TW202007703A - Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element - Google Patents
Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element Download PDFInfo
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- TW202007703A TW202007703A TW108124623A TW108124623A TW202007703A TW 202007703 A TW202007703 A TW 202007703A TW 108124623 A TW108124623 A TW 108124623A TW 108124623 A TW108124623 A TW 108124623A TW 202007703 A TW202007703 A TW 202007703A
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- Taiwan
- Prior art keywords
- liquid crystal
- crystal display
- sealant
- display element
- compound
- Prior art date
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 111
- 239000000565 sealant Substances 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title abstract description 18
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- 239000011347 resin Substances 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 238000003860 storage Methods 0.000 claims abstract description 28
- 239000004642 Polyimide Substances 0.000 claims abstract description 27
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- 238000012360 testing method Methods 0.000 claims abstract description 13
- 230000006835 compression Effects 0.000 claims abstract description 12
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- 239000003505 polymerization initiator Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims description 64
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- 125000000524 functional group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 3
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- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
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- 239000007822 coupling agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical class [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
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- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
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- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
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- 239000004814 polyurethane Substances 0.000 description 1
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- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
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- 239000000454 talc Substances 0.000 description 1
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- 150000003512 tertiary amines Chemical class 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Liquid Crystal (AREA)
- Sealing Material Composition (AREA)
Abstract
Description
本發明係關於一種即便於異型加工時亦可維持優異之接著性之液晶顯示元件用密封劑。又，本發明係關於一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。The present invention relates to a sealant for a liquid crystal display element that can maintain excellent adhesion even during profile processing. In addition, the present invention relates to an upper and lower conduction material and a liquid crystal display element formed by using the sealant for liquid crystal display elements.
近年來，作為液晶顯示元件之製造方法，就產距時間（tact time）之縮短、液晶使用量之最佳化等觀點而言，使用如專利文獻1、專利文獻2所揭示般之被稱為滴下法之液晶滴下方式，該滴下法使用含有硬化性樹脂、光聚合起始劑及熱硬化劑之光熱併用硬化型密封劑。In recent years, as a method of manufacturing a liquid crystal display element, from the viewpoints of shortening the tact time and optimizing the amount of liquid crystal used, the use of such as disclosed in Patent Document 1 and Patent Document 2 is called The liquid crystal dropping method of the dropping method, which uses a photo-thermal combined hardening type sealant containing a curable resin, a photopolymerization initiator and a thermosetting agent.
滴下法中，首先，於2片附電極之透明基板之一透明基板上，藉由滴塗（dispense）形成長方形之密封圖案。繼而，於密封劑未硬化之狀態下將液晶之微滴滴滿透明基板之框內整個面，其後立即使另一透明基板重合，對密封部照射紫外線等光進行暫時硬化。其後，進行加熱使其正式硬化，而製作液晶顯示元件。藉由於減壓下進行基板之貼合，能夠以極高之效率製造液晶顯示元件，該滴下法成為當前液晶顯示元件之製造方法之主流。In the dropping method, first, a rectangular sealing pattern is formed on one of the two transparent substrates with electrodes by dispense. Then, the droplets of the liquid crystal are dripped over the entire surface of the frame of the transparent substrate in a state where the sealant is not cured, and immediately after that, another transparent substrate is overlapped, and the sealing portion is irradiated with light such as ultraviolet rays to temporarily cure. Thereafter, heating is performed to formally harden the liquid crystal display element. By bonding the substrates under reduced pressure, the liquid crystal display element can be manufactured with extremely high efficiency, and the dropping method has become the mainstream of current methods of manufacturing liquid crystal display elements.
且說，於行動電話、攜帶型遊戲機等各種附有液晶面板之移動式機器普及之當代，要求最多的課題即為機器之小型化。作為機器之小型化之手法，可列舉液晶顯示部之窄邊緣化，例如將密封部之位置配置於黑矩陣下方（以下，亦稱為窄邊緣設計）。伴隨此種窄邊緣設計，密封劑之塗佈位置位於聚醯亞胺等配向膜上之情況變多。 先前技術文獻 專利文獻In addition, in the contemporary era in which mobile devices such as mobile phones and portable game consoles with liquid crystal panels are popular, the most demanded issue is the miniaturization of the devices. As a method of miniaturizing the device, a narrow edge of the liquid crystal display part can be cited, for example, the position of the sealing part is arranged below the black matrix (hereinafter, also referred to as a narrow edge design). With such a narrow edge design, the application position of the sealant is often on the alignment film such as polyimide. Prior technical literature Patent Literature
專利文獻1：日本特開2001-133794號公報 專利文獻2：日本特開平5-295087號公報Patent Document 1: Japanese Patent Laid-Open No. 2001-133794 Patent Document 2: Japanese Patent Laid-Open No. 5-295087
[發明所欲解決之課題][Problems to be solved by the invention]
本發明之目的在於提供一種即便於異型加工時亦可維持優異之接著性之液晶顯示元件用密封劑。又，本發明之目的在於提供一種使用上述液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。 [解決課題之技術手段]An object of the present invention is to provide a sealant for liquid crystal display elements that can maintain excellent adhesiveness even during profile processing. In addition, an object of the present invention is to provide an upper and lower conduction material and a liquid crystal display element using the above-mentioned sealant for a liquid crystal display element. [Technical means to solve the problem]
本發明之液晶顯示元件用密封劑含有硬化性樹脂與聚合起始劑及/或熱硬化劑，該液晶顯示元件用密封劑其藉由依據JIS K 6852之常態試驗測得之硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度為30 kgf/cm2 以上，且硬化物於25℃之儲存彈性模數（storage elastic modulus）為2.5 GPa以下。 以下，對本發明進行詳細說明。The sealant for liquid crystal display elements of the present invention contains a curable resin and a polymerization initiator and/or a thermosetting agent. The sealant for liquid crystal display elements has a cured product measured at 25° C. by a normal test according to JIS K 6852 The compression shear strength of polyimide is 30 kgf/cm 2 or more, and the storage elastic modulus of the hardened product at 25°C is 2.5 GPa or less. Hereinafter, the present invention will be described in detail.
近年來，正在進行使用藉由凹槽（notch）加工等異型加工而加工為矩形以外之異型形狀之面板的液晶顯示元件之開發，然而尤其是於製造窄邊緣設計之液晶顯示元件時進行異型加工之情形時，有時會在加工過程中發生基板剝落之問題。 本發明人為了防止此種異型加工時之基板之剝落，研究了藉由使用柔軟之材料作為用於液晶顯示元件用密封劑之硬化性樹脂，而使硬化物之儲存彈性模數成為特定值以下。然而，僅藉由降低儲存彈性模數無法充分地防止異型加工時之基板之剝落。因此，本發明人研究了不僅將硬化物之儲存彈性模數設為特定值以下，且將利用密封劑使聚醯亞胺基板彼此接著時之壓縮剪切接著強度設為特定值以上。其結果為，發現獲得即便於異型加工時亦可維持優異之接著性之液晶顯示元件用密封劑，從而完成本發明。In recent years, the development of liquid crystal display elements using panels with irregular shapes such as notch processing and other irregular shapes is being developed. However, in particular, special-shaped processing is performed when manufacturing liquid crystal display elements with a narrow edge design In this case, sometimes the problem of substrate peeling occurs during processing. In order to prevent the peeling of the substrate during the special-shaped processing, the present inventors studied to use a soft material as a curable resin for a liquid crystal display element sealant, so that the storage elastic modulus of the cured product becomes below a certain value . However, only by reducing the storage elastic modulus can not sufficiently prevent the peeling of the substrate during the profile processing. Therefore, the inventors studied not only to set the storage elastic modulus of the cured product to a specific value or less, but also to set the compression shear adhesive strength when the polyimide substrates are bonded to each other using a sealant to a specific value or more. As a result, it was found that a sealing compound for liquid crystal display elements that can maintain excellent adhesiveness even during profile processing is obtained, and the present invention has been completed.
關於本發明之液晶顯示元件用密封劑，藉由依據JIS K 6852之常態試驗測得之硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度之下限為30 kgf/cm2 。藉由上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度為30 kgf/cm2 以上，且後述之硬化物於25℃之儲存彈性模數為2.5 GPa以下，從而使得本發明之液晶顯示元件用密封劑即便於異型加工時亦可維持優異之接著性。上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度之較佳之下限為35 kgf/cm2 。 上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度之較佳之上限無特別限制，實質性之上限為100 kgf/cm2 。 再者，上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度可利用以下之方法測定。 即，首先，於長度45 mm、寬度25 mm、厚度0.7 mm之ITO基板以100 nm左右之膜厚塗佈聚醯亞胺溶液，經處理而獲得基板（聚醯亞胺基板），準備2片該基板，於其中一基板上以接著時之直徑為3 mm之方式點塗密封劑。使另一聚醯亞胺基板以於長邊方向上錯開10 mm之方式經由密封劑重合於點塗有密封劑之聚醯亞胺基板。其後，使用金屬鹵化物燈等照射100 mW/cm2 之光30秒鐘後，於120℃加熱1小時，而使密封劑硬化，獲得試片。對於所獲得之試片，可藉由進行依據JIS K 6852之常態試驗測定壓縮剪切接著強度。Regarding the sealant for liquid crystal display elements of the present invention, the lower limit of the compressive shear adhesion strength of the hardened product to polyimide at 25° C. measured at 25° C. according to JIS K 6852 is 30 kgf/cm 2 . The compressive shear adhesion strength of the hardened product at 25°C for polyimide is 30 kgf/cm 2 or more, and the storage elastic modulus of the hardened product to be described later at 25°C is 2.5 GPa or less, thereby making the present invention The sealant for liquid crystal display elements can maintain excellent adhesion even when profiled. The lower limit of the compressive shear adhesion strength of the above hardened product at 25°C for polyimide is 35 kgf/cm 2 . The upper limit of the hardened material at 25°C for the compression shear adhesion strength of polyimide is not particularly limited, and the substantial upper limit is 100 kgf/cm 2 . In addition, the compression shear strength of the hardened product at 25°C with respect to polyimide can be measured by the following method. That is, first, a polyimide solution is applied to an ITO substrate with a length of 45 mm, a width of 25 mm, and a thickness of 0.7 mm at a film thickness of about 100 nm, and a substrate (polyimide substrate) is obtained by processing, and two pieces are prepared. On this substrate, a sealant was spot-applied on one of the substrates with a diameter of 3 mm. The other polyimide substrate was overlapped with the sealant-coated polyimide substrate via the sealant so as to be offset by 10 mm in the longitudinal direction. Thereafter, after irradiating with light of 100 mW/cm 2 for 30 seconds using a metal halide lamp or the like, it was heated at 120° C. for 1 hour to harden the sealant to obtain a test piece. For the obtained test piece, the compression shear adhesive strength can be measured by performing a normal test according to JIS K 6852.
關於本發明之液晶顯示元件用密封劑，其硬化物於25℃之儲存彈性模數之上限為2.5 GPa。藉由上述硬化物於25℃之儲存彈性模數為2.5 GPa以下，且上述之硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度為30 kgf/cm2 以上，從而使得本發明之液晶顯示元件用密封劑即便於異型加工時亦可維持優異之接著性。上述硬化物於25℃之儲存彈性模數之較佳之上限為2.0 GPa，更佳之上限為1.5 GPa。 又，就使被接著體貼合時之接著性之觀點而言，上述硬化物於25℃之儲存彈性模數之較佳之下限為0.1 GPa，更佳之下限為1.0 GPa。 再者，作為測定上述儲存彈性模數之硬化物，使用如下述般硬化而成者：於使用金屬鹵化物燈等對密封劑照射100 mW/cm2 之光30秒鐘後，於120℃加熱1小時使其硬化。又，該硬化物係指液晶顯示元件中用於基板等之貼合或密封之密封劑硬化物。 又，上述儲存彈性模數可使用動態黏彈性測定裝置（例如，IT計測制御公司製造，「DVA-200」等），以拉伸模式、試片寬度5 mm、厚度0.35 mm、抓持寬度25 mm、升溫速度10℃/分鐘、頻率10 Hz之條件進行測定。With regard to the sealant for liquid crystal display elements of the present invention, the upper limit of the storage elastic modulus of the cured product at 25°C is 2.5 GPa. The storage elastic modulus of the above-mentioned hardened product at 25°C is 2.5 GPa or less, and the compressive shear adhesion strength of the above-mentioned hardened product to polyimide at 25°C is 30 kgf/cm 2 or more, thereby making the present invention The sealant for liquid crystal display elements can maintain excellent adhesion even when profiled. The upper limit of the storage elastic modulus of the hardened product at 25°C is preferably 2.0 GPa, and the upper limit is more preferably 1.5 GPa. In addition, from the viewpoint of adhesion when the adherend is bonded, the storage elastic modulus of the hardened product at 25°C is preferably lower than 0.1 GPa, and more preferably lower than 1.0 GPa. In addition, as the hardened material for measuring the above storage elastic modulus, a material hardened as follows is used: after irradiating 100 mW/cm 2 of light with a sealant using a metal halide lamp or the like for 30 seconds, it is heated at 120°C Harden it in 1 hour. In addition, this hardened|cured material means the hardened|cured material of the sealing compound used for bonding or sealing of a board|substrate etc. in a liquid crystal display element. In addition, the storage elastic modulus can be measured using a dynamic viscoelasticity measuring device (for example, "DVA-200" manufactured by IT Measurement & Manufacturing Co., Ltd.) in a tensile mode, with a test piece width of 5 mm, a thickness of 0.35 mm, and a grip width of 25 mm, heating rate 10℃/min, frequency 10 Hz.
關於本發明之液晶顯示元件用密封劑，其硬化物之玻璃轉移溫度之較佳之上限為75℃。藉由上述硬化物之玻璃轉移溫度為75℃以下，從而使得本發明之液晶顯示元件用密封劑成為於異型加工時接著性更加優異者。上述硬化物之玻璃轉移溫度之更佳之上限為70℃。 又，就防透濕性等觀點而言，上述硬化物之玻璃轉移溫度之較佳之下限為30℃，更佳之下限為35℃。 再者，於本說明書中，上述「玻璃轉移溫度」係指藉由動態黏彈性測定而獲得之損耗正切（tanδ）之極大之中，出現起因於微布朗運動之極大時之溫度。上述玻璃轉移溫度可利用使用黏彈性測定裝置等之習知公知之方法測定。 又，作為測定上述玻璃轉移溫度之硬化物，與測定上述儲存彈性模數之硬化物同樣地使用使密封劑硬化而成者。With regard to the sealant for liquid crystal display elements of the present invention, the preferable upper limit of the glass transition temperature of the cured product is 75°C. Since the glass transition temperature of the hardened product is 75° C. or lower, the sealant for liquid crystal display elements of the present invention is more excellent in the adhesion during profile processing. The upper limit of the glass transition temperature of the hardened product is more preferably 70°C. In addition, from the viewpoint of moisture permeability resistance, the lower limit of the glass transition temperature of the cured product is preferably 30°C, and the lower limit is more preferably 35°C. Furthermore, in this specification, the above-mentioned "glass transition temperature" refers to the temperature at which the maximum due to the micro-Brownian motion occurs among the maximum of the loss tangent (tan δ) obtained by dynamic viscoelasticity measurement. The above-mentioned glass transition temperature can be measured by a well-known method using a viscoelasticity measuring device or the like. In addition, as the cured product for measuring the glass transition temperature, the one obtained by curing the sealant is used in the same manner as the cured product for measuring the storage elastic modulus.
對於後述之硬化性樹脂、聚合起始劑及/或熱硬化劑、以及填充劑等其他成分，藉由選擇其等之種類及調整含有比率，可將上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度、及上述硬化物於25℃之儲存彈性模數設為上述範圍。For other components such as the curable resin, the polymerization initiator and/or the thermosetting agent, and the filler described below, by selecting the type and adjusting the content ratio, the above-mentioned cured product can be cured at 25°C The compressive shear adhesion strength of the amine and the storage elastic modulus of the hardened product at 25°C are set in the above range.
本發明之液晶顯示元件用密封劑含有硬化性樹脂。 上述硬化性樹脂較佳為含有：具有聚合性官能基與柔軟骨架之化合物（以下，亦稱為「具有柔軟骨架之硬化性樹脂」）。藉由含有上述具有柔軟骨架之硬化性樹脂，從而容易將上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度、及上述硬化物於25℃之儲存彈性模數設為上述範圍。The sealing compound for liquid crystal display elements of this invention contains curable resin. The curable resin preferably contains a compound having a polymerizable functional group and a flexible skeleton (hereinafter, also referred to as "curable resin having a flexible skeleton"). By containing the above-mentioned hardening resin having a soft skeleton, it is easy to set the compressive shear adhesion strength of the hardened product to polyimide at 25°C, and the storage elastic modulus of the hardened product at 25°C to the above range .
作為上述聚合性官能基，例如可列舉：(甲基)丙烯醯基、環氧基等。又，上述具有柔軟骨架之硬化性樹脂較佳為於1分子中具有2個以上之上述聚合性官能基。 再者，於本說明書中，上述「(甲基)丙烯醯基」係指丙烯醯基或甲基丙烯醯基。Examples of the polymerizable functional group include (meth)acryloyl and epoxy groups. In addition, the curable resin having a flexible skeleton preferably has two or more polymerizable functional groups in one molecule. In addition, in this specification, the "(meth)acryloyl group" means an acryloyl group or methacryloyl group.
上述柔軟骨架較佳為選自由環狀內酯之開環結構、環氧烷（alkylene oxide）結構、及橡膠結構所組成之群之至少1種，更佳為環狀內酯之開環結構及/或橡膠結構，進而較佳為環狀內酯之開環結構。藉由使用具有此種柔軟骨架之硬化性樹脂，從而更加容易將上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度、及上述硬化物於25℃之儲存彈性模數設為上述範圍。The above-mentioned flexible skeleton is preferably at least one selected from the group consisting of a ring-opening structure of a cyclic lactone, an alkylene oxide structure, and a rubber structure, and more preferably a ring-opening structure of a cyclic lactone and The rubber structure is more preferably a ring-opening structure of a cyclic lactone. By using a curable resin having such a soft skeleton, it is easier to set the compression shear adhesion strength of the cured product at 25°C for polyimide and the storage elastic modulus of the cured product at 25°C The above range.
作為上述環狀內酯，例如可列舉：γ-十一內酯、ε-己內酯、γ-癸內酯、σ-十二內酯、γ-壬內酯（γ-nonalactone）、γ-壬內酯（γ-nonanolactone）、γ-戊內酯、σ-戊內酯、β-丁內酯、γ-丁內酯、β-丙內酯、σ-己內酯、7-丁基-2-氧雜環庚烷酮（7-butyl-2-oxepanone）等。其中，較佳為開環時主骨架之直鏈部分之碳數為5〜7者。Examples of the cyclic lactones include γ-undecalactone, ε-caprolactone, γ-decalactone, σ-dodecalactone, γ-nonalactone, and γ- Non-lactone (γ-nonanolactone), γ-valerolactone, σ-valerolactone, β-butyrolactone, γ-butyrolactone, β-propiolactone, σ-caprolactone, 7-butyl- 2-oxepanone (7-butyl-2-oxepanone), etc. Among them, it is preferable that the carbon number of the linear portion of the main skeleton is 5 to 7 when the ring is opened.
作為上述環氧烷結構，例如可列舉：環氧乙烷結構、環氧丙烷結構、環氧丁烷結構等。其中，較佳為環氧丁烷結構。Examples of the alkylene oxide structure include an ethylene oxide structure, a propylene oxide structure, and a butylene oxide structure. Among them, a butylene oxide structure is preferred.
上述橡膠結構較佳為於主鏈具有不飽和鍵之結構、或於主鏈具有聚矽氧烷骨架之結構。 作為上述於主鏈具有不飽和鍵之結構，例如可列舉：於主鏈具有因共軛二烯之聚合而產生之骨架之結構等。 作為上述因共軛二烯之聚合而產生之骨架，例如可列舉：丙烯腈-丁二烯骨架、聚丁二烯骨架、聚異戊二烯骨架、苯乙烯-丁二烯骨架、聚異丁烯骨架、聚氯丁二烯骨架等。 其中，上述橡膠結構較佳為具有丙烯腈-丁二烯骨架之結構。The above rubber structure is preferably a structure having an unsaturated bond in the main chain or a structure having a polysiloxane skeleton in the main chain. Examples of the structure having an unsaturated bond in the main chain include a structure having a skeleton generated by polymerization of conjugated diene in the main chain. Examples of the skeleton generated by the polymerization of the conjugated diene include acrylonitrile-butadiene skeleton, polybutadiene skeleton, polyisoprene skeleton, styrene-butadiene skeleton, and polyisobutylene skeleton. , Polychloroprene skeleton, etc. Among them, the rubber structure is preferably a structure having an acrylonitrile-butadiene skeleton.
上述具有柔軟骨架之硬化性樹脂之分子量之較佳之下限為100，較佳之上限為10萬。藉由上述具有柔軟骨架之硬化性樹脂之分子量為該範圍，從而更加容易將上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度、及上述硬化物於25℃之儲存彈性模數設為上述範圍。上述具有柔軟骨架之硬化性樹脂之分子量之更佳之下限為200，更佳之上限為5萬。 再者，於本說明書中，關於上述「分子量」，對於分子結構被特定出之化合物而言，係根據結構式而求出者，但對於聚合度之分佈較廣之化合物及改質部位不特定之化合物而言，有時使用重量平均分子量表示。又，上述「重量平均分子量」係利用凝膠滲透層析法（GPC）使用四氫呋喃作為溶劑進行測定，根據聚苯乙烯換算求出之值。作為利用GPC測定根據聚苯乙烯換算之重量平均分子量時所使用之管柱，例如可列舉：Shodex LF-804（昭和電工公司製造）等。The preferable lower limit of the molecular weight of the above-mentioned curable resin having a soft skeleton is 100, and the preferable upper limit is 100,000. With the molecular weight of the hardening resin having a soft skeleton in this range, it is easier to apply the compression shear strength of the hardened product to polyimide at 25°C, and the storage elastic modulus of the hardened product at 25°C. The number is set to the above range. The lower limit of the molecular weight of the hardenable resin having a soft skeleton is more preferably 200, and the upper limit is more preferably 50,000. In addition, in this specification, regarding the above "molecular weight", for a compound whose molecular structure is specified, it is obtained based on the structural formula, but it is not specific for a compound with a wide distribution of polymerization degree and a modified site In terms of compounds, weight average molecular weight is sometimes used. In addition, the above-mentioned "weight average molecular weight" is measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and is a value calculated in terms of polystyrene. Examples of the column used when measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko).
作為上述具有柔軟骨架之硬化性樹脂，具體而言，例如可列舉：己內酯改質雙酚A型環氧(甲基)丙烯酸酯、己內酯改質雙酚F型環氧(甲基)丙烯酸酯、己內酯改質雙酚E型環氧(甲基)丙烯酸酯、環氧乙烷改質雙酚A型環氧(甲基)丙烯酸酯、環氧乙烷改質雙酚F型環氧(甲基)丙烯酸酯、環氧乙烷改質雙酚E型環氧(甲基)丙烯酸酯、環氧丙烷改質雙酚A型環氧(甲基)丙烯酸酯、環氧丙烷改質雙酚F型環氧(甲基)丙烯酸酯、環氧丙烷改質雙酚E型環氧(甲基)丙烯酸酯、含封端胺基之丁二烯-丙烯腈（ATBN）改質環氧(甲基)丙烯酸酯、含封端羧基之丁二烯-丙烯腈（CTBN）改質環氧(甲基)丙烯酸酯、(甲基)丙烯酸改質異戊二烯橡膠、(甲基)丙烯酸改質丁二烯橡膠、(甲基)丙烯酸改質聚矽氧橡膠、己內酯改質雙酚A型環氧樹脂、己內酯改質雙酚F型環氧樹脂、己內酯改質雙酚E型環氧樹脂、環氧乙烷改質雙酚A型環氧樹脂、環氧乙烷改質雙酚F型環氧樹脂、環氧乙烷改質雙酚E型環氧樹脂、環氧丙烷改質雙酚A型環氧樹脂、環氧丙烷改質雙酚F型環氧樹脂、環氧丙烷改質雙酚E型環氧樹脂、NBR改質雙酚A型環氧樹脂、ATBN改質環氧樹脂、CTBN改質環氧樹脂、環氧改質異戊二烯橡膠、環氧改質丁二烯橡膠、環氧改質聚矽氧橡膠等。 上述具有柔軟骨架之硬化性樹脂可單獨地使用，亦可組合2種以上使用。 再者，於本說明書中，上述所謂「(甲基)丙烯酸酯」係指丙烯酸酯或甲基丙烯酸酯，上述所謂「環氧(甲基)丙烯酸酯」係指使環氧化合物中之全部環氧基與(甲基)丙烯酸反應而成之化合物。Specific examples of the above-mentioned curable resin having a flexible skeleton include caprolactone modified bisphenol A epoxy (meth)acrylate and caprolactone modified bisphenol F epoxy (methyl ) Acrylate, caprolactone modified bisphenol E epoxy (meth)acrylate, ethylene oxide modified bisphenol A epoxy (meth)acrylate, ethylene oxide modified bisphenol F Type epoxy (meth) acrylate, ethylene oxide modified bisphenol E type epoxy (meth) acrylate, propylene oxide modified bisphenol A epoxy (meth) acrylate, propylene oxide Modified bisphenol F epoxy (meth) acrylate, propylene oxide modified bisphenol E epoxy (meth) acrylate, butadiene-acrylonitrile (ATBN) modified with blocked amine groups Epoxy (meth) acrylate, modified butadiene-acrylonitrile (CTBN) containing blocked carboxyl groups, epoxy (meth) acrylate, (meth) acrylic modified isoprene rubber, (meth ) Acrylic modified butadiene rubber, (meth)acrylic modified polysiloxane rubber, caprolactone modified bisphenol A epoxy resin, caprolactone modified bisphenol F epoxy resin, caprolactone Modified bisphenol E type epoxy resin, ethylene oxide modified bisphenol A type epoxy resin, ethylene oxide modified bisphenol F type epoxy resin, ethylene oxide modified bisphenol E type epoxy resin Resin, propylene oxide modified bisphenol A epoxy resin, propylene oxide modified bisphenol F epoxy resin, propylene oxide modified bisphenol E epoxy resin, NBR modified bisphenol A epoxy resin Resin, ATBN modified epoxy resin, CTBN modified epoxy resin, epoxy modified isoprene rubber, epoxy modified butadiene rubber, epoxy modified polysiloxane rubber, etc. The above-mentioned curable resin having a soft skeleton may be used alone or in combination of two or more. In addition, in this specification, the above-mentioned "(meth)acrylate" refers to acrylate or methacrylate, and the above-mentioned "epoxy (meth)acrylate" refers to all epoxy in the epoxy compound A compound formed by the reaction of (meth)acrylic group
上述硬化性樹脂較佳為以調整上述硬化物之於25℃之對於聚醯亞胺之壓縮剪切接著強度、及上述硬化物於25℃之儲存彈性模數，或進一步提高貼合被接著體時之接著性或低液晶污染性等為目的，含有上述具有柔軟骨架之硬化性樹脂以外之其他硬化性樹脂。 於含有上述其他硬化性樹脂之情形時，上述具有柔軟骨架之硬化性樹脂於上述硬化性樹脂100重量份中之含量之較佳之下限為30重量份，較佳之上限為90重量份。藉由上述具有柔軟骨架之硬化性樹脂之含量為該範圍，從而更加容易將上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度、及上述硬化物於25℃之儲存彈性模數設為上述範圍。上述具有柔軟骨架之硬化性樹脂之含量之更佳之下限為50重量份，更佳之上限為70重量份。 又，較佳為於上述硬化性樹脂100重量份中含有20重量份以上且80重量份以下之上述具有柔軟骨架之硬化性樹脂中之具有上述環狀內酯之開環結構之硬化性樹脂。The curable resin is preferably adjusted to adjust the compressive shear adhesion strength of the cured product at 25°C to the polyimide, and the storage elastic modulus of the cured product at 25°C, or to further increase the bonded object For the purpose of time adhesion, low liquid crystal contamination, etc., it contains curable resins other than the above-mentioned curable resins having a soft skeleton. When the other curable resins are contained, the lower limit of the content of the curable resin having a flexible skeleton in 100 parts by weight of the curable resin is preferably 30 parts by weight, and the upper limit is preferably 90 parts by weight. With the content of the hardening resin having a soft skeleton in this range, it is easier to apply the compression shear strength of the hardened product to polyimide at 25°C and the storage elastic modulus of the hardened product at 25°C. The number is set to the above range. The more preferable lower limit of the content of the above-mentioned hardenable resin having a soft skeleton is 50 parts by weight, and the more preferable upper limit is 70 parts by weight. In addition, it is preferable to contain 20 parts by weight or more and 80 parts by weight or less of the curable resin having a soft skeleton and a curable resin having a ring-opening structure of the cyclic lactone in 100 parts by weight of the curable resin.
作為上述其他硬化性樹脂，例如可列舉：不具有柔軟骨架之其他環氧化合物或不具有柔軟骨架之其他(甲基)丙烯酸化合物等。再者，於本說明書中，上述所謂「(甲基)丙烯酸」係指丙烯酸或甲基丙烯酸，上述所謂「(甲基)丙烯酸化合物」係指具有(甲基)丙烯醯基之化合物。Examples of the other curable resins include other epoxy compounds that do not have a flexible skeleton or other (meth)acrylic compounds that do not have a flexible skeleton. In addition, in this specification, the said "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the said "(meth)acrylic compound" means the compound which has a (meth)acryloyl group.
作為上述其他環氧化合物，例如可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚E型環氧樹脂、雙酚S型環氧樹脂、2,2'-二烯丙基雙酚A型環氧樹脂、氫化雙酚型環氧樹脂、間苯二酚型環氧樹脂、聯苯型環氧樹脂、硫醚（sulfide）型環氧樹脂、二苯醚型環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂、苯酚酚醛清漆型環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂、二環戊二烯酚醛清漆型環氧樹脂、聯苯酚醛清漆型環氧樹脂、萘酚酚醛清漆型環氧樹脂、環氧丙基胺型環氧樹脂、環氧丙基酯化合物等。Examples of the other epoxy compounds include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, bisphenol S epoxy resin, and 2,2'-diene. Propyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, resorcinol epoxy resin, biphenyl epoxy resin, sulfide epoxy resin, diphenyl ether epoxy resin Resin, dicyclopentadiene epoxy resin, naphthalene epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenol Novolac epoxy resin, naphthol novolac epoxy resin, epoxypropylamine epoxy resin, epoxypropyl ester compound, etc.
又，上述硬化性樹脂亦可含有於1分子中具有環氧基與(甲基)丙烯醯基之化合物作為上述其他環氧化合物。作為此種化合物，例如可列舉部分(甲基)丙烯酸改質環氧樹脂等，其藉由使於1分子中具有2個以上環氧基之環氧化合物之一部分之環氧基與(甲基)丙烯酸反應而獲得。In addition, the curable resin may contain a compound having an epoxy group and a (meth)acryloyl group in one molecule as the other epoxy compound. As such a compound, for example, a partially (meth)acrylic modified epoxy resin, etc. may be mentioned, which is composed of a part of the epoxy group and (methyl ) Acrylic acid is obtained by reaction.
作為上述其他(甲基)丙烯酸化合物，較佳為環氧(甲基)丙烯酸酯。又，就更加容易將上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度、及上述硬化物於25℃之儲存彈性模數設為上述範圍之觀點而言，上述其他(甲基)丙烯酸化合物較佳為於1分子中具有2個以上之(甲基)丙烯醯基之多官能(甲基)丙烯酸化合物。又，就上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度之觀點而言，較佳為不含有於1分子中具有1個(甲基)丙烯醯基之單官能(甲基)丙烯酸化合物。As the other (meth)acrylic compound described above, epoxy (meth)acrylate is preferred. In addition, from the viewpoint that it is easier to set the compressive shear adhesion strength of the hardened material at 25°C to polyimide and the storage elastic modulus of the hardened material at 25°C to the above range, the other (A The group) acrylic compound is preferably a polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups in one molecule. In addition, from the viewpoint of the compressive shear adhesion strength of the above-mentioned hardened product to polyimide at 25°C, it is preferable not to contain a monofunctional (meth)acryl amide group having one (meth)acryl group in one molecule. Base) acrylic compounds.
作為上述環氧(甲基)丙烯酸酯，例如可列舉藉由依據常規方法於鹼性觸媒之存在下使環氧化合物與(甲基)丙烯酸反應而獲得者等。Examples of the epoxy (meth)acrylates include those obtained by reacting an epoxy compound with (meth)acrylic acid in the presence of an alkaline catalyst according to a conventional method.
作為用於合成上述環氧(甲基)丙烯酸酯之原料之環氧化合物，可列舉與上述之其他環氧化合物相同者。Examples of the epoxy compound used as a raw material for synthesizing the above-mentioned epoxy (meth)acrylate include the same as the above-mentioned other epoxy compounds.
上述硬化性樹脂可單獨地使用，亦可組合2種以上使用。The above-mentioned curable resins may be used alone or in combination of two or more.
本發明之液晶顯示元件用密封劑較佳為將硬化性樹脂中之(甲基)丙烯醯基與環氧基之合計中之(甲基)丙烯醯基之含有比率設為50莫耳%以上95莫耳%以下。The sealant for liquid crystal display elements of the present invention preferably has a content ratio of (meth)acryloyl group in the total of (meth)acryloyl group in epoxy resin and epoxy group set to 50 mol% or more 95 mol% or less.
本發明之液晶顯示元件用密封劑含有聚合起始劑及/或熱硬化劑。 作為上述聚合起始劑，例如可列舉：藉由光照射產生自由基之光自由基聚合起始劑、或藉由加熱產生自由基之熱自由基聚合起始劑等。The sealing agent for liquid crystal display elements of this invention contains a polymerization initiator and/or a thermosetting agent. Examples of the polymerization initiator include a photoradical polymerization initiator that generates radicals by light irradiation, or a thermal radical polymerization initiator that generates radicals by heating.
作為上述光自由基聚合起始劑，就反應性之觀點而言，較佳為含有肟酯（oxime ester）化合物及9-氧硫
作為上述肟酯化合物，例如可列舉：1-(4-(苯硫基)苯基)-1,2-辛二酮2-(O-苯甲醯肟）、O-乙醯基-1-(6-(2-甲基苯甲醯基)-9-乙基-9H-咔唑-3-基)乙酮肟、下述式（1）所表示之化合物、下述式（2）所表示之化合物等。Examples of the oxime ester compound include 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyl oxime) and O-acetoyl-1- (6-(2-methylbenzyl)-9-ethyl-9H-carbazol-3-yl)ethanone oxime, compound represented by the following formula (1), represented by the following formula (2) Represented compounds, etc.
上述式（1）、上述式（2）中之芳香環中之氫原子亦可經取代基取代。作為該取代基，例如可列舉：甲基、乙基、丙基等。The hydrogen atom in the aromatic ring in the above formula (1) and the above formula (2) may be substituted with a substituent. Examples of the substituent include methyl, ethyl, and propyl.
上述9-氧硫
作為上述9-氧硫
式（3-2）中，n為1〜10（平均值）。In formula (3-2), n is 1 to 10 (average value).
上述式（3-1）、上述式（3-2）中之芳香環中之氫原子亦可經取代基取代。作為該取代基，例如可列舉：甲基、乙基、丙基等。The hydrogen atom in the aromatic ring in the above formula (3-1) and the above formula (3-2) may be substituted with a substituent. Examples of the substituent include methyl, ethyl, and propyl.
作為上述肟酯化合物及上述9-氧硫
作為上述其他光自由基聚合起始劑，具體而言，例如可列舉：1-羥基環己基苯基酮、2-苄基-2-二甲基胺基-1-(4-
上述光自由基聚合起始劑可單獨地使用，亦可組合2種以上使用。The photo radical polymerization initiator may be used alone or in combination of two or more.
作為上述熱自由基聚合起始劑，例如可列舉由偶氮化合物或有機過氧化物等構成者。其中，就抑制液晶污染之觀點而言，較佳為由偶氮化合物構成之起始劑（以下，亦稱為「偶氮起始劑」），更佳為由高分子偶氮化合物構成之起始劑（以下，亦稱為「高分子偶氮起始劑」）。 再者，於本說明書中，上述所謂「高分子偶氮化合物」係指具有偶氮基，且藉由熱生成可使(甲基)丙烯醯基硬化之自由基之數量平均分子量為300以上之化合物。Examples of the above-mentioned thermal radical polymerization initiator include those composed of an azo compound or an organic peroxide. Among them, from the viewpoint of suppressing liquid crystal contamination, an initiator composed of an azo compound is preferred (hereinafter, also referred to as "azo initiator"), and more preferably composed of a polymer azo compound Starter (hereinafter, also referred to as "polymer azo initiator"). In addition, in this specification, the above-mentioned "polymer azo compound" means an azo group, and the number average molecular weight of the radicals that can harden the (meth)acryloyl group by heat generation is 300 or more Compound.
上述高分子偶氮化合物之數量平均分子量之較佳之下限為1000，較佳之上限為30萬。藉由上述高分子偶氮化合物之數量平均分子量為該範圍，從而可防止對液晶造成不良影響，且容易與硬化性樹脂混合。上述高分子偶氮化合物之數量平均分子量之更佳之下限為5000，更佳之上限為10萬，進而較佳之下限為1萬，進而較佳之上限為9萬。 再者，於本說明書中，上述數量平均分子量係利用凝膠滲透層析法（GPC）使用四氫呋喃作為溶劑進行測定，根據聚苯乙烯換算求出之值。作為利用GPC測定根據聚苯乙烯換算之數量平均分子量時所使用之管柱，例如可列舉：Shodex LF-804（昭和電工公司製造）等。The preferable lower limit of the number average molecular weight of the above polymer azo compound is 1,000, and the preferable upper limit is 300,000. With the number average molecular weight of the above-mentioned polymer azo compound being in this range, it is possible to prevent adverse effects on the liquid crystal, and it is easy to mix with the curable resin. The more preferable lower limit of the number average molecular weight of the above-mentioned polymer azo compound is 5000, the more preferable upper limit is 100,000, the more preferable lower limit is 10,000, and the more preferable upper limit is 90,000. In addition, in this specification, the said number average molecular weight is the value measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and it is calculated based on polystyrene conversion. Examples of the column used when measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko).
作為上述高分子偶氮化合物，例如可列舉具有「聚環氧烷或聚二甲基矽氧烷等單元經由偶氮基而複數個鍵結之結構」者。 作為具有聚環氧烷等單元經由上述偶氮基而複數個鍵結之結構之高分子偶氮化合物，較佳為具有聚環氧乙烷結構者。 作為上述高分子偶氮化合物，具體而言，例如可列舉：4,4'-偶氮雙(4-氰基戊酸)與聚伸烷基二醇之縮聚物、或4,4'-偶氮雙(4-氰基戊酸)與具有封端胺基之聚二甲基矽氧烷之縮聚物等。 作為上述高分子偶氮起始劑之市售品，例如可列舉：VPE-0201、VPE-0401、VPE-0601、VPS-0501、VPS-1001（均為FUJIFILM WAKO PURE CHEMICAL公司製造）等。 又，作為非高分子之偶氮起始劑，例如可列舉：V-65、V-501（均為FUJIFILM WAKO PURE CHEMICAL公司製造）等。Examples of the polymer azo compound include a structure in which units such as polyalkylene oxide or polydimethylsiloxane are bonded via azo groups. The polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide is bonded via the azo group is preferably a polyethylene oxide structure. Specific examples of the polymer azo compound include, for example, a polycondensate of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or 4,4'-a Polycondensates of bis(4-cyanovaleric acid) and polydimethylsiloxane with blocked amine groups. Examples of commercially available products of the above-mentioned polymer azo initiators include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by FUJIFILM WAKO PURE CHEMICAL). In addition, examples of non-polymer azo initiators include V-65 and V-501 (all manufactured by FUJIFILM WAKO PURE CHEMICAL).
作為上述有機過氧化物，例如可列舉：酮過氧化物、過氧縮酮、氫過氧化物、二烷基過氧化物、過氧酯、二醯基過氧化物、過氧化二碳酸酯等。Examples of the organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, and peroxydicarbonates. .
上述熱自由基聚合起始劑可單獨地使用，亦可組合2種以上使用。The above-mentioned thermal radical polymerization initiator may be used alone or in combination of two or more.
上述聚合起始劑之含量相對於上述硬化性樹脂100重量份，較佳之下限為0.01重量份，較佳之上限為10重量份。藉由上述聚合起始劑之含量為該範圍，從而使得所獲得之液晶顯示元件用密封劑成為抑制液晶污染，且保存穩定性或硬化性更加優異者。上述聚合起始劑之含量之更佳之下限為0.1重量份，更佳之上限為5重量份。The content of the polymerization initiator relative to 100 parts by weight of the curable resin is preferably a lower limit of 0.01 parts by weight and a preferred upper limit of 10 parts by weight. When the content of the polymerization initiator is within this range, the obtained sealing compound for liquid crystal display elements can suppress the contamination of liquid crystals and have more excellent storage stability or curability. The more preferable lower limit of the content of the polymerization initiator is 0.1 part by weight, and the more preferable upper limit is 5 parts by weight.
上述熱硬化劑較佳為含有胺加成化合物。藉由使用上述胺加成化合物作為上述熱硬化劑，從而使得所獲得之液晶顯示元件用密封劑成為可兼具於低溫之熱硬化性與保存穩定性，且低液晶污染性更加優異者。The thermosetting agent preferably contains an amine addition compound. By using the above-mentioned amine addition compound as the above-mentioned thermosetting agent, the obtained sealing compound for a liquid crystal display element can have both low-temperature thermosetting properties and storage stability, and is more excellent in low liquid crystal contamination.
作為上述胺加成化合物，例如可列舉藉由使咪唑化合物或一至三級胺等胺系化合物與環氧化合物等反應而獲得之加成體等。Examples of the amine addition compound include adducts obtained by reacting an amine compound such as an imidazole compound or primary to tertiary amines with an epoxy compound and the like.
作為上述胺加成化合物之市售品，例如可列舉：Ajinomoto Fine-Techno公司製造之胺加成化合物、四國化成工業公司製造之胺加成化合物、三菱化學公司製造之胺加成化合物、ADEKA公司製造之胺加成化合物、T&K TOKA公司製造之胺加成化合物等。 作為上述Ajinomoto Fine-Techno公司製造之胺加成化合物，例如可列舉：Amicure PN-23、Amicure PN-23J、Amicure PN-H、Amicure PN-31、Amicure PN-31J、Amicure PN-40、Amicure PN-40J、Amicure PN-50、Amicure PN-F、Amicure MY-24、Amicure MY-H等。 作為上述四國化成工業公司製造之胺加成化合物，例如可列舉P-0505等。 作為上述三菱化學公司製造之胺加成化合物，例如可列舉P-200等。 作為上述ADEKA公司製造之胺加成化合物，例如可列舉：ADEKA HARDENER EH-5001P、ADEKA HARDENER EH-5057PK、ADEKA HARDENER EH-5030S、ADEKA HARDENER EH-5011S等。 作為上述T&K TOKA公司製造之胺加成化合物，例如可列舉：Fujicure-FXR-1036、Fujicure-FXR-1020、Fujicure-FXR-1081等。Examples of commercially available products of the above-mentioned amine addition compounds include amine addition compounds manufactured by Ajinomoto Fine-Techno Corporation, amine addition compounds manufactured by Shikoku Chemical Industry Co., Ltd., amine addition compounds manufactured by Mitsubishi Chemical Corporation, and ADEKA. Amine addition compounds manufactured by the company, amine addition compounds manufactured by T&K TOKA, etc. Examples of the amine addition compound manufactured by Ajinomoto Fine-Techno include Amicure PN-23, Amicure PN-23J, Amicure PN-H, Amicure PN-31, Amicure PN-31J, Amicure PN-40, Amicure PN -40J, Amicure PN-50, Amicure PN-F, Amicure MY-24, Amicure MY-H, etc. Examples of the amine addition compound manufactured by Shikoku Chemical Industry Co., Ltd. include P-0505. Examples of the amine addition compound manufactured by Mitsubishi Chemical Corporation include P-200. Examples of the amine addition compound manufactured by the aforementioned ADEKA company include ADEKA HARDENER EH-5001P, ADEKA HARDENER EH-5057PK, ADEKA HARDENER EH-5030S, ADEKA HARDENER EH-5011S, and the like. Examples of the amine addition compound manufactured by T&K TOKA include Fujicure-FXR-1036, Fujicure-FXR-1020, Fujicure-FXR-1081, and the like.
作為上述胺加成化合物以外之其他熱硬化劑，例如可列舉：有機酸醯肼、多酚系化合物、酸酐等。其中，較好地使用有機酸醯肼。Examples of the thermosetting agent other than the amine addition compound include organic acid hydrazine, polyphenol compounds, and acid anhydrides. Among them, the organic acid hydrazine is preferably used.
作為上述有機酸醯肼，例如可列舉：1,3-雙(肼基羰乙基)-5-異丙基乙內醯脲、癸二酸二醯肼、間苯二甲酸二醯肼、己二酸二醯肼、丙二酸二醯肼等。 作為上述有機酸醯肼之市售品，例如可列舉：Otsuka Chemical公司製造之有機酸醯肼、Japan Finechem公司製造之有機酸醯肼、Ajinomoto Fine-Techno公司製造之有機酸醯肼等。 作為上述Otsuka Chemical公司製造之有機酸醯肼，例如可列舉：SDH、ADH等。 作為上述Japan Finechem公司製造之有機酸醯肼，例如可列舉：MDH等。 作為上述Ajinomoto Fine-Techno公司製造之有機酸醯肼，例如可列舉：Amicure VDH、Amicure VDH-J、Amicure UDH等。Examples of the organic acid hydrazine include 1,3-bis(hydrazinocarbonylethyl)-5-isopropylhydantoin, dihydrazide sebacate, dihydrazide isophthalate, and hexane Diacid hydrazine diacid, dihydrazine malonate, etc. Examples of commercially available products of the above-mentioned organic acid hydrazide include organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazide manufactured by Japan Finechem Co., and organic acid hydrazide manufactured by Ajinomoto Fine-Techno. Examples of the organic acid hydrazide manufactured by the above-mentioned Otsuka Chemical Company include SDH and ADH. Examples of the organic acid hydrazide manufactured by Japan Finechem Corporation include MDH and the like. Examples of the organic acid hydrazide manufactured by Ajinomoto Fine-Techno Company include Amicure VDH, Amicure VDH-J, and Amicure UDH.
上述熱硬化劑可單獨地使用，亦可組合2種以上使用。The above-mentioned thermosetting agents may be used alone or in combination of two or more.
上述熱硬化劑之含量相對於上述硬化性樹脂100重量份，較佳之下限為1重量份，較佳之上限為50重量份。藉由上述熱硬化劑之含量為該範圍，從而可於不使所獲得之液晶顯示元件用密封劑之塗佈性等變差之情況下使熱硬化性更加優異。上述熱硬化劑之含量之更佳之上限為30重量份。The content of the above-mentioned thermosetting agent is preferably 1 part by weight with respect to 100 parts by weight of the above-mentioned curable resin, and the preferred upper limit is 50 parts by weight. With the content of the above-mentioned thermosetting agent in this range, the thermosetting property can be made more excellent without deteriorating the coating properties of the obtained sealing compound for liquid crystal display elements. The more preferable upper limit of the content of the above-mentioned thermosetting agent is 30 parts by weight.
本發明之液晶顯示元件用密封劑較佳為以提高黏度、藉由應力分散效應而進一步提高接著性、改善線膨脹率、提高硬化物之耐濕性等為目的，含有填充劑。又，藉由含有上述填充劑，從而更加容易將上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度、及上述硬化物於25℃之儲存彈性模數設為上述範圍。The sealant for a liquid crystal display element of the present invention preferably contains a filler for the purpose of increasing viscosity, further improving adhesion by stress dispersion effect, improving linear expansion rate, improving moisture resistance of the cured product, and the like. In addition, by containing the filler, it is easier to set the compressive shear adhesion strength of the cured product at 25°C to the polyimide and the storage elastic modulus of the cured product at 25°C in the above range.
作為上述填充劑，可使用無機填充劑或有機填充劑。 作為上述無機填充劑，例如可列舉：矽石、滑石、玻璃珠、石棉、石膏、矽藻土、膨潤石、膨潤土、蒙脫石、絹雲母、活性白土、氧化鋁、氧化鋅、氧化鐵、氧化鎂、氧化錫、氧化鈦、碳酸鈣、碳酸鎂、氫氧化鎂、氫氧化鋁、氮化鋁、氮化矽、硫酸鋇、矽酸鈣等。 作為上述有機填充劑，例如可列舉：聚酯微粒子、聚胺酯（polyurethane）微粒子、乙烯系聚合物微粒子、丙烯酸聚合物微粒子等。 上述填充劑可單獨地使用，亦可組合2種以上使用。As the above-mentioned filler, an inorganic filler or an organic filler can be used. Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, Magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, etc. Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, and the like. These fillers may be used alone or in combination of two or more.
上述填充劑之含量相對於上述硬化性樹脂100重量份，較佳之下限為10重量份，較佳之上限為80重量份。藉由上述填充劑之含量為該範圍，從而使得於不使塗佈性等變差之情況下改善接著性等效果更加優異，且更加容易將上述硬化物於25℃之對於聚醯亞胺之壓縮剪切接著強度、及上述硬化物於25℃之儲存彈性模數設為上述範圍。上述填充劑之含量之更佳之下限為30重量份，更佳之上限為60重量份。The content of the filler is 100 parts by weight of the curable resin, and the lower limit is preferably 10 parts by weight, and the upper limit is preferably 80 parts by weight. When the content of the filler is within this range, the effect of improving adhesion and the like without deteriorating the coating property and the like is more excellent, and it is easier to apply the cured product at 25° C. to polyimide. The compression shear adhesive strength and the storage elastic modulus of the hardened product at 25°C are set in the above range. The more preferable lower limit of the content of the filler is 30 parts by weight, and the more preferable upper limit is 60 parts by weight.
本發明之液晶顯示元件用密封劑較佳為含有矽烷偶合劑。上述矽烷偶合劑主要具有作為用於使密封劑與基板等良好地接著之接著助劑之作用。The sealing agent for liquid crystal display elements of the present invention preferably contains a silane coupling agent. The above-mentioned silane coupling agent mainly has a role as an adhesion aid for good adhesion of the sealant to the substrate and the like.
作為上述矽烷偶合劑，例如可較好地使用3-胺基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-異氰酸基丙基三甲氧基矽烷等。該等矽烷偶合劑之提高與基板等之接著性之效果優異，藉由與硬化性樹脂化學鍵結而可抑制硬化性樹脂流出至液晶中。 上述矽烷偶合劑可單獨地使用，亦可組合2種以上使用。As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-iso Cyanopropyl trimethoxysilane etc. These silane coupling agents have an excellent effect of improving adhesion to substrates and the like, and can chemically bond with the curable resin to suppress the outflow of the curable resin into the liquid crystal. The above-mentioned silane coupling agent may be used alone or in combination of two or more.
本發明之液晶顯示元件用密封劑100重量份中之上述矽烷偶合劑之含量之較佳之下限為0.1重量份，較佳之上限為10重量份。藉由上述矽烷偶合劑之含量為該範圍，從而抑制液晶污染之發生，且提高接著性之效果更加優異。上述矽烷偶合劑之含量之更佳之下限為0.3重量份，更佳之上限為5重量份。The preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is 0.1 part by weight, and the preferable upper limit is 10 parts by weight. With the content of the silane coupling agent in this range, the occurrence of liquid crystal contamination is suppressed, and the effect of improving the adhesion is more excellent. The lower limit of the content of the silane coupling agent is more preferably 0.3 part by weight, and the upper limit is more preferably 5 parts by weight.
本發明之液晶顯示元件用密封劑亦可含有遮光劑。藉由含有上述遮光劑，從而使得本發明之液晶顯示元件用密封劑可較好地用作遮光密封劑。The sealing compound for liquid crystal display elements of this invention may contain a light-shielding agent. By containing the above-mentioned light-shielding agent, the sealing agent for liquid crystal display elements of this invention can be used suitably as a light-shielding sealing agent.
作為上述遮光劑，例如可列舉：氧化鐵、鈦黑、苯胺黑、花青黑、富勒烯、碳黑、樹脂被覆型碳黑等。其中，較佳為鈦黑。Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Among them, titanium black is preferred.
上述鈦黑係相較於對於波長300 nm以上800 nm以下之光之平均透過率，對於紫外線區域附近、尤其是波長370 nm以上450 nm以下之光之透過率更高之物質。即，上述鈦黑係具有如下性質之遮光劑：藉由充分地遮斷可見光區域之波長之光而對本發明之液晶顯示元件用密封劑賦予遮光性，另一方面使紫外線區域附近之波長之光透過。因此，使用能夠藉由上述鈦黑之透過率更高之波長（370 nm以上450 nm以下）之光使得反應開始者作為上述光自由基聚合起始劑，藉此可進一步增強本發明之液晶顯示元件用密封劑之光硬化性。又，作為本發明之液晶顯示元件用密封劑所含有之遮光劑，較佳為高絕緣性之物質，鈦黑亦可較好地作為高絕緣性之遮光劑。 上述鈦黑之每1 μm之光學濃度（OD值）較佳為3以上，更佳為4以上。上述鈦黑之遮光性越高越好，上述鈦黑之OD值之較佳之上限無特別限制，通常為5以下。The above-mentioned titanium black has a higher transmittance than the average transmittance for light having a wavelength of 300 nm or more and 800 nm or less, and light in the vicinity of the ultraviolet region, especially light having a wavelength of 370 nm or more and 450 nm or less. That is, the above-mentioned titanium black is a light-shielding agent having the following properties: the light-shielding property is given to the sealing agent for liquid crystal display elements of the present invention by sufficiently blocking the light of the wavelength in the visible light region, and on the other hand, the light of the wavelength near the ultraviolet region Through. Therefore, the use of light with a higher wavelength (370 nm or more and 450 nm or less) through the above-mentioned titanium black to enable the reaction starter to act as the above-mentioned photo-radical polymerization initiator can thereby further enhance the liquid crystal display of the present invention The photocurability of the sealant for components. In addition, the opacifier contained in the sealing compound for liquid crystal display elements of the present invention is preferably a highly insulating substance, and titanium black can also be preferably used as a highly insulating opacifier. The optical density (OD value) per 1 μm of the titanium black is preferably 3 or more, and more preferably 4 or more. The higher the light shielding property of the titanium black, the better. The preferable upper limit of the OD value of the titanium black is not particularly limited, but is usually 5 or less.
上述鈦黑雖即便未經表面處理亦發揮充分之效果，但亦可使用經表面處理之鈦黑，如表面經偶合劑等有機成分處理者、或經氧化矽、氧化鈦、氧化鍺、氧化鋁、氧化鋯、氧化鎂等無機成分被覆者等。其中，就可更進一步提高絕緣性之觀點而言，較佳為經有機成分處理者。 又，使用含有上述鈦黑作為遮光劑之本發明之液晶顯示元件用密封劑所製造之液晶顯示元件由於具有充分之遮光性，故而可實現不會發生漏光而具有高對比度、具有優異之影像顯示品質之液晶顯示元件。Although the above-mentioned titanium black exerts sufficient effects even without surface treatment, surface-treated titanium black can also be used, such as those treated with organic components such as coupling agents, or silicon oxide, titanium oxide, germanium oxide, and aluminum oxide , Zirconium oxide, magnesium oxide and other inorganic components are covered. Among them, from the viewpoint that the insulating property can be further improved, those treated with organic components are preferred. In addition, the liquid crystal display element manufactured using the sealing agent for liquid crystal display elements of the present invention containing the above titanium black as a light-shielding agent has sufficient light-shielding properties, and therefore can achieve high contrast and excellent image display without light leakage Quality liquid crystal display element.
作為上述鈦黑之市售品，例如可列舉：三菱綜合材料公司製造之鈦黑、AKO KASEI公司製造之鈦黑等。 作為上述三菱綜合材料公司製造之鈦黑，例如可列舉：12S、13M、13M-C、13R-N、14M-C等。 作為上述AKO KASEI公司製造之鈦黑，例如可列舉：Tilack D等。Examples of the commercially available titanium black products include titanium black manufactured by Mitsubishi Materials Corporation and titanium black manufactured by AKO KASEI Corporation. Examples of the titanium black manufactured by Mitsubishi Materials Corporation include 12S, 13M, 13M-C, 13R-N, and 14M-C. Examples of the titanium black manufactured by AKO KASEI include Tilack D and the like.
上述鈦黑之比表面積之較佳之下限為13 m2 /g，較佳之上限為30 m2 /g，更佳之下限為15 m2 /g，更佳之上限為25 m2 /g。 又，上述鈦黑之體積電阻之較佳之下限為0.5 Ω・cm，較佳之上限為3 Ω・cm，更佳之下限為1 Ω・cm，更佳之上限為2.5 Ω・cm。The preferable lower limit of the specific surface area of the above titanium black is 13 m 2 /g, the preferable upper limit is 30 m 2 /g, the more preferable lower limit is 15 m 2 /g, and the more preferable upper limit is 25 m 2 /g. In addition, the preferable lower limit of the volume resistance of the above titanium black is 0.5 Ω·cm, the preferable upper limit is 3 Ω·cm, the more preferable lower limit is 1 Ω·cm, and the more preferable upper limit is 2.5 Ω·cm.
關於上述遮光劑之一次粒徑，只要為液晶顯示元件之基板間之距離以下，則無特別限定，較佳之下限為1 nm，較佳之上限為5000 nm。藉由上述遮光劑之一次粒徑為該範圍，從而可於不使所獲得之液晶顯示元件用密封劑之塗佈性等變差之情況下使遮光性更加優異。上述遮光劑之一次粒徑之更佳之下限為5 nm，更佳之上限為200 nm，進而較佳之下限為10 nm，進而較佳之上限為100 nm。 再者，上述遮光劑之一次粒徑可使用NICOMP 380ZLS（PARTICLE SIZING SYSTEMS公司製造），使上述遮光劑分散於溶劑（水、有機溶劑等）中而測定。The primary particle size of the above-mentioned opacifier is not particularly limited as long as the distance between the substrates of the liquid crystal display element is less than the preferred lower limit is 1 nm, and the preferred upper limit is 5000 nm. When the primary particle size of the above-mentioned light-shielding agent is in this range, the light-shielding property can be made more excellent without deteriorating the coating properties of the obtained sealing compound for liquid crystal display elements. The preferred lower limit of the primary particle size of the above-mentioned opacifier is 5 nm, the more preferred upper limit is 200 nm, the further preferred lower limit is 10 nm, and the further preferred upper limit is 100 nm. In addition, the primary particle diameter of the said sunscreen can be measured using NICOMP 380ZLS (made by PARTICLE SIZING SYSTEMS), and dispersing the said sunscreen in a solvent (water, organic solvent, etc.).
本發明之液晶顯示元件用密封劑100重量份中之上述遮光劑之含量之較佳之下限為5重量份，較佳之上限為80重量份。藉由上述遮光劑之含量為該範圍，從而可於不使所獲得之液晶顯示元件用密封劑之接著性、硬化後之強度、及繪圖性降低之情況下，進一步發揮提高遮光性之效果。上述遮光劑之含量之更佳之下限為10重量份，更佳之上限為70重量份，進而較佳之下限為30重量份，進而較佳之上限為60重量份。The lower limit of the content of the light-shielding agent in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is preferably 5 parts by weight, and the upper limit is preferably 80 parts by weight. With the content of the above-mentioned light-shielding agent in this range, the effect of improving the light-shielding property can be further exerted without reducing the adhesiveness, strength after hardening, and drawability of the obtained sealant for liquid crystal display elements. The lower limit of the content of the above-mentioned opacifier is more preferably 10 parts by weight, the more preferable upper limit is 70 parts by weight, the more preferable lower limit is 30 parts by weight, and the more preferable upper limit is 60 parts by weight.
本發明之液晶顯示元件用密封劑亦可視需要進而含有應力緩和劑、反應性稀釋劑、觸變劑、間隔物、硬化促進劑、消泡劑、調平劑、聚合抑制劑等添加劑。The sealing agent for liquid crystal display elements of the present invention may further contain additives such as a stress relaxation agent, a reactive diluent, a thixotropic agent, a spacer, a hardening accelerator, a defoaming agent, a leveling agent, and a polymerization inhibitor, if necessary.
作為製造本發明之液晶顯示元件用密封劑之方法，例如可列舉以下方法等：使用勻相分散機、均質攪拌機、萬能攪拌機、行星式混合機、捏合機、三輥研磨機等混合機，將硬化性樹脂、聚合起始劑及/或熱硬化劑、及視需要所添加之矽烷偶合劑等添加劑進行混合。As a method of manufacturing the sealing agent for liquid crystal display elements of the present invention, for example, the following methods may be mentioned: a mixer such as a homogeneous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roll mill, etc. is used. Additives such as curable resin, polymerization initiator and/or thermosetting agent, and silane coupling agent added as needed.
藉由向本發明之液晶顯示元件用密封劑中摻合導電性微粒子，從而可製造上下導通材料。此種含有本發明之液晶顯示元件用密封劑與導電性微粒子之上下導通材料亦為本發明之一。By blending conductive fine particles into the sealant for liquid crystal display elements of the present invention, a vertical conduction material can be manufactured. Such a top-to-bottom conductive material containing the sealing compound for liquid crystal display elements of the present invention and conductive fine particles is also one of the present invention.
作為上述導電性微粒子，可使用金屬球、於樹脂微粒子之表面形成有導電金屬層者等。其中，於樹脂微粒子之表面形成有導電金屬層者藉由樹脂微粒子之優異之彈性而能夠於不損傷透明基板等之情況下實現導電連接，因此較佳。As the conductive fine particles, a metal ball, a conductive metal layer formed on the surface of the resin fine particles, or the like can be used. Among them, those having a conductive metal layer formed on the surface of the resin microparticles can achieve conductive connection without damaging the transparent substrate or the like due to the excellent elasticity of the resin microparticles, which is preferable.
使用本發明之液晶顯示元件用密封劑或本發明之上下導通材料而成之液晶顯示元件亦為本發明之一。A liquid crystal display element using the sealing compound for liquid crystal display elements of the present invention or the upper and lower conduction materials of the present invention is also one of the present invention.
本發明之液晶顯示元件用密封劑可較好地用於利用液晶滴下法之液晶顯示元件之製造。作為利用液晶滴下法製造本發明之液晶顯示元件之方法，例如可列舉以下方法等。 首先，進行以下步驟：藉由網版印刷、滴塗塗佈等於基板上塗佈本發明之液晶顯示元件用密封劑，形成框狀之密封圖案。繼而，進行以下步驟：於本發明之液晶顯示元件用密封劑等未硬化之狀態下，將液晶之微滴滴下塗佈於密封圖案之框內整個面，其後立即使另一基板重合。其後，進行對密封圖案部分照射紫外線等光使密封劑暫時硬化之步驟、及對暫時硬化之密封劑進行加熱使其正式硬化之步驟，藉由以上方法可獲得液晶顯示元件。 發明之效果The sealing agent for liquid crystal display elements of this invention can be used suitably for the manufacture of a liquid crystal display element by the liquid crystal dropping method. As a method of manufacturing the liquid crystal display element of the present invention by the liquid crystal dropping method, for example, the following methods can be cited. First, the following steps are performed: a screen-shaped seal pattern is formed by screen printing and drip coating equal to applying the sealant for a liquid crystal display element of the present invention on a substrate. Then, the following steps are performed: in a state where the sealant for liquid crystal display elements of the present invention and the like are not cured, droplets of liquid crystal are dropped and applied to the entire surface of the frame of the seal pattern, and immediately after that, another substrate is overlapped. Thereafter, a step of irradiating the sealing pattern portion with light such as ultraviolet rays to temporarily harden the sealant, and a step of heating the temporarily hardened sealant to formally harden the liquid crystal display element can be obtained by the above method. Effect of invention
根據本發明，可提供一種即便於異型加工時亦可維持優異之接著性之液晶顯示元件用密封劑。又，根據本發明，可提供一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。According to the present invention, it is possible to provide a sealant for a liquid crystal display element that can maintain excellent adhesiveness even during profile processing. In addition, according to the present invention, it is possible to provide an upper and lower conduction material and a liquid crystal display element using the sealant for a liquid crystal display element.
以下，揭示實施例對本發明進而詳細地進行說明，但本發明並非僅限定於該等實施例。Hereinafter, the present invention will be described in further detail by revealing examples, but the present invention is not limited to these examples.
（實施例1〜8、比較例1〜4） 依據表1中所記載之摻合比，使用行星式攪拌機（Thinky公司製造，「去泡攪拌太郎」）將各材料混合，其後進而使用三輥研磨機進行混合，藉此製備實施例1〜8及比較例1〜4之液晶顯示元件用密封劑。 於長度45 mm、寬度25 mm、厚度0.7 mm之2片聚醯亞胺基板之一基板上以接著時之直徑為3 mm之方式點塗所獲得之液晶顯示元件用密封劑。使另一聚醯亞胺基板以於長邊方向上錯開10 mm之方式經由密封劑重合於點塗有密封劑之聚醯亞胺基板。其後，使用金屬鹵化物燈等照射100 mW/cm2 之紫外線（波長365 nm）30秒鐘後，於120℃加熱1小時，而使密封劑硬化，獲得試片。對所獲得之試片，使用自動立體測圖儀AGX（島津製作所製造），藉由依據JIS K 6852之常態試驗，測定於25℃之壓縮剪切接著強度。將結果示於表1。 又，對所獲得之各液晶顯示元件用密封劑，使用金屬鹵化物燈照射100 mW/cm2 之紫外線（波長365 nm）30秒鐘後，於120℃加熱1小時，而獲得硬化物。對所獲得之硬化物，使用動態黏彈性測定裝置，以試片寬度5 mm、厚度0.35 mm、抓持寬度25 mm、升溫速度10℃/分鐘、頻率10 Hz之條件測定儲存彈性模數。又，求出損耗正切（tanδ）之極大值之溫度作為玻璃轉移溫度。使用DVA-200（IT計測制御公司製造）作為上述動態黏彈性測定裝置。將儲存彈性模數及玻璃轉移溫度之測定結果示於表1。(Examples 1 to 8, Comparative Examples 1 to 4) According to the blending ratio described in Table 1, each material was mixed using a planetary mixer (manufactured by Thinky, "Defoaming and Mixing Taro"), and then used three The roller grinder was mixed, thereby preparing the sealants for liquid crystal display elements of Examples 1 to 8 and Comparative Examples 1 to 4. On one of the two polyimide substrates with a length of 45 mm, a width of 25 mm, and a thickness of 0.7 mm, a sealant for liquid crystal display elements was spot-coated with a diameter of 3 mm. The other polyimide substrate was overlapped with the sealant-coated polyimide substrate via the sealant so as to be offset by 10 mm in the longitudinal direction. Thereafter, after irradiating 100 mW/cm 2 of ultraviolet light (wavelength 365 nm) for 30 seconds using a metal halide lamp or the like, the sealant was cured by heating at 120° C. for 1 hour to obtain a test piece. For the obtained test piece, an autostereograph AGX (manufactured by Shimadzu Corporation) was used to measure the compression shear adhesion strength at 25°C by a normal test in accordance with JIS K 6852. The results are shown in Table 1. Furthermore, the obtained sealing compound for liquid crystal display elements was irradiated with 100 mW/cm 2 of ultraviolet light (wavelength 365 nm) for 30 seconds using a metal halide lamp, and then heated at 120° C. for 1 hour to obtain a cured product. Using the dynamic viscoelasticity measuring device for the obtained hardened product, the storage elastic modulus was measured under the conditions of test piece width 5 mm, thickness 0.35 mm, grip width 25 mm, heating rate 10°C/min, frequency 10 Hz. Furthermore, the temperature at which the maximum value of the loss tangent (tanδ) is obtained is taken as the glass transition temperature. As the above dynamic viscoelasticity measuring device, DVA-200 (manufactured by IT Measurement Manufacturing Co., Ltd.) was used. Table 1 shows the measurement results of the storage elastic modulus and glass transition temperature.
＜評價＞ 對實施例及比較例中所獲得之各液晶顯示元件用密封劑進行以下之評價。將結果示於表1。<Evaluation> The following evaluation was performed about each sealing compound for liquid crystal display elements obtained in the Example and the comparative example. The results are shown in Table 1.
（異型加工時之接著性） 使間隔物微粒子（積水化學工業公司製造，「Micropearl SI-H050」）1重量份分散於實施例及比較例中所獲得之各液晶顯示元件用密封劑100重量份。繼而，將分散有間隔物微粒子之密封劑滴塗塗佈於2片附有經過摩擦處理之配向膜及透明電極之基板（長度75 mm、寬度75 mm、厚度0.7 mm）之一基板上。密封劑之塗佈形狀為與於長度45 mm、寬度55 mm之範圍之上部具有長度5 mm、寬度10 mm之邊緣部分之液晶顯示元件之顯示區域對應的線寬0.7 mm之框狀。繼而，將液晶（Chisso公司製造，「JC-5004LA」）之微滴滴下塗佈於密封劑之框內整個面，其後立即使另一基板貼合，使用金屬鹵化物燈對密封劑部分照射100 mW/cm2 之紫外線（波長365 nm）30秒鐘後，於120℃加熱1小時，藉此獲得液晶顯示元件。關於實施例及比較例中所獲得之各液晶顯示元件用密封劑，分別各製作10單元液晶顯示元件。 對所獲得之各液晶顯示元件，進行使用微型研磨機對密封周邊及邊緣部分進行加工直至距密封邊界1 mm為止之研磨試驗。研磨試驗後，將全部單元均未發生因剝落或破裂而造成之液晶漏液之情形設為「◎」、將1單元以上且未達4單元之液晶顯示元件發生液晶漏液之情形設為「○」、將4單元以上且未達7單元之液晶顯示元件發生液晶漏液之情形設為「Δ」、將7單元以上之液晶顯示元件發生液晶漏液之情形設為「×」，以此評價接著性。(Adhesion during profile processing) 1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Industry Co., Ltd., "Micropearl SI-H050") was dispersed in 100 parts by weight of each sealant for liquid crystal display elements obtained in Examples and Comparative Examples . Then, the sealant in which the fine particles of the spacers were dispersed was applied onto one substrate of two substrates (length 75 mm, width 75 mm, thickness 0.7 mm) with an alignment film and a transparent electrode subjected to rubbing treatment. The coating shape of the sealant is a frame shape with a line width of 0.7 mm corresponding to the display area of the liquid crystal display element having an edge portion of 5 mm in length and 10 mm in width above the range of 45 mm in length and 55 mm in width. Then, droplets of liquid crystal (manufactured by Chisso Corporation, "JC-5004LA") were dropped onto the entire surface of the frame of the sealant, and immediately after that, another substrate was bonded, and the sealant was partially irradiated with a metal halide lamp After 30 seconds of ultraviolet light (wavelength 365 nm) of 100 mW/cm 2 , it was heated at 120°C for 1 hour, thereby obtaining a liquid crystal display element. About the sealing compound for liquid crystal display elements obtained by the Example and the comparative example, 10 unit liquid crystal display elements were each produced. For each obtained liquid crystal display element, a grinding test was performed using a micro-grinding machine to process the periphery and edge of the seal until it was 1 mm from the seal boundary. After the grinding test, the case where no liquid crystal leakage due to peeling or cracking occurred in all the units was set to "◎", and the case where liquid crystal leakage occurred in the liquid crystal display element of 1 unit or more and less than 4 units was set to "○", the liquid crystal display element of more than 4 units and less than 7 units is set to "Δ", and the liquid crystal display element of 7 units or more is set to "×". Evaluation of adherence.
[表1]
根據本發明，可提供一種即便於異型加工時亦可維持優異之接著性之液晶顯示元件用密封劑。又，根據本發明，可提供一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。According to the present invention, it is possible to provide a sealant for a liquid crystal display element that can maintain excellent adhesiveness even during profile processing. In addition, according to the present invention, it is possible to provide an upper and lower conduction material and a liquid crystal display element using the sealant for a liquid crystal display element.
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2019
- 2019-07-11 WO PCT/JP2019/027484 patent/WO2020013272A1/en not_active Ceased
- 2019-07-11 JP JP2019545829A patent/JP6835980B2/en active Active
- 2019-07-12 TW TW108124623A patent/TWI848961B/en active
-
2021
- 2021-01-28 JP JP2021012037A patent/JP2021073530A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| TWI848961B (en) | 2024-07-21 |
| JP2021073530A (en) | 2021-05-13 |
| JPWO2020013272A1 (en) | 2020-08-06 |
| JP6835980B2 (en) | 2021-02-24 |
| WO2020013272A1 (en) | 2020-01-16 |
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