KR101279877B1 - Photocurable composition for liquid crystal display panel seal, and liquid crystal display panel - Google Patents

Abstract

0.1-4 mass% of nonionic surfactant whose HLB value is 10 or more with respect to photocurable composition solid content whole quantity, The photocurable composition for liquid crystal display panel seals characterized by the above-mentioned.
It is preferable that the said nonionic surfactant is alkylene oxide modified polydimethylsiloxane. It has the outstanding electrical property and adhesiveness, and has the outstanding adhesiveness with respect to the board | substrate for liquid crystal cells which has a base material which makes SiOx, SiNx, and ITO electrode the surface especially with plastics.

Description

Photocurable composition for liquid crystal display panel seal and liquid crystal display panel {PHOTOCURABLE COMPOSITION FOR LIQUID CRYSTAL DISPLAY PANEL SEAL, AND LIQUID CRYSTAL DISPLAY PANEL}

The present invention relates to a photocurable composition for a liquid crystal display panel seal, and more particularly, to a photocurable composition for a photocationic curable liquid crystal display panel seal.

In general, a liquid crystal display panel is configured by opposing a rear substrate including a thin film transistor, a pixel electrode, an alignment film, and the like, and a front substrate including a color filter, an electrode, an alignment film, and the like, and encapsulating a liquid crystal between both substrates. And the sealing agent is used for the purpose of sticking two board | substrates together.

In recent years, in order to reduce the thickness and weight of a liquid crystal display panel, or to provide flexibility, it has been studied to replace the materials of both the front substrate and the front back substrate from conventional glass to plastic. However, the sealant used conventionally is mostly developed for glass, and it was difficult to use it as it is. In the case of using a thermosetting sealant mainly composed of epoxy-based thermosetting resins, the curing agent is often hardened at 150 ° C. However, in the case of bonding substrates having different temperature differences or thermal expansion coefficients between the upper and lower substrates, the panels are cooled to room temperature. When it did, there existed a problem that a liquid crystal display panel bent. For the purpose of avoiding this, a method of adding a curing catalyst such as an inorganic solid acid such as silica or an organic acid such as salicylic acid to the epoxy resin and performing a curing reaction at a low temperature of 40 ° C. or lower is also attempted (for example, a patent document). 1), hardening takes a long time and is not practical.

On the other hand, the photocurable sealing agent (for example, refer patent document 2) which has an acrylate etc. as a main component is suitable for a plastic board | substrate, since hardening in a short time is possible without requiring heat for hardening. However, since acrylate has large curing shrinkage, adhesiveness is weak, and it may peel off by a simple impact etc., and there existed a problem practically. Moreover, although the photocurable component and the thermosetting component are used together and the photocurable sealant which semicurs | cures by photocuring for the first time and then fully hardens by heating (usually using heating at the time of annealing) is also known (for example, a patent) Documents 3 to 6), too, had poor adhesion to plastic substrates and had problems in practical use.

On the other hand, the photocurable sealing agent (for example, refer patent document 7) which has an optical binary curing system which uses together the photocationic curable which has epoxy as a main component, and the acrylate which has photoradical curable, etc. requires heat for hardening. Not only can it be cured in a short time, but also the photo-opening reaction can be used to significantly improve the adhesion between the organic protective layer and SiOx. However, the adhesion to the surface of the SiNx or ITO electrode base material is weak, and there is a problem that the base material that can be used is limited.

[Prior Art Literature]

[Patent Literature]

Patent Document 1: Japanese Patent Application Laid-Open No. 11-153800

Patent Document 2: Japanese Patent Application Laid-Open No. 2005-171135

Patent Document 3: Japanese Patent Application Laid-Open No. 5-295087

Patent Document 4: Japanese Patent Application Laid-Open No. 2005-18022

Patent Document 5: Japanese Patent Application Laid-Open No. 2006-23582

Patent Document 6: Japanese Patent Application Laid-Open No. 3-188186

Patent Document 7: Japanese Patent Application Laid-Open No. 2008-96575

SUMMARY OF THE INVENTION [

[Problems to be solved by the invention]

SUMMARY OF THE INVENTION The problem to be solved by the present invention is excellent electrical properties and adhesiveness, in particular, a plastic material, having an excellent adhesion to a substrate for a liquid crystal cell having a substrate having SiOx, SiNx, ITO electrode as the adhesive surface It is providing the photocurable composition for liquid crystal display panel sealing.

[Means for solving the problem]

MEANS TO SOLVE THE PROBLEM This inventor solved the said subject by adding a small amount of nonionic surfactants to the photocurable composition for liquid crystal display panel seals.

Since surfactants have a surface tension lowering ability, they mainly provide or improve wettability, permeability, electrodeposition property, bubble stability, flowability, leveling property, antifoaming property, emulsification property, dispersibility, water / oil repellency. Or additives used for the purpose. The present inventors found that a specific surfactant can enhance the adhesiveness of the liquid crystal sealant and does not reduce the voltage retention.

That is, this invention provides the photocurable composition for liquid crystal display panel seals which contains 0.1-4 mass% of nonionic surfactant whose HLB value is 10 or more with respect to photocurable composition solid content whole quantity.

Moreover, this invention provides the liquid crystal display panel using the photocurable composition for liquid crystal display panel seals of the said base material.

[Effects of the Invention]

ADVANTAGE OF THE INVENTION According to this invention, the liquid crystal display panel which has the outstanding electrical property and adhesiveness, and has outstanding adhesiveness with respect to the board | substrate for liquid crystal cells which has a base material which makes SiOx, SiNx, and ITO electrode an adhesion surface especially using plastic as a material. The photocurable composition for sealing is obtained.

[Mode for Carrying Out the Invention]

(Nonionic surfactant)

As a nonionic surfactant used by this invention, the thing which alkylene oxide added to the higher alcohol, higher amine, higher fatty acid, or silicone main chain can be used, for example. Specifically, for example, polyoxyethylene alkyl ether, polyoxyethylene propylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, polyoxyethylene sterol, polyoxyethylene hydrogen Hydrogenated sterol, polyoxyethylene alkylphenyl formaldehyde condensate, polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyglycerol fatty acid ester, polyoxyethylene glycerin fatty acid ester, poly Oxyethylene alkyl ether acetic acid is preferable, More preferably, alkylene oxide modified silicone type surfactants, such as an alkylene oxide modified polydimethylsiloxane, are preferable since they are excellent in adhesive enhancement and do not reduce voltage retention.

Specifically, even when a small amount of the silicone-based surfactant represented by the general formula (1) to which the alkylene oxide is added to the silicon main chain is added, it is more preferable from the viewpoint of providing excellent adhesion.

(One)

In the general formula (1), R represents a hydrogen atom, a butyl group or an acetyl group, x, y, z, a and b represent integers of repeating units, x is 0 ≦ x ≦ 50 and y is 1 ≦ y ≤ 10, z is 0 ≤ z ≤ 10, a is 1 ≤ a ≤ 200 and b is 0 ≤ b ≤ 100.

Especially, it is more preferable that a which is the repeating unit number of the ethylene oxide chain in the said General formula (1) is a <= 100. By setting a ≦ 100, the hydrophobic portion and the hydrophilic portion are appropriately mixed in the nonionic surfactant represented by the general formula (1), and thus tends to tend to develop adhesiveness.

The said nonionic surfactant may have an epoxy group. By having an epoxy group, it is more preferable because it introduces into the structure of a curable composition by photocationic hardening, and acts favorably on adhesiveness.

A commercial item can be used for the said nonionic surfactant, For example, the "BT" series by Nikko Chemicals Corporation, the "Nonipol" series by Sanyosei Co., Ltd., "D-" "P-" series by Takemoto Yushi Corporation , Polyether-modified silicones such as `` sappinol '' series made by Air Products, `` orpin '' series made by Nisshin Chemical Co., Ltd., `` EMALEX DAPE '' series made by Nippon Emulsion Co., Ltd., product made by Toray Dow Corning or Shin-Etsu Chemical Co., Ltd. Can be.

In this invention, the HLB value of the said nonionic surfactant is 10 or more. Especially, it is most preferable that it is 11-14. If the HLB value is less than 10, the adhesion to SiOx, ITO, and SiNx surfaces tends to be lost. On the other hand, if the HLB value exceeds 15, adverse effects on the electrical properties tend to occur, which is not preferable.

In addition, the HLB value is used as an index indicating the hydrophilicity and lipophilicity of the surfactant, and some calculation methods have been proposed. For example, the nonionic surfactant HLB value is represented by the following formula,

[Number 1]

HLB = [{(Molecular Weight of Ethylene Oxide Chain) / (Molecular Weight of Surfactant)} × 100] ÷ 5

Can be defined as

The nonionic surfactant is added to the photocurable composition for a liquid crystal display panel seal of the present invention (hereinafter sometimes abbreviated as "photocurable composition for seals") in a very small amount so that the SiOx, SiNx or ITO electrode is used as the adhesive surface. Since it exhibits about the base material to be mentioned, the board | substrate for plastic liquid crystal cells provided with these members can be adhere | attached favorably. In order to raise adhesive force more, it is preferable that it is the range of 0.1-4.0 mass% with respect to solid content whole quantity of the photocurable composition for seals of this invention, and 0.1-2.0 mass% is the most preferable. If the amount added is too large, elution to the liquid crystal occurs, which leads to a decrease in the voltage retention, which is not preferable because the electrical properties are affected.

(Photocurable composition for liquid crystal display panel seal)

Although the cured form of the photocurable composition for liquid crystal display panel seals of this invention may be a radical photocuring system, a cationic photocuring system, or what used these together, what used the cation photocuring system or a radical photocuring system and a cationic photocuring system together is used together. Since it is excellent in the balance of the light beam hardenability and the adhesiveness with respect to the board | substrate which has SiOx, SiNx, or ITO on the surface, and can exhibit the effect of this invention more, it is preferable.

(Composition of Cationic Photocuring System)

A composition of a cationic photocuring system (hereinafter referred to as a cationic photocurable composition) is a composition containing a cationic polymerizable compound and a cationic photopolymerization initiator. The cationically polymerizable compound is not particularly limited as long as it is a known conventional compound having an epoxy group, an oxetanyl group, and a vinyl ether group which are generally used in the field of UV curing. However, since the compound which has an oxetanyl group has few hydroxyl groups produced | generated by superposition | polymerization, since it is disadvantageous in adhesiveness with a plastic substrate with a large deformation | transformation compared with a glass substrate, it is more preferable to suppress it by using a small amount.

As a cationically polymerizable compound which has one or more epoxy groups in 1 molecule, For example, bisphenol-A epoxy resin (brand name "Epiclon 850CRP", "Epiclon 850S", "Epiclon 1050", "Epiclon 1050" made by DIC Corporation) 1055 "), Bisphenol F type epoxy resin (brand name" Epiclon 830CRP "made by DIC Corporation," Epiclon 830 ", bisphenol S type epoxy resin (brand name" Epiclon EXA1514 "made by DIC Corporation), hydrogenated bisphenol type epoxy Resin (brand name "Epiclon EXA7015" made by DIC Corporation), propylene oxide addition bisphenol A type epoxy resin (brand name "EP-4000S" made by Asahi Denka Co., Ltd.), resorcinol type epoxy resin (brand name "EX- made by Nagase Camtex company) 201 "), biphenyl type epoxy resin (brand name" Epicoat YX-4000H "made in Japan epoxy resin company), dicyclopentadiene type epoxy resin (brand name" EP-4088S "made by Asahi Denka Corporation), naphthalene type epoxy resin (DIC Product name "Epiclon HP4032", "Epiclon EXA-4700", phenol novolak-type epoxy resin (brand name "epiclon N-770" made by DIC Corporation), orthocresol novolak-type epoxy resin (product made in DIC Corporation) Naphthalene phenol novolak-type epoxy resins, such as biphenyl novolak-type epoxy resins, such as "Epiclon N-670-EXP-S") and NC-3000P (made by Nippon Kayaku Co., Ltd.), and ESN-165S (made by Todogase Co., Ltd.) , Epicoat 630 (made in Japan epoxy resin company), rubber modified type epoxy resin (brand name "PB3600" made by Daicel Chemical Co., Ltd.), bisphenol A type episulfide resin (brand name "epi coat YL-7000" made in Japan epoxy resin company) The alicyclic epoxy resin (The brand name "Celoxide 2021", "Celoxide 2080", "Celoxide 3000", "EHPE" by Daicel Chemical Co., Ltd.), etc. are mentioned.

As a commercial item of the cationically polymerizable compound which has the said 1 or more vinyl ether group, 4-vinyloxy butanol (brand name "Vinyl-4-hydroxybutylether" by BASF Corporation), triethylene glycol divinyl ether (brand name "Rapi-Cure by ISP company") DVE-3 "), 1, 4- cyclohexane dimethanol divinyl ether (brand name" CHDVE "by Nippon Carbide Co., Ltd.), etc. are mentioned.

As a cationically polymerizable compound which has 1 or more oxetanyl group in 1 molecule, 3-ethyl-3- (phenoxymethyl) oxetane (brand name "OXT-211" by Toagosei Co., Ltd.), 3-ethyl is mentioned, for example. 3- (cyclohexyl) methyl oxetane (trade name "CHOX" by Toagosei Co., Ltd.) etc. are mentioned. Examples of the compound having two or more oxetane rings include 1,4-bis [{(3-ethyloxetan-1-yl) methoxy} methyl] benzene (trade name "OXT-121" manufactured by Toagosei Co., Ltd.), 1,3 -Bis [(3-ethyloxetan-3-yl) methoxy] benzene (trade name "OXT-223" made by Toagosei Co., Ltd.), bis [1-ethyl (3-oxetanyl)] methyl ether (made by Toagosei Co., Ltd.) Brand name "OXT-221"), phenol novolak oxetane (brand name "PNOX-1009" made by Toagosei Co., Ltd.), 4,4'-bis [{(3-ethyloxetane-1 yl) methoxy} methyl] Biphenyl (trade name "OXBP" by the Ubegosan Co., Ltd.) is mentioned.

Among the above cationically polymerizable compounds, the cohesive force is obtained by the use of the interaction between the aromatic rings and is advantageous for adhesion, and therefore, the polymerizable compound having an epoxy group having an aromatic ring is particularly preferable. Specifically, bisphenol A type epoxy resin (brand name "Epiclon 850CRP", "Epiclon 850S", "Epiclon 1050", "Epiclon 1055" made by DIC Corporation), bisphenol F type epoxy resin (brand name "made by DIC Corporation" Epiclonal 830CRP "," epiclon 830 "), and the like.

In particular, since a viscosity is low and the dilution effect with the compound represented by General formula (1) is also high, bisphenol-A epoxy resin (brand name "Epiclon 850CRP" made by DIC Corporation), bisphenol F-type epoxy resin (brand name "made by DIC Corporation" Epiclonal 830CRP '') is particularly preferred.

Moreover, as cationic photoinitiator, onium salts, such as an aromatic diazonium salt, an aromatic iodonium salt, and an aromatic sulfonium salt, are mentioned, for example. When using the said cationic photoinitiator, the preferable minimum of the wavelength range of the light to irradiate is 300 nm, and a preferable upper limit is 420 nm.

Commercially available among these onium salts include, for example, Optomer SP-150, Optomer SP-151, Optomer SP-170, Optomer SP-171 (all manufactured by Asahi Denka Co., Ltd.), and UVE-1014 (General). Electronics Co., Ltd.), Irgacure 261 (product made by Chiba Co., Ltd.), Sanade SI-60L, Sanade SI-80L, UVI-6990 (manufactured by Union Carbide), BBI-103, MPI-103, TPS-103, MDS- 103, DTS-103, NAT-103, NDS-103 (all made by Midori Chemical Co., Ltd.), Sanade SI-100L (all made by Sanshin Chemical Co., Ltd.), CI-2064, CI-2639, CI-2624, CI-2481 ( Nippon Soda Co., Ltd., RHODORSIL PHOTOINITIATOR 2074 (made by Rhone-Poulenc), CD-1012 (made by Satomer), etc. are mentioned. Among them, the Optomer SP-150 is more preferable because it is difficult to cause electrode corrosion by the onium salt, and effective hardenability is easily obtained.

The said cationic photoinitiator may be used independently and may use 2 or more types together. Moreover, you may use together sensitizers, such as anthracene type and a thioxanthone type as needed. In addition, it is although it does not specifically limit as a compounding ratio of the said cationic photoinitiator, Usually, it is used within the range of 0.1-10 mass% with respect to cationically polymerizable compound whole quantity. If it is less than 0.1 mass%, there exists a possibility that the sclerosis | hardenability of the sealing agent of this invention may become inadequate, and when it exceeds 10 mass%, the cationic photoinitiator which did not react at all may remain and elute to a liquid crystal. Especially, 0.3-3 mass% is preferable.

(Composition of radical photocuring system)

The composition of a radical photocuring system (henceforth a radical photocurable composition) is a composition containing a radically polymerizable compound and a radical photoinitiator. The radically polymerizable compound is not particularly limited as long as it is a known conventional compound having a (meth) acryloyl group generally used in the field of UV curing, but when used as a liquid crystal display panel seal, it is more difficult to mix with a liquid crystal. It can be used preferably. However, in order to avoid excessive curing shrinkage, (meth) acrylates such as dipentaerythritol (penta / hexa) acrylate and pentaerythritol tetraacrylate, which are said to have a large curing shrinkage, should be suppressed with a small amount of use. desirable. Moreover, since the radically polymerizable compound which has a carboxylic acid group may react with an epoxy group during storage, and may raise a composition viscosity rapidly, it is preferable to suppress it by use of a small amount.

Epoxy obtained by modifying with polyester (meth) acrylate and epichlorohydrin having ester bond in the main chain structure called "photopolymerizable oligomer" and having at least two (meth) acryloyl groups in the field of UV curing ( (Meth) acrylate modified with meta) acrylate, ethyl oxide, propylene oxide, cyclic lactone and the like can also be preferably used. However, when the acrylate having a urethane group is combined with a cationic curing system, curing inhibition by the urethane group occurs, and therefore it is preferable to suppress the acrylate with a small amount of use.

As a specific example of the (meth) acrylate used by this invention, the glycerin monomethacrylate (brand name "Blemmer GLM" by Nippon Yushi Corporation) and acryloyloxy ethyl phthalate (made by Koeisha Chemical Co., Ltd.) are mentioned, for example. Brand name "HOA-MPE"), benzyl (meth) acrylate (brand name "biscoat # 160" made by Osaka Yuki Chemical Co., Ltd.), nonylphenoxy polyethylene glycol acrylate (brand name "Aronix M111" made by Toagosei Corporation, " Aronix M113 "," Aronix M117 "), ECH modified phenoxyacrylate (brand name" Aronix M5700 "made by Toagosei Co., Ltd.), EO modified succinic acid acrylate (brand name" HOA-MS "made by Koeisha Chemical Co., Ltd.) ), (Meth) acryloyl group, such as EO modified phosphate methacrylate (brand name "P-1M" made by Koeisha Chemical Co., Ltd.), rosin modified epoxy acrylate (brand name "beamset 101" made by Arakawa Chemical Co., Ltd.) Having one ) Acrylic, bis (acryloyl ethyl) hydroxyethyl isocyanurate (brand name "Aronix M215" made by Toagosei Co., Ltd.), EO modified bisphenol A diacrylate (brand name "ADPE-150" made by Nippon Yushi Corporation) , PO modified bisphenol A diacrylate (brand name "ADBP-200" made by Nippon Yushi Corporation), ECH modified bisphenol A type acrylate (brand name "DICLITE UE8200" made by DIC Chemical Co., Ltd.), ECH modified phthalic acid diacrylate (Nagase Chemical Brand name "DA-721" made by Sisa, ECH modified hexahydrophthalic acid diacrylate (brand name "DA-722" made by Nagase Chemical Co., Ltd.), and tricyclodecane dimethanol diacrylate (brand name "IRR214 made by Daicel UCB company") ), Rosin modified ester acrylate (brand name "beamset 115B" made by Arakawa Chemical Co., Ltd.), EO modified phosphate dimethacrylate (brand name "P-2M" by Koeisha Chemical Co., Ltd.), tris (acryloyloxy Ethyl) isocy Nourate (brand name "Aronix M315" made by Doagosei Co., Ltd.), dimethylol propane tetraacrylate (brand name "Aronix M408" made by Doagosei Corporation), dipentaerythritol hexaacrylate (brand name "Kaya made by Nippon Kayaku Co., Ltd.") Rad DPHA ''), two or more (meth) acryloyl groups, such as caprolactone modified dipentaerythritol hexaacrylate (trade name "Kayarad DPCA-30", "Kayarad DPCA-120" made by Nippon Kayaku Co., Ltd.) (Meth) acrylate which has, etc. are mentioned.

In particular, among the radically polymerizable compounds, (meth) acrylate modified with lactone and (meth) acrylate modified with rosin are particularly preferable because they soften the curable composition and make adhesiveness advantageous. Specifically, lactone modified hydroxy pivalate neopentyl glycol diacrylate (brand name "HX620" made by Nippon Kayaku Co., Ltd.), lactone modified BPA epoxy phthalic acid ester diacrylate (brand name "evercryl 3708" made by Daicel Cytec company) And rosin-modified epoxy acrylate (trade name "Beamset 101" manufactured by Arakawa Chemical Industries).

The usage-amount of the said (meth) acrylate will not be specifically limited if it is a range which does not impair the range of this invention. Specifically, it is preferable that it is the range of 20-70 mass% with respect to solid content whole quantity of the photocurable composition for sealing of this invention.

Moreover, as a radical photoinitiator, benzophenone, 2, 2- diethoxy acetophenone, benzyl, benzoyl isopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, thioxanthone, etc. can be used, for example. have. These radical photoinitiators may be used independently and may use 2 or more types together.

Moreover, the maleimide compound which has photoinitiation property can also be used. As a specific example of the maleimide compound which has photoinitiation ability, the maleimide compound of Unexamined-Japanese-Patent No. 2000-19868 and Unexamined-Japanese-Patent No. 2004-070297 is mentioned, for example.

The said radical photoinitiator may be used independently and may use 2 or more types together. Moreover, although it does not specifically limit as a compounding ratio of the said radical photoinitiator, It uses within the range of 0.1-20 mass% with respect to radically polymerizable compound whole quantity. If it is less than 0.1 mass%, there exists a possibility that the sclerosis | hardenability of the sealing agent of this invention may become inadequate, and when it exceeds 10 mass%, the cationic photoinitiator which did not react at all may remain and elute to a liquid crystal. Especially, 0.3-10 mass% is preferable.

In addition, when using together a radical photocuring system and a cationic photocuring system, the compound which has both groups of a radically polymerizable group and a cationically polymerizable group can also be used. As a polymeric compound which has both groups of a radically polymerizable group and a cationically polymerizable group, for example, in a commercially available BPF epoxy half acrylate and BPA epoxy half acrylate (trade name "UVa1561" by Daicel Cytec Co., Ltd.) and one molecule The compound in which one part of the epoxy groups of the compound which has multiple epoxy groups was made to react (meth) acrylic acid, and was (meth) acryloylated is mentioned.

Especially, BPA epoxy half acrylate and BPF epoxy half acrylate have a high dilution effect with the compound represented by General formula (1), and are more preferable.

In the present invention, a radical photocuring system and a cationic photocuring system are used in combination, specifically, in the composition, a composition in which the (meth) acryloyl group and the epoxy group coexist as a radical photocuring system as a radical photocuring system is used for light irradiation. The epoxy group is more preferable because the cationic polymerization and the (meth) acryloyl group can be radically polymerized and cured, and can be firmly adhered to the substrate. In this case, in order to advance superposition | polymerization more efficiently, it is preferable to use together the cationic photoinitiator which carries out cationic polymerization of an epoxy group in the said photocurable composition together with the radical photoinitiator which radical-polymerizes a (meth) acryloyl group.

(Other component silane coupling agent)

Moreover, in order to improve adhesiveness, the photocurable composition for liquid crystal display panel seals of this invention can also mix a well-known conventional silane coupling agent. Among such silane coupling agents, a silane coupling agent having a polymerizable group such as a (meth) acryloyl group or an epoxy group may be copolymerized with a compound represented by the general formula (1) at the time of photocuring to obtain high adhesiveness. It is especially preferable because there is.

As a silane coupling agent which has a polymeric group, 3- (meth) acryloyloxypropyl trimethoxysilane, 3-epoxyoxypropyl trimethoxysilane, etc. are mentioned, for example. As a commercial item of the silane coupling agent which has such a polymeric group, For example, brand names "KBM503", "KBE503", "KBM502", "KBE502", "KBM5102", "KBM5103", "KBM5103" made by Shin-Etsu Chemical Co., Ltd. And the like.

As for the usage-amount in the case of using the said silane coupling agent together, it is preferable to use in 0.1-10 mass% with respect to the amount of all curable compositions, and the range of 1-5 mass% is especially preferable. When the ratio of a silane coupling agent is less than 0.1 mass%, sufficient adhesive effect may not be obtained, and there exists a possibility that phase separation may occur in the quantity exceeding 10 mass%. The minimum with more preferable is 0.5 mass part, and a more preferable upper limit is 5 mass parts.

(Other ingredients etc.)

To the photocurable composition for sealing of the present invention, known additives and fillers may be appropriately added in accordance with the purpose of viscosity adjustment, storage stability and the like.

For example, a filler is added for the purpose of the adhesive improvement of the photocurable composition for sealings of this invention by the stress dispersion effect, the improvement of a linear expansion rate, etc. For example, talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, diatomaceous earth, magnesium oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, barium sulfate, gypsum, calcium silicate And organic fillers such as inorganic fillers such as talc, glass beads, sericite activated clay, and bentonite, polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles.

Although it does not specifically limit as a compounding ratio of the said filler, 1-100 mass% is preferable with respect to the said curable composition amount. In 1 mass% or less, the effect which added filler is hardly obtained, and in quantity exceeding 100 mass%, there exists a possibility that handling property, such as drawing property, of the photocurable composition for seals of this invention may be reduced. A minimum with more preferable 5 mass parts and a more preferable upper limit are 50 mass parts.

(Viscosity)

The photocurable composition for liquid crystal display panel seals of this invention can be used more suitably as a liquid crystal sealing agent for manufacture of the liquid crystal display element by the dropping method mentioned later that the viscosity measured at 25 degreeC using the E-type viscosity meter is 100 Pa.s or more. Can be.

When it is less than 100 Pa.s, when manufacturing a liquid crystal display panel by the dropping method, the shape of the seal pattern formed on the transparent substrate cannot be maintained, and a sealant component may elute in a liquid crystal, and liquid crystal contamination may arise. The minimum with more preferable is 100 Pa.s, and a more preferable upper limit is 500 Pa.s. When it exceeds 500 Pa.s, the drawing property of the sealant of this invention is not enough, and manufacture of the liquid crystal display panel by a dropping method may become difficult. It does not specifically limit as an E-type viscometer which measures a viscosity at this time, For example, "DV-III" made from Brookfield, etc. can be used.

(Sealing agent for liquid crystal display panel)

The photocurable composition for liquid crystal display panel seals of this invention can be used as a sealing agent at the time of creating a liquid crystal display panel, and also as a sealing agent which seals an injection hole after inject | pouring a liquid crystal material into a liquid crystal display panel.

The liquid crystal display panel is obtained by applying the photocurable composition for sealing a liquid crystal display panel of the present invention to any one of the substrate surfaces of the front or rear substrate provided with, for example, a thin film transistor, a pixel electrode, an alignment film, a color filter, an electrode, and the like. Then, the other substrate is bonded together, light is irradiated from the substrate surface side of the said board | substrate, or the side surface of the said board | substrate, and the photocurable composition for liquid crystal display panel seals of this invention is hardened. Next, after inject | pouring a liquid crystal into the obtained liquid crystal cell, a liquid crystal display panel can be created by sealing an injection hole with a sealing agent.

Moreover, the liquid crystal display panel apply | coats the photocurable composition for liquid crystal display panel seals of this invention in liquid phase on the outer edge part of the said any one board | substrate surface, and the liquid crystal is dripped in this After that, it can also be produced by a method of photocuring after bonding the other substrate under vacuum.

In order to apply | coat the photocurable composition for liquid crystal display panel seals of this invention to a board | substrate surface, you may use a dispenser or the screen printing method may be used. In that case, it is common to apply | coat at line width 0.08-0.1 mm and line height 5-50 micrometers.

Ultraviolet rays or visible rays are preferable, and the light of the wavelength of 300 nm-400 nm is especially preferable for the light used in order to harden the photocurable composition for liquid crystal display panel seals of this invention. As a light source, a high pressure mercury lamp, a metal halide lamp, etc. can be used, for example. If the illuminance of the said light source is 500 W / m <^2> or more, hardening is fast and it is preferable. The amount of light to be irradiated can be cured satisfactorily if it is 20000 J / m <^2> or more in conversion amount. Moreover, although the photocurable composition for liquid crystal display panel seals of this invention shows favorable photocurability also in air atmosphere, since it can harden | cure with a small amount of accumulated light, if it hardens photocuring in inert gas atmosphere, such as nitrogen, it is more preferable.

[Example]

Hereinafter, an Example and a comparative example demonstrate this invention concretely. "Part" in an Example and a comparative example shows a "mass part" unless there is particular notice. Moreover, evaluation about adhesiveness and voltage retention was performed as follows.

<Base material used for adhesive test>

(Front (SiN) x Glass)

An alkali free glass plate (product name "cornig1737" manufactured by Corning Corporation) having a thickness of 0.7 mm was sputtered to form a (SiN) x layer having a thickness of about 50 nm to obtain an alkali free glass plate with (SiN) x.

(Plastic film with front ITO)

A polyether sulfone film (trade name "FS-5300 made by Sumitomo Bakelite Co., Ltd.) having an ITO film formed over the entire surface thereof was used.

(Front Acrylic Coated Glass)

The alkali-free glass plate (product name "cornig1737 made by Corning Corporation) of 0.7 mm in thickness was coated with acryl in accordance with Example 1 of Unexamined-Japanese-Patent No. 3321858, and it was set as the alkali free glass plate with a front acrylic coating.

(Front (SiN) x attached plastic film)

A (SiN) x layer having a thickness of 50 nm was formed on the entire surface of a polycarbonate film (trade name "Panlite" of Teijin Chemical Co., Ltd.) having a thickness of 0.125 mm according to Example 3 Example C of JP-A-2006-57121. It was set as the PC film substrate with SiN) x.

(Plastic film with front (SiO) x)

The PES film substrate (Sumitomo Bakelite brand name "FST1300") with (SiO) x which sputtered formed the SiOx layer was used.

(Glass with front ITO)

An alkali-free glass plate (product name "cornig1737" manufactured by Corning Corporation) having a thickness of 0.7 mm was sputtered to form an ITO layer so as to have a surface resistance of 100?, To give an alkali-free glass plate with ITO.

<Combination of base materials used for adhesive test>

The combination of the said board | substrates is as follows.

Combination A: Plastic film with front ITO / Glass with front (SiN) x

Combination B: Plastic film with front ITO / Front acrylic coated glass

Combination C: Plastic film with front side (SiN) x / Glass with front side (SiN) x

Combination D: Plastic film with front side (SiN) x / Front acrylic coated glass

Combination E: Plastic film with front side (SiO) x / Glass with front side (SiN) x

Combination F: Plastic film with front (SiO) x / Glass with front ITO

<Example of Adhesion Test Combination A>

1 mass% of spherical spacer "Haya-Bead L-11S" whose average particle diameter is about 5.5 micrometers is added to the photocurable composition for sealing mentioned later, and it is a stirring degassing machine (brand name "Awatorrentaro AR250" made by Tinki Corporation). Stirring and defoaming were performed, and it was set as the sample.

"Plastic film with front ITO", which was ejected from a syringe tip equipped with a 0.2 mm diameter precision nozzle and cut out at 150 mm x 15 mm in advance using a table-type coating robot (trade name "SHOT MINI" manufactured by Musashi Engineering, Inc.). Was applied in a straight line over a length of 9 cm so as to be parallel to the major axis direction of the substrate. On this, "glass with front (SiN) x" (size 95x15 mm) was superposed so that the said surface might become parallel to the surface of the said plastic film.

Next, after pressurizing 0.1 MPa for 2 minutes using the EHC company quartz pressure pressurization apparatus, it is 500 W / using the high pressure metal halide lamp from the said "glass with front (SiN) x" side in the state which pressurized. Ultraviolet rays of m ² were irradiated for 40 seconds. Irradiation at this time was performed in air atmosphere through the quartz window of the said pressure hardening apparatus with a quartz window. This obtained the evaluation sample whose adhesive width is 1 mm and the thickness of an adhesive layer is 5.5 micrometers.

The peeling load calculated | required by the optimum straight line method of JIS K 6854-1 by carrying out the said evaluation sample bonded together by the floating roller method peeling test (90-degree peeling at the speed | rate of 100 mm / min) of JIS K 6854-1 ( Adhesive strength (mN / mm) was calculated | required by dividing mN) by adhesive width.

<Creation of liquid crystal display panel for voltage retention test>

1. Manufacturing of liquid crystal display panel 1 (injection method)

On 5 sheets of glass substrate "RZ-B107N1N" with ITO by EHC company, 5% ethanol dispersion liquid of spacer "LH11S" by Hayakawa Rubber Co., Ltd. was sprayed. Next, after applying the photocurable composition for sealing to each one glass substrate with ITO using a dispenser, about 1 mm width so that two liquid crystal injection openings may be provided in the outer edge part of a board | substrate, two glass substrates Were bonded so as to face each other, and 500 W / m ² ultraviolet light was irradiated to the said sealant part for 40 second using a high pressure metal halide lamp in nitrogen atmosphere, and the blood cell was produced. After injecting a liquid crystal composition for driving TFT (thin film transistor) (composition is described later) under vacuum into a two-blood cell, the liquid crystal composition is masked so as not to be directly exposed to ultraviolet rays, and then the two blood cells are sealed with a sealable photocurable composition, Under nitrogen atmosphere, 500 W / m <^2> ultraviolet-rays were re-irradiated for 40 second using the high pressure metal halide lamp, and the liquid crystal display panel was produced.

2. Production of liquid crystal display panel 2 (loading method)

Two glass substrates RS-B107M1N (with rubbing oriented film and with ITO) by EHC Corporation were prepared, and 5% ethanol dispersion liquid of spacer "LH11S" by Hayakawa Rubber Co., Ltd. was sprayed on one of them. Next, the sealing material produced in Example 6 was further applied to one glass substrate in a rectangular shape with a seal width of about 1 mm at the outer edge of the substrate using a dispenser. Next, the liquid crystal composition for TFT (thin film transistor) drive (composition is mentioned later) was dripped inside the rectangular sealant on this board | substrate, and the rubbing direction of two glass substrates was orthogonal, and the bonded cell was produced. After returning this cell to atmospheric pressure and the space | interval between board | substrates became the size of a spacer, 500 W / m <^2> ultraviolet-rays were irradiated to the said sealant part for 40 second using high pressure metal halide etc., and the TN type liquid crystal display panel was produced. .

This liquid crystal display panel was sandwiched between two orthogonal polarizing plates, and the liquid crystal display element was created. When the voltage was not applied, the display was transparent to show a clear display. When the voltage was applied, the electrode portion of the cell did not pass the light, resulting in dark display, showing a good display state.

3. Liquid crystal composition for TFT (thin film transistor) drive used for liquid crystal display panel preparation

The following three types were used as a liquid crystal composition for TFT (thin film transistor) drive used in a present Example.

Liquid Crystal Composition (1)

Physical Properties of Liquid Crystal Composition (1)

Dielectric anisotropy (△ ε): 5.30

Specific resistance value: 5.2 × 10 ¹⁴ Ωm

Liquid crystal composition (2)

Physical Properties of Liquid Crystal Composition (2)

Dielectric anisotropy (△ ε): -3.1

Birefringence (Δn): 0.07

Specific resistance value: 5.6 × 10 ¹⁴ Ωm

Liquid Crystal Composition (3)

Physical Properties of Liquid Crystal Composition (3)

Dielectric anisotropy (△ ε): 4.7

Birefringence (Δn): 0.29

Specific resistance value: 1.6 × 10 ¹⁴ Ωm

<Voltage retention test>

60 degreeC 90% RH wet heat exposure test was done for the liquid crystal display panel produced by any one of said methods, and the voltage retention after 120 hours was measured. The voltage retention applied 64 microseconds of the initial voltage of 5 V of alternating current to the liquid crystal display panel at 24 degreeC, and computed the value which multiplied 100 by the voltage ratio before and after the frame time of 167 milliseconds.

Example 1 (HLB = 12)

25 parts of diepoxy compounds having bisphenol A skeleton (brand name "EPICRON 850CRP made by DIC Chemical Co., Ltd." 20 parts of epoxy ester acrylates (trade name "Ebecryl 3708" by Daicel Cytec Co., Ltd.) obtained by making γ-caprolactone and ethyl hydroxyethyl acrylate sequentially react with the reaction intermediate obtained by making epoxy and the phthalic anhydride react. 10 parts of a type | mold epoxy half acrylate (The brand name "UVa1561 made by Daicel Cytec Co., Ltd." were melt | dissolved at 140 degree | times. Then, caprolactone modified hydroxy pivalate neopentyl glycol diacrylate (made by Nippon Kayaku Co., Ltd.), stirring at 120 degreeC. 25 parts of brand name "KAYARAD HX620"), ten parts of rosin modified epoxy acrylate (brand name "beamset 101" made by Arakawa Chemical Co., Ltd.) The mixture was kept at room temperature, and 1 part of ethylene oxide and propylene oxide-modified polydimethylsiloxane compound (hereinafter referred to as Compound A) which are nonionic surfactants (trade name "KF6011" manufactured by Shin-Etsu Chemical Co., Ltd., HLB = 12) It added and stirred well.

2,2 which is a sulfonium salt type | system | group photocationic initiator (brand name "SP150" by Asahi Denka Co., Ltd.), 5.0 parts of silane coupling agents (brand name "KBM5103" of Shin-Etsu Chemical Co., Ltd.), and a radical photoinitiator. After adding dimethoxy-2-phenylacetophenone (trade name "IRGACURE 651" of Chiba Specialty Chemicals), stirring it while heating and dissolving as necessary, 5 parts of trade name "RY-200S" made by Nippon Aerosol Co., Ltd. is added. It knead | mixed with 3 rolls and obtained the photocurable composition A for liquid crystal display panel seals.

About the photocurable composition A for liquid crystal display panel seals, while producing a liquid crystal display panel by the method of the said liquid crystal display panel preparation 1, it evaluated according to the said evaluation method, and the result was shown in Table 1.

Example 2 (HLB = 14)

Instead of using 1 part of the compound (A) in Example 1, except that 1 part of the polydimethylsiloxane compound (B) (trade name "TSF-4440", HLB = 14 manufactured by Dore Dow Corning) was modified. Obtained the photocurable composition for liquid crystal display panel sealing according to the method as described in Example 1. About the said composition, the liquid crystal display panel was produced by the method of the said liquid crystal display panel preparation 1, and it evaluated in accordance with the said evaluation method, and the result was shown in Table 1.

Example 3 (HLB = 10)

1 part of polydimethylsiloxane compound (C) (trade name "KF-353" manufactured by Shin-Etsu Chemical Co., Ltd., HLB = 10, 430 mPas) modified with polyethylene oxide in place of 1 part of compound (A) in Example 1 Except for being used, the photocurable composition for liquid crystal display panel seals was obtained according to the method as described in Example 1. About the said composition, the liquid crystal display panel was produced by the method of the said liquid crystal display panel preparation 1, and it evaluated in accordance with the said evaluation method, and the result was shown in Table 1.

Example 4 (HLB = 13)

Polydimethylsiloxane compound (D) modified by polyethylene oxide, polypropylene oxide, and glycidyl ether group instead of 1 part of compound (A) in Example 1 (brand name "X22-4741" made by Shin-Etsu Chemical Co., Ltd.) And HLB = 13) Except using 0.75 part, the photocurable composition for liquid crystal display panel sealing was obtained according to the method as described in Example 1. About the said composition, the liquid crystal display panel was produced by the method of the said liquid crystal display panel preparation 1, and it evaluated in accordance with the said evaluation method, and the result was shown in Table 1.

Example 5 (HLB = 13, 0.3 parts)

Polydimethylsiloxane compound (D) modified by polyethylene oxide, polypropylene oxide, and glycidyl ether group instead of 1 part of compound (A) in Example 1 (brand name "X22-4741" made by Shin-Etsu Chemical Co., Ltd.) And HLB = 13) except having used 0.3 part, the photocurable composition for liquid crystal display panel sealing was obtained according to the method as described in Example 1. About the said composition, the liquid crystal display panel was produced by the method of the said liquid crystal display panel preparation 1, and it evaluated in accordance with the said evaluation method, and the result was shown in Table 1.

Example 6 (HLB = 13, 1.5 parts)

Polydimethylsiloxane compound (D) (The brand name "X22-4741 made from Shin-Etsu Chemical Co., Ltd.") modified in the polyethylene oxide, the polypropylene oxide, and the glycidyl ether group instead of 1 part of the compound (A) in Example 1, A photocurable composition for sealing a liquid crystal display panel was obtained according to the method as described in Example 1 except that 0.3 parts of HLB = 13) was used. About the said composition, the liquid crystal display panel was produced by the method of the said liquid crystal display panel preparation 1, and it evaluated in accordance with the said evaluation method, and the result was shown in Table 1.

Example 7 (Use of oxetane)

Except for using 10 parts of a biphenol-type oxetane compound (trade name "OXBP" manufactured by Ubegosan Co., Ltd.) instead of 10 parts of an epoxy compound having a bisphenol A skeleton in Example 4 (trade name "EPICRON 1050" manufactured by DIC Corporation), The photocurable composition for liquid crystal display panel seal was obtained according to the method as described in Example 1. About this composition, while producing a liquid crystal display panel by the method of the said liquid crystal display panel manufacture 1, it evaluated according to the said evaluation method The results are shown in Table 1.

Example 8 (HLB = 13, Comparison with Reference Document 7)

Polydimethylsiloxane compound (D) modified by polyethylene oxide, polypropylene oxide, and glycidyl ether group instead of 1 part of compound (A) in Example 1 (brand name "X22-4741" made by Shin-Etsu Chemical Co., Ltd.) , 10 parts of the compound (EP) represented by the following general formula described in Ref. 7 instead of 10 parts of an epoxy compound (the brand name "EPICRON 1050" made by DIC Corporation) having a bisphenol A skeleton as 1.0 part of HLB = 13) Obtained the photocurable composition for liquid crystal display panel sealing according to the method as described in Example 1. About this composition, while producing a liquid crystal display panel by the method of the said liquid crystal display panel manufacture 1, according to the said evaluation method It evaluated and the result was shown in Table 1.

(EP)

Example 9 (HLB = 13.6, 1.0 parts)

Example 1 except for using 1.0 part of the polyoxyethylene lauryl ether compound (trade name "Emulgen 109P", HLB = 13 manufactured by Kaoga Chemical Co., Ltd.) instead of 1 part of Compound (A) According to the method as described in 1, the photocurable composition for liquid crystal display panel seals was obtained. About the said composition, the liquid crystal display panel was produced by the method of the said liquid crystal display panel preparation 1, and it evaluated in accordance with the said evaluation method, and the result was shown in Table 1.

Example 10 (HLB = 15.5, 1.0 parts)

1.0 part of monolauryl decaglyceryl compound (The brand name "DECAGLYN-1-L", HLB = 15.5 made by Nikko Chemicals, Inc.) was used instead of 1 part of compound (A) in Example 1. A photocurable composition for liquid crystal display panel seals was obtained in the same manner as in Example 1. About the said composition, the liquid crystal display panel was produced by the method of the said liquid crystal display panel preparation 1, and it evaluated in accordance with the said evaluation method, and the result was shown in Table 1.

Example 11 (HLB = 15.0, 1.0 parts)

Other than using 1.0 part of the polyoxyethylene sorbitan monooleic acid ester compound (brand name "TO-10V", HLB = 15.0 made by Nikko Chemicals, Inc.) instead of 1 part of compound (A) in Example 1 Obtained the photocurable composition for liquid crystal display panel sealing according to the method as described in Example 1. About the said composition, the liquid crystal display panel was produced by the method of the said liquid crystal display panel preparation 1, and it evaluated in accordance with the said evaluation method, and the result was shown in Table 1.

Example 12 (HLB = 16.3, 1.0 parts)

In Example 1, the compound represented by the following general formula which modified | denatured 1- (allyloxy) -2, 3- epoxy propane by C11-14 alcohol and ethylene oxide instead of 1 part of compound (A) ( ER) (trade name "ER-30" manufactured by ADEKA, HLB = 16.3, 65% aqueous solution) was dehydrated by freeze-drying, except that 1.0 part was used, and the liquid crystal display was carried out according to the method as described in Example 1 The photocurable composition for panel sealing was obtained. About the said composition, the liquid crystal display panel was produced by the method of the said liquid crystal display panel preparation 1, and it evaluated in accordance with the said evaluation method, and the result was shown in Table 1.

(ER)

In the above general formula, R is an alkyl group having 10 to 14 carbon atoms, n represents an integer of a repeating unit, and n = 30.

Comparative Example 1 (without additives)

The photocurable composition for liquid crystal display panel seals was obtained according to the method as described in Example 1 except not adding 1 part of compounds (A) in Example 1. About the said composition, the liquid crystal display panel was produced by the method of the said liquid crystal display panel preparation 1, and it evaluated in accordance with the said evaluation method, and the result was shown in Table 1.

Comparative Example 2 (HLB = 5)

A polydimethylsiloxane compound (E) (modified by Shin-Etsu Chemical Co., Ltd., brand name "KF-6015" manufactured by Shin-Etsu Chemical Co., Ltd., HLB = 5), instead of 1 part of Compound (A) in Example 1 Obtained the photocurable composition for liquid crystal display panel sealing according to the method as described in Example 1. About the said composition, the liquid crystal display panel was produced by the method of the said liquid crystal display panel preparation 1, and it evaluated in accordance with the said evaluation method, and the result was shown in Table 1.

Comparative Example 3 (HLB = 7)

A polydimethylsiloxane compound (E) (modified by Shin-Etsu Chemical Co., Ltd., brand name "KF-6012" manufactured by Shin-Etsu Chemical Co., Ltd., HLB = 7), instead of 1 part of Compound (A) in Example 1, was modified. Obtained the photocurable composition for liquid crystal display panel sealing according to the method as described in Example 1. About the said composition, the liquid crystal display panel was produced by the method of the said liquid crystal display panel preparation 1, and it evaluated in accordance with the said evaluation method, and the result was shown in Table 1.

Comparative Example 4 (HLB = 12, 5 parts added)

A photocurable composition for sealing a liquid crystal display panel was obtained according to the method as described in Example 1 except that 1 part of the compound (A) in Example 1 was made into 5 parts. About the said composition, the liquid crystal display panel was produced by the method of the said liquid crystal display panel preparation 1, and it evaluated in accordance with the said evaluation method, and the result was shown in Table 1.

[Comparative Example 5] (no additives, comparison with Cited Reference 7)

Except not adding the polydimethylsiloxane compound (D) (The brand name "X22-4741 made by Shin-Etsu Chemical Co., Ltd., HLB = 13" modified in the polyethylene oxide, the polypropylene oxide, and the glycidyl ether group in Example 9). Obtained the photocurable composition for liquid crystal display panel sealing according to the method as described in Example 7. About the said composition, the liquid crystal display panel was produced by the method of the said liquid crystal display panel preparation 1, and it evaluated in accordance with the said evaluation method, and the result was shown in Table 1.

Comparative Example 6 (HLB = 9.6, 1.0 parts)

A polyoxyethylene sorbitan monostearic acid ester compound (trade name "TS-106" manufactured by Nikko Chemicals, HLB = 9.6) was used instead of 1 part of Compound (A) in Example 1, except that 1.0 part was used. And the photocurable composition for sealing was obtained according to the method as described in Example 1. About the said composition, the liquid crystal display panel was produced by the method of the said liquid crystal display panel preparation 1, and it evaluated in accordance with the said evaluation method, and the result was shown in Table 1.

Comparative Example 7 (1.0 parts of fluorine-based surfactant)

Example 1 except that 1.0 part of a perfluoroalkyl ethylene oxide compound (trade name "Megapack F-444" by DIC Corporation) was used instead of 1 part of compound (A). The photocurable composition for sealing was obtained according to the method as described in. About the said composition, the liquid crystal display panel was produced by the method of the said liquid crystal display panel preparation 1, and it evaluated in accordance with the said evaluation method, and the result was shown in Table 1.

[Table 1]

In Table 1, x shows "easy peeling and inability to measure".

As a result, in the liquid crystal display panel using the photocurable composition for sealing obtained in Examples 1-12, the voltage retention showed 90% or more, and adhesive strength was also favorable.

Comparative Examples 1 and 5 are examples in which a nonionic surfactant is not added. In addition, Comparative Examples 2, 3 and 6 are examples in which HLB added a nonionic surfactant of less than 10, and Comparative Example 7 is an example in which a fluorine-based surfactant was added. All were inferior in adhesiveness. In addition, the comparative example 4 is an example in which addition amount exceeds 4 mass%, and voltage retention fell.

Claims (6)

A cationically polymerizable compound, a photocationic polymerization initiator, a radically polymerizable compound, a radical photopolymerization initiator, and a nonionic surfactant having an HLB value of 10 or more,
The cationically polymerizable compound is a compound having at least one group selected from the group consisting of an epoxy group, an oxetanyl group and a vinyl ether group in a molecule,
The radically polymerizable compound is a compound having a (meth) acryloyl group,
Content of the nonionic surfactant whose said HLB value is 10 or more is 0.1-4 mass% with respect to photocurable composition solid content whole quantity, The photocurable composition for liquid crystal display panel seals characterized by the above-mentioned. The method of claim 1,
The nonionic surfactant,
The photocurable composition for liquid crystal display panel seals which is a C6 or more higher alcohol, a C6 or more higher amine, a C6 or more higher fatty acid, or a nonionic surfactant which alkylene oxide added to the silicone main chain, or polyglycerol fatty acid ester. The method according to claim 1 or 2,
The photocurable composition for liquid crystal display panel seals whose said nonionic surfactant is alkylene oxide modified polydimethylsiloxane. delete delete The photocurable composition for liquid crystal display panel seals of Claim 1 or 2 is used, The liquid crystal display panel characterized by the above-mentioned.