylamine Tertiary organic amines such as n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, and other tertiary organic amines such as tetramethylammonium hydroxide Amines, etc., or a combination of the above.
觸媒的使用量根據種類、溫度等反應條件等而異,並可適當地設定,例如基於所有矽烷化合物為1莫耳,該觸媒的添加量為0.01莫耳至5莫耳,較佳為0.03莫耳至3莫耳,更佳為0.05莫耳至1莫耳。 The amount of catalyst used varies depending on the reaction conditions such as type, temperature, etc., and can be appropriately set. For example, based on 1 mol of all silane compounds, the addition amount of the catalyst is 0.01 mol to 5 mol, preferably 0.03 to 3 mol, more preferably 0.05 to 1 mol.
基於安定性觀點,待聚縮合反應結束後,較佳為將從反應液中分餾的有機溶劑層以水清洗。進行該清洗時,較佳為使用包含少量鹽的水,例如0.2重量%左右的硝酸銨水溶液等進行清洗。清洗可進行至清洗後的水層成為中性為止,然後將有機溶劑層視需要以無水硫酸鈣、分子篩(molecular sieves)等乾燥劑進行乾燥後,去除有機溶劑,即可獲得聚矽氧烷化合物。 From the viewpoint of stability, after the completion of the polycondensation reaction, the organic solvent layer fractionated from the reaction liquid is preferably washed with water. When performing this washing | cleaning, it is preferable to wash | clean with water containing a small amount of salt, for example, about 0.2 weight% of ammonium nitrate aqueous solution etc. The cleaning can be performed until the water layer after the cleaning becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate, molecular sieves, etc. as needed, and then the organic solvent is removed to obtain a polysiloxane compound. .
聚矽氧烷化合物與乙烯性不飽和化合物(b3)反應而得到本發明的聚矽氧烷(B)。聚矽氧烷化合物與乙烯性不飽和化合物(b3)的反應可在觸媒與有機溶劑的存在下進行。另外,聚矽氧烷化合物與乙烯性不飽和化合物(b3)的反應亦可在硬化促進劑的存在下進行。 The polysiloxane compound and the ethylenically unsaturated compound (b3) are reacted to obtain the polysiloxane (B) of the present invention. The reaction between the polysiloxane compound and the ethylenically unsaturated compound (b3) can be performed in the presence of a catalyst and an organic solvent. The reaction between the polysiloxane compound and the ethylenically unsaturated compound (b3) may be performed in the presence of a hardening accelerator.
上述步驟(ii)的觸媒的具體例與步驟(i)的的觸媒的具體例相同,在此不另行贅述。 The specific example of the catalyst in step (ii) is the same as the specific example of the catalyst in step (i), and is not repeated here.
基於乙烯性不飽和化合物(b3)為100重量份,觸媒的使用量可為0重量份至100重量份,較佳為0.01重量份至50重量份,更佳為0.1重量份至20重量份。 Based on 100 parts by weight of the ethylenically unsaturated compound (b3), the catalyst may be used in an amount of 0 to 100 parts by weight, preferably 0.01 to 50 parts by weight, and more preferably 0.1 to 20 parts by weight .
上述步驟(ii)的有機溶劑並沒有特別限制,可與步驟(i)的有機溶劑以及本發明液晶配向劑中所含的溶劑(D)為相同或不同。上述有機溶劑的具體例較佳為2-丁酮、2-己酮、甲基異丁基酮、醋酸正丁酯,或其組合。 The organic solvent in the step (ii) is not particularly limited, and may be the same as or different from the organic solvent in the step (i) and the solvent (D) contained in the liquid crystal alignment agent of the present invention. Specific examples of the organic solvent are preferably 2-butanone, 2-hexanone, methyl isobutyl ketone, n-butyl acetate, or a combination thereof.
上述硬化促進劑的的具體例包括芐基二甲基胺、2,4,6-三 (二甲基胺基甲基)苯酚、環己基二甲基胺、三乙醇胺等的三級胺;2-甲基咪唑、2-正庚基咪唑、2-正十一烷基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-芐基-2-甲基咪唑、1-芐基-2-苯基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、1-(2-氰基乙基)-2-甲基咪唑、1-(2-氰基乙基)-2-正十一烷基咪唑、1-(2-氰基乙基)-2-苯基咪唑、1-(2-氰基乙基)-2-乙基-4-甲基咪唑、2-苯基-4-甲基-5-羥甲基咪唑、2-苯基-4,5-二(羥甲基)咪唑、1-(2-氰基乙基)-2-苯基-4,5-二[(2’-氰基乙氧基)甲基]咪唑、1-(2-氰基乙基)-2-正十一烷基咪唑鎓苯偏三酸鹽(1-(2-cyanoethyl)-2-n-undecanyl imidazolium trimellitate)、1-(2-氰基乙基)-2-苯基咪唑鎓苯偏三酸鹽、1-(2-氰基乙基)-2-乙基-4-甲基咪唑鎓苯偏三酸鹽、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]乙基-s-三嗪、2,4-二胺基-6-(2’-正十一烷基咪唑基)乙基-s-三嗪、2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]乙基-s-三嗪、2-甲基咪唑的異氰脲酸加成物、2-苯基咪唑的異氰脲酸加成物、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]乙基-s-三嗪的異氰脲酸加成物等的咪唑化合物;二苯基膦(diphenylphosphine)、三苯基膦、亞磷酸三苯基酯(triphenyl phosphite)等的有機磷化合物;芐基三苯基氯化鏻(benzyl triphenyl phosphonium chloride)、四-正丁基溴化鏻(tetra-n-butyl phosphonium bromide)、甲基三苯基溴化鏻(methyl triphenyl phosphonium bromide)、乙基三苯基溴化鏻(ethyl triphenyl phosphonium bromide)、正丁基三苯基溴化鏻、四苯基溴化鏻、乙基三苯基碘化鏻、乙基三苯基鏻乙酸鹽、四正丁基鏻-O,O-二乙基 偶磷二硫代硫酸鹽(tetra-n-butyl phosphonium-O,O-diethyl phosphorodithionate)、四正丁基鏻苯并三唑鹽(tetra-n-butylphosphonium benzotriazolate)、四正丁基鏻四氟硼酸鹽(tetra-n-butylphosphonium tetrafluoroborate)、四正丁基鏻四苯基硼酸鹽(tetra-n-butyl phosphonium tetraphenylborate)、四苯基鏻四苯基硼酸鹽(tetraphenyl phosphonium tetraphenylborate)等的四級鏻鹽;1,8-二氮雜雙環[5.4.0]十一烯-7或其有機酸鹽等的二氮雜雙環烯烴;辛酸鋅、辛酸錫、乙醯丙酮鋁錯合物(aluminium acetylacetone complex)等的有機金屬化合物;四乙基溴化銨、四-正丁基溴化銨、四乙基氯化銨、四-正丁基氯化銨等的四級銨鹽;三氟化硼(boron trifluoride)、硼酸三苯酯等的硼化合物;氯化鋅、四氯化錫等的金屬鹵素化合物;雙氰胺(dicyandiamide)或胺與環氧樹脂的加成物等胺加成型促進劑等的高熔點分散型潛在性硬化促進劑;將上述咪唑化合物、有機磷化合物或四級鏻鹽等硬化促進劑的表面以聚合物包覆的微膠囊(microcapsule)型潛在性硬化促進劑;胺鹽型潛在性硬化促進劑;路易斯酸鹽、布忍斯特酸鹽(Bronsted acid salt)等高溫解離型的熱陽離子聚合型潛在性硬化促進劑等潛在性硬化促進劑等。 Specific examples of the hardening accelerator include benzyldimethylamine, 2,4,6-tris Tertiary amines such as (dimethylaminomethyl) phenol, cyclohexyldimethylamine, triethanolamine; 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2- Phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl 4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- (2-cyano Ethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis (hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-phenyl-4,5-bis [(2'-cyanoethoxy) methyl Group) imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-n-undecanyl imidazolium trimellitate, 1- ( 2-cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2, 4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazole ) Ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4 ' -Methylimidazolyl- (1 ')] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4 -Imidazole compounds such as diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine isocyanurate adducts; diphenylphosphine, triphenyl Organophosphorus compounds such as phenylphosphine and triphenyl phosphite; benzyl triphenyl phosphonium chloride, tetra-n-butyl phosphonium bromide), methyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, Ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium-O, O-diethyl Tetra-n-butyl phosphonium-O, O-diethyl phosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium benzotriazolate Tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butyl phosphonium tetraphenylborate, tetraphenyl phosphonium tetraphenylborate, etc. ; Diazabicyclic olefins such as 1,8-diazabicyclo [5.4.0] undecene-7 or its organic acid salts; zinc octoate, tin octoate, aluminum acetylacetone complex And other organometallic compounds; quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride; boron trifluoride (boron boron compounds such as trifluoride) and triphenyl borate; metal halogen compounds such as zinc chloride and tin tetrachloride; amine addition accelerators such as dicyandiamide or adducts of amines and epoxy resins High melting point dispersion type latent hardening accelerator; the above-mentioned imidazole compound Organophosphorus compounds or quaternary phosphonium salts and other hardening accelerators with polymer-encapsulated microcapsule-type latent hardening accelerators; amine salt-type latent hardening accelerators; Lewis acid salts, buturonic acid salts (Bronsted acid salt) and other high-temperature dissociation-type thermal cationic polymerization-type latent hardening accelerators.
硬化促進劑的具體例較佳為包括四乙基溴化銨、四-正丁基溴化銨、四乙基氯化銨及四-正丁基氯化銨等的四級銨鹽。 Specific examples of the hardening accelerator are preferably quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride.
上述反應的反應溫度可為0℃至200℃,較佳為50至150℃。上述反應的反應時間可為0.1小時至50小時,較佳為0.5小 時至20小時。 The reaction temperature of the above reaction may be 0 ° C to 200 ° C, and preferably 50 to 150 ° C. The reaction time of the above reaction may be from 0.1 hours to 50 hours, preferably 0.5 hours. Time to 20 hours.
基於聚合物(A)的使用量為100重量份,聚矽氧烷(B)的使用量為3至25重量份,較佳為4至20重量份,且更佳為5至15重量份。 Based on the use amount of the polymer (A) being 100 parts by weight, the use amount of the polysiloxane (B) is 3 to 25 parts by weight, preferably 4 to 20 parts by weight, and more preferably 5 to 15 parts by weight.
若液晶配向劑不使用聚矽氧烷(B),則液晶顯示元件有耐紫外線衰退性不佳的問題。 If the polysiloxane (B) is not used for the liquid crystal alignment agent, the liquid crystal display element has a problem of poor UV resistance.
光聚合性化合物(C)為由式(3)表示的化合物。 The photopolymerizable compound (C) is a compound represented by the formula (3).
式(3)中,R1各自獨立表示由式(3-1)至式(3-5)表示的聚合性官能基、氫原子、鹵素原子、-CN、-CF3、-CF2H、-CFH2、-OCF3、-OCF2H、-N=C=O、-N=C=S或碳數為1至20的烷基,其中烷基中任意的-CH2-可經-O-、-S-、-SO2-、-CO-、-COO-、-OCO-、-CH=CH-、-CF=CF-或-C≡C-取代,且含氫原子的官能基中,任意的氫原子可經鹵素原子或-CN取代;R1的至少一者為由式(3-1)至式(3-5)表示的聚合性官能基;Y獨立表示碳數為3至20的飽和或不飽和的獨立環、縮合環或螺環的2價基,其中環中任意的-CH2-可經-O-取代,任意的-CH=可經-N=取代,任意的-H可經鹵素原子、-CN、-NO2、-NC、-N=C=O、-N=C=S、經1至3個具有 碳數為1至4的烷基或苯基取代的矽基、碳數為1至10的直鏈烷基、碳數為1至10的支鏈烷基或碳數為1至10的鹵烷基取代,且烷基中,任意的-CH2-可經-O-、-CO-、-COO-、-OCO-、-OCOO-、-CH=CH-或-C≡C-取代;Z各自獨立表示單鍵或碳數為1至20的伸烷基,其中,伸烷基中任意的-CH2-可經-O-、-S-、-SO2-、-CO-、-COO-、-OCO-、-OCOO-、-CH=CH-、-CF=CF-、-CH=N-、-N=CH-、-N=N-、-N(O)=N-或-C≡C-取代,且任意的-H可經鹵素原子、碳數為1至10的烷基或碳數為1至10的鹵烷基取代;f表示1至6的整數,且當f為2至6的整數時,多個-Y-Z-為相同或不同。 In formula (3), R 1 each independently represents a polymerizable functional group represented by formula (3-1) to formula (3-5), a hydrogen atom, a halogen atom, -CN, -CF 3 , -CF 2 H, -CFH 2 , -OCF 3 , -OCF 2 H, -N = C = O, -N = C = S, or an alkyl group having 1 to 20 carbon atoms, wherein any -CH 2 in the alkyl group may be passed through- Functional group substituted with O-, -S-, -SO 2- , -CO-, -COO-, -OCO-, -CH = CH-, -CF = CF-, or -C≡C-, and containing a hydrogen atom In the formula, an arbitrary hydrogen atom may be substituted by a halogen atom or -CN; at least one of R 1 is a polymerizable functional group represented by formula (3-1) to formula (3-5); Y independently represents a carbon number of 3 Divalent group of saturated or unsaturated independent ring, condensed ring or spiro ring to 20, wherein any -CH 2 -in the ring may be substituted by -O-, any -CH = may be substituted by -N =, any -H can pass through a halogen atom, -CN, -NO 2 , -NC, -N = C = O, -N = C = S, through 1 to 3 alkyl or phenyl groups having 1 to 4 carbon atoms. Substituted silyl, linear alkyl having 1 to 10 carbons, branched alkyl having 1 to 10 carbons, or haloalkyl having 1 to 10 carbons, and in the alkyl group, any -CH 2 - may be -O -, - CO -, - COO -, - OCO -, - OCOO -, - CH = CH- or -C≡C- Z each independently represents a single bond or an alkylene group having a carbon number of 1 to 20, wherein the extension of any alkyl -CH 2 - may be -O -, - S -, - SO 2 -, - CO -, - COO-, -OCO-, -OCOO-, -CH = CH-, -CF = CF-, -CH = N-, -N = CH-, -N = N-, -N (O) = N- or -C≡C- substitution, and any -H may be substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms; f represents an integer of 1 to 6, and when f When it is an integer of 2 to 6, a plurality of -YZ- are the same or different.
由式(3-1)至式(3-5)表示的聚合性官能基如下所示。 The polymerizable functional groups represented by the formulas (3-1) to (3-5) are shown below.
式(3-1)至式(3-5)中,R2表示氫原子、鹵素原子、-CF3或碳數為1至5的烷基。 In the formulae (3-1) to (3-5), R 2 represents a hydrogen atom, a halogen atom, -CF 3 or an alkyl group having 1 to 5 carbon atoms.
式(3)中,R1的至少一者較佳為為由式(3-1)至式(3-3)表示的聚合性官能基。 In the formula (3), at least one of R 1 is preferably a polymerizable functional group represented by the formula (3-1) to the formula (3-3).
式(3)中,具體而言,Y各自獨立表示1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、萘-2,6-二基、四氫化萘-2,6-二基、芴-2,7-二基、雙環[2.2.2]辛烷-1,4-二基、雙環[3.1.0]己烷-3,6-二基或三蝶烯-1,4-二基的二價基團;在環中的任意的-CH2-可經-O-取代,任意的-CH=可經-N=取代,任意的-H可經鹵素原子、-CN、-NO2、-NC、-N=C=O、-N=C=S、經1至3個具有碳數為1至4的烷基或苯基取代的矽基、碳數為1至10的直鏈烷基或支鏈烷基,或者碳數為1至10的鹵烷基取代;且於烷基中,任意的-CH2-可經-O-、-CO-、-COO-、-OCO-、-OCOO-、-CH=CH-或-C≡C-取代。 In formula (3), specifically, Y each independently represents 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, tetra Naphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] octane-1,4-diyl, bicyclo [3.1.0] hexane-3,6-diyl Or a divalent group of triptycene-1,4-diyl; any -CH 2 -in the ring may be substituted with -O-, any -CH = may be substituted with -N =, any -H Silicon substituted by halogen atom, -CN, -NO 2 , -NC, -N = C = O, -N = C = S, substituted by 1 to 3 alkyl or phenyl groups having 1 to 4 carbon atoms Group, linear or branched alkyl group having 1 to 10 carbon atoms, or haloalkyl group having 1 to 10 carbon atoms; and in the alkyl group, any -CH 2 -can be replaced by -O-, -CO-, -COO-, -OCO-, -OCOO-, -CH = CH- or -C≡C-.
Y較佳為各自獨立表示選自由式(3-6)至式(3-30)表示的官能基所組成的族群中的至少一者。 Y is preferably each independently represented by at least one selected from the group consisting of functional groups represented by formula (3-6) to formula (3-30).
式(3-6)至式(3-30)中,R3表示鹵素原子、碳數為1至3的烷基、碳數為1至3的烷氧基或碳數為1至3的鹵烷基。 In the formulae (3-6) to (3-30), R 3 represents a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen group having 1 to 3 carbon atoms. alkyl.
光聚合性化合物(C)較佳為選自由式(3-31)至式(3-42)表示的化合物所組成的族群中的至少一者。 The photopolymerizable compound (C) is preferably at least one selected from the group consisting of compounds represented by the formulas (3-31) to (3-42).
式(3-31)至式(3-42)中,R4各自獨立表示氫原子或甲基;R5各自獨立表示氫原子、鹵素原子、甲基、-CF3、-OCH3、苯基或同一碳原子上的2個R5形成碳數為6至15的飽和或不飽和的烴環;g及h各自獨立表示1至20的整數。 In the formulae (3-31) to (3-42), each of R 4 independently represents a hydrogen atom or a methyl group; each of R 5 independently represents a hydrogen atom, a halogen atom, a methyl group, -CF 3 , -OCH 3 , or phenyl group. Or two R 5 on the same carbon atom form a saturated or unsaturated hydrocarbon ring having 6 to 15 carbon atoms; g and h each independently represent an integer of 1 to 20.
光聚合性化合物(C)的具體例更佳為包括由式(3-43)至式(3-97)表示的化合物的至少一者。 Specific examples of the photopolymerizable compound (C) include at least one of the compounds represented by the formula (3-43) to the formula (3-97).
光聚合性化合物(C)特佳為包括由式(3-44)至式(3-50)或式(3-69)至式(3-97)表示的化合物中的至少一者。當光聚合性化合物(C)為式(3-44)至式(3-50)或式(3-69)至式(3-97)所示的化合物時,所製造的液晶顯示元件的耐紫外線衰退性特別佳。 The photopolymerizable compound (C) is particularly preferably at least one of compounds represented by the formula (3-44) to the formula (3-50) or the formula (3-69) to the formula (3-97). When the photopolymerizable compound (C) is a compound represented by formula (3-44) to formula (3-50) or formula (3-69) to formula (3-97), the resistance of the produced liquid crystal display element Ultraviolet decay is particularly good.
光聚合性化合物(C)可單獨使用或組合多種來使用。 The photopolymerizable compound (C) may be used alone or in combination.
基於聚合物(A)的使用量為100重量份,光聚合性化合物(C)的使用量為1至35重量份,較佳為3至30重量份,且更佳為5至25重量份。 The use amount of the photopolymerizable compound (C) is 1 to 35 parts by weight, preferably 3 to 30 parts by weight, and more preferably 5 to 25 parts by weight based on the use amount of the polymer (A).
若液晶配向劑不使用光聚合性化合物(C),則液晶顯示元件有色相不均的問題。 If the photopolymerizable compound (C) is not used for the liquid crystal alignment agent, the liquid crystal display element has a problem of uneven hue.
本發明的液晶配向劑中所使用的溶劑並無特別的限制,只要是可溶解聚合物(A)、聚矽氧烷(B)與其他任意成份且並不與其產生反應即可,較佳為同前述合成聚醯胺酸中所使用的溶劑,同時,亦可併用合成該聚醯胺酸時所使用的貧溶劑。 The solvent used in the liquid crystal alignment agent of the present invention is not particularly limited, as long as it dissolves the polymer (A), the polysiloxane (B) and other arbitrary components and does not react therewith, it is preferably The same solvents as those used in the synthesis of the polyamic acid may be used together with the lean solvents used in the synthesis of the polyamino acid.
溶劑(D)的具體例包括但不限於N-甲基-2-吡咯烷酮(N-methyl-2-pyrrolidone,NMP)、γ-丁內酯、γ-丁內醯胺、4-羥基-4-甲基-2-戊酮、乙二醇單甲基醚、乳酸丁酯、乙酸丁酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯、乙二醇甲基醚、乙二醇乙基醚、乙二醇正丙基醚、乙二醇異丙基醚、乙二醇正丁基醚(ethylene glycol n-butyl ether)、乙二醇二甲基醚、乙二醇乙基醚乙酸酯、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯或N,N-二甲基甲醯胺或N,N-二甲基乙醯胺(N,N-dimethyl acetamide)等。溶劑(D)可以單獨使用或者組合多種來使用。 Specific examples of the solvent (D) include, but are not limited to, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, γ-butyrolactam, 4-hydroxy-4- Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol Ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (ethylene glycol n-butyl ether), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate or N, N-dimethylformamide or N, N- N, N-dimethyl acetamide and so on. The solvent (D) can be used alone or in combination.
基於聚合物(A)的使用量為100重量份,溶劑(D)的使用量為800至4000重量份,較佳為900至3500重量份,且更佳為1000至3000重量份。 Based on 100 parts by weight of the polymer (A), 800 to 4000 parts by weight of the solvent (D), preferably 900 to 3500 parts by weight, and more preferably 1000 to 3000 parts by weight.
在不影響本發明的功效的範圍內,液晶配向劑還可選擇性地添加添加劑(E),其中添加劑(E)包括具有至少兩個環氧基的化合物、具有官能性基團的矽烷化合物,或其組合。 To the extent that the efficacy of the present invention is not affected, the liquid crystal alignment agent may optionally add an additive (E), wherein the additive (E) includes a compound having at least two epoxy groups, a silane compound having a functional group, Or a combination.
具有至少兩個環氧基的化合物包括但不限於乙二醇二環氧丙基醚、聚乙二醇二環氧丙基醚、丙二醇二環氧丙基醚、三丙二醇二環氧丙基醚、聚丙二醇二環氧丙基醚、新戊二醇二環氧丙基醚、1,6-己二醇二環氧丙基醚、丙三醇二環氧丙基醚、2,2-二溴新戊二醇二環氧丙基醚、1,3,5,6-四環氧丙基-2,4-己二醇、N,N,N’,N’-四環氧丙基-間-二甲苯二胺、1,3-雙(N,N-二環氧丙基胺基甲基)環己烷、N,N,N’,N’-四環氧丙基-4,4’-二胺基二苯基甲烷、3-(N,N-二環氧丙基)胺基丙基三甲氧基矽烷,或上述化合物的組合。 Compounds having at least two epoxy groups include, but are not limited to, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-di Bromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl- M-xylylenediamine, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4 '-Diaminodiphenylmethane, 3- (N, N-diepoxypropyl) aminopropyltrimethoxysilane, or a combination of the above compounds.
上述具有至少兩個環氧基的化合物可單獨使用或組合多種來使用。 The above compounds having at least two epoxy groups may be used alone or in combination.
基於聚合物(A)的使用量為100重量份,具有至少兩個環氧基的化合物的使用量可為0至40重量份,且較佳為0.1重量份至30重量份。 The use amount of the compound having at least two epoxy groups may be 0 to 40 parts by weight, and preferably 0.1 to 30 parts by weight based on the use amount of the polymer (A).
具有官能性基團的矽烷化合物的具體例包括但不限於3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-脲基丙基三甲氧基矽烷(3-ureidopropyltrimethoxy silane)、3-脲基丙基三乙氧基矽烷、N-乙氧基羰基-3-胺基丙基三甲氧基矽烷、N-乙氧基羰基-3-胺基丙基三乙氧基矽烷、N-三乙氧基矽烷基丙基三伸乙三胺、N-三甲氧基矽烷基丙基三伸乙三胺、10-三甲氧基矽烷基-1,4,7-三吖癸烷、10-三乙氧基矽烷基-1,4,7-三吖癸烷、9-三甲氧基矽烷基-3,6-二吖壬基醋酸酯、9-三乙氧基矽烷基-3,6-二吖壬基醋酸酯、N-苯甲基-3-胺基丙基三甲氧基矽烷、N-苯甲基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-雙(氧化乙烯)-3-胺基丙基三甲氧基矽烷、N-雙(氧化乙烯)-3-胺基丙基三乙氧基矽烷,或上述化合物的組合。 Specific examples of the silane compound having a functional group include, but are not limited to, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2 -Aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl Methyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyl Trimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriamine Ethylenetriamine, 10-trimethoxysilyl-1,4,7-triazine, 10-triethoxysilyl-1,4,7-triazine, 9-trimethoxysilane -3,6-diazinyl acetate, 9-triethoxysilyl-3,6-diazinyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane , A combination -3- N- bis (oxyethylene) -3-aminopropyl trimethoxy Silane, N- bis (oxyethylene) aminopropyl triethoxysilane Silane, or the above compounds.
添加劑(E)可以單獨使用或組合多種來使用。 The additive (E) may be used alone or in combination.
基於聚合物(A)的使用量為100重量份,具有官能性基 團的矽烷化合物的使用量可為0至10重量份,且較佳為0.5重量份至10重量份。 Based on 100 parts by weight of the polymer (A), it has a functional group The amount of the silane compound used may be 0 to 10 parts by weight, and preferably 0.5 to 10 parts by weight.
基於聚合物(A)的總使用量為100重量份,添加劑(E)的使用量較佳為0.5重量份至50重量份,且更佳為1重量份至45重量份。 The use amount of the additive (E) is preferably 0.5 to 50 parts by weight, and more preferably 1 to 45 parts by weight based on the total use amount of the polymer (A).
本發明的液晶配向劑的製備方法並無特別的限制,可採用一般的混合方法來製備。舉例而言,先將以上述方式製備而成的聚合物(A)、聚矽氧烷(B)、光聚合性化合物(C)混合均勻形成混合物。接著,於溫度為0℃至200℃的條件下添加溶劑(D),並選擇性地加入添加劑(E),最後以攪拌裝置持續攪拌至溶解即可。另外,較佳的是於20℃至60℃的溫度下添加溶劑(D)。 The method for preparing the liquid crystal alignment agent of the present invention is not particularly limited, and it can be prepared by a general mixing method. For example, the polymer (A), polysiloxane (B), and photopolymerizable compound (C) prepared in the above manner are first mixed uniformly to form a mixture. Next, the solvent (D) is added under the condition of a temperature of 0 ° C. to 200 ° C., and the additive (E) is optionally added. Finally, the stirring is continued with a stirring device until dissolved. In addition, it is preferable to add the solvent (D) at a temperature of 20 ° C to 60 ° C.
在25℃下,本發明的液晶配向劑的黏度通常為15cps至35cps,較佳為17cps至33cps,且更佳為20cps至30cps。 At 25 ° C, the viscosity of the liquid crystal alignment agent of the present invention is usually 15 cps to 35 cps, preferably 17 cps to 33 cps, and more preferably 20 cps to 30 cps.
將本發明的液晶配向劑塗佈於基板後,必要時經由預烤(pre-bake)、後烤(post-bake)等加熱處理所得的塗膜來直接作為液晶配向膜使用。又,可對該塗膜進行摩擦(rubbing)、照射偏振光或特定波長的光等、或離子束等處理,又,或在將電壓施加於液晶充填後的液晶顯示元件的狀態下照射紫外線,以作為表面 控制垂直配向膜。 After the liquid crystal alignment agent of the present invention is applied to a substrate, if necessary, a coating film obtained through a pre-bake, post-bake, or other heat treatment is used as a liquid crystal alignment film. The coating film may be subjected to rubbing, irradiation with polarized light or light of a specific wavelength, or an ion beam, or ultraviolet rays may be irradiated while a voltage is applied to the liquid crystal display element after the liquid crystal is filled. As a surface Controls vertical alignment film.
此時,所使用的基板只要是透明性高的基板即可,並無特別限定。基板例如是玻璃板、聚碳酸酯、聚(甲基)丙烯酸酯、聚醚碸、聚芳酯、聚氨酯(polyurethane)、聚碸、聚醚、聚醚酮、三甲基戊烯、聚烯烴、聚對苯二甲酸乙二酯、(甲基)丙烯腈、三乙酸纖維素、二乙酸纖維素或乙酸丁酸纖維素(cellulose acetate butyrate)等。而就製程簡單化的觀點而言,基板較佳為使用形成有液晶驅動用的銦錫氧化物(Indium Tin Oxide,ITO)電極等的基板。又,反射型液晶顯示元件若為僅單側基板時,亦可使用矽晶圓等不透明物,另外,此時的電極也可使用鋁等反射光的材料。 In this case, the substrate used is not particularly limited as long as it is a substrate having high transparency. The substrate is, for example, a glass plate, polycarbonate, poly (meth) acrylate, polyether, polyarylate, polyurethane, polyfluorene, polyether, polyetherketone, trimethylpentene, polyolefin, Polyethylene terephthalate, (meth) acrylonitrile, cellulose triacetate, cellulose diacetate, or cellulose acetate butyrate and the like. From the viewpoint of simplification of the process, the substrate is preferably a substrate on which an indium tin oxide (ITO) electrode for liquid crystal driving is formed. When the reflective liquid crystal display element is a single-sided substrate, an opaque material such as a silicon wafer may be used. In addition, an electrode at this time may be made of a material that reflects light.
液晶配向劑的塗佈方法並無特別限定,例如是網版印刷(screen printing)、平板印刷(offset printing)、柔版印刷(flexo printing)等的印刷法、噴墨法、噴塗法、輥塗佈法、浸漬、狹縫塗佈(slit coating)、旋轉塗佈等。從生產性方面來看,工業上廣泛採用的轉印印刷法也可適用於本發明。 The application method of the liquid crystal alignment agent is not particularly limited, and examples thereof include a printing method such as screen printing, offset printing, flexo printing, inkjet method, spraying method, and roller coating. Cloth, dipping, slit coating, spin coating, etc. From the viewpoint of productivity, the transfer printing method widely used in industry is also applicable to the present invention.
以上述的方法塗佈液晶配向劑後,經預烤及後烤處理可形成塗膜。塗佈液晶配向劑後的預烤步驟,雖非必要,但塗佈後至後烤的時間,各基板均未固定時,或塗佈後未馬上後烤時,較佳為進一步進行預烤步驟。此預烤步驟只要是因基板的搬送等不會使塗膜形狀變形的程度下,使有機溶劑揮發即可。預烤處理的條件並無特別限定,例如是在40℃至150℃的任意溫度下進行,較佳為50℃至120℃,更佳為60℃至100℃。預烤處理可於0.1 分鐘至30分鐘的任意時間內進行,較佳為進行0.5分鐘至15分鐘,更佳為進行1分鐘至5分鐘。 After the liquid crystal alignment agent is applied by the method described above, a coating film can be formed through pre-baking and post-baking treatments. Although the pre-baking step after applying the liquid crystal alignment agent is not necessary, it is preferable to further perform the pre-baking step when the substrates are not fixed after coating or when the substrates are not baked immediately after coating. . In this pre-baking step, the organic solvent may be volatilized to such an extent that the shape of the coating film is not deformed due to the transportation of the substrate or the like. The conditions for the pre-baking treatment are not particularly limited, and for example, it is performed at any temperature of 40 ° C to 150 ° C, preferably 50 ° C to 120 ° C, and more preferably 60 ° C to 100 ° C. Pre-baking process can be at 0.1 It is performed at any time from minutes to 30 minutes, preferably from 0.5 minutes to 15 minutes, and more preferably from 1 minute to 5 minutes.
後烤處理的條件並無特別限定,例如是在100℃至350℃的任意溫度下進行,較佳為120℃至300℃,更佳為150℃至250℃。後烤處理可於5分鐘至240分鐘的任意時間內進行,較佳為進行10分鐘至100分鐘,更佳為進行20分鐘至90分鐘。上述加熱可藉由一般公知方法,例如可以加熱板、熱風循環爐或紅外線爐進行加熱。 The conditions of the post-baking treatment are not particularly limited, and for example, it is performed at any temperature of 100 ° C to 350 ° C, preferably 120 ° C to 300 ° C, and more preferably 150 ° C to 250 ° C. The post-baking treatment may be performed at any time from 5 minutes to 240 minutes, preferably 10 minutes to 100 minutes, and more preferably 20 minutes to 90 minutes. The heating can be performed by a generally known method, for example, a heating plate, a hot-air circulation furnace, or an infrared furnace can be used for heating.
後烤後所得的液晶配向膜的厚度並無特別限定,例如可為1至1000nm,較佳為5至500nm,更佳為10至300nm。 The thickness of the liquid crystal alignment film obtained after the post-baking is not particularly limited, and may be, for example, 1 to 1000 nm, preferably 5 to 500 nm, and more preferably 10 to 300 nm.
本發明的液晶顯示元件包括由本發明的液晶配向劑所形成的液晶配向膜。本發明的液晶顯示元件可以如下述方法製造。 The liquid crystal display element of the present invention includes a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention. The liquid crystal display element of this invention can be manufactured as follows.
詳言之,本發明的液晶顯示元件可藉由上述方法於基板上形成液晶配向膜後,以公知方法製作液晶晶胞(cell)而得。液晶顯示元件的具體例,例如具備液晶晶胞的垂直配向型液晶顯示元件,其中液晶晶胞具有:對向配置的2片基板、設置於基板間的液晶層,以及設置於基板與液晶層之間並藉由本發明的液晶配向劑所形成的上述液晶配向膜。 In detail, the liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above method, and then fabricating a liquid crystal cell by a known method. Specific examples of the liquid crystal display element include, for example, a vertical alignment type liquid crystal display element including a liquid crystal cell. The liquid crystal cell includes: two substrates arranged opposite to each other, a liquid crystal layer provided between the substrates, and a substrate and the liquid crystal layer. The liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention is used.
具體而言,具備液晶晶胞的垂直配向型液晶顯示元件,其中液晶晶胞是由以下方式來製作:將本發明的液晶配向劑塗佈 於2片基板上,並藉由預烤及後烤處理而形成液晶配向膜,接著,使此液晶配向膜以對向的方式配置2片基板,並於此2片基板之間挾持著以液晶構成的液晶層,即接觸液晶配向膜而設置液晶層,最後,對液晶配向膜及液晶層施加電壓,同時照射紫外線。 Specifically, a vertical alignment type liquid crystal display element including a liquid crystal cell, wherein the liquid crystal cell is produced by applying the liquid crystal alignment agent of the present invention A liquid crystal alignment film is formed on the two substrates by pre-baking and post-baking processes. Then, the two substrates are arranged in an opposite manner to the liquid crystal alignment film, and a liquid crystal is held between the two substrates. The formed liquid crystal layer is a liquid crystal layer that is disposed in contact with the liquid crystal alignment film. Finally, a voltage is applied to the liquid crystal alignment film and the liquid crystal layer, and ultraviolet rays are irradiated at the same time.
如上述使用藉由本發明的液晶配向劑所形成的液晶配向膜,一邊對液晶配向膜及液晶層施加電壓,一邊照射紫外線,而使聚合性化合物進行聚合,同時使聚矽氧烷所具有的乙烯性不飽和基彼此進行反應,或者使該乙烯性不飽和基與聚合性化合物進行反應,可使液晶的配向更有效率地被固定化,而形成耐紫外線衰退性佳與無色相不均的液晶顯示元件。 As described above, the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention is used to polymerize a polymerizable compound while irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, and at the same time, the ethylene contained in the polysiloxane is polymerized. The organic unsaturated groups react with each other, or the ethylenically unsaturated group reacts with the polymerizable compound, so that the alignment of the liquid crystal can be more efficiently fixed, and a liquid crystal having excellent ultraviolet decay resistance and colorless phase unevenness can be formed. Display element.
將此液晶層挾持於2片基板間的方法,例如是下述兩種公知的方法: The method of holding this liquid crystal layer between two substrates is, for example, the following two known methods:
(方法一) (method one)
準備形成有液晶配向膜的一對基板,於其中一片基板的液晶配向膜上散佈珠粒(beads)等的間隔物(spacer),並使該二液晶配向膜以對向的方式再貼合另一片基板,接著減壓注入液晶,並且進行封止。 A pair of substrates having a liquid crystal alignment film formed is prepared, and spacers such as beads are spread on the liquid crystal alignment film of one of the substrates, and the two liquid crystal alignment films are bonded to each other in an opposite manner. One substrate was then injected with liquid crystal under reduced pressure and sealed.
(方法二) (Method Two)
準備形成有液晶配向膜的一對基板,於其中一片基板的液晶配向膜上散佈珠粒等的間隔物後,將液晶滴下,然後使該二液晶配向膜以對向的方式再貼合另一片基板,並且進行封止。 A pair of substrates with a liquid crystal alignment film is prepared. After spacers such as beads are spread on the liquid crystal alignment film of one of the substrates, the liquid crystal is dropped, and then the two liquid crystal alignment films are bonded to each other in an opposite manner. The substrate is sealed.
在上述兩種方法中,間隔物的厚度,較佳為1至30μm,更 佳為2至10μm。 In the above two methods, the thickness of the spacer is preferably 1 to 30 μm , and more preferably 2 to 10 μm .
對液晶配向膜及液晶層施加電壓、同時照射紫外線而製造液晶晶胞的步驟,例如將電壓施加於設置於基板上的電極間,以對液晶配向膜及液晶層外加電場,保持此電場的狀態下,照射紫外線。其中,對電極間施加的電壓,例如5Vp-p至30Vp-p,較佳為5Vp-p至20Vp-p。紫外線的照射量,例如1J至60J,較佳為40J以下,更佳為10J以下。紫外線照射量越少,越能抑制因構成液晶顯示元件的液晶或材料的破壞所產生的信賴性低下,且藉由減少紫外線照射時間可提高製造效率。本發明即使以較少的紫外線照射量也可提高應答速度,因此即使以例如5J程度的低照射量,也可形成應答速度充分快速的液晶顯示元件。 A step of applying a voltage to the liquid crystal alignment film and the liquid crystal layer while irradiating ultraviolet rays to produce a liquid crystal cell. For example, a voltage is applied between electrodes provided on a substrate to apply an electric field to the liquid crystal alignment film and the liquid crystal layer to maintain the state of the electric field. Under UV light. The voltage applied between the electrodes is, for example, 5Vp-p to 30Vp-p, and preferably 5Vp-p to 20Vp-p. The amount of ultraviolet irradiation is, for example, 1J to 60J, preferably 40J or less, and more preferably 10J or less. The smaller the amount of ultraviolet irradiation, the lower the reliability caused by the destruction of the liquid crystal or the material constituting the liquid crystal display element can be suppressed, and the manufacturing efficiency can be improved by reducing the ultraviolet irradiation time. According to the present invention, the response speed can be increased even with a small amount of ultraviolet radiation, and therefore, even at a low radiation amount of about 5 J, a liquid crystal display element having a sufficiently fast response speed can be formed.
如此,對液晶配向膜及液晶層施加電壓,同時照射紫外線時,可使聚合性化合物進行反應形成聚合物,除此之外,聚矽氧烷所具有的乙烯性不飽和基亦可於紫外線照射時彼此間進行反應’或者與聚合性化合物進行反應。藉由上述反應,可使液晶配向膜獲得較佳的固化結構,使得所得的液晶顯示元件具有耐紫外線衰退性佳與無色相不均的性質。 In this way, when a voltage is applied to the liquid crystal alignment film and the liquid crystal layer and ultraviolet rays are simultaneously irradiated, the polymerizable compound can be reacted to form a polymer. In addition, the ethylenically unsaturated group of the polysiloxane can also be irradiated with ultraviolet rays When reacting with each other 'or with a polymerizable compound. By the above reaction, the liquid crystal alignment film can obtain a better cured structure, so that the obtained liquid crystal display element has the properties of good resistance to ultraviolet decay and uneven coloring.
另外,上述液晶配向劑不僅可作為製造表面控制垂直配向型(SCVA)液晶顯示器等垂直配向方式的液晶顯示元件用的液晶配向劑使用,亦可適用於藉由摩擦處理或光配向處理所製作的液晶配向膜的用途。 In addition, the above-mentioned liquid crystal alignment agent can be used not only as a liquid crystal alignment agent for manufacturing liquid crystal display elements of a vertical alignment method such as a surface-controlled vertical alignment type (SCVA) liquid crystal display, but also can be applied to those produced by rubbing treatment or light alignment treatment. Use of liquid crystal alignment film.
上述液晶包括向列型液晶或碟狀型液晶等。液晶的具體 例包括但不限於具有正介電異方向性的液晶,其可以使用例如聯苯類液晶(biphenyl-based liquid crystals)、苯基環己烷類液晶(phenyl cyclohexane-based liquid crystal)、酯類液晶、三聯苯類液晶(terphenyl liquid crystal)、聯苯基環己烷類液晶(biphenyl cyclohexane-based liquid crystals)、嘧啶類液晶(pyrimidine-based liquid crystals)、二噁烷類液晶(dioxane-based liquid crystals)、雙環辛烷類液晶(bicyclooctane-based liquid crystals)、立方烷類液晶(cubane-based liquid crystals),或上述液晶的組合。此外,在前述液晶中還可以進一步添加例如氯化膽甾醇(cholesteryl chloride)、膽甾醇壬酸酯(cholesteryl nonanoate)、膽甾醇碳酸酯(cholesteryl carbonate)等膽甾型液晶(cholesteric liquid crystal);以商品名「C-15」、「CB-15」(默克公司製造)進行銷售的手性劑;對癸氧基苯亞甲基-對胺基-2-甲基丁基肉桂酸酯(p-decyloxybenzylidene-p-amino-2-methyl butyl cinnamate)等強介電性液晶(ferroelectric liquid crystal)等進行使用。 The liquid crystal includes a nematic liquid crystal or a dish-shaped liquid crystal. LCD specific Examples include, but are not limited to, liquid crystals with positive dielectric anisotropy. Biphenyl-based liquid crystals, phenyl cyclohexane-based liquid crystals, and ester liquid crystals can be used, for example. , Terphenyl liquid crystal, biphenyl cyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals ), Bicyclooctane-based liquid crystals, cubic-based liquid crystals, or a combination of the above liquid crystals. In addition, a cholesteric liquid crystal such as cholesteryl chloride, cholesteryl nonanoate, and cholesteryl carbonate may be further added to the liquid crystal; Chiral agents sold under the trade names "C-15" and "CB-15" (Merck); p-decyloxymethylene-p-amino-2-methylbutyl cinnamate (p -decyloxybenzylidene-p-amino-2-methyl butyl cinnamate) and other ferroelectric liquid crystals are used.
另外,液晶的具體例也可包括具有負介電異方向性的液晶,其可以使用例如二氰基苯類液晶(dicyanobenzene-based liquid crystal)、噠嗪類液晶(pyridazine-based liquid crystal)、希夫鹼類液晶(Schiff base-based liquid crystal)、氧化偶氮類液晶(azoxy-based liquid crystal)、聯苯類液晶(biphenyl-based liquid crystal)、苯基環己烷類液晶(phenyl cyclohexane-based liquid crystal),或上述液晶的組合。 In addition, specific examples of the liquid crystal may include a liquid crystal having a negative dielectric anisotropy. For example, dicyanobenzene-based liquid crystal, pyridazine-based liquid crystal, Greek Schiff base-based liquid crystal, azoxy-based liquid crystal, biphenyl-based liquid crystal, phenyl cyclohexane-based liquid crystal), or a combination of the above liquid crystals.
本發明將就以下實施例來作進一步說明,但應瞭解的是,該等實施例僅為例示說明,而不應被解釋為本發明實施的限制。 The present invention will be further described with reference to the following examples, but it should be understood that these examples are merely illustrative and should not be construed as limitations of the implementation of the present invention.
以下說明聚合物(A)的合成例A-1-1至合成例A-1-6: The following describes Synthesis Example A-1-1 to Synthesis Example A-1-6 of the polymer (A):
在容積500毫升的四頸燒瓶上設置氮氣入口、攪拌器、冷凝管及溫度計,並導入氮氣。然後,在四頸燒瓶中,加入1.16克(0.0025莫耳)的由式(II-10)表示的二胺化合物(簡稱為a2-1-1)、4.86克(0.045莫耳)的對-二胺苯(簡稱為a2-2-1)、0.49克(0.0025莫耳)的4,4’-二胺基二環己基甲烷(簡稱為a2-2-4)以及80克的N-甲基-2-吡咯烷酮(簡稱為NMP),並於室溫下攪拌至溶解。接著,加入9.80克(0.05莫耳)的1,2,3,4-環丁烷四羧酸二酐(簡稱為a1-1)及20克的NMP,並於室溫下反應2小時。待反應結束後,將反應溶液倒入1500毫升水中,以使聚合物析出。然後,過濾所得的聚合物,並重複以甲醇清洗及過濾三次,置入真空烘箱中,以溫度60℃進行乾燥後,即可得聚合物(A-1-1)。 A 500 ml four-necked flask was provided with a nitrogen inlet, a stirrer, a condenser, and a thermometer, and nitrogen was introduced. Then, in a four-necked flask, 1.16 g (0.0025 mol) of a diamine compound (abbreviated as a2-1-1) represented by the formula (II-10) and 4.86 g (0.045 mol) of p-di Aminobenzene (abbreviated as a2-2-1), 0.49 g (0.0025 mole) of 4,4'-diaminodicyclohexylmethane (abbreviated as a2-2-4), and 80 g of N-methyl- 2-Pyrrolidone (abbreviated as NMP), and stirred at room temperature until dissolved. Next, 9.80 g (0.05 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (abbreviated as a1-1) and 20 g of NMP were added and reacted at room temperature for 2 hours. After the reaction is completed, the reaction solution is poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, repeatedly washed with methanol and filtered three times, put into a vacuum oven, and dried at a temperature of 60 ° C. to obtain a polymer (A-1-1).
合成例A-1-2至合成例A-1-6是以與合成例A-1-1相同的 步驟來分別製備聚合物(A-1-2)至聚合物(A-1-6),並且其不同處在於:改變單體的種類及其使用量(如表1所示)。 Synthesis Examples A-1-2 to A-1-6 are the same as Synthesis Example A-1-1 The steps are to separately prepare the polymer (A-1-2) to the polymer (A-1-6), and the difference is that the type of the monomer and the amount of use thereof are changed (as shown in Table 1).
以下說明聚合物(A)的合成例A-2-1至合成例A-2-11: The following describes Synthesis Example A-2-1 to Synthesis Example A-2-11 of Polymer (A):
在容積500毫升的四頸燒瓶上設置氮氣入口、攪拌器、冷凝管及溫度計,並導入氮氣。然後,在四頸燒瓶中,加入1.16克(0.0025莫耳)的由式(II-10)表示的二胺化合物(簡稱為a2-1-1)、4.86克(0.045莫耳)的對-二胺苯(簡稱為a2-2-1)、0.49克(0.0025莫耳)的4,4’-二胺基二環己基甲烷(簡稱為a2-2-4)以及80克的N-甲基-2-吡咯烷酮(簡稱為NMP),並於室溫下攪拌至溶解。接著,加入9.80克(0.05莫耳)的1,2,3,4-環丁烷四羧酸二酐(簡稱為a1-1)及20克的NMP。於室溫下反應6小時後,加入97克的NMP、2.55克的醋酸酐及19.75克的吡啶,升溫至60℃,且持續攪拌2小時,以進行醯亞胺化反應。待反應結束後,將反應溶液倒入1500毫升水中,以使聚合物析出。然後,過濾所得的聚合物,並重複以甲醇清洗及過濾三次,置入真空烘箱中,以溫度60℃進行乾燥後,即可得聚合物(A-2-1)。 A 500 ml four-necked flask was provided with a nitrogen inlet, a stirrer, a condenser, and a thermometer, and nitrogen was introduced. Then, in a four-necked flask, 1.16 g (0.0025 mol) of a diamine compound (abbreviated as a2-1-1) represented by the formula (II-10) and 4.86 g (0.045 mol) of p-di Aminobenzene (abbreviated as a2-2-1), 0.49 g (0.0025 mole) of 4,4'-diaminodicyclohexylmethane (abbreviated as a2-2-4), and 80 g of N-methyl- 2-Pyrrolidone (abbreviated as NMP), and stirred at room temperature until dissolved. Next, 9.80 g (0.05 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (abbreviated as a1-1) and 20 g of NMP were added. After reacting at room temperature for 6 hours, 97 g of NMP, 2.55 g of acetic anhydride, and 19.75 g of pyridine were added, the temperature was raised to 60 ° C., and stirring was continued for 2 hours to carry out the imidization reaction. After the reaction is completed, the reaction solution is poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, and repeatedly washed with methanol and filtered three times, put into a vacuum oven, and dried at a temperature of 60 ° C. to obtain a polymer (A-2-1).
合成例A-2-2至合成例A-2-11是以與合成例A-2-1相同 的步驟來分別製備聚合物(A-2-2)至聚合物(A-2-11),並且其不同處在於:改變單體的種類及其使用量(如表1所示)。 Synthesis Examples A-2-2 to A-2-11 are the same as Synthesis Example A-2-1 Steps to prepare the polymer (A-2-2) to the polymer (A-2-11), and the difference is that the type of monomer and its amount of use are changed (as shown in Table 1).
表1中簡稱所對應的化合物如下所示。 The compounds corresponding to the abbreviations in Table 1 are shown below.
以下說明聚矽氧烷(B)的合成例B-1至合成例B-7: The following describes Synthesis Example B-1 to Synthesis Example B-7 of the polysiloxane (B):
在容積500毫升的三頸燒瓶上設置攪拌器、冷凝管及溫度計。然後,在三頸燒瓶中,加入0.3莫耳的4-縮水甘油醚基丁基三甲氧基矽烷(以下簡稱為GBTMS)、0.7莫耳的甲基三甲氧基矽烷(以下簡稱為MTMS)以及6克的丙二醇單甲基醚(以下簡稱為PGME),並於室溫下一邊攪拌一邊於30分鐘內添加三乙胺(Triethylamine,以下簡稱為TEA)水溶液(20克TEA/200克H2O)。接著,將三頸燒瓶浸漬於30℃的油浴中並攪拌30分鐘,然後於30分鐘內將油浴升溫至90℃,待溶液的內溫達到75℃時,持續加熱攪拌進行聚縮合6小時。待反應結束後,取出有機層並使用0.2重量%的硝酸銨水溶液進行清洗後,即可獲得含聚矽氧烷化合物的溶液。 A 500 ml three-necked flask was equipped with a stirrer, a condenser, and a thermometer. Then, in a three-necked flask, 0.3 mol of 4-glycidyl ether butyltrimethoxysilane (hereinafter referred to as GBTMS), 0.7 mol of methyltrimethoxysilane (hereinafter referred to as MTMS) and 6 Grams of propylene glycol monomethyl ether (hereinafter referred to as PGME), and triethylamine (hereinafter referred to as TEA) aqueous solution (20 grams of TEA / 200 grams of H 2 O) was added within 30 minutes while stirring at room temperature. . Next, the three-necked flask was immersed in an oil bath at 30 ° C. and stirred for 30 minutes, and then the oil bath was heated to 90 ° C. within 30 minutes. When the internal temperature of the solution reached 75 ° C., the mixture was continuously heated and stirred for 6 hours . After the reaction is completed, the organic layer is taken out and washed with a 0.2% by weight ammonium nitrate aqueous solution to obtain a solution containing a polysiloxane compound.
接著,將0.1莫耳的富馬酸單乙酯(以下簡稱為MEF)及0.2克硬化促進劑UCAT 18X(三亞普羅(SAN-APRO)公司製)加入含聚矽氧烷化合物的溶液。然後,將三頸燒瓶浸漬於30℃的油浴中並攪拌10分鐘,然後於30分鐘內將油浴升溫至115℃,待溶液的內溫達到100℃時,持續加熱攪拌24小時。待反應結束後,取出有機層並進行水洗後,使用硫酸鎂進行乾燥,去除溶劑後,即可獲得聚矽氧烷(B-1)。 Next, 0.1 mol of monoethyl fumarate (hereinafter abbreviated as MEF) and 0.2 g of a hardening accelerator UCAT 18X (manufactured by SAN-APRO) were added to the solution containing a polysiloxane compound. Then, the three-necked flask was immersed in an oil bath at 30 ° C. and stirred for 10 minutes, and then the oil bath was heated to 115 ° C. within 30 minutes. When the internal temperature of the solution reached 100 ° C., heating and stirring were continued for 24 hours. After the reaction is completed, the organic layer is taken out, washed with water, dried with magnesium sulfate, and the solvent is removed to obtain polysiloxane (B-1).
合成例B-2至合成例B-7的聚矽氧烷(B-2)至聚矽氧烷(B-7)是以與合成例B-1相同的步驟來製備,並且其不同處在於:改變聚矽氧烷(B)的反應物的種類及其使用量、觸媒及溶劑的種類及其使用量、反應溫度及聚縮合時間(如表2所示)。 The polysiloxane (B-2) to polysiloxane (B-7) of Synthesis Example B-2 to Synthesis Example B-7 were prepared in the same procedure as Synthesis Example B-1, and were different in that : Change the kind of reactant of polysiloxane (B) and its use amount, the kind of catalyst and solvent and its use amount, reaction temperature and polycondensation time (as shown in Table 2).
合成例B’-1至合成例B’-3的聚矽氧烷(B’-1)至聚矽氧烷(B’-3)是以與合成例B-1相同的步驟來製備,並且其不同處在於:改變聚矽氧烷(B)的反應物的種類及其使用量、觸媒及溶劑的種類及其使用量、反應溫度及聚縮合時間(如表2所示)。 The polysiloxanes (B'-1) to (B'-3) of Synthesis Example B'-1 to Synthesis Example B'-3 were prepared in the same steps as those of Synthesis Example B-1, and The difference lies in that: the type of the reactant of the polysiloxane (B) and its use amount, the type of the catalyst and the solvent and their use amount, the reaction temperature and the polycondensation time (shown in Table 2).
表2中簡稱所對應的化合物如下所示。 The compounds corresponding to the abbreviations in Table 2 are shown below.
以下說明液晶配向劑、液晶配向膜以及液晶顯示元件的實施例1至實施例15以及比較例1至比較例12: Examples 1 to 15 and Comparative Examples 1 to 12 of the liquid crystal alignment agent, the liquid crystal alignment film, and the liquid crystal display element will be described below:
秤取100重量份的聚合物(A-1-1)、5重量份的聚矽氧烷(B-1)、8重量份的由式(3-43)表示的光聚合性化合物(C-1)、1200重量份的N-甲基-2-吡咯烷酮(簡稱為D-1)以及1200重量份的乙二醇正丁基醚(簡稱為D-2),並且在室溫下,以攪拌裝置持續攪拌至溶解,即可形成實施例1的液晶配向劑。 100 parts by weight of the polymer (A-1-1), 5 parts by weight of the polysiloxane (B-1), and 8 parts by weight of the photopolymerizable compound (C- 1), 1200 parts by weight of N-methyl-2-pyrrolidone (abbreviated as D-1) and 1200 parts by weight of ethylene glycol n-butyl ether (abbreviated as D-2), and at room temperature, using a stirring device By continuing to stir until dissolved, the liquid crystal alignment agent of Example 1 can be formed.
使用上述所得的液晶配向劑,以下述所示的順序製作液晶晶胞。將液晶配向劑以旋轉塗佈的方式,分別塗佈於兩片具有ITO電極的玻璃基板上,其中,該ITO電極為線/間距(Line/Space)各自為5μm的狹縫狀(slit)圖案。接著,於加熱板上以80℃預烤2分鐘後,再於循環烘箱中以220℃進行20分鐘的後烤,即可形成實施例1的液晶配向膜。 Using the obtained liquid crystal alignment agent, a liquid crystal cell was produced in the procedure shown below. The liquid crystal alignment agent was spin-coated on two glass substrates each having an ITO electrode, wherein the ITO electrode was a slit pattern with a line / space of 5 μm each. . Next, pre-bake at 80 ° C. for 2 minutes on a hot plate, and post-bake at 220 ° C. for 20 minutes in a circulating oven to form the liquid crystal alignment film of Example 1.
對於上述2片上面形成了液晶配向膜的玻璃基板,其中一片上塗佈熱壓膠,另一片散佈4μm的間隔物。接著,將兩片玻璃基板進行貼合,再以熱壓機施以10kg的壓力,在溫度為150℃ 的條件下進行熱壓貼合。然後,以液晶注入機(島津製作所製造,型號為ALIS-100X-CH)注入液晶)後,利用紫外光硬化膠封住液晶注入口,並以紫外光燈照光使其硬化。接著,於兩個ITO電極之間施加20Vp-p交流電,並在液晶為驅動狀態下照射30J的紫外線後,即可獲得實施例1的液晶顯示元件。將實施例1的液晶顯示元件以後述各評價方式進行評價,其結果如表3所示。 For the two glass substrates on which the liquid crystal alignment film was formed, one of the glass substrates was coated with a hot-pressing adhesive, and the other was dispersed with a 4 μm spacer. Next, the two glass substrates were bonded together, and then a pressure of 10 kg was applied by a hot press, and the bonding was performed by hot pressing at a temperature of 150 ° C. Then, a liquid crystal injection machine (made by Shimadzu Corporation, model: ALIS-100X-CH) was used to inject the liquid crystal, and then the liquid crystal injection port was sealed with an ultraviolet curing adhesive, and then cured by irradiation with an ultraviolet light. Next, an alternating current of 20 Vp-p was applied between the two ITO electrodes, and 30 J of ultraviolet rays were irradiated while the liquid crystal was in a driving state to obtain a liquid crystal display element of Example 1. The liquid crystal display element of Example 1 was evaluated by each evaluation method described later, and the results are shown in Table 3.
實施例2至實施例15的液晶配向劑、液晶配向膜及液晶顯示元件是以與實施例1相同的步驟分別製備,並且其不同處在於:改變成分的種類及其使用量,如表3所示。將實施例2至15所製得液晶顯示元件以後述評價方式進行評價,其結果如表3所示。 The liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element of Example 2 to Example 15 were separately prepared in the same steps as in Example 1, and the difference was that the type of the component and the amount of use were changed, as shown in Table 3. Show. The liquid crystal display elements obtained in Examples 2 to 15 were evaluated in an evaluation method described later, and the results are shown in Table 3.
比較例1至比較例12的液晶配向劑、液晶配向膜及液晶顯示元件是以與實施例1相同的步驟分別製備,不同的地方在於:改變成分的種類及其使用量,如表4所示。對比較例1至比較例12所製得液晶顯示元件以後述評價方式進行評價,其結果如表4所示。 The liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element of Comparative Example 1 to Comparative Example 12 were separately prepared in the same steps as in Example 1. The difference was that the type of the component and the amount of use were changed, as shown in Table 4. . The liquid crystal display elements obtained in Comparative Examples 1 to 12 were evaluated in the evaluation method described later, and the results are shown in Table 4.
表3及表4中簡稱所對應的化合物如下所示。 The compounds corresponding to the abbreviations in Tables 3 and 4 are shown below.
醯亞胺化率是指透過聚合物中的醯胺酸官能基數目和醯亞胺環數目的合計量為基準,計算醯亞胺環數目所佔的比例,以百分率表示。 The fluorene imidization ratio refers to the total number of fluorene imine functional groups and the number of fluorene imine rings in the polymer, and the ratio of the number of fluorene imine rings is calculated as a percentage.
檢測的方法是將合成例的聚合物分別進行減壓乾燥後,溶解於適當的氘化溶劑(deuteration solvent),例如:氘化二甲基亞碸中,以四甲基矽烷作為基準物質,從室溫(例如25℃)下測定1H-核磁共振(1H-Nuclear magnetic resonance,1H-NMR)的結果,再由數學式(1)即可求得醯亞胺化率(%)。 The detection method is to separately dry the polymer of the synthesis example under reduced pressure, and then dissolve it in an appropriate deuteration solvent (for example, deuterated dimethylsulfinium), using tetramethylsilane as a reference material, and 1 H-NMR measurement results (1 H-Nuclear magnetic resonance, 1 H-NMR) at room temperature (e.g. 25 ℃), then from equation (1) can be obtained (PEI) ratio (%).
△1:NH基質子在10ppm附近的化學位移(chemical shift)所產生的峰值(peak)面積;△2:其他質子的峰值面積;α:聚合物的前驅物(聚醯胺酸)中的NH基的1個質子相對於其他質子的個數比例。 △ 1: Peak area generated by chemical shift of NH matrix protons around 10ppm; △ 2: Peak areas of other protons; α: NH in polymer precursor (polyamic acid) Proportion of the number of one proton of the base relative to the number of other protons.
液晶顯示元件的耐紫外線衰退性是以液晶顯示元件的電壓保持率來評價。進一步而言,液晶顯示元件的電壓保持率的量測方法如下所述。 The ultraviolet decay resistance of a liquid crystal display element was evaluated by the voltage holding ratio of the liquid crystal display element. Furthermore, the measurement method of the voltage holding ratio of a liquid crystal display element is as follows.
利用電氣測量機台(東陽公司製,型號Model 6254)分別測量實施例及比較例的液晶顯示元件的電壓保持率。測試條件是施加4伏特電壓,歷時2毫秒後解除電壓,並量測解除起1667毫秒後的電壓保持率(計為V1)。接著,將液晶顯示元件以30mJ/cm2的紫外光(紫外光照射機型號為KN-SH48K1;光能興業製造)照射後,以相同測試條件測量經紫外光照射後的電壓保持率(計為V2)。最後,以數學式(2)計算即可獲得電壓保持率變化百分比(計為VUV-decay(%))。電壓保持率變化百分比越低,代表液晶顯示元件的耐紫外線衰退性越佳。 The voltage holding ratios of the liquid crystal display elements of the examples and comparative examples were measured using an electrical measuring machine (manufactured by Toyo Co., Ltd. Model 6254). The test condition is to apply a voltage of 4 volts, and release the voltage after 2 milliseconds, and measure the voltage retention rate (counted as V1) after 1667 milliseconds since the release. Next, after the liquid crystal display element was irradiated with 30 mJ / cm 2 of ultraviolet light (ultraviolet irradiation machine model: KN-SH48K1; manufactured by Kogyo Kogyo), the voltage retention rate after ultraviolet light irradiation was measured under the same test conditions (calculated as V2). Finally, the percentage change of the voltage holding rate (calculated as V UV-decay (%)) can be obtained by calculating with mathematical formula (2). The lower the percentage change in the voltage holding ratio, the better the UV-resistant decay resistance of the liquid crystal display element.
電壓保持率變化百分比的評價基準如下所示。 The evaluation criteria for the percentage change in voltage holding ratio are shown below.
◎:VUV-decay<3% ◎: V UV-decay <3%
○:3%≦VUV-decay<5% ○: 3% ≦ V UV-decay <5%
△:5%≦VUV-decay<10% △: 5% ≦ V UV-decay <10%
╳:10%≦VUV-decay ╳: 10% ≦ V UV-decay
將實施例及比較例的液晶顯示元件在標準C光源的背光源照射下,透過偏光板觀察液晶顯示元件是否有色相不均的產生。色相不均的評價基準如下所示。 The liquid crystal display elements of the examples and comparative examples were irradiated with a backlight of a standard C light source, and the liquid crystal display elements were observed through a polarizing plate to see if the liquid crystal display elements had uneven hue. The evaluation criteria of hue unevenness are shown below.
◎:未出現色相不均。 :: No unevenness in hue occurred.
○:出現輕微色相不均,但不明顯。 ○: Slight unevenness in hue occurs, but it is not obvious.
△:出現明顯色相不均。 △: Significant uneven hue appears.
╳:出現嚴重色相不均。 ╳: Severe hue unevenness occurs.
由表3以及表4得知,與同時使用聚合物(A)、聚矽氧烷(B)及光聚合性化合物(C)的液晶配向劑所製得的液晶顯示元件(實施例1至實施例15)相比,未使用二胺化合物(a2-1)的比較例1、比較例2、比較例9、比較例10、比較例12的液晶顯示元件以及未使用聚矽氧烷(B)的比較例3至比較例6、比較例9至比較例11的液晶顯示元件不具耐紫外線衰退性。並且,與同時使用聚合物(A)、聚矽氧烷(B)及光聚合性化合物(C)的液晶配向劑所製得的液晶顯示元件(實施例1至實施例15)相比,未使用光聚合性化合物(C)的比較例7、比較例8、比較例11、比較例12的液晶顯示元件有嚴重色相不均的問題。 From Tables 3 and 4, it is known that the liquid crystal display elements (Examples 1 to Implementation) prepared with a liquid crystal alignment agent using the polymer (A), polysiloxane (B), and photopolymerizable compound (C) together Example 15) In contrast, the liquid crystal display elements of Comparative Example 1, Comparative Example 2, Comparative Example 9, Comparative Example 10, Comparative Example 12 without using the diamine compound (a2-1), and without using polysiloxane (B) The liquid crystal display elements of Comparative Examples 3 to 6 and Comparative Examples 9 to 11 do not have ultraviolet decay resistance. In addition, compared with a liquid crystal display element (Examples 1 to 15) obtained by using a liquid crystal alignment agent of a polymer (A), a polysiloxane (B) and a photopolymerizable compound (C), The liquid crystal display elements of Comparative Example 7, Comparative Example 8, Comparative Example 11, and Comparative Example 12 using the photopolymerizable compound (C) had a problem of severe hue unevenness.
另外,當使用醯亞胺化率為30%至90%的聚合物(A)(即聚合物(A-2-4)至聚合物(A-2-9))時(實施例9至實施例14)時,液晶顯示元件的耐紫外線衰退性更佳。 In addition, when using a polymer (A) having an imidization ratio of 30% to 90% (ie, a polymer (A-2-4) to a polymer (A-2-9)) (Examples 9 to Examples) In the case of Example 14), the liquid crystal display element has better UV degradation resistance.
又,當使用含特定乙烯性不飽和基的聚矽氧烷(B)(即聚矽氧烷(B-2)至聚矽氧烷(B-6))時(實施例2至實施例5、實施例8至實施例11、實施例13及實施例14),可進一步改善液晶顯示元件的色相不均的問題。 When polysiloxane (B) (i.e., polysiloxane (B-2) to polysiloxane (B-6)) containing a specific ethylenically unsaturated group is used (Example 2 to Example 5) (Example 8 to Example 11, Example 13 and Example 14), the problem of uneven hue of the liquid crystal display element can be further improved.
此外,當使用由式(3-31)至式(3-42)表示的化合物中的至少一者作為光聚合性化合物(C)(實施例3至實施例5、實施例7、實施例10、實施例11、實施例14及實施例15)時,液晶顯示元件的耐紫外線衰退性更佳。 In addition, when at least one of the compounds represented by the formulae (3-31) to (3-42) is used as the photopolymerizable compound (C) (Examples 3 to 5, Example 7, and Example 10) (Example 11, Example 14, and Example 15), the liquid crystal display element has better resistance to ultraviolet decay.
另外,當聚合物(A)含有式(III-1)、式(III-2)表示的二胺化合物時(實施例3、實施例4、實施例8、實施例9、實施例12),可進一步改善液晶顯示元件的色相不均的問題。 When the polymer (A) contains a diamine compound represented by formula (III-1) or formula (III-2) (Example 3, Example 4, Example 8, Example 9, Example 12), The problem of uneven hue of the liquid crystal display element can be further improved.
綜上所述,本發明的表面控制垂直配向型液晶配向劑中,除了含有聚合物以及溶劑之外,更將光聚合性化合物添加於液晶配向劑中,而非如聚合物穩定配向型般將光聚合性化合物添加於液晶層中,因此解決了習知液晶層受到雜質污染的問題。 In summary, in the surface-controlled vertical alignment type liquid crystal alignment agent of the present invention, in addition to the polymer and the solvent, a photopolymerizable compound is added to the liquid crystal alignment agent instead of the polymer stable alignment type. The photopolymerizable compound is added to the liquid crystal layer, thereby solving the problem that the conventional liquid crystal layer is contaminated with impurities.
另一方面,本發明的液晶配向劑含有特定乙烯性不飽和基的聚矽氧烷,而使液晶顯示元件的耐紫外線衰退性佳;並且含有光聚合性化合物,而使液晶顯示元件的無色相不均的問題,因此適用於製造液晶配向膜及液晶顯示元件。 On the other hand, the liquid crystal alignment agent of the present invention contains a polyethylsiloxane having a specific ethylenically unsaturated group, so that the liquid crystal display element has excellent ultraviolet decay resistance, and contains a photopolymerizable compound to make the liquid crystal display element colorless. The problem of unevenness is therefore suitable for manufacturing a liquid crystal alignment film and a liquid crystal display element.
雖然本發明已以實施例揭露如上,然其並非用以限定本發明,任何所屬技術領域中具有通常知識者,在不脫離本發明的精神和範圍內,當可作些許的更動與潤飾,故本發明的保護範圍當視後附的申請專利範圍所界定者為準。 Although the present invention has been disclosed as above with the examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some modifications and retouching without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be determined by the scope of the attached patent application.
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