KR100619770B1 - Uv and heat curable sealing composition for liquid crystal display - Google Patents

Abstract

The present invention eliminates the use of low molecular weight monomers or reactive or non-reactive diluents which may be present in the composition and miscible with liquid crystals. Prevents liquid crystal contamination by miscibility with liquid crystal during the time when the encapsulant contacts the liquid crystal in the unreacted state, and adds a light and / or a thermal curing initiator to the epoxy (meth) acrylate oligomer for use during the liquid crystal display driving. High reliability light and heat curable liquid crystal display panel liquid crystal inlet encapsulation which can fundamentally prevent trace amounts of unreacted photocuring agent from eluting or degrading to contaminate the liquid crystal or contaminating the liquid crystal with the unreacted photocuring initiator. It is to provide the first. The object of the present invention is to convert the light and heat curable liquid crystal display panel liquid crystal inlet encapsulant into light and heat curable epoxy acrylate oligomer, urethane oligomer type light curing agent addition epoxy acrylate and urethane oligomer type latent heat curing agent addition epoxy acrylate. It can achieve by constructing.

Liquid crystal display, panel, encapsulant, acrylate, epoxy

Description

Light and heat curable liquid crystal display panel encapsulant {UV AND HEAT CURABLE SEALING COMPOSITION FOR LIQUID CRYSTAL DISPLAY}             

1 is a conceptual diagram of a liquid crystal display panel encapsulation.

2 is a conceptual diagram of a test piece for measuring the adhesion of the liquid crystal display panel encapsulant.

3 is a phase transition behavior morphology according to the temperature change of the thermotropic liquid crystal.

4 is a conceptual view of the evaluation of moisture permeability after curing of a liquid crystal display panel encapsulant.

Explanation of symbols on the main parts of the drawings

1: liquid crystal display 11: liquid crystal inlet encapsulant (END-SEALANT)

12: liquid crystal injection hole 13: sealant for liquid crystal panel bonding (MAIN-SEALANT)

14: upper liquid crystal panel 15: lower liquid crystal panel

16: image display part (liquid crystal) 17: electrode

22, 23: indium tin oxide deposited glass (ITO glass)

31: complete isotropic phase

32: Initiation of transition from anisotropic to isotropic (iso-anisotropic co-exist phase)

33: complete anisotropic phase

41: calcium chloride

42: cured film molded from sealing agent composition of the present invention

The present invention relates to a light and heat curable liquid crystal display panel liquid crystal inlet encapsulant, and more specifically, to a light and heat curable epoxy acrylate oligomer and a urethane oligomer type photocuring agent added. Epoxy acrylate and urethane oligomer type latent thermal curing agent addition It is related with the light-and-heat-curable liquid crystal display panel liquid crystal injection hole sealing agent characterized by containing epoxy acrylate.

1 is a conceptual view of a liquid crystal display panel encapsulation bonding, in which a spacer and a sealant 13 for bonding a liquid crystal panel are coated on upper and lower liquid crystal panels 14 and 15 made of oriented indium tin oxide glass. After that, the mixture is heated and cured, and the liquid crystal 16 is injected thereinto to produce the same. After injecting the liquid crystal, the liquid crystal inlet 12 is sealed with the encapsulant 11 to finish the process of the liquid crystal panel. Currently, the heat-curable epoxy oligomer is used for the sealant 13 for liquid crystal panel bonding mainly used, and the ultraviolet-curable urethane or the epoxy oligomer is used for the liquid crystal inlet encapsulant 11. The liquid crystal panel bonding sealant 13 is not a problem for the contamination of the liquid crystal because the liquid crystal is injected after the heat-curable epoxy resin is applied around the panel substrate and the upper and lower plates are bonded and the heat curing is completed. It is characterized by strong adhesion peculiar to a cured epoxy oligomer. However, in the case of the liquid crystal inlet encapsulant, a combination of ultraviolet curing or ultraviolet curing with heat curing is used, and the components of the encapsulant may contaminate the liquid crystal because they directly contact the liquid crystal in an unreacted state during the process. Therefore, in the case of the liquid crystal inlet encapsulant which is in direct contact with the liquid crystal in the uncured state, the following characteristics according to the curing reaction process are required for liquid crystal contamination.

First, in the uncured state, the liquid crystal does not contaminate the liquid crystal even after contact with the liquid crystal for a certain time.

Secondly, do not contaminate the liquid crystal during the UV / thermal curing reaction in contact with the liquid crystal; and

Third, it is required that the encapsulant should not be contaminated by other impurities such as unreacted substances remaining after the reaction is completed.

In addition, as the physical properties of the liquid crystal inlet encapsulant, a high adhesive strength of 30kgf / ㎠ or more is required, and in order to eliminate the effects of deterioration of the adhesive force due to external moisture penetration and poor liquid crystal alignment, under 65 ° C and 95RH% conditions A water transmission of 30 g / cm 3 * 24 hrs or less is required for 24 hours. In addition, after applying the encapsulant to the liquid crystal inlet of the panel, high viscosity (about 100,000 cps or more, 25 ℃) and thixotropic to prevent flow is required. Currently, some examples of applying an epoxy (meth) acrylate oligomer as an ultraviolet curable liquid crystal injection encapsulating agent have been reported, and these are the case of using an alicyclic epoxy (meth) acrylate oligomer (US Pat. A liquid crystal inlet encapsulant (US Pat. 5,596,024) of a composition comprising a composition containing a glycidyl functional group capable of heating reaction with a (meth) acrylate oligomer and containing a monomer for improving water resistance has been reported.

When the alicyclic epoxy (meth) acrylate oligomer is used as in US Pat. No. 4,703,338, the adhesive strength of the encapsulant can be improved to some extent, but the thermal and chemical properties of the bisphenol A aromatic epoxy (meth) acrylate Compared with oligomers, there are disadvantages, and when the photoreactive diluent is added to adjust the viscosity as in U.S. Patent No. 5,596,024, the liquid crystals are likely to be contaminated by the vulcanization of the uncured low molecular weight monomer even after photocuring. It may adversely affect the driving of the manufactured display.

In addition, as in the above two patents, the migration of the decomposed photocuring initiator into the liquid crystal, which may occur in a simple blending application for applying the photocurable initiator as the encapsulant for encapsulating the liquid crystal panel, may also cause contamination of the liquid crystal. In the case of the conventional UV-curable liquid crystal injection encapsulation encapsulant, since it is applied to the package after curing using only ultraviolet rays, the internal strain generated during the curing reaction of the encapsulant retains its internal temperature and Under the conditions of humidity, expansion and contraction may occur, which may cause a decrease in adhesion.

On the other hand, patent WO02092718, which deals with the contents of the liquid crystal panel bonding sealant and the liquid crystal inlet encapsulant for a liquid crystal display, discloses a relatively high molecular weight oligomeric light that forms a urethane bond using a photocuring agent which also contains a hydroxyl group. Curing agent is specified. However, no mention has been made of the reliability and curing characteristics of the liquid crystal of the photocuring agent. Although it contains a reactor that enables UV reaction, it is difficult to expect sufficient UV reactivity only by the characteristics of a mono-functional, but rather a photocuring agent oligomer cleaved without participating in the reaction by a photocuring reaction. There is a problem in that the possibility of migrating into portions of the liquid crystal can be rather increased.

Therefore, it does not contaminate the liquid crystal when it is in contact with the liquid crystal for a certain period of time in the uncured state, does not contaminate the liquid crystal during the ultraviolet and / or thermal curing reaction in contact with the liquid crystal, and does not contaminate the liquid crystal even after the curing reaction is completed. There is a demand for the development of a liquid crystal inlet encapsulant in which the liquid crystal is not contaminated by other impurities.

Accordingly, the present inventors have added and combined a photocuring agent and / or a latent thermosetting monomer with an epoxy acrylate oligomer, so that the curing agent monomer becomes a liquid crystal upon contact with the liquid crystal in uncured state for a predetermined time or during light and / or heat curing. A light and thermosetting liquid crystal display panel liquid crystal inlet encapsulant which does not deviate, does not contaminate liquid crystals due to unreacted monomers after the curing reaction is completed, and dramatically increases the durability of the liquid crystal display which does not affect the driveability of liquid crystals. Developed.

The present invention provides a highly reliable light and thermosetting liquid crystal display panel liquid crystal which can fundamentally prevent contamination of liquid crystals by dramatically reducing miscibility with liquid crystals before and after curing, which is a problem of conventional liquid crystal display panel liquid crystal inlet encapsulants. To provide an inlet encapsulant.

The present invention eliminates the use of low molecular weight monomers or reactive or non-reactive diluents which may be present in the composition and miscible with liquid crystals. It is to provide a highly reliable light and thermosetting liquid crystal display panel liquid crystal inlet encapsulant that can prevent the liquid crystal contamination by miscibility with the liquid crystal during the time when the encapsulant contacts the liquid crystal in the unreacted state.

In addition, the present invention is an unreacted photocuring initiator in which a small amount of unreacted photocuring agent elutes or decomposes during liquid crystal display operation by contaminating or decomposing liquid crystals by adding and reacting a photocuring initiator to an epoxy (meth) acrylate oligomer. It is an object of the present invention to provide a highly reliable light and heat curable liquid crystal display panel liquid crystal inlet encapsulant which can fundamentally prevent contamination of liquid crystals.

The present invention uses a latent epoxy thermal curing agent by addition reaction to an epoxy (meth) acrylate oligomer, so that a small amount of unreacted latent thermal curing agent is eluted or decomposed during liquid crystal display operation to contaminate the liquid crystal or low molecular weight during the thermal curing process. It is intended to provide a highly reliable light and heat curable liquid crystal display panel encapsulant having a strong adhesive force as well as preventing contamination of the liquid crystal by an unreacted latent heat curing agent present as a monomer.

Another object of the present invention is to encapsulate the liquid crystal inlet of the liquid crystal display panel, and then heat cured after ultraviolet curing, thereby improving adhesion and high reliability light and heat, which is not inferior to conventional encapsulation agents in other physical properties such as water resistance and viscosity. It is to provide a curable liquid crystal display panel encapsulant.

The above object of the present invention can be achieved by using a light and heat curable liquid crystal display panel encapsulant by adding a light and heat curable epoxy acrylate oligomer, a urethane oligomer type photocuring agent and a urethane oligomer type latent heat curing agent to an epoxy acrylate. Can be.

The light and thermosetting liquid crystal display panel liquid crystal inlet encapsulant of the present invention,

(1) a light and heat curable epoxy acrylate oligomer represented by the following general formula (I),

(2) addition of urethane oligomer type photocuring agent and urethane oligomer type latent heat curing agent represented by the following general formula (V) Epoxy acrylate and

(3) It is characterized by containing an inorganic additive (first type).

<Formula (Ⅰ)>

(In General Formula (I), F represents a hydrogen, a hydroxyl group or a methyl group, R ₁ , R ₂ represents a hydrogen or a methyl group, and R ₃ represents a glycidyl ether or di glycidyl ether functional group.)

<Formula (V)>

(In formula (V), R ₁ , R ₂ are hydrogen, hydroxyl group or methyl group, R ₄ is di- or tri-isocyanate compound, R ₅ is hydroxyl group-containing photocuring agent, R ₆ is latent thermal curing agent. Indicates.)

In addition, the light and heat-curable liquid crystal display panel liquid crystal inlet sealing agent of the present invention,

(1) a light and heat curable epoxy acrylate oligomer represented by the general formula (I),

(2) Epoxy acrylate addition of urethane oligomer type photocuring agent represented by the following general formula (V-1),

(3) a urethane oligomer-type latent heat curing agent addition epoxy acrylate represented by the following general formula (V-2), and

(4) It is characterized by containing an inorganic additive (second type).

<Formula (V-1)>

(In said general formula (V-1), R <_1> , R <_2> represents a hydrogen, a hydroxyl group, or a methyl group, R <_4> represents a di- or tri-isocyanate compound, and R <_5> represents a hydroxyl group containing photocuring agent.)

<Formula (V-2)>

(In said general formula (V-2), R <_1> , R <_2> represents a hydrogen, a hydroxyl group, or a methyl group, R <_4> represents a di- or triisocyanate compound, and R <_6> represents a latent thermosetting agent.)

The light and heat curable liquid crystal display panel liquid crystal inlet encapsulant of the present invention may further include a curing catalyst in the encapsulant.

The light and heat curable liquid crystal display panel liquid crystal inlet encapsulant of the first type according to the present invention,

40 parts by weight to 65 parts by weight of light and heat curable epoxy acrylate oligomer represented by general formula (I), addition of urethane oligomer type photocuring agent and urethane oligomer type latent thermal curing agent represented by general formula (V) It is preferable to contain 10-30 weight part of epoxy acrylates, and 15 weight part-45 weight part of inorganic additives,

The second type of light and thermosetting liquid crystal display panel liquid crystal inlet encapsulant of the present invention,

40 parts by weight to 65 parts by weight of the light and heat curable epoxy acrylate oligomer represented by the general formula (I), and 1 part by weight of the epoxy acrylate addition epoxy acrylate represented by the general formula (V-1). Weight part, urethane oligomer type latent heat hardener addition epoxy acrylate represented by said general formula (V-2) It is preferable to contain 10-30 weight part and 15 weight part-45 weight part of inorganic additives.

In addition, the light and heat curable liquid crystal display panel encapsulant of the present invention may be added 15 to 45 parts by weight of a curing catalyst.

The photo- and heat-curable epoxy acrylate oligomers represented by the general formula (I) may be synthesized by reacting bisphenol-type epoxy oligomers with acrylic compounds such as acrylic acid, methacrylic acid, and derivatives thereof in a conventional manner. .

The compound represented by the above general formula (V) is a compound in which a urethane oligomer-type photocuring agent and a urethane oligomer-type latent heat curing agent are added to an epoxy acrylate, which is represented by the following general formula (II) The urethane oligomer type photocuring agent and / or latent thermosetting agent represented by general formula (IV) can be reacted by addition and synthesize | combined.

<Formula (II)>

(In said general formula (II), F represents a hydrogen, a hydroxyl group, or a methyl group, and R <_1> , R <_2> represents a hydrogen or a methyl group.)

<Formula (Ⅳ)>

(In the general formula (IV), R ₄ represents a di- or triisocyanate compound, R ₅ represents a hydroxyl group-containing photocuring agent, and R ₆ represents a latent thermal curing agent.)

In addition, in the general formula (V-1) The compound to be represented is a compound in which a urethane oligomer-type photocuring agent is added to an epoxy acrylate, a photocurable epoxy diacrylate represented by the general formula (II) and a urethane oligomer-type photocuring agent represented by the following general formula (IV-1). Can be synthesized by addition reaction.

<Formula (IV-1)>

(In the general formula (IV-1), R ₄ represents a di- or triisocyanate compound, and R ₅ represents a hydroxyl group-containing photocuring agent.)

In addition, to the general formula (V-2) The compound shown is a urethane oligomer type latent heat curing agent added to an epoxy acrylate, and a urethane oligomer type represented by the following general formula (IV-2) to a photocurable epoxy diacrylate represented by the general formula (II). It can be synthesized by addition reaction of the latent thermal curing agent.

<Formula (IV-2)>

(In the general formula (IV-2), R ₄ represents a di- or tri-isocyanate compound, and R ₆ represents a latent thermosetting agent.)

The photocurable epoxy diacrylate represented by the general formula (II) may be synthesized by reacting an epoxy oligomer having an epoxy group at both terminals and an acrylic compound with a reaction catalyst in a conventional manner.

The compound represented by the general formula (IV) may be synthesized by urethane-reacting a bifunctional or trifunctional isocyanate compound with a photocuring agent and a latent thermal curing agent containing a hydroxyl group,

The compound represented by the general formula (IV-1) may be synthesized by urethane reaction of a bifunctional or trifunctional isocyanate compound with a photocuring agent containing a hydroxyl group,

The compound represented by the general formula (IV-2) can be synthesized by urethane-reacting a bifunctional or trifunctional isocyanate compound with a latent thermosetting agent.

As described above, in the present invention, the isocyanate compound, the photocuring agent, and / or the latent thermosetting agent may be used in urethane to fundamentally prevent contamination of the liquid crystal generated by the dehydration of the curing agent monomer to the liquid crystal. This is possible because the light and thermal curing agents are themselves contained in the molecular structure of the epoxy (meth) acrylate oligomer containing a curing functional group.

Hereinafter, the present invention will be described in more detail.

The photocurable and heat curable epoxy (meth) acrylate oligomers represented by the general formula (I) preferably have a molecular weight of 500 grams per mole (g / mol) to 3000 grams per mole (g / mol). When the molecular weight is less than 500 g / mol, the miscibility with the liquid crystal increases, and there is a concern that the liquid crystal may be contaminated when contacted with the liquid crystal in the unreacted state. When the molecular weight exceeds 3000 grams per mol (g / mol), the molecular weight Increasing the viscosity may cause excessively high viscosity, which makes the process very difficult to handle.

Synthesis of the photo-curable and heat-curable epoxy acrylate oligomer represented by the general formula (I) is, for example, after adding a bisphenol-type epoxy oligomer and triphenylphosphine as a catalyst to the reactor, the temperature is 80 ~ 100 ℃ After the temperature was raised, the nitrogen gas was sufficiently refluxed and the stirring speed was maintained at 100 to 200 rpm. When the temperature is stabilized at 80 ~ 100 ℃, the prepared acrylic compound prepared in advance by reacting with attention to the exotherm for 6 hours at the reaction temperature 100 ~ 110 ℃ it can synthesize a compound represented by the general formula (I). . Synthesis reaction is reacted to the point where no acrylic compound remains through GPC, and when completed, the compound is cooled and stored at room temperature.

Compound represented by the above general formula (Ⅰ) synthesized as above, is finally non-present inside the reaction and the reaction is K ^+, Cl ^-, subjected to a high purity refining process in order to remove Na ⁺ ions.

For one embodiment of the purification process, after dividing the compound 100g into a 1000ml beaker, 100g of methyl ethyl ketone is dissolved sufficiently, and then 300g of high-purity 4th distilled water was added to 30 minutes at room temperature. Stir at 100 to 300 rpm. After stirring, the mixture was transferred to a 1000 ml separatory funnel and allowed to stand until sufficient phase separation proceeded. After about 1 to 2 hours, when the phase separation is completed sufficiently, the fourth distilled water is removed, and the compound solution is transferred to a 1000 ml beaker, and 300 g of high-purity fourth distilled water is added thereto, followed by stirring at 300 rpm for 30 minutes at room temperature to purify the process. The process is repeated three more times to obtain a compound solution represented by the above general formula (I), which is finally dissolved in methyl ethyl ketone. Finally, the solution is vacuum-purified for 4 hours at a high pressure vacuum of 10-4 torr at 80-90 ° C. to remove water and solvent remaining in the oligomer. A part of the sample is taken to confirm the presence of methyl ethyl ketone through GPC, and the purification process is completed when the moisture content is 500 ppm or less using a moisture meter.

The urethane oligomer type photocuring agent and urethane oligomer type latent thermal curing agent represented by the said general formula (V) are added The epoxy acrylate preferably has a number average molecular weight of 500 grams per mole (g / mol) to 3500 grams per mole (g / mol).

When the molecular weight distribution is out of range, the same problem may occur as when the molecular weight distribution of Formula (I) is out.

Addition of the urethane oligomer type photocuring agent and the urethane oligomer type latent heat curing agent represented by the said general formula (V) The epoxy acrylate is a photocurable epoxy diacrylate represented by the above general formula (II) having a number average molecular weight of 500 grams per mole (g / mol) to 3500 grams per mole (g / mol) and a number average molecular weight of 500 grams It can be synthesized by addition reaction of the urethane oligomer-type light and latent thermal curing agent represented by the general formula (IV), which is per mole (g / mol) to 2000 grams per mole (g / mol).

It is preferable that the urethane oligomer type photocuring agent addition epoxy acrylate represented by the said General formula (V-1) has a number average molecular weight of 500 grams per mole (g / mol) to 3500 grams per mole (g / mol).

When the molecular weight distribution is out of range, the same problem may occur as when the molecular weight distribution of Formula (I) is out.

The urethane oligomer type photocuring agent addition epoxy acrylate represented by the general formula (V-1) has a number average molecular weight of 500 grams per mole (g / mol) to 3500 grams per mole (g / mol). The photocurable epoxy diacrylate represented by) and the urethane oligomer fluorescent material represented by the general formula (IV-1) having a number average molecular weight of 500 grams per mole (g / mol) to 2000 grams per mole (g / mol). It can synthesize | combine by making a hardening agent react.

The urethane acrylate oligomer type latent heat curing agent addition epoxy acrylate oligomer represented by the general formula (V-2) has an average molecular weight of 500 grams per mole (g / mol) to 3500 grams per mole (g / mol). desirable.

When the molecular weight distribution is out of range, the same problem may occur as when the molecular weight distribution of Formula (I) is out.

The urethane acrylate oligomer type latent heat curing agent addition epoxy acrylate represented by the general formula (V-2) has an average molecular weight of 500 grams per mole (g / mol) to 2500 grams per mole (g / mol). Photocurable epoxy diacrylate represented by formula (II) and a compound represented by the above general formula (IV-2) having a number average molecular weight of 500 grams per mole (g / mol) to 2000 grams per mole (g / mol) It can be synthesized by reacting.

The following compounds are suitable as compounds for the synthesis of the compounds represented by general formulas (I) to (V-2) according to the present invention.

As an epoxy oligomer which has an epoxy group at the both ends for manufacture of the photocurable epoxy diacrylate represented by the said General formula (II), what is suitable as a bisphenol-type epoxy oligomer is a bisphenol-A oligomer, a bisphenol-F oligomer, and a reduced bisphenol-A oligomer And reduced bisphenol F-type oligomers, caprolactone-modified epoxy oligomers (product name Flaccel GL61 manufactured by Daicel Chemical Industries, Inc.), and phenol novolac epoxy oligomers.

As the acrylic compound, acrylic acid, methacrylic acid, derivatives thereof, and the like, which are generally added with stabilizers such as polymerization inhibitors, and according to the present invention, they are purified by high purity in a method such as vacuum distillation at 100 ° C to 140 ° C. .

As said bifunctional or trifunctional isocyanate compound, For example, Isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, 4,4'-methylenebis (cyclohexyl) diisocyanate, xylene diisocyanate, tetramethyl xylene diisocyanate, Trimethylhexamethylene diisocyanate, 1,5-naphthalene diisocyanate, paraphenylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, or mixtures thereof, under the name Vestanat TMDI from Degussa HDI-based modified aliphatic polyisocyanate (1,3,5-tris (6-isocyanatohexyl) -1,3,5-triazine-2,4,6-tree containing isocyanurate and modified isocyanurate) On), Nippon Polyurethane Industry Co., Ltd. product name C-HXR, Acro Chemical company name Luxate HT2000 HDI trimmer). Most preferably, isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, modified isocyanurate-containing HDI-based modified aliphatic polyisocyanate, and the like are particularly preferably represented by the following general formula (III). It is a trifunctional isocyanate compound like the isocyanate compound shown.

<Formula (III)>

(In General Formula (III), R ₇ , R ₈ and R ₉ represent a hydroxyl group or an isocyanate functional group.)

As a photocuring agent containing the said hydroxyl group For example, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl propane-1-one containing a hydroxyl group at one end {2-hydroxy-1- [4- (2-hydroxy ethoxy) phenyl] -2-methyl propane-1-one} {product made by Ciba-Geigy, product name Irgacure2959}, 2-hydroxy-2-methyl-1-phenylpropane-1- {2-hydroxy-2-methyl-1-phenylpropane-1-on} {product made by Ciba-Geigy, product name Irgacure1173}, (1-hydroxycyclohexyl) -phenyl-methanone {( 1-hydroxy-cyclohexyl) -phenyl-methanone} {manufactured by Ciba-Geigy, product name Irgacure184}, or a mixture of the compounds (product name Irgacure1000 of the manufacturer) may be used.

The photocuring agent containing the said hydroxyl group It is purified and used for high purity. As an example of the purification method, after dissolving the photocuring agent in high-purity HPLC grade methanol, it is left at -20 ℃ for 12 hours, the precipitated photocuring agent is collected and pulverized finely, and again has a pressure of 10-4torr It can be purified through a vacuum purification process to remove residual methanol and water using a vacuum equipment. The final high purity purified product obtained in this way is sealed and stored in a container that does not penetrate moisture.

Suitable compounds for the latent thermal curing agent include dimiandiamide-based product name Amicure CG1400 or copper CG325, ACR Company's product name 3615S, which is a latent curing agent of Air Products of the United States. For example, the modified hydrazide-based product name Ajicure VDH (4-isopropyl-2,5-dioxoimidazolidine-1,3-di (propionohydrazide), Ajicure ADH (Adipic dihydrazide), IDH (Isophthalic dihydrazide), etc. The latent thermal curing agent It is purified and used for high purity.

In addition, the inorganic additives that lower the UV light curing reaction of epoxy acrylate and polymerization shrinkage during heat curing and improve the mechanical properties of the cured product have a particle size of 50 nanometers (nm) to 5 micrometers (μm) in size. Ranges include synthetic silica (Degus Aerosil R200, R202, R972, R8200 series, OX50, OK607) and pulverized natural mineral based calcium carbonate, talc, silica, spherical silica, silane coupling agent modified silica, alumina silicate, Whiskers, zeolites, etc. are mentioned.

The inorganic additive is purified before use.

As a suitable curing catalyst that can be added to the liquid crystal inlet sealant of the present invention, a compound having an alicyclic bis dimethyl urea structure is preferable as a compound containing an amine functional group. As such a compound, for example, the product name Ajicure PN23 of Ajinomoto, Japan, the product name U-CAT 3503N of San-Apro, and 3- (3,4-dichlorophenyl) -1,1-dimethyl urea, etc. For example.

Hereinafter, although an Example demonstrates this invention, this invention is not necessarily limited to a following example.

Example

[Example of Purification of Raw Material Compound]

Purification of Acrylic Acid

Temperature of 120 ℃ while stirring 250g of acrylic acid by using vacuum distillation tube which is filled with copper gauze and cooling distillation tube with 1000ml round bottom flask, vacuum pump, cooling water tank and heating device. Vacuum distillation was carried out under 3 hours. 200 g of purified acrylic acid collected in the flask contained in the cooling water tank was sufficiently cooled and collected. The collected purified acrylic acid was analyzed by a moisture measurement method to prepare a raw material having a water content of 300 ppm or less.

[Refining of Photocuring Agent Containing Hydroxyl Group]

(1-hydroxy-cyclohexyl) -phenyl-methanone} (Ciba-Geigy), product name Irgacure184 } 40 g were dissolved and then left at -20 ° C for 12 hours. Then, the precipitated photocuring agent is collected and pulverized finely, and then subjected to a vacuum purification process for removing residual methanol and water using a vacuum equipment having a pressure of 10-4torr. The final high purity purified product obtained in this way was sealed in a container which did not penetrate UV and moisture.

[Example of Purification of Potential Thermal Curing Agent]

Ajicure VDH (4-isopropyl-2,5-dioxoimidazolidine-1,3-di (propionohydrazide), a product name of Ajinomoto Co., Ltd., in Japan, was used as a latent heat curing agent. After dissolving in high-purity methanol to prepare a saturated solution, the mixture was left for 12 hours at -20 ° C. Then, the latent thermal curing agent was collected, ground finely, and then vacuum equipment having a pressure of 10-4 torr was again prepared. Vacuum purification process to remove residual methanol and water, the final high-purity purified product obtained in this way is sealed and stored in a space protected from moisture and heat.

[High Purification Purification of Inorganic Additives]

30 g of alumina silicate was added to 100 g of high-purity fourth distilled water, followed by stirring at 300 rpm for 30 minutes at room temperature to remove impurities and ions three times to obtain 98 g of high-purity alumina silicate. The alumina silicate was sufficiently dried under the conditions of 70 to 100 ° C. and purified by completely removing the remaining water at a pressure of 10 −4 torr.

Synthesis Example 1-6

[Synthesis of Compound Represented by General Formula (I)]

Triphenyl as a polymerization catalyst and bisphenol A type epoxy oligomer (380 g / mol) (Korea, Kukdo Chemical Co. Phosphine was added and the reaction temperature was raised to 80 ° C., and then purified acrylic acid prepared in advance at the reactor temperature of 80 ° C. was gradually added to control the exothermic reaction by the heat of reaction. It sustained and obtained the light and thermosetting epoxy acrylate oligomer represented by general formula (I). The end of the reaction was 6 hours after the addition of acrylic acid, when the residual acrylic acid was consumed by the reaction through gel permeation chromatography (GPC) analysis and was not detected.

The molecular weight and viscosity distribution of the light and heat curable epoxy acrylate oligomers represented by the general formula (I) synthesized above are shown in Table 5 below.

 division Reaction ratio                                              Input amount (g)                                               Catalyst content (g) YD128                                              Acrylic acid YD128 Acrylic acid Synthesis Example 1                                              One 0.4 461.783 38.217 1.5 Synthesis Example 2                                              One 0.6 444.785 55.215 1.5 Synthesis Example 3                                              One 0.9 421.512 78.488 1.5 Synthesis Example 4                                              One 1.4 387.7 112.3 1.5 Synthesis Example 5                                              One 1.7 369.90 130.1 1.5 Synthesis Example 6                                              One 2 353.659 146.34 1.5

Synthesis Example 7

[Synthesis of Compound Represented by General Formula (II)]

Into a 1 liter round bottom three-necked flask with a stirrer, 354.83 g of bisphenol F-type epoxy oligomer (352 g / mol) (trade name YDF170, Kukdo Chemical Co., Ltd., Korea) and 5 g of triphenylphosphine were added as a polymerization catalyst. It heats up to 80 degreeC which is a temperature. When the temperature of the reactor was fixed at 80 ° C., 145.16 g of purified acrylic acid was slowly added to control the exothermic reaction by the heat of reaction, and the reaction was continued at 110 ° C. to 120 ° C. to obtain 500 g of a photocurable epoxy acrylate oligomer. The end point of the reaction was the end point when all residual acrylic acid was consumed by the reaction through gel permeation chromatography (GPC) analysis after 6 hours of acrylic acid was not detected.

Synthesis Example 8

[Synthesis of Compound Represented by General Formula (IV-1)]

45.48 g of isophorone diisocyanate was added to a 1000-neck three-necked round bottom flask equipped with a stirrer and heated to 60 ° C., followed by a photocuring agent containing 0.25 g of dibutyltin dilaurate and a hydroxyl group (Shibagaiki, Japan). 46.9 g of the product name Darocur 1173) was sufficiently stirred and dipped into isophorone diisocyanate fixed at 60 ° C. at a rate of 20 drops per minute to give a reaction to obtain 100 g of a urethane oligomer-type photocuring agent. 2 hours after the completion of the drop, 5 g of the sample was taken and the reaction was terminated when the theoretical isocyanate content dropped to 8% or less using the urethane reaction titration method. The reaction product was placed in a storage container, filled with nitrogen, and sealed to prevent moisture from penetrating.

Synthesis Example 9

[Synthesis of Compound Represented by General Formula (IV-2)]

37.09 g of isophorone diisocyanate was added to a 1000 ml three-necked round bottom flask equipped with a stirrer and heated up to 30 ° C., followed by 0.25 g of dibutyl tin dilaurate and a latent thermosetting agent (Ajinomoto Co., Ltd. After dissolving 62.9 g of VDH) in excess acetone, the mixture was sufficiently stirred and dipped in an isophorone diisocyanate fixed at 30 ° C. at a rate of 20 drops per minute to obtain a 100 g urethane oligomer-type latent thermosetting agent. 2 hours after completion of the drop, 5 g of the sample was collected and the reaction was terminated when the theoretical isocyanate content dropped to 5.6% or less by using a urethane reaction titration method. The reaction product was placed in a storage container, filled with nitrogen, and sealed to prevent moisture from penetrating.

Synthesis Example 10-15

[Synthesis of Compound Represented by General Formula (V-1)]

A photocurable epoxy acrylate oligomer (General Formula II) synthesized in Synthesis Example 7 and a urethane oligomer photocuring agent (General Formula IV-1) synthesized in Synthesis Example 8 in a three-neck round bottom flask with a stirrer; Dibutyl tin dilaurate as a reaction catalyst is added to the reaction ratio (or the raw material input amount) as shown in Table 2, then heated to 60 ℃ and reacted at 250rpm for 6 hours under nitrogen reflux conditions. After 6 hours of stirring, the reaction was terminated by checking the residual isocyanate group present in the reaction product by FT-IR until the reaction disappeared completely, thereby adding a urethane oligomer-type photocuring agent-added epoxy acrylate represented by the general formula (V-1). Got it.

The molecular weight and viscosity distribution of the urethane oligomer type photocuring agent addition epoxy acrylate represented by the above-described general formula (V-1) are shown in Table 5 below.

 division Reaction ratio                                              Input amount (g)                                               Catalyst content (g) General formula (Ⅱ)                                              General formula (Ⅳ-1) General formula (Ⅱ) General formula (Ⅳ-1) Synthesis Example 10                                              One 0.3 314.27 185.73 0.25 Synthesis Example 11                                              One 0.6 229.5 270.85 0.25 Synthesis Example 12                                              One One 168.35 331.65 0.25 Synthesis Example 13                                              One 1.4 133.05 366.95 0.25 Synthesis Example 14                                              One 1.7 114.97 385.03 0.25 Synthesis Example 15                                              One 2 101.22 398.79 0.25

Synthesis Example 16-21

[Synthesis of Compound Represented by General Formula (V-2)]

A photocurable epoxy acrylate oligomer (General Formula II) synthesized in Synthesis Example 2 and a urethane oligomer-type latent thermosetting agent synthesized in Synthesis Example 4 in a three-neck round bottom flask with a stirrer (General Formula IV-2) And dibutyltin dilaurate as a synthesis catalyst in the following reaction ratio (or feed amount) as shown in Table 3, and then heated to 30 ° C. and reacted at 250 rpm for 8 hours under nitrogen reflux conditions. After 6 hours of stirring, the reaction was terminated by confirming the residual isocyanate group present in the reactant by FT-IR and proceeding until the reaction disappeared completely. The urethane oligomer type latent thermal curing agent added epoxy acryl represented by the general formula (V-2). The rate was obtained.

The molecular weight and viscosity distribution of the urethane oligomer type latent heat curing agent addition epoxy acrylate represented by the above-described general formula (V-2) are shown in Table 5 below.

 division Reaction ratio                                              Input amount (g)                                               Catalyst content (g) General formula (Ⅱ)                                              General formula (Ⅳ-2) General formula (Ⅱ) General formula (Ⅳ-2) Synthesis Example 16                                              One 0.3 297.97 202.03 0.25 Synthesis Example 17                                              One 0.6 212.22 287.78 0.25 Synthesis Example 18                                              One One 153.37 346.63 0.25 Synthesis Example 19                                              One 1.4 120.08 379.92 0.25 Synthesis Example 20                                              One 1.7 103.26 396.74 0.25 Synthesis Example 21                                              One 2 90.58 409.42 0.25

Synthesis Example 22

[Synthesis of Compound Represented by General Formula (IV)]

29.2 g of isophorone diisocyanate was added to a 1000-neck three-necked round bottom flask equipped with a stirrer and heated to 60 ° C., followed by a photocuring agent containing 0.25 g of dibutyl tin dilaurate and a hydroxyl group (Shibagaiki, Japan). After mixing 29.46 g of Darocur 1173) product namely with sufficient stirring, the reaction proceeds by dropping 20 drops per minute at a rate of 20 drops per minute to isophoronediisocyanate fixed at 60 ° C to induce a urethane reaction of an isocyanate and a photocuring agent. After 2 hours of reaction, the reaction temperature was cooled to 30 ° C. when the ratio reached to the theoretical NCO% of 5.52% or less through the reagent titration method of the urethane reaction. Then, 41.34 g of a latent thermal curing agent (product name VDH manufactured by Ajinomoto Co., Ltd., Japan) was dissolved in an excess of acetone, stirred sufficiently, and reacted by dropping it at a rate of 20 drops per minute to a reactant fixed at 30 ° C. Proceed. After 4 hours from the reaction time, a small amount of sample is taken and the reaction proceeds until no residual isocyanate group remains through FT-IR.

Synthesis Example 23-28

[Synthesis of Compound Represented by General Formula (V)]

In a three-necked round bottom flask with a stirrer, a urethane oligomer-type light and thermal curing agent (formula IV) synthesized in Synthesis Example 22 mentioned above and 0.25 g of dibutyltin dilaurate were used as a reaction catalyst. The reaction mixture was added at the same reaction ratio (or input amount of raw materials), and then heated to 60 ° C. and reacted at 250 rpm for 6 hours under nitrogen reflux conditions. After 6 hours of reaction, a small amount of samples are taken using FT-IR to determine the presence of unreacted residual isocyanate to determine the end of the reaction.

 division Reaction ratio                                              Input amount (g)                                               Catalyst content (g) General formula (Ⅱ) General formula (Ⅳ-2) General formula (Ⅱ) General formula (Ⅳ-2) Synthesis Example 23 One 0.3 67.53 32.48 0.25 Synthesis Example 24 One 0.6 50.97 49.03 0.25 Synthesis Example 25 One One 38.42 61.58 0.25 Synthesis Example 26 One 1.4 30.82 69.18 0.25 Synthesis Example 27 One 1.7 26.84 73.16 0.25 Synthesis Example 28 One 2 23.78 76.23 0.25

           <Molecular weight and viscosity distribution of the compound> division Number average molecular weight (g / mol) Viscosity (cps, 25 ° C, 65% RH) Synthesis Example 1 600 24,000 Synthesis Example 2 2,100 38,000 Synthesis Example 3 2,500 67,000 Synthesis Example 4 2,800 94,000 Synthesis Example 5 4,600 160,000 Synthesis Example 6 420 18,000 Synthesis Example 7 2,200 34,000 Synthesis Example 8 900 12,000 Synthesis Example 9 1,400 20,000 Synthesis Example 10 1,050 40,000 Synthesis Example 11 1,480 44,000 Synthesis Example 12 1,800 46,000 Synthesis Example 13 2,000 55,000 Synthesis Example 14 3,000 80,000 Synthesis Example 15 480 36,000 Synthesis Example 16 1,600 37,000 Synthesis Example 17 1,900 42,000 Synthesis Example 18 2,200 50,000 Synthesis Example 19 2,800 66,000 Synthesis Example 20 3,300 96,000 Synthesis Example 21 460 36,000 Synthesis Example 22 1,600 28,000 Synthesis Example 23 1,750 31,000 Synthesis Example 24 1,900 44,000 Synthesis Example 25 2,300 60,000 Synthesis Example 26 2,500 68,000 Synthesis Example 27 3,800 107,000 Synthesis Example 28 420 22,000

[High Purification Purification of Each Composite]

450 g of each of the compounds synthesized in Synthesis Examples 1-6, Synthesis Examples 10-15 and 16-21, and Synthesis Examples 23-28 were each added to a 3-liter reactor, and then dissolved in 300 g of reagent-level methyl ethyl ketone. I was. Then, 1 kg of ultra high purity distilled water (4th distilled water) was added thereto, followed by stirring for 2 hours at 40 ° C., and then left for 3 hours. The solution portion of the compound synthesized by Synthesis Example except the ultra high purity distilled water layer separated therefrom. Only each was separated. This process was carried out by quantitative analysis (measured by Dionex model name DX-500) of Na ⁺ , K ⁺ and Cl ^- ions dissolved in separated distilled water layers until each ion was detected below 30 ppm. Repeated (three times). Ultra-pure distilled water remaining while sufficiently agitating using a vacuum distillation apparatus equipped with a cooling water tank and a cold trap after the solution was finally heated to 40 to 50 ° C. in which the concentration of the contained ions was 30 ppm or less. And methyl ethyl ketone as a solvent were removed. A small amount of this vacuum distillation process was extracted at a time when no defoaming was generated (lasting for 6 hours) to verify the presence of residual monomers and other impurities through FTIR, GPC, and moisture analyzer (Metrohm, model name 756KF, 728). stirrer) to quantify the residual moisture. If residual monomer and other impurities are not present and the residual water content is quantified to 300 ppm or less, the process is completed and 350 g of each of the purified Synthesis Examples 1-6, Synthesis Examples 10-15 and 16-21, and Synthesis Examples 23-28 are completed. The synthesized compound was obtained.

Example 1-4

55 parts by weight of each of the light and heat curable epoxy arcrelate oligomers represented by General Formula (I) obtained in Synthesis Example 1-4, and the urethane oligomer type represented by the above general formula (V-1) obtained in Synthesis Example 10-13. 2 parts by weight of each of the light curing agent-added epoxy acrylate, 15 parts by weight of each of the urethane oligomer-type latent heat curing agent addition epoxy acrylate represented by the general formula (V-2) obtained in Synthesis Example 16-19, and a refined inorganic filler As a total amount of the Aerosil R200 28 parts by weight of the German Degusa as a total amount of 100g, and then uniformly mixed using a three-roll mill at room temperature to light and heat-curable liquid crystal display panel liquid crystal inlet encapsulation agent according to the present invention The composition was formulated.

Comparative Example 1-2

55 parts by weight of each of the light represented by the general formula (I) obtained in Synthesis Example 5-6 and the heat curable epoxy acrylate oligomer, and the urethane oligomer type represented by the general formula (V-1) obtained in Synthesis Example 14-15. 2 parts by weight of the curing agent addition epoxy acrylate each, 15 parts by weight of the urethane oligomer type latent heat curing agent addition epoxy acrylate represented by the general formula (V-2) obtained in Synthesis Example 20-21, and as an inorganic filler, 28 parts by weight of Aerosil 200, manufactured by Kook Degus Co., Ltd. was added in a total amount of 100 g, and an encapsulant composition was uniformly mixed using a 3-roll mill at room temperature.

Example 5-8

55 parts by weight of each of the light and thermosetting epoxy acrylate oligomers represented by General Formula (I) obtained in Synthesis Example 1-4, and the urethane oligomer type photocuring agent represented by the general formula (V) obtained in Synthesis Examples 23-26. And urethane oligomer type latent thermal curing agent addition Each 25 parts by weight of epoxy acrylate and an inorganic filler, 20 parts by weight of Aerosil200 from Degussa, Germany, were added to a total amount of 100 g, and then uniformly mixed using a 3-roll mill at room temperature to obtain light and A thermosetting liquid crystal display panel liquid crystal inlet encapsulant composition was prepared.

Comparative Example 3-4

55 parts by weight of each of the light and heat curable epoxy acrylate oligomers represented by General Formula (I) obtained in Synthesis Example 5-6, a urethane oligomer type photocuring agent represented by the general formula (V) obtained in Synthesis Examples 27-28, and Urethane oligomer type latent heat curing agent addition Each 25 parts by weight of epoxy acrylate and 20 parts by weight of Aerosil 200, manufactured by Degussa, Germany, were added so as to have a total amount of 100 g, and then a composition was uniformly mixed using a 3-roll mill at room temperature.

[Comparative Example 5]

55 parts by weight of light and heat-curable epoxy acrylate oligomer represented by General Formula (I) obtained in Synthesis Example 1, and a hydroxyl group which is a monomer type used in Synthesis Example 8 (synthesis of compound represented by General Formula (IV-1)). 2 parts by weight of a light curing agent (product name Darocur 1173 manufactured by Shiba-Gaigi Co., Ltd.), and a latent thermal curing agent (Ajinomoto, Japan) which is a monomer type used in Synthesis Example 9 (synthesis of a compound represented by formula (IV-2)). 15 parts by weight of the product name VDH) and 28 parts by weight of Aerosil200 from Degu, Germany, were added to a total amount of 100 g as a purified inorganic filler, and then a composition was uniformly mixed using a 3-roll mill at room temperature.

[Comparative Example 6-8]

75 parts by weight of the light and heat curable epoxy acrylate oligomer represented by General Formula (I) obtained in Synthesis Example 1, 3 parts by weight of the urethane oligomer type photocuring agent represented by General Formula (IV-1) obtained in Synthesis Example 12, and synthesis 17 parts by weight, 28 parts by weight and 38 parts by weight of Aerosil200, manufactured by Degusa, Germany, as an inorganic filler, was added to the mixture mixed with 22 parts by weight of the urethane oligomer-type latent heat curing agent represented by Formula (IV-2) obtained in Example 18. The parts were mixed and uniformly mixed using a 3-roll mill at room temperature as Comparative Examples 6, 7 and 8.

[Test Example]

[Preparation of liquid crystal sample]

As shown in Table 6 below, a light and heat curable liquid crystal display panel liquid crystal inlet encapsulant of the present invention (Example 1-8) and a compound thereof (General Formulas I, V, V-1, and V-2) and Comparative Examples A liquid crystal sample for evaluating liquid crystal reliability for evaluating the influence of the encapsulant of 1 to 5 on the liquid crystal was produced and prepared according to the following method.

0.1 g of each of the encapsulating agent and the compound to be evaluated were put in a 7 ml glass bottle, and then 1 g of uncontaminated pure liquid crystal was added and the glass bottle was sealed. After being left at room temperature for 1 hour in this state, UV curing was carried out at an irradiation dose of 3 J / cm ² having an intensity of at least 500 mW, and immediately followed by a thermal curing process in an oven at 120 ° C. for 1 hour. After that, the mixture was left to stand for 2 hours in an oven set at 200 ° C. for further contact with the encapsulant and the compound to be evaluated. Then, the glass bottle was opened, and only the liquid crystal part was taken out to obtain moisture for liquid crystal reliability evaluation. Store in a cool, dark, controlled condition below 50 RH%.

[Measurement of transition temperature of liquid crystal sample]

Small amounts (0.03 g) of each of the prepared liquid crystal samples were collected and the contamination was determined by measuring a transition temperature inherent in the liquid crystal using a polarizing microscope equipped with a hot-stage. The hot stage used has an accuracy of ± 0.1 ° C or higher. The hot stage used in the present invention used a model name FP90 manufactured by Mettler-Toledo, and the polarization microscope used Nikon's model name Optiphot-2 pol having a polarization angle of 0 ° to 270 °. JVC's CCD camera was used as the equipment to monitor the images. The image analysis program used for image observation was made using Media cybernetics Image Pro Plus v.1.2 and the magnification was fixed at 40 times.

The experimental slide glass was placed on the heating part of the hot stage, and the sample liquid crystal was dropped onto the observation part and fixed to cover glass without bubbles. Then, the start temperature was set at 25 ° C. and the end temperature was 100 ° C., and then the liquid crystal sample part was heated at a heating rate of 3 ° C./min. Through the observation of the liquid crystal phase of the polarization state during the heating process it was recorded that the point of phase transition from the anisotropy (1 in Figure 3) isotropic (3 in Figure 3) inherent in the thermotropic liquid crystal according to the temperature change. This reliability evaluation was performed both pure liquid crystals and the above-mentioned liquid crystal sample and repeated three times for each sample to obtain the average value is shown in Table 6 below. Non-pollution criteria of liquid crystals are based on the non-pollution range of ± 0.5 ° C with respect to the phase transition temperature of pure liquid crystals.

[Measurement of Contamination Level Using Gas Chromatography of Liquid Crystal Sample]

The contamination evaluation of each liquid crystal sample prepared above is determined using gas chromatography. Gas chromatography is referred to as "GC" unless stated otherwise. GC used M600D model applied to HP-1 type 50m column of Younglin Science, and compared with the characteristic peak of uncontaminated pure liquid crystal as compared with the transition temperature of liquid crystal. The presence or absence of an additive liquid crystal characteristic peak is observed. As in the example of measuring the transition temperature of the sample liquid crystal, repetitive results were obtained three times per sample to determine whether the liquid crystal was contaminated. The results are shown in Table 6 below. The non-contamination criterion of the liquid crystal is based on the non-contamination criterion that is not added to the GC analysis peak of the pure liquid crystal.

[Measurement of Contamination Level Using Measurement Method of Resistivity of Liquid Crystal Sample]

The liquid crystal contamination was evaluated by measuring the change in specific resistance of each liquid crystal sample prepared above. The specific resistance value of pure liquid crystal that is not contaminated with the equipment for measuring the specific resistance value of liquid crystal (Merck Korea Co., Toyo Corporation, model name SR-6517) is maintained at room temperature 24 ℃ ~ 25 ℃ and relative humidity 65RH% After the measurement under the humidity condition, the specific resistance value of the liquid crystal sample is measured under the same environmental conditions, and the change range of the two liquid crystals is determined based on whether the liquid crystal is contaminated. The evaluation standard uses non-contaminated liquid crystals as the standard for reducing the change in the range of two liquid crystals less than 10 ² units.The average value is derived by measuring three times in the same way for one liquid crystal sample to give reproducibility. It is shown in Table 6 below.

                         <Evaluation result of liquid crystal reliability> division POM GC Specific resistance ℃ Impurity Number ㎝ · cm Non-polluting pure liquid crystal 82 N / A 3.28 * 10E + 13 Example 1 (Synthesis Example 1 + 10 + 16) 78.4 4 1.69 * 10E + 11 Example 2 (Synthesis Example 2 + 11 + 17) 80.6 2 2.27 * 10E + 12 Example 3 (Synthesis Example 3 + 12 + 18) 81.8 0 2.19 * 10E + 13 Example 4 (Synthesis Example 4 + 13 + 19) 81.7 0 3.79 * 10E + 13 Example 5 (Synthesis Example 1 + 23) 78.8 4 7.13 * 10E + 09 Example 6 (Synthesis Example 2 + 24) 80.4 3 2.63 * 10E + 12 Example 7 (Synthesis Example 3 + 25) 81.6 0 4.81 * 10E + 13 Example 8 (Synthesis Example 4 + 26) 81.7 0 1.97 * 10E + 13 General formula I 81 One 2.35 * 10E + 11 General Formula V 81.4 0 3.15 * 10E + 13 General Formula V-1 81.5 0 6.10 * 10E + 13 General formula V-2 81.5 0 2.87 * 10E + 13 Comparative Example 1 (Synthesis Example 5 + 14 + 20) 81.5 0 5.13 * 10E + 13 Comparative Example 2 (Synthesis Example 6 + 15 + 21) 79.8 2 4.48 * 10E + 12 Comparative Example 3 (Synthesis Example 5 + 27) 81.7 0 3.92 * 10E + 13 Comparative Example 4 (Synthesis Example 5 + 28) 80.6 2 2.35 * 10E + 12 Comparative Example 5 77.8 6 7.11 * 10E + 10 Comparative Example 6 81.6 0 5.82 * 10E + 13 Comparative Example 7 81.6 0 3.36 * 10E + 13 Comparative Example 8 81.8 0 8.13 * 10E + 13

Adhesion Test

In order to evaluate the adhesive force of the encapsulant of Examples 1 to 8 and the encapsulant of Comparative Examples 1 to 5 according to the present invention to the glass substrate, the glass untreated surface having a specification of 0.7 mm thick, 3 cm wide and 7 cm long It was cross-bonded by dropping 0.01 g on the substrate as shown in FIG.

After cross-bonding the glass substrate, UV curing was carried out at a dose of 3 J / cm ² having a strength of at least 500mW and a thermal curing process in an oven at 120 ℃ for 1 hour to prepare a specimen for evaluation of adhesion.

Using the prepared specimens, as in the method of Figure 2, based on the cross-bond strength evaluation method to evaluate the adhesive force using a tensile tester of the United States Instron, and the results are shown in Table 7 below.

[Linear expansion coefficient test]

In order to evaluate the coefficient of linear expansion, prepared by using the encapsulant of Examples 1 to 8 and the encapsulant of Comparative Examples 1 to 5 according to the present invention to a cube having a height of 3mm in width and width, and then thermodynamic analysis by UV and heat curing Using a device (TMA, TA Instrument model name TA2960 / 2940), the high temperature linear expansion coefficient was evaluated while raising the temperature at a temperature increase rate of 10 ° C./min from -30 ° C. to 200 ° C. using a liquid nitrogen environment. Shown in

[Water resistance test]

In order to evaluate the water resistance of the encapsulant of Examples 1 to 8 and the encapsulant of Comparative Examples 1 to 5 according to the present invention, the films were molded in the following manners, respectively.

After coating the encapsulant using a bar coater on a Teflon-coated flat glass, and using a UV curing machine to form a cured film at an irradiation dose of 3.0 J / cm ² with a strength of at least 500mW, 120 It was placed in an oven at 0 ℃ heat curing for 1 hour to prepare a "sample film" of a thickness of 0.1mm.

Take the sample film in the size of 100mm × 100mm, respectively, and measure the weight (A), soak it in distilled water for 25 hours and store it for 72 hours. Was measured and dried for 1 week at room temperature and humidity to measure the weight (C). Finally, the weight change rate and extraction rate were calculated using the following equations and are shown in Table 7 below.

               % Change in weight = (B-A) / A × 100

               % Extraction = (A-C) / A × 100

[Hardness Test]

In order to determine the degree of cure, the encapsulant of Examples 1 to 8 and the encapsulant of Comparative Examples 1 to 5 according to the present invention were coated on a flat glass with a Teflon coating using a bar coater, and then UV Using a curing machine to form a cured film at a dose of 3.0 J / cm ² with a minimum strength of 500mW, and then placed in a 120 ℃ oven heat-cured for 1 hour to prepare a "sample film" of a thickness of 1mm.

After measuring the initial weight (Wo) of each sample film, the mixture was extracted in a soxhlet extraction flask for 24 hours using methyl ethyl ketone as a solvent, and then the residue was dried at 50 ° C. for 72 hours and reweighed (W1). ) And the gel fraction (hardening degree) was calculated by the following equation.

Gel fraction (hardness) (%) = W ₁ / W _o × 100

[Water vapor transmission test]

For the encapsulant of Examples 1 to 8 and the encapsulant of Comparative Examples 1 to 5 according to the present invention using the equipment as shown in Figure 4 in accordance with KS M 6882 under light conditions of 65 ℃, 95% relative humidity for 24 hours And the moisture permeability after heat curing. At this time, high density polyethylene wax was used as the sealing material. Using the cured liquid crystal injection hole encapsulation oligomer composition, the moisture permeability was calculated using the weight ratio of calcium chloride before moisture permeability evaluation and the weight after moisture permeability evaluation.

                            <Property Evaluation Results> division Adhesive force (kgf / ㎠) Coefficient of linear expansion (cm / cm ℃) Water resistance (%) Moisture permeability (g / cm3 * 24hrs) Hardness (%) Example 1 46 36.3 * 10E-4 4.41 29.81 99.21 Example 2 54 22.8 * 10E-5 2.38 30.66 99.22 Example 3 55 36.1 * 10E-5 3.15 28.45 <99.95 Example 4 53 19.8 * 10E-5 3.07 27.66 <99.95 Example 5 44 54.7 * 10E-4 4.98 35.74 99.08 Example 6 50 35.9 * 10E-5 2.37 28.11 <99.95 Example 7 55 40.3 * 10E-3 3.55 30.94 <99.95 Example 8 54 18.3 * 10E-5 3.09 27.35 <99.95 Comparative Example 1 57 38.8 * 10E-5 2.96 27.47 <99.95 Comparative Example 2 46 27.4 * 10E-4 5.35 33.62 99.47 Comparative Example 3 52 41.8 * 10E-5 3.17 23.61 <99.95 Comparative Example 4 54 36.4 * 10E-5 3.3 27.48 <99.95 Comparative Example 5 48 44.9 * 10E-4 7.88 32.76 98.94 Comparative Example 6 49 41.8 * 10E-3 3.45 27.93 <99.95 Comparative Example 7 54 36.4 * 10E-5 3.08 26.29 <99.95 Comparative Example 8 57 44.9 * 10E-5 2.97 28.27 <99.95

As can be seen from the results shown in Table 7, the composition developed in the present invention has excellent adhesion when used for bonding the liquid crystal panel, can reduce the influence on the orientation and electrical properties of the liquid crystal, and excellent water resistance and moisture permeability An anxiety that can cause liquid crystal alignment defects of liquid crystal panel products because it has a very high gel fraction (hardening degree) of 99.9% or more, and there is no possibility of unreacted monomers or other compositions desorb into the liquid crystal panel after UV and thermal reactions. Factors can be drastically reduced.

In addition, considering the linear expansion rate up to 200 ℃, it shows the numerical range that can sufficiently maintain the cell gap uniformity of the liquid crystal panel according to the temperature change, which can improve the reliability of the liquid crystal panel products according to the temperature change. There is this. For a more fundamental evaluation result, the liquid crystal phase transition temperature, the GC, and the liquid crystal specific resistance of the liquid crystal reliability of the composition developed in the present invention were measured, respectively. As shown in Table 6, the transition temperature and the specific resistance of the liquid crystal were It showed excellent property preservation on the same level as the characteristic evaluation result of the pure liquid crystals uncontaminated, and it can be confirmed through GC results that no foreign matters were lost to the liquid crystals. As described above, the TFT adhesive panel encapsulation sealant composition of the present invention is not only excellent in adhesive strength compared to existing products, but also excellent in moisture resistance and moisture permeability of the cured sealant and excellent in dimensional stability due to changes in external temperature. The product reliability can be further improved, and the non-pollution reliability of the liquid crystal before and after curing is very excellent, and thus it is very suitable for application to a high reliability liquid crystal panel sealing bonding sealant.

Claims (14)

(1) a light and heat curable epoxy acrylate oligomer represented by the following general formula (I), (2) addition of urethane oligomer type photocuring agent and urethane oligomer type latent heat curing agent represented by the following general formula (V) Epoxy acrylate and (3) An optical and thermosetting liquid crystal display panel liquid crystal inlet encapsulant comprising an inorganic additive. <Formula (Ⅰ)>

(In General Formula (I), F represents a hydrogen, a hydroxyl group or a methyl group, R ₁ , R ₂ represents a hydrogen or a methyl group, and R ₃ represents a glycidyl ether or di glycidyl ether functional group.) <Formula (V)>

(In formula (V), R ₁ , R ₂ are hydrogen, hydroxyl group or methyl group, R ₄ is di- or tri-isocyanate compound, R ₅ is hydroxyl group-containing photocuring agent, R ₆ is latent thermal curing agent. Indicates.) The photo- and heat-curable epoxy acrylate oligomer represented by the general formula (I) has a molecular weight of 500 grams per mole (g / mol) to 3000 grams per mole (g / mol). Addition of urethane oligomer type photocuring agent and urethane oligomer type latent thermal curing agent represented by (V) Epoxy acrylate is a light and heat curable liquid crystal display panel liquid crystal inlet encapsulant, characterized in that the molecular weight of 500 grams per mol (g / mol) to 3500 grams per mol (g / mol). The light and heat curable epoxy acrylate oligomer represented by the general formula (I) is 40 to 65 parts by weight, the urethane oligomer type photocuring agent and the urethane oligomer type represented by the general formula (V) Latent thermal curing agent addition 10 to 30 parts by weight of epoxy acrylate and 15 to 45 parts by weight of an inorganic additive is contained, the light and heat curable liquid crystal display panel liquid crystal inlet encapsulant. The method of claim 1, wherein the inorganic additive is one or a mixture of two or more selected from synthetic silica, calcium carbonate, talc, silica, spherical silica, silane coupling agent-modified silica, alumina silicate, whisker, zeolite and 50 nanometers. (nm) to 5 micron (μm) particles of the light and heat curable liquid crystal display panel liquid crystal inlet encapsulant. The light and heat curable liquid crystal display panel liquid crystal inlet encapsulant according to any one of claims 1 to 4, wherein the encapsulant contains a curing catalyst. 6. The liquid crystal inlet of claim 5, wherein the curing catalyst is a thermosetting catalyst having an alicyclic bis dimethyl urea structure as a compound containing an amine functional group. Encapsulant. 7. The liquid crystal inlet encapsulant of claim 6, wherein the curing catalyst is contained in an amount of 15 parts by weight to 45 parts by weight. (1) a light and heat curable epoxy acrylate oligomer represented by the general formula (I), (2) urethane oligomer-type light curing agent addition epoxy acrylate represented by the following general formula (V-1), (3) a urethane oligomer-type latent heat curing agent addition epoxy acrylate represented by the following general formula (V-2), and (4) An optical and thermosetting liquid crystal display panel liquid crystal inlet encapsulant comprising an inorganic additive. <Formula (V-1)>

(In said general formula (V-1), R <_1> , R <_2> represents a hydrogen, a hydroxyl group, or a methyl group, R <_4> represents a di- or tri-isocyanate compound, and R <_5> represents a hydroxyl group containing photocuring agent.) <Formula (V-2)>

(In said general formula (V-2), R <_1> , R <_2> represents a hydrogen, a hydroxyl group, or a methyl group, R <_4> represents a di- or triisocyanate compound, and R <_6> represents a latent thermosetting agent.) The photo- and heat-curable epoxy acrylate oligomer represented by the general formula (I) has a molecular weight of 500 grams per mole (g / mol) to 3000 grams per mole (g / mol). The urethane oligomer-type curing agent addition epoxy acrylate represented by (V-1) has a molecular weight of 500 grams per mole (g / mol) to 2000 grams per mole (g / mol), and is represented by the general formula (V-2). The urethane oligomer-type latent thermal curing agent-added epoxy acrylate represented is a light and heat curable liquid crystal display panel liquid crystal inlet bag, characterized in that the molecular weight is 500 grams per mole (g / mol) to 3500 grams per mole (g / mol). My. 9. The light and heat curable epoxy acrylate represented by the general formula (I) is 40 parts by weight to 65 parts by weight of the oligomer, and the urethane oligomer type photocuring agent addition epoxy represented by the general formula (V-1). 1 to 10 parts by weight of acrylate, the urethane oligomer type latent heat curing agent addition epoxy acrylate represented by the general formula (V-2) 10 to 30 parts by weight, 15 to 45 parts by weight of the inorganic additive is contained light- and heat-curable liquid crystal display panel liquid crystal inlet encapsulant. The method according to claim 8, wherein the inorganic additive is one or a mixture of two or more selected from synthetic silica, calcium carbonate, talc, silica, spherical silica, silane coupling agent-modified silica, alumina silicate, whisker, zeolite and 50 nanometers. (nm) to 5 micron (μm) particles of the light and heat curable liquid crystal display panel liquid crystal inlet encapsulant. The liquid crystal inlet encapsulant according to any one of claims 8 to 11, wherein the encapsulant contains a thermosetting catalyst. 13. The liquid crystal inlet of claim 12, wherein the curing catalyst is a thermosetting catalyst having an alicyclic bis dimethyl urea structure as a compound containing an amine functional group. Encapsulant. The liquid crystal inlet encapsulant of claim 13, wherein the curing catalyst is contained in an amount of 15 parts by weight to 45 parts by weight.

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