KR20100070110A - (meth)acrylate compound, uv curable resin composition using the same, optical film and optical product - Google Patents

Abstract

PURPOSE: A (meth)acrylate compound, a UV-curable resin composition including thereof, and an optical element and an optical film using thereof are provided to secure the quality of optical products, and to improve the transparency, the refractive index, and the surface hardness. CONSTITUTION: A (meth)acrylate compound is marked with chemical formula 1. In the chemical formula 1, X and Y are O or S, respectively. R is either hydrogen or methyl. R1 is either a substituted or non-substituted aryl group with C1~C20, an arylalkyl group, or a heteroaryl group. R2 is selected from the group consisting of phenyl, naphthyl, aryl, aryl(C1-C6 alkylene)-, the heteroaryl, or heteroaryl(C1-C6 alkylene)-. N is an integer selected from 1~10.

Description

(Meth) acrylate compound, photocurable resin composition comprising the same, optical film and optical device using the same {(Meth) acrylate Compound, UV Curable Resin Composition using the Same, Optical Film And Optical Product}

The present invention relates to a (meth) acrylate compound, a photocurable resin composition comprising the same, an optical film and an optical device using the same, and more particularly, when used in a photocurable resin composition, Meta) acrylate compounds and photocurable resin compositions which are cured rapidly by irradiation with ultraviolet rays, including those, particularly photocurable resin compositions useful for producing optical components such as lenses, optical discs, prisms and lens sheets in mold polymerization It is about. The photocurable resin composition according to the invention is also suitable for use as a surface coating material of plastic film substrates used in optical materials such as light management films.

In backlighting computer displays or other display systems, optical films are commonly used to guide light. For example, in a backlit display, the light management film uses prismatic structures (also sometimes referred to as microstructures) to guide light along the viewing axis (ie, the axis substantially perpendicular to the display).

Inducing light improves the brightness of the display seen by the user and allows the system to consume less power to achieve the desired on-axis illuminance level. Films for turning or directing light can also be used in a wide variety of other optical designs, such as projection displays, traffic signals and illuminated signs.

The composition used to prepare the light management film for guiding light preferably has the ability to simulate the microstructures necessary to provide light induction upon curing. It is also desirable that the glass transition temperature (Tg) of the cured composition is high enough to retain shape during storage and use. It is also desirable for the light management film made of the cured composition to exhibit high brightness. Finally, the composition used to make the light management film advantageously has a high refractive index.

There are a variety of materials currently available for light management films, but there is a continuing need to meet increasingly stringent requirements for the materials used to make such films, especially for light management film applications in curing.

Accordingly, an object of the present invention is to provide a novel (meth) acrylate compound capable of securing a high refractive index when applied to a photocurable resin composition.

In addition, the present invention includes the (meth) acrylate compound, and has another object to provide a photocurable resin composition having high transparency, refractive index and surface hardness of a cured product, and excellent productivity, dimensional accuracy, and heat resistance.

Furthermore, another object of the present invention is to provide an optical film manufactured using the photocurable resin composition.

Another object of the present invention to provide an optical device having the optical film.

The present invention for achieving the above object provides a (meth) acrylate compound, characterized by the following formula (1).

(Formula 1)

(In Formula 1, X and Y are each independently O or S, R is hydrogen or methyl, R ₁ is substituted or unsubstituted C ₁ -C ₂₀ aryl, arylalkyl or heteroaryl, and R ₂ is phenyl , Naphthyl, aryl, aryl (C ₁ -C ₆ alkylene)-, heteroaryl or heteroaryl (C ₁ -C ₆ alkylene)-, each of which is halogen, C ₁ -C ₄ alkyl, C _1- Substituted with 0 to 5 substituents independently selected from C ₄ alkoxy, (C ₁ -C ₄ alkyl) S-, C ₁ -C ₄ haloalkyl and C ₁ -C ₄ haloalkoxy, n is an integer from 1 to 10 to be.)

In addition, the present invention provides a photocurable resin composition comprising a (meth) acrylate compound (A) represented by the formula (1).

The photocurable resin composition may include a polyfunctional (meth) acrylate oligomer (B), a (meth) acrylate monomer (C) and a photoinitiator (D).

It is preferable that the refractive index of the (meth) acrylate compound (A) represented by the said Formula (1) is 1.55 or more at 25 degreeC.

The (meth) acrylate compound (A) represented by Formula 1 may be included in an amount of 5 to 85 parts by weight based on 100 parts by weight of the total composition. The multifunctional (meth) acrylate oligomer (B) may have a polyfunctional (refractive index of 1.53 or more) It is preferable to include a meth) acrylate oligomer.

The polyfunctional (meth) acrylate oligomer (B) preferably contains 10 to 70 parts by weight based on 100 parts by weight of the total composition.

It is preferable that the said (meth) acrylate monomer (C) contains the low viscosity (meth) acrylate monomer whose refractive index is 1.50 or more and 25 degreeC viscosity is 1-500 cps.

The low viscosity (meth) acrylate monomer preferably contains 1 to 60 parts by weight based on 100 parts by weight of the total composition. The photoinitiator (D) may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total composition.

In order to achieve another object of the present invention, the present invention provides an optical film, characterized in that is prepared using the photocurable resin composition.

The optical film may be provided with a microstructure pattern on one surface or both surfaces.

The optical film may be prepared by putting the photocurable resin composition in a mold capable of forming a microstructure pattern on one or both surfaces thereof and curing the same.

In addition, the optical film may be prepared by applying the photocurable resin composition on one side or both sides, and then curing it by passing through a casting drum having an intaglio pattern disc of a microstructure.

In order to achieve another object of the present invention, the present invention provides an optical device comprising the optical film.

Preferably, the optical element is a display device. In this case, the optical film may be used as a brightness enhancing film.

In addition, the optical element is characterized in that the lighting device. In this case, the optical film may be used as a light conduit film.

As the photocurable resin composition according to the present invention includes the (meth) acrylate compound represented by the formula (1), it is possible to maintain the performance of the optical product well, high transparency, high refractive index and surface hardness of the cured product, productivity, dimensions It shows the characteristic which is excellent in precision and heat resistance.

The photocurable resin composition according to the invention is thus combined with a liquid crystal backlighting display, a projection display, a traffic signal, an illumination sign, an optical lens, a fresnel lens, an optical disc, a diffusion film, a holographic substrate, a conventional lens, a prism or a mirror. There is an effect that can be usefully applied to the manufacture of optical products such as light management film (LMF) for use as a substrate.

Hereinafter, the present invention will be described in more detail. Since the following description is a detailed description of one embodiment, the scope of the rights defined by the claims is not limited, even if there is a assertive, limited expression.

The present invention provides a (meth) acrylate compound represented by the following formula (1).

(Formula 1)

(In Formula 1, X and Y are O or S, R is hydrogen or methyl group, R ₁ is substituted or unsubstituted C ₁ -C ₂₀ aryl, arylalkyl or heteroaryl, R ₂ is phenyl, naphthyl, Aryl, aryl (C ₁ -C ₆ alkylene)-, heteroaryl or heteroaryl (C ₁ -C ₆ alkylene)-, each of which is halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, (C ₁ -C ₄ alkyl) substituted with 0 to 5 substituents independently selected from S-, C ₁ -C ₄ haloalkyl and C ₁ -C ₄ haloalkoxy, n is an integer from 1 to 10.)

The (meth) acrylate compound of Formula 1 reacts an aryl compound including an intramolecular carboxylic acid group with a compound having an epoxide under a triphenylphosphine catalyst to form a (meth) acrylate ester bond using (meth) acrylic acid. It can be prepared by the formation and can be represented by the following scheme 1.

(Scheme 1)

In Scheme 1, X and Y are O or S, R is hydrogen or methyl, R ₁ is substituted or unsubstituted C ₁ -C ₂₀ aryl, arylalkyl or heteroaryl, and R ₂ is phenyl, naphthyl, aryl , Aryl (C ₁ -C ₆ alkylene)-, heteroaryl or heteroaryl (C ₁ -C ₆ alkylene)-, each of which is halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, ( C ₁ -C ₄ alkyl) S-, C ₁ -C ₄ haloalkyl and C ₁ -C ₄ haloalkoxy are substituted with 0 to 5 substituents independently selected from n and n is an integer from 1 to 10.

Here, as the aryl compound containing a carboxylic acid group, it is more preferable to use an aryl compound containing two or more carboxylic acid groups in a molecule. Talic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, melic acid, 2-methoxyisophthalic acid, arc Morphthalic acid, 1,3-phenylenediacetic acid, 4-carboxyphenoxyacetic acid, 1,4-phenylenenedipropic acid, 4,4'-oxybisbenzoic acid, 4,4'-thiobisbenzo Iqic acid, 4,4'-isopropylenebisbenzoic acid, 4,4'-carbonylbisbenzoic acid, 4,4'-oxybisdibenzoic acid, 4,4'-thiobisdibenzoic acid, 4,4 ' -Biphenyldicarboxylic acid, diphenic acid, 2,2'-dithiosalicylic acid, 5,5'-dithiobis (2-nitrobenzoic acid), pamoic acid, 1,4-naphthalene Carboxylic acid, or the like can be used 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4,5,8-naphthalene tetracarboxylic acid.

Epoxide in Scheme 1 is prepared by the reaction of epichlorohydrin with an aromatic nucleophile, in particular in the presence of a base can be prepared by reacting an aromatic nucleophile with epichlorohydrin, the molar ratio of nucleophile to epichlorohydrin about 2 It can be produced by reacting with 1: 1.

The (meth) acrylate compound represented by Chemical Formula 1 according to the present invention may have a high refractive index, and thus may be usefully used in a photocurable resin composition applied to an optical component material.

Therefore, this invention provides the photocurable resin composition containing the (meth) acrylate compound (A) represented by the said General formula (1). More preferably, the photocurable resin composition is a (meth) acrylate compound (A), a polyfunctional (meth) acrylate oligomer (B), a (meth) acrylate monomer (C) and a photoinitiator ( D).

(A) Methaacrylate compound of formula (1)

Since the structure of the methacrylate compound (A) represented by the formula (1) is as described above, a detailed description of the structure will be omitted.

Among the (meth) acrylate compounds (A) represented by the above formula (1), it is preferable to use a photocurable resin composition according to the present invention having a refractive index of 1.55 or more at 25 ° C. in order to obtain high refractive index characteristics.

The (meth) acrylate compound (A) is preferably contained 5 to 85 parts by weight based on 100 parts by weight of the total curable resin composition, when the addition amount is less than 5 parts by weight, it is difficult to meet the expectation of improving the refractive index, When the added amount is more than 85 parts by weight, it is difficult to achieve sufficient surface hardness improvement.

(B) polyfunctional (meth) acrylate oligomer

The photocurable resin composition according to the present invention includes a polyfunctional (meth (acrylate oligomer (B)). The (meth) acrylate oligomer (B) includes a polyfunctional (meth) acrylate having a refractive index of 1.53 or more, and specifically Examples include (meth) acrylic acid or hydroxy substituted (meth) acrylates with di-epoxides such as bisphenol-A diglycidyl ether; bisphenol-F diglycidyl ether; tetrabromo bisphenol-A diglyci Dyl ether; tetrabromo bisphenol-F diglycidyl ether; 1,3-bis- {4- [1-methyl-1- (4-oxiraylmethoxy-phenyl) -ethyl] -phenoxy} -propane -2-ol; 1,3-bis {2,6-dibromo-4- [1- (3,5-dibromo-4-oxiranylmethoxy-phenyl) -1-methyl-ethyl] -phenoxy } -Propan-2-ol; 1- (3- (2- (4-((oxirane-2-yl) methoxy) phenyl) propan-2-yl) phenoxy) -3- (4- (2 -(4-((oxirane-2-yl) methoxy) phenyl) propan-2-yl) phenoxy) propan-2-ol Any one or a compound selected from the compound produced by the combination reaction thereof can be used.Examples of the compound produced by the combination reaction include acrylic acid 3- (4- {1- [4- (3-acrylo) Yloxy-2-hydroxy-propoxy) -3,5-dibromo-phenyl] -1-methyl-ethyl} -2,6-dibromo-phenoxy) -2-hydroxy-propyl ester; acrylic acid 3 -[4- (1- {4- [3- (4- {1- [4- (3-Acryloyloxy-2-hydroxy-propoxy) -3,5-dibromo-phenyl] -1 -Methyl-ethyl} -2,6-dibromo-phenoxy) -2-hydroxy-propoxy] -3,5-dibromo-phenyl} -1-methyl-ethyl) -2,6-dibromo- Phenoxy] -2-hydroxy-propyl ester, 2,2-bis (4- (2- (meth) acryloxyethoxy) phenyl) propane, 2,2-bis ((4- (meth) acryloxy ) Phenyl) propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytriethoxyphenyl) prop Lophane, 2,2-bis (4- (meth) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypentaethoxyphenyl) propane, 2 , 2-bis (4- (meth) acryloyloxyethoxy-3,5-dibromophenyl) propane, 2,2-bis (4- (meth) acryloyloxydiethoxy-3,5 Dibromophenyl) propane, bis (4- (meth) acryloyloxypentaethoxy-3,5-dibromophenyl) propane, bis (4- (meth) acryloyloxyphenyl) methane, Bis (4- (meth) acryloyloxyethoxyphenyl) methane, bis (4- (meth) acryloyloxydiethoxyphenyl) methane, bis (4- (meth) acryloyloxytrie Methoxyphenyl) methane, bis (4- (meth) acryloyloxytetraethoxyphenyl) methane, bis (4- (meth) acryloyloxypentaethoxyphenyl) methane, bis (4- (meth ) Acryloyloxydiethoxyphenyl) sulfone, bis (4- (meth) acryloyloxypentaethoxyphenyl) sulfone, Bis (4- (meth) acryloyloxydiethoxyphenyl) sulfide, bis (4- (meth) acryloyloxypentaethoxyphenyl) sulfide, bis (4- (meth) acryloyloxydiethoxy -3,5-dimethylphenyl) sulfide, bis (4- (meth) acryloyloxypentaethoxy-3,5-dimethylphenyl) sulfide, and the like.

The polyfunctional (meth) acrylate oligomer (B) is preferably contained 10 to 70 parts by weight based on 100 parts by weight of the total curable resin composition, when the content is less than 10 parts by weight, it is difficult to obtain the desired refractive index, the content is If it exceeds 70 parts by weight, the initial color coordinates may deteriorate.

(C) (meth) acrylate monomer

The (meth) acrylate monomer (C) is contained in the photocurable resin composition which concerns on this invention. The (meth) acrylate monomer (C) is used to lower the viscosity for the composition and includes a low viscosity (meth) acrylate having a refractive index of 1.5 or more and a viscosity of 1 to 500 cps at 25 ° C.

More specifically, the low viscosity (meth) acrylate is 2-hydroxy-3- (o-phenylphenoxy) propyl acrylate, 2-hydroxy-3- (m-phenylphenoxy) propyl acrylate, 2 -Hydroxy-3- (p-phenylphenoxy) propyl acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, neopentyl glycol benzoate (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate and 2-phenylsulfanylethyl (meth) acrylate, 2-naphthoxyethyl (meth) acrylate, 1-naphthoxyethyl At least 1 sort (s) chosen from the group which consists of (meth) acrylate and cumylethyl (meth) acrylate can be used.

Since the (meth) acrylate monomer (C) is preferably 1 to 60 parts by weight based on 100 parts by weight of the total curable resin composition, when the content is less than 1 part by weight, it is difficult to expect a sufficient viscosity drop, and the content is 60 parts by weight. If it exceeds, there is a problem that the refractive index falls.

(D) photoinitiator

The photocurable resin composition which concerns on this invention contains a photoinitiator (D). As said photoinitiator (D), it can select and use from what is generally used in the said field | area. In particular, a benzene ether, benzyl ketal, alpha hydroxy alkylphenone, amino alkyl phenone, phosphine oxide can be used. For example, 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1, diphenyl ketone benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-1- On, 4-hydroxy cyclophenyl ketone, dimethoxy-2-phenylatetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-knoloacetophenone, 4,4- Dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenyl-phosphineoxide, bis (2,9-dimethoxybenzoyl)- 2,4,4-trimethylpentylphosphine oxide or bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like can be used alone or in combination. Preferably, it is preferable to use two or more photoinitiators by selecting one or more from the group of benzene ethers, benzyl ketals, alpha hydroxy alkyl phenones, and amino alkyl phenone initiators, and one from phosphine oxides.

The photoinitiator is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the total photocurable resin composition, the content is less than 0.1 parts by weight of the curing rate is slow, if the content exceeds 10 parts by weight there is a problem that the yellowing phenomenon is severe.

To the photocurable resin composition according to the present invention described above, additives added to a conventional photocurable resin composition can be further added within a range that does not change the characteristics of the present invention. For example, silicone modification or fluorine modification additives may be included to impart releasability with the polymeric mold. These additives are commercially available products such as BYK-323, BYK-331, BYK-333, BYK-337, BYK-373, BYK-375, BYK-377, BYK-378, Daegu's TEGO Glide 410, TEGO Glide 411, TEGO Glide 415, TEGO Glide 420, TEGO Glide 432, TEGO Glide 435, TEGO Glide 440, TEGO Glide 450, TEGO Glide 455, TEGO Rad 2100, TEGO Rad 2200N, TEGO Rad 2250, TEGO Rad 2300, TEGO Rad 2500, 3M's FC-4430, FC-4432 and the like can be used.

The curable composition according to the present invention can be prepared by simply blending the components of the composition while efficiently mixing the aforementioned components to produce a homogeneous mixture. When preparing a product from the curable composition, it is often desirable to remove bubbles by applying vacuum or the like with gentle heating if the mixture is viscous. The curable resin composition according to the present invention comprising the above-mentioned components has a refractive index of at least about 1.50, in particular at least about 1.53, more particularly at least about 1.55 as the (meth) acrylate compound represented by the formula (1) having a particularly high refractive index is included. It may be abnormal.

According to the present invention, there is provided an optical film produced using the curable resin composition according to the present invention described above. At this time, the optical film is preferably formed with a microstructure pattern on one side or both sides.

Forming a microstructure pattern on one surface or both surfaces of the optical film may be made in various ways.

For example, the optical film may be prepared by putting the curable resin composition into a mold capable of forming a microstructure pattern on one or both surfaces thereof and curing the same.

Thereafter, ultraviolet rays are irradiated on the surface opposite to the substrate coated with the curable resin composition to cure the curable resin composition. This method is particularly suitable for producing optical films in which microstructure patterns are continuously formed on one or both sides of a substrate.

At this time, in order to harden the photocurable resin composition which concerns on this invention, it can harden | cure using UV ray. The wavelength of the UV rays may be about 1800 to about 4000 kHz. Suitable wavelengths of UV rays include, for example, UVA, UVB, UVC, UVV, and the like, and their wavelengths are well known in the art. Lamp systems used to generate such radiation include ultraviolet lamps and discharge lamps (eg, xenon, metal halides, metal arcs, low or high pressure mercury vapor discharge lamps, etc.). Curing means both polymerization and crosslinking to form a non-tacky material.

The above optical film can be used in various optical elements. Optical elements to which the optical film can be applied include, for example, backlighting displays, projection displays, traffic signals, lighting signs, optical lenses, fresnel lenses, optical discs, diffuser films, holographic substrates, conventional lenses, prisms or mirrors. It can be used in the substrate in combination with.

In particular, the optical film may be usefully used as a brightness enhancing film for the purpose of enhancing the brightness in the display device among the optical elements. In addition, the optical film is a light conduit film (light path pipe) which is a device for illumination among optical elements It can be usefully used.

1 illustrates an example in which an optical film is applied to a display device, but the present invention is not limited thereto.

As shown in FIG. 1, the backlighting liquid crystal display device 10 includes an optical film 11. The optical film 11 is shown to be located between the diffuser 12 and the liquid crystal display panel 14. The backlighting liquid crystal display also has a light source 16, such as a fluorescent lamp, a light path 18 for transporting light to reflect toward the liquid crystal display panel 14, and a white reflector for reflecting light toward the liquid crystal display panel 14 as well. (17). The optical film 11 increases the luminous intensity of the liquid crystal display panel 14 by aiming the light emitted from the light path 18, thereby producing a sharper image by the liquid crystal display panel, and for generating the selected luminous intensity. The power of the light source 16 can be reduced.

In this case, the optical film 11 includes a series of prisms 21 exemplified by triangular prisms 22, 24, 26, 28, as shown in FIG. 2. For example, each prism has a first face 30 and a second face 32. Prisms 22, 24, 26, 28 are formed on substrate 34 having a first surface 36 on which the prism is formed and a substantially flat or planar second surface 38 opposite the first surface.

The backlighting liquid crystal display device 10 including the optical film described above may be usefully applied to devices such as computers, personal televisions, video recorders, mobile communication equipment, and automobile and aircraft instrument displays.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention, it is obvious to those skilled in the art that the scope of the present invention is not limited to these examples.

Synthesis Example 1 Synthesis of Phthalic Acid 1- (2-hydroxy-4-phenylsulfanylbutyl) ester 2- (2-hydroxy-3-phenylsulfanylpropyl) ester

In a 1000 ml flask equipped with a mechanical stirrer, a water bath, an addition funnel, a water-jet condenser, and a sparge, 177.5 g of phthalic acid, 321 g of thiophenolglycidyl ether, 1 g of triphenylphosphine, and Semi-Grade GP 0.5 Join g and react at 90 ° C. for about 5 hours. The end point of the reaction was determined to be 2 mgKOH / g or less by measuring the acid value.

Synthesis Example 2 Synthesis of Phthalic Acid 1- (2-acryloyloxy-4-phenylsulfanylbutyl) ester 2- (2-acryloyl-3-phenylsulfanylpropyl) ester

135 g phthalic acid 1- (2-hydroxy-4-phenylsulfa prepared in Synthesis Example 1 above in a 1000 ml flask equipped with a mechanical stirrer, oil bath, addition funnel, Deanstock, water-spray condenser and air bubbler Nylbutyl) ester 2- (2-hydroxy-3-phenylsulfanylpropyl) ester, 90 mL acrylic acid, 12 g sulfuric acid, 1 g hydroquinone, 500 mL toluene were added sequentially. The reaction starts at 90 ° C. while bubbling air into the solution. Water produced during the reaction is recovered via Deanstock. The reaction was terminated by calculating the number of moles of water recovered from Dean Stark. After completion of the reaction, the contents of the flask were poured into a separating funnel with distilled water and 300 mL toluene. The aqueous layer was removed and the organic layer was washed with water, diluted sodium hydroxide until the organic layer and the aqueous layer were relatively transparent. The organic layer was dried over MgSO ₄ and the solvent removed by rotary evaporation to give a clear liquid. The composition of the isolated product, namely phthalic acid 1- (2-acryloyloxy-4-phenylsulfanylbutyl) ester 2- (2-acryloyl-3-phenylsulfanylpropyl) ester, was determined by 1 H-NMR spectroscopy. Confirmation by the assay.

{3.01 (t, 2H), 4.49 (t, 2H), 4.83 (m, 1H), 5.8 (t, 1H), 6.05 (t, 1H), 6.43 (t, 1H), 7.02-7.18 (m, Ph ), 7.58-8.08 (m, Ph)}

Synthesis Example 3 Synthesis of Phthalic Acid Bis [3- (biphenyl-2-yloxy) -2-hydroxypropyl] ester

In a 1000 ml flask equipped with a mechanical stirrer, a water bath, an addition funnel, a water-spray condenser, and a sparge, 177.5 g of phthalic acid, 367 g of biphenylglycidyl ether, 1 g of triphenylphosphine, and Semi-Grade GP 0.5 Join g and react at 90 ° C. for about 5 hours. The end point of the reaction was determined to be 2 mgKOH / g or less by measuring the acid value.

Synthesis Example 4 Synthesis of Phthalic Acid Bis [2-acroyloxy-3- (biphenyl-2-yloxy) -2-propyl] ester

170 g phthalic acid bis [3- (biphenyl-2-yloxy) prepared in Synthesis Example 3 above in a 1000 ml flask equipped with a mechanical stirrer, an oil bath, an addition funnel, a Deanstock, a water-jet condenser and an air bubbler. ) -2-hydroxypropyl] ester, 90 mL acrylic acid, 12 g sulfuric acid, 1 g hydroquinone, 500 mL toluene were added sequentially. The reaction starts at 90 ° C. while bubbling air into the solution. The water produced during the reaction is recovered via Deanstock. The reaction was terminated by calculating the number of moles of water recovered from Dean Stark. After completion of the reaction, the contents of the flask were poured into a separating funnel with distilled water and 300 mL toluene. The aqueous layer was removed and the organic layer was washed with water, diluted sodium hydroxide until the organic layer and the aqueous layer were relatively transparent. The organic layer was dried over MgSO ₄ and the solvent removed by rotary evaporation to give a clear liquid. The composition of the isolated product, ie phthalic acid bis [2-acryloyloxy-3- (biphenyl-2-yloxy) -2-propyl] ester, was confirmed by 1 H-NMR spectroscopy.

{4.18 (t, 2H), 4.49 (t, 2H), 5.06 (t, 1H), 6.83 (t, 1H), 6.43 (t, 1H), 6.88 (t, 1H), 7.11-7.32 (m, Ph ), 7.37-8.08 (m, Ph)}

<Examples 1 to 9, Comparative Examples 1 and 2>

Each component was mixed at a weight ratio shown in Table 1 below to prepare a photocurable resin composition.

ingredient Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Synthesis Example 2 75 60 10 50 90 3 4 30 Synthesis Example 4 75 30 SE-650 10 30 55 60 75 10 30 60 EB-600 10 20 15 75 PT-011 10 5 20 25 5 32 16 10 5 20 20 I-184 4 4 4 4 4 4 4 4 4 4 4 I-819 One One One One One One One One One One One

SE-650: Thiobisphenol Epoxy Diacrylate (Shin-A T & C)

EB-600: Bisphenol A Epoxy Diacrylate (SK-cytec)

PT-011: 2-phenylsulfanylethyl (meth) acrylate (hygroconcentrate))

I-184: 1-hydroxy-cyclohexylphenyl ketone (Ciba)

I-819: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba)

Experimental Example

Using the photocurable resin compositions prepared in Examples 1 to 9 Comparative Examples 1 and 2, the physical properties were evaluated as shown below, and the results are shown in Table 2.

(1) Physical properties before curing of the composition

Viscosity: The viscosity at 25 ° C. was measured using a rotational viscometer according to JIS K7117.

Refractive index: The refractive index is measured by using a refractometer (model name: 1T, Japan ATAGO ABBE) to measure the refractive index of the composition. The light source for the measurement was a D-beam sodium lamp of 589.3 nm.

(2) Prism Sheet Fabrication

The prism sheet was prepared by applying the composition on a PET film and engraving using a polymer mold. The curing condition was 1000mJ light metal halide lamp. Cut.

(3) all-optical characteristics

Except for the existing prism sheet of the backnight unit of the LM170E01 panel, the assembled prism sheet was replaced and reassembled. The average value was measured by measuring color coordinates. At this time, each measurement is expressed as a percentage of the value measured with the existing prism sheet.

(4) Adhesive force evaluation (falling number / 100)

The fabricated sheet is cut into 100 matrix structures in an area of 10 × 10 mm, and then the number of separated matrices is indicated while adhering the tape on it and strongly releasing it vertically.

(5) mountain splitting

After mounting the coated film on the 17-inch backlight unit as shown in No. 2, the backlight unit is mounted on a device that reciprocates 60 times per minute and reciprocates for 10 hours. If it's D, 7 ~ 9 is C, 4 ~ 6 is B, 1 ~ 3 is A, if not S, it's S. 3 is a photomicrograph of a shredding phenomenon.

Example Comparative example One 2 3 4 5 6 7 8 9 One 2 Viscosity 670 950 1100 750 500 1100 2100 720 830 1900 1500 Refractive index 1.593 1.591 1.577 1.585 1.605 1.559 1.55 1.6 1.596 1.542 1.537 Adhesion 0 0 0 One 12 23 7 0 0 18 15 Luminance (%) 104.3 104.2 101.3 102.1 105 99.5 99.2 104.8 104.6 98.9 98.3 Color coordinates (%, X / Y) 0.01 /
-0.01 0.01 /
0.01 0.005
/0.01 0.01 /
0.02 0.02 /
0.02 0.04 /
0.03 0.05 /
0.05 0.01 /
-0.01 0.01 /
0.01 0.03 /
0.03 0.01 /
-0.01 Mountain crossing S S S A D D B S S C D

As shown in Table 2, Examples 1 to 9 to which the (meth) acrylate compound represented by Chemical Formula 1 was added can be confirmed to have a significantly higher refractive index than Comparative Examples 1 and 2 to which the same was not added. In the case of Examples 5 to 7, in which the addition amount of the (meth) acrylate compound represented by the formula (1) was not added within the preferred range of the present invention, the examples 1 to 4, 8 to 9, wherein the addition amount was added within the preferred range of the present invention It can be seen that the physical properties are somewhat reduced compared to.

1 is a schematic view showing an example in which an optical film is applied to a display device.

FIG. 2 is a partially enlarged view of an optical film applied to FIG. 1. FIG.

Claims (19)

(Meth) acrylate compound characterized by the following formula (1). (Formula 1)

(In Formula 1, X and Y are each independently O or S, R is hydrogen or a methyl group, R ₁ is substituted or unsubstituted C ₁ -C ₂₀ aryl, arylalkyl or heteroaryl, and R ₂ is phenyl , Naphthyl, aryl, aryl (C ₁ -C ₆ alkylene)-, heteroaryl or heteroaryl (C ₁ -C ₆ alkylene)-, each of which is halogen, C ₁ -C ₄ alkyl, C _1- Substituted with 0 to 5 substituents independently selected from C ₄ alkoxy, (C ₁ -C ₄ alkyl) S-, C ₁ -C ₄ haloalkyl and C ₁ -C ₄ haloalkoxy, n is an integer from 1 to 10 to be.) The photocurable resin composition containing the (meth) acrylate compound (A) represented by following General formula (1). (Formula 1)

(In Formula 1, X and Y are each independently O or S, R is hydrogen or a methyl group, R ₁ is substituted or unsubstituted C ₁ -C ₂₀ aryl, arylalkyl or heteroaryl, and R ₂ is phenyl , Naphthyl, aryl, aryl (C ₁ -C ₆ alkylene)-, heteroaryl or heteroaryl (C ₁ -C ₆ alkylene)-, each of which is halogen, C ₁ -C ₄ alkyl, C _1- Substituted with 0 to 5 substituents independently selected from C ₄ alkoxy, (C ₁ -C ₄ alkyl) S-, C ₁ -C ₄ haloalkyl and C ₁ -C ₄ haloalkoxy, n is an integer from 1 to 10 to be.) The photocurable resin composition according to claim 2, wherein the composition comprises a polyfunctional (meth) acrylate oligomer (B), a (meth) acrylate monomer (C) and a photoinitiator (D). The photocurable resin composition according to claim 3, wherein the refractive index of the compound having the structure of Chemical Formula 1 is 1.55 or more at 25 ° C. The photocurable resin composition according to claim 3, wherein the (meth) acrylate compound (A) represented by Formula 1 includes 5 to 85 parts by weight based on 100 parts by weight of the total photocurable resin composition. The photocurable resin composition according to claim 3, wherein the polyfunctional (meth) acrylate oligomer (B) comprises a polyfunctional (meth) acrylate oligomer having a refractive index of 1.53 or more. The photocurable resin composition according to claim 3, wherein the polyfunctional (meth) acrylate oligomer (B) comprises 10 to 70 parts by weight based on 100 parts by weight of the total photocurable resin composition. The photocurable resin composition according to claim 3, wherein the (meth) acrylate monomer (C) comprises a low viscosity (meth) acrylate monomer having a refractive index of 1.50 or more and a viscosity of 1 to 500 cps at 25 ° C. 9. The photocurable resin composition according to claim 8, wherein the low viscosity (meth) acrylate monomer contains 1 to 60 parts by weight based on 100 parts by weight of the total photocurable resin composition. The photocurable resin composition according to claim 3, wherein the photoinitiator (D) is included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total composition. An optical film produced by using the photocurable resin composition according to any one of claims 2 to 10. The optical film of claim 11, wherein the optical film has a microstructure pattern on one or both surfaces thereof. The optical film of claim 12, wherein the optical film is formed by putting the photocurable resin composition into a mold capable of forming a microstructure pattern on one or both surfaces thereof, and curing the optical film. The optical film of claim 12, wherein the optical film is formed by applying the photocurable resin composition to one or both surfaces thereof, and then passing the casting drum having a negative pattern original plate having a fine structure and then curing the optical film. An optical element comprising the optical film of claim 11. The optical device according to claim 15, wherein the optical device is a display device. The optical device according to claim 16, wherein the optical film is used as a brightness enhancing film. 16. An optical device according to claim 15, wherein the optical device is an illuminating device. 19. An optical device according to claim 18, wherein the optical film is used as a light conduit film.

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