JP4875440B2 - Sealant composition for liquid crystal dropping method and method for producing liquid crystal display panel using the same - Google Patents

Description

  The present invention relates to a sealing agent for a liquid crystal dropping method, and more particularly to a sealing agent for a liquid crystal dropping method having good viscosity stability and good adhesion reliability when left under a high temperature and high humidity for a long time.

  In a current liquid crystal display panel, a main sealant is applied so as to form a liquid crystal injection hole on one glass substrate to be bonded, and bonding is performed by thermosetting. Then, after injecting liquid crystal through a liquid crystal injection hole in a vacuum, the liquid crystal injection part is manufactured by a method of sealing with an ultraviolet curable end sealant. The above-mentioned liquid crystal display panel production method has a long process time for injecting liquid crystal, the thermal strain due to a high temperature of around 150 ° C. when thermosetting is performed, the adhesion of the glass substrate is lowered, the position shift, the gap variation, There are problems such as seepage from the sealant.

  As a method for solving these problems, a photocurable acrylic adhesive mainly composed of acrylic ester or methacrylic ester (Patent Document 1), a mixed system of a photocurable epoxy adhesive and an acrylic resin (Patent Document) 2) The thing which uses the partially acrylated or partially methacrylated product of the epoxy resin as a main component and limits the blending of other raw materials and uses both photocuring and thermosetting (Patent Document 3 and Patent Document 4) has been proposed. These photo-curing sealants are liquid crystal dripping type sealants that can be cured at room temperature and in a short time by light irradiation, shortening the process time for panel preparation, and the glass substrate for liquid crystal is quickly fixed. The problem of the panel preparation method using the curable epoxy resin is solved.

However, the photo-curing acrylic adhesive mainly composed of acrylic acid ester or methacrylic acid ester, and the mixed system of photo-curing epoxy adhesive and acrylic resin have the required adhesion and high temperature and high humidity. In other words, the requirements such as adhesion reliability when left for a long time, maintenance of electro-optical characteristics of the liquid crystal, and no alignment disorder are not satisfied. A combination of photocuring and thermosetting, mainly composed of partially acrylated or partially methacrylic epoxy resin, has good adhesive properties, adhesion reliability when left under high temperature and high humidity for a long time, and electro-optical properties of liquid crystals. Problems such as maintenance and not causing disorder of alignment are improved, but viscosity stability is poor, the line width becomes narrow at the time of application as the viscosity increases, and the number of times the liquid crystal dropping method sealing agent is replaced in the dispenser increases. There are problems such as a decrease in the yield of the sealing agent for liquid crystal dropping method and the liquid crystal display panel due to these problems. On the other hand, liquid crystal sealants (Patent Document 5, Patent Document 6, Patent Document 7) and organic EL sealants (Patent Document 8) for the purpose of preventing the liquid crystal sealant component from dissolving into the liquid crystal material are proposed. However, no satisfactory one has been obtained in terms of viscosity stability, originally required adhesion, and adhesion reliability when left for a long time under high temperature and high humidity.
Japanese Patent No. 2846842 JP 2001-83531 A Japanese Patent No. 3162179 Japanese Patent No. 3583326 JP-A-2005-208115 JP 2005-232370 A JP 2006-23581 A JP 2004-163766 A

  The purpose of the present invention is excellent in display properties such as viscosity stability, coating suitability, electro-optical properties of liquid crystal panels, and alignment disorder, and when left for a long time under the adhesive strength of liquid crystal display panels and high temperature and high humidity It is providing the sealing compound for liquid crystal dropping methods, and the sealing agent for liquid crystal dropping methods excellent in the adhesive strength of this.

As a result of intensive studies in view of the above circumstances, the inventors of the present invention have, as a result, required a (meth) acrylic resin (A) having a hydrogen-bonding functional group amount of 0 mol / g as a sealing agent composition for a liquid crystal dropping method. I found something. That is
[1] A sealing agent composition for a liquid crystal dropping method which essentially comprises a (meth) acrylic resin (A) having a hydrogen bonding functional group amount of 0 mol / g.
[2] The amount of the hydrogen bonding functional group is 1.5 × 10 ⁻³ mol / g or more with respect to 100 parts by weight of the (meth) acrylic resin (A) having a hydrogen bonding functional group amount of 0 mol / g. (Meth) acrylic resin (a) 0-30 parts by weight epoxy resin (b) 1-60 parts by weight latent epoxy curing agent (c) 1-30 parts by weight photoinitiator (d) 0.5-10 parts by weight filler (E) 1-40 weight part is contained, The sealing compound composition for liquid crystal dropping methods as described in [1] characterized by the above-mentioned.
[3] The liquid crystal dropping method according to [1] or [2], wherein the number average molecular weight of the (meth) acrylic resin (A) having a hydrogen bonding functional group amount of 0 mol / g is 520 or more. Sealant composition.
[4] The liquid crystal dropping method, wherein the (meth) acrylic resin (A) according to any one of [1] to [3] contains at least a (meth) acrylic resin modified with a caprolactone derivative Sealant composition.
[5] A liquid crystal display characterized in that the sealing composition for liquid crystal dropping method according to any one of [1] to [4] is applied onto a cell substrate, the liquid crystal is dropped, and then a pair of cell substrates are bonded together. Panel manufacturing method.
[6] A liquid crystal display panel produced by the production method according to [5].
It is.

  The sealing composition for the liquid crystal dropping method of the present invention has good adhesion and adhesion reliability when left for a long time under high temperature and high humidity, maintains the electro-optical characteristics of the liquid crystal, does not cause alignment disorder, etc. Improve display reliability of LCD panels. Furthermore, since the viscosity stability at the time of use is excellent, the yield of the sealing agent for liquid crystal dropping method and the yield of the liquid crystal display panel can be improved.

Hereinafter, the sealing agent composition for liquid crystal dropping method in the present invention will be described in detail.
Definition of (meth) acrylic resin and epoxy resin In recent years, many resins having epoxy groups and (meth) acrylic groups have been synthesized, but they can be classified as epoxy resins such as acrylated epoxy resins, or epoxy resins. They are called acrylates and are classified as acrylic resins, and are not clearly defined. Therefore, in the present invention, the following criteria are rationally described.
The (meth) acrylic resin in the present invention means a resin containing no epoxy group. The epoxy resin means a resin containing at least one epoxy group.
Furthermore, the (meth) acrylic resin of this invention means the compound before hardening with light, a heat | fever, etc., and it describes with (meth) acrylate. Moreover, the epoxy resin of this invention means the compound before making it harden | cure, and what hardened | cured is distinguished as an epoxy resin hardened | cured material and an epoxy hardened | cured material.

[ (Meth) acrylic resin (A) having a hydrogen bonding functional group amount of 0 mol / g ]
The sealing agent composition for a liquid crystal dropping method in the present invention essentially comprises a (meth) acrylic resin (A) having a hydrogen bonding functional group amount of 0 mol / g. In this condition, the adhesiveness and the adhesive reliability when left for a long time under high temperature and high humidity are excellent. In addition, the (meth) acrylic resin in this invention shows an acrylic resin, a methacrylic resin, an acrylic resin, and a methacrylic resin.

The hydrogen bondable functional group in the present invention means a hydrogen bondable functional group in the curable resin, such as a functional group or a residue having hydrogen bondability. Specifically, —OH group, —NH ₂ group, —NHR group (R represents an aliphatic hydrocarbon, aromatic, or a derivative thereof), —CONH ₂ group, —NHOH group, or curable resin And a functional group having a residue of —NHCO— bond, —NH— bond, —CONHCO— bond, —NH—NH— bond, and the like. Among these, the —OH group is most preferred as the hydrogen bonding functional group in the present invention.
Moreover, the amount of hydrogen bondable functional groups in the present invention is obtained by dividing the number of hydrogen bondable functional groups in one molecule of the curable resin by the molecular weight of the curable resin. The curable resin means (meth) acrylic resin and epoxy resin.

  Specific examples of the (meth) acrylic resin having a hydrogen bondable functional group amount of 0 mol / g in the present invention include, for example, 4 mol or more of ethylene oxide per 1 mol of bisphenols such as bisphenol A, bisphenol S, bisphenol F and bisphenol AD. Alternatively, di (meth) acrylate of diol obtained by adding propylene oxide; di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate; adding 6 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane Diol or tri (meth) acrylate of triol obtained by the above; triol tri (meth) acrylate obtained by adding 3 mol or more of lactone to 1 mol of trimethylolpropane; pentaerythritol, dipentaerythritol Poly (meth) acrylates; caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate; poly (meth) acrylates of caprolactone-modified pentaerythritol; poly (meth) acrylates of caprolactone-modified dipentaerythritol; caprolactone-modified hydroxypivalic acid neo Examples include pentyl glycol di (meth) acrylate. In addition, diglycidyl ethers of bisphenols such as bisphenol A diglycidyl ether, and (meth) acrylates such as aromatic dicarboxylic acids typified by phthalic anhydride, isophthalic acid, terephthalic acid, pyromellitic acid, or derivatives thereof (Meth) acrylate etc. which modified | denatured after making it react with the reaction material of these are mentioned. Of these, at least a (meth) acrylic resin (A) modified with a caprolactone derivative is preferable because the adhesive strength is remarkably improved.

  Of these, when used as a sealing agent composition for a liquid crystal dropping method in the present invention, the (meth) acrylic resin (A) which is liquid at 25 ° C. is preferred in order to enhance dispersibility in the sealing agent. A (meth) acrylic resin having at least one (meth) acrylic group and epoxy group in one molecule is also preferred.

  Furthermore, the number average molecular weight by GPC of (meth) acrylic resin (A) is 520 or more, preferably 520 to 4000, more preferably 610 to 2000. Thereby, when it is set as the sealing compound composition for liquid crystal dropping methods, the high display characteristic of a liquid crystal display panel is securable.

[ (Meth) acrylic resin (a) having a hydrogen bonding functional group amount of 1.5 × 10 ⁻³ mol / g or more ]
Specific examples of the (meth) acrylic resin (a) having a hydrogen bondable functional group amount of 1.5 × 10 ⁻³ mol / g or more in the present invention include hydroxyalkyl acrylates such as hydroxyethyl acrylate and hydroxybutyl acrylate. , (Meth) acrylic resin, bisphenol A, bisphenol S, bisphenol F, bisphenol AD obtained by the reaction of polyhydric alcohols such as pentaerythritol tri (meth) acrylate and sorbitol tri (meth) acrylate with (meth) acrylic acid And (meth) acrylic resins obtained by reaction of polyvalent glycidyl ether compounds such as aromatic diols represented by (meth) acrylic acid and the like. A (meth) acrylic resin having at least one (meth) acrylic group and epoxy group in one molecule is also preferred. A (meth) acrylic resin having at least one (meth) acrylic group and epoxy group in one molecule is also preferred. Two or more of these (meth) acrylic resins may be used in combination.
Among these, a (meth) acrylic resin obtained by a reaction between a polyvalent glycidyl ether compound and (meth) acrylic acid, which has at least one (meth) acrylic group and epoxy group in the molecule. A (meth) acrylic resin having a functional group amount of 1.5 × 10 ⁻³ mol / g or more is also preferred.

In the present invention, the amount of the hydrogen bonding functional group is 1.5 × 10 ⁻³ mol / g or more, and the amount of the (meth) acrylic resin (a) used is that the hydrogen bonding functional group amount is 0 mol / g (meta ) 0 to 30 parts by weight is preferable with respect to 100 parts by weight of the acrylic resin (A). Thereby, when it is set as the sealing compound composition for liquid crystal dropping methods, the outstanding viscosity stability is shown. Furthermore, the number average molecular weight of the (meth) acrylic resin (a) having a hydrogen bondable functional group amount of 1.5 × 10 ⁻³ mol / g or more is 520 or more, preferably 520 to 2000. Thereby, when it is set as the sealing compound composition for liquid crystal dropping methods, the high display characteristic of a liquid crystal display panel is securable.

[ Epoxy resin (b) ]
The epoxy resin (b) used in the present invention includes, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol and other polyalkylene glycols, dimethylolpropane, Aliphatic polyvalent glycidyl ether compounds obtained by reaction of polyhydric alcohols typified by trimethylolpropane, spiroglycol, glycerin and the like and epichlorohydrin; typified by bisphenol A, bisphenol S, bisphenol F, bisphenol AD, etc. Aromatic diols, diols modified with ethylene glycol, propylene glycol, and alkylene glycol, and epichlorohydride Aromatic polyvalent glycidyl ether compound obtained by reaction with azodihydride; Aliphatic polyvalent glycidyl ester compound obtained by reaction of aliphatic dicarboxylic acid typified by adipic acid, itaconic acid and epichlorohydrin; isophthalic acid, terephthalic acid Aromatic polyvalent glycidyl ester compound obtained by reaction of aromatic dicarboxylic acid represented by acid, pyromellitic acid and epichlorohydrin; aliphatic polyvalent glycidyl ether obtained by reaction of hydroxydicarboxylic acid compound and epichlorohydrin Ester compound or aromatic polyvalent glycidyl ether ester compound; Aliphatic polyvalent glycidyl ether compound, aliphatic polyvalent glycidyl amine compound obtained by reaction of aliphatic diamine typified by polyethylene diamine and epichlorohydrin; Aromatic polyvalent glycidylamine compounds obtained by the reaction of aromatic diamines such as nylmethane, aniline, metaxylylenediamine, etc. with epichlorohydrin; hydantoin-type polyvalent obtained by the reaction of hydantoin and its derivatives with epichlorohydrin Glycidyl compounds; novolak resins derived from phenol or cresol and formaldehyde; novolac polyvalent glycidyl ether compounds obtained by reaction of polyphenols typified by polyalkenylphenols and copolymers thereof with epichlorohydrin; epoxidized polybutadiene, Epoxidized diene polymers such as epoxidized polyisoprene; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexane carbonate, bis Specific examples include (2,3-epoxycyclopentyl) ether.

Although it does not specifically limit about molecular weight, Usually, the epoxy resin of number average molecular weight 300-2000 can be used. It is preferable to use those epoxy resins that have been highly purified by a molecular distillation method or the like.
The use amount of the epoxy resin of the present invention is preferably 1 to 60 parts by weight with respect to 100 parts by weight of the (meth) acrylic resin (A) having a hydrogen bonding functional group amount of 0 mol / g. By using the epoxy resin in such an amount, compatibility is developed, and high adhesion reliability can be secured when a sealing agent composition for a liquid crystal dropping method is used.

[ Latent epoxy curing agent (c) ]
As the latent epoxy curing agent (c) used in the present invention, known ones such as organic acid dihydrazide compounds, imidazole and derivatives thereof, dicyandiamide, aromatic amines and the like can be used. Among these, dihydrazide-based thermosetting agents are preferable, and specific examples include adipic acid dihydrazide, isophthalic acid dihydrazide, sebacic acid dihydrazide, and 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin. . The amount of the latent epoxy curing agent used in the present invention is preferably 1 to 30 parts by weight. Within this range, adhesion reliability under high temperature and high humidity conditions is exhibited, and viscosity stability can be secured.

[ Photoinitiator (d) ]
It does not specifically limit as a photoinitiator (d) used for this invention, It is possible to use a well-known material. Specific examples include benzophenone, 2,2-diethoxyacetophenone, benzyl, benzoyl isopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, and thioxanthone. As a quantity of the photoinitiator used for this invention, 0.5-10 weight part is preferable with respect to 100 weight part of (meth) acrylic resins (A) whose hydrogen bonding functional group amount is 0 mol / g. Within this range, it is preferable in that the curability by light irradiation and the hygroscopicity of the cured substance can be suppressed.

[Filler (e)]
The filler (e) used in the present invention is used for the purpose of adjusting the viscosity, reducing the thermal stress of the cured product, and the like, and inorganic materials and organic materials can be used. The inorganic filler can be selected from known inorganic compounds. Specifically, for example, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate, kaolin, talc, asbestos Powder, quartz powder, mica, glass fiber, etc. As the inorganic filler, kaolin, talc and glass fiber are preferable.
The organic filler can be selected from known organic compounds, and is not particularly limited. Specifically, for example, a material obtained by copolymerizing polymethyl methacrylate, polystyrene and monomers copolymerizable therewith can be used. Is possible.
The particle diameter of the filler is not particularly limited as long as it does not affect the display panel, but it is preferable to use a filler having a particle diameter of 2 μm or less.
The amount of the filler used is such that the amount of the hydrogen bonding functional group is greater than 0 mol / g and less than 1.5 × 10 ⁻³ mol / g of (meth) acrylic resin (A) 100 parts by weight. 40 parts by weight. Within this range, a thermal stress reduction effect is manifested, and the workability viscosity can be suppressed.

In the present invention, additives such as a thermosetting catalyst, a coupling agent, an ion trap agent, and an ion exchanger can be used as necessary in addition to the above-described components.
In the present invention, additives such as a thermosetting catalyst, a coupling agent, an ion trap agent, and an ion exchanger can be used as necessary in addition to the above-described components.

  In the present invention, a solvent may be contained. Solvents include, for example, ketone solvents such as cyclohexanone, ether solvents such as diethylene glycol dimethyl ether, methyl carbitol, ethyl carbitol and butyl carbitol, acetate solvents such as diethylene glycol diacetate and alkoxydiethylene glycol monoacetate, toluene And hexane. The content of the solvent in the liquid crystal dropping method sealing agent composition in the present invention is preferably 0.1% or less, more preferably 0.03% or less. This range is preferable because the display characteristics of the liquid crystal display panel can be ensured.

<Method for Preparing Liquid Crystal Sealant Composition>
There is no particular limitation on the method for preparing the liquid crystal sealant composition of the present invention, and it can be obtained by mixing each of the above components by a conventional method. For mixing, for example, a known kneading machine such as a double-arm stirrer, a roll kneader, a twin screw extruder, a ball mill kneader or the like may be used. It can be hermetically filled, stored and transported. In addition, in order to maintain viscosity stability, as a temperature concerning the sealing compound for liquid crystal dropping methods of this invention at the time of adjustment, -15 degreeC-35 degreeC is preferable, More preferably, it is 10 degreeC-less than 30 degreeC.

  The liquid crystal dropping method sealing agent composition of the present invention preferably has a viscosity at 2.5 rpm of 50 to 450 Pa · s by an E-type viscometer at 25 ° C., and more preferably has a viscosity of 2.5 rpm of 150 to 450 Pa.・ It is in the range of s. By maintaining the initial viscosity characteristics within that range, it is preferable because application workability without application unevenness can be exhibited. In particular, if the viscosity at 2.5 rpm by an E-type viscometer at 25 ° C. is an initial viscosity of 50 Pa · s or more, it is preferable because the seal shape retention after coating is excellent, and an initial viscosity of 150 Pa · s or more is more preferable. . Further, an initial viscosity of 450 Pa · s or less is preferable because it can ensure the dispense applicability with a nozzle diameter of 0.15 to 0.5 mm.

<Liquid crystal display panel and manufacturing method thereof>
The liquid crystal display panel of the present invention is manufactured by a liquid crystal dropping method using the liquid crystal dropping method sealing agent composition obtained as described above. An example of the manufacturing method will be described below.
A spacer having a preset gap width is mixed with the sealing composition for a liquid crystal dropping method of the present invention and defoamed. Further, a pair of glass substrates for liquid crystal cells is used, and the liquid crystal sealing agent composition is applied to a frame shape with a dispenser on one glass substrate for liquid crystal cells. Next, a liquid crystal material corresponding to the internal capacity of the panel after the glass substrates forming a pair are bonded is precisely dropped into the frame. Then, the other glass is made to oppose and the glass substrate is bonded together by irradiating ultraviolet rays in an amount of 500 to 18000 mJ / cm ² . Further, after that, it is heated for about 30 minutes to 1 hour at a temperature of 100 ° C. to 140 ° C. and sufficiently cured to form a liquid crystal display panel.
Examples of the liquid crystal cell substrate used include a glass substrate and a plastic substrate. In the substrate group described above, naturally, a transparent electrode represented by indium oxide, an alignment film represented by polyimide, etc., and other so-called glass for constituting a liquid crystal cell, in which an inorganic ion shielding film is applied to a necessary part. A substrate or the same plastic substrate is used.
There is no particular limitation on the method for applying the liquid crystal dropping method sealing agent composition to the liquid crystal cell substrate. For example, the screen printing application method or the dispenser application method may be used.

<Analysis method>
1) The amount of epoxy was calculated by a method of titrating the amount of hydrochloric acid consumed by the epoxy group after dissolving the resin in a hydrochloric acid-dioxane solution.
2) The oxirane oxygen concentration was calculated by performing hydrogen bromide titration.
3) The acid value was calculated from the consumption of ethanolic 0.1N KOH added dropwise by dissolving the resin in diethyl ether / ethanol solution, adding phenolphthalein ethanol solution, and the solution became colorless.
4) For the measurement of the number average molecular weight of the synthesized (meth) acrylic resin, gel permeation chromatography (GPC-MALLS) with a multi-angle light scattering device was used. The measurement conditions are as follows.
Body: Showa Denko KK, System 21
Eluent: Tetrahydrofuran Flow rate: 1.0 ml / min Column: GPC KF-802.5 manufactured by Shodex
Detector: Multi-angle light scattering detector DAWN from Wyatt Technology
<Cleaning of curable resin with ultra pure water>
The cleaning method of the curable resin in the present invention will be described. Unless otherwise noted, washing of the curable resin means this method. Dissolve the curable resin in the same weight of toluene, add 0.7μS / cm or less of ultrapure water, and stir and mix in a separatory funnel equipped with a stirrer, separating the toluene layer and the half-weighted water layer. Left to stand. Thereafter, only the water layer was discharged. At this time, sodium hydroxide equivalent to or higher than the acid value of the curable resin was dissolved in ultrapure water. Furthermore, ultrapure water was added, stirring, mixing, standing and separation were performed, and ultrapure water washing was repeated until the final ultrapure water had an electric conductivity of 1 μS / cm.

<Column purification of curable resin>
The column purification method of the curable resin in the present invention will be described. Unless otherwise noted, column purification of a curable resin means this method. A curable resin was dissolved in toluene, silica gel was used as a filler, and one or more of hexane, toluene, tetrahydrofuran, ethyl acetate, and chloroform were mixed and used as an eluent. Column purification is performed one or more times, increasing the number as necessary. Unless otherwise noted, solvent removal was performed at 70 ° C. under reduced pressure to remove the solvent.

Hereinafter, the present invention will be described in detail by way of representative examples.
(Synthesis Example 1)
Column-purified and ultrapure water-washed 2-hydroxyethyl methacrylate 6-hexanolide adduct (Plexel FM1D, molecular weight: 244, manufactured by Daicel Chemical) 488.6 g (2 mol), bisphenol F diglycidyl ether 312.3 g (1 mol) ), 2 g of triethanolamine and 1 g of methylhydroquinone were mixed and heated and stirred at 90 ° C. under dry air bubbling, and the stirring was continued until the acid value reached 2 mgKOH / g. This methacrylic resin was washed with ultrapure water to obtain a methacrylic resin in which 100% of the epoxy groups were methacrylated. It was 2.5 * 10 < ^-3 > mol / g when the amount of hydrogen bondable functional groups of the obtained liquid methacrylic resin (a-1) was computed. The number average molecular weight by GPC-MALLS of the obtained methacrylic resin (a-1) was 801, which was a single peak.
[Example 1]
When the amount of hydrogen-bonding functional groups of the acrylic resin (A-1) obtained by washing the column purified caprolactone-modified trimethylolpropane triacrylate (Ebecryl 2740, manufactured by Daicel Cytec) with ultrapure water was calculated, it was 0 mol / g. there were. The number average molecular weight by GPC-MALLS of the obtained acrylic resin (A-1) was 639, which was a single peak. The obtained acrylic resin (A-1), the (meth) acrylic resin (a-1) obtained in Synthesis Example 1, and Epicron 850CRP (b-1) (bisphenol A type epoxy resin: manufactured by Dainippon Ink and Chemicals, Inc.) Amicure VDH (c) (manufactured by Ajinomoto Fine Chemical), Irgacure 184 (d-1) (1-hydroxycyclohexyl phenyl ketone: manufactured by Ciba Specialty Chemicals), SO-E1 (e-1) (ultra high purity silica) : Manufactured by Admatechs), KBM-403 (silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.) in the blending amounts shown in Table 1 and then kneaded thoroughly using a three roll, E-type viscosity A sealant composition for liquid crystal dropping method (S-1) having a viscosity of 300 Pa · s at 25 ° C. by a total (2.5 rpm) was obtained. A 5 μm spacer was added to S-1 and evaluation as a sealing agent for the following liquid crystal dropping method was performed.

1. The viscosity at 25 ° C. of the viscosity-stable liquid crystal dropping method sealing agent (S-1) is measured, and the value is used as a reference. A sealing agent for liquid crystal dropping method (S-1) is placed in a polyethylene container, sealed, and stored under constant conditions at 23 ° C. After the elapse of 7 days, the viscosity was measured under the same conditions, and the increase rate was determined as follows.
○: Less than 20% Δ: 20% or more and less than 50% ×: 50% or more Viscosity stability after heating In the same manner as described above, the liquid crystal dropping method sealing agent (S-1) was placed in a polyethylene container, sealed, kept at 50 ° C. for 2 hours, and then stored under constant conditions at 23 ° C. . After 72 hours, the viscosity was measured under the same conditions, and the increase rate was determined as follows.
○: Less than 20% Δ: 20% or more and less than 50% ×: 50% or more 3. Application suitability After filling a 10 cc syringe with a sealing agent for liquid crystal dropping method (S-1), defoaming was performed. Drawing was performed with a dispenser (Shot Master: manufactured by Musashi Engineering). The application was performed at a speed of 4 cm per second. Superiority or inferiority was judged according to the following criteria.
◯: There was no seepage and stringing, and the linearity was good. Δ: There was no seepage and stringing, but the linearity was poor.
X: Exudation and stringing occur and applicability is extremely poor.
4. Adhesive strength A liquid crystal dropping method sealant (S-1) was screen-printed in a 1 mm diameter circle on a 25 mm × 45 mm 4 mm thick non-alkali glass, and a pair of similar glasses were bonded together in a cross shape. , 2000 mJ / cm ² of UV irradiation, followed by heating at 120 ° C. for 1 hour. After storage for 24 hours in a constant temperature bath at 25 ° C. and 50% humidity, the obtained test piece was measured for flat tensile strength at a pulling speed of 2 mm / min using a tensile tester (manufactured by Intesco).
5. Adhesive strength after high-temperature and high-humidity accelerated test Screen-printed sealing agent for liquid crystal dropping method (S-1) on non-alkali glass of 25 mm × 45 mm thickness 4 mm in a 1 mm diameter circle, and a pair of similar glasses After being bonded to a cross, ultraviolet irradiation of 2000 mJ / cm ² was performed, followed by heating at 120 ° C. for 1 hour. Furthermore, it is stored for 20 hours in a high-temperature and high-humidity acceleration tester (ETAC PLAMOUNT PM422 manufactured by Enomoto Kasei Co., Ltd.) having a temperature of 121 ° C., a humidity of 100% and a pressure of 2.1 atm. After storage, the tensile strength of the obtained test piece was measured using a tensile test apparatus (manufactured by Intesco) at a pulling speed of 2 mm / min.
6). Evaluation of electrical properties of liquid crystal panel On a 40 mm × 45 mm glass substrate (RT-DM88-PIN, manufactured by EHC) with a transparent electrode and an alignment film, a sealant for liquid crystal dropping method (S-1) was dispensed (shot master). : Made by Musashi Engineering Co., Ltd., drawn on a 35mm x 40mm formwork with a line width of 0.5mm and a thickness of 50µm, and then a liquid crystal material (MLC-11900-000: Merck) corresponding to the panel capacity after bonding (Manufactured by Kogyo Co., Ltd.) was precisely dropped using a dispenser, and a pair of glass substrates were bonded together under reduced pressure, and ultraviolet rays were irradiated at 2000 mJ / cm ² . Subsequently, heating was performed at 120 ° C. for 1 hour, and a high-temperature and high-humidity operation test was performed for 1000 hours under the conditions of 60 ° C. and 95% humidity, and the voltage holding ratio after the test was measured.
A voltage holding ratio of 98% or more was judged as ◯, 95% or more and less than 98 as Δ, and less than 95% as x.
7). Except that the irradiation 1000 mJ / cm ² display characterization ultraviolet of the liquid crystal display panel, in the same manner as described above to create a liquid crystal panel was. The obtained liquid crystal display panel was visually observed for color unevenness generated in the liquid crystal around the seal portion before and after being left at 65 ° C. and 95% RH for 1000 hours.
This liquid crystal panel was driven with a DC power supply device at an applied voltage of 5 V, and the panel display characteristics were evaluated and judged depending on whether or not the liquid crystal display function in the vicinity of the liquid crystal sealant functions normally from the beginning of driving. In this judgment method, the symbol “◯” indicates that the liquid crystal display function can be exhibited until the sealing, and the display characteristics are good. The symbol Δ was shown as being inferior, and the symbol X was shown as being markedly inferior in the display characteristics when an abnormality in the display function was observed beyond 0.3 mm in the vicinity of the seal.
All evaluation results are shown in Table 2.

(Synthesis Example 2)
296.2 g (2 mol) of phthalic anhydride, 97.07.0 g (2 mol) of 6-hexanolide adduct of 2-hydroxyethyl acrylate (PLAXEL FA3, manufactured by Daicel Chemical; molecular weight: 459), 4 g of triethylamine, hydroquinone 0 1.9 g was heated and stirred at 110 ° C., and after the acid value reached 48 mg KOH / g, bisphenol F diglycidyl ether 312.4 g (1 mol) and tetrabutylammonium bromide 6.4 g were added at 90 ° C. Heating and stirring were continued until the value became 2 mgKOH / g. Subsequently, this solution was dissolved in toluene, subjected to column purification, and then washed with ultrapure water. The number average molecular weight of the obtained acrylic resin by GPC-MALLS was 1526, which was a single peak. Further, 140.6 g (0.1 mol) of this acrylic resin, 250 g of toluene and 2.0 g of triethylamine were mixed, and 90.6 g (1.0 mol) of acrylic acid chloride was added dropwise, followed by stirring with heating at 90 ° C. for 5 hours. Was done. After the obtained solution was washed with ultrapure water, column purification was performed, and ultrapure water was washed again. It was 0 mol / g when the amount of hydrogen bondable functional groups of the obtained acrylic resin (A-2) was calculated. Moreover, the number average molecular weight by GPC-MALLS of the obtained acrylic resin (A-2) was 1634, and was a single peak.
[Example 2]
(Meth) acrylic resin (A-2), Epicron 850CRP (b-1) (bisphenol A type epoxy resin: manufactured by Dainippon Ink and Chemicals), Amicure VDH (c) (manufactured by Ajinomoto Fine Chemical) obtained in Synthesis Example 2 , Irgacure 184 (d-1) (1-hydroxycyclohexyl phenyl ketone: manufactured by Ciba Specialty Chemicals), SO-E1 (e-1) (ultra high purity silica: manufactured by Admatechs), KBM-403 (silane) Coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.) was sufficiently kneaded with a Dalton mixer using three rolls in the blending amounts shown in Table 1, and the viscosity at 25 ° C. with an E-type viscometer (2.5 rpm) was 450 Pa · The sealing compound composition (S-2) for liquid crystal dropping method of s was obtained. Table 2 shows the results of evaluation as a sealing agent for the liquid crystal dropping method using this S-2.
(Synthesis Example 3)
136 g (1 mol) of pentaerythritol, 457 g (4.0 mol) of ε-caprolactone, 18 g of p-toluenesulfonic acid, 1.2 g of hydroquinone monomethyl ether and 600 g of toluene were mixed at 95 ° C. to obtain 317 g (4.4 mol) of acrylic acid. ) Was added dropwise over 2 hours, and the reaction was terminated when the amount of water distilled by azeotropy with toluene reached 64 ml. This reaction solution was washed with ultrapure water, further purified with a column, and then washed with ultrapure water again. It was 0 mol / g when the amount of hydrogen bonding functional groups of the obtained liquid methacrylic resin (A-3) was computed. The number average molecular weight by GPC-MALLS of the obtained methacrylic resin (A-3) was 809, which was a single peak.
[Example 3]
(Meth) acrylic resin (A-3) obtained in Synthesis Example 3, (Meth) acrylic resin (a-1) obtained in Synthesis Example 1, and Epicron 850CRP (b-1) (bisphenol A type epoxy resin: Dainippon Ink and Chemicals), Amicure VDH (c) (Ajinomoto Fine Chemicals), Irgacure 184 (d-1) (1-hydroxycyclohexyl phenyl ketone: Ciba Specialty Chemicals), SG-2000 (e- 2) (Talc: manufactured by Nihon Talc) and KBM-403 (silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed thoroughly in a Dalton mixer using three rolls in the blending amounts shown in Table 1, and the E type A sealant composition for liquid crystal dropping method (S-3) having a viscosity of 150 Pa · s at 25 ° C. by a viscometer (2.5 rpm) was obtained. Table 2 shows the results of evaluation using this S-3 as a sealant for the liquid crystal dropping method.
[Comparative Example 1]
(Meth) acrylic resin (a-1) obtained in Synthesis Example 1, photoinitiator Irgacure 651 (d-2) (2,2-dimethoxy-1,2-diphenylethane-1-one; Ciba Specialty・ Dalton mixer with chemicals), Baikalox CR-10 (e-3) (alumina; Baikowski), KBM-403 (silane coupling agent: Shin-Etsu Chemical Co., Ltd.) After mixing, the mixture was sufficiently kneaded using three rolls to obtain a liquid crystal dropping method sealing agent composition (C-1) having a viscosity of 300 Pa · s at 25 ° C. using an E-type viscometer (2.5 rpm). . Table 2 shows the results of evaluation using this C-1 as a sealing agent for the liquid crystal dropping method.
(Synthesis Example 4)
Dissolve 190 g of phenol novolac epoxy resin N-770 (Dainippon Ink) in 500 mL of toluene, add 0.1 g of triphenylphosphine to make a uniform solution, and then add 35 g of acrylic acid over 2 hours under reflux and stirring. Then, the mixture was stirred under reflux for 6 hours. Further, ultrapure water washing and column purification were performed. The obtained resin was dissolved in a hydrochloric acid-dioxane solution, and then the epoxy equivalent was measured to obtain a phenol novolac type epoxy resin (b-2) in which 50% of the epoxy groups were modified with acrylic acid.
(Synthesis Example 5)
520 g of polyoxyalkylene bisphenol A diglycidyl ether EP4000S (epoxy equivalent 260 g / eq: manufactured by ADEKA), 0.75 g of p-methoxyphenol, 0.75 g of triethylamine, and 72 g of acrylic acid were stirred at 90 ° C. while refluxing. The reaction was allowed for 5 hours. The obtained resin was washed with ultrapure water and subjected to column purification to obtain 50% partially acrylated propylene oxide bisphenol A epoxy resin (b-3).

[Comparative Example 2]
Epoxy resin (b-2) obtained in Synthesis Example 4, epoxy resin (b-3) obtained in Synthesis Example 5, Amicure VDH (c) (manufactured by Ajinomoto Fine Chemicals), 2,2-diethoxyacetophenone (D-3), SO-E1 (e-1) (ultra-high-purity silica: manufactured by Admatechs), KBM-403 (silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.) at the blending amounts shown in Table 1, Dalton After mixing with a mixer, the mixture is sufficiently kneaded using three rolls, and a liquid crystal dropping method sealing agent composition (C-2) having a viscosity of 40 Pa · s at 25 ° C. by an E-type viscometer (2.5 rpm) is obtained. It was. Table 2 shows the results of evaluation as a sealing agent for the liquid crystal dropping method using this C-2.
(Synthesis Example 6)
200 g of Epicron 850CRP (b-1) (bisphenol A type epoxy resin: manufactured by Dainippon Ink & Chemicals), 100 g of methacrylic acid, 900 g of toluene, 0.4 g of triethylamine, and 0.4 g of paramethoxyphenol were mixed at 8 ° C. Stir with heating for hours. Furthermore, by performing ultrapure water washing and column purification, a solid methacrylic resin was obtained at 25 ° C. in which 100% of the epoxy groups were methacrylated. The amount of the hydrogen bonding functional group of the obtained methacrylic resin (a-2) was calculated to be 3.9 × 10 ⁻³ mol / g. The number average molecular weight by GPC-MALLS of the obtained methacrylic resin (a-2) was 513, which was a single peak.
(Synthesis Example 7)
200 g of Epicron 850CRP (b-1) (bisphenol A type epoxy resin: manufactured by Dainippon Ink and Chemicals), 50 g of methacrylic acid, 180 g of toluene, 0.4 g of triethylamine and 0.4 g of paramethoxyphenol were mixed at 8 ° C. Stir with heating for hours. Furthermore, by performing ultrapure water washing and column purification, an epoxy resin (b-4) in which 50% of the epoxy groups were methacrylated was obtained. The number average molecular weight by GPC-MALLS of the obtained epoxy resin (b-4) was 427, which was a single peak.

[Comparative Example 3]
Acrylic resin (a-2) obtained in Synthesis Example 6, 2-hydroxyethyl acrylate (a-3) (hydrogen bonding functional group amount: 8.6 × 10 ⁻³ mol / g), Epicron 850CRP (b− 1) (Bisphenol A type epoxy resin: manufactured by Dainippon Ink and Chemicals), epoxy resin (b-4) obtained in Synthesis Example 7, Amicure VDH (c) (manufactured by Ajinomoto Fine Chemicals), Irgacure 184 (d-1) (1-hydroxycyclohexyl phenyl ketone: manufactured by Ciba Specialty Chemicals), SO-E1 (e-1) (ultra-high purity silica: manufactured by Admatex), KBM-403 (silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.) ) Was mixed with a Dalton mixer in the compounding amounts shown in Table 1, and then sufficiently kneaded using three rolls, and 25 ° C. using an E-type viscometer (2.5 rpm). Definitive viscosity was obtained a liquid crystal dropping process sealant composition 100 Pa · s to (C-3). Table 2 shows the results of evaluation using C-3 as a sealing agent for liquid crystal dropping method.
(Synthesis Example 8)
Epiclone 850CRP (b-1) (bisphenol A type epoxy resin: manufactured by Dainippon Ink and Chemicals) 680 g, p-methoxyphenol 1 g, triethylamine 1 g, and acrylic acid 288 g were refluxed and stirred at 110 ° C. while feeding air. Reacted for hours. The resulting resin was washed with ultrapure water and subjected to column purification to obtain a solid acrylic resin (a-4) at 25 ° C. The number average molecular weight of the obtained acrylic resin by GPC-MALLS was 484, which was a single peak. The amount of the hydrogen bonding functional group was calculated to be 4.1 × 10 ⁻³ mol / g.

[Comparative Example 4]
Acrylic resin (a-4), Amicure VDH (c) (manufactured by Ajinomoto Fine Chemicals), 2,2-diethoxyacetophenone (d-3), SO-E1 (e-1) (ultra-high) obtained in Synthesis Example 8 Purified silica (manufactured by Admatechs) and KBM-403 (silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed with a Dalton mixer in the blending amounts shown in Table 1, and then sufficiently kneaded using three rolls. A sealant composition for liquid crystal dropping method (C-4) having a viscosity of 350 Pa · s at 25 ° C. with a mold viscometer (2.5 rpm) was obtained. Table 2 shows the results of evaluation using C-4 as a sealing agent for liquid crystal dropping method.

[Comparative Example 5]
Epoxy resin bis (3,5-bis-hydroxymethyl-4-glycidyloxyphenyl) methane (b-5), Amicure VDH (c) (manufactured by Ajinomoto Fine Techno Co.), SO-E1 (e- 1) (Ultra high-purity silica: manufactured by Admatechs), KBM-403 (silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed with a Dalton mixer in the blending amounts shown in Table 1, and sufficient using three rolls. To obtain a sealant composition for liquid crystal dropping method (C-5) having a viscosity of 500 Pa · s at 25 ° C. measured by an E-type viscometer (2.5 rpm). Evaluation as a sealing agent for liquid crystal dropping method was carried out using this C-5. The evaluation results are shown in Table 2.

[Comparative Example 6]
Column-purified Blemmer GMR (glycerol dimethacrylate, manufactured by Nippon Oil &Fats; molecular weight 228.3, hydrogen bondable functional group amount; 4.4 × 10 ⁻³ mol / g) (a-5), Epicron 850CRP (b-1) (Bisphenol A type epoxy resin: manufactured by Dainippon Ink and Chemicals), Amicure VDH (c) (manufactured by Ajinomoto Fine Chemical), 2,2-diethoxyacetophenone (d-3), SO-E1 (e-1) ( Ultra high purity silica (manufactured by Admatechs) and KBM-403 (silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed with a Dalton mixer at the blending amounts shown in Table 1, and then kneaded thoroughly using three rolls. A sealing agent composition for liquid crystal dropping method (C-6) having a viscosity of 350 Pa · s at 25 ° C. by an E-type viscometer (2.5 rpm) was obtained. Evaluation as a sealing agent for liquid crystal dropping method was carried out using this C-6. The evaluation results are shown in Table 2.

Claims (5)

100 parts by weight of (meth) acrylic resin (A ) having a hydrogen bonding functional group amount of 0 mol / g ,
(Meth) acrylic resin (a) having a hydrogen bonding functional group amount of 1.5 × 10 ⁻³ mol / g or more, 0 to 30 parts by weight;
1 to 60 parts by weight of epoxy resin (b),
1-30 parts by weight of latent epoxy curing agent (c),
0.5-10 parts by weight of photoinitiator (d),
The sealing compound composition for liquid crystal dropping methods containing 1 to 40 weight part of fillers (e) . Hydrogen-bonding functional group amount is 0 mol / g (meth) number average molecular weight of the acrylic resin (A) is 520 or more, a liquid crystal dropping process sealant composition according to claim 1. The sealing composition for liquid crystal dropping method according to claim 1 or 2, wherein the (meth) acrylic resin (A) contains a (meth) acrylic resin modified with at least a caprolactone derivative. The manufacturing method of the liquid crystal display panel which bonds a pair cell substrate after apply | coating the sealing compound composition for liquid crystal dropping methods as described in any one of Claims 1-3 on a cell substrate, dripping a liquid crystal. A liquid crystal display panel produced by the production method according to claim 4 .