TWI689578B - Sealant for liquid crystal display element, upper and lower conduction materials, and liquid crystal display element - Google Patents

Sealant for liquid crystal display element, upper and lower conduction materials, and liquid crystal display element Download PDF

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TWI689578B
TWI689578B TW105117135A TW105117135A TWI689578B TW I689578 B TWI689578 B TW I689578B TW 105117135 A TW105117135 A TW 105117135A TW 105117135 A TW105117135 A TW 105117135A TW I689578 B TWI689578 B TW I689578B
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西出勝則
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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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
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    • 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
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Abstract

本發明之目的在於提供一種可見光硬化性優異，且能夠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 sealing compound for liquid crystal display elements which is excellent in visible light curability and can suppress contamination of liquid crystals. In addition, an object of the present invention is to provide an upper and lower conduction material and a liquid crystal display element using the sealant for a liquid crystal display element.

本發明係一種液晶顯示元件用密封劑，其含有硬化性樹脂及光自由基聚合起始劑，上述光自由基聚合起始劑含有下述式(1)所示之化合物。 The present invention is a sealant for a liquid crystal display element, which contains a curable resin and a photo radical polymerization initiator, and the photo radical polymerization initiator contains a compound represented by the following formula (1).

式(1)中，2個X分別獨立表示氫原子可被-OR1基取代之苯基，各X可具有2個以上之-OR1基，於2個X具有合計2個以上之-OR1基之情形時，各-OR1基可相同，亦可不同。R1表示氫或碳數1~3之烷基。n表示1~10之整數。 In formula (1), two Xs independently represent a phenyl group in which a hydrogen atom may be substituted with an -OR 1 group, each X may have two or more -OR 1 groups, and two Xs have a total of two or more -OR In the case of 1 radical, each -OR 1 radical may be the same or different. R 1 represents hydrogen or an alkyl group having 1 to 3 carbon atoms. n represents an integer from 1 to 10.

Figure 105117135-A0202-11-0001-1
Figure 105117135-A0202-11-0001-1

Description

液晶顯示元件用密封劑、上下導通材料、及液晶顯示元件 Sealant for liquid crystal display element, upper and lower conduction materials, and liquid crystal display element

本發明係關於一種可見光硬化性優異，且能夠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 visible light curability and can suppress contamination of liquid crystals. In addition, the present invention relates to an upper and lower conduction material and a liquid crystal display element formed by using the sealant for liquid crystal display elements.

近年來，作為液晶顯示單元等液晶顯示元件之製造方法，就生產時間縮短、使用液晶量之最佳化等觀點而言，一直使用如專利文獻1、專利文獻2中所揭示之使用含有硬化性樹脂、光聚合起始劑及熱硬化劑的光熱併用硬化型密封劑之被稱為滴下法的液晶滴下方式。 In recent years, as a method of manufacturing a liquid crystal display element such as a liquid crystal display unit, from the viewpoint of shortening the production time and optimizing the amount of liquid crystal used, the use of curability-containing materials as disclosed in Patent Document 1 and Patent Document 2 has been used. A liquid crystal dropping method called a dropping method in which a resin, a photopolymerization initiator, and a thermosetting agent are combined with light and heat of a curing type sealant.

關於滴下法，首先，於2塊附電極之基板之一者藉由分注形成長方形狀之密封圖案。繼而，於密封劑為未硬化之狀態下將液晶之微小滴滴下至基板之密封框內，使其於真空下與另一基板重疊，並對密封部照射紫外線等光而進行暫時硬化。之後，加熱進行正式硬化，而製作液晶顯示元件。當前，該滴下法正成為液晶顯示元件之製造方法之主流。 Regarding the dropping method, first, a rectangular sealing pattern is formed by dispensing into one of the two substrates with electrodes. Then, in a state where the sealant is uncured, small droplets of liquid crystal are dropped into the sealing frame of the substrate to overlap with another substrate under vacuum, and the sealing portion is irradiated with ultraviolet light or the like to temporarily cure. After that, heating is performed to complete hardening to produce a liquid crystal display element. At present, the dropping method is becoming the mainstream of the manufacturing method of liquid crystal display elements.

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正不斷普及之現今，設備之小型化為最首要謀求之課題。作為設備之小型化之手法，可列舉液晶顯示部之窄邊緣化，例如進行將密封部之位置 配置於黑矩陣下(以下，亦稱為窄邊緣設計)。 However, as mobile devices such as mobile phones, portable game consoles and other mobile devices with liquid crystal panels are becoming increasingly popular, miniaturization of devices is the most important issue. As a method of miniaturizing the device, the narrow edge of the liquid crystal display section can be cited, for example, the position of the sealing section It is arranged under the black matrix (hereinafter, also referred to as narrow edge design).

然而，就窄邊緣設計而言，由於密封劑配置於黑矩陣之正下方，故而存在如下問題：若進行滴下法，則於使密封劑光硬化時，所照射之光會被遮擋，光難以到達密封劑之內部且硬化變得不充分。如此，若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，容易產生液晶污染。 However, in terms of narrow-edge design, since the sealant is disposed directly under the black matrix, there is a problem that if the drip method is performed, when the sealant is light-hardened, the irradiated light is blocked and the light is difficult to reach Inside the sealant and hardening becomes insufficient. In this way, if the curing of the sealant becomes insufficient, there is a problem that the uncured sealant component elutes into the liquid crystal, and liquid crystal contamination is likely to occur.

於專利文獻3中揭示有將高感度之光聚合起始劑摻合於密封劑。然而，僅摻合高感度之光聚合起始劑，無法充分地使密封劑進行光硬化。又，於專利文獻4中揭示有將高感度之光聚合起始劑及增感劑組合而摻合於密封劑。然而，存在因使用增感劑而容易產生液晶污染之問題。 Patent Document 3 discloses that a high-sensitivity photopolymerization initiator is blended with a sealant. However, only blending a high-sensitivity photopolymerization initiator cannot sufficiently photo-harden the sealant. In addition, Patent Document 4 discloses that a high-sensitivity photopolymerization initiator and a sensitizer are combined and blended into a sealant. However, there is a problem that liquid crystal contamination is easily generated due to the use of a sensitizer.

又，習知之滴下法中多使用摻合有具有自由基聚合性之硬化性樹脂及光自由基聚合起始劑之密封劑，且為了使該自由基聚合性化合物進行光硬化而照射紫外線，但存在因照射紫外線而使液晶劣化等問題。因此，考慮使用400nm以下之截止濾波器等並利用可見光區域之波長的光使密封劑進行光硬化，但於此種情形時，存在無法充分地獲得光自由基聚合起始劑的感度之問題。 In addition, in the conventional dripping method, a sealant mixed with a radically polymerizable curable resin and a photoradical polymerization initiator is often used, and ultraviolet rays are irradiated in order to photoharden the radically polymerizable compound, but There is a problem such as deterioration of liquid crystal due to irradiation of ultraviolet rays. Therefore, it is considered to use a cut-off filter of 400 nm or less and use the light with a wavelength in the visible light region to photocure the sealant. However, in this case, there is a problem that the sensitivity of the photoradical polymerization initiator cannot be sufficiently obtained.

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 Literature 2: International Publication No. 02/092718

專利文獻3：國際公開第2011/002028號 Patent Literature 3: International Publication No. 2011/002028

專利文獻4：日本特開2010-286640號公報 Patent Document 4: Japanese Patent Laid-Open No. 2010-286640

本發明之目的在於提供一種可見光硬化性優異且能夠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 liquid crystal display elements which is excellent in visible light curability and can suppress contamination of liquid crystals. In addition, an object of the present invention is to provide an upper and lower conduction material and a liquid crystal display element using the sealant for a liquid crystal display element.

本發明係一種液晶顯示元件用密封劑，其含有硬化性樹脂及光自由基聚合起始劑，上述光自由基聚合起始劑含有下述式(1)所示之化合物。 The present invention is a sealant for a liquid crystal display element, which contains a curable resin and a photo radical polymerization initiator, and the photo radical polymerization initiator contains a compound represented by the following formula (1).

Figure 105117135-A0202-12-0003-2
Figure 105117135-A0202-12-0003-2

式(1)中，2個X分別獨立表示氫原子可被-OR1基取代之苯基，各X可具有2個以上之-OR1基，於2個X具有合計2個以上之-OR1基之情形時，各-OR1基可相同，亦可不同。R1表示氫或碳數1~3之烷基。n表示1~10之整數。 In formula (1), two Xs independently represent a phenyl group in which a hydrogen atom may be substituted with an -OR 1 group, each X may have two or more -OR 1 groups, and two Xs have a total of two or more -OR In the case of 1 radical, each -OR 1 radical may be the same or different. R 1 represents hydrogen or an alkyl group having 1 to 3 carbon atoms. n represents an integer from 1 to 10.

本發明人驚奇地發現：具有特定結構之化合物對液晶之污染性低，且於可見光下高感度地產生自由基。因此，本發明人等發現：藉由摻合該化合物作為光自由基聚合起始劑，能夠獲得可見光硬化性優異，且能夠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 inventors have surprisingly found that a compound having a specific structure has low pollution to liquid crystals and generates free radicals with high sensitivity under visible light. Therefore, the present inventors have found that by blending this compound as a photo-radical polymerization initiator, a sealant for liquid crystal display elements which is excellent in visible light curability and can suppress liquid crystal contamination can be obtained, and the present invention has been completed.

本發明之液晶顯示元件用密封劑含有光自由基聚合起始劑。 The sealing agent for liquid crystal display elements of this invention contains a photo radical polymerization initiator.

上述光自由基聚合起始劑含有上述式(1)所示之化合物。藉由含有上述式(1)所示之化合物，本發明之液晶顯示元件用密封劑成為可見光硬化性優異，且能夠抑制液晶污染者。 The photo radical polymerization initiator contains the compound represented by the above formula (1). By containing the compound represented by the above formula (1), the sealing compound for liquid crystal display elements of the present invention is excellent in visible light curability and can suppress contamination of liquid crystals.

上述式(1)中，作為X，例如可列舉：苯基、2-羥基苯基、3-羥基苯基、4-羥基苯基、2-甲氧基苯基、3-甲氧基苯基、4-甲氧基苯基、2-乙氧基苯基、3-乙氧基苯基、4-乙氧基苯基等。其中，較佳為苯基、4-甲氧基苯基，更佳為苯基。 In the above formula (1), examples of X include phenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl , 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, etc. Among them, phenyl and 4-methoxyphenyl are preferred, and phenyl is more preferred.

上述式(1)中，n表示1~10之整數。其中，n較佳為2~6之整數，更佳為3~5之整數。 In the above formula (1), n represents an integer of 1-10. Among them, n is preferably an integer of 2 to 6, more preferably an integer of 3 to 5.

上述式(1)所示之化合物之重量平均分子量的較佳下限為900。藉由上述式(1)所示之化合物之重量平均分子量為900以上，所獲得之液晶顯示元件用密封劑成為低液晶污染性更優異者。關於上述式(1)所示之化合物的重量平均分子量之上限，並無特別限定，就合成之容易性、操作性及與硬化性樹脂之相溶性等觀點而言，較佳為未達1300。上述式(1)所示之化合物的重量平均分子量之更佳下限為950，更佳上限為1100。 The preferable lower limit of the weight average molecular weight of the compound represented by the above formula (1) is 900. When the weight average molecular weight of the compound represented by the above formula (1) is 900 or more, the obtained sealant for liquid crystal display elements becomes more excellent in low liquid crystal contamination. The upper limit of the weight average molecular weight of the compound represented by the above formula (1) is not particularly limited, but it is preferably not more than 1300 from the viewpoints of ease of synthesis, workability, and compatibility with the curable resin. The more preferable lower limit of the weight average molecular weight of the compound represented by the above formula (1) is 950, and the more preferable upper limit is 1100.

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)進行測量並藉由聚苯乙烯換算而求出之值。作為藉由GPC測量基於聚苯乙烯換算之重量平均分子量時之管柱，例如可舉Shodex LF-804(昭和電工公司製造)等。 In this specification, the weight average molecular weight is measured by gel permeation chromatography (GPC) and calculated by polystyrene conversion. As a column for measuring the weight average molecular weight based on polystyrene conversion by GPC, for example, Shodex LF-804 (manufactured by Showa Denko) and the like can be mentioned.

關於上述式(1)所示之化合物之含量，相對於硬化性樹脂100重量份，較佳下限為0.3重量份，較佳上限為10重量份。藉由上述式(1) 所示之化合物之含量為0.3重量份以上，所獲得之液晶顯示元件用密封劑成為光硬化性更優異者。藉由上述式(1)所示之化合物之含量為10重量份以下，所獲得之液晶顯示元件用密封劑成為耐候性、保存穩定性及低液晶污染性更優異者。上述式(1)所示之化合物的含量之更佳下限為0.5重量份，更佳上限為5重量份，進而較佳之下限為1重量份。 Regarding the content of the compound represented by the above formula (1), with respect to 100 parts by weight of the curable resin, the lower limit is preferably 0.3 parts by weight, and the upper limit is preferably 10 parts by weight. With the above formula (1) The content of the compound shown is 0.3 parts by weight or more, and the obtained sealing compound for liquid crystal display elements becomes more excellent in photocurability. When the content of the compound represented by the above formula (1) is 10 parts by weight or less, the obtained sealant for liquid crystal display elements becomes more excellent in weather resistance, storage stability, and low liquid crystal contamination. The more preferable lower limit of the content of the compound represented by the above formula (1) is 0.5 parts by weight, the more preferable upper limit is 5 parts by weight, and the more preferable lower limit is 1 part by weight.

本發明之液晶顯示元件用密封劑於不引起液晶污染等不良影響之範圍內，除上述式(1)所示之化合物以外，還可含有其他光自由基聚合起始劑。 The sealant for liquid crystal display elements of the present invention may contain other photo-radical polymerization initiators in addition to the compound represented by the above formula (1) within a range that does not cause adverse effects such as liquid crystal contamination.

作為上述其他光自由基聚合起始劑，例如可列舉：二苯甲酮系化合物、苯乙酮系化合物、醯基膦氧化物系化合物、二茂鈦系化合物、肟酯系化合物、安息香醚系化合物、二苯乙二酮、9-氧硫

Figure 105117135-A0202-12-0005-19
等。 Examples of the other photoradical polymerization initiators include benzophenone-based compounds, acetophenone-based compounds, acetylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, and benzoin ether-based compounds. Compounds, benzophenone, 9-oxygen sulfide
Figure 105117135-A0202-12-0005-19
Wait.

上述其他光自由基聚合起始劑之中，作為市售者，例如可列舉：IRGACURE 184、IRGACURE 369、IRGACURE 379、IRGACURE 651、IRGACURE 819、IRGACURE 907、IRGACURE 2959、IRGACURE OXE01、Lucirin TPO(均為巴斯夫公司製造)、安息香甲醚、安息香乙醚、安息香丙醚(均為東京化成工業公司製造)、Adeka Optomer N-1414、Adeka Optomer N-1717、Adeka Optomer N-1919、Adeka ARKLS NCI-839、Adeka ARKLS NCI-930等(均為艾迪科公司製造)。 Among the other photo-radical polymerization initiators mentioned above, as commercially available, for example, IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, Lucirin TPO (all are (Made by BASF), benzoin methyl ether, benzoin ether, benzoin propyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), Adeka Optomer N-1414, Adeka Optomer N-1717, Adeka Optomer N-1919, Adeka ARKLS NCI-839, Adeka ARKLS NCI-930, etc. (all manufactured by Adiko).

本發明之液晶顯示元件用密封劑含有硬化性樹脂。 The sealing compound for liquid crystal display elements of this invention contains curable resin.

上述硬化性樹脂較佳含有具有(甲基)丙烯醯基之化合物。 The curable resin preferably contains a compound having a (meth)acryloyl group.

再者，於本說明書中，上述所謂「(甲基)丙烯醯基」，意指丙烯醯基或甲基丙烯醯基。 In addition, in this specification, the above-mentioned "(meth)acryloyl group" means an acryloyl group or methacryloyl group.

作為上述具有(甲基)丙烯醯基之化合物，例如可列舉：藉由使具有羥基之化合物與(甲基)丙烯酸進行反應所獲得之(甲基)丙烯酸酯化合物、藉由使(甲基)丙烯酸與環氧化合物進行反應所獲得之環氧(甲基)丙烯酸酯、藉由使具有羥基之(甲基)丙烯酸衍生物與異氰酸酯化合物進行反應所獲得之(甲基)丙烯酸胺酯(urethane(meth)acrylate)等。 Examples of the compound having a (meth)acryloyl group include (meth)acrylate compounds obtained by reacting a compound having a hydroxyl group with (meth)acrylic acid, and (meth) Epoxy (meth)acrylate obtained by reacting acrylic acid with an epoxy compound, and urethane(meth)acrylate obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound meth)acrylate) etc.

再者，於本說明書中，上述所謂「(甲基)丙烯酸」，意指丙烯酸或甲基丙烯酸，上述所謂「(甲基)丙烯酸酯」，意指丙烯酸酯或甲基丙烯酸酯，上述所謂「環氧(甲基)丙烯酸酯」，意指使環氧化合物中之所有環氧基與(甲基)丙烯酸反應而得之化合物。 Furthermore, in this specification, the above-mentioned "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the above-mentioned "(meth)acrylate" means acrylate or methacrylate, the above-mentioned " "Epoxy (meth)acrylate" means a compound obtained by reacting all epoxy groups in an epoxy compound with (meth)acrylic acid.

上述(甲基)丙烯酸酯化合物之中，作為單官能者，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)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(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)丙烯酸環己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸苄酯、(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、甲氧基乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、乙基卡必醇(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸2-苯氧基乙酯、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、(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯、醯亞胺(甲基)丙烯酸酯、琥珀酸2-(甲基)丙烯醯氧基(acryloyloxy)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、(甲基)丙烯酸環氧丙酯、磷酸2-(甲基)丙烯醯氧基乙酯等。 Among the above (meth)acrylate compounds, examples of monofunctional ones include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, third butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Ester, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, (meth) ) Cyclohexyl acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid 2-hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxy (meth)acrylate Ethyl ester, 2-butoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethyl carbitol ( Methacrylates, tetrahydrofurfuryl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (Meth)acrylate, (meth)acrylic acid 2,2,2-trifluoroethyl, (meth)acrylic acid 2,2,3,3-tetrafluoropropyl ester, (meth Group) 1H,1H,5H-octafluoropentyl acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, amide imide (meth)acrylate, succinic acid 2-(meth)acryloyloxy ethyl ester, hexahydrophthalic acid 2-(meth)acrylic acid ethyl ester, phthalic acid 2-(meth)acrylic acid ethyl acetate Ester 2-hydroxypropyl ester, glycidyl (meth)acrylate, 2-(meth)acrylic acid ethyl phosphate.

又，上述(甲基)丙烯酸酯化合物之中，作為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、2-正丁基-2-乙基-1,3-丙二醇二(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、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(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、二羥甲基二環戊二烯基二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、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, among the above (meth)acrylate compounds, examples of bifunctional ones include 1,3-butanediol di(meth)acrylate and 1,4-butanediol di(meth)acrylic acid. Ester, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-n Butyl-2-ethyl-1,3-propanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate Methacrylates, polyethylene glycol di(meth)acrylates, dipropylene glycol di(meth)acrylates, tripropylene glycol di(meth)acrylates, polypropylene glycol (meth)acrylates, ethylene oxide Alkane addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F di(meth)acrylate, dimethylol Dicyclopentadienyl di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified isocyanurate di(meth)acrylate, (meth) 2-Hydroxy-3-(meth)acrylic propyl acrylate, 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，上述(甲基)丙烯酸酯化合物之中，作為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、新戊四醇三(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、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, among the above (meth)acrylate compounds, examples of trifunctional or more include trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth) Base) acrylate, propylene oxide addition trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylol propane tri (meth) acrylate, neopentaerythritol tri (methyl) Acrylic ester, ethylene oxide Alkane addition isocyanurate tri(meth)acrylate, glycerin tri(meth)acrylate, propylene oxide addition glycerin tri(meth)acrylate, tri(meth)acrylic acid ethoxylate phosphate Ester, di-trimethylolpropane tetra (meth) acrylate, neopentaerythritol tetra (meth) acrylate, di neopentaerythritol penta (meth) acrylate, di neopentaerythritol hexa (meth) Base) acrylate, etc.

作為上述環氧(甲基)丙烯酸酯，例如可舉藉由按照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所獲得者等。 Examples of the epoxy (meth)acrylates include those obtained by reacting an epoxy compound and (meth)acrylic acid in the presence of an alkaline catalyst according to a conventional method.

作為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，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、環氧丙胺型環氧樹脂、烷基多元醇型環氧樹脂、橡膠改質型環氧樹脂、環氧丙酯化合物、雙酚A型環硫(episulfide)樹脂等。 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 ring Oxygen resin, thioether epoxy resin, diphenyl ether epoxy resin, dicyclopentadiene epoxy resin, naphthalene epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin Resin, dicyclopentadiene novolac epoxy resin, biphenol novolac epoxy resin, naphthol novolac epoxy resin, glycidylamine epoxy resin, alkyl polyol epoxy resin, rubber Modified epoxy resin, glycidyl ester compound, bisphenol A episulfide resin, etc.

上述雙酚A型環氧樹脂之中，作為市售者，例如可列舉：jER828EL、jER1001、jER1004(均為三菱化學公司製造)、EPICLON 850CRP(DIC公司製造)等。上述雙酚F型環氧樹脂之中，作為市售者，例如可列舉jER806、jER4004(均為三菱化學公司製造)等。 Among the above-mentioned bisphenol A type epoxy resins, commercially available examples include jER828EL, jER1001, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON 850CRP (manufactured by DIC Corporation), and the like. Among the bisphenol F-type epoxy resins mentioned above, examples of commercially available products include jER806 and jER4004 (all manufactured by Mitsubishi Chemical Corporation).

上述雙酚S型環氧樹脂之中，作為市售者，例如可舉EPICLON EXA1514(DIC公司製造)等。 Among the bisphenol S-type epoxy resins mentioned above, as a commercially available product, for example, EPICLON EXA1514 (manufactured by DIC Corporation) can be cited.

上述2,2'-二烯丙基雙酚A型環氧樹脂之中，作為市售者，例如可舉 RE-810NM(日本化藥公司製造)等。 Among the above-mentioned 2,2'-diallylbisphenol A type epoxy resins, as a commercially available one, for example, RE-810NM (manufactured by Nippon Kayaku) and others.

上述氫化雙酚型環氧樹脂之中，作為市售者，例如可舉EPICLON EXA7015(DIC公司製造)等。 Among the above-mentioned hydrogenated bisphenol-type epoxy resins, as a commercially available product, for example, EPICLON EXA7015 (manufactured by DIC Corporation) can be cited.

上述環氧丙烷加成雙酚A型環氧樹脂之中，作為市售者，例如可舉EP-4000S(艾迪科公司製造)等。 Among the above-mentioned propylene oxide-added bisphenol A epoxy resins, as a commercially available product, for example, EP-4000S (manufactured by ADICO) can be cited.

上述間苯二酚型環氧樹脂之中，作為市售者，例如可舉EX-201(長瀨化成公司製造)等。 Among the resorcinol type epoxy resins mentioned above, as a commercially available product, for example, EX-201 (manufactured by Nagase Chemicals) can be mentioned.

上述聯苯型環氧樹脂之中，作為市售者，例如可舉jER YX-4000H(三菱化學公司製造)等。 Among the biphenyl epoxy resins mentioned above, as a commercially available product, for example, jER YX-4000H (manufactured by Mitsubishi Chemical Corporation) can be cited.

上述硫醚型環氧樹脂之中，作為市售者，例如可舉YSLV-50TE(新日鐵住金化學公司製造)等。 Among the above-mentioned thioether epoxy resins, YSLV-50TE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) may be mentioned as a commercially available product.

上述二苯醚型環氧樹脂之中，作為市售者，例如可舉YSLV-80DE(新日鐵住金化學公司製造)等。 Among the above diphenyl ether-type epoxy resins, YSLV-80DE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and the like may be mentioned as a commercially available product.

上述二環戊二烯型環氧樹脂之中，作為市售者，例如可舉EP-4088S(艾迪科公司製造)等。 Among the above-mentioned dicyclopentadiene-type epoxy resins, as a commercially available product, for example, EP-4088S (manufactured by Adiko) can be cited.

上述萘型環氧樹脂之中，作為市售者，例如可舉EPICLON HP4032、EPICLON EXA-4700(均為DIC公司製造)等。 Among the above naphthalene-type epoxy resins, as a commercially available product, for example, EPICLON HP4032, EPICLON EXA-4700 (all manufactured by DIC Corporation), etc. may be mentioned.

上述苯酚酚醛清漆型環氧樹脂之中，作為市售者，例如可舉EPICLON N-770(DIC公司製造)等。 Among the phenol novolac-type epoxy resins mentioned above, as a commercially available product, for example, EPICLON N-770 (manufactured by DIC Corporation) can be cited.

上述鄰甲酚酚醛清漆型環氧樹脂之中，作為市售者，例如可舉EPICLON N-670-EXP-S(DIC公司製造)等。 Among the ortho-cresol novolac-type epoxy resins mentioned above, as a commercially available product, for example, EPICLON N-670-EXP-S (manufactured by DIC) can be cited.

上述二環戊二烯酚醛清漆型環氧樹脂之中，作為市售者，例如可舉 EPICLON HP7200(DIC公司製造)等。 Among the above dicyclopentadiene novolac-type epoxy resins, as a commercially available one, for example, EPICLON HP7200 (made by DIC), etc.

上述聯苯酚醛清漆型環氧樹脂之中，作為市售者，例如可舉NC-3000P(日本化藥公司製造)等。 Among the biphenol novolac-type epoxy resins, as a commercially available product, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) can be cited.

上述萘酚酚醛清漆型環氧樹脂之中，作為市售者，例如可舉ESN-165S(新日鐵住金化學公司製造)等。 Among the above naphthol novolak-type epoxy resins, as a commercially available product, for example, ESN-165S (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) may be mentioned.

上述環氧丙胺型環氧樹脂之中，作為市售者，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。 Among the above-mentioned glycidylamine-type epoxy resins, commercially available examples include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation), and the like.

上述烷基多元醇型環氧樹脂之中，作為市售者，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。 Among the above-mentioned alkyl polyol-type epoxy resins, examples of commercially available products include ZX-1542 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), EPICLON 726 (manufactured by DIC), and Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd. ), DENACOL EX-611 (made by Nagase Chemical Co., Ltd.), etc.

上述橡膠改質型環氧樹脂之中，作為市售者，例如可列舉YR-450、YR-207(均為新日鐵住金化學公司製造)、Epolead PB(大賽璐公司製造)等。 Among the rubber-modified epoxy resins mentioned above, YR-450, YR-207 (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epolead PB (manufactured by Daicel Corporation) and the like can be cited as commercially available ones.

上述環氧丙酯化合物之中，作為市售者，例如可舉DENACOL EX-147(長瀨化成公司製造)等。 Among the above glycidyl ester compounds, as a commercially available product, for example, DENACOL EX-147 (manufactured by Nagase Chemicals Co., Ltd.) can be cited.

上述雙酚A型環硫樹脂之中，作為市售者，例如可舉jER YL-7000(三菱化學公司製造)等。 Among the bisphenol A-type episulfide resins mentioned above, as a commercially available product, for example, jER YL-7000 (manufactured by Mitsubishi Chemical Corporation) can be cited.

上述環氧化合物之中，作為其他市售者，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。 Among the above-mentioned epoxy compounds, as other commercial vendors, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, jER1032 ( All are made by Mitsubishi Chemical Corporation), EXA-7120 (made by DIC Corporation), TEPIC (made by Nissan Chemical Corporation), etc.

上述環氧(甲基)丙烯酸酯之中，作為市售者，例如可列舉EBECRYL860、EBECRYL3200、EBECRYL3201、EBECRYL3412、EBECRYL3600、EBECRYL3700、EBECRYL3701、EBECRYL3702、EBECRYL3703、EBECRYL3800、EBECRYL6040、EBECRYL RDX63182(均為大賽璐湛新公司製造)、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 EsterM-600A、Epoxy Ester40EM、Epoxy Ester70PA、Epoxy Ester200PA、Epoxy Ester80MFA、Epoxy Ester3002M、Epoxy Ester3002A、Epoxy Ester1600A、Epoxy Ester3000M、Epoxy Ester3000A、Epoxy Ester200EA、Epoxy Ester400EA(均為共榮社化學公司製造)、Denacol Acrylate DA-141、Denacol Acrylate DA-314、Denacol Acrylate DA-911(均為長瀨化成公司製造)等。 Among the above-mentioned epoxy (meth)acrylates, as a commercially available product, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBECRYL RDX63 (Made by the new company), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin Nakamura Chemical Industry Company), Epoxy EsterM-600A, Epoxy Ester40EM, Epoxy Ester70PA, Epoxy Ester200PA, Epoxy Ester80MFA, Epoxy Ester3002M, Epoxy Ester3002A, Epoxy Ester1600A, Epoxy Ester3000M, Epoxy Ester3000A, Epoxy Ester200EA, Epoxy Ester400EA (all manufactured by Kyoeisha Chemical Company), Denacol Acrylate DA-141, Denacol Acrylate Acrylate DA-911 (all manufactured by Nagase Chemical Co., Ltd.), 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2當量與具有2個異氰酸酯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 aforementioned (meth)acrylic acid amine ester can be obtained, for example, by reacting 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 catalyst-based tin compound .

作為成為上述(甲基)丙烯酸胺酯之原料之異氰酸酯化合物，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、聚合MDI、1,5-萘二異氰酸酯、降

Figure 105117135-A0202-12-0011-9
烷二異氰酸酯、聯甲苯胺二異氰酸酯、伸茬基二異氰酸酯(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、四甲基伸茬基二異氰酸酯、1,6,11-十一烷三異氰酸酯等。 Examples of the isocyanate compound that becomes the raw material of the amine (meth)acrylate 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,
Figure 105117135-A0202-12-0011-9
Alkyl diisocyanate, tolidine diisocyanate, stubble diisocyanate (XDI), hydrogenated XDI, urethane diisocyanate, triphenylmethane triisocyanate, tri(isocyanatophenyl) phosphorothioate, tetramethyl extension Stubble 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、聚己內酯二醇等多元醇與過量的異氰酸酯化合物之反應所獲得之經鏈延長的異氰酸酯化合物。 In addition, as the isocyanate compound, for example, ethylene glycol, Propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and other polyols and excess isocyanate compound obtained by the reaction chain Extended isocyanate compound.

作為成為上述(甲基)丙烯酸胺酯的原料之具有羥基之(甲基)丙烯酸衍生物，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、聚乙二醇等二元醇之單(甲基)丙烯酸酯，或三羥甲基乙烷、三羥甲基丙烷、甘油等三元醇之單(甲基)丙烯酸酯或二(甲基)丙烯酸酯，或雙酚A型環氧(甲基)丙烯酸酯等環氧(甲基)丙烯酸酯等。 Examples of the (meth)acrylic acid derivative having a hydroxyl group as a raw material of the amine (meth)acrylate include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, and 1, Mono(meth)acrylates of diols such as 4-butanediol and polyethylene glycol, or mono(meth)acrylates of triols such as trimethylolethane, trimethylolpropane, and glycerin Or epoxy (meth)acrylates such as di(meth)acrylate or bisphenol A epoxy (meth)acrylate.

上述(甲基)丙烯酸胺酯之中，作為市售者，例如可列舉：M-1100、M-1200、M-1210、M-1600(均為東亞合成公司製造)、EBECRYL230、EBECRYL270、EBECRYL4858、EBECRYL8402、EBECRYL8804、EBECRYL8803、EBECRYL8807、EBECRYL9260、EBECRYL1290、EBECRYL5129、EBECRYL4842、EBECRYL210、EBECRYL4827、EBECRYL6700、EBECRYL220、EBECRYL2220(均為大賽璐湛新公司製造)、Artresin UN-9000H、Artresin UN-9000A、Artresin UN-7100、Artresin UN-1255、Artresin UN-330、Artresin UN-3320HB、Artresin UN-1200TPK、Artresin SH-500B(均為根上工業公司製造)、U-2HA、U-2PHA、U-3HA、U-4HA、U-6H、U-6LPA、U-6HA、U-10H、U-15HA、U-122A、U-122P、U-108、U-108A、U-324A、U-340A、U-340P、U-1084A、U-2061BA、UA-340P、UA-4100、UA-4000、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)、AI-600、AH-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。 Among the above-mentioned (meth)acrylate amine esters, as a commercially available product, for example, M-1100, M-1200, M-1210, M-1600 (all manufactured by East Asia Synthetic Corporation), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYLArt20, UN-Art, Res. , Artresin UN-1255, Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK, Artresin SH-500B (all made by Genshang Industrial Company), U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6LPA, U-6HA, U-10H, U-15HA, U-122A, U-122P, U-108, U-108A, U-324A, U-340A, U-340P, U- 1084A, U-2061BA, UA-340P, UA-4100, UA-4000, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A (all made by Shin Nakamura Chemical Industry Company) ), AI-600, AH-600, AT-600, UA-101I, UA -101T, UA-306H, UA-306I, UA-306T (all manufactured by Kyoeisha Chemical Company), etc.

關於上述具有(甲基)丙烯醯基之化合物，就抑制對液晶之不良影響之方面而言，較佳為具有-OH基、-NH-基、-NH2基等氫鍵性單元者。 The compound having a (meth)acryloyl group is preferably one having a hydrogen bonding unit such as a -OH group, a -NH- group, and a -NH 2 group in terms of suppressing the adverse effects on the liquid crystal.

又，關於上述具有(甲基)丙烯醯基之化合物，就反應性高之方面而言，較佳為分子中具有2~3個(甲基)丙烯醯基者。 In addition, the compound having the (meth)acryloyl group is preferably one having 2 to 3 (meth)acryloyl groups in the molecule in terms of high reactivity.

為了使所獲得之液晶顯示元件用密封劑之接著性提昇，上述硬化性樹脂亦可含有環氧化合物。 In order to improve the adhesiveness of the obtained sealing compound for liquid crystal display elements, the said curable resin may contain an epoxy compound.

作為上述環氧化合物，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，或部分(甲基)丙烯酸改質環氧樹脂等。 Examples of the epoxy compound include an epoxy compound used as a raw material for synthesizing the epoxy (meth)acrylate, or a partially (meth)acrylic modified epoxy resin.

再者，於本說明書中，上述所謂部分(甲基)丙烯酸改質環氧樹脂，意指1分子中具有環氧基及(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個以上環氧基之環氧化合物之一部分環氧基與(甲基)丙烯酸進行反應而獲得。 In addition, in this specification, the so-called partially (meth)acrylic modified epoxy resin means a compound having one or more epoxy groups and (meth)acryloyl groups in one molecule, for example, by It is obtained by reacting a part of epoxy groups of an epoxy compound having two or more epoxy groups with (meth)acrylic acid in one molecule.

於上述硬化性樹脂含有上述具有(甲基)丙烯醯基之化合物及上述環氧化合物之情形時，較佳以(甲基)丙烯醯基與環氧基之比成為30：70~95：5之方式摻合上述具有(甲基)丙烯醯基之化合物及上述環氧化合物。藉由(甲基)丙烯醯基之比率為30%以上，所獲得之液晶顯示元件用密封劑成為低液晶污染性更優異者。藉由(甲基)丙烯醯基之比率為95%以下，所獲得之液晶顯示元件用密封劑成為接著性更優異者。 When the curable resin contains the compound having the (meth)acryloyl group and the epoxy compound, the ratio of the (meth)acryloyl group to the epoxy group is preferably 30:70 to 95:5 The above compound having the (meth)acryloyl group and the above epoxy compound are blended. When the ratio of (meth)acryloyl group is 30% or more, the obtained sealing compound for liquid crystal display elements becomes more excellent in low liquid crystal contamination. When the ratio of (meth)acryl acetyl group is 95% or less, the obtained sealing compound for liquid crystal display elements becomes more excellent in adhesiveness.

本發明之液晶顯示元件用密封劑可含有增感劑。 The sealing agent for liquid crystal display elements of this invention may contain a sensitizer.

關於上述增感劑，就對上述式(1)所示之化合物的光增感效果優異之 方面而言，較佳含有胺系增感劑。 Regarding the above-mentioned sensitizer, the compound having an excellent photosensitizing effect on the compound represented by the above formula (1) In terms of aspect, it is preferable to contain an amine-based sensitizer.

作為上述胺系增感劑，例如可列舉：下述式(2)所示之化合物、4,4'-雙(二乙胺基)二苯甲酮、2-(二甲胺基)苯甲酸乙酯、4-(二甲胺基)苯甲酸乙酯、4-(二甲胺基)苯甲酸2-乙基己酯、4-(二甲胺基)苯甲酸異戊酯、4-(二甲胺基)苯甲酸丁氧基乙酯等。其中，就所獲得之液晶顯示元件用密封劑成為硬化性優異者之方面而言，較佳為下述式(2)所示之化合物。 Examples of the amine-based sensitizer include compounds represented by the following formula (2), 4,4′-bis(diethylamino)benzophenone, and 2-(dimethylamino)benzoic acid Ethyl ester, ethyl 4-(dimethylamino)benzoate, 2-ethylhexyl 4-(dimethylamino)benzoate, isoamyl 4-(dimethylamino)benzoate, 4-( Dimethylamino) butoxyethyl benzoate, etc. Among them, the compound represented by the following formula (2) is preferable in that the obtained sealant for liquid crystal display elements is excellent in curability.

Figure 105117135-A0202-12-0014-3
Figure 105117135-A0202-12-0014-3

式(2)中，z表示1以上之整數，P為(聚)乙二醇、(聚)丙二醇、(聚)丁二醇、甘油、三羥甲基丙烷、二-三羥甲基丙烷、新戊四醇、二新戊四醇，或己內酯多元醇之殘基。 In formula (2), z represents an integer of 1 or more, and P is (poly)ethylene glycol, (poly)propylene glycol, (poly)butanediol, glycerin, trimethylolpropane, di-trimethylolpropane, Residues of neopentaerythritol, dipentaerythritol, or caprolactone polyol.

上述式(2)中，z表示1以上之整數，較佳下限為2，較佳上限為6。藉由上述z為2以上，所獲得之液晶顯示元件用密封劑成為低液晶污染性更優異者。藉由上述z為6以下，黏度不會變得過高，從而成為操作性更優異者。 In the above formula (2), z represents an integer of 1 or more, preferably the lower limit is 2, and the upper limit is preferably 6. When z is 2 or more, the obtained sealant for liquid crystal display elements becomes more excellent in low liquid crystal contamination. When z is 6 or less, the viscosity does not become too high, and the operability is more excellent.

上述式(2)中，P為(聚)乙二醇、(聚)丙二醇、(聚)丁二醇、甘油、三羥甲基丙烷、二-三羥甲基丙烷、新戊四醇、二新戊四醇，或己內酯多元醇之殘基。 In the above formula (2), P is (poly)ethylene glycol, (poly)propylene glycol, (poly)butanediol, glycerin, trimethylolpropane, di-trimethylolpropane, neopentyltetraol, diethylene glycol The residue of neopentaerythritol, or caprolactone polyol.

上述式(2)中之P的分子量之較佳下限為100，較佳上限為2000。藉由P之分子量為100以上，所獲得之液晶顯示元件用密封劑成為低液晶污染性更優異者。藉由P之分子量為2000以下，黏度不會變得過高，從而成為操作性更優異者。 The preferred lower limit of the molecular weight of P in the above formula (2) is 100, and the preferred upper limit is 2000. When the molecular weight of P is 100 or more, the obtained sealant for liquid crystal display elements becomes more excellent in low liquid crystal contamination. When the molecular weight of P is 2000 or less, the viscosity will not become too high, and thus it will become more excellent in operability.

上述式(2)所示之化合物較佳式(2)中之z為2且P為聚乙二醇之殘基。 In the compound represented by the above formula (2), it is preferred that z in formula (2) is 2 and P is a residue of polyethylene glycol.

上述增感劑之中，作為上述胺系增感劑以外者，例如可列舉：蒽衍生物、蒽醌衍生物、香豆素衍生物、9-氧硫

Figure 105117135-A0202-12-0015-10
衍生物、酞青素衍生物等。 Among the above sensitizers, examples of the amine-based sensitizers include anthracene derivatives, anthraquinone derivatives, coumarin derivatives, and 9-oxosulfur.
Figure 105117135-A0202-12-0015-10
Derivatives, phthalocyanin derivatives, etc.

作為上述蒽衍生物，例如可列舉：9,10-二丁氧基蒽、9,10-二乙氧基蒽、9,10-二丙氧基蒽等。 Examples of the anthracene derivatives include 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and the like.

作為上述蒽醌衍生物，例如可列舉：2-乙基蒽醌、1-甲基蒽醌、1,4-二羥基蒽醌、2-(2-羥基乙氧基)蒽醌等。 Examples of the anthraquinone derivatives include 2-ethylanthraquinone, 1-methylanthraquinone, 1,4-dihydroxyanthraquinone, 2-(2-hydroxyethoxy)anthraquinone, and the like.

作為上述香豆素衍生物，例如可舉：7-二乙胺基-4-甲基香豆素等。 Examples of the coumarin derivatives include 7-diethylamino-4-methylcoumarin and the like.

作為上述9-氧硫

Figure 105117135-A0202-12-0015-11
衍生物，例如可列舉：2,4-二乙基9-氧硫
Figure 105117135-A0202-12-0015-13
、2-氯9-氧硫
Figure 105117135-A0202-12-0015-12
、4-異丙基9-氧硫
Figure 105117135-A0202-12-0015-14
、1-氯-4-丙基9-氧硫
Figure 105117135-A0202-12-0015-15
等。 As the above 9-oxygen sulfur
Figure 105117135-A0202-12-0015-11
Derivatives, for example: 2,4-diethyl 9-oxysulfide
Figure 105117135-A0202-12-0015-13
, 2-chloro9-oxysulfur
Figure 105117135-A0202-12-0015-12
, 4-isopropyl 9-oxysulfur
Figure 105117135-A0202-12-0015-14
, 1-chloro-4-propyl 9-oxysulfur
Figure 105117135-A0202-12-0015-15
Wait.

作為上述酞青素衍生物，例如可列舉酞青素等。 Examples of the phthalocyanine derivatives include phthalocyanine.

又，亦可使用作為上述其他光自由基聚合起始劑而列舉之二苯甲酮系化合物作為增感劑。 In addition, benzophenone-based compounds exemplified as the other photo-radical polymerization initiators may be used as a sensitizer.

關於上述增感劑之含量，相對於硬化性樹脂100重量份，較佳下限為0.1重量份，較佳上限為2重量份。藉由上述增感劑之含量為該範 圍，能夠維持所獲得之液晶顯示元件用密封劑之優異低液晶污染性，並且發揮更高之增感效果。上述增感劑之含量之更佳下限為0.2重量份，更佳上限為1重量份。 Regarding the content of the sensitizer, with respect to 100 parts by weight of the curable resin, the lower limit is preferably 0.1 part by weight, and the upper limit is preferably 2 parts by weight. With the content of the above sensitizer as this range It is possible to maintain the excellent low liquid crystal contamination of the obtained sealant for liquid crystal display elements and exert a higher sensitizing effect. The more preferable lower limit of the content of the sensitizer is 0.2 parts by weight, and the more preferable upper limit is 1 part by weight.

上述式(1)所示之化合物與上述增感劑之含有比例較佳以重量比計為式(1)所示之化合物：增感劑=1：0.1~1：0.7。藉由上述式(1)所示之化合物與上述增感劑之含有比例為該範圍內，本發明之液晶顯示元件用密封劑成為抑制液晶污染之效果及可見光硬化性特別優異者。上述式(1)所示之化合物與上述增感劑之含有比例更佳為式(1)所示之化合物：增感劑=1：0.2~1：0.6。 The content ratio of the compound represented by the formula (1) and the sensitizer is preferably the compound represented by the formula (1) in terms of weight ratio: sensitizer = 1: 0.1 to 1: 0.7. When the content ratio of the compound represented by the formula (1) and the sensitizer is within this range, the sealing compound for a liquid crystal display element of the present invention is particularly excellent in the effect of suppressing liquid crystal contamination and the visible light curability. The content ratio of the compound represented by the formula (1) and the sensitizer is more preferably the compound represented by the formula (1): sensitizer = 1: 0.2 to 1: 0.6.

本發明之液晶顯示元件用密封劑亦可含有熱自由基聚合起始劑。 The sealing agent for liquid crystal display elements of this invention may also contain a thermal radical polymerization initiator.

作為上述熱自由基聚合起始劑，例如可列舉由偶氮化合物、有機過氧化物等構成者。其中，較佳為由高分子偶氮化合物構成之起始劑(以下，亦稱為「高分子偶氮起始劑」)。 Examples of the above-mentioned thermal radical polymerization initiator include those composed of an azo compound and an organic peroxide. Among them, an initiator composed of a polymer azo compound (hereinafter, also referred to as "polymer azo initiator") is preferred.

再者，於本說明書中，所謂高分子偶氮起始劑，意指具有偶氮基且藉由熱而生成可使(甲基)丙烯醯氧基硬化之自由基的數量平均分子量為300以上之化合物。 In addition, in this specification, the term "polymeric azo initiator" means that the number average molecular weight of a radical having an azo group and generated by heat that can harden the (meth)acryloyloxy group is 300 or more. Of compounds.

上述高分子偶氮起始劑之數量平均分子量之較佳下限為1000，較佳上限為30萬。藉由上述高分子偶氮起始劑之數量平均分子量為該範圍，能夠防止對液晶之不良影響並且更容易地混合於硬化性樹脂中。上述高分子偶氮起始劑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。 The preferred lower limit of the number average molecular weight of the above polymer azo initiator is 1,000, and the preferred upper limit is 300,000. When the number average molecular weight of the above-mentioned polymer azo initiator is within this range, it is possible to prevent adverse effects on the liquid crystal and to more easily mix in the curable resin. The more preferable lower limit of the number average molecular weight of the above polymer azo initiator is 5000, the more preferable upper limit is 100,000, the more preferable lower limit is 10,000, and the more preferable upper limit is 90,000.

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)進行測量並藉由聚苯乙烯換算而求出之值。作為藉由GPC測量基於聚苯乙烯換算之數量平均分子量時之管柱，例如可舉Shodex LF-804(昭和電工公司製造)等。 In addition, in this specification, the said number average molecular weight is the value measured by gel permeation chromatography (GPC) and converted by polystyrene. As a column for measuring the number average molecular weight based on polystyrene conversion by GPC, for example, Shodex LF-804 (manufactured by Showa Denko KK) and the like can be mentioned.

作為上述高分子偶氮起始劑，例如可列舉經由偶氮基鍵結有多個聚環氧烷(polyalkylene oxide)或聚二甲基矽氧烷等單元之結構者。 Examples of the polymer azo initiator include a structure in which a plurality of units such as polyalkylene oxide or polydimethylsiloxane are bonded via an azo group.

作為上述具有經由偶氮基鍵結有多個聚環氧烷等單元之結構之高分子偶氮起始劑，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，具體而言，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。 As the polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide is bonded via an azo group, those having a polyethylene oxide structure are preferred. As such a polymer azo initiator, for example, a polycondensate of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or 4,4'-azo Polycondensates of bis(4-cyanovaleric acid) and polydimethylsiloxane having terminal amine groups, etc. Specifically, for example, VPE-0201, VPE-0401, VPE-0601, VPS-0501 , VPS-1001 (all manufactured by Wako Pure Chemical Industries), etc.

又，作為非高分子之偶氮化合物之例，可列舉V-65、V-501(均為和光純藥工業公司製造)等。 In addition, as examples of non-polymer azo compounds, V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.), etc. may be mentioned.

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、過氧化二烷基、過氧酯、過氧化二醯基、過氧化二碳酸酯等。 Examples of the organic peroxide include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.

關於上述熱自由基聚合起始劑之含量，相對於上述硬化性樹脂100重量份，較佳下限為0.05重量份，較佳上限為10重量份。藉由上述熱自由基聚合起始劑之含量為該範圍，抑制因未反應之熱自由基聚合起始劑而引起之液晶污染，並且所獲得之液晶顯示元件用密封劑成為熱硬化性更優異者。上述熱自由基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 radical polymerization initiator, with respect to 100 parts by weight of the curable resin, the lower limit is preferably 0.05 parts by weight, and the upper limit is preferably 10 parts by weight. With the content of the above-mentioned thermal radical polymerization initiator being in this range, the liquid crystal contamination caused by unreacted thermal radical polymerization initiator is suppressed, and the obtained sealant for liquid crystal display elements becomes more thermosetting By. The more preferable lower limit of the content of the above-mentioned thermal radical polymerization initiator is 0.1 part by weight, and the 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 compound 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 hydrazide include, for example, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, and malonic acid dihydrazide.

上述有機酸醯肼之中，作為市售者，例如可列舉：SDH、ADH(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。 Among the above-mentioned organic acid hydrazides, as a commercially available product, for example, SDH, ADH (all made by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J (all Ajinomoto Fine- 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。藉由上述熱硬化劑之含量為1重量份以上，所獲得之液晶顯示元件用密封劑成為熱硬化性更優異者。藉由上述熱硬化劑之含量為50重量份以下，所獲得之液晶顯示元件用密封劑之黏度不會變得過高，從而成為塗佈性更優異者。上述熱硬化劑之含量之更佳上限為30重量份。 Regarding the content of the above-mentioned thermosetting agent, with respect to 100 parts by weight of the above-mentioned curable resin, the lower limit is preferably 1 part by weight, and the upper limit is preferably 50 parts by weight. When the content of the thermosetting agent is 1 part by weight or more, the obtained sealing compound for liquid crystal display elements becomes more excellent in thermosetting property. When the content of the above-mentioned thermosetting agent is 50 parts by weight or less, the viscosity of the obtained sealing compound for liquid crystal display elements does not become too high, so that it becomes more excellent in coatability. The upper limit of the content of the above-mentioned thermosetting agent is more preferably 30 parts by weight.

為了實現黏度之提昇、藉由應力分散效果之接著性之改善、線膨脹率之改善、硬化物之耐濕性之進一步提昇等，本發明之液晶顯示元件用密封劑較佳含有填充劑。 In order to achieve an increase in viscosity, an improvement in adhesion by a stress dispersion effect, an improvement in linear expansion rate, and a further improvement in moisture resistance of a cured product, the sealant for liquid crystal display devices of the present invention preferably contains a filler.

作為上述填充劑，例如可列舉：滑石、石棉、二氧化矽、矽藻土、膨潤石、膨潤土、碳酸鈣、碳酸鎂、氧化鋁、蒙脫石、氧化鋅、氧化鐵、氧化鎂、氧化錫、氧化鈦、氫氧化鎂、氫氧化鋁、玻璃珠粒、氮化矽、硫酸鋇、石膏、矽酸鈣、絹雲母、活性白土、氮化鋁等無機填充劑，或聚酯微粒子、聚胺酯微粒子、乙烯聚合物微粒子、丙烯酸聚合物微粒子 等有機填充劑。該等填充劑可單獨使用，亦可將2種以上併用。 Examples of the filler include talc, asbestos, silica, diatomaceous earth, bentonite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, and tin oxide , Titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite, activated clay, aluminum nitride and other inorganic fillers, or polyester particles, polyurethane particles , Vinyl polymer particles, acrylic polymer particles And other organic fillers. These fillers can be used alone or in combination of two or more.

本發明之液晶顯示元件用密封劑100重量份中之上述填充劑的含量之較佳下限為10重量份，較佳上限為70重量份。藉由上述填充劑之含量為10重量份以上，成為接著性之改善等效果更優異者。藉由上述填充劑之含量為70重量份以下，所獲得之液晶顯示元件用密封劑之黏度不會變得過高，從而成為塗佈性更優異者。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。 The preferable lower limit of the content of the filler in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is 10 parts by weight, and the preferable upper limit is 70 parts by weight. When the content of the filler is 10 parts by weight or more, it becomes a more excellent effect such as improvement in adhesion. When the content of the filler is 70 parts by weight or less, the viscosity of the obtained sealing compound for liquid crystal display elements does not become too high, and thus becomes more excellent in coatability. 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含有矽烷偶合劑。上述矽烷偶合劑主要具有作為用以使密封劑與基板等良好地接著之接著助劑之作用。 The sealing agent for liquid crystal display elements of the present invention preferably contains a silane coupling agent. The above-mentioned silane coupling agent mainly has a role as an adhesion aid for good adhesion of the sealant and the substrate.

作為上述矽烷偶合劑，就提昇與基板等之接著性之效果優異、藉由與硬化性樹脂進行化學鍵結而可抑制硬化性樹脂向液晶中流出之方面而言，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-環氧丙氧基丙基三甲氧基矽烷、3-異氰酸酯基丙基三甲氧基矽烷等。該等矽烷偶合劑可單獨使用，亦可將2種以上併用。 As the above-mentioned silane coupling agent, since it has an excellent effect of improving adhesion with a substrate and the like, and chemical bonding with a curable resin can suppress the outflow of the curable resin into the liquid crystal, for example, it can be preferably used: 3 -Aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, etc. These silane coupling agents can be used alone or in combination of two or more.

本發明之液晶顯示元件用密封劑100重量份中之上述矽烷偶合劑的含量之較佳下限為0.1重量份，較佳上限為10重量份。藉由上述矽烷偶合劑之含量為該範圍，成為抑制液晶污染之產生並且提昇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。 The preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 0.1 part by weight, and the preferable upper limit is 10 parts by weight. When the content of the above-mentioned silane coupling agent falls within this range, it is more effective in suppressing the generation of liquid crystal contamination and improving the adhesion. The lower limit of the content of the silane coupling agent is more preferably 0.3 part by weight, and the upper limit is more preferably 5 parts by weight.

本發明之液晶顯示元件用密封劑亦可含有遮光劑(shielding agent)。藉由含有上述遮光劑，本發明之液晶顯示元件用密封劑能夠較佳地 用作遮光密封劑。 The sealing agent for liquid crystal display elements of this invention may contain a shielding agent. By containing the above-mentioned light-shielding agent, the sealing compound for liquid crystal display elements of this invention can be preferably Used as shading sealant.

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，較佳為鈦黑。 Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Among them, titanium black is preferred.

上述鈦黑係與對波長300~800nm之光的平均透射透射率相比較，對紫外線區域附近，尤其是波長370~450nm之光的透射率提高之物質。即，上述鈦黑係具有如下性質之遮光劑：藉由充分地遮蔽可見光區域之波長的光而對本發明之液晶顯示元件用密封劑賦予遮光性，另一方面，使紫外線區域附近之波長之光透射。作為於本發明之液晶顯示元件用密封劑中所含有之遮光劑，較佳為絕緣性高之物質，作為絕緣性高之遮光劑，亦較佳為鈦黑。 The above-mentioned titanium black is a substance that has improved transmittance in the vicinity of the ultraviolet region, especially light with a wavelength of 370 to 450 nm, compared with the average transmittance for light with a wavelength of 300 to 800 nm. That is, the above-mentioned titanium black is a light-shielding agent having the property of giving light-shielding properties to the sealing agent for liquid crystal display elements of the present invention by sufficiently shielding light of wavelengths in the visible light region, and on the other hand, making light of wavelengths near the ultraviolet region transmission. The light-shielding agent contained in the sealant for liquid crystal display elements of the present invention is preferably a material with high insulation, and the light-shielding agent with high insulation is also preferably titanium black.

上述鈦黑即便為未經表面處理者亦發揮充分之效果，亦可使用表面經偶合劑等有機成分進行處理者，或經氧化矽、氧化鈦、氧化鍺、氧化鋁、氧化鋯、氧化鎂等無機成分被覆者等經表面處理之鈦黑。其中，經有機成分處理者就能夠進一步提昇絕緣性之方面而言較佳。 The above titanium black exerts sufficient effects even if it has not been surface-treated. It can also be treated with organic components such as coupling agents on the surface, or silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, etc. Titanium black with surface treatment such as those coated with inorganic ingredients. Among them, those treated with organic components are preferred in terms of further improvement in insulation.

又，使用含有上述鈦黑作為遮光劑之本發明之液晶顯示元件用密封劑所製造的液晶顯示元件由於具有充分之遮光性，故而能夠實現無光之漏出且具有高對比度並且具有優異之圖像顯示品質之液晶顯示元件。 Moreover, the liquid crystal display element manufactured using the sealing compound for liquid crystal display elements of the present invention containing the above titanium black as a light-shielding agent has sufficient light-shielding properties, so it can realize leakage without light, has high contrast, and has excellent images Display quality liquid crystal display device.

上述鈦黑之中，作為市售者，例如可列舉：12S、13M、13M-C、13R-N、14M-C(均為三菱綜合材料公司製造)、Tilack D(赤穗化成公司製造)等。 Among the above-mentioned titanium blacks, as a commercially available product, for example, 12S, 13M, 13M-C, 13R-N, 14M-C (all manufactured by Mitsubishi Materials Corporation), Tilack D (manufactured by Aksui Chemical Co., Ltd.), etc. may be mentioned. .

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 preferable lower limit of the volume resistance of the above 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的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。藉由上述遮光劑之一次粒徑為該範圍，不會使所獲得之液晶顯示元件用密封劑之塗佈性等變差，從而能夠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100nm。 The primary particle size of the light-shielding agent is not particularly limited as long as the distance between the substrates of the liquid crystal display element is less than the preferred lower limit is 1 nm, and the preferred upper limit is 5 μm. When the primary particle diameter of the above-mentioned light-shielding agent is in this range, the coating properties of the obtained sealing compound for liquid crystal display elements will not be deteriorated, and it is possible to produce a more excellent light-shielding property. The preferred lower limit of the primary particle size of the above-mentioned opacifier is 5 nm, the preferred upper limit is 200 nm, the preferred lower limit is 10 nm, and the preferred 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)中進行測量。 In addition, the primary particle diameter of the said sunscreen agent can be measured using NICOMP 380ZLS (made by PARTICLE SIZING SYSTEMS Co., Ltd.) by dispersing the said sunscreen agent in a solvent (water, organic solvent, etc.).

本發明之液晶顯示元件用密封劑100重量份中之上述遮光劑的含量之較佳下限為5重量份，較佳上限為80重量份。藉由上述遮光劑之含量為5重量份以上，所獲得之液晶顯示元件用密封劑成為遮光性更優異者。藉由上述遮光劑之含量為80重量份以下，所獲得之液晶顯示元件用密封劑成為對基板之密接性、硬化後之強度及描繪性更優異者。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 sealing compound for liquid crystal display elements of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight. When the content of the above-mentioned light-shielding agent is 5 parts by weight or more, the obtained sealing agent for liquid crystal display elements becomes more excellent in light-shielding property. When the content of the light-shielding agent is 80 parts by weight or less, the obtained sealant for liquid crystal display elements becomes more excellent in adhesion to the substrate, strength after curing, and drawability. The more preferable lower limit of the content of the above-mentioned sunscreen agent is 10 parts by weight, the more preferable upper limit is 70 parts by weight, the more preferable lower limit is 30 parts by weight, and the more preferable upper limit is 60 parts by weight.

作為製造本發明之液晶顯示元件用密封劑之方法，例如可列舉使用勻相分散機、均質混合機、萬能混合機、行星式混合機、捏合機、三輥研磨機等混合機，將硬化性樹脂、9-氧硫

Figure 105117135-A0202-12-0021-16
系聚合起始劑、胺系增感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。 As a method of manufacturing the sealing agent for liquid crystal display elements of the present invention, for example, a mixer such as a homogenous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mill can be used. Resin, 9-oxygen sulfur
Figure 105117135-A0202-12-0021-16
It is a method of mixing additives such as polymerization initiator, amine sensitizer, and silane coupling agent added as needed.

藉由將導電性微粒子摻合於本發明之液晶顯示元件用密封劑，能夠製造上下導通材料。又，此種含有本發明之液晶顯示元件用密封劑及導電性微粒子之上下導通材料亦為本發明之一。 By blending conductive fine particles into the sealant for a liquid crystal display element of the present invention, a vertical conduction material can be manufactured. Moreover, such a top-to-bottom conducting material containing the sealing compound for liquid crystal display elements of this invention and conductive fine particles is also one of this invention.

作為上述導電性微粒子，可使用在金屬球、樹脂微粒子之表面形成有導電金屬層者等。其中，較佳為在樹脂微粒子之表面形成有導電金屬層者，其原因在於：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。 As the conductive fine particles, those in which a conductive metal layer is formed on the surface of metal balls or resin fine particles can be used. Among them, it is preferable that a conductive metal layer is formed on the surface of the resin microparticles because the excellent elasticity of the resin microparticles enables conductive connection without damaging the transparent substrate or the like.

又，具有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的液晶顯示元件亦為本發明之一。 Moreover, the liquid crystal display element which has the sealing compound for liquid crystal display elements of this invention, or the upper-lower conduction material of this invention is also one of this invention.

作為製造本發明之液晶顯示元件之方法，例如可列舉具有如下步驟之方法等：於附ITO薄膜等之電極的玻璃基板或聚對酞酸乙二酯基板等2塊基板之一者，將本發明之液晶顯示元件用密封劑等藉由網版印刷、分注器塗佈等形成長方形狀之密封圖案的步驟；於本發明之液晶顯示元件用密封劑等為未硬化之狀態下，將液晶之微小滴滴下塗佈於基板之密封框內，並於真空下使其與另一基板重疊的步驟；對本發明之液晶顯示元件用密封劑等密封圖案部分照射紫外線等光使密封劑暫時硬化的步驟；及對暫時硬化之密封劑進行加熱使其正式硬化的步驟。 As a method of manufacturing the liquid crystal display element of the present invention, for example, a method having the following steps may be mentioned: one of two substrates such as a glass substrate with electrodes such as ITO thin films or a polyethylene terephthalate substrate, etc. The sealing agent for liquid crystal display elements of the invention is a step of forming a rectangular sealing pattern by screen printing, dispenser coating, etc.; in the state where the sealing agent for liquid crystal display elements of the present invention is uncured, the liquid crystal The tiny drops are applied to the sealing frame of the substrate and overlapped with another substrate under vacuum; the sealing pattern part of the sealing compound for liquid crystal display elements of the present invention is irradiated with ultraviolet light or the like to temporarily harden the sealing compound Step; and the step of heating the temporarily hardened sealant to formally harden it.

根據本發明，能夠提供一種可見光硬化性優異，且能夠抑制液晶污染之液晶顯示元件用密封劑。又，根據本發明，能夠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 which is excellent in visible light curability and can suppress contamination of liquid crystals. Furthermore, according to the present invention, it is possible to provide an upper and lower conduction material and a liquid crystal display element using the sealant for a liquid crystal display element.

1‧‧‧對單面之一半進行了鉻蒸鍍之基板 1‧‧‧ Substrate with chromium vapor deposition on one and a half of one side

11‧‧‧鉻蒸鍍部 11‧‧‧Cr deposition department

2‧‧‧對整個單面進行了鉻蒸鍍之基板 2‧‧‧ Substrate with chromium vapor deposition on the entire single side

21‧‧‧鉻蒸鍍部 21‧‧‧Cr deposition department

3‧‧‧位置A 3‧‧‧Position A

4‧‧‧位置B 4‧‧‧Position B

5‧‧‧位置C 5‧‧‧Position C

圖1係對遮光部硬化性之評價方法進行說明之示意圖。 FIG. 1 is a schematic diagram illustrating the evaluation method of the curability of the shading portion.

以下，列舉實施例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 further detail with examples, but the present invention is not limited to these examples.

(實施例1~9、比較例1~4) (Examples 1 to 9, Comparative Examples 1 to 4)

按照表1、2所記載之摻合比，將各材料使用行星式攪拌機(新基公司製造，「脫泡練太郎」)進行混合，之後，進而使用三輥研磨機進行混合，藉此製備實施例1~9、比較例1~4之各液晶顯示元件用密封劑。 According to the blending ratios listed in Tables 1 and 2, each material was mixed using a planetary mixer (manufactured by Shinki Corporation, "Defoaming Taro"), and then mixed using a three-roll mill to prepare and implement Sealants for liquid crystal display elements of Examples 1 to 9 and Comparative Examples 1 to 4.

再者，表中之「Omnipol 910」為式(1)之X為苯基、n為3~5，且重量平均分子量為1032之化合物，「Omnipol ASA」為式(2)中之z為2，且P為聚乙二醇之殘基之化合物。 Furthermore, "Omnipol 910" in the table is a compound of formula (1) where X is phenyl, n is 3 to 5, and the weight average molecular weight is 1032, and "Omnipol ASA" is z in formula (2) is 2 , And P is a compound of polyethylene glycol residues.

<評價> <evaluation>

針對實施例及比較例所獲得之各液晶顯示元件用密封劑進行以下評價。將結果示於表1、2。 The following evaluation was performed about each sealing compound for liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.

(光硬化性) (Photohardenability)

將使間隔物微粒子(積水化學工業公司製造，「Micropearl SI-H050」)1重量份分散於實施例及比較例所獲得之各液晶顯示元件用密封劑100重量份中而成者塗佈於玻璃基板上，並於該基板重疊相同尺寸之玻璃基板，繼而，使用金屬鹵素燈照射100mW/cm2之光10秒鐘，而製作光硬化性試片。關於光照射，進行無截止濾波器之情形及有400nm以下截止濾波器之情形 之2種模式，並針對各模式分別製作3塊試片。使用紅外分光裝置(BIORAD公司製造，「FTS3000」)，將815~800cm-1之波峰面積設為來自丙烯醯基之波峰面積，測量來自丙烯醯基的波峰面積之光照射前後之變化量，藉此進行光硬化性之評價。來自丙烯醯基之波峰面積係將845~820cm-1之波峰面積作為參考波峰面積而導出。將於光照射後來自丙烯醯基之波峰面積減少90%以上之情形設為「◎」，將於光照射後來自丙烯醯基之波峰面積減少80%以上、未達90%之情形設為「○」，將於光照射後來自丙烯醯基之波峰面積減少70%以上、未達80%之情形設為「△」，將於光照射後來自丙烯醯基的波峰面積之減少未達70%之情形設為「×」，對光硬化性進行評價。 1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Industry Co., Ltd., "Micropearl SI-H050") was dispersed in 100 parts by weight of each sealant for liquid crystal display elements obtained in Examples and Comparative Examples and applied to glass On the substrate, a glass substrate of the same size was superimposed on the substrate, and then a metal halide lamp was irradiated with light of 100 mW/cm 2 for 10 seconds to produce a photo-curable test piece. Regarding the light irradiation, two modes were performed without a cut filter and with a cut filter below 400 nm, and 3 test pieces were produced for each mode. Using an infrared spectrometer (manufactured by Biorad, "FTS3000"), set the peak area of 815 to 800 cm -1 as the peak area from the acrylic base, and measure the amount of change before and after light irradiation from the peak area of the acrylic base. This evaluates the photocurability. The peak area from acryl is derived from the peak area of 845~820cm -1 as the reference peak area. Set the case where the peak area from acryl base decreases by more than 90% after light irradiation is set to "◎", and the case that the peak area from acryl base decreases by more than 80% and does not reach 90% after light irradiation is set to "○", the case where the peak area from acrylic base is reduced by more than 70% and less than 80% after light irradiation is set to "△", and the peak area from acrylic base is not reduced by 70% after light irradiation In the case of "×", the photocurability was evaluated.

再者，來自丙烯醯基之波峰面積於光照射前後之變化量係採用根據3塊試片所獲得之平均值。 In addition, the amount of change in the peak area from the acryl group before and after light irradiation is the average value obtained from three test pieces.

(液晶污染性) (Liquid crystal pollution)

使間隔物微粒子(積水化學工業公司製造，「Micropearl SI-H050」)1重量份分散於實施例及比較例所獲得之各液晶顯示元件用密封劑100重量份中，製成液晶顯示元件用密封劑，以密封劑之線寬成為1mm之方式利用分注器塗佈於2塊附透明電極之基板之一者。繼而，將液晶(智索公司製造，「JC-5004LA」)之微小滴滴下塗佈於附透明電極之基板的密封劑之框內整個面，並立即貼合另一附透明電極之基板，對密封劑部分使用金屬鹵素燈照射100mW/cm2之紫外線30秒鐘，進而於120℃加熱1小時使密封劑硬化，而獲得液晶顯示元件。關於光照射，進行無截止濾波器之情形及有400nm以下截止濾波器之情形之2種模式，並針對各模式分別製作3塊液晶顯示元件。 1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Industry Co., Ltd., "Micropearl SI-H050") was dispersed in 100 parts by weight of each sealant for liquid crystal display elements obtained in Examples and Comparative Examples to prepare a seal for liquid crystal display elements The agent is applied to one of the two substrates with transparent electrodes using a dispenser so that the line width of the sealant becomes 1 mm. Then, the tiny drops of liquid crystal (manufactured by Chisuo Corporation, "JC-5004LA") were dropped onto the entire surface of the frame of the sealant applied to the substrate with transparent electrodes, and immediately attached to another substrate with transparent electrodes. The sealant part was irradiated with 100 mW/cm 2 of ultraviolet light for 30 seconds using a metal halogen lamp, and further heated at 120° C. for 1 hour to harden the sealant to obtain a liquid crystal display element. Regarding light irradiation, two modes are performed without a cut-off filter and with a cut-off filter of 400 nm or less, and three liquid crystal display elements are produced for each mode.

針對所獲得之液晶顯示元件，利用目視對設為60℃施加1000小時電壓之狀態後的密封劑附近之液晶污染進行確認。 Regarding the obtained liquid crystal display element, the liquid crystal contamination in the vicinity of the sealant after applying a voltage of 60° C. for 1000 hours was visually confirmed.

液晶污染係根據3塊液晶顯示元件之色不均進行判斷，根據色不均之程度，將於所有液晶顯示元件完全無色不均之情形設為「◎」，將於至少1塊液晶顯示元件略微有色不均之情形設為「○」，將於至少1塊液晶顯示元件有少許色不均之情形設為「△」，將於至少1塊液晶顯示元件有相當多色不均之情形設為「×」，從而對液晶污染性進行評價。 The liquid crystal contamination is judged based on the color unevenness of the three liquid crystal display elements. According to the degree of color unevenness, the situation where all liquid crystal display elements are completely colorless is set to "◎", and at least one liquid crystal display element is slightly The color unevenness is set to "○", and at least one liquid crystal display element has a slight color unevenness to "△", and the at least one liquid crystal display element has a considerable color unevenness to "X" to evaluate the liquid crystal contamination.

再者，評價為「◎」、「○」之液晶顯示元件為實用上完全無問題之等級。 In addition, the liquid crystal display elements evaluated as "◎" and "○" are practically problem-free.

(遮光部硬化性) (Curability of shading part)

對實施例及比較例所獲得之各液晶顯示元件用密封劑之遮光部硬化性，以如下所示之方式對各測量點的丙烯醯基之轉化率進行測量而進行評價。圖1係對遮光部硬化性之評價方法進行說明之示意圖。 The light-shielding portion curability of each sealant for liquid crystal display elements obtained in Examples and Comparative Examples was measured and evaluated by measuring the conversion rate of the propylene acetyl group at each measurement point as follows. FIG. 1 is a schematic diagram illustrating the evaluation method of the curability of the shading portion.

分別準備對康寧公司製造之玻璃(長度30mm、寬度30mm、厚度0.7mm)的單面之一半進行了鉻蒸鍍之基板1及對整個單面進行了鉻蒸鍍之基板2(圖1(a))。於基板1之經鉻蒸鍍之面側的中央部分別塗佈於實施例及比較例所獲得之於各液晶顯示元件用密封劑添加有5μm之聚合物珠粒1重量%而成之組成物20mg，並使基板1之塗佈有各組成物之面側與基板2之經鉻蒸鍍之面側重疊，之後充分地進行按壓(圖1(b))。 Separately prepare a substrate 1 that has been chromium-evaporated on one and a half sides of a glass (30 mm in length, 30 mm in width, and 0.7 mm in thickness) manufactured by Corning, and a substrate 2 that has been chromium-evaporated on the entire single surface (Figure 1(a )). A composition obtained by adding 5 μm of polymer beads of 5 μm to each liquid crystal display element sealant obtained in Examples and Comparative Examples was applied to the central portion of the substrate 1 on the chromium vapor-deposited surface side, respectively 20 mg, and the surface side of the substrate 1 on which each composition is applied overlaps the surface side of the substrate 2 where the chromium is vapor-deposited, and thereafter, it is sufficiently pressed (FIG. 1( b )).

繼而，對重疊之基板自基板1面側使用金屬鹵素燈通過400nm以下截止濾波器照射100mW/cm2之紫外線30秒鐘。使用切刀將基板1、2剝下，藉由顯微IR法，針對紫外線直接照射部(位置A)、自紫外線直接照射部旁 距遮光部側15μm之點(位置B)及自紫外線直接照射部旁距遮光部側30μm之點(位置C)上的密封劑(圖1(c))，使用紅外分光裝置(BIORAD公司製造，「FTS3000」)對來自丙烯醯基之波峰進行確認。 Then, the superimposed substrate was irradiated with ultraviolet light of 100 mW/cm 2 through a cut-off filter of 400 nm or less from a surface side of the substrate 1 using a metal halogen lamp for 30 seconds. The substrates 1 and 2 are peeled off with a knife, and the direct irradiation of ultraviolet rays (position A), a point 15 μm from the side of the light-shielding portion beside the direct irradiation portion of ultraviolet rays (position B), and direct irradiation from ultraviolet rays are performed by the micro IR method The sealant (Figure 1(c)) at a point (position C) 30 μm from the side of the light-shielding part side was confirmed by using an infrared spectrometer (manufactured by Biorad Co., Ltd., “FTS3000”) from the peak of acryl.

將815~800cm-1之波峰面積設為來自丙烯醯基之波峰面積，並對來自丙烯醯基的波峰面積之光照射前後之變化量進行測量，藉此進行光硬化性之評價。來自丙烯醯基之波峰面積係將845~820cm-1之波峰面積作為參考波峰面積而導出。將於光照射後來自丙烯醯基之波峰面積減少90%以上之情形設為「◎」，將於光照射後來自丙烯醯基之波峰面積減少80%以上、未達90%之情形設為「○」，將於光照射後來自丙烯醯基之波峰面積減少70%以上、未達80%之情形設為「△」，將於光照射後來自丙烯醯基的波峰面積之減少未達70%之情形設為「×」，從而對光硬化性(遮光部硬化性)進行評價。 The peak area from 815 to 800 cm -1 is set as the peak area from the acryl group, and the amount of change before and after light irradiation of the peak area from the acryl group is measured to evaluate the photohardenability. The peak area from acryl is derived from the peak area of 845~820cm -1 as the reference peak area. Set the case where the peak area from acryl base decreases by more than 90% after light irradiation is set to "◎", and the case that the peak area from acryl base decreases by more than 80% and does not reach 90% after light irradiation is set to "○", the case where the peak area from acrylic base is reduced by more than 70% and less than 80% after light irradiation is set to "△", and the peak area from acrylic base is not reduced by 70% after light irradiation In the case of "×", the photo-curability (light-curing portion curability) was evaluated.

Figure 105117135-A0202-12-0027-4
Figure 105117135-A0202-12-0027-4

Figure 105117135-A0202-12-0028-5
Figure 105117135-A0202-12-0028-5

[產業上之可利用性] [Industry availability]

根據本發明，能夠提供一種可見光硬化性優異，且能夠抑制液晶污染之液晶顯示元件用密封劑。又，根據本發明，能夠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 which is excellent in visible light curability and can suppress contamination of liquid crystals. Furthermore, according to the present invention, it is possible to provide an upper and lower conduction material and a liquid crystal display element using the sealant for a liquid crystal display element.

Claims (4)

一種液晶顯示元件用密封劑，含有硬化性樹脂(不包括1分子中具有2個以上之巰基的聚巰基單體、1分子中具有2個以上之碳-碳雙鍵的多烯單體，及藉由該聚巰基單體與該多烯單體之反應所形成的硫醚寡聚物之組合)及光自由基聚合起始劑，其特徵在於：該光自由基聚合起始劑含有下述式(1)所示之化合物；
Figure 105117135-A0305-02-0032-1
 式(1)中，2個X分別獨立表示氫原子可被-OR1基取代之苯基，各X可具有2個以上之-OR1基，於2個X具有合計2個以上之-OR1基之情形時，各-OR1基可相同，亦可不同；R1表示氫或碳數1~3之烷基；n表示1~10之整數。 A sealant for liquid crystal display elements, containing a curable resin (excluding polythiol monomers having more than two thiol groups in one molecule, polyene monomers having more than two carbon-carbon double bonds in one molecule, and The combination of the thioether oligomer formed by the reaction of the polythiol monomer and the polyene monomer) and the photo radical polymerization initiator, characterized in that the photo radical polymerization initiator contains the following The compound represented by formula (1);
Figure 105117135-A0305-02-0032-1
 In formula (1), two Xs independently represent a phenyl group in which a hydrogen atom may be substituted with an -OR 1 group, each X may have two or more -OR 1 groups, and two Xs have a total of two or more -OR In the case of 1 group, each -OR 1 group may be the same or different; R 1 represents hydrogen or an alkyl group having 1 to 3 carbon atoms; n represents an integer of 1 to 10. 如申請專利範圍第1項之液晶顯示元件用密封劑，其含有遮光劑(shielding agent)。 For example, the sealant for liquid crystal display elements according to item 1 of the patent application scope contains a shielding agent. 一種上下導通材料，其含有申請專利範圍第1或2項之液晶顯示元件用密封劑及導電性微粒子。 A top-to-bottom conductive material, which contains the sealant for liquid crystal display elements and conductive fine particles of item 1 or 2 of the patent application. 一種液晶顯示元件，其具有申請專利範圍第1或2項之液晶顯示元件用密封劑或申請專利範圍第3項之上下導通材料。 A liquid crystal display element having a sealant for liquid crystal display elements of patent application item 1 or 2 or an upper and lower conductive material of patent application item 3.
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