CN1798786A - Curable resin composition, sealant for liquid crystal display element, and liquid crystal display element - Google Patents

Abstract

The purpose of the present invention is to provide a curable resin composition which, when used as a sealant for a liquid crystal display element in a process for producing a liquid crystal display element by a liquid crystal dropping filling method, causes little contamination of liquid crystal, has good adhesion to glass, and does not cause cell gap unevenness, a sealant for a liquid crystal display element, and a liquid crystal display element. The curable resin composition of the present invention contains a curable resin that is cured by light and/or heat, and a polymerization initiator, and the curable resin is a crystalline acrylic-modified epoxy resin having a acryloyl group and an epoxy group in one molecule.

Description

Curable resin composition, sealant for liquid crystal display element, and liquid crystal display element

technical field

The present invention relates to less contamination of liquid crystals, good bonding with substrates, and no generation of cells when used as a sealant for liquid crystal display elements in the process of manufacturing liquid crystal display elements by a liquid crystal drop fill process (drop fill process) Curable resin composition with uneven cell gap, sealant for liquid crystal display element, and liquid crystal display element.

Background technique

In the past, liquid crystal display elements such as liquid crystal display units were produced by making two transparent substrates with electrodes facing each other at a predetermined interval, sealing their surroundings with a sealant composed of a curable resin composition, and making the seal The liquid crystal is solidified to form a unit, and then the liquid crystal is injected into the unit from the liquid crystal injection port provided therein, and then the liquid crystal injection port is sealed with a sealant or a sealing agent.

That is, first, on any one of the two transparent substrates with electrodes, a seal pattern is formed by screen printing, and a liquid crystal injection port is provided in the seal pattern using a thermosetting sealant. Pre-bake the sealant to dry the solvent in the sealant. Then, make the two substrates face each other with a spacer in between, align them and stick them together, heat press at 110-220°C for 10-90 minutes, adjust the gap near the sealing part, and then Heat in the furnace at 110-220°C for 10-120 minutes to make the sealant actually cure. Next, liquid crystal is injected through the liquid crystal injection port, and finally the liquid crystal injection port is sealed with a sealing agent, thereby producing a liquid crystal display element.

However, according to this production method, there are the following problems: dislocation due to thermal deformation, uneven gap, decreased adhesion between the sealant and the substrate, etc.; bubbles generated by residual solvent due to thermal expansion, resulting in uneven gap, The seal is damaged; the curing time of the seal is long; the pre-baking process is complicated; the usable time of the sealant is shortened due to the volatilization of the solvent; it takes a long time to inject the liquid crystal, etc. Especially in recent large liquid crystal display elements, it takes a lot of time to inject liquid crystals, and this has become a very serious problem.

On the other hand, the manufacturing method of the liquid crystal display element called the drop filling method using the photocuring heat-curing combination type sealing agent was examined. In the drop-fill method, first, a sealant is printed by screen printing on one of two transparent substrates with electrodes, thereby forming a rectangular seal pattern (sealing portion). Then, liquid crystal droplets are applied dropwise on the entire frame surface of the transparent substrate while the sealant is not cured, and another transparent substrate is laminated immediately thereafter, and the sealed portion is irradiated with ultraviolet rays for provisional curing. Then, during the annealing of the liquid crystal, it is actually cured by heating to produce a liquid crystal display element. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured very efficiently. This drop filling method is expected to become a main method of manufacturing liquid crystal display devices in the future.

However, in the method of manufacturing a liquid crystal display device by the drop filling method, there are several problems that must be overcome.

The first problem is the liquid crystal pollution problem. In the drop filling method, since there is a step in which the uncured sealant directly contacts the liquid crystal, there is a big problem that the sealant component is eluted into the liquid crystal to contaminate the liquid crystal. When liquid crystal contamination occurs, alignment disorder of the liquid crystal occurs around the sealant, which causes display defects such as color unevenness.

For example, as curable resins in curable resin compositions conventionally used as sealants, partial (meth)acryloyl compounds of bisphenol A epoxy resins (Patent Documents 1-5), (methyl ) acrylate resin (Patent Document 6), etc., but since these curable resins have a polarity value close to that of liquid crystal materials, they show a property of easy affinity, so they tend to be eluted into liquid crystals.

In addition, the polymerization initiator mixed in the sealant as an active radical generating agent is also a cause of contamination of liquid crystals. In the past, low-molecular-weight organic compounds were used as polymerization initiators mixed in sealants. Such polymerization initiators were easily eluted in liquid crystals. In addition, residues derived from polymerization initiators remained after polymerization, so the residues passed through The liquid crystal is eluted into the liquid crystal to cause contamination of the liquid crystal, or becomes an outgassed gas due to heating at the time of reorientation of the liquid crystal, causing a decrease in bonding force between glass substrates and generation of gaps.

In view of this, Patent Document 7 discloses a transparent polymer substance formed by polymerization of a transparent polymer substance forming material containing a photopolymerizable composition and a photopolymerization initiator having a (meth)acryloyloxy group. A liquid crystal device supported between two transparent substrates. Since the liquid crystal device does not use a low-molecular-weight polymerization initiator, the residue of the polymerization initiator after the polymerization is difficult to elute in the liquid crystal, thereby improving the display such as disordered liquid crystal orientation and uneven color to some extent. bad question. However, in addition to not being able to completely prevent the elution of the residue in the liquid crystal, it has not yet been solved that the polymerization initiator in contact with the liquid crystal when it is not cured is eluted in the liquid crystal, or the residue of the polymerization initiator after curing has not been solved. The object becomes the problem of outgassing due to the heating when the liquid crystal is re-aligned.

In addition, an alkoxysilane compound mixed as an adhesion aid is also a cause of liquid crystal contamination. As far as previous sealants are concerned, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-isocyanatopropyl Although alkoxysilane compounds such as trimethoxysilane are used as adhesion aids, these alkoxysilane compounds also have the property of being easily eluted in liquid crystals.

The second problem is the bonding property of the sealant. In general, a sealant composed of an ultraviolet curable resin composition has weak bonding force to a glass substrate compared to a conventional sealant composed of a thermosetting resin composition. In addition, in order to improve the heat resistance, the improvement of the sealant tends to increase the glass transition temperature of the resin, but the higher the glass transition temperature of the resin, the lower the adhesion to the glass substrate. A method of adding a silane coupling agent is known as a method of improving adhesion to a glass substrate, but not only the adhesion improvement effect is insufficient, but also the silane coupling agent is eluted in the liquid crystal to cause contamination of the liquid crystal.

Patent Document 8 discloses an epoxy resin adhesive composition containing core-shell particles consisting of a core layer made of a resin with a glass transition temperature of 45°C and a glass The shell layer is composed of a resin with a melting temperature of 105°C. In the thermosetting reaction of the epoxy resin, the rubber component of the core-shell particles swells due to heating and absorbs external impact to improve the impact resistance of the resin composition, thereby improving the peel bonding force. However, since this method is based on the premise that the core-shell particles are swollen by heating, the UV-curable resin composition (or in the combination of UV-curable and thermal-curable compositions, the substance that is first UV-cured ) may not be effective in improving the joinability.

The third problem is the problem of uneven gaps. When manufacturing a liquid crystal display device by the drop filling method, the curability of conventional sealants by photocuring may be too high, and the linear expansion coefficient after photocuring may become large, and unevenness of the cell gap may occur due to substrate misalignment. And other issues.

Accordingly, there is a need for a curable resin composition that can be used for a liquid crystal display element sealant that has solved the problem of liquid crystal contamination, adhesiveness of the sealant, and gap unevenness.

Patent Document 1: Japanese Unexamined Patent Publication No. 6-160872

Patent Document 2: Japanese Unexamined Patent Publication No. 1-243029

Patent Document 3: Japanese Unexamined Patent Publication No. 7-13173

Patent Document 4: Japanese Unexamined Patent Publication No. 7-13174

Patent Document 5: Japanese Unexamined Patent Publication No. 7-13175

Patent Document 6: JP-A-7-13174

Patent Document 7: Japanese Unexamined Patent Publication No. 5-264980

Patent Document 8: JP-A-7-224144

Contents of the invention

In view of the above circumstances, the object of the present invention is to provide a liquid crystal display element when used as a liquid crystal display element sealant in the process of manufacturing a liquid crystal display element by the drop filling method, which has little pollution to the liquid crystal, good adhesion with the substrate, and does not produce Curable resin composition with uneven cell gap, sealant for liquid crystal display element, and liquid crystal display element.

The inventors of the present invention have intensively studied the problem of liquid crystal contamination, and found that by selecting specific curable resins, polymerization initiators, and adhesion aids, even uncured liquid crystals can be obtained when used as a sealant for liquid crystal display elements. A curable resin composition that does not easily contaminate liquid crystals even when in contact with liquid crystals in this state has completed the first, second and third inventions so far. Among them, the first present invention solves the problem of liquid crystal contamination caused by curable resins, the second present invention solves the problem of liquid crystal contamination caused by polymerization initiators, and the third present invention solves the problem of liquid crystal contamination caused by adhesion aids. The problem of liquid crystal contamination. Therefore, the present inventions 1-3 can be implemented independently, but when several implementations are combined, better effects can be obtained.

The first present invention is a curable resin composition comprising a curable resin cured by light and/or heat and a polymerization initiator. A (meth)acrylic modified epoxy resin formed by the reaction of oxygen resin and (meth)acrylic acid.

(Meth)acryl-modified epoxy resin has (meth)acryloyl group (acryl) and epoxy group in one molecule, so it can be cured by light or heat. Therefore, if the curable resin composition of the first present invention is used as a sealant for liquid crystal display elements, it can be temporarily sealed by irradiating light and then cured by heating. method for the manufacture of liquid crystal display elements.

Such a (meth)acrylic-modified epoxy resin may hardly contaminate liquid crystals because the crystalline epoxy resin used as a raw material has high purity and a low impurity content. In addition, (meth)acrylic acid in this specification means acrylic acid or methacrylic acid. In addition, the so-called crystalline resin in the description of the present invention refers to a resin with a sharp and clear melting point peak and a crystallinity of more than 10% when measuring differential heat with a differential scanning calorimeter. Resin with no sharp and clear melting point peak and crystallinity of 10% or less when measured by scanning calorimeter.

The aforementioned (meth)acrylic-modified epoxy resin is preferably crystalline. Since the crystalline (meth)acrylic-modified epoxy resin has high crystallinity, the intermolecular interaction is strong, and even if the uncured resin comes into contact with the liquid crystal, it may hardly contaminate the liquid crystal.

The above-mentioned (meth)acrylic-modified epoxy resin preferably has a melting point of 80° C. or lower. When it exceeds 80 degreeC, it will be necessary to heat at high temperature at the time of mixing, and problems, such as gelatinization, will arise. A preferable lower limit is 40°C. If it is less than 40° C., the cohesive strength may decrease, and the adhesiveness of the cured product obtained by curing the curable resin composition of the present invention may decrease.

The aforementioned (meth)acrylic acid-modified epoxy resin is preferably a resin in which the total number of sulfur atoms and oxygen atoms in the resin skeleton is 5-10. If it is less than 5, the polarity of molecules may become low and liquid crystals may be easily contaminated, and if it exceeds 10, moisture resistance may be poor.

The preferable lower limit of the value obtained by dividing the total number of sulfur atoms and oxygen atoms in the resin skeleton by the total number of atoms of the (meth)acrylic modified epoxy resin is 0.08, and the preferable upper limit is 0.14. If it is less than 0.08, the polarity may become low and the liquid crystal may be easily contaminated, and if it exceeds 0.14, the moisture resistance may be poor.

The said (meth)acryl-modified epoxy resin can be manufactured by making a crystalline epoxy resin and (meth)acrylic acid react.

The above-mentioned crystalline epoxy resin is not particularly limited, and examples thereof include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, hydroquinone epoxy resins, and biphenyl epoxy resins. Oxygen resins, stilbene-type epoxy resins, sulfide-type epoxy resins, ether-type epoxy resins, naphthalene-type epoxy resins, and derivatives thereof.

The melting point of the crystalline epoxy resin used as the above raw material is preferably 140° C. or lower. If it exceeds 140°C, gelation may occur during the modification reaction. A more preferable upper limit is 120°C. In addition, a preferable lower limit is 40°C. If it is lower than 40 degreeC, crystallinity may fall.

The method for reacting the crystalline epoxy resin and (meth)acrylic acid is not particularly limited, and conventionally known methods can be used.

When the above-mentioned crystalline epoxy resin and (meth)acrylic acid are reacted, it is preferable to use a basic catalyst. The above-mentioned basic catalyst is not particularly limited, and examples thereof include N,N-dimethylaniline, triethylamine, triethylamine, and triethylamine. Phenylphosphine, ferric chloride, zinc chloride, vanadium chloride, etc.

In addition, when the above-mentioned crystalline epoxy resin and (meth)acrylic acid are reacted, it is preferable to react 1-0.5 equivalent of (meth)acrylic acid with respect to 1 equivalent of epoxy group in the presence of the above-mentioned basic catalyst.

In curable resin composition of 1st this invention, the preferable minimum of the compounding quantity of the said (meth)acryl-modified epoxy resin is 10 weight%, and the preferable upper limit is 50 weight%. If it is less than 10% by weight, the adhesiveness of the cured product obtained by curing may decrease, and if it exceeds 50% by weight, the composition may crystallize.

The curable resin composition of the present invention may contain other curable resins other than the above-mentioned (meth)acryl-modified epoxy resin.

Examples of such curable resins include (meth)acrylates, vinyl derivatives, styrene derivatives, and epoxy resins. Among them, (meth)acrylates, epoxy resins, and oxetane resins are suitable from the viewpoint of rapid reaction and good bonding properties.

It is preferable that the said curable resin has a hydrogen bonding functional group in a molecule|numerator. Thereby, bonding between curable resins can be improved, and it is difficult to contaminate the crystal even when it comes into contact with the crystal. The above-mentioned curable resin preferably has two or more addition-reactive functional groups in the molecule, more preferably two or more and four or less. Thereby, the remaining amount of unreacted resin after curing can be reduced, and it is possible to prevent the unreacted resin from contaminating the liquid crystal.

Examples of the (meth)acrylate include urethane (meth)acrylate having a urethane bond, epoxy (meth)acrylate derived from a compound having a glycidyl group and (meth)acrylic acid, Polyols or polyester polyols containing three or more OH groups in one molecule, (meth)acrylates derived from (meth)acrylic acid with one or more OH groups remaining, etc.

Examples of the urethane (meth)acrylate include diisocyanates such as isophorone diisocyanate and derivatives of reactive compounds capable of addition reaction with isocyanates, such as acrylic acid and hydroxyethyl acrylate, and the like. These derivatives can also be chain-extended with caprolactone and polyols, etc. In addition, examples of commercially available products include U-122P, U-340P, U-4HA, U-1084A (all manufactured by Shin-Nakamura Chemical Co., Ltd.), KRM7595, KRM7610, and KRM7619 (all manufactured by Daicel UCB Co., Ltd.).

Examples of the above-mentioned epoxy (meth)acrylates include epoxy (meth)acrylates derived from bisphenol A epoxy resins and propylene glycol diglycidyl ether, and epoxy (meth)acrylates derived from (meth)acrylic acid. . In addition, examples of commercially available products include EA-1020, EA-6320, and EA-5520 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxy ester 70PA, and epoxy ester 3002A (all manufactured by Kyoeisha Chemical Co., Ltd.). wait.

Examples of (meth)acrylic acid esters derived from polyols or polyester polyols containing three or more OH groups in one molecule and (meth)acrylic acid in a state where one or more OH groups remain are, for example, methyl methacrylate , tetrahydrofurfuryl methacrylate, benzyl methacrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, polyethylene glycol dimethacrylate, 1 , 4-Butanediol Dimethacrylate, 1,6-Hexanediol Dimethacrylate, Trimethylolpropane Triacrylate, Pentaerythritol Triacrylate, Glycerin Dimethacrylate, 2-Hydroxy- 3-acryloxypropyl methacrylate, etc.

The above-mentioned epoxy resin is not particularly limited, and examples thereof include (meth)acryl-modified epoxy resins, urethane-modified (meth)acryloyl epoxy resins, and the like.

Examples of the (meth)acrylic-modified epoxy resins include novolak-type epoxy resins, bisphenol-type epoxy resins, biphenyl-type epoxy resins, naphthalene-type epoxy resins, tris(hydroxyphenyl)alkane Partial (meth)acryloyl compounds such as base type epoxy resin, tetrakis (hydroxyphenyl) alkyl type epoxy resin, cycloaliphatic epoxy resin, etc. Among them, partial (meth)acryloyl compounds of novolak-type epoxy resins are preferable. This is because the storage stability of the sealant and the like of the present invention can be further improved by using a novolac-type epoxy resin as the base resin, compared with a linear bisphenol-type epoxy resin.

The raw material epoxy resin of the above-mentioned (meth)acrylic modified epoxy resin, for example, as the novolac type, phenol novolac type, cresol novolac type, biphenyl novolac type, triphenol novolak type, bisphenol novolak type, etc. Cyclopentadiene novolac type, etc. Bisphenol type includes bisphenol A type, bisphenol F type, 2,2'-diallyl bisphenol A type, hydrogenated bisphenol type, polyoxypropylene bisphenol A-type cycloaliphatic epoxy resin, etc. These may be used alone or in combination of two or more.

As a commercially available product of the above-mentioned epoxy resin, as the above-mentioned bisphenol A type epoxy resin, for example, Epico-To 828, Epico-To 834, Epico-To 1001, Epico-To 1004 (all are Japan Epoxy Resin Co., Ltd. Epicron 850, Epichrome 860, Epichrome 4055 (all manufactured by Dainippon Ink Chemical Industry Co., Ltd.), etc., as the above-mentioned bisphenol F-type epoxy resin, for example, Epico-to 807 (manufactured by Nippon Epoxy Resin Co., Ltd.), Epiclon 830 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), etc., as the phenol novolac type epoxy resin, for example, Epiclon N-740, N-770, N-775 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), 152, 154 (manufactured by Nippon Epoxy Resin Co., Ltd.), etc. Examples of the above-mentioned cresol novolac type include Epiclon N-660, N-665, N-670, N-673, N-680, N-695, N -665-EXP, N-672-EXP (manufactured by Dainippon Ink Chemical Co., Ltd.), etc.

In addition, examples of the above-mentioned cycloaliphatic epoxy resins include Ceroxide 2021, Ceroxide 2080, and Ceroxide 3000 (all manufactured by Daicel UBC), etc., as partial (meth)acrylization of the above-mentioned epoxy resins. Examples thereof include those obtained by reacting an epoxy resin and (meth)acrylic acid in the presence of a basic catalyst by a conventional method.

An epoxy resin having a desired acrylation rate can be obtained by appropriately changing the compounding amount of the above-mentioned epoxy resin and the compounding amount of (meth)acrylic acid. Specifically, the preferred lower limit of the carboxylic acid is 0.1 equivalents, the preferred upper limit is 0.5 equivalents, the more preferred lower limit is 0.2 equivalents, and the more preferred upper limit is 0.4 equivalents to 1 equivalent of the epoxy group.

As the above-mentioned urethane-modified (meth)acryloyl epoxy resin, for example, a resin obtained by reacting a polyhydric alcohol with a difunctional or higher isocyanate and then reacting it with a hydroxyl group-containing (meth)acryl A method of reacting an acryl monomer and glycidol; a method of reacting a (meth)acryloyl monomer or glycidol having a hydroxyl group with a difunctional or higher isocyanate without using a polyol; It is a method of reacting glycidol with an isocyanate group-containing (meth)acrylate monomer.

Specifically, for example, first, 1 mol of trimethylolpropane and 3 mol of isophorone diisocyanate are reacted under a tin-based catalyst. The resin is obtained by reacting isocyanate groups remaining in the obtained compound with hydroxyethyl acrylate as a hydroxyl group-containing acryl monomer and glycidol as a hydroxyl group-containing epoxy compound.

It does not specifically limit as said polyhydric alcohol, For example, ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly)propylene glycol etc. are mentioned.

The above-mentioned isocyanate is not particularly limited as long as it is more than difunctional, and examples thereof include isophorone diisocyanate, 2,4-tolylylene diisocyanate, 2,6-tolylylene diisocyanate, hexamethylene diisocyanate, and hexamethylene diisocyanate. Isocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polycondensed MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, benzidine Diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl)phosphorothioate, tetramethylxylene diisocyanate, 1 , 6,10-undecane triisocyanate, etc.

The hydroxyl group-containing (meth)acrylate monomer is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, Mono(meth)acrylate of dihydric alcohols such as diol; mono(meth)acrylate and di(meth)acrylate of trihydric alcohols such as trimethylolethane, trimethylolpropane, glycerin; Epoxy acrylate such as bisphenol A modified epoxy acrylate, etc. These may be used alone or in combination of two or more.

The second present invention is a curable resin composition containing a curable resin cured by light and/or heat and a polymerization initiator, wherein the polymerization initiator contains in one molecule A radical polymerization initiator that dissociates into two active radical species when irradiated with light and/or heat, and a radical polymerization initiator and a hydrogen-bonding functional group.

In the above-mentioned radical polymerization initiator, the radical polymerization initiator refers to a functional group that dissociates into two active radical species when irradiated with light and/or heat to initiate a radical polymerization reaction. Among them, a radical polymerization initiator having a radical polymerization initiator that dissociates into two active radical species under the action of light is suitable for the drop filling method, and is therefore preferable. Examples of such radical polymerization initiators include carbonyl groups, sulfur-containing groups, azo groups, and organic peroxide-containing groups, among which those represented by the following general formulas (1) to (6) are suitable. Structural groups, etc.

[chemical formula 1]

In the above general formulas (1)-(6), R ¹ , R ² and R ³ each independently represent an alkyl group with 1-6 carbon atoms, a hydrogen atom, a hydroxyl group, an alkoxy group with 1-6 carbon atoms radical, (meth)acryloyl, phenyl, R ⁴ , R ⁵ , R ⁶ and R ⁷ represent a cyano group, an alkyl group with a carbon number of 1-6, a hydrogen atom, a hydroxyl group, and a carbon number of 1-6 An alkoxy group, (meth)acryloyl group, an aromatic ring that may have an alkyl group or a halogen group with a carbon number of 1-6,

[chemical formula 2]

Represents an aromatic ring which may have an alkyl group or a halogen group having 1 to 6 carbon atoms. Among them, groups having structures represented by the above-mentioned general formulas (1)-(4) that are dissociated into active radical species by absorbing relatively weak light are more preferred, and are further preferred from the viewpoint of the generation rate of active radicals. A group having a structure represented by the above general formula (1).

The above-mentioned hydrogen bonding functional group is not particularly limited as long as it is a hydrogen bonding functional group or residue, etc., and examples thereof include OH groups, NH _groups , NHR groups (R represents aromatic or aliphatic hydrocarbons, and these Derivatives), COOH group, _CONH2 group, NHOH group, and groups with residues such as NHCO bond, NH bond, CONHCO bond, NH-NH bond, etc. in the molecule.

Since the radical polymerization initiator has such a hydrogen-bonding functional group, even if the uncured curable resin composition of the second invention contacts liquid crystals, the radical polymerization initiator is difficult to elute, and liquid crystal contamination is less likely to occur.

The above-mentioned radical polymerization initiator preferably contains two or more of the above-mentioned hydrogen-bonding functional groups in one molecule. In addition, it is preferable that both of the two active radical species generated by dissociation of the radical polymerization initiator by irradiation with light and/or heat have at least one hydrogen-bonding functional group. That is, the above-mentioned hydrogen-bonding functional group is preferably arranged in the molecule so that when the radical polymerization initiator is dissociated by irradiation of light and/or heat to generate two active radical species, any active radical species has at least one hydrogen. key functional groups. Thus, even if all the generated active radical species come into contact with the liquid crystal, since the above-mentioned polymerization initiator stays in the curable resin composition, the components of the polymerization initiator are difficult to elute in the liquid crystal, and liquid crystal contamination is less likely to occur.

It is also preferable that the above-mentioned radical polymerization initiator has two or more reactive functional groups in one molecule. By having such a reactive functional group in the molecule, the radical polymerization initiator itself forms a copolymer with the curable resin and is fixed, so that the residue of the polymerization initiator does not elute in the liquid crystal after the polymerization is completed. In addition, Heating during liquid crystal reorientation will not become outgassing.

The above-mentioned reactive functional group is not particularly limited as long as it is a functional group that can be combined with a curable resin described later through a polymerization reaction, and examples thereof include cyclic ether groups such as epoxy groups and oxetanyl groups, (methyl ) acryloyl, styrene, etc. Among them, a (meth)acryloyl group or an epoxy group is suitable.

Among the two or more reactive functional groups of the radical polymerization initiator, at least one is preferably a (meth)acryloyl group, and at least one is preferably a cyclic ether group.

In addition, both of the active radical species generated by the dissociation of the radical polymerization initiator by irradiation of light and/or heat preferably have at least one reactive functional group. That is, the above-mentioned reactive functional group is preferably configured in the molecule so that when the radical polymerization initiating group is dissociated by irradiation of light and/or heat to generate two active radical species, any one of the active radical species has at least one reactive functional group. As a result, all the generated active radical species form a copolymer with the curable resin and are fixed, so that the residue of the polymerization initiator does not elute in the liquid crystal after the polymerization is completed. In addition, when the liquid crystal is reoriented, it is heated Nor will it become an evolved gas.

The preferable lower limit of the number average molecular weight of the said radical polymerization initiator is 300. If it is less than 300, the radical polymerization initiator component may elute in the liquid crystal, and the orientation of the liquid crystal may be easily disturbed. A preferable upper limit is 3000. When it exceeds 3000, it may become difficult to adjust the viscosity of the curable resin composition of 2nd this invention.

The aforementioned radical polymerization initiator preferably has a molar absorptivity at 350 nm measured in acetonitrile of 2 million to 10,000 M ^-1 ·cm ^-1 . If it is less than 200M ^-1 ·cm ^-1 , when it is used as a sealant for liquid crystal display elements, it may not be fully cured unless it is irradiated with high-energy rays with a wavelength of 350nm or less. And get worse. If it exceeds 10,000 M ^-1 ·cm ^-1 , when used as a sealant for liquid crystal display elements, when irradiated with ultraviolet light having a wavelength of about 350 nm, only the surface may be cured first, and the inside may not be sufficiently cured. More preferably, it is 300-3000 M ^-1 ·cm ^-1 .

In addition, in this specification, the above-mentioned molar absorptivity refers to ε( ^{M- 1} ·cm ^-1 ) value.

[mathematical formula 1]

Log(I _o /I)=εcd (7)

In addition, in the above-mentioned formula (7), I represents the intensity of transmitted light, I _o represents the intensity of the transmitted light of acetonitrile pure solvent, c represents the molar concentration (M), d represents the thickness (cm) of the solution layer, Log (I _o /I) indicates absorbance.

The radical polymerization initiator described above preferably has a molar absorptivity at 430 nm measured in acetonitrile of 100 M ⁻¹ ·cm ⁻¹ or less. If it exceeds 100M ^-1 ·cm ^-1 , active radicals are generated by light having a wavelength in the visible region, and the operability becomes very poor. The method for producing the radical polymerization initiator is not particularly limited, and conventionally known methods can be used. For example, (meth)acrylic acid or (meth)acryloyl chloride is used. A method for carrying out (meth)acrylic esterification of alcohol derivatives of polymerization initiators and hydroxyl groups; a compound having two or more free radical polymerization initiators and hydroxyl or amino groups in the molecule and a compound with two or more epoxy groups in the molecule A method of reacting an epoxy group of a compound; making a compound having two or more radical polymerization initiators and hydroxyl or amino groups in the molecule react with an epoxy group of a compound having two or more epoxy groups in the molecule, The method of reacting the remaining epoxy groups with (meth)acrylic acid or (meth)acrylate monomers or styrene monomers with active hydrogen groups; A method in which the above-mentioned hydroxyl group (meth)acrylic acid is esterified after reacting a compound with a hydroxyl group or an amino group with a cyclic ester compound or a carboxylic acid compound with a hydroxyl group; After synthesizing a urethane derivative with a compound of a hydroxyl group or an amino group and a difunctional isocyanate derivative, another isocyanate is mixed with (meth)acrylic acid, glycidol, a (meth)acrylate monomer with a hydroxyl group, styrene mono Body and other reaction methods, etc.

As a compound which has two or more epoxy groups in the said molecule, a difunctional epoxy resin compound is mentioned, for example.

The bifunctional epoxy resin compound is not particularly limited, and examples thereof include bisphenol A-type epoxy compounds, bisphenol F-type epoxy resins, bisphenol AD-type epoxy resins, hydrogenated epoxy resins, and novolaks. Type epoxy resin, urethane-modified epoxy resin, nitrogen-containing epoxy resin epoxidized m-xylylenediamine, etc., rubber-modified epoxy resin containing polybutadiene or nitrile rubber (NBR), etc. . These bifunctional epoxy resin compounds may be solid or liquid.

The (meth)acrylate monomer having a hydroxyl group is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, poly Mono(meth)acrylate of dihydric alcohols such as ethylene glycol; mono(meth)acrylate and di(meth)acrylate of trihydric alcohols such as trimethylolethane, trimethylolpropane, and glycerin wait. These may be used alone or in combination of two or more.

Examples of the difunctional isocyanate derivatives include diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), naphthalene Diisocyanate (NDI), benzylidine diisocyanate (TPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMHDI), etc.

The preferable lower limit of the compounding quantity of the said radical polymerization initiator in the 2nd curable resin composition of this invention is 0.1 weight part with respect to 100 weight part of curable resins, and a preferable upper limit is 15 weight part. When it is less than 0.1 weight part, the 2nd curable resin composition of this invention may not fully harden, and when it exceeds 15 weight part, storage stability may fall. A more preferable lower limit is 1 part by weight, and a more preferable upper limit is 7 parts by weight.

The curable resin composition of this invention may contain other radical polymerization initiators other than the said radical polymerization initiator. Such other radical polymerization initiators are not particularly limited as long as they generate radicals under the action of light and/or heat.

Examples of the radical polymerization initiator that generates radicals under the action of heat include peroxides such as lauroyl peroxide, benzoyl peroxide, and cumyl peroxide; azobisisobutyronitrile, etc. Azo compounds, etc.

Examples of radical polymerization initiators that generate radicals under the action of light include acetophenone compounds, benzophenone compounds, benzoin compounds, benzoin ether compounds, acylphosphine oxide compounds, thioxanthone compounds, and compounds etc. Specifically, examples include benzophenone, 2,2-diethoxyacetophenone, benzil, benzoyl isopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl Ketones, thioxanthone, etc. These other radical polymerization initiators may be used alone or in combination of two or more.

The preferable lower limit of content of the said other radical polymerization initiator in the curable resin composition of this invention is 0.1 weight part with respect to 100 weight part of said curable resins, and a preferable upper limit is 10 weight part. If it is less than 0.1 weight part, hardening may not be sufficient and when it exceeds 10 weight part, liquid crystal may be polluted by the residue of a radical polymerization initiator. A more preferable lower limit is 1 part by weight, and a more preferable upper limit is 5 parts by weight.

The third present invention is a curable resin composition containing a curable resin cured by light and/or heat, a polymerization initiator, and an adhesion aid, wherein the adhesion aid It is an alkoxysilane compound with a molecular weight of 500 or more, and/or an alkoxysilane compound with a molecular weight of 200 or more and a hydrogen-bonding functional group value of 2×10 ^-3 to 7×10 ^-3 mol/g.

In addition, the above-mentioned so-called alkoxysilane compound is a compound represented by the following general formula (8).

[chemical formula 3]

-Si(OR ¹ ) _n R ² _(3-n) (8)

In formula (8), R ¹ and R ² are each independent, and examples of the structure include hydrocarbon groups and hydrogen, but methyl, ethyl, and propyl groups are more preferable. In addition, n is an integer of 1-3.

The third curable resin composition of the present invention containing an alkoxysilane compound having a molecular weight of 500 or more among such alkoxysilane compounds can be used as a sealant for liquid crystal display elements to produce liquid crystal displays by liquid crystal drop filling method. During the process of components, there will be no liquid crystal contamination due to adhesion aids.

Such an alkoxysilane compound having a molecular weight of 500 or more is not particularly limited, and examples include tris(3-trimethoxysilylpropyl)isocyanurate, N-triethoxysilylpropyl Quinine urethane, (tridecafluoro-1,1,2,2,-tetrahydrooctyl)triethoxysilane, (heptadecafluoro-1,1,2,2,-tetrahydrodecyl) Triethoxysilane, bis[(3-methyldimethoxysilyl)propyl]polypropylene oxide, bis(glutaric acid (Pentantione-t))titanium-O,O-bis(oxo Ethyl)-aminopropyltriethoxysilane, etc. For these alkoxysilane compounds, commercially available products such as those manufactured by Chitsuso Corporation and Arakawa Chemical Co., Ltd. ("Composelan E202") may be used, or may be synthesized from alkoxysilanes having reactive groups and/or polymerizable groups.

In addition, the third curable resin composition of the present invention containing an alkoxysilane compound having a molecular weight of 200 or more and a hydrogen-bonding functional group value of 2×10 ^-3 to 7×10 ^-3 mol/g among the alkoxysilane compounds Even if it is used as a sealant for liquid crystal display elements in the process of manufacturing liquid crystal display elements by the liquid crystal drop filling method, there will be no liquid crystal contamination due to the adhesion aid.

In addition, the above-mentioned hydrogen-bonding functional group value can be calculated from the following formula (9).

[mathematical formula 2]

Hydrogen-bonding functional group value (mol/g) = number of hydrogen-bonding functional groups in one molecule/molecular weight

(9)

The hydrogen-bonding functional group in the above-mentioned alkoxysilane compound is not particularly limited as long as it is a hydrogen-bonding functional group or residue other than the _-NH group. For example, -OH group, -SH group, -NHR group (R represents aromatic hydrocarbon or aliphatic hydrocarbon, or derivatives of these), -COOH group, -NHOH group and other functional groups, and -NHCO- group, -NH- group, -CONHCO- existing in the molecule , -NH-NH- and other residues.

The alkoxysilane compound having a molecular weight of 200 or more and a hydrogen-bonding functional group value of 2×10 ^-3 to 7×10 ^-3 mol/g is not particularly limited, and examples thereof include N-3-acryloyloxy (Acryloxi)-2-hydroxypropyl)-3-aminopropyltriethoxysilane, 3-(N-allylamino)propyltrimethoxysilane, bis(2-hydroxyethyl)-3- Aminopropyltriethoxysilane, bis[3-(triethoxysilyl)propyl]urea, bis(trimethoxysilylpropyl)amine, bis[3-(trimethoxysilyl) propyl)]ethylenediamine, 3-(2,4-dinitrophenylamino)propyltriethoxysilane, N-(hydroxyethyl)-N-methylaminopropyltrimethoxysilane , 2-hydroxy-4-(3-triethoxypropoxy) diphenyl ketone, 3-mercaptopropyltrimethoxysilane, O-(methacryloyloxyethyl)-N-(three Ethoxysilylpropyl)urethane, N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, N-phenylaminopropyltrimethyl Oxysilane, N-1-phenethyl-N'-triethoxysilylpropylurea, O-(propargyloxy)-N-(triethoxysilylpropyl)urethane , (3-triethoxysilylpropyl)-tert-butylcarbamate, N-(3-triethoxysilylpropyl)-4-hydroxybutanamide, (S)-N -Triethoxysilylpropyl-O-menthyl carbamate, 3-(triethoxysilylpropyl)-p-nitrobenzamide, N-(triethoxymethyl Silylpropyl)-O-polyethylene oxide urethane, N-triethoxysilylpropyl quinine urethane, N-triethoxysilylpropyl quinine (kinin) urethane , N-[5-(trimethoxysilyl)-2-aza-1-oxo-pentyl]caprolactam, O-(vinyloxyethyl)-N-(triethoxysilyl Propyl) urethane, etc. As these alkoxysilane compounds having a molecular weight of 200 or more and a hydrogen-bonding functional group value of 2×10 ⁻³ to 7×10 ⁻³ mol/g, commercially available products such as Chitsuso Corporation can be used, for example. In addition, these alkoxysilane compounds can also be synthesized from commercially available alkoxysilanes having reactive functional groups such as NH ₂ groups, NCO groups, acryloyl groups, and epoxy groups. For example, an equivalent reaction product of 3-aminopropyltrimethoxysilane and Karenz MOI (manufactured by Showa Denko Co., Ltd.); Equal reactants, 3-aminopropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and 2-hydroxyethyl acrylate Equal reactants of ester resin, equal reactants of 3-isocyanatopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and 3-epoxypropylene Equal reactants of oxypropyltrimethoxysilane, equal reactants of 3-glycidoxypropyltrimethoxysilane and 2-hydroxyethyl acrylate resin, 3-glycidoxypropyl Equal reactants of trimethoxysilane and 3-mercaptopropyltrimethoxysilane, etc.

The aforementioned alkoxysilane compound with a molecular weight of 500 or more and the alkoxysilane compound with a molecular weight of 200 or more and a hydrogen-bonding functional group value of 2×10 ^-3 to 7×10 ^-3 mol/g may be used alone or in combination. Use the above combinations.

The above-mentioned alkoxysilane compound preferably has at least one polymerizable functional group and/or reactive functional group. Thereby, when the curable resin composition of the third invention is cured, the above-mentioned alkoxysilane compound is embedded in the cured product, so it does not elute in the liquid crystal after curing.

The above-mentioned polymerizable functional group and reactive functional group are not particularly limited as long as they are reactive functional groups that react with radically polymerizable, cationically polymerizable, or anionically polymerizable functional groups or active hydrogen.

As said polymerizable functional group, an acryloyl group, a methacryloyl group, an epoxy group, a vinyl group etc. are mentioned, for example. As a reactive functional group which reacts with the said active hydrogen, an isocyanate group, an acryloyl group, a methacryloyl group, an epoxy group etc. are mentioned, for example. Among these, at least one selected from epoxy groups, acryloyl groups, and methacryloyl groups is suitable because it is cured together with common sealant curing components and is more difficult to dissolve in liquid crystals.

The preferable lower limit of the compounding quantity of the said alkoxysilane compound in curable resin composition of 3rd this invention is 0.1 weight part with respect to 100 weight part of curable resins, and a preferable upper limit is 20 weight part. If it is less than 0.1 parts by weight, the functions of adhesive strength and water resistance may not be fully exhibited, and if it exceeds 20 parts by weight, basic performances such as curability may be impaired as a curable resin composition.

The inventors of the present invention have intensively studied the bonding property of the sealant, and found that by mixing resin particles having a specific core-shell structure with a curable resin composition whose cured product has a glass transition temperature of a specific value after curing, Even when curing with light, the bonding property with the substrate can be significantly improved, and thus the fourth invention has been completed.

The fourth present invention is a curable resin composition containing a curable resin cured under the action of light and/or heat, a polymerization initiator, and resin microparticles, the resin microparticles having rubber A core particle composed of a resin that is elastic and has a glass transition temperature below -10°C and a shell layer formed on the surface of the above core particle is composed of a resin with a glass transition temperature of 50-150°C. The glass transition temperature measured by the dynamic viscoelasticity measurement method (DMA method) under the conditions of 1 minute and a frequency of 10 Hz is 120° C. or above.

The resin particles have a core particle composed of a resin having rubber elasticity and a glass transition temperature of -10°C or lower, and a shell layer composed of a resin having a glass transition temperature of 50-150°C formed on the surface of the core particle.

In addition, in the present specification, unless otherwise specified, the glass transition temperature refers to a temperature measured under the condition of a temperature increase rate of 10° C./min by a common DSC method.

The aforementioned resin having rubber elasticity and having a glass transition temperature of -10°C or lower is not particularly limited, and is suitable, for example, a polymer of (meth)acryloyl monomer.

Examples of the (meth)acryloyl monomer include ethyl acrylate, propyl acrylate, n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate, butyl methacrylate, and Esters etc. These (meth)acryloyl monomers may be polymerized alone, or two or more types may be copolymerized.

There are no particular limitations on the above-mentioned resin having a glass transition temperature of 50-150° C. Examples thereof include isopropyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, methyl Polymers obtained by polymerizing methyl acrylate, styrene, 4-chlorostyrene, 2-ethylstyrene, acrylonitrile, vinyl chloride, etc. These monomers may be used alone or in combination of two or more.

The particle size of the resin fine particles can be appropriately selected according to the purpose of use of the curable resin composition of the fourth invention. When used as a sealant for liquid crystal display elements, the preferred lower limit is 0.01 μm, and the preferred upper limit is 5 μm. Within this range, the surface area of the resin particles relative to the curable resin is sufficiently large, the swelling effect of the core layer can be effectively expressed, and the gap between the substrates can be secured when used as a sealant for liquid crystal display elements. operability.

There is no particular limitation on the method for producing the above-mentioned resin microparticles, and the following method is enumerated: a core particle is formed by emulsion polymerization using only a monomer constituting a core, and then a monomer constituting a shell is added and polymerized to form a shell on the surface of the core particle. layer.

The preferable lower limit of the compounding quantity of the said resin fine particle in the 4th curable resin composition of this invention is 15 weight part with respect to 100 weight part of said curable resins, and a preferable upper limit is 50 weight part. If it is less than 15 parts by weight, a sufficient bondability improvement effect may not be obtained, and if it exceeds 50 parts by weight, the degree of thickening may exceed the desired level. A more preferable upper limit is 20 parts by weight.

The cured product of the curable resin composition of the fourth invention has a glass transition temperature of 120°C or higher as measured by the dynamic viscoelasticity measurement method (DMA method) at a heating rate of 5°C/min and a frequency of 10 Hz. If it is less than 120° C., even if the above-mentioned resin fine particles are added, the effect of improving the adhesion to the glass substrate cannot be obtained. The upper limit of the glass transition temperature is not particularly limited, but a preferable upper limit is 180°C. If the temperature exceeds 180°C, the bondability may not be sufficiently obtained. A more preferable upper limit is 150°C.

In addition, the cured product refers to a cured product cured under the action of light and/or heat.

The curable resin composition of the fourth invention preferably has an adhesive strength of 150 N/cm ² or more when bonding glass substrates and curing them. If it is less than 150 N/cm ² , the strength of the obtained liquid crystal display device may not be sufficient.

In addition, the said adhesive strength can be calculated|required from the tensile strength required when peeling off two glass substrates after bonding two glass substrates using curable resin composition of this invention, and making it harden, for example.

The inventors of the present invention have intensively studied the problem of uneven gaps, and found that if a curable resin composition containing inorganic fine particles and exhibiting a specific average linear expansion coefficient is used, uneven cell gaps will not occur due to substrate misalignment, Thus far, the fifth and sixth inventions have been completed.

A fifth present invention is a curable resin composition, which is a curable resin combination comprising a curable resin cured by light and/or heat, a polymerization initiator, and inorganic particles having an average particle diameter of 1 μm or less The average linear expansion coefficient α ₁ of the cured product from a temperature 40°C lower than the glass transition temperature to a temperature 10°C lower than the glass transition temperature when it is cured only under the action of light is 1×10 ^-4 -5×10 ^-4 /°C, and the average linear expansion coefficient α ₂ between a temperature 10°C higher than the glass transition temperature and a temperature 40°C higher than the glass transition temperature is 2×10 ^-4 -1×10 ^{- 3} /°C.

A sixth aspect of the present invention is a curable resin composition comprising a curable resin cured by light and/or heat, a polymerization initiator, and inorganic particles having an average particle diameter of 1 μm or less It is characterized in that the average linear expansion coefficient _α1 between the temperature of the cured product when it is cured under the action of light and heat between the temperature 40°C lower than the glass transition temperature and the temperature 10°C lower than the glass transition temperature is 5×10 ^-5 -1×10 ^-4 /°C, and the average linear expansion ratio α ₂ between a temperature 10°C higher than the glass transition temperature and a temperature 40°C higher than the glass transition temperature is 1×10 ^-4 -3×10 ^-4 /°C.

As curable resin used for the curable resin composition of 5th and 6th this invention, resin which has a cyclic ether group and a radically polymerizable functional group in one molecule is suitable. Thus, the curable resin compositions of the fifth and sixth inventions can have both photocurability and thermosetting properties, and are used as sealants, sealing agents, and vertical guides for the manufacture of liquid crystal display devices using the drop filling method. When at least one of the transparent materials is used, it can be temporarily cured by light irradiation and then actually cured by heating.

The cyclic ether group of the curable resin used in the above-mentioned fifth and sixth curable resin compositions of the present invention is not particularly limited, and an epoxy group or an oxetanyl group is suitable, for example. In addition, the radical polymerizable functional group in the above-mentioned reactive resin is not particularly limited, and a (meth)acryloyl group is suitable, for example.

The total functional group equivalent weight of the cyclic ether group and the radically polymerizable functional group in the curable resin used in the curable resin composition of the above-mentioned fifth and sixth present inventions preferably has a lower limit of 2.5 mmol/g, and a preferable upper limit of 5.5 mmol /g. When it is less than 2.5 mmol/g, heat resistance and moisture resistance may be inferior, and when it exceeds 5.5 mmol/g, the adhesiveness to a board|substrate etc. may be insufficient.

The functional group equivalent weight of the radically polymerizable functional group in the curable resin used in the curable resin compositions of the fifth and sixth inventions described above preferably has a lower limit of 2.0 mmol/g, and a preferable upper limit of 5.0 mmol/g. When it is less than 2.0 mmol/g, heat resistance and moisture resistance may be inferior, and when it exceeds 5.0 mmol/g, the adhesiveness to a board|substrate etc. may be insufficient.

The value obtained by dividing the equivalent of radically polymerizable functional groups in the curable resin used in the curable resin compositions of the fifth and sixth inventions by the equivalent of cyclic ether groups preferably has a lower limit of 1 and an upper limit of 9. If it is less than 1, the photoreactivity may decrease, and even if light is irradiated to the sealant after adjusting the gap, not only temporary initial curing will not occur, but also the elution to the liquid crystal will increase. If it exceeds 9, the adhesion and moisture permeability may be compromised. Insufficient in terms of.

From the viewpoint of reducing compatibility with liquid crystals and eliminating contamination, the curable resin used in the curable resin compositions of the above-mentioned fifth and sixth inventions is preferably a resin having a hydroxyl group and/or a urethane bond. From the viewpoint of improving heat resistance, it preferably has at least one molecular skeleton selected from a biphenyl skeleton, a naphthalene skeleton, a bisphenol skeleton, and a partial (meth)acryloyl compound of a novolak-type epoxy resin.

The curable resin used in the curable resin compositions of the above-mentioned fifth and sixth inventions more preferably has a cyclic structure having 24 or less atoms. Here, the term "atomic number" refers to the sum of the atomic numbers of carbon, hydrogen, oxygen, and the like in molecules constituting the above-mentioned ring structure. When the number of atoms exceeds 24, the linear expansion coefficient described later may not be satisfied, or the heat resistance may be poor.

The lower limit of the equivalent weight of the ring structure in the curable resin used in the curable resin compositions of the fifth and sixth inventions is preferably 1.5 mmol/g, and the upper limit is preferably 6.0 mmol/g. If it is less than 1.5 mmol/g, the linear expansion coefficient may become large and may not satisfy the range described later, and if it exceeds 6.0 mmol/g, the adhesiveness to a substrate or the like may be insufficient.

The atoms constituting the ring structure are not particularly limited, but the skeleton structure is preferably carbon atoms, and such a ring structure is preferably aromatic.

There are no particular limitations on the above-mentioned aromaticity, and examples thereof include benzene, indene, naphthalene, tetralin, anthracene, and phenanthrene.

The number average molecular weight of the curable resin used in the curable resin compositions of the above fifth and sixth present inventions preferably has a lower limit of 300, and a preferable upper limit of 550. If it is less than 300, the alignment of the liquid crystal may be disturbed by eluting to the liquid crystal, and if it exceeds 550, the preparation of a sealant, a sealing agent, or a vertical conductive material may become difficult due to viscosity.

The above-mentioned inorganic fine particles have the function of preventing curing shrinkage of the curable resin compositions of the fifth and sixth inventions and realizing the following linear expansion coefficient.

The above-mentioned inorganic fine particles are not particularly limited, and examples thereof include silica, diatomaceous earth, aluminum oxide, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, Barium sulfate, gypsum, calcium silicate, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, silicon nitride, montmorillonite, kaolin, allophane, potassium titanate, zeolite, sepiolite , calcium carbonate, calcium oxide, magnesium oxide, ferrite, hematite, aluminum borate and other substances. Among them, silica and alumina are suitable.

The shape of the inorganic fine particles is not particularly limited, and regular or irregular shapes such as spherical, needle-like, and plate-like shapes are exemplified.

The above-mentioned inorganic particles may also be surface-treated with at least one selected from imidazole silane compounds, epoxy silane compounds, and aminosilane compounds. The above-mentioned compounds contain a structure in which an imidazole skeleton and an alkoxysilyl group are combined through a spacer. By performing such a surface treatment, the affinity between the above-mentioned inorganic particles and the above-mentioned reactive resin can be increased, and at the same time, the function of these as a silane coupling agent, bonding force, and storage stability can be improved.

The upper limit of the average particle diameter of the said inorganic fine particle is 1 micrometer. If it exceeds 1 μm, the surface of the cured product obtained by curing the photothermally curable resin composition of the present invention under the action of light and/or heat will become uneven, and the precision of the cell gap will be poor. A preferable lower limit is 0.01 μm, and a preferable upper limit is 0.1 μm. If it is less than 0.01 μm, thixotropy may become high and aggregates may be generated.

The preferable lower limit of content of the said inorganic particle in curable resin composition of 5th and 6th this invention is 10 weight part with respect to 100 weight part of curable resins, and a preferable upper limit is 50 weight part. A more preferable lower limit is 15 parts by weight, and a more preferable upper limit is 35 parts by weight.

The average linear expansion of the cured product from a temperature 40°C lower than the glass transition temperature to a temperature 10°C lower than the glass transition temperature when the curable resin composition of the present invention is cured only by irradiating light The ratio α ₁ is 1×10 ^-4 -5×10 ^-4 /°C, and the average linear expansion ratio α ₂ between the temperature 10°C higher than the glass transition temperature and the temperature 40°C higher than the glass transition temperature 2×10 ^-4 -1×10 ^-3 /°C. If the average linear expansion rate α ₁ is less than 1×10 ^-4 /°C, or the average linear expansion rate α ₂ is less than 2 × 10 ^-4 /°C, it can be used as a sealant and sealer for liquid crystal display devices produced by the drop filling method. In the case of an agent and a vertical conductive material, even if temporary curing is performed by light irradiation and then actual curing is performed by heating, the adhesion to the substrate or the like becomes insufficient, and sufficient bonding properties cannot be obtained. If the average linear expansion rate α ₁ exceeds 5×10 ^-4 /°C, or the average linear expansion rate α ₂ exceeds 1×10 ^-3 /°C, uneven cell gaps will occur due to displacement of the substrate during temporary curing.

In the curable resin composition of the sixth invention, when it is cured under the action of light and heat, the temperature of the cured product is between 40°C lower than the glass transition temperature and 10°C lower than the glass transition temperature. The average linear expansion rate α ₁ is 5×10 ^-5 -1×10 ^-4 /°C, and the average linear expansion between a temperature 10°C higher than the glass transition temperature and a temperature 40°C higher than the glass transition temperature The rate α ₂ is 1×10 ^-4 -3×10 ^-4 /°C. If the average linear expansion rate α ₁ is less than 5×10 ^-5 /°C, or the average linear expansion rate α ₂ is less than 1 × 10 ^-4 /°C, it can be used as a sealant and sealer for liquid crystal display devices produced by the drop filling method. In the case of an agent and a vertical conductive material, even if temporary curing is performed by light irradiation and then actual curing is performed by heating, the adhesion to the substrate or the like becomes insufficient, and sufficient bonding properties cannot be obtained. If the average linear expansion ratio α ₁ exceeds 1×10 ^-4 /°C, or the average linear expansion ratio α ₂ exceeds 3×10 ^-4 /°C, the obtained liquid crystal display device is poor in heat resistance and cooling-heat cycle characteristics.

The curable resins of the first to third inventions described above mainly solve the liquid crystal contamination problem, the curable resins of the fourth invention mainly solve the bonding problem, and the curable resin compositions of the fifth to sixth inventions mainly solve the problem of liquid crystal contamination. The problem of unit gaps. These can be implemented independently, but can be applied to the sealing compound for liquid crystal display elements used when manufacturing a liquid crystal display device by the drop filling method by using in combination within the range which does not hinder each objective.

The curable resin composition of the 1st-6th invention may contain a hardening|curing agent. The curing agent is not particularly limited, and examples thereof include amine compounds, polyhydric phenol compounds, acid anhydride compounds, and the like.

The above-mentioned so-called amine compound refers to a compound having more than one 1-3 grade amino group in the molecule, such as aromatic amines such as m-phenylenediamine and diaminodiphenylmethane; 2-methylimidazole, 1,2-diphenyl Imidazole compounds such as methylimidazole and 1-cyanoethyl-2-methylimidazole; imidazoline compounds such as 2-methylimidazoline; dihydrazide compounds such as sebacic acid dihydrazide and isophthalic acid dihydrazide; Dicyandiamide etc. In addition, amine adducts such as Amiquia PN-23 and Amiquia MY-24 commercially available from MSG Fine Technology Co., Ltd. can also be used.

Examples of the polyhydric phenolic compound include polyphenol compounds such as Epicure 170 and Epicure YL6065 commercially available from Japan Epoxy Resin Corporation; novolak-type phenolic resins such as Epicure MP402FPI; and the like.

As said acid anhydride, Epicure YH306, YH307 etc. which are marketed by Japan Epoxy Resin Co., Ltd. are mentioned, for example.

These curing agents may be used alone or in combination of two or more. Among them, solid amine compounds are more suitable from the viewpoint of good low-temperature curability when mixed with a curable resin and good effective life. Among the above-mentioned solid amine compounds, those having a melting point of 100° C. or higher are more preferable from the viewpoint of storage stability of the curable composition.

The preferable lower limit of content of the said curing agent in the curable resin composition of 1st-6th this invention is 0.1 weight part with respect to 100 weight part of said curable resins, and a preferable upper limit is 100 weight part. If it is less than 0.1 parts by weight, curing may be insufficient, and if it exceeds 100 parts by weight, the storage stability of the curable resin composition may deteriorate. A more preferable lower limit is 1 part by weight, and a more preferable upper limit is 50 parts by weight.

The curable resin composition of the first to sixth inventions may additionally contain a thixotropic agent for adjusting thixotropy, a gap adjuster, an antifoaming agent, a leveling agent, a polymerization inhibitor, fillers such as fillers, and the like as needed.

The method for producing the curable resin composition of the first to sixth present inventions is not particularly limited, and examples thereof include a method of mixing the above-mentioned curable resin, a polymerization initiator, and various additives mixed as necessary by a conventionally known method. wait. At this time, in order to remove ionic impurities, it may be brought into contact with an ion-adsorbing solid such as layered silicate mineral.

Moreover, when manufacturing curable resin composition of 1st - 6th this invention, it is preferable to perform the process of filtering using a filter after mixing the component which comprises curable resin composition.

Usually, since the affinity between the curable resin and the curing agent or filler is not necessarily high, if the components are only mixed by ordinary methods, the curing agent and filler cannot be sufficiently dispersed in the resin, and a part of them will be formed by aggregation. Condensate. Even if such agglomerates are generated, when the sealing compound for liquid crystal display elements is produced by the conventional method, the cell gap can be adjusted by the heat press process, so there is almost no influence. However, when liquid crystal display elements are produced by the drop filling method, since there is no cell gap adjustment process by hot pressing, if agglomerates with large particle sizes are contained in the sealant for liquid crystal display elements, it will affect the obtained liquid crystal display elements. the unit gap.

By filtering with a filter after mixing the components constituting the curable resin composition, aggregates with relatively large particle diameters affecting the cell gap can be reliably removed, so that cell gap defects caused by the above-mentioned aggregates do not occur.

The manufacturing method of curable resin composition which has the process of filtering using a filter after mixing the components which comprise curable resin composition is also one of this invention.

The above-mentioned filter is not particularly limited as long as it can remove aggregates having a particle diameter at least to the extent that it affects the cell gap of the target liquid crystal display element. It is preferable to remove aggregates having a particle diameter twice or larger than the cell gap of the target liquid crystal display element, and it is also preferable to remove aggregates having a particle diameter larger than the cell gap of the target liquid crystal display element. Among them, in the case of a liquid crystal display element in which the element formed on a transparent substrate such as a circuit is related to part or all of the sealing portion, the width of the sealing portion is narrower than the actual cell gap to the extent that it corresponds to the size of the element, so it is more preferable Agglomerates having a particle size equal to or greater than the width of the narrowed sealing portion can be removed.

As such a filter, for example, a filter with a trapping efficiency of 70% or more for particles having a particle size equal to or greater than the target distance between the substrates of the liquid crystal display element (cell gap); a flow rate of 2 L/min, a pressure of 4.6 N/ Filters with an air flow resistance value of 10 mmH ₂ O or more in cm ² of air.

In addition, since the curable resin composition has a high viscosity, it is preferable to pressurize the curable resin composition during the above-mentioned filtration. Therefore, as the above-mentioned filter, it is preferable that it can withstand even if it is pressurized. As such a filter, a filter made of metal such as stainless steel, ceramics, or the like is suitable.

In addition, in the above-mentioned filtration step, it is preferable to lower the temperature during filtration so as to suppress the curing reaction, but in order to reduce the viscosity of the above-mentioned curable resin composition as much as possible to improve the filtration efficiency, it is preferable to heat within a range that does not cause curing. The aforementioned curable resin composition. As for the temperature of the said curable resin composition at the time of the said filtration, a preferable minimum is 25 degreeC, and a preferable upper limit is 70 degreeC. If it is out of this range, the filtration efficiency may deteriorate, and the viscosity of the filtrate may increase due to the prolonged heating time during filtration, which may increase the degree of viscosity increase of the sealant during storage or use. The lower limit is more preferably 30°C, and the upper limit is more preferably 60°C.

In addition, the constituent components of the curable resin composition, particularly the curing agent, are preferably selected from components capable of suppressing an increase in the viscosity of the curable resin composition near normal temperature.

It is preferable to fully mix the components which comprise a curable resin composition before performing a filtration process using the said filter. When mixing is insufficient, the quantity of the component removed by a filter may increase, and the sealing compound for liquid crystal display elements which has the performance which meets a design standard may not be obtained.

The mixing method is not particularly limited, and examples thereof include methods using conventional planetary mixers, three-roll mixers, and the like.

In the curable resin composition of the present invention, it is preferable that the content of particles having a particle size equal to or larger than the target distance between liquid crystal display element substrates is 30% by weight or less.

When the curable resin composition of the 1st-6th present invention is used as a sealant for liquid crystal display elements to manufacture liquid crystal display elements by the liquid crystal drop filling method, there is little pollution to liquid crystals, good adhesion to the substrate, and no Cell spacing is not uniform.

The sealing compound for liquid crystal display elements formed using the curable resin composition of this invention is also one of this invention.

The sealing agent (endsealant) for liquid crystal display elements formed using the curable resin composition of this invention is also one of this invention.

In addition, in a liquid crystal display element, a vertical conduction material is generally used in order to conduct vertical conduction between opposing electrodes on two transparent substrates. The said vertical conduction material is comprised by making curable resin composition contain electroconductive fine particle.

The vertical conduction material for liquid crystal display elements containing the curable resin composition of this invention and electroconductive fine particles is also one of this invention.

There are no particular limitations on the above-mentioned conductive particles, and examples thereof include metal particles; particles formed by metal plating on resin matrix particles (hereinafter referred to as metal-plated particles); metal-plated particles on resin matrix particles. Fine particles formed by covering with a resin or the like (hereinafter referred to as covered metal-plated fine particles); and these metal fine particles, metal-plated fine particles, fine particles having protrusions on the surface of the covered metal-plated fine particles, and the like. Among them, gold-plated or copper-plated metal-plated fine particles or coated metal-plated fine particles are preferable from the viewpoint of uniform dispersion in the resin composition and good electrical conductivity.

As for the compounding quantity of the said electroconductive fine particle with respect to 100 weight part of said curable resin compositions, a preferable minimum is 0.2 weight part, and a preferable upper limit is 5 weight part.

There are no particular limitations on the method of producing the vertical conduction material for liquid crystal display elements of the present invention, and examples thereof include mixing the above-mentioned curable resin composition, the above-mentioned conductive fine particles, etc. according to a prescribed mixing amount, and then using a vacuum planetary stirrer, etc. mixed methods, etc.

There is no particular limitation as a method of manufacturing a liquid crystal display element using at least one of the sealant for liquid crystal display elements of the present invention, the sealing agent for liquid crystal display elements of the present invention, and the vertical conduction material for liquid crystal display elements of the present invention. For example, It can be produced by the following method. On one of two transparent substrates with electrodes, such as an ITO film, the sealant for liquid crystal display elements of the present invention is formed into a rectangular seal pattern by screen printing, dispenser coating, or the like. Also, on another transparent substrate, the liquid crystal display element of the present invention is coated with a vertical conduction material using a dispenser or the like to form a pattern for vertical conduction on predetermined electrodes. In addition, conductive fine particles may be contained in the sealant instead of the vertical conduction material and may be used for vertical conduction. Next, in the uncured state of the sealant, liquid crystal fine droplets are applied dropwise on the entire surface of the transparent substrate frame, and another transparent substrate is immediately superimposed on the uncured state of the upper and lower conduction materials, and applied to the sealing part. And the upper and lower conduction materials are partially irradiated with ultraviolet rays to cure them. When the sealant for liquid crystal display elements of the present invention and the upper and lower conduction material for liquid crystal display elements of the present invention have thermosetting properties, they are then heated and cured in an oven at 100-200°C for 1 hour to make them completely cured, thereby producing liquid crystal display elements .

A liquid crystal display element formed using at least one of the sealant for liquid crystal display elements of the present invention, the sealing agent for liquid crystal display elements of the present invention, and the vertical conduction material for liquid crystal display elements of the present invention is also one of the present invention.

In addition, the present inventors have intensively studied liquid crystal display elements manufactured by the drop filling method, and found that when the alignment film and the sealant are in contact, contamination of the liquid crystal material is likely to occur, and poor image display is likely to occur. Therefore, display defects can be effectively prevented by forming a structure in which the alignment film and the sealant do not contact in the liquid crystal display element.

The following liquid crystal display element is also one of the present invention, wherein a pair of transparent substrates having an orientation film formed on at least a part of one surface are arranged opposite to each other at a certain interval through a sealant formed around its periphery, and at the same time The surfaces formed with the alignment film face each other, and a liquid crystal material is sealed in the space formed by the transparent substrate and the sealant, wherein the alignment film and the sealant are not in contact with each other.

Description of drawings

Fig. 1 is a partially enlarged sectional view showing an example of a liquid crystal display element of the present invention.

Fig. 2 is a horizontal sectional view showing an example of a liquid crystal display element of the present invention.

Fig. 3 is a partially enlarged cross-sectional view showing an example of a conventional liquid crystal display element.

In the figure,

10, 30 liquid crystal display components

11, 31 transparent substrate

12, 32 sealant

13, 33 orientation film

14, 34 liquid crystal material

Detailed ways

Fig. 1 is a partially enlarged cross-sectional view which simulates an example of a liquid crystal display element of the present invention,

Fig. 2 is a horizontal sectional view showing an example of a liquid crystal display element of the present invention.

As shown in FIG. 1 , a liquid crystal display element 10 of the present invention has a structure in which two transparent substrates 11 having an alignment film 13 formed on their surfaces are bonded with a sealant 12 interposed therebetween so that the alignment films 13 face each other.

Also, although not shown, a transparent electrode made of, for example, a tin-doped indium oxide film (ITO film) or the like is formed between the transparent substrate 11 and the alignment film 13 .

Such a transparent electrode can be formed on the surface of the above-mentioned transparent substrate by a known vacuum evaporation method, a spray method, a hot-melt method, a dipping method, or the like.

In addition, as shown in FIG. 2, in the liquid crystal display element 10 of the present invention, the sealant 12 is formed around the periphery of the transparent substrate 11, and the alignment film 13 is formed in the area surrounded by the sealant 12 on the surface of the transparent substrate 11. , and not in contact with the sealant 12.

In the liquid crystal display element 10 of the present invention, the sealing agent 12 and the alignment film 13 need only be in contact with each other, but the distance between them is preferably 5 μm or more. If it is less than 5 μm, display defects may not be prevented.

In addition, the liquid crystal display element of the present invention is not particularly limited to the structure shown in FIG. 1 and FIG. The structure of the component.

The transparent substrate constituting the liquid crystal display element of the present invention is not particularly limited, and examples thereof include known substances conventionally used in liquid crystal display elements such as glass and resin. In addition, the size and thickness of the above-mentioned transparent substrate are not particularly limited, and can be appropriately determined according to the size of the target liquid crystal display element.

In addition, the above-mentioned alignment film is not particularly limited, and alignment films conventionally used in liquid crystal display elements can be used, but polyamide polyamide is usually used in view of good heat resistance, chemical resistance, and adhesion to transparent substrates. imine.

The liquid crystal display device of the present invention having such a structure can be produced, for example, by the following method.

First, on the specified positions on both sides of the transparent glass substrate with two electrodes such as ITO film, use flexographic printing, gravure printing, inkjet printing, screen printing and spin coating method to form polyimide A rectangular alignment film composed of equal components. At this time, an attempt was made not to form an alignment film at the application position of the sealant.

Then, after performing an orientation treatment such as rubbing treatment on the above-mentioned alignment film, a sealant is formed around the above-mentioned alignment film by screen printing, dispenser coating, etc. in the vicinity of the outer periphery of the above-mentioned transparent substrate at a position not in contact with the alignment film. shaped seal pattern.

Next, in an uncured state of the sealant, fine droplets of liquid crystal are applied dropwise to the entire surface inside the frame of the transparent substrate, and another transparent substrate is superimposed immediately, and the sealed portion is irradiated with ultraviolet rays to be cured. When the above-mentioned sealant is heat-curable, it can be heated and cured in an oven at 80-200° C. for 0.5-2 hours to make it completely cured, so as to manufacture the liquid crystal display element of the present invention.

In the liquid crystal display element of the present invention, since the alignment film formed on the transparent substrate is not in contact with the sealant, the liquid crystal material is difficult to be polluted near the periphery of the sealant formed where the contamination of the liquid crystal material is most likely to occur, so high quality can be obtained. Display the image.

The effect of the invention

According to the present invention, when used as a sealant for liquid crystal display elements in the process of manufacturing liquid crystal display elements by the drop filling method, there is little contamination of liquid crystals, good adhesion to substrates, and no unevenness in cell gaps. Curable resin composition, sealing compound for liquid crystal display elements, and liquid crystal display elements.

Example

The present invention is described in more detail below by embodiment, but the present invention is not limited to these

Example.

(Example 1)

1000 parts by weight of a crystalline epoxy resin represented by the following general formula (10) (manufactured by Shinichi Chemical Co., Ltd.: YSLV-80XY, melting point 78° C.), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine and 200 parts by weight of acrylic acid as a reaction catalyst were stirred and refluxed at 90° C. for 5 hours while transporting air to obtain non-crystalline (meth)acrylic acid modified epoxy resin (50% part acryloyl).

[chemical formula 4]

In the formula, G represents a glycidyl group.

Add 134 parts by weight of trimethylolpropane, 0.2 parts by weight of BHT as a polymerization initiator, 0.01 parts by weight of dibutyltin dilaurate as a reaction catalyst, and 666 parts by weight of isophorone diisocyanate, and stir and reflux at 60°C Under the conditions of reaction for 2 hours. Then, 25.5 parts by weight of 2-hydroxyethyl acrylate and 111 parts by weight of glycidol were added, and the mixture was stirred and refluxed at 90° C. for 2 hours while feeding air. 100 parts by weight of the obtained resin was filtered through a column filled with 10 parts by weight of quartz and kaolin natural bonding product (manufactured by Hofman Mineral Co., Ltd., Silitin V85) to absorb ionic impurities in the reactant, thereby obtaining urethane Modified part of acryloyl compound.

40 parts by weight of the obtained (meth)acrylic-modified epoxy resin, 20 parts by weight of urethane-modified partial acrylic product, and a hydrazide-type curing agent (manufactured by Miso Fine Technology Co., Ltd., Amicuyua VDH) as a latent heat curing agent 15 parts by weight, 1 part by weight of 2,2-diethoxyacetophenone as a photopolymerization initiator, 23 parts by weight of silicon oxide particles (average particle diameter: 1.5 μm), γ-glycidoxypropyltrimethoxy 1 part by weight of base silane was mixed well using a three-roll mixer until a uniform liquid was formed, thereby obtaining a curable resin composition.

A liquid crystal display device was produced using the obtained curable resin composition as a sealing compound for liquid crystal display elements.

That is, on one of two transparent substrates with transparent electrodes, a sealant is applied with a dispenser so as to draw a rectangular frame. Next, liquid crystal (manufactured by Chitsuso Co., Ltd., JC-5004LA) was sprayed onto the entire surface of the transparent substrate frame, immediately superimposed on another transparent substrate, and the sealed part was irradiated with ultraviolet rays at an intensity of 100 mW/ ^cm2 using a high-pressure mercury lamp. 30 seconds. Then, the liquid crystal was annealed at 120° C. for 1 hour, and thermally cured to obtain a liquid crystal display device.

(Example 2)

1000 parts by weight of a crystalline epoxy resin represented by the following general formula (11) (manufactured by Shinichi Chemical Co., Ltd.: YSLV-80DE, melting point 79° C.), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine of the reaction catalyst, 200 parts by weight of acrylic acid were stirred and refluxed at 90° C. while conveying air and made to react for 5 hours to obtain crystalline (meth)acrylic acid modified epoxy resin (50% part propylene acylate).

In addition to replacing the non-crystalline (meth)acrylic modified epoxy resin (50% partially acrylated) with this crystalline (meth)acrylic modified epoxy resin (50% partially acrylated), the adoption and implementation A curable resin composition was prepared in the same manner as in Example 1, and a liquid crystal display device was fabricated using this as a sealant.

[chemical formula 5]

In the formula, G represents a glycidyl group.

(comparative example 1)

35 parts by weight of urethane acrylate represented by the following general formula (12) (manufactured by Kyoeisha Chemical Co., Ltd., AH-600), 15 parts by weight of 2-hydroxybutyl acrylate, and 50 parts by weight of isobornyl acrylate (ISOBONIL) A curable resin composition composed of 3 parts by weight of benzophenone and 3 parts by weight of benzophenone is mixed to form a uniform liquid, thereby obtaining a photocurable sealant, which is used to manufacture a liquid crystal display device.

[chemical formula 6]

In the formula, R ¹ represents an alkyl chain having 5 carbon atoms.

(comparative example 2)

50 parts by weight of bisphenol A type epoxy resin represented by the following general formula (13) (manufactured by Japan Epoxy Resin Co., Ltd., Epico-to 828US), 25 parts by weight of a hydrazide curing agent (manufactured by Nippon Hydrazine Industry Co., Ltd., NDH) The curable resin composition in parts by weight was thoroughly mixed with a three-roll mixer until a uniform liquid was formed, thereby obtaining a sealant, which was used to manufacture a liquid crystal display device.

[chemical formula 7]

For the liquid crystal display devices produced by Examples 1 and 2 and Comparative Examples 1 and 2, before and after standing at 60° C. and 95% RH for 500 hours, the color unevenness that occurred in the liquid crystal at the periphery of the sealing portion was observed with the naked eye. Evaluation of liquid crystal contamination performance was based on the following four stages: ◎ (no color unevenness at all); ○ (slight color unevenness was observed); △ (some color unevenness was observed); × (color unevenness was fairly clear) . In addition, among them, evaluation was performed using 5 samples for each part.

The results are shown in Table 1. Evaluation of Color Nonuniformity Example 1 ○ Example 2 ◎ Comparative example 1 x Comparative example 2 x

(Example 3)

The curable resin composition obtained in the same manner as in Example 1 was thoroughly mixed with a three-roll mixer until a uniform liquid was formed, and then, a metal plated with gold as conductive fine particles was mixed with respect to 100 parts by weight of the curable resin composition. 2 parts by weight of plating fine particles (Micropal AU-206 manufactured by Sekisui Chemical Co., Ltd.) were mixed with a vacuum planetary mixer to prepare a vertical conduction material for liquid crystal display elements.

A liquid crystal display device was produced in the same manner as in Example 1, except that the obtained vertical conduction material was coated on the vertical conduction electrode through a dispenser to form a vertical conduction pattern on the transparent substrate.

The obtained liquid crystal display device was left in an environment of 60° C. and 95% RH for 500 hours, and the conductivity was good at this time.

(Example 4)

(1) Manufacture of radical polymerization initiator

50 moles of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (manufactured by Ciba Specialty Chemicals Inc.) were added to the reaction flask , heated and dissolved in a dry air atmosphere.

0.05 moles of dibutyltin dilaurate and 100 moles of 2-methacryloyloxyethylene isocyanate (manufactured by Showa Denko) were slowly added dropwise thereto, and after the addition was completed, they were reacted at 90°C until detected by infrared light. Absorption spectroscopic analysis confirmed that no isocyanate group remained, and then purified to obtain a radical polymerization initiator A represented by the following formula (14).

[chemical formula 8]

(2) Preparation of curable resin composition

3 parts by weight of the obtained radical polymerization initiator A, 40 parts by weight of a partially acrylated epoxy resin (made by Daicel Yu-shi-bi Co., Ltd., UVAC1561) as a curable resin, 40 parts by weight of an acrylate-modified epoxy resin (EB3700 manufactured by Daicel Yu-shi-bi- Co., Ltd.) 20 parts by weight, 15 parts by weight of spherical silica (manufactured by Admatex Co., Ltd., SO-C1) as a filler, Fujikyua-FXR- 1030 (manufactured by Fuji Chemical Industry Co., Ltd.) 15 parts by weight, 1 part by weight of γ-glycidoxypropyltrimethoxysilane as a coupling agent, and mixed well with a paint roller until a uniform liquid was formed, thereby obtaining a curable resin composition .

(3) Production of liquid crystal display elements

Disperse 1 part by weight of spacer particles (Micropal SP-2055 manufactured by Sekisui Chemical Industry Co., Ltd.) in 100 parts by weight of the curable resin composition obtained, and apply it on both sides with a dispenser as a sealant for liquid crystal display elements. One of the substrates is a glass substrate with a rubbed alignment film and a transparent electrode.

Next, liquid crystal (manufactured by Chitsuso Co., Ltd., JC-5004LA) was dripped and coated on the entire surface of the sealant frame of the glass substrate with a transparent electrode, and another glass substrate with a transparent electrode was immediately superimposed on the sealant. Partially irradiated with ultraviolet light at 100 mW/ ^cm2 for 30 seconds with a high-pressure mercury lamp.

Then, it was heated at 120 degreeC for 1 hour, it was made to thermoset, and the liquid crystal display element was obtained.

(Example 5)

Add 50 moles of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one to the reaction flask, and heat it under a dry air atmosphere dissolve.

Under the condition that the reaction temperature does not exceed 90°C, slowly add 0.05 moles of dibutyltin dilaurate and 50 moles of 2-methacryloxyethylene isocyanate dropwise, After reacting until no remaining isocyanate groups were confirmed by infrared absorption spectroscopic analysis, purification was carried out to obtain an intermediate a represented by the following formula (15).

[chemical formula 9]

50 mol of the obtained intermediate a was charged into the reaction flask, and heated and dissolved in a dry air atmosphere. Under the condition that the reaction temperature does not exceed 90°C, 0.05 moles of dibutyltin dilaurate and 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate (Degsa Corporation) are slowly added dropwise thereto. system, TMHDI) 50 moles, after the dropwise addition, slowly add 2-hydroxyethyl acrylate dropwise under the condition that the reaction temperature does not exceed 90°C, and react at 90°C until it is confirmed by infrared absorption spectrum analysis that there is no residual The isocyanate group is then purified to obtain a radical polymerization initiator B represented by the following formula (16).

[chemical formula 10]

In the above general formula (16), A represents 2,2,4- and 2,4,4-trimethylhexamethylene.

Except having used the radical polymerization initiator B instead of the radical polymerization initiator A, the curable resin composition was prepared by the method similar to Example 4, and the liquid crystal display element was produced.

(Example 6)

100 mol of the intermediate a produced in Example 5 was added to the reaction flask, and heated and dissolved in a dry air atmosphere. Slowly add 0.1 moles of dibutyltin dilaurate and 50 moles of 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate dropwise therein under the condition that the reaction temperature does not exceed 90°C, After completion of the dropwise addition, it was reacted at 90° C. until no remaining isocyanate groups were confirmed by infrared absorption spectroscopic analysis, and then purified to obtain a radical polymerization initiator C represented by the following formula (17).

[chemical formula 11]

In the above general formula (17), A represents 2,2,4- and 2,4,4-trimethylhexamethylene.

Except having used the radical polymerization initiator C instead of the radical polymerization initiator A, a curable resin composition was prepared by the method similar to Example 4, and the liquid crystal display element was produced.

(Example 7)

Add 50 moles of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one to the reaction flask, and heat it under a dry air atmosphere dissolve. Slowly add 0.05 moles of dibutyltin dilaurate and 50 moles of 3-isopropenyl-α, α-dimethylbenzyl isocyanate dropwise therein under the condition that the reaction temperature does not exceed 90°C. After reacting at 90° C. until no remaining isocyanate groups were confirmed by infrared absorption spectroscopic analysis, purification was carried out to obtain an intermediate b represented by the following formula (18).

[chemical formula 12]

50 mol of the obtained intermediate b was charged into the reaction flask, and heated and dissolved in a dry air atmosphere. Slowly add 0.05 moles of dibutyltin dilaurate and 50 moles of 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate dropwise therein under the condition that the reaction temperature does not exceed 90°C, After the dropwise addition, glycidol was slowly added dropwise under the condition that the reaction temperature did not exceed 90°C, and reacted at 90°C until it was confirmed by infrared absorption spectrum analysis that there were no remaining isocyanate groups, and then refined to obtain the following A radical polymerization initiator D represented by formula (19).

[chemical formula 13]

Except having used the radical polymerization initiator D instead of the radical polymerization initiator A, the curable resin composition was prepared by the method similar to Example 4, and the liquid crystal display element was produced.

(comparative example 3)

Except having used "Daroquia 1173" (manufactured by Ciba Specialty Chemicals Inc.) instead of the radical polymerization initiator A, a curable resin composition was prepared in the same manner as in Example 4, and a liquid crystal display element was produced.

(comparative example 4)

Except having used "Irgacyua 184" (manufactured by Ciba Specialty Chemicals Inc.) instead of the radical polymerization initiator A, a curable resin composition was prepared in the same manner as in Example 4 to produce a liquid crystal display element.

The radical polymerization initiators, curable resin compositions, and liquid crystal display elements obtained in Examples 4-7 and Comparative Examples 3 and 4 were evaluated by the following methods.

The results are shown in Table 2.

(Measurement of liquid crystal resistivity retention)

0.5 g of the curable resin composition was added to an ampoule (inner diameter: 10.0 mm), and 0.5 g of liquid crystal was added. Put this bottle in an oven at 120° C. for 1 hour, and after returning to room temperature (25° C.), use a liquid crystal resistivity measuring device (manufactured by Toa Denpa Kogyo Co., Ltd., Model SM-8210) for the liquid crystal part, and use an electrode for liquid as an electrode. (manufactured by Ando Electric Co., Ltd., LE-21 type), the liquid crystal resistivity was measured in a standard temperature and humidity state (20° C., 65% RH). In addition, the liquid crystal resistivity retention rate was calculated|required by the following formula.

[mathematical formula 3]

Retention rate of liquid crystal resistivity (%)=(use liquid crystal resistivity after adding sealant/use liquid crystal resistivity when no sealant is added)×100

(Measurement of change in nematic-isotropic liquid transition point (N-I point))

0.5 g of the curable resin composition was added to an ampoule (inner diameter: 10.0 mm), and 0.5 g of liquid crystal was added. The bottle was placed in an oven at 120° C. for 1 hour, and after returning to room temperature (25° C.), the liquid crystal portion was placed on an aluminum plate, and the peak temperature was measured at a heating rate of 10° C./min. In addition, MDSC (manufactured by TA Insturumenes) was used as a thermal analysis device. The nematic-isotropic liquid transition point change was obtained from the following formula.

[mathematical formula 4]

N-I point change (°C) = (N-I point of liquid crystal when no sealant is added) - (N-I point of liquid crystal after adding sealant)

(jointness evaluation)

Disperse 1 part by weight of spacer particles (Micropal SP-2055 manufactured by Sekisui Chemical Industry Co., Ltd.) in 100 parts by weight of the curable resin composition, place it at the center of the slide glass, and stack another slide glass on it. The sealant was spread to make the thickness uniform, and ultraviolet rays were irradiated with a high-pressure mercury lamp at 100 mW/cm ² for 30 seconds. Then, it heated at 120 degreeC for 1 hour, and obtained the joint test piece. The adhesive strength of this test piece was measured with the tensiometer.

(Evaluation of liquid crystal display panels (evaluation of color unevenness))

About the obtained liquid crystal display element, the disorder of the liquid crystal orientation near the sealing compound immediately after manufacture and 1000 hours of operation tests on the condition of 65 degreeC95%RH was evaluated with the naked eye according to the following criteria. Also, the number of samples is six.

◎: No color unevenness at all

○: Slight color unevenness

△: Some color unevenness

×: Color unevenness is fairly clear

[Table 2] Liquid crystal resistivity retention (%) NI point change (℃) Evaluation of zygosity (N/cm ² ) LCD panel evaluation Example 4 80.2 -2.03 470 ◎ Example 5 88.3 -1.81 510 ◎ Example 6 84.8 -2.43 392 ◎ Example 7 76.4 -2.53 451 ◎ Comparative example 3 7.8 -4.29 363 △ Comparative example 4 4.2 -5.13 314 x

(Embodiment 8)

The curable resin composition obtained in the same manner as in Example 4 was thoroughly mixed with a three-roll mixer until a uniform liquid was formed, and then, the conductive fine particles of gold-plated metal were mixed with respect to 100 parts by weight of the curable resin composition. 2 parts by weight of plating fine particles (Micropal AU-206 manufactured by Sekisui Chemical Co., Ltd.) were mixed with a vacuum planetary mixer to prepare a vertical conduction material for liquid crystal display elements.

A liquid crystal display element was produced in the same manner as in Example 4, except that the obtained vertical conduction material was coated on the vertical conduction electrode via a dispenser to form a vertical conduction pattern on the transparent substrate.

The obtained liquid crystal display device was left in an environment of 60° C. and 95% RH for 500 hours, and the conductivity was good at this time.

(Example 9)

(Synthesis of compound (1))

Add diphenyl sulfide (10 mol), aluminum chloride (10 mol), and carbon disulfide (2 L) into a three-neck flask equipped with a dropping funnel, a mechanical stirrer, and a hydrogen chloride gas collector, and stir at 0°C. Isobutyryl chloride (10 mol) was slowly added dropwise to the reaction solution under the condition that the reaction solution did not exceed 10° C., and stirred at room temperature for 24 hours after the dropwise addition was completed. Ice water was added to the reaction solution to stop the reaction, and the organic layer was extracted with chloroform, washed with ion-exchanged water, and dried over anhydrous magnesium sulfate. The solution was concentrated and purified under reduced pressure to obtain a compound (1) having a structure shown in the following formula (20).

[chemical formula 14]

(Synthesis of compound (2))

Add compound (1) (5 mol), aluminum chloride (5 mol), and carbon disulfide (1 L) into a three-neck flask equipped with a dropping funnel, a mechanical stirrer, and a hydrogen chloride gas collector, and stir at 0°C. Benzoyl chloride (5 mol) was slowly added dropwise to the reaction solution under the condition that the reaction solution did not exceed 10° C., and stirred at room temperature for 24 hours after the dropping was completed. Ice water was added to the reaction solution to stop the reaction, and the organic layer was extracted with chloroform, washed with ion-exchanged water, and dried over anhydrous magnesium sulfate. This solution was concentrated and purified under reduced pressure to obtain a compound (2) having a structure shown in the following formula (21).

[chemical formula 15]

(Synthesis of Radical Polymerization Initiator A)

Compound (2) (2 mol), dimethyl sulfoxide (2 L) and methanol solution of potassium hydroxide (potassium hydroxide: 2 mol/ethanol: 100 mL) were added to a flask under nitrogen, and stirred at room temperature. Paraformaldehyde (2 mol of aldehyde units) was added to this solution, and it stirred at room temperature for 5 hours. Hydrochloric acid was added to the solution for neutralization, and the organic layer was extracted with ethyl acetate, washed with ion-exchanged water, and dried over anhydrous magnesium sulfate. This solution was concentrated and purified under reduced pressure to obtain a radical polymerization initiator A having a structure shown in the following formula (22).

[chemical formula 16]

2 parts by weight of radical polymerization initiator A, 40 parts by weight of partially acrylated epoxy resin (manufactured by Daicel ユ-シ-ビ-, UVAC1561), bisphenol A epoxy acrylate resin (Daycel ユ-シ-ビ) -The-social system, EB3700) 20 weight mix, heating it to 70 ° C to dissolve the free radical polymer dictator A, and then stir with a planetary stirring device to obtain a mixture.

15 parts by weight of spherical silica (manufactured by Admatex, SO-C1), 5 parts by weight of epoxy thermosetting agent (manufactured by Otsuka Chemical Co., Ltd., ADH), and coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed into the mixture as a filler. system, KBM403) 1 part by weight, stirred with a planetary stirring device, and then dispersed with three ceramic rollers to obtain a curable resin composition.

Disperse 1 part by weight of spacer particles (manufactured by Sekisui Chemical Industry Co., Ltd., Micropal SP-2055) in 100 parts by weight of the curable resin composition obtained, and as a sealant for liquid crystal display elements, two tapes were completed. The rubbing-treated alignment film and the transparent electrode are coated on one substrate of the glass substrate with a dispenser.

Next, liquid crystal (manufactured by Chitsuso Co., Ltd., JC-5004LA) is dripped onto the entire surface of the sealant frame of the glass substrate with a transparent electrode, immediately superimposed another glass substrate with a transparent electrode, and applied to the sealant part. A high-pressure mercury lamp with a filter that cuts off light below 350 nm was irradiated at 50 mW/cm ² for 20 seconds to cure it, thereby obtaining a liquid crystal display element.

(Example 10)

(Synthesis of Radical Polymerization Initiator B)

The compound (2) (1 mol) described in Example 9 was added to the reaction flask, and heated and dissolved in a dry air atmosphere. 0.001 mol of dibutyltin dilaurate and 1 mol of 2-methacryloyloxyethylene isocyanate (manufactured by Showa Denko Co., Ltd.) were slowly added dropwise thereto, and then reacted at 90° C. until After confirming that no isocyanate group remained by infrared absorption spectrum analysis at °C, it was purified to obtain a radical polymerization initiator B having a structure shown in the following formula (23).

[chemical formula 17]

A curable resin composition was prepared in the same manner as in Example 9, except that radical polymerization initiator B was used instead of radical polymerization initiator A in Example 9.

Then, a liquid crystal display element was obtained in the same manner as in Example 9 using the obtained curable resin composition.

(Example 11)

(Synthesis of Radical Polymerization Initiator C)

The compound (2) (1 mol) described in Example 9 was added to the reaction flask, and heated and dissolved in a dry air atmosphere. Under the condition that the reaction temperature does not exceed 90°C, 0.001 moles of dibutyltin dilaurate and 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate (Degsa Corporation) are slowly added dropwise thereto. 0.5mol), after the dropwise addition, slowly add 2-hydroxyethyl acrylate (0.5mol) dropwise under the condition that the reaction temperature does not exceed 90°C, and react at 90°C until it is confirmed by infrared absorption spectrum analysis The radical polymerization initiator C having the structure shown in the following formula (24) was obtained by purifying after removing the remaining isocyanate group.

[chemical formula 18]

Wherein, A in formula (24) represents 2,2,4- and 2,4,4-trimethylhexamethylene.

Except having used the radical polymerization initiator C instead of the radical polymerization initiator A of Example 9, it carried out similarly to Example 9, and obtained the curable resin composition.

Then, a liquid crystal display element was obtained in the same manner as in Example 9 using the obtained curable resin composition.

(Example 12)

(Synthesis of radical polymerization initiator D)

2-Carboxymethoxythioxan-9-one (1 mol) was added to the reaction flask, and it was heated and dissolved in a dry air atmosphere. 0.001 mol of dibutyltin dilaurate and 1 mol of 2-methacryloyloxyethylene isocyanate (manufactured by Showa Denko Co., Ltd.) were slowly added dropwise thereto, and then reacted at 90° C. until After confirming that no isocyanate group remained by infrared absorption spectrum analysis at °C, it was purified to obtain a radical polymerization initiator D having a structure shown in the following formula (25).

[chemical formula 19]

Except having used the radical polymerization initiator D instead of the radical polymerization initiator A of Example 9, it carried out similarly to Example 9, and obtained the curable resin composition.

Then, a liquid crystal display element was obtained in the same manner as in Example 9 using the obtained curable resin composition.

(comparative example 5)

A curable resin composition was obtained in the same manner as in Example 9 except that Irgacyua 2959 (manufactured by Nagase Sangyo Co., Ltd.) was used instead of the radical polymerization initiator A in Example 9.

Then, a liquid crystal display element was obtained in the same manner as in Example 9 using the obtained curable resin composition.

(comparative example 6)

Except having used Irgacyua 651 (made by Nagase Sangyo Co., Ltd.) instead of the radical polymerization initiator A of Example 9, it carried out similarly to Example 9, and obtained the curable resin composition.

Then, a liquid crystal display element was obtained in the same manner as in Example 9 using the obtained curable resin composition.

The radical polymerization initiators, curable resin compositions, and liquid crystal display elements obtained in Examples 9-12 and Comparative Examples 5 and 6 were evaluated by the following methods, and the respective results are shown in Table 3 below.

(Measurement of molar absorptivity)

Prepare a radical polymerization initiator solution with acetonitrile (manufactured by Dojin Chemical Co., Ltd.) using ultraviolet absorption spectroscopy. The sample concentration is 1.0×10 ^-4 M. , manufactured by Shimadzu Corporation) to measure the absorbance. The molar absorptivity is the value obtained by dividing the measured absorbance by the molar concentration (M) of the solution and the thickness (cm) of the cell.

(Liquid crystal resistivity retention measurement)

0.5 g of the curable resin composition was added to an ampoule bottle (inner diameter: 10.0 mm), and 0.5 g of liquid crystal was added. The bottle was placed in an oven at 120° C. for 1 hour, and after returning to room temperature (25° C.), a liquid crystal resistivity measuring device (manufactured by KEITHLEY Instruments, 6517A) was used for the liquid crystal part, and a liquid electrode (manufactured by Ando Electric Co., Ltd.) was used as an electrode. , LE-21 type), in the standard temperature and humidity state (20 ℃, 65% RH) to measure the liquid crystal resistivity, so as to obtain the liquid crystal resistivity retention rate.

(Nematic-isotropic liquid transition point (N-I point) change measurement)

0.5 g of the curable resin composition was added to an ampoule (inner diameter: 10.0 mm), and 0.5 g of liquid crystal was added. Put the bottle in an oven at 120°C for 1 hour, and after returning to room temperature (25°C), put the liquid crystal part on an aluminum plate, measure the temperature at a rate of 10°C/min and measure the peak temperature to determine the nematic type - Isotropic liquid transition point and nematic-isotropic liquid transition point variation. In addition, MDSC (manufactured by TA Insturumenes) was used as a thermal analysis device.

(Measurement of conversion rate of acryloyl group)

1 part by weight of spacer particles (manufactured by Sekisui Chemical Industry Co., Ltd., Micropal SP-2055) was dispersed in 100 parts by weight of the obtained curable resin composition, and placed in the center of glass (manufactured by Corning Co., Ltd., 1737), Another glass (manufactured by Corning Co., Ltd., 1737) was stacked thereon to spread the curable resin composition and make the thickness uniform, thereby producing a test piece.

The prepared test piece was irradiated with 50 mW/cm ² for 20 seconds by a high-pressure mercury lamp equipped with a filter that cuts off light of 350 nm or less. Then, one piece of glass on the test piece was peeled off and measured using an infrared spectrophotometer (EXCALIBUR FTS3000MX, manufactured by BIO RAD). The conversion is calculated by comparing the peak area of the acryl group before curing (815-800 cm ^-1 ) and the peak area of the acryl group after curing (815-800 cm ^-1 ) measured separately with the reference peak area (845-820 cm ^-1 ). Rate. The conversion ratio of the acryloyl group was calculated from the following formula.

[mathematical formula 5]

Conversion rate of acryloyl group = {1-(peak area of acryloyl group after curing/standard peak area after curing)/(peak area of acryloyl group before curing/standard peak area before curing)}×100

(jointness evaluation)

Disperse 1 part by weight of spacer particles (Micropal SP-2055 manufactured by Sekisui Chemical Industry Co., Ltd.) in 100 parts by weight of the curable resin composition, place it at the center of the slide glass, and stack another slide glass on it. The curable resin composition was developed to have a uniform thickness, and irradiated with a high-pressure mercury lamp at 50 mW/cm ² for 20 seconds with a filter that cuts off light of 350 nm or less. Then, it heated at 120 degreeC for 1 hour, and obtained the joint test piece. The adhesive strength of this test piece was measured with the tensiometer.

(Evaluation of liquid crystal display panels (evaluation of color unevenness))

About the obtained liquid crystal display element, the disorder of the liquid crystal orientation near the sealant was evaluated with the naked eye according to the following criteria immediately after manufacture and after operating test on 65 degreeC95%RH condition for 1000 hours. Also, the number of samples is six.

◎: No color unevenness at all

○: Slight color unevenness

△: Some color unevenness

×: Color unevenness is fairly clear

[table 3] Molar absorptivity (M ^-1 ·cm ^-1 ) Liquid crystal resistivity retention (%) NI point change (℃) Acryloyl conversion rate (%) Evaluation of zygosity (N/cm ² ) LCD panel evaluation Example 9 1900 80 -1.6 95 450 ◎ Example 10 1500 70 -1.8 95 420 ◎ Example 11 1200 65 -1.4 95 410 ◎ Example 12 1200 75 -1.8 90 480 ◎ Comparative Example 5 50 40 -1.4 20 400 x Comparative Example 6 150 5 -6.5 80 360 △

(Example 13)

The curable resin composition obtained in the same manner as in Example 9 was thoroughly mixed with a three-roll mixer until a uniform liquid was formed, and then, metal electroconductive fine particles to be plated with gold were mixed with respect to 100 parts by weight of the curable resin composition. 2 parts by weight of plating fine particles (Micropal AU-206 manufactured by Sekisui Chemical Co., Ltd.) were mixed with a vacuum planetary mixer to prepare a vertical conduction material for liquid crystal display elements.

A liquid crystal display element was produced in the same manner as in Example 9, except that the obtained vertical conduction material was coated on the vertical conduction electrode via a dispenser to form a vertical conduction pattern on the transparent substrate.

The obtained liquid crystal display element was similarly evaluated for a liquid crystal display panel (evaluation of color unevenness), and the disorder of liquid crystal alignment in the vicinity of the vertical conductive material was visually observed, and there was no color unevenness at all. In addition, the conductivity was also good.

(Example 14)

70 parts by weight of a partially acrylated epoxy resin (made by Daicel Yu-shi-bi Co., Ltd., UVAC1561) as a curable resin, bisphenol F-type epoxy resin (made by Dainippon Ink Chemical Industry Co., Ltd., Epichrome 830S) 30 parts by weight, 20 parts by weight of spherical silica (manufactured by Adomafine Co., Ltd., SO-Cl) as a filler, 40 parts by weight of Amiquia VDH (manufactured by Miso Fine Technology Co., Ltd.) as a curing agent, and 40 parts by weight as a photoradical polymerization initiator A composition consisting of 3 parts by weight of Irugakuyua 907 (manufactured by Ciba Specialty Chemicals Inc.) was mixed until a uniform liquid was formed to obtain a stock solution of a curable resin composition.

Composelan E202 (manufactured by Arakawa Chemical Co., Ltd., average molecular weight 560) was mixed with 100 parts by weight of the obtained curable resin composition stock solution to prepare a curable resin composition.

A liquid crystal display device was produced using the obtained curable resin composition as a sealing compound for liquid crystal display elements.

That is, on one of two transparent substrates with transparent electrodes, a sealant is applied with a dispenser so as to draw a rectangular frame. Next, liquid crystal (manufactured by Chitsuso Co., Ltd., JC-5004LA) was sprayed onto the entire surface of the frame of the transparent substrate, and another transparent substrate was superimposed immediately, and the sealed part was irradiated with ultraviolet rays at an intensity of 50 mW/cm ² using a high-pressure mercury lamp. 120 seconds. Then, while annealing the liquid crystal at 120° C. for 1 hour, the sealant for liquid crystal display elements was thermally cured to obtain a liquid crystal display element.

(Example 15)

An alkoxysilane compound was produced by making 1 mol of 3-isocyanate trimethoxysilane and 1 mol of Epichrome EXA-7120 (manufactured by Dainippon Ink Chemicals) react at 70° C. for 12 hours in the presence of a tin catalyst. The molecular weight of the alkoxysilane compound is about 655.

A curable resin composition was prepared by mixing 5 parts by weight of the obtained alkoxysilane compound with 100 parts by weight of the stock solution of the curable resin composition produced in Example 14.

Except having used the obtained curable resin composition, the liquid crystal display element was produced by the method similar to Example 14.

(Example 16)

With respect to 100 parts by weight of the curable resin composition stock solution made in Example 14, N-1-phenylethyl-N'-triethoxysilylpropyl urea (molecular weight 349.5, hydrogen bonding functional group value 5.72 ×10 ^-3 mol/g) 5 parts by weight to prepare a curable resin composition.

Except having used the obtained curable resin composition, the liquid crystal display element was produced by the method similar to Example 14.

(Example 17)

1 mol of 3-aminopropyltrimethoxysilane and 1 mol of 3-acryloyloxypropyltrimethoxysilane were reacted at 70 degreeC for 12 hours, and the alkoxysilane compound was produced. The molecular weight of the alkoxysilane compound was about 413, and the hydrogen-bonding functional group value was 2.42×10 ^-3 mol/g.

A curable resin composition was prepared by mixing 5 parts by weight of the obtained alkoxysilane compound with 100 parts by weight of the stock solution of the curable resin composition produced in Example 14.

Except having used the obtained curable resin composition, the liquid crystal display element was produced by the method similar to Example 14.

(Example 18)

An alkoxysilane compound was prepared by reacting 1 mol of 3-aminopropyltrimethoxysilane with 1 mol of Karenz MOI for 12 hours. The molecular weight of this alkoxysilane compound was about 334, and the hydrogen-bonding functional group value was 2.99×10 ^-3 mol/g.

A curable resin composition was prepared by mixing 5 parts by weight of the obtained alkoxysilane compound with 100 parts by weight of the stock solution of the curable resin composition produced in Example 14.

Except having used the obtained curable resin composition, the liquid crystal display element was produced by the method similar to Example 14.

(Example 19)

1 mol of 3-isocyanate trimethoxysilane and 1 mol of 2-hydroxyethyl methacrylate were reacted at 70 degreeC for 12 hours in presence of a tin catalyst, and an alkoxysilane compound was produced. The molecular weight of this alkoxysilane compound was about 271, and the hydrogen-bonding functional group value was 3.69×10 ^-3 mol/g.

A curable resin composition was prepared by mixing 5 parts by weight of the obtained alkoxysilane compound with 100 parts by weight of the stock solution of the curable resin composition produced in Example 14.

Except having used the obtained curable resin composition, the liquid crystal display element was produced by the method similar to Example 14.

(comparative example 7)

Only the stock solution of the curable resin composition produced in Example 14 (the curable resin composition before mixing Comporasen E202) was used as the curable resin composition.

Except having used the obtained curable resin composition, the liquid crystal display element was produced by the method similar to Example 14.

(comparative example 8)

A curable resin composition was prepared by mixing 3 parts by weight of 3-glycidoxypropyltrimethoxysilane and 100 parts by weight of the stock solution of the curable resin composition prepared in Example 14.

Except having used the obtained curable resin composition, the liquid crystal display element was produced by the method similar to Example 14.

(comparative example 9)

A curable resin composition was prepared by mixing 3 parts by weight of 3-methacryloxypropyltrimethoxysilane and 100 parts by weight of the stock solution of the curable resin composition produced in Example 14.

Except having used the obtained curable resin composition, the liquid crystal display element was produced by the method similar to Example 14.

(evaluate)

Adhesiveness, moisture-resistant adhesiveness, and color unevenness of the liquid crystal display element of the curable resin compositions obtained in Examples 14-19 and Comparative Examples 7-9 were evaluated by the following methods.

(1) Evaluation of zygosity

3 parts by weight of polymer hollow particles (manufactured by Sekisui Chemical Industry Co., Ltd., Micropal SP) with an average particle diameter of 5 μm were dispersed in 100 parts by weight of the curable resin composition with a planetary stirring device to form a uniform liquid, which was A small amount was placed at the center of the slide, and another slide was superimposed on it for development, and then irradiated with ultraviolet light at an intensity of 100 mW/cm ² for 30 seconds.

Then, it heated at 100 degreeC for 1 hour, and obtained the joint test piece. About the obtained test piece, the adhesive strength was measured using the automatic recorder (made by Shimadzu Corporation).

(2) Moisture-resistant bonding evaluation

The same bonding sheet as that produced in bonding evaluation was stored in saturated water vapor at 120° C. and 2 atmospheres for 24 hours, and then the bonding strength was measured using an automatic recorder (manufactured by Shimadzu Corporation).

(3) Evaluation of color unevenness

About the obtained liquid crystal display element, the color unevenness which arises in the liquid crystal around a sealing part was observed with the naked eye, and it evaluated in accordance with the following criteria.

◎: No color unevenness at all

○: Almost no color unevenness

△: Slight color unevenness

×: There is considerable color unevenness

[Table 4] Bondability (N/cm ² ) Moisture resistance bonding (N/cm ² ) Evaluation of Color Nonuniformity Example 14 392 343 ◎ Example 15 451 392 ◎ Example 16 353 304 ◎ Example 17 363 314 ◎ Example 18 402 343 ◎ Example 19 441 392 ◎ Comparative Example 7 216 20 ◎ Comparative Example 8 392 314 x Comparative Example 9 343 294 x

(Example 20)

The curable resin composition obtained in the same manner as in Example 14 was thoroughly mixed with a three-roll mixer until a uniform liquid was formed, and then a metal plated with gold as conductive fine particles was mixed with respect to 100 parts by weight of the curable resin composition. 2 parts by weight of plating fine particles (Micropal AU-206 manufactured by Sekisui Chemical Co., Ltd.) were mixed with a vacuum planetary mixer to prepare a vertical conduction material for liquid crystal display elements.

A liquid crystal display element was fabricated in the same manner as in Example 14, except that the obtained vertical conduction material was applied on a transparent substrate with a dispenser to form a vertical conduction pattern on the vertical conduction electrode.

The conductivity of the obtained liquid crystal display element was favorable.

(Example 21)

(1) Preparation of curable resin composition

60 parts by weight of bisphenol A type epoxy acrylate (made by Daicel UCB Co., Ltd., EB3700) as a resin having a radically polymerizable functional group, bisphenol A type epoxy resin (made by Japan Epoxy Resin Co., Ltd.: Epico-to 828 ) and 2 parts by weight of a radical photopolymerization initiator (manufactured by Ciba Specialty Chemicals Inc.: IR-651) were mixed, heated to 70°C to dissolve the photoradical polymerization initiator, and then carried out with a planetary stirring device. Stir to obtain a mixture.

10 parts by weight of core-shell microparticles (manufactured by Nippon Zeon Corporation: F-351), 16 parts by weight of spherical silica (manufactured by Adomafine Corporation, SO-C1), and a thermosetting agent (manufactured by Otsuka Chemical Co., Ltd., ADH) 2 parts by weight, mixed and stirred with a planetary stirring device, and then dispersed with three ceramic rollers to obtain a curable resin composition.

(2) Measurement of the glass transition temperature of the cured product

The obtained curable resin composition is coated into a rectangular sheet of 5×35×0.35 mm, irradiated with ultraviolet light of 100 mW intensity for 30 seconds, and then heat-treated at 120° C. for 60 minutes to cure it, and obtain a test for measurement. piece.

The elastic modulus E' and tan δ were obtained in the temperature range of 20°C to 180°C with a dynamic viscoelasticity measuring device (DMA), and the glass transition temperature of the cured product of the curable resin composition was measured from the values, and found to be 50°C.

(3) Bonding test

With respect to 100 parts by weight of the obtained curable resin composition, 5 parts by weight of short glass fiber separators of 5 μm were mixed, and the mixed material was finely dropped on an alkali-free glass substrate (manufactured by Corning: #1737), and the The same glass substrate was adhered thereon in a cross shape. After irradiating ultraviolet rays with an intensity of 100 mW for 30 seconds, heat treatment was performed at 120° C. for 60 minutes to cure, and a test piece for measurement was obtained.

Each glass substrate was fixed on chucks distributed up and down, and the tensile strength was determined under the condition of a tensile speed of 5 mm/sec, which was defined as the adhesive strength. The bonding strength was 180 N/cm ² .

(comparative example 10)

60 parts by weight of bisphenol A type epoxy acrylate (made by Daicel UCB Co., Ltd., EB3700) as a resin having a radically polymerizable functional group, bisphenol A type epoxy resin (made by Japan Epoxy Resin Co., Ltd.: Epico-to 828 ) and 2 parts by weight of a radical photopolymerization initiator (manufactured by Ciba Specialty Chemicals Inc.: IR-651) were mixed, heated to 70°C to dissolve the photoradical polymerization initiator, and then carried out with a planetary stirring device. Mix and stir to obtain a mixture. In this mixture, 26 parts by weight of spherical silica (manufactured by Adomaphyin Co., Ltd., SO-C1) and 2 parts by weight of a thermosetting agent (manufactured by Otsuka Chemical Co., Ltd., ADH) were mixed, mixed and stirred with a planetary stirrer, and then three Ceramic rollers were used to disperse the mixture to obtain a curable resin composition.

For the obtained curable resin composition, the glass transition temperature and adhesive strength of the cured product were measured by the same method as in Example 21, and the glass transition temperature was 150° C., and the adhesive strength was 80 N/cm ² .

(comparative example 11)

60 parts by weight of propylene oxide-added bisphenol A type epoxy acrylate (manufactured by Kyoeisha Chemical Co., Ltd.: 3002A), bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd.) Made by the company: EPICO-TO828) 10 parts by weight, photoradical polymerization initiator (manufactured by Ciba Specialty Chemicals Inc.: IR-651) 2 parts by weight mixed, and heated to 70°C to dissolve the photoradical polymerization initiator, Then, it was stirred with a planetary stirring device to obtain a mixture. 10 parts by weight of core-shell microparticles (manufactured by Nippon Zeon Corporation: F-351), 16 parts by weight of spherical silica (manufactured by Adomafine Corporation, SO-C1), and a thermosetting agent (manufactured by Otsuka Chemical Co., Ltd., ADH) 2 parts by weight, mixed and stirred with a planetary stirring device, and then dispersed with three ceramic rollers to obtain a curable resin composition.

For the obtained curable resin composition, the glass transition temperature and adhesive strength of the cured product were measured in the same manner as in Example 21. The glass transition temperature was 100°C and the adhesive strength was 90 N/cm ² .

(Example 22)

The curable resin composition obtained in the same manner as in Example 21 was thoroughly mixed using a three-roll mixer until a uniform liquid was formed, and then mixed with gold-plated metal as conductive fine particles with respect to 100 parts by weight of the curable resin composition. 2 parts by weight of plating fine particles (Micropal AU-206 manufactured by Sekisui Chemical Co., Ltd.) were mixed with a vacuum planetary mixer to prepare a vertical conduction material for liquid crystal display elements.

On one of the two transparent substrates with transparent electrodes, the curable resin composition obtained in Example 21 was applied as a sealant with a dispenser to draw a rectangular frame. Furthermore, on another transparent substrate, the dispenser for the obtained vertical conduction material was coated on the electrodes for vertical conduction to form a pattern for vertical conduction. Next, liquid crystal (manufactured by Chitsuso Co., Ltd., JC-5004LA) was drip-coated on the entire surface of the transparent substrate frame on which the sealant was applied, and another transparent substrate was immediately superimposed, and the sealing part and the upper and lower conduction material parts were used. A high-pressure mercury lamp irradiates ultraviolet light at an intensity of 100 mW/ ^cm2 for 30 seconds. Then, the liquid crystal was annealed at 120° C. for 1 hour, and thermally cured to obtain a liquid crystal display device.

The obtained liquid crystal display device had good conductivity.

(Example 23)

(A) Synthesis of Acrylic Modified Phenol Novolac Epoxy Resin

1000 parts by weight of a liquid phase phenol novolac epoxy resin (D.E.N.431 manufactured by Dow Chemical Corporation), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 200 parts by weight of acrylic acid The mixture was stirred and refluxed at 90° C. for 5 hours while supplying air. 100 parts by weight of the obtained resin was filtered through a column filled with 10 parts by weight of quartz and kaolin natural bonding product (manufactured by Hoffman Mineral Co., Ltd., Silitin V85) to absorb ionic impurities in the reactant, thereby obtaining acrylic acid modification. Resistant phenol novolak epoxy resin (50% partial acryloyl).

(B) Synthesis of urethane-modified partial acryloyl compounds

Add 134 parts by weight of trimethylolpropane, 0.2 parts by weight of BHT as a polymerization initiator, 0.01 parts by weight of dibutyltin dilaurate as a reaction catalyst, and 666 parts by weight of isophorone diisocyanate, and stir and reflux at 60°C And it was made to react for 2 hours. Then, 25.5 parts by weight of 2-hydroxyethyl acrylate and 111 parts by weight of glycidol were added, and the mixture was stirred and refluxed at 90° C. for 2 hours while feeding air. 100 parts by weight of the obtained resin was filtered through a column filled with 10 parts by weight of quartz and kaolin natural bonding product (manufactured by Hofman Mineral Co., Ltd., Silitin V85) to absorb ionic impurities in the reactant, thereby obtaining urethane Modified part of acryloyl compound.

With 40 weight parts of acrylic acid modified phenol novolac epoxy resins obtained in (A), 20 weight parts of urethane modified partial acryloyls obtained in (B), as the hydrazide type curing agent of latent thermosetting agent ( Made by Miso Fine Technology Co., Ltd., 15 parts by weight of Amicyua VDH), 1 part by weight of 2,2-diethoxyacetophenone as a photopolymerization initiator, 23 parts by weight of silicon oxide particles (average particle diameter: 0.5 μm), γ - A curable resin composition consisting of 1 part by weight of glycidoxypropyltrimethoxysilane was thoroughly mixed using a three-roll mixer until a uniform liquid was formed, thereby obtaining a sealant.

On one of the two transparent substrates with transparent electrodes, the obtained sealant was applied with a dispenser so as to draw a rectangular frame. Next, liquid crystal (manufactured by Chitsuso Co., Ltd., JC-5004LA) was sprayed onto the entire surface of the frame of the transparent substrate, and another transparent substrate was superimposed immediately, and the sealed part was irradiated with ultraviolet rays at 100 mW/ ^cm2 for 30 seconds with a high-pressure mercury lamp. . Then, the liquid crystal was annealed at 120° C. for 1 hour, and thermally cured to fabricate a liquid crystal display device.

(Example 24)

(C) Synthesis of Acrylic Modified Propylene Oxide Bisphenol A Epoxy Resin

1440 parts by weight of liquid-phase polyoxyalkylene bisphenol A diglycidyl ether (manufactured by Asahi Denka Industries, Ltd., EP4000S), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, and 2 parts by weight of triethylamine as a reaction catalyst. Parts by weight, 200 parts by weight of acrylic acid were stirred and refluxed at 90° C. for 5 hours while feeding air. 100 parts by weight of the obtained resin was filtered through a column filled with 10 parts by weight of quartz and kaolin natural bonding product (manufactured by Hoffman Mineral Co., Ltd., Silitin V85) to absorb ionic impurities in the reactant, thereby obtaining acrylic acid modification. Propylene oxide bisphenol A epoxy resin (50% partial acryloyl).

In addition to using 20 parts by weight of acrylic modified propylene oxide bisphenol A epoxy resin obtained from (C) instead of 20 parts by weight of urethane-modified partial acryloyl obtained from Example 23 (B), a hydrazide type curing A sealant was obtained in the same manner as in Example 23 except that 15 parts by weight of a hydrazide-type curing agent (manufactured by Nippon Hydrazine Industry Co., Ltd., NDH) was replaced by 15 parts by weight of a hydrazide-type curing agent (manufactured by Miso Fain Techno Co., Ltd., Amikua VDH), and a liquid crystal display device was produced using it. .

(comparative example 12)

A curing agent consisting of 35 parts by weight of urethane acrylate (manufactured by Kyoeisha Chemical Co., Ltd., AH-600), 15 parts by weight of 2-hydroxybutyl acrylate, 50 parts by weight of isobornyl acrylate, and 3 parts by weight of benzophenone Mix with a permanent resin composition to form a uniform liquid to obtain a light-curable sealant, which is used to manufacture liquid crystal display devices.

(comparative example 13)

A curable resin composition composed of 50 parts by weight of bisphenol A epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., Epico-to 828US) and 25 parts by weight of a hydrazide curing agent (manufactured by Nippon Hydrazine Industry Co., Ltd., NDH) was used A three-roll mixer was thoroughly mixed until a uniform liquid was formed, thereby obtaining a sealant, which was used to fabricate a liquid crystal display device.

For the sealants made in Examples 23 and 24 and Comparative Examples 12 and 13, the following methods were used to evaluate the average linear expansion coefficient after photocuring and photothermal curing, as well as the volume resistance value after curing and the dielectric strength at 100 kHz. Constant, tensile modulus, and color unevenness of the obtained liquid crystal display device were evaluated by the following method.

(Average linear expansion rate after photocuring and photothermal curing)

The sealant was thinly and uniformly coated on the polyvinyl fluoride substrate, and then cured by ultraviolet light under the condition of 3000mJ/cm ² , thereby producing a photocured sample with a size of 15mm×4mm and a thickness of 0.6mm. In addition, the sealant is thinly and uniformly coated on the polyvinyl fluoride substrate, and then UV-cured under the condition of 3000mJ/cm ² , and then heat-cured under the condition of 120°C for 1 hour, so that the size is 15mm×4mm, thick 0.6mm photothermally cured samples.

Using "EXSTAR6000TMA/SS" manufactured by Seiko Electronics Co., Ltd., under the measurement conditions of initial temperature: 35°C, heating end temperature: 150°C, heating rate: 5°C/min, holding time: 0min, the prepared light-cured samples and light-cured samples were measured. Average linear expansion of heat cured samples.

Calculate the temperature from the temperature 40°C lower than the glass transition temperature to the temperature 10°C lower than the glass transition temperature for the cured product when it is cured only by the action of light and the cured product when it is cured by the action of light and heat from the obtained value between the average linear expansion rate α ₁ , and the average linear expansion rate α ₂ from a temperature 10°C higher than the glass transition temperature to a temperature 40°C higher than the glass transition temperature.

(Volume resistance value after curing)

Thinly and evenly coat the sealant on the chrome-deposited surface of the chrome-deposited glass substrate, and then perform ultraviolet curing to form a UV-cured product with a size of 85mm×85mm and a thickness of 3mm, place a chrome-deposited glass substrate on it and The chromium vapor-deposited surface was placed on the ultraviolet cured product side, a load was applied, and a test sample was prepared by heating and pressing on a hot plate at 120° C. for 1 hour. The area (S (cm ² )) of the sealant in the sample was measured, and a constant voltage generating device (manufactured by Kenwood Co., Ltd., PA 36-2A modulated DC power supply) was used between the chrome-deposited surfaces of the opposing chrome-deposited glass substrates. A constant voltage (V(V)) was applied, and the current (A(A)) flowing in the film was measured with an ammeter (R644C digital multimeter, manufactured by Advantest Co., Ltd.). When the film pressure of the sealant is T (cm), the volume resistivity (Ω.cm) was obtained by the following formula.

[mathematical formula 6]

Volume resistivity (Ω cm) = (V × S) / (A × T)

Wherein, the applied voltage is DC 500V, and the conduction time is 1 minute.

(dielectric constant at 100kHz after curing)

The sealant was applied thinly and uniformly on the glass substrate, and then cured to produce a test sample with a size of 60 mm×60 mm and a thickness of 3 mm. According to the method of ASTM D150, the measurement is carried out at a frequency of 100 kHz with an electrode for dielectric measurement (manufactured by Yokogawa HP Co., Ltd., HP16451B) and an LCR meter (manufactured by Hewlett Packard Co., Ltd., 4284A) by the electrode non-contact method (gap method). .

(tensile modulus after curing)

The sealant was thinly and evenly coated on the polyvinyl fluoride substrate, and then UV-cured to form a UV-cured product with a size of 50mm×5mm and a thickness of 0.5mm, and then heated at 120°C for 1 hour to prepare a test sample.

Use "RSA II" manufactured by Tei-Ei Instruments Inc., length between clamps: 30mm, temperature conditions: initial temperature: room temperature, heating end temperature: 150°C, heating rate: 5°C/min, and specify the data to be obtained Interval, lower limit elastic rate: 10Pa, lower limit dynamic force: 0.008N, measurement frequency: 10Hz, deformation (E>108): 0.1%, static/dynamic ratio: 0, upper limit stretch rate: 50%, stretch index: 1 The tensile modulus of the prepared test sample was measured under the conditions.

(Evaluation of color unevenness)

For the obtained liquid crystal display device, before and after 60° C., 95% RH, 500 hours, the color unevenness generated in the liquid crystal was observed with the naked eye, and the evaluation was based on the following four-level criteria: ◎ (no color unevenness at all); ○ ( Slight color unevenness); △ (some color unevenness); × (color unevenness considerably). In addition, among them, evaluation was performed using 5 samples for each part.

[table 5] Example 23 Example 24 Comparative Example 12 Comparative Example 13 Reactive resin composition (weight part) Acrylic Modified Phenol Novolac Epoxy Resin 40 40 - - Urethane acrylate - - 35 - Urethane partially modified acryloyl 20 - - - Acrylic modified propylene oxide bisphenol A epoxy resin - 20 - - 2-Hydroxybutyl Acrylate - - 15 - Bisphenol A epoxy resin - - - 50 Isobornyl Acrylate - - 50 - Hydrazide curing agent (VDH) 15 - - - Hydrazide curing agent (NDH) - 15 - 25 Silica particles twenty three twenty three - - evaluate Average linear expansion rate α ₁ (/°C) after photocuring 2×10 ^-4 2×10 ^-4 9×10 ^-5 - Average linear expansion rate α ₂ (/°C) after photocuring 8×10 ^-4 8×10 ^-4 4×10 ^-4 - Average linear expansion rate α ₁ (/°C) after photothermal curing 7×10 ^-5 8× ^10-5 8× ^10-5 3×10 ^-5 Average linear expansion coefficient α ₂ (/°C) after photothermal curing 2×10 ^-4 3×10 ^-4 3×10 ^-4 1×10 ^-4 Volume resistance value (Ω.cm) 1.5×10 ¹³ 2.1×10 ¹³ 1.2×10 ¹³ 3.0×10 ¹³ Dielectric constant (100kHz) 3.4 3.2 3.4 3.1 Tensile modulus (MPa) 2000 1000 2000 4000 Color unevenness evaluation (initial stage) ◎○◎○◎ ◎○◎○◎ ○○○○○ ××××× Color unevenness evaluation (after humidity resistance evaluation) ◎○◎○◎ ◎○◎○◎ ××××× ×××××

(Example 25)

The curable resin composition obtained in the same manner as in Example 23 was thoroughly mixed with a three-roll mixer until a uniform liquid was formed, and then, gold-plated metal as conductive fine particles was mixed with respect to 100 parts by weight of the curable resin composition. 2 parts by weight of plating fine particles (Micropal AU-206 manufactured by Sekisui Chemical Co., Ltd.) were mixed with a vacuum planetary mixer to prepare a vertical conduction material for liquid crystal display elements.

A liquid crystal display device was fabricated in the same manner as in Example 23, except that the obtained vertical conduction material dispenser was coated on the vertical conduction electrode on the transparent substrate to form a vertical conduction pattern.

The obtained liquid crystal display device was evaluated for color unevenness in the same manner, and the color unevenness generated in the liquid crystal near the vertical conductive material was observed with the naked eye, and the result was an evaluation result of ◯ or higher. In addition, the conductivity was also good.

(Example 26)

1000 parts by weight of a liquid phase phenol novolac epoxy resin (D.E.N.431 manufactured by Dow Chemical Corporation), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 200 parts by weight of acrylic acid The mixture was stirred and refluxed at 90° C. for 5 hours while supplying air. 100 parts by weight of the obtained resin was filtered through a column filled with 10 parts by weight of quartz and kaolin natural bonding product (manufactured by Hoffman Mineral Co., Ltd., Silitin V85) to absorb ionic impurities in the reactant, thereby obtaining acrylic acid modification. Resistant phenol novolak epoxy resin (50% partial acryloyl).

Add 134 parts by weight of trimethylolpropane, 0.2 parts by weight of BHT as a polymerization initiator, 0.01 parts by weight of dibutyltin dilaurate as a reaction catalyst, and 666 parts by weight of isophorone diisocyanate, and stir and reflux at 60°C And it was made to react for 2 hours. Then, 25.5 parts by weight of 2-hydroxyethyl acrylate and 111 parts by weight of glycidol were added, and the mixture was stirred and refluxed at 90° C. for 2 hours while feeding air. 100 parts by weight of the obtained resin was filtered through a column filled with 10 parts by weight of quartz and kaolin natural bonding product (manufactured by Hofman Mineral Co., Ltd., Silitin V85) to absorb ionic impurities in the reactant, thereby obtaining urethane Modified part of acryloyl compound.

With respect to 40 parts by weight of the obtained acrylic-modified phenol novolac epoxy resin and 20 parts by weight of the urethane-modified partial acrylic product, a hydrazide-type curing agent (manufactured by Miso Fain Techno Co., Ltd. , melting point 160°C) 15 parts by weight, 2,2-diethoxyacetophenone as a photopolymerization initiator 1 part by weight, silicon oxide particles (average particle diameter: 1.5 μm) 23 parts by weight, γ-epoxypropylene 1 part by weight of oxypropyltrimethoxysilane was fully mixed using a three-roll mixer to obtain a mixture.

The obtained mixture was filtered using Bekipore 10 μm (manufactured by Nichidai Co., Ltd.) as a filter at a temperature of 40° C. and a pressure of 45 N/cm ² to obtain a curable resin composition. Use this as a sealant for liquid crystal display elements.

On one of the two transparent substrates with transparent electrodes, the obtained sealant for liquid crystal display elements was coated with a dispenser so that a rectangular frame was drawn. Next, liquid crystal (manufactured by Chitsuso Co., Ltd., JC-5004LA) was sprayed onto the entire surface of the frame of the transparent substrate, and another transparent substrate was superimposed immediately, and the sealed part was irradiated with ultraviolet rays at 100 mW/ ^cm2 for 30 seconds with a high-pressure mercury lamp. . Then, the liquid crystal was annealed at 120° C. for 1 hour to be thermally cured, thereby producing a liquid crystal display element. In addition, the cell gap of this liquid crystal display element was set to 5 μm.

(comparative example 14)

Except having not filtered with a filter, the curable resin composition was produced by the method similar to Example 26, and this was used as the sealing compound for liquid crystal display elements. Moreover, the liquid crystal display element was produced by the method similar to Example 26 using the obtained sealing compound for liquid crystal display elements.

(evaluate)

About the sealing compound for liquid crystal display elements and the liquid crystal display element produced by Example 26 and Comparative Example 14, the following method performed the foreign material inspection and the evaluation of the cell gap.

(1) Foreign matter inspection

Accurately weigh 2 mL of sealant for liquid crystal display elements on a 10 μm SUS sieve (φ75-h20), drop acetone from the top at 1.2 mL/min, and count the number of foreign objects remaining on the sieve with a 16-fold magnifying glass. The same operation was performed for n=5, and the average value thereof was obtained.

(2) Unit gap evaluation

Use a 16x magnifying glass to inspect the unit gap with the naked eye for defects.

[Table 6] The number of foreign objects (pieces) With or without cell gaps Example 26 0 none Comparative Example 14 115.6 have

(Example 27)

(1) Synthesis of Acrylic Modified Phenol Novolac Epoxy Resin

1000 parts by weight of a liquid phase phenol novolac epoxy resin (D.E.N.431 manufactured by Dow Chemical Corporation), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 200 parts by weight of acrylic acid The mixture was stirred and refluxed at 90° C. for 5 hours while supplying air. 100 parts by weight of the obtained resin was filtered through a column filled with 10 parts by weight of quartz and kaolin natural bonding product (manufactured by Hoffman Mineral Co., Ltd., Silitin V85) to absorb ionic impurities in the reactant, thereby obtaining acrylic acid modification. Resistant phenol novolak epoxy resin (50% partial acryloyl).

(2) Synthesis of urethane-modified partial acryloyl compounds

Add 134 parts by weight of trimethylolpropane, 0.2 parts by weight of BHT as a polymerization initiator, 0.01 parts by weight of dibutyltin dilaurate as a reaction catalyst, and 666 parts by weight of isophorone diisocyanate, and stir and reflux at 60°C And it was made to react for 2 hours. Then, 25.5 parts by weight of 2-hydroxyethyl acrylate and 111 parts by weight of glycidol were added, and the mixture was stirred and refluxed at 90° C. for 2 hours while feeding air. 100 parts by weight of the obtained resin was filtered through a column filled with 10 parts by weight of quartz and kaolin natural bonding product (manufactured by Hofman Mineral Co., Ltd., Silitin V85) to absorb ionic impurities in the reactant, thereby obtaining urethane Modified part of acryloyl compound.

(3) Preparation of sealant

40 parts by weight of the obtained acrylic-modified phenol novolak epoxy resin, 20 parts by weight of urethane-modified partial acryloyl, and a hydrazide-type curing agent (manufactured by Miso Fain Techno, Amikua VDH) as a latent heat curing agent 15 Parts by weight, 1 part by weight of 2,2-diethoxyacetophenone as a photopolymerization initiator, 23 parts by weight of silicon oxide particles (average particle diameter: 1.5 μm), γ-glycidoxypropyltrimethoxy A curable resin composition consisting of 1 part by weight of silane was thoroughly mixed with a three-roll mixer until a uniform liquid was formed, thereby obtaining a sealant.

(4) Manufacture of liquid crystal display elements

On predetermined positions on the surfaces of the two transparent substrates with transparent electrodes, a rectangular alignment film made of polyimide (Nissan Chemical Co., Ltd., Suneva-(SE-7492)) was formed by flexographic printing. Then, the obtained sealant was applied with a dispenser to draw a rectangular frame so as not to come into contact with the alignment film of one of the transparent substrates.

Next, liquid crystal (manufactured by Chitsuso Co., Ltd., JC-5004LA) was drip-coated on the entire surface of the transparent substrate frame, and the surface of the other transparent substrate on which the alignment film was formed was immediately superimposed, and the high-pressure mercury lamp for the sealant was energized with 100 mW. /cm ² irradiated with ultraviolet light for 30 seconds. Then, the liquid crystal was annealed at 120° C. for 1 hour to be thermally cured, thereby producing a liquid crystal display element.

When the obtained liquid crystal display element was observed with the naked eye, it was confirmed that the sealant and the alignment film were not in contact.

(comparative example 15)

A liquid crystal display element was produced in the same manner as in Example 27, except that a sealant in contact with the alignment film was formed on the surface of the transparent substrate with the transparent electrode.

As an evaluation of the color unevenness of the liquid crystal display elements produced in Example 27 and Comparative Example 15, the liquid crystal alignment near the sealant was confirmed with the naked eye immediately after production and after an operation test at 65° C. and 95% RH for 1,000 hours. disordered situation. Also, the number of samples is ten.

As a result, it was confirmed that the liquid crystal display element in Example 27 had no color unevenness at all, but the liquid crystal display element in Comparative Example 15 had a small amount of color unevenness mainly in the peripheral portion. Moreover, when the color unevenness part of the liquid crystal display element produced by the comparative example 15 was analyzed by Tof-sims, the component of a sealing compound was observed.

Industrial availability

According to the present invention, when used as a sealant for liquid crystal display elements in the process of manufacturing liquid crystal display elements by the drop filling method, there is little contamination of liquid crystals, good adhesion to glass, and curing that does not cause uneven cell gaps. Resin composition, sealant for liquid crystal display element and liquid crystal display element.

Claims (34)

1. curable resin composition, it is to contain the curable resin composition that solidified curable resin and polymerization starter take place under the effect of light and/or heat, it is characterized in that described curable resin (methyl) acrylic modified epoxy resin for making crystallinity Resins, epoxy and (methyl) vinylformic acid react and form.

2. curable resin composition as claimed in claim 1 is characterized in that, (methyl) acrylic modified epoxy resin is crystalline.

3. curable resin composition as claimed in claim 1 or 2 is characterized in that, the fusing point of (methyl) acrylic modified epoxy resin is 80 ℃ or below it.

4. as claim 1,2 or 3 described curable resin compositions, it is characterized in that, (methyl) acrylic modified epoxy resin in its resin matrix sulphur atom and total number of Sauerstoffatom be 5-10.

5. as claim 1,2,3 or 4 described curable resin compositions, it is characterized in that, (methyl) acrylic modified epoxy resin, remove with the total atom number that the value of sulphur atom and the total number of Sauerstoffatom is 0.08-0.14 in the resin matrix.

6. curable resin composition, it is to contain the curable resin composition that solidified curable resin and polymerization starter take place under the effect of light and/or heat, it is characterized in that, described polymerization starter is, the radical polymerization initiator that contains radical polymerization initiating radical and hydrogen bond functional group in a part, described radical polymerization initiating radical are dissociated into two living radical kinds at irradiates light and/or when hot.

7. curable resin composition as claimed in claim 6 is characterized in that, under the condition of irradiates light and/or heat, two living radical kinds that produced through dissociating of radical polymerization initiating radical all have at least one hydrogen bond functional group.

8. as claim 6 or 7 described curable resin compositions, it is characterized in that radical polymerization initiator also has plural reactive functional groups in a part.

9. curable resin composition as claimed in claim 8, it is characterized in that, under the condition of irradiates light and/or heat, two living radical kinds that produced through dissociating of radical polymerization initiating radical all have at least one hydrogen bond functional group and at least one reactive functional groups.

10. as claim 6,7,8 or 9 described curable resin compositions, it is characterized in that the radical polymerization initiating radical has the structure with following general formula (1) expression,

[Chemical formula 1]

In the formula (1), R ¹And R ²Expression hydrogen atom, hydroxyl, carbonatoms are the alkyl of 1-6, alkoxyl group or the phenyl that carbonatoms is 1-6, and

[Chemical formula 2]

It is the alkyl of 1-6 or the aromatic nucleus of halogen radical that expression can have carbonatoms.

11., it is characterized in that at least one is (methyl) acryl and/or ring-type ether in the reactive functional groups as each described curable resin composition in the claim 6 to 10.

12., it is characterized in that hydrogen bond functional group is urethane groups and/or hydroxyl as each described curable resin composition in the claim 6 to 11.

13., it is characterized in that the number-average molecular weight of radical polymerization initiator is more than 300 as each described curable resin composition in the claim 6 to 12.

14., it is characterized in that radical polymerization initiator is as each described curable resin composition in the claim 6 to 13, in acetonitrile, measure, the molar absorptivity under 350nm is 200-1 ten thousand M ^-1Cm ^-1Radical polymerization initiator.

15. curable resin composition as claimed in claim 14 is characterized in that, the molar absorptivity under 430nm radical polymerization initiator, that measure in acetonitrile is 100M ^-1Cm ^-1Or below it.

16. curable resin composition, it is to contain the curable resin composition that solidified curable resin, polymerization starter and bonding auxiliary agent take place under the effect of light and/or heat, it is characterized in that, described bonding auxiliary agent be molecular weight 500 or alkoxysilane compound containing trialkylsilyl group in molecular structure more than it and/or molecular weight be 200 or more than it and hydrogen bond functional group value be 2 * 10 ^-3-7 * 10 ^-3The alkoxysilane compound containing trialkylsilyl group in molecular structure of mol/g.

17. curable resin composition as claimed in claim 16 is characterized in that, alkoxysilane compound containing trialkylsilyl group in molecular structure has at least more than one polymerizability functional group and/or reactive functional groups.

18. curable resin composition as claimed in claim 17 is characterized in that, polymerizability functional group and/or reactive functional groups are to be selected from least a group of epoxy group(ing), acryl and methacryloyl.

19. curable resin composition, it is to contain under the effect of light and/or heat the solidified curable resin takes place, the curable resin composition of polymerization starter and resin particle, it is characterized in that, described resin particle has core particle and is formed on the lip-deep shell of described core particle, described core particle is formed for-10 ℃ or resin below it by having caoutchouc elasticity and second-order transition temperature, described shell is that 50-150 ℃ resin is formed by second-order transition temperature, and is 5 ℃/minute at heat-up rate, frequency is to be that the second-order transition temperature of the cured article measured of DMA method is 120 ℃ or more than it with the dynamic viscoelastic method of masurement under the condition of 10Hz.

20. curable resin composition as claimed in claim 19 is characterized in that, the median size of resin particle is 0.01-5 μ m.

21., it is characterized in that having caoutchouc elasticity and second-order transition temperature is the polymkeric substance of (methyl) acryl monomer for the following resin of-10 ℃ or its as claim 19 or 20 described curable resin compositions.

22., it is characterized in that bonding strength glass substrate is bonding and when making it to solidify is 150N/cm as claim 19,20 or 21 described curable resin compositions ²Or more than it.

23. curable resin composition, it is to contain that under the effect of light and/or heat solidified curable resin, polymerization starter and median size to take place be the curable resin composition of 1 μ m or the inorganic particulate below it, it is characterized in that the temperature that the ratio second-order transition temperature of the cured article when only having taken place to solidify is low 40 ℃ arrives than the average linear expansion rate α between the temperature of low 10 ℃ of second-order transition temperature under the effect of light ₁Be 1 * 10 ^-4-5 * 10 ^-4/ ℃, and the temperature higher 10 ℃ than second-order transition temperature arrives than the average linear expansion rate α between the high 40 ℃ temperature of second-order transition temperature ₂Be 2 * 10 ^-4-1 * 10 ^-3/ ℃.

24. curable resin composition, it is to contain that under the effect of light and/or heat solidified curable resin, polymerization starter and median size to take place be the curable resin composition of 1 μ m or the inorganic particulate below it, it is characterized in that the temperature that the ratio second-order transition temperature of the cured article when having taken place to solidify is low 40 ℃ arrives than the average linear expansion rate α between the temperature of low 10 ℃ of second-order transition temperature under the effect of light and heat ₁Be 5 * 10 ^-5-1 * 10 ^-4/ ℃, and the temperature higher 10 ℃ than second-order transition temperature arrives than the average linear expansion rate α between the high 40 ℃ temperature of second-order transition temperature ₂Be 1 * 10 ^-4-3 * 10 ^-4/ ℃.

25., it is characterized in that the combined amount of inorganic particles is the 10-20 weight part with respect to curable resin 100 weight parts as claim 23 or 24 described curable resin compositions.

26. a curable resin composition is characterized in that, the content of particle diameter above particle of distance between the substrate of target liquid crystal display device is 30 weight % or below it.

27. the manufacture method of a curable resin composition is characterized in that, has to use strainer to carry out filtering operation after the composition that will form curable resin composition mixes.

28. the manufacture method of curable resin composition as claimed in claim 27 is characterized in that, strainer is 70% or more than it for the collection efficiency of particle diameter above particle of distance between the substrate of target liquid crystal display device.

29. the manufacture method as claim 27 or 28 described curable resin compositions is characterized in that, the circulation flow is that 2L/ minute, pressure are 4.6N/cm ²Air the time, the air flowing resistance value of strainer is 10mmH ₂O or more than it.

30. a sealing material for liquid crystal display device is characterized in that, is made up of each the described curable resin composition in the claim 1 to 26.

31. a used for liquid crystal display element sealing compound is characterized in that, is made up of each the described curable resin composition in the claim 1 to 26.

32. conductive material about the used for liquid crystal display element is characterized in that, contains each described curable resin composition and electrically conductive microparticle in the claim 1 to 26.

33. liquid crystal display device, it is characterized in that at least a formation about the described sealing material for liquid crystal display device of use claim 30, the described used for liquid crystal display element sealing compound of claim 31 and the described used for liquid crystal display element of claim 32 in the conductive material.

34. liquid crystal display device, wherein, to at least a portion on a surface, be formed with a pair of transparency carrier of alignment films, middle across centering near the sealing agent that forms its periphery, certain interval that is separated by is oppositely arranged, make simultaneously be formed with described alignment films the surface relatively to, and enclose in the space that forms by described transparency carrier and sealing agent liquid crystal material arranged, wherein, described alignment films does not contact mutually with described sealing agent.