JP7246733B2 - Sealant for liquid crystal drop method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a sealant for a liquid crystal dropping method.

In the manufacturing method of the liquid crystal display element, the dropping method is a method that can create a panel by directly dropping the liquid crystal in the closed loop of the sealant, bonding them together in a vacuum, and releasing the vacuum. This dripping method has many advantages such as a reduction in the amount of liquid crystal used and a shortened injection time of the liquid crystal into the panel, and is currently the mainstream method for manufacturing liquid crystal panels using large substrates. In the method including the dripping method, the seal and liquid crystal are applied, and after bonding, the gap is formed, the alignment is performed, and the seal is cured mainly by ultraviolet curing.

Patent Document 1 describes a liquid crystal sealant containing a powdery organic thixotropic agent (thixotropic agent) as a raw material of the sealant (Patent Document 1).

JP 2011-197654 A

In the dropping method, the sealant is applied onto the substrate using a dispenser, but the application is interrupted between substrates or between patterns. At that time, the sealing agent containing the powdery thixotropic agent described in Patent Document 1 drips at the tip of the nozzle, and this causes a problem that the sealing agent cannot be applied with a specified line width.

An object of the present invention is to provide a sealant for a liquid crystal dripping method in which the occurrence of dripping is reduced.

As a result of investigation, the present inventors have found that the above problems can be solved by using a liquid thixotropic agent, and have completed the present invention.
The present invention relates to the following [1] to [6].
[1] (A) a curable resin, (B) a polymerization initiator and/or (C) a thermosetting agent, (D) a liquid thixotropic agent, and (E) a filler (however, in the case of a powder thixotropic agent, (not included), sealing agent for liquid crystal dropping method.
[2] (D) The sealant for liquid crystal dropping method according to [1], wherein the liquid thixotropic agent is an ester-based liquid thixotropic agent.
[3] (D) The liquid thixotropic agent is one or more selected from the group consisting of polyether phosphoric acid esters and fatty acid esters.
[4] (A) The curable resin contains one or more selected from the group consisting of partially (meth)acrylated epoxy resins of bifunctional or higher functional epoxy resins and combinations of epoxy resins and acrylic resins, [1 ] to [3] for liquid crystal dropping method.
[5] The sealant for a liquid crystal dropping method according to any one of [1] to [4], further comprising one or more additional components selected from the group consisting of a silane coupling agent and a powder thixotropic agent. Sealed liquid crystal display.
[6] A liquid crystal display sealed with the liquid crystal dropping method sealing agent according to any one of [1] to [5].

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal dripping construction methods with which generation|occurrence|production of dripping was reduced is provided.

Preferred embodiments of the present invention are described below. As used herein, "glycidyl" means 2,3-epoxypropyl. "Methylglycidyl" means 2,3-epoxy-2-methylpropyl. "Epoxy group" includes at least one of glycidyl group and methylglycidyl group. "(Meth)acryloyl group" means at least one of acryloyl group (CH ₂ =CH ₂ -C(=O)-) and methacryloyl group (CH ₂ =CH(CH ₃ )-C(=O)-) include. "Optionally substituted" means "substituted or unsubstituted."

[Sealant for Liquid Crystal Dropping Method]
The sealant for the liquid crystal dropping method (hereinafter also simply referred to as "sealant") comprises (A) a curable resin, (B) a polymerization initiator and/or (C) a heat curing agent, and (D) a liquid thixotropic and (E) a filler (but not a powder thixotropic agent).
The sealant has reduced solubility in liquid crystals and can prevent contamination of the liquid crystals.

(Curable resin)
The curable resin (hereinafter also referred to as “component (A)”) is a curable component of the sealant. The curable resin is appropriately selected from cationically polymerizable resins, radically polymerizable resins and/or anionically polymerizable resins according to the type of polymerization initiator and/or thermosetting agent contained in the sealant. Examples of such curable resins include resins having unsaturated groups and/or epoxy groups. The curable resin may be one kind or a combination of two or more kinds.

<Resin Having Unsaturated Group>
Examples of the unsaturated group-containing resin (hereinafter also referred to as “component (a1)”) include conventional unsaturated group-containing resins that are used as the main ingredient of sealants for the liquid crystal dropping method. Here, "unsaturated group" means an ethylenically unsaturated group and/or an acetylenically unsaturated group. Resins having unsaturated groups include (meth)acrylate compounds, aliphatic acrylamide compounds, alicyclic acrylamide compounds, acrylamide compounds containing aromatics, N-substituted acrylamide compounds, diene polymers (e.g., polybutadiene polymers, poly isoprene polymer, etc.), preferably an acrylic resin having a (meth)acryloyl group. The functionality of the (meth)acrylate compounds can be monofunctional, difunctional or trifunctional or higher. Also, the (meth)acrylate compound preferably does not have an amide bond.

Monofunctional (meth)acrylate compounds include hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isooctyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate. , dicyclopentanyl (meth)acrylate, cyclohexyloxyethyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, isomyristyl (meth)acrylate, lauryl (meth)acrylate One or more compounds selected from the group consisting of acrylates, tert-butyl (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, paracumylphenoxyethylene glycol (meth)acrylate, and ethoxylated phenyl (meth)acrylate are preferred. .

Examples of bifunctional (meth)acrylate compounds include tricyclodecanedimethanol di(meth)acrylate, dimethyloldicyclopentane di(meth)acrylate, EO-modified 1,6-hexanediol di(meth)acrylate, EO-modified Bisphenol A di(meth)acrylate, PO-modified bisphenol A di(meth)acrylate, polyester di(meth)acrylate (eg, ARONIX M-6100, manufactured by Toagosei Co., Ltd.), polyethylene glycol di(meth)acrylate (eg, 4G , manufactured by Shin-Nakamura Chemical Co., Ltd.), and silicon di(meth)acrylate (eg, EBECRYL 350, manufactured by Daicel-Ornex Co., Ltd.). Here, "EO" means ethylene oxide and "PO" means propylene oxide.

Examples of trifunctional or higher polyfunctional (meth)acrylate compounds include EO-modified glycerol tri(meth)acrylate (trifunctional), PO-modified glycerol tri(meth)acrylate (trifunctional), pentaerythritol tri(meth)acrylate ( trifunctional), dipentaerythritol hexa(meth)acrylate (hexafunctional) and pentaerythritol tetra(meth)acrylate (tetrafunctional) are preferred.

Furthermore, as resins having unsaturated groups, epoxy resins in which all of the epoxy groups of the epoxy resin have been modified with (meth)acrylic acid, and epoxy resins in which all of the epoxy groups of the epoxy resin have been modified with a modifying compound having unsaturated groups Epoxy resins may be mentioned.
The unsaturated group-containing resin may be one or a combination of two or more.

<Resin having an epoxy group>
As the epoxy group-containing resin (hereinafter also referred to as "component (a2)"), there may be mentioned conventional epoxy group-containing resins that are used as the main agent of sealant for liquid crystal dripping method. The resin having an epoxy group is not particularly limited as long as it has one or more epoxy groups. Resins having one epoxy group include aromatic epoxy resins and aliphatic epoxy resins.

Bifunctional or higher epoxy resins are not particularly limited, and include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, Bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, phenol having a triphenol methane skeleton A novolac type epoxy resin and the like can be mentioned. In addition, diglycidyl-etherified products of bifunctional phenols, diglycidyl-etherified products of bifunctional alcohols, their halides, and hydrogenated products can also be used. Further, trifunctional and tetrafunctional epoxy resins include epoxy resins described in JP-A-2012-077202. Although the functionality of the di- or higher functional epoxy resin is not particularly limited, it is preferably from 2 to 4.
The epoxy group-containing resin may be one or a combination of two or more.

<Resin Having Unsaturated Group and Epoxy Group>
As the resin having an unsaturated group and an epoxy group (hereinafter also referred to as "component (a3)"), a conventional resin having both an unsaturated group and an epoxy group, which is used as the main agent of a sealant for the liquid crystal dropping method, is used. mentioned. The resin having an unsaturated group and an epoxy group is preferably a resin having one or more (meth)acryloyl groups and one or more epoxy groups. is particularly preferred.

<<Partial (meth)acrylated epoxy resin of bifunctional or higher epoxy resin>>
Partially (meth)acrylated epoxy resin of bifunctional or more functional epoxy resin means a resin in which some epoxy groups in the epoxy resin are reacted with (meth)acrylic acid, that is, epoxy groups and It has both (meth)acryloyl groups.

A partially (meth)acrylated epoxy resin can be obtained by reacting a bifunctional or higher functional epoxy resin with (meth)acrylic acid. The epoxy resin having a functionality of 2 or more is as described above for the resin having an epoxy group, including preferred embodiments.

The partially (meth)acrylated epoxy resin preferably contains 10 to 90 mol% (meth)acrylic groups, more preferably 40 to 60 mol %. Partially (meth)acrylated epoxy resins include compounds containing one or more epoxy groups and one or more (meth)acrylic groups in one molecule. In addition, the partially (meth)acrylated epoxy resin is a compound having two or more epoxy groups in one molecule and no (meth)acrylic group, which corresponds to an unreacted epoxy compound in the raw material epoxy resin. and a compound having two (meth)acrylic groups in one molecule and having no epoxy groups, which corresponds to a compound in which all the epoxy groups of the epoxy compound have reacted with (meth)acrylic acid. obtain.
Resins having unsaturated groups and epoxy groups may be used alone or in combination of two or more.

<Preferred embodiment>
The curable resin is one or more selected from the group consisting of (a3) a resin having an unsaturated group and an epoxy group and a combination of (a1) a resin having an unsaturated group and (a2) a resin having an epoxy group. It preferably contains one or more selected from the group consisting of partially (meth)acrylated epoxy resins of bifunctional or higher functional epoxy resins and combinations of epoxy resins and acrylic resins. When the curable resin contains (a3) a resin having an unsaturated group and an epoxy group, it is further selected from the group consisting of (a1) a resin having an unsaturated group and (a2) a resin having an epoxy group. It may contain one or more resins.

(Polymerization initiator and/or thermosetting agent)
The polymerization initiator (hereinafter also referred to as “component (B)”) is a component that can make the sealant a radically curable, anionically curable and/or cationically curable composition. The thermosetting agent (hereinafter, also referred to as "component (C)") is a component that allows the sealant to be a thermosetting composition. The polymerization initiator and/or thermosetting agent can be appropriately selected according to the type of curable resin contained in the sealant and desired curing conditions (energy ray curing and/or thermosetting). Therefore, the sealant may contain either one of the polymerization initiator and the heat curing agent, or may contain both the polymerization initiator and the heat curing agent.

<Polymerization initiator>
Polymerization initiators include radical polymerization initiators, anionic polymerization initiators and/or cationic polymerization initiators. The polymerization initiator is a component that serves as a radical generating source for radical polymerization, an anion generating source for anionic polymerization, and a cation generating source for cationic polymerization of the curing component contained in the sealing agent.

Radical polymerization initiators include benzoins, acetophenones, benzophenones, thioxanthones, α-acyloxime esters, phenylglyoxylates, benzils, azo compounds, diphenyl sulfide compounds, acylphosphine oxide compounds, Examples include benzoin ethers, anthraquinones, organic peroxides, and the like. The radical polymerization initiator preferably has a low solubility in liquid crystals and has a reactive group that does not gasify the decomposed product when irradiated with light. Further, as a radical polymerization initiator, a compound obtained by reacting a compound having at least two epoxy groups and dimethylaminobenzoic acid, which is described in WO2012/077720, and at least two epoxy groups. A polymerization initiator that is a mixture of a compound obtained by reacting a compound having a hydroxythioxanthone with hydroxythioxanthone is preferred.

Examples of anionic polymerization initiators include imidazoles, amines, phosphines, organic metal salts, metal chlorides, organic peroxides and the like.

Cationic polymerization initiators include onium salts, iron allene complexes, titanocene complexes, arylsilanol aluminum complexes, Lewis acid compounds, Bronsted acid compounds, benzylsulfonium salts, thiophenium salts, thiolanium salts, benzylammonium, pyridinium salts, hydrazinium salts, Examples thereof include carboxylic acid esters, sulfonic acid esters, amineimides, sulfone compounds, sulfonic acid esters, sulfonimides, disulfonyldiazomethanes, and amines.

The polymerization initiator is commercially available or can be prepared according to known methods.
The polymerization initiator may be one kind or a combination of two or more kinds.

<Heat curing agent>
The heat curing agent is not particularly limited, but includes amine-based heat curing agents such as organic acid dihydrazide compounds, amine adducts, imidazole and its derivatives, dicyandiamide, aromatic amines, epoxy-modified polyamines, and polyaminourea, and VDH ( 1,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin), ADH (adipic acid dihydrazide), UDH (7,11-octadecane-1,18-dicarbohydrazide) and LDH (octadecane-1, 18-dicarboxylic acid dihydrazide); polyamine compounds sold by ADEKA Co., Ltd. as ADEKA HARDNER EH5030S; Ajinomoto Fine-Techno Co., Ltd., Amicure PN-23, Amicure PN-30, Amicure MY- 24, Amicure MY-H, etc., are preferred.
The thermosetting agent may be one or a combination of two or more.

(Liquid thixotropic agent)
The liquid thixotropic agent (hereinafter also referred to as "component (D)") is a component that imparts thixotropy to the sealant. "Liquid" means not containing powder components.

Examples of liquid thixotropic agents include ester-based, amide-based, and polyvalent carboxylic acid-based liquid thixotropic agents.
Examples of the ester-based liquid thixotropic agent include a phosphoric acid ester liquid thixotropic agent and a fatty acid ester liquid thixotropic agent. As the phosphate ester, a polyether-based phosphate ester is preferred. Examples of the polyether phosphate include esters of polyoxyethylene alkyl ether phosphates, esters of polyoxyethylene alkylphenyl ether phosphates, and esters of higher alcohol phosphates.
The liquid thixotropic agent is preferably an ester-based liquid thixotropic agent, and particularly preferably a polyether phosphoric acid ester liquid thixotropic agent or a fatty acid ester liquid thixotropic agent.
Commercially available liquid thixotropic agents include Disparlon 3500, Disparlon 3600N, Disparlon 3900EF (manufactured by Kusumoto Kasei Co., Ltd.), RCM-100 (manufactured by Kyoeisha Chemical Co., Ltd.), BYK-R606, BYK-405, BYK-R605, etc. (Bik Chemie・Japan Co., Ltd.) and the like.
The liquid thixotropic agents may be one or a combination of two or more.

(Filler (but not powder thixotropic agent))
A filler (but not a powder thixotropic agent) (hereinafter also referred to as "component (E)") is used to control the viscosity of the sealing agent, improve the strength of the cured product obtained by curing the sealing agent, or improve the linear expansion property. It is added for the purpose of improving the adhesion reliability of the sealant by suppressing it. Fillers include inorganic fillers and organic fillers.

Inorganic fillers include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titania, alumina, zinc oxide, silica (excluding fumed silica), kaolin, talc, glass beads, sericite activated clay, Bentonite, aluminum nitride, and silicon nitride.

Examples of organic fillers include polymethyl methacrylate, polystyrene, copolymers obtained by copolymerizing the monomers constituting these with other monomers, polyester fine particles, polyurethane fine particles, rubber fine particles, and copolymers having a high glass transition temperature. Examples include core-shell type particles composed of a shell containing a polymer and a core of a copolymer having a low glass transition temperature.

The inorganic filler is preferably silica filler. Also, the organic filler is preferably core-shell type particles.
A commercial item can be used for the filler. Commercially available silica fillers include Seahoster KE series (KE-C50, etc.). Core-shell type particles include the Zephiac series (F-351, etc., manufactured by Aica Kogyo Co., Ltd.).
Each filler may be one or a combination of two or more.

(additional ingredients)
The sealant may contain one or more additional components selected from the group consisting of silane coupling agents, powder thixotropic agents, photosensitizers, and additional resins. Further components are not components (A) to (E) described above.

<Silane coupling agent>
A silane coupling agent (hereinafter also referred to as "component (F)") is added for the purpose of further increasing the adhesive strength. The silane coupling agent is not particularly limited and includes γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like.
The silane coupling agent may be one or a combination of two or more.

<Powder thixotropic agent>
The sealant can contain a powder thixotropic agent (hereinafter also referred to as "component (G)") within the range where the effects of the present invention are exhibited. The powder thixotropic agent may be dissolved or dispersed in a solvent.

Powder thixotropic agents include inorganic or organic powder thixotropic agents. Here, examples of the inorganic powder thixotropic agent include fumed silica. Examples of organic powder thixotropic agents include amide-based (polyhydroxycarboxylic acid amide-based), castor oil-based, polyethylene oxide-based, and polyhydroxycarboxylic acid ester-based powdery thixotropic agents.

A commercially available product can be used as the powder thixotropic agent. Commercially available products of fumed silica include TG-308F (manufactured by Cabot Corporation) and RY200 (manufactured by Nippon Aerosil Co., Ltd.). Commercially available powder thixotropic agents other than fumed silica include Disparlon 305, Disparlon 4300, Disparlon 6650, Disparlon 6500, Disparlon 6700 and Disparlon F9050 (manufactured by Kusumoto Kasei Co., Ltd.).

It is highly compatible with resins having (meth)acryloyloxy groups, and is likely to exhibit the effect of improving the thixotropic properties of sealing agents for liquid crystal dripping methods. preferable.
The powder thixotropic agent may be one or a combination of two or more.

<Further resin>
The further resin is a resin other than the curable resin used as the main ingredient of the liquid crystal sealant, and includes conventional resins having neither unsaturated groups nor epoxy groups. Examples of resins having neither unsaturated groups nor epoxy groups include modified epoxy resins in which all of the epoxy groups of the epoxy resin have been modified with modified compounds having no unsaturated groups, hydroxyl group-containing compounds and isocyanate group-containing compounds. A formed urethane resin and the like can be mentioned.

(Content of each component)
The content of component (A) is preferably 50 to 99 parts by weight, particularly preferably 60 to 90 parts by weight, per 100 parts by weight of the sealing agent.
The content of component (a3) is preferably 30 to 100 parts by weight, particularly preferably 50 to 100 parts by weight, per 100 parts by weight of component (A).
The content of component (B) is preferably 0.1 to 5 parts by weight, particularly preferably 1 to 5 parts by weight, per 100 parts by weight of component (A).
The content of component (C) is preferably 5 to 50 parts by weight, particularly preferably 10 to 40 parts by weight, per 100 parts by weight of component (A).
The content of component (D) is preferably 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, with respect to the total of 100 parts by weight of components (A) to (E). is particularly preferred.
The content of component (E) is preferably 2 to 40 parts by weight, more preferably 5 to 30 parts by weight, per 100 parts by weight of components (A) to (E) combined.
The amount of component (F) is preferably 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, with respect to the total of 100 parts by weight of components (A) to (E). more preferred.
The content of component (G) is preferably 0.1 to 5 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of components (A) to (E) in total. is more preferred.
The content of further components other than the components described above is preferably 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, with respect to 100 parts by weight of components (A) to (E) in total. Part is more preferred.

(Characteristic)
The viscosity of the sealant for the liquid crystal dropping method is not particularly limited as long as it is a viscosity normally used as a sealant, but it is preferably 200,000 to 500,000 mPa s, and more preferably 200,000 to 400,000 mPa s. Especially preferred. The viscosity can be measured by the method described in Examples below.

(Curing method)
The sealant can be cured by irradiation with energy rays such as ultraviolet rays, by applying heat, or by applying heat before, after, or simultaneously with irradiation with energy rays such as ultraviolet rays. Therefore, the sealant is a light (energy ray) curable, thermosetting, or energy ray and thermosetting composition.

(Application)
A cured product of the sealant for the liquid crystal dropping method is used for sealing the liquid crystal display. Therefore, the present invention also covers a liquid crystal display sealed with a sealant.
As a method for manufacturing a liquid crystal display, a dispenser is used to apply a sealant to one of two electrode-attached transparent substrates to form a pattern of the sealant. and immediately bonding the other transparent substrate, and irradiating the seal pattern portion with light such as ultraviolet rays, heating the sealant, or irradiating the seal pattern portion with energy rays such as ultraviolet rays. , before, after, or simultaneously curing by applying heat.

Specific embodiments of the present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

（Ｂ）重合開始剤
（ｂ－１）開始剤１：ＷＯ２０１２／０７７７２０号公報の段落００５８に記載された、下記構造式を有する開始剤である。

（ｂ－２）開始剤２：ＷＯ２０１２／０７７７２０号公報の段落００６０に記載された、下記構造式を有する開始剤である。

[Ingredients used]
(A) Curable resin (a-1) (meth)acrylic-modified epoxy resin: Compound 1; "Compound B" having the following structural formula described in paragraph 0092 of WO2014/057871.

(B) Polymerization Initiator (b-1) Initiator 1: An initiator having the following structural formula described in paragraph 0058 of WO2012/077720.

(b-2) Initiator 2: An initiator having the following structural formula described in paragraph 0060 of WO2012/077720.

(C) Heat curing agent (c-1) Polyamine compound (EH-5030S, manufactured by ADEKA)

(D) Liquid thixotropic agent (d-1) Polyether phosphate (Disparon 3500, manufactured by Kusumoto Kasei Co., Ltd.)
(d-2) Fatty acid ester (RCM-100, manufactured by Kyoeisha Chemical Co., Ltd.)

(E) filler (e-1) inorganic filler; silica filler (Seahoster KE-C50, manufactured by Nippon Shokubai Co., Ltd.)
(e-2) organic filler; core-shell type acrylic resin filler (Zefiac F-351, manufactured by Aica Kogyo Co., Ltd.)

(F) Powder thixotropic agent (f-1) Hydrophobic fumed silica (TG-308F, manufactured by Cabot Corporation)
(f-2) Hydrophobic fumed silica (RY200, manufactured by Nippon Aerosil Co., Ltd.)
(f-3) Amide-based powder thixotropic agent (Disparon 6500, manufactured by Kusumoto Kasei Co., Ltd.)
(G) Silane coupling agent (g-1) 3-glycidoxypropyltriethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
(H) Polymerization inhibitor (h-1) 2,6-di-t-butyl-4-cresol (BHT, manufactured by Kanto Chemical Co., Ltd.)

[Examples 1-2 and Comparative Examples 1-5]
After mixing in the compounding amounts (parts by weight) shown in Table 1 below, the sealants of Examples and Comparative Examples were sufficiently kneaded with a three-roll mill (C-4 3/4×10, manufactured by Inoue Seisakusho Co., Ltd.). manufactured. The sealants of Examples and Comparative Examples were evaluated by the following tests.

<Measurement of properties>
(viscosity)
Using an E-type viscometer (RE105U manufactured by Toki Sangyo Co., Ltd.), the viscosity was measured at 25° C. and cone rotor rotation speeds of 0.5 rpm, 2.5 rpm and 5.0 rpm.
(Thixotropic ratio)
The value of "viscosity at 0.5 rpm/viscosity at 5.0 rpm" measured in the above "(viscosity)" was taken as the thixotropic ratio.

(epoxy equivalent)
The epoxy equivalent was measured according to JISK7236:2001.

(Drip test)
A syringe (manufactured by Musashi Engineering, volume 30 ml) equipped with a nozzle was filled with 10 g of a sealant and allowed to stand for 3 hours. The presence or absence of a liquid pool at the tip of the nozzle was visually confirmed to evaluate the presence or absence of dripping.

(Applicability test)
Using a sealant applicator (manufactured by Musashi Engineering) and a nozzle (manufactured by Musashi Engineering, nozzle diameter 0.3 mm), drawing was performed on the ITO substrate at a coating speed of 150 mm/s and a nozzle gap of 30 μm. The presence or absence of breakage of the seal was visually observed to evaluate the applicability.

(Orientation test)
An ITO substrate (403005XG-10SQ1500A, manufactured by Geomatec Co., Ltd.) was dried after washing with pure water, and a polyimide-based alignment liquid (Sunever SE-7492, manufactured by Nissan Chemical Industries, Ltd.) was dropped (0.4 MPa, 5.5 psi) using an air dispenser. 0 seconds), the spin coater reached 5000 rpm in 10 seconds, and was then uniformly coated under the conditions of keeping for 20 seconds. After uniform application, pre-baking (1 minute) on a hot plate at 85° C. and post-baking (60 minutes) in an oven at 230° C. produced a substrate with a polyimide alignment film.

A frame is formed by applying a sealant to the substrate coated with the alignment film, liquid crystal is dropped in the frame, and the counter substrate is bonded under vacuum, and then irradiated with UV (accumulated light intensity: 200 mJ/cm ² ) through a mask. , 120° C. for 60 minutes to form a cell. The cell was observed with a microscope for transmitted polarized light to confirm whether or not there was any unevenness. Orientation was evaluated according to the following criteria.
O: There is no unevenness.
x: There is unevenness.

(Adhesion strength test)
A sealant was applied to positions of 15mm x 3mm and 15mm x 21mm on an ITO substrate (30mm x 30mm x 0.5mmt) on which 6μm spacers were dispersed, and the diameter of the sealant after bonding was 1.5 to 2.5mmφ. Dot application was applied so as to cover the range. After that, the same type of substrate (23 mm × 23 mm × 0.5 mmt) is bonded together and irradiated with ultraviolet light at an integrated light amount of 3,000 mJ/cm ² (irradiation device: UVX-01224S1, manufactured by Ushio Inc.) to cure at 120 ° C. It was heated in an oven for 60 minutes to prepare a cured product test piece. Using an Autograph (TG-2kN, manufactured by Minebea Co., Ltd.), a test piece was fixed and a position of 15 mm×25 mm was punched out from the substrate at a rate of 5 mm/min to measure the adhesive strength.

The results are shown in Tables 1 and 2.

The sealants of Examples were excellent in both dripping property and applicability. In particular, a comparison between Example 1 and Comparative Example 4, and between Example 2 and Comparative Example 5 revealed that, among organic thixotropic agents, when a liquid thixotropic agent was used, dripping property and applicability were improved. It turns out that it is excellent in both.
On the other hand, the sealing agents of Comparative Examples 1 to 5 did not contain a liquid thixotropic agent.
The sealants of Comparative Examples 1 and 2 contained only an inorganic powder thixotropic agent as the thixotropic agent, and were inferior in coatability.
By comparing Comparative Examples 1 and 3, when the content of the inorganic powder thixotropic agent as the thixotropic agent was small, the dripping property was inferior.
The sealant of Comparative Example 4 contained an organic powder thixotropic agent as a thixotropic agent, and therefore was inferior in dripping property.
A comparison between Comparative Examples 5 and 4 shows that when the content of the organic powder thixotropic agent as the thixotropic agent is increased, both the dripping property and the coatability are inferior.

Claims (4)

(A) a curable resin, (B) a polymerization initiator and/or (C) a thermosetting agent, and (D) a liquid that is one or more selected from the group consisting of polyether-based phosphate esters and fatty acid esters A sealant for a liquid crystal dropping method, comprising a thixotropic agent, (E) a filler (but not a powder thixotropic agent) , and a powder thixotropic agent . 2. The curable resin according to claim 1 , wherein (A) the curable resin contains one or more selected from the group consisting of partially (meth)acrylated epoxy resins of bifunctional or higher functional epoxy resins and combinations of epoxy resins and acrylic resins. sealant for liquid crystal drop method. Furthermore, the sealant for liquid crystal dripping methods according to claim 1 or 2 , further comprising a silane coupling agent . A liquid crystal display sealed with the liquid crystal dropping method sealant according to any one of claims 1 to 3 .