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TWI872025B - Sealant for liquid crystal element, vertical conductive material and liquid crystal element - Google Patents

Sealant for liquid crystal element, vertical conductive material and liquid crystal element Download PDF

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TWI872025B
TWI872025B TW108124247A TW108124247A TWI872025B TW I872025 B TWI872025 B TW I872025B TW 108124247 A TW108124247 A TW 108124247A TW 108124247 A TW108124247 A TW 108124247A TW I872025 B TWI872025 B TW I872025B
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liquid crystal
sealant
meth
compound
acrylate
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TW202005990A (en
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山脇大輝
樋口勲夫
高橋駿介
柴田大輔
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日商積水化學工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/30—Nitriles
    • C08F222/32—Alpha-cyano-acrylic acid; Esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
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    • 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

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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Liquid Crystal (AREA)
  • Sealing Material Composition (AREA)

Abstract

本發明之目的在於提供一種液晶元件用密封劑，其對長波長之光的深部硬化性優異，且可抑制液晶向密封劑插入或由密封劑所導致之液晶污染。又，本發明之目的在於提供一種使用該液晶元件用密封劑而成之上下導通材料及液晶元件。 本發明之液晶元件用密封劑含有硬化性樹脂及光聚合起始劑，上述光聚合起始劑含有9-氧硫 （thioxanthone）化合物及肟酯（oxime ester）化合物。The purpose of the present invention is to provide a sealant for a liquid crystal element, which has excellent deep curing properties to long-wavelength light and can inhibit the insertion of liquid crystal into the sealant or liquid crystal contamination caused by the sealant. In addition, the purpose of the present invention is to provide a top-bottom conductive material and a liquid crystal element formed by using the sealant for a liquid crystal element. The sealant for a liquid crystal element of the present invention contains a curable resin and a photopolymerization initiator, and the photopolymerization initiator contains 9-oxysulfide (thioxanthone) compounds and oxime ester compounds.

Description

液晶元件用密封劑、上下導通材料及液晶元件Sealant for liquid crystal element, vertical conductive material and liquid crystal element

本發明係關於一種對長波長之光的深部硬化性優異、可抑制液晶向密封劑插入或由密封劑所導致之液晶污染的液晶元件用密封劑。又，本發明係關於一種使用該液晶元件用密封劑而成之上下導通材料及液晶元件。 The present invention relates to a sealant for liquid crystal elements that has excellent deep curing properties against long-wavelength light and can inhibit the insertion of liquid crystal into the sealant or liquid crystal contamination caused by the sealant. In addition, the present invention relates to an upper and lower conductive material and a liquid crystal element formed using the sealant for liquid crystal elements.

近年，作為液晶顯示單元等液晶元件之製造方法，自產距時間(tact time)縮短、使用液晶量之最佳化等觀點而言，採用如專利文獻1、專利文獻2中所揭示之利用光熱並用硬化型密封劑之稱為滴下法之液晶滴下方式。 In recent years, as a manufacturing method for liquid crystal elements such as liquid crystal display units, from the perspective of shortening the tact time and optimizing the amount of liquid crystal used, a liquid crystal dropping method called a dropping method using light and heat and a curing sealant as disclosed in Patent Documents 1 and 2 has been adopted.

於滴下法中，首先，於2塊附電極之透明基板之一者上藉由滴塗(dispense)形成框狀之密封圖案。繼而，於密封劑未硬化之狀態下將液晶之微滴滴至透明基板之框內整個面，立刻與另一透明基板貼合，對密封部照射紫外線等光而進行暫時硬化。其後，於液晶退火時加熱而進行正式硬化，從而製作液晶元件。若於減壓下進行基板之貼合，則可以極高之效率製造液晶元件，該滴下法成為當前液晶元件之製造方法的主流。 In the drip method, first, a frame-shaped sealing pattern is formed by dispensing on one of the two transparent substrates with electrodes. Then, before the sealant is cured, tiny drops of liquid crystal are dropped onto the entire surface of the frame of the transparent substrate, and the other transparent substrate is immediately bonded together, and the sealing part is irradiated with ultraviolet light for temporary curing. Afterwards, the liquid crystal is heated during annealing to formally cure, thereby manufacturing a liquid crystal element. If the substrates are bonded under reduced pressure, liquid crystal elements can be manufactured with extremely high efficiency, and this drip method has become the mainstream method for manufacturing liquid crystal elements at present.

然而，於行動電話、攜帶型遊戲機等各種附液晶面板之移動設備普及之當代，裝置之小型化為最追求之課題。作為裝置之小型化之方法，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)。 However, in the current era when various mobile devices with LCD panels such as mobile phones and portable game consoles are becoming popular, the miniaturization of devices is the most pursued topic. As a method of miniaturizing devices, narrowing the edge of the liquid crystal display part can be cited, for example, arranging the position of the sealing part under the black matrix (hereinafter also referred to as narrow edge design).

然而，於窄邊緣設計之情形時因密封劑配置於黑矩陣之正下方， 故若進行滴下法，則存在使密封劑光硬化時所照射之光受到遮擋、光無法到達密封劑之內部從而硬化變得不充分之問題。若如此密封劑之硬化變得不充分，則存在以下問題：未硬化之密封劑成分溶出至液晶中，溶出之密封劑成分於液晶中進行硬化反應，而導致發生液晶污染。 However, in the case of a narrow edge design, since the sealant is placed directly below the black matrix, if the drip method is used, there is a problem that the light irradiated during the photocuring of the sealant is blocked, and the light cannot reach the inside of the sealant, resulting in insufficient curing. If the sealant is not sufficiently cured, there is the following problem: the uncured sealant components are dissolved into the liquid crystal, and the dissolved sealant components undergo a curing reaction in the liquid crystal, resulting in liquid crystal contamination.

又，通常，作為使密封劑光硬化之方法而進行紫外線之照射，但特別是於液晶滴下法中，滴下液晶後為了使密封劑硬化而照射紫外線，因此存在液晶發生劣化之問題。對此，為了防止由紫外線所導致之液晶之劣化，摻合對可見光區域的長波長之光的反應性優異之光聚合起始劑，介隔截止濾光鏡等藉由長波長之光進行光硬化。 In addition, usually, ultraviolet irradiation is performed as a method for photocuring the sealant, but in particular in the liquid crystal dropping method, ultraviolet irradiation is performed to cure the sealant after dropping the liquid crystal, so there is a problem of liquid crystal degradation. In order to prevent the degradation of liquid crystal caused by ultraviolet rays, a photopolymerization initiator with excellent reactivity to long-wavelength light in the visible light region is mixed, and a cutoff filter is used to perform photocuring by long-wavelength light.

[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 Publication No. 2001-133794

專利文獻2：國際公開第02/092718號 Patent document 2: International Publication No. 02/092718

本發明之目的在於提供一種對長波長之光的深部硬化性優異、可抑制液晶向密封劑插入或由密封劑所導致之液晶污染的液晶元件用密封劑。又，本發明之目的在於提供一種使用該液晶元件用密封劑而成之上下導通材料及液晶元件。 The purpose of the present invention is to provide a sealant for liquid crystal elements that has excellent deep curing properties to long-wavelength light and can inhibit the insertion of liquid crystal into the sealant or liquid crystal contamination caused by the sealant. In addition, the purpose of the present invention is to provide an upper and lower conductive material and a liquid crystal element formed by using the sealant for liquid crystal elements.

本發明係一種液晶元件用密封劑，其含有硬化性樹脂及光聚合起 始劑，上述光聚合起始劑含有9-氧硫

Figure 108124247-A0305-12-0003-10
(thioxanthone)化合物及肟酯(oxime ester)化合物。 The present invention is a sealing agent for a liquid crystal element, which contains a curable resin and a photopolymerization initiator, wherein the photopolymerization initiator contains 9-oxysulfide
Figure 108124247-A0305-12-0003-10
(thioxanthone) compounds and oxime ester compounds.

以下，對本發明進行詳述。 The present invention is described in detail below.

近年，對裸眼3D液晶面板或液晶天線等單元間隙較大之液晶元件進行開發。於對如此單元間隙較大之液晶元件使用以往之密封劑，藉由長波長之光進行光硬化之情形時，存在以下問題：於液晶退火時等液晶插入密封劑，從而發生密封破裂而液晶漏出，或液晶受到密封劑之污染。本發明人等認為，單元間隙較大之液晶元件中發生液晶向密封劑之插入或由密封劑所導致之液晶污染之原因在於，密封劑之厚度變厚，因此即便是以往藉由可見光可充分硬化之密封劑亦無法硬化至深部。對此，本發明人等研究出將9-氧硫

Figure 108124247-A0305-12-0003-11
化合物與肟酯化合物組合而用作密封劑所用之光聚合起始劑。其結果，發現可獲得對長波長之光的深部硬化性優異、可抑制液晶向密封劑插入或由密封劑所導致之液晶污染的液晶元件用密封劑，從而完成本發明。 In recent years, development has been conducted on liquid crystal elements with larger cell gaps, such as naked-eye 3D liquid crystal panels and liquid crystal antennas. When using conventional sealants for such liquid crystal elements with larger cell gaps and performing photocuring with long-wavelength light, there are the following problems: the liquid crystal is inserted into the sealant during liquid crystal annealing, causing the seal to break and the liquid crystal to leak out, or the liquid crystal is contaminated by the sealant. The inventors of the present invention believe that the reason for the insertion of liquid crystal into the sealant or the contamination of liquid crystal by the sealant in liquid crystal elements with larger cell gaps is that the thickness of the sealant becomes thicker, so even the sealant that can be fully cured by visible light in the past cannot be cured to a deep level. In response to this, the inventors of the present invention have developed a method of injecting 9-oxysulfur into the sealant.
Figure 108124247-A0305-12-0003-11
The present invention was completed by combining a compound with an oxime ester compound as a photopolymerization initiator for a sealant. As a result, it was found that a sealant for a liquid crystal element that has excellent deep curing properties to long-wavelength light and can suppress the insertion of liquid crystal into the sealant or liquid crystal contamination caused by the sealant can be obtained.

本發明之液晶元件用密封劑含有光聚合起始劑。 The sealant for liquid crystal elements of the present invention contains a photopolymerization initiator.

上述光聚合起始劑含有9-氧硫

Figure 108124247-A0305-12-0003-16
化合物。藉由將上述9-氧硫
Figure 108124247-A0305-12-0003-17
化合物與後述肟酯化合物組合而用作上述光聚合起始劑，本發明之液晶元件用密封劑成為對長波長之光的深部硬化性優異者。 The above-mentioned photopolymerization initiator contains 9-oxysulfide
Figure 108124247-A0305-12-0003-16
Compound. By adding the above 9-oxosulfur
Figure 108124247-A0305-12-0003-17
When the compound is used as the above-mentioned photopolymerization initiator in combination with the oxime ester compound described later, the liquid crystal element sealant of the present invention becomes one with excellent deep curing property against long-wavelength light.

再者，於本說明書中，上述「9-氧硫

Figure 108124247-A0305-12-0003-12
化合物」意指具有9-氧硫
Figure 108124247-A0305-12-0003-14
基(thioxanthonyl group)之化合物，上述「9-氧硫
Figure 108124247-A0305-12-0003-13
基」意指9-側氧-9H-硫
Figure 108124247-A0305-12-0003-15
-基。 Furthermore, in this specification, the above-mentioned "9-oxysulfur
Figure 108124247-A0305-12-0003-12
Compounds are compounds having 9-oxosulfur
Figure 108124247-A0305-12-0003-14
The above-mentioned "9-oxysulfur
Figure 108124247-A0305-12-0003-13
"Hydroxyl" means 9-oxo-9H-sulfur
Figure 108124247-A0305-12-0003-15
-base.

上述9-氧硫

Figure 108124247-A0305-12-0003-18
化合物較佳為於主鏈之末端具有9-氧硫
Figure 108124247-A0305-12-0003-19
基。 The above 9-oxysulfur
Figure 108124247-A0305-12-0003-18
The compound preferably has a 9-oxosulfur group at the end of the main chain.
Figure 108124247-A0305-12-0003-19
base.

又，上述9-氧硫

Figure 108124247-A0305-12-0003-20
化合物較佳為於1分子中具有3個以上之9-氧硫
Figure 108124247-A0305-12-0003-22
基。藉由上述9-氧硫
Figure 108124247-A0305-12-0003-21
化合物於1分子中具有3個以上之9-氧硫
Figure 108124247-A0305-12-0003-23
基，所獲得之液晶元件用密封劑成為對長波長之光的深部硬化性更優異者。 Furthermore, the above 9-oxysulfur
Figure 108124247-A0305-12-0003-20
The compound preferably has three or more 9-oxosulfur groups in one molecule.
Figure 108124247-A0305-12-0003-22
By the above 9-oxysulfur
Figure 108124247-A0305-12-0003-21
The compound has three or more 9-oxosulfur groups in one molecule.
Figure 108124247-A0305-12-0003-23
The obtained liquid crystal element sealant has a more excellent deep curing property against long-wavelength light.

上述9-氧硫

Figure 108124247-A0305-12-0004-24
化合物較佳為具有醯胺鍵。藉由上述9-氧硫
Figure 108124247-A0305-12-0004-25
化合物具有醯胺鍵，所獲得之液晶元件用密封劑之極性增強，因此，成為液晶污染性較低之密封劑。 The above 9-oxysulfur
Figure 108124247-A0305-12-0004-24
The compound preferably has an amide bond.
Figure 108124247-A0305-12-0004-25
The compound has an amide bond, and the polarity of the obtained sealant for liquid crystal elements is enhanced, thereby becoming a sealant with low liquid crystal contamination.

於上述9-氧硫

Figure 108124247-A0305-12-0004-27
化合物具有醯胺鍵之情形時，上述9-氧硫
Figure 108124247-A0305-12-0004-26
化合物之醯胺鍵當量之較佳之上限為300。藉由上述9-氧硫
Figure 108124247-A0305-12-0004-28
化合物之醯胺鍵當量為300以下，所獲得之液晶元件用密封劑成為對長波長之光的深部硬化性更優異者。上述9-氧硫
Figure 108124247-A0305-12-0004-29
化合物之醯胺鍵當量之更佳之上限為280。 In the above 9-oxysulfur
Figure 108124247-A0305-12-0004-27
When the compound has an amide bond, the above 9-oxosulfur
Figure 108124247-A0305-12-0004-26
The preferred upper limit of the amide bond equivalent of the compound is 300.
Figure 108124247-A0305-12-0004-28
When the amide bond equivalent of the compound is 300 or less, the obtained liquid crystal element sealant has a more excellent deep curing property against long-wavelength light.
Figure 108124247-A0305-12-0004-29
A more preferred upper limit of the amide bond equivalent of the compound is 280.

又，上述9-氧硫

Figure 108124247-A0305-12-0004-30
化合物之醯胺鍵當量之較佳之下限並無特別，實質性下限為150。 Furthermore, the above 9-oxysulfur
Figure 108124247-A0305-12-0004-30
There is no particular lower limit for the preferred amide bond equivalent of the compound, and the practical lower limit is 150.

再者，於本說明書中，上述「醯胺鍵當量」係上述9-氧硫

Figure 108124247-A0305-12-0004-31
化合物之重量(g)除以上述9-氧硫
Figure 108124247-A0305-12-0004-32
化合物中所含之醯胺鍵之莫耳數(mol)而求出之值。 In this specification, the above-mentioned "amide bond equivalent" refers to the above-mentioned 9-oxosulfur
Figure 108124247-A0305-12-0004-31
The weight of the compound (g) is divided by the above 9-oxosulfur
Figure 108124247-A0305-12-0004-32
The value calculated based on the molar number (mol) of amide bonds contained in the compound.

上述9-氧硫

Figure 108124247-A0305-12-0004-33
化合物之分子量的較佳之下限為1000。藉由上述9-氧硫
Figure 108124247-A0305-12-0004-35
化合物之分子量為1000以上，所獲得之液晶元件用密封劑成為低液晶污染性更優異者。上述9-氧硫
Figure 108124247-A0305-12-0004-34
化合物之分子量之更佳之下限為1200。 The above 9-oxysulfur
Figure 108124247-A0305-12-0004-33
The preferred lower limit of the molecular weight of the compound is 1000.
Figure 108124247-A0305-12-0004-35
When the molecular weight of the compound is 1000 or more, the obtained liquid crystal element sealant has a lower liquid crystal contamination property.
Figure 108124247-A0305-12-0004-34
A more preferable lower limit of the molecular weight of the compound is 1,200.

又，自與硬化性樹脂之相容性或所獲得之液晶元件用密封劑之作業性等觀點而言，上述9-氧硫

Figure 108124247-A0305-12-0004-36
化合物之分子量的較佳之上限為2000。 Furthermore, from the viewpoint of compatibility with the curable resin or workability of the obtained liquid crystal element sealant, the above-mentioned 9-oxysulfide
Figure 108124247-A0305-12-0004-36
The preferred upper limit of the molecular weight of the compound is 2,000.

再者，於本說明書中，上述「分子量」對於分子結構特定之化合物係自結構式求出之分子量，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存在使用數量平均分子量表示之情況。又，於本說明書中，上述「數量平均分子量」係藉由凝膠滲透層析法(GPC)使用四氫呋喃作為溶劑進行測定，基於聚苯乙烯換算而求出之值。作為藉由GPC測定基於聚苯乙烯換算之數量平均分子量時所用之管柱，例如可列舉Shodex LF-804(昭和電工公司製造)等。 Furthermore, in this specification, the above "molecular weight" is the molecular weight obtained from the structural formula for compounds with specific molecular structures, and the number average molecular weight is sometimes used to represent compounds with a wide distribution of polymerization degrees and compounds with unspecified modified sites. In addition, in this specification, the above "number average molecular weight" is a value obtained by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converted based on polystyrene. As a column used when measuring the number average molecular weight based on polystyrene conversion by GPC, for example, Shodex LF-804 (manufactured by Showa Denko K.K.) can be cited.

作為上述9-氧硫

Figure 108124247-A0305-12-0004-37
化合物，具體而言，較佳為下述式(1-1)所表示之化合物及下述式(1-2)所表示之化合物之至少任一者。 As the above 9-oxosulfur
Figure 108124247-A0305-12-0004-37
Specifically, the compound is preferably at least one of a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2).

Figure 108124247-A0305-12-0005-1
Figure 108124247-A0305-12-0005-1

Figure 108124247-A0305-12-0005-2
Figure 108124247-A0305-12-0005-2

於式(1-2)中，n為1~10(平均值)。 In formula (1-2), n is 1~10 (average value).

上述式(1-1)、上述式(1-2)中之芳香環之氫原子可經取代基取代。作為該取代基，例如可列舉：甲基、乙基、丙基等。 The hydrogen atom of the aromatic ring in the above formula (1-1) and the above formula (1-2) may be substituted by a substituent. Examples of the substituent include methyl, ethyl, propyl, etc.

上述9-氧硫

Figure 108124247-A0305-12-0005-43
化合物與後述肟酯化合物之合計中的上述9-氧硫
Figure 108124247-A0305-12-0005-45
化合物之含有比例的較佳之下限為30重量%，較佳之上限為80重量%。藉由上述9-氧硫
Figure 108124247-A0305-12-0005-42
化合物之含有比例於該範圍內，所獲得之液晶元件用密封劑成為對長波長之光的深部硬化性更優異者。上述9-氧硫
Figure 108124247-A0305-12-0005-41
化合物之含有比例的更佳之下限為45重量%，更佳之上限為70重量%。 The above 9-oxysulfur
Figure 108124247-A0305-12-0005-43
The above-mentioned 9-oxosulfur
Figure 108124247-A0305-12-0005-45
The preferred lower limit of the content ratio of the compound is 30% by weight, and the preferred upper limit is 80% by weight.
Figure 108124247-A0305-12-0005-42
When the content ratio of the compound is within the above range, the obtained liquid crystal element sealant has a more excellent deep curing property against long-wavelength light.
Figure 108124247-A0305-12-0005-41
A more preferable lower limit of the content ratio of the compound is 45% by weight, and a more preferable upper limit is 70% by weight.

上述光聚合起始劑含有肟酯化合物。藉由將上述肟酯化合物與上述9-氧硫

Figure 108124247-A0305-12-0005-44
化合物組合而用作上述光聚合起始劑，本發明之液晶元件用密封劑成為對長波長之光的深部硬化性優異者。 The photopolymerization initiator contains an oxime ester compound.
Figure 108124247-A0305-12-0005-44
When the above-mentioned compound combination is used as the photopolymerization initiator, the liquid crystal element sealant of the present invention becomes excellent in deep curing property against long-wavelength light.

再者，於本說明書中，上述「肟酯化合物」意指具有肟酯骨架之化合物。 Furthermore, in this specification, the above-mentioned "oxime ester compound" means a compound having an oxime ester skeleton.

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(2)所表示之化合物、下述式(3)所表示之化合物等。 Examples of the above-mentioned oxime ester compounds include: 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyl oxime), O-acetyl-1-(6-(2-methylbenzoyl)-9-ethyl-9H-carbazole-3-yl)ethanone oxime, compounds represented by the following formula (2), compounds represented by the following formula (3), etc.

Figure 108124247-A0305-12-0006-3
Figure 108124247-A0305-12-0006-3

Figure 108124247-A0305-12-0006-4
Figure 108124247-A0305-12-0006-4

上述式(2)、上述式(3)中之芳香環之氫原子可經取代基取代。作為該取代基，例如可列舉：甲基、乙基、丙基等。 The hydrogen atom of the aromatic ring in the above formula (2) and the above formula (3) may be substituted by a substituent. Examples of the substituent include methyl, ethyl, propyl, etc.

上述9-氧硫

Figure 108124247-A0305-12-0006-38
化合物與上述肟酯化合物之合計含量相對於硬化性樹脂100重量份，較佳之下限為1重量份，較佳之上限為15重量份。藉由上述9-氧硫
Figure 108124247-A0305-12-0006-39
化合物與上述肟酯化合物之合計含量於該範圍內，所獲得之液晶元件用密封劑成為對長波長之光的深部硬化性更優異者。上述9-氧硫
Figure 108124247-A0305-12-0006-40
化合物與上述肟酯化合物之合計含量的更佳之下限為2重量份，更佳之上限為8重量份。 The above 9-oxysulfur
Figure 108124247-A0305-12-0006-38
The total content of the compound and the above-mentioned oxime ester compound is preferably 1 part by weight and 15 parts by weight, relative to 100 parts by weight of the curable resin.
Figure 108124247-A0305-12-0006-39
When the total content of the compound and the oxime ester compound is within the above range, the obtained liquid crystal element sealant has a more excellent deep curing property against long-wavelength light.
Figure 108124247-A0305-12-0006-40
The more preferable lower limit of the total content of the compound and the above-mentioned oxime ester compound is 2 parts by weight, and the more preferable upper limit is 8 parts by weight.

本發明之液晶元件用密封劑含有硬化性樹脂。 The sealant for the liquid crystal element of the present invention contains a curable resin.

上述硬化性樹脂較佳為含有(甲基)丙烯酸化合物。 The above-mentioned hardening resin preferably contains a (meth) acrylic acid compound.

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(urethane(meth)acrylate)等。其中，較佳為環氧(甲基)丙烯酸酯。又，上述(甲基)丙烯酸化合物自反應性之觀點而言，較佳為 於1分子中具有2個以上之(甲基)丙烯醯基。 Examples of the above-mentioned (meth) acrylic acid compounds include (meth) acrylic acid ester compounds, epoxy (meth) acrylic acid esters, and (meth) acrylic acid amine esters (urethane (meth) acrylate). Among them, epoxy (meth) acrylic acid esters are preferred. In addition, from the viewpoint of self-reactivity, the above-mentioned (meth) acrylic acid compounds preferably have 2 or more (meth) acrylic acid groups in one molecule.

再者，於本說明書中，上述「(甲基)丙烯酸基」意指丙烯酸基或甲基丙烯酸基，上述「(甲基)丙烯酸化合物」意指具有(甲基)丙烯醯基之化合物，上述「(甲基)丙烯醯基」意指丙烯醯基或甲基丙烯醯基。又，上述「(甲基)丙烯酸酯」意指丙烯酸酯或甲基丙烯酸酯。進而，上述「環氧(甲基)丙烯酸酯」係表示使環氧化合物中之所有環氧基與(甲基)丙烯酸反應而獲得之化合物。 Furthermore, in this specification, the above-mentioned "(meth)acrylic group" means an acrylic group or a methacrylic group, the above-mentioned "(meth)acrylic compound" means a compound having a (meth)acrylic group, and the above-mentioned "(meth)acrylic group" means an acryl group or a methacrylic group. Moreover, the above-mentioned "(meth)acrylate" means an acrylate or a methacrylate. Furthermore, the above-mentioned "epoxy (meth)acrylate" means a compound obtained by reacting all epoxy groups in an epoxy compound 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)丙烯酸異莰酯(isobornyl(meth)acrylate)、(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)丙烯醯氧基乙酯、六氫鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯、鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯2-羥基丙酯、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 (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. isomyristyl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-Ethoxyethyl (meth)acrylate, 2-Butoxyethyl (meth)acrylate, 2-Phenoxyethyl (meth)acrylate, Methoxyethylene glycol (meth)acrylate, Methoxypolyethylene glycol (meth)acrylate, Phenoxydiethylene glycol (meth)acrylate, Phenoxypolyethylene glycol (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, Ethyl carbitol (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2, 3,3-tetrafluoropropyl, 1H,1H,5H-octafluoropentyl (meth)acrylate, imide (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxyethyl phthalate 2-hydroxypropyl, 2-(meth)acryloyloxyethyl phosphate, glycidyl (meth)acrylate, etc.

又，作為上述(甲基)丙烯酸酯化合物中之二官能者，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。 In addition, as the bifunctional (meth)acrylate compounds mentioned above, for example, 1,3-butanediol di(meth)acrylate, 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 glycol di(meth)acrylate, ethylene oxide added bisphenol A di(meth)acrylate, propylene oxide added bisphenol A di(meth)acrylate, ethylene oxide added bisphenol F di(meth)acrylate, dihydroxymethyl dicyclopentadiene di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, (meth)acrylate 2-hydroxy-3-(meth)acryloyloxypropyl, carbonate diol di(meth)acrylate, 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三官能以上者，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, as the trifunctional or higher functional (meth)acrylate compounds mentioned above, for example, trihydroxymethylpropane tri(meth)acrylate, ethylene oxide addition trihydroxymethylpropane tri(meth)acrylate, propylene oxide addition trihydroxymethylpropane tri(meth)acrylate, caprolactone modified trihydroxymethylpropane tri(meth)acrylate, ethylene oxide addition isocyanuric acid tri(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tri(meth)acryloyloxyethyl phosphate, di-trihydroxymethylpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. can be cited.

作為上述環氧(甲基)丙烯酸酯，例如可列舉藉由使環氧化合物與(甲基)丙烯酸按照常規方法於鹼性觸媒之存在下反應而獲得者等。 As the above-mentioned epoxy (meth) acrylate, for example, there can be cited those obtained by reacting an epoxy compound with (meth) acrylic acid in the presence of an alkaline catalyst according to a conventional method.

關於作為用於合成上述環氧(甲基)丙烯酸酯之原料的環氧化合物，例如可列舉：雙酚A型環氧化合物、雙酚F型環氧化合物、雙酚S型環氧化合物、2,2'-二烯丙基雙酚A型環氧化合物、氫化雙酚型環氧化合物、環氧丙烷加成 雙酚A型環氧化合物、間苯二酚型環氧化合物、聯苯型環氧化合物、硫醚型環氧化合物、二苯醚型環氧化合物、二環戊二烯型環氧化合物、萘型環氧化合物、苯酚酚醛清漆型環氧化合物、鄰甲酚酚醛清漆型環氧化合物、二環戊二烯酚醛清漆型環氧化合物、聯苯酚醛清漆型環氧化合物、萘酚酚醛清漆型環氧化合物、縮水甘油胺型環氧化合物、烷基多元醇型環氧化合物、橡膠改質型環氧化合物、縮水甘油酯化合物等。 Regarding the epoxy compounds used as raw materials for synthesizing the above-mentioned epoxy (meth) acrylate, for example, there can be listed: bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, 2,2'-diallylbisphenol A type epoxy compounds, hydrogenated bisphenol type epoxy compounds, epoxy propane addition bisphenol A type epoxy compounds, resorcinol type epoxy compounds, biphenyl type epoxy compounds, thioether type epoxy compounds, dimethicone type epoxy compounds, Phenyl ether type epoxy compounds, dicyclopentadiene type epoxy compounds, naphthalene type epoxy compounds, phenol novolac type epoxy compounds, o-cresol novolac type epoxy compounds, dicyclopentadiene novolac type epoxy compounds, biphenyl novolac type epoxy compounds, naphthol novolac type epoxy compounds, glycidylamine type epoxy compounds, alkyl polyol type epoxy compounds, rubber modified epoxy compounds, glycidyl ester compounds, etc.

作為上述雙酚A型環氧化合物中之市售者，例如可列舉：jER828EL、jER1004(均為三菱化學公司製造)、EPICLON EXA-850CRP(DIC公司製造)等。 Examples of the commercially available bisphenol A type epoxy compounds include: jER828EL, jER1004 (both manufactured by Mitsubishi Chemical Corporation), EPICLON EXA-850CRP (manufactured by DIC Corporation), etc.

作為上述雙酚F型環氧化合物中之市售者，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 compounds include jER806 and jER4004 (both manufactured by Mitsubishi Chemical Corporation).

作為上述雙酚S型環氧化合物中之市售者，例如可列舉：EPICLON EXA1514(DIC公司製造)等。 Examples of commercially available bisphenol S-type epoxy compounds include: EPICLON EXA1514 (manufactured by DIC Corporation).

作為上述2,2'-二烯丙基雙酚A型環氧化合物中之市售者，例如可列舉：RE-810NM(日本化藥公司製造)等。 Examples of commercially available 2,2'-diallylbisphenol A type epoxy compounds include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).

作為上述氫化雙酚型環氧化合物中之市售者，例如可列舉：EPICLON EXA7015(DIC公司製造)等。 Examples of commercially available hydrogenated bisphenol epoxy compounds include: EPICLON EXA7015 (manufactured by DIC Corporation).

作為上述環氧丙烷加成雙酚A型環氧化合物中之市售者，例如可列舉：EP-4000S(ADEKA公司製造)等。 Examples of commercially available propylene oxide-added bisphenol A type epoxy compounds include EP-4000S (manufactured by ADEKA Corporation) and the like.

作為上述間苯二酚型環氧化合物中之市售者，例如可列舉：EX-201(長瀨化成公司製造)等。 Examples of commercially available resorcinol-type epoxy compounds include EX-201 (manufactured by Nagase Chemicals Co., Ltd.).

作為上述聯苯型環氧化合物中之市售者，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 compounds include: jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).

作為上述硫醚型環氧化合物中之市售者，例如可列舉：YSLV-50TE(新日 鐵住金化學公司製造)等。 Examples of commercially available sulfide-type epoxy compounds include: YSLV-50TE (manufactured by Nippon Steel & Sumitomo Metal Chemicals Co., Ltd.).

作為上述二苯醚型環氧化合物中之市售者，例如可列舉：YSLV-80DE(新日鐵住金化學公司製造)等。 Examples of commercially available diphenyl ether epoxy compounds include: YSLV-80DE (manufactured by Nippon Steel & Sumitomo Metal Chemicals Co., Ltd.) etc.

作為上述二環戊二烯型環氧化合物中之市售者，例如可列舉：EP-4088S(ADEKA公司製造)等。 Examples of commercially available dicyclopentadiene-type epoxy compounds include EP-4088S (manufactured by ADEKA Corporation).

作為上述萘型環氧化合物中之市售者，例如可列舉：EPICLON HP4032、EPICLON EXA-4700(均為DIC公司製造)等。 Examples of the commercially available naphthalene-type epoxy compounds include: EPICLON HP4032, EPICLON EXA-4700 (both manufactured by DIC Corporation), etc.

作為上述苯酚酚醛清漆型環氧化合物中之市售者，例如可列舉：EPICLON N-770(DIC公司製造)等。 Examples of commercially available phenol novolac-type epoxy compounds include: EPICLON N-770 (manufactured by DIC Corporation) etc.

作為上述鄰甲酚酚醛清漆型環氧化合物中之市售者，例如可列舉：EPICLON N-670-EXP-S(DIC公司製造)等。 Examples of the above-mentioned o-cresol novolac epoxy compounds that are commercially available include: EPICLON N-670-EXP-S (manufactured by DIC Corporation), etc.

作為上述二環戊二烯酚醛清漆型環氧化合物中之市售者，例如可列舉：EPICLON HP7200(DIC公司製造)等。 Examples of commercially available dicyclopentadiene novolac-type epoxy compounds include: EPICLON HP7200 (manufactured by DIC Corporation).

作為上述聯苯酚醛清漆型環氧化合物中之市售者，例如可列舉：NC-3000P(日本化藥公司製造)等。 Examples of commercially available biphenyl novolac epoxy compounds include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).

作為上述萘酚酚醛清漆型環氧化合物中之市售者，例如可列舉：ESN-165S(新日鐵住金化學公司製造)等。 Examples of commercially available naphthol novolac epoxy compounds include ESN-165S (manufactured by Nippon Steel & Sumitomo Metal Chemicals Co., Ltd.).

作為上述縮水甘油胺型環氧化合物中之市售者，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 the above-mentioned glycidylamine-type epoxy compounds that are commercially available include: jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation), etc.

作為上述烷基多元醇型環氧化合物中之市售者，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(長瀨化成公司製造)等。 Examples of commercially available alkyl polyol epoxy compounds include: ZX-1542 (manufactured by Nippon Steel & Sumitomo Metal Chemicals), EPICLON 726 (manufactured by DIC Corporation), Epolight 80MFA (manufactured by Kyoeisha Chemicals), and DENACOL EX-611 (manufactured by Nagase Chemicals).

作為上述橡膠改質型環氧化合物中之市售者，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 the rubber-modified epoxy compounds that are commercially available include: YR-450, YR-207 (both manufactured by Nippon Steel & Sumitomo Metal Chemicals Co., Ltd.), Epolead PB (manufactured by Daicel Corporation), etc.

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(長瀨化成公司製造)等。 Examples of commercially available glycidyl ester compounds include DENACOL EX-147 (manufactured by Nagase Chemicals Co., Ltd.).

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)、XAC4151(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。 Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Chemicals), XAC4151 (manufactured by Asahi Kasei), jER1031, jER1032 (all manufactured by Mitsubishi Chemical), EXA-7120 (manufactured by DIC), TEPIC (manufactured by Nissan Chemical), etc.

作為上述環氧(甲基)丙烯酸酯中之市售者，例如可列舉：DAICEL-ALLNEX公司製造之環氧(甲基)丙烯酸酯、新中村化學工業公司製造之環氧(甲基)丙烯酸酯、共榮社化學公司製造之環氧(甲基)丙烯酸酯、長瀨化成公司製造之環氧(甲基)丙烯酸酯等。 Examples of commercially available epoxy (meth)acrylates include epoxy (meth)acrylate manufactured by DAICEL-ALLNEX, epoxy (meth)acrylate manufactured by Shin-Nakamura Chemical Industry, epoxy (meth)acrylate manufactured by Kyoeisha Chemical, and epoxy (meth)acrylate manufactured by Nagase Chemicals.

作為上述DAICEL-ALLNEX公司製造之環氧(甲基)丙烯酸酯，例如可列舉：EBECRYL860、EBECRYL3200、EBECRYL3201、EBECRYL3412、EBECRYL3600、EBECRYL3700、EBECRYL3701、EBECRYL3702、EBECRYL3703、EBECRYL3708、EBECRYL3800、EBECRYL6040、EBECRYL RDX63182等。 Examples of epoxy (meth)acrylates manufactured by the aforementioned DAICEL-ALLNEX company include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, EBECRYL RDX63182, etc.

作為上述新中村化學工業公司製造之環氧(甲基)丙烯酸酯，例如可列舉：EA-1010、EA-1020、EA-5323、EA-5520、EA-CHD、EMA-1020等。 Examples of epoxy (meth)acrylates manufactured by the aforementioned Shin-Nakamura Chemical Industry Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020, etc.

作為上述共榮社化學公司製造之環氧(甲基)丙烯酸酯，例如可列舉：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等。 Examples of epoxy (meth) acrylates manufactured by the aforementioned Kyoeisha Chemical Co., Ltd. include 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, etc.

作為上述長瀨化成公司製造之環氧(甲基)丙烯酸酯，例如可列舉： DENACOL ACRYLATE DA-141、DENACOL ACRYLATE DA-314、DENACOL ACRYLATE DA-911等。 Examples of epoxy (meth) acrylates manufactured by the aforementioned Nagase Chemicals include: DENACOL ACRYLATE DA-141, DENACOL ACRYLATE DA-314, DENACOL ACRYLATE DA-911, etc.

上述(甲基)丙烯酸胺酯例如可藉由使具有羥基之(甲基)丙烯酸衍生物於觸媒量之錫系化合物存在下與多官能異氰酸酯化合物反應而獲得。 The above-mentioned (meth) acrylate amine ester can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with a multifunctional isocyanate compound in the presence of a catalytic amount of a tin-based compound.

作為上述多官能異氰酸酯化合物，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、二苯基甲烷-4,4'-二異氰酸酯(MDI)、氫化MDI、聚合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、二甲苯二異氰酸酯(XDI)、氫化XDI、離胺酸二異氰酸酯、三苯甲烷三異氰酸酯、三(異氰酸基苯基)硫代磷酸酯、四甲基二甲苯二異氰酸酯、1,6,11-十一烷三異氰酸酯等。 Examples of the above-mentioned polyfunctional isocyanate compounds include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl)phosphorothioate, tetramethylxylene diisocyanate, 1,6,11-undecane triisocyanate, etc.

又，作為上述多官能異氰酸酯化合物，亦可使用藉由多元醇與過量之多官能異氰酸酯化合物反應而獲得之經擴鏈之多官能異氰酸酯化合物。 Furthermore, as the above-mentioned polyfunctional isocyanate compound, an expanded polyfunctional isocyanate compound obtained by reacting a polyol with an excess of a polyfunctional isocyanate compound may 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 above-mentioned polyols include ethylene glycol, propylene glycol, glycerin, sorbitol, trihydroxymethylpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, etc.

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 derivatives having a hydroxyl group include: hydroxy alkyl mono(meth)acrylate, mono(meth)acrylate of a diol, mono(meth)acrylate or di(meth)acrylate of a triol, epoxy(meth)acrylate, etc.

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 above-mentioned mono(meth)acrylate hydroxyalkyl ester include: 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, etc.

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 above-mentioned diols include ethylene glycol, propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, polyethylene glycol, etc.

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 above-mentioned triols include trihydroxymethylethane, trihydroxymethylpropane, glycerol, etc.

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 above-mentioned epoxy (meth) acrylate include bisphenol A type epoxy acrylate, etc.

作為上述(甲基)丙烯酸胺酯中之市售者，例如可列舉：東亞合成公司製造之(甲基)丙烯酸胺酯、DAICEL-ALLNEX公司製造之(甲基)丙烯酸胺酯、根上工業公司製造之(甲基)丙烯酸胺酯、新中村化學工業公司製造之(甲基)丙烯酸胺酯、共榮社化學公司製造之(甲基)丙烯酸胺酯等。 Examples of the commercially available (meth)acrylic amine esters include: (meth)acrylic amine esters manufactured by Toagosei Co., Ltd., (meth)acrylic amine esters manufactured by DAICEL-ALLNEX Co., Ltd., (meth)acrylic amine esters manufactured by Negami Industries Co., Ltd., (meth)acrylic amine esters manufactured by Shin-Nakamura Chemical Industries Co., Ltd., and (meth)acrylic amine esters manufactured by Kyoeisha Chemical Co., Ltd.

作為上述東亞合成公司製造之(甲基)丙烯酸胺酯，例如可列舉：M-1100、M-1200、M-1210、M-1600等。 Examples of (meth)acrylic amines manufactured by the aforementioned Toa Synthetics include: M-1100, M-1200, M-1210, M-1600, etc.

作為上述DAICEL-ALLNEX公司製造之(甲基)丙烯酸胺酯，例如可列舉：EBECRYL210、EBECRYL220、EBECRYL230、EBECRYL270、EBECRYL1290、EBECRYL2220、EBECRYL4827、EBECRYL4842、EBECRYL4858、EBECRYL5129、EBECRYL6700、EBECRYL8402、EBECRYL8803、EBECRYL8804、EBECRYL8807、EBECRYL9260等。 Examples of (meth)acrylic amines manufactured by the above-mentioned DAICEL-ALLNEX company include EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260, etc.

作為上述根上工業公司製造之(甲基)丙烯酸胺酯，例如可列舉：Artresin UN-330、Artresin SH-500B、Artresin UN-1200TPK、Artresin UN-1255、Artresin UN-3320HB、Artresin UN-7100、Artresin UN-9000A、Artresin UN-9000H等。 Examples of (meth)acrylic amines manufactured by the aforementioned Negami Industries include Artresin UN-330, Artresin SH-500B, Artresin UN-1200TPK, Artresin UN-1255, Artresin UN-3320HB, Artresin UN-7100, Artresin UN-9000A, Artresin UN-9000H, etc.

作為上述新中村化學工業公司製造之(甲基)丙烯酸胺酯，例如可列舉：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等。 Examples of (meth)acrylic amine esters manufactured by the aforementioned Shin-Nakamura Chemical Industry Co., Ltd. include: 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, etc.

作為上述共榮社化學公司製造之(甲基)丙烯酸胺酯，例如可列舉：AH-600、AI-600、AT-600、UA-101I、UA-101T、UA-306H、UA-306I、UA-306T等。 Examples of (meth)acrylic amines manufactured by the aforementioned Kyoeisha Chemical Company include: AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T, etc.

為了提高所獲得之液晶元件用密封劑之接著性等，上述硬化性樹脂可含有環氧化合物。作為上述環氧化合物，例如可列舉上述作為用於合成環 氧(甲基)丙烯酸酯之原料之環氧化合物、部分(甲基)丙烯酸改質環氧化合物等。 In order to improve the adhesion of the obtained sealant for liquid crystal elements, the curable resin may contain an epoxy compound. Examples of the epoxy compound include the epoxy compound used as a raw material for synthesizing epoxy (meth)acrylate, and partially (meth)acrylic acid-modified epoxy compounds.

再者，於本說明書中，上述部分(甲基)丙烯酸改質環氧化合物意指例如可藉由使於1分子中具有2個以上之環氧基之環氧化合物之一部分環氧基與(甲基)丙烯酸反應而獲得之於1分子中具有分別1個以上之環氧基及(甲基)丙烯醯基之化合物。 Furthermore, in this specification, the above-mentioned partially (meth)acrylic acid-modified epoxy compound means, for example, a compound having one or more epoxy groups and one or more (meth)acrylic acid groups in one molecule, which can be obtained by reacting a part of the epoxy groups of an epoxy compound having two or more epoxy groups in one molecule with (meth)acrylic acid.

於上述硬化性樹脂含有上述(甲基)丙烯酸化合物及上述環氧化合物之情形時、或含有上述部分(甲基)丙烯酸改質環氧化合物之情形時，較佳為將上述硬化性樹脂中之(甲基)丙烯醯基與環氧基之合計中的(甲基)丙烯醯基之比率設為30莫耳%以上且95莫耳%以下。藉由上述(甲基)丙烯醯基之比率於該範圍內，所獲得之液晶元件用密封劑成為抑制發生液晶污染、並且接著性更優異者。 When the curable resin contains the (meth)acrylic compound and the epoxy compound, or contains the partially (meth)acrylic modified epoxy compound, it is preferred that the ratio of the (meth)acrylic group in the total of the (meth)acrylic group and the epoxy group in the curable resin be set to 30 mol% or more and 95 mol% or less. When the ratio of the (meth)acrylic group is within this range, the obtained sealant for liquid crystal elements suppresses liquid crystal contamination and has better adhesion.

自使所獲得之液晶元件用密封劑之低液晶污染性更優異之觀點而言，上述硬化性樹脂較佳具有-OH基、-NH-基、-NH2基等氫鍵性單元。 From the viewpoint of making the obtained liquid crystal element sealant more excellent in low liquid crystal contamination property, the above-mentioned curable resin preferably has a hydrogen bonding unit such as -OH group, -NH- group, -NH2 group, etc.

上述硬化性樹脂可單獨使用，亦可2種以上組合使用。 The above-mentioned hardening resins can be used alone or in combination of two or more.

本發明之液晶元件用密封劑可於無損本發明之目的之範圍內含有熱聚合起始劑。 The sealant for liquid crystal elements of the present invention may contain a thermal polymerization initiator within the scope that does not impair the purpose of the present invention.

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高分子偶氮起始劑。 As the above-mentioned thermal polymerization initiator, for example, those composed of azo compounds, organic peroxides, etc. can be listed. Among them, the polymer azo initiator composed of polymer azo compounds is preferred.

上述熱聚合起始劑可單獨使用，亦可2種以上組合使用。 The above-mentioned thermal polymerization initiators can be used alone or in combination of two or more.

再者，於本說明書中，上述「高分子偶氮化合物」意指具有偶氮基，藉由熱而生成可使(甲基)丙烯醯氧基硬化之自由基之數量平均分子量為300以上之化合物。 Furthermore, in this specification, the above-mentioned "polymer azo compound" means a compound having an azo group and generating free radicals with a number average molecular weight of 300 or more that can cure (meth)acryloyloxy groups by heat.

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於該範圍內，可抑制液晶污染，且可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。 The preferred lower limit of the number average molecular weight of the above-mentioned high molecular weight azo compound is 1000, and the preferred upper limit is 300,000. When the number average molecular weight of the above-mentioned high molecular weight azo compound is within this range, liquid crystal contamination can be suppressed and it can be easily mixed with a curable resin. The preferred lower limit of the number average molecular weight of the above-mentioned high molecular weight azo compound is 5000, and the preferred upper limit is 100,000, and the further preferred lower limit is 10,000, and the further preferred upper limit is 90,000.

作為上述高分子偶氮化合物，例如可列舉具有下述結構者，該結構由多個聚環氧烷或聚二甲基矽氧烷等單元經由偶氮基鍵結而成。 As the above-mentioned high molecular weight azo compound, for example, there can be cited those having the following structure, which is composed of multiple units such as polyepoxide or polydimethylsiloxane bonded via azo groups.

作為具有多個聚環氧烷等單元經由上述偶氮基鍵結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。 As a high molecular weight azo compound having a structure in which a plurality of polyoxyalkylene units are bonded via the above-mentioned azo groups, a polyoxyethylene structure is preferred.

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、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 above-mentioned high molecular weight azo compounds, specifically, for example, there can be listed: condensation products of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, condensation products of 4,4'-azobis(4-cyanovaleric acid) and polydimethylsiloxane having terminal amino groups, etc.

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FUJIFILM Wako Pure Chemical Industries公司製造)等。 Examples of the commercially available polymer azo compounds include: VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all manufactured by FUJIFILM Wako Pure Chemical Industries).

又，作為非高分子之偶氮化合物，例如可列舉：V-65、V-501(均為FUJIFILM Wako Pure Chemical Industries公司製造)等。 In addition, non-polymer azo compounds include, for example: V-65, V-501 (both manufactured by FUJIFILM Wako Pure Chemical Industries), etc.

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 above-mentioned organic peroxides include ketone peroxides, peroxyketal, hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates, etc.

上述熱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0.05重量份，較佳之上限為10重量份。藉由上述熱聚合起始劑之含量為0.05重量份以上，本發明之液晶元件用密封劑成為熱硬化性更優異者。藉由上述熱聚合起始劑之含量為10重量份以下，本發明之液晶元件用密封劑成為低液晶污染性或保存穩定性更優異者。上述熱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 above-mentioned thermal polymerization initiator relative to 100 parts by weight of the above-mentioned curable resin is preferably 0.05 parts by weight, and the preferably upper limit is 10 parts by weight. When the content of the above-mentioned thermal polymerization initiator is 0.05 parts by weight or more, the sealant for the liquid crystal element of the present invention becomes a sealant with better thermal curing properties. When the content of the above-mentioned thermal polymerization initiator is 10 parts by weight or less, the sealant for the liquid crystal element of the present invention becomes a sealant with better low liquid crystal contamination or storage stability. The preferably lower limit of the content of the above-mentioned thermal polymerization initiator is 0.1 parts by weight, and the preferably upper limit is 5 parts by weight.

本發明之液晶元件用密封劑可含有熱硬化劑。 The sealant for the liquid crystal element of the present 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 above-mentioned heat curing agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyphenol compounds, acid anhydrides, etc. Among them, organic acid hydrazides are preferably used.

上述熱硬化劑可單獨使用，亦可2種以上組合使用。 The above-mentioned thermosetting agents can be used alone or in combination of two or more.

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 above-mentioned organic acid hydrazides include: sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, etc.

作為上述有機酸醯肼中之市售者，例如可列舉：Otsuka Chemical公司製造之有機酸醯肼、Ajinomoto Fine-Techno公司製造之有機酸醯肼等。 Examples of the commercially available organic acid hydrazides include organic acid hydrazides manufactured by Otsuka Chemical Co., Ltd. and organic acid hydrazides manufactured by Ajinomoto Fine-Techno Co., Ltd.

作為上述Otsuka Chemical公司製造之有機酸醯肼，例如可列舉：SDH、ADH等。 Examples of organic acid hydrazides manufactured by the aforementioned Otsuka Chemical Company include SDH, ADH, etc.

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、Amicure UDH-J等。 Examples of organic acid hydrazides manufactured by the aforementioned Ajinomoto Fine-Techno include: Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J, etc.

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於該範圍內，可於不使所獲得之液晶元件用密封劑之塗佈性等變差之情況下使熱硬化性更優異。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 and the upper limit is preferably 50 parts by weight relative to 100 parts by weight of the above-mentioned curable resin. By keeping the content of the above-mentioned thermosetting agent within this range, the thermosetting property can be made better without deteriorating the coating property of the obtained liquid crystal element sealant. The upper limit of the content of the above-mentioned thermosetting agent is more preferably 30 parts by weight.

為了提高黏度、改善應力分散效果所致之接著性、改善線膨脹率等，本發明之液晶元件用密封劑較佳為含有填充劑。又，藉由含有上述填充劑，易於將觸變指數設為後述範圍。 In order to increase viscosity, improve adhesion due to stress dispersion effect, improve linear expansion rate, etc., the sealant for liquid crystal elements of the present invention preferably contains a filler. In addition, by containing the above-mentioned filler, it is easy to set the thixotropic index to the range described below.

作為上述填充劑，可使用無機填充劑或有機填充劑。 As the above-mentioned filler, an inorganic filler or an organic filler can be used.

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。 Examples of the above-mentioned inorganic fillers include: silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, aluminum oxide, 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.

作為上述有機填充劑，例如可列舉：聚酯微粒子、聚胺酯微粒子、乙烯基聚合物微粒子、丙烯酸聚合物微粒子等。 Examples of the above-mentioned organic fillers include polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, acrylic polymer microparticles, etc.

上述填充劑可單獨使用，亦可2種以上組合使用。 The above fillers can 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30重量份，較佳之上限為100重量份。藉由上述填充劑之含量於該範圍內，可於不使塗佈性等變差之情況下使接著性之改善等效果更優異。上述填充劑之含量之更佳之下限為45重量份，更佳之上限為80重量份。 The content of the above filler is preferably 30 parts by weight and the upper limit is 100 parts by weight relative to 100 parts by weight of the above curable resin. When the content of the above filler is within this range, the effect of improving adhesion can be improved without deteriorating the coating properties. The lower limit of the content of the above filler is preferably 45 parts by weight and the upper limit is preferably 80 parts by weight.

本發明之液晶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將密封劑與基板等良好地接著之接著助劑之作用。 The sealant for liquid crystal elements of the present invention preferably contains a silane coupling agent. The above-mentioned silane coupling agent mainly serves as a bonding aid for well bonding the sealant to the substrate, etc.

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，藉由與硬化性樹脂化學鍵結而可抑制硬化性樹脂向液晶中流出。 As the above-mentioned silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-butyltrimethoxysilane, 3-glyceryloxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, etc. can be preferably used. These have excellent effects in improving adhesion with substrates, etc., and can inhibit the curable resin from flowing out into the liquid crystal by chemically bonding with the curable resin.

上述矽烷偶合劑可單獨使用，亦可2種以上組合使用。 The above-mentioned silane coupling agents can be used alone or in combination of two or more.

本發明之液晶元件用密封劑100重量份中之上述矽烷偶合劑之含量的較佳之下限為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於該範圍內，而成為抑制發生液晶污染、並且提高接著性之效果更優異者。上述矽烷偶合劑之含量的更佳之下限為0.3重量份，更佳之上限為5重量份。 The preferred lower limit of the content of the above-mentioned silane coupling agent in 100 parts by weight of the sealant for liquid crystal elements of the present invention is 0.1 parts by weight, and the preferred upper limit is 10 parts by weight. When the content of the above-mentioned silane coupling agent is within this range, the effect of suppressing liquid crystal contamination and improving adhesion is better. The preferred lower limit of the content of the above-mentioned silane coupling agent is 0.3 parts by weight, and the preferred upper limit is 5 parts by weight.

本發明之液晶元件用密封劑進而可根據需要含有反應性稀釋劑、觸變劑、間隔劑、硬化促進劑、消泡劑、調平劑、聚合抑制劑等添加劑。 The sealant for liquid crystal elements of the present invention may further contain additives such as reactive diluents, modifiers, spacers, curing accelerators, defoamers, levelers, polymerization inhibitors, etc. as needed.

作為製造本發明之液晶元件用密封劑之方法，例如可列舉使用勻相分散機、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、光聚合起始劑及根據需要添加之矽烷偶合劑等進行混合之方法等。 As a method for manufacturing the sealant for the liquid crystal element of the present invention, for example, there can be cited a method of mixing a curable resin, a photopolymerization initiator, and a silane coupling agent added as needed using a mixer such as a homogenizer, a homogenizer, a universal mixer, a planetary mixer, a kneader, or a three-roll grinder.

本發明之液晶元件用密封劑之觸變指數之較佳之下限為1.2，較佳之上限為3.0。藉由上述觸變指數於該範圍內，所獲得之液晶元件用密封劑成 為液晶之插入防止性更優異者。上述觸變指數之更佳之下限為1.3，更佳之上限為2.0。 The preferred lower limit of the tactile index of the sealant for liquid crystal elements of the present invention is 1.2, and the preferred upper limit is 3.0. By having the above tactile index within this range, the sealant for liquid crystal elements obtained becomes one with better resistance to liquid crystal insertion. The preferred lower limit of the above tactile index is 1.3, and the preferred upper limit is 2.0.

再者，於本說明書中，上述觸變指數意指使用E型黏度計於25℃、0.5rpm之條件下測得之黏度除以於25℃、5.0rpm之條件下測得之黏度而得出之值。 Furthermore, in this specification, the above-mentioned throttling index means the value obtained by dividing the viscosity measured at 25°C and 0.5rpm using an E-type viscometer by the viscosity measured at 25°C and 5.0rpm.

藉由在本發明之液晶元件用密封劑中摻合導電性微粒子，可製造上下導通材料。含有本發明之液晶元件用密封劑及導電性微粒子之上下導通材料亦為本發明之一。 By mixing conductive microparticles into the sealant for liquid crystal elements of the present invention, a vertical conductive material can be produced. The vertical conductive material containing the sealant for liquid crystal elements of the present invention and conductive microparticles is also one of the present invention.

作為上述導電性微粒子，可使用於金屬球、樹脂微粒子之表面形成導電金屬層而成者等。其中，於樹脂微粒子之表面形成導電金屬層而成者藉由樹脂微粒子之優異彈性，能夠於不損傷透明基板等之情況下進行導電連接，因此較佳。 As the above-mentioned conductive microparticles, metal balls and resin microparticles with conductive metal layers formed on their surfaces can be used. Among them, those with conductive metal layers formed on the surfaces of resin microparticles are preferred because they can be electrically connected without damaging transparent substrates, etc., due to the excellent elasticity of the resin microparticles.

使用本發明之液晶元件用密封劑或本發明之上下導通材料而成之液晶元件亦為本發明之一。 A liquid crystal element made using the sealant for liquid crystal elements of the present invention or the upper and lower conductive materials of the present invention is also one of the present inventions.

作為本發明之液晶元件，較佳為窄邊緣設計之液晶元件。具體而言，較佳為液晶顯示部之周圍的框部分之寬度為2mm以下。 As the liquid crystal element of the present invention, it is preferred to be a liquid crystal element with a narrow edge design. Specifically, it is preferred that the width of the frame portion around the liquid crystal display portion is less than 2 mm.

又，製造本發明之液晶元件時之本發明的液晶元件用密封劑之塗佈寬度較佳為1mm以下。 Furthermore, when manufacturing the liquid crystal element of the present invention, the coating width of the sealant for the liquid crystal element of the present invention is preferably less than 1 mm.

作為製造本發明之液晶元件之方法，可較佳地使用液晶滴下法，具體而言，例如可列舉具有以下之各步驟之方法等。 As a method for manufacturing the liquid crystal element of the present invention, the liquid crystal dropping method can be preferably used. Specifically, for example, a method having the following steps can be listed.

首先，進行如下步驟：於具有ITO薄膜等電極及配向膜之2塊透明基板之一者上藉由網版印刷、分注器塗佈等塗佈本發明之液晶元件用密封劑，從而形成框狀之密封圖案。繼而，進行如下步驟：於本發明之液晶元件用密封劑未硬化之狀態下將液晶之微滴滴下塗佈於基板的密封圖案之框內，於真空下與另一透明基板重合。其後，進行如下步驟：藉由對本發明之液晶元件用密封劑之密封 圖案部分照射紫外線、或介隔截止濾光鏡等照射長波長之光，而使密封劑光硬化，藉由進行以上各步驟之方法可獲得液晶元件。又，除使上述密封劑光硬化之步驟以外，亦可進行對密封劑加熱而使之熱硬化之步驟。 First, the following steps are performed: the sealant for the liquid crystal element of the present invention is applied on one of the two transparent substrates having electrodes such as ITO thin films and alignment films by screen printing, dispenser coating, etc., thereby forming a frame-shaped sealing pattern. Then, the following steps are performed: when the sealant for the liquid crystal element of the present invention is not cured, droplets of liquid crystal are applied to the frame of the sealing pattern of the substrate, and overlapped with the other transparent substrate under vacuum. Thereafter, the following steps are performed: the sealant is photocured by irradiating the sealing pattern portion of the sealant for the liquid crystal element of the present invention with ultraviolet rays, or irradiating with long-wavelength light through a cutoff filter, etc., and the liquid crystal element can be obtained by performing the above steps. In addition to the step of photocuring the sealant, a step of heat-curing the sealant may also be performed.

根據本發明，可提供一種對長波長之光的深部硬化性優異、可抑制液晶向密封劑插入或由密封劑所導致之液晶污染的液晶元件用密封劑。又，根據本發明，可提供一種使用該液晶元件用密封劑而成之上下導通材料及液晶元件。 According to the present invention, a sealant for liquid crystal elements can be provided which has excellent deep curing property to long-wavelength light and can suppress the insertion of liquid crystal into the sealant or liquid crystal contamination caused by the sealant. In addition, according to the present invention, an upper and lower conductive material and a liquid crystal element formed by using the sealant for liquid crystal elements can be provided.

以下，列舉實施例對本發明更詳細地進行說明，然而，本發明並未僅限定於該等實施例。 The present invention is described in more detail below with reference to the following embodiments; however, the present invention is not limited to these embodiments.

(式(1-1)所表示之化合物之製作) (Preparation of the compound represented by formula (1-1))

向稀釋於甲苯300g中之2-(2-羥基乙基硫代)-9,10-蒽醌19.5g中，歷時1小時滴加稀釋於甲苯300g中之六亞甲基二異氰酸酯縮二脲變異體(三井化學公司製造，「Takenate D-165N」)14g，獲得上述式(1-1)所表示之化合物。作為反應觸媒，使用二丁基二月桂酸錫(東京化成工業公司製造)0.01g。為了提昇所獲得之化合物之純度，反覆進行3次利用甲苯與異丙醇之再結晶作業。再者，所獲得之上述式(1-1)所表示之化合物之結構藉由1H-NMR、13C-NMR及FT-IR進行確認。 To 19.5 g of 2-(2-hydroxyethylthio)-9,10-anthraquinone diluted in 300 g of toluene, 14 g of hexamethylene diisocyanate biuret variant (manufactured by Mitsui Chemicals, "Takenate D-165N") diluted in 300 g of toluene was added dropwise over a period of 1 hour to obtain the compound represented by the above formula (1-1). As a reaction catalyst, 0.01 g of dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used. In order to improve the purity of the obtained compound, the recrystallization operation using toluene and isopropanol was repeated 3 times. Furthermore, the structure of the obtained compound represented by the above formula (1-1) was confirmed by 1 H-NMR, 13 C-NMR and FT-IR.

(式(2)所表示之化合物之製作) (Preparation of the compound represented by formula (2))

(1)化合物A之合成 (1) Synthesis of compound A

於二氯甲烷50mL中添加氯化鋁7.36g，進而於0℃分數次添加二苯硫醚9.31g。繼而，於0℃添加氯乙醯氯5.56g，於室溫攪拌2小時後，於0℃添加氯化鋁7.33g及4-甲基戊醯氯7.06g，攪拌一晚。於將所獲得之反應混合物注入至冰水中後，藉由二氯甲烷對有機層進行萃取。利用MgSO4對所萃取之溶液進行乾燥並濃縮，藉由管柱層析法對殘留物進行純化，藉此，獲得作為白色粉末之下述式(4)所表示之化合物A。 7.36 g of aluminum chloride was added to 50 mL of dichloromethane, and then 9.31 g of diphenyl sulfide was added in portions at 0°C. Subsequently, 5.56 g of chloroacetyl chloride was added at 0°C, and after stirring at room temperature for 2 hours, 7.33 g of aluminum chloride and 7.06 g of 4-methylpentyl chloride were added at 0°C, and stirred overnight. After the obtained reaction mixture was poured into ice water, the organic layer was extracted with dichloromethane. The extracted solution was dried and concentrated with MgSO4 , and the residue was purified by column chromatography to obtain compound A represented by the following formula (4) as a white powder.

Figure 108124247-A0305-12-0020-5
Figure 108124247-A0305-12-0020-5

(2)化合物B之合成 (2) Synthesis of compound B

於丙酮30mL中添加1.0g所獲得之化合物A後，進而添加碳酸鉀1.11g及柳醛0.73g，於回流下攪拌3小時。在室溫於所獲得之反應混合物中添加水後，添加鹽酸使其酸性化，獲得沈澱物。藉由過濾回收所獲得之沈澱物，並對其進行乾燥，藉此，獲得下述式(5)所表示之化合物B。 After adding 1.0 g of the obtained compound A to 30 mL of acetone, 1.11 g of potassium carbonate and 0.73 g of salicylic aldehyde were further added, and the mixture was stirred under reflux for 3 hours. After adding water to the obtained reaction mixture at room temperature, hydrochloric acid was added to acidify the mixture to obtain a precipitate. The obtained precipitate was recovered by filtration and dried to obtain the compound B represented by the following formula (5).

Figure 108124247-A0305-12-0020-6
Figure 108124247-A0305-12-0020-6

(3)化合物C之合成 (3) Synthesis of compound C

於乙酸乙酯10mL中添加1.0g所獲得之化合物B後，進而添加氯化羥銨0.35g及吡啶5mL，於回流下攪拌3小時。於室溫將所獲得之反應混合物注入水中後，藉由乙酸乙酯對有機層進行萃取。利用MgSO4對所萃取之溶液進行乾燥並濃 縮，藉由管柱層析法對粗產物進行純化，藉此，獲得作為淡黃色固體之下述式(6)所表示之化合物C。 After adding 1.0 g of the obtained compound B to 10 mL of ethyl acetate, 0.35 g of hydroxyammonium chloride and 5 mL of pyridine were added, and the mixture was stirred under reflux for 3 hours. The obtained reaction mixture was poured into water at room temperature, and the organic layer was extracted with ethyl acetate. The extracted solution was dried and concentrated with MgSO 4 , and the crude product was purified by column chromatography to obtain compound C represented by the following formula (6) as a light yellow solid.

Figure 108124247-A0305-12-0021-7
Figure 108124247-A0305-12-0021-7

(4)式(2)所表示之化合物之合成 (4) Synthesis of the compound represented by formula (2)

於乙酸乙酯14mL中添加300mg所獲得之化合物C後，進而添加乙醯氯78.5mg及三乙胺111mg，於室溫攪拌3小時。於將所獲得之反應混合物注入水中後，藉由乙酸乙酯對有機層進行萃取。對所萃取之溶液進行濃縮，藉由管柱層析法對粗產物進行純化，藉此，獲得上述式(2)所表示之化合物。再者，所獲得之式(2)所表示之化合物之結構藉由1H-NMR、13C-NMR及FT-IR進行確認。 After adding 300 mg of the obtained compound C to 14 mL of ethyl acetate, 78.5 mg of acetyl chloride and 111 mg of triethylamine were added, and the mixture was stirred at room temperature for 3 hours. After the obtained reaction mixture was poured into water, the organic layer was extracted with ethyl acetate. The extracted solution was concentrated, and the crude product was purified by column chromatography to obtain the compound represented by the above formula (2). Furthermore, the structure of the obtained compound represented by formula (2) was confirmed by 1 H-NMR, 13 C-NMR and FT-IR.

(式(3)所表示之化合物之製作) (Preparation of the compound represented by formula (3))

於上述「(1)化合物A之合成」中，使用正辛醯氯8.53g代替4-甲基戊醯氯7.06g，除此以外，與上述「(式(2)所表示之化合物之製作)」相同地操作，從而獲得上述式(3)所表示之化合物。再者，所獲得之式(3)所表示之化合物之結構藉由1H-NMR、13C-NMR及FT-IR進行確認。 The same operation as in the above "(Preparation of the compound represented by formula (2))" was performed except that 8.53 g of n-octyl chloride was used instead of 7.06 g of 4-methylpentyl chloride in the above "(1) Synthesis of compound A" to obtain the compound represented by formula (3). The structure of the obtained compound represented by formula (3) was confirmed by 1 H-NMR, 13 C-NMR and FT-IR.

(實施例1~9及比較例1~5) (Examples 1 to 9 and Comparative Examples 1 to 5)

按照表1、2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」)將各材料進行混合後，進而使用三輥研磨機進行混合，藉此，製備實施例1~9及比較例1~5之液晶元件用密封劑。 According to the blending ratios listed in Tables 1 and 2, each material was mixed using a planetary mixer (manufactured by Thinky, "Defoaming Mixer Taro"), and then mixed using a three-roll grinder to prepare the sealing agents for liquid crystal elements of Examples 1 to 9 and Comparative Examples 1 to 5.

<評價> <Evaluation>

對於實施例及比較例中所獲得之各液晶元件用密封劑，進行以下之評價。將結果表示於表1、2中。 The following evaluations were performed on each of the sealants for liquid crystal elements obtained in the examples and comparative examples. The results are shown in Tables 1 and 2.

(觸變指數) (Trigger Index)

對於實施例及比較例中所獲得之各液晶元件用密封劑，使用E型黏度計(東機產業公司製造，「VISCOMETER TV-22」)於25℃、0.5rpm之條件及25℃、5.0rpm之條件下對黏度進行測定。 For each of the sealants for liquid crystal elements obtained in the embodiments and comparative examples, the viscosity was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., "VISCOMETER TV-22") at 25°C and 0.5 rpm and 25°C and 5.0 rpm.

藉由將於25℃、0.5rpm之條件下測得之黏度除以於25℃、5rpm之條件下測得之黏度，從而算出觸變指數。 The thixotropic index is calculated by dividing the viscosity measured at 25°C and 0.5 rpm by the viscosity measured at 25°C and 5 rpm.

(深部硬化性) (Deep sclerosis)

將間隔劑微粒子(積水化學工業公司製造，「Micropearl GS-L300」)1重量份分散於實施例及比較例中所獲得之各液晶元件用密封劑100重量份中。繼而，將密封劑填充於滴塗用之注射器(武藏高科技公司製造，「PSY-10E」)中，進行脫泡處理後，藉由分注器(武藏高科技公司製造，「SHOTMASTER300」)塗佈於玻璃基板上。藉由真空貼合裝置於5Pa之減壓下於該基板貼合同尺寸之玻璃基板，從而獲得單元間隙為300μm之單元。使用金屬鹵化物燈對所獲得之單元之密封劑部分照射100mW/cm2之光30秒。光照射係介隔對波長420nm以下之光進行截止之截止濾光鏡(420nm截止濾光鏡)進行。 1 part by weight of spacer microparticles ("Micropearl GS-L300" manufactured by Sekisui Chemical Industries, Ltd.) was dispersed in 100 parts by weight of the sealant for each liquid crystal element obtained in the embodiment and the comparative example. Then, the sealant was filled in a syringe for dripping ("PSY-10E" manufactured by Musashi High-Tech Corporation), defoamed, and then applied to a glass substrate using a dispenser ("SHOTMASTER300" manufactured by Musashi High-Tech Corporation). A glass substrate of the same size was bonded to the substrate under a reduced pressure of 5 Pa using a vacuum bonding device to obtain a cell with a cell gap of 300 μm. The sealant portion of the obtained cell was irradiated with 100 mW/ cm2 light for 30 seconds using a metal halide lamp. Light irradiation was performed through a cutoff filter (420nm cutoff filter) that cuts off light with a wavelength of 420nm or less.

使用紅外分光裝置(BIORAD公司製造，「FTS3000」)進行密封劑之FT-IR測定，測定源自(甲基)丙烯醯基之峰於光照射前後之變化量。將光照射後源自(甲基)丙烯醯基之峰減少90%以上之情形設為「◎」，將減少80%以上且未達90%之情形設為「○」，將減少70%以上且未達80%之情形設為「△」，將光照射後之源自(甲基)丙烯醯基之峰之減少未達70%之情形設為「×」，而對深部硬化性進行評價。 The sealant was measured by FT-IR using an infrared spectrometer (manufactured by BIORAD, "FTS3000") to measure the change in the peak derived from (meth)acryloyl groups before and after light irradiation. The peak derived from (meth)acryloyl groups was marked as "◎" when it decreased by more than 90% after light irradiation, "○" when it decreased by more than 80% but less than 90%, "△" when it decreased by more than 70% but less than 80%, and "×" when the peak derived from (meth)acryloyl groups decreased by less than 70% after light irradiation to evaluate the deep curability.

(插入防止性) (Insertion prevention)

將間隔劑微粒子(積水化學工業公司製造，「Micropearl SP-250」)1重量份分散於實施例及比較例中所獲得之各液晶元件用密封劑100重量份中。繼而，將 密封劑填充於滴塗用之注射器(武藏高科技公司製造，「PSY-10E」)中，進行脫泡處理。藉由分注器(武藏高科技公司製造，「SHOTMASTER300」)將脫泡處理後之密封劑以成為線寬1mm之框狀之方式塗佈於2塊附經摩擦之配向膜及透明電極之基板之一者。 1 part by weight of spacer particles ("Micropearl SP-250" manufactured by Sekisui Chemical Industry Co., Ltd.) was dispersed in 100 parts by weight of each sealant for liquid crystal elements obtained in the embodiment and the comparative example. Then, the sealant was filled in a syringe for dripping ("PSY-10E" manufactured by Musashi High-Tech Co., Ltd.) and defoamed. The defoamed sealant was applied to one of the two substrates with rubbed alignment films and transparent electrodes in a frame shape with a line width of 1 mm using a dispenser ("SHOTMASTER300" manufactured by Musashi High-Tech Co., Ltd.).

繼而，將液晶(Chisso公司製造，「JC-5004LA」)之微滴滴下塗佈於附透明電極之基板之密封劑之框內整個面，立刻將另一基板貼合。其後，使用金屬鹵化物燈對密封劑部分照射100mW/cm2之光30秒，進而於120℃加熱1小時，從而獲得液晶元件(單元間隙為50μm)。光照射係介隔對波長420nm以下之光進行截止之截止濾光鏡(420nm截止濾光鏡)進行。 Then, droplets of liquid crystal (manufactured by Chisso, "JC-5004LA") were applied to the entire surface of the sealant frame of the substrate with transparent electrodes, and the other substrate was immediately attached. After that, the sealant part was irradiated with 100mW/ cm2 light for 30 seconds using a metal halide lamp, and then heated at 120℃ for 1 hour to obtain a liquid crystal element (cell gap of 50μm). The light irradiation was performed through a cutoff filter (420nm cutoff filter) that cuts off light with a wavelength of less than 420nm.

對於所獲得之液晶元件，進行密封圖案之形狀觀察。其結果，將密封圖案之形狀未被內部之液晶打亂者設為「◎」，將密封圖案之形狀稍微混亂者設為「○」，將密封圖案之形狀大幅混亂者設為「△」，將液晶突破密封圖案而露出至外部者設為「×」，而對插入防止性進行評價。 The shape of the sealing pattern of the obtained liquid crystal element was observed. As a result, the shape of the sealing pattern was not disturbed by the liquid crystal inside, and was set as "◎", the shape of the sealing pattern was slightly disturbed, and the shape of the sealing pattern was set as "△", and the shape of the sealing pattern was greatly disturbed, and the shape of the liquid crystal broke through the sealing pattern and exposed to the outside was set as "×", and the insertion prevention was evaluated.

(低液晶污染性) (Low liquid crystal contamination)

對於與上述「(插入防止性)」相同地操作而獲得之液晶元件，藉由目視對於25℃、50%RH之環境下施加1小時電壓之狀態後之液晶配向混亂度(顯示不均)進行確認。 For the liquid crystal element obtained by the same operation as the above "(Insertion Prevention)", the liquid crystal alignment disorder (display unevenness) was confirmed by visual inspection after voltage was applied for 1 hour in an environment of 25°C and 50%RH.

將完全未觀察到液晶元件顯示不均之情形設為「◎」，將於液晶元件之密封劑附近(周邊部)觀察到少量輕微之顯示不均之情形設為「○」，將周邊部存在明顯之較深之顯示不均之情形設為「△」，將明顯之較深之顯示不均不僅存在於周邊部、且擴散至中央部之情形設為「×」，而對低液晶污染性進行評價。 The case where no display unevenness of the liquid crystal element was observed was marked as "◎", the case where a small amount of display unevenness was observed near the sealant of the liquid crystal element (periphery) was marked as "○", the case where obvious and deeper display unevenness existed in the peripheral part was marked as "△", and the case where obvious and deeper display unevenness existed not only in the peripheral part but also spread to the central part was marked as "×", and the low liquid crystal contamination was evaluated.

再者，評價為「◎」、「○」之液晶元件係實際使用完全不存在問題之水準，「△」之液晶元件係根據設計而可能存在問題之水準，「×」之液晶元件係經不起實際使用之水準。 Furthermore, the liquid crystal components rated as "◎" and "○" are at a level where there are no problems in actual use, the liquid crystal components rated as "△" are at a level where there may be problems due to the design, and the liquid crystal components rated as "×" are at a level that cannot withstand actual use.

Figure 108124247-A0305-12-0024-8
Figure 108124247-A0305-12-0024-8

Figure 108124247-A0305-12-0025-9
Figure 108124247-A0305-12-0025-9

[產業上之可利用性] [Industrial availability]

根據本發明，可提供一種對長波長之光的深部硬化性優異、可抑制液晶向密封劑插入或由密封劑所導致之液晶污染的液晶元件用密封劑。又， 根據本發明，可提供一種使用該液晶元件用密封劑而成之上下導通材料及液晶元件。 According to the present invention, a sealant for liquid crystal elements can be provided which has excellent deep curing property against long-wavelength light and can suppress the insertion of liquid crystal into the sealant or liquid crystal contamination caused by the sealant. In addition, according to the present invention, an upper and lower conductive material and a liquid crystal element formed by using the sealant for liquid crystal elements can be provided.

Claims (9)

一種液晶元件用密封劑，其含有硬化性樹脂及光聚合起始劑，上述光聚合起始劑含有9-氧硫 （thioxanthone）化合物及肟酯（oxime ester）化合物， 上述肟酯化合物係下述式（3）所表示之化合物， 上述9-氧硫 化合物之分子量為1000以上且2000以下， 上述9-氧硫 化合物與上述肟酯化合物之合計中的上述9-氧硫 化合物之含有比例為30重量%以上且80重量%以下， 。 A sealing agent for a liquid crystal element, comprising a curable resin and a photopolymerization initiator, wherein the photopolymerization initiator contains 9-oxysulfide (thioxanthone) compound and oxime ester compound, the oxime ester compound is a compound represented by the following formula (3), the above 9-oxothio The molecular weight of the compound is 1000 or more and 2000 or less. The above-mentioned 9-oxysulfur The content ratio of the compound is 30% by weight or more and 80% by weight or less, . 如請求項1所述之液晶元件用密封劑，其中，上述9-氧硫 化合物於1分子中具有3個以上之9-氧硫 基（thioxanthonyl group）。The sealant for a liquid crystal element as claimed in claim 1, wherein the 9-oxysulfide The compound has three or more 9-oxosulfur groups in one molecule. thioxanthonyl group. 如請求項1或2所述之液晶元件用密封劑，其中，上述9-氧硫 化合物具有醯胺鍵。The sealant for a liquid crystal element as claimed in claim 1 or 2, wherein the 9-oxysulfide The compound has an amide bond. 如請求項3所述之液晶元件用密封劑，其中，上述9-氧硫 化合物之醯胺鍵當量為300以下。The sealant for a liquid crystal element as claimed in claim 3, wherein the 9-oxysulfide The amide bond equivalent of the compound is 300 or less. 如請求項1或2所述之液晶元件用密封劑，其含有填充劑。The sealant for a liquid crystal element as described in claim 1 or 2 contains a filler. 如請求項5所述之液晶元件用密封劑，其中，上述填充劑之含量相對於上述硬化性樹脂100重量份為30重量份以上且100重量份以下。The sealant for a liquid crystal element as described in claim 5, wherein the content of the filler is 30 parts by weight or more and 100 parts by weight or less based on 100 parts by weight of the curable resin. 如請求項1或2所述之液晶元件用密封劑，其觸變指數為1.2以上且3.0以下。The sealant for a liquid crystal element as described in claim 1 or 2 has a thixotropic index of not less than 1.2 and not more than 3.0. 一種上下導通材料，其含有請求項1、2、3、4、5、6或7所述之液晶元件用密封劑及導電性微粒子。A vertical conductive material comprising the sealant for liquid crystal elements as described in claim 1, 2, 3, 4, 5, 6 or 7 and conductive microparticles. 一種液晶元件，其使用請求項1、2、3、4、5、6或7所述之液晶元件用密封劑或請求項8所述之上下導通材料而成。A liquid crystal element, which is made using the sealant for liquid crystal elements described in claim 1, 2, 3, 4, 5, 6 or 7 or the top and bottom conductive material described in claim 8.
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