KR100850465B1 - Brome modified acrylate resin composition having high refractive index and optical film containing the same - Google Patents

Abstract

A bromine modified acrylate resin composition and an optical film comprising the same are disclosed. The disclosed bromine modified acrylate resin composition is prepared by reacting a bromine modified poly epoxy compound containing at least one bromine atom and a half ester acrylate compound containing carboxylic acid, and includes a bromine modified acrylate having a bromine structure in its molecule; Reactive monomers having at least one vinyl group or (meth) acrylate group; And a photopolymerization initiator.

Accordingly, the disclosed bromine-modified acrylate resin composition and the optical film including the same may improve refractive index, curability, adhesion, wear resistance, and light transmittance, and reduce curling.

Description

Bromine modified acrylate resin composition having a high refractive index and an optical film comprising the same {Brome modified acrylate resin composition having high refractive index and optical film containing the same}

1 is a perspective view of a prism film prepared using a bromine-modified acrylate resin according to an embodiment of the present invention.

<Explanation of symbols for the main parts of the drawings>

10: prism film 11: base layer

12: optical layer α: angle

p: pitch

The present invention relates to a bromine-modified acrylate resin composition and an optical film comprising the same, and more particularly, to a bromine-modified acrylate resin composition having improved refractive index, curability, adhesion, abrasion resistance, and light transmittance and reduced curling. It relates to an optical film comprising the same.

Acrylate resins having a high refractive index are used in optical products such as optical lenses, optical films, or optical media. In particular, the optical film may be used in a display product such as a liquid crystal display or a plasma display panel, and among them, the optical film is mainly used for the purpose of improving the brightness of the backlight unit disposed at the rear of the liquid crystal display. For example, Korean Patent Publication No. 2001-0012340 discloses an optical product made of a polymerizable composition comprising a brominated monomer having a high refractive index. However, the bromine-based acrylate resin in the published patent has a low molecular weight and high hardness has a problem that is easily broken due to the occurrence of a crack phenomenon during coating and curing on the film. Also, in this case, there is a problem that curling (curling) phenomenon of the film tends to occur over time due to the difference in shrinkage between the coating surface and the film.

In addition, Korean Patent No. 0444824 discloses a resin composition for a prism film using fluorene acrylate. However, the prism film using the fluorene acrylate resin proposed here has many limitations in use due to the lack of abrasion resistance, hardness, toughness, adhesiveness, etc. required in the film for improving light transmittance.

An object of the present invention is to provide a bromine-modified acrylate resin composition with improved refractive index and an optical film comprising the same.

Another object of the present invention is to provide a bromine-modified acrylate resin composition having improved curability.

Still another object of the present invention is to provide a bromine-modified acrylate resin composition having improved adhesion.

Still another object of the present invention is to provide a bromine-modified acrylate resin composition having improved abrasion resistance.

Still another object of the present invention is to provide an optical film including a bromine-modified acrylate resin composition having improved light transmittance.

Still another object of the present invention is to provide an optical film including a bromine-modified acrylate resin composition having reduced curling phenomenon.

According to the invention,

A reaction product of a bromine modified poly epoxy compound containing at least one bromine atom and an acrylate compound containing a carboxylic acid, the bromine modified acrylate having a bromine structure in its molecule;

Reactive monomers having at least one vinyl group or (meth) acrylate group; And

Provided is a bromine-modified acrylate resin composition comprising a photopolymerization initiator.

According to one embodiment of the present invention, the bromine-modified poly epoxy compound has a number average molecular weight of 200 ~ 3000.

According to another embodiment of the present invention, the acrylate compound containing carboxylic acid is at least one selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid dimer, lactone modified acrylic acid, and half ester acrylate.

According to another embodiment of the invention, the half ester acrylate is a reaction product of carboxylic anhydride and hydroxy acrylate.

According to another embodiment of the present invention, the bromine modified acrylate is a catalytic reaction product of the bromine modified poly epoxy compound and the half ester acrylate compound.

According to another embodiment of the present invention, the bromine-modified acrylate resin composition, the bromine-modified acrylate resin composition 10 to 80 parts by weight, 20 to 90 parts by weight of the reactive monomer, and 0.5 to 15 parts by weight of the photopolymerization initiator Include.

Also according to the invention,

An optical film including a polymerization product of a bromine-modified acrylate resin composition according to any one of the above embodiments is provided.

According to an embodiment of the present invention, the optical film is a prism sheet or a contrast ratio enhancing film.

Also according to the invention,

A display apparatus employing an optical film according to any one of the above embodiments is provided.

Hereinafter, preferred embodiments of the present invention will be described in detail.

Bromine-modified acrylate resin composition according to an embodiment of the present invention comprises a bromine-modified acrylate, a reactive monomer, and a photopolymerization initiator.

The bromine modified acrylate has a bromine structure in the molecule, and is prepared by reacting a bromine modified poly epoxy compound containing at least one bromine atom and a half ester acrylate compound containing carboxylic acid. The bromine-modified poly epoxy compound has a bromine-based structure and has an epoxy group at its terminal, and has a number average molecular weight between 200 and 3000. In this case, when the number average molecular weight is less than 200, the cured coating film is liable to be broken when the resin composition containing the bromine-modified acrylate is coated on the substrate, and when the number average molecular weight exceeds 3000, the curing rate is slow and the surface It is not preferable because the hardness is low and the adjustment of the refractive index is not easy.

The bromine modified poly epoxy compound is mono bromo bisphenol A diglycidyl ether, dibromo bisphenol A diglycidyl ether, tribromo bisphenol A diglycidyl ether, tetra bromo bisphenol A diglycidyl Ether, pentabromo bisphenol A diglycidyl ether, hexa bromo bisphenol A diglycidyl ether, mono bromo bisphenol F diglycidyl ether, dibromo bisphenol F diglycidyl ether, tribromo bisphenol F diglycidyl ether, tetra bromo bisphenol F diglycidyl ether, penta bromo bisphenol F diglycidyl ether, hexa bromo bisphenol F diglycidyl ether, mono bromo bisphenol S diglycidyl ether , Dibromo bisphenol S diglycidyl ether, tribromo bisphenol S diglycidyl ether, tetrabromo bisphenol S diglycidyl ether, penta Lomo bisphenol S diglycidyl ether, hexa bromo bisphenol S diglycidyl ether, mono bromo hydrogenated bisphenol A diglycidyl ether, dibromo hydrogenated bisphenol A diglycidyl ether, tribromo number Amplified bisphenol A diglycidyl ether, tetra bromo hydrogenated bisphenol A diglycidyl ether, penta bromo hydrogenated bisphenol A diglycidyl ether, hexa bromo hydrogenated bisphenol A diglycidyl ether, monobro Parent Hydrogenated Bisphenol F diglycidyl ether, Dibromo Hydrogenated Bisphenol F diglycidyl ether, Tribromo Hydrogenated Bisphenol F diglycidyl ether, Tetrabromo Hydrogenated Bisphenol F diglycidyl ether, Pentabromo Hydrogenated Bisphenol F diglycidyl ether, Hexabromo Hydrogenated Bisphenol F diglycidyl ether, Monobromo Hydrogenated Bisphenol S diglycidyl ether , Dibromo hydrogenated bisphenol S diglycidyl ether, tribromo hydrogenated bisphenol S diglycidyl ether, tetra bromo hydrogenated bisphenol S diglycidyl ether, pentabromo hydrogenated bisphenol S diglyci Dyl ether, hexa bromo hydrogenated bisphenol S diglycidyl ether, or compounds thereof may be used.

As the acrylate compound, acrylic acid, methacrylic acid, acrylic acid dimer, lactone-modified acrylic acid, half ester acrylate, or a compound thereof may be used. Here, the half ester acrylate is prepared by the reaction of carboxylic anhydride and hydroxy acrylate. Examples of the carboxylic anhydride include dibasic carboxylic acids such as phthalic anhydride, maleic anhydride or hexahydrophthalic anhydride, or 3,4-dimethoxyphthalic anhydride, 4,5-dimethoxyphthalic anhydride, and 3,6-dihydride anhydride. Oxyphthalic acid, 3,6-dihydroxy-4-methylphthalic anhydride, 3,6-dimethoxy-4,5-methylene dihydroxy phthalic anhydride, 3,4-dimethyl phthalic anhydride, 3,6-dimethyl phthalic anhydride , 4,5-dimethyl phthalic anhydride, 3-methyl phthalic anhydride, 4-methyl phthalic anhydride, 3-methoxy phthalic anhydride, 4-methoxyphthalic acid, 3-methoxy-4,6-dimethyl phthalic anhydride, 4-iso Propyl-3,5,6-trimethoxy phthalic anhydride, 4-hydroxy phthalic anhydride, 3-hydroxy-4-methoxy phthalic anhydride, 3-hydroxy-5-methoxy phthalic anhydride, 6-hydroxy- 4-methoxy-3-methyl phthalic anhydride, 6-isobutyl-3,4-dimethyl phthalic anhydride, 3-propyl phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride , 2,3,3`, 4`-biphenyltetracarboxylic dianhydride, 3,3`, 4,4`-biphenyltetracarboxylic dianhydride, 3,3`, 4,4`-benzo Phenonetetracarboxylic dianhydride, bis (3,4-dicarboxylphenyl) ether dianhydride, bis (3,4-dicarboxylphenyl) methane dianhydride, methyl-3,6-endo methylenetetrahydrophthalic anhydride Or phthalic anhydride derivatives such as 3,6-endo methylenetetra hydrophthalic anhydride, or the like, or mixtures thereof may be used. The hydroxy acrylate is hydroxy ethyl acrylate, hydroxypropyl acrylate, hydroxy butyl acrylate, caprolactone modified hydroxy acrylate, glycerol diacrylate, pentaerythritol triacrylate, ethoxylated pentaerythritol Triacrylate, propoxylated pentaerythritol triacrylate, dimethylol propane triacrylate, ethoxylated dimethylol propane triacrylate, propoxylated dimethylol propane triacrylate, dipentaerythritol pentaacrylate, Sorbitol pentaacrylate, or mixtures thereof may be used.

When the bromine-modified poly epoxy compound and the half ester acrylate compound react to produce bromine-modified acrylate, a polymerization inhibitor is used. The polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, tertiary butyl catechol, para-benzoquinone, hydroquinone, phenoxyazine, butylated hydroxytoluene, pyrogallol, monotertiary-butylhydroquinone Dibutylbutyl hydroquinone, or a mixture thereof may be used, and the amount thereof is preferably 0.001 to 1.0 parts by weight based on the total weight of the reactants.

In addition, the bromine-modified acrylate may be produced by a catalytic reaction, in which case the catalyst is triethyl amine, benzyldimethyl amine, benzyltrimethyl ammonium chloride, benzyl triethyl ammonium chloride, tetramethyl ammonium chlorite, tetra butyl Ammonium chloride, tetra ethyl ammonium chloride, tetra ethyl ammonium bromide, tetra butyl ammonium bromide, or mixtures thereof can be used. The amount of the catalyst used is preferably between 0.01 to 1.0 parts by weight based on the total weight of the reactants. Here, when the amount of the catalyst used is less than 0.01 part by weight, the reaction rate is too slow and not preferable. When the amount is more than 1.0 part by weight, the reaction proceeds too vigorously and is not preferable.

In addition, various additives other than the catalyst may be used in the preparation of the bromine-modified acrylate.

Hereinafter, the bromine-modified acrylate manufacturing method will be described in detail.

First, with 1 equivalent of half ester acrylate compound containing carboxylic acid based on 1 equivalent of bromine-modified polyepoxy compound, the polymerization inhibitor and the catalyst are placed in a reactor and heated to 58-62 ° C. while stirring, and maintained for 1 hour. .

Thereafter, when the reaction is stable, the temperature is raised to 68 to 72 ° C, 78 to 82 ° C, and 88 to 92 ° C at a rate of 0.4 to 0.6 ° C / min, respectively, and then gradually maintained at each temperature for 50 to 70 minutes. The reaction is finally performed at 98 to 100 ° C. for 22 to 26 hours.

The end point of the reaction can be obtained by measuring the epoxy equivalent or the acid value, it is measured every hour to confirm the completion of the reaction.

After the reaction is completed, cooled to 58 to 62 ℃ at a rate of 2 to 3 ℃ / min, filtered and packaged.

A bromine-modified acrylate resin composition having a high refractive index of the present invention is prepared by mixing the bromine-modified acrylate, a reactive monomer, and a photopolymerization initiator. At this time, bromine-modified acrylate is used in a proportion of 10 to 80 parts by weight, 20 to 90 parts by weight of a reactive monomer, and 0.5 to 15 parts by weight of a photopolymerization initiator. If the content of the bromine-modified acrylate is less than 10 parts by weight, the refractive index is not preferable, and if it exceeds 85 parts by weight, the viscosity control is not easy, which is not preferable. In addition, if the content of the reactive monomer is less than 20 parts by weight, the curing rate is slow, which is not preferable. If it exceeds 80 parts by weight, the refractive index is low, which is not preferable. In addition, when the content of the photopolymerization initiator is less than 0.5 parts by weight, the curing is not good, and if it is more than 15 parts by weight, the curing proceeds rapidly and the curing rate is difficult to control, which is not preferable.

The reactive monomer may be a monomer having a vinyl group such as en-vinyl caprolactam. Further, the reactive monomers may be selected from benzyl acrylate, dicyclopentadiene acrylate, cyclohexyl acrylate, phenoxy ethyl acrylate, phenoxy diethylene glycol acrylate, phenoxy tetraethylene glycol acrylate, phenoxy hexaethylene glycol Monofunctional monomers such as acrylate, 4-hydroxy butyl acrylate or cyclohexane di methanol mono acrylate, neopentyl acrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, tris Oxyethyl) isocyanurate diacrylate, dimethylol tricyclodecane diacrylate or monomer with bifunctional groups such as ethylene oxide addition bisphenol A diacrylate, ethylene oxide 3 molar addition trimethylol propane triacrylic Ethylene oxide 6 mole addition type trimethylol propane triacrylate, pentaerythritol triacrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexaacrylate or caprolactone modified dipentaerythritol hexaacryl Monomers having at least trifunctional groups such as rates, or mixtures thereof.

The photopolymerization initiator is benzophenone, benzophenone derivative, benzoin, benzoin alkyl ether benzyl dimethyl ketal, 1-hydroxy cyclohexyl phenyl ketone, diethoxy acetophenone, phosphine oxide, amino acetophenone, 2-hydroxy-2 -Methyl-1-phenylpropano-1-non, 2-benzyl-2-dimethylamide-1- (4-morpholinaphenyl) -butanane, or a mixture thereof.

Hereinafter, a method of manufacturing an optical film using a bromine-modified acrylate resin composition according to an embodiment of the present invention will be described.

First, the bromine modified acrylate resin composition is apply | coated on a base film, without using a solvent.

Subsequently, the prism pattern is UV-cured while passing through the roll on which the prism pattern is etched to form the prism pattern.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments, but the present invention is not limited thereto.

Example

( Production of Bromine Modified Acrylate )

Example 1

185.6 g of toluene as solvent, 400 g of bromine-modified polyepoxy (monobromo bisphenol A diglycidyl ether) with a number average molecular weight of 400, 528 g of half ester acrylate which is a reaction product of phthalic anhydride and hydroxy ethyl acrylate, polymerization inhibitor 1.0 g of hydroquinone and 0.2 g of dimethyl benzylamine as catalysts were charged into a four-necked flask and gradually heated up to 60 ° C while stirring. When the temperature was constant, the temperature was maintained for 1 hour, and then sequentially heated to a temperature of 70 ° C., 80 ° C., and 90 ° C., and maintained at each temperature for 1 hour. Subsequently, it heated up at 100 degreeC and made it react at this temperature for 20 hours. After completion of the reaction, the vacuum was reduced to distill the toluene completely at 70 ° C.

A polymerization product of a transparent liquid, that is, 915 g of bromine-modified acrylate was obtained, with a refractive index of 1.6012.

Example 2

188 g of toluene as solvent, 400 g of bromine-modified polyepoxy (monobromo bisphenol A diglycidyl ether) having a number average molecular weight of 400, 540 g of half ester acrylate which is a reaction product of hexahydrophthalic anhydride and hydroxy ethyl acrylate, and polymerization prohibited 1.0 g of hydroquinone as a agent and 0.2 g of dimethyl benzylamine as catalysts were charged into a four-necked flask and gradually heated up to 60 ° C while stirring. When the temperature was constant, the temperature was maintained for 1 hour, and then sequentially heated to a temperature of 70 ° C., 80 ° C., and 90 ° C., and maintained at each temperature for 1 hour. Subsequently, it heated up at 100 degreeC and made it react at this temperature for 20 hours. After completion of the reaction, the vacuum was reduced to distill the toluene completely at 70 ° C.

A polymerization product of a transparent liquid, ie, bromine-modified acrylate, was obtained, at which time the refractive index was 1.5935.

Example 3

166.4 g of toluene as solvent, 400 g of bromine-modified polyepoxy (monobromo bisphenol A diglycidyl ether) having a number average molecular weight of 400, 432 g of half ester acrylate, a reaction product of succinic anhydride and hydroxy ethyl acrylate, polymerization inhibitor 1.0 g of hydroquinone and 0.2 g of dimethyl benzylamine as catalysts were charged into a four-necked flask and gradually heated up to 60 ° C while stirring. When the temperature was constant, the temperature was maintained for 1 hour, and then sequentially heated to a temperature of 70 ° C., 80 ° C., and 90 ° C., and maintained at each temperature for 1 hour. Subsequently, it heated up at 100 degreeC and made it react at this temperature for 20 hours. After completion of the reaction, the vacuum was reduced to distill the toluene completely at 70 ° C.

A polymerization product of a transparent liquid, that is, 819 g of bromine-modified acrylate, was obtained with a refractive index of 1.5823.

Example 4

235.6 g of toluene as solvent, 650 g of bromine-modified polyepoxy (monobromo bisphenol A diglycidyl ether) having a number average molecular weight of 400, 528 g of half ester acrylate which is a reaction product of phthalic anhydride and hydroxy ethyl acrylate, polymerization inhibitor 1.0 g of hydroquinone and 0.2 g of dimethyl benzylamine as catalysts were charged into a four-necked flask and gradually heated up to 60 ° C while stirring. When the temperature was constant, the temperature was maintained for 1 hour, and then sequentially heated to a temperature of 70 ° C., 80 ° C., and 90 ° C., and maintained at each temperature for 1 hour. Subsequently, it heated up at 100 degreeC and made it react at this temperature for 20 hours. After completion of the reaction, the vacuum was reduced to distill the toluene completely at 70 ° C.

A polymerization product of a transparent liquid, that is, 1152 g of bromine-modified acrylate, was obtained with a refractive index of 1.6038.

(Preparation, photocuring, and physical property measurement of bromine modified acrylate resin composition)

Examples 5-8

Bromine-modified acrylate resin compositions were obtained by mixing bromine-modified acrylate, reactive acrylate (or vinyl-based) monomers, and photopolymerization initiators obtained in Examples 1 to 4 in various ratios. The component ratio of each said composition is shown in Table 1 below. In addition, the respective compositions were cured with an ultraviolet lamp to prepare an optical film, and the physical properties of each optical film were measured and shown in Table 2 below. In addition, the physical properties of the conventional acrylate resin composition and the optical film prepared therefrom does not contain the bromine-modified acrylate of Examples 1 to 4 are shown in Table 1 and Table 2 as Comparative Example 1.

Table 1 Composition ratio of acrylate resin composition

Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Compounding ratio (part by weight) Compound of Example 1 100 - - - - Compound of Example 2 - 100 - - - Compound of Example 3 - - 100 - - Compound of Example 4 - - - 100 - RDX-51027 (Note 1) - - - - 100 N-vinyl caprolactam 20 20 20 20 20 Phenoxy ethyl acrylate 20 20 20 20 20 Benzyl acrylate 10 10 10 10 10 TPO (Note 2) 3 3 3 3 3 Irgacure-184 (Note 3) 3 3 3 3 3

(Note 1) Bromine acrylate of Cytec Co., Ltd.

(Note 2) Photoinitiator: 2,4,6-trimethyl benzoyl phosphine oxide

(Note 2) Photoinitiator: 1-hydroxy cyclohexyl phenyl ketone

Table 2 Physical Properties of Optical Films Prepared with an Acrylate Resin Composition

Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Refractive Index (25 Degrees) 1.5630 1.5611 1.5584 1.5602 1.5532 Curability (mJ / cm ² ) 200 200 200 200 250 Pencil hardness H H F H F Adhesion 100/100 100/100 100/100 100/100 85/100 Abrasion Resistance (mg) 19 22 27 35 68 Curling property Good Good Very good Good Bad

The physical properties of the optical films prepared from the compositions of Examples 5 to 8 and Comparative Example 1 were measured or evaluated by the following method.

1) Refractive index: Using a Atago 3T, the Abe Refractometer, manufactured by Atago, the readings with the same scale were read up to the fourth decimal place.

2) Curability: The energy required to cure the coating layer was calculated with an ultraviolet curing device composed of 120W high pressure mercury lamp after coating with a thickness of 20 microns on a 200 x 200 mm PET sheet.

3) Pencil Hardness: The tip of the pencil was flattened with sandpaper 400 and the edges were sharpened. Thereafter, the pencil was applied to the test surface of the optical film with a 1Kg load at an inclination of 45 degrees, and then moved closely by about 30 mm in length at a speed of about 3 mm / sec in the direction of the pencil lead. Then, repeating the above procedure five times per pencil of the same hardness while changing the position of the scratch, wipe the graphite of the pencil attached to each test surface of the optical film with a rubber eraser or gauze to examine the groove state of the test surface It was. In this case, 5 times of soft pencils should be used to ensure that there are no more than 3 scratches. The total running length is 30mm, and 10mm from the beginning of each line is excluded from the judgment. The hardness of the pencil is higher in order of 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, and 6H.

4) Adhesiveness: Draw 11 horizontal lines and vertical lines with a line spacing of 1.5mm on the coated surface of PET film so that the number of cells becomes 100 spaces, and then attach 3M cello tape No. 600 and immediately remove it. It was measured by counting the number (ASTM D3359).

5) Abrasion resistance (mg): Wear resistance was measured by applying 500g load to abrading wheel and rotating 100 cycles by using Taber's Taber abraser and measuring the weight (mg) that was reduced due to wear. The smaller the weight, the better the wear resistance.

6) Curling property: After coating the photocurable resin on the PET film, and cured using UV, it was cut into a square of 100 ㅧ 100mm size. After cutting to the point of 20mm at both corners in the diagonal direction of the film (X-shaped ablation), it was left for 30 minutes in a drying oven at a temperature of 150 ℃ so that both sides of the film do not touch the floor. Thereafter, the film was placed on a flat plate, and the height of the highest portion of the film that was raised from the bottom was measured.

(Production of Prism Film Using Bromine Modified Acrylate Resin Composition and Its Physical Properties)

Examples 9-12

Using the bromine-modified acrylate resin composition of Examples 1 to 4, as shown in FIG. 1, triangular prism films 10 having an angle α of 90 degrees and a pitch p of 50 μm were manufactured. In addition, the results of measuring the luminance by employing each of the prism films 10 in the luminance meter are shown in Table 3 below. In FIG. 1, the prism film 10 includes a base layer 11 made of a PET film and the like, and an optical layer 12 made of a bromine-modified acrylate resin composition. In addition, using the acrylate resin composition of Comparative Example 1, a triangular prism film having an angle of 90 degrees and a pitch of 50 μm was produced, similar to that of FIG. 1, and the luminance was measured by employing the prism film in a luminance meter. One result is shown in Table 3 below.

Table 3 Physical Properties of Prismatic Films Made of an Acrylate Resin Composition

Example 9 Example 10 Example 11 Example 12 Comparative Example 2 Luminance (nit) 3923 3892 3805 3839 3790 Relative luminance ratio (% of comparative example) 103.5 102.7 100.4 101.3 100

1) Luminance: The produced prism film was cut into a 19-inch sheet, and employed in Topcon's SR3 spectro radiometer, and the luminance was measured. The prism film was placed on a diffuser film of a 19 inch panel, and luminance of 25 points was measured in the front direction and used as an average value.

2) Relative luminance ratio: The relative luminance ratio was calculated by dividing each of the luminance of Examples 9 to 12 by the luminance of Comparative Example 2.

Bromine-modified acrylate resin composition having the above configuration has a higher refractive index than the conventional acrylate resin, excellent adhesion to various substrates, high hardness and excellent wear resistance. In addition, since the composition has excellent light transmittance and hardness, when the optical film is manufactured using the composition, the hardness is increased and the luminance of the display device is increased as compared with the case of using the conventional acrylate resin composition. In addition, the composition is not only optical films such as industrial optical lenses used for cameras, copiers, printers, optical lenses for eyeglass materials, and display devices such as LCDs, but also optical films such as prism sheets or contrast ratio enhancement films, as well as plastic hard coating materials and various It can also be used as a coating material.

Although the present invention has been described with reference to the examples, these are merely exemplary, and those skilled in the art will understand that various modifications and equivalent other embodiments are possible therefrom. Therefore, the true technical protection scope of the present invention will be defined by the technical spirit of the appended claims.

According to the present invention, an improved refractive index bromine-modified acrylate resin composition and an optical film including the same may be provided.

In addition, according to the present invention, an improved bromine-modified acrylate resin composition may be provided.

In addition, according to the present invention, an improved bromine-modified acrylate resin composition may be provided.

In addition, according to the present invention, an improved wear resistance bromine modified acrylate resin composition may be provided.

In addition, according to the present invention, an optical film including a bromine-modified acrylate resin composition with improved light transmittance may be provided.

In addition, according to the present invention, an optical film including a bromine-modified acrylate resin composition with reduced curling may be provided.

Claims (16)

A reaction product of a bromine modified poly epoxy compound containing at least one bromine atom and an acrylate compound containing a carboxylic acid, the bromine modified acrylate having a bromine structure in its molecule; Reactive monomers having at least one vinyl group or (meth) acrylate group; And Bromine-modified acrylate resin composition comprising a photopolymerization initiator. The method of claim 1, The bromine-modified poly epoxy compound has a bromine-modified acrylate resin composition, characterized in that the number average molecular weight is 200 ~ 3000. The method of claim 1, The bromine modified poly epoxy compounds include mono bromo bisphenol A diglycidyl ether, dibromo bisphenol A diglycidyl ether, tribromo bisphenol A diglycidyl ether, tetrabromo bisphenol A diglycidyl ether , Pentabromo bisphenol A diglycidyl ether, hexa bromo bisphenol A diglycidyl ether, mono bromo bisphenol F diglycidyl ether, dibromo bisphenol F diglycidyl ether, tribromo bisphenol F Diglycidyl ether, tetra bromo bisphenol F diglycidyl ether, penta bromo bisphenol F diglycidyl ether, hexa bromo bisphenol F diglycidyl ether, mono bromo bisphenol S diglycidyl ether, Dibromo bisphenol S diglycidyl ether, tribromo bisphenol S diglycidyl ether, tetrabromo bisphenol S diglycidyl ether, pentab Lomo bisphenol S diglycidyl ether, hexa bromo bisphenol S diglycidyl ether, mono bromo hydrogenated bisphenol A diglycidyl ether, dibromo hydrogenated bisphenol A diglycidyl ether, tribromo number Amplified bisphenol A diglycidyl ether, tetra bromo hydrogenated bisphenol A diglycidyl ether, penta bromo hydrogenated bisphenol A diglycidyl ether, hexa bromo hydrogenated bisphenol A diglycidyl ether, monobro Parent Hydrogenated Bisphenol F diglycidyl ether, Dibromo Hydrogenated Bisphenol F diglycidyl ether, Tribromo Hydrogenated Bisphenol F diglycidyl ether, Tetrabromo Hydrogenated Bisphenol F diglycidyl ether, Penta bromo hydrogenated bisphenol F diglycidyl ether, hexa bromo hydrogenated bisphenol F diglycidyl ether, mono bromo hydrogenated bisphenol S diglycidyl ether, Dibromo Hydrogenated Bisphenol S diglycidyl ether, Tribromo Hydrogenated Bisphenol S diglycidyl ether, Tetrabromo Hydrogenated Bisphenol S diglycidyl ether, Pentabromo Hydrogenated Bisphenol S diglycidyl Bromine-modified acrylate resin composition, characterized in that at least one selected from the group consisting of ether, and hexa bromo hydrogenated bisphenol S diglycidyl ether. The method of claim 1, The carboxylic acid-containing acrylate compound is bromine-modified acrylate resin composition, characterized in that at least one selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid dimer, lactone modified acrylic acid, and half ester acrylate. The method of claim 4, wherein The half ester acrylate is bromine-modified acrylate resin composition, characterized in that the reaction product of carboxylic anhydride and hydroxy acrylate. The method of claim 5, The carboxylic acid anhydride is a dibasic carboxylic acid of phthalic anhydride, maleic anhydride or hexahydrophthalic anhydride, or 3,4-dimethoxyphthalic anhydride, 4,5-dimethoxyphthalic anhydride, 3,6-dihydroxyphthalic anhydride, 3,6-dihydroxy-4-methylphthalic anhydride, 3,6-dimethoxy-4,5-methylene dihydroxy phthalic anhydride, 3,4-dimethyl phthalic anhydride, 3,6-dimethyl phthalic anhydride, 4, 5-dimethylphthalic anhydride, 3-methylphthalic anhydride, 4-methylphthalic anhydride, 3-methoxyphthalic anhydride, 4-methoxyphthalic acid, 3-methoxy-4,6-dimethylphthalic anhydride, 4-isopropyl-3 , 5,6-trimethoxy phthalic anhydride, 4-hydroxy phthalic anhydride, 3-hydroxy-4-methoxy phthalic anhydride, 3-hydroxy-5-methoxy phthalic anhydride, 6-hydroxy-4-meth Methoxy-3-methyl phthalic anhydride, 6-isobutyl-3,4-dimethyl phthalic anhydride, 3-propyl phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,3,3`, 4`- Biphenyltetracarboxylic dianhydride, 3,3`, 4,4`-biphenyltetracarboxylic dianhydride, 3,3`, 4,4`-benzophenonetetracarboxylic dianhydride, bis (3 , 4-dicarboxylphenyl) ether dianhydride, bis (3,4-dicarmoxylphenyl) methane dianhydride, methyl-3,6-endo methylenetetrahydrophthalic anhydride or 3,6-endomethylenetetrahydro anhydride A bromine-modified acrylate resin composition, which is a phthalic anhydride derivative of phthalic acid or a mixture of the dibasic carboxylic acid and the phthalic anhydride derivative. The method of claim 5, The hydroxy acrylate is hydroxy ethyl acrylate, hydroxypropyl acrylate, hydroxy butyl acrylate, caprolactone modified hydroxy acrylate, glycerol diacrylate, pentaerythritol triacrylate, ethoxylated pentaerythritol tri Acrylate, propoxylated pentaerythritol triacrylate, dimethylol propane triacrylate, ethoxylated dimethylol propane triacrylate, propoxylated dimethylol propane triacrylate, dipentaerythritol pentaacrylate, and Bromine-modified acrylate resin composition, characterized in that at least one selected from the group consisting of sorbitol pentaacrylate. The method of claim 1, The bromine-modified acrylate is a bromine-modified acrylate resin composition, characterized in that the reaction product of the bromine-modified poly epoxy compound and the acrylate compound containing the carboxylic acid. The method of claim 8, The reaction product is triethyl amine, benzyldimethyl amine, benzyltrimethyl ammonium chloride, benzyl triethyl ammonium chloride, tetra methyl ammonium chlorite, tetra butyl ammonium chloride, tetra ethyl ammonium chloride, tetra ethyl ammonium bromide, and tetra butyl ammonium bromide Bromine-modified acrylate resin composition, characterized in that produced by the reaction using at least one selected from the group consisting of a catalyst. The method of claim 1, The reactive monomer is bromine-modified acrylate resin composition, characterized in that the en-vinyl caprolactam. The method of claim 1, The reactive monomers include benzyl acrylate, dicyclopentadiene acrylate, cyclohexyl acrylate, phenoxy ethyl acrylate, phenoxy diethylene glycol acrylate, phenoxy tetraethylene glycol acrylate, phenoxy hexaethylene glycol acrylate , Monomer having one functional group of 4-hydroxy butyl acrylate or cyclohexane di methanol mono acrylate, neopentyl acrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, tris (2-hydroxyethyl) iso Monomers having a bifunctional group of cyanurate diacrylate, dimethylol tricyclodecane diacrylate or ethylene oxide addition bisphenol A diacrylate, and ethylene oxide 3 mole addition trimethylol propane triacrylate, ethylene jade At least 6 side molar addition type trimethylol propane triacrylate, pentaerythritol triacrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexa acrylate or caprolactone modified dipentaerythritol hexa acrylate Bromine-modified acrylate resin composition, characterized in that at least one selected from the group consisting of monomers having a tri-functional group. The method of claim 1, The photopolymerization initiator is benzophenone, benzophenone derivative, benzoin, benzoin alkyl ether benzyl dimethyl ketal, 1-hydroxy cyclohexyl phenyl ketone, diethoxy acetophenone, phosphine oxide, amino acetophenone, 2-hydroxy-2 Bromine modification, characterized in that at least one selected from the group consisting of -methyl-1-phenylpropano-1-non, and 2-benzyl-2-dimethylamide-1- (4-morpholinaphenyl) -butanane Acrylate resin composition. The method of claim 1, A bromine modified acrylate resin composition comprising 10 to 80 parts by weight of the bromine modified acrylate resin composition, 20 to 90 parts by weight of the reactive monomer, and 0.5 to 15 parts by weight of the photopolymerization initiator. An optical film comprising a polymerization product of a bromine-modified acrylate resin composition according to any one of claims 1 to 13. The method of claim 14, An optical film, which is in the form of a prism sheet or a contrast ratio enhancing film. Display apparatus employing the optical film according to claim 14.

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