TW201819505A - Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element - Google Patents
Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element Download PDFInfo
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- TW201819505A TW201819505A TW106133276A TW106133276A TW201819505A TW 201819505 A TW201819505 A TW 201819505A TW 106133276 A TW106133276 A TW 106133276A TW 106133276 A TW106133276 A TW 106133276A TW 201819505 A TW201819505 A TW 201819505A
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- Prior art keywords
- liquid crystal
- meth
- crystal display
- acrylate
- display element
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 121
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 45
- 238000007789 sealing Methods 0.000 title claims abstract description 37
- 239000004020 conductor Substances 0.000 title claims abstract description 10
- -1 acrylic compound Chemical class 0.000 claims abstract description 89
- 150000001875 compounds Chemical class 0.000 claims abstract description 58
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- 239000003999 initiator Substances 0.000 claims abstract description 34
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- 239000000565 sealant Substances 0.000 claims description 61
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- 239000010419 fine particle Substances 0.000 claims description 6
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
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- 238000011109 contamination Methods 0.000 abstract description 16
- 230000001747 exhibiting effect Effects 0.000 abstract 1
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- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 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
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- JRSJRHKJPOJTMS-UHFFFAOYSA-N trimethoxy(2-phenylethenyl)silane Chemical compound CO[Si](OC)(OC)C=CC1=CC=CC=C1 JRSJRHKJPOJTMS-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 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
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000011787 zinc oxide Substances 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)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Mathematical Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Liquid Crystal (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本發明係關於一種遮光部硬化性優異，且可抑制液晶污染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, which is excellent in the light-shielding portion and has a curable property and can suppress liquid crystal contamination. The present invention also relates to a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.
近年來，作為液晶顯示單元等液晶顯示元件之製造方法，就產距時間(Tact Time)縮短、使用液晶量之最佳化等觀點而言，使用如專利文獻1、專利文獻2所揭示的被稱為滴下法之液晶滴下方式，該方式係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者。 In recent years, as a method for manufacturing a liquid crystal display element such as a liquid crystal display unit, from the viewpoints of shortening the production time (Tact Time) and optimizing the amount of liquid crystal used, the methods described in Patent Documents 1 and 2 are used. The liquid crystal dropping method, which is called a dripping method, is a method in which a photo-thermal combined hardening sealant containing a curable resin, a photopolymerization initiator, and a thermosetting agent is used.
於滴下法中，首先，藉由點膠(dispense)於2片附電極之透明基板之一片上形成長方形狀之密封圖案。其次，於密封劑未硬化之狀態下將液晶之微小液滴滴至透明基板之框內整個面，立即與另一片透明基板重疊，對密封部照射紫外線等光而進行暫時硬化。其後，於液晶退火時進行加熱而進行正式硬化，從而製作液晶顯示元件。若於減壓下進行基板之貼合，則可以極高效率製造液晶顯示元件，目前該滴下法成為液晶顯示元件之製造 方法之主流。 In the dropping method, first, a rectangular seal pattern is formed on one of the two transparent substrates with electrodes by dispensing. Next, in the state where the sealant is not hardened, minute liquid droplets of the liquid crystal are dropped on the entire surface inside the frame of the transparent substrate, and immediately overlap with another transparent substrate, and the sealing portion is irradiated with light such as ultraviolet rays to be temporarily hardened. Thereafter, the liquid crystal display element is produced by heating and performing main curing during the annealing of the liquid crystal. If the substrates are bonded under reduced pressure, the liquid crystal display element can be manufactured with extremely high efficiency. At present, the dripping method has become the mainstream of the manufacturing method of the liquid crystal display element.
另外，於行動電話、攜帶型遊戲機等各種附液晶面板之移動設備已普及之現今，裝置之小型化為最被需要之課題。作為使裝置小型化之方法，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(以下，亦稱為窄邊緣設計)。 In addition, nowadays, various mobile devices with a liquid crystal panel, such as a mobile phone and a portable game machine, have become widespread, and miniaturization of the device is the most required issue. As a method for miniaturizing the device, narrow edge of the liquid crystal display portion can be cited, for example, the position of the sealing portion is arranged under a black matrix (hereinafter, also referred to as a narrow edge design).
然而，窄邊緣設計存在如下問題：由於將密封劑配置於黑矩陣之正下方，故而若進行滴下法，則使密封劑光硬化時所照射之光被遮蔽，光未到達至密封劑之內部從而硬化變得不充分。若如上所述密封劑之硬化變得不充分，則存在如下問題：未硬化之密封劑成分溶出至液晶中，而於液晶中會進行由所溶出之密封劑成分引起之硬化反應，由此導致產生液晶污染。 However, the narrow edge design has the following problems: Since the sealant is arranged directly below the black matrix, if the dropping method is performed, the light irradiated when the sealant is light-cured is blocked, and the light does not reach the inside of the sealant, thereby Hardening becomes insufficient. If the hardening of the sealant becomes insufficient as described above, there is a problem that an unhardened sealant component is eluted into the liquid crystal, and a hardening reaction caused by the dissolved sealant component proceeds in the liquid crystal, thereby causing Liquid crystal pollution occurs.
作為抑制液晶污染之方法，於專利文獻3中揭示有於密封劑中摻合高感度之光聚合起始劑之情況。然而，若僅摻合高感度之光聚合起始劑，則無法於遮光部充分地抑制液晶污染。 As a method for suppressing liquid crystal contamination, Patent Document 3 discloses a case where a high-sensitivity photopolymerization initiator is added to a sealant. However, if only a high-sensitivity photopolymerization initiator is blended, liquid crystal contamination cannot be sufficiently suppressed in the light-shielding portion.
先前技術文獻 Prior art literature
專利文獻 Patent literature
專利文獻1：日本特開2001-133794號公報 Patent Document 1: Japanese Patent Laid-Open No. 2001-133794
專利文獻2：國際公開第02/092718號 Patent Document 2: International Publication No. 02/092718
專利文獻3：國際公開第2012/002028號 Patent Document 3: International Publication No. 2012/002028
本發明之目的在於提供一種遮光部硬化性優異，且可抑制液晶污染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。 An object of the present invention is to provide a sealant for a liquid crystal display element that is excellent in the light-shielding portion and has a curable property and can suppress liquid crystal contamination. Another object of the present invention is to provide a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.
本發明係一種液晶顯示元件用密封劑，其係含有硬化性樹脂與光聚合起始劑者，上述硬化性樹脂含有(甲基)丙烯酸化合物及芳香族環氧化合物，上述光聚合起始劑含有下述式(1)所表示之化合物，上述硬化性樹脂與上述光聚合起始劑之SP值之差為2.5以下。 The present invention is a sealant for a liquid crystal display element, which contains a curable resin and a photopolymerization initiator, the curable resin contains a (meth) acrylic compound and an aromatic epoxy compound, and the photopolymerization initiator contains For the compound represented by the following formula (1), the difference between the SP values of the curable resin and the photopolymerization initiator is 2.5 or less.
以下對本發明詳細地進行說明。 The present invention will be described in detail below.
本發明人認為即便使用高感度之光聚合起始劑亦無法使遮光部硬化性充分地提高之原因在於：光聚合起始劑對於硬化性樹脂之較低溶解性。因此，本發明人發現，藉由以SP值之差成為特定值以下之方式組合特定化合物而用作硬化性樹脂及作為光聚合起始劑，可獲得遮光部硬化性優異，且 可抑制液晶污染之液晶顯示元件用密封劑，從而完成本發明。 The present inventors believe that the reason why the light-shielding part can not sufficiently improve the curing property of the light-shielding portion even when using a high-sensitivity photopolymerization initiator is that the photopolymerization initiator has relatively low solubility to the curable resin. Therefore, the present inventors have found that by combining specific compounds so that the difference between the SP values becomes equal to or lower than a specific value, the compound can be used as a curable resin and as a photopolymerization initiator to obtain excellent light-shielding part curing properties and suppress liquid crystal contamination A sealing agent for a liquid crystal display element has been completed to complete the present invention.
本發明之液晶顯示元件用密封劑含有硬化性樹脂。 The sealing agent for liquid crystal display elements of this invention contains a curable resin.
上述硬化性樹脂含有(甲基)丙烯酸化合物及芳香族環氧化合物。藉由將上述(甲基)丙烯酸化合物與上述芳香族環氧化合物組合使用，所獲得之液晶顯示元件用密封劑成為兼顧接著性與液晶污染之效果優異者。 The curable resin contains a (meth) acrylic compound and an aromatic epoxy compound. By using the (meth) acrylic compound and the aromatic epoxy compound in combination, the obtained sealing agent for a liquid crystal display element becomes an excellent one having both the adhesiveness and liquid crystal contamination.
再者，於本說明書中，所謂上述「(甲基)丙烯酸」，意指丙烯酸或甲基丙烯酸，所謂上述「(甲基)丙烯酸化合物」，意指具有(甲基)丙烯醯基之化合物，所謂上述「(甲基)丙烯醯基」，意指丙烯醯基或甲基丙烯醯基。又，本說明書中，所謂上述「芳香族環氧化合物」，意指具有芳香環與環氧基之化合物。 In addition, in the present specification, the "(meth) acrylic acid" means acrylic acid or methacrylic acid, and the "(meth) acrylic compound" means a compound having a (meth) acryl group, The above-mentioned "(meth) acrylfluorenyl" means acrylfluorenyl or methacrylfluorenyl. In the present specification, the "aromatic epoxy compound" means a compound having an aromatic ring and an epoxy group.
作為上述(甲基)丙烯酸化合物，例如可列舉：(甲基)丙烯酸酯化合物、環氧(甲基)丙烯酸酯、(甲基)丙烯酸胺酯等。其中，較佳為環氧(甲基)丙烯酸酯。又，就反應性之高低而言，上述(甲基)丙烯酸化合物較佳為分子中具有2個以上之(甲基)丙烯醯基者。 Examples of the (meth) acrylic compound include (meth) acrylate compounds, epoxy (meth) acrylates, and (meth) acrylates. Among these, epoxy (meth) acrylate is preferable. In terms of the level of reactivity, the (meth) acrylic compound is preferably one having two (meth) acrylfluorenyl groups in the molecule.
再者，於本說明書中，所謂上述「(甲基)丙烯酸酯」，意指丙烯酸酯或甲基丙烯酸酯，所謂上述「環氧(甲基)丙烯酸酯」，係表示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。 In addition, in the present specification, the "(meth) acrylate" means an acrylate or a methacrylate, and the "epoxy (meth) acrylate" means that an epoxy compound A compound obtained by reacting all epoxy groups with (meth) acrylic acid.
作為上述(甲基)丙烯酸酯化合物中之單官能者，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸異肉豆蔻 酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰基酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-丁氧基乙酯、(甲基)丙烯酸2-苯氧基乙酯、甲氧基乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、苯氧基二乙二醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠酯、乙基卡必醇(甲基)丙烯酸酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、(甲基)丙烯酸1H,1H,5H-八氟戊酯、醯亞胺(甲基)丙烯酸酯、(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯、琥珀酸2-(甲基)丙烯醯氧乙酯、六氫鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯、2-羥基丙基鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯、磷酸2-(甲基)丙烯醯氧基乙酯、(甲基)丙烯酸縮水甘油酯等。 Examples of the monofunctional compound in the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate. Ester, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate , Isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, ( Isoamyl (meth) acrylate, dicyclopentene (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxy (meth) acrylate Ethyl ester, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (Meth) acrylate, phenoxydiethyl Alcohol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethylcarbitol (meth) acrylate, (meth) acrylate 2 , 2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, fluorenimine (methyl ) Acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acrylic acid ethoxyethyl succinate, 2-hexamethyl phthalate 2- (Meth) acrylic acid ethoxyethyl ester, 2-hydroxypropyl phthalate 2- (meth) acrylic acid ethoxylate, 2- (meth) acrylic acid ethoxylate phosphate, (methyl ) Glycidyl acrylate and the like.
又，作為上述(甲基)丙烯酸酯化合物中之2官能者，例如可列舉：1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、2-正丁基-2-乙基-1,3-丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、環氧乙烷加成雙酚A二(甲基)丙烯酸酯、環氧丙烷加成雙酚A二(甲基)丙烯酸酯、環氧乙烷加成雙酚F二(甲基)丙烯酸酯、二(甲基)丙烯酸二羥 甲基二環戊二烯酯、環氧乙烷改質異三聚氰酸二(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、碳酸酯二醇二(甲基)丙烯酸酯、聚醚二醇二(甲基)丙烯酸酯、聚酯二醇二(甲基)丙烯酸酯、聚己內酯二醇二(甲基)丙烯酸酯、聚丁二烯二醇二(甲基)丙烯酸酯等。 Examples of the bifunctional compound in the (meth) acrylate compound include 1,3-butanediol di (meth) acrylate and 1,4-butanediol di (meth) acrylate. , 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, ethylene glycol di (Meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2 -Ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl Alcohol di (meth) acrylate, ethylene oxide addition bisphenol A di (meth) acrylate, propylene oxide addition bisphenol A di (meth) acrylate, ethylene oxide addition bisphenol F di (meth) acrylate, dimethylol dicyclopentadiene di (meth) acrylate, ethylene oxide modified isotricyanate di (meth) acrylate, (meth) acrylic acid 2-Hydroxy-3- (meth) propylene ethoxypropyl ester, carbonate diol di (meth) propylene Ester, polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol di (meth) ) Acrylate, etc.
又，作為上述(甲基)丙烯酸酯化合物中之3官能以上者，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷加成三羥甲基丙烷三(甲基)丙烯酸酯、環氧丙烷加成三羥甲基丙烷三(甲基)丙烯酸酯、己內酯改質三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷加成異三聚氰酸三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、環氧丙烷加成甘油三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、磷酸三(甲基)丙烯醯氧基乙酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等。 In addition, examples of the tri- or more functional group in the (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, and ethylene oxide-added trimethylolpropane tri (methyl) ) Acrylate, propylene oxide addition trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, ethylene oxide addition isocyanuric acid Acid tri (meth) acrylate, glycerol tri (meth) acrylate, propylene oxide addition glycerol tri (meth) acrylate, neopentyl tetraol tri (meth) acrylate, phosphate tri (meth) acrylate Acrylic ethoxyethyl, di-trimethylolpropane tetra (meth) acrylate, neopentaerythritol tetra (meth) acrylate, dinepentaerythritol penta (meth) acrylate, dineopentyl Tetraol hexa (meth) acrylate and the like.
作為上述環氧(甲基)丙烯酸酯，例如可列舉：依據常規方法使環氧化合物與(甲基)丙烯酸於鹼性觸媒之存在下進行反應而獲得者等。 Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst in accordance with a conventional method.
作為用以合成上述環氧(甲基)丙烯酸酯之原料的環氧化合物，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、環氧丙烷加成雙酚A型環氧樹脂、間苯二酚型環氧樹脂、聯苯型環氧樹脂、硫醚型環氧樹脂、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、縮水甘油胺型環氧樹脂、烷基多元醇型環氧樹脂、橡膠改質型環氧樹脂、 縮水甘油酯化合物等。 Examples of the epoxy compound used as a raw material for synthesizing the epoxy (meth) acrylate include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and 2, 2'-diallyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl epoxy Resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin , Dicyclopentadiene novolac epoxy resin, biphenol novolac epoxy resin, naphthol novolac epoxy resin, glycidylamine epoxy resin, alkyl polyol epoxy resin, rubber modification Quality epoxy resin, glycidyl ester compound, etc.
作為上述雙酚A型環氧樹脂中之市售者，例如可列舉：jER828EL、jER1004(均為三菱化學公司製造)；EPICLON EXA-830CRP、EPICLON EXA-850CRP(DIC公司製造)等。 Examples of commercially available bisphenol A epoxy resins include jER828EL and jER1004 (both manufactured by Mitsubishi Chemical Corporation); EPICLON EXA-830CRP and EPICLON EXA-850CRP (manufactured by DIC Corporation).
作為上述雙酚F型環氧樹脂中之市售者，例如可列舉：jER806、jER4004(均為三菱化學公司製造)等。 Examples of commercially available bisphenol F-type epoxy resins include jER806 and jER4004 (both manufactured by Mitsubishi Chemical Corporation).
作為上述雙酚S型環氧樹脂中之市售者，例如可列舉：EPICLON EXA1514(DIC公司製造)等。 Examples of a commercially available bisphenol S-type epoxy resin include EPICLON EXA1514 (manufactured by DIC Corporation).
作為上述2,2'-二烯丙基雙酚A型環氧樹脂中之市售者，例如可列舉：RE-810NM(日本化藥公司製造)等。 Examples of the commercially available 2,2'-diallyl bisphenol A type epoxy resin include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
作為上述氫化雙酚型環氧樹脂中之市售者，例如可列舉：EPICLON EXA7015(DIC公司製造)等。 As a marketer among the said hydrogenated bisphenol-type epoxy resins, Epiclon EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
作為上述環氧丙烷加成雙酚A型環氧樹脂中之市售者，例如可列舉：EP-4000S(ADEKA公司製造)等。 Examples of a commercially available propylene oxide-added bisphenol A type epoxy resin include EP-4000S (manufactured by ADEKA).
作為上述間苯二酚型環氧樹脂中之市售者，例如可列舉：EX-201(Nagase ChemteX公司製造)等。 As a marketer among the said resorcinol-type epoxy resins, EX-201 (made by Nagase ChemteX company) etc. are mentioned, for example.
作為上述聯苯型環氧樹脂中之市售者，例如可列舉：jER YX-4000H(三菱化學公司製造)等。 Examples of the commercially available biphenyl type epoxy resin include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
作為上述硫醚型環氧樹脂中之市售者，例如可列舉：YSLV-50TE(新日鐵住金化學公司製造)等。 Examples of a commercially available thioether-type epoxy resin include YSLV-50TE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.).
作為上述二苯醚型環氧樹脂中之市售者，例如可列舉：YSLV-80DE(新日鐵住金化學公司製造)等。 Examples of a commercially available diphenyl ether type epoxy resin include YSLV-80DE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and the like.
作為上述二環戊二烯型環氧樹脂中之市售者，例如可列舉：EP-4088S(ADEKA公司製造)等。 Examples of a commercially available dicyclopentadiene type epoxy resin include EP-4088S (manufactured by ADEKA).
作為上述萘型環氧樹脂中之市售者，例如可列舉：EPICLON HP 4032、EPICLON EXA-4700(均為DIC公司製造)等。 Examples of the commercially available naphthalene-type epoxy resin include EPICLON HP 4032 and EPICLON EXA-4700 (both manufactured by DIC Corporation).
作為上述苯酚酚醛清漆型環氧樹脂中之市售者，例如可列舉：EPICLONN-770(DIC公司製造)等。 As a commercially available one among the said phenol novolak-type epoxy resins, EPICLONN-770 (made by DIC Corporation) etc. are mentioned, for example.
作為上述鄰甲酚酚醛清漆型環氧樹脂中之市售者，例如可列舉：EPICLONN-670-EXP-S(DIC公司製造)等。 Examples of the commercially available o-cresol novolac-type epoxy resin include EPICLONN-670-EXP-S (manufactured by DIC Corporation) and the like.
作為上述二環戊二烯酚醛清漆型環氧樹脂中之市售者，例如可列舉：EPICLON HP7200(DIC公司製造)等。 Examples of a commercially available dicyclopentadiene novolac epoxy resin include EPICLON HP7200 (manufactured by DIC Corporation).
作為上述聯苯酚醛清漆型環氧樹脂中之市售者，例如可列舉：NC-3000P(日本化藥公司製造)等。 As a marketer of the said biphenol novolak-type epoxy resin, NC-3000P (made by Nippon Kayakusho), etc. are mentioned, for example.
作為上述萘酚酚醛清漆型環氧樹脂中之市售者，例如可列舉：ESN-165S(新日鐵住金化學公司製造)等。 As a marketer of the said naphthol novolak-type epoxy resin, ESN-165S (made by Nippon Steel & Sumikin Chemical Co., Ltd.) etc. are mentioned, for example.
作為上述縮水甘油胺型環氧樹脂中之市售者，例如可列舉：jER630(三菱化學公司製造)、EPICLON 430(DIC公司製造)、TETRAD-X(三菱瓦斯化學公司製造)等。 Examples of a commercially available glycidylamine type epoxy resin include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation), and the like.
作為上述烷基多元醇型環氧樹脂中之市售者，例如可列舉：ZX-1542(新日鐵住金化學公司製造)、EPICLON 726(DIC公司製造)、Epolight 80MFA(共榮社化學公司製造)、DENACOL EX-611(Nagase ChemteX公司製造)等。 As a marketer of the above-mentioned alkyl polyol type epoxy resin, for example, ZX-1542 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), EPICLON 726 (manufactured by DIC Corporation), and Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) ), DENACOL EX-611 (manufactured by Nagase ChemteX) and the like.
作為上述橡膠改質型環氧樹脂中之市售者，例如可列舉：YR-450、 YR-207(均為新日鐵住金化學公司製造)；Epolead PB(Daicel公司製造)等。 Examples of commercially available rubber modified epoxy resins include YR-450 and YR-207 (both manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.); Epolead PB (made by Daicel).
作為上述縮水甘油酯化合物中之市售者，例如可列舉：DENACOL EX-147(Nagase ChemteX公司製造)等。 Examples of a commercially available glycidyl ester compound include DENACOL EX-147 (manufactured by Nagase ChemteX).
作為上述環氧化合物中之其他市售者，例如可列舉：YDC-1312、YSLV-80XY、YSLV-90CR(均為新日鐵住金化學公司製造)；XAC 4151(旭化成公司製造)；jER1031、jER1032(均為三菱化學公司製造)；EXA-7120(DIC公司製造)；TEPIC(日產化學公司製造)等。 Examples of other commercially available epoxy compounds include: YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.); XAC 4151 (made by Asahi Kasei Corporation); jER1031, jER1032 (All manufactured by Mitsubishi Chemical Corporation); EXA-7120 (made by DIC Corporation); TEPIC (made by Nissan Chemical Corporation), etc.
作為上述環氧(甲基)丙烯酸酯中之市售者，例如可列舉：EBECRYL 860、EBECRYL 3200、EBECRYL 3201、EBECRYL 3412、EBECRYL 3600、EBECRYL 3700、EBECRYL 3701、EBECRYL 3702、EBECRYL 3703、EBECRYL 3800、EBECRYL 6040、EBECRYL RDX 63182(均為DAICEL-ALLNEX公司製造)；EA-1010、EA-1020、EA-5323、EA-5520、EA-CHD、EMA-1020(均為新中村化學工業公司製造)；Epoxy Ester M-600A、Epoxy Ester 40EM、Epoxy Ester 70PA、Epoxy Ester 200PA、Epoxy Ester 80MFA、Epoxy Ester 3002M、Epoxy Ester 3002A、Epoxy Ester 1600A、Epoxy Ester 3000M、Epoxy Ester 3000A、Epoxy Ester 200EA、Epoxy Ester 400EA(均為共榮社化學公司製造)；DENACOL Acrylate DA-141、DENACOL Acrylate DA-314、DENACOL Acrylate DA-911(均為Nagase ChemteX公司製造)等。 As marketers of the aforementioned epoxy (meth) acrylates, for example, EBECRYL 860, EBECRYL 3200, EBECRYL 3201, EBECRYL 3412, EBECRYL 3600, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, EBECRYL 3800, EBECRYL 6040, EBECRYL RDX 63182 (both manufactured by DAICEL-ALLNEX); EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (both manufactured by Shin Nakamura Chemical Industry Company); Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester All are manufactured by Kyoeisha Chemical Co., Ltd.); DENACOL Acrylate DA-141, DENACOL Acrylate DA-314, DENACOL Acrylate DA-911 (all manufactured by Nagase ChemteX), and the like.
上述(甲基)丙烯酸胺酯例如可藉由使具有羥基之(甲基)丙烯酸衍生物2當量與具有2個異氰酸基之異氰酸酯化合物1當量於觸媒量之 錫系化合物存在下進行反應而獲得。 The (meth) acrylic acid amine ester can be reacted, for example, by making 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group and 1 equivalent of an isocyanate compound having 2 isocyanate groups in the presence of a tin-based compound having a catalytic amount. And get.
作為上述異氰酸酯化合物，例如可列舉：異佛爾酮二異氰酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、二苯甲烷-4,4'-二異氰酸酯(MDI)、氫化MDI、高分子MDI、1,5-萘二異氰酸酯、降莰烷二異氰酸酯、聯甲苯胺二異氰酸酯、苯二甲基二異氰酸酯(XDI)、氫化XDI、離胺酸二異氰酸酯、三苯甲烷三異氰酸酯、三(異氰酸酯基苯基)硫代磷酸酯、四甲基苯二甲基二異氰酸酯、1,6,11-十一烷三異氰酸酯等。 Examples of the isocyanate compound include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diisocyanate. Benzyl-4,4'-diisocyanate (MDI), hydrogenated MDI, polymer MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, benzylamine diisocyanate, xylylene diisocyanate (XDI) , Hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) phosphorothioate, tetramethylxylylene diisocyanate, 1,6,11-undecane triisocyanate, etc. .
又，作為上述異氰酸酯化合物，例如亦可使用：藉由多元醇與過量之異氰酸酯化合物之反應而獲得之經鏈延長的異氰酸酯化合物。 As the isocyanate compound, for example, a chain-extended isocyanate compound obtained by reacting a polyol with an excessive amount of an isocyanate compound can also be used.
作為上述多元醇，例如可列舉：乙二醇、丙二醇、甘油、山梨糖醇、三羥甲基丙烷、碳酸酯二醇、聚醚二醇、聚酯二醇、聚己內酯二醇等。 Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerol, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.
作為上述具有羥基之(甲基)丙烯酸衍生物，例如可列舉：單(甲基)丙烯酸羥基烷基酯、二元醇之單(甲基)丙烯酸酯、三元醇之單(甲基)丙烯酸酯或二(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯等。 Examples of the (meth) acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono (meth) acrylate, mono (meth) acrylate of a diol, and mono (meth) acrylic acid of a triol. Esters or di (meth) acrylates, epoxy (meth) acrylates, and the like.
作為上述單(甲基)丙烯酸羥基烷基酯，例如可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等。 Examples of the hydroxyalkyl mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and the like 4-hydroxybutyl (meth) acrylate and the like.
作為上述二元醇，例如可列舉：乙二醇、丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、聚乙二醇等。 Examples of the glycol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol.
作為上述三元醇，例如可列舉：三羥甲基乙烷、三羥甲基丙烷、甘油等。 Examples of the triol include trimethylolethane, trimethylolpropane, and glycerol.
作為上述環氧(甲基)丙烯酸酯，例如可列舉：雙酚A型環氧丙烯酸酯等。 Examples of the epoxy (meth) acrylate include a bisphenol A epoxy acrylate and the like.
作為上述(甲基)丙烯酸胺酯中之市售者，例如可列舉：M-1100、M-1200、M-1210、M-1600(均為東亞合成公司製造)；EBECRYL 210、EBECRYL 220、EBECRYL 230、EBECRYL 270、EBECRYL 1290、EBECRYL 2220、EBECRYL 4827、EBECRYL 4842、EBECRYL 4858、EBECRYL 5129、EBECRYL 6700、EBECRYL 8402、EBECRYL 8803、EBECRYL 8804、EBECRYL 8807、EBECRYL 9260(均為DAICEL-ALLNEX公司製造)；Artresin UN-330、Artresin SH-500B、Artresin UN-1200TPK、Artresin UN-1255、Artresin UN-3320HB、Artresin UN-7100、Artresin UN-9000A、Artresin UN-9000H(均為根上工業公司製造)；U-2HA、U-2PHA、U-3HA、U-4HA、U-6H、U-6HA、U-6LPA、U-10H、U-15HA、U-108、U-108A、U-122A、U-122P、U-324A、U-340A、U-340P、U-1084A、U-2061BA、UA-340P、UA-4000、UA-4100、UA-4200、UA-4400、UA-5201P、UA-7100、UA-7200、UA-W2A(均為新中村化學工業公司製造)；AH-600、AI-600、AT-600、UA-101I、UA-101T、UA-306H、UA-306I、UA-306T(均為共榮社化學公司製造)等。 Examples of commercially available amine (meth) acrylates include: M-1100, M-1200, M-1210, and M-1600 (all manufactured by Toa Kosei Corporation); EBECRYL 210, EBECRYL 220, EBECRYL 230, EBECRYL 270, EBECRYL 1290, EBECRYL 2220, EBECRYL 4827, EBECRYL 4842, EBECRYL 4858, EBECRYL 5129, EBECRYL 6700, EBECRYL 8402, EBECRYL 8803, EBECRYL 8804, EBECRYL 8807, EBECRYL 9260ALL (all manufactured by EXICE) Artresin UN-330, Artresin SH-500B, Artresin UN-1200TPK, Artresin UN-1255, Artresin UN-3320HB, Artresin UN-7100, Artresin UN-9000A, Artresin UN-9000H (all manufactured by Genji Industrial Corporation); U- 2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000, UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA- 7200, UA-W2A (all manufactured by Xinzhongcun Chemical Industry Company); AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (all (Kyoeisha Chemical Co., Ltd.)
上述硬化性樹脂100重量份中上述(甲基)丙烯酸化合物之含量之較佳下限為20重量份，較佳上限為80重量份。藉由使上述(甲基)丙烯酸化合物之含量為該範圍，所獲得之液晶顯示元件用密封劑成為遮光部硬化性及低液晶污染性更優異者。上述(甲基)丙烯酸化合物之含量之更佳下限 為30重量份，更佳上限為70重量份。 A preferable lower limit of the content of the (meth) acrylic compound in 100 parts by weight of the curable resin is 20 parts by weight, and a preferable upper limit is 80 parts by weight. When the content of the (meth) acrylic compound is within this range, the obtained sealing agent for a liquid crystal display element becomes more excellent in light-shielding portion hardening properties and low liquid crystal contamination properties. A more preferable lower limit of the content of the (meth) acrylic compound is 30 parts by weight, and a more preferable upper limit is 70 parts by weight.
作為上述芳香族環氧化合物，例如可列舉：成為用以合成上述環氧(甲基)丙烯酸酯之原料之環氧化合物中具有芳香環者、或者具有芳香環之部分(甲基)丙烯酸改質環氧化合物等。 Examples of the aromatic epoxy compound include those having an aromatic ring in an epoxy compound which is a raw material for synthesizing the epoxy (meth) acrylate, or a modified (meth) acrylic acid having a portion of the aromatic ring. Epoxy compounds, etc.
再者，於本說明書中，所謂上述部分(甲基)丙烯酸改質環氧化合物，意指於1分子中具有環氧基與(甲基)丙烯醯基各1個以上之化合物，例如可藉由使1分子中具有2個以上之環氧基之環氧化合物中一部分環氧基與(甲基)丙烯酸進行反應而獲得。 In addition, in this specification, the above-mentioned partially (meth) acrylic modified epoxy compound means a compound having one or more epoxy groups and (meth) acrylfluorene groups in one molecule, and can be borrowed, for example. It is obtained by reacting a part of epoxy groups in an epoxy compound having two or more epoxy groups in one molecule with (meth) acrylic acid.
上述硬化性樹脂100重量份中上述芳香族環氧化合物之含量之較佳下限為10重量份，較佳上限為70重量份。藉由使上述芳香族環氧化合物之含量為該範圍，所獲得之液晶顯示元件用密封劑成為兼顧遮光部硬化性與接著性之效果更優異者。上述芳香族環氧化合物之含量之更佳下限為20重量份，更佳上限為60重量份。 A preferable lower limit of the content of the aromatic epoxy compound in 100 parts by weight of the curable resin is 10 parts by weight, and a preferable upper limit is 70 parts by weight. By setting the content of the aromatic epoxy compound to be in this range, the obtained sealing agent for a liquid crystal display element becomes more excellent in the effect of achieving both the light-shielding portion curing property and the adhesiveness. A more preferable lower limit of the content of the aromatic epoxy compound is 20 parts by weight, and a more preferable upper limit is 60 parts by weight.
上述(甲基)丙烯酸化合物及上述芳香族環氧化合物較佳為具有雙酚骨架。藉由上述(甲基)丙烯酸化合物及上述芳香族環氧化合物具有雙酚骨架，而成為更容易使“由上述式(1)所表示之化合物所構成之光聚合起始劑”溶解者。 The (meth) acrylic compound and the aromatic epoxy compound preferably have a bisphenol skeleton. When the (meth) acrylic compound and the aromatic epoxy compound have a bisphenol skeleton, it becomes easier to dissolve the "photopolymerization initiator composed of the compound represented by the formula (1)".
上述硬化性樹脂較佳為含有順丁烯二醯亞胺化合物。 The curable resin preferably contains a maleimide compound.
藉由上述硬化性樹脂含有上述順丁烯二醯亞胺化合物，而成為更容易使“由上述式(1)所表示之化合物所構成之光聚合起始劑”溶解者。 When the said curable resin contains the said cis-butene diimine compound, it becomes easy to melt | dissolve "the photoinitiator which consists of a compound represented by the said Formula (1)".
再者，於本發明中，上述順丁烯二醯亞胺化合物並不包含於光聚合起始劑中而是包含於硬化性樹脂中。 In the present invention, the above-mentioned maleimide compound is not included in the photopolymerization initiator but is included in the curable resin.
就反應性之觀點而言，上述順丁烯二醯亞胺化合物較佳為於1分子中具有2個以上之順丁烯二醯亞胺基之多官能順丁烯二醯亞胺化合物，更佳為含有下述式(2)所表示之化合物及/或下述式(3)所表示之化合物。 From the viewpoint of reactivity, the above-mentioned maleimide compound is preferably a polyfunctional maleimide compound having two or more maleimide groups in one molecule, and more preferably It preferably contains a compound represented by the following formula (2) and / or a compound represented by the following formula (3).
式(2)中，R1表示碳數2~3之伸烷基，n為2~40之整數。 In formula (2), R 1 represents an alkylene group having 2 to 3 carbon atoms, and n is an integer of 2 to 40.
式(3)中，R2表示碳數1~40之2價脂肪族基。 In formula (3), R 2 represents a divalent aliphatic group having 1 to 40 carbon atoms.
上述式(3)中，R2之碳數較佳為12~36。又，R2較佳為具有脂肪族環。 In the formula (3), the carbon number of R 2 is preferably 12 to 36. R 2 preferably has an aliphatic ring.
作為上述式(3)所表示之化合物，具體而言，例如可列舉：1,20-雙順丁烯二醯亞胺-10,11-二辛基-二十烷(下述式(4-1)所表示之化合物)、1-伸庚基順丁烯二醯亞胺-2-伸辛基順丁烯二醯亞胺-4-辛基-5 -庚基環己烷(下述式(4-2)所表示之化合物)、1,2-二伸辛基順丁烯二醯亞胺-3-辛基-4-己基環己烷(下述式(4-3)所表示之化合物)等。該等可藉由美國專利第5973166號說明書所記載之方法等進行合成。 Specific examples of the compound represented by the formula (3) include 1,20-bis-cis-butenediamidine-10,11-dioctyl-icosane (the following formula (4- 1) Compound represented by 1), 1-heptyl-cis-butenedifluorenimine-2-octyl-cis-butene-diimide-4-octyl-5 -heptylcyclohexane (the following formula (4 -2), a compound represented by the above formula), 1,2-di-octyl cis-butenediamidine-3-octyl-4-hexylcyclohexane (the compound represented by the following formula (4-3)), and the like. These can be synthesized by the method described in the specification of US Patent No. 5,973,166.
上述硬化性樹脂100重量份中上述順丁烯二醯亞胺化合物 之含量之較佳下限為2重量份，較佳上限為20重量份。藉由使上述順丁烯二醯亞胺化合物之含量為該範圍，而變得更容易使“由上述式(1)所表示之化合物所構成之光聚合起始劑”溶解，且所獲得之液晶顯示元件用密封劑成為兼顧遮光部硬化性與低液晶污染性之效果更優異者。上述順丁烯二醯亞胺化合物之含量之更佳下限為5重量份，更佳上限為15重量份。 A preferable lower limit of the content of the cisbutadieneimine compound in 100 parts by weight of the curable resin is 2 parts by weight, and a preferable upper limit is 20 parts by weight. By making the content of the above-mentioned maleimide compound into this range, it becomes easier to dissolve the "photopolymerization initiator consisting of the compound represented by the above formula (1)", and the obtained The sealant for a liquid crystal display element is more excellent in the effect of balancing light-shielding part hardening and low liquid-crystal stain | pollution property. A more preferable lower limit of the content of the above-mentioned maleimide compound is 5 parts by weight, and a more preferable upper limit is 15 parts by weight.
上述硬化性樹脂亦可於不阻礙本發明之目的之範圍內含有脂肪族環氧化合物等其他硬化性樹脂。 The said curable resin may contain other curable resins, such as an aliphatic epoxy compound, in the range which does not inhibit the objective of this invention.
上述硬化性樹脂整體之平均SP值之較佳上限為24。藉由上述硬化性樹脂整體之平均SP值為24以下，而成為更容易使“由上述式(1)所表示之化合物所構成之光聚合起始劑”溶解者。上述硬化性樹脂整體之平均SP值之更佳上限為23.8。 A preferable upper limit of the average SP value of the entire curable resin is 24. When the average SP value of the entire curable resin is 24 or less, it becomes easier to dissolve the "photopolymerization initiator composed of the compound represented by the formula (1)". A more preferable upper limit of the average SP value of the entire curable resin is 23.8.
再者，於本說明書中，上述「SP值」意指溶解度參數，且藉由Fedors之推算法而算出。又，上述「平均SP值」係基於重量分率之SP值平均。 In addition, in this specification, the said "SP value" means a solubility parameter, and is calculated by the inferred algorithm of Fedors. The "average SP value" is an average of the SP values based on the weight fraction.
上述硬化性樹脂整體之重量平均分子量之較佳下限為340，較佳上限為1萬。藉由上述硬化性樹脂整體之重量平均分子量為該範圍，而成為更容易使“由上述式(1)所表示之化合物所構成之光聚合起始劑，’溶解者。上述硬化性樹脂整體之重量平均分子量之更佳下限為700，較佳上限為3000。 A preferable lower limit of the weight average molecular weight of the entire curable resin is 340, and a preferable upper limit is 10,000. When the weight-average molecular weight of the entire curable resin is within this range, it becomes easier to make "the photopolymerization initiator composed of the compound represented by the formula (1)" dissolved. A more preferable lower limit of the weight average molecular weight is 700, and a preferable upper limit is 3000.
再者，於本說明書中，上述「重量平均分子量」係利用凝膠滲透層析法(GPC)進行測定，且根據聚苯乙烯換算而求出之值。作為藉由GPC而對由聚苯乙烯換算所得之重量平均分子量進行測定時所使用之管柱，例如可列舉：Shodex LF-804(昭和電工公司製造)等。 In addition, in this specification, the said "weight average molecular weight" is a value measured by gel permeation chromatography (GPC) and calculated | required by polystyrene conversion. 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).
本發明之液晶顯示元件用密封劑含有光聚合起始劑。 The sealing agent for liquid crystal display elements of this invention contains a photoinitiator.
上述光聚合起始劑含有上述式(1)所表示之化合物。藉由使用上述式(1)所表示之化合物作為上述光聚合起始劑，本發明之液晶顯示元件用密封劑成為遮光部硬化性優異者。 The photopolymerization initiator contains a compound represented by the formula (1). By using the compound represented by the above formula (1) as the photopolymerization initiator, the sealing agent for a liquid crystal display element of the present invention is excellent in light-shielding part curing properties.
關於上述式(1)所表示之化合物之含量，相對於上述硬化性樹脂100重量份，較佳下限為0.1重量份，較佳上限為5重量份。藉由使上述式(1)所表示之化合物之含量為該範圍，所獲得之液晶顯示元件用密封劑成為兼顧遮光部硬化性與低液晶污染性之效果更優異者。上述式(1)所表示之化合物之含量之更佳下限為0.5重量份，更佳上限為2重量份。 With respect to the content of the compound represented by the formula (1), a preferable lower limit is 0.1 part by weight and a preferable upper limit is 5 parts by weight based on 100 parts by weight of the curable resin. When the content of the compound represented by the formula (1) is within this range, the obtained sealant for a liquid crystal display element becomes more excellent in the effect of achieving both the light-shielding portion hardening property and the low liquid crystal contamination property. A more preferable lower limit of the content of the compound represented by the formula (1) is 0.5 part by weight, and a more preferable upper limit is 2 parts by weight.
本發明之液晶顯示元件用密封劑亦可於不妨礙本發明之目的之範圍內，含有上述式(1)所表示之化合物以外之其他光聚合起始劑。 The sealing agent for liquid crystal display elements of this invention may contain the photoinitiator other than the compound represented by said Formula (1) in the range which does not prevent the objective of this invention.
本發明之液晶顯示元件用密封劑係上述硬化性樹脂與上述光聚合起始劑之SP值之差為2.5以下。藉由上述硬化性樹脂與上述光聚合起始劑之SP值之差為2.5以下，所獲得之液晶顯示元件用密封劑成為遮光部硬化性及低液晶污染性優異者。上述硬化性樹脂與上述光聚合起始劑之SP值之差更佳為2.3以下，進而較佳為2.0以下。 The sealant for liquid crystal display elements of the present invention is that the difference between the SP values of the curable resin and the photopolymerization initiator is 2.5 or less. When the difference between the SP value of the curable resin and the photopolymerization initiator is 2.5 or less, the obtained sealant for a liquid crystal display element is excellent in light-shielding portion hardening properties and low liquid crystal contamination properties. The difference in SP value between the curable resin and the photopolymerization initiator is more preferably 2.3 or less, and even more preferably 2.0 or less.
再者，上述「SP值之差」，意指平均SP值之差。即，上述硬化性樹脂與上述光聚合起始劑之SP值之差意指上述硬化性樹脂整體之平均SP值與上述光聚合起始劑整體之平均SP值的差。 In addition, the above-mentioned "difference in SP value" means a difference in average SP value. That is, the difference between the SP value of the curable resin and the photopolymerization initiator means the difference between the average SP value of the entire curable resin and the average SP value of the entire photopolymerization initiator.
本發明之液晶顯示元件用密封劑亦可含有熱聚合起始劑。 The sealing agent for liquid crystal display elements of this invention may contain a thermal polymerization initiator.
作為上述熱聚合起始劑，例如可列舉：由偶氮化合物、有機過氧化物等所構成者。其中，較佳為由高分子偶氮化合物所構成之起始劑(以下， 亦稱為「高分子偶氮起始劑」)。 Examples of the thermal polymerization initiator include an azo compound, an organic peroxide, and the like. Among these, an initiator composed of a polymer azo compound (hereinafter, also referred to as a “polymer azo initiator”) is preferred.
再者，於本說明書中，所謂高分子偶氮化合物，意指具有偶氮基且藉由熱而生成自由基的數量平均分子量為300以上之化合物。 In the present specification, the term “polymer azo compound” means a compound having an azo group and having a number average molecular weight of 300 or more that generates radicals by heat.
上述高分子偶氮化合物之數量平均分子量之較佳下限為1000，較佳上限為30萬。藉由使上述高分子偶氮化合物之數量平均分子量為該範圍，可抑制液晶污染並且容易地與硬化性樹脂混合。上述高分子偶氮化合物之數量平均分子量之更佳下限為5000，更佳上限為10萬，進而較佳之下限為1萬，進而較佳之上限為9萬。 A preferable lower limit of the number average molecular weight of the above-mentioned polymer azo compound is 1,000, and a preferable upper limit is 300,000. When the number average molecular weight of the above-mentioned polymer azo compound is within this range, liquid crystal contamination can be suppressed and easily mixed with the curable resin. A more preferable lower limit of the number average molecular weight of the above polymer azo compound is 5000, a more preferable upper limit is 100,000, a more preferable lower limit is 10,000, and a more preferable upper limit is 90,000.
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)進行測定，且根據聚苯乙烯換算而求出之值。作為藉由GPC對由聚苯乙烯換算所得之數量平均分子量進行測定時之管柱，例如可列舉：Shodex LF-804(昭和電工公司製造)等。 In addition, in this specification, the said number average molecular weight is a value measured by gel permeation chromatography (GPC), and calculated | required by polystyrene conversion. Examples of the column used when measuring the number average molecular weight obtained by polystyrene conversion by GPC include Shodex LF-804 (manufactured by Showa Denko Corporation).
作為上述高分子偶氮化合物，例如可列舉：具有經由偶氮基鍵結有多個聚環氧烷或聚二甲基矽氧烷等單元而成之結構者。 Examples of the polymer azo compound include a structure in which a plurality of units such as polyalkylene oxide or polydimethylsiloxane are bonded via an azo group.
作為具有上述經由偶氮基鍵結有多個聚環氧烷等單元而成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。作為此種高分子偶氮起始劑，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)與具有末端胺基之聚二甲基矽氧烷之縮聚物等。 As the polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via an azo group, it is preferable to have a polyethylene oxide structure. Examples of such a polymer azo initiator include a polycondensate of 4,4'-azobis (4-cyanovaleric acid) and a polyalkylene glycol, or 4,4'-azo A polycondensate of bis (4-cyanovaleric acid) and polydimethylsiloxane having a terminal amine group, and the like.
作為上述高分子偶氮化合物中之市售者，例如可列舉：VPE-0201、VPE-0401、VPE-0601、VPS-0501、VPS-1001(均為和光純藥工業公司製造)等。 Examples of the commercially available polymer azo compound include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.).
又，作為由並非高分子之偶氮化合物所構成之熱聚合起始劑，例如可列舉：V-65、V-501(均為和光純藥工業公司製造)等。 Examples of the thermal polymerization initiator composed of an azo compound other than a polymer include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
作為上述有機過氧化物，例如可列舉：過氧化酮、過氧縮酮、過氧化氫、二烷基過氧化物(dialkyl peroxide)、過氧酯、二醯基過氧化物(diacyl peroxide)、過氧化二碳酸酯等。 Examples of the organic peroxide include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, Peroxydicarbonate and the like.
關於上述熱聚合起始劑之含量，相對於硬化性樹脂100重量份，較佳下限為0.05重量份，較佳上限為10重量份。藉由使上述熱聚合起始劑為該範圍，所獲得之液晶顯示元件用密封劑成為抑制液晶污染並且保存穩定性或硬化性更優異者。上述熱聚合起始劑之含量之更佳下限為0.1重量份，更佳上限為5重量份。 Regarding the content of the thermal polymerization initiator, the lower limit is preferably 0.05 parts by weight, and the upper limit is preferably 10 parts by weight based on 100 parts by weight of the curable resin. By making the said thermal-polymerization initiator into this range, the obtained sealing compound for liquid crystal display elements will become a thing which suppresses liquid crystal contamination and is more excellent in storage stability or hardenability. A more preferable lower limit of the content of the thermal polymerization initiator is 0.1 part by weight, and a more preferable upper limit is 5 parts by weight.
本發明之液晶顯示元件用密封劑亦可含有熱硬化劑。 The sealing agent for liquid crystal display elements of this invention may contain a thermosetting agent.
作為上述熱硬化劑，例如可列舉：有機酸醯肼、咪唑衍生物、胺化合物、多酚系化合物、酸酐等。其中，可較佳地使用有機酸醯肼。 Examples of the thermosetting agent include organic acid hydrazine, imidazole derivatives, amine compounds, polyphenol compounds, and acid anhydrides. Among them, the organic acid hydrazine can be preferably used.
作為上述有機酸醯肼，例如可列舉：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。 Examples of the organic acid hydrazine include dihydrazine sebacate, dihydrazine isophthalate, dihydrazine adipate, and dihydrazine malonate.
作為上述有機酸醯肼中之市售者，例如可列舉：SDH、ADH、MDH(均為大塚化學公司製造)；Amicure VDH、Amicure VDH-J、Amicure UDH、Amicure UDH-J(均為Ajinomoto Fine-Techno公司製造)等。 Examples of the commercially available organic acid hydrazine include SDH, ADH, and MDH (all manufactured by Otsuka Chemical Co., Ltd.); Amicure VDH, Amicure VDH-J, Amicure UDH, and Amicure UDH-J (all are Ajinomoto Fine) -Made by Techno).
關於上述熱硬化劑之含量，相對於上述硬化性樹脂100重量份，較佳下限為1重量份，較佳上限為50重量份。藉由使上述熱硬化劑之含量為該範圍，可不使所獲得之液晶顯示元件用密封劑之塗佈性等變差而製成熱硬化性更優異者。上述熱硬化劑之含量之更佳上限為30重量份。 With respect to the content of the thermosetting agent, a preferred lower limit is 1 part by weight and a preferred upper limit is 50 parts by weight based on 100 parts by weight of the curable resin. By setting the content of the above-mentioned thermosetting agent to be in this range, it is possible to obtain a more excellent thermosetting property without deteriorating the coatability and the like of the obtained sealing agent for a liquid crystal display element. A more preferable upper limit of the content of the heat curing agent is 30 parts by weight.
就使硬化物之柔軟性或接著性等提高，或者抑制液晶滲入密封劑侵入或密封劑溶出至液晶等觀點而言，本發明之液晶顯示元件用密封劑較佳為含有柔軟粒子。 It is preferable that the sealing agent for liquid crystal display elements of this invention contains a soft particle from a viewpoint of improving the softness | flexibility, adhesiveness, etc. of a hardened | cured material, or suppressing penetration | invasion of a liquid crystal into a sealing agent, or elution of a sealing agent to a liquid crystal.
作為上述柔軟粒子，例如可列舉：聚矽氧系粒子、乙烯系粒子、胺酯系粒子、氟系粒子、腈系粒子等。其中，較佳為聚矽氧系粒子、乙烯系粒子。 Examples of the soft particles include polysiloxane particles, vinyl particles, amine ester particles, fluorine particles, and nitrile particles. Among these, polysiloxane particles and vinyl particles are preferred.
作為上述聚矽氧系粒子，就樹脂中之分散性之觀點而言，較佳為聚矽氧橡膠粒子。 As said silicone particle | grains, a silicone rubber particle is preferable from a viewpoint of the dispersibility in resin.
作為上述乙烯系粒子，可較佳地使用(甲基)丙烯酸粒子。上述(甲基)丙烯酸粒子可藉由公知之方法使成為原料之單體進行聚合而獲得。具體而言，例如可列舉：於自由基聚合起始劑之存在下使單體進行懸浮聚合之方法；藉由於自由基聚合起始劑之存在下使非交聯之種子粒子吸收單體而使種子粒子膨潤從而進行種子聚合的方法等。 As the vinyl-based particles, (meth) acrylic particles can be preferably used. The (meth) acrylic particles can be obtained by polymerizing a monomer serving as a raw material by a known method. Specifically, for example, a method of suspension polymerization of a monomer in the presence of a radical polymerization initiator; a method in which non-crosslinked seed particles absorb the monomer in the presence of a radical polymerization initiator; A method in which seed particles are swollen to perform seed polymerization and the like.
作為用以形成上述(甲基)丙烯酸粒子之原料之單體，例如可列舉：(甲基)丙烯酸烷基酯類、含氧原子之(甲基)丙烯酸酯類、含腈單體、含氟(甲基)丙烯酸酯類等單官能單體。 Examples of the monomer used as a raw material for forming the (meth) acrylic particles include alkyl (meth) acrylates, (meth) acrylates containing oxygen atoms, nitrile-containing monomers, and fluorine-containing monomers. Monofunctional monomers such as (meth) acrylates.
作為上述(甲基)丙烯酸烷基酯類，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯等。 Examples of the (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylate. (Hexyl) hexyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearin (meth) acrylate Esters, cyclohexyl (meth) acrylate, isofluorenyl (meth) acrylate, and the like.
作為上述含氧原子之(甲基)丙烯酸酯類，例如可列舉：(甲基)丙烯酸2 -羥基乙酯、(甲基)丙烯酸甘油酯、聚氧乙烯(甲基)丙烯酸酯、(甲基)丙烯酸縮水甘油酯等。 Examples of the (meth) acrylates containing oxygen atoms include 2-hydroxyethyl (meth) acrylate, glyceryl (meth) acrylate, polyoxyethylene (meth) acrylate, and (meth) ) Glycidyl acrylate and the like.
作為上述含腈單體，例如可列舉：(甲基)丙烯腈等。 Examples of the nitrile-containing monomer include (meth) acrylonitrile.
作為上述含氟(甲基)丙烯酸酯類，例如可列舉：(甲基)丙烯酸三氟甲酯、(甲基)丙烯酸五氟乙酯等。 Examples of the fluorine-containing (meth) acrylates include trifluoromethyl (meth) acrylate and pentafluoroethyl (meth) acrylate.
其中，就均聚物之Tg較低，可使施加1g負荷時之變形量變大之方面而言，較佳為(甲基)丙烯酸烷基酯類。 Among them, alkyl (meth) acrylates are preferred because the homopolymer has a low Tg and can increase the amount of deformation when a load of 1 g is applied.
又，為了具有交聯結構，亦可使用四羥甲基甲烷四(甲基)丙烯酸酯、四羥甲基甲烷三(甲基)丙烯酸酯、四羥甲基甲烷二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、(聚)四亞甲基二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、異三聚氰酸骨架三(甲基)丙烯酸酯等交聯性單體。其中，就交聯點間分子量較大，可使施加1g負荷時之變形量變大之方面而言，較佳為(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、(聚)四亞甲基二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯。 In order to have a crosslinked structure, tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dinepentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (Meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (poly) tetramethylene di (meth) acrylate, 1, Crosslinkable monomers such as 4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and isotricyanic acid skeleton tri (meth) acrylate. Among them, (poly) ethylene glycol di (meth) acrylate and (poly) propylene glycol di (methyl) are preferred because the molecular weight between the crosslinking points is large and the amount of deformation can be increased when a load of 1 g is applied. Acrylate), (poly) tetramethylene di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate.
關於上述交聯性單體之使用量，於成為用以形成上述(甲基)丙烯酸系粒子之原料之單體整體中，較佳下限為1重量%，較佳上限為90重量%。藉由使上述交聯性單體之使用量為1重量%以上，耐溶劑性提高，與其他密封劑成分混練時不會引起膨潤等問題而容易均一地分散。藉由使上述交聯性單體之使用量為90重量%以下，可使回覆率變低。上述交聯性 單體之使用量之更佳下限為3重量%，更佳上限為80重量%。 As for the usage-amount of the said crosslinkable monomer, in the whole monomer which becomes the raw material for forming the said (meth) acrylic-type particle, a preferable minimum is 1 weight%, and a preferable upper limit is 90 weight%. When the amount of the crosslinkable monomer used is 1% by weight or more, the solvent resistance is improved, and problems such as swelling and the like are not caused when kneaded with other sealant components, and it is easy to uniformly disperse. When the use amount of the crosslinkable monomer is 90% by weight or less, the response rate can be reduced. A more preferable lower limit of the amount of the crosslinkable monomer used is 3% by weight, and a more preferable upper limit is 80% by weight.
進而，除該等丙烯酸系單體以外，亦可使用苯乙烯系單體、乙烯醚類、羧酸乙烯酯類、不飽和烴、含鹵素單體、三聚氰酸三烯丙酯、異三聚氰酸三烯丙酯、偏苯三甲酸三烯丙酯、二乙烯苯、鄰苯二甲酸二烯丙酯、二烯丙基丙烯醯胺、二烯丙醚、γ-(甲基)丙烯醯氧基丙基三甲氧基矽烷、乙烯基三甲氧基矽烷等單體。 Furthermore, in addition to these acrylic monomers, styrene-based monomers, vinyl ethers, vinyl carboxylates, unsaturated hydrocarbons, halogen-containing monomers, triallyl cyanurate, isotris Triallyl polycyanate, triallyl trimellitate, divinylbenzene, diallyl phthalate, diallyl allylamine, diallyl ether, γ- (meth) propylene Monomethoxypropyltrimethoxysilane, vinyltrimethoxysilane and other monomers.
作為上述苯乙烯系單體，例如可列舉：苯乙烯、α-甲基苯乙烯、三甲氧基矽烷基苯乙烯等。 Examples of the styrene-based monomer include styrene, α-methylstyrene, and trimethoxysilylstyrene.
作為上述乙烯醚類，例如可列舉：甲基乙烯醚、乙基乙烯醚、丙基乙烯醚等。 Examples of the vinyl ethers include methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether.
作為上述羧酸乙烯酯類，例如可列舉：乙酸乙烯酯、丁酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯等。 Examples of the vinyl carboxylic acid esters include vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate, and the like.
作為上述不飽和烴，例如可列舉：乙烯、丙烯、異戊二烯、丁二烯等。 Examples of the unsaturated hydrocarbon include ethylene, propylene, isoprene, and butadiene.
作為上述含鹵素單體，例如可列舉：氯乙烯、氟乙烯、氯苯乙烯等。 Examples of the halogen-containing monomer include vinyl chloride, vinyl fluoride, and chlorostyrene.
作為上述(甲基)丙烯酸粒子，亦可較佳地使用核殼(甲基)丙烯酸酯共聚物微粒子。 As the (meth) acrylic particles, core-shell (meth) acrylate copolymer fine particles can also be preferably used.
作為上述核殼(甲基)丙烯酸酯共聚物微粒子中之市售者，例如可列舉：F351(瑞翁化成公司製造)等。 As a commercially available one of the core-shell (meth) acrylate copolymer fine particles, for example, F351 (manufactured by Ruiwon Chemical Co., Ltd.) and the like are mentioned.
又，作為上述乙烯系粒子，例如亦可使用聚二乙烯苯粒子、聚氯丁二烯粒子、丁二烯橡膠粒子等。 In addition, as the vinyl-based particles, for example, polydivinylbenzene particles, polychloroprene particles, butadiene rubber particles, and the like can be used.
上述柔軟粒子之平均粒徑之較佳下限為0.01μm，較佳上限為10μm。藉由使上述柔軟粒子之平均粒徑為該範圍，而成為提高所獲得之 液晶顯示元件用密封劑之硬化物之柔軟性或接著性之效果更優異者。上述柔軟粒子之平均粒徑之更佳下限為0.1μm，更佳上限為8μm。 The preferable lower limit of the average particle diameter of the soft particles is 0.01 μm, and the preferable upper limit is 10 μm. When the average particle diameter of the soft particles is in this range, the effect of improving the flexibility or adhesion of the cured product of the obtained sealing agent for a liquid crystal display element is more excellent. A more preferable lower limit of the average particle diameter of the soft particles is 0.1 μm, and a more preferable upper limit is 8 μm.
再者，於本說明書中，上述柔軟粒子之平均粒徑意指藉由下述測定而獲得之值：針對摻合於密封劑之前之粒子，使用雷射繞射式粒度分佈測定裝置進行測定。作為上述雷射繞射式粒度分佈測定裝置，可使用Mastersizer 2000(Malvern公司製造)等。 In addition, in this specification, the average particle diameter of the said soft particle means the value obtained by the measurement which measured the particle | grains before mixing with the sealing agent using the laser diffraction type particle size distribution measuring device. As the above-mentioned laser diffraction type particle size distribution measurement device, Mastersizer 2000 (manufactured by Malvern) can be used.
上述柔軟粒子之硬度之較佳下限為10，較佳上限為50。藉由使上述柔軟粒子之硬度為該範圍，而成為提高所獲得之液晶顯示元件用密封劑之硬化物之柔軟性或接著性之效果更優異者。上述柔軟粒子之硬度之更佳下限為20，更佳上限為40。 The preferable lower limit of the hardness of the soft particles is 10, and the preferable upper limit is 50. By making the hardness of the said soft particle into this range, it becomes the one which is more excellent in the effect of improving the softness | flexibility or adhesiveness of the hardened | cured material of the sealing compound for liquid crystal display elements obtained. A more preferable lower limit of the hardness of the soft particles is 20, and a more preferable upper limit is 40.
再者，於本說明書中，上述柔軟粒子之硬度意指藉由依據JIS K6253之方法而測得之A型硬度計硬度。 In addition, in this specification, the hardness of the said soft particle means the hardness of the A-type durometer measured by the method based on JIS K6253.
本發明之液晶顯示元件用密封劑100重量份中之上述柔軟粒子之含量的較佳下限為5重量份，較佳上限為50重量份。藉由上述柔軟粒子之含量為該範圍，而成為提高所獲得之液晶顯示元件用密封劑之硬化物之柔軟性或接著性之效果更優異者。上述柔軟粒子之含量之更佳下限為10重量份，更佳上限為30重量份。 The preferable lower limit of the content of the soft particles in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 5 parts by weight, and the preferable upper limit is 50 parts by weight. When the content of the soft particles is within this range, the effect of improving the flexibility or adhesiveness of the cured product of the obtained sealant for a liquid crystal display element is more excellent. A more preferable lower limit of the content of the soft particles is 10 parts by weight, and a more preferable upper limit is 30 parts by weight.
本發明之液晶顯示元件用密封劑較佳為以黏度之提高、利用應力分散效果之接著性之改善、線膨脹率之改善等為目的而含有填充劑。 The sealing agent for a liquid crystal display element of the present invention preferably contains a filler for the purpose of improving viscosity, improving adhesiveness by using a stress dispersion effect, and improving linear expansion ratio.
作為上述填充劑，例如可列舉：無機填充劑、或上述柔軟粒子所含有者以外之有機填充劑。 Examples of the filler include inorganic fillers and organic fillers other than those contained in the soft particles.
作為上述無機填充劑，例如可列舉：二氧化矽、滑石、玻璃珠、石棉、 石膏、矽藻土、膨潤石、膨土、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。 Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, and oxide Iron, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, and the like.
本發明之液晶顯示元件用密封劑100重量份中上述填充劑之含量的較佳下限為10重量份，較佳上限為70重量份。藉由使上述填充劑之含量為該範圍，不會使塗佈性等變差而成為接著性之改善等效果更優異者。上述填充劑之含量之更佳下限為20重量份，更佳上限為60重量份。 A preferable lower limit of the content of the filler in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 10 parts by weight, and a preferable upper limit is 70 parts by weight. When the content of the filler is in this range, the coating properties and the like are not deteriorated, and the effects such as improvement of adhesion are more excellent. The more preferable lower limit of the content of the filler is 20 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“作為用以將密封劑與基板等良好地進行接著之接著助劑的作用”。 It is preferable that the sealing agent for liquid crystal display elements of this invention contains a silane coupling agent. The above-mentioned silane coupling agent mainly has a "function as a bonding aid for adhering a sealant to a substrate and the like well".
作為上述矽烷偶合劑，例如可較佳地使用3-胺基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-異氰酸基丙基三甲氧基矽烷等。該等之提高與基板等之接著性之效果優異，且藉由與硬化性樹脂進行化學鍵結，可抑制硬化性樹脂流入液晶中。該等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, and 3-isocyanate can be preferably used. Acid propyltrimethoxysilane and the like. These effects are excellent in improving the adhesion to a substrate and the like, and by chemically bonding with a curable resin, it is possible to suppress the curable resin from flowing into the liquid crystal. These silane coupling agents may be used alone or in combination of two or more kinds.
本發明之液晶顯示元件用密封劑100重量份中上述矽烷偶合劑之含量的較佳下限為0.1重量份，較佳上限為10重量份。藉由使上述矽烷偶合劑之含量為該範圍，而成為抑制液晶污染之產生並且提高接著性之效果更優異者。上述矽烷偶合劑之含量之更佳下限為0.3重量份，更佳上限為5重量份。 A preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 0.1 part by weight, and a preferable upper limit is 10 parts by weight. When the content of the silane coupling agent is in this range, the effect of suppressing the occurrence of liquid crystal contamination and improving the adhesion is more excellent. A more preferable lower limit of the content of the silane coupling agent is 0.3 part by weight, and a more preferable upper limit is 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，本發明之液晶顯示元件用密封劑可較佳地用作遮光密封劑。 The sealing agent for liquid crystal display elements of this invention may contain a light-shielding agent. By containing the said 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(cyanine black)、富勒烯、碳黑、樹脂被覆型碳黑等。其中，就絕緣性較高之方面而言，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 in terms of high insulation properties.
上述鈦黑即便為未經表面處理者，亦發揮充分之效果，但亦可使用表面經偶合劑等有機成分處理者、或者經氧化矽、氧化鈦、氧化鍺、氧化鋁、氧化鋯、氧化鎂等無機成分被覆者等的經表面處理之鈦黑。其中，經有機成分處理者於可更為提高絕緣性之方面上較佳。 The above-mentioned titanium black has sufficient effects even if it is not surface-treated, but it can also be treated with organic components such as coupling agents on its surface, or silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconia, and magnesium oxide Surface-treated titanium black such as inorganic component coatings. Among them, those treated with an organic component are more preferable in that the insulation properties can be further improved.
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而製造的液晶顯示元件具有充分之遮光性，因此可實現沒有光之漏出且具有較高之對比度，具有優異之圖像顯示品質之液晶顯示元件。 In addition, the liquid crystal display element manufactured by using the sealant for liquid crystal display elements of the present invention containing the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding properties, and therefore, it can realize no leakage of light and have a high contrast, and has an excellent figure Liquid crystal display elements with display quality.
作為上述鈦黑中之市售者，例如可列舉：12S、13M、13M-C、13R-N、14M-C(均為Mitsubishi Materials公司製造)；Tilack D(赤穗化成公司製造)等。 Examples of the commercially available titanium black include 12S, 13M, 13M-C, 13R-N, and 14M-C (all manufactured by Mitsubishi Materials); Tilack D (manufactured by Akaho Kasei).
上述鈦黑之比表面積之較佳下限為13m2/g，較佳上限為30m2/g，更佳下限為15m2/g，更佳上限為25m2/g。 The preferable lower limit of the specific surface area of the 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.
又，上述鈦黑之體積電阻之較佳下限為0.5Ω‧cm，較佳上限為3Ω‧cm，更佳下限為1Ω‧cm，更佳上限為2.5Ω‧cm。 In addition, the preferred lower limit of the volume resistance of the titanium black is 0.5Ω‧cm, the preferred upper limit is 3Ω‧cm, the more preferred lower limit is 1Ω‧cm, and the more preferred upper limit is 2.5Ω‧cm.
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，較佳下限為1nm，較佳上限為5μm。藉由使上述遮光劑之一次粒徑為該範圍，可不使所獲得之液晶顯示元件用密封劑之塗佈性等變差而製成遮光性更優異者。上述遮光劑之一次粒徑之更佳下限為5nm，更佳上限為200nm，進而較佳之下限為10nm，進而較佳之上限為100 nm。 The primary particle diameter of the light-shielding agent is not particularly limited as long as it is equal to or less than the distance between the substrates of the liquid crystal display element. The preferred lower limit is 1 nm, and the preferred upper limit is 5 μm. By making the primary particle diameter of the said light-shielding agent into this range, it can be made into the thing which is more excellent in light-shielding property, without deteriorating the coating property of the obtained sealing compound for liquid crystal display elements. A more preferable lower limit of the primary particle diameter of the above-mentioned sunscreen is 5 nm, a more preferable upper limit is 200 nm, a more preferable lower limit is 10 nm, and a more preferable upper limit is 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)中而進行測定。 The primary particle diameter of the light-shielding agent can be measured by using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS), dispersing the light-shielding agent in a solvent (water, organic solvent, etc.).
本發明之液晶顯示元件用密封劑100重量份中上述遮光劑之含量的較佳下限為5重量份，較佳上限為80重量份。藉由上述遮光劑之含量為該範圍，可不使所獲得之液晶顯示元件用密封劑對於基板之接著性或硬化後之強度或描畫性降低而發揮更優異之遮光性。上述遮光劑之含量之更佳下限為10重量份，更佳上限為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 preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight. When the content of the light-shielding agent is within this range, it is possible to exhibit more excellent light-shielding properties without reducing the adhesiveness of the obtained sealing agent for a liquid crystal display element to a substrate or the strength or drawability after curing. A more preferable lower limit of the content of the light-shielding agent is 10 parts by weight, a more preferable upper limit is 70 parts by weight, a more preferable lower limit is 30 parts by weight, and a more preferable upper limit is 60 parts by weight.
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：使用均相分散機、均質攪拌機、萬能攪拌機、行星式攪拌機、捏合機、三輥研磨機等混合機，將硬化性樹脂、光聚合起始劑、及視需要添加之矽烷偶合劑等添加劑進行混合之方法等。 Examples of the method for producing the sealant for a liquid crystal display element of the present invention include, for example, using a homomixer, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roll mill, and the like to harden the resin, A method for mixing a photopolymerization initiator and additives such as a silane coupling agent as needed.
可藉由於本發明之液晶顯示元件用密封劑中摻合導電性微粒子而製造上下導通材料。又，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。 The conductive fine particles can be mixed with the sealant for a liquid crystal display element of the present invention to produce a vertical conductive material. In addition, such a sealant for a liquid crystal display element of the present invention and a conductive material for upper and lower conductive particles are also one aspect 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彈性，可不會損傷透明基板等而實現導電連接，故而較佳。 As the conductive fine particles, metal balls, those having a conductive metal layer formed on the surface of the resin fine particles, and the like can be used. Among them, those having a conductive metal layer formed on the surface of the resin microparticles are preferred because of the excellent elasticity of the resin microparticles so that a conductive connection can be achieved without damaging the transparent substrate or the like.
又，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 sealant for a liquid crystal display element of the present invention or the vertical conductive material of the present invention is also one aspect of the present invention.
作為製造本發明之液晶顯示元件之方法，可較佳地使用液晶滴下法，具體而言，例如可列舉具有以下各步驟之方法等。 As a method for manufacturing the liquid crystal display element of the present invention, a liquid crystal dropping method can be preferably used. Specifically, for example, a method having the following steps and the like can be cited.
首先，進行如下步驟：藉由網版印刷、點膠機塗佈等，將本發明之液晶顯示元件用密封劑塗佈於附ITO薄膜等電極之玻璃基板或聚對苯二甲酸乙二酯基板等2片基板之一片上，形成框狀之密封圖案。其次進行如下步驟：於本發明之液晶顯示元件用密封劑未硬化之狀態下將液晶之微小液滴滴至基板之密封圖案之框內並進行塗佈，於真空下與另一片基板重疊。其後，進行如下步驟：對本發明之液晶顯示元件用密封劑之密封圖案部分照射紫外線等光而使密封劑進行光硬化，藉由此方法而可獲得液晶顯示元件。又，除上述使密封劑進行光硬化之步驟以外，亦可進行對密封劑進行加熱而使之熱硬化之步驟。 First, the following steps are performed: applying the sealant for a liquid crystal display element of the present invention to a glass substrate or a polyethylene terephthalate substrate with an electrode such as an ITO film by screen printing, coating by a dispenser, or the like. Wait for one of the two substrates to form a frame-shaped seal pattern. Next, the following steps are performed: in the state where the sealant for a liquid crystal display element of the present invention is not hardened, minute liquid droplets of liquid crystal are dropped into a frame of a sealing pattern of a substrate and coated, and overlapped with another substrate under vacuum. Thereafter, the following steps are performed: the sealing pattern portion of the sealant for a liquid crystal display element of the present invention is irradiated with light such as ultraviolet rays to light-cure the sealant, and a liquid crystal display element can be obtained by this method. Further, in addition to the above-mentioned step of photo-curing the sealant, a step of heating the sealant and thermally curing the sealant may be performed.
根據本發明，可提供一種遮光部硬化性優異，且可抑制液晶污染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 is excellent in the light-shielding portion and that can suppress liquid crystal contamination. Furthermore, according to the present invention, it is possible to provide a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.
以下，揭示實施例而對本發明進一步詳細地進行說明，但本 發明並不僅限定於該等實施例。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
(雙酚A型環氧丙烯酸酯低聚物之合成) (Synthesis of bisphenol A epoxy acrylate oligomer)
於附帶冷卻管、攪拌翼之四口燒瓶中加入雙酚A型環氧樹脂170g(0.5mol)、丙烯酸86.5g(1.2mol)、三苯基膦2.6g(0.01mol)、及二丁基羥基甲苯0.2g(0.001mol)，於油浴中以120℃攪拌12小時。作為上述雙酚A型環氧樹脂，使用DIC公司製造之試劑。作為上述丙烯酸，使用東京化成工業公司製造之試劑。作為上述三苯基膦，使用東京化成工業公司製造之試劑。作為上述二丁基羥基甲苯，使用東京化成工業公司製造之試劑。 170 g (0.5 mol) of bisphenol A epoxy resin, 86.5 g (1.2 mol) of acrylic acid, 2.6 g (0.01 mol) of triphenylphosphine, and dibutyl hydroxyl were added to a four-necked flask equipped with a cooling tube and a stirring wing. 0.2 g (0.001 mol) of toluene was stirred in an oil bath at 120 ° C. for 12 hours. As the bisphenol A epoxy resin, a reagent manufactured by DIC Corporation was used. As the acrylic acid, a reagent manufactured by Tokyo Chemical Industry Co., Ltd. was used. As the triphenylphosphine, a reagent manufactured by Tokyo Chemical Industry Co., Ltd. was used. As the dibutylhydroxytoluene, a reagent manufactured by Tokyo Chemical Industry Co., Ltd. was used.
反應結束後，進行利用蒸餾水之洗淨、真空乾燥、及過濾，而獲得雙酚A型環氧丙烯酸酯低聚物(分子量4500、分散度2.5)。 After completion of the reaction, washing with distilled water, vacuum drying, and filtration were performed to obtain a bisphenol A type epoxy acrylate oligomer (molecular weight 4500, dispersion degree 2.5).
再者，所獲得之雙酚A型環氧丙烯酸酯低聚物係根據1H-NMR及GC-Ms進行了結構之確認。 The structure of the obtained bisphenol A epoxy acrylate oligomer was confirmed by 1 H-NMR and GC-Ms.
(雙酚A型環氧甲基丙烯酸酯低聚物之合成) (Synthesis of bisphenol A epoxy methacrylate oligomer)
於附帶冷卻管、攪拌翼之四口燒瓶中加入雙酚A型環氧樹脂170g(0.5mol)、甲基丙烯酸103.3g(1.2mol)、三苯基膦2.6g(0.01mol)、及二丁基羥基甲苯0.2g(0.001mol)，於油浴中以120℃攪拌12小時。作為上述雙酚A型環氧樹脂，使用DIC公司製造之試劑。作為上述甲基丙烯酸，使用東京化成工業公司製造之試劑。作為上述三苯基膦，使用東京化成工業公司製造之試劑。作為上述二丁基羥基甲苯，使用東京化成工業公司製造之試劑。 170 g (0.5 mol) of bisphenol A epoxy resin, 103.3 g (1.2 mol) of methacrylic acid, 2.6 g (0.01 mol) of triphenylphosphine, and dibutyl ether were added to a four-necked flask equipped with a cooling tube and a stirring wing. 0.2 g (0.001 mol) of hydroxytoluene was stirred in an oil bath at 120 ° C. for 12 hours. As the bisphenol A epoxy resin, a reagent manufactured by DIC Corporation was used. As the methacrylic acid, a reagent manufactured by Tokyo Chemical Industry Co., Ltd. was used. As the triphenylphosphine, a reagent manufactured by Tokyo Chemical Industry Co., Ltd. was used. As the dibutylhydroxytoluene, a reagent manufactured by Tokyo Chemical Industry Co., Ltd. was used.
反應結束後，進行利用蒸餾水之洗淨、真空乾燥、及過濾，而獲得雙酚A型環氧甲基丙烯酸酯低聚物(分子量3200、分散度2.2)。 After the reaction was completed, washing with distilled water, vacuum drying, and filtration were performed to obtain a bisphenol A epoxy methacrylate oligomer (molecular weight 3200, dispersion degree 2.2).
再者，所獲得之雙酚A型環氧甲基丙烯酸酯低聚物係根據1H-NMR及GC-Ms進行了結構之確認。 In addition, the structure of the obtained bisphenol A epoxy methacrylate oligomer was confirmed by 1 H-NMR and GC-Ms.
(實施例1~12、比較例1~5) (Examples 1 to 12, Comparative Examples 1 to 5)
依據表1~3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」)將各材料混合後，進而使用三輥研磨機進行混合，藉此製備實施例1~12、比較例1~5之液晶顯示元件用密封劑。 According to the blending ratios described in Tables 1 to 3, the materials were mixed using a planetary mixer ("Defoaming Stirred Taro" manufactured by Thinky), and then mixed using a three-roll mill to prepare Examples 1 to 12. Sealants for liquid crystal display elements of Comparative Examples 1 to 5.
<評價> <Evaluation>
針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1~3。 The following evaluations were performed about each sealing agent for liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Tables 1 to 3.
(光聚合起始劑之溶解性) (Solubility of Photopolymerization Initiator)
針對實施例及比較例中所獲得之各液晶顯示元件用密封劑，於各密封劑中所使用之硬化性樹脂100g中加入各密封劑中所使用之光聚合起始劑2g，於120℃之烘箱中進行加熱。將加熱開始後，未達5分鐘時完全溶解之情形設為「○○○」，將於5分鐘以上且未達10分鐘時完全溶解之情形設為「○○」，將於10分鐘以上且未達30分鐘時完全溶解之情形設為「○」，將雖於30分鐘內溶解但產生溶解殘留之情形設為「△」，將經過30分鐘亦未完全溶解之情形設為「×」而評價光聚合起始劑之溶解性。 For each of the sealants for liquid crystal display elements obtained in the examples and comparative examples, 2 g of a photopolymerization initiator used in each sealant was added to 100 g of the curable resin used in each sealant, and the temperature was 120 ° C. Heating in an oven. Set "○○○" when it is completely dissolved within 5 minutes after the start of heating, and set it as "○○" when it is completely dissolved within 5 minutes and less than 10 minutes. A case where it completely dissolves before 30 minutes is set to "○", a case where it dissolves within 30 minutes but remains dissolved is set to "△", and a case where it does not completely dissolve after 30 minutes is set to "x". The solubility of the photopolymerization initiator was evaluated.
(遮光部硬化性) (Light-shielding part hardening)
首先，準備厚度0.7mm之康寧玻璃之半面經鉻蒸鍍的基板A、與前表面經鉻蒸鍍之基板B。繼而，對於在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，利用行星式攪拌裝置使平均粒徑5μm之間隔粒子(積水化學工業公司製造，「Micropearl SP-2050」)1重量份均勻地分 散。繼而，將分散有該間隔粒子之密封劑塗佈於基板A之中央部(鉻蒸鍍部與非蒸鍍部之交界)，貼合基板B後充分地壓碎密封劑，使用金屬鹵素燈，自基板A側照射100mW/cm2之紫外線30秒鐘。 First, a substrate A on which half of the Corning glass having a thickness of 0.7 mm was subjected to chromium vapor deposition, and a substrate B having a front surface to which chromium was vapor deposited were prepared. Next, with respect to 100 parts by weight of each of the sealants for liquid crystal display elements obtained in the Examples and Comparative Examples, spacer particles having an average particle diameter of 5 μm (made by Sekisui Chemical Industry Co., Ltd., "Micropearl SP-2050") were used with a planetary stirring device. ) 1 part by weight is uniformly dispersed. Next, the sealant in which the spacer particles are dispersed is applied to the central portion of the substrate A (the boundary between the chromium vapor-deposited portion and the non-evaporated portion), the substrate B is bonded, and the sealant is sufficiently crushed. 100 mW / cm 2 of ultraviolet rays were irradiated from the substrate A side for 30 seconds.
其後，使用切割器將基板A及B剝離，針對距離紫外線直接照射部50μm之位置(因鉻蒸鍍而被遮光之部分)上之密封劑，藉由顯微IR(infrared radiation，紅外線輻射)法測定光譜，並藉由以下之方法求出密封劑中之(甲基)丙烯醯基之轉化率。即，將815~800cm-1之峰面積設為(甲基)丙烯醯基之峰面積，將845~820cm-1之峰面積設為參考峰面積，藉由下述式而算出(甲基)丙烯醯基之轉化率。將(甲基)丙烯醯基之轉化率為80%以上之情形設為「○」，將30%以上且未達80%之情形設為「△」，將未達30%之情形設為「×」而評價遮光部硬化性。 After that, the substrates A and B were peeled off using a cutter, and the sealant on a position 50 μm away from the direct ultraviolet irradiation portion (the portion which was shielded by chromium vapor deposition) was subjected to microscopic IR (infrared radiation). The spectrum was measured by the method, and the conversion rate of the (meth) acrylfluorenyl group in the sealant was determined by the following method. That is, a peak area of 815 to 800 cm -1 is a peak area of (meth) acrylfluorenyl group, a peak area of 845 to 820 cm -1 is a reference peak area, and (methyl) is calculated by the following formula. Conversion rate of propylene fluorenyl. The case where the conversion rate of (meth) acrylfluorenyl group is 80% or more is set to "○", the case where the conversion rate is 30% or more and less than 80% is set to "△", and the case that is less than 30% is set to " × ", and the light-shielding portion was evaluated for its hardenability.
(甲基)丙烯醯基之轉化率=(1-(紫外線照射後之(甲基)丙烯醯基之峰面積/紫外線照射後之參考峰面積)/(紫外線照射前之(甲基)丙烯醯基之峰面積/紫外線照射前之參考峰面積))×100 Conversion rate of (meth) acrylfluorene group = (1- (peak area of (meth) acrylfluorene group after ultraviolet irradiation / reference peak area after ultraviolet radiation) / (meth) acrylamine before ultraviolet radiation Base peak area / reference peak area before UV irradiation)) × 100
(液晶顯示元件之顯示性能(低液晶污染性)) (Display performance of liquid crystal display elements (low liquid crystal pollution))
對於在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，利用行星式攪拌裝置使平均粒徑5μm之間隔粒子(積水化學工業公司製造，「Micropearl SP-2050」)1重量份均勻地分散。繼而，將該分散有間隔粒子之密封劑填充於點膠用之注射器(Musashi Engineering公司製造，「PSY-10E」)中，進行脫泡處理後，利用點膠機(Musashi Engineering公司製造，「SHOTMASTER 300」)，於2片附ITO薄膜之透明電極基板之一片上將密封劑塗佈成框狀。繼而，利用液晶滴下裝置將TN液晶(Chisso 公司製造，「JC-5001LA」)之微小液滴滴至密封劑之框內並進行塗佈，利用真空貼合裝置，於5Pa之真空下貼合另一片透明電極基板，而獲得單元。使用金屬鹵素燈，對所獲得之單元照射100mW/cm2之紫外線30秒鐘後，於120℃加熱1小時而使密封劑硬化，而獲得液晶顯示元件。 With respect to 100 parts by weight of each of the sealing compounds for liquid crystal display elements obtained in the examples and comparative examples, spacer particles having an average particle diameter of 5 μm ("Micropearl SP-2050", manufactured by Sekisui Chemical Industry Co., Ltd.) were used with a planetary stirring device. 1 Parts by weight are uniformly dispersed. Next, the sealant in which the spacer particles were dispersed was filled in a syringe for dispensing ("Musashi Engineering Co., Ltd." PSY-10E "), and after performing a defoaming treatment, a dispenser (Musashi Engineering Co.," SHOTMASTER " 300 ″), apply the sealant into a frame on one of the two transparent electrode substrates with ITO film. Next, a tiny liquid droplet of TN liquid crystal (manufactured by Chisso Corporation, "JC-5001LA") was dropped into the frame of the sealant using a liquid crystal dropping device, and applied, and a vacuum bonding device was used to bond another liquid under a vacuum of 5 Pa. One piece of transparent electrode substrate to obtain the unit. The obtained unit was irradiated with 100 mW / cm 2 of ultraviolet rays for 30 seconds using a metal halide lamp, and then heated at 120 ° C. for 1 hour to harden the sealant to obtain a liquid crystal display element.
針對所獲得之液晶顯示元件，利用目視觀察密封部周邊之液晶(尤其是角隅部)，將未確認到顯示不均或線殘像之情形設為「○」，將清楚地確認到顯示不均或線殘像之情形設為「△」，將確認到嚴重之顯示不均或線殘像之情形設為「×」而評價液晶顯示元件之顯示性能(低液晶污染性)。 Regarding the obtained liquid crystal display element, visually observe the liquid crystal (especially the corner portion) around the sealing portion, and set the case where no display unevenness or line afterimage is confirmed to "○", and clearly display unevenness The case of an after-image or an after-image was set to "△", and the case where a serious display unevenness was confirmed or the case of an after-image of an image was set to "×" to evaluate the display performance of the liquid crystal display element (low liquid crystal contamination).
[產業上之可利用性] [Industrial availability]
根據本發明，可提供一種遮光部硬化性優異，且可抑制液晶污染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 is excellent in the light-shielding portion and that can suppress liquid crystal contamination. Furthermore, according to the present invention, it is possible to provide a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.
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| JP2020138996A (en) * | 2019-02-26 | 2020-09-03 | 味の素株式会社 | Resin composition |
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| EP1405888A1 (en) | 2001-05-16 | 2004-04-07 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
| JP4380359B2 (en) * | 2004-02-20 | 2009-12-09 | Ｊｓｒ株式会社 | Radiation-sensitive resin composition for spacer formation, spacer, method for forming the spacer, and liquid crystal display element |
| US20090061117A1 (en) * | 2005-05-09 | 2009-03-05 | Yuichi Oyama | Sealant for one drop fill process, vertically conducting material and liquid crystal display device |
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| JP5152868B2 (en) * | 2009-06-11 | 2013-02-27 | 日本化薬株式会社 | Visible light curable liquid crystal sealant and liquid crystal display cell using the same |
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| JP2014006325A (en) * | 2012-06-22 | 2014-01-16 | Nippon Kayaku Co Ltd | Liquid crystal sealing agent and liquid crystal display cell using the same |
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