KR20110060597A - Curing resin composition for liquid crystal dropping method and method for manufacturing the same - Google Patents

Abstract

PURPOSE: A curable resin composition for a liquid crystal dropping method is provided to ensure little contamination of liquid crystal, uniform hardening performance, and excellent storage stability. CONSTITUTION: A curable resin composition for a liquid crystal dropping method comprises the steps of: mixing components of a curable resin composition; removing foreign materials through a filter; and removing bubbles using a defoamer. The sealant composition for the liquid crystal display device comprises 100.0 parts by weight of modified epoxy resin including partially (meth)acrylate group; 5-30 parts by weight of a monomer represented by chemical formula (1); 1-10 parts by weight of thermosetting material; and 1-5 parts by weight of photopolymerization initiator.

Description

Curable resin composition for liquid crystal dropping method and its manufacturing method {CURING RESIN COMPOSITION FOR LIQUID CRYSTAL DROPPING METHOD AND METHOD FOR MANUFACTURING THE SAME}

The present invention relates to a curable resin composition for a liquid crystal dropping method and a method for producing the same, and more particularly, the dispersion stability of the curable resin and the inorganic material is achieved, the curing performance is uniform, the curing time can be shortened, and the storage stability The present invention relates to a curable resin composition for a liquid crystal dropping method which is excellent in contamination with liquid crystals and has excellent adhesive strength after curing, and a method for producing the same.

Liquid crystal display (LCD), which is being actively researched and developed recently, is a kind of flat panel display (FPD) and has a structure in which the overall structure includes two substrates and a liquid crystal interposed between the two substrates.

In the manufacturing process of the liquid crystal display device, in order to interpose liquid crystal between two substrates, a sealant composition is applied to an edge of any one of the two substrates, the two substrates are bonded together, and then the process of curing the sealant composition is performed. You have to go through.

However, since the sealant composition or the cured product thereof comes into direct contact with the liquid crystal during or after the curing process, the curing process should be performed quickly and the sealant composition or the cured product should not be eluted into the liquid crystal. In addition, in order to improve the reliability of the liquid crystal display device against external force, the cured product needs to have a high adhesive strength.

On the other hand, in order to enlarge and mass-produce a liquid crystal display device, the photocuring and thermosetting combined use method is generally used, and the adhesive agent using an epoxy partial acrylate resin is used at this time.

The liquid crystal dropping method used for the enlargement and mass production of a liquid crystal display device uses a photocuring and thermosetting combination sealant composition, forms a sealant composition pattern on one transparent substrate, drops a liquid crystal on the inside, and transparent on the other side. It is a manufacturing method of a liquid crystal display device which overlaps and seals a board | substrate.

However, in the liquid crystal dropping method, the liquid crystal and the uncured sealant composition are mutually contacted, so that the components of the sealant composition are eluted into the liquid crystal, thereby causing liquid crystal contamination of the liquid crystal.

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a resin composition for sealants used in a liquid crystal dropping method, which provides a curable resin composition for a liquid crystal dropping method having a very low contaminant to liquid crystals, a uniform curing performance, and excellent storage stability, and a method for producing the same. will be.

In order to solve the above problems, the present invention is a method for producing a curable resin composition used in the liquid crystal dropping method, after mixing the components of the curable resin composition after removing foreign matter through a filter to remove the air bubbles using a deaerator. It provides the manufacturing method of curable resin composition for liquid crystal dropping methods containing a process.

The present invention also includes a curable resin composition for a liquid crystal dropping method prepared by the above production method and containing a monomer represented by the formula (1) (In the formula (1), X is O, S or NH, R ₁ is H or CH ₃ , and R ₂ is an alkyl group of C _1-30 or an aryl group of C _3-30 .

The present invention also, in part, 100 parts by weight of the modified epoxy resin containing a (meth) acrylate group, 5 to 30 parts by weight of the monomer represented by the formula (1), 1 to 10 parts by weight of the thermosetting agent and 1 to 5 parts by weight of the photopolymerization initiator It provides the sealant composition for liquid crystal display elements containing a part.

According to the present invention, the dispersion stability of the curable resin and the organic and inorganic to ensure uniform curing performance, excellent storage stability, less contamination to the liquid crystal, curable resin composition for liquid crystal dropping method excellent in adhesive strength after curing Can be obtained.

Hereinafter, the present invention will be described in detail.

The manufacturing method of the curable resin composition for liquid crystal dropping method of this invention is a manufacturing method of the curable resin composition used for a liquid crystal dropping method, after mixing each component of the said curable resin composition, removes a foreign material through a filter, and then uses a degassing machine. Characterized in that it comprises a step of removing bubbles.

In the method of preparing the curable resin composition of the present invention, after mixing each component of the resin composition, the foreign material is removed through a filter, and then subjected to a process of removing air bubbles using a deaerator, thereby uniformly mixing each component of the resin compositions. And by promoting the dispersion, there is a feature that can increase the dispersion uniformity.

Therefore, the curable resin composition prepared by the method of preparing the curable resin composition of the present invention has the advantages of uniform curing performance, excellent storage stability, low contamination to liquid crystal, and excellent adhesive strength after curing.

The process of removing bubbles using the degassing machine may be performed by, for example, a process of degassing by rotating and revolving a mixture of the components of the curable resin composition in a degassing machine.

Preferably, the process of defoaming by passing the step of rotating the mixture of the curable resin composition for about 20 to 40 minutes, and then idle for about 20 to 40 minutes, or of the curable resin composition The mixture may be subjected to a defoaming process by simultaneously rotating and rotating for about 20 to 40 minutes.

When the rotational speed and rotational speed (rpm) is too small, it may be difficult to achieve the effect of improving the dispersion stability of the curable resin composition, such as, the rotational speed and rotational revolution (rpm) of the rotation is 500rpm respectively As mentioned above, it is preferable that the said revolution is 200 rpm or more.

In one preferred example, the curable resin composition may include a monomer represented by the following formula (1).

(1)

(One)

(In the formula (1), X is O, S or NH, R ₁ is H or CH ₃ , R ₂ is an alkyl or aryl group of C _1-30 .)

Moreover, in one preferable example, the said curable resin composition is 100 weight part of modified epoxy resins which contain a (meth) acrylate group partially, 5-30 weight part of monomers represented by following General formula (1), and 1 to 1 thermosetting agent It may comprise 10 parts by weight and 1 to 5 parts by weight of the photopolymerization initiator.

(1)

(One)

(In the formula (1), X is O, S or NH, R ₁ is H or CH ₃ , R ₂ is an alkyl group of C _1-30 or an aryl group of C _3-30 .)

The monomer represented by the general formula (1) and the modified epoxy resin allow the curable resin composition to be cured rapidly by thermosetting and photocuring, and have a function of imparting linearity and adhesiveness to a resin composition applied to a substrate or the like. do.

R ₂ is ethylene glycol, glycerin, sorbitol, trimethylol propane, (poly) propylene glycol, 1,3-propane diol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, mono (meth) acrylate , Trimethylolethane, trimethylolpropane, diisocyanate, tolylene diisocyanate, xylene diisocyanate, isophorone diisocyanate, tolidine, diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, caprolactone ethyl ester , N-3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- [5- (trimethoxy silyl) -2-1-oxo-pentyl] caprolactam, O- ( Vinyloxyethyl) -N- (triethoxysilylpropyl) urethane, gamma-undecalactone, epsilon-caprolactone, gamma-decaractone, alpha-dodecaractone, gamma-nonalactone, gamma-nonanolactone, Gamma-Valerolactone, Alpha-Ballet Lactone, beta, butyrolactone, gamma-least one selected from the enemy hexanoate lactone and 7-butyl-2-oxide Sefar the group consisting of non-butyrolactone, beta-propiolactone, alpha.

The (meth) acrylate-modified epoxy resin partially comprises at least one resin selected from the group consisting of noblock type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, trisphenol methane type epoxy resins, and bisphenol type epoxy resins. It may be used alone or in combination of two or more.

The curable resin composition may further include 10 to 40 parts by weight of at least one additive selected from the group consisting of an inorganic filler, a thixotropic regulator and a silane coupling agent.

As the partially (meth) acrylate-modified epoxy resin, a resin having a viscosity of 1000 to 15000 cps may be used, and preferably a resin having 5000 to 10000 cps may be used. The viscosity of the (meth) acrylate modified epoxy resin can be controlled in part by adjusting the viscosity of the epoxy resin before synthesis of the resin.

When the viscosity of the (meth) acrylate-modified epoxy resin is lower than 1000 cps, there is a problem that inherent characteristics such as adhesiveness of the (meth) acrylate-modified epoxy resin are partially difficult to be exhibited, and when it is 15000 cps or more. There is a problem of lowering the overall viscosity and dispersion stability of the curable resin composition.

As the thermosetting agent, it is preferable to use a latent thermosetting agent that hardening does not occur at a low temperature of 20 ° C or lower and hardening occurs at a high temperature of 40 ° C or higher. As the latent thermosetting agent, one type of thermosetting agent selected from the group consisting of imidazole type, dihydrazide type and amine type thermosetting agents can be used. In particular, it is preferable to use a dihydrazide-type hardening | curing agent in order to prevent the contamination of the liquid crystal of the liquid crystal display element manufactured, and to improve the adhesive force with a board | substrate.

Specific examples of the imidazole type curing agent include 2-methylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, P-0505 (manufactured by Shikoku Corporation), and the like. Can be. Specific examples of the dihydrazide-based curing agents include amcure VDH, amcure UDH (manufactured by Ajinomoto Co., Ltd.), ADH, SDH, DDH, IDH (manufactured by Otsuka Chemical Co., Ltd.), and NDH (manufactured by Nippon Hydrazine Industry Co., Ltd.). . Moreover, as a specific example of an amine-type hardening | curing agent, it is a cure PN-23, an cure PN-H, an cure PN-31, an cure PN-40, an cure PN-23J, an cure PN-31J, an cure PN -40J, amcure MY-24, amcure MY-H, amcure MY-HK-1, amcure AH-203, amcure AH-300, amcure AH-154, amcure AH-163 (manufactured by Ajinomoto Co., Ltd.) ), And the like. The amount of the thermosetting agent may be used in an amount of 1 to 10 parts by weight based on 100 parts by weight of the modified epoxy resin including a (meth) acrylate group.

The photopolymerization initiator is a benzoin compound, acetophenones, benzophenones, thioxanthones, anthraquinones, α-acyl oxime esters, phenylglyoxylates, benzyls, azo compounds, thiphenyl sulfide compounds , Acylphosphineoxy compound, organic pigment compound, iron-phthalocyanine compound and the like can be used. Specifically, at least one selected from the group consisting of benzophenone, 2,2-diethoxyacetophenone, benzyl, benzoylisopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, and thioxanthone can be used. have.

The content of the photopolymerization initiator may be used in an amount of 1 to 5 parts by weight based on 100 parts by weight of the modified epoxy resin including the (meth) acrylate group. Compounds that can be used as the photopolymerization initiator may be used alone or in combination of two or more.

As the inorganic filler, fillers such as silica or talc can be used. In addition, the maximum size of the particles as the filler may be used that is 5㎛ or less. If the maximum particle size exceeds 5 μm, the cell gap is not maintained during glass adhesion of the upper and lower glass plates of the liquid crystal display device, thereby causing defects. Preferably, an inorganic filler having an average particle diameter of 2 µm or less and having a uniform particle distribution may be used.

Although the type of the inorganic filler is not particularly limited, the inorganic filler may be, for example, silica, diatomaceous earth, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, barium sulfate, Gypsum, calcium silicate, talc, glass beads, mica, talc, bentonite, aluminum nitride, silicon nitride, potassium titanate, zeolite, calcia, magnesia and ferrite. The inorganic fillers may be used alone or in combination of two or more.

The content of the inorganic filler may preferably be 10 to 40 parts by weight based on 100 parts by weight of the modified epoxy resin including a (meth) acrylate group. If the content of the inorganic filler exceeds 50 parts by weight, there is a problem that 10 viscosity of the sealant composition is excessively increased.

Meanwhile, an organic filler may be used in addition to the inorganic filler. Examples of the organic filler that can be used in combination with the inorganic filler include methyl methacrylate, polystyrene, and copolymers of monomers copolymerizable therewith.

In addition to the thixotropic agent and the silane coupling agent, the other additives may further include photoinitiation accelerators, leveling agents, viscosity regulators, surfactants, plasticizers, ultraviolet absorbers, and the like.

Examples of the thixotropic regulator include methyl cellulose, methyl ethyl ketone peroxide, polyethylene oxide wax, modified polypropylene emulsion, polyamide wax, organic clay, alkyl sulfate, hydroxyl ethyl cellulose, hydroxyl acid esters, and polyvinyl alcohol. , Polydimethyl siloxane, unsaturated carboxylic acid monomers, hydroxide carboxylic acid amides, ethylene glycol, diethylene glycol, alkaline earth metal hydroxides, alkaline earth metal carbonates and the like can be used.

In addition to the above-mentioned additives, inorganic particles having an average particle size of 100 nm or less can be used as the additive. For example, a small amount of fine silica, zeolite, alumina, aluminum stearate, alumina hydroxide, mica, bentonite, or the like, which can be used as the inorganic filler, can be used.

The total content of the additives included in the composition may be 10 to 40 parts by weight based on 100 parts by weight of the modified epoxy resin including a (meth) acrylate group.

This invention also provides curable resin composition for liquid crystal dropping methods manufactured by the said manufacturing method, and containing the monomer represented by following General formula (1).

(One)

(In the formula (1), X is O, S or NH, R ₁ is H or CH ₃ , R ₂ is an alkyl group of C _1-30 or an aryl group of C _3-30 .)

The curable resin composition has a small content of moisture and air, exhibits excellent dispersion stability, and has characteristics such as excellent adhesion, storage stability and linearity on a substrate by the monomer of the formula (1).

R ₂ is ethylene glycol, glycerin, sorbitol, trimethylol propane, (poly) propylene glycol, 1,3-propane diol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, mono (meth) acrylate , Trimethylolethane, trimethylolpropane, diisocyanate, tolylene diisocyanate, xylene diisocyanate, isophorone diisocyanate, tolidine, diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, caprolactone ethyl ester , N-3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- [5- (trimethoxy silyl) -2-1-oxo-pentyl] caprolactam, O- ( Vinyloxyethyl) -N- (triethoxysilylpropyl) urethane, gamma-undecalactone, epsilon-caprolactone, gamma-decaractone, alpha-dodecaractone, gamma-nonalactone, gamma-nonanolactone, Gamma- valerolactone, alpha-ballet At least one selected from the group consisting of lolactone, beta, butyrolactone, gamma-butyrolactone, beta-propiolactone, alpha-hexanolactone and 7-butyl-2-oxepanone.

The present invention also, in part, 100 parts by weight of the modified epoxy resin containing a (meth) acrylate group, 5 to 30 parts by weight of the monomer represented by the following formula (1), 1 to 10 parts by weight of the thermosetting agent and 1 to 5 photopolymerization initiator It provides the sealant composition for liquid crystal display elements containing a weight part.

(One)

(In the formula (1), X is O, S or NH, R ₁ is H or CH ₃ , R ₂ is an alkyl group of C _1-30 or an aryl group of C _3-30 .)

The sealant composition for a liquid crystal display device exhibits excellent dispersion stability when used in the liquid crystal dropping method by the modified epoxy resin containing the (meth) acrylate group and the monomer represented by the formula (1), the curing time is very short, and the adhesiveness This is an excellent feature. In addition, when the coating on the substrate of the liquid crystal is excellent in the linearity there is an advantage that can minimize the contamination to the liquid crystal.

R ₂ is ethylene glycol, glycerin, sorbitol, trimethylol propane, (poly) propylene glycol, 1,3-propane diol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, mono (meth) acrylic Rate, trimethylolethane, trimethylolpropane, diisocyanate, tolylene diisocyanate, xylene diisocyanate, isophorone diisocyanate, tolidine, diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocytate, caprolactone ethyl Ester, N-3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- [5- (trimethoxy silyl) -2-1-oxo-pentyl] caprolactam, O- (Vinyloxyethyl) -N- (triethoxysilylpropyl) urethane, gamma-undecalactone, epsilon-caprolactone, gamma-decaractone, alpha-dodecaractone, gamma-nonalactone, gamma-nonanolactone , Gamma-valerolactone, alpha-ballet At least one selected from the group consisting of lolactone, beta, butyrolactone, gamma-butyrolactone, beta-propiolactone, alpha-hexanolactone and 7-butyl-2-oxepanone.

The sealant composition for a liquid crystal display device comprising the modified epoxy resin partially containing the (meth) acrylate group and the monomer represented by the following general formula (1) is a curable resin composition for a liquid crystal dropping method, and preferably 1500mJ / cm ² What is hardened | cured by passing through the photocuring step of UV hardening above and the thermosetting step thermosetting at the temperature of 70 degreeC or more can be used.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are only for illustrating the present invention, and the protection scope of the present invention is not limited to the following Examples.

Example

Example 1

65 g of partial (meth) acrylate epoxy resin, 6 g of hydroxy ester (meth) acrylate monomer, 2 g of photopolymerization initiator, 20 g of inorganic filler, 3 g of silane coupling agent, 2 g of MDH (Malonic acid dihydrazide, product of Aldrich) and Amicure as a thermosetting agent After mixing 2 g of UR (air product manufactured), milling sufficiently with a three-roll mill, filtering the composition to remove the foreign substance by rotating a degassing agitator (vacuum defoaming stirring mixer, UFO-S5, manufacturer EME, Japan) After vacuum degassing at 750 rpm for rotation and 500 rpm for 30 minutes, a sealant composition was obtained.

Comparative example

Comparative Example 1

65 g of partial (meth) acrylate epoxy resin, 6 g of hydroxy ester (meth) acrylate monomer, 2 g of photopolymerization initiator, 20 g of inorganic filler, 3 g of silane coupling agent, 2 g of MDH (Malonic acid dihydrazide, product of Aldrich) and Amicure as a thermosetting agent After mixing 2 g of UR (air product manufactured), milling sufficiently with a three-roll mill, filtering the composition to remove the foreign substance by rotating a degassing agitator (vacuum defoaming stirring mixer, UFO-S5, manufacturer EME, Japan) After vacuum degassing for 30 minutes at a rotation of 450rpm and a revolution of 100rpm to obtain a sealant composition.

Comparative Example 2

65 g of partial (meth) acrylate epoxy resin, 6 g of hydroxy ester (meth) acrylate monomer, 2 g of photopolymerization initiator, 20 g of inorganic filler, 3 g of silane coupling agent, 2 g of MDH (Malonic acid dihydrazide, product of Aldrich) and Amicure as a thermosetting agent 2 g of UR (from Air Products) was blended, milled sufficiently with a 3-roll mill, and filtered to obtain a sealant composition from which foreign materials were removed.

Comparative Example 3

65 g of partial (meth) acrylate epoxy resin, 6 g of hydroxy ester (meth) acrylate monomer, 2 g of photopolymerization initiator, 20 g of inorganic filler, 3 g of silane coupling agent, 2 g of MDH (Malonic acid dihydrazide, product of Aldrich) and Amicure as a thermosetting agent After mixing 2 g of UR (from Air Products) and 0.1 g of antifoaming agent (BYK 141, manufactured by BYK), the mixture was sufficiently milled with a three-roll mill, and then filtered to obtain a sealant composition from which foreign substances were removed.

Comparative Example 4

65 g of partial (meth) acrylate epoxy resin, 6 g of hydroxy ester (meth) acrylate monomer, 2 g of photopolymerization initiator, 20 g of inorganic filler, 3 g of silane coupling agent, 2 g of MDH (Malonic acid dihydrazide, product of Aldrich) and Amicure as a thermosetting agent 2 g of UR (air product manufactured) and 0.05 g of antifoaming agent (BYK 141, manufactured by BYK) were blended and sufficiently milled with a 3-roll mill, followed by a filter to obtain a sealant composition from which foreign materials were removed.

The compositions formulated to obtain the sealant compositions in Example 1 and Comparative Examples 1-4 are shown in Table 1 below.

TABLE 1

Resin filler PI Coupling agent Hardener Antifoam Defoaming R _A R _B R _C F _A F _B Photoinitiator Silane compound C _A C _B rotating revolution time Example 1 32.5 32.5 6 10 10 2 3 2 2 750 500 30 minutes Comparative Example 1 32.5 32.5 6 10 10 2 3 2 2 450 100 30 minutes Comparative Example 2 32.5 32.5 6 10 10 2 3 2 2 Comparative Example 3 32.5 32.5 6 10 10 2 3 2 2 0.1 Comparative Example 4 32.5 32.5 6 10 10 2 3 2 2 0.05

In Table 1 above, all units are g. Resin (resin) was used as a mixture of R _A , R _B , R _C , R _A is a bisphenol A- diglycidyl (diglycidyl) compound with a molar ratio of (meth) acrylate group and epoxy group of 1: 1 a partial (meth) acrylate compounds, R _B is a compound having an epoxy (meth) acrylate deception without a bisphenol A- diglycidyl compound, R _C is hydroxy ester (meth) acrylate monomer. As a filler (inorganic filler), F _A and F _B were mixed and used, F _A is SP-15 (manufactured by Osaka kasel), and F _B is Aerosil 200 (manufactured by Degus). As a PI (photo initiator, photopolymerization initiator), TPO (Iracure TPO, manufactured by Ciba) was used. The silane compound used as the coupling agent is Z-6040 (manufactured by Dow Corning). As a thermosetting agent, C _A and C _B were mixed and used, C _A is MDH (Malonic acid dihydrazide, manufactured by Aldrich), and C _B is Amicure UR (Air Products).

Characterization of Sealant Compositions

Linearity evaluation

The sealant composition obtained in Example 1 and Comparative Examples 1 to 4 was applied to the center of the dispenser (Shot master 300S, manufactured by Musashi Engineering) on the edge of the cleaned ITO glass substrate (manufactured by Samsung Corning Precision Glass), and the same glass The substrate was superimposed on it. UV curing (2000mJ / cm ² ) and then heat curing (120 ℃, 30min) to observe the frame border under a microscope. For each specimen, the linearity was evaluated using a microscope, and the results are shown in Table 2 below.

◎ good linearity

X: Poor linearity

Adhesion Evaluation

The sealant compositions obtained in Example 1 and Comparative Examples 1 to 4 were respectively applied to the central portion of the cleaned ITO glass substrate (Samsung Corning Precision Glass), and the same glass substrate was superimposed thereon. After UV curing (2000mJ / cm ² ) was thermally cured (120 ℃, 30min) to prepare a specimen for measuring the adhesive strength. Each specimen was evaluated for adhesive strength using a tensile strength meter (HK5T, manufactured by Tinius Olsen), and the results are shown in Table 2 below.

Pressure Cooker Test (PCT)

After the adhesive strength measurement specimens prepared for the evaluation of adhesion strength were stored for 6 hours at 121 ° C., 100% RH, and 2 atm, each specimen was evaluated for tensile strength using a tensile strength meter. It is shown in Table 2 below.

Liquid crystal contamination (T _N-1 )

1 g of each of the sealant compositions obtained in Example 1 and Comparative Examples 1 to 4 was taken into an ampoule bottle, and then 1 g of liquid crystal was placed in the ampoule bottle and left for 1 hour. UV curing (2000mJ / cm ²⁾ after a thermal curing (120 ℃, 30min), and using a DSC measurement apparatus of T _N-1 values and the blank liquid crystal for each sample at a heating rate of 5 ℃ / min T _{N- 1} value was measured. The closer the T _N-1 value of each sample to the T _N-1 value of the blank liquid crystal is, the less contamination is caused by the liquid crystal. Thus, when there is a change in the value of 0.5 ° C. or more, it was evaluated as a defect. Indicated.

Storage stability

After the sealant compositions obtained in Examples 1 and Comparative Examples 1 to 4 were stored at room temperature for 2 weeks, the viscosity was measured by a spindle viscometer. When the viscosity after two weeks compared with the initial viscosity, it was evaluated as good when the change rate is within 100%, poor when more than 100%, the results are shown in Table 2 below.

TABLE 2

Linearity Adhesion PCT TNI Storage stability bubble Uplifting Linearity One 2 3 4 5 One 2 3 4 5 Example 1 none none ○ 1.8 1.7 1.7 1.6 1.7 1.8 1.7 1.7 1.7 1.8 Good Good Comparative Example 1 has exist has exist X 1.7 1.8 1.4 1.2 1.0 1.6 1.8 0.9 1.0 1.0 Good Good Comparative Example 2 has exist has exist X 1.0 1.8 1.7 1.0 1.8 1.8 1.0 0.9 1.7 1.9 Good Good Comparative Example 3 has exist has exist X 1.0 1.4 1.2 1.0 0.9 1.0 1.1 1.0 0.9 0.8 Bad Bad Comparative Example 4 has exist has exist X 1.0 1.2 1.1 1.0 1.0 1.0 0.9 1.0 1.0 1.1 Bad Bad

Referring to Table 2, the sealant composition prepared through the Examples of the present invention as compared to the sealant composition prepared through the Comparative Example assures an overall uniform adhesive performance, it can be confirmed that the excellent adhesion after the PCT conditions. .

Claims (15)

As a manufacturing method of curable resin composition used for a liquid crystal dropping method, A method for producing a curable resin composition for a liquid crystal dropping method comprising the step of removing foreign matter through a filter after mixing the respective components of the curable resin composition, and then removing bubbles using a deaerator. The method of claim 1, The process of removing bubbles using the degassing machine is a process for degassing the mixture of the components of the curable resin composition by rotating and revolving in a degassing machine. The method of claim 2, The rotation is 500rpm or more, the revolving method of producing a curable resin composition, characterized in that for rotating at a rotational speed (rpm) of 200rpm or more. The method of claim 1, The curable resin composition comprises a monomer represented by the following general formula (1). [Formula 1]

(One) (In the formula (1), X is O, S or NH, R ₁ is H or CH ₃ , R ₂ is an alkyl or aryl group of C _1-30 .) The method of claim 1, The curable resin composition is 100 parts by weight of a modified epoxy resin partially containing (meth) acrylate group; 5 to 30 parts by weight of monomer represented by the following formula (1); 1 to 10 parts by weight of a thermosetting agent; And Curable resin composition for liquid crystal dropping methods containing 1-5 weight part of photoinitiators. [Formula 1]

(One) (In the formula (1), X is O, S or NH, R ₁ is H or CH ₃ , R ₂ is an alkyl or aryl group of C _1-30 .) The method according to claim 4 or 5, R ₂ is ethylene glycol, glycerin, sorbitol, trimethylol propane, (poly) propylene glycol, 1,3-propane diol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, mono (meth) acrylate , Trimethylolethane, trimethylolpropane, diisocyanate, tolylene diisocyanate, xylene diisocyanate, isophorone diisocyanate, tolidine, diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, caprolactone ethyl ester , N-3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- [5- (trimethoxy silyl) -2-1-oxo-pentyl] caprolactam, O- ( Vinyloxyethyl) -N- (triethoxysilylpropyl) urethane, gamma-undecalactone, epsilon-caprolactone, gamma-decaractone, alpha-dodecaractone, gamma-nonalactone, gamma-nonanolactone, Gamma-Valerolactone, Alpha-Ballet Curable resin composition, characterized in that at least one selected from the group consisting of lactone, beta, butyrolactone, gamma-butyrolactone, beta-propiolactone, alpha-hexanolactone and 7-butyl-2-oxepanone Manufacturing method. The method according to claim 4 or 5, The curable resin composition further comprises 10 to 40 parts by weight of at least one additive selected from the group consisting of an inorganic filler, a thixotropic regulator and a silane coupling agent. The method of claim 5, The viscosity of the modified epoxy resin is a method for producing a curable resin composition, characterized in that 1000 to 15000cps. The method of claim 5, The modified epoxy resin is a method for producing a curable resin composition, characterized in that at least one selected from the group consisting of a noblock type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, tris phenol methane type epoxy resin and bisphenol type epoxy resin. . The method of claim 5, The thermosetting agent is a method for producing a curable resin composition, characterized in that at least one member selected from the group consisting of imidazole series, dihydrazide series and amine series. The method of claim 5, The photopolymerization initiator is a benzoin compound, acetophenones, benzophenones, thioxanthones, anthraquinones, α-acyl oxime esters, phenylglyoxylates, benzyls, azo compounds, thiphenyl sulfide compounds And at least one selected from the group consisting of acylphosphineoxy compounds, organic dye compounds, and iron-phthalocyanine compounds. The method of claim 5, The thixotropic modifier is methyl cellulose, methyl ethyl ketone peroxide, polyethylene oxide wax, modified polypropylene emulsion, polyamide wax, organo clay, alkyl sulfate, hydroxyl ethyl cellulose, hydroxyl acid esters, polyvinyl alcohol , Polydimethyl siloxane, unsaturated carboxylic acid monomers, hydroxide carboxylic acid amides, ethylene glycol, diethylene glycol, alkaline earth metal hydroxides and alkaline earth metal carbonates. Manufacturing method. Curable resin composition for liquid crystal dropping methods manufactured by the manufacturing method of Claim 1, and containing the monomer represented by following General formula (1). [Formula 1]

(One) (In the formula (1), X is O, S or NH, R ₁ is H or CH ₃ , R ₂ is an alkyl group of C _1-30 or an aryl group of C _3-30 .) 100 parts by weight of a modified epoxy resin containing a (meth) acrylate group, a liquid crystal comprising 5 to 30 parts by weight of a monomer represented by the following formula (1), 1 to 10 parts by weight of a thermosetting agent and 1 to 5 parts by weight of a photopolymerization initiator Sealant composition for display element. [Formula 1]

(One) (In the formula (1), X is O, S or NH, R ₁ is H or CH ₃ , R ₂ is an alkyl group of C _1-30 or an aryl group of C _3-30 .) The method of claim 14, The sealant composition for a liquid crystal display device is a sealant composition for a liquid crystal display device, characterized in that it is cured through a photocuring step of UV curing at 1500mJ / cm ² or more and a thermosetting step of thermosetting at a temperature of 70 ℃ or more.