WO2010058767A1 - 液晶滴下工法用シール剤及び液晶表示素子 - Google Patents
液晶滴下工法用シール剤及び液晶表示素子 Download PDFInfo
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- WO2010058767A1 WO2010058767A1 PCT/JP2009/069484 JP2009069484W WO2010058767A1 WO 2010058767 A1 WO2010058767 A1 WO 2010058767A1 JP 2009069484 W JP2009069484 W JP 2009069484W WO 2010058767 A1 WO2010058767 A1 WO 2010058767A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2003/1034—Materials or components characterised by specific properties
- C09K2003/1062—UV-curable materials
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1341—Filling or closing of cells
- G02F1/13415—Drop filling process
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/02—Materials and properties organic material
- G02F2202/022—Materials and properties organic material polymeric
- G02F2202/023—Materials and properties organic material polymeric curable
Definitions
- the present invention stably manufactures a liquid crystal display element without being accidentally cured even when it is exposed to weak light that is not intended to cure the sealing agent at the time of manufacturing a liquid crystal display element by a liquid crystal dropping method.
- the present invention relates to a sealing agent for liquid crystal dropping method.
- this invention relates to the liquid crystal display element which uses this sealing compound for liquid crystal dropping methods.
- a method for manufacturing a liquid crystal display element such as a liquid crystal display cell has been in the direction of adopting a liquid crystal dropping method in place of a conventional vacuum injection method from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used.
- a liquid crystal dropping method for example, from a photothermosetting resin composition containing a photocurable acrylic resin and a photopolymerization initiator, and a thermosetting epoxy resin and a thermopolymerization initiator.
- a liquid crystal dropping method sealing agent hereinafter also simply referred to as “sealing agent” is used.
- liquid crystal dropping method first, a seal pattern is formed on one of two transparent substrates with electrodes by screen printing. Next, fine droplets of liquid crystal are dropped onto the entire surface of the transparent substrate in a state where the sealant is uncured, the other transparent substrate is immediately overlaid, and the seal portion is irradiated with ultraviolet rays for temporary curing. Thereafter, heating is performed during liquid crystal annealing to perform main curing, thereby obtaining a liquid crystal display element. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency (for example, Patent Documents 1 and 2).
- liquid crystal display elements are also required to be downsized.
- As a means for downsizing the liquid crystal display element there is a narrow frame of the liquid crystal display unit. Along with the narrowing of the frame of the liquid crystal display part, the place where the sealing agent is arranged in the panel is also limited, and even if the ultraviolet ray is irradiated to cure the sealing agent, there may be a place where the ultraviolet ray is not irradiated. . For example, there are places where ultraviolet rays of several tens to several hundreds of ⁇ m are not irradiated under the wiring of the array.
- the sealant may be accidentally cured by the interior lighting of the work room or the illumination of various devices in the process prior to the UV irradiation process, which is originally intended to be cured.
- This problem is most likely to occur when there is a weak light source for alignment in the substrate bonding step in which oxygen having a polymerization inhibiting action is extremely reduced.
- the rate of occurrence of erroneous curing increases dramatically.
- the present invention stably manufactures a liquid crystal display element without being accidentally cured even when it is exposed to weak light that is not intended to cure the sealing agent at the time of manufacturing a liquid crystal display element by a liquid crystal dropping method. It aims at providing the sealing compound for liquid crystal dropping methods which can be performed. Moreover, an object of this invention is to provide the liquid crystal display element which uses this sealing compound for liquid crystal dropping methods.
- the present invention is a liquid crystal dropping method sealant containing a curable resin, a UV radical initiator and a radical polymerization inhibitor, wherein the curable resin comprises a curable resin having a (meth) acryl group and an epoxy group. And the ratio of the (meth) acrylic group to the epoxy group is 60:40 to 95: 5, and the UV radical initiator is measured at 350 nm measured in acetonitrile.
- the curable resin comprises a curable resin having a (meth) acryl group and an epoxy group.
- the ratio of the (meth) acrylic group to the epoxy group is 60:40 to 95: 5, and the UV radical initiator is measured at 350 nm measured in acetonitrile.
- For liquid crystal dropping method having an extinction coefficient of 500 ml ⁇ g ⁇ 1 ⁇ cm ⁇ 1 or more and a blending amount of the radical polymerization inhibitor of 0.1 to 0.4 parts by weight with respect to 100 parts by weight of the curable resin It is a sealing agent.
- the present inventors include a curable resin having a high content ratio of (meth) acrylic groups and a high reactivity of radical reaction, and a UV radical initiator having a high reactivity, so that a portion where ultraviolet rays are not irradiated is present.
- a specific amount of radical polymerization inhibitor to the sealing agent with improved UV curable properties so that it can be reliably cured even in some cases, it is exposed to weak light that is not intended to cure the sealing agent.
- the present inventors have found that a sealing agent capable of stably producing a liquid crystal display element can be obtained without being accidentally cured even if there is a case, and the present invention has been completed.
- the sealing agent of the present invention contains a curable resin.
- the curable resin is one in which a curable resin having a (meth) acryl group and a curable resin having an epoxy group coexist.
- the curable resin having the (meth) acrylic group is not particularly limited.
- an ester compound obtained by reacting a (meth) acrylic acid with a compound having a hydroxyl group, (meth) acrylic acid and an epoxy compound are reacted.
- Epoxy (meth) acrylate obtained by making it react, urethane (meth) acrylate obtained by making the (meth) acrylic acid derivative which has a hydroxyl group react with isocyanate, etc. are mentioned.
- the ester compound obtained by reacting the above (meth) acrylic acid with a compound having a hydroxyl group is not particularly limited, and examples of monofunctional compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 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, Lahydrofurfuryl (meth) acrylate, benzyl
- Examples of the bifunctional ester compound obtained by reacting the above (meth) acrylic acid with a compound having a hydroxyl group include 1,4-butanediol di (meth) acrylate and 1,3-butanediol diester.
- ester compounds obtained by reacting the above (meth) acrylic acid with a compound having a hydroxyl group those having three or more functional groups include, for example, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene Oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) 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 ( Data) acrylate, glycerin tri (me
- the epoxy (meth) acrylate obtained by reacting the (meth) acrylic acid and the epoxy compound is not particularly limited.
- an epoxy resin and (meth) acrylic acid are combined in the presence of a basic catalyst according to a conventional method. And the like obtained by reacting with.
- the epoxy compound used as a raw material for synthesizing the epoxy (meth) acrylate is not particularly limited.
- Examples of commercially available products include bisphenol A such as Epicoat 828EL and Epicoat 1004 (both manufactured by Japan Epoxy Resin Co., Ltd.).
- Type epoxy resin bisphenol F type epoxy resin such as Epicoat 806 and Epicoat 4004 (both made by Japan Epoxy Resin), bisphenol S type epoxy resin such as Epicron EXA1514 (made by DIC), and RE-810NM (Nipponization) 2,2'-diallyl bisphenol A type epoxy resin such as Yakuhin), hydrogenated bisphenol type epoxy resin such as Epicron EXA7015 (made by DIC), and propylene oxide-added bisphenol such as EP-4000S (made by ADEKA)
- A-type epoxy resin resorcinol-type epoxy resin such as EX-201 (manufactured by Nagase ChemteX), biphenyl-type epoxy resin such as Epicoat YX-4000H (manufactured by Japan Epoxy Resin), YSLV-50TE (Tohto Kasei) ), Epoxy ether resins such as YSLV-80DE (manufactured by Toto Kasei), dicyclopentadiene epoxy resins such as EP
- Naphthalene type epoxy resins such as EXA-4700 (all made by DIC), phenol novolac type epoxy resins such as Epicron N-770 (made by DIC), Epicron N-670-EXP-S (made by DIC), etc.
- Orthocresol novolac type epoxy resin Dicyclopentadiene novolac type epoxy resin such as Piclon HP7200 (manufactured by DIC), biphenyl novolac type epoxy resin such as NC-3000P (manufactured by Nippon Kayaku Co., Ltd.), naphthalene phenol such as ESN-165S (manufactured by Tohto Kasei Co., Ltd.)
- Novolac type epoxy resin Glycidylamine type epoxy resin such as Epicoat 630 (manufactured by Japan Epoxy Resin), Epicron 430 (manufactured by DIC), TETRAD-X (manufactured by Mitsubishi Gas Chemical Company), ZX-1542 (Tohto Kasei Co.,
- the epoxy (meth) acrylate obtained by reacting the (meth) acrylic acid with an epoxy compound is, for example, 360 parts by weight of EX-201 (manufactured by Nagase ChemteX Corporation) as a resorcinol type epoxy resin. Obtained by reacting 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 210 parts by weight of acrylic acid for 5 hours while stirring at 90 ° C. while feeding air. Can do.
- EX-201 manufactured by Nagase ChemteX Corporation
- Examples of commercially available epoxy (meth) acrylates include, for example, Eveacryl 3700, Evekril 3600, Evekril 3701, Evekril 3703, Evekrill 3200, Evekrill 3201, Evekril 3600, Evekril 3702, Evekril 3412, Evekril 860, Evekril RDX63182 , Evecri 6040, Evekril 3800 (all manufactured by Daicel Cytec), EA-1020, EA-1010, EA-5520, EA-5323, EA-CHD, 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, Poxy ester 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA, Epoxy ester 400EA (all manufactured by Kyoe
- the urethane (meth) acrylate obtained by reacting the isocyanate with a (meth) acrylic acid derivative having a hydroxyl group is, for example, a (meth) acrylic acid derivative 2 having a hydroxyl group with respect to 1 equivalent of a compound having two isocyanate groups.
- the equivalent weight can be obtained by reacting in the presence of a catalytic amount of a tin-based compound.
- Isocyanate that is a raw material for urethane (meth) acrylate obtained by reacting the above-mentioned isocyanate with a (meth) acrylic acid derivative having a hydroxyl group is not particularly limited.
- Isocyanate which is a raw material of urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylic acid derivative with the isocyanate is not particularly limited.
- ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly ) Chain-extended isocyanate compounds obtained by reaction of polyols such as propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and excess isocyanate can also be used.
- the (meth) acrylic acid derivative having a hydroxyl group which is a raw material for the urethane (meth) acrylate obtained by reacting the isocyanate with a hydroxyl group-containing (meth) acrylic acid derivative, is not particularly limited.
- 2-hydroxyethyl Commercial products such as (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, 1 Mono (meth) acrylates of dihydric alcohols such as 1,3-butanediol, 1,4-butanediol, polyethylene glycol, etc., mono (meth) acrylates of trivalent alcohols such as trimethylolethane, trimethylolpropane, glycerin or the like (Meth) acrylates, epoxy acrylates such as bisphenol A-modified epoxy acrylate.
- the urethane (meth) acrylate obtained by reacting the isocyanate with a (meth) acrylic acid derivative having a hydroxyl group includes, for example, 134 parts by weight of trimethylolpropane and 0.2 part by weight of BHT as a polymerization inhibitor. And 0.01 parts by weight of dibutyltin dilaurate as a reaction catalyst and 666 parts by weight of isophorone diisocyanate are reacted at 60 ° C. with stirring under reflux for 2 hours, and then 51 parts by weight of 2-hydroxyethyl acrylate is added. It can be obtained by reacting for 2 hours at 90 ° C. while refluxing while feeding air.
- urethane (meth) acrylates include, for example, M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), Evecryl 230, Evekril 270, Evekril 4858. , Evekril 8402, Evekrill 8804, Evekrill 8803, Evekrill 8807, Evekrill 9260, Evekrill 1290, Evekril 5129, Evekril 4842, Evekril 4827, Evekril 6700, Evekril 220, Evekyle Rine Tech Co., Ltd.
- the curable resin having the (meth) acryl group is preferably one having a hydrogen bonding unit such as —OH group, —NH— group, —NH 2 group, etc. from the viewpoint of suppressing adverse effects on the liquid crystal.
- Epoxy (meth) acrylate is particularly preferred from the standpoint of ease.
- the curable resin having a (meth) acryl group preferably has 2 to 3 (meth) acryl groups in the molecule because of its high reactivity.
- the reactive functional group is an acryl group from the high reactivity of the curable resin which has the said (meth) acryl group.
- the epoxy resin-containing curable resin is not particularly limited.
- examples of commercially available resins include bisphenol A type epoxy resins such as Epicoat 828EL and Epicoat 1004 (all manufactured by Japan Epoxy Resin Co., Ltd.), Epicoat 806, 2, such as bisphenol F type epoxy resin such as Epicoat 4004 (all made by Japan Epoxy Resin), bisphenol S type epoxy resin such as Epicron EXA1514 (made by DIC), RE-810NM (made by Nippon Kayaku Co., Ltd.), etc.
- 2'-diallyl bisphenol A type epoxy resin hydrogenated bisphenol type epoxy resin such as Epicron EXA7015 (manufactured by DIC), propylene oxide-added bisphenol A type epoxy resin such as EP-4000S (manufactured by ADEKA), EX- 201 Resorcinol type epoxy resin such as Sechemtex), biphenyl type epoxy resin such as Epicoat YX-4000H (Japan Epoxy Resin), sulfide type epoxy resin such as YSLV-50TE (manufactured by Tohto Kasei), YSLV- Ether type epoxy resins such as 80DE (manufactured by Toto Kasei Co., Ltd.), dicyclopentadiene type epoxy resins such as EP-4088S (manufactured by ADEKA), and naphthalenes such as Epicron HP4032 and Epicron EXA-4700 (both manufactured by DIC) Type epoxy resins, phenol novolac type epoxy resins such as Epicron N-770
- the curable resin having an epoxy group may be, for example, a compound having a (meth) acryl group and an epoxy group in one molecule.
- a compound having a (meth) acryl group and an epoxy group in one molecule for example, a compound obtained by reacting a part of an epoxy group of a compound having two or more epoxy groups with (meth) acrylic acid, and the like can be mentioned.
- the compound obtained by reacting a part of the epoxy groups having two or more epoxy groups with (meth) acrylic acid is prepared by, for example, reacting an epoxy resin and (meth) acrylic acid with a basic catalyst according to a conventional method. It is obtained by reacting in the presence. Specifically, for example, 190 g of phenol novolac type epoxy resin N-770 (manufactured by DIC) is dissolved in 500 mL of toluene, and 0.1 g of triphenylphosphine is added to this solution to obtain a uniform solution, and acrylic acid is added to this solution. 36 g was added dropwise over 2 hours under reflux stirring, and further reflux stirring was performed for 6 hours. Next, by removing toluene, a novolac-type solid modified epoxy resin in which 50 mol% of epoxy groups reacted with acrylic acid was obtained. Yes (in this case 50% partially acrylated).
- the ratio of (meth) acrylic group to epoxy group in the curable resin is 60:40 to 95: 5.
- the ratio of the (meth) acrylic group is less than 60 mol%, the curing component with ultraviolet rays is reduced to cause display unevenness, or the portion not irradiated with ultraviolet rays cannot be sufficiently cured.
- the ratio of the (meth) acrylic group exceeds 95 mol%, the adhesive strength decreases.
- the preferable lower limit of the ratio of the (meth) acrylic group is 65 mol%, the more preferable lower limit of the ratio of the (meth) acrylic group is 70 mol%, and the more preferable lower limit is 80 mol%.
- the sealing agent for liquid crystal dropping method of the present invention contains a UV radical initiator.
- the UV radical initiator has an extinction coefficient at 350 nm measured in acetonitrile of 500 ml ⁇ g ⁇ 1 ⁇ cm ⁇ 1 or more.
- Such a UV radical initiator has high reactivity, and when used in combination with the above curable resin, the sealing agent for liquid crystal dropping method of the present invention can be reliably cured even when there is a portion not irradiated with ultraviolet rays. it can.
- the extinction coefficient is less than 500 ml ⁇ g ⁇ 1 ⁇ cm ⁇ 1 , display unevenness occurs, or a portion not irradiated with ultraviolet rays cannot be sufficiently cured.
- a preferable upper limit of the extinction coefficient is 30000 ml ⁇ g ⁇ 1 ⁇ cm ⁇ 1 .
- UV radical initiators examples include Irgacure 907 (1520 ml ⁇ g ⁇ 1 ⁇ cm ⁇ 1 ), Irgacure 819 (3200 ml ⁇ g ⁇ 1 ⁇ cm ⁇ 1 ), Irgacure 651 (820 ml ⁇ g- 1 ⁇ cm ⁇ 1 ), Irgacure 369 (23000 ml ⁇ g ⁇ 1 ⁇ cm ⁇ 1 ), Irgacure 379 (20500 ml ⁇ g ⁇ 1 ⁇ cm ⁇ 1 ), Irgacure OXE01 (18000 ml ⁇ g ⁇ 1 ⁇ cm ⁇ 1 ) Irgacure 1300 (9800 ml ⁇ g ⁇ 1 ⁇ cm ⁇ 1 ), Irgacure 1800 (3100 ml ⁇ ⁇ 1 ⁇ cm ⁇ 1 ), Irgacure 1870 (3600 ml ⁇ g ⁇ 1 ⁇ 1 ⁇
- content of the said UV radical initiator is not specifically limited, A preferable minimum is 0.1 weight part and a preferable upper limit is 10 weight part with respect to 100 weight part of resin which has the said (meth) acryl group.
- content of the UV radical initiator is less than 0.1 parts by weight, the liquid crystal dropping method sealing agent of the present invention may not be sufficiently cured.
- content of the said UV radical initiator exceeds 10 weight part, storage stability may fall.
- the sealing agent for liquid crystal dropping method of the present invention contains a radical polymerization inhibitor.
- the radical polymerization inhibitor include 2,6-di-t-butylcresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl ⁇ - (3,5-di-).
- the blending amount of the radical polymerization inhibitor is such that the lower limit is 0.1 parts by weight and the upper limit is 0.4 parts by weight with respect to 100 parts by weight of the curable resin.
- the radical polymerization inhibitor is quickly consumed by radicals generated slightly when weak light is present during the production of the liquid crystal display element. In other words, when it is exposed to weak light that is not intended to cure the sealant, it is accidentally cured.
- the blending amount of the radical polymerization inhibitor exceeds 0.4 parts by weight, the ultraviolet curing property of the obtained sealing agent is remarkably lowered, and it may not be cured even when irradiated with ultraviolet rays for the purpose of curing the sealing agent.
- the said radical polymerization inhibitor is mix
- the compounding quantity is with respect to 100 weight part of curable resin which has a (meth) acryl group normally. It is about 0.05 part by weight, and hardly remains in the final sealant.
- the sealing agent for liquid crystal dropping method of the present invention preferably further contains a thermal epoxy curing agent.
- curing agent is not specifically limited, For example, organic acid hydrazide, an imidazole derivative, an amine compound, a polyhydric phenol type compound, an acid anhydride etc. are mentioned. Among these, solid organic acid hydrazide is preferable.
- the solid organic acid hydrazide is not particularly limited.
- sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, others Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J (all of which are Ajinomoto Fine Techno) And ADH (manufactured by Otsuka Chemical Co., Ltd.).
- a preferable minimum is 1 weight part and a preferable upper limit is 50 weight part with respect to 100 weight part of curable resin which has the said epoxy group.
- the content of the thermal epoxy curing agent is less than 1 part by weight, the liquid crystal dropping method sealing agent of the present invention may not be sufficiently cured.
- the content of the thermal epoxy curing agent exceeds 50 parts by weight, the viscosity of the sealing agent for liquid crystal dropping method of the present invention is increased, and the coating property and the like may be impaired.
- curing agent is 30 weight part.
- the sealing agent for liquid crystal dropping method of the present invention preferably further contains a silane coupling agent.
- a silane coupling agent for example, ⁇ -aminopropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -isocyanatopropyltrimethoxysilane and the like are preferably used.
- the sealing agent for liquid crystal dropping method of the present invention preferably contains a filler for the purpose of improving the adhesiveness by the stress dispersion effect, improving the linear expansion coefficient, and the like.
- 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, and aluminum hydroxide.
- Inorganic fillers such as silicon nitride, barium sulfate, gypsum, calcium silicate, glass beads, sericite activated clay, and aluminum nitride, and organic fillers such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles .
- the sealing agent for the liquid crystal dropping method of the present invention further comprises a reactive diluent for adjusting viscosity, a thixotropic agent for adjusting thixotropy, a spacer such as polymer beads for adjusting panel gap, if necessary, It may contain a curing accelerator such as P-chlorophenyl-1,1-dimethylurea, an antifoaming agent, a leveling agent, a thermal radical initiator and the like.
- the sealing agent for liquid crystal dropping method of the present invention preferably contains as little solvent as possible in the sealing agent, and of course, the viscosity of the sealing agent is temporarily increased during the sealing agent manufacturing process as well as not mixing the solvent as a blend. It is not preferable to mix a solvent for the purpose of lowering.
- the liquid crystal dropping method sealing agent of the present invention is produced by mixing the curable resin having the (meth) acrylic group, a UV radical initiator, a radical polymerization inhibitor, and an additive to be blended as necessary. can do. At this time, it is preferable to carry out the production under conditions where radicals are unlikely to be generated so as not to consume a small amount of the incorporated radical polymerization inhibitor. For example, when mixing using a ball mill, a large amount of radicals may be generated. On the other hand, generation of radicals can be suppressed by using a planetary stirrer (for example, manufactured by Shinky Co., Ltd., Awatori Nertaro series).
- a planetary stirrer for example, manufactured by Shinky Co., Ltd., Awatori Nertaro series.
- the liquid crystal display element manufactured using the sealing agent for liquid crystal dropping methods of this invention is also one of this invention.
- the liquid crystal display element when a liquid crystal display element is manufactured by a liquid crystal dropping method, the liquid crystal display element can be stably cured without being erroneously cured even when exposed to weak light that is not intended to cure the sealant. It is possible to provide a sealant for a liquid crystal dropping method capable of producing a liquid crystal. Moreover, according to this invention, the liquid crystal display element which uses this sealing compound for liquid crystal dropping methods can be provided.
- Examples 1 to 7 and Comparative Examples 1 to 7 In accordance with the blending ratios described in Tables 1 and 2, each material was mixed using a planetary stirrer (manufactured by Sinky Corporation, “Awatori Nertaro”), and then further mixed using three rolls. The sealants for liquid crystal dropping method of 1 to 7 and Comparative Examples 1 to 7 were prepared.
- UV radical initiator used in Examples and Comparative Examples, the measured extinction coefficient at 350nm in acetonitrile, Irgacure 184 350ml ⁇ g -1 ⁇ cm -1, Irgacure 651 820 ml ⁇ g -1 ⁇ cm ⁇ 1 and Irgacure 819 were 3200 ml ⁇ g ⁇ 1 ⁇ cm ⁇ 1 .
- the obtained sealing agent for liquid crystal dropping method was drawn on a substrate on which a black matrix (BM) and a transparent electrode were formed with a dispenser so as to draw a frame. Subsequently, fine droplets of liquid crystal (manufactured by Chisso Corporation, “JC-5004LA”) were dropped onto the entire surface of the substrate frame, and another substrate with a transparent electrode (without BM) was immediately overlaid. At this time, the drawing was performed so that the line width of the crushed sealant was about 1.2 mm, and 0.3 mm of the sealant overlapped with BM.
- BM black matrix
- JC-5004LA fine droplets of liquid crystal
- the sealing material is thermally cured by irradiating UV light at 100 mW / cm 2 for 30 seconds from the substrate side on which the BM is formed using 100 mW / cm 2 and further performing liquid crystal annealing at 120 ° C. for 1 hour.
- an element for liquid crystal display was obtained.
- For the obtained liquid crystal display panel visually observe the color unevenness that occurs in the vicinity of the seal part. If there is no color unevenness, “ ⁇ ”, if there is almost no color unevenness, “ ⁇ ”, if there is a little color unevenness. The case where there was considerable “ ⁇ ” and uneven color was evaluated as “x” in four stages. The above observation was performed in a state where no power was supplied (non-lighting) and a state where power was supplied (lighting).
- Adhesive strength 3 parts by weight of polymer beads having an average particle diameter of 5 ⁇ m (“Micropearl SP”, manufactured by Sekisui Chemical Co., Ltd.) are dispersed by a planetary stirrer with respect to 100 parts by weight of the obtained liquid crystal dropping method sealing agent.
- a planetary stirrer To obtain a uniform solution. A very small amount of the obtained liquid was placed in the center of a glass substrate Corning 1737 (20 mm ⁇ 50 mm ⁇ 0.7 mmt), and the same type of glass substrate was overlaid thereon to spread the liquid crystal dropping method sealant. In that state, 100 mW / cm 2 of ultraviolet rays were irradiated for 30 seconds. Then, it heated at 120 degreeC for 1 hour, and obtained the adhesion test piece. About the obtained test piece, the adhesive strength was measured using the tension gauge (comparative unit: N / cm ⁇ 2 >).
- the obtained sealing agent for liquid crystal dropping method was applied in a spot shape on a slide glass, placed in a glass transparent vacuum desiccator and left under a fluorescent lamp in a vacuum state of 3 torr. After being left for 5, 20, and 60 minutes, a glass slide not coated with a liquid crystal dropping method sealant was bonded to a predetermined gap distance. At this time, whether or not the applied sealing agent for the liquid crystal dropping method was crushed was visually observed, and the case where it was crushed was evaluated as “ ⁇ ”, and the case where it was not crushed was evaluated as “x”.
- a substrate 1 having chromium deposited on one half of a 0.7 mm thick Corning glass and a substrate 2 having chromium deposited on the front surface were prepared (FIG. 1A).
- the sealing agent for liquid crystal dropping method was applied to the boundary portion between the portion where the chromium deposition was performed on the substrate 1 and the portion where the chromium deposition was not performed, and the substrate 2 was bonded together and then sufficiently crushed. As a result, the sealing agent for the liquid crystal dropping method spread widely on the substrate (FIG. 1B).
- the bonded substrate was irradiated with ultraviolet light at 100 mW / cm 2 for 30 seconds from the surface of the substrate 1 (FIG. 1B). Thereafter, the substrate 1 and the substrate 2 are broken, and chromium deposition is performed from the boundary between the portion directly irradiated with ultraviolet rays (the location 1, the portion not covered with chromium deposition) and the portion not subjected to chromium deposition.
- the sealant on the spot (place 2), the spot 200 ⁇ m (place 3), and the spot (place 4) containing 300 ⁇ m in the applied part was collected (FIG. 1 (c)).
- the spectrum of the collected sealant was measured by a microscopic IR method, and the conversion rate of the (meth) acryl functional group in the sealant was determined from each spectrum.
- the peak area of 810 m ⁇ 1 was used for quantification of the (meth) acryl functional group.
- the liquid crystal display element when a liquid crystal display element is manufactured by a liquid crystal dropping method, the liquid crystal display element can be stably cured without being erroneously cured even when exposed to weak light that is not intended to cure the sealant. It is possible to provide a sealant for a liquid crystal dropping method capable of producing a liquid crystal. Moreover, according to this invention, the liquid crystal display element which uses this sealing compound for liquid crystal dropping methods can be provided.
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Abstract
Description
液晶滴下工法による液晶表示素子の製造には、例えば、光硬化性のアクリル樹脂と光重合開始剤、及び、熱硬化性のエポキシ樹脂と熱重合開始剤を含有する、光熱硬化型樹脂組成物からなる液晶滴下工法用シール剤(以下、単に「シール剤」ともいう。)が用いられる。
液晶表示部の狭額縁化に伴い、シール剤がパネル中に配置される場所も制限され、シール剤を硬化させるために紫外線を照射しても、紫外線が照射されない箇所が生じてしまうことがある。例えば、アレイの配線下には数十μm~数百μmの紫外線が照射されない箇所が生じる。
以下に本発明を詳述する。
上記硬化性樹脂は、(メタ)アクリル基を有する硬化性樹脂とエポキシ基を有する硬化性樹脂とが共存するものである。
上記UVラジカル開始剤は、アセトニトリル中で測定した350nmにおける吸光係数が500ml・g-1・cm-1以上である。このようなUVラジカル開始剤は反応性が高く、上記硬化性樹脂と組み合わせて用いることにより、本発明の液晶滴下工法用シール剤は、紫外線が照射されない箇所がある場合でも確実に硬化させることができる。上記吸光係数が500ml・g-1・cm-1未満であると、表示ムラが発生したり、紫外線が照射されない箇所を充分に硬化させることができなかったりする。上記吸光係数の好ましい上限は30000ml・g-1・cm-1である。
上記ラジカル重合禁止剤は、例えば、2,6-ジ-t-ブチルクレゾール、ブチル化ヒドロキシアニソール、2,6-ジ-t-ブチル-4 -エチルフェノール、ステアリルβ-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)、2,2’-メチレンビス(4-エチル-6-t-ブチルフェノール)、4,4’-チオビス-3-メチル-6-t-ブチルフェノール)、4,4-ブチリデンンビス(3-メチル-6-t-ブチルフェノール)、3,9 -ビス[1,1-ジメチル-2-[β-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ]エチル]、2,4,8,10-テトラオキサスピロ[5,5]ウンデカン、テトラキス-[メチレン-3-(3’,5’-ジ-t-ブチル-4’-ヒドロキシフェニル)プロピオネート]メタン、1,3,5-トリス(3’,5’-ジ-t-ブチル-4’-ヒドロキシベンジル)-sec-トリアジン-2,4,6-(1H,3H,5H)トリオン、ハイドロキン、パラメトキシフェノール等が挙げられる。これらのラジカル重合禁止剤は単独で用いてもよく、2種以上を併用してもよい。
なお、上記ラジカル重合禁止剤は、上記(メタ)アクリル基を有する硬化性樹脂の合成段階でも配合されているが、配合量は通常(メタ)アクリル基を有する硬化性樹脂100重量部に対して0.05重量部程度であり、最終的なシール剤にはほとんど残留はしていない。
上記熱エポキシ硬化剤は特に限定されず、例えば、有機酸ヒドラジド、イミダゾール誘導体、アミン化合物、多価フェノール系化合物、酸無水物等が挙げられる。なかでも、固形の有機酸ヒドラジドが好適である。
上記シランカップリング剤としては、例えば、γ-アミノプロピルトリメトキシシラン、γ-メルカプトプロピルトリメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-イソシアネートプロピルトリメトキシシラン等が好適に用いられる。
上記フィラーは、例えば、タルク、石綿、シリカ、珪藻土、スメクタイト、ベントナイト、炭酸カルシウム、炭酸マグネシウム、アルミナ、モンモリロナイト、酸化亜鉛、酸化鉄、酸化マグネシウム、酸化錫、酸化チタン、水酸化マグネシウム、水酸化アルミニウム、窒化珪素、硫酸バリウム、石膏、珪酸カルシウム、ガラスビーズ、セリサイト活性白土、窒化アルミニウム等の無機フィラーや、ポリエステル微粒子、ポリウレタン微粒子、ビニル重合体微粒子、アクリル重合体微粒子等の有機フィラーが挙げられる。
EX-201(レゾルシノール型エポキシ樹脂)111gをトルエン500mLに溶解させ、これにトリフェニルホスフィン0.1gを加え、均一な溶液とした。この溶液にアクリル酸72gを還流撹拌下2時間かけて滴下後、更に還流撹拌を8時間行った。
次に、トルエンを除去することによって、全てのエポキシ基をアクリル基に変成したエポキシアクリレート(EX-201アクリル変性品)を合成した。
EX-201(レゾルシノール型エポキシ樹脂)111gをトルエン500mLに溶解させ、これにトリフェニルホスフィン0.1gを加え、均一な溶液とした。この溶液にメタクリル酸85gを還流撹拌下2時間かけて滴下後、更に還流撹拌を8時間行った。
次に、トルエンを除去することによって、全てのエポキシ基をアクリル基に変成したエポキシアクリレート(EX-201メタクリル変性品)を合成した。
N-770(フェノールノボラック型エポキシ樹脂)190gをトルエン500mLに溶解させ、この溶液にトリフェニルホスフィン0.1gを加え、均一な溶液とし、この溶液にアクリル酸36gを還流撹拌下2時間かけて滴下後、更に還流撹拌を6時間行い、次に、トルエンを除去することによって50mol%のエポキシ基をアクリル基に変性した部分アクリル化エポキシアクリレート(N-770部分アクリル変性品)を得た。
表1、2に記載した配合比に従い、各材料を、遊星式撹拌機(シンキー社製、「あわとり練太郎」)を用いて混合後、更に3本ロールを用いて混合させることにより実施例1~7、比較例1~7の液晶滴下工法用シール剤を調製した。
実施例及び比較例で得られた液晶滴下公報用シール剤を以下の方法により評価した。
結果を表1、2に示した。
ブラックマトリックス(BM)と透明電極とが形成された基板に、得られた液晶滴下工法用シール剤を枠を描くようにディスペンサーで描画した。続いて液晶(チッソ社製、「JC-5004LA」)の微小滴を基板の枠内全面に滴下塗布し、すぐに別の透明電極付き基板(BMなし)を重ね合わせた。このとき、押しつぶされたシール剤の線幅が約1.2mmであり、そのうちの0.3mmがBMと重なるように描画した。
得られた液晶表示パネルについてシール部近辺に生じる色むらを目視にて観察し、色むらが全くない場合を「◎」、色むらがほとんどない場合を「○」、少し色むらがある場合を「△」、色むらがかなりある場合を「×」と、4段階で評価した。
上記観察は、通電しない状態(非点灯)と通電した状態(点灯)とでそれぞれ行った。
得られた液晶滴下工法用シール剤100重量部に対して平均粒径5μmのポリマービーズ(積水化学工業社製、「ミクロパールSP」)3重量部を遊星式撹拌装置によって分散させ、均一な液とした。得られた液の極微量をガラス基板コーニング1737(20mm×50mm×0.7mmt)の中央部に取り、同型のガラス基板をその上に重ね合わせて液晶滴下工法用シール剤を押し広げた。その状態で100mW/cm2の紫外線を30秒照射した。その後、120℃で1時間加熱を行い、接着試験片を得た。得られた試験片について、テンションゲージを用いて接着強度を測定した(比較単位:N/cm2)。
得られた液晶滴下工法用シール剤をスライドガラス上に点状に塗布し、ガラス製の透明真空デシケータに入れ3torrの真空にした状態で蛍光灯の下に放置した。
5、20及び60分間放置後、液晶滴下工法用シール剤を塗布していないスライドガラスを、所定のギャップ間距離となるように貼り合わせた。このとき、塗布していた液晶滴下工法用シール剤が潰れるかどうかを目視にて観察し、潰れた場合を「○」と、潰れない場合を「×」と評価した。
厚さ0.7mmのコーニングガラスの半面にクロム蒸着を施した基板1と、前面にクロム蒸着を施した基板2とを準備した(図1(a))。
基板1のクロム蒸着を施した部分と、していない部分との境界部に液晶滴下工法用シール剤を点状に塗布し、基板2を貼り合わせてから充分に押しつぶした。これにより、液晶滴下工法用シール剤は基板上に大きく広がった(図1(b))。
Claims (3)
- 硬化性樹脂、UVラジカル開始剤及びラジカル重合禁止剤を含有する液晶滴下工法用シール剤であって、
前記硬化性樹脂は、(メタ)アクリル基を有する硬化性樹脂とエポキシ基を有する硬化性樹脂とが共存するものであって、前記(メタ)アクリル基とエポキシ基との比が60:40~95:5であり、
前記UVラジカル開始剤は、アセトニトリル中で測定した350nmにおける吸光係数が500ml・g-1・cm-1以上であり、
前記ラジカル重合禁止剤の配合量が前記硬化性樹脂100重量部に対して0.1~0.4重量部である
ことを特徴とする液晶滴下工法用シール剤。 - (メタ)アクリル基はアクリル基であることを特徴とする請求項1記載の液晶滴下工法用シール剤。
- 請求項1又は2記載の液晶滴下工法用シール剤を用いて製造されたことを特徴とする液晶表示素子。
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