KR20140039314A

KR20140039314A - Liquid crystal sealing material and liquid crystal display cell using same

Info

Publication number: KR20140039314A
Application number: KR1020147001603A
Authority: KR
Inventors: 히데유키 오타; 에이이치 니시하라; 다이스케 이마오카; 사키 요시다; 겐타 스가와라
Original assignee: 닛뽄 가야쿠 가부시키가이샤
Priority date: 2011-07-03
Filing date: 2012-06-29
Publication date: 2014-04-01
Also published as: JP2013015645A; CN103649824A; CN103649824B; JP5748273B2; WO2013005692A1; TW201319109A

Abstract

It is an object of the present invention to provide a liquid crystal sealing agent for a liquid crystal dropping method which has a fast reaction by heat, very low contamination with liquid crystals through the process, excellent storage stability, and excellent cured product properties such as moisture resistance reliability.
Liquid crystal sealing agent of this invention (a) Curable resin which consists of 1 type (s) or 2 or more types chosen from an epoxy resin, (meth) acrylic epoxy resin, and partial (meth) acrylic epoxy resin which have active hydrogen in a molecule | numerator (a And hydrogen contained in a hydroxyl group as active hydrogen), and (b) a thermosetting agent.

Description

Liquid crystal sealing agent and liquid crystal display cell using the same {LIQUID CRYSTAL SEALING MATERIAL AND LIQUID CRYSTAL DISPLAY CELL USING SAME}

The present invention relates to a liquid crystal sealing agent having good curability by heat. More specifically, it is related with the liquid crystal sealing agent which has favorable curability by heat, is excellent also in storage stability, and also excellent in moisture resistance of hardened | cured material, etc., and its hardened | cured material.

Background Art [0002] Along with the recent enlargement of a liquid crystal display cell, a so-called liquid crystal dropping method has been proposed as a method of manufacturing a liquid crystal display cell (Patent Documents 1 and 2). Specifically, the liquid crystal is sealed by dropping liquid crystal on the inner side of a bank of a liquid crystal sealer formed on one of the substrates, and then bonding the other substrates to each other.

However, in the liquid crystal dropping method, since the liquid crystal sealing agent in the uncured state contacts the liquid crystal, the components of the liquid crystal sealing agent are dissolved (dissolved) in the liquid crystal at that time, thereby lowering the resistance value of the liquid crystal and causing display defects near the seal. There is this.

In order to solve this problem, a liquid crystal sealing agent for a liquid crystal dropping method has been used for practical use (Patent Literatures 3 and 4). In the liquid crystal dropping method using the liquid crystal sealant, the liquid crystal sealant sandwiched between the substrates is irradiated with light to primary cure, followed by heating to secondary cure. According to this method, the uncured liquid crystal sealant can be quickly cured by light, and dissolution (dissolution) of the liquid crystal sealant component into the liquid crystal can be suppressed. In addition, the photocuring alone also causes a problem of insufficient adhesive strength due to curing shrinkage or the like during photocuring. However, in the case of the photothermal combined use, such a problem can be solved by secondary curing by heating.

However, in recent years, with the miniaturization of liquid crystal display elements, a shielding portion that does not reach the liquid crystal sealant by the metal wiring portion of the array substrate of the liquid crystal display element or the black matrix portion of the color filter substrate is generated, The problem of bad is becoming more serious than before. That is, due to the presence of the light-shielding portion, the primary curing by the light becomes insufficient, and a large amount of uncured components remains in the liquid crystal sealant. In this state, when proceeding to the secondary curing step by heat, the dissolution of the uncured component into the liquid crystal is accelerated by heat, resulting in display failure in the vicinity of the seal.

In order to solve this problem, various examinations to improve the thermal reactivity have been made. In the light-shielding portion, it is an attempt to suppress liquid crystal contamination by quickly reacting a liquid crystal sealant which is not sufficiently cured by light from a low temperature. For example, Patent Documents 5 and 6 disclose a method using a thermal radical initiator. Moreover, in patent documents 7-9, the method of using polyhydric carboxylic acid as a hardening accelerator is disclosed.

However, generally, since a radical generate | occur | produces a radical little by little even at normal temperature, a thermal radical initiator has the problem that storage stability and working stability of liquid crystal sealing agent are bad. Moreover, since a hardening accelerator like polyhydric carboxylic acid acts as a catalyst and does not react by itself and is accepted by chemical bonding in hardened | cured material, it has a problem that it melt | dissolves in a liquid crystal and produces display defects.

As mentioned above, although the liquid crystal sealing agent is developed very vigorously, the liquid crystal sealing agent which has excellent thermal reactivity, and also has favorable storage stability, and has low liquid crystal contamination, has not yet been realized.

Japanese Patent Application Laid-Open No. 63-179323 Japanese Patent Laid-Open No. 10-239694 Japanese Patent Publication No. 3583326 Japanese Laid-Open Patent Publication No. 2004-61925 Japanese Patent Application Laid-Open No. 2004-126211 Japanese Laid-Open Patent Publication No. 2009-8754 International Publication No. 2007/138870 Japanese Laid-Open Patent Publication 2008-15155 Japanese Unexamined Patent Publication No. 2009-139922

The present invention relates to a liquid crystal sealing agent which is cured only by heating or light heat combination, and because the reaction by heat is fast, it is very low in contamination to the liquid crystal through the process, and also excellent in storage stability, and in terms of moisture resistance and reliability. The liquid crystal sealing agent for liquid crystal dropping methods which is excellent also in cargo characteristic is proposed.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, as for the present inventors, curable resin which consists of 1 type (s) or 2 or more types chosen from an epoxy resin, a (meth) acrylic epoxy resin, and a partial (meth) acrylic epoxy resin which has active hydrogen in a molecule | numerator (but active The liquid crystal sealing agent containing hydrogen as a hydrogen group except for hydrogen) is excellent in the said thermal reactivity, As a result, it was found that liquid crystal contamination can also be suppressed, Furthermore, it was found that it is also excellent in storage stability, and this invention Came to complete.

That is, this invention relates to following 1) -13). In addition, in this specification, with respect to component (a), "(a) 1 type or 2 types chosen from an epoxy resin, (meth) acrylic epoxy resin, and partial (meth) acrylic epoxy resin which have active hydrogen in a molecule | numerator In order to avoid the trouble of describing "curable resin which consists of the above", it may describe as "component (a) curable resin."

One)

(a) Curable resin which consists of 1 type (s) or 2 or more types chosen from an epoxy resin, (meth) acrylic epoxy resin, and partial (meth) acrylic epoxy resin which have active hydrogen in a molecule | numerator (however, a hydroxyl group as active hydrogen) Hydrogen contained in) is excluded), and (b) a thermosetting agent, the liquid crystal sealing agent characterized by the above-mentioned.

2)

Liquid crystal sealing agent as described in said 1) whose said component (a) is a (meth) acrylic epoxy resin which has active hydrogen in a molecule | numerator.

3)

Liquid crystal sealing agent as described in said 1) or 2) whose said component (a) is a (meth) acrylic epoxy resin which has a carboxyl group, a sulfanyl group, or an amino group in a molecule | numerator.

4)

The liquid crystal sealing agent in any one of said 1) -3) whose said component (a) is a (meth) acrylic epoxy resin which has a carboxyl group in a molecule | numerator.

5)

Liquid crystal sealing agent in any one of said 1) -4) whose said component (a) is an acrylated resorcinol diglycidyl ether which has a carboxyl group in a molecule | numerator.

6)

(C) Curable resin which consists of 1 type (s) or 2 or more types chosen from an epoxy resin, a (meth) acrylic epoxy resin, and a partial (meth) acrylic epoxy resin which do not have active hydrogen in a molecule | numerator (however, active hydrogen The liquid crystal sealing agent in any one of said 1) -5) containing the hydrogen contained in a hydroxyl group as an exclusion).

7)

The liquid crystal sealing agent in any one of said 1) -6) which is 5 mass parts-50 mass parts when content of the said component (a) makes the total amount of liquid crystal sealing agent 100 mass parts.

8)

Liquid crystal sealing agent in any one of said 1) -7) whose said component (b) thermosetting agent is a polyhydric hydrazide compound.

9)

Liquid crystal sealing agent of said 8) whose said component (b) thermosetting agent is 1 or 2 or more hydrazide compounds represented by following formula (1).

[Chemical Formula 1]

[In formula, R <^1> -R <^3> is respectively independently a hydrogen atom or following formula (2).

(2)

(Wherein n represents an integer of 1 to 6)

Represents a molecular skeleton represented by

10)

Furthermore, the liquid crystal sealing agent in any one of said 1) -9) containing (d) silane coupling agent.

11)

Furthermore, the liquid crystal sealing agent in any one of said 1) -10) containing (e) inorganic filler.

12)

Furthermore, the liquid crystal sealing agent in any one of said 1) -11) containing (f) photoinitiator.

13)

The liquid crystal display cell sealed with the hardened | cured material obtained by hardening | curing the liquid crystal sealing agent in any one of said 1) -12).

Since the reaction rate at the time of thermosetting is quick, the liquid crystal sealing agent of this invention has sufficient sclerosis | hardenability even under the wiring which light is hard to reach in the light-heat combined use type liquid crystal dropping method, for this reason, It is possible to ensure the manufacture of a highly reliable liquid crystal display panel, and furthermore, it is possible to apply to the liquid crystal dropping method of curing the liquid crystal sealing agent only by heat.

The liquid crystal sealing agent of this invention uses curable resin which consists of 1 type (s) or 2 or more types chosen from an epoxy resin, (meth) acrylic epoxy resin, and partial (meth) acrylic epoxy resin which have active hydrogen in a component (a) molecule. It contains. However, in the analysis of the active hydrogen, hydrogen contained in the hydroxyl group is excluded. Since a hydroxyl group generally has a large acid dissociation constant (pKa) and the nucleophilicity of the hydroxyl group itself is weak, it is difficult to function as a catalyst. In practice conventional epoxyacrylates have secondary hydroxyl groups, but do not function as reaction catalysts upon thermal curing. In this invention, favorable thermal reactivity can be implement | achieved by having this curable resin. In addition, since the curable resin has a functional group that reacts with light or heat such as a (meth) acryloyl group or an epoxy group, the amount of the curable resin that is accepted in the cured product and dissolved in the liquid crystal can be suppressed dramatically, It does not impair display characteristics.

In addition, in this specification, "(meth) acryl" means one or both of "acryl" and "methacryl". In addition, in this specification, "(meth) acryloyl" means the one or both of "acryloyl" and "methacryloyl".

As said active hydrogen, active hydrogen contained in a carboxyl group, a sulfanyl group, an amino group, a sulfo group, a phospho group, etc. are mentioned. That is, as said component (a), for example, the (meth) acrylic epoxy resin and partial (meth) acrylic epoxy resin which have a carboxyl group, a sulfanyl group, an amino group, a sulfo group, a phospho group, etc. in a molecule | numerator, and a carboxyl group in a molecule | numerator, Curable resin containing 1 type (s) or 2 or more types chosen from the epoxy resin which has a thiol group, an amino group, a sulfo group, a phospho group, etc. is mentioned. Among the functional groups containing active hydrogen, a carboxyl group, a thiol group, an amino group is preferable, and a carboxyl group is particularly preferable from the function as a catalyst and the ease of synthesis. For example, as an epoxy resin which has an amino group, amine modified bisphenol A-type epoxy acrylate EBECRYL3703 (made by Daicel Cytec Co., Ltd.) etc. can be obtained easily as a commercial item.

As curable resin of a component (a), a (meth) acrylic-ized epoxy resin is more preferable than an epoxy resin or a partial (meth) acrylic-ized epoxy resin. Since the (meth) acrylated epoxy resin reacts quickly with light, it is possible to further suppress dissolution into liquid crystal. This curable resin can be obtained by making an acid anhydride, polyhydric carboxylic acid, etc. react with the (meth) acrylic epoxy resin obtained by well-known reaction of an epoxy resin and (meth) acrylic acid, for example.

Specifically, first, a predetermined equivalent ratio of (meth) acrylic acid, a catalyst (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstilbin and the like), and polymerization are carried out in an epoxy resin. An inhibitor (for example, metoquinone, hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene, etc.) is added, for example, a (meth) acrylic epoxy by performing esterification reaction at 80-110 degreeC. Obtain the resin. An acid anhydride is reacted with the obtained (meth) acrylic epoxy resin by the method of Unexamined-Japanese-Patent No. 49-2601, Unexamined-Japanese-Patent No. 3-143911, Unexamined-Japanese-Patent No. 5-32746, etc., for example. The (meth) acrylated epoxy resin which has active hydrogen in a molecule | numerator can be obtained. Here, although it does not specifically limit as an epoxy resin used as a raw material, A bifunctional or more epoxy resin is preferable, For example, resorcinol diglycidyl ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S Epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type Epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, phenol novolak type epoxy resin having triphenol methane skeleton, and other diglycidyl ethers of bifunctional phenols And diglycidyl ether compounds of difunctional alcohols, and their halides and hydrogenated substances. Among these, resorcinol diglycidyl ether, bisphenol A type epoxy resin, and bisphenol F type epoxy resin are preferable, and resorcinol diglycidyl ether is especially preferable.

When content of a component (a) makes the total amount of the liquid crystal sealing agent of this invention 100 mass parts, it is preferable that they are 5 mass parts-50 mass parts, and it is especially preferable that they are 5 mass parts-30 mass parts. When the component (a) is too small, sufficient thermosetting is not obtained. On the contrary, when the component (a) is excessively large, the liquid crystal sealing agent becomes high in viscosity, which causes a limitation in the blending of other components.

Although the thermosetting agent which is the component (b) used as a liquid crystal sealing agent of this invention is not specifically limited, A polyhydric amine, a polyhydric phenol, a hydrazide compound, etc. are mentioned, A polyhydric hydrazide compound is used especially preferably. . For example, aromatic hydrazide such as terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,6-pyridine dihydrazide, 1,2,4-benzene Trihydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, pyromellitic acid tetrahydrazide, and the like. Moreover, if it is an aliphatic hydrazide compound, For example, form hydrazide, acetohydrazide, propionic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydride, for example. Dragizide, adipic dihydrazide, pimelic acid dihydrazide, 1,4-cyclohexanedihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, imino diacetic acid dihydrazide, N, N '-Hexamethylenebis semicarbazide, trihydrazide citrate, nitriloacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1,3-bis (hydrazinocarbonoethyl) -5 -A dihydrazide compound having a hydantoin skeleton such as isopropyl hydantoin, preferably a valinhydantoin skeleton (skeleton in which the carbon atom of the hydantoin ring is substituted with an isopropyl group), the above formula The compound etc. which are represented by (1) are mentioned. As a compound represented by said (1), for example, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, and tris (2-hydr) Lazinocarbonylethyl) isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanurate, bis (2-hydrazinocarbonylethyl) isocyanurate, etc. may be mentioned. If it is a structure of 1), it is not limited to these. From the balance of curing reactivity and latentness, isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2 -Hydrazinocarbonylethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanurate, and particularly preferably Tris (2-hydrazinocarbonylethyl) isocyanurate.

When content of a component (b) makes the total amount of the liquid crystal sealing agent of this invention 100 mass parts, it is preferable that they are 1 mass part-20 mass parts, More preferably, they are 2 mass parts-15 mass parts, Two types You may mix and use the above.

The liquid crystal sealing agent of this invention consists of 1 type, or 2 or more types chosen from an epoxy resin, a (meth) acrylic epoxy resin, and a partial (meth) acrylic epoxy resin which do not have active hydrogen in a molecule as a component (c). You may contain resin (however, hydrogen contained in a hydroxyl group as active hydrogen is excluded). Examples thereof include epoxy resins, mixtures of epoxy resins and (meth) acrylated epoxy resins, (meth) acrylated epoxy resins, and partially (meth) acrylated epoxy resins. It is preferable that all the components (c) used by this invention are low in contamination and solubility with respect to a liquid crystal, and examples of a preferable epoxy resin include bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, and phenol furnace. Volac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain type epoxy resin, glycidyl ester type epoxy resin, hydantoin type Epoxy resins, isocyanurate type epoxy resins, phenol novolac type epoxy resins having a triphenol methane skeleton, diglycidyl ether compounds of difunctional phenols, diglycidyl ether compounds of difunctional alcohols, and These halides, hydrogenated substances, etc. are mentioned, It is not limited to these. A (meth) acryloylated epoxy resin and a partial (meth) acryloylated epoxy resin can be obtained by well-known reaction of an epoxy resin and (meth) acrylic acid. For example, a predetermined equivalent ratio of (meth) acrylic acid, a catalyst (e.g., benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstilbin, etc.), and an polymerization inhibitor in an epoxy resin (For example, metoquinone, hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene, etc.) is added, and it is obtained by performing esterification reaction at 80-110 degreeC, for example. Although it does not specifically limit as an epoxy resin used as a raw material, A bifunctional or more functional epoxy resin is preferable, For example, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a bisphenol S-type epoxy resin, a phenol novolak-type epoxy resin , Cresol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester epoxy resin, hydantoin epoxy resin, iso Cyanurate type epoxy resins, phenol novolac type epoxy resins having a triphenol methane skeleton, diglycidyl ether compounds of difunctional phenols, diglycidyl ether compounds of difunctional alcohols, their halides, hydrogen Additives etc. are mentioned. Of these, bisphenol-type epoxy resins and novolak-type epoxy resins are more preferable from the viewpoint of liquid crystal contamination. The ratio of the epoxy group to the (meth) acryloyl group is not limited, and is appropriately selected from the viewpoints of process suitability and liquid crystal stain resistance.

When the liquid crystal sealing agent of this invention contains a component (c), the usage-amount is appropriately determined in consideration of the workability and physical property of the liquid crystal sealing agent obtained. Usually, when the total amount of liquid crystal sealing agent is 100 mass parts, it is preferable that they are 20 mass parts-80 mass parts, More preferably, they are 30 mass parts-70 mass parts.

In the liquid crystal sealing agent of this invention, adhesive strength improvement and moisture-proof reliability improvement can be aimed at using a component (d) silane coupling agent. Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, and the like. When content which occupies for the liquid crystal sealing agent of a silane coupling agent (d) makes the total amount of the liquid crystal sealing agent of this invention 100 mass parts, 0.05 mass part-3 mass parts are preferable.

In the liquid crystal sealing agent of this invention, adhesive strength improvement and moisture-proof reliability improvement can be aimed at using a component (e) inorganic filler. As this (e) inorganic filler, fused silica, crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide , Magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum bisulfide, asbestos, etc., preferably fused silica, crystalline silica, silicon nitride, boron nitride , Calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, aluminum silicate, more preferably fused silica, crystalline silica, alumina, talc. These inorganic fillers may be used by mixing two or more kinds. If the average particle diameter is too large, 3 m or less is appropriate, and preferably 2 m or less, since the average particle diameter causes defects such as gap formation during bonding of the upper and lower glass substrates at the time of manufacturing a narrow gap liquid crystal cell. to be. The particle diameter can be measured by a laser diffraction scattering particle size distribution analyzer (dry) (manufactured by Seishin Corporation; LMS-30).

Content in the liquid crystal sealing agent of the inorganic filler (e) which can be used as a liquid crystal sealing agent of this invention is 3 mass parts-60 mass parts normally when the total amount of the liquid crystal sealing agent of this invention is 100 mass parts, It is preferable. Preferably it is 5 mass parts-50 mass parts. When the content of the inorganic filler is too small, the bonding strength to the glass substrate is lowered and the moisture resistance reliability is also poor, so that the lowering of the bonding strength after moisture absorption is also increased. On the other hand, when there is too much content of an inorganic filler, it may not be crushed well and the gap formation of a liquid crystal cell may become impossible.

The liquid crystal sealing agent of this invention may contain the component (f) radical photopolymerization initiator, in order to make it the curable liquid crystal sealing compound for photothermal combinations. The radical photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals by irradiation of UV or visible light and initiates a chain polymerization reaction. Examples thereof include benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, and diethyl thi. Oxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane, 2, 4, 6- trimethyl benzoyl diphenyl phosphine oxide, etc. are mentioned. Moreover, it is preferable to use the thing which has a (meth) acryloyl group in a molecule | numerator from a liquid-crystal contamination property, for example, 2-methacryloyl oxyethyl isocyanate and 1- [4- (2-hydroxyethoxy ) -Phenyl] -2-hydroxy-2methyl-1-propane-1-one is preferably used. This compound can be prepared by the method described in WO 2006/027982.

Content in the liquid crystal sealing agent of the component (f) photoinitiator which can be used as a liquid crystal sealing agent of this invention is 0.5 mass part-20 mass parts normally, when the total amount of the liquid crystal sealing agent of this invention is 100 mass parts. Preferably, they are 1 mass part-15 mass parts.

In the liquid crystal sealing agent of this invention, you may use the monomer and oligomer of (meth) acrylic acid ester further as needed. Examples of such monomers and oligomers include reactants of dipentaerythritol and (meth) acrylic acid, reactants of dipentaerythritol caprolactone and (meth) acrylic acid, and the like. It is not particularly limited.

The liquid crystal sealing agent of this invention can further mix | blend hardening accelerators, organic fillers, such as an organic acid and imidazole, and additives, such as a pigment, a leveling agent, an antifoamer, and a solvent, as needed.

As an example of a method of obtaining the liquid crystal sealing agent of the present invention, there is the following method. First, (c) component and (f) component are heat-dissolved as needed for (a) component. Subsequently, after cooling to room temperature, (b) component is added, (d) component, (e) component, and an organic filler, an antifoamer, a leveling agent, a solvent, etc. are added as needed, and a well-known mixing apparatus, for example The liquid crystal sealing agent of this invention can be manufactured by mixing uniformly with three rolls, a sand mill, a ball mill, etc., and filtering by a metal mesh.

The liquid crystal display cell of this invention arrange | positions a pair of board | substrates which provided the predetermined electrode in the board | substrate at predetermined intervals, seals the circumference with the liquid crystal sealing agent of this invention, and liquid crystal was enclosed in the clearance gap. The type of the liquid crystal to be enclosed is not particularly limited. Here, a board | substrate is comprised with the combination board | substrate which has light transmittance in at least one which consists of glass, quartz, a plastic, silicon, etc. As the manufacturing method, after adding a spacer (gap control material), such as glass fiber, to the liquid crystal sealing agent of this invention, the liquid crystal sealing agent is apply | coated to one of the pair of board | substrates using a dispenser, a screen printing apparatus, etc. After that, temporary curing is performed at 80 ° C to 120 ° C as necessary. Thereafter, liquid crystal is dropped on the inside of the bank of the liquid crystal sealing agent, and the other glass substrate is superposed in a vacuum to form a gap. After gap formation, the liquid crystal display cell of this invention can be obtained by hardening at 90 degreeC-130 degreeC for 1 hour-2 hours. When used as a photothermal additive type, ultraviolet rays are irradiated to the liquid crystal seal part by an ultraviolet ray irradiator to effect photo curing. The ultraviolet irradiation dose is preferably 500 mJ / cm 2 to 6000 mJ / cm 2, and more preferably 1000 mJ / cm 2 to 4000 mJ / cm 2. Then, the liquid crystal display cell of this invention can be obtained by hardening at 90 degreeC-130 degreeC for 1-2 hours as needed. The liquid crystal display cell of the present invention thus obtained is free of display defects due to liquid crystal contamination, and is excellent in adhesion and humidity resistance reliability. As a spacer, glass fiber, silica beads, polymer beads, etc. are mentioned, for example. The diameter varies depending on the purpose, but is usually 2 µm to 8 µm, preferably 4 µm to 7 µm. The usage-amount is 0.1-4 mass parts normally with respect to 100 mass parts of liquid crystal sealing agents of this invention, Preferably it is 0.5-2 mass parts, More preferably, it is about 0.9-1.5 mass parts.

The liquid crystal sealing agent of this invention is very favorable in thermosetting, and it hardens | cures rapidly in the heating process in the liquid crystal dropping method. Therefore, the dissolution of the constituent components into the liquid crystal is very small, and it is possible to reduce the display defect of the liquid crystal display cell. In addition, since it is excellent in storage stability, it is suitable for the production of a liquid crystal display cell. Further, since the cured product is excellent in various cured properties such as adhesive strength, heat resistance and moisture resistance, it is possible to manufacture a liquid crystal display cell having excellent reliability by using the liquid crystal sealing agent of the present invention. The liquid crystal display cell manufactured using the liquid crystal sealing material of the present invention also satisfies the characteristics required for a liquid crystal display cell having a high voltage holding ratio and a low ion density.

Example

Hereinafter, the present invention will be described in more detail by way of Synthesis Examples and Examples, but the present invention is not limited to these Examples. In addition, unless otherwise indicated, it is a mass reference | standard that it is "part" and "%" in a main body.

Synthesis Example 1 Synthesis of Epoxyacrylate of Bisphenol A-type Epoxy Resin

282.5 g of bisphenol A type epoxy resins (product name: YD-8125, manufactured by Shinnitetsu Chemical Co., Ltd.) were dissolved in 266.8 g of toluene, 0.8 g of dibutylhydroxytoluene was added thereto, and the temperature was raised to 60 ° C. Then, 117.5 g of 100% equivalent of acrylic acid of an epoxy group was added, it heated up to 80 degreeC again, 0.6 g of trimethylammonium chloride which is a reaction catalyst was added to this, and it stirred at 98 degreeC for about 30 hours, and obtained the reaction liquid. . The reaction solution was washed with water and toluene was distilled off to obtain 395 g of an epoxy acrylate (acrylated bisphenol A epoxy resin) of the desired type (KAYARAD ^RTM R-93100).

Synthesis Example 2: Synthesis of Acid Anhydride Adduct of Bisphenol A-type Epoxyacrylate

4.84 g of bisphenol A type epoxy acrylate obtained in the synthesis example 1, 0.049 g of 4-dimethylamino pyridine, 6.07 g of triethylamine, and 1000 ml of methylene chloride were added, and it stirred and dissolved at room temperature, and then 18.3 g of tetrahydro phthalic anhydride was added. Added and stirred at room temperature for 3 hours. After wash | cleaning the obtained reaction liquid 6 times, methylene chloride was distilled off and 7 g of bisphenol-A epoxy acrylates which have a carboxyl group were obtained in a molecule | numerator. LC MS (m / z) = 787 (MH), IR 1709 cm- ¹ (COOH).

[Synthesis example 3: synthesis | combination of acrylated resorcin diglycidyl ether]

181.2 g of resorcinin diglycidyl ether (Nagase Chemtex Co., Ltd.) was dissolved in 266.8 g of toluene, 0.8 g of dibutylhydroxytoluene was added to this as a polymerization inhibitor, and it heated up to 60 degreeC. Then, 117.5 g of 100% equivalent of acrylic acid of an epoxy group was added, it heated up to 80 degreeC again, 0.6 g of trimethylammonium chloride which is a reaction catalyst was added to this, and it stirred at 98 degreeC for about 30 hours, and obtained the reaction liquid. . The reaction liquid was washed with water and toluene was distilled off to obtain 253 g of an epoxy acrylate (acrylated resorcin diglycidyl ether) of the desired resorcinin diglycidyl ether.

[Synthesis example 4: synthesis | combination of the acid anhydride adduct of acrylated resorcin diglycidyl ether]

3.66 g of epoxy acrylate of resorcin diglycidyl ether obtained in Synthesis Example 3, 0.049 g of 4-dimethylaminopyridine, 6.07 g of triethylamine, and 1000 ml of methylene chloride were added thereto, followed by stirring at room temperature to dissolve. 11.8 g of acid were added and stirred at room temperature for 2 hours. After washing the obtained reaction liquid 6 times, methylene chloride was distilled off and 5 g of acrylated resorcinol diglycidyl ether which has a carboxyl group in a molecule | numerator was obtained. LC MS (m / z) = 561 (MH), IR 1705 cm ⁻¹ (COOH).

[Examples 1-3 and Comparative Examples 1-4]

After mixing and stirring each curable resin component (component (a), (c)) in the ratio shown in following Table 1, it melt | dissolved by heating at 90 degreeC. After heating and dissolving a radical photopolymerization initiator (component (f)) there, it is cooled to room temperature, and a silane coupling agent (component (d)), an inorganic filler (component (e)), and a thermosetting agent (component (b)) After adding and stirring, it disperse | distributed with three roll mills, it filtered by the metal mesh (635 mesh), and prepared the sealing compound for liquid crystal dropping methods of Examples 1-3.

In addition, curable resin component (component (c)) was heated at 90 degreeC by the ratio shown to following Table 1 similarly. After heating and dissolving a radical photopolymerization initiator (component (f)) there, it is cooled to room temperature, and a silane coupling agent (component (d)), an inorganic filler (component (e)), and a thermosetting agent (component (b)) After adding and stirring a hardening accelerator, it disperse | distributed with three roll mills, was filtered by the metal mesh (635 mesh), and the sealing compound for liquid crystal dropping methods of Comparative Examples 1-4 was prepared.

The evaluation test was conducted in the following manner.

(Measurement of adhesive strength)

1 g of 5 micrometers glass fiber was added to 100 g of the obtained liquid crystal sealing agent as a spacer, and it stirred and mixed. After apply | coating this liquid crystal sealing agent on the glass substrate of 50 mm x 50 mm, bonding the glass piece of 1.5 mm x 1.5 mm on this liquid crystal sealing agent, and irradiating the ultraviolet-ray of 3000 mJ / cm <2> with a UV irradiator, oven It was thrown in and thermosetted at 120 degreeC for 1 hour. The shear adhesive strength of the glass piece was measured by the bond tester (SS-30WD: Seisin Corporation make). The results are shown in Table 1.

(Measurement of moisture-proof adhesive strength)

The same measurement sample as in the above adhesive strength test was prepared. After the measurement sample was put into a pressure cooker tester (TPC-411: manufactured by Tabbyespec Co., Ltd.) for 12 hours under conditions of 121 ° C, 2 atmospheres, and a humidity of 100%, the shear bond strength of the glass piece was measured by the bond tester. It was. The results are shown in Table 1.

(Moisture absorption measurement)

The obtained liquid crystal sealing agent was sandwiched between polyethylene terephthalate (PET) films and formed into a thin film having a thickness of 100 μm, and then irradiated with ultraviolet light of 3000 mJ / cm 2 by a UV irradiator, and then put into an oven and thermally cured at 120 ° C. for 1 hour. After hardening, PET film was peeled off and it was set as the sample. After measuring the weight of the sample, it was left to stand in 60 degreeC and 90% RH environment for 12 hours, and the weight measurement was performed again. Table 1 shows the weight change rate (%) with respect to the initial weight.

(Port life measurement)

The viscosity change of the obtained liquid crystal sealing agent at 25 캜 was measured. The viscosity measurement after leaving for 72 hours on 25 degreeC and 50 RH% conditions was performed, and the viscosity increase rate (%) with respect to initial stage viscosity was calculated | required. The results are shown in Table 1.

(Production of liquid crystal cell for evaluation)

An alignment film liquid (PIA-5540-05A; manufactured by Chisso Co., Ltd.) was applied to the substrate having the transparent electrode formed thereon, followed by firing and rubbing treatment. Liquid crystal sealing agent was dispensed to this board | substrate so that the line | wire width after bonding might be set to 1 mm, and it was set as the main seal and dummy seal, and the microdroplets of liquid crystal (JC-5015LA; Chisso Corporation) were dripped in the frame of the seal pattern. An in-plane spacer (Nosuko spacer KSEB-525F; manufactured by NUSCO CORPORATION; a gap width of 5 占 퐉 after the bonding) was dispersed and thermally fixed on the substrate subjected to another rubbing treatment, and the liquid crystal was dropped . After opening to form a gap and masking only in a seal pattern frame, after irradiating 50 mJ / cm <2> of ultraviolet-rays with a UV irradiator, it put into oven and thermosetted at 120 degreeC for 1 hour, and manufactured the liquid crystal test cell for evaluation It was.

The insertion resistance of the seal of the produced liquid crystal cell for evaluation and the liquid-crystal orientation disorder of the seal vicinity were observed with the polarization microscope, and evaluation was performed according to the criteria shown below about insertion resistance and liquid crystal orientation of the seal vicinity. The results are shown in Table 1.

(Evaluation of Insertion Resistance)

(Double-circle): The insertion of the liquid crystal with respect to a seal is less than 0.2 mm, and it is a level which does not have any problem in sealing of a liquid crystal.

(Circle): Insertion of the liquid crystal with respect to a seal is 0.2 mm or more and less than 0.4 mm, and it is a level which does not have any problem in sealing of a liquid crystal.

(Triangle | delta): The insertion of the liquid crystal with respect to a seal is 0.4 mm or more and less than 0.6 mm, and it is a level which does not have any problem in sealing of a liquid crystal.

X: Insertion of the liquid crystal with respect to a seal is 0.6 mm or more and less than 1.0 mm, and it is a level which does not have any problem in sealing of a liquid crystal.

XX: The seal is broken, and the cell can not be formed.

(Evaluation of Liquid Crystal Alignment Near the Seal)

?: The alignment disorder of the liquid crystal is less than 0.2 mm from the seal.

?: The alignment disturbance of the liquid crystal is 0.2 mm or more and less than 0.4 mm from the seal.

?: The alignment disorder of the liquid crystal is 0.4 mm or more and less than 0.6 mm from the seal.

X: The alignment disorder of the liquid crystal is 0.6 mm or more and less than 1.0 mm from the seal.

XX: The seal is broken, and the cell can not be formed.

(Cure speed measurement)

The liquid crystal sealant thus obtained was measured for its complex viscosity ratio using a dynamic viscoelasticity measurement apparatus (Rheosol-G5000, manufactured by Ubitech Co., Ltd.). The setting of the dynamic viscosity modulus measuring device is as follows. Cone: Parallel cone having a diameter of 20 mm, frequency: 1 Hz, deformation angle: 3 deg. The temperature was raised from 30 ° C to 120 ° C at a rate of 18 ° C / minute, and then maintained at 120 ° C. Table 1 shows the time when the viscosity reached 10000 Pa · s.

From the result of Table 1, the comparative example 1 which does not contain a hardening accelerator component is inferior to sclerosis | hardenability, and, as a result, has generate | occur | produced orientation defect in panel display characteristic. Moreover, although the CIC acid, the dodecane diacid, and the thermal radical initiator were used as a hardening accelerator, although the improvement of sclerosis | hardenability is achieved, there exists a problem in liquid-crystal contamination property and moisture-resistant adhesiveness. On the other hand, about Examples 1-3, it is confirmed that other characteristics are also a level which can be used, realizing hardening improvement. In particular, in Examples 1 and 2, very excellent results are shown in all the characteristics.

From these results, it can be said that the liquid crystal sealing agent of this invention is excellent in workability by the point which is excellent in storage stability and sclerosis | hardenability, and is excellent in liquid crystal display cell from the point which is excellent in liquid-crystal contamination property, moisture resistance adhesiveness, and panel display characteristics. It can be said that reliability can be achieved.

Industrial availability

Since the liquid crystal sealing agent of this invention is excellent in workability, it enables the stable production of a liquid crystal display cell, and also contributes to ensuring long-term reliability of a liquid crystal display cell.

Claims

The method according to claim 1,
Liquid crystal sealing agent whose said component (a) is the (meth) acrylic-ized epoxy resin which has active hydrogen in a molecule | numerator.

3. The method according to claim 1 or 2,
Liquid crystal sealing agent whose said component (a) is a (meth) acrylic epoxy resin which has a carboxyl group, a sulfanyl group, or an amino group in a molecule | numerator.

4. The method according to any one of claims 1 to 3,
Liquid crystal sealing agent whose said component (a) is a (meth) acrylic epoxy resin which has a carboxyl group in a molecule | numerator.

5. The method according to any one of claims 1 to 4,
Liquid crystal sealing agent whose said component (a) is acrylated resorcinol diglycidyl ether which has a carboxyl group in a molecule | numerator.

6. The method according to any one of claims 1 to 5,
(C) Curable resin which consists of 1 type (s) or 2 or more types chosen from an epoxy resin, a (meth) acrylic epoxy resin, and a partial (meth) acrylic epoxy resin which do not have active hydrogen in a molecule | numerator (however, active hydrogen Liquid crystal sealing agent containing hydrogen, except for hydrogen contained in a hydroxyl group).

7. The method according to any one of claims 1 to 6,
The liquid crystal sealing agent which is 5 mass parts-50 mass parts when content of the said component (a) makes the total amount of liquid crystal sealing agent 100 mass parts.

8. The method according to any one of claims 1 to 7,
Liquid crystal sealing agent whose said component (b) thermosetting agent is a polyhydric hydrazide compound.

The method of claim 8,
Liquid crystal sealing agent whose said component (b) thermosetting agent is 1 or 2 or more hydrazide compounds represented by following formula (1).
[Chemical Formula 1]

[In formula, R <^1> -R <^3> is respectively independently a hydrogen atom or following formula (2).
(2)

(Wherein n represents an integer of 1 to 6)
Represents a molecular skeleton represented by

10. The method according to any one of claims 1 to 9,
Furthermore, (d) liquid crystal sealing agent containing a silane coupling agent.

11. The method according to any one of claims 1 to 10,
Furthermore, (e) liquid crystal sealing agent containing an inorganic filler.

12. The method according to any one of claims 1 to 11,
Furthermore, (f) liquid crystal sealing agent containing a radical photopolymerization initiator.

The liquid crystal display cell sealed with the hardened | cured material obtained by hardening | curing the liquid crystal sealing agent of any one of Claims 1-12.