KR20100052744A - Amine-based curing agent, curable resin composition and flat panel display having cured product thereof - Google Patents

Abstract

PURPOSE: An amine-based curing agent, a curable resin composition, and a flat panel display including the curing material thereof are provided to rapidly cure the composition at the low temperature, and to minimize the discharge of the composition. CONSTITUTION: An amine-based curing agent is marked as chemical formula 1, or chemical formula 2. In the chemical formula 2, X refers to an alkyl group or an allyl group. R1 and R2 are selected from the group consisting of hydrogen, the alkyl group, a hydroxy alkyl group, or a (meth)acrylc group, respectively. In the chemical formula 2, n refers to an integer of 1~8. X refers to the alkyl group or the allyl group. A curable resin composition contains a curing resin, a photopolymerization initiator and the amine-based curing agent.

Description

A flat panel display device comprising an amine-based curing agent, a curable resin composition, and a cured product of the curable resin composition {AMINE-BASED CURING AGENT, CURABLE RESIN COMPOSITION AND FLAT PANEL DISPLAY HAVING CURED PRODUCT THEREOF}

The present invention relates to a flat panel display device comprising an amine curing agent, 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 interposed between the two substrates. In order to interpose the liquid crystal between the two substrates, the curable resin composition is applied to the edge of any one of the two substrates, the two substrates are bonded together, and then the curable resin composition must be cured. However, since the curable resin composition or the cured product thereof comes into direct contact with the liquid crystal during or after the curing process, the curing process should be performed quickly, and the curable resin composition or the cured product may not be eluted into the liquid crystal. Should be. In addition, in order to improve the reliability of the liquid crystal display device against external forces, the cured product needs to have a strong adhesive strength.

The present invention is an amine-based curing agent capable of low-temperature curing of the curable resin composition while minimizing the dissolution of the curable resin composition or its cured product during or after the curing process, a curable resin composition comprising the same and a cured product of the curable resin composition. It provides a flat panel display comprising a.

The present invention provides a flat panel display comprising an amine-based curing agent capable of improving the adhesive strength of the cured product of the curable resin composition and the storage stability of the curable resin composition, the curable resin composition comprising the same, and the cured product of the curable resin composition. .

An amine curing agent according to an aspect of the present invention is represented by the following formula (1) or (2).

In Chemical Formulas 1 and 2, n is an integer of 1 to 8, X is an alkyl group or an allyl group, and R ₁ and R ₂ are each independently selected from H, an alkyl group, a hydroxyalkyl group, or a (meth) acryl group. .

On the other hand, the curable resin composition according to an aspect of the present invention includes at least one amine-based curing agent of the curable resin, photopolymerization initiator, and two amine-based curing agents represented by the formula (1) and (2), respectively.

Here, the content of each component of the curable resin composition may be 100 parts by weight of the curable resin, 1 to 10 parts by weight of the photopolymerization initiator, and 1 to 10 parts by weight of the amine curing agent.

On the other hand, the flat panel display according to an aspect of the present invention includes a sealant cured product, the sealant cured product is obtained by curing the curable resin composition, the adhesive strength is 1 N / ㎠ or more.

According to the present invention, the curable resin composition can be cured at low temperature, and the dissolution of the curable resin composition or the cured product thereof can be minimized during or after the curing process. In addition, it is possible to improve the adhesive strength of the cured product obtained through the curing process and the storage stability of the curable resin composition.

Hereinafter, a flat panel display including an amine curing agent according to an aspect of the present invention, a curable resin composition containing the same, and a cured product of the curable resin composition will be described in detail.

The amine-based curing agent according to an aspect of the present invention is a latent thermosetting agent in which curing does not occur at less than 120 ° C. and curing occurs at 120 ° C. or more. The amine curing agent may be represented by the following Chemical Formulas 1 and 2, respectively.

[Formula 1]

[Formula 2]

In Formulas 1 and 2, n is an integer of 1 to 8, X is an alkyl group or an allyl group, and R ₁ and R ₂ are each independently selected from H, an alkyl group, a hydroxyalkyl group, or a (meth) acryl group. .

Here, the alkyl group of X is not particularly limited, but may be, for example, a substituted or unsubstituted C ₁ -C ₃₀ alkyl group.

The allyl group of X is not particularly limited, but may be, for example, a substituted or unsubstituted C ₃ -C ₃₀ allyl group.

The alkyl group of each of R ₁ and R ₂ is not particularly limited, but may be, for example, a substituted or unsubstituted C ₁ -C ₃₀ alkyl group.

The hydroxyalkyl group of each of R ₁ and R ₂ is not particularly limited, but may be, for example, a substituted or unsubstituted C ₁ -C ₂₀ hydroxyalkyl group.

Existing hardening | curing agents include the said imidazole type hardening | curing agents, such as 2-methylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, and P-0505 (manufactured by Shikoku); Dihydrazide-based curing agents such as Amcure VDH, Amcure VDH-J, and Amcure UDH (manufacturer: Ajinomoto); And amine curing agents such as Amicure PN-23, Amicure PN-H, and Amicure PN-31. Conventional curing agents are limited to improve the characteristics such as shortening the curing time, adhesive strength, dissolution properties, etc., the curing agent according to the present invention has the characteristics that can improve the disadvantages of the existing curing agent.

On the other hand, the curable resin composition according to an aspect of the present invention includes at least one amine-based curing agent of the curable resin, photopolymerization initiator, and two amine-based curing agents represented by the formula (1) and (2), respectively. 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. Here, since the said amine hardening | curing agent is the same as that mentioned above, only the characteristic is demonstrated below except the overlapping description.

As the curable resin, both thermosetting and photocuring may be used, and the curing resin is not particularly limited. For example, a partial (meth) acrylate epoxy resin can be used. The partial (meth) acrylate epoxy resin can be obtained through the reaction of a compound having an (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. In addition, the compound which has the said (meth) acryl group may have an epoxy group further, and the compound which has the said epoxy group may have an additional (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 and bisphenol type epoxy resins, and these alone or in combination of two or more thereof. Can be used.

The viscosity of the partial (meth) acrylate epoxy resin may be 30,000 to 200,000 cps. If the viscosity is less than 30,000 cps, there is a problem that the storage stability of the curable resin composition is inferior, and if the viscosity exceeds 200,000 cps, the storage stability of the curable resin composition and the gelation phenomenon may appear.

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, benzoyl isopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, thioxanthone, etc. may be used alone or in combination of two or more thereof. Can be.

The content of the photopolymerization initiator may be 1 to 10 parts by weight based on 100 parts by weight of the curable resin. When 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 in that photocuring of the curable resin composition does not occur sufficiently. When the content of the photopolymerization initiator exceeds 10 parts by weight, liquid crystal contamination by the photopolymerization initiator may occur.

As the amine curing agent, those represented by Formulas 1 and 2 may be used alone or in combination.

The content of the amine-based curing agent may be 1 to 10 parts by weight based on 100 parts by weight of the curable resin. If the content of the amine-based curing 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 occur sufficiently, and when it exceeds 10 parts by weight, liquid crystal contamination by the amine-based curing agent may occur. have.

Examples of the other additives include sensitizers, colorants, antifoaming agents, coupling agents, fillers, and the like.

Among them, inorganic fillers such as silica and talc, organic fillers, and the like may be used. The average particle diameter of the filler is preferably even, and the particle size may vary depending on the type of 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.

The content of the filler may be 5 to 30 parts by weight based on 100 parts by weight of the curable resin. When the content of the filler exceeds 30 parts by weight based on 100 parts by weight of the curable resin, a problem may occur in that the viscosity of the resin composition is increased.

Meanwhile, the flat panel display according to the present invention includes a sealant cured product in an edge region of the flat panel display, and the sealant cured product may be obtained by curing the curable resin composition described above. The adhesive strength of the sealant cured product may be 1 N / cm 2 or more. If the adhesive strength is not greater than 1 N / cm 2, it is difficult to secure the reliability of the flat panel display by external force.

Since the flat panel display device may include a sealant cured product, the present invention is not limited by the type thereof. For example, any one of a liquid crystal display device, a plasma display panel (PDP), and an organic light emitting display device (OLED) may be used. Can be.

The application range of each of the amine curing agent and the curable resin composition according to the present invention is not limited to the flat panel display. For example, the curable resin composition according to the present invention may be applied to all applications in which the existing curable resin composition may be used in addition to the flat panel display.

According to the above, the curable resin composition of the present invention can be cured at low temperature, and can minimize the dissolution of the curable resin composition or its cured product during or after the curing process. In addition, it is possible to improve the adhesive strength of the cured product obtained through the curing process and the storage stability of the curable resin composition.

Hereinafter, the present invention will be described in detail through the following synthesis examples and examples, but the present invention is not limited thereto.

Synthesis Example

Synthesis Example 1 Synthesis of Amine Curing Agent

After dissolving 100 g of 4,4-methylene bisphenyl isocyanate in 1000 g of toluene, after lowering temperature to 0 degreeC, 60 g of 2-methylamino ethanol was dripped over 2 hours. Thereafter, the temperature was raised to room temperature and then stirred for 2 hours to obtain a white precipitate. The precipitate was washed with hexane and dried in vacuo to give 150 g of the polymer of Formula 3, and ¹ H-NMR data for the polymer is shown in FIG. 1.

Synthesis Example 2 Synthesis of Amine Curing Agent

100 g of the polymer obtained in Synthesis Example 1 was dissolved in 1000 g of acetone, and then 80 g of methacrylic anhydride, 55 g of triethylamine, 6 g of DMAP, and 5 g of hydroquinone were added thereto to dissolve it. Thereafter, the mixture was stirred for 3 hours in a reflux reaction. Thereafter, after the temperature was lowered to room temperature, the reaction product was extracted using a 10% sodium hydroxide solution and methylene chloride, and the reaction product was reprecipitated with hexane, followed by drying to obtain 80 g of the polymer of Chemical Formula 4 below. And ¹ H-NMR data for the polymer is shown in FIG. 2.

EXAMPLE

Example 1 Preparation of Curable Resin Composition

74 g of partial (meth) acrylate epoxy resin, 5 g of latent thermosetting agent of Synthesis Example 1 as a thermosetting agent, 1 g of photopolymerization initiator, and 20 g of inorganic filler were blended, and then sufficiently milled with a 3-roll mill, followed by rotating revolving defoamer. Vacuum defoaming treatment was performed to obtain a curable resin composition.

Example 2 Preparation of Curable Resin Composition

A curable resin composition was obtained in the same manner as in Example 1 except that 5 g of the latent thermosetting agent of Synthesis Example 2 was used as the thermosetting agent.

Comparative Example 1: Preparation of Curable Resin Composition

A curable resin composition was obtained in the same manner as in Example 1, except that 5 g of dihydrazide-based VDH-J was used as the thermosetting agent.

Comparative Example 2: Curable Resin Composition

A curable resin composition was obtained in the same manner as in Example 1 except that 5 g of imidazole-based P-0505 was used as the thermosetting agent.

Comparative Example 3: Curable Resin Composition

A curable resin composition was obtained in the same manner as in Example 1, except that 5 g of amine-based PN-23 was used as the thermosetting agent.

Curable Resin Composition Property Evaluation

1. Storage stability

The curable resin compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were respectively stored at room temperature for 2 weeks, and then the viscosity was measured by a spindle viscometer. When the initial viscosity change rate of the measured viscosity is less than 100% was good, 100% or more was evaluated as poor, the results are shown in Table 1 below.

2. Liquid Crystal Reactivity

After putting 1g of the curable resin compositions of Examples 1 and 2 and Comparative Examples 1 to 3 into ampoules, respectively, 1g of liquid crystal was placed in the ampoules and left for 1 hour. Thereafter, UV curing (2000 mJ / cm 2) was performed, followed by thermosetting (120 ° C., 40 min). Then, using a DSC measurement apparatus was measured for T _NI value of the blank liquid crystal at a heating rate of 5 ℃ / min and measuring the T _NI value of the thermal curing is complete, each sample. The closer the T _NI value of each sample is to the T _NI value of the blank liquid crystal, the less pollutant the liquid crystal has. Is shown in Table 1 below.

3. Adhesive strength

The curable resin compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were applied to the central portion of the cleaned ITO glass substrate (manufacturer: Samsung Corning Precision Glass), and then the same ITO glass substrate was superimposed thereon. Thereafter, UV curing (2000mJ / cm 2) was performed, and thermal curing (120 ° C., 40 min) was performed to prepare respective specimens for measuring adhesive strength. Adhesive strength was measured using a tensile strength meter (Tinius Olsen) for each of the prepared specimens, the results are shown in Table 1 below.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Storage stability Good Good Bad Bad Bad Liquid crystal reactivity Good Good Good Bad Bad Adhesive strength
(N / ㎠) 1.2 1.5 0.8 0.5 0.4

Referring to Table 1, the curable resin composition prepared through the embodiments of the present invention is not only excellent overall storage stability than the curable resin composition prepared through the comparative example, but also less reactivity with the liquid crystal, adhesive strength It was found to be excellent.

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.

1 is a diagram showing a ¹ H-NMR spectrum of an amine curing agent obtained in Synthesis Example 1 of the present invention.

2 is a diagram showing a ¹ H-NMR spectrum of an amine curing agent obtained in Synthesis Example 2 of the present invention.

Claims (9)

An amine hardener represented by the following formula.

(In the above formula, X is an alkyl group or an allyl group, R ₁ and R ₂ are each independently selected from H, an alkyl group, a hydroxyalkyl group, or a (meth) acryl group.) An amine hardener represented by the following formula.

(In the above formula, n is an integer from 1 to 8, X is an alkyl group or an allyl group, R ₁ is selected from H, an alkyl group, a hydroxyalkyl group, or a (meth) acryl group.) Curable resin composition containing curable resin, a photoinitiator, and at least 1 type of amine-type hardener among 2 types of amine-type hardeners represented by following General formula (1) and (2), respectively.

           (One)

                        (2) (In Chemical Formulas 1 and 2, n is an integer from 1 to 8, X is an alkyl group or an allyl group, R ₁ and R ₂ are each independently selected from H, an alkyl group, a hydroxyalkyl group, or a (meth) acryl group.) The method of claim 3, The content of each component of the curable resin composition is 100 parts by weight of the curable resin, 1 to 10 parts by weight of the photopolymerization initiator, and 1 to 10 parts by weight of the amine curing agent, characterized in that the curable resin composition. The method of claim 3, Said curable resin is a partial (meth) acrylate epoxy resin, Curable resin composition characterized by the above-mentioned. The method of claim 5, 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 curable resin composition characterized by the above-mentioned. The method of claim 3, Curable resin composition, characterized in that the viscosity of the curable resin is 30,000 to 200,000 cps. A flat panel display device comprising a sealant cured product, The said sealant hardened | cured material is obtained by hardening of the curable resin composition of Claim 3, and the adhesive strength of the said sealant hardened | cured material is 1 N / cm <2> or more, The flat panel display device characterized by the above-mentioned. The method of claim 8, And the flat panel display is a liquid crystal display.

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