KR20170125216A - High reflective organic-inorganic hybrid solution and its manufacturing method - Google Patents

Abstract

The present invention relates to a high refractive organic-inorganic hybrid composition and to a manufacturing method thereof, wherein the manufacturing method comprises the following steps: dispersing inorganic nanoparticles in a solvent to prepare a nanoparticle dispersion; adding an aromatic silane surface modifier and a high refractive monomer to a nanoparticle dispersion and stirring the mixture; heat treating the mixed nanoparticle dispersion by heat treatment using a reflux reaction; and evaporating and condensing the surface-treated nanoparticle dispersion, in which it is possible to increase the inorganic nanoparticle content without causing gelation, and thus the brightness of the backlight unit (BLU) can be improved by coating the high refractive organic-inorganic hybrid composition manufactured on a prism film.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-

The present invention relates to a high-index organic-inorganic hybrid composition and a method for producing the same, and more particularly, to an environmentally friendly high-refractive organic / inorganic hybrid composite capable of stably increasing the content of inorganic nanoparticles and a method for producing the same.

As is well known, a liquid crystal display (LCD) is provided with a backlight unit (BLU) serving as a light source on a rear surface or a side surface in order to supply light without supplying light by itself. The backlight unit BLU reflects light emitted from a cold cathode fluorescent lamp (CCFL), a light emitting diode (LED), or the like used as a light source according to a mounting position, And a diffusing sheet for diffusing the returned light in the emitting direction and having a luminance such as a prism film for raising the luminance by refracting and condensing the light emitted from the diffusing sheet, An improvement film or the like may be provided.

Here, the prism film is a prism film that diffuses light in a direction other than a vertical direction (that is, an emitting direction) in a process of diffusing light passing through the diffusion sheet, That is, an emission direction), thereby improving the efficiency of light incident on the panel.

On the other hand, in the display market such as mobile, 3D and smart TV, slimmer and low power consumption are recently required, and in order to maintain and improve the required optical characteristics while minimizing parts in order to meet the required characteristics, High condensing characteristics of the same prism film are required. Especially, as the use of mobile market such as netbook and mobile phone is increasing and UHD (Ultra HD, 3840 X 2160 pixel implementation) is gradually commercialized in FHD (full HD, 1920X1080 pixel implementation), resolution is increased 4 times, It is inevitable to develop a high-luminance prism film for improving the luminance of the backlight unit (BLU).

Accordingly, a high-refractive-index hybrid coating solution capable of improving the brightness of a backlight unit (BLU) has been developed by coating a prism film with a high refractive index organic hybrid composition.

Conventionally, an organic hybrid monomer for preparing a hybrid coating solution having a high refractive index and an organic solvent is surface-treated with MPTMS (? -Methacryloxy propyl trimethoxy silane) to prepare a monomer, which is dispersed in a solvent and dispersed in a solvent Redispersed, and then the solvent was removed using an evaporative condenser. However, when the content of the inorganic nanoparticles is set to 40% or more, the above method has a problem that GEL is likely to occur in the concentration process.

As a method for improving this, there is a method of increasing the content of inorganic nanoparticles by surface treatment with methoxy-ethoxy acetic acid (MEEAA). However, in this case, the acidity of acetic acid is serious, and there is an inconvenience to the operator in the actual coating operation, and there is a problem in environmentally unfavorable.

Therefore, it is necessary to develop a method of manufacturing an environmentally friendly hybrid organic high refractive index coating solution while increasing the content of inorganic nanoparticles without causing GEL.

1. Registration No. 10-1099008 (registered on December 20, 2011): Hybrid optical sheet for backlight 2. Registration No. 10-1392186 (Registered on Apr. 29, 2014): Method for producing diffusion laminate sheet for composite film and composite film produced thereby

SUMMARY OF THE INVENTION It is an object of the present invention to provide a high-refractive-index hybrid composition capable of improving the brightness of a backlight unit (BLU) by coating a prism film with a high refractive index organic hybrid composition.

It is another object of the present invention to provide a method for producing an environmentally friendly high refractive index organic hybrid composition while stably increasing the content of inorganic nanoparticles in the production of an inorganic nanoparticle dispersion for making a high refractive index organic hybrid coating solution.

However, these problems are illustrative, and the technical idea of the present invention is not limited thereto.

In order to accomplish the above object, the high refractive index organic hybrid composition according to the present invention may contain inorganic nanoparticles modified with an aromatic silane surface modifier in a high refractive index monomer in a solid content of at least 45% by weight .

In one embodiment of the present invention, the inorganic nanoparticles may include at least one particle selected from zirconia (ZrO 2), titania (TiO 2), barium titanate (BaTiO 3) and zinc oxide (ZnO).

In one embodiment of the present invention, the aromatic silane-based surface modifier is selected from the group consisting of 3- (n-styrylmethyl-2-aminoethylamino) -propyltrimethoxysilane hydrochloride, 3- 2-aminoethylamino) -propyltrimethoxysilane, and styrylethyltrimethoxysilane. The term " a "

In one embodiment of the present invention, the aromatic silane surface modifier may be added in an amount of 0.1-10 parts by weight based on 100 parts by weight of the inorganic nanoparticles.

In one embodiment of the present invention, the high refractive monomer is selected from the group consisting of phenoxyethylmethacrylate, phenoxy-2-methylethylmethacrylate, phenoxyethoxyethylmethacrylate, 3-hydroxy-2- Propyl methacrylate, benzyl methacrylate, phenylthioethyl acrylate, 2-naphthylthioethyl acrylate, 1-naphthylthioethyl acrylate, 2,4,6-tribromophenoxyethylacrylate, 2, 4-dibromophenoxyethyl acrylate, 2-bromophenoxyethyl acrylate, 1-naphthyloxyethyl acrylate, 2-naphthyloxyethyl acrylate, phenoxy 2-methylethyl acrylate, phenoxy Methoxyethyl acrylate, 3-phenoxy-2-hydroxypropyl acrylate, and the like.

In one embodiment of the present invention, the high refractive index organic hybrid composition may further include an ultraviolet curable oligomer and a photopolymerization initiator.

In one embodiment of the present invention, the ultraviolet-curable oligomer may include at least one material selected from urethane acrylate, epoxy acrylate, polyester acrylate, polyester acrylate and silicone acrylate.

In one embodiment of the present invention, the photopolymerization initiator is at least one selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphine (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and 2-hydroxy-2-methyl-1-phenyl-propane-1-source.

According to an aspect of the present invention, there is provided a method for preparing a high-refractive-index organic hybrid composition, which comprises dispersing inorganic nanoparticles in a solvent to prepare a nanoparticle dispersion, mixing the nanoparticle dispersion with an aromatic silane- Adding and mixing high-refractive-index monomers, heat treating the mixed nanoparticle dispersion liquid using a reflux reaction, and evaporating and condensing the surface-treated nanoparticle dispersion liquid.

In one embodiment of the present invention, the solvent may include at least one selected from the group consisting of methanol, acetone and Methyl ethyl ketone.

In one embodiment of the present invention, the step of preparing the nanoparticle dispersion comprises the steps of: preparing a dispersion solution by stirring the solvent and the dispersant; adding the inorganic nanoparticles to the dispersion solution so as to be wetted; Stirring and dispersing the dispersion solution to which the inorganic nanoparticles are added, and ball milling and dispersing the dispersion solution.

In one embodiment of the present invention, the dispersant may include at least one selected from a polyester dispersant, a polyacrylate dispersant, and a polyester dispersant.

In one embodiment of the present invention, the aromatic silane-based surface modifier is selected from the group consisting of 3- (n-styrylmethyl-2-aminoethylamino) -propyltrimethoxysilane hydrochloride, 3- 2-aminoethylamino) -propyltrimethoxysilane, and styrylethyltrimethoxysilane. The term " a "

In one embodiment of the present invention, the aromatic silane surface modifier may be added in an amount of 0.1-10 parts by weight based on 100 parts by weight of the inorganic nanoparticles.

In one embodiment of the present invention, the high refractive index organic hybrid composition may include the surface-modified inorganic nanoparticles in a solid content of at least 45% by weight.

In one embodiment of the present invention, the method further comprises, after the step of evaporating and condensing the nanoparticle dispersion, mixing the evaporated and condensed nanodisperse solution with a coating mixture comprising an ultraviolet curable oligomer and a photopolymerization initiator and evaporating and condensing .

According to the technical idea of the present invention, the high-refractive-index organic hybrid composition can improve the brightness of a backlight unit (BLU) by coating a high refractive index organic hybrid composition on a prism film.

In addition, it is possible to provide a method for producing an environmentally friendly high refractive index organic hybrid composition while stably increasing the content of inorganic nanoparticles in the production of an inorganic nanoparticle dispersion for making a high refractive index organic hybrid coating solution.

The effects of the present invention described above are exemplarily described, and the scope of the present invention is not limited by these effects.

1 is a schematic view showing the surface modification of nanoparticles by grafting of a silane-based surface modifier according to the present invention.
2 is a schematic view showing a method for producing an organic-inorganic hybrid composition according to the present invention.
3 is a photograph showing the reflux reactor according to the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. It will be apparent to those skilled in the art that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art. The scope of technical thought is not limited to the following examples. Rather, these embodiments are provided so that this disclosure will be more thorough and complete, and will fully convey the scope of the invention to those skilled in the art. As used herein, the term "and / or" includes any and all combinations of one or more of the listed items. The same reference numerals denote the same elements at all times. Further, various elements and regions in the drawings are schematically drawn. Accordingly, the technical spirit of the present invention is not limited by the relative size or spacing depicted in the accompanying drawings.

In the high refractive index organic hybrid composition according to the present invention, the inorganic nanoparticles whose surfaces have been modified with an aromatic silane surface modifier in the high refractive index monomers may be dispersed in a solid content of at least 45% by weight. In particular, the high refractive index organic hybrid composition may include the surface-modified inorganic nano-particles in a solid content of 45 wt% to 80 wt%, and may have a viscosity range of 500-2000 cPs.

If the inorganic nanoparticles are less than 45% by weight, the viscosity and coating properties of the composition are advantageous. However, even if the refractive index of the inorganic nanoparticles is high, the effect is insignificant for the refractive index and the luminance increase of the entire high refractive index organic hybrid composition. Is more than 80% by weight, the refractive index of the entire composition may be increased, but since the viscosity of the composition increases, the nanoparticles aggregate during evaporation and condensation to cause haze, .

1 is a schematic view showing the surface modification of nanoparticles by grafting of a silane-based surface modifier according to the present invention. A silane-based surface modifier may be used as the surface modifier of the inorganic nanoparticles. Nanoparticle surface modification and grafting techniques are needed to prevent agglomeration of inorganic nanoparticles and increase their bonding to polymeric resins. Silane compounds are generally used for surface modification of fillers such as inorganic nanoparticles and organic pigments. The silane has the advantage of being thermally stable, permeable, and easy to modify the surface.

The silane-based surface modifier has two or more different reactors in the molecule. One is a methoxy group and an ethoxy group which are chemically bonded to metal oxide nanoparticles by hydrolysis, and the other is a vinyl group, an epoxy group, and a methacrylic group, which are reactors for chemically bonding with various polymer resins which are organic materials . Therefore, it is known that it serves as an intermediary for connecting organic and inorganic materials which are difficult to bond normally.

In particular, an aromatic silane-based surface modifier may be used as the surface modifier of the inorganic nanoparticles. An aromatic silane surface modifier can be used to increase the refractive index of the surface modifier and to stably increase the content of the inorganic nanoparticles.

The inorganic nanoparticles may include at least one or more particles selected from zirconia (ZrO2), titania (TiO2), barium titanate (BaTiO3) and zinc oxide (ZnO) Particles.

The aromatic silane surface modifier may be at least one selected from the group consisting of 3- (n-styrylmethyl-2-aminoethylamino) -propyltrimethoxysilane hydrochloride, 3- (n-styrylmethyl- Methoxy silane, and styryl ethyl trimethoxy silane.

The aromatic silane-based surface modifier may include a benzene ring that can chemically bond to inorganic nanoparticles including a methoxy group and can increase the refractive index of the surface modifier, and a styrene group having a vinyl group that chemically bonds with various polymer resins that are organic materials Lt; / RTI > The surface of the inorganic nanoparticles is modified by using the aromatic silane surface modifier to uniformly form an aromatic styrene group on the surface to suppress the aggregation of the inorganic nanoparticles in the monomer and to increase the binding force with the monomer, Even when the nanoparticles contain at least 45% by weight of the nanoparticles, they can be stably dispersed without GEL formation.

The aromatic silane-based surface modifier may be added in an amount of 0.1-10 parts by weight based on 100 parts by weight of the inorganic nanoparticles. By modifying the surface of the inorganic nanoparticles using the silane-based surface modifier in such a content range, The inorganic nanoparticles can be dispersed in the polymer resin.

The high refractive index monomers are preferably selected from the group consisting of phenoxyethyl methacrylate, phenoxy-2-methylethyl methacrylate, phenoxyethoxyethyl methacrylate, 3-hydroxy-2-hydroxypropyl methacrylate, benzyl methacrylate , Phenylthioethyl acrylate, 2-naphthylthioethyl acrylate, 1-naphthylthioethyl acrylate, 2,4,6-tribromophenoxyethyl acrylate, 2,4-dibromophenoxyethyl acrylate , 2-bromophenoxyethyl acrylate, 1-naphthyloxyethyl acrylate, 2-naphthyloxyethyl acrylate, phenoxy 2-methylethyl acrylate, phenoxyethoxyethyl acrylate, 3-phenoxy 2-hydroxypropyl acrylate, and a methacrylate monomer having a mono- and di-functional group containing at least one substance selected from the group consisting of a polyfunctional monomer and a polyfunctional monomer.

In particular, a polyfunctional monomer has characteristics such as curability, crosslinking, abrasion resistance and weatherability, and can play a large role in raising the refractive index of an ultraviolet curable coating agent having a close relationship with the brightness of the prism film. Are preferably selected so that the viscosity of the organic component is less than about 1000 cPs.

The high refractive index organic hybrid composition may further include an ultraviolet curable oligomer and a photopolymerization initiator.

The ultraviolet curable oligomer has the greatest tendency to UV curing rate and physical properties (for example, adhesive force, abrasion resistance, vulcanization resistance, etc.), and physical properties and optical properties of the coating film can be determined according to the backbone. In embodiments of the present invention, at least one material selected from urethane acrylate, epoxy acrylate, polyester acrylate, polyester acrylate and silicone acrylate may be included.

It is known that urethane acrylate can realize various properties and physical properties depending on the kinds of polyol and diisocyanate used in oligomer synthesis, and has excellent properties such as toughness, flexibility and flex resistance.

Epoxy acrylates are classified into a bisphenol A type and a novolac type according to their basic structure and are known to have excellent properties such as adhesiveness to substrates, heat resistance, and chemical resistance.

It is also known that polyester acrylate is produced by ester reaction of various acids and glycols and has excellent properties such as hardness and stain resistance, and silicone acrylate is excellent in physical properties such as heat resistance and elasticity.

In addition, photopolymerization initiators can be added to induce polymerization by ultraviolet light to ultraviolet-curable oligomers and high-refraction monomers such as 1-hydroxycyclohexyl phenyl ketone (Irgacure 184), 2,4,6 (Lucirin TPO), ethyl 2,4,6-trimethylbenzoyl phenylphosphinate (Lucirin TPO-L), bis (2,4,6-trimethylbenzoylphenylphosphonate) (Irgacure 819) and 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocure 1173) . ≪ / RTI >

In order to improve the surface leveling, slipperiness, releasability, dispersibility and the like, a high-refractive index organic hybrid composition may further contain a silicone additive, a fluorine-based additive, an acrylic additive and the like. By weight may be added in an amount of 0.01-10 parts by weight.

Accordingly, the high-refractive index organic hybrid composition according to the present invention is characterized in that inorganic nanoparticles whose surfaces have been modified with an aromatic silane surface modifier in a high refractive index monomer are dispersed in a solid content of at least 45% by weight and coated on the prism film, And is excellent in dispersibility and transparent, so that it has no light scattering property and brightness and light transmittance can be improved.

2 is a schematic view showing a method for producing an organic-inorganic hybrid composition according to the present invention. The method for preparing a high refractive index organic hybrid composition according to the present invention includes the steps of preparing a nanoparticle dispersion by dispersing inorganic nanoparticles in a solvent, adding an aromatic silane surface modifier and a high refractive monomer to the nanoparticle dispersion, Treating the dispersion of mixed nanoparticles with heat using a refluxing reaction, and evaporating and condensing the surface-treated nanoparticle dispersion.

The silane-based surface modifier and the high-refraction monomer are added to the nanoparticle dispersion, stirred, and then subjected to a surface treatment using a reflux reaction, thereby suppressing aggregation in the organic resin and improving the compatibility with the resin and the bonding strength .

The surface-treating step may be performed by grafting for 20 to 50 hours using a reflux reaction at 50 to 80 ° C, and the evaporation condensation step may be a step for condensing the solution with the residual organic solvent and impurities The solvent can be evaporated at a temperature ranging from 40 to 80 DEG C in a pressure range of from 0.01 to 0.2 MPa to vaporize and evaporate the solvent.

If the temperature is lower than 40 ° C in the pressure range of 0.01-0.2 MPa, the unreacted materials will not be distilled well. If the temperature exceeds 80 ° C, the nanoparticles will agglomerate due to heat, It can be evaporated and condensed according to the temperature range of -80 ℃.

The solvent may include at least one selected from the group consisting of methanol, acetone and Methyl ethyl ketone. Such a solvent can improve the dispersion stability without causing aggregation of nanoparticles in the coating material by adjusting the polarity of the solvent, and can simultaneously improve the solubility of the organic monomer and oligomer and the solubility of the dispersant.

Further, when grafting the surface of nanoparticles with a silane surface modifier in the future, a solvent excellent in solubility in water added for solubility and hydrolysis of the silane compound can be used. In case of performing evaporation condensation, The boiling point may be less than 200 ° C so that volatility is favorable.

In particular, when methanol is used as a solvent, the solubility in nanodispersion or high refractive monomer is excellent and viscosity can be lowered, and it is excellent in viscosity, transmittance and liquid refractive index because it is excellent in compatibility and point of view .

The step of preparing the nanoparticle dispersion may include the steps of: preparing a dispersion solution by stirring the solvent and the dispersant; adding the inorganic nanoparticles to the dispersion solution and agitating the solution to be wetted; And ball milling and dispersing the added dispersion solution. The inorganic nanoparticles can be dispersed using a ball miller or a vertical miller.

The ball (bead) used for the ball milling may be a ceramic material ball made of alumina or zirconia and may use a ball having the same size or a size of 2 or more. The ball size, the milling time, Speed can be adjusted. The size of the ball can be set in the range of 0.01-20 mm and the rotation speed of the ball miller can be set in the range of 50-1000 rpm for 1-300 hours, The particles can be milled to a fine size and can have a uniform size distribution.

The dispersant may be a polyester dispersant, a polyacrylate dispersant, a polyester dispersant, or the like. The dispersant has a polar group affinity for polarity such as a hydroxyl group, a carboxyl group and an amine group for adsorbing on the surface of the inorganic nanoparticles to generate an electrostatic repulsive force, The effect of steric hindrance is exhibited by the structure so that the interval between the pigments can be maintained to prevent the pigments from being re-agglomerated.

Especially. A polyacrylate dispersant having an amine value of 0 mgKOH / g can be used. The polyacrylate dispersant has a linear CC backbone, which produces an anchoring group that works with a variety of pigments, while the other group acts as an acrylate resin, allowing adjacent pigments to re-agglomerate To the effect of steric hindrance. However, since the pigment-affinity group of the amine group in the dispersant surrounding the inorganic nanoparticles is a functional group of the base, the dispersion stability of the organic pigment may be lowered by reacting with the functional group of the organic monomer or oligomer.

The dispersing agent may be dispersed in an amount of 0.1 to 25 parts by weight based on 100 parts by weight of the nano-particle dispersion. When the dispersant is used in an amount of 25 parts by weight or more, the refractive index of the nanoparticle dispersion liquid and the final prism coating liquid may be lowered.

After the step of evaporating and condensing the nanoparticle dispersion, the evaporation condensed nanodispersion solution may be mixed with a coating mixture comprising an ultraviolet curable oligomer and a photopolymerization initiator and evaporated and condensed. The hygroscopic organic hybrid composition may be prepared by mixing 20 to 70% by weight of an ultraviolet curable oligomer and 0.1 to 10% by weight of a photopolymerization initiator and evaporating and condensing the mixture.

Herein, the evaporation condensation can be carried out according to the temperature range of 40-80 ° C. and the pressure range of 0.01-0.2 MPa. In the high-refractive-index organic hybrid composition prepared as described above, the surface-modified inorganic nano- To 45% by weight, and may have a viscosity of 500-2000 cPs.

Therefore, by coating the high refractive index organic hybrid composition according to the present invention on the prism film, the refractive index and the dispersibility are excellent and transparent, so that the light scattering property can be improved and the brightness and light transmittance can be improved.

Further, the present invention can suppress the aggregation phenomenon in the organic resin by applying the silane-based surface modifier and the high-refraction monomer to the nanoparticle dispersion solution together and stirring the mixture, and then performing the surface treatment using the reflux reaction, And the bonding force can be improved.

In addition, the present invention relates to a process for surface treatment of nanoparticles and a method for preparing a high refractive index organic hybrid composition by performing a surface treatment of nanoparticles in a single reactor capable of reflux cooling and evaporative condensation, The production yield can be improved.

The high refractive index organic hybrid composition prepared through the process described above can realize excellent liquid refractive index and brightness and can improve the luminance by about 4% or more as compared with the composition comprising only the organic UV curable resin.

First, the high-refractive-index organic hybrid composition prepared according to an embodiment of the present invention can be used for a prism film provided in a backlight unit (BLU). The shape of the prism film is not particularly limited, Or the modified prism film may be modified, substituted or improved without departing from the scope of the present invention.

Further, the present invention can provide various types of optical devices including an optical film (or an optical sheet), and the composition or the cured product thereof can be utilized as a material or parts contained in an optical device. For example, the composition or the cured product thereof may be contained in an optical device in the form of an optical film (or an optical sheet), and such prismatic film may be applied to various optical devices.

Meanwhile, a general prism film manufacturing process can be roughly classified into two types: a method using a hard mold formed by plating a roll with nickel or copper and then bite, a method using a polymer And a method of using a soft mold made of a resin.

However, sheet manufacturers prefer a soft mold method in which the production cost of a mold is about one third lower than that of a hard mold. This is because a hard mold is manufactured, a mold is manufactured by imprinting using the manufactured hard mold For example, a thermal imprinting method, a UV imprinting method, or the like can be used as the imprinting method. Recently, the UV imprinting method is used.

The present invention is characterized by providing a high refractive index organic hybrid composition more suitable for manufacturing a prism film by the soft mold process.

The base material (or base material sheet) of the prism film of the present invention may be formed of a transparent material that transmits light. For example, the substrate sheet may be manufactured by extrusion, casting, or the like, of at least one material selected from acrylic resin, polycarbonate resin, and polymethyl methacrylate (PMMA) resin, and the substrate film may be polyethylene terephthalate terephthalate (PET) film, and the like.

The prism pattern formed on the prism film may include an ultraviolet curable resin and inorganic nanoparticles dispersed in the ultraviolet curable resin, and the prism pattern may include a high refractive index organic hybrid including an ultraviolet curable resin and inorganic nanoparticles dispersed in the ultraviolet curable resin Can be prepared by photocuring the composition.

Specifically, the ultraviolet ray curable resin is cured to form a polymer resin, the inorganic nano particles can be dispersed in the polymer resin in the prism film, and the prism pattern is formed by injecting a high refractive index organic hybrid composition into a mold having a prismatic shape, And can be formed by pressing.

The inorganic nanoparticles dispersed in the prism pattern can improve not only the refractive index of the prism film but also the transmittance of the prism film and the transmittance of the prism film, The brightness of light passing through the film can be improved.

In a soft mold, a sheet defective rate can be lowered by slowing the sheet mass production rate due to the problem of releasability. The hybrid composition of a high refractive index organic / inorganic hybrid composition is coated on a polyethylene terephthalate (PET) film with a soft mold and a high pressure mercury lamp and a metal halide lamp And irradiating it with ultraviolet light and curing it, a prism pattern can be formed.

The amount of ultraviolet light is preferably from 50 to 300 mJ / cm < 2 > at the time of pattern formation of the prism film coated with the hybrid composition of the present invention. When the amount of ultraviolet light is 300 mJ / cm 2 or more, abrasion resistance, brightness, and adhesion can be improved. However, the releasability with the mold is inferior and the productivity may be decreased. As a result of deterioration in optical characteristics of the prism film due to yellowing due to curing Lt; / RTI > When the amount of light is 50 mJ / cm 2 or less, the amount of curing is insufficient, so that productivity is increased due to securing releasability, but other properties are deteriorated.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, details of the present invention will be described with reference to examples and experimental examples.

1. Nanoparticle dispersion

1-1. Selection of dispersant

Using ZrO2 and TiO2 nanoparticles, a comparative evaluation was carried out using Additive-A (acid value: 129 mgKOH / g, refractive index: 1.42) and Additive-B (acid value: 53 mgKOH / g, refractive index: 1.40) Respectively.

1-2. Selection of solvent

The organic solvent used for the dispersion of ZrO2 and TiO2 nanoparticles was one having a large polar value (sp value). Here, the polarity value of the solvent is a solubility parameter (delta), and is a measure of the polarity of the solvent. The polarity value of the solvent is a value represented by the aggregation energy density and the molecular capacity as shown by the following formula (1).

(Equation 1)? = (? Ev / V) 1/2

△ Ev: Cohesive energy density

V: Molecular capacity

IPA (parameter 11.5, boiling point 82.6 ° C, refractive index 1.38) was used as the dispersion solvent of the ZrO 2 and TiO 2 nanoparticle dispersions in consideration of the dispersibility, solubility parameter, compatibility with water, and boiling point of ZrO 2 and TiO 2 nanoparticles, MEK (parameter 9.27, boiling point 79.64 占 폚, refractive index 1.38), methanol (parameter 14.28, boiling point 64.7 占 폚, refractive index 1.33) can be used.

1-3. Preparation of ZrO ₂ , TiO ₂ nanoparticle dispersion

The dispersions of ZrO ₂ nanoparticles and TiO ₂ nanoparticles were prepared on the basis of the dispersant of 1-1. The dispersing agent and the dispersion solvent were stirred until a homogeneous solution was obtained. Then, the inorganic nanoparticles were added to the nanoparticles to preliminarily agitate the nanoparticles for about 1 hour to wet the dispersed solution. Thereafter, the mixture was transferred to a jar filled with a ZrO ₂ ball having a diameter of 0.1 mm, and ball mill dispersion was performed at a uniform speed (about 200 rpm) for 72 hours (three days) to prepare a nanoparticle dispersion.

1-4. Evaluation of dispersibility of ZrO ₂ and TiO ₂ nanoparticles

Table 1 shows experimental conditions and evaluation results for securing optimum dispersion conditions of ZrO ₂ nanoparticle dispersions. Table 2 shows experimental conditions and evaluation results for ensuring optimal dispersion conditions of TiO 2 nanoparticle dispersions.

division Product Name Nanoparticle dispersion-1 Nanoparticle dispersion-2 Nanoparticle Dispersion-3 Nanoparticle dispersion-4 Nanoparticle dispersion-5 ZrO ₂ powder - 20 20 20 20 20 Dispersant Additive-B 5 5 5 - - Additive-A - - - 5 6 Dispersed solvent IPA 75 MEK 75 Methanol 75 75 74 Total 100 100 100 100 100 Dispersion time 96hr 96hr 96hr 96hr 96hr Layer separation
(Visual observation) 24hr after layer separation
Occur Layer separation after 12hr
Occur 168 hr later layer separation
Occur No layer separation No layer separation

division Product Name Nanoparticle dispersion-6 Nanoparticle Dispersion-7 Nanoparticle dispersion-8 Nanoparticle dispersion-9 Nanoparticle dispersion-10 TiO ₂ powder - 20 20 20 20 20 Dispersant Additive-B 5 5 5 - - Additive-A - - - 5 6 Dispersed solvent IPA 75 MEK 75 Methanol 75 75 74 Total 100 100 100 100 100 Dispersion time 96hr 96hr 96hr 96hr 96hr Layer separation
(Visual observation) 24hr after layer separation
Occur Layer separation after 12hr
Occur 168 hr later layer separation
Occur No layer separation No layer separation

As a result of evaluation, it was found that both of the ZrO2 and TiO2 nanoparticles were dispersed in methanol (Methanol (R)) when dispersed using IPA (Nanoparticle Dispersion 1, Nanoparticle Dispersion 6) and MEK (Nanoparticle Dispersion 2 and Nanoparticle Dispersion 7) ) Was used as a dispersing solvent (Nanoparticle Dispersion-3, Nanoparticle Dispersion-8), the particle size distribution was excellent. Additive-A, which has a higher acid value than that of dispersing using Additive-B as a dispersant, -4, nanoparticle dispersion-9), the layer separation was also excellent and the particle size distribution became smaller. In the case of Nanoparticle Dispersion-5 and Nanoparticle Dispersion-10, the content of the dispersant was increased to 30% of the particles, and the particle size distribution became smaller. However, since the refractive index of the nanoparticle dispersion was low 1.33, 1.35) may affect the refractive index of the coating liquid for the final prism.

1-5. Evaluation of dispersion time

In order to confirm the dispersibility of the nanoparticle dispersion according to the dispersion time, based on the blending of the nanoparticle dispersion-4 and the nanoparticle dispersion-9, 96 hours (4 days), 132 hours (4.5 days) Dispersion was carried out for 168 hours (168 days) (Nanoparticle dispersion-12, Nanoparticle dispersion-15) and 192 hours (Nanoparticle dispersion-13, Nanoparticle dispersion-16) And the results are shown in Table 3. < tb > < TABLE > When dispersed up to 168 hr, it was confirmed that the aggregated particles were further dispersed at an average particle size of about 39.8 nm and about 40.0 nm, respectively. When dispersed up to 192 hr, it was 41.2 nm and 40.7 nm, The dispersion time was confirmed to be 168 hr.

division ZrO2 powder TiO2 powder Sample name Nanoparticle dispersion-4 Nanoparticle dispersion-11 Nanoparticle dispersion-12 Nanoparticle dispersion-13 Nanoparticle dispersion-9 Nanoparticle dispersion-14 Nanoparticle dispersion-15 Nanoparticle dispersion-16 Dispersion time 96hr 132hr 168hr 192hr 96hr 132hr 168hr 192hr Average particle size (nm) 68.3 52.6 39.8 41.2 69.9 53.9 40 40.7

2. Preparation of organic / inorganic hybrid composition

Hydrolysis and grafting of a silane-based surface modifier having functional groups capable of reacting with UV curable high refractive index monomers, oligomers and coating materials on the surface of nanoparticles of a dispersion using ZrO ₂ nanoparticles and TiO ₂ nanoparticles, And the surface modified hybrid nanocomposite dispersion was used to prepare an organic hybrid composition.

2-1. Selection of surface modifier

The nanoparticle surface modification experiment was carried out by using a dispersion using ZrO ₂ nanoparticles and a dispersion using TiO ₂ nanoparticles, adding the amount and type of silane surface modifier, and adding the amount of inorganic nanoparticles. Table 4 shows the physical properties and structures of the silane-based surface modifier according to the kind thereof. The silane surface modifiers were tested by using amino, methacrylic clock, epoxy and aromatic styrene.

Chemical name Refractive index rescue Comparative Example 1 3-aminopropyl triethoxysilane 1.420

Comparative Example 2 3-methacyloxypropyl methyldimethoxylsilane 1.433

Comparative Example 3 3-glycidoxypropyl triethoxysilane 1.425

Example 1 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane hydrochloride 1.395

Example 2 3- (n-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane 1.390

Example 3 스틸ylethyltrimethoxysilane 1.505

3 is a photograph showing the reflux reactor according to the present invention. 30 g of methanol was added to 200 g of the dispersion using the dispersion using the ZrO ₂ nanoparticles and the dispersion using the TiO ₂ nanoparticles. The amount of each of the silanes was varied. The monomer A (refractive index, 1.59) And surface modification was carried out by grafting at 65 to 70 ° C for 24 hours using a refluxing reaction. Thereafter, the solution in which the surface modification step was completed was subjected to evaporation (0.09 MPa, 40 ° C) to volatilize the remaining organic solvent and impurities, and the compatibility with the organic resin and the dispersibility were compared. As a result, in the case of surface treatment with the amino system (Comparative Example 1) and the epoxy system (Comparative Example 3) surface modifier, the gel was solidified at the evaporation condensation stage and the viscosity became very high, and the haze of the solution also became relatively high, It was not transparent. This result is similar to the result of mixing with high refractive monomer without surface treatment using a silane surface modifier, and as a result of evaporation condensation, it is considered that silane is not grafted sufficiently on the surface of nanoparticles. (Comparative Example 2) and an aromatic silane-based surface modifier (Examples 1 to 3) in an amount of 0.5 wt% based on the nanoparticle content, the viscosity was low and the transparency was excellent Respectively.

The amount of the inorganic nanoparticles was measured with respect to the case of using the methacrylic clock surface modifier (Comparative Example 2) and the aromatic silane surface modifier (Examples 1 to 3), which show relatively low viscosity and excellent transparency The surface modification of nanoparticles was carried out.

When the surface treatment was conducted using the methacrylic rock surface modifier (Comparative Example 2), the GEL was advanced in the concentration process when the content of the inorganic nanoparticles was 40%, while the aromatic silane surface modifier (Examples 1 to 3) , The inorganic nanoparticles were stably dispersed in the case of 40% and 45% of the inorganic nanoparticles without GEL formation, and the GEL formation proceeded when the inorganic nanoparticles were contained in an amount of 50% by weight or more.

Therefore, it was confirmed that even when the aromatic silane-based surface modifier (Examples 1 to 3) was used and the inorganic nanoparticles were contained in an amount of 45 wt% or more, they were stably dispersed without GEL formation. Examples 1 to 3 using an aromatic silane-based surface modifier modified the surface of inorganic nanoparticles to uniformly form an aromatic styrene group on the surface to inhibit the aggregation of inorganic nanoparticles in the monomer, And it was confirmed that it was dispersed stably.

2-2. Manufacture of high-refractive index organic / inorganic hybrid composition

Based on the results of the previous experiments, aromatic silane (especially styrylethyltrimethoxysilane) was selected as the silane surface modifier, and the type of solvent was changed during the surface modification of the nanoparticles (Methanol, Acetone, MEK) and the viscosity of the organic hybrid monomer Experiments were conducted to lower the haze.

First, the dispersion of nanoparticles was mixed with each solvent at a weight ratio of 10: 1 and diluted. Then, the aromatic styrene type surface modifier was added in an amount of 0.5 wt% based on the nanoparticle content and uniformly stirred. Then, the monomer A (domestic A company, refractive index 1.59) was mixed so that the content of the nanoparticles became 20 to 50 wt%, heat was applied for 24 hours using a reflux reaction at 65 to 70 ° C, and grafting was carried out Respectively. It is possible to uniformly form an aromatic styrene group on the surface of the nanoparticles so that the aggregation of the particles in the monomer can be suppressed and the binding force with the monomer can be enhanced. After the grafting, the solvent was evaporated by evaporation at 40 ° C at 0.09 MPa to prepare a high-refractive index organic hybrid composition.

Tables 5 and 6 show the evaluation results of physical properties of the hybrid monomer having high refractive index based on the kind of solvent. Table 5 shows the ZrO2 nanoparticle dispersion, and Table 6 shows the TiO2 nanoparticle dispersion.

menstruum ZrO ₂ content
(wt%) * Viscosity (cPs) Transmittance
(@ 550 nm,%) Liquid refractive index GEXP-1 Methanol 40.8 1774 89.1 1.628 GEXP-2 Acetone 41.3 1937 83.7 1.637 GEXP-3 MEK 39.9 2864 77.2 1.624 GEXP-4 Methanol 20.8 423 92.4 1.602 GEXP-5 Methanol 50.1 - - 1.660

  * Evaluation condition: calcination at 800 ° C for 2 hours, calculation using the following formula

             B / A * 100 (%) (where A is the weight before firing and B is the weight after firing)

solvent TiO ₂ content
(wt%) * Viscosity (cPs) Transmittance
(@ 550 nm,%) Liquid refractive index GEXP-6 Methanol 40.1 2145 81.6 1.657 GEXP-7 Acetone 39.6 2531 75.5 1.623 GEXP-8 MEK 41.4 3572 72.9 1.622 GEXP-9 Methanol 21.8 621 79.3 1.600 GEXP-10 Methanol 51.1 - - 1.659

 * Evaluation condition: calcination at 800 ° C for 2 hours, calculation using the following formula

             B / A * 100 (%) (where A is the weight before firing and B is the weight after firing)

In order to improve the characteristics of organic / inorganic hybrid monomers, it was found that when methanol was used as a solvent, the viscosity, permeability, and liquid refractive index were superior in all aspects of the surface modification of the nanoparticles and the transparency This is because the methanol has excellent solubility in ZrO ₂ , TiO ₂ nanodispersion and high refractive monomer, which can lower the viscosity and is excellent in compatibility and viscosity.

The high-refractive-index organic hybrid composition according to the present invention modifies the surface of inorganic nano-particles using an aromatic silane-based surface modifier to uniformly form aromatic styrenic groups on the surface to inhibit the aggregation of inorganic nanoparticles in the monomer, Even when the inorganic nanoparticles contain the inorganic nanoparticles in an amount of 45 wt% or more by enhancing the bonding force with the monomer, the GEL can be stably dispersed without causing GEL.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims. Will be apparent to those of ordinary skill in the art.

Claims (16)

Wherein the inorganic nanoparticles whose surface is modified with an aromatic silane surface modifier are dispersed in a high refractive index monomer in a range of at least 45% by weight as solids.
The method according to claim 1,
Wherein the inorganic nanoparticles comprise at least one particle selected from zirconia (ZrO2), titania (TiO2), barium titanate (BaTiO3) and zinc oxide (ZnO).
The method according to claim 1,
The aromatic silane surface modifier may be at least one selected from the group consisting of 3- (n-styrylmethyl-2-aminoethylamino) -propyltrimethoxysilane hydrochloride, 3- (n-styrylmethyl- Methoxysilane, and styrylethyltrimethoxysilane. The high-refractive-index organic hybrid composition according to claim 1,
The method of claim 3,
Wherein the aromatic silane-based surface modifier is added in an amount of 0.1-10 parts by weight based on 100 parts by weight of the inorganic nanoparticles.
The method according to claim 1,
The high refractive index monomers are preferably selected from the group consisting of phenoxyethyl methacrylate, phenoxy-2-methylethyl methacrylate, phenoxyethoxyethyl methacrylate, 3-hydroxy-2-hydroxypropyl methacrylate, benzyl methacrylate , Phenylthioethyl acrylate, 2-naphthylthioethyl acrylate, 1-naphthylthioethyl acrylate, 2,4,6-tribromophenoxyethyl acrylate, 2,4-dibromophenoxyethyl acrylate , 2-bromophenoxyethyl acrylate, 1-naphthyloxyethyl acrylate, 2-naphthyloxyethyl acrylate, phenoxy 2-methylethyl acrylate, phenoxyethoxyethyl acrylate, 3-phenoxy Hydroxy-2-hydroxypropyl acrylate, wherein the methacrylate monomer is a methacrylate monomer having at least one functional group selected from the group consisting of a hydroxyl group,
The method according to claim 1,
The high-refractive-index organic hybrid composition further comprises an ultraviolet-curable oligomer and a photopolymerization initiator.
The method according to claim 6,
Wherein the ultraviolet-curable oligomer comprises at least one material selected from urethane acrylate, epoxy acrylate, polyester acrylate, polyester acrylate and silicone acrylate.
The method according to claim 6,
The photopolymerization initiator is preferably at least one selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoyl phenylphosphinate, bis -Trimethylbenzoyl) -phenylphosphine oxide, and 2-hydroxy-2-methyl-1-phenyl-propane-1-one.
Dispersing inorganic nanoparticles in a solvent to prepare a nanoparticle dispersion;
Adding an aromatic silane surface modifier and a high refractive monomer to the nanoparticle dispersion and stirring the same;
Applying a heat treatment to the mixed nanoparticle dispersion liquid using a reflux reaction; And
And evaporating and condensing the surface-treated nanoparticle dispersion.
10. The method of claim 9,
Wherein the solvent comprises at least one selected from the group consisting of methanol, acetone, and methyl ethyl ketone (MEK).
10. The method of claim 9, wherein preparing the nanoparticle dispersion comprises:
Stirring the solvent and the dispersant to prepare a dispersion solution;
Adding the inorganic nanoparticles to the dispersion solution and stirring the organic nanoparticles so as to be wetted; And
And ball milling and dispersing the dispersion solution to which the inorganic nanoparticles are added.
10. The method of claim 9,
Wherein the dispersant is at least one selected from a polyester dispersant, a polyacrylate dispersant, and a polyester dispersant.
10. The method of claim 9,
The aromatic silane surface modifier may be at least one selected from the group consisting of 3- (n-styrylmethyl-2-aminoethylamino) -propyltrimethoxysilane hydrochloride, 3- (n-styrylmethyl- Methoxysilane, and styrylethyltrimethoxysilane. 2. A method for preparing a high-refractive-index organic hybrid composition according to claim 1,
10. The method of claim 9,
Wherein the aromatic silane-based surface modifier is added in an amount of 0.1-10 parts by weight based on 100 parts by weight of the inorganic nanoparticles.
10. The method of claim 9,
Wherein the high refractive index organic hybrid composition comprises a surface modified inorganic nanoparticle in a solid content of at least 45% by weight.
10. The method of claim 9,
Further comprising, after the step of evaporating and condensing the nanoparticle dispersion, mixing the evaporated and condensed nanodisperse solution with a coating mixture comprising an ultraviolet curable oligomer and a photopolymerization initiator followed by evaporation and condensation.

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