JPS60217231A - Photosetting resin composition for sealing - Google Patents

Abstract

PURPOSE:The titled composition that is obtained by using a butadiene polymer or copolymer bearing epoxy groups, an epoxy resin and a photosensitive aromatic onium compound, thus showing good adhesion, sealing properties, high resistance to chilling and heating cycles and being suitably used as a sealer for liquid crystal elements. CONSTITUTION:The objective composition contains (A) 10-70, preferably 20- 60pts.wt. of a resin which is obtained by treating a butadiene homo- or copolymer with an organic peroxide, thus has the polymer as the main-chain skeleton and 1.5 or more, on the average every molecule, of epoxy group on its chain terminal and/or side chains, (B) 90-30, preferably 80-40pts.wt. of alycyclic, bisphenol-A, bisphenol-F, novolac or hydrogenated bisphenol-A type epoxy resin and (C) 0.5-10, preferably 2-5pts.wt., based on 100pts.wt. of A+B, of a photosensitive onium salt, e.g., triphenylsulfonium hexafluoroantimonate.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a photocurable resin composition for sealing. More specifically, in manufacturing a liquid crystal cell, the periphery of the cell is sealed at the same time as two substrates are bonded together, and the liquid crystal injection port formed for injecting the liquid crystal is sealed tightly after the liquid crystal is injected. The present invention relates to a photocurable resin composition for sealing that has excellent adhesive properties, sealing properties, cold and heat cycle resistance, and suitability for liquid crystals. [Prior art and its problems] Generally, liquid crystal cells used in display devices are made by bonding two glass or plastic substrates together with a peripheral sealant such as organic epoxy resin or inorganic frit glass. It is formed by seaming them together while maintaining the gap between them. A typical example of a resin sealing method is to use screen printing to apply sealant to a substrate to form the outer periphery of the cell, then attach a spacer to another substrate, and then apply the sealant to the substrate. There is a way to harden it. At this time, a small hole is made in a part of the cell as an injection port for injecting the liquid crystal after the cell is formed, and after the liquid crystal is injected into the cell, it is stopped with a sealant to maintain airtightness. ing. Conventionally, one-component or two-component type epoxy thermosetting resin compositions have been used as these peripheral sealants. For example, as such prior art document, Japanese Patent Publication No. 58-2206
No. 0 is mentioned, but since the compositions of this sealant were eluted into the liquid crystal, abnormalities in liquid crystal alignment and deterioration of the liquid crystal frequently occurred. In addition, since the resin curing process is performed at high temperatures and over a long period of time, there may be problems with quality control, such as minute cracks occurring in the sealant or substrate material due to curing shrinkage, or productivity problems, such as difficulty in line production. That left a big problem. On the other hand, in the case of a liquid crystal injection port sealant, it must be cured and bonded in contact with the liquid crystal, and cannot be heated at high temperatures to prevent deterioration of the liquid crystal. Therefore, curing of the sealant requires a long time at low temperatures, which may cause alignment abnormalities and poor curing due to elution of the sealant composition into the liquid crystal, resulting in problems in terms of quality, quality control, and production. It had become a big problem. In order to solve these problems, various applications of photocurable sealants have been studied. For example, such prior art documents include JP-A No. 153651/1983 and JP-A No. 56-1989.
No. 53169 is mentioned, but since these sealants have insufficient adhesive properties, when external pressure is applied to the liquid crystal cell, the resin sealing part peels off and the liquid crystal inside protrudes to the outside. In addition, there was a problem that the bond between the glass and the sealant broke due to cold and heat resistant cycles, and the liquid crystal in the cell leaked. Also,
Even if the cured product has sufficient adhesive strength in common with peripheral sealants and injection port sealants, air may enter the cell through the cured resin due to lack of barrier properties, which is one of the sealing properties. There were problems such as bubbles forming in the liquid crystal cell. Furthermore, since the photocuring reaction takes place in a very short time compared to conventional methods, the cured product contains components that can be eluted into the liquid crystal even after curing is completed, and as a result, the driving current value of the liquid crystal increases over time. However, there were problems such as decreased reliability as a display device. For this reason, there are no photocurable resin compositions that have the performance as a peripheral sealant, and the performance of photocurable compositions that can be used as an injection port sealant is at an extremely low level. There has been a strong desire to develop a photocurable sealant that has excellent adhesion, thermal cycleability, sealing properties such as gas barrier properties, and suitability for liquid crystals such as low elution properties. On the other hand, Japanese Patent Publications No. 52-14277 and Japanese Patent Publication No. 52-142 disclose the use of aromatic onium salts as polymerization initiators to cure epoxy resins by UV irradiation.
No. 78, Special Publication No. 52-14279, etc.
Among these, epoxy resins that can be polymerized into a high molecular weight state as one component of the composition are described, but the commonly used resin metals, collectively called epoxy resins, are made of aromatic onium salts. The present inventors have confirmed that the composition does not make it curable. Glycidylamine-type epoxy resins, such as polyethylene glycol diglycidyl ether, known as flexible epoxy resin, and p-xylylenediamine tetraglycidylamine, known as heat-resistant epoxy resin, can be cured using other curing methods, such as acid anhydride or A cured product can be obtained by blending an epoxy curing agent such as dicyandiamide and heating, but a cured product could not be obtained even if an aromatic onium salt was blended and irradiated with ultraviolet rays. Furthermore, when the composition described in the Examples of the above-mentioned prior art document is used as a liquid crystal injection hole sealant, the cured product has a low glass transition point Tg and lacks barrier properties, or the cured product has low resistance to cold and heat cycles. The liquid crystal cell had poor performance and bubbles were generated inside the liquid crystal cell. Moreover, these compositions that cause visual abnormalities also have the disadvantage that the liquid crystal driving current value increases over time. 6- Because of these points, there has been no similar example of a photocurable resin composition for sealing a liquid crystal cell in a photocationic polymerization system using an aromatic onium salt of an epoxy resin. [Problems to be Solved by the Invention] The present invention eliminates the drawbacks of the conventional thermosetting type, photocuring type, peripheral area, injection port, and sealing agent, and has strong adhesive strength. To provide a photocurable resin composition for sealing that can produce high-quality liquid crystal cells having excellent sealing and sealing properties and cold and heat cycle resistance more simply and in a shorter time than conventional manufacturing processes. be. [Means for Solving the Problems] As a result of intensive studies in view of the above-mentioned points, the present inventors have discovered that a butadiene homopolymer or copolymer resin containing an epoxy group, an epoxy resin, and a photosensitive, aromatic A resin composition containing a group onium salt as an essential component is used as a sealant and sealant, and after screen printing the sealant on a substrate and pressing the opposite substrate, it is sealed by irradiation with active energy rays. The present inventors have discovered that the intended purpose of the present invention can be achieved by photo-curing, further filling the liquid crystal, and then photo-curing the inlet with a sealant, thereby completing the present invention. That is, the present invention uses a butadiene homopolymer or a butadiene copolymer as the main chain skeleton, and has an average of at least 1 epoxy group per molecule at the molecular terminal and/or side chain.
．． A resin component having 5 or more and one selected from the group consisting of alicyclic epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, Novo 2 Tsuku type epoxy resin, hydrogenated bisphenol A epoxy resin, or A photocurable resin composition for sealing which contains as essential components component (C) of two or more epoxy resins and a photosensitive aromatic onium salt. It is a wearable photocurable resin composition. [Specific explanation] The butadiene homopolymer or butadiene copolymer used in the present invention is used as the main chain skeleton, and the molecular terminal and/or
Or, the epoxy group in the side chain is at least 1.0% on average per molecule.
A resin component having 5 or more is a) obtained by treating a butadiene homopolymer or a butadiene copolymer (hereinafter abbreviated as butadiene-based polymer) with an organic peroxide to epoxidize the double bonds in the constituent units. Epoxidized polybutadiene, such as epoxidized polybutadiene BF-1000, obtained by treating 1,2-polybutadiene with peracetic acid,'
, BP-2000 (trade name of Adeka Argus ■), etc. b) Terminal epoxidized butadiene-based polymer with an epoxy group introduced at the molecular end by telomerization during polymerization, for example, butadiene alone or a mixture of other monomers copolymerizable with it such as pentadiene, hexadiene, isoprene, etc. A reaction intermediate (living polymer) obtained by living anionic polymerization at low temperatures in the presence of an alkali metal catalyst such as sodium or lithium.
9 - a halogenated alkylene oxide of the general formula, e.g.
An epoxidized butadiene-based polymer obtained by treating with epichlorohydrin and adding an epoxy group to the end of the polymer chain. C) Polybutadiene-modified epoxy obtained by esterifying a butadiene-based polymer having a carboxyl group in the molecule and an epoxy resin [Jli, e.g.
No. 5-137125 Publication No. 5-137125 Obtained by the method disclosed in Nippon Soda's trademark Hoxin EPB-12, EPB-13,
EPB-14, EPB-17, EPB-25, EPB-27, EPB-42, EPB-44 Tobu Kasei (product name Evo) -) YR-102, -10-207, ACR Epoxy R-1309, ACR Epoxy X-1363, ACR Epoxy X-1374, etc. manufactured by &lNCR ■ can be used. The various butadiene-based polymer support components having 1.5 or more epoxy groups in one molecule may be used alone or in a mixture of two or more. This one
The amount of the butadiene-based polymer having 165 or more epoxy groups in the molecule is 10 to 70 parts by weight, preferably 20 to 60 parts by weight, based on the total amount of the polymer and component (B). Department. If the above maximum limit of 70 parts by weight of the component (2) is exceeded, the amount of the flexible component in the composition will be excessive and the Tg of the cured product will drop significantly, resulting in insufficient barrier properties. On the other hand, if the amount is less than the above-mentioned minimum limit of 10 parts by weight, it is not preferable because the stress relaxation component decreases, causing cracks in the cured product during curing or poor adhesion at the adherend interface. Components of the epoxy resin used in the present invention are: 1) Alicyclic epoxy resins, such as Union Carbide Company (U, C, C) (7) Product names ERL-4221, 4289, 4206, 4234 , II) bisphenol A type epoxy resin,
For example, the product name of Yuka Shell Epoxy■ is Epicote 82.
7, 828, 834, 836, 1001, 1
004, 1007; 60971 Dow Chemical Company's product names DER330, 331, 337, 661, 664; Dainippon Ink Chemical Koji product names Epicron 8001 1010, 1000. 3010 i Tobu Kasei ■ trade name Evo) -) YD-128, Dobu-134, YD
-8125 Ill) Bisphenol F-type tree jL For example, oil-based shell epoxy ■ trade name Epicote 807; Tobu Kasei ■ trade name Evoto-) YDF-17 (1 Dainippon Ink Industries ■ trade name Evicron 830, 831 1V ) Novolak-type epoxy resins, such as oil-based shell epoxy (trade names: Epicote 152 and 154; DOW Chemical Company's trade names: DEN-431 and 438)
, 439; Ciba Geigy's product name EPN-1138, ECN
-1235. Trade names of Dainippon Ink Chemical ■Epicrin N-740, Epicurean N-680, Epicurean N-695, Epicurean N-565, Epicurean
-577V) Hydrogenated bisphenol A diglycidyl ether resin, for example, ADEKA RIN EP-4080 manufactured by Kadenka Kogyo ■,
etc. can be used. These various epoxy resin components may be used alone or in a mixed system of two or more. The amount of ingredients used in this epoxy resin is:
It is blended in an amount of 90 to 30 parts by weight, preferably 13 to 80 to 40 parts by weight, based on the total amount of components (2) and (6). Epoxy resin has a hardness T
It provides a cured product with a high g content, and when cured with an aromatic onium salt, it has particularly excellent curing properties and cures in a short time, but it has drawbacks such as the cured product being brittle and having poor cold and thermal shock resistance. The usage range described above is set for . Photosensitive aromatic onium salts used in the present invention (as the Q component, aromatic onium salts of group IV elements shown in Japanese Patent Publication No. 52-14277; Aromatic onium salts of group Ma elements and aromatic onium salts of group Va elements shown in Japanese Patent Publication No. 52-14279 can be used.More specifically, for example, triphenylphenacylphosphonium tetrafluoroborate. , triphenylsulfonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, etc. can be used.These onium salts release silicate acid when irradiated with active energy 14-rays such as ultraviolet rays, which initiates cationic polymerization of epoxy. The amount of photosensitive aromatic onium salt (C) component used is (4)
0.5 to 1 per 100 parts by weight of the total amount of component (B) and
0 parts by weight, preferably 2 to 5 parts by weight. If the amount of onium salt added is less than 0.5 parts by weight, curing by active energy rays will be insufficient, and the cured product will have a low Tg and insufficient barrier properties. Furthermore, low molecular weight substances in the cured product are eluted into the liquid crystal and cause poor alignment of the liquid crystal. On the other hand, if the amount added is more than 10 parts by weight at the upper limit of the range, the decomposition product of the aromatic onium salt will gradually dissolve into the liquid crystal, which tends to increase the drive current value of the liquid crystal. If the above-mentioned aromatic onium salt is insufficiently compatible with the mixture of components (A) and [F]), use the onium salt dissolved in an appropriate solvent such as acetonitrile, propylene carbonate, or cellosolve. be able to. A solvent can be used in the resin composition according to the present invention for the purpose of improving the workability of screen printing, especially when used as a sealant around a liquid crystal cell. , esters, ethers, aliphatic or aromatic hydrocarbons, or chlorinated hydrocarbons, which do not damage the emulsion of the screen are used. The amount of the solvent to be used is preferably such that the weight ratio of the solvent contained in the composition is within 20 parts by weight. The resin composition according to the present invention may contain a reactive diluent having one or more epoxy groups in the molecule in order to reduce the viscosity of the composition or adjust the reactivity. Examples of the reactive diluent mentioned here include butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, p-butylphenyl glycidyl ether, glycerin glycidyl ether, neopentyl glycol diglycidyl ether, etc. Available for use. The blending amount is within a range that does not impair the adhesion and liquid crystal suitability, which are the objectives of the present invention, but is preferably within 20 parts by weight based on 100 parts by weight of the total amount of the other components. Furthermore, various modifying additives can be added to the resin composition according to the present invention as required for modifying physical properties or for purposes of use. For example, granular or acicular spacers to maintain proper spacing between liquid crystal cells; fillers such as silica and glass beads; silicone-based, titanate-based, and other coupling agents to improve adhesion and moisture resistance. ; Thixotropic properties imparting agents such as Aerosil and Bentone to impart screen printability; Leveling agents such as Fluorade; extender pigments such as aluminum hydroxide and barium hydroxide; Modified polymeric substances can also be incorporated. In order to cure the resin composition according to the present invention, a wavelength of 200
Ultraviolet light of ~400 nm is effective. Examples of this radiation source include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp. Other active energy rays that can be used for curing include 17-visible light, X-rays, and electron beams. Further, although the present composition is sufficiently cured by irradiation with active energy rays and exhibits sufficient properties for the intended purpose, even better properties can be obtained by leaving it in a heating chamber after irradiation. An example of this temperature range is 50 to 80°C for 2 to 20 hours. The photocurable resin composition for sealing according to the present invention has excellent adhesive properties, cold and heat cycle resistance, flexibility, etc., and is fast curing, so it can be used as a sealant for liquid crystal cells. It can also be used as an adhesive for other optically transparent materials such as glass and plastic. For example, camera lenses, eyeglass lenses, other optical lenses, stereo dials, decorative laminated glass, automotive laminated glass, heat insulating laminated glass, advertising films, printing □
Adhesion of vegetation boards, connection or temporary attachment of die bonding lead wires, temporary attachment of chip components mounted on printed circuit boards,
It can also be applied to protective coatings for electronic circuits, surface protection for parts, adhesion related to laser discs, resin for molding, sealing of small parts, f-tuting, adhesion of coil terminals, and liquid crystal cells. The use of the photocurable resin composition for sealing is not limited to the following. [Example] Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited only to these Examples. In addition,
Parts in the examples are parts by weight. Example 1 Molecular weight approximately L500 produced by anion living method
Epoxidized 1゜2-polybutadiene BF-1000 (Adeka Argus ■) with an oxygen content of 7.7 hours Product name) 50 parts and alicyclic epoxy resin ERL corresponding to component (6) -
Mix well 50 parts of 4221 (U, C1C company trade name). Next, component (C), triphenylsulfonium hexafluoroantimonate (propylene carbonate 50
% solution) 4 parts, Aerosil +380 (Japan Aerosil■
(trade name) 2 and parts were mixed well and kneaded to obtain a photocurable resin composition for sealing of the present invention for sealing liquid crystal injection holes [1]. Example 2 46 parts of sodium dispersion was added to 5,000 parts of tetrahydrofuran in which 46 parts of 1.2-diphenylbenzene had been dissolved, and the mixture was kept at -60°C, and 886 parts of butadiene was added dropwise over 2 hours. It was further kept at -60°C for 1 hour. Next, 185 parts of epichlorohydrin was added dropwise to this and mixed well. After washing this product twice with an equal volume of water, tetrahydrofuran was distilled off under reduced pressure and the number average molecular
3i1370 epoxy oxirane oxygen content 2.01%
A terminally epoxidized polybutadiene corresponding to component (g) in the present invention was obtained. Next, 30 parts of the terminal epoxidized polybutadiene and alicyclic epoxy resin E corresponding to component (6) were added.
RL-4299 (U, C1C0 company product name) 70 copies, (
C) Component triphenylphenacylphosphonium tetrafluoroborate (50% propylene carbonate solution)
5 parts, epoxy group-containing silane coupling agent 3-4
03 (trade name of Shin-Etsu Silicone Ball) and 3802 parts of Aerosil+ were thoroughly kneaded to obtain a sealing photocurable resin composition [2] of the present invention for sealing liquid crystal injection holes. Example 3 Polybutadiene-modified epoxy resin N15so Evoxin EPB-27 (Nippon Soda ■ trade name) obtained by reacting an epoxy resin with 1,2-polybutadiene having a carboxyl group at the molecular end produced by the anion living method 20 parts, EOCN- which is a novolak type epoxy resin;
103 (Nippon Kayaku ■trade name), 70 parts of Evototo ■8125 (Tobu Kasei ■trade name), which is a bisphenol A type epoxy resin, and 10 parts of diethylene glycol mono-n-butyl ether acetate were thoroughly mixed. Then,
Add and mix 10 parts of triphenylsulfonium hexafluoroantimonate (propylene carbonate 50% solution) and 12 parts of Aerosil+320, mix well with three paint rollers, and use a spacer with a diameter of 5 μm.
A photocurable resin composition for sealing [3] for sealing around the periphery of a liquid crystal cell [3] was obtained by mixing two parts of single glass fibers having a length of 15 to 30 μm (manufactured by Optical Glass Manufacturing Co., Ltd.). Example 4 HycarCTBN13, a butadiene-acrylotolyl copolymer with a carboxyl group at the end of the molecule
00 x 13 50 parts and 550 parts of bisphenol A type epoxy resin EVO)-TOYD-812 were charged into a separable flask equipped with a stirrer, a reflux condenser, a nitrogen blowing tube, and a thermometer, and stirred under a nitrogen atmosphere. While reacting at 130℃ for 4 hours, the acid
A polybutadiene-modified epoxy resin was obtained. Next, 50 parts of the polybutadiene-modified epoxy resin, 50 parts of bisphenol F type epoxy resin Epicote 807 (trade name of Yuka Shell Epoxy ■), and 12 parts of diethylene glycol mono-n-butyl ether acetate were added and mixed well. Then 8 parts of triphenylphenacylphosphonium tetraborate (50% propylene carbonate solution), 1 part of IQ3M-403 and Aerosil+3
After adding 8,014 parts and kneading well with three paint rollers, 3 parts of S22-Spacer glass single fibers (described above) were mixed to obtain a sealing photocurable resin composition for sealing the periphery of a liquid crystal cell [ 4] was obtained. Example 5' Epoxidation of epoxy oxirane with an oxygen content of 77 cm 1, 2
- Polybutadiene BF-100,050 parts, alicyclic epoxy resin ERL-429,950 parts, triphenylphosphonium hexafluoroantimonate (propylene carbonate 50% solution) 6 parts, and Aerosil 43,802 parts were thoroughly kneaded with three paint rollers, and then the spacer Four parts of glass single fibers (described above) were mixed to obtain a sealing photocurable resin composition [5] for sealing around a liquid crystal cell. Comparative Example 1 Alicyclic epoxy resin tJVR-6100 (U,
C, C, company product name) 60 parts and flexibility-imparting epoxy resin U
40 parts of VR-6351 (trade name of U, C, C Company), 8 parts of triphenylsulfonium hexafluoroantimonate (50 parts of glopyrene carbonate solution), KBM
-4,031 parts of Aerosil and 43,802 parts of Aerosil were thoroughly kneaded to obtain a photocurable resin composition [6] for sealing an epoxy photocationic polymerization type liquid crystal injection hole, which is outside the scope of the claims of the present patent. Comparative Example 2 100 parts of Araldite MY-720 (trade name, Ciba Geigy), which is N,N'-tetraglycidyl p-phenylenediamine, and 10 parts of triphenylphenacylphosphonium tetrafluoroborate (50% propylene carbonate solution) were mixed together. They were mixed to obtain a photocurable resin composition [7]. Comparative Example 3 Trifunctional acrylate A-'IMP (Shin Nakamura Chemical ■
100 parts of product name), 1 part of penzyldimethoxyethyl ketal, and 2 parts of Aerogyrna 380 are thoroughly kneaded to obtain a photocurable resin composition for use in sealing injection holes of acrylic photoradical polymerization type liquid crystals, which is outside the scope of the claims of this patent. [8] was obtained. Comparative Example 4 Bisphenol A epoxy resin Epicoat 828 (
100 parts (trade name of Yuka Shell Epoxy ■), Novolac type epoxy resin =≠Kyotewo Nae Epicor) 152 (trade name of Yuka Shell Epoxy ■) 50 parts, Evolai (neopentyl glycol diglycidyl ether) 150ONP
After mixing 50 parts (trade name of Kyoeisha Yushi Kagaku Kogyo ■) and 40 parts of Aerosil 138,040 parts, they were thoroughly kneaded with three paint rollers, and 5 parts of spacer single glass fibers (mentioned above) were mixed to obtain an epoxy resin composition. Ta. Furthermore, the epoxy resin composition is coated with a polyamide curing agent TOMIDE+2500.
Add 50 parts (trade name of Fuji Kasei Kogyo ■) and 1.6 parts of 2-ethyl-4-methylimidazole and mix well to obtain a thermosetting resin composition for sealing the periphery of a liquid crystal cell.

[9] was obtained. [1] obtained in Examples 1 to 5 and Comparative Examples 1 to 4 above
] ~

Regarding the curable resin compositions [9], first, the curing characteristics of these compositions were measured by the method described below, and the results are shown in Table 1. Furthermore, a glass plate (thickness 0.55 wg) that had been subjected to ion diffusion prevention treatment, electrode formation, and orientation treatment by conventional methods was printed with Suff 25-screen [3], [4], [5]. ,

The resin composition [9] was applied to the outer periphery of the cell. Next [3], [
For [4], after leaving at 80℃ for 15 minutes ([5], [
9] without going through this process), the same treated glass plate used earlier was placed on top and crimped. This was cured by irradiating it with ultraviolet rays for a predetermined period of time from a distance of 10 meters using a high-pressure mercury lamp (80 W/cWL) while keeping it in the crimped state. (For some samples, an after-cure of 60'C x 1 hour was performed after irradiation with ultraviolet rays.) Next, liquid crystal was encapsulated by the vacuum method, and [1
], [2], (6), and (8) were used to seal the liquid crystal injection hole, and irradiated with ultraviolet rays from a distance of 10 crn for a predetermined period of time using a high-pressure mercury lamp (80 W/cm). The resin composition was cured to produce a liquid crystal cell. Next, each of the samples A to I of the liquid crystal cell shown in Table 1 produced in this way was evaluated for sealing properties, high temperature and high temperature and high humidity durability, liquid crystal cell drive current conversion rate, cold and heat cycle resistance, etc. A performance test was conducted and the results are shown in Table 2. <Curing characteristic measurement> [1] ~

The curable resin composition [9] was JIS-G-
1% - Apply on a 3303 tin plate using a 6m11 doctor blade, and cure by irradiating ultraviolet rays for a predetermined period of time from a distance of 10crn using a high-pressure mercury lamp (80W/cm>) for [1] to [8]. (However, [3], [4]
), leave it at 80℃ for 15 minutes and then irradiate it with ultraviolet light).

Regarding [9], heat curing was performed at 120° C. for 6 hours after coating. Next, the properties of these cured resin compositions and the anchor chain hardness of the cured coating films were determined, and furthermore, these peeled coating films were measured using a dynamic viscoelasticity measuring machine Rheopyblon DDV-I[1-E].
Displacement ±0.01 by A (manufactured by Toyo Baldwin)
The viscoelasticity was measured at a temperature of 6 mm, a frequency of 35 Herz1, and a heating rate of 2° C./min, and the Tg and molecular weight between crosslinking points were measured. 27- [Note] 1) Ultraviolet irradiation time using high-pressure mercury lamp (80 W/cm), distance 10 m 2) Heating conditions by hot air open 3) Current value change rate ts) -U = -2 x 1 x 100I. Io: Initial current value of liquid crystal cell IA: Current value of liquid crystal cell after 400 hours at 80° C., 90% RH [Effects of the present invention] The photocurable resin composition for sealing obtained by the present invention is shown in Table 1. As such, it has better properties compared to conventional epoxy photocationic polymerization systems, and also has better curability and higher Tg than other sealing resins. It also has a significantly longer pot life than the two-component type.Also, as shown in Table 2, it has excellent adhesive properties, sealing properties, and durability as a liquid crystal cell peripheral sealant and injection hole sealant. It is clear that it contributes to labor saving in the liquid crystal cell manufacturing process due to its cold-heat cycle property.30-6 Contents of the Amendment Procedural Amendment March 1985 =/F Date Manabu Shiga, Commissioner of the Japan Patent Office 1, Incident Indication of 1982 Patent Office No. 70896 2, Name of the invention: Photocurable resin composition for sealing 3, Relationship with the amended party case Patent applicant [Co., Ltd.] 100 2-2-1 Otemachi, Chiyoda-ku, Tokyo No. (4
30) Nippon Soda Co., Ltd. Representative: Takeo Sannomiya Nippon Soda Co., Ltd. 10) Correct "parts by weight" in the bottom line of page 13 to "% by weight". 1) "Above" on page 6, line 14 of the specification is changed to "said"
Correct. 2) On page 10, line 9 (including the formula), "with an epoxy group" is corrected to "by introducing an epoxy group." 3) r207 on page 11, line 1. J r207;J
Correct. 4) Change “parts by weight” from lines 8 to 9 on page 11 to “% by weight”.
” is corrected. 5) “1 part by weight” on page 11, line 10 of the same page is “% by weight”
Correct. 6) Correct "parts by weight" in lines 10 and 11 of page 11 to "% by weight". 7) Change “parts by weight” in line 13 of page 11 to “% by weight”
Correct. 8) Correct "Union Carbide Company" in the second line from the bottom of No. 11 to "Union Carbide Company." 9) rCY252 on page 12, lines 9-10, C
Y250, CY260, CY280J as rGY25
2. Corrected to GY2501, GY260, and GY280J. 2-. 12) Change “weight ratio” in line 6 of page 16 to “weight ratio”
Correct. 13) In the 3rd line from the bottom of No. 16, ``Amount of ingredients'' is corrected to ``Amounts of these ingredients.'' 14) On page 23, line 6 from the bottom, "1 Union Carbide Company" is corrected to "Union Carbide Company." 15) Correct "Table 14" in the 6th line from the bottom of No. 26 to "Table 2". 16) Correct r 0.016J in the third line from the bottom of No. 27 to r 0.025J. 17) 1 comparison example 1 in the upper column of Table 1 on page 28,
"Comparative ratio 2", "Comparative example 3", and "Comparative example 4" are corrected to "Comparative example 1,""Comparative example 2,""Comparative example 3," and "Comparative example 4." 18) r of [Note] 3) in Table 1, page 28 of the same 0.016
Correct J to rO,025J. 19) "Table 2" at the top of page 29 is corrected to "Table 2."-'t-

Claims (1)

[Claims] 1. The following components: The main chain skeleton is a butadiene homopolymer or a butadiene copolymer, and the average number of epoxy groups per molecule is at least 1. A photocurable resin composition for sealing, comprising a resin having five or more of the following: (6) an epoxy resin; and (C) a photosensitive aromatic onium salt as essential components. 2. The epoxy resin of @ component is one selected from the group consisting of alicyclic epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, and hydrogenated bisphenol A type epoxy resin. or the first claim which is two or more types of resins.
The photocurable resin composition for sealing as described in 1. The mixing ratio of the prisoner and component 03) is 10 to 70 for component (8).
parts by weight, component (6) is 90 to 30 parts by weight, (C)
The ingredients are 0 parts per 100 parts by weight of the total amount of the prisoner and component (6).
, 5 to 10 parts by weight of the photocurable resin composition for sealing according to claim 1.