TW201130956A - Sealing compound for liquid crystal dropping process - Google Patents

Abstract

The issue of the invention is that since a sealing compound for a liquid crystal dropping process according to the invention is applied in the liquid crystal dropping process, a precision coating of stable sealing width can be performed for a display panel, and the viscosity variation of the sealing compound placed under 25 degrees Celsius can be reduced. Accordingly, while performing optical irradiation under a condition of being in contact with liquid crystals, the liquid crystal pollution problem is restricted at the minimum degree. The display panel completed by thermal curing, in the reliability experiment, the sealing compound may not be peeled off and does not leak liquid crystals as well. The solution means of the invention is a sealing compound for liquid crystal dropping process, containing (A) constituent and (B) constituent as necessary constituents and being obtained by thermal curing and photo-curing. The (A) constituent is an epoxy resin having fluorene skeletons; The (B) constituent is a (metha)acrylic based resin having isocyanuric acid skeletons.

Description

201130956, the invention description: [Technical field of the invention] This is a liquid crystal dripping work having a low liquid crystal contamination (4) which has excellent (four) coating property and preservability, and has a small change in the ratio of the agent to the electric charge (4) [Prior Art] In terms of assembly, it used to be a sealant. As a component of the sealant, it is widely used as an oxygen resin or a curable (mercapto) acrylic resin. 'Previous system 2 goes to the main seal _ after contact with the liquid crystal after hardening, but in the case of two: '', but in the unhardened state, it contacts the end sealant of the liquid crystal, and the number of eves shows uneven brightness. Various problems. 199 : 1 and non-patent document 2 mention about the terminal sealant: Mountain = respective problem points. In the non-patent document i, the detection revealed by the epoxy tree Caused by causality. Calling _ By the previous assembly method can not improve the efficiency of the work, so the near method becomes the mainstream. That is, a method of hardening the surface agent in contact with the sealant B' sub-surface agent. In the case of sealing, the seals which have both thermosetting and photohardenability are only hot and hard, and when the contact with the liquid crystal is in contact with the liquid crystal, it may cause dyeing. In other respects, When the stick is hardened, it will be produced after the main agent is applied: the sputum is not sturdy, and the part will cause hardening and shattering to make the ingredients dissolve out.

S. Liquid crystal dripping jade method is attracting attention in terms of liquid crystal contamination. In addition, the liquid crystal display panel is also expected to reduce the width of the coating liquid bead (_) 3/25 201130956 ^Extension, the part shown. Especially in the case of large panels, because the coating distance from the green is smaller than the small secret length, 'the width of the rotating coating is uneven.' The worst case is when the pressure is 2:=3=2^humidity_, 2 atmospheres. In the reliability test of the Xiaoyan Temple, there will be a coating of the sealant of the smoke 4, which is only ΓΐίΛ possibility. ^ It is not enough. Special axis _: Load: at === to join Filling _ square" only j: its (four) low 1% of the resin component, the agent used to lightly increase the viscosity. It is not clear whether the coating stability can be maintained by using the filling lion degree. US) C and fine f are similarly suitable for the __1 method (the literature of the rouge can be cited as Patent Document 2. The patent of the patent document 2) has a different isocyanuric acid 2 in the _ base. X 'special _: 2 ==== purpose, its special fine olefinic tree such as the same refinement step on the liquid crystal stains difficult to touch (four) whether it is produced as a human = Lee has a (four) ring Oxygen resin has been unveiled from the past [previously] The use of the literature 1 has not been explicitly disclosed. [Patent Document]: ==Open No. __ pamphlet patent L L 4224526 = literature; No. 4/25 201130956 Non-Patent Document 1 The 23rd Sakamoto LCD Society Symposium Presentation Preliminary 2PA06 "Crystal Crystal Injecting Chromatogram Effect Solution (Analytical Method) - Injection Port in Actual Liquid Crystal Cell The analysis of the cause of the failure of the display of the part of the Ministry of Environmental Science and Technology 2" The first draft of the 23rd session of the Society of Liquid Crystal Society, "The effect of the sealant on the LCD display failure" [Summary of the invention] [The problem to be solved by the invention] The sealing agent for liquid crystal dropping method is difficult to coat in liquid crystal pollution The sealing property 'save stability and the like are all competing. [Means for Solving the Problem] The present inventors have tried to achieve the above object, and thus the present invention is completed; An epoxy resin having a skeleton of the material = = a (meth)acrylic resin having a hetero-cyanuric acid skeleton as a necessary knife, and which is thermally hardened and photohardened by a liquid crystal dropping method Invention. * The film of the present invention - the form of death (ie, the first item of the patent scope), contains the (Α) component, (Β) component, thermal hardener and photoinitiator as essential components, and A sealing agent for a liquid crystal dropping method which is thermally cured and photohardened. (Α) component: an epoxy resin (Β) component having a first skeleton: a (fluorenyl) acrylic resin having a hetero-cyanuric acid skeleton. The second embodiment (ie, claiming the second item of the patent scope) is a sealant for a liquid crystal dropping method according to the invention of the invention, wherein: the composition of the sapphire component, the thermal hardener and the photoinitiator The basic composition is about 100 C when the viscosity is 100~]70P 5/25 201130956 Apply for the three implementation forms (ie, the third item of the patent scope), for example, as (c) two or three of the second-party liquid crystal dripping method sealant, of which two'丨 丨 具有 环氧 环氧 环氧 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = The phase transition temperature difference is 〇~2 (rc. The sealing agent is densely used in the liquid crystal dropping method described above. [Effect of the invention] ^ The sealing width is stabilized by using the liquid crystal dropping method sheet of the present invention in the liquid helium dropping method Precision coating, while 'C placed, the viscosity of the sealant is also low. Further, in the display panel which is completed after the thermal curing in the state of the crystal contact, and the display panel which is completed after the thermal curing, the sealing portion does not peel off and the liquid does not occur. [Complex method] Take the money and correct it. (A) ^Knife used for making money, = If there is an epoxy resin having a skeleton, there is no particular limitation. For example, an epoxy resin having an s skeleton represented by the formula (1) can be used.

^^P--(CH2CH2〇)-CH2-CH-CH CH2-CH.CH2-(OCH2CH2)n-〇(1) 6/25 201130956 (Ί, each independently hydrogen or fluorenyl, n-series are independently 〇 5 5 5 5 5 5 5 5 5 5 5 5 5 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪 大阪These are the same. The component (B) which can be used in the present invention is not limited as long as it is a (fluorenyl)acrylic resin having an isomeric cyanide skeleton. (Hereinafter, the acrylonitrile group and the mercapto propylene group are collectively referred to as "(indenyl) acrylonitrile group." Further, the acrylic resin and the mercaptopropionic acid resin are collectively referred to as "(曱The "p-glycolic acid-based resin" is preferably a compound having a structure represented by the general formula (2) and having two or three (meth)-thracene groups in one molecule. 〇 〇 R1 X-〇CH2CH2 xCH2CH20-(C0(CH2)n0)-C-c=CH2

NN 0 ? 〇R1 CH2〇H2〇~(CO(CH2)n〇)firC~C=CH2 (2) (X is hydrogen, or R1 0 H2C = 0-£-(〇(CH2)nC〇)i Further, each of R1 is independently hydrogen or a fluorenyl group, and n is each independently 0 to 5, and m is each independently 0 to 2.) More preferably, it has 3 (fluorenyl) acrylonitrile groups in one molecule. There is a compound having a structure represented by the general formula (3).

S 7/25 201130956 R10 〇 O R' H5C=C-C-(0(CH2)nC0),-^)CH2CH2N II CH^HjO-tCOtCH^nOJsrC-^CH;

CH2CH2〇-(CO(CH2)nO)nTC-C=CH2 (3) (R1 is each independently hydrogen or a fluorenyl group, and n is each independently 0 to 5, and the m systems are each independently 0 to 2. Further, it is more preferable that the η of the general formula (3) which is commercially easy to start is all 5, the compound in which m is all 1 or the compound in which m is all 0. Specific examples of the component (B) include M-21 5 (compound of the following chemical formula (4)) having an iso-cyanuric acid skeleton in the Aronix series manufactured by Toagosei Co., Ltd., and M-313. (The mass ratio of the compound containing the following chemical formula (4) to the compound of the following chemical formula (5) is 30: 70 to 40: 60), Μ-3] 5 (containing the compound of the following chemical formula (4) and The mass ratio of the compound of the formula (5) is 3: 97 to 13: 87), Μ-327 (the compound of j+k+Ι and 3 in the following chemical formula (6)), etc., Xinzhongcun Chemical Industry Co., Ltd. A-9300 (compound of the following chemical formula (5)), A-9300-]CL (compound of j+k+Ι and 1 in the following chemical formula (6)), etc. , but not limited to this. Hoch2ch

, person N 〇 〇

〇 /ch2ch2o-c-ch=ch2

CH2CH2〇-C-CH=CH 2 (4) 8/25 8 (5)201130956 · 〇〇H2C=CH-C-〇CH2CH2, JL pu _L ? 2 2,n/^\n/ch2ch2〇-c- Ch=ch. 0'

N , , 0 CH2 〇 H2 〇 〇 C-CH=CH, H2C=CH^(0(^ σ

MO 'rC-CH^CH, I oCH2CH2〇-(C〇(CH2)5〇)r^CH=CH2 (6) The sealing agent for liquid crystal dropping method of the present invention, which can also be used as a compound of the base The compound (c) which is used in the present invention is a compound which exhibits Ρ and has one or more propylene groups and/or decyl propylene (hereinafter, i molecule) The compound of propylene is also a "partial".) The part of the acid-fused epoxy compound is subjected to the reverse bank iitm as described below. In this reaction, a propylene (tetra) acid having two oxygen compounds and a (meth) propyl group in one molecule is used to make a soil of a polyvalent epoxy compound, To introduce a (meth)acrylic acid group. In this case, not only the polymerization is carried out, but only a part of the epoxy groups are subjected to the ring-opening water σ (under the squat, early, and 屯 is referred to as "esterification").

Oh; -〇-CH~~CH~ - 〇-c - 1: (3) As the polyvalent epoxy compound as the precursor, an epoxy compound having two or more epoxy groups in the above-mentioned one molecule can be used. Among them, an aliphatic polyfunctional liquid epoxy such as ι ι 9/25 201130956 butanediol = glycidyl ether, 1 > 6-hexanediol diglycidyl ether, or trimethomethyl triglycidyl ether = double test compound such as t-dihydrate (4), double-shrinkage, etc.; (4) fine (four) compound wire-type epoxy compound; nail-type condensate body, etc. Oxide oxidized (4) double _ bioepoxidized dicyclopentadiene and benzoic benzoic acid with hydrazone, alicyclic bone (four) secret epoxy compound; naphthalene and The secret type of the micro-organisms of the micro-organisms of the Wei-Hua-Wings is not limited to this. From the viewpoint of price and supply stability, it is taken as a bis-epoxy compound having a double-time (tetra) epoxy compound, and a bisphenol derivative epoxy compound. Preferably, propionic acid is the above-mentioned carboxylic acid or methacrylic acid having a (meth)acryl fluorenyl group. As a representative partial acrylated epoxy compound, a compound having one epoxy group and one (meth) propylene in the oxime molecule can be cited. That is, the compound is equivalent to the stoichiometry of the chemical conversion of acetoacetate having two epoxy groups (only 0.5 of the equivalent epoxy groups per equivalent of the epoxy group) Preferably, the (meth)acrylic acid is preferably used in the range of 0.5 to 0.6 equivalents. The lining is carried out according to the general method of the toilet. In general, the two kinds of In the presence of an organic catalyst, it is heated and recombined, and is easily and quantitatively =. As an alkaline catalyst, it can be used as a basic catalyst: base:: base gasification, triphenylphosphine, triphenyl (10) St Part of the acrylic acid (tetra) epoxy compound can also be used as 4 materials = 10/25 8 201130956 ^ As a product of the (4) A-type epoxy tree, it can be listed as a product. The secret of the system; fine 561, etc. 1 In the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The more the compound, the more the functional group which is unrelated to the reaction of the epoxy group and the thermal hardening described later, so that the heat-hardening day θ θ is difficult to enter, which hinders The formation of a chemical network. In other words, there is a tendency for the total amount of exhaust gas generated by the hardened material to increase. Therefore, in order to remove the compound which is acetated as the entire epoxy group as an impurity, the temperature portion The C-transfer epoxy compound is preferably subjected to the present invention. All of the oxygen-releasing products of the present invention have a ratio of oxygen to a di-base of a betaxyloxy group: (methyl) propylene (s). 60, better for Η): 90~30: 70. The amount of the component (8), the component (〇, other epoxy resins to be described later, and other mouth groups), the acid resin, may be adjusted to the above range. & / 2, the content of (C) is _ _ / relative to the resin component described later. It is preferably 5 to 40% by weight, more preferably 1 to 3 % by weight. For the use of the secret surface, the use of the agent can make the secret epoxy resin (4). In particular, the angle represented by the double-aged epoxy resin is known. The m-ring adduct compound is micro-used as a latent hardener. As heat hardening

Amicure, Tasmania Chemical Industry Co., Ltd. J7ujicure Foundation II / 25 201130956 :: Cheng (5) 1 - Suction Co., Ltd. made a "column = not limited to this temple. Also, although it can be listed 2 · Mimi Sit, 2-ethyl taste. Sit, 2·propyl 岐 岐 (4) aryl hydrate of the compound hydrate; 2, ethyl taste:; :: γτ tart; malonate Lu ^ + ^ , ]53.Φ )_5_isopropylhydantoin and other 肼 compounds; secret imine, more than two:: amine, tertiary phosphine, quaternary salt, quaternary salt, etc., but not limited to In addition, it is also possible to use two or more types in combination. In the liquid crystal sealing agent of the invention, a hot air drying furnace or the like is used, and hunting is performed to make the reaction into hardenability, which is called thermosetting. In the present invention, it is necessary to thermally harden the liquid crystal panel at a temperature of 80 to MOt without causing damage. It is preferable that the composition is _ (4) component, (the age of the fat, the total weight of the fat component - the mass part) The addition of the hot one-way shell is less than the above-mentioned addition amount and the curing amount is poor. The sealing compound for liquid crystal dropping method of the present invention includes a photoinitiator... The photoinitiator used in the present invention can be exemplified by an energy beam such as an external ray, an X-ray, an electron beam or the like, which generates a free light = a base photoinitiator and a Bronsted acid or a Louise taxi. The compound having a (meth) two-alkenyl group is related to the (4) crystal-based magnetic sealing agent of the present invention, which is a hardening property obtained by hardening the t-line, which is called photohardening.

As a specific example of the above-mentioned radical photoinitiator, U 12/25 201130956 diphenylethyl from _, diethoxy stupid ~ 継 曱 曱 曱 曱 曱 曱 撼 撼 撼 撼 撼 撼2-morpholinyl (4_" Shirt, "Working Base% Base Ketone, 2-Methyl Soil (4 曱 曱 base) Propane-1-one, 2-Bistyl-2 - 曱美丝基) D-W-2-indolyl small i, phenotypes of phenotypes; benzoin, stupid methine methyl, ^ 钔 钔 丙基 propyl ether, benzoin isobutyl ether, etc. Class; diphenyl fluorene, o-branched benzyl toluene based material " base - diphenyl sulfide, .3, 3 ^ ^ butyl emulsified _ diphenyl modulate, 2, yttrium trimethyl Stupid call 2 rhyme reduction)

Ltr ) Triterpene ammonium methoxide, etc., dipyryl 2- propyl hydrazine ^ isopropyl (four) ton _ '2, 4 _ ii s trace 1, 3 ton ton copper, bismuth - gas ice propoxy D Sebutone, dibasic·9 (four) tons of materials are found, but Asia and Africa are limited to these. The gas salt of the above-mentioned cationic photoinitiator: a salt, a barium salt, etc., specifically, a cumbersome two = salt, a heavy nitrogen six gas disc acid salt, a benzene diazo six acid salt, 44, _ Double [雔二/, _ acid salt, triphenyl sulfonium hexafluoroborate, acid bismuth, _ again?乙;乙乳基phenyl)dihydrothio]phenylthiobishexafluoroscale II:=Fluoric acid salt, diphenyl-locked iron six-salt salt, these t ^ In addition, it is not limited to the total amount of the (meth) =,) component, (<2) component, and other (methyl) propylene glycolate (described later). (meth) propylene-based resin component total mass 13/25 201130956 The dye photoinitiator is preferably 0. 丨 by mass, photohardenability, / radish initiator less than 0.] dyeing. Further, when it is larger than 5 gentlemen, when the liquid crystal is caused to come into contact with the liquid crystal, the liquid crystal is contaminated, and when the liquid is contaminated, the exhaust gas is generated. The liquid helium is dropped into the sealant for the working method in order to simplify the inhibitor. If the addition amount of the polymerization inhibitor is too good, the reactivity will become better, but on the other hand, the reactivity will become two = stable. For the liquid crystal dropping method, the seal is used for the phase 0 0 / ^ n mountain ~ n00 Berry%' Add 0 paste ~ 〇 1 and. The two-body example can be exemplified by hydrogen styrene, methoxy hydrogen only = diyl group, stupid diterpene and the like hydrazine polymerization inhibitor: two = 2, 4, a tributyl butyl, 2 - tert-butyl * dimethyl Butyl butyl dibutyl _ 4 · nonyl phenol, 7 4 a. one, 6--- inhibit m-amine amine ==== (four) age-based polymerization of piperidine, 1,4-two 9 r < soil-·Λ6 ,6-tetramethyl^ 2 9 6 ,:,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Base, 4, geninotetramethyl, 4-benzyl oxime, 9 ? a < Λ疋-1 gas free from "polymerization" fresh,,: it: from the base of nitrogen oxides from the agent two = = external agent And the inorganic filling composition. The composition of the lover knife is composed of a basic composition including a thermosetting agent and a photoinitiator, a thermosetting agent and a photoinitiator. P, the basic composition is composed of a resin component and a liquid crystal dropping method sealing, and the so-called resin component is a resin component of the component (A) and the component (β). Specifically, Among the acrylic resin, the bismuth (C) component, other epoxy resin, and enamel resin component, A) Ingredients 14/25 201130956 (B) Ingredients are essential ingredients. *The reason for the surface of the coating is that the county is affected by the viscosity of the core, and the viscosity of the core is affected by the addition. In order to maintain the coating properties, the basic: preferably is the outline. Miscellaneous ratio (10) 2 | one; _ with fillers will reduce the correction, shooting occurs the coating liquid beads break f. Colony 3 surface coating 2 = 17 〇 Pa, S high when 'even if only a small amount of added" month soil cloth operation% will A wire drawing occurs (cobwebbing). ^Invented liquid crystal dropping method (4) sealing money, ^ damage dry square, can also contain (eight) ingredients and (other epoxy difficult), (B) ingredients and (c = month: below 'also known as "other (methyl The acrylic acid eucalyptus has both 曰i and the above (meth)acrylic resin, and also contains the t-reactive t-reactive diluent or monomer of the above-mentioned propyl group. It is preferable to modify bisphenol a (in the range of the characteristics of the liquid crystal dropping method of the present invention, it is also suitable for care, 0 release) v without knowing the metal powder, calcium carbonate, talc, strontium of the present invention. ::^, / miscellaneous materials, etc.; inorganic fillers such as oxidized Ming; _35, oxidized Ming, hydrogen filling, plastic sword, antioxidant,, Xiao ^ 祛. Filling, core-shell filling 5 Adding two kinds of equalizing swords, rheology control agents, etc.: the coupling strength to the resin strength, the subsequent strength, the enthalpy, the composition, the hardened material, the preservation property, etc. are all excellent. It is suitable to adjust. The amount of y used is as long as the difference of the liquid crystal dropping method of the present invention is 〇t or more and 2.0°c or less, more #=, W, Good phase transfer temperature is better for the heart, lower than said. Phase f <5/25 201130956 The transfer temperature difference is contaminated by liquid crystal, and the display is contaminated. The liquid crystal dropping work θ 2nd, the greater the temperature difference The phase transition temperature difference of the sealant described in the examples described later is not measured. The liquid crystal turtle _ _ which is produced by the present invention is not particularly limited, and may be used by: The method of the agent's fat component, the thermosetting agent, and the method of light-initiating, the mixing procedure of the above-mentioned tree agent, and the basic composition of the polymerization, the filling, and the like, the mixing time, and 1 ^ The method of mixing the temples, etc. The liquid crystal dropping device, the device, and the like of the present invention are also not particularly limited. The manufacture of the device, that is, the present invention = the sealing agent can be suitably used for the sealing of the liquid crystal display liquid crystal dropping method Agent: 2:: For the use of the upper liquid, drip the working method, sealant, and the workmanship ~ can prevent the display brightness unevenness and (4) materials, can get the device. ', the liquidity display is still guilty [implementation Example] Next, an example pair is given. The invention is not limited to the examples. The steps are described in detail, but the present invention is the following components: (1) basic composition (resin component) Comparative Examples 1 to 3 > In order to modulate the sealing agent for liquid crystal dropping method.

It is divided into 1 epoxy resin with the first skeleton, and the epoxy resin of the frame is "(10) OL PG-Gang (made by Osaka Gas Chennai Co., Ltd.), and 八 epoxy resin type epoxy resin with rack" jERl52 (Japan Ep〇Xy Resin shares 16/25 201130956 limited company system)" (B) Ingredients: (mercapto) acrylic resin with iso-cyanuric acid skeleton • Caprolactone modified type: "AronixM-327 (made by East Asia Synthetic Co., Ltd.) • Ethylene oxide modified type: “Aronix M-215 (manufactured by Toagosei Co., Ltd.)” (C) Ingredients. 1 molecule has an epoxy group and a (fluorenyl) acrylate group. Compound • Partially esterified bisphenol A epoxy resin: “UVACURE1561 (Daice]-Cytec Co., Ltd.)” Other components (mercapto) acrylic resin without iso-cyanuric acid skeleton* Bisphenol A type Epoxy acrylate: "EBECRYL3700 (manufactured by Daicel-Cytec Co., Ltd.)" • Acrylic I, "Light Acrylate ΓΒ-ΧΑ (manufactured by Kyoeisha Chemical Co., Ltd.)" (photoinitiator) • 2, 2-dimethoxy-],2-diphenylethane-1-one: "IRG ACURE651 (manufactured by Ciba Specialty Chemicals) (thermosetting agent) • Dimethyl malonate: “MDH (manufactured by FINECHEM, Japan)” (2) Filler organic filler • Core-shell filler: “ZEFIAC F351S ( 17/25 201130956 Inorganic Filler • Vermiculite Powder: “SEAHOSTAR KE-C30 (manufactured by Sakamoto Co., Ltd.)” (A) component (or (A,) component) The components (8) and (C) were stirred in a blender for 30 minutes. After that, add other ingredients and then mix +> 0 minutes. The detailed modulation amounts are in accordance with Table 1, and the numbers are all expressed in parts by mass. [Table Π Raw material name PG-100 Example 1 10 Example 2 10 Comparative Example 1 ΙΓ !!丨·ΜΙ Comparative imitation 4 2 _Comparative example t jER152 10 '---- M-327 30 30 ' M-215 30 -——~~~~-- UVACURE1561 20 20 20 20 —------- 100 EBECRYL3700 40 40 40 40 —----~ IB-XA 30 ~----. IP.GACURE651 1 1 1 1 —--- Call 1 MDH 5 5 5 5 ~~~*—---- 5 F351S 20 20 30 35 15 KE-C30 20 20 20 20 20 Total (overall) 146 146 156 161 14] '*** *'----- Total (basic composition) 106 106 106 106 106 ----- The composition of all components except the powder component of the organic filler and the inorganic filler is used as a basic composition, and The EHD type viscometer (manufactured by Toki Sangyo Co., Ltd.) was subjected to subtraction measurement at 25. The results are summarized in Table 2. The numbers are all expressed in [Pa.s]. 18/25 201130956 [Table 2] Raw material name__Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Viscosity of basic composition 130 160 50 - 20 190 For Examples I and 2, Comparative Example 1 In the liquid crystal dropping method of 3, the phase transition temperature measurement, the specific resistance measurement, the peel strength test, the storage property test, and the coating test were carried out. The results are summarized in Table 3. [Measurement of phase transition temperature] The phase transition temperature measurement is one of the methods for evaluating the contamination of liquid crystals. It has been confirmed that the difference between the phase difference temperature of the contaminated liquid crystal and the original phase transition temperature is larger. Contaminated. After 〇15 g of the liquid crystal sealing agent was added to the sample bottle, 1.3⁄4 of liquid crystal (ZLI-4792 manufactured by Merck Co., Ltd.) was added. Place the aforementioned vial into the 〇〇. After 10 hours, the hot air drying oven was taken out and placed at room temperature for an hour. The supernatant (liquid crystal) was taken out from the sample bottle, and the phase transition degree (endothermic peak temperature) measured by a differential scanning calorimeter DSC6200 (manufactured by Seik〇 Instruments Co., Ltd.) was measured. On the other hand, the phase transition temperature of the liquid crystal after the liquid crystal sealing agent was not contacted and subjected to the same treatment was measured in advance. As a result, the 曰 phase transition temperature was 94. (: The difference between the above two temperatures (absolute 値) is taken as the "phase transition temperature difference (.〇", and is determined as the liquid crystal contamination by the following criteria: Standard. Wooden spoon 〇: phase transition temperature difference is less than △ : phase transition temperature difference is 1.5~2. 〇t X : phase transition temperature difference is greater than 2. 〇 °C [specific resistance measurement] 19/25 201130956 Specific resistance measurement is one of the methods for evaluating the contamination of liquid crystals. It is confirmed that the difference between the contaminated liquid crystal and the original specific resistance, the greater the change of the specific resistance, the more the liquid crystal is considered to be contaminated. After adding the liquid crystal sealing agent to the sample bottle, 'add 1 · 5g of liquid crystal (Merck ZLI-4792, manufactured by Co., Ltd.) Put the sample vial into a hot air drying oven at 1 〇〇C for 10 hours, remove it and leave it at room temperature for one hour. Remove the supernatant (liquid crystal) from the vial. In the liquid electrode LE21 (manufactured by Ando Electric Co., Ltd.), the liquid crystal specific resistance was measured by a liquid crystal specific resistance measuring system (manufactured by Toyo Techn i Co., Ltd.) and an ElectiOmeter Model 6517A (manufactured by ICElTHLEY) at a voltage of 10 V for 5 seconds. .on the other hand The specific resistance of the liquid crystal after the liquid crystal sealing agent was not contacted and subjected to the same treatment was measured in advance. As a result, the specific resistance was 2.0 > (10) 3 Ω * ιπ. The enthalpy calculated by the following formula was regarded as the "specific resistance ratio" The standard of liquid crystal contamination is set by the following criteria. The more serious the liquid crystal pollution is, the smaller the specific resistance is. 〇: The specific resistance ratio is greater than 0.1 △: The specific resistance ratio is 0.1 to 0.01 X: The specific resistance ratio is less than 0.01 [ Mathematical formula 1] Factory "Specific resistance after test" (Q'm) "Specific resistance ratio =------------ "Initial specific resistance" (Q_m) [Next strength test] Sealant It is applied to one of the non-experimentable glass sheets (50 mm ><25 mm x 〇.7 mm) and is bonded to the other alkali-free glass plate to form a cross shape, and the sealant is sufficiently dispersed on the bonding surface. Fixed. High-pressure mercury lamp with lamp height of 15cm, illumination of 100mW for 30 seconds, 120°C for X1 hour, 20/25 8 201130956 for test>{. After returning to room temperature, test the test piece with glass The two private solids of the panel are stretched in the direction of peeling at a stretching speed of 5Qmm/min, and measured. The maximum load until the test piece is destroyed is used as the "initial peel strength (N/m)". In addition, a plurality of the above test pieces are prepared and placed in a 2rc, 2 atm environment of the pressure steel test. The test piece after 24 hours was subjected to the same measurement. The peel strength at this time was defined as "peel strength (N/m) after the test". "Initial peel strength _])" and "test under the waste force" After the peeling strength (N/m), the "peel strength retention ratio (%)" was calculated by the following formula as a standard for resistance to high pressure and high humidity. One after another: peel strength retention rate is greater than 9〇% △ ·· Peel strength retention rate is 90~60% X · Peel strength retention rate is less than [Math 2] "Testing Xianxian rate - "peel strength I after test" >* ] 〇π i initial peel strength": N/m: [preservation test] After 1 hour of resin blending, EHD type viscometer (made by Toki Sangyo Co., Ltd.) at 25 °c The viscosity was measured and determined as "initial viscosity (Pa.s)". Also 'at 25. After 12 hours of squatting, the 疋妯 degree was measured in the same manner as the initial viscosity and was defined as "viscosity after test (pa·S)". (According to JISK5600_2-3 as the standard.) According to the following formula, the "point change rate (%)" is calculated from "the viscosity after test (s)" and "initial viscosity (Pa.s)" as a preservative standard. 〇: viscosity change rate is less than 30% △: viscosity change rate is 30~5〇〇/0 21 /25 201130956 χ : viscosity change rate is greater than 50% [Math 3] "Viscosity after test" (.1=> ^!._,) In the "initial 15 degrees": "_1:: "viscosity change rate" (%) = - one ** - ----------- κ 1〇〇f Initial viscosity j (Pa-s) [Coating property test] A linear pattern of 50 mm in length was continuously applied to a glass plate for 10 minutes by the following method. The coating pattern was confirmed at a magnification of 100 times on a CCD camera. Coating machine: Shot Master 300 manufactured by Musashi Engineering Co., Ltd. Nozzle: 0 4ΟΟμΓπ Precision nozzle gap: 30μτπ Coating speed: 100mm/sec Coating pressure: lOOkPa Refer to the shape of Figure 1 to Figure 3 for reference, as judged by To evaluate the "coating characteristics". 〇: No coating liquid droplet breaks and maintains line width (Fig. 1) △: No coating liquid bead breaks, but line width is not maintained (Fig. 2), or there is drawing condition χ: There is coating liquid bead break (Fig. 3) [Comprehensive evaluation] Each test item will be scored as follows, and the sum will be defined as "comprehensive evaluation". When it exceeds 7 minutes, it can be used as a sealant for liquid crystal dropping method. 22/25 201130956 〇: 2 minutes △ : 1 minute X : 0 points [Table 3] Test item Example 1 Example 2 Comparative example 1 Comparative example 2 Comparative example 3 Phase transition temperature difference 〇〇X △ X Specific resistance ratio 〇 〇X Δ X Peel strength retention rate 〇〇Δ Δ 〇 Viscosity change rate 〇Δ 〇X 〇Coating characteristics 〇〇Δ X 〇Comprehensive evaluation 10 9 4 Λ 6 As Examples 1 and 2 are compared with Comparative Examples 1 and 3 It has been found that by using the component (A) of the present invention, it is observed that the phase transition temperature difference and the specific resistance ratio tend to be good compared to the conventional epoxy resin. The two characteristics of Tienan 'it can be said that the liquid crystal/L article' has low contamination to the liquid crystal. Further, in Comparative Example 2, although an acrylic monomer was used, as compared with Examples 1 and 2 and Comparative Example 2, in Comparative Example 2, the coating properties were not excellent. Comparative Example 2 As shown in Table 2, the viscosity of the basic composition tends to be low due to the addition of the acrylic monomer. However, the viscosity of the liquid crystal sealing agent is improved by adding a large amount of the filler. This is the cause of the coating destabilization of Comparative Example 2, and it is necessary to maintain the viscosity of the basic composition at a certain degree of relativeness. In Comparative Example 3, a partially esterified epoxy resin widely used in the field of liquid crystal sealing agents was used as a resin component. From the results of Comparative Example 3, it was found that the epoxy resin of the starting material had high liquid crystal contamination, and therefore, when a partially esterified epoxy resin was used alone, a tilt of the phase transition temperature difference and the specific resistance ratio was observed to be 23/ 25 201130956 to. [Industrial Applicability] In a large-sized liquid crystal display panel, a manufacturing method by a liquid crystal dropping method has become mainstream. The liquid crystal sealing agent of the present invention has characteristics of low liquid crystal contamination and high peeling hardness necessary for the liquid crystal dropping method, and exhibits stable characteristics on the operation surface such as coatability and preservability. Since it is possible to cope with a large display element that consumes a line tact time (1 ine tact), the present invention can cope with a small display element and can be used for assembly of panels of various sizes. In addition, the present application is based on Japanese Patent Application No. 2010-025855, filed on Jan. [Brief Description of the Drawings] Fig. 1 is a photograph showing the criterion for determining the coating characteristics as "〇" in the coatability test. Fig. 2 is a photograph showing the criterion for determining the coating property as "Δ" in the coatability test. Fig. 3 is a photograph showing the judgment criterion of the coating property as "X" in the coatability test. [Main component symbol description] 24/25 8

Claims (1)

201130956 七 2. 4. Patent application scope: : Type = dripping process sealant, which is necessary as a product) = thermosetting agent and photoinitiator, and heat hardening and light (A) component - Epoxy resin having an anthracene skeleton = (meth) propylene-based resin. ^ Patent pending to the liquid crystal drop method of the fat component, the aforementioned 埶 hardened shirt is the first 4 i ώ 具 具 具 具 幻 幻 幻 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; Below C is 00~17〇Pa.s. 2 Please patent scope! Or a liquid crystal sealing method for a liquid crystal sealing method, wherein the liquid component comprises a liquid crystal sealing having an epoxy group and a range of any one of the first to third aspects of the present invention. The transfer temperature difference is 〇~2 〇t. Two types of liquid crystal display elements are used, which are obtained by using a liquid crystal dropping method sealing agent according to any one of the first to third aspects of the patent. § -5/25