KR20160093176A - Novel fluorene-containing (meth)acrylic compound, curable composition comprising the same, optical sheet prepared therefrom, and optical display apparatus comprising the same - Google Patents

Abstract

A fluorene-containing (meth)acrylic compound of the present invention is displayed with chemical formula 1. In chemical formula 1, X1, X2, X3, X4, X5, and X6 are oxygen (O) or sulfur (S). In the first chemical formula, Y1 and Y2 are hydrogen or methyl. In chemical formula 1, n is the integer of 0 to 10. The purpose of the present invention is to provide a chemical composition including a novel fluorene-containing (meth)acrylic compound having a high refractive index and a low viscosity, an optical sheet formed from the chemical composition, and an optical display apparatus including the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel fluorene group-containing (meth) acrylic compound, a curable composition containing the same, an optical sheet formed therefrom, and an optical display device comprising the same. TECHNICAL FIELD [0001] The present invention relates to a novel fluorene group- , And OPTICAL DISPLAY APPARATUS COMPRISING THE SAME}

The present invention relates to a novel fluorene group-containing (meth) acrylic compound, a curable composition containing the same, an optical sheet formed therefrom, and an optical display device comprising the same.

A liquid crystal display device includes a base film and an optical sheet including an optical pattern formed on the base film. A light guide plate may be disposed under the optical sheet, or another optical sheet may be disposed between the optical sheet and the light guide plate. The optical sheet refracts light emitted from the light guide plate and emits the light. In order to increase the brightness of the liquid crystal display device, the refractive index of the optical sheet must be increased. The curable composition comprises a high refractive index monomer to increase the refractive index. However, there are limits to increasing the refractive index due to the other monomers included with high refractive index monomers.

Further, a protective sheet or another optical sheet may be further formed on the optical sheet. The optical pattern can be influenced by the contact of the optical pattern layer of the optical sheet with the protective sheet or the like and the brightness of the liquid crystal display device can be lowered so that it is necessary to improve the scratch resistance in addition to the refractive index.

The background art of the present invention is disclosed in Korean Patent Publication No. 2013-0074115.

It is an object of the present invention to provide a novel fluorene group-containing (meth) acrylic compound having a high refractive index and a low viscosity, a curable composition containing the same, an optical sheet formed therefrom, and an optical display device comprising the same.

Another object of the present invention is to provide a novel fluorene group-containing (meth) acrylic compound having excellent brightness and scratch resistance, a curable composition containing the same, an optical sheet formed therefrom, and an optical display device comprising the same.

The above and other objects of the present invention can be achieved by the present invention described below.

The fluorene group-containing (meth) acrylic compound, which is one aspect of the present invention, is represented by the following formula (1).

[Chemical Formula 1]

Wherein X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ are oxygen (O) or sulfur (S), Y ₁ and Y ₂ are hydrogen or a methyl group, Lt; / RTI >

The curable composition, which is another aspect of the present invention, may contain the fluorene group-containing (meth) acrylic compound.

An optical sheet, which is another aspect of the present invention, may be formed from the curable composition.

An optical display device that is another aspect of the present invention may include the optical sheet.

Disclosed is a novel fluorene group-containing (meth) acrylic compound having a high refractive index and a low viscosity, excellent in luminance and scratch resistance, a curable composition containing the same, an optical sheet formed therefrom, and an optical display device Effect.

1 is a perspective view of an optical sheet according to an embodiment of the present invention.
Fig. 2 is a cross-sectional view taken along line XY in Fig. 1. Fig.
3 is a perspective view of an optical sheet according to another embodiment.
4 is a perspective view of an optical display device according to one embodiment.
5 is a perspective view of a composite optical sheet according to one embodiment.
6 is a ¹ H-NMR graph of Production Example 1.

As used herein, "(meth) acryl" means acryl and / or methacryl.

The fluorene group-containing (meth) acrylic compound of the present invention is represented by the following formula (1).

[Chemical Formula 1]

Wherein X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ are oxygen (O) or sulfur (S), Y ₁ and Y ₂ are hydrogen or a methyl group, Lt; / RTI >

The fluorene group-containing (meth) acrylic compound can be applied to a curable composition without limitation, and can be applied to, for example, an optical film, and is particularly advantageous for forming an optical pattern film.

X ₁ , X ₂ , X ₃ and X ₄ are oxygen (O) or sulfur (S), and in particular, X ₁ and X ₂ are fluorene The refractive index of the (meth) acrylic compound can be increased, and the refractive index of the optical sheet formed therefrom is also high. In addition, the monomer of formula (1) has a viscosity of 800 cPs or less, especially a viscosity lower than n according to n, which can lower the viscosity of the curable composition.

Specifically, the refractive index of the fluorene group-containing (meth) acrylic compound may be 1.60 to 1.70, specifically 1.62 to 1.70, more specifically 1.63 to 1.70. The refractive index of the optical sheet is not lowered within the above range, and the brightness of the optical sheet can be increased.

The fluorene group-containing (meth) acrylic compound may have a viscosity at 25 ° C of 100 cPs to 800 cPs, specifically 250 cPs to 750 cPs, more specifically 400 cPs to 700 cPs. The scratch resistance of the optical sheet is enhanced in the above-mentioned range, the adhesion is good, and the processability is good.

The fluorene group-containing (meth) acrylic compound can be prepared by the following method.

Specifically, 9-fluorenone represented by the following formula 1-1 is reacted with an aromatic compound represented by the following formula 1-2 to prepare an intermediate represented by formula 1-3. For example, 9-fluorenone represented by the following formula (1-1), an aromatic compound represented by the formula (1-2) and toluene are stirred, AlCl ₃ is added as a catalyst, and further stirred at room temperature for 15 hours do. The obtained reaction product is washed with water, and dichloromethane is added thereto, followed by extraction and drying to obtain an intermediate compound of the formula 1-3.

[Formula 1-1]

[Formula 1-2]

(In the formula 1-2, Y ₁ and Y ₂ are -OH group or -SH group)

[Formula 1-3]

(Wherein X ₁ and X ₂ are oxygen (O) or sulfur (S), and X ₃ and X ₄ are -OH group or -SH group,

To the prepared intermediate, n of the above formula (1) is controlled with ethylene oxide (EO). For example, methanol is added to a mixture of the above-mentioned intermediate and NaOMe to completely dissolve and stir the reaction product. After that, chloroethanol is added to introduce ethylene oxide (EO) group. In the case of preparing the compound of the formula (1) wherein n = 0, the process of introducing the ethylene oxide group may be omitted.

After the obtained compound is dissolved in THF, triethylamine is slowly added dropwise while stirring. Then, acryolyl chloride solution is slowly added dropwise under ice-bath and stirred. After confirming the reaction through TLC monitoring (after 2 hours), the THF was removed under reduced pressure, and the organic material was dissolved in dichloromethane, washed three times with water and subjected to column chromatography (hexane: ethylacetate = 5: 1, rf value: 0.4) To obtain a compound represented by the following general formula (1).

[Chemical Formula 1]

Wherein X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ are oxygen (O) or sulfur (S), Y ₁ and Y ₂ are hydrogen or a methyl group, Lt; / RTI >

Hereinafter, the curable composition which is another aspect of the present invention will be described.

The curable composition of the present invention may contain the fluorene group-containing (meth) acrylic compound. As a result, the refractive index of the optical sheet can be increased to increase the luminance, and the scratch resistance is also excellent.

Specifically, the curable composition may include at least one of fluorene group-containing (meth) acrylic compounds represented by the following general formulas (1a) to (1h).

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

[Formula 1e]

(1f)

[Formula 1g]

[Chemical Formula 1h]

The curable composition may contain 5 wt% to 85 wt%, specifically 5 wt% to 80 wt%, more specifically 5 wt% to 75 wt% of the fluorene group-containing (meth) acrylic compound. In the above-mentioned range, the optical pattern layer and / or the optical sheet are excellent in balance of scratch resistance, brightness, refractive index, transparency and workability.

The fluorene group-containing (meth) acrylic compound is excellent in scratch resistance, high in refractive index and brightness, and low in viscosity and refractive index. Therefore, the fluorene group-containing (meth) acrylic compound can be applied in various ways according to the use, and monomers having a low viscosity may not be added separately.

In one embodiment, the curable composition comprises 40% to 95% by weight, specifically 45% to 90%, more specifically 55% to 80% by weight, of the fluorene group-containing (meth) . Within the above range, the curable composition is excellent in scratch resistance, transparency and workability, and the viscosity is suitable for coating.

In another embodiment, the curable composition may comprise from 25 wt% to 75 wt%, specifically from 35 wt% to 70 wt% of the fluorene group-containing (meth) acrylic compound. In the above-mentioned range, the optical sheet has excellent scratch resistance, transparency, impact resistance, and the like, and does not lower the refractive index of the optical sheet, thereby realizing high brightness.

In another embodiment, the curable composition may contain the fluorene group-containing (meth) acrylic compound in an amount of 5 wt% to 40 wt%, specifically 10 to 30 wt%. The refractive index of the optical sheet is not lowered within the above-mentioned range, and high brightness can be realized, and transparency, impact resistance and adhesion are excellent.

The curable composition may further comprise an initiator. The initiator cures the monomer contained in the curable composition to form an optical pattern. The initiator may include at least one of a conventional photocurable initiator and a heat curing initiator. For example, phosphine oxide, formate, phosphate and the like can be used, but not always limited thereto.

The initiator may be contained in the curable composition in an amount of 0.1 to 10% by weight, more preferably 1 to 5% by weight, based on the solids content. In this range, the curing can be completed and the remaining amount of the initiator remains, .

The curable composition may further comprise a crosslinking agent. The crosslinking agent is a trifunctional or more (meth) acrylic monomer and cured together with the monomers of formula (1) and the non-phosphorus monomer to increase the degree of crosslinking of the optical sheet to improve the scratch resistance of the optical sheet. , For example, trifunctional or hexafunctional (meth) acrylic monomers, which may be used singly or in combination of two or more.

Specifically, the refractive index of the crosslinking agent can be 1.45 to 1.55, and the transparency and the refractive index of the optical sheet can be increased within the above range.

The crosslinking agent may contain from 2 to 9 photocurable functional groups (e.g., (meth) acrylate groups), which may be used alone or in combination of two or more. Specifically, the cross-linking agent may have an aromatic group to further increase the refractive index.

The crosslinking agent may be contained in the curable composition in an amount of 0 to 20% by weight, for example, 1 to 20% by weight, more preferably 3 to 15% by weight, based on the solid content. In the above range, the degree of crosslinking of the optical sheet is increased to impart scratch resistance and impact resistance And it is possible to improve the adhesion property.

The curable composition may further include conventional additives. The additives may include, but are not limited to, leveling agents, antistatic agents, surfactants, colorants, and the like. In addition, the curable composition may be prepared as a solvent-free solventless type or may further include a solvent to increase the coating property of the composition. For example, methyl ethyl ketone or the like may be used.

In embodiments, the curable composition may have a viscosity at 25 [deg.] C of from 800 to 2,000 cPs, specifically from 1,000 cPs to 2,000 cPs, more specifically from 800 cPs to 1,600 cPs, .

Another aspect of the invention relates to an optical sheet formed from the curable composition. 1 is a perspective view of an optical sheet according to an embodiment of the present invention.

The optical sheet 100 according to one embodiment of the present invention has a light outgoing surface that is a top surface and a light incident surface that is a bottom surface, And an optical pattern layer (120) formed on the base film (110). The optical pattern layer 120 is formed from a curable composition containing a fluorene group-containing (meth) acrylic compound represented by the general formula (1).

The base film 110 includes a light incidence surface and supports the optical pattern layer 120. The thickness of the base film 110 is not limited but may be 10 to 300 占 퐉, specifically 50 to 125 占 퐉, Lt; / RTI >

The base film 110 may be formed of the same or different material as the optical pattern layer 120, and may be a transparent film formed of, for example, a thermoplastic resin or a composition containing the thermoplastic resin. Specifically, the thermoplastic resin may be a polyester resin including a polyethylene terephthalate resin and a polyethylene naphthalate resin, a polyacetal resin, a (meth) acrylic resin, a polycarbonate resin, a styrene resin, a vinyl resin, a polyphenylene ether Butadiene-styrene copolymer resin, poly (meth) acrylate resin, polyaryl sulfone resin, polyether sulfone resin, polyether sulfone resin, polyether sulfone resin, polyether sulfone resin, , A polyphenylene sulfide-based resin, and a fluorine-based resin.

The optical pattern layer 120 includes a light exit surface and refracts and emits the light incident from the base film 110. The optical pattern layer 120 is formed with one or more optical patterns on the base film. 1 illustrates a case where a triangle is a prism in a cross section. However, the optical pattern is not limited thereto. The optical pattern may be a prism, a microlens pattern, a lenticular lens pattern, an emboss pattern or an emboss pattern having a polygonal cross section (a polygon having 4 to 10 sides) May be included.

Referring to FIG. 2, the height of the optical pattern layer 120, that is, the optical pattern may be the same or different for each pattern. Specifically, the height H may be about 10 to about 40 μm, for example, about 10 to about 30 μm And there may be no moiré in the above range and a light converging effect. The pitch P of the optical pattern layer 120 may be the same or different for each pattern. Specifically, the pitch may be about 10 to about 60 占 퐉, for example, about 20 to about 60 占 퐉, There is no condensation effect. The apex angle alpha of the optical pattern can be 80 DEG to 100 DEG, and the brightness enhancement effect can be obtained in the above range.

The optical sheet 100 includes the above-mentioned acrylic compound not containing a halogen element, so that the yellowing phenomenon can be prevented and the environment friendliness can be enhanced.

The optical sheet 100 includes the fluorene group-containing (meth) acrylic compound, In a state in which an aging pole (AG pol: pole having an anti-glare (AG) layer having strength of 2H) and a weight having a weight between 0 and 100 g are sequentially placed on the optical pattern layer, The weight of the first weight, which starts to damage the optical pattern layer after three round trips of AG Pol, may be 15 g or more. The influence of the optical pattern due to the contact with the protective sheet or the optical sheet in the above-described range is small, and the brightness of the liquid crystal display device is not lowered.

The above optical sheet 100 includes the fluorene group-containing (meth) acrylic compound, and is excellent in luminance, refractive index and scratch resistance.

The optical sheet 100 may include the fluorene group-containing (meth) acrylic compound and have a luminance gain value of 2.1% or more, for example, 2.1% to 3%. The efficiency and visibility of the optical display device are excellent in the above range. The luminance gain value of the optical sheet means a rate at which the luminance is increased when the optical sheet is further included in the backlight unit for a liquid crystal display. The brightness gain value of the optical sheet was measured using a LED lamp (samsung LED, 8 elements) as a light source, a 3.97-inch liquid crystal display panel in which a light guide plate (3M ESR), a diffuser plate (LMS, DLAS-38D) Using a backlight unit, luminance (cd / cm ² ) at five points was measured using a luminance meter (model name: BM7 Japan TOPCON Co., current 20 mA) to obtain an average value A. An optical sheet was further placed on a diffuser plate in a backlight unit for a 3.97-inch liquid crystal display panel in which a light guide plate (3M company ESR) and a diffusion plate (LMS, DLAS-38D) (Cd / cm < ² >) at five points by using the same luminance meter to obtain an average value B, and the luminance gain value of the optical sheet can be obtained from the following equation (1)

<Formula 1>

Luminance gain value = (A-B) / A x 100

In the optical sheet 100, the refractive index of the optical pattern layer may be 1.56 to 1.68, for example, 1.56 to 1.65. By the high refractive index in the above range, the brightness of the optical sheet 100 becomes high.

3 shows an optical sheet according to another embodiment of the present invention. The optical sheet 200 includes a base film 110, an optical pattern layer 120 formed on the base film 110 and a coating layer 130 formed under the base film 110. The optical pattern layer 120 may have a refractive index of about 1.58 or more and the optical pattern layer 120 may have a hmax of about 5 占 퐉 or more. As a result, the refractive index of the optical sheet can be increased to increase the brightness and the scratch resistance can be improved. Further, since the coating layer 130 is further formed, the diffusing effect of the optical sheet can be further enhanced, and moir 辿 caused by the optical pattern can be prevented. Except that a coating layer is further formed, and therefore only the coating layer will be described in the following.

The coating layer 130 may be formed of an ultraviolet curable resin, and may have a thickness of 1 to 10 占 퐉 and may be used in the optical sheet in the above range.

The coating layer 130 may be a diffusion coating layer, and a pattern for diffusing function, for example, an irregular pattern may be formed. The concavo-convex pattern can be formed by a sand blast method, a hot press method, a casting method of a transparent resin, or a method of dispersing fine particles on the back surface of a substrate film. As an example, a method of transferring the concavo-convex pattern of the pull roll formed by a sand blasting method in which irregularities are formed by hitting the surface of a pull roll with a bead having a diameter of 1 탆 to 200 탆 is transferred to the other surface of the base film . Specifically, an ultraviolet curable resin is injected between a pull roll formed with a concavo-convex pattern and a base film so that the pull roll is allowed to pass over the base film while being in contact with the ultraviolet curable resin. At this time, it is possible to form the light-diffusing layer on the base film by curing the UV by irradiating the curable resin.

4 is a perspective view of an optical display device according to an embodiment of the present invention.

4, a liquid crystal display 400 according to an exemplary embodiment of the present invention includes a light source 410, a light guide plate 420 for guiding light emitted from the light source 410, a reflective sheet 420 disposed below the light guide plate 420, A diffusion sheet 430 disposed on the upper side of the light guide plate 420 and an optical sheet 440 disposed on the diffusion sheet 430. [ The optical sheet 440 may include an optical sheet according to embodiments of the present invention.

A light source cover 410a may be disposed outside the light source 410 of the backlight unit. Here, although not shown, a liquid crystal display panel and an antireflection layer are sequentially stacked on the liquid crystal display device 400 to constitute a liquid crystal display device.

The light source 410 generates light, and various light sources such as a linear light source lamp, a planar light source lamp, a CCFL, or an LED may be used.

The light guide plate 420 guides the light generated by the light source 410 to the diffusion sheet 430, and may be omitted when a direct-type light source is employed.

The reflective sheet 450 reflects light generated from the light source 410 and supplies the light to the diffusion sheet 430.

The diffusion sheet 430 diffuses and scatters the light incident through the light guide plate 420 and supplies the light to the composite optical sheet 540.

The optical sheet 440 functions to refract light incident through the diffusion sheet 430 and focus the light on a plane of a liquid crystal display panel (not shown). The optical sheet 440 may be formed of various shapes and shapes such as a shape of a light collecting portion and an angle of an inclined surface of a light collecting portion according to various design goals such as high condensing efficiency, wide viewing angle, prevention of moire phenomenon, Combinations are possible and are being applied commercially.

The optical sheet may be a composite optical sheet in which two or more optical sheets are laminated. Figure 5 shows a composite optical sheet according to one embodiment of the present invention.

The composite optical sheet 300 includes a first optical sheet 320 and a second optical sheet 340 formed on the first optical sheet. At least one of the first optical sheet 320 and the second optical sheet 340 may be an optical sheet of the present invention.

In one embodiment, the first optical sheet 320 is formed of the optical sheet of the present invention. In this case, by increasing the refractive index of the first optical sheet, light can be emitted with high luminance. The first optical sheet is formed from a composition comprising 5% to 65% by weight, specifically 5% to 60% by weight, more specifically 10% to 60% by weight, of the fluorene group-containing (meth) . The refractive index of the optical sheet is high in the above-mentioned range to realize high brightness and excellent in transparency, impact resistance and adhesion.

In another embodiment, the second optical sheet 340 may be formed of the optical sheet of the present invention. In this case, the second optical sheet contains 30% by weight to 85% by weight, specifically 35% by weight to 80% by weight, more specifically 40% by weight to 80% by weight, of the fluorene group-containing (meth) &Lt; / RTI &gt; In the above range, the optical sheet has excellent scratch resistance, transparency and impact resistance, and does not lower the refractive index of the optical sheet, thereby realizing high brightness and excellent scratch resistance.

More specifically, the composite optical sheet 300 includes a first optical sheet 320 including a first base film 305 and a first optical pattern layer 310 formed on the first base film 305, And a second optical sheet 340 formed on the first optical sheet 320 and including a second optical film layer 330 formed on the second base film 335 and the second base film 335, The second optical sheet 340 may include the optical sheet of the embodiment of the present invention.

The first optical sheet 320 emits the light incident from the light guide plate (not shown in FIG. 4) to the second optical sheet 340. 5 illustrates a case where the first optical pattern layer 310 is a triangular prism layer. However, the first optical pattern layer is not limited thereto, and may be a prism having a polygonal cross section (a polygon having 4 to 10 sides) A lens pattern, a lenticular lens pattern, an emboss pattern, or a combination thereof.

5, the longitudinal direction of the first optical pattern layer 310 of the first optical sheet 320 is denoted by y1, the pitch direction thereof is denoted by x1, and the second optical pattern layer 330 of the second optical sheet 340 X2 in the longitudinal direction and y2 in the pitch direction, the angle formed by y1 and x2 may be 85to 95 and may be, for example, about 90 [deg.]. In the above range, the luminance gain value increases.

The first optical sheet 320 and the second optical sheet 340 are in a detachable state without being adhered to each other.

The first base film (305) may be formed of the same or different resin as the second base film (335).

The first optical pattern layer 310 may be formed of a curable composition containing the fluorene group-containing (meth) acrylic compound to increase the refractive index of the first optical sheet to emit light at high luminance.

The composite optical sheet 300 may have a luminance gain value of 2.9% or more, for example, 2.9% to 5%. The luminance is improved in the above range. The luminance gain value of the composite optical sheet means a rate at which the luminance is increased when the composite optical sheet is further included in the backlight unit for a liquid crystal display. The luminance gain value of the composite optical sheet was measured using a 3.97-inch liquid crystal display panel (hereinafter referred to as &quot; LED &quot;) in which a light guide plate (samsung LED, 8 elements) The luminance (cd / cm ² ) at five points is measured using a luminance meter (model name: BM7 Japan TOPCON Co., current 20 mA) using a backlight unit for a light source. In a backlight unit for a 3.97-inch liquid crystal display panel in which a light guide plate (3M company ESR) and a diffusion plate (LMS, DLAS-38D) were laminated in sequence as the same light source, a composite optical sheet was further placed on a diffuser plate (Cd / cm &lt; ² &gt;) at five points is measured using the same luminance meter to obtain an average value B and the luminance gain value of the composite optical sheet is calculated from the following equation You can get:

<Formula 1>

Luminance gain value = (AB) / A x 100

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

Example

Production Example 1-1

9-fluorenone (0.277 mol, 50 g), 4-hydroxybenzenethiol (0.55 mol, 70 g) and 500 mL of toluene were added to a 1 L round bottom flask and stirred. The addition of 5 mol% AlCl _3, and the mixture was stirred further at room temperature for 15 hours. The obtained reaction product was washed with water, extracted with dichloromethane, and dried to obtain an intermediate compound. (Yield: 99%)

The obtained intermediate compound was dissolved in 200 mL of THF in the presence of 9,9-dimercapto para -phenol fluorine (29 mmol, 12 g) in a 500 mL two neck flask, and then triethylamine triethylamine, 60 mmol, 8 mL) was slowly added dropwise while stirring. Then 10 mL of acryolyl chloride (60 mmol, 4.9 mL) in THF was slowly added dropwise over 30 minutes under ice-bath. After confirming the reaction through TLC monitoring (2 hours elapsed), the THF was removed under reduced pressure, the organic material was dissolved in dichloromethane, washed three times with water, and purified through column chromatography (hexane: ethylacetate = 5: 1) , And a viscosity of 700 cPs. (Fig. 6 is a ¹ H-NMR graph of the following Formula 1a).

[Formula 1a]

Production Example 1-2

9-fluorenone (0.277 mol, 50 g), 4-hydroxybenzenethiol (0.55 mol, 70 g) and 500 mL of toluene were added to a 1 L round bottom flask and stirred. 5 mol% AlCl ₃ was added and stirred further at RT for 15 hours. The obtained reaction product was washed with water, extracted with dichloromethane, and dried to obtain an intermediate compound. (Yield: 99%)

The intermediate compound (29 mmol, 12 g) and NaOMe (60 mmol, 3.240 g) were added to a 500-mL two-neck flask and 300 mL of methanol was added to dissolve the reaction completely. After that, 60 mmol of chloroethanol was added and ethylene oxide (EO) group was introduced once.

The obtained intermediate compound was dissolved in 200 mL of THF in the presence of 9,9-dimercapto para -phenol fluorine (29 mmol, 12 g) in a 500 mL two neck flask, and then triethylamine triethylamine, 60 mmol, 8 mL) was slowly added dropwise while stirring. Then 10 mL of acryolyl chloride (60 mmol, 4.9 mL) in THF was slowly added dropwise over 30 minutes under ice-bath. After confirming the reaction through TLC monitoring (after 2 hours), the THF was removed under reduced pressure, and the organics were dissolved in dichloromethane. The organic material was washed 3 times with water and purified through column chromatography (hexane: ethylacetate = 5: 1) , A viscosity of 550 cPs, was prepared and its presence was confirmed. . ^{1 H-NMR (400MHz, CDCl} 3) δ ppm 7.32 ~ 7.19 (m, 4H), 7.15 ~ 7.05 (m, 4H), 6.91 ~ 6.82 (m, 4H), 6.65 ~ 6.49 (t, 2H), 6.38 ~ 2H), 6.05-5.95 (t, 2H), 4.32-4.30 (t, 4H), 3.90-3.87 (t, 4H)

[Chemical Formula 1b]

Production Example 1-3

9-fluorenone (0.277 mol, 50 g), 4-hydroxybenzenethiol (0.55 mol, 70 g) and 500 mL of toluene were added to a 1 L round bottom flask and stirred. The addition of 5 mol% AlCl _3, and the mixture was stirred further at room temperature for 15 hours. The obtained reaction product was washed with water, extracted with dichloromethane, and dried to obtain an intermediate compound. (Yield: 99%)

The intermediate compound (29 mmol, 12 g) and NaOMe (60 mmol, 3.240 g) were added to a 500-mL two-neck flask and 300 mL of methanol was added to dissolve the reaction completely. After that, 60 mmol of chloroethanol was added and ethylene oxide (EO) group was introduced twice.

The obtained intermediate compound was dissolved in 200 mL of THF in the presence of 9,9-dimercapto para -phenol fluorine (29 mmol, 12 g) in a 500 mL two neck flask, and then triethylamine amine, 60 mmol, 8 mL) was slowly added dropwise while stirring. Then 10 mL of acryolyl chloride (60 mmol, 4.9 mL) in THF was slowly added dropwise over 30 minutes under ice-bath. After confirming the reaction through TLC monitoring (after 2 hours), the THF was removed under reduced pressure, and the organics were dissolved in dichloromethane. The organic material was washed 3 times with water and purified through column chromatography (hexane: ethylacetate = 5: 1) , A viscosity of 490 cPs, was prepared and its presence was confirmed. ^{1 H-NMR (400MHz, CDCl} 3) δ ppm 7.32 ~ 7.19 (m, 4H), 7.15 ~ 7.05 (m, 4H), 6.91 ~ 6.82 (m, 4H), 6.65 ~ 6.49 (t, 2H), 6.38 ~ (M, 2H), 6.05-5.95 (t, 2H), 4.31-4.26 (bs, 8H), 3.88-3.85 (bs,

 [Chemical Formula 1c]

Production Example 2-1

39.5 mL (0.54 mol) of triethylamine, 50 g (0.271 mol) of cyanuric chloride and 400 mL of tetrahydrofuran (THF) were added to a 1 L round bottom flask, followed by stirring. Then, 100 mL of tetrahydrofuran (THF) in which 59.7 g (0.54 mol) of thiophenol was dissolved was dropped dropwise for 20 minutes. Thereafter, the reaction was allowed to proceed at room temperature for 3 hours. After the completion of the reaction, the resulting salt was removed under reduced pressure. The obtained solid product was purified by chromatography (eluent: hexane / ethyl acetate = 5: 1) to obtain an intermediate represented by the following formula (II-1a) in white.

[Formula 2-1a]

5 g (15 mmol) of the intermediate 1,3-dithiophenol triazine chloride prepared above and 1.1 mL (15 mmol) of triethylamine were added to a 250 mL round bottom flask at 0 ^° C Lt; / RTI &gt; 100 mL of THF (tetrahydrofuran) was added, and then 3.48 g (30 mmol) of hydroxyethyl acrylate was dropwise added dropwise for 20 minutes. The whole reaction mixture was stirred at 0 ^° C for about 1 hour, and then filtered to remove the generated salt. The resulting solid product was purified by chromatography (eluent: hexane / ethyl acetate = 5: 1) to obtain a white solid acrylic compound (refractive index: 1.68) represented by the following formula 2-1b. ^{1 H-NMR (400MHz, CDCl} 3) δ ppm 7.41 ~ 7.39 (d, 2H), 7.35 ~ 7.32 (t, 3H), 7.27 ~ 7.24 (m, 5H), 6.48 (d, 1H), 6.16 (dd, 1H), 5.86 (d, IH), 4.30 (d, 2H), 3.88

[Formula 2-1b]

Production example 2-2

39.5 mL (0.54 mol) of triethylamine, 50 g (0.271 mol) of cyanuric chloride and 900 mL of tetrahydrofuran (THF) were added to a 2 L round bottom flask and stirred. Then, 100 mL of tetrahydrofuran (THF) in which 90.3 g (0.54 mol) of 2-thiobenzothiazole was dissolved was dropped dropwise in a dropwise manner for 60 minutes. The reaction was then allowed to proceed at room temperature for 8 hours. After the completion of the reaction, the resulting salt was removed under reduced pressure. The obtained solid product was recrystallized using an acetone / hexane solvent to obtain a pale yellow intermediate of formula (2-2a) shown by the formula (6-1).

[Formula 2-2a]

5 g (11.2 mmol) of the above-prepared intermediate 1,3-dithiobenzothiazole triazine chloride and 0.8 mL (11.2 mmol) of triethylamine were added to a 250 mL round bottom flask, ^Was stirred at 0 &lt; 0 &gt; C. Thereafter, 2.6 g (22.4 mmol) of hydroxyethyl acrylate was dropped by dropwise for 20 minutes. The whole reaction mixture was stirred at 0 ^° C for about 1 hour, and then filtered to remove the generated salt. The resulting solid product was purified by chromatography (elution: hexane / ethyl acetate = 10: 1) to obtain a white solid acrylic compound (refractive index: 1.70) represented by the following Chemical Formula 2-2b.

[Chemical Formula 2-2b]

Production Example 2-3

39.5 mL (0.54 mol) of triethylamine, 50 g (0.271 mol) of cyanuric chloride and 900 mL of tetrahydrofuran (THF) were added to a 2 L round bottom flask and stirred. Then, 100 mL of tetrahydrofuran (THF) in which 90.3 g (0.54 mol) of 2-thiobenzothiazole was dissolved was dropped dropwise for 60 minutes in a dropwise manner. The reaction was then allowed to proceed at room temperature for 8 hours. After the completion of the reaction, the resulting salt was removed under reduced pressure. The obtained solid product was recrystallized using an acetone / hexane solvent to obtain a pale yellow intermediate represented by Formula 2-3a, represented by the following Formula 11-1.

[Chemical Formula 2-3a]

To a 250 mL round bottom flask was added 4.45 g (10 mmol) of the intermediate 1,3-dithiobenzothiazole triazine chloride prepared above and 0.8 mL (11 mmol) of triethylamine ) ^Was stirred at 0 ^° C. 1.6 g (10 mmol) of 2-mercaptoethyl acrylate was then added dropwise dropwise. The whole reaction mixture was stirred at 0 ^° C for about 1 hour, and then filtered to remove the generated salt. The resulting solid product was purified by chromatography (eluent: hexane / ethyl acetate = 20: 1) to obtain a yellowish solid acrylic compound (refractive index: 1.68) represented by the following formula (2-3b). ^{1 H-NMR (400MHz, CDCl} 3) δ ppm 8.25 (d, 2H), 7.70 (d, 2H), 7.43 (t, 2H), 7.38 (m, 2H), 6.45 (d, 1H), 6.16 (dd , 5.86 (d, 1 H), 4.30 (d, 2H), 3.86 (d, 2H)

 [Formula 2-3b]

Production example 3-1

9,9-bis (4-hydroxyphenyl) fluorene (Daerim Chemical, grade lot.No EM118-14-003N, 100 mmol, 35 g) was dissolved in 300 mL THF in a 1 L two-necked flask, amine, 240 mmol, 32 mL) was slowly added dropwise while stirring. Then 100 mL of THF solution of acryolyl chloride (200 mmol, 16 mL) was added dropwise slowly over 30 minutes under ice-bath. After the THF was removed under reduced pressure, the organic material was dissolved in dichloromethane, washed three times with water, and purified by column chromatography (hexane: ethylacetate = 10: 1) Was prepared and its presence was confirmed.

 [Chemical Formula 3]

(Formula 3a) has a refractive index of 1.60 and a viscosity of 790 cPs.

Production example 3-2

9,9-bis (4-hydroxyphenyl) fluorene (Daerim Chemical, grade lot.No EM118-14-003N, 100 mmol, 35 g) was dissolved in 200 mL of THF in a 1 L two-necked flask, , 200 mmol, 8 g) in 10 mL H ₂ O was slowly added dropwise while stirring for 3 hours. Then, 100 mL of THF solution of 2-chloroethylacrylate (250 mmol, 33.65 g) was slowly added dropwise while stirring, and then the temperature was raised to reflux while confirming the reaction through TLC monitoring. Ten hours later, THF was removed under reduced pressure. And washed three times with water. The solution was purified through column chromatography (hexane: ethylacetate = 7: 1) to prepare a compound 3b and its presence was confirmed.

(3b)

(Formula 3b) has a refractive index of 1.59 and a viscosity of 600 cPs.

Example 1

52% by weight of the fluorene-containing (meth) acrylic compound (refractive index: 1.64, viscosity: 700 cPs) represented by the formula 1a prepared in Preparation Example 1-1 and the compound represented by the formula 2-1b prepared in Preparation Example 2-1 , 3 wt% of a crosslinking agent (PN662NT, refractive index: 1.503) and 3 wt% of an initiator (TPO, manufactured by BASF, refractive index: 1.6) were mixed and stirred to obtain a curable A composition was prepared. A curable composition was coated on one surface of a PET (polyethylene terephthalate) film (manufacturer: MITSUBISHI, trade name: T910E, thickness: 75 占 퐉) for a transparent substrate film and the same height of 12 占 퐉, pitch of 24 占 퐉, The pattern was applied to the coating using a pattern roll having a triangular pattern knitted therein and cured at 350 mJ / cm ² to prepare an optical sheet.

Example 2

10% by weight of a fluorene-containing (meth) acrylic compound (refractive index: 1.64, viscosity: 700 cPs) represented by the formula 1a prepared in Preparation Example 1-1, 44% by weight of a fluorene-containing (meth) acrylic compound (refractive index: 1.636, viscosity: 550 cPs) and 40% by weight of a (meth) acrylic compound represented by the formula 2-1b prepared in Preparation Example 2-1, a crosslinking agent PN662NT (Refractive index: 1.503, manufactured by MIWON SPECIAL CHEMICAL Co., Ltd.) and 3 wt% of an initiator (TPO, manufactured by BASF, refractive index: 1.6) were mixed and stirred to prepare a curable composition. A curable composition was coated on one surface of a PET (polyethylene terephthalate) film (manufacturer: MITSUBISHI, trade name: T910E, thickness: 75 占 퐉) for a transparent substrate film and the same height of 12 占 퐉, pitch of 24 占 퐉, The pattern was applied to the coating using a pattern roll having a triangular pattern knitted therein and cured at 350 mJ / cm ² to prepare an optical sheet.

Example 3

The procedure of Example 1 was repeated except that the fluorene-containing (meth) acrylic compound represented by Formula 1c prepared in Preparation Example 1-3 was used instead of the fluorene-containing (meth) acrylic compound represented by Formula 1a in Example 1, To prepare an optical sheet.

Example 4

(Meth) acryl-based compound represented by the formula 2-2b prepared in Preparation Example 2-2 was used instead of the (meth) acrylic-based compound of the formula 2-1b in Example 1, To prepare an optical sheet.

Example 5

(Meth) acrylic compound represented by Formula 1b prepared in Preparation Example 1-2 was used in place of the fluorene-containing (meth) acrylic compound represented by Formula 1a in Example 1, An optical sheet was prepared in the same manner as in Example 1 except that the (meth) acrylic compound represented by the formula 2-2b prepared in Preparation Example 2-2 was used instead of the (meth) acrylic compound.

Example 6

(Meth) acrylic compound represented by Formula 1b prepared in Preparation Example 1-2 was used in place of the fluorene-containing (meth) acrylic compound represented by Formula 1a in Example 1, An optical sheet was prepared in the same manner as in Example 1, except that the (meth) acrylic compound represented by Formula 2-3b prepared in Preparation Example 2-3 was used instead of the (meth) acrylic compound.

Example 7

The procedure of Example 6 was repeated except that the fluorene-containing (meth) acrylic compound represented by Formula 1c prepared in Preparation Example 1-3 was used instead of the fluorene-containing (meth) acrylic compound represented by Formula 1b in Example 6, To prepare an optical sheet.

Example 8

The procedure of Example 7 was repeated except that (meth) acrylic compound represented by Formula 2-2b prepared in Preparation Example 2-2 was used instead of (meth) acrylic compound represented by Formula 2-3b in Example 7, To prepare an optical sheet.

Comparative Example 1

(Refractive index: 1.60, viscosity: 790 cPs) prepared in Preparation Example 3-1 was used in place of the fluorene-containing (meth) acrylic compound represented by Formula (1a) To prepare an optical sheet.

Comparative Example 2

(Refractive index: 1.60, viscosity: 790 cPs) prepared in Production Example 3-1 was used in place of the fluorene-containing (meth) acrylic compound represented by Formula (Refractive index: 1.59, viscosity: 600 cPs) prepared in Preparation Example 3-2 was used instead of the (meth) acryl-containing compound .

The above Table 1 is expressed in units of% by weight.

The properties of the optical sheets of the prepared examples and comparative examples were evaluated by the following methods and are shown in Table 2.

Property evaluation method

(1) Refractive index: Using a refractometer (model name: 3T, Japan ATAGO ABBE), the refractive indexes of the optical sheets prepared in Examples and Comparative Examples were measured. The light source for the measurement was a 589.3 nm D-light sodium lamp.

(2) Luminance gain: A backlight for a 3.97-inch liquid crystal display panel in which a LED lamp (samsung LED, 8 elements) is used as a light source and a light guide plate (3M ESR) and a diffusion plate (LMS, DLAS- (Cd / cm &lt; ² &gt;) at five points was measured using a luminance meter (model name: BM7 Japan TOPCON Corp., current 20 mA), and an average value A was obtained. In the backlight unit for a 3.97-inch liquid crystal display panel in which the same light source was used and a light guide plate (3M company ESR) and a diffuser plate (LMS, DLAS-38D) were laminated in sequence, the optical sheets of the example and comparative example were further placed on the diffuser plate (The base film of the optical sheet was directed to the diffusion plate side), and the luminance (cd / cm ² ) at five points was measured using the same luminance meter to obtain an average value B. (BA) / A x 100.

(3) Scratch resistance: The AG Pol for 40 "TV was placed on the optical pattern layer of the optical sheet, and the AG Pol for 40" TV was turned back and forth three times at intervals of 5 cm with the weights between 0 and 100 g being raised. And the weight of the first weight at which the optical pattern layer begins to be damaged is measured. The larger the weight of the weight, the higher the scratch resistance.

(4) Transparency: The curable composition is diluted with methyl ethyl ketone (MEK) to a concentration of 50%, and clear coating is performed on the polyethylene terephthalate film (PET) using # 3 BAR. (Good), -1% or + 1% when (ba) / ax 100 is -1% to + 1% when the transmittance of PET before coating is a and the transmittance of PET after coating is b When it is poor, it is evaluated as bad. The transmittance is measured at a wavelength of 380 nm to 780 nm.

Refractive index Luminance gain (%) Scratch resistance (g) Transparency
Transmittance
(%)
(380 to 780 nm) Example 1 1.630 2.9 5.5 95 Example 2 1.628 2.5 5.2 95 Example 3 1.624 2.8 5 94 Example 4 1.655 2.7 4.5 93 Example 5 1.65 2.9 5 92 Example 6 1.652 2.5 6 95 Example 7 1.628 2.1 5.9 91 Example 8 1.633 2.6 6.1 94 Comparative Example 1 1.60 2 4 94 Comparative Example 2 1.599 1.5 3.3 95

As shown in Table 2, the examples including the fluorene group-containing (meth) acrylic compound represented by the general formula (1) have high refractive index and excellent brightness as well as excellent transparency and scratch resistance. However, it can be seen that the comparative example which does not contain the fluorene group-containing (meth) acrylic compound represented by the general formula (1) does not satisfy the effect of the present invention in the refractive index, the luminance and the scratch resistance.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.

Claims (11)

(Meth) acrylic compound having a fluorene group represented by the following formula (1):
[Chemical Formula 1]

Wherein X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ are oxygen (O) or sulfur (S), Y ₁ and Y ₂ are hydrogen or a methyl group, Lt; / RTI &gt;
The fluorine-containing (meth) acrylic compound according to claim 1, wherein the fluorine-containing (meth) acrylic compound has a refractive index of 1.60 to 1.70.
The fluorine-containing (meth) acrylic compound according to claim 1, wherein the fluorine-containing (meth) acrylic compound has a viscosity of 100 cPs to 800 cPs at 25 ° C.
A curable composition comprising the fluorene group-containing (meth) acrylic compound of claim 1.
5. The curable composition according to claim 4, wherein the curable composition comprises at least one of a fluorene group-containing (meth) acrylic compound represented by the following general formulas (1a) to (1h)
[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

&Lt; RTI ID = 0.0 &

[Formula 1e]

(1f)

[Formula 1g]

[Chemical Formula 1h]

.
The curable composition according to claim 4, wherein the fluorene group-containing (meth) acrylic compound is contained in an amount of 5 wt% to 85 wt%.
5. The curable composition of claim 4, wherein the composition further comprises at least one of an initiator and a crosslinker based on solids.
An optical sheet formed from the curable composition of any one of claims 4 to 7.
The optical sheet according to claim 8, wherein the optical sheet includes an optical pattern layer, and the refractive index of the optical pattern layer is 1.56 to 1.68.
An optical display device comprising the optical sheet of claim 8.
The optical display device according to claim 10, wherein the optical display device includes a first optical sheet and a second optical sheet formed on the first optical sheet,
Wherein at least one of the first optical sheet and the second optical sheet is the optical sheet of claim 8,
When the first optical sheet is formed of the optical sheet of claim 8, the optical pattern layer included in the optical sheet is formed from a curable composition containing 5 to 65% by weight of a fluorene group-containing (meth) acrylic compound,
When the second optical sheet is formed of the optical sheet of claim 8, the optical pattern layer included in the optical sheet is formed from a curable composition containing 30 to 85% by weight of a fluorene group-containing (meth) acrylic compound Lt; / RTI &gt;

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