JPS61213217A - Photosetting resin composition for sealing - Google Patents

Abstract

PURPOSE:To obtain the titled composition having excellent adhesivity, sealability, thermal cycle resistance, etc., and useful for the sealing of a liquid crystal cell, by compounding specific butadiene resin with epoxy resin, photo- detecting aromatic onium salt and sensitizer having polymerizable substituent group. CONSTITUTION:The objective composition can be produced by compounding (A) a butadiene resin having butadiene homo(or co)polymer as a main skeleton and containing >=1.5 epoxy groups on an average in the molecular terminal and/or side chain in one molecule with (B) one or more epoxy resins belonging to the alicyclic type, (hydrogenated) bisphenol A-type, bisphenol F-type, or novalac-type epoxy resin, (C) a photo-detecting aromatic onium salt (e.g. hexafluoroantimonic acid triphenylphosphonium salt) and (D) a sensitizer containing polymerizable substituent group (e.g. vinylanthrancene). Preferably, the weight ratio of A:B is (10-70):(90-30), and that of (A+B):C:D are 100:(0.1-5):(0.001-0.5).

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a photocurable composition for sealing. More specifically, in manufacturing a liquid crystal cell, adhesive properties are used to bond two substrates together, seal the cell periphery, and seal the liquid crystal injection port formed for injecting the liquid crystal after the liquid crystal is injected; The present invention relates to a photocurable composition for sealing that has excellent sealing properties, cold and heat cycle resistance, and suitability for liquid crystals. [Prior Art] Liquid crystal cells generally used in display devices are made by keeping a predetermined gap between two glass or plastic substrates using a peripheral sealant such as organic epoxy resin or inorganic frit glass. is formed by joining. A typical example of a resin sealing method is to use screen printing to apply a sealant to a substrate to form the outer periphery of the cell, sandwich the spacer, and then attach another substrate. There is a method of curing the sealant. At this time, a small hole is made in a part of the cell as an injection port to inject the liquid crystal after the cell is formed, and after the liquid crystal is injected into the cell, it is sealed with a sealant to maintain airtightness. I have to. Conventionally, one-component or two-component type epoxy thermosetting compositions have been used as these peripheral sealants. However, because the sealant compositions were eluted into the liquid crystal, abnormalities in liquid crystal alignment and deterioration of the liquid crystal frequently occurred. In addition, since it requires a long curing process at high temperatures, it cannot be applied to plastic films; when different types of glass are bonded together, the cells may become cracked; and because curing shrinkage is large, when used in large display devices, Quality and quality control issues such as cell distortion or long heat curing processes must be batch-processed, which disrupts the continuity of the cell manufacturing line and reduces productivity. There remained 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 temperature, and as a result, alignment abnormalities and curing failures occur due to elution of the sealant composition into the liquid crystal, resulting in problems in terms of quality, quality control, and production. had become a big problem. In order to solve these problems, various applications of photocurable sealants have been studied. These photo-curable resin systems are of the photo-radical type, which radically polymerizes diacrylic monomers and oligomers using a photo-radical initiator, and the photo-cation type, which uses an aromatic onium salt as an initiator to cationically polymerize the epoxy resin by light irradiation. It can be broadly divided into Japanese Patent Application Laid-Open No. 153-1989 as a prior art document of the photo-radical type
No. 651 and JP-A-58-44420, but in the polymerization of acrylic or methacrylic, internal stress is generated due to volume waves during polymerization, resulting in insufficient adhesion and the use as a peripheral sealant. could not. Furthermore, even if the cured product has adhesive properties that can be used as a liquid crystal injection port sealant, air may enter the cells through the cured product and create bubbles due to lack of barrier properties, which is one of the sealing properties. There was a problem. On the other hand, as a prior art document of the photocation type,
No. 14277, Special Publication No. 52-14278, Special Publication No. 14278
-14.279 publication etc. are mentioned. When the composition described in this example is used as a liquid crystal injection port sealant, the cured product has a low glass transition point (hereinafter referred to as Tg) and lacks barrier properties, and the cured product has poor cold and heat cycle resistance. Air bubbles were generated inside the liquid crystal cell. Furthermore, with the above-mentioned simple combination of egoxy resin and photosensitive onium salt, the progress of curing by light irradiation is slower than that of the photo-radical type, and when this composition is used as a liquid crystal injection port sealant, internal curing Due to its poor properties, it elutes into the liquid crystal at the contact interface with the liquid crystal, disturbing the alignment of the liquid crystal and increasing the liquid crystal driving current value. When a large amount of onium salt, a photoinitiator, was used to accelerate the curing speed, many decomposition products of the aromatic onium salt were generated and eluted from the cured product into the liquid crystal, increasing the liquid crystal drive current value. . On the other hand, the use of sensitizers has been studied in an attempt to effectively utilize photosensitive onium salts and improve the curing speed. Such prior art documents include JP-A-59-147001 and S, P, Papp.
s, etc. al; “Photographic 5cienc
e and Engineering”23, [3]
, 140 (1979). In this sensitized system, by optimizing the amount of onium salt used, it was possible to improve the curing speed and reduce the amount of onium salt decomposition products. When used as a sealing agent, the elution of such low-molecular-weight compounds increases the liquid crystal cell drive current value over time. For these reasons, there are no photocurable compositions that have satisfactory performance as peripheral sealants, and photocurable compositions that can be used as injection port sealants have an extremely low level of performance. This is a photocurable sealant that has short-curing properties, excellent adhesive properties, thermal cycleability, sealing properties such as gas barrier properties, and suitability for liquid crystals such as low elution from cured products. There was a need for development. [Problems to be Solved by the Invention] The present invention solves a problem in the prior art described above, in that although the photocationic polymerization system of the epoxy resin has good adhesive properties, it encapsulates a large amount of leachable low molecules. In view of this, by finding a composition that reduces the amount of leachable low molecules remaining in the cured product, we have created a composition that has strong adhesive strength, excellent sealing and sealing properties, and cold and heat resistance. It is an object of the present invention to provide a photocurable composition for sealing that can produce a high-quality liquid crystal cell having cycleability more simply and in a shorter time than conventional production processes. [Means for Solving the Problems] As a result of intensive studies in view of the above-mentioned points, the present inventors have found a long-term solution for systems using aromatic onium salts as cationic polymerization initiators for synthetic resins. We found a raw material resin that does not affect the liquid crystal when it comes into contact with the liquid crystal over time, and at the same time added a sensitizer with a polymerizable substituent to this system. A composition with a fast curing speed and good internal curability was obtained. Furthermore, it has been found that in this system, the amount of onium salt added to provide the optimum cured product is reduced compared to when no sensitizer is added. The elution of the sensitizer from the cured product obtained by irradiating a composition using a sensitizer having a polymerizable substituent is as follows: The present inventors have found that the amount of liquid crystal cells is very low compared to that of conventional liquid crystal cells, and that they have good moisture resistance and heat resistance over time in long-term liquid crystal cell abuse tests, leading to the completion of the present invention. That is, the present invention provides butadiene which has a butadiene homopolymer or a butadiene copolymer as its main chain skeleton, and which has at least 1.5 or more groups per molecule on average at the molecular terminal and/or side chain. system resin, [F]) alicyclic epoxy resin, bisphenol All epoxy resin, bisphenol FI
At least one epoxy resin selected from the group consisting of J epoxy resin, novolac type edoxy resin, and hydrogenated bisphenol A type epoxy resin, (C) a photosensitive aromatic onium salt, and (B) a polymerizable substituent. This is a photocurable composition for sealing which contains a sensitizer having the following as an essential component, and is a photocurable composition for sealing which is rapidly cured by irradiation with active energy rays. A butadiene resin whose main chain skeleton is a butadiene homopolymer or a butadiene polymer used in the present invention, and which has an average of at least 1.5 or more epoxy groups per molecule at the molecular terminal and/or side chain. a) Epoxidized nobutadiene obtained by treating butadiene homopyrimer or butadiene codelimer (hereinafter abbreviated as butadiene-based polymer) with an organic peroxide to epoxidize the double bonds in the constituent units. , For example, epoxidized polybutadiene BF-100018F obtained by treating 1,2-polybutadiene with peracetic acid
-2000 (Adeka Argus ■ trade name) and the like. 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.
is treated with a halogenated alkylene oxide represented by the general formula, such as epichlorohydrin, to introduce an epoxy group at the end of the polymer chain. C) A polybutadiene-modified epoxy resin obtained by esterifying a butadiene-based pirimer having a carboxyl group in the molecule and an eixy resin, for example, JP-A-55-
Meiko Hoxin EPB-12, EPB-13, EPB-14, EPB-17, and EPB-25, manufactured by Nippon Soda ■, obtained by the method described in Publication No. 137125
, EPB-27, EPB-42, EPB-44
i Tobu Kasei brand name Neat tote YR-102, YR-
207; Product name of NCR ■ ACR Epoxy R-
1309, X-1363, X-1374, etc. can be used. The various types of butadiene resin carrier components having 1.5 or more epoxy groups in one molecule may be used alone or in a mixture of two or more. 1 in this molecule
．． The amount of butadiene-based resin containing component having 5 or more epoxy groups is 1% to the total amount of components (3) and [F]).
0 to 703ii1, preferably 2
It is 0 to 60% by weight. (4) 7 of the above maximum limits for ingredients;
If it exceeds 0% by weight, the amount of 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 weight is less than the above-mentioned minimum limit of 10%, it is not preferable because the stress relaxation component decreases, causing cracks in the cured product during curing and poor adhesion at the adherend interface. The epoxy resin of component (D) used in the present invention includes alicyclic epoxy resin, bisphenol A type epoxy resin,
One or more epoxy resins selected from the group consisting of bisphenol F-type epoxy resins, novolac-type epoxy resins, and hydrogenated and suphenol A-type epoxy resins, 1) Alicyclic epoxy resins, such as Union. Carbide Company (U, C, C,) product name ER
L-4221, 4289, 4206, 4234,
4205, 4299, tJVR-6100i Ciba Geigi product name CY-179, CY-178, C
Y-180, CY-175; Chisso ■ brand name CX-221, CX-289, C
X-206, CX-301, CX-313; Daicel ■ trade name Celoxide-202111) Bisphenol A type Eixy resin, for example, oil-based shell Eixys
Product names: Epicote 827, Epicote 828, Epicote 834, Epicote 8
36, 1001, 1004, 1007; Ciba Geigy's trade name Araldite GY250. Same G
Y-260, GY2801 Araldite 6071
, 6084, 6097; Dow Chemical Co.'s trade name DER330, 331, 337, 661, 664; Dainippon Ink & Chemicals Co., Ltd.'s trade name Epicron 800. 1010, 1000. 3010; Trade name of Tobu Kasei ■ d) -to YD-128, Do YD-134, YD-8125 fil) Bisphenol F type resin, such as Yuka Shell Epoxy ■ Trade name Epicote 807; Tobu Kasei ■ Product name: YDF-170; Dainippon Ink Co., Ltd.'s product name: Epicron 8301 1v) Novolak-type edexy resins, such as oleaginous shell epoxy (trade name: Epicort 152, 154); Dow Chemical Company's products: Name DEN-431, DEN-438
, 439; Ciba Geigy's product name EPN-1138, ECN -
1235; Trade name of Dainippon Ink Chemical ■ Epicron N-740゜Epicron N-680, Epiclon N-695, Epiclon N-565, Epiclon N
-5■) Hydrogenated bisphenol A diglycidyl ether resin, for example, Adeka Resin EP-4 manufactured by Jiryuka Kogyo ■ can be used. These various engineered 2-oxy resins of component 03) may be used alone or in a mixed system of two or more. The amount of this epoxy resin [F] component used is (A
) and component (B) in an amount of 90 to 30% by weight, preferably 80 to 40% by weight. Epoxy resin provides a cured product with a high Tg, and when cured with an aromatic onium salt, it has particularly excellent curability and cures in a short time, but the cured product is brittle and has poor cold and thermal shock resistance. The usage range described above is set because of the disadvantages such as. As the photosensitive aromatic onium salt of component C) used in the present invention, aromatic onium salts of group ■a elements shown in Japanese Patent Publication No. 52-14277, Japanese Patent Publication No. 52-142
Aromatic onium salts of Ma group elements shown in Japanese Patent Publication No. 78 and aromatic onium salts of Va group elements shown in Japanese Patent Publication No. 14279/1988 can be used. More specifically, for example, triphenylphenacylphosphonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, etc. can be used. When these onium salts are irradiated with active energy rays such as ultraviolet rays and visible rays, they release silicate acids, which initiate cationic polymerization of epoxy. The amount of the photosensitive aromatic onium salt (C) component used is 0.1 to 5 parts by weight, preferably 0.15 to 4 parts by weight, based on 100 parts by weight of the total amount of the photosensitive aromatic onium salt (C). . Addition of onium salt is 0
If the amount is less than 1 part by weight, curing by active energy rays will be insufficient, and the cured product will have a low Tg and insufficient barrier properties. In addition, low-molecular substances in the cured product elute into the liquid crystal, causing poor alignment of the liquid crystal.On the other hand, if the addition exceeds the upper limit of 5 parts by weight, the decomposed products of the aromatic onium salt gradually elute into the liquid crystal. death,
There is a tendency to increase the driving current value of liquid crystal. If the aromatic onium salt is insufficiently compatible with the mixture of components (3) and (), the onium salt is dissolved in an appropriate solvent, such as acetonitrile, propylene carbonate, or cellosolve solvent. be able to. ↓ The component (used in the present invention) is a sensitizer having a polymerizable substituent, as shown by the following formula, 320 to 500n
It is a polynuclear aromatic compound or a polynuclear heterocyclic compound, or a derivative thereof, which has a polymerizable substituent in the molecule having absorption in the ultraviolet and visible regions of m. Examples of the polymerizable substituent X include vinyl groups, vinyl ether groups, inzorobenyl groups, acryloyl groups, methacryloyl groups, allyl groups, epoxy groups, or organic compounds containing bicycloorthoesters, spiroorthoesters, or spiroorthocarbonates. Residues are exemplified. Examples of polynuclear aromatic compounds or polynuclear heterocyclic compounds Y include naphthalene, anthracene, zena/threne, pyrene,
Naphthacene, yrylene, R-ntacene, etc.; polynuclear heterocyclic compounds such as quinoline, phthalazine, quinoxaline, acridine, 7
Enazine, phenanthroline, phenothiazine, eosin, methyleosine, etc. As derivatives, substituents such as hydroxy, methoxy, amine, carboxyl, nitro, chloro, bromo, etc. are introduced singly or in combination, or in combination of two or more types. Examples include compounds such as The amount of sensitizer [F]) component used is the total amount of sensitizer and (B) component 1
0.00 parts by weight, o, ooi to 0.5 parts by weight. If the sensitizer exceeds the above-mentioned maximum limit of 0.5 parts by weight, the sensitizer may not be eluted from the cured product, resulting in poor alignment of the liquid crystal after forming the liquid crystal cell. Furthermore, upon curing, the curing properties tend to be poor. On the other hand, if the amount is less than the above-mentioned minimum limit of 0.001 part by weight, the effect of adding the sensitizer, that is, the effect of improving curability and improving the properties of the cured product, etc. is not significant. In addition to the above-mentioned ^~p components, the composition according to the present invention may optionally contain photocationic polymerization using the radical polymerization initiating ability of radicals generated by photodecomposition of aromatic onium salts,
Acrylic ester or methacrylic ester monomers can be used within a range that does not impair the effects of the present invention in order to effect curing using a photoradical polymerization system. These various acrylic ester or methacrylic ester monomers may be used alone, or two or more types may be used in combination. [F]) It is within 40 parts by weight based on 100 parts by weight of the total amount of components. A solvent can be used in the composition of the present invention for the purpose of improving the workability of screen printing, especially when used as a liquid crystal cell peripheral sealant. Examples of this solvent include ketone-based, Various solvents belonging to ester, ether, aliphatic or aromatic hydrocarbons or chlorinated hydrocarbons which do not disturb the emulsion of the screen are used. The amount of solvent used is such that the weight ratio contained in the composition is 20]
Within ii%. The composition according to the present invention may contain a reactive diluent having one or more epoxy groups in its 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-ethyl glycidyl ether, ferric glycidyl ether, p-butylphenyl glycidyl ether, glycerin glycidyl ether, and neointhyl glycidyl ether. Glycidyl ether and the like can be used. The amount of the reactive diluent used is within a range that does not impair the adhesiveness and suitability for liquid crystals, which are the objectives of the present invention, but preferably (A
) and component (B) within 20 parts by weight based on 100 parts by weight of the total amount. Furthermore, various modifying additives may be added to the composition according to the present invention as required for modifying physical properties or for purposes of use. For example, in the manufacture of liquid crystal cells, granular or needle-like particles are used to maintain appropriate spacing between liquid crystal cells; fillers such as silica and glass beads; and fillers that improve adhesion and moisture resistance. Silicone-based, titanate-based, and other coupling agents; Printing such as Aerosil and Bentone to provide screen printability;
A hamic imparting agent; a leveling agent such as Florade; an extender pigment such as aluminum hydroxide or barium hydroxide; and an improved polymer substance such as petroleum resin, rosin, nylon, or acrylic resin can also be blended. To cure the composition according to the present invention, wavelengths of 320 to 5
00 UV and visible light are effective. Examples of this radiation source include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, and an argon gas laser. Other active energy rays that can be used for curing include X-rays and electron beams. Furthermore, although the present composition is sufficiently cured by irradiation with active energy rays and exhibits properties that meet the intended purpose, even better properties can be obtained by leaving the composition in a heating chamber after irradiation. An example of this temperature range is 50 to 80'Cf2 to 20 hours. In addition, the photocurable composition for sealing according to the present invention has adhesive properties,
It has excellent cold and heat cycle resistance, flexibility, etc., and is fast curing, so it is not only used as a sealant for liquid crystal cells, but also used for other light-transmitting materials such as glass and plastic. It can also be used as an adhesive. For example, adhesion of camera lenses, eyeglass lenses, other optical lenses, stereo dials, decorative laminated glass, automotive laminated glass, insulating laminated glass, advertising films, printing typesetting boards, etc., connection of die bonding lead wires, and temporary bonding. Applications for temporary fixing of chip components mounted on printed circuit boards, protective coatings for electronic circuits, surface protection of parts, adhesives related to laser discs, resin for molding, sealing of small parts, botting, and adhesion of coil terminals. However, the use of the photocurable composition for sealing liquid crystal cells is not limited. [Function] The initiation mechanism of the aromatic onium salt, which is a photocationic initiator, is shown in the following formula. For example, in the case of a sulfonium salt, Ar' (where X- is BF4- or PF ,
-Ar -S" X- or AsF6- or 5bF6
−, Ar" Ar, Ar', At"
represents a monovalent aromatic hydrocarbon group. ) Ar 3 S"X-4 (Ar 3 S"X-) "2A
r” −〉Ar −Ar Ar ” + ZH−1) ArH+ Z ” The aromatic onium salt is decomposed by light irradiation and releases protonic acid having cationic polymerization ability as shown by the symbol in the formula.This photodecomposition The reaction occurs due to the absorption of ultraviolet light and visible light by the cation moiety exemplified by Ar3S'' in the formula. however,
This cation part is J, V, Cr1vello et, a
Report of “Journal of Pol-yme”
r 5icence Polymer Chemist
ry Edition” 17+ pages 977-999
(1979), the maximum absorption wavelength (lambda ms below the wavelength of the absorption peak apex, referred to as x; a single compound may have a plurality of wavelengths) is usually at a short ultraviolet wavelength of 300 nm or less. For this reason, cationic polymerization was not initiated by irradiation with the bright lines of a mercury lamp, such as the l-line (365 nm) or t-line (436 nm), which is a light source often used for photocuring, and argon laser, whose use has been considered in recent years. Further, the molecular extinction coefficient ε of these aromatic onium salts at 1 ml×K was about 2QOOOO, which is a large value when considering the energy distribution in the wavelengths of various light sources. For this reason, soda glass is often used as a cell transparent plate as a sealant for forming liquid crystal cells, which is one of the main uses of this composition, and soda glass absorbs most of the light of 300 nm or less. In order to cure the composition by transmitting the light, a long period of light irradiation was required. In addition, as a liquid crystal injection port sealant, which is one of its main uses, in some cases, a build-up of about 1 m thick is required, so the light attenuation inside the composition is large due to the size of ε mentioned above. Therefore, the amount of active species for cationic polymerization generated inside was small. Therefore, internal curing properties were poor, and in order to improve this, improvements were required to fundamentally improve photosensitivity, such as increasing the amount of aromatic onium salts, even though this would reduce liquid crystal resistance. was. It is known that a sensitizer is used in photosensitive resins for the purpose of expanding the wavelength range to which they are sensitive. Most of these polymerization systems involve radicals, but S. P. Pappas at, a.
l; “Photographic 5science a
nd Engineering”Yu, (3), 1
40 (1979) and US Pat. No. 4,063,054. The present inventors further investigated the effect of adding a sensitizer in such an epoxy photocationic polymerization system, and found that although improvements in curability and expansion of the photosensitive wavelength range toward longer wavelengths were observed in the prior art literature on preplants, Patent No. 406C40
The barrier of the cured product of the present inventors is that not all compositions using the "cationically polymerizable monomer" listed as an essential component in No. 54 are suitable as liquid crystal cell sealants. It has been criticized for consideration of sexuality. Also,
It has become clear from the inventors' study of the components eluted from the cured product that the weight composition of the aromatic onium salt and sensitizer exemplified in these documents is not suitable as a liquid crystal cell sealant. It's here. On the other hand, the effectiveness of adding a sensitizer is not only limited to the above-mentioned curability and expansion of the photosensitive wavelength range, but also from the viewpoint of effective use of the photoinitiator within the composition. It is also effective because it reduces the amount of components and shows good moisture resistance and heat resistance over time in a liquid crystal cell abuse test. The present inventors investigated the elution behavior of epoxy photocationic products from various cured products and the temporal changes in the liquid crystal cell driving current value in a liquid crystal cell abuse test. It was found that when a resin is selected, the increase in liquid crystal cell driving current value over time depends on the amount of the aromatic onium salt used as an initiator and its photodecomposition product. However, studies by the present inventors have revealed that in the above-mentioned low-molecular sensitization system, the sensitizer itself, which is a low-molecular compound, is eluted from the cured product and affects the liquid crystal cell drive current value. Furthermore, if a sensitizer with a polymerizable substituent is used instead of this low-molecular sensitizer, the sensitizer will be incorporated into the cured product through chemical bonds during the stage where the assembled product is cured by light irradiation. Therefore, it was found that elution from this cured product was at an extremely low level, did not increase over time, and did not cause the liquid crystal cell drive current value to increase over time. The effect of adding a sensitizer in the composition of the present invention cannot be evaluated under appropriate conditions by simply examining the shortening of hardening time, as used in the literature on preculture, due to the above-mentioned elution problem. Here, the present inventors measured the temperature dispersion of the dynamic viscoelasticity of the cured product film, evaluated the effectiveness of the sensitizer addition based on the Tg and molecular weight between crosslinking points of the obtained cured product, and The figure shows the relationship between the amount of sensitizer added, the Tg of the cured product, and the molecular weight between crosslinking points. From FIG. 1, by adding a sensitizer, the Tg of the cured product increases and the molecule it (Mc) between crosslinking points decreases. The other curve has a maximum, and as the amount of sensitizer added further increases, Tg gradually decreases and Me increases. From this, it is clear that the addition of a sensitizer has the effect of improving the properties of the cured product. Furthermore, since excessive addition of a sensitizer deteriorates the properties of the cured product, it is clear that there is an appropriate range for the amount of sensitizer used. [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-d IJ Butadiene BP-1000 (Adeka Argus ■) corresponding to component (3) of the present invention obtained by treating 1,2-polybutadiene with peracetic acid and having an oxygen content of 77 Product name) 5
Alicyclic epoxy resin ERL corresponding to component (with 0 parts)
Mix well 50 parts of -4299 (trade name of U, C, C Company). Next, component (C), triphenylsulfonium hexafluoroantimonate (furopylene carbonate 50
A photocurable composition (1-A) for sealing a liquid crystal injection port of the present invention was prepared by adding 1 part of a sensitizer solution and vinyl anthracene as a sensitizer component in the following amounts and kneading thoroughly. ~(1-D
) was obtained. Amount of vinyl anthracene added (parts) Composition
Product I X 1 0-2 (1-A) 5 X 1 0-2 (1-81 1
-C:]2X10' (1-
D) Example 2 In advance, 4 parts of (rylene 3,4.9110-tetracarboxylic acid anhydride and 25 parts of 2-hydroxyethyl methacrylate) were subjected to a half-esterification reaction at 950°C overnight to form a polymerizable substituent. Perylene 3,9-dicarboxylic acid-4,10-di(2-isopropenylcarbonyloxyethyl) ester and 2-
A mixture of hydroxyethyl methacrylate (2-A) was obtained. Next, polybutadiene-modified epoxy resin Nl5SO epoxy resin corresponding to component (2) in the present invention obtained by reacting an epoxy resin with x+2-7 butadiene having a carboxyl group at the molecular end produced by the anion living method -27 (Nippon Soda ■Product name) 30 copies and [F]
) Alicyclic epoxy resin hepoxide-2 corresponding to the component
Mix well 70 parts of 021 (Daicel Chemical ■ trade name). Next, component (C), triphenylphenacylphosphonium tetrafluoroborate (propylene carbonate) 5
0 parts% solution) 5 parts, sensitizer a synthesized above: 1) component perylene 3,9-dicarboxylic acid-4,71-di(2
- a mixture of isoprodicarbonyloxyethyl) ester and 2-hydroxyethyl methacrylate 0.05
(0.01 part as a sensitizer) and knead well to obtain the photocurable composition for sealing the liquid crystal injection port of the present invention (
2-B) was obtained. Example 3 In advance, 20.5 parts of methyleosin and 111 parts of epichlorohydrin were placed in a four-bottle flask equipped with a reflux condenser, a thermometer, and a stirring device, and 5 parts of the solvent dimethylformamide were added.
0 parts, catalytic crown ether (15-crown -5
) After reacting at 80° C. for 3 days in the presence of 0.7 parts, the reaction mixture was washed with water, extracted with diethyl ether, and recrystallized.
A sensitizer methyleosin-glycidyl ether with 5 parts of polymerizable substituents was obtained. Na l$r BY then 1.2-
Add 46 parts of sodium dispersion to 5000 parts of dissolved tetrahydrofuran and make 160 parts of diphenyl puffs.
℃, 886 parts of butadiene was added dropwise over 2 hours, and after the dropwise addition was completed, the mixture 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 equal volumes of water, tetrahydrofuran was distilled off under reduced pressure and the number average molecular weight was 137.
A terminally epoxidized prbutadiene corresponding to component (2) in the present invention was obtained with an oxygen content of 2.01% and an epoxyoxirane oxygen content of 2.01%. Next, 1. 30 parts of the terminally modified polybutadiene and 50 parts of bisphenol A epoxy resin YTR tote YD-8125 (Tobu Kasei brand name) corresponding to component [F]), which also corresponds to component (2). Novolac type epoxy resin EOCN103 (Nippon Kayaku ■Product name) 26
Mix well. Next, (3 parts of diphenyliodonium tetrafluoroborate as component 0, 0.0 parts of sensitizer methyleosin-glycidyl ether (mentioned above) as component (2))
5 parts and 12 parts of Aerosilna 380 (Japan Aerosil ■ trade name) were added and mixed, and after kneading well with three paint rollers, a spacer with a diameter of 5 μm and a length of 15 ~
Two parts of a 30 μm single glass fiber (manufactured by Chuyu Optical Glass Manufacturing Co., Ltd.) were mixed to obtain a photocurable sealing composition [3] for sealing around a liquid crystal cell. Example 4 HycarCTBN13, a butadiene-acrylonitrile 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 (YD-812) in a stirrer,
Pour into a Seno ξ rubble flask equipped with a reflux condenser, nitrogen blowing tube, and thermometer, and stir for 13 minutes under nitrogen atmosphere.
The reaction was carried out at 0° C. for 4 hours to obtain a polybutadiene-modified epoxy resin with an acid value of 0.6. Next, 50 parts of the polybutadiene-modified epoxy resin, 5 parts of the bisphenol FW epoxy resin Epicoat 807 (oil-based shell epoxy ■ trade name)
Add 0 parts of triphenylsulfonium hexafluoroantimonate (50% solution of fluoropylene carbonate) and 0 parts of vinylanthracene as a sensitizer.
．． 005 parts, epoxy silane coupling agent 3-403
(Shin-Etsu Silicone ■Product name) 1 part, Aerosil ÷ 380
After adding 14 parts and kneading well with three paint rollers, 3 parts of glass single fibers (described above) as a coating material were mixed to obtain a photocurable sealing composition for sealing the periphery of a liquid crystal cell [4]
I got it. Comparative Example 1 A composition obtained by removing only the sensitizer vinylanthracene from the composition of Example 1 was taken and thoroughly kneaded to obtain a composition [5] for use in sealing a liquid crystal injection port which deviates from the scope of the claims of the present invention. Comparative Example 2 A composition was prepared in which only the sensitizer vinylanthracene having a polymerizable substituent was removed from the composition of Example 1, and 0.01 part of a sensitizer anthracene having no polymerizable substituent was added instead. By thoroughly kneading the mixture, a composition [6] which deviated from the scope of the claims of the present invention was obtained. Comparative Example 3 100 parts of Araldite MY-720 (trade name, Ciba Geigy), which is N,N'-tetraglycidyl roof unilene diamine, and 5 parts of triphenylphenacylphosphonium tetrafluoroborate (50 fluoropylene carbonate multi-solution) were used. Sensitizer (2-A) synthesized in Example 2 0.05
The components were thoroughly mixed to obtain composition [7]. Comparative Example 4 Using 60 parts of alicyclic epoxy resin UVR-6100 (product name of U, C, C) and flexible resin in the same manner as described in technical document 449654 on photoepoxy polymerization of Union Carbide Co. (U, C, C) Sex-imparting epoxy resin UVR-6351 (
U, ClC company brand name) 40 parts, triphenylsulfonium hexafluoroantimonate (50% propylene carbonate solution) 4 parts, Aerosil *380 12 parts,
After mixing 31 parts of IGIM-40 and kneading well with a triple-throw Indian roller, the spacer glass single fibers (mentioned above) 2
A composition [8] for peripheral sealing was obtained by mixing the above components. Comparative Example 5 A composition for peripheral sealing by removing only the sensitizer methyleosin-glycidyl ether having a polymerizable substituent from the composition of Example 3, and sensitizing and mixing the sensitizer without a polymerizable substituent. thing

[9] was obtained. (1-A) obtained in Examples 1 to 4 and Comparative Examples 1 to 5
) ~ (1-D), (2-B, l, [3], [4], [5
], [6], [7], [8],

Using each of the compositions [9], the curing properties and liquid crystal cell sealing properties were measured by the following methods. <Curing property measurement> The curable compositions obtained in Example 1 and Comparative Example 1 (1-
A) to (1-D) and [5] to JIS-G3303
It was applied onto a pre-Φ board using a 6 miA doctor blade, and irradiated with light for 3.5 seconds from a distance of 10 mm using a high-pressure mercury lamp (80 W/cm) to obtain a cured coating film. The viscoelasticity was measured using a dynamic viscoelasticity measurement device Rheopybron DDV-I-EA (Toyo Baldwin) at a displacement of ±0.025 m, a frequency of 35 Herz, and a heating rate of 2°C/min, and the resulting cured product was The Tg and the molecular weight between crosslinking points are shown in FIG. For convenience, the peak temperature of the loss modulus (E) was used as Tg, and the molecular weight between crosslinking points was determined from rubber elasticity theory. In addition, (1
-B), (2-B), [3]~

[9] Characteristics of each composition and measurement of liquid crystal cell sealing properties by curing by irradiation with light for a predetermined period of time using a high-pressure mercury lamp (80 W/tan) at a distance of 10 times> Ion diffusion prevention treatment, electrode formation and [3], [4], [8], obtained in Example 3.4 and Comparative Example 4.5 by screen printing on an oriented glass plate (thickness 0.55 tam),

Each composition [9] was applied to the outer periphery of the cell. Next, the same treated glass plate used earlier was placed on top and crimped. This was irradiated with light for a predetermined period of time from a distance of 10 scratches using a high-pressure mercury lamp (80 W/equipment) in the crimped state to cure the composition. Next, a liquid crystal was sealed by vacuum method, and Example 1
．． 2 and Comparative Example 1.2 (1-B), (2-
The liquid crystal injection port was sealed using each of the compositions B], (5), and [6], and a high-pressure mercury lamp (80 W/m) was used.
The composition was cured by irradiating light from a distance of 10 cWL for a predetermined period of time to produce a liquid crystal cell. Next, each sample A-HK of the liquid crystal cell produced in this manner was subjected to performance tests such as sealing performance, high temperature and high temperature and high humidity durability, liquid crystal cell drive current value change rate, and cold/heat cycle resistance. The results are shown in Table 2. [Effects of the Invention] As shown in Table 1 and FIG. It has a height of Furthermore, the light wavelength range that can be effectively used for photocuring is extended to longer wavelengths. Furthermore, as shown in Table 1, the components eluted from the photocured product are reduced. Furthermore, as shown in Table 2, it has extremely excellent adhesion, sealing properties, and cold/heat cycle resistance as a liquid crystal cell peripheral sealant and injection port sealant, which helps save labor in the liquid crystal cell manufacturing process. The contribution is clear.

[Brief explanation of drawings]

Figure 1 shows the Tg of the cured product obtained from the viscoelasticity measurement of the photocured film of the compositions (1-A) to (1-D] and [5] and the molecule Ik (Me) between the crosslinking points as a sensitizer. This is a diagram plotted against additive loans.

Claims (3)

[Claims] (1) (A) A butadiene-based resin that has a butadiene homopolymer or butadiene copolymer as its main chain skeleton and has an average of at least 1.5 or more epoxy groups per molecule at the molecular terminal and/or side chain, (B ) at least one epoxy resin selected from the group consisting of alicyclic epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, and hydrogenated bisphenol A epoxy resin; (C) light sensing; 1. A photocurable composition for sealing, comprising as essential components a sensitizer having a polymerizable substituent and (D) a sensitizer having a polymerizable substituent. (2) The sensitizer having a polymerizable substituent is a vinyl group, a vinyl ether group, an isopropenyl group, an acryloyl group,
A polynuclear aromatic compound or a polynuclear heterocyclic compound having at least one substituent selected from the group consisting of a methacryloyl group, an allyl group, an epoxy group, and an organic residue containing a bicycloorthoester, a spiroorthoester, or a spiroorthocarbonate. The photocurable composition for sealing according to claim (1), which is a compound or a derivative thereof. (3) In the blending of components (A), (B), (C) and (D), the blending ratio of components (A) and (B) is 10 to 70 parts by weight of component (A) and component (B). 90 to 30 parts by weight, 0.1 to 5 parts by weight of component (C) and 0.001 to 0.001 parts by weight of component (D) based on 100 parts by weight of the total amount of components (A) and (B).
The photocurable composition for sealing according to claim (1), wherein the amount is 0.5 parts by weight.