JP6683429B2 - Curable resin particles used in a sealing agent for a liquid crystal dropping method, a sealing agent for a liquid crystal dropping method, and a liquid crystal display element - Google Patents

Description

  The present invention relates to curable resin particles used for a sealant for a liquid crystal dropping method. The present invention also relates to a sealant for a liquid crystal dropping method using the above curable resin particles, and a liquid crystal display element.

  In recent years, the liquid crystal display device manufacturing method can shorten the tact time and easily optimize the amount of liquid crystal used. Therefore, instead of the liquid crystal dropping method using a photo-curing and heat-curing type sealant, It's starting.

  In the liquid crystal dropping method, first, a sealant is applied to one of the two transparent substrates with electrodes by dispensing to form a frame-shaped seal pattern. Next, while the sealant is in an uncured state, microdroplets of liquid crystal are dropped on the entire surface of the transparent substrate frame, and the other transparent substrate is immediately overlaid, and the sealant is irradiated with light such as ultraviolet rays to temporarily cure. I do. After that, the sealant that has been temporarily cured during liquid crystal annealing is heated and fully cured to form a seal portion, and a liquid crystal display element is manufactured. If the transparent substrates are attached under reduced pressure, a liquid crystal display device can be manufactured with extremely high efficiency. In recent years, this liquid crystal dropping method has become the mainstream of the method for manufacturing a liquid crystal display element.

  By the way, mobile devices with various liquid crystal panels, such as mobile phones and portable game machines, are in widespread use, and downsizing of the device is currently the most demanded issue. As a method of downsizing, there is a narrow frame of the liquid crystal display unit (hereinafter, also referred to as “narrow frame design”). For example, the seal portion may be disposed under the wiring due to the narrow frame.

  In addition, the sealant used in the liquid crystal dropping method is required to have a uniform thickness and a property capable of adhering members on both sides at appropriate intervals and absorbing impact. Therefore, particles may be mixed with the sealant. The particles can control the distance between the members with high accuracy and can reduce the impact.

  Such a sealant is disclosed, for example, in Patent Document 1 below. Patent Document 1 describes that rubber powder such as silicone rubber powder is used as the particles.

JP, 2009-139922, A

  When a liquid crystal display element having a narrow frame design is manufactured by the liquid crystal dropping method, there is a portion where light does not hit the seal portion due to the wiring. As a result, there is a problem in that the adhesiveness of the seal portion does not easily become sufficiently high. For this reason, in the sealant for liquid crystal display devices containing the silicone rubber powder as described in Patent Document 1, the content of the curable component such as the photocurable component is small, so that the adhesiveness of the seal part is particularly low. It has been found by the present inventors that there is a problem that it tends to occur.

  Further, when the silicone rubber powder as described in Patent Document 1 is used, the adhesive force is poor at the silicone rubber powder portion in contact with the liquid crystal display element member, so that the adhesiveness of the entire seal portion is likely to be further lowered. It has been found by the present inventors that there is a problem.

  Furthermore, when the silicone rubber powder as described in Patent Document 1 is used, the liquid crystal may be contaminated due to the silicone rubber powder. Further, due to the characteristic of the material called silicone, the moisture permeability becomes high, which may cause unevenness in the liquid crystal display.

  An object of the present invention is to provide a curable resin particle for use in a liquid crystal dropping method sealant, which can enhance the adhesiveness of the seal portion and the liquid crystal contamination preventing property using the liquid crystal dropping method sealant in a liquid crystal display device. That is. Another object of the present invention is to provide a sealant for a liquid crystal dropping method and a liquid crystal display element, which use the above curable resin particles.

  According to a broad aspect of the present invention, it is a photo-curable or thermo-curable particle that is used for a liquid crystal dropping method sealant that is cured by irradiation with light or heating, and is a photo-curable compound or a thermo-curable compound. Provided is a curable resin particle (hereinafter, may be abbreviated as a curable resin particle) used for a sealant for a liquid crystal dropping method that is formed.

  In a specific aspect of the curable resin particles according to the present invention, the photocurable compound or the thermosetting compound is an epoxy compound or a (meth) acrylic compound.

  In a specific aspect of the curable resin particle according to the present invention, the curable resin particle is a thermosetting particle that is used in a sealant for a liquid crystal dropping method that is cured by heating and flows at 23 ° C. It is a semi-cured particle formed by advancing the curing of an epoxy compound having a property or a (meth) acrylic compound having a fluidity at 23 ° C.

  In a specific aspect of the curable resin particles according to the present invention, the particle diameter is 0.5 μm or more and 80 μm or less.

  In a specific aspect of the curable resin particles according to the present invention, the curable resin particles include a light shielding agent.

  In one specific aspect of the curable resin particles according to the present invention, when the compressive displacement when a load of 1 g is applied at 23 ° C. is L3 and the particle diameter is Dn, L3 / Dn is expressed as a percentage of 1 g. The strain is 20% or more.

  In one specific aspect of the curable resin particles according to the present invention, the curable resin particles include a polymerization initiator or a thermosetting agent.

  According to a broad aspect of the present invention, there is provided a sealant for a liquid crystal dropping method, which comprises a thermosetting compound having fluidity at 23 ° C., a polymerization initiator or a thermosetting agent, and the above-mentioned curable resin particles. It

  In a specific aspect of the sealant for a liquid crystal dropping method according to the present invention, a thermosetting compound contained in the sealant for a liquid crystal dropping method and having fluidity at 23 ° C. when heated and a liquid crystal dropping method for a liquid crystal dropping method. The curable resin particles contained in the sealant can be thermoset so as to chemically bond with each other.

  In a specific aspect of the sealant for liquid crystal dropping method according to the present invention, the sealant for liquid crystal dropping method does not contain a photocurable component.

  According to a broad aspect of the present invention, a first liquid crystal display element member, a second liquid crystal display element member, the first liquid crystal display element member, and the second liquid crystal display element member are provided. A seal portion that seals the outer peripheries of the first liquid crystal display element member and the second liquid crystal display element member in a facing state, and the first liquid crystal display element inside the seal portion. And a liquid crystal disposed between the second liquid crystal display element member, and the seal portion is formed by thermally curing a sealant for a liquid crystal dropping method. Provided is a liquid crystal display device, wherein the sealing agent for a construction method contains a thermosetting compound having fluidity at 23 ° C., a thermosetting agent, and the above-mentioned curable resin particles.

  In a particular aspect of the liquid crystal display element according to the present invention, in the seal portion, a thermosetting compound having fluidity at 23 ° C., which is contained in the sealant for liquid crystal dropping method, and the sealant for liquid crystal dropping method. The heat-curable resin particles contained in are thermally cured so as to chemically bond with each other.

  The curable resin particles according to the present invention are used as a sealant for a liquid crystal dropping method which is cured by irradiation with light or heating. The curable resin particles according to the present invention are particles that are photo-curable or thermo-curable, and are formed of a photo-curable compound or a thermo-curable compound. Therefore, in a liquid crystal display device, a sealing agent for a liquid crystal dropping method is used. It is possible to enhance the adhesiveness of the used seal portion and the liquid crystal contamination prevention property.

FIG. 1 is a sectional view showing a liquid crystal display device using curable resin particles according to an embodiment of the present invention.

  Hereinafter, the present invention will be described in detail. In addition, in this specification, "(meth) acryl" means one or both of "acryl" and "methacryl", and "(meth) acryloyl" means one or both of "acryloyl" and "methacryloyl". , "(Meth) acrylate" means one or both of "acrylate" and "methacrylate".

(Curable resin particles)
The curable resin particles (hereinafter, may be abbreviated as curable resin particles) used for the sealant for liquid crystal dropping method according to the present invention are used for the sealant for liquid crystal dropping method, which is cured by irradiation of light or heating. .

  The curable resin particles according to the present invention are particles that can be photocured or thermoset, and are formed of a photocurable compound or a thermosetting compound. The curable resin particles according to the present invention can be photo-cured or heat-cured, and therefore are different from particles having neither photo-curable nor thermo-curable.

  Since the present invention is provided with the above-mentioned constitution, in the liquid crystal display device, the adhesiveness of the seal portion using the sealant for the liquid crystal dropping method and the liquid crystal contamination preventing property can be enhanced. Since the curable resin particles are particles, they function as a gap control material in the sealant for the liquid crystal dropping method. As a result, by the seal portion formed of the sealant for the liquid crystal dropping method, the two liquid crystal display element members adhered by the seal portion can be attached at appropriate intervals. Furthermore, since the curable resin particles are contained in the sealant for liquid crystal dropping method, migration of the liquid crystal to the sealant for liquid crystal dropping method is blocked. The curable resin particles also function as a liquid crystal outflow prevention material. Therefore, the liquid crystal contamination prevention property of the seal part using the sealant for the liquid crystal dropping method is enhanced.

  Furthermore, since the curable resin particles are photocurable or heat curable and are formed of a photocurable compound or a thermosetting compound, the curable resin particles themselves also exert an adhesive function. Therefore, the adhesiveness of the seal portion using the sealant for the liquid crystal dropping method is effectively increased. On the other hand, for example, when non-curable silicone particles or non-curable epoxy resin particles are used, the particles do not improve the adhesiveness, but rather reduce the adhesiveness, and The adhesiveness of the part becomes low.

  As the photocurable compound or the thermosetting compound, the compounds described in the section of the sealant for liquid crystal dropping method described later can be appropriately used.

  From the viewpoint of further enhancing the adhesiveness, the photocurable compound or the thermosetting compound is preferably an epoxy compound or a (meth) acrylic compound.

  The curable resin particles used in the sealant for a liquid crystal dropping method according to the present invention are suitably used for a sealant for a liquid crystal dropping method that is cured by heating. From the viewpoint of further enhancing the adhesiveness or the viewpoint of enhancing the light-shielding property, the curable resin particles are preferably thermosetting particles. From the viewpoint of further improving the adhesiveness, the curable resin particles are preferably formed of an epoxy compound or a (meth) acrylic compound. From the viewpoint of further increasing the adhesiveness, semi-cured particles formed by proceeding the curing of an epoxy compound having fluidity at 23 ° C. or a (meth) acrylic compound having fluidity at 23 ° C. are preferable. . In the semi-cured particles, an epoxy compound and a (meth) acrylic compound may be used in combination. From the viewpoint of further enhancing the adhesiveness, the curable resin particles are preferably formed of an epoxy compound. The semi-cured particles may be formed of a (meth) acrylic compound. The epoxy compound having fluidity at 23 ° C. and the (meth) acrylic compound having fluidity at 23 ° C. need not be solid at 23 ° C. and have fluidity such as liquid. The semi-cured particles are particles that have been cured but have not been cured yet and can be cured.

  From the viewpoint of controlling the distance between the two liquid crystal display element members adhered by the seal portion with high accuracy, the particle diameter of the curable resin particles is preferably 0.5 μm or more, more preferably 1 μm or more, and further preferably It is 3 μm or more, preferably 80 μm or less, more preferably 50 μm or less, and further preferably 10 μm or less.

  From the viewpoint of enhancing the light shielding property, the curable resin particles preferably contain a light shielding agent. By using the above light-shielding agent, the liquid crystal display element sealant can be preferably used as a light-shielding sealant. The sealant for a liquid crystal display element is preferably a sealant for a liquid crystal dropping method.

  The liquid crystal display device manufactured by using the sealant for liquid crystal display device containing the curable resin particles containing the light shielding agent has a sufficient light shielding property, and thus has a high contrast without light leakage and an excellent image. A liquid crystal display device having display quality can be realized.

  Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, and carbon black. Titanium black or carbon black is preferred.

  The above-mentioned titanium black and carbon black exert a sufficient effect even if they are not surface-treated. The surface is treated with titanium black whose surface is treated with an organic component such as a coupling agent or titanium black which is coated with an inorganic component such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide and magnesium oxide. Titanium black can also be used. Titanium black that has been treated with an organic component is preferable because it can enhance the insulating property.

  The compressive displacement when a load of 1 g was applied to the curable resin particles at 23 ° C. is L3. The particle diameter of the curable resin particles is Dn. The strain of 1 g expressed as a percentage of L3 / Dn is preferably 20% or more, more preferably 30% or more, still more preferably 35% or more, preferably 50% or less, more preferably 40% or less. When the strain is equal to or more than the lower limit, the contact area of the curable resin particles with the liquid crystal display element member becomes large, and the adhesiveness of the seal portion is further enhanced. When the strain is equal to or less than the upper limit, the thickness of the seal portion can be appropriately maintained.

  The compression displacement L3 is measured as follows.

  A compression displacement L3 is obtained by applying a load of 1 g to one particle using a micro compression tester and measuring the displacement amount at that time.

  The curable resin particles preferably contain a polymerization initiator or a thermosetting agent. In this case, the curable resin particles can be satisfactorily photo-cured or heat-cured. However, the curable resin particles do not have to include a polymerization initiator and a thermosetting agent. In this case, the curable resin particles can be photo-cured or heat-cured by the action of the polymerization initiator or the thermosetting agent contained in the liquid crystal dropping method sealing agent. In this case, the curable resin particles may be entirely photo-cured or heat-cured, or only the surface thereof may be photo-cured or heat-cured. More preferably, the curable resin particles contain a thermosetting agent. As the above-mentioned polymerization initiator and the above-mentioned thermosetting agent, the compounds described in the section of the sealing agent for liquid crystal dropping method described later can be appropriately used.

  When the curable resin particles contain a polymerization initiator, in the material for forming the curable resin particles, the polymerization is performed with respect to a total of 100 parts by weight of the photocurable compound and the thermosetting compound. The content of the initiator is preferably 0.1 part by weight or more, more preferably 1 part by weight or more, preferably 30 parts by weight or less, more preferably 10 parts by weight or less, still more preferably 5 parts by weight or less. When the curable resin is formed of a photocurable compound, the content of the polymerization initiator is preferably 0.1 part by weight or more, more preferably 100 parts by weight of the photocurable compound. Is 1 part by weight or more, preferably 30 parts by weight or less, more preferably 10 parts by weight or less, and further preferably 5 parts by weight or less. When the content of the polymerization initiator is at least the above lower limit, the curable resin particles can be sufficiently cured. When the content of the polymerization initiator is at most the above upper limit, the storage stability of the curable resin particles will be high.

  When the curable resin particles contain a thermosetting agent, the content of the thermosetting agent is preferably 100 parts by weight of the thermosetting compound in the material for forming the curable resin particles. It is 1 part by weight or more, preferably 50 parts by weight or less, and more preferably 30 parts by weight or less. When the content of the thermosetting agent is at least the above lower limit, the curable resin particles can be sufficiently thermoset. When the content of the thermosetting agent is not more than the upper limit, the viscosity of the curable resin particles does not become too high.

(Sealant for liquid crystal dropping method)
The sealant for the liquid crystal dropping method (hereinafter, may be abbreviated as a sealant) is cured by irradiation with light or heating. The sealing agent contains a photocurable component or a thermosetting component and the curable resin particles. The sealing agent preferably contains a thermosetting component. The sealing agent may or may not contain a photocurable component. The sealant may be irradiated with light or may not be irradiated with light for curing. In addition, when the said sealing agent does not contain a photocurable component, you may store under irradiation of light.

  The thermosetting component preferably contains a thermosetting compound having fluidity at 23 ° C. and a polymerization initiator or a thermosetting agent. In this case, a polymerization initiator and a thermosetting agent may be used together. The thermosetting compound having fluidity at 23 ° C. easily wets and spreads on the surface of the curable resin particles and enhances the adhesiveness of the seal portion.

  With respect to 100 parts by weight of the thermosetting compound, the content of the curable resin particles is preferably 3 parts by weight or more, more preferably 5 parts by weight or more, preferably 70 parts by weight or less, more preferably 50 parts by weight. Below the section. When the content of the curable resin particles is not less than the above lower limit and not more than the above upper limit, the adhesiveness of the resulting liquid crystal dropping construction sealing agent is further improved.

  Examples of the thermosetting compound include oxetane compounds, epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenol compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds and polyimide compounds. As for the said thermosetting compound, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of further improving the adhesiveness and long-term reliability, the thermosetting compound preferably contains a (meth) acrylic compound, and more preferably contains an epoxy (meth) acrylate. The “(meth) acrylic compound” means a compound having a (meth) acryloyl group. The “epoxy (meth) acrylate” means a compound obtained by reacting (meth) acrylic acid with all epoxy groups in the epoxy compound.

  Examples of the epoxy compound that is a raw material for synthesizing the epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and 2,2′-diallyl bisphenol A type epoxy resin. , Hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol Novolac type epoxy resin, ortho-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphth Ren phenol novolak type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber-modified epoxy resins, glycidyl ester compounds, and bisphenol A type episulfide resins.

  Examples of commercially available bisphenol A type epoxy resins include jER828EL, jER1001, and jER1004 (all manufactured by Mitsubishi Chemical Corporation); Epicron 850-S (manufactured by DIC Corporation).

  Examples of commercially available bisphenol F type epoxy resins include jER806 and jER4004 (both manufactured by Mitsubishi Chemical Corporation).

  Examples of commercially available bisphenol S-type epoxy resins include Epiclon EXA1514 (manufactured by DIC).

  Examples of commercially available products of the 2,2'-diallyl bisphenol A type epoxy resin include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.) and the like.

  Examples of commercial products of the hydrogenated bisphenol type epoxy resin include Epiclon EXA7015 (manufactured by DIC).

  Examples of commercial products of the propylene oxide-added bisphenol A type epoxy resin include EP-4000S (manufactured by ADEKA).

  Examples of commercially available resorcinol type epoxy resins include EX-201 (manufactured by Nagase Chemtex) and the like.

  Examples of commercial products of the above-mentioned biphenyl type epoxy resin include jERYX-4000H (manufactured by Mitsubishi Chemical Corporation).

  Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).

  Examples of commercial products of the diphenyl ether type epoxy resin include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like.

  Examples of commercially available products of the dicyclopentadiene type epoxy resin include EP-4088S (manufactured by ADEKA).

  Examples of commercially available naphthalene type epoxy resins include Epiclon HP4032 and Epiclon EXA-4700 (both manufactured by DIC).

  Examples of commercially available phenol novolac type epoxy resins include Epiclon N-770 (manufactured by DIC).

  Examples of commercially available products of the above-mentioned ortho-cresol novolac type epoxy resin include Epicron N-670-EXP-S (manufactured by DIC).

  Examples of commercially available products of the dicyclopentadiene novolac type epoxy resin include Epiclon HP7200 (manufactured by DIC).

  Examples of commercially available products of the above biphenyl novolac type epoxy resin include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) and the like.

  Examples of commercially available naphthalenephenol novolac type epoxy resins include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).

  Examples of commercially available products of the glycidyl amine type epoxy resin include jER630 (manufactured by Mitsubishi Chemical Corporation); Epicron 430 (manufactured by DIC Corporation); TETRAD-X (manufactured by Mitsubishi Gas Chemical Company).

  Examples of commercially available products of the above alkyl polyol type epoxy resin include ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); Epicron 726 (manufactured by DIC Co.); Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.); Denacol EX-611 (Nagase Chemtex). Manufactured by the company) and the like.

  Examples of commercially available products of the rubber-modified epoxy resin include YR-450 and YR-207 (both are manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); Epolide PB (manufactured by Daicel).

  Examples of commercial products of the glycidyl ester compound include Denacol EX-147 (manufactured by Nagase Chemtex).

  Examples of commercially available bisphenol A type episulfide resins include jERYL-7000 (manufactured by Mitsubishi Chemical Corporation).

  Other commercially available products of the above epoxy resin include, for example, YDC-1312, YSLV-80XY, and YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); XAC4151 (manufactured by Asahi Kasei Corporation); jER1031 and jER1032 (both are Mitsubishi). Chemical company); EXA-7120 (manufactured by DIC); TEPIC (manufactured by Nissan Chemical Co., Ltd.) and the like.

  Examples of commercially available products of the epoxy (meth) acrylates, e.g., EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, and EBECRYLRDX63182 (all manufactured by Daicel Orunekusu Co.); EA- 1010, EA-1020, EA-5323, EA-5520, EA-CHD, and EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.); epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA. , Epoxy ester 80MFA, Epoxy Ester 3002M, Epoxy ester 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA, and Epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.); Denacol acrylate DA-141, Denacol acrylate DA-314, And Denacol Acrylate DA-911 (both manufactured by Nagase Chemtex).

  Examples of the (meth) acrylic compound other than the epoxy (meth) acrylate include an ester compound obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, and a (meth) acrylic compound having a hydroxyl group in an isocyanate compound. Examples thereof include urethane (meth) acrylate obtained by reacting an acid derivative.

  As the ester compound obtained by reacting the (meth) acrylic acid with a compound having a hydroxyl group, any one of a monofunctional ester compound, a bifunctional ester compound, and a trifunctional or higher functional ester compound may be used. .

  Examples of the monofunctional ester compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and isobutyl (meth). ) Acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, Methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethylcarbitol ( ) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2, 2,3,3-Tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, imide (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) Acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) acrylate Relate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, bicyclopentenyl (meth) acrylate, isodecyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 2- (Meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, glycidyl (meth) acrylate, and 2- (meth ) Acryloyloxyethyl phosphate and the like can be mentioned.

  Examples of the bifunctional ester compound include 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9. -Nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) Acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate , Propylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, dimethylol dicyclopentadienyl di (meth) acrylate, 1,3 -Butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di ( (Meth) acrylate, polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, and poly Taj diol di (meth) acrylate.

  Examples of the trifunctional or higher functional ester compound include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, and ethylene oxide-added trimethylolpropane tri (meth) acrylate. Acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, Pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide addition group Serintori (meth) acrylate, and tris (meth) acryloyloxyethyl phosphate, and the like.

  The urethane (meth) acrylate is obtained, for example, by reacting 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group with 1 equivalent of an isocyanate compound having two isocyanate groups in the presence of a catalytic amount of a tin compound. be able to.

  Examples of the isocyanate compound which is a raw material of the urethane (meth) acrylate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4. '-Diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris ( Isocyanate phenyl) thiophosphate, tetramethyl xylene diisocyanate, and 1,6,10-undecanetri Isocyanate, and the like.

  As the isocyanate compound which is a raw material of the urethane (meth) acrylate, for example, a polyol such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, or polycaprolactone diol. And a chain-extended isocyanate compound obtained by reaction with an excess of isocyanate can also be used.

  Examples of the (meth) acrylic acid derivative having a hydroxyl group, which is a raw material of the urethane (meth) acrylate, include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. And commercially available products such as 2-hydroxybutyl (meth) acrylate; divalent ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol. Alcohol mono (meth) acrylate; Trihydric alcohol mono (meth) acrylate and di (meth) acrylate such as trimethylolethane, trimethylolpropane, and glycerin; Epoxy (meth) such as bisphenol A type epoxy acrylate Acrylate, and the like.

  Examples of commercially available urethane (meth) acrylates include M-1100, M-1200, M-1210, and M-1600 (all manufactured by Toagosei Co., Ltd.); EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803. , EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, and EBECRYL2220 (all manufactured by Daicel Orunekusu Co.); Art resin UN-9000H, Art resin UN-9000A, ART rESIN UN-7100, Art Resin UN-1 55, ART RESIN UN-330, ART RESIN UN-3320HB, ART RESIN UN-1200TPK, and ART RESIN SH-500B (all manufactured by Negami Kogyo Co., Ltd.); U-122P, U-108A, U-340P, U-4HA. , U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA. -4400, UA-340P, U-3HA, UA-7200, U-2061BA, U-10H, U-122A, U-340A, U-108, U-6H, and UA-4000 (all are Shin-Nakamura Chemical Co., Ltd. AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, A-306T, and UA-306I (all manufactured by Kyoeisha Chemical Co., Ltd.).

From the viewpoint of suppressing adverse effects on the liquid crystal, the (meth) acrylic compound preferably has a hydrogen-bonding unit such as —OH group, —NH— group, and —NH ₂ group.

  From the viewpoint of increasing the reactivity, the (meth) acrylic compound preferably has two or three (meth) acryloyl groups.

  From the viewpoint of improving the adhesiveness of the sealant for a liquid crystal display element, the thermosetting compound may contain an epoxy compound.

  Examples of the epoxy compound include an epoxy compound which is a raw material for synthesizing the epoxy (meth) acrylate, a partial (meth) acrylic modified epoxy compound, and the like.

  The partial (meth) acryl-modified epoxy compound means a compound having at least one epoxy group and at least one (meth) acryloyl group. The partial (meth) acrylic modified epoxy compound can be obtained, for example, by reacting (meth) acrylic acid with a part of two or more epoxy groups in a compound having two or more epoxy groups.

  Examples of commercially available products of the above-mentioned partial (meth) acrylic modified epoxy compound include KRM8287 (manufactured by Daicel Ornex).

  When the (meth) acrylic compound and the epoxy compound are used as the thermosetting compound, the epoxy group is preferably 20 in 100 mol% of the total of the (meth) acryloyl group and the epoxy group in the entire thermosetting compound. It is at least mol%, preferably at most 50 mol%. When the epoxy group content is less than or equal to the upper limit, the solubility of the liquid crystal display element sealant in the liquid crystal is low, and liquid crystal contamination is further unlikely to occur, and the display performance of the liquid crystal display element is further improved.

  Examples of the polymerization initiator include radical polymerization initiators and cationic polymerization initiators. As the polymerization initiator, only one kind may be used, or two or more kinds may be used in combination.

  Examples of the radical polymerization initiator include a photoradical polymerization initiator that generates a radical upon irradiation with light and a thermal radical polymerization initiator that generates a radical upon heating.

  The radical polymerization initiator has a markedly higher curing speed than the thermosetting agent. Therefore, by using a radical polymerization initiator, it is possible to suppress the occurrence of seal break and liquid crystal contamination, and also suppress the springback which is likely to occur due to the curable resin particles.

  Examples of the photoradical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthone.

  Examples of commercially available photoradical polymerization initiators include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucilin TPO (all of BASF ether, benzoin ethyl benzoin, benzoin, benzoin, benzoin, benzoin, benzoin; Ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.) and the like can be mentioned.

  Examples of the thermal radical polymerization initiator include azo compounds and organic peroxides. Azo compounds are preferred, and polymer azo initiators composed of polymer azo compounds are more preferred.

  The high molecular weight azo compound means a compound having an azo group, producing a radical capable of curing a (meth) acryloyloxy group by heat, and having a number average molecular weight of 300 or more.

  The number average molecular weight of the above-mentioned polymeric azo initiator is preferably 1,000 or more, more preferably 5,000 or more, further preferably 10,000 or more, preferably 300,000 or less, more preferably 100,000 or less, further preferably 90,000 or less. Is. When the number average molecular weight of the polymeric azo initiator is at least the above lower limit, the polymeric azo initiator is unlikely to adversely affect the liquid crystal. When the number average molecular weight of the polymeric azo initiator is not more than the above upper limit, mixing with the thermosetting compound becomes easy.

  The number average molecular weight is a value determined by polystyrene conversion by measurement by gel permeation chromatography (GPC). Examples of columns used for GPC measurement include Shodex LF-804 (Showa Denko KK).

  Examples of the polymer azo initiator include polymer azo initiators having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.

  The polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group preferably has a polyethylene oxide structure. Examples of such polymeric azo initiators include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid). And a polycondensation product of polydimethylsiloxane having a terminal amino group. Specific examples include VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001, and V-501 ( Wako Pure Chemical Industries, Ltd.) and the like can be mentioned.

  Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxy ester, diacyl peroxide, and peroxydicarbonate.

  As the above cationic polymerization initiator, a photocationic polymerization initiator can be preferably used. The above-mentioned photocationic polymerization initiator generates a protonic acid or a Lewis acid upon irradiation with light. The type of the photocationic polymerization initiator is not particularly limited, and may be an ionic photoacid generating type or a nonionic photoacid generating type.

  Examples of the above-mentioned photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts; iron-allene complexes; titanocene complexes; arylsilanol-aluminum complexes and other organometallic complexes. Is mentioned.

  Examples of commercially available photocationic polymerization initiators include ADEKA OPTOMER SP-150, ADEKA OPTOMER SP-170 (all manufactured by ADEKA), and the like.

  In the liquid crystal dropping method sealing agent, the content of the polymerization initiator is preferably 0.1 part by weight or more, more preferably 1 part by weight or more, and preferably 100 parts by weight of the thermosetting compound. The amount is 30 parts by weight or less, more preferably 10 parts by weight or less, and further preferably 5 parts by weight or less. When the content of the polymerization initiator is at least the above lower limit, the liquid crystal display element sealing agent can be sufficiently cured. When the content of the polymerization initiator is at most the above upper limit, the storage stability of the liquid crystal display device sealing agent will be high.

  Examples of the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, and acid anhydrides. An organic acid hydrazide that is solid at 23 ° C. is preferably used. As for the said thermosetting agent, only 1 type may be used and 2 or more types may be used together.

  Examples of the organic acid hydrazide solid at 23 ° C. include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, and malonic acid dihydrazide. To be

  Examples of commercially available organic acid hydrazides solid at 23 ° C. include Amicure VDH and Amicure UDH (all manufactured by Ajinomoto Fine-Techno Co., Ltd.); SDH, IDH, ADH, MDH (all manufactured by Otsuka Chemical Co., Ltd.) and the like. Is mentioned.

  In the above-mentioned sealing agent for liquid crystal dropping method, the content of the thermosetting agent is preferably 1 part by weight or more, preferably 50 parts by weight or less, and more preferably 30 parts by weight with respect to 100 parts by weight of the thermosetting compound. It is less than or equal to parts by weight. When the content of the thermosetting agent is at least the above lower limit, the sealing agent for liquid crystal display elements can be sufficiently thermoset. When the content of the thermosetting agent is less than or equal to the upper limit, the viscosity of the liquid crystal display element sealing agent does not become too high, and the coatability becomes good.

  The liquid crystal display element sealant preferably contains a curing accelerator. By using the above curing accelerator, the sealing agent can be sufficiently cured without heating at a high temperature.

  Examples of the curing accelerator include polyvalent carboxylic acids having an isocyanuric ring skeleton, epoxy resin amine adducts, and the like, and specifically, for example, tris (2-carboxymethyl) isocyanurate, tris (2-carboxy). Ethyl) isocyanurate, tris (3-carboxypropyl) isocyanurate, bis (2-carboxyethyl) isocyanurate, and the like.

  In the liquid crystal dropping method sealing agent, the content of the curing accelerator is preferably 0.1 part by weight or more and preferably 10 parts by weight or less with respect to 100 parts by weight of the thermosetting compound. When the content of the curing accelerator is at least the above lower limit, the sealing agent for liquid crystal display elements is sufficiently cured, and heating at high temperature is not necessary for curing. When the content of the curing accelerator is not more than the above upper limit, the adhesiveness of the liquid crystal display element sealant becomes high.

  The sealant for liquid crystal display element preferably contains a filler for the purpose of improving viscosity, improving adhesiveness due to stress dispersion effect, improving coefficient of linear expansion, and improving moisture resistance of the cured product.

  Examples of the filler include talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, water. Inorganic fillers such as aluminum oxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite, activated clay and aluminum nitride, polyester particles, polyurethane particles, vinyl polymer particles, acrylic polymer particles, and Examples include organic fillers such as core-shell acrylate copolymer particles. Only 1 type may be used for the said filler and 2 or more types may be used together.

  The content of the filler is preferably 10% by weight or more, more preferably 20% by weight or more, preferably 70% by weight or less, more preferably 60% by weight or less, in 100% by weight of the liquid crystal display element sealing agent. Is. When the content of the filler is at least the above lower limit, effects such as improvement in adhesiveness are sufficiently exhibited. When the content of the filler is equal to or less than the upper limit, the viscosity of the liquid crystal display element sealing agent does not become too high, and the coatability becomes good.

  The liquid crystal display device sealing agent preferably contains a silane coupling agent. The above-mentioned silane coupling agent mainly has a role as an adhesion aid for favorably adhering the sealant to the substrate and the like. As the silane coupling agent, only one kind may be used, or two or more kinds may be used in combination.

  The silane coupling agent is excellent in the effect of improving the adhesiveness to the substrate and the like, and can chemically inhibit the outflow of the curable resin into the liquid crystal by being chemically bonded to the curable resin. -Phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are preferable.

  The content of the silane coupling agent in 100% by weight of the liquid crystal display device sealing agent is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, and preferably 20% by weight or less. More preferably, it is 10% by weight or less. When the content of the silane coupling agent is at least the above lower limit, the effect of blending the silane coupling agent will be sufficiently exhibited. When the content of the silane coupling agent is less than or equal to the above upper limit, the contamination of liquid crystal by the liquid crystal display element sealing agent can be further suppressed.

  The liquid crystal display element sealant may contain a light-shielding agent. By using the above light-shielding agent, the liquid crystal display element sealant can be preferably used as a light-shielding sealant.

  Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Titanium black is preferred.

  A liquid crystal display device manufactured by using a sealant for a liquid crystal display device containing a light-shielding agent has a sufficient light-shielding property, and therefore has a high contrast without light leakage, and a liquid crystal display having excellent image display quality. The device can be realized.

  The titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly in the light having a wavelength of 370 to 450 nm, as compared with the average transmittance for light having a wavelength of 300 to 800 nm. The titanium black has a property of imparting a light-shielding property to the sealant for a liquid crystal display device by sufficiently shielding light having a wavelength in the visible light region, while having a property of transmitting light having a wavelength near the ultraviolet region. . It is preferable that the light-shielding agent contained in the liquid crystal display element sealant has a high insulating property, and titanium black is suitable as the light-shielding agent having a high insulating property.

  The optical density (OD value) per 1 μm of the titanium black is preferably 3 or more, more preferably 4 or more. The higher the light-shielding property of the titanium black, the better. The OD value of the titanium black has no particular upper limit, but the OD value is usually 5 or less.

  The above-mentioned titanium black and carbon black exert a sufficient effect even if they are not surface-treated. Titanium black whose surface is treated with an organic component such as a coupling agent or titanium black whose surface is coated with an inorganic component such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide and magnesium oxide Titanium black can also be used. Titanium black that has been treated with an organic component is preferable because it can enhance the insulating property.

  Examples of the commercially available titanium black include 12S, 13M, 13M-C, 13R-N, and 14M-C (all manufactured by Mitsubishi Materials); Tilak D (manufactured by Ako Kasei).

The specific surface area of the titanium black is preferably 13 m ² / g or more, more preferably 15 m ² / g or more, preferably 30 m ² / g or less, more preferably 25 m ² / g or less.

  The volume resistance of the titanium black is preferably 0.5 Ω · cm or more, more preferably 1 Ω · cm or more, preferably 3 Ω · cm or less, more preferably 2.5 Ω · cm or less.

  The primary particle size of the light shielding agent affects the distance between the two liquid crystal display element members. The primary particle size of the light-shielding agent is preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more, preferably 5 μm or less, more preferably 200 nm or less, further preferably 100 nm or less. When the primary particle diameter of the light-shielding agent is not less than the lower limit, the viscosity and thixotropy of the sealant for liquid crystal display elements are unlikely to increase significantly, and workability is improved. When the primary particle diameter of the light-shielding agent is not more than the upper limit, the coatability of the liquid crystal display element sealing agent will be good.

  The content of the light-shielding agent is preferably 5% by weight or more, more preferably 10% by weight or more, and further preferably 30% by weight or more, based on 100 parts by weight of the thermosetting compound having fluidity at 23 ° C. It is preferably 80% by weight or less, more preferably 70% by weight or less, still more preferably 60% by weight or less. When the content of the light shielding agent is at least the above lower limit, sufficient light shielding properties can be obtained. When the content of the light-shielding agent is not more than the upper limit, the adhesiveness of the sealant for a liquid crystal display element and the strength after curing are increased, and the drawing property is further increased.

  The liquid crystal display element sealant contains, if necessary, a stress relaxation agent, a reactive diluent, a thixotropic agent, a spacer, a curing accelerator, a defoaming agent, a leveling agent, a polymerization inhibitor, and other additives. You may.

  The method for producing the sealant for a liquid crystal display element is not particularly limited, and examples thereof include a thermosetting compound using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a triple roll. And a polymerization initiator or a thermosetting agent, curable resin particles, and an additive such as a silane coupling agent which is optionally added.

  The viscosity of the sealant for liquid crystal display device at 25 ° C. and 1 rpm is preferably 50,000 Pa · s or higher, preferably 500,000 Pa · s or lower, and more preferably 400,000 Pa · s or lower. When the viscosity is equal to or higher than the lower limit and equal to or lower than the upper limit, the coatability of the sealant for liquid crystal display device becomes good. The viscosity is measured using an E-type viscometer.

  From the viewpoint of further increasing the adhesive strength, further increasing the liquid crystal contamination preventing property, and effectively lowering the moisture permeability, when the liquid crystal dropping method sealing agent is heated, it is included in the liquid crystal dropping method sealing agent. It is preferable that the above-mentioned thermosetting compound having fluidity at 23 ° C. and the above-mentioned curable resin particles contained in the sealant for liquid crystal dropping method can be thermoset so as to be chemically bonded. The heating temperature is a temperature at which the sealing agent for liquid crystal display elements is thermally cured, and is preferably 100 ° C. or higher, and preferably 150 ° C. or lower.

(Liquid crystal display element)
A liquid crystal display device can be obtained by using the sealing agent containing the curable resin particles. The liquid crystal display element includes a first liquid crystal display element member, a second liquid crystal display element member, the first liquid crystal display element member, and the second liquid crystal display element member facing each other. A seal portion that seals the outer peripheries of the first liquid crystal display element member and the second liquid crystal display element member, and the first liquid crystal display element member and the seal portion inside the seal portion. And a liquid crystal arranged between the second liquid crystal display element member. In this liquid crystal display element, a liquid crystal dropping method is applied, and the seal portion is formed by thermosetting a sealing agent for the liquid crystal dropping method.

  FIG. 1 is a sectional view showing a liquid crystal display device using curable resin particles according to an embodiment of the present invention.

The liquid crystal display element 1 shown in FIG. 1 has a pair of transparent glass substrates 2. The transparent glass substrate 2 has an insulating film (not shown) on the opposite surface. Examples of the material of the insulating film include SiO _{2 and the} like. The transparent electrode 3 is formed on the insulating film of the transparent glass substrate 2. Examples of the material of the transparent electrode 3 include ITO. The transparent electrode 3 can be formed by patterning by photolithography, for example. An alignment film 4 is formed on the transparent electrode 3 on the surface of the transparent glass substrate 2. As a material of the alignment film 4, polyimide or the like is mentioned.

  A liquid crystal 5 is enclosed between the pair of transparent glass substrates 2. A plurality of spacer particles 7 are arranged between the pair of transparent glass substrates 2. The spacing between the pair of transparent glass substrates 2 is regulated by the plurality of spacer particles 7. A seal portion 6 is arranged between the peripheral edges of the pair of transparent glass substrates 2. The seal portion 6 prevents the liquid crystal 5 from flowing out. The seal portion 6 contains particles 6A obtained by curing curable resin particles. In the liquid crystal display element 1, the member located above the liquid crystal 5 is the first liquid crystal display element member, and the member located below the liquid crystal is the second liquid crystal display element member.

  From the viewpoint of further enhancing the adhesive force, further enhancing the liquid crystal contamination preventing property, and effectively lowering the moisture permeability, the above-mentioned seal portion exhibits fluidity at 23 ° C. contained in the liquid crystal dropping method sealant. It is preferable that the thermosetting compound contained therein and the curable resin particles contained in the sealant for the liquid crystal dropping method are thermally cured so as to chemically bond with each other.

  The liquid crystal display element shown in FIG. 1 is an example, and the structure of the liquid crystal display element can be appropriately changed.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The invention is not limited to the following examples.

(Example 1)
(1) Preparation of Curable Resin Particles Used for Sealant for Liquid Crystal Dropping Method An aqueous solution A was prepared by mixing 2500 parts by weight of ion-exchanged water and 1.25 parts by weight of polyoxyethylene (9) lauryl ether. In this aqueous solution A, 45 parts by weight of a modified epoxy acrylate (“EBECRYL3708” manufactured by Daicel-Onex), 15 parts by weight of a biphenyl ether type epoxy resin acrylic acid addition oligomer (“KRM8030” manufactured by Daicel-Onex), 1,2-octane 1 part by weight of dione, 1- [4- (phenylthio)-, 2- (0-benzoyloxime)] ("OXE01" manufactured by BASF), and 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd. KBM403 ") was added and stirred with a planetary stirrer. Then, after emulsifying with a Shirasu Porous Glass (SPG) membrane (pore average diameter of about 5 μm), the emulsion was added into a separable flask.

While stirring the emulsion in the separable flask, the emulsion was irradiated with ultraviolet rays of 100 mW / cm ² for 20 seconds using a metal halide lamp, and then the emulsion was semi-cured at 60 ° C. for 5 hours (curing condition). , Particles were obtained. The obtained particles were centrifuged and freeze-dried to obtain curable resin particles used as a sealant for the liquid crystal dropping method.

(Example 2)
Curable resin particles used for a sealant for a liquid crystal dropping method in the same manner as in Example 1 except that 1 part by weight of silica (“Admafine SO-C1” manufactured by Admatechs Co., Ltd.) was added to the aqueous solution A. Got

(Example 3)
Biphenyl ether type epoxy resin Acrylic acid addition oligomer was changed to bisphenol E type epoxy resin methacrylic acid addition oligomer (manufactured by Daicel Ornex Co., "KRM8276"), in the same manner as in Example 1, and a seal for liquid crystal dropping method. Curable resin particles used for the agent were obtained.

(Comparative Example 1)
Cured resin particles were obtained in the same manner as in Example 1 except that the curing conditions were changed from 60 ° C. for 5 hours to 120 ° C. for 1 hour, and curing was completed.

(Comparative example 2)
Instead of the curable resin particles used for the sealant for the liquid crystal dropping method, prepare a silicone powder (particles) obtained by removing coarse particles by passing a silicone powder (“KMP-601” manufactured by Shin-Etsu Chemical Co., Ltd.) through a 8 μm sieve. did. The silicone powder is used as particles used in the sealant for the liquid crystal dropping method of Comparative Example 2.

(Evaluation)
(1) Particle size The curable resin particles, the cured resin particles, and the silicone powder thus obtained were measured for average particle size using a laser diffraction particle size distribution analyzer (“Mastersizer 2000” manufactured by Malvern Instruments Ltd.), and averaged. The value was calculated.

(2) Prevention of liquid crystal contamination Preparation of sealant for liquid crystal dropping method:
50 parts by weight of bisphenol A type epoxy methacrylate (thermosetting compound, "KRM7985" manufactured by Daicel Ornex) and 20 parts by weight of caprolactone-modified bisphenol A type epoxy acrylate (thermosetting compound, "EBECRYL3708" manufactured by Daicel Ornex) And 30 parts by weight of partially acrylic modified bisphenol E type epoxy resin (thermosetting compound, "KRM8276" manufactured by Daicel Ornex Co., Ltd.) and 2,2-dimethoxy-2-phenylacetophenone (photoradical polymerization initiator, BASF Japan Co., Ltd.). "IRGACURE 651"), 2 parts by weight, malonic acid dihydrazide (thermosetting agent, "MDH" manufactured by Otsuka Chemical Co., Ltd.) 10 parts by weight, obtained particles 30 parts by weight, silica (filler, manufactured by Admatechs " Admafine SO-C2 20 parts by weight, 2 parts by weight of 3-glycidoxypropyltrimethoxysilane (silane coupling agent, "KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.), and core-shell acrylate copolymer fine particles (stress relaxation agent, ZEON) Chemical compound "F351") and blended with a planetary stirrer (Shinky's "Awatori Kentaro"), and then uniformly mixed with a three-roll ceramic roll to seal the liquid crystal display device. Got

Fabrication of liquid crystal display device:
1 part by weight of spacer particles having an average particle size of 5 μm (“Micropearl SP-205” manufactured by Sekisui Chemical Co., Ltd.) was uniformly dispersed in 100 parts by weight of the obtained sealant for each liquid crystal display element by a planetary stirrer. Then, the obtained spacer-containing sealant was filled in a dispensing syringe (“PSY-10E” manufactured by Musashi Engineering Co., Ltd.) to perform defoaming treatment. Then, using a dispenser ("SHOTMMASTER 300" manufactured by Musashi Engineering Co., Ltd.), a sealant was applied on a transparent electrode substrate with an ITO thin film so as to draw a rectangular frame. Subsequently, TN liquid crystal (“JC-5001LA” manufactured by Chisso Corporation) is applied with a minute drop by a liquid crystal dropping device, and the other transparent substrate is attached under a vacuum of 5 Pa using a vacuum attachment device. I matched it. The bonded cells were irradiated with 100 mW / cm ² of ultraviolet rays for 30 seconds using a metal halide lamp, and then heated at 120 ° C. for 1 hour to thermally cure the sealant, thereby setting a liquid crystal display element (cell gap 5 μm). Obtained.

Evaluation method of liquid crystal contamination prevention:
With respect to the obtained liquid crystal display element, display unevenness occurring in the liquid crystal around the seal portion (particularly the corner portion) was visually observed. The liquid crystal contamination preventive property was judged according to the following criteria.

[Criteria for liquid crystal contamination prevention]
○: No display unevenness △: Conspicuous display unevenness occurred ×: Severe display unevenness occurred

(3) Low moisture permeability (evaluation of color unevenness of liquid crystal display device driven after storage under high temperature and high humidity)
The liquid crystal display device obtained by the evaluation of (2) above was prepared.

Evaluation method of low moisture permeability:
The obtained liquid crystal display element was stored for 36 hours in an environment of a temperature of 80 ° C. and a humidity of 90% RH, and then a voltage drive of AC 3.5 V was performed, and the periphery of the halftone sealant was visually observed. Low moisture permeability was judged according to the following criteria.

[Criteria for low moisture permeability]
○ ○: No color unevenness around the seal part ○: Very slight color unevenness △: Conspicuous color unevenness ×: Severe color unevenness

(4) Adhesiveness 1 part by weight of spacer particles having an average particle diameter of 5 μm (“Micropearl SP-205” manufactured by Sekisui Chemical Co., Ltd.) per 100 parts by weight of the sealant for each liquid crystal display element produced in (2) above. The spacer-containing sealant was uniformly dispersed by a planetary stirrer, and the obtained spacer-containing sealant was filled in a dispensing syringe (“PSY-10E” manufactured by Musashi Engineering Co., Ltd.) to perform defoaming treatment. A minute amount of this is taken in the center of Corning glass 1737 (20 mm x 50 mm x thickness 1.1 mm), the same type of glass is placed on top of it and the sealant for liquid crystal dropping method is spread, and heated at 120 ° C for 1 hour. Then, the sealant was heat-cured to obtain an adhesion test piece. The adhesive strength (N / cm ² ) of each of the obtained adhesive test pieces was measured using a tension gauge.

(5) Liquid Crystal Insertion Preventing Property The shape of the seal pattern was observed with respect to the liquid crystal display device produced in (2) above. The liquid crystal insertion preventive property was judged according to the following criteria.

[Criteria for preventing liquid crystal insertion]
○ ○: The shape of the seal pattern is not disturbed by the liquid crystal inside ○: The shape of the seal pattern is slightly disturbed △: The shape of the seal pattern is disturbed, but the liquid crystal does not break through the seal pattern No ×: Liquid crystal broke through the seal pattern and leaked to the outside

  The results are shown in Table 1 below.

DESCRIPTION OF SYMBOLS 1 ... Liquid crystal display element 2 ... Transparent glass substrate 3 ... Transparent electrode 4 ... Alignment film 5 ... Liquid crystal 6 ... Seal part 6A ... Particles in which curable resin particles are cured 7 ... Spacer particles

Claims (12)

Used as a sealant for the liquid crystal dropping method, which is cured by light irradiation or heating,
In the sealing agent for the liquid crystal dropping method, the curable resin particles used as a gap control material,
A curable resin particle which is a photo-curable or thermo-curable particle and which is formed of a photo-curable compound or a thermo-curable compound and is used for a sealant for a liquid crystal dropping method.   The curable resin particle used for the sealant for a liquid crystal dropping method according to claim 1, wherein the photocurable compound or the thermosetting compound is an epoxy compound or a (meth) acrylic compound. Used as a sealant for the liquid crystal dropping method that is cured by heating,
Particles that can be heat-cured, and are semi-cured particles formed by advancing the curing of an epoxy compound having fluidity at 23 ° C or a (meth) acrylic compound having fluidity at 23 ° C. Alternatively, the curable resin particles used in the sealant for a liquid crystal dropping method according to item 2.   Curable resin particles used for the sealant for a liquid crystal dropping method according to any one of claims 1 to 3, having a particle diameter of 0.5 µm or more and 80 µm or less.   Curable resin particles containing a light-shielding agent for use in the sealant for a liquid crystal dropping method according to any one of claims 1 to 4.   The compression displacement when a load of 1 g is applied at 23 ° C. is L3, and the particle size is Dn, the strain of 1 g expressed as a percentage of L3 / Dn is 20% or more. 1. A curable resin particle used for the sealant for the liquid crystal dropping method according to item 1.   The curable resin particle according to claim 1, further comprising a polymerization initiator or a thermosetting agent. A thermosetting compound having fluidity at 23 ° C.,
With a polymerization initiator or a thermosetting agent,
A sealant for a liquid crystal dropping method, comprising the curable resin particles according to claim 1.   When heated, the thermosetting compound contained in the sealant for liquid crystal dropping method and having fluidity at 23 ° C. and the curable resin particles contained in the sealant for liquid crystal dropping method are chemically bonded to each other. The sealant for a liquid crystal dropping method according to claim 8, which is heat-curable.   The sealant for a liquid crystal dropping method according to claim 8, which does not contain a photocurable component. A first liquid crystal display element member;
A second liquid crystal display element member;
The outer periphery of the first liquid crystal display element member and the second liquid crystal display element member is sealed in a state where the first liquid crystal display element member and the second liquid crystal display element member face each other. The sealing part,
A liquid crystal disposed inside the seal portion and between the first liquid crystal display element member and the second liquid crystal display element member,
The seal portion is formed by thermosetting a sealant for a liquid crystal dropping method,
A liquid crystal display, wherein the sealing agent for the liquid crystal dropping method includes a thermosetting compound having fluidity at 23 ° C., a thermosetting agent, and the curable resin particles according to claim 1. element.   In the seal portion, the thermosetting compound contained in the sealant for liquid crystal dropping method and having fluidity at 23 ° C. and the curable resin particles contained in the sealant for liquid crystal dropping method are chemically bonded. 12. The liquid crystal display element according to claim 11, which is heat-cured.

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