TW201609851A - Curable resin having excellent post-curing flexibility, methacrylated curable resin, and liquid crystal sealing agent composition - Google Patents

Curable resin having excellent post-curing flexibility, methacrylated curable resin, and liquid crystal sealing agent composition Download PDF

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TW201609851A
TW201609851A TW104110448A TW104110448A TW201609851A TW 201609851 A TW201609851 A TW 201609851A TW 104110448 A TW104110448 A TW 104110448A TW 104110448 A TW104110448 A TW 104110448A TW 201609851 A TW201609851 A TW 201609851A
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TWI662055B (en
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Kensuke Miyazaki
Taikou Usui
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Kyoritsu Chemical & Co Ltd
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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

The purpose of the present invention is to provide a curable resin that has low liquid crystal staining properties, that does not easily affect liquid crystal alignment properties, and that forms a cured material that is flexible such that a state of adhesion can be maintained without problems even when a flexible liquid crystal display is bent. The purpose of the present invention is also to provide a liquid crystal sealing agent composition that includes the curable resin. The present invention is a curable resin represented by formula (1). (In the formula, X, R1, R2, Y, and ring A are prescribed groups, and m is a number from 1 to 7.)

Description

具有優良硬化後柔軟性的硬化性樹脂、(甲基)丙烯酸硬化性樹脂、及液晶密封劑組成物 Curable resin having excellent flexibility after hardening, (meth)acrylic curable resin, and liquid crystal sealant composition

本發明係關於即使在硬化後亦可表現優良柔軟性，且使用於液晶密封劑的硬化性樹脂及(甲基)丙烯酸化硬化性樹脂、及含有此等硬化性樹脂之液晶密封劑組成物者。 The present invention relates to a curable resin, a (meth) acrylate-curable resin, and a liquid crystal sealant composition containing the curable resin, which exhibit excellent flexibility and can be used for a liquid crystal sealing agent even after curing. .

對於液晶面板等液晶顯示裝置之製造，例如於構成液晶面板之2片基板中任一基板的外圍塗布液晶密封劑，於任一基板上滴下所定量液晶，將2片基板在真空下貼合後恢復至大氣壓中，進而將液晶填充於基板彼此間，使液晶密封劑進行硬化的液晶滴落法為普及。 In the manufacture of a liquid crystal display device such as a liquid crystal panel, for example, a liquid crystal sealing agent is applied to the periphery of any of the two substrates constituting the liquid crystal panel, and the liquid crystal is dispensed onto any of the substrates, and the two substrates are bonded under vacuum. The liquid crystal dropping method in which the liquid crystal sealing agent is hardened by returning to the atmospheric pressure and filling the liquid crystal between the substrates is popular.

在液晶滴落法中，由高速硬化之觀點來看，將環氧丙烯酸酯系化合物作為主劑的自由基聚合反應性化合物可廣泛地使用於液晶密封劑(例如參照專利文獻1)。 In the liquid crystal dropping method, a radical polymerization-reactive compound containing an epoxy acrylate-based compound as a main component can be widely used for a liquid crystal sealing agent (see, for example, Patent Document 1).

[先行技術文獻] [Advanced technical literature] [專利文獻] [Patent Literature]

[專利文獻1]特開2007-297470號公報 [Patent Document 1] JP-A-2007-297470

[發明之概要] [Summary of the Invention]

在液晶滴落法中，於2片基板中任一片上將密封劑成框架狀下進行塗佈後形成框架密封，於任一基板上滴落液晶，在真空下貼合兩基板，以UV照射將液晶密封劑進行光硬化後，在液晶之NI點(Nematic Isotropic point)以上的溫度下進行熱養生，熱硬化液晶密封劑之同時定向液晶。 In the liquid crystal dropping method, the sealant is applied in a frame shape on either of the two substrates to form a frame seal, and the liquid crystal is dropped on any of the substrates, and the two substrates are bonded under vacuum to be irradiated with UV. After the liquid crystal sealing agent is photocured, heat curing is performed at a temperature equal to or higher than the Nematic Isotropic point of the liquid crystal, and the liquid crystal sealing agent is thermally hardened while aligning the liquid crystal.

如電視般的大型面板時，因面板較大，故自液晶滴落處至框架密封有著一定以上距離，滴落液晶貼合面板後至照射UV之間，液晶與未硬化狀態的液晶密封劑並未接觸，或接觸時間較為短，主要為液晶密封劑為先經光硬化後再與液晶接觸。 When a large panel such as a TV is used, since the panel is large, there is a certain distance from the liquid crystal drop to the frame seal, and the liquid crystal is sealed between the liquid crystal and the uncured liquid crystal sealant. No contact, or a short contact time, mainly because the liquid crystal sealing agent is first cured by light and then contacted with the liquid crystal.

另一方面，近年來因智慧型手機或平板電腦型端末等普及而增加需求量的小型液晶面板中，自液晶滴落處至框架密封的距離較為短，故自貼合至照射UV之間，液晶密封劑以未硬化的狀態下與液晶接觸，或接觸時間較為長。因此，比過去在液晶密封劑之未硬化狀態下的液晶污染性成為問題。 On the other hand, in recent years, in small liquid crystal panels that have increased demand due to the popularity of smart phones or tablet computers, the distance from the liquid crystal drop to the frame seal is relatively short, so that the self-adhesive to the UV is irradiated. The liquid crystal sealing agent is in contact with the liquid crystal in an uncured state, or the contact time is long. Therefore, liquid crystal contamination property in the uncured state of the liquid crystal sealing agent has become a problem.

將含有過去環氧/丙烯酸系化合物之環氧化合物作為主劑的自由基聚合反應性液晶密封劑，對於解決該問題所需的要件並未完全令人滿足。 A radically polymerizable reactive liquid crystal sealing agent containing an epoxy compound of a conventional epoxy/acrylic compound as a main component is not entirely satisfactory for solving the problem.

又，近年來，期待電子紙等安全而輕量且可自由折疊的可撓性液晶顯示器的市場發展。前述可撓性液晶顯示器為取代過去剛直玻璃基板，而使用如塑質薄膜等柔軟基板而製造。 Moreover, in recent years, the market development of a flexible liquid crystal display which is safe, lightweight, and freely foldable, such as electronic paper, is expected. The flexible liquid crystal display is manufactured by using a flexible substrate such as a plastic film instead of the conventional rigid glass substrate.

對於液晶密封劑，因過去者為形成比較剛直的硬化物，故雖適用於如玻璃之形狀變化較少的基板之黏著上，但對於由薄膜等柔軟基板所成的可撓性顯示器，在過去製品中，藉由彎曲或基板收縮所造成的形狀變化會產生破壞或剝離等現像，故對於該用途並非充分適用。 In the past, a liquid crystal sealing agent is used for forming a relatively rigid cured product. Therefore, it is suitable for adhesion to a substrate having a small change in shape of glass. However, in the past, a flexible display made of a flexible substrate such as a film has been used in the past. In the product, the shape change caused by the bending or the shrinkage of the substrate causes damage or peeling, and the like, and thus is not sufficiently applicable for the purpose.

由如此觀點來看，特別作為適用於可撓性液晶顯示器的密封劑，於硬化後亦要求具有充分柔軟性之液晶密封劑。 From such a viewpoint, in particular, as a sealant applied to a flexible liquid crystal display, a liquid crystal sealing agent having sufficient flexibility is required after curing.

由上述得知，本發明之課題為提供一種即使在彎曲可撓性液晶顯示器時，亦可無問題下形成具有可維持黏著狀態的柔軟性之硬化物，且液晶污染性較低對於液晶配向性難造成影響的硬化性樹脂及含有該硬化性樹脂之液晶密封劑組成物。 In view of the above, it is an object of the present invention to provide a cured product having a softness capable of maintaining an adhesive state without any problem even when a flexible liquid crystal display is bent, and liquid crystal contamination is low for liquid crystal alignment. A curable resin which is hard to be affected and a liquid crystal sealant composition containing the curable resin.

本發明為包含以下態樣。 The present invention encompasses the following aspects.

(1)下述式(1)所示硬化性樹脂： 〔式中，m為1~7之範圍的數，R1各彼此獨立為氫原子、縮水甘油基或甲基縮水甘油基，R2各彼此獨立為氫原子或甲基，A環各彼此獨立為碳原子數、及雜原子數合計為5以上，且含有1個以上芳香環、或雜芳香環之基，X彼此獨立為氫原子、羥基、縮水甘油基氧基、或甲基縮水甘油基氧基，Y為下述式(1a)： (式中，Y1各彼此獨立為碳原子數2~5的伸烷基，n為1~250的範圍之數)、下述式(1b)： (式中，Y2各彼此獨立為直接結合或碳數1或者2的伸烷基，R3各彼此獨立為氫原子或甲基，p與q各彼此獨立為0以上之數，且這些合計為1~200的範圍之數)、或前述式(1b)中不飽和鍵的一部分或全部經氫化的結構之基，有關前述R1及X，縮水甘油基或甲基縮水甘油基之R1、與縮水甘油基氧基或甲基縮水甘油基氧基之X的合計 之個數平均x為1以上〕。 (1) A curable resin represented by the following formula (1): Wherein m is a number in the range of 1 to 7, and R 1 each independently represents a hydrogen atom, a glycidyl group or a methyl glycidyl group, and each of R 2 is independently a hydrogen atom or a methyl group, and each of the A rings is independent of each other. The total number of carbon atoms and the number of hetero atoms is 5 or more, and one or more aromatic rings or heteroaromatic rings are contained, and X is independently a hydrogen atom, a hydroxyl group, a glycidyloxy group, or a methyl glycidyl group. Oxy group, Y is the following formula (1a): (wherein Y 1 is each independently an alkylene group having 2 to 5 carbon atoms, and n is a number ranging from 1 to 250), and the following formula (1b): (wherein Y 2 is each independently a direct alkyl group or a C 1 or 2 alkyl group, and R 3 is each independently a hydrogen atom or a methyl group, and p and q are each independently 0 or more, and these totals the base structure is in the range of 1 to 200), or the formula (1b) unsaturated bonds in a part or all hydrogenated, For the R 1 and X, glycidyl group or glycidyl group R & lt methyl 1 The number average X of the total of X of the glycidyloxy group or the methyl glycidyloxy group is 1 or more.

(2)(1)所記載的硬化性樹脂，其中前述式(1)中，於A環所含之碳原子數為4~40，氧原子數為0~5，氮原子數為0~5，硫原子數為0~5，且於A環所含之環結構的數為1~5。 (2) The curable resin according to (1), wherein, in the formula (1), the number of carbon atoms in the ring A is 4 to 40, the number of oxygen atoms is 0 to 5, and the number of nitrogen atoms is 0 to 5. The number of sulfur atoms is 0 to 5, and the number of ring structures contained in the ring A is 1 to 5.

(3)將(1)或(2)所記載的硬化性樹脂之環氧基、羥基及不飽和鍵的至少一部分與(甲基)丙烯酸及/或(甲基)丙烯酸酐進行反應所得之(甲基)丙烯酸化硬化性樹脂。 (3) A reaction of at least a part of an epoxy group, a hydroxyl group, and an unsaturated bond of the curable resin described in (1) or (2) with (meth)acrylic acid and/or (meth)acrylic anhydride ( Methyl) acrylated curable resin.

(4)含有(1)或(2)所記載的硬化性樹脂及/或(3)所記載的(甲基)丙烯酸化硬化性樹脂之液晶密封劑組成物。 (4) A liquid crystal sealing agent composition containing the curable resin described in (1) or (2) and/or the (meth) acrylate-curable resin described in (3).

(5)於前述液晶密封劑組成物中之硬化性樹脂及/或(甲基)丙烯酸化硬化性樹脂的含有量為5~95重量%之(4)所記載的液晶密封劑組成物。 (5) The liquid crystal sealant composition according to (4), wherein the content of the curable resin and/or the (meth) acrylate-curable resin in the liquid crystal sealant composition is 5 to 95% by weight.

(6)前述液晶密封劑組成物為進一步含有具有乙烯性不飽和基及/或環氧基之化合物H(但，除前述硬化性樹脂及(甲基)丙烯酸化硬化性樹脂以外)之(4)或(5)所記載的液晶密封劑組成物。 (6) The liquid crystal sealing agent composition further contains a compound H having an ethylenically unsaturated group and/or an epoxy group (except for the curable resin and the (meth) acrylate-curable resin) (4) Or the liquid crystal sealant composition as described in (5).

依據本發明可提供即使在彎曲可撓性液晶顯示器之情況下，亦無問題下形成具有可維持黏著狀態的柔軟性之硬化物，且液晶污染性較低，對於液晶配向性難造 成影響之硬化性樹脂及含有該硬化性樹脂之液晶密封劑組成物。 According to the present invention, it is possible to provide a cured product having a softness capable of maintaining an adhesive state without any problem even in the case of a curved flexible liquid crystal display, and liquid crystal contamination is low, and it is difficult to form a liquid crystal alignment property. A curable resin that affects and a liquid crystal sealant composition containing the curable resin.

[實施發明之形態] [Formation of the Invention]

以下詳細說明本發明。且本說明書中所謂(甲基)丙烯酸表示甲基丙烯酸及/或丙烯酸，所謂(甲基)丙烯酸酯表示甲基丙烯酸酯及/或丙烯酸酯。 The invention is described in detail below. In the present specification, (meth)acrylic acid means methacrylic acid and/or acrylic acid, and the (meth)acrylate means methacrylate and/or acrylate.

[本發明之硬化性樹脂] [Cure resin of the present invention]

本發明之硬化性樹脂如下述式(1)所示。 The curable resin of the present invention is represented by the following formula (1).

本發明之硬化性樹脂為具有記載m字的括弧所含括的區塊之由醚部位或所定基Y所成的柔軟部位，將本發明之硬化性樹脂經硬化所得之硬化物可考慮為該柔軟部位可發揮柔軟性或橡膠彈性者，其具有優良柔軟性。如式(1)所示，本發明之硬化性樹脂具有柔軟性高分子結構，藉此可考慮本發明之硬化性樹脂的硬化物之交聯密度可適度地降低，亦可使前述柔軟性發揮。 The curable resin of the present invention is a soft portion formed of an ether moiety or a predetermined group Y in a block included in the brackets of the m-shape, and the cured product obtained by curing the curable resin of the present invention can be considered as The soft part can exhibit softness or rubber elasticity, and it has excellent softness. As shown in the formula (1), the curable resin of the present invention has a flexible polymer structure, and it is considered that the crosslink density of the cured product of the curable resin of the present invention can be appropriately lowered, and the softness can be exerted. .

又，具有前述柔軟部位之同時，本發明之硬化性樹脂具有如A環之含有芳香環之結構，具有如此所定 結構的本發明之硬化性樹脂的液晶污染性為低。 Further, while having the soft portion, the curable resin of the present invention has a structure containing an aromatic ring such as ring A, and has such a structure The curable resin of the present invention having a structure has low liquid crystal contamination.

(有關m) (about m)

式(1)中，m為1~7的範圍之數，由本發明之硬化性樹脂的黏度或處理性之觀點來看，以1~5的範圍之數為佳，以1~3的範圍之數為較佳。本發明之硬化性樹脂例如可藉由後述製造方法而製造，此時有時變成m之數相異的複數種類化合物之混合物的情況。 In the formula (1), m is in the range of 1 to 7, and from the viewpoint of the viscosity or handleability of the curable resin of the present invention, it is preferably in the range of 1 to 5, and in the range of 1 to 3. The number is preferred. The curable resin of the present invention can be produced, for example, by a production method described below, and in some cases, a mixture of a plurality of compounds having different numbers of m may be used.

(有關X) (about X)

式(1)中，X各彼此獨立為氫原子、羥基、縮水甘油基氧基、或甲基縮水甘油基氧基。X為羥基、縮水甘油基氧基或甲基縮水甘油基氧基時，如後述該部分可引起交聯反應，又於該部分可導入(甲基)丙烯酸基。 In the formula (1), each of X is independently a hydrogen atom, a hydroxyl group, a glycidyloxy group or a methyl glycidyloxy group. When X is a hydroxyl group, a glycidyloxy group or a methyl glycidyloxy group, this part can generate a crosslinking reaction, and a (meth)acrylic group can be introduce|transduced in this part.

由低液晶污染性之觀點來看，作為如此X以羥基及縮水甘油基氧基為佳。 From the viewpoint of low liquid crystal contamination, it is preferred that X is a hydroxyl group or a glycidyloxy group.

(有關R1) (about R 1 )

對於上述式(1)，R1各彼此獨立為氫原子、縮水甘油基或甲基縮水甘油基。如後述，含有R1之基可引起交聯反應，又於該部分可導入(甲基)丙烯酸基。且m為2以上的數時，於有記載m字的括弧所含括的區塊中之R1彼此亦獨立為可彼此相同或相異者。 With respect to the above formula (1), R 1 each independently represents a hydrogen atom, a glycidyl group or a methyl glycidyl group. As will be described later, the group containing R 1 may cause a crosslinking reaction, and a (meth)acrylic group may be introduced into the portion. When m is a number of 2 or more, R 1 in the block included in the brackets in which the m-shape is included is also independent of each other or may be identical to each other.

由低液晶污染性之觀點來看，作為如此R1以 氫原子及縮水甘油基為佳。 From the viewpoint of low liquid crystal contamination, R 1 is preferably a hydrogen atom or a glycidyl group.

而對於上述式(1)所示本發明之硬化性樹脂，縮水甘油基或甲基縮水甘油基之R1及縮水甘油基氧基或甲基縮水甘油基氧基之X(換言之具有環氧基之R1及X)的合計個數之平均x為1以上，較佳為2以上。如此硬化性樹脂具有一定以上數目的交聯性基，且藉由具有上述柔軟部位，一邊確保液晶密封劑所要求的硬化性．接著性下，一邊達成硬化物之優良柔軟性(以下亦稱為「硬化後柔軟性」)。 Further, in the curable resin of the present invention represented by the above formula (1), R 1 of a glycidyl group or a methyl glycidyl group and X of a glycidyloxy group or a methyl glycidyloxy group (in other words, an epoxy group) The average x of the total number of R 1 and X) is 1 or more, preferably 2 or more. The curable resin has a certain number of crosslinkable groups, and the hardenability required for the liquid crystal sealant is ensured by having the above-mentioned soft portion. Next, the excellent softness of the cured product (hereinafter also referred to as "softness after hardening") is achieved.

前述x由含有後述本發明之硬化性樹脂的液晶密封劑組成物，例如影響黏度之塗佈性等作業性、與例如影響交聯密度之硬化後強度等物理特性之觀點來看，如前述以2以上為佳，較佳為2~16，更佳為2~8。 The above-mentioned x is a liquid crystal sealant composition containing the curable resin of the present invention to be described later, for example, from the viewpoints of workability such as coating properties affecting viscosity, and physical properties such as post-hardening strength which affects crosslink density, as described above. 2 or more is preferable, preferably 2 to 16, more preferably 2 to 8.

且有關x，可藉由高速液體層析法(HPLC)及液體層析質量分析(LC-MS)或凝膠過濾/浸透層析法(GPC/GFC)，測定硬化性樹脂之平均分子量及分子量分布，進一步測定硬化性樹脂之環氧當量後，由該測定結果算出上述式(1)中之x。 For x, the average molecular weight and molecular weight of the curable resin can be determined by high speed liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC-MS) or gel filtration/impregnation chromatography (GPC/GFC). After the measurement, the epoxy equivalent of the curable resin is further measured, and x in the above formula (1) is calculated from the measurement results.

(有關R2) (about R 2 )

對於上述式(1)，R2各彼此獨立為氫原子或甲基，由本發明之硬化性樹脂之低液晶污染性的觀點來看，以氫原子為佳。且m為2以上之數時，於有記載m字的括弧所含括的區塊中之R2彼此亦為獨立而可彼此相同或相 異。 In the above formula (1), R 2 is each independently a hydrogen atom or a methyl group, and from the viewpoint of low liquid crystal contamination of the curable resin of the present invention, a hydrogen atom is preferred. When m is 2 or more, R 2 in the block included in the parentheses in which m is described is also independent from each other and may be identical or different from each other.

(有關A環) (about A ring)

對於上述式(1)，A環各彼此獨立為碳原子數、及雜原子數之合計為5以上，且含有1個以上芳香環、或雜芳香環之基。所謂碳原子數及雜原子數之合計為5以上為表示，若由A環全體來看時的構成環之碳原子及雜原子、結合於環構成原子具有碳原子或雜原子之基者，含有此等之全體碳原子及雜原子數之合計為5以上者。 In the above formula (1), each of the A rings is independently a carbon atom number and a total number of hetero atoms of 5 or more, and contains one or more aromatic rings or a heteroaromatic ring. The total number of carbon atoms and the number of hetero atoms is 5 or more, and is represented by a carbon atom or a hetero atom constituting the ring when viewed from the entire A ring, and a base having a carbon atom or a hetero atom bonded to the ring constituent atom. The total number of carbon atoms and hetero atoms in these is 5 or more.

對於A環，由本發明之硬化性樹脂及後述液晶密封劑組成物之黏度、處理性的觀點來看，含有此之碳原子數為4~40，氧原子數為0~5，氮原子數為0~5，硫原子數為0~5，且於A環所含之環結構的數以1~5者為佳。 The A ring is composed of a curable resin of the present invention and a liquid crystal sealant composition to be described later, and has a carbon atom number of 4 to 40, an oxygen atom number of 0 to 5, and a nitrogen atom number. 0 to 5, the number of sulfur atoms is 0 to 5, and the number of ring structures contained in the ring A is preferably 1 to 5.

於A環內所含之環結構(芳香環及雜芳香環)可單獨存在1種，亦可存在2種以上之複數種，前述環結構可為單環結構亦可為縮合環結構。又，這些環結構亦可存在介著直接鍵結或連結基所結合之複數者。 The ring structure (aromatic ring and heteroaromatic ring) contained in the ring A may be used alone or in combination of two or more kinds. The ring structure may be a single ring structure or a condensed ring structure. Further, these ring structures may also be present in combination with direct bonding or linking groups.

作為該連結基的例子，可舉出碳數1~4的伸烷基、碳數2~4的亞烷基、醚基、酯基、酮基、硫醚基、磺醯基等。又，上述式(1)中之結合於A環之氧原子及X與A環亦可介著該連結基而結合。 Examples of the linking group include an alkylene group having 1 to 4 carbon atoms, an alkylene group having 2 to 4 carbon atoms, an ether group, an ester group, a ketone group, a thioether group, and a sulfonyl group. Further, the oxygen atom bonded to the A ring and the X ring and the A ring in the above formula (1) may be bonded via the linking group.

又，這些環結構可各獨立具有取代基。作為如此取代基之例子，可舉出烷基、烷氧基、醯基、甲醯 基、羧基、酯基、氰基、硝基、磺酸基、醯胺基、羥基、巰基、矽基等。 Further, these ring structures may each independently have a substituent. Examples of such a substituent include an alkyl group, an alkoxy group, a decyl group, and a formazan group. Base, carboxyl group, ester group, cyano group, nitro group, sulfonic acid group, decylamino group, hydroxyl group, fluorenyl group, fluorenyl group and the like.

作為含於A環之環結構的例子，可舉出苯環、萘環、茀環、蒽環、呋喃環、吡咯環、噻吩環、咪唑環、噁唑環、噻唑環、吡啶環、噻嗪環、以及於這些環上結合前述取代基者等。 Examples of the ring structure contained in the ring A include a benzene ring, a naphthalene ring, an anthracene ring, an anthracene ring, a furan ring, a pyrrole ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, and a thiazine ring. a ring, and a combination of the above substituents on these rings.

且，m為2以上的數時，於有記載m字的括弧所含括的區塊中之A環同彼此亦可獨立為彼此相同或相異者。 Further, when m is a number of 2 or more, the A rings in the blocks included in the brackets in which the m-shape is included may be independently the same or different from each other.

(有關Y) (about Y)

其次對於上述式(1)中之Y為將下述式(1a)、(1b)或該式(1b)中之不飽和鍵的一部分或全部經氫化的結構基。且，m為2以上的數時，於有記載m字的括弧所含括的區塊中之Y彼此或獨立可彼此相同或相異。 Next, Y in the above formula (1) is a structural group obtained by hydrogenating a part or all of the unsaturated bond in the following formula (1a), (1b) or the formula (1b). Further, when m is a number of 2 or more, Y in the block included in the brackets in which the m-shape is included may be identical or different from each other or independently.

對於式(1a)，Y1各彼此獨立為碳原子數2~5的伸烷基，n為1~250的範圍之數。作為前述伸烷基之例子，可舉出伸乙基、伸丙基、三伸甲基、四伸甲基及新戊基等。由本發明之硬化性樹脂的硬化後柔軟性及液晶 污染性之觀點來看，Y1係以伸乙基或四伸甲基為佳，由前述柔軟性及本發明之硬化性樹脂的處理性之觀點來看，n以5~70的範圍之數為佳，更佳為10~50的範圍之數。 In the formula (1a), Y 1 is each independently an alkylene group having 2 to 5 carbon atoms, and n is a number ranging from 1 to 250. Examples of the alkylene group include an exoethyl group, a propyl group, a trimethyl group, a tetramethyl group, a neopentyl group and the like. From the viewpoint of flexibility after curing and liquid crystal contamination of the curable resin of the present invention, Y 1 is preferably an ethyl or tetramethyl group, and the flexibility and the handleability of the curable resin of the present invention are From the point of view, n is preferably in the range of 5 to 70, more preferably in the range of 10 to 50.

且，n為2以上的數時，記載n字的括弧所含括的各重複單位中之Y1彼此亦為獨立為可彼此相同或相異。 Further, when n is a number of 2 or more, Y 1 in each of the repeating units included in the brackets in the n-shape is also independent from each other so as to be identical or different from each other.

且對於式(1b)，Y2各彼此獨立為直接結合或碳數1或者2的伸烷基，R3各彼此獨立為氫原子或甲基，p與q各彼此獨立為0以上之數，且此等合計為1~200的範圍之數。且p或q為2以上時，這些記載的字之括弧所含括的重複單位雖以複數形式存在，但這些各重複單位中之R3彼此亦為獨立為可彼此相同或相異。又，這些重複單位若為上述之p或q的範圍，即可以無規方式結合。 And for the formula (1b), each of Y 2 is independently a direct alkyl group or a C 1 or 2 alkyl group, and each of R 3 is independently a hydrogen atom or a methyl group, and p and q are each independently 0 or more. And these totals are in the range of 1 to 200. When p or q is 2 or more, the repeating units included in the parentheses of these recited words exist in plural form, but R 3 in each of the repeating units is also independent from each other so as to be identical or different from each other. Further, if these repeating units are in the range of p or q described above, they can be combined in a random manner.

P與q之合計數由本發明之硬化性樹脂的處理性及硬化後柔軟性之觀點來看，以5~70的範圍之數為佳，更佳為10~50的範圍之數。 The total count of P and q is preferably in the range of 5 to 70, more preferably in the range of 10 to 50, from the viewpoint of handleability of the curable resin of the present invention and flexibility after curing.

(有關m、n、p、q) (about m, n, p, q)

有關以上說明之式(1)中表示所定區塊(重複單位)之數的m，可藉由後述本發明之硬化性樹脂的合成原料之裝入量、或由該樹脂(或後述之(甲基)丙烯酸化硬化性樹脂)的GPC測定結果而可概算得知。n、及p、q 之合計值可藉由硬化性樹脂(或後述之(甲基)丙烯酸化硬化性樹脂)的GPC測定結果而概算得知，又這些亦可由硬化性樹脂的合成原料之GPC測定結果而概算得知。且對於p、q之各值可藉由IR等進行分析。 The m indicating the number of the predetermined blocks (repeating units) in the above formula (1) can be charged by the synthetic raw material of the curable resin of the present invention described later, or by the resin (or (hereinafter described) The results of GPC measurement of the acrylate-based sclerosing resin can be estimated. n, and p, q The total value can be estimated from the results of GPC measurement of a curable resin (or a (meth) acrylate-curable resin to be described later), and these can also be estimated from the GPC measurement results of the synthetic raw material of the curable resin. . And for each value of p and q, it can be analyzed by IR or the like.

<硬化性樹脂之特性> <Characteristics of Curable Resin>

以上說明的本發明之硬化性樹脂之黏度一般為1000~2000000mPa．s。如後述，本發明之硬化性樹脂為適用於液晶密封劑之用途上，但使用於該用途時，由確保液晶密封劑為適度黏性的觀點來看，硬化性樹脂之黏度以3000~2000000mPa．s為佳。且，對於本說明書中之黏度為25℃時，使用E型黏度計所測定之數值。 The viscosity of the curable resin of the present invention described above is generally 1000~2000000 mPa. s. As described later, the curable resin of the present invention is suitable for use in a liquid crystal sealing agent. However, when used for this purpose, the viscosity of the curable resin is 3,000 to 2,000,000 mPa from the viewpoint of ensuring a proper viscosity of the liquid crystal sealing agent. s is better. Further, for the viscosity in the present specification of 25 ° C, the value measured by the E-type viscometer is used.

硬化性樹脂的黏度為，例如藉由變更式(1)中之m等及/或變更硬化性樹脂中之羥基(例如R1為氫原子時)的存在比等可調整。 The viscosity of the curable resin can be adjusted, for example, by changing m or the like in the formula (1) and/or changing the existence ratio of the hydroxyl group in the curable resin (for example, when R 1 is a hydrogen atom).

又，將硬化性樹脂使用於液晶密封劑時，由可兼具接著性與柔軟性的觀點來看，該環氧當量以400~10000g/eq為佳，較佳為500~5000g/eq。且硬化性樹脂之環氧當量可藉由硬化性樹脂之平均分子量、與以上述式(1)中記載m字的括弧所含括的每區塊(重複單位)之環氧基(例如縮水甘油基之R1)的數做調整。 Further, when the curable resin is used for the liquid crystal sealing agent, the epoxy equivalent is preferably from 400 to 10,000 g/eq, more preferably from 500 to 5,000 g/eq, from the viewpoint of having both adhesiveness and flexibility. Further, the epoxy equivalent of the curable resin may be an epoxy group (for example, glycidol per block (repeating unit) included in the m-shaped brackets in the above formula (1) by the average molecular weight of the curable resin. The number of bases R 1 ) is adjusted.

且本發明之硬化性樹脂的NI點變化較小。所謂前述NI點為液晶自向列相至各向同性相(等方相)進行相轉移時的溫度(相轉移溫度可使用差示熱分析裝置自 吸熱吸收峰頂所測定得知)。液晶之NI點係由液晶各成分之混合組成所決定，在各配合有固有值。若液晶污染性高的原料或者密封劑與液晶混合時，會引起NI點的巨大變化，相反地若原料或者密封劑的液晶污染性為低時，NI點的變化較小。 Further, the NI point change of the curable resin of the present invention is small. The aforementioned NI point is the temperature at which the liquid crystal is phase-transferred from the nematic phase to the isotropic phase (isotropic phase) (the phase transition temperature can be measured by using a differential thermal analysis device. The endothermic absorption peak is determined by the measurement). The NI point of the liquid crystal is determined by the mixed composition of the liquid crystal components, and each has a unique value. When a raw material or a sealant having a high liquid crystal contamination is mixed with a liquid crystal, a large change in the NI point is caused. Conversely, if the liquid crystal contamination of the raw material or the sealant is low, the change in the NI point is small.

具體而言，本發明之硬化性樹脂的NI點變化通常為-5℃~+5℃之範圍，較佳為-3℃~+3℃之範圍。且NI點變化之測定方法的詳細內容如後述實施例所說明。 Specifically, the NI point change of the curable resin of the present invention is usually in the range of -5 ° C to + 5 ° C, preferably in the range of -3 ° C to + 3 ° C. The details of the measurement method of the NI point change are described in the examples below.

[(甲基)丙烯酸化硬化性樹脂] [(Methyl) acrylated curable resin]

本發明之硬化性樹脂可為將(甲基)丙烯酸及/或(甲基)丙烯酸酐進行反應所得之(甲基)丙烯酸化硬化性樹脂。(甲基)丙烯酸基的烯烴部位可引起交聯反應，對於前述(甲基)丙烯酸化硬化性樹脂，一邊擔保液晶密封劑所要求的黏著性，一邊可達成優良柔軟性。 The curable resin of the present invention may be a (meth) acrylate-curable resin obtained by reacting (meth)acrylic acid and/or (meth)acrylic anhydride. The (meth)acrylic group-containing olefin moiety can cause a crosslinking reaction, and the (meth)acrylic-curable resin can achieve excellent flexibility while securing the adhesiveness required for the liquid crystal sealing agent.

對本發明之硬化性樹脂之(甲基)丙烯酸基的導入，更具體為對於前述硬化性樹脂之環氧基(例如R1為縮水甘油基時)、羥基及不飽和鍵(例如Y為式(1b)之基時)的至少一部分引起。且，縮藉由(甲基)丙烯酸基之加成等可使環氧基開環而產生羥基，但對於該羥基可進一步進行(甲基)丙烯酸基之導入。 The introduction of the (meth)acrylic group of the curable resin of the present invention is more specifically an epoxy group for the curable resin (for example, when R 1 is a glycidyl group), a hydroxyl group, and an unsaturated bond (for example, Y is a formula ( At least a portion of the base of 1b) is caused. Further, the epoxy group may be opened by ring-opening to form a hydroxyl group by addition of a (meth)acryl group, but the introduction of a (meth)acrylic group may be further carried out for the hydroxyl group.

且(甲基)丙烯酸基之導入可藉由於本發明之硬化性樹脂，使(甲基)丙烯酸系化合物，例如丙烯酸、甲基丙烯酸、又這些無水物、酯化合物、或酸鹵素化 物等進行反應而進行。 And the (meth)acrylic group can be introduced by the curable resin of the present invention to halogenate a (meth)acrylic compound such as acrylic acid, methacrylic acid, these anhydrates, ester compounds, or acids. The reaction is carried out by reacting the substance or the like.

<(甲基)丙烯酸化硬化性樹脂之特性> <Characteristics of (meth) acrylated curable resin>

本發明之(甲基)丙烯酸化硬化性樹脂與本發明之硬化性樹脂同樣地，顯示使用於液晶密封劑的較佳特性。 The (meth) acrylate-curable resin of the present invention exhibits preferable properties for use in a liquid crystal sealing agent, similarly to the curable resin of the present invention.

即本發明之(甲基)丙烯酸化硬化性樹脂的黏度通常為1000~2000000mPa．s，由對液晶密封劑確保其適度黏性的觀點來看，以3000~2000000mPa．s為佳。 That is, the viscosity of the (meth) acrylated curable resin of the present invention is usually 1000 to 2000000 mPa. s, from the viewpoint of ensuring its moderate viscosity to the liquid crystal sealing agent, it is 3000~2000000mPa. s is better.

且本發明之(甲基)丙烯酸化硬化性樹脂的NI點變化小，該NI點變化通常在-5℃~+5℃之範圍，較佳為-3℃~+3℃之範圍。 Further, the (meth) acrylated curable resin of the present invention has a small change in the NI point, and the change in the NI point is usually in the range of -5 ° C to + 5 ° C, preferably in the range of -3 ° C to + 3 ° C.

[硬化性樹脂之製造方法] [Method for Producing Curable Resin]

其次對於本發明之硬化性樹脂的製造方法做說明。 Next, a method of producing the curable resin of the present invention will be described.

前述硬化性樹脂之製造方法含有將下述式(2)或(3)所示化合物E與下述式(4)所示化合物F進行反應的步驟。 The method for producing the curable resin includes a step of reacting the compound E represented by the following formula (2) or (3) with the compound F represented by the following formula (4).

對於式(2)及(3)，Y1、n、Y2、R3、p及q如上述定義，R4各彼此獨立為、氫原子、縮水甘油基或甲基縮水甘油基。且式(3)中，記載p或q字的括弧所含括的重複單位中之不飽和鍵的一部分或全部可被氫化。 For the formulae (2) and (3), Y 1 , n, Y 2 , R 3 , p and q are as defined above, and each of R 4 is independently a hydrogen atom, a glycidyl group or a methyl glycidyl group. Further, in the formula (3), a part or all of the unsaturated bonds in the repeating unit included in the parentheses of the p or q character may be hydrogenated.

又，對於式(4)，X及A環如上述定義，R5為氫原子、縮水甘油基或甲基縮水甘油基。 Further, with respect to the formula (4), the X and A rings are as defined above, and R 5 is a hydrogen atom, a glycidyl group or a methyl glycidyl group.

例如於化合物E的分子末端所存在的-OR4為縮水甘油基氧基或甲基縮水甘油基氧基時，化合物F中之-OR5或X中的至少任一方為羥基，藉由這些縮水甘油基或甲基縮水甘油基與羥基之間的開環反應，於化合物E末端會連結化合物F。而視必要，所得之化合物(後述合成中間體G，此為於分子內具有一個以上環氧基時，此為本發明之硬化性樹脂)中之游離羥基(例如藉由開環反應所新產生的羥基)的至少一部分藉由如後述之縮水甘油基醚化，將x調整至1以上，得到式(1)中之m為1時的本發明之硬化性樹脂。 For example, when -OR 4 present at the molecular terminal of the compound E is a glycidyloxy group or a methyl glycidyloxy group, at least one of -OR 5 or X in the compound F is a hydroxyl group, and these shrinkage A ring-opening reaction between a glyceryl group or a methyl glycidyl group and a hydroxyl group, and a compound F is bonded to the terminal of the compound E. And if necessary, the obtained compound (the synthetic intermediate G described later, which is a curable resin having one or more epoxy groups in the molecule, which is a curable resin of the present invention) is newly produced (for example, by a ring-opening reaction) At least a part of the hydroxyl group is adjusted to 1 or more by the glycidyl ether to be described later, and the curable resin of the present invention in which m in the formula (1) is 1 is obtained.

又，對於化合物F，若為將-OR5及X為羥基等環氧基進行開環所得之基時，該-OR5及X中任一皆可與化合物E之縮水甘油基氧基或甲基縮水甘油基氧基進行反應。對於如此所得之化合物，視必要將游離羥基藉由如後述之縮水甘油基醚化，可得到式(1)中之m為2以上的本發明之硬化性樹脂。且，m可藉由化合物E及F之裝入量而做調節，即使對於-OR5及X同時開環環氧基的基時，亦可藉由裝入量的調整而得到m為1的本發明之硬化性樹脂。 Further, in the case where the compound F is a group obtained by ring-opening an epoxy group such as -OR 5 and X as a hydroxyl group, any of the -OR 5 and X may be a glycidyloxy group or a compound E. The glycidyloxy group is reacted. The compound thus obtained can be obtained by etherifying a free hydroxyl group with a glycidyl group as described later to obtain a curable resin of the present invention in which m in the formula (1) is 2 or more. Further, m can be adjusted by the amounts of the compounds E and F, and even when the groups of -OR 5 and X are simultaneously opened with an epoxy group, m can be obtained by adjusting the amount of loading. The curable resin of the present invention.

且，化合物E及F可單獨使用各1種，亦可組合2種以上使用。 Further, the compounds E and F may be used alone or in combination of two or more.

式(2)或(3)所示化合物E之分子量以500~10000為佳。且，本說明書中之分子量為藉由GPC所測定之標準聚苯乙烯換算的數平均分子量。 The molecular weight of the compound E represented by the formula (2) or (3) is preferably from 500 to 10,000. Further, the molecular weight in the present specification is a number average molecular weight in terms of standard polystyrene measured by GPC.

雖化合物E及F可為販賣品，或由出售的化合物依據公知方法而容易調製。例如R4為氫原子，Y1為伸乙基之式(2)的化合物E係可得到作為聚乙二醇而具有種種重複單位數(n)者，適宜地選擇具有所望範圍之n的化合物即可。又，n可由聚乙二醇之GPC測定結果概算出。 Although the compounds E and F may be sold, or the compound to be sold is easily prepared according to a known method. For example, the compound E wherein R 4 is a hydrogen atom and Y 1 is an ethyl group of the formula (2) can be obtained as a polyethylene glycol and has various repeating unit numbers (n), and a compound having a desired range of n is suitably selected. Just fine. Further, n can be calculated from the GPC measurement result of polyethylene glycol.

又，聚乙二醇因與可導入環氧氯丙烷等縮水甘油基或甲基縮水甘油基之化合物(以下亦稱為「環氧化化合物」)進行而可於聚乙二醇之末端導入縮水甘油基等，此可將R4自氫原子容易地轉換為縮水甘油基等。此 說明如以下，此屬於R4或R5為氫原子之化合物E及F的其他例子。 Further, polyethylene glycol can be introduced into glycidol at the end of polyethylene glycol by a compound which can introduce a glycidyl group such as epichlorohydrin or a methyl glycidyl group (hereinafter also referred to as "epoxidized compound"). The base or the like can easily convert R 4 from a hydrogen atom to a glycidyl group or the like. This description is as follows, and other examples of the compounds E and F in which R 4 or R 5 is a hydrogen atom.

又，可得到R4為氫原子，Y1為伸丙基之式(2)的化合物E為作為聚丙烯醚甘醇之具有種種重複單位數(n)者。例如可舉出EXCENOL420、EXCENOL720、EXCENOL1020、EXCENOL2020(以上為旭硝子公司製)等。 Further, the compound E of the formula (2) wherein R 4 is a hydrogen atom and Y 1 is a propyl group is a compound having a plurality of repeating units (n) as a polypropylene ether glycol. For example, EXCENOL 420, EXCENOL 720, EXCENOL 1020, and EXCENOL 2020 (above, manufactured by Asahi Glass Co., Ltd.) may be mentioned.

又，R4為氫原子，Y1為三伸甲基之式(2)的化合物E例如可依據特表2013-515144號公報所記載的方法，製造具有種種重複單位數(n)之聚三伸甲基醚甘醇。 Further, the compound E of the formula (2) wherein R 4 is a hydrogen atom and Y 1 is a trimethyl group can be produced, for example, according to the method described in JP-A-2013-515144, to produce a poly 3 having various repeating unit numbers (n). Methyl ether glycol is stretched.

又，可得到R4為氫原子，Y1為四伸甲基之式(2)的化合物E為作為聚四伸甲基醚甘醇具有種種重複單位數(n)者。例如可舉出PTMG650、PTMG850、PTMG1000、PTMG1300、PTMG1500、PTMG1800、PTMG2000(以上三菱化學公司製)等。 Further, the compound E of the formula (2) wherein R 4 is a hydrogen atom and Y 1 is a tetramethyl group is a compound having a plurality of repeating units (n) as polytetramethyl ether glycol. For example, PTMG650, PTMG850, PTMG1000, PTMG1300, PTMG1500, PTMG1800, PTMG2000 (made by Mitsubishi Chemical Corporation), etc. are mentioned.

又，可得到R3為氫原子，R4為氫原子之式(3)的化合物E為作為末端羥基導入聚丁二烯具有種種重複單位數(p、q)者。例如可舉出NISSO PB G-1000、G-2000(以上日本曹達公司製)、Poly bd R-45HT(出光興產公司製)等。 Further, the compound E of the formula (3) wherein R 3 is a hydrogen atom and R 4 is a hydrogen atom is one in which the number of repeating units (p, q) is introduced into the polybutadiene as a terminal hydroxyl group. For example, NISSO PB G-1000, G-2000 (made by the above-mentioned Japan Soda Co., Ltd.), Poly bd R-45HT (made by Idemitsu Kosan Co., Ltd.), etc. are mentioned.

又，可得到R3為氫原子，R4為氫原子，記載p或q字的括弧所含括的重複單位中之不飽和鍵的一部分或全部經氫化的式(3)之化合物E為作為末端羥基導入 聚丁二烯的氫化物具有種種重複單位數(p、q)者。例如可舉出NISSO-PB GI-1000、GI-2000(以上日本曹達公司製)等。 Further, R 3 is a hydrogen atom, R 4 is a hydrogen atom, and a part or all of the unsaturated bond in the repeating unit included in the parentheses included in the p or q character is hydrogenated as the compound E of the formula (3). The hydride in which the terminal hydroxyl group is introduced into the polybutadiene has various repeating unit numbers (p, q). For example, NISSO-PB GI-1000, GI-2000 (made by the above-mentioned Japanese Soda Co., Ltd.), etc. are mentioned.

又，可得到R3為甲基，R4為氫原子的式(3)之化合物E為作為末端羥基導入聚異戊二烯具有種種重複單位數(p、q)者。例如可舉出Poly ip(出光興產公司製)等。 Further, the compound E of the formula (3) wherein R 3 is a methyl group and R 4 is a hydrogen atom is one in which the number of repeating units (p, q) is introduced into the polyisoprene as a terminal hydroxyl group. For example, Poly ip (made by Idemitsu Kosan Co., Ltd.) or the like can be mentioned.

可得到R3為甲基，R4為氫原子，記載p或q字的括弧所含括的重複單位中之不飽和鍵的一部分或全部經氫化的式(3)之化合物E為作為末端羥基導入聚異戊二烯之氫化物具有種種重複單位數(p、q)者。例如可舉出EPOL(出光興產公司製)等。 R 3 is a methyl group, R 4 is a hydrogen atom, and a part or all of the unsaturated bond in the repeating unit included in the parentheses included in the p or q character is hydrogenated. The compound E of the formula (3) is a terminal hydroxyl group. The hydride to which polyisoprene is introduced has various repeating unit numbers (p, q). For example, EPOL (made by Idemitsu Kosan Co., Ltd.) and the like can be mentioned.

又，作為R5為氫原子，X為羥基，A環為滿足規定原子數及環結構數之化合物F，可舉出間苯二酚、2-(4-羥基苯基)乙醇、雙酚A、雙酚M、雙酚P、1,6-萘二醇、2-乙基-9,10-蒽二醇、3,4-噻吩二醇、9,9-雙(4-羥基-3-甲基苯基)茀等。 Further, R 5 is a hydrogen atom, X is a hydroxyl group, and ring A is a compound F satisfying a predetermined number of atoms and a ring structure, and examples thereof include resorcin, 2-(4-hydroxyphenyl)ethanol, and bisphenol A. , bisphenol M, bisphenol P, 1,6-naphthalenediol, 2-ethyl-9,10-nonanediol, 3,4-thiophenediol, 9,9-bis(4-hydroxy-3- Methylphenyl) hydrazine and the like.

又，作為R5為氫原子，X為氫原子，A環為滿足規定之原子數及環結構數的化合物F，可舉出酚、4-α-枯酚、4-甲氧基酚、4-羥基喹啉等。。 Further, R 5 is a hydrogen atom, X is a hydrogen atom, and ring A is a compound F satisfying a predetermined number of atoms and a ring structure, and examples thereof include phenol, 4-α- cumol, 4-methoxyphenol, and 4 - hydroxyquinoline and the like. .

化合物E中之R4及化合物F中之R5由各所得之硬化性樹脂的硬化後柔軟性及低液晶污染性之觀點來看，以R4及R5的一方為氫原子，另一方為縮水甘油基者為佳。 R 4 in the compound E and R 5 in the compound F are one of R 4 and R 5 being a hydrogen atom from the viewpoint of softening flexibility and low liquid crystal contamination of each of the obtained curable resins, and the other is Glycidyl base is preferred.

化合物E與化合物F欲生成本發明之硬化性樹脂，例如將化合物E與化合物F在鹼之存在下進行反應後，視必要將所得之合成中間體G在適當觸媒存在下，與適當環氧化化合物進行反應。上述反應中欲使硬化性樹脂中之m為1~7，較佳為1~5，更佳為1~3的範圍之數，可調整裝入量。前述化合物可單獨使用1種亦可組合2種以上使用。 Compound E and Compound F are intended to form a curable resin of the present invention. For example, after reacting Compound E with Compound F in the presence of a base, the resulting synthesis intermediate G is optionally epoxidized in the presence of a suitable catalyst. The compound is reacted. In the above reaction, m in the curable resin is adjusted to be in the range of 1 to 7, preferably 1 to 5, more preferably 1 to 3. These compounds may be used alone or in combination of two or more.

對於m之數，在後述實施例之情況下，在合成合成中間體G時可控制如以下。例如合成例1中之化合物E-1中之環氧基與雙酚A(相當於化合物F)之當量比雖為1.0：2.5，將該比若在1.0：2.0或1.0：1.5時，m數會增大。相反地，若為1.0：10或1.0：100、1.0：1000等時不會成為未達1。 The number of m can be controlled as follows in the case of synthesizing the synthesis intermediate G in the case of the examples described later. For example, the equivalent ratio of the epoxy group in the compound E-1 to the bisphenol A (corresponding to the compound F) in the synthesis example 1 is 1.0:2.5, and the ratio is 1.0:2.0 or 1.0:1.5, the number of m is Will increase. Conversely, if it is 1.0:10 or 1.0:100, 1.0:1000, etc., it will not become less than 1.

且，由反應性觀點來看，化合物E中之R4及化合物F中之R5的一方為氫原子，另一方為縮水甘油基或甲基縮水甘油基者為佳。 Further, from the viewpoint of reactivity, it is preferred that one of R 4 in the compound E and R 5 in the compound F is a hydrogen atom, and the other is a glycidyl group or a methyl glycidyl group.

作為上述鹼，由反應迅速進行與合成成本之觀點來看，以氫氧化鈉、氫氧化鉀等鹼金屬氫氧化物、碳酸鈉、碳酸鉀等鹼金屬碳酸鹽、氯化四甲基銨、氯化甲基三辛基銨、氯化甲基十三烷基銨、氯化苯甲基三甲基銨等第四級銨鹽為佳，氫氧化鈉或第四級銨鹽較佳。這些鹼可作為水溶液形式使用為佳，但視情況可將粉末或固形之鹼與水同時或者各別加入。又，這些鹼可單獨使用1種亦可組合2種以上使用。 As the above-mentioned base, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal carbonate such as sodium carbonate or potassium carbonate, tetramethylammonium chloride or chlorine is used from the viewpoint of rapid reaction and synthesis cost. A fourth-order ammonium salt such as methyltrioctylammonium chloride, methyltridecylammonium chloride or benzyltrimethylammonium chloride is preferred, and sodium hydroxide or a fourth-order ammonium salt is preferred. These bases may preferably be used in the form of an aqueous solution, but the powder or solid base may be added simultaneously or separately with water as the case may be. Further, these bases may be used alone or in combination of two or more.

鹼之使用量由反應迅速進行與合成成本觀點來看，以R4為氫原子，R5為縮水甘油基之情況，鹼為羥基的當量以上即可，R4為縮水甘油基或甲基縮水甘油基，R5為氫原子之情況為觸媒量即可，化合物F之羥基的0.0001~0.1當量。 The amount of the base used is such that R 4 is a hydrogen atom, R 5 is a glycidyl group, and the base is a hydroxyl group equivalent or more, and R 4 is a glycidyl group or a methyl group. The glyceryl group may be a catalyst atom when R 5 is a hydrogen atom, and 0.0001 to 0.1 equivalent of the hydroxyl group of the compound F.

環氧化化合物之使用量，以對於含於原料化合物之羥基為0.05~20當量，較佳為0.05~15當量。該使用量可藉由目的之硬化性樹脂中之環氧基的平均個數x而調整，對於羥基即使使用大過剩量，亦不會提高x之原料化合物的羥基平均個數。 The epoxidized compound is used in an amount of 0.05 to 20 equivalents, preferably 0.05 to 15 equivalents, based on the hydroxyl group contained in the starting compound. The amount of use can be adjusted by the average number x of epoxy groups in the curable resin of interest, and even if a large excess amount is used for the hydroxyl group, the average number of hydroxyl groups of the raw material compound of x is not increased.

作為觸媒，由反應時間、成本、反應活性之觀點來看，以三甲基胺、三辛基胺、十三烷基胺等第三級胺、氯化四甲基銨、氯化甲基三辛基銨、氯化甲基十三烷基銨、氯化苯甲基三甲基銨等第四級銨鹽為佳，以第四級銨鹽為較佳。這些可單獨使用1種，亦可組合2種以上使用。 As a catalyst, a tertiary amine such as trimethylamine, trioctylamine or tridecylamine, tetramethylammonium chloride or methyl chloride is used from the viewpoint of reaction time, cost, and reactivity. A fourth-order ammonium salt such as trioctyl ammonium, methyl tridecyl ammonium chloride or benzyl trimethyl ammonium chloride is preferred, and a fourth-order ammonium salt is preferred. These may be used alone or in combination of two or more.

觸媒之使用量由一邊抑制副反應一邊確保適當的反應速度的觀點來看，對於原料化合物所含之羥基而言，以0.0001~0.5當量為佳，較佳為0.01~0.1當量。 The amount of the catalyst used is preferably from 0.0001 to 0.5 equivalents, preferably from 0.01 to 0.1 equivalents, based on the hydroxyl group contained in the raw material compound from the viewpoint of suppressing the side reaction and ensuring an appropriate reaction rate.

與上述鹼之反應，以50~250℃為佳，較佳為70~200℃，更佳為100~170℃下進行，與上述環氧化化合物之反應，以25~100℃為佳，較佳為30~80℃，更佳為40~60℃下進行。反應時可使用烴、醚或酮等對於反應為惰性的溶劑，但使用過剩的環氧化化合物時，該化合 物因可作為溶劑功能，故這些溶劑並分必需。 The reaction with the above base is preferably 50 to 250 ° C, preferably 70 to 200 ° C, more preferably 100 to 170 ° C, and the reaction with the above epoxidized compound is preferably 25 to 100 ° C, preferably. It is carried out at 30 to 80 ° C, more preferably 40 to 60 ° C. A solvent inert to the reaction such as a hydrocarbon, an ether or a ketone may be used in the reaction, but when an excess epoxidized compound is used, the compound is used. Since the cause acts as a solvent, these solvents are necessary.

反應終了後之硬化性樹脂的純化可依據常法進行，例如將過剩環氧化化合物餾去後，視必要加入烴等非水溶性溶劑後，藉由除去經水洗所生成之食鹽及觸媒，可得到目的的本發明之硬化性樹脂。 The purification of the curable resin after the completion of the reaction can be carried out according to a usual method. For example, after the excess epoxidized compound is distilled off, if necessary, a water-insoluble solvent such as a hydrocarbon is added, and then the salt and the catalyst formed by washing with water are removed. The desired curable resin of the present invention is obtained.

本發明之硬化性樹脂的製造方法，由作為化合物E及化合物F可使用泛用原料之觀點來看，在化合物E中之R4為縮水甘油基的化合物E1(化合物E之二縮水甘油基醚化物；例如聚乙二醇二縮水甘油基醚)，化合物F中之R5為氫原子的化合物F1(例如雙酚A)時，以含有將前述化合物E1與前述化合物F1進行反應，得到前述化合物E1與前述化合物F1之合成中間體G的步驟1、與將合成中間體G之羥基經環氧化後，得到前述合成中間體G之羥基的一部分或全部皆被環氧化之硬化性樹脂的步驟2為佳。 In the method for producing a curable resin of the present invention, from the viewpoint of using a general-purpose raw material as the compound E and the compound F, the compound E1 in which R 4 is a glycidyl group in the compound E (the diglycidyl ether of the compound E) When the compound F1 (for example, bisphenol A) wherein R 5 is a hydrogen atom in the compound F, the compound E1 is reacted with the compound F1 to obtain the compound Step 1 of synthesizing intermediate G of E1 and the above compound F1, and step 2 of obtaining a curable resin in which a part or all of the hydroxyl group of the synthesis intermediate G is epoxidized after epoxidation of the hydroxyl group of the synthesis intermediate G It is better.

<(甲基)丙烯酸化硬化性樹脂之製造方法> <Method for Producing (Methyl) Acrylate Curable Resin>

進一步經由將硬化性樹脂在鹼性觸媒存在下，與(甲基)丙烯酸系化合物進行反應的步驟3，於環氧基、羥基、及不飽和鍵之至少一部分導入(甲基)丙烯酸基可得到本發明之(甲基)丙烯酸化硬化性樹脂。 Further, the step (3) of reacting the curable resin with the (meth)acrylic compound in the presence of a basic catalyst may introduce a (meth)acrylic group into at least a part of the epoxy group, the hydroxyl group, and the unsaturated bond. The (meth) acrylated curable resin of the present invention is obtained.

作為鹼性觸媒，可使用使用於環氧樹脂與(甲基)丙烯酸之反應的公知鹼性觸媒。又，亦可使用將鹼性觸媒載持於聚合物之聚合物載持鹼性觸媒。作為鹼性 觸媒，以3價有機磷化合物、其鹽、胺化合物及其鹽為佳。這些鹼性觸媒可單獨使用1種，亦可組合2種以上使用。且，鹼性觸媒之鹼性原子為磷及/或氮。 As the basic catalyst, a known basic catalyst used for the reaction of an epoxy resin with (meth)acrylic acid can be used. Further, a base catalyst in which a basic catalyst is supported on a polymer may be used. As alkaline The catalyst is preferably a trivalent organic phosphorus compound, a salt thereof, an amine compound or a salt thereof. These alkaline catalysts may be used alone or in combination of two or more. Further, the basic atom of the basic catalyst is phosphorus and/or nitrogen.

作為3價有機磷化合物，可舉出如三乙基次膦、三-n-丙基次膦、三-n-丁基次膦之烷基次膦類及其鹽、三苯基次膦、三-m-甲苯基次膦、參(2,6-二甲氧基苯基)次膦等芳基次膦類及其鹽、三苯基亞磷酸酯、三乙基亞磷酸酯、參(壬基苯基)亞磷酸酯等亞磷酸三酯類及其鹽等。其中亦以三苯基次膦為佳。 Examples of the trivalent organophosphorus compound include alkylphosphinic acid such as triethylphosphinylphosphite, tri-n-propylphosphinic acid, tri-n-butylphosphinic acid, and salts thereof, and triphenylphosphinium. Aryl phosphines such as tris-m-tolylphosphine, ginseng (2,6-dimethoxyphenyl)phosphine and salts thereof, triphenylphosphite, triethyl phosphite, ginseng A phosphite triester such as a nonylphenyl phosphite and a salt thereof. Among them, triphenylphosphinium is also preferred.

作為3價有機磷化合物之鹽，可舉出三苯基次膦．乙基溴化物、三苯基次膦．丁基溴化物、三苯基次膦．辛基溴化物、三苯基次膦．癸基溴化物、三苯基次膦．異丁基溴化物、三苯基次膦．丙基氯化物、三苯基次膦．戊基氯化物、三苯基次膦．己基溴化物等。 The salt of the trivalent organic phosphorus compound is exemplified by triphenylphosphinium. Ethyl bromide, triphenylphosphinium. Butyl bromide, triphenylphosphinium. Octyl bromide, triphenylphosphinium. Mercapto bromide, triphenylphosphinium. Isobutyl bromide, triphenylphosphinium. Propyl chloride, triphenylphosphinium. Amyl chloride, triphenylphosphinium. Hexyl bromide and the like.

作為胺化合物，可舉出二乙醇胺等第二級胺、三乙醇胺、二甲基苯甲基胺、參二甲基胺基甲基酚、參二乙基胺基甲基酚等第3級胺、1,5,7-三氮雜聯環〔4.4.0〕癸-5-烯(TBD)、7-甲基-1,5,7-三氮雜聯環〔4.4.0〕癸-5-烯(Me-TBD)、1,8-二氮雜雙環〔5.4.0〕十一-7-烯(DBU)、6-二丁基胺基-1,8-二氮雜雙環〔5.4.0〕十一-7-烯、1,5-二氮雜雙環〔4.3.0〕壬-5-烯(DBN)、1,1,3,3-四甲基脈等強鹼性胺。其中亦以1,5,7-三氮雜聯環〔4.4.0〕癸-5-烯(TBD)為佳。 Examples of the amine compound include a third-grade amine such as a second-order amine such as diethanolamine, triethanolamine, dimethylbenzylamine, dimethylaminomethylphenol or cis-diethylaminomethylphenol. 1,5,7-triazabicyclo[4.4.0]non-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]癸-5 -ene (Me-TBD), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 6-dibutylamino-1,8-diazabicyclo[5.4. 0] eleven-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,1,3,3-tetramethyl vein and other strongly basic amine. Among them, 1,5,7-triazabicyclo[4.4.0]non-5-ene (TBD) is preferred.

作為胺化合物之鹽，可舉出氯化苯甲基三甲 基銨、氯化苯甲基三乙基銨、及前述強鹼性胺之鹽等。 As a salt of an amine compound, benzyl chloroformate is exemplified. A solution of a base ammonium, benzyltriethylammonium chloride, and a salt of the above strongly basic amine.

作為載持鹼性觸媒之聚合物，並無特別限定，可使用將聚苯乙烯以二乙烯基苯進行交聯之聚合物或將丙烯酸樹脂以二乙烯基苯進行交聯的聚合物等。這些聚合物係對於以下溶劑及原料、生成物為不溶者，該溶劑為使用於藉由含有步驟1或步驟1及2之製造方法所得之硬化性樹脂與(甲基)丙烯酸系化合物之反應的溶劑(例如甲基乙基酮、甲基異丁基酮、甲苯等)及原料、生成物。又，這些聚合物可單獨使用1種，或組合2種以上使用。 The polymer carrying the basic catalyst is not particularly limited, and a polymer obtained by crosslinking polystyrene with divinylbenzene or a polymer obtained by crosslinking an acrylic resin with divinylbenzene can be used. These polymers are insoluble in the following solvents, raw materials, and products which are used for the reaction of a curable resin obtained by the production method containing the step 1 or the steps 1 and 2 with a (meth)acrylic compound. A solvent (for example, methyl ethyl ketone, methyl isobutyl ketone, toluene, etc.), a raw material, and a product. Further, these polymers may be used alone or in combination of two or more.

聚合物載持鹼性觸媒可藉由將鹼性觸媒於不溶性聚合物使其進行化學結合、或將鹼性觸媒導入於單體，聚合單體後，以二乙烯基苯等交聯單體進行3次元交聯而製造，藉由如此交聯，可成為對於甲基乙基酮、甲基異丁基酮、甲苯等溶劑為不溶的聚合物載持鹼性觸媒。 The polymer-supporting alkaline catalyst can be chemically bonded to the insoluble polymer by a basic catalyst, or the basic catalyst can be introduced into the monomer, and the monomer can be crosslinked by divinylbenzene or the like after polymerizing the monomer. The monomer is produced by a three-dimensional cross-linking, and by such cross-linking, it is possible to carry a basic catalyst for a polymer insoluble in a solvent such as methyl ethyl ketone, methyl isobutyl ketone or toluene.

作為聚合物載持鹼性觸媒，具體可舉出二苯基膦聚苯乙烯、1,5,7-三氮雜聯環〔4.4.0〕癸-5-烯聚苯乙烯、N,N-(二異丙基)胺基甲基聚苯乙烯、N-(甲基聚苯乙烯)-4-(甲基胺基)吡啶等。這些聚合物載持鹼性觸媒可單獨使用1種亦可組合2種以上使用。 Specific examples of the carrier-supporting basic catalyst include diphenylphosphine polystyrene, 1,5,7-triazadicyclo[4.4.0]non-5-ene polystyrene, and N,N. -(diisopropyl)aminomethylpolystyrene, N-(methylpolystyrene)-4-(methylamino)pyridine, and the like. These polymers may be used alone or in combination of two or more.

作為聚合物載持鹼性觸媒，可使用販賣品。作為販賣品的聚合物載持鹼性觸媒，例如可舉出PS-PPh3(二苯基膦聚苯乙烯、Biotage公司製)、PS-TBD(1,5,7-三氮雜聯環〔4.4.0〕癸-5-烯聚苯乙烯、Biotage公司製)等。 As the polymer-supporting alkaline catalyst, a vending product can be used. Examples of the carrier-supporting basic catalyst include PS-PPh 3 (diphenylphosphine polystyrene, manufactured by Biotage Co., Ltd.), and PS-TBD (1,5,7-triazole hybrid ring). [4.4.0] 癸-5-ene polystyrene, manufactured by Biotage Co., Ltd.).

對於本發明之(甲基)丙烯酸化硬化性樹脂之製造方法，藉由含有步驟1或步驟1及2之製造方法所得之硬化性樹脂與(甲基)丙烯酸系化合物之反應步驟中之溫度以60~120℃為佳，較佳為80~120℃，更佳為90~110℃。 The method for producing the (meth) acrylate-hardening resin of the present invention is carried out by the temperature in the reaction step of the curable resin obtained by the production method of the step 1 or the steps 1 and 2 and the (meth)acrylic compound. 60 to 120 ° C is preferred, preferably 80 to 120 ° C, more preferably 90 to 110 ° C.

在觸媒存在下，使藉由含有步驟1或步驟1及2之製造方法所得之硬化性樹脂與(甲基)丙烯酸系化合物進行反應時，預防使凝膠化，必需將反應系統內及反應系統上的氣相氧濃度保持在適當量。例如在積極地將空氣吹入反應系統內時，引起觸媒之氧化，會導致活性降低之情況而必須加以注意。 In the presence of a catalyst, when the curable resin obtained by the production method of the step 1 or the steps 1 and 2 is reacted with a (meth)acrylic compound, gelation is prevented, and it is necessary to react the reaction system and the reaction. The gas phase oxygen concentration on the system is maintained at an appropriate amount. For example, when air is actively blown into the reaction system, oxidation of the catalyst is caused, which causes a decrease in activity and must be taken care of.

對於藉由含有步驟1或步驟1及2之製造方法所得的硬化性樹脂與(甲基)丙烯酸系化合物之反應，因藉由該反應所得之(甲基)丙烯酸化硬化性樹脂可藉由紫外線等活性能量線而硬化，故在可遮住紫外線之容器內反應者為佳。又，藉由含有步驟1或步驟1及2之製造方法所得之硬化性樹脂與(甲基)丙烯酸系化合物之反應，欲防止氣相聚合，雖可在對於硬化性樹脂顯示良溶劑性的迴流溶劑存在下進行，但該情況下，於反應終了後必需除去溶劑。因此，前述反應在無溶劑下進行為佳。作為迴流溶劑，可舉出丙酮、甲基乙基酮、甲苯等。 The reaction of the curable resin obtained by the production method comprising the step 1 or the steps 1 and 2 with the (meth)acrylic compound, the (meth) acrylated curable resin obtained by the reaction can be ultraviolet-ray-treated It is hardened by the active energy ray, so it is preferable to react in a container that can block ultraviolet rays. Moreover, by reacting the curable resin obtained by the production method of the step 1 or the steps 1 and 2 with the (meth)acrylic compound, it is possible to prevent the vapor phase polymerization, and it is possible to exhibit a good solvent reflux for the curable resin. The solvent is carried out in the presence of a solvent, but in this case, it is necessary to remove the solvent after the end of the reaction. Therefore, the above reaction is preferably carried out without a solvent. Examples of the reflux solvent include acetone, methyl ethyl ketone, toluene, and the like.

[液晶密封劑組成物] [Liquid Crystal Sealant Composition]

本發明之硬化性樹脂及(甲基)丙烯酸化硬化性樹脂 (以下綜合此等亦稱為「本發明之硬化性樹脂等」)具有上述說明之種種特性，具有作為液晶密封劑使用的較佳黏度、低液晶污染性及優良硬化後柔軟性。 Curable resin and (meth) acrylated curable resin of the present invention (hereinafter, referred to as "the curable resin of the present invention" or the like) has various characteristics as described above, and has a preferable viscosity as a liquid crystal sealing agent, low liquid crystal contamination, and excellent flexibility after curing.

因此，使用本發明之硬化性樹脂等之液晶密封劑組成物具有優良處理性，在液晶滴落法中，即使在未硬化狀態下與液晶接觸之情況下，因難對於液晶配向性造成影響，故難以阻礙液晶之配向性，而使用於如可撓性液晶顯示器的可撓性裝置時，即使將夾住經硬化之液晶密封劑的可撓性基板進行彎曲時，因該優良柔軟性或應力緩和效果可使液晶密封部分的龜裂或自基板之剝離等難以產生。 Therefore, the liquid crystal sealant composition using the curable resin or the like of the present invention has excellent handleability, and in the liquid crystal dropping method, even when it is in contact with the liquid crystal in an uncured state, it is difficult to affect the liquid crystal alignment property. Therefore, it is difficult to hinder the alignment of the liquid crystal, and when used in a flexible device such as a flexible liquid crystal display, even when the flexible substrate sandwiching the cured liquid crystal sealing agent is bent, the excellent flexibility or stress is caused. The tempering effect makes it difficult to cause cracking of the liquid crystal sealing portion or peeling from the substrate.

具體而言，本發明之液晶密封劑組成物的黏度通常為1000~2000000mPa．s，以10000~1000000mPa．s為佳。又，液晶密封劑組成物的黏度可藉由本發明之硬化性樹脂等結構，或以下說明之液晶密封劑組成物的含有成分中之成分或溶劑的添加而調節。 Specifically, the viscosity of the liquid crystal sealant composition of the present invention is usually 1000 to 2000000 mPa. s, to 10000~1000000mPa. s is better. In addition, the viscosity of the composition of the liquid crystal sealing agent can be adjusted by a structure such as a curable resin of the present invention or a component or a solvent of a component of the liquid crystal sealing agent composition described below.

如此含有本發明之硬化性樹脂等的本發明之液晶密封劑組成物中，將此硬化的液晶密封劑硬化物之貯藏彈性率由柔軟性觀點來看，通常室溫(25℃)下1.0×103~3.0×109Pa，較佳為1.0×103~1.0×109Pa。且貯藏彈性率之測定方法在後述實施例之項目中詳細說明。 In the liquid crystal sealing agent composition of the present invention containing the curable resin or the like of the present invention, the storage elastic modulus of the cured liquid crystal sealing agent cured product is usually 1.0 × at room temperature (25 ° C) from the viewpoint of flexibility. 10 3 to 3.0 × 10 9 Pa, preferably 1.0 × 10 3 to 1.0 × 10 9 Pa. The method for measuring the storage modulus of elasticity is described in detail in the items of the examples to be described later.

又，使本發明之液晶密封劑組成物進行硬化所得之液晶密封劑硬化物的玻璃轉移溫度(Tg)由柔軟性觀點來看，通常80℃以下，以40℃以下為佳，較佳為 30℃以下，更佳為室溫(25℃)以下，特佳為-80~25℃。 In addition, the glass transition temperature (Tg) of the cured liquid crystal sealing agent obtained by curing the liquid crystal sealing agent composition of the present invention is usually 80 ° C or lower, preferably 40 ° C or lower, preferably from the viewpoint of flexibility. It is 30 ° C or less, more preferably room temperature (25 ° C) or less, and particularly preferably -80 to 25 ° C.

本發明之液晶密封劑組成物為含有本發明之硬化性樹脂等，但前述液晶密封劑組成物中之硬化性樹脂等含有量通常5~95重量%，由對柔軟性、接著性及液晶配向性之影響的觀點來看，較佳為10~95重量%。 The liquid crystal sealing agent composition of the present invention contains the curable resin of the present invention or the like, but the content of the curable resin or the like in the liquid crystal sealing agent composition is usually 5 to 95% by weight, and the flexibility, adhesion, and liquid crystal alignment are used. From the viewpoint of the influence of sex, it is preferably from 10 to 95% by weight.

又，本發明之液晶密封劑組成物配合該用途所要求的各種特性，將以下所說明之各種成分在不損害本發明之效果的範圍下可進一步含有。 Moreover, the liquid crystal sealing agent composition of the present invention can further contain various components described below in accordance with various properties required for the application without departing from the effects of the present invention.

<化合物H> <Compound H>

本發明之液晶密封劑組成物亦可含有本發明之硬化性樹脂等其他硬化成分，例如與作為液晶密封劑之主劑所使用之過去具有乙烯性不飽和基及/或環氧基之化合物H(例如將雙酚A型環氧樹脂之環氧基的一部分經(甲基)丙烯酸酯化的寡聚物)之同時添加本發明之硬化性樹脂等的液晶密封劑組成物，與僅添加化合物H的情況相比，液晶密封劑硬化物的柔軟性大大地提高。 The liquid crystal sealing agent composition of the present invention may contain other hardening components such as a curable resin of the present invention, for example, a compound H having an ethylenically unsaturated group and/or an epoxy group used as a main component of a liquid crystal sealing agent. (For example, a liquid crystal sealant composition such as a curable resin of the present invention is added to a (meth)acrylated oligomer of a bisphenol A type epoxy resin), and only a compound is added. In the case of H, the softness of the liquid crystal sealant cured product is greatly improved.

作為具有乙烯性不飽和基之化合物H，可舉出(甲基)丙烯酸酯化合物、脂肪族丙烯醯基化合物、脂環式丙烯醯基化合物、含有芳香族之丙烯醯基化合物或N-取代丙烯醯基系化合物。 Examples of the compound H having an ethylenically unsaturated group include a (meth) acrylate compound, an aliphatic propylene fluorenyl compound, an alicyclic propylene fluorenyl compound, an aromatic propylene fluorenyl compound or an N-substituted propylene. A sulfhydryl compound.

作為前述(甲基)丙烯酸酯化合物，可舉出對異丙苯苯氧基乙二醇(甲基)丙烯酸酯、t-丁基(甲 基)丙烯酸酯、乙氧基化苯基(甲基)丙烯酸酯、苯甲基(甲基)丙烯酸酯、縮水甘油基(甲基)丙烯酸酯作為代表的脂肪族(甲基)丙烯酸酯、芳香環含有(甲基)丙烯酸酯。 Examples of the (meth) acrylate compound include p-isopropylphenoxyethylene glycol (meth) acrylate and t-butyl (A). Acrylate, ethoxylated phenyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate as a representative aliphatic (meth) acrylate, aromatic The ring contains (meth) acrylate.

又，作為具有乙烯性不飽和基之化合物H，亦可舉出一官能性、二官能性、三官能性或多官能性自由基聚合性不飽和化合物。 Further, examples of the compound H having an ethylenically unsaturated group include monofunctional, difunctional, trifunctional or polyfunctional radically polymerizable unsaturated compounds.

作為前述一官能性自由基聚合性不飽和化合物，由液晶密封劑組成物之黏度、可撓性的確保觀點來看，以由選自由羥基乙基(甲基)丙烯酸酯、苯甲基(甲基)丙烯酸酯、四氫糠基(甲基)丙烯酸酯、異辛基(甲基)丙烯酸酯、環己基(甲基)丙烯酸酯、異冰片基(甲基)丙烯酸酯、二環戊基(甲基)丙烯酸酯、環己氧基乙基(甲基)丙烯酸酯、二環戊氧基乙基(甲基)丙烯酸酯、二環戊烯氧基乙基(甲基)丙烯酸酯、異肉荳蔻(甲基)丙烯酸酯、月桂基(甲基)丙烯酸酯、tert-丁基(甲基)丙烯酸酯及二乙二醇單乙基醚(甲基)丙烯酸酯所成群的1種以上化合物為佳，以選自由異冰片基(甲基)丙烯酸酯、四氫糠基(甲基)丙烯酸酯、二環戊基(甲基)丙烯酸酯、二環戊烯氧基乙基(甲基)丙烯酸酯及環己基(甲基)丙烯酸酯所成群的1種以上化合物為較佳。 The monofunctional radically polymerizable unsaturated compound is selected from the group consisting of hydroxyethyl (meth) acrylate and benzyl (methyl acrylate) from the viewpoint of viscosity and flexibility of the liquid crystal sealing agent composition. Acrylate, tetrahydrofurfuryl (meth) acrylate, isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentyl ( Methyl) acrylate, cyclohexyloxyethyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, different meat One or more compounds in groups of soybean meal (meth) acrylate, lauryl (meth) acrylate, tert-butyl (meth) acrylate, and diethylene glycol monoethyl ether (meth) acrylate Preferably, it is selected from the group consisting of isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyloxyethyl (methyl) One or more compounds in which an acrylate and a cyclohexyl (meth) acrylate are grouped are preferred.

作為前述二官能性自由基聚合性不飽和化合物，由液晶密封劑組成物之黏度、可撓性的確保觀點來看，以選自由三環癸烷二甲醇二(甲基)丙烯酸酯、二羥 甲基二環戊烷二(甲基)丙烯酸酯、EO改性1,6-已二醇二(甲基)丙烯酸酯、EO改性雙酚A二(甲基)丙烯酸酯、PO改性雙酚A二(甲基)丙烯酸酯、聚酯二(甲基)丙烯酸酯(例如ARONIX M-6100、東亞合成公司製)、聚乙二醇二(甲基)丙烯酸酯(例如4G、新中村化學工業公司製)、及矽二(甲基)丙烯酸酯(例如EBECRYL 350、大賽璐．Orunekusu公司製)所成群的1種以上化合物為佳，以二羥甲基二環戊烷二(甲基)丙烯酸酯及/或EO或者PO改性雙酚A二(甲基)丙烯酸酯為較佳。其中亦以不具有羥基而具有雙酚A骨架的(甲基)丙烯酸酯為佳，作為如此(甲基)丙烯酸酯，已有自共榮公司化學(股)的輕丙烯酸酯BP-4EAL(雙酚A之EO加成物二丙烯酸酯)、BP-4PA(雙酚A之PO加成物二丙烯酸酯)等被販賣。 The difunctional radically polymerizable unsaturated compound is selected from the group consisting of tricyclodecane dimethanol di(meth)acrylate and dihydroxyl from the viewpoint of viscosity and flexibility of the liquid crystal sealing agent composition. Methyl dicyclopentane di(meth)acrylate, EO modified 1,6-hexanediol di(meth)acrylate, EO modified bisphenol A di(meth)acrylate, PO modified double Phenol A di(meth)acrylate, polyester di(meth)acrylate (for example, ARONIX M-6100, manufactured by Toagosei Co., Ltd.), polyethylene glycol di(meth)acrylate (for example, 4G, Shin-Nakamura Chemical Co., Ltd.) It is preferable to use one or more compounds in groups of bismuth (meth) acrylate (for example, EBECRYL 350, manufactured by Osei. Orunekusu Co., Ltd.), and dimethylol dicyclopentane di(methyl) Acrylate and/or EO or PO modified bisphenol A di(meth)acrylate is preferred. Among them, a (meth) acrylate having a bisphenol A skeleton which does not have a hydroxyl group is preferred, and as such a (meth) acrylate, a light acrylate BP-4EAL (double) from Kyoritsu Chemical Co., Ltd. The EO adduct diacrylate of phenol A), BP-4PA (PO adduct diacrylate of bisphenol A), etc. are sold.

作為前述三官能性或多官能性自由基聚合性不飽和化合物，由液晶密封劑組成物之黏度、可撓性的確保觀點來看，以選自由EO改性甘油三(甲基)丙烯酸酯(三官能)、PO改性甘油三(甲基)丙烯酸酯(三官能)、季戊四醇三(甲基)丙烯酸酯(三官能)、二季戊四醇六(甲基)丙烯酸酯(六官能)及季戊四醇四(甲基)丙烯酸酯(四官能)所成群的1種以上化合物為佳，以EO改性甘油三(甲基)丙烯酸酯為較佳。 The trifunctional or polyfunctional radical polymerizable unsaturated compound is selected from EO-modified glycerol (meth) acrylate from the viewpoint of viscosity and flexibility of the liquid crystal sealing agent composition. Trifunctional), PO modified tris(meth)acrylate (trifunctional), pentaerythritol tri(meth)acrylate (trifunctional), dipentaerythritol hexa(meth)acrylate (hexafunctional) and pentaerythritol tetra ( One or more compounds in which a group of methyl) acrylates (tetrafunctional) are grouped are preferred, and EO-modified glycerol tri(meth)acrylate is preferred.

其次作為具有環氧基之化合物H，以選自由雙酚A型環氧化合物、雙酚F型環氧化合物、雙酚AD型 環氧化合物、酚酚醛清漆型環氧化合物、甲酚酚醛清漆型環氧化合物、萘型環氧化合物、間苯二酚型環氧化合物、這些氫化化合物及脂環型環氧化合物所成群的至少1種化合物為佳，較佳為選自由雙酚A型環氧化合物、雙酚F型環氧化合物、萘型環氧化合物及間苯二酚型環氧化合物所成群的至少1種化合物，更佳為雙酚A型環氧化合物。 Next, as the compound H having an epoxy group, selected from the group consisting of a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, and a bisphenol AD type. Epoxy compound, phenol novolak type epoxy compound, cresol novolak type epoxy compound, naphthalene type epoxy compound, resorcinol type epoxy compound, these hydrogenated compounds and alicyclic epoxy compounds are grouped At least one compound is preferred, and at least one compound selected from the group consisting of a bisphenol A epoxy compound, a bisphenol F epoxy compound, a naphthalene epoxy compound, and a resorcinol epoxy compound is preferred. More preferably, it is a bisphenol A type epoxy compound.

作為雙酚A型環氧化合物之具體例，有DIC公司製EPICLON850S、860、1055、EXA-850CRP等。 Specific examples of the bisphenol A type epoxy compound include EPICLON 850S, 860, 1055, and EXA-850 CRP manufactured by DIC Corporation.

作為氫化雙酚A型環氧化合物的具體例，有ADEKA公司製KRM-2408、JER公司製之YX-8034等。 Specific examples of the hydrogenated bisphenol A type epoxy compound include KRM-2408 manufactured by ADEKA Co., Ltd., and YX-8034 manufactured by JER Corporation.

作為雙酚F型環氧化合物的具體例，有DIC公司製EPICLON830S等。 Specific examples of the bisphenol F-type epoxy compound include EPICLON 830S manufactured by DIC Corporation.

作為萘型環氧化合物之具體例，有DIC公司製EPICLON HP-4032D、HP-7200H等。 Specific examples of the naphthalene type epoxy compound include EPICLON HP-4032D and HP-7200H manufactured by DIC Corporation.

作為酚酚醛清漆型環氧化合物的具體例，有DIC公司製EPICLON N-740、N-770等。 Specific examples of the phenol novolak type epoxy compound include EPICLON N-740 and N-770 manufactured by DIC Corporation.

作為甲酚酚醛清漆型環氧化合物的具體例，有DIC公司製EPICLON N-660、N-670等。 Specific examples of the cresol novolac type epoxy compound include EPICLON N-660 and N-670 manufactured by DIC Corporation.

作為間苯二酚型環氧化合物之具體例，有Nagase Chemtex公司製DenacolEX-201等。 Specific examples of the resorcinol type epoxy compound include Denacol EX-201 manufactured by Nagase Chemtex Co., Ltd., and the like.

作為脂環型環氧化合物的具體例，有3,4-環氧環己烯基甲基-3’,4’-環氧環己烯羧酸酯(Daicel Chemical Industries,Ltd.製CELLOXIDE2021P)、1,2：8,9-二環氧檸檬烯(Daicel Chemical Industries,Ltd.製 CELLOXIDE3000)、1,2-環氧-4-乙烯基環己烷(Daicel Chemical Industries,Ltd.製CELLOXIDE2000)、2,2-雙(羥基甲基)-1-丁醇之1,2-環氧-4-(2-環氧乙烷基)環己烷加成物(Daicel Chemical Industries,Ltd.製EHPE3150)等。 Specific examples of the alicyclic epoxy compound include 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate (CELLOXIDE 2021P manufactured by Daicel Chemical Industries, Ltd.). 1,2:8,9-diepoxylimene (manufactured by Daicel Chemical Industries, Ltd.) CELLOXIDE3000), 1,2-epoxy-4-vinylcyclohexane (CELLOXIDE 2000 manufactured by Daicel Chemical Industries, Ltd.), 1,2-epoxy 2,2-bis(hydroxymethyl)-1-butanol 4-(2-oxiranyl)cyclohexane adduct (EHPE 3150 manufactured by Daicel Chemical Industries, Ltd.) and the like.

作為具有乙烯性不飽和基及環氧基之化合物H，可舉出將環氧基含有化合物與(甲基)丙烯酸系化合物進行反應所得之部分(甲基)丙烯酸酯改性環氧化合物，作為該化合物以將雙酚A型環氧樹脂與(甲基)丙烯酸進行反應所得之部分(甲基)丙烯酸化環氧化合物為佳。 The compound H having an ethylenically unsaturated group and an epoxy group is a partial (meth) acrylate-modified epoxy compound obtained by reacting an epoxy group-containing compound with a (meth)acrylic compound, and The compound is preferably a partially (meth)acrylated epoxy compound obtained by reacting a bisphenol A type epoxy resin with (meth)acrylic acid.

將前述雙酚A型環氧樹脂與(甲基)丙烯酸進行反應所得之部分(甲基)丙烯酸化環氧化合物，例如可如下而得。 A part of the (meth) acrylated epoxy compound obtained by reacting the bisphenol A type epoxy resin with (meth)acrylic acid can be obtained, for example, as follows.

首先將雙酚A型環氧樹脂與(甲基)丙烯酸在鹼性觸媒，較佳為在3價有機磷酸化合物及/或胺化合物之存在下進行反應。此時的反應比對於環氧基1當量而言為(甲基)丙烯酸10~90當量%之比率。其次將該反應生成物經過濾、離心分離及/或水洗等處理後除去鹼性觸媒而純化。作為前述鹼性觸媒，可使用於環氧樹脂與(甲基)丙烯酸之反應所使用的公知鹼性觸媒。又，亦可使用將鹼性觸媒載持於聚合物之聚合物載持鹼性觸媒。 First, the bisphenol A type epoxy resin and (meth)acrylic acid are reacted in the presence of a basic catalyst, preferably a trivalent organic phosphoric acid compound and/or an amine compound. The reaction at this time is a ratio of 10 to 90 equivalent % of (meth)acrylic acid to 1 equivalent of the epoxy group. Next, the reaction product is purified by filtration, centrifugation, and/or washing, and then removing the basic catalyst. As the basic catalyst, a known basic catalyst used for the reaction between an epoxy resin and (meth)acrylic acid can be used. Further, a base catalyst in which a basic catalyst is supported on a polymer may be used.

如上述說明，於本發明之液晶密封劑組成物中可含有各種化合物H，本發明之硬化性樹脂等中不含乙 烯性不飽和基之情況為，作為前述化合物H以自由基聚合性化合物的具有上述乙烯性不飽和基之化合物為佳。 As described above, the liquid crystal sealant composition of the present invention may contain various compounds H, and the curable resin of the present invention does not contain B. In the case of the ethylenically unsaturated group, the compound H is preferably a compound having the above-mentioned ethylenically unsaturated group as a radically polymerizable compound.

又，以上說明之化合物H可單獨使用1種，或組合2種以上使用。 Further, the compound H described above may be used alone or in combination of two or more.

<光聚合起始劑> <Photopolymerization initiator>

本發明之液晶密封劑組成物可含有本發明之硬化性樹脂等，而含有之情況下，作為將化合物H進行光聚合時的自由基產生源而可含有光聚合起始劑。光聚合起始劑並無特別限定，可使用公知化合物，可單獨使用1種或組合2種以上使用。 The liquid crystal sealing agent composition of the present invention may contain a curable resin or the like of the present invention, and may contain a photopolymerization initiator as a source of radical generation when the compound H is photopolymerized. The photopolymerization initiator is not particularly limited, and a known compound can be used. These may be used alone or in combination of two or more.

作為前述光聚合起始劑，可舉出安息香類、苯乙酮類、二苯甲酮類、噻噸酮類、α-醯肟酯類、苯基乙醛酸類、苯甲基類、偶氮系化合物、二苯基硫化物系化合物、醯基次膦氧化物系化合物、安息香醚類及蒽醌類等，較佳為對液晶之溶解性低，且該自身在光照射時具有反應性基而不使分解物氣化。 Examples of the photopolymerization initiator include benzoin, acetophenone, benzophenone, thioxanthone, α-oxime ester, phenylglyoxylic acid, benzyl group, and azo. a compound, a diphenyl sulfide compound, a decylphosphine oxide compound, a benzoin ether, an anthraquinone, etc., preferably having low solubility to liquid crystals, and having a reactive group upon irradiation with light Without gasifying the decomposition product.

<光增感劑> <Light sensitizer>

本發明之液晶密封劑組成物一般為使其光硬化，欲提高此時對光之感度，可具有光增感劑。作為前述光增感劑可使用過去公知之各種化合物，並無特別限制，光增感劑可單獨使用1種，或組合2種以上使用。 The composition of the liquid crystal sealing agent of the present invention is generally light-hardened, and may have a photosensitizer if it is intended to improve the sensitivity to light at this time. The light sensitizer can be used in the form of a conventionally known compound, and is not particularly limited. The photosensitizer may be used singly or in combination of two or more.

作為前述光增感劑，由硬化性觀點來看，例 如可舉出羰基化合物、有機硫化合物、過硫化物、氧化還原系化合物、偶氮及二偶氮化合物、鹵素化合物、光還原性色素等。 As the light sensitizer, from the viewpoint of curability, an example Examples thereof include a carbonyl compound, an organic sulfur compound, a persulfide compound, a redox compound, an azo and a diazo compound, a halogen compound, and a photoreductive dye.

作為光增感劑，具體為如N-甲基吖啶酮、N-丁基吖啶酮之吖啶酮衍生物；其他可舉出α,α-二乙氧基苯乙酮、苯甲基、芴酮、呫噸酮、鈾醯化合物等，又作為上述光聚合起始劑之例子所舉出的亦可作為光增感劑之功能者。 The photosensitizer is specifically an acridone derivative such as N-methylacridone or N-butylacridone; the others may be α,α-diethoxyacetophenone or benzyl. Further, as an example of the photopolymerization initiator, the fluorenone, the xanthone, the uranium quinone compound, and the like can also be used as a function of the photosensitizer.

<硬化劑> <hardener>

由提高本發明之液晶密封劑組成物的接著性之觀點來看，可於前述液晶密封劑組成物中含有硬化劑。前述硬化劑並無特別限定，可使用公知化合物。 From the viewpoint of improving the adhesion of the liquid crystal sealing agent composition of the present invention, a curing agent can be contained in the liquid crystal sealing agent composition. The curing agent is not particularly limited, and a known compound can be used.

作為前述硬化劑，由接著性觀點來看有胺系硬化劑，例如以有機酸二醯肼化合物、咪唑及其衍生物、二氰二醯胺、芳香族胺、環氧改性聚胺、聚胺基脲等為佳。這些硬化劑可單獨使用1種，亦可組合2種以上使用。 As the curing agent, there are an amine-based curing agent from the viewpoint of adhesion, for example, an organic acid diterpene compound, imidazole and a derivative thereof, dicyandiamide, an aromatic amine, an epoxy-modified polyamine, and a poly Aminourea and the like are preferred. These curing agents may be used alone or in combination of two or more.

<硬化促進劑> <hardening accelerator>

本發明之液晶密封劑組成物由促進硬化成分(本發明之硬化性樹脂等或上述所說明之化合物H等)的硬化反應之觀點來看，可含有硬化促進劑，硬化促進劑可單獨使用1種，或組合2種以上使用。 The liquid crystal sealing agent composition of the present invention may contain a curing accelerator from the viewpoint of curing reaction of the curing component (the curable resin of the present invention or the above-described compound H or the like), and the curing accelerator may be used alone. Use of two or more types in combination.

作為該較佳例子，可舉出2-甲基咪唑、2-乙基咪唑及2-乙基-4-甲基咪唑等咪唑類、2-(二甲基胺基甲基)酚及1,8-二氮雜雙環〔5.4.0〕十一-7-烯(DBU)等第3級胺類；三苯基次膦等次膦類；辛基酸錫等金屬化合物等。 Preferred examples of the examples include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, and 2-(dimethylaminomethyl)phenol and 1, a third-order amine such as 8-diazabicyclo[5.4.0]undec-7-ene (DBU); a phosphine such as triphenylphosphinyl; a metal compound such as tin octylate;

<填充物> <filler>

本發明之液晶密封劑組成物由黏度控制、接著信賴性、線膨張性抑制之觀點來看，可含有填充物。作為前述填充物，可使用無機填充物及有機填充物，這些可單獨使用1種，亦可組合2種以上使用。 The liquid crystal sealing agent composition of the present invention may contain a filler from the viewpoint of viscosity control, reliability, and linear expansion. As the filler, an inorganic filler and an organic filler may be used, and these may be used alone or in combination of two or more.

作為前述無機填充物，可舉出碳酸鈣、碳酸鎂、硫酸鋇、硫酸鎂、矽酸鋁、氧化鈦、氧化鋁、氧化鋅、二氧化矽、高嶺土、滑石、玻璃珠、絹雲母活性白土、膨潤土、窒化鋁、及氮化矽等。 Examples of the inorganic filler include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, aluminum oxide, zinc oxide, cerium oxide, kaolin, talc, glass beads, and sericite-activated clay. Bentonite, aluminum telluride, and tantalum nitride.

作為前述有機填充物，可舉出聚甲基丙烯酸甲基、聚苯乙烯、構成這些的單體與其他單體經共聚合所得之共聚物、聚酯微粒子、聚胺基甲酸酯微粒子、橡膠微粒子、及由含有具有高玻璃轉移溫度之共聚物的外殼與含有具有低玻璃轉移溫度之共聚物的核心所構成之核心外殼型粒子等。作為核心外殼型粒子，可舉出Ganz化成公司製Zefi ACK系列(F351等)等。 Examples of the organic filler include polymethyl methacrylate, polystyrene, copolymers obtained by copolymerizing monomers constituting these and other monomers, polyester fine particles, polyurethane fine particles, and rubber. Microparticles, core shell-type particles composed of a shell containing a copolymer having a high glass transition temperature, and a core containing a copolymer having a low glass transition temperature. Examples of the core-shell type particles include the Zefi ACK series (F351, etc.) manufactured by Ganz Chemical Co., Ltd., and the like.

藉由添加非反應成分之填充物，可減低自液晶密封劑之漏氣的觀點來看，構成填充物之粒子平均粒子 徑通常為0.1~3μm，較佳為0.5~3μm。且，填充物之平均粒子徑可藉由HORIBA公司製雷射衍射/散亂式粒子徑分布測定裝置(例如HORIBA公司製Partica LA-950V2)所測定。 By adding a filler of a non-reactive component, the average particle of the particles constituting the filler can be reduced from the viewpoint of leakage of the liquid crystal sealing agent The diameter is usually 0.1 to 3 μm, preferably 0.5 to 3 μm. Further, the average particle diameter of the filler can be measured by a laser diffraction/scattering particle diameter distribution measuring device (for example, Partica LA-950V2 manufactured by HORIBA Co., Ltd.) manufactured by HORIBA.

<矽烷偶合劑> <decane coupling agent>

本發明之液晶密封劑組成物在達成本發明之效果的範圍內，可含有矽烷偶合劑。矽烷偶合劑可單獨使用1種，或組合2種以上使用。 The liquid crystal sealing agent composition of the present invention may contain a decane coupling agent within the range in which the effects of the present invention are achieved. The decane coupling agent may be used alone or in combination of two or more.

由兼併硬化本發明之液晶密封劑組成物所成的液晶密封劑硬化物之接著性及柔軟性之觀點來看，作為矽烷偶合劑，可舉出選自由四甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷、四異丙氧基矽烷、四丁氧基矽烷、二甲氧基二乙氧基矽烷、二甲氧基二異丙氧基矽烷、二乙氧基二異丙氧基矽烷、二乙氧基二丁氧基矽烷等四烷氧基矽烷類；甲基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三異丙氧基矽烷、乙基三乙氧基矽烷、乙基三丁氧基矽烷、環己基三乙氧基矽烷、苯基三異丙氧基矽烷、乙烯基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷等三烷氧基矽烷類；及二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、二乙基二乙氧基矽烷、二乙基二丁氧基矽烷、苯基乙基二乙氧基矽烷等二烷氧基矽烷類所成群之至少1種矽烷偶合劑為佳、彼等中，亦以選自由甲基三甲氧基矽烷、甲基三乙氧基矽 烷、甲基三異丙氧基矽烷、乙基三乙氧基矽烷、乙基三丁氧基矽烷、環己基三乙氧基矽烷、苯基三異丙氧基矽烷、乙烯基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷及3-甲基丙烯醯氧基丙基三甲氧基矽烷所成群之至少1種三烷氧基矽烷系矽烷偶合劑為較佳，以3-環氧丙氧基丙基三甲氧基矽烷為更佳。 From the viewpoint of the adhesion and flexibility of the cured liquid crystal sealant formed by the liquid crystal sealant composition of the present invention, the decane coupling agent is selected from the group consisting of tetramethoxynonane and tetraethoxy. Decane, tetrapropoxydecane, tetraisopropoxydecane, tetrabutoxydecane, dimethoxydiethoxydecane, dimethoxydiisopropoxydecane, diethoxydiisopropyloxy Tetraalkoxydecanes such as decane, diethoxydibutoxydecane; methyltrimethoxydecane, methyltriethoxydecane, methyltriisopropoxydecane, ethyltriethoxy Decane, ethyl tributoxydecane, cyclohexyltriethoxydecane, phenyltriisopropoxydecane, vinyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3- a trialkoxy decane such as methacryloxypropyltrimethoxydecane; and dimethyldimethoxydecane, dimethyldiethoxydecane, diethyldiethoxydecane, and diethyl At least one decane coupling agent in groups of dialkoxy decanes such as bisbutoxy decane and phenylethyl diethoxy decane Jia, in their drawn up selected from the group consisting of methyl trimethoxy Silane, methyl triethoxy silicon Alkane, methyl triisopropoxy decane, ethyl triethoxy decane, ethyl tributoxy decane, cyclohexyl triethoxy decane, phenyl triisopropoxy decane, vinyl trimethoxy decane Preferably, at least one trialkoxydecane-based decane coupling agent is a group of 3-glycidoxypropyltrimethoxydecane and 3-methacryloxypropyltrimethoxydecane. 3-glycidoxypropyltrimethoxydecane is more preferred.

[實施例] [Examples]

以下將本發明藉由實施例做具體說明，但本發明並未限定於此等實施例。且實施例及比較例所使用之化合物係由如以下所述製造。 The present invention will be specifically described by way of examples, but the invention is not limited thereto. Further, the compounds used in the examples and comparative examples were produced as described below.

[比較合成例1]部分甲基丙烯酸化雙酚A型環氧樹脂 [Comparative Synthesis Example 1] Partially methacrylated bisphenol A type epoxy resin

混合雙酚A型環氧樹脂(EXA850CRP、DIC股份有限公司製)340.0g、甲基丙烯酸(東京化成公司製)90.4g、三苯基次膦(東京化成公司製)0.5g、及BHT(二丁基羥基甲苯)100mg並在100℃進行6小時攪拌。得到淡黃色透明黏稠物之部分甲基丙烯酸化雙酚A型環氧樹脂418.0g。 Mixed with bisphenol A type epoxy resin (EXA850CRP, manufactured by DIC Co., Ltd.), 340.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 90.4 g, triphenylphosphinium (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.5 g, and BHT (two) Butylhydroxytoluene) 100 mg and stirred at 100 ° C for 6 hours. A portion of the methacrylated bisphenol A type epoxy resin of 418.0 g was obtained as a pale yellow transparent viscous material.

[合成例1]甲基丙烯酸化硬化性樹脂1 [Synthesis Example 1] methacrylic acid curable resin 1

將(1)聚乙二醇#1000(LION公司製)2000.0g(4.0當量/羥基)、環氧氯丙烷2220.0g(6.0當量)、苯甲基 三甲基銨氯化物74.3g(0.10當量)放入於附有機械攪拌機、溫度計、溫度調節器、凝縮器、Dean-Stark trap及滴液漏斗之5公升三口圓底燒瓶。 (1) Polyethylene glycol #1000 (manufactured by LION Co., Ltd.) 2000.0 g (4.0 equivalent/hydroxyl group), epichlorohydrin 2220.0 g (6.0 equivalent), benzyl group 74.3 g (0.10 equivalent) of trimethylammonium chloride was placed in a 5 liter three-neck round bottom flask equipped with a mechanical stirrer, thermometer, temperature regulator, condenser, Dean-Stark trap and dropping funnel.

其次，將混合物一邊在50托爾(torr)之高真空下攪拌，一邊加熱至約50至60℃並激烈迴流環氧氯丙烷。將600.0g的48%NaOH水溶液經2小時慢慢地添加於混合物中。當生成共沸物時，水/環氧氯丙烷混合物中，將環氧氯丙烷一邊回到反應系統，一邊繼續攪拌。 Next, the mixture was heated to about 50 to 60 ° C while stirring under a high vacuum of 50 torr and the epichlorohydrin was vigorously refluxed. 600.0 g of a 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. When an azeotrope is formed, in the water/epichlorohydrin mixture, the epichlorohydrin is continuously stirred while returning to the reaction system.

添加終了後經3小時繼續攪拌。其次，將反應混合物冷卻至室溫，加入氯仿3L，並以3L之水洗淨6次。將所得之有機相溶劑經減壓餾去而除去，得到1150.0g的白色蠟狀固體之化合物E-1。 Stirring was continued for 3 hours after the end of the addition. Next, the reaction mixture was cooled to room temperature, 3 L of chloroform was added, and the mixture was washed 6 times with 3 L of water. The obtained organic phase solvent was distilled off under reduced pressure to give the compound (1,1,1,1, g, as white white solid).

(2)將化合物E-1(950.0g(1.7當量/環氧基))、及雙酚A(988.0g(2.5當量))放入茄型燒瓶中，加熱攪拌至液溫至150℃。添加4%NaOH水溶液2.9g，並在150℃進行6小時攪拌。 (2) Compound E-1 (950.0 g (1.7 equivalents/epoxy group)) and bisphenol A (988.0 g (2.5 equivalents)) were placed in an eggplant type flask, and the mixture was heated and stirred until the liquid temperature reached 150 °C. 2.9 g of a 4% aqueous NaOH solution was added, and the mixture was stirred at 150 ° C for 6 hours.

冷卻液溫至60℃以下，加入氯仿2L，以1%NaOH水溶液2L洗淨6次，以水2L洗淨6次。 The temperature of the coolant was adjusted to 60 ° C or lower, 2 L of chloroform was added, and the mixture was washed 6 times with 2 L of 1% NaOH aqueous solution, and washed 6 times with 2 L of water.

於所得之有機相加入硫酸鎂，經乾燥後以過濾等濾出固體成分，將所得之有機相溶劑藉由減壓餾去餾去，得到997.0g的淡黃色透明黏稠物之合成中間體的反應物G-1。 After adding magnesium sulfate to the obtained organic phase, the solid component was filtered off by filtration, and the obtained organic phase solvent was distilled off under reduced pressure to obtain 997.0 g of a pale yellow transparent viscous synthetic intermediate. Matter G-1.

(3)將反應物G-1(997.0g)、環氧氯丙烷(1423.0g)、及苯甲基三甲基銨氯化物(47.5g)放入於 附有機械攪拌機、溫度計、溫度調節器、凝縮器、Dean-Stark trap及滴液漏斗之5公升三口圓底燒瓶。 (3) The reactant G-1 (997.0 g), epichlorohydrin (1423.0 g), and benzyltrimethylammonium chloride (47.5 g) were placed in A 5 liter three-neck round bottom flask with mechanical mixer, thermometer, thermostat, condenser, Dean-Stark trap and dropping funnel.

其次，將混合物在50托爾(torr)之高真空下一邊攪拌一邊加熱至約50至60℃，激烈迴流環氧氯丙烷。將384.0g之48%NaOH水溶液經2小時慢慢添加於混合物中。產生共沸物時，水/環氧氯丙烷混合物中，將環氧氯丙烷一邊回到反應系統，一邊繼續攪拌。添加終了後，繼續攪拌3小時。 Next, the mixture was heated to about 50 to 60 ° C while stirring under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 384.0 g of a 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. When an azeotrope is produced, in the water/epichlorohydrin mixture, the epichlorohydrin is continuously stirred while returning to the reaction system. After the addition was completed, stirring was continued for 3 hours.

其次，將反應混合物冷卻至室溫，加入氯仿2L，並以2L的水洗淨6次。將所得之有機相溶劑經減壓餾去後除去，得到982.0g之淡黃色黏稠物的樹脂1。 Next, the reaction mixture was cooled to room temperature, 2 L of chloroform was added, and washed 6 times with 2 L of water. The obtained organic phase solvent was distilled off under reduced pressure and then evaporated to give 982.0 g of pale yellow viscous resin.

(4)混合100.0g之樹脂1、甲基丙烯酸8.6g、三苯基次膦0.5g、及BHT 20mg，並在100℃進行5小時攪拌。得到107.0g之淡黃色黏稠物的甲基丙烯酸化硬化性樹脂1。 (4) 100.0 g of a resin 1, 8.6 g of methacrylic acid, 0.5 g of triphenylphosphinium, and 20 mg of BHT were mixed, and stirred at 100 ° C for 5 hours. 107.0 g of a pale yellow viscous methacrylate-curable resin 1 was obtained.

[合成例2]甲基丙烯酸化硬化性樹脂2 [Synthesis Example 2] methacrylic acid curable resin 2

(1)將聚四伸甲基醚甘醇(PTMG)1000(三菱化學公司製)500.0g(1.0當量/羥基)、環氧氯丙烷555.0g(6.0當量)、苯甲基三甲基銨氯化物18.6g(0.10當量)放入於附有機械攪拌機、溫度計、溫度調節器、凝縮器、Dean-Stark trap及滴液漏斗之2公升三口圓底燒瓶。 (1) Polytetramethyl ether glycol (PTMG) 1000 (manufactured by Mitsubishi Chemical Corporation) 500.0 g (1.0 equivalent/hydroxyl), epichlorohydrin 555.0 g (6.0 equivalent), benzyltrimethylammonium chloride 18.6 g (0.10 equivalent) of the compound was placed in a 2 liter three-neck round bottom flask equipped with a mechanical stirrer, thermometer, temperature regulator, condenser, Dean-Stark trap and dropping funnel.

其次，將混合物一邊在50托爾(torr)之高真空下進行攪拌，一邊加熱至約50至60℃並激烈迴流環 氧氯丙烷。將150.0g的48%NaOH水溶液經2小時慢慢地添加於混合物中。產生共沸物時，水/環氧氯丙烷混合物中，將環氧氯丙烷一邊回到反應系統，一邊繼續攪拌。添加終了後，繼續攪拌3小時。 Next, the mixture was stirred while stirring under a high vacuum of 50 torr, heated to about 50 to 60 ° C and vigorously refluxed. Oxychloropropane. 150.0 g of a 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. When an azeotrope is produced, in the water/epichlorohydrin mixture, the epichlorohydrin is continuously stirred while returning to the reaction system. After the addition was completed, stirring was continued for 3 hours.

其次，將反應混合物冷卻至室溫後加入氯仿，以1L的水洗淨4次。將所得之有機相溶劑經減壓餾去後除去，得到459.0g的白色蠟狀固體之化合物E-2。 Next, the reaction mixture was cooled to room temperature, and then chloroform was added thereto, and the mixture was washed 4 times with 1 L of water. The obtained organic phase solvent was evaporated under reduced pressure, and then evaporated, m.

(2)將化合物E-2(132.0g(0.20當量/環氧基))、及雙酚A(114.0g(2.5當量))放入於茄型燒瓶，加熱攪拌至液溫成為150℃。添加4%NaOH水溶液0.3g，在150℃進行6小時攪拌。冷卻至液溫60℃以下，加入氯仿500mL，以1%NaOH水溶液1L洗淨3次，以水1L洗淨3次。 (2) Compound E-2 (132.0 g (0.20 equivalent/epoxy group)) and bisphenol A (114.0 g (2.5 equivalent)) were placed in an eggplant type flask, and the mixture was heated and stirred until the liquid temperature became 150 °C. 0.3 g of a 4% NaOH aqueous solution was added, and the mixture was stirred at 150 ° C for 6 hours. After cooling to a liquid temperature of 60 ° C or less, 500 mL of chloroform was added, and the mixture was washed three times with 1 L of a 1% NaOH aqueous solution, and washed three times with 1 L of water.

於所得之有機相中加入硫酸鎂，乾燥後以過濾等過濾出固體成分，將所得之有機相溶劑藉由減壓餾去除去，得到140.0g之淡黃色透明黏稠物的合成中間體之反應物G-2。 Magnesium sulfate was added to the obtained organic phase, and after drying, the solid component was filtered by filtration or the like, and the obtained organic phase solvent was removed by distillation under reduced pressure to obtain a reaction product of a synthetic intermediate of 140.0 g of a pale yellow transparent viscous material. G-2.

(3)將反應物G-2(140.0g)、環氧氯丙烷(195.0g)、及苯甲基三甲基銨氯化物(6.5g)放入於附有機械攪拌機、溫度計、溫度調節器、凝縮器、Dean-Stark trap及滴液漏斗之1公升三口圓底燒瓶。 (3) The reactant G-2 (140.0 g), epichlorohydrin (195.0 g), and benzyltrimethylammonium chloride (6.5 g) were placed in a mechanical mixer, thermometer, and temperature regulator. 1 liter three-neck round bottom flask with condenser, Dean-Stark trap and dropping funnel.

其次，將混合物一邊進行50托爾(torr)之高真空下攪拌，一邊加熱至約50至60℃，並使環氧氯丙烷激烈迴流。53.0g之48%NaOH水溶液經2小時慢慢地 添加於混合物中。產生共沸物時，水/環氧氯丙烷混合物中，將環氧氯丙烷一邊回到反應系統，一邊繼續攪拌。添加終了後，繼續攪拌3小時。其次將反應混合物冷卻至室溫後加入氯仿500mL，並以500mL之水洗淨4次。將所得之有機相溶劑經減壓餾去後除去，得到129.0g之淡黃色黏稠物的樹脂2。 Next, the mixture was heated to about 50 to 60 ° C while stirring under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 53.0g of 48% NaOH aqueous solution slowly over 2 hours Add to the mixture. When an azeotrope is produced, in the water/epichlorohydrin mixture, the epichlorohydrin is continuously stirred while returning to the reaction system. After the addition was completed, stirring was continued for 3 hours. Next, the reaction mixture was cooled to room temperature, and then 500 mL of chloroform was added, and washed four times with 500 mL of water. The obtained organic phase solvent was distilled off under reduced pressure and then evaporated to give 129.0 g of pale yellow viscous resin.

(4)混合48.6g之樹脂2、甲基丙烯酸4.3g、三苯基次膦0.3g、及BHT 10mg，並在100℃下進行6小時攪拌。得到50.6g之淡黃色黏稠物的甲基丙烯酸化硬化性樹脂2。 (4) 48.6 g of the resin 2, 4.3 g of methacrylic acid, 0.3 g of triphenylphosphinium, and 10 mg of BHT were mixed, and stirred at 100 ° C for 6 hours. 50.6 g of a methacrylate-curable resin 2 of a pale yellow viscous material was obtained.

[合成例3]甲基丙烯酸化硬化性樹脂3 [Synthesis Example 3] methacrylate-curable resin 3

(1)將NISSO-PB G-1000(日本曹達公司製)350.0g(0.50當量/羥基)、環氧氯丙烷370.0g(8.0當量)、苯甲基三甲基銨氯化物9.3g(0.10當量)放入於附有機械攪拌機、溫度計、溫度調節器、凝縮器、Dean-Stark trap及滴液漏斗之2公升三口圓底燒瓶。 (1) NISSO-PB G-1000 (manufactured by Nippon Soda Co., Ltd.) 350.0 g (0.50 equivalent/hydroxyl), epichlorohydrin 370.0 g (8.0 equivalent), and benzyltrimethylammonium chloride 9.3 g (0.10 equivalent) ) Placed in a 2 liter three-neck round bottom flask with a mechanical stirrer, thermometer, thermostat, condenser, Dean-Stark trap and dropping funnel.

其次，將混合物一邊進行50托爾(torr)之高真空下攪拌，一邊加熱至約50至60℃，並使環氧氯丙烷激烈迴流。將75.0g之48%NaOH水溶液經2小時慢慢地添加於混合物中。產生共沸物時，水/環氧氯丙烷混合物中，將環氧氯丙烷一邊回到反應系統，一邊繼續攪拌。添加終了後，繼續攪拌3小時。 Next, the mixture was heated to about 50 to 60 ° C while stirring under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 75.0 g of a 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. When an azeotrope is produced, in the water/epichlorohydrin mixture, the epichlorohydrin is continuously stirred while returning to the reaction system. After the addition was completed, stirring was continued for 3 hours.

其次，將反應混合物冷卻至室溫，並加入氯 仿500mL後以500mL的水洗淨6次。將所得之有機相溶劑經減壓餾去後除去，得到298.0g之透明黏稠物的化合物E-3。 Next, the reaction mixture is cooled to room temperature and chlorine is added. After imitating 500 mL, it was washed 6 times with 500 mL of water. The obtained organic phase solvent was distilled off under reduced pressure, and then was evaporated to yield 298.0 g of the compound E-3.

(2)將化合物E-3(96.5g(0.10當量/環氧基))、雙酚A(68.5g(3.0當量))、苯甲基三甲基銨氯化物0.9g(0.050當量)及甲基異丁基酮100.0g放入於茄型燒瓶中，一邊加熱迴流至液溫為120℃，一邊進行20小時攪拌。液溫冷卻至60℃以下，加入氯仿300mL，並以1%NaOH水溶液300mL洗淨5次，以水300mL洗淨5次。 (2) Compound E-3 (96.5 g (0.10 equivalent/epoxy group)), bisphenol A (68.5 g (3.0 equivalent)), benzyltrimethylammonium chloride 0.9 g (0.050 equivalent) and 100.0 g of isobutyl ketone was placed in an eggplant type flask, and the mixture was heated and refluxed until the liquid temperature was 120 ° C, and the mixture was stirred for 20 hours. The liquid temperature was cooled to 60 ° C or less, and 300 mL of chloroform was added thereto, and the mixture was washed 5 times with 300 mL of a 1% NaOH aqueous solution, and washed with water 300 mL for 5 times.

於所得之有機相中加入硫酸鎂，乾燥後經過濾等濾出固體成分，將所得之有機相溶劑經減壓餾去後除去，得到75.5g之淡黃色透明黏稠物的合成中間體之反應物G-3。 Magnesium sulfate was added to the obtained organic phase, and after drying, the solid component was filtered off by filtration or the like, and the obtained organic phase solvent was distilled off under reduced pressure to give a reaction product of 75.5 g of a pale yellow transparent viscous synthetic intermediate. G-3.

(3)將反應物G-3(75.5g)、環氧氯丙烷(112.5g)、及苯甲基三甲基銨氯化物(2.8g)放入於附有機械攪拌機、溫度計、溫度調節器、凝縮器、Dean-Stark trap及滴液漏斗之500mL的三口圓底燒瓶中。 (3) The reactant G-3 (75.5g), epichlorohydrin (112.5g), and benzyltrimethylammonium chloride (2.8g) were placed in a mechanical mixer, thermometer, and temperature regulator. , a condenser, a Dean-Stark trap, and a dropping funnel in a 500 mL three-neck round bottom flask.

其次將混合物一邊進行50托爾(torr)之高真空下攪拌，一邊加熱至約50至60℃，並使環氧氯丙烷激烈迴流。將23.0g之48%NaOH水溶液經2小時慢慢地添加於混合物中。產生共沸物時，水/環氧氯丙烷混合物中，將環氧氯丙烷一邊回到反應系統，一邊繼續攪拌。添加終了後，繼續攪拌3小時。 Next, the mixture was stirred while stirring under a high vacuum of 50 torr, and heated to about 50 to 60 ° C, and the epichlorohydrin was vigorously refluxed. 23.0 g of a 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. When an azeotrope is produced, in the water/epichlorohydrin mixture, the epichlorohydrin is continuously stirred while returning to the reaction system. After the addition was completed, stirring was continued for 3 hours.

其次，將反應混合物冷卻至室溫，並加入氯仿300mL，以300mL的水洗淨6次。將所得之有機相溶劑經減壓餾去後除去，得到54.4g的淡黃色黏稠物之樹脂3。 Next, the reaction mixture was cooled to room temperature, and 300 mL of chloroform was added thereto, and the mixture was washed 6 times with 300 mL of water. The obtained organic phase solvent was distilled off under reduced pressure and then evaporated to yield 54.4 g of pale yellow viscous resin.

(4)混合50.0g的樹脂3、甲基丙烯酸3.3g、三苯基次膦0.2g、及BHT 10mg，並在100℃進行5小時攪拌。得到47.0g之淡黃色黏稠物的甲基丙烯酸化硬化性樹脂3。 (4) 50.0 g of the resin 3, 3.3 g of methacrylic acid, 0.2 g of triphenylphosphinium, and 10 mg of BHT were mixed, and stirred at 100 ° C for 5 hours. 47.0 g of a methacrylate-curable resin 3 of a pale yellow viscous material was obtained.

[合成例4]甲基丙烯酸化硬化性樹脂4 [Synthesis Example 4] methacrylate-curable resin 4

(1)將NISSO-PB GI-1000(日本曹達公司製)300.0g(0.40當量/羥基)、環氧氯丙烷296.0g(8.0當量)、苯甲基三甲基銨氯化物7.4g(0.10當量)放入於附有機械攪拌機、溫度計、溫度調節器、凝縮器、Dean-Stark trap及滴液漏斗之2公升三口圓底燒瓶。 (1) NISSO-PB GI-1000 (manufactured by Nippon Soda Co., Ltd.) 300.0 g (0.40 equivalent/hydroxyl group), epichlorohydrin 296.0 g (8.0 equivalent), and benzyltrimethylammonium chloride 7.4 g (0.10 equivalent) ) Placed in a 2 liter three-neck round bottom flask with a mechanical stirrer, thermometer, thermostat, condenser, Dean-Stark trap and dropping funnel.

其次將混合物一邊進行50托爾(torr)的高真空下攪拌，一邊加熱至約50至60℃，並使環氧氯丙烷激烈迴流。將60.0g的48%NaOH水溶液經2小時慢慢地添加於混合物中。產生共沸物時，水/環氧氯丙烷混合物中，將環氧氯丙烷一邊回到反應系統，一邊繼續攪拌。添加終了後，繼續攪拌3小時。 Next, the mixture was heated to about 50 to 60 ° C while stirring under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 60.0 g of a 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. When an azeotrope is produced, in the water/epichlorohydrin mixture, the epichlorohydrin is continuously stirred while returning to the reaction system. After the addition was completed, stirring was continued for 3 hours.

其此，將反應混合物冷卻至室溫，並加入氯仿500mL，以500mL的水洗淨6次。將所得之有機相溶劑經減壓餾去後除去，得到264.0g的透明黏稠物之化合 物E-4。 Thereafter, the reaction mixture was cooled to room temperature, and 500 mL of chloroform was added thereto, and the mixture was washed 6 times with 500 mL of water. The obtained organic phase solvent was distilled off under reduced pressure to give 264.0 g of a transparent viscous compound. E-4.

(2)將化合物E-4(80.0g(0.060當量/環氧基))、雙酚A(57.1g(4.0當量))、苯甲基三甲基銨氯化物0.9g(0.080當量)及甲基異丁基酮100.0g放入於茄型燒瓶，一邊加熱迴流至液溫為120℃，一邊進行20小時攪拌。液溫冷卻至60℃以下，加入氯仿300mL，並以1%NaOH水溶液300mL洗淨5次，以水300mL洗淨5次。 (2) Compound E-4 (80.0 g (0.060 equivalent/epoxy group)), bisphenol A (57.1 g (4.0 equivalent)), benzyltrimethylammonium chloride 0.9 g (0.080 equivalent) and 100.0 g of isopropyl isobutyl ketone was placed in an eggplant type flask, and the mixture was heated and refluxed until the liquid temperature was 120 ° C, and the mixture was stirred for 20 hours. The liquid temperature was cooled to 60 ° C or less, and 300 mL of chloroform was added thereto, and the mixture was washed 5 times with 300 mL of a 1% NaOH aqueous solution, and washed with water 300 mL for 5 times.

於所得之有機相中加入硫酸鎂，乾燥後藉由過濾等將固體成分濾出，將所得之有機相溶劑藉由減壓餾去除去，得到80.0g的淡黃色黏稠物之合成中間體的反應物G-4。 Magnesium sulfate was added to the obtained organic phase, and after drying, the solid component was filtered off by filtration or the like, and the obtained organic phase solvent was removed by distillation under reduced pressure to obtain a reaction mixture of 80.0 g of a pale yellow viscous compound. Matter G-4.

(3)將反應物G-4(80.0g)、環氧氯丙烷(88.8g)、及苯甲基三甲基銨氯化物(3.0g)放入於附有機械攪拌機、溫度計、溫度調節器、凝縮器、Dean-Stark trap及滴液漏斗之500mL的三口圓底燒瓶。 (3) The reactants G-4 (80.0 g), epichlorohydrin (88.8 g), and benzyltrimethylammonium chloride (3.0 g) were placed in a mechanical mixer, thermometer, and temperature regulator. 500 mL three-neck round bottom flask with condenser, Dean-Stark trap and dropping funnel.

其次將混合物一邊進行50托爾(torr)的高真空下攪拌，一邊加熱至約50至60℃，並使環氧氯丙烷激烈迴流。將24.0g的48%NaOH水溶液經2小時慢慢地添加於混合物中。產生共沸物時，水/環氧氯丙烷混合物中，將環氧氯丙烷一邊回到反應系統，一邊繼續攪拌。添加終了後，繼續攪拌3小時。 Next, the mixture was heated to about 50 to 60 ° C while stirring under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 24.0 g of a 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. When an azeotrope is produced, in the water/epichlorohydrin mixture, the epichlorohydrin is continuously stirred while returning to the reaction system. After the addition was completed, stirring was continued for 3 hours.

其次，將反應混合物冷卻至室溫，並加入氯仿300mL，再以300mL的水洗淨6次。將所得之有機相 溶劑經減壓餾去後除去，得到56.0g的淡黃色黏稠物之樹脂4。 Next, the reaction mixture was cooled to room temperature, and 300 mL of chloroform was added thereto, followed by washing 6 times with 300 mL of water. The resulting organic phase The solvent was distilled off under reduced pressure to give 56.0 g of pale yellow viscous resin.

(4)將50.0g的樹脂4、甲基丙烯酸3.0g、三苯基次膦0.2g、及BHT 10mg進行混合並在100℃進行12小時攪拌。得到47.0g之淡黃色黏稠物之甲基丙烯酸化硬化性樹脂4。 (4) 50.0 g of the resin 4, 3.0 g of methacrylic acid, 0.2 g of triphenylphosphinium, and 10 mg of BHT were mixed and stirred at 100 ° C for 12 hours. 47.0 g of a methacrylate-curable resin 4 of a pale yellow viscous material was obtained.

[合成例5]甲基丙烯酸化硬化性樹脂5 [Synthesis Example 5] methacrylate-curable resin 5

(1)將化合物E-2(96.0g(0.15當量/環氧基))、4-α-枯酚(30.0g(1.0當量))、苯甲基三甲基銨氯化物1.4g(0.050當量)放入於茄型燒瓶，一邊加熱迴流至液溫為120℃，一邊進行30小時攪拌。液溫冷卻至60℃以下，得到125.0g的淡黃色黏稠物之合成中間體的反應物G-5。 (1) Compound E-2 (96.0 g (0.15 equivalent/epoxy group)), 4-α- cumol (30.0 g (1.0 equivalent)), benzyltrimethylammonium chloride 1.4 g (0.050 equivalent) The flask was placed in an eggplant type flask and heated under reflux until the liquid temperature was 120 ° C, and the mixture was stirred for 30 hours. The liquid temperature was cooled to 60 ° C or lower to obtain 125.0 g of a reaction product G-5 of a synthetic intermediate of a pale yellow viscous material.

(2)將反應物G-5(125.0g)、環氧氯丙烷(150.0g)、及苯甲基三甲基銨氯化物(2.8g)放入於附有機械攪拌機、溫度計、溫度調節器、凝縮器、Dean-Stark trap及滴液漏斗之500mL三口圓底燒瓶。 (2) The reactants G-5 (125.0 g), epichlorohydrin (150.0 g), and benzyltrimethylammonium chloride (2.8 g) were placed in a mechanical mixer, thermometer, and temperature regulator. 500 mL three-neck round bottom flask with condenser, Dean-Stark trap and dropping funnel.

其次將混合物一邊進行50托爾(torr)的高真空下攪拌，一邊加熱至約50至60℃，並使環氧氯丙烷激烈迴流。將30.0g的48%NaOH水溶液經2小時慢慢地添加於混合物中。產生共沸物時，水/環氧氯丙烷混合物中，將環氧氯丙烷一邊回到反應系統，一邊繼續攪拌。添加終了後，繼續攪拌3小時。 Next, the mixture was heated to about 50 to 60 ° C while stirring under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 30.0 g of a 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. When an azeotrope is produced, in the water/epichlorohydrin mixture, the epichlorohydrin is continuously stirred while returning to the reaction system. After the addition was completed, stirring was continued for 3 hours.

其此，將反應混合物冷卻至室溫，並加入氯仿500mL，以500mL的水洗淨6次。將所得之有機相溶劑經減壓餾去後除去，得到130.0g的淡黃色黏稠物之樹脂5。 Thereafter, the reaction mixture was cooled to room temperature, and 500 mL of chloroform was added thereto, and the mixture was washed 6 times with 500 mL of water. The obtained organic phase solvent was distilled off under reduced pressure, and then evaporated to give 130.0 g of pale yellow viscous resin.

(3)將63.5g的樹脂5、甲基丙烯酸4.3g、三苯基次膦0.1g、及BHT 13mg進行混合後在100℃進行6小時攪拌。得到66.0g的淡黃色黏稠物之甲基丙烯酸化硬化性樹脂5。 (3) 63.5 g of the resin 5, 4.3 g of methacrylic acid, 0.1 g of triphenylphosphinium, and 13 mg of BHT were mixed, and the mixture was stirred at 100 ° C for 6 hours. 66.0 g of a methacrylate-curable resin 5 of a pale yellow viscous material was obtained.

[合成例6]甲基丙烯酸化硬化性樹脂6 [Synthesis Example 6] methacrylate-curable resin 6

(1)將化合物E-2(64.0g(0.10當量/環氧基))、及間苯二酚(27.5g(2.5當量))放入於茄型燒瓶，加熱攪拌至液溫為120℃。添加4%NaOH水溶液0.2g，在120℃進行24小時攪拌。冷卻至液溫為60℃以下，加入氯仿300mL，並以水300mL洗淨4次。 (1) Compound E-2 (64.0 g (0.10 equivalent/epoxy group)) and resorcin (27.5 g (2.5 equivalent)) were placed in an eggplant type flask, and the mixture was heated and stirred until the liquid temperature was 120 °C. 0.2 g of a 4% NaOH aqueous solution was added, and the mixture was stirred at 120 ° C for 24 hours. The mixture was cooled to a liquid temperature of 60 ° C or lower, and 300 mL of chloroform was added thereto, and washed with water 300 mL for 4 times.

於所得之有機相中加入硫酸鎂，乾燥後以過濾等將固體成分濾出，將所得之有機相溶劑經減壓餾去除去，得到60.5g的淡黃色透明黏稠物之合成中間體的反應物G-6。 Magnesium sulfate is added to the obtained organic phase, and after drying, the solid component is filtered off by filtration or the like, and the obtained organic phase solvent is removed by distillation under reduced pressure to obtain 60.5 g of a pale yellow transparent viscous synthetic intermediate. G-6.

(2)將反應物G-6(60.5g)、環氧氯丙烷(102.0g)、及苯甲基三甲基銨氯化物(3.4g)放入於附有機械攪拌機、溫度計、溫度調節器、凝縮器、Dean-Stark trap及滴液漏斗的500mL三口圓底燒瓶。 (2) The reactant G-6 (60.5 g), epichlorohydrin (102.0 g), and benzyltrimethylammonium chloride (3.4 g) were placed in a mechanical mixer, thermometer, and temperature regulator. 500 mL three-neck round bottom flask with condenser, Dean-Stark trap and dropping funnel.

其次將混合物一邊進行50托爾(torr)的高 真空下攪拌，一邊加熱至約50至60℃，並使環氧氯丙烷激烈迴流。將28.0g的48%NaOH水溶液經2小時慢慢地添加於混合物中。產生共沸物時，水/環氧氯丙烷混合物中，將環氧氯丙烷一邊回到反應系統，一邊繼續攪拌。添加終了後，繼續攪拌3小時。其次，冷卻反應混合物至室溫，加入氯仿300mL，並以300mL的水洗淨6次。將所得之有機相溶劑經減壓餾去後除去，得到48.0g的淡黃色黏稠物之樹脂6。 Next, the mixture is made to a height of 50 torr. The mixture was heated under vacuum to about 50 to 60 ° C, and the epichlorohydrin was vigorously refluxed. 28.0 g of a 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. When an azeotrope is produced, in the water/epichlorohydrin mixture, the epichlorohydrin is continuously stirred while returning to the reaction system. After the addition was completed, stirring was continued for 3 hours. Next, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and washed 6 times with 300 mL of water. The obtained organic phase solvent was distilled off under reduced pressure and then evaporated to yield 48.0 g of pale yellow viscous resin 6 .

(3)將44.6g之樹脂6、甲基丙烯酸4.3g、三苯基次膦0.1g、及BHT 10mg進行混合並在100℃進行14小時攪拌。得到42.8g的淡黃色黏稠物之甲基丙烯酸化硬化性樹脂6。 (3) 44.6 g of the resin 6, 4.3 g of methacrylic acid, 0.1 g of triphenylphosphinium, and 10 mg of BHT were mixed and stirred at 100 ° C for 14 hours. 42.8 g of a methacrylate-curable resin 6 of a pale yellow viscous material was obtained.

[合成例7]甲基丙烯酸化硬化性樹脂7 [Synthesis Example 7] methacrylate-curable resin 7

(1)將化合物E-2(53.0g(0.080當量/環氧基))、及2-(4-羥基苯基)乙醇(11.1g(1.0當量))放入於茄型燒瓶，加熱攪拌至液溫為120℃。添加苯甲基三甲基銨氯化物(3.0g(0.20當量))，在120℃進行24小時攪拌。冷卻至液溫為60℃以下，加入氯仿300mL，以1%NaOH水溶液300mL洗淨1次，以水300mL洗淨5次。 (1) Compound E-2 (53.0 g (0.080 equivalent/epoxy group)) and 2-(4-hydroxyphenyl)ethanol (11.1 g (1.0 equivalent)) were placed in an eggplant type flask, and the mixture was heated and stirred until The liquid temperature was 120 °C. Benzyltrimethylammonium chloride (3.0 g (0.20 equivalent)) was added, and the mixture was stirred at 120 ° C for 24 hours. After cooling to a liquid temperature of 60 ° C or less, 300 mL of chloroform was added, and the mixture was washed once with 300 mL of a 1% NaOH aqueous solution, and washed with water 300 mL for 5 times.

於所得之有機相中加入硫酸鎂，乾燥後藉由過濾等將固體成分濾出，將所得之有機相溶劑經減壓餾去除去，得到59.0g的淡黃色透明黏稠物之合成中間體的反 應物G-7。 Magnesium sulfate is added to the obtained organic phase, and after drying, the solid component is filtered off by filtration or the like, and the obtained organic phase solvent is removed by distillation under reduced pressure to give 59.0 g of a pale yellow transparent viscous compound. Reagent G-7.

(2)將反應物G-7(59.0g)、環氧氯丙烷(93.3g)、及苯甲基三甲基銨氯化物(3.1g)放入於附有機械攪拌機、溫度計、溫度調節器、凝縮器、Dean-Stark trap及滴液漏斗的500mL的三口圓底燒瓶。 (2) The reactants G-7 (59.0 g), epichlorohydrin (93.3 g), and benzyltrimethylammonium chloride (3.1 g) were placed in a mechanical mixer, thermometer, and temperature regulator. 500 mL three-neck round bottom flask with condenser, Dean-Stark trap and dropping funnel.

其次將混合物一邊進行50托爾(torr)的高真空下攪拌，一邊加熱至約50至60℃，並使環氧氯丙烷激烈迴流。將25.2g的48%NaOH水溶液經2小時慢慢地添加於混合物中。產生共沸物時，水/環氧氯丙烷混合物中，將環氧氯丙烷一邊回到反應系統，一邊繼續攪拌。添加終了後，繼續攪拌3小時。其次將反應混合物冷卻至室溫，加入氯仿300mL，並以300mL的水洗淨6次。將所得之有機相溶劑經減壓餾去後除去，得到50.5g的淡黃色黏稠物之樹脂7。 Next, the mixture was heated to about 50 to 60 ° C while stirring under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 25.2 g of a 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. When an azeotrope is produced, in the water/epichlorohydrin mixture, the epichlorohydrin is continuously stirred while returning to the reaction system. After the addition was completed, stirring was continued for 3 hours. Next, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed 6 times with 300 mL of water. The obtained organic phase solvent was distilled off under reduced pressure and then evaporated to yield 50.5 g of pale yellow viscous resin.

(3)將47.3g的樹脂7、甲基丙烯酸5.2g、三苯基次膦0.1g、及BHT 10mg進行混合並在100℃進行7小時攪拌。得到51.0g的淡黃色黏稠物之甲基丙烯酸化硬化性樹脂7。 (3) 47.3 g of the resin 7, 5.2 g of methacrylic acid, 0.1 g of triphenylphosphinium, and 10 mg of BHT were mixed and stirred at 100 ° C for 7 hours. 51.0 g of a methacrylate-curable resin 7 of a pale yellow viscous material was obtained.

[合成例8]甲基丙烯酸化硬化性樹脂8 [Synthesis Example 8] methacrylate-curable resin 8

(1)將化合物E-2(94.0g(0.15當量/環氧基))、及酚(21.2g(1.5當量))放入於茄型燒瓶中，加熱攪拌至液溫為120℃。添加苯甲基三甲基銨氯化物(2.8g(0.10當量))，在120℃進行24小時攪拌。將液溫冷 卻至60℃以下，加入甲基異丁基酮300mL，以1%NaOH水溶液300mL洗淨2次，以水300mL洗淨4次。 (1) Compound E-2 (94.0 g (0.15 equivalent/epoxy group)) and phenol (21.2 g (1.5 equivalent)) were placed in an eggplant type flask, and the mixture was heated and stirred until the liquid temperature was 120 °C. Benzyltrimethylammonium chloride (2.8 g (0.10 equivalent)) was added, and the mixture was stirred at 120 ° C for 24 hours. Cool the liquid However, to 60 ° C or less, 300 mL of methyl isobutyl ketone was added, and the mixture was washed twice with 300 mL of a 1% NaOH aqueous solution, and washed with water 300 mL for 4 times.

於所得之有機相中加入硫酸鎂，並乾燥後藉由過濾等濾出固體成分，將所得之有機相溶劑藉由減壓餾去除去，得到90.0g的淡黃色透明黏稠物之合成中間體的反應物G-8。 Magnesium sulfate is added to the obtained organic phase, and after drying, the solid component is filtered off by filtration or the like, and the obtained organic phase solvent is removed by distillation under reduced pressure to obtain a synthetic intermediate of 90.0 g of a pale yellow transparent viscous material. Reactant G-8.

(2)將反應物G-8(90.0g)、環氧氯丙烷(130.0g)、及苯甲基三甲基銨氯化物(2.6g)放入於附有機械攪拌機、溫度計、溫度調節器、凝縮器、Dean-Stark trap及滴液漏斗之500mL的三口圓底燒瓶。 (2) The reactants G-8 (90.0 g), epichlorohydrin (130.0 g), and benzyltrimethylammonium chloride (2.6 g) were placed in a mechanical mixer, thermometer, and temperature regulator. 500 mL three-neck round bottom flask with condenser, Dean-Stark trap and dropping funnel.

其次將混合物一邊進行50托爾(torr)的高真空下攪拌，一邊加熱至約50至60℃，並使環氧氯丙烷激烈迴流。將21.0g的48%NaOH水溶液經2小時慢慢地添加於混合物中。產生共沸物時，水/環氧氯丙烷混合物中，將環氧氯丙烷一邊回到反應系統，一邊繼續攪拌。添加終了後，繼續攪拌3小時。其次將反應混合物冷卻至室溫，加入氯仿300mL，並以300mL的水洗淨6次。將所得之有機相溶劑經減壓餾去後除去，得到80g的淡黃色黏稠物之樹脂8。 Next, the mixture was heated to about 50 to 60 ° C while stirring under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 21.0 g of a 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. When an azeotrope is produced, in the water/epichlorohydrin mixture, the epichlorohydrin is continuously stirred while returning to the reaction system. After the addition was completed, stirring was continued for 3 hours. Next, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed 6 times with 300 mL of water. The obtained organic phase solvent was distilled off under reduced pressure, and then evaporated to give 80 g of pale yellow viscous resin.

(3)將57.6g的樹脂8、甲基丙烯酸3.5g、三苯基次膦0.1g、及BHT 10mg進行混合並在100℃下進行13小時攪拌。得到59.2g的淡黃色黏稠物之甲基丙烯酸化硬化性樹脂8。 (3) 57.6 g of the resin 8, 3.5 g of methacrylic acid, 0.1 g of triphenylphosphinium, and 10 mg of BHT were mixed and stirred at 100 ° C for 13 hours. 59.2 g of a methacrylate-curable resin 8 of a pale yellow viscous material was obtained.

[合成例9]甲基丙烯酸化硬化性樹脂9 [Synthesis Example 9] methacrylate-curable resin 9

(1)將化合物E-2(63.0g(0.10當量/環氧基))、及9,9-雙(4-羥基-3-甲基苯基)茀(95.0g(2.5當量))、1-丁醇(80.0g)放入茄型燒瓶，在120℃進行加熱迴流。添加苯甲基三甲基銨氯化物(0.9g(0.050當量))，在120℃進行20小時攪拌。冷卻至液溫為60℃以下，加入氯仿300mL，以1%NaOH水溶液300mL洗淨14次，以水300mL洗淨5次。 (1) Compound E-2 (63.0 g (0.10 equivalent/epoxy group)), and 9,9-bis(4-hydroxy-3-methylphenyl)anthracene (95.0 g (2.5 equivalent)), 1 Butanol (80.0 g) was placed in an eggplant type flask, and heated under reflux at 120 °C. Benzyltrimethylammonium chloride (0.9 g (0.050 equivalent)) was added, and the mixture was stirred at 120 ° C for 20 hours. After cooling to a liquid temperature of 60 ° C or less, 300 mL of chloroform was added, and the mixture was washed 14 times with 300 mL of a 1% NaOH aqueous solution, and washed with water 300 mL for 5 times.

於所得之有機相中加入硫酸鎂，乾燥後以過濾等濾出固體成分，將所得之有機相溶劑藉由減壓餾去除去，得到56.0g的淡黃色透明黏稠物之合成中間體的反應物G-9。 Magnesium sulfate is added to the obtained organic phase, and after drying, the solid component is filtered off by filtration or the like, and the obtained organic phase solvent is removed by distillation under reduced pressure to give 56.0 g of a pale yellow transparent viscous synthetic intermediate. G-9.

(2)將反應物G-9(56.0g)、環氧氯丙烷(111.0g)、及苯甲基三甲基銨氯化物(2.2g)放入於附有機械攪拌機、溫度計、溫度調節器、凝縮器、Dean-Stark trap及滴液漏斗之500mL的三口圓底燒瓶。 (2) The reactants G-9 (56.0 g), epichlorohydrin (111.0 g), and benzyltrimethylammonium chloride (2.2 g) were placed in a mechanical mixer, thermometer, and temperature regulator. 500 mL three-neck round bottom flask with condenser, Dean-Stark trap and dropping funnel.

其次將混合物一邊進行50托爾(torr)的高真空下攪拌，一邊加熱至約50至60℃，並使環氧氯丙烷激烈迴流。將18.0g的48%NaOH水溶液經2小時慢慢地添加於混合物中。產生共沸物時，水/環氧氯丙烷混合物中，將環氧氯丙烷一邊回到反應系統，一邊繼續攪拌。添加終了後，繼續攪拌3小時。其次將反應混合物冷卻至室溫，加入氯仿300mL，並以300mL的水洗淨6次。將所得之有機相溶劑經減壓餾去後除去，得到54.0g的淡黃色 黏稠物之樹脂9。 Next, the mixture was heated to about 50 to 60 ° C while stirring under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 18.0 g of a 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. When an azeotrope is produced, in the water/epichlorohydrin mixture, the epichlorohydrin is continuously stirred while returning to the reaction system. After the addition was completed, stirring was continued for 3 hours. Next, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed 6 times with 300 mL of water. The obtained organic phase solvent was distilled off under reduced pressure to give 54.0 g of pale yellow. Viscosity resin 9.

(3)將51.0g的樹脂9、甲基丙烯酸4.3g、三苯基次膦0.1g、及BHT 10mg進行混合並在100℃進行9小時攪拌。得到49.8g的淡黃色黏稠物之甲基丙烯酸化硬化性樹脂9。 (3) 51.0 g of the resin 9, 4.3 g of methacrylic acid, 0.1 g of triphenylphosphinium, and 10 mg of BHT were mixed and stirred at 100 ° C for 9 hours. 49.8 g of a methacrylate-curable resin 9 of a pale yellow viscous material was obtained.

[合成例10]甲基丙烯酸化硬化性樹脂10 [Synthesis Example 10] methacrylate-curable resin 10

(1)將PEG-2000(東邦化學工業公司製)1000.0g(1.0當量/羥基)、環氧氯丙烷925.0g(10當量)、苯甲基三甲基銨氯化物18.6g(0.10當量)放於附有機械攪拌機、溫度計、溫度調節器、凝縮器、Dean-Stark trap及滴液漏斗之5公升三口圓底燒瓶。 (1) PEG-2000 (manufactured by Toho Chemical Co., Ltd.) 1000.0 g (1.0 equivalent/hydroxyl group), epichlorohydrin 925.0 g (10 equivalents), and benzyltrimethylammonium chloride 18.6 g (0.10 equivalents) A 5 liter three-neck round bottom flask with mechanical stirrer, thermometer, thermostat, condenser, Dean-Stark trap and dropping funnel.

其次將混合物一邊進行50托爾(torr)的高真空下攪拌，一邊加熱至約50至60℃，並使環氧氯丙烷激烈迴流。將150.0g的48%NaOH水溶液經2小時慢慢地添加於混合物中。產生共沸物時，水/環氧氯丙烷混合物中，將環氧氯丙烷一邊回到反應系統，一邊繼續攪拌。 Next, the mixture was heated to about 50 to 60 ° C while stirring under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 150.0 g of a 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. When an azeotrope is produced, in the water/epichlorohydrin mixture, the epichlorohydrin is continuously stirred while returning to the reaction system.

添加終了後，繼續攪拌3小時。其次，將反應混合物冷卻至室溫後加入氯仿，以1L的水洗淨3次。將所得之有機相溶劑經減壓餾去後除去，得到760.0g的白色蠟狀固體之化合物E-5。 After the addition was completed, stirring was continued for 3 hours. Next, the reaction mixture was cooled to room temperature, and then chloroform was added thereto, and the mixture was washed three times with 1 L of water. The obtained organic phase solvent was evaporated under reduced pressure, and then evaporated to ethylamine.

(2)將化合物E-5(220.0g(0.20當量/環氧基))、及雙酚A(31.0g(1.4當量))放於茄型燒瓶，加熱攪拌至液溫為110℃。添加苯甲基三甲基銨氯化物 1.9g，並在110℃進行20小時攪拌。 (2) Compound E-5 (220.0 g (0.20 equivalent/epoxy group)) and bisphenol A (31.0 g (1.4 equivalent)) were placed in an eggplant type flask, and the mixture was heated and stirred until the liquid temperature was 110 °C. Addition of benzyltrimethylammonium chloride 1.9 g and stirred at 110 ° C for 20 hours.

冷卻至液溫為60℃以下，加入氯仿300mL，以1%NaOH水溶液300mL洗淨3次，以水300mL洗淨6次。 After cooling to a liquid temperature of 60 ° C or less, 300 mL of chloroform was added, and the mixture was washed three times with 300 mL of a 1% NaOH aqueous solution, and washed three times with 300 mL of water.

於所得之有機相中加入硫酸鎂，乾燥後以過濾等將固體成分濾出，將所得之有機相溶劑經減壓餾去除去，得到110.0g的淡黃色透明黏稠物之合成中間體的反應物G-10。 Magnesium sulfate was added to the obtained organic phase, and after drying, the solid component was filtered off by filtration or the like, and the obtained organic phase solvent was removed by distillation under reduced pressure to obtain a reaction product of 110.0 g of a pale yellow transparent viscous synthetic intermediate. G-10.

(3)將反應物G-10(108.0g)、環氧氯丙烷(175.0g)、及苯甲基三甲基銨氯化物(2.3g)放入於附有機械攪拌機、溫度計、溫度調節器、凝縮器、Dean-Stark trap及滴液漏斗之1公升三口圓底燒瓶。 (3) The reactants G-10 (108.0 g), epichlorohydrin (175.0 g), and benzyltrimethylammonium chloride (2.3 g) were placed in a mechanical mixer, thermometer, and temperature regulator. 1 liter three-neck round bottom flask with condenser, Dean-Stark trap and dropping funnel.

其次將混合物一邊進行50托爾(torr)的高真空下攪拌，一邊加熱至約50至60℃，並使環氧氯丙烷激烈迴流。將19.0g的48%NaOH水溶液經2小時慢慢地添加於混合物中。產生共沸物時，水/環氧氯丙烷混合物中，將環氧氯丙烷一邊回到反應系統，一邊繼續攪拌。添加終了後，繼續攪拌3小時。 Next, the mixture was heated to about 50 to 60 ° C while stirring under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 19.0 g of a 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. When an azeotrope is produced, in the water/epichlorohydrin mixture, the epichlorohydrin is continuously stirred while returning to the reaction system. After the addition was completed, stirring was continued for 3 hours.

其次將反應混合物冷卻至室溫，加入氯仿300mL，並以300mL的水洗淨6次。將所得之有機相溶劑經減壓餾去後除去，得到92.0g的白色蠟狀固體之樹脂10。 Next, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed 6 times with 300 mL of water. The obtained organic phase solvent was distilled off under reduced pressure, and then evaporated to yield 92.0 g of white waxy solid resin.

(4)將21.7g的樹脂10、甲基丙烯酸1.1g、苯甲基三甲基銨氯化物0.1g、甲苯50.0g、及BHT 15mg 進行混合並在100℃進行7小時攪拌。其次，將反應混合物冷卻至室溫，並加入氯仿100mL，以100mL的水洗淨3次。將所得之有機相溶劑經減壓餾去後除去，得到17.0g的白色蠟狀固體之甲基丙烯酸化硬化性樹脂10。 (4) 21.7 g of resin 10, 1.1 g of methacrylic acid, 0.1 g of benzyltrimethylammonium chloride, 50.0 g of toluene, and 15 mg of BHT The mixture was mixed and stirred at 100 ° C for 7 hours. Next, the reaction mixture was cooled to room temperature, and 100 mL of chloroform was added thereto, and the mixture was washed three times with 100 mL of water. The obtained organic phase solvent was distilled off under reduced pressure, and then removed to yield 17.0 g of a white waxy solid methacrylate-hardened resin.

[合成例11]甲基丙烯酸化硬化性樹脂11 [Synthesis Example 11] methacrylate-curable resin 11

(1)將聚四伸甲基醚甘醇(PTMG)2000(三菱化學公司製)500.0g(0.50當量/羥基)、環氧氯丙烷463.0g(10當量)、苯甲基三甲基銨氯化物9.3g(0.10當量)放入於附有機械攪拌機、溫度計、溫度調節器、凝縮器、Dean-Stark trap及滴液漏斗之2公升三口圓底燒瓶。 (1) Polytetramethyl ether glycol (PTMG) 2000 (manufactured by Mitsubishi Chemical Corporation) 500.0 g (0.50 equivalent/hydroxyl group), epichlorohydrin 463.0 g (10 equivalents), benzyltrimethylammonium chloride 9.3 g (0.10 equivalent) was placed in a 2 liter three-neck round bottom flask equipped with a mechanical stirrer, thermometer, thermostat, condenser, Dean-Stark trap and dropping funnel.

其次將混合物一邊進行50托爾(torr)的高真空下攪拌，一邊加熱至約50至60℃，並使環氧氯丙烷激烈迴流。將75.0g的48%NaOH水溶液經2小時慢慢地添加於混合物中。產生共沸物時，水/環氧氯丙烷混合物中，將環氧氯丙烷一邊回到反應系統，一邊繼續攪拌。 Next, the mixture was heated to about 50 to 60 ° C while stirring under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 75.0 g of a 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. When an azeotrope is produced, in the water/epichlorohydrin mixture, the epichlorohydrin is continuously stirred while returning to the reaction system.

添加終了後，繼續攪拌3小時。其次，將反應混合物冷卻至室溫後加入氯仿，以1L的水洗淨3次。將所得之有機相溶劑經減壓餾去後除去，得到450.0g的白色蠟狀固體之化合物E-6。 After the addition was completed, stirring was continued for 3 hours. Next, the reaction mixture was cooled to room temperature, and then chloroform was added thereto, and the mixture was washed three times with 1 L of water. The obtained organic phase solvent was evaporated under reduced pressure, and then evaporated, m.

(2)將化合物E-6(127.0g(0.10當量/環氧基))、及雙酚A(15.0g(1.4當量))放入於茄型燒瓶，加熱攪拌至液溫為110℃。添加苯甲基三甲基銨氯化物0.9g，在110℃進行20小時攪拌。 (2) Compound E-6 (127.0 g (0.10 equivalent/epoxy group)) and bisphenol A (15.0 g (1.4 equivalent)) were placed in an eggplant type flask, and the mixture was heated and stirred until the liquid temperature was 110 °C. 0.9 g of benzyltrimethylammonium chloride was added, and the mixture was stirred at 110 ° C for 20 hours.

冷卻至液溫為60℃以下，加入氯仿300mL，以1%NaOH水溶液300mL洗淨3次，以水300mL洗淨6次。 After cooling to a liquid temperature of 60 ° C or less, 300 mL of chloroform was added, and the mixture was washed three times with 300 mL of a 1% NaOH aqueous solution, and washed three times with 300 mL of water.

於所得之有機相中加入硫酸鎂，乾燥後以過濾等將固體成分濾出，將所得之有機相溶劑經減壓餾去除去，得到120.0g的淡黃色透明黏稠物之合成中間體的反應物G-11。 Magnesium sulfate is added to the obtained organic phase, and after drying, the solid component is filtered off by filtration, and the obtained organic phase solvent is removed by distillation under reduced pressure to obtain a reaction product of 120.0 g of a pale yellow transparent viscous synthetic intermediate. G-11.

(3)將反應物G-11(117.0g)、環氧氯丙烷(125.0g)、及苯甲基三甲基銨氯化物(2.5g)放入於附有機械攪拌機、溫度計、溫度調節器、凝縮器、Dean-Stark trap及滴液漏斗的1公升三口圓底燒瓶。 (3) The reactants G-11 (117.0 g), epichlorohydrin (125.0 g), and benzyltrimethylammonium chloride (2.5 g) were placed in a mechanical mixer, thermometer, and temperature regulator. 1 liter three-neck round bottom flask with condenser, Dean-Stark trap and dropping funnel.

其次將混合物一邊進行50托爾(torr)的高真空下攪拌，一邊加熱至約50至60℃，並使環氧氯丙烷激烈迴流。將20.0g的48%NaOH水溶液經2小時慢慢地添加於混合物中。產生共沸物時，水/環氧氯丙烷混合物中，將環氧氯丙烷一邊回到反應系統，一邊繼續攪拌。添加終了後，繼續攪拌3小時。 Next, the mixture was heated to about 50 to 60 ° C while stirring under a high vacuum of 50 torr, and the epichlorohydrin was vigorously refluxed. 20.0 g of a 48% aqueous NaOH solution was slowly added to the mixture over 2 hours. When an azeotrope is produced, in the water/epichlorohydrin mixture, the epichlorohydrin is continuously stirred while returning to the reaction system. After the addition was completed, stirring was continued for 3 hours.

其次將反應混合物冷卻至室溫，加入氯仿300mL，並以300mL的水洗淨6次。將所得之有機相溶劑經減壓餾去除去，得到92.0g的淡黃色黏稠物之樹脂11。 Next, the reaction mixture was cooled to room temperature, 300 mL of chloroform was added, and the mixture was washed 6 times with 300 mL of water. The obtained organic phase solvent was evaporated under reduced pressure to give 92.0 g of pale yellow viscous resin.

(4)將55.0g的樹脂11、甲基丙烯酸2.6g、三苯基次膦0.1g、及BHT 10mg進行混合並在100℃進行7小時攪拌。得到54.0g的淡黃色黏稠物之甲基丙烯酸化硬化性樹脂11。 (4) 55.0 g of the resin 11, 2.6 g of methacrylic acid, 0.1 g of triphenylphosphinium, and 10 mg of BHT were mixed and stirred at 100 ° C for 7 hours. 54.0 g of a methacrylate-curable resin 11 of a pale yellow viscous material was obtained.

[光聚合起始劑之製造] [Manufacture of photopolymerization initiator]

在實施例及比較例所使用之光聚合起始劑如以下製造。 The photopolymerization initiators used in the examples and comparative examples were produced as follows.

<光聚合起始劑1之製造> <Manufacture of Photopolymerization Initiator 1>

將DenacolEX-830(PEG400之二縮水甘油基醚Nagase Chemtex公司製)26.8g(0.10當量/環氧基)、4-二甲基胺基安息香酸16.5g(1.0當量)、苯甲基三甲基銨氯化物3.7g(0.20當量)、MIBK(甲基異丁基酮)25.0g放入於燒瓶中，在110℃進行24小時攪拌。將反應混合物冷卻至室溫，溶解於氯仿50g中，再以水100ml洗淨6次。將有機相溶劑減壓餾去後得到35.3g的光聚合起始劑1。 Denacol EX-830 (manufactured by PEG400 diglycidyl ether Nagase Chemtex) 26.8 g (0.10 equivalent/epoxy group), 4-dimethylamino benzoic acid 16.5 g (1.0 equivalent), benzyltrimethyl 3.7 g (0.20 equivalent) of ammonium chloride and 25.0 g of MIBK (methyl isobutyl ketone) were placed in a flask, and stirred at 110 ° C for 24 hours. The reaction mixture was cooled to room temperature, dissolved in 50 g of chloroform, and washed 6 times with 100 ml of water. The organic phase solvent was distilled off under reduced pressure to give 35.3 g of photopolymerization initiator.

<光聚合起始劑2之製造> <Manufacture of Photopolymerization Initiator 2>

將DenacolEX-830(PEG400之二縮水甘油基醚Nagase Chemtex公司製)26.8g(0.10當量/環氧基)、2-羥基-9H-噻噸-9-酮22.8g(1.0當量)、苯甲基三甲基銨氯化物3.7g(0.20當量)、MIBK 40.0g放入於燒瓶中，在110℃進行72小時攪拌。將反應混合物冷卻至室溫，溶解於氯仿50g，以水100ml洗淨6次。將有機相溶劑減壓餾去，得到36.2g的光聚合起始劑2。 Denacol EX-830 (manufactured by PEG400 diglycidyl ether Nagase Chemtex) 26.8 g (0.10 equivalent/epoxy group), 2-hydroxy-9H-thioxan-9-one 22.8 g (1.0 equivalent), benzyl group 3.7 g (0.20 equivalent) of trimethylammonium chloride and 40.0 g of MIBK were placed in a flask, and stirred at 110 ° C for 72 hours. The reaction mixture was cooled to room temperature, dissolved in 50 g of chloroform, and washed 6 times with 100 ml of water. The organic phase solvent was distilled off under reduced pressure to give 36.2 g of photopolymerization initiator.

[實施例1~11及比較例1] [Examples 1 to 11 and Comparative Example 1]

將以合成例及比較合成例所製造之各部分甲基丙烯酸化雙酚A型環氧樹脂、甲基丙烯酸化硬化性樹脂1~11、光聚合起始劑1及2、與硬化劑之EH-5030S(ADEKA製(聚胺系化合物))，以如下述表1所示配合量(重量份)進行混合後，使用3根輥混合機(井上製作所製C-43/4×10)充分地混練後得到實施例1~11及比較例1之液晶密封劑組成物。 Each part of the methacrylated bisphenol A type epoxy resin, the methacrylate-curable resin 1-11, the photopolymerization initiator 1 and 2, and the hardening agent EH manufactured by the synthesis example and the comparative synthesis example. -5030S (manufactured by ADEKA (polyamine compound)) was mixed with a blending amount (parts by weight) as shown in the following Table 1, and then fully used with three roll mixers (C-43/4×10 manufactured by Inoue Co., Ltd.). After the kneading, the liquid crystal sealant compositions of Examples 1 to 11 and Comparative Example 1 were obtained.

對於以合成例及比較合成例所製造之各化合物、以及此等的液晶密封劑組成物藉由以下試驗進行評估。 Each of the compounds produced by the synthesis examples and the comparative synthesis examples, and the liquid crystal sealant compositions thereof were evaluated by the following tests.

[試驗條件] [Test conditions]

對於部分甲基丙烯酸化雙酚A型環氧樹脂、甲基丙烯酸化硬化性樹脂1~9、及1，測定環氧當量、黏度及NI點變化，對於甲基丙烯酸化硬化性樹脂10測定環氧當量及NI點變化，對於光聚合起始劑1及2測定黏度及NI點變化，對於硬化劑(EH-5030S)測定NI點變化，對於實施例1~11及比較例1所製造之液晶密封劑組成物的硬化物，測定其Tg及各種溫度中之貯藏彈性率。 For the partially methacrylated bisphenol A type epoxy resin and the methacrylic acid curable resin 1 to 9, and 1, the epoxy equivalent, the viscosity, and the change of the NI point were measured, and the ring of the methacrylate-curable resin 10 was measured. Oxygen equivalent and NI point change, viscosity and NI point change were measured for photopolymerization initiators 1 and 2, and NI point change was measured for hardener (EH-5030S), and liquid crystals manufactured in Examples 1 to 11 and Comparative Example 1 were measured. The cured product of the sealant composition was measured for its Tg and storage modulus at various temperatures.

(1)環氧當量測定 (1) Determination of epoxy equivalent

以JISK7236：2001記載之條件進行測定。 The measurement was carried out under the conditions described in JIS K7236:2001.

(2)黏度測定 (2) Viscosity measurement

使用E型黏度計(東機產業公司製RE105U)在25℃下進行測定。 The measurement was performed at 25 ° C using an E-type viscometer (RE105U manufactured by Toki Sangyo Co., Ltd.).

如以下選擇轉子及轉數。 Select the rotor and number of revolutions as follows.

部分甲基丙烯酸化雙酚A型環氧樹脂：3°×R7.7轉子、轉數10rpm Partially methacrylated bisphenol A epoxy resin: 3° × R7.7 rotor, 10 rpm

甲基丙烯酸化硬化性樹脂1：3°×R7.7轉子、轉數15rpm Methacrylate-hardening resin 1: 3° × R7.7 rotor, number of revolutions 15 rpm

甲基丙烯酸化硬化性樹脂2：3°×R7.7轉子、轉數15rpm Methacrylic acid curable resin 2: 3° × R7.7 rotor, number of revolutions 15 rpm

甲基丙烯酸化硬化性樹脂3：3°×R7.7轉子、轉數0.5rpm Methacrylate-hardening resin 3: 3° × R7.7 rotor, revolution 0.5 rpm

甲基丙烯酸化硬化性樹脂4：3°×R7.7轉子、轉數0.2rpm Methyl acrylate-hardening resin 4: 3° × R7.7 rotor, number of revolutions 0.2 rpm

甲基丙烯酸化硬化性樹脂5：1°34’×R24轉子、轉數2.0rpm Methacrylate-hardening resin 5: 1°34'×R24 rotor, number of revolutions 2.0 rpm

甲基丙烯酸化硬化性樹脂6：3°×R14轉子、轉數5.0rpm Methacrylate-hardening resin 6: 3° × R14 rotor, revolutions 5.0 rpm

甲基丙烯酸化硬化性樹脂7：1°34’×R24轉子、轉數5.0rpm Methacrylate sclerosing resin 7: 1° 34' × R24 rotor, revolutions 5.0 rpm

甲基丙烯酸化硬化性樹脂8：1°34’×R24轉子、轉數2.0rpm Methacrylate-hardening resin 8: 1°34'×R24 rotor, number of revolutions 2.0 rpm

甲基丙烯酸化硬化性樹脂9：3°×R7.7轉子、轉數2.0rpm Methacrylate-hardening resin 9: 3° × R7.7 rotor, number of revolutions 2.0 rpm

甲基丙烯酸化硬化性樹脂11：3°×R7.7轉子、轉數15rpm Methacrylate-hardening resin 11: 3° × R7.7 rotor, number of revolutions 15 rpm

(3)NI點變化測定 (3) NI point change measurement

部分甲基丙烯酸化雙酚A型環氧樹脂、甲基丙烯酸化硬化性樹脂1~11、光聚合起始劑1及2、硬化劑(EH-5030S)於各樣品瓶中加入0.1g，再加入液晶(MLC-11900-080，默克公司製)1g。將此瓶在120℃烤箱中放置1小時，之後在室溫下靜置而恢復至室溫(25℃)後，取出液晶部分，藉由0.2μm濾器過濾，作為評估用液晶試品。 Partially methacrylated bisphenol A epoxy resin, methacrylic acid curable resin 1-11, photopolymerization initiator 1 and 2, hardener (EH-5030S) were added to each sample vial 0.1g, and then Liquid crystal (MLC-11900-080, manufactured by Merck & Co., Inc.) was added in an amount of 1 g. The bottle was allowed to stand in an oven at 120 ° C for 1 hour, and then allowed to stand at room temperature to return to room temperature (25 ° C), and then the liquid crystal portion was taken out and filtered through a 0.2 μm filter to obtain a liquid crystal sample for evaluation.

NI點之測定為使用差示掃描型熱量計(DSC，珀金埃爾默公司製、PYRIS6)，將評估用液晶試樣10mg封入於鋁樣品盤，在昇溫速度5℃/分之條件下進行。且將上述液晶10mg封入於鋁樣品盤，以昇溫速度5℃/分之條件下進行測定之結果作為對照組。 The NI point was measured by using a differential scanning calorimeter (DSC, manufactured by PerkinElmer, PYRIS6), and 10 mg of the liquid crystal sample for evaluation was sealed in an aluminum sample pan at a temperature elevation rate of 5 ° C /min. . Further, 10 mg of the above liquid crystal was sealed in an aluminum sample pan, and the measurement was carried out under the conditions of a temperature increase rate of 5 ° C /min.

對照組的吸熱吸收峰頂(相轉移溫度)TB與評估用液晶之吸熱吸收峰頂(相轉移溫度)TE的差TE-TB作為NI點變化。由抑制液晶密封劑之含有成分對於液晶之溶離，穩定地確保液晶之配向，提高顯示特性之觀點來看，NI點變化之絶對值越小越佳。 The difference TE-TB of the endothermic absorption peak (phase transition temperature) TB of the control group and the endothermic absorption peak (phase transition temperature) TE of the liquid crystal for evaluation was changed as the NI point. From the viewpoint of suppressing the dissolution of the liquid crystal sealing agent-containing component to the liquid crystal, stably ensuring the alignment of the liquid crystal, and improving the display characteristics, the absolute value of the change in the NI point is preferably as small as possible.

(4)Tg測定 (4) Tg determination

對於以實施例1~11及比較例1所製造之液晶密封劑 組成物，注入於長度5cm、寬度5mm、厚度0.5mm之型，將紫外線(以UV照射裝置：UVX-01224S1、USHIO電機公司製、100mW/cm2/365nm進行30秒)以積分光量3000mJ/cm2照射並使其硬化後，在120℃之熱風烤箱中進行1小時熱硬化，作成硬化物試驗片。 The liquid crystal sealing agent compositions manufactured in Examples 1 to 11 and Comparative Example 1 were injected into a type having a length of 5 cm, a width of 5 mm, and a thickness of 0.5 mm, and ultraviolet rays were used (UV irradiation apparatus: UVX-01224S1, manufactured by USHIO Electric Co., Ltd.). At 100 mW/cm 2 /365 nm for 30 seconds, the integrated light amount was 3000 mJ/cm 2 and hardened, and then heat-cured in a hot air oven at 120 ° C for 1 hour to prepare a cured test piece.

將所得之硬化物試驗片使用動態黏彈性測定裝置(DMA、精工電子公司製之DMS6100)，將變形模式拉伸，在頻率數1.0Hz下，於-50℃~100℃之範圍以2℃/分使其昇溫下進行測定。將所得之結果的損失正接tanδ中之吸收峰頂溫度作為Tg。 The obtained cured test piece was stretched in a deformation mode using a dynamic viscoelasticity measuring apparatus (DMA, DMS6100 manufactured by Seiko Instruments Inc.) at a frequency of 1.0 Hz at a temperature of -50 ° C to 100 ° C at 2 ° C / The measurement was carried out by subjecting it to temperature rise. The loss of the obtained result was taken as the Tg of the absorption peak top temperature in tan δ.

(5)貯藏彈性率測定 (5) Determination of storage modulus

對於在實施例1~11及比較例1所製造之液晶密封劑組成物，在與Tg之相同條件下進行硬化物試驗片之作成及藉由動態黏彈性測定裝置(DMA、精工電子公司製之DMS6100)進行測定。對於所得結果中，取出在各溫度之貯藏彈性率值。 The liquid crystal sealant compositions produced in Examples 1 to 11 and Comparative Example 1 were subjected to the preparation of a cured test piece under the same conditions as Tg and by a dynamic viscoelasticity measuring device (DMA, Seiko Instruments Inc.). DMS6100) was measured. For the obtained results, the storage modulus values at each temperature were taken out.

將以上評估結果與實施例1~11及比較例1之液晶密封劑組成物的配合組成同時表示於下述表1。 The composition of the above evaluation results and the liquid crystal sealant compositions of Examples 1 to 11 and Comparative Example 1 are shown in Table 1 below.

Claims (6)

一種硬化性樹脂，其為下述式(1)所示者： 〔式中，m為1~7的範圍之數，X彼此獨立為氫原子、羥基、縮水甘油基氧基、或甲基縮水甘油基氧基，R1各彼此獨立為氫原子、縮水甘油基或甲基縮水甘油基，R2各彼此獨立為氫原子或甲基，A環各彼此獨立為碳原子數、及雜原子數之合計為5以上，且含有1個以上芳香環、或雜芳香環之基，Y為下述式(1a)： (式中，Y1各彼此獨立為碳原子數2~5的伸烷基，n為1~250的範圍之數)、下述式(1b)： (式中，Y2各彼此獨立為直接結合或碳數1或者2的伸 烷基，R3各彼此獨立為氫原子或甲基，p與q各彼此獨立為0以上的數，且這些合計為1~200的範圍之數)、或前述式(1b)中之不飽和鍵的一部分或全部經氫化的結構之基，有關前述R1及X，縮水甘油基或甲基縮水甘油基之R1與縮水甘油基氧基或甲基縮水甘油基氧基之X的合計個數之平均x為1以上〕。 A curable resin which is represented by the following formula (1): Wherein m is a number in the range of 1 to 7, and X each independently represents a hydrogen atom, a hydroxyl group, a glycidyloxy group, or a methyl glycidyloxy group, and each of R 1 is independently a hydrogen atom or a glycidyl group. Or a methyl glycidyl group, each of R 2 is independently a hydrogen atom or a methyl group, and each of the A rings is independently a carbon atom and a total number of hetero atoms is 5 or more, and one or more aromatic rings or heteroaromatic groups are contained. The base of the ring, Y is the following formula (1a): (wherein Y 1 is each independently an alkylene group having 2 to 5 carbon atoms, and n is a number ranging from 1 to 250), and the following formula (1b): (wherein Y 2 is each independently a direct alkyl group or a C 1 or 2 alkyl group, and R 3 is each independently a hydrogen atom or a methyl group, and p and q are each independently a number of 0 or more, and these totals structure yl hydrogenated part or all of the unsaturated bonds is in the range of 1 to 200), or the formula (. IB), the relevant R 1 and X, glycidyl group or the methyl glycidyl R a methyl group or a glycidyl group with the glycidyl group of X number of total average x is from 1 or more]. 如請求項1之硬化性樹脂，其中對於前述式(1)，於A環所含的碳原子數為4~40，氧原子數為0~5，氮原子數為0~5，硫原子數為0~5，且於A環所含的環結構數為1~5。 The curable resin according to claim 1, wherein for the above formula (1), the number of carbon atoms contained in the ring A is 4 to 40, the number of oxygen atoms is 0 to 5, the number of nitrogen atoms is 0 to 5, and the number of sulfur atoms is It is 0~5, and the number of ring structures contained in the A ring is 1~5. 一種(甲基)丙烯酸化硬化性樹脂，其特徵為將如請求項1或2之硬化性樹脂的環氧基、羥基及不飽和鍵的至少一部分與(甲基)丙烯酸及/或(甲基)丙烯酸酐進行反應所得者。 A (meth) acrylate-hardening resin characterized in that at least a part of an epoxy group, a hydroxyl group and an unsaturated bond of the curable resin of claim 1 or 2 is bonded to (meth)acrylic acid and/or (methyl group) The one obtained by the reaction of acrylic anhydride. 一種液晶密封劑組成物，其特徵為含有如請求項1或2之硬化性樹脂及/或請求項3之(甲基)丙烯酸化硬化性樹脂者。 A liquid crystal sealant composition characterized by containing the curable resin of claim 1 or 2 and/or the (meth) acrylated curable resin of claim 3. 如請求項4之液晶密封劑組成物，其中前述液晶密封劑組成物中之硬化性樹脂及/或(甲基)丙烯酸化硬化性樹脂的含有量為5~95重量%。 The liquid crystal sealant composition according to claim 4, wherein the content of the curable resin and/or the (meth) acrylate-curable resin in the liquid crystal sealant composition is 5 to 95% by weight. 如請求項4或5之液晶密封劑組成物，其中前述液晶密封劑組成物為進一步含有具有乙烯性不飽和基及/或環氧基之化合物H(但，除前述硬化性樹脂及(甲基) 丙烯酸化硬化性樹脂以外)。 The liquid crystal sealant composition according to claim 4, wherein the liquid crystal sealant composition further contains a compound H having an ethylenically unsaturated group and/or an epoxy group (however, in addition to the aforementioned curable resin and (methyl) ) Other than acrylated curable resin).
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