TWI490238B - An acrylic resin composition, an alignment film formed, and a three-dimensional liquid Crystal display - Google Patents
An acrylic resin composition, an alignment film formed, and a three-dimensional liquid Crystal display Download PDFInfo
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Description
本發明是有關於一種丙烯酸系樹脂組成物,特別是指一種包含特定含量比例且具有長碳鏈官能基之丙烯酸酯的丙烯酸系樹脂組成物。The present invention relates to an acrylic resin composition, and more particularly to an acrylic resin composition comprising an acrylate having a specific content ratio and having a long carbon chain functional group.
在液晶顯示器中,一般需要利用一配向膜以使液晶分子依照特定方向排列。而在裸視三維液晶顯示器中,該配向膜對於液晶的錨定力(anchoring force)及配向均勻性對於最終呈現出之三維畫面的影像品質至關重要,其是指該配向膜經過定向摩擦而能使液晶分子朝向一特定方向整齊且均勻排列的能力。若該配向膜對於液晶的錨定力或配向均勻性不足,將導致三維液晶顯示器產生顯著的配向區域差異,造成影像訊號傳遞失真,使得呈現出之三維畫面的影像品質低落,進而使使用者在透過該三維液晶顯示器觀看三維畫面時,產生影像色差或重疊等不良視覺現象。In liquid crystal displays, it is generally desirable to utilize an alignment film to align liquid crystal molecules in a particular direction. In the naked-view three-dimensional liquid crystal display, the anchoring force and alignment uniformity of the alignment film for the liquid crystal are crucial for the image quality of the finally rendered three-dimensional image, which means that the alignment film is subjected to directional friction. The ability to align liquid crystal molecules neatly and evenly in a particular direction. If the alignment film has insufficient anchoring force or alignment uniformity to the liquid crystal, the three-dimensional liquid crystal display will have a significant difference in the alignment area, causing distortion of the image signal transmission, and the image quality of the three-dimensional image presented is low, thereby enabling the user to When viewing a three-dimensional picture through the three-dimensional liquid crystal display, undesirable visual phenomena such as image chromatic aberration or overlap occur.
因此,本發明之第一目的,即在提供一種丙烯 酸系樹脂組成物,能有效提升對於液晶的配向均勻性。Therefore, the first object of the present invention is to provide a propylene The acid resin composition can effectively improve the alignment uniformity of the liquid crystal.
於是本發明丙烯酸系樹脂組成物包含丙烯酸酯組分、光起始劑及黏結劑。其中,該丙烯酸酯組分包括一由下式(I)所示的第一丙烯酸酯:CH2 =CRCOO(CH2 )n CH3 (I)Thus, the acrylic resin composition of the present invention contains an acrylate component, a photoinitiator, and a binder. Wherein the acrylate component comprises a first acrylate represented by the following formula (I): CH 2 =CRCO(CH 2 ) n CH 3 (I)
在式(I)中,R表示氫或甲基,及n表示7~17。其中,以該丙烯酸系樹脂組成物的總重為100 wt%,該第一丙烯酸酯之含量範圍為10~19 wt%。In the formula (I), R represents hydrogen or a methyl group, and n represents 7 to 17. Wherein, the total weight of the acrylic resin composition is 100 wt%, and the content of the first acrylate is in the range of 10 to 19 wt%.
本發明之第二目的,即在提供一種配向膜,是將一如上所述的丙烯酸系樹脂組成物進行塗佈後,再經過曝光後所形成,適用在改善形成於其上之反應型液晶的配向均勻性。A second object of the present invention is to provide an alignment film which is formed by coating an acrylic resin composition as described above and then exposing it, and is suitable for improving a reactive liquid crystal formed thereon. Orientation uniformity.
本發明之第三目的,即在提供一種具有良好配向均勻性的三維液晶顯示器,包含一透明基板、一形成在該透明基板上的聚醯亞胺膜、一形成在該聚醯亞胺膜上的液晶層及一與該液晶層接觸且如上所述的配向膜,其中,該配向膜與該液晶層所構成的界面是呈波浪狀(wave-shape)。A third object of the present invention is to provide a three-dimensional liquid crystal display having good alignment uniformity, comprising a transparent substrate, a polyimide film formed on the transparent substrate, and a polyimine film formed on the polyimide film. a liquid crystal layer and an alignment film which is in contact with the liquid crystal layer and has an interface formed by the alignment film and the liquid crystal layer in a wave-shape.
本發明丙烯酸系樹脂組成物之功效在於:藉由包含特定含量比例且具有長碳鏈官能基的第一丙烯酸酯,可形成能對液晶產生良好之配向均勻性的配向膜,並可製成三維液晶顯示器。The effect of the acrylic resin composition of the present invention is that an alignment film capable of producing a good alignment uniformity to a liquid crystal can be formed by a first acrylate containing a specific content ratio and having a long carbon chain functional group, and can be formed into a three-dimensional shape. LCD Monitor.
本發明之其他的特徵及功效,將於參照圖式的 實施方式中清楚地呈現,其中:圖1是一偏光顯微鏡照片,說明本發明應用例1之三維液晶顯示器的配向結果;圖2是一偏光顯微鏡照片,說明本發明應用例2之三維液晶顯示器的配向結果;圖3是一偏光顯微鏡照片,說明比較應用例1之三維液晶顯示器的配向結果;圖4是一偏光顯微鏡照片,說明比較應用例2之三維液晶顯示器的配向結果。Other features and effects of the present invention will be described with reference to the drawings. It is clearly shown in the embodiment, wherein: FIG. 1 is a polarizing microscope photograph illustrating the alignment result of the three-dimensional liquid crystal display of the application example 1 of the present invention; and FIG. 2 is a polarizing microscope photograph illustrating the three-dimensional liquid crystal display of the application example 2 of the present invention. Fig. 3 is a polarizing microscope photograph illustrating the alignment result of the three-dimensional liquid crystal display of Comparative Example 1, and Fig. 4 is a polarizing microscope photograph illustrating the alignment result of the three-dimensional liquid crystal display of Comparative Example 2.
本發明丙烯酸系樹脂組成物包含丙烯酸酯組分、光起始劑及黏結劑。其中,該丙烯酸酯組分包括一由下式(I)所示的第一丙烯酸酯:CH2 =CRCOO(CH2 )n CH3 (I)The acrylic resin composition of the present invention contains an acrylate component, a photoinitiator, and a binder. Wherein the acrylate component comprises a first acrylate represented by the following formula (I): CH 2 =CRCO(CH 2 ) n CH 3 (I)
在式(I)中,R表示氫或甲基,及n表示7~17。其中,以該丙烯酸系樹脂組成物的總重為100 wt%,該第一丙烯酸酯之含量範圍為10~19 wt%。In the formula (I), R represents hydrogen or a methyl group, and n represents 7 to 17. Wherein, the total weight of the acrylic resin composition is 100 wt%, and the content of the first acrylate is in the range of 10 to 19 wt%.
以該丙烯酸系樹脂組成物的總重為100 wt%,當該第一丙烯酸酯之含量低於10 wt%時,其所形成的配向膜不足以對液晶產生均勻的配向性;當該第一丙烯酸酯之含量高於19 wt%時,其所形成的配向膜硬度不足,使得該丙烯酸系樹脂組成物成膜後進行定向摩擦(rubbing)的效果不佳,進而造成後續塗佈之液晶無法配向。較佳地,該第一丙烯酸酯之含量範圍為13~17 wt%。The total weight of the acrylic resin composition is 100 wt%, and when the content of the first acrylate is less than 10 wt%, the alignment film formed is insufficient to produce uniform alignment to the liquid crystal; When the content of the acrylate is more than 19% by weight, the hardness of the alignment film formed is insufficient, so that the effect of rubbing after the film formation of the acrylic resin composition is poor, and the liquid crystal which is subsequently coated cannot be aligned. . Preferably, the content of the first acrylate ranges from 13 to 17 wt%.
該第一丙烯酸酯具有C8 ~C18 的長碳鏈官能基,可用以加強該丙烯酸系樹脂組成物成膜後進行定向摩擦時的順向能力,並增加對於液晶的錨定力,使得液晶不易受到地貌曲面影響而滑動。當該第一丙烯酸酯具有少於8個碳的長碳鏈官能基時,該丙烯酸系樹脂組成物成膜後進行定向摩擦時的順向能力不佳,其所形成的配向膜對於液晶不具有良好的配向均勻性;當該第一丙烯酸酯具有多於18個碳的長碳鏈官能基時,該丙烯酸系樹脂組成物在常溫下呈現霧狀,難以透光並進行後續加工及應用。較佳地,該第一丙烯酸酯具有C12 ~C18 的長碳鏈官能基。The first acrylate has a long carbon chain functional group of C 8 ~ C 18 , which can be used to enhance the forward direction of the acrylic resin composition after directional rubbing, and increase the anchoring force to the liquid crystal, so that the liquid crystal It is not easily affected by the surface of the terrain and slides. When the first acrylate has a long carbon chain functional group of less than 8 carbons, the acrylic resin composition has poor forward direction when oriented rubbing after film formation, and the formed alignment film does not have liquid crystal for the liquid crystal. Good alignment uniformity; when the first acrylate has a long carbon chain functional group of more than 18 carbons, the acrylic resin composition exhibits a haze at normal temperature, is difficult to transmit light, and is subjected to subsequent processing and application. Preferably, the first acrylate has a C 12 ~ C 18 long carbon chain functional group.
較佳地,該第一丙烯酸酯是選自於長興化工市售的EM-2191[含有丙烯酸辛酯及丙烯酸癸酯(octyl-decyl acrylate)]、EM-215[含有丙烯酸月桂酯(lauryl acrylate)]或EM-218[含有丙烯酸十八酯(stearyl acrylate)]。Preferably, the first acrylate is commercially available from Changxing Chemical Co., Ltd. EM-2191 [containing octyl acrylate and octyl-decyl acrylate], EM-215 [containing lauryl acrylate] ] or EM-218 [containing stearyl acrylate].
較佳地,該丙烯酸酯組分還包括一含有至少一OCH2 CH2 基團的第二丙烯酸酯,用以增進其所形成的配向膜的配向力。Preferably, the acrylate component further comprises a second acrylate containing at least one OCH 2 CH 2 group to enhance the alignment force of the alignment film formed thereby.
較佳地,該第二丙烯酸酯是選自於丙烯酸2-(2-乙氧基乙氧基)乙酯[2-(2-ethoxyethoxy)ethyl acrylate,EOEOEA]、丙烯酸2-苯氧基乙酯(2-phenoxyethyl acrylate,PHEA)、丙烯酸2-(對-異丙苯基苯氧基)乙酯[2-(p -cumylphenoxy)ethyl acrylate,CPEA]、丙烯酸2-(鄰-苯基苯氧基)乙酯[2-(o -phenylphenoxy)ethyl acrylate,OPPEA]、丙烯酸乙氧基化苯氧基乙酯(ethoxylated(3)phenoxyl acrylate,PH(3EO)A)或其組合。較佳地,該第二丙烯酸酯是選自於丙烯酸2-(2- 乙氧基乙氧基)乙酯(EOEOEA)、丙烯酸2-苯氧基乙酯(PHEA)或其組合。更佳地,該第二丙烯酸酯是選自於長興化工市售的EM-210(含有PHEA)、EM-211(含有EOEOEA)或其組合。Preferably, the second acrylate is selected from 2-(2-ethoxyethoxy)ethyl acrylate, EOEOEA, 2-phenoxyethyl acrylate (2-phenoxyethyl acrylate, PHEA), 2-( p- cumylphenoxy)ethyl acrylate, CPEA, 2-(o-phenylphenoxy) acrylate Ethyl 2-[ o- phenylphenoxy)ethyl acrylate, OPPEA], ethoxylated (3) phenoxyl acrylate, PH (3EO) A, or a combination thereof. Preferably, the second acrylate is selected from the group consisting of 2-(2-ethoxyethoxy)ethyl acrylate (EOEOEA), 2-phenoxyethyl acrylate (PHEA) or a combination thereof. More preferably, the second acrylate is EM-210 (containing PHEA), EM-211 (containing EOEOEA), or a combination thereof, which is commercially available from Changxing Chemical.
在本發明之具體實施例中,該丙烯酸酯組分還包括長興化工市售的EM-223[含有三伸丙二醇二丙烯酸酯(tripropylene glycol diacrylate)]、EM-2108(含有CPEA)、DR-U026[含有脂肪族胺基丙烯酸酯(aliphatic urethane acrylate)]、FS-2250[含有茀系丙烯酸酯(fluorene-based acrylate)]或其組合。In a specific embodiment of the present invention, the acrylate component further comprises EM-223 [containing tripropylene glycol diacrylate], EM-2108 (containing CPEA), DR-U026, which is commercially available from Changxing Chemical Co., Ltd. [containing an aliphatic urethane acrylate], FS-2250 [containing fluorene-based acrylate] or a combination thereof.
較佳地,該光起始劑是一紫外光起始劑。更佳地,該紫外光起始劑是Ciba公司市售的I-184、I-819、I-173或TPO。在本發明之具體實施例中,該光起始劑是Ciba公司市售的I-184[含有1-羥基環己基苯基甲酮(1-hydroxycyclohexyl phenyl ketone)]。Preferably, the photoinitiator is an ultraviolet light initiator. More preferably, the ultraviolet light initiator is commercially available I-184, I-819, I-173 or TPO from Ciba Corporation. In a particular embodiment of the invention, the photoinitiator is commercially available I-184 [containing 1-hydroxycyclohexyl phenyl ketone] from Ciba Corporation.
較佳地,該黏結劑是PMMA型黏結劑、聚氨酯丙烯酸酯(PU acrylate)型黏結劑、矽氧烷(Siloxane)丙烯酸酯型黏結劑、液態橡膠丙烯酸酯型黏結劑。在本發明之具體實施例中,該黏結劑是雙鍵化工市售的353H(含有PMMA)。Preferably, the binder is a PMMA type binder, a urethane acrylate type binder, a siloxane acrylate type binder, and a liquid rubber acrylate type binder. In a particular embodiment of the invention, the binder is 353H (containing PMMA) commercially available from Double Bond Chemicals.
較佳地,本發明丙烯酸系樹脂組成物還包含一消泡劑。在本發明之具體實施例中,該消泡劑是金普利公司市售的WD-608[含有含矽丙烯酸酯(Silicon-acrylate)]。Preferably, the acrylic resin composition of the present invention further comprises an antifoaming agent. In a specific embodiment of the invention, the antifoaming agent is WD-608 [containing Silicone-acrylate] commercially available from Cooper.
本發明之配向膜,是將一如上所述的丙烯酸系 樹脂組成物進行塗佈後,再經過曝光後所形成。在本發明之具體實施例中,該配向膜是將一如上所述的丙烯酸系樹脂組成物塗佈於一聚對苯二甲酸乙二酯(PET)基板上,經滾壓(rolling)製程,再經過紫外光曝光,並進行定向摩擦後所形成。The alignment film of the present invention is an acrylic system as described above After the resin composition is applied, it is formed by exposure. In a specific embodiment of the present invention, the alignment film is coated on a polyethylene terephthalate (PET) substrate by an acrylic resin composition as described above, and is subjected to a rolling process. It is exposed to ultraviolet light and formed by directional rubbing.
較佳地,在形成該配向膜的丙烯酸系樹脂組成物中,該丙烯酸酯組分還包括一含有至少一OCH2 CH2 基團的第二丙烯酸酯。Preferably, in the acrylic resin composition forming the alignment film, the acrylate component further comprises a second acrylate containing at least one OCH 2 CH 2 group.
本發明三維液晶顯示器,包含一透明基板、一形成在該透明基板上的聚醯亞胺膜、一形成在該聚醯亞胺膜上的液晶層及一與該液晶層接觸且如上所述的配向膜,其中,該配向膜與該液晶層的界面是呈波浪狀。The three-dimensional liquid crystal display of the present invention comprises a transparent substrate, a polyimide film formed on the transparent substrate, a liquid crystal layer formed on the polyimide film, and a liquid crystal layer in contact with the liquid crystal layer as described above. An alignment film, wherein an interface between the alignment film and the liquid crystal layer is wavy.
依據下表1所列之配方組成及用量比例(wt%),在常溫常壓下予以混合而得到本發明實施例1~2及比較例1~3之丙烯酸系樹脂組成物。The acrylic resin compositions of Examples 1 to 2 and Comparative Examples 1 to 3 of the present invention were obtained by mixing at normal temperature and normal pressure according to the formulation and the amount (wt%) listed in Table 1 below.
分別將上述實施例1~2及比較例1~3的丙烯酸系樹脂組成物塗佈於聚對苯二甲酸乙二酯(PET)基板上,經凸輪滾壓製程,再經過紫外光(1000 mJ/cm2 )曝光,形成波浪狀的連續凹狀膜,再進行定向摩擦後,分別得到應用例1~2及比較應用例1~3的配向膜。其中,比較應用例3的配向膜由於含有過多的長碳鏈官能基,導致其硬度不足,使得進行定向摩擦的效果不佳,進而造成後續塗佈之液晶無法配向。The acrylic resin compositions of the above Examples 1 to 2 and Comparative Examples 1 to 3 were applied onto a polyethylene terephthalate (PET) substrate, and subjected to a cam rolling process, followed by ultraviolet light (1000 mJ). /cm 2 ) Exposure, a wavy continuous concave film was formed, and after oriented rubbing, the alignment films of Application Examples 1 to 2 and Comparative Application Examples 1 to 3 were respectively obtained. Among them, the alignment film of Comparative Application Example 3 contained too many long carbon chain functional groups, resulting in insufficient hardness, so that the effect of performing directional rubbing was not good, and the subsequent applied liquid crystal could not be aligned.
分別將向列型反應性液晶高分子(Nematic reactive liquid crystal polymer)塗佈於上述配向膜,再覆蓋上表面形成有聚醯亞胺膜的玻璃,最後再經過紫外光曝光以固化液晶,分別得到應用例1~2及比較應用例1~2的三維液晶顯示器,並利用偏光顯微鏡分別觀察其配向結果, 結果分別如圖1~圖4所示。A Nematic reactive liquid crystal polymer is applied to the alignment film, and a glass having a polyimide film formed on the upper surface is coated thereon, and finally exposed to ultraviolet light to cure the liquid crystal, respectively. Application Examples 1 to 2 and Comparative Application Examples 1 to 2 of the three-dimensional liquid crystal display, and the alignment results were observed by a polarizing microscope, The results are shown in Figures 1 to 4, respectively.
參見圖1~圖4,應用例1~2的三維液晶顯示器無明顯的配向區域差異,顯示其具有良好的配向均勻性。參見圖3及圖4,比較應用例1及2的三維液晶顯示器具有顯著的配向區域明暗差異(分別如圖中箭頭所指),由於其缺乏長碳鏈官能基或含量不足,導致配向較不均勻,因此將使得透過該等三維液晶顯示器觀看三維畫面時出現影像色差或重疊現象。Referring to FIG. 1 to FIG. 4, the three-dimensional liquid crystal display of Application Examples 1 to 2 has no obvious alignment area difference, and shows that it has good alignment uniformity. Referring to FIG. 3 and FIG. 4, the three-dimensional liquid crystal display of Comparative Application Examples 1 and 2 has significant difference in brightness and darkness of the alignment area (as indicated by the arrows in the figure), and the alignment is less due to lack of long carbon chain functional groups or insufficient content. Uniform, thus causing image chromatic aberration or overlap when viewing a three-dimensional picture through the three-dimensional liquid crystal display.
綜上所述,由於本發明丙烯酸系樹脂組成物包含10~19 wt%具有C8 ~C18 之長碳鏈官能基的第一丙烯酸酯,能有效加強該丙烯酸系樹脂組成物形成配向膜後進行定向摩擦時的順向能力,可對液晶產生均勻的配向性,並增加對於液晶的錨定力,使得液晶不易受到地貌曲面影響而滑動,故確實能達成本發明之目的。As described above, since the acrylic resin composition of the present invention contains 10 to 19% by weight of the first acrylate having a long carbon chain functional group of C 8 to C 18 , the acrylic resin composition can be effectively strengthened to form an alignment film. The forward directional ability during directional rubbing can produce uniform alignment to the liquid crystal and increase the anchoring force to the liquid crystal, so that the liquid crystal is not easily affected by the surface of the surface and slides, so the object of the present invention can be achieved.
惟以上所述者,僅為本發明之較佳實施例而已,當不能以此限定本發明實施之範圍,即大凡依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾,皆仍屬本發明專利涵蓋之範圍內。The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the patent application scope and patent specification content of the present invention, All remain within the scope of the invention patent.
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CN111148769B (en) * | 2017-09-27 | 2023-01-10 | 大日本印刷株式会社 | Liquid crystal composition, phase difference film and method for producing same, transfer laminate, optical member and method for producing same, and display device |
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US7959990B2 (en) * | 2005-09-20 | 2011-06-14 | Rolic Ag | Functionalized photoreactive compounds |
TW201219494A (en) * | 2010-11-12 | 2012-05-16 | Daxin Materials Corp | comprising urethane (alkyl)acrylate or polyurethane (alkyl)acrylate, polyalkylene glycol alkyl ether (alkyl)acrylate, alkyl (alkyl)acrylate and photo-initiator; and having high tensility and transmittance, weatherability and good mechanical properties |
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CN1277132C (en) * | 2003-12-26 | 2006-09-27 | 奇美实业股份有限公司 | Light sensitive resin composition for color filter |
CN102200688B (en) * | 2010-03-23 | 2012-10-03 | 奇美实业股份有限公司 | Photosensitive resin composition, black matrix prepared from the photosensitive resin composition, and application of the black matrix |
KR101351624B1 (en) * | 2010-12-31 | 2014-01-15 | 제일모직주식회사 | Adhesive composition and a method for assembling module of mobile phone using the same |
JP5884325B2 (en) * | 2011-07-15 | 2016-03-15 | Jsr株式会社 | Color filter, liquid crystal display element, and method of manufacturing color filter |
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US7959990B2 (en) * | 2005-09-20 | 2011-06-14 | Rolic Ag | Functionalized photoreactive compounds |
TW201219494A (en) * | 2010-11-12 | 2012-05-16 | Daxin Materials Corp | comprising urethane (alkyl)acrylate or polyurethane (alkyl)acrylate, polyalkylene glycol alkyl ether (alkyl)acrylate, alkyl (alkyl)acrylate and photo-initiator; and having high tensility and transmittance, weatherability and good mechanical properties |
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