TWI682991B - Liquid crystal sealing agent and liquid crystal display cell using the same - Google Patents

Abstract

An objective of this invention relates to a liquid crystal sealing agent for liquid crystal dropping method to be cured by heat. The provided liquid crystal sealing agent for liquid crystal dropping method has an extremely low circuit corrosion after humidity resistance test and has low liquid crystal contamination, and excellent in general characteristic such as adhesive strength and the likes, therefore capable of realize high fineness, high response, low driving voltage and long lifetime of liquid crystal display cell.

The present invention provides a liquid crystal sealing agent for liquid crystal dropping method containing (A) a curable compound, wherein, a cured article obtained by thermal curing at 130℃ for 1 hour without exposure to ultraviolet light has a water absorption ratio of 2.0% or less based on JIS-K7209, and has a moisture permeability of 130g/m²＊24h or less based on JIS-K7129.

Description

Liquid crystal sealant and liquid crystal display unit using the liquid crystal sealant

The present invention relates to a liquid crystal sealant that is hardened by heat, and is a liquid crystal sealant used in a liquid crystal dropping method. More specifically, it relates to a liquid crystal sealing agent for a liquid crystal dropping method in which the corrosion resistance of the wiring after the moisture resistance test is extremely low, and the general characteristics such as low liquid crystal contamination and adhesion strength are excellent.

With the increase in size of liquid crystal display cells in recent years, a so-called liquid crystal dropping method with higher mass productivity has been proposed as a method of manufacturing liquid crystal display cells (refer to Patent Document 1 and Patent Document 2). Specifically, it is a method of manufacturing a liquid crystal display unit in which liquid crystal is dropped into the dam of a liquid crystal sealant formed on one substrate, and then another substrate is bonded to thereby seal the liquid crystal.

However, the liquid crystal dropping method is because the uncured liquid crystal sealant is in contact with the liquid crystal. At this time, the components of the liquid crystal sealant will dissolve (dissolve) in the liquid crystal to reduce the resistance value of the liquid crystal, resulting in the problem of poor display near the seal point.

To solve this problem, it is now used as a liquid crystal dropping method The liquid crystal sealant is a combination of light and heat, and has been put into practical use (Patent Documents 3 and 4). The liquid crystal dropping method using this liquid crystal sealant is characterized by irradiating light to the liquid crystal sealant sandwiched on the substrate to harden it once, then heating it and hardening it again. According to this method, the uncured liquid crystal sealant can be quickly cured by light, and the dissolution (dissolution) of the liquid crystal sealant component in the liquid crystal can be suppressed. Furthermore, the problem of insufficient adhesive strength due to hardening shrinkage and the like during light hardening occurs only during light hardening, but if it is a combination of light and heat, the secondary hardening by heating can be used to obtain a stress relief effect, which has It can also solve the advantages of such problems.

By making this photothermosetting liquid crystal dropping method for liquid crystal sealants practical, the liquid crystal dropping method has become a commonly used method.

With the practical application of the above-mentioned liquid crystal dropping method, even a large-sized liquid crystal display unit can be easily manufactured, and the result is related to the spread of liquid crystal displays.

On the other hand, this liquid crystal dropping method sometimes still has disadvantages in the quality of the manufactured liquid crystal display unit. One is the problem of defects in the driving of liquid crystals after humidity resistance reliability. This problem is a problem also caused by the liquid crystal display unit manufactured by the conventional liquid crystal injection method, but it is particularly noticeable in the liquid crystal display unit manufactured by the liquid crystal dropping method. In order to solve this problem, various studies have been conducted in the past. For example, by adding a thermal radical polymerization initiator and a hardening accelerator, the reaction rate is increased, or a material with low solubility in liquid crystal is used as a constituent component.

However, these studies have not reached the realization of the liquid crystal sealing agent for the liquid crystal dropping method that can fully solve the above-mentioned problems.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 63-179323

[Patent Document 2] Japanese Patent Laid-Open No. 10-239694

[Patent Document 3] Japanese Patent No. 3583326

[Patent Document 4] Japanese Patent Laid-Open No. 2004-61925

[Patent Document 5] Japanese Patent Laid-Open No. 2004-126211

[Patent Document 6] Japanese Patent Laid-Open No. 2009-8754

[Patent Literature 7] International Publication No. 2008/004455

The present invention relates to a liquid crystal sealing agent for a liquid crystal dropping method that can be hardened by heat, and proposes a liquid crystal sealing agent for a liquid crystal dropping method, which has extremely low corrosion of wiring after a humidity resistance test, and even with low liquid crystal contamination, The general characteristics such as strength are also excellent. Therefore, those who can achieve high definition, high-speed response, low-voltage driving, and long life of liquid crystal display devices have been proposed.

In order to solve the above-mentioned driving defects, the inventors have found that it is caused by wiring corrosion after the humidity resistance test. This wiring corrosion is affected by insufficient UV curing under the black matrix. The invention of the present invention was completed almost only through the moisture permeability and water absorption of the position hardened by heat.

That is, the present invention relates to the following 1) to 14). In this specification, when it is described as "(meth)acrylic acid", it means "acrylic acid" and/or "methacrylic acid". In addition, the "liquid crystal sealing agent for liquid crystal dropping method" system is sometimes described as "liquid crystal sealing agent".

1) A liquid crystal sealing agent for a liquid crystal dropping method, which contains (A) a curable compound, wherein a cured product obtained by heat curing at 130°C for 1 hour without irradiating ultraviolet rays, the water absorption measured in accordance with JIS-K7209 The rate is 2.0% or less, and the moisture permeability measured in accordance with JIS-K7129 is 130 g/m ² *24h or less.

2) The liquid crystal sealing agent for liquid crystal dropping method as described in 1) above, further containing (B) a thermal radical polymerization initiator.

3) The liquid crystal sealing agent for liquid crystal dropping method as described in 1) or 2) above, wherein the component (B) thermal radical polymerization initiator does not contain oxygen-oxygen bond (-OO-) and A nitrogen-nitrogen bond (-N=N-) thermal radical polymerization initiator.

4) The liquid crystal sealing agent for liquid crystal dropping method as described in any one of 1) to 3) above, further containing (C) an optical radical polymerization initiator.

5) The liquid crystal sealing agent for liquid crystal dropping method as described in any one of 1) to 4) above, further containing (D) a filler, and the content rate of the filler in the total liquid crystal sealing agent is 20% by mass or more .

6) The liquid crystal sealing agent for liquid crystal dropping method as described in any one of 1) to 5) above, wherein the component (D) is (D-1) an organic filler and (D-2) an inorganic filler mixture.

7) The liquid crystal for liquid crystal dropping method as described in any one of 1) to 6) above The sealing agent, wherein the content of the inorganic filler of the aforementioned component (D-2) in the total liquid crystal sealing agent is 20% by mass or more.

8) The liquid crystal sealing agent for liquid crystal dropping methods as described in any one of 1) to 7) above, wherein the curable compound of the component (A) is an epoxy (meth)acrylate compound.

9) The liquid crystal sealing agent for liquid crystal dropping method as described in any one of 1) to 7) above, wherein the curable compound of the component (A) is an epoxy (meth)acrylate compound and an epoxy compound mixture.

10) The liquid crystal sealing agent for liquid crystal dropping methods as described in any one of 1) to 9) above, further containing (E) a thermosetting agent.

11) The liquid crystal sealing agent for liquid crystal dropping method as described in 10) above, wherein the thermosetting agent of the component (E) is an organic acid hydrazide.

12) The liquid crystal sealing agent for liquid crystal dropping method as described in any one of 1) to 11) above, further containing (F) a silane coupling agent.

13) A method for manufacturing a liquid crystal display unit, comprising the steps of: in a liquid crystal display unit composed of two substrates, the liquid crystal according to any one of 1) to 12) formed on a substrate After dropping the liquid crystal inside the dam of the liquid crystal sealant using the dropping method, it is bonded to another substrate, and then hardened by light and/or heat.

14) A liquid crystal display unit in which a hardened product obtained by hardening the liquid crystal sealing agent for liquid crystal dropping method described in any one of 1) to 12) above is sealed.

The liquid crystal sealing agent for liquid crystal dropping method of the present invention can Wiring corrosion is suppressed to the maximum extent, and even with low liquid crystal contamination and excellent adhesion strength, it is extremely useful as a liquid crystal sealant for liquid crystal display elements.

Fig. 1 is a diagram showing the hardening width of the shading portion. A liquid crystal sealant added with 1 w% of 5 μm glass fiber is applied to the center of the etched chrome plated glass substrate, and the black matrix substrate is used as the counter substrate and bonded, and fixed with a jig (before ultraviolet irradiation). After irradiating 3000 mJ/cm ² of ultraviolet rays from the chromium-etched glass substrate side, the two substrates that had been bonded were peeled off, and the portion where the light was shaded under the chromium was confirmed with a microscope, and the hardening width of the shade portion was measured.

The liquid crystal sealing agent of the present invention contains (A) a curable compound.

The component (A) is not particularly limited as long as it undergoes polymerization reaction by light or heat, and examples thereof include a curable compound having a (meth)acryloyl group and a curable compound having an epoxy group.

Examples of the hardening compound having a (meth)acryloyl group include (meth)acrylate and epoxy (meth)acrylate. (Meth)acrylates include, for example, benzyl methacrylate, cyclohexyl methacrylate, glycerol dimethacrylate, glycerol triacrylate, EO modified glycerol triacrylate, neopentyl alcohol acrylate , Trimethylolpropane triacrylate, ginseng (acryloxyethyl) tripolyisocyanate, dipentaerythritol hexaacrylate, fluoroethanolamine triacrylate, etc. Epoxy (meth)acrylate can be prepared by a well-known method by the reaction of an epoxy compound and (meth)acrylic acid. Become the original The epoxy compound of the material is not particularly limited, but a bifunctional or more epoxy compound is preferred, and examples thereof include bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, and bisphenol S-type epoxy compounds. Phenol novolac epoxy compound, cresol novolac epoxy compound, bisphenol A novolac epoxy compound, bisphenol F novolac epoxy compound, alicyclic epoxy compound, aliphatic chain epoxy Compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, hydantoin type epoxy compounds, triisocyanate type epoxy compounds, phenol novolac type epoxy compounds with a triphenol methane skeleton , Other, diglycidyl etherate of difunctional phenols such as catechol and resorcinol, diglycidyl etherate of difunctional alcohols, and their halides and hydrides. Among these, an epoxy compound having a resorcinol skeleton is preferred from the viewpoint of liquid crystal contamination, for example, resorcinol diglycidyl ether and the like. In addition, the ratio of the epoxy group to the (meth)acryloyl group is not limited, and can be appropriately selected from the viewpoints of step suitability and liquid crystal contamination.

Therefore, it is preferable that the hardening compound having a (meth)acryloyl group is a hardening compound having a (meth)acryloyloxy group and having a resorcinol skeleton, for example, resorcinol diglycidyl ether Acrylate, methacrylate of resorcinol diglycidyl ether.

Examples of the hardenable compound having an epoxy group include epoxy compounds. The epoxy compound is not particularly limited, but a bifunctional or more epoxy compound is preferred, and examples thereof include bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, and phenols. Novolac epoxy compound, cresol novolac epoxy compound, bisphenol A novolac epoxy compound Bisphenol F novolac epoxy compound, alicyclic epoxy compound, aliphatic chain epoxy compound, glycidyl ester epoxy compound, glycidyl amine epoxy compound, hydantoin type Epoxy compound, tripolyisocyanate epoxy compound, phenol novolac epoxy compound with triphenol methane skeleton, other, diglycidyl etherate of difunctional phenols, diglycidyl ether of difunctional alcohols Compounds, their halides, hydrides, etc. Among these, from the viewpoint of liquid crystal contamination, bisphenol-type epoxy compounds and novolac-type epoxy compounds are preferred.

Two or more kinds of hardening compounds with (meth)acryloyl oxy groups and epoxy groups can be used. Mixing (meth)acrylated epoxy compounds and epoxy compounds is the special feature of the present invention. A good attitude.

The content of the component (A) in the liquid crystal sealant of the present invention is usually 30 to 75% by mass, preferably 40 to 65% by mass. Furthermore, especially when the epoxy compound and the (meth)acrylated epoxy compound are used in combination, the content of the epoxy compound in the component (A) is usually 3 to 30% by mass, preferably 5 to 20% by mass, more preferably It is 8 to 15% by mass.

The liquid crystal sealant of the present invention is a cured product which is heat-cured at 130°C for 1 hour without being irradiated with ultraviolet rays, and has a water absorption rate of 2.0% or less measured in accordance with JIS-K7209 (method D) (where the test conditions are 60°C , 90% of the environment). The water absorbed by the liquid crystal sealant is used to promote the decomposition of organic substances in the liquid crystal sealant, and even transport the decomposed products and impurity ions out of the liquid crystal sealant.

The water absorption rate is preferably 1.8% or less, and more preferably 1.6% or less.

The liquid crystal sealant of the present invention is a cured product which is heat-cured at 130° C. for 1 hour without being irradiated with ultraviolet rays, and has a moisture permeability of 130 g/m ² *24h or less measured in accordance with the method of JIS-K7129 (Method A). Because the water penetrating the liquid crystal sealant has a great influence on the corrosion of wiring. In addition, if Lyssy L80-5000 manufactured by Systech illinois is used, it can be measured in accordance with JIS-K7129 (Method A). The test temperature was set at 60°C.

The moisture permeability is preferably below 110 g/m ² *24h, more preferably below 90 g/m ² *24h.

The liquid crystal sealant of the present invention can use (B) thermal radical polymerization initiator to improve the curing speed and curing degree.

TMH、C、V、22、MC、Percure^RTMAH、AL、HB、Perbutyl^RTMH、C、ND、L、Percumyl^RTMH、D、Peroyl^RTMIB、 IPP、Perocta^RTMND、(日油股份有限公司製)等。 The thermal radical polymerization initiator is not particularly limited as long as it is a compound that generates free radicals by heating to start a chain polymerization reaction, but examples thereof include organic peroxides, azo compounds, and benzoin compounds. , Benzoin ether compound, acetophenone compound, tetraphenyl-1,2-ethylene glycol (benzopinacol), etc., tetraphenyl-1,2-ethylene glycol is suitable for use. For example, as organic peroxides, the following commercially available products are available: Kayamek ^RTM A, M, R, L, LH, SP-30C, Perkadox CH-50L, BC-FF, Cadox B-40ES, Perkadox 14, Trigonox ^RTM 22-70E, 23-C70, 121, 121-50E, 121-LS 50E, 21-LS50E, 42, 42LS, Kayaester ^RTM P-70, TMPO-70, CND-C70, OO-50E, AN, Kayabutyl ^RTM B, Perkadox 16, Kayacarbon ^RTM BIC-75, AIC-75 (made by AKZO Co., Ltd.), Permek ^RTM N, H, S, F, D, G, Perhexa ^RTM H, HC,

TMH, C, V, 22, MC, Percure ^RTM AH, AL, HB, Perbutyl ^RTM H, C, ND, L, Percumyl ^RTM H, D, Peroyl ^RTM IB, IPP, Perocta ^RTM ND, (Nippon Oil Co., Ltd. System) etc.

As the azo compound, the following commercially available products can be obtained: VA-044, V-070, VPE-0201, VSP-1001 (Wako Pure Chemical Industries, Ltd.), and the like. In this manual, the superscript RTM means a registered trademark.

The component (B) is preferably a thermal radical polymerization initiator having no oxygen-oxygen bond (-O-O-) or nitrogen-nitrogen bond (-N=N-) in the molecule. Thermal radical polymerization initiators with an oxygen-oxygen bond (-OO-) or a nitrogen-nitrogen bond (-N=N-) in the molecule will generate a large amount of oxygen or nitrogen when generating free radicals, so they will appear in the liquid crystal The sealant is cured in a state where bubbles are left, and there is a possibility that characteristics such as adhesive strength are reduced. It is particularly suitable to use a thermal radical polymerization initiator of tetraphenyl-1,2-ethylene glycol series (including those chemically modified by tetraphenyl-1,2-ethylene glycol). Specific examples include tetraphenyl-1,2-ethylene glycol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, and 1,2-diethoxy- 1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1, 2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetra(4-methoxyphenyl)ethane, 1,2- Bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(triethylsiloxy)-1,1,2,2-tetraphenylethane Alkanes, 1,2-bis(third butyldimethylsilyloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsilyloxy-1,1 ,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-third butyl dimethyl Based siloxy-1,1,2,2-tetraphenylethane, etc., preferably 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsilyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-third-butyldimethylsilyloxy-1,1,2, 2-tetraphenylethane, 1,2-bis(trimethylsilicon Oxy)-1,1,2,2-tetraphenylethane, more preferably 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1, 2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane, especially the best 1,2-bis(trimethylsiloxy)-1,1,2,2 -Tetraphenylethane.

The above-mentioned tetraphenyl-1,2-ethylene glycol is commercially available from Tokyo Chemical Industry Co., Ltd., Wako Pure Chemical Industries, Ltd. In addition, the hydroxyl etherification of tetraphenyl-1,2-ethylene glycol can be easily synthesized by a well-known method. In addition, the hydroxysilyl etherification of tetraphenyl-1,2-ethylene glycol can be achieved by the basic contact of the corresponding tetraphenyl-1,2-ethylene glycol and various silylating agents in pyridine, etc. It is prepared by heating under the medium. Examples of the silylation agent include trimethylchlorosilane (TMCS), hexamethyldisilazane (HMDS), and N,O-bis(trimethylsilyl), which are generally known as trimethylsilylation agents. Group) trifluoroacetamide (BSTFA) or triethyl chlorosilane (TECS) as a triethyl silylation agent, and tert-butyl methyl silane (TBMS) as a third butyl dimethyl silylation agent Wait. These reagents can be easily obtained from silicon derivative manufacturers. The reaction amount of the silylating agent is preferably 1.0 to 5.0 times the molar ratio of 1 mole of the hydroxyl group of the target compound. More preferably, it is 1.5 to 3.0 times mole. If it is less than 1.0 times mole, the reaction efficiency is poor and the reaction time becomes longer, so thermal decomposition is promoted. If it is more than 5.0 times mole, separation becomes poor during recovery, or purification becomes difficult.

The component (B) is preferably made finer in particle size and uniformly dispersed. If the average particle size is too large, it may cause defects such as the gap when the upper and lower glass substrates are bonded smoothly when manufacturing a narrow gap liquid crystal display unit, so it is preferably 5 μm or less, more preferably 3 μm or less. In addition, it may be fine even if it is miniaturized endlessly, but the lower limit is usually about 0.1 μm. The particle size system can be laser diffraction/scattering particle size distribution analyzer (dry type) (shares have Limited company Seishin enterprise system; LMS-30) determination.

The content of the component (B) is preferably 0.0001 to 10% by mass, more preferably 0.0005 to 5% by mass, and particularly preferably 0.001 to 3% by mass in the total amount of the liquid crystal sealant.

The liquid crystal sealant of the present invention may use (C) a photo-radical polymerization initiator, and is a liquid-crystal sealant of a photothermal combination type.

The photo-radical polymerization initiator is not particularly limited as long as it generates radicals by irradiation of ultraviolet rays or visible light and initiates a chain polymerization reaction, but examples include benzyl dimethyl acetal , 1-hydroxycyclohexyl phenyl ketone, diethyl thioxanthone, diphenyl ketone, 2-ethyl anthraquinone, 2-hydroxy-2-methyl propyl benzene, 2-methyl-[4- (Methylthio)phenyl)-2-morpholinyl-1-propane, 2,4,6-trimethylbenzyl diphenylphosphine oxide, camphorquinone, 9- stilbene, diphenyl diphenyl Thioether, etc. Specific examples include IRGACURE ^RTM 651, 184, 2959, 127, 907, 369, 379EG, 819, 784, 754, 500, OXE01, OXE02, DAROCURE ^RTM 1173, LUCIRIN ^RTM TPO (any one is manufactured by BASF Corporation) ), SEIKUOL ^RTM Z, BZ, BEE, BIP, BBI (any one is manufactured by Seiko Chemical Co., Ltd.), etc.

In addition, from the viewpoint of liquid crystal contamination, those having a (meth)acrylic group in the molecule are preferred, and for example, 2-methacryloxyethyl isocyanate and 1-[4-(2-hydroxyethyl Oxygen)-phenyl]-2-hydroxy-2methyl-1-propane-1-one reaction product. This compound can be produced by the method described in International Publication No. 2006/027982.

In addition, from the viewpoint of improving the curability of the light-shielding portion that is not sufficiently irradiated with light due to wiring or a black matrix, the absorption coefficient at 350 nm measured in acetonitrile is preferably 500 ml‧g ⁻¹ ‧cm or more. For example, IRGACURE ^RTM 651907, 369, 379EG, 819, 784, OXE01, OXE02, LUCIRIN ^RTM TPO (any one is manufactured by BASF), diethyl thioxanthone, benzophenone, etc.

The content of the component (C) photo-radical polymerization initiator used in the liquid crystal sealant of the present invention in the liquid crystal sealant is usually 0.1 to 20% by mass in the total amount of the liquid crystal sealant of the present invention. It is preferably 0.2 to 15% by mass.

The liquid crystal sealant of the present invention can use the filler (D) to improve the adhesive strength. The filler may be (D-1) organic filler, or (D-2) inorganic filler, or a mixture thereof, but it has different functions from each other, and a mixture of the two is preferred.

Of the total amount of liquid crystal sealing agent, the content of (D) filler is usually 5 to 70% by mass, preferably 10 to 60% by mass. Further, when the content of the filler (D) is 20% by mass or more, the effect of the invention of the present invention can be exerted particularly remarkably, and particularly preferably 20 to 50% by mass.

Examples of the component (D-1) organic filler system include urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and polysiloxane fine particles. In addition, the polysiloxane fine particle system is preferably KMP-594, KMP-597, KMP-598 (manufactured by Shin-Etsu Chemical Co., Ltd.), Torayfil ^RTM E-5500, 9701, and EP-2001 (manufactured by Dow Corning Toray). The formate microparticle system is preferably JB-800T, HB-800BK (Genshang Industrial Co., Ltd.), and the styrene microparticle system is Rabalon ^RTM T320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, SJ6300C (manufactured by Mitsubishi Chemical) ) Is preferred, and the styrene olefin microparticle system is preferably Septon ^RTM SEPS2004, SEPS2063.

These organic fillers may be used alone or in combination of two or more. Two or more types can be used for the core-shell structure. Among these, acrylic fine particles and polysiloxane fine particles are preferable.

When using the above-mentioned acrylic fine particles, acrylic rubber having a core-shell structure composed of two types of acrylic rubbers is preferred. Particularly preferred is a core layer of n-butyl acrylate and a shell layer of methyl methacrylate. This is Zefiac ^RTM F-351 sold by AICA Industries Co., Ltd.

In addition, the above-mentioned polysiloxane fine particle system may, for example, be an organic polysiloxane cross-linked powder or a linear dimethyl polysiloxane cross-linked powder. Examples of the composite polysiloxane rubber include a polysiloxane compound (for example, a polyorganosilicon silsesquioxane compound) coated on the surface of the polysiloxane rubber. Among these microparticles, the ultra-fine polysiloxane compound of linear dimethyl polysiloxane cross-linked powder polysiloxane rubber or polysiloxane compound coated with linear dimethyl polysiloxane cross-linked powder Rubber particles. These can be used alone or in combination of two or more. Moreover, it is preferable that the shape of the rubber powder is a spherical shape with little viscosity increase after addition. When the component (D) is used in the liquid crystal sealant of the present invention, the total amount of the liquid crystal sealant is usually 5 to 50% by mass, preferably 5 to 40% by mass.

The component (D-2) inorganic fillers include, for example, silicon dioxide, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, and oxide Magnesium, zirconia, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., preferably molten Dioxin Silicon dioxide, crystalline silicon dioxide, silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, aluminum silicate, preferably mica , Alumina, talc. These inorganic fillers can be used by mixing two or more kinds.

If the average particle size of the inorganic filler is too large, it may cause defects such as gap formation when the upper and lower glass substrates are bonded when manufacturing a narrow gap liquid crystal cell, so 2000 nm or less is suitable, preferably 1000 nm or less , Even better is below 300nm. The lower limit is preferably about 10 nm, and more preferably about 100 nm. The particle size was measured with a laser diffraction/scattering particle size distribution analyzer (dry type) (manufactured by Seishine Corporation; LMS-30).

When an inorganic filler is used in the liquid crystal sealant of the present invention, the total amount of the liquid crystal sealant may be about 10 to 50% by mass, but when it is 20% by mass or more, the effect of the present invention is more significant. The super good line is 20 to 50% by mass.

The liquid crystal sealing agent of this invention may contain (E) thermosetting agent.

The thermal hardener is different from the above-mentioned component (B) thermal radical polymerization initiator, and means a thermal hardener that does not generate radicals when heated. Specifically, it can be nucleophilically reacted by non-covalent electron pairs or anions in the molecule, and examples thereof include polyamines, polyphenols, and organic acid hydrazine compounds. But not subject to such restrictions. Among these, the organic acid hydrazine compound is particularly suitable for use. For example, aromatic hydrazide dihydrazide terephthalate, dihydrazide isophthalate, 2,6-naphthoic acid dihydrazide, 2,6-pyridine dihydrazide, 1,2,4-benzene Trihydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, pyromellitic acid tetrahydrazide Hydrazine, etc. Moreover, if it is an aliphatic hydrazide compound, for example, methyl hydrazine, acetohydrazine, propionate hydrazide, oxalate dihydrazine, malonate dihydrazide, succinic dihydrazide, glutaric dihydrazide, Adipic acid dihydrazide, pimelic acid dihydrazide, sebacic acid dihydrazide, 1,4-cyclohexane dihydrazide, tartrate dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide Hydrazine, N,N'-hexamethylene bishalcarbazide, trihydrazide citrate, trihydrazide nitroacetate, trihydrazide cyclohexanetricarboxylate, 1,3-bis(hydrazinocarbonylethyl) )-5-Isopropyl hydantoin and the like having a hydantoin skeleton, preferably having a valeric acid hydantoin skeleton (a skeleton in which the carbon atom of the hydantoin ring is replaced by an isopropyl group) Acylhydrazine compound, ginseng (1-hydrazinocarbonylmethyl) trimer isocyanate, ginseng (2-hydrazinocarbonylethyl) trimer isocyanate, ginseng (1-hydrazinocarbonylethyl) trimer isocyanate, ginseng (3- Hydrazinocarbonylpropyl) trimer isocyanate, bis(2-hydrazinocarbonylethyl) trimer isocyanate, etc. From the balance of hardening reactivity and potential, preferred are dihydrazide isophthalate, dihydrazide malonate, dihydrazide adipate, ginseng (1-hydrazinocarbonylmethyl) trimerization Cyanic acid, ginseng (1-hydrazinocarbonylethyl) trimer isocyanate, ginseng (2-hydrazinocarbonylethyl) trimer isocyanate, ginseng (3-hydrazinocarbonylpropyl) trimer isocyanate, especially the best ginseng ( 2-hydrazinocarbonylethyl) trimeric isocyanate.

The component (E) system may be used alone, or two or more types may be mixed. When the component (E) is used in the liquid crystal sealant of the present invention, it is usually 0.1 to 10% by mass, preferably 1 to 5% by mass in the total liquid crystal sealant.

In the liquid crystal sealant of the present invention, a silane coupling agent can be added as the component (F) to improve the adhesive strength or moisture resistance.

The component (F) is exemplified by 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxy Propylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-(2- (Aminoethyl) 3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethyl Oxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N-(2-(vinylbenzylamino)ethyl)3-aminopropyltrimethoxysilane Hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, etc. These silane coupling agents are KBM series, KBE series, etc. sold by Shin-Etsu Chemical Co., Ltd., etc., so they can be easily obtained from the market. When the component (F) is used in the liquid crystal sealant of the present invention, it is preferably 0.05 to 3% by mass in the total liquid crystal sealant.

The liquid crystal sealant of the present invention is further provided with additives such as organic acid or imidazole hardening accelerators, radical polymerization inhibitors, pigments, leveling agents, defoaming agents, solvents, etc. as needed.

Examples of the hardening accelerator system include organic acids and imidazole.

Examples of the organic acid system include organic carboxylic acid and organic phosphoric acid, but organic carboxylic acid is preferred. Specific examples include aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid phthalic acid, trimellitic acid, benzophenone tetracarboxylic acid, and furandicarboxylic acid, succinic acid, and hexyl acid. Diacid, dodecanedioic acid, sebacic acid, thiodipropionic acid, cyclohexanedicarboxylic acid, ginseng (2-carboxymethyl) trimer isocyanate, ginseng (2-carboxyethyl) trimer isocyanate, See (2-carboxypropyl) trimer isocyanate, bis(2-carboxyethyl) trimer isocyanate, etc.

、2,4-二胺基-6(2’-十一碳基咪唑(1’))乙基-s-三

、2,4-二胺基-6(2’-乙基-4-甲基咪唑(1’))乙基-s-三

、2,4-二胺基-6(2’-甲基咪唑(1’))乙基-s-三

/三聚異氰酸加成物、2-甲基咪唑三聚異氰酸之2：3加成物、2-苯基咪唑三聚異氰酸加成物、2-苯基-3,5-二羥基甲基咪唑、2-苯基-4-羥基甲基-5-甲基咪唑、1-氰乙基-2-苯基-3,5-二氰乙氧基甲基咪唑等。 Further, the imidazole compound system includes, for example, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzene Methyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl -2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1')) ethyl-s-tri

, 2,4-Diamino-6 (2'-undecylimidazole (1')) ethyl-s-tri

, 2,4-Diamino-6 (2'-ethyl-4-methylimidazole (1')) ethyl-s-tri

, 2,4-Diamino-6 (2'-methylimidazole (1')) ethyl-s-tri

/Trimer isocyanate adduct, 2-methylimidazole trimer isocyanate 2:3 adduct, 2-phenylimidazole trimer isocyanate adduct, 2-phenyl-3,5 -Dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, etc.

When the hardening accelerator is used in the liquid crystal sealant of the present invention, it is usually 0.1 to 10% by mass, preferably 1 to 5% by mass, in the total amount of the liquid crystal sealant.

-2,4,6-(1H,3H,5H)三酮、對甲氧基酚、4-甲氧基-1-萘酚、硫代二苯基胺、N-亞硝基苯基羥基胺之鋁鹽、商品名Adekastab LA-81、商品名Adek stab LA-82(ADEKA股份有限公司製)等，但不限定於該等。該等之中，以萘醌系、氫醌系、亞硝基系哌啶系之自由基聚合抑制劑為較佳，以萘醌、2-羥基萘醌、氫醌、2，6-二-第三丁基-P-甲酚、Polystop 7300P(伯東股份有限公司製)為更佳，以Polystop 7300P(伯東股份有限公司製)為最佳。 The radical polymerization inhibitor is not particularly limited as long as it is a compound that reacts with a radical generated from a photo radical polymerization initiator or a thermal radical polymerization initiator to inhibit polymerization, and quinone-based, Piperidine series, hindered phenol series, nitroso series, etc. Specific examples include naphthoquinone, 2-hydroxynaphthoquinone, 2-methylnaphthoquinone, 2-methoxynaphthoquinone, 2,2,6,6-tetramethylpiperidine-1-oxide (2 ,2,6,6-tetramethylpiperidine-1-oxyl), 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxide, 2,2,6,6-tetramethyl-4 -Methoxypiperidine-1-oxide, 2,2,6,6-tetramethyl-4-phenoxypiperidine-1-oxide, hydroquinone, 2-methylhydroquinone, 2-methyl Oxyhydroquinone, p-benzoquinone, butylated hydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butylcresol, stearyl β-( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-sulfur Bis-3-methyl-6-tert-butylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 3,9-bis[1,1- Dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl], 2,4,8,10-tetraoxaspiro[ 5,5] Undecane, [-methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenylpropionate)methane, 1,3,5-ginseng (3',5'-di-tert-butyl-4'-hydroxybenzyl)-second-tri

-2,4,6-(1H,3H,5H)trione, p-methoxyphenol, 4-methoxy-1-naphthol, thiodiphenylamine, N-nitrosophenylhydroxylamine Aluminum salt, trade name Adekastab LA-81, trade name Adek stab LA-82 (made by ADEKA Corporation), etc., but not limited to these. Among these, free radical polymerization inhibitors of naphthoquinone system, hydroquinone system, and nitroso piperidine system are preferred, and naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2,6-di- The third butyl-P-cresol and Polystop 7300P (made by Bodong Co., Ltd.) are more preferable, and Polystop 7300P (made by Bodong Co., Ltd.) is the best.

The content of the radical polymerization inhibitor is the total amount of the liquid crystal sealant of the present invention, preferably 0.0001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and particularly preferably 0.01 to 0.2% by mass.

As an example of the method for producing the liquid crystal sealant of the present invention, there are the following methods. First, the component (A) and the component (C) as needed are heated and dissolved. Then, after cooling to room temperature, component (F) is added as needed, and component (B), component (D), component (E), antifoaming agent, leveling agent, solvent, etc. are further added as needed. The mixing device such as a three-roll mill, sand mill, ball mill, etc. is uniformly mixed and filtered through a metal mesh, whereby the liquid crystal sealant of the present invention can be manufactured.

In the liquid crystal display unit of the present invention, a pair of substrates on which a predetermined electrode has been formed are opposed to each other at a predetermined interval, the periphery is sealed with the liquid crystal sealant of the present invention, and liquid crystal is enclosed in the gap. The type of liquid crystal enclosed is not particularly limited. Here, the substrate is composed of a substrate composed of glass, quartz, plastic, silicon, etc., and having at least one surface having a combination of light permeability. The manufacturing method is that after adding a spacer (gap control material) such as glass fiber to the liquid crystal sealant of the present invention, after applying the liquid crystal sealant to one surface of the pair of substrates using a dispenser, a screen printing device, or the like, Temporarily harden at 80 to 120°C as needed. Thereafter, liquid crystal was dropped inside the bank of the liquid crystal sealant, another glass substrate was overlapped in a vacuum, and gap formation was performed. After the gap is formed, curing is performed at 90 to 130°C for 1 to 2 hours, thereby producing the liquid crystal display unit of the present invention. In addition, when used as a combination of light and heat, the liquid crystal sealant is irradiated with ultraviolet rays by an ultraviolet irradiator to make it photocured. Based ultraviolet irradiation amount is preferably 500 to 10000mJ / cm ^2, more preferably to 1000 based 6000mJ / cm ² of irradiation amount is preferred. Thereafter, if necessary, curing is carried out at 90 to 130° C. for 1 to 2 hours, thereby producing the liquid crystal display unit of the present invention. The liquid crystal display unit of the present invention obtained in this way is free of display defects due to liquid crystal contamination, and is excellent in adhesion and moisture resistance reliability. Examples of the spacer system include glass fibers, silica particles, and polymer particles. The diameter varies depending on the purpose, but it is usually 2 to 8 μm, preferably 4 to 7 μm. The use amount thereof is usually 0.1 to 4% by mass, preferably 0.5 to 2% by mass, and more preferably about 0.9 to 1.5% by mass relative to 100% by mass of the liquid crystal sealant of the present invention.

The liquid crystal sealant of the present invention has a reduction in wiring corrosion Of effect. This result can eliminate driving defects after the humidity resistance test. Moreover, it is excellent in low liquid crystal contamination, and its cured material is also excellent in various cured product characteristics such as adhesive strength and heat resistance. From the above, by using the liquid crystal sealant of the present invention, a liquid crystal display unit excellent in reliability can be realized. In addition, the liquid crystal display unit manufactured using the liquid crystal sealant of the present invention sufficiently satisfies the characteristics necessary for a liquid crystal display unit, such as a high voltage retention rate and a low ion density.

[Example]

Hereinafter, the present invention will be described in more detail by examples, but the present invention is not limited to the examples. In addition, as long as there is no special record, "parts" and "%" in this article are quality standards.

[Synthesis Example 1] [Synthesis of full acrylate of resorcinol diglycidyl ether] [step 1]

In a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer, 5500 g of resorcinol, 37000 g of epichlorohydrin, and 500 g of tetramethylammonium chloride were added and dissolved under stirring, and the temperature was raised to 70°C. Then, 4000 g of flake-shaped sodium hydroxide was added in batches over 100 parts in 100 minutes, and post-reaction was carried out at 70°C for 1 hour. After the reaction was completed, 15000 g of water was added and washed with water, and excess epichlorohydrin and the like were distilled off from the oil layer under reduced pressure at 130°C. 22200 g of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70°C. Under stirring, 1000 g of a 30% sodium hydroxide aqueous solution was added, and after the reaction was carried out for 1 hour, it was washed three times with 5550 g of water, and methyl isobutyl was distilled off under reduced pressure at 180°C. Base ketone to prepare 10550g of resorcinol diglycidyl ether. The epoxy equivalent of the obtained epoxy compound was 129 g/eq.

[Step 2]

181.2 g of resorcinol diglycidyl ether obtained in Synthesis Example 1 above was dissolved in 266.8 g of toluene, and 0.8 g of dibutylhydroxytoluene was added as a polymerization inhibitor, and the temperature was raised to 60°C. After that, 117.5 g of acrylic acid having an epoxy equivalent of 100% was added, and the temperature was raised to 80°C, 0.6 g of trimethylammonium chloride as a reaction catalyst was added thereto, and the mixture was stirred at 98°C for about 30 hours. The obtained reaction liquid was washed with water, and toluene was distilled off, thereby obtaining 253 g of acrylate of the target resorcinol diglycidyl ether.

[Synthesis Example 2] [Synthesis of full acrylate of bisphenol A epoxy compound]

282.5g of bisphenol A epoxy compound (product name: YD-8125, manufactured by Nippon Steel Chemical Co., Ltd.) was dissolved in 266.8g of toluene, and 0.8g of dibutylhydroxytoluene was added as a polymerization inhibitor, and the temperature was raised to 60℃. After that, 117.5 g of acrylic acid with an epoxy equivalent of 100% was added, and the temperature was raised to 80° C., 0.6 g of trimethylammonium chloride as a reaction catalyst was added thereto, and the mixture was stirred at 98° C. for about 30 hours to prepare a reaction. liquid. This reaction liquid was washed with water, and toluene was distilled off, thereby obtaining 395 g of an acrylate of the intended bisphenol A epoxy compound.

[Synthesis Example 3] [Synthesis of 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane]

To market commercially available tetraphenyl-1,2-ethylene glycol (Tokyo Chemical Industry Co., Ltd. 100% (0.28 mol) dissolved in 350 parts of dimethyl formaldehyde. 32 parts (0.4 moles) of pyridine as an alkali catalyst and 150 parts (0.58 moles) of BASFA (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as a silylating agent were added thereto, and the temperature was raised to 70°C and stirred for 2 hours . The resulting reaction solution was cooled, and while stirring, 200 parts of water was added to precipitate the product and deactivate the unreacted silylating agent. After the precipitated product was filtered and separated, it was thoroughly washed with water. Then, the resulting product was dissolved in acetone, and water was added to recrystallize it for purification. 105.6 parts of 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane (yield 88.3%) was obtained.

As a result of analysis by HPLC (high-speed liquid chromatography), the purity was 99.0% (area percentage).

[Modulation of Examples 1 to 5, Comparative Examples 1 to 4]

The photo-radical polymerization initiator (component (C)) was added to the hardening compound (component (A)) such as the compound synthesized in Synthesis Example 1 and the compound synthesized in Synthesis Example 2 at the ratio shown in Table 1 below, to Heat and dissolve at 90℃. Cool to room temperature, add thermal radical polymerization initiator (component (B)), silane coupling agent (component (F)), thermal hardener (component (E)), organic filler (component (D-1)) ), inorganic filler (component (D-2)), etc., after stirring, dispersed with a three-roll mill and filtered through a metal mesh (635 mesh) to prepare a sealant for liquid crystal dropping method (Examples 1 to 5, Comparative Example) 1 to 4).

[Determination of water absorption]

The liquid crystal sealant manufactured in the examples and the comparative examples is sandwiched between parylene Ethylene formate (PET) film was put into a 130°C oven for 1 hour as a film with a thickness of 100 μm and cured. After curing, the PET film was peeled off to obtain a sealant cured film, which was cut into 20 mm × 50 mm The short sign is used as a sample piece. The obtained sample piece was stabilized under the conditions of 25°C and 50% RH for 24 hours according to JIS-K7209 D method, and the initial weight was measured, and after absorbing water for 24 hours under the conditions of 60°C and 90% RH , Determine the weight as the weight after water absorption. After the measurement, the water absorption rate was calculated according to the following formula.

Water absorption (%) = ((weight after water absorption (g)-initial weight (g)) / initial weight (g)) × 100 (%)

[Determination of moisture permeability]

A sealant hardened film was produced by the same method as the water absorption rate, and cut into a square shape of 90 mm×90 mm, which was used as a sample piece. This sample piece was subjected to the measurement of the moisture permeability in accordance with the JIS-K7129 A method of Lyssy L80-5000 manufactured by Systech Illinois under the temperature condition of 60°C.

[Evaluation of electrode corrosion in high temperature and high humidity test]

Using the liquid crystal sealants manufactured in Examples and Comparative Examples, a liquid crystal cell for evaluation with a cell gap of 5 μm was produced, and the occurrence of electrode corrosion in the high temperature and high humidity test was confirmed. The test method is shown below.

To each 2 g of the liquid crystal sealant, 0.02 g of glass fibers with a diameter of 5 μm was added as a spacer, mixed and deaerated, and filled in a 5 ml syringe. On a glass substrate with ITO transparent electrodes, use a dispenser (SHOTMASTER 300: manufactured by Taken Engineering Co., Ltd.) to fill in The liquid crystal sealant of the syringe is coated into a rectangular sealing pattern of 30 mm×40 mm, and then, tiny drops of liquid crystal (MLC-3007: manufactured by Merk Co., Ltd.) are dropped into the sealing pattern frame. On another ITO glass substrate, in-plane spacers (Natocospacer KSEB-525F: manufactured by Natoco Co., Ltd.: the gap width after bonding is 5 μm), and heat-fixed, using a bonding device in vacuum After the substrates dropped into the liquid crystal are bonded, the atmosphere is connected to form a gap. Since it is assumed that it is difficult to irradiate the sealant to the wiring shading portion of ultraviolet rays, a metal halide lamp (made by Ushio Electric Co., Ltd.) is irradiated with a low irradiation amount of 500mJ/cm2 (100mW/cm2 under 5 seconds) to semi-harden the seal pattern Then, it was further put into a 130° C. oven for 1 hour to thermally harden the seal pattern to prepare a liquid crystal cell for evaluation. A function generator (FG-281: manufactured by TEXIO‧Technology Co., Ltd.) was applied with a sine wave voltage of 10V and 100Hz under a high-temperature and high-humidity condition of 60°C and 90%RH, and the resulting liquid crystal cell for evaluation was put into use for 240 hours. The sealing part for evaluation was observed with a microscope, and the electrode corrosion was evaluated according to the following criteria.

○: No corrosion of the ITO electrode was observed at the periphery of the seal.

△: The corrosion of the ITO electrode was slightly observed at the periphery of the seal.

×: Corrosion of the ITO electrode was observed at the periphery of the seal.

[Evaluation of liquid crystal pollution]

For each liquid crystal sealant manufactured in Examples and Comparative Examples, apply about 100 mg of the sealant to the bottom of a 10 ml vial, and then add liquid crystal (MLC- 3007: Merk Co., Ltd.). The resulting vial was heated and kept at 130°C for 1 hour, and then cooled to room temperature for 30 minutes. The supernatant of each liquid crystal was separated by decantation, and the resistance value was measured with a digital ultra-high resistance meter (R8340: manufactured by Advantest Co., Ltd.), which was the specific resistance relative to the value of the liquid crystal without sealant. The value is determined based on the following criteria.

○: 5.0×10 ¹² or more

△: 5.0×10 ¹¹ or more, less than 5.0×10 ¹²

×: Less than 5.0×10 ¹¹

[Evaluation of Curability of Shade]

As shown in Figure 1, a liquid crystal sealant with 3μm glass fiber 1w% added is applied to the center of the etched chrome plated glass substrate, and the black matrix substrate is used as the counter substrate and bonded together, and fixed with a jig (UV Before irradiation). After irradiating 3000 mJ/cm ² of ultraviolet rays from the chromium-etched glass substrate side, the two bonded substrates are peeled off, and the portion under chromium that is shielded from light is confirmed with a microscope, and the hardened width of the light shielding portion is measured.

○: 30μm or more

△: 10μm or more, less than 30μm

×: less than 10μm

A-1: Fully acrylate of resorcinol diglycidyl ether (Synthesis Example 1)

A-2: Fully acrylate of bisphenol A epoxy resin (Synthesis Example 2)

A-3: Modification of caprolactone (6 mol) dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.: DPCA-60)

A-4: Bisphenol A epoxy resin (manufactured by Nippon Kayaku Co., Ltd.: RE-310S)

A-5: Bisphenol A epoxy resin high molecular weight body (Nippon Steel & Sumitomo Chemical Co., Ltd.: YD-012)

A-6: Ethylene oxide modified bisphenol S type epoxy resin (synthesized by the method described in Japanese Patent No. 4211942)

B-1: 1,2-bis(trimethylsilyloxy)-1,1,2,2-tetraphenylethane (Synthesis Example 3 was crushed to an average of 1.9 μm using a jet mill)

B-2: Polycondensate of 4,4’-azobis (4-cyanovaleric acid) and polyethylene glycol (molecular weight: 2000) (Wako Pure Chemical Industries, Ltd.: VPE-0201)

C-1: 2-Methacryloyloxyethyl isocyanate and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one Reaction product (synthesized by the method described in International Publication 2006/027982)

C-2: 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyl oxime)] (manufactured by BASF: IRGACURE OXE-01

C-3: 2,4-Diethylthioxanthone (made by Nippon Kayaku Co., Ltd.: DETX-S)

D-1-1: Polymethacrylate-based organic fine particles (AICA Industries Co., Ltd.: F-351S)

D-2-1: Spherical silica (made by Shin-Etsu Chemical Co., Ltd.: X-24-9163A)

D-2-2: Spherical silica (produced by Tokuyama Co., Ltd.: Sunseal SSP-07DM)

E-1: Ginseng (2-hydrazinocarbonylethyl) triisocyanate finely pulverized product (made by Japan Finechem Co., Ltd.: HCIC, finely pulverized to 1.5 μm with a jet mill)

F-1: 3-glycidoxypropyltrimethoxysilane (manufactured by JNC Corporation: Sila-Ace S-510)

F-2: N-2 (aminoethyl) 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.: KBM-603)

O-1: Piperidine derivative of nitroso series (made by Bodong Co., Ltd.: Polystop 7300P)

O-2: ginseng (3-carboxyethyl) triisocyanate (manufactured by Shikoku Chemical Industry Co., Ltd.: CIC acid, finely pulverized with a jet mill to an average particle size of 1.5 μm)

From the results in Table 1, it is understood that Examples 1 to 5 in which the water absorption rate and moisture permeability of the cured product hardened only by heat are below a certain level have no wiring corrosion, and show excellent results with low liquid crystal contamination. On the other hand, the liquid crystal sealant described in the comparative example has corrosion of wiring, and has a problem in the long-term reliability of the liquid crystal display unit. From this fact, it can be said that the invention of the present invention is a liquid crystal sealant with excellent reliability after a moisture resistance test, and the reliability of a liquid crystal display unit manufactured using this liquid crystal sealant is also excellent.

[Possibility of industrial use]

The liquid crystal sealant of the present invention has very little effect on the liquid crystal display characteristics, so that it is possible to achieve high definition, high speed response, low voltage drive, and long life of the liquid crystal display element. In addition, since the adhesive strength and humidity resistance are excellent, it is possible to manufacture a highly reliable liquid crystal display element.

Claims (12)

A liquid crystal sealing agent for a liquid crystal dropping method, comprising (A) a hardening compound, (D) a filler and (E) a thermosetting agent, wherein the content of the filler in the total liquid crystal sealing agent is 20% by mass Above, the cured product obtained by heat curing at 130°C for 1 hour without irradiation of ultraviolet rays has a water absorption rate of 2.0% or less according to JIS-K7209 and a moisture permeability of 130 g/m ² according to JIS-K7129 ＊Under 24h. The liquid crystal sealing agent for liquid crystal dropping method as described in item 1 of the patent application scope further contains (B) a thermal radical polymerization initiator. The liquid crystal sealing agent for liquid crystal dropping method as described in item 1 or 2 of the patent application scope, wherein the aforementioned component (B) thermal radical polymerization initiator does not contain oxygen-oxygen bond (-OO-) and A nitrogen-nitrogen bond (-N=N-) thermal radical polymerization initiator. The liquid crystal sealing agent for liquid crystal dropping method as described in item 1 or 2 of the scope of patent application further contains (C) photo radical polymerization initiator. The liquid crystal sealing agent for liquid crystal dropping methods as described in item 1 or 2 of the patent application range, wherein the aforementioned component (D) is a mixture of (D-1) organic filler and (D-2) inorganic filler. The liquid crystal sealing agent for liquid crystal dropping methods as described in item 5 of the patent application range, wherein the content of the inorganic filler in the component (D-2) in the total liquid crystal sealing agent is 20% by mass or more. Liquid crystal for liquid crystal dropping method as described in item 1 or 2 of patent scope The sealant, wherein the curable compound of the aforementioned component (A) is an epoxy (meth)acrylate compound. The liquid crystal sealing agent for liquid crystal dropping methods as described in item 1 or 2 of the patent application range, wherein the curable compound of the component (A) is a mixture of an epoxy (meth)acrylate compound and an epoxy compound. The liquid crystal sealing agent for liquid crystal dropping method as described in item 1 or 2 of the patent application range, wherein the thermosetting agent of the component (E) is an organic acid hydrazine. The liquid crystal sealing agent for liquid crystal dropping method as described in item 1 or 2 of the patent application scope further contains (F) silane coupling agent. A method for manufacturing a liquid crystal display unit, comprising the steps of: in a liquid crystal display unit composed of two substrates, the liquid crystal according to any one of items 1 to 10 of the patent application range formed on a substrate After dropping liquid crystal into the inside of the embankment of liquid crystal sealant, the other substrate is bonded, and then it is hardened by light and/or heat. A liquid crystal display unit is one in which a cured product obtained by curing a liquid crystal sealing agent for liquid crystal dropping method as described in any one of claims 1 to 10 is sealed.

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