Photocurable composition, sealant for liquid crystal display device, and liquid crystal display device

Abstract

A photocurable composition according to the present invention contains a curable resin component, a photopolymerization initiator and an inorganic filler. The curable resin component contains a multifunctional curable compound which has two or more ethylenically unsaturated double bonds. The multifunctional curable compound includes a first multifunctional curable compound and a second multifunctional curable compound, which are different from each other. The content ratio of the multifunctional curable compound is 85 parts by mass to 100 parts by mass relative to 100 parts by mass of the curable resin component. The viscosity at 25°C is 200,000 mPa∙s to 400,000 mPa∙s.

Description

【Technical Field】 【0001】 The present invention relates to a photocurable composition, a sealing material for a liquid crystal display device, and a liquid crystal display device. 【Background Art】 【0002】 Conventionally, a liquid crystal display element (for example, a liquid crystal display cell) has been manufactured by a liquid crystal droplet method. In this method, first, a sealant containing a curable resin, a photo radical polymerization initiator and / or a thermal radical polymerization initiator is applied to the outer periphery of the surface of a substrate with one electrode to form a substantially rectangular seal pattern. Next, while the sealant is in an uncured state, minute droplets of liquid crystal are dropped into the seal pattern frame provided on the substrate. Next, under vacuum, another substrate with an electrode is bonded to the surface of the substrate with one electrode, and the sealant is cured (photo-cured and / or thermally cured) to manufacture a liquid crystal display element. 【0003】 As a sealant used in the liquid crystal droplet method, for example, a sealant for a liquid crystal display element containing bisphenol A type epoxy acrylate, a thermal radical polymerization initiator, and a photo radical polymerization initiator has been proposed (see, for example, Example 8 of Patent Document 1). Such a sealant for a liquid crystal display element cures by heating after light irradiation. 【0004】 Further, in Patent Document 1, a sealant for a liquid crystal display element containing bisphenol A type epoxy acrylate and a photo radical polymerization initiator without containing a thermal radical polymerization initiator has been proposed (see, for example, Example 9 of Patent Document 1). Such a sealant for a liquid crystal display element cures only by light irradiation without heating. 【Prior Art Documents】 【Patent Documents】 【0005】 【Patent Document 1】 International Publication No. 2016 / 194871 pamphlet 【Summary of the Invention】 [Problems that the invention aims to solve] 【0006】 On the other hand, in Example 8 of Patent Document 1, the sealant for the liquid crystal display element is cured by heating, which has the drawback that the sealant cannot be cured if the substrate has low heat resistance. In addition, the heating process has the drawback of reducing productivity. 【0007】 However, as shown in Example 9 of Patent Document 1, curing the sealant solely by light curing has the drawback of reduced adhesiveness. 【0008】 Furthermore, if the sealant is dispensed from a nozzle, good dispensing performance from the nozzle is required. 【0009】 The present invention provides a photocurable composition having excellent adhesion and discharge properties from a nozzle, a sealing material for a liquid crystal display device containing the photocurable composition, and a liquid crystal display device comprising a cured product of the sealing material for the liquid crystal display device. [Means for solving the problem] 【0010】 The present invention [1] is a photocurable composition comprising a curable resin component, a photopolymerization initiator, and an inorganic filler, wherein the curable resin component comprises a polyfunctional curable compound having two or more ethylenically unsaturated double bonds, the polyfunctional curable compound comprises a first polyfunctional curable compound and a second polyfunctional curable compound that are different from each other, the content ratio of the polyfunctional curable compound is 85 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the curable resin component, and the viscosity at 25°C is 200,000 mPa·s or more and 400,000 mPa·s or less. 【0011】 The present invention [2] comprises the photocurable composition described in [1] above, wherein either the first polyfunctional curable compound or the second polyfunctional curable compound is an epoxy (meth)acrylate, the epoxy (meth)acrylate is a reaction product of an epoxy compound and a carboxyl group-containing vinyl monomer, the carboxyl group-containing vinyl monomer is a reaction product of a hydroxyl group-containing vinyl monomer and a polybasic acid, and the epoxy (meth)acrylate is a compound represented by the following formula (1). [ka] (In formula (1) above, R1 represents a hydrogen atom or a methyl group, R2 represents a structure derived from a hydroxyl group-containing vinyl monomer, and R3 represents a structure derived from a polybasic acid.) 【0012】 The present invention [3] includes the photocurable composition described in [1] or [2] above, wherein the inorganic filler content is 10% by mass or more. 【0013】 The present invention [4] comprises a photocurable composition according to any one of the above [1] to [3], wherein the inorganic filler is at least one selected from the group consisting of silica, alumina, and talc. 【0014】 The present invention [5] further comprises a photocurable composition according to any one of the above [1] to [4], which includes a coupling agent. 【0015】 The present invention [6] further comprises a photocurable composition according to any one of the above [1] to [5], wherein the composite particles comprise a core and a shell covering the core. 【0016】 The present invention [7] comprises a photocurable composition according to any one of the above [1] to [6], wherein the photopolymerization initiator has at least one skeleton selected from the group consisting of an oxime ester skeleton, a thioxanthone skeleton, and an anthraquinone skeleton. 【0017】 The present invention [8] includes a sealing material for a liquid crystal display device, which contains the photocurable composition according to any one of [1] to [7] above. 【0018】 The present invention [9] includes a liquid crystal display device, which includes a substrate with a first electrode, a substrate with a second electrode arranged to face the substrate with the first electrode, liquid crystal interposed between the substrate with the first electrode and the substrate with the second electrode, and a cured product of the sealing material for a liquid crystal display device according to [8] above that adheres to the peripheral ends of the substrate with the first electrode and the substrate with the second electrode. 【0019】 The present invention

[10] includes the liquid crystal display device according to [9] above, in which the substrates of the substrate with the first electrode and the substrate with the second electrode are polymer films. 【Effects of the Invention】 【0020】 The curable resin component of the photocurable composition of the present invention contains a polyfunctional curable compound having two or more ethylenically unsaturated double bonds. Further, the polyfunctional curable compound contains a first polyfunctional curable compound and a second polyfunctional curable compound that are different from each other. Further, the content ratio of the polyfunctional curable compound is within a predetermined range. Further, the photocurable composition contains an inorganic filler. Further, the viscosity of the photocurable composition at 25°C is within a predetermined range. Therefore, it is excellent in adhesiveness and dischargeability from the nozzle. 【0021】 The sealing material for a liquid crystal display device of the present invention contains the photocurable composition of the present invention. Therefore, it is excellent in adhesiveness and dischargeability from the nozzle. 【0022】 The liquid crystal display device of the present invention includes a cured product of the sealing material for a liquid crystal display device of the present invention. Therefore, it is excellent in adhesiveness. 【Brief Description of the Drawings】 【0023】 [Figure 1]Figures 1A to 1C show a method of manufacturing a liquid crystal display device by a liquid crystal droplet method using a sealing material for a liquid crystal display device. Figure 1A shows a step of applying a sealing material for a liquid crystal display device to the outer periphery of the surface of a substrate with one electrode to form a substantially rectangular seal pattern. Figure 1B shows a step of dropping minute droplets of liquid crystal into the seal pattern frame of the substrate 1 with one electrode while the sealing material for the liquid crystal display device is in an uncured state. Figure 1C shows a step of manufacturing a liquid crystal display device by bonding another substrate with an electrode to the surface of the substrate with one electrode under vacuum and photocuring the sealing material for the liquid crystal display device. 【Embodiments for Carrying Out the Invention】 【0024】 The photocurable composition contains a curable resin component, a photopolymerization initiator, and an inorganic filler. 【0025】 <Curable Resin Component> The curable resin component contains a polyfunctional curable compound. 【0026】 The polyfunctional curable compound has two or more ethylenically unsaturated double bonds. 【0027】 Examples of the polyfunctional curable compound include polyfunctional epoxy (meth)acrylate, polyfunctional (meth)acrylic acid alkyl ester, and polyfunctional urethane (meth)acrylate. Preferably, the polyfunctional curable compound is polyfunctional epoxy (meth)acrylate. Here, (meth)acrylate means methacrylate and / or acrylate. 【0028】 Examples of the polyfunctional epoxy (meth)acrylate include a first polyfunctional epoxy (meth)acrylate which is a reaction product of an epoxy compound and a carboxy group-containing vinyl monomer. 【0029】 Examples of epoxy compounds include difunctional epoxy compounds. Examples of difunctional epoxy compounds include diglycidyl ether compounds. Examples of diglycidyl ether compounds include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, and neopentyl glycol diglycidyl ether. Preferably, bisphenol A diglycidyl ether is used as the epoxy compound. 【0030】 Epoxy compounds can be used alone or in combination of two or more types. 【0031】 Examples of carboxyl group-containing vinyl monomers include (meth)acrylic acid, maleic anhydride, maleic acid, fumaric acid, itaconic acid, and crotonic acid. 【0032】 Furthermore, carboxyl group-containing vinyl monomers can also be found as reaction products of hydroxyl group-containing vinyl monomers with polybasic acids. 【0033】 Examples of hydroxyl group-containing vinyl monomers include hydroxyl group-containing acrylic monomers. Examples of hydroxyl group-containing acrylic monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Preferably, 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate are used as hydroxyl group-containing vinyl monomers. More preferably, 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate are used as hydroxyl group-containing vinyl monomers. 【0034】 Hydroxyl group-containing vinyl monomers can be used alone or in combination of two or more types. 【0035】 Examples of polybasic acids include saturated dibasic acids. Examples of saturated dibasic acids include saturated aliphatic dibasic acids, saturated alicyclic dibasic acids, and aromatic dibasic acids. 【0036】 Examples of saturated aliphatic dibasic acids include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, hexylsuccinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylsuccinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and their acid anhydrides. Preferably, succinic anhydride is used as a saturated aliphatic dibasic acid. 【0037】 Examples of saturated alicyclic dibasic acids include hemitic acid, 1,2-hexahydrophthalic acid, 1,1-cyclobutanedicarboxylic acid, and their acid anhydrides. 【0038】 Examples of aromatic dibasic acids include phthalic acids (orthophthalic acid, isophthalic acid, terephthalic acid), trimellitic acid, pyromellitic acid, and their acid anhydrides. A preferred example of an aromatic dibasic acid is phthalic acid. 【0039】 Examples of polybasic acids include saturated aliphatic dibasic acids and aromatic dibasic acids. 【0040】 Polybasic acids can be used alone or in combination of two or more types. 【0041】 To react the hydroxyl group-containing vinyl monomer with a polybasic acid, the hydroxyl group-containing vinyl monomer, the polybasic acid, and, if necessary, a polymerization inhibitor (e.g., p-methoxyphenol) are mixed together and heated. 【0042】 In the above reaction, the hydroxyl group-containing vinyl monomer is blended such that, for every mole of hydroxyl groups in the hydroxyl group-containing vinyl monomer, the amount of carboxyl groups of the polybasic acid is, for example, 1.8 moles or more, and for example, 2.2 moles or less. 【0043】 Furthermore, in the above reaction, the reaction temperature is, for example, 60°C or higher, preferably 80°C or higher, and also, for example, 120°C or lower, preferably 100°C or lower. The reaction time is, for example, 1 hour or more, and also, for example, 12 hours or less. 【0044】 This process yields a carboxyl group-containing vinyl monomer, which is the reaction product of a hydroxyl group-containing vinyl monomer and a polybasic acid. 【0045】 Preferably, carboxyl group-containing vinyl monomers include reaction products of hydroxyl group-containing vinyl monomers and polybasic acids. More preferably, carboxyl group-containing vinyl monomers include reaction products of 2-hydroxyethyl acrylate and succinic anhydride, reaction products of 2-hydroxypropyl acrylate and phthalic anhydride, reaction products of 2-hydroxypropyl acrylate and succinic anhydride, reaction products of 2-hydroxyethyl acrylate and phthalic anhydride, and reaction products of 2-hydroxyethyl methacrylate and succinic anhydride. Even more preferably, carboxyl group-containing vinyl monomers include reaction products of 2-hydroxypropyl acrylate and succinic anhydride, and reaction products of 2-hydroxyethyl acrylate and phthalic anhydride. 【0046】 Carboxylic acid-containing vinyl monomers can be used alone or in combination of two or more types. 【0047】 To react the epoxy compound with the carboxyl group-containing vinyl monomer, the epoxy compound and the carboxyl group-containing vinyl monomer are mixed and heated. 【0048】 In the above reaction, the epoxy compound is blended such that, for every mole of epoxy groups in the epoxy compound, the amount of carboxyl groups of the carboxyl group-containing vinyl monomer is, for example, 1.8 moles or more, and for example, 2.2 moles or less. 【0049】 Furthermore, in the above reaction, the reaction temperature is, for example, 60°C or higher, preferably 80°C or higher, and also, for example, 120°C or lower, preferably 100°C or lower. The reaction time is, for example, 1 hour or more, and also, for example, 12 hours or less. 【0050】 This yields a first polyfunctional epoxy (meth)acrylate. 【0051】 Among such first polyfunctional epoxy (meth)acrylates, preferred examples include compounds represented by the following formula (1). [ka] In formula (1) above, R1 represents a hydrogen atom or a methyl group. 【0052】 Furthermore, in formula (1) above, R2 represents a structure derived from the hydroxyl group-containing vinyl monomer. More specifically, when the hydroxyl group-containing vinyl monomer is represented by formula (2) below, R2 represents X. More specifically, X represents the alkylene group corresponding to the alkyl of the hydroxyalkyl ester in the hydroxyl group-containing vinyl monomer. More specifically, X represents an alkylene group having 1 to 4 carbon atoms. Even more specifically, it represents an ethylene group and a 2-propylene group. [ka] 【0053】 In formula (1) above, R3 represents a structure derived from the polybasic acid. Specifically, when the polybasic acid is represented as HOOC-Y-COOH, R3 represents Y. Specifically, Y is a divalent bonding group. Examples of bonding groups include bonding groups that do not contain aromatic rings and alicyclic rings, bonding groups that contain aromatic rings, and bonding groups that contain alicyclic rings. Examples of bonding groups that do not contain aromatic rings and alicyclic rings include alkylene groups having 1 to 20 carbon atoms. Examples of alkylene groups having 1 to 20 carbon atoms include linear alkylene groups having 1 to 20 carbon atoms and branched alkylene groups having 1 to 20 carbon atoms. Examples of linear alkylene groups having 1 to 20 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, tetradecylene, hexadecylene, octadecylene, and eicosilene. Examples of branched alkylene groups having 1 to 20 carbon atoms include isopropylene, isobutylene, s-butylene, t-butylene, isopentylene, s-pentylene, 2-methylhexylene, 2-ethylhexylene, and isodecylene. Examples of bonding groups containing aromatic rings include phenylene, naphthylene, and anthracenylene groups. Examples of bonding groups containing alicyclic rings include cyclohexylene and cyclopentylene groups. 【0054】 Among such first polyfunctional epoxy (meth)acrylates, preferred examples include the compound represented by formula (3) below (hereinafter referred to as compound (3)), the compound represented by formula (4) below (hereinafter referred to as compound (4)), the compound represented by formula (5) below (hereinafter referred to as compound (5)), the compound represented by formula (6) below (hereinafter referred to as compound (6)), and the compound represented by formula (7) below (hereinafter referred to as compound (7)). 【0055】 [ka] 【0056】 More preferably, the first polyfunctional epoxy (meth)acrylate is compound (5) and compound (6). 【0057】 The first polyfunctional epoxy (meth)acrylate can also be a commercially available product. An example of such a commercially available product is Ebecryl 3701 (compound (5), manufactured by Daicel Ornex Corporation). 【0058】 Furthermore, as an example of a polyfunctional epoxy (meth)acrylate, a second polyfunctional epoxy (meth)acrylate can be obtained by ring-opening the epoxy compound (preferably bisphenol A diglycidyl ether) with the polybasic acid (preferably phthalic anhydride), modifying it with ε-caprolactone, and then reacting it with the hydroxyl group-containing vinyl monomer. 【0059】 Examples of such secondary polyfunctional epoxy (meth)acrylates include the compound represented by the following formula (8) (hereinafter referred to as compound (8)). [ka] In equation (8) above, n represents an integer between 1 and 3, inclusive. 【0060】 The second polyfunctional epoxy (meth)acrylate can also be a commercially available product. An example of such a commercially available product is Ebecryl 3708 (compound (8), manufactured by Daicel Ornex Corporation). 【0061】 Polyfunctional curable compounds should not be used alone, but rather in combination of two or more types. In other words, the polyfunctional curable compound should include a first polyfunctional curable compound and a second polyfunctional curable compound that are distinct from each other. 【0062】 Preferably, two types of polyfunctional curable compounds are used in combination. That is, the polyfunctional curable compound consists of a first polyfunctional curable compound and a second polyfunctional curable compound. 【0063】 More preferably, both the first polyfunctional curable compound and the second polyfunctional curable compound are first polyfunctional epoxy (meth)acrylates, or both the first polyfunctional curable compound and the second polyfunctional curable compound are second polyfunctional epoxy (meth)acrylates, or one of the first polyfunctional curable compound and the second polyfunctional curable compound is first polyfunctional epoxy (meth)acrylate and the other is second polyfunctional epoxy (meth)acrylate. 【0064】 More preferably, one of the first polyfunctional curable compound and the second polyfunctional curable compound is a first polyfunctional epoxy (meth)acrylate, and the other is a second polyfunctional epoxy (meth)acrylate. 【0065】 In such cases, the content of the first polyfunctional epoxy (meth)acrylate is, for example, 30% by mass or more, preferably 45% by mass or more, and for example, 80% by mass or less, preferably 60% by mass or less, relative to the curable resin component. 【0066】 Furthermore, the content ratio of the first polyfunctional epoxy (meth)acrylate is, for example, 30 parts by mass or more, preferably 45 parts by mass or more, and for example, 90 parts by mass or less, preferably 60 parts by mass or less, based on 100 parts by mass of the total amount of the first polyfunctional epoxy (meth)acrylate and the second polyfunctional epoxy (meth)acrylate. 【0067】 Furthermore, the content of the second polyfunctional epoxy (meth)acrylate is, for example, 5% by mass or more, preferably 20% by mass or more, more preferably 35% by mass or more, and for example, 65% by mass or less, preferably 55% by mass or less, relative to the curable resin component. 【0068】 Furthermore, the content of the second polyfunctional epoxy (meth)acrylate is, for example, 10 parts by mass or more, preferably 40 parts by mass or more, and for example, 70 parts by mass or less, preferably 55 parts by mass or less, based on 100 parts by mass of the total amount of the first polyfunctional epoxy (meth)acrylate and the second polyfunctional epoxy (meth)acrylate. 【0069】 Furthermore, the mass ratio of the content of the first polyfunctional epoxy (meth)acrylate to the content of the second polyfunctional epoxy (meth)acrylate is, for example, 0.90 or more, preferably 0.95 or more, more preferably 1.01 or more, even more preferably 1.10 or more, or, for example, 8.00 or less, preferably 3.00 or less, more preferably 1.50 or less, even more preferably 1.30 or less, and particularly preferably 1.20 or less. 【0070】 Furthermore, more preferably, the viscosity of the first polyfunctional curable compound is higher than the viscosity of the second polyfunctional curable compound. In other words, more preferably, the polyfunctional curable compound comprises a first polyfunctional curable compound with relatively high viscosity and a second polyfunctional curable compound with relatively low viscosity. 【0071】 A polyfunctional curable compound can achieve both adhesion and discharge properties from a nozzle if it contains a first polyfunctional curable compound with relatively high viscosity and a second polyfunctional curable compound with relatively low viscosity. 【0072】 In such cases, the viscosity of the first polyfunctional curable compound at 60°C is, for example, 5000 mPa·s or more, and for example, 9000 mPa·s or less. 【0073】 Furthermore, the viscosity of the second polyfunctional curable compound at 60°C is, for example, 2000 mPa·s or more, and for example, less than 5000 mPa·s. 【0074】 The ratio of the viscosity of the first polyfunctional curable compound at 60°C to the viscosity of the second polyfunctional curable compound at 60°C is, for example, greater than 1, preferably 1.5 or more, and for example, 5 or less. 【0075】 The method for measuring the viscosity will be described in detail in the examples below. 【0076】 In such cases, the content of the first polyfunctional curable compound is, for example, 30% by mass or more, preferably 45% by mass or more, and for example, 80% by mass or less, preferably 60% by mass or less, relative to the curable resin component. 【0077】 Furthermore, the content ratio of the first polyfunctional curable compound is, for example, 30 parts by mass or more, preferably 45 parts by mass or more, and for example, 90 parts by mass or less, preferably 60 parts by mass or less, based on 100 parts by mass of the total amount of the first polyfunctional curable compound and the second polyfunctional curable compound. 【0078】 Furthermore, the content ratio of the second polyfunctional curable compound is, for example, 5% by mass or more, preferably 20% by mass or more, more preferably 35% by mass or more, and for example, 65% by mass or less, preferably 55% by mass or less, relative to the curable resin component. 【0079】 Furthermore, the content ratio of the second polyfunctional curable compound is, for example, 10 parts by mass or more, preferably 40 parts by mass or more, and for example, 70 parts by mass or less, preferably 55 parts by mass or less, based on 100 parts by mass of the total amount of the first polyfunctional curable compound and the second polyfunctional curable compound. 【0080】 Furthermore, the mass ratio of the content of the first polyfunctional curable compound to the content of the second polyfunctional curable compound is, for example, 0.90 or more, preferably 0.95 or more, more preferably 1.01 or more, even more preferably 1.10 or more, or, for example, 8.00 or less, preferably 3.00 or less, more preferably 1.50 or less, even more preferably 1.30 or less, and particularly preferably 1.20 or less. 【0081】 Furthermore, more preferably, the first polyfunctional curable compound having a relatively high viscosity is a first polyfunctional epoxy (meth)acrylate, and the second polyfunctional curable compound having a relatively low viscosity is a second polyfunctional epoxy (meth)acrylate. 【0082】 Furthermore, the content ratio of the polyfunctional curable compound is 85 parts by mass or more, preferably 90 parts by mass or more, more preferably 95 parts by mass or more, and 100 parts by mass or less, per 100 parts by mass of the curable resin component. 【0083】 If the content of the polyfunctional curable compound is above the lower limit mentioned above, adhesion and discharge performance from the nozzle can be improved. 【0084】 On the other hand, if the content of the polyfunctional curable compound is below the above lower limit, the adhesiveness and discharge performance from the nozzle will decrease. 【0085】 Furthermore, the curable resin component may include a monofunctional curable compound as needed. 【0086】 Examples of monofunctional curable compounds include monofunctional epoxy (meth)acrylates, monofunctional alkyl (meth)acrylates, and monofunctional urethane (meth)acrylates. Preferably, monofunctional alkyl (meth)acrylates are used as monofunctional curable compounds. 【0087】 Examples of monofunctional (meth)acrylate alkyl esters include monofunctional (meth)acrylate alkyl esters that do not contain a ring structure, and monofunctional (meth)acrylate alkyl esters that contain a ring structure. 【0088】 Examples of monofunctional alkyl (meth)acrylates that do not contain a ring structure include alkyl (meth)acrylates having 1 to 20 carbon atoms. Examples of alkyl (meth)acrylates having 1 to 20 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, and lauryl (meth)acrylate. 【0089】 Examples of monofunctional alkyl (meth)acrylates containing a ring structure include isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. 【0090】 Preferably, monofunctional alkyl (meth)acrylates include monofunctional alkyl (meth)acrylates containing a ring structure. More preferably, dicyclopentenyloxyethyl (meth)acrylate is included as a monofunctional alkyl (meth)acrylate. Even more preferably, dicyclopentenyloxyethyl acrylate is included as a monofunctional alkyl (meth)acrylate. 【0091】 Monofunctional curable compounds can be used alone or in combination of two or more types. 【0092】 The content ratio of the monofunctional curable compound is, for example, 0 parts by mass or more, and for example, 15 parts by mass or less, preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, per 100 parts by mass of the curable resin component. 【0093】 If the content of the monofunctional curable compound is below the above upper limit, adhesion and discharge performance from the nozzle can be improved. 【0094】 The curable resin component preferably consists of a polyfunctional curable compound and does not contain a monofunctional curable compound. 【0095】 The content of the curable resin component is 80% by mass or more, preferably 85% by mass or more, and for example, 95% by mass or less, relative to the photocurable composition. 【0096】 <Photopolymerization initiator> A known photopolymerization initiator is selected. 【0097】 The photopolymerization initiator preferably has at least one skeleton selected from the group consisting of an oxime ester skeleton, a thioxanthone skeleton, and an anthraquinone skeleton. 【0098】 The photopolymerization initiator exhibits excellent photocuring properties, preferably having at least one skeleton selected from the group consisting of an oxime ester skeleton, a thioxanthone skeleton, and an anthraquinone skeleton. 【0099】 Examples of photopolymerization initiators having an oxime ester skeleton include 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyl oxime) and ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime). Preferably, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime) is used as a photopolymerization initiator having an oxime ester skeleton. 【0100】 Examples of photopolymerization initiators having a thioxanthone skeleton include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone, which are thioxanthone compounds. 【0101】 Furthermore, as photopolymerization initiators having a thioxanthone skeleton, compounds having a thioxanthone skeleton as described in International Publication No. 2017 / 002362 can also be used. 【0102】 Examples of photopolymerization initiators having an anthraquinone skeleton include 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone. 【0103】 Furthermore, as photopolymerization initiators having an anthraquinone skeleton, compounds having a thioxanthone skeleton as described in International Publication No. 2017 / 002362 can also be used. 【0104】 The photopolymerization initiator more preferably has an oxime ester skeleton. In other words, the photopolymerization initiator more preferably includes a photopolymerization initiator having an oxime ester skeleton. 【0105】 Photopolymerization initiators can be used alone or in combination of two or more types. 【0106】 The content ratio of the photopolymerization initiator is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, and for example, 3 parts by mass or less, preferably 1 part by mass or less, per 100 parts by mass of the curable resin component. 【0107】 The content of the photopolymerization initiator is, for example, 0.1% by mass or more, preferably 0.3% by mass or more, and for example, 5% by mass or less, preferably 1% by mass or less, relative to the photocurable composition. 【0108】 <Inorganic filler> Inorganic fillers are added to improve adhesion. Furthermore, by adjusting the viscosity through the addition of inorganic fillers, the discharge performance from the nozzle can be improved. 【0109】 Examples of inorganic fillers include oxides (e.g., alumina), hydroxides, carbonates, sulfates, silica, talc, silicates, fluorides, phosphates, and clay minerals. 【0110】 The inorganic filler is preferably at least one selected from the group consisting of silica, alumina, and talc. 【0111】 Adhesion and discharge from the nozzle can be further improved if the inorganic filler is at least one selected from the group consisting of silica, alumina, and talc. 【0112】 Inorganic fillers can be used alone or in combination of two or more types. 【0113】 The inorganic filler content is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and for example, 30 parts by mass or less, per 100 parts by mass of the curable resin component. 【0114】 Furthermore, the inorganic filler content is, for example, 5% by mass or more, preferably 10% by mass or more from the viewpoint of improving adhesion, more preferably 15% by mass or more from the viewpoint of further improving adhesion, and also, for example, 30% by mass or less, relative to the photocurable composition. 【0115】 <Method for producing a photocurable composition> A photocurable composition is obtained by mixing a curable resin component, a photopolymerization initiator, and an inorganic filler. 【0116】 Furthermore, composite particles may preferably be incorporated into the above mixture. In other words, the photocurable composition preferably contains composite particles. 【0117】 Composite particles are added to improve adhesion. 【0118】 The composite particle comprises a core and a shell that covers the core. 【0119】 Specifically, the core and shell are polymers of, for example, alkyl (meth)acrylates. Examples of alkyl (meth)acrylates include alkyl (meth)acrylates having an alkyl moiety with 1 to 12 carbon atoms. Examples of alkyl (meth)acrylates having an alkyl moiety with 1 to 12 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate. 【0120】 Preferably, such composite particles include those in which the core is a polymer of n-butyl acrylate and the shell is a polymer of methyl methacrylate. 【0121】 Furthermore, in such composite particles, the glass transition temperature of the shell is higher than that of the core. 【0122】 Commercially available composite particles can also be used. For example, Zephyrac F351 (manufactured by Aica Kogyo Co., Ltd.) is one such commercially available product. 【0123】 The content ratio of composite particles is, for example, 1 part by mass or more, preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and for example, 20 parts by mass or less, preferably 10 parts by mass or less, per 100 parts by mass of the curable resin component. 【0124】 Furthermore, a coupling agent may be added to the above mixture. In other words, the photocurable composition contains a coupling agent. 【0125】 Coupling agents are added to improve adhesion. 【0126】 The coupling agent is not particularly limited. Examples of coupling agents include epoxy group-containing silane coupling agents, amino group-containing silane coupling agents, and (meth)acryloyl group-containing silane coupling agents. Preferably, a (meth)acryloyl group-containing silane coupling agent is used. 【0127】 Examples of (meth)acryloyl group-containing silane coupling agents include 2-methacryloyloxyethyltrimethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, and 3-acryloyloxypropyltrimethoxysilane. Preferably, 3-methacryloyloxypropyltriethoxysilane is used as a (meth)acryloyl group-containing silane coupling agent. 【0128】 The content of the coupling agent is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, and for example, 5% by mass or less, preferably 2% by mass or less, relative to the photocurable composition. 【0129】 Furthermore, additives may be incorporated into the above mixture. In other words, the photocurable composition contains additives. Examples of additives include curing accelerators, defoamers, leveling agents, and polymerization inhibitors. 【0130】 The additive content is, for example, 10% by mass or less, preferably 5% by mass or less, relative to the photocurable composition. 【0131】 This is used to produce a photocurable composition. 【0132】 The viscosity of the photocurable composition at 25°C is 200,000 mPa·s or higher, preferably 250,000 mPa·s or higher, more preferably 300,000 mPa·s or higher, and 400,000 mPa·s or lower. 【0133】 If the viscosity is above the lower limit and below the upper limit, the discharge performance from the nozzle will improve. 【0134】 The method for measuring the viscosity will be described in detail in the examples below. 【0135】 <Effects and Effects> The photocurable composition contains an inorganic filler. Therefore, its adhesive properties can be improved. Furthermore, its viscosity can be adjusted, improving its discharge performance from the nozzle. 【0136】 Furthermore, the curable resin component includes a polyfunctional curable compound. The polyfunctional curable compound also includes a first polyfunctional curable compound and a second polyfunctional curable compound, which are distinct from each other. The content ratio of the polyfunctional curable compound is within a predetermined range. Therefore, it exhibits excellent adhesion and discharge properties from the nozzle. 【0137】 Furthermore, the viscosity of the photocurable composition at 25°C is within a predetermined range. Therefore, it exhibits excellent discharge properties from the nozzle. 【0138】 Furthermore, the photocurable composition cures with light. Therefore, even if the substrate (described later) to which the photocurable composition is applied has low heat resistance, the photocurable composition can still be cured. In addition, because the photocurable composition cures with light, it offers excellent productivity. 【0139】 Furthermore, such photocurable compositions have excellent adhesive properties and extrusion properties from nozzles, making them suitable for use as sealing materials for liquid crystal display devices. 【0140】 <Sealing material for liquid crystal display devices> The sealing material for liquid crystal display devices contains a photocurable composition. 【0141】 Because the sealing material for liquid crystal display devices contains a photocurable composition, it exhibits excellent adhesion and extrusion properties from the nozzle. 【0142】 More specifically, this sealing material for liquid crystal displays can be suitably used in the manufacture of liquid crystal displays using the liquid crystal drop method. The following describes in detail a method for manufacturing a liquid crystal display using this sealing material. 【0143】 In detail, in the liquid crystal drop method, as shown in Figure 1A, a liquid crystal display sealing material 2 is applied to the outer periphery of the surface of a substrate 1 with one electrode, which serves as the first electrode substrate, to form a roughly rectangular sealing pattern 3. At this time, the liquid crystal display sealing material 2 is discharged from the nozzle 10. 【0144】 Examples of electrode-equipped substrates 1 include glass substrates and polymer films (e.g., PET (polyethylene terephthalate) film, TAC (triacetyl cellulose) film, and polycarbonate film). This sealing material for liquid crystal displays allows for the manufacture of liquid crystal displays even with substrates that have low heat resistance; therefore, polymer films are preferred as electrode-equipped substrates 1. 【0145】 Next, as shown in Figure 1B, while the liquid crystal display sealing material 2 is still uncured, tiny droplets of liquid crystal 4 are dropped into the sealing pattern 3 frame of one electrode-equipped substrate 1. 【0146】 Next, as shown in Figure 1C, a liquid crystal display device is manufactured by bonding another electrode-equipped substrate 5 (a substrate similar to the electrode-equipped substrate 1) as a second electrode-equipped substrate to the surface of one electrode-equipped substrate under vacuum, and then photocuring the liquid crystal display device sealant 2. Such a liquid crystal display device comprises a first electrode-equipped substrate 1, a second electrode-equipped substrate 5 positioned opposite the first electrode-equipped substrate 1, liquid crystal interposed between the first electrode-equipped substrate 1 and the second electrode-equipped substrate 5, and a cured product of the liquid crystal display device sealant that adheres the peripheral edges of the first electrode-equipped substrate 1 and the second electrode-equipped substrate 5. 【0147】 Because the liquid crystal display device sealant 2 has excellent dispensing properties from the nozzle, it exhibits excellent coating properties even when the liquid crystal display device sealant 2 is dispensed from the nozzle 10. 【0148】 Furthermore, because the liquid crystal display sealant 2 is photocurable, it can be cured even if the substrate 1 has low heat resistance. Also, because the liquid crystal display sealant 2 is photocurable, it offers excellent productivity. 【0149】 Furthermore, because the sealing material 2 for liquid crystal display devices has excellent adhesive properties, it can reliably bond one electrode-equipped substrate 1 to the other electrode-equipped substrate 5. [Examples] 【0150】 Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to the following examples. Unless otherwise specified, "parts" and "%" are based on mass. Furthermore, specific numerical values ​​such as blending ratios (content), physical properties, and parameters used in the following description may be replaced with the corresponding upper limits (numerical values ​​defined as "less than or equal to" or "less than") or lower limits (numerical values ​​defined as "greater than or equal to" or "greater than") of the blending ratios (content), physical properties, and parameters described in the "Modes for Carrying Out the Invention" above. 【0151】 <Details of ingredients> The product names and abbreviations of the components used in each manufacturing example, each embodiment, and each comparative example are described in detail below. Ebecryl3708: The above compound (8), manufactured by Daicel Ornex Corporation, viscosity at 60°C: 3500 mPa·s FA-512AS: Monofunctional curable compound, dicyclopentenyloxyethyl acrylate, Manufactured by Showa Denko Materials Co., Ltd. Ebecryl3700: Bisphenol A type epoxy acrylate, viscosity at 60°C 4300 mPa·s OXE-02: Photopolymerization initiator, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(0-acetyloxime) Omnipol-910: Polyethylene glycol 200-di(β-4(4-(2-dimethylamino-2-benzyl)butanonylphenyl)piperazine), manufactured by IGM. SO-C1: Silica particles, inorganic filler, manufactured by Admatex Corporation. DAW-01: Alumina particles, inorganic filler, manufactured by Denka Co., Ltd. F351: Core-shell particles in which the core is a polymer of n-butyl acrylate and the shell is a polymer of methyl methacrylate, trade name "Zephyr F351", manufactured by Aica Kogyo Co., Ltd., KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.), coupling agent: methacryloyloxypropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. 【0152】 <Production of polyfunctionally curable compounds> Manufacturing Example 1 116 g of 2-hydroxyethyl acrylate, 0.1 g of p-methoxyphenol (as a polymerization inhibitor), and 100 g of succinic anhydride were placed in a flask, and the mixture was reacted at 90°C under reflux stirring for 5 hours with dry air introduced. Next, 170 g of bisphenol A diglycidyl ether was added, and the mixture was reacted similarly at 90°C under reflux stirring for 5 hours. The resulting compound was washed 20 times with ultrapure water. Compound (3) was thus prepared. 【0153】 Manufacturing Example 2 130 g of 2-hydroxypropyl acrylate, 0.1 g of p-methoxyphenol (polymerization inhibitor), and 148 g of phthalic anhydride were placed in a flask, and the mixture was reacted at 90°C under reflux stirring for 5 hours with dry air introduced. Next, 170 g of bisphenol A diglycidyl ether was added, and the mixture was reacted similarly at 90°C under reflux stirring for 5 hours. The resulting compound was washed 20 times with ultrapure water. Compound (4) was thus prepared. 【0154】 Manufacturing Example 3 130 g of 2-hydroxypropyl acrylate, 0.1 g of p-methoxyphenol (polymerization inhibitor), and 100 g of succinic anhydride were placed in a flask, and the mixture was reacted at 90°C under reflux stirring for 5 hours with dry air introduced. Next, 170 g of bisphenol A diglycidyl ether was added, and the mixture was reacted similarly at 90°C under reflux stirring for 5 hours. The resulting compound was washed 20 times with ultrapure water. Compound (5) was thus prepared. 【0155】 Manufacturing Example 4 116 g of 2-hydroxyethyl acrylate, 0.1 g of p-methoxyphenol (polymerization inhibitor), and 148 g of phthalic anhydride were placed in a flask, and the mixture was reacted at 90°C under reflux stirring for 5 hours with dry air introduced. Next, 170 g of bisphenol A diglycidyl ether was added, and the mixture was reacted similarly at 90°C under reflux stirring for 5 hours. The resulting compound was washed 20 times with ultrapure water. Compound (6) was thus prepared. 【0156】 Manufacturing Example 5 130 g of 2-hydroxyethyl methacrylate, 0.1 g of p-methoxyphenol (polymerization inhibitor), and 100 g of succinic anhydride were placed in a flask, and the mixture was reacted at 90°C under reflux stirring for 5 hours with dry air introduced. Next, 170 g of bisphenol A diglycidyl ether was added, and the mixture was reacted similarly at 90°C under reflux stirring for 5 hours. The resulting compound was washed 20 times with ultrapure water. Compound (7) was thus prepared. 【0157】 Manufacturing Example 6 A polyfunctional curable compound was prepared in accordance with the synthesis of epoxy acrylate in Example 1 of Japanese Patent Publication No. 2011-186486. 【0158】 <Manufacturing of photopolymerization initiators> Manufacturing example 7 Thioxanthone compounds were prepared according to Synthesis Example 14 in International Publication No. 2017 / 002362. 【0159】 Manufacturing Example 8 Anthraquinone compounds were prepared according to Synthesis Example 6 in International Publication No. 2017 / 002362. 【0160】 <Manufacturing of photocurable compositions> Example 1 1 , and Comparative Example 1 to Comparative Example 16 Based on the formulations described in Tables 1 and 2, the components were mixed using a three-roller system to obtain a uniform liquid. This produced a photocurable composition. 【0161】 <Rating> [viscosity] The viscosity was measured for the polyfunctional curable compounds of each manufacturing example and the photocurable compositions of each example and comparative example. Specifically, viscosity was measured using an E-type viscometer (TVE-35L viscometer, manufactured by Toki Sangyo Co., Ltd., rotor name: 3°×R9.7) in accordance with the cone-plate viscometer method of JIS K5600-2-3 (2014). The rotation speed of the cone plate during measurement was set to 2.5 rpm. The measurement temperature was 60°C for the polyfunctional curable compounds and 25°C for the photocurable compositions. 【0162】 The viscosity of the polyfunctional curable compound in Production Example 1 at 60°C was 7000 mPa·s. The viscosity of the polyfunctional curable compound in Production Example 2 at 60°C was 6000 mPa·s. The viscosity of the polyfunctional curable compound in Production Example 3 at 60°C was 6600 mPa·s. The viscosity of the polyfunctional curable compound in Production Example 4 at 60°C was 7000 mPa·s. The viscosity of the polyfunctional curable compound in Production Example 5 at 60°C was 5400 mPa·s. The viscosity of the photocurable compositions at 25°C is shown in Tables 1 and 2. 【0163】 [Discharge performance from the nozzle] 30 g of the photocurable composition from each example and comparative example was filled into a 10 cc syringe and then degassed. Next, a low-pressure-drop nozzle with a nozzle diameter of 0.25 mmφ (AI Mechatec: SL nozzle) was attached. After a 3-minute test discharge, the photocurable composition adhering to the nozzle tip was completely wiped off, and the syringe was allowed to stand still for 2 minutes. After 2 minutes, it was visually checked whether the photocurable composition had accumulated at the nozzle tip. The discharge performance from the nozzle was evaluated based on the following criteria. The results are shown in Tables 1 and 2. {standard} ○: Almost no photocurable composition was dispensed from the nozzle tip. ×: The photocurable composition had accumulated at the nozzle tip or had dripped down. 【0164】 [Adhesiveness] To 100 parts by mass of the photocurable composition in each example and comparative example, 2 parts by mass of polymer beads (Sekisui Chemical Co., Ltd.: Micropearl SP) with an average particle size of 5 μm were added, and the photocurable composition was dispersed using a planetary stirring device. Next, a transparent electrode ITO was pre-formed on a 25 mm × 45 mm glass substrate (RT-DM88-PIN, EHC Corporation), and a seal pattern was formed by applying the photocurable composition (dispersed photocurable composition) to the center of the substrate with a thickness of 5 μm, so that the diameter of the circle after bonding would be approximately 4.2 mm, using a screen printing plate to form a seal pattern with a diameter of 1.5 mmφ. Then, another glass substrate was bonded perpendicularly to the glass substrate with the seal pattern under atmospheric pressure. Finally, 3000 mJ / cm² was applied. 2 The photocurable composition was cured by irradiating it with visible light (light with a wavelength of 370-450 nm). Test specimens were then produced. 【0165】 A 0.5 mm section from the center of the short side of the glass specimen was pressed vertically at a speed of 37.5 mm / min using an indentation tester (Model 210, Intesco), and the stress at which the seal peeled off was measured. This stress value was defined as the adhesive strength. The adhesiveness was evaluated based on the following criteria. The results are shown in Tables 1 and 2. 【0166】 ◎: The stress was 5N or higher. Or, the base material cracked before the seal peeled off. ○: The stress was between 3N and less than 5N. ×: The stress was less than 3N. 【0167】 [Table 1] 【0168】 [Table 2] 【0169】 The above invention is provided as an illustrative embodiment of the present invention, but this is merely illustrative and should not be interpreted restrictively. Modifications of the present invention that are obvious to those skilled in the art are included in the claims below. [Industrial applicability] 【0170】 The photocurable composition and sealing material manufacturing method for liquid crystal display devices of the present invention are suitably used, for example, in the manufacture of liquid crystal display devices. The liquid crystal display device of the present invention is suitably used, for example, in the manufacture of image display elements. [Explanation of symbols] 【0171】 1. Substrate with first electrode 5. Substrate with second electrode

Claims

[Claim 1] It contains a curable resin component, a photopolymerization initiator, and an inorganic filler. The curable resin component comprises a polyfunctional curable compound having two or more ethylenically unsaturated double bonds. The polyfunctional curable compound comprises a first polyfunctional curable compound and a second polyfunctional curable compound that are different from each other. The content ratio of the polyfunctional curable compound is 85 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the curable resin component. The viscosity at 25°C is between 200,000 mPa·s and 400,000 mPa·s. The stress measured by the following test is 3N or more. Furthermore, it contains composite particles, The composite particle comprises a core and a shell covering the core, and is a photocurable composition. Test: 2 parts by mass of polymer beads with an average particle size of 5 μm are added to 100 parts by mass of the photocurable composition and dispersed using a planetary stirring device. Next, the photocurable composition is applied to the center of a 25 mm x 45 mm glass substrate with a transparent electrode ITO pre-formed on it, using a screen printing plate, to form a seal pattern with a diameter of 1.5 mm, such that the diameter of the circle after bonding to the substrate with a thickness of 5 μm will be approximately 4.2 mm. Then, another glass substrate is bonded perpendicularly to the glass substrate with the seal pattern in atmospheric pressure. Finally, 3000 mJ / cm² is applied. ２ The photocurable composition is cured by irradiating it with visible light (light with a wavelength of 370-450 nm). This is used to manufacture a test specimen. A 0.5 mm section from the center of the short side of the glass specimen toward the center is pressed vertically at a speed of 37.5 mm / min using an indentation tester, and the stress at which the seal peels off is measured. [Claim 2] Either the first polyfunctional curable compound or the second polyfunctional curable compound is an epoxy (meth)acrylate, The epoxy (meth)acrylate is a reaction product of an epoxy compound and a carboxyl group-containing vinyl monomer. The carboxyl group-containing vinyl monomer is a reaction product of a hydroxyl group-containing vinyl monomer and a polybasic acid. The photocurable composition according to claim 1, wherein the epoxy (meth)acrylate is a compound represented by the following formula (1). 【Chemistry 1】 (In formula (1) above, R1 represents a hydrogen atom or a methyl group, R2 represents a structure derived from a hydroxyl group-containing vinyl monomer, and R3 represents a structure derived from a polybasic acid.) [Claim 3] The photocurable composition according to claim 1, wherein the content of the inorganic filler is 10% by mass or more. [Claim 4] The photocurable composition according to claim 1, wherein the inorganic filler is at least one selected from the group consisting of silica, alumina, and talc. [Claim 5] Furthermore, the photocurable composition according to claim 1, further comprising a coupling agent. [Claim 6] The photocurable composition according to claim 1, wherein the photopolymerization initiator has at least one skeleton selected from the group consisting of an oxime ester skeleton, a thioxanthone skeleton, and an anthraquinone skeleton. [Claim 7] A sealing material for liquid crystal display devices comprising the photocurable composition described in claim 1. [Claim 8] A substrate with a first electrode, A second electrode-equipped substrate is positioned opposite the first electrode-equipped substrate, A liquid crystal interposed between the first electrode substrate and the second electrode substrate, A liquid crystal display device comprising a cured product of the sealing material for liquid crystal display devices according to claim 7, which is used to bond the peripheral edges of the substrate with the first electrode and the substrate with the second electrode. [Claim 9] The liquid crystal display device according to claim 8, wherein the substrates in the first electrode substrate and the second electrode substrate are polymer films.