JP2005115255A - Liquid crystal sealing agent and liquid crystal display cell using the same - Google Patents

Liquid crystal sealing agent and liquid crystal display cell using the same Download PDF

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JP2005115255A
JP2005115255A JP2003352411A JP2003352411A JP2005115255A JP 2005115255 A JP2005115255 A JP 2005115255A JP 2003352411 A JP2003352411 A JP 2003352411A JP 2003352411 A JP2003352411 A JP 2003352411A JP 2005115255 A JP2005115255 A JP 2005115255A
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liquid crystal
sealing agent
general formula
agent
group
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Inventor
Toyofumi Asano
Masahiro Hirano
Masahiro Imaizumi
Masaru Kudo
Eiichi Nishihara
Naoyuki Ochi
雅裕 今泉
勝 工藤
雅浩 平野
豊文 浅野
直之 落
栄一 西原
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Nippon Kayaku Co Ltd
日本化薬株式会社
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal sealing agent having high adhesion strength, extremely low staining property for a liquid crystal, and excellent storage stability, and to provide a liquid crystal display cell having excellent reliability which can be manufactured by using the above liquid crystal sealing agent in a liquid crystal dropping method. <P>SOLUTION: The liquid crystal sealing agent contains as essential components: (a) a photosetting resin; (b) a photopolymerization initiator; (c) an epoxy resin; (d) a thermosetting agent; and (e) a borate compound expressed by general formula (1), general formula (2) or general (3). In each formula, R1 represents a hydrogen atom, a lower alkyl group or an aryl group, and each of R2, R3, R4, R5, R6 and R7 represents a lower alkylene group or an aryl group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a liquid crystal sealant and a liquid crystal display cell using the same. More specifically, after the liquid crystal is dropped inside the photothermographic combination type liquid crystal sealant weir formed around one substrate, the other substrate is bonded and the liquid crystal sealant is cured to thereby form the liquid crystal. The present invention relates to a liquid crystal sealant used for manufacturing a liquid crystal display cell to be sealed and a liquid crystal display cell manufactured using the same.

  With the recent increase in size of liquid crystal display cells, a so-called liquid crystal dropping method with higher mass productivity has been proposed as a method for manufacturing liquid crystal display cells (see Patent Document 1 and Patent Document 2). Specifically, it is a method of manufacturing a liquid crystal display cell in which liquid crystal is sealed by dropping liquid crystal inside a liquid crystal sealing agent weir formed on one substrate and then bonding the other substrate.

  However, in the liquid crystal dropping method, the liquid crystal sealant first contacts the liquid crystal in an uncured state, and at this time, the liquid crystal sealant component dissolves in the liquid crystal and the specific resistance of the liquid crystal is lowered. There is a problem, and it is not widely used as a mass production method of liquid crystal display cells.

  In the liquid crystal dropping method, three methods of a thermosetting method, a photocuring method, and a photothermal curing combined method are considered as a curing method after the liquid crystal sealant is bonded. In the thermosetting method, there is a problem that the liquid crystal leaks from the liquid crystal sealant in the middle of curing, which has been reduced in viscosity due to expansion of the liquid crystal due to heating, and a problem that the components of the liquid crystal sealant whose viscosity has been reduced dissolves in the liquid crystal. These problems are difficult to solve and have not yet been put into practical use.

  On the other hand, the liquid crystal sealant used in the photocuring method includes two types of cationic polymerization type and radical polymerization type depending on the type of photopolymerization initiator. With regard to the cationic polymerization type liquid crystal sealing agent (see Patent Document 3), ions are generated during photocuring, so when this is used in a liquid crystal dropping method, the ionic component is eluted in the liquid crystal in the contact state, and the liquid crystal There is a problem of lowering the specific resistance. Further, the radical polymerization type liquid crystal sealant (see Patent Document 4) has a problem that the adhesive strength is not sufficient because of the large shrinkage during photocuring. Furthermore, as a problem related to both the cationic polymerization type and radical polymerization type photocuring methods, the light shielding part where the liquid crystal sealant is not exposed to light by the metal wiring part of the array substrate of the liquid crystal display cell and the black matrix part of the color filter substrate. Therefore, there arises a problem that the light-shielding portion becomes uncured.

  As described above, the thermosetting method and the photocuring method have various problems. Actually, the photothermal curing combined method is considered to be the most practical method, and various liquid crystal sealing agents have been proposed (patents). Literature 5, Patent Literature 6). The photothermal curing combined method is characterized in that the liquid crystal sealant sandwiched between the substrates is irradiated with light to be primarily cured and then heated to be secondarily cured. It is important that the liquid crystal sealant used in the photothermal curing combined method does not contaminate the liquid crystal in each step before and after light irradiation and before and after heat curing. Sex matters.

  On the other hand, the sealant is applied to the substrate by a dispensing method in the liquid crystal cell manufacturing process, but there arises a problem that the seal width varies when the discharge pressure changes due to the viscosity change. Frequent replacement of the sealant in the manufacturing process not only lowers the effective usage rate of the sealant but also impairs the stability of quality in the liquid crystal cell production line. There is a need for sealing agents. However, the conventionally known photothermal curing combined type liquid crystal sealing agent is considered to have a very poor pot life because it uses epoxy resin and (meth) acrylate resin as main components and dihydrazides and amines as thermosetting agents ( Patent Document 5, Patent Document 6). These thermosetting agents are selected from the viewpoint of not causing thermal damage to the liquid crystal, assuming low temperature rapid curing at 120 ° C. for about 1 hour, and it is therefore considered that the pot life is sacrificed.

  For the thickening of epoxy resin, (meth) acrylate resin, and sealant containing thermosetting agent, not only the reaction of epoxy resin and thermosetting agent of thermosetting component, but also thermosetting component (meth) acrylate resin and thermosetting Since the contribution of the agent reaction is large, measures against both reactions are required. As a method for achieving both low temperature rapid curing and pot life with an epoxy resin composition, a method of microencapsulating a curing agent or a curing accelerator is generally known. Further, Patent Document 7 includes a method of adding latency to an epoxy resin composition by blending a cyclic borate compound and a phenol compound.

  As described above, the photothermal curing combined use type liquid crystal sealant for the liquid crystal dropping method that has been proposed in the past is satisfactory in all of the liquid crystal contamination, adhesive strength, pot life at room temperature, and low temperature curing. It is not something that can be done.

JP-A 63-179323 JP-A-10-239694 JP 2001-89743 A JP-A-01-243029 Japanese Patent No. 3162179 JP 2001-133794 A JP-A-9-26822

  In the present invention, after a liquid crystal is dropped inside a liquid crystal sealing agent weir formed on one substrate, the other substrate is bonded, a liquid crystal sealing portion is irradiated with light, and a liquid crystal display cell is manufactured by heat curing. The liquid crystal sealant used in the liquid crystal dripping method is extremely low in contamination with the liquid crystal throughout the process, and even if an uncured part is generated in the shaded part, the sealant component is almost not eluted into the liquid crystal. The present invention proposes a liquid crystal sealant that is excellent in low-temperature curability and at the same time has a good pot life.

The present inventors have completed the present invention as a result of intensive studies to solve the above-mentioned problems. That is, the present invention
(1) A liquid crystal seal comprising (a) a photocurable resin, (b) a photopolymerization initiator, (c) an epoxy resin, (d) a thermosetting agent, and (e) a boric acid ester compound. Agent,
(2) (e) The borate compound is represented by the general formula (1)

(Wherein R1 represents a hydrogen atom, a lower alkyl group or an aryl group, and R2 represents a lower alkylene group or an aryl group),
General formula (2)

(Wherein R3 and R4 may be the same or different and represent a lower alkylene group or an aryl group) or general formula (3)

(Wherein R5, R6 and R7 may be the same or different and represent a lower alkylene group or an aryl group)
The liquid crystal sealing agent according to (1), which contains a borate ester compound represented by:

(3) The liquid crystal sealing agent according to (1) or (2), wherein (a) the photocurable resin is an epoxy (meth) acrylate resin,
(4) The liquid crystal sealing agent according to any one of (1) to (3), which contains a phenolic compound (f),
(5) The liquid crystal sealant according to any one of (1) to (4), wherein the content of the epoxy resin in the liquid crystal sealant is 5% by weight to 50% by weight,
(6) (d) The liquid crystal sealing agent according to any one of (1) to (5), wherein the thermosetting agent is a dihydrazide.
(7) The liquid crystal sealant according to (6), wherein the dihydrazide is a dihydrazide having an isophthalic acid dihydrazide and / or a valine hydantoin skeleton,

(8) (e) The content of the boric acid ester compound represented by the general formula (1), the general formula (2) or the general formula (3) in the liquid crystal sealant is 0.01% by weight to 10% by weight ( The liquid crystal sealant according to any one of 2) to (7).
(9) (g) The liquid crystal sealing material according to any one of (1) to (8), which contains a silane coupling agent,
(10) (g) The liquid crystal sealing agent according to (9), wherein the silane coupling agent is a silane coupling agent having an amino group.
(11) A liquid crystal display cell sealed with a cured product of the liquid crystal sealing agent according to any one of (1) to (10).
(12) After the liquid crystal is dropped inside the liquid crystal sealing agent weir described in any one of (1) to (109) formed on one substrate, the other substrate is bonded and cured. Manufacturing method of liquid crystal display cell,
About.

By using the liquid crystal sealing agent of the present invention, which has excellent adhesive strength, low liquid crystal contamination, and good storage stability, in the liquid crystal dropping method, it has become possible to produce a liquid crystal display cell with excellent reliability.

Hereinafter, the present invention will be described in detail.
The (a) photocurable resin used in the present invention is not particularly limited as long as the elution property to the liquid crystal is low, but an epoxy (meth) acrylate resin is particularly preferable from the viewpoint of liquid crystal contamination. This epoxy acrylate resin or epoxy methacrylate resin (a) component can be obtained by esterifying acrylic acid or methacrylic acid to an epoxy resin having at least two epoxy groups in the molecule. This synthesis reaction can be performed by a generally known method. For example, a predetermined equivalent ratio of acrylic acid or methacrylic acid to an epoxy resin (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstibine, etc.) and a polymerization inhibitor (for example, methoquinone, Hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene and the like) are added and the esterification reaction is performed at 80 to 110 ° C., for example.

  Examples of the photopolymerization initiator (b) used in the present invention include radical-generating photopolymerization initiators such as benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diethylthioxanthone, benzophenone, 2-ethylanthraquinone, 2 -Hydroxy-2-methylpropiophenone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. An initiator having sensitivity in the vicinity of i-line (365 nm) that has a relatively small influence on liquid crystal characteristics and low liquid crystal contamination is preferable. As such an initiator, specifically, 6,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole, 3,6-bis (d2-methyl-2-morpholinopropionyl)- Examples thereof include 9-n-octylcarbazole and 1,7-bis (9-acridyl) heptane.

  In the liquid crystal sealing agent of the present invention, the blending ratio of the (b) radical generating photopolymerization initiator to the component (a) is preferably 0.1 to 10 parts by weight, particularly preferably 100 parts by weight of the component (a). Is 0.5 to 3 parts by weight. If the amount of the radical-generating photopolymerization initiator is less than 0.1 parts by weight, the photocuring reaction is not sufficient, and if it exceeds 10 parts by weight, the amount of the initiator is too much and the liquid crystal is contaminated by the initiator and the cured resin properties. Decrease is a problem.

  Although it does not specifically limit as an epoxy resin (c) used by this invention, It is preferable that it is an epoxy resin which is hard to elute with respect to a liquid crystal from a liquid crystal contamination viewpoint. As such an epoxy resin, for example, bisphenol S type epoxy resin (formula (4)),

Resorcin diglycidyl ether multimer (formula (5)),

(In the formula, n represents an integer of 1 to 10.)
Diglycidyl ether of ethylene oxide-added bisphenol S (formula (6)),

Diglycidyl ether of ethylene oxide-added bisphenolfluorene (formula (7)),

However, it is not limited to these.

  The amount of hydrolyzable chlorine in the epoxy resin used in the present invention is 600 ppm or less, preferably 300 ppm or less. If the amount of hydrolyzable chlorine exceeds 600 ppm, the contamination of the liquid crystal sealant with respect to the liquid crystal may become a problem. The amount of hydrolyzable chlorine is quantified by, for example, dissolving about 0.5 g of epoxy resin in 20 ml of dioxane, refluxing with 5 ml of 1N KOH / ethanol solution for 30 minutes, and titrating with 0.01N silver nitrate solution. Can do.

  The liquid crystal sealing agent of the present invention contains a thermosetting agent (d). The thermosetting agent is not particularly limited as long as it forms a cured product by reacting with an epoxy resin, but when heated, the liquid crystal sealant starts a reaction quickly and uniformly without contaminating the liquid crystal. In use, it is important that there is little change in viscosity over time at room temperature. As a thermosetting condition, in the case of the liquid crystal dropping method, a low temperature curing ability at about 120 ° C. for about 1 hour is generally required in order to minimize deterioration of characteristics of the liquid crystal to be enclosed. In view of the above points, it is particularly preferable to use polyfunctional hydrazides and polyvalent amines as the thermosetting agent in the liquid crystal sealant of the present invention.

  In the present invention, polyfunctional dihydrazides refer to those having two or more hydrazide groups in the molecule. Specific examples thereof include carbohydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, and adipic acid dihydrazide. , Adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecanediodihydrazide, hexadecanediohydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide dihydrazide diacid dihydrazide dihydrazide dihydrazide Acid dihydrazide, terephthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 4,4-bisbenzenedihydrazide, 1,4-naphthoic acid dihydrazide, 2, -Pyridinedihydrazide, 1,2,4-benzenetrihydrazide, pyromellitic acid tetrahydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, 1,3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin Examples thereof include, but are not limited to, dihydrazides having a valine hydantoin skeleton.

  When polyfunctional dihydrazide is used as a curing agent, it is preferable to finely disperse the particle size in order to obtain a latent curing agent. Of the polyfunctional dihydrazides, dihydrazide is preferred, and from the viewpoint of liquid crystal contamination, particularly preferred are isophthalic acid dihydrazide and dihydrazide having a valine hydantoin skeleton. The average particle diameter is preferably 3 μm or less, and more preferably 2 μm or less, because if the average particle size is too large, it becomes a cause of defects such as failure to form a gap when the upper and lower glass substrates are bonded together when manufacturing a narrow gap liquid crystal cell. Similarly, the maximum particle size is preferably 8 μm or less, more preferably 5 μm or less. The particle size of the curing agent can be measured with a laser diffraction / scattering particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30).

  In the liquid crystal sealing agent of the present invention, the blending ratio of the thermosetting agent (d) component is preferably 0.8 to 1.5 equivalents, more preferably 0.9 to 0.1 equivalents of the epoxy group equivalent of the component (c). 1.2 equivalents. When the amount of the component (d) is less than 0.8 equivalent, the thermosetting reaction becomes insufficient and the adhesive force and the glass transition point tend to be lowered. On the other hand, when the equivalent is more than 1.5, the curing agent remains, the adhesive force is lowered, and the pot life may be deteriorated.

The borate ester (e) used in the present invention is a borate ester compound in which a ring is formed, and the compound represented by the general formula (1), the general formula (2) or the general formula (3) described above is used. Can be mentioned.
In the general formula (1), lower alkyl as R1 represents a C1-C10 linear / branched / cyclic aliphatic hydrocarbon, preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, n -A C1-C10 alkyl group such as a pentyl group. Examples of the aryl group include a phenyl group, a pyrrolyl group, and a thienyl group. The lower alkylene as R2 includes C1-C10 linear, branched, cyclic saturated or unsaturated hydrocarbons, preferably C1-C10 linear such as ethylene group, propylene group, 2,2-dimethyltrimethylene group. Or it is a branched alkylene group, As an aryl group, a phenyl group, a pyrrolyl group, a thienyl group etc. are mentioned. A preferable compound in the general formula (1) includes a compound in which R1 is an n-butyl group and R2 is a 2,2-dimethyltrimethylene group.

In the general formula (2), the lower alkylene group and aryl group of R3 and R4 are the same as described in the general formula (1). In the general formula (2), a combination of compounds in which R3 and R4 are both 2,2-dimethyltrimethylene groups is particularly preferable.
In the general formula (3), the lower alkylene group and aryl group of R5, R6 and R7 are the same as described in the general formula (1). In the general formula (3), a combined compound in which R5 and R7 are both 2,2-dimethyltrimethylene groups and R6 is a methylene group is particularly preferable.

In particular, representative examples of the boric acid ester (e) include tris-o-phenylene bisborate, bis-o-phenylene pyroborate, bis-2,3-dimethylethylene pyroborate, bis-2,2-dimethyl. Examples include trimethylene pyroborate and 2,2-oxybis (5,5-dimethyl-1,3,2-dioxaborinane).
These boric acid esters (e) used in the present invention can be obtained by using, for example, a synthesis method described in JP-A-6-325618 or a method analogous thereto.

  Representative examples of the (f) phenolic compound used in the liquid crystal sealant of the present invention include catechol, 4-t-butylcatechol, pyrogallol, resorcin, hydroquinone, phloroglicinol, bisphenol A, bisphenol F, and dihydroxybiphenyl. , Compounds such as dihydroxynaphthalene, 1,1,1-tris (4-hydroxyphenyl) ethane and bis (4-hydroxyphenylsulfone), novolak-type or resol-type phenolic resins, and phenolic polymers such as polyvinylphenol .

  In order to improve the adhesive strength, the liquid crystal sealing agent of the present invention preferably contains (g) a silane coupling agent. Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3 Chloropropyl methyl dimethoxy silane, silane coupling agents such as 3-chloropropyl trimethoxysilane. These silane coupling agents may be used in combination of two or more. Among these, in order to obtain better adhesive strength, the silane coupling agent is preferably a silane coupling agent having an amino group. By using a silane coupling agent, an adhesive strength is improved and a liquid crystal sealing agent having excellent moisture resistance reliability can be obtained.

  If necessary, the liquid crystal sealant according to the present invention may further contain additives such as organic solvents, organic fillers, inorganic fillers, pigments, leveling agents and antifoaming agents.

  In order to obtain the liquid crystal sealant of the present invention, the liquid crystal sealant of the present invention can be produced by uniformly mixing the above components with a known mixing apparatus such as a roll mill, a sand mill, a ball mill or the like. If necessary, filtration and defoaming treatment may be performed.

The liquid crystal display cell of the present invention is a cell in which a pair of substrates having predetermined electrodes formed on a substrate are arranged opposite to each other at a predetermined interval, the periphery is sealed with the liquid crystal sealant of the present invention, and liquid crystal is sealed in the gap. is there. The kind of liquid crystal to be sealed is not particularly limited. Here, the substrate is composed of a combination of substrates made of at least one of glass, quartz, plastic, silicon, etc. and having light transmission properties. For example, after adding a spacer (gap control material) such as glass fiber to the liquid crystal sealant of the present invention, the liquid crystal sealant is applied to one of the pair of substrates by a dispenser or the like to form a weir. Later, liquid crystal is dropped inside the liquid crystal sealant, and the other glass substrate is overlaid in a vacuum to create a gap. After forming the gap, the liquid crystal seal portion is irradiated with ultraviolet rays by an ultraviolet irradiator to be photocured. Ultraviolet irradiation amount is preferably 500mJ / cm 2 ~6000mJ / cm 2 , more preferably the dose of 1000mJ / cm 2 ~4000mJ / cm 2 is preferred. Then, the liquid crystal display cell of this invention can be obtained by hardening at 90-130 degreeC for 1-2 hours. The liquid crystal display cell of the present invention thus obtained has no display defects due to liquid crystal contamination, and has excellent adhesion and moisture resistance reliability. Examples of the spacer include glass fiber, silica beads, polymer beads and the like. The diameter varies depending on the purpose, but is usually 2 to 8 μm, preferably 4 to 7 μm. The amount used is usually 0.1 to 4 parts by weight, preferably 0.5 to 2 parts by weight, more preferably about 0.9 to 1.5 parts by weight, based on 100 parts by weight of the liquid crystal sealant of the present invention. is there.

  Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1
80 parts by weight of epoxy acrylate of bisphenol F epoxy resin, 20 parts by weight of RE-203 (manufactured by Nippon Kayaku Co., Ltd .; epoxy equivalent 233 g / eq, bisphenol S type epoxy resin with ethylene oxide), radical-generating photopolymerization 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole (manufactured by Asahi Denka Kogyo Co., Ltd., Adekaoptomer N-1414) as an initiator, and 2, borate as 2, 0.5 parts by weight of 2-oxybis (5,5-dimethyl-1,3,2-dioxaborinane), 0.5 parts by weight of PN-80 (manufactured by Nippon Kayaku Co., Ltd., phenol novolac resin), aminosilane coupling agent ( N-β (aminoethyl) γ-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Silicone, K BM-603) 1.3 parts by weight was heated and dissolved at 90 ° C. to obtain a resin solution. After cooling to room temperature, isophthalic acid dihydrazide (trade name IDH-S; finely pulverized jet mill pulverized grade manufactured by Otsuka Chemical Co., Ltd., melting point 224 ° C., active hydrogen equivalent 48.5 g / eq, average particle diameter 1.7 μm, maximum particle size 7 μm) 10 parts by weight, alumina (manufactured by CI Kasei Co., Ltd., SPC-Al, average particle size 1.0 μm), 13 parts by weight, rubber (manufactured by Kureha Chemical Industry Co., Ltd., Paraloid EXL-2655), The liquid crystal sealant of the present invention was obtained by dispersing and kneading 3.9 parts by weight of an average particle size of 0.2 μm with a mill. The viscosity (25 ° C.) of the liquid crystal sealant was 230 Pa · s (R-type viscometer (manufactured by Toki Sangyo Co., Ltd.))

Comparative Example 1
A liquid crystal sealing agent was obtained in the same manner as in Example 1 except that borate ester 2,2-oxybis (5,5-dimethyl-1,3,2-dioxaborinane) was not added. The viscosity (25 ° C.) of the liquid crystal sealant was 270 Pa · s. (R type viscometer (manufactured by Toki Sangyo Co., Ltd.))

(Storage stability test)
About 2 g of the liquid crystal sealant of each of Example 1 and Comparative Example 1 was left in a test room at room temperature of 25 ° C., and the viscosity change was followed. The results are shown in Table 1.

(LCD contamination test)
The specific resistance of the contact liquid crystal, which is an index of contamination of the liquid crystal, is measured by adding 0.1 g of a liquid crystal sealant to a sample bottle, adding 1 ml of liquid crystal (MLC-6866-100), and then placing it in a 120 ° C. oven. Charge for 1 hour, then leave at room temperature for 0.5 hour. Only the liquid crystal was taken out from the sample bottle after the treatment, and was put into the liquid electrode LE21 (manufactured by Ando Electric Co., Ltd.), and the specific resistance of the liquid crystal after 4 minutes was measured at a measurement voltage of 10V with an Advantest electrometer R-8340. The results are shown in Table 1. Here, in comparison with the specific resistance value of the liquid crystal processed in the same manner without contacting the liquid crystal sealant, the specific resistance value of the liquid crystal processed in contact with the liquid crystal sealant is the number of digits of the specific resistance value of the contact liquid crystal. Those that did not decrease by one digit or more were judged as good. The results are shown in Table 2.

(Adhesive strength test)
1 g of 5 μm glass fiber is added as a spacer to 100 g of the obtained liquid crystal sealant, and mixed and stirred. After applying this liquid crystal sealing agent on a glass substrate of 50 mm × 50 mm, laminating a glass piece of 1.5 mm × 1.5 mm on the liquid crystal sealing agent, and irradiating 2000 mJ / cm 2 of ultraviolet rays with a UV irradiator, It was cured by putting it in a 120 ° C. oven for 1 hour. The shear adhesive strength of the glass piece was measured. The results are shown in Table 2.

(Glass transition point)
The obtained liquid crystal sealant was sandwiched between polyethylene terephthalate (PET) films to form a thin film having a thickness of 100 μm, irradiated with 2000 mJ / cm 2 of ultraviolet rays by a UV irradiator, and then charged in a 120 ° C. oven for 1 hour to cure, After curing, the PET film was peeled off to prepare a sample. The glass transition temperature was measured in a tensile mode using a TMA tester (manufactured by Vacuum Riko Co., Ltd.) The results are shown in Table 2.

  As shown in Table 2, the physical properties necessary for the sealant, such as liquid crystal contamination, adhesive strength, and glass transition temperature, are also good values in both Example 1 and Comparative Example 1. However, with respect to storage stability, as shown in Table 1, the liquid crystal sealant of Comparative Example 1 has a viscosity of about 20% in 2 days at 25 ° C., whereas the liquid crystal sealant of Example 1 The sealant showed almost no thickening. Therefore, the liquid crystal sealant of Example 1 shows almost no difference in curing properties compared to the liquid crystal sealant of Comparative Example 1, but the liquid crystal sealant of the present invention is extremely excellent in storage stability. It can be said that it is a sealing agent.

Table 1
Example 1 Comparative Example 1
Initial viscosity (Pa · s) 230 270
25 ° C. × 24 hours later 230 300
25 ° C x 48 hours later 240 330

Table 2
Example 1 Comparative Example 1
Liquid crystal contamination test Good Good Adhesive strength (MPa) 85.5 84.9
Glass transition temperature (° C) 96.0 96.5

Claims (12)

  1. A liquid crystal sealing agent comprising (a) a photocurable resin, (b) a photopolymerization initiator, (c) an epoxy resin, (d) a thermosetting agent, and (e) a boric acid ester compound.
  2. (E) The borate ester compound is represented by the general formula (1)
    (Wherein R1 represents a hydrogen atom, a lower alkyl group or an aryl group, and R2 represents a lower alkylene group or an aryl group),
    General formula (2)
    (Wherein R3 and R4 may be the same or different and represent a lower alkylene group or an aryl group) or general formula (3)
    (Wherein R5, R6 and R7 may be the same or different and represent a lower alkylene group or an aryl group)
    The liquid crystal sealant according to claim 1, which is a compound represented by the formula:
  3. The liquid crystal sealant according to claim 1 or 2, wherein (a) the photocurable resin is an epoxy (meth) acrylate resin.
  4. (F) Liquid crystal sealing agent in any one of Claims 1 thru | or 3 containing a phenol type compound.
  5. (C) The liquid crystal sealant according to any one of claims 1 to 4, wherein the content of the epoxy resin in the liquid crystal sealant is 5% by weight to 50% by weight.
  6. (D) The liquid crystal sealant according to any one of claims 1 to 5, wherein the thermosetting agent is a dihydrazide.
  7. The liquid crystal sealant according to claim 6, wherein the dihydrazide is a dihydrazide having an isophthalic acid dihydrazide and / or a valine hydantoin skeleton.
  8. (E) The content of the boric acid ester compound represented by the general formula (1), the general formula (2) or the general formula (3) in the liquid crystal sealant is 0.01% by weight to 10% by weight. 8. The liquid crystal sealant according to any one of 7 above.
  9. (G) Liquid crystal sealing agent of any one of Claims 1 thru | or 8 containing a silane coupling agent.
  10. (G) The liquid crystal sealing agent according to claim 9, wherein the silane coupling agent is a silane coupling agent having an amino group.
  11. The liquid crystal display cell sealed with the hardened | cured material of the liquid-crystal sealing compound of any one of Claims 1 thru | or 10.
  12. 11. A liquid crystal display comprising: a liquid crystal is dropped inside the liquid crystal sealing agent weir according to claim 1 formed on one substrate, and the other substrate is bonded and cured. Cell manufacturing method.
JP2003352411A 2003-10-10 2003-10-10 Liquid crystal sealing agent and liquid crystal display cell using the same Pending JP2005115255A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006003432A (en) * 2004-06-15 2006-01-05 Sekisui Chem Co Ltd Sealant for liquid crystal display element, vertically conducting material, and the liquid crystal display element
US7728948B2 (en) 2007-04-26 2010-06-01 Semiconductor Energy Laboratory Co., Ltd. Liquid crystal display device and manufacturing method
JP2011090213A (en) * 2009-10-23 2011-05-06 Sekisui Chem Co Ltd Sealing agent for liquid crystal drop-fill process, vertical conducting material and liquid crystal display element
JP2011232631A (en) * 2010-04-28 2011-11-17 Mitsui Chemicals Inc Method for manufacturing liquid crystal display panel and liquid crystal display panel
JP5353008B2 (en) * 2005-11-25 2013-11-27 株式会社スリーボンド Curable composition
JP2016172801A (en) * 2015-03-17 2016-09-29 東洋インキScホールディングス株式会社 Active energy ray-polymerizable resin composition and laminate

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006003432A (en) * 2004-06-15 2006-01-05 Sekisui Chem Co Ltd Sealant for liquid crystal display element, vertically conducting material, and the liquid crystal display element
JP5353008B2 (en) * 2005-11-25 2013-11-27 株式会社スリーボンド Curable composition
US7728948B2 (en) 2007-04-26 2010-06-01 Semiconductor Energy Laboratory Co., Ltd. Liquid crystal display device and manufacturing method
US8269943B2 (en) 2007-04-26 2012-09-18 Semiconductor Energy Laboratory Co., Ltd. Liquid crystal display device and manufacturing method thereof
US8704971B2 (en) 2007-04-26 2014-04-22 Semiconductor Energy Laboratory Co., Ltd. Liquid crystal display device and manufacturing method thereof
JP2011090213A (en) * 2009-10-23 2011-05-06 Sekisui Chem Co Ltd Sealing agent for liquid crystal drop-fill process, vertical conducting material and liquid crystal display element
JP2011232631A (en) * 2010-04-28 2011-11-17 Mitsui Chemicals Inc Method for manufacturing liquid crystal display panel and liquid crystal display panel
JP2016172801A (en) * 2015-03-17 2016-09-29 東洋インキScホールディングス株式会社 Active energy ray-polymerizable resin composition and laminate

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