KR20110111844A - Transparent and highly heat resistant epoxy curing resin and preparation method thereof - Google Patents

Abstract

The present invention relates to a high heat resistant transparent epoxy cured resin and a method for manufacturing the same, and more particularly to a high heat resistant transparent epoxy cured resin and a method for manufacturing the same that can be stably used in the manufacturing process of a flexible LCD panel. The high heat-resistant transparent epoxy cured resin of the present invention has excellent glass transition temperature and mechanical properties, and has a low coefficient of thermal expansion, which can be used in the manufacturing process of an LCD panel using an existing glass substrate. By changing the phase difference of the pattern cell of the LCD panel can be minimized can be used in the manufacture of a flexible LCD panel (flexible LCD panel).

Description

High heat resistant transparent epoxy cured resin and its manufacturing method {TRANSPARENT AND HIGHLY HEAT RESISTANT EPOXY CURING RESIN AND PREPARATION METHOD THEREOF}

The present invention relates to a high heat resistant transparent epoxy cured resin and a method for manufacturing the same, and more particularly to a high heat resistant transparent epoxy cured resin and a method for manufacturing the same that can be stably used in the manufacturing process of a flexible LCD panel.

Liquid crystal display (LCD) uses the principle that the liquid crystal's molecular arrangement is disturbed and does not pass through the light when a certain voltage is applied, and it has better visibility and the same power consumption than the color cathode ray tube. Compared with the plasma display device (PDP) or the field emission display device (FED) in recent years, mobile phones and computer monitors are not only small, but also have a small amount of heat generation and can be manufactured thinner, which makes them easier to flatten. Is emerging as a next-generation display device such as a television.

Such liquid crystal displays generally include an LCD panel and a backlight unit. The LCD has excellent color reproducibility, high color temperature and white balance. In order to satisfy the characteristics of the LCD, the substrate of the LCD panel is transparent and the substrate is deformed even at the high temperature of the LCD manufacturing process over 200 ° C. It is required to be made of a material having high heat resistance so as to minimize the phase difference change of the pattern cell.

Fluorene epoxy resins and fluorene hydroxyepoxy acrylate resins derived therefrom are known as resins having excellent heat resistance.

Japanese Patent Application No. 3448694 discloses a technique for producing a polyurethane having a chemically stable fluorene skeleton having heat resistance represented by the following Chemical Formula 1 by reacting bis (hydroxyphenyl) fluorene (BHPF) with diisocyanate. Doing.

[Formula 1]

Korean Unexamined Patent Publication No. 2005-0001477 discloses a technique for preparing a heat resistant epoxy resin having excellent transparency represented by the following Chemical Formula 2 by reacting bis (hydroxyphenyl) fluorene (BHPF) with epichlorohydrin.

[Formula 2]

U.S. Patent No. 6,007,007 describes a polymer consisting of a polyfunctional epoxide compound of a glycidyl ether of a polyhydric phenol derived from 4,4 '-[9-fluorenylidene] diphenol. Disclosed is a production technique of an epoxy resin composition represented by the following Chemical Formula 3, which is excellent in low temperature curing property and storage stability prepared by curing an isocyanate compound of diisocyanate as a curing agent.

(3)

The present inventors earnestly studied to develop an epoxy resin having better transparency and heat resistance than the resin disclosed in the above-mentioned document, and as a result, 9,9-bis (4-hydroxyphenyl) fluorene (BHPF) or 9,9-bis When using an epoxy cured resin synthesized by reacting a compound of (aminophenyl) fluorene (BAPF) with an isocyanate compound and epichlorohydrin as a substrate of an LCD panel, even in a high temperature LCD process, The present invention has been completed to realize that it is possible to minimize the phase difference change of the pattern cell of the LCD panel due to misalignment.

An object of the present invention is to provide a high heat-resistant transparent epoxy cured resin that can be used as a material of a display that requires transparency and heat resistance and a method of manufacturing the same.

In order to achieve the above object, the present invention is synthesized by reacting epichlorohydrin with a compound of 9,9-bis (4-hydroxyphenyl) fluorene (BHPF) and an isocyanate compound represented by the following formula (4) It provides a heat resistant transparent epoxy cured resin.

[Formula 4]

R1 to R16 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having O—R groups; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) Is selected from the group consisting of.

The present invention also provides a high heat-resistant transparent epoxy cured resin synthesized by reacting 9,9-bis (aminophenyl) fluorene (BAPF) represented by the following formula (5) with a compound of an isocyanate compound and epichlorohydrin.

[Chemical Formula 5]

R1 to R16 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having an OR group; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) Is selected from the group consisting of.

As the isocyanate compound used in the present invention, an aliphatic or aromatic isocyanate compound may be used, and methylene diphenyl diisocyanate represented by the following Chemical Formula 6 is more preferably used.

[Formula 6]

.

.

The present invention is synthesized by reacting epichlorohydrin with a compound of 9,9-bis (4-hydroxyphenyl) fluorene (BHPF) represented by the formula (4) and methylene diphenyl diisocyanate represented by the formula (6) It provides a high heat resistant transparent epoxy cured resin composition represented by the following formula (7).

[Formula 7]

.

.

In addition, the present invention is 9,9-bis (4-hydroxyphenyl) fluorene (BHPF) represented by the formula (4) or 9,9-bis (aminophenyl) fluorene (BAPF) and isocyanate represented by the formula (5) Reacting and synthesizing the compound (step 1);

Epichlorohydrin and the compound obtained by reacting 9,9-bis (4-hydroxyphenyl) fluorene (BHPF) or 9,9-bis (aminophenyl) fluorene (BAPF) with an isocyanate compound in step 1 Dissolving in a solvent, followed by mixing and reacting to obtain a high heat-resistant transparent epoxy cured resin composition (step 2); And

It provides a method for producing a high heat resistant transparent epoxy cured resin comprising the step (step 3) of curing the high heat resistant transparent epoxy cured resin composition obtained in step 2 using a curing agent and a curing initiator.

Hereinafter will be described in detail step by step the manufacturing method of a high heat-resistant transparent epoxy cured resin of the present invention.

First, 9,9-bis (4-hydroxyphenyl) fluorene (BHPF) or 9,9-bis (aminophenyl) fluorene (BAPF) is synthesized by reacting an isocyanate compound (step 1).

More specifically, 9,9-bis (4-hydroxyphenyl) fluorene (BHPF) represented by the formula (4) or 9,9-bis (aminophenyl) fluorene (BAPF) represented by the formula (5) After stirring and dissolving in a solvent in a reaction tank, an isocyanate compound and a catalyst are added, and reacted at 95-105 degreeC, and it synthesize | combines.

The organic solvent may be dimethylformamide, dimethylacetamide, methylene chloride, N-methylpyrrolidone, dimethyl sulfoxide and the like, but is not limited thereto.

Dibutyl tin dilaurate (DBTDL) may be used as the catalyst, but is not limited thereto.

9,9-bis (4-hydroxyphenyl) fluorene (BHPF) and 9,9-bis (aminophenyl) fluorene (BAPF) in the method for producing a high heat-resistant transparent epoxy cured resin of the present invention 9,9-bis (4-hydroxyphenyl) fluorene (BHPF) represented by 4 and 9,9-bis (aminophenyl) fluorene (BAPF) represented by Formula 5 may be used.

Next, in the step 1, 9,9-bis (4-hydroxyphenyl) fluorene (BHPF) or 9,9-bis (aminophenyl) fluorene (BAPF) and an isocyanate compound are reacted with epichlorochloride. Hydrin is dissolved in a solvent, mixed and reacted to obtain a high heat-resistant transparent epoxy cured resin composition (step 2).

More specifically, the compound of 9,9-bis (4-hydroxyphenyl) fluorene (BHPF) or 9,9-bis (aminophenyl) fluorene (BAPF) and an isocyanate compound obtained in step 1 was epichloromethane. It is added to a solvent together with a hydrin and a catalyst, mixed in a reactor, and then heated to a temperature of 30 to 80 ° C. After the reaction by adding an aqueous sodium hydroxide solution to the mixture and after washing, drying and recrystallization process it can be obtained a high heat-resistant transparent epoxy cured resin composition of the present invention.

As the solvent used in step 2, 1,4-dioxane (1,4-dioxane) or the like may be used, but is not limited thereto.

In addition, the catalyst used in step 2 may be teraethyl ammonium bromide or the like, but is not limited thereto.

In one embodiment of the present invention, the high heat resistant transparent epoxy cured resin composition may be a high heat resistant transparent epoxy cured resin composition represented by the following formula (7).

[Formula 7]

.

.

Finally, the high heat resistant transparent epoxy cured resin composition obtained in step 2 is cured using a curing agent and a curing initiator to prepare a high heat resistant transparent epoxy cured resin of the present invention (step 3).

As the curing agent, an amine curing agent, an anhydride curing agent or an alcohol curing agent can be used.

As the curing initiator in the present invention, a photocuring initiator including titanium oxide, benzoin alkyl ether, aromatic ketone, aromatic ketal, thioxanthone, and the like may be used, and azo compounds, peroxy ester compounds, and peroxy dicarbonates. A thermal curing initiator may be used including a compound, acyl peroxide, and the like, but is not limited thereto.

As such, the method of curing the epoxy cured resin composition using a curing agent and a curing initiator can be easily carried out by a person skilled in the art to which the present invention pertains, and thus a detailed description thereof will be omitted.

The present invention can be used in the manufacturing process of the LCD panel using the existing glass substrate by providing a high heat-resistant transparent epoxy cured resin having excellent glass transition temperature, mechanical properties and low coefficient of thermal expansion, and shrinkage of the substrate in the high temperature LCD manufacturing process. It is possible to minimize the phase difference change of the pattern cell of the LCD panel due to the expansion can be used in the manufacture of the flexible LCD panel.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

< Example >

< Example  1> High heat resistant transparent epoxy Cured resin  Produce

7.013 g of bis (hydroxyphenyl) fluorene and 50 ml of dimethylformamide were added to a 3-neck separation reactor equipped with a stirrer, a nitrogen inlet, and a condenser, and dissolved by vigorous stirring at 90 ° C. for 1 hour. 10.01 g of methylene diphenyl diisocyanate and 0.1 g of dibutyltin dilaurate were added as a catalyst and reacted at a temperature ranging from 95 to 105 ° C. for 3 hours. The reactant thus obtained was precipitated in methanol, filtered and dried to give a composite of bis (hydroxyphenyl) fluorene and methylene diphenyl diisocyanate.

17.02 g of a compound of bis (hydroxyphenyl) fluorene and methylene diphenyl diisocyanate obtained above, 15 ml of epichlorohydrin and 0.745 g of teraethyl ammonium bromide were added to a solvent of 3.427 ml of 1,4-dioxane. The mixture was heated in a 3-neck separation reactor and heated up to 65 ° C while stirring. Thereafter, 12.76 ml of an aqueous sodium hydroxide solution (50% by weight of NaOH) was administered to the mixture of the reactor for 1 hour, and then reacted for 2 hours to obtain a white reactant. The reactants were placed in a rotary evaporator to remove sodium hydroxide, washed with deionized water, dried in a vacuum oven, recrystallized with acetone and ethanol 5: 1 solvent, and then in a vacuum oven for 12 hours. Drying yielded a high heat resistant transparent epoxy cured resin composition.

 The high heat resistant transparent epoxy cured resin composition of the present invention was prepared by curing the high heat resistant transparent epoxy cured resin composition of the present invention using a curing agent and a curing initiator.

Claims (15)

A high heat-resistant transparent epoxy cured resin, which is synthesized by reacting epichlorohydrin with a reactant of 9,9-bis (4-hydroxyphenyl) fluorene (BHPF) and an isocyanate compound represented by Formula 4 below:
[Chemical Formula 4]

R1 to R16 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having an OR group; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) Selected from the group consisting of. A high heat resistant transparent epoxy cured resin, which is synthesized by reacting epichlorohydrin with a reactant of 9,9-bis (aminophenyl) fluorene (BAPF) and an isocyanate compound represented by Formula 5 below:
[Chemical Formula 5]

R1 to R16 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having an OR group; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) Selected from the group consisting of.
The method according to claim 1 or 2,
The isocyanate compound is a high heat resistant transparent epoxy cured resin, characterized in that the aliphatic or aromatic isocyanate compound.
The method according to claim 3,
The isocyanate compound is a high heat resistant transparent epoxy cured resin, characterized in that methylene diphenyl diisocyanate represented by the following formula (6):
[Formula 6]

.
A high heat resistant transparent epoxy cured resin composition represented by the following general formula (7):
[Formula 7]

.
By reacting 9,9-bis (4-hydroxyphenyl) fluorene (BHPF) represented by the formula (4) or 9,9-bis (aminophenyl) fluorene (BAPF) represented by the formula (5) and an isocyanate compound Synthesizing (step 1);
Epichlorohydrin and the compound obtained by reacting 9,9-bis (4-hydroxyphenyl) fluorene (BHPF) or 9,9-bis (aminophenyl) fluorene (BAPF) with an isocyanate compound in step 1 Dissolving in a solvent, followed by mixing and reacting to obtain a high heat-resistant transparent epoxy cured resin composition (step 2); And
Curing the high heat resistant transparent epoxy cured resin composition obtained in step 2 using a curing agent and a curing initiator (step 3)
Method for producing a high heat resistant transparent epoxy cured resin comprising:
[Chemical Formula 4]

[Chemical Formula 5]

R1 to R16 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having an OR group; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) Selected from the group consisting of.
The method of claim 6,
The isocyanate compound is an aliphatic or aromatic isocyanate compound, characterized in that the high heat-resistant transparent epoxy cured resin.
The method according to claim 7,
The isocyanate compound is a methylene diphenyl diisocyanate represented by the following formula (methylene diphenyl diisocyanate) method of producing a high heat resistant transparent epoxy cured resin:
[Formula 6]

.
The method of claim 6,
In Step 1, 9,9-bis (4-hydroxyphenyl) fluorene (BHPF) or 9,9-bis (aminophenyl) fluorene (BAPF) and an isocyanate compound are mixed in a 2: 1 to 2.5: 1 molar ratio. Method of producing a high heat-resistant transparent epoxy cured resin characterized in that the reaction.
The method of claim 6,
Epichlorohydrin and the compound obtained by reacting 9,9-bis (4-hydroxyphenyl) fluorene (BHPF) or 9,9-bis (aminophenyl) fluorene (BAPF) with an isocyanate compound in step 2 To dissolve in a solvent, mix and react, and then add and react with an aqueous sodium hydroxide solution to react the transparent heat-resistant cured epoxy resin.
The method of claim 6,
The curing agent is an amine-based curing agent, an anhydride-based curing agent or an alcohol-based curing agent, characterized in that the manufacturing method of high heat-resistant transparent epoxy cured resin.
The method of claim 6,
The curing initiator is a method of producing a high heat-resistant transparent epoxy cured resin, characterized in that the photocuring initiator or thermal curing initiator.
The method of claim 12,
The photocuring initiator is selected from the group consisting of titanium oxide, benzoin alkyl ether, aromatic ketone, aromatic ketal and thioxanthone, and the thermal curing initiator is an azo compound, a peroxyester compound, a peroxy dicarbonate compound and an acyl Method for producing a high heat-resistant transparent epoxy cured resin, characterized in that selected from the group consisting of peroxides.
9,9-bis (4-hydroxyphenyl) fluorene (BHPF) represented by the formula (4) or 9,9-bis (aminophenyl) fluorene (BAPF) represented by the formula (5) LCD panel manufactured using a high heat resistant transparent epoxy cured resin prepared by reacting epichlorohydrin as a substrate:
[Chemical Formula 4]

[Chemical Formula 5]

R1 to R16 are each independently hydrogen; Alkyl or cycloalkyl group having 1 to 12 carbon atoms; Allyl or substituted allyl in which the carbon number is 1 to 12; halogen; Alkoxy groups having an OR group; CnF (2n + 1) Perfuloro-alkyl group having 1 to 12 integer values n and CnCl (2n + 1) Perchloro-alkyl having 1 to 12 integer values n ) Selected from the group consisting of.
The method according to claim 14,
The high heat-resistant transparent epoxy cured resin is an LCD panel, characterized in that prepared by curing the high heat-resistant transparent epoxy cured resin composition represented by the following formula (7):
[Formula 7]

.