WO2016021628A1 - 液晶滴下工法用シール剤、上下導通材料、及び、液晶表示素子 - Google Patents
液晶滴下工法用シール剤、上下導通材料、及び、液晶表示素子 Download PDFInfo
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- WO2016021628A1 WO2016021628A1 PCT/JP2015/072207 JP2015072207W WO2016021628A1 WO 2016021628 A1 WO2016021628 A1 WO 2016021628A1 JP 2015072207 W JP2015072207 W JP 2015072207W WO 2016021628 A1 WO2016021628 A1 WO 2016021628A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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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
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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
Definitions
- the present invention relates to a sealant for a liquid crystal dropping method capable of satisfying both suppression of seal break and liquid crystal contamination and suppression of gap failure due to springback. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods.
- Patent Document 1 and Patent Document 2 a method for manufacturing a liquid crystal display element such as a liquid crystal display cell has been disclosed in, for example, Patent Document 1 and Patent Document 2 from the conventional vacuum injection method from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used.
- a liquid crystal dropping method called a dripping method using such a photothermal combined curing type sealant has become the mainstream.
- a rectangular seal pattern is formed on one of two transparent substrates with electrodes by dispensing.
- a liquid crystal micro-droplet is dropped on the entire surface of the transparent substrate frame with the sealant being uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays to perform temporary curing.
- heating is performed at the time of liquid crystal annealing to perform main curing, and a liquid crystal display element is manufactured. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency.
- the liquid crystal Since the uncured sealant comes into contact with the liquid crystal, the liquid crystal is inserted into the sealant, a seal break occurs and the liquid crystal leaks out, or the uncured photocurable resin elutes after the temporary curing process. There was a problem that the liquid crystal may be contaminated.
- An object of the present invention is to provide a sealing agent for a liquid crystal dropping method capable of achieving both suppression of seal break and liquid crystal contamination and suppression of gap failure due to springback. Moreover, an object of this invention is to provide the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods.
- the present invention is a liquid crystal dropping method sealing agent used in the production of a liquid crystal display element by a liquid crystal dropping method, which contains a curable resin, a polymerization initiator and / or a thermosetting agent, and flexible particles,
- the particles are a sealing agent for a liquid crystal dropping method in which the mode particle size is 1.07 times or more the median particle size in the particle size distribution.
- the present inventors blended soft particles in a liquid crystal dropping method sealing agent, and caused the soft particles to serve as a barrier between other sealing agent components and liquid crystal, thereby generating seal breakage and liquid crystal contamination.
- a cell gap defect due to springback may occur in the obtained liquid crystal display element. Therefore, as a result of intensive studies, the present inventors have determined that, by blending soft particles having a mode particle size larger than a specific value by a specific value larger than the median particle size in the particle size distribution, it is possible to suppress seal break and liquid crystal contamination and to perform springback. It has been found that a sealing agent for a liquid crystal dropping method capable of achieving both suppression of gap defects can be obtained, and the present invention has been completed.
- the sealant for a liquid crystal dropping method of the present invention is used for manufacturing a liquid crystal display element by a liquid crystal dropping method.
- the sealing agent for liquid crystal dropping method of the present invention contains flexible particles.
- the flexible particles serve as a barrier between the other sealing agent component and the liquid crystal, preventing the liquid crystal from being inserted into the sealing agent and the sealing agent from being eluted into the liquid crystal. Have a role to play. Further, by blending the flexible particles, it is possible to prevent the substrate from being displaced until the sealing agent is cured after the substrates are bonded together.
- the flexible particles have a mode particle size of 1.07 or more times the median particle size in the particle size distribution.
- the mode particle diameter of the flexible particle is 1.07 times or more of the median particle diameter, both the seal break and liquid crystal contamination can be suppressed, and the cell gap defect can be suppressed by springback.
- the flexible particles preferably have a mode particle size larger than 1.07 times the median particle size, and more preferably larger than 1.10 times.
- the mode particle size, the median particle size, the maximum particle size, the minimum particle size, and the average particle size in the flexible particles are measured using a Coulter type particle size distribution measuring device. The value obtained by doing.
- Multisizer 4 manufactured by Beckman Coulter, Inc.
- 0.1 g of particles are added to 10 g of methanol to be acclimatized, and ultrasonic dispersion is performed for 5 minutes.
- the “mode particle size” means a particle size indicating the maximum frequency of the particle size distribution by volume frequency.
- a computer system for data processing (Beckman -It can be calculated using a device connected to Coulter).
- the aperture pore diameter is 50 ⁇ m
- the measurement range of 1 to 30 ⁇ m is divided into 300
- the frequency value is calculated on a volume basis
- the particle diameter indicating the maximum frequency can be calculated.
- the “medium particle size” means a particle size when the volume of particles larger than the particle size occupies 50% of the volume of all particles in the particle size distribution by volume frequency.
- the particle size distribution measured by using the apparatus can be calculated using an apparatus connected to a computer system for data processing (manufactured by Beckman Coulter).
- the aperture pore size is 50 ⁇ m
- the measurement range of 1-30 ⁇ m is divided into 300
- the frequency value is calculated on a volume basis
- the particle size of 50% from the smallest volume integral is the medium.
- the particle diameter can be calculated.
- the “maximum particle size” is a particle size distribution measured using the Coulter type particle size distribution measuring device. As the particle size increases from the mode particle size, the volume frequency decreases continuously, and the particles are detected. The particle diameter immediately before being stopped is defined as the maximum particle diameter. Note that particles whose volume frequency is detected discontinuously are highly likely to be aggregated particles, and are therefore excluded from the maximum particle size.
- the “minimum particle size” is 1.05 ⁇ m, which is the lower limit of detection with a 50 ⁇ m aperture used uniformly, regardless of the sample to be measured.
- the “average particle size” can be calculated using a device connected to a data processing computer system (manufactured by Beckman Coulter, Inc.) in the particle size distribution measured using the Coulter particle size distribution measuring device. .
- the pore diameter of the aperture is 50 ⁇ m
- the measurement range of 1 to 30 ⁇ m is divided into 300
- the average particle diameter can be calculated on a volume basis.
- D90 to be described later means a particle diameter when the volume of particles larger than the particle diameter occupies 10% of the volume of all particles in the particle size distribution by volume frequency, and the above-mentioned Coulter type particle size distribution measuring apparatus is used.
- the measured particle size distribution can be calculated using a device connected to a data processing computer system (manufactured by Beckman Coulter).
- the aperture pore diameter is 50 ⁇ m
- the measurement range of 1 to 30 ⁇ m is divided into 300
- the particle diameter of 90% from the smaller volume integral ratio can be calculated as D90.
- the flexible particle has a D90 in the cumulative distribution of less than 1.40 times the median particle size. It is preferable that it is less than 1.35 times.
- the above-mentioned flexible particles have a particle size distribution that is 2 ⁇ m smaller than the median particle size from the minimum particle size in terms of particle size distribution from the viewpoint of more effectively achieving both seal break and liquid crystal contamination suppression and suppression of cell gap failure by springback.
- W / Z ⁇ 1.1 where the ratio of volume frequency up to W (%) and the ratio of volume frequency from the particle diameter 2 ⁇ m larger than the median particle diameter to the maximum particle diameter is Z (%). It is preferable that W / Z ⁇ 1.2.
- the above-mentioned flexible particles have a medium particle size from 2 ⁇ m smaller than the medium particle size in the particle size distribution.
- X + Y ⁇ 60 where X (%) is the volume frequency ratio to the diameter and Y (%) is the volume frequency ratio from the median particle diameter to the particle diameter 2 ⁇ m larger than the median particle diameter.
- X + Y ⁇ 70 is more preferable.
- the above-mentioned flexible particles have a maximum particle size from a particle size 2 ⁇ m larger than the median particle size, from the viewpoint of more effectively suppressing seal break and liquid crystal contamination and suppressing cell gap failure by springback.
- the total volume frequency that is, Z is less than 10% of the total, and the total volume frequency from the smallest particle diameter to a particle diameter 2 ⁇ m smaller than the median particle diameter, ie, the W is Preferably it is less than 20%.
- Examples of a method for setting the mode particle diameter of the soft particles to 1.07 times or more of the median particle size include, for example, a method of classifying soft particles whose mode particle size is less than 1.07 times the median particle size. And a method of mixing two or more kinds of soft particles having different particle size distributions.
- Examples of the method for classifying the flexible particles include wet classification and dry classification. Of these, wet classification is preferable, and wet sieving classification is more preferable. Specifically, for example, a method in which a slurry in which flexible particles are dispersed in an appropriate dispersion medium is sieved using a high-precision sieve or the like having uniform openings is preferably used.
- the flexible particles preferably have a maximum particle size of 100% or more of the cell gap of the liquid crystal display device and 5 to 50 ⁇ m. If the maximum particle size of the flexible particles is less than 100% of the cell gap of the liquid crystal display element or less than 5 ⁇ m, seal breakage and liquid crystal contamination may not be sufficiently suppressed. If the maximum particle diameter of the flexible particles exceeds 50 ⁇ m, spring back may occur, and the resulting liquid crystal dropping method sealant may have poor adhesion, or a gap defect may occur in the resulting liquid crystal display element. is there. A more preferable upper limit of the maximum particle diameter of the flexible particles is 12 ⁇ m, and a more preferable upper limit is 15 ⁇ m. The maximum particle size of the flexible particles is preferably 2.6 times or less of the cell gap.
- the maximum particle size of the flexible particles exceeds 2.6 times the cell gap, a springback occurs, and the obtained liquid crystal dropping method sealant is inferior in adhesiveness or the obtained liquid crystal display element has a gap defect. May occur.
- a more preferable upper limit of the maximum particle diameter of the flexible particles is 2.2 times the cell gap, and a more preferable upper limit is 1.7 times the cell gap.
- the cell gap of the liquid crystal display element is not limited because it varies depending on the display element, but the cell gap of a general liquid crystal display element is 2 to 10 ⁇ m.
- the content ratio of particles having a particle diameter of 5 ⁇ m or more in the particle size distribution of the flexible particles measured by the Coulter type distribution measuring device is preferably 60% or more by volume frequency.
- the content ratio of particles having a particle diameter of 5 ⁇ m or more is less than 60% in terms of volume frequency, seal breakage and liquid crystal contamination may not be sufficiently suppressed.
- the content ratio of particles having a particle diameter of 5 ⁇ m or more is more preferably 80% or more.
- the flexible particles contain 100% or more of the cell gap of the liquid crystal display element by 70% or more of the particle size distribution in the entire flexible particles from the viewpoint of further exerting the effect of suppressing the occurrence of seal break and liquid crystal contamination. It is preferable that the liquid crystal display element is composed only of particles having a cell gap of 100% or more.
- the preferable lower limit of the average particle diameter of the flexible particles is 2 ⁇ m, and the preferable upper limit is 15 ⁇ m. If the average particle size of the flexible particles is less than 2 ⁇ m, the occurrence of seal breaks and liquid crystal contamination may not be sufficiently suppressed. When the average particle diameter of the flexible particles exceeds 15 ⁇ m, the obtained sealing agent for liquid crystal dropping method may be inferior in adhesiveness, or a gap defect may occur in the obtained liquid crystal display element.
- a more preferable lower limit of the average particle diameter of the flexible particles is 4 ⁇ m, a more preferable upper limit is 12 ⁇ m, and a further preferable lower limit is 5 ⁇ m.
- the coefficient of variation (hereinafter also referred to as “CV value”) of the flexible particles is preferably 30% or less.
- the CV value of the particle diameter of the flexible particles exceeds 30%, a cell gap defect may be caused.
- the CV value of the particle diameter of the flexible particles is more preferably 28% or less.
- the CV value of the particle diameter is a numerical value obtained by the following formula in the particle size distribution measured using the Coulter particle size distribution measuring apparatus.
- CV value of particle diameter (%) (standard deviation of particle diameter / average particle diameter) ⁇ 100
- the maximum particle diameter, average particle diameter, and CV value are within the above-mentioned ranges by classification by the above-described method. Can be inside.
- flexible particles having a particle diameter of less than 100% of the cell gap of the liquid crystal display element do not contribute to the suppression of seal break and liquid crystal contamination, and may increase the thixo value when mixed with a sealant. It is preferable to remove it.
- the above-mentioned flexible particles have a compression displacement from the load value for the origin when the load is applied to the reverse load value as L1, and the unloading displacement from the reverse load value when the load is released to the load value for the origin.
- L2 / L1 is preferably 80% or less. If the recovery rate of the flexible particles exceeds 80%, the effect of suppressing the occurrence of seal breaks and liquid crystal contamination may not be sufficiently exhibited.
- a more preferable upper limit of the recovery rate of the flexible particles is 70%, and a more preferable upper limit is 60%.
- grain can be derived
- the flexible particles preferably have a 1 g strain expressed as a percentage of L3 / Dn as a percentage of 30% or more when the compression displacement when a load of 1 g is applied is L3 and the particle diameter is Dn. If the 1 g strain of the flexible particles is less than 30%, the effect of suppressing the occurrence of seal break and liquid crystal contamination may not be sufficiently exhibited. A more preferable lower limit of 1 g strain of the flexible particles is 40%.
- the 1 g strain of the flexible particles can be derived by applying a load of 1 g to each particle using a micro compression tester and measuring the amount of displacement at that time.
- the flexible particles preferably have a fracture strain expressed as a percentage of L4 / Dn of 50% or more, where L4 is the compression displacement when the particles are broken and Dn is the particle diameter.
- L4 is the compression displacement when the particles are broken
- Dn is the particle diameter.
- the fracture strain of the flexible particles can be derived by applying a load to one particle using a micro compression tester and measuring the displacement at which the particle breaks.
- the compression displacement L4 is calculated as the time when the particle breaks when the amount of displacement increases discontinuously with respect to the applied load. If the deformation does not break even if the load is increased, the fracture strain is considered to be 100% or more.
- the flexible particles have a preferable lower limit of the glass transition temperature of ⁇ 200 ° C. and a preferable upper limit of 40 ° C.
- the lower the glass transition temperature of the flexible particles the better the sealing breakage and liquid crystal contamination.
- the temperature is lower than -200 ° C, the particles may be handled with difficulty or the sealing agent may be crushed during heating. In some cases, the sealing agent in the middle of curing and the liquid crystal come into contact with each other to cause liquid crystal contamination.
- the glass transition temperature of the flexible particles exceeds 40 ° C., a gap defect may occur.
- a more preferable lower limit of the glass transition temperature of the flexible particles is ⁇ 150 ° C., and a more preferable upper limit is 35 ° C.
- the glass transition temperature of the said flexible particle shows the value measured by the differential scanning calorimetry (DSC) based on "the plastics transition temperature measuring method" of JISK7121.
- the flexible particles include silicone particles, vinyl particles, urethane particles, fluorine particles, and nitrile particles. Of these, silicone particles and vinyl particles are preferable.
- the silicone-based particles are preferably silicone rubber particles from the viewpoint of dispersibility in the resin.
- examples of commercially available silicone particles include KMP-594, KMP-597, KMP-598, KMP-600, KMP-601, KMP-602 (manufactured by Shin-Etsu Chemical Co., Ltd.), Trefil E- 506S, EP-9215 (manufactured by Dow Corning Toray), etc., and these may be used by adjusting the mode particle size to be 1.07 times or more of the median particle size by classification or mixing. it can.
- grains may be used independently and 2 or more types may be used together.
- the (meth) acrylic particles are preferably used as the vinyl particles.
- the (meth) acrylic particles can be obtained by polymerizing monomers as raw materials by a known method. Specifically, for example, a method in which a monomer is suspension-polymerized in the presence of a radical polymerization initiator, and a seed particle is swollen by absorbing the monomer into a non-crosslinked seed particle in the presence of a radical polymerization initiator. And a seed polymerization method.
- the mode particle size of the obtained particles is less than 1.07 times the median particle size
- the mode particle size is 1.07 times or more of the median particle size by classification or mixing. adjust.
- the “(meth) acryl” means acryl or methacryl.
- Examples of the monomer that is a raw material for forming the (meth) acrylic particles include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and hexyl (meth).
- Alkyl (meth) such as acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, etc.
- oxygen-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate, etc.
- (meth) nitrile and containing monomers such as acrylonitrile, trifluoromethyl (meth) acrylate, monofunctional monomer such as a fluorine-containing (meth) acrylates such as pentafluoroethyl (meth) acrylate.
- alkyl (meth) acrylates are preferable because the Tg of the homopolymer is low and the deformation amount when a 1 g load is applied can be increased.
- the “(meth) acrylate” means acrylate or methacrylate.
- tetramethylol methane tetra (meth) acrylate tetramethylol methane tri (meth) acrylate, tetramethylol methane di (meth) acrylate, trimethylol propane tri (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, ( Poly) tetramethylene di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, isocyanuric acid
- the preferable lower limit is 1% by weight and the preferable upper limit is 90% by weight in the whole monomer.
- the amount of the crosslinkable monomer used is 1% by weight or more, the solvent resistance is improved, and when kneaded with various sealant raw materials, problems such as swelling do not occur and it becomes easy to disperse uniformly.
- the amount of the crosslinkable monomer used is 90% by weight or less, the recovery rate can be lowered, and problems such as springback are less likely to occur.
- a more preferable lower limit of the amount of the crosslinkable monomer used is 3% by weight, and a more preferable upper limit is 80% by weight.
- styrene monomers such as styrene and ⁇ -methylstyrene
- vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether, vinyl acetate, vinyl butyrate, and laurin.
- Acid vinyl esters such as vinyl acid and vinyl stearate, unsaturated hydrocarbons such as ethylene, propylene, isoprene and butadiene, halogen-containing monomers such as vinyl chloride, vinyl fluoride and chlorostyrene, triallyl (iso ) Using monomers such as cyanurate, triallyl trimellitate, divinylbenzene, diallylphthalate, diallylacrylamide, diallyl ether, ⁇ - (meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, vinyltrimethoxysilane Good .
- vinyl particles for example, polydivinylbenzene particles, polychloroprene particles, butadiene rubber particles and the like may be used.
- urethane-based particles examples include Art Pearl (manufactured by Negami Kogyo Co., Ltd.) and Dimic Beads (manufactured by Dainichi Seika Kogyo Co., Ltd.). It can be used by adjusting so that the particle size is 1.07 times or more of the median particle size.
- the preferable lower limit of the hardness of the flexible particles is 10, and the preferable upper limit is 50.
- the obtained sealing agent for liquid crystal dropping method may be inferior in adhesiveness, or a gap defect may occur in the obtained liquid crystal display element.
- the more preferable lower limit of the hardness of the soft particles is 20, and the more preferable upper limit is 40.
- the hardness of the said flexible particle means the durometer A hardness measured by the method based on JISK6253.
- the content of the soft particles is preferably 15 parts by weight with respect to 100 parts by weight of the curable resin, and 50 parts by weight with a preferable upper limit. If the content of the flexible particles is less than 15 parts by weight, the elution of the sealing agent into the liquid crystal may not be sufficiently prevented. If the content of the soft particles exceeds 50 parts by weight, the obtained liquid crystal dropping method sealing agent may be inferior in applicability and adhesiveness.
- grain is 20 weight part, and a more preferable upper limit is 40 weight part.
- the sealing agent for liquid crystal dropping method of the present invention contains a curable resin.
- the curable resin preferably contains a (meth) acrylic resin. Since the sealing agent for liquid crystal dropping method of the present invention can be cured quickly, it contains a (meth) acrylic resin as a curable resin and a radical polymerization initiator described later as a polymerization initiator. Preferably, it becomes possible to quickly cure the liquid crystal dropping method sealing agent of the present invention only by heating, and even in a liquid crystal display element with a narrow frame design, the occurrence of liquid crystal contamination can be sufficiently suppressed, It is more preferable to contain a (meth) acrylic resin and a thermal radical polymerization initiator described later. More preferably, the curable resin contains an epoxy (meth) acrylate.
- the “(meth) acrylic resin” means a resin having a (meth) acryloyl group
- the “(meth) acryloyl group” means an acryloyl group or a methacryloyl group.
- the “epoxy (meth) acrylate” means a compound obtained by reacting all epoxy groups in the epoxy resin with (meth) acrylic acid.
- Examples of the epoxy resin used as a raw material for synthesizing the epoxy (meth) acrylate include, for example, 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 epoxy resin, ortho-cresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphtha Emissions phenol novolak type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compounds, bisphenol A type episulfide resins.
- Examples of commercially available bisphenol A type epoxy resins include jER828EL, jER1001, jER1004 (all manufactured by Mitsubishi Chemical Corporation), Epicron 850-S (manufactured by DIC Corporation), and the like.
- As what is marketed among the said bisphenol F-type epoxy resins jER806, jER4004 (all are the Mitsubishi Chemical company make) etc. are mentioned, for example.
- As what is marketed among the said bisphenol S-type epoxy resins, Epicron EXA1514 (made by DIC Corporation) etc. are mentioned, for example.
- Examples of commercially available 2,2′-diallylbisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
- Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
- Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
- Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
- Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
- Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
- Examples of commercially available glycidylamine type epoxy resins include jER630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
- Examples of commercially available alkyl polyol type epoxy resins include ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epiklon 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611. (Manufactured by Nagase ChemteX Corporation).
- Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epolide PB (manufactured by Daicel Corporation), and the like.
- Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
- Examples of commercially available bisphenol A type episulfide resins include jERYL-7000 (manufactured by Mitsubishi Chemical Corporation).
- epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), jER1031, jER1032 (all Also, Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation), TEPIC (Nissan Chemical Corporation) and the like.
- Examples of commercially available epoxy (meth) acrylates include, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRY3603 EA-1010, EA-1020, EA-5323, EA-5520, 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, Epoxy ester 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA, Epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Den
- Examples of the (meth) acrylic resin other than the epoxy (meth) acrylate include, for example, an ester compound obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, and a (meth) acryl having a hydroxyl group on the isocyanate compound.
- Examples thereof include urethane (meth) acrylate obtained by reacting an acid derivative.
- examples of the monofunctional compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n -Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (Meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Dr
- bifunctional ester compound examples include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol 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 di ( ) Acrylate, neopentyl glycol di (meth) acrylate,
- those having three or more functions include, for example, trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, caprolactone-modified tri Methylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide-added glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (meth) acryloyloxyethyl Phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol pent
- 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-based compound. be able to.
- Examples of the isocyanate compound used as a raw material for the urethane (meth) acrylate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4.
- MDI '-Diisocyanate
- 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, tetramethylxylene diisocyanate, 1,6,11-undecanetriiso Aneto and the like.
- isocyanate compound examples include those obtained by reacting a polyol such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, propylene glycol, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol with an excess of an isocyanate compound. It is also possible to use chain-extended isocyanate compounds.
- 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).
- Hydroxyalkyl mono (meth) acrylates such as acrylate and 2-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol Mono (meth) acrylates of dihydric alcohols such as mono (meth) acrylates of trivalent alcohols such as trimethylolethane, trimethylolpropane, glycerin, etc. Epoxy (meth) acrylate of rate, and the like.
- Examples of commercially available urethane (meth) acrylates include M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700 , Art resin N-1255, Art Resin UN-330, Art Resin UN-3320HB, Art Resin UN-1200TPK, Art Resin SH-500B (all manufactured by Negami Industrial Co., Ltd.), U-122P, U-108A, U-340P,
- the (meth) acrylic resin preferably has 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.
- the (meth) acrylic resin preferably has 2 to 3 (meth) acryloyl groups in the molecule because of its high reactivity.
- the said curable resin may contain an epoxy resin for the purpose of improving the adhesiveness of the sealing agent for liquid crystal dropping methods obtained.
- said epoxy resin the epoxy resin used as the raw material for synthesize
- the partial (meth) acryl-modified epoxy resin means a resin having one or more epoxy groups and (meth) acryloyl groups in one molecule, for example, two or more epoxy groups. It can be obtained by reacting a part of the epoxy group of the resin having a methacrylic acid with (meth) acrylic acid.
- Examples of commercially available partial (meth) acrylic-modified epoxy resins include UVACURE 1561 (manufactured by Daicel Ornex).
- a preferable upper limit of the ratio of the epoxy group to the total amount of the (meth) acryloyl group and the epoxy group in the entire curable resin is 50 mol%.
- the ratio of the epoxy group exceeds 50 mol%, the resulting liquid crystal dropping method sealing agent is highly soluble in liquid crystals, causing liquid crystal contamination, and the resulting liquid crystal display element may be inferior in display performance. is there.
- a more preferable upper limit of the ratio of the epoxy group is 20 mol%.
- the sealing agent for liquid crystal dropping method of the present invention contains a polymerization initiator and / or a thermosetting agent. Especially, it is preferable to contain a radical polymerization initiator as a polymerization initiator.
- Springback is influenced not only by the influence of the particle size distribution of the soft particles, but also by the curing rate of the sealant. Since the radical polymerization initiator can significantly increase the curing rate as compared with the thermosetting agent, the effect of suppressing the occurrence of springback that is likely to occur due to the flexible particles by using in combination with the flexible particles. It can be further improved.
- the radical polymerization initiator examples include a thermal radical polymerization initiator that generates radicals by heating, a photo radical polymerization initiator that generates radicals by light irradiation, and the like.
- the radical polymerization initiator has a much faster curing rate than the thermosetting agent. Therefore, by using the radical polymerization initiator, it is possible to suppress the occurrence of seal breaks and liquid crystal contamination, and the flexible Springback that tends to occur by blending particles can be more effectively suppressed.
- the sealing compound for liquid crystal dropping methods obtained can be hardened rapidly with a heat
- thermal radical polymerization initiator what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
- a polymer azo initiator composed of a polymer azo compound is preferable.
- the polymer azo initiator means a compound having an azo group and generating a radical capable of curing a (meth) acryloyloxy group by heat and having a number average molecular weight of 300 or more. .
- the preferable lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferable upper limit is 300,000.
- the number average molecular weight of the polymer azo initiator is less than 1000, the polymer azo initiator may adversely affect the liquid crystal.
- the number average molecular weight of the polymeric azo initiator exceeds 300,000, mixing with the curable resin may be difficult.
- the more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
- the said number average molecular weight is a value calculated
- GPC gel permeation chromatography
- Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).
- polymer azo initiator examples include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
- polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group those having a polyethylene oxide structure are preferable.
- Examples of such a polymer azo initiator include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid) Examples thereof include polycondensates of polydimethylsiloxane having a terminal amino group, such as VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all of which are Wako Pure Chemical Industries, Ltd.) Manufactured) and the like.
- Examples of the azo initiator other than the polymer azo initiator include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
- organic peroxide examples include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
- photo radical polymerization initiator examples include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthones, and the like.
- photo radical polymerization initiators examples include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, all manufactured by Rusilin TPO ), Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.) and the like.
- a cationic polymerization initiator may be used as the polymerization initiator.
- a photocationic polymerization initiator can be suitably used.
- the cationic photopolymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be of an ionic photoacid generation type or a nonionic photoacid generation type. It may be.
- photocationic polymerization initiator examples include onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts, organometallic complexes such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes. Is mentioned.
- photocationic polymerization initiators examples include Adekaoptomer SP-150 and Adekaoptomer SP-170 (both manufactured by ADEKA).
- the content of the polymerization initiator is preferably 0.1 parts by weight and preferably 30 parts by weight with respect to 100 parts by weight of the curable resin. If the content of the polymerization initiator is less than 0.1 parts by weight, the obtained sealing agent for liquid crystal dropping method may not be sufficiently cured. When content of the said polymerization initiator exceeds 30 weight part, the storage stability of the sealing compound for liquid crystal dropping methods obtained may fall.
- a more preferable lower limit of the content of the polymerization initiator is 1 part by weight, a more preferable upper limit is 10 parts by weight, and a still more preferable upper limit is 5 parts by weight.
- thermosetting agent examples include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Among these, solid organic acid hydrazide is preferably used.
- Examples of the solid organic acid hydrazide include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
- Examples thereof include Amicure VDH, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co., Ltd.), SDH, IDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), MDH (manufactured by Nippon Finechem Co., Ltd.), and the like.
- the content of the thermosetting agent is preferably 1 part by weight with respect to 100 parts by weight of the curable resin, and 50 parts by weight with respect to the preferable upper limit.
- the content of the thermosetting agent is less than 1 part by weight, the resulting sealing agent for liquid crystal dropping method may not be sufficiently cured.
- content of the said thermosetting agent exceeds 50 weight part, the viscosity of the sealing compound for liquid crystal dropping methods obtained will become high too much, and applicability
- the upper limit with more preferable content of the said thermosetting agent is 30 weight part.
- the sealing agent for liquid crystal dropping method of the present invention preferably contains a 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 and epoxy resin amine adducts. Specific examples include tris (2-carboxymethyl) isocyanurate, tris (2-carboxyl). And ethyl) isocyanurate, tris (3-carboxypropyl) isocyanurate, and bis (2-carboxyethyl) isocyanurate.
- the content of the curing accelerator is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin. If the content of the curing accelerator is less than 0.1 parts by weight, the resulting liquid crystal dropping method sealing agent may not be sufficiently cured, or heating at a high temperature may be required for curing. is there. When content of the said hardening accelerator exceeds 10 weight part, the sealing compound for liquid crystal dropping methods obtained may become inferior to adhesiveness.
- the sealing agent for liquid crystal dropping method of the present invention preferably contains a filler for the purpose of improving the viscosity, improving the adhesiveness due to the stress dispersion effect, improving the linear expansion coefficient, and improving the 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, aluminum nitride, polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, core shell acrylate Examples include organic fillers such as copolymer fine particles. These fillers may be used alone or in combination of two or more.
- the preferable lower limit of the content of the filler is 10% by weight and the preferable upper limit is 70% by weight with respect to the entire liquid crystal dropping method sealing agent.
- the content of the filler is less than 10% by weight, effects such as improvement in adhesiveness may not be sufficiently exhibited.
- content of the said filler exceeds 70 weight%, the viscosity of the sealing compound for liquid crystal dropping methods obtained will become high, and applicability
- the more preferable lower limit of the content of the filler is 20% by weight, and the more preferable upper limit is 60% by weight.
- the sealing agent for liquid crystal dropping method of the present invention preferably contains a silane coupling agent.
- the silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.
- silane coupling agent since it is excellent in the effect which improves adhesiveness with a board
- -Phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, etc. are preferably used .
- These silane coupling agents may be used alone or in combination of two or more.
- the content of the silane coupling agent is such that the preferred lower limit is 0.1% by weight and the preferred upper limit is 20% by weight with respect to the entire liquid crystal dropping method sealing agent. If the content of the silane coupling agent is less than 0.1% by weight, the effect of blending the silane coupling agent may not be sufficiently exhibited. When content of the said silane coupling agent exceeds 20 weight%, the sealing compound for liquid crystal dropping methods obtained may contaminate a liquid crystal.
- the more preferable lower limit of the content of the silane coupling agent is 0.5% by weight, and the more preferable upper limit is 10% by weight.
- the sealing agent for liquid crystal dropping method of the present invention may contain a light shielding agent.
- the sealing compound for liquid crystal dropping methods of this invention can be used suitably as a light shielding sealing agent.
- Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Of these, titanium black is preferable.
- Titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370 to 450 nm, compared to the average transmittance for light having a wavelength of 300 to 800 nm. That is, the above-described titanium black sufficiently shields light having a wavelength in the visible light region, thereby providing light shielding properties to the sealing agent for liquid crystal dropping method of the present invention, while transmitting light having a wavelength in the vicinity of the ultraviolet region.
- a shading agent As the light-shielding agent contained in the liquid crystal dropping method sealing agent of the present invention, a highly insulating material is preferable, and titanium black is also preferable as the highly insulating light-shielding agent.
- the titanium black preferably has an optical density (OD value) per ⁇ m of 3 or more, more preferably 4 or more.
- OD value optical density
- the OD value of the titanium black is not particularly limited, but is usually 5 or less.
- the above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
- the liquid crystal display device manufactured using the sealing agent for liquid crystal dropping method of the present invention containing the above-described titanium black as a light-shielding agent has a sufficient light-shielding property, and thus has a high contrast without light leakage. A liquid crystal display element having excellent image display quality can be realized.
- titanium black examples include 12S, 13M, 13M-C, 13R-N, 14M-C (all manufactured by Mitsubishi Materials Corporation), Tilak D (manufactured by Ako Kasei Co., Ltd.), and the like. Can be mentioned.
- the preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferable upper limit is 30 m 2 / g, the more preferable lower limit is 15 m 2 / g, and the more preferable upper limit is 25 m 2 / g.
- the preferred lower limit of the volume resistance of the titanium black is 0.5 ⁇ ⁇ cm, the preferred upper limit is 3 ⁇ ⁇ cm, the more preferred lower limit is 1 ⁇ ⁇ cm, and the more preferred upper limit is 2.5 ⁇ ⁇ cm.
- the primary particle diameter of the light-shielding agent is not particularly limited as long as it is equal to or less than the cell gap of the liquid crystal display element, but the preferred lower limit is 1 nm and the preferred upper limit is 5 ⁇ m.
- the primary particle diameter of the light-shielding agent is less than 1 nm, the viscosity and thixotropy of the obtained liquid crystal dropping method sealing agent are greatly increased, and workability may be deteriorated.
- the primary particle diameter of the light-shielding agent exceeds 5 ⁇ m, the coating property of the obtained liquid crystal dropping method sealing agent on the substrate may be deteriorated.
- the more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm, the more preferable upper limit is 200 nm, the still more preferable lower limit is 10 nm, and the still more preferable upper limit is 100 nm.
- the content of the light-shielding agent is preferably 5% by weight and preferably 80% by weight with respect to the whole liquid crystal dropping method sealing agent. If the content of the light shielding agent is less than 5% by weight, sufficient light shielding properties may not be obtained. When the content of the light-shielding agent is more than 80% by weight, the adhesion of the obtained sealing agent for liquid crystal dropping method to the substrate and the strength after curing may be lowered, or the drawing property may be lowered.
- the more preferable lower limit of the content of the light-shielding agent is 10% by weight, the more preferable upper limit is 70% by weight, the still more preferable lower limit is 30% by weight, and the still more preferable upper limit is 60% by weight.
- the sealing agent for the liquid crystal dropping method of the present invention further includes a reactive diluent for adjusting the viscosity, a spacer such as a polymer bead for adjusting the panel gap, an antifoaming agent, a leveling agent, and a polymerization inhibitor, if necessary.
- a reactive diluent for adjusting the viscosity for adjusting the viscosity
- a spacer such as a polymer bead for adjusting the panel gap
- an antifoaming agent such as a polymer bead for adjusting the panel gap
- an antifoaming agent such as a leveling agent
- a polymerization inhibitor if necessary.
- additives such as other coupling agents may be contained.
- the method for producing the sealing agent for liquid crystal dropping method of the present invention is not particularly limited, and for example, a curable resin using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll. And a method of mixing a polymerization initiator and / or a thermosetting agent, flexible particles, and an additive such as a silane coupling agent added as necessary.
- the preferred lower limit of the viscosity measured at 25 ° C. and 1 rpm using an E-type viscometer is 50,000 Pa ⁇ s
- the preferred upper limit is 500,000 Pa ⁇ s.
- a more preferable upper limit of the viscosity is 400,000 Pa ⁇ s.
- a vertical conduction material can be manufactured by mix
- Such a vertical conduction material containing the sealing agent for liquid crystal dropping method of the present invention and conductive fine particles is also one aspect of the present invention.
- the conductive fine particles for example, metal balls, or those obtained by forming a conductive metal layer on the surface of resin fine particles can be used.
- the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.
- the liquid crystal display element which has the sealing compound for liquid crystal dropping methods of this invention or the vertical conduction material of this invention is also one of this invention.
- the sealing agent for the liquid crystal dropping method of the present invention is applied to one of two transparent substrates such as a glass substrate with electrodes such as an ITO thin film or a polyethylene terephthalate substrate.
- the process of forming a rectangular seal pattern by screen printing, dispenser application, etc., the liquid crystal drop method sealing agent of the present invention is uncured, and liquid crystal microdrops are dropped on the entire surface of the transparent substrate and applied immediately.
- a method of superposing another substrate and a step of heating and curing the sealing agent for liquid crystal dropping method of the present invention is a method for producing the liquid crystal display element of the present invention.
- irradiating light such as an ultraviolet-ray
- the sealing compound for liquid crystal dropping methods which can satisfy
- the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods can be provided.
- the sealing agent for organic EL display elements of an Example and a comparative example shall be used for manufacture of the organic EL display element whose cell gap is 5 micrometers.
- Silicone rubber particles (manufactured by Shin-Etsu Chemical Co., Ltd., “KMP-601”) are dispersed in methanol, classified by wet sieving with a sieve of 8 ⁇ m openings, and those that have passed through the sieve are collected and dried to obtain silicone rubber particles The soft particle A which is a classification processed product was obtained.
- As the sieve a polyimide film having a hole with extremely high accuracy obtained by applying ultrahigh precision fine processing with a laser was used.
- the mode particle size, the median particle size, the maximum particle size, the minimum particle size, and the average measured using a Coulter type distribution measuring device Particle size, D90, CV value of particle size, ratio W of volume frequency from minimum particle size to particle size 2 ⁇ m smaller than median particle size, volume from particle size 2 ⁇ m less than median particle size to median particle size
- Silicone rubber particles (manufactured by Shin-Etsu Chemical Co., Ltd., “KMP-601”) are dispersed in methanol and classified by wet sieving with an 8 ⁇ m mesh sieve. Wet sieve classification was performed using a sieve of No. 5, and the remaining material on the sieve was recovered and dried to obtain flexible particles B which were classified products of silicone rubber particles. As the sieve, a polyimide film having a hole with extremely high accuracy obtained by applying ultrahigh precision fine processing with a laser was used.
- the mode particle diameter, the median particle diameter, the maximum particle diameter, the minimum particle diameter, the average particle diameter, D90, and the CV value of the particle diameter, W, X measured in the same manner as the flexible particle A , Y, and Z are shown in Table 1.
- Silicone rubber particles (manufactured by Shin-Etsu Chemical Co., Ltd., “KMP-601”) are dispersed in methanol, classified by wet sieving with a sieve of 10 ⁇ m openings, and those passing through the sieve are collected and dried to obtain silicone rubber particles The soft particle C which is a classification treatment product of was obtained.
- As the sieve a polyimide film having a hole with extremely high accuracy obtained by applying ultrahigh precision fine processing with a laser was used.
- the mode particle diameter, the median particle diameter, the maximum particle diameter, the minimum particle diameter, the average particle diameter, D90, and the CV value of the particle diameter, W, X, measured in the same manner as the flexible particle A , Y, and Z are shown in Table 1.
- Preparation of flexible particles F 75 parts by weight of polytetramethylene glycol diacrylate, 21 parts by weight of styrene, and 4 parts by weight of benzoyl peroxide were mixed and dissolved uniformly to obtain a monomer mixture.
- the obtained monomer mixture was put into a reaction vessel containing a 1% by weight aqueous solution of polyvinyl alcohol and stirred for 2 to 4 hours to adjust the particle size so that the monomer droplets had a predetermined particle size. .
- reaction was performed for 9 hours in 85 degreeC nitrogen atmosphere, and the unclassified polymer particle was obtained.
- the obtained unclassified polymer particles were washed several times with hot water and dried.
- Preparation of flexible particles G 75 parts by weight of polytetramethylene glycol diacrylate, 21 parts by weight of styrene, and 4 parts by weight of benzoyl peroxide were mixed and dissolved uniformly to obtain a monomer mixture.
- the obtained monomer mixture was put into a reaction vessel containing a 1% by weight aqueous solution of polyvinyl alcohol and stirred for 2 to 4 hours to adjust the particle size so that the monomer droplets had a predetermined particle size. .
- reaction was performed for 9 hours in 85 degreeC nitrogen atmosphere, and the unclassified polymer particle was obtained.
- the obtained unclassified polymer particles were washed several times with hot water and dried.
- the mixture was dispersed in methanol, and subjected to wet sieving with a sieve having an opening of 8 ⁇ m.
- the particles that passed through the sieving were collected and dried to obtain flexible particles G that were classified into vinyl particles.
- a polyimide film having a hole with extremely high accuracy obtained by applying ultrahigh precision fine processing with a laser was used as the sieve.
- the mode particle diameter, the median particle diameter, the maximum particle diameter, the minimum particle diameter, the average particle diameter, D90, and the CV value of the particle diameter, W, X measured in the same manner as the flexible particle A , Y, and Z are shown in Table 1.
- Example 1 As a curable resin, 70 parts by weight of a bisphenol A type epoxy acrylate (manufactured by Daicel Ornex, "EBECRYL3700”) and 30 parts by weight of a bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation, “jER806”), as a thermal radical polymerization initiator 7 parts by weight of a polymeric azo initiator (Wako Pure Chemical Industries, “VPE-0201”), 8 parts by weight of sebacic acid dihydrazide (manufactured by Otsuka Chemical, “SDH”) as a thermosetting agent, and 30 parts by weight of flexible particles A Parts, 10 parts by weight of silica as a filler ("Admafine SO-C2" manufactured by Admatechs), and 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-” as a silane coupling agent) 403
- Examples 2 to 10, Comparative Examples 1 to 4 In accordance with the blending ratios described in Tables 2 and 3, each material was mixed using a planetary stirrer (“Shinky Netaro” manufactured by Shinky Co., Ltd.) in the same manner as in Example 1, and then further 3 rolls. Were used to prepare sealants for liquid crystal dropping methods of Examples 2 to 10 and Comparative Examples 1 to 4.
- the “KMP-601 unclassified product” used in Comparative Example 1 was obtained by using silicone rubber particles (“KMP-601” manufactured by Shin-Etsu Chemical Co., Ltd.) without classification.
- the “KMP-600 unclassified product” used is a silicone rubber particle (“KMP-600” manufactured by Shin-Etsu Chemical Co., Ltd.) used without being classified.
- Product is a silicone elastomer composite particle (Toray Dow Corning Co., Ltd., "9701 Cosmetic Powder”) that is used as it is without classification.
- Table 1 shows the median particle diameter, maximum particle diameter, minimum particle diameter, average particle diameter, D90, CV value of particle diameter, W, X, Y, and Z.
- a one-round sealant (dummy seal) was applied to the outer periphery. Thereafter, fine droplets of TN liquid crystal (manufactured by Chisso Corporation, “JC-5001LA”) were dropped and applied with a liquid crystal dropping device, and the other transparent substrate was bonded with a vacuum bonding device under a vacuum of 5 Pa.
- the cell after bonding was irradiated with 100 mW / cm 2 of ultraviolet light for 30 seconds using a high-pressure mercury lamp, and then heated at 125 ° C. for 60 minutes to thermally cure the sealant to obtain a liquid crystal display element.
- the sealing compound for liquid crystal dropping methods which can satisfy
- the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods can be provided.
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Abstract
Description
しかしながら、滴下工法で狭額縁設計の液晶表示素子を製造すると、ブラックマトリックスによりシール部に光の当たらない箇所が存在するため、充分に光照射されず硬化が進行しない光硬化性樹脂の部分が生じ、未硬化のシール剤が液晶と接するため、液晶がシール剤に差し込み、シールブレイクが発生して液晶が漏れ出してしまうことや、仮硬化工程後に未硬化の光硬化性樹脂が溶出してしまい、液晶が汚染されることがあるという問題があった。
以下に本発明を詳述する。
しかしながら、このような柔軟粒子を配合した場合、得られる液晶表示素子にスプリングバックによるセルギャップ不良が発生することがあった。
そこで本発明者らは鋭意検討した結果、粒度分布において、最頻粒子径が中位粒子径よりも特定の値以上大きい柔軟粒子を配合することにより、シールブレイクや液晶汚染の抑制とスプリングバックによるギャップ不良の抑制とを両立できる液晶滴下工法用シール剤を得ることができることを見出し、本発明を完成させるに至った。
本発明の液晶滴下工法用シール剤は、柔軟粒子を含有する。
上記柔軟粒子は、液晶表示素子を製造する際に、他のシール剤成分と液晶との間の障壁となって、液晶がシール剤に差し込むこと、及び、シール剤が液晶へ溶出することを防止する役割を有する。また、上記柔軟粒子を配合することにより、基板を貼り合わせた後、シール剤が硬化するまでの基板のずれを防止することができる。
なお、本明細書において、上記柔軟粒子における、最頻粒子径、中位粒子径、最大粒子径、最小粒子径、及び、平均粒子径は、コールター式粒度分布測定装置を用いて粒度分布を測定することにより得られる値を意味する。上記コールター式分布測定装置としてはマルチサイザー4(ベックマン・コールター社製)等を用いることができ、具体的には、粒子0.1gをメタノール10gに添加して馴染ませ、超音波分散を5分間行い粒子分散液を調製し、サンプルスタンド内の電解液「ISOTON II」(ベックマン・コールター社製)の入ったビーカーに、得られた粒子分散液を測定装置の表示濃度が5%になるまでスポイトで注入する。この濃度にすることにより、再現性のある測定値を得ることができる。測定は2回行い、算出された値の算術平均値を用いる。
具体的には例えば、柔軟粒子を適当な分散媒に分散させたスラリーを、目開きが均一に揃った高精度篩等を用いて篩う方法が好適に用いられる。
また、上記柔軟粒子の最大粒子径は、セルギャップの2.6倍以下であることが好ましい。上記柔軟粒子の最大粒子径がセルギャップの2.6倍を超えると、スプリングバックを起こし、得られる液晶滴下工法用シール剤が接着性に劣るものとなったり、得られる液晶表示素子にギャップ不良が生じたりすることがある。上記柔軟粒子の最大粒子径のより好ましい上限はセルギャップの2.2倍、更に好ましい上限はセルギャップの1.7倍である。
なお、液晶表示素子のセルギャップは、表示素子により異なるため限定されないが、一般的な液晶表示素子のセルギャップは、2~10μmである。
なお、本明細書において粒子径のCV値とは、上記コールター式粒度分布測定装置を用いて測定された粒度分布において、下記式により求められる数値のことである。
粒子径のCV値(%)=(粒子径の標準偏差/平均粒子径)×100
なお、上記柔軟粒子の回復率は、微小圧縮試験機を用いて、粒子1個に一定負荷(1g)をかけ、その負荷を除去した後の回復挙動を解析することにより導出することができる。
なお、上記柔軟粒子の1g歪みは、微小圧縮試験機を用いて、粒子1個に1gの負荷をかけ、その時の変位量を測定することにより導出することができる。
なお、上記柔軟粒子の破壊歪みは、微小圧縮試験機を用いて、粒子1個に負荷をかけていき、その粒子が破壊する変位量を測定することにより導出することができる。上記圧縮変位L4は、負荷荷重に対して変位量が不連続に大きくなる時点を、粒子が破壊した時点として算出する。負荷荷重を大きくしても変形するだけで破壊しない場合、破壊歪みは100%以上と考える。
なお、上記柔軟粒子のガラス転移温度は、JIS K 7121の「プラスチックスの転移温度測定方法」に基づいた示差走査熱量測定(DSC)により測定される値を示す。
上記シリコーン系粒子のうち市販されているものとしては、例えば、KMP-594、KMP-597、KMP-598、KMP-600、KMP-601、KMP-602(信越化学工業社製)、トレフィルE-506S、EP-9215(東レ・ダウコーニング社製)等が挙げられ、これらを分級や混合等により最頻粒子径が中位粒子径の1.07倍以上となるように調整して用いることができる。上記シリコーン系粒子は、単独で用いられてもよいし、2種以上が併用されてもよい。
上記(メタ)アクリル粒子は、原料となる単量体を公知の方法により重合させることで得ることができる。具体的には例えば、ラジカル重合開始剤の存在下で単量体を懸濁重合する方法、ラジカル重合開始剤の存在下で非架橋の種粒子に単量体を吸収させることにより種粒子を膨潤させてシード重合する方法等が挙げられる。得られた粒子の最頻粒子径が中位粒子径の1.07倍未満である場合には、分級や混合等により最頻粒子径が中位粒子径の1.07倍以上となるように調整する。
なお、本明細書において、上記「(メタ)アクリル」とは、アクリル又はメタクリルを意味する。
なお、本明細書において、上記「(メタ)アクリレート」とは、アクリレート又はメタクリレートを意味する。
なお、本明細書において上記柔軟粒子の硬度は、JIS K 6253に準拠した方法により測定されるデュロメータA硬さを意味する。
上記硬化性樹脂は、(メタ)アクリル樹脂を含有することが好ましい。
本発明の液晶滴下工法用シール剤は、速やかに硬化させることができるため、硬化性樹脂として(メタ)アクリル樹脂を含有し、かつ、重合開始剤として後述するラジカル重合開始剤を含有することが好ましく、加熱のみで本発明の液晶滴下工法用シール剤を速やかに硬化させることが可能となり、狭額縁設計の液晶表示素子であっても、液晶汚染の発生を充分に抑制することができるため、(メタ)アクリル樹脂と後述する熱ラジカル重合開始剤とを含有することがより好ましい。
上記硬化性樹脂は、エポキシ(メタ)アクリレートを含有することがより好ましい。
なお、本明細書において、上記「(メタ)アクリル樹脂」とは、(メタ)アクリロイル基を有する樹脂を意味し、上記「(メタ)アクリロイル基」とは、アクリロイル基又はメタクリロイル基を意味する。また、上記「エポキシ(メタ)アクリレート」とは、エポキシ樹脂中の全てのエポキシ基を(メタ)アクリル酸と反応させた化合物のことを意味する。
上記ビスフェノールF型エポキシ樹脂のうち市販されているものとしては、例えば、jER806、jER4004(いずれも三菱化学社製)等が挙げられる。
上記ビスフェノールS型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンEXA1514(DIC社製)等が挙げられる。
上記2,2’-ジアリルビスフェノールA型エポキシ樹脂のうち市販されているものとしては、例えば、RE-810NM(日本化薬社製)等が挙げられる。
上記水添ビスフェノール型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンEXA7015(DIC社製)等が挙げられる。
上記プロピレンオキシド付加ビスフェノールA型エポキシ樹脂のうち市販されているものとしては、例えば、EP-4000S(ADEKA社製)等が挙げられる。
上記レゾルシノール型エポキシ樹脂のうち市販されているものとしては、例えば、EX-201(ナガセケムテックス社製)等が挙げられる。
上記ビフェニル型エポキシ樹脂のうち市販されているものとしては、例えば、jERYX-4000H(三菱化学社製)等が挙げられる。
上記スルフィド型エポキシ樹脂のうち市販されているものとしては、例えば、YSLV-50TE(新日鉄住金化学社製)等が挙げられる。
上記ジフェニルエーテル型エポキシ樹脂のうち市販されているものとしては、例えば、YSLV-80DE(新日鉄住金化学社製)等が挙げられる。
上記ジシクロペンタジエン型エポキシ樹脂のうち市販されているものとしては、例えば、EP-4088S(ADEKA社製)等が挙げられる。
上記ナフタレン型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンHP4032、エピクロンEXA-4700(いずれもDIC社製)等が挙げられる。
上記フェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンN-770(DIC社製)等が挙げられる。
上記オルトクレゾールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンN-670-EXP-S(DIC社製)等が挙げられる。
上記ジシクロペンタジエンノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンHP7200(DIC社製)等が挙げられる。
上記ビフェニルノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、NC-3000P(日本化薬社製)等が挙げられる。
上記ナフタレンフェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、ESN-165S(新日鉄住金化学社製)等が挙げられる。
上記グリシジルアミン型エポキシ樹脂のうち市販されているものとしては、例えば、jER630(三菱化学社製)、エピクロン430(DIC社製)、TETRAD-X(三菱ガス化学社製)等が挙げられる。
上記アルキルポリオール型エポキシ樹脂のうち市販されているものとしては、例えば、ZX-1542(新日鉄住金化学社製)、エピクロン726(DIC社製)、エポライト80MFA(共栄社化学社製)、デナコールEX-611(ナガセケムテックス社製)等が挙げられる。
上記ゴム変性型エポキシ樹脂のうち市販されているものとしては、例えば、YR-450、YR-207(いずれも新日鉄住金化学社製)、エポリードPB(ダイセル社製)等が挙げられる。
上記グリシジルエステル化合物のうち市販されているものとしては、例えば、デナコールEX-147(ナガセケムテックス社製)等が挙げられる。
上記ビスフェノールA型エピスルフィド樹脂のうち市販されているものとしては、例えば、jERYL-7000(三菱化学社製)等が挙げられる。
上記エポキシ樹脂のうちその他に市販されているものとしては、例えば、YDC-1312、YSLV-80XY、YSLV-90CR(いずれも新日鉄住金化学社製)、XAC4151(旭化成社製)、jER1031、jER1032(いずれも三菱化学社製)、EXA-7120(DIC社製)、TEPIC(日産化学社製)等が挙げられる。
また、上記(メタ)アクリル樹脂は、反応性の高さから分子中に(メタ)アクリロイル基を2~3個有するものが好ましい。
上記エポキシ樹脂としては、例えば、上記エポキシ(メタ)アクリレートを合成するための原料となるエポキシ樹脂や、部分(メタ)アクリル変性エポキシ樹脂等が挙げられる。
なお、本明細書において上記部分(メタ)アクリル変性エポキシ樹脂とは、1分子中にエポキシ基と(メタ)アクリロイル基とをそれぞれ1つ以上有する樹脂を意味し、例えば、2つ以上のエポキシ基を有する樹脂の一部分のエポキシ基を(メタ)アクリル酸と反応させることによって得ることができる。
なかでも、重合開始剤としてラジカル重合開始剤を含有することが好ましい。スプリングバックは、上記柔軟粒子の粒度分布の影響だけでなくシール剤の硬化速度にも影響を受ける。上記ラジカル重合開始剤は、熱硬化剤に比べて硬化速度が格段に速くすることができるため、上記柔軟粒子と組み合わせて用いることにより、上記柔軟粒子により発生しやすいスプリングバックの発生を抑制する効果に更に優れるものとすることができる。
上述したように、上記ラジカル重合開始剤は熱硬化剤に比べて硬化速度が格段に速いため、ラジカル重合開始剤を用いることにより、シールブレイクや、液晶汚染の発生を抑制し、かつ、上記柔軟粒子を配合することにより発生しやすいスプリングバックもより効果的に抑制できる。
なかでも、得られる液晶滴下工法用シール剤を熱により速やかに硬化させることができるため、熱ラジカル重合開始剤が好ましい。
なお、本明細書において高分子アゾ開始剤とは、アゾ基を有し、熱によって(メタ)アクリロイルオキシ基を硬化させることができるラジカルを生成する、数平均分子量が300以上の化合物を意味する。
なお、本明細書において、上記数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)で測定を行い、ポリスチレン換算により求められる値である。GPCによってポリスチレン換算による数平均分子量を測定する際のカラムとしては、例えば、Shodex LF-804(昭和電工社製)等が挙げられる。
上記アゾ基を介してポリアルキレンオキサイド等のユニットが複数結合した構造を有する高分子アゾ開始剤としては、ポリエチレンオキサイド構造を有するものが好ましい。このような高分子アゾ開始剤としては、例えば、4,4’-アゾビス(4-シアノペンタン酸)とポリアルキレングリコールの重縮合物や、4,4’-アゾビス(4-シアノペンタン酸)と末端アミノ基を有するポリジメチルシロキサンの重縮合物等が挙げられ、具体的には例えば、VPE-0201、VPE-0401、VPE-0601、VPS-0501、VPS-1001(いずれも和光純薬工業社製)等が挙げられる。
また、高分子アゾ開始剤以外のアゾ開始剤の例としては、例えば、V-65、V-501(いずれも和光純薬工業社製)等が挙げられる。
上記カチオン重合開始剤としては、光カチオン重合開始剤を好適に用いることができる。上記光カチオン重合開始剤は、光照射によりプロトン酸又はルイス酸を発生するものであれば特に限定されず、イオン性光酸発生タイプのものであってもよいし、非イオン性光酸発生タイプであってもよい。
上記光カチオン重合開始剤としては、例えば、芳香族ジアゾニウム塩、芳香族ハロニウム塩、芳香族スルホニウム塩等のオニウム塩類、鉄-アレン錯体、チタノセン錯体、アリールシラノール-アルミニウム錯体等の有機金属錯体類等が挙げられる。
上記チタンブラックは、1μmあたりの光学濃度(OD値)が、3以上であることが好ましく、4以上であることがより好ましい。上記チタンブラックの遮光性は高ければ高いほどよく、上記チタンブラックのOD値に好ましい上限は特にないが、通常は5以下となる。
また、遮光剤として上記チタンブラックを含有する本発明の液晶滴下工法用シール剤を用いて製造した液晶表示素子は、充分な遮光性を有するため、光の漏れ出しがなく高いコントラストを有し、優れた画像表示品質を有する液晶表示素子を実現することができる。
また、上記チタンブラックの体積抵抗の好ましい下限は0.5Ω・cm、好ましい上限は3Ω・cmであり、より好ましい下限は1Ω・cm、より好ましい上限は2.5Ω・cmである。
なお、実施例及び比較例の有機EL表示素子用封止剤は、セルギャップが5μmの有機EL表示素子の製造に用いられるものとする。
シリコーンゴム粒子(信越化学工業社製、「KMP-601」)をメタノール中に分散させ、8μmの目開きの篩で湿式篩分級し、篩を通過したものを回収して乾燥させ、シリコーンゴム粒子の分級処理品である柔軟粒子Aを得た。篩はポリイミドフィルムにレーザーで超高精度微細加工を施して得た極めて精度の高い穴を有するものを用いた。
得られた柔軟粒子Aについて、コールター式分布測定装置(ベックマン・コールター社製、「マルチサイザー4」)を用いて測定した最頻粒子径、中位粒子径、最大粒子径、最小粒子径、平均粒子径、D90、粒子径のCV値、最小粒子径から中位粒子径よりも2μm小さい粒子径までの体積頻度の割合W、中位粒子径から2μm小さい粒子径から中位粒子径までの体積頻度の割合X、中位粒子径から中位粒子径よりも2μm大きい粒子径までの体積頻度の割合Y、中位粒子径よりも2μm大きい粒子径から最大粒子径までの体積頻度の割合Zを表1に示した。
上記コールター式分布測定装置による測定は、粒子0.1gをメタノール10gに添加して馴染ませ、超音波分散を5分間行い粒子分散液を調製し、サンプルスタンド内の電解液「ISOTON II」(ベックマン・コールター社製)の入ったビーカーに、得られた粒子分散液を測定装置の表示濃度が5%になるまでスポイトで注入した。測定は2回行い、算出された値の算術平均値を用いた。
シリコーンゴム粒子(信越化学工業社製、「KMP-601」)をメタノール中に分散させ、8μmの目開きの篩で湿式篩分級し、篩を通過したものを回収し、次いで、5μmの目開きの篩で湿式篩分級し、篩に残ったものを回収して乾燥させ、シリコーンゴム粒子の分級処理品である柔軟粒子Bを得た。篩はポリイミドフィルムにレーザーで超高精度微細加工を施して得た極めて精度の高い穴を有するものを用いた。
得られた柔軟粒子Bについて、柔軟粒子Aと同様にして測定した最頻粒子径、中位粒子径、最大粒子径、最小粒子径、平均粒子径、D90、粒子径のCV値、W、X、Y、及び、Zを表1に示した。
シリコーンゴム粒子(信越化学工業社製、「KMP-601」)をメタノール中に分散させ、10μmの目開きの篩で湿式篩分級し、篩を通過したものを回収して乾燥させ、シリコーンゴム粒子の分級処理品である柔軟粒子Cを得た。篩はポリイミドフィルムにレーザーで超高精度微細加工を施して得た極めて精度の高い穴を有するものを用いた。
得られた柔軟粒子Cについて、柔軟粒子Aと同様にして測定した最頻粒子径、中位粒子径、最大粒子径、最小粒子径、平均粒子径、D90、粒子径のCV値、W、X、Y、及び、Zを表1に示した。
シリコーンゴム粒子(信越化学工業社製、「KMP-601」)を精密空気分級機(日清エンジニアリング社製、「ターボクラシファイア TC-15」)にて供給速度5kg/h、回転数10000rpmの条件で分級し、柔軟粒子Dを得た。
得られた柔軟粒子Dについて、柔軟粒子Aと同様にして測定した最頻粒子径、中位粒子径、最大粒子径、最小粒子径、平均粒子径、D90、粒子径のCV値、W、X、Y、及び、Zを表1に示した。
シリコーン樹脂粒子(モメンティブ・パフォーマンス・マテリアルズ社製、「トスパール1100」)55重量部と、シリコーン樹脂粒子(モメンティブ・パフォーマンス・マテリアルズ社製、「トスパール2000B」)45重量部とを、粉体混合器(日本コークス工業社製、「FMミキサ(FM5RC/I)」)を用いて均一に撹拌混合し、柔軟粒子Eを得た。
得られた柔軟粒子Eについて、柔軟粒子Aと同様にして測定した最頻粒子径、中位粒子径、最大粒子径、最小粒子径、平均粒子径、D90、粒子径のCV値、W、X、Y、及び、Zを表1に示した。
ポリテトラメチレングリコールジアクリレート75重量部と、スチレン21重量部と、過酸化ベンゾイル4重量部とを混合し、均一に溶解させ、モノマー混合液を得た。得られたモノマー混合液をポリビニルアルコール1重量%水溶液の入った反応釜に投入し、2~4時間撹拌することで、モノマーの液滴が所定の粒子径になるよう、粒子径調整を行った。次いで、85℃の窒素雰囲気下で9時間反応を行い、未分級重合体粒子を得た。得られた未分級重合体粒子を熱水にて数回洗浄し乾燥させた。その後、メタノール中に分散させ、10μmの目開きの篩で湿式篩分級し、篩を通過したものを回収して乾燥させ、ビニル系粒子の分級処理品である柔軟粒子Fを得た。篩はポリイミドフィルムにレーザーで超高精度微細加工を施して得た極めて精度の高い穴を有するものを用いた。
得られた柔軟粒子Fについて、柔軟粒子Aと同様にして測定した最頻粒子径、中位粒子径、最大粒子径、最小粒子径、平均粒子径、D90、粒子径のCV値、W、X、Y、及び、Zを表1に示した。
ポリテトラメチレングリコールジアクリレート75重量部と、スチレン21重量部と、過酸化ベンゾイル4重量部とを混合し、均一に溶解させ、モノマー混合液を得た。得られたモノマー混合液をポリビニルアルコール1重量%水溶液の入った反応釜に投入し、2~4時間撹拌することで、モノマーの液滴が所定の粒子径になるよう、粒子径調整を行った。次いで、85℃の窒素雰囲気下で9時間反応を行い、未分級重合体粒子を得た。得られた未分級重合体粒子を熱水にて数回洗浄し乾燥させた。その後、メタノール中に分散させ、8μmの目開きの篩で湿式篩分級し、篩を通過したものを回収して乾燥させ、ビニル系粒子の分級処理品である柔軟粒子Gを得た。篩はポリイミドフィルムにレーザーで超高精度微細加工を施して得た極めて精度の高い穴を有するものを用いた。
得られた柔軟粒子Gについて、柔軟粒子Aと同様にして測定した最頻粒子径、中位粒子径、最大粒子径、最小粒子径、平均粒子径、D90、粒子径のCV値、W、X、Y、及び、Zを表1に示した。
硬化性樹脂としてビスフェノールA型エポキシアクリレート(ダイセル・オルネクス社製、「EBECRYL3700」)70重量部及びビスフェノールF型エポキシ樹脂(三菱化学社製、「jER806」)30重量部と、熱ラジカル重合開始剤として高分子アゾ開始剤(和光純薬工業社製、「VPE-0201」)7重量部と、熱硬化剤としてセバシン酸ジヒドラジド(大塚化学社製、「SDH」)8重量部と、柔軟粒子A30重量部と、充填剤としてシリカ(アドマテックス社製、「アドマファインSO-C2」)10重量部と、シランカップリング剤として3-グリシドキシプロピルトリメトキシシラン(信越化学工業社製、「KBM-403」)1重量部とを配合し、遊星式撹拌装置(シンキー社製、「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合させて液晶滴下工法用シール剤を得た。
表2、3に記載された配合比に従い、各材料を、実施例1と同様にして、遊星式撹拌機(シンキー社製「あわとり練太郎」)を用いて混合した後、更に3本ロールを用いて混合することにより実施例2~10、比較例1~4の液晶滴下工法用シール剤を調製した。
なお、比較例1で用いた「KMP-601未分級品」は、シリコーンゴム粒子(信越化学工業社製、「KMP-601」)を分級せずにそのまま用いたものであり、比較例2で用いた「KMP-600未分級品」は、シリコーンゴム粒子(信越化学工業社製、「KMP-600」)を分級せずにそのまま用いたものであり、比較例3で用いた「9701未分級品」は、シリコーンエラストマー複合粒子(東レ・ダウコーニング社製、「9701 コスメティックパウダー」)を分級せずにそのまま用いたものであり、それぞれについて、柔軟粒子Aと同様にして測定した最頻粒子径、中位粒子径、最大粒子径、最小粒子径、平均粒子径、D90、粒子径のCV値、W、X、Y、及び、Zを表1に示した。
実施例及び比較例で得られた各液晶滴下工法用シール剤について以下の評価を行った。
実施例及び比較例で得られた各液晶滴下工法用シール剤100重量部に対して平均粒子径4.7μmのスペーサー粒子(積水化学工業社製、「ミクロパールSI」)1重量部を遊星式撹拌装置によって均一に分散させ、得られたシール剤をディスペンス用のシリンジ(武蔵エンジニアリング社製、「PSY-10E」)に充填し、脱泡処理を行ってから、ディスペンサー(武蔵エンジニアリング社製、「SHOTMASTER300」)にて、2枚のITO薄膜付きの透明電極基板のうちの一方に長方形の枠を描く様にシール剤(メインシール)を塗布し、続いて、セルを真空に保持するため、更に外周に一周シール剤(ダミーシール)を塗布した。その後、TN液晶(チッソ社製、「JC-5001LA」)の微小滴を液晶滴下装置にて滴下塗布し、他方の透明基板を、真空貼り合わせ装置にて5Paの真空下にて貼り合わせた。貼り合わせた後のセルに高圧水銀ランプを用いて100mW/cm2の紫外線を30秒間照射した後、125℃で60分間加熱してシール剤を熱硬化させ、液晶表示素子を得た。
得られた液晶表示素子のセルギャップを測定し、セル内が均一に4~5μmとなっていた場合を「◎」、セル内のほぼ全体に4~5μmのギャップがとれていた場合を「○」、セル内に4~5μmのギャップがとれていない箇所が多く又は広く存在した場合を「△」、セルが形成できなかった場合を「×」としてセルギャップを評価した。結果を表2、3に示した。
上記「(セルギャップ)」の評価にて得られた液晶表示素子について、シール部周辺の液晶(特にコーナー部)に生じる表示むらを目視にて観察し、表示むらが全く無かった場合を「◎」、表示むらがほとんど無かった場合を「○」、表示むらがはっきりと確認された場合を「△」、酷い表示むらが確認された場合又はセルが形成できなかった場合を「×」として液晶汚染性を評価した。結果を表2、3に示した。
実施例及び比較例で得られた各液晶滴下工法用シール剤0.5重量部を、エタノール30重量部中に投入し、35℃で1時間撹拌を行った後、ろ過を行うことでシール剤から柔軟微粒子を取り出した。
各シール剤から取り出した柔軟粒子について、上記「(柔軟粒子Aの調製)」と同様にして測定した、最頻粒子径、中位粒子径、最大粒子径、最小粒子径、平均粒子径、粒子径のCV値、W、X、Y、及び、Zを表4に示した。
Claims (9)
- 液晶滴下工法による液晶表示素子の製造に用いる液晶滴下工法用シール剤であって、
硬化性樹脂と、重合開始剤及び/又は熱硬化剤と、柔軟粒子とを含有し、
前記柔軟粒子は、粒度分布において、最頻粒子径が中位粒子径の1.07倍以上であることを特徴とする液晶滴下工法用シール剤。 - 柔軟粒子は、粒度分布において、累積分布におけるD90が中位粒子径の1.40倍未満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。
- 柔軟粒子は、粒度分布において、最小粒子径から中位粒子径よりも2μm小さい粒子径までの体積頻度の割合をW(%)、中位粒子径よりも2μm大きい粒子径から最大粒子径までの体積頻度の割合をZ(%)としたとき、W/Z≧1.1であることを特徴とする請求項1又は2記載の液晶滴下工法用シール剤。
- 柔軟粒子は、粒度分布において、中位粒子径よりも2μm小さい粒子径から中位粒子径までの体積頻度の割合をX(%)、中位粒子径から中位粒子径よりも2μm大きい粒子径までの体積頻度の割合をY(%)としたとき、X+Y≧60であることを特徴とする請求項1、2又は3記載の液晶滴下工法用シール剤。
- 柔軟粒子は、粒度分布において、中位粒子径よりも2μm大きい粒子径から最大粒子径までの体積頻度の合計が全体の10%未満であり、かつ、最小粒子径から中位粒子径よりも2μm小さい粒子径までの体積頻度の合計が全体の20%未満であることを特徴とする請求項1、2、3又は4記載の液晶滴下工法用シール剤。
- 柔軟粒子は、最大粒子径が、液晶表示素子のセルギャップの100%以上であり、かつ、5~50μmであることを特徴とする請求項1、2、3、4又は5記載の液晶滴下工法用シール剤。
- 遮光剤を含有することを特徴とする請求項1、2、3、4、5又は6記載の液晶滴下工法用シール剤。
- 請求項1、2、3、4、5、6又は7記載の液晶滴下工法用シール剤と、導電性微粒子とを含有することを特徴とする上下導通材料。
- 請求項1、2、3、4、5、6若しくは7記載の液晶滴下工法用シール剤又は請求項8記載の上下導通材料を有することを特徴とする液晶表示素子。
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