KR20210106365A - Photo-polymerizable composition, optical element prepared therefrom, and display device - Google Patents

Abstract

The present invention relates to a photopolymerizable composition capable of forming an optical member exhibiting improved optical properties including excellent light transmittance, low haze and a high refractive index, an optical member manufactured therefrom, and a display device. The photopolymerizable composition includes: at least one olefin-based monomer having a photocurable functional group; metal oxide particles; an amine compound having an amine group and a photocurable functional group; and a photopolymerization initiator.

Description

Photopolymerizable composition, optical member and display device formed therefrom {PHOTO-POLYMERIZABLE COMPOSITION, OPTICAL ELEMENT PREPARED THEREFROM, AND DISPLAY DEVICE}

The present invention relates to a photopolymerizable composition capable of forming an optical member exhibiting improved optical properties including excellent light transmittance, low haze and high refractive index, an optical member formed therefrom, and a display device.

In the case of a light-transmitting optical film having a structured prism, the luminance increase rate varies depending on the refractive index of the resin constituting the prism structure. In general, as the refractive index of the resin constituting the prism increases, the luminance increase rate increases. Therefore, with respect to the light-transmitting optical film, research and development is being conducted in the direction of increasing the refractive index of the resin constituting the prism structure.

However, in general, the resin constituting the prism is formed of an organic compound, and the refractive index range that can be adjusted with the organic compound is known to have a theoretical upper limit of about 1.65, so the adjustable refractive index range is narrow compared to the inorganic compound. In addition, in the case of increasing the refractive index of the resin formed of the organic compound, the viscosity of the monomer composition is increased, so that the processability is lowered or the UV stability is lowered, and thus there are many technical limitations.

Moreover, in the case of forming the resin and the optical film using a conventional photopolymerizable composition as a monomer composition, surface hardening often did not occur sufficiently due to the influence of oxygen in the air during the photocuring of the monomer composition. As a result, the resin and the optical film had a problem in that haze increased, and light transmittance such as ultraviolet transmittance and visibility were lowered. To this end, a method of performing the curing process under an inert gas atmosphere such as nitrogen has been considered, but this may result in a large increase in manufacturing cost.

Accordingly, the present invention provides a photopolymerizable composition capable of forming an optical member exhibiting improved optical properties including excellent light transmittance, low haze and high refractive index by suppressing an increase in haze during the curing process.

The present invention also provides an optical member formed of the photopolymerizable composition and exhibiting improved optical properties including excellent light transmittance, low haze and high refractive index.

Another object of the present invention is to provide a display device including the optical member.

The present invention relates to at least one olefinic monomer having a photocurable functional group;

metal oxide particles;

an amine compound having an amine group and a photocurable functional group; and

Provided is a photopolymerizable composition comprising a photoinitiator.

The present invention also provides a substrate; and a cured film including a cured product of the photopolymerizable composition. In such an optical member, the cured product may include a polymer including a unit in which photocurable functional groups of the olefinic monomer and the amine compound are cross-linked, and a dispersant and a metal oxide dispersed on the polymer.

Also, the present invention provides a display device including the optical member.

The photopolymerizable composition described herein enables the formation of a cured film satisfying a high refractive index and an optical member including the same. In addition, due to the action of the amine compound included in the photopolymerizable composition, it is possible to greatly reduce the problem of reduced surface hardening due to the influence of oxygen, and as a result, light transmittance such as low haze and excellent ultraviolet transmittance and high visibility Formation of an optical member becomes possible.

In addition, in the curing process of the photopolymerizable composition, since the application of a nitrogen atmosphere, etc. is not necessary, the economic feasibility of the overall process can also be greatly improved.

Accordingly, the optical member formed with the photopolymerizable composition has a low manufacturing cost, and exhibits low haze, high refractive index, excellent light transmittance and visibility, etc., thereby greatly contributing to the improvement of properties of a display device.

Hereinafter, the present invention will be described in more detail. The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

Also, the meaning of "comprising" as used herein in the context of the present invention embodies a particular characteristic, region, integer, step, operation, element and/or component, and other characteristic, region, integer, step, operation, element and/or It does not exclude the presence or addition of ingredients.

In the present specification, (meth) acrylate is meant to include both acrylate and methacrylate.

Hereinafter, embodiments will be described in detail so that those of ordinary skill in the art can easily implement it. The embodiment may be implemented in several different forms, and is not limited to the specific embodiment described herein.

According to one embodiment of the invention, at least one olefinic monomer having a photocurable functional group;

metal oxide particles;

an amine compound having an amine group and a photocurable functional group; and

A photopolymerizable composition comprising a photoinitiator is provided.

The photopolymerizable composition of one embodiment includes the olefinic monomer together with the metal oxide particles. By using such an olefinic monomer, the photopolymerizable composition has excellent processability such as application and film formation. In addition, by using the olefinic monomer together with the metal oxide particles, it is possible to form a cured film that satisfies a high refractive index required for an optical member, such as a transmissive optical film, and an optical member including the same.

And, it was confirmed that by the action of a predetermined amine compound included in the photopolymerizable composition, it was possible to significantly reduce the problem of a decrease in the degree of surface hardening due to the influence of oxygen. This is because during the curing process, the photocurable functional group of the amine compound participates in the curing reaction together with the olefinic monomer, and the amine group of the amine compound captures oxygen radicals in the air, so that the reactivity of the polymerization initiator can be increased. looks like

Therefore, when the photopolymerizable composition of one embodiment is photocured to form a cured film and an optical member, a high degree of surface hardening is achieved even in an air atmosphere, and the cured film has low haze, excellent light transmittance such as UV transmittance, and high visibility can be displayed. In addition, in the curing process of the photopolymerizable composition, since the application of a nitrogen atmosphere, etc. is not necessary, the economic feasibility of the overall process can also be greatly improved.

Therefore, by using the photopolymerizable composition, it is possible to form an optical member exhibiting low haze, high refractive index, excellent light transmittance and visibility while having a low manufacturing cost, thereby greatly contributing to the improvement of characteristics of a display device. have.

Specifically, each component used in the photopolymerizable composition will be described below.

The photopolymerizable composition of one embodiment is a basic monomer for forming a cured film matrix, and includes at least one olefinic monomer having a photocurable functional group.

The olefinic monomer may form a basic resin constituting a cured film by cross-linking polymerization of the photocurable functional group through a photopolymerization initiator through a photocuring process to be described later.

In a preferred embodiment, the olefinic monomer may have an absolute viscosity (measured at 25° C.) of 1 cP to 30 cP, or 2 cP to 25 cP. As the olefinic monomer satisfies this absolute viscosity range, the composition of one embodiment may have an absolute viscosity suitable for an inkjet application process, for example, an absolute viscosity of 5 to 30 cP. Accordingly, the composition of one embodiment including the same has excellent processability by an inkjet application process, etc., and enables the formation of a cured film having excellent heat resistance and mechanical properties and good coating film properties. In addition, the cured film and the optical member formed of the composition of one embodiment may have a high refractive index of 1.6 or more due to the interaction between the olefinic monomer and the metal oxide particles to be described later.

If the absolute viscosity of the olefinic monomer is less than 1 cP, it may cause deterioration of heat resistance or mechanical properties of the photopolymerizable composition. can cause In addition, when the absolute viscosity of the olefinic monomer exceeds 30 cP, the ink jet may not be discharged or the discharge amount may decrease, thereby making it very difficult to proceed with the ink jet application process.

For reference, the viscosity of the olefinic monomer or photopolymerizable composition described herein means an absolute viscosity value measured at 25° C., and this absolute viscosity is a viscometer well known in the art, for example, a Brookfield viscometer. can be measured using

Meanwhile, examples of the above-described olefinic monomer are not particularly limited, and an olefinic monomer having a photocurable functional group including a (meth)acrylate group may be appropriately used in consideration of appropriate viscosity characteristics, curing characteristics, and the like.

Examples of the olefinic monomer include a mono(meth)acrylate-based compound or a di(meth)acrylate-based compound, and more specifically, an aliphatic mono(meth)acrylate having 6 to 20 carbon atoms, and 6 to carbon atoms. 30 alicyclic mono (meth) acrylate, aromatic mono (meth) acrylate having 8 to 30 carbon atoms, aliphatic di (meth) acrylate having 6 to 30 carbon atoms, alicyclic di (meth) acrylate having 6 to 40 carbon atoms and at least one selected from the group consisting of aromatic di(meth)acrylates having 8 to 40 carbon atoms may be used.

In addition, according to a more preferred embodiment, the olefin-based monomer has an absolute viscosity so that the monomer composition of the embodiment exhibits viscosity characteristics more suitable for an inkjet application process, etc., and a cured film formed therefrom can exhibit a high refractive index in a desired range, etc. It may include at least one selected from the group consisting of a first olefinic monomer having a (measured at 25°C) of 1cP or more and 7cP or less and a second olefinic monomer having an absolute viscosity (measured at 25°C) of 8cP or more and 30cP or less.

From the viewpoint of achieving the viscosity characteristics and refractive index, according to a more preferred embodiment, the olefin-based monomer may include a first olefin-based monomer having a low viscosity and a second olefin-based monomer having a high viscosity. More specifically, with respect to 100 parts by weight of the total of the olefinic monomer, 10 to 90 parts by weight, or 20 to 80 parts by weight of the first olefinic monomer, and 10 to 90 parts by weight, or 20 to 90 parts by weight of the second olefinic monomer 80 parts by weight.

As such, as the olefinic monomer, the low-viscosity first olefin-based monomer and the high-viscosity second olefin-based monomer are used together in a predetermined ratio, so that the processability of the photopolymerizable composition including the same is further improved by the inkjet coating process, etc. , the cured film and optical member formed therefrom may exhibit more improved heat resistance or optical properties such as low haze.

As the first or second olefinic monomer, a compound known to satisfy a certain viscosity in the range of the above-described olefinic monomer may be selected and used without particular limitation.

For example, specific examples of the first olefinic monomer include benzyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, ethoxy ethyl (meth) acrylate, and dicyclophene. and at least one selected from the group consisting of tenyl (meth) acrylate and dicyclopentanyl (meth) acrylate. In addition, various (meth) acrylate-based monomers known to have low viscosity may be used.

In addition, specific examples of the second olefinic monomer include dicyclopentenyl oxyethyl (meth) acrylate, phenoxy ethyl (meth) acrylate, phenoxy benzyl (meth) acrylate, isobornyl (meth) acrylate , 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, 2-vinyloxyethoxy At least one selected from the group consisting of ethyl (meth) acrylate and tripropylene glycol di (meth) acrylate, and other various (meth) acrylate-based monomers known to have a high viscosity in the above-mentioned range may be used can

The above-described olefinic monomer may be included in an amount of 5 wt% to 88 wt%, or 15 wt% to 85 wt%, based on 100 wt% of the total photopolymerizable composition. If the content of the olefin-based monomer is too low, the uniformity of the metal oxide particles after the formation of the coating film is deteriorated, and the viscosity increases, so that inkjet ejection may be difficult. In addition, when the olefin-based content is excessively high, it may be difficult to achieve a high refractive index of the cured film and the optical member.

On the other hand, the photopolymerizable composition of one embodiment includes metal oxide particles. These metal oxide particles are dispersed on a cured film formed by photocuring the olefin-based monomer, enabling the cured film and an optical member including the same to achieve a high refractive index.

The metal oxide particles, for example, have an average particle diameter (D50) of 25 to 45 nm, or 30 to 40 nm, based on the secondary particle diameter of the dispersed medium, and the group consisting of Zn, Zr, Ti, Hf and Ce. Oxide particles containing a metal element selected from may be used.

Among these, from the viewpoint of achieving a high refractive index, zirconium (Zr) oxide particles can be used more preferably. In addition, as the metal oxide particles satisfy the above-described average particle diameter range, the photopolymerizable composition of one embodiment can be easily adjusted to have a viscosity range suitable for an inkjet application process, etc., while the haze of the cured film is lowered. Optical properties This can be improved.

The above-described metal oxide particles may be included in an amount of 10 wt% to 70 wt%, or 10 wt% to 65 wt%, based on 100 wt% of the total photopolymerizable composition. If the content of the metal oxide particles is excessively low, it may be difficult to achieve a high refractive index. On the contrary, if the content thereof is excessively high, the uniformity of the metal oxide particles after forming a coating film is deteriorated, and the viscosity increases, so that inkjet ejection may be difficult.

On the other hand, the photopolymerizable composition of one embodiment includes an amine compound having an amine group and a photocurable functional group. In the process of photocuring the composition of one embodiment to form a cured film and an optical member, the amine compound may promote the reaction of the initiator by capturing oxygen radicals in the air, etc., in the amine compound. Furthermore, the photocurable functional group in the amine compound may participate in a curing reaction together with the monomer to form a crosslink. Due to the action of the amine compound, the cured film and the optical member formed of the composition of one embodiment may exhibit a high degree of surface hardening, thereby exhibiting excellent optical properties such as low haze and improved light transmittance.

Examples of such amine compounds include a photocurable functional group, for example, a functional group capable of forming a cross-linkage with the photocurable functional group of the above-mentioned monomer, together with an amine group in the molecule, and in a more specific example, a photocurable functional group of the same kind as the monomer Any compound having a (meth)acrylate group can be used. In addition, in order to more effectively trap the oxygen radicals and the like to further increase the degree of surface hardening of the cured film, it is more preferable that the amine compound includes a tertiary or higher amine structure in the molecule.

Specific examples of the amine compound include a compound of Formula 1 below, ethyl dimethylamino benzoate, butoxyethyl dimethylamino benzoate, bis(diethylamino)benzophenone, bis(2-hydroethyl)-toluidine , ethylhexyl-(dimethylamino)benzoate, 2-(dimethylamino)ethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(diisopropylamino)ethyl (meth)acrylate , 2-(acryloyloxy)ethyl 4-(dimethylamino)benzoate, 2-ethylhexyl 4-(dimethylamino)benzoate, ethyl 2-(dibutylamino)methyl acrylate and 4,4- (oxybis(ethane-2, 1-diyl))bis(oxy)bis(dimethylaniline) may be at least one selected from the group consisting of, and various compounds having an amine group and a photocurable functional group may also be used. Of course there are:

[Formula 1]

In Formula 1, R ₁ and R ₂ each independently represent an alkyl group having 1 to 5 carbon atoms, R ₃ is an alkyl group having 1 to 20 carbon atoms, an ether group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amine group or a (meth)acrylate group.

In addition, a commercially available amine-based photocurable compound can also be used as the amine compound. Examples of such a commercialized compound include P115 (manufactured by SK Cytec), MIRAMER AS2010 (manufactured by Miwon Corporation), or MIRAMER AS5142 (manufactured by Miwon Corporation). and the like.

The above-described amine compound may be included in an amount of 0.1 wt% to 10 wt%, or 0.5 wt% to 9 wt%, based on 100 wt% of the total photopolymerizable composition. When the content of the amine compound is too low, the surface hardening degree is lowered and the haze of the cured film and the optical member may be increased. The refractive index may be lowered.

The photopolymerizable composition of the above-described embodiment includes a photopolymerization initiator. The photopolymerization initiator may initiate and promote the photocuring reaction of the above-described olefinic monomer and amine compound. In addition, by the action of the amine compound, the initiation of the photocuring reaction and the like can be made more effectively.

As the photopolymerization initiator, any initiator previously known to initiate and promote a photocuring reaction of a photocurable functional group such as a (meth)acrylate group may be used.

Examples of the photopolymerization initiator include at least one selected from the group consisting of triazine-based, benzoin-based, benzophenone-based, imidazole-based, xanthone-based, oxime ester-based and acetophenone-based compounds. More specific examples of the photopolymerization initiator include 2,4-bistrichloromethyl-6-p-methoxystyryl-s-triazine, 2-p-methoxystyryl-4,6-bistrichloromethyl- s-triazine, 2,4-trichloromethyl-6-triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine, 2- (o-chlorophenyl) -4,5- Diphenyl imidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl) imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenyl imidazole Dimer, 2-(o-methoxyphenyl)-4,5-diphenyl imidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl imidazole dimer, 2,4-di (p-methoxyphenyl)-5-phenyl imidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenyl imidazole dimer, 2-(p-methylmercaptophenyl)- 4,5-diphenyl imidazole dimer, [1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazolyl-3-yl]-1-(O-acetyloxime), benzophenone, p-(diethylamino)benzophenone, 2,2-dichloro-4-phenoxyacetophenone, 2,2-diethoxyacetophenone, 2-dodecylthioxanthone, 2,4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2,2-bis-2-chlorophenyl-4,5,4,5-tetraphenyl-2-1,2-biimidazole, (E)-2-(acetoxyimino )-1-(9,9-diethyl-9H-fluorene-2-yl)butanone, (E)-1-(9,9-dibutyl-7-nitro-9H-fluorene-2-yl ) Ethanone O-acetyl oxime, (Z)-2-(acetoxyimino)-1-(9,9-diethyl-9H-fluorene-2-yl)propanone, Irgacure 369, Irgacure 651, Irgacure 907 , Darocur TPO, Irgacure 819, OXE-01, OXE-02, OXE-03, OXE-04, Adeka's N-1919, NCI-831 and NCI-930. A photopolymerization initiator known in the art can be widely used without particular limitation.

The above-described photopolymerization initiator may be included in an amount of 0.1 wt% to 10 wt%, or 0.5 wt% to 7 wt%, based on 100 wt% of the total photopolymerizable composition. If the content of the photopolymerization initiator is too low, photocuring may not occur properly. Conversely, if the content thereof is excessively high, the accumulated transmittance of the cured film may be reduced to, for example, 90% or less.

The photopolymerizable composition of one embodiment may further include a dispersing agent in addition to each component described above. Such a dispersant may be included in the above-described photopolymerizable composition to improve dispersion stability of other components such as metal oxide particles.

The kind of such dispersing agent is not particularly limited, and any dispersing agent previously known to be usable for improving dispersibility of metal oxide particles and the like may be used. Examples of such a dispersant include at least one selected from the group consisting of an acrylic dispersant, an epoxy dispersant, and a silicone dispersant.

The dispersant may be included in an amount of 0.1 wt% to 30 wt%, or 0.5 wt% to 20 wt%, based on 100 wt% of the total photopolymerizable composition. According to the content of the dispersant, the metal oxide particles and the like are uniformly dispersed, so that a desired refractive index range of the cured film may be more effectively achieved. However, if the content of the dispersant is excessively high, the viscosity of the photopolymerizable composition may increase and processability may be deteriorated.

Meanwhile, the photopolymerizable composition of one embodiment may further include other additives in consideration of additional required physical properties or fairness. As a non-limiting example, when the photopolymerizable composition is applied, an additive capable of improving film thickness uniformity or surface smoothness or improving adhesion between the photopolymerizable composition and the substrate may be further included. Such additives may include at least one selected from a surfactant, a silane-based coupling agent, and a crosslinking agent compound.

For example, based on 100 parts by weight of the total content of the photopolymerizable composition, 0.1 parts by weight to 30 parts by weight of the melamine crosslinking agent compound is included, or 0.1 parts by weight to 30 parts by weight of a silane-based coupling agent is included, or 0.1 parts by weight of a surfactant To 5 parts by weight may be further included, and of course, two or more additives may be included in combination among them.

In addition, the composition of one embodiment described above may be prepared in a solvent-free type that does not include a separate solvent or liquid medium. The composition serves as a medium for dissolving or dispersing other components in which the olefinic monomer and the like are dissolved, thereby making it possible to manufacture such a solvent-free type. As a result, since the drying process for removing the solvent or the like after application can be omitted or minimized, the processability using the composition of the one embodiment can be further improved.

The photopolymerizable composition of an embodiment including each of the above-described components may have an absolute viscosity (measured at 25° C.) of 5 to 30 cP or 11 cP to 30 cP. The absolute viscosity may be measured using a well-known viscosity measuring instrument, for example, a Brookfield viscosity measuring instrument, in the same manner as the above-described olefinic monomer. As the photopolymerizable composition of one embodiment satisfies this viscosity range, it is possible to form a cured film having excellent heat resistance and mechanical properties, and not only excellent processability by an inkjet coating process, but also good coating film formation by an inkjet coating process this becomes possible

If the viscosity of the final composition is too low, the discharge characteristics may be deteriorated due to nozzle drying and clogging. Moreover, when the viscosity of a composition is too high, there exists a problem that discharge amount falls and a pattern and surface formation do not occur.

Meanwhile, according to another embodiment of the present invention, a cured film including a cured product of the above-described photopolymerizable composition and an optical member including the same are provided. Such an optical member may include a substrate; and the cured film formed on the substrate. In addition, as the cured film is formed by photocuring after the photopolymerizable composition of one embodiment is applied on a substrate by an inkjet coating process, a polymer including a unit in which the photocurable functional groups of the olefinic monomer and the amine compound are crosslinked; , may mainly include a cured product including a dispersant and a metal oxide dispersed on the polymer.

More specifically, the cured product includes an olefin resin crosslinked by curing of an olefinic monomer, and the olefin resin may be further crosslinked with a photocurable functional group of the amine compound. In addition, on the olefin resin matrix having such a cross-linked structure, the metal oxide particles and, optionally, a dispersing agent and a component derived from a photopolymerization initiator, etc. may be dispersed. However, most of the photopolymerization initiator is decomposed during the curing process and may not substantially remain in the cured product and the optical member.

In such a cured product, the olefin resin is a polymer crosslinked from one or more olefinic monomers, and the form thereof is not particularly limited, and depending on the type of monomer and the mechanism of the polymerization reaction, a homo copolymer, a block copolymer, It may have various forms, such as a random copolymer or a graft copolymer.

As the cured film including the cured product is formed of the photopolymerizable composition of one embodiment having a viscosity suitable for an inkjet coating process, excellent heat resistance and mechanical properties, and good coating film properties may be exhibited. In addition, the cured film may have a high refractive index of, for example, 1.6 or more, or 1.6 to 2.0, or 1.6 to 1.65, due to the interaction of the olefinic monomer and metal oxide particles, and a high surface hardening degree due to the action of the amine compound For example, 3% or less, or 1% or less, or 0 to 1%, or 0.01 to 0.8%, or 0.1 to 0.3% of low haze and excellent UV transmittance and light transmittance and visibility. . In this case, the refractive index may mean a value measured with respect to a wavelength of 555 to 575 nm (average) using an ellipsometer.

In the above-described optical member, a well-known substrate such as bare glass may be used as the substrate.

In addition, the optical member, by using a Mayer bar, a coating applicator or inkjet equipment, etc., applying the photopolymerizable composition of the above-described embodiment on the substrate, for example, in an air atmosphere, LED lamp or metal halide It may be manufactured by a method of performing photocuring by exposing using a lamp or the like. At this time, the photopolymerizable composition is applied in the form of a single film and then photocured to form an optical member in the form of a general optical film. have. In this case, the optical member may be in the form of a patterned film in which a cured film patterned in a polyhedral shape such as a prism structure is formed on a substrate.

The optical member such as the above-described optical film or pattern film may have a general thickness according to the type or structure of an applied display device, for example, may have a thickness adjusted within the range of 0.01 μm to 1000 μm.

In addition, the optical member may have a sensitivity value of 3J or less, and a light transmittance of 90% or more. The sensitivity may be measured by comparing absorbance measurement results before and after exposure using an FT-IR spectrophotometer. More specifically, the 1650 ~ 1750cm ^-1 of C = O peak and 780 ~ 880cm ^-1 C = C integrating the peak seeking the conversion rate, and the sensitivity may mean that the saturated exposure amount at a conversion rate is 80% or more. In addition, the light transmittance may mean an average transmittance measured at a wavelength of 380 to 780 nm using a UV-VIS spectrophotometer for an optical member such as an optical film.

까지 분당 10

씩 승온하여 TGA로 측정된, 5 중량% Loss 온도가 270

이상이 될 수 있어, 우수한 내열성을 나타낼 수 있다. And, the optical film is 900 at room temperature

up to 10 per minute

The temperature was raised step by step and the 5 wt% loss temperature measured by TGA was 270

It may be abnormal, and excellent heat resistance may be exhibited.

Since the optical member of another embodiment, such as the above-described optical film or pattern film, satisfies excellent optical properties, heat resistance, and mechanical properties, it can be applied to various display devices and greatly contribute to improving properties thereof.

Accordingly, according to another embodiment of the present invention, a display device including the optical member is provided.

The configuration of the display device to which the optical member such as the optical film or the pattern film is applied may follow a conventional configuration well known in the art, except that the optical member of the other embodiments described above is applied, and thus additional description thereof will be omitted. do it with

Hereinafter, examples are presented to help the understanding of the invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto.

Comparative Examples 1 to 3, Reference Examples 1 to 16 and Examples 1 to 54: Preparation of photopolymerizable composition and optical film

First, each compound was mixed with the composition of the monomers shown in Tables 1 to 3 to prepare the olefinic monomers used in the preparation of the photopolymerizable compositions of Examples, Reference Examples and Comparative Examples, respectively. In addition, with the composition shown in Tables 4 to 6, the photopolymerizable compositions of Comparative Examples, Reference Examples and Examples were prepared by mixing the olefinic monomer and the remaining components.

After each composition was put into the inkjet equipment, it was applied to bare glass to form a single film so as to have a thickness of 20 μm.

Then, in an air atmosphere, using a belt type metal halide UV irradiation device (120W/cm ² ) to which a 330 to 440 nm UV filter is applied, the single film is irradiated with an exposure amount of 1.5J/cm ^{2 ,} An optical film including a cured film of a synthetic composition was prepared. At this time, the thickness of the cured film formed on the optical film was maintained at 20㎛.

For each of the optical films of Comparative Examples and Examples, physical properties such as refractive index, haze, and viscosity were measured by the following method, and the results are shown in Tables 7 to 9.

* Method of measuring physical properties of optical films

1) Sensitivity

It was measured by comparing the absorbance measurement results before and after exposure using an FT-IR spectrophotometer. 1650 ~ 1750cm ^-1 and the C = O peak and 780 ~ 880cm ^-1 C = C integrating the peak seeking the conversion rate, and the sensitivity was measured and calculated from the amount of exposure that is saturated at a conversion rate is 80% or more.

Judgment

○: When the sensitivity value is 3J or less

X: When the sensitivity value exceeds 3J

2) refractive index

For the optical film, the refractive index (555-575 nm average) was measured using an ellipsometer.

Judgment

○: When the measurement value of the refractive index of the optical film is 1.6 or more

X: When the refractive index measurement value of the optical film is less than 1.6

3) light transmittance

For the optical film, the average transmittance at 380 to 780 nm was measured using a UV-VIS spectrophotometer (Cary4000, Agilent).

Judgment

○: When the average transmittance value is 90% or more

X: When the average transmittance value is less than 90%

4) Haze

The haze was measured using a haze meter COH 400 manufactured by NIPPON DENSHOKU.

Judgment

○: When the haze measurement value is 1.0% or less

△: When the haze measurement value is more than 1.0% and less than or equal to 3.0%

X: When the haze measurement value exceeds 3.0%

5) Viscosity (absolute viscosity)

For each of the photopolymerizable compositions and olefinic monomers of Comparative Examples and Examples, the absolute viscosity of each was measured using a viscometer (trade name: Brook Field viscometer) at a temperature of 25 °C.

Judgment

○: When the absolute viscosity value is 5 to 30 cP

X: When the absolute viscosity value is out of the above range

6) Inkjet Fairness

By changing the nozzle temperature of the inkjet equipment, it was checked whether the surface was formed.

Judgment

Surface formation at nozzle temperature 25~50℃ = ○

No face formation at nozzle temperature 25~50℃ = X

7) heat resistance

까지 분당 10

씩 승온하면서 측정하였다. 이때 TGA 장비는 TA Instruments社 장비를 사용하였다.Heat resistance was measured using TGA equipment. After sampling the pattern film formed during sensitivity measurement, use TGA equipment to

up to 10 per minute

Measurements were made while the temperature was increased. In this case, TGA equipment was used by TA Instruments.

Judgment

이상인 경우O: TGA 5wt% Weight loss Temp. 270

If more than

미만인 경우X: TGA 5wt% Weight loss Temp. 270

less than

Example No. Monomer ratio (wt%) benzyl acrylate
(2cP) Lauryl Acrylate
(4 cP) isodecyl acrylate
(5 cP) Phenoxyethyl acrylate
(9cP) isobornyl acrylate
(8 cP) Phenoxybenzyl acrylate
(10 cP) hexanediol diacrylate
(12 cP) Dipropylene glycol diacrylate
(15 cP) Triethylene glycol diacrylate
(20 cP) Tripropylene glycol diacrylate
(25 cP) One 100 2 100 3 100 4 100 5 100 6 100 7 100 8 100 9 100 10 100 11 100 12 100 13 100 14 100 15 100 16 100 17 100 18 100 19 100 20 40 60 21 40 60 22 40 60 23 40 60 24 40 60 25 40 60 26 40 60 27 40 60 28 40 60 29 30 70 30 20 80 31 40 60 32 30 70 33 20 80 34 40 60 35 30 70 36 20 80 37 20 80

Example
(or comparative example) No. Monomer ratio (wt%) methyl acrylate
(0.5 cP) benzyl acrylate
(2cP) Lauryl Acrylate
(4 cP) isodecyl acrylate
(5 cP) Phenoxyethyl acrylate
(9cP) isobornyl acrylate
(8 cP) Phenoxybenzyl acrylate
(10 cP) hexanediol diacrylate
(12 cP) 38 100 39 20 80 40 20 80 41 20 80 42 20 80 43 20 80 44 20 80 45 20 80 46 20 80 47 20 80 48 20 80 49 20 80 50 20 80 51 20 80 52 20 80 53 20 80 54 20 80 Comparative Example 1 40 60 Comparative Example 2 40 60 Comparative Example 3 40 60

Reference example No. Monomer ratio (wt%) Methyl acrylate (0.5 cP) Lauryl Acrylate (4cP) Phenoxyethyl acrylate (9cP) Isobornylacrylate (8cP) Biphenylmethylacrylate (40cP) One 20 80 2 20 80 3 20 80 4 20 80 5 20 80 6 100 7 100 8 100 9 20 80 10 80 20 11 40 60 12 40 60 13 40 60 14 40 60 15 40 60 16 40 60

division metal oxide
(ZrO ₂ ) Dispersant (wt%) Monomer (wt%) photopolymerization initiator
(weight%) amine compounds
(weight%) average
particle size
(D50;nm) content (wt%) A B C D E F G A B C D E Example 1 30 65 6 21 5 3 Example 2 30 60 6 26 5 3 Example 3 30 55 5.5 31.5 5 3 Example 4 30 50 5 37 5 3 Example 5 30 40 4 48 5 3 Example 6 30 10 One 81 5 3 Example 7 30 50 5 37 5 3 Example 8 30 50 5 37 5 3 Example 9 30 50 5 37 5 3 Example 10 30 50 5 37 5 3 Example 11 30 50 5 37 5 3 Example 12 30 50 5 37 5 3 Example 13 35 40 4 48 5 3 Example 14 35 40 4 48 5 3 Example 15 35 40 4 48 5 3 Example 16 35 40 4 48 5 3 Example 17 35 40 4 48 5 3 Example 18 35 40 4 48 5 3 Example 19 35 40 4 48 5 3 Example 20 30 40 5 52 5 3 Example 21 30 40 5 52 5 3 Example 22 30 40 5 47 5 3 Example 23 30 40 5 47 5 3 Example 24 30 40 5 47 5 3 Example 25 30 40 5 49.5 5 0.5 Example 26 30 40 5 45 5 5 Example 27 30 35 5 47 5 8 Example 28 30 35 5 52 5 One 2 Example 29 30 50 5 37 5 3 Example 30 30 50 5 37 5 3 Example 31 30 35 3.5 53.5 5 3 Example 32 30 35 3.5 53.5 5 3 Example 33 30 35 3.5 53.5 5 3 Example 34 30 35 3.5 43.5 15 3 Example 35 30 35 3.5 43.5 15 3 Example 36 30 35 3.5 43.5 15 3 Example 37 30 35 3.5 28.5 30 3

Note) Photoinitiator type A: [1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazolyl-3-yl]-1-(O-acetyloxime)

B: OXE-01

C: Darocure TPO

D: (E)-2-(acetoxyimino)-1-(9,9-diethyl-9H-fluorene-2-yl)butanone

E: Irgacure 819

F: Irgacure 369

G: Irgacure 907

Note) Amine compound type

A: ethyl dimethylamino benzoate

B: butoxyethyl dimethylamino benzoate

C: diethylaminoethyl (meth)acrylate

D: P115 (manufactured by SK Cytec)

E: MIRAMER AS2010 (manufactured by Miwon Corporation)

Note) Dispersant: acrylic polymer-containing dispersant (commercially available)

division Metal oxide ¹⁾ dispersant
(weight%) monomer
(weight%) photopolymerization initiator
(weight%) amine compounds
(weight%) average
particle size
(D50; nm) content
(weight%) A B C D E F G A B C D E Example 38 30 60 6 30 One 3 Example 39 37 50 5 37 5 3 Example 40 37 50 5 37 5 3 Example 41 37 50 5 37 5 3 Example 42 37 50 5 37 5 3 Example 43 30 50 5 37 5 3 Example 44 30 50 5 37 5 3 Example 45 30 50 5 37 5 3 Example 46 30 50 5 37 5 3 Example 47 30 50 5 37 5 3 Example 48 30 50 5 42 5 3 Example 49 30 50 5 42 5 3 Example 50 40 50 5 37 5 3 Example 51 40 50 5 37 5 3 Example 52 40 50 5 37 5 3 Example 53 40 50 5 37 5 3 Example 54 40 50 5 37 5 3 Comparative Example 1 30 35 5 55 5 Comparative Example 2 30 40 5 50 5 Comparative Example 3 30 50 5 40 5

Note 1) Metal oxide particles: Examples and Comparative Examples 1 to 3 all use _{ZrO 2 .} Note) The types of photoinitiator, amine compound and dispersant are the same as Note) in Table 4.

division Metal oxide ¹⁾ dispersant
(weight%) monomer
(weight%) photopolymerization initiator
(weight%) amine compounds
(weight%) average
particle size
(D50; nm) content
(weight%) A B C D E F G A B C D E Reference Example 1 7 50 5 37 5 3 Reference Example 2 20 50 5 37 5 3 Reference example 3 50 50 5 37 5 3 Reference Example 4 80 50 5 37 5 3 Reference Example 5 100 50 5 37 5 3 Reference Example 6 30 50 5 37 5 3 Reference Example 7 30 50 5 37 5 3 Reference Example 8 30 35 4 53 5 3 Reference Example 9 30 45 5 42 5 3 Reference example 10 30 50 5 37 5 3 Reference Example 11 30 42.95 5 47 5 0.05 Reference Example 12 30 35 5 44 5 11 Reference Example 13 TiO2 20 35 5 52 5 3 Reference Example 14 TiO2 50 40 5 47 5 3 Reference Example 15 ZnO 20 40 5 47 5 3 Reference Example 16 ZnO 50 40 5 47 5 3

Note 1) Metal oxide particles: All of Reference Examples 1 to 13 use _{ZrO 2 .} Reference Examples 14 to 16 are separately described for each composition. Note) The types of photoinitiator, amine compound and dispersant are the same as Note) in Table 4.

division Sensitivity refractive index permeability Haze absolute viscosity Inkjet Fairness heat resistance Example 1 ○ ○ ○ ○ ○ ○ ○ Example 2 ○ ○ ○ ○ ○ ○ ○ Example 3 ○ ○ ○ ○ ○ ○ ○ Example 4 ○ ○ ○ ○ ○ ○ ○ Example 5 ○ ○ ○ ○ ○ ○ ○ Example 6 ○ ○ ○ ○ ○ ○ ○ Example 7 ○ ○ ○ ○ ○ ○ ○ Example 8 ○ ○ ○ ○ ○ ○ ○ Example 9 ○ ○ ○ ○ ○ ○ ○ Example 10 ○ ○ ○ ○ ○ ○ ○ Example 11 ○ ○ ○ ○ ○ ○ ○ Example 12 ○ ○ ○ ○ ○ ○ ○ Example 13 ○ ○ ○ ○ ○ ○ ○ Example 14 ○ ○ ○ ○ ○ ○ ○ Example 15 ○ ○ ○ ○ ○ ○ ○ Example 16 ○ ○ ○ ○ ○ ○ ○ Example 17 ○ ○ ○ ○ ○ ○ ○ Example 18 ○ ○ ○ ○ ○ ○ ○ Example 19 ○ ○ ○ ○ ○ ○ ○ Example 20 ○ ○ ○ ○ ○ ○ ○ Example 21 ○ ○ ○ ○ ○ ○ ○ Example 22 ○ ○ ○ ○ ○ ○ ○ Example 23 ○ ○ ○ ○ ○ ○ ○ Example 24 ○ ○ ○ ○ ○ ○ ○ Example 25 ○ ○ ○ ○ ○ ○ ○ Example 26 ○ ○ ○ ○ ○ ○ ○ Example 27 ○ ○ ○ ○ ○ ○ ○ Example 28 ○ ○ ○ ○ ○ ○ ○ Example 29 ○ ○ ○ ○ ○ ○ ○ Example 30 ○ ○ ○ ○ ○ ○ ○ Example 31 ○ ○ ○ ○ ○ ○ ○ Example 32 ○ ○ ○ ○ ○ ○ ○ Example 33 ○ ○ ○ ○ ○ ○ ○ Example 34 ○ ○ ○ ○ ○ ○ ○ Example 35 ○ ○ ○ ○ ○ ○ ○ Example 36 ○ ○ ○ ○ ○ ○ ○ Example 37 ○ ○ ○ ○ ○ ○ ○

division Sensitivity refractive index permeability Haze Viscosity Inkjet Fairness heat resistance Example 38 ○ ○ ○ ○ ○ ○ ○ Example 39 ○ ○ ○ ○ ○ ○ ○ Example 40 ○ ○ ○ ○ ○ ○ ○ Example 41 ○ ○ ○ ○ ○ ○ ○ Example 42 ○ ○ ○ ○ ○ ○ ○ Example 43 ○ ○ ○ ○ ○ ○ ○ Example 44 ○ ○ ○ ○ ○ ○ ○ Example 45 ○ ○ ○ ○ ○ ○ ○ Example 46 ○ ○ ○ ○ ○ ○ ○ Example 47 ○ ○ ○ ○ ○ ○ ○ Example 48 ○ ○ ○ ○ ○ ○ ○ Example 49 ○ ○ ○ ○ ○ ○ ○ Example 50 ○ ○ ○ ○ ○ ○ ○ Example 51 ○ ○ ○ ○ ○ ○ ○ Example 52 ○ ○ ○ ○ ○ ○ ○ Example 53 ○ ○ ○ ○ ○ ○ ○ Example 54 ○ ○ ○ ○ ○ ○ ○ Comparative Example 1 ○ ○ ○ X ○ ○ ○ Comparative Example 2 ○ ○ ○ X ○ ○ ○ Comparative Example 3 ○ ○ ○ X ○ ○ ○

division Sensitivity refractive index permeability Haze Viscosity Inkjet Fairness heat resistance Reference Example 1 ○ ○ ○ △ X ○ ○ Reference Example 2 ○ ○ ○ △ X ○ ○ Reference example 3 ○ ○ ○ △ ○ ○ ○ Reference Example 4 ○ ○ ○ △ ○ ○ ○ Reference Example 5 ○ ○ ○ △ ○ ○ ○ Reference Example 6 ○ ○ ○ △ X X X Reference Example 7 ○ ○ ○ △ X X ○ Reference Example 8 ○ ○ ○ △ X X ○ Reference Example 9 ○ ○ ○ △ X X X Reference example 10 ○ ○ ○ △ ○ ○ ○ Reference Example 11 ○ ○ ○ △ ○ ○ ○ Reference Example 12 ○ ○ ○ △ X ○ ○ Reference Example 13 ○ ○ ○ △ ○ ○ ○ Reference Example 14 ○ ○ ○ △ ○ ○ ○ Reference Example 15 ○ ○ ○ △ ○ ○ ○ Reference Example 16 ○ ○ ○ △ ○ ○ ○

Looking at the results of Tables 7 and 8, it was confirmed that Examples 1 to 54 exhibited low haze while having good refractive index and viscosity compared to Comparative Examples 1 to 3. In addition, compared to the comparative examples, the embodiment is superior in sensitivity, transmittance, and heat resistance as well as fairness by the inkjet coating process, so it is expected to contribute to performance improvement when applied as an optical member in a display device.

On the other hand, Reference Examples 1 to 16 of Table 9 showed a lower haze than Comparative Examples, and was confirmed to be applicable for forming an optical member of a display device.

Claims (20)

at least one olefinic monomer having a photocurable functional group;
metal oxide particles;
an amine compound having an amine group and a photocurable functional group; and
A photopolymerizable composition comprising a photoinitiator.
The photopolymerizable composition of claim 1, wherein the photocurable functional group of the olefinic monomer or the amine compound comprises a (meth)acrylate group.
According to claim 1, wherein the olefinic monomer is an aliphatic mono (meth) acrylate having 6 to 20 carbon atoms, an alicyclic mono (meth) acrylate having 6 to 30 carbon atoms, an aromatic mono (meth) acrylate having 8 to 30 carbon atoms. , At least one selected from the group consisting of aliphatic di (meth) acrylates having 6 to 30 carbon atoms, alicyclic di (meth) acrylates having 6 to 40 carbon atoms and aromatic di (meth) acrylates having 8 to 40 carbon atoms. A photopolymerizable composition.
The photopolymerizable composition of claim 1 , wherein the olefinic monomer has an absolute viscosity (measured at 25° C.) of 1 cP to 30 cP.
5. The method of claim 4, wherein the olefinic monomer is composed of a first olefinic monomer having an absolute viscosity (measured at 25°C) of 1cP or more and 7cP or less and a second olefinic monomer having an absolute viscosity (measured at 25°C) of 8cP or more and 30cP or less. A photopolymerizable composition comprising at least one selected from the group.
According to claim 5, wherein the first olefinic monomer is benzyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, ethoxy ethyl (meth) acrylate, dicyclopentenyl ( A photopolymerizable composition comprising at least one selected from the group consisting of meth) acrylate, and dicyclopentanyl (meth) acrylate.
6. The method of claim 5,
The second olefinic monomer is dicyclopentenyl oxy ethyl (meth) acrylate, phenoxy ethyl (meth) acrylate, phenoxy benzyl (meth) acrylate, isobornyl (meth) acrylate, 1,6-hexane Diol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, 2-vinyloxyethoxyethyl (meth)acrylate And a photopolymerizable composition comprising at least one selected from the group consisting of tripropylene glycol di (meth) acrylate.
The photopolymerizable composition according to claim 5, comprising 10 to 90 parts by weight of the first olefinic monomer and 10 to 90 parts by weight of the second olefinic monomer, based on 100 parts by weight of the total of the olefinic monomer.
The method according to claim 1, wherein the metal oxide particles have an average particle diameter (D50) of 25 to 45 nm based on the secondary particle diameter of the dispersed medium,
A photopolymerizable composition comprising a metal element selected from the group consisting of Zn, Zr, Ti, Hf and Ce.
According to claim 1, wherein the amine compound is a compound of Formula 1, ethyl dimethylamino benzoate, butoxyethyl dimethylamino benzoate, bis (diethylamino) benzophenone, bis (2-hydroethyl) -tol Ruidine, ethylhexyl-(dimethylamino)benzoate, 2-(dimethylamino)ethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(diisopropylamino)ethyl (meth) acrylate, 2-(acryloyloxy)ethyl 4-(dimethylamino)benzoate, 2-ethylhexyl 4-(dimethylamino)benzoate, ethyl 2-(dibutylamino)methyl acrylate and 4, A photopolymerizable composition comprising at least one selected from the group consisting of 4-(oxybis(ethane-2, 1-diyl))bis(oxy)bis(dimethylaniline):
[Formula 1]

In Formula 1, R ₁ and R ₂ each independently represent an alkyl group having 1 to 5 carbon atoms, R ₃ is an alkyl group having 1 to 20 carbon atoms, an ether group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amine group or a (meth)acrylate group.
The photopolymerizable composition according to claim 1, wherein the photopolymerization initiator comprises at least one selected from the group consisting of triazine-based, benzoin-based, benzophenone-based, imidazole-based, xanthone-based, oxime ester-based and acetophenone-based compounds.
The photopolymerizable composition of claim 1, further comprising at least one dispersant selected from the group consisting of an acrylic dispersant, an epoxy dispersant, and a silicone dispersant.
According to claim 12, Based on 100% by weight of the total of the photopolymerizable composition,
5 wt% to 88 wt% of an olefinic monomer;
10 wt% to 70 wt% of metal oxide particles;
0.1 to 10% by weight of an amine compound;
0.1% by weight to 30% by weight of a dispersant; and
A photopolymerizable composition comprising; 0.1 wt% to 10 wt% of a photoinitiator.
The photopolymerizable composition according to claim 1, wherein the absolute viscosity (measured at 25° C.) is 5 cP to 30 cP.
write; and
The optical member containing the cured film containing the hardened|cured material of the photopolymerizable composition of any one of Claims 1-14.
The optical member of claim 15 , wherein the cured product includes a polymer including a unit in which photocurable functional groups of the olefinic monomer and the amine compound are crosslinked, and a dispersant and a metal oxide dispersed on the polymer.
The optical member according to claim 15, wherein the cured film has a refractive index of 1.6 or more and a haze of 3% or less.
The optical member according to claim 15, which is used as an optical film.
The optical member according to claim 15, wherein the cured film is patterned in a polyhedral shape. A display device comprising the optical member of claim 15 .