TW201434874A - Method for manufacturing liquid-crystal display cells and liquid-crystal display cells obtained via said method - Google Patents

Abstract

Provided is a method for manufacturing liquid-crystal display cells wherein liquid crystal does not penetrate a liquid-crystal sealant during the manufacturing process. The use of this manufacturing method allows an extremely high degree of stability in the manufacture of liquid-crystal display cells and also allows takt-time reductions, allowing even higher-volume production. In this method for manufacturing liquid-crystal display cells comprising two substrates, after liquid-crystal droplets are placed inside liquid-crystal-sealant enclosures formed on one substrate, the other substrate is bonded thereto, and ultraviolet light and/or heat is then used to cure the liquid-crystal sealant. The liquid-crystal sealant contains an organic filler (a), and the mean particle diameter (A, in μm) of said organic filler (a) and the cell gap (B, in μm) between the liquid-crystal display cells satisfy relation (1). (1) 1.0 μm ≤A-B ≤9.0 μm.

Description

Method for manufacturing liquid crystal display unit and liquid crystal display unit obtained by the method

The present invention relates to a method of fabricating a liquid crystal display unit and a liquid crystal display unit manufactured by the method. More specifically, it is a manufacturing method capable of stably manufacturing a liquid crystal display unit without permeating liquid crystal sealing agent in a manufacturing step, and a liquid crystal display unit manufactured by the method.

In recent years, as a method of manufacturing a liquid crystal display unit, a liquid crystal dropping method (liquid crystal dropping method) having a higher mass productivity has been proposed as a method of manufacturing a liquid crystal display unit (Patent Document 1 and Patent Literature) 2). Specifically, the liquid crystal dropping method is a manufacturing method in which a liquid crystal is immersed in the inside of a bank formed by a liquid crystal sealing agent on one of the substrates, and the other substrate is bonded to each other, and then the liquid crystal sealing agent is cured.

However, in the liquid crystal dropping method, since the liquid crystal is in contact with the liquid crystal sealing agent before the liquid crystal sealing agent is hardened, the phenomenon of penetration of the liquid crystal sealing agent due to the pressure of the liquid crystal may occur, and in the worst case, the liquid crystal sealing agent The collapse of the embankment caused the liquid crystal to leak out and was considered a problem. This problem occurs in the liquid crystal dropping method in which light and heat are used in combination, and may occur in a portion which is not sufficiently irradiated with ultraviolet rays due to the shadow of wiring or the like. Also, not purple External line irradiation, in which the liquid crystal sealing agent is hardened only by heat, is a particularly large problem. In order to solve this problem, it is necessary to increase the precision of the liquid crystal dropping amount. However, even in this case, the liquid crystal expands during the hardening step of the liquid crystal sealing agent, that is, heating, and it is difficult to completely suppress the above-described infiltration phenomenon.

In order to solve this problem, various technologies have been proposed regarding liquid crystal sealing agents.

In Patent Document 3, organic bentonite is used to attempt to solve the above problems. This method has a certain effect on the penetration of liquid crystal, but it is difficult to say that it is sufficient.

Patent Document 4 describes a method of performing a B-stage treatment of a liquid crystal sealing agent by using a liquid crystal sealing agent using fumed silica (fumed silica) or polythiol. However, this method has the disadvantage that the steps become longer and the device requiring this step is disadvantageous.

Patent Document 5 discloses a liquid crystal sealing agent for a liquid crystal dropping method which uses a thermal radical polymerization initiator to prevent penetration by increasing the curing rate.

Thus, the above problems have been attempted to be solved only by the improvement of the liquid crystal sealing agent, but it is actually difficult to achieve. Therefore, it is necessary to improve both the design of the liquid crystal display unit and the design of the liquid crystal encapsulant thereof. However, a method for solving the above problems has not been proposed, and a method of manufacturing a liquid crystal display unit capable of sufficiently suppressing penetration of liquid crystal into a liquid crystal sealing agent has not been established.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Laid-Open Patent Publication No. SHO63-179323

Patent Document 2: Japanese Laid-Open Patent Publication No. Hei 10-239694

Patent Document 3: Japanese Patent Laid-Open Publication No. 2010-14771

Patent Document 4: Japanese Laid-Open Patent Publication No. 2011-150181

Patent Document 5: International Publication No. 2011/061910

The present invention relates to a liquid crystal display unit and a method of fabricating the same. More specifically, a method of manufacturing a liquid crystal display unit which can stably produce liquid crystal sealing agent without infiltrating a liquid crystal sealing agent in a manufacturing step, and a liquid crystal display unit manufactured by the method are proposed.

As a result of intensive studies, the present inventors have found that when the cell gap of the liquid crystal display unit composed of two substrates is in a certain relationship with the average particle diameter of the organic filler contained in the liquid crystal sealing agent, liquid crystal can be prevented from penetrating into the liquid crystal sealing. The present invention has been accomplished by a method of manufacturing a liquid crystal display unit in an agent.

In the present specification, "(meth)acrylate" means "acrylate and/or methacrylate", and "(meth)acryloyl group means "acryloyl group and/or methacryloyl group" base".

Further, in the present specification, the average particle diameter may be described as an average particle diameter, but both of them are synonymous.

That is, the present invention relates to the following 1) to 6).

1)

In a liquid crystal display unit comprising two substrates, a liquid crystal is dropped on a bank of a bank formed of a liquid crystal sealing agent formed on one of the substrates, and the other substrate is bonded to the substrate. a manufacturing method for hardening the liquid crystal sealing agent by ultraviolet rays and/or heat, wherein

The liquid crystal sealing agent contains (a) an organic filler, and when the average particle diameter of the (a) organic filler is A (μm) and the cell gap of the liquid crystal display unit is B (μm), The following formula (1):

1.0 μm ≦A-B ≦ 9.0 μm‧‧‧(1).

2)

The method for producing a liquid crystal display unit according to the above 1), wherein the curing step of the liquid crystal sealing agent is performed only by heat.

3)

The liquid crystal display unit according to the above aspect, wherein the liquid crystal sealing agent further contains (b) a thermal radical polymerization initiator and (c) a curable compound having a (meth) acrylonitrile group.

4)

The method for producing a liquid crystal display unit according to the above 1), wherein the (a) organic filler is rubber fine particles.

5)

The method for producing a liquid crystal display unit according to the above 4, wherein the rubber fine particles are made of acrylate rubber, styrene rubber, styrene olefin rubber or polyoxymethylene rubber.

6)

A liquid crystal display unit manufactured by the manufacturing method according to any one of the above 1) to 5).

According to the method of manufacturing a liquid crystal display unit of the present invention, since the liquid crystal does not penetrate into the liquid crystal sealing agent in the manufacturing step, the liquid crystal can be manufactured extremely stably. Display unit. Moreover, the production cycle can be shortened, so that further mass production can be improved.

The manufacturing method of the liquid crystal display unit of the present invention is related to In the liquid crystal display unit including the substrate, the liquid crystal is dropped on the inside of the bank formed of the liquid crystal sealing agent formed on one of the substrates, and the other substrate is bonded to the substrate, and then the liquid crystal is irradiated by ultraviolet rays and/or heat. A method of manufacturing a sealant hardening. That is, the liquid crystal dropping method is involved.

As described in the prior art item, in the liquid crystal dropping method, since the liquid crystal is in contact with the liquid crystal sealing agent before the liquid crystal sealing agent is hardened, the phenomenon that the liquid crystal penetrates into the liquid crystal sealing agent due to the pressure of the liquid crystal may occur, or The bank formed by the liquid crystal sealing agent collapses, and the liquid crystal leaks out.

The liquid crystal dropping method is organically contained in the liquid crystal sealing agent When the average particle diameter A (μm) of the filler is maintained in a certain relationship with the cell gap B (μm) of the liquid crystal display unit, the penetration of the liquid crystal into the liquid crystal sealing agent can be greatly reduced. This should be an organic filler that is compressed by the pressure of the upper and lower substrates to function as a bank to resist the pressure of liquid crystal expansion.

This certain relationship is the relationship shown in the above formula (1). When the value of A-B is less than 1.0 μm, the compression of the organic filler is insufficient, and if it is more than 9.0 μm, the cell gap of the liquid crystal display unit cannot be compressed to the intended gap. The value of A-B is more preferably 2.0 μm or more and 8.0 μm or less, and particularly preferably 2.0 μm or more and 6.0 μm or less.

Here, the average particle diameter of the organic filler can be produced by a laser diffraction or scattering particle size distribution analyzer (dry type) (Seishin Co., Ltd.; LMS-30) and the like.

The liquid crystal sealing agent used in the method for producing a liquid crystal display unit of the present invention contains (a) an organic filler (hereinafter also referred to as component (a)). The (a) organic filler is not particularly limited as long as the average particle diameter satisfies the above conditions, and examples thereof include polyamide fine particles such as nylon 6, nylon 12 and nylon 66; and fluorine such as tetrafluoroethylene or vinylidene fluoride. Microparticles; olefin-based fine particles such as polyethylene and polypropylene; polyester microparticles such as polyethylene terephthalate or polyethylene naphthalate; natural rubber, isoprene rubber, acrylate rubber, etc. Rubber particles and the like.

The above (a) organic filler is preferably rubber fine particles. Examples of the rubber fine particles include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), butyl rubber (IIR), and acrylonitrile. Rubber (NBR), ethylene-propylene rubber (EPM, EP), chloroprene rubber (CR), acrylate rubber (ACM, ANM), chlorosulfonated polyethylene rubber (CSM), polyurethane rubber (PUR), poly The silicone rubber (Si, SR), the fluororubber (FKM, FPM), the polysulfide rubber (Thiokol), and the like may be individual rubber fine particles, or may be formed into a core-shell structure using two or more kinds. It is also possible to use two or more types together. Among these, acrylate rubber, styrene rubber, styrene olefin rubber, or polyoxyethylene rubber is preferable, and acrylate rubber or polyoxyethylene rubber is particularly preferable.

In the case of using an acrylate rubber, an acrylate rubber having a core-shell structure formed of two acrylate rubbers is preferable, and particularly preferably, the core layer is n-butyl acrylate and the shell layer is methyl methacrylate. This is the Zefiac ^RTM F-351 sold by Aica Industries.

Moreover, examples of the polyoxyxylene rubber include an organic polyoxyalkylene crosslinked product powder, a linear dimethyl polyoxyalkylene crosslinked powder, and the like. Further, as the composite polyoxyxene rubber, for example, the surface of the above polyoxyxene rubber is coated with a polyoxyxylene resin (for example, polyorganosilsesquioxane resin). Among these rubber fine particles, particularly preferably a linear dimethyl polyoxyalkylene crosslinked powder, a polyoxyxylene rubber or a polyoxynoxy resin coated with a linear dimethyl polyoxyalkylene crosslinked powder. Composite polyoxynized rubber microparticles. These may be used alone or in combination of two or more. Further, the shape of the rubber powder is preferably a spherical shape in which the viscosity after the addition is less increased.

Specific examples of the above-mentioned organic filler (a) include, as a polyoxyxene rubber, KMP594, KMP597, KMP598 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), EP2001 (manufactured by Toray Dow Corning Co., Ltd.), and as a polyurethane rubber, JB-800T, HB-800BK (above is manufactured by Gensei Industrial Co., Ltd.); as acrylate rubber, AFX-8 (manufactured by Sekisui Chemicals Co., Ltd.), F351S (manufactured by Aica Industrial Co., Ltd.), W- 341, Metablen series (above manufactured by Mitsubishi Rayon Co., Ltd.); as styrene rubber, Rabalon series (manufactured by Mitsubishi Chemical Corporation); as styrene olefin rubber, TR series (manufactured by JSR Co., Ltd.), Septon Series (manufactured by Kuraray Co., Ltd.), etc. But it is not limited to these.

In the liquid crystal sealing agent used in the present invention, the content of the organic filler (a) is 5 to 50 parts by mass, preferably 5 to 40 parts by mass, per 100 parts by mass of the total amount of the liquid crystal sealing agent.

Further, in order to realize the constitution of the present invention, the organic filler is subjected to a classification operation to obtain a material having a desired average particle diameter. Do this too Helps to remove coarse particles and prepares organic fillers with a sharper particle size distribution. Since the coarse particles cause poor cell gap of the liquid crystal, it is preferable to carry out the classification operation.

The grading operation can be carried out, for example, by using a jet mill JM-0202 (manufactured by Seishin Co., Ltd.), and then using a gas stream classifier Classiel N05 (manufactured by Seishin Co., Ltd.). Further, in order to perform this operation more efficiently, a dispersing agent or the like can be used.

The manufacturing method of the liquid crystal display unit of the invention has little leakage due to liquid crystal Into the liquid crystal sealing agent, it can also be applied to the liquid crystal dropping method which is carried out only by heat. The liquid crystal dropping method which is carried out only by heat is more preferable from the viewpoint of production tempo and the like.

Liquid crystal dense used in the method of manufacturing a liquid crystal display unit of the present invention The sealing agent is not limited to other constituent components as long as it contains the (a) organic filler satisfying the above conditions, and preferably contains (b) a thermal radical polymerization initiator, and (c) has a (meth) acrylonitrile group. The case of a hardening compound.

The (b) thermal radical polymerization initiator is not particularly limited as long as it is a radical generated by heating, and the compound which starts the chain polymerization reaction is not particularly limited, and examples thereof include an organic peroxide, an azo compound, a benzoin compound, and a benzoin ether. As the compound, an acetophenone compound, tetraphenylethylene glycol or the like, tetraphenylethylene glycol is preferably used. For example, as organic peroxides, there are 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-LS50E, 21-LS50E, 42, 42LS, Kayaester ^RTM P-70, TMPO-70, CND-C70, OO-50E, AN, Kayabutyl ^RTM B, Perkadox16, Kayacarbon ^RTM BIC-75 , AIC-75 (above is manufactured by Akzo Co., Ltd.), Permeck ^RTM N, H, S, F, D, G, Perhexa ^RTM H, HC, TMH, C, V, 22, MC, Percure ^RTM AH, Commercial products such as AL, HB, Perbutyl ^RTM H, C, ND, L, Percumyl ^RTM H, D, Peroyl ^RTM IB, IPP, and Perocta ^RTM ND (manufactured by Nippon Oil Co., Ltd.) are available. In addition, as an azo compound, commercially available products such as VA-044, V-070, VPE-0201, VSP-1001, etc. (the above is manufactured by Wako Pure Chemical Industries Co., Ltd.) are available. In addition, in this specification, the superscript RTM means a registered trademark.

As the above (b) thermal radical polymerization initiator, it is preferred that the thermal radical polymerization initiation does not have an oxygen-oxygen bond (-OO-) or a nitrogen-nitrogen bond (-N=N-) in the molecule. Agent. a thermal radical polymerization initiator having an oxygen-oxygen bond (-OO-) or a nitrogen-nitrogen bond (-N=N-) in the molecule, which generates a large amount of oxygen and nitrogen when generating a radical, so The liquid crystal sealing agent is hardened in the state of residual bubbles, and the characteristics such as adhesion strength are lowered. It is particularly suitable to use a tetraphenyl glycol-based thermal radical polymerization initiator (including chemically modified tetraphenylethylene glycol). Specific examples thereof include tetraphenylethylene 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- Tetrakis(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetrakis(4-methoxyphenyl)ethane, 1,2-bis(trimethyl) 1,0,1,2,2-tetraphenylethane, 1,2-bis(triethyldecyloxy)-1,1,2,2-tetraphenylethane, 1, 2-bis(t-butyldimethylmethyloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylphosphonium-1,1,2,2 -tetraphenylethane, 1-hydroxy-2-triethyldecyloxy -1,1,2,2-tetraphenylethane, 1-hydroxy-2-tert-butyldimethyloxyl-1,1,2,2-tetraphenylethane, etc., preferably 1-hydroxy-2-trimethylphosphonium-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethyldecyloxy-1,1,2,2-tetraphenyl Ethylethane, 1-hydroxy-2-tert-butyldimethyloxy-1,1,2,2-tetraphenylethane, 1,2-bis(trimethyldecyloxy)-1 1,2,2-tetraphenylethane, more preferably 1-hydroxy-2-trimethylphosphonium-1,1,2,2-tetraphenylethane, 1,2-double (three Methyl decyloxy)-1,1,2,2-tetraphenylethane, particularly preferably 1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenyl alkyl.

The above tetraphenylethylene glycol is commercially available as Tokyo Chemical Industry Co., Ltd., and Wako Pure Chemical Industries Co., Ltd., and the like. Further, the hydroxyl group of tetraphenylethylene glycol is etherified, and can be easily synthesized by a known method. Further, the hydroxy oxime of tetraphenylethylene glycol can be synthesized by a method in which a corresponding tetraphenylethylene glycol and various decylating agents are heated under a basic catalyst such as pyridine. As the decylating agent, for example, trimethylchlorodecane (TMCS), hexamethyldioxane (HMDS), and N,O-bis(trimethylsulfonyl) of a conventional trimethylsulfonating agent can be mentioned. Trifluoroacetamide (BSTFA) or triethylchlorodecane (TECS) as a triethylsulfonating agent, third butylmethyldecane (TBMS) as a third butyldimethylalkylating agent, and the like. Such reagents are readily available from markets such as oxime derivative manufacturers. The reaction amount of the alkylating agent is preferably 1.0 to 5.0 times moles per mole of the hydroxyl group of the target compound. More preferably 1.5 to 3.0 times Mo. If it is less than 1.0 times mole, the reaction efficiency is poor, and the reaction time is lengthened to promote thermal decomposition. If it is more than 5.0 times Moule, it is difficult to separate during recovery and it becomes difficult to refine.

The (b) thermal radical polymerization initiator preferably has a fine particle diameter and is uniformly dispersed. If the average particle diameter is too large, a liquid crystal display with a narrow gap is produced. In the case of a unit, the gap may not be formed smoothly when the upper and lower glass substrates are bonded together, and therefore it is preferably 5 μm or less, and more preferably 3 μm or less. Further, although it can be made thin without limitation, the lower limit is usually about 0.1 μm. The particle diameter can be measured by a laser diffraction, a scattering type particle size distribution analyzer (dry type) (manufactured by Seishin Co., Ltd.; LMS-30).

(b) the content of the thermal radical polymerization initiator, as will be achieved by the present invention When the total amount of the liquid crystal sealing agent used is 100 parts by mass, it is preferably 0.0001 to 10 parts by mass, more preferably 0.0005 to 5 parts by mass, particularly preferably 0.001 to 3 parts by mass.

The (c) curable compound having a (meth)acryl fluorenyl group may, for example, be (meth) acrylate or epoxy (meth) acrylate. Examples of the (meth) acrylate include benzyl methacrylate, cyclohexyl methacrylate, glyceryl dimethacrylate, glyceryl triacrylate, EO-modified glycerin triacrylate, pentaerythritol acrylate, and the like. Hydroxymethylpropane triacrylate, propylene (propylene oxyethyl) isomeric cyanurate, dipentaerythritol hexaacrylate, phloroglucin triacrylate, and the like. The epoxy group (meth) acrylate can be obtained by a known method by reacting an epoxy resin with (meth)acrylic acid. The epoxy resin as a raw material is not particularly limited, and is preferably a bifunctional or higher epoxy resin, and examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and phenol. Novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin , glycidyl ester type epoxy resin, epoxy propylamine type epoxy resin, ethyl urethane type epoxy resin, iso-cyanate type epoxy resin, and trisphenol methane skeleton a phenol novolac type epoxy resin, a di-glycidyl ether compound of a difunctional phenol such as catechol or resorcin, a diepoxypropyl ether compound of a difunctional alcohol, and the like Halides, hydrides, and the like. Among these, from the viewpoint of liquid crystal contamination, an epoxy resin having a resorcinol skeleton is preferable, and examples thereof include resorcinol diglycidyl ether. Further, the ratio of the epoxy group to the (meth) acrylonitrile group is not limited, and may be appropriately selected from the viewpoints of step suitability and liquid crystal contamination.

Therefore, a preferred curable compound having a (meth)acryl fluorenyl group is a curable resin having a (meth)acryl fluorenyl group and further having a resorcinol skeleton, such as resorcinol diepoxypropane Ethylene acrylate or resorcinol diglycidyl ether methacrylate.

In addition, (c) the content percentage of the curable compound having a (meth) acrylonitrile group in the liquid crystal sealing agent is preferably 30 to 90 parts by mass when the total amount of the liquid crystal sealing agent is 100 parts by mass. In the range, it is preferably 40 to 80 parts by mass.

Among the above (c) curable compounds having a (meth)acryl fluorenyl group, it is preferred to contain a compound having three (methyl groups) in one molecule. A compound having three (meth) acrylonitrile groups in one molecule has excellent crosslinking resistance (reaction rate), so that excellent penetration resistance can be achieved. Further, in the case of using this method, the method of increasing the amount of the thermal radical polymerization initiator or the like is used to improve the reactivity, and the workability is also excellent.

As a compound having three (meth) acrylonitrile groups in one molecule, for example, KAYARAD ^RTM PET-30, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DPEA-12, GPO- 303, TMPTA, THE-330, TPA-320, TPA-330, D-310, D-330, RP-1040, UX-5000, DPHA-40H (above manufactured by Nippon Kayaku Co., Ltd.), NK ester ^RTM A-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A- TMMT, A-9550, A-DPH (above, New Nakamura Chemical Industry Co., Ltd.), SR295, SR350, SR355, SR399, SR494, CD501, SR502, CD9021, SR9035, SR9041 (above, manufactured by Satomer Co., Ltd.). Among these, it is preferred that the molar average molecular weight is 800 or more, and for example, KAYARAD ^RTM DPCA-20, DPCA-30, DPEA-12 is preferable. Further, it is preferably a curable compound containing an oxidized C1-C4 alkylene group (-ORO-) in the molecule, and particularly preferably KAYARAD ^RTM DPEA-12.

Liquid crystal density used in the method of manufacturing a liquid crystal display unit of the present invention The sealing agent may contain a curable resin having an epoxy group, a thermosetting agent, a decane coupling agent, an inorganic filler, or a hardening, in addition to the component (a) and the components (b) and (c) which are contained as needed. Promoters, pigments, coating agents, defoamers, solvents, etc.

By using the above-mentioned curable resin having an epoxy group, it is possible to achieve stickiness The improvement in strength. The curable resin having an epoxy group is not particularly limited, and is preferably a bifunctional or higher epoxy resin, and examples thereof include a bisphenol A epoxy resin, a bisphenol F epoxy resin, and a bisphenol S ring. Oxygen resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain Epoxy resin, epoxy propyl ester epoxy resin, epoxy propylamine epoxy resin, intramethylene urea resin, isomeric cyanate epoxy resin, a phenol novolak type epoxy resin having a trisphenol methane skeleton; other, such as a di-glycidyl ether of a difunctional phenol; a diepoxy ether ether of a difunctional alcohol; and the halides and hydrides thereof Wait. Among these, from the viewpoint of liquid crystal contamination, a bisphenol type epoxy resin or a novolak type epoxy resin is preferable. When the total amount of the liquid crystal sealing agent is 100 parts by mass, the content of the epoxy resin having an epoxy group is about 1 to 30 parts by mass.

The above-mentioned thermosetting agent is not particularly limited, and examples thereof include polyvalent amines, polyvalent phenols, and hydrazine compounds, and solid organic acid strontium is particularly preferably used. For example, barium salicylate, barium benzoate, barium 1-naphthoate, diterpene terephthalate, diterpene isophthalate, diammonium 2,6-naphthoic acid may be mentioned. Anthracene, 2,6-pyridinedifluorene, 1,2,4-benzenetriazole, tetramethylphosphonium tetrabenzoate, tetraterpene tetrahydrofuranate, and the like. Further, examples of the aliphatic hydrazine compound include formazan, acetamidine, cesium propionate, bismuth oxalate, diammonium malonate, diterpene succinate, and bismuth glutarate. , diammonium adipate, dipimepyridinium diphosphate, diterpene sebacate, 1,4-cyclohexane dioxime, diterpene tartrate, diterpene malate, iminodiacetic acid醯肼, N, N'-hexamethylene bis-urea urea, triterpene citrate, trimethyl hydrazine acetate, triterpene Cyclohexane tricarboxylate, 1,3-bis(decylcarbonyl) a carbendazim skeleton of 5-aminoethyl carbazide or the like, preferably having a valine carbendazim skeleton (a skeleton in which a carbon atom of the uremone ring is substituted with an isopropyl group) Diterpenoid compound, ginseng (1-mercaptocarbonylmethyl)isocyanate, ginseng (2-mercaptocarbonylethyl)isocyanate, ginseng (3-mercaptocarbonylpropyl) Cyanurate, bis(2-mercaptocarbonylethyl)isocyanate, and the like. The heat hardener may be used alone or in combination of two or more. Hardened by In terms of the balance between reactivity and latent property, it is preferably diterpene isophthalate, diammonium malonate, diammonium adipate, diterpene sebacate, ginseng (1-mercaptocarbonyl) Isoisocyanate, ginseng (2-mercaptocarbonylethyl)isocyanate, ginseng (2-mercaptocarbonylethyl)isocyanate, ginseng (3-mercaptocarbonyl) Propyl) isocyanurate, particularly preferably diammonium malonate or diterpene sebacate. When the total amount of the liquid crystal sealing agent is 100 parts by mass, the content is about 1 to 30 parts by mass.

The above decane coupling agent can be used to improve the adhesion strength or the moisture resistance reliability. As the decane coupling agent, for example, 3-glycidoxypropyltrimethoxydecane or 3-glycidoxypropylmethyl group can be mentioned. Methoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, N-phenyl-γ-amine Propyltrimethoxydecane, N-(2-aminoethyl) 3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl) 3-aminopropylmethyl Trimethoxydecane, 3-aminopropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, vinyltrimethoxydecane, N-(2-(vinylbenzylamino)ethyl 3-aminopropyltrimethoxydecane hydrochloride, 3-methylpropenyloxypropyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxy Base decane and the like. These decane coupling agents are easily available from the market because of the KBM series and KBE series sold by Shin-Etsu Chemical Co., Ltd. When the total amount of the liquid crystal sealing agent used in the present invention is 100 parts by mass, the content of the decane coupling agent in the liquid crystal sealing agent is preferably 0.05 to 3 parts by mass.

The above inorganic filler can be used to improve the adhesion strength or the moisture resistance reliability. As the inorganic filler, for example, molten cerium oxide, Crystalline cerium oxide, cerium carbide, cerium nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesia, zirconia, aluminum hydroxide, magnesium hydroxide , calcium citrate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., preferably molten cerium oxide, crystalline cerium oxide, cerium nitride Boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium citrate, aluminum citrate, more preferably molten cerium oxide, crystalline cerium oxide, aluminum oxide ,talc. These inorganic fillers may be used in combination of two or more kinds. When the average particle diameter is too large, a liquid crystal cell having a narrow gap is formed, which may cause a gap or the like to be formed when the upper and lower glass substrates are bonded together. Therefore, it is preferably 3 μm or less, preferably 2 μm or less. The particle diameter can be measured by a laser diffraction, a scattering type particle size distribution analyzer (dry type) (manufactured by Seishin Co., Ltd.; LMS-30). When the content of the liquid crystal sealing agent used in the present invention is 100 parts by mass, the content of the inorganic filler is usually 1 to 60 parts by mass, preferably 1 to 40 parts by mass. If the amount of the inorganic filler is too small, the adhesion strength to the glass substrate is lowered, and the moisture resistance reliability is also inferior, so that the adhesion strength after moisture absorption may be further lowered. On the other hand, if the content of the inorganic filler is too large, it is difficult to be compressed and there is a possibility that the gap of the liquid crystal cell is hard to form.

The hardening accelerator agent may, for example, be an organic acid or an imidazole. The organic acid may, for example, be an organic carboxylic acid or an organic phosphoric acid, and is preferably an organic carboxylic acid. Specific examples thereof include aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenone tetracarboxylic acid, and furan dicarboxylic acid, and succinic acid. Diacid, dodecanedioic acid, azelaic acid, sulfur Dipropionic acid, cyclohexanedicarboxylic acid, ginseng (2-carboxymethyl)isocyanate, ginseng (2-carboxyethyl)isocyanate, ginseng (2-carboxypropyl) Isocyanurate, bis(2-carboxyethyl)isocyanate, and the like.

Further, examples of the imidazole compound include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzoyl. 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyano Ethyl-2-undecylimidazole, 2,4-diamino-6(2'-methylimidazolium(1'))ethyl-s-triazine, 2,4-diamino-6(2 '-undecylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6(2'-ethyl-4-methylimidazolium (1'))ethyl-s- Triazine, 2,4-diamino-6(2'-methylimidazolium(1'))ethyl-s-triazine and isomeric cyanuric acid adduct, 2-methylimidazolium isocyanocyanate Acid 2:3 adduct, 2-phenylimidazolium isocyanurate adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5 -methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and the like.

When the total amount of the liquid crystal sealing agent is 100 parts by mass, the content of the curing accelerator in the liquid crystal sealing agent is usually 0.1 to 10 parts by mass. 0.5 to 5 parts by mass.

In the liquid crystal display unit of the present invention, one of the specific electrodes is formed on the substrate, and the substrate is opposed to each other at a predetermined interval, and the periphery is sealed with a liquid crystal sealing agent, and the liquid crystal is sealed in the gap. The type of liquid crystal to be enclosed is not particularly limited. Here, the substrate is made of a substrate having a combination of at least one surface formed of glass, quartz, plastic, tantalum or the like. In the method of adding a spacer (spacer, gap control material) such as glass fiber to a liquid crystal sealing agent, the liquid crystal sealing agent is applied onto one surface of the pair of substrates by a dispenser or a screen printing device. Temporary hardening at 80~120 °C as needed. Thereafter, liquid crystal is dropped on the inside of the bank composed of the liquid crystal sealing agent, and the other substrate is superposed in a vacuum to perform gap formation. Depending on the case, it is also possible to drop liquid crystal on the substrate to which the liquid crystal sealing agent is not applied, but none of them affects the effects of the present invention. Further, in order to achieve an appropriate cell gap, it is preferable to apply an in-plane separator (for example, Natoco spacer or the like) to one substrate in advance. After the spacer is formed, the irradiation can also need to 1000mJ / cm ² ~ 6000mJ / cm ² of ultraviolet rays, after curing at 90 ~ 130 ℃ 1 to 2 hours, to thereby obtain a liquid crystal display unit according to the present invention.

Liquid crystal density used in the method of manufacturing a liquid crystal display unit of the present invention The sealant can be obtained, for example, by the following method. First, the curable resin having an epoxy group is dissolved and mixed as needed in (c) minutes. The decane coupling agent is then dissolved in the mixture as needed. Then, the component (a), the component (b), and, if necessary, a thermal curing agent, an inorganic filler, an antifoaming agent, a coating agent, a solvent, and the like are added, and a known mixing device, for example, three rolls, a sand mill, or the like is added. After ball mills and the like are uniformly mixed, they are filtered through a metal sieve.

Manufacturing method of liquid crystal display unit according to the present invention, as in manufacturing In the step, the liquid crystal does not penetrate into the liquid crystal sealing agent, so that the liquid crystal display unit can be manufactured extremely stably. Moreover, the production cycle can be shortened, so that further mass production can be improved.

Further, the liquid crystal display unit of the present invention has a high voltage holding ratio and a low ion density, and is also required as a liquid crystal display unit.

[Examples]

Hereinafter, the present invention will be described in detail by way of synthesis examples, manufacturing examples, and examples. It is to be understood that the invention is not limited to the embodiments. In addition, unless otherwise stated, “parts” and “%” in this document are quality standards.

[Synthesis Example 1]

Synthesis of [1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane]

100 parts (0.28 mol) of commercially available tetraphenylethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 350 parts of dimethylformaldehyde. 32 parts of pyridine was added thereto as a basic catalyst (0.4 mol), and BSTFA (manufactured by Shin-Etsu Chemical Co., Ltd.) 150 parts (0.58 mol) as a decylating agent, and the temperature was raised to 70 ° C, followed by stirring for 2 hours. The obtained reaction liquid was cooled, and 200 parts of water was added while stirring, and the product was precipitated while the unreacted decylating agent was deactivated. The precipitated product was separated by filtration and washed thoroughly with water. Then, the obtained product was dissolved in acetone, and water was added thereto to recrystallize and purify. 105.6 parts of the desired 1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane (yield 88.3%) was obtained.

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

[Synthesis Example 2]

[Synthesis of all-acrylates of resorcinol diglycidyl ether]

181.2 g of resorcinol diglycidyl ether (EX-201: manufactured by Nagase ChemteX Co., Ltd.) was dissolved in 266.8 g of toluene, and 0.8 g of dibutylhydroxytoluene was added thereto as a polymerization inhibitor, and the temperature was raised to 60 ° C. . Thereafter, 117.5 g of acrylic acid having an epoxy group equivalent of 100% was added, and the temperature was further raised to 80 ° C. 0.6 g of trimethylammonium chloride was added thereto, and the mixture was stirred at 98 ° C for about 30 hours to obtain a reaction liquid. By washing the reaction liquid and distilling off toluene, the benzene is obtained between the ends. Epoxy acrylate of phenol diglycidyl ether 293g. The theoretical value of the reactive base equivalent of the obtained epoxy acrylate was 183.

[Production Examples 1 to 5 of Liquid Crystal Sealant]

The liquid crystal sealing agent was produced by using the components (a), (b), (c) and the like in the amounts shown in Table 1 below. The manufacturing method is as follows.

First, a curable resin having an epoxy group is heated and dissolved in the component (c). After cooling to room temperature, a decane coupling agent, a component (a), a component (b), a thermosetting agent, an inorganic filler, and a curing accelerator are sequentially added, and uniformly mixed with three rolls, and then a metal sieve (635 mesh) is used. filter.

Ingredient (a)-1: Polyoxyethylene rubber powder (manufactured by Shin-Etsu Chemical Co., Ltd.: KMP-594; average particle size 5 μm)

Ingredient (a)-2: Polyoxynized rubber powder (manufactured by Shin-Etsu Chemical Co., Ltd.: KMP-598; average particle diameter 13 μm)

Ingredient (a)-3: Polyurethane rubber (Gan Shang Industrial Co., Ltd.: JB-800T; average particle size 6 μm)

Ingredient (a)-4: Polyurethane rubber (Gan Shang Industrial Co., Ltd.: JB-800BK; average particle size 8 μm)

Ingredient (a)-5: Acrylate rubber (Ji Shui Chemical Industry Co., Ltd.: AFX-8; average particle size 8 μm)

Component (b): 1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane (Comparative Example 1 was finely pulverized by a jet mill to an average particle diameter of 1.9 μm)

Component (c)-1: Total acrylate of resorcinol diglycidyl ether (Synthetic Example 2)

Ingredient (c)-2: Ethylene oxide modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.: DPEA-12)

Epoxy resin having an epoxy group: ethylene oxide addition bisphenol S type epoxy resin (synthesized by the method described in Japanese Patent No. 4211942)

Thermal hardener: ginseng (2-mercaptocarbonylethyl) isocyanurate finely pulverized product (manufactured by Japan Finechem Co., Ltd.: HCIC is finely pulverized by a jet mill to an average particle diameter of 1.5 μm)

Decane coupling agent-1: 3-glycidoxypropyltrimethoxydecane (manufactured by Chisso Co., Ltd.: Sila-Ace S-510)

Decane coupling agent-2: N-2 (aminoethyl) 3-aminopropyl triethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-603)

Hardening accelerator: ginseng (3-carboxyethyl) isocyanurate (manufactured by Shikoku Chemicals Co., Ltd.: CIC acid is finely pulverized by a jet mill to an average particle diameter of 1.5 μm)

Inorganic filler: spherical cerium oxide (Shin-Etsu Chemical Industry Co., Ltd. Division manufacturing: X-24-9163A; average particle size 110nm)

[Insulation tolerance evaluation of liquid crystal]

Three kinds of liquid crystal display units having cell gaps of 3 μm, 4 μm, and 5 μm were produced using the liquid crystal sealing agents produced in Production Examples 1 to 5 of the liquid crystal sealing agent, and the penetration property was observed. The test method is as follows.

1 g of a glass fiber having a diameter of 3 μm, 4 μm, or 5 μm (PF-30S, PF-40S, or PF-50S; manufactured by Nippon Electric Glass Co., Ltd.) was added as a separator to 100 g of each of the liquid crystal sealing agents, and the mixture was stirred and defoamed. , fill to the syringe. On the glass substrate with the ITO transparent electrode, a liquid crystal sealant prefilled into the syringe was used to apply a seal pattern and a dummy seal pattern using a dispenser (SHOTMASTER 300: manufactured by Musashi Engineering Co., Ltd.). The cloth was then dropped into a frame of a sealing pattern of liquid crystal (MLC-3007; manufactured by Merck Co., Ltd.). The in-plane partition (Natoco spacer KSEB-310F, KSELB-410NPF, or KSEB-525F; manufactured by Natoco Co., Ltd.) was spread on another rubbing-treated glass substrate; the gap after bonding was 3 μm wide. 4 μm or 5 μm) and thermally bonded, and a substrate which has been previously dropped into the liquid crystal is attached in a vacuum using a bonding apparatus. After the atmosphere was connected and a gap was formed, it was allowed to stand for 10 minutes, and then placed in an oven at 120 ° C for 1 hour to heat-harden. Then, the interface between the sealant and the liquid crystal was observed with a polarizing microscope, and evaluated by the following criteria. The results are shown in Table 2.

○: No penetration of the liquid crystal into the sealant was observed.

△: A small amount of liquid crystal was observed to penetrate into the sealant.

×: Liquid crystal permeation into the sealant was observed.

Table 2

*: The cell gap is not uniform and the LCD unit cannot be produced.

As is clear from the results of Table 2, in Examples 1 to 9, the liquid crystal display unit could be manufactured without penetrating the liquid crystal. However, in Comparative Examples 1 and 2, the liquid crystal display unit could not be manufactured due to penetration or gap failure. Therefore, the advantages of the present invention can be confirmed.

[Industry Utilization]

According to the method for producing a liquid crystal display unit of the present invention, since the liquid crystal does not penetrate into the liquid crystal sealing agent in the manufacturing step, the liquid crystal display unit can be manufactured extremely stably. Moreover, the production cycle can be shortened, so that further mass production can be improved.

Claims (6)

In a liquid crystal display unit comprising two substrates, a liquid crystal is dropped on a bank of a bank formed of a liquid crystal sealing agent formed on one of the substrates, and the other substrate is bonded to the substrate. And a method for producing the liquid crystal sealing agent by ultraviolet rays and/or heat, wherein the liquid crystal sealing agent contains (a) an organic filler, and the average particle diameter of the (a) organic filler is set to A. (μm), when the cell gap of the liquid crystal display unit is B (μm), the following formula (1) is satisfied: 1.0 μm ≦ AB ≦ 9.0 μm. . . (1). The method of manufacturing a liquid crystal display unit according to claim 1, wherein the hardening step of the liquid crystal sealing agent is performed only by heat. The method for producing a liquid crystal display unit according to claim 1, wherein the liquid crystal sealing agent further contains (b) a thermal radical polymerization initiator and (c) a curable compound having a (meth)acryl fluorenyl group. The method of manufacturing a liquid crystal display unit according to claim 1, wherein the (a) organic filler is rubber fine particles. The method of manufacturing a liquid crystal display unit according to claim 4, wherein the rubber fine particles are composed of acrylate rubber, styrene rubber, styrene olefin rubber or polyoxymethylene rubber. A liquid crystal display unit manufactured by the manufacturing method according to any one of claims 1 to 5.