KR101033827B1 - Curable resin composition, flat panel display having cured product from the same and method of manufacturing flat panel display - Google Patents

Abstract

Disclosed are a curable resin composition, a flat panel display including a cured product of the curable resin composition, and a method of manufacturing a flat panel display. Curable resin composition is 100 parts by weight of curable resin; 1 to 25 parts by weight of a urethane (meth) acrylate compound; 1 to 10 parts by weight of the photopolymerizable initiator; And 1 to 10 parts by weight of a thermosetting agent.

Description

Curable resin composition, flat panel display device including cured product of curable resin composition, and method for manufacturing flat panel display device {CURABLE RESIN COMPOSITION, FLAT PANEL DISPLAY HAVING CURED PRODUCT FROM THE SAME AND METHOD OF MANUFACTURING FLAT PANEL DISPLAY}

The present invention relates to the manufacture of a flat panel display device comprising a curable resin composition and a cured product of the curable resin composition.

A liquid crystal display (LCD), which is a type of flat panel display (FPD), includes two substrates and a liquid crystal layer interposed between the two substrates. In order to interpose the liquid crystal layer between the two substrates, the curable resin composition is added to the edge of any one of the two substrates, and the liquid crystal is dropped on the one of the substrates, and then the two substrates are removed. After bonding, the curable resin composition must be cured to form a sealant cured product. However, since the curable resin composition or the sealant cured product is in direct contact with the liquid crystal during or after the curing process, the curing process should be performed quickly, and the curable resin composition or sealant cured product may not be eluted into the liquid crystal. Should be. In addition, the sealant cured product needs to have a strong adhesive strength in order to improve the reliability of the liquid crystal display device against external force. In addition, in order to improve process productivity, the storage stability of the curable resin composition and the linearity of the cured cured product should be excellent.

The present invention provides a curable resin composition capable of quickly curing the curable resin composition while minimizing the dissolution of the curable resin composition or the cured product thereof during or after the curing process, and a flat panel display including the cured product of the curable resin composition. Provided is a method of manufacturing a flat panel display device using the curable resin composition.

The present invention provides a curable resin composition capable of improving the storage stability of the curable resin composition and the adhesive strength of the cured product, a flat panel display device comprising a cured product of the curable resin composition, and a method of manufacturing a flat panel display device using the curable resin composition. To provide.

The present invention provides a curable resin composition in which a cured product can have high elasticity, a flat panel display device containing a cured product of the curable resin composition, and a method of manufacturing a flat panel display device using the curable resin composition.

This invention provides the curable resin composition which can improve the linearity of hardened | cured material, the flat panel display containing the hardened | cured material of this curable resin composition, and the manufacturing method of the flat panel display apparatus using this curable resin composition.

Curable resin composition according to an aspect of the present invention 100 parts by weight of curable resin; 1 to 25 parts by weight of a urethane (meth) acrylate compound; 1 to 10 parts by weight of the photopolymerizable initiator; And 1 to 10 parts by weight of a thermosetting agent.

Here, the curable resin composition according to an aspect of the present invention is 1 to 7 parts by weight of the silane coupling agent; And 0.02 to 7 parts by weight of a thixotropic modifier. In addition to this, the curable resin composition according to an aspect of the present invention may further include 10 to 40 parts by weight of the filler.

Here, the curable resin may include at least one functional group selected from an acrylic group, a methacryl group and an epoxy group.

Here, the curable resin may be a partial (meth) acrylate epoxy resin. The partial (meth) acrylate epoxy resin can be obtained through the reaction of a compound having a (meth) acryl group and a compound having an epoxy group.

Here, the urethane (meth) acrylate compound may be represented by the following formula (1).

이되, n은 1 내지 10의 정수이고, R₃은 수소원자 또는 메틸기이고, m은 1 내지 5의 정수이다.In Chemical Formula 1, R ₁ is an aromatic compound, an aliphatic compound, or an aliphatic cyclic compound, and R ₂ is

N is an integer of 1 to 10, R ₃ is a hydrogen atom or a methyl group, and m is an integer of 1 to 5.

The urethane (meth) acrylate compound represented by Formula 1 may be obtained through a urethane reaction using an isocyanate compound as a raw material.

Meanwhile, the flat panel display device according to an aspect of the present invention includes a sealant cured product, and the sealant cured product may be obtained by curing the curable resin composition.

On the other hand, a flat panel display device according to an aspect of the present invention includes a sealant cured product, the sealant cured product is a step of applying the curable resin composition on a substrate; Irradiating light on the curable resin composition such that the applied curable resin composition is photocured; And applying heat to the curable resin composition such that the curable resin composition to which the light is irradiated is thermoset.

According to the present invention, the curable resin composition can be quickly cured, and elution of the curable resin composition or the cured product thereof can be minimized during or after the curing process. In addition, the storage stability of the curable resin composition and the adhesive strength of the cured product can be improved. The cured product may have a high elasticity. For this reason, even if a large external force is applied to the cured product, not only the elastic force of the cured product but also the flexibility may be secured, thereby minimizing the occurrence of cracks and foreign substances. In addition, since the linearity of the cured product may be improved, the cured product may be formed in a desired pattern, and process variation may be minimized. Thereby, process productivity of the flat panel display device containing the sealant hardened | cured material obtained by hardening of the said curable resin composition can be improved.

EMBODIMENT OF THE INVENTION Hereinafter, the curable resin composition which concerns on one aspect of this invention, the flat panel display device containing the hardened | cured material of this curable resin composition, and the manufacturing method of the flat panel display device using this curable resin composition are demonstrated in detail.

Curable resin composition according to an aspect of the present invention comprises a curable resin, a urethane (meth) acrylate compound, a photopolymerizable initiator and a thermosetting agent. In addition, the curable resin composition according to an aspect of the present invention may further include other additives within the range of not lowering its properties as necessary. Hereinafter, each component of the said curable resin composition is demonstrated in detail.

<Curable resin>

As the curable resin, both thermosetting and photocuring may be used, and the curable resin is not particularly limited. For example, a curable resin containing at least one functional group selected from an acryl group, a methacryl group and an epoxy group can be used.

A partial (meth) acrylate epoxy resin is mentioned as an example of such curable resin. The partial (meth) acrylate epoxy resin can be obtained through the reaction of a compound having a (meth) acryl group and a compound having an epoxy group. For example, it can be obtained by reacting (meth) acrylic acid and an epoxy resin in the presence of a basic catalyst. The compound having the (meth) acryl group used as a raw material for synthesizing the partial (meth) acrylate epoxy resin may further have an epoxy group, and the compound having the epoxy group may further have a (meth) acryl group. .

Examples of the partial (meth) acrylate epoxy resins include noblock type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, trisphenol methane type epoxy resins, bisphenol type epoxy resins, and the like. Can be used in combination.

The viscosity of the partial (meth) acrylate epoxy resin may be 70,000 to 200,000 cps. When the viscosity is less than 70,000 cps, there is a problem in that the storage stability of the curable resin composition is inferior, and when the viscosity is more than 200,000 cps, the storage stability of the curable resin composition may decrease and gelation may occur.

<Urethane (meth) acrylate compound>

Although it does not specifically limit as said urethane (meth) acrylate compound, For example, what is obtained through the urethane reaction which uses an isocyanate type compound as a raw material can be used. Here, the isocyanate compound is a generic term for a monoisocyanate compound, a diisocyanate compound, a triisocyanate compound, a polyisocyanate compound, or a modified product thereof, and in the present invention, these may be used alone or in combination of two or more thereof.

The urethane (meth) acrylate compound, for example, may be represented by the following formula (1).

[Formula 1]

이되, n은 1 내지 10의 정수이고, R₃은 수소원자 또는 메틸기이고, m은 1 내지 5의 정수이다.In Chemical Formula 1, R ₁ is an aromatic compound, an aliphatic compound, or an aliphatic cyclic compound, and R ₂ is

N is an integer of 1 to 10, R ₃ is a hydrogen atom or a methyl group, and m is an integer of 1 to 5.

The aromatic compounds that may be selected as the above R ₁ include, but are not particularly limited, and for example, can be used aromatic compounds of C ₆ -C _30. In addition, the aliphatic compound which may be selected as R ₁ is not particularly limited, but for example, an aliphatic compound of C ₁ -C ₃₀ may be used. In addition, the aliphatic cyclic compound which may be selected as R ₁ is not particularly limited, but for example, an aliphatic cyclic compound of C ₃ -C ₂₀ may be used.

 Meanwhile, examples of commercialized urethane (meth) acrylate compounds include EBECRYL 210, EBECRYL 220, EBECRYL 230, EBECRYL 244, EBECRYL 245, EBECRYL 264, EBECRYL 265, EBECRYL 270, EBECRYL 280, and EBECRYL 284 manufactured by Cytec. , EBECRYL 285, EBECRYL 294, EBECRYL 1290, EBECRYL 2002, EBECRYL 2003, EBECRYL 4820, EBECRYL 5129, EBECRYL 6202, EBECRYL 8402, etc., manufactured by Miwon Corp. , MIRAMER PU280, MIRAMER PU310, MIRAMER PU320, MIRAMER PU321, MIRAMER PU330, MIRAMER PU340, MIRAMER PU350, MIRAMER PU370, MIRAMER PU372, MIRAMER PU460, MIRAMER PU610, MIRAMER PU620, MIRAMER PU640, MIRAMER PU664 and the like. In addition, aliphatic urethane acrylates manufactured by SARTOMER include CN9002, CN9004, CN9005, CN9006, CN9007, CN9178, CN9290US, CN940, CN9788, CN989, CN9893, CN996, CN9009, CN9010, CN3211, CN9001, CN2920 , CN3102, CN959, CN9011, CN929, CN945B85, CN945A60, CN962, CN964, CN965, CN991, CN980, CN981, CN968, CN983, CN984, CN9019, CN2921, CN2922, CN9008, CN9013, CN9018, CN966B85, etc. Examples of the acrylates include CN3101, CN2901, CN2902, CN9167US, CN9782, CN9783, CN992, CN994, CN999, CN997, CN3210, CN2600, CN975, CN978, CN972, and the like. The commercialized urethane (meth) acrylate compounds may be used alone or in combination of two or more thereof.

By the addition of the urethane (meth) acrylate compound, the curable resin composition according to an aspect of the present invention may not only be hardened quickly but the cured product may have a strong adhesive force. In addition, the cured product may have a high elasticity by the urethane series. For this reason, the hardened | cured material may be easily cracked or a foreign material does not generate | occur | produce, even by a large external force.

The content of the urethane (meth) acrylate compound may be 1 to 25 parts by weight based on 100 parts by weight of the curable resin. When the content of the urethane (meth) acrylate compound is less than 1 part by weight based on 100 parts by weight of the curable resin, it may not express the required improvement properties and may act as an impurity, and when it exceeds 25 parts by weight, it does not participate in the reaction. Excess compounds may act as impurities, for example, liquid crystal contamination.

<Photoinitiator>

The photopolymerization initiator may be any one that initiates radical polymerization, but is not particularly limited. Examples thereof include benzoin-based compounds, acetophenones, benzophenones, thioxanthones, anthraquinones, and α-acyl oxime esters. , Phenylglyoxylates, benzyls, azo compounds, thiphenylsulfide compounds, acylphosphineoxy compounds, organic pigment compounds, iron-phthalocyanine compounds and the like can be used alone or in combination of two or more thereof. have. For example, benzophenone, 2,2-diethoxyacetophenone, benzyl, benzoylisopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, thioxanthone, etc. may be used alone or as the photopolymerization initiator. The above combination can be used.

The content of the photopolymerization initiator may be 1 to 10 parts by weight based on 100 parts by weight of the curable resin. If the content of the photopolymerization initiator is less than 1 part by weight with respect to 100 parts by weight of the curable resin, there is a problem that the photocuring of the curable resin composition does not occur sufficiently. If the content of the photopolymerization initiator exceeds 10 parts by weight, the unreacted photopolymerization initiator may act as an impurity.

<Thermosetting agent>

The thermosetting agent is not particularly limited, but for example, a latent thermosetting agent may be used in which curing occurs at a high temperature, for example, 120 ° C. or higher, instead of curing at a low temperature.

Examples of the latent thermosetting agent include imidazole type, dihydrazide type, amine type and the like. Examples of the imidazole type thermosetting agent include 2-methylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, P-0505 (manufactured by Shikoku Corporation), and the like. Examples of the dihydrazide type thermosetting agent include amcure VDH, amcure UDH (manufactured by Ajinomoto Co., Ltd.), ADH, SDH, DDH, IDH (manufactured by Otsuka Chemical Co., Ltd.), NDH (manufactured by Nippon Hydrazine Industry Co., Ltd.), and the like. Examples of the amine type thermosetting agent include amcure PN-23, amcure PN-H, amcure PN-31, amcure PN-40, amcure PN-23J, amcure PN-31J, amcure PN-40J, amcure MY-24, Amicure MY-H, Amicure MY-HK-1, Amicure AH-203, Amicure AH-300, Amicure AH-154, Amicure AH-163 (manufactured by Ajinomoto Co., Ltd.). These may be used alone or in combination of two or more thereof. Among them, it is preferable to use a dihydrazide type thermosetting agent from the viewpoint of storage stability, liquid crystal contamination, and adhesion improvement.

The content of the thermosetting agent may be 1 to 10 parts by weight based on 100 parts by weight of the curable resin. If the content of the thermosetting agent is less than 1 part by weight based on 100 parts by weight of the curable resin, there is a problem that the thermosetting of the curable resin composition does not sufficiently occur. If the content of the thermosetting agent exceeds 10 parts by weight, the unreacted thermosetting agent may act as an impurity. .

<Other additives>

The other additives include silane coupling agents, thixotropic agents, fillers, photoinitiators, leveling agents, viscosity modifiers, surfactants, plasticizers, ultraviolet absorbers, etc., which may be used alone or in combination of two or more thereof. Can be used.

Among them, the silane coupling agent is not particularly limited as used for improving the adhesive strength of the cured product, but for example, a vinyl group-containing silane compound, an amino group-containing silane compound, a (meth) acryloxy group-containing silane compound, an epoxy group A containing silane compound, a mercapto group containing silane compound, etc. can be used individually or in combination of 2 or more types.

Examples of the vinyl group-containing silane compound include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and the like. Examples of the amino group-containing silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -(2-aminoethyl) aminopropylmethyldimethoxysilane, etc. are mentioned. Examples of the (meth) acryloxy group-containing silane compound include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropyl Methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, etc. are mentioned. Examples of the epoxy group-containing silane compound include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. . Examples of the mercapto group-containing silane compound include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and the like.

The content of the silane coupling agent may be 1 to 7 parts by weight based on 100 parts by weight of the curable resin. If the content of the silane coupling agent is less than 1 part by weight with respect to 100 parts by weight of the curable resin, the effect is insignificant, and if it exceeds 7 parts by weight, there is a problem in that storage stability and coating property of the curable resin composition are inferior.

The thixotropic modifier is not particularly limited, but for example, methyl cellulose, methyl ethyl ketone peroxide, polyethylene oxide wax, modified polypropylene emulsion, polyamide wax, organo clay, alkyl sulfate, hydroxyl ethyl cellulose, Hydroxyl esters, polyvinyl alcohols, polydimethyl siloxanes, unsaturated carboxylic acid monomers, hydroxide carboxylic acid amides, ethylene glycol, diethylene glycol, alkaline earth metal hydroxides, alkaline earth metal carbonates, etc. It can be used in combination of two or more kinds. In addition, inorganic particles having an average particle size of 100 nm or less can be used as the thixotropic regulator. For example, a small amount of fine silica, zeolite, alumina, aluminum stearate, alumina hydroxide, mica, bentonite, and the like may be used as the thixotropic regulator.

The thixotropic regulator may be present in an amount of 0.02 to 7 parts by weight based on 100 parts by weight of the curable resin. When the content of the thixotropic regulator is less than 0.02 parts by weight based on 100 parts by weight of the curable resin, not only the thixotropic effect is insignificant but the straightness of the cured product may be degraded. When the content of the thixotropic agent is greater than 7 parts by weight, the viscosity control of the curable resin composition There is a problem that this is not easy.

As the filler, an inorganic filler and / or an organic filler may be used.

Examples of the inorganic fillers include 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 White earth, bentonite, aluminum nitride, silicon nitride, potassium titanate, zeolite, calcia, magnesia, ferrite, and the like. These may be used alone or in combination of two or more thereof.

The particle size of the inorganic filler is preferably even, and the particle size may vary depending on the type of the flat panel display. For example, when applying curable resin composition to a liquid crystal display device, it is preferable that the maximum particle size of a filler is 5 micrometers or less. This is because when the maximum particle size of the filler exceeds 5 μm, it is difficult to maintain a cell gap of the liquid crystal display. More preferably, an inorganic filler is one having a uniform particle size and an average particle diameter of 2 μm or less.

As an example of the said organic filler, the material which copolymerized methyl methacrylate, polystyrene, and the monomer copolymerizable with this is mentioned.

The content of the filler may be 10 to 40 parts by weight based on 100 parts by weight of the curable resin. If the content of the filler is less than 10 parts by weight based on 100 parts by weight of the curable resin, the effect is insignificant, and if it exceeds 40 parts by weight, there is a problem that the viscosity of the curable resin composition is increased.

Meanwhile, the flat panel display device according to the present invention includes a sealant cured product in an edge region of the flat panel display device. The sealant cured product may be obtained by curing the curable resin composition described above. Although the present invention is not limited by the type of the flat panel display, for example, it may be any one of a liquid crystal display, a plasma display panel (PDP), and an organic light emitting display (OLED).

In order to manufacture the flat panel display device including the sealant cured product, first, the curable resin composition is coated on a substrate, and the curable resin composition is irradiated with light so that the applied curable resin composition is photocured. Heat can be applied to the curable resin composition so that the irradiated curable resin composition is thermoset. As such, the sealant cured product may be formed through photocuring and thermosetting of the curable resin composition.

Here, as a coating method of the said curable resin composition, it can select arbitrarily from the spin coating method, the sol-gel method, the dip coating method, the casting method, the printing method, the spray method, etc., for example. In addition, since the coating thickness changes with the required conditions, this invention is not limited by this. In addition, since the light source, light irradiation amount, light irradiation time, thermosetting temperature, time, etc. of the said light irradiation vary with the specification of the said curable resin composition, its component ratio, etc., this invention is not limited by this.

As mentioned above, although forming the sealant hardened | cured material of a flat panel display device using the said curable resin composition was demonstrated as an example, the use of the curable resin composition which concerns on this invention is not limited to this. That is, the curable resin composition according to the present invention is applicable to all fields in which the existing curable resin composition can be used.

According to the above, the curable resin composition of the present invention can be cured quickly, and can minimize the dissolution of the curable resin composition or its cured product during or after the curing process. In addition, the storage stability of the curable resin composition and the adhesive strength of the cured product can be improved. In addition, it is possible not only to improve the straightness of the cured product but also to produce a cured product having high elasticity.

Hereinafter, the present invention will be described in detail through the following Synthesis Examples, Examples and Test Examples, but the present invention is not limited thereto.

[Synthesis Example]

Synthesis Example Synthesis of Partial (meth) acrylate Epoxy Resin

700 g of liquid bisphenol A diglycidyl epoxy resin (KER 828, manufactured by Kumho Pienbi Co., Ltd.) and a catalyst were charged with 1 g of triethylamine and 2 g of 4-methoxy phenol, and the temperature was raised to 80 ° C while stirring. Thereafter, 200 g of acrylic acid was added dropwise, and the mixture was stirred under reflux for 5 hours. Thereafter, toluene and 1% oxalic acid were added to the obtained partial epoxy acrylate resin, followed by stirring to remove ions, thereby obtaining a partial (meth) acrylate epoxy resin. The synthesized partial (meth) acrylate epoxy resin was measured by GPC. As a result, 46% of the diacrylate resin in which the epoxy group was ring-opened by acrylic acid and the epoxy group was completely acrylated was contained. 45% was included and 9% of unreacted epoxy resin was included.

[Example]

&Lt; Example 1 >

60 g of partial (meth) acrylate epoxy resin synthesized in the above synthesis example, 5 g of ADH (Adipic Dehydrazide) of dihydrazide series of Ajinomoto as a latent thermosetting agent, 2 g of Darocur TPO from Ciba as a photopolymerization initiator, urethane (meta ) 3 g of EBECRYL 5129 (Aromatic hexafuntional urethane acrylate, molecular weight 800) which is an aromatic urethane compound of Cytec as a acrylate compound, 2 g of KBM-403 (3-glycidoxypropyl trimethoxysilane) of Shin-Etsu Corp. as a silane coupling agent, 25 g of spherical silica (SO-E1) manufactured by Adomatec Co., Ltd. as an inorganic filler, and 1 g of hydroxyl ethyl cellulose as a thixotropic modifier were mixed, followed by primary mixing through a premixing process. Thereafter, milling was sufficiently performed with a 3-roll mill, and after the filter step, vacuum defoaming treatment was performed with a rotating revolving deaerator to obtain a curable resin composition.

<Example 2>

A curable resin composition was obtained in the same manner as in Example 1 except that 10 g of EBECRYL 5129 manufactured by Sectec was used as the urethane (meth) acrylate compound.

<Example 3>

A curable resin composition was obtained in the same manner as in Example 1, except that 15 g of EBECRYL 5129, manufactured by Sectec, was used as the urethane (meth) acrylate compound.

<Example 4>

A curable resin composition was obtained through the same procedure as in Example 1, except that 20 g of EBECRYL 5129, manufactured by Sectec, was used as the urethane (meth) acrylate compound.

Example 5

A curable resin composition was obtained in the same manner as in Example 1, except that CN9004 (Difuntional aliphatic urethane acrylate oligomer), an aliphatic urethane compound manufactured by Sartomer, was used alone as a urethane (meth) acrylate compound.

<Example 6>

Except that the aromatic urethane and aliphatic urethane compounds, that is, two compounds, were used as the urethane (meth) acrylate compounds, and the ratio of the aromatic urethane and aliphatic urethane compounds was 20:80. The curable resin composition was obtained through the same process. At this time, the total amount of the urethane (meth) acrylate compound was the same as in Example 1, and the aliphatic urethane acrylate compound used was CN9004 manufactured by Satomer, and the aromatic urethane acrylate compound was Miramer PU640 (Hexafunctional aromatic urethane acrylate) manufactured by Miwon Corporation. It was.

<Example 7>

A curable resin composition was obtained in the same manner as in Example 6 except that the ratio of the aromatic urethane and aliphatic urethane compounds was 50:50.

<Example 8>

A curable resin composition was obtained in the same manner as in Example 6 except that the ratio of the aromatic urethane compound and the aliphatic urethane compound was 80:20.

Example 9

A curable resin composition was obtained in the same manner as in Example 6, except that Miramer PU640, which was manufactured by Miwon Corporation, was used alone as a urethane (meth) acrylate compound.

Comparative Example 1

A curable resin composition was obtained in the same manner as in Example 1, except that the urethane (meth) acrylate compound was not used.

Comparative Example 2

A curable resin composition was obtained in the same manner as in Example 1, except that 0.5 g of EBECRYL 5129 manufactured by Sectec was used as the urethane (meth) acrylate compound.

Comparative Example 3

A curable resin composition was obtained through the same procedure as in Example 1 except that 30 g of EBECRYL 5129, manufactured by Sectec, was used as the urethane (meth) acrylate compound.

The physical properties of the curable resin compositions prepared through Examples 1 to 9 and Comparative Examples 1 to 3 were evaluated as in the following Test Examples, and the results are shown in Table 1 below.

Test Example 1 Measurement of Heat Curing Time

Differential Scanning Calorie (DSC) was used to measure the thermal curing time for each curable resin composition. At this time, the thermosetting time was defined as the time when the hardening degree of each curable resin composition becomes 95% or more.

Test Example 2 Adhesion Measurement

After applying each curable resin composition to the center part of the cleaned ITO glass substrate (manufacturer: Samsung Corning Fine Glass), the same ITO glass substrate was superimposed on it. Thereafter, UV curing (2000mJ / cm 2) was performed, and thermal curing (120 ° C., 40 min) was performed to prepare respective specimens for measuring adhesion. Adhesive strength was measured for each specimen prepared using a tensile strength meter (Tinius Olsen), and the adhesive strength per unit area was determined based on the following criteria.

◎: 1.5N / cm 2 or more

○: 1.0 N / cm 2 or more but less than 1.5 N / cm 2

Δ: 0.5 N / cm 2 or more but less than 1.0 N / cm 2

×: less than 0.5N / cm 2

<Test Example 3> Measurement of viscosity stability (Pot Life)

A small amount of 25 g of each curable resin composition was distributed to each vial, which was then left at room temperature to measure the change in viscosity from 1 day to 7 days. The viscometer used was Brookfield's RVDV II + pro, and the measurement conditions were 25 ° C., spindle # 29 and spindle speed 1.0 rpm. The viscosity change rate after 7 days was converted into the viscosity change rate after the initial viscosity and 7 days of aging, and the value divided by the conversion date was calculated as the daily average viscosity increase rate.

Test Example 4 Line Uniformity

Each curable resin composition was applied onto the ITO glass substrate using a sealant coating equipment, and then temporarily cured using UV (2000 mJ / cm 2) and pressure using a bonding machine. At this time, the sealant coating equipment was used Shotmaster 300S manufactured by Musashi, the diameter of the dispensing nozzle was 250㎛, discharge pressure was 100KPa. After the temporary curing, heat curing was performed at 120 ° C. for 40 minutes to form a sealant cured product. The width of the sealant cured product was approximately 1.5 mm. Subsequently, the linearity index was calculated using Equation 1 below, and linearity was determined based on the following criteria using the following linearity index.

◎: linearity index is within 1%

○: linearity index is within 2%

△: linearity index is within 3%

×: linearity index is 3% or more

In Equation 1, D denotes an average width value of the cured product of the sealant, as shown in FIG. 1, and d represents a bumpy degree of the sealant cured product, minus the minimum width value of the sealant cured product. It means the value.

<Test Example 5> Liquid crystal contamination

After putting 1g of each curable resin composition into the ampoule bottle, 1g of liquid crystals (made by Merck, TN, and VA mode) were put into the said ampoule bottle, and it was left to stand for 1 hour. Then, UV curing (2000mJ / ㎠) was carried out, and thermal curing (120 ℃, 20 minutes) was carried out. Thereafter, the Tni of the blank liquid crystal was measured at a rate of 10 ° C./min using a DSC, and the Tni of the liquid crystal in each sample of the thermosetting was measured. Since the smaller the difference between the measured Tni (80.8 ° C.) of the blank liquid crystal and the Tni of the liquid crystal in the thermosetting sample is smaller, the liquid crystal contamination is less, so that the liquid crystal contamination was determined based on the following criteria.

(Double-circle): Tni deviation is less than 0.5 degreeC

(Circle): Tni deviation is 0.5 or more and less than 1.0 degreeC

(Triangle | delta): Tni deviation is 1.0 or more and less than 2.0 degreeC

×: Tni deviation is 2.0 ° C or more

Urethane acrylate
compound Thermosetting
time
(minute) Adhesion Viscosity Stability
(7 days later
Viscosity increase rate)
(%) Linearity LCD contamination
(℃) Addition amount
(g) Addition rate (%) Aromatic Aliphatic Example 1 3 100 0 22 ○ 17 ◎ ○ Example 2 10 100 0 20 ○ 16 ◎ ○ Example 3 15 100 0 18 ○ 13 ◎ ○ Example 4 20 100 0 18 ○ 10 ◎ △ Example 5 3 0 100 31 ◎ 17 ◎ ◎ Example 6 3 20 80 30 ◎ 17 ◎ ◎ Example 7 3 50 50 27 ◎ 19 ◎ ◎ Example 8 3 80 20 25 ○ 21 ◎ ○ Example 9 3 100 0 21 ○ 22 ◎ ○ Comparative Example 1 0 0 0 30 ○ 19 ◎ ◎ Comparative Example 2 0.5 100 0 30 ○ 19 ◎ ◎ Comparative Example 3 30 100 0 16 △ 9 ◎ X

Referring to Table 1, the heat curing time of Examples 1 to 4 was about 20 minutes and the adhesion was good, while Comparative Examples 1 and 2 had a relatively long heat curing time. In addition, Comparative Example 3, although the heat curing time was small, it can be seen that the adhesive force is inferior to Examples 1 to 4. It was found that Examples 1 to 6 were somewhat superior to Comparative Examples 1 and 2 in terms of viscosity stability. In addition, in terms of liquid crystal contamination, Examples 5 to 7 were very good, but Comparative Example 3 was bad.

While the embodiments of the present invention have been described above, it will be understood by those skilled in the art that the present invention may be implemented in other specific forms without changing the technical spirit or essential features thereof.

Therefore, it should be understood that the above-described embodiments are provided so that those skilled in the art can fully understand the scope of the present invention. Therefore, it should be understood that the embodiments are to be considered in all respects as illustrative and not restrictive, The invention is only defined by the scope of the claims.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure for demonstrating the linearity index of the hardened | cured material obtained by hardening of curable resin composition concerning the Example and comparative example of this invention.

Claims (11)

100 parts by weight of a partial (meth) acrylate epoxy resin; 1 to 25 parts by weight of a urethane (meth) acrylate compound represented by the following formula (1); 1 to 10 parts by weight of the photopolymerizable initiator; And 1 to 10 parts by weight of dihydrazide latent thermal curing agent Sealant resin composition for flat panel display for display device comprising a.

(One) (In the formula 1, R ₁ is an aromatic compound, an aliphatic compound, or an aliphatic cyclic compound, R ₂ is

N is an integer from 1 to 10, R ₃ is a hydrogen atom or a methyl group, m is an integer from 1 to 5. The method of claim 1, 1 to 7 parts by weight of the silane coupling agent; And 0.02 to 7 parts by weight of thixotropic modifier Sealant resin composition for flat panel display further comprising. The method according to claim 1 or 2, 10 to 40 parts by weight of filler Sealant resin composition for flat panel display further comprising. delete delete The method of claim 1, The said (meth) acrylate epoxy resin is obtained through reaction of the compound which has a (meth) acryl group, and the compound which has an epoxy group, The sealant resin composition for flat panel display devices characterized by the above-mentioned. delete The method of claim 1, The urethane (meth) acrylate compound represented by the said General formula (1) is obtained through the urethane reaction which uses an isocyanate type compound as a raw material, The curable resin composition characterized by the above-mentioned. A flat panel display comprising the sealant formed by curing the sealant resin composition according to claim 1. 10. The method of claim 9, And the flat panel display is a liquid crystal display. In the manufacturing method of the flat panel display device containing the sealant hardened | cured material obtained through hardening of a sealant resin composition, Applying the sealant resin composition of claim 1 onto a substrate; Irradiating light on the sealant resin composition such that the applied sealant resin composition is photocured; And Applying heat to the sealant resin composition such that the sealant resin composition irradiated with the light is thermally cured Method of manufacturing a flat panel display comprising a.

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