TW405055B - Production process of liquid crystal display panel, seal material for liquid crystal cell and liquid crystal display - Google Patents

Abstract

This invention relats to a liquid crystal display apparatus formed by sealing a liquid crystal between two substrates with electrodes and alignment film with a seal material, comprising a liquid crystal panel produced in a production process comprising the steps of attaching two substrates in a vacuum, compressing in atmospheric pressure to have a uniform cell gap, a temporary hardening process of the seal material by ultraviolet ray irradiation and a main hardening process of the seal material by heating as the essential processes, wherein a radically polymerizable curing resin is used in a liquid crystal seal material. By comprising the processes, a production method of a liquid crystal display panel having a uniform cell gap. Without dislocation of the alightment between substrates, or discharge of uncured component of a seal material to the liquid crystal, capable of having a seal material firmly attached to the substrates even at panel corner portions, having an excellent straightness and moisture resistance of the seal material can be provided.

Description

Printed by the Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs __ V. Description of the Invention (Field of the Invention) The present invention relates to a sealing material for a liquid crystal display device. The manufacturing process of the sealing material for the liquid crystal device includes a liquid crystal display panel which is sealed by applying a liquid crystal sealing material in a production process. BACKGROUND OF THE INVENTION In a general method for producing a liquid crystal display device including a liquid crystal display panel, the display panel includes two transparent substrates, the substrates include electrodes subjected to alignment treatment, and the liquid crystal is sealed therebetween. The method includes alignment of the substrates with an interval The two substrates are connected to each other, compressed by a compression plate, weighted or vacuum-encapsulated to make it a uniform cell gap, and then heat-hardened, see jP_A_59_232315 or JP-B-6-68669. In the production method of a liquid crystal display panel, when a weight or a compression plate is used as a pressure to make it have a uniform cell gap, the stress on the substrate becomes uneven. The sealing material peeling phenomenon occurs everywhere. When the vacuum encapsulation is applied as the method of applying compression, the problem of displacement of the alignment substrate arises from the shrinkage of the vacuum encapsulation bag during compression. An example of a liquid crystal sealing material (hereinafter referred to as a sealing material) that connects two substrates and seals a liquid crystal includes an encapsulated thermosetting epoxy resin, such as "STRUCTBOND XN-21-F" produced by MITSUI TOATSU Chemica Bu INC. The problems caused by this sealing material containing thermosetting epoxy resin are, for example, the displacement of the two substrates that are initially aligned and connected. Due to the high hardening temperature, the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1! t —--— II Sleep Γ f Jing first read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs _M_5055 _ ^ _ V. Invention. Explain that (X) (150 C) causes warping of the substrate and long hardening time. Stomach 7 solves this kind of problem. 'Ultraviolet-curable sealing material can be used.' A sealing material containing an ultraviolet-curable component and a thermosetting component, and a double-type sealing material that overlaps a thermosetting-curable seal and an ultraviolet-curable component. . @ 夕 1 Examples of the wire-curable sealing material include materials containing a (meth) acrylic monomer and which can be hardened by radical polymerization. Herein, "(meth) acrylic acid monomer" is a compound of Table 1, which includes at least one selected from the group consisting of acrylic acid monomer, acrylate monomer, methacrylate monomer, and Its derivatives. Since the curing shrinkage caused by ultraviolet rays is quite significant, and the seal curing rate caused by radical polymerization during curing is very low, problems in fixing and moisture resistance will occur. To prevent such hardening shrinkage, the use of denatured urea acrylate is proposed in JP-A-7-13173 and JP-A-7-13174. But urea acrylate expands with heat and is not heat resistant. Especially when the annealing process is performed to ensure a uniform display plane of the liquid crystal display device, because the annealing temperature needs to be a nematic-isotropic phase transition temperature (typically from 80 ° C to 120 ° C or higher) Due to the expansion of the sealing material containing urea acrylate, for example, in a liquid crystal display device containing a liquid crystal display panel, the critical voltage is irregular due to the height of the gap near the sealing portion of the liquid crystal display panel. For examples of sealing materials containing both UV-curable components and thermosetting components, see JP-A-4-11223 and JP-A-6-160872, which have a revised paper size that applies Chinese National Standard (CNS) A4 Specifications (210 X 297 mm)------- I —I! · Install i ί I p I Order-! -Line 1 (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___ 40Γι055 β7 ___ 5. Description of the invention (price) Good hardening rate. The known product is "WorldROCKX-8700" produced by KYORITSU Chemical and Co., LTD. Because it contains both a UV-curable component and a thermosetting component, it contains a resin, which is obtained by polymerizing the following : UV-curable (meth) acrylic monomer or oligomer, and epoxy resin as thermosetting component. In UV-curing, the epoxy resin interferes with (meth) acrylic monomer or The radical polymerization of oligomers requires a large amount of ultraviolet energy. In addition, because the thermosetting component is an epoxy resin, it is necessary to heat cure at high temperatures for a long time, which may cause good production due to curling of the glass substrate. The problem of lowering the rate. The method of using a double-type seal is found in JP-A-3-273215 and JP-A-4-11223. The seal contains a thermosetting sealing material at the edge of the liquid crystal, and at the same time a UV-curable seal is added. In addition, the method for manufacturing a liquid crystal display panel further includes the steps of adding and filling liquid crystals. This step is to form a dense layer on a substrate that has been subjected to an electrode alignment process. Between the step of sealing the material and the step of connecting the opposing substrates through a spacer method, because the unhardened sealing material and the liquid crystal touch each other, the sealing material needs to be polymerized by a radical polymerization process, and it can be UV-cured. If a monomer or oligomer polymerized by cationic polymerization is used, such as the aromatic diazonium salt of the Lewis acid, triallyl sulfonium salt, diallyl sulfonium salt, triallyl selenium salt And cationic compounds such as metal dicyclopentadiene compounds as photoinitiators, the ionic initiator will be drawn into the liquid crystal, causing problems such as poor alignment of the liquid crystal and an increase in the amount of current. Therefore, in jp_A_62_ 89〇 It is recommended to use the double sealing method in 25, where the edge of the liquid crystal is free (please read the precautions on the back before filling this page) -I --IIII l · I — —— — —— — — This paper size applies to China Standard (CNS) A4 specification (210 X 297 Gongchu) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ---- 10505 ·, w ___— _ V. Description of the invention (f) UV-curing type based on polymerization Seal, _use_㈣㈣. Because the sealing width required for the above-mentioned double sealing method is twice the general sealing width ', it is necessary to restrict the commercial design of the liquid crystal display panel. The number of copies has been reduced, and the smaller electrode terminal parts for installation are described in the present invention. The purpose of this document is to provide a high-quality, reliable axis LCD display panel. Gap, there is no alignment shift between the substrates. The composition of the dense bulk material is to the liquid crystal. The liquid crystal display panel contains a sealing material, which is firmly connected to the substrate, even at the corner. And sealing ability. Another object of the present invention is to provide a liquid crystal sealing material which simultaneously uses an external hardening component and a thermosetting component for a liquid crystal display panel of a liquid crystal display device having excellent adhesion and moisture resistance. Does not interfere with free-radical polymerization, does not require long-term thermosetting at high temperatures, and does not produce poor alignment between liquid crystals, and can be freed by monomers or oligomers containing only (meth) lacrylic acid Polymerized monomers or oligomers, and the present invention provides a high-quality and reliable liquid crystal display device including a liquid crystal display panel sealed by the liquid crystal sealing material. In order to achieve the above object, the method for manufacturing a liquid crystal display device of the present invention includes the following steps: A sealing material is used to form a sealing portion at an electrode-side end of at least one of two substrates including an electrode to be sealed. The sealing material includes One UV standard for this paper is applicable to China Solid State Standard (CNS) A4 (21〇X 297 mm) ------------- Installation ------ Order ---- Line, (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

405055 Z V. Description of the invention (s) The hardened resin component and the ~ thermosetting resin component are connected to the two substrates through a spacer, and at least the sealing portion is irradiated with ultraviolet rays to temporarily harden the sealing portion, and the sealing portion is heated for supply. Master hardening. In this method, the joining process is preferably performed at a reduced atmospheric pressure. In this context, the reduced atmospheric pressure is expressed as a pressure of about 0.4 to 1.0 Torr. In the above method, it is preferable to perform an alignment process on the electrode-containing substrate. In the above method, the weight ratio of the ultraviolet curing resin component to the thermosetting resin component is preferably from 60:40 to 90:10. A method for manufacturing a liquid crystal display panel according to the present invention includes the following steps: forming a sealing resin composition on a portion to be sealed on a surface of a first transparent substrate on which an electrode is mounted, the resin composition including a ~ hardened resin and starting the A hardener for the hardening process of the hardening resin, which connects the surface of the second transparent substrate on which the electrode is mounted and the surface of the first transparent substrate on which the electrode is mounted, puts liquid crystal in the gap between the first and second transparent substrates to be connected, and borrows The two transparent substrates with electrodes are connected from the above-mentioned sealing resin composition, and a step of hardening the hardening resin is performed so that the hardening rate is 80% or more. This paper size applies to the Chinese National Standard (CNS) A4 specification (21 () χNuo Gonglu) — I— I 111 --- installed ·! —Order 11 11! -Thread r- (Please read the precautions on the back before filling out this page) A7 405055 B7 5. & Description of the invention In the above procedure, it is best to include in the hardener of the sealing resin composition A UV hardener, a hardening process of starting a hardened resin with ultraviolet radiation 'and a hardening process including a heat curing agent, starting with a hardening resin by heating' wherein the process of hardening the hardened resin includes a first process, which consists of Irradiation—ultraviolet rays to the sealing resin composition, so that the curing rate of the cured resin is at least 60%, and includes a second procedure, which is after the first procedure, the sealing resin composition is heated to make the curing rate of the cured resin At least 80%. In the above procedure, it is preferable to include an ultraviolet curing agent in the curing agent of the sealing resin composition, to initiate the curing procedure of the curing resin by irradiation with ultraviolet rays, and to include a particle-type heat curing agent to initiate the curing of the resin by heating. The hardening process of the hardening resin includes a first process of irradiating an ultraviolet ray to the sealing resin composition so that the hardening rate of the hardening resin is at least 50%, and a second process of After the first procedure, the resin composition is sealed by heating so that the hardening rate of the hardened resin is at least 80%. In the above procedure, it is best to use a pair of large-area transparent substrates with electrodes to mount multiple liquid crystal display panels, so that the pair of large-area transparent substrates with electrodes can be each of a plurality of liquid crystal display panels Do multiple splits. In the above procedure, it is preferable to form a liquid crystal display panel by dropping liquid crystal between the step of forming a seal and the step of connecting two substrates having electrodes. The sealing material for a liquid crystal display panel of the present invention includes an ultraviolet curing component and a thermosetting component. These components include (meth) acrylate derived from an epoxy resin, (formaldehyde) (Meth) acrylic acid ester, a photoinitiator, a heat curing agent, and an inorganic filler are used as basic ingredients. Among them, the Chinese national standard (CNS) A4 specification ( 210 X 297 mm) (Please read the precautions on the back before filling out this page > --Binding · -------- Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative 405055 5. Description of the invention (7) Percentage of the weight of the sealing material ((meth) acryiic acid ester) contains 5 to 10% (meth) acrylate [per molecule Contains multiple (meth) acrylic residues] and contains 2 to 10% (meth) acrylic esters [one (meth) acrylic residue per molecule]. Among the above-mentioned sealing materials, the best The (A Based) Acrylate accounts for 40 to 70% by weight in the sealing material, and is a bisphenol A type or a phenolic lacquer type. In the above-mentioned sealing materials, it is preferable that the photoinitiator accounts for 3 to 5% by weight, and selected from the group consisting of: acetophenone type light initiator 'benzoin type light initiator and benzophenone type light initiator. In the above-mentioned sealing material, Preferably, the heat curing agent accounts for 2 to 5% by weight of the sealing material, and is selected from the group consisting of hydrazine, aromatic amine, acid anhydride, and imidazole. In the above sealing material, it is preferable that the heat curing agent is particles Type of heat curing agent, whose average particle size is 3 / zm or less. In the above-mentioned sealing material, it is preferable to include a silane coupling agent, which accounts for 2 to 7% by weight of the seal, and select from the following group: shrinkage Glyceryl ethoxysilane and glycidyl methoxysilane. In the above-mentioned sealing material, it is preferable that the average size of the inorganic filler is 1.5 // m or less, and accounts for 8 to 2 in the sealing material. 〇% by weight, and choose from the following groups: hydrated magnesium silicate, calcium carbonate Aluminum carbonate and silicon oxide. The liquid crystal display panel of the present invention includes two substrates having electrodes and connected to each other via a resin composition sealed. The resin composition mainly includes a hard paper and is sized for the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) I ------ itr ._------- line (Please read the precautions on the back before filling out this page) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 405055 B7 5. Description of the invention (ii) The resin has a hardening rate of 80% or more. In the above panel, the mixing ratio of the ultraviolet curing resin component and the thermosetting resin component is preferably 60:40 to 90:10. In the above-mentioned panel, the hardening agent for hardening the hardening resin is preferably a radical polymerization initiator to initiate a radical polymerization action of the hardening resin. As described above, the present invention relates to a liquid crystal display panel including two substrates, the substrate having electrodes, and sealed liquid crystals therebetween. The manufacturing method includes a seal forming process step, and a sealing material is used in the liquid crystal display. A sealing portion is formed on the electrode-side end of at least one of the two substrates of the panel. The sealing material includes an ultraviolet curing agent component and a thermal curing agent component. The manufacturing method further includes a first curing step, which irradiates ultraviolet rays to The sealing resin composition has a hardening rate of at least 50 to 60%, and a second step is to heat the sealing resin composition so that the hardening rate of the hardening resin is at least 80%. According to the manufacturing method of the liquid crystal display panel of the present invention, since the connection process of two substrates containing electrodes is performed in a vacuum and compression process to obtain a uniform cell gap, which is performed under atmospheric pressure, it can be obtained without Aligned shifted uniform cell gap. Because the sealing material contains both an ultraviolet hardening component and a thermosetting component, and a temporary hardening process is performed to irradiate the sealing portion of the unit cell with ultraviolet light, so unlike traditional thermosetting sealing, there will be problems such as: the sealing material is reduced due to its viscosity. Leakage damages the alignment, cutting seal material and the alignment displacement of the substrate. In particular, 'If the UV hardened paper of the sealing material is UV-cured, the Chinese standard (CNS) A4 specification (210 X 297 public love> -------- II 111111-- Order i —! —--, (Please read the notes on the back before filling out this page} Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (γ) The hardening rate of the chemical composition is at least 50% To 60%, it can prevent the increase in voltage due to the sealing material dragging into the liquid crystal, and the liquid crystal is not cluttered. Moreover, if the curing rate of the sealing material is at least 80% after the main hardening, when cutting the substrate It can prevent the corners of the panel from peeling, so the present invention can produce a high-yield and reliable liquid crystal display device. The sealing material used in the liquid crystal display panel of the present invention contains a% hardening component and a thermosetting component, and these components include derived from The epoxy (meth) acrylate, (meth) acrylate, a photoinitiator, a heat curing agent, and an inorganic filler are used as the basic components. Among them, the Score, (Meth) acrylate contains 5 to 10% of (_yl) acrylate [multiple (meth) acrylic residues per molecule], 1 contains 2 to 10% of (meth) acrylate [per The molecule contains ~ (methyl > acrylic residue]. In the above-mentioned sealing material, 40 to 70% by weight of the epoxy (meth) acrylic sealing material is a bisphenol A type or ^ Wake up paint type. ≫ In the above-mentioned sealing materials, the light initiator preferably accounts for 5% by weight of the seal, and it is selected from the following group: phenethyl_ type $ agent, benzoin type light starter And benzophenone light starter ^ ^ @In the above sealing materials, the heat curing agent preferably accounts for the weight percentage of the sealing material, and it is selected from the following group: hydrazine, aromatic face, spoon 2 to 5 Mi Wah. For women, anhydrides, and in the above-mentioned sealing materials, the thermal curing agent is preferably ~ particles $ _ \ chemical agent, the average particle size is 3 #m or less. This paper size applies to Chinese National Standards (CNS) A4 specification (210 X 297 mm) ------------- IIIII I--Order .--- — — 111! (Please read the precautions on the back before filling this page ) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (π) In the above sealing materials, it is better to account for 7% by weight. Choose from the following group: glycidyl_ethoxyl alkane And glycidyl methoxy sand. In the above sealing materials, the average size of the inorganic filler is 5

Mm or less, and 8 to 20% by weight of the sealing material, and selected from the group: hetero-magnesium hydrate, carbon oxide sand. It is preferable that the sealing material for the liquid crystal display surface produced by the manufacturing method includes a step of adding liquid crystal between the step of forming the sealing material and connecting the two substrates containing electrodes. The present invention _ Guan Shen Zhi contains-liquid is difficult to show, it contains liquid crystal, this liquid crystal is sealed by any of the above sealing materials. In the above-mentioned liquid crystal display device, it is preferable that the liquid crystal display panel is produced by a manufacturing method that includes a step of dropping a liquid crystal between the step of forming the sealing material and the step of connecting two substrates containing electrodes. According to the above-mentioned principle [the sealing material of the present invention includes an ultraviolet curing component and a critical component 'which includes an epoxy compound-derived acrylic acid ester, (meth) acrylic acid ester, a photoinitiator, and a thallium curing agent. In addition, the thermosetting agent can be alternately connected with a resin component, and the resin can be polymerized through radical polymerization by irradiating ultraviolet rays with a surface ultraviolet curing component to polymerize the resin component. Α As described above, because the sealing material of the present invention is not Contains the epoxy tree, so it does not require long-term heating to harden the epoxy resin, so it will not destroy the viscosity of the sealing material due to adhesion, and the frequency of substrate alignment or substrate curling after connection will not occur. Because it does not contain ring_lipid, it is hardened in UV 13. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ------------- Package ------ — — Order --------- line., {Please read the notes on the back before filling out this page) 405055 V. Description of the invention (in fh, interference with (meth) acrylates derived from epoxy compounds The danger of free radical polymerization of According to this, a liquid crystal display device including a liquid crystal display panel, preferably the liquid crystal is loosely sealed by the liquid crystal sealing material, the liquid crystal display device has excellent adhesion and moisture resistance, and can provide good display quality and It can be said that 0 does not have the risk of poor liquid crystal alignment or increased current. Furthermore, the sealing material of the present invention is hardened by radical polymerization and has a high reaction rate in ultraviolet curing, even when a dropwise addition is applied. During the procedure, that is, the sealing material is formed on one of the two substrates with the electrode with alignment treatment. Before the liquid crystal is dropped between the two substrates (the two substrates are connected to each other by a spacer), the alignment state of the liquid crystal or Electrical properties will not be significantly affected. Especially even after UV curing, by selecting a thermosetting agent to polymerize the thermosetting sealing material at a temperature lower than the annealing temperature of the liquid crystal panel, the manufacturing efficiency will not decrease. Accordingly, even a drop With the addition of the program, it is still possible to efficiently provide a liquid crystal display device with good display quality. Moreover, in the composition of the sealing material of the present invention, When a dropwise addition process is performed, a sealing material is formed on the substrate containing the electrode, the electrode has been subjected to alignment processing, the opposing substrates are connected by a spacer method, and the liquid crystal is dropped in between, because it is derived from the ring The thermal expansion of the (meth) acrylate of the oxygen compound is relatively small and it can be radically polymerized. Therefore, it is possible to prevent the leakage of the components of the sealing material caused by the contact between the unhardened liquid crystal sealing material and the liquid crystal, resulting in an increase in current flow or poor alignment. Moreover, since (meth) acrylates generally derived from epoxy compounds are obtained in the form of oligomers, they are used in the form of oligomers as the constituent material of the present invention. This paper size applies to Chinese national standards (CNS) A4 size (210 X 297 mm) (Please read the precautions on the back before filling this page)

· I I ---- Order I ------- I I Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

C A7g 5. Description of the invention ((1) Regarding (meth) acrylates containing multiple (meth) propionic acid residues in each molecule, it helps to increase the hardening density, facilitates thermosetting, and achieves a high temperature. Reliable sealing material. When this component is less than 5% by weight in the sealing material, the cross-link density becomes insufficient to provide a liquid crystal display device with high thermosetting reliability and moisture resistance. On the other hand, when the amount When it exceeds 10% by weight, 'hardening shrinkage will significantly prevent the achievement of good bonding properties. Since (meth) acrylates containing a (meth) acrylic residue in each molecule have less hardening shrinkage, it is best to do A component to suppress hardening shrinkage. Also, 'in the monomer stage before polymerization, it provides a solvent derived from a (meth) acrylate of an epoxy compound, and is provided as a viscous material when a sealing material is applied to a substrate in printing When the proportion of the component in the sealing material is 2% by weight or less, the curing shrinkage of the sealing material becomes too large, and a liquid crystal display device with high adhesion cannot be obtained. On the other hand, if the proportion exceeds 10% by weight, the cross-linking density becomes too low to obtain a locally heat-resistant and moisture-resistant liquid crystal display device. Moreover, this component is too much, and the unhardened component is easy to drag Into the liquid crystal, causing problems such as poor alignment and increased current. A photoinitiator provides a source of free radical generation, which is necessary for the UV polymerization of the (meth) acrylic monomer or oligomer component. A heat-curing agent helps the cross-linking caused by heating and the hardening caused by the heat of the polymer components generated by the above-mentioned ultraviolet polymerization, so it can improve the adhesion and heat resistance. Silane coupling agents can further improve the moisture resistance. Inorganic concrete fillers can help adhesion, such as improving peel strength and adjusting the viscosity of sealing materials. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back first (Fill in this page again) i! 1 Order, il! I-Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed A7 A7 Explanatory note (because) Since the sealing material of the present invention contains the above-mentioned components, even if it is hardened by radical polymerization, it has excellent adhesion and moisture resistance to provide high display quality and reliability. The present invention will be explained below A better example. The (meth) acrylate derived from an epoxy compound is preferably a bisphenol A type or a phenolic lacquer type, and accounts for 40 to 70% by weight of the liquid crystal sealing material. When printing When the sealing material is applied, its viscosity is preferably bisphenol A type and acid aldehyde lacquer type epoxy (meth) acrylic acid whose viscosity can be appropriately adjusted. Moreover, it is not easy to compare with modified urea acrylate The thermal expansion is the best. Because 40 to 70% by weight can eliminate the hardening shrinkage caused by the increase in the ratio of other monomer components, poor liquid crystal alignment, increased current flow, high or low viscosity when applied by printing Such as hysteresis, so this is a better choice. The photoinitiator selected from the following groups can be smoothly polymerized with the wavelength of a general ultraviolet lamp, and this group includes: an acetophenone-type photoinitiator, a benzoin-type photoinitiator, and diphenyl A ketone type light initiator. Furthermore, because such photoinitiators have a relatively long pot life, and are sufficient to eliminate the danger of excessive polymerization during the adjustment of the sealing material or during the application of the sealing material to the substrate by printing, it is a better choice. If the ratio of the photo-initiator is too low, since ultraviolet curing cannot proceed smoothly, unhardened components can leak into the liquid crystal and cause poor alignment of the liquid crystal. On the other hand, if the ratio is too high, since ultraviolet curing cannot be performed sufficiently, there may arise a problem that, for example, an excessive amount of a photoinitiator leaks into the liquid crystal and increases the current 値. Therefore, it is preferable that a photoinitiator of 3 to 5% by weight is contained in the liquid crystal sealing material. The best heat curing agent is selected from the following groups: hydrazine, aromatic amines, and standards applicable to China National Standard (CNS) A4 specifications (210 χ 297 mm) — II Pack — 1 — Order ·! -Line} I- (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 405055 B7 V. Description of the invention (丨 屮) Acid anhydride and imidazole The curing temperature is lower than the general decomposition temperature, so the danger of the liquid crystal being damaged by heat can be avoided. In addition, because such a thermosetting agent has a long service life, that is, 8 hours or more at room temperature, during the adjustment of the sealing material or the printing of the sealing material on the substrate, the thermal curing agent can be prevented from performing excessive cross-linking polymerization. Danger, so this is the better choice. Since a particle heat curing agent having an average particle size of 3 m or less has a longer pot life and does not prevent radical polymerization in ultraviolet curing, this is a better choice. Because the average particle size is 3em or less, and is smaller than the gap between the two substrates of the liquid crystal display panel adjusted by a spacer, the risk of gap defects can be avoided, so this is a better choice. The lower limit of the average particle size of the thermal curing agent is not particularly limited, but is generally about 1 // m. Because the silane coupling agent selected from glycidyl ethoxysilane and glycidyl methoxyl oxane can further improve the moisture resistance effect, this is a better choice. If the ratio of the silane coupling agent is too low, the moisture resistance of the liquid crystal display panel cannot be improved. If the proportion of the silane coupling agent is too high, a poor alignment of the liquid crystal may occur because the sealing material leaks into the liquid crystal. Therefore, it is preferable that the silane coupling agent in the liquid crystal sealing material accounts for 2 to 7% by weight of the sealing material to avoid this problem. Because inorganic fillers selected from hydrated magnesium silicate, calcium carbonate, aluminum carbonate, and silicon oxide can be used, and the average particle size is smaller or smaller, it is easier to do, which can improve the adhesion, and when the sealing material When printing and coating, its viscosity can be easily adjusted, so this is the better choice. The application of inorganic fillers with an average particle size of 1.5 # m or less can apply the Chinese National Standard (CNS) A4 specification (210 X 297 mm) at the seal material ^ paper size ^ -------- -------- Φ, (Please read the notes on the back before filling out this page) Printed by the Consumers 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 ^ όϋ55 V. Description of invention (C) Fully distributed in the materials' And the average particle size is smaller than the gap between the two substrates of the liquid crystal display panel to be adjusted in a spacer manner, so gap defects do not occur, so this is a better choice. The lower limit of the average particle size of the inorganic filler is not particularly limited, but generally, small particles of about 15 nm are the best. If the ratio of the inorganic filler is too low, the adhesion cannot be sufficiently improved. If the ratio is too high, it is not suitable to apply a sealing material to a substrate by a printing method, and a gap of a predetermined distance between the two substrates cannot be maintained. Therefore, it is better to use inorganic fillers in the sealing material in an amount of 8 to 20% by weight to avoid this problem. Adjust the proportion of (meth) acrylate containing at least one (meth) acrylic acid residue in each molecule, and adjust the inorganic filler in the above-mentioned mixing amount margin, and then seal with appropriate viscosity The material is suitable for alignment adjustment after printing and substrate connection, and can make the production of liquid crystal display devices highly efficient. For particles with an average size of 1 _5 # m, because this improves the thixotropic properties of the sealing material, a liquid crystal display device with excellent display quality can be obtained without causing problems such as Liquid crystal alignment problems caused by leakage of materials or cutting of sealing materials. Brief description of the drawings: Fig. 1 is an oblique view of a connection procedure of two substrates containing electrodes in an example of the present invention, the electrodes having been subjected to alignment processing. Fig. 2 shows a procedure for temporarily hardening a liquid crystal by ultraviolet irradiation in an example of the present invention. FIG. 3 shows the 18 paper sizes of the liquid crystal display panel produced by the manufacturing method of the $ 0 example of the present invention, which is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297). ------------- Install ---------Order --------- line, (Please read the notes on the back before filling out this page} Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 405055 A) An oblique view. Fig. 4 is a partially enlarged view of a sealing portion of the liquid crystal display panel in Fig. 3. Fig. 5 is a cross-sectional view of a liquid crystal display panel used in an exemplary liquid crystal display device of the present invention. Fig. 6 is A plan view showing a peeling strength test of a substrate of a liquid crystal display panel in an example of the present invention. FIG. 7 is a side view of a peeling strength test of a substrate of a liquid crystal display panel in an example of the present invention. FIG. 8 is a liquid crystal display in an example of the present invention. An oblique view of a liquid crystal dripping during a dropping process of a panel manufacturing method. Fig. 9 is a sectional view of a process of connecting a substrate to an opposite substrate, in which liquid crystal is dropped and a spacer material is interposed therebetween. Schematic element symbol description 1 A, 1 B. Glass substrate 2. Glass Spacer material 3. Sealing material 4A ~ 4D. Fixed feet 5A, 5B. Spacer 6. Vacuum chamber 7. Cell 8. UV cover 9. Opening 10. Alignment film This paper applies Chinese national standard (cns) aT ^ (210 χ 297 public love) --- (Please read the precautions on the back before filling out this page) --------------- I I order 1 III! Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Α7 _B7 V. Description of the invention ((Ί) 11 · Transparent electrical i 12A, 12B. Glass substrate 1 3. Liquid crystal I4 · Liquid distributor 21. Pressure gauge pressure column 2 3. LCD display panel holder 2 4. Liquid crystal Display panel 2 4 A. Upper substrate 24B. Lower substrate 25. Support of the liquid crystal display panel 26. Base 27. Detailed description of the pulse motor invention (first example) The first example of the manufacturing method of the liquid crystal display panel of the present invention includes: forming A sealing part procedure, a procedure for temporarily curing ultraviolet rays to connect substrates, and a main curing procedure using liquid crystal sealing material as a basic component. The procedure for connecting two substrates by a spacer is performed in a vacuum, and at atmospheric pressure Force as a way to press There is a uniform gap, and the substrate is compressed by the uniform force, so as to provide a unit cell with a uniform gap. Therefore, for example, the problem of peeling of the sealing material after the temporary hardening of ultraviolet rays can be solved easily. ^ ^ When using atmospheric pressure for vacuum encapsulation, Since the bag · θ # 10 ^ ills —-- I --- pack i — — — — — — Order ·! I-line, (Please read the precautions on the back before filling this page) 20

The X degree of this paper applies the Chinese National Standard (CNS) A4 specification (210 x 297 mm). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 0〇05κ 5: Description of the invention (/ f) causes the substrate alignment to shift. However, when only the atmospheric pressure is used as the compression method, a uniform pressure is applied to the entire substrate to prevent the alignment displacement of the substrate. As the spacer material, any material that can determine the substrate gap can be used. Examples include glass fibers, resin beads, and glass beads. The spacer material may be contained only in the sealing material 'or only in the effective display portion, but it is preferable to use a certain spacer material in the sealing material and the effective display portion respectively so as to have a uniform gap in the substrate. Any resin containing an ultraviolet curing component and a thermosetting component can be used as the resin of the sealing material of the present invention. However, a UV-curing component hardened by radical polymerization is more suitable because its interaction with liquid crystal is extremely small. The resin of the best sealing material is a polyfunctional acrylate resin, which contains bisphenol A type vinyl acrylate oligomers such as "SP-1563" and "SP_i5i9," produced by SHOWA HIGHPOLYMER CO. LTD. And polyfunctional methacrylate resin. Regarding the components of the liquid crystal sealing material of the present invention, if necessary, ultraviolet or thermal polymerization initiators, sensitizers, reaction diluents, and polymerization accelerators can be added. The heat curing agent of liquid crystal sealing material in the present invention is preferably an amine type heat curing agent, such as “Epikure Z” and “Epikure 150”, an imidazole type heat curing agent, such as “Epikure EMI-24”, an acid anhydride type heat curing agent. , Such as “Epikure YH-306”, which is produced by YUKA SHELL EPOXY CO., LTD, and hydrazine type heat curing agent, such as “VDH”, “UDH”, “LDH”, produced by AJINOMOTO CO., LTD , Because these heat-cured papers are again suitable for China National Standard (CNS) A4 (210 X 297 mm) I ------- I. ^ 7 · —! · I 1 (Please read the note on the back first Please fill in this page for matters) A7 405055 B7 V. It is stated that the agent will not interact with the liquid crystal, and is better than the heating temperature and service life. Figure 1 An oblique view shows the process of connecting the substrate in a vacuum display. Two of the electrodes with alignment treatment are included. A substrate 1A of the substrate includes a glass bead spacer material 2 for controlling the cell gap. In another substrate 1B, a sealing material 3 containing glass fiber 'ultraviolet curing component and thermosetting component is printed to form the two substrates. And is fixed by the fixed feet 4A to 4D and supported by the movable spacer plates 5A and 5B, so the two substrates will not touch each other until a proper vacuum state is obtained. In this state, the pressure in the vacuum chamber 6 It drops to 10 to 0.4 Ton. Then, the spacers 5A and 5B are removed, and the substrates 1A and 1B are connected. Thereafter, the vacuum chamber 6 is leaked to compress the substrates connected to each other by atmospheric pressure to generate a unit cell 7. Because the atmospheric pressure acts uniformly on the entire substrate without biasing pressure, a good unit cell with uniform cell gaps and no alignment displacement can be obtained. A part is covered by an ultraviolet cover 8 to irradiate only the sealing portion with ultraviolet rays, and the sealing material 3 is temporarily hardened as shown in FIG. 2. In order to improve the adhesiveness of the sealing material, the main hardening is performed. Procedure: By applying both UV hardening and thermosetting hardening sealing material to allow the sealing material to be temporarily hardened by UV irradiation after the unit cell is generated, therefore, as shown in FIG. 4, an excellent direct completion, no release or Cutting sealing material. Furthermore, by heat curing, a sealing material containing excellent adhesiveness and moisture resistance can be obtained. This paper size is applicable to the Chinese National Standard (CNS) A4 ‘Gate χ 297 public reply '(Please read the precautions on the back before filling this page)-· 装 i I! I Order ·! !! 1-Line Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ ----- 05055__B7____ V. Invention Description) After the main hardening process, cut the unit cell 7 and leave the electrode terminal Liquid crystal is filled in the opening 9 and the opening is sealed, and a liquid crystal display panel is completed. The edges of the sealing part of the liquid crystal display panel produced by the above procedure can be well aligned. This is because the sealing material is temporarily hardened by ultraviolet rays, and the improvement of the polymerizability increases the viscosity of the sealing material and eliminates the sealing material. Release into the alignment film. The manufacturing method of the liquid crystal display panel of this example is a procedure of applying a liquid crystal sealing material to connect two transparent substrates containing electrodes so that a predetermined gap is formed between the two substrates, and then liquid crystal is poured into the gap. The liquid crystal sealing material used to produce a liquid crystal display panel in the above-mentioned method includes an ultraviolet curing component and a thermosetting component. Regarding the resin to be used, which contains an ultraviolet curable component and a thermosetting component, it is preferable to use an acrylate resin and a methacrylate resin which undergo a curing process by radical polymerization. When an epoxy resin is used, a cationic photoinitiator is used as the ultraviolet hardener ', so high ultraviolet energy is required, and the polymerization speed of the epoxy resin is slow. When a cationic initiator is released into the liquid crystal, display quality is impaired due to an increase in current and poor alignment. Examples of the acrylate resin and the methacrylate resin include "SP-1519" and "SP-1563", which are produced by SHOWA HIGHPOLYMER CO., LTD. As the photoinitiator, an acetophenone-type photoinitiator, a benzoin-type photoinitiator, and a benzophenone-type photoinitiator can be used. Examples of photoinitiators include "Irgacure 651" and "Irgacure 907" manufactured by CIBA GEIGY JAPAN LTD. Regarding the heat curing agent, you can use the aromatic 2 3 I -------------! Order --- — — — — — (Please read the precautions on the back before filling in this page> This paper size applies to China National Standard (CNS) A4 specification (210 mm) 405055 A7 B7____ 5. Description of the invention (Μ)

Thermal curing agent, thermal curing agent of imidazole type, thermal curing agent of acid anhydride, thermal curing agent of hydrazine type, and thermal curing agent of organic peroxide type. Examples of the aromatic-type heat curing agent include "Epikure 2" and "Epikure 150" produced by YUKA SHELL EPOXY CO., LTD. Examples of the imidazole-type heat curing agent include "Epikure EMI · 24" manufactured by YUKA SHELL EPOXY CO., LTD. Examples of the acid anhydride type heat curing agent include "Epikure YH-306" produced by YUKA SHELL EPOXY CO., LTD. Examples of the hydrazine type heat curing agents include "UDH", "LDH" and "VDH" produced by AJINOMOTO CO., LTD. Examples of the organic peroxide type heat curing agent include "PERBUTYL 0", "PERBUTYL 355", "PERBUTYL L", "PERBUTYL Z", and "PERBUTYL IF" produced by NOF Corporation. [Second example] The generation procedure of the liquid crystal display panel of Example 2 of the present invention will be described with the attached table and drawings. Fig. 5 is a sectional view showing a liquid crystal display panel produced in the manufacturing method of the present invention. The structure of the liquid crystal display panel of this example is formed by applying a glass bead spacer material 2 between two substrates 12A and 12B with aligned electrodes to control the cell gap, and then the substrates 12A and 12B are sealed with a material. 3 are connected, and the liquid crystal 13 is sealed with the sealing material 3. The number 11 in FIG. 5 indicates a transparent electrode not formed on the main surfaces of the substrates 12A and 12B. Numeral 10 is an alignment film formed on the main surfaces of the substrates 12A and 12B to cover the transparent electrode 11. The alignment 10 film does not overlap the formation region of the sealing material 3. The size of this paper is applicable to Chinese national standard (CNS> A4 specification (210; — — — — — — — I I --- I — order -------- line (please read the precautions on the back before filling) (This page) 297 mm printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs)

4Q ^ 055 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention Ux) Material 3 is a sealing material containing UV-curable and thermosetting components. A liquid crystal display panel having the above-mentioned structure with a hardened state of various sealing materials 3 was produced, and the relationship between the resin hardening rate and the properties of the liquid crystal display panel was examined. Tables 1 and 2 show the composition of the UV-curable and thermosetting sealing materials used in this example. Table 3 shows the components of the ultraviolet-curable sealing material. Table 4 shows the relationship between the curing rate and curing conditions (ultraviolet irradiation time) of the curing resin. The curing resin in the sealing material is an epoxy acrylate ("SP-1563" produced by SHOWA HIGHPOLYMER CO., LTD.) ). In Table 4, the components of the 'sealing material A' are shown in Table 1. The components of the sealing material B are shown in Table 2, and the components of the sealing material C are shown in Table 3. Ingredient ratio (% by weight) Epoxy acrylate "SP-1563" produced by SHOWA HIGHPOLYMER CO_, LTD. 60 Isopentaerythritol triacrylate 15 γ-Glycidyloxypropylmethoxydiethoxy Silane 2 "Irgacure 651", produced by CIBA GEIGY JAPAN LTD. 3 "Epikure Z", produced by YUKA SHELL EPOXY CO., LTD. 5 25 > Paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 male) (%) ^ --- I--1 — t ·! (Please read the precautions on the back before filling out this page) Α7 40δ055 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Explanation of φ) --- Oxidation Silicon type filling material _ 15 Table 2 Composition ratio (% by weight) Epoxy acrylate "SP-1563", produced by SHOWA HIGHPOLYMER CO., LTD. 60 isopentaerythritol triacrylate 15 γ glycidyloxypropyl Methoxydiethoxysilane 2 "Irgacure 65Γ, produced by CIBA GEIGY JAPAN LTD. 3 hydrazine type heat curing agent" UDH ", produced by AJINOMOTO CO ·, LTD. 5 silicon oxide type filler material 15 Table 3 Ingredient ratio (% by weight %) Epoxy acrylate "SP-1563", produced by SHOWA HIGHPOLYMER CO., LTD. 65 Isopentaerythritol triacrylate 15 γ-glycidyloxypropylmethoxydiethoxysilane 2 "Irgacure 651 ", Installed by CIBA GEIGY JAPAN 3 26 I! —Order! 1-line > (Please read the precautions on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ) 405055 B7 A7 f Ming Tie- LTD. Production of silicon oxide filling materials 15 Table 4 Sealing / time 30 seconds 45 seconds 1 minute 3 minutes 5 minutes Sealing material A 40% 45% 50% 60% 60% Sealing material B 55 % 60% 60% 65% 65% Sealing material C 55% 60% 60% 65% 65% Here, the hardening rate is the amount of change in the carbon-carbon double bond (C = C) portion before and after the hardening reaction. And measured by FT-IR. That is, the proportion of the reacted C = C double bond portion to the C = C double bond portion of the entire hardened resin region. Table 5 shows the properties (appearance), and Table 6 shows the values at 1V, Current at 100HZ. Packing -------- Order --------- Line (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6 Seal / time 30 seconds 45 seconds 1 minute 3 minutes 5 minutes Sealing material A 3.5μΑ 3.5μΑ 3.5μΑ 2.6μΑ 2.6μΑ Sealing material B 2 · 8μΑ 2 · 6μΑ 2.5μΑ 2.5μΑ 2.5 μ A 2 7 Table 5 Seal / time 3 0 seconds 45 seconds 1 3 points 5 points Sealing material AXXX 〇〇Sealing material B 〇〇〇 ◎ ◎ Sealing material C 〇〇〇 ◎ ◎ This paper size applies to Chinese national standards (CNS> A4 size (210 X 297 mm) 405055 A7

High-pressure mercury lamp "HGQ-2000" produced by Japan's STORAGE BATTERY CQ., LTD. The 20 degree of irradiation is used to irradiate the sealing material.

As can be seen in Tables 4 to 6, the hardening rate of 60% or more of ultraviolet radiation can be visually determined in all sealing materials A (Table 丨), sealing materials B (Table 2), and sealing materials C (Table 3 ) To obtain a liquid crystal display panel having excellent display properties. In particular, when the ultraviolet curable component and the thermosetting curable component are used in the sealing material A at the same time, because the contained thermal curing agent ("Epikure Z" produced by γυκΑ SHELL EPOXY CO., LTD) is a liquid aromatic amine ', Then the thermosetting agent tends to be diluted into the liquid crystal. Therefore, in order to achieve a satisfactory level of display properties, the hardening rate of the hardened resin must be equal to or more than 60% to prevent the unhardened components of the unhardened resin and the thermosetting agent from being diluted in the liquid crystal. When a sealing material B (Table 2) containing an ultraviolet curing component and a thermosetting curing component is used, because the contained thermosetting agent ("UDH" produced by ΑΠΝΟΜΟΤΟ CO., LTD) is a particle type The hydrazine-type compound 'so the heat curing agent does not tend to dilute into the liquid crystal. In this example, similarly to the example of the UV-curing sealing material c (Table 3) containing no thermosetting agent, the curing rate of the hardening resin is 50% or more, so that the uncured components and the thermosetting agent can be prevented from being diluted to Can be obtained in liquid crystal— 2 8 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 feet) I installed ------- ^ order ----- I --- line ( Please read the precautions on the back before filling this page) 5405055, Description of the invention ("Satisfactory display level. From this we can know that ... using the same UV irradiation level, one particle type of thermosetting agent is better than one Liquid type heat curing agent. This is because the particle type heat curing agent can be hardened in a short period of time to improve productivity. Tables 7 to 9 show the hardening conditions (heated state) and the above-mentioned sealing material A (Table 1) and sealing material. The relationship between the hardening rate of B (Table 2) and the sealing material c (Table 3), and the relationship between heat curing of the hardened resin in different states after the above-mentioned ultraviolet reaction has been saturated. Similar faces_ (〇: = 〇 (Please read the notes on the back before filling in this page> 12 small 24 hours 90% 90% 90% 90% 90% 90% 90% 90% 90% --Installation! --Order ------ I--Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economy 8 Temperature / Time 1 hour 2 hours 5 hours 100 ° C 70% 70% --- i 75% 110 ° c 70% 70% --- 75% 29 12 hours 24 hours 80% 85% 80% 85% Table 7 Temperature / Time 1 Hours 2 hours'-~ 5 hours 100 ° C 75% 80%-85% 110 ° C 75% 80% 85% 120 ° C 80% 85% 1 ~ ---- 85% 130 ° C 85% 85 % 90% This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 405055 Table 9 Temperature / Time 1 hour 2 hours 5 hours 12 hours 24 hours 100. 65% 65% 65% 65% 65 % 110 ° C 65% 65% 65% 65% 65% 65% 120 ° C 65% 65% 65% 65% 65% 130 ° C 65% 65% 65% 65% 65% (Please read the notes on the back before filling (This page) A7 B7 statement explaining f 120 ...-80% 85% 85% 90% 90% 130 ° C 85% 85% 90% 90% 90% Adhesive properties after heat hardening. Table 10 Temperature / time 1 hour 2 hours 5 hours 12 hours 24 hours loot: 4.8 kgf 5.0 kgf 5.5 kgf 5.8 kgf 5.8 kgf 110 ° C 4.8 kgf 5.0 kgf 5.5 kgf 5.8 kgf 5.8 kgf 120 ° C 5.3 kgf 5.5 kgf 5.8 kgf 5.8 kgf 5.8 kgf 130 ° C 5.3 kgf 5.5 kgf 5.8 kgf 5.8 kgf 5.8 kgf 3 0 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 405055 V. Description of the invention d) Table 11 Temperature / Time 1 ----- 1 hour 2 hours 5 hours 12 hours 24 hours 100 ° c 4.0 4.0 kgf 4.5 kgf 5.0 kgf 5.3 kgf ll〇〇c -τ · 4 〇kgf 4.0 kgf 4.5 kgf 5.0 kgf 5.3 kgf-~~ t 120 ° c ^ ο kgf 5.5 kgf 5.8 kgf 6.0 kgf 6.0 kgf ---- 130 ° C 5.0_kgf_ 5.5 kgf 5.8 kgf 6.0 kgf 6.0 kgf (Please read the precautions on the back before filling this page > -I 1111 Temperature / Time _______ 1W, 2 hours 5 hours 12 hours 24 hours 100 ° c 3.5_k ^ f 3.5 kgf 3.5 kgf 4.0 kgf 4.0 kgf ------- ll〇〇c 3.5 kgf 3.5 kgf 3.5 kgf 4.0 kgf 4.0 kgf 120 ° C 3.8 k ^ f 3.8 kgf 3.8 kgf 4.0 kgf 4.0 kgf 130 ° c 3.8 kgf 3.8 kgf 3.8 kgf 4.0 kgf 4.0 kgf Intellectual Property of the Ministry of Economy These adhesive properties printed by the Bureau's Consumer Cooperatives were measured by the methods shown in Figures 6 and 7. Figure 6 shows a test device for peel strength testing. Figure 7 shows the test device. The paper dimensions are applicable to Chinese national standards ( CNS) A4 size (210 X 297 mm) 405055 A7 ------- B7 _________ 5. Side view of the invention description (> 1). In Figures 6 and 7, 'Number 21 gauge pressure gauge, 22 is pressure Column, 23 is a liquid crystal display panel holder, 24 is a liquid crystal display panel to be measured. It includes an upper substrate 24A and a lower substrate 24B, 25 is a support of a liquid crystal display panel, 26 is a base, and 27 is a pulse motor. The sealing width of the measured liquid crystal display panel was 1 mm. The measured liquid crystal display panel 24 is fixed on the base 26 'by using a pulse motor to move the bottom 26 upward and rise, so that the lower substrate 24B is pressed by the pressure column 22. When the upper substrate 24A is separated from the lower substrate 24B ', the compression power measured by the pressure gauge 21 is determined as the peel strength. From Tables 7 to 12, sealing materials containing UV-curable components and thermosetting components have a peel strength of 5 kgf and more, and a hardening rate of 80% or more of the hardening resin, which prevents subsequent cutting processes. Danger of substrate peeling caused by the split cell. On the other hand, the 'ultraviolet-curable sealing material cannot change the curing rate after heating, so this ultraviolet-curable sealing material cannot improve the adhesion. Therefore, a substrate and a sealing material with sufficient adhesiveness cannot be obtained by using only an ultraviolet curing type sealing material. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). From the above results, we can know that by using a UV-curing sealing material containing UV-curable components and thermosetting components, The UV-curing resin in the sealing material has a curing rate of 60% or more (when the sealing material contains a particle-type heat curing agent, the curing rate is 50% or more), and the resin is cured in the heat-curing sealing material. With a curing rate of 80% or more, a liquid crystal display panel having excellent display properties, strong adhesion of the sealing material and the substrate, and high mechanical strength can be obtained. In particular, a rapid hardening speed is provided in the first hardening stage of ultraviolet hardening to allow the substrate to be fixed without causing misalignment. So can 3 2

A7

V. Description of the Invention Gc) Prevent defective products caused by misalignment and improve production efficiency. 405055 (Example 3) Since the liquid crystal display panel used in the liquid crystal display device of Example 3 has a radical polymerizable sealing material containing an ultraviolet curing component and a thermosetting component, high reliability and display quality can be achieved. FIG. 5 shows a cross-sectional view of the liquid crystal display panel of this example, and detailed descriptions will be omitted here. Hereinafter, the components of the sealing material will be specifically described. As the (meth) acrylate derived from an epoxy compound, it is preferable to use an epoxy compound-derived (meth) acrylate of the bisphenol A type or a phenolic epoxy type epoxy acrylate. Examples of the bisphenol A-type (meth) acrylate derived from an epoxy compound include glycidyl ether-modified diacrylates of the bisphenol A type. Examples of (meth) acrylic acid esters derived from epoxy compounds of the novolak type include glycidyl ether-denatured diacrylates of the novolak type. In this example, a bisphenol A epoxy acrylate oligomer "SP-1563" is used and produced by SHOWA HIGHPOLYMER CO., LTD. Examples of (meth) acrylic acid esters containing a plurality of (meth) acrylic acid residues per molecule include isopentaerythritol triacrylate and isopentaerythritol tetraacrylate. In this example, an isopentaerythritol triacrylate "Viscoat # 300" is used, which is produced by Osaka Organic Chemical Industry LTD. Examples of (meth) acrylic acid esters containing a (meth) acrylic acid residue per molecule include tetrahydrofurfuryl acrylate, 2-hydroxypropyl acrylate, etc. 3 3 This paper is in accordance with Chinese national standards (CNS ) A4 size (210 X 297 mm) (Please read the precautions on the back before filling out this page) Binding --------- Line of Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperative Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Employee Consumer Cooperatives 405055 A7 __B7___ 5. Description of the invention (¾ I) and ethoxy diethylene glycol acrylate. In this example, ethoxydiethylene glycol acrylate "EC-A" is used, and is produced by KYOEISHA Chemical Co., LTD. Preferred photoinitiators are acetophenone-type photoinitiators, benzoin-type photoinitiators, and benzophenone-type photoinitiators. Examples of the acetophenone-type light initiator include diethoxyacetophenone, 4-t-butyl-bicycloacetophenone, and 2,2-dimethoxy-2-phenylacetone. Examples of the benzoin type light initiator include benzoin, benzoin ethyl ether, and benzyl methyl ketal. Examples of the benzophenone type light initiator include benzophenone, 4-phenylbenzophenone, and hydroxybenzophenone. In this example, 2,2-dimethoxy-2-phenylacetone "Irgacure 651" is used and manufactured by CIBA GEIGY JAPAN LTD. Preferred thermal curing agents are hydrazine-type thermal curing agents, aromatic amine-type thermal curing agents, acid anhydride thermal curing agents, and imidazole-type thermal curing agents. Examples of the hydrazine-type heat curing agent include 7,11-octadecadiene hydrazine and dihydrazine adipate. Examples of the aromatic amine-type heat curing agent include diaminodiphenylmethane and methylphenylenediamine. Examples of the acid anhydride type heat curing agent include hexahydrophthalic anhydride and tetrahydrophthalic anhydride. Examples of the imidazole-type heat curing agent include 2-ethylmethylimidazole, 2-methylimidazole, and 1-benzyl-2-methylimidazole. In this example, a hydrazine-type thermal curing homogeneous Γ UDH ”is produced by AJINOMOTO CO., LTD, and the average particle size of the sealing material is adjusted to 3〆m after three times of rolling when kneading the sealing material, or a similar size is used. "Epikure Z" of denatured aromatic amines is produced by YUKA SHELL EPOXY CO., LTD. As for the silane coupling agent, glycidyl ethoxysilane and glycidyl methoxysilane are preferred. In this example, Use r-glycidyl oxygen 34 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) Packing ---- 1 ---- Order ------ Line '' (Please read the back first Please fill in this page for the matters needing attention) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 405055 V. Description of Invention (P)

Propyltrimethoxysilane "KBM 403", which is SHIN-ETSU

Produced by Chemical CO_, LTD. Preferred inorganic fillers are hydrated magnesium silicate, calcium carbonate, aluminum carbonate, and silicon oxide. In this example, the hydrated magnesium silicate "Super Talc SG-95" produced by Nippon TALC CO., LTD was used, with an average particle diameter of 1.4 # m, and the second particle produced by Nippon AEROCIL CO., LTD was used. Silicon oxide "Aerocil R202" with an average particle size of 15 nm. In UV curing, high-pressure mercury lamps are generally used, and the irradiation conditions depend on the type of lamp, the composition and amount of the sealing material, and the distance from the lamp. Therefore, the hardening conditions can be adjusted according to the irradiation conditions. There are no particular restrictions on energy, but for example an irradiation condition of approximately 500 m to 600 is used. In this example, the high-pressure mercury lamp "HGQ-2000" used is produced by STORAGE BATTERY CO., LTD. Its ultraviolet irradiation wavelength is 420 nm or shorter, and the irradiation intensity is 20 mW / cm2 for 2 minutes. , And added to the sealing material, so that it contains 4800 mJ of irradiation energy. The thermosetting conditions vary depending on the type of thermosetting agent and the types and ratios of other materials. Although not particularly limited, the conditions adopted are one hour or longer at 100 ° C to 150 ° C. In this example, the adopted condition is 120 ° C for I2 hours, which is equal to the annealing conditions of the liquid crystal display panel. (Example 4) FIG. 5 shows a cross-sectional view of a liquid crystal display panel used for evaluation. Because the structure and parts have already been explained, we will not repeat them here. Table 13 shows the composition, proportion, initial adhesion and the pressure at 2 atmospheres. 3 5 This paper size is applicable to China National Standard (CNS) A4 specifications (210 X 297 mm). ------ line < < Please read the notes on the back before filling out this page) Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 405055 A7 B7 _____. V. Description of Invention (Μ) Power, 120%, Adhesion after pressure baking test (hereinafter abbreviated as PCT) for 8 hours at 120 ° C, and changes in display properties and currents of the LCD panel after 1000 hours at 120 ° C for high temperature test 'and in The display properties and current changed after 60 hours of humidity resistance test at 60 ° C and 95%. Table 13 Example Comparative Example ABCABC “SP-1563” 65 60 65 50 70 65 “Viscoat # 300” 5 10 5 5 5 7 “EC-A” 5 5 5 20 7 “KBM 403” 3 3 3 3 3 3 “Irgacure 651 ”5 5 5 5 5 5“ Epikure Z ”4 4 4 4“ UDH ”4“ Super Talc SG-95 ”10 10 10 10 10 10“ Aerosil R202 ”3 3 3 3 3 3 At the beginning of adhesion ◎ ◎ ◎ ◎ X Δ PCT 8 hours ◎ ◎ ◎ XX Current 値 120. . , 1000 hours ◎ ◎ Δ △ 〇 60 ° C '95%' 1000 hours ◎ ◎ ◎ X ◎ X Appearance evaluation 120. . 、 〇〇〇〇 ◎ ◎ ◎ X ◎ ◎ 3 6 This paper size is applicable to the national standard (CNS) A4 specifications (210 X 297 mm) Packing -------- Order ------ --Line < V (please read the precautions on the back before filling this page) 405055 A7 V. The invention is cute (ii B7 at 60 ° C '95%' 1000 hours ◎ ◎ ◎ X ◎ ◎ Economic Zou Intellectual Property Bureau Printed by the employee's consumer cooperation ◎ Good '〇 No problem in use, △ Not enough for future use, X unavailability evaluation criteria are based on the usability of OA equipment such as general personal computers and word processors. Mark "△ "Insufficient future use" means that it may not be suitable for harsh environments, which refers to those developed in the near future, such as in-car or outdoor applications. Examples A and B each contain 5% and 10% (Meth) acrylate containing multiple (meth) acrylic residues "Viscoat # 300". Examples A and C each have a denatured aromatic amine "Epikure Z" and a hydrazine type "UDH" as heat Curing agent. Other components and ratios are the same. Comparative Example A contains (meth) acrylate, which contains 20% The amount (%) of (meth) acrylic acid residue "EC-A" per molecule. Comparative Example B does not have "EC-A". Comparative Example C does not have a thermosetting agent. When Comparative Example A exists at a high temperature for a period of time After that, the liquid crystal alignment becomes worse. In addition, the current 値 increases in the moisture resistance test and the high temperature test, which deteriorates the display quality of the liquid crystal display device. After the high temperature test or the high voltage test, the liquid crystals in Comparative Examples B and C The properties of the display panel did not cause any problems. However, the initial adhesion of Comparative Example B was poor, and the adhesion of Comparative Example C after PCT was poor. From the above results, we can know that: Examples A, B, and C are good sealing materials. , Which can provide a reliable liquid crystal display device, including good display products 3 7 < Please read the precautions on the back before filling this page)

-I ------- 1 I I! I

National Standard (CNS) A4 specification (210 X 297 mm) ί 05055: 5. Description of the invention-quality 'and no problem in the case of adhesion, high temperature and high humidity. (Example 5) Hereinafter, an example of the liquid crystal display device of the present invention will be described. The liquid crystal display device is formed by a dropping method, that is, a sealing material is formed on one of two substrates of an electrode having alignment processing. The two substrates are connected by a spacer, and a liquid crystal is dropped between them. The dropping method will be described in FIGS. 8 and 9. Fig. 8 is a perspective view illustrating a procedure of dropping liquid crystals in a process of manufacturing a liquid crystal display panel in a liquid crystal display device. The cross-sectional view of FIG. 9 shows a process for manufacturing a liquid crystal display panel in a liquid crystal display device by connecting a substrate and another opposing substrate through a spacer material, the former substrate has been dripped by the liquid crystal. In Fig. 8, the sealing material 3 is formed on the inner side of the substrate 12B to which the alignment-treated electrode is applied by screen printing in a random pattern. The liquid crystal 13 is dropped into the area surrounded by the sealing material by the liquid dispenser 14. In Fig. 9, the glass bead spacer material 2 is uniformly and fixed on the inside of a substrate 12A containing an alignment-treated electrode, which is opposite to the substrate 12B on which the liquid crystal is placed. Then, the substrates 12A and 12B are connected to each other, and this is performed in the vacuum chamber 6 in the depressurization of 0.4 to 1.0 Torr. The substrate is pressurized by further atmospheric pressure to control the gap. Table 14 shows the composition, proportion, and alignment of the liquid crystal on the edge of the sealed portion, and the change in current and appearance after 1000 hours of high temperature test at 120 ° C. Hourly moisture resistance test 3 8 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -1 — I ----- Order · I — 11111 · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, 405055 (5. Description of the invention) Current changes and appearance evaluation. Table 14 Comparative Example of DuPont Printing Examples of Employees' Co-operation in the Intellectual Property Bureau of the Ministry of Economic Affairs DEFDEF “SP-1563” 68 60 68 62 58 55 “Viscoat # 300” 5 5 5 8 15 5 “EC-A” 2 10 2 9 2 9 "Epicoat 802" 10 "KBM 403" 3 3 3 3 3 3 "Irgacure 65 1" 5 5 5 5 5 5 "Epikure Z" 4 4 4 "UDH" 4 "Super Talc SG-95" 10 10 10 10 10 10 "Aerosil R202" 3 3 3 3 3 3 Orientation of the sealing edge ◎ ◎ ◎ XX Current 値 120 ° C, 1000 hours ◎ ◎ ◎ 〇 ◎ 〇60 ° C '95%' 1000 hours ◎ ◎ ◎ X ◎ X Appearance Evaluation 120 ° C, 100,000 ◎ ◎ ◎ 〇〇〇〇 9 (Please read the notes on the back before filling this page) -I-I I ----- Order ----- --- · This paper size is applicable to the National Standard (CNS) A4 (210 X 297 mm) A7 405055_B7

V. 1 ^ ηΒ · ί «πρ / ^ ___________-_, 14 VAJ / 4 V 60 ° C '95%' 1000 hours ◎ ◎ ◎ X ◎ X ◎ Good, 〇 No problem in use, △ is not enough for the future Printed with 'x Unavailable Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives Printed examples D and E are (meth) acrylates containing 2% and 10% by weight, each containing a (meth) acrylic residue per molecule " EC-A ". Examples D and F each contain a denatured aromatic amine "Epikure Z" and a hydrazine type "UDH" as heat curing agents. Other ingredients and ratios are the same. Comparative Example D does not contain a thermal curing agent "Epikure Z". Comparative Example A contains 15% by weight (meth) acrylate in excess and contains multiple (meth) acrylic acid residues "Viscoat # 300" per molecule. Comparative Example F contains "Epicoat 802" produced by YUKA SHELL EPOXY CO., LTD as an epoxy resin, and a heat curing agent equivalent to the epoxy resin. From the above results, it can be seen that in Comparative Examples E and F, the 'unhardened component' tends to be diluted in the liquid crystal, while the area where the sealing edge alignment is poor in the liquid crystal is large, and the uranium invasion display area is large. Moreover, in Comparative Examples D and F, it was found to be unreliable by the moisture resistance test, and the current 値 was increased. The reason includes that the unhardened component is diluted by water or high-temperature liquid crystal. This is because it contains a large amount of components not related to ultraviolet polymerization and hardening, such as epoxy resin, and the lack of a heat curing agent reduces the cross-linking density and deteriorates the moisture resistance. As a result, the absorption of moisture is increased, thereby reducing the moisture resistance. On the other hand, examples D, E, and F show that under the high temperature and humidity environment, 40 paper sizes are applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) — — — — — — — — — — — -Install! r-Order-JI —-- 11r (Please read the precautions on the back before filling out this page) 405055 A7 B7 V. Description of the invention (the sealing position is still in good alignment and excellent reliability. Based on this, apply this The sealing material of the invention can obtain a liquid crystal display device with good display quality and reliability, which is the same even if it is applied to the production including the dropping method. -Line &\; (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 1 This paper size is applicable _ National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

A8 B8 C8 D8 405055 6. Scope of Patent Application 1. A method for manufacturing a liquid crystal display device, including the following steps: A sealing material is used to form a seal on the electrode-side end of at least one of the substrates to be sealed with electrodes. In part, the two substrates are connected by a spacer, at least the sealing portion is irradiated with ultraviolet rays to temporarily harden the sealing portion to provide a hardening rate of at least 50%, and the sealing portion is heated as the main hardening to increase the hardening. The rate is at least 80%, wherein the sealing material comprises a monomer or oligomer of (meth) acrylate derived from an epoxy compound, (meth) acrylic acid ester ), A photoinitiator, a heat curing agent, and an inorganic filler, wherein (meth) acrylic acid ester contains 5 to 10% based on the weight percentage of the sealing material (Meth) acrylic acid ester [which contains multiple (meth) acrylic acid residues per molecule] and contains 12 to 10% (meth) acrylic acid ester [which contains one (meth) acrylic acid per molecule) Dilute acid residue Matter], which sealing material may be UV curable and thermally curable, wherein the sealing material after free-radical polymerization. 2. The method for manufacturing a liquid crystal display device according to item 1 of the scope of patent application, wherein the connection procedure is performed under reduced atmospheric pressure. 3. The method for manufacturing a liquid crystal display device according to item 1 of the patent application, wherein the substrate having the electrodes is subjected to an alignment treatment. (Please read the precautions on the back before filling this page) • Install --- 丨 II--Order ---- I!! Line. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 2 This paper size applies to China Standard (CNS) A4 specification (210 x 297 mm) A8 B8 C8 D8 405055 VI. Patent application scope k coffee 4. A method of manufacturing a liquid crystal display panel 'contains the following steps · Preparation of a sealing material, which includes a derivative derived from a ring Monomers or oligomers of (meth) acrylate of oxygen compounds, (meth) acrylic acid ester, a photoinitiator, a heat curing agent And an inorganic filler, wherein (meth) acrylic acid ester contains 5 to 10% of (meth) acrylic acid ester [each Multiple (meth) acrylic residues in the molecule] and 2 to 10% (meth) acrylic esters [one (meth) acrylic residue in each molecule], and the sealing material is UV-curable And heat curing, wherein the sealing material undergoes polymerization, The portion to be sealed on the surface of the transparent substrate 'forms the sealing material containing the hardening resin and the hardener of the initial hardening resin, and the liquid crystal is added dropwise to the area surrounded by the sealing material to connect a second transparent substrate on which the electrode is installed Surface to the surface of a first transparent substrate on which electrodes have been mounted, and the two transparent substrates with electrodes are connected by the above-mentioned sealing material, wherein the manufacturing method includes the first procedure of irradiating ultraviolet rays to the sealing material, and the first procedure The second process of increasing the hardening by heating the sealing material later, the hardening resin of the middle sealing material is hardened to hard after the first process: the rate is two% or more, and the hardening rate after the second process is 8 ()% Or more. … 5. If you apply for the liquid crystal of item 4 in the application, the hardening resin of the sealing material will be hardened after this procedure. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm (please (Please read the notes on the back before filling this page.) Packing -------- 'I.Order ------------ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A8 405055 I VI.Application The patent range is 60% or more, and the hardening rate is 80% or more after the second procedure. 6. The method of manufacturing a liquid crystal display panel according to item 4 of the patent application range, wherein the heat curing agent is a particle type heat Curing agent 'its average particle size is smaller or smaller. 7. A method for manufacturing a liquid crystal display panel as described in the fourth item of the patent application' wherein a pair of large-area transparent substrates with electrodes are used to mount a plurality of liquid crystal display panels, This allows the pair of large-area transparent substrates with electrodes to be divided into multiple liquid crystal display panels. 8. A sealing material composition for a liquid crystal display panel 'comprises a (meth) acrylate derived from an epoxy compound ( (meth) acrylate) Polymer or oligomer, (meth) acrylic acid ester, a photoinitiator, a heat curing agent, and an inorganic filler 'wherein' is expressed as a percentage of the weight of the sealing material ' (Meth) acrylic acid ester contains 5 to 10% of (meth) acrylic acid ester [which contains multiple (meth) acrylic residues per molecule] 'and contains 2 to 10% of (Methyl) propionic acid vinegar [which contains one (meth) propionic acid residue per molecule] 'and the sealing material can be UV-cured and heat-cured, wherein the sealing material has undergone radical polymerization. 9. If applied Sealing material for liquid crystal display panel in the scope of the patent No. 8 3 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)-Binding .: -------- Printed by A8, B8, C8, D8, 405055, Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Patented composition, which is derived from the (meth) acrylate moray eel of epoxy compounds or Oligomers to 70% by weight of the sealing material, and Health_Epoxy compound from bisphenol A and phenolic lacquer. 10 • Seal tree composition for liquid crystal display panels such as the scope of patent application No. 8 wherein the photoinitiator accounts for 3 to 3 5% by weight, and select from the following groups: acetophenone photoinitiator, benzoin photoinitiator, and benzophenone photoinitiator. U. For the liquid crystal display of item 8 of the application The sealing material composition of the plate, wherein the thermal curing agent accounts for 2 to 纟% by weight of the sealing material, and is selected from the group consisting of: 醯 胼, aromatic amine, and acid. 12. The material composition of the _Liquid Display Panel of _Please Special Item_8, in which the thermal curing agent is a particle-forming agent, and its square size is 3 # m or less. 13. For example, the _ material composition for liquid crystal display of item 8 of the patent range, which further contains-Shayuan weighing mixture, accounted for = weight percentage, and select from the following group: _ water glycerol ^ and glycidyl methoxy Silane. Oxygen lane wonderful courtyard 14 · _ | Conversion of _8 axis liquid crystal material composition, in which the average size of the inorganic filler is 丨 = This paper size is applicable to China National Standard (CNS) A4 (210 x 297) -^ 111111-¾ ^ --— — — — — — ^ ------- II ^ I (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A8 B8 C8 D8 405055, the scope of application for patents accounts for 8 to 20% by weight of the sealing material. The following options are selected: hydrated magnesium, carbon, and carbon. Is a liquid crystal display surface. The transparent surface at the beginning will be difficult. There is no reaction, and the seals are connected to each other, wherein the sealing material undergoes a compensation process, in which the two materials of the sealing material increase the second most hardening, and wherein the self-hardening rate of the sealing material is more than π. (&Meth; acrylamide (meth) acryla monomer or acid: =: yHC---inorganic traces which are bionic to epoxy compounds) ) Propionate (—h) acrylic acid ⑻ di = which contains multiple (methyl) propane dimers per molecule], Containing from 2 to (meth) Cool degenerate acid [which contains per molecule a (meth) Li acid residue], and the sealing material may be UV curable and thermally curable 'wherein the sealing material after free-radical polymerization. -------------- Installation --------- Order --------- Line · (Please read the precautions on the back before filling this page) Economy The Ministry of Intellectual Property Bureau's employees' cooperatives print private papers in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm)