JP2020076794A - Sealant composition for liquid crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealant composition for a liquid crystal display element having high light-shielding property against visible light and high photocurability against ultraviolet light. SOLUTION: The sealant composition for a liquid crystal display element of the present invention contains a curable compound (A), a photopolymerization initiator (B) and zirconium nitride (C). [Selection diagram] None

Description

  The present invention relates to a sealant composition for liquid crystal display devices containing a curable compound, a photopolymerization initiator and zirconium nitride.

  In manufacturing a liquid crystal display device such as a liquid crystal panel, for example, a sealant composition for a liquid crystal display element is applied to the outer periphery of one of the two substrates constituting the liquid crystal panel, and a predetermined amount is applied to either substrate. The liquid crystal dropping method is one in which the liquid crystal is dropped, the two substrates are bonded together under vacuum, and then returned to atmospheric pressure to fill the liquid crystal between the substrates to cure the sealant composition for liquid crystal display elements. It is popular.

  In the liquid crystal dropping method, a sealant is applied to one of the two substrates in a frame shape to form a frame seal, liquid crystal is dropped onto either of the substrates, and the two substrates are bonded together under vacuum to obtain active energy. The liquid crystal display element sealant composition is photocured by irradiation with rays. At present, the sealing agent composition for liquid crystal display elements is subsequently cured by heat, and as the sealing agent composition for liquid crystal display elements, a composition that is cured by light and heat is used.

  In a liquid crystal display, a black matrix is formed to prevent light leakage. However, since the liquid crystal display element sealant composition is applied to the outer periphery of the substrate, the liquid crystal display element sealant composition does not have a light-shielding property, so that the liquid crystal display element sealant composition can be used as a backlight. Light leaks out and the display quality is impaired. Further, recent liquid crystal displays are required to have higher definition, higher brightness and narrower frame, and further promote the above problems.

  In order to solve such a problem, Patent Document 1 describes a light-shielding sealant for liquid crystal display elements, which contains titanium black in order to impart light-shielding properties to the sealant composition for liquid crystal display elements. However, the light transmittance of titanium black has a light transmittance peak at 450 to 500 nm, and in order to sufficiently block visible light, it is necessary to include a large amount in the sealant, and as a result, light curing Was hindering me.

JP 2005-292801 A

Therefore, there has been a demand for a sealant composition for a liquid crystal display device, which has a high light-shielding property against a visible light.
An object of the present invention is to provide a sealant composition for liquid crystal display devices, which has a high light-shielding property against visible light and a high photocurability against ultraviolet light.

The present invention relates to, for example, the following.
[1] A sealant composition for a liquid crystal display device containing a curable compound (A), a photopolymerization initiator (B) and zirconium nitride (C).
[2] The sealant composition for a liquid crystal display element according to [1], wherein the compounding amount of the component (B) is 0.1 to 10 parts by weight with respect to 100 parts by weight of the component (A).
[3] The sealant composition for a liquid crystal display device according to [1] or [2], wherein the component (B) contains a polyether compound having a dialkylaminobenzoyl group.
[4] The sealant composition for liquid crystal display devices according to any one of [1] to [3], wherein the component (B) contains thioxanthones.
[5] The sealant composition for liquid crystal display device according to any one of [1] to [3], wherein the component (A) contains a partially (meth) acrylated epoxy resin.
[6] The sealant composition for liquid crystal display devices according to any one of [1] to [4], which further contains a thermosetting agent (D).
[7] A liquid crystal display sealed with the cured product of the sealant composition for liquid crystal display device according to any one of [1] to [6].

  The sealant composition for liquid crystal display devices of the present invention has a high light-shielding property against visible light and a high photocurability against ultraviolet light.

<Sealant composition for liquid crystal display device>
The sealant composition for liquid crystal display devices includes a curable compound (A), a photopolymerization initiator (B) and zirconium nitride (C) (hereinafter also referred to as component (A), component (B) and component (C), respectively). )including.

[Curable compound (A)]
The curable compound contained in the sealant for a liquid crystal display element includes a resin curable by light, and a resin curable by both light and heat is preferable. Examples thereof include epoxy resin, (meth) acrylated epoxy resin, partial (meth) acrylated epoxy resin, and (meth) acrylic resin. The curable compound is preferably a partially (meth) acrylated epoxy resin. In the present specification, (meth) acrylic means methacrylic and / or acrylic, and (meth) acrylate means methacrylate and / or acrylate. Further, the (meth) acrylated epoxy resin means a resin in which all epoxy groups in the epoxy resin have reacted with (meth) acrylic acid. Partially (meth) acrylated epoxy resin means a resin in which some epoxy groups in the epoxy resin have reacted with (meth) acrylic acid, that is, the resin has an epoxy group and a (meth) acrylic group.

  The type of epoxy resin is not particularly limited, and bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac. Type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, triphenol methane Examples thereof include phenol novolac type epoxy resins having a skeleton. In addition, diglycidyl ether compounds of difunctional phenols, diglycidyl ether compounds of difunctional alcohols and their halides, hydrogenated products and the like can also be used. Polyfunctional epoxy resins can also be used and include, for example, trifunctional and tetrafunctional epoxy resins. Further, the epoxy resin described in JP 2012-077202 A can be used.

  The (meth) acrylated epoxy resin and the partial (meth) acrylated epoxy resin can be obtained by the reaction of the epoxy resin and the (meth) acrylic acid. Specifically, the epoxy resin has a predetermined equivalent ratio of (meth) acrylic acid, a catalyst (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstibine, etc.), and a polymerization inhibitor (for example, , Metoquinone, hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene, etc.) and perform an esterification reaction at, for example, 80 to 110 ° C. to (meth) acrylate all or part of the epoxy groups. it can. The epoxy resin used as a raw material is not particularly limited, and examples thereof include the epoxy resins exemplified above.

  In the partially (meth) acrylated epoxy resin, the ratio of the (meth) acrylic group is preferably 10 to 90 mol% with respect to the total number of moles of the (meth) acrylic group and the epoxy group in the resin. It is preferably 40 to 60 mol%. The partially (meth) acrylated epoxy resin preferably contains a compound containing one or more epoxy groups and one or more (meth) acrylic groups in one molecule.

  The (meth) acrylic resin is not particularly limited as long as it is a resin having a methacrylic and / or an acrylic group, and examples thereof include (meth) acrylic acid ester.

  As the (meth) acrylic resin, a hydroxy group-containing (meth) acrylate can be used, and for example, a hydroxyalkyl (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxy). Butyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc., polyol (meth) acrylate (glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, ditrimethylolpropane di (meth)) Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc., alkylene oxide-added polyol (meth) acrylate (eg, alkylene oxide-added trimethylolpropane di (meth) acrylate, alkylene oxide-added pentaerythritol tri-acrylate) (Meth) acrylate, alkylene oxide addition dipentaerythritol penta (meth) acrylate, etc.) and the like.

  As the (meth) acrylic resin, an alicyclic (meth) acrylate can be used, for example, a monocyclic (meth) acrylate such as cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, Bicyclic (meth) acrylates such as isobornyl (meth) acrylate and norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, adamantyl ( Examples thereof include tricyclic (meth) acrylates such as (meth) acrylate.

  As the (meth) acrylic resin, a (meth) acrylate containing at least one selected from polyisoprene, polybutadiene, and polyurethane in its skeleton can be used. As a commercial product of a (meth) acrylate oligomer having a polyisoprene skeleton, for example, "UC-203M" (average molecular weight 35000) manufactured by Kuraray Co., Ltd. is mentioned, and as a commercial product of a (meth) acrylate oligomer containing polybutadiene in the skeleton. Examples include "TE2000" (weight average molecular weight 2500) manufactured by Nippon Soda Co., Ltd.

The curable compound may be used alone or in combination of two or more kinds, and it is preferable that the curable compound contains a partial (meth) acrylated epoxy resin from the viewpoint that it can be cured by both light and heat. Bisphenol A type epoxy resin is more preferable.
The compounding amount of the curable compound in the sealant composition for liquid crystal display devices is not particularly limited, but is preferably 10 to 90% by weight, more preferably 20 to 85% by weight, and further preferably 30 to 80% by weight.

[Photopolymerization initiator (B)]
The sealant composition for liquid crystal display elements is cured by light. Therefore, it contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it is a compound that generates a radical or a cation by light and initiates a polymerization reaction.
Among the light, a compound that initiates a polymerization reaction with ultraviolet light, specifically, light with a wavelength of 100 to 400 nm is preferable, and a compound that initiates a polymerization reaction with light with a wavelength of 340 to 400 nm is more preferable.

  Photopolymerization initiators include benzoins, acetophenones, benzophenones, thioxanthones, α-acyloxime esters, phenylglyoxylates, benzyls, azo compounds, diphenyl sulfide compounds, acylphosphine oxide compounds, dialkyls. Examples thereof include polyether compounds having an aminobenzoyl group, benzoin ethers and anthraquinones, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes. Among these, in addition to those classified as photoinitiating compounds, there are those classified as visible light sensitizing compounds, but in the present invention, they have a photosensitizing action and function as a photopolymerization initiator. Those which are generally classified as visible light sensitizing compounds are photopolymerization initiators. It is preferable that the photopolymerization initiator has a low solubility in liquid crystal, and has a structure such that the photopolymerization initiator itself does not generate a decomposition product or does not gasify the decomposition product. The photopolymerization initiator may be used alone or in combination of two or more.

The photopolymerization initiator may be a combination of a photoinitiating compound and a visible light sensitizing compound. The photoinitiating compound is photoexcited by the visible light sensitizing compound and becomes a polymerization initiation species.
In the photopolymerization initiator of the present invention, the molar ratio of the photoinitiating compound to the visible light sensitizing compound (photoinitiating compound / visible light sensitizing compound) is preferably from the viewpoint of supplying stable and sufficient radicals. It is 1/5 to 5/1, more preferably 1/3 to 3/1, and further preferably 1/2 to 2/1.

式中、ｎ１は、０〜５０であり、好ましくは１〜４５である。 The photopolymerization initiator preferably contains a polyether compound having a dialkylaminobenzoyl group, which is a photoinitiating compound. Further, it is preferable to contain thioxanthones which are visible light sensitizing compounds. It is preferable to use a polyether compound having a dialkylaminobenzoyl group and thioxanthones in combination. As the polyether compound having a dialkylaminobenzoyl group, the compound represented by the following formula (1B-1) is more preferable, and as the thioxanthones, the compound represented by the following formula (1B-2) is more preferable. A combination of a compound represented by the following formula (1B-1) and a compound represented by the following formula (1B-2), which is a combination of a photoinitiating compound and a visible light sensitizing compound, is more preferable.

In the formula, n1 is 0 to 50, preferably 1 to 45.

式中、ｎ２は、０〜５０であり、好ましくは１〜４５である。

In the formula, n2 is 0 to 50, preferably 1 to 45.

  The compounding amount of the photopolymerization initiator is not particularly limited, but is preferably 0.1 to 10.0 parts by weight, and more preferably 0.5 to 5.0 parts by weight with respect to 100 parts by weight of the curable compound. is there.

[Zirconium nitride (C)]
Zirconium nitride has a maximum light transmittance at a light wavelength of 300 to 400 nm, and exhibits uniform and high light-shielding performance when the light wavelength exceeds 400 nm. That is, there is a significant difference in light transmittance between the ultraviolet region and the other regions.
Therefore, by combining this zirconium nitride and the above photopolymerization initiator that initiates polymerization by light in the ultraviolet region, the sealant composition for a liquid crystal display device of the present invention is cured by the ultraviolet light, and also in a region other than the ultraviolet light. Excellent light shielding property against the light of

  Thus, zirconium nitride has an excellent light-shielding property with respect to light in a region other than ultraviolet rays, whereby light leakage of the liquid crystal display element can be prevented. Along with that, as a photopolymerization initiator, a compound that initiates polymerization by light in the ultraviolet region, more preferably by using a compound that initiates polymerization by light in the wavelength region of 300 to 400 nm in combination with this zirconium nitride, The curable compound can be sufficiently cured.

窒化ジルコニウムの市販品としては、三菱マテリアル電子化成株式会社製ＵＢ−１等が挙げられる。
窒化ジルコニウムの配合量としては、特に限定されないが、硬化性化合物１００重量部に対して、好ましくは１〜５０重量部、より好ましくは５〜４０重量部、さらに好ましくは１０〜３０重量部である。 Zirconium nitride preferably has an average primary particle size of 20 to 50 nm. The average primary particle diameter is obtained by the following equation from the specific surface area obtained by the BET equation when nitrogen is used.

Examples of commercially available zirconium nitride include UB-1 manufactured by Mitsubishi Materials Denshi Kasei Co., Ltd.
The compounding amount of zirconium nitride is not particularly limited, but is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, and further preferably 10 to 30 parts by weight with respect to 100 parts by weight of the curable compound. ..

<< Further ingredients >>
The sealant composition for liquid crystal display devices may optionally contain the following additional components as long as the object of the present invention is not impaired.

[Thermal Curing Agent (D) and Thermal Radical Initiator (E)]
The sealant composition for liquid crystal display devices can be used after being cured by heat in addition to light.
When it is cured by heat, it preferably contains a heat curing agent and a heat radical initiator.

  The thermosetting agent is not particularly limited, and examples thereof include amine-based thermosetting agents such as organic acid dihydrazide compounds, amine adducts, imidazole and its derivatives, dicyandiamide, aromatic amines, epoxy-modified polyamines, and polyaminoureas. Among them, VDH (1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin), ADH (adipic acid dihydrazide), UDH (7,11-octadecadiene-1,18-dicarbohydrazide) and LDH ( Organic acid dihydrazides such as octadecane-1,18-dicarboxylic acid dihydrazide); from ADEKA, ADEKA HARDNER EH5030S, from Ajinomoto Fine-Techno, Amicure PN-23, Amicure PN-30, Amicure MY-24, Amicure MY-H, etc. Is preferred as the amine adduct. These thermosetting agents may be used alone or in combination. The blending amount of the thermosetting agent is not particularly limited, but is preferably 1 to 40 parts by weight, and more preferably 5 to 35 parts by weight with respect to 100 parts by weight of the curable compound.

  The type of thermal radical polymerization initiator is not particularly limited, and examples thereof include an azo compound and an organic peroxide. Examples of the azo compound include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and polydimethyl having 4,4′-azobis (4-cyanopentanoic acid) and a terminal amino group. Examples thereof include polycondensation products of siloxane. Examples of organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, and peroxydicarbonates. The blending amount of the thermal radical polymerization initiator (E) is not particularly limited, but is preferably 0.1 to 25 parts by weight, more preferably 0.5 to 15 parts by weight with respect to 100 parts by weight of the curable compound (A). Parts by weight.

[Filler (F)]
The sealant composition for liquid crystal display devices may contain a filler.
The filler is a liquid crystal display element sealant composition by controlling the viscosity of the liquid crystal display element sealant composition, improving the strength of the cured product obtained by curing the liquid crystal display element sealant composition, or suppressing linear expansion. It is added for the purpose of improving adhesion reliability. The filler is not particularly limited, and examples thereof include known inorganic fillers and organic fillers. As inorganic fillers, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, alumina, zinc oxide, silicon dioxide, kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, and silicon nitride. Is mentioned. As the organic filler, poly (meth) acrylic acid ester such as polymethylmethacrylate, poly (meth) acrylic acid ethyl, polystyrene, a copolymer obtained by copolymerizing a monomer constituting these, and another monomer, polyester Examples thereof include fine particles, polyurethane fine particles, and rubber fine particles, and organic fillers are particularly preferable from the viewpoint of stress relaxation. The compounding amount of the filler is preferably 2 to 40 parts by weight, and more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the curable compound.

[Coupling agent (G)]
The sealant composition for liquid crystal display devices may include a coupling agent.
The coupling agent is added for the purpose of further improving the adhesiveness with the liquid crystal display substrate. The coupling agent is not particularly limited, and examples thereof include γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. These coupling agents may be used alone or in combination of two or more. The amount of the coupling agent is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the curable compound.

[Other]
The liquid crystal display element sealant composition may contain a dispersant, a coloring component such as a pigment or a dye, a storage stabilizer, a plasticizer, a viscoelasticity adjusting agent, and a surface active adjusting agent (wetting agent or defoaming agent). Good. Coloring components such as pigments and dyes are preferably used within a range that does not affect the ultraviolet transmittance.

<< Physical property values >>
The OD value per 1 μm of thickness of the cured product obtained by curing the liquid crystal display element sealant composition under the conditions described in the examples is from 0.01 to 3 from the viewpoint of preventing light leakage from the backlight. 0 is preferable and 0.02 to 2.0 is more preferable.
The OD value is a value calculated by the following formula.
OD (λ) = log ₁₀ T (λ) −log ₁₀ I (λ)
Here, (λ) is the wavelength, T (λ) is the amount of transmitted light in the wavelength band, and I (λ) is the amount of incident light in the wavelength band. The OD value can be measured by the method described in the examples.

  The viscosity of the sealant composition for liquid crystal display device at 25 ° C. is not particularly limited, but is preferably 100 to 3,000,000 mPa · s, and more preferably 200 to 2,000,000 mPa · s. , 300 to 1,500,000 mPa · s is particularly preferable. Within such a range, flow is unlikely to occur when applied to the liquid crystal, and contamination of the liquid crystal can be suppressed. The viscosity is a value measured using an E-type viscometer.

<< Production method >>
The sealant composition for liquid crystal display devices can be produced by mixing the above-mentioned essential components and optional components as necessary.

<Liquid crystal display>
A liquid crystal display sealed with a cured product of a sealant composition for a liquid crystal display element is a sealant composition for a liquid crystal display element in which a transparent substrate such as a facing glass or resin is bonded to a transparent substrate such as a facing glass or a resin. A cured product of the product, and a liquid crystal sealed with a transparent substrate such as glass and a resin and a cured product of the sealant composition for a liquid crystal display device, which face each other.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Synthesis example 1]
Synthesis of curable compound Prepare a 500 ml glass 4-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, and use 340 g (2.0 equivalents / epoxy group) of bisphenol A type epoxy resin; ), Methacrylic acid 86.1 g (1.0 equivalent), PS-PPh ₃ (triphenylphosphinopolystyrene, 2.0 mmol / g) [manufactured by Biotage] 750 mg (1.5 meq / TPP (triphenylphosphine) ) The catalyst amount (g) was mixed and stirred at 100 to 110 ° C using an oil bath. The reaction value was titrated with sodium hydroxide (1N / 100), the residual amount of methacrylic acid was calculated, and the reaction rate was calculated from the amount of methacrylic acid added at the beginning and the residual amount of methacrylic acid, and the reaction rate was 99.5. The reaction was carried out by heating and stirring until the content became at least%. The reaction liquid was cooled to 60 ° C., and PS-PPh ₃ as a catalyst was removed with a nylon mesh NY-10HC (manufactured by Sefar, Switzerland) having an opening of 10 μm to obtain a partially methacrylic epoxy resin (A-1). The epoxy equivalent of the obtained resin was 468 g / eq.

[Synthesis example 2]
Synthesis of Compound B-1 (n1 = 6 to 9) Denacol EX-830 (diglycidyl ether of PEG400 (n1 = 6 to 9) manufactured by Nagase Chemtex) 26.8 g (0.1 epoxy equivalent), 4-dimethyl Aminobenzoic acid 16.5 g (0.1 equivalent), benzyltrimethylammonium chloride 3.71 g (0.02 equivalent), MIBK (methyl isobutyl ketone) 25 g were put in a flask and stirred at 110 ° C. for 24 hours using an oil bath. did. The reaction mixture was cooled to room temperature, dissolved in 50 g of chloroform and washed 6 times with 100 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 35.3 g of compound B-1.

[Synthesis example 3]
Synthesis of Compound B-2 (n2 = 6 to 9) Denacol EX-830 (Diglycidyl ether of PEG400 (n2 = 6 to 9) manufactured by Nagase Chemtex) 26.8 g (0.1 epoxy equivalent), 2-hydroxy -9H-thioxanthen-9-one 22.83 g (0.1 equivalent), benzyltrimethylammonium chloride 3.71 g (0.02 equivalent) and MIBK 40 g were put in a flask and stirred at 110 ° C for 72 hours using an oil bath. did. The reaction mixture was cooled to room temperature, dissolved in 50 g of chloroform and washed 6 times with 100 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 36.2 g of compound B-2.

[Measuring method]
(1) Test piece preparation method The compositions of Examples and Comparative Examples were applied to 0.05 mmt release PET coated with 6 μm spacers, 0.05 mmt release PET was overlaid on the coated surface, and the release PET was coated. The upper and lower surfaces of the laminate in which the composition was sandwiched between were further sandwiched by 0.5 mmt glass, and the upper and lower surfaces of the laminate sandwiched in the glass were sandwiched by clips and left still for a while, while UV 3,000 mJ was applied from one side. / Cm ² was irradiated as measurement sample 1, and UV 3,000 mJ / cm ² was irradiated from one surface and then cured in a hot air circulation oven at 120 ° C. for 60 minutes to be measurement sample 2.

(2) OD value Measurement sample 2 was measured using a black and white transmission densitometer (X-Rite 361T (V), manufactured by X-Rite).
(3) Gap Measurement In Sample 2, the height of the cured composition between the release PETs was used as the gap, and the gap was measured with a micrometer.
(4) In the photocurable group reaction rate measurement sample 1, the release PET on the side not irradiated with UV was peeled off, and FT-IR measurement by a germanium ATR method (apparatus: Spectrum One, manufactured by Perkin-Elmer) was performed.
The reaction rate was determined as follows.
The reaction rate (conversion rate) of the (meth) acrylic group was calculated from the peak area of the (meth) acrylic group in the obtained IR spectrum. Specifically, the reduction of the area of absorption of (meth) acrylic group from 1620 to 1650 cm ⁻¹ was calculated based on the area of absorption of double bond of benzene ring from 1480 to 1520 cm ⁻¹ .

[Example 1]
100 parts by weight (100 g) of the partially-methacrylated epoxy resin (A-1) as the curable compound (A), 2 parts by weight of the compound B-1 and 2 parts by weight of the compound B-2 as the photopolymerization initiator (B), 22.8 parts by weight of thermosetting agent (D), 1.5 parts by weight of coupling agent (G), 10 parts by weight of zirconium nitride (C) are added and mixed, and a sealant composition for liquid crystal display device is prepared. Got
In [Example 2] to [Example 4] and [Comparative Example 1] to [Comparative Example 6], the composition shown in Table 1 was obtained in the same manner as in Example 1 to obtain a sealant composition for a liquid crystal display element.

The components described by abbreviations in Table 1 are as follows.
Zirconium Nitride: "UB-1" manufactured by Mitsubishi Materials Electronic Chemical Co., Ltd.
Titanium black: "13M-T" manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.
Carbon black: "# 2600" manufactured by Mitsubishi Chemical Corporation
Thermosetting agent: "ADEKA HARDNER EH-5030" manufactured by ADEKA
Coupling agent: 3-glycidoxypropyltriethoxysilane "KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.

Claims (7)

  A sealant composition for a liquid crystal display device, which comprises a curable compound (A), a photopolymerization initiator (B) and zirconium nitride (C).   The sealant composition for liquid crystal display device according to claim 1, wherein the compounding amount of the component (B) is 0.1 to 10 parts by weight with respect to 100 parts by weight of the component (A).   The sealant composition for a liquid crystal display device according to claim 1, wherein the component (B) contains a polyether compound having a dialkylaminobenzoyl group.   The sealant composition for a liquid crystal display element according to claim 1, wherein the component (B) contains thioxanthones.   The sealant composition for liquid crystal display devices according to claim 1, wherein the component (A) contains a partially (meth) acrylated epoxy resin.   The sealant composition for liquid crystal display elements according to claim 1, further comprising a thermosetting agent (D).   A liquid crystal display, which is sealed with a cured product of the sealant composition for liquid crystal display element according to any one of claims 1 to 6.