TW200540537A - Curable resin composition for liquid crystal displays, sealing material for the liquid crystal dispensing method, transfer materials, and liquid crystal displays - Google Patents

Abstract

The invention aims at providing a curable resin composition for liquid crystal displays which little causes liquid crystal contamination and can give liquid crystal displays permitting high-quality images having little color irregularity when used as the sealing material in the production of liquid crystal displays by the dispenser method even if the dispenser method is not accompanied with the irradiation with ultraviolet rays; a sealing material for the liquid crystal dispensing method which consists of the composition; transfer materials; and liquid crystal displays. The composition is one curable by heating alone which comprises as the resin component only a curable resin bearing in the molecule both functional groups capable of hydrogen bonding and at least one kind of functional groups selected from the group consisting of epoxy, oxetane, and episulfide groups and having a value of 3.5 x 10<SP>-3</SP> or above as obtained by dividing the number of functional groups capable of hydrogen bonding in the molecule by the weight-average molecular weight and which further contains a thermal curing agent and/or a cationic polymerization initiator.

Description

200540537 IX. Description of the invention ... [Technical field to which the invention belongs] The present invention relates to a curable resin composition for a liquid crystal display element, whether it is used as a sealant or not when the liquid crystal display element is manufactured by a dropping method. When the liquid crystal display element is manufactured by the dropping method by ultraviolet irradiation, it is not easy to cause liquid crystal stains, and it can produce a liquid crystal display element with high image quality with few stains. In addition, the present invention relates to a hardening method for a liquid crystal display element. Resin composition, which is less susceptible to liquid crystal contamination, and can produce liquid crystal display elements with high image quality and fewer color spots; in addition, the present invention relates to a liquid crystal composed of the curable resin composition for the liquid crystal display element A sealing agent for a dropping method, a vertical conductive material, and a liquid crystal display element. [Prior art] In the past, the manufacturing method of liquid crystal display elements such as liquid crystal display units is that two substrates with electrodes are opposed to each other at a predetermined interval, and the periphery is sealed with a sealant made of a hardening resin composition. The unit, from one of them, injects liquid crystal into the unit through a liquid crystal injection port provided, and then closes the liquid crystal injection port with a sealant or a sealing agent. In the method described above, first of all, for two substrates with electrodes, i substrates are formed with a thermosetting sealant by a brush of a net to form a sealing pattern provided with liquid crystal injection: 60 to 10 (rc Pre-bake to dry the heart clams in the sealant. Secondly, the two substrates are aligned and bonded to each other by holding the spacers, and hot pressed at 11 () ~ 22 (rc for ig ~ ⑽ minutes) ， Tuning 5 200540537 The distance between the vicinity of the entire seal. De @ ampere heating in the furnace at 110 ~ 220 ° C for 10 ~ 120 minutes to make the sealant officially stone bearing # # / / d., Two people, from the liquid crystal injection port will After the liquid crystal is injected, the liquid crystal display element is sealed by a sealing agent to make a liquid crystal display element. 疋 According to the other manufacturing methods, there are the following problems: deviations in position and spacing due to forces. , Reduction of adhesion between the sealant and the substrate, etc. 'Residual lotion will thermally expand and generate air bubbles, resulting in gaps.

, Or eai pass' long sealing and hardening time; complicated pre-baking procedures; the sealant can have a shorter service life due to solvent volatilization, and the night crystal injection time / long is particularly bad. For large-scale liquid crystal display devices in recent years In terms of liquid crystal injection, too long a time is a serious problem. ^ In this regard, a method of manufacturing a liquid crystal display element called a dripping method using a photo-hardening and heat-curing type seal was also discussed. Dropping: To: ‘First, one of the two substrates with electrodes is formed into a rectangular seal pattern with a dlspensor. Secondly, the entire surface of the frame of the substrate is coated with liquid crystal micro-liquid in the state where the sealant has not yet hardened, and the other substrate is quickly stacked, and the sealing portion is irradiated with purple for the second time to harden temporarily. After that, the substrate is hardened by heating during the liquid crystal annealing to produce a liquid crystal display device. As long as the substrates are bonded under reduced pressure, a liquid crystal display element can be manufactured from extremely high efficiency. In the future, it is expected that this dripping method will become the mainstream of the manufacturing method of liquid crystal display devices. The sealing agent for a liquid crystal display element used in the aforementioned dropping method is, for example, disclosed in Patent Document 丨 a light-hardening heat-curing and use in a sealing agent, which is photo-hardened with free radicals generated by ultraviolet irradiation, Furthermore, it heat-hardens with the thermosetting agent contained. 6 200540537 On the other hand, in Patent Document 2, Patent Document 3, Patent Document 4, Patent Document 5, and Patent Document 6, a sealant using a cationically polymerizable compound has been proposed as a sealant without using a thermosetting agent. Approach. This type of sealant using a cationically polymerizable compound has advantages not only in terms of storage stability, excellent low-temperature quick-curing properties, short time required for hardening, but also shortening manufacturing time compared with a sealant using a thermosetting agent, which is an advantage . However, in terms of the dropping method, the sealant in the uncured state during the manufacturing process will directly contact the liquid crystal, so the components of the sealant may be dissolved in the liquid crystal. In the obtained liquid crystal display device, the liquid crystal alignment appears. Problems such as troubles and reduction of the voltage holding rate of the display element. In particular, the development of liquid crystal panels in recent years has been accompanied by a reduction in power consumption for mobile applications and the like, and they tend to use liquid crystals with low driving voltages (low-voltage liquid crystals). This low-voltage type liquid crystal ’has a particularly large dielectric anisotropy, which makes it easy to catch impurities, which can cause significant disorder of liquid crystal alignment or decrease in voltage retention of the display element.

In addition, with the increase in the size of substrates in recent years, the amount of energy required to irradiate ultraviolet rays has increased. Therefore, problems such as the increase in the size of ultraviolet irradiation devices have led to the production of liquid crystal display elements by the dropping method. The method of irradiation has high expectations. However, in the case where the ultraviolet light-emitting device is not used, the time during which it is in an uncured state becomes longer, the alignment disorder caused by heat curing, and the weight of the display element are dropped. Due to the liquid crystal positional deviation, the voltage retention rate due to liquid crystal contamination is reduced, etc. 200540537 [Japanese Patent Document 1] JP 2001-133794 [Japanese Patent Document 2] JP 10-330717 [Japan Patent Document 3] JP 2001-142079 [Japanese Patent Document 4] JP 2002-3 17172 [Japanese Patent Document 5] JP 2003-96184 [Japanese Patent Document 6] JP 2003 -961 No. 85 [Contents of the invention] ... The present invention is in the above-mentioned state, and its purpose is to provide a curable resin composition for a liquid crystal display device, which is used as a seal when a liquid crystal display element is manufactured by a dropping method. When used as an agent or when used as a sealant in the manufacture of liquid crystal display elements by a dripping method without ultraviolet irradiation, it is not easy to cause liquid crystal contamination, and can produce image quality with few stains. The liquid crystal display element; Further object of the present invention is to provide a display of the liquid crystal constituting the liquid crystal dropping method of the curable resin composition with a sealant member, transfer material and a liquid crystal display element. Means for Solving the Problem The first invention is a curable resin composition for a liquid crystal display device. The resin component has only one component having a hydrogen-bonding functional group and one selected from epoxy groups and oxetane in one molecule. A hardening resin having at least one functional group in a group consisting of a base and an episulfide group, and a value obtained by dividing the number of hydrogen-bonding functional groups in a molecule by a weight average molecular weight of 3.5 × 10 · 3 or more; and a thermosetting agent And / or a cationic polymerization initiator. The second invention of the present invention is a hardenable intestinal composition 8 200540537 for liquid crystal display elements. The resin component is only: i molecule has a hydrogen bonding functional group and optional oxygen-producing group, oxetanyl group, and episulfide. At least one functional group in the group formed by the physical group, the number of hydrogen-bonding functional groups in i 1 molecule divided by weight: average eight: hardened resin with a value of 3.5X or more as well as the polymerizability of softening the heart Resin; and contains thermosetting-and 1 = daughter polymerization initiator. W ^ 3. The present invention is a type of hardening resin for liquid crystal display elements: 'contains. 1 molecule having a hydrogen bonding functional group and selected from epoxy, oxa-butanyl, and episulfide groups. A curable resin having at least one type of functional group in the group and a value obtained by dividing the number of hydrogen-bonding functional groups in one molecule by a weight average molecular weight of 3.5 × 3 or more, and a cationic polymerization initiator. ... The present invention is described in detail below. As a result of diligent research, the inventor found that if the curable resin composition used in the sealant has only the resin component: the molecule has more than a specific hydrogen-bonding functional group and is selected from epoxy groups and oxygen The curable resins of at least i functional groups in the group consisting of heterocycline group and episulfide group can be used to produce liquid crystal display elements without dropping ultraviolet rays, and the liquid crystal is not polluted. There is no liquid crystal display element with disordered liquid crystal alignment and a reduced voltage holding ratio of the core element. Thus, the curable resin composition for a liquid crystal display element of the present invention (hereinafter also referred to as the resin composition of the first invention) was completed. Furthermore, as a result of intensive research by the present inventors, it was found that if the curable resin composition used in the sealant contains a resin component in the resin molecule: it has a functional group having a specific hydrogen bond or more and an epoxy group, The hardening resin having at least one functional group in the group consisting of oxetane 9 200540537 group and% sulfide group, and the polymerizable resin having a softening temperature of 5 (rc or higher) are the same as the resin composition of the present invention. In the case of manufacturing a night crystal display element by a dropping method without ultraviolet irradiation, the liquid crystal is not polluted, so that the curable resin composition for a liquid crystal display element of the present invention (hereinafter also referred to as the second The resin composition of the present invention). Furthermore, as a result of intensive research, the inventor found that if the liquid crystal display element is produced by a conventional method for curing the sealant, the resin A 丨 has Hydrogen-bonding functional group and at least one kind of functional group selected from the group consisting of epoxy group, oxetanyl group and episulfide group, and the number of hydrogen-bonding functional groups in one molecule is divided A resin with a weight-average molecular weight of 3.5x10 or more and a cationic polymerization initiator in combination will not cause contamination of the liquid crystal, and can obtain a liquid crystal display device without liquid crystal alignment disorder and reduced voltage retention of the display device. Thus, the curable resin composition for a liquid crystal display element of the third aspect of the present invention (hereinafter also referred to as the resin composition of the third aspect of the present invention) has been completed. In the following description, it is not particularly distinguished between the i, 帛 2 and the ^ Case of the resin composition of the present invention 'is simply referred to as "the resin composition of the present invention". The resin composition of the first invention has only the resin component: the i molecule has a hydrogen-bonding functional group and an option. The value obtained by dividing at least one functional group in the group consisting of an epoxy group, an oxo group, and an episulfide group, and the number of hydrogen-bonding functional groups in i Uon divided by the weight average molecular weight is 35xl0_3 or more. Resin. 200540537 The resin composition of the second aspect of the present invention has only one resin component: one or more molecules having a specific hydrogen-bonding functional group and selected from epoxy groups, oxetanyl groups, and episulfides. A curable resin having at least one functional group in the group and a polymerizable resin having a softening temperature of 50 ° C or higher. The above-mentioned curable resin contained in the resin composition of the first aspect of the present invention has a self-selecting ring in one molecule. It has at least one type of functional group in the group consisting of an oxy group, an oxetanyl group, and an episulfide group, and therefore exhibits appropriate thermosetting properties. Compared with conventional sealants for liquid crystal display elements, It contains a large amount of hydrogen-bonding functional groups and has high polarity. Therefore, even if the resin composition of the first invention is in contact with liquid crystal in an uncured state, the hardenability of the resin composition of the first invention The resin is still not easily dissolved in the liquid crystal, and it is difficult to cause liquid crystal contamination and color spots to occur in the liquid crystal display element. The resin composition of the second aspect of the present invention contains the same hardening resin as the resin composition of the first aspect of the present invention. It exhibits appropriate thermosetting properties, and has a larger amount of hydrogen-bonding functional groups in the molecule and higher polarity than conventional sealants for liquid crystal display elements. In addition, the polymerizable resin contained in addition to the curable resin has a softening temperature of 5 (rc or higher), so that fluidity does not increase in an unheated state. Therefore, even if the resin composition of the second invention is In contact with the liquid crystal in an uncured state, the hardening resin and the polymerizable resin in the resin composition of the second invention are still not easily dissolved in the liquid crystal, and it is not easy to cause liquid crystal contamination and color spots to occur in the liquid crystal display element. The softening temperature referred to in this specification is a temperature at which the solid polymerizable resin is softened by heat, and is measured in accordance with the JIS κ 7234 ring and ball method, and indicates the temperature at which the test method is in a state prescribed by the test method. 11 200540537 ^ No. 1, No. 1 2 The resin composition of the present invention is not only used as a sealant for the manufacture of liquid crystal displays by ordinary dropping methods such as outside radiation and heating, even if it is used as a dropping method without ultraviolet irradiation. T-seal zirconia used in the manufacture of liquid crystal display elements_Neither soluble in liquid crystal towels, can produce liquid crystal display elements with high image quality with few color spots : In the resin composition of the second aspect of the present invention, the lower limit of the value obtained by dividing the number of hydrogen-bonding functional groups in the curable resin knife by the weight average molecular weight is 3 · 5 × 1 () _ 3. If less than 3 · 5χ5 () .3, the amount of the hydrogen-bonding functional group contained in the molecule of the curable resin is small, and the polarity of the curable resin will be lowered °, so that the resin composition # 2 of the present invention is not subjected to ultraviolet irradiation In the case where the sealing agent for a liquid crystal display element used in the dropping method is used, the uncured hardening resin component will dissolve into the liquid crystal and cause liquid crystal contamination. The lower limit is preferably 4.0 × 3-3 mol / g. The number of the hydrogen-bonding functional groups mentioned above is a value calculated by the following formula 当 when the compound having a hydrogen-bonding functional group is a single compound *. The number of hydrogen-bonding H g 旎 groups (ΗX) = (The number of hydrogen-bonding functional groups in the molecule X of the compound X (weight average molecular weight of the compound X) ⑴ When the compound having a hydrogen-bonding functional group is composed of a plurality of resin mixtures, the number of the above-mentioned hydrogen-bonding functional groups Can each be hydrogen bonded 2 The content per unit weight (weight fraction) of the compound is different by weight. For example, when a compound having a hydrogen-bonding functional group is composed of a compound A, a dagger B, and a compound c, if each The hydrogen of the compound 鐽 12 200540537 ^ B When the base numbers are Ha, Ηβ and heart, respectively, the number of hydrogen-bonding functional groups is calculated by the following formula (2). Hydrogen bond g (Habc) = HAPA + HBPB + Hcpc In the formula (2), Pα represents the weight fraction of the compound α. The hydrogen-bonding functional group is not particularly limited as long as it is a argon-bonding functional group or a residue, and examples thereof include a fluorenyl group. , Nη2 group, NHR group (R represents aromatic, aliphatic hydrocarbons or derivatives thereof), COH group, COH2 group, NZO group, etc., or a CDR bond, NZO in the molecule Among the residues such as a bond, a CONHC0 bond, and a NΗ—NΗ bond, a via group and / or a urethane group are preferred. In the resin composition of the first and second inventions, the curable resin has at least i kinds of functional groups selected from the group consisting of an epoxy group, an oxetanyl group, and an episulfide group in one molecule. Above 2 is preferred. #This reduces the amount of residual unreacted substances after the cross-linking reaction, and can control the dyeing of the liquid crystal caused by the residual unreacted substances. The above-mentioned functional group contained in H i / molecule is preferably 6 or less. The reason is that if it exceeds 6, the hardening shrinkage will increase, and the subsequent force will decrease. There is no particular limitation on the epoxy-based curable resin on the soil hexamethylene. For example, bis (3-alkylmethyl-4-epoxypropyloxy- 5-methylphenyl) methylbenzene, bis (3,5 ~~ bis-transylmethyl-*-epoxypropyloxy) methane represented by the following formula (2), and the following formula (3) Represented compounds, etc. In addition, = can be produced by, for example, isocyanate and an epoxy compound having a radical, and reacting a polyhydric alcohol with a difunctional or higher isocyanate to produce: radical = 13 200540537 ester compound, Then, the terminal isocyanate group of the urethane compound is reacted with an epoxy compound having an alkyl group, and the like. The epoxy compound having a hydroxyl group is not particularly limited, and examples thereof include sugar alcohols.

Λ? Ί? H3 ch3 η ο CH2,0-c-N-CH2-CHrCH-CHr〒-CH2H0 ~ H2〇 ^ A (3) ch3 has a hydrogen-bonding functional group in one molecule and 2 or more oxygen The curable resin of heterocyclobutane is not particularly limited, and examples thereof include those obtained by reacting an isocyanate with an oxetane compound having a hydroxyl group, and reacting a polyol with a monofunctional or higher isocyanate to produce an amine group. A formate compound, and the resultant obtained by reacting an isocyanate group at the terminal of the urethane compound with a oxetane compound having a rosyl group. The polyhydric alcohol is not particularly limited, and examples thereof include ethylene glycol, glycerin, 14 200540537 sorbitol, trimethylolpropane, and (poly) propylene glycol. The above-mentioned difunctional or higher isocyanate is not particularly limited as long as it is difunctional or higher. Examples include isoflurone diisocyanate, 2,4-fluorenephenylene diisocyanate, 2,6-fluorenephenylene diisocyanate, Hexamethylene diisocyanate, dimethylhexamethylene diisocyanate, diphenylmethane-1,4,4-diisocyanate (MDI), hydrogenated MDI, polymellitic acid mdi, u —naphthalene diisocyanate IS , Norbornane diisocyanate, toludine diisocyanate, monotolyl diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate) Phenyl) thiophosphoric acid vinegar, tetramethylxylene diisocyanate, WH) 111-triisocyanate, and the like. The octane compound having an L group is not particularly limited, and examples thereof include 3-ethyl-3, 3-methyl-Atathione &amp; methylmethyloxetane, and the like. Examples of such an oxetane-containing oxetane compound include those sold in Tanaka, for example, "Atanacolu EO0" manufactured by Ube Kosan Co., Ltd., and the like.

Into the knife Ning has a hydrogen atomic nature f. It is hard to inject this group with a hardening tree of 2 or more epoxy groups and heterocyclobutanyl groups, and the tree can also be, for example, isocyanate and a compound with residual soil lice or enough. The isocyanate above the cyanocyclobutane compound reaction of the base is the same as the epoxidized compound having a hydroxyl group, and there is no particular limitation on the oxo ring having two or two oxygen groups. Same as above. The knife has a hydrogen-bonding functional group B-b group and 2 or more cyclic vulcanization. "15 200540537 The hardening resin is not particularly limited. 'For example, the above-mentioned epoxy resin having a hydrogen-bonding functional group is potassium thiocyanate. Made of denatured hardening resin. In the resin compositions of the first and second inventions, the preferable lower limit of the weight-average molecular weight of the curable resin is 300. If it is less than 300, it may cause contamination if it is contained in the liquid crystal. The upper limit of the weight average molecular weight is not limited: if it exceeds 5 M ', it may be difficult to adjust the viscosity of the resin composition of the i-th and the second inventions.

The resin composition of the second aspect of the present invention further contains a polymerizable resin having a softening temperature of 50 &lt; t or more (preferably 80 C or more) in addition to the above-mentioned curable resin in terms of resin components. If it is less than 50 ° C, using the resin composition of the second aspect of the present invention as a sealant for a liquid crystal display element, and when a liquid crystal display element is manufactured by a dropping method, the liquid crystal displayed on the obtained liquid crystal display element is caused by a polymerizable resin. Stains, etc. appear. The upper limit of the softening temperature of the polymerizable resin is not particularly limited, but is 120. (: The following is preferred. If it exceeds 120 ° C, the workability when mixed with other components may be deteriorated. The polymerizable resin is not particularly limited as long as the softening temperature is 50 ° C or higher. For example, epoxy resin, oxetane resin or episulfide resin, (fluorenyl) acrylic resin, etc. These polymerizable resins can be used alone or in combination of two or more. Rings with a softening temperature of 50 ° C or more The oxyresin is not particularly limited, and examples of the varnish-type resin include novolac-type, cresol-type, varnish-type, tri-phenol-type varnish, and dicyclopentadiene-type varnish. Examples thereof include bisphenol A type, bisphenol F type, 2,2′-di-dipropyl 16 200540537 aged A type, hydrogenated bisphenol type, and polyoxypropylene double hope epoxy resin. The resin can be used alone or in combination ^ Among them, in order to have excellent water resistance or more.

Mi ^ ^ ^ is also suitable for &gt; Moon Lacquer Type Epoxy Resin, and 'Novolac Lacquer Type' is more preferred. "Yuefei phenol lacquer epoxy resin: commercially available among other epoxy resins. For example, in the case of double alpha type, we can mention the special service of Epico, Epico 2012, Epico 〇03, Aite 1004 (the above are all made by Japan Epoxy Co., Ltd.); In terms of the double-F type, there may be Aipike 4GG4P, Aipike 7 (the above are all Japanese epoxy resins) (Manufactured by the company); for lacquer-type epoxy resins, there are Aipikelong N-740, Aipikelong N_77〇, Aipikelong small 775 (the above are manufactured by Dainippon Ink Chemical Company), Aipike Kate 152, Aipike 154 (all of which are manufactured by Japan Epoxy Resin Company); For the paint type epoxy resin, Aipike N-660, Aipike N_665, Aipike Long N-670, Aipikeron N_673, Aipikelong N_68〇, Aipikelong n_695, Aipikelong N_665-EXP, Aipikelong N_672_Εχρ (the above are manufactured by Daiyoshi Ink Chemical Co., Ltd.); Examples of the cyclovarnish type resin include XD-1001 (made by Nippon Kayaku Co., Ltd.) and ΕχΑ7200_Η (made by Dainippon Ink Industry Co., Ltd.); Examples of lipids include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.); examples of naphthol varnish resins include NC-7000L (Nippon Kayaku Co., Ltd.); and ST of hydrogenated bisphenol A resin. -5080 (manufactured by Tohto Kasei Co., Ltd.), etc. The oxetane resin having a softening temperature of 50 ° C or higher is not particularly limited. For example, novolak oxetane (manufactured by Toya Synthetic Co., Ltd. 17 200540537) PNOX-1009), etc.-The above-mentioned softening temperature is 50 ° C: The above episulfide resin is not particularly limited, and examples thereof include those obtained by reacting a commercially available epoxy resin with potassium thiocyanate. The polymerizable resin is also It may further have a hydrogen bond It B group in one molecule. This polymer resin is more difficult to dissolve in liquid a because of its higher polarity. The hydrogen bond functional group that this polymer resin can contain may be Examples are the same as the hydrogen-bonding functional group contained in the curable resin. I 苐 1 and 苐 2 The resin composition of the present invention contains a thermosetting agent and / or a cationic polymerization initiator. 忒 Thermal curing Agent and / or cationic polymerization initiator It is a substance which reacts and cross-links with epoxy groups and the like in the curable resin by heating. The second invention may further contain a radical initiator as the case may be. It is preferable to use a melting point of 1 for the above-mentioned thermal curing agent. Latent hardener above 〇〇〇c. When using a thermal hardener with a melting point of 10 ° C or lower, storage stability may be significantly reduced. • Examples of the above-mentioned thermal hardener include 1, 3 [Hydrazinecarboxyethyl-5-isopropylhein] and other hydrazine compounds, dicyandiamine, guanidine derivatives, 1-cyanoethyl-2-phenylimidazole, N- [ 2- (2-methyl-1,1-imidazolyl) ethyl] urea, 2,4-dicyano-6- [2, -methylimidazolyl ((1 ')]-ethyl-s-triazine , N, N'-bis (2-methyl-1-1-imidazolylethyl) urea, N, N '-(2-Amidino-J-imidazolylethyl) -hexamethylenediamine, 2-benzene Imidazole derivatives such as methyl-4 monomethyl-5hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, denatured aliphatic 18 200540537 polyamine, tetraazacis ^ — 分 ^ 知 Knowing Butene of formula I anhydride, ethylene glycol bis (anhydrotrimellitate stupid triglycerides) S Fan anhydride, etc., with various amine adduct of epoxy resin and the like. These can be used alone or in combination of two or more. As the above-mentioned heat curing agent, a surface of the solid curing agent particles can be used as a coating curing agent drawn by fine particles. If such a coating hardener is used, a resin composition having high storage stability can be obtained even if a hardener is blended in advance. The blending amount of the above-mentioned thermosetting agent is not particularly limited, and the lower limit is preferably relative to the above-mentioned hardening resin (the total amount of the hardening resin and the poly-human resin in the resin composition of the second aspect of the invention)! Parts by weight, preferably: The upper limit is 50 parts by weight. If it is less than i parts by weight, the performance of heat hardening ㈣, sometimes! 2. The resin composition of the second aspect of the present invention cannot be sufficiently hardened, and if it exceeds 5G parts by weight, not only the improvement of hardenability cannot be seen, but also the physical properties of the obtained hardened material will be adversely affected. The above-mentioned cationic polymerization initiator is not particularly limited as long as it can generate a protonic acid or a Lewis acid by heating. (Manufactured by Asahi Denka Chemical Industry Co., Ltd.), Sanaide SI-60, Sanaide SI_80, Sanaide Magical SI-110, Sanaide SI-U5, Sanaide SI_15〇, Sanaide sii60, Sanyam SM80, Sana There are SI_Hungry, San Aide si 8QL, San Ji, Ji, San Aide SI_11GL, San Aide 81 • Pei (both are Sanxin Chemical 2 = manufacturing), etc. These cationic polymerization initiators can be used alone or more than 2 kinds. Ι7Γ The blending amount of the above-mentioned cationic polymerization initiator is not particularly limited, and is relative to the above-mentioned curable resin (in the resin composition of the second invention, it is hardenable 19 200540537 Shuyue Ji and the total amount of polymerizable resin) ⑽ weight The lower limit is preferably 〇ι. The upper limit of the car is better than J 〇 parts by weight. If it is less than 0.001 parts by weight, then the effect of insufficient power cannot be obtained. If it exceeds 10 parts by weight, then Not only can't see the improvement of hardenability, For the physical properties of the resulting cured product will be adversely affected. A method for producing first and second resin composition of the present invention is not particularly limited, piece goods, may include the above-mentioned curable resin (resin and polymeric), a thermosetting agent

And / or fluorene cationic polymerization initiator and the like are mixed by a conventionally known method. In this case, in order to remove ionic impurities, it is also possible to make contact with ion-adsorbing solids such as layered silicate minerals. The resin composition of the first aspect of the present invention has at least 1 of a resin component having a hydrogen bonding s energy group and an epoxy group, an oxetanyl group, and an episulfide group. This type of functional group is a hardening resin with a value of 3 · 5 × 10_3 or more obtained by dividing the number of hydrogen-bonding functional groups in the molecule of I 1 by the weight-average molecular weight. Thus, even when a liquid crystal display element is manufactured by a dropping method without ultraviolet irradiation, When used as a sealant, it is 80% superior in thermosetting properties. It will not cause liquid stains due to the dissolution of non-hardened hardening resin. It can be used to prevent the liquid crystal from being easily contaminated and to display images with less stains. Liquid crystal display element. The resin composition of the second aspect of the present invention has only one resin component: at least one group having a hydrogen-bonding functional group and one selected from an epoxy group, an oxetanyl group, and an episulfide group. Types of functional groups, and the number of hydrogen-bonding functional groups in the molecule divided by the weight-average molecular weight is a hardening resin with a value of 3 5 × 10_3 or more and a polymerizable resin with a softening temperature of 50 t or more. 20 200540537 When it is used as a sealant in the manufacture of liquid crystal display elements by the dropping method of ultraviolet irradiation, it has excellent thermosetting property, and it will hardly cause liquid crystal pollution due to the dissolution of uncured hardening resin and polymerizable resin. 、 Liquid crystal display element that can display images with few spots. Furthermore, it is excellent in storage stability, and is also excellent in low-temperature rapid curing. The resin composition of the third aspect of the present invention contains: at least one functional group in a group selected from the group consisting of a hydrogen-bonding functional group and an epoxy group, an oxetanyl group, and an episulfide group, 1 丨 The number of hydrogen-bonding functional groups in the molecule divided by the weight-average molecular weight is a hardening tree having a value of 3 · 5χ10.3 or more in the above-mentioned hardening resin contained in the resin composition of the third aspect of the present invention. The conventional sealant for liquid crystal display elements contains a large amount of hydrogen-bonding functional groups in the molecule and has high polarity. Therefore, even when the resin composition of the present invention is in contact with liquid crystal in an uncured state, the third The tree of the invention • The hardening resin in the lipid composition is not easily dissolved in the liquid crystal. In addition, since the cationic polymerization initiator included in the third month and the third month may use shellfish script or Lewis acid due to light irradiation, the hardening resin in the resin composition of the third invention may be irradiated with ultraviolet rays. Hardening occurs immediately, and the hardening time can be shortened. Also, the curable resin in the resin composition of the third invention may have a (meth) acrylic group. In this case, the curable resin is excellent in photocurability. In the resin composition of the third aspect of the present invention, the lower limit of the value obtained by dividing the number of hydrogen-bonding functional groups in the molecule of 1 21 200540537 by the molecular weight is 35 x 10. If it is less than 3.5 · 1 (T3, then The amount of the chlorine-bonding functional group contained in one molecule of the above-mentioned curable resin is small, and the polarity of the curable resin becomes low. The liquid crystal display using the resin composition of the third aspect of the present invention as a dropping method When using a sealant for parts, the uncured hardening resin component will dissolve into the liquid crystal and contaminate the liquid crystal. The preferred lower limit is 4.0x10-3m0 / g.

The lower limit of the weight-average molecular weight of the curable resin in the resin composition of the third invention is 300. If it is less than 300, it may dissolve into the liquid. The upper limit of the weight average molecular weight is not particularly limited, but if it exceeds 50,000, it may be difficult to adjust the viscosity of the resin composition of the third invention. The lower limit is more preferably 600. The curable resin in the resin composition of the third aspect of the present invention preferably has at least one functional group of at least one functional group selected from the group consisting of epoxy groups, oxetanyl groups, and episulfide groups having at least two functional groups. Thereby, the amount of residual f unreacted substances after the cross-linking reaction becomes extremely small, and the liquid pollution caused by the remaining unreacted substances can be controlled. However, the functional group contained in the i molecule is preferably 6 or less. If it exceeds 6, the hardening shrinkage becomes large, and this may cause a decrease in adhesion. As the curable resin in the resin composition of the third aspect of the present invention, the same ones as those described in the above-mentioned resin composition of the second and third aspects of the present invention are mentioned. The polymer composition is a polymer resin with a softening temperature of 5Q or more (more preferably 8 (rc or more)) as the resin component. The method of dripping a sealant for a polymerizable resin is used to produce a liquid crystal breakage. After temporary hardening by ultraviolet radiation, 22 200540537 will start to heat up in the formal hardening process until the μ mol r κ mouth resin is completely hardened. There will be some time delay during this period of time. The fluidity of the polymerizable tree, so the influent 0 ^ A After reviewing the results, it was found that to use a polymerizable resin with a softening temperature of 5 (rc, the polymer resin can be lowered. The liquidity can minimize the degree of such liquid crystal contamination. If it is less than 50 ° C, the resin composition of the mistletoe, 丄 Λ, 丄 _ + Zanyue of the third invention is regarded as liquid crystal

· When using a sealant for parts, and using liquid crystal display elements to manufacture liquid crystal display elements, it is considered that the liquid crystal display elements obtained may be contaminated with liquid crystal due to polymerizable resin. Caused by stains and so on. The upper limit of the softening temperature is not particularly limited, and is preferably 12 (rc or less. If it is exceeded, the workability when mixed with other constituent components may be reduced. In the above polymerizable resin, only I softening temperature is 纟 50. The above is not particularly limited, and examples thereof include epoxy resin, oxetane resin, or episulfide resin. These polymerizable resins may be used alone or in combination of two or more kinds. In terms of the resin, the same as the polymerizable resin described in the resin composition of the above-mentioned second invention. The resin composition of the third invention may further contain a radically polymerizable resin as a resin component. The radical polymerization reaction of a radically polymerizable resin upon UV irradiation ^ is more rapid-curing than the cationic polymerization of a cationic polymerizable compound. If such a radical polymerization reaction is used in combination, the third invention When the resin composition is used as a sealant used in the dropping method to manufacture a liquid crystal display device, it will harden after being exposed to ultraviolet rays. 23 200540537 The time is shortened. The radical polymerizable resin is not particularly limited, and preferably a curable resin having a (meth) acrylate group. The curable resin having a (meth) acrylate group is not particularly limited, From the viewpoint of preventing liquid crystal contamination, it is more preferable to have (meth) acrylate groups and hydrogen-bonding functional groups in one molecule. More preferably, the value obtained by dividing the number of hydrogen-bonding functional groups by the weight average molecular weight is 3 · 5χ1. (At least Γ3. In the present specification, the (meth) acrylate group means an acrylate group or a methacrylic acid group. The (meth) acrylate group and a hydrogen bond are included in one molecule. The radically polymerizable resin having a functional group is not particularly limited, and examples thereof include (meth) acrylic acid 2-monohydroxyethyl ester, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid. 2— Fluorenyl propyl ester, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, ( Methacrylic acid 3-Hydroxy-3 Methyl butyl, 2-hydroxy-3-phenoxypropyl (meth) acrylate, epoxy (meth) acrylate or urethane (meth) acrylate, etc. Among them, weather resistance In consideration of excellent adhesiveness, epoxy (meth) acrylate and / or urethane (meth) acrylate are suitable. Examples of the marketer of the (meth) acrylate epoxy ester include Epoxy ester M600A, epoxy ester 7〇ρα, epoxy ester 2000A, epoxy ester 800MFA, epoxy resin 3002M, epoxy ester 3000A, epoxy ester 1600A, epoxy ester 3000M , Epoxy ester 300A, epoxy ester 200EA, epoxy ester 400EA (the above are manufactured by Gongrong Co., Ltd.) EB3700 (Diesel UCB); ea_552〇, 24 200540537 EA CHD (the above are all new Nakamura Chemical Co., Ltd.). The marketers of the (meth) acrylic acid urethanes may include, for example, EB230, EB4858, EB8402, EB1264, EB9, eb22, and EB222〇 (all of which are manufactured by Shell UCB); M- 1100, M-1200, M-1 600 (the above are all manufactured by Toa Synthesis). The lower limit of the content of ϊ in the radically polymerizable resin in the resin composition of the third aspect of the present invention is relative to the above-mentioned curable resin (when the above-mentioned softening: degree is J0.... Including this polymerizable tree moon king) 100 parts by weight is i parts by weight, and the preferred upper limit is 2⑼ parts by weight. '&quot; Without severe stings, the effect of shortening the hardening time can hardly be obtained. Right, once 200 parts is used, there is a possibility that the adhesion force will be reduced. A more preferred upper limit is ⑽ parts by weight, and a particularly preferred upper limit is 40 parts by weight. The resin composition of the third invention contains a cationic polymerization initiator. The cationic polymerization initiator is not particularly limited as long as it can generate protonic acid or Lewis acid upon irradiation with light, and examples thereof include iron-propadiene complexes, aromatic diazonium salts, and aromatic iodine. Salt, aromatic sulfonium salt, pyridinium salt, aluminum complex / silanolate, halogenated alkyl-substituted triazine derivative, trifluoromethanesulfonic acid-N-fluorenimide derivative, benzenesulfonic acid-N —Fluorenimide derivatives, methanesulfonic acid—N—fluorenimide derivatives, tribromofluorenylphenylsulfonic acid derivatives, and the like. Commercially available cationic polymerization initiators such as OPTO SP_15, OPTO SP_17〇, OPTO 8ρ · ΐ7ΐ (the above are all manufactured by Asahi Chemical Industry Co., Ltd.); UVE_1〇14 (Manufactured by Teraru Electronics Co., Ltd. D. Irujacoya-261 (manufactured by Jibage Geigy); UVI-699〇 (manufactured by Union Carbet), BBI-103, MPI-103, TPS_1〇3 , 25 200540537 DTS-103, NAT-103, NDS-103 (the above are all manufactured by Midel Chemical Co., Ltd.); CI-2064, CI-2639, CI-2624, CI-2481 (the above are manufactured by Japan Soda Co., Ltd.); RHODORSIL PHOTOINITIATOR 2074 (manufactured by Ronnie Plant), CD-10 12 (manufactured by Sartmore), etc. These cationic polymerization initiators can be used alone or in combination of two or more. In the resin composition of the third invention The preferable lower limit of the compounding amount of the above-mentioned cationic polymerization initiator is relative to the above-mentioned curable resin (when the above-mentioned polymerizable resin having a softening temperature of 50 ° C or more is included, including all of the polymerizable resin) 1 00 The weight part is 0.1 weight part, and a preferable upper limit is i 0 weight part. If it is less than 0.1 weight part If the photopolymerization initiation capability is insufficient, no effect can be obtained, and if it exceeds 10 parts by weight, not only does the improvement of hardenability not be exhibited, but the physical properties of the obtained hardened product will be adversely affected. The resin composition of the third invention may also contain Thermal hardener. This thermal hardener is a cross-linking agent that reacts with epoxy groups and the like contained in the hardenable resin, and has a combination of the resin composition of the present invention after curing and adhesion and moisture resistance. The function of improving the properties. The above-mentioned heat curing agent can be suitably used with a melting point of 10 (above rc = agent. The right is the heat curing agent below the point of loot, storage stability will show that the above-mentioned heat curing agent can be listed on the toilet ^ 0 ^ The same as the thermal hardener described in the resin composition of the present invention in the second and second aspects. The blending amount of the above-mentioned thermal hardener is not particularly limited, as compared with the hard resin (when having the softening temperature described above).愔 π 也 ^ Also polymerizable resins above 50c] It states that it includes the polymerization amount + 100% by weight of the sigma-bearing tree), preferably lower 26 200540537 is limited to 1 part by weight, and the preferred upper limit is 20 parts by weight. If not Full! By weight, the hardening performance due to heat is poor, and sometimes the resin composition of the third invention cannot be sufficiently hardened. If it exceeds 20 parts by weight, not only does the improvement of hardenability not appear, but also the resulting hardened product will not be improved. Physical properties cause adverse effects. When the resin composition of the third aspect of the present invention contains the above-mentioned radical polymerizable resin, it is preferable to further contain a photoradical polymerization initiator. Generally, the cationic polymerization initiator does not decompose. It is possible to generate free radicals during the process and use them to harden the radical polymerizable resin. However, based on increasing the hardening speed and the concentration of the cross-linking / Sp eve | A polymerization initiator is preferred. The photo-radical polymerization initiator is not particularly limited, and it is preferably one having a reactive double bond and a photo-reaction starting portion. As long as such a radical polymerization initiator is used, not only a sufficient reaction can be imparted to the sealant for a liquid crystal display element, but also the liquid crystal will not be contaminated by ingress into the liquid crystal. Among them, benzoin (ether) compounds having a reactive double bond and a via group and / or a urethane bond are suitable. The so-called benzoin compounds are benzoin and benzoin scales. Examples of the reactive double bond include allyl, ethyl ether, and (meth) acrylic groups. Among them, a (meth) acrylic group is suitable in terms of reactivity. With such a reactive double bond, the weather resistance of the sealant for a liquid crystal display device obtained by using the resin composition of the third invention can be improved. The benzoin (scaly) -based compound may have one or both of a bond via an amino group and a urethane bond. When the benzoin (ether) compound does not have a hydroxyl group 27 200540537 and a urethane bond, it may be dissolved in the liquid crystal. In the above-mentioned benzoin (ether) compounds, the reactive double bond and the radical and / or urethane bond may be located at any position of the benzoin (ether) skeleton to have the following general formula ( 4) The molecular skeleton shown is preferred. As long as a compound having a related molecular skeleton is used as a photo-radical polymerization initiator, the residue can be reduced and the amount of outgassing can be reduced.

R

(4) The following aliphatic hydrocarbon residue chains. If R, then the initiation of photoradical polymerization will be caused by the steric hindrance of the substituents. In the formula, 'R represents nitrogen, and the carbon number 4 is an aliphatic hydrocarbon residue with a carbon number of more than 4, although it can increase storage stability, But the reactivity decreases.

The compound Dan La is represented by the formula (4), π 4 β is not to not equal to 1, and the compound Q Η HO η, for example, is represented by the following general formula (5).

y I o -N-C-〇-y_〇_ | _gh ^ CH2 (5) In the formula, 'R represents hydrogen, carbon number 4 and carbon number 13 or less, two functional ... month aliphatic chain residue, X represents For the residue of this isomer derivative, Y represents an aliphatic group having a carbon number of 28,2005,40,537 or less, or a residue whose carbon-to-oxygen atomic ratio is 3 or less. If χ is a carbon number exceeding The residue of a bifunctional isocyanate derivative of 13-2 is sometimes easily dissolved in liquid crystals. If fluorene is an aliphatic hydrocarbon residue having more than 4 carbon atoms or a residue having a carbon to oxygen atomic ratio exceeding 3, there are It is easy to dissolve in liquid crystals at the time. 'As for the photo-radical polymerization initiator, benzophenone, 2,2-diethoxyethylacetophenone, benzoin, and benzyl isopropyl ether can also be mentioned. , Benzyl dimethyl sig alcohol, 1-ylcyclohexyl phenone, thioxan, etc. These photo-free radical-based polymerization initiators can be used alone or in combination of two or more. In the resin composition of the third invention The lower limit of the blending amount of the photo-radical polymerization initiator is preferably lower than that of the above-mentioned curable resin (when it has the above-mentioned softening temperature of 4 50.... Including the entire amount of this polymerizable resin) 100 parts by weight is 0.05 parts by weight, and the preferred upper limit is 15 parts by weight. If less than 0.5 parts by weight, the resin composition of the third aspect of the present invention may harden | Insufficient, if it exceeds 5 parts by weight, the hygroscopicity of the obtained hardened product may become high. | 筮 The method for producing the resin composition of the third aspect of the present invention is not particularly limited, and examples include the above-mentioned hardenability. The resin, thermosetting agent, and / or cationic polymerization = initiator and the components added as appropriate are mixed by a conventionally known method. At this time, in order to remove ionic impurities, it can also be mixed with layered silicate minerals. The hardening resin contained in the resin composition of the third aspect of the present invention is composed of epoxy resin, oxetanyl group and episulfide soil selected from 1 knife. At least one functional group in the group, so it exhibits good thermosetting properties. 29 200540537 1 hydrogen bond contained in one molecule

In order to shorten the curing time, the unit production time at the time of manufacture can be shortened, and compared with the conventional sealant for liquid crystal display elements, it has a large B & M base and high polarity. Therefore, even if the first product is in contact with the liquid crystal in an uncured state, the resin composition of the present invention can be blended with various additives to improve adhesion, and is not particularly limited, as long as the adhesion of the resin composition of the present invention can be improved. For example, in the copolymer of acrylonitrile and butadiene, CTBN (made by Ube Kosan Co., Ltd., • CTBN1300x3 l, CTBN1300x8, CTBN1300x13) with a COOH group at the end, and copolymerization of butadiene can be mentioned. The end of the product is COB-based CTB (made by Ube Kosan Co., Ltd., CTBN2000X162), and the end is amine-based ATBN (made by Ube Kosan Co., Ltd.

(ATBN1300X16), elastomers such as nbr and copolymers of methacrylic acid, crosslinked NBR (made by JSR Corporation, XEr_91), fine particles such as crosslinked BR, and amine-terminated difluorenyl silicone, epoxy Silicone modification products such as terminal dimethyl silicone. The above additives are preferably fine particles having a core-shell (core-shell particles). The core-shell particles are not particularly limited, and examples thereof include Staphyroid "AC-3355", "AC-3816", "AC-3 364", "AC-3832", "AC-4030" (The above are manufactured by Ganzi Co., Ltd.), "F_351" (manufactured by Jeton), Mita Valley Pree "S-2001", "W-30〇A", rw_341 200540537-(All above are Mitsubishi Leon Corporation Manufacturing) and so on. In addition, the average particle diameter of the core-shell particles is not particularly limited, and a preferred lower limit is (UHP, a preferred upper limit is 5 cores. If the mouth is not full, the adhesiveness of the resin composition of the present invention can hardly be improved. In addition, it is sometimes difficult to uniformly disperse in the resin composition of the present invention. If it exceeds 5 #m, the resin composition of the present invention is not used as a sealant during the manufacture of a crystal display element, and the element cannot be made. The distance becomes smaller. Lu further, the resin composition of the present invention can also be mixed with a gelling agent. Among them, the i-th and the second tree-moon compositions of the present invention, which are not subjected to ultraviolet irradiation in the dropping method, contain The gelling agent is particularly preferred. The gelling agent is not particularly limited, and examples thereof include a copolymer of methacrylic acid and an alkyl compound. Examples of commercially available gelling agents include F 320. ", F-301", rF_34〇 "(all of which are manufactured by Jie Weng). The resin composition of the present invention may also contain a silane coupling agent. The silane coupling agent is mainly used as the resin composition of the present invention. Liquid crystal display element In the case of using an agent, it has a function as a bonding aid to improve the adhesion to a transparent substrate.-The silane coupling agent is not particularly limited, and is based on being excellent in the effect of improving the adhesion to a substrate and the like. From the viewpoint of chemically bonding to a curable resin to prevent it from flowing into the liquid crystal material, for example, γ-aminopropylpropyloxysilyl sulfopropyltrioxolite, γ-epoxy @ oxypropyl Trimethoxysilane, isocyanate propyltrimethoxysilane, etc. 'or imidazole silane compounds having a structure in which an imidazole skeleton and an alkoxyallyl group are separated by a spacer 31 200540537 can be used alone or in combination. The above composition is specialized. The Shirayaki coupling coupler composition may also contain fillers to take advantage of the stress dispersing effect. At last, it is compatible, and the linear swelling coefficient is improved. Examples include, but are not limited to, dioxide Bu Ye Ai ..., special iron oxide, oxidation •, oxidation: oxygen oxidation,

Magnesium carbonate, sulphuric acid, ditin, titanium dioxide, hydroxide hydroxide, hydroxide ', barium barium h, Shi Xi_, talc, glass beads, sericite clay, elephantite, nitrite, nitrided stone And other inorganic fillers. The resin composition invented by the material may contain a separator for adjusting the rheological properties, such as a spacer, a defoaming agent, a leveling agent, a presensitizer, a polymerization inhibitor, and a viscosity adjustment agent to adjust the panel pitch. Reactive diluents, etc. A sealant for a liquid crystal dropping method composed of a curable resin composition for a liquid crystal display element of the present invention is also one aspect of the present invention. On the right, the hardened tree test object for a liquid crystal display element of the present invention and / or the conductive sealing particles in the sealant for a liquid crystal dropping method of the present invention can be used to produce a vertical conductive material. If such an upper and lower conductive material is used, the conductive connection of the electrodes of the transparent substrate can be performed without contaminating the liquid crystal. The hardening resin composition for a liquid crystal display element of the present invention and the liquid crystal dropping method of the present invention can be used. It is also one aspect of the present invention to use a sealant and a conductive material for conducting the fine particles. The above-mentioned conductive fine particles are not particularly limited. Metal balls, those having a conductive metal layer formed on the surfaces of the resin fine particles, etc., and those having a conductive metal layer formed on the surfaces of the resin fine particles, because the resin particles have 32 200540537 • Excellent elasticity ' Therefore, the conductive connection can be performed without causing damage to the transparent substrate and the like. A liquid crystal display element using the sealant for the liquid crystal dropping method of the present invention and / or the upper and lower conductive materials of the present invention is also one of the present invention. ADVANTAGE OF THE INVENTION According to this invention, the hardening resin composition for liquid crystal display elements can be provided, whether it is used as a sealant when manufacturing a liquid crystal display element by the dripping method, or a liquid punch is manufactured by the dripping method which does not perform ultraviolet irradiation. When the display element is used as a sealant, it is not easy to cause liquid crystal staining, and a liquid crystal display element with high image quality and few color spots can be manufactured. In addition, the present invention can provide a curable resin composition for a liquid crystal display element. It is not easy to cause liquid crystal pollution, and can produce liquid crystal display elements with high image quality and few color spots. In addition, the present invention can provide a sealant for a liquid crystal dropping method composed of the hardening resin composition for the liquid crystal display element. 2. Conductive materials and liquid crystal display elements. 1 [Embodiments] The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. (Synthesis of epoxy resin (1)) In a dry air environment, 2,2,4 ~ trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (5 Moore) and dibutyltin dilaurate (5 millimoles) were stirred, but the sugar alcohol (100 moles) was not more than 60. (: The method is slowly dripped, and after dropping 33 200540537 2 bundles, the isocyanate group = resin ⑴ is further analyzed by infrared absorption spectrum analysis. Hydrogen-bondable Miyagaki earthenware in 1 molecule of the obtained epoxy resin 除 is divided by the weight The value of the average molecular weight was set to 5.58 × 10-3. (Synthesis of epoxy resin (2))… In a krypton air atmosphere, 2,4-toluene j and cyanide S were added to the reaction flask (5 Mo). )) And dibutyltin dilaurate (2 $ mole) • Dibutyltin 'and then the sugar alcohol (Mole) are slowly dripped in a way that does not exceed the voyage: after the drop is completed, the infrared absorption spectrum is further used. The reaction was carried out at 60 ° C in such a manner that the isoramic acid group (near】-) no longer remained to obtain an epoxy resin (2). The obtained epoxy resin had a hydrogen bonding property of ^ molecules. The value of the number of functional groups divided by the weight-average molecular weight is Mb 10) 〇 (Synthesis of oxetane compound (1)) In a dry air atmosphere t, 2,2,4_triple I Γΐhexadecane is added to the reaction flask. Molybdenum isocyanate) and dibutyltin dilaurate (54 Moore) were blended, Germany will be 3…, silly will be 3 ethyl a 3-hydroxymethyl oxetan di manufactured by the Ministry of Industry Co., Ltd., "Atanacolu EH0J) (1 Moore). No more than 60 c Τ is slowly dripped, after the dripping is completed-proceeding for aviation: the off-site absorption spectrum analysis is carried out in such a way that the isocyanate group (around 227 ° cm) no longer remains, and oxetane is obtained Compound). The number of hydrogen-bonding functional soils in the molecule i of the obtained oxetane compound ⑴ divided by the weight-average molecular weight is 4.52 × 1 0 · 3. (Synthesis of oxetane compound (2)) 34 200540537

In a dry air environment, add 2,4-tolyl diisocyanate (5 moles) and dibutyltin dilaurate (2.5 mmoles) to the reaction flask, and then stir 3 -ethyl_ 3 _Hydroxymethyloxetane (manufactured by Ube Kosan Co., Ltd., "Atanacolu EΗO") (10 Moore) slowly dripped so as not to exceed 60 c, and further dropped to 60 after dripping was completed. It uses infrared absorption spectroscopy to analyze the reaction at 60 ° C so that the isocyanate group (near 2270 cm · 1) no longer remains, to obtain an oxetane compound (2). The number of known hydrogen-bonding functional groups in the molecule of the known oxa% butane compound (2) divided by the weight-average molecular weight is 4.93 × 1 0-3. (Example 1) 60 parts by weight of an epoxy resin (2), a latent heat curing agent (made by Aki Technology Co., Ltd., one part by weight of Amike, Dioxide = (average particle diameter 1.5 // m) 25 parts by weight, silane coupling agent &amp; monoglycidoxypropyl monomethoxysilane) 丨 parts by weight, 10 parts by weight of gelling agent (manufactured by Jie Weng Co., Ltd., \ _340), stirring with a planetary stirring device Thereafter, a ceramic tortoise was used as a knife to obtain a curable resin composition for a liquid crystal display element. (Example 2) ^ Divide the bis (3,5-bis-hydroxymethyl-4-cyclo: propyl "group) methane (the number of hydrogen-bonding functional groups in one molecule by the weight average expressed by the above formula (2) The value obtained in the knife is 4.62 × 10-3) 60 parts by weight, a cationic polymerization initiator (manufactured by New Chemical Industry Co., Ltd., SI-100L), and spar dioxide (Beiping = diameter ^ ㈣25 parts by weight, 2 parts by weight of coupling agent (glycidyloxypoxy-methoxysilane), 10 parts by weight of gelling agent (manufactured by Jie Weng Company, 34〇) in a planetary mixing device After the mixing, ceramic 35 200540537 was used as a knife to obtain a curable resin composition for a liquid crystal display element. (Example 3) Take a person? Emulsion resin 0) 20 parts by weight, epoxy resin (2) 20 parts by weight of bisphenol A type epoxy resin (made by Japan Epoxy Resin Co., Ltd., Erpi Tate 1004: the number of hydrogen-bonding functional groups in one molecule divided by the weight average fraction: the amount obtained The value is 3.57X10-3, the softening temperature is 9rc, the weight average is ^) 20 parts by weight of the mixture is heated, and the mixture is stirred with a planetary mixing device until it becomes To the solution. Add latency to the resulting mixture = hardener (Ajinomoto Precision Technology Co., Ltd., Amikeya VDH_J) 20 parts by weight, dioxide dioxide particles (average particle size l.Wm) 25 weight Parts, 2 parts by weight of Shixiyan coupling agent (glycidoxypropyltrimethoxy residue), 10 parts by weight of gelation d (manufactured by Jieyu Co., F_34〇), and performed with a planetary drop device After stirring, three ceramic rolls were used to disperse to obtain a curable resin composition for a liquid crystal display element. (Example 4) X 10 parts by weight of epoxy resin and 20 parts by weight of epoxy resin (2) were used as a poly mouth 11 month-old novolac epoxy resin (manufactured by Dainippon Ink Co., Ltd. ^ N 770 · 1 molecule divided by the number of hydrogen-bonding functional groups in the molecule average weight: the value obtained is 0, softening temperature 70 , Weight-average molecular weight _) The mixture of Sichuan heavy weight parts is heated and stirred with a planetary mixing device until a homogeneous solution is added. To the resulting mixture, a cationic polymerization initiator (manufactured by Erxin Chemical Industry Co., Ltd., San Aide SM ·), Stone dioxide eve particles ( Average particle diameter 1.5 / ζ m) 25 parts by weight, silane coupling agent (r-glycidoxypropyldimethoxysilane) 2 parts by weight, gelling agent (manufactured by Jie Weng Company, 36 200540537 $ _) It is known that after stirring with a planetary agitation device, a ceramic resin is used to make a curable resin composition for a liquid crystal display element. (Example 5)

〃 Divide the bis (3,5—bis—transylmethyl_4_cyclo = propyl foxy) methyl chloride represented by the above formula (2) (divide the number of hydrogen-bonding functional groups in one molecule by the weight average molecular weight) The obtained value was 5.0 × 10,3 parts by weight, as a polymerizable resin, bisphenol A type propylene oxide acetic acid (manufactured by Daischel Corporation, EB37〇) i 〇 = quantity, ring Oxyacrylic acid (produced by Kyoei Chemical Co., Ltd., Noodles) is used to perform a smashing operation with a star-type stool mixing device until it becomes a homogeneous solution. A photo-radical polymerization initiator (for Gibbart) is added to the obtained mixture. 1 part by weight of IRGACURE manufactured by the Chemical Division, heated to dissolve the radical polymerization initiator, and then stirred with a planetary stirring device. Further, a cationic polymerization initiator (manufactured by Asahi Denka Kogyo Co., Ltd. SP-170H 4 parts by weight, silica dioxide particles (average particle # i 5㈣15 parts by weight, silane coupling agent (r-glycidoxypropyltrimethoxysilane) by weight using a planetary stirring device , 3 rollers made of ceramics are used for dispersion to obtain rigidity for liquid crystal display elements (Example 6) The bis (3,5-bis-hydroxymethyl-4, -epoxypropyloxy) methane (hydrogen bond in one molecule) is represented by the formula (2). The value obtained by dividing the number of functional functional groups by the weight-average molecular weight is 5.00 × 10 · 3) 20 parts by weight, 10 parts by weight of the oxetane compound (1), and bisphenol A type epoxy propylene acid as a polymerizable resin 30 parts by weight of vinegar (manufactured by Deschel UCB, EB3700) was stirred with a planetary stirring device until a homogeneous solution was obtained. To the obtained 37 200540537 mixture, a photoradical polymerization initiator (Gibbat Chemical Co., Ltd.) was added. Manufacturing, IRGACURE 651) 1 part by weight, heating to dissolve the radical polymerization initiator, and then stirring with a planetary stirring device to obtain a mixture. To the obtained mixture, a cationic polymerization initiator (manufactured by Asahi Denka Kogyo Co., Ltd., Austria Protomer SP-170) 1 part by weight, silicon dioxide particles (average particle size by weight, 1 part by weight of silane coupling agent (r-glycidoxypropyltrimethoxysilane), fed with a planetary stirring device After stirring, three rollers made of ceramics were used to disperse to obtain a hardenable resin composition for liquid crystal display elements. (Example 7) 双 The double (3,5-double-warp) represented by the above formula (2) was used. Methyl-4-cyclocyclopropyloxy) methylbenzene (the number of hydrogen-bonding functional groups in one molecule divided by the weight average molecular weight is 5.0x10, 20 parts by weight, oxetane compound (2) 10 parts by weight of Shuangpan A-type epoxy propylene vinegar (Diesel UCB, EB37GG) 3 () parts by weight as a polymerizable resin is stirred with a planetary agitator until a homogeneous solution is obtained. 1 part by weight of a photo-radical polymerization initiator (IRGACURE 651, manufactured by Gibbart Chemical Co., Ltd.) is added to the obtained mixture, and the radical polymerization initiator is dissolved after heating, and then further carried out in a planetary apparatus. A mixture was obtained. 1 part by weight of a cationic polymerization initiator (manufactured by Asahi Denka Kogyo SP_m) was added to the mixture of # 2, stone dioxide particles (average particle weight, stone yaki coupling agent (7 —propylene oxide) 1 part by weight of oxypropyl succinic lactate syrup) was dispensed with a planetary stirrer device, and 3 hard rolls made of ceramics were used to obtain a hardening tree 38 200540537 for a liquid crystal display device. (Comparison Example 1) Molecular steaming hall treatment of Shuangpan A-type epoxy resin (manufactured by Dainippon Ink Industry Co., Ltd., 850 CRp · · J points :, α-pandania, 1 lice bond function in the knife The base number is divided by 乂: = the value obtained by the sub-quantity is 0, the liquid is at room temperature, the weight average, 0) 60 parts by weight of the mixture is stirred with a planetary stirring device until it becomes a homogenous trough. Add the obtained mixture to Latent

^ Agent ^ made by Zhisu Precision Technology Co., Ltd., Amikeya delete]) 30 replacement parts, 25 parts by weight of stone dioxide particles (average particle size 15 # m), Shixiyan coupling agent (epoxypropylene oxide) The propyltrimethoxy group suppresses the weight part, 10 parts by weight of the gelling agent (manufactured by Jie Weng Co., Ltd., F_340), and stirs it in a lamp with a planetary stirring device, and then makes 3 liquid crystals to make a liquid crystal display element. A hardening resin composition is used. (Comparative Example 2) The molecule 4 is treated with Shuangpan A-type epoxy resin (made by Dainippon Ink Industry Co., Ltd., Epicon 850CRP: i. The number of hydrogen-bonding functional groups in the molecule is divided by: Weight: The value obtained in the average knife is 0, and it is liquid at normal temperature. The average weight of the knife is 34G) and the mixture of 6G parts by weight is transferred by a planetary device. Cationic poly mouth (Shichi (_ manufactured by New Chemical Industry Co., Ltd., San Aide, Dioxin particles (average particle size 15 &quot; called 25 parts by weight, silane coupling agent (glycidyloxypropyl dioxonite) Burning weight parts, gelling agent (F 34G made by Jeton) 10 parts by weight After the planetary scrambler was used for the scramble, the three pieces of Taumann I were dispersed to obtain a cured resin group 39 200540537 for a liquid crystal display device. (Comparative Example 3) The molecular steaming process was performed on the double hope A-ring. Oxygen resin (manufactured by Dainippon Ink Industry Co., Ltd., Epicon 85GCRP: 1, the number of hydrogen-bonding functional groups divided by the weight-average molecular weight, the value is ^ at room temperature, the average weight is 34G in a liquid knife) 4G weight s parts 2. As a polymerizable resin, a two-year-old a-type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., Epikete 2004: i, the number of chlorine-bond functional groups in the molecule divided by the weight-average molecular weight) η ·:

Softening temperature m :, weight average molecular weight 168G) 2G parts by weight of the mixture is heated and stirred with a planetary mixing device until it becomes a homogeneous solution. To the obtained mixture, 3 () parts by weight of Lai-type hardener (manufactured by Ajinomoto Precision Technology Co., Ltd., Amikeya VDH]), dioxin particles (average particle size of 25, and Shibuya) Mixture Bu—glycidoxypropyltrimethoxysilane) 1 part by weight, gelling agent (manufactured by Jie Weng Company, P-340) 1〇1 parts, after mixing in a planetary mixing device, Three rollers made of ceramics were dispersed to obtain a curable resin composition for a liquid crystal display element. (Comparative Example 4) A molecular distillation treatment of a bisphenol A type epoxy resin (made by Dainippon Ink Industry Co., Ltd., Epiplon 85GCRP: 丨 the number of hydrogen-bonding functional groups in the molecule divided by the weight average molecular weight is 0, Liquid at normal temperature, weight average weight 340) 40 parts by weight, as a polymerizable resin Shuangpan A-type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., 2004) The value of the number of hydrogen-bonding functional groups divided by the weight average molecular weight is 3 57χΐ〇_3, softening temperature, weight average molecular weight) 2Q parts by weight of the mixture 200540537 heating, mixing with a planetary mixing device until uniform Dissolve to a halt. A cationic polymerization initiator (manufactured by Sanxin Chemical Industry Co., Ltd. SI_1OOL), 25 parts by weight of silica particles (average particle size 15 #m), and a silane coupling agent propylene oxide were added to the mixture. Oxypropyltrimethoxysilane) 1 part by weight, gelling agent (manufactured by Jeton Corporation, f_34〇) i0 2 parts by weight and then dispersed in a star-type mixing device, and then dispersed in m 3 pieces A curable resin composition for a liquid crystal display element. (Comparative Example 5) The value obtained by dividing the number of hydrogen-bonding functional groups in the molecule by a molecular distillation treatment of a bisphenol A type epoxy resin (made by Dainippon Ink Industries, Epiplon 85GCRP ·· i) by the weight average molecular weight 〇, liquid at normal temperature, weight average molecular weight 340) 30 parts by weight, as a polymerizable resin bisphenol A type epoxy acrylate (manufactured by Descher UCB, EB37〇) 10 parts by weight, epoxy A mixture of 20 parts by weight of acrylate (manufactured by Kyoei Chemical Co., Ltd., 80 MFA) was stirred with a planetary stirring device until a homogeneous solution was obtained. 1 part by weight of a photo radical polymerization initiator (IRGACURE 651, manufactured by Gibbart Chemical Co., Ltd.) was added to the obtained mixture, and the radical polymerization initiator was heated to 700 ° C. to dissolve the mixture, followed by stirring with a planetary stirring device. A mixture was obtained. To the obtained mixture was added 1 part by weight of a cationic polymerization initiator (manufactured by Asahi Denka Kogyo Co., Ltd. sp_17〇), 5 parts by weight of silicon dioxide particles (average particle diameter 1.5 # m), and a silane coupling agent (Shin-Etsu Chemical Co., Ltd. Made by the company, KBM403) 1 part by weight, stirred with a planetary stirring device, and then dispersed with 3 rolls made by P Xunman to obtain a curable resin composition for a liquid crystal display element. Curable resin of 200540537 The compositions prepared in Examples 1 to 7 and Comparative Examples i to 5 were evaluated by the following methods. The results are shown in Table 1. (Next test) 1 part by weight of spacer particles (manufactured by Sekisui Chemical Co., Ltd. OT UACr Tea A, "Particle beads SI-H055") were dispersed in a liquid phase-a round of mn nondan ... / curable resin composition for metal parts. 〇In severe injuries, use the liquid crystal dripping method.

The agent is placed in the central part of glass (made by Kunning Valley Co., 37), and another piece of glass (made by Kunning Valley Co., is laminated, and the sealant is pressed and stretched to a uniform thickness.) Use a metal gear lamp to irradiate ⑽mWW for 30 seconds, and further heat for 30 minutes (Examples 1 to 4 and Comparative Examples 1 to 4); 隹 γ This J 4 is not directly exposed to UV radiation at 120 ° c) Heating for 1 hour) to obtain the next test piece. For this test piece, a tension gauge was used to measure the adhesion strength. For test pieces that were left for _hours under the conditions of M and 95, the tension juice was also used. Measure the adhesive strength (adhesive force after high temperature and high humidity test). (Evaluation of storage stability) The curable resin composition was stored in an ambient atmosphere of 23t and 50% rh, using an E-type viscometer (25 ° c 'lrp _Measure the viscosity and compare it with the initial viscosity to calculate the time period when the value doubled. (Liquid crystal display element evaluation (spot evaluation)) Spacer particles (made by Sekisui Chemical Industry Co., Ltd., "particle beads SI_H055") 1 Weight share Scattered in 100 parts by weight of the curable resin composition for a liquid crystal display element, and used as a sealing agent for a liquid crystal dropping method. For two pieces of film, the thickness of the alignment film and the substrate t with electrodes is 1 mm. The sealant is applied by a dispenser. Next, a small drop of liquid crystal (manufactured by Jisuo Corporation, Jc. 5000LA) is applied to the entire surface of the sealant frame of the electrode substrate, and immediately applied. Attach another substrate with electrodes, and harden the sealant using a metal lamp at 100 mW / cm2 for 30 seconds, and then heat it at 12 ° C for 30 minutes (Examples 1 to 4). And Comparative Examples 1 to 4 were directly heated at 120 C without UV irradiation) to obtain a liquid crystal display element.

With respect to the obtained liquid crystal display panel, the liquid crystal alignment nano-IL near the sealant after the operation test was observed visually immediately after the liquid crystal display panel was manufactured and after the operation was performed under the conditions of 65 ° C and 95% RH. The degree was evaluated based on the following criteria. ◎: Totally no stains 〇: Only slight stains △ • Some stains x: Many stains 43 200540537

[11 Example 7 3 months 3000mJ / cm2 + 120 ° Cx60 minutes 460 460 ◎ ◎ Example 6 3 months 3000mJ / cm2 + 120 ° Cx60 minutes 450 450 ◎ ◎ Example 5 3 months 3000mJ / cm2 + 120 ° Cx60 minutes 460 450 ◎ ◎ Example 4 3 months 120 ° Cx60 minutes 480 470 ◎ ◎ Example 3 10 days 120 ° Cx60 minutes 490 410 ◎ ○ Example 2 3 months 120 ° Cx60 minutes 470 470 ◎ ◎ Example 1 10 days 120 ° Cx60 minutes 440 380 ◎ 〇 Storage stability and hardening conditions Immediately after being maintained at high temperature and high humidity. Immediately after production and operation tests are completed, the force of the liquid crystal display element is compared. Example 5 3 months 3000mJ / cm2 + 120 ° Cx60 minutes 480 480 〇 &lt; Comparative Example 4 3 months 120 ° Cx60 minutes 440 420 〇X Comparative Example 3 10 days 120 ° Cx60 minutes 480 410 &lt; X Comparative Example 2 3 months 120 ° Cx60 minutes 450 450 〇X Comparative Example 1 10 days 120 ° Cx60 minutes 460 390 &lt; X Storage stability Hardening conditions Immediately after being maintained at high temperature and high humidity Immediately after fabrication After completion of the operation test Adhesion (N / cm2) Image of the liquid crystal display element 200540537 From Table 1, we can see Example Shu ~ 7 produced the curable resin composition 'high bonding strength and storage stability are also not reach the degree of practical problems. In addition, in a liquid crystal display element produced as a sealing agent for a liquid crystal dropping method, color spots were almost not observed before and after passing the high-temperature and high-humidity test, so that it was practically no problem at all. Resin composition, but a crystal display element made of this resin, in contrast, the hardening produced in Comparative Example ^ 5 has the same degree of adhesion and stability.

An object was used as a liquid prepared with a sealing agent for a liquid crystal dropping method, and a stain was observed. Usability •… 丨 ~ such as-, 丨, ~ '丨 卞 When using a hardening resin $' 疋 m method to manufacture a liquid crystal display element, it is used as a seal 2: In the case of use, or by a dropping method without ultraviolet irradiation When used as a sealant for liquid elements, liquid crystal stains are less likely to cause: Type: Manufacturing of liquid crystal display elements with high image quality with few stains; and liquid crystal methods made of the hardening resin composition for liquid crystal display elements. Encapsulant, upper and lower conductive materials, and liquid crystal display elements. [Schematic description] None [Description of main component symbols] None 45

Claims (1)

200540537-% 10. Scope of patent application: 1 · A hardening resin composition for liquid crystal display elements, which is characterized in that: 'The resin component is only: 1 molecule has a hydrogen-bonding functional group and a self-selecting cyclic milk group and an oxa group. Hardness of at least one type of B-month &amp; group in the group consisting of cyclobutanyl group and episulfide group and the number of hydrogen-bonding functional groups in one molecule divided by the weight average molecular weight of 3.5 × 1 or more Resin; and contains a thermosetting agent and / or a cationic polymerization initiator. 2. · A curable resin composition for a liquid crystal display element, characterized in that _ is the only component in the resin: it has a hydrogen-bonding functional group in one molecule and is selected from an epoxy group, an oxetanyl group, and a cyclic group. At least one functional group in the group consisting of sulfide groups, and the number of hydrogen-bonding functional groups in one molecule is divided by the weight average molecule, and the amount obtained is a hardening resin having a value of 3.5x10-3 or more and a softening temperature of 1. Polymerizable resin at 50 C or higher; and contains a thermosetting agent and / or a cationic polymerization initiator. 3. A curable resin composition for a liquid crystal display element, comprising: 1 molecule having a hydrogen-bonding functional group and selected from epoxy groups, oxacyclobutane groups, and episulfide groups. A curable resin having at least one functional group in the group and a value obtained by dividing the number of hydrogen-bonding functional groups in the i molecule by the weight-average molecular weight of 3 · 5 × 10 3 or more, and a cationic polymerization initiator. 4. The hardenable resin composition for liquid crystal display elements such as the scope of patent application No. 3, which further contains a polymerizable resin having a softening temperature of 5 ° C or higher. 5. The scope of patent applications No. 1, 2, 3, or 4 The curable resin composition for liquid crystal display elements, wherein one molecule of the curable resin has a choice of 46 200540537 10. Patent application scope: 1. A curable resin composition for liquid crystal display elements, characterized in that Only: There are at least one functional group in a group consisting of a hydrogen-bonding functional group and an epoxy group, an oxetanyl group, and an episulfide group in one molecule, and the number of hydrogen-bonding functional groups in one molecule A hardening resin having a value of 3 · 5 X10 · 3 or more divided by a weight average molecular weight; and containing a thermosetting agent and / or a cationic polymerization initiator. 2 · A hardening resin composition for a liquid crystal display element, It is characterized by 'only one resin component: one molecule having a hydrogen bonding functional group and at least one functional group selected from an epoxy group, an oxetanyl group, and an episulfide group' and 1 A hardening resin having a value of 3.5X10 · 3 or more and a polymerizable resin having a softening temperature of 50 C or more, obtained by dividing the number of hydrogen-bonding functional groups in the molecule by a weight-average molecular weight; and containing a thermosetting agent and / or cationic polymerization Initiator 3. A curable resin composition for a liquid crystal display element, characterized in that it contains: 1 molecule having a hydrogen-bonding functional group and selected from an epoxy group, an oxetanyl group, and an episulfide group. A hardening resin and a cationic polymerization initiator having at least one functional group in a group and a number obtained by dividing the number of hydrogen-bonding functional groups in one molecule by a weight average molecular weight of 3 · 5 × 10 · 3 or more, and a cationic polymerization initiator. The hardening resin composition for liquid crystal display elements in the scope of the patent application No. 3 further contains a polymerizable resin having a softening temperature of 500 ° C. or higher. 5 · If the liquid crystal in the scope of the patent application is No. 1, 2, 3 or 4 Display element 47 200540537 A curable resin composition, in which the molecule of the curable resin has at least one selected from the group consisting of an epoxy group, an oxetanyl group, and an episulfide group. Kedar can be two or more. 6. The scope of patented Shu, 3, 4 or 5 of the liquid crystal display element with a curable resin composition, wherein the curable resin weight average molecular weight of 300 or more. 7. A sealant for a liquid crystal display element, comprising a hardened resin composition for a liquid crystal display element according to claim 1, 2, 3, 4, 5, or 6. 8. An upper and lower conduction material, characterized in that it contains a hardening resin composition for liquid crystal display elements with the scope of patent applications Nos. 1, 2, 3, 4, and 5 or 6 and / or a patent application scope The sealing agent for liquid crystal display elements of Item 7 and conductive fine particles. 9 · Liquid crystal display elements, which are characterized by Lifan, U · nephew * &quot;, Irakawa Ding won the seventh item in the range a gg-one day ^ sealant for extraordinary parts and / or application | 第 8 Items above and below are made of general materials. Η ^ 一 'Schema: None 48 200540537 VII. Designated Representative 囷 · (1) The designated representative in this case is: (No). (2) Brief description of the component symbols in this representative figure: None 8. If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: