Curing resin composition, sealant for liquid crystal display element, up-and-down conductive material, and liquid crystal display element

Abstract

An object of the present application is to provide a curable resin composition capable of inhibiting deformation of an adherend caused by a force from the outside or internal stress. In addition, an object of the present application is to provide a sealant for liquid crystal display elements, an up-and-down conductive material, and a liquid crystal display element each of which is made using the curable resin composition. The curable resin composition of the present application contains a curable resin and a photopolymerization initiator, and a minimum value of a loss elastic modulus in a temperature rising process in which a temperature is raised at a temperature rising rate of 10°C / min from 25°C to 120°C is 1.5 MPa or more when a photo-cured product obtained by irradiating 3000 mJ / cm 2 of ultraviolet rays to the curable resin composition is subjected to dynamic viscoelasticity measurement.

Description

Technical Field

[0001] This invention relates to a curable resin composition capable of suppressing deformation of adhered materials caused by external forces or internal stress. Furthermore, this invention relates to sealants for liquid crystal display elements, top and bottom conductive materials, and liquid crystal display elements made using this curable resin composition. Background Technology

[0002] In recent years, as a manufacturing method for liquid crystal display elements, from the viewpoint of shortening production cycle time and optimizing the amount of liquid crystal used, a liquid crystal dropping process, also known as the dropping process, has been used, as disclosed in Patent Documents 1 and 2, which uses a photothermal curing sealant containing a curable resin, a photopolymerization initiator, and a thermosetting agent.

[0003] In the droplet process, firstly, a rectangular sealing pattern is formed on one of two transparent substrates with electrodes by dispensing. Next, while the sealant is not yet cured, tiny drops of liquid crystal are added to the entire frame of the transparent substrate, and the other transparent substrate is immediately overlapped. The sealed area is then irradiated with ultraviolet light or other light for pre-curing. Finally, heating is applied for curing to produce the liquid crystal display element. By bonding the substrates under reduced pressure, liquid crystal display elements can be manufactured with extremely high efficiency, and this droplet process is currently the mainstream method for manufacturing liquid crystal display elements.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2001-133794

[0007] Patent Document 2: Japanese Patent Application Publication No. 5-295087 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] When using conventional curable resin compositions as sealants for liquid crystal display elements to manufacture liquid crystal display elements, deformation of the substrate may occur during substrate handling, heating processes, etc., due to external forces such as support pins or the inherent internal stress of the substrate.

[0010] The object of this invention is to provide a curable resin composition capable of suppressing deformation of the adhered material caused by external forces or internal stress. Furthermore, the object of this invention is to provide a sealant for a liquid crystal display element, a top and bottom conductive material, and a liquid crystal display element made using this curable resin composition.

[0011] Methods for solving problems

[0012] This invention relates to a curable resin composition containing a curable resin and a photopolymerization initiator, which, when irradiated with 3000 mJ / cm², provides a curable resin composition suitable for use with photopolymerization. 2 When the photocured material obtained by ultraviolet light is heated from 25°C to 120°C at a heating rate of 10°C / min, the minimum loss modulus of elasticity in the heating process is greater than 1.5 MPa.

[0013] The present invention will now be described in detail.

[0014] The inventors discovered that, for a light-cured product of a curable resin composition, by ensuring that the minimum loss modulus of elasticity during a heating process in which dynamic viscoelasticity is measured at a heating rate of 10°C / min from 25°C to 120°C is above a specific value, deformation of the adherend caused by external forces and internal stress can be suppressed, thus completing the present invention.

[0015] The reason why the minimum loss modulus of elasticity of the photocurable resin composition of the present invention during the heating process is 1.5 MPa or more can suppress the deformation of the adhered material caused by the deformation of the substrate due to external forces such as support pins or the internal stress of the substrate during the heating process is as follows: In the actual heating process, which is usually carried out by heating to about 120°C, the external forces or internal stress of the substrate applied to the entire substrate can be mitigated by the photocurable resin composition. Therefore, it can be considered that by making the minimum loss modulus of elasticity of the photocurable material during the heating process 1.5 MPa or more, such an effect can be achieved.

[0016] Regarding the curable resin composition of the present invention, irradiation of the above-mentioned curable resin composition at 3000 mJ / cm 2 The UV-cured material obtained by exposing ultraviolet light has a minimum loss modulus of 1.5 MPa or more during a heating process in which the temperature is increased from 25°C to 120°C at a heating rate of 10°C / min. By ensuring that the minimum loss modulus of the UV-cured material during the heating process is 1.5 MPa or more, the curable resin composition of the present invention can suppress deformation of the adhered material caused by external forces and internal stresses. Preferably, the minimum loss modulus of the UV-cured material during the heating process is 3.0 MPa or more.

[0017] Furthermore, from a descriptive point of view, the minimum loss modulus of the aforementioned photocurable material during the heating process is preferably 1000 MPa or less, and more preferably 800 MPa or less.

[0018] It should be noted that, as the aforementioned photocurable material, the curable resin composition was irradiated with 3000 mJ / cm² using a metal halide lamp through a cutoff filter of 340 nm. 2 A photocured material is obtained by curing it with ultraviolet light (wavelength 365nm). 3000mJ / cm² 2 For example, exposure to ultraviolet light for 30 seconds at 100 mW / cm 2 It is done using ultraviolet light.

[0019] In addition, the minimum loss modulus of elasticity of the aforementioned photocured material during the heating process can be measured using a dynamic viscoelasticity measuring device (such as the "DVA-200" manufactured by IT Measurement & Control Co., Ltd.), under the conditions of tensile mode, test piece width of 5 mm, thickness of 0.35 mm, clamping width of 25 mm, heating rate of 10 °C / min, holding temperature of 120 °C, and frequency of 10 Hz.

[0020] For the curable resin composition of the present invention, irradiation of the above-mentioned curable resin composition with 3000 mJ / cm 2 After exposure to ultraviolet light, the photothermal cured material is obtained by heating at 120°C for 1 hour. The preferred lower limit of the storage modulus of this photothermal cured material at a temperature of glass transition temperature plus 40°C is 50 MPa. By ensuring that the storage modulus of the photothermal cured material at a temperature of glass transition temperature plus 40°C is 50 MPa or higher, the curable resin composition of the present invention exhibits excellent low liquid crystal contamination when used as a sealant for liquid crystal display elements. A more preferred lower limit of the storage modulus of this photothermal cured material at a temperature of glass transition temperature plus 40°C is 80 MPa.

[0021] Furthermore, from the viewpoint of adhesion to the substrate, the preferred upper limit of the storage modulus of the photothermal curing material at a temperature of glass transition temperature plus 40°C is 1000 MPa, and a more preferred upper limit is 800 MPa.

[0022] It should be noted that, as the aforementioned photothermal cured product, the curable resin composition was irradiated with a metal halide lamp through a cutoff filter of less than 340 nm at a rate of 100 mW / cm². 2 The photothermal cured product is obtained by applying ultraviolet light (wavelength 365nm) for 30 seconds and then heating it at 120℃ for 1 hour.

[0023] Furthermore, the aforementioned glass transition temperature refers to the temperature at which the maximum value of the loss tangent (tanδ) obtained by dynamic viscoelasticity measurement occurs due to micro Brownian motion. This glass transition temperature can be measured using conventionally known methods employing dynamic viscoelasticity measuring devices, etc.

[0024] Furthermore, the storage modulus of the photothermal curing material at a temperature 40°C above the glass transition temperature can be measured using a dynamic viscoelasticity measuring device (e.g., IT Measurement & Control Co., Ltd., “DVA-200”), under the following conditions: tensile mode, test piece width 5 mm, thickness 0.35 mm, clamping width 25 mm, heating rate 10°C / min, and frequency 10 Hz.

[0025] The curable resin composition of the present invention contains a curable resin and a photopolymerization initiator.

[0026] In the curable resin composition of the present invention, by adjusting the type and content of the curable resin, the photopolymerization initiator, and other components, the minimum loss modulus of the photocurable material during the heating process and the storage modulus of the photocurable material at a temperature of glass transition temperature plus 40°C are easily within the aforementioned ranges.

[0027] Specifically, the minimum loss modulus of the aforementioned photocurable material during the heating process can be adjusted by combining a polyfunctional (meth)acrylic acid compound having two or more (meth)acryloyl groups in one molecule with a trifunctional (meth)acrylic acid compound having an isocyanuric acid backbone and having three (meth)acryloyl groups in one molecule. Furthermore, the storage modulus of the aforementioned photocurable material at a temperature of glass transition temperature plus 40°C can be adjusted by combining a polyfunctional (meth)acrylic acid compound having two or more (meth)acryloyl groups in one molecule with a trifunctional (meth)acrylic acid compound having an isocyanuric acid backbone and having three (meth)acryloyl groups in one molecule.

[0028] The aforementioned curable resin preferably comprises a polyfunctional (meth)acrylic acid compound having two or more (meth)acryloyl groups per molecule, and a trifunctional (meth)acrylic acid compound having an isocyanuric acid backbone and having three (meth)acryloyl groups per molecule. By using these compounds in combination, it is easy to minimize the loss modulus of elasticity of the aforementioned photocurable material during the heating process, and to achieve the storage modulus of the photocurable material at a temperature of glass transition temperature plus 40°C within the aforementioned range. Furthermore, by using these compounds in combination, the resulting curable resin composition exhibits excellent low liquid crystal contamination and adhesion to alignment films when used as a sealant for liquid crystal display elements.

[0029] It should be noted that even compounds with three (meth)acryloyl groups in one molecule are not treated as polyfunctional (meth)acrylic acid compounds as described above, but rather as trifunctional (meth)acrylic acid compounds with an isocyanuric acid skeleton and three (meth)acryloyl groups in one molecule.

[0030] In addition, in this specification, "(meth)acryloyl" refers to acryloyl or methacryloyl, and "(meth)acrylic acid" refers to acrylic acid or methacrylic acid.

[0031] The aforementioned multifunctional (meth)acrylic acid compound is preferably a multifunctional aliphatic (meth)acrylic acid compound having three or more (meth)acryloyl groups per molecule. From the viewpoint of suppressing deformation of the adhered material, a multifunctional aliphatic (meth)acrylic acid compound having four or more (meth)acryloyl groups per molecule is more preferred. On the other hand, from the viewpoint of adhesiveness, a multifunctional aliphatic (meth)acrylic acid compound having three (meth)acryloyl groups per molecule is more preferred.

[0032] Examples of polyfunctional aliphatic (meth)acrylic acid compounds having three or more (meth)acryloyl groups in one molecule include trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanuric acid tri(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tri(meth)acryloyloxyethyl phosphate, bis(trimethylolpropane)tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and ethylene oxide-modified dipentaerythritol hexa(meth)acrylate.

[0033] It should be noted that in this specification, "(meth)acrylate" refers to acrylate or methacrylate.

[0034] Among the aforementioned polyfunctional (meth)acrylate compounds, compounds other than those having three or more (meth)acryloyl groups in one molecule include, for example, difunctional (meth)acrylate compounds, difunctional aliphatic epoxy (meth)acrylates, polyfunctional aromatic epoxy (meth)acrylates, difunctional aliphatic urethane (meth)acrylates, and polyfunctional aromatic urethane (meth)acrylates. Difunctional aliphatic epoxy (meth)acrylates and polyfunctional aromatic epoxy (meth)acrylates are preferred.

[0035] It should be noted that, in this specification, "epoxy (meth)acrylate" refers to a compound obtained by reacting all the epoxy groups in an epoxy compound with (meth)acrylic acid.

[0036] In addition, examples of the aforementioned difunctional (meth)acrylate compounds include 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 2-n-butyl-2-ethyl-1,3-propanediol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, and polypropylene glycol dimethacrylate. Diol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F di(meth)acrylate, dihydroxymethyldicyclopentadienyl di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, carbonate glycol di(meth)acrylate, polyether glycol di(meth)acrylate, polyester glycol di(meth)acrylate, polycaprolactone glycol di(meth)acrylate, polybutadiene glycol di(meth)acrylate, etc.

[0037] Examples of the above-mentioned difunctional aliphatic epoxy (meth)acrylates or polyfunctional aromatic epoxy (meth)acrylates include substances obtained by reacting a difunctional aliphatic epoxy compound or a polyfunctional aromatic epoxy compound with (meth)acrylate in the presence of a basic catalyst using conventional methods.

[0038] Examples of the aforementioned difunctional aliphatic epoxy compounds or polyfunctional aromatic epoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2'-diallyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenolic resin, o-cresol phenolic resin, dicyclopentadiene phenolic resin, biphenyl phenolic resin, naphthol phenolic resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, and glycidyl ester compounds.

[0039] Commercially available examples of the aforementioned bisphenol A type epoxy resins include jER828EL, jER1004 (both manufactured by Mitsubishi Chemical Corporation), and EPICLON850 (manufactured by DIC Corporation).

[0040] Commercially available examples of the aforementioned bisphenol F type epoxy resins include jER806, jER4004 (both manufactured by Mitsubishi Chemical Corporation), and EPICLON EXA-830CRP (manufactured by DIC Corporation).

[0041] Commercially available examples of the aforementioned bisphenol E type epoxy resins include EPOMIKR710 (manufactured by Mitsui Chemicals Co., Ltd.).

[0042] Commercially available examples of the aforementioned bisphenol S-type epoxy resins include EPICLONEX A-1514 (manufactured by DIC Corporation).

[0043] Commercially available examples of the aforementioned 2,2'-diallyl bisphenol A type epoxy resins include, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).

[0044] Commercially available examples of the aforementioned hydrogenated bisphenol type epoxy resins include EPICLON EXA-7015 (manufactured by DIC Corporation).

[0045] Commercially available examples of the aforementioned propylene oxide addition bisphenol A type epoxy resins include, for example, EP-4000S (manufactured by ADEKA).

[0046] Commercially available examples of the aforementioned resorcinol-type epoxy resins include, for example, EX-201 (manufactured by Nagase ChemteX).

[0047] Commercially available examples of the aforementioned biphenyl-type epoxy resins include, for example, jERYX-4000H (manufactured by Mitsubishi Chemical Corporation).

[0048] Commercially available products among the aforementioned thioether-type epoxy resins include, for example, YSLV-50TE (manufactured by NIPPON STEELC Chemical & Material Co., Ltd.).

[0049] Commercially available examples of the aforementioned diphenyl ether type epoxy resins include YSLV-80DE (manufactured by NIPPON STEELC Chemical & Material Co., Ltd.).

[0050] Commercially available examples of the aforementioned dicyclopentadiene-type epoxy resins include EP-4088S (manufactured by ADEKA).

[0051] Commercially available examples of the aforementioned naphthalene-type epoxy resins include EPICLONHP-4032 and EPICLON EXA-4700 (both manufactured by DIC).

[0052] Commercially available examples of the aforementioned phenolic epoxy resins include EPICLON N-770 (manufactured by DIC Corporation).

[0053] Commercially available products among the aforementioned o-cresol phenolic epoxy resins include, for example, EPICLON N-670-EXP-S (manufactured by DIC Corporation).

[0054] Commercially available examples of the aforementioned dicyclopentadiene phenolic epoxy resins include EPICLON HP-7200 (manufactured by DIC).

[0055] Commercially available examples of the aforementioned biphenyl phenolic epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).

[0056] Commercially available examples of the aforementioned naphthol phenolic epoxy resins include ESN-165S (manufactured by NIPPON STEELC Chemical & Material Co., Ltd.).

[0057] Commercially available products among the aforementioned glycidylamine type epoxy resins include, for example, jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON430 (manufactured by DIC Corporation), and TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation).

[0058] Commercially available examples of the aforementioned alkyl polyol type epoxy resins include ZX-1542 (manufactured by NIPPON STEELC Chemical & Material), EPICLON726 (manufactured by DIC), Epolight 80MFA (manufactured by Kyoei Chemical Co., Ltd.), and Denacol EX-611 (manufactured by Nagase ChemteX).

[0059] Commercially available examples of the aforementioned rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by NIPPON STEEL Chemical & Material), and Epolead PB (manufactured by DAICEL).

[0060] Commercially available examples of the aforementioned glycidyl ester compounds include, for example, Denacol EX-147 (manufactured by NagaseChemteX).

[0061] Other commercially available epoxy compounds mentioned above include YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by NIPPON STEEL Chemical & Material), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, jER1032 (both manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), and TEPIC (manufactured by Nissan Chemical Corporation).

[0062] The aforementioned difunctional aliphatic urethane (meth)acrylate or polyfunctional aromatic urethane (meth)acrylate can be obtained, for example, by reacting a hydroxyl-containing (meth)acrylate derivative with a difunctional aliphatic isocyanate compound or a polyfunctional aromatic isocyanate compound in the presence of a catalytic amount of a tin-based compound.

[0063] Examples of the above-mentioned difunctional aliphatic isocyanate compounds or polyfunctional aromatic isocyanate compounds include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymerized MDI, 1,5-naphthalene diisocyanate, norbornene diisocyanate, dimethylbiphenyl diisocyanate, phenylmethylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tri(isocyanate phenyl)thiophosphate, tetramethylphenylmethylene diisocyanate, and 1,6,11-undecane triisocyanate.

[0064] In addition, as the above-mentioned difunctional aliphatic isocyanate compound or the above-mentioned polyfunctional aromatic isocyanate compound, a chain-extended difunctional aliphatic isocyanate compound or polyfunctional aromatic isocyanate compound obtained by reacting a polyol with an excess of an isocyanate compound can also be used.

[0065] Examples of such polyols include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate glycol, polyether glycol, polyester glycol, and polycaprolactone glycol.

[0066] Examples of the above-mentioned (meth)acrylic acid derivatives having hydroxyl groups include hydroxyalkyl mono(meth)acrylates, mono(meth)acrylates of diols, mono(meth)acrylates or di(meth)acrylates of triols, epoxy (meth)acrylates, etc.

[0067] Examples of the above-mentioned mono(meth)acrylate hydroxyalkyl esters include 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, and 4-hydroxybutyl(meth)acrylate.

[0068] Examples of the aforementioned diols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol.

[0069] Examples of the aforementioned triols include trimethylolethane, trimethylolpropane, and glycerol.

[0070] Examples of the aforementioned epoxy (meth)acrylates include, for example, bisphenol A type epoxy acrylates.

[0071] Examples of trifunctional (meth)acrylic acid compounds having an isocyanuric acid skeleton and having three (meth)acryloyl groups in one molecule include ethoxylated isocyanuric acid tri(meth)acrylate and ε-caprolactone-modified tri-(2-(meth)acryloyloxyethyl)isocyanurate.

[0072] The weight ratio of the polyfunctional aliphatic (meth)acrylic acid compound having three or more (meth)acryloyl groups per molecule to the trifunctional (meth)acrylic acid compound having an isocyanuric acid backbone and having three (meth)acryloyl groups per molecule (polyfunctional aliphatic (meth)acrylic acid compound having three or more (meth)acryloyl groups per molecule: trifunctional (meth)acrylic acid compound having an isocyanuric acid backbone and having three (meth)acryloyl groups per molecule) is preferably 1:9 to 9:1. By setting the weight ratio of the polyfunctional aliphatic (meth)acrylic acid compound having three or more (meth)acryloyl groups per molecule to the trifunctional (meth)acrylic acid compound having an isocyanuric acid backbone and having three (meth)acryloyl groups per molecule to this range, the resulting curable resin composition, when used as a sealant for liquid crystal display elements, exhibits superior low liquid crystal contamination and adhesion to alignment films.

[0073] Of the 100 parts by weight of the aforementioned curable resin, the preferred lower limit for the total content of the polyfunctional aliphatic (meth)acrylic acid compound having three or more (meth)acryloyl groups per molecule and the trifunctional (meth)acrylic acid compound having an isocyanuric acid backbone and having three (meth)acryloyl groups per molecule is 1 part by weight, and the preferred upper limit is 20 parts by weight. By ensuring that the total content of the polyfunctional aliphatic (meth)acrylic acid compound having three or more (meth)acryloyl groups per molecule and the trifunctional (meth)acrylic acid compound having an isocyanuric acid backbone and having three (meth)acryloyl groups per molecule is within this range, it is easier to make the minimum loss modulus of elasticity of the aforementioned photocurable material during the heating process and the storage modulus of the photocurable material at a temperature of glass transition temperature plus 40°C within the aforementioned range. The preferred lower limit for the total content of the above-mentioned polyfunctional aliphatic (meth)acrylic acid compound having three or more (meth)acryloyl groups in one molecule and the above-mentioned trifunctional (meth)acrylic acid compound having an isocyanuric acid skeleton and having three (meth)acryloyl groups in one molecule is 2 parts by weight, and the preferred upper limit is 17 parts by weight.

[0074] For purposes such as minimizing the loss modulus of elasticity of the aforementioned photocurable material during the heating process, optimizing the storage modulus of the photocurable material at a temperature 40°C above its glass transition temperature, or further improving its adhesion and reducing liquid crystal contamination when used as a sealant for liquid crystal display elements, the curable resin preferably contains other curable resins besides the aforementioned polyfunctional (meth)acrylic acid compounds and the aforementioned trifunctional (meth)acrylic acid compounds having an isocyanuric acid backbone and having three (meth)acryloyl groups per molecule. Epoxy compounds and monofunctional (meth)acrylic acid compounds are suitable as the aforementioned other curable resins.

[0075] As the aforementioned epoxy compounds, the aforementioned difunctional aliphatic epoxy compounds and the aforementioned polyfunctional aromatic epoxy compounds can be used.

[0076] As the aforementioned epoxy compounds, epoxy compounds having one (meth)acryloyl group in one molecule from partially (meth)acrylic acid modified epoxy resins are also suitable.

[0077] It should be noted that, in this specification, the aforementioned (meth)acrylic acid modified epoxy resin refers to a compound that can be obtained by reacting a portion of the epoxy groups of an epoxy compound having two or more epoxy groups with (meth)acrylic acid, and that has one or more epoxy groups and (meth)acryloyl groups in one molecule.

[0078] Commercially available examples of the aforementioned (meth)acrylic acid modified epoxy resins include UVACURE1561 and KRM8287 (both manufactured by DAICEL ALLNEX).

[0079] Examples of the aforementioned monofunctional (meth)acrylic acid compounds include, for example, monofunctional (meth)acrylate compounds.

[0080] Examples of the aforementioned monofunctional (meth)acrylate compounds include, for instance, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecanyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and so on. 2-Butoxyethyl methacrylate, 2-phenoxyethyl methacrylate, methoxyethylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl methacrylate, ethyl carbitol (meth)acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H,1H,5H-octafluoropentyl methacrylate, imide (meth)acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl 2-hydroxypropyl phthalate, 2-(meth)acryloyloxyethyl phosphate, glycidyl methacrylate, etc.

[0081] The curable resin composition of the present invention contains a photopolymerization initiator.

[0082] Photoradical polymerization initiators are suitable as the aforementioned photopolymerization initiators.

[0083] Examples of photoradical polymerization initiators include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanoceramsite compounds, oxime ester compounds, benzoin ether compounds, and thioxanone compounds.

[0084] Examples of photoradical polymerization initiators include 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4-morpholino)phenyl)-1-butanone, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxy-2-methyl-1-propane-1-one, 1-(4-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyl oxime), and 2,4,6-trimethylbenzoyl diphenylphosphine oxide.

[0085] The above-mentioned photopolymerization initiators can be used alone or in combination of two or more.

[0086] The preferred lower limit for the content of the photopolymerization initiator relative to 100 parts by weight of the aforementioned curable resin is 0.5 parts by weight, and the preferred upper limit is 10 parts by weight. By keeping the content of the photopolymerization initiator within this range, the resulting curable resin composition exhibits superior storage stability and photocurability. A more preferred lower limit for the content of the photopolymerization initiator is 1 part by weight, and a more preferred upper limit is 7 parts by weight.

[0087] The curable resin composition of the present invention may contain a thermal polymerization initiator.

[0088] Thermal free radical polymerization initiators are suitable as the aforementioned thermal polymerization initiators.

[0089] Examples of thermal free radical polymerization initiators include those composed of azo compounds and organic peroxides. From the viewpoint of suppressing liquid crystal contamination when the obtained cured resin composition is used as a sealant for liquid crystal display elements, initiators composed of azo compounds (hereinafter also referred to as "azo initiators") are preferred, and initiators composed of polymeric azo compounds (hereinafter also referred to as "polymeric azo initiators") are more preferred.

[0090] The above-mentioned thermal free radical polymerization initiators can be used alone or in combination of two or more.

[0091] It should be noted that, in this specification, the term "high molecular weight azo compound" refers to a compound having an azo group and a number-average molecular weight of 300 or more that generates a free radical capable of curing (meth)acryloyl groups through heating.

[0092] The preferred lower limit for the number-average molecular weight of the aforementioned polymeric azo compound is 1000, and the preferred upper limit is 300,000. By ensuring that the number-average molecular weight of the aforementioned polymeric azo compound is within this range, it is possible to prevent adverse effects on the liquid crystal when the obtained cured resin composition is used as a sealant for liquid crystal display elements, and it can be easily mixed into the cured resin. A more preferred lower limit for the number-average molecular weight of the aforementioned polymeric azo compound is 5000, a more preferred upper limit is 100,000, a further preferred lower limit is 10,000, and a further preferred upper limit is 90,000.

[0093] It should be noted that, in this specification, the number-average molecular weight mentioned above is a value obtained by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converted to polystyrene. Examples of columns used for determining the number-average molecular weight based on polystyrene conversion by GPC include Shodex LF-804 (manufactured by Showa Denko Corporation).

[0094] Examples of such polymeric azo compounds include those having a structure in which multiple polyepoxides, polydimethylsiloxanes, or other units are bonded together by means of an azo group.

[0095] As for the aforementioned polymeric azo compound having a structure in which multiple polyoxyalkylene units are bonded by means of an azo group, a polymeric azo compound having a polyoxyethylene structure is preferred.

[0096] Specifically, examples of the aforementioned high molecular weight azo compounds include condensation polymers of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycols, and condensation polymers of 4,4'-azobis(4-cyanovaleric acid) and polydimethylsiloxanes having terminal amino groups.

[0097] Commercially available products among the aforementioned polymeric azo initiators include, for example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd.).

[0098] In addition, examples of non-polymeric azo initiators include V-65 and V-501 (both manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd.).

[0099] Examples of the aforementioned organic peroxides include peroxide ketones, peroxide ketals, hydrogen peroxide, dialkyl peroxides, peroxide esters, diacyl peroxides, and peroxydicarbonates.

[0100] The preferred lower limit for the content of the thermal polymerization initiator relative to 100 parts by weight of the aforementioned curable resin is 0.1 parts by weight, and the preferred upper limit is 10 parts by weight. By keeping the content of the thermal polymerization initiator within this range, better stability and thermosetting properties are maintained. A more preferred lower limit for the content of the thermal polymerization initiator is 0.3 parts by weight, and a more preferred upper limit is 5 parts by weight.

[0101] The curable resin composition of the present invention preferably contains a thermosetting agent.

[0102] Examples of thermosetting agents include organic acid hydrazides, imidazole derivatives, amine compounds, polyphenolic compounds, and acid anhydrides. Among these, solid organic acid hydrazides are particularly suitable.

[0103] Examples of solid organic acid hydrazides include 1,3-bis(hydrazinoethyl)-5-isopropylhydantoin, sebacate dihydrazide, isophthalic acid dihydrazide, adipate dihydrazide, malonate dihydrazide, etc.

[0104] Commercially available examples of the aforementioned solid organic acid hydrazides include those manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazides manufactured by JAPAN FINECHEM Co., Ltd., and organic acid hydrazides manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0105] Examples of organic acid hydrazides manufactured by Otsuka Chemical Co., Ltd. include SDH and ADH.

[0106] Examples of organic acid hydrazides manufactured by JAPAN FINECHEM include MDH.

[0107] Examples of organic acid hydrazides manufactured by Ajinomoto Fine-Techno include Amicure VDH, Amicure VDH-J, and Amicure UDH.

[0108] The above-mentioned thermosetting agents can be used alone or in combination of two or more.

[0109] The preferred lower limit for the content of the thermosetting agent relative to 100 parts by weight of the aforementioned curable resin is 1 part by weight, and the preferred upper limit is 50 parts by weight. By making the content of the thermosetting agent 1 part by weight or more, the thermosetting properties of the resulting curable resin composition are more excellent. By making the content of the thermosetting agent 50 parts by weight or less, the coatability and storage stability of the resulting curable resin composition are more excellent. The more preferred upper limit for the content of the thermosetting agent is 30 parts by weight.

[0110] The curable resin composition of the present invention may contain fillers for purposes such as increasing viscosity, improving adhesion based on stress dispersion effect, improving linear expansion rate, and improving the moisture resistance of cured products.

[0111] Inorganic fillers and organic fillers can be used as the aforementioned fillers.

[0112] Examples of inorganic fillers mentioned above include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, chlorophyll, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, and calcium silicate.

[0113] Examples of organic fillers mentioned above include polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, and acrylic polymer microparticles.

[0114] The above-mentioned fillers can be used alone or in combination of two or more.

[0115] The preferred lower limit for the content of the filler in 100 parts by weight of the curable resin composition of the present invention is 10 parts by weight, and the preferred upper limit is 70 parts by weight. By keeping the content of the filler within this range, the effects of improving adhesion are more superior without deteriorating coatability, etc. A more preferred lower limit for the content of the filler is 20 parts by weight, and a more preferred upper limit is 60 parts by weight.

[0116] The curable resin composition of the present invention may contain a silane coupling agent. The aforementioned silane coupling agent primarily functions as an adhesive aid for effectively bonding the curable resin composition to a substrate or similar material.

[0117] As the aforementioned silane coupling agents, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, and 3-isocyanate propyltrimethoxysilane are suitable examples. They exhibit excellent adhesion to substrates and the like, and when the resulting curable resin composition is used as a sealant for liquid crystal display elements, chemical bonding with the curable resin can suppress the outflow of the curable resin into the liquid crystal.

[0118] The above-mentioned silane coupling agents can be used alone or in combination of two or more.

[0119] The preferred lower limit of the content of the silane coupling agent in 100 parts by weight of the curable resin composition of the present invention is 0.1 parts by weight, and the preferred upper limit is 10 parts by weight. By setting the content of the silane coupling agent within this range, the effect of improving adhesion is more excellent. The more preferred lower limit of the content of the silane coupling agent is 0.3 parts by weight, and the more preferred upper limit is 5 parts by weight.

[0120] The curable resin composition of the present invention may contain a light-blocking agent. By containing the aforementioned light-blocking agent, the curable resin composition of the present invention is suitable for use as a light-blocking sealant.

[0121] Examples of opacifiers include iron oxide, titanium black, aniline black, anthocyanin black, fullerene, carbon black, and resin-coated carbon black. Among these, titanium black is preferred.

[0122] The aforementioned titanium black is a substance with a higher average transmittance for light in the vicinity of the ultraviolet region, particularly light with wavelengths of 370 nm or more and 450 nm or less, than for light with wavelengths of 300 nm or more and 800 nm or less. In other words, the aforementioned titanium black is a light-shielding agent that imparts light-shielding properties to the curable resin composition of the present invention by sufficiently blocking light wavelengths in the visible light region, while allowing light with wavelengths near the ultraviolet region to pass through. Therefore, as the aforementioned photopolymerization initiator, by using a photopolymerization initiator capable of initiating the reaction using light with wavelengths where the transmittance of the aforementioned titanium black increases, the photocurability of the curable resin composition of the present invention can be further increased. Furthermore, as a light-shielding agent contained in the curable resin composition of the present invention, a substance with high insulating properties is preferred, and titanium black is also suitable as a light-shielding agent with high insulating properties.

[0123] The optical density (OD value) per 1 μm of the aforementioned titanium black is preferably 3 or higher, more preferably 4 or higher. Higher opacity of the aforementioned titanium black is better. For the OD value of the aforementioned titanium black, there is no particular upper limit, but it is generally 5 or lower.

[0124] The aforementioned titanium black exhibits sufficient effectiveness even without surface treatment. However, surface-treated titanium black, such as titanium black treated with organic components like coupling agents, or titanium black coated with inorganic components like silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, or magnesium oxide, can also be used. From the viewpoint of further improving insulation, titanium black treated with organic components is preferred.

[0125] Furthermore, liquid crystal display elements manufactured using the curable resin composition of the present invention, incorporating the aforementioned titanium black as a light-blocking agent, as a sealant for liquid crystal display elements have sufficient light-blocking properties, thus enabling the realization of liquid crystal display elements with high contrast and excellent image display quality without light leakage.

[0126] Commercially available titanium black products, such as those manufactured by Mitsubishi Materials Corporation and Akaho Chemical Corporation, are examples.

[0127] Examples of titanium black manufactured by Mitsubishi Materials Corporation include 12S, 13M, 13M-C, 13R-N, and 14M-C.

[0128] Examples of titanium black manufactured by Akaho Chemical Co., Ltd. include Tilack D.

[0129] The preferred lower limit for the specific surface area of ​​the aforementioned titanium black is 13m². 2 / g, with a preferred upper limit of 30m 2 / g, with a more preferred lower limit of 15m 2 / g, with a more preferred upper limit of 25m 2 / g.

[0130] In addition, the preferred lower limit of the volume resistivity of the above-mentioned titanium black is 0.5 Ω·cm, the preferred upper limit is 3 Ω·cm, the more preferred lower limit is 1 Ω·cm, and the more preferred upper limit is 2.5 Ω·cm.

[0131] When the obtained curable resin composition is used as a sealant for liquid crystal display elements, the primary particle size of the light-blocking agent is not particularly limited as long as it is less than or equal to the distance between the substrates of the liquid crystal display element. A preferred lower limit is 1 nm, and a preferred upper limit is 5000 nm. By setting the primary particle size of the light-blocking agent to this range, superior light-blocking properties can be achieved without deteriorating the coatability or other properties of the obtained curable resin composition. A more preferred lower limit for the primary particle size of the light-blocking agent is 5 nm, a more preferred upper limit is 200 nm, a further preferred lower limit is 10 nm, and a further preferred upper limit is 100 nm.

[0132] It should be noted that the primary particle size of the above-mentioned opacifier can be determined using a NICOMP380ZLS (manufactured by PARTICLE SIZING SYSTEMS) to disperse the opacifier in a solvent (water, organic solvent, etc.).

[0133] The preferred lower limit of the content of the above-mentioned opaque agent in 100 parts by weight of the curable resin composition of the present invention is 5 parts by weight, and the preferred upper limit is 80 parts by weight. By keeping the content of the above-mentioned opaque agent within this range, superior opacity can be achieved without significantly reducing the adhesion, cured strength, and drawability of the obtained curable resin composition. A more preferred lower limit of the content of the above-mentioned opaque agent is 10 parts by weight, a more preferred upper limit is 70 parts by weight, a further preferred lower limit is 30 parts by weight, and a further preferred upper limit is 60 parts by weight.

[0134] The curable resin composition of the present invention may further contain, as needed, additives such as stress relaxants, reactive diluents, thixotropic agents, spacers, curing accelerators, defoamers, leveling agents, and polymerization inhibitors.

[0135] As a method for manufacturing the curable resin composition of the present invention, examples include mixing the curable resin, photopolymerization initiator, thermosetting agent, and additives such as silane coupling agent added as needed using a homogenizer, homogenizer, universal mixer, planetary mixer, kneader, three-roll mill, or other mixer.

[0136] The curable resin composition of the present invention is suitable for use as a sealant for liquid crystal display elements. A sealant for liquid crystal display elements made using the curable resin composition of the present invention is also part of the present invention.

[0137] By incorporating conductive microparticles into the curable resin composition of the present invention, it is possible to manufacture a material with vertically and horizontally conductive properties. Such a material containing the curable resin composition of the present invention and conductive microparticles is also part of the present invention.

[0138] As the aforementioned conductive particles, metal spheres, particles with a conductive metal layer formed on the surface of resin particles, etc., can be used. Among them, particles with a conductive metal layer formed on the surface of resin particles are suitable because the excellent elasticity of resin particles allows for conductive bonding without damaging transparent substrates, etc.

[0139] A liquid crystal display element made using the liquid crystal display element sealant of the present invention or the upper and lower conductive material of the present invention is also one of the present inventions.

[0140] The sealant for liquid crystal display elements of the present invention is suitable for use in the manufacture of liquid crystal display elements based on liquid crystal droplet technology.

[0141] As a method for manufacturing the liquid crystal display element of the present invention by liquid crystal droplet process, the following methods can be cited as examples.

[0142] First, a process is performed to form a frame-shaped sealing pattern on a substrate using the sealant for liquid crystal display elements of the present invention, through screen printing, dispensing, or other methods. Next, while the sealant for liquid crystal display elements of the present invention is still uncured, tiny droplets of liquid crystal are applied to the entire surface within the frame of the sealing pattern, and then another substrate is immediately overlapped. Then, a process is performed to pre-cur the sealant by irradiating the sealing pattern portion of the sealant for liquid crystal display elements of the present invention with ultraviolet light, and a process is performed to heat the pre-cured sealant to fully cure it. Through this method, a liquid crystal display element can be obtained.

[0143] Invention Effects

[0144] According to the present invention, a curable resin composition capable of suppressing deformation of the adhered material caused by external forces or internal stress can be provided. Furthermore, according to the present invention, a sealant for a liquid crystal display element, an upper and lower conductive material, and a liquid crystal display element made using the curable resin composition can be provided. Detailed Implementation

[0145] The present invention will be described in more detail below with reference to specific embodiments, but the present invention is not limited to these embodiments.

[0146] (Examples 1-5 and Comparative Examples 1-5)

[0147] The materials in the proportions listed in Table 1 were mixed using a planetary mixer (THINKY Corporation, "Defoaming Rentaro"), and then further mixed using a three-roll mill, thereby preparing the curable resin compositions of Examples 1-5 and Comparative Examples 1-5.

[0148] (Minimum loss modulus of elasticity of UV-cured material during the heating process)

[0149] For each of the obtained curable resin compositions, a UV-cured product was obtained by irradiating it with 100 mW / cm² ultraviolet light (wavelength 365 nm) for 30 seconds through a metal halide lamp with a cutoff filter below 340 nm. For the obtained UV-cured products, the minimum loss modulus of elasticity during the heating process was measured using a dynamic viscoelasticity measuring device (IT Measurement & Control Co., Ltd., "DVA-200") under the following conditions: tensile mode, test piece width 5 mm, thickness 0.35 mm, clamping width 25 mm, heating rate 10 °C / min, holding temperature 120 °C, and frequency 10 Hz. The results are shown in Table 1.

[0150] (Storage modulus of the photothermal curing material at its glass transition temperature plus 40°C)

[0151] For each of the obtained curable resin compositions, irradiation with a metal halide lamp at 100 mW / cm² was performed through a cutoff filter below 340 nm. 2After 30 seconds of exposure to ultraviolet light (wavelength 365nm), the sample was heated at 120°C for 1 hour to obtain a photocured product. The dynamic viscoelasticity of the obtained photocured product was measured using a dynamic viscoelasticity measuring device (IT Measurement & Control Co., Ltd., "DVA-200") under tensile mode, with a sample width of 5mm, a thickness of 0.35mm, a clamping width of 25mm, a heating rate of 10°C / min, and a frequency of 10Hz. The temperature at which the loss tangent (tanδ) reached its maximum value was determined as the glass transition temperature. Next, the storage modulus of the obtained photocured product was measured at a temperature 40°C above the glass transition temperature using the same dynamic viscoelasticity measuring device (IT Measurement & Control Co., Ltd., "DVA-200") under tensile mode, with a sample width of 5mm, a thickness of 0.35mm, a clamping width of 25mm, a heating rate of 10°C / min, and a frequency of 10Hz. The results are shown in Table 1.

[0152] <Evaluation>

[0153] The curable resin compositions obtained in the Examples and Comparative Examples were evaluated as follows. The results are shown in Table 1.

[0154] (Adhesion to the alignment film)

[0155] One part by weight of spacer particles (manufactured by Sekisui Chemicals, Inc., “Micropearl SP-2050”) with an average particle size of 5 μm was uniformly dispersed relative to 100 parts by weight of each curable resin composition obtained in the Examples and Comparative Examples using a planetary stirrer. A very small amount of the curable resin composition with dispersed spacer particles was taken to the center of a glass substrate (20 mm × 50 mm × 0.7 mm thick) with a TN polyimide orientation film (manufactured by Nissan Chemical Co., Ltd., “SE7492”) on its surface, and a glass substrate of the same type was stacked on top. The curable resin composition was spread and irradiated with a metal halide lamp at 100 mW / cm². 2 After being exposed to ultraviolet light (wavelength 365nm) for 30 seconds, the curable resin composition was heated at 120°C for 1 hour to cure, thus obtaining an adhesive test piece.

[0156] The bond strength of the obtained bonded test pieces was determined using a tension meter.

[0157] (Low liquid crystal contamination)

[0158] One part by weight of spacer particles with an average particle size of 5 μm was dispersed in 100 parts by weight of each curable resin composition obtained in the Examples and Comparative Examples. SI-H040 (manufactured by Sekisui Chemicals Co., Ltd.) was used as the spacer particles. Next, the curable resin composition was filled into a dispensing syringe and degassed. A PSY-10E (manufactured by Musashi Engineering Co., Ltd.) was used as the dispensing syringe. The degassed curable resin composition was applied in a frame shape with a line width of 1 mm onto one of two substrates (375 mm in length and 305 mm in width) with a rubbed alignment film and a transparent electrode. A SHOTMASTER300 (manufactured by Musashi Engineering Co., Ltd.) was used as the dispensing syringe.

[0159] Next, tiny droplets of liquid crystal are deposited onto the entire surface of a curable resin composition within a frame on a substrate with transparent electrodes, and then immediately bonded to another substrate. A JC-5004LA (manufactured by Chisso Corporation) is used as the liquid crystal. The curable resin composition is then irradiated with a metal halide lamp at 100 mW / cm². 2 After being exposed to ultraviolet light (wavelength 365nm) for 30 seconds, the liquid crystal display element is obtained by heating at 120°C for 1 hour.

[0160] For the obtained liquid crystal display element, visual confirmation was made that the liquid crystal alignment disorder (display unevenness) was caused by applying a voltage for 1 hour at 80°C and 90%RH.

[0161] The case where no display unevenness is observed in the liquid crystal display element is marked as "○", the case where display unevenness exists near the curable resin composition of the liquid crystal display element (peripheral portion) is marked as "△", and the case where display unevenness extends not only to the peripheral portion but also to the central portion is marked as "×". Low liquid crystal contamination is evaluated.

[0162] (The resistance to deformation of the adhered object)

[0163] One part by weight of spacer particles with an average particle size of 5 μm was dispersed in 100 parts by weight of each curable resin composition obtained in the Examples and Comparative Examples. SI-H040 (manufactured by Sekisui Chemicals Co., Ltd.) was used as the spacer particles. Next, the curable resin composition was filled into a dispensing syringe and degassed. A PSY-10E (manufactured by Musashi Engineering Co., Ltd.) was used as the dispensing syringe. The degassed curable resin composition was applied in a frame shape with a line width of 1 mm to the inner side of one of two glass substrates (400 mm in length, 300 mm in width, and 0.7 mm in thickness), 1 cm from each side of the surface of the glass substrate. A SHOTMASTER300 (manufactured by Musashi Engineering Co., Ltd.) was used as the dispensing syringe. Then, one glass substrate is bonded to another through the coated curable resin composition, and the curable resin composition is irradiated with a metal halide lamp at 100 mW / cm². 2 The sample was exposed to ultraviolet light (wavelength 365nm) for 30 seconds and then heated at 120℃ for 1 hour to obtain the test piece.

[0164] The obtained test piece was fixed on a support (360 mm in length, 10 mm in width, and 10 mm in height), with 20 mm of each long side of the test piece exposed evenly. Next, 0.5 kg weights were suspended from the center of each end of the long side of the test piece. After heating at 120°C for 1 hour, the piece was cooled to 25°C for a deformation test. Using the test piece before the deformation test as a reference, the warpage height of the substrate in the test piece after the deformation test was measured (the displacement of both ends of the long side in the direction of suspension).

[0165] The warpage height of the substrate is marked as “◎” if it is less than 0.8 mm, marked as “○” if it is 0.8 mm or more but less than 1 mm, marked as “△” if it is 1 mm or more but less than 2 mm, and marked as “×” if it is 2 mm or more. The deformation resistance of the adhered object is evaluated.

[0166] [Table 1]

[0167]

[0168] Industrial availability

[0169] According to the present invention, a curable resin composition capable of suppressing deformation of the adhered material caused by external forces or internal stress can be provided. Furthermore, according to the present invention, a sealant for a liquid crystal display element, an upper and lower conductive material, and a liquid crystal display element made using the curable resin composition can be provided.

Claims

1. A curable resin composition, characterized in that, It contains curable resin and photopolymerization initiator. The curable resin comprises a polyfunctional (meth)acrylic acid compound having two or more (meth)acryloyl groups in one molecule, and a trifunctional (meth)acrylic acid compound having an isocyanuric acid skeleton and having three (meth)acryloyl groups in one molecule. The polyfunctional (meth)acrylic acid compound is a polyfunctional aliphatic (meth)acrylic acid compound having three or more (meth)acryloyl groups in one molecule. Irradiation of the cured resin composition to 3000 mJ / cm 2 When the photocured material obtained by ultraviolet light is heated from 25°C to 120°C at a heating rate of 10°C / min, the minimum loss modulus of elasticity in the heating process is greater than 1.5 MPa.

2. The curable resin composition according to claim 1, wherein, The curable resin composition was irradiated with 3000 mJ / cm 2 After being exposed to ultraviolet light, the photothermal cured material is obtained by heating at 120°C for 1 hour. The storage modulus of the photothermal cured material at a temperature of glass transition temperature plus 40°C is 50 MPa or higher.

3. A sealant for a liquid crystal display element, which is made using the curable resin composition according to claim 1 or 2.

4. A conductive material comprising the curable resin composition of claim 1 or 2 and conductive microparticles.

5. A liquid crystal display element, which is made using the liquid crystal display element sealant of claim 3 or the top and bottom conductive material of claim 4.

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